Boron-containing cyclic releasing compound and color conversion film containing the same

Abstract

The present disclosure relates to novel photoluminescent complexes comprising a BODIPY moiety covalently attached to a blue light absorbing xanthenoisoquinoline derivative, and color conversion films and backlight units employing same.

Description

[Technical field]

[0001] [CROSS REFERENCE TO RELATED APPLICATIONS] This application claims priority to U.S. Provisional Patent Application No. 63 / 311,640, filed February 18, 2022, and U.S. Provisional Patent Application No. 63 / 346,756, filed May 27, 2022, the entire disclosures of which are incorporated herein by reference.

[0002] The present disclosure relates to compounds used in color conversion films, as well as backlight units and display devices comprising the color conversion films. [Background technology]

[0003] Unless otherwise indicated in this disclosure, the materials described in this disclosure are not prior art to the claims of this application and are not admitted to be prior art by inclusion in this section.

[0004] In color reproduction, a 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 realized by using pure spectral primaries, was developed to provide a larger color gamut and result in a more realistic representation of visible colors viewed through a display. It is believed that devices that can provide a wider gamut may enable displays to depict more vivid colors.

[0005] As high-definition large-screen displays become more common, there is an increasing demand for displays with higher performance, thinner and more advanced features. Current light-emitting diodes (LEDs) are obtained by exciting a blue light source with a green, red or yellow phosphor to obtain a white light source. However, the full width at half maximum (FWHM) of the emission peaks of current green and red phosphors is very large, usually exceeding 40 nm, resulting in overlapping of the green and red spectra, resulting in color rendering that is completely indistinguishable from each other. This overlap leads to poor color rendering and a reduced color gamut.

[0006] To compensate for the loss of color gamut, a method has been developed to use films containing quantum dots in combination with LEDs. Quantum dots have a number of drawbacks, including toxicity, low efficiency, expensive encapsulation processes, and size uniformity.

[0007] Therefore, a need exists for improved performance in color conversion films, backlight units, and display devices. Summary of the Invention

[0008] The photoluminescent complexes described herein can be used to improve the contrast between distinguishable colors in televisions, computer monitors, smart devices, and any other devices that utilize color displays. The photoluminescent complexes of the present disclosure provide novel color conversion dye complexes with good blue light absorption and narrow emission bandwidths, with full width at half maximum (FWHM) of the emission band less than about 40 nm. In some embodiments, the photoluminescent complexes absorb light at a first wavelength and emit light at a second wavelength that is longer than the first wavelength. The photoluminescent complexes disclosed herein can be utilized in color conversion films used in light emitting devices. The color conversion films of the present disclosure reduce color degradation by reducing overlap in the color spectrum, resulting in high quality color rendering.

[0009] In some embodiments, the photoluminescent complexes described herein can include a blue light absorbing xanthenoisoquinoline derivative, a linker conjugate that is an unsubstituted ester or a substituted ester, and a boron-dipyrromethene (BODIPY) moiety, where the linker conjugate covalently bonds the xanthenoisoquinoline derivative and the BODIPY moiety, where the xanthenoisoquinoline derivative absorbs light energy at a first excitation wavelength and transfers the energy to the BODIPY moiety, where the BODIPY moiety absorbs energy from the xanthenoisoquinoline derivative and emits light energy at a second, longer wavelength, and where the photoluminescent complex has an emission quantum yield of greater than 80%.

[0010] In some embodiments, the xanthenoisoquinoline derivative has the general formula: [ka] (In the formula, R 10 can be a bond, H, a C1-C4 alkyl group, or an optionally substituted aryl group. In some embodiments, the optionally substituted aryl group is [ka] In some embodiments, the BODIPY moiety can include Formula 1 or Formula 2, as shown below: [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 are independently H, a C1-C3 alkyl, an optionally substituted aryl group, or an optionally substituted ether group; R 7 , R 8 , and R 9 are independently H or a methyl group (-CH3), L1, L2, and L3 are linker complexes and may independently comprise an optionally substituted ester moiety.

[0011] In some embodiments, R 3 and R 4 may each be an aryl group, such as a phenyl group. In some embodiments, the aryl group may be an optionally substituted aryl group. In some embodiments, the optionally substituted aryl group may be [ka] In some embodiments, the optionally substituted aryl group can be: [ka] may include.

[0012] In some embodiments, linker conjugates L1, L2, and L3 are independently [ka] It could be.

[0013] In some embodiments, linker conjugates L1, L2, and L3 are independently [ka] It could be.

[0014] In some embodiments, the color conversion film may include a transparent substrate layer and a color conversion layer. In some embodiments, the color conversion layer may include a resin matrix including poly(butyl acrylate) or poly(methyl methacrylate) and a photoluminescent complex including a compound described herein dispersed within the resin matrix. In some embodiments, the color conversion film may further include a singlet oxygen quencher. In some embodiments, the color conversion film may further include a free radical scavenger. In some embodiments, the color conversion film may have a thickness between 10 μm and 200 μm. In some embodiments, the film may absorb light in a wavelength range of about 400 nm to about 590 nm and emit light in a wavelength range of about 600 nm to about 620 nm.

[0015] In some embodiments, a method of preparing a color conversion film is described, which may include dissolving a photoluminescent complex of the above embodiments and a binder resin in a solvent and applying the mixture to one of the opposing surfaces of a transparent substrate.

[0016] In some embodiments, a backlight unit is described, which can include the color conversion film described above.

[0017] In some embodiments, a display device is described, which may include the backlight unit described above.

[0018] The present application provides a photoluminescent complex having excellent color gamut and luminescence properties, a method for manufacturing a color conversion film using the photoluminescent complex, and a backlight unit including the color conversion film. These and other embodiments are described in more detail below. [Brief description of the drawings]

[0019] [Figure 1]1 is a graph showing the absorption and emission spectra of one embodiment of a photoluminescent complex (compound 5). [Diagram 2] 1 is a graph showing the absorption and emission spectra of one embodiment of a photoluminescent complex (compound 6). [Diagram 3] 1 is a graph showing the absorption and emission spectra of one embodiment of a photoluminescent complex (compound 7). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0020] The present disclosure includes photoluminescent complexes and their use in color conversion films, backlight units, and / or display devices. Photoluminescent complexes can be used to improve and enhance the transmission of one or more desired emission bandwidths in a color conversion film. In some embodiments, the photoluminescent complexes can enhance the transmission of a desired first emission bandwidth and also reduce the transmission of a second emission bandwidth. For example, a color conversion film can enhance the contrast or intensity between two or more colors and enhance their discrimination from one another. The present disclosure describes photoluminescent complexes that can enhance the contrast or intensity between two colors and enhance their discrimination from one another. The present disclosure also includes methods for preparing the color conversion films described herein.

[0021] As used herein, when a compound or chemical structure is referred to as "substituted", it may contain one or more substituents. A substituted group is based on an unsubstituted parent structure, in which one or more hydrogen atoms on the parent structure are independently replaced with one or more substituents. A substituent may have one or more substituents on the parent structure. In one or more forms, the substituents may be independently selected from an optionally substituted alkyl, alkenyl, or C3-C7 heteroalkyl. The term "optionally substituted" includes a parent structure that may or may not be substituted as defined above.

[0022] As used herein, the term "alkyl" group refers to an aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl" group, meaning that it does not contain any alkene or alkyne moieties. The alkyl moiety may also be an "unsaturated alkyl" moiety, meaning that it contains at least one alkene or alkyne moiety. An "alkene" moiety refers to a group having at least one carbon-carbon double bond (-C=C-), and an "alkyne" moiety refers to a group having at least one carbon-carbon triple bond (-C≡C-). The alkyl moiety, whether saturated or unsaturated, may be branched, straight, or cyclic.

[0023] The alkyl moiety may have 1 to 6 carbon atoms (whether or not indicated herein, numerical ranges such as "1 to 6" refer to each integer within the given range, e.g., "1 to 6 carbon atoms" means that the alkyl group may have 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc., up to and including 6 carbon atoms, although this definition also includes the term "alkyl" where no numerical range is specified). The alkyl group of the compounds specified herein may be designated as "C1 to C6 alkyl" or a similar designation. As merely an example, "C1 to C6 alkyl" indicates that there are 1 to 6 carbon atoms in the alkyl chain, i.e., the alkyl chain is methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or t-butyl. Thus, C1 to C6 alkyl includes C1 to C2 alkyl, C1 to C3 alkyl, C1 to C4 alkyl, and C1 to C5 alkyl. The alkyl group may 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.

[0024] As used herein, the term "heteroalkyl" refers to an alkyl group, as defined herein, in which one or more member carbon atoms are replaced by nitrogen, oxygen, or sulfur. 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-CH2-N(CH3)-CH3, -CH2-S-CH2-CH3, -CH2-CH2-S(O)-CH3. Additionally, up to two heteroatoms may be consecutive, such as, for example, -CH2-NH-O-CH3.

[0025] The term "aromatic" refers to a planar ring having a delocalized π-electron system containing 4n+2 (where n is an integer) π-electrons. An aromatic ring may be formed from 5, 6, 7, 8, 9, or 10 or more atoms. An aromatic may be optionally substituted. The term "aromatic" includes both carbocyclic aryl (e.g., phenyl) and heterocyclic aryl (i.e., "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.

[0026] As used herein, the term "aryl" refers to an aromatic ring in which each of the atoms forming the ring is a carbon atom. The aryl ring can be formed by 5, 6, 7, 8, or 9 or more carbon atoms. The aryl group can be substituted or unsubstituted. Examples of aryl groups include, but are not limited to, phenyl, naphthalenyl, phenanthrenyl, and the like.

[0027] 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.

[0028] As used herein, the term "halogen" means fluorine, chlorine, bromine, and iodine.

[0029] The terms "bond," "bonded," "direct bond," or "single bond," as used herein, refer 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.

[0030] The term "moiety" as used herein refers to a specific segment or functional group of a molecule. A chemical moiety is often recognized as a chemical entity embedded within or added to a molecule.

[0031] The term "ester" refers to a chemical moiety having the formula -COOR, where R is an alkyl, cycloalkyl, aryl, heteroaryl (bonded through a ring carbon), and heterocyclic moiety (bonded through a ring carbon). Any hydroxyl or carboxyl side chain on the compounds described herein may be esterified. Any suitable method may be used to prepare the ester.

[0032] Use of the term "may" or "could" should be interpreted as abbreviations of "is" or "is not", alternatively "will" or "will not" or "will not" or "will not". For example, the statement "the binder resin may include poly(methyl methacrylate)" should be interpreted as, for example, "in some embodiments, the binder resin includes poly(methyl methacrylate)" or "in some embodiments, the binder resin does not include poly(methyl methacrylate)".

[0033] As used herein, the term "BODIPY" refers to a compound having the general formula: [ka] BODIPY compounds consist of a dipyrromethene moiety 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.

[0034] As used herein, the term "xanthenoisquinoline" or "xanthenoisquinoline derivative" refers to a compound of the general formula: [ka] The IUPAC name for the xanthenoisoquinoline core is 1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione.

[0035] The present disclosure relates to photoluminescent complexes that absorb light energy at a first wavelength and emit light energy at a second, longer wavelength. The photoluminescent complexes of the present disclosure include an absorbing light-emitting moiety and an emitting light-emitting moiety linked via a linker, the distance between them being optimized so that the absorbing light-emitting moiety transfers its energy to an acceptor light-emitting moiety, which then emits the energy at a second wavelength that is greater than the absorbed first wavelength.

[0036] In some embodiments, the photoluminescent complex described herein comprises a blue light absorbing xanthenoisoquinoline derivative (XI derivative), a linker conjugate, and a boron-dipyrromethene (BODIPY) moiety. In some embodiments, the linker conjugate can covalently link the xanthenoisoquinoline derivative to the BODIPY moiety. In some embodiments, the xanthenoisoquinoline derivative absorbs light at a first excitation wavelength and transfers the energy to the BODIPY moiety, which then emits light energy at a second wavelength that is longer than the first wavelength. The energy transfer from the excited xanthenoisoquinoline derivative to the BODIPY moiety is believed to occur via Förster resonance energy transfer (FRET). This idea is due to the absorption / emission spectrum of the photoluminescent complex, which has two major absorption bands, one in the blue light absorption band (xanthenoisoquinoline derivative) and the other in the BODIPY absorption band, and only one emission band at the emission wavelength of the BODIPY moiety (see Figures 1-3).

[0037] In one embodiment, the photoluminescent complex may have a high emission quantum yield. In some embodiments, the emission quantum yield may be greater than 50%, 60%, 70%, 80%, or 90%. In some embodiments, the emission quantum yield may be greater than 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%. The emission quantum yield may be measured by dividing the number of photons emitted by the number of photons absorbed, which is equal to the emission efficiency of the light-emitting moiety. In some embodiments, the absorbing light-emitting moiety may have an emission quantum yield greater than 80%. In some embodiments, the quantum yield may 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%), 0.95 (95%), or may be up to (100%). Quantum yield measurements on photoluminescent complex films may be performed by a spectrophotometer, for example, a Quantaurus-QY spectrophotometer (Hamamatsu, Inc., Campbell, Calif., USA).

[0038] In some embodiments, the photoluminescent complex has an emission band that may have a full width at half maximum (FWHM) of less than 40 nm. The FWHM is the width of the emission band in nanometers at an emission intensity that is half the maximum emission intensity for the band. In some embodiments, the photoluminescent complex has an emission band FWHM value of about 55 nm or less, about 50 nm or less, about 45 nm or less, about 40 nm or less, about 35 nm or less, about 30 nm or less, about 25 nm or less, about 20 nm or less, or about 39 nm, about 40 nm, or about 41 nm.

[0039] In some embodiments, the photoluminescent complex may have a Stokes shift of 45 nm or more. As used herein, the term "Stokes shift" refers to the distance between the excitation peak of a photoluminescent complex (or a portion thereof) and the emission peak of the photoluminescent complex (or a portion thereof). In some embodiments, the Stokes shift of the photoluminescent complex may be about 45 nm to 50 nm, about 50 nm to 55 nm, about 55 nm to 60 nm, about 60 nm to 65 nm, about 65 nm to 70 nm, about 70 nm to 75 nm, about 75 nm to 80 nm, about 80 nm to 85 nm, about 85 nm to 90 nm, about 90 nm to 95 nm, about 95 nm to 100 nm, or more than about 100 nm, or any number within the range defined by any of these values. In some embodiments, the Stokes shift of the photoluminescent complex can be greater than 100 nm, greater than 120 nm, greater than 130 nm, greater than 140 nm, greater than 150 nm, or greater than 170 nm. For example, the Stokes shift between the blue light absorbing moiety and the emission peak of the BODIPY moiety can be any number or range disclosed herein.

[0040] The photoluminescent complexes of the present disclosure may have tunable emission wavelengths, which may be tuned to between about 600 nm and about 645 nm by incorporating different substituents on the BODIPY moiety.

[0041] In some embodiments, the photoluminescent complex can absorb light energy at one or more wavelengths. In some embodiments, the xanthenoisoquinoline portion of the photoluminescent complex can absorb light. In some embodiments, the BODIPY portion of the photoluminescent complex can absorb light. In some embodiments, both the BODIPY portion of the photoluminescent complex and the xanthenoisoquinoline portion of the photoluminescent complex can absorb light. In some embodiments, the photoluminescent complex xanthenoisoquinoline moiety may have a peak absorption maximum wavelength between about 400 nm to about 470 nm, about 400 nm to 405 nm, about 405 nm to 410 nm, about 410 nm to 415 nm, about 415 nm to 420 nm, about 420 nm to 425 nm, about 425 nm to 430 nm, about 430 nm to 435 nm, about 435 nm to 440 nm, about 440 nm to 445 nm, about 445 nm to 450 nm, about 450 nm to 455 nm, about 455 nm to 460 nm, about 460 nm to 465 nm, or about 465 nm to 470 nm. In some embodiments, the BODIPY portion of the photoluminescent complex may have a peak absorption maximum wavelength between about 500 nm to about 600 nm, about 500 nm to 510 nm, about 510 nm to 520 nm, about 520 nm to 530 nm, about 530 nm to 540 nm, about 540 nm to 550 nm, about 550 nm to 555 nm, about 555 nm to 560 nm, about 560 nm to 565 nm, about 565 nm to 570 nm, about 570 nm to 575 nm, about 575 nm to 585 nm, about 585 nm to 590 nm, about 590 nm to 600 nm, about 570 nm to 585 nm, or any wavelength within a range defined by any of these values.In some embodiments, the photoluminescent complex has a wavelength of about 400 nm to about 405 nm, about 405 nm to 410 nm, about 410 nm to 415 nm, about 415 nm to 420 nm, about 420 nm to 425 nm, about 425 nm to 430 nm, about 430 nm to 435 nm, about 435 nm to 440 nm, about 440 nm to 445 nm, about 445 nm to 450 nm, about 450 nm to 455 nm, about 455 nm to 460 nm, about 460 nm to 465 nm, about 465 nm to 470 nm, about 500 nm to 600 nm, The absorbance wavelength may be between about 500 nm to 510 nm, about 510 nm to 520 nm, about 520 nm to 530 nm, about 530 nm to 540 nm, about 540 nm to 550 nm, about 550 nm to 555 nm, about 555 nm to 560 nm, about 560 nm to 565 nm, about 565 nm to 570 nm, about 570 nm to 575 nm, about 575 nm to 585 nm, about 585 nm to 590 nm, about 590 nm to 600 nm, about 570 nm to 585 nm, or any wavelength within a range defined by any of these values.

[0042] In another embodiment, the photoluminescent complex may have an emission peak wavelength between about 595 nm to about 645 nm, about 595 to 600 nm, about 600 to 605 nm, about 605 to 610 nm, about 610 nm to 615 nm, about 615 nm to 620 nm, about 620 nm to 625 nm, about 625 nm to 630 nm, about 630 nm to 635 nm, about 635 nm to 640 nm, about 640 nm to 645 nm, about 605 nm to 620 nm, or any wavelength within a range defined by any of these values.

[0043] Other embodiments include photoluminescent complexes, in which the spatial distance between the blue light absorbing xanthenoisoquinoline derivative and the BODIPY moiety is adjusted via a linker conjugate to improve the energy transfer of the blue light absorbing xanthenoisoquinoline derivative to the BODIPY moiety. In some embodiments, the linker conjugate covalently bonds the blue light absorbing xanthenoisoquinoline derivative and the BODIPY moiety. In some embodiments, the xanthenoisoquinoline derivative absorbs light energy at a first excitation wavelength and transfers the energy to the BODIPY moiety, and the BODIPY moiety absorbs energy from the xanthenoisoquinoline derivative and emits light energy at a second, longer wavelength, and the photoluminescent complex has an emission quantum yield of more than 80%.

[0044] In some embodiments, the compound has the general formula: [ka] (In the formula, R 10 are blue light absorbing xanthenoisoquinoline derivatives in which: may be independently H, methyl (-CH3), an optionally substituted alkyl group, or an optionally substituted aryl group. In some embodiments, the optionally substituted alkyl group may be a trifluoromethyl group (-CF3) or a trichloromethyl group (-CCl3). In some embodiments, the optionally substituted aryl group may be a phenyl group. In some embodiments, the optionally substituted aryl group may be a substituted phenyl group or a benzyl group. In some embodiments, the optionally substituted aryl group may include a trifluoromethyl group. In some embodiments, the optionally substituted aryl group may be [ka] It could be.

[0045] In some embodiments, the linker conjugate covalently connects the blue light absorbing xanthenoisoquinoline derivative to the BODIPY moiety. The linker conjugate can be adjusted to optimize the spatial distance between the blue light absorbing xanthenoisoquinoline derivative and the BODIPY moiety. Optimizing the spatial distance between the xanthenoisoquinoline derivative and the BODIPY moiety can improve the quantum yield. In some embodiments, the distance separating the blue light absorbing xanthenoisoquinoline derivative and the BODIPY moiety can be about 8 Å or more. In some embodiments, the linker conjugate maintains the distance between the blue light absorbing xanthenoisoquinoline derivative and the BODIPY moiety.

[0046] In some embodiments, the photoluminescent complex comprises a linker conjugate that covalently attaches the blue light absorbing xanthenylisoquinoline derivative to the BODIPY moiety. In some embodiments, the linker conjugate can comprise a single bond between the xanthenylisoquinoline derivative and the BODIPY moiety.

[0047] In some embodiments, the linker conjugate (e.g., L1, L2 and / or L3) can include an optionally substituted C2-C7 ester group. When the linker conjugate includes a substituted ester group, the linker conjugate has the following structure: [ka] It can be one of the following:

[0048] In some embodiments, the linker conjugate may include an unsubstituted ester group, and the linker conjugate has the following structure: [ka] It can be one of the following:

[0049] It should be understood that linker complexes L1, L2, and L3 may be the same or different. In some embodiments, L1, L2, and L3 may all be the same. In some embodiments, L1, L2, and L3 may all be different. In some embodiments, L1 and L2 may be the same and L3 is different. All possible permutations of linker complexes are contemplated.

[0050] The photoluminescent complexes of the present disclosure may include a BODIPY moiety, which has the following general formula: [ka] may have:

[0051] In some embodiments, R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 is independently selected from a bond, H, C1-C3 alkyl, aryl, or ether. In some embodiments, the aryl group may be substituted. In some embodiments, the substituted aryl group is [ka] In some embodiments, the substituted aryl group can be: [ka] In some embodiments, R 7 , R 8 , and R 9 may be independently selected from a bond, H, or a methyl group (-CH3).

[0052] The BODIPY moiety of the present disclosure is R 3 and R 4 may each be an aryl group, e.g., a phenyl group; R 1 , R 2 , R 5and / or R 6 is a bond, or H, a substituted aryl group, e.g. [ka] It may be a BODIPY moiety which may also be

[0053] Photoluminescent complexes of the present disclosure may be represented by the following structure, which is provided for illustrative purposes and should not be construed as limiting in any way: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] or a combination of any of these compounds.

[0054] It is believed that the compounds described herein may be suitable for combination with poly(butyl acrylate), also known as PBA.

[0055] Some embodiments include a color conversion film that includes a color conversion layer that includes a resin matrix and a photoluminescent complex as described above dispersed within the resin matrix. In some embodiments, the color conversion film can be described as including one or more complexes as described herein.

[0056] Some embodiments include color converting films that can have a thickness of about 1 μm to about 200 μm, about 1 μm to 5 μm, about 5 μm to 10 μm, about 10 μm to 15 μm, about 15 μm to 20 μm, about 20 μm to 40 μm, about 40 μm to 80 μm, about 80 μm to 120 μm, about 120 μm to 160 μm, about 160 μm to 200 μm, or about 10 μm, or any thickness within a range defined by any of these values.

[0057] In some embodiments, the color conversion film may further include a transparent substrate layer. The transparent substrate layer has two opposing surfaces, where the color conversion layer may be disposed on the surface of the transparent layer that is adjacent to the light emitting source and be in physical contact with it. The transparent substrate is not particularly limited, and a person skilled in the art may select a transparent substrate from those used in the art. Some non-limiting examples of transparent substrates include PE (polyethylene), PP (polypropylene), PEN (polyethylene naphthalate), PC (polycarbonate), PMA (polymethyl acrylate), PMMA (polymethyl methacrylate), CAB (cellulose acetate butyrate), PVC (polyvinyl chloride), PET (polyethylene terephthalate), PETG (glycol modified polyethylene terephthalate), PDMS (polydimethylsiloxane), COC (cycloolefin copolymer), PGA (polyglycolide or polyglycolic acid), PLA (polylactic acid), PCL (polycaprolactone), PEA (polyethylene adipate), PHA (polyhydroxyalkanoate), PHBV (poly(3-hydroxybutyrate-co-3-hydroxyvalerate)), PBE (polybutylene terephthalate), PTT (polytrimethylene terephthalate). Any of the aforementioned resins may be the corresponding / respective monomers and / or polymers.

[0058] In some embodiments, the binder resin may include poly(methyl methacrylate), also known as PMMA. In some embodiments, the binder resin may include poly(butyl acrylate), also known as PBA. In some embodiments, the binder resin may be a copolymer mixture including 50%, 75%, 95% butyl acrylate copolymer / monomer. It is believed that compared to PMMA, the poly(butyl acrylate) matrix may provide a more non-polar environment (having n-butyl alkyl chains in the structure). It is believed that the non-polar environment in PBA may cause the chromophore dyes to aggregate or stack with each other in the matrix, facilitating charge transfer, which generally results in a slightly lower quantum yield in PBA.

[0059] In some embodiments, the transparent substrate may have two opposing surfaces. In some embodiments, the color conversion film may be disposed on one of the opposing surfaces and in physical contact with it. In some embodiments, the surface of the transparent substrate on which the color conversion film is not disposed may be adjacent to the light source. The substrate may function as a support during the preparation of the color conversion film. The type of substrate used is not particularly limited, and the material and / or thickness are not limited, as long as it is transparent and can function as a support. A person skilled in the art will be able to determine which material and thickness should be used as the support substrate.

[0060] Some embodiments include a method of making a color conversion film, the method including dissolving a photoluminescent compound described herein and a binder resin in a solvent and applying the mixture to a surface of a transparent substrate.

[0061] Binder resins that can be used with the photoluminescent complex(es) include resins such as acrylic resins, polycarbonate resins, ethylene-vinyl alcohol copolymer resins, ethylene-vinyl acetate copolymer resins and their saponification products, AS resins, polyester resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins, polyvinyl phosphonic acid (PVPA), polystyrene resins, phenolic resins, phenoxy resins, polysulfone, nylon, cellulose 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 binder resin can include polymethacrylate (PMMA). In some embodiments, the binder resin can include poly(butyl acrylate) (PBA).

[0062] Any suitable solvent or combination of solvents may be used to dissolve or disperse the complex and resin. In some embodiments, the solvent is an alkanes 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™. Cellosolve™ acetate, propylene glycol and its derivatives, such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, and dipropylene glycol dimethyl ether, ketones, such as acetone, methyl amyl ketone, cyclohexanone, and acetophenone, ethers, such as dioxane and tetrahydrofuran, The solvent may be toluene, ethyl ether, butyl ether, 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 dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.

[0063] Some embodiments include a backlight unit, which may include the color conversion film described above.

[0064] Other embodiments may include a display device, which may include a backlight unit as described herein.

[0065] Unless otherwise indicated, all numbers expressing properties such as amounts of ingredients, molecular weights, reaction conditions, and the like used in the specification and embodiments should be understood to be modified in all cases by the term "about". Thus, unless indicated to the contrary, the numerical parameters set forth in the specification and accompanying embodiments are approximations that may vary depending on the desired properties sought to be obtained. At least, not as an attempt to limit the application of the doctrine of equivalents. Within 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.

[0066] For the disclosed processes and / or methods, the functions performed in the processes and methods may be realized in various orders, as may be indicated by the context. Moreover, the outlined steps and operations are presented only as examples, and some steps and operations may be optional, combined into fewer steps and operations, or expanded into additional steps and operations.

[0067] This disclosure may at times describe different components contained within or in conjunction with different other components, and such depicted structures are merely exemplary, and many other structures may be realized that achieve the same or similar functionality.

[0068] Generally, the terms used in this disclosure and the accompanying embodiments (e.g., the text of the accompanying embodiments) are 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.). Furthermore, when a specific number of elements is introduced, this may be interpreted to mean at least the number recited, as may be indicated by the context (e.g., the bare recitation of "two descriptions" without other qualifiers means at least two descriptions of two or more descriptions). As used in this disclosure, any disjunction and / or disjunction phrase expressing two or more alternative terms should be understood to contemplate the possibility of including one of the terms, either of the terms, or both terms. For example, the phrase "A or B" will be understood to include the possibilities of "A" or "B" or "A and B."

[0069] The terms "a," "an," "the," and similar referents used in the context of describing this disclosure (particularly in the context of the following embodiments) should be construed to include 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") set forth herein is intended merely to better clarify the disclosure and does not pose a limitation on the scope of any embodiment. Language in this specification should not be construed as indicating any non-embodied element essential to the practice of the disclosure.

[0070] Groupings of alternative elements or embodiments disclosed herein should not be construed as limiting. Each group member may be referenced and embodied individually or in any combination with other members of the group or other elements found herein. It is anticipated that for reasons of convenience and / or patentability, one or more members of a group may be included in or deleted from a group. When such inclusions or deletions are made, the specification is deemed to satisfy the description of all Markush groups used in the appended embodiments, to include the modified group.

[0071] Certain embodiments are described herein, including the best mode known to the inventors for carrying out the present disclosure. Of course, variations of these described embodiments will become apparent to those skilled in the art upon reading the above description. The inventors anticipate that those skilled in the art will use such variations as necessary, and the inventors intend for the present disclosure to be carried out in ways other than as specifically described herein. Thus, the embodiments include all modifications and equivalents of the subject matter described in the embodiments, as permitted by applicable law. Moreover, any combination of the above elements in all possible variations thereof is contemplated, unless otherwise indicated herein or clearly contradicted by context. Finally, it should be understood that the embodiments disclosed herein are illustrative of the principles of the embodiments. Other variations that may be used are within the scope of the embodiments. Thus, by way of example, but not limitation, alternative embodiments may be utilized in accordance with the teachings of the present specification. Thus, the embodiments are not limited to those precisely shown and described.

[0072] Embodiment Embodiment 1 A photoluminescent complex comprising: A blue light absorbing xanthenoisoquinoline derivative; a linker conjugate which is an unsubstituted ester or a substituted ester; a boron-dipyrromethene (BODIPY) moiety; Including, A photoluminescent complex, wherein a linker conjugate covalently bonds a xanthenoisoquinoline derivative and a BODIPY moiety, the xanthenoisoquinoline derivative absorbs light energy at a first excitation wavelength and transfers the energy to the BODIPY moiety, the BODIPY moiety absorbs energy from the xanthenoisoquinoline derivative and emits light energy at a second, longer wavelength, and the photoluminescent complex has an emission quantum yield of greater than 80%.

[0073] Embodiment 2 A xanthenoisquinoline derivative having the general formula: [ka] (In the formula, R 0 is a bond, H, a C1-C4 alkyl group, or an optionally substituted aryl group.

[0074] Embodiment 3 The BODIPY moiety has the general formula: [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 is independently selected from a bond, H, C1-C3 alkyl, aryl, and / or ether; R 7 , R 8 , and R 9 can be independently selected from a bond, H, or a methyl group (-CH3); The photoluminescent complex of embodiment 1, wherein L1, L2, and L3 are independent linker conjugates, which are unsubstituted esters or substituted esters.

[0075] Embodiment 4 R 3 and R 4 The photoluminescent complex of embodiment 3, wherein may include an aryl group.

[0076] Embodiment 5. The photoluminescent complex of embodiment 4, wherein the aryl group comprises a phenyl group.

[0077] Embodiment 6 The photoluminescent conjugate of embodiment 4, wherein the phenyl group comprises a 4-trifluoromethylphenyl group or a 3,5-bis(trifluoromethyl)phenyl group.

[0078] Embodiment 7 A substituted aryl group is [ka] The photoluminescent complex of embodiment 3, which may be:

[0079] Embodiment 8: An ether group [ka] The photoluminescent complex of embodiment 3, which may be:

[0080] Embodiment 9: The linker is [ka] The photoluminescent complex of embodiment 1 may be selected from:

[0081] Embodiment 10: The unsubstituted ester linker is [ka] 10. The photoluminescent complex of embodiment 1, 2, 3, 4, 5, 6, 7, 8, or 9, wherein

[0082] Embodiment 11: The substituted ester of the linker conjugate has the following structure: [ka] 10. The photoluminescent complex of embodiment 1, 2, 3, 4, 5, 6, 7, 8 or 9, wherein

[0083] Embodiment 12. A photoluminescent complex having the following structure: [ka] [ka] [ka] [ka] [ka] [ka] [ka] or a combination thereof.

[0084] Embodiment 13 A color conversion film comprising: A transparent substrate layer; a color conversion layer including a resin matrix including butyl acrylate; At least one photoluminescent complex comprising the photoluminescent compound of embodiment 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12 dispersed in a resin matrix; Including color conversion film.

[0085] Embodiment 14 The color conversion film of embodiment 13, further comprising a singlet oxygen quencher.

[0086] Embodiment 15 The color converting film of embodiment 13, further comprising a free radical scavenger.

[0087] Embodiment 16 The color converting film of embodiment 13, wherein the film has a thickness of between about 10 μm and about 200 μm.

[0088] Embodiment 17 The color conversion film of embodiment 13, wherein the film absorbs light in the wavelength range of about 400 nm to about 600 nm and emits light in the wavelength range of about 575 nm to about 645 nm.

[0089] Embodiment 18 A method of making a color conversion film, comprising the steps of: Dissolving the photoluminescent complex of embodiment 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 and a binder resin in a solvent; applying the mixture to one of the opposing surfaces of a transparent substrate; A method comprising:

[0090] Embodiment 19 A backlight unit comprising the color conversion film of embodiment 13.

[0091] Embodiment 20 A display device comprising the backlight unit of embodiment 19. EXAMPLES

[0092] It has been discovered that embodiments of the photoluminescent complexes described herein have improved performance compared to other forms of dyes used in color conversion films. These advantages are further illustrated by the following examples, which are intended to be merely illustrative of the disclosure and are not intended to limit the scope or underlying principles in any way.

[0093] Example 1.1 Comparative example 1 (CE-1): [ka]

[0094] CE-1: 0.75 g of 4-hydroxyl-2,6-dimethylbenzaldehyde (5 mmol) and 1.04 g of 2,4-dimethylpyrrole (11 mmol) were 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 at room temperature under an argon gas atmosphere. DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoquinone) (2.0 g) was added to the resulting solution, and the mixture was stirred overnight. The next day, the solution was filtered and then washed with dichloromethane to obtain dipyrrolmethane (1.9 g). Then, 1.0 g of dipyrrolmethane was dissolved in 60 mL of THF. 5 mL of trimethylamine was added to the solution, followed by degassing for 10 minutes. After degassing, 5 mL of trifluoroboron-diethyl ether was slowly added, followed by heating at 70°C for 30 minutes. The resulting solution was loaded onto silica gel and purified by flash chromatography using dichloromethane as eluent. The desired fractions were collected and dried under reduced pressure to give 0.9 g of an orange solid (76% yield). LCMS (APCI+): C 21 H 24 Calculated for BF2N2O (M+H)=369; Found: 369. 1 H NMR (400 MHz, chloroform-d) δ 6.64(s, 2H), 5.97(s, 2H), 4.73(s, 1H), 2.56(s, 6H), 2.09(s, 6H), 1.43(s, 6H).

[0095] Example 1.2 Comparative Example 2 (CE-2): CE-2 was synthesized as described in Wakamiya, Atsushi et al. Chemistry Letters, 37(10), 1094-1095; 2008. CE-2 has the following structure: [ka]

[0096] Example 2 Synthesis of photoluminescent complexes: Example 2.1: PLC-1 Synthesis of compound 1 [ka]

[0097] Compound 1.1: To a solution of benzaldehyde (5 mmol), 4-methoxyacetophenone (995 mg, 5 mmol) in 10 mL ethanol, add 10% aqueous sodium hydroxide (5 mL) dropwise. Stir the mixture for 15 min, filter and wash with 20 mL ethanol / water (1:1) to obtain a white solid.

[0098] Compound 1.2: To a solution of compound 1.1 (4.2 mmol) in 15 mL ethanol, nitromethane (2.7 mL, 50 mmol) is added followed by potassium hydroxide pellets (47 mg, 0.8 mmol). The mixture is stirred at 70 °C under inert atmosphere for 30 min. 100 mL of water is added to the solution and the mixture is extracted with ethyl acetate (EA) (50 ml x 3). The organic phase is collected and loaded onto silica gel and purified by flash chromatography using an eluent of hexane / EA (0% to 25% DCM). The main peak is collected and after removal of the solvent under reduced pressure, a colorless liquid is obtained.

[0099] Compound 1.3: Step 1: To a solution of compound 1.2 (10 mmol) in 80 mL tetrahydrofuran (THF) and 50 mL methanol (MeOH) is added potassium hydroxide (KOH) powder (1.12 g, 20 mmol) at 0° C. The mixture is stirred for 10 minutes and then transferred to an addition funnel. This solution is added dropwise to a solution of concentrated sulfuric acid (H2SO4) (12 mL) in methanol (50 mL) at 0° C. over 1 hour. The resulting mixture is stirred at 0° C. for an additional hour and then slowly poured onto 300 g of ice. The ice and organic mixture is extracted with ethyl acetate (200 mL×2), washed with 10% aqueous potassium carbonate (K2CO3) solution (100 mL), brine (100 mL), and dried over magnesium sulfate (MgSO4). After filtering off the solid, the solvent is removed under reduced pressure to give a liquid that was carried on to the next step reaction without further purification.

[0100] Step 2: A mixture of the liquid from the above reaction (9 mmol) and ammonium acetate (3.54 g, 46 mmol) in 20 mL acetic acid is heated at 100° C. for 5 h. After cooling to room temperature, the mixture is worked up with water (200 mL) and extracted with ethyl acetate (250 mL). The organic phase is washed with brine, loaded onto silica gel, and purified by flash chromatography using an eluent of hexane / dichloromethane (DCM) (0% to 50% DCM). The main peak is collected and the solvent is removed to give a solid.

[0101] Compound 1.4: To a mixture of compound 1.3 (1.36 mmol), 2,4,6-trimethylbenzaldehyde (0.101 g, 0.68 mmol) in 25 mL of DCE, p-TsOH (0.05 g) is added and stirred at 60 °C for 24 h under argon atmosphere. The solution is cooled to room temperature, then DDQ (0.17 g, 0.75 mmol) is added to the solution and stirred for 1 h. To the resulting mixture at 0 °C, TEA (0.75 mL, 5.25 mmol) and BF3-Et2O (2.0 mL, 16.5 mmol) are added at 0 °C. The mixture is then stirred at 50 °C for 1 h and cooled to room temperature. The resulting mixture is diluted with 100 mL of DCM, washed with water, dried over MgSO4, loaded onto silica gel, and purified by flash chromatography using an eluent of hexane / DCM (0% to 50% DCM). Collect the desired peak and remove the solvent to give a dark purple solid.

[0102] Compound 1.5: To a solution of compound 1.4 (1.0 mmol) in 20 mL of anhydrous DCM was added BBr3 (1.1 mmol) at -78°C. The mixture was stirred at -78°C for 2 h, then poured into water and extracted with DCM. The organic phase was collected and dried over MgSO4. After removing the solvent under reduced pressure, the desired product is obtained.

[0103] Compound 1: A mixture of compound 1.5 (0.1 mmol), 2-(4-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (compound 5.5, see below, 0.3 mmol), diisopropylcarbodiimide (DIC) (0.63 mmol), dimethylaminopyridine (DMAP) / TsOH salt (58 mg, 0.2 mmol) in DCM (10 mL) is stirred at room temperature overnight. The resulting solution is loaded onto silica gel and purified by flash chromatography using an eluent of DCM / EA (0% to 10% EA). The desired peak is collected and the solvent is removed to give the product as a solid.

[0104] Synthesis of compound 2 [ka] [ka]

[0105] Compound 2.1: A mixture of 4-hydroxy-2,4-dimethylbenzaldehyde (0.1 mmol), 2-(4-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (compound 5.5, see below, 0.15 mmol), DIC (0.63 mmol), DMAP / TsOH salt (58 mg, 0.2 mmol) in DCM (10 mL) is stirred at room temperature overnight. The resulting solution is loaded onto silica gel and purified by flash chromatography using an eluent of DCM / EA (0% to 10% EA). The desired peak is collected and the solvent is removed to give the product as a solid.

[0106] Compound 2.2 To a mixture of compound 1.3 (1.36 mmol) and compound 2.1 (0.68 mmol) in 25 mL of DCE, p-TsOH (0.05 g) is added and stirred at 60° C. for 24 h under argon atmosphere. The solution is cooled to room temperature, then DDQ (0.17 g, 0.75 mmol) is added to the solution and stirred for 1 h. To the resulting mixture at 0° C., TEA (0.75 mL, 5.25 mmol) and BF3-Et2O (2.0 mL, 16.5 mmol) are added at 0° C. The mixture is then stirred at 50° C. for 1 h and cooled to room temperature. The resulting mixture is diluted with 100 mL of DCM, washed with water, dried over MgSO4, loaded onto silica gel, and purified by flash chromatography using an eluent of DCM / EA (0% to 10% EA). The desired peak is collected and the solvent is removed to give a dark purple solid.

[0107] Compound 2.3 To a solution of compound 2.2 (1.0 mmol) in 20 mL of anhydrous DCM is added BBr3 (1.1 mmol) at -78°C. The mixture is stirred at -78°C for 2 h, then poured into water and extracted with DCM. The organic phase is collected and dried over MgSO4. After removing the solvent under reduced pressure, the desired product can be obtained.

[0108] Compound 2: A mixture of compound 2.3 (0.1 mmol), 2-(4-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (compound 5.5, 0.3 mmol), DIC (0.63 mmol), DMAP / TsOH salt (58 mg, 0.2 mmol) in DCM (10 mL) is stirred at room temperature overnight. The resulting solution is loaded onto silica gel and purified by flash chromatography using an eluent of DCM / EA (0% to 10% EA). The desired peak is collected and the solvent is removed to give the product as a solid.

[0109] Synthesis of compound 3 [ka]

[0110] Compound 3: A mixture of compound 7.7 (see below, 0.1 mmol), 2-(4-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (compound 5.5, see below, 0.3 mmol), DIC (0.63 mmol), DMAP / TsOH salt (58 mg, 0.2 mmol) in DCM (10 mL) is stirred at room temperature overnight. The resulting solution is loaded onto silica gel and purified by flash chromatography using an eluent of DCM / EA (0% to 10% EA). The desired peak is collected and the solvent is removed to give the product as a solid.

[0111] Synthesis of compound 4 [ka] [ka]

[0112] Compound 4.4 To a mixture of compound 3.3 (1.36 mmol) and compound 2.4 (0.68 mmol) in 25 mL of DCE, p-TsOH (0.05 g) is added and stirred at 60° C. for 24 h under argon atmosphere. The solution is cooled to room temperature, then DDQ (0.17 g, 0.75 mmol) is added to the solution and stirred for 1 h. To the resulting mixture at 0° C., TEA (0.75 mL, 5.25 mmol) and BF3-Et2O (2.0 mL, 16.5 mmol) are added at 0° C. The mixture is then stirred at 50° C. for 1 h and cooled to room temperature. The resulting mixture is diluted with 100 mL of DCM, washed with water, dried over MgSO4, loaded onto silica gel, and purified by flash chromatography using an eluent of DCM / EA (0% to 10% EA). The desired peak is collected and the solvent is removed to give a dark purple solid.

[0113] Compound 4.5 To a solution of compound 4.4 (1.0 mmol) in 20 mL of anhydrous DCM is added BBr3 (1.1 mmol) at -78°C. The mixture is stirred at -78°C for 2 h, then poured into water and extracted with DCM. The organic phase is collected and dried over MgSO4. After removing the solvent under reduced pressure, the desired product is obtained.

[0114] Compound 4: A mixture of compound 4.5 (0.1 mmol), 2-(4-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (compound 5.5, 0.3 mmol), DIC (0.63 mmol) and DMAP / TsOH salt (58 mg, 0.2 mmol) in DCM (10 mL) is stirred at room temperature overnight. The resulting solution is loaded onto silica gel and purified by flash chromatography using an eluent of DCM / EA (0% to 10% EA). The desired peak is collected and the solvent is removed to give the product as a solid.

[0115] Synthesis of compound 5 [ka] [ka]

[0116] Compound 5.1: (6-(4-bromo-2-nitrophenoxy)-1H,3H-benzo[de]isochromene-1,3-dione): A mixture of 4-bromo-1,8-naphthalic anhydride (2.77 g, 10 mmol), 4-bromo-2-nitrophenol (3.27 g, 15 mmol) was degassed under vacuum for 30 min, then anhydrous NMP (50 mL) was added, followed by sodium hydroxide (0.2 g, 5 mmol) and copper powder (0.318 g, 5 mmol). The mixture was sparged with argon for 20 min and then heated at 180° C. overnight under argon atmosphere. After cooling to room temperature, 50 mL of 20% aqueous hydrochloric acid was added dropwise to the solution, followed by 50 mL of water. The resulting mixture was allowed to stand for 3 h, then filtered to collect the precipitate, which was dried under vacuum to give 4.6 g of crude product. The crude product was dispersed in 30 mL of acetone and stirred at room temperature overnight to dissolve impurities. Filtration and drying in vacuum afforded a tan solid (compound 5.1) (3.3 g, 80% yield) as the desired product. LCMS (APCI+): C 18 Calculated for H9BrNO6 (M+H)=413.95; Found: 414. 1 H NMR(400MHz,TCE-d2) δ 8.70(dd,J=8.4,1.2Hz,1H), 8.63(dd,J=7.3,1.2Hz,1H), 8.41(d,J=8.3Hz,1H), 8.2 4(d,J=2.4Hz,1H), 7.89~7.79(m,2H), 7.20(d,J=8.7Hz,1H), 6.82(d,J=8.3Hz,1H).

[0117] Compound 5.2 (6-(2-amino-4-bromophenoxy)-1H,3H-benzo[de]isochromene-1,3-dione): A mixture of compound 5.1 (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 cooling to room temperature, 100 mL of water was added to the mixture with stirring. The resulting mixture was filtered, washed with water, and dried in air and in vacuum to give a solid (compound 5.2) (1.35 g, 82% yield). LCMS (APCI-): C 18 H 10Calculated for BrNO4=382.98; Found: 383. 1 H NMR (400MHz, DMSO-d6) δ 9.01~8.26 (m, 3H), 7.96 (s, 1H), 6.93 (dd, J=85.2, 36.5Hz, 4H), 5.54 (s, 2H).

[0118] Compound 5.3 (9-Bromo-1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione): Compound 5.2 (2.65 g, 6.9 mmol) was dispersed in acetic acid (50 mL) / water (10 mL) and cooled to 0 °C. Pre-cooled hydrochloric acid (2.8 mL, 34.5 mmol) was added under stirring, followed by dropwise addition of sodium nitrite solution (3.57 g, 52 mmol) in 15 mL of water at 0 °C. The whole was stirred at 0 °C for 1 h, then transferred to an addition funnel and added dropwise to copper sulfate solution (12 g, 47 mmol, in 140 mL of water) at 130 °C over 1 h. After cooling to room temperature, the precipitate was collected by filtration, washed with water (100 mL x 3), and then stirred in 50 mL of acetone at 40 °C for 30 min. Filtration and drying in air and then in vacuum gave a tan solid (compound 5.3) (1.76 g, 70% yield). LCMS (APCI+): C 18 Calculated for H8BrO4 (M+H)=366.95; found: 367. 1 H NMR(400MHz,d2-TCE) δ 8.51(dd,J=12.3,8.1Hz,2H), 8.12(d,J=2.3Hz,1H), 7.86(d,J=7.9Hz,1H), 7.60(dd,J=8.8,2.3Hz,1H), 7.28(d,J=8.3Hz,1H), 7.23(d,J=8.8Hz,1H).

[0119] Compound 5.4 (2-(4-(9-Bromo-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid): A mixture of compound 5.3 (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. The mixture was then heated to 165° C. and kept at this temperature for 3 h. TLC and LCMS showed about 95% conversion with no observable side reactions. The mixture was cooled to 50° C. It was then poured into an acetone solution (40 mL), which was pre-cooled by a water-ice bath. The mixture was kept at 0° C. for 2 h and then kept stirring at room temperature overnight. The solid was collected by vacuum filtration and washed with acetone (4 mL). It was then dried in a vacuum oven at 100° C. for 3 hours to give pure compound 5.4 as a tan solid (395.0 mg, 73% yield). MS (APCI): 26 H 14 BrNO5([M+H] + ) Calculated value = 500 Actual value: 500. 1 H NMR(400MHz,CDCl2CDCl2) δ 8.65(d,J=8.0Hz,1H), 8.62(d,J=8.0Hz,1H), 8.21(dd,J=6.4Hz,2.4Hz,1H), 7.99(bs,1H), 7.95(t,J=7.6Hz ,1H), 7.67(dd,J=8.4Hz,2.4Hz,1H), 7.53(d,J=8.0Hz,2H), 7.37(d,J=8.4Hz,1H), 7.32(m,3H), 2.94(s,2H).

[0120] Compound 5.5 (2-(4-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid): A mixture of compound 5.4 (400.0 mg, 0.80 mmol), 4-(trifluoromethyl)phenylboronic acid (262.2 mg, 1.6 mmol), Pd(dppf)Cl2 (41.0 mg, 0.056 mmol) and 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 to 80° C. and the reaction was kept at this temperature overnight. The reaction was monitored using TLC. After completion, the reaction was worked up by the addition of 0.1 N HCl (150 ml) and EtOAc (150 ml). The aqueous phase was further extracted with THF (150 ml x 3). The combined organic phase was dried over anhydrous Na2SO4, concentrated under rotary evaporator and purified by flash chromatography using DCM (0% -> 40%, containing 0.1% TFA) in EtOAc as eluent to give pure compound 5.5 as a yellow / tan solid (363.0 mg, 80% yield). MS (APCI): C 33 H 18 F3NO5([M+H] + ) Calculated value = 566 Actual value: 566. 1 H NMR(400MHz,DMSO-d6)8.76(m,1H), 8.56(m,2H), 8.52(dd,J=8.0Hz,J=3.2Hz,1H), 8.15(m,2H), 8.06(m,1H), 7.94(d,J =8.0Hz,2H), 7.66(dd,J=8.0Hz,J=4.0Hz,1H), 7.53(m,1H), 7.45(d,J=8.0Hz,2H), 7.33(d,J=8.0Hz,2H), 3.72(s,2H).

[0121] Compound 5.6. (3,7-bis(4-bromophenyl)-5,5-difluoro-10-mesityl-1,9-diphenyl-5H-4λ 4 ,5λ 4 -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine): Step 1: A mixture of 2-(4-bromophenyl)-4-phenyl-1H-pyrrole (synthesized according to ref. Synlett, 2016, 27(11), 1738-1742; 1.0 g, 3.36 mmol), 2,4,6-trimethylbenzaldehyde (also called mesitaldehyde, 0.249 g, 1.68 mmol) and p-TsOH·HO (100 mg) in 80 mL of 1,2-dichloroethane was degassed and then heated at 60 °C for 40 h. LCMS analysis showed that the major product was m / e + = 727 peak indicating the desired product.

[0122] Step 2: At room temperature, DDQ (454 mg, 2 mmol) was added to the mixture obtained from step 1, and the whole was stirred at room temperature for 1 h. LCMS analysis showed that the starting material was - = 724 showing complete conversion to the desired product with a peak at 724.

[0123] Step 3: With ice bath cooling, triethylamine (0.85 mL, 6 mmol) and BF3-diethyl etherate (1.1 mL, 9 mmol) were added to the mixture from step 2. The whole was heated at 50° C. for 1 h, then more triethylamine (0.5 mL) and BF3-diethyl etherate (0.5 mL) were added and the mixture was heated for another 1 h. LCMS analysis showed that the reaction was m / e - The main peak at 0.05% NMR (Hz)=772 indicated completion. The mixture was diluted with 50 mL of dichloromethane and washed twice with water and once with brine. The organic phase was collected and concentrated to 100 mL, then loaded onto silica gel and purified by flash chromatography using an eluent of hexane / dichloromethane (gradient 40% to 100% dichloromethane). The main fractions were collected and concentrated under reduced pressure and the solvent removed to give a solid which was washed with methanol, then filtered and dried in air to give a purple solid (1.06 g, 81.6% yield). 1H NMR(400MHz,chloroform-d) δ 7.81~7.73(m,4H), 7.61~7.54(m,4H), 6.97~6.90(m,2H), 6.85(dd,J=8.3,6.9Hz,4H), 6.78~6.71(m,4H), 6.42(s,2H), 6.00(s,2H), 1.98(s,6H), 1.85(s,3H).LCMS(APCI-):C 42 H 31 Calculated for BBr2F2N2: 772.1; Found: 772.

[0124] Compound 5.7 (3,3'-((5,5-difluoro-10-mesityl-1,9-diphenyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-3,7-diyl)bis(4,1-phenylene))bis(prop-2-yn-1-ol)): A mixture of compound 5.6 (200 mg, 0.258 mmol), CuI (10 mg, 0.052 mmol), Pd(PPh3)2Cl2 (36 mg, 0.052 mmol), and propargyl alcohol (56 mg, 1.0 mmol) in 5 mL of triethylamine was degassed and then heated at 80 °C overnight under argon atmosphere. The resulting mixture was diluted with 200 mL of DCM. The DCM solution was washed with 0.1N aqueous HCl (100 mL) and water (100 mL), then loaded onto silica gel and purified by flash chromatography using an eluent of DCM / ethyl acetate (0% to 50% ethyl acetate). The main peak was collected and concentrated under reduced pressure to give a red solid (compound 5.7) (150 mg, 80.4% yield).

[0125] Compound 5 ((5,5-difluoro-10-mesityl-1,9-diphenyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-3,7-diyl)bis(4,1-phenylene))bis(prop-2-yn-3,1-diyl)bis(2-(4-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xanthen[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate LCMS (APCI-): A mixture of compound 5.7 (30 mg, 0.0415 mmol), 2-(4-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (compound 5.5, 70 mg, 0.124 mmol), DIC (0.1 mL, 0.63 mmol), DMAP / TsOH salt (29 mg, 0.1 mmol) in DCM (8 mL) was stirred at room temperature overnight. The resulting mixture was loaded onto silica gel and purified by flash chromatography using an eluent of DCM / EA (0% to 10% EA). The desired peak was collected and the solvent was removed, which should give the product as a solid (compound 5) (20 mg, 26% yield). LCMS (APCI-): C 114 H 69 BF8N4O 10 Calculated value: 1816.50; Measured value: 1816. 1 H NMR(400MHz,d2-TCE) δ 8.50(dd,J=14.5,8.1Hz,4H), 8.12(d,J=2.1Hz,2H), 7.91(d,J=8.1Hz,2H), 7.83(d,J =8.2Hz,4H), 7.75~7.61(m,10H), 7.49(dd,J=18.5,8.2Hz,8H), 7.39(d,J=8.6Hz,2H) , 7.24(t,J=7.9Hz,6H), 6.87(t,J=7.4Hz,2H), 6.77(t,J=7.5Hz,4H), 6.66(d,J=7.5H z,4H), 6.41(s,2H), 5.95(s,2H), 4.93(s,4H), 3.76(s,4H), 1.88(s,6H), 1.77(s,3H).

[0126] Synthesis of compound 6 [ka]

[0127] Compound 6.1 (2-(4-(9-(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid): A 100 mL vial was equipped with a stir bar. The vial was charged with compound 5.4 (400.0 mg, 0.80 mmol), 3,5-bis(trifluoromethyl)phenylboronic acid (262.2 mg, 1.6 mmol), Pd(dppf)Cl2 (41.0 mg, 0.056 mmol) and K2CO3 (412.6 mg, 2.2 mmol) in THF / DMF / H2O (22 ml / 4.4 ml / 2.2 ml) and degassed at room temperature. The reaction mixture was heated to 80° C. and the reaction was kept at this temperature overnight. The reaction was monitored using TLC. After completion, the reaction was worked up by the addition of 0.1N HCl (150 ml) and EtOAc (150 ml). The aqueous phase was further extracted with THF (150 ml x 3). The combined organic phase was dried over anhydrous Na2SO4, concentrated under rotary evaporator and purified by flash chromatography using DCM (0% -> 40%, containing 0.1% TFA) in EtOAc as eluent to give pure compound 6.1 as a yellow / tan solid (311.0 mg, 61% yield). MS (APCI): C 34 H 17 F6NO5([M+H] + ) Calculated value = 634 Actual value: 634. 1 H NMR (400MHz, DMSO-d6) 8.73(m,1H), 8.46(m,5H), 8.10(m,2H), 7.57(m,1H), 7.42(d,J=8.0Hz,2H), 7.40(m,1H), 7.30(d,J=8.0Hz,2H), 3.72(s,2H).

[0128] Compound 6 ((5,5-difluoro-10-mesityl-1,9-diphenyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-3,7-diyl)bis(4,1-phenylene))bis(prop-2-yn-3,1-diyl)bis(2-(4-(9-(3,5-bis-(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl) Acetate: A mixture of compound 5.7 (93 mg, 0.129 mmol), 2-(4-(9-(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (compound 6.1) (325 mg, 0.514 mmol), DIC (0.2 mL, 1.26 mmol), and DMAP (61 mg, 0.5 mmol) in 10 mL anhydrous DCM was stirred at room temperature overnight. The resulting solution was loaded onto silica gel and purified by flash chromatography using an eluent of DCM / EA (0% to 10% EA). The main peak was collected, concentrated under reduced pressure, and then triturated with MeOH containing 5% water to break down the product. The desired product was collected by filtration and dried in air as a dark red-brown solid (compound 6) (100 mg, 48.6% yield). 1 H NMR(400MHz,TCE) δ 8.53(dd,J=14.6,8.1Hz,4H), 8.12(d,J=2.2Hz,2H), 7.97(d,J=8.3Hz,6H), 7.90~7.78(m,6H), 7.68(dd,J=8.6,2.1Hz,2H), 7.57~7.38(m,10H), 7.25(dd ,J=17.0,8.3Hz,6H), 6.87(t,J=7.4Hz,2H), 6.77(t,J=7.5Hz,4H), 6.70~6. 58(m,4H), 6.41(s,2H), 4.93(s,4H), 3.76(s,4H), 1.88(s,6H), 1.77(s,3H).

[0129] Synthesis of compound 7 [ka] [ka]

[0130] Compound 7.1 ((E)-3-(3,5-bis(trifluoromethyl)phenyl)-1-(4-methoxyphenyl)prop-2-en-1-one): To a solution of 3,5-bis(trifluoromethyl)benzaldehyde (1.21 g, 5 mmol), 4'-methoxyacetophenone (0.75 g, 5 mmol) in 10 mL ethanol was added aqueous NaOH (0.5 g in 5 mL water) pre-cooled in an ice bath. The resulting mixture was stirred at room temperature for 20 min, and a white precipitate was observed. 5 mL of water was added to the mixture, which was stirred for an additional 10 min, and the resulting suspension was filtered and dried in air to give a white solid (compound 7.1) (1.38 g, 74% yield). 1 H NMR(400MHz,d2-TCE) δ 8.02~7.94(m,4H), 7.82(s,1H), 7.71(d,J=15.7Hz,1H), 7.56(d,J=15.7Hz,1H), 6.98~6.91(m,2H), 3.82(s,3H), 1.51(s,2H).

[0131] Compound 7.2 (3-(3,5-bis(trifluoromethyl)phenyl)-1-(4-methoxyphenyl)-4-nitrobutan-1-one): A mixture of compound 7.1 (4.233 g, 11.3 mmol), nitromethane (10 mL, 186 mmol), and KOH (150 mg, 2.68 mmol) was sparged with argon for 10 min and then heated at 70° C. for 30 min. The resulting mixture was poured into 300 mL of water and extracted with EA. The organic phase was collected, dried over MgSO4, and the solvent was then removed to give a liquid (compound 7.2) (5.21 g, quantitative yield). LCMS (APCI+): C 19 H 16 Calculated for F6NO4: 436.09 (M+H); Found: 436. 1H NMR(400MHz,d2-TCE) δ 7.87~7.78(m,2H), 7.78~7.66(m,3H), 6.91~6.82(m,2H), 4.84(dd,J=13.2,5.9Hz,1H) , 4.67(dd,J=13.2,8.7Hz,1H), 4.33~4.22(m,1H), 3.79(s,3H), 3.34(d,J=6.9Hz,2H).

[0132] Compound 7.3 (3-(3,5-bis(trifluoromethyl)phenyl)-4,4-dimethoxy-1-(4-methoxyphenyl)butan-1-one): To a solution of compound 7.2 (11 mmol) in 80 mL THF / 50 mL MeOH, KOH powder (1.23 g, 22 mmol) was added at 0° C., the mixture was stirred at 0° C. for 10 min, and then transferred to an addition funnel. The solution was added dropwise to a solution of 12 mL concentrated H2SO4 in methanol (50 mL) at 0° C. over 1 h. The resulting mixture was stirred at 0° C. for another 1 h, and then poured onto 300 g ice. The mixture was extracted with EA (200 ml×2). The organic phase was collected, washed with brine, and dried over MgSO4. After filtering off the solid, the solvent was removed under reduced pressure to give a liquid (compound 7.3) (4.5 g, 90% yield), which was carried on to the next step without further purification. LCMS(APCI-):C 21 H 19 Calculated for F6O4: 449.13 (MH); Found: 449. 1 H NMR(400MHz,d2-TCE) δ 7.86~7.81(m,2H), 7.75~7.70(m,2H), 7.65(s,1H), 6.87~6.82(m,2H), 4.35(d,J=4.8Hz,1H ), 3.77(s,3H), 3.77~3.71(m,1H), 3.49(dd,J=17.8,4.7Hz,1H), 3.31(s,3H), 3.26(s,3H).

[0133] Compound 7.4 (4-(3,5-bis(trifluoromethyl)phenyl)-2-(4-methoxyphenyl)-1H-pyrrole): A mixture of compound 7.3 (10 mmol), NHOAc (3.85 g, 50 mmol) in acetic acid (20 mL) was heated at 100° C. for 5 h. The resulting mixture was poured into 300 mL of water, extracted with EA (200 mL), washed with brine, dry loaded onto silica gel and purified by flash chromatography using an eluent of hexane / DCM (0% to 50% DCM). The main peak was collected and the solvent was removed to give a bluish solid (2.5 g, 65% yield). LCMS (APCI+): C 19 H 14 Calculated for F6NO: 386.09 (M+H); Found: 386. 1 H NMR(400MHz,d2-TCE) δ 8.49(s,1H), 7.87(s,2H), 7.58(s,1H), 7.44~7.37(m,2H), 7.19~7.13(m,1H), 6.93~6.85(m,2H), 6.69~6.64(m,1H), 3.77(s,3H).

[0134] Compound 7.5 (1,9-bis(3,5-bis(trifluoromethyl)phenyl)-5,5-difluoro-10-mesityl-3,7-bis(4-methoxyphenyl)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine): Step 1: A mixture of compound 7.4 (0.524 g, 1.36 mmol), 2,4,6-trimethylbenzaldehyde (0.101 g, 0.68 mmol) in 25 mL of DCE containing 0.05 g of TsOH as a catalyst was degassed and heated at 60° C. overnight. LCMS analysis showed m / e + One major peak at =901 indicates the reaction is complete.

[0135] Step 2: To the above mixture, DDQ (0.22 g, 0.97 mmol) was added and stirred at room temperature for 30 minutes. LCMA analysis showed m / e - = 898.

[0136] Step 3: To the above solution was added TEA (1.0 mL), BF3-Et2O (2 mL) and then heated at 50°C for 1 h. The resulting mixture was diluted with DCM (200 mL), washed with water, then loaded onto silica gel and purified by flash chromatography using an eluent of hexane / DCM (0% to 50% DCM). The desired peak was collected and the solvent was removed to give a blue solid (400 mg, 62% yield). LCMS (APCI-): C 48 H 33 BF 14 Calculated for N2O2: 936.24; Found: 946. 1 H NMR(400MHz,d2-TCE) δ 7.89~7.83(m,4H), 7.38(s,2H), 7.21~7.16(m,4H), 6.97~6.91(m,4H), 6.46(s,2H), 5.94(s,2H), 3.81(s,6H), 1.92(s,6H), 1.69(s,3H).

[0137] Compound 7.6 ((Z)-4-(3-(3,5-bis(trifluoromethyl)phenyl)-2-(3-(3,5-bis(trifluoromethyl)phenyl)-5-(4-hydroxyphenyl)-1H-pyrrol-2-yl)(mesityl)methylene)-2H-pyrrol-5-yl)phenol): To a solution of compound 7.5 (215 mg, 0.227 mmol) in 10 mL of anhydrous DCM was added BBr3 (0.15 mL, 1.5 mmol) at -78 °C. The whole was stirred from -78 °C to room temperature overnight. 10 mL of MeOH was added to the mixture to quench the excess BBr3. The mixture was stirred at room temperature for 2 h, then diluted with 100 mL of DCM, washed with water, and then concentrated to about 20 mL. Hexane (30 mL) was added to the solution to precipitate the desired product. Filtration and drying in air gave a green gold solid (150 mg, 76% yield). LCMS (APCI-): C 46 H 30 F 12 Calculated for N2O2: 870.21; Found: 870. 1H NMR(400MHz,MeOD) δ 8.10(d,J=12.3Hz,2H), 7.95(d,J=8.3Hz,2H), 7.84~7.73(m,3H), 7.60(s,1H), 7.53(s,2H), 7.49(s,1H), 7.29(d,J=8.6Hz,2H), 7.03(d ,J=8.3Hz,2H), 6.91(d,J=8.5Hz,2H), 6.81(d,J=8.5Hz,2H), 6.72(s,1H), 6.11(s,1H), 2.14(d,J=6.8Hz,3H), 2.09(s,3H), 1.96(s,3H).

[0138] Compound 7.7 (4,4'-(1,9-bis(3,5-bis(trifluoromethyl)phenyl)-5,5-difluoro-10-mesityl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-3,7-diyl)diphenol): To a mixture of compound 7.6 (140 mg, 0.16 mmol) in 10 mL of DEC was added TEA (0.154 mL, 1 mmol), BF3-Et2O (0.185 mL, 1.5 mmol) at room temperature. The resulting mixture was heated at 60 °C for 2 h. After cooling to room temperature, the mixture was loaded onto silica gel and purified by flash chromatography using an eluent of DCM / EA (0% to 20% EA). The main peak was collected and the solvent was removed under reduced pressure to give a dark blue solid (120 mg, 82% yield). LCMA(APCI-):C 46 H 29 BF 14 Calculated for N2O2: 918.21; Found: 918. 1 H NMR(400MHz,TCE) δ 7.85~7.77(m,4H), 7.38(s,2H), 7.20~7.15(m,4H), 6.91~6.83(m,4H), 6.46 (s,2H), 5.94(s,2H), 5.91(s,18H), 5.09(s,2H), 1.92(s,6H), 1.69(s,3H).

[0139] Compound 7 (1,9-bis(3,5-bis(trifluoromethyl)phenyl)-5,5-difluoro-10-mesityl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-3,7-diyl)bis(4,1-phenylene)bis(2-(4-(9-(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate : A mixture of compound 7.7 (80 mg, 0.087 mmol), 2-(4-(9-(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (compound 6.1) (220 mg, 0.348 mmol), DIC (0.1 mL, 0.63 mmol), DMAP / TsOH salt (29 mg, 0.1 mmol) in DCM (10 mL) was stirred at room temperature overnight. The resulting mixture was diluted with 20 mL of DCM, then loaded onto silica gel and purified by flash chromatography using an eluent of DCM / EA (0% to 10% EA). The main peak was collected and concentrated under reduced pressure, then triturated with MeOH and the solid was crashed out. After filtration and drying in air, a dark purple crystalline solid (123 mg, 66% yield) was obtained. 1 H NMR(400MHz,TCE) δ 8.59~8.39(m,4H), 8.09(d,J=2.2Hz,2H), 7.97(s,4H), 7.92(dd,J=8.4,6 .0Hz,6H), 7.85(s,2H), 7.72(dd,J=8.6,2.1Hz,2H), 7.56(d,J=8.2Hz,4H ), 7.46(d,J=8.6Hz,2H), 7.39(s,2H), 7.30(d,J=8.1Hz,4H), 7.27~7.16( m,10H), 6.51(s,2H), 5.96(s,2H), 3.95(s,4H), 1.94(s,6H), 1.70(s,3H).

[0140] Synthesis of compound 8 [ka] [ka]

[0141] Compound 8.1 ((E)-1-(4-bromophenyl)-3-(4-(trifluoromethyl)phenyl)prop-2-en-1-one): 4-Trifluoromethylbenzaldehyde (870 mg, 5 mmol) and 4-bromoacetophenone (995 mg, 5 mmol) were dissolved in 10 mL ethanol. To the solution was added sodium hydroxide solution (0.5 g in 5 mL water) dropwise at room temperature. A white precipitate formed immediately. The mixture was stirred for 15 min, filtered and washed with 20 mL ethanol / water (1:1 v / v) to give a white solid. LCMS (APCI-): C 16 H 10 Calculated for BrF3O: 353.99; Found: 354. 1 H NMR(400MHz,d2-TCE) δ 7.85~7.77(m,2H), 7.76~7.65(m,3H), 7.61(dd,J=8.6,2.5Hz,4H), 7.44(d,J=15.7Hz,1H).

[0142] Compound 8.2 (1-(4-bromophenyl)-4-nitro-3-(4-(trifluoromethyl)phenyl)butan-1-one): A mixture of (E)-1-(4-bromophenyl)-3-(4-(trifluoromethyl)phenyl)prop-2-en-1-one (compound 8.1, 1.5 g, 4.2 mmol), nitromethane (2.7 mL, 50 mmol), KOH (47 mg, 0.8 mmol) in 15 mL ethanol was sonicated for 1 min and then heated at 70 °C for 30 min. The resulting solution was poured into water (100 mL) and extracted with ethyl acetate (3 x 50 mL). The organic phase was collected, dry loaded onto silica gel, and purified by flash chromatography using an eluent of hexane / EA (0% to 25% EA). The main peak was collected and the solvent was removed to give a colorless liquid (compound 8.2) (1.36 g, 77.8% yield). LCMS(APCI-):C 17 H 13 Calculated for BrF3NO3: 415.00; Found: 415. 1H NMR(400MHz,d2-TCE) δ 7.73~7.65(m,2H), 7.59~7.50(m,4H), 7.34(d,J=8.1Hz,2H), 4.77(dd,J=12.8, 6.3Hz, 1H), 4.63 (dd, J=12.8, 8.4Hz, 1H), 4.24~4.13 (m, 1H), 3.41~3.25 (m, 2H).

[0143] Compound 8.3 (1-(4-bromophenyl)-4,4-dimethoxy-3-(4-(trifluoromethyl)phenyl)butan-1-one): To a solution of compound 8.2 (4.16 g, 10 mmol) in 80 mL THF / 50 mL MeOH at 0 °C was added powdered KOH (1.12 g, 20 mmol). The mixture was stirred at room temperature for 10 min and then transferred to an addition funnel. This solution was added dropwise over 1 h to a solution of MeOH (50 mL) containing 12 mL of concentrated H2SO4. The resulting mixture was stirred for an additional 1 h at 0 °C and then slowly poured onto 300 g of ice. The ice-organics mixture was extracted with ethyl acetate (200 mL x 2). The organic phase was washed with 10% aqueous K2CO3 (100 mL), brine (100 mL) and dried over MgSO4. After filtering off the solid, the solution was concentrated under reduced pressure to give a liquid (4.2 g, 90% yield) which was carried on to the next step without further purification.

[0144] Compound 8.4 (2-(4-bromophenyl)-4-(4-(trifluoromethyl)phenyl)-1H-pyrrole): A mixture of compound 8.3 (4.0 g, 9.28 mmol), ammonium acetate (3.54 g, 46 mmol) in 20 mL of acetic acid was heated at 100° C. for 5 h. After cooling to room temperature, the reaction mixture was worked up with water (200 mL) and extracted with ethyl acetate (250 mL). The organic phase was collected, washed with brine, dry loaded onto silica gel, and purified by flash chromatography using an eluent of hexane / DCM (0% to 50% DCM). After collecting the main peak and removing the solvent, a bluish solid was obtained as the desired product (compound 8.4) (2.7 g, 86% yield). LCMS (APCI+): C 17 H 12Calculated for BrF3N: 366.00 (M+H); Found: 366. 1 H NMR(400MHz,d2-TCE) δ 8.54(s,1H), 7.62~7.50(m,4H), 7.50~7.42(m,2H), 7.39~7.28(m,2H), 7.16(dd,J=2.8,1.7Hz,1H), 6.76(dd,J=2.8,1.7Hz,1H).

[0145] Compound 8.5 (3,7-bis(4-bromophenyl)-5,5-difluoro-10-mesityl-1,9-bis(4-(trifluoromethyl)phenyl)-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine): Step 1: A mixture of compound 8.4 (0.5 g, 1.36 mmol), 2,4,6-trimethylbenzaldehyde (0.101 g, 0.68 mmol), TsOH (0.05 g) in anhydrous DCE (25 mL) was heated under argon at 60° C. overnight. LCMS analysis showed the condensation reaction was complete.

[0146] Step 2: DDQ (0.27 g, 0.12 mmol) was added to the above solution and stirred at room temperature for 45 min. LCMS analysis showed that the oxidation reaction was complete.

[0147] Step 3: To the mixture from above, TEA (0.75 mL, 5.25 mmol), BF3-Et2O (2.0 mL, 16.5 mmol) were added at room temperature. The resulting mixture was heated at 50° C. for 1 h. After cooling to room temperature, the mixture was diluted with 100 mL of DCM, washed with water, dried over MgSO4, then loaded onto silica gel and purified by flash chromatography using an eluent of hexane / DCM (0% to 50% DCM). The main peak was collected and the solvent was removed under reduced pressure to give a dark purple solid (400 mg, 65% yield). LCMS (APCI-): C 44 H 29 Calculated for BBr2F8N2: 906.07; Found: 906. 1H NMR(400MHz,d2-TCE) δ 7.80~7.67(m,4H), 7.58~7.47(m,4H), 7.04(d,J=8.1Hz,4H), 6.79(d,J=7.9Hz,4H), 6.42(s,2H), 5.93(s,2H), 1.87(s,6H), 1.76(s,3H).

[0148] Compound 8.6 (3,3'-((5,5-difluoro-10-mesityl-1,9-bis(4-(trifluoromethyl)phenyl)-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-3,7-diyl)bis(4,1-phenylene))bis(prop-2-yn-1-ol)): A mixture of compound 8.5 (220 mg, 0.242 mmol), CuI (10 mg, 0.052 mmol), Pd(PPh3)2Cl2 (36 mg, 0.052 mmol), and prop-2-yn-1-ol (56 mg, 1.0 mmol) in 8 mL of TEA was degassed three times by freeze-thaw protocol and then heated at 80 °C under argon overnight. The resulting mixture was diluted with DCM (100 mL) and washed with 0.1N HCl aqueous solution. The organic phase was collected, loaded onto silica gel, and purified by flash chromatography using an eluent of DCM / EA (0% to 50% EA). After removal of the solvent, a dark solid was obtained as the desired product (compound 8.6, 60 mg, 40% yield). LCMS (APCI-): C 50 H 35 Calculated for BF8N2O2: 858.27; Found: 858. 1 H NMR(400MHz,TCE) δ 7.90~7.76(m,4H), 7.52~7.40(m,4H), 7.04(d,J=8.1Hz,4H), 6.79(d,J=8.0Hz, 4H), 6.46(s,2H), 5.93(s,2H), 4.45(d,J=5.6Hz,4H), 1.87(s,6H), 1.76(s,3H).

[0149] Compound 8 ((5,5-difluoro-10-mesityl-1,9-bis(4-(trifluoromethyl)phenyl)-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-3,7-diyl)bis(4,1-phenylene))bis(prop-2-yn-3,1-diyl)yl)bis(2-(4-(9-(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xanthen[2,1,9-def]isoquinoline-2(3H )-yl)phenyl)acetate: A mixture of compound 8.6 (60 mg, 0.07 mmol), 2-(4-(9-(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (compound 6.1, 176 mg, 0.28 mmol), DIC (0.1 mL, 0.63 mmol), and DMAP (24 mg, 0.2 mmol) in 10 mL anhydrous DCM was stirred at room temperature overnight. The resulting solution was diluted with 20 mL of DCM, loaded onto silica gel, and purified by flash chromatography using an eluent of DCM / EA (0% to 10% EA). The main desired peak was collected, concentrated under reduced pressure, and then triturated with MeOH to give a dark solid (90 mg, 61% yield). 1 H NMR(400MHz,TCE) δ 8.53(dd,J=15.4,8.1Hz,4H), 8.12(d,J=2.2Hz,2H), 8.04~7.93(m,6H), 7.91~7.79(m,6H), 7.69(dd,J=8.6,2.1Hz,2H), 7.59~7.39(m,10H), 7 .31~7.17(m,6H), 7.04(d,J=8.1Hz,4H), 6.79(d,J=7.9Hz,4H), 6.46(s ,2H), 5.93(s,2H), 4.93(s,4H), 3.76(s,4H), 1.87(s,6H), 1.76(s,3H).

[0150] Synthesis of compound 9 [ka] [ka]

[0151] Compound 9.1 (5,11-Dibromo-1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione): A 2 L, 2-neck round bottom flask was equipped with a stir bar and fitted with a long finned condenser. 1H,3H-Isochromeno[6,5,4-mna]xanthene-1,3-dione (synthesized according to ref: RSC Adv., 2014, 4, 53072-53078) (34.688 mmol, 10.00 g) was added to the flask, followed by ortho-dichlorobenzene (1000 mL). The reaction mixture was stirred at room temperature and Br2 (416.26 mmol, 21.3 mL) was added. The second neck was stoppered and the reaction mixture was heated open to air at 75 °C using an aluminum heat block over the weekend. The reaction mixture was cooled to room temperature and the solids were filtered off. The filtrate was diluted with hexane (about 20% of the volume) and the second precipitate was filtered off. Both precipitates were dried in vacuum at 100° C. Orangeish solid, 10.866 g total (69.9% yield). Both had similar LCMS and NMR. MS (APCI): Chemical formula: C 18 Calculated for H6Br2O4 (M+H)=445; Found: 445. 1 H NMR(400MHz,TCE) δ 9.47(dd,J=8.4,1.5Hz,1H), 8.76(d,J=14.2Hz,2H), 7.72~7.63(m,1H), 7.56(dd,J=8.3,1.4Hz,1H), 7.46(ddd,J=8.5,6.7,1.9Hz,1H).

[0152] Compound 9.2 (2-(4-(5,11-dibromo-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid): Compound 9.2 was synthesized similarly to compound 5.4 above from compound 9.1 (7.000 mmol, 3.136 g), 2-(4-aminophenyl)acetic acid (14.00 mmol, 2.117 g), and DMAP (2.100 mmol, 257 mg) in anhydrous DMF (65 mL) at 160° C. The crude reaction mixture was cooled to 0° C., quenched with 6N HCl (approx. 5 mL), and diluted with water (up to approx. 350 mL). The precipitate was filtered off and washed with water. The product (compound 9.2) was dried by suction and used in the next reaction without further purification. The yield is assumed to be 100%. MS (APCI): Chemical formula: C 26 H 13 Calculated for Br2NO5 (M+H)=578; Found: 578.

[0153] Compound 9.3 (2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid): Compound 9.3 was synthesized from compound 9.2 (3.500 mmol, 2.034 g), (4-(trifluoromethyl)phenyl)boronic acid (14.00 mmol, 2.659 g), K2CO3 (19.25 mmol, 2.661 g), and Pd(dppf)Cl2 (0.0245 mmol, 179 mg) in THF (60 mL), DMF (12 mL), and water (6 mL) with heating at 80 °C overnight under argon atmosphere. The crude reaction mixture was evaporated to dryness in vacuo, taken up in DCM, and evaporated in vacuo onto approximately 35 g of flash silica gel. Purification by flash chromatography on silica gel (220 g, equilibrated 0% EtOAc / DCM, eluted 0% (10 CV) to 15.3% EtOAc / DCM (15.3 CV) to 40% EtOAc / DCM (10 CV) to isocratic 40% EtOAc / DCM). EtOAc contained 0.1% v / v TFA. Fractions containing product were evaporated to dryness in vacuo. 2.000 g (80.3%) of a tan solid was obtained. MS (APCI): Formula: C 40 H21 Calculated for F6NO5 (M+H)=710; Found: 710. 1 H NMR(400MHz,DMSO) δ 12.44(s,1H), 8.47(s,1H), 8.23(s,1H), 8.02(d,J=8.1Hz,2H), 7.97~7.88(m,4H), 7.75(d,J=8.0Hz ,2H), 7.49~7.37(m,3H), 7.31(d,J=8.2Hz,1H), 7.30~7.24(m,2H), 7.02~6.91(m,2H), 3.68(s,2H).

[0154] Compound 9 ((5,5-difluoro-10-mesityl-1,9-diphenyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-3,7-diyl)bis(4,1-phenylene))bis(prop-2-yn-3,1-diyl)bis(2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xanthen[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate ester: A mixture of compound 5.7 (50 mg, 0.069 mmol), 2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (compound 9.3, 200 mg, 0.28 mmol), DMAP (24 mg, 0.2 mmol), and DIC (0.1 mL, 0.63 mmol) in anhydrous DCM (10 mL) was stirred at room temperature over the weekend. The resulting mixture was loaded onto silica gel and purified by flash chromatography using an eluent of DCM / EA (0% to 10% EA). The major red peak was collected and concentrated under reduced pressure. The resulting solid was triturated with MeOH, filtered, and dried in air to give a dark solid (compound 9, 100 mg, 69% yield). 1H NMR(400MHz,CD2Cl2) δ 8.69(s,2H), 8.46(s,2H), 7.95~7.77(m,16H), 7.68~7.61(m,4H), 7.58~7.47( m,8H), 7.38(ddd,J=8.5,7.2,1.5Hz,2H), 7.34~7.27(m,4H), 7.23(dd,J=8.3,1 .3Hz,2H), 7.11(dd,J=8.4,1.5Hz,2H), 6.98~6.82(m,8H), 6.80~6.73(m,4H), 6.48(s,2H), 6.01(s,2H), 5.00(s,4H), 3.83(s,4H), 1.97(s,6H), 1.85(s,3H).

[0155] Synthesis of compound 10 [ka]

[0156] Compound 10.1 (2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid): Compound 10.1 was synthesized from compound 9.2 (3.500 mmol, 2.034 g), (3,5-bis(trifluoromethyl)phenyl)boronic acid (14.00 mmol, 3.611), KCO (19.25 mmol, 2.661 g), and Pd(dppf)Cl (0.0245 mmol, 179 mg) in THF (60 mL), DMF (12 mL), and water (6 mL) with heating at 80 °C overnight under argon atmosphere. The crude reaction mixture was evaporated to dryness in vacuo, taken up in DCM and evaporated in vacuo onto approximately 35 g of flash silica gel. Purification was achieved by flash chromatography on silica gel (220 g, equilibrated 0% EtOAc / DCM, eluted 0% (10 CV) to 15.3% EtOAc / DCM (15.3 CV) to 0% EtOAc / DCM (10 CV) to isocratic 40% EtOAc / DCM). EtOAc contained 0.1% v / v TFA. 1.710 g (57.6% yield) of a brownish yellow solid was obtained. MS (APCI): Chemical formula: C 42 H19 F 12 Calculated for NO5 (M+H)=846; Found: 846. 1 H NMR(400MHz,DMSO) δ 12.45(s,1H), 8.62(s,1H), 8.52(d,J=1.7Hz,2H), 8.36(s,1H), 8.30(s, 1H), 8.26(d,J=1.6Hz,2H), 8.24(s,1H), 7.50(ddd,J=8.5,7.2,1.5Hz,1H ), 7.46~7.38(m,2H), 7.37~7.27(m,2H), 7.14(dd,J=8.3,1.2Hz,1H), 6.98(ddd,J=8.4,7.2,1.3Hz,1H), 6.85(dd,J=8.3,1.5Hz,1H), 3.69(s,2H).

[0157] Compound 10 ((5,5-difluoro-10-mesityl-1,9-diphenyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-3,7-diyl)bis(4,1-phenylene))bis(prop-2-yn-3,1-diyl)bis(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xanthen[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate ester: A mixture of compound 5.7 (50 mg, 0.069 mmol), 2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (compound 10.1, 236 mg, 0.28 mmol), DMAP (24 mg, 0.2 mmol), and DIC (0.1 mL, 0.63 mmol) in anhydrous DCM (10 mL) was stirred at room temperature over the weekend. The resulting mixture was loaded onto silica gel and purified by flash chromatography using an eluent of DCM / EA (0% to 10% EA). The major red peak was collected and concentrated under reduced pressure. The resulting solid (compound 10) was triturated with MeOH, filtered, and dried in air to give a dark solid (130 mg, 79% yield). 1H NMR (400MHz, CD2Cl2) δ 8.75(s,2H), 8.51(s,2H), 8.31~8.26(m,4H), 8.05(d,J=16.1Hz,8H), 7.91~7.84(m, 4H), 7.59~7.48(m,8H), 7.44(ddd,J=8.6,6.9,1.7Hz,2H), 7.36~7.28(m,4H), 7.23( dd,J=8.3,1.3Hz,2H), 7.03~6.90(m,6H), 6.85(dd,J=8.4,6.8Hz,4H), 6.80~6.73(m ,4H), 6.48(s,2H), 6.01(s,2H), 5.01(s,4H), 3.84(s,4H), 1.98(s,6H), 1.85(s,3H).

[0158] Synthesis of Compound 11

change

[0159] Compound 11.1: 4-(3,7-bis(4-bromophenyl)-5,5-difluoro-1,9-diphenyl-5H-4,5-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinin-10-yl)-3,5-dimethylphenol: A 100 mL two-neck round-bottom flask was fitted with an air condenser and a stir bar. 2-(4-bromophenyl)-4-phenyl-1H-pyrrole (1.0 g, 3.35 mmol) and 4-hydroxyl-2,6-dimethylbenzaldehyde (251.9 mg, 1.68 mmol) were added to the flask, followed by anhydrous dichloroethane (35 mL). The reaction mixture was sparged with Ar for 30 min, then p-TsOH·HO (57.3 mg, 0.30 mmol) was added. The reaction solution was heated to 60°C and kept at this temperature overnight. The reaction was then cooled to room temperature and DDQ (608.4 mg, 2.68 mmol) was added. The reaction was kept at room temperature for 30 min. BF3·OEt2 (2.5 mL, 20.1 mmol) and Et3N (1.9 mL, 13.4 mmol) were then added at room temperature. The reaction mixture was heated to 50°C and kept at this temperature for 2 h. The reaction mixture was loaded with silica gel and purified by flash chromatography using DCM in hexanes (0%→100%) as the eluent to give pure compound 11.1 as a dark purple to gold solid (560.0 mg, 43% yield). MS (APCI): Formula: C 41 H 29 BBr2F2N2O([MH] - ) Calculated value = 774 Actual value: 774. 1 H NMR (400MHz, CDCl2CDCl2) 7.81(m,4H), 7.62(m,4H), 7.02(m,2H), 6.95(m,4H), 6.78(m,4H), 6.47(s,2H), 5.71(s,2H), 4.27(s,1H), 1.98(s,6H).

[0160] Compound 11.2: 3,3'-((5,5-difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-1,9-diphenyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-3,7-diyl)bis(4,1-phenylene))bis(prop-2-yn-1-ol): A 100 mL Schlenk tube was equipped with a stir bar. To the tube was added compound 11.1 (155.0 mg, 0.20 mmol), CuI (7.6 mg, 0.04 mmol), PdCl2(PPh3)2 (28.1 mg, 0.04 mmol), and prop-2-yn-1-ol (44.8 mg, 0.8 mmol), followed by anhydrous Et3N (5 mL). The reaction mixture was sparged with N2 for 30 min. The reaction mixture was heated to 80°C and kept at this temperature for 8 h. LCMS showed the reaction was complete. DCM (50 ml) and 0.5 M HCl (100 mL) were added. The aqueous phase was further extracted with DCM (50 ml x 3). The combined organic phase was concentrated on a rotary evaporator and the crude was purified by flash chromatography using EtOAc in DCM (0% -> 50%) as the eluent to give pure 11.2 as a dark purple solid (111.0 mg, 77% yield). MS (APCI): Formula: C 47 H 35 BF2N2O3([MH] - ) Calculated value = 724 Actual value: 724. 1 H NMR(400MHz,CDCl2CDCl2)7.92(m,4H), 7.55(m,4H), 7.02(m,2H), 6.94(m,4H), 6.79(m,4H), 6. 51(s,2H), 5.71(s,2H), 4.54(d,J=6.0Hz,4H), 4.27(s,1H), 1.98(s,6H), 1.77(t,J=6.0Hz,2H).

[0161] Compound 11: ((10-(4-(2-(4-(9-(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dimethylphenyl)-5,5-difluoro-1,9-diphenyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f] [1,3,2]diazaborinine-3,7-diyl)bis(4,1-phenylene))bis(prop-2-yn-3,1-diyl)bis(2-(4-(9-(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: A 25 mL vial was equipped with a stir bar. To the vial was added compound 11.2 (72.4 mg, 0.10 mmol), compound 6.1 (379.0 mg, 0.60 mmol), DIC (176.4 mg, 1.40 mmol), and DMAP (55.0 mg, 0.45 mmol), followed by anhydrous DCM (15 ml). The reaction mixture was kept at room temperature for 5 days, and after 24 hours, DIC (25.2 mg, 0.20 mmol) was added. The reaction mixture was loaded with silica gel and purified by flash chromatography using EtOAc in DCM (0%→10%) as eluent to give pure compound 11 as a dark red-purple solid. The solid was further triturated with EtOAc / MeOH (2 ml / 10 ml) to give compound 12. The solid was further purified by flash chromatography using EtOAc in hexane (0%→60%) and EtOAc in DCM (0%→10%) as eluent, then triturated with DCM / EtOAc / MeOH (9:1:1), and this cycle was repeated twice to give pure 11 (137.0 mg, 53% yield). 1 H NMR(400MHz,CDCl2CDCl2)8.64(m,6H), 8.25(m,3H), 8.11(m,9H), 7.93(m,7H), 7.79(m,3H), 7.57(m,13H), 7.37( m,9H), 7.01(m,6H), 6.77(m,4H), 6.52(s,2H), 6.11(s,2H), 5.02(s,4H), 3.90(s,2H), 3.85(s,4H), 2.05(s,6H).

[0162] Synthesis of compound 12 [ka]

[0163] Compound 12: ((10-(4-(2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dimethylphenyl)-5,5-difluoro-1,9-diphenyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f] [1,3,2]diazaborinine-3,7-diyl)bis(4,1-phenylene))bis(prop-2-yn-3,1-diyl)bis(2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: A 25 mL vial was equipped with a stir bar. To the vial was added compound 11.2 (50.0 mg, 0.07 mmol), compound 9.3 (261.5 mg, 0.42 mmol), DIC (123.5 mg, 0.98 mmol), and DMAP (38.0 mg, 0.32 mmol), followed by anhydrous DCM (11 ml). The reaction mixture was kept at room temperature overnight. The reaction mixture was loaded with silica gel and purified by flash chromatography using EtOAc in DCM (0%→10%) as eluent to give compound 12 as a dark red-purple solid. The solid was further triturated with EtOAc / MeOH (2 ml / 10 ml) to give compound 12. The solid was further purified by flash chromatography using EtOAc in hexanes (0%→60%) and EtOAc in DCM (0%→10%) as eluents, then triturated with DCM / EtOAc / MeOH (10:1:10), and this cycle was repeated twice to give pure compound 12 (139.0 mg, 71% yield). 1H NMR (400MHz, CDCl2CDCl2)8.72(s,1H), 8.69(s,2H), 8.49(s,1H), 8.46(s,2H), 7.87(m,22H), 7.62(m,16H), 7.41(m,5H) , 7.31(m,7H), 7.00(m,12H), 6.76(m,4H), 6.51(s,2H), 6.10(s,2H), 5.01(s,4H), 3.90(s,2H), 3.85(s,4H), 2.04(s,6H).

[0164] Synthesis of compound 13

change

[0165] Compound 13: ((10-(4-(2-(4-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dimethylphenyl)-5,5-difluoro-1,9-diphenyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f] [1,3,2]diazaborinine-3,7-diyl)bis(4,1-phenylene))bis(prop-2-yn-3,1-diyl)bis(2-(4-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: A 25 mL vial was equipped with a stir bar. To the vial was added compound 11.2 (50.0 mg, 0.07 mmol), compound 5.5 (237.5 mg, 0.42 mmol), DIC (123.5 mg, 0.98 mmol), and DMAP (38.0 mg, 0.32 mmol), followed by anhydrous DCM (11 ml). The reaction mixture was kept at room temperature overnight. The reaction mixture was loaded with silica gel and purified by flash chromatography using EtOAc in DCM (0%→10%) as eluent to give 14 as a dark red-purple solid. The solid was further triturated with EtOAc / MeOH (2 ml / 10 ml) to give compound 13. The solid was further purified by flash chromatography using EtOAc in hexanes (0%→60%) and EtOAc in DCM (0%→10%) as eluents, then triturated with DCM / EtOAc / MeOH (10:1:1), this cycle was repeated twice to give pure compound 13 (100.0 mg, 60% yield). 1 H NMR(400MHz,CDCl2CDCl2)8.63(m,6H), 8.10(m,10H), 7.77(m,15H), 7.57(m,11H), 7.39(m,11H), 6.9 9(m,6H), 6.77(m,4H), 6.52(s,2H), 6.11(s,2H), 5.02(s,4H), 3.90(s,2H), 3.86(s,4H), 2.05(s,6H).

[0166] Synthesis of compound 14 [ka]

[0167] Compound 14: ((10-(4-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dimethylphenyl)-5,5-difluoro-1,9-diphenyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f] [1,3,2]diazaborinine-3,7-diyl)bis(4,1-phenylene))bis(prop-2-yn-3,1-diyl)bis(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: A 25 mL vial was equipped with a stir bar. To the vial was added compound 11.2 (50.0 mg, 0.07 mmol), compound 10.1 (355.8 mg, 0.42 mmol), DIC (123.5 mg, 0.98 mmol), and DMAP (38.0 mg, 0.32 mmol), followed by anhydrous DCM (11 ml). The reaction mixture was kept at room temperature overnight. The reaction mixture was loaded with silica gel and purified by flash chromatography using EtOAc in DCM (0%→10%) as eluent to give compound 14 as a dark red-purple solid. The solid was further triturated with EtOAc / MeOH (2 ml / 10 ml) to give compound 14. The solid was further purified by flash chromatography using EtOAc in hexanes (0%→60%) and EtOAc in DCM (0%→10%) as eluents, then triturated with DCM / EtOAc / MeOH (9:1:10), and this cycle was repeated twice to give pure compound 14 (163.0 mg, 73% yield). 1H NMR(400MHz,CDCl2CDCl2)8.77(s,1H), 8.73(s,2H), 8.52(s,1H), 8.50(s,2H), 8.26(m,6H), 8.04(m,12H), 7.92(m,4H), 7.58(m,10H), 7.48(m,3H) , 7.40(m,2H), 7.34(m,4H), 7.27(m,3H), 6.99(m,12H), 6.76(m,4H), 6.51 (s,2H), 6.10(s,2H), 5.01(s,4H), 3.90(s,2H), 3.85(s,4H), 2.04(s,6H).

[0168] Example 3: Manufacturing color conversion film The glass substrate was prepared substantially as follows: A 1.1 mm thick glass substrate measuring 1 inch by 1 inch was cut to size. The glass substrate was then cleaned with detergent and deionized (DI) water, rinsed with fresh DI water, and sonicated for about 1 hour. The glass was then immersed in isopropanol (IPA) and sonicated for about 1 hour. The glass substrate was then immersed 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.

[0169] A 25 wt% solution of poly(methyl methacrylate) (PMMA) (average molecular weight 120000 by GPC, MilliporeSigma, Burlington, Massachusetts, USA) was prepared in toluene. The PMMA polymer prepared in toluene was stirred overnight at 60°C until completely dissolved. [PMMA] CAS: 9011-14-7; [Toluene] CAS: 108-88-3.

[0170] The 25% PMMA solution (3.4 mL) prepared above was added to 2 mg of the chromophore dye prepared above in a sealed container, mixed well using a vortex for 5 minutes, and sonicated for 30 minutes. The PMMA / chromophore solution was then spin-coated onto the prepared glass substrate at 1000 RPM for 20 seconds. The resulting wet coating had a thickness of about 10 μm. In this manner, three samples were prepared for absorption, emission / FWHM, and quantum yield measurements, respectively. The spin-coated samples were baked in an oven at 150° C. for 5 minutes to evaporate the residual solvent. Other examples were performed similarly, except that poly(butyl acrylate) solution was utilized instead of PMMA solution. Poly(butyl acrylate) (PBA) solution (molecular weight about 99000 by GPC) was purchased from Sigma Aldrich (CAS: 9003-49-0).

[0171] For absorption spectrum measurements, a 1 inch × 1 inch sample was inserted into a Shimadzu UV-3600 UV-VIS-NIR spectrophotometer (Shimadzu Instruments, Inc., Columbia, MD, USA).

[0172] Fluorescence spectra of 1 inch × 1 inch film samples prepared as described above were determined using a Fluorolog spectrofluorometer (Horiba Scientific, Edison, NJ, USA) with the excitation wavelength set at their respective maximum absorbance wavelengths. Emission maxima and FWHM are shown in Table 1.

[0173] The normalized absorption and emission spectra of compound 5 are shown in Figure 1. The normalized absorption and emission spectra of compound 6 are shown in Figure 2. The normalized absorption and emission spectra of compound 7 are shown in Figure 3.

[0174] The quantum yield of the 1 inch x 1 inch sample prepared as above was determined by a Hamamatsu C11347 absolute PL quantum yield spectrometer (Hamamatsu Inc., Campbell, CA, USA). The wavelength was scanned from 390 nm to 450 nm (as the excitation wavelength) every 30 nm and the quantum yield was measured. A film with a size of 0.5 inch x 0.5 inch was removed from the glass for measurement. The QY results at 450 nm are reported in Table 1. The structures of the compounds in the table can be found in the above description and examples.

[0175] [Table 1] [Table 2]

Claims

1. A photoluminescent complex comprising: a blue light absorbing xanthenoisoquinoline derivative; a linker conjugate comprising an unsubstituted or substituted ester; a boron-dipyrromethene (BODIPY) moiety; and Including, the linker conjugate covalently links the xanthenoisoquinoline derivative and the BODIPY moiety; the xanthenoisoquinoline derivative absorbs light energy at a first excitation wavelength and transfers energy to the BODIPY moiety; the BODIPY moiety absorbs the energy from the xanthenoisoquinoline derivative and emits a second, longer wavelength light energy; A photoluminescent complex, wherein the photoluminescent complex has an emission quantum yield of greater than 80%.

2. The xanthenoisoquinoline derivative has the general formula: 【Chemistry 1】 (In the formula, R １０ is H, C １ ~C ４ an alkyl group or an optionally substituted aryl group, R １１ is H or an optionally substituted aryl group.

3. The BODIPY moiety has the general formula: 【Chemistry 2】 (In the formula, R ２ , R ３ , R ４ , and R ５ are independently H, C １ ~C ３ an alkyl, an optionally substituted aryl, or an ether group; R ７ , R ８ , and R ９ are independently H or methyl (—CH ３ ) and L １ , L ２ , and L ３ is a linker conjugate, said linker conjugate being independently an unsubstituted ester or a substituted ester.

4. R ３ and R ４ 4. The photoluminescent complex of claim 3, wherein is an optionally substituted aryl group.

5. 5. The photoluminescent complex of claim 4, wherein the optionally substituted aryl group comprises a 4-trifluoromethylphenyl group or a 3,5-bis(trifluoromethyl)phenyl group.

6. 5. The photoluminescent complex of claim 4, wherein the optionally substituted aryl group is a phenyl group.

7. the linker complex 【Transformation 3】 2. The photoluminescent complex of claim 1, comprising:

8. the unsubstituted ester linker conjugate being 【Chemistry 4】 or a combination thereof.

9. The photoluminescent complex is 【Transformation 5】 【Transformation 6】 【Transformation 7】 【Transformation 8】 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】 10. The photoluminescent complex of claim 1, comprising:

10. A color conversion film, A transparent substrate layer; a color conversion layer including a resin matrix; a photoluminescent complex comprising the photoluminescent compound of claim 1 dispersed within the resin matrix; Including color conversion film.

11. The color conversion film of claim 10 , wherein the resin matrix comprises poly(methyl methacrylate).

12. The color conversion film of claim 10 , wherein the resin matrix comprises poly(butyl acrylate).

13. The color conversion film of claim 10, wherein the film has a thickness of about 10 μm to about 200 μm.

14. The color conversion film of claim 10 , further comprising a singlet oxygen quencher or a free radical scavenger.

15. 11. The color conversion film of claim 10, wherein the film absorbs light in the wavelength range of about 400 nm to about 590 nm and emits light in the wavelength range of about 600 nm to about 620 nm.

16. A method of making a color conversion film, comprising: Dissolving the photoluminescent complex according to claim 1 and a binder resin in a solvent; applying the mixture to one of the opposing surfaces of a transparent substrate; A method comprising:

17. The method of claim 16 , wherein the resin matrix comprises poly(methyl methacrylate).

18. The method of claim 16 , wherein the resin matrix comprises poly(butyl acrylate).

19. A backlight unit comprising the color conversion film according to claim 10 , 11 , 12 , 13 , 14 , or 15 .

20. A display device comprising the backlight unit according to claim 19.

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