THE SAME

Inventors: Shijun Zheng, Jeffrey R. Hammaker, Hiep Luu, Peng Wang, Jie Cai, Xinliang Ding, and Tissa

Sajoto

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application No. 63/152,309, filed February 22, 2021, and U.S. Provisional Application No. 63/278,904, filed November 12, 2021, which are incorporated by reference in their entireties.

BACKGROUND

In color reproduction the gamut, or color gamut, is a certain complete subset of colors available on a device such as a television or monitor. For example, Adobe™ Red Green Blue (RGB), a wide-gamut color space achieved by using pure spectral primary colors, was developed to provide a broader color gamut and offer a more realistic representation of visible colors viewed through a display. It is believed that a device which could provide a wider gamut could enable the display to portray more vibrant colors.

As high-definition large screen displays become more common, the demand for higher performance, slimmer and highly functional displays has increased. Current light emitting diodes (LEDs) are obtained by a blue light source exciting a green phosphor, a red phosphor or a yellow phosphor to obtain a white light source. However, the full width half maximum (FWHM) of the emission peak of the current green and red phosphors are quite large usually greater than 40 nm, resulting in the green and red color spectrums overlapping and rendering colors that are not fully distinguishable from one another. This overlap leads to poor color rendition and the deterioration of the color gamut.

To correct the deterioration in the color gamut, methods have been developed using films containing quantum dots in combination with LEDs. However, there are problems with the use of quantum dots. First, cadmium-based quantum dots are extremely toxic and are banned from use in many countries due to health safety issues. Second, non-cadmium-based quantum dots have a very low efficiency in converting blue LED light to green and red light. Thirdly, quantum dots require expensive encapsulating processes for protection against moisture and oxygen. Lastly, the cost of using quantum dots is high, because of the difficulties in controlling size uniformity during the production process. Therefore, there exists a need for improving performance in color conversion films, backlight units, and display devices.

SUMMARY

Photoluminescent complexes described herein may be used to improve the contrast between distinguishable colors in televisions, computer monitors, smart devices and any other device that utilizes color displays. The photoluminescent complexes of the present disclosure provides novel color converting dye complex with good blue light absorbance and narrow emissions bandwidths, e.g., with a full width half maximum [FWHM] of emission band of less than 40 nm. In some embodiments, a photoluminescent complex absorbs light of a first wavelength and emits light of a second higher wavelength than the first wavelength. The photoluminescent complexes disclosed herein can be utilized with a color conversion film for use in light emitting apparatuses. The color conversion film of the present disclosure reduced color deterioration by reducing overlap within the color spectrum resulting in high quality color rendition.

Some embodiments include a photoluminescent complex, wherein the photoluminescent complex may comprise: a blue light absorbing moiety; a linker complex wherein the linker complex is an substituted ester, a unsubstituted ester, a substituted ether, or a unsubstituted ether; and a boron- dipyrromethene (BODIPY) moiety. In some embodiments, the blue light absorbing moiety is a xanthenoisoquinoline derivative. In some embodiments, the linker complex can covalently link the xanthenoisoquinoline derivative to the BODIPY moiety. In some embodiments, the xanthenoisoquinoline derivative absorbs light of a first excitation wavelength and transfers an energy to the BODIPY moiety. In some embodiments, the BODIPY moiety absorbs the energy from the xanthenoisoquinoline derivative and emits a light energy of a second higher wavelength.

In some embodiments, the blue light absorbing moiety is a naphthalimide derivative. In some embodiments, the linker complex can covalently link the naphthalimide derivative to the BODIPY moiety. In some embodiments, the naphthalimide derivative absorbs light of a first excitation wavelength and transfers an energy to the BODIPY moiety. In some embodiments, the BODIPY moiety absorbs the energy from the naphthalimide derivative and emits a light energy of a second higher wavelength.

In some embodiments, the photoluminescent complex has an emission quantum yield greater than 80%. In some embodiments, the photoluminescent complex can have an emission band with a full width half maximum [FWHM] of up to 40 nm. In some embodiments, the photoluminescent complex can have a Stokes shift, the difference between the excitation peak of the blue light absorbing moiety and the emission peak of the BODIPY moiety, of equal to or greater than 45 nm. In some embodiments, the xanthenoisoquinoline derivative can be of the following general formula: , wherein each R ⁰ and R ¹⁰ may independently be a hydrogen (H), a C ₁ -C ₄ alkyl g oup, a t uo o ethyl group, an alkoxy group, -(OCH ₂ CH ₂ ) _n -OCH ₃ (wherein n is 1, 2, 3, or 4), or an optionally substituted aryl group. In some embodiments, the naphthalimide derivative can be of the following general formula: , wherein each R ⁰ and R ¹⁰ may independently be a hydrogen (H), a C ₁ -C ₄ alkyl g roup, a trifluoromethyl group, an alkoxy group, -(OCH2CH2)n-OCH3 (wherein n is 1, 2, 3, or 4), or an optionally substituted aryl group In some embodiments, the BODIPY moiety can be of the following general formula:

. In some embodiments, R ¹ and R ⁶ may independently be a hydrogen (H), an alkyl group, or an alkene group. In some embodiments R ³ and R ⁴ may be a C ₁ - C ₂ alkyl. In some embodiments, R ² and R ⁵ may be a hydrogen (H), an alkyl, a cyano (-CN), -C(=O)- (OCH ₂ CH ₂ ) _n -OCH ₃ (wherein n is 1, 2, 3, or 4), an alkyl ester, or an aryl ester. In some embodiments, R ⁷ and R ⁸ may be a hydrogen (H), a methyl group, a halide, or a C ₁ -C ₃ alkoxy group. Some embodiments include a color conversion film. In some examples, the color conversion film may comprise: a color conversion layer; wherein the color conversion layer includes a resin matrix; and a photoluminescent complex, as described herein, dispersed within the resin matrix. In some embodiments, the color conversion film may have a thickness between 1 µm to about 200 µm. In some embodiments, the color conversion film of the present disclosure can absorb blue light in the 400 nm to about 480 nm range and emit light in the 500 nm to about 560 nm wavelength range. Another embodiment includes a color conversion film that can absorb blue light in the 400 nm to about 480 nm range and emit light in the 575 nm to about 645 nm wavelength range. In some embodiments, the color conversion film can further comprise a transparent substrate layer. In some embodiments, the transparent substrate layer comprises two opposing surfaces, wherein the color conversion layer is disposed on one of the opposing surfaces. In some embodiments, the color conversion film of the present disclosure may comprise a singlet oxygen quencher. In some embodiments, the color conversion film may further comprise a radical scavenger. Some embodiments include a method for preparing the color conversion film, the method comprises: dissolving an aforedescribed photoluminescent complex and a binder resin within a solvent; and applying the mixture on one of the transparent substrates opposing surfaces. Some embodiments include a backlight unit including a color conversion film described herein. Some embodiments include a display device including the backlight unit described herein. The present application provides a photoluminescent complex having excellent color gamut and luminescent properties, a method for manufacturing color conversion films using the photoluminescent complexes, and a backlight unit including the color conversion film. These and other embodiments are described in greater detail below. BRIEF DESCRIPTION OF THE DRAWINGS FIG.1 is a graph depicting the absorption spectra of one embodiment of a photoluminescent complex (PLC-1). FIG.2 is a graph depicting the emission spectra of one embodiment of a photoluminescent complex (PLC-1). FIG.3 is a graph depicting the absorption and emission spectra of one embodiment of a photoluminescent complex (PLC-2) DETAILED DESCRIPTION The present disclosure is related to photoluminescent compounds and complexes for use in color conversion films, backlight units, and display devices. The current disclosure describes photoluminescent complexes and their uses in color conversion films. The photoluminescent complex may be used to improve and enhance the transmission of one or more desired emissive bandwidths within a color conversion film. In some embodiments, the photoluminescent complex can both enhance the transmission of a desired first emissive bandwidth and decrease the transmission of a second emissive bandwidth. For example, a color conversion film can enhance the contrast or intensity between two or more colors, increasing the distinction from one another. The present disclosure includes a photoluminescent complex that can enhance the contrast or intensity between two colors, increasing their distinction from one another. As used herein, when a compound or chemical structure is referred to as being “substituted” it can include one or more substituents. A substituted group is derived from the unsubstituted parent structure wherein one or more hydrogen atoms on the parent structure have been independently replaced by one or more substituent groups. In one or more forms, the substituent groups may be independently selected from an optionally substituted alkyl, alkenyl, or a C3-C7 heteroalkyl. An alkyl moiety may be branched, straight chain (i.e., unbranched), or cyclic. In some embodiments, the alkyl moiety may have 1 to 8 carbon atoms. The alkyl group of the compounds designated herein may be designated as “C ₁ -C ₈ alkyl” or similar designations. By way of example only, “ C ₁ -C ₈ alkyl” indicates that there are 1, 2, 3, 4, 5, 6, 7, or 8 carbon atoms in the alkyl chain, i.e., the alkyl chain is methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, and any isomers thereof. Thus, C ₁ -C ₈ alkyl includes C ₁ -C ₂ alkyl, C ₁ -C ₃ alkyl, C ₁ -C ₄ alkyl, C ₁ - C ₅ alkyl, C ₁ -C ₆ alkyl, C ₁ -C ₇ alkyl, and C ₁ -C ₈ alkyl. Alkyl groups can be substituted or unsubstituted. Typical alkyl groups include, but are in no way limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, hexyl, ethenyl, propenyl, butenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. The term “heteroalkyl” as used herein refers to an alkyl group, as defined herein, in which one or more of the constituent carbon atoms have been replaced by a nitrogen, oxygen, or sulphur. Examples include but are not limited to, -CH ₂ -O-CH ₃ , -CH ₂ -CH ₂ -O-CH ₃ , -CH ₂ -NH-CH ₃ , -CH ₂ -N(CH ₃ )-CH ₃ , -CH ₂ -CH ₂ -NH-CH ₃ , -CH ₂ -CH ₂ -N(CH ₃ )-CH ₃ , -CH ₂ -S -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -S(O)-CH ₃ . In addition, up to two heteroatoms may be consecutive, such as, by way of example, -CH ₂ -NH-O-CH ₃ , etc. The term “aromatic” refers to a planar ring having a delocalized π-electron system containing 4n+2 π electrons, where n is an integer. Aromatic rings can be formed from five, six, seven, eight, nine, or more than nine atoms. Aromatic rings can be optionally substituted. The term “aromatic” includes both carbocyclic aryl (e.g., phenyl) and heterocyclic aryl (or “heteroaryl” or heteroaromatic”) group (e.g., pyridine). The term includes monocyclic or fused-ring polycyclic (i.e., rings which share adjacent pairs of carbon atoms) groups. The term “hydrocarbon ring” refers to a monocyclic or polycyclic ring or ring system that contains only carbon and hydrogen and may be saturated. Monocyclic hydrocarbon rings include groups having from 3 to 12 carbon atoms. Illustrative examples of monocyclic groups include the following moieties: , and the like. Illustrative examples of polycyclic groups include the following moieties: y p , y p , y , tetrahydropentalene]. The term “aryl” as used herein refers to an aromatic ring wherein each of the atoms forming the ring is a carbon atom. Aryl rings can be formed by five, six, seven, eight, or more than eight carbon atoms. Aryl groups can be substituted or unsubstituted. Examples of aryl groups include, but are not limited to phenyl, naphthalenyl, phenanthrenyl, etc. The term “aralkyl” refers to an alkyl group substituted with an aryl. Non-limiting aralkyl groups include benzyl, phenethyl; and the like. The term “heteroaryl” refers to an aryl group that includes one or more ring heteroatoms selected from nitrogen, oxygen and sulfur, wherein the heteroaryl group has from 4 to 10 atoms in its ring system. It is understood that the heteroaryl ring can have additional heteroatoms in the ring. In heteroaryls that have two or more heteroatoms, those two or more heteroatoms can be the same or different from one another. Heteroaryls can be optionally substituted. An N-containing heteroaryl moiety refers to an aryl group in which a skeletal atom of the ring is a nitrogen atom. Illustrative examples of heteroaryl groups include the following moieties: pyrrole, imidazole etc. The term “halogen” as used herein refers to fluorine, chlorine, bromine, and iodine The term “bond”, “bonded”, “direct bond” or “single bond” as used herein refers to a chemical bond between two atoms or to two moieties when the atoms joined by the bond are considered to be part of a larger structure. The term “moiety” as used herein refers to a specific segment or functional group of a molecule. Chemical moieties are often recognized chemical entities embedded in or appended to a molecule. The term “cyano” or “nitrile” as used herein refers to any organic compound that contains a - CN functional group. The term “ester” refers to a chemical moiety with the formula -COOR, where R comprises alkyl, cycloalkyl, aryl, heteroaryl (bonded through a ring carbon) or heterocyclic (bonded through a ring carbon). Any hydroxy, or carboxyl side chain on the compounds described herein can be esterified. Any suitable procedures and specific groups to make such esters may be utilized. As used herein the term “ether” refers to a chemical moiety that contains an oxygen atom connected to two alkyl or aryl groups with the general formula of R-O-R’, where R and R’ are alkyl and/or aryl. Similarly, the term “alkoxy” refers to a chemical moiety that contains an oxygen atom bonded to an alkyl group that is further bonded to an alkyl or aryl group. As used herein the term “ketone” refers to the chemical moiety that contains a carbonyl group (a carbon-oxygen double bond) connected to two alkyl or aryl groups with the general formula of RC(=O)R’, where R and R’ are alkyl and/or aryl. The term “BODIPY” as used herein, refers to a chemical moiety with the formula:

The BODIPY moiety may be composed of a dipyrromethene complexed with a di-substituted boron atom, typically a BF ₂ unit. The IUPAC name for the BODIPY core (i.e., without any substituents) is 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene. The term “xanthenoisoquinoline” or “xanthenoisoquinoline derivative” as used herein, refers to a chemical moiety with the formula: e.g., 1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione. The term “naphthalimide” or “naphthalimide derivative” as used herein, refers to a chemical moiety with the formula: . The present disclosure related to photoluminescent complexes that absorb light energy of a first wavelength and emit light energy in a second higher wavelength. The photoluminescent complex of the present disclosure comprises an absorbing luminescent moiety and an emitting luminescent moiety that are coupled through a linker such that their distance is adjusted for the absorbing luminescent moiety to transfer its energy to the acceptor luminescent moiety, wherein the acceptor luminescent moiety then emits out at a second wavelength that is larger than the absorbed first wavelength. In some embodiments, a photoluminescent complex comprises: a blue light absorbing moiety, a linker complex, and a boron-dipyrromethene (BODIPY) moiety. In some embodiments, the blue light absorbing moiety is a xanthenoisoquinoline derivative. In some embodiments, the linker complex can covalently link the xanthenoisoquinoline derivative to the BODIPY moiety. In some embodiments, the xanthenoisoquinoline derivative absorbs light of a first excitation wavelength and transfers energy to the BODIPY moiety, the BODIPY moiety then emits a light energy of a second wavelength, wherein the light energy of the second wavelength is higher than the first wavelength. In some embodiments, the blue light absorbing moiety is a naphthalimide derivative. In some embodiments, the linker complex can covalently link the naphthalimide derivative to the BODIPY moiety. In some embodiments, the naphthalimide derivative absorbs light of a first excitation wavelength and transfers energy to the BODIPY moiety, the BODIPY moiety then emits a light energy of a second wavelength, wherein the light energy of the second wavelength is higher than the first wavelength. It is believed that energy transfer from the excited xanthenoisoquinoline derivative or naphthalimide derivative to the BODIPY moiety occurs through a Förster resonance energy transfer (FRET). This belief is due to the absorbance/emission spectra of the photoluminescent complexes where there are two major absorption bands, one at the blue light absorption band (xanthenoisoquinoline derivative or naphthalimide derivative) and one at the BODIPY absorption band, and only one emission band located at the BODIPY moieties emission wavelength (see FIGS.1 and 2). In some embodiments, the photoluminescent complex can have a high emission quantum yield. In some embodiments, the emission quantum yield can be greater than 50%, 60%, 70%, 80%, or 90%. In some embodiments, the emission quantum yield can be greater than 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%. Emission quantum yield can be measured by dividing the number of photons emitted by the number of photons absorbed, which is equivalent to the emission efficiency of the luminescent moiety. In some embodiments, the absorbing luminescent moiety, may have an emission quantum yield greater than 80%. In some embodiments, the quantum yield can be greater than 0.8 (80%), 0.81 (81%), 0.82 (82%), 0.83 (83%), 0.84 (84%), 0.85 (85%), 0.86 (86%), 0.87 (87%), 0.88 (88%), 0.89 (89%), 0.9 (90%), 0.91 (91%), 0.92 (92%), 0.93 (93%), 0.94 (94%), or 0.95 (95%), and may be up to nearly 1 (100%). Quantum yield measurements in film can be made by spectrophotometer, e.g., Quantaurus-QY spectrophotometer (Hamamatsu, Inc., Campbell, CA, USA). In some embodiments, the photoluminescent complex has an emission band, the emission band can have a full width half maximum (FWHM) of less than 40 nm. The FWHM is the width of the emission band in nanometers at the emission intensity that is half of the maximum emission intensity for the band. In some embodiments, the photoluminescent complex has an emission band FWHM value that is less than or equal to about 35 nm, less than or equal to about 30 nm, less than or equal about 25 nm, less than or equal to about 20 nm. In some embodiments, the photoluminescent complex can have a Stokes shift that is equal to or greater than 45 nm. As used herein the term “Stokes shift” means the distance between the excitation peak of the blue light absorbing moiety and the emission peak of the BODIPY moiety. The photoluminescent complex of the current disclosure can have a tunable emission wavelength. By substituting in different substituents to the BODIPY moiety the emission wavelength can be tuned between about 500 nm to about 560 nm or any number bound by this range. In some embodiments, the blue light absorbing moiety can have a peak absorption maximum between about 400 nm to about 470 nm wavelength. In some embodiment, the peak absorption can be between about 400 nm to about 405 nm, about 405-410 nm, about 410-415 nm, about 415-420 nm, about 420-425 nm, about 425-430 nm, about 430-435 nm, about 435-440 nm, about 440-445 nm, about 445-450 nm, about 450-455 nm, about 455-460 nm, about 460-465 nm, about 465-470 nm, or any wavelength in a range bounded by any of these values. In some embodiments, the photoluminescent complex can have an emission peak between about 500 nm and about 560 nm. In some embodiments, the emission peak can be between about 500 nm to about 515 nm, about 515 nm to about 520 nm, about 520 nm to about 525 nm, about 525 nm to about 530 nm, about 530 nm to about 535 nm, about 535 nm to about 540 nm, about 540 nm to about 545 nm, about 545 nm to about 550 nm, about 550 nm to about 555 nm, about 555 nm to about 560 nm, or any wavelength in a range bounded by any these ranges. Some embodiments include the photoluminescent complex wherein the blue light absorbing xanthenoisoquinline or derivative and the BODIPY moiety’s spatial distance is adjusted through the linker complex, for transfer of the blue light absorbing xanthenoisoquinoline derivative’s energy to the BODIPY moiety. Other embodiments include the photoluminescent complex wherein the blue light absorbing naphthalimide derivative and the BODIPY moiety’s spatial distance is adjusted through the linker complex, for transfer of the blue light absorbing naphthalimide derivative’s energy to the BODIPY moiety. The present disclosure includes a photoluminescent complex (PLC), wherein the photoluminescent complex may comprise a blue light absorbing xanthenoisoquinoline derivative, a linker complex, and a BODIPY moiety. The linker complex covalently links the blue light absorbing xanthenoisoquinoline derivative and the BODIPY moiety. In some embodiments, the xanthenoisoquinoline derivative absorbs light energy of a first excitation wavelength and transfers an energy to the BODIPY moiety, wherein the BODIPY moiety absorbs the energy from the xanthenoisoquinoline derivative and emits a light energy of a second higher wavelength, and wherein the photoluminescent complex has an emission quantum yield greater than 80%. Some embodiments include a blue light absorbing xanthenoisoquinoline derivative, wherein the blue light absorbing xanthenoisoquinoline derivative may be of the following general formula: , wherein, R ⁰ and R ¹⁰ may be a hydrogen (H), a C ₁ -C ₄ alkyl group (e.g. methyl, n-butyl, t-butyl, etc.), a trifluoromethyl group, an optionally substituted aryl group, -(OCH ₂ CH ₂ )n-OCH ₃ , wherein n is 1, 2, 3, or 4, or an alkoxy group. In some embodiments, R ¹⁰ is C _1-4 alkyl, such as methyl, ethyl, n-propyl, isopropyl, butyl, t-butyl, etc. In some embodiments, R ¹⁰ is t-butyl.

In some embodiments, R ¹⁰ may be unsubstituted phenyl, , In some embodiments, R ¹⁰ may be unsubstituted phenyl. In some embodiments, R ¹⁰ may be In some embo ¹⁰ diments, R may be ome embodiments, R ¹⁰ may be . In some embodiments, R ¹⁰ may be some embodiments, R ¹⁰ may be . In some embodiments, R ¹⁰ may be . In some embodiments, R ¹⁰ may be n some embodiments, R ¹⁰ may be In some embodiments, R ¹⁰ may comprise an alkoxy moiety, including, but not limited to, methoxy (-OMe), or . In some embodiments, R ¹⁰ may be methoxy. In some embodiments, R ¹⁰ may be . Some embodiments include a photoluminescent complex (PLC), wherein the photoluminescent complex may comprise a blue light absorbing naphthalimide derivative, a linker complex, and a BODIPY moiety. The linker complex covalently links the blue light absorbing naphthalimide derivative and the BODIPY moiety. In some embodiments, the naphthalimide derivative absorbs light energy of a first excitation wavelength and transfers an energy to the BODIPY moiety, wherein the BODIPY moiety absorbs the energy from the naphthalimide derivative and emits a light energy of a second higher wavelength. In such embodiments, the photoluminescent complex has an emission quantum yield greater than 80%. Some embodiments include a blue light absorbing naphthalimide derivative, wherein the blue light absorbing naphthalimide derivative may be of the following general formula: , wherein R ⁰ and R ¹⁰ are defined as above for the xanthenoisoquinoline derivatives. The linker complex covalently links the blue absorbing xanthenoisoquinoline derivative (or the naphthalimide derivative) with the BODIPY moiety. The linker complex can be tuned to adjust the spatial distance between the blue light absorbing xanthenoisoquinoline derivative (or the naphthalimide derivative) and the BODIPY moiety. By adjusting the spatial distance between the xanthenoisoquinoline derivative (or the naphthalimide derivative) and the BODIPY, the quantum yield maybe tuned. In some embodiments, the distance separating the blue light absorbing xanthenoisoquinoline derivative (or the naphthalimide derivative) and the BODIPY moiety can be about 8 Å or less. The linker complex can maintain a distance between the blue light absorbing xanthenoisoquinoline derivative (or the naphthalimide derivative) and the BODIPY moiety. In some embodiments, the photoluminescent complex comprises a linker complex, wherein the linker complex covalently links the blue light absorbing xanthenoisoquinoline derivative to the BODIPY moiety. In some embodiments, the linker complex can comprise a single bond between the xanthenoisoquinoline derivative and the BODIPY moiety. In many embodiments, the photoluminescent complex comprises a linker complex, wherein the linker complex covalently links the blue light absorbing naphthalimide derivative to the BODIPY moiety. In some embodiments, the linker complex can comprise a single bond between the naphthalimide derivative and the BODIPY moiety. In some embodiments, the linker complex can comprise a substituted ester, an unsubstituted ester, a substituted ether, or an unsubstituted ether. In some embodiments, the linker complex can comprise an optionally substituted ester group. In some embodiments, the linker complex comprises a substituted ester group, wherein the linker complex may have the following structure: , In some embodiments, the linker complex may comprise an unsubstituted ester group, wherein the linker complex may have the following structure: , In some embodiments, the linker complex may be: In some embodiments, the linker complex may be: . In some embodiments, the linker complex may be: . In some embodiments, the linker complex may be: . In some embodiments, the linker complex may be: In some embodiments, the linker complex may be: . In some embodiments, the linker complex may be: -O(CH ₂ ) ₆ -. In some embodiments, the linker complex may be: . In some embodiments, the linker complex may be: . In some embodiments, the linker complex may be: . In some embodiments, the linker complex may be: . In some embodiments, the linker complex may be: . In some embodiments, the linker complex may be: . In some embodiments, the linker complex may be: . In some embodiments, the linker complex may be: . In some embodiments, the linker complex may be: . In some embodiments, the linker complex may be: . In some embodiments, the linker complex may be: . In some embodiments, the linker complex may be: . In some embodiments, the linker complex may be: In some embodiments, the linker complex may be: -O(CH ₂ ) ₆ -. In some embodiments, the linker complex may be: . The photoluminescent complex of the current disclosure can comprise a BODIPY moiety. The BODIPY moiety can have the following general formula:

, wherein R ¹ and R ⁶ can be independently selected from a hydrogen (H), a saturated or unsaturated alkyl group, e.g., a methyl group, and / or an alkene group; wherein R ³ and R ⁴ can be independently selected from a C ₁ -C ₂ alkyl, e.g., a methyl group; wherein R ² and R ⁵ , can be independently selected from a hydrogen (H), a saturated alkyl, an unsaturated alkyl, a cyano (-CN), an alkyl ester (e.g., ethyl ester, 2-ethyl-hexyl ester, 2,2,2- trifluoroeethyl ester, a glycol ester), or an aryl ester (e.g., a benzyl ester (-COOCH ₂ Ph)); wherein R ⁷ and R ⁸ can be independently selected from a hydrogen (H), a C ₁ -C ₃ alkyl (e.g., methyl (-CH ₃ )), a halide (e.g., F or Cl), and/or a C ₁ -C ₃ alkoxy, (e.g., methoxy (-OCH ₃ )); and wherein L can represent the linker complex comprising an optionally substituted ester or an optionally substituted ether linker. In some embodiments, the BODIPY moiety of the present disclosure may be a BODIPY moiety wherein R ¹ , R ³ , R ⁴ and R ⁶ are each a methyl; R ² and R ⁵ are may be a substituted ester group, wherein the substituted ester group comprises a C ₁ -C ₇ alkyl chain or a polyglycol chain;R ⁷ and R ⁸ are each a methyl; and L comprises a linker complex.

In some embodiments, R ² and R ⁵ may be independently , , , or . In some embodiments, R ² is . In some embodiments, R ² is In some embodiments, R ² is . In some embodiments, R ² is In some embodiments, R ² is or In some embodiments, R ⁵ is In some embodiments, R ⁵ is . In some embodiments, R ⁵ is . In some embodiments, R ⁵ is In some embodiments, R ⁵ is The photoluminescent complex of the present disclosure may be represented by the following which are provided for purpose of illustration and are in no way to be construed as limiting:

(PLC-1), C-2),

(PLC-3), ( C-4),

C-5), ( LC-6),

C-7), LC-8),

(PLC-9), (PLC-10), (LC-11),

(PLC-12), (PLC-13), LC-14),

(PLC-15), ( C-16), LC-17), C-18),

( LC-19), (PLC-20), PLC-21), C-22),

(PLC-23), (PLC-24), ( C-25),

(PLC-26), (PLC-27), ( LC-29), LC-32),

C-33), LC-34), C-35), LC-36),

( C-37), (PLC-38), ( C-39), and/or ( LC-40). Some embodiments include a photoluminescent complex, wherein the photoluminescent complex comprises a blue light absorbing xanthenoisoquinoline derivative. The blue light absorbing xanthenoisoquinoline derivative can comprise an organic lumiphore. In some embodiments, the xanthenoisoquinoline derivative may have a maximum absorbance in the light in the range of 400 nm to about 480 nm, about 400 nm to about 410 nm, about 410 nm to about 420 nm, about 420 nm to about 430 nm, about 430 nm to about 440 nm, about 440 nm to about 450 nm, about 450 nm to about 460 nm, about 460 nm to about 470 nm, about 470 nm to about 480 nm, or any wavelength in a range that is bounded by any of these values. In some embodiments, the photoluminescent complex can have an absorbance maximum peak of about 450 nm. In other embodiments, the blue light absorbing xanthenoisoquinoline derivative can have a maximum peak absorbance of about 405 nm. In still other embodiments, the blue light absorbing xanthenoisoquinoline derivative can have a maximum peak absorbance of about 480 nm. Some embodiments include a photoluminescent complex, wherein the photoluminescent complex comprises a blue light absorbing naphthalimide derivative. The blue light absorbing naphthalimide derivative can comprise an organic lumiphore. In some embodiments, the naphthalimide derivative may have a maximum absorbance in the light in the range of 400 nm to about 480 nm, about 400 nm to about 410 nm, about 410 nm to about 420 nm, about 420 nm to about 430 nm, about 430 nm to about 440 nm, about 440 nm to about 450 nm, about 450 nm to about 460 nm, about 460 nm to about 470 nm, about 470 nm to about 480 nm, or any wavelength in a range that is bounded by any of these values. In some embodiments, the photoluminescent complex can have an absorbance maximum peak of about 450 nm. In other embodiments, the blue light absorbing naphthalimide derivative can have a maximum peak absorbance of about 405 nm. In still other embodiments, the blue light absorbing naphthalimide derivative can have a maximum peak absorbance of about 480 nm. Some embodiments include a color conversion film, wherein the color conversion film comprises: a color conversion layer wherein the color conversion layer includes a resin matrix and photoluminescent complexes, described above, dispersed within the resin matrix. In some embodiments, the color conversion film may comprise one or more of the complexes described herein. Some embodiments include the color conversion film which may be about 1 µm to about 200 µm thick. In some embodiments, the color conversion film has a thickness of about 1 µm to about 5 µm, about 5 µm to about 10 µm, about 10 µm to about 15 µm, about 15 µm to about 20 µm, about 20 µm to about 40 µm, about 40 µm to about 80 µm, about 80 µm to about 120 µm, about 120 µm to about 160 µm about 160 µm to about 200 µm, or any thickness in a range bounded by any value above. In some embodiments, the color conversion film can absorb light in the wavelength range of about 400 nm to about 480 nm and can emit light in the wavelength range of about 500 nm to about 560 nm. In some embodiments, the color conversion film can further comprise a transparent substrate layer. The transparent substrate layer has two opposing surfaces, wherein the color conversion layer can be disposed on and in physical contact with the surfaces of the transparent layer that will be adjacent to a light emitting source. The transparent substrate is not particularly limited and one skilled in the art would be able to choose a transparent substrate from those used in the art. Some non- limiting examples of transparent substrates include PE (polyethylene), PP (polypropylene), PEN (polyethylene naphthalate), PC (polycarbonate), PMA (polymethyl acrylate), PMMA (Polymethylmethacrylate), CAB (cellulose acetate butyrate), PVC (polyvinylchloride), PET (polyethyleneterephthalate), PETG (glycol modified polyethylene terephthalate), PDMS (polydimethylsiloxane), COC (cyclo olefin copolymer), PGA (polyglycolide or polyglycolic acid), PLA (polylactic acid), PCL (polycaprolactone), PEA (polyethylene adipate), PHA (polyhydroxy alkanoate), PHBV (poly(3-hydroxybutyrate-co-3hydroxyvalerate)), PBE (polybutylene terephthalate), PTT (polytrimethylene terephthalate). Any of the aforedescribed , alone or in combination, may comprise the transparent substrate layer. In some embodiments, the transparent substrate may have two opposing surfaces. In some embodiments, the color conversion film may be disposed on and in physical contact with one of the opposing surfaces. In some embodiments, the side of the transparent substrates without color conversion film disposed thereon, may be adjacent to a light source. In some examples, the substrate may function as a support during the preparation of the color conversion film. The type of substrates used are not particularly limited, and the material and/or thickness is not limited, as long as it is transparent and capable of functioning as a support. A person skilled in the art could determine which material and thickness to use as a supporting substrate. Some embodiments include a method for preparing the color conversion film, wherein the method comprises: dissolving a photoluminescent compound, described herein, and a binder resin within a solvent; and applying the mixture on to the surface of the transparent substrate. The binder resin which can be used with the photoluminescent complex(s) includes resins such as acrylic resins, polycarbonate resins, ethylene-vinyl alcohol copolymer resins, ethylene-vinyl acetate copolymer resins and saponification products thereof, AS resins, polyester resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins, polyvinylphosphonic acid (PVPA), polystyrene resins, phenolic resins, phenoxy resins, polysulfone, nylon, cellulosic resins, and cellulose acetate resins. In some embodiments, the binder resin can be a polyester resin and/or acrylic resin. In some embodiments, the solvent which can be used for dissolving or dispersing the complex and the resin can include an alkane, such as butane, pentane, hexane, heptane, and octane; cycloalkanes, such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane; alcohols, such as ethanol, propanol, butanol, amyl alcohol, hexanol, heptanol, octanol, decanol, undecanol, diacetone alcohol, and furfuryl alcohol; Cellosolves™, such as Methyl Cellosolve™, Ethyl Cellosolve™, Butyl Cellosolve™, Methyl Cellosolve™ acetate, and Ethyl Cellosolve™ acetate; propylene glycol and its derivatives, such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, and dipropylene glycol dimethyl ether; ketones, such as acetone, methyl amyl ketone, cyclohexanone, and acetophenone; ethers, such as dioxane and tetrahydrofuran; esters, such as butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate, ethyl 2-hydroxybutyrate, ethyl acetoacetate, methyl lactate, ethyl lactate, and methyl 3-methoxypropionate; halogenated hydrocarbons, such as chloroform, methylene chloride, and tetrachloroethane; aromatic hydrocarbons, such as benzene, toluene, xylene, and cresol; and highly polar solvents, such as dimethyl formamide, dimethyl acetamide, and N-methylpyrrolidone. Some embodiments include a backlight unit, wherein the backlight unit may include the aforedescribed color conversion film. Other embodiments include a display device, wherein the device may include the backlight unit described hereinto. Unless otherwise indicated, all numbers expressing quantities of ingredients, properties, such as, molecular weight, reaction conditions, and so forth used in the specification and embodiments are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and attached embodiments are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, and not as an attempt to limit the application of the doctrine of equivalents. To the scope of the embodiments, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. For the processes and/or methods disclosed, the functions performed in the processes and methods may be implemented in differing order, as may be indicated by context. Furthermore, the outlined steps and operations are only provided as examples and some of the steps and operations may be optional, combined into fewer steps and operations, or expanded into additional steps and operations. This disclosure may sometimes illustrate different components contained within, or connected with, different other components. Such depicted architectures are merely examples, and many other architectures can be implemented which achieve the same or similar functionality. The terms used in this disclosure and in the appended embodiments, (e.g., bodies of the appended embodiments) are generally intended as “open” terms (e.g., the term “including” should be interpreted as “including, but not limited to,” the term “having” should be interpreted as “having at least,” the term “includes” should be interpreted as “includes, but not limited to,” etc.). In addition, if a specific number of elements is introduced, this may be interpreted to mean at least the recited number, as may be indicated by context (e.g., the bare recitation of “two recitations,” without other modifiers, means at least two recitations of two or more recitations). As used in this disclosure, any disjunctive word and/or phrase presenting two or more alternative terms should be understood to contemplate the possibilities of including one of the terms, either of the terms, or both terms. For example, the phase “A or B”: will be understood to include the possibilities of “A” or “B” or “A and B.” The terms “a,” “an,” “the” and similar referents used in the context of describing the present disclosure (especially in the context of the following embodiments) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The use of any and all examples, or representative language (e.g., “such as”) provided herein is intended merely to better illuminate the present disclosure and does not pose a limitation on the scope of any embodiments. No language in the specification should be construed as indicating any non-embodied element essential to the practice of the present disclosure. Groupings of alternative elements or embodiments disclosed herein are not to be construed as limitations. Each group member may be referred to and embodied individually or in any combination with other members of the group or other elements found herein. It is anticipated that one or more members of a group may be included in, or deleted from, a group for reasons of convenience and/or patentability. When any such inclusion or deletion occurs, the specification is deemed to contain the group as modified thus fulfilling the written description of all Markush groups used in the appended embodiments. Certain embodiments include the best mode known to the inventors for carrying out the present disclosure. Of course, variations on these embodiments, will become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventor expects skilled artisans to employ such variations as appropriate, and the inventors intend for the present disclosure to be practiced otherwise than specifically described herein. Accordingly, the embodiments include all modifications and equivalents of the subject matter recited in the embodiments as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is contemplated unless otherwise indicated herein or otherwise clearly contradicted by context. In closing, it is to be understood that the embodiments disclosed herein are illustrative of the principles of the embodiments. Other modifications that may be employed are within the scope of the embodiments. Thus, by way of example, but not of limitation, alternative embodiments may be utilized in accordance with the teachings herein. Accordingly, the embodiments are not limited to the embodiments precisely as shown and described.

EMBODIMENTS Embodiment 1 A photoluminescent complex comprising: a blue light absorbing moiety; a linker complex; and a boron-dipyrromethene (BODIPY) moiety; wherein the linker complex covalently links the blue light absorbing moiety and the BODIPY moiety, wherein the blue light absorbing moiety absorbs light energy of a first excitation wavelength and transfers an energy to the BODIPY moiety, wherein the BODIPY moiety absorbs the energy from the blue light absorbing moiety and emits a light energy of a second higher wavelength, and wherein the photoluminescent complex has an emission quantum yield greater than 80%. Embodiment 2 The photoluminescent complex of embodiment 1, wherein the blue light absorbing moiety is a xanthenoisoquinoline derivative. Embodiment 3 The photoluminescent complex of embodiment 2, wherein the xanthenoisoquinoline derivative is of the general formula: , wherein R ⁰ is independently selected from hydrogen (H), C ₁ -C ₃ alkyl, optional substituted aryl, or optional substituted heteroaryl. Embodiment 4 The photoluminescent complex of embodiment 1, wherein the blue light absorbing moiety is a naphthalimide derivative. Embodiment 5 The photoluminescent complex of embodiment 4, wherein the naphthalimide derivative is of the general formula:

, wherein R ⁰ is independently selected from a hydrogen (H), a substituted or unsubstituted aryl, a -CF _3, a 3,5-bis(trifluoromethyl)phenyl ( re is no substitution for R ⁰ ; wherein X is independently selected from a oxygen (O) or a sulfur (S); and wherein R ¹ is independently selected from a hydrogen (H), a substituted or unsubstituted aryl, a C ₁ -C ₅ alkyl, a phenyl, a 3,5-bis(trifluoromethyl)phenyl ( ifluoromethyl)phenyl ( ), a 4-(tert-butyl)phenyl ( ), a 4-(2-(2-(2- methoxyethoxy)ethoxy)ethoxy)phenyl ( here is no substitution for R1. Embodiment 6 The photoluminescent complex of embodiment 1, wherein the BODIPY moiety is of the general formula:

, wherein R ¹ and R ⁶ are independently selected from a hydrogen (H), a saturated or unsaturated alkyl group, or an alkene group; wherein R ³ and R ⁴ are independently selected from a C ₁ -C ₂ alkyl; wherein R ² and R ⁵ are independently selected from a hydrogen (H), a saturated alkyl, an unsaturated alkyl, a cyano (-CN), an alkyl ester (-COOCH ₂ CH ₃ ), an aryl ester (-COOCH ₂ Ar), or EtO ₂ C; and wherein R ⁷ and R ⁸ are independently selected from a hydrogen (H), a methyl group, a halide, or a C ₁ -C ₃ alkoxy. Embodiment 7 The photoluminescent complex of embodiment 6, wherein R ¹ , R ³ , R ⁴ , and R ⁶ are independently selected from a C ₁ -C ₃ alkyl or a methyl group; wherein R ² and R ⁵ are independently selected from a C ₁ -C ₃ ester group or a CH ₃ CH2CO2 ester; and wherein R ⁷ and R ⁸ are independently selected from a methyl group. Embodiment 8 The photoluminescent complex of embodiment 1, wherein the BODIPY moiety comprises the following structure: Embodiment 9 The photoluminescent complex of embodiment 1, wherein the BODIPY moiety comprises the following structure:

. Embodiment 10 The photoluminescent complex of embodiment 6, wherein L is a linker complex that can be substituted ester, a unsubstituted ester, a substituted ether, or a unsubstituted ether. Embodiment 11 The photoluminescent complex of embodiment 10, wherein the unsubstituted ester comprises one of the following structures: or . Embodiment 12 The photoluminescent complex of embodiment 10, wherein the substituted ester comprises one of the following structures: , Embodiment 13 The photoluminescent complex of embodiment 10, wherein the unsubstituted and/or substituted ether comprises one of the following structures: Embodiment 14 The photoluminescent complex as in embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, or 13, wherein the photoluminescent complex comprises one of the following structures:

(PLC-15), (PLC-16),

(PLC-20), or Embodiment 15 A color conversion film comprising: a transparent substrate layer; a color conversion layer, wherein the color conversion layer includes a resin matrix; and a photoluminescent complex, wherein the photoluminescent compound comprises the photoluminescent complex as in embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14, dispersed within the resin matrix. Embodiment 16 The color conversion film of embodiment 15, further comprising a singlet oxygen quencher. Embodiment 17 The color conversion film of embodiment 15, further comprising a radical scavenger. Embodiment 18 The color conversion film of embodiment 15, wherein the color conversion film has a thickness of between 10 μm and 200 μm. Embodiment 19 The color conversion film of embodiment 15, wherein the color conversion film absorbs light in about 400 nm to about 480 nm wavelength range and emits light in the 500 nm to about 560. Embodiment 20 A method for preparing the color conversion film as in embodiments 15, 16, 17, 18, or 19, the method comprising: dissolving the photoluminescent complex as in embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14, and a binder resin within a solvent; and applying the mixture to one of the transparent substrates opposing surfaces. Embodiment 21 A backlight unit comprising the color conversion film as in embodiments 15, 16, 17, 18, or 19. Embodiment 22 A display device including the back-light unit of embodiment 21.

EXAMPLES It has been discovered that embodiments of the photoluminescent complexes described herein have improved performance as compared to other forms of dyes used in color conversion films. These benefits are further demonstrated by the following examples, which are intended to be illustrative of the disclosure only but are not intended to limit the scope or underlying principles in any way. Example 1.1 Comparative example 1 (CE-1) CE-1: 0.75 g of 4-hydoxyl-2,6-dimethylvenzaldehyde (5 mmol) and 1.04 g of 2,4- dimethylpyrrole (11 mmol) was dissolved in 100 mL of anhydrous dichloromethane. The solution was degassed for 30 minutes. Then one drop of trifluoroacetic acid was added. The solution was stirred overnight under argon gas atmosphere at room temperature. To the resulting solution, DDQ (2.0g) was added and the mixture was stirred overnight. The next day the solution was filtered and then washed with dichloromethane resulting in a dipyrrolemethane (1.9g). Next, 1.0 g of dipyrrolemethane was dissolved in 60 mL of THF. 5 mL of trimethylamine was added to the solution and then degassed for 10 minutes. After degassing, 5 mL of trifluoroboron-diethylether was added slowly followed by heating for 30 minutes at 70 °C. The resulting solution was loaded on a silica gel and purified by flash chromatography using dichloromethane as the eluent. The desired fraction was collected and dried under reduced pressure to yield 0.9 g or an orange solid (76% yield). LCMS (APCI+): calculated for C ₂₁ H ₂₄ BF ₂ N ₂ O (M+H) = 369; found: 369. ¹ H NMR (400 MHz, Chloroform-d) δ 6.64 (s, 2H), 5.97 (s, 2H), 4.73 (s, 1H), 2.56 (s, 6H), 2.09 (s, 6H), 1.43 (s, 6H). Example 1.2 Comparative Example 2 (CE-2): was synthesis as described in Wakamiya, Atsushi et al. Chemistry Letters, 37(10), 1094-1095; 2008 Example 2 Synthesis of Photoluminescent Complexes (PLC) Synthesis of PLC-1

Compound PLC-1.1 Step1: A mixture of ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (1.0g, 6.0 mmol), 4-hydroxy- 2,6-dimethylbenzaldehyde (0.449g, 3.0 mmol) and tosylic acid (50 mg, 0.29mmol) in 50 mL 1,2- dichloroethane was degassed and stirred at room temperature overnight. LCMS analysis shows that one main peak with m/e+ = 467. Step 2: To the resulting solution, DDQ (0.817g, 3.6 mmol) was added then stirred for 30 min at room temperature. LCMS analysis shows that all starting material was converted to desired product with m/e+ =465. Step 3: With ice-bath cooling, 1.7 mL triethylamine and 2.2 mL BF ₃ -diethyl ether were added sequentially to the mixture from step 2. The whole was heated at 50 ºC for one hour. LCMS analysis shows ~30% conversion. To the mixture, additional 1mL triethylamine and 1 mL BF3-diethyl ether was added, the whole was heated at 50 ºC for additional one hour. LCMS analysis shows that all stating materials were converted to desired BODIPY product with m/e+ = 513, m/e- = 512. The reaction mixture was submitted directly to silica gel and purified by flash chromatography using eluents of hexanes/ethyl acetate (0% → 30% ethyl acetate). The main desired peak was collected, and removal of solvents gave an orange solid (1.0g, in 65% yield). LCMS (APCI): calculated for C27H32BF2N2O5 (M+H): 513.2; Found: 513. 1H NMR (400 MHz, Chloroform-d) δ 7.26 (s, 3H), 6.68 (s, 2H), 4.29 (q, J = 7.1 Hz, 4H), 2.84 (s, 6H), 2.05 (s, 6H), 1.34 (t, J = 7.1 Hz, 6H). Compound PLC-1.2 A mixture of 2-nitrophenol (6.6g, 48 mmol), KOH powder (2.4g, 43 mmol) was mixed and stirred under vacuum for 30 min, then copper powder (0.4 g) was added, followed by 100 mL anhydrous DMF. The mixture was stirred for 5 min, then 4-chloronaphthalic anhydride (5.1g, 22 mmol) was added. The whole was degassed then heated at reflux for 1.5 hr. After cooled to room temperature, 100mL 20% hydrochloride acid was added dropwise into the resulted reaction mixture, which was allowed to sit for 2 hrs. The precipitate was collected by filtration, then was dried under vacuum overnight to give yellow brown solid (4.6g). It was further purified by stirred in refluxed acetic acid (50 mL) for 2 hrs, then cooled to room temperature. Filtration and dried in air gave a yellow solid (3.0g, in 41% yield). Confirmed by LCMS (APCI): calculated for C ₁₈ H ₁₀ NO ₆ (M+H): 336.0; Found: 336.1H NMR (400 MHz, Chloroform-d) δ 8.80 (dd, J = 8.5, 1.2 Hz, 1H), 8.72 (dd, J = 7.3, 1.2 Hz, 1H), 8.50 (d, J = 8.2 Hz, 1H), 8.19 (dd, J = 8.2, 1.7 Hz, 1H), 7.90 (dd, J = 8.5, 7.3 Hz, 1H), 7.79 (td, J = 7.9, 1.7 Hz, 1H), 7.54 (td, J = 8.0, 1.3 Hz, 1H), 7.39 (dd, J = 8.3, 1.2 Hz, 1H), 6.89 (d, J = 8.2 Hz, 1H). Compound PLC-1.3 A mixture of 4-(2-nitrophenoxyl)-1,8-naphthalic anhydride (2.0g, 6 mmol) and iron powder (<10um, 0.91g, 16 mmol) in acetic acid (75 mL) was heated to reflux for 30 min. The resulting solution was poured into water (220mL). The resulted precipitate was collected by filtration and washed with water and dried thoroughly in air then under vacuum to afford a yellow solid (1.65g, in 90% yield). Confirmed by LCMS (APCI): calculated for C ₁₈ H ₁₂ NO ₄ (M+H): 306.1; Found: 306. Compound PLC-1.4 Compound 4-(2-aminophnoxy)-1,8-naphthalic anhydride (1.5g, 4.9mmol), was dispersed in acetic acid (35mL) and cooled to 0 ºC. While being stirred, precooled hydrochloric acid (3mL, 37 mmol) was added, then sodium nitrite solution (3.29g, 46 mmol) in 12 mL water was added dropwise at 0 ºC. The whole was stirred for one hour at 0 ºC, then was transferred into additional funnel, and dropped into a refluxed copper sulfate solution (5.08g, 20 mmol, in 50 mL water) over one-hour period. After cooled to room temperature, the precipitate was collected by filtration, washed with water, then dried in air then in vacuum to give a yellow solid (0.92g, in 65% yield). Confirmed by LCMS (APCI): calculated for C ₁₈ H ₈ O ₄ (M-): 288.0; Found: 288.1H NMR (400 MHz, Chloroform-d) δ 8.61 (dd, J = 17.1, 8.1 Hz, 2H), 8.09 (d, J = 8.0 Hz, 1H), 7.97 (d, J = 7.9 Hz, 1H), 7.59 (t, J = 7.7 Hz, 1H), 7.40 (t, J = 8.1 Hz, 2H), 7.33 (d, J = 8.4 Hz, 1H). Compound PLC-1.5

A mixture of 1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione (100mg, 0.347 mmol), 2-(4- aminophenyl)acetic acid (135mg, 0.9 mmol) in 5mL DMF was heated 165 ºC for 2 hrs in microwave reactor. After cooled to 50 ºC, to the resulted solution, 1.5 mL acetone was added dropwise to form yellow precipitate, which was collected by filtration and washed with acetone, dried in air to give a yellow solid (88mg, in 61% yield). Confirmed by LCMS (APCI): calculated for C ₂₆ H ₁₅ NO ₅ (M-): 421.1; Found: 421.1H NMR (400 MHz, DMSO-d6) δ 8.27 (d, J = 45.1 Hz, 4H), 7.67 – 7.00 (m, 8H), 3.58 (s, 2H). Compound PLC-1

A mixture of compound PLC-1.5 (36mg, 0.086 mmol), compound PLC-1.1 (40 mg, 0.078 mmol), DMAP/TsOH salt (59mg, 0.2 mmol) and DIC (0.1 mL, 0.63 mmol) in 5 mL DCM was stirred room temperature overnight, then at 45 ºC for 2 hrs. The reaction mixture was submitted to silica gel and purified by flash chromatography using eluents of DCM/ethyl acetate (0% to 10% ethyl acetate). The desired product peak was collected and concentrated under reduced pressure. The resulting solid was further washed with methanol and dried in air to give an orange solid (38mg, in 53% yield). Confirmed by LCMS (APCI): calculated for C ₅₃ H ₄₄ BF ₂ N ₃ O ₉ (M-): 915.3; Found: 915.1H NMR (400 MHz, ) δ 8.55 (dd, J = 18.8, 8.1 Hz, 2H), 8.04 (d, J = 7.7 Hz, 1H), 7.93 (d, J = 8.0 Hz, 1H), 7.52 (dd, J = 19.7, 8.0 Hz, 3H), 7.40 – 7.23 (m, 5H), 6.96 (s, 2H), 4.19 (q, J = 7.1 Hz, 4H), 3.92 (s, 2H), 3.37 (s, 1H), 2.75 (s, 6H), 2.54 (d, J = 3.3 Hz, 1H), 2.06 (s, 6H), 1.64 (s, 6H), 1.25 (t, J = 7.1 Hz, 6H). Synthesis of PLC-2

Compound PLC-2.1 A mixture of 1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione (100mg, 0.347 mmol), 4-(4- aminophenyl)butanoic acid (125 mg, 0.7 mmol) in 5 mL DMF was heated at 165 ºC for 2.5 hrs in microwave reactor. To the mixture, 15 mL acetone was added, the resulted precipitate was collected by filtration and dried in air to give a yellow solid (120 mg, in 77% yield). Confirmed by LCMS (APCI): calculated for C ₂₈ H ₁₉ NO ₅ (M-): 449.1; Found: 449.1H NMR (400 MHz, DMSO-d6) δ 8.38 (d, J = 41.6 Hz, 4H), 7.81 – 6.97 (m, 8H), 2.69 – 2.64 (m, 2H), 2.26 (t, J = 7.2 Hz, 2H), 1.87 (p, J = 7.2 Hz, 2H). Compound PLC-2

A mixture of compound PLC-1.5 (45mg, 0.1 mmol), compound PLC-1.1 (40 mg, 0.078 mmol), DMAP/TsOH salt (59mg, 0.2 mmol) and DIC (0.1 mL, 0.63 mmol) in 5 mL DCM was stirred room temperature overnight, then at 45 ºC for 2 hrs. The reaction mixture was submitted to silica gel and purified by flash chromatography using eluents of DCM/ethyl acetate (0% to 10% ethyl acetate). The desired product peak was collected and concentrated under reduced pressure. The resulting solid was further washed with methanol and dried in air to give an orange solid (46 mg, in 62% yield). Confirmed by LCMS (APCI): calculated for C ₅₅ H ₄₉ BF ₂ N ₃ O ₉ (M+H): 944.3; Found: 944.1H NMR (400 MHz, ) δ 8.54 (dd, J = 18.7, 8.1 Hz, 2H), 7.40 – 7.25 (m, 5H), 7.20 (d, J = 8.3 Hz, 2H), 6.93 (s, 2H), 4.19 (q, J = 7.1 Hz, 4H), 2.80 (t, J = 7.6 Hz, 2H), 2.75 (s, 6H), 2.62 (t, J = 7.4 Hz, 2H), 2.10 (t, J = 7.6 Hz, 2H), 2.06 (s, 6H), 1.65 (s, 6H), 1.25 (t, J = 7.1 Hz, 6H). Synthesis of PLC-3 A mixture of 4-bromo-1,8-naphthalic anhydride (2.77g, 10 mmol), 4-bromo-2-nitrophenol (3.27g, 15 mmol) was degassed under vacuum for 30 min, then anhydrous NMP (50 mL) was added, followed by addition of sodium hydroxide (0.2g, 5mmol) and copper powder (0.318 g, 5 mmol). The mixture was sparged with argon for 20 min, then heated at 180 ºC overnight under argon atmosphere. After cooled down to room temperature, to the solution, 50mL 20% hydrochloride acid aqueous solution was added dropwise, then added 50 mL water. The resulted mixture was allowed to stand for 3 hrs, then filtered to collect the precipitate, which was dried in vacuum to afford 4.6g crude product. The crude product was dispersed in 30 mL acetone and stirred overnight at room temperature to dissolve the impurities. Filtration and dried in vacuum gave a brown yellow solid as desired product (3.3g, in 80% yield). LCMS (APCI+): calculated for C18H9BrNO6 (M+H) = 413.95; Found: 414.1H NMR (400 MHz, TCE-d2) δ 8.70 (dd, J = 8.4, 1.2 Hz, 1H), 8.63 (dd, J = 7.3, 1.2 Hz, 1H), 8.41 (d, J = 8.3 Hz, 1H), 8.24 (d, J = 2.4 Hz, 1H), 7.89 – 7.79 (m, 2H), 7.20 (d, J = 8.7 Hz, 1H), 6.82 (d, J = 8.3 Hz, 1H). Compound PLC-3.2 A mixture of compound PLC-3.1 (1.5 g, 3.6 mmol), iron powder (0.60 g, 10.8 mmol) in acetic acid (50 mL) was heated at 125 ºC for 30 min. After cooled to room temperature, to the mixture, 100 mL water was added while stirring. The resulted mixture was filtered and washed with water, dried in air and vacuum to give a solid (1.35 g, in 82% yield). LCMS (APCI-): calculated for C18H10BrNO4 = 382.98; Found: 383. 1H NMR (400 MHz, DMSO-d6) δ 9.01 – 8.26 (m, 3H), 7.96 (s, 1H), 6.93 (dd, J = 85.2, 36.5 Hz, 4H), 5.54 (s, 2H). Compound PLC-3.3 PLC-3.2 (2.65g, 6.9mmol), was dispersed in acetic acid (50mL)/water (10mL) and cooled to 0 ºC. While being stirred, precooled hydrochloric acid (2.8mL, 34.5 mmol) was added, then sodium nitrite solution (3.57g, 52 mmol) in 15 mL water was added dropwise at 0 ºC. The whole was stirred for one hour at 0 ºC, then was transferred into additional funnel, and dropped into a copper sulfate solution (12g, 47 mmol, in 140 mL water) over one hour period at 130 ºC. After cooled to room temperature, the precipitate was collected by filtration, washed with water (100mL × 3), then stirred in 50 mL acetone at 40 ºC for 30 min. Filtration, dried in air then in vacuum gave a brown yellow solid (1.76g, in 70% yield). LCMS (APCI+): calculated for C ₁₈ H ₈ BrO ₄ (M+H) = 366.95; Found: 367. 1H NMR (400 MHz, d2-TCE) δ 8.51 (dd, J = 12.3, 8.1 Hz, 2H), 8.12 (d, J = 2.3 Hz, 1H), 7.86 (d, J = 7.9 Hz, 1H), 7.60 (dd, J = 8.8, 2.3 Hz, 1H), 7.28 (d, J = 8.3 Hz, 1H), 7.23 (d, J = 8.8 Hz, 1H). Compound PLC-3.4 A mixture of PLC-3.3 (400.0 mg, 1.1 mmol), 4-aminophenylacetic acid (329.4 mg, 2.2 mmol) and DMAP (9.3 mg, 0.080 mmol) in DMF (8 mL) was degassed at room temperature. Then the mixture was heated up to 165 ºC and has been kept at this temperature for 3 hrs. TLC and LCMS showed ~95% conversion without observable side-reaction. The mixture was cooled down to 50 ºC. Then it was poured into an acetone solution (40 mL), which has been pre-chilled by water-ice bath. The mixture has been kept at 0 ºC for 2 hrs and then has been kept stirring at room temperature overnight. The solid was collected through vacuum filtration and washed by acetone (4 mL). And it was dried by vacuum oven at 100 ºC for 3 hrs to provide the pure compound PLC-3.4 as a yellow brown solid 395.0 mg, 73% yield. MS (APCI): calculated for C ₂₆ H ₁₄ BrNO ₅ ([M+H]+) = 500 found: 500.1H NMR (400 MHz, CDCl ₂ CDCl ₂ ) δ 8.65 (d, J = 8.0 Hz, 1H), 8.62 (d, J = 8.0 Hz, 1H), 8.21 (dd, J = 6.4 Hz, 2.4 Hz, 1H), 7.99 (bs, 1H), 7.95 (t, J = 7.6 Hz, 1H), 7.67 (dd, J = 8.4 Hz, 2.4 Hz, 1H), 7.53 (d, J = 8.0 Hz, 2H), 7.37 (d, J = 8.4 Hz, 1H), 7.32 (m, 3H), 2.94 (s, 2H). Compound PLC-3.5

A mixture of compound PLC-3.4 (400.0 mg, 0.80 mmol), 4-(trifluoromethyl)phenylboronic acid (262.2 mg, 1.6 mmol), Pd(dppf)Cl2 (41.0 mg, 0.056 mmol) and K ₂ CO ₃ (298.0 mg, 2.2 mmol) in THF/DMF/H2O (22 ml/ 4.4 ml/ 2.2 ml) was degassed at room temperature. The reaction mixture was heated up to 80 ºC and the reaction has been kept at this temperature overnight. TLC was used to monitor the reaction. After the completion, the reaction was worked up by the addition of 0.1N HCl (150 ml) and EtOAc (150 ml). The aqueous phase was further extracted by THF (150 ml*3). The combined organic phases were dried over anhydrous Na ₂ SO ₄ , concentrated under rotavapor and purified by flash chromatography, using DCM in EtOAc (0-40%, with 0.1% TFA) as an eluant to provide the pure RL-naphthalimide derivative PLC-3.5 as a yellow/ yellow brown solid.363.0 mg, 80% yield. MS (APCI): calculated for C ₃₃ H ₁₈ F ₃ NO ₅ ([M+H]+) = 566 found: 566.1H NMR (400 MHz, DMSO-d ₆ ) 8.76 (m, 1H), 8.56 (m, 2H), 8.52 (dd, J = 8.0 Hz, J = 3.2 Hz, 1H), 8.15 (m, 2H), 8.06 (m, 1H), 7.94 (d, J = 8.0 Hz, 2H), 7.66 (dd, J = 8.0 Hz, J = 4.0 Hz, 1H), 7.53 (m, 1H), 7.45 (d, J = 8.0 Hz, 2H), 7.33 (d, J = 8.0 Hz, 2H), 3.72 (s, 2H). Compound PLC-3

A mixture of compound PLC-3.5 (50mg, 0.089 mmol), compound PLC-3.6 (30mg, 0.059 mmol), DMAP/TsOH salt (15mg, 0.051 mmol) and EDC•HCl (60mg, 0.31mmol) in 5 mL DCM was stirred room temperature overnight. The reaction mixture was submitted to silica gel and purified by flash chromatography using eluents of DCM/ethyl acetate (0% to 10% ethyl acetate). The desired product peak was collected and concentrated under reduced pressure. The resulting solid was reprecipitated with ethyl acetate/methanol and dried in air to give an orange solid (45mg, in 72%). LCMS (APCI-): calculated for C ₆₀ H ₄₇ BF ₅ N ₃ O ₉ : 1059.33; Found: 1059.1H NMR (400 MHz, Methylene Chloride-d ₂ ) δ 8.73 (d, J = 7.9 Hz, 1H), 8.66 (d, J = 8.3 Hz, 1H), 8.39 (d, J = 2.2 Hz, 1H), 8.17 (d, J = 8.0 Hz, 1H), 7.86 (dt, J = 11.4, 8.4 Hz, 5H), 7.64 (d, J = 8.3 Hz, 2H), 7.57 (d, J = 8.6 Hz, 1H), 7.43 (d, J = 8.3 Hz, 1H), 7.41 – 7.35 (m, 2H), 7.09 (s, 2H), 4.30 (q, J = 7.1 Hz, 4H), 4.05 (s, 2H), 2.84 (s, 6H), 2.18 (s, 6H), 1.77 (s, 6H), 1.36 (t, J = 7.1 Hz, 6H). Synthesis of PLC-4

A 1 L 2N round bottom flask was placed in an aluminum heat block and charged with a stir bar. The flask was fitted with a finned condenser/gas adapter, stopper and flow control valve. The system was flushed with argon. To the flask was added 6-bromo-1H,3H-benzo[de]isochromene-1,3- dione (40.0 mmol, 11.084 g) and 4-(tert-butyl)-2-nitrophenol (60.0 mmol, 11.712g), followed by anhydrous NMP (150 mL). To the flask was added NaOH (20.0 mmol, 800 mg) and copper (powder) (20.0 mmol, 1271 mg), followed by anhydrous NMP (25 mL). The flask was stirred under argon atmosphere with the heat block set to 170 °C. The reaction was stirred at this temperature overnight. The reaction mixture was cooled to room temperature and treated with water (175 mL) and 1N HCl (44 mL). The reaction mixture was stirred for 30 minutes, then filtered off, washing with water. The precipitate was transferred to a flask with acetone/DCM and evaporated to dryness, then azeotroped with toluene. The crude product was dissolved in a small amount of DCM and treated with methanol (300 mL). The DCM and some of the methanol were removed by rotary evaporation with a hot water bath (80 °C). When all of the DCM was removed, the mixture was cooled to room temperature and the solid was filtered off. Gives a tan powder, 8.180g (52% yield). MS (APCI): calculated for C ₂₂ H ₁₇ NO ₆ (M+H) = 392; found: 392.1H NMR (400 MHz, Tetrachloroethane-d ₂ ) δ 8.82 (dd, J = 8.4, 1.2 Hz, 1H), 8.71 (dd, J = 7.3, 1.2 Hz, 1H), 8.49 (d, J = 8.3 Hz, 1H), 8.16 (d, J = 2.4 Hz, 1H), 7.91 (dd, J = 8.4, 7.3 Hz, 1H), 7.80 (dd, J = 8.6, 2.4 Hz, 1H), 7.34 (d, J = 8.6 Hz, 1H), 6.91 (d, J = 8.3 Hz, 1H), 1.43 (s, 9H). Compound PLC-4.2 A 250 mL 2N round bottom flask was placed in an aluminum heat block and charged with a stir bar. The flask was fitted with a finned condenser/gas adapter, stopper and flow control valve. The system was flushed with argon. To the flask was added Compound (6-(4-(tert-butyl)-2-nitrophenoxy)- 1H,3H-benzo[de]isochromene-1,3-dione) (10.0 mmol, 3.914 g) and 2-MeTHF (70 mL). With stirring at room temperature, added HCl in water (100 mmol, 4.0N, 25 mL) and SnCl ₂ .2H ₂ O (40.0 mmol, 9.024 g). The reaction mixture was stirred under argon atmosphere with the heat block set to 90 °C for 30 minutes. The reaction mixture was cooled to 0 °C and made basic with aqueous 2N NaOH to pH ~8 (pH paper). Filtered off the solids (slow filtration), then washed the resulting solids with 2-MeTHF (8 X 100mL). The filtrate was transferred to a separative funnel and the layers separated. The organic layer was dried over MgSO ₄ , filtered, and evaporated to dryness in vacuo. Gives 3.743 g (quantitative yield). Used in the next step without further purification. MS (APCI): calculated for C ₂₂ H ₁₉ NO ₄ (M+H) = 362; found: 362. ¹ H NMR (400 MHz, Tetrachloroethane-d ₂ ) δ 8.88 (dd, J = 8.4, 1.2 Hz, 1H), 8.69 (dd, J = 7.3, 1.2 Hz, 1H), 8.48 (d, J = 8.4 Hz, 1H), 7.89 (dd, J = 8.4, 7.3 Hz, 1H), 7.03 – 6.93 (m, 3H), 6.88 (dd, J = 8.4, 2.3 Hz, 1H), 1.35 (s, 9H). Compound PLC-4.3 A 40 mL vial was charged with a stir bar, NaNO2 (30.0 mmol, 2.070g), and water (10 mL). The vial was stirred in an ice-water bath at 0 °C. A 100 mL round bottom flask was charged with a stir bar and compound (6-(2-amino-4-(tert-butyl)phenoxy)-1H,3H-benzo[de]isochromen e-1,3-dione) (4.00 mmol, 1.446 g). To the flask was added glacial AcOH (30 mL) and con. HCl (20.0 mmol, 12.1N, 1.65 mL). The mixture was stirred at room temperature for a few minutes, then placed in an ice-water bath and stirred for ~1 minute. Began adding the solution of NaNO ₂ before the acetic acid begins to freeze. The NaNO ₂ was added over a period of a period of ~10 minutes. The diazo solution was stirred at 0 °C for 1 hour. While the diazo solution was stirring, prepared a 250 mL 2N round bottom flask with a large stir bar. The flask was fitted with a finned condenser and a dropping funnel. The flask was clamped by the off-center neck and the dropping funnel was placed in the off-center neck, so the solution would hit the top of the vortex when stirring. To this flask was added CuSO ₄ .5H ₂ O (27.4 mmol, 6.842 g) and water (80 mL). About 15 minutes before the diazo solution was done, began heating the copper solution to 130 °C. The diazo solution was transferred to the dropping funnel when the solution reached 130 °C and began adding the diazo solution dropwise with high-speed stirring over a period of ~30 minutes. When the addition was finished, the solution was heated for another 1-2 minutes, then cooled in a room temperature water bath. The precipitate was filtered off, washing with water. The precipitate was dried by suction, then the crude precipitate was dissolved/suspended in DCM and evaporated to dryness onto ~10g flash silica gel. Purified by flash chromatography on silica gel (220g, solid load, equilibrate 50% DCM/hexanes, eluting 50% DCM/hexanes (2 CV) → 100% DCM (20 CV) → isocratic DCM (15 CV) → 0% EtOAc/DCM (0 CV) → 1% EtOAc/DCM (10 CV)). The product tails. Fractions containing product were evaporated to dryness in vacuo. Gives 528 mg (38% yield). MS (APCI): calculated for C ₂₂ H ₁₆ O ₄ (M+H) = 345; found: 345. ¹ H NMR (400 MHz, Tetrachloroethane-d ₂ ) δ 8.61 (d, J = 7.9 Hz, 1H), 8.56 (d, J = 8.4 Hz, 1H), 8.05 (d, J = 2.2 Hz, 1H), 8.01 (d, J = 8.0 Hz, 1H), 7.66 (dd, J = 8.8, 2.2 Hz, 1H), 7.38 (d, J = 8.7 Hz, 1H), 7.34 (d, J = 8.4 Hz, 1H), 1.44 (s, 9H). Compound PLC-4.4 Compound PLC-4.4 was synthesized from Compound PLC-4.3 – 9-(tert-butyl)-1H,3H- isochromeno[6,5,4-mna]xanthene-1,3-dione (1.191 mmol, 410 mg) and 2-(4-aminophenyl)acetic acid (2.98 mmol, 450 mg) in anhydrous DMF (10 mL), and the mixture was heated at 160 °C for 2 hours. After workup and precipitation, obtained the product, 579 mg (quantitative yield). MS (APCI): calculated for C30H23NO5 (M+H) = 478; found: 478. ¹ H NMR (400 MHz, DMSO-d6) δ 8.48 (d, J = 7.9 Hz, 1H), 8.44 (d, J = 8.3 Hz, 1H), 8.38 (d, J = 8.1 Hz, 1H), 8.27 (d, J = 2.4 Hz, 1H), 7.69 (dd, J = 8.8, 2.3 Hz, 1H), 7.45 – 7.38 (m, 4H), 7.31 – 7.27 (m, 2H), 3.68 (s, 2H), 1.41 (s, 9H). Compound PLC-4 PLC-4 was synthesized from PLC-1.1 (0.050 mmol, 39.9 mg), PLC-4.4 – 2-(4-(9-(tert-butyl)-1,3- dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acet ic acid (0.075 mmol, 35.8 mg), DMAP.pTsOH salt (0.100 mmol, 29.4 mg), and EDC.HCl (0.075 mmol, 14.4 mg) in a manner similar to PLC-3. The crude product was purified in the usual way and triturated with hot MeOH. The product was dried in a vacuum oven at ~110 C. Gives 44.1 mg of an orange solid (91% yield). MS (APCI): calculated for C ₃₀ H ₂₃ NO ₅ (M-) = 971; found: 971. ¹ H NMR (400 MHz, Methylene Chloride-d ₂ ) δ 8.66 (d, J = 7.9 Hz, 1H), 8.59 (d, J = 8.3 Hz, 1H), 8.13 (d, J = 2.3 Hz, 1H), 8.06 (d, J = 8.0 Hz, 1H), 7.64 (dd, J = 8.7, 2.3 Hz, 1H), 7.62 – 7.56 (m, 2H), 7.39 – 7.30 (m, 4H), 7.05 (s, 2H), 4.27 (q, J = 7.1 Hz, 4H), 4.01 (s, 2H), 2.80 (s, 6H), 2.14 (s, 6H), 1.73 (s, 6H), 1.44 (s, 9H), 1.32 (t, J = 7.1 Hz, 6H). Synthesis of Compound PLC-5

To a mixture of PLC-1.7 (290mg, 1.0mmol) in ortho-dichlorobenzene (30mL), was added bromine (1.98g, 12 mmol). The mixture was heated at 75 °C for 30 hr. After cooled to room temperature, the solid was collected by filtration, dried in air to give 290mg yellow solid as desired product. The filtrate was loaded on silica gel and purified by flash chromatography using eluents of hexanes/dichloromethane (50% → 100% dichloromethane). The desired fraction was collected and removal of solvents to give 110mg yellow solid. Total product of 400mg was obtained in 89.7% yield. LCMS (APCI-): calculated for C ₁₈ H ₆ Br ₂ O ₄ (M-): 443.9; found 444. ¹ H NMR (400 MHz, d ₂ -TCE) δ 9.40 (dd, J = 8.5, 1.5 Hz, 1H), 8.71 (s, 1H), 8.67 (s, 1H), 7.60 (ddd, J = 8.4, 7.1, 1.5 Hz, 1H), 7.48 (dd, J = 8.3, 1.4 Hz, 1H), 7.38 (ddd, J = 8.5, 7.1, 1.4 Hz, 1H). Compound PLC-5.2 A mixture of PLC-5.1 (1576-85) (190mg, 0.426mmol), 4-(4-aminophenyl)butanoic acid (180 mg, 0.64 mmol), 4-(N,N-dimethylamino)-pyridine (4mg) in anhydrous N,N-dimethylformamide (DMF) (4mL) was heated at 165 °C for 2.5 hrs. after cooled to room temperature and stand overnight, the solid was collected by filtration, which was washed with acetone and dried in vacuum oven at 90 °C for 1hr to give a yellow solid (220mg, in 84.5% yield). LCMS (APCI-): calculated for C28H17Br2NO5 (M-): 604.95; found: 605. ¹ H NMR (400 MHz, DMSO-d6) δ 9.42 (dd, J = 8.6, 1.5 Hz, 1H), 8.57 (d, J = 4.6 Hz, 2H), 7.83 – 7.68 (m, 1H), 7.63 – 7.44 (m, 2H), 7.34 (d, J = 8.3 Hz, 2H), 7.31 – 7.16 (m, 2H), 2.67 (dd, J = 4.8, 2.8 Hz, 2H), 2.28 (t, J = 7.4 Hz, 2H), 1.95 – 1.80 (m, 2H). Compound PLC-5.3 A mixture of compound PLC-5.2 (100 mg, 0.165 mmol), (3,5- bis(trifluoromethyl)phenyl)boronic acid (170mg, 0.66 mmol), Pd(dppf)Cl2 (20mg, 0.027mmol) and potassium carbonate (138mg, 1 mmol) in THF/water (5 mL/0.5 mL) was degassed then heated at 80 °C for 2hrs. After cooled to room temperature, the precipitate was collected by filtration, washed with acetone, then dried in vacuum oven at 90 ºC for 2hr. A yellow solid was obtained (142mg, in 94% yield). LCMS (APCI-): calculated for C ₄₄ H ₂₃ F ₁₂ NO ₅ (M-): 873.14; found: 873. ¹ H NMR (400 MHz, d2-TCE) δ 8.65 (s, 1H), 8.40 (s, 1H), 8.17 (s, 2H), 7.96 (d, J = 19.3 Hz, 4H), 7.38 (d, J = 8.4 Hz, 1H), 7.33 (d, J = 8.0 Hz, 2H), 7.18 (d, J = 8.0 Hz, 3H), 6.90 (d, J = 6.3 Hz, 2H), 2.72 (t, J = 7.6 Hz, 2H), 2.38 (t, J = 7.4 Hz, 2H), 2.03 – 1.93 (m, 2H). Compound PLC-5 A mixture of PLC-3.6 (1576-30) (30mg, 0.058mmol), PLC-5.3 (1576-88) (70 mg, 008 mmol), DIC (0.1 mL, 0.63 mmol) and DMAP/p-TsOH (30 mg, 0.1 mmol) in DCM (5mL) was stirred at room temperature for 40 hrs. The resulted mixture was then loaded on silica gel, purified by flash chromatography using eluents of DCM/ethyl acetate (0% → 5% ethyl acetate). The desired main orange color faction was collected. After removal of solvents, the resulting solid was washed with methanol. The desired product was obtained after filtration and dried in air as orange solid (61 mg, 77% yield). LCMS (APCI-): calculated for C71H52BF14N3O9 = 1367.36; Found: 1367. ¹ H NMR (400 MHz, d2-TCE) δ 8.66 (s, 1H), 8.41 (s, 1H), 8.18 (s, 2H), 7.96 (d, J = 18.8 Hz, 4H), 7.38 (d, J = 8.2 Hz, 3H), 7.20 (dd, J = 14.5, 8.3 Hz, 3H), 7.02 – 6.84 (m, 4H), 4.19 (q, J = 7.2 Hz, 4H), 2.80 (m, 2H), 2.75 (s, 6H), 2.61 (t, J = 7.3 Hz, 2H), 2.10 (m, 2H), 2.06 (s, 6H), 1.64 (s, 6H), 1.25 (t, J = 7.1 Hz, 6H). Synthesis of Compound PLC-6

A mixture of PLC-3.3 (550 mg, 1.5 mmol), 4-(4-aminophenyl)butanoic acid (537 mg, 3 mmol) and DMAP (12.2mg, 0.1 mmol) in 10 mL DMF was heated at 165 ºC for 2.5 hrs in microwave reactor. The resulted solution was dropped into 50 mL acetone while stirring. Precipitate formed and was filtered and dried in vacuum oven at 60 ºC for overnight to afford the desired product as brown yellow solid (0.49g, in 62% yield). LCMS (APCI-): calculated for C ₂₈ H ₁₈ BrNO ₅ = 527.04; Found: 527. ¹ H NMR (400 MHz, DMSO-d ₆ ) δ 8.54 (d, J = 2.3 Hz, 1H), 8.41 (dd, J = 9.9, 8.0 Hz, 2H), 8.33 (d, J = 7.9 Hz, 1H), 7.71 (dd, J = 8.8, 2.3 Hz, 1H), 7.39 (dd, J = 8.6, 4.2 Hz, 2H), 7.25 (d, J = 8.0 Hz, 2H), 7.17 (d, J = 7.9 Hz, 2H), 2.63 – 2.55 (m, 2H), 2.27 – 2.15 (m, 2H), 1.87 – 1.73 (m, 2H). Compound PLC-6.2

A mixture of PLC-6.1 (385 mg, 0.729 mmol), 3,5-bis-(trifluoromethyl)phenylboronic acid (374 mg, 1.45 mmol), Pd(dppf)Cl ₂ (36 mg, 0.05 mmol), potassium carbonate (276 mg, 2 mmol) in cosolvents of THF/DMF/water (20mL/4mL/2mL) was degassed, then heated at 80 ºC for overnight. The mixture was worked up with 200mL ethyl acetate and 50 mL 0.6 N hydrochloric acid aqueous solution. The aqueous phase was extracted with ethyl acetate (100 mL x 2). The organic phase was collected and washed with brine (100mL x 2), dried over sodium sulfate, then dry loaded on silica gel and purified by flash chromatography using eluents of DCM/EA (0% to 40% EA with 0.1% TFA). The main desired fraction was collected, removal of solvents under reduced pressure gave a yellow solid (340mg, in 70.5% yield). LCMS (APCI-): calculated for C36H21F6NO5 = 661.13; Found: 661. ¹ H NMR (400 MHz, d2- TCE) δ 8.57 (dd, J = 19.2, 8.1 Hz, 2H), 8.18 (d, J = 2.2 Hz, 1H), 8.05 (d, J = 8.0 Hz, 1H), 8.03 – 7.98 (m, 2H), 7.87 (s, 1H), 7.72 (dd, J = 8.6, 2.2 Hz, 1H), 7.48 (d, J = 8.6 Hz, 1H), 7.33 (d, J = 8.3 Hz, 3H), 7.21 – 7.12 (m, 2H), 2.72 (t, J = 7.6 Hz, 2H), 2.39 (t, J = 7.3 Hz, 2H), 2.04 – 1.97 (m, 2H). Compound PLC-6

A mixture of PLC-6.2 (49mg, 0.075 mmol), PLC-3.6 (25.6 mg, 0.05 mmol), DMAP/TsOH salt (20mg, 0.068 mmol) and DIC (0.1 mL, 0.63 mmol) in 5 mL DCM was stirred room temperature overnight. The reaction mixture was submitted to silica gel and purified by flash chromatography using eluents of DCM/ethyl acetate (0% to 10% ethyl acetate). The desired product peak was collected and concentrated under reduced pressure. The resulting solid was further washed with methanol and dried in air to give an orange solid (50mg, in 86%). LCMS (APCI-: calculated for C63H50BF8N3O9 (M-): 1155.35; found: 1155. ¹ H NMR (400 MHz, d2-TCE) δ 8.60 (d, J = 7.9 Hz, 1H), 8.55 (d, J = 8.4 Hz, 1H), 8.18 (d, J = 2.2 Hz, 1H), 8.05 (d, J = 8.1 Hz, 1H), 8.03 – 7.99 (m, 2H), 7.87 (s, 1H), 7.72 (dd, J = 8.6, 2.2 Hz, 1H), 7.48 (d, J = 8.6 Hz, 1H), 7.36 (dd, J = 15.9, 8.2 Hz, 3H), 7.21 (d, J = 8.2 Hz, 2H), 6.93 (s, 2H), 4.19 (q, J = 7.1 Hz, 4H), 2.81 (t, J = 7.5 Hz, 2H), 2.75 (s, 6H), 2.62 (t, J = 7.4 Hz, 2H), 2.11 (t, J = 7.5 Hz, 2H), 2.06 (s, 6H), 1.65 (s, 6H), 1.25 (t, J = 7.1 Hz, 6H). Synthesis of Compound PLC-7

A mixture of 1H,3H-thioxantheno[2,1,9-def]isochromene-1,3-dione (458 mg, 1.5 mmol), 4-(4- aminophenyl)butanoic acid (537 mg, 3 mmol) and DMAP (14mg, 0.11 mmol) in 10 mL DMF was heated at 165 ºC for 2.5 hrs in microwave reactor. The resulted solution was dropped into 60 mL acetone while stirring. Orange precipitate formed, and was filtered and washed with diethyl ether, dried in air to give an orange solid (546 mg), which was further dried in vacuum oven at 100 ºC for 3 hrs to afford the desired product as orange solid (500mg, in 71.7% yield). Confirmed by LCMS (APCI-): calculated for C ₂₈ H ₁₉ NO ₄ S (M-) = 465.10; Found: 465. ¹ H NMR (400 MHz, DMSO-d ₆ ) δ 8.55 (d, J = 8.4 Hz, 1H), 8.52 – 8.46 (m, 2H), 8.32 (d, J = 8.0 Hz, 1H), 7.78 (d, J = 8.0 Hz, 1H), 7.65 – 7.58 (m, 1H), 7.52 (tt, J = 7.2, 5.5 Hz, 2H), 7.37 – 7.30 (m, 2H), 7.30 – 7.23 (m, 2H), 2.69 (t, J = 7.4 Hz, 2H), 2.29 (t, J = 7.3 Hz, 2H), 1.88 (p, J = 7.5 Hz, 2H). Compound PLC-7

A mixture of PLC-3.6 (25.6 mg, 0.05mmol), PLC-7.1 (35 mg, 0.075 mmol), EDC•HCl (110mg, 0.57 mmol) and DMAP/p-TsOH (20 mg, 0.068 mmol) in DCM (5mL) was stirred at room temperature overnight. The resulted mixture was then loaded on silica gel, purified by flash chromatography using eluents of DCM/ethyl acetate (0% → 5% ethyl acetate). The main green fraction was collected and concentrated under reduced pressure, then triturated with methanol. After filtration and dried in air, an orange solid was obtained (40mg, in 83% yield). LCMS (APCI-): calculated for C55H48BF2N3O8S (M-) = 959.32; Found: 959. ¹ H NMR (400 MHz, d2-TCE) δ 8.56 (d, J = 8.1 Hz, 1H), 8.35 (d, J = 8.0 Hz, 1H), 8.19 (dd, J = 8.7, 4.4 Hz, 2H), 7.51 (d, J = 8.0 Hz, 1H), 7.45 – 7.30 (m, 5H), 7.20 (d, J = 8.2 Hz, 2H), 6.93 (s, 2H), 4.19 (q, J = 7.1 Hz, 4H), 2.80 (t, J = 7.6 Hz, 2H), 2.75 (s, 6H), 2.62 (t, J = 7.5 Hz, 2H), 2.11 (q, J = 7.6 Hz, 2H), 2.06 (s, 6H), 1.65 (s, 6H), 1.25 (t, J = 7.1 Hz, 6H). Synthesis of Compound PLC-8 Compound PLC-8.1 A mixture of compound PLC-6.1 (385 mg, 0.729 mmol), phenylboronic acid (178 mg, 1.45 mmol), Pd(dppf)Cl ₂ (36 mg, 0.05 mmol), potassium carbonate (276 mg, 2 mmol) in cosolvents of THF/DMF/water (20mL/4mL/2mL) was degassed, then heated at 80 ºC for overnight. The mixture was worked up with 200mL ethyl acetate and 50 mL 0.6 N hydrochloric acid aqueous solution. The aqueous phase was extracted with ethyl acetate (100 mL x 2). The organic phase was collected and washed with brine (100mL x 2), dried over sodium sulfate, then dry loaded on silica gel and purified by flash chromatography using eluents of DCM/EA (0% to 40% EA with 0.1% TFA). The main desired fraction was collected, removal of solvents under reduced pressure gave a yellow solid (250mg, in 65% yield). LCMS (APCI-): calculated for C34H23NO5: 525.16; Found: 525. ¹ H NMR (400 MHz, TCE-d2) δ 8.55 (dd, J = 19.5, 8.1 Hz, 2H), 8.20 (d, J = 2.1 Hz, 1H), 8.01 (d, J = 8.1 Hz, 1H), 7.72 (dd, J = 8.6, 2.1 Hz, 1H), 7.62 (d, J = 7.3 Hz, 2H), 7.51 – 7.28 (m, 7H), 7.17 (d, J = 8.2 Hz, 2H), 2.72 (t, J = 7.7 Hz, 2H), 2.39 (t, J = 7.3 Hz, 2H), 1.99 (q, J = 7.2 Hz, 2H). Compound PLC-8 A mixture of compound PLC-8.1 (39.4mg, 0.075 mmol), PLC-3.6 (25.6mg, 0.05 mmol), DIC (0.1 mL, 0.63 mmol), DMAP/TsOH (20mg, 0.068 mmol) in DCM (5mL) was stirred at room temperature overnight. The resulted mixture was loaded on silica gel, purified by flash chromatography using eluents of DCM/EA (0% → 10% EA). The desired main fraction was collected, concentrated under reduced pressure, and reprecipitated in DCM/methanol to give an orange solid (45 mg, in 88% yield). LCMA (APCI-): calculated for C ₆₁ H ₅₂ BF ₂ N ₃ O ₉ : 1019.38; Found: 1019. ¹ H NMR (400 MHz, d2-TCE) δ 8.56 (dd, J = 19.5, 8.1 Hz, 2H), 8.20 (d, J = 2.1 Hz, 1H), 8.02 (d, J = 8.1 Hz, 1H), 7.73 (dd, J = 8.6, 2.1 Hz, 1H), 7.66 – 7.58 (m, 2H), 7.45 (q, J = 8.4, 7.9 Hz, 3H), 7.37 (dd, J = 7.8, 5.7 Hz, 3H), 7.32 (d, J = 8.4 Hz, 1H), 7.21 (d, J = 8.2 Hz, 2H), 6.93 (s, 2H), 4.19 (q, J = 7.1 Hz, 4H), 2.81 (t, J = 7.6 Hz, 2H), 2.75 (s, 6H), 2.62 (t, J = 7.5 Hz, 2H), 2.11 (q, J = 7.6 Hz, 2H), 2.06 (s, 6H), 1.65 (s, 6H), 1.25 (t, J = 7.1 Hz, 6H). Synthesis of Compound PLC-9 Compound PLC-9.1

A mixture of 4-bromo-1,8-naphthalic anhydride (2.77 g, 10 mmol), 4-bromo-2-nitrophenol (3.27 g, 15 mmol) was degassed under vacuum for 30 min, then anhydrous NMP (50 mL) was added, followed by addition of sodium hydroxide (0.2 g, 5mmol) and copper powder (0.318 g, 5 mmol). The mixture was sparged with argon for 20 min, then heated at 180 °C overnight under argon atmosphere. After cooled down to room temperature, to the solution, 50 mL 20% hydrochloride acid aqueous solution was added dropwise, then added 50 mL water. The resulted mixture was allowed to stand for 3 hrs, then filtered to collect the precipitate, which was dried in vacuum to afford 4.6 g crude product. The crude product was dispersed in 30 mL acetone and stirred overnight at room temperature to dissolve the impurities. Filtration and dried in vacuum gave a brown yellow solid as desired product (3.3 g, in 80% yield). LCMS (APCI+): calculated for C18H9BrNO6 (M+H) = 413.95; Found: 414. ¹ H NMR (400 MHz, TCE-d2) δ 8.70 (dd, J = 8.4, 1.2 Hz, 1H), 8.63 (dd, J = 7.3, 1.2 Hz, 1H), 8.41 (d, J = 8.3 Hz, 1H), 8.24 (d, J = 2.4 Hz, 1H), 7.89 – 7.79 (m, 2H), 7.20 (d, J = 8.7 Hz, 1H), 6.82 (d, J = 8.3 Hz, 1H). Compound PLC-9.2 A mixture of PLC-9.1 (1.5 g, 3.6 mmol), iron powder (0.60 g, 10.8 mmol) in acetic acid (50 mL) was heated at 125 °C for 30 min. After cooled to room temperature, to the mixture, 100 mL water was added while stirring. The resulted mixture was filtered and washed with water, dried in air and vacuum to give a solid (1.35 g, in 82% yield). LCMS (APCI-): calculated for C ₁₈ H ₁₀ BrNO ₄ = 382.98; Found: 383. ¹ H NMR (400 MHz, DMSO-d6) δ 9.01 – 8.26 (m, 3H), 7.96 (s, 1H), 6.93 (dd, J = 85.2, 36.5 Hz, 4H), 5.54 (s, 2H). Compound PLC-9.3 PLC-9.2 (2.65 g, 6.9 mmol), was dispersed in acetic acid (50 mL)/water (10 mL) and cooled to 0 ºC. While being stirred, precooled hydrochloric acid (2.8 mL, 34.5 mmol) was added, then sodium nitrite solution (3.57 g, 52 mmol) in 15 mL water was added dropwise at 0 ºC. The whole was stirred for one hour at 0 ºC, then was transferred into additional funnel, and dropped into a copper sulfate solution (12 g, 47 mmol, in 140 mL water) over one hour period at 130 ºC. After cooled to room temperature, the precipitate was collected by filtration, washed with water (100 mL × 3), then stirred in 50 mL acetone at 40 ºC for 30 min. Filtration, dried in air then in vacuum gave a brown yellow solid (1.76 g, in 70% yield). LCMS (APCI+): calculated for C18H8BrO4 (M+H) = 366.95; Found: 367. ¹ H NMR (400 MHz, d2-TCE) δ 8.51 (dd, J = 12.3, 8.1 Hz, 2H), 8.12 (d, J = 2.3 Hz, 1H), 7.86 (d, J = 7.9 Hz, 1H), 7.60 (dd, J = 8.8, 2.3 Hz, 1H), 7.28 (d, J = 8.3 Hz, 1H), 7.23 (d, J = 8.8 Hz, 1H). Compound PLC-9.4 A mixture of PLC-9.3 (550 mg, 1.5 mmol), 4-(4-aminophenyl)butanoic acid (537 mg, 3 mmol) and DMAP (12.2 mg, 0.1 mmol) in 10 mL DMF was heated at 165 ºC for 2.5 hrs in microwave reactor. The resulted solution was dropped into 50 mL acetone while stirring. Precipitate formed and was filtered and dried in vacuum oven at 60 ºC for overnight to afford the desired product as brown yellow solid (0.49 g, in 62% yield). LCMS (APCI-): calculated for C28H18BrNO5 = 527.04; Found: 527. ¹ H NMR (400 MHz, DMSO-d6) δ 8.54 (d, J = 2.3 Hz, 1H), 8.41 (dd, J = 9.9, 8.0 Hz, 2H), 8.33 (d, J = 7.9 Hz, 1H), 7.71 (dd, J = 8.8, 2.3 Hz, 1H), 7.39 (dd, J = 8.6, 4.2 Hz, 2H), 7.25 (d, J = 8.0 Hz, 2H), 7.17 (d, J = 7.9 Hz, 2H), 2.63 – 2.55 (m, 2H), 2.27 – 2.15 (m, 2H), 1.87 – 1.73 (m, 2H). Compound PLC-9.4 Compound PLC-9.5 A mixture of PLC-9.4 (385 mg, 0.729 mmol), 3,5-bis-(trifluoromethyl)phenylboronic acid (374 mg, 1.45 mmol), Pd(dppf)Cl2 (36 mg, 0.05 mmol), potassium carbonate (276 mg, 2 mmol) in cosolvents of THF/DMF/water (20mL/4mL/2mL) was degassed, then heated at 80 ºC for overnight. The mixture was worked up with 200mL ethyl acetate and 50 mL 0.6 N hydrochloric acid aqueous solution. The aqueous phase was extracted with ethyl acetate (100 mL x 2). The organic phase was collected and washed with brine (100 mL x 2), dried over sodium sulfate, then dry loaded on silica gel and purified by flash chromatography using eluents of DCM/EA (0% to 40% EA with 0.1% TFA). The main desired fraction was collected, removal of solvents under reduced pressure gave a yellow solid (340mg, in 70.5% yield). LCMS (APCI-): calculated for C ₃₆ H ₂₁ F ₆ NO ₅ = 661.13; Found: 661. ¹ H NMR (400 MHz, d2- TCE) δ 8.57 (dd, J = 19.2, 8.1 Hz, 2H), 8.18 (d, J = 2.2 Hz, 1H), 8.05 (d, J = 8.0 Hz, 1H), 8.03 – 7.98 (m, 2H), 7.87 (s, 1H), 7.72 (dd, J = 8.6, 2.2 Hz, 1H), 7.48 (d, J = 8.6 Hz, 1H), 7.33 (d, J = 8.3 Hz, 3H), 7.21 – 7.12 (m, 2H), 2.72 (t, J = 7.6 Hz, 2H), 2.39 (t, J = 7.3 Hz, 2H), 2.04 – 1.97 (m, 2H). Compound PLC-1.1 Step1: A mixture of ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (1.0g, 6.0 mmol), 4-hydroxy- 2,6-dimethylbenzaldehyde (0.449g, 3.0 mmol) and tosylic acid (50 mg, 0.29mmol) in 50 mL 1,2- dichloroethane was degassed and stirred at room temperature overnight. LCMS analysis shows that one main peak with m/e ⁺ = 467. Step 2: To the resulting solution, DDQ (0.817g, 3.6 mmol) was added then stirred for 30 min at room temperature. LCMS analysis shows that all starting material was converted to desired product with m/e ⁺ =465. Step 3: With ice-bath cooling, 1.7 mL triethylamine and 2.2 mL BF ₃ -diethyl ether were added sequentially to the mixture from step 2. The whole was heated at 50 ºC for one hour. LCMS analysis shows ~30% conversion. To the mixture, additional 1mL triethylamine and 1 mL BF ₃ -diethyl ether was added, the whole was heated at 50 ºC for additional one hour. LCMS analysis shows that all stating materials were converted to desired BODIPY product with m/e ⁺ = 513, m/e- = 512. The reaction mixture was submitted directly to silica gel and purified by flash chromatography using eluents of hexanes/ethyl acetate (0% → 30% ethyl acetate). The main desired peak was collected, and removal of solvents gave an orange solid (1.0g, in 65% yield). LCMS (APCI): calculated for C27H32BF2N2O5 (M+H): 513.2; Found: 513. ¹ H NMR (400 MHz, Chloroform-d) δ 7.26 (s, 3H), 6.68 (s, 2H), 4.29 (q, J = 7.1 Hz, 4H), 2.84 (s, 6H), 2.05 (s, 6H), 1.34 (t, J = 7.1 Hz, 6H). Compound PLC-9

A mixture of PLC-9.5 (49mg, 0.075 mmol), PLC-3.6 (25.6 mg, 0.05 mmol), DMAP/TsOH salt (20mg, 0.068 mmol) and DIC (0.1 mL, 0.63 mmol) in 5 mL DCM was stirred room temperature overnight. The reaction mixture was submitted to silica gel and purified by flash chromatography using eluents of DCM/ethyl acetate (0% to 10% ethyl acetate). The desired product peak was collected and concentrated under reduced pressure. The resulting solid was further washed with methanol and dried in air to give an orange solid (50mg, in 86%). LCMS (APCI-: calculated for C ₆₃ H ₅₀ BF ₈ N ₃ O ₉ (M-): 1155.35; found: 1155. ¹ H NMR (400 MHz, d2-TCE) δ 8.60 (d, J = 7.9 Hz, 1H), 8.55 (d, J = 8.4 Hz, 1H), 8.18 (d, J = 2.2 Hz, 1H), 8.05 (d, J = 8.1 Hz, 1H), 8.03 – 7.99 (m, 2H), 7.87 (s, 1H), 7.72 (dd, J = 8.6, 2.2 Hz, 1H), 7.48 (d, J = 8.6 Hz, 1H), 7.36 (dd, J = 15.9, 8.2 Hz, 3H), 7.21 (d, J = 8.2 Hz, 2H), 6.93 (s, 2H), 4.19 (q, J = 7.1 Hz, 4H), 2.81 (t, J = 7.5 Hz, 2H), 2.75 (s, 6H), 2.62 (t, J = 7.4 Hz, 2H), 2.11 (t, J = 7.5 Hz, 2H), 2.06 (s, 6H), 1.65 (s, 6H), 1.25 (t, J = 7.1 Hz, 6H). Synthesis of Compound PLC-10

A 1 L 2N round bottom flask was placed in an aluminum heat block and charged with a stir bar. The flask was fitted with a finned condenser/gas adapter, stopper and flow control valve. The system was flushed with argon. To the flask was added 6-bromo-1H,3H-benzo[de]isochromene-1,3- dione (40.0 mmol, 11.084 g) and 4-(tert-butyl)-2-nitrophenol (60.0 mmol, 11.712g), followed by anhydrous NMP (150 mL). To the flask was added NaOH (20.0 mmol, 800 mg) and copper (powder) (20.0 mmol, 1271 mg), followed by anhydrous NMP (25 mL). The flask was stirred under argon atmosphere with the heat block set to 170 °C. The reaction was stirred at this temperature overnight. The reaction mixture was cooled to room temperature and treated with water (175 mL) and 1N HCl (44 mL). The reaction mixture was stirred for 30 minutes, then filtered off, washing with water. The precipitate was transferred to a flask with acetone/DCM and evaporated to dryness, then azeotroped with toluene. The crude product was dissolved in a small amount of DCM and treated with methanol (300 mL). The DCM and some of the methanol were removed by rotary evaporation with a hot water bath (80 °C). When all of the DCM was removed, the mixture was cooled to room temperature and the solid was filtered off. Gives a tan powder, 8.180g (52% yield). MS (APCI): calculated for C ₂₂ H ₁₇ NO ₆ (M+H) = 392; found: 392. ¹ H NMR (400 MHz, Tetrachloroethane-d ₂ ) δ 8.82 (dd, J = 8.4, 1.2 Hz, 1H), 8.71 (dd, J = 7.3, 1.2 Hz, 1H), 8.49 (d, J = 8.3 Hz, 1H), 8.16 (d, J = 2.4 Hz, 1H), 7.91 (dd, J = 8.4, 7.3 Hz, 1H), 7.80 (dd, J = 8.6, 2.4 Hz, 1H), 7.34 (d, J = 8.6 Hz, 1H), 6.91 (d, J = 8.3 Hz, 1H), 1.43 (s, 9H). Compound PLC-10.2 A 250 mL 2N round bottom flask was placed in an aluminum heat block and charged with a stir bar. The flask was fitted with a finned condenser/gas adapter, stopper and flow control valve. The system was flushed with argon. To the flask was added PLC-10.1 (10.0 mmol, 3.914 g) and 2-MeTHF (70 mL). With stirring at room temperature, added HCl in water (100 mmol, 4.0N, 25 mL) and SnCl ₂ .2H ₂ O (40.0 mmol, 9.024 g). The reaction mixture was stirred under argon atmosphere with the heat block set to 90 °C for 30 minutes. The reaction mixture was cooled to 0 °C and made basic with aqueous 2N NaOH to pH ~8 (pH paper). Filtered off the solids (slow filtration), then washed the resulting solids with 2-MeTHF (8 X 100mL). The filtrate was transferred to a separatory funnel and the layers separated. The organic layer was dried over MgSO ₄ , filtered, and evaporated to dryness in vacuo. Gives 3.743 g (quantitative yield). Used in the next step without further purification. MS (APCI): calculated for C ₂₂ H ₁₉ NO ₄ (M+H) = 362; found: 362. ¹ H NMR (400 MHz, Tetrachloroethane-d2) δ 8.88 (dd, J = 8.4, 1.2 Hz, 1H), 8.69 (dd, J = 7.3, 1.2 Hz, 1H), 8.48 (d, J = 8.4 Hz, 1H), 7.89 (dd, J = 8.4, 7.3 Hz, 1H), 7.03 – 6.93 (m, 3H), 6.88 (dd, J = 8.4, 2.3 Hz, 1H), 1.35 (s, 9H). Compound PLC-10.3 A 40 mL vial was charged with a stir bar, NaNO ₂ (30.0 mmol, 2.070 g), and water (10 mL). The vial was stirred in an ice-water bath at 0 °C. A 100 mL round bottom flask was charged with a stir bar and PLC-10.2 (4.00 mmol, 1.446 g). To the flask was added glacial AcOH (30 mL) and con. HCl (20.0 mmol, 12.1N, 1.65 mL). The mixture was stirred at room temperature for a few minutes, then placed in an ice-water bath and stirred for ~1 minute. Began adding the solution of NaNO2 before the acetic acid begins to freeze. The NaNO2 was added over a period of a period of ~10 minutes. The diazo solution was stirred at 0 °C for 1 hour. While the diazo solution was stirring, prepared a 250 mL 2N round bottom flask with a large stir bar. The flask was fitted with a finned condenser and a dropping funnel. The flask was clamped by the off-center neck and the dropping funnel was placed in the off- center neck, so the solution would hit the top of the vortex when stirring. To this flask was added CuSO ₄ .5H ₂ O (27.4 mmol, 6.842 g) and water (80 mL). About 15 minutes before the diazo solution was done, began heating the copper solution to 130 °C. The diazo solution was transferred to the dropping funnel when the solution reached 130 °C and began adding the diazo solution dropwise with high- speed stirring over a period of ~30 minutes. When the addition was finished, the solution was heated for another 1-2 minutes, then cooled in a room temperature water bath. The precipitate was filtered off, washing with water. The precipitate was dried by suction, then the crude precipitate was dissolved/suspended in DCM and evaporated to dryness onto ~10 g flash silica gel. Purified by flash chromatography on silica gel (220 g, solid load, equilibrate 50% DCM/hexanes, eluting 50% DCM/hexanes (2 CV) → 100% DCM (20 CV) → isocratic DCM (15 CV) → 0% EtOAc/DCM (0 CV) → 1% EtOAc/DCM (10 CV)). The product tails. Fractions containing product were evaporated to dryness in vacuo. Gives 528 mg (38% yield). MS (APCI): calculated for C22H16O4 (M+H) = 345; found: 345. ¹ H NMR (400 MHz, Tetrachloroethane-d2) δ 8.61 (d, J = 7.9 Hz, 1H), 8.56 (d, J = 8.4 Hz, 1H), 8.05 (d, J = 2.2 Hz, 1H), 8.01 (d, J = 8.0 Hz, 1H), 7.66 (dd, J = 8.8, 2.2 Hz, 1H), 7.38 (d, J = 8.7 Hz, 1H), 7.34 (d, J = 8.4 Hz, 1H), 1.44 (s, 9H). Compound PLC-10.4 PLC-10.4 was synthesized from PLC-10.3 (1.525 mmol, 525 mg), 4-(4-aminophenyl)butanoic acid (3.05 mmol, 546 mg), and DMAP (0.111 mmol, 14 mg) in a manner similar to PLC-1. The crude reaction mixture was diluted with acetone (25 mL) and water (50 mL). The resulting precipitate was filtered off, washing with 1:1 acetone:water. The resulting solid was dried in a vacuum oven at ~110 °C. Gives a yellow solid, 738 mg (96% yield). MS (APCI): calculated for C32H +H) = 506; found: 506. ¹ H NMR (400 MHz, DMSO-d6) δ 12.12 (s, 1H), 8.48 – 8.29 (m, 3H), 8.23 (d, J = 2.3 Hz, 1H), 7.68 (dd, J = 8.8, 2.3 Hz, 1H), 7.43 – 7.30 (m, 4H), 7.25 (d, J = 7.9 Hz, 2H), 2.75 – 2.64 (m, 2H), 2.30 (t, J = 7.4 Hz, 2H), 1.88 (p, J = 7.5 Hz, 2H), 1.41 (s, 9H). Compound PLC-10 Compound 10 was synthesized from PLC-1.1 (0.050 mmol, 25.6 mg), PLC-10.4 (0.075 mmol, 37.9 mg), DMAP.pTsOH salt (0.100 mmol, 29.4 mg), and EDC.HCl (0.075 mmol, 14.4 mg) in a manner similar to Compound 2. The crude reaction mixture was diluted with hexanes (20 mL) and loaded onto ~15 g flash silica gel in a loader. Purified by flash chromatography (120 g, solid load, equilibrate 80% DCM/hexanes, eluting 80% DCM/hexanes 2 CV) → 100% DCM (10 CV) → isocratic DCM (10 CV) → 0% EtOAc/DCM (0 CV) → 2% EtOAc/DCM (30 CV)). Fractions containing product were evaporated to dryness. The product was triturated with hot MeOH. The solid was dried in a vacuum oven at ~110 °C. Gives an orange solid, 46.5 mg (93% yield). MS (APCI): calculated for C ₅₇ H ₅₂ BF ₂ N ₃ O ₉ (M-) = 999; found: 999. ¹ H NMR (400 MHz, Tetrachloroethane-d ₂ ) δ 8.66 (d, J = 7.9 Hz, 1H), 8.60 (d, J = 8.4 Hz, 1H), 8.08 (d, J = 2.3 Hz, 1H), 8.05 (d, J = 8.1 Hz, 1H), 7.64 (dd, J = 8.8, 2.2 Hz, 1H), 7.49 – 7.43 (m, 2H), 7.41 – 7.34 (m, 2H), 7.32 – 7.27 (m, 2H), 7.02 (s, 2H), 4.28 (q, J = 7.1 Hz, 4H), 2.89 (t, J = 7.6 Hz, 2H), 2.84 (s, 6H), 2.71 (t, J = 7.4 Hz, 2H), 2.26 – 2.11 (m, 8H), 1.45 (s, 9H), 1.34 (t, J = 7.1 Hz, 6H). Synthesis of Compound PLC-11

PLC-6.3 (6.3 g, 17.159 mmol, 1 eq) was suspended in 35 mL DMSO anhydrous, glycine (2.31 g, 30.77 mmol, 1.8 eq) was added to the reaction mixture at room temperature. The resulting mixture was stirred at 130 °C for 1 hour (the mixture was not dissolved), it was then heated to 160 °C for 1hr, LMCMS shown reaction was completed. After cooling to room temperature, the solid product was filtered, washed with water (250 mL) then dried in vacuo-oven to gain 6.5 g greenish yellow solid, yield 90%. MS (APCI): calculated for C ₂₀ H ₁₀ BrNO ₅ (M-H) = 423; found: 423.1H NMR (400 MHz, DMSO-d6) δ 8.65 (s, 1H), 8.50 (s, 1H), 8.46 (d, J = 8.2 Hz, 2H), 8.09 (d, J = 8.0 Hz, 2H), 7.99 (d, J = 8.7 Hz, 1H), 7.87 (d, J = 8.0 Hz, 2H), 7.58 (d, J = 8.6 Hz, 1H), 7.45 (d, J = 8.4 Hz, 1H), 4.71 (s, 2H). Compound PLC-11.2

PLC-11.1 (7.0 g, 16.50 mmol, 1eq) was suspended in 2-MeTHF (150ml), added 4- (trifluoromethyl)benzeneboronic acid (5.648 g, 29.7 mmol, 1.8 eq), K ₂ CO ₃ (4.65 g, 33 mmol, 2eq), H2O (15 ml) Pd(dppf)Cl2 · DCM ( 269.5 mg, 0.33 mmol, 0.02eq).Vac- Fill Argon cycle 3 times, the resulting mixture was stirred & heated at 95 °C under Argon atmosphere 12 hours, the mixture was cooled to room temperature, added stirred with 1N HCl (20 ml) for 15 minutes then holding at room temperature 1 hours. The solid was filtered, stirred with DMF at room temperature 15 minutes then filtered, the greenish yellow solid was washed with MeOH, then dried in vacuo-oven to obtain 6.70 g greenish yellow solid which was used next step without further purification. 83% yield. MS (APCI): calculated for C ₂₇ H ₁₄ F ₃ NO ₅ (M-) = 489; found: 489. ¹ H NMR (400 MHz, DMSO-d ₆ ) δ 8.52 (s, 1H), 8.37 (q, J = 8.1, 7.7 Hz, 3H), 8.04 (d, J = 7.9 Hz, 2H), 7.93 (d, J = 8.7 Hz, 1H), 7.84 (d, J = 8.0 Hz, 2H), 7.49 (d, J = 8.6 Hz, 1H), 7.34 (d, J = 8.3 Hz, 1H), 4.67 (s, 2H).

Compound PLC-11 PLC-11.2 (73.4 mg, 0.15 mmol, 1.5eq) was suspended in DCM anhydrous (10.0 ml), added PLC- 11.3 (51.2 mg, 0.100 mmol, 1 eq), DMAP-pTSA (58.8 mg, 0.2 mmol, 2eq), EDC.HCl (57.5 mg, 0.3 mmol, 3 eq), stirred at room temperature, under Argon atmosphere, 5 hours. Diluted with DCM (150 ml), filtered, washed the solid with 50 ml DCM, collected the filtrate, loaded onto 80 g SiO2 column, eluting with Hex-DCM (1/1), DCM only then 0.5% EA in DCM, after washing with MeOH, gained 87 mg yellow solid, yield 78%. MS (APCI): calculated for C ₅₄ H ₄₃ BF ₅ N ₃ O ₉ (M-) = 983; found: 983. ¹ H NMR (400 MHz) δ 8.64 (d, J = 7.9 Hz, 1H), 8.59 (d, J = 8.3 Hz, 1H), 8.20 (d, J = 2.1 Hz, 1H), 8.03 (d, J = 8.2 Hz, 1H), 7.72 (dd, J = 8.5, 2.0 Hz, 4H), 7.46 (d, J = 8.6 Hz, 1H), 7.34 (d, J = 8.4 Hz, 1H), 7.01 (s, 2H), 5.15 (s, 2H), 4.17 (q, J = 7.1 Hz, 4H), 2.74 (s, 6H),2.06 (s, 5H), 1.96 (s, 1H), 1.61 (s, 5H), 1.51 (s, 12H), 1.23 (t, J = 7.1 Hz, 5H). Synthesis of Compound PLC-12

PLC-11.2 (73.4 mg, 0.15 mmol, 3eq) was suspended in DCM anhydrous (10.0 ml), added PLC- 12.1 (39.93 mg, 0.05 mmol, 1 eq), DMAP-pTSA (58.8 mg, 0.2 mmol, 4 eq), EDC.HCl (47.92 mg, 0.25 mmol, 5 eq), stirred at room temperature, under Argon atmosphere, 5 hours, diluted with DCM (150 ml), filtered, washed solid with 50 ml DCM, collected the filtrate, loaded onto 80 g SiO ₂ column, eluting with Hex-DCM (1/1) , DCM only then 0.5% EA in DCM then washed with MeOH, gained 80 mg, yield 77%. MS (APCI): calculated for C ₆₄ H ₄₇ BF ₅ N ₃ O ₉ (M-) = 1107; found: 1107. ¹ H NMR (400 MHz, ) δ 8.64 (d, J = 7.9 Hz, 1H), 8.59 (d, J = 8.4 Hz, 1H), 8.20 (d, J = 2.1 Hz, 1H), 8.03 (d, J = 8.1 Hz, 1H), 7.72 (dd, J = 8.5, 2.1 Hz, 4H), 7.46 (d, J = 8.6 Hz, 1H), 7.34 (d, J = 8.3 Hz, 1H), 7.32 – 7.18 (m, 9H), 7.00 (s, 2H), 5.17 (s, 4H), 5.14 (s, 2H), 2.74 (s, 6H), 2.04 (s, 6H), 1.61 (s, 6H). Synthesis of Compound PLC-13 Compound PLC-13.1

PLC-6.1 (6.3 g, 17.159 mmol, 1 eq) was suspended in 35 mL DMSO anhydrous, glycine (2.31 g, 30.77 mmol, 1.8 eq) was added to the reaction mixture at RT. The resulting mixture was stirred at 130 °C for 1 hour (the mixture was not dissolved), it was then heated to 160 °C for 1hr, LMCMS shown reaction was completed. After cooling to room temperature, the solid product was filtered, washed with water (250 mL) then dried in vacuo-oven to gain 6.5g greenish yellow solid, yield 90%. MS (APCI): calculated for C ₂₀ H ₁₀ BrNO ₅ (M-H) = 423; found: 423. ¹ H NMR (400 MHz, DMSO-d6) δ 8.65 (s, 1H), 8.50 (s, 1H), 8.46 (d, J = 8.2 Hz, 2H), 8.09 (d, J = 8.0 Hz, 2H), 7.99 (d, J = 8.7 Hz, 1H), 7.87 (d, J = 8.0 Hz, 2H), 7.58 (d, J = 8.6 Hz, 1H), 7.45 (d, J = 8.4 Hz, 1H), 4.71 (s, 2H). Compound PLC-13.2 PLC-13.1 (4.24 g, 10.0 mmol, 1eq) was suspended in 2-MeTHF (150ml), H ₂ O (5.0 ml), added 4- (tert-butyl) benzeneboronic acid (3.56 g, 20 mmol, 2 eq), K ₂ CO ₃ (2.76 g, 20 mmol, 2eq), Pd(dppf)Cl ₂ · DCM (163.3 mg, 0.2 mmol, 0.02eq). The reaction mixture was degassed by Vac-Fill Argon cycle 3 times, stirred & heated at 95 °C under Argon atmosphere 12 hours. After cooling to room temperature, added ethyl acetate (150 ml) acidified with 1N HCl to pH 4-5. Organic layer was washed with water, separated, concentrated. The residue was stirred in DMF (15 ml), filtered to obtain a solid which was washed with MeOH (50 mL) then dried in vacuo-oven to gain 4.1 g greenish yellow solid product, 85% yield. MS (APCI): calculated for C ₃₀ H ₂₃ NO ₅ (M-) = 477; found: 477. ¹ H NMR (400 MHz, DMSO-d6) δ 8.33 (d, J = 6.1 Hz, 3H), 8.24 (d, J = 7.9 Hz, 1H), 7.95 (s, 1H), 7.78 (d, J = 8.3 Hz, 1H), 7.70 (d, J = 7.9 Hz, 2H), 7.50 (d, J = 7.9 Hz, 2H), 7.39 (d, J = 8.3 Hz, 1H), 7.29 (d, J = 8.2 Hz, 1H), 4.52 (s, 2H), 2.89 (s, 3H), 2.73 (s, 3H), 2.54 – 2.47 (m, 21H), 1.34 (s, 10H). Compound PLC-13 PLC-13.2 (71.62 mg, 0.15 mmol, 1.5eq) was suspended in DCM anhydrous (10.0 ml), added PLC- 13.3 (58.5 mg, 0.1 mmol, 1 eq), DMAP-pTSA (58.8 mg, 0.2 mmol, 2eq), EDC.HCl (57.5 mg, 0.3 mmol, 3 eq), stirred at room temperature, under Argon atmosphere, 5 hours, diluted with DCM (150 ml), filtered, washed the solid with 50 ml DCM, collected the filtrate, loaded onto 80 g SiO ₂ column, eluting with Hex-DCM (1/1), DCM only then 0.5% EA in DCM. The crude was loaded onto 80 g SiO ₂ column, eluting with Hex-DCM (1/1), DCM only then 0.5% EA in DCM then washed with MeOH, gained 80 mg, yield 84.3%. MS (APCI): calculated for C ₅₇ H ₅₂ BF ₂ N ₃ O ₉ (M-) = 971; found: 971. ¹ H NMR (400 MHz, ) δ 8.64 (d, J = 7.9 Hz, 1H), 8.59 (d, J = 8.4 Hz, 1H), 8.20 (d, J = 2.1 Hz, 1H), 8.03 (d, J = 8.1 Hz, 1H), 7.72 (dd, J = 8.5, 2.1 Hz, 4H), 7.46 ( z, 1H), 7.34 (d, J = 8.3 Hz, 1H), 7.32 – 7.18 (m, 9H), 7.00 (s, 2H), 5.17 (s, 4H), 5.14 (s, 2H), 2.74 (s, 6H), 2.04 (s, 6H), 1.61 (s, 6H). Synthesis of Compound PLC-14

PLC-13.2 (71.62 mg, 0.15 mmol, 1.5eq) was suspended in DCM anhydrous (10.0 ml), added PLC- 12.1 (63.65 mg, 0.100 mmol, 1 eq), DMAP-pTSA (58.8 mg, 0.2 mmol, 2eq), EDC.HCl (57.5 mg, 0.3 mmol, 3 eq), stirred at room temperature, under Argon atmosphere, 5 hours, diluted with DCM (150 ml), filtered, washed the solid with 50 ml DCM, collected the filtrate, loaded onto 80 g SiO2 column, eluting with Hex-DCM (1/1), DCM only then 0.5% EA in DCM. The good fractions were concentrated then washed with MeOH, gained 85 mg, yield 77%. MS (APCI): calculated for C ₆₇ H ₅₆ BF ₂ N ₃ O ₉ (M-) = 1095; found: 1095. ¹ H NMR (400 MHz) δ 8.63 (d, J = 7.9 Hz1H), 8.58 (d, J = 8.4 Hz, 1H), 8.21 (d, J = 2.1 Hz, 1H), 8.02 (d, J = 8.1 Hz, 1H), 7.73 (dd, J = 8.6, 2.1 Hz, 1H), 7.56 (d, J = 8.3 Hz, 2H), 7.46 (d, J = 8.4 Hz, 2H), 7.42 (d, J = 8.6 Hz, 1H), 7.32 (d, J = 8.4 Hz, 1H), 7.30 –7.17 (m, 10H), 7.00 (s, 2H), 5.17 (s, 5H), 5.14 (s, 2H), 2.74 (s, 6H), 2.04 (s, 6H), 1.61 (s, 6H), 1.31 (s, 9H). Synthesis of Compound PLC-15 Compound PLC-3.4

A mixture of PLC-3.3 (400.0 mg, 1.1 mmol), 4-aminophenylacetic acid (329.4 mg, 2.2 mmol) and DMAP (9.3 mg, 0.080 mmol) in DMF (8 mL) was degassed at room temperature. Then the mixture was heated up to 165 ºC and has been kept at this temperature for 3 hrs. TLC and LCMS showed ~95% conversion without observable side-reaction. The mixture was cooled down to 50 ºC. Then it was poured into an acetone solution (40 mL), which has been pre-chilled by water-ice bath. The mixture has been kept at 0 ºC for 2 hrs and then has been kept stirring at room temperature overnight. The solid was collected through vacuum filtration and washed by acetone (4 mL). And it was dried by vacuum oven at 100 ºC for 3 hrs to provide the pure compound PLC-3.4 as a yellow brown solid 395.0 mg, 73% yield. MS (APCI): calculated for C ₂₆ H ₁₄ BrNO ₅ ([M+H] ⁺ ) = 500 found: 500. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) δ 8.65 (d, J = 8.0 Hz, 1H), 8.62 (d, J = 8.0 Hz, 1H), 8.21 (dd, J = 6.4 Hz, 2.4 Hz, 1H), 7.99 (bs, 1H), 7.95 (t, J = 7.6 Hz, 1H), 7.67 (dd, J = 8.4 Hz, 2.4 Hz, 1H), 7.53 (d, J = 8.0 Hz, 2H), 7.37 (d, J = 8.4 Hz, 1H), 7.32 (m, 3H), 2.94 (s, 2H). Compound PLC-15.1 A mixture of PLC-3.4 (175.0 mg, 0.35 mmol), 4-tert-butylphenylboronic acid (124.6 mg, 0.70 mmol), Pd(dppf)Cl2 (18.0 mg, 0.025 mmol) and K ₂ CO ₃ (130.4 mg, 0.95 mmol) in THF-DMF-H ₂ O (10 mL/ 2 mL/ 1 mL) was degassed at room temperature. Then the mixture was heated up to 80 ºC and has been kept at this temperature overnight. TLC and LCMS showed the completion of the reaction. The mixture was cooled down to room temperature. Then it was added with 0.1 HCl (75 mL) and EtOAc (75 mL). Once separated by separation funnel, the aqueous solution was further extracted with THF (75 mL*3) after it was saturated with NaCl. The combined organic phase was dried over anhydrous Na ₂ SO ₄ , then it was filtered and concentrated under rotavapor, and purified by silica gel flash chromatography to provide PLC-15.1 as a yellow solid using 0-40% EtOAc in DCM with 0.1% TFA as an eluant, 76.0 mg, 39% yield. MS (APCI): calculated for C ₃₆ H ₂₇ NO ₅ ([M-H]-) = 553 found: 553. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) δ 8.69 (d, J = 8.0 Hz, 1H), 8.64 (d, J = 8.4 Hz, 1H), 8.24 (d, J = 8.4 Hz, 1H), 8.03 (d, J = 8.0 Hz, 1H), 7.76 (dd, J = 8.4 Hz, 2.0 Hz, 1H), 7.53 (m, 7H), 7.33 (m, 4H), 3.77 (s, 2H), 1.40 (s, 9H). Compound PLC-15 To the vial, PLC-1.1 (30.0 mg, 0.059 mmol), PLC-15.1 (64.8 mg, 0.12 mmol), EDC•HCl (56.6 mg, 0.30 mmol) and DMAP•TsOH (35.4 mg, 0.12 mmol) were added, followed by anhydrous DCM (3 ml). The reaction mixture has been kept at room temperature overnight. After the completion of the reaction, the mixture was loaded with silica gel and purified by flash chromatography, using DCM in EtOAc (0-4%) as an eluant to provide the pure RL-naphthalimide-BODIPY PLC-15 as an orange yellow solid. The solid was further triturated with EtOAc (0.5 mL) and MeOH (15 ml) to deliver RL- naphthalimide-BODIPY PLC-15, 48.0 mg, 78% yield. MS (APCI): calculated for C63H56BF2N3O9 ([M-H]-) = 1047 found: 1047. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.68 (d, J = 8.0 Hz, 1H), 8.63 (d, J = 8.0 Hz, 1H), 8.30 (d, J = 2.0 Hz, 1H), 8.10 (d, J = 8.0 Hz, 1H), 7.82 (dd, J = 8.0 Hz, 2.0 Hz, 1H), 7.65 (m, 4H), 7.53 (m, 3H), 7.39 (m, 3H), 7.05 (s, 2H), 4.28 (q, J = 7.2 Hz, 4H), 4.01 (s, 2H), 2.84 (s, 6H), 2.16 (s, 6H), 1.74 (s, 6H), 1.40 (s, 9H), 1.34 (t, J = 7.2 Hz, 6H). Synthesis of Compound PLC-16 A 100 mL vial was fitted with a stir bar. To the vial, PLC-3.4 (400.0 mg, 0.80 mmol), 3,5- bis(trifluoromethyl)phenylboronic acid (262.2 mg, 1.6 mmol), Pd(dppf)Cl2 (41.0 mg, 0.056 mmol) and K ₂ CO ₃ (412.6 mg, 2.2 mmol) in THF/DMF/H ₂ O (22 ml/ 4.4 ml/ 2.2 ml) was degassed at room temperature. The reaction mixture was heated up to 80 ºC and the reaction has been kept at this temperature overnight. TLC was used to monitor the reaction. After the completion, the reaction was worked up by the addition of 0.1N HCl (150 ml) and EtOAc (150 ml). The aqueous phase was further extracted by THF (150 ml*3). The combined organic phases were dried over anhydrous Na2SO4, concentrated under rotavapor and purified by flash chromatography, using DCM in EtOAc (0-40%, with 0.1% TFA) as an eluant to provide the pure RL-naphthalimide derivative PLC-16.1 as a yellow/ yellow brown solid.311.0 mg, 61% yield. MS (APCI): calculated for C ₃₄ H ₁₇ F ₆ NO ₅ ([M+H] ⁺ ) = 634 found: 634. ¹ H NMR (400 MHz, DMSO-d6) 8.73 (m, 1H), 8.46 (m, 5H), 8.10 (m, 2H), 7.57 (m, 1H), 7.42 (d, J = 8.0 Hz, 2H), 7.40 (m, 1H), 7.30 (d, J = 8.0 Hz, 2H), 3.72 (s, 2H). Compound PLC-16 A 25 mL vial was fitted with a stir bar. To the vial, PLC-1.1 (40.0 mg, 0.078 mmol), PLC-16.1 (98.9 mg, 0.16 mmol), EDC•HCl (74.8 mg, 0.39 mmol) and DMAP•TsOH (46.8 mg, 0.16 mmol) were added, followed by anhydrous DCM (4 ml). The reaction mixture has been kept at room temperature overnight. After the completion of the reaction, the mixture was loaded with silica gel and purified by flash chromatography, using DCM in EtOAc (0-4%) as an eluant to provide the pure RL-naphthalimide- BODIPY PLC-16 as an orange yellow solid. The solid was further triturated with EtOAc (0.5 mL) and MeOH (15 ml) to deliver RL-naphthalimide-BODIPY PLC-16, 58.0 mg, 66% yield. MS (APCI): calculated for C61H46BF8N3O9 ([M-H]-) = 1127 found: 1127. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.70 (d, J = 8.0 Hz, 1H), 8.65 (d, J = 8.0 Hz, 1H), 8.28 (d, J = 2.4 Hz, 1H), 8.15 (d, J = 8.0 Hz, 1H), 8.11 (m, 2H), 7.96 (bs, 1H), 7.81 (dd, J = 8.0 Hz, 2.4Hz, 1H), 7.61 (m, 3H), 7.41 (m, 3H), 7.05 (s, 2H), 4.28 (q, J = 7.2 Hz, 4H), 4.01 (s, 2H), 2.84 (s, 6H), 2.16 (s, 6H), 1.73 (s, 6H), 1.34 (t, J = 7.2 Hz, 6H). Synthesis of Compound PLC-17

A 250 mL 2N round bottom flask was placed in an aluminum heat block and charged with a stir bar. The flask was fitted with a finned condenser/gas adapter and flow control valve. The system was flushed with argon. To the flask was added 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol (11.0 mmol, 2.421 g), 1-bromo-2-(2-(2-methoxyethoxy)ethoxy)ethane (10.0 mmol, 2.48 mL), anhydrous DMF (25 mL), and K ₂ CO ₃ (11.0 mmol, 1.520 g). The reaction mixture was stirred under argon atmosphere at room temperature for 5 minutes, then the heat block was set at 50 ° C and the reaction mixture was stirred for 6 hours at 50 °C, then room temperature over the weekend. The reaction mixture was diluted with water (~200 mL), then extracted with ethyl ether (3 X 100 mL). The combined ether layers were washed with saturated aq. NaHCO ₃ solution (50 mL), brine (50 mL), dried over MgSO ₄ , filtered and evaporated to dryness in vacuo. Gives a light yellow oil (4.166 g, 114% yield). NMR indicates it is a mixture of the desired product and the starting bromo-glycol, ~57% product estimated). Used without further purification in the next step. MS (APCI): calculated for C19H31BO6 (M+H) = 367; found: 367. ¹ H NMR (400 MHz, Methanol-d4) δ 7.69 – 7.63 (m, 2H), 6.95 – 6.90 (m, 2H), 4.18 – 4.11 (m, 2H), 3.86 – 3.82 (m, 2H), 3.72 – 3.67 (m, 2H), 3.66 – 3.60 (m, 2H), 3.54 – 3.48 (m, 4H), 3.34 (s, 3H). Compound PLC-17.2 A 500 mL 2N round bottom flask was placed in an aluminum heat block and charged with a stir bar. The flask was fitted with a finned condenser/gas adapter, stopper and flow control valve. The system was flushed with argon. To the flask was added 6-bromo-1H,3H-benzo[de]isochromene-1,3- dione (60.0 mmol, 16.626 g) and 4-bromo-2-nitrophenol (120.0 mmol, 26.160g), followed by anhydrous NMP (250 mL). To the flask was added NaOH (30.0 mmol, 1200 mg) and copper (powder) (30.0 mmol, 1907 mg), followed by anhydrous NMP (250 mL). The flask was stirred under argon atmosphere and the heat block was set to 170 °C and the reaction stirred at this temperature for 6 hours, then at room temperature overnight. The room temperature reaction was quenched with aq. 1N HCl (60 mL). The reaction mixture was transferred to a 2L Erlenmeyer flask and diluted to ~1100 mL total volume with water with vigorous stirring. The slurry was stirred for one hour at room temperature, then the precipitate was filtered off, washing with water. The crude product was dried by suction for about 10 minutes, then suspended in methanol (~350 mL) and stirred at room temperature for 45 minutes. The precipitate was filtered off, dried by suction for ~10 minutes, then the precipitate was suspended in acetone (120 mL) and stirred at room temperature for 45 minutes. The precipitate was filtered off, washing with a small amount of acetone. The precipitate was dried by suction for ~30 minutes, then dried in a vacuum oven at ~110 °C overnight. Gives a light brown powder, 16.54 g (67% yield). MS (APCI): calculated for C ₁₈ H ₈ BrNO ₆ (M+H) = 414; found: 414. ¹ H NMR (400 MHz, DMSO-d ₆ ) δ 8.75 (dd, J = 8.4, 1.1 Hz, 1H), 8.63 (dd, J = 7.3, 1.1 Hz, 1H), 8.50 (d, J = 2.4 Hz, 1H), 8.44 (d, J = 8.2 Hz, 1H), 8.12 (dd, J = 8.8, 2.5 Hz, 1H), 7.99 (dd, J = 8.5, 7.3 Hz, 1H), 7.61 (d, J = 8.8 Hz, 1H), 7.18 (d, J = 8.3 Hz, 1H). Compound PLC-17.3

A 1L 3N round bottom flask was placed in an aluminum heat block and charged with a stir bar. The flask was fitted with a finned condenser/gas adapter, stopper and flow control valve. The system was flushed with argon. To the flask was added PLC-17.2 (26.37 mmol, 10.923 g), SnCl ₂ .2H ₂ O (105.5 mmol, 23.799 g), and HCl (4.0N, 263.7 mmol, 65.9 mL), followed by 2MeTHF (185 mL). The reaction mixture was stirred under argon and the heat block was set to 90 °C. The reaction mixture was stirred at 90 °C for 30 minutes, then cooled to room temperature. The mixture was stirred and titrated to pH ~8 with aqueous 2N NaOH. The tin salts were removed by filtration and the filter cake washed with 2MeTHF (6X50 mL). The aqueous layer was treated with NaCl until saturated, then the layers were separated. The aqueous layers were extracted with 2MeTHF (2X50 mL), then the combined 2MeTHF layers were dried over MgSO ₄ , filtered and evaporated to dryness in vacuo, followed by drying the solid at ~110 °C overnight in a vacuum oven. Gives 9.444 g (93% yield). MS (APCI): calculated for C18H10BrNO4 (M+H) = 384; found: 384. ¹ H NMR (400 MHz, Tetrachloroethane-d2) δ 8.86 (dd, J = 8.4, 1.2 Hz, 1H), 8.68 (dd, J = 7.3, 1.2 Hz, 1H), 8.48 (d, J = 8.3 Hz, 1H), 7.89 (dd, J = 8.4, 7.3 Hz, 1H), 7.11 (d, J = 2.1 Hz, 1H), 7.03 – 6.91 (m, 3H). Compound PLC-17.4 A 100 mL recovery flask was charged with a stir bar. To the flask was added NaNO ₂ (154.9 mmol, 10.688 g) and water (45 mL). This flask was stirred in an ice-water bath at 0 °C. A separate 500 mL recovery flask was charged with a stir bar. To the flask was added PLC-17.3 (20.65 mmol, 7.933 g), acetic acid (150 mL), and con. HCl (12.1N, 103.2 mmol, 8.6 mL). The mixture was stirred at room temperature for 5 minutes, then cooled for ~1 minute in an ice-water bath at 0 °C. Immediately began adding the solution of NaNO ₂ . The addition was done over a period of ~15 minutes. The crude diazo solution was stirred at 0 °C for one hour. While the diazo solution was stirring, a 1L 3N round bottom flask was set up in an aluminum heat block with a large stir bar and a finned condenser. To the flask was added CuSO4.5H ₂ O (140.4 mmol, 35.059 g) and water (420 mL). The mixture was stirred at room temperature. About 15 minutes before the diazo solution was finished, the CuSO4 solution was heated to 130 °C. With high-speed stirring, the diazo solution was added to the CuSO4 solution using a peristaltic pump and chemically-resistant tubing over a period of 45 minutes. When the addition was finished, the mixture was heated for ~1 minute at 130 °C, then placed in a room temperature water bath to bring down the temperature rapidly. The crude product was filtered off, washing with water. The crude precipitate was boiled in methanol (~100 mL), then cooled to 0 °C (ice-water bath) and filtered off, washing with methanol. Then the crude product was heated to ~95 °C in toluene (~75 mL), then cooled to 0 °C (ice-water bath), then allowed to stand overnight and come to room temperature. The precipitate was filtered off, washing with a small amount of toluene. The crude product was dried by suction, then in a vacuum oven at ~110 °C. Gives a yellowish solid, 5.538 g (73% yield). MS (APCI): calculated for C18H7BrO4 (M+H) = 367; found: 367. ¹ H NMR (400 MHz, Tetrachloroethane-d2) δ 8.61 (d, J = 7.9 Hz, 1H), 8.58 (d, J = 8.4 Hz, 1H), 8.19 (d, J = 2.2 Hz, 1H), 7.94 (d, J = 8.0 Hz, 1H), 7.69 (dd, J = 8.8, 2.3 Hz, 1H), 7.35 (s, 0H), 7.31 (d, J = 8.8 Hz, 1H). Compound PLC-17.5 A 100 mL 2N round bottom flask was placed in an aluminum heat block and charged with a stir bar. The flask was fitted with a finned condenser/gas adapter and flow control valve. The system was flushed with argon. To the flask was added PLC-17.4 (0.702 mmol, 250mg), 2-(4- aminophenyl)acetic acid (1.754 mmol, 265 mg), and DMAP (0.0512 mmol, 6.3 mg), followed by anhydrous DMF (10 mL). The reaction mixture was stirred under argon and the heat block set to 170 °C. The reaction mixture was stirred at 170 °C for 9 hours, then at room temperature. The crude reaction mixture was diluted with 75 mL of water. This mixture was stirred for 5 minutes, then the crude product was filtered off, drying by suction for 5 minutes. The wet precipitate was dried in a vacuum oven at ~110 °C overnight. Gives a yellowish powder, 366mg (107% yield). NMR shows about 10-15% dimethyl amide by-product. MS (APCI): calculated for C ₂₆ H ₁₄ BrNO ₅ (M+H) = 500; found: 500. ¹ H NMR (400 MHz, DMSO-d6) δ 8.60 (d, J = 2.3 Hz, 1H), 8.49 – 8.45 (m, 2H), 8.39 (d, J = 8.1 Hz, 1H), 7.80 – 7.75 (m, 1H), 7.48 – 7.43 (m, 2H), 7.43 – 7.38 (m, 2H), 7.31 – 7.27 (m, 2H), 3.67 (s, 2H). Compound PLC-17.6 A 250 mL 2N round bottom flask was placed in an aluminum heat block and charged with a stir bar. The flask was fitted with a finned condenser/gas adapter and flow control valve. The system was flushed with argon. To the flask was added Compound PLC-17.5 (2.00 mmol, 1001 mg), Compound 17.1 (4.00 mmol, 1465 mg), K ₂ CO ₃ (5.50 mmol, 760 mg), and Pd(dppf)Cl ₂ (0.140 mmol, 102 mg), followed by THF (60 mL), DMF (12 mL), and water (6 mL). The reaction mixture was stirred under argon and sparged with nitrogen for 10 minutes. The nitrogen sparge was stopped and stirring under argon was continued. The heat block was set at 80 °C for 2 hours. The reaction mixture was quenched with 6N HCl (5 mL) and diluted with water (50 mL) and THF (50 mL). Sodium chloride was added until the water layer was saturated, then the layers were separated, and the aqueous layer was extracted with THF (3X50 mL). The combined organic layers were washed with brine (50 mL), dried over MgSO4, filtered, and evaporated to dryness in vacuo (including DMF). The crude product was evaporated onto ~50 g flash silica gel and placed in a loader. Purified by flash chromatography on silica gel (220g, solid load, equilibrate 100% DCM, eluting 100% DCM (2 CV) → 40% (EtOAc/0.1% TFA)/DCM (20CV) → 70% (EtOAc/0.1% TFA)/DCM (20 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a yellow solid, 722 mg (55% yield). MS (APCI): calculated for C ₃₉ H ₃₃ NO ₉ (M+H) = 660; found: 660. ¹ H NMR (400 MHz, DMSO-d ₆ ) δ 8.57 (d, J = 2.2 Hz, 1H), 8.52 (s, 2H), 8.48 (d, J = 8.3 Hz, 1H), 7.90 (dd, J = 8.7, 2.2 Hz, 1H), 7.84 – 7.78 (m, 2H), 7.55 (d, J = 8.7 Hz, 1H), 7.48 (d, J = 8.3 Hz, 1H), 7.41 (d, J = 8.1 Hz, 2H), 7.33 – 7.26 (m, 2H), 7.12 – 7.07 (m, 2H), 4.22 – 4.14 (m, 2H), 3.82 – 3.76 (m, 2H), 3.68 (s, 2H), 3.65 – 3.59 (m, 2H), 3.58 – 3.51 (m, 4H), 3.48 – 3.41 (m, 2H), 3.25 (s, 3H). Compound PLC-17

A 40 mL vial was charged with a stir bar, followed by PLC-17.6 (0.075 mmol, 49.5 mg), PLC-1.1 – diethyl 5,5-difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-1,3,7,9-tetra methyl-5H-4l4,5l4- dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxyla te (0.050 mmol, 25.6 mg), DMAP.pTsOH salt (0.100 mmol, 29.4 mg), and EDC.HCl (0.200 mmol, 38.3 mg), followed by anhydrous DCM. The vial was capped, and the reaction mixture stirred at room temperature overnight. The crude reaction was quenched with a few drops of TFA and loaded onto ~65 g flash silica gel in a loader. Purified by flash chromatography on silica gel (120 g, solid load, equilibrate 100% DCM, eluting 100% DCM (3 CV) → 10% EtOAc/DCM (10 CV) →40% EtOAc/DCM (10 CV)). Fractions containing product were evaporated to dryness in vacuo. The crude product was dried in a vacuum oven at ~110 °C. Gives an orange solid, 52 mg (90% yield). MS (APCI): calculated for C ₆₆ H ₆₂ BF ₂ N ₃ O ₁₃ (M-) = 1153; found: 1153. ¹ H NMR (400 MHz, Tetrachloroethane-d2) δ 8.68 (d, J = 7.9 Hz, 1H), 8.63 (d, J = 8.4 Hz, 1H), 8.25 (d, J = 2.1 Hz, 1H), 8.11 (d, J = 8.2 Hz, 1H), 7.78 (dd, J = 8.6, 2.1 Hz, 1H), 7.68 – 7.61 (m, 4H), 7.50 (d, J = 8.6 Hz, 1H), 7.43 – 7.35 (m, 3H), 7.12 – 7.07 (m, 2H), 7.05 (s, 2H), 4.28 (q, J = 7.1 Hz, 4H), 4.22 (t, J = 4.8 Hz, 2H), 4.01 (s, 2H), 3.90 (t, J = 4.8 Hz, 2H), 3.78 – 3.73 (m, 2H), 3.72 – 3.62 (m, 4H), 3.59 – 3.54 (m, 2H), 3.38 (s, 3H), 2.84 (s, 6H), 2.16 (s, 6H), 1.74 (s, 6H), 1.34 (t, J = 7.1 Hz, 6H). Synthesis of Compound PLC-18 Compound PLC-18.1 A 50 mL 2N round bottom flask was placed in an aluminum heat block and charged with a stir bar. The flask was fitted with a finned condenser/gas adapter, stopper and flow control valve. The system was flushed with argon. To the flask was added PLC-6.3 (3.00 mmol, 1101 mg), ethanolamine (12.0 mmol, 0.725 mL), and DMAP (0.900 mmol, 110 mg), followed by anhydrous DMF (8 mL). The reaction mixture was stirred under argon and the heat block was set to 165 °C. The reaction mixture was stirred at this temperature for 3 hours, then the reaction mixture was cooled to room temperature. The solvent was evaporated to dryness in vacuo. The residue was triturated with water (50 mL) and 6N aqueous HCL (10 mL). The mixture was sonicated for a few minutes, then stirred at room temperature for 30 minutes, then the solid product was filtered off, washing with water. The crude filter cake was dried in a vacuum oven at ~110 °C overnight. Gives a dark brownish solid, 1.038 g (84% yield. MS (APCI): calculated for C ₂₀ H ₁₂ BrNO ₄ (M+H) = 410; found: 410. Compound PLC-18.2 PLC-18.2 was synthesized from PLC-18.1 (2.531 mmol, 1.038 g), (4- (trifluoromethyl)phenyl)boronic acid (5.062 mmol, 961 mg), K ₂ CO ₃ (6.960 mmol, 962 mg), and Pd(dppf)Cl2 (0.177 mmol, 130 mg) in THF/DMF/H ₂ O (60 mL/12 mL/6 mL) at 80 °C for 30 minutes in a manner similar to PLC-17.6. The crude product was precipitated by adding water (100 mL), then filtering off the resulting solid, washing with water. The crude product was triturated with methanol, then dried in a vacuum oven at ~110 °C overnight. Gives 1.017 g (84% yield). MS (APCI): calculated for C ₂₇ H ₁₆ F ₃ NO ₄ (M+H) = 476; found: 476. ¹ H NMR (400 MHz, TCE) δ 8.66 (d, J = 7.8 Hz, 1H), 8.61 (d, J = 8.3 Hz, 1H), 8.25 (d, J = 2.2 Hz, 1H), 8.06 (d, J = 8.0 Hz, 1H), 7.83 – 7.75 (m, 5H), 7.52 (d, J = 8.6 Hz, 1H), 7.37 (d, J = 8.4 Hz, 1H), 4.45 (t, J = 5.2 Hz, 2H), 3.98 (q, J = 5.3 Hz, 2H), 2.49 (t, J = 5.5 Hz, 1H). Compound PLC-18.3 A 250 mL 2N round bottom flask was placed in an aluminum heat block and charged with a stir bar. The flask was fitted with a finned condenser/gas adapter, stopper and flow control valve. The system was flushed with argon. To the flask was added PLC-18.2 (2.124 mmol, 1.01 g), pTsCl (6.372 mmol, 1.215 g), anhydrous DMF (20 mL), and Et3N (6.372 mmol, 0.888 mL). The reaction mixture was stirred under argon and heated to 80 °C for 2 hours. An unexpected reaction occurred when the tosylate was displaced in situ by chloride ion. The reaction mixture was cooled to room temperature and diluted with water (100 mL). The crude product was filtered off, washing with water. The crude product was triturated with MeOH. The product was dried in a vacuum oven at ~110 °C overnight. Gives 974 mg of an orange solid (93% yield). MS (APCI): calculated for C ₂₇ H ₁₅ ClF ₃ NO ₃ (M+H) = 494; found: 494. ¹ H NMR (400 MHz, TCE) δ 8.67 (d, J = 7.9 Hz, 1H), 8.62 (d, J = 8.3 Hz, 1H), 8.27 (d, J = 2.2 Hz, 1H), 8.08 (d, J = 7.9 Hz, 1H), 7.86 – 7.73 (m, 5H), 7.53 (d, J = 8.6 Hz, 1H), 7.39 (d, J = 8.4 Hz, 1H), 4.56 (t, J = 6.9 Hz, 2H), 3.87 (t, J = 6.8 Hz, 2H). Compound PLC-18.4

A 100 mL 2N round bottom flask was placed in an aluminum heat block and charged with a stir bar. The flask was fitted with a finned condenser/gas adapter, stopper and flow control valve. To the flask was added PLC-18.3 (0.607 mmol, 300 mg), 4-hydroxy-2,6-dimethylbenzaldehyde (1.336 mmol, 201 mg), and K ₂ CO ₃ (1.215 mmol, 168 mg), followed by anhydrous DMF (20 mL). The reaction mixture was stirred under argon and the heat block was set to 100 °C. The reaction mixture was stirred under argon atmosphere for 8 hours, then room temperature overnight. The crude reaction mixture was diluted with water (~100 mL) and the precipitate filtered off, washing with water. The crude product was dissolved in DCM and evaporated to dryness. The crude product was re-dissolved in DCM and evaporated onto flash silica gel (~20 g). Purified by flash chromatography on silica gel (120 g, solid load, equilibrate 70% hexanes/DCM, eluting 70% hexanes/DCM (2 CV) → 100% DCM/hexanes (10 CV) → isocratic 100% DCM/hexanes (5 CV) → 0% EtOAc/DCM (0 CV) → isocratic 0% EtOAc/DCM (10 CV) → 40% EtOAc/DCM (40 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives 48 mg (13% yield) of a yellow solid. MS (APCI): calculated for C ₃₆ H ₂₄ F ₃ NO ₀ (M-) = 607; found: 607. ¹ H NMR (400 MHz, TCE) δ 10.41 (s, 1H), 8.69 (d, J = 7.8 Hz, 1H), 8.64 (d, J = 8.3 Hz, 1H), 8.27 (d, J = 2.1 Hz, 1H), 8.09 (d, J = 8.1 Hz, 1H), 7.85 – 7.75 (m, 5H), 7.53 (d, J = 8.6 Hz, 1H), 7.39 (d, J = 8.3 Hz, 1H), 6.66 (s, 2H), 4.65 (t, J = 6.2 Hz, 2H), 4.38 (t, J = 6.2 Hz, 2H), 2.57 (s, 6H). Compound PLC-18 A 100 mL 2N round bottom flask was placed in an aluminum heat block and charged with a stir bar. The flask was fitted with a finned condenser/gas adapter, stopper and flow control valve. The system was flushed with argon. To the flask was added PLC-18.4 (0.0741 mmol, 45 mg) ethyl 2,4- dimethyl-1H-pyrrole-3-carboxylate (0.1556 mmol, 26 mg), followed by anhydrous DCE (15 mL). Under argon atmosphere, the reaction mixture was sparged with nitrogen for 10 minutes. A couple of small granules of pTsOH.H ₂ O were gathered onto the end of a spatula and these were dipped in the reaction mixture. Stirring and sparging with nitrogen were continued for another 5 minutes. The nitrogen sparge was stopped and the reaction mixture was stirred at under argon atmosphere. The heat block was set to 85 °C and the reaction mixture stirred at this temperature overnight. TLC shows complete conversion to the desired dipyrrolomethane. The reaction mixture was cooled to room temperature in a water bath. To the flask was added DDQ (0.111 mmol, 25 mg) and the reaction mixture was stirred at room temperature for one hour. TLC indicates complete oxidation to dipyrromethene. To the flask was added Et ₃ N (0.593mmol, 0.139 mL) and BF ₃ .OEt ₂ (0.110 mmol, 0.111 mL). The addition of both reagents was repeated after 2 minutes, then the heat block was set to 60 °C and the reaction mixture stirred at this temperature for 2 hours under argon. The crude BODIPY was loaded onto flash silica gel directly (~25g). Purified by flash chromatography on silica gel (80g, solid load, equilibrate 80% DCM/hexanes, eluting 50% DCM/hexanes (2 CV) → 100 DCM/hexanes (10 CV) → isocratic 100% DCM/hexanes (10 CV) → 0% EtOAc/DCM (0 CV) → isocratic 0% EtOAc/DCM (5 CV) → 40% EtOAc/DCM (40 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 50 mg (70% yield). MS (APCI): calculated for C54H45BF5N3O8 (M-) = 969; found: 969. ¹ H NMR (400 MHz, TCE) δ 8.70 (d, J = 7.9 Hz, 1H), 8.65 (d, J = 8.4 Hz, 1H), 8.28 (d, J = 2.2 Hz, 1H), 8.09 (d, J = 8.1 Hz, 1H), 7.85 – 7.75 (m, 5H), 7.53 (d, J = 8.6 Hz, 1H), 7.40 (d, J = 8.3 Hz, 1H), 6.78 (s, 2H), 4.67 (t, J = 6.3 Hz, 2H), 4.36 (t, J = 6.4 Hz, 2H), 4.25 (q, J = 7.1 Hz, 4H), 2.81 (s, 6H), 2.05 (s, 6H), 1.67 (s, 6H), 1.32 (t, J = 7.1 Hz, 6H). Synthesis of Compound PLC-19

To the flask, PLC-6.3 (1.5 g, 4.1 mmol), 2-(2-aminoethoxy)ethan-1-ol (859.0 mg, 8.2 mmol) and DMAP (35.1 mg, 0.3 mmol) in DMF (30 ml) was degassed at room temperature. The reaction mixture was heated up to 165 ºC and the reaction has been kept at this temperature for 2 hrs. TLC and LCMS showed the completion of the reaction. The reaction was cooled down to room temperature. H ₂ O (70 ml) was added to precipitate the product. The precipitate was collected by filtration. The solid was washed by H ₂ O (150 ml) and further dried in a vacuum oven at 100 ºC for 3 hours to provide PLC-19.1 as a yellow solid for the next step without further purification.1.45 g, 78% yield. MS (APCI): calculated for C ₂₂ H ₁₆ BrNO ₅ ([M-H]-) = 454 found: 454. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.62 (d, J = 8.0 Hz, 1H), 8.59 (d, J = 8.0 Hz, 1H), 8.19 (d, J = 2.4 Hz, 1H), 7.92 (d, J = 8.0 Hz, 1H), 7.65 (dd, J = 8.0 Hz, J = 2.4 Hz, 2H), 7.33 (d, J = 8.0 Hz, 1H), 7.29 (d, J = 8.0 Hz, 1H), 4.42 (t, J = 5.6 Hz, 2H), 3.85 (t, J = 5.6 Hz, 2H), 3.67 (m, 4H). Compound PLC-19.2 A 250 mL flask was fitted with a stir bar. To the flask, PLC-19.1 (800.0 mg, 1.8 mmol), 4- (trifluoromethyl)phenylboronic acid (670.0 mg, 3.5 mmol), Pd(dppf)Cl ₂ (90.6 mg, 0.1 mmol) and K ₂ CO ₃ (659.5 mg, 4.8 mmol) in THF/DMF/H ₂ O (48 ml/ 9.6 ml/ 4.8 ml) was degassed at room temperature. The reaction mixture was heated up to 80 ºC and the reaction has been kept at this temperature overnight. TLC was used to monitor the reaction. After the completion, the reaction was worked up by the addition of H ₂ O (150 ml) added to precipitate the product. The precipitate was collected by filtration. The solid was washed by H ₂ O (200 ml) and MeOH (20 ml), and further dried in a vacuum oven at 100 ºC for 3 hours to provide PLC-19.2 as a yellow green solid for the next step without further purification. Quantitative yield. MS (APCI): calculated for C ₂₉ H ₂₀ F ₃ NO ₅ ([M+H] ⁺ ) = 520 found: 520. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.67 (d, J = 8.0 Hz, 1H), 8.61 (d, J = 8.0 Hz, 1H), 8.26 (d, J = 2.0 Hz, 1H), 8.07 (d, J = 8.0 Hz, 1H), 7.79 (m, 5H), 7.52 (d, J = 8.4 Hz, 1H), 7.38 (d, J = 8.4 Hz, 1H), 5.11 (bs, 1H), 4.44 (t, J = 1.6 Hz, 2H), 3.86 (t, J = 1.6 Hz, 2H), 3.68 (m, 4H). Compound PLC-19.3A and PLC-19.3B

A 100 mL flask was fitted with a stir bar. To the flask, PLC-19.2 (900.0 mg, 1.7 mmol) and DMF/THF (18 ml/ 6 ml) were added. The solution was degassed at room temperature. Methanesulfonyl chloride (595.4 mg, 5.2 mmol) and TEA (526.2 mg,5.2 mmol) were added. Then the solution heated up to 90 ºC and it has been kept at this temperature for 20 minutes. TLC was used to monitor the reaction. After the completion, the reaction was worked up by the addition of H ₂ O (150 ml) added to precipitate the product. The precipitate was collected by filtration. The solid was washed by H ₂ O (100 ml) and MeOH (15 ml), and further dried in a vacuum oven at 100 ºC for 3 hours to provide a mixture of PLC-19.3A and PLC-19.3B as a yellow solid for the next step without further purification. Quantitative yield. For PLC-19.3A, MS (APCI): calculated for C ₃₀ H ₂₂ F ₃ NO ₇ S ([M+H] ⁺ ) = 598 found: 598. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.65 (d, J = 8.0 Hz, 1H), 8.60 (d, J = 8.0 Hz, 1H), 8.26 (d, J = 2.0 Hz, 1H), 8.07 (d, J = 8.0 Hz, 1H), 7.78 (m, 5H), 7.52 (d, J = 8.4 Hz, 1H), 7.38 (d, J = 8.4 Hz, 1H), 4.44 (t, J = 2.0 Hz, 2H), 4.35 (m, 2H), 3.86 (t, J = 2.0 Hz, 2H), 3.81 (m, 2H), 3.01 (s, 3H). For PLC-19.3B, MS (APCI): calculated for C ₂₉ H ₁₉ ClF ₃ NO ₄ ([M-H]-) = 537 found: 537. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.66 (d, J = 8.0 Hz, 1H), 8.61 (d, J = 8.0 Hz, 1H), 8.26 (d, J = 2.0 Hz, 1H), 8.07 (d, J = 8.0 Hz, 1H), 7.79 (m, 5H), 7.52 (d, J = 8.4 Hz, 1H), 7.37 (d, J = 8.4 Hz, 1H), 4.43 (t, J = 2.0 Hz, 2H), 3.86 (t, J = 2.0 Hz, 2H), 3.81 (t, J = 1.6 Hz, 2H), 3.63 (t, J = 1.6 Hz, 2H). Compound PLC-19.4 To a 100 ml flask, NaH (15.4 mg, 0.4 mmol) and DMF (5 ml) was added, followed by the addition of 4-hydroxy-2,6-methylbenzaldehyde (43.6 mg, 0.3 mmol). The mixture has been kept stirring at room temperature for 10 minutes. The PLC-19.3B (104.0 mg, 0.2 mmol) was added. The reaction was heated up to 160 ºC and has been kept stirring at this temperature overnight. TLC (50% EtOAc in Hexane) showed the completion of the reaction. The reaction mixture was purified by silica gel flash chromatography using EtOAc in DCM (0-40%) as an eluant to provide pure compound PLC- 19.4 as an orange yellow solid, 73.0 mg, 59% yield. MS (APCI): calculated for C ₃₈ H ₂₈ F ₃ NO ₆ ([M+H] ⁺ ) = 652 found: 652. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) δ 10.20 (s, 1H), 8.61 (d, J = 8.0 Hz, 1H), 8.56 (d, J = 8.0 Hz, 1H), 8.22 (d, J = 2.0 Hz, 1H), 8.00 (d, J = 8.0 Hz, 1H), 7.81 (m, 5H), 7.50 (d, J = 8.0 Hz, 1H), 7.32 (d, J = 8.0 Hz, 1H), 6.56 (s, 2H), 4.44 (t, J = 2.0 Hz, 2H), 4.00 (m, 2H), 3.92 (t, J = 2.0 Hz, 2H), 3.86 (m, 2H), 2.45 (s, 6H). Compound PLC-19 A 100 mL 2 neck round bottomed flask was fitted with an air condenser and a stir bar. To the flask, PLC-19.4 (73.0 mg, 0.1 mmol) and ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (39.0 mg, 0.2 mmol) were added, followed by anhydrous dichloroethane (7 ml). The reaction mixture was sparged with Ar for 30 minutes, then p-TsOH•H ₂ O (0.7 mg, 0.006 mmol) was added. The reaction solution was heated up to 85 ºC and has been kept at this temperature overnight. Then the reaction was cooled down to room temperature and DDQ (13.7 mg, 0.06 mmol) was added. The reaction was kept at room temperature for 30 minutes. Then BF ₃ •OEt ₂ (0.16 mL, 1.3 mmol) and Et ₃ N (0.12 mL, 0.9 mmol) were added at room temperature. The reaction mixture was heated up to 60 ºC and has been kept at this temperature for 1 hour. The reaction mixture was loaded with silica gel and purified by flash chromatography, using EtOAc in DCM (0-10%) as an eluant to provide the pure PLC-19 as an orange solid, 38.0 mg, 36% yield. MS (APCI): calculated for C ₅₆ H ₄₉ BF ₅ N ₃ O ₉ ([M-H]-) = 1013 found: 1013. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.68 (d, J = 8.0 Hz, 1H), 8.63 (d, J = 8.0 Hz, 1H), 8.27 (d, J = 2.4 Hz, 1H), 8.08 (d, J = 8.0 Hz, 1H), 7.79 (m, 5H), 7.52 (d, J = 8.0 Hz, 1H), 7.38 (d, J = 8.0 Hz, 1H), 6.69 (s, 2H), 4.48 (t, J = 6.0 Hz, 2H), 4.26 (q, J = 7.2 Hz, 4H), 4.14 (m, 2H), 3.92 (m, 4H), 2.82 (s, 6H), 2.05 (s, 6H), 1.70 (s, 6H), 1.33 (t, J = 7.2 Hz, 6H). Compound PLC-20 PLC-20.1 (1.223 g, 3.33 mmol, 1 eq) was suspended in 35 mL DMSO anhydrous, 5-amino-1- pentanol (0.687 g, 6.66 mmol, 2 eq) was added to the reaction mixture at room temperature. The resulting mixture was stirred at 160 ºC for 45 minutes, LMCMS shown reaction was completed. After cooling to room temperature, the solid product was filtered, washed with water (250 mL) then MeOH (100 mL), dried in vacuo-oven to gain 1.2 g greenish yellow solid, yield 85%. MS (APCI): calculated for C ₂₃ H ₁₈ BrNO ₄ (M-) = 453; found: 453. ¹ H NMR (400 MHz) δ 8.52 (d, J = 7.8 Hz, 1H), 8.48 (d, J = 8.3 Hz, 1H), 8.09 (d, J = 2.3 Hz, 1H), 7.82 (d, J = 8.0 Hz, 1H), 7.54 (dd, J = 8.8, 2.3 Hz, 1H), 7.23 (d, J = 8.3 Hz, 1H), 7.19 (d, J = 8.8 Hz, 1H), 4.14 – 4.02 (m, 2H), 3.64 – 3.49 (m, 2H), 1.68 (p, J = 7.7 Hz, 2H), 1.60 – 1.54 (m, 2H), 1.41 (q, J = 8.0 Hz, 2H), 1.28 (s, 1H). Compound PLC-20.3

PLC-20.2 (1.13 g, 2.5 mmol, 1eq) was suspended in DMF (10 ml), H ₂ O (5 ml), added 4- trifluoromethyl) benzene boronic acid (0.949 g, 5.0 mmol, 2 eq), K ₂ CO ₃ (0.691 g, 5.0 mmol, 2eq), Pd(dppf)Cl2 · DCM (40.8 mg, 0.05 mmol, 0.02eq). The mixture was degassed by Vac-Fill Argon cycle 3 times, stirred & heated at 90 ºC 5 hours. The reaction mixture was cooled to room temperature, water was added. The resulting mixture was hold at room temperature 12 hours. The greenish yellow solid was filtered, washed with water then MeOH to obtain 1.24 g greenish yellow solid, yield 95%. MS (APCI): calculated for C ₃₀ H ₂₂ F ₃ NO ₄ (M-) = 517; found: 517. ¹ H NMR (400 MHz) δ 8.56 (d, J = 7.9 Hz, 1H), 8.51 (d, J = 8.3 Hz, 1H), 8.17 (d, J = 2.1 Hz, 1H), 7.97 (d, J = 8.0 Hz, 1H), 7.69 (dd, J = 10.3, 1.9 Hz, 4H), 7.42 (d, J = 8.6 Hz, 1H), 7.28 (d, J = 8.3 Hz, 1H), 4.09 (t, J = 7.5 Hz, 2H), 3.57 (q, J = 6.2 Hz, 2H), 1.69 (p, J = 7.8 Hz, 2H), 1.61 – 1.54 (m, 2H), 1.42 (q, J = 8.0 Hz, 2H), 1.28 (t, J = 5.5 Hz, 1H). Compound PLC-20.4 Reflux (HBr 48% bp:126 ºC) the mixture of PLC-20.3 (0.66 g, 1.288 mmol) and 48% aqueous HBr (20.0 ml) by heating block at 120 ºC for 5 h with stirring. After cooling to room temperature, the mixture was poured to ice water, the solid was filtered, washed with water, dried in vacuo-oven to obtain 82% desired compound containing with unreacted SM. Gained 0.7 g greenish yellow solid, yield 93%. Product was used next step without further purification. MS (APCI): calculated for C30H21BrF3NO3 (M-) = 581; found: 581. ¹ H NMR (400 MHz) δ 8.57 (d, J = 7.9Hz, 1H), 8.51 (d, J = 8.3 Hz, 1H), 8.18 (d, J = 2.2 Hz, 1H), 7.98 (d, J = 7.9 Hz, 1H), 7.69 (dd, J = 9.6, 2.0 Hz, 4H), 7.43 (d, J = 8.6 Hz, 1H), 7.28 (d, J = 8.3 Hz,1H), 4.09 (t, J = 7.5 Hz, 3H), 3.38 (t, J = 6.7 Hz, 2H), 1.97 – 1.81 (m, 2H), 1.69 (t, J = 7.8 Hz, 2H). Compound PLC-20.5 A mixture of 2,6-dimethyl-4-hydroxybenxaldehyde (60.08 mg, 0.4 mmol, 1 eq), K ₂ CO ₃ (110.56 mg, 0.8 mmol, 2eq), NaI (4.6 mg, cat. amount) and PLC-20.4 (243.76 mg, 0.42 mmol, 1.05 eq) in DMF anhydrous (4.0 ml) was mixing together by sonicating for 10 minutes before stirred at 65 ^o C, under Argon atmosphere 24 hours. After cooling to room temperature, the mixture was concentrated to dryness, washed solid with (50 ml x 2) hot water, the yellow solid was collected by filtering. The crude was sonicating with MeOH at 65 ºC, cooled, filtering and dried in vacuo oven. The product was used next step without further purification, gained 257 mg, yield 98 %. MS (APCI): calculated for C ₃₉ H ₃₀ F ₃ NO ₅ (M-) = 649; found: 649. ¹ H NMR (400 MHz, ) δ 10.33 (s, 1H), 8.56 (d, J = 7.8 Hz, 1H), 8.51 (d, J = 8.4 Hz, 1H), 8.17 (d, J = 2.2 Hz, 1H), 7.98 (d, J = 8.0 Hz, 1H), 7.69 (dd, J = 9.0, 1.9 Hz, 5H), 7.43 (d, J = 8.6 Hz, 1H), 7.28 (d, J = 8.3 Hz, 1H), 6.51 (s, 2H), 4.11 (t, J = 7.6 Hz, 3H), 3.94 (t, J = 6.4 Hz, 2H), 2.50 (s, 6H), 1.76 (dt, J = 24.1, 7.8 Hz, 4H). Compound PLC-20

Step 1: In a 50 ml vial was equipped with: septum cap, magnetic stirring bar; a mixture of compound benzyl 2,4-dimethyl-1H -pyrrole-3-carboxylate (68.55 mg, 0.41 mmol, 2.05eq), PLC-20.5 (129.93 mg, 0.2 mmol, 1 eq in 1,2-dichloroethane (DCE) anhydrous (4 ml) was bubbling with Argon and stirred at room temperature 15 minutes, 1 ml mixture of 50 ml DCE + 5 drop TFA was added in one portion. The resulting mixture was then stirred at 68 ºC under Argon atmosphere for 24 hrs. LCMS shown only 50% starting materials were consumed. 8 mg pTSA was added and the RX was further stirred at 90 ºC for 45 minutes, LCMS shown starting materials were completely converted. The crude product was used in situ next step without further purification. Step 2: The above mixture was cooled to RT, 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (0.148 g, 0.625 mmol) was added in one portion. The resulting mixture was stirred at room temperature 1/2 hour. TLC and LCMS shown starting materials were converted completely. Step 3: The above mixture was cooled to 0 ºC then stirred with triethylamine (0.25 ml, 3.48 mmol) for 15 minutes. BF3 etherate (071 mL, 2.76 mmol) was added dropwise. The resulting reaction mixture was stirred at 86 ºC under Argon atmosphere for 45 minutes; cooled to 0 ºC quenched with EtOH (2 ml), and the solvents were removed by rotavapor. The residue was chromatographed on column of silica gel (80 g), eluting with DCM only (1CV) then DCM/ EtOAc (98:2) and then washed with EtOH to afford the pure title product (1574-114) as orange yellow solid (0.120g, 59 % total yield base on 1574-112 aldehyde SM. MS (APCI): calculated for C ₅₇ H ₅₁ BF ₅ N ₃ O ₈ (M-) = 1011; found: 1011. ¹ H NMR (400 MHz, ) δ 8.57 (d, J = 7.9 Hz, 1H), 8.52 (d, J = 8.3 Hz, 1H), 8.17 (d, J = 2.3 Hz, 1H), 7.98 (d, J = 8.0 Hz, 1H), 7.69 (dd, J = 9.5, 1.8 Hz, 5H), 7.42 (d, J = 8.6 Hz, 1H), 7.28 (d, J = 8.3 Hz, 1H), 6.65 (s, 2H), 4.18 (q, J = 7.1 Hz, 4H), 4.12 (t, J = 7.6 Hz, 2H), 3.93(t, J = 6.5 Hz, 2H), 2.73 (s, 6H), 1.99 (s, 6H), 1.82 (t, J = 7.3 Hz, 2H), 1.79 – 1.69 (m, 2H), 1.64 (s, 6H), 1.56 (s, 2H), 1.24 (t, J = 7.1 Hz, 6H).2.28 – 2.19 (m, 4H), 2.06 – 1.85 (m, 4H), 0.78 (d, J = 14.2 Hz, 2H). Compound PLC-21 PLC-20.1 (1.223 g, 3.33 mmol, 1 eq) was suspended in 35 mL DMSO anhydrous, 5-amino-1- pentanol (0.687 g, 6.66 mmol, 2 eq) was added to the reaction mixture at room temperature. The resulting mixture was stirred at 160 ºC for 3 days, LMCMS shown reaction was completed. After cooling to room temperature, the solid product was filtered, washed with water (250 mL) then MeOH (100 mL), dried in vacuo-oven to gain 1.2 g greenish yellow solid, yield 92%. MS (APCI): calculated for C ₂₃ H ₁₈ BrNO ₄ (M-) = 425; found: 425. ¹ H NMR (400 MHz) δ 8.56 (d, J = 7.9 Hz, 1H), 8.52 (d, J = 8.4 Hz, 1H), 8.13 (d, J = 2.3 Hz, 1H), 7.86 (d, J = 7.9 Hz, 1H), 7.57 (dd, J = 8.8, 2.3 Hz, 1H), 7.26 (d, J = 8.4 Hz, 1H), 7.22 (d, J = 8.8 Hz, 1H), 4.24 (t, J = 6.1 Hz, 2H), 3.48 (q, J = 6.1 Hz, 2H), 3.06 (t, J = 6.9 Hz, 1H), 1.95 – 1.83 (m, 2H). Compound PLC-21.2 PLC-21.1 (1.06 g, 2.5 mmol, 1eq) was suspended in DMF (10 ml), H ₂ O (5 ml), added 4- trifluoromethyl) benzene boronic acid (0.949 g, 5.0 mmol, 2 eq), K ₂ CO ₃ (0.691 g, 5.0 mmol, 2eq), Pd(dppf)Cl2 · DCM (40.8 mg, 0.05 mmol, 0.02eq). The mixture was degassed by Vac-Fill Argon cycle 3 times, stirred & heated at 90 ºC 5 hours. The reaction mixture was cooled to room temperature, water was added. The resulting mixture was holding at room temperature 12 hours. The greenish yellow solid was filtered, washed with water then MeOH to obtain 1.04 g greenish yellow solid, yield 85%. MS (APCI): calculated for C30H22F3NO4 (M-) = 517; found: 517. ¹ H NMR (400 MHz) δ 8.56 (d, J = 7.9 Hz, 1H), 8.51 (d, J = 8.3 Hz, 1H), 8.17 (d, J = 2.1 Hz, 1H), 7.97 (d, J = 8.0 Hz, 1H), 7.69 (dd, J = 10.3, 1.9 Hz, 4H), 7.42 (d, J = 8.6 Hz, 1H), 7.28 (d, J = 8.3 Hz, 1H), 4.09 (t, J = 7.5 Hz, 2H), 3.57 (q, J = 6.2 Hz, 2H), 1.69 (p, J = 7.8 Hz, 2H), 1.61 – 1.54 (m, 2H), 1.42 (q, J = 8.0 Hz, 2H), 1.28 (t, J = 5.5 Hz, 1H). Compound PLC-21.3 A mixture of PLC-21.2 (1.6 g, 3.2 mmol) and 48% aqueous HBr (30.0 ml) heated to refluxed by heating block at 130 ºC for 3 days with stirring. The same volume of 48% aq HBr was added for 2 more times in the next 2 days, total amount was 90 ml. After cooling to room temperature, the mixture was poured to ice water, the solid was filtered, washed with water, dried in vacuo-oven to obtain 82% desired compound containing with unreacted SM. Gained 1.7 g greenish yellow solid, yield 96%. Product was used next step without further purification. MS (APCI): calculated for C ₃₀ H ₂₁ BrF ₃ NO ₃ (M- ) = 551; found: 551. ¹ H NMR (400 MHz) δ 8.55 (d, J = 7.9 Hz, 1H), 8.50 (d, J = 8.4 Hz, 1H), 8.15 (d, J = 2.2 Hz, 1H), 7.96 (d, J = 8.0 Hz, 1H), 7.70 (s, 5H), 7.41 (d, J = 8.6 Hz, 1H), 7.27 (d, J = 8.3 Hz, 1H), 4.22 (t, J = 7.1 Hz, 2H), 3.45 (t, J = 6.8 Hz, 2H), 2.25 (q, J = 6.9 Hz, 2H). Compound PLC-21.4 A mixture of 2,6-dimethyl-4-hydroxybenxaldehyde (60.08 mg, 0.4 mmol, 1 eq), K ₂ CO ₃ (110.56 mg, 0.8 mmol, 2eq), NaI (4.6 mg, cat. amount) and PLC-21.3 (231.98 mg, 0.42 mmol, 1.05 eq) in DMF anhydrous (4.0 ml) was mixing together by sonicating for 10 minutes before stirred at 65 ^o C, under Argon atmosphere 24 hours. After cooling to room temperature, the mixture was concentrated to dryness, washed solid with (50 ml x 2) hot water, the yellow solid was collected by filtering. The crude was sonicating with MeOH at 65 ^o C, cooled, filtering and dried in vacuo oven. The product was used next step without further purification, gained 239 mg, yield 96%. MS (APCI): calculated for C ₃₇ H ₂₆ F ₃ NO ₅ (M-) = 621; found: 621. ¹ H NMR (400 MHz, ) δ 10.34 (s, 1H), 8.56 (d, J = 7.7 Hz, 1H), 8.51 (d, J = 8.3 Hz, 1H), 8.18 (d, J = 2.2 Hz, 1H), 7.98 (d, J = 7.9 Hz, 1H), 7.70 (dd, J = 7.4, 2.3 Hz, 6H), 7.44 (d, J = 8.6 Hz, 1H), 7.29 (d, J = 8.2 Hz, 1H), 6.46 (s, 2H), 4.30 (t, J = 7.0 Hz, 2H), 4.09 (t, J = 5.9 Hz, 2H), 2.47 (s, 6H), 2.17 (t, J = 6.7 Hz, 2H). Compound PLC-21

Step 1: In a 50 ml vial was equipped with: septum cap, magnetic stirring bar; a mixture of compound benzyl 2,4-dimethyl-1H -pyrrole-3-carboxylate (68.55 mg, 0.41 mmol, 2.05eq), PLC-21.4 (124.32 mg, 0.2 mmol, 1 eq in 1,2-dichloroethane (DCE) anhydrous (4 ml) was bubbling with Argon and stirred at room temperature 15 minutes, 1 ml mixture of 50 ml DCE + 5 drop TFA was added in one portion. The resulting mixture was then stirred at 68 ºC under Argon atmosphere for 24 hrs LCMS shown only 50% starting materials were consumed. 8 mg pTSA was added and the RX was further stirred at 90 ºC for 45 minutes, LCMS shown starting materials were completely converted. The crude product was used in situ next step without further purification. Step 2: The above mixture was cooled to room temperature, 2,3-Dichloro-5,6-dicyano-1,4- benzoquinone (DDQ) (0.148 g, 0.625 mmol) was added in one portion. The resulting mixture was stirred at room temperature 1/2 hour. TLC and LCMS shown starting materials were converted completely. Step 3: The above mixture was cooled to 0 ºC then stirred with triethylamine (0.25 ml, 3.48 mmol) for 15 minutes. BF3 etherate (071 mL, 2.76 mmol) was added dropwise. The resulting reaction mixture was stirred at 86 ºC under Argon atmosphere for 45 minutes; cooled to 0 ºC quenched with EtOH (2 ml), and the solvents were removed by rotavapor. The residue was chromatographed on column of silica gel (80 g), eluting with DCM only (1CV) then DCM/ EtOAc (98:2) and then washed with EtOH to afford the pure title product PLC-21 as orange yellow solid (0.097g, 49 % total yield base on PLC-21 aldehyde SM). MS (APCI): calculated for C ₅₅ H ₄₇ BF ₅ N ₃ O ₈ (M-) = 983; found: 983. ¹ H NMR (400 MHz, ) δ 8.56 (d, J = 7.9 Hz, 1H), 8.51 (d, J = 8.3 Hz, 1H), 8.17 (d, J = 2.1 Hz, 1H), 7.98 (d, J = 8.0 Hz, 1H), 7.69 (dd, J = 8.8, 2.0 Hz, 5H), 7.42 (d, J = 8.6 Hz, 1H), 7.28 (d, J = 8.3 Hz, 1H), 6.58 (s, 2H), 4.33 (t, J = 7.1 Hz, 2H), 4.18 (q, J = 7.1 Hz, 4H), 4.08 (t, J = 6.2 Hz, 2H), 2.73 (s, 6H), 2.19 (t, J = 6.8 Hz, 2H), 1.63 (s, 6H), 1.53 (s, 8H), 1.25 (t, J = 7.1 Hz, 6H). Synthesis of Compound PLC-22 Compound PLC-22.1: A mixture of Compound PLC-27.1 (vide supra) (9-bromo-2-(3-hydroxypropyl)-1H-xantheno[2,1,9- def]isoquinoline-1,3(2H)-dione) (330 mg, 0.778 mmol), (2,4,6-triisopropylphenyl)boronic acid (290mg, 1.17 mmol), Pd(PPh3)4 (80mg, 0.069 mmol), K ₂ CO ₃ (320 mg, 2.32 mmol) in 1,4-dioxane/DMF/water (15mL/3 mL/1.5 mL) was degassed and heated at 90 ºC for 24 hours. The resulted mixture was worked up with water and ethyl acetate. The organic phase was collected and loaded on silica gel, purified by flash chromatography using eluents of DCM/EA (0% → 40% EA). The desired fraction was collected, after removal of solvents under reduced pressure, a yellow solid was obtained (210mg, in 49% yield). LCMS (APCI-): Calcd for C36H37NO4: 547.27; Found: 547. ¹ H NMR (400 MHz, d2-TCE) δ 8.60 – 8.48 (m, 2H), 7.93 – 7.76 (m, 2H), 7.45 – 7.24 (m, 3H), 6.99 (s, 2H), 4.25 (t, J = 6.1 Hz, 2H), 4.01 (q, J = 7.2 Hz, 2H), 3.47 (t, J = 5.5 Hz, 2H), 2.88 (p, J = 6.8 Hz, 1H), 2.65 – 2.43 (m, 2H), 1.89 (d, J = 6.2 Hz, 2H), 1.24 (d, J = 6.9 Hz, 6H), 1.03 (t, J = 7.1 Hz, 12H). Compound PLC-22.2: To a solution of compound 1612-48 (210 mg, 0.384 mmol) in 20 mL DCM was added carbon tetrabromide (CBr4, 252mg, 0.76 mmol), triphenylphosphine (203 mg, 0.77 mmol) at room temperature. The whole was stirred for 30 min. TLC shows the reaction has completed. The mixture was loaded on silica gel and purified by flash chromatography using eluents of hexanes/DCM (0% → 100% DCM). The desired fraction was collected, concentrated under reduced pressure to give a yellow solid (100mg, in 43% yield). LCMS (APCI+): Calcd for C ₃₆ H ₃₇ BrNO ₃ (M+H): 610.19; Found: 610. ¹ H NMR (400 MHz, d2-TCE) δ 8.52 (dd, J = 8.1, 2.5 Hz, 2H), 8.00 – 7.72 (m, 2H), 7.45 – 7.19 (m, 3H), 6.98 (s, 2H), 4.23 (t, J = 7.0 Hz, 2H), 3.44 (t, J = 6.8 Hz, 2H), 3.01 – 2.80 (m, 1H), 2.69 – 2.45 (m, 2H), 2.26 (q, J = 6.9 Hz, 2H), 1.24 (d, J = 6.9 Hz, 6H), 1.03 (t, J = 6.9 Hz, 12H). Compound PLC-22: A mixture of compound PLC-22.1 (50 mg, 0.082 mmol), compound PLC1.1 (58.5 mg, 0.10 mmol), K2CO3 (20.7 mg, 0.15 mmol) in anhydrous DMF, was sonicated for 3 minuntes, then heated at 75 ºC for 5 hours under argon atmosphere. The resulted mixture was diluted with 100 mL DCM, washed with 0.1N HCl aqueous solution (50 mL x 2), dried over MgSO ₄ , concentrated to 50 mL then loaded on silica gel, and purified by flash chromatography using eluents of DCM/EA (0% → 5% EA). The main desired fraction was collected, concentrated and triturated with methanol followed by filtration to give a dark red solid (70 mg, in 76.6% yield). LCMS (APCI-): Calcd for C69H60BCl2F2N3O4: 1113.40; Found: 1113. ¹ H NMR (400 MHz, d2-TCE) δ 8.63 – 8.43 (m, 2H), 8.08 – 7.72 (m, 4H), 7.46 – 7.13 (m, 9H), 6.94 (d, J = 31.3 Hz, 4H), 6.38 (s, 2H), 4.35 (t, J = 6.8 Hz, 2H), 4.12 (t, J = 5.9 Hz, 2H), 2.98 – 2.77 (m, 1H), 2.54 (q, J = 6.8 Hz, 6H), 2.23 (d, J = 6.0 Hz, 6H), 2.04 – 1.89 (m, 4H), 1.23 (d, J = 6.9 Hz, 6H), 1.02 (dd, J = 6.9, 3.5 Hz, 12H). Synthesis of Compound PLC-23 Compound PLC-23.2 4-(3-(9-(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xanthe no[2,1,9-def] isoquinolin-2(3H)-yl) propoxy)-2,6-dimethylbenzaldehyde A mixture of 2,6-dimethyl-4-hydroxybenxaldehyde (30.04 mg mg, 0.4 mmol, 1 eq), K ₂ CO ₃ (55.28 mg, 0.4 mmol, 2eq), NaI (2.3 mg, cat. amount) and PLC-23.1 (130.2735 mg, 0.21 mmol, 1.05 eq) in DMF anhydrous (4.0 ml) was mixed by sonicating for 10 minutes before stirred at 65 ºC, under Argon atmosphere 24 hours. After cooling to RT, the mixture was concentrated to dryness. The residue was washed with (50 ml x 2) hot water, the yellow solid was collected by filtering. The solid was then sonicating with MeOH at 65 ºC, cooled, then filtered and dried in vacuo oven, the product was used next step without further purification, gained 135 mg, yield 85%. MS (APCI): calculated for Chemical Formula: C38H25F6NO5 (M-) = 689; found: 689. ¹ H NMR (400 MHz) δ 10.34 (s, 1H), 8.57 (d, J = 7.9 Hz, 1H), 8.52 (d, J = 8.3 Hz, 1H), 8.16 (d, J = 2.2 Hz, 1H), 8.02 (d, J = 8.9 Hz, 2H), 7.86 (s, 1H), 7.70 (dd, J = 8.6, 2.1 Hz, 1H), 7.47 (d, J = 8.6 Hz, 1H), 7.30 (d, J = 8.3 Hz, 1H), 6.46 (s, 2H), 4.30 (t, J = 7.1 Hz, 2H), 4.09 (t, J = 6.0 Hz, 2H), 2.47 (s, 3H), 2.18 (t, J =6.6 Hz, 2H). Compound PLC-23: Diethyl 10-(4-(3-(9-(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H- xantheno[2,1,9-def]isoquinolin-2(3H)-yl)propoxy)-2,6-dimethy lphenyl)-5,5-difluoro-1,3,7,9- tetramethyl-5H-4 l ⁴ ,5 l ⁴ -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dica rboxylate Step 1: In a 50 ml vial was equipped with: septum cap, magnetic stirring bar; a mixture of compound benzyl 2,4-dimethyl-1H -pyrrole-3-carboxylate (58.19 mg, 0.348 mmol, 2.1eq), 1643-005 (115 mg, 0.166 mmol, 1 eq) in 1,2-dichloroethane (DCE) anhydrous (4 ml) was bubbling with Argon and stirred at RT 15 minutes.8 mg pTSA was added and the RX was stirred at 85 ºC for 45 minutes, LCMS shown starting materials were completely converted. The crude product was used in situ next step without further purification. Step 2: The above mixture was cooled to RT, 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (0.113 g, 0.498 mmol, 3eq) was added in one portion. The resulting mixture was stirred at room temperature 1/2 hour. TLC and LCMS shown starting materials were converted completely. Step 3: The above mixture was cooled to 0 ºC then stirred with triethylamine (0.462 ml, 3.48 mmol. 3.32 mmol, 20 eq) for 15 minutes. BF3 etherate (1.224 mL, 9.96mmol, 60 eq) was added dropwise. The resulting reaction mixture was sonicated at room temperature under Argon atmosphere for 10 minutes; then stirred at 60 ºC for 45 minutes then stirred at RT 16 hrs. After quenching with EtOH (2 ml), the reaction mixture was concentrated by rotavapor. The residue was washed with hot water, the crude product was chromatographed by column of silica gel (80 g), eluting with DCM only (1CV) then DCM/ EtOAc (98:2) and then washed with EtOH to afford the pure title product (1643-006) as orange yellow solid (105 mg, 60 % total yield base on 1643-005 aldehyde SM). MS (APCI): calculated for Chemical Formula: C56H46BF8N3O8 (M-) = 6891051.; found: 1051. ¹ H NMR (400 MHz) δ 8.59 (d, J = 7.8 Hz, 1H), 8.52 (d, J = 8.3 Hz, 1H), 8.17 (d, J = 2.2 Hz, 1H), 8.03 (d, J = 8.1 Hz, 1H), 8.00 (d, J = 1.5 Hz, 2H), 7.86 (s, 1H), 7.69 (dd, J = 8.6, 2.2 Hz, 1H), 7.46 (d, J = 8.6Hz, 1H), 7.30 (d, J = 8.3 Hz, 1H), 6.59 (s, 2H), 4.34 (t, J = 7.1 Hz, 2H), 4.18 (q, J = 7.1 Hz, 4H), 4.08 (t, J= 6.2 Hz, 2H), 2.73 (s, 6H), 2.25 – 2.13 (m, 2H), 1.95 (s, 6H), 1.63 (s, 6H), 1.25 (t, J = 7.1 Hz, 6H). Synthesis of Compound PLC-24 Compound PLC-24.1: 4'-(tert-butyl)-3-nitro-[1,1'-biphenyl]-4-ol 4-Bromo-2-nitro-phenol (5.45 g, 25.0 mmol) and 4-(t-butyl)benzene boronic acid (5.563 g, 31.25 mmol) were dissolved in Dioxane (100 mL) at room temperature and stirred for 5 min. After a clear solution was formed, Pd (PPh ₃ ) ₂ Cl ₂ (0.175g, 0.25 mmol), and a solution of 4N aq. soln. K ₂ CO ₃ (25.0 ml, 50 mmol, 2 eq) were added quickly; the mixture was degassed by Vac-Fil Nitrogen cycle 3 times before heating for 4 hrs at 80 °C. After reaction was cooled to RT, the pH was adjusted to 5-6 with 4N HCl aq. soln., extracted with ethyl acetate (250 mL), passed through a short pad of celite. The pad was washed with EA (150 ml x2). The organic layers were combined and washed with brine (25 mL), dried over anhydrous MgSO ₄ , and concentrated under reduced pressure. The residue was dissolved into Hex: EA (95:5) (150 ml), the dark color solid was filtered off by filtering through short pad of celite, the filtrate was concentrated to obtain a yellow solid which was triturated with Hexanes to give 3.8 yellow solid, yield 56%. MS (APCI): calculated for Chemical Formula: C ₁₆ H ₁₇ NO ₃ (M-) = 271; found: 271. ¹ H NMR (400 MHz, Chloroform-d) δ 10.57 (s, 1H), 8.32 (d, J = 2.3 Hz, 1H), 7.83 (dd, J = 8.7, 2.4 Hz, 1H), 7.50 (d, J = 1.5 Hz, 4H), 7.23 (d, J = 8.7 Hz, 1H), 1.37 (s, 9H). Compound PLC-24.2: 6-((4'-(tert-butyl)-3-nitro-[1,1'-biphenyl]-4-yl)oxy)-1H,3H- benzo[de]isochromene-1,3-dione Mixing of 4-bromonaphthalic anhydride (10 g, 36 mmol, 1.15 eq), 4'-(tert-butyl)-3-nitro-[1,1'- biphenyl]-4-ol (1574-71) (8.5 g, 31.32 mmol, 1eq), NaOH (0.864 g, 21.6 mmol, 0.6eq) in NMP anhydrous (65 mL), added copper powder (1.371g, 21.6mmol, 0.6 eq) the resulting mixture was degassed by Vac-Fil Nitrogen cycle 3 times before heating and stirring at 145 ºC under N2 atmosphere for 5hrs, then RT overnight. The RX mixture was worked up with HCl aq sol.; after standing at RT 12 hour, the brow solid was precipitated, filtered, washed with hot MeOH (250 ml x3) to obtain (10.8 g, 23.1 mmol) light brown solid, yield 73 %, purity 86%. MS (APCI): calculated for Chemical Formula: C ₂₈ H ₂₁ NO ₆ (M-) = 467; found: 467 Compound PLC-24.3: 6-((3-amino-4'-(tert-butyl)-[1,1'-biphenyl]-4-yl) oxy)-1H,3H- benzo[de]isochromene-1,3-dione To a mixture of compound PLC-24.2 (4.885g, 10.45 mmol, 1.0 eq) in 2-MeTHF (70.0 mL) and HCl (4 M, 26.1 mL, 10 eq) was added SnCl ₂ .2H ₂ O (9.4 g, 41.75 mmol, 4.0 eq) in one portion. The mixture was stirred at 90 °C for 1/2 hr. TLC (Hexanes/Ethyl acetate = 7:3) and LCMS showed the reaction was completed. The white solid was filtered off, washed with EA/2-MeTHF (1:1) (100 mLx 2). The combined organic filtrates were washed with water, separated, concentrated under reduced pressure to give a sticky sold residue. The crude product was washed with hot water 100 mL at 50 ºC for 1/2 hour, filtered then drying under reduced pressure to gained 1574-78 (4.5 g, 10.28 mmol) was obtained as a yellow brown solid.98% yield. MS (APCI): calculated for Chemical Formula: C ₂₈ H ₂₃ NO ₄ (M-) = 437; found: 437 Compound PLC-24.4: 9-(4-(tert-butyl) phenyl)-1H,3H-isochromeno[6,5,4-mna] xanthene-1,3-dione Compound PLC-24.3 (1.844 g, 4.215 mmol, 1.0 eq) in AcOH (28.5 mL) and H ₂ O (9.0 mL) was added dropwise HCl conc. (2.445 mL) and NaNO ₂ (2.9 g, 42.15 mmol, 10 eq) in H ₂ O (9mL) at 0 °C and stirred at 0 °C for 1 hr. The above solution was added to CuSO ₄ 5H ₂ O (4.35 g, 17.42 mmol, 4.1 eq) in H ₂ O (175 ml), AcOH (11 ml) via a dropping funnel at 130 °C over a period of 1/2 hr. After the addition was completed, the resulting was continued stirring at the same temperature 130 °C further 15 mins. The mixture was filtered and washed with H ₂ O (3x100 mL). →0.445g crude product was triturated EtOH → 0.42 g pure compound, yield 30%. MS (APCI): calculated for Chemical Formula: C28H20O4 (M-) = 420; found: 420 Compound PLC-24.5: 9-(4-(tert-butyl) phenyl)-2-(3-hydroxypropyl)-1H-xantheno[2,1,9-def] isoquinoline-1,3(2H)-dione Compound PLC-24.4 (0.420 g,1.0 mmol, 1.0 eq) in DMSO anhydrous (4 mL) was added 3-amino-1- propanol (0.300 g, 4.0 mmol, 4.0 eq) at rt the resulting mixture was stirred over a period of 45 minutes at 130 °C. After the reaction was completed, DMSO were removed by filtering. The solid was washed with water (50 mlx3) and dried in vacuo- oven to achieve 0.45 g yellow solid; yield 94%. MS (APCI): calculated for Chemical Formula: C ₃₁ H ₂₇ NO ₄ (M-) = 477; found: 477. ¹ H NMR (400 MHz, Chloroform- d) δ 10.44 (s, 2H), 8.65 (d, J = 7.8 Hz, 1H), 8.60 (d, J = 8.3 Hz, 1H), 8.25 (d, J = 2.0 Hz, 1H), 8.03 (d, J = 8.0 Hz, 1H), 7.76 (dd, J = 8.6, 2.1 Hz, 1H), 7.61 (d, J = 8.3 Hz, 2H), 7.54 (d, J = 8.2 Hz, 2H), 7.45 (d, J = 8.6 Hz, 1H), 7.32 (d, J = 8.3 Hz, 1H), 6.50 (s, 2H), 4.42 (t, J = 6.9 Hz, 2H), 4.17 (t, J = 6.2 Hz, 2H), 2.54 (s, 6H), 2.28 (s, 2H), 1.40 (s, 9H). Compound PLC-24.6: 2-(3-bromopropyl)-9-(4-(tert-butyl) phenyl)-1H-xantheno[2,1,9-def] isoquinoline-1,3(2H)-dione. A mixture of compound 24.5 (0.453g, 0.95 mmol) and 48% aqueous HBr (20 ml) was stirred and heated by heating block at 130 °C for 8 h. LCMS shown the SM was completely consumed. The mixture was cooled to RT and standing at RT 16 hours. Yellow solid was filtered, washed with water several times, dried in vacuo oven to gain 0.275g, yield 96%. Product was used next step without further purification. MS (APCI): calculated for Chemical Formula: C31H26BrNO3(M-) = 540; found: 540. ¹ H NMR (400 MHz) δ 8.59 (d, J = 7.8 Hz, 1H), 8.53 (d, J = 8.4 Hz, 1H), 8.19 (s, 1H), 7.99 (d, J= 8.0 Hz, 1H), 7.72 (d, J = 8.7 Hz, 1H), 7.55 (d, J = 8.0 Hz, 2H), 7.45 (d, J = 8.0 Hz, 2H), 7.41 (d, J = 8.5 Hz, 1H), 7.29 (d, J = 8.4 Hz, 1H), 4.25 (s, 2H), 3.48 (d, J = 6.1 Hz, 2H), 3.16 (d, J = 6.8 Hz, 1H), 1.90 (s, 2H), 1.31 (s, 9H). Compound PLC-24.7: 4-(3-(9-(4-(tert-butyl) phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def] isoquinolin- 2(3H)-yl) propoxy)-2,6-dimethylbenzaldehyde. A mixture of 2,6-dichloro-4-hydroxybenxaldehyde (Combi Block, cas#60964-09-2), QF-6704, Batch 31758, 95% pure) (32 mg mg, 0.159 mmol, 1 eq), K ₂ CO ₃ (32.5 mg, 0.23.5 mmol, 1.47 eq), NaI (2.3 mg, cat. amount) and 1643-011 (96.74 mg, 0.179 mmol, 1.125 eq) in DMF anhydrous (1.0 ml) was mixed together by sonicating for 10 minutes before stirred at 85 ^o C, under Argon atmosphere 4 hours. LCMS shown only 10% conversion. The mixture was then heated and stirred to 65 ^o C for 5hrs. After cooling to RT, the mixture was concentrated to dryness, washed the solid with (50 ml x 2) hot water, the yellow solid was collected by filtering then sonicating with MeOH at rt, filtered and dried in vacuo oven, the product was used next step without further purification, gained 27.0 mg of 1643-015, yield 75%. MS (APCI): calculated for Chemical Formula: C ₄₀ H ₃₅ NO ₅ (M-) = 609; found: 609. ¹ H NMR (400 MHz, Chloroform-d) δ 10.44 (s, 2H), 8.65 (d, J = 7.8 Hz, 1H), 8.60 (d, J = 8.3 Hz, 1H), 8.25 (d, J = 2.0 Hz, 1H), 8.03 (d, J = 8.0 Hz, 1H), 7.76 (dd, J = 8.6, 2.1 Hz, 1H), 7.61 (d, J = 8.3 Hz, 2H), 7.54 (d, J = 8.2 Hz, 2H), 7.45 (d, J = 8.6 Hz, 1H), 7.32 (d, J = 8.3 Hz, 1H), 6.50 (s, 2H), 4.42 (t, J = 6.9 Hz, 2H), 4.17 (t, J = 6.2 Hz, 2H), 2.54 (s, 6H), 2.28 (s, 2H), 1.40 (s, 9H). Compound PLC-24: Diethyl 10-(4-(3-(9-(4-(tert-butyl) phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def] isoquinolin-2(3H)-yl) propoxy)-2,6-dimethylphenyl)-5,5-difluoro-1,3,7,9-tetramethy l-5H-4l4,5l4- dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxyla te Step 1: In a 50 ml vial was equipped with: septum cap, magnetic stirring bar; a mixture of compound 1643-015 (68.28 mg, 0.112 mmol, 1eq), ethyl 2,4-dimethyl-1H -pyrrole-3-carboxylate (38.4 mg, 0.23 mmol, 2.05eq), in 1,2-dichloroethane (DCE) anhydrous (2 ml) was bubbling with Argon and stirred at RT 15 minutes, 4 mg pTSA was added and the RX was further stirred at 86 ºC for 45 minutes, LCMS shown starting materials were completely converted. The crude product was used in situ next step without further purification. Step 2: The above mixture was cooled to RT, 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (79.45 mg, 0.35 mmol) was added in one portion. The resulting mixture was stirred at room temperature 1/2 hour. TLC and LCMS shown starting materials were converted completely. Step 3: The above mixture was cooled to 0 ºC then stirred with triethylamine (0.125 ml, 1.74 mmol) for 15 minutes. BF3 etherate (0.71 mL, 2.76 mmol) was added dropwise. The resulting reaction mixture was stirred at 86 ºC under Argon atmosphere for 45 minutes; cooled to 0 ºC quenched with EtOH (2 ml), and the solvents were removed by rotavapor. The residue was chromatographed on column of silica gel (80 g), eluting with DCM only (1CV) then DCM/ EtOAc (98:2) and then washed with EtOH to afford the pure title product (1643-017) as orange yellow solid (40 mg, 36 % total yield base on 1643- 015 aldehyde SM). MS (APCI): calculated for Chemical Formula: C ₅₈ H ₅₆ BF ₂ N ₃ O ₈ (M-) = 971; found: 971. ¹ H NMR (400 MHz, Chloroform-d) δ 8.65 (d, J = 7.8 Hz,1H), 8.60 (d, J = 8.3 Hz, 1H), 8.24 (d, J = 2.1 Hz, 1H), 8.03 (d, J = 8.0 Hz, 1H), 7.75 (dd, J = 8.6, 2.1 Hz, 1H), 7.61 (d, J= 8.4 Hz, 2H), 7.56 – 7.49 (m, 2H), 7.44 (d, J = 8.6 Hz,1H), 7.32 (d, J = 8.4 Hz, 1H), 6.64 (s, 2H), 4.45 (t, J = 6.9Hz, 2H), 4.28 (q, J = 7.1 Hz, 4H), 4.15 (t, J = 6.3 Hz, 2H),2.83 (s, 6H), 2.30 (t, J = 6.7 Hz, 2H), 2.02 (s, 6H), 1.71 (s, 6H), 1.56 (s, 6H), 1.40 (s, 9H), 1.33 (t, J = 7.1 Hz, 6H). Synthesis of compound PLC-25 Compound PLC-25.1: 9-bromo-2-(4-hydroxybutyl)-1H-xantheno[2,1,9-def]isoquinolin e-1,3(2H)-dione A 100 mL flask was fitted with a stir bar. To the flask, compound PLC-3.3 (1.0 g, 2.7 mmol), 4- aminobutan-1-ol (485.3 mg, 5.4 mmol) and DMAP (23.1 mg, 0.19 mmol) in DMF (20 ml) was degassed at room temperature. The reaction mixture was heated up to 165 ºC and the reaction has been kept at this temperature for 2.5 hrs. TLC and LCMS showed the completion of the reaction. The reaction was cooled down to room temperature. H ₂ O (80 ml) was added. The solid product was collected by vacuum filtration and washed with H ₂ O (100 ml) and further dried in a vacuum oven at 100 ºC for 3 hours to provide compound PLC-25.1 as a brown solid for the next step without further purification. 908.0 mg, 77% yield. MS (APCI): calculated for Chemical Formula: C ₂₂ H ₁₆ BrNO ₄ ([M-H]-) = 438 found: 438. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.62 (d, J = 8.0 Hz, 1H), 8.58 (d, J = 8.0 Hz, 1H), 8.19 (d, J = 2.4 Hz, 1H), 7.93 (d, J = 8.0 Hz, 1H), 7.64 (dd, J = 8.0 Hz, J = 2.4 Hz, 2H), 7.32 (d, J = 8.0 Hz, 1H), 7.28 (d, J = 8.0 Hz, 1H), 4.20 (t, J = 7.2 Hz, 2H), 3.83 (t, J = 6.0 Hz, 2H), 1.82 (m, 2H), 1.69 (m, 2H). Compound PLC-25.2: 2-(4-hydroxybutyl)-9-(4-(trifluoromethyl)phenyl)-1H-xantheno [2,1,9- def]isoquinoline-1,3(2H)-dione A 250 mL flask was fitted with a stir bar. To the flask, compound PLC-25.1 (900.0 mg, 2.1 mmol), 4- (trifluoromethyl)phenylboronic acid (780.0 mg, 4.1 mmol), Pd(dppf)Cl ₂ (107.5 mg, 0.15 mmol) and K ₂ CO ₃ (782.5 mg, 5.7 mmol) in THF/DMF/H ₂ O (60 ml/ 12 ml/ 6 ml) was degassed at room temperature. The reaction mixture was heated up to 80 ºC and the reaction has been kept at this temperature overnight. TLC was used to monitor the reaction. After the completion, the reaction was worked up by the addition of H ₂ O (150 ml) added to precipitate the product. The precipitate was collected by filtration. The solid was washed by H ₂ O (200 ml) and MeOH (20 ml), and further dried in a vacuum oven at 100 ºC for 3 hours to provide compound 25.2 as a yellow solid for the next step without further purification.990.0 mg, 94% yield. MS (APCI): calculated for Chemical Formula: C29H20F3NO4 ([M+H] ⁺ ) = 504 found: 504. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.67 (d, J = 8.0 Hz, 1H), 8.61 (d, J = 8.0 Hz, 1H), 8.27 (d, J = 2.4 Hz, 1H), 8.08 (d, J = 8.0 Hz, 1H), 7.80 (m, 5H), 7.52 (d, J = 8.4 Hz, 1H), 7.38 (d, J = 8.4 Hz, 1H), 4.22 (t, J = 7.2 Hz, 2H), 3.73 (t, J = 6.0 Hz, 2H), 1.84 (m, 4H). Compound PLC-25.3: 4-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9 -def]isoquinolin- 2(3H)-yl)butyl 4-methylbenzenesulfonate A 100 mL flask was fitted with a stir bar. To the flask, compound PLC-25.2 (200.0 mg, 0.40 mmol) and DCE (20 ml) were added. The solution was degassed at room temperature. p-toluenesulfonic anhydride (519.0 mg, 1.6 mmol) and TEA (221.0 µL, 1.6 mmol) were added. Then the solution heated up to 90 °C and it has been kept at this temperature for 4 hours. TLC and LCMS were used to monitor the reaction. More DCE (20 mL), p-toluenesulfonic anhydride (519.0 mg, 1.6 mmol) and was added. The reaction was cooled down to room temperature. H ₂ O (100 ml), TEA (221.0 µL, 1.6 mmol) were added. The reaction has been kept at 90 ºC overnight. The mixture was extracted with DCM (150 ml *3) after H ₂ O (150 ml) was added to stop the reaction. The combined organic phase was dried over anhydrous Na2SO4 and concentrated under vacuum rotavapor to provide compound PLC-25.3 as a yellow solid, which was used for the next step without further purification. MS (APCI): calculated for Chemical Formula: C36H26F3NO6S ([M-H]-) = 657 found: 657. ¹ H NMR (400 MHz, CDCl3) 8.55 (d, J = 8.0 Hz, 1H), 8.51 (d, J = 8.0 Hz, 1H), 8.16 (d, J = 2.0 Hz, 1H), 7.92 (d, J = 8.0 Hz, 1H), 7.76 (m, 7H), 7.41 (d, J = 8.4 Hz, 1H), 7.32 (d, J = 8.0 Hz, 2H), 7.24 (d, J = 8.0 Hz, 1H), 4.10 (m, 4H), 2.42 (s, 3H), 1.76 (m, 4H). Compound PLC-25.4: 4-(4-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2, 1,9- def]isoquinolin-2(3H)-yl)butoxy)-2,6-dimethylbenzaldehyde A 25 ml vial was charged with compound PLC-25.3 (131.5 mg, 0.20 mmol) and 4-hydroxy-2,6- methylbenzaldehyde (33.0 mg, 0.22 mmol) in DMF (5 mL). The solution was degassed at room temperature, K ₂ CO ₃ (41.4 mg, 0.30 mmol) was added. The reaction was further degassed at room temperature. Then it was warmed up to 65 ºC and has been kept stirring at this temperature overnight. TLC (50% EtOAc in Hexane) showed the completion of the reaction. The reaction mixture was purified by silica gel flash chromatography using EtOAc in Hexane (0-40%-60%) as an eluant to provide pure compound PLC-25.4 as a solid, 30.0 mg, 24% yield over two steps. MS (APCI): calculated for Chemical Formula: C ₃₈ H ₂₈ F ₃ NO ₅ ([M-H]-) = 635 found: 635. ¹ H NMR (400 MHz, CDCl ₃ ) δ 10.43 (s, 1H), 8.64 (d, J = 8.0 Hz, 1H), 8.60 (d, J = 8.0 Hz, 1H), 8.23 (d, J = 2.4 Hz, 1H), 8.02 (d, J = 8.0 Hz, 1H), 7.77 (s, 4H), 7.74 (dd, J = 8.0 Hz, 2.0 Hz, 1H), 7.47 (d, J = 8.0 Hz, 1H), 7.31 (d, J = 8.0 Hz, 1H), 6.56 (s, 2H), 4.28 (t, J = 6.8 Hz, 2H), 4.07 (t, J = 6.0 Hz, 2H), 1.94 (m, 6H), 1.58 (m, 4H). Compound PLC-25: Diethyl 10-(4-(4-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xanthen o[2,1,9- def]isoquinolin-2(3H)-yl)butoxy)-2,6-dimethylphenyl)-5,5-dif luoro-1,3,7,9-tetramethyl-5H-4l4,5l4- dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxyla te A 100 mL 2 neck round bottomed flask was fitted with an air condenser and a stir bar. To the flask, compound 25.4 (67.0 mg, 0.1 mmol) and ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (37.0 mg, 0.2 mmol) were added, followed by anhydrous dichloroethane (7 ml). The reaction mixture was sparged with Ar for 30 minutes, then p-TsOH•H ₂ O (0.67 mg, 0.006 mmol) was added. The reaction solution was heated up to 85 ºC and has been kept at this temperature overnight. Then the reaction was cooled down to room temperature and DDQ (13.7 mg, 0.06 mmol) was added. The reaction was kept at room temperature for 30 minutes. Then BF3•OEt2 (0.16 mL, 1.3 mmol) and Et3N (0.12 mL, 0.9 mmol) were added at room temperature. The reaction mixture was heated up to 60 ºC and has been kept at this temperature for 1 hour. More BF3•OEt2 (0.16 mL, 1.3 mmol) and Et3N (0.12 mL, 0.9 mmol) were added at room temperature. The reaction mixture was heated up to 60 ºC and has been kept at this temperature for 3 hours. The reaction mixture was loaded with silica gel and purified by flash chromatography, using EtOAc in DCM (0-10%-14%) as an eluant to provide the pure compound PLC- 25 as an orange solid, 12.0 mg, 11% yield. MS (APCI): calculated for Chemical Formula: C56H49BF5N3O8 ([M-H]-) = 997 found: 997. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.68 (d, J = 8.0 Hz, 1H), 8.62 (d, J = 8.0 Hz, 1H), 8.28 (d, J = 2.0 Hz, 1H), 8.09 (d, J = 8.0 Hz, 1H), 7.79 (m, 5H), 7.52 (d, J = 8.0 Hz, 1H), 7.39 (d, J = 8.0 Hz, 1H), 6.75 (s, 2H), 4.27 (m, 6H), 4.07 (m, 2H), 2.82 (s, 6H), 2.07 (s, 6H), 1.97 (m, 4H), 1.72 (s, 6H), 1.33 (t, J = 7.2 Hz, 6H). Synthesis of compound PLC-26 Compound PLC-26.2: 4-(2-(2-(2-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xanth eno[2,1,9- def]isoquinolin-2(3H)-yl)ethoxy)ethoxy)ethoxy)-2,6-dimethylb enzaldehyde A 25 ml vial was charged with compound PLC-26.1 (186.6 mg, 0.26 mmol) and 4-hydroxy-2,6- methylbenzaldehyde (43.0 mg, 0.29 mmol) in DMF (5 mL). The solution was degassed at room temperature, K ₂ CO ₃ (53.8 mg, 0.39 mmol) was added. The reaction was further degassed at room temperature. Then it was warmed up to 65 ºC and has been kept stirring at this temperature overnight. TLC (50% EtOAc in Hexane) showed the completion of the reaction. The reaction mixture was purified by silica gel flash chromatography using EtOAc in Hexane (0-40%-60%) as an eluant to provide pure compound PLC-26.2 as a yield solid, 70.0 mg, 39% yield over two steps. MS (APCI): calculated for Chemical Formula: C40H32F3NO7 ([M-H]-) = 695 found: 695. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) δ 10.30 (s, 1H), 8.58 (d, J = 8.0 Hz, 1H), 8.54 (d, J = 8.0 Hz, 1H), 8.16 (d, J = 2.0 Hz, 1H), 7.95 (d, J = 8.0 Hz, 1H), 7.79 (s, 4H), 7.75 (dd, J = 8.0 Hz, 2.0 Hz, 1H), 7.44 (d, J = 8.0 Hz, 1H), 7.28 (d, J = 8.0 Hz, 1H), 6.40 (s, 2H), 4.43 (t, J = 6.0 Hz, 2H), 3.90 (t, J = 4.4 Hz, 2H), 3.84 (t, J = 6.0 Hz, 2H), 3.72 (m, 6H), 2.48 (s, 6H). Compound PLC-26: Diethyl 10-(4-(2-(2-(2-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H- xantheno[2,1,9-def]isoquinolin-2(3H)-yl)ethoxy)ethoxy)ethoxy )-2,6-dimethylphenyl)-5,5-difluoro- 1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3, 2]diazaborinine-2,8-dicarboxylate A 100 mL 2 neck round bottomed flask was fitted with an air condenser and a stir bar. To the flask, compound PLC-26.2 (70.0 mg, 0.1 mmol) and ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (35.3 mg, 0.2 mmol) were added, followed by anhydrous dichloroethane (5 ml). The reaction mixture was sparged with Ar for 30 minutes, then p-TsOH•H ₂ O (3.7 mg, 0.03 mmol) was added. The reaction solution was heated up to 65 ºC and has been kept at this temperature overnight. Then the reaction was cooled down to room temperature and DDQ (12.4 mg, 0.06 mmol) was added. The reaction was kept at room temperature for 30 minutes. Then BF ₃ •OEt ₂ (0.15 mL, 1.2 mmol) and Et ₃ N (0.11 mL, 0.8 mmol) were added at room temperature. The reaction mixture was heated up to 60 ºC and has been kept at this temperature for 1 hour. The reaction mixture was loaded with silica gel and purified by flash chromatography, using EtOAc in DCM (0-10%) as an eluant to provide the pure compound PLC- 26 as an orange solid, 28.0 mg, 26% yield. MS (APCI): calculated for Chemical Formula: C ₅₈ H ₅₃ BF ₅ N ₃ O ₁₀ ([M-H]-) = 1057 found: 1057. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.67 (d, J = 8.0 Hz, 1H), 8.62 (d, J = 8.0 Hz, 1H), 8.26 (d, J = 2.4 Hz, 1H), 8.07 (d, J = 8.0 Hz, 1H), 7.79 (bs, 4H), 7.77 (dd, J = 8.0 Hz, 2.0 Hz, 1H), 7.51 (d, J = 8.0 Hz, 1H), 7.37 (d, J = 8.0 Hz, 1H), 6.73 (s, 2H), 4.45 (t, J = 6.0 Hz, 2H), 4.27 (q, J = 7.2 Hz, 4H), 4.09 (m, 2H), 3.84 (m, 4H), 3.74 (m, 4H), 2.82 (s, 6H), 2.07 (s, 6H), 1.72 (s, 6H), 1.33 (t, J = 7.2 Hz, 6H). Synthesis of compound PLC-27

Compound PLC-27.1: 9-bromo-2-(3-hydroxypropyl)-1H-xantheno[2,1,9-def]isoquinoli ne-1,3(2H)- dione A 100 mL flask was fitted with a stir bar. To the flask, compound PLC-3.3 (500.0 mg, 1.4 mmol), 3- aminopropan-1-ol (204.6 mg, 2.7 mmol) and DMAP (11.6 mg, 0.1 mmol) in DMF (15 ml) was degassed at room temperature. The reaction mixture was heated up to 165 ºC and the reaction has been kept at this temperature for 2 hrs. TLC and LCMS showed the completion of the reaction. The reaction was cooled down to room temperature. H ₂ O (85 ml) was added to precipitate the product. The precipitate was collected by filtration. The solid was washed by H ₂ O (150 ml) and further dried in a vacuum oven at 100 ºC for 3 hours to provide compound PLC-27.1 as a yellow solid for the next step without further purification.455.0 mg, 79% yield. MS (APCI): calculated for Chemical Formula: C ₂₁ H ₁₄ BrNO ₄ ([M-H]-) = 423 found: 423. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.62 (d, J = 8.0 Hz, 1H), 8.59 (d, J = 8.0 Hz, 1H), 8.18 (s, 1H), 7.91 (d, J = 8.0 Hz, 1H), 7.64 (dd, J = 8.0 Hz, J = 2.0 Hz, 1H), 7.33 (d, J = 8.0 Hz, 1H), 7.28 (d, J = 8.0 Hz, 1H), 4.32 (t, J = 6.0 Hz, 2H), 3.56 (m, 2H), 3.16 (bs, 1H), 1.98 (m, 2H). Compound PLC-27.2: 2-(3-hydroxypropyl)-9-(perfluorophenyl)-1H-xantheno[2,1,9-de f]isoquinoline- 1,3(2H)-dione A 100 mL flask was fitted with a stir bar. To the flask, compound PLC-27.1 (400.0 mg, 0.9 mmol), (perfluorophenyl)boronic acid (240.0 mg, 1.1 mmol), Pd2(dba)3 (43.0 mg, 0.05 mmol), CsF (285.6 mg, 1.9 mmol), Ag2O (259.4 mg, 1.1 mmol) and (t-Bu)3P (1.9 ml, 1.9 mmol) in DMF (30 ml) was degassed at room temperature. The reaction mixture was heated up to 80 ºC and the reaction has been kept at this temperature overnight. TLC was used to monitor the reaction. After the completion, the reaction was purified by silica gel flash chromatography using EtOAc in Hexane (5-10-50-70%) as an eluant to provide pure compound PLC-27.2 as a yellow solid, 136.0 mg, 28% yield. MS (APCI): calculated for Chemical Formula: C27H14F5NO4 ([M-H]-) = 511 found: 511. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.57 (d, J = 8.0 Hz, 1H), 8.55 (d, J = 8.0 Hz, 1H), 8.07 (s, 1H), 7.92 (d, J = 8.0 Hz, 1H), 7.53 (d, J = 8.0 Hz, 1H), 7.46 (d, J = 8.0 Hz, 1H), 7.32 (d, J = 8.0 Hz, 1H), 4.25 (t, J = 6.0 Hz, 2H), 3.48 (m, 2H), 3.07 (t, J = 6.8 Hz, 1H), 1.90 (m, 2H). Compound PLC-27.3: 2-(3-bromopropyl)-9-(perfluorophenyl)-1H-xantheno[2,1,9-def] isoquinoline- 1,3(2H)-dione A 100 mL flask was fitted with a stir bar. To the flask, compound PLC-27.2 (136.0 mg, 0.3 mmol), CBr ₄ (176.3 mg, 0.5 mmol), PPh ₃ (140.2 mg, 0.5 mmol) and DCE (12 ml) were added. The solution was degassed at room temperature. The reaction has been kept at this temperature for 30 minutes. TLC and LCMS were used to monitor the reaction. After the completion, the reaction was purified by silica gel flash chromatography using EtOAc in Hexane (5-10-50-70%) as an eluant to provide pure compound PLC-27.3 as a yellow solid, 116.0 mg, 76% yield. MS (APCI): calculated for Chemical Formula: C27H13BrF5NO3 ([M+H] ⁺ ) = 573 found: 573. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.64 (d, J = 8.0 Hz, 1H), 8.61 (d, J = 8.0 Hz, 1H), 8.15 (d, J = 1.6 Hz, 1H), 7.99 (d, J = 8.0 Hz, 1H), 7.61 (m, 1H), 7.54 (d, J = 8.0 Hz, 1H), 7.39 (d, J = 8.0 Hz, 1H), 4.32 (t, J = 6.8 Hz, 2H), 3.54 (t, J = 6.8 Hz, 2H), 2.34 (quintet, J = 6.8 Hz, 2H). Compound PLC-27.4: 4-(3-(1,3-dioxo-9-(perfluorophenyl)-1H-xantheno[2,1,9-def]is oquinolin-2(3H)- yl)propoxy)-2,6-dimethylbenzaldehyde To a 25 ml vial, compound PLC-27.3 (50.0 mg, 0.09 mmol), 4-hydroxy-2,6-dimethylbenzaldehyde (15.7 mg, 0.1 mmol), K ₂ CO ₃ (24.0 mg, 0.2 mmol) and DMF (2 ml) were added. The mixture has been sonicated at room temperature for 2 minutes. Then it was warmed up to 75 ºC and has been kept stirring at this temperature for 4 hours. TLC (50% EtOAc in Hexane) showed the completion of the reaction. The reaction mixture was purified by silica gel flash chromatography using EtOAc in DCM (0- 40%) as an eluant to provide pure compound PLC-27.4 as a yellow solid, 29.0 mg, 48% yield. MS (APCI): calculated for Chemical Formula: C ₃₆ H ₂₂ F ₅ NO ₅ ([M-H]-) = 643 found: 643. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) δ 10.43 (s, 1H), 8.63 (d, J = 8.0 Hz, 1H), 8.59 (d, J = 8.0 Hz, 1H), 8.15 (bs, 1H), 7.99 (d, J = 8.0 Hz, 1H), 7.61 (d, J = 8.0 Hz, 1H), 7.54 (d, J = 8.0 Hz, 1H), 7.38 (d, J = 8.0 Hz, 1H), 6.55 (s, 2H), 4.39 (t, J = 6.8 Hz, 2H), 4.17 (t, J = 6.8 Hz, 2H), 2.56 (s, 6H), 2.26 (quintet, J = 6.8 Hz, 2H). Compound PLC-27: Diethyl 10-(4-(3-(1,3-dioxo-9-(perfluorophenyl)-1H-xantheno[2,1,9- def]isoquinolin-2(3H)-yl)propoxy)-2,6-dimethylphenyl)-5,5-di fluoro-1,3,7,9-tetramethyl-5H-4l4,5l4- dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxyla te A 50 mL 2 neck round bottomed flask was fitted with an air condenser and a stir bar. To the flask, compound 27.4 (60.0 mg, 0.1 mmol) and ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (32.7.0 mg, 0.2 mmol) were added, followed by anhydrous dichloroethane (5 ml). The reaction mixture was sparged with Ar for 30 minutes, then p-TsOH•H ₂ O (0.7 mg, 0.006 mmol) was added. The reaction solution was heated up to 65 ºC and has been kept at this temperature overnight. Then the reaction was cooled down to room temperature and DDQ (11.2 mg, 0.05 mmol) was added. The reaction was kept at room temperature for 30 minutes. Then BF3•OEt2 (0.13 mL, 1.1 mmol) and Et3N (0.10 mL, 0.7 mmol) were added at room temperature. The reaction mixture was heated up to 60 ºC and has been kept at this temperature for 1 hour. The reaction mixture was loaded with silica gel and purified by flash chromatography, using EtOAc in DCM (0-10%) as an eluant to provide the pure compound PLC-27 as an orange solid, 77.0 mg, 85% yield. MS (APCI): calculated for Chemical Formula: C54H43BF7N3O8 ([M- H]-) = 1005 found: 1005. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.64 (d, J = 8.0 Hz, 1H), 8.61 (d, J = 8.0 Hz, 1H), 8.15 (bs, 1H), 8.00 (d, J = 8.0 Hz, 1H), 7.61 (d, J = 8.0 Hz, 1H), 7.54 (d, J = 8.0 Hz, 1H), 7.39 (d, J = 8.0 Hz, 1H), 6.67 (s, 2H), 4.41 (t, J = 6.8 Hz, 2H), 4.27 (q, J = 7.2 Hz, 4H), 4.171 (t, J = 6.8 Hz, 2H), 2.82 (s, 6H), 2.28 (quintet, J = 6.8 Hz, 2H), 2.05 (s, 6H), 1.72 (s, 6H), 1.34 (t, J = 7.2 Hz, 6H). Synthesis of Compound PLC-29

Compound PLC-29.1: 6-(2-nitro-4-(trifluoromethyl)phenoxy)-1H,3H-benzo[de]isochr omene-1,3- dione A 1 L 2N round bottom flask was placed in an aluminum heat block and charged with a stir bar. The flask was fitted with a finned condenser/gas adapter, stopper and flow control valve. The system was flushed with argon. To the flask was added 6-bromo-1H,3H-benzo[de]isochromene-1,3-dione (40.0 mmol, 11.084 g) and 2-nitro-4-(trifluoromethyl)phenol (60.0 mmol, 8.44 mL), followed by anhydrous NMP (150 mL). To the flask was added NaOH (20.0 mmol, 800 mg) and copper (powder) (20.0 mmol, 1271 mg), followed by anhydrous NMP (25 mL). The flask was stirred under argon atmosphere with the heat block set to 170 ° C. The reaction was stirred at this temperature overnight. The reaction mixture was cooled to room temperature and treated with water (175 mL) and 1N HCl (44 mL). The reaction was further diluted with water (325 mL) to give a sticky precipitate. The reaction mixture was decanted from the sticky precipitate, washing with water. The crude product was evaporated to dryness in vacuo, then dissolved in DCM and evaporated onto ~65g flash silica gel. Purified by flash chromatography on silica gel (330g, solid load, equilibrate 100% hexanes, eluting 100% (2 CV) → 100% DCM (20 CV)). Fractions containing product were collected and evaporated to dryness in vacuo. Gives a light brown solid, 1.558 g (10% yield) which is about 80% pure. Used in the next step without further purification. MS (APCI): calculated for Chemical Formula: C19H8F3NO6 (M+H) = 404; found: 404. Compound PLC-29.2: (6-(2-amino-4-(trifluoromethyl)phenoxy)-1H,3H-benzo[de]isoch romene-1,3- dione) Compound PLC-29.2 was synthesized from Compound PLC-29.1 (3.47 mmol, 1.400 g), (13.88 mmol, 3131 mg), 4N HCl (34.7 mmol, 8.7 mL) in 2MeTHF (30 mL) in a manner similar to the methods described above. After the usual workup, the product was sufficiently pure to use in the next step. Gives 877 mg (68% yield). MS (APCI): calculated for Chemical Formula: C ₁₉ H ₁₀ F ₃ NO ₄ (M+H) = 374; found: 374. ¹ H NMR (400 MHz, Tetrachloroethane-d ₂ ) δ 8.85 (dd, J = 8.4, 1.2 Hz, 1H), 8.69 (dd, J = 7.3, 1.2 Hz, 1H), 8.49 (d, J = 8.3 Hz, 1H), 7.91 (dd, J = 8.4, 7.3 Hz, 1H), 7.20 (d, J = 2.0 Hz, 1H), 7.17 – 7.07 (m, 2H), 6.98 (d, J = 8.3 Hz, 1H), 4.07 (s, 2H). Compound PLC-29.3: (9-(trifluoromethyl)-1H,3H-isochromeno[6,5,4-mna]xanthene-1, 3-dione) Compound PLC-29.3 was synthesized from Compound PLC-29.2 (2.344 mmol, 875 mg), NaNO ₂ (17.58 mmol, 1.213 g), con. HCl (11.72 mmol, 12.1N, 0.969 mL), and CuSO ₄ .5H ₂ O (16.06 mmol, 4.009g). The crude product was evaporated onto ~30g flash silica gel in vacuo. Purified by flash chromatography on silica gel (220g, solid load, no equilibration, eluting 100% hexanes (2 CV) → 100% DCM (20 CV) → isocratic DCM + 0.5% EtOAc modifier). Fractions containing product were evaporated to dryness in vacuo. Gives a yellow solid, 509 mg (61% yield). MS (APCI): calculated for Chemical Formula: C19H7F3O4 (M+H) = 357; found: 357. ¹ H NMR (400 MHz, Tetrachloroethane-d2) δ 8.64 (d, J = 7.9 Hz, 1H), 8.60 (d, J = 8.3 Hz, 1H), 8.34 – 8.28 (m, 1H), 8.04 (d, J = 7.9 Hz, 1H), 7.82 (dd, J = 8.9, 2.0 Hz, 1H), 7.52 (d, J = 8.6 Hz, 1H), 7.40 (d, J = 8.3 Hz, 1H). Compound PLC-29.4: (2-(4-(1,3-dioxo-9-(trifluoromethyl)-1H-xantheno[2,1,9-def]i soquinolin-2(3H)- yl)phenyl)acetic acid) Compound PLC-29.4 was synthesized from Compound PLC-29.3 (0.702 mmol, 250 mg), 2-(4- aminophenyl)acetic acid (1.754 g, 265 mg), and DMAP (0.0521 mmol, 6.3 mg) in DMF (10 mL) in a manner similar to the methods described above. After workup and trituration, the compound was dried in a vacuum oven at ~140 ° C. Gives 366 mg (107% yield). MS (APCI): calculated for Chemical Formula: C ₁₉ H ₇ F ₃ O ₄ (M+H) = 490; found: 490. ¹ H NMR (400 MHz, DMSO-d ₆ ) δ 8.65 (d, J = 2.2 Hz, 1H), 8.45 – 8.37 (m, 4H), 7.90 (dd, J = 8.8, 2.2 Hz, 1H), 7.62 – 7.56 (m, 1H), 7.45 – 7.38 (m, 2H), 7.31 – 7.24 (m, 2H), 3.68 (s, 2H). Compound PLC-29: Diethyl 10-(4-(2-(4-(1,3-dioxo-9-(trifluoromethyl)-1H-xantheno[2,1,9 - def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dimethylphenyl) -5,5-difluoro-1,3,7,9-tetramethyl-5H- 4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dic arboxylate Compound PLC-29 was synthesized from Compound PLC-1.1 (0.050 mmol, 25.6 mg), Compound PLC- 29.4 (0.075 mmol, 37 mg), DMAP.pTsOH salt (0.100 mmol, 29.4 mg), and EDC.HCl (0.150 mmol, 28.8 mg) in a manner similar to the methods described above. The crude product was diluted with hexanes and loaded onto ~30g flash silica gel in a solid loader. Purified by flash chromatography on silica gel (80g, solid load, no equilibration, eluting 100% hexanes/0.5% EtOAc modifier (2 CV) → 100% DCM/0.5% EtOAc modifier (10 CV) → 100% DCM/1% EtOAc modifier (20 CV) → 100% DCM/2% EtOAc modifier (20 CV) → 100% DCM/4% EtOAc modifier (20 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 46 mg (94% yield). MS (APCI): calculated for Chemical Formula: C54H43BF5N3O9 (M-) = 983; found: 983. ¹ H NMR (400 MHz, Tetrachloroethane-d2) δ 8.68 (d, J = 7.8 Hz, 1H), 8.64 (d, J = 8.3 Hz, 1H), 8.34 (d, J = 2.1 Hz, 1H), 8.07 (d, J = 8.0 Hz, 1H), 7.81 (dd, J = 8.9, 2.0 Hz, 1H), 7.67 – 7.62 (m, 2H), 7.52 (d, J = 8.6 Hz, 1H), 7.41 (d, J = 8.3 Hz, 1H), 7.40 – 7.35 (m, 2H), 7.05 (s, 2H), 4.28 (q, J = 7.1 Hz, 4H), 4.01 (s, 2H), 2.84 (s, 6H), 2.16 (s, 6H), 1.73 (s, 6H), 1.34 (t, J = 7.1 Hz, 6H). Synthesis of Compound PLC-32 Compound PLC-32.1: 9-bromo-2-(6-hydroxyhexyl)-1H-xantheno[2,1,9-def]isoquinolin e-1,3(2H)-dione Compound PLC-32.1 was synthesized from Compound PLC-3.3 (6.534 mmol, 2.401g), 6-aminohexan- 1-ol (13.08 mmol, 1533 mg), and DMAP 1.962 mmol, 240 mg) in a manner like the methods described above. The crude product was filtered off and washed with water, then the wet precipitate was used in the next step with no further purification. MS (APCI): calculated for Chemical Formula: C24H20BrNO4 (M+H) = 466; found: 466. Compound PLC-32.2 2-(6-hydroxyhexyl)-9-(4-(trifluoromethyl)phenyl)-1H-xantheno [2,1,9- def]isoquinoline-1,3(2H)-dione Compound PLC-32.2 was synthesized from Compound PLC-32.1 (assume 100% yield, 6.534 mmol, 3.047 g), (4-(trifluoromethyl)phenyl)boronic acid (13.068 mmol, 2.482 g), K ₂ CO ₃ (17.969 mmol, 2483 mg), and Pd(dppf)Cl2 (0.4574 mmol, 335 mg) in THF (120 mL)/DMF (24 mL)/H ₂ O 12 mL) at 80 ° C in a manner like the methods described above. After adding water and filtering, the resulting precipitate was washed with water, then methanol. The product was dried by suction, then dried in vacuo. Gives 1.191 g (34% yield, based on Compound PLC-3.3, 2 steps). MS (APCI): calculated for Chemical Formula: C ₃₁ H ₂₄ F ₃ NO ₄ (M+H) = 532; found: 532. Compound PLC-32.3: 2-(6-bromohexyl)-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2 ,1,9- def]isoquinoline-1,3(2H)-dione A 250 mL 2N RBF was charged with a stir bar and fitted with a gas adapter/finned condenser and a flow control. To the flask was added Compound PLC-32.2 (2.239 mmol, 1.190 g), followed by 48% HBr/H ₂ O (30 mL). The heat block was set to 130 ° C and the reaction mixture stirred at this temperature for 3 hours. Another portion of 48% HBr/H ₂ O (30 mL) was added, and the reaction mixture stirred at 130 ° C overnight. The reaction mixture was cooled to room temperature and diluted with water (~100 mL), then the precipitate was filtered off, washing with water, then methanol. The product was loaded onto ~25g of silica gel in a loader. Purify by flash chromatography on silica gel (120g, solid load, equilibrate0% EtOAc/DCM, 0% (2 CV) → 10% EtOAc/DCM (20 CV)). Collect fractions with product and evaporate to dryness in vacuo. Gives material that is about 80% pure. Gives a yellow solid, 1.073 g (80% yield). MS (APCI): calculated for Chemical Formula: C ₃₁ H ₂₃ BrF ₃ NO ₃ (M+H) = 594; found: 594. ¹ H NMR (400 MHz, TCE) δ 8.63 (d, J = 7.9 Hz, 1H), 8.58 (d, J = 8.3 Hz, 1H), 8.23 (d, J = 2.1 Hz, 1H), 8.03 (d, J = 8.0 Hz, 1H), 7.84 – 7.73 (m, 5H), 7.49 (d, J = 8.6 Hz, 1H), 7.34 (d, J = 8.3 Hz, 1H), 4.19 – 4.09 (m, 2H), 3.44 (td, J = 6.8, 1.9 Hz, 2H), 1.90 (p, J = 6.9 Hz, 2H), 1.75 (p, J = 7.8 Hz, 2H), 1.57 – 1.38 (m, 4H). Compound PLC-32.4 4-((6-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2 ,1,9- def]isoquinolin-2(3H)-yl)hexyl)oxy)-2,6-dimethylbenzaldehyde Compound PLC-32.4 was synthesized from Compound PCL-32.3 (0.200 mmol, 119 mg), 4-hydroxy-2,6- dimethylbenzaldehyde (0.300 mmol, 45 mg), and K ₂ CO ₃ (0.260 mmol, 36 mg) in dry DMF (10 mL). The reaction mixture was sonicated for 15 minutes, then stirred in a heating block at 65 ° C for 7 hours. The heat was turned off and water was added to the warm reaction mixture (~100 mL), which does not give a precipitate. The water layer was saturated with NaCl, then extracted with THF (1 X 200 mL, 2 X 50 mL). The combined organic layers were dried over MgSO ₄ , filtered, and evaporated to dryness in vacuo. The crude product was dissolved in DCM and loaded onto ~5g silica gel in a loader. Purified by flash chromatography on silica gel (80g, solid load, equilibrate 70% DCM/hexanes, eluting 70% (2 CV) → 100% DCM/hexanes (5 CV) → isocratic 100% DCM/hexanes (5 CV) → 0% EtOAc/DCM (0 CV) → isocratic 0% EtOAc/DCM (5 CV) → 10% EtOAc/DCM (20 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a yellow solid, 95 mg (71% yield). MS (APCI): calculated for Chemical Formula: C ₄₀ H ₃₂ F ₃ NO ₅ (M+H) = 664; found: 664. ¹ H NMR (400 MHz, TCE) δ 10.42 (s, 1H), 8.64 (d, J = 7.9 Hz, 1H), 8.59 (d, J = 8.3 Hz, 1H), 8.25 (d, J = 2.2 Hz, 1H), 8.05 (d, J = 8.0 Hz, 1H), 7.84 – 7.74 (m, 5H), 7.51 (d, J = 8.5 Hz, 1H), 7.36 (d, J = 8.3 Hz, 1H), 6.60 (s, 2H), 4.20 – 4.15 (m, 2H), 4.01 (t, J = 6.4 Hz, 2H), 2.59 (s, 6H), 1.89 – 1.70 (m, 4H), 1.60 – 1.43 (m, 4H). Compound PLC-32: Diethyl 10-(4-((6-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xanthe no[2,1,9- def]isoquinolin-2(3H)-yl)hexyl)oxy)-2,6-dimethylphenyl)-5,5- difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4- dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxyla te Compound PLC-32 was synthesized from Compound PLC-32.4 (0.1401 mmol, 93 mg), ethyl 2,4- dimethyl-1H-pyrrole-3-carboxylate (0.0.2943 mmol, 49 mg) in dry DCE (20 mL), followed by pTsOH.H ₂ O (0.0140 mmol, 2.7 mg), then DDQ (0.0.2382 mmol, 54 mg) 2X Et3N (1.121 mmol, 0..156 mL) and BF3.OEt2 (1.682 mmol, 0..208 mL) in a manner similar to Compound 32. The crude reaction mixture was diluted with hexanes (~25%), then loaded onto ~5g silica gel in a loader. Purified by flash chromatography on silica gel (80g, solid load, equilibrate 70% DCM/hexanes, eluting 70% (2 CV) → 100% DCM/hexanes (5 CV) → isocratic 100% DCM/hexanes (5 CV) → 0% EtOAc/DCM (0 CV) → isocratic 0% EtOAc/DCM (5 CV) → 10% EtOAc/DCM (20 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 26 mg (18% yield). MS (APCI): calculated for Chemical Formula: C ₅₈ H ₅₃ BF ₅ N ₃ O ₈ (M+H) = 1026; found: 1026. ¹ H NMR (400 MHz, TCE) δ 8.56 (d, J = 7.8 Hz, 1H), 8.51 (d, J = 8.4 Hz, 1H), 8.16 (d, J = 2.3 Hz, 1H), 7.97 (d, J = 8.0 Hz, 1H), 7.77 – 7.65 (m, 5H), 7.42 (d, J = 8.6 Hz, 1H), 7.27 (d, J = 8.3 Hz, 1H), 6.66 (s, 2H), 4.18 (q, J = 7.1 Hz, 4H), 4.10 (dd, J = 8.8, 6.6 Hz, 2H), 3.92 (t, J = 6.5 Hz, 2H), 2.74 (s, 6H), 1.99 (s, 6H), 1.82 – 1.67 (m, 4H), 1.65 (s, 6H), 1.52 – 1.38 (m, 4H), 1.24 (t, J = 7.1 Hz, 6H). Synthesis of Compound PLC-33

Compound PLC-33.1: 2-(2-(2-methoxyethoxy)ethoxy)ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate) A 100 mL 2N RBF was charged with a stir bar and fitted with a gas adapter/finned condenser and a flow control. The system was flushed with argon. To the flask was added NaH (60% mineral oil, 45.00 mmol, 1800 mg). The mixture was stirred at room temperature and carefully added 2-(2-(2- methoxyethoxy)ethoxy)ethan-1-ol (90.00 mmol, 14.4 mL). When the production of hydrogen gas has ceased, ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (30.00 mmol, 5.016 g) was added. The system was closed and stirred under argon atmosphere. The heat block was set to 130 ° C and the reaction mixture stirred at this temperature for 30 minutes. LCMS indicates ~45:55 product:starting material. The reaction was continued for several more hours at 130 ° C with little change in ratio. A vent was installed on the top of the findenser and was opened to allow the escape of ethanol. After heating for ~5 hours, less than 5% of the starting ester remained. The reaction mixture was cooled to room temperature and water was added. No precipitate formed, so the reaction mixture was treated with NaCl to break the emulsion, then extracted with ethyl acetate (3 X 100 mL). The combined organic layers were washed with brine (50 mL), dried over MgSO4, filtered and evaporated to dryness in vacuo. Gives a dark brown oil. The vial was heated under argon flow at 140 ° C to remove excess alcohol. Gives 6.839 g (80% yield). MS (APCI): calculated for Chemical Formula: C ₁₄ H ₂₃ NO ₅ (M+H) = 286; found: 286. ¹ H NMR (400 MHz, TCE) δ 8.07 (s, 1H), 6.39 (dd, J = 2.3, 1.2 Hz, 1H), 4.38 – 4.31 (m, 2H), 3.81 – 3.74 (m, 2H), 3.69 – 3.65 (m, 2H), 3.65 – 3.58 (m, 4H), 3.56 – 3.50 (m, 2H), 3.35 (s, 3H), 2.48 (s, 3H), 2.23 (d, J = 1.1 Hz, 3H). Compound PLC-33.2: Bis(2-(2-(2-methoxyethoxy)ethoxy)ethyl) 5,5-difluoro-10-(4-hydroxy-2,6- dimethylphenyl)-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2 -c:2',1'-f][1,3,2]diazaborinine-2,8- dicarboxylate Compound PLC-33.2 was synthesized from Compound PLC-33.1 (3.588 mmol, 1024 mg), 4-hydroxy- 2,6-dimethylbenzaldehyde (1.750 mmol, 263 mg), and pTsOH.H ₂ O (0.175 mmol, 33 mg), then DDQ (2.975 mmol, 675 mg) and 2X Et3N (14.00 mmol, 1.95 mL) and BF3.OEt2 (14.00 mmol, 2.59 mL) in dry DCE (50 mL) at room temperature, then 50 ° C in a manner like the methods above. The crude reaction mixture was loaded onto ~30g of silica gel in a loader. Purify by flash chromatography on silica gel (120g, equilibrate 30% EtOAc/DCM, eluting 30% (2 CV), → 100% EtOAc (20 CV)). Elutes as a broad peak. Fractions containing product were evaporated to dryness in vacuo. Gives a thick, gummy product, 1.055g (80% yield). MS (APCI): calculated for Chemical Formula: C37H51BF2N2O11 (M+H) = 749; found: 749. ¹ H NMR (400 MHz, TCE) δ 6.61 (s, 2H), 4.28 (t, J = 4.8 Hz, 4H), 3.67 (t, J = 4.8 Hz, 4H), 3.59 – 3.48 (m, 12H), 3.47 – 3.38 (m, 4H), 3.27 (s, 7H), 2.75 (s, 6H), 1.97 (s, 6H), 1.66 (s, 6H). Compound PLC-33: Bis(2-(2-(2-methoxyethoxy)ethoxy)ethyl) 10-(4-(2-(4-(1,3-dioxo-9-(4- (trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2 (3H)-yl)phenyl)acetoxy)-2,6- dimethylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4- dipyrrolo[1,2-c:2',1'- f][1,3,2]diazaborinine-2,8-dicarboxylate Compound PLC-33.2 (0.045 mmol, 34 mg), Compound PLC-3.5 (0.07875 mmol, 45 mg), DMAP.pTsOH salt (0.090 mmol, 27 mg), and EDC.HCl (0.180 mmol, 35 mg) were combined in a 40 mL screw cap vial with a stir bar. To the vial was added dry DCM (10 mL) and the reaction mixture stirred at room temperature for 90 minutes. The crude reaction mixture was loaded onto ~20g of silica gel in a loader. Purified by flash chromatography on silica gel (80g, solid load, equilibrate 10% EtOAc/DCM, eluting 50% (2 CV) → 100% EtOAC (20 CV)). Gives an orange solid, 36 mg (62% yield). MS (APCI): calculated for Chemical Formula: C ₇₀ H ₆₇ BF ₅ N ₃ O ₁₅ (M+H) = 1296; found: 1296. ¹ H NMR (400 MHz, TCE) δ 8.69 (d, J = 7.8 Hz, 1H), 8.64 (d, J = 8.3 Hz, 1H), 8.29 (d, J = 2.2 Hz, 1H), 8.11 (d, J = 8.1 Hz, 1H), 7.85 – 7.76 (m, 5H), 7.66 – 7.61 (m, 2H), 7.55 (d, J = 8.6 Hz, 1H), 7.41 (d, J = 8.3 Hz, 2H), 7.40 – 7.34 (m, 2H), 7.06 (s, 2H), 4.38 (dd, J = 5.9, 3.7 Hz, 4H), 4.01 (s, 2H), 3.79 – 3.72 (m, 4H), 3.68 – 3.55 (m, 12H), 3.55 – 3.48 (m, 4H), 3.35 (s, 6H), 2.85 (s, 6H), 2.16 (s, 6H), 1.74 (s, 6H). Synthesis of Compound PLC-34

Compound PLC-34: Bis(2-(2-(2-methoxyethoxy)ethoxy)ethyl) 5,5-difluoro-10-(4-(2-(4-(9-(4-(2-(2-(2- methoxyethoxy)ethoxy)ethoxy)phenyl)-1,3-dioxo-1H-xantheno[2, 1,9-def]isoquinolin-2(3H)- yl)phenyl)acetoxy)-2,6-dimethylphenyl)-1,3,7,9-tetramethyl-5 H-4l4,5l4-dipyrrolo[1,2-c:2',1'- f][1,3,2]diazaborinine-2,8-dicarboxylate Compound PLC-33.2 (0.045 mmol, 34 mg), Compound PLC-17.6 (0.0675 mmol, 45 mg), ), DMAP.pTsOH salt (0.090 mmol, 27 mg), and EDC.HCl (0.1350 mmol, 30 mg) were combined in a 40 mL screw cap vial with a stir bar and synthesized in a manner similar to the methods above. The crude product was loaded onto ~20g of silica gel in a loader. Purified by flash chromatography (80g, solid load, equilibrate 30% EtOAc/DCM, eluting 30% (2 CV) → 100% EtOAc (20 CV) → isocratic 100% EtOAc until product fully elutes). Elutes as a broad peak. Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 34 mg (54% yield). MS (APCI): calculated for Chemical Formula: C ₇₆ H ₈₂ BF ₂ N ₃ O ₁₉ (M+H) = 1391; found: 1391. ¹ H NMR (400 MHz, TCE) δ 8.68 (d, J = 7.9 Hz, 1H), 8.63 (d, J = 8.3 Hz, 1H), 8.25 (d, J = 2.1 Hz, 1H), 8.11 (d, J = 8.2 Hz, 1H), 7.78 (dd, J = 8.7, 2.1 Hz, 1H), 7.64 (dd, J = 8.6, 2.3 Hz, 4H), 7.50 (d, J = 8.6 Hz, 1H), 7.44 – 7.34 (m, 3H), 7.09 (d, J = 8.7 Hz, 2H), 7.06 (s, 2H), 4.38 (t, J = 4.9 Hz, 4H), 4.22 (t, J = 4.8 Hz, 2H), 4.01 (s, 2H), 3.90 (t, J = 4.8 Hz, 2H), 3.76 (dt, J = 5.5, 2.7 Hz, 6H), 3.71 – 3.54 (m, 18H), 3.54 – 3.49 (m, 4H), 3.38 (s, 3H), 3.35 (s, 6H), 2.85 (s, 6H), 2.16 (s, 6H), 1.74 (s, 6H). Synthesis of Compound PLC-35 Compound PLC-35.1: 2,2,2-trifluoroethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate Compound PLC-35.1 was synthesized from ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (12.00 mmol, 2.006 g), NaH (60% mineral oil, 36.00 mmol, 1440 mg), and 2,2,2-trifluoroethan-1-ol (120.0 mmol, 8.74 mL) in a manner similar to the methods above at 130 ° C. Because of the lower boiling point of the target alcohol, all solvents were vented and 2,2,2-trifluoroethan-1-ol (8.74 mL) was added again. Conversion could only be driven to about ~20%. The crude material was loaded onto ~20g of silica gel in a loader. Purified by flash chromatography on silica gel (120g, solid load, equilibrate 10% EtOAc/hexanes, eluting 10% (2 CV) → 50% EtOAc/hexanes (20 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives 468 mg (18% yield). MS (APCI): calculated for Chemical Formula: C ₉ H ₁₀ F ₃ NO ₂ (M+H) = 222; found: 222. ¹ H NMR (400 MHz, TCE) δ 8.12 (s, 1H), 6.42 (dd, J = 2.3, 1.2 Hz, 1H), 4.61 (q, J = 8.6 Hz, 2H), 2.49 (s, 3H), 2.24 (d, J = 1.1 Hz, 3H). Compound PLC-35.2 Bis(2,2,2-trifluoroethyl) 5,5-difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-1,3,7,9- tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazab orinine-2,8-dicarboxylate Compound PLC-35.2 was synthesized from Compound PLC-35.1 (1.575 mmol, 348 mg), 4-hydroxy-2,6- dimethylbenzaldehyde (0.750 mmol, 113 mg), ), and pTsOH.H ₂ O (0.300 mmol, 57 mg), then DDQ (1.275 mmol, 289 mg) and 2X Et ₃ N (6.00 mmol, 0.84 mL) and BF ₃ .OEt ₂ (9.00 mmol, 1.10 mL) in dry DCE (20 mL) at 60 ° C, then 50 ° C in a manner similar to the methods described above. The crude reaction mixture diluted 1:1 with hexanes, then was loaded onto ~30g of silica gel in a loader. Purified by flash chromatography on silica gel (220g, solid load, equilibrate 5% EtOAc/hexanes, eluting 5% (2 CV) → 30% EtOAc/hexanes (10 CV). Fractions containing product were evaporated to dryness. Gives an orange solid, 208 mg (45% yield). MS (APCI): calculated for Chemical Formula: C ₂₇ H ₂₅ BF ₈ N ₂ O ₅ (M+H) = 621; found: 621. ¹ H NMR (400 MHz, TCE) δ 6.72 (s, 2H), 4.63 (q, J = 8.5 Hz, 4H), 2.85 (s, 6H), 2.07 (s, 6H), 1.77 (s, 6H). Compound PLC-38: Bis(2,2,2-trifluoroethyl) 10-(4-(2-(4-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H- xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6- dimethylphenyl)-5,5-difluoro-1,3,7,9- tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazab orinine-2,8-dicarboxylate Compound 35.2 (0.060 mmol, 37 mg), Compound 3.5 (0.105 mmol, 59 mg), DMAP.pTsOH salt (0.120 mmol, 35 mg), and EDC.HCl (0.240 mmol, 46 mg) were combined in a 40 mL screw cap vial with a stir bar and dry DCM (10 mL) and synthesized in a manner similar to Compound 36. The solvents were evaporated and the crude reaction mixture taken up in toluene and loaded onto ~20g silica gel in a loader. Purified by flash chromatography on silica gel (80g, solid load, equilibrate 0% EtOAc/toluene, eluting 0% (2 CV) → 0.5% EtOAc modifier on 0% EtOAc/toluene. Product elutes rapidly. Gives an orange solid, 21 mg (30% yield). MS (APCI): calculated for Chemical Formula: C ₆₀ H ₄₁ BF ₁₁ N ₃ O ₉ (M+H) = 1168; found: 1168. ¹ H NMR (400 MHz, TCE) δ 8.69 (d, J = 7.9 Hz, 1H), 8.64 (d, J = 8.3 Hz, 1H), 8.29 (d, J = 2.2 Hz, 1H), 8.11 (d, J = 8.1 Hz, 1H), 7.85 – 7.76 (m, 5H), 7.68 – 7.61 (m, 2H), 7.55 (d, J = 8.7 Hz, 1H), 7.40 (s, 0H), 7.40 – 7.35 (m, 2H), 4.63 (q, J = 8.5 Hz, 4H), 4.02 (s, 2H), 2.86 (s, 6H), 2.16 (s, 6H), 1.76 (s, 6H). Synthesis of Compound PLC-36

Compound PLC-36.1: tert-butyl 4-(2-(3-hydroxypropyl)-1,3-dioxo-2,3-dihydro-1H-xantheno[2,1 ,9- def]isoquinolin-9-yl)benzoate Compound PLC-36.1 was synthesized from Compound 27.1 (1.30 mmol, 552 mg), (4-(tert- butoxycarbonyl)phenyl)boronic acid (2.60 mmol, 577 mg), K ₂ CO ₃ (3.575 mmol, 494 mg), and Pd(dppf)Cl ₂ (0.0910 mmol, 67 mg) in THF (30 mL)/DMF (6 mL)/water (3 mL) at 80 ° C similar to Compound 32.2. After water was added, the product was filtered, off, washed with water, then washed with methanol. The compound was dried by suction, then dried in vacuo. Gives a brown- yellow solid, 633 mg (93% yield). MS (APCI): calculated for Chemical Formula: C ₃₂ H ₂₇ NO ₆ (M+H) = 522; found: 522. ¹ H NMR (400 MHz, TCE) δ 8.66 (d, J = 7.9 Hz, 1H), 8.61 (d, J = 8.3 Hz, 1H), 8.27 (d, J = 2.2 Hz, 1H), 8.13 (d, J = 8.0 Hz, 2H), 8.06 (d, J = 7.9 Hz, 1H), 7.80 (dd, J = 8.6, 2.1 Hz, 1H), 7.74 (d, J = 8.0 Hz, 2H), 7.51 (d, J = 8.6 Hz, 1H), 7.37 (d, J = 8.3 Hz, 1H), 4.33 (t, J = 6.0 Hz, 2H), 3.57 (q, J = 6.0 Hz, 2H), 3.20 (t, J = 6.9 Hz, 1H), 2.07 – 1.91 (m, 2H), 1.64 (s, 9H). Compound 36.2: tert-butyl 4-(2-(3-bromopropyl)-1,3-dioxo-2,3-dihydro-1H-xantheno[2,1,9 - def]isoquinolin-9-yl)benzoate A 100 mL 2N round bottom flask was placed in an aluminum heat block and charged with a stir bar. The flask was fitted with a finned condenser/gas adapter and flow control valve. The system was flushed with argon. To the flask was added Compound PLC-36.1 (1.208 mmol, 630 mg) and dry DCM (30 mL). With stirring at room temperature under argon was added Et3N (2.416 mmol, 0.337 mL), followed by PBr3 (0.046 mL). The reaction mixture was stirred at room temperature for 15 minutes. To the flask was added PBr3 (2.416 mmol, 0.230 mL) and stirring continued at room temperature for 2 hours. The crude reaction mixture was partitioned between DCM (50 mL) and water (25 mL).10 mL of brine was added to break the emulsion and the layers were separated. The reaction mixture was acidified with AcOH, then the reaction mixture was extracted with DCM (3 X 50 mL). The combined organic layers were dried over MgSO ₄ , filtered, and evaporated to dryness in vacuo. The crude product was dissolved in DCM and loaded onto ~20g of silica gel in a loader. Purified by flash chromatography on silica gel. (80g, solid load, equilibrate 0% EtOAc/DCM, eluting 0% (2 CV) → 10% EtOAc/DCM (20 CV)). Fractions containing the product were evaporated to dryness in vacuo. Gives a yellow solid, 192 mg, 27% yield. Most of the starting material goes to unidentified by-products. MS (APCI): calculated for Chemical Formula: C ₃₂ H ₂₆ BrNO ₅ (M+H) = 584; found: 584. ¹ H NMR (400 MHz, TCE) δ 8.64 (d, J = 7.9 Hz, 1H), 8.59 (d, J = 8.3 Hz, 1H), 8.27 (d, J = 2.2 Hz, 1H), 8.17 – 8.09 (m, 2H), 8.05 (d, J = 8.0 Hz, 1H), 7.80 (dd, J = 8.6, 2.1 Hz, 1H), 7.77 – 7.69 (m, 2H), 7.50 (d, J = 8.6 Hz, 1H), 7.36 (d, J = 8.3 Hz, 1H), 4.31 (t, J = 7.1 Hz, 2H), 3.54 (t, J = 6.8 Hz, 2H), 2.34 (p, J = 6.9 Hz, 2H), 1.64 (s, 9H). Compound PLC-36.3 tert-butyl 4-(2-(3-(4-formyl-3,5-dimethylphenoxy)propyl)-1,3-dioxo-2,3- dihydro- 1H-xantheno[2,1,9-def]isoquinolin-9-yl)benzoate Compound PLC-36.3 was synthesized from Compound PLC-36.2 (0.1540 mmol, 90 mg), 4-hydroxy-2,6- dimethylbenzaldehyde (0.308 mmol, 46 mg), and K ₂ CO ₃ in dry DMF (10 mL) in a manner similar to Compound 34.4. The crude reaction was diluted with crushed ice (~100g). Once it had all melted, the crude product was filtered off, washing with water. The product was dried by suction, then dissolved in DCM and evaporated to dryness in vacuo. Gives a quantitative yield of a yellow solid. MS (APCI): calculated for Chemical Formula: C ₄₁ H ₃₅ NO ₇ (M+H) = 654; found: 654. ¹ H NMR (400 MHz, TCE) δ 10.43 (s, 1H), 8.65 (d, J = 7.9 Hz, 1H), 8.59 (d, J = 8.3 Hz, 1H), 8.28 (d, J = 2.1 Hz, 1H), 8.16 – 8.10 (m, 2H), 8.07 (d, J = 8.0 Hz, 1H), 7.80 (dd, J = 8.6, 2.1 Hz, 1H), 7.78 – 7.70 (m, 2H), 7.37 (d, J = 8.4 Hz, 1H), 6.55 (s, 2H), 4.39 (t, J = 7.0 Hz, 2H), 4.18 (t, J = 6.0 Hz, 2H), 2.56 (s, 6H), 2.26 (p, J = 6.5 Hz, 2H), 1.64 (s, 9H). Compound PLC-36: Diethyl 10-(4-(3-(9-(4-(tert-butoxycarbonyl)phenyl)-1,3-dioxo-1H-xan theno[2,1,9- def]isoquinolin-2(3H)-yl)propoxy)-2,6-dimethylphenyl)-5,5-di fluoro-1,3,7,9-tetramethyl-5H-4l4,5l4- dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxyla te Compound PLC-36 was synthesized from Compound PLC-36.3 (0.154 mmol, 100 mg), ethyl 2,4- dimethyl-1H-pyrrole-3-carboxylate (0.308 mmol, 52 mg) in dry DCE (20 mL), followed by TFA (0.020 mL) at room temperature, then DDQ (0.262 mmol, 59 mg) 2X Et ₃ N (1.232 mmol, 0.17 mL) and BF3.OEt2 (1.848 mmol, 0.23 mL) in a manner similar to the methods described above. The crude reaction mixture was diluted with hexanes and loaded onto ~20g of silica gel in a loader. Purified by flash chromatography on silica gel (120g, solid load, equilibrate 0% EtOAc/toluene, eluting 0% (2 CV) → 1% EtOAc/toluene (30 CV)). Only partial separation. Fractions containing pure product were evaporated to dryness in vacuo. Gives 56 mg pure (36% yield). MS (APCI): calculated for Chemical Formula: C ₅₉ H ₅₆ BF ₂ N ₃ O ₁₀ (M+H) = 1016; found: 1016. ¹ H NMR (400 MHz, TCE) δ 8.66 (d, J = 7.9 Hz, 1H), 8.60 (d, J = 8.3 Hz, 1H), 8.29 (d, J = 2.1 Hz, 1H), 8.16 – 8.10 (m, 2H), 8.08 (d, J = 8.0 Hz, 1H), 7.80 (dd, J = 8.6, 2.1 Hz, 1H), 7.75 (d, J = 8.3 Hz, 2H), 7.51 (d, J = 8.6 Hz, 1H), 7.38 (d, J = 8.3 Hz, 1H), 6.67 (s, 2H), 4.42 (t, J = 7.1 Hz, 2H), 4.27 (q, J = 7.1 Hz, 4H), 4.17 (t, J = 6.1 Hz, 2H), 2.82 (s, 6H), 2.28 (p, J = 6.3 Hz, 2H), 2.04 (s, 6H), 1.72 (s, 6H), 1.64 (s, 9H), 1.34 (t, J = 7.1 Hz, 6H). Synthesis of Compound PLC-37 Compound PLC-37.1: 2-ethylhexyl 2,4-dimethyl-1H-pyrrole-3-carboxylate A 100 mL 2N RBF was charged with a stir bar and fitted with a gas adapter/finned condenser and a flow control. The system was flushed with argon. To the flask was added NaH (60% mineral oil, 36.00 mmol, 1440 mg). The mixture was stirred at room temperature and carefully added 2-ethylhexan-1- ol (120.00 mmol, 18.8 mL). When the production of hydrogen gas has ceased, ethyl 2,4-dimethyl-1H- pyrrole-3-carboxylate (12.00 mmol, 2.006 g) was added. The system was closed and stirred under argon atmosphere. The heat block was set to 130 ° C and the reaction mixture stirred at this temperature with the vent open for 30 minutes. The vent was closed and the system heated at 130 ° C for 2 hours, then the vent was opened again for ~30 minutes. The system was heated closed for ~2 hours again, at which point there is no ethyl ester remaining by LCMS. The reaction mixture was cooled to room temperature and quenched with sat. NH ₄ Cl solution, then diluted with water (~100 mL). The mixture was extracted with DCM (1X 100 mL, 2 X 50 mL). The combined organic layers were dried over MgSO ₄ , filtered, and evaporated to dryness in vacuo. Gives a dark brown oil. The vial was heated under argon flow at 140 ° C to remove excess alcohol. Gives a brown oil, 2.920 g (97% yield). MS (APCI): calculated for Chemical Formula: C ₁₅ H ₂₅ NO ₂ (M+H) = 252; found: 252. ¹ H NMR (400 MHz, TCE) δ 4.20 – 4.05 (m, 2H), 3.53 (d, J = 4.9 Hz, 2H), 2.49 (s, 3H), 2.24 (d, J = 1.0 Hz, 3H), 1.75 – 1.56 (m, 4H), 1.52 – 1.16 (m, 17H), 1.00 – 0.79 (m, 13H). Compound PLC-37.2: Bis(2-ethylhexyl) 5,5-difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-1,3,7,9- tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazab orinine-2,8-dicarboxylate Compound PLC-37.2 was synthesized from Compound PLC-37.1 (4.20 mmol, 1056 mg), 4-hydroxy- 2,6-dimethylbenzaldehyde (2.00 mmol,300 mg), and TFA (0.200 mL), then DDQ (3.40 mmol, 772 mg) and 2X Et3N (16.00 mmol, 2.20 mL) and BF ₃ .OEt ₂ (24.00 mmol, 3.0 mL) in dry DCE (20 mL) at room temperature, then 50 ° C in a manner similar to Compound 32. The crude reaction mixture was loaded onto ~65g of silica gel in a loader. Purify by flash chromatography on silica gel (220g, equilibrate 0% EtOAc/hexanes, eluting 0% (2 CV), → 20% EtOAc/hexanes (30 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a thick, gummy product, 614 mg (45% yield). MS (APCI): calculated for Chemical Formula: C ₃₉ H ₅₅ BF ₂ N ₂ O ₅ (M+H) = 681; found: 681. ¹ H NMR (400 MHz, TCE) δ 6.71 (s, 2H), 4.24 – 4.07 (m, 4H), 2.84 (s, 6H), 2.07 (s, 6H), 1.75 (s, 6H), 1.48 – 1.22 (m, 16H), 0.96 – 0.82 (m, 10H). Compound PLC-37: Bis(2-ethylhexyl) 10-(4-(2-(4-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H- xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6- dimethylphenyl)-5,5-difluoro-1,3,7,9- tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazab orinine-2,8-dicarboxylate Compound PLC-37.2 (0.075 mmol, 51 mg), Compound PLC-3.5 (0.113 mmol, 64 mg), DMAP.pTsOH salt (0..150 mmol, 44 mg), and EDC.HCl (0.300 mmol, 58 mg) were combined in a 40 mL screw cap vial with a stir bar. To the vial was added dry DCM (10 mL) and the reaction mixture stirred at room temperature for 90 minutes. The crude reaction mixture was loaded onto ~20g of silica gel in a loader. Purified by flash chromatography on silica gel (220g, solid load, equilibrate 10% EtOAc/hexanes, eluting 10% (2 CV) → 50% EtOAC/hexanes (20 CV)). Gives an orange solid, 69 mg (75% yield). MS (APCI): calculated for Chemical Formula: C ₇₂ H ₇₁ BF ₅ N ₃ O ₉ (M+H) = 1229; found: 1229. ¹ H NMR (400 MHz, TCE) δ 8.69 (d, J = 7.9 Hz, 1H), 8.64 (d, J = 8.3 Hz, 1H), 8.29 (d, J = 2.2 Hz, 1H), 8.11 (d, J = 8.1 Hz, 1H), 7.85 – 7.77 (m, 5H), 7.67 – 7.62 (m, 2H), 7.55 (d, J = 8.6 Hz, 1H), 7.42 (d, J = 8.3 Hz, 1H), 7.40 – 7.35 (m, 2H), 7.07 (s, 2H), 4.23 – 4.08 (m, 4H), 4.02 (s, 2H), 2.85 (s, 6H), 2.16 (s, 6H), 1.74 (s, 6H), 1.69 – 1.56 (m, 2H), 1.48 – 1.22 (m, 16H), 0.95 – 0.80 (m, 12H). Synthesis of Compound PLC-38 Compound PLC-38.1: 9-(4-butylphenyl)-2-(3-hydroxypropyl)-1H-xantheno[2,1,9-def] isoquinoline- 1,3(2H)-dione Compound PLC-38.1 was synthesized from Compound PLC-27.1 (1.500 mmol, 636 mg), (4- butylphenyl)boronic acid (3.00 mmol, 534 mg), K ₂ CO ₃ (4.125 mmol, 570 mg), and Pd(dppf)Cl ₂ (0.105 mmol, 77 mg) in THF (30 mL)/DMF (6 mL)/water (3 mL) at 80 ° C in a manner similar to Compound 32.2. The precipitated compound was filtered off, washed with water, and dried in vacuo. Gives a brown-yellow solid, 655 mg (92% yield). MS (APCI): calculated for Chemical Formula: C ₃₁ H ₂₇ NO ₄ (M+H) = 478; found: 478. ¹ H NMR (400 MHz, TCE) δ 8.66 (d, J = 7.9 Hz, 1H), 8.61 (d, J = 8.4 Hz, 1H), 8.26 (d, J = 2.1 Hz, 1H), 8.06 (d, J = 8.0 Hz, 1H), 7.79 (dd, J = 8.6, 2.1 Hz, 1H), 7.61 (d, J = 7.9 Hz, 2H), 7.48 (d, J = 8.6 Hz, 1H), 7.41 – 7.30 (m, 3H), 4.34 (t, J = 6.1 Hz, 2H), 3.57 (q, J = 6.0 Hz, 2H), 3.24 (t, J = 6.9 Hz, 1H), 2.70 (t, J = 7.7 Hz, 2H), 2.06 – 1.92 (m, 2H), 1.75 – 1.64 (m, 2H), 1.42 (h, J = 7.4 Hz, 2H), 0.98 (t, J = 7.3 Hz, 3H). Compound PLC-38.2: 3-(9-(4-butylphenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquin olin-2(3H)- yl)propyl 4-methylbenzenesulfonate A 100 mL 2N round bottom flask was placed in an aluminum heat block and charged with a stir bar. The flask was fitted with a finned condenser/gas adapter and flow control valve. The system was flushed with argon. To the flask was added Compound PLC-38.1 (0.325 mmol, 155 mg), 4- methylbenzenesulfonic anhydride (1.30 mmol, 424 mg), and dry DCE (20 mL). The reaction mixture was stirred under argon at room temperature and Et ₃ N was added (1.463 mmol, 0.20 mL). The reaction mixture was stirred under argon and the heat block was set to 90 ° C and stirred at this temperature for one hour. The reaction was cooled to room temperature and loaded onto ~15 g silica gel in a loader. Purified by flash chromatography on silica gel (80g, solid load, equilibrate 0% EtOAc/DCM, eluting 0% (2 CV) → 10% EtOAc/DCM (10 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a yellow solid, 157 mg (77% yield). MS (APCI): calculated for Chemical Formula: C38H33NO6S (M+H) = 632; found: 632. ¹ H NMR (400 MHz, TCE) δ 8.61 (d, J = 7.9 Hz, 1H), 8.56 (d, J = 8.4 Hz, 1H), 8.24 (d, J = 2.2 Hz, 1H), 8.04 (d, J = 8.1 Hz, 1H), 7.81 – 7.72 (m, 3H), 7.61 (d, J = 8.1 Hz, 2H), 7.47 (d, J = 8.6 Hz, 1H), 7.40 – 7.27 (m, 5H), 4.19 (dt, J = 11.9, 6.6 Hz, 4H), 2.70 (t, J = 7.8 Hz, 2H), 2.42 (s, 3H), 2.19 – 2.07 (m, 2H), 1.76 – 1.64 (m, 2H), 1.42 (h, J = 7.3 Hz, 2H), 0.98 (t, J = 7.4 Hz, 3H). Compound PLC-38.3: 4-(3-(9-(4-butylphenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoq uinolin-2(3H)- yl)propoxy)-2,6-dimethylbenzaldehyde Compound 46.3 was synthesized from Compound PLC-38.2 (0.119 mmol, 75 mg), ), 4-hydroxy-2,6- dimethylbenzaldehyde (0.356 mmol, 53 mg), and K ₂ CO ₃ (0.332 mmol, 46 mg) in dry DMF (10 mL). The reaction mixture was sonicated for 15 minutes, then stirred in a heating block at 65 ° C for 7 hours. The heat was turned off and ~25g of crushed ice was added to the reaction mixture. Water (~90 mL) was added, and the product was filtered off, washing with water. The product was dried by suction, then in vacuo. Gives a yellow solid, 72 mg (100% yield). MS (APCI): calculated for Chemical Formula: C40H35NO5 (M+H) = 610; found: 610. ¹ H NMR (400 MHz, TCE) δ 10.43 (s, 1H), 8.63 (d, J = 7.9 Hz, 1H), 8.58 (d, J = 8.3 Hz, 1H), 8.25 (d, J = 2.1 Hz, 1H), 8.05 (d, J = 8.0 Hz, 1H), 7.78 (dd, J = 8.6, 2.1 Hz, 1H), 7.61 (d, J = 7.9 Hz, 2H), 7.47 (d, J = 8.6 Hz, 1H), 7.39 – 7.29 (m, 3H), 6.55 (s, 2H), 4.38 (t, J = 7.1 Hz, 2H), 4.17 (t, J = 6.0 Hz, 2H), 2.70 (t, J = 7.8 Hz, 2H), 2.56 (s, 6H), 2.26 (p, J = 6.7 Hz, 2H), 1.67 (p, J = 7.6 Hz, 2H), 1.42 (h, J = 7.4 Hz, 2H), 0.98 (t, J = 7.3 Hz, 3H). Compound PLC-38: Diethyl 10-(4-(3-(9-(4-butylphenyl)-1,3-dioxo-1H-xantheno[2,1,9-def] isoquinolin- 2(3H)-yl)propoxy)-2,6-dimethylphenyl)-5,5-difluoro-1,3,7,9-t etramethyl-5H-4l4,5l4-dipyrrolo[1,2- c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate Compound PLC-38 was synthesized from Compound PCL-38.3 (0.118 mmol, 72 mg), ethyl 2,4- dimethyl-1H-pyrrole-3-carboxylate (0.307 mmol, 51 mg) in dry DCE (20 mL), followed by TFA (1% v/v), then DDQ (0.201 mmol, 46 mg) 2X Et3N (0.944 mmol, 0.130 mL) and BF3.OEt2 (1.420 mmol, 0.175 mL) at 80 ° C, then 50 ° C in a manner similar to Compound 32. The crude reaction mixture was loaded onto ~20g silica gel in a loader. Purified by flash chromatography on silica gel (80g, solid load, equilibrate 0% EtOAc/hexanes, eluting 0% (2 CV) → 50% EtOAc/hexanes (30 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 21 mg (18% yield). MS (APCI): calculated for Chemical Formula: C ₅₈ H ₅₆ BF ₂ N ₃ O ₈ (M+H) = 972; found: 972. ¹ H NMR (400 MHz, TCE) δ 8.65 (d, J = 7.9 Hz, 1H), 8.59 (d, J = 8.4 Hz, 1H), 8.26 (d, J = 2.1 Hz, 1H), 8.07 (d, J = 8.1 Hz, 1H), 7.78 (dd, J = 8.6, 2.1 Hz, 1H), 7.65 – 7.57 (m, 2H), 7.48 (d, J = 8.6 Hz, 1H), 7.37 (d, J = 8.6 Hz, 1H), 7.34 (d, J = 8.2 Hz, 2H), 6.67 (s, 2H), 4.42 (t, J = 7.1 Hz, 2H), 4.27 (q, J = 7.1 Hz, 4H), 4.17 (t, J = 6.2 Hz, 2H), 2.82 (s, 6H), 2.70 (t, J = 7.7 Hz, 2H), 2.34 – 2.23 (m, 2H), 2.04 (s, 6H), 1.77 – 1.62 (m, 8H), 1.42 (h, J = 7.4 Hz, 2H), 1.34 (t, J = 7.1 Hz, 6H), 0.98 (t, J = 7.3 Hz, 3H). Synthesis of Compound PLC-39

Compound PLC-39.2: 4-(3-(9-(tert-butyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquin olin-2(3H)- yl)propoxy)-2,6-dimethylbenzaldehyde Compound PLC-39.2 was synthesized from Compound 39.1 (0.601 mmol, 279 mg), 4-hydroxy-2,6- dimethylbenzaldehyde (1.802 mmol, 270 mg), and K ₂ CO ₃ (1.682 mmol, 232 mg) in dry DMF (15 mL). The reaction mixture was sonicated for 15 minutes, then stirred in a heating block at 65 ° C for 7 hours. The crude reaction was diluted with ~100 mL of water and the product filtered off. The crude precipitate was dissolved in DCM and evaporated to dryness in vacuo. The product was dissolved in DCM and loaded onto ~20g of silica gel in a loader. Purified by flash chromatography on silica gel (40g, solid load, equilibrate 0% EtOAc/DCM, eluting 0% (2 CV) → 10% EtOAc/DCM (20 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a yellow solid, 301 mg (94% yield). MS (APCI): calculated for Chemical Formula: C ₃₄ H ₃₁ NO ₅ (M+H) = 534; found: 534. ¹ H NMR (400 MHz, TCE) δ 10.43 (s, 1H), 8.63 (d, J = 7.9 Hz, 1H), 8.57 (d, J = 8.4 Hz, 1H), 8.06 (d, J = 2.3 Hz, 1H), 8.01 (d, J = 8.0 Hz, 1H), 7.62 (dd, J = 8.8, 2.3 Hz, 1H), 7.37 (d, J = 8.7 Hz, 1H), 7.33 (d, J = 8.3 Hz, 1H), 6.56 (s, 2H), 4.38 (t, J = 7.0 Hz, 2H), 4.17 (t, J = 6.0 Hz, 2H), 2.57 (s, 6H), 2.25 (q, J = 6.6 Hz, 2H), 1.44 (s, 9H). Compound PLC-39: Diethyl 10-(4-(3-(9-(4-(tert-butyl)phenyl)-1,3-dioxo-1H-xantheno[2,1 ,9- def]isoquinolin-2(3H)-yl)propoxy)-2,6-dimethylphenyl)-5,5-di fluoro-1,3,7,9-tetramethyl-5H-4l4,5l4- dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxyla te Compound PLC-39 was synthesized from Compound PLC-39.2 (0.275 mmol, 147 mg) and ethyl 2,4- dimethyl-1H-pyrrole-3-carboxylate (0.413 mmol, 69 mg) in dry DCE (40 mL), followed by pTsOH.H2O (0.110 mmol, 21 mg), then DDQ (0.468 mmol, 106 mg) 2X Et3N (2.20 mmol, 0.31 mL) and BF3.OEt2 (3.30 mmol, 0.41 mL) in a manner similar to Compound 32. The crude reaction mixture was diluted with hexanes and loaded onto ~20g of silica gel in a loader. Purified by flash chromatography on silica gel (120g, solid load, equilibrate 0% EtOAc/DCM, eluting 0% (2 CV) → 10% EtOAc/DCM (50 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 71 mg (29% yield). MS (APCI): calculated for Chemical Formula: C ₅₈ H ₅₆ BF ₂ N ₃ O ₈ (M+H) = 972; found: 972. ¹ H NMR (400 MHz, TCE) δ 8.65 (d, J = 7.9 Hz, 1H), 8.58 (d, J = 8.4 Hz, 1H), 8.07 (d, J = 2.3 Hz, 1H), 8.03 (d, J = 8.1 Hz, 1H), 7.62 (dd, J = 8.7, 2.2 Hz, 1H), 7.36 (d, J = 8.7 Hz, 1H), 7.33 (d, J = 8.3 Hz, 1H), 6.68 (s, 2H), 4.42 (t, J = 7.0 Hz, 2H), 4.28 (q, J = 7.1 Hz, 4H), 4.16 (t, J = 6.2 Hz, 2H), 2.83 (s, 6H), 2.28 (p, J = 5.8 Hz, 2H), 2.05 (s, 6H), 1.72 (s, 6H), 1.44 (s, 9H), 1.34 (t, J = 7.1 Hz, 6H). Synthesis of Compound PLC-40 Compound PLC-40.1: 9-( 6-(2-amino-4-(tert-butyl)phenoxy)-2-(2-hydroxyethyl)-1H- benzo[de]isoquinoline-1,3(2H)-dione Compound PLC-40.1 was synthesized from Compound PLC-4.2 (8.827 mmol, 3.190 g), ethanolamine (17.65 mmol, 1.066 mL), and DMAP (2.648 mmol, 324 mg), followed by 200 proof ethanol (70 mL) in a manner similar to the methods described above. The crude precipitate was filtered off, dissolved in acetone, and evaporated to dryness in vacuo. Gives a brown-yellow solid, 2.777 g (78% yield). MS (APCI): calculated for Chemical Formula: C ₂₄ H ₂₄ N ₂ O ₄ (M+H) = 405; found: 405. ¹ H NMR (400 MHz, TCE) δ 8.80 (dd, J = 8.4, 1.2 Hz, 1H), 8.67 (dd, J = 7.3, 1.2 Hz, 1H), 8.46 (d, J = 8.3 Hz, 1H), 7.84 (dd, J = 8.4, 7.3 Hz, 1H), 7.02 – 6.92 (m, 3H), 6.87 (dd, J = 8.4, 2.3 Hz, 1H), 4.42 (t, J = 5.2 Hz, 2H), 3.95 (t, J = 5.2 Hz, 2H), 3.74 (s, 2H), 2.39 (s, 1H), 1.35 (s, 9H). Compound PLC-40.2: 9-(tert-butyl)-2-(2-hydroxyethyl)-1H-xantheno[2,1,9-def]isoq uinoline-1,3(2H)- dione Compound PLC-40.2 was synthesized from Compound PLC-40.1 (6.863 mmol, 2.776 g), NaNO ₂ (51.475 mmol, 3.552 g), con HCl (34.317 mmol, 2.83 mL), and CuSO ₄ .5H ₂ O (46.67 mmol, 11.653 g) in a manner similar to the methods described above. The crude product was ~10% acetate ester. It was cleaved with K ₂ CO ₃ in the same manner as Compound 52.2. The crude cleavage mixture was dissolved in acetone and evaporated onto ~20g of silica gel and placed in a loader. Purified by flash chromatography on silica gel (120g, solid load, equilibrate 0% EtOAc/DCM, eluting (2 CV) → 85% EtOAc/DCM (20 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a yellow solid, 732 mg (27% yield). MS (APCI): calculated for Chemical Formula: C24H21NO4 (M+H) = 388; found: 388. Compound PLC-40.3: 2-(2-bromoethyl)-9-(tert-butyl)-1H-xantheno[2,1,9-def]isoqui noline-1,3(2H)- dione Compound PLC-40.3 was synthesized from Compound PLC-40.2 (1.884 mmol, 730 mg), perbromomethane (2.826 mmol, 937 mg), and PPh3 (2.826 mmol, 741 mg) in dry DCM (80 mL) in a manner similar to Compound 50.3. The crude reaction mixture was loaded onto ~30g of silica gel in a loader. Purified by flash chromatography on silica gel (120g, solid load, equilibrate 0% EtOAc/DCM, eluting 0% (2 CV) → 15% EtOAc/DCM (20 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a yellow solid, 556 mg (44% yield). NMR shows it to be only ~50% pure. MS (APCI): calculated for Chemical Formula: C ₂₄ H ₂₀ BrNO ₃ (M+H) = 450; found: 450. ¹ H NMR (400 MHz, TCE) δ 8.62 (d, J = 7.9 Hz, 1H), 8.57 (d, J = 8.4 Hz, 1H), 8.04 (d, J = 2.3 Hz, 1H), 7.98 (d, J = 8.0 Hz, 1H), 7.62 (dd, J = 8.7, 2.2 Hz, 1H), 7.35 (d, J = 8.7 Hz, 1H), 7.31 (d, J = 8.4 Hz, 1H), 4.58 (t, J = 7.6 Hz, 2H), 3.73 – 3.65 (m, 2H), 1.44 (s, 9H). Compound PLC4.4: 4-(2-(9-(tert-butyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquin olin-2(3H)- yl)ethoxy)-2,6-dimethylbenzaldehyde Compound PLC-40.4 was synthesized from Compound PLC-40.3 (0.450 mmol, 203 mg), 4-hydroxy-2,6- dimethylbenzaldehyde (1.350 mmol, 203 mg), and K ₂ CO ₃ (1.260 mmol, 174 mg) in dry DMF (10 mL) in a manner similar to the methods described above. The crude product was filtered off, washed with water, dissolved in DCM, and evaporated to dryness. Dissolved in DCM and evaporated onto ~20g of silica gel and placed in a loader. Purified by flash chromatography on silica gel (120g, solid load, equilibrate 0% EtOAc/DCM, eluting 0% (2 CV) → 15% EtOAc/DCM (20 CV)). Fractions containing product were evaporated to dryness. The reaction was run again in the same way. Both purified products were combined to give 64 mg of a yellow solid (13% yield). MS (APCI): calculated for Chemical Formula: C ₃₃ H ₂₉ NO ₅ (M+H) = 520; found: 520. ¹ H NMR (400 MHz, TCE) δ 10.41 (s, 1H), 8.66 (d, J = 7.9 Hz, 1H), 8.60 (d, J = 8.3 Hz, 1H), 8.06 (d, J = 2.2 Hz, 1H), 8.01 (d, J = 8.0 Hz, 1H), 7.62 (dd, J = 8.7, 2.2 Hz, 1H), 7.36 (d, J = 8.7 Hz, 1H), 7.33 (d, J = 8.4 Hz, 1H), 6.66 (s, 2H), 4.64 (t, J = 6.2 Hz, 2H), 4.37 (t, J = 6.2 Hz, 2H), 2.57 (s, 6H), 1.44 (s, 9H). Compound PLC-40: Diethyl 10-(4-(2-(9-(tert-butyl)-1,3-dioxo-1H-xantheno[2,1,9-def]iso quinolin- 2(3H)-yl)ethoxy)-2,6-dimethylphenyl)-5,5-difluoro-1,3,7,9-te tramethyl-5H-4l4,5l4-dipyrrolo[1,2- c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate Compound PLC-40 was synthesized from Compound PLC-40.4 (0.121 mmol, 63 mg), ethyl 2,4- dimethyl-1H-pyrrole-3-carboxylate (0.263 mmol, 44 mg), in dry DCE (20 mL), followed by pTsOH.H2O (0.0182 mmol, 4 mg), then DDQ (0.158 mmol, 36 mg) 2X Et3N (0.970 mmol, 0.140 mL) and BF3.OEt2 (1.455 mmol, 0.180 mL) in a manner similar to the methods described above. The crude reaction mixture was loaded onto ~20g of silica gel in a loader. Purified by flash chromatography on silica gel (120g, solid load, equilibrate 0% EtOAc/hexanes, eluting 0% (2 CV) → 75% EtOAc/hexanes (30 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 78 mg (73% yield). MS (APCI): calculated for Chemical Formula: C ₅₁ H ₅₀ BF ₂ N ₃ O ₈ (M+H) = 882; found: 882. ¹ H NMR (400 MHz, TCE) δ 8.68 (d, J = 7.9 Hz, 1H), 8.62 (d, J = 8.3 Hz, 1H), 8.07 (d, J = 2.3 Hz, 1H), 8.03 (d, J = 8.1 Hz, 1H), 7.63 (dd, J = 8.8, 2.2 Hz, 1H), 7.36 (t, J = 8.9 Hz, 2H), 6.78 (s, 2H), 4.66 (t, J = 6.5 Hz, 2H), 4.35 (t, J = 6.4 Hz, 2H), 4.25 (q, J = 7.1 Hz, 4H), 2.81 (s, 6H), 2.05 (s, 6H), 1.67 (s, 6H), 1.44 (s, 9H), 1.32 (t, J = 7.1 Hz, 6H). Example 3 Fabrication of a Color Conversion Film A glass substrate was prepared in substantially the following manner. A 1.1 mm thick glass substrate measuring 1-inch X 1-inch was cut to size. The glass substrate was then washed with detergent and deionized (DI) water, rinsed with fresh DI water, and sonicated for about 1 hour. The glass was then soaked in isopropanol (IPA) and sonicated for about 1 hour. The glass substrate was then soaked in acetone and sonicated for about 1 hour. The glass was then removed from the acetone bath and dried with nitrogen gas at room temperature. A 20 wt% solution of Poly(methylmethacrylate) (PMMA) (average M.W.120,000 by GPC from MilliporeSigma, Burlington, MA, USA) copolymer in cyclopentanone (99.9% pure) was prepared. The prepared copolymer was stirred overnight at 40 °C. [PMMA] CAS: 9011-14-7; [Cyclopentanone] CAS: 120-92-3 The 20% PMMA solution prepared above (4g) was added to 3 mg of the photoluminescent complex made as described, e.g., PLC-1 or PLC-2, above in a sealed container and mixed for about 30 minutes. The PMMA/lumiphore solution was then spin coated onto a prepared glass substrate at 1000 RPM for 20 s and then 500 RPM for 5 s. The resulting wet coating had a thickness of about 10 µm. the samples were covered with aluminum foil before spin coating to protect them from exposure to light. Three samples each were prepared in this manner for each for Emission/FWHM and quantum yield. The spin coated samples were baked in a vacuum oven at 80 °C for 3 hours to evaporate the remaining solvent. The 1-inch X 1-inch sample was inserted into a Shimadzu, UV-3600 UV-VIS- NIR spectrophotometer (Shimadzu Instruments, Inc., Columbia, MD, USA). All device operations were performed inside a nitrogen-filled glove-box. The resulting absorption/emission spectrum for PCL-1 is shown in FIGs.1 and 2, while the resulting absorption/emission spectrum for PCL-2 is shown in FIG. 3. The fluorescence spectrum of a 1-inch X 1-inch film sample prepared as described above was determined using a Fluorolog spectrofluorometer (Horiba Scientific, Edison, NJ, USA) with the excitation wavelength set at the respective maximum absorbance wavelength. The maximum emission and FWHM are shown in Table 1. The quantum yield of a 1-inch X 1-inch sample prepared as described above were determined using a Quantarus-QY spectrophotometer (Hamamatsu Inc., Campbell CA, USA) was excited at the respective maximum absorbance wavelength. The results are reported in Table 1. The results of the film characterization (absorbance peak wavelength, FWHM, and quantum yield) are shown in Table 1 below. Table 1