BORON-CONTAINING CYCLIC EMISSIVE COMPOUNDS AND COLOR CONVERSION FILM CONTAINING THE SAME

Inventors: Shijun Zheng, Jeffrey R. Hammaker, Peng Wang, Tissa Sajoto, Jie Cai, Isamu Kitahara, and Hiep Luu

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application No. 63/152,301, filed February 22, 2021, which is incorporated by reference in its entirety.

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. Third, 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 complexes with good blue light absorbance and narrow emissions bandwidths, with the 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 xanthenoisoquinoline derivative: a linker complex comprising an optionally substituted ester or an optionally substituted ether; and a boron- dipyrromethene (BODIPY) moiety. 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 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. I some embodiments, the xanthenoisoquinoline derivative can be of the following general formula: , wherein R° and R ¹⁰ may independently be a hydrogen (H), a C1-C4 alkyl group, or an optionally substituted aryl group.

In some embodiments, the BODIPY moiety can be of the following general formulae:

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are independently selected from a hydrogen atom (H), a C1-C3 alkyl group, an optionally substituted aryl group, or an ether group. In some embodiments, R ⁷ , R ⁸ , and R ⁹ may be independently selected from a hydrogen atom (H), a methyl group (-CH3), or —Cl.

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 at least one photoluminescent complex, as described herein, dispersed within the resin matrix. In some embodiments, the color conversion film may have a thickness between about 1 pm to about 200 pm. In some embodiments, the color conversion film of the present disclosure can absorb blue light in a wavelength range of about 400 nm to about 480 nm and emit light in a wavelength range of about 510 nm to about 560 nm. Another embodiment includes a color conversion film that can absorb blue light in a wavelength range of about 400 nm to about 480 nm and emit light in a wavelength range of about 575 nm to about 645 nm. 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.

Some embodiments include a method for preparing the color conversion film. In some embodiments, the method comprises: dissolving an aforedescribed photoluminescent complex and a binder resin within a solvent and applying the mixture on one of the transparent substrate's 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 and emission spectra of one embodiment of a photoluminescent complex (PLC-1).

FIG. 2 is a graph depicting the absorption and emission spectra of one embodiment of a photoluminescent complex (PLC-2).

FIG. 3 is a graph depicting the absorption and emission spectra of one embodiment of a photoluminescent complex (PLC-4).

FIG. 4 is a graph depicting the absorption and emission spectra of one embodiment of a photoluminescent complex (PLC-5).

DETAILED DESCRIPTION

The present disclosure is related to photoluminescent compounds and complexes for use in color conversion films, backlight units, and display devices.

In some embodiments, the current disclosure includes 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 may 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 between, or the intensity of, two or more colors, increasing the distinction from one another. The present disclosure describes a photoluminescent complex that can enhance the contrast between, or the intensity of, 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 compound is derived from the unsubstituted parent structure wherein one or more hydrogen atoms on the parent structure are independently replaced by one or more substituent groups. The parent structure may have one, two, three, or more substituent groups. In some embodiments, the substituent group(s) 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 "Ci-Cs alkyl" or similar designations. By way of example only, "Ci-Cs 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, Ci-Cg alkyl includes C1-C2 alkyl, C1-C3 alkyl, C1-C4 alkyl, Ci- C ₅ alkyl, Ci-Ce alkyl, C1-C7 alkyl, and Ci-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 atom. Examples include, but are not limited to, -CH2-O-CH3, -CH2-CH2-O-CH3, -CH2-NH-CH3, -CH2-N(CH3)-CH3, -CH2-CH2-NH-CH3, -CH2-CH ₂ -N(CH ₃ )-CH3, -CH2-S-CH2-CH3, -CH2-CH ₂ -S(O)-CH ₃ . In some embodiments, up to two heteroatoms may be consecutive, such as, by way of example, -CH2-NH-O-CH3, etc.

The term "aromatic" refers to a planar ring having a delocalized n-electron system containing 4n+2 n 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 or naphthylenyl) and heterocyclic aryl (or "heteroaryl" or heteroaromatic") groups (e.g., pyridine). The term includes monocyclic or fused-ring polycyclic (i.e., rings which share adjacent pairs of carbon atoms) groups.

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 byfive, 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 radical, as defined herein, substituted with an aryl, as defined herein. Non-limiting aralkyl groups include benzyl, phenethyl; and the like.

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 "ester" refers to a chemical moiety with the formula -COOR, where R is alkyl, cycloalkyl, aryl, heteroaryl (bonded through a ring carbon) or heterocyclic (bonded through a ring carbon). Any hydroxyl moiety, or carboxyl moiety of the compounds described herein may be esterified. Any suitable method or procedure may be employed to prepare any ester derivative.

The term "BODIPY" as used herein, refers to a chemical moiety with the formula: The BODIPY moiety may be composed of dipyrromethene structure complexed with a disubstituted boron atom, typically a BF2 unit. The IUPAC name for the BODIPY core is 4,4-difluoro-4- bora-3a,4a-diaza-s-indacene.

The term "xanthenoisoquinoline" or "xanthenoisoquinoline derivative" or "XI derivative" as used herein, refers to a chemical moiety with the formula: , e.g., lH-xantheno[2,l,9-def]isoquinoline-l,3(2H)-dione.

The present disclosure relates to photoluminescent complexes that absorb light energy of 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 optimized for the absorbing luminescent moiety to transfer its energy to the acceptor luminescent moiety, wherein the acceptor luminescent moiety then emits energy at a second wavelength that is larger than the absorbed first wavelength.

In some embodiments, a photoluminescent complex comprises: a blue light absorbing xanthenoisoquinoline derivative (XI derivative); a linker complex; and a boron-dipyrromethene (BODIPY) moiety. In some embodiments, the linker complex may 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, and 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 (absorbed) wavelength. It is believed that energy transfer from the excited xanthenoisoquinoline derivative to the BODIPY moiety occurs through a Forster 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) and one at the BODIPY absorption band, and only one emission band located at the BODIPY moiety's emission wavelength (see FIGs. 1, 2, 3 and 4). In some embodiments, the photoluminescent complex can have a high emission quantum yield. In some examples, 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 having 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, or 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 incorporating certain substituents into the BODIPY moiety, the emission wavelength can be tuned to a wavelength between about 610 nm to about 645 nm.

In some embodiments, the blue light absorbing moiety may have a peak absorption maximum wavelength between about 400 nm to about 470 nm. In some embodiments, the peak absorption wavelength may 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 wavelength between about 610 nm to about 645 nm, about 610-615 nm, about 615 nm-620 nm, about 620-625 nm, about 625-630 nm, about 630-635 nm, about 635-640 nm, about 640-645 nm, or any wavelength in a range bounded by any of these values. The photoluminescent complexes of the present disclosure 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 emitting BODIPY moiety. In some embodiments, the xanthenoisoquinoline derivative absorbs light energy of a first excitation wavelength and transfers the 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. In some embodiments, the photoluminescent complex has an emission quantum yield greater than 80%. In some embodiments, the photoluminescent complex is constructed in such a way that the blue light absorbing xanthenoisoquinoline derivative and the BODIPY moiety's spatial distance is optimized through the linker complex. In some examples, the transfer of the blue light absorbing xanthenoisoquinoline derivative's energy to the BODIPY moiety may be tuned to optimize the quantum yield of the photoluminescent complex.

Some embodiments include a blue light absorbing xanthenoisoquinoline derivative (XI derivative), wherein the blue light absorbing xanthenoisoquinoline derivative may be of the following general formula: xantheno[2,l,9-def]isoquinoline-l,3(2H)-dione, wherein R° and R ¹⁰ can be selected from a hydrogen atom (H), a methyl, or an optionally substituted aryl. In some embodiments, the optionally substituted aryl group can be a substituted phenyl or benzyl group.

In some embodiments, the optionally substituted aryl group of R° and/or R ¹⁰ can be substituted with a trifluoromethyl group. In some embodiments, the optionally substituted aryl may be 3,5-bis(trifluromethyl)phenyl: In some embodiments, the optionally substituted aryl of R° and/or R ¹⁰ may be 4-

In some embodiments, the optionally substituted aryl of R° and/or R ¹⁰ may be:

The linker complex covalently links the blue absorbing xanthenoisoquinoline derivative with the BODIPY moiety. In some embodiments, the linker complex may be tuned to optimize the spatial distance between the blue light absorbing xanthenoisoquinoline derivative and the BODIPY moiety. By optimizing the spatial distance between the xanthenoisoquinoline derivative and the BODIPY, the quantum yield may be optimized. In some embodiments, the distance separating the blue light absorbing xanthenoisoquinoline derivative and the BODIPY moiety can be about 8 A or greater.

In some embodiments, the linker complex of the photoluminescent complex covalently links the blue light absorbing xanthenoisoquinoline derivative to the BODIPY moiety. In some embodiments, the linker complex may comprise a single bond between the xanthenoisoquinoline derivative and the BODIPY moiety.

In some embodiments, the linker complex may comprise an optionally substituted ester group. In some examples, the linker may comprise an optionally substituted ether group. In some embodiments, the linker complex may comprise both an optionally substituted ester group and an optionally substituted ether group. In some embodiments, the linker complex may comprise an optionally substituted C2-C7 ester group. When the linker complex comprises a substituted ester group, the linker complex can be selected from among one of the following structures: In some embodiments, the linker complex may comprise an unsubstituted ester group. When the linker complex comprises an unsubstituted ester group, the linker complex is one of the following In some embodiments, the linker complex may comprise an optionally substituted C2-C5 ether group. When the linker complex comprises an optionally substituted ether group, the linker complex may , wherein n is 2, 3, 4, or 5.

In some embodiments, the linker complex may be: , wherein n is 1, 2, or 3.

In some embodiments, the linker complex may be:

, wherein n is 1, 2, or 3.

In some embodiments, the linker complex may be:

In some embodiments, the linker complex may be:

Some embodiments include a BODIPY derivative, having the following general formulae:

In some embodiments, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are independently selected from a hydrogen atom (H), a C1-C3 alkyl group, an optionally substituted aryl group, or an ether group. In some embodiments, R ⁷ , R ⁸ , and R ⁹ can be independently selected from a hydrogen atom (H), a methyl group (-CH3), or — Cl.

The BODIPY moiety of the present disclosure may be a BODIPY moiety wherein R ³ and R ⁴ can each be an aryl group, e.g., a phenyl group. In some embodiments, R ¹ , R ² , R ⁵ and /or R ⁶ may independently be a hydrogen atom (H), a substituted aryl group, e.g., a phenyl group diphenyl group (e.g., and / or a diphenyl group bearing a C2-C10 alkyl ether group (

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:

combination thereof.

Some embodiments include a color conversion film comprising: a color conversion layer comprising a resin matrix and one or more of the photoluminescent complexes described herein dispersed within the resin matrix.

Some embodiments include the color conversion film which may be about 1 pm to about 200 pm thick. In some embodiments, the color conversion film may be about 1-5 pm, about 5-10 pm, about 10-15 pm, about 1- 20 pm, about 20-40 pm, about 40-80 pm, about 80-120 pm, about 120-160 pm about 160-200 pm, or any thickness in a range bounded by any of these ranges.

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 610 nm to about 645 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 surface 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 suitable transparent substrate. Some non-limiting examples of transparent substrates include PE (polyethylene), PP (polypropylene), PEN (polyethylene naphthalate), PC (polycarbonate), PMA (polymethylacrylate), 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-3- hydroxyvalerate)), PBE (polybutylene terephthalate), PTT (polytrimethylene terephthalate). Any of the aforedescribed resins, 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 substrate without the 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. Any suitable substrate material and thickness may be employed 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 may be used with the photoluminescent complex(es) 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 an acrylic resin.

In some embodiments, the solvent which may be used for dissolving or dispersing the photoluminescent 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 tetra hydrofuran; 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 may describe a display device, the device may include the backlight unit described herein.

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. 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 are described herein, including the best mode known to the inventors for carrying out the present disclosure. Of course, variations on these described 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

1. A photoluminescent complex comprising: a blue light absorbing xanthenoisoquinoline derivative; a linker complex, wherein the linker complex is an unsubstituted ester or substituted ester; and a boron-dipyrromethene (BODIPY) moiety; wherein the linker complex covalently links the xanthenoisoquinoline derivative and the BODIPY moiety, wherein 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%.

2. The photoluminescent complex of embodiment 1, wherein the xanthenoisoquinoline derivative is of the general formula:

, wherein R° is a bond, an H, a C1-C3 methyl group, or an optionally

4. The photoluminescent complex of embodiment 1 wherein the BODIPY moiety is of the general formula: wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are independently selected from a bond, an H, C1-C3 alkyl, aryl and/ or an ether; and wherein R ⁷ , R ⁸ , and R ⁹ can be independently selected from a bond, H, or a methyl group (-CH3).

5. The photoluminescent complex of embodiment 4, wherein R3 and R4 can each be an aryl group, e.g., a phenyl group;

6. The photoluminescent complex of embodiment 5, wherein the aryl group can be a phenyl group.

7. The photoluminescent complex of embodiment 4, wherein the substituted aryl group can be a phenyl group ( ), or a diphenyl group (

8. The photoluminescent complex of embodiment 4, wherein the ether group can be a C2-C10 alkyl ether group (

9. The photoluminescent complex of embodiment 1, wherein the linker can be selected from

10. The photoluminescent complex of embodiment 1, wherein the unsubstituted ester linker is 11. The photoluminescent complex of embodiment 1, 2, 3, 4, 5, 6, 7 , 8, 9, 10 and 11, wherein the substituted ester of the linker complex is one of the following structures:

12. The photoluminescent complex of embodiment 1, wherein the photoluminescent complex is one of the following structures:

Chemical Formula: C ₁₁₀ H75BF 2N4O10 Exact Mass: 1660.55 Molecular Weight: 1661.63

PLC-1

Chemical Formula: C ₁₃ 2H ₁₁₅ BF2N4O ₁₆ Exact Mass: 2060.84 Molecular Weight: 2062.19

PLC-3

Chemical Formula: C-|42H ₈ 3BF26N ₄ 0-IO Exact Mass: 2508.58 Molecular Weight: 2510.01

PLC-5 or a combination thereof.

13. A color conversion film comprising: a transparent substrate layer; a color conversion layer, wherein the color conversion layer includes a resin matrix; and at least one photoluminescent complex, wherein the at least one photoluminescent compound is comprised the photoluminescent compound of embodiment 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12, dispersed within the resin matrix.

14. The color conversion film of embodiment 13, further comprising a singlet oxygen quencher.

15. The color conversion film of embodiment 13, further comprising a radical scavenger.

16. The color conversion film of embodiment 13, wherein the film has a thickness of between 10 pm and 200 pm.

17. The color conversion film of embodiment 13, wherein the film absorbs light in about 400 nm to about 480 nm wavelength range and emits light in the 575 nm to about 645 nm wavelength range.

18. A method for preparing the color conversion film, the method comprising: dissolving the photoluminescent complex of embodiment 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and a binder resin within a solvent; and applying the mixture to one of the transparent substrates opposing surfaces.

19. A backlight unit including the color conversion film of embodiment 13.

20. A display device including the back-light unit of embodiment 19.

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-dimethylbenzaldehyde (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. (2,3- Dichloro-5,6-dicyano-l,4-benzoquinone ) (2.0 g) was added and the mixture was stirred overnight. The next day the solution was filtered and then washed with dichloromethane resulting in a dipyrrolemethane (1.9 g). 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 C21H24BF2N2O (M+H) = 369; found: 369. 1H NMR (400 MHz, Chloroform-d) 8 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 synthesized as described in Wakamiya,

Atsushi et al. Chemistry Letters, 37(10), 1094-1095; 2008

Example 2: Synthesis of Photoluminescent Complexes:

Synthesis of Compound PLC-1:

Compound l-(4-bromophenyl)-4-nitro-3-phenylbutan-l-one (PLC-1.1): To a solution of LDA (lithium diisopropylamide) (2.00 M, 176 mL, 1.50 eq) in THF (tetrahydrofuran) (300 mL) at -78 °C was added compound l-(4-bromophenyl)ethan-l-one (70.1 g, 352 mmol, 1.50 eq) and stirred for 30 min at -78 °C. Compound (E)-(2-nitrovinyl)benzene (35.0 g, 235 mmol, 1.00 eq) was added to the mixture at -78 °C and stirred for 1 hr. Thin layer chromatography (TLC) (Petroleum ether : Ethyl acetate = 5 : 1) showed compound (E)-(2-nitrovinyl)benzene was consumed and new spot was formed. The reaction mixture was quenched by addition NH ₄ CI aq. 200 mL at -70 °C and extracted with ethyl acetate (EtOAc) 600 mL (200 mL * 3), dried over Na2SO ₄ , filtered, and concentrated under reduced pressure to give a residue. The residue was purified by column chromatography (SiC>2, Petroleum ether/Ethyl acetate = 1/0 to 5/1). Compound l-(4-bromophenyl)- 4-nitro-3-phenylbutan-l-one (PLC-1.1) (40.0 g, 115 mmol, 48.9% yield) was obtained as a white solid, which was confirmed by ¹ HNMR. ¹ HNMR: (400MHz, MeOD): 8 7.95 - 7.78 (m, 2H), 7.70 - 7.63 (m, 2H), 7.38 - 7.28 (m, 4H), 7.28 - 7.19 (m, 1H), 4.97 - 4.88 (m, 1H), 4.83 - 4.74 (m, 1H), 4.22 - 4.10 (m, 1H), 3.51 (dq, J = 7.0, 17.5 Hz, 2H).

Compound 2-(4-bromophenyl)-4-phenyl-lH-pyrrole (PLC-1.2): To a mixture of compound l-(4-bromophenyl)-4-nitro-3-phenylbutan-l-one (PLC-1.1) (40.0 g, 115 mmol, 1.00 eq), Sulfur (11.1 g, 345 mmol, 3.00 eq), NH ₄ OAc (53.1 g, 689 mmol, 6.00 eq) and morpholine (30.0 g, 345 mmol, 30.3 mL, 3.00 eq) was stirred at 80 °C for 1 hr. TLC (Petroleum ether/Ethyl acetate = 5/1) showed compound l-(4-bromophenyl)-4-nitro-3-phenylbutan-l-one (PLC-1.1) was consumed and new spot was formed. The reaction mixture was quenched by addition H2O (200 mL) at 15 °C, and extracted with EtOAc 600 mL (200 mL x 3). The combined organic layers were concentrated under reduced pressure to give a residue. The residue was purified by column chromatography (SiC>2, Petroleum ether/Ethyl acetate = 1/0-5/1) and was further purified by washing with MTBE (Methyl tert-butyl ether) (100 mL). Compound 2-(4-bromophenyl)-4-phenyl-lH-pyrrole (PLC-1.2) (10.6 g, 35.2 mmol, 30.6% yield, 99% purity) was obtained as a blue solid, which was confirmed by ¹ HNMR. ¹ HNMR: (400MHz, DMSO-d6): 8 11.5 (br d, J = 0.9 Hz, 1H), 7.64 - 7.56 (m, 4H), 7.56 - 7.51 (m, 2H), 7.35 (dd, J = 1.8, 2.6 Hz, 1H), 7.30 (t, J = 7.8 Hz, 2H), 7.15 - 7.07 (m, 1H), 6.99 (t, J = 2.0 Hz, 1H).

Compound PLC-1.3: Step-1: A mixture of 2-(4-bromophenyl)-4-phenyl-lH-pyrrole (PLC-1.2) (1.0 g, 3.36 mmol), 2,4,6-trimethylbenzaldehyde (0.249 g, 1.68 mmol) and tosylic acid (50 mg) in 1,2- dichloroethane (80 mL) was heated at 50 ⁹ C for 24 hrs. LCMS analysis shows that the main peak is desired product with m/e+ = 111.

Step-2: To the mixture from step-1, DDQ. (2,3-Dichloro-5,6-dicyano-l,4-benzoquinone) (454 mg, 2 mmol) was added, and stirred for one hour at room temperature. LCMS analysis shows that the reaction completed with one main peak of m/e- = 724. Step-3: To the mixture from step-2, triethylamine (0.85 mL, 6 mmol), boron trifluoride diethyl etherate (BF3*OEt2) (1.1 mL, 9 mmol) were added at 0 ⁵ C. The whole was heated at 50 ⁵ C for one hour. Another potion of triethylamine (0.5 mL) and BF3*OEt2 (0.5 mL) were added, and the mixture was heated at 50 ⁹ C for additional one hour. LCMS shows that the reaction completed with main peak of m/e' = 772. The mixture was diluted with 50 mL dichloro-methane (DCM), then washed with water twice, brine once, then concentrated to 100 mL and loaded onto silica gel, purified by flash chromatography using eluents of hexanes/DCM (40% 100% DCM). The main desired peak was collected, after removal of solvent under reduced pressure, desired product was obtained as a purple solid (1.06 g, in 81.6% yield). Confirmed by LCMS (APCI): calcd for C ₄ 2H3iBBr2F2N2 (M-): 770.1; Found: 770. ^J H NMR (400 MHz, Chloroform-d) 8 7.81 - 7.73 (m, 4H), 7.61 - 7.53 (m, 4H), 6.99 - 6.90 (m, 2H), 6.85 (dd, J = 8.3, 6.9 Hz, 4H), 6.78 - 6.71 (m, 4H), 6.42 (s, 2H), 6.00 (s, 2H), 1.98 (s, 6H), 1.85 (s, 3H).

Compound PLC-1.4: A mixture of compound PLC-1.3 (160 mg, 0.207 mmol), 4-(4, 4,5,5- tetramethyl-l,3,2-dioxaborolan-2-yl)phenol (120 mg, 0.54 mmol), tetrakis(triphenylphosphine)palladium(0) (Pd(PPh3) ₄ ) (25 mg, 0.022 mol), potassium carbonate (140 mg, 1.01 mmol) in 1,4-dioxane/water (8 mL/1 mL) was degassed then heated at 120 ⁹ C for 90 min in a microwave reactor. The resulted mixture was diluted with 20 mL DCM, loaded on silica gel, and purified by flash chromatography using eluents of DCM/Ethyl acetate (0% 20% ethyl acetate). The desired main peak was collected, after removal of solvent under reduced pressure, the desired product was obtained as a dark solid (130 mg, in 79% yield). ¹ H NMR (400 MHz, TCE-d2) 6 7.98 - 7.91 (m, 4H), 7.62 - 7.54 (m, 4H), 7.54 - 7.46 (m, 4H), 6.92 - 6.85 (m, 4H), 6.84 (d, J = 2.1 Hz, 2H), 6.82 - 6.74 (m, 4H), 6.73 - 6.66 (m, 4H), 6.46 (s, 2H), 5.92 (s, 2H), 4.88 (s, 2H), 1.92 (s, 6H), 1.78 (s, 3H).

Compound PLC-1.5: A mixture of 2-nitrophenol (6.6 g, 48 mmol), KOH powder (2.4 g, 43 mmol) was mixed and stirred under vacuum for 30 min, then copper powder (0.4 g) was added, followed by 100 mL anhydrous dimethyl formamide (DMF). The mixture was stirred for 5 min, then 4- chloronaphthalic anhydride (5.1 g, 22 mmol) was added. The whole was degassed then heated at reflux for 1.5 hr. After cooled to room temperature, 100 mL 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 (4.6 g). 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): calcd for CI ₈ HION0 ₆ (M+H): 336.0; Found: 336. ^J H NMR (400 MHz, Chloroform-d) 8 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-1.6: A mixture of 4-(2-nitrophenoxyl)-l,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 (220 mL). The resulted precipitate was collected by filtration and washed with water and dried thoroughly in air then under vacuum to afford a yellow solid (1.65 g, in 90% yield). Confirmed by LCMS (APCI): calcd for C18H12NO4 (M+H): 306.1; Found: 306. Compound PLC-1.7: 4-(2-aminophnoxy)-l,8-naphthalic anhydride (PLC-1.6)(1.5 g, 4.9 mmol), was dispersed in acetic acid (35 mL) and cooled to 0 ⁵ C. While being stirred, precooled hydrochloric acid (3 mL, 37 mmol) was added, then sodium nitrite solution (3.29 g, 46 mmol) in 12 mL water was added dropwise at 0 °C. The whole was stirred for one hour at 0 -C, then was transferred into additional funnel, and dropped into a refluxed copper sulfate solution (5.08 g, 20 mmol, in 50 mL water) over one-hour period. After cooled to room temperature, the precipitate was collected by filtration, washed with water, ethyl acetate, then dried in air then in vacuum to give a yellow solid (0.92 g, in 65% yield). Confirmed by LCMS (APCI): Calcd for C18H8O4 (M-) : 288.0; Found: 288. ¹ H NMR (400 MHz, Chloroform-d) 8 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-1.8: A mixture of lH,3H-isochromeno[6, 5, 4-mna]xanthene-l, 3-dione (PLC- 1.7) (100 mg, 0.347 mmol), 4-(4-aminophenyl)butanoic acid (125 mg, 0.7 mmol) in 5 mL DMF was heated at 165 ⁹ C 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 ( P LC-1.8)( 120 mg, in 77% yield). Confirmed by LCMS (APCI): calcd for C28H19NO5 ( M-): 449.1; Found: 449. ¹ H NMR (400 MHz, DMSO-d6) 8 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-1: A mixture of compound PLC-1.4 (80 mg, 0.1 mmol), compound PLC-1.8 (100 mg, 0.222 mmol), 4-Dimethylaminopyridinium/p-toluenesulfonate (DMAP/TsOH salt) (59 mg, 0.2 mmol), N,N'-diisopropylcarbodiimide (DIC) (0.15 mL) in 6 mL DCM was stirred at room temperature overnight, then at 45 ⁹ C for 2 hrs. The resulted mixture was loaded on silica gel and purified by flash chromatography using eluents of dichloromethane (DCM)/ethyl acetate (0% 10% ethyl acetate). The desired di-coupled product was collected as the 2nd main peak. After removal of solvents, washed with methanol and dried in air, the desired product was obtained as a dark solid (25 mg, in 15% yield). Confirmed by HNMR. ^J H NMR (400 MHz, TCE-d2) 8 8.49 (dd, J = 16.0, 8.1 Hz, 4H), 7.99 (d, J = 8.2 Hz, 6H), 7.85 (d, J = 8.0 Hz, 2H), 7.63 (dd, J = 8.5, 3.7 Hz, 8H), 7.50 (t, J = 7.8 Hz, 2H), 7.42 - 7.25 (m, 8H), 7.25 - 7.08 (m, 10H), 6.84 (dt, J = 36.5, 7.3 Hz, 6H), 6.70 (d, J = 7.5 Hz, 4H), 6.48 (s, 2H), 5.93 (s, 2H), 2.80 (t, J = 1 Hz, 4H), 2.63 (t, J = 7.4 Hz, 4H), 2.11 (t, J = 7.7 Hz, 4H), 1.92 (s, 6H), 1.78 (s, 3H).

Synthesis of Compound PLC-2:

Compound PLC-2.1: (4',4"'-(5,5-difluoro-10-mesityl-l,9-diphenyl-5H-4l4,5l4-dip yrrolo[l,2- c:2',l'-f] [l,3,2]d iaza borinine-3,7-diyl)bis( [1, l'-biphenyl]-3-ol)) : A 30 mL wide-neck microwave vial (Anton-Parr) was charged with a stir bar, Compound PLC-1.3 (0.300 mmol, 232 mg), 3-(4, 4,5,5- tetramethyl-l,3,2-dioxaborolan-2-yl)phenol (0.800 mmol, 177 mg), K2CO3 (1.60 mmol, 221 mg), and Pd(PPha)4 (0.030 mmol, 34.7 mg). To the vial was added dioxane (8 mL) and water (1 mL). The vial was sealed with a septum and sparged with argon with stirring at room temperature for 5 minutes. The septum was changed for a snap cap and septum and the sample was irradiated in the microwave synthesizer for 90 minutes at a target temperature of 120 °C. The crude reaction mixture was evaporated to dryness and dissolved in a small volume of DCM and loaded onto ~60 mL of silica in a solid loader. Purified by flash chromatography on silica gel (120 g, solid load, equilibrate 100% hexanes, eluting with 100% hexanes (2 CV), 60% EtOAc/hexanes (30 CV) ) . Fractions with product were evaporated to dryness in vacuo to give a dark red solid, 173 mg (in 72% yield). ¹ H NMR (400 MHz, Tetrachloroethane-d2) 8 8.05 (d, J = 8.5 Hz, 4H), 7.70 (d, J = 8.5 Hz, 4H), 7.35 (t, J = 7.8 Hz, 2H), 7.27 (dt, J = 7.9, 1.2 Hz, 2H), 7.15 (dd, J = 2.5, 1.6 Hz, 2H), 7.00 - 6.93 (m, 2H), 6.91 - 6.83 (m, 6H), 6.82 - 6.76 (m, 4H), 6.56 (s, 2H), 6.02 (s, 2H), 4.94 (s, 2H), 2.00 (s, 6H), 1.87 (s, 3H). MS (APCI): calculated for Chemical Formula: C54H41BF2N2O2 (M-) = 798; found: 798. Compound PLC-2: ((5,5-difluoro-10-mesityl-l,9-diphenyl-5H-4l4,5l4-dipyrrolo[ l,2-c:2',l'- f][l,3,2]diazaborinine-3,7-diyl)bis([l,l'-biphenyl]-4',3-diy l) bis(4-(4-(l,3-dioxo-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)butanoate)): A 40 mL screw-cap vial was charged with a stir bar, Compound PLC-2.1 (0.015 mmol, 12.0 mg), 4-(4-(l,3-dioxo-lH-xantheno[2,l,9-def]isoquinolin-2(3H)- yl)phenyl)butanoic acid (PLC-1.8) (0.0375 mmol, 16.8 mg), and DMAP.pTsOH salt (0.0075 mmol, 2.2 mg). The vial was sealed with a screw cap under air and placed in a pre-heated aluminum heat block set at 70 ° C. The reaction mixture was stirred at 70 ° C for a few minutes, then N,N'- diisopropylcarbodiimide (DIC) (0.060 mmol, 0.0094 mL) was added. The vial was sealed with a screwcap and stirred at 70 ° C for 28 h, then at room temperature for the rest of the weekend. TLC shows the reaction is not done. The vial was reheated to 70 ° C and more 4-(4-(l,3-dioxo-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)butanoic acid (PLC-1.8) (0.0221 mmol, 9.9 mg) and N,N'- diisopropylcarbodiimide (DIC) (0.060 mmol, 0.0094 mL) were added, followed by 4 mL anhydrous THF (to improve solubility of all reaction components). The reaction mixture was stirred at 70 ° C for 90 minutes, at which point TLC showed completion of the reaction. The solvents were evaporated to dryness in vacuo, dissolved in a small amount of toluene, and loaded onto ~10 g of silica gel in a solid loader. Purified by flash chromatography on silica gel (80 g, solid load, equilibrate 100% toluene, elute with 100% toluene (2 CV), then 20% EtOAc/toluene (30 CV)). Removal of solvents gives a red solid, 22.0 mg (in 88% yield). NMR (400 MHz, Chloroform-d) 8 8.59 (dd, J = 13.1, 8.1 Hz, 4H), 8.08 - 7.99 (m, 6H), 7.89 (d, J = 8.0 Hz, 2H), 7.68 (d, J = 8.5 Hz, 4H), 7.57 - 7.49 (m, 4H), 7.49 - 7.31 (m, 12H), 7.30 - 7.22 (m, 6H), 7.09 (ddd, J = 8.0, 2.4, 1.1 Hz, 2H), 6.98 - 6.91 (m, 2H), 6.86 (t, J = 7.6 Hz, 4H), 6.81 - 6.75 (m, 4H), 6.51 (s, 2H), 6.01 (s, 2H), 2.85 (t, J = 7.6 Hz, 4H), 2.68 (t, J = 7.4 Hz, 4H), 2.17 (p, J = 7.6 Hz, 4H), 2.02 (s, 6H), 1.86 (s, 3H).

Compound PLC-3:

Compound PLC-3.1 (Ethyl 2-(4'-(octyloxy)-[l,l'-biphenyl]-4-yl)-4-phenyl-lH-pyrrole-3 - carboxylate): All ground-glass joints were taped with Teflon tape. A 250 mL 2N RBF was placed in an aluminum heat block and pre-heated to 90 ° C. The flask was fitted with an air condenser with a septum on top, a glass stopper in the second neck and charged with a stir bar. The flask was flushed with argon via needle through the top of the air condenser and then charged with zinc ((granules, 10- 20 mesh), 80.0 mmol, 5.231 g). To the flask was added anhydrous THF (20 mL), followed by methanesulfonic acid (0.500 mmol, 0.0325 mL). The reaction mixture was stirred at 90 ° C for 5 minutes, then 4'-(octyloxy)-[l,l'-biphenyl]-4-carbonitrile (15.0 mmol, 4.611 g) was added. A syringe pump was setup and benzyl 2-bromoacetate (22.5 mmol, 3.56 mL) was added dropwise over 1 hour with stirring at 90 ° C. The reaction mixture was heated for 20 hours at 90 °C. An additional portion of anhydrous THF (10 mL) was added (to replace solvent lost via evaporation) the reaction temperature was lowered to 85 ° C. Added beta-nitrostyrene (10.0 mmol, 1.491 g), immediately followed by iron trichloride (FeCL) (6.00 mmol, 973 mg) and the reaction mixture was heated at one hour at 85 ° C under argon. The reaction mixture was complete as confirmed by TLC. The reaction was removed from heat and diluted with ethyl acetate (200 mL) and water (100 mL), then acidified with 6N HCI/water solution (20 mL) and brine (50 mL) was added to break an emulsion. The layers were separated. An attempt to wash the organic layer with water (100 mL) resulted in another emulsion. The emulsion was broken by the addition of 6N HCI and brine as before. The organic layer was dried over MgSO ₄ , filtered, and evaporated to dryness in vacuo. The crude product was evaporated onto 10:1 Celite:flash SiC>2 and purified by flash chromatography on silica gel (330 g, solid load, equilibrate 10% DCM/hexanes, elute with 10% DCM/hexanes (2 CV), 100% DCM (20 CV)) . Fractions containing product were evaporated to dryness in vacuo to give 1.409 g of an off-white solid, in 25% yield. ¹ H NMR (400 MHz, Tetrachloroethane-d2) 8 8.52 (d, J = 2.5 Hz, 1H), 7.57 (d, J = 7.4 Hz, 6H), 7.48 - 7.43 (m, 2H), 7.39 - 7.28 (m, 3H), 7.26 - 7.17 (m, 3H), 7.02 (d, J = 8.8 Hz, 2H), 6.95 - 6.90 (m, 2H), 6.87 (d, J = 2.6 Hz, 1H), 5.10 (s, 2H), 4.02 (t, J = 6.6 Hz, 2H), 1.82 (p, J = 6.8 Hz, 2H), 1.54 - 1.43 (m, 2H), 1.43 - 1.25 (m, 8H), 0.95 - 0.88 (m, 3H). MS (APCI): calculated for Chemical Formula: C33H37NO3 (M+H) = 496; found: 496.

Compound PLC-3.2: (2-Hydroxyethyl 2-(4'-(octyloxy)-[l,l'-biphenyl]-4-yl)-4-phenyl-lH- pyrrole-3-carboxylate): A 100 mL 2 neck round bottom flask was placed in an aluminum heat block and fitted with a finned condenser and charged with a stir bar. The heat block was pre-heated to 120 °C. To the flask was added Compound PLC-3.1 (0.479 mmol, 267 mg) and sodium hydride (Na H) (9.575 mmol, 230 mg, 60% in mineral oil, 383 mg). The second neck was fitted with a septum and a needle to vent pressure. To the flask was carefully added anhydrous ethylene glycol with stirring at 120 ⁰ C, allowing hydrogen gas to escape. When all of the hydrogen gas had vented, the septum was removed and replaced with a glass stopper. The reaction temperature was increased to 150 ⁰ C and the reaction mixture stirred for one hour at this temperature. The reaction was progressing slowly (monitored by LCMS), so the rate of stirring was increased to overcome the insolubility of the starting material in ethylene glycol. The reaction was heated at 150 ⁰ C with very vigorous stirring for 3 hours, then at room temperature overnight. The reaction was complete in the morning. The reaction mixture was diluted with water (100 mL) and acidified with 6N HCI/water solution (10 mL). After stirring for one hour at room temperature, the precipitate was filtered off, washing with water. The crude precipitate was dissolved in ethyl acetate and DCM and evaporated to dryness. The crude product was evaporated in vacuo onto flash silica gel and purified by flash chromatography on silica gel (120g, equilibrate with 100% hexanes, solid load, elute with 100% hexanes (2 CV), 5% EtOAc/hexanes (0 CV) to 100% EtOAc (30 CV)). Fractions containing product were collected and evaporated to dryness in vacuo to give 127 mg of an off-white solid, in 51% yield. ¹ H NMR (400 MHz, Tetrachloroethane-d2) 6 8.54 (d, J = 2.4 Hz, 1H), 7.66 (s, 4H), 7.59 (d, J = 8.7 Hz, 2H), 7.50 - 7.45 (m, 2H), 7.44 - 7.39 (m, 2H), 7.38 - 7.32 (m, 1H), 7.01 (d, J = 8.8 Hz, 2H), 6.87 (d, J = 2.5 Hz, 1H), 4.12 - 4.06 (m, 2H), 4.01 (t, J = 6.6 Hz, 2H), 3.55 - 3.47 (m, 2H), 1.81 (p, J = 6.7 Hz, 2H), 1.53 - 1.42 (m, 2H), 1.42 - 1.27 (m, 8H), 0.97 - 0.86 (m, 3H). MS (APCI): calculated for Chemical Formula: C33H37NO4 (M+H) = 512; found: 512.

Compound PLC-3.3: (bis(2-hydroxyethyl) 5,5-difluoro-10-mesityl-3,7-bis(4'-(octyloxy)-[l,l'- biphenyl]-4-yl)-l,9-diphenyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l '-f][l,3,2]diazaborinine-2,8-dicarboxylate) (PLC-3.3) : To a 40 mL screw-capped vial was added a stir bar, Compound PLC-3.2 (0.244 mmol, 125 mg), and mesitaldehyde (0.1283 mmol, 0.00189 mL). The headspace was purged with argon and then the vial was sealed with a screw-cap septum and placed in a pre-heated aluminum heat block at 75 °C. To the vial was added anhydrous DCE (5 mL) and the solution was sparged with nitrogen at 75 ⁰ C with stirring for 10 minutes, then pTsOH (0.0.0366 mmol, 7.0 mg) was added along with anhydrous DCE (3 mL). Sparging with nitrogen was continued at 75 °C for another 10 minutes. The gas was switched to static argon and the reaction mixture was stirred under argon at 75 °C overnight. The next morning, additional mesitaldehyde (0.0339 mmol, 5.03 mg) was added and the reaction mixture stirred at 75 °C under argon for an additional 30 minutes, at which point TLC shows no starting material. The reaction was removed from heating and DDQ. (2,3-dichloro-5,6-dicyano-l,4- benzoquinone ) (0.1586 mmol, 36 mg) was added and the reaction mixture was stirred at room temperature for 1 minute, then returned to the heat block and stirred at 75 ° C for 30 minutes to complete the oxidation. The reaction mixture was cooled to 0 °C and boron trifluoride diethyl etherate (BF3*OEt2) (1.098 mmol, 0.136 mL) and triethylamine (0.732 mmol, 0.102 mL) were added in rapid succession with stirring. The reaction mixture was stirred at 0 °C for 1 minute, then the addition of BF3*OEt2 (1.098 mmol, 0.136 mL) and triethylamine (0.732 mmol, 0.102 mL) was repeated. After stirring for an additional minute at 0 °C, the reaction was returned to the heat block and stirred at 75 °C for 2 hours. Added more and BF3*OEt2 (1.464 mmol, 0.181 mL) and triethylamine (0.732 mmol, 0.102 mL) at 75 °C and continued stirring 45 minutes, at which point all of the dipyrromethene had been consumed by TLC. To an Erlenmeyer flask was added flash silica gel (40 mL) and the reaction mixture was diluted into this flask with DCM (~100 mL). The reaction was quenched by adding methanol (25 mL). The reaction mixture was evaporated to dryness in vacuo onto silica gel. The crude reaction was purified by flash chromatography on silica gel (80 g, solid load, equilibrate with 100% hexanes, elute with 100% hexanes (2 CV), 26% EtOAc/hexanes (19.7 CV), 100% EtOAc (15 CV)). Fractions containing product were evaporated to dryness in vacuo to give 35 mg of a reddish blue solid, in 24% yield. MS (APCI): calculated for Chemical Formula: C76H81BF2N2O8 (M-) = 1199; found: 1199.

Compound PLC-3 (bis(2-((4-(4-(l,3-dioxo-3,6-dihydroanthra[2,l,9-def]isoquin olin-2(lH)- yl)phenyl)butanoyl)oxy)ethyl) 5,5-difluoro-10-mesityl-3,7-bis(4'-(octyloxy)-[l,l'-biphenyl ]-4-yl)- l,9-diphenyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diaza borinine-2,8-dicarboxylate): A 40 mL screw-cap vial was placed in an aluminum heat block and charged with a stir bar. To the vial was added PLC-3.3 (0.0146 mmol, 17.5 mg) and 4-(4-(l,3-dioxo-lH-xantheno[2,l,9-def]isoquinolin-2(3H)- yl)phenyl)butanoic acid (0.0438 mmol, 19.6 mg) (PLC-1.8), and DMAP. pTsOH salt (0.0073 mmol, 2.1 mg). To the vial was added anhydrous DCM (4 mL). The vial was sealed with a PTFE-lined screw cap and sonicated for about 30 seconds. With stirring at room temperature, N,N'-diisopropylcarbodiimide (DIC) (0.073 mmol, 0.0114 mL) was added. The sealed vial was stirred under air for 5 minutes at room temperature, then heat block was set to 45 °C and the reaction mixture stirred at this temperature overnight. In the morning, the DCM was evaporated under a stream of nitrogen and the solvent replaced by anhydrous dichloroethane (DCE) (4 mL). The heat block temperature was raised to 70 °C and the reaction mixture stirred for one hour at this temperature to complete the reaction. The crude reaction mixture was loaded onto a cartridge packed with 60 mL of flash silica gel and purified by flash chromatography on silica gel (80 g, equilibrate with 100% hexanes, eluting with 100% hexanes (2 CV), 70% EtOAc/hexanes (40 CV)). Fractions containing the product were evaporated to dryness in vacuo to give 15.3 mg of a dark-colored solid (in 57.3% yield). ¹ H NMR (400 MHz, Chloroform-d) 6 8.61 (dd, J = 16.2, 8.1 Hz, 4H), 8.07 (dd, J = 8.1, 1.5 Hz, 2H), 7.94 (d, J = 8.0 Hz, 2H), 7.68 (d, J = 8.1 Hz, 4H), 7.60 - 7.50 (m, 10H), 7.40 - 7.33 (m, 4H), 7.29 (d, J = 8.3 Hz, 6H), 7.21 (d, J = 8.3 Hz, 4H), 6.97 - 6.88 (m, 6H), 6.86 - 6.76 (m, 8H), 5.95 (s, 2H), 3.96 (t, J = 6.6 Hz, 4H), 3.94 - 3.88 (m, 4H), 3.64 - 3.58 (m, 4H), 2.63 (t, J = 7.6 Hz, 4H), 2.20 (t, J = 7.4 Hz, 4H), 2.00 (s, 6H), 1.88 (p, J = 7.6 Hz, 4H), 1.82 (s, 3H), 1.80 - 1.73 (m, 4H), 1.45 (p, J = 6.7 Hz, 4H), 1.38 - 1.19 (m, 16H), 0.92 - 0.84 (m, 6H).

Synthesis of Compound PLC-4:

Compound PLC-4.1: To a mixture of PLC-1.7 (290 mg, 1.0 mmol) in ortho-dichlorobenzene (30 mL), was added bromine (1.98 g, 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 290 mg 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 110 mg yellow solid. Total product of 400 mg was obtained in 89.7% yield. LCMS (APCI-): calcd for CisHeB^CU (M-): 443.9; found 444. ^J H NMR (400 MHz, d2-TCE)

6 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-4.2: A mixture of PLC-4.1 (190 mg, 0.426 mmol), 4-(4-aminophenyl)butanoic acid (180 mg, 0.64 mmol), 4-(N,N-dimethylamino)-pyridine (4 mg) in anhydrous N,N- dimethylformamide (DMF) (4 mL) 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 1 hr to give a yellow solid (220 mg, in 84.5% yield). LCMS (APCI-): calcd for C2 ₈ Hi ₇ Br2NO ₅ (M-): 604.95; found: 605. ^J H NMR (400 MHz, DMSO-d ₆ ) 6 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-4.3: A mixture of compound PLC-4.2 (100 mg, 0.165 mmol), (3,5- bis(trifluoromethyl)phenyl)boronic acid (170 mg, 0.66 mmol), [l,l'-bis (diphenylphosphino)ferrocene]palladium (II) dichloride (PdfdppfJCh) (20 mg, 0.027 mmol) and potassium carbonate (138 mg, 1 mmol) in THF/water (5 mL/0.5 mL) was degassed then heated at 80 °C for 2 hrs. After cooled to room temperature, the precipitate was collected by filtration, washed with acetone, then dried in vacuum oven at 90 °C for 2 hr. A yellow solid was obtained (142 mg, in 94% yield). LCMS (APCI-): calcd for C44H23F12NO5 (M-): 873.14; found: 873. ^J H NMR (400 MHz, d2-TCE) 8 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-4: A mixture of compound PLC-1.4 (20 mg, 0.025 mmol), PLC-4.3 (55 mg, 0.0626 mmol), 4-dimethylaminopyridinium/p-toluenesulfonate (DMAP/TsOH salt) (30 mg, 0.1 mmol), N,N'-diisopropylcarbodiimide (DIC) (0.1 mL) in 5 mL DCM was stirred at room temperature for 60 hrs. The mixture was loaded on silica gel, purified by flash chromatography using eluents of dichloromethane/ethyl acetate (0% 5% ethyl acetate). The desired fraction was collected, concentrated under reduced pressure. The resulted solid was washed with methanol and dried in air to give the desired product as dark green solid (18 mg, in 29% yield). ¹ H NM R (400 MHz, d2-TCE) 6 8.64 (s, 2H), 8.40 (s, 2H), 8.16 (s, 4H), 8.05 - 7.88 (m, 12H), 7.63 (dd, J = 8.6, 2.9 Hz, 8H), 7.44 - 7.32 (m, 6H), 7.27 - 7.08 (m, 10H), 6.96 - 6.83 (m, 6H), 6.79 (t, J = 7.6 Hz, 4H), 6.70 (d, J = 7.4 Hz, 4H), 6.47 (s, 2H), 5.93 (s, 2H), 2.80 (t, J = 7.6 Hz, 4H), 2.62 (t, J = 7.2 Hz, 4H), 2.17 - 2.03 (m, 4H), 1.92 (s, 6H), 1.78 (s, 3H). Synthesis of Compound: PLC-5:

Compound PLC-5: A mixture of PLC-2.1 (20 mg, 0.025 mmol), PLC-4.3 (61 mg, 0.07 mmol), 4- dimethylaminopyridinium/p-toluenesulfonate (DMAP/TsOH salt) (20 mg, 0.068 mmol), N-(3- dimethylaminopropyl)-N'-ethyicarbodiimide hydrochloride (EDC-HCI) (134 mg, 0.7 mmol) in 5 mL dichloromethane was stirred at 40 °C overnight. The resulted mixture was loaded on silica gel, purified by flash chromatography using eluents of hexanes/ethyl acetate (0% 20% ethyl acetate). The desired fraction was collected and concentrated under reduced pressure. The resulted solid was washed with methanol, dried in air to give the desired product as dark green solid (20 mg, in 32% yield). NMR (400 MHz, d2-TCE) 8 8.64 (s, 2H), 8.39 (s, 2H), 8.16 (d, J = 1.6 Hz, 4H), 8.04 - 7.87 (m, 12H), 7.64 (d, J = 8.3 Hz, 4H), 7.49 (s, 2H), 7.45 - 7.28 (m, 10H), 7.19 (dd, J = 17.8, 8.1 Hz, 6H), 7.04 (s, 2H), 6.95 - 6.83 (m, 6H), 6.78 (t, J = 7.4 Hz, 4H), 6.69 (d, J = 7.3 Hz, 4H), 6.47 (s, 2H), 5.94 (s, 2H), 2.80 (t, J = 7.8 Hz, 4H), 2.63 (t, J = 7.4 Hz, 4H), 2.16 - 2.02 (m, 4H), 1.91 (s, 6H), 1.78 (s, 3H).

Synthesis of Compound PLC-6:

Compound PLC-6.1: A mixture of 4-bromo-l,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, 5 mmol) 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, 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 4.6 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+): calcd for CisHgBrNOe (M+H) = 413.95; Found: 414. NMR (400 MHz, TCE-d2) 8 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-6.2: A mixture of compound PLC-6.1 (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-): calcd for Ci ₈ Hi ₀ BrNO ₄ = 382.98; Found: 383. NMR (400 MHz, DMSO-d ₆ ) 6 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-6.3: Compound PLC-6.2 (2.65 g, 6.9 mmol), was dispersed in acetic acid (50 mL)/water (10 mL) and cooled to 0 ^e C. 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 ^e C. The whole was stirred for one hour at 0 °C, 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 ^e C. After cooled to room temperature, the precipitate was collected by filtration, washed with water (100 mL x 3), then stirred in 50 mL acetone at 40 ^e C for 30 min. Filtration, dried in air then in vacuum gave a brown yellow solid (1.76g, in 70% yield). LCMS (APCI+): calcd for Ci ₈ H ₈ BrO ₄ (M+H) = 366.95; Found: 367. *H NMR (400 MHz, d2-TCE) 8 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-6.4: A mixture of compound PLC-6.3 (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 ^e C 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 ^e C for overnight to afford the desired product as brown yellow solid (0.49 g, in 62% yield). LCMS (APCI-): calcd for C ₂₈ Hi ₈ BrNO ₅ = 527.04; Found: 527. ^J H NMR (400 MHz, DMSO-d ₆ ) 6 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-6.5: A mixture of compound PLC-6.4 (385 mg, 0.729 mmol), 3,5-bis- (trifluoromethyl)phenylboronic acid (374 mg, 1.45 mmol), PdfdppfJCh (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 ^e C 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 (lOOmL 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 (340 mg, in 70.5% yield). LCMS (APCI-): Calcd for C36H21F6NO5 = 661.13; Found: 661.^ NMR (400 MHz, d2-TCE) 8 8.57 (dd, J= 19.2, 8.1 Hz, 2H), 8.18 (d, 7 = 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 compound PLC-1.4 (20 mg, 0.025 mmol), compound PLC-6.5 (52.9 mg, 0.08 mmol), DMAP/TsOH salt (20 mg, 0.068 mmol), EDC»HCI (110 mg, 0.57 mmol) in 5 mL DCM was stirred at room temperature overnight. The resulted mixture was loaded on silica gel, purified by flash chromatography using eluents of DCM/ethyl acetate (0% 10% ethyl acetate). The desired red fraction was collected. After removal of solvents, the solid was washed with methanol and dried in air, the desired product was obtained as a dark solid (34 mg, in 65% yield). Confirmed by ^J H NMR (400 MHz, Methylene Chloride-d ₂ ) 6 8.64 (d, J = 7.8 Hz, 2H), 8.57 (d, J = 8.3 Hz, 2H), 8.28 (d, J = 2.2 Hz, 2H), 8.17 (s, 4H), 8.11 - 7.96 (m, 8H), 7.83 (dd, J = 8.6, 2.2 Hz, 2H), 7.78 - 7.70 (m, 8H), 7.55 (d, J = 8.6 Hz, 2H), 7.52 - 7.45 (m, 4H), 7.37 - 7.28 (m, 6H), 7.27 - 7.20 (m, 4H), 7.05 - 6.97 (m, 2H), 6.92 (dd, J = 8.4, 6.7 Hz, 4H), 6.88 - 6.81 (m, 4H), 6.58 (s, 2H), 6.08 (s, 2H), 2.92 (t, J = 1 Hz, 4H), 2.75 (t, J

= 7.4 Hz, 4H), 2.23 (p, J = 7.6 Hz, 4H), 2.06 (s, 6H), 1.91 (s, 3H).

Synthesis of Compound PLC-7:

Compound PLC-7.1: A mixture of PLC-1.7 (lH,3H-isochromeno[6,5,4-mna]xanthene-l,3- dione) (100 mg, 0.347 mmol), 2-(4-aminophenyl)acetic acid (135 mg, 0.9 mmol) in 5 mL DMF was heated 165 ^e C for 2 hrs in microwave reactor. After cooled to 50 °C, 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 (88 mg, in 61% yield). Confirmed by LCMS (APCI): Calcd for C26Hi ₅ NO ₅ (M-): 421.1; Found: 421. NMR (400 MHz, DMSO-d ₆ ) 6 8.27 (d, 7 = 45.1 Hz, 4H), 7.67 -

7.00 (m, 8H), 3.58 (s, 2H).

Compound PLC-7: A mixture of compound PLC-1.4 (40mg, 0.05 mmol), compound PLC-7.1 (67 mg, 0.16 mmol), DMAP/TsOH salt (20 mg, 0.068 mmol), EDC»HCI (110 mg, 0.57mmol) in 10 mL DCM was stirred at room temperature overnight, then heated at 40 °C for overnight. The resulted mixture was loaded on silica gel and purified by flash chromatography using eluents of DCM/ethyl acetate (0% 10% ethyl acetate). The desired red fraction was collected. After removal of solvents, the solid was triturated with methanol and dried in air, the desired product was obtained as a dark solid (38 mg, in 47% yield). Confirmed by ^J H NMR (400 MHz, d2-TCE) 8 8.46 (dd, J = 19.0, 8.1 Hz, 4H), 7.99 (d, J = 8.3 Hz, 6H), 7.81 (d, J = 8.2 Hz, 2H), 7.67 - 7.60 (m, 8H), 7.56 (d, J = 8.2 Hz, 4H), 7.51 (t, J = 7.7 Hz, 2H), 7.35 - 7.26 (m, 8H), 7.18 (dd, J = 8.5, 2.0 Hz, 6H), 6.87 (d, J = 7.6 Hz, 2H), 6.79 (t, J = 7.5 Hz, 4H), 6.71 (d, J = 7.3 Hz, 4H), 6.48 (s, 2H), 5.93 (s, 2H), 3.95 (s, 4H), 1.92 (s, 6H), 1.78 (s, 3H).

Synthesis of Compound PLC-8:

Compound PLC-8.1 A mixture of compound PLC-6.4 (649 mg, 1.23 mmol), 4-

(trifluoromethyl)phenylboronic acid (467 mg, 2.46 mmol), PdfdppfJCL (45 mg, 0.06 mmol), potassium carbonate (345 mg, 2.5 mmol) in cosolvents of THF/DMF/water (30mL/6mL/3mL) was degassed, then heated at 80 ^e C for overnight. The mixture was worked up with 300mL ethyl acetate and 50 mL 0.6 N hydrochloric acid aqueous solution. The aqueous phase was extracted with ethyl acetate (150 mL x 3). The organic phase was collected and washed with brine (lOOmL x 2), dried over sodium sulfate, then dry loaded on silica gel and purified by flash chromatography using eluents of DCM/EA (0% to 80% EA with 0.1% TFA). The main desired fraction was collected, removal of solvents under reduced pressure gave a yellow solid (414mg, in 57% yield). ^J H NMR (400 MHz, d2-TCE) 8 8.55 (dd, J = 18.1, 8.1 Hz, 2H),

8.16 (d, J = 2.2 Hz, 1H), 8.00 (d, J = 8.1 Hz, 1H), 7.68 (dd, J = 8.6, 2.1 Hz, 1H), 7.66 - 7.59 (m, 2H), 7.43

(d, J = 8.6 Hz, 1H), 7.32 (tt, J = 8.2, 4.2 Hz, 5H), 7.20 - 7.13 (m, 2H), 2.72 (t, J = 7.6 Hz, 2H), 2.39 (t, J =

7.3 Hz, 2H), 1.99 (q, J = 7.4 Hz, 2H).

Compound PLC-8: A mixture of compound PLC-1.4 (26 mg, 0.0326 mmol), compound PLC-8.1 (59 mg, 0.1 mmol), DMAP/TsOH salt (15 mg, 0.051 mmol), EDC»HCI (60 mg, 0.31 mmol) in 5 mL DCM was stirred at room temperature overnight. The resulted mixture was loaded on silica gel, and purified by flash chromatography using eluents of DCM/ethyl acetate (0% 10% ethyl acetate). The desired red fraction was collected. After removal of solvents, the solid was washed with methanol and dried in air, the desired product was obtained as a dark solid (46 mg, in 72% yield). ¹ H NMR (400 MHz, d2- TCE) 8 8.51 (dd, J= 18.1, 8.1 Hz, 4H), 8.11 (d, J = 2.2 Hz, 2H), 7.97 (dd, J= 17.1, 8.2 Hz, 6H), 7.71 - 7.56 (m, 14H), 7.39 (dd, J = 10.8, 8.4 Hz, 6H), 7.27 (dd, J = 13.0, 8.3 Hz, 6H), 7.23 - 7.17 (m, 4H), 7.17 - 7.10 (m, 4H), 6.94 - 6.84 (m, 2H), 6.79 (t, J = 7.5 Hz, 4H), 6.70 (d, J = 7.1 Hz, 4H), 6.48 (s, 2H), 5.93 (s, 2H), 2.80 (t, J = 7.5 Hz, 4H), 2.63 (t, J = 7.3 Hz, 4H), 2.12 (q, J = 7.6 Hz, 4H), 1.92 (s, 6H), 1.78 (s, 3H).

Synthesis of Compound PLC-9:

Compound PLC-9.1: 2-(9-bromo-l,3-dioxo-lH-xantheno[2,l,9-def] isoquinolin-2(3H)- yl)acetic acid. Compound 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 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 1 hr, 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 Chemical Formula: C2oHioBrN0 ₅ (M-) = 424; found: 424. ¹ H NMR (400 MHz, DMSO-d6) 8 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-9.2 2-(9-(4-(tert-butyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9-def] isoquinolin-

2(3 H )-yl)acetic acid (Compound PLC-9.1) (4.24 g, 10.0 mmol, leq) was suspended in 2-methyl-THF (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)CI 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 IN HCI 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 Chemical Formula: C30H23NO5 (M- ) = 477; found: 477. ^J H NMR (400 MHz, DMSO-d6) 8 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-9: (5,5-difluoro-10-mesityl-l,9-diphenyl-5H-4 A ⁴ , 5 X ⁴ -dipyrrolo[l,2-c:2',l'- f] [l,3,2]diaza borinine-3,7-d iyl)bis( [l,l'-biphenyl]-4',4-diyl)bis(2-(9-(4-(tert-butyl)phenyl)-l, 3-d ioxo- lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)acetate): Compound PLC-9.2 (143.25 mg, 0.30 mmol, 3eq) was suspended in DCM anhydrous (10.0 ml), added PLC-1.4 (39.93 mg, 0.05 mmol, 1 eq) , DMAP- pTSA (58.8 mg, 0.2 mmol, 4 eq), EDC. HCI (47.92 mg, 0.25 mmol, 5 eq), stirred at rt, 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 79 mg, yield 91%. ⁴ H NMR (400 MHz, ) 6 8.62 (d, J = 7.9 Hz, 2H), 8.56 (d, J = 8.4 Hz, 2H), 8.19 (d, J = 2.1 Hz, 2H), 8.04 - 7.97 (m, 3H), 7.95 (s, 4H), 7.71 (dd, J = 8.6, 2.1 Hz, 2H), 7.61 (dd, J = 8.6, 1.9 Hz, 8H), 7.57 - 7.53 (m, 4H), 7.45 (d, J = 8.5 Hz, 4H), 7.40 (d, J = 8.6 Hz, 2H), 7.29 (d, J = 8.3 Hz, 2H), 7.20 (d, J = 8.6 Hz, 5H), 6.86 (d, J = 7.5 Hz, 3H), 6.78 (t, J = 7.5 Hz, 4H), 6.69 (d, J = 7.2 Hz, 4H), 6.46 (s, 2H), 5.14 (s, 5H), 1.91 (s, 7H), 1.77 (s, 4H), 1.31 (s, 18H).

Synthesis of Compound PLC-10:

Compound PLC-10.1: 2-(l,3-dioxo-9-(4-(trifluoromethyl) phenyl)-lH-xantheno[2,l,9-def] isoqu inolin-2(3 H)-yl) acetic acid. Compound PLC-9.1 (7.0 g, 16.50 mmol, leq) was suspended in 2- methyl-THF (150 mL), added 4-(trifluoromethyl) benzeneboronic acid (5.648 g, 29.7 mmol, 1.8 eq), K2CO3 (4.65 g, 33 mmol, 2eq), H2O (15 mL) PdfdppfJCL • DCM ( 269.5 mg, 0.33 mmol, 0.02 eq). 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 IN HCI (20 mL) for 15 minutes then holding at RT 1 hours. The solid was filtered, stirred with DMF at RT 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 Chemical Formula: C27H14FNO5 (M-) = 489; found: 489. ⁴ H NMR (400 MHz, DMSO-d6) 8 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-10: (5,5-difluoro-10-mesityl-l,9-diphenyl-5H-4 A ⁴ , 5 X ⁴ -dipyrrolo[l,2-c:2',l'- f] [l,3,2]diaza borinine-3,7-d iyl)bis( [l,l'-biphenyl]-4',4-diyl)bis(2-(l,3-dioxo-9-(4- (trifluoromethyl)phenyl)-lH-xantheno[2,l,9-def]isoquinolin-2 (3H)-yl)acetate). Compound PLC-10.1 (73.4 mg, 0.15 mmol, 3eq) was suspended in DCM anhydrous (10.0 ml), added Compound PLC-1.4 (39.93 mg, 0.05 mmol, 1 eq) , DMAP-pTSA (58.8 mg, 0.2 mmol, 4 eq), EDC. HCI (47.92 mg, 0.25 mmol, 5 eq), stirred at rt, under Argon atmosphere, 5 hours, diluted with DCM (150 ml), filtered, washed 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 then washed with MeOH, gained 82 mg, yield 94%. ⁴ H NMR (400 MHz) 8 8.63 (d, J = 7.9 Hz, 1H), 8.58 (d, J = 8.3 Hz, 1H), 8.19 (d, J = 2.1 Hz, 1H), 8.01 (d, J = 8.2 Hz, 1H), 7.96 (d, J = 8.3 Hz, 2H), 7.71 (d, J = 2.5 Hz, 4H), 7.61 (d, J = 8.1 Hz, 3H), 7.45 (d, J = 8.6 Hz, 1H), 7.32 (d, J = 8.4 Hz, 1H), 7.20 (d, J = 8.6 Hz, 2H), 6.87 (t, J = 7.3 Hz, 1H), 6.78 (t, J = 7.6 Hz, 2H), 6.69 (d, J = 7.5 Hz, 2H), 6.45 (s, 2H), 5.24 (s, 1H), 5.14 (s, 2H), 1.96 (s, 1H), 1.91 (s, 3H), 1.77 (s, 2H), 1.18 (d, J = 6.5 Hz, 6H).

Synthesis of Compound PLC-11:

Compound PLC-11.1: (3,7-bis(4-bromophenyl)-10-(2,6-dichlorophenyl)-5,5-difluoro -l,9- diphenyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazabori nine): 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 2-(4-bromophenyl)-4-phenyl-lH-pyrrole (3.00 mmol, 895 mg) and 2,6-dichlorobenzaldehyde (1.530 mmol, 268 mg), followed by anhydrous dichloroethane (40 mL). Under argon atmosphere, the reaction mixture was sparged with nitrogen for 2 minutes, then pTsOH.F O (0.450 mmol, 86 mg) was added, followed by an additional 10 mL of anhydrous dichloroethane. TLC shows spot to spot conversion to the desired dipyrrolomethane in 15 minutes at room temperature. The nitrogen sparge was discontinued and the reaction mixture stirred under argon. The reaction mixture was stirred overnight under argon. The next day, DDQ. (1.80 mmol, 409 mg) was added, followed by anhydrous dichloroethane, and the reaction mixture stirred at room temperature for one hour. To the reaction mixture was added EtaN (13.5 mmol, 1.7 mL) and BFa.0Et2 (9.00 mmol, 1.3 mL) and the reaction mixture stirred for 2 minutes at room temperature. The addition of EtaN (13.5 mmol, 1.7 mL) and BFa.0Et2 (9.00 mmol, 1.3 mL) was repeated, and then the reaction mixture was stirred at room temperature for one hour. The heat block was set to 80 ° C and the reaction mixture stirred at this temperature for one hour. The reaction mixture was cooled to room temperature, diluted with 300 mL of ethyl acetate, and quenched by adding methanol (25 mL). The reaction mixture was extracted with saturated aqueous NaHCOa (3 X 100 mL), brine (50 mL), dried over MgSO ₄ , filtered and evaporated to dryness in vacuo. The crude product was dissolved in DCM and evaporated onto ~40 mL of flash silica gel in vacuo. Purified by flash chromatography on silica gel (220g, solid load, equilibrate 50% toluene/hexanes, eluting CV)) . Fractions containing product were evaporated to dryness in vacuo. Gives 748 mg of a dark pink solid, 62% yield (based on pyrrole). MS (APCI): calculated for Chemical Formula: C39H23BBr2Cl2F2N2 (M- ) = 796; found: 796. ^J H NMR (400 MHz, Tetrachloroethane-d ₂ ) 6 7.87 - 7.79 (m, 4H), 7.66 - 7.59 (m, 4H), 7.03 - 6.90 (m, 10H), 6.57 - 6.44 (m, 5H).

Compound PLC-11.2: (4',4"'-(10-(2,6-dichlorophenyl)-5,5-difluoro-l,9-diphenyl-5 H-4l4,5l4- dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-3,7-diyl)bis([l ,l ^l -biphenyl]-4-ol)): PLC-11.2 was synthesized from PLC-11.1 (0.650 mmol, 519 mg), (4-hydroxyphenyl)boronic acid (3.90 mmol, 538 mg), K2CO3 (15.02 mmol, 2.075 g), and PdfdppfJCL (0.065 mmol, 48 mg) in anhydrous THF (100 mL) and water (10 mL) in a manner similar to the procedures above. The crude reaction mixture was quenched with acetic acid (10 mL) and flash silica gel was added (~40 mL). The crude reaction mixture was evaporated to dryness in vacuo. Purified by flash chromatography on silica gel (120g, equilibrate 100% hexanes, eluting 100% hexanes (2 100% EtOAc (30 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a dark-colored solid, 501 mg (93% yield). MS (APCI): calculated for Chemical Formula: C51H33BCI2F2N2O2 (M-) = 824; found: 824. ¹ H NMR (400 MHz, Tetrachloroethane-d ₂ ) 6 8.10 - 8.01 (m, 4H), 7.73 - 7.64 (m, 4H), 7.63 - 7.54 (m, 4H), 7.08 - 6.89 (m, 14H), 6.62 - 6.45 (m, 5H).

Compound PLC-11: ((10-(2,6-dichlorophenyl)-5,5-difluoro-l,9-diphenyl-5H-4l4,5 l4- dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-3,7-diyl)bis([l ,l'-biphenyl]-4',4-diyl) bis(4-(4-(l,3-dioxo- lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)butanoate) ): PLC-11 was synthesized from PLC- 11.2 (0.100 mmol, 83 mg), PLC-1.8 (0.300 mmol, 135 mg), DMAP.pTsOH salt (0.400 mmol, 118 mg), and EDC.HCI (0.250 mmol, 48 mg) in anhydrous EtOAc (5 mL). The addition of EDC.HCI (0.250 mmol, 48 mg) was repeated to give complete reaction. The reaction mixture was evaporated to dryness in vacuo, dissolved in DCM, loaded onto flash silica gel (~40 mL in a solid loader), and purified by flash chromatography on silica gel (120g, equilibrate 100% DCM, eluting 100% DCM (2 CV) 10% EtOAc/DCM (30 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives 116 mg (69% yield). MS (APCI): calculated for Chemical Formula: C107H67BCI2F2N4O10 (M-) = 1686; found: 1686. ^J H NMR (400 MHz, Methylene Chloride-d ₂ ) 6 8.65 (d, J= 7.9 Hz, 2H), 8.60 (d, J= 8.3 Hz, 2H), 8.22 (s, 4H), 8.14 (dd, J = 8.0, 1.6 Hz, 2H), 8.02 (d, J = 8.0 Hz, 2H), 7.74 - 7.67 (m, 4H), 7.63 - 7.54 (m, 6H), 7.50 (s, 4H), 7.46 - 7.30 (m, 18H), 7.29 - 7.24 (m, 4H), 7.20 - 7.13 (m, 4H), 7.06 - 7.00 (m, 8H), 4.04 (s, 4H), 2.76 (hept, J = 7.0 Hz, 4H), 1.16 (d, J = 6.8 Hz, 24H). Synthesis of Compound PLC-12:

Compound PLC-12.1: A mixture of lH,3H-isochromeno[6, 5, 4-mna]xanthene-l, 3-dione

(Compound PLC-1.7) (lOOmg, 0.347 mmol), 2-(4-aminophenyl)acetic acid (135 mg, 0.9 mmol) in 5mL DMF was heated 165 ^e C for 2 hrs in microwave reactor. After cooled to 50 °C, 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): Calcd for C26H15NO5 (M-): 421.1; Found: 421. ^J H NMR (400 MHz, DMSO-de) 6 8.27 (d, J = 45.1 Hz, 4H), 7.67 - 7.00 (m, 8H), 3.58 (s, 2H).

Compound PLC-12 ((10-(2,6-dichlorophenyl)-5,5-difluoro-l,9-diphenyl-5H-4l4,5 l4- dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-3,7-diyl)bis([l ,l'-biphenyl]-4',4-diyl)bis(2-(4-(l,3-dioxo- lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetate)): PLC-12 was synthesized from PLC-12.1 (0.020 mmol, 16.5 mg), ), 2-(4-(l,3-dioxo-lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)p henyl)acetic acid (0.060 mmol, 25.3 mg), DMAP.pTsOH salt (0.080 mmol, 23.6 mg), and EDC.HCI (0.060 mmol, 11.5 mg). The crude reaction mixture was evaporated to dryness, dissolved in DCM, and loaded onto flash silica gel (~5g) in a solid loader. Purified by flash chromatography on silica gel (80g, equilibrate 100% DCM, eluting 100% DCM (2 CV) 10% EtOAc/DCM (30 CV)). Fractions containing product were evaporated to dryness, then triturated with hot methanol. The solid was filtered off and dried in a vacuum oven at ~110 ° C. Gives a bluish solid, 19.8 mg (61% yield). MS (APCI): calculated for Chemical Formula: C103H59BCI2F2N4O10 (M-) = 1630; found: 1630. ¹ H NMR (400 MHz, Methylene Chloride-ck) 6 8.45 - 8.34 (m, 4H), 8.04 (d, J = 8.1 Hz, 4H), 7.93 - 7.84 (m, 2H), 7.78 - 7.65 (m, 10H), 7.61 (d, J = 8.0 Hz, 4H), 7.56 - 7.46 (m, 2H), 7.40 - 7.21 (m, 12H), 7.12 - 7.01 (m, 6H), 7.01 - 6.92 (m, 6H), 6.64 - 6.46 (m, 5H), 4.03 (s, 4H).

Synthesis of Compound PLC-13:

Compound PLC-13.1 (6-(4-(tert-butyl)-2-nitrophenoxy)-lH,3H-benzo[de]isochromen e-l,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-lH,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 IN HCI (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 Chemical Formula: C22H17NO6 (M+H) = 392; found: 392. NMR (400 MHz, Tetrachloroethane-d ₂ ) 6 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-13.2 (6-(2-amino-4-(tert-butyl)phenoxy)-lH,3H-benzo[de]isochromen e-l,3- dione): 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 13.1 (10.0 mmol, 3.914 g) and 2- MeTHF (70 mL). With stirring at room temperature, added HCI in water (100 mmol, 4. ON, 25 mL) and SnCl2.2H2O (40.0 mmol, 9.024 g). The reaction mixture was stirred under argon atmosphere with the heat block set to 90 ⁰ C for 30 minutes. The reaction mixture was cooled to 0 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 lOOmL). 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 Chemical Formula: C22H19NO4 (M+H) = 362; found: 362. ¹ H NMR (400 MHz, Tetrachloroethane-ck) 6 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-13.3 (9-(tert-butyl)-lH,3H-isochromeno[6, 5, 4-mna]xanthene-l, 3-dione): 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 ⁰ C. A 100 mL round bottom flask was charged with a stir bar and Compound 13.2 (4.00 mmol, 1.446 g). To the flask was added glacial AcOH (30 mL) and con. HCI (20.0 mmol, 12. IN, 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 NaNC>2 before the acetic acid begins to freeze. The NaNCh was added over a period of a period of ~10 minutes. The diazo solution was stirred at 0 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 CUSO4.5H2O (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 highspeed 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% 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 Chemical Formula: C22H16O4 (M+H) = 345; found: 345. NMR (400 MHz, Tetrachloroethane-d ₂ ) 6 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-13.4: (4-(4-(9-(tert-butyl)-l,3-dioxo-lH-xantheno[2,l,9-def]isoqui nolin- 2(3H)-yl)phenyl)butanoic acid): Compound 13.4 was synthesized from Compound 13.3 (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 the procedures described above. 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 ⁰ C. Gives a yellow solid, 738 mg (96% yield). MS (APCI): calculated for Chemical Formula: C32H27NO5 (M+H) = 506; found: 506. ¹ H NMR (400 MHz, DMSO-de) 6 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-13 ((5,5-difluoro-10-mesityl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'- f][l,3,2]diazaborinine-3,7-diyl)bis([l,l'-biphenyl]-4',4-diy l) bis(4-(4-(9-(tert-butyl)-l,3-dioxo-lH- xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)butanoate)): PLC-13 was synthesized from 4', 4"- (5,5-difluoro-10-mesityl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f] [l,3,2]diazaborinine-3,7-diyl)bis([l,l'- biphenyl]-4-ol) (Compound PLC-1.4) (0.050 mmol, 39.9 mg), PLC-13.4 (0.150 mmol, 75.8 mg), DMAP.pTsOH salt (0.200 mmol, 58.9 mg), and EDC.HCI (0.150 mmol, 28.8 mg) in a manner similar to the procedures described above. The crude reaction mixture was diluted 2:1 with hexanes and loaded onto ~15g of flash silica gel in a solid loader. Purified by flash chromatography on silica gel (120g, solid load, equilibrate 40% DCM/hexanes, eluting 40% DCM/hexanes (2 CV) isocratic DCM + 1% EtOAc modifier. Fractions containing product were evaporated to dryness in vacuo. The product was triturated with hot MeOH and the resulting solid was dried in a vacuum oven at ~110 ° C. Gives 78.8 mg of a dark red solid (89% yield). MS (APCI): calculated for Chemical Formula: C106H83BF2N4O10 (M-) = 1773; found: 1773. *H NMR (400 MHz, Tetrachloroethane-d ₂ ) 6 8.61 (d, J = 7.9 Hz, 2H), 8.56 (d, J= 8.3 Hz, 2H), 8.08 (d, J= 8.3 Hz, 4H), 8.06 (d, J= 2.3 Hz, 2H), 7.99 (d, J= 8.1 Hz, 2H), 7.76 - 7.68 (m, 8H), 7.63 (dd, J = 8.7, 2.2 Hz, 2H), 7.47 (d, J = 8.3 Hz, 4H), 7.36 (d, J = 8.7 Hz, 2H), 7.30

(dd, J = 8.3, 1.7 Hz, 6H), 7.26 - 7.20 (m, 4H), 7.01 - 6.94 (m, 2H), 6.88 (t, J = 7.5 Hz, 4H), 6.80 (d, J = 7.0 Hz, 4H), 6.57 (s, 2H), 6.02 (s, 2H), 2.89 (t, J = 7.6 Hz, 4H), 2.72 (t, J = 7.4 Hz, 4H), 2.20 (p, J = 7.5 Hz, 4H),

2.01 (s, 6H), 1.87 (s, 3H), 1.45 (s, 18H).

Synthesis of Compound PLC-14:

Compound PLC-14.1: (2-(4-(9-(tert-butyl)-l,3-dioxo-lH-xantheno[2,l,9-def]isoqui nolin- 2(3H)-yl)phenyl)acetic acid): Compound PLC-14.1 was synthesized from Compound PLC-13.3 (1.191 mmol, 410 mg) and 2-(4-aminophenyl)acetic acid (2.98 mmol, 450 mg) in anhydrous DMF (10 mL) in a manner similar to Compound 1. After workup and precipitation, obtained the product, 579 mg (quantitative yield). MS (APCI): calculated for Chemical Formula: C30H23NO5 (M+H) = 478; found: 478. NMR (400 MHz, DMSO-d ₆ ) 6 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-14 ((5,5-difluoro-10-mesityl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'- f][l,3,2]diazaborinine-3,7-diyl)bis([l,l'-biphenyl]-4',4-diy l) bis(2-(4-(9-(tert-butyl)-l,3-dioxo-lH- xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetate)): Compound PLC-14 was synthesized from 4',4"'-(5,5-difluoro-10-mesityl-5H-4l4,5l4-dipyrrolo[l,2-c:2 ',l'-f][l,3,2]diazaborinine-3,7- diyl)bis( [ l,l'-biphenyl]-4-ol) (PLC-1.4) (0.050 mmol, 39.9 mg), Compound PLC-14.1 (0.150 mmol, 71.6 mg), DMAP.pTsOH salt (0.200 mmol, 58.9 mg), and EDC.HCI (0.150 mmol, 28.8 mg) in a manner similar to Compound 2. After purification in the usual way, the product was triturated with hot MeOH. The product was dried in a vacuum oven at ~110 ⁰ C. Gives a dark red solid, 57.3 mg (67% yield). MS (APCI): calculated for Chemical Formula: C102H75BF2N4O10 (M-) = 1716; found: 1716. ¹ H NMR (400 MHz, Tetrachloroethane-d ₂ ) 6 8.53 (d, J = 7.9 Hz, 2H), 8.48 (d, J = 8.3 Hz, 2H), 8.05 (d, J = 2.3 Hz, 2H), 8.03 - 7.98 (m, 4H), 7.91 (d, J = 8.0 Hz, 2H), 7.75 - 7.69 (m, 8H), 7.65 - 7.58 (m, 6H), 7.37 - 7.33 (m, 4H), 7.32

(d, J = 8.7 Hz, 2H), 7.28 - 7.23 (m, 4H), 7.18 (d, J = 8.3 Hz, 2H), 7.00 - 6.93 (m, 2H), 6.91 - 6.84 (m, 4H), 6.84 - 6.78 (m, 4H), 6.55 (s, 2H), 6.04 (s, 2H), 4.03 (s, 4H), 2.03 (s, 6H), 1.87 (s, 3H), 1.45 (s, 18H).

Synthesis of Compound PLC-15:

Compound PLC-15.1 ((E)-l-(4-bromophenyl)-3-(4-(tert-butyl)phenyl)prop-2-en-l-o ne): A

500 mL round bottom flask was charged with a stir bar, l-(4-bromophenyl)ethan-l-one (40.0 mmol, 7.960 g), 4-(tert-butyl)benzaldehyde (40.0 mmol, , 6.489g, 6.69 mL), and ethanol (200 proof, 80 mL). With stirring at room temperature was added KOH (78.4 mmol, 4.399g). The reaction mixture was stirred vigorously at room temperature. Within 2-3 minutes, a precipitate formed, so stirring speed was increased to maintain a stirred slurry. After 30 minutes, TLC indicates complete consumption of starting materials. The reaction mixture was poured into stirred water (500 mL). This mixture was stirred at room temperature for 5 minutes, then the solid filtered off, washing with water. The precipitate was dried in a vacuum oven at 110 ⁰ C overnight. NMR indicates the presence of impurities, so the solid was triturated with methanol. This did not improve purity, so the material was purified by column chromatography on silica gel (330g, mixture evaporated onto silica gel, equilibrate 100% hexanes, eluting 100% hexanes (2 CV) 10% EtOAc/hexanes (20 CV)). Fractions containing product were evaporated to dryness in vacuo to give an off-white solid. Gives 8.983 g (65% yield). MS (APCI): calculated for Chemical Formula: CigHigBrO (M+H) = 343; found: 343. ¹ H NMR (400 MHz, Tetrachloroethane-d ₂ ) 6 7.92 - 7.85 (m, 2H), 7.79 (d, J = 15.6 Hz, 1H), 7.70 - 7.65 (m, 2H), 7.64 - 7.59 (m, 2H), 7.47 (d, J = 8.4 Hz, 2H), 7.44 (d, J = 15.6 Hz, 1H), 1.35 (s, 9H).

Compound PLC-15.2 (l-(4-bromophenyl)-3-(4-(tert-butyl)phenyl)-4-nitrobutan-l-o ne): A 250 mL 2N round bottom flask was charged with a stir bar and fitted with a finned condenser, gas adapter, and flow control valve. The system was flushed with argon, then charged with PLC-15.1 (8.898 g, 25.92 mmol), ethanol (200 proof, T1 mL), nitromethane (28 mL), and KOH (5.184 mmol, 291 mg). The reaction mixture was stirred under argon and heated in an aluminum heating block to 95 ° C. After 30 minutes, TLC indicates complete consumption of starting material. The flask was removed from the heating block and placed in an ice-water bath and cooled to about room temperature. The reaction mixture was partitioned with ethyl acetate (100 mL) and water (100 mL), with a little bit of solid NaCI added to break the emulsion. The layers were separated, the organic layer dried over MgSO ₄ , filtered, and concentrated to dryness in vacuo. The resulting yellow oil was triturated with hexanes while warm to give a solid. The solid was stirred overnight at room temperature, then filtered off, washing with hexanes. The resulting off-white solid was dried in a vacuum oven at 80 ° C. Gives 9.10 g (87% yield). MS (APCI): calculated for Chemical Formula: C2oH22BrNOs (M+H) = 404; found: 404. ¹ H NMR (400 MHz, Tetrachloroethane-d ₂ ) 6 7.82 - 7.75 (m, 2H), 7.66 - 7.59 (m, 2H), 7.37 - 7.32 (m, 2H), 7.22 - 7.15 (m, 2H), 4.81 (dd, J = 12.5, 6.7 Hz, 1H), 4.68 (dd, J = 12.5, 8.0 Hz, 1H), 4.16 (p, J = 7.1 Hz, 1H), 3.44 (dd, J = 17.9, 6.1 Hz, 1H), 3.36 (dd, J = 17.9, 7.5 Hz, 1H), 1.29 (s, 9H).

Compound PLC-15.3 (l-(4-bromophenyl)-3-(4-(tert-butyl)phenyl)-4,4-dimethoxybut an-l- one): A 500 mL round bottom flask was charged with a stir bar. To the flask was added PLC-15.2 (22.51 mmol, 9.10 g), followed by anhydrous THF (235 mL) and methanol (120 mL). The reaction mixture was stirred vigorously at room temperature, then KOH (58.35 mmol) was added to the flask. The reaction mixture was stirred at room temperature. In a separate 2N IL round bottom flask, carefully prepare a mixture of H2SO4 (25 mL) and methanol (120 mL). Clamp the flask by the off-center neck and carefully stopper. After 90 minutes, the reaction mixture was added to an addition funnel in the off-center neck. The IL flask was cooled in an ice-water bath at 0 ⁰ C. The H2SO ₄ /MeOH mixture was stirred vigorously and the solution added dropwise. Appears to be an outgassing and the atmosphere above the liquid turns brown-orange. The addition was performed over a period of 2.5 hours. The reaction mixture was stirred for an additional hour, then the mixture transferred to a 2L Erlenmeyer flask. To the stirred mixture was added water (300 mL), followed by 2N NaOH (~250 mL) to give a pH of approximately 10. The solution was partitioned with DCM (2X300mL). The combined organic layers were dried over MgSC>4, filtered, and concentrated to dryness in vacuo. The resulting brown oil solidifies overnight. ¹ H NMR indicates a mixture of ~75% dimethyl acetal and 25% aldehyde. The mixture was used in the next step without further purification.

Compound PLC-15.4 (2-(4-bromophenyl)-4-(4-(tert-butyl)phenyl)-lH-pyrrole): A 100 mL 2N round bottom flask was charged with a stir bar and fitted with a finned condenser, gas adapter, and flow control. The system was flushed with argon. To the flask was added crude PLC-15.3 (assume 100% yield) and NH ₄ OAc (109.4 mmol, 8.432 g), followed by glacial acetic acid (35 mL). The reaction mixture was stirred under argon and heated in an aluminum heat block at 100 ° C. TLC at 5 hours indicates complete consumption of aldehyde and acetal. The reaction mixture was quenched by pouring into stirred water (300 mL). The resulting precipitate was collected by vacuum filtration, washing with water. Dried in a vacuum oven at ~80 ° C. Gives a dark grey solid, 7.56g (95% yield, based on Compound 1.2). MS (APCI): calculated for Chemical Formula: C2oH2oBrN (M+H) = 354; found: 354. ¹ H NMR (400 MHz, DMSO-de) 6 8.49 (s, 1H), 7.56 - 7.51 (m, 2H), 7.51 - 7.47 (m, 2H), 7.43 - 7.37 (m, 4H), 7.16 (dd, J = 2.7, 1.7 Hz, 1H), 6.81 (dd, J= 2.8, 1.7 Hz, 1H), 1.35 (s, 9H).

Compound PLC-15.5 (3,7-bis(4-bromophenyl)-l,9-bis(4-(tert-butyl)phenyl)-5,5-di fluoro-10- mesityl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborin ine): A 250 mL 2N round bottom flask was charged with a stir bar and fitted with a finned condenser, gas adapter, and flow control. The system was flushed with argon. To the flask was added PLC-15.4 (2.0 mmol, 709 mg), mesitaldehyde (2.50 mmol, 0.369 mL), and anhydrous dichloroethane (50 mL). While under argon atmosphere and with stirring at room temperature, the reaction mixture was sparged with nitrogen gas for 10 minutes. To the flask was added pTsOH.H ₂ O (0.300 mmol, 57 mg) and stirring and sparging with nitrogen gas was continued for another 10 minutes. The flask was stirred under static argon and heated with an aluminum heat block at 80 ° C overnight. The reaction mixture was cooled to room temperature and DDQ. (1.70 mmol, 386 mg) was added and stirring continued at room temperature under argon for one hour. To the reaction mixture was added EtaN (8.00 mmol, 1.11 mL) and BFa.0Et2 (12.0 mmol, 1.48 mL). The reaction mixture was stirred at room temperature for 2 minutes, then the addition of EtaN (8.00 mmol, 1.11 mL) and BFa.0Et2 (12.0 mmol, 1.48 mL) was repeated. The flask was placed back in the heat block and the heat block was set at 80 ° C. The reaction mixture was stirred at 80 ° C for 90 minutes. The reaction mixture was cooled to room temperature, then the volume was doubled by the addition of hexanes and stirring continued at room temperature overnight. The reaction mixture was loaded onto 65g of flash silica gel in a solid loader. Purified by flash chromatography on silica gel (330g, equilibrate 100% hexanes, eluting 100% hexanes (2 CV) 40% toluene/hexanes (30 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a red-pink solid, 236 mg (27% yield). MS (APCI): calculated for Chemical Formula: CsoH47BBr2F2N2 (M-) = 882; found: 882. ¹ H NMR (400 MHz, Tetrachloroethane-d ₂ ) 6 7.84 - 7.78 (m, 4H), 7.64 - 7.59 (m, 4H), 6.89 - 6.84 (m, 4H), 6.69 - 6.63 (m, 4H), 6.45 (s, 2H), 6.02 (s, 2H), 1.97 (s, 6H), 1.88 (s, 3H), 1.19 (s, 18H).

Compound PLC-15.6 (4',4"'-(l,9-bis(4-(tert-butyl)phenyl)-5,5-difluoro-10-mesit yl-5H- 4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-3,7-diy l)bis(([l,l'-biphenyl]-4-ol))): Compound PLC-15.6 was synthesized from PLC-15.5 (0.205 mmol, 181 mg), (4-hydroxyphenyl)boronic acid (1.228 mmol, 169 mg), K2CO3 (1.228 mmol, 170 mg), and PdfdppfJCk (0.0512 mmol, 37.4 mg) in THF (8 mL) and water (0.8 mL) in a microwave synthesizer at 110 ⁰ C in a manner similar to Compound 10.1. The crude reaction mixture was loaded onto ~65g flash silica gel in a loader. Purified by flash chromatography on silica gel (220g, equilibrate 100% toluene, eluting 100% toluene (2 CV) 10% EtOAc/toluene (20 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a dark purple-red solid, 115 mg (62% yield). MS (APCI): calculated for Chemical Formula: C62H57BF2N2O2 (M-) = 910; found: 910. ^J H NMR (400 MHz, Tetrachloroethane-d ₂ ) 8 7.99 - 7.90 (m, 4H), 7.62 - 7.54 (m, 4H), 7.54 - 7.47 (m, 4H), 6.89 - 6.82 (m, 4H), 6.81 - 6.75 (m, 4H), 6.65 - 6.56 (m, 4H), 6.45 (s, 2H), 5.94 (s, 2H), 4.94 (s, 2H), 1.91 (s, 6H), 1.80 (s, 3H), 1.11 (s, 18H).

Compound PLC-15 ((l,9-bis(4-(tert-butyl)phenyl)-5,5-difluoro-10-mesityl-5H-4 l4,5l4- dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-3,7-diyl)bis([l ,l'-biphenyl]-4',4-diyl) bis(4-(4-(9-(3,5- bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9-def] isoquinolin-2(3H)- yl)phenyl)butanoate)): Compound PLC-15 was synthesized from PLC-15.6 (0.0201 mmol, 18.3 mg), 4- (4-(9-(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno [2,l,9-def]isoquinolin-2(3H)- yl)phenyl)butanoic acid (PLC-6.5) (0.0603 mmol, 38.2 mg), DMAP.pTsOH salt (0.0804 mmol, 23.7 mg), and EDC.HCI (0.0804 mmol, 15.4 mg). The crude reaction mixture was loaded onto ~25g of flash silica gel in a loader. Purified by flash chromatography on silica gel (120g, solid load, equilibrate 100% hexanes, eluting 100% hexanes (3 CV) 100% DCM/1% EtOAc modifier (0 CV) 100% DCM/1%

EtOAc modifier (15 CV) 100% DCM/2% EtOAc modifier 100% DCM/3% EtOAc modifier 100% DCM/4% EtOAc modifier (track separation of yellow impurity from product and ramp up EtOAc until they elute separately)). Fractions containing product were evaporated to dryness in vacuo. Gives a dark red solid, 38.6 mg (90% yield). ¹ H NMR (400 MHz, Tetrachloroethane-d ₂ ) 6 8.65 (d, J = 7.9 Hz, 2H), 8.59 (d, J = 8.3 Hz, 2H), 8.24 (d, J = 2.2 Hz, 2H), 8.13 - 8.04 (m, 10H), 7.95 (s, 2H), 7.80 (dd, J = 8.7, 2.1 Hz, 2H), 7.75 - 7.69 (m, 8H), 7.67 - 7.62 (m, 4H), 7.56 (d, J = 8.6 Hz, 2H), 7.41 - 7.34 (m, 6H), 7.30 - 7.23 (m, 4H), 6.88 (d, J = 8.4 Hz, 4H), 6.70 (d, J = 8.2 Hz, 4H), 6.56 (s, 2H), 6.03 (s, 2H), 4.04 (s, 4H), 2.01 (s, 6H), 1.89 (s, 3H), 1.21 (s, 18H). Synthesis of Compound PLC-16:

Compound PLC-16.1 (3,7-bis(4-bromophenyl)-l,9-bis(4-(tert-butyl)phenyl)-10-(2, 6- dichlorophenyl)-5,5-difluoro-5H-4l4,5l4-dipyrrolo[l,2-c:2',l '-f][l,3,2]diazaborinine): PLC-16.1 was synthesized from PLC-15.4 (2.0 mmol, 709 mg), 2,6-dichlorobenzaldehyde (1.0 mmol, 175 mg), pTsOH.I-hO (0.300 mmol, 57 mg), DDQ. (1.30 mmol, 295 mg), Et3N (8.00 mmol, 1.12 mL), and BFa.0Et2 (12.0 mmol, 1.48 mL) in anhydrous DCE (25 mL) in a manner similar to the above methods. The dipyrromethane step was performed at room temperature instead of 80 °C. The crude reaction mixture was diluted to twice the volume with hexanes and loaded onto ~60g flash silica gel in a loader. Purified by flash chromatography on silica gel (330g, solid load, no equilibration eluting 100% hexanes 50% toluene/hexanes (20 CV)) . Fractions containing product were evaporated to dryness in vacuo. Gives a dark red-pink solid, 483 mg (53% yield). MS (APCI): calculated for Chemical Formula: C ₄ 7H ₃ 9BBr2Cl2F2N2 (M-) = 908; found: 908. ^J H NMR (400 MHz, Tetrachloroethane-*) 6 7.87 - 7.78 (m, 4H), 7.66 - 7.59 (m, 4H), 6.97 - 6.87 (m, 8H), 6.53 - 6.37 (m, 5H), 1.18 (s, 18H).

Compound PLC-16.2 (4',4"'-(l,9-bis(4-(tert-butyl)phenyl)-10-(2,6-dichloropheny l)-5,5- difluoro-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazabori nine-3,7-diyl)bis(([l,l'-biphenyl]-4-ol))): PLC-16.2 was synthesized from PLC-16.1 (0.205 mmol, 181 mg), (4-hydroxyphenyl)boronic acid (1.228 mmol, 169 mg), K2CO3 (1.228 mmol, 170 mg), and PdfdppfJCk (0.0512 mmol, 37.4 mg) in THF (8 mL) and water (0.8 mL) in a microwave synthesizer at 110 ⁰ C in a manner similar to Compound 10.1. The crude reaction mixture was loaded onto ~65g flash silica in a loader. Purified by flash chromatography on silica gel (220g, solid load, no equilibration, eluting 100% toluene (2 CV) 10% EtOAc/toluene (20 CV)) . Fractions containing product were evaporated to dryness in vacuo. Gives a dark red-purple solid, 117 mg (61% yield). MS (APCI): calculated for Chemical Formula: C59H49BCI2F2N2O2 (M-) = 936; found: 936. *H NMR (400 MHz, Tetrachloroethane-*) 8 8.08 - 8.03 (m, 4H), 7.71 - 7.66 (m, 4H), 7.62 - 7.57 (m, 4H), 6.94 (d, J = 7.2 Hz, 12H), 6.57 (s, 2H), 6.51 (d, J = 1.3 Hz, 1H), 6.49 (s, 1H), 6.41 (dd, J = 9.0, 7.0 Hz, 1H), 5.03 (s, 2H), 1.19 (s, 18H).

Compound PLC-16 ((l,9-bis(4-(tert-butyl)phenyl)-10-(2,6-dichlorophenyl)-5,5- difluoro-5H- 4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-3,7-diy l)bis([l,l'-biphenyl]-4',4-diyl) bis(4-(4-(9- (3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9 -def]isoquinolin-2(3H)- yl)phenyl)butanoate)): Compound PLC-16 was synthesized from PLC-16.2 (0.030 mmol, 28.1 mg), 4- (4-(9-(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno [2,l,9-def]isoquinolin-2(3H)- yl)phenyl)butanoic acid (PLC-6.5) (0.090 mmol, 57 mg), DMAP.pTsOH salt (0.120 mmol, 35.3 mg), and EDC.HCI (0..120 mmol, 23 mg) in a manner similar to the above methods. The crude reaction mixture was diluted with hexanes and loaded onto ~30g flash silica in a loader. Purified by flash chromatography on silica gel (80g, equilibrate 100% hexanes/0.5% EtOAc modifier, eluting 100% hexanes/0.5% EtOAc modifier 2 CV) 100% DCM/0.5% EtOAc modifier (0 CV) isocratic 100% DCM/0.5% EtOAc modifier c modifier modifier (30 CV)). Fractions containing product were evaporated to dryness in vacuo. The crude product was triturated with hot methanol. The product was dried in a vacuum oven at ~110 ⁰ C. Gives a dark red solid, 47.6 mg (73% yield). ¹ H NMR (400 MHz, Tetrachloroethane-*) 6 8.65 (d, J = 7.8 Hz, 2H), 8.59 (d, J = 8.3 Hz, 2H), 8.24 (d, J = 2.2 Hz, 2H), 8.14 - 8.04 (m, 10H), 7.95 (s, 2H), 7.80 (dd, J = 8.6, 2.1 Hz, 2H), 7.77 - 7.69 (m, 8H), 7.65 (d, J = 8.3 Hz, 4H), 7.56 (d, J = 8.6 Hz, 2H), 7.37 (dd, J = 8.3, 5.6 Hz, 6H), 7.30 - 7.24 (m, 4H), 6.95 (s, 8H), 6.59 (s, 2H), 6.54 - 6.48 (m, 2H), 6.42 (dd, J = 9.0, 7.0 Hz, 1H), 4.04 (s, 4H), 1.19 (s, 18H). Synthesis of Compound PLC-17:

Compound PLC-17.1: 2-(4-(9-bromo-l,3-dioxo-lH-xantheno[2,l,9-def]isoquinolin-2( 3H)- yljphenyljacetic acid: A mixture of compound PLC-6.3 (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 ^e C 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 ^e C. 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 ^e C for 2 hrs and then has been kept stirring at room temperature overnight. The solid was collected through vaccum filtration and washed by acetone (4 mL). And it was dried by vacuum oven at 100 ^e C for 3 hrs to provide the pure compound as a yellow brown solid 395.0 mg, 73% yield. MS (APCI): calculated for Chemical Formula: C26Hi4BrNO ₅ ([M+H] ⁺ ) = 500 found: 500. NMR (400 MHz, CDCI ₂ CDCI ₂ ) 6 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-17.2: 2-(4-(l,3-dioxo-9-(4-(trifluoromethyl)phenyl)-lH-xantheno[2, l,9- def]isoquinolin-2(3H)-yl)phenyl)acetic acid: A 100 mL vial was fitted with a stir bar. To the vial, compound PLC-17.1 (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 K2CO3 (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 ^e C 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 HCI (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 Na2SO 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 as a yellow/ yellow brown solid. 363.0 mg, 80% yield. MS (APCI): calculated for Chemical Formula: C33H18F3NO5 ([M+H] ⁺ ) = 566 found: 566. 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-17: (l,9-bis(4-(tert-butyl)phenyl)-5,5-difluoro-10-mesityl-5H-4l 4,5l4- dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-3,7-diyl)bis([l ,l'-biphenyl]-4',4-diyl) bis(2-(4-(l,3-dioxo- 9-(trifluoromethyl)-lH-xantheno[2,l,9-def]isoquinolin-2(3H)- yl)phenyl)acetate)): Compound PLC- 17 was synthesized from Compound PLC-17.2 (0.025 mmol, 22.8 mg), Compound PLC-15.6 (0.075 mmol, 37 mg), DMAP.pTsOH salt (0.100 mmol, 29 mg), and EDC. HCI (0..125 mmol, 24 mg) in a manner similar to the methods described above. The crude reaction mixture was diluted with hexanes and loaded onto ~30g of flash silica gel in a loader. Purified by flash chromatography on silica gel (80g, solid load, equilibrate 100% hexanes, eluting 100% hexanes (2 CV) 100% DCM (0 CV) 100% DCM 100% DCM/1% EtOAc modifier (until compound elutes)). Fractions containing product were evaporated to dryness in vacuo. The product was triturated with hot methanol. The product was dried in a vacuum oven at ~110 ⁰ C. Gives a dark red solid, 42 mg (91% yield). MS (APCI): calculated for Chemical Formula: CiieHsiBFsN^io (M-) = 1853; found: 1853. ¹ H NMR (400 MHz, Tetrachloroethane- d ₂ ) 6 8.54 (d, J = 7.8 Hz, 2H), 8.51 (d, J = 8.3 Hz, 2H), 8.21 (d, J = 2.1 Hz, 2H), 7.98 (d, J = 8.2 Hz, 4H), 7.91 (d, J = 8.1 Hz, 2H), 7.71 (dd, J = 8.9, 2.0 Hz, 2H), 7.67 - 7.59 (m, 8H), 7.59 - 7.52 (m, 4H), 7.41 (d, J = 8.6 Hz, 2H), 7.31 - 7.24 (m, 6H), 7.21 - 7.14 (m, 4H), 6.83 - 6.76 (m, 4H), 6.61 (d, J = 8.3 Hz, 4H), 6.46 (s, 2H), 5.94 (s, 2H), 3.95 (s, 4H), 1.92 (s, 6H), 1.80 (s, 3H), 1.11 (s, 18H).

Synthesis of Compound PLC-18:

Compound PLC-18.1 (2-(4-(9-(4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)-l,3 -dioxo- lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid): Compound PLC-18.1 was synthesized from Compound PLC-17.1 (2.00 mmol, 1001 mg), 2-(4-(2-(2-(2- methoxyethoxy)ethoxy)ethoxy)phenyl)-4,4,5,5-tetramethyl-l,3, 2-dioxaborolane (4.00 mmol, 1465 mg), K2CO3 (5.50 mmol, 760 mg), and PdfdppfJCL (0.140 mmol, 102 mg) in THF (60 mL), DMF (12 mL), and water (6 mL) at 80 ⁰ C for 2 hours in a manner similar to Compound 2.3. The crude product reaction mixture was quenched with 6N HCI (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 MgSC>4, filtered, and evaporated to dryness in vacuo (including DMF). The crude product was evaporated onto ~50g 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) Fractions containing product were evaporated to dryness in vacuo. Gives a yellow solid, 722 mg (55% yield). MS (APCI): calculated for Chemical Formula: C39H33NO9 (M+H) = 660; found: 660. ¹ H NMR (400 MHz, DMSO-de) 6 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-18 ((5,5-difluoro-10-mesityl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'- f][l,3,2]diazaborinine-3,7-diyl)bis([l,l'-biphenyl]-4',4-diy l) bis(2-(4-(9-(4-(2-(2-(2- methoxyethoxy)ethoxy)ethoxy)phenyl)-l,3-dioxo-lH-xantheno[2, l,9-def]isoquinolin-2(3H)- yljphenyljacetate)): Compound PLC-18 was synthesized from 4',4"'-(5,5-difluoro-10-mesityl-5H- 4l4,5l4-dipyrrolo[l,2-c:2', l'-f] [ l,3,2]d iaza borinine-3,7-d iyl) bis( [1, l'-biphenyl]-4-ol) (PLC-1.4, 0.040 mmol, 32 mg), Compound PLC 18.1 (0.120 mmol, 79.2 mg), DMAP.pTsOH salt (0.160 mmol, 47.1 mg), and EDC.HCI (0.200 mmol, 38.3 mg) in a manner similar to the above described methods. The crude product was loaded onto ~65g flash silica gel in a loader. Purified by flash chromatography on silica gel (120g, solid load, equilibrate 100% DCM, eluting 100% DCM (2 100% DCM/0.5% MeOH modifier (1 CV) 100% DCM/1% MeOH modifier (1 CV) 100% DCM/2% MeOH modifier (20 CV) 100% DCM/3% MeOH modifier (5 CV)). Product elutes too slowly with 2% MeOH, but elutes rapidly with 3% MeOH modifier. Fractions containing pure product were evaporated to dryness in vacuo. Gives a dark red powder, 40.8 mg (52.8% yield). MS (APCI): calculated for Chemical Formula: C120H95BF2N4O18 (M-) = 1929; found: 1929. *H NMR (400 MHz, Tetrachloroethane-d ) 8 8.61 (d, J = 7.8 Hz, 2H), 8.56 (d, J = 8.3 Hz, 2H), 8.18 (d, J = 2.2 Hz, 2H), 8.08 (d, J = 8.2 Hz, 4H), 8.00 (d, J = 8.2 Hz, 2H), 7.79 - 7.68 (m, 10H), 7.64 (t, J = 8.5 Hz, 8H), 7.46 (d, J = 8.6 Hz, 2H), 7.41 - 7.35 (m, 4H), 7.31 (d, J = 8.4 Hz, 2H), 7.29 - 7.24 (m, 4H), 7.12 - 7.04 (m, 4H), 6.97 (t, J = 7.2 Hz, 2H), 6.88 (t, J = 7.5 Hz, 4H), 6.80 (d, J = 7.1 Hz, 4H), 6.57 (s, 2H), 6.02 (s, 2H), 4.22 (t, J = 4.8 Hz, 4H), 4.04 (s, 4H), 3.90 (t, J = 4.8 Hz, 4H), 3.78 - 3.72 (m, 4H), 3.72 - 3.62 (m, 8H), 3.59 - 3.53 (m, 4H), 3.38 (s, 6H), 2.02 (s, 6H), 1.87 (s, 3H).

Synthesis of Compound PLC-19:

Compound PLC-19.1: ((E)-l-(4-bromophenyl)-3-(4-octylphenyl)prop-2-en-l-one):

Compound PLC-19.1 was synthesized from l-(4-bromophenyl)ethan-l-one (22.9 mmol, 4.557 g), 4- octylbenzaldehyde (22.9 mmol, 5.00 g), and KOH (44.89 mmol, 2.519 g) in 200 proof EtOH (35 mL) at room temperature in a manner similar to the method described above. The crude product was precipitated by adding water, filtered off, and recrystallized from 200 proof EtOH. Gives an off-white solid, 8.197 g (90% yield). MS (APCI): calculated for Chemical Formula: C23H2?BrO (M+H) = 399; found: 399. *H NMR (400 MHz, TCE) 6 7.91 - 7.85 (m, 2H), 7.79 (d, J = 15.6 Hz, 1H), 7.70 - 7.64 (m, 2H), 7.61

- 7.55 (m, 2H), 7.44 (d, J = 15.7 Hz, 1H), 7.29 - 7.23 (m, 2H), 2.70 - 2.60 (m, 2H), 1.66 - 1.61 (m, 2H), 1.39 - 1.20 (m, 10H), 0.92 - 0.86 (m, 3H).

Compound PLC-19.2 (l-(4-bromophenyl)-4-nitro-3-(4-octylphenyl)butan-l-one): Compound

PLC-19.2 was synthesized from Compound PLC-19.1 (20.52 mmol, 8.197 g) and KOH (4.104 mmol, 230 mg) in nitromethane (22 mL) and 200 proof ethanol (22 mL) at 95 ° C for one hour in a manner similar to method described above. The crude reaction mixture was partitioned between 100 mL of water and 100 mL of EtOAc. A small amount of NaCI breaks the emulsion. The layers were separated, the organic layer was dried over MgSO ₄ , filtered and evaporated to dryness in vacuo. Gives a thick, brown oil, 9.34 g (99% yield). MS (APCI): calculated for Chemical Formula: C24H3oBrNOa (M+H) = 460; found: 460. NMR (400 MHz, TCE) 8 7.81 - 7.74 (m, 2H), 7.67 - 7.59 (m, 2H), 7.16 (s, 4H), 4.81 (dd, J= 12.4, 6.6 Hz, 1H), 4.67 (dd, J = 12.5, 8.0 Hz, 1H), 4.15 (p, J = 6.8 Hz, 1H), 3.43 (dd, J = 17.9, 6.2 Hz, 1H), 3.36 (dd, J= 17.9, 7.5 Hz, 1H), 2.62 - 2.51 (m, 2H), 1.61 - 1.50 (m, 4H), 1.38 - 1.22 (m, 10H), 0.94 - 0.84 (m, 3H).

Compound PLC-19.3 (l-(4-bromophenyl)-4,4-dimethoxy-3-(4-octylphenyl)butan-l-on e): Compound PLC-19.3 was synthesized from Compound PLC-19.2 (20.29 mmol, 9.34 g) and KOH (52.54 mmol, 2.948 g) in dry THF (225 mL) and dry MeOH (115 mL) in a manner similar to the method described above. This solution was added dropwise to a solution of 95% H2SO4 (25 mL) in dry MeOH (120 mO) at 0 ⁰ C. After workup and evaporation of all solvents in vacuo, gives a brown oil, 8.13 g (82% yield). Mixture of dimethyl acetal and aldehyde. MS (APCI): calculated for Chemical Formula: C ₂ 6H35BrO ₃ (M+H) = 475; found: 475.

Compound PLC-19.4 (2-(4-bromophenyl)-4-(4-octylphenyl)-lH-pyrrole): Compound PLC- 19.4 was synthesized from Compound PLC-19.3 (20.29 mmol, assume 100% from previous step), NH4OAC (109.4 mmol, 8.432 g) in AcOH (35 mL) at 100 ⁰ C in a manner similar to method described above. After heating overnight at 100 ⁰ C, the reaction mixture was cooled to room temperature and water was added. The resulting precipitate was filtered off, dissolved in DCM, dried over MgSO ₄ , and evaporated to dryness. The product was recrystallized from 200 proof ethanol. Gives a purple-blue solid, 3.652 g (41% yield). MS (APCI): calculated for Chemical Formula: C24H2sBrN (M+H) = 410; found: 410. ^J H NMR (400 MHz, TCE) 8 8.49 (s, 1H), 7.56 - 7.50 (m, 2H), 7.50 - 7.44 (m, 2H), 7.43 - 7.37 (m, 2H), 7.19 (d, J = 8.3 Hz, 2H), 7.15 (t, J = 2.1 Hz, 1H), 6.81 (dd, J = 2.6, 1.6 Hz, 1H), 2.66 - 2.56 (m, 2H), 1.70 - 1.56 (m, 4H), 1.42 - 1.21 (m, 8H), 0.94 - 0.83 (m, 3H).

Compound PLC-19.5 (3,7-bis(4-bromophenyl)-5,5-difluoro-10-mesityl-l,9-bis(4- octylphenyl)-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diaza borinine): Compound PLC-19.5 was synthesized from Compound PLC-19.4 (2.10 mmol, 862 mg), 2,4,6-trimethylbenzaldehyde (1.00 mmol, 0.148 mL), and pTsOH.H ₂ O (0.400 mmol, 76 mg), then DDQ. (1.700 mmol, 386 mg) and 2X Et ₃ N (8.00 mmol, 1.11 mL) and BF3.OEt2 (12.00 mmol, 1.50 mL) in dry DCE (20 mL) at 60 ⁰ C, then 50 ⁰ C in a manner similar to the method described above. The crude reaction mixture was diluted with hexanes (~250 mL) and washed with 6N HCL (50 mL), water (50 mL), sat. NaHCOs (2X100 mL), and brine (50 mL). The organic layer was dried over MgSO ₄ , filtered, and evaporated to dryness in vacuo. Dissolved the crude in hexanes and loaded onto 65g silica gel in a loader. Purified by flash chromatography on silica gel (220g, solid load, equilibrate 100% hexanes, eluting 100% hexanes (2 CV) 30% EtOAc/hexanes (30 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a deep red solid, 512 mg (51% yield). MS (APCI): calculated for Chemical Formula: C ₅ 8H63BBr2F2N2 (M+H) = 995; found: 995. ^! H NMR (400 MHz, TCE) 6 7.83 - 7.76 (m, 4H), 7.66 - 7.57 (m, 4H), 6.68 (d, J = 8.2 Hz, 4H), 6.64 (d, J = 8.1 Hz, 4H), 6.43 (s, 2H), 6.04 (s, 2H), 2.46 - 2.35 (m, 4H), 1.97 (s, 6H), 1.89 (s, 3H), 1.44 (p, j = 6.8 Hz, 4H), 1.38 - 1.21 (m, 22H), 0.95 - 0.86 (m, 6H).

Compound PLC-19.6 (4',4"'-(5,5-difluoro-10-mesityl-l,9-bis(4-octylphenyl)-5H-4 l4,5l4- dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-3,7-diyl)bis([l ,l ^l -biphenyl]-4-ol)): Compound PLC-19.6 was synthesized from Compound PLC-19.5 (0.200 mmol, 200 mg), 4-(4,4,5,5-tetramethyl-l,3,2- dioxaborolan-2-yl)phenol (0.800 mmol, 176 mg), K2CO3 (4.60 mmol, 636 mg), and Pd (dppfJCL (0.020 mmol, 15 mg) in THF (10 mL) and water (2 mL) in a manner similar to the methods described above at 110 ⁰ C in the microwave synthesizer for 3 h. The THF and water were evaporated in vacuo and the reaction mixture dissolved in DCM and loaded onto ~40g of silica gel in a loader. Purified by flash chromatography on silica gel (220g, solid load, equilibrate 0% EtOAc/hexanes, eluting 0% (2 CV) 5% EtOAc/hexanes (30 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a dark red solid, 99 mg (48% yield). MS (APCI): calculated for Chemical Formula: C70H73BF2N2O2 (M+H) = 1023; found: 1023. *H NMR (400 MHz, TCE) 8 8.08 - 7.98 (m, 4H), 7.71 - 7.62 (m, 4H), 7.62 - 7.54 (m, 4H), 6.98 - 6.89 (m, 4H), 6.73 - 6.64 (m, 8H), 6.52 (s, 2H), 6.05 (s, 2H), 4.98 (s, 2H), 2.41 (dd, J = 8.8, 6.7 Hz, 4H), 2.00 (s, 6H), 1.90 (s, 3H), 1.53 - 1.39 (m, 4H), 1.38 - 1.26 (m, 20H), 0.96 - 0.87 (m, 6H).

Compound PLC-19: ((5,5-difluoro-10-mesityl-l,9-bis(4-octylphenyl)-5H-4l4,5l4- dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-3,7-diyl)bis([l ,l'-biphenyl]-4',4-diyl) bis(2-(4-(l,3-dioxo- 9-(4-(trifluoromethyl)phenyl)-lH-xantheno[2,l,9-def]isoquino lin-2(3H)-yl)phenyl)acetate)):

Compound 42 was synthesized from Compound 42.1 (0.0400 mmol, 41 mg), ), Compound 36.4 (0.120 mmol, 68 mg), DMAP.pTsOH salt (0.160 mmol, 47 mg), and EDC.HCI (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 crude product was loaded onto ~20g 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 (30 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a deep red solid, 52 mg (61% yield). ^J H NMR (400 MHz, TCE) 8 8.63 (d, J = 7.8 Hz, 2H), 8.58 (d, 7 = 8.3 Hz, 2H), 8.23 (d, J = 2.3 Hz, 2H), 8.07 (d, J = 8.2 Hz, 4H), 8.02 (d, J = 8.1 Hz, 2H), 7.83 - 7.75 (m, 10H), 7.75 - 7.69 (m, 8H), 7.65 (d, J = 8.4 Hz, 4H), 7.52 (d, J = 8.6 Hz, 2H), 7.41 - 7.36 (m, 4H), 7.34 (d, J = 8.3 Hz, 2H), 7.26 (d, J = 8.6 Hz, 4H), 6.75 - 6.63 (m, 8H), 6.54 (s, 2H), 6.05 (s, 2H), 4.04 (s, 4H), 2.42 (t, J = 7.7 Hz, 4H), 2.01 (s, 6H), 1.91 (s, 3H), 1.51 - 1.39 (m, 4H), 1.37 - 1.25 (m, 20H), 0.95 - 0.88 (m, 6H). Synthesis of Compound PLC-2O

Compound PLC-20.1: (4',4"'-(5,5-difluoro-10-mesityl-l,9-bis(4-octylphenyl)-5H-4 l4,5l4- dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-3,7-diyl)bis([l ,l'-biphenyl]-3-ol)): Compound PLC-20.1 was synthesized from Compound PLC-19.5 (0.200 mmol, 200 mg), (3-hydroxyphenyl)boronic acid (0.800 mmol, 110 mg), K2CO3 (4.60 mmol, 636 mg), and Pd(dppf)Ch (0.020 mmol, 15 mg) in THF (10 mL) and water (2 mL) in a manner similar to the methods described above at 110 ⁰ C in the microwave synthesizer for 3 h. The THF and water were evaporated in vacuo and the reaction mixture dissolved in DCM and loaded onto ~40g of silica gel in a loader. Purified by flash chromatography on silica gel (220g, solid load, equilibrate 0% EtOAc/hexanes, eluting 0% (2 CV) 5% EtOAc/hexanes (30 CV)).

Fractions containing product were evaporated to dryness in vacuo. Gives a dark red solid, 101 mg (49% yield). MS (APCI): calculated for Chemical Formula: C70H73BF2N2O2 (M+H) = 1023; found: 1023. ¹ H NMR (400 MHz, TCE) 8 7.95 (d, J = 8.3 Hz, 4H), 7.66 - 7.54 (m, 4H), 7.26 (t, J = 7.9 Hz, 2H), 7.17 (dt, J = 7.9, 1.2 Hz, 2H), 7.05 (t, J = 2.0 Hz, 2H), 6.76 (ddd, J = 8.0, 2.6, 1.0 Hz, 2H), 6.64 - 6.54 (m, 8H), 6.44 (s, 2H), 5.96 (s, 2H), 4.86 (s, 2H), 2.32 (t, J = 7.8 Hz, 4H), 1.43 - 1.29 (m, 4H), 1.19 (d, J = 16.2 Hz, 20H), 0.87 -

0.78 (m, 6H).

Compound PLC-20: ((5,5-difluoro-10-mesityl-l,9-bis(4-octylphenyl)-5H-4l4,5l4- dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-3,7-diyl)bis([l ,l'-biphenyl]-4',3-diyl) bis(2-(4-(l,3-dioxo- 9-(4-(trifluoromethyl)phenyl)-lH-xantheno[2,l,9-def]isoquino lin-2(3H)-yl)phenyl)acetate)): Compound PLC-20 was synthesized from Compound PLC 20.1 (0.0400 mmol, 41 mg), Compound PLC- 17.2 (0.140 mmol, 79 mg), DMAP.pTsOH salt (0.160 mmol, 47 mg), and EDC. HCI (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 the methods described above. The crude product was loaded onto ~40g of silica gel in a loader. Purified by flash chromatography on silica gel (220g, solid load, equilibrate 0% EtOAc/DCM, eluting 0% (2 10% EtOAc/DCM (30 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a deep red solid, 47 mg (55% yield). ¹ H NMR (400 MHz, TCE) 6 8.61 (d, J = 7.9 Hz, 2H), 8.57 (d, J = 8.3 Hz, 2H), 8.21 (d, J = 2.2 Hz, 2H), 8.08 (d, J = 8.2 Hz, 4H), 8.00 (d, J = 8.2 Hz, 2H), 7.82 - 7.72 (m, 14H), 7.63 (d, J = 8.3 Hz, 4H), 7.59 (d, J = 7.9 Hz, 2H), 7.52 - 7.44 (m, 6H), 7.40 - 7.35 (m, 4H), 7.33 (d, J = 8.3 Hz, 2H), 7.14 (ddd, J = 8.0, 2.3, 1.0 Hz, 2H), 6.74 - 6.63 (m, 8H), 6.54 (s, 2H), 6.05 (s, 2H), 4.04 (s, 4H), 2.41 (t, J = 7.8 Hz, 4H), 2.00 (s, 6H), 1.90 (s, 3H), 1.53 - 1.39 (m, 4H), 1.37 - 1.26 (m, 20H), 0.91 (t, J = 6.7 Hz, 6H).

Synthesis of Compound PLC-21:

Compound PLC-21.1: 2-(4-(9-(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xanthe no[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetic acid: A 100 mL vial was fitted with a stir bar. To the vial, compound PLC-17.1 (400.0 mg, 0.80 mmol), 3,5-bis(trifluoromethyl)phenylboronic acid (262.2 mg, 1.6 mmol), Pd(dppf)Ch (41.0 mg, 0.056 mmol) and K2CO3 (412.6 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 ^e C 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 HCI (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 Na2SO 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-21.1 as a yellow/ yellow brown solid. 311.0 mg, 61% yield. MS (APCI): calculated for Chemical Formula: C34H17F6NO5 ([M+H] ⁺ ) = 634 found: 634. ^J 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-21: A 25 mL vial was fitted with a stir bar. To the vial, compound PLC-1.4 (40.0 mg, 0.05 mmol), compound PLC-21.1 (158.4 mg, 0.25 mmol), EDC»HCI (76.7 mg, 0.40 mmol) and DMAP»TsOH (75.0 mg, 0.25 mmol) were added, followed by anhydrous DCM (4 ml). The reaction mixture has been kept at room temperature for 48 hours. 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 compound PLC-21 as a dark purple solid. The solid was further triturated with EtOAc (1 mL) and MeOH (20 ml) to deliver RL-naphthalimide- BODIPY 1605-108, 60.0 mg, 60% yield. MS (APCI): couldn't be observed by our LCMS system. ¹ H NMR (400 MHz, CDCI2CDCI2) 8.65 (d, J = 8.0 Hz, 2H), 8.59 (d, J = 8.0 Hz, 2H), 8.24 (d, J = 2.4 Hz, 2H), 8.08 (m, 10H), 7.95 (s, 2H), 7.80 (dd, J = 8.0 Hz, 2.4 Hz, 2H), 7.73 (m, 8H), 7.65 (m, 4H), 7.56 (d, J = 8.0 Hz, 2H),

7.38 (m, 6H), 7.26 (m, 4H), 6.97 (m, 2H), 6.88 (t, J= 8.0 Hz, 4H), 6.79 (m, 4H), 6.57 (s, 2H), 6.02 (s, 2H), 4.04 (s, 4H), 2.01 (s, 6H), 1.87 (s, 3H).

Synthesis of Compound PLC-22: Compound PLC-22.1: (9-bromo-2-(5-hydroxypentyl)-lH-xantheno [2,1,9-def] isoquinoline-

1,3(2 H)-dione). Compound PLC-6.3 (1.223 g, 3.33 mmol, 1 eq) was suspended in 35 mL DMSO anhydrous, 5-amino-l-pentanol (1.5 g, 20.0 mmol, 6 eq) was added to the reaction mixture at RT. The resulting mixture was stirred at 160 °C 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 C23Hi8BrNO ₄ (M-) = 453; found: 453. MS (APCI): calculated for Chemical Formula: C23HisBrNO ₄ (M-) = 452.; found: 452. NMR (400 MHz) 8 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, 7 = 8.3 Hz, 1H), 7.19 (d, 7 = 8.8 Hz, 1H), 4.14 - 4.02 (m, 2H), 3.64 - 3.49 (m, 2H), 1.68 (p, 7 = 7.7 Hz, 2H), 1.60 - 1.54 (m, 2H), 1.41 (q, 7 = 8.0 Hz, 2H), 1.28 (s, 1H).

Compound PLC-22.2: (2-(5-hydroxypentyl)-9-(4-(trifluoromethyl) phenyl)-lH- xantheno[2,l,9-def] isoquinoline-l,3(2H)-dione): Compound PLC-22.1 (1.13 g, 2.5 mmol, leq) 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)CI ₂ • DCM (40.8 mg, 0.05 mmol, 0.02eq). The mixture was degassed by Vac- Fill Argon cycle 3 times, stirred & heated at 90 °C 5 hours. The reaction mixture was cooled to room temperature, water was added. The resulting mixture was hold at RT 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 Chemical Formula: C3oH22F3N0 ₄ (M-) = 517; found: 517. *H NMR (400 MHz) 8 8.56 (d, 7 = 7.9 Hz, 1H), 8.51 (d, 7 = 8.3 Hz, 1H), 8.17 (d, 7 = 2.1 Hz, 1H), 7.97 (d, 7 = 8.0 Hz, 1H), 7.69 (dd, 7 = 10.3, 1.9 Hz, 4H), 7.42 (d, 7 = 8.6 Hz, 1H), 7.28 (d, 7 = 8.3 Hz, 1H), 4.09 (t, 7 = 7.5 Hz, 2H), 3.57 (q, 7 = 6.2 Hz, 2H), 1.69 (p, 7 = 7.8 Hz, 2H), 1.61 - 1.54 (m, 2H), 1.42 (q, 7 = 8.0 Hz, 2H), 1.28 (t, 7 = 5.5 Hz, 1H).

Compound PLC-22.3: (2-(5-bromopentyl)-9-(4-(trifluoromethyl) phenyl)-lH-xantheno[2,l,9- def] isoquinoline-l,3(2H)-dione): Reflux (HBr 48% bp:126 °C) the mixture of PLC-22.2 (0.66 g, 1.288 o mmol) and 48% aqueous HBr (20.0 ml) by heating block at 120 C for 5 h with stirring. After cooling to RT, 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 0.7g greenish yellow solid, yield 93%. Product was used next step without further purification. MS (APCI): calculated for C ₃ oH2iBrF ₃ N03 (M-) = 581; found: 581. *H NMR (400 MHz) 8 8.57 (d, 7 = 7.9Hz, 1H), 8.51 (d, 7 = 8.3 Hz, 1H), 8.18 (d, 7 = 2.2 Hz, 1H), 7.98 (d, 7 = 7.9 Hz, 1H), 7.69 (dd, 7 = 9.6, 2.0 Hz, 4H), 7.43 (d, 7 = 8.6 Hz, 1H), 7.28 (d, 7 = 8.3 Hz,lH), 4.09 (t, 7 = 7.5 Hz, 3H), 3.38 (t, 7 = 6.7 Hz, 2H), 1.97 - 1.81 (m, 2H), 1.69 (t, 7 = 7.8 Hz, 2H). Compound PLC-22: 2'-(5,5-difluoro-10-mesityl-l,9-diphenyl-5H-4 I ⁴ , 5 l ⁵ -dipyrrolo[l,2-c:2',l'- f][l,3,2]diazaborinine-3,7-diyl)bis([l,l'-biphenyl]-4',4-diy l))bis(oxy))bis(pentane-5,l-diyl))bis(9-(4- (trifluoromethyl)phenyl)-lH-xantheno[2,l,9-def]isoquinoline- l,3(2H)-dione). Compound 22.3 (7.625 mg, 0.15 mmol, 3eq) was suspended in DCM anhydrous (10.0 ml), added compound 1.4 (39.93 mg, 0.05 mmol, 1 eq), K ₂ CO ₃ (20.73 mg, 0.15 mmol, 3eq), the mixture was stirred at 65 °C, under Argon atmosphere, 45 minutes. The mixture was concentrated to dryness, washed solid with 50 ml water, dissolved to DCM, loaded onto 80 g SiO2 column, eluting with Hex-DCM (1/1), DCM only then 0.5% EA in DCM, washed with MeOH, gained 82 mg, yield 94%. ¹ H NMR (400 MHz) 6 8.50 (d, J = 7.9 Hz, 2H), 8.45 (d, J = 8.3 Hz, 2H), 8.10 (d, J = 2.1 Hz, 2H), 7.94 (d, J = 8.2 Hz, 4H), 7.90 (d, J = 8.1 Hz, 2H), 7.68 (s, 7H), 7.65 (dd, J = 8.6, 2.2 Hz, 2H), 7.58 (d, J = 8.4 Hz, 4H), 7.50 (d, J = 8.7 Hz, 4H), 7.37 (d, J = 8.6 Hz, 2H), 7.21 (d, J = 8.3 Hz, 2H), 6.88 (t, J = 8.0 Hz, 6H), 6.79 (t, J = 7.5 Hz, 4H), 6.69 (d, J = 7.1 Hz, 4H), 6.46 (s, 2H), 4.11 (t, J = 7.4 Hz, 4H), 3.95 (t, J = 6.4 Hz, 4H), 1.91 (s, 6H), 1.88 - 1.68 (m, 11H).

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 (4 g) was added to 3 mg of the photoluminescent complex made as described 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 pm. 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 PLC-1 is shown in FIG.l. The resulting absorption/emission spectrum for PLC-2 is shown in FIG. 2. The resulting absorption/emission spectrum for PLC-4 is shown in FIG.3. The resulting absorption/emission spectrum for PLC-5 is shown in FIG.4.

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.