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, color conversion films comprising the photoluminescent complexes, and backlight units employing the same.

Description

[Technical field]

[0001] [CROSS REFERENCE TO RELATED APPLICATIONS] This application claims priority to U.S. Provisional Patent Application No. 63 / 311,579, filed February 18, 2022, and U.S. Provisional Patent Application No. 63 / 379,583, filed October 14, 2022, the entire disclosures of which are incorporated herein by reference.

[0002] The present disclosure relates to compounds used in color conversion films, and to backlight units and display devices including 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, films containing quantum dots have been developed in combination with LEDs, but 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 dyes with good blue light absorption and narrow emission bandwidth, with a full width at half maximum (FWHM) of the emission band less than 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] Some embodiments include a photoluminescent complex comprising a blue light absorbing xanthenoisoquinoline derivative, a linker conjugate comprising an unsubstituted or substituted ester, and a boron-dipyrromethene (BODIPY) moiety. In some embodiments, the linker conjugate can covalently bond the xanthenoisoquinoline derivative to 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. In some embodiments, the BODIPY moiety absorbs energy from the xanthenoisoquinoline derivative and emits light energy at a second, longer wavelength. In some embodiments, the photoluminescent complex has an emission quantum yield of greater than 80%.

[0010] In some embodiments, the photoluminescent complexes can have an emission band with a full width at half maximum (FWHM) of up to 40 nm.

[0011] In some embodiments, the photoluminescent complex can have a Stokes shift, which is the difference between the excitation peak of the blue light absorbing moiety and the emission peak of the BODIPY moiety, of 45 nm or more.

[0012] In some embodiments, the photoluminescent complex has the formula: [ka] may have:

[0013] In some embodiments, the xanthenoisoquinoline derivative has the following general formula: [ka] (In the formula, R 9 is H, a C1-C4 alkyl group, or an optionally substituted aryl group, and the substituted functional group can be an optionally substituted C1-C3 methyl group, for example, trifluoromethyl (-CF3).

[0014] Some embodiments include a color conversion film including a transparent substrate layer, a color conversion layer, and at least one photoluminescent complex. In some embodiments, the color conversion layer may include a resin matrix. In some embodiments, the at least one photoluminescent complex is dispersed within the resin matrix. In some embodiments, the resin matrix may include poly(butyl acrylate). In some embodiments, the color conversion film may have a thickness between 10 μm and about 200 μm. In some embodiments, the color conversion film of the present disclosure may absorb blue light in the range of 400 nm to about 480 nm and emit light in the wavelength range of 510 nm to about 560 nm. Another embodiment includes a color conversion film that may absorb blue light in the range of 400 nm to about 480 nm and emit light in the wavelength range of 575 nm to about 645 nm. In some embodiments, the color conversion film may further include a transparent substrate layer. In some embodiments, the transparent substrate layer comprises two opposing surfaces and the color conversion layer is disposed on one of the opposing surfaces.

[0015] Some embodiments include a method of making a color conversion film, the method including dissolving a photoluminescent complex and a binder resin in a solvent and applying the mixture to one of the opposing surfaces of a transparent substrate.

[0016] Some embodiments include a backlight unit comprising the color conversion films described herein.

[0017] Some embodiments include a display device comprising a backlight unit as described herein.

[0018] The present application provides a photoluminescent complex having excellent color gamut and luminescence properties, a method for manufacturing a color conversion film including 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 (PLC-1). [Diagram 2] 1 is a graph showing the absorption and emission spectra of one embodiment of a photoluminescent complex (PLC-2). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0020] The present disclosure relates to photoluminescent boron-containing cyclic emissive complexes and their use in color conversion films, backlight units, and display devices. These complexes are often more simply referred to as photoluminescent complexes. Photoluminescent complexes can be used to improve and enhance the transmittance of one or more desired emission bandwidths in color conversion films. In some embodiments, the photoluminescent complexes can increase the transmittance of a first desired emission bandwidth and decrease the transmittance of a second emission bandwidth. For example, the color conversion film can enhance the contrast or intensity between two or more colors and enhance their differentiation from one another. The present disclosure also includes a method of making the color conversion films described herein.

[0021] As used herein, when a compound or chemical structure is referred to as "substituted" or "optionally substituted," it can contain one or more substituents. A substituted group is derived from an unsubstituted parent structure, where one or more hydrogen atoms on the parent structure are independently replaced by one or more substituents. In one or more forms, the substituents can be independently selected from an optionally substituted alkyl, alkenyl, or C3-C7 heteroalkyl.

[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 1-6 carbon atoms (whether or not indicated herein), and numerical ranges such as "1-6" refer to each integer within the given range, for example, "1-6 carbon atoms" means that the alkyl group may have 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc., including up to 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-C6 alkyl" or a similar designation. By way of example only, "C1-6 alkyl" indicates that there are 1-6 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-C6 alkyl includes C1-C2 alkyl, C1-C3 alkyl, C1-C4 alkyl, and C1-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 esters of the present disclosure.

[0032] The terms "may" or "could" should be interpreted as shorthand for "is" or "is not", alternatively "will" or "will not" or "will not" or "will not" etc. For example, the statement "the color converting film may include a transparent substrate layer" should be interpreted as, for example, "in some embodiments, the color converting film includes a transparent substrate layer" or "in some embodiments, the color converting film does not include a transparent substrate layer".

[0033] As used herein, the term "BODIPY" refers to a compound of the formula: [ka] and includes a dipyrromethene 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. In some embodiments, L is a linker conjugate.

[0034] As used herein, the term "xanthenioisoquinoline" or "xanthenioisoquinoline derivative" or "XI" refers to a compound of the formula: [ka] It refers to a chemical moiety having the formula:

[0035] The IUPAC name for the xanthenoisoquinoline core is 1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione.

[0036] 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.

[0037] Some embodiments include a photoluminescent complex. In some embodiments, the photoluminescent complex includes a blue light absorbing xanthenoisoquinoline derivative, a linker conjugate, and a boron-dipyrromethene (BODIPY) moiety. In some embodiments, the linker conjugate may covalently bond the xanthenoisoquinoline derivative to the BODIPY moiety. In some embodiments, the photoluminescent complex may be represented by the formula BLX, where B is a BODIPY moiety, L is a linker conjugate, and X is a xanthenoisoquinoline derivative. In some embodiments, the photoluminescent complex may be represented by the following chemical formula: [ka] It may be expressed as:

[0038] In some embodiments, the xanthenoisoquinoline derivative absorbs light at a first excitation wavelength and transfers energy to the BODIPY moiety, which then emits light energy at a second wavelength longer than the first wavelength. It is believed that the energy transfer from the excited xanthenoisoquinoline derivative to the BODIPY moiety occurs via Förster resonance energy transfer (FRET). This idea is due to the absorption / emission spectrum of the photoluminescent complex, which has two main absorption bands, one at the blue light absorption band (xanthenoisoquinoline derivative) and the other at the BODIPY absorption band, and only one emission band at the emission wavelength of the BODIPY moiety (see Figures 1 and 2).

[0039] In one embodiment, the photoluminescent complex may have a high emission quantum yield. In some embodiments, the emission quantum yield may be about 50%, about 55%, about 60%, about 65%, or about 70%, about 75%, about 80%, about 85%, about 90%, or more than about 90%. The emission quantum yield can 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 of more than 80%. In some embodiments, the quantum yield can be greater than 0.8 (80%), 0.81 (81%), 0.82 (82%), 0.83 (83%), 0.84 (84%), 0.85 (85%), 0.86 (86%), 0.87 (87%), 0.88 (88%), 0.89 (89%), 0.9 (90%), 0.91 (91%), 0.92 (92%), 0.93 (93%), 0.94 (94%), 0.95 (95%), or can be close to maximum (100%). Quantum yield measurements on films can be performed by a spectrophotometer, for example, a Quantaurus-QY spectrophotometer (Hamamatsu, Inc., Campbell, Calif., USA).

[0040] 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 35 nm or less, about 30 nm or less, about 25 nm or less, or about 20 nm or less. In some embodiments, the FWHM is about 20 nm to about 25 nm, about 25 nm to 30 nm, about 30 nm to 35 nm, or about 35 nm to 40 nm.

[0041] 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.

[0042] In some embodiments, the photoluminescent complexes of the present disclosure may have a tunable (or adjustable) emission wavelength. In some embodiments, the emission wavelength may be adjusted to about 610 nm to about 645 nm by utilizing different substituents on the BODIPY moiety. In some examples, the photoluminescent complexes may have an emission peak wavelength between about 610 nm to about 645 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, or any wavelength within the range defined by any of these values.

[0043] In some embodiments, the photoluminescent complex may absorb light energy at one or more wavelengths. In some embodiments, the xanthenoisoquinoline moiety of the photoluminescent complex may absorb light. In some embodiments, the BODIPY moiety of the photoluminescent complex may absorb light. In some embodiments, both the BODIPY moiety of the photoluminescent complex and the xanthenoisoquinoline moiety of the photoluminescent complex may absorb light. In some embodiments, the blue light absorbing xanthenoisoquinoline moiety of the photoluminescent complex may have a peak absorption maximum wavelength between about 400 nm and about 470 nm. In some embodiments, the peak absorption may be between 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, or any wavelength within a range defined by any of these values. 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, 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 The absorbance wavelength may be between 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, or any wavelength within a range defined by any of these values.

[0044] 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. In some embodiments, the photoluminescent complex has an emission quantum yield of more than 80%.

[0045] Some embodiments include blue light absorbing xanthenoisoquinolinic derivatives (XI derivatives), which have the general formula: [ka] (In the formula, R 9 may independently be H, methyl, or an optionally substituted aryl group; R 10 are independently H, C 1~4 In some embodiments, the optionally substituted aryl group may be a substituted phenyl group or a substituted benzyl group. In some embodiments, the aryl group may be substituted with a trifluoromethyl moiety. In some embodiments, the substituted aryl group may be [ka] It could be.

[0046] The linker complex L covalently connects the blue light absorbing xanthenoisoquinoline derivative to the BODIPY moiety. The linker complex can be adjusted to optimize the spatial distance between the blue light absorbing xanthenoisoquinoline derivative and the BODIPY moiety. Adjusting 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. The linker complex can maintain the distance between the blue light absorbing xanthenoisoquinoline derivative and the BODIPY moiety. In other embodiments, the linker complex can include a single bond between the xanthenoisoquinoline derivative and the BODIPY moiety.

[0047] In some embodiments, the linker conjugate may include an optionally substituted C1-C6 ester group. When the linker conjugate includes a substituted ester group, the linker conjugate has the following structure: [ka] may include one of:

[0048] In some embodiments, the linker conjugate may include an unsubstituted ester group. When the linker conjugate includes an unsubstituted ester group, the linker conjugate has the following structure: [ka] may include one of:

[0049] In some embodiments, the linker conjugate may include a substituted ester linker. The substituted ester linker has the following structure: [ka] may include one of:

[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 , R 6 may be independently selected from H, C1-C3 alkyl, aryl, ester, or ether. In some embodiments, R 7 and R 8 may be independently selected from H or a methyl group (-CH). In some embodiments, R 2 and R 5 are independently H or C1-C 12 In some embodiments, R 2 and / or R 5 has the following structure: [ka] may include one of:

[0052] The BODIPY moiety of the present disclosure is R 3 and R 4 may each be an optionally substituted aryl group, e.g., a phenyl group; R 1 , R 2 , R 5 and R 6 are independently H, a substituted aryl group (e.g., an optionally substituted phenyl group, e.g., [ka] may be a BODIPY moiety.

[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] or a combination of any of these structures.

[0054] Some embodiments include a color conversion film, which includes a color conversion layer including 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.

[0055] Some embodiments include color conversion films that may be about 1 μm to about 200 μm thick. In some embodiments, the color conversion film may be described as having a thickness of about 1 μm to about 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 any thickness within a range defined by any of these values.

[0056] In some embodiments, the color conversion film can absorb light with wavelengths from 400 nm to about 480 nm and emit light in the range of about 610 nm to about 645 nm, while in other embodiments, the color conversion film can emit light in the range of 610 nm to about 645 nm.

[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), PBA (polybutylacrylate), (acrylic acid). A suitable polymer may be [HAB5] (Nitto Denko Corporation, Osaka, Japan). Any of the aforementioned resins may be the corresponding respective monomers and / or polymers.

[0058] 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.

[0059] 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.

[0060] 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 butyl acrylate. In some embodiments, the binder resin can be a copolymer mixture including 50%, 75%, 95% butyl acrylate [copolymer]. It is believed that poly(butyl acrylate) (PBA) matrix can provide a more non-polar environment (having n-butyl alkyl chains in the structure) compared to PMMA. It is believed that the non-polar environment in PBAs causes the chromophore dyes to aggregate / stack more with each other in the matrix, which can lead to charge transfer, resulting in generally lower quantum yields in PBAs.

[0061] Solvents that may be used to dissolve or disperse the complexes and resins include 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, Furans, esters such as butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate, ethyl 2-hydroxybutyrate, ethyl acetoacetate, methyl lactate, ethyl lactate, and methyl 3-methoxypropionate, halogenated hydrocarbons such as chloroform, methylene chloride, and tetrachloroethane, aromatic hydrocarbons such as benzene, toluene, xylene, and cresol, and highly polar solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone may be mentioned.

[0062] Some embodiments include a backlight unit, which may include the color conversion film described above.

[0063] Other embodiments may include a display device, which may include a backlight unit as described herein.

[0064] 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.

[0065] 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.

[0066] This disclosure may at times describe different components contained within or in conjunction with different other components, and such depicted configurations are merely exemplary, and many other configurations may be realized that achieve the same or similar functionality.

[0067] 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."

[0068] The terms "a," "an," "the," and similar referents used in the context of describing this disclosure (particularly in the context of the embodiments below) should be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The use of any and all examples or representative language (e.g., "such as") 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 the specification should not be construed as indicating any non-embodied element essential to the practice of the disclosure.

[0069] 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.

[0070] 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.

[0071] 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%.

[0072] 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.

[0073] Embodiment 3 An optionally substituted aryl group is [ka] 3. The photoluminescent complex of embodiment 2, comprising:

[0074] Embodiment 4 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, ester, and / or ether; R 7 and R 8 can be independently selected from a bond, H, or a methyl group (-CH3); The photoluminescent complex of embodiment 1, wherein L1 is a linker conjugate, which is an unsubstituted ester or a substituted ester.

[0075] Embodiment 5 R 3 and R 4 may each be an aryl group, e.g., a phenyl group; A photoluminescent complex according to embodiment 4.

[0076] Embodiment 6. The photoluminescent complex of embodiment 5, wherein the aryl group can be a phenyl group.

[0077] Embodiment 7: The phenyl group is [ka] 7. The photoluminescent complex of embodiment 6, comprising:

[0078] Embodiment 8: An ether [ka] The photoluminescent complex of embodiment 4, which may be:

[0079] Embodiment 9 R 2 and R 5 The photoluminescent complex of embodiment 4, wherein each of

[0080] Embodiment 10: The ester group is C1-C 12 ester( [ka] 10. The photoluminescent complex of embodiment 9, wherein

[0081] Embodiment 11: The linker is [ka] 2. The photoluminescent complex of embodiment 1, comprising:

[0082] Embodiment 12: The unsubstituted ester linker is [ka] 2. The photoluminescent complex of embodiment 1, comprising:

[0083] Embodiment 13. The method according to claim 1, wherein the substituted ester of the linker conjugate has the following structure: [ka] 13. The photoluminescent complex of embodiment 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, wherein

[0084] Embodiment 14. A photoluminescent complex having the following structure: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] or a combination thereof.

[0085] Embodiment 15 A color conversion film comprising: A transparent substrate layer; a color conversion layer including a resin matrix; At least one photoluminescent complex comprising the photoluminescent compound of embodiment 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14 dispersed in a resin matrix; Including color conversion film.

[0086] Embodiment 16. The color converting film of embodiment 15, wherein the resin matrix comprises polybutylacrylate.

[0087] Embodiment 17 The color conversion film of embodiment 15, further comprising a singlet oxygen quencher.

[0088] Embodiment 18. The color converting film of embodiment 15, further comprising a free radical scavenger.

[0089] Embodiment 19. The color converting film of embodiment 15, wherein the film has a thickness between 10 μm and 200 μm.

[0090] Embodiment 20 The color conversion film of embodiment 15, wherein the film absorbs light in the wavelength range of about 400 nm to about 480 nm and emits light in the wavelength range of 575 nm to about 645 nm.

[0091] Embodiment 21 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, 12, 13, or 14 and a binder resin in a solvent; applying the mixture to one of the opposing surfaces of a transparent substrate; A method comprising:

[0092] Embodiment 22. The method of embodiment 21, wherein the binder resin comprises polybutyl acrylate (HAB5).

[0093] Embodiment 23 A backlight unit comprising the color conversion film of embodiment 15, 16, 17, 18, 19, or 20.

[0094] Embodiment 24 A display device comprising the backlight unit of embodiment 23. EXAMPLES

[0095] 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 merely to illustrate the disclosure and are not intended to limit the scope or underlying principles in any way.

[0096] Example 1.1 Comparative example 1 (CE-1): [ka]

[0097] 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. 1H 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).

[0098] Example 1.2 Comparative example 2 (CE-2): Comparative Example 2 was synthesized as described in Wakamiya, Atsushi et al. Chemistry Letters, 37(10), 1094-1095; 2008.

[0099] Example 2. Synthesis of photoluminescent complexes: Synthesis of compound PLC-1 [ka]

[0100] Compound PLC-1.1: A mixture of 4-bromo-1,8-naphthalic anhydride (2.77 g, 10 mmol), 4-bromo-2-nitrophenol (3.27 g, 15 mmol) was degassed under vacuum for 30 minutes, 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 minutes 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 hours, 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 gave a tan solid (3.3 g, 80% yield) as the desired product. LCMS (APCI+): C 18 Calculated for H9BrNO6 (M+H)=413.95; Found: 414. 1H 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).

[0101] Compound PLC-1.2: A mixture of PLC-1.1 (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 (1.35 g, 82% yield). LCMS (APCI-): C 18 H 10 Calculated 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).

[0102] Compound PLC-1.3: PLC-1.2 (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 while 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×3), and then stirred in 50 mL of acetone at 40° C. for 30 min. Filtration and drying in air and then vacuum gave a tan solid (1.76 g, 70% yield). LCMS (APCI+): C 18 Calculated for H8BrO4 (M+H)=366.95; found: 367. 1H 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).

[0103] Compound PLC-1.4: 2-(4-(9-bromo-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid: A mixture of PLC-1.3 (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 obtain pure compound PLC-1.4 as a tan solid (395.0 mg, 73% yield). MS (APCI): Chemical formula: C 26 H 14 Calculated for BrNO5 ([M+H]+)=500; Found: 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).

[0104] Compound PLC-1.5: 2-(4-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-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 PLC-1.4 (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 / HO (22 mL / 4.4 mL / 2.2 mL) and degassed at room temperature. The reaction mixture was heated to 80 °C and maintained at this temperature overnight. The reaction was monitored using TLC. Upon 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 PLC-1.5 as a yellow / tan solid (363.0 mg, 80% yield). MS (APCI): Formula: C 33 H 18 Calculated for F3NO5 ([M+H]+)=566; Found: 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).

[0105] Compound PLC-1.6: Step 1: A mixture of 2-(4-bromophenyl)-4-phenyl-1H-pyrrole (PLC-1.2) (1.0 g, 3.36 mmol), 4-hydroxyl-2,6-dimethylbenzaldehyde (0.252 g, 1.68 mmol) and p-TsOH (50 mg) in 1,2-dichloroethane (50 mL) was heated at 60° C. for 48 h. LCMS analysis shows that the main peak is the desired product with m / e+=727.

[0106] Step 2: To the mixture from step 1, DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoquinone) (570 mg, 2.51 mmol) was added and stirred at room temperature for 30 min. LCMS analysis shows the reaction is complete with a major peak at m / e-=723.

[0107] Step 3: To the mixture from step 2, triethylamine (1.7 mL, 12 mmol), boron trifluoride diethyl etherate (BF3·OEt2) (3.5 mL, 28 mmol) were added at 0°C. The whole was heated at 50°C for 1 h. LCMS shows the reaction is complete with a main peak at m / e-=772. The mixture was diluted with 100 mL of dichloromethane (DCM), then washed twice with water and once with brine, then loaded onto silica gel and purified by flash chromatography using an eluent of hexane / DCM (0% to 100% DCM). The second main desired peak was collected and after removing the solvent under reduced pressure, the desired product was obtained as a purple solid (0.45 g, 34.6% yield). Confirmed by LCMS (APCI): C 41 H 29 Calculated for BBr2F2N2O(M-): 772.07; Found: 772. 1 H NMR (400MHz,d2-TCE) δ 7.84~7.64(m,4H), 7.61~7.42(m,4H), 7.03~6.81(m,6H), 6.77~6.64(m,4H), 6.38(s,2H), 5.62(s,2H), 1.89(s,6H).

[0108] Compound PLC-1: A mixture of PLC-1.6 (50 mg, 0.0645 mmol), 2-(4-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (50 mg, 0.089 mmol), DIC (0.15 mL, 0.945 mmol), DMAP / p-TsOH (50 mg, 0.17 mmol) in DCM (5 mL) was stirred at room temperature overnight, then diluted with 20 mL of DCM, loaded onto silica gel, and purified by flash chromatography using an eluent of hexane / DCM (0% to 100% DCM). The main desired fraction was collected. The solvent was removed under reduced pressure, triturated with methanol, and filtered to give a dark purple solid (40 mg, 47% yield). LCMS (APCI-): C 74 H 45 Calculated for BBr2F5N3O5: 1319.19; Found: 1319. 1 H NMR(400MHz,d2-TCE) δ 8.59(dd,J=19.2,8.1Hz,2H), 8.21(d,J=2.1Hz,1H), 8.03(d,J=8.1Hz,1H), 7.78~7.67(m,9H), 7.57~7.43(m,7H), 7.3 2(dd,J=17.5,8.3Hz,3H), 7.00~6.85(m,6H), 6.74~6.63(m,4H), 6.38(s,2H), 6.02(s,2H), 3.81(s,2H), 1.96(s,6H).

[0109] Synthesis of compound PLC-3 [ka]

[0110] Compound PLC-3.4: A mixture of PLC-1.3 (550 mg, 1.5 mmol), 4-(4-aminophenyl)butanoic acid (537 mg, 3 mmol) and DMAP (12.2 mg, 0.1 mmol) in 10 mL of DMF was heated in a microwave reactor at 165° C. for 2.5 h. The resulting solution was added dropwise to 50 mL of acetone with stirring. A precipitate formed, which was filtered and dried overnight in a vacuum oven at 60° C. to give the desired product as a tan solid (0.49 g, 62% yield). LCMS (APCI-): C 28 H 18 Calculated for BrNO5=527.04; Found: 527. 1 H NMR(400MHz,DMSO-d6) δ 8.54(d,J=2.3Hz,1H), 8.41(dd,J=9.9,8.0Hz,2H), 8.33(d,J=7.9Hz,1H), 7.71(dd,J=8.8,2.3Hz,1H), 7.39(dd,J=8. 6,4.2Hz,2H), 7.25(d,J=8.0Hz,2H), 7.17(d,J=7.9Hz,2H), 2.63~2.55(m,2H), 2.27~2.15(m,2H), 1.87~1.73(m,2H).

[0111] Compound PLC-3.5: A mixture of PLC-3.4 (649 mg, 1.23 mmol), 4-(trifluoromethyl)phenylboronic acid (467 mg, 2.46 mmol), Pd(dppf)Cl2 (45 mg, 0.06 mmol), potassium carbonate (345 mg, 2.5 mmol) in a cosolvent of THF / DMF / water (30 mL / 6 mL / 3 mL) was degassed and then heated at 80 °C overnight. The mixture was worked up with 300 mL of ethyl acetate and 50 mL of 0.6 N aqueous hydrochloric acid. The aqueous phase was extracted with ethyl acetate (150 mL x 3). The organic phase was collected, washed with brine (100 mL x 2), dried over sodium sulfate, then dry loaded onto silica gel and purified by flash chromatography using an eluent of DCM / EA (0% → 80% EA with 0.1% TFA). The main desired fraction was collected and the solvent removed under reduced pressure to give a yellow solid (414 mg, 57% yield). 1H NMR(400MHz,d2-TCE) δ 8.55(dd,J=18.1,8.1Hz,2H), 8.16(d,J=2.2Hz,1H), 8.00(d,J=8.1Hz,1H), 7.68(dd,J=8.6,2.1Hz,1H), 7.66~7.59(m,2H), 7.43(d ,J=8.6Hz,1H), 7.32(tt,J=8.2,4.2Hz,5H), 7.20~7.13(m,2H), 2.72(t,J=7.6Hz,2H), 2.39(t,J=7.3Hz,2H), 1.99(q,J=7.4Hz,2H).

[0112] Compound PLC-3: A mixture of PLC-1.6 (77.5 mg, 0.1 mmol), 4-(4-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)butanoic acid (100 mg, 0.17 mmol), DIC (0.1 mL, 0.63 mmol), DMAP / p-TsOH (29 mg, 0.1 mmol) in DCM (8 mL) was stirred at room temperature overnight, then diluted with 10 mL of DCM, loaded onto silica gel, and purified by flash chromatography using an eluent of DCM / EA (0% to 5% EA). The main desired fraction was collected, concentrated under reduced pressure, triturated with methanol, and filtered to give a dark red solid (90 mg, 67% yield). LCMS (APCI-): C 76 H 49 Calculated for BBr2F5N3O5: 1347.21; Found: 1347. 1H NMR(400MHz,d2-TCE) δ 8.57(dd,J=18.8,8.1Hz,2H), 8.20(d,J=2.1Hz,1H), 8.02(d,J=8.1Hz,1H), 7.72(dt,J=8. 6,2.7Hz,9H), 7.57~7.49(m,4H), 7.46(d,J=8.6Hz,1H), 7.41~7.36(m,2H), 7.33(d,J=8.3H) z,1H), 7.26~7.17(m,2H), 7.02~6.84(m,6H), 6.68(dt,J=6.9,1.4Hz,4H), 6.38(s,2H), 5.9 9(s,2H), 2.76(t,J=7.5Hz,2H), 2.47(t,J=7.4Hz,2H), 2.05(p,J=7.5Hz,2H), 1.96(s,6H).

[0113] Synthesis of compound PLC-4 [ka]

[0114] Compound PLC-4.1: ((E)-1-(4-(tert-butyl)phenyl)-3-phenylprop-2-en-1-one): A 100 mL collection flask was equipped with a stir bar. To the flask was added 1-(4-(tert-butyl)phenyl)ethan-1-one (10.0 mmol, 1.83 mL), benzaldehyde (10.0 mmol, 1.00 mL), and 200 proof ethanol (5 mL). The mixture was stirred at room temperature and water (2.4 mL) was added followed by the dropwise addition of 5M KOH (12.00 mmol, 2.4 mL) over 45 seconds. The reaction was stirred vigorously at room temperature for 6 hours. The reaction mixture was diluted with water (50 mL) and stirred for 10 minutes. The precipitate was filtered off and washed with water. Suction dried, then dissolved in DCM and evaporated to dryness in vacuo. 2.386 g (90% yield) of an off-white solid was obtained. MS(APCI):Chemical formula:C 19 H 20 Calculated for O (M+H)=265; Found: 265. 1H NMR(400MHz,TCE) δ 8.01~7.95(m,2H), 7.80(d,J=15.7Hz,1H), 7.70~7.64(m,2H), 7.57(d,J=11.0Hz,1H), 7.55~7.52(m,2H), 7.49~7.43(m,3H), 1.37(s,9H).

[0115] Compound PLC-4.2: (1-(4-(tert-butyl)phenyl)-4-nitro-3-phenylbutan-1-one): Compound PLC-4.2 was synthesized similarly to PLC-2.2 (see below) from compound PLC-4.1 (9.018 mmol, 2.384 g) and KOH (1.804 mmol, 101 mg) in 200 proof ethanol (11 mL) and nitromethane (11 mL) at 95° C. for 1 hour. The crude reaction mixture was partitioned between water (100 mL) and EtOAc (100 mL). A small amount of NaCl was added to break the emulsion. The organic layer was dried over MgSO4, filtered, and evaporated to dryness in vacuo. 2.784 g (95% yield) of a brown oil was obtained. MS (APCI): Chemical formula: C 20 H 23 Calculated for NO3 (M+H)=326; Found: 326. 1 H NMR(400MHz,TCE) δ 7.90~7.83(m,2H), 7.52~7.46(m,2H), 7.40~7.34(m,2H), 7.34~7.26(m,3H), 4.85(dd,J=12.5,6.3Hz,1H), 4.69(dd,J= 12.5,8.3Hz,1H), 4.21(tt,J=8.1,6.2Hz,1H), 3.47(dd,J=17.8,6.1Hz,1H), 3.39(dd,J=17.8,7.8Hz,1H), 1.34(s,9H).

[0116] Compound PLC-4.4: (2-(4-(tert-butyl)phenyl)-4-phenyl-1H-pyrrole): PLC-4.2 (6.822 mmol, 2.220 g) was treated with KOH (17.66 mmol, 991 mg) in dry THF (75 mL) and dry MeOH (40 mL), then this solution was added dropwise into an ice-cold mixture of dry methanol (40 mL) and 96% H2SO4 (8.5 mL). After addition, the reaction was allowed to warm to room temperature. The reaction was kept at room temperature for an additional 1 h. LCMS showed the reaction was complete. The reaction solution was poured onto crushed ice and extracted with EtOAc (150 ml x 3). The combined organic phase was washed with 10% (wt / wt) Na2CO3 in H2O and then washed with brine. After drying over anhydrous Na2SO4, the solution was concentrated under vacuum rotary evaporator to give the desired product PLC-4.3 as an oil, which was used in the next step without further purification. The crude product was confirmed to be dimethyl acetal by LCMS and NMR. The crude acetal was dissolved in acetic acid (15 mL) and treated with ammonium acetate (33.155 mmol). After heating at 100° C. overnight, the reaction mixture was cooled to room temperature and water was added. The resulting precipitate was filtered off, dissolved in DCM and dried over MgSO4. The crude precipitate was evaporated onto approximately 20 g of silica gel and the silica was placed in a loader. Purification was achieved by flash chromatography on silica gel (120 g, solids, equilibration 20% EtOAc / Hexane, elution 0% (2 CV) to 20% EtOAc / Hexane (15 CV)). The product-containing fractions were evaporated to dryness in vacuo. 1452 mg of the desired product PLC-4.4 was obtained as a light blue-purple solid (77.3% yield from compound PLC 4.2). MS (APCI): Chemical formula: C 20 H 21 Calculated for N (M+H)=276; Found: 276. 1 H NMR(400MHz,TCE) δ 8.51(s,1H), 7.63~7.55(m,2H), 7.50~7.41(m,4H), 7.38(t,J=7.7Hz,2H), 7.26~7 .19(m,1H), 7.16(dd,J=2.7,1.7Hz,1H), 6.80(dd,J=2.7,1.7Hz,1H), 1.36(s,9H).

[0117] Compound PLC-4.5: (4-(3,7-bis(4-(tert-butyl)phenyl)-5,5-difluoro-1,9-diphenyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-10-yl)-3,5-dimethylphenol): PLC-4.5 was dissolved in PLC-4.4 (1.00 mmol, 275 mg) and 4-hydroxy-2,6-dimethyl The product was synthesized from benzaldehyde (0.500 mmol, 75 mg) and pTsOH·H2O (0.200 mmol, 38 mg), followed by DDQ (0.850 mmol, 193 mg) and 2×Et3N (4.00 mmol, 0.56 mL) and BF3·OEt2 (6.00 mmol, 0.74 mL) in dry DCE (50 mL) at 60 °C and then 50 °C. The crude reaction mixture was diluted with hexane and loaded onto about 20 g of silica gel in a loader. Purification was performed by flash chromatography on silica gel (120 g, solids, equilibrated 0% EtOAc / hexane, eluted 0% (2 CV) to 20% EtOAc / hexane (20 CV)). The fractions containing the product were evaporated to dryness in vacuo. 219 mg (30% yield) of a deep red solid was obtained. MS(APCI):Chemical formula:C 49 H 47 Calculated for BF2N2O (M+H)=729; Found: 729. 1 H NMR(400MHz,TCE) δ 7.96~7.89(m,4H), 7.56~7.46(m,4H), 7.05~6.98(m,2H), 6.98~6.90(m,4H), 6.86 ~6.76(m,4H), 6.51(s,2H), 5.70(s,2H), 4.21(s,1H), 1.98(s,6H), 1.38(s,18H).

[0118] Compound PLC-4: (4-(3,7-bis(4-(tert-butyl)phenyl)-5,5-difluoro-1,9-diphenyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-10-yl)-3,5-dimethylphenyl 2-(4-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xanthen[ 2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate):PLC-4 was synthesized similarly to PLC-2 (see below) from PLC-4.5 (0.075 mmol, 55 mg), PLC-1.5 (0.113 mmol, 64 mg), DMAP·pTsOH salt (0.1108 mmol, 33 mg), and EDC·HCl (0.0831 mmol, 16 mg). The crude reaction mixture was diluted with hexane and loaded onto approximately 20 g of silica gel in a loader. Purification was achieved by flash chromatography on silica gel (80 g, solids, equilibrated 0% EtOAc / hexane, eluted 0% (2 CV) to 50% EtOAc / hexane (30 CV)). Fractions containing the product were evaporated to dryness in vacuo. 81 mg (84% yield) of a deep red solid was obtained. MS (APCI): Chemical formula: C 82 H 63 Calculated for BF5N3O5 (M+H)=1276; Found: 1276. 1 H NMR(400MHz,TCE) δ 8.70(d,J=7.8Hz,1H), 8.65(d,J=8.3Hz,1H), 8.29(d,J=2.2Hz,1H), 8.11(d,J=8.0Hz,1H), 7.93(d,J=8.3Hz,4H), 7.86~7.74(m,5H), 7.64 ~7.48(m,7H), 7.48~7.35(m,3H), 7.09~6.91(m,6H), 6.83~6.74(m,4H), 6.52(s,2H), 6.10(s,2H), 3.90(s,2H), 2.06(s,6H), 1.38(s,18H).

[0119] Synthesis of compound PLC-2: [ka]

[0120] Compound PLC-2.1: ((E)-1-(4-isobutylphenyl)-3-phenylprop-2-en-1-one): PLC-2.1 was synthesized similarly to PLC-4.1 from 1-(4-isobutylphenyl)ethan-1-one (19.57 mmol, 3.540 g), benzaldehyde (19.57 mmol, 2.077 g) and 5N NaOH / water (23.48 mmol, 4.70 mL) in 200 proof EtOH (10 mL) and water (4.70 mL). 4.844 g (94% yield) of an off-white solid was obtained. MS (APCI): Chemical formula: C 19 H 20 Calculated for O (M+H)=265; Found: 265. 1 H NMR(400MHz,TCE) δ 7.99~7.92(m,2H), 7.80(d,J=15.7Hz,1H), 7.71~7.64(m,2H), 7.56(d,J=15.7Hz,1H), 7.45(p,J=3. 5Hz,3H), 7.34~7.28(m,2H), 2.57(d,J=7.2Hz,2H), 1.92(hept,J=6.8Hz,1H), 0.93(d,J=6.6Hz,6H).

[0121] Compound PLC-2.2: (1-(4-isobutylphenyl)-4-nitro-3-phenylbutan-1-one): PLC-2.2 was synthesized similarly to PLC-4.1 (18.323 mmol, 4.844 g) and KOH (2.346 mmol, 137 mg) in nitromethane (15 mL) and 200 proof ethanol (15 mL) at 95° C. The reaction mixture was worked up similarly to PLC-4.2 to give 5.753 g (97% yield) of a brown oil that solidified very slowly at room temperature. MS (APCI): Chemical formula: C 20 H 23 Calculated for NO3 (M+H)=326; Found: 326. 1H NMR(400MHz,TCE) δ 7.87~7.80(m,2H), 7.41~7.33(m,2H), 7.33~7.27(m,3H), 7.25(d,J=8.2Hz) ,2H), 4.85(dd,J=12.5,6.3Hz,1H), 4.69(dd,J=12.5,8.4Hz,1H), 4.20(tt, J=8.2,6.2Hz,1H), 3.47(dd,J=17.9,6.1Hz,1H), 3.39(dd,J=17.9,7.8Hz,1H), 2.53(d,J=7.2Hz,2H), 1.89(hept,J=6.8Hz,1H), 0.90(d,J=6.6Hz,6H).

[0122] Compound PLC-2.3: (2-(4-isobutylphenyl)-4-phenyl-1H-pyrrole): PLC-2.3 was synthesized similarly to PLC-4.3 from PLC-2.2 (17.670 mmol, 5.570 g) and KOH (45.765 mmol, 2.568 g) in dry THF (200 mL) and dry methanol (100 mL) followed by 96% H2SO4 (22 mL) and dry MeOH (100 mL) at 0 °C. The crude product was purified similarly to PLC-4.3. 2.981 g (61% yield from PLC-2.2) of a blue-purple solid was obtained. MS (APCI): Chemical formula: C 20 H 21 Calculated for N (M+H)=276; Found: 276. 1 H NMR(400MHz,TCE) δ 8.51(s,1H), 7.61~7.55(m,2H), 7.48~7.42(m,2H), 7.38(t,J=7.7Hz,2H), 7.26~7.17(m,3H), 7.16(dd,J=2.7,1 .7Hz,1H), 6.80(dd,J=2.8,1.7Hz,1H), 2.50(d,J=7.2Hz,2H), 1.89(hept,J=6.8Hz,1H), 0.93(d,J=6.6Hz,6H).

[0123] Compound PLC-2.4: (4-(5,5-difluoro-3,7-bis(4-isobutylphenyl)-1,9-diphenyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-10-yl)-3,5-dimethylphenol): PLC-2.4 was synthesized by dissolving PLC-2.3 (2.00 mmol, 551 mg), 4-hydroxy-2,6-dimethylbenzene, 1,2-dimethylphenyl-4-(4-(5,5-difluoro-3,7-bis(4-isobutylphenyl)-1,9-diphenyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-10-yl)-3,5-dimethylphenol in a 100 mL flask. The compound was synthesized as in PLC-4.4 from pTsaldehyde (1.00 mmol, 150 mg) and pTsOH·H2O (0.300 mmol, 57 mg), followed by DDQ (1.70 mmol, 386 mg) and 2×Et3N (8.000 mmol, 1.12 mL) and BF3·OEt2 (12.00 mmol, 1.48 mL) in dry DCE (50 mL) at 60 °C and then 50 °C. The compound was purified as in PLC-4.4 to give 219 mg (30% yield) of a deep red solid. MS (APCI): Chemical formula: C 49 H 47 Calculated for BF2N2O (M+H)=729; found 729. 1 H NMR(400MHz,TCE) δ 7.87(d,J=8.1Hz,4H), 7.26(d,J=8.2Hz,4H), 7.05~6.98(m,2H), 6.98~6.89(m,4H), 6.83~6.75(m,4H), 6 .50(s,2H), 5.70(s,2H), 4.19(s,1H), 2.55(d,J=7.1Hz,4H), 2.03~1.84(m,8H), 0.94(d,J=6.6Hz,12H).

[0124] Compound PLC-2: (4-(5,5-difluoro-3,7-bis(4-isobutylphenyl)-1,9-diphenyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-10-yl)-3,5-dimethylphenyl 2-(4-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate. PLC-2 was synthesized similarly to PLC-4 from PLC-2.5 (0.075 mmol, 55 mg), PLC-1.6 (0.113 mmol, 64 mg), DMAP·pTsOH salt (0.1108 mmol, 33 mg) and EDC·HCl (0.0831 mmol, 16 mg). The product was purified as in PLC-4 to give 74 mg (77% yield) of a deep red solid. MS (APCI): Chemical formula: C 82 H 63 Calculated for BF5N3O5 (M+H)=1276; Found: 1276. 1 H NMR(400MHz,TCE) δ 8.70(d,J=7.9Hz,1H), 8.65(d,J=8.4Hz,1H), 8.29(d,J=2.2Hz,1H), 8.11(d,J=8.1Hz,1H), 7.89(d,J =7.9Hz,4H), 7.84~7.77(m,5H), 7.62~7.57(m,2H), 7.55(d,J=8.6Hz,1H), 7.42(d,J=8.3Hz,1H), 7.4 1~7.36(m,2H), 7.27(d,J=8.0Hz,4H), 7.08~6.93(m,6H), 6.82~6.73(m,4H), 6.51(s,2H), 6.10(s,2H) ), 3.90(s,2H), 2.55(d,J=7.1Hz,4H), 2.05(s,6H), 1.92(hept,J=6.9Hz,2H), 0.95(d,J=6.6Hz,12H).

[0125] Synthesis of compound PLC-5 [ka]

[0126] Compound PLC-5.1: (E)-3-Phenyl-1-(p-tolyl)prop-2-en-1-one: A 200 mL flask was equipped with a stir bar. To the flask was added compound (4-methylphenyl)methyl ketone (10.0 g, 74.5 mmol) and benzaldehyde (8.3 g, 78.2 mmol) along with EtOH (100 ml). To this solution was added NaOH (17.9 mL, 5M in H2O) dropwise. After addition, the reaction mixture was kept at room temperature for 3 hours. TLC and LCMS showed the reaction was complete. The reaction mixture was diluted with 50 mL of H2O. The product was collected by vacuum filtration, washed with 50 mL of H2O / 10 mL of EtOH, and then further dried by lyophilization to give PLC-5.1 as a white solid (15.5 g, 93% yield) for the next step without further purification. MS (APCI): Chemical Formula: C 16 H 14 Calculated for O ([MH]−)=222; Found: 222. 1 H NMR (400MHz, CDCl3), 7.94(m,2H), 7.81(d,J=16.0Hz,1H), 7.65(m,2H), 7.54(d,J=16.0Hz,1H), 7.42(m,3H), 7.31(m,2H), 2.44(s,3H).

[0127] Compound PLC-5.2: 4-Nitro-3-phenyl-1-(p-tolyl)butan-1-one: A 100 mL flask was fitted with a stir bar. To the flask was added compound PLC-5.1 (4.0 g, 18.0 mmol), nitromethane (20 mL) and EtOH (20 mL). To the mixture was added KOH (201.9 mg, 3.6 mmol). The reaction mixture was degassed at room temperature and then heated to 95° C. and held at this temperature for 40 minutes. The reaction was monitored using LCMS. Upon completion, the reaction was cooled to room temperature and worked up by adding H2O (200 ml). The solution was extracted with EtOAc (150 mL×3). A small amount of NaCl was added during extraction to aid in the separation of the organic phase from the aqueous phase. The combined organic phase was dried over anhydrous Na2SO4 and concentrated by rotary evaporation to give PLC-5.2 as a brown liquid, which was used in the next step without further purification. Quantitative yield. MS(APCI):Chemical formula:C17 H 17 Calculated for NO3 ([MH]-)=283; Found: 283. 1 H NMR(400MHz,CDCl2CDCl2), 7.83(m,2H), 7.32(m,7H), 4.85(dd,J=12.4Hz,6.4Hz,1H), 4. 68(dd,J=12.4Hz,8.4Hz,1H), 4.20(m,1H), 3.42(qd,J=17.6Hz,6.0Hz,2H), 2.42(s,3H).

[0128] Compound PLC-5.3: 4,4-Dimethoxy-3-phenyl-1-(p-tolyl)butan-1-one: A 100 mL flask was fitted with a stir bar. To the flask was added compound PLC-5.2 (5.1 g, 18.0 mmol), THF (200 mL), and MeOH (102 ml). To this solution was added KOH (2.5 g, 45.0 mmol) in one portion. The solution was kept at room temperature for 1 hour. Meanwhile, a solution of H2SO4 (22 mL) in MeOH (106 mL) was cooled to 0° C. The previous solution was then added dropwise to the H2SO4 solution at 0° C. via an addition funnel. After the addition, the reaction was allowed to warm to room temperature. The reaction was kept at room temperature for an additional hour. LCMS showed the reaction was complete. The reaction solution was poured onto crushed ice and extracted with EtOAc (150 ml×3). The combined organic phase was washed with 10% (w / w) Na2CO3 in H2O and then with brine. After drying over anhydrous Na2SO4, the solution was concentrated under vacuum rotary evaporator to give PLC-5.3 as a brown oil, which was used in the next step without further purification. MS (APCI): Chemical formula: C 19 H 22 Calculated for O3([MH]-)=252; Found: 252. 1 H NMR(400MHz,CDCl2CDCl2), 7.82(m,2H), 7.28(m,7H), 4.46(d,J=5.6Hz,1H), 3.70(m,1H), 3.50(d d,J=17.6Hz,5.6Hz,1H), 3.35(s,3H), 3.34(dd,J=17.6Hz,8.8Hz,1H), 3.29(s,3H), 2.41(s,3H).

[0129] Compound PLC-5.4: 4-Phenyl-2-(p-tolyl)-1H-pyrrole: A 100 ml flask was charged with PLC-5.3 (5.4 g, 18.0 mmol) and NH4·OAc (6.7 g, 87.5 mmol) in AcOH (21.5 mL). The solution was degassed at room temperature. It was then heated to 100° C. and kept stirring at this temperature for 5 h. TLC (50% EtOAc in hexanes) showed the reaction was complete. The reaction mixture was quenched by the addition of H2O (150 mL) and extracted with DCM (150 mL×3). The combined organic phase was washed with saturated NaHCO3 and brine. After drying over anhydrous Na2SO4, the solution was concentrated under rotary evaporation and purified by silica gel flash chromatography using DCM in hexane (0%→100%) as eluent to give pure compound PLC-5.4 as a light purple solid (3.5 g, 82% yield over three steps). MS (APCI): Chemical formula: C 17 H 15 Calculated for N ([MH]-)=233; Found: 233. 1 H NMR(400MHz,CDCl2CDCl2) δ 8.50(s,1H), 7.58(m,2H), 7.43(m,2H), 7.38(m,2H), 7.23(m,3H), 7.16(m,1H), 6.79(m,1H), 2,38(s,3H).

[0130] Compound PLC-5.5: 4-(5,5-difluoro-1,9-diphenyl-3,7-di-p-tolyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-10-yl)-3,5-dimethylphenol: A 100 mL two-neck round-bottom flask was fitted with an air condenser and a stir bar. To the flask was added PLC-5.4 (530.0 mg, 2.3 mmol) and 4-hydroxyl-2,6-dimethylbenzaldehyde (170.6 mg, 1.1 mmol), followed by anhydrous dichloroethane (DCE, 25 ml). The reaction mixture was sparged with Ar for 30 min, then p-TsOH·H2O (38.0 mg, 0.2 mmol) was added. The reaction solution was heated to 60 °C and held at this temperature overnight. The reaction was then cooled to room temperature and DDQ (412.0 mg, 1.8 mmol) was added. The reaction was kept at room temperature for 30 min. Then BF3·OEt2 (0.84 mL, 6.8 mmol) and Et3N (0.63 mL, 4.6 mmol) were added at room temperature. The reaction mixture was heated to 50° C. and kept at this temperature for 1 h. Additional BF3·OEt2 (1.2 mL) and Et3N (0.8 mL) were added at room temperature. The reaction mixture was kept at 50° C. for an additional 1 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 PLC-5.5 as a dark purple to gold solid (333.0 mg, 45% yield). MS (APCI): Formula: C 43 H 35 Calculated for BF2N2O ([MH]-)=644; Found: 644. 1 H NMR(400MHz,CDCl2CDCl2), 7.83(m,4H), 7.30(m,4H), 7.01(m,2H), 6.93(m,4H) , 6.79(m,4H), 6.45(s,2H), 5.70(s,2H), 4.21(s,1H), 2.44(s,6H), 1.98(s,6H).

[0131] Compound PLC-5: 4-(5,5-difluoro-1,9-diphenyl-3,7-di-p-tolyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-10-yl)-3,5-dimethylphenyl 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. Compounds 1644-31 (65.0 mg, 0.10 mmol), 1621-29 (84.5 mg, 0.15 mmol), DIC (50.5 mg, 0.40 mmol) and DMAP·TsOH (58.8 mg, 0.20 mmol) were added to a vial followed by anhydrous DCM (7 ml). The reaction mixture was kept at room temperature overnight. After completion of the reaction, the reaction mixture was loaded with silica gel and purified by flash chromatography using DCM in hexane (20%→100%) and EtOAc in DCM (0%→8%) as eluents to obtain pure 1644-32 as a dark red-purple solid. The solid was further triturated with MeOH (10 ml) to obtain PLC-5 (61.0 mg, 51% yield). MS (APCI): Chemical formula: C 76 H 51 Calculated for BF5N3O5 ([MH]-)=1192; Found: 1192. 1 H NMR(400MHz,CDCl2CDCl2), 8.70(d,J=8.0Hz,1H), 8.66(d,J=8.0Hz,1H), 8.29(d,J=2.0Hz,1H), 8.12(d,J=8.0Hz,1H), 7.82(m,9H), 7.58(m,3H), 7.40(m,3H), 7.30(m,4H), 6.99(m,6H), 6.78(m,4H), 6.46(s,2H), 6.10(s,2H), 3.90(s,2H), 2.44(s,6H), 2.06(s,6H).

[0132] Synthesis of compound PLC-6 [ka]

[0133] Compound PLC-6: 4-(5,5-difluoro-1,9-diphenyl-3,7-di-p-tolyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-10-yl)-3,5-dimethylphenyl 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 a vial was added compound PLC-5.5 (65.0 mg, 0.10 mmol), compound 6.1 (95.0 mg, 0.15 mmol, see the synthesis procedure in International Application PCT / US2022 / 076912, filed September 23, 2022), DIC (50.5 mg, 0.40 mmol) and DMAP·TsOH (58.8 mg, 0.20 mmol), followed by anhydrous DCM (7 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%→8%→14%) as the eluent to obtain pure PLC-6 as a dark red-purple solid. The solid was further triturated with MeOH (10 ml) to obtain 1644-34 (48.0 mg, 38% yield). MS (APCI): Chemical formula: C 77 H 50 Calculated for BF8N3O5 ([MH]-)=1260; Found: 1260. 1 H NMR(400MHz,CDCl2CDCl2), 8.71(d,J=8.0Hz,1H), 8.66(d,J=8.0Hz,1H), 8.28(d ,J=2.4Hz,1H), 8.15(d,J=8.0Hz,1H), 8.11(bs,2H), 7.96(bs,1H), 7.83(m,4H), 7 .82(dd,J=8.0Hz,2.4Hz,1H), 7.59(m,3H), 7.42(m,3H), 7.30(m,4H), 6.99(m,6H) ), 6.78(m,4H), 6.46(s,2H), 6.10(s,2H), 3.90(s,2H), 2.44(s,6H), 2.06(s,6H).

[0134] Synthesis of compound PLC-7 [ka]

[0135] Compound PLC-7: 4-(5,5-difluoro-1,9-diphenyl-3,7-di-p-tolyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-10-yl)-3,5-dimethylphenyl 4-(4-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)butanoate: A 25 mL vial was equipped with a stir bar. Compounds PLC-5.5 (65.0 mg, 0.10 mmol), PLC-3.5 (89.0 mg, 0.15 mmol), DIC (50.5 mg, 0.40 mmol) and DMAP·TsOH (58.8 mg, 0.20 mmol) were added to a vial, followed by anhydrous DCM (7 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 hexanes (0%→60%) as the eluent to give pure PLC-7 as a dark red-purple solid. The solid was further triturated with MeOH (10 ml) to give PLC-7 (115.0 mg, 94% yield). MS (APCI): Chemical formula: C 78 H 55 Calculated for BF5N3O5 ([MH]-)=1220; Found: 1220. 1 H NMR(400MHz,CDCl2CDCl2), 8.60(d,J=8.0Hz,1H), 8.55(d,J=8.0Hz,1H), 8.20(d,J=2.4Hz,1 H), 8.03(d,J=8.0Hz,1H), 7.73(m,9H), 7.46(d,J=2.8Hz,1H), 7.38(m,2H), 7.34(d,J=2.8Hz, 1H), 7.22(m,5H), 7.19(dd,J=8.0Hz,2.4Hz,1H), 6.91(m,6H), 6.69(m,4H), 6.37(s,2H), 5.99 (s,2H), 2.77(t,J=7.6Hz,2H), 2.47(d,J=7.6Hz,2H), 2.35(s,6H), 2.05(m,2H), 1.96(s,6H).

[0136] Synthesis of compound PLC-8 [ka]

[0137] Compound PLC-8.1: (E)-1-(p-tolyl)-3-(4-(trifluoromethyl)phenyl)prop-2-en-1-one: A 100 mL flask was equipped with a stir bar. To the flask was added compound (4-methylphenyl)methyl ketone (2.0 g, 14.9 mmol) and 4-trifluoromethylbenzaldehyde (2.7 g, 15.6 mmol) along with EtOH (15 ml). To this solution was added NaOH (3.6 mL, 5M in H2O) dropwise. After the addition, the reaction mixture was kept at room temperature for 1 hour. TLC and LCMS showed the reaction was complete. The reaction mixture was diluted with 50 mL of H2O. The product was collected by vacuum filtration, washed with 50 mL of H2O, and then further dried by lyophilization to give PLC-8.1 as a white solid (4.25 g, 98% yield) for the next step without further purification. MS(APCI):Chemical formula:C 17 H 13 Calculated for F3O ([MH]-)=290; Found: 290. 1 H NMR (400MHz, CDCl3), 7.94(m,2H), 7.83(d,J=16.0Hz,1H), 7.76(m,2H), 7.69(m,2H), 7.60(d,J=16.0Hz,1H), 7.35(m,2H), 2.44(s,3H).

[0138] Compound PLC-8.2: 4-Nitro-1-(p-tolyl)-3-(4-(trifluoromethyl)phenyl)butan-1-one: A 100 mL flask was fitted with a stir bar. To the flask was added PLC-8.1 (2.0 g, 6.9 mmol), nitromethane (8 mL) and EtOH (8 mL). To the mixture was added KOH (77.4 mg, 1.4 mmol). The reaction mixture was degassed at room temperature and then heated to 95° C. and held at this temperature for 30 minutes. The reaction was monitored using LCMS. Upon completion, the reaction was cooled to room temperature and worked up by adding H2O (150 ml). The solution was extracted with EtOAc (100 mL×3). A small amount of NaCl was added during extraction to aid in separation of the organic phase from the aqueous phase. The combined organic phase was dried over anhydrous Na2SO4 and concentrated by rotary evaporation to give PLC-8.2 as a brown liquid, which was used in the next step without further purification. Quantitative yield. MS (APCI): Chemical formula: C 18 H 16 Calculated for F3NO3 ([M+H]+)=352; Found: 352. 1 H NMR(400MHz,CDCl2CDCl2), 7.81(m,2H), 7.61(m,2H), 7.43(m,2H), 7.28(m,2H), 4.88(dd,J=12.8Hz,6 .0Hz,1H), 4.71(dd,J=12.8Hz,8.4Hz,1H), 4.28(m,1H), 3.42(qd,J=17.6Hz,6.4Hz,2H), 2.42(s,3H).

[0139] Compound PLC-8.3: 4,4-Dimethoxy-1-(p-tolyl)-3-(4-(trifluoromethyl)phenyl)butan-1-one: A 250 mL flask was fitted with a stir bar. To the flask was added PLC-8.2 (2.4 g, 6.9 mmol), THF (77 mL) and MeOH (39 ml). To the solution was added KOH (967.9 mg, 17.3 mmol) in one portion. The solution was kept at room temperature for 1 h. Meanwhile, a solution of H2SO4 (9 mL) in MeOH (41 mL) was cooled to 0 °C. The previous solution was then added dropwise to the H2SO4 solution via an addition funnel at 0 °C. After the addition, the reaction was allowed to warm to room temperature. The reaction was kept at room temperature for an additional hour. LCMS showed the reaction was complete. The reaction solution was poured onto crushed ice and extracted with EtOAc (150 ml x 3). The combined organic phase was washed with 10% (w / w) Na2CO3 in H2O and then with brine. After drying over anhydrous Na2SO4, the solution was concentrated under vacuum rotary evaporator to give PLC-8.3 as a brown oil, which was used in the next step without further purification. MS (APCI): Chemical formula: C 20 H 21 F3O3([M-OMe]+) = 335; Found: 335. 1 H NMR(400MHz,CDCl2CDCl2), 7.82(m,2H), 7.55(m,2H), 7.46(m,2H), 7.26(m,2H), 4.46(d,J=5.2Hz,1H), 3.78(td,J=9.2 Hz,5.2Hz,1H), 3.53(dd,J=17.6Hz,4.8Hz,1H), 3.37(s,3H), 3.36(dd,J=17.6Hz,8.8Hz,1H), 3.31(s,3H), 2.41(s,3H).

[0140] Compound PLC-8.4: 2-(p-tolyl)-4-(4-(trifluoromethyl)phenyl)-1H-pyrrole: A 100 ml flask was charged with PLC-8.3 (2.5 g, 6.9 mmol) and NH4·OAc (2.6 g, 33.5 mmol) in AcOH (8.5 mL). The solution was degassed at room temperature. It was then heated to 100° C. and kept stirring at this temperature for 5 h. TLC (50% EtOAc in hexanes) showed the reaction was complete. The reaction mixture was quenched by the addition of H2O (40 mL) and extracted with DCM (60 mL×3). The combined organic phase was washed with saturated NaHCO3 and brine. After drying over anhydrous Na2SO4, the solution was concentrated on a rotary evaporator and purified by silica gel flash chromatography using DCM in hexanes (0%→100%) as the eluent to give pure PLC-8.4 as a blue solid (1.4 g, 65% yield over three steps). MS (APCI): Chemical formula: C 18 H 14 Calculated value for F3N ([MH]-) = 300; measured value: 300. 1 H NMR (400MHz, CDCl2CDCl2) δ 8.59(s,1H), 7.67(m,2H), 7.61(m,2H), 7.44(m,2H), 7.24(m,3H), 6.80(m,1H), 2.39(s,3H).

[0141] Compound PLC-8.5: 4-(5,5-difluoro-3,7-di-p-tolyl-1,9-bis(4-(trifluoromethyl)phenyl)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-10-yl)-3,5-dimethylphenol: A 100 mL two-neck round-bottom flask was fitted with an air condenser and a stir bar. To the flask was added PLC-8.4 (602.6 mg, 2.0 mmol) and 4-hydroxyl-2,6-dimethylbenzaldehyde (150.2 mg, 1.0 mmol), followed by anhydrous dichloroethane (22 mL). The reaction mixture was sparged with Ar for 30 min, then p-TsOH·H2O (34.2 mg, 0.2 mmol) was added. The reaction solution was heated to 60 °C and held at this temperature overnight. The reaction was then cooled to room temperature and DDQ (454.0 mg, 2.0 mmol) was added. The reaction was kept at room temperature for 30 min. BF3·OEt2 (1.5 mL, 12.0 mmol) and Et3N (1.1 mL, 8.0 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 PLC-8.5 as a dark blue-purple solid (642.0 mg, 82% yield). MS (APCI): Formula: C 45 H 33 Calculated for BF8N2O ([MH]-)=780; Found: 780. 1 H NMR (400MHz, CDCl2CDCl2), 7.83(m,4H), 7.31(m,4H), 7.20(4H), 6.90(m,4H), 6.50(s,2H), 5.70(s,2H), 4.36(bs,1H), 2.44(s,6H), 1.95(s,6H).

[0142] Compound PLC-8: 4-(5,5-difluoro-3,7-di-p-tolyl-1,9-bis(4-(trifluoromethyl)phenyl)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-10-yl)-3,5-dimethylphenyl 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 a vial were added PLC-8.5 (78.0 mg, 0.10 mmol), PLC-1.5 (84.5 mg, 0.15 mmol), DIC (50.5 mg, 0.40 mmol) and DMAP·TsOH (58.8 mg, 0.20 mmol), followed by anhydrous DCM (8 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%→8%→10%) as the eluent to give pure PLC-8 as a dark red-purple solid. The solid was further triturated with MeOH (10 ml) to give PLC-8 (15.0 mg, 11% yield). MS (APCI): Chemical formula: C 78 H 49 BF 11 Calculated for N3O5 ([MH]-)=1327; Found: 1327. 1 H NMR(400MHz,CDCl2CDCl2), 8.71(d,J=8.0Hz,1H), 8.66(d,J=8.0Hz,1H), 8.29(d,J=2.0Hz,1H), 8.12(d,J=8.0Hz,1H), 7.82(m,9H), 7.56(m,3H), 7.34(m,11H), 6.90(m,4H), 6.51(s,2H), 6.16(s,2H), 3.85(s,2H), 2.45(s,6H), 2.05(s,6H).

[0143] Synthesis of compound PLC-9 [ka]

[0144] Compound PLC-9.1: (E)-1-(4-isobutylphenyl)-3-(4-(trifluoromethyl)phenyl)prop-2-en-1-one: A 100 mL flask was equipped with a stir bar. To the flask was added compound (4-isobutylphenyl)methyl ketone (2.0 g, 11.3 mmol) and 4-trifluoromethylbenzaldehyde (2.1 g, 11.9 mmol) along with EtOH (15 ml). To the solution was added NaOH (2.7 mL, 5M in H2O) dropwise. After the addition, the reaction mixture was kept at room temperature for 1 hour. TLC and LCMS showed the reaction was complete. The reaction mixture was diluted with 50 mL of H2O. The product was collected by vacuum filtration, washed with 50 mL of H2O, and then further dried by lyophilization to give PLC-9.1 as a white solid (3.66 g, 97% yield) for the next step without further purification. MS(APCI):Chemical formula:C 20 H 19 Calculated for F3O ([MH]-)=332; Found: 332. 1 H NMR(400MHz, CDCl3), 7.96(m,2H), 7.79(d,J=16.0Hz,1H), 7.77(m,2H), 7.70(m,2H), 7.61 (d,J=16.0Hz,1H), 7.32(m,2H), 2.58(d,J=7.2Hz,2H), 1.93(m,1H), 0.94(d,J=6.8Hz,6H).

[0145] Compound PLC-9.2: 1-(4-isobutylphenyl)-4-nitro-3-(4-(trifluoromethyl)phenyl)butan-1-one: A 100 mL flask was fitted with a stir bar. To the flask was added PLC-9.1 (2.0 g, 6.0 mmol), nitromethane (7 mL) and EtOH (7 mL). To the mixture was added KOH (67.3 mg, 1.2 mmol). The reaction mixture was degassed at room temperature and then heated to 95° C. and held at this temperature for 30 minutes. The reaction was monitored using LCMS. Upon completion, the reaction was cooled to room temperature and worked up by adding H2O (150 ml). The solution was extracted with EtOAc (100 mL×3). A small amount of NaCl was added during extraction to aid in separation of the organic phase from the aqueous phase. The combined organic phase was dried over anhydrous Na2SO4 and concentrated by rotary evaporation to give PLC-9.2 as a brown liquid, which was used in the next step without further purification. Quantitative yield. MS (APCI): Chemical formula: C 21 H 22 Calculated for F3NO3 ([M+H]+)=394; Found: 394. 1 H NMR(400MHz,CDCl2CDCl2), 7.83(m,2H), 7.62(m,2H), 7.44(m,2H), 7.25(m,2H), 4.88(dd,J=12.8Hz,6.0Hz,1H), 4.71(dd,J= 12.8Hz,8.4Hz,1H), 4.29(m,1H), 3.43(qd,J=18.0Hz,7.6Hz,2H), 2.53(d,J=7.2Hz,2H), 1.87(m,1H), 0.90(d,J=7.8Hz,6H).

[0146] Compound PLC-9.3: 1-(4-isobutylphenyl)-4,4-dimethoxy-3-(4-(trifluoromethyl)phenyl)butan-1-one: A 250 mL flask was fitted with a stir bar. To the flask was added compound PLC-9.2 (2.4 g, 6.0 mmol), THF (67 mL) and MeOH (34 ml). To the solution was added KOH (841.7 mg, 15.0 mmol) in one portion. The solution was kept at room temperature for 1 hour. Meanwhile, a solution of H2SO4 (8 mL) in MeOH (36 mL) was cooled to 0° C. The previous solution was then added dropwise to the H2SO4 solution at 0° C. via an addition funnel. After the addition, the reaction was allowed to warm to room temperature. The reaction was kept at room temperature for an additional hour. LCMS showed the reaction was complete. The reaction solution was poured onto crushed ice and extracted with EtOAc (150 ml×3). The combined organic phase was washed with 10% (w / w) Na2CO3 in H2O and then with brine. After drying over anhydrous Na2SO4, the solution was concentrated under vacuum rotary evaporator to give PLC-9.3 as a brown oil, which was used in the next step without further purification. MS (APCI): Chemical formula: C 23 H 27 Calculated for F3O3 ([M-OMe]+)=378; Found: 378. 1 H NMR(400MHz,CDCl2CDCl2), 7.83(m,2H), 7.55(m,2H), 7.46(m,2H), 7.22(m,2H), 4.46(d,J=5.2Hz,1H), 3.78(td,J=9.2Hz,5.2Hz,1H), 3.54(d d,J=17.6Hz,4.8Hz,1H), 3.39(dd,J=17.6Hz,8.8Hz,1H), 3.38(s,3H), 3.32(s,3H), 2.52(d,J=7.2Hz,1H), 1.88(m,1H), 0.90(d,J=6.4Hz,6H).

[0147] Compound PLC-9.4: 2-(4-isobutylphenyl)-4-(4-(trifluoromethyl)phenyl)-1H-pyrrole: A 100 ml flask was charged with PLC-9.3 (2.5 g, 6.0 mmol) and NH4·OAc (2.2 g, 29.2 mmol) in AcOH (7.2 mL). The solution was degassed at room temperature. It was then heated to 100° C. and kept stirring at this temperature for 5 h. TLC (50% EtOAc in hexanes) showed the reaction was complete. The reaction mixture was quenched by the addition of H2O (40 mL) and extracted with DCM (60 mL×3). The combined organic phase was washed with saturated NaHCO3 and brine. After drying over anhydrous Na2SO4, the solution was concentrated under rotary evaporation and purified by silica gel flash chromatography using DCM in hexanes (0%→100%) as eluent to give pure compound PLC-9.4 as a light gray blue solid (1.6 g, 78% yield over three steps). MS (APCI): Chemical formula: C 21 H 20 Calculated for F3N ([MH]-)=343; Measured: 343. 1 H NMR(400MHz,CDCl2CDCl2) δ 8.60(s,1H), 7.67(m,2H), 7.62(m,2H), 7.45(m,2H), 7.20(m,3H), 6.82(m,1H), 2.50(d,J=7.2Hz,1H), 1.89(m,1H), 0.93(d,J=6.4Hz,1H).

[0148] Compound PLC-9.5: 4-(5,5-difluoro-3,7-bis(4-isopentylphenyl)-1,9-bis(4-(trifluoromethyl)phenyl)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-10-yl)-3,5-dimethylphenol: A 100 mL two-neck round-bottom flask was fitted with an air condenser and a stir bar. To the flask was added PLC-9.4 (686.8 mg, 2.0 mmol) and 4-hydroxyl-2,6-dimethylbenzaldehyde (150.2 mg, 1.0 mmol), followed by anhydrous dichloroethane (22 mL). The reaction mixture was sparged with Ar for 30 min, then p-TsOH·HO (34.2 mg, 0.2 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 (454.0 mg, 2.0 mmol) was added. The reaction was kept at room temperature for 30 min. BF3·OEt2 (1.5 mL, 12.0 mmol) and Et3N (1.1 mL, 8.0 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 PLC-9.5 as a dark blue-purple solid (669.0 mg, 77% yield). MS (APCI): Formula: C 51 H 45 Calculated for BF8N2O ([MH]-)=864; Found: 864. 1 H NMR(400MHz,CDCl2CDCl2), 7.88(m,4H), 7.27(m,4H), 7.19(4H), 6.90(m,4H), 6.55(s,2H), 5.70 (s,2H), 4.40(bs,1H), 2.54(d,J=7.2Hz,4H), 1.96(s,6H), 1.93(m,2H), 0.94(d,J=6.4Hz,12H).

[0149] Compound PLC-9: 4-(5,5-difluoro-3,7-bis(4-isobutylphenyl)-1,9-bis(4-(trifluoromethyl)phenyl)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-10-yl)-3,5-dimethylphenyl 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 a vial were added PLC-9.5 (43.2 mg, 0.05 mmol), PLC-1.5 (40.0 mg, 0.07 mmol), DIC (25.2 mg, 0.20 mmol) and DMAP·TsOH (29.4 mg, 0.10 mmol) followed by anhydrous DCM (5 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%→8%→10%) as eluent to give pure PLC-9 as a dark red-purple solid. The solid was further triturated with MeOH (10 ml) to give PLC-9 (19.0 mg, 27% yield). MS (APCI): Chemical formula: C 84 H 61 BF 11 Calculated for N3O5 ([MH]-)=1411; Found: 1411. 1 H NMR(400MHz,CDCl2CDCl2), 8.70(d,J=8.0Hz,1H), 8.66(d,J=8.0Hz,1H), 8.30(d,J=2.0Hz,1H), 8.12(d,J=8.0Hz,1H), 7.85(m,9H), 7.55(m,3H), 7.4 0(m,3H), 7.26(m,8H), 6.90(m,4H), 6.56(s,2H), 6.16(s,2H), 3.85(s,2H) , 2.56(d,J=6.8Hz,4H), 2.04(s,6H), 1.93(m,2H), 0.94(d,J=7.4Hz,12H).

[0150] Synthesis of compound PLC-10 [ka]

[0151] Compound PLC-10.1: (6-(4-(tert-butyl)-2-nitrophenoxy)-1H,3H-benzo[de]isochromene-1,3-dione): A 1 L 2-neck round bottom flask was placed in an aluminum heat block and a stir bar was added. The flask was fitted with a finned condenser / gas adapter, a stopper, and a flow control valve. The system was flushed with argon. To the flask was added 6-bromo-1H,3H-benzo[de]isochromene-1,3-dione (40.0 mmol, 11.084 g) and 4-(tert-butyl)-2-nitrophenol (60.0 mmol, 11.712 g), followed by anhydrous NMP (150 mL). To the flask was added NaOH (20.0 mmol, 800 mg) and copper (powder) (20.0 mmol, 1271 mg), followed by anhydrous NMP (25 mL). The flask was stirred under an argon atmosphere with a heat block set to 170°C. The reaction was stirred at this temperature overnight. The reaction mixture was cooled to room temperature and treated with water (175 mL) and 1N HCl (44 mL). The reaction mixture was stirred for 30 minutes, then filtered off and washed with water. The precipitate was transferred to a flask containing acetone / DCM, evaporated to dryness, and then azeotroped with toluene. The crude product was dissolved in a small amount of DCM and treated with methanol (300 mL). The DCM and part of the methanol were removed by rotary evaporation using a hot water bath (80°C). Once all the DCM was removed, the mixture was cooled to room temperature and the solid was filtered off. 8.180 g of a deep-colored powder (52% yield) was obtained. MS (APCI): Chemical formula: C 22 H 17 Calculated for NO6 (M+H)=392; Found: 392. 1 H NMR (400 MHz, tetrachloroethane-d2) δ 8.82 (dd, J = 8.4, 1.2 Hz, 1H), 8.71 (dd, J = 7.3, 1.2 Hz, 1H), 8.49 (d, J = 8.3 Hz, 1H), 8.16 (d, J = 2.4 Hz, 1H), 7.91 (dd, J = 8.4, 7.3 Hz, 1H), 7.80 (dd, J = 8.6, 2.4 Hz, 1H), 7.34 (d, J = 8.6 Hz, 1H), 6.91 (d, J = 8.3 Hz, 1H), 1.43 (s, 9H).

[0152] Compound PLC-10.2: (6-(2-amino-4-(tert-butyl)phenoxy)-1H,3H-benzo[de]isochromene-1,3-dione): A 250 mL two-neck round bottom flask was placed in an aluminum heat block and a stir bar was added. The flask was fitted with a finned condenser / gas adapter, a stopper, and a flow control valve. The system was flushed with argon. To the flask was added PLC-10.1 (10.0 mmol, 3.914 g) and 2-MeTHF (70 mL). With stirring at room temperature, HCl (100 mmol, 4.0 N, 25 mL) in water and SnCl2·2H2O (40.0 mmol, 9.024 g) were added. The reaction mixture was stirred for 30 minutes under an argon atmosphere with the heat block set to 90 °C. The reaction mixture was cooled to 0 °C and basified to pH approx. 8 (pH paper) with 2 N aqueous NaOH. The solid was filtered off (slow filtration) and the resulting solid was then washed with 2-MeTHF (8 x 100 mL). The filtrate was transferred to a separatory funnel and the layers were separated. The organic layer was dried over MgSO4, filtered and evaporated to dryness in vacuo. 3.743 g (quantitative yield) was obtained. It was used in the next step without further purification. MS (APCI): Chemical formula: C 22 H 19 Calculated for NO4 (M+H)=362; Found: 362. 1 H NMR (400 MHz, tetrachloroethane-d2) δ 8.88 (dd, J = 8.4, 1.2 Hz, 1H), 8.69 (dd, J = 7.3, 1.2 Hz, 1H), 8.48 (d, J = 8.4 Hz, 1H), 7.89 (dd, J = 8.4, 7.3 Hz, 1H), 7.03–6.93 (m, 3H), 6.88 (dd, J = 8.4, 2.3 Hz, 1H), 1.35 (s, 9H).

[0153] Compound PLC-10.3: (9-(tert-butyl)-1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione): A 40 mL vial was charged with a stir bar, NaNO2 (30.0 mmol, 2.070 g) and water (10 mL). The vial was stirred in an ice-water bath at 0 °C. A 100 mL round bottom flask was charged with a stir bar and PLC-10.2 (4.00 mmol, 1.446 g). To the flask was added glacial AcOH (30 mL) and concentrated HCl (20.0 mmol, 12.1 N, 1.65 mL). The mixture was stirred at room temperature for several minutes, then placed in an ice-water bath and stirred for about 1 minute. The solution of NaNO2 was started to be added before the acetic acid began to freeze. The NaNO2 was added over about 10 minutes. The diazo solution was stirred at 0 °C for 1 hour. While the diazo solution was stirring, a 250 mL two-neck round bottom flask containing a large stir bar was prepared. The flask was fitted with a finned condenser and an addition funnel. The flask was clamped with an off-center neck and the addition funnel was placed on the off-center neck so that the solution hit the top of the vortex when stirring. To this flask was added CuSO4·5H2O (27.4 mmol, 6.842 g) and water (80 mL). Approximately 15 min before the diazo solution was obtained, heating of the copper solution to 130 °C was started. When the solution reached 130 °C, the diazo solution was transferred to the addition funnel and the dropwise addition of the diazo solution was started with rapid stirring over a period of approximately 30 min. Once the addition was complete, the solution was heated for an additional 1-2 min and then cooled in a room temperature water bath. The precipitate was filtered off and washed with water. The precipitate was dried by suction and then the crude precipitate was dissolved / suspended in DCM and evaporated to dryness onto approximately 10 g of flash silica gel. Purification by flash chromatography on silica gel (220 g, solids, equilibration 50% DCM / Hexanes, elution 50% DCM / Hexanes (2 CV) → 100% DCM (20 CV) → isocratic DCM (15 CV) → 0% EtOAc / DCM (0 CV) → 1% EtOAc / DCM (10 CV)). Product tail. Fractions containing product were evaporated to dryness in vacuo. Obtained 528 mg (38% yield). MS (APCI): Formula: C 22 H 16 Calculated for O4 (M+H)=345; Found: 345. 1H NMR (400 MHz, tetrachloroethane-d2) δ 8.61 (d, J = 7.9 Hz, 1H), 8.56 (d, J = 8.4 Hz, 1H), 8.05 (d, J = 2.2 Hz, 1H), 8.01 (d, J = 8.0 Hz, 1H), 7.66 (dd, J = 8.8, 2.2 Hz, 1H), 7.38 (d, J = 8.7 Hz, 1H), 7.34 (d, J = 8.4 Hz, 1H), 1.44 (s, 9H).

[0154] Compound PLC-10.4: (2-(4-(9-(tert-butyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid): PLC-10.4 was synthesized similarly to PLC-1.4 from PLC-10.3 (1.191 mmol, 410 mg) and 2-(4-aminophenyl)acetic acid (2.98 mmol, 450 mg) in anhydrous DMF (10 mL). After workup and precipitation, 579 mg (quantitative yield) of product was obtained. MS (APCI): Chemical formula: C 30 H 23 Calculated for NO5 (M+H)=478; Found: 478. 1 H NMR (400 MHz, DMSO-d6) δ 8.48 (d, J = 7.9 Hz, 1H), 8.44 (d, J = 8.3 Hz, 1H), 8.38 (d, J = 8.1 Hz, 1H), 8.27 (d, J = 2.4 Hz, 1H), 7.69 (dd, J = 8.8, 2.3 Hz, 1H), 7.45-7.38 (m, 4H), 7.31-7.27 (m, 2H), 3.68 (s, 2H), 1.41 (s, 9H) (see also a similar synthesis of compound PLC-27.2 (U.S. Provisional Patent Application No. 63 / 278,944, filed November 12, 2021)).

[0155] Compound PLC-10: 4-(5,5-difluoro-3,7-bis(4-isobutylphenyl)-1,9-bis(4-(trifluoromethyl)phenyl)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-10-yl)-3,5-dimethylphenyl 2-(4-(9-(tert-butyl)-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 a vial were added PLC-9.5 (60.0 mg, 0.07 mmol), PLC-10.4 (39.8 mg, 0.08 mmol), DIC (35.3 mg, 0.28 mmol) and DMAP·TsOH (41.2 mg, 0.14 mmol), followed by anhydrous DCM (6 ml). The reaction mixture was kept at room temperature over the weekend. The reaction mixture was loaded onto silica gel and purified by flash chromatography using EtOAc in DCM (0%→8%→10%) as the eluent to give pure PLC-10 as a dark red-purple solid. The solid was further triturated with MeOH (19 ml) to give PLC-10 (26.0 mg, 28% yield). MS (APCI): Chemical formula: C 81 H 66 Calculated value for BF8N3O5 ([MH] - )=1324;Actual value: 1324. 1 H NMR(400MHz,CDCl2CDCl2), 8.69(d,J=8.0Hz,1H), 8.63(d,J=8.0Hz,1H), 8.09(d,J=2 .0Hz,1H), 8.06(d,J=8.0Hz,1H), 7.89(m,4H), 7.64(dd,J=8.8Hz,2.4Hz,1H), 7.55(m ,2H), 7.37(m,4H), 7.27(m,8H), 6.90(m,4H), 6.56(s,2H), 6.16(s,2H), 3.85(s,2H), 2.55(d,J=7.2Hz,4H), 2.04(s,6H), 1.93(m,2H), 1.45(s,9H), 0.95(d,J=7.8Hz,12H).

[0156] Synthesis of compound PLC-11 [ka]

[0157] Compound PLC-11: 4-(5,5-difluoro-3,7-bis(4-isobutylphenyl)-1,9-bis(4-(trifluoromethyl)phenyl)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-10-yl)-3,5-dimethylphenyl-4-(4-(9-(tert-butyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)butanoate: A 25 mL vial was equipped with a stir bar. To the vial were added PLC-9.5 (60.0 mg, 0.07 mmol), PLC-11.1 (see also similar synthesis of PLC-26.4 (U.S. Provisional Patent Application No. 63 / 278,944, filed November 12, 2021)) (42.0 mg, 0.08 mmol), DIC (35.3 mg, 0.28 mmol) and DMAP·TsOH (41.2 mg, 0.14 mmol), followed by anhydrous DCM (6 ml). The reaction mixture was kept at room temperature over the weekend. The reaction mixture was loaded with silica gel and purified by flash chromatography using EtOAc in DCM (0% → 8% → 10%) as the eluent to give pure PLC-11 as a dark red-purple solid. The solid was further triturated with MeOH (19 ml) to give PLC-11 (33.0 mg, 35% yield). MS (APCI): Chemical formula: C 83 H 70 Calculated value for BF8N3O5 ([MH] - )=1352;Actual value: 1352. 1H NMR(400MHz,CDCl2CDCl2), 8.67(d,J=8.4Hz,1H), 8.61(d,J=8.4Hz,1H), 8.09(d,J=2.4Hz,1H) , 8.06(d,J=8.0Hz,1H), 7.89(m,4H), 7.64(dd,J=8.4Hz,2.4Hz,1H), 7.46(m,2H), 7.37(m,2H), 7.28(m,10H), 6.90(m,4H), 6.56(s,2H), 6.13(s,2H), 2.84(t,J=8.0Hz,2H), 2.56(d,J=7.8Hz, 4H), 2.55(m,2H), 2.11(m,2H), 2.03(s,6H), 1.92(m,2H), 1.45(s,9H), 0.94(d,J=6.4Hz,12H).

[0158] Synthesis of compound PLC-12 [ka]

[0159] Compound PLC-12: (4-(5,5-difluoro-3,7-bis(4-isobutylphenyl)-1,9-diphenyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-10-yl)-3,5-dimethylphenyl 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):PLC-12 was synthesized similarly to PLC-2 from PLC-13.6 (see below, 0.0823 mmol, 70 mg), PLC-2.5 (0.0549 mmol, 40 mg), DMAP·pTsOH salt (0.110 mmol, 32 mg), and EDC·HCl (0.192 mmol, 37 mg) in dry DCM (10 mL). The crude reaction mixture was diluted with hexane and loaded onto approximately 20 g of flash silica gel in a loader. Purification was performed by flash chromatography on silica gel (120 g, equilibration 0% EtOAc / DCM, elution isocratic 0%). The fractions containing the product were evaporated to dryness in vacuum. 62 mg (73% yield) of a deep red solid was obtained. MS (APCI): Chemical formula: C91 H 64 BF 14 Calculated for N3O5 (M+H)=1556; Found: 1556. 1 H NMR(400MHz,TCE) δ 8.78(s,1H), 8.52(s,1H), 8.32~8.24(m,2H), 8.08(s,1H), 8.03(s,3H), 7.88(d,J=8.0Hz,4H) , 7.60(d,J=8.3Hz,2H), 7.49(ddd,J=8.5,6.1,2.7Hz,1H), 7.41(d,J=8.3Hz,2H), 7.27(dd,J=7 .8,4.7Hz,5H), 7.07~6.88(m,8H), 6.78(dt,J=6.7,1.5Hz,4H), 6.51(s,2H), 6.09(s,2H), 3.90 (s,2H), 2.55(d,J=7.1Hz,4H), 2.05(s,6H), 1.92(hept,J=6.6Hz,2H), 0.95(d,J=6.6Hz,12H).

[0160] Synthesis of compound PLC-13 [ka]

[0161] Compound PLC-13.1: (6-(2-nitrophenoxy)-1H,3H-benzo[de]isochromene-1,3-dione): A mixture of 2-nitrophenol (6.6 g, 48 mmol), KOH powder (2.4 g, 43 mmol) was mixed and stirred under vacuum for 30 minutes, then copper powder (0.4 g) was added, followed by 100 mL of anhydrous DMF. The mixture was stirred for 5 minutes, then 4-chloronaphthalic anhydride (5.1 g, 22 mmol) was added. The whole was degassed and then heated under reflux for 1.5 hours. After cooling to room temperature, 100 mL of 20% hydrochloric acid was added dropwise to the resulting reaction mixture, which was left for 2 hours. The precipitate was collected by filtration and then dried under vacuum overnight to give a tan solid (4.6 g). This was further purified by stirring in refluxing acetic acid (50 mL) for 1 hour and then cooling to room temperature. Filtration and drying in air gave a yellow solid (3.0 g, 41% yield). Confirmed by LCMS (APCI): C18 H 10 Calculated for NO6 (M+H): 336.0; Found: 336. 1 H NMR(400MHz,chloroform-d) δ 8.80(dd,J=8.5,1.2Hz,1H), 8.72(dd,J=7.3,1.2Hz,1H), 8.50(d,J=8.2Hz,1H), 8.19(dd,J=8.2,1.7Hz,1H), 7.90(dd,J=8. 5,7.3Hz,1H), 7.79(td,J=7.9,1.7Hz,1H), 7.54(td,J=8.0,1.3Hz,1H), 7.39(dd,J=8.3,1.2Hz,1H), 6.89(d,J=8.2Hz,1H).

[0162] Compound PLC-13.2: (6-(2-aminophenoxy)-1H,3H-benzo[de]isochromene-1,3-dione): A mixture of PLC-13.1 (2.0 g, 6 mmol) and iron powder (<10 μm, 0.91 g, 16 mmol) in acetic acid (75 mL) was heated to reflux for 30 min. The resulting solution was poured into water (220 mL). The resulting precipitate was collected by filtration, washed with water, and thoroughly dried in air and then under vacuum to give a yellow solid (1.65 g, 90% yield). Confirmed by LCMS (APCI): C 18 H 12 Calculated for NO4 (M+H): 306.1; Found: 306.

[0163] Compound PLC-13.3: (1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione): PLC-13.2 (1.5 g, 4.9 mmol) was dispersed in acetic acid (35 mL) and cooled to 0° C. Pre-cooled hydrochloric acid (3 mL, 37 mmol) was added under stirring, followed by dropwise addition of sodium nitrite solution (3.29 g, 46 mmol) in 12 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 refluxing copper sulfate solution (5.08 g, 20 mmol, in 50 mL of water) over 1 h. After cooling to room temperature, the precipitate was collected by filtration, washed with water and acetone, and then dried in air and then in vacuum to give a yellow solid (0.92 g, 65% yield). Confirmed by LCMS (APCI): C 18 Calculated for H8O4 (M-): 288.0; Found: 288.

[0164] Compound PLC-13.4: (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. To the flask was added PLC-13.3 (34.688 mmol, 10.00 g) 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 at 75° C. open to the atmosphere over the weekend using an aluminum heat block. The reaction mixture was cooled to room temperature and the solids were filtered off. The filtrate was diluted with hexanes (approximately 20% of the volume) and the second precipitate was filtered off. Both of these precipitates were dried in vacuum at 100° C. Orange solid, total 10.866 g (69.9% yield). Both showed 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).

[0165] Compound PLC-13.5: (2-(4-(5,11-dibromo-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid: A 100 mL 2-neck round bottom flask was equipped with a stir bar, a finned condenser / gas adapter, and a flow control valve. The system was flushed with argon. To the flask was added PLC-13.4 (7.000 mmol, 3.136 g), 2-(4-aminophenyl)acetic acid (14.00 mmol, 2.117 g), DMAP (2.100 mmol, 257 mg), and anhydrous DMF (65 mL). The reaction mixture was heated in an aluminum block set at 160° C. for 5 hours. The crude reaction mixture was cooled to 0° C., quenched with 6 N HCl (approximately 5 mL), and diluted with water (up to approximately 350 mL). The precipitate was filtered off and washed with water. The product 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.

[0166] Compound PLC-13.6: (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): A 250 mL, 2-neck round bottom flask was equipped with a stir bar, a finned condenser / gas adapter, and a flow control valve. The system was flushed with argon. To the flask was added PLC-13.5 (3.500 mmol, 2.034 g), (3,5-bis(trifluoromethyl)phenyl)boronic acid (14.00 mmol, 3.611 g), K2CO3 (19.25 mmol, 2.661 g), THF (60 mL), DMF (12 mL), and water (6 mL). The reaction mixture was stirred at room temperature under argon for several minutes, then Pd(dppf)Cl2 (0.0245 mmol, 179 mg) was added. The headspace was flushed with argon for 1 minute, then the flow control valve was closed. The reaction mixture was stirred and heated in an aluminum heat block at 80°C for 3 hours. The crude reaction mixture was evaporated to dryness in vacuo, dissolved 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, eluting 0% (10 CV) → 15.3% EtOAc / DCM (15.3 CV) → 40% EtOAc / DCM (10 CV) → isocratic 40% EtOAc / DCM). EtOAc contained 0.1% v / v TFA. Obtained 1.710 g (57.6% yield) of a tan solid. MS (APCI): Formula: C 42 H 19 F 12 Calculated for NO5 (M+H)=846; Found: 846. 1H 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)。

[0167] Compound PLC-13: (Diethyl 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-1,3,7,9-tetramethyl-5H-414,514-dipyrrolo[1,2-c:2',1'- f][1,3,2]diazaborinine-2,8-dicarboxylate: PLC-13.6 (0.113 mmol, 80 mg), PLC-13.7 (diethyl-5,5-difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate (International Synthesized as described in Publication No. 2021188392, 0.0750 mmol, 38 mg) and DMAP·pTsOH salt (0.150 mmol, 44 mg) were placed in a 40 mL screw cap vial with a stir bar. Dry DCM (10 mL) was added to the vial and the mixture was stirred to obtain a solution. DIC (0.263 mmol, 0.41 mL) was added to the vial. The reaction was capped and stirred at room temperature overnight. The crude reaction mixture was diluted with hexanes and loaded onto approximately 20 g of flash silica gel in a loader. Purified by flash chromatography on silica gel (120 g, equilibrated 0% EtOAc / hexanes, eluted 0% (2 CV) → 50% EtOAc / hexanes (30 CV)). Fractions containing the product were evaporated to dryness in vacuo. 70 mg (78% yield) of an orange solid was obtained. MS (APCI): Chemical formula: C 65 H 46 Calculated for BF8N3O9 (M+H)=1176; Found: 1176. 1H NMR(400MHz,TCE) δ 8.71(s,1H), 8.48(s,1H), 7.95~7.80(m,6H), 7.66(t,J=8.4Hz,4H), 7.4 7~7.35(m,3H), 7.31(dd,J=8.3,1.3Hz,1H), 7.10(dd,J=8.4,1.5Hz,1H), 7.05(s,2H), 6.96(ddd,J=8.4,7.1,1.4Hz,1H), 4.28(q,J=7.1Hz,4H),4. 02(s,2H), 2.84(s,6H), 2.15(s,6H), 1.73(s,6H), 1.34(t,J=7.1Hz,6H).

[0168] Synthesis of compound PLC-14 [ka]

[0169] Compound PLC-14.1: (4-formyl-3,5-dimethylphenyl 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: PLC-14.1 was synthesized from PLC-13.6 (0.150 mmol, 127 mg), 4-hydroxy-2,6-dimethylbenzaldehyde (0.450 mmol, 68 mg), DMAP·pTsOH salt (0.300 mmol, 88 mg) and EDC·HCl (0.525 mmol, 101 mg) in dry dichloromethane (20 mL) and stirred overnight at room temperature. The crude reaction mixture was loaded onto approximately 25 g of flash silica gel in a loader. Purification was achieved by flash chromatography on silica gel (80 g, equilibrated 0% EtOAc / hexanes, eluted 0% (2 CV) → 50% EtOAc / EtOAc (20 CV)). NMR shows approximately 40 mol% 4-hydroxy-2,6-dimethylbenzaldehyde. Used as is in the next step. Obtained 120 mg (81% yield) of a yellow solid. MS (APCI): Chemical formula: C 51 H 27 F 12 Calculated for NO6 (M+H)=978; Found: 978. 1H NMR(400MHz,TCE) δ 10.55(s,1H)、8.76(s,1H)、8.51(s,1H)、8.27(d,J=1.6Hz,2H)、8.07(s,1H)、8.03(t,J=2.3Hz,3H)、7.65~7.57(m,2H)、7.49(ddd,J=8.6,6.1,2.6Hz,1H)、7.41~7.35(m,2H)、7.31~7.23(m,1H)、7.05~6.95(m,2H)、6.92(s,2H)、4.01(s,2H)、2.62(s,6H)。

[0170] Compound PLC-14: (Diethyl 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-3,7-dimethyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate): A 100 mL 2-neck round bottom flask was equipped with a stir bar, a finned condenser / gas adapter, and a flow control valve and placed in an aluminum heat block. The system was flushed with argon. To the flask was added PLC-14.1 (0.289 mmol, 120 mg), ethyl 2-methyl-1H-pyrrole-3-carboxylate (0.578 mmol, 87 mg), and anhydrous DCE (20 mL). The system was stirred at room temperature, the headspace was flushed with argon for 30 seconds, and then pTsOH·H2O (0.0868 mmol, 16 mg) was added. The headspace was flushed for an additional 30 seconds, then the system was closed and stirred under argon. The reaction mixture was heated at 50 °C and stirred overnight. The reaction mixture was cooled to room temperature and DDQ (0.492 mmol, 111 mg) was added. The reaction was stirred at room temperature for 30 minutes, then Et3N (2.313 mmol, 0.32 mL), and BF3·OEt2 (3.468 mmol, 0.43 mL) were added. After 1 min, the addition of Et3N (2.313 mmol, 0.32 mL) and BF3·OEt2 (3.468 mmol, 0.43 mL) was repeated. The reaction was heated to 50° C. and stirred for 1 h. The crude reaction mixture was evaporated under reduced pressure to remove most of the DCE and then loaded onto approximately 25 g of flash silica gel in a loader. Purification was achieved by flash chromatography on silica gel (120 g, equilibrated 0% EtOAc / toluene, eluted 0% (2 CV) → 10% EtOAc / toluene (60 CV)). Fractions containing the product were evaporated to dryness in vacuo. 106 mg (66% yield) of an orange solid was obtained. MS (APCI): Formula: C 67 H 44 BF 14 Calculated for N3O9 (M+H)=1312; Found: 1312.1 H NMR(400MHz,TCE) δ 8.77(s,1H), 8.51(s,1H), 8.29~8.25(m,2H), 8.07(s,1H), 8.03(d,J=1. 9Hz,3H), 7.70~7.61(m,2H), 7.49(ddd,J=8.5,5.9,2.8Hz,1H), 7.43~7.3 6(m,2H), 7.32~7.24(m,1H), 7.08(s,2H), 7.05~6.95(m,4H), 4.26(q,J=7 .1Hz,4H), 4.04(s,2H), 2.93(s,6H), 2.17(s,6H), 1.32(t,J=7.1Hz,6H).

[0171] Example 3. Preparation of thin films for optical characterization 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.

[0172] 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.

[0173] 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. The data for PLC-1 and PLC-2 prepared in PMMA are shown in Tables 2 and 3 below. PLC-1 and PLC-2 were also prepared in poly(butyl acrylate) (PBA), where the PBA solution was used instead of the PMMA solution. Poly(butyl acrylate) (PBA) solution (average molecular weight about 99000 by GPC) was purchased from Sigma Aldrich (CAS: 9003-49-0). Data for PLC-1 and PLC-2 prepared in PBA are shown in Tables 2 and 3 below.

[0174] 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).

[0175] Fluorescence spectra of 1 inch x 1 inch film samples prepared as described above were determined using a Fluorolog spectrofluorometer (Horiba Scientific, Edison, NJ, USA) with excitation wavelengths set at their respective maximum absorbance wavelengths. Maximum emission and FWHM are shown in Table 1.

[0176] The absorption / emission spectrum obtained for PLC-1 is shown in Figure 1. The absorption / emission spectrum obtained for PLC-2 is shown in Figure 2.

[0177] The quantum yield of the 1 inch × 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 to measure the quantum yield. A film with a size of 0.5 inch × 0.5 inch was removed from the glass for measurement. The QY results at 450 nm are reported in Table 1.

[0178] 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 excitation wavelengths set at their respective maximum absorption wavelengths. Emission maxima and FWHM are shown in Table 1.

[0179] The quantum yields of 1 inch × 1 inch samples prepared as above were determined using a Quantarus-QY spectrophotometer (Hamamatsu Inc., Campbell, CA, USA) with excitation at their respective maximum absorption wavelengths. The results are reported in Table 1.

[0180] The results of film characterization (absorbance peak wavelength, FWHM, and quantum yield) are shown in Table 1.

[0181] [Table 1] [Table 2] [Table 3] [Table 4] [Table 5] [Table 6] [Table 7] [Table 8]

[0182] Furthermore, the quantum yield results of the PMMA and PBA / AA films as described above are provided in Tables 2 and 3 below.

[0183] [Table 9]

[0184] [Table 10]

Claims

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

2. The xanthenoisoquinoline derivative has the general formula: 【Chemistry 1】 (In the formula, R ９ is H or an optionally substituted aryl group, R １０ is H, C １ ~C ４ 2. The photoluminescent complex of claim 1, wherein R is an alkyl group or an optionally substituted aryl group.

3. The optionally substituted aryl group is 【Chemistry 2】 3. The photoluminescent complex of claim 2, comprising:

4. The BODIPY moiety has the general formula: 【Transformation 3】 (In the formula, R １ , R ２ , R ３ , R ４ , R ５ , R ６ are independently H, C １～ C ３ alkyl, aryl, ester, or ether; R ７ and R ８ are independently H or a methyl group (—CH ３ ) and 2. The photoluminescent complex of claim 1, wherein L is a linker conjugate comprising an unsubstituted ester or a substituted ester.

5. R ３ and R ４ 5. The photoluminescent complex of claim 4, wherein is independently H, methyl, or an optionally substituted aryl group.

6. The optionally substituted aryl group is 【Chemistry 4】 6. The photoluminescent complex of claim 5, comprising:

7. R ２ and R ５ The photoluminescent complex of claim 4 , wherein is an ester.

8. The ester is 【Transformation 5】 8. The photoluminescent complex of claim 7, wherein:

9. the linker conjugate is a substituted ester; 【Transformation 6】 2. The photoluminescent complex of claim 1, comprising:

10. the linker conjugate is an unsubstituted ester; 【Transformation 7】 2. The photoluminescent complex of claim 1, comprising:

11. The substituted ester of the linker conjugate is 【Transformation 8】 2. The photoluminescent complex of claim 1, wherein

12. The photoluminescent complex is 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】 【Chemistry 14】 【Chemistry 15】 or a combination thereof.

13. 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.

14. The color conversion film of claim 13 , wherein the resin matrix comprises poly(methyl methacrylate).

15. The color conversion film of claim 13 , wherein the resin matrix comprises poly(butyl acrylate).

16. 14. The color conversion film of claim 13, wherein the film has a thickness between 10 μm and 200 μm.

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

18. A method for 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:

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

20. A backlight unit comprising the color conversion film according to claim 13, 14, 15, 16, or 17.

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

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