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Title:
ORGANOMETALLIC COMPLEXES AND RELATED COMPOSITIONS AND METHODS
Document Type and Number:
WIPO Patent Application WO/2018/198096
Kind Code:
A2
Abstract:
Provided herein is a coordination complex of Formula (I): wherein - - - - - is a coordinate bond; where M is a metal; X1, X2, X3, X4, X5, X6, and X7 are each independently selected from a heteroatom; R1, R2, R3, R4, R7, and R8 are each independently selected from H and a saturated or unsaturated, substituted or unsubstituted, cyclic or linear hydrocarbon comprising from 1 to 8 carbon atoms; R5 and R6 are each independently selected from H and a saturated or unsaturated, substituted or unsubstituted, cyclic or linear hydrocarbon comprising from 1 to 8 carbon atoms; and n is an integer.

Inventors:
KREUTZ FERNANDO THOME (BR)
DA SILVA CAMERON CAPELETTI (BR)
MARTINS FELIPE TERRA (BR)
MAIA LAURO JUNE QUEIROZ (BR)
DO NASCIMENTO NETO JOSE ANTONIO (BR)
Application Number:
PCT/IB2018/052957
Publication Date:
November 01, 2018
Filing Date:
April 28, 2018
Export Citation:
Click for automatic bibliography generation   Help
Assignee:
KREUTZ FERNANDO THOME (BR)
International Classes:
C07F3/00
Other References:
See references of EP 3615546A4
Download PDF:
Claims:
Claims

1 . A coordination complex of Formula (I) :

Formula (I) wherein is a coordinate bond;

where M is a metal;

Xi, X2, X3, X4, X5, Χε, and Xzare each independently selected from a heteroatom;

R\ R2, R3, R4, R7, and R8 are each independently selected from H and a saturated or unsaturated, substituted or unsubstituted, cyclic or linear hydrocarbon comprising from 1 to 8 carbon atoms;

R5 and R6 are each independently selected from H and a saturated or unsaturated, substituted or unsubstituted, cyclic or linear hydrocarbon comprising from 1 to 8 carbon atoms; and

n is an integer.

2. The coordination complex of claim 1 , wherein M is a metal selected from the group consisting of Zn, Cd, Hg, and a transition metal with 2 valence electrons.

3. The coordination complex of claim 2, wherein M is Cd.

4. The coordination complex of any one of claims 1 to 3, wherein at least one of Xi and X2 is N.

5. The coordination complex of claim 4, wherein Xi and X2 are both N.

6. The coordination complex of any one of claims 1 to 5, wherein X3, X4, X5, Χε, and Xzare each independently selected from the group consisting of O, S, and Se.

7. The coordination complex of claim 6, wherein at least one of X3, X4, X5, Χε, and X IS O.

8. The coordination complex of claim 6 or 7, wherein X3, X4, X5, Χε, and X7 are the same. 9. The coordination complex of any one of claims 6 to 8, wherein each of X3, X4, X5, Χε, and X7 is O.

10. The coordination complex of any one of claims 1 to 9, wherein at least one of R\ R2, R3, R4 is NH2.

1 1 . The coordination complex of claim 10, wherein one of R\ R2, R3, R4 is NH2 and three of R\ R2, R3, R4 are H.

12. The coordination complex of claim 1 1 , wherein the NH2 is disordered over two occupancy sites.

13. The coordination complex of claim 12, wherein the NH2 is disordered over the two occupancy sites with an occupancy factor of about 50%. 14. The coordination complex of any one of claims 1 to 13, wherein at least one of R5 and R6 is CH3.

15. The coordination complex of claim 14, wherein R5 and R6are both CH3. 16. The coordination complex of any one of claims 1 to 15, wherein at least one of R7 and R8 is H.

17. The coordination complex of claim 16, wherein R7 and R8 are both H.

18. The coordination complex of any one of claims 1 to 17, wherein n is 1 .

19. The coordination complex of any one of claims 1 to 17, wherein n is from about 1 to about 100, such as from about 1 to about 75, such as from about 1 to about 50, such as from about 1 to about 25, such as from about 1 to about 20, such as from about 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, or 19 to about 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19, or 20.

20. The coordination complex of any one of claims 1 to 19, of Formula (II):

Formula (II)

21 . The coordination complex of any one of claims 1 to 20, of Formula (III):

Formula (III)

22. A coordination complex comprising the formula [Cd(C4H5N3)(C2H302)2(H20)]n, wherein n is an integer.

23. The coordination complex of claim 22, wherein n is 1 .

24. The coordination complex of claim 22, wherein n is from about 1 to about 100, such as from about 1 to about 75, such as from about 1 to about 50, such as from about 1 to about 25, such as from about 1 to about 20, such as from about 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, or 19 to about 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19, or 20.

25. The coordination complex of any one of claims 22 to 24, comprising the formula

[Cd(aminopyrazine)(acetate)2(H20)]n.

26. A coordination complex comprising a central metal atom coordinated by a nitrogen atom of aminopyrazine, two bidentate ligands, and an oxygen atom of water.

27. The coordination complex of claim 26, wherein the bidentate ligands are selected from formate and acetate, optionally wherein at least one O is substituted with S or Se. 28. A coordination polymer comprising the coordination complex of any one of claims 1 to 27.

29. The polymer of claim 28, forming a one-dimensional polymer chain. 30. A solution comprising the coordination complex of any one of claims 1 to 28.

31 . The solution of claim 30, wherein the coordination complex is monomeric.

32. A crystalline compound of the following structure:

33. A blue emitting crystal form based on a cadmium coordination polymer comprising an external quantum efficiency of greater than 70%.

A cr stalline compound comprising the following powder X-ray diffraction pattern

2 theta ( )

35. A crystalline compound comprising x-ray diffraction peaks at the following 2Θ positions, within a ±0.200° range: (peaks with normalized intensities equal or higher than 10% are listed)

8.105;

12.474;

13.184;

13.797;

14.327;

15.347;

16.251 ;

16.979;

20.127;

23.857;

24.068

24.327

26.546

34.253

35.462

36.063

36.233

36.868

37.148

and

39.641 .

36. A monomer of the crystalline compound of any one of claim 32 to 35.

37. The monomer of claim 36, in solution. 38. An OLED comprising an anode, a cathode, and therebetween a light-emitting layer comprising the coordination complex of any one of claims 1 to 27, the coordination polymer of claim 28 or 29, or the crystalline compound of any one of claims 32 to 35.

39. A novelty item comprising the coordination complex of any one of claims 1 to 27, the coordination polymer of claim 28 or 29, the solution of claims 30 or 31 , the crystalline compound of any one of claims 32 to 35, or the monomer of claim 36 or 37.

40. A peptide comprising the coordination complex of any one of claims 1 to 27, the coordination polymer of claim 28 or 29, the solution of claims 30 or 31 , the crystalline compound of any one of claims 32 to 35, or the monomer of claim 36 or 37.

41 . The peptide of claim 40, wherein the peptide is an antibody or antigen.

Description:
ORGANOMETALLIC COMPLEXES AND RELATED COMPOSITIONS AND METHODS

Field

The present invention relates to coordination complexes. More specifically, the present invention is, in aspects, concerned with blue light-emitting coordination complexes, related polymers and compositions, and methods of making and using same.

Background

Organic light emitting devices (OLEDs) as solid state lighting sources have meant the enterprise of display technologies 1-3 . In this context, the search for new light-emitting materials in the solid state with maximum external quantum efficiency (EQE) in the visible spectral range is desired to improve the performance of electronic devices and has attracted interest of many chemists of materials and electronics companies 4-9 . The higher the external efficiency of a light- emitter, the higher will be its applicability into OLEDs of practical uses. In this context, photoluminescence assessment is the first step in the screening of such new promising candidates 7 ' 8 10-17 . Recently, heavy-metal complexes have been extensively explored in order to obtain high internal quantum efficiency (IQE) in the solid state, approaching 100% 7 ' 8 ' 14-16 ' 18-22 , even though EQE does not reach ca. 50%.

There is a need for alternative compositions to overcome or mitigate at least some of the deficiencies of the prior art, or to provide a useful alternative.

Summary

In accordance with an aspect, there is provided a

Other features and advantages of the present invention will become apparent from the following detailed description. It should be understood, however, that the detailed description and the specific examples while indicating embodiments of the invention are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from said detailed description.

Description of the Figures

The present invention will be further understood from the following description with reference to the Figures, in which:

Figure 1 (A) shows the asymmetric unit of the organometallic complex based on cadmium (II), aminopyrazine and acetate. Thermal ellipsoids at a 50% probability represent atoms, except for hydrogen atoms (represented as spheres of arbitrary radius). In addition, two disordered sites were found for the nitrogen atom of the amino group, which were freely refined with an occupancy factor rate of about 50% each. Figure 1 (B) shows an expanded one- dimensional polymer chain along the Cd-N1 bond. The hydrogen atoms were hidden for clarity. Figure 1 (C) shows the crystal structure drawing of [Cd(C4H 4 N 3 )( C2H 3 02)2(H 2 0)] n . Cyan dashed lines outline hydrogen bonds. CH hydrogens and NH2 group fraction with 48.0(2)% occupancy, which is bonded to carbon vicinal to that holding the shown 52.0(2)% NH 2 sites, were omitted for clarity.

Figures 2 (A) and 2 (B) show the photoluminescent spectra of the organometallic complex of the present invention with observed and normalized intensities, respectively. The internal and external quantum yields were calculated and measured 74.64 ± 0.02% and 55.0 ± 0.1 %, respectively.

Figure 3 shows a chromaticity diagram. It is noted that the organometallic complex based on cadmium (II), aminopyrazine and acetate exhibits a very saturated and pure blue color.

Figure 4 shows the diffuse reflectance spectrum of the organometallic complex based on cadmium (II), aminopyrazine and acetate.

Figure 5 (A) shows a photoluminescence emission spectrum of the

[Cd(C 4 H4N3)(C2H 3 02)2(H20)]n crystals under excitation at 365 nm. Figure 6 (B) shows CIE 1931 color coordinates of the PL emission, represented by the blue star symbol.

Figure 6 (A) shows a photograph of a flask containing the cadmium (ll)-based complex, aminopyrazine and acetate taken under normal light. Figure 6 (B) shows a photograph of the flask in a darkroom under UVA light, but with the lid of the instrument blocking the UVA light. Figure 6 (C) shows a photograph of the flask in a darkroom under UVA light at 366nm.

Figure 7 (A) shows a photograph of 5mg of the cadmium (ll)-based complex diluted in 1 mL of water (right). The left microtube was used as a control and contained only distilled water. Figure 7 (B) shows a photograph of 5mg of the cadmium (ll)-based complex diluted in 1 mL of 96% ethanol (right). The left microtube was used as a control and contained only 96% ethanol.

Figure 8 shows serial dilution of the cadmium (ll)-based complex in water (1 :2 up to 1 : 262144) under a UVA light (wavelength 365 nm, 6W).

Detailed Description

Described herein, in aspects, are novel bright deep-blue emitting crystal forms based on a simple cadmium coordination polymer with an impressive EQE of 75.4%, which means, at least up to now, the most efficient photoluminescent material in the solid state for the fabrication of blue OLED devices. Furthermore, its synthesis is achieved at room temperature in one solution preparation step needing only low cost reagents (cadmium acetate dihydrate and aminopyrazine in equimolar ratio) and vehicle (ethyl alcohol), followed by slow vehicle evaporation and isolation of the monophasic product crystalline material, adding still more attractive advantages to this material. Definitions

For purposes herein, the chemical elements are identified in accordance with the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 75 th Ed., inside cover, and specific functional groups are generally defined as described therein.

Additionally, general principles of organic chemistry, as well as specific functional moieties and reactivity, are described in Organic Chemistry, Thomas Sorrell, University Science Books,

Sausalito, 1999; Smith and March March's Advanced Organic Chemistry, 5 th Edition, John Wiley & Sons, Inc., New York, 2001 ; Larock, Comprehensive Organic Transformations, VCH

Publishers, Inc., New York, 1989; Carruthers, Some Modern Methods of Organic Synthesis, 3 rd Edition, Cambridge University Press, Cambridge, 1987.

In understanding the scope of the present application, the articles "a", "an", "the", and

"said" are intended to mean that there are one or more of the elements. Additionally, the term "comprising" and its derivatives, as used herein, are intended to be open ended terms that specify the presence of the stated features, elements, components, groups, integers, and/or steps, but do not exclude the presence of other unstated features, elements, components, groups, integers and/or steps. The foregoing also applies to words having similar meanings such as the terms, "including", "having" and their derivatives.

It will be understood that any aspects described as "comprising" certain components may also "consist of" or "consist essentially of," (or vice versa) wherein "consisting of" has a closed-ended or restrictive meaning and "consisting essentially of" means including the components specified but excluding other components except for materials present as impurities, unavoidable materials present as a result of processes used to provide the components, and components added for a purpose other than achieving the technical effect of the invention. For example, a composition defined using the phrase "consisting essentially of" encompasses any known pharmaceutically acceptable additive, excipient, diluent, carrier, and the like. Typically, a composition consisting essentially of a set of components will comprise less than 5% by weight, typically less than 3% by weight, more typically less than 1 % by weight of non-specified components. It will be understood that any component defined herein as being included may be explicitly excluded from the claimed invention by way of proviso or negative limitation, such as any specific compounds whether implicitly or explicitly defined herein.

In addition, all ranges given herein include the end of the ranges and also any intermediate range points, whether explicitly stated or not.

Finally, terms of degree such as "substantially", "about" and "approximately" as used herein mean a reasonable amount of deviation of the modified term such that the end result is not significantly changed. These terms of degree should be construed as including a deviation of at least ±5% of the modified term if this deviation would not negate the meaning of the word it modifies.

Complexes

The organometallic complex [Cd(C4H 4 N 3 )( C2H 3 02)2(H 2 0)] n is an infinite 1 D coordination polymer made up of Cd 2+ transition metal ions spaced by 7.5660(4) A through an

aminopyrazine (Figure 1 ). Each Cd 2+ center is seven-coordinated by two nitrogens from two bidentate aminopyrazine molecules, four oxygens from two bidentate acetate anions and one oxygen atom from one water molecule. Its coordination geometry can be described as somewhat distorted pentagonal bipyramidal, with oxygens forming the distorted basal plane [root-mean square deviation (RMSD) from the least-square plane calculated through them of 0.272 A] and the nitrogens occupying the axial positions. Therefore, acetate anions are almost perpendicular to aminopyrazine. The angles between their mean planes range from 83.38(17)° to 86.14(18)°. The bond angles O— Cd— O around the metal ion range from 83.66(9)° to 86.24(9)° while the N— Cd— N angle measures 175.33(12)°. The Cd— O aC et coordination bonds range between 2.360(2) A and 2.464(2) A, while the Cd— O w coordination bond measures 2.273(3) A. The Cd— N a m P yz coordination bonds measure 2.398(3) A.

As aforementioned, this complex can be described as a polymeric structure formed by

[Cd(C4H 4 N3)(C2H 3 02)2(H20)]n units, which can be expanded by means of the Cd— N

coordination bond (Figure 1 ). Furthermore, all hydrogen bonding functionalities are saturated in this structure. There is a classical intramolecular hydrogen bond between the amine group and one acetate anion. The amine group is also an intermolecular hydrogen bonding donor to another acetate anion from a neighboring chain packed perpendicular to the [010] with a rise of 2.15 A normal to the [201 ] (Figure 1 ). Even though the amine group is disordered over two occupancy site sets, both of them have the same contact pattern with slight differences in their metrics, which is reflected in their similar refined site occupancy factors (52.0(2)% and 48.0(2)%). Polymeric chains packed perpendicular to the [010] are also strongly kept in contact through hydrogen bonds between water and acetate ligands, which propagate infinitely along the [001 ] (Figure 1 ). These two patterns of intermolecular hydrogen bonds bearing either amine or water as donors to acetate ligands alternate perpendicularly to the [010] and give rise to a 3D network of strongly hydrogen bonded polymeric chains.

Thus, described herein is a coordination complex of Formula (I):

Formula (I) In Formula I, is a coordinate bond; M is a metal; Xi, X2, X3, X4, X5, Χε, and X7 are each independently selected from a heteroatom; R 1 , R 2 , R 3 , R 4 , R 7 , and R 8 are each

independently selected from H and a saturated or unsaturated, substituted or unsubstituted, cyclic or linear hydrocarbon comprising from 1 to 8 carbon atoms; R 5 and R 6 are each independently selected from H and a saturated or unsaturated, substituted or unsubstituted, cyclic or linear hydrocarbon comprising from 1 to 8 carbon atoms; and n is an integer.

Typically, M is a metal selected from the group consisting of Zn, Cd, Hg, and a transition metal with 2 valence electrons and, more typically, M is Cd.

Typically, at least one of Xi and X2 is N and, more typically, Xi and X2 are both N.

In typical aspects, X3, X4, X5, Χε, and X are each independently selected from the group consisting of O, S, and Se. For example, in certain aspects, at least one of X3, X4, X5, Χε, and X7 is O. In aspects, X3, X4, X5, Χε, and X are the same and thus, in certain aspects, each of X3, X4,

Typically, at least one of R\ R 2 , R 3 , R 4 is NH 2 . In certain aspects, one of R\ R 2 , R 3 , R 4 is NH 2 and three of R\ R 2 , R 3 , R 4 are H. The NH 2 may be disordered over two occupancy sites, typically with an occupancy factor of about 50%. In typical aspects, at least one of R 5 and R 6 is CH 3 and, in other aspects, R 5 and R 6 are both CH 3 .

Typically, at least one of R 7 and R 8 is H and, in other aspects, R 7 and R 8 are both H.

In certain aspects, n is 1 . In other aspects, n is from about 1 to about 100, such as from about 1 to about 75, such as from about 1 to about 50, such as from about 1 to about 25, such as from about 1 to about 20, such as from about 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, or 19 to about 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19, or 20.

In particular aspects, the coordination complex is of Formula (II):

Formula (II)

In other particular aspects, the coordination complex is of Formula (III):

Formula (III) In other particular aspects, the coordination complex comprises the formula [Cd(C4H 5 N3)(C2H 3 02)2(H20)]n, wherein n is an integer, for example, the coordination complex may comprise the formula [Cd(aminopyrazine)(acetate)2(H 2 0)] n .

As will be understood, the coordination complex described herein may comprise a central metal atom coordinated by a nitrogen atom of aminopyrazine, two bidentate ligands, and an oxygen atom of water. The bidentate ligands may be selected from formate and acetate and, optionally, at least one oxygen atom may be substituted with S or Se.

Coordination Polymers and Crystalline Compounds

The coordination complexes described herein may be polymerized to result in a coordination polymer. The coordination polymer typically forms a one-dimensional polymer chain.

Typically, the coordination polymers form a crystalline compound. The crystalline compound is typically of the following structure:

Further described herein is a blue emitting crystal form based on a cadmium

coordination polymer comprising an external quantum efficiency of greater than 70%.

Also described herein is a crystalline compound comprising the following powder X-ray diffraction pattern:

t eta

The crystalline compound described herein may also be defined in terms of its x-ray diffraction peaks. For example, the crystalline compound described herein may have x-ray diffraction peaks at the following 2Θ positions, within a ±0.200° range: (peaks with normalized intensities equal or higher than 10% are listed)

8.105;

12. .474;

13. .184;

13. .797;

14. .327;

15. .347;

16. .251 ;

16. .979;

20. .127;

23. .857;

24. .068

24. .327

26. .546

34. .253

35. .462

36. .063

36. .233

36. .868 37.148

and

39.641 . OLED Devices

The compounds described herein are particularly useful in a light-emitting layer of OLED technology. To this regard, the compounds can be employed in many OLED device

configurations using small molecule materials, oligomeric materials, polymeric materials, or combinations thereof. These include very simple structures comprising a single anode and cathode to more complex devices, such as passive matrix displays comprised of orthogonal arrays of anodes and cathodes to form pixels, and active-matrix displays where each pixel is controlled independently, for example, with thin film transistors (TFTs).

There are numerous configurations of the organic layers wherein the compounds described herein can be successfully practiced. Typical OLEDs require an anode, a cathode, and an organic light-emitting layer located between the anode and cathode. Additional layers may be employed as will be understood by a skilled person.

For example, a typical OLED is comprised of a substrate, an anode, a hole-injecting layer, a hole-transporting layer, a light-emitting layer, a hole- or exciton-blocking layer, an electron-transporting layer, and a cathode. Typically, an exciton-blocking layer on the anode side of the light-emitting layer and/or a hole-blocking layer on the cathode side of the light emitting layer are included as well. These layers are described in more detail below. Note that the substrate may alternatively be located adjacent to the cathode, or the substrate may actually constitute the anode or cathode. The organic layers between the anode and cathode are conveniently referred to as the organic EL element. Also, the total combined thickness of the organic layers is typically less than 500 nm.

Typically, the anode and cathode of the OLED are connected to a voltage/current source through electrical conductors. The OLED is operated by applying a potential between the anode and cathode such that the anode is at a more positive potential than the cathode. Holes are injected into the organic EL element from the anode and electrons are injected into the organic EL element at the cathode. Enhanced device stability can sometimes be achieved when the OLED is operated in an AC mode where, for some time period in the cycle, the potential bias is reversed and no current flows. Other Uses

The compounds described herein have been identified as being particularly useful, in aspects, in OLED devices. However, it will be understood that these compounds may be used in any manner in which conventional UV-activated compounds are used. For example, in aspects, the compounds described herein find use as a research tool, in diagnostics, in various items such as toys, dolls, card games, paints, textiles, balloons, cosmetics, and foodstuffs or any other article or composition designed to glow illuminated with light of an appropriate wavelength. In such aspects, the compounds described herein may be used as a monomer or an oligomer. Such an oligomer may have from about 2 to about 20 monomer units, such as from about 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, or 19 monomer units to about 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19, or 20 monomer units.

For example, the compounds described herein in aspects may be used in novelty items designed for entertainment, recreation and amusement, and include, but are not limited to: toys, such as squirt guns, toy cigarettes, toy "Halloween" eggs, footbags and board/card games; finger paints and other paints, slimy play material; textiles, such as clothing, such as shirts, hats and sports gear suits, threads and yarns; bubbles in bubble making toys and other toys that produce bubbles; balloons; figurines; personal items, such as cosmetics, bath powders, body lotions, gels, powders and creams, nail polishes, make-up, hair colorants or hair conditioners, mousses or other such products, toothpastes and other dentifrices, soaps, body paints, and bubble bath; items such as inks, paper; foods, such as gelatins, icings and frostings; fish food; plant food; and beverages, such as beer, wine, champagne, soft drinks, and ice cubes and ice in other configurations; fountains, including liquid "fireworks" and other such jets or sprays or aerosols of compositions that are solutions, mixtures, suspensions, powders, pastes, particles or other suitable form.

Any article of manufacture that can be combined with a light-emitting compounds described herein and thereby provide entertainment, recreation and/or amusement, including use of the items for recreation or to attract attention, such as for advertising goods and/or services that are associated with a logo or trademark is contemplated herein. Such uses may be in addition to or in conjunction with or in place of the ordinary or normal use of such items. As a result of the combination, the items glow or produce, such as in the case of squirt guns and fountains, a glowing fluid or spray of liquid or particles in the presence of UV light. The novelty in the novelty item in aspects derives from its light emission.

Methods for diagnosis and visualization of tissues in vivo or in situ using compositions containing the compounds described herein are also contemplated in aspects. For example, the compounds described herein can, in aspects, be used in conjunction with diagnostic systems that rely on fluorescence for visualizing tissues in situ. Such systems are typically useful for visualizing and detecting neoplastic tissue and specialty tissue, such as during non-invasive and invasive procedures.

The systems typically include compositions containing conjugates that include a tissue specific, such as a tumor-specific, targeting agent linked to one or more than one compound described herein. In other aspects, tissue-specific targeting agents are linked to microcarriers that are coupled with, one or more than one compound described herein. The compounds may be linked directly to a peptide, such as an antibody or antigen, or may be linked through use of a functional agent or bifunctional agent.

Thus, in aspects, compounds described herein may be fused or otherwise coupled to antibodies directed to target tissues in plants or animals. For example, it may be desirable to label tumors in animals and to follow metastases by coupling the compound described herein to cells within the tumor. The compounds described herein may be prepared as conjugates with moieties which are able to target tissues or cells. Typical targeting moieties are specific binding partners for a material displayed on tissues or cells. Typical targeting moieties are antibodies and ligands for receptors.

The compounds described herein may also be used to label reagents in assays such as immunoassays. In one example, a sandwich assay may be employed wherein one specific binding partner to an analyte is a capture moiety which immobilizes the analyte and a second specific binding partner is used to label the immobilized analyte. The compounds described herein may be used directly as a label on the labeling binding partner or on a secondary binding partner such as, for example, the use of a second antibody-bearing label to couple to a first antibody directly bound to analyte.

In other aspects, methods for diagnosing diseases, particularly infectious diseases, using chip methodology involving the compounds described herein are provided. In particular, the chip typically includes an integrated photodetector that detects the photons emitted by the fluorescence-generating system. In one aspect, the chip is made using an integrated circuit with an array, such as an X-Y array, of photodetectors. The surface of the circuit is treated to render it inert to conditions of the diagnostic assays for which the chip is intended, and is adapted, such as by derivatization for linking molecules, such as antibodies. A selected antibody or panel of antibodies, such as an antibody specific for a bacterial antigen, is affixed to the surface of the chip above each photodetector. After contacting the chip with a test sample, the chip is contacted with a second antibody linked to a compound described herein. If any of the antibodies linked to a component of a fluorescence-generating system are present on the chip, light will be generated and detected by the photodetector. The photodetector is operatively linked to a computer, which is programmed with information identifying the linked antibodies, records the event, and thereby identifies antigens present in the test sample.

Other assays using the compounds described herein are also contemplated. Any assay or diagnostic method known used by those of skill in the art that employs fluorescent molecules is contemplated herein.

Thus, antibodies or peptides conjugated to the compounds described herein are also provided. These antibodies, monoclonal or polyclonal, and peptides can be prepared employing standard techniques, known to those of skill in the art.

It will be understood that the compounds described herein may be used in addition to other light emitting systems, such as bioluminescence or fluorescence, to enhance or create an array of different colors. For example, they may be used in combinations such that the color of, for example, a beverage changes over time, or includes layers of different colors.

It will be understood that any compounds or compositions described herein for medical, diagnostic, topical, or ingestible use should be pharmaceutically acceptable and therefore nontoxic and safe to apply to the area in which it is intended, such as the skin, hair, and/or eyes and/or to ingest.

The foregoing applications are merely exemplary. In general, the compounds described herein can be used in any application where fluorescent labels are employed, including assay modifications such as fluorescence polarization and fluorescence quenching assays, flow cytometry, fluorescence activated cell sorting, immunofluorescence assays, and point of care devices.

Kits

Kits containing the compounds described herein for use in the methods, including those described herein, are provided. In one aspect, kits containing an article of manufacture and appropriate reagents for generating fluorescence are provided. In aspects, the kits contain soap compositions, with typically a moderate pH, such as between about 5 and about 8, and a UV light source, such as a black light, are provided herein. These kits, for example, can be used with a bubble-blowing or producing toy. These kits can also include a reloading or charging cartridge or can be used in connection with a food.

In another aspect, the kits are used for detecting and visualizing neoplastic tissue and other tissues and include a composition that contains the compound described herein. The compounds described herein may be "ready-to-use" or they may be in prodrug form, requiring an activating agent in order to emit light in response to UV excitation. Thus, in aspects, these kits may include two compositions, a first composition containing the compound formulated for systemic administration (or in some aspects local or topical application), and a second composition containing the component or components required to render the compound reactive to UV Light. Instructions for administration will be included in aspects.

In other aspects, the kits are used for detecting and identifying diseases, particularly infectious diseases, for example by using multi-well assay devices and include a multi-well assay device containing a plurality of wells, each having an integrated photodetector, to which an antibody or panel of antibodies specific for one or more infectious agents are attached, and a composition containing a secondary antibody, such as an antibody specific for the infectious agent that is linked to a compound described herein, which, in the presence of UV light, emits blue light that is detected by the photodetector of the device to indicate the presence of the infectious agent.

The above disclosure generally describes the present invention. A more complete understanding can be obtained by reference to the following specific Examples. These

Examples are described solely for purposes of illustration and are not intended to limit the scope of the invention. Changes in form and substitution of equivalents are contemplated as circumstances may suggest or render expedient. Although specific terms have been employed herein, such terms are intended in a descriptive sense and not for purposes of limitation.

Examples

Example 1 -Synthesis of Complex

About 41 .2 mg of aminopyrazine was dissolved in 10 ml of ethyl alcohol at room temperature and the mixture was stirred until it was completely dissolved. Meanwhile, 20.4 mg of doped cadmium (II) acetate was dissolved in 10 ml of distilled water. Subsequently, the two solutions were mixed and held at 25 °C until the solvent evaporated, resulting in a crystalline solid identified as complex 1 .

All reflections data were collected on an APEX II CCD detector of a Bruker-AXS Kappa

Duo diffractometer using MoKa radiation from an 1 μ≤ microsource with multilayer optics. The structure was solved by direct methods of phase retrieval and then refined by full-matrix least squares on F 2 with anisotropic thermal parameters for all non-hydrogen atoms while the hydrogen atoms had their displacement parameters fixed and set to isotropic ( Uiso(H) = 1 .2 U;q(CH or NH 2 ) or 1 .5U;q(water or CH 3 ). The hydrogen positions were either calculated and constrained following a riding model or located from the difference Fourier map and then fixed (water hydrogens only). Also, the NH 2 group was found to be disordered over two sites sets whose nitrogen occupancies were refined freely and then imposed to their corresponding hydrogens.

Using a powder X-ray diffraction technique, it was confirmed that complex 1 was quantitatively synthesized, / ' . e., near 100% yield, as a substantially pure monophasic crystalline solid, with negligible crystalline or amorphous impurities such as side products or non- consumed reagents. This was determined through the superimposition of all observed diffraction peaks to corresponding ones predicted by the elucidated single crystal structure.

Example 2 - Fluorescence Spectrum and Complex Quantum Yield

The fluorescence emission spectrum for the solid sample of complex 1 was measured using a Fluorolog FL3-221 Horiba Jobin-Yvon fluorimeter. Measurements were made of the excitation spectrum of this sample in the 200 to 280 nm range and the emission spectrum of 280 to 700 nm. The solid sample was glued to the support and positioned at 45 ° to the front- side cell.

For the quantum yield calculations, the average of three excitation spectrum readings of the complex 1 sample in the 276 nm range and the 400 nm emission was averaged.

Subsequently, the area of the spectrum curve obtained using the software of the fluorimeter itself was calculated. The quantum yield measurements were taken from the light absorption measurements of the samples and luminescence emission measurements of the standards and samples. The internal quantum yield of the sample (φϊηί) was determined by comparison with the quantum yield of the barium sulfate used as standard, according to the equation below: where:

R1 = Area of absorption spectrum curve of BaSC sample;

R2 = Curve area of the absorption spectrum of the complex 1 sample;

E1 = Area of the sample emission curve of BaSC ; and

E2 = Area of the emission spectrum curve of the complex 1 sample. Example 3 - Photoluminescence Emission Spectrum

Photoluminscence(PL) measurements were recorded using a double monochromator and a Hamamatsu photomultiplier tube as detector (Fluorolog FL3-221 from Horiba Jobin- Yvon), under excitation from a Xe arc lamp delivering 450 W. To this equipment, was coupled by means optical fibers, an integrating sphere (Quanta-D from Horiba Jobin-Yvon) of

Spectralon™. The excitation reflectance and emission spectra were collected, using the entrance andexit slits fixed at 0.8 nm bandpass, and each emission spectra point was collected at each 1 .0 nm. The IQE, EQE, and emission color coordinates values were determined by means of the FluorEssence V3.5 software, furnished with the Fluorolog FL3-221

spectrofluorimeter and Quanta-φ integrating sphere from Horiba Jobin-Yvon.

Photoluminescence excitation and emission spectra were recorded using a double monochromator and a Hamamatsu photomultiplier tube as detector (Fluorolog FL3-221 from Horiba Jobin-Yvon), under excitations from a Xe arc lamp delivering 450 W. The bandpass was fixed at 0.7 nm, and each point was collected at each 0.7 nm. The emission color coordinates were determined using the experimental setup based on the PL emission spectra recorded by an integrating sphere and the software FluorEssence V 3.5 furnished with the spectrofluorimeter (Fluorolog FL3-221 , Horiba Jobin-Yvon).

In Figure 5(a), the photoluminescence (PL) emission spectrum is presented under an excitation wavelength of 365 nm. The excitation spectrum was acquired monitoring the emission at 410 nm, which resulted in a broad band emission between 370 nm and 520 nm (ultraviolet, violet, blue and green emissions), with the maximum at 410 nm corresponding to deep-blue color (colorimetric coordinates x = 0.167 and y = 0.037; for blue color x = 0.17 and y = 0.00). The colorimetric coordinates of our sample were included in the CIE 1931 chromaticity diagram of the Figure 5(b).

An impressive EQE of 75.4(9)% was observed with a corresponding IQE of 77.7(9)%. To the best of our knowledge, an EQE of approximately 64% has been achieved for green phosphorescent OLEDs, 23 while this value attained 37% for blue thermally activated delayed fluorescence (TADF) OLEDs. 16

Thus described herein is a solid state material with the highest energy conversion rate from UV to visible light known thus far. The next steps will consist of fabricating high- performance blue OLED devices with this crystal form. Example 4 - Naked Eye Visible Light Emission

About 13.7 mg of aminopyrazine was dissolved in 3 ml of ethyl alcohol at room temperature and the mixture was stirred until it was completely dissolved. Meanwhile, 6.8 mg of doped cadmium (II) acetate was dissolved in 10 ml of distilled water. Subsequently, the two solutions were mixed. The mixture was transfer to a glass flask and held at 25 °C until the solvent evaporated. The flask containing the crystals was then place under UVA light

(wavelength 365 nm, 6W). A clear blue light was visible to the naked eye, as shown in Figures 6a, 6b, and 6c.

Example 5 - Naked Eve Visible Light Emission - Solubilization

About 5 mg of complex 1 was diluted in 1 mL of distilled water or 96% ethanol. After 5 min under agitation the vials containing the solubilized compounds (water or ethanol) were place under a UVA light (wavelength 365 nm, 6W). A control vial containing only the solvent was used as a control. A clear blue light was visible to the naked eye. Figure 7a shows complex 1 dissolved in water and Figure 7b shows complex 1 dissolved in ethanol).

Example 6 - Naked Eye Visible Light Emission - Solubilization Using Limiting Dilution

About 5 mg of complex 1 was diluted in 1 mL of distilled water. After 5 min under agitation, the solubilized complex was serially diluted with water as shown in Table 1 below. After dilution, the microtubes containing the diluted complex were place under a UVA light (wavelength 365 nm, 6W) as shown in Figure 8.

Table 1 : Serial dilution of complex 1 .

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The above disclosure generally describes the present invention. Although specific terms have been employed herein, such terms are intended in a descriptive sense and not for purposes of limitation.

All publications, patents and patent applications cited above are herein incorporated by reference in their entirety to the same extent as if each individual publication, patent or patent application was specifically and individually indicated to be incorporated by reference in its entirety.

Although preferred embodiments of the invention have been described herein in detail, it will be understood by those skilled in the art that variations may be made thereto without departing from the spirit of the invention or the scope of the appended claims.