Boron-containing cyclic light-emitting compound and color conversion film containing the same

Abstract

This disclosure generally relates to photoluminescent composites, and to color conversion films including the photoluminescent composites and their use in backlight units and display devices. In one embodiment, the photoluminescent composite includes a boron-dipyrrole methylene (BODIPY) moiety covalently bonded to the portion absorbing blue light.

Description

Cross-references to related applications

[0001] This application claims priority to U.S. Provisional Application No. 63 / 604,239, filed November 30, 2023, the entire contents of which are incorporated herein by reference. Background Technology

[0002] In color reproduction, the color gamut, or color gamut, is a specific, complete subset of colors that can be used on a device such as a television or monitor. For example, a wide color gamut color space has been achieved using the three pure spectral primary colors (red, green, and blue) and has been developed to provide an even wider color gamut and more realistic visible colors as seen through a display. However, if a device can provide a wider color gamut, the display can potentially display more vibrant colors.

[0003] As high-definition large-screen displays become more common, the demand for higher-performance, thinner, and more functional displays is also increasing. Current light-emitting diodes (LEDs) obtain white light by exciting green, red, or yellow phosphors with a blue light source. However, the full width at half maximum (FWHM) of the emission peaks of current green and red phosphors is quite large, typically greater than 40 nm, causing overlap in the green and red spectra and making it impossible to completely distinguish between colors. This overlap, in particular, leads to poor color rendering and color gamut degradation.

[0004] To correct color gamut degradation, methods have been developed that combine LEDs with films containing quantum dots. However, some quantum dots, such as cadmium-based quantum dots, are highly toxic and banned in many countries due to health and safety concerns. Furthermore, non-cadmium-based quantum dots are extremely inefficient at converting blue LED light into green and red light. Quantum dots also require expensive encapsulation processes to prevent moisture and oxygen contamination. The cost of using quantum dots is also high due to the difficulty in controlling dimensional uniformity during the manufacturing process.

[0005] In light of the foregoing, further contributions are needed in this technological field. Summary of the Invention

[0006] The photoluminescent composites described herein can be used to improve the contrast between distinguishable colors in televisions, computer monitors, smart devices, and other devices utilizing color displays. The photoluminescent composites described herein provide a color conversion dye composite with good blue light absorption and a narrow emission bandwidth, for example, its emission band's full width at half maximum (FWHM) is less than about 40 nm. In some forms, the photoluminescent composite absorbs light of a first wavelength and emits light of a second wavelength, wherein the second wavelength is higher than the first wavelength. In some forms, the photoluminescent composites described herein can be used in conjunction with color conversion films in light-emitting devices. Color conversion films can exhibit reduced color degradation by decreasing overlap within the chromatogram, thereby producing high-quality color rendering.

[0007] In one embodiment, the photoluminescent complex includes a blue light-absorbing moiety; a linking complex, which may be a substituted ester, an unsubstituted ester, a substituted ether, or an unsubstituted ether; and a boron-dipyrrole methylene (BODIPY) moiety. In some forms, the blue light-absorbing moiety is a xanthone isoquinoline derivative. In some forms, the linking complex covalently links the xanthone isoquinoline derivative to the BODIPY moiety. In some forms, the xanthone isoquinoline derivative absorbs light of a first excitation wavelength and transfers energy to the BODIPY moiety, and the BODIPY moiety absorbs energy from the xanthone isoquinoline derivative and emits light of a second excitation wavelength greater than the first excitation wavelength.

[0008] In some forms, one or more of the photoluminescent composites described herein may exhibit an emission quantum yield greater than 80%. In some forms, the photoluminescent composites may exhibit an emission band with a full width at half maximum (FWHM) of up to 40 nm.

[0009] In some forms, one or more of the photoluminescent composites described herein may have a Stokes shift (e.g., the difference between the excitation peak of the blue light-absorbing portion and the emission peak of the BODIPY portion) equal to or greater than 45 nm.

[0010] In some forms where the portion absorbing blue light is a xanthonisoquinoline derivative, the xanthonisoquinoline derivative can be according to the following general formula: , where each R 11 It is independently selected from hydrogen (H), C1-C3 alkyl, optionally substituted aryl, and optionally substituted heteroaryl.

[0011] In some forms, the BODIPY part can be based on the following general formula: .

[0012] In other forms, the BODIPY part can be based on the following general formula: .

[0013] In one or more of these forms, each X can be independently selected from O, NH and N-CH2, R 1 and R 6 It can be independently selected from hydrogen, saturated or unsaturated alkyl groups, such as methyl, isopropyl or isobutyl, aryl and alkenyl, R 3 and R 4 It can be independently a C1-C2 alkyl group, R 2 and R 5 It can be independently selected from hydrogen, alkyl, cyano (-CN), -C(=O)-(OCH2CH2) n -OCH3 (where n is 1, 2, 3 or 4), alkyl esters (e.g., -COOCH2CH3), and aryl esters (-COOCH2Ar), and R 7 and R 8 It can be independently selected from C1-C3 alkyl groups and optionally substituted aryl groups. In some forms where each X is N-CH2, the -CH2 groups are linked to each other. In some forms, R... 2 and / or R 5 Can be or In some forms, R 7 and / or R 8 Can be or In some implementations, R 1 and R 6 It can be independently selected from C1-C3 alkyl groups, such as methyl or isopropyl, and isobutyl, and R 2 and R 5 It can be a C1-C3 ester independently.

[0014] In some forms, L can have one of the following structures: , , and In other forms, L can have one of the following structures: , and In other forms, L can have one of the following structures: , , , , and .

[0015] In one embodiment, the color conversion film includes a color conversion layer comprising a resin matrix, and the photoluminescent composite described herein is dispersed within the resin matrix. In some forms, the color conversion film may have a thickness between 1 µm and about 200 µm. In some forms, the color conversion film may absorb blue light in the wavelength range of about 400 nm to about 480 nm and emit light in the wavelength range of about 500 nm to about 560 nm. In other forms, the color conversion film may absorb blue light in the wavelength range of about 400 nm to about 480 nm and emit light in the wavelength range of about 575 nm to about 645 nm. In some forms, the color conversion film may also include a transparent substrate layer. In some forms, the transparent substrate layer includes two opposing surfaces, and the color conversion layer is disposed on one of the opposing surfaces.

[0016] In some forms, the color conversion films disclosed herein may also include singlet oxygen quenchers and / or free radical scavengers.

[0017] In another embodiment, the method for preparing the color conversion film includes dissolving the photoluminescent composite and binder resin described herein in a solvent and coating the mixture onto the surface of a transparent substrate.

[0018] In yet another embodiment, the backlight unit includes the color conversion film described herein. In yet another embodiment, the display device includes the backlight unit described herein.

[0019] In some respects, the photoluminescent composites described herein exhibit excellent color gamut and luminescence properties. Methods for fabricating color conversion films using the photoluminescent composites described herein are also provided, as well as backlight units including the color conversion films. These and other embodiments are described in more detail below. Detailed Implementation

[0020] This disclosure relates to photoluminescent compounds and composites for use in color conversion films, backlight units, and display devices, and other possibilities. The photoluminescent composites described herein can be used to improve and enhance the transmission of one or more desired emission bandwidths within a color conversion film. In some forms, the photoluminescent composite can enhance the transmission of a first desired emission bandwidth and reduce the transmission of a second emission bandwidth. For example, the color conversion film can enhance the contrast or intensity between two or more colors, thereby increasing their difference from each other. In some aspects, the photoluminescent composites described herein can enhance the contrast or intensity between two colors, thereby increasing their difference from each other.

[0021] As used herein, when a compound or chemical structure is referred to as “substituted,” it may include one or more substituents. For example, a substituted group may be derived from an unsubstituted parent structure in which one or more hydrogen atoms in the parent structure have been independently replaced by one or more substituents. In one or more forms, the substituents may be independently selected from optionally substituted alkyl, alkenyl, and C3-C7 heteroalkyl groups.

[0022] The alkyl moiety mentioned herein may be branched, straight-chain (i.e., unbranched), or cyclic. In some embodiments, the alkyl moiety may have 1 to 8 carbon atoms. The alkyl group of the compounds specified herein may be designated as "C1-C8 alkyl" or similar names. By way of example only, "C1-C8 alkyl" means that the alkyl chain contains 1, 2, 3, 4, 5, 6, 7, or 8 carbon atoms, that is, the alkyl chain may be methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, and any of their isomers. Therefore, C1-C8 alkyl includes C1-C2 alkyl, C1-C3 alkyl, C1-C4 alkyl, C1-C5 alkyl, C1-C6 alkyl, C1-C7 alkyl, and C1-C8 alkyl. The alkyl group may be substituted or unsubstituted. Typical alkyl groups include (but are not limited to) methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, vinyl, propenyl, butenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.

[0023] As used herein, the term "heteroalkyl" refers to an alkyl group as defined herein in which one or more of the constituting carbon atoms have been substituted with 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, and -CH2-CH2-S(O)-CH3. Additionally, up to two heteroatoms may be consecutive, such as in CH2-NH-O-CH3.

[0024] As used herein, the term "aromatic" refers to a planar ring having a delocalized π-electron system containing 4n+2 π electrons, where n is an integer. Aromatic rings can be formed of five, six, seven, eight, nine, or more than nine atoms. Aromatic rings may be optionally substituted. The term "aromatic" includes both carbocyclic aryl (e.g., phenyl) and heterocyclic aryl (or "heteroaryl" or "heteroaromatic") (e.g., pyridine). The term includes monocyclic or fused polycyclic (i.e., rings sharing adjacent carbon atom pairs) groups.

[0025] As used herein, the term "aryl" refers to an aromatic ring in which each of the atoms forming the ring is a carbon atom. An aryl ring can be formed from five, six, seven, eight, or more than eight carbon atoms. Aryl groups can be substituted or unsubstituted. Examples of aryl groups include (but are not limited to) phenyl, naphthyl, and phenanthrene.

[0026] As used herein, the term "heteroaryl" refers to an aryl group comprising one or more cyclic heteroatoms selected from nitrogen, oxygen, and sulfur, wherein the heteroaryl group has 4 to 10 atoms in its ring system. It should be understood that the heteroaryl ring may contain other heteroatoms. In heteroaryl groups having two or more heteroatoms, these two or more heteroatoms may be the same or different from each other. The heteroaryl group may optionally be substituted. An N-containing heteroaryl moiety refers to an aryl group whose ring skeleton atom is a nitrogen atom. Non-limiting examples of heteroaryl groups include pyrrole and imidazole moieties.

[0027] The term "halogen" as used in this article refers to fluorine, chlorine, bromine, and iodine.

[0028] As used in this article, the terms “bond,” “bonded,” “direct bond,” or “single bond” refer to a chemical bond between two atoms, or, when the atoms bonded by the bond are considered part of a larger structure, to a chemical bond between two parts.

[0029] As used herein, the term "part" refers to a specific segment or functional group of a molecule. A chemical part is a generally recognized chemical entity that is embedded in or attached to a molecule.

[0030] As used herein, the terms “cyano” or “nitrile” refer to any organic compound containing a -CN functional group.

[0031] The term "ester" refers to a chemical moiety having the formula -COOR, where R is an alkyl, cycloalkyl, aryl, heteroaryl (by cyclic carbon bonding), or heterocyclic (by cyclic carbon bonding). Any hydroxyl or carboxyl side chain on the compounds described herein can be esterified. Such esters can be prepared using any suitable procedure and specific functional groups.

[0032] As used herein, the term "ether" refers to a chemical moiety containing an oxygen atom bonded to two alkyl or aryl groups, of the general formula RO-R', where R and R' are alkyl and / or aryl groups. Similarly, the term "alkoxy" refers to a chemical moiety containing an oxygen atom bonded to an alkyl group, which is further bonded to an alkyl or aryl group.

[0033] As used herein, the term "ketone" refers to a chemical moiety containing a carbonyl group (carbon-oxygen double bond) linked to two alkyl or aryl groups, with the general formula RC(=O)R', where R and R' are alkyl and / or aryl groups.

[0034] As used herein, the term "BODIPY" refers to the chemical part according to formula (I) or formula (II): (Formula I); (Formula II).

[0035] The BODIPY moiety can be composed of a dipyrromethene complexed with a disubstituted boron atom (such as a BF2 unit). The IUPAC name for the BODIPY core (i.e., without any substituents) is 4,4-difluoro-4-boron-3a,4a-diaza-s-indacene.

[0036] As used herein, the terms "xantonisoquinoline" or "xantonisoquinoline derivative" refer to the chemical part according to the following formula: . One non-limiting example includes 1H-xanthondo[2,1,9-def]isoquinoline-1,3(2H)-dione.

[0037] In one aspect, this disclosure relates to a photoluminescent composite that absorbs light energy of a first wavelength and emits light energy at a second wavelength higher than the first wavelength. In one form, the photoluminescent composite may include an absorbing luminescent portion and an emitting luminescent portion, the two portions being coupled by a linking group such that adjusting the distance between them causes the absorbing luminescent portion to transfer its energy to the acceptor luminescent portion, wherein the acceptor luminescent portion then emits energy at a second wavelength greater than the absorbed first wavelength.

[0038] In one embodiment, the photoluminescent composite includes a blue light-absorbing portion, a linker complex, and a boron-dipyrrole methylene (BODIPY) portion. In some forms, the blue light-absorbing portion is a xanthonisoquinoline derivative, and the linker complex covalently links the xanthonisoquinoline derivative to the BODIPY portion. In some forms, the xanthonisoquinoline derivative absorbs light of a first excitation wavelength and transfers energy to the BODIPY portion, which then emits light energy of a second wavelength, wherein the second wavelength light energy is higher than the first wavelength.

[0039] While not intended to be bound by any particular theory, it is believed that the energy transfer from the excited xanthonisoquinoline derivative to the BODIPY moiety occurs via Förster resonance energy transfer (FRET). This view is attributed to the absorption / emission spectrum of the photoluminescent complex, which exhibits two main absorption bands, one at the blue light absorption band (xanthonisoquinoline derivative) and one at the BODIPY absorption band, and only one emission band at the emission wavelength of the BODIPY moiety.

[0040] In some forms, the photoluminescent composites described herein can exhibit high emission quantum yields. For example, in some forms, the emission quantum yield can be greater than about 50%, about 60%, about 70%, about 80%, or about 90%. In some forms, the emission quantum yield can be greater than about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, or about 95%. The emission quantum yield can be measured by dividing the number of emitted photons by the number of absorbed photons, and it is equal to the emission efficiency of the emitting portion. In some forms, the absorbing emitting portion can have an emission quantum yield greater than about 80%. In some forms, the quantum yield can be greater than about 0.8 (80%), about 0.81 (81%), about 0.82 (82%), about 0.83 (83%), about 0.84 (84%), about 0.85 (85%), about 0.86 (86%), about 0.87 (87%), about 0.88 (88%), about 0.89 (89%), about 0.9 (90%), about 0.91 (91%), about 0.92 (92%), about 0.93 (93%), about 0.94 (94%), or about 0.95 (95%), and can be at most approximately 1 (100%). Quantum yield measurements in membranes can be determined using a spectrophotometer, such as the Quantaurus-QY spectrophotometer (Hamamatsu, Inc., Campbell, CA, USA).

[0041] In some forms, the photoluminescent composites described herein may include an emission band having a full width at half maximum (FWHM) of less than about 40 nm. FWHM is the width (in nanometers) of an emission band at which the emission intensity is half the maximum emission intensity of that band. In some forms, the photoluminescent composites described herein may include emission band FWHM values ​​of less than or equal to about 35 nm, less than or equal to about 30 nm, less than or equal to about 25 nm, or less than or equal to about 20 nm.

[0042] In some forms, the photoluminescent composites described herein may have a Stokes shift equal to or greater than about 45 nm. As used herein, the term "Stokes shift" means the distance between the excitation peak of the blue light-absorbing portion and the emission peak of the BODIPY portion.

[0043] In some forms, the photoluminescent composites described herein may have tunable emission wavelengths. For example, by substituting the BODIPY moiety with different substituents, the emission wavelength can be adjusted to a value between about 500 nm and about 560 nm, or any value defined therefrom.

[0044] In some forms, the portion absorbing blue light may have a maximum absorption peak between a wavelength of about 400 nm and about 480 nm. In some embodiments, the maximum absorption peak of the portion absorbing blue light may be between about 400 nm and about 405 nm, about 405 nm and about 410 nm, about 410 nm and about 415 nm, about 415 nm and about 420 nm, about 420 nm and about 425 nm, about 425 nm and about 430 nm, about 430 nm and about 435 nm, about 435 nm and about 440 nm, about 440 nm and about 445 nm, about 445 nm and about 450 nm, about 450 nm and about 455 nm, about 455 nm and about 460 nm, about 460 nm and about 465 nm, about 465 nm and about 470 nm, about 470 nm and about 475 nm, about 475 nm and about 480 nm, or any wavelength within the range defined by any of these values.

[0045] In some forms, the photoluminescent composites described herein may have an emission peak between about 500 nm and about 560 nm. In some embodiments, the emission peak may be between about 500 nm and about 515 nm, about 515 nm and about 520 nm, about 520 nm and about 525 nm, about 525 nm and about 530 nm, about 530 nm and about 535 nm, about 535 nm and about 540 nm, about 540 nm and about 545 nm, about 545 nm and about 550 nm, about 550 nm and about 555 nm, about 555 nm and about 560 nm, or any wavelength within the range defined by any of these ranges.

[0046] In some forms of photoluminescent complexes, the spatial distance between the blue light-absorbing xatonisoquinoline or its derivative and the BODIPY moiety is adjusted by connecting the complex in order to transfer the energy of the blue light-absorbing xatonisoquinoline derivative to the BODIPY moiety.

[0047] In one embodiment, the photoluminescent composite (PLC) comprises a xanthonisoquinoline derivative that absorbs blue light, a linker complex, and a BODIPY moiety. The linker complex covalently links the blue-light-absorbing xanthonisoquinoline derivative and the BODIPY moiety. In some forms, the xanthonisoquinoline derivative absorbs light energy of a first excitation wavelength and transfers energy to the BODIPY moiety, while the BODIPY moiety absorbs energy from the xanthonisoquinoline derivative and emits light energy of a second, higher wavelength. In some forms, the photoluminescent composite exhibits an emission quantum yield greater than 80%.

[0048] Some of the embodiments disclosed herein may include blue light-absorbing xanthonisoquinoline derivatives, which may have the following general formula: , Where R 11 and R 12 It can be independently hydrogen (H), C1-C4 alkyl (e.g., methyl, n-butyl, tert-butyl, etc.), trifluoromethyl, or optionally substituted aryl, for example... or -(OCH2CH2) n -OCH3, where n is 1, 2, 3 or 4, optionally substituted with a heteroaryl group or alkoxy group.

[0049] In some forms, R 12 For hydrogen, C 1-4 Alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, butyl, or tert-butyl. In some forms, R 12 It is tert-butyl.

[0050] In some forms, R 12 It can be unsubstituted phenyl, , , , , , , or .

[0051] In some forms, the photoluminescent complex may include a linker complex (L) that covalently links a blue-light-absorbing xatonisoquinoline derivative to the BODIPY moiety. In some embodiments, the linker complex may include a single bond between the xatonisoquinoline derivative and the BODIPY moiety.

[0052] In some forms, the linking complex may be a substituted ester, an unsubstituted ester, a substituted ether, or an unsubstituted ether, with only a few non-limiting examples provided. In some embodiments, the linking complex may be an optionally substituted ester group.

[0053] In some embodiments, the linker complex is a substituted ester group and has one of the following structures: , and .

[0054] In some embodiments, the linker complex may be an unsubstituted ester group and have one of the following structures: , , and .

[0055] In some implementations, the linker complex may be: .

[0056] In some implementations, the linker complex may be: .

[0057] In some implementations, the linker complex may be: .

[0058] In some implementations, the linker complex may be: .

[0059] In some implementations, the linker complex may be: .

[0060] In some implementations, the linker complex may be: .

[0061] In some implementations, the linker complex may be: -O(CH2)6-.

[0062] In some implementations, the linker complex may be: .

[0063] In some implementations, the linker complex may be: .

[0064] In some implementations, the linker complex may be: .

[0065] In some implementations, the linker complex may be: .

[0066] In some implementations, the linker complex may be: .

[0067] In some implementations, the linker complex may be: .

[0068] In some implementations, the linker complex may be: .

[0069] The BODIPY portion included in the photoluminescent composite described herein may be according to Formula I or Formula II: (Formula I) (Equation II) Where R 1 and R 6 It can be independently selected from hydrogen and saturated or unsaturated alkyl groups, such as methyl, n-propyl, isopropyl, n-butyl, or isobutyl; Where R3 It can be a C1-C2 alkyl group, such as methyl, and R 4 It can be a C1-C2 alkyl group, such as methyl; Where R 2 and R 5 It can be independently selected from hydrogen, saturated alkyl, unsaturated alkyl, cyano (-CN), alkyl esters (e.g., ethyl ester, 2-ethylhexyl ester, 2,2,2-trifluoroethyl ester, ethylene glycol ester), and aryl esters (e.g., phenyl ester (-COOCH2Ph)); Where R 7 and R 8 It can be independently selected from C1-C3 alkyl groups and optionally substituted aryl groups; Each X can be independently selected from O, NH, and N-CH2; and Wherein L may represent a linking complex, which includes an optionally substituted ester or optionally substituted ether linking group. In some embodiments, L may be selected from one of the following structures: , , , , , , , , , , , and .

[0070] In some embodiments, the compound may be based on the following: (Formula I), Each R 11 The substituents are independently selected from hydrogen (H), C1-C3 alkyl, optionally substituted aryl and optionally substituted heteroaryl, and other substituents are as previously defined.

[0071] In some forms, the BODIPY portion described herein may be a BODIPY portion, where R 1 R 3 R 4 and R 6 Each is a methyl group; R 2 and R 5 Each is a substituted ester group, wherein the substituted ester group is a C1-C7 alkyl chain or a polyethylene glycol chain; R 7 and R 8 Each is a methyl group; and L is a linking group.

[0072] In some implementations, the BODIPY portion of this disclosure may be a BODIPY portion, wherein R1 and R 6 It can be a C1-C3 alkyl group, such as methyl and / or isopropyl.

[0073] In some implementation schemes, R 2 and R 5 It can be one of the following independently: , , , , and .

[0074] In some forms, R 2 for .

[0075] In some forms, R 2 for .

[0076] In some forms, R 2 for .

[0077] In some forms, R 2 for .

[0078] In some forms, R 2 for .

[0079] In some forms, R 5 for .

[0080] In some forms, R 5 for .

[0081] In some forms, R 5 for .

[0082] In some forms, R 5 for .

[0083] In some forms, R 5 for .

[0084] In some forms, R 7 and R 8 It can be an optionally substituted phenyl group. In some forms, R 7 and R 8 It can be either an unsubstituted benzyl group or an unsubstituted biphenyl group.

[0085] In some implementation schemes, R7 and R 8 Can be independently selected from methyl ( ), phenyl ), (3,5-Di-tert-butylphenyl), (Unsubstituted para-biphenyl) (unsubstituted meta-phenyl) and (2-Ethylhexylacetyl).

[0086] The photoluminescent composite of this disclosure may be represented by the following, which is provided for illustrative purposes and should in no way be construed as limiting: (PLC-1) (PLC-2) (PLC-3) (PLC-4) (PLC-5) (PLC-6) (PLC-7) (PLC-8) (PLC-9) (PLC-10) (PLC-11) (PLC-12) (PLC-13) (PLC-14) (PLC-15) (PLC-16) (PLC-17) (PLC-18) (PLC-19).

[0087] In one embodiment, the photoluminescent complex comprises a xatonine isoquinoline derivative that absorbs blue light. In some forms, the xatonine isoquinoline derivative that absorbs blue light may include an organic luminescent group. In some forms, the xatonine isoquinoline derivative may have maximum light absorption in the ranges of about 400 nm to about 480 nm, about 400 nm to about 410 nm, about 410 nm to about 420 nm, about 420 nm to about 430 nm, about 430 nm to about 440 nm, about 440 nm to about 450 nm, about 450 nm to about 460 nm, about 460 nm to about 470 nm, about 470 nm to about 480 nm, or any wavelength within the range defined by any of these values. In some forms, the photoluminescent complex may have a maximum absorption peak of about 450 nm. In other forms, the xatonine isoquinoline derivative that absorbs blue light may have a maximum absorption peak of about 405 nm. In other forms, xatonine isoquinoline derivatives that absorb blue light can have a maximum absorption peak of about 480 nm.

[0088] In one embodiment, the color conversion film includes a color conversion layer comprising a resin matrix and at least one photoluminescent composite described herein dispersed within the resin matrix.

[0089] In some forms, the color conversion film may include a thickness of about 1 µm to about 200 µm. In some forms, the color conversion film has the following thicknesses: about 1 µm to about 5 µm, about 5 µm to about 10 µm, about 10 µm to about 15 µm, about 15 µm to about 20 µm, about 20 µm to about 40 µm, about 40 µm to about 80 µm, about 80 µm to about 120 µm, about 120 µm to about 160 µm, about 160 µm to about 200 µm, or any thickness within the range defined by any of the above values.

[0090] In some forms, the color conversion film can absorb light in the wavelength range of about 400 nm to about 480 nm and emit light in the wavelength range of about 500 nm to about 560 nm.

[0091] In some forms, the color conversion film may further include a transparent substrate layer. The transparent substrate layer may include two opposing surfaces, and the color conversion layer may be disposed on one or more surfaces of the transparent layer that are adjacent to and in physical contact with the light source. The transparent substrate is not particularly limited and may include one or more of the following: 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 (ethylene glycol-modified polyethylene terephthalate), PDMS (polydimethylsiloxane), COC (cyclic olefin copolymer), PGA (polyglycolic acid or polyglycolic acid), PLA (polylactic acid), PCL (polycaprolactone), PEA (polyethylene adipate), PHA (polyhydroxyalkanoate), PHBV (poly(3-hydroxybutyrate-co-3-hydroxyvalerate)), PBE (polybutylene terephthalate), and PTT (polypropylene terephthalate), with only a few non-limiting examples provided.

[0092] As indicated above, in some forms, the transparent substrate may have two opposing surfaces, and the color conversion film may be disposed on and in physical contact with one of the opposing surfaces. In some forms, the side of the transparent substrate on which the color conversion film is not disposed may be adjacent to the light source. In some forms, the substrate may act as a support during the fabrication of the color conversion film. The type of substrate used is not specifically limited, and the material and / or thickness are not limited, as long as it is transparent and capable of acting as a support.

[0093] In some forms, the color conversion film may include a singlet oxygen quencher. In some embodiments, the color conversion film may additionally or alternatively include a free radical scavenger.

[0094] In one embodiment, a method for preparing a color conversion film includes dissolving a photoluminescent compound and an adhesive resin described herein in a solvent and coating the mixture onto the surface of a transparent substrate.

[0095] Examples of adhesive resins that can be used with photoluminescent composites 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, polysulfones, nylon, cellulose resins, and cellulose acetate resins. In one or more forms, the adhesive resin may be a polyester resin and / or an acrylic resin.

[0096] In some forms, solvents that can be used to dissolve or disperse photoluminescent complexes and resins may include: alkanes, such as butane, pentane, hexane, heptane, and octane; cycloalkanes, such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane; alcohols, such as ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, decanol, undecylol, diacetone alcohol, and furfuryl alcohol; and Cellosolve™, such as Methyl Cellosolve™, Ethyl Cellosolve™, Butyl Cellosolve™, Methyl Cellosolve™ acetate, and Ethyl Cellosolve™ acetate. 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 pentyl ketone, cyclohexanone and acetophenone; ethers, such as dioxane and tetrahydrofuran; esters, such as butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate, ethyl 2-hydroxybutyrate, ethyl acetoacetate, methyl lactate, ethyl lactate and methyl 3-methoxypropionate; halogenated hydrocarbons, such as chloroform, dichloromethane and tetrachloroethane; aromatic hydrocarbons, such as benzene, toluene, xylene and cresol; and highly polar solvents, such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone.

[0097] In another embodiment, the backlight unit may include the color conversion film described herein.

[0098] In yet another embodiment, the display device may include the backlight unit described herein.

[0099] Example It has been found that embodiments of the photoluminescent composites described herein exhibit improved performance compared to other forms of dyes used in color conversion films. These benefits are further demonstrated by the following examples, which are intended to illustrate this disclosure only and are not intended to limit the scope or underlying principles in any way.

[0100] Example 1.1 Comparison with Example 1 (CE-1) CE-1: Dissolve 0.75 g of 4-hydroxy-2,6-dimethylbenzaldehyde (5 mmol) and 1.04 g of 2,4-dimethylpyrrole (11 mmol) in 100 mL of anhydrous dichloromethane. Degas the solution for 30 minutes. Then add one drop of trifluoroacetic acid. Stir the solution overnight at room temperature under an argon atmosphere. Add DDQ (2.0 g) to the resulting solution and stir the mixture overnight. The next day, filter the solution and wash with dichloromethane to give dipyrrolemethane (1.9 g). Then, dissolve 1.0 g of dipyrrolemethane in 60 mL of THF. Add 5 mL of trimethylamine to the solution and degas for 10 minutes. After degassing, slowly add 5 mL of trifluoroboron-diethyl ether and heat at 70 °C for 30 minutes. Load the resulting solution onto silica gel and purify it by rapid chromatography using dichloromethane as the eluent. The desired fraction was collected and dried under reduced pressure to give 0.9 g of orange solid (76% yield). LCMS (APCI+): C 21 H 24 Calculated value of BF2N2O (M+H) = 369; Measured value: 369. 1 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).

[0101] Example 1.2 Comparative Example 2 (CE-2): involving the synthesis described in Chemistry Letters, 37(10), 1094-1095 (2008), by Wakamiya, Atsushi et al. Example 1.3 compared to Example 2 (CE-3): Synthesis procedure of compound CE-3 Compound CE3.2 (6-(2-aminophenoxy)-1H,3H-benzo[de]isochromene-1,3-dione): A mixture of compound CE-3.1 (2.0 g, 6 mmol) and iron powder (<10 μm, 0.91 g, 16 mmol) in acetic acid (75 mL) was heated to reflux and maintained for 30 min. The resulting solution was poured into water (220 mL). The precipitate was collected by filtration, washed with water, and dried thoroughly in air and then under vacuum to give a yellow solid (1.65 g, 90% yield). The concentration was confirmed by LCMS (APCI): C 18 H12 Calculated value of NO4(M+H): 306.1; Measured value: 306.

[0102] Compound CE-3.3 (1H,3H-isocyaneno[6,5,4-mna]xanthon-1,3-dione): Compound CE-3.3 (1.5 g, 4.9 mmol) was dispersed in acetic acid (35 mL) and cooled to 0 °C. While stirring, pre-cooled hydrochloric acid (3 mL, 37 mmol) was added, followed by dropwise addition of sodium nitrite solution (3.29 g, 46 mmol) in 12 mL of water at 0 °C. All reactants were stirred at 0 °C for one hour, then transferred to another funnel and added dropwise over one hour to refluxed copper sulfate solution (5.08 g, 20 mmol, in 50 mL of water). After cooling to room temperature, the precipitate was collected by filtration, washed with water and acetone, and then dried in air and under vacuum to give a yellow solid (0.92 g, 65% yield). The concentration was confirmed by LCMS (APCI): C 18 Calculated value of H8O4(M-): 288.0; Measured value: 288.

[0103] Compound CE-3.4 (5,11-dibromo-1H,3H-isocyaneno[6,5,4-mna]xanthon-1,3-dione): A 2 L 2N round-bottom flask was fitted with a stir bar and a long-finned condenser. Compound CE-1.1 (34.688 mmol, 10.00 g) was added to the flask, followed by o-dichlorobenzene (1000 mL). The reaction mixture was stirred at room temperature, and Br2 (416.26 mmol, 21.3 mL) was added. A second neck stopper was placed, and the reaction mixture was heated over the weekend with an aluminum heating block at 75 °C in open air. The reaction mixture was cooled to room temperature, and the solid was filtered off. The filtrate was diluted with hexane (approximately 20% by volume), and the second precipitate was filtered off. Both precipitates were dried under vacuum at 100 °C. A total of 10.866 g of orange-yellow solid (69.9% yield) was obtained. Both exhibited similar LCMS and NMR. MS (APCI): Chemical formula: C 18 The calculated value of H6Br2O4(M+H) is 445; the measured value is also 445. 1H NMR (400 MHz, TCE) δ 9.47 (dd, J= 8.4, 1.5 Hz, 1H), 8.76 (d, J = 14.2 Hz, 2H), 7.72 - 7.63 (m, 1H), 7.56 (dd,J = 8.3, 1.4 Hz, 1H), 7.46 (ddd, J = 8.5, 6.7, 1.9 Hz, 1H).

[0104] Compound CE-3.5 (2-(4-(5,11-dibromo-1,3-dioxo-1H-xanthonro[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)acetic acid): A 100 mL 2N round-bottom flask was fitted with a stir bar and equipped with a long-finned condenser / gas adapter and flow controller. The system was flushed with argon. Compound CE-3.4 (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) were added to the flask. The reaction mixture was heated in an aluminum block set to 160 °C for 5 hours. The crude reaction mixture was cooled to 0 °C, quenched with 6N 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 subsequent reactions without further purification. 100% yield is assumed. MS (APCI): Chemical formula: C 26 H 13 Calculated value of Br2NO5(M+H) = 578; Measured value: 578.

[0105] Compound CE-3.8: A mixture of ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (1.0 g, 6.0 mmol), 4-hydroxy-2,6-dimethylbenzaldehyde (0.449 g, 3.0 mmol), and p-toluenesulfonic acid (p-TsOH) (50 mg, 0.29 mmol) in 50 mL of dichloroethane (DCE) was degassed and stirred overnight at room temperature. Liquid chromatography-mass spectrometry (LCMS) analysis showed the reaction was complete, with the major peak at m / e+ = 467. 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (0.817 g, 3.6 mmol) was added to the resulting mixture, and all reactants were stirred at room temperature for 30 min. LCMS analysis indicated the reaction was complete, with the major peak at m / e+ = 465. Under ice bath cooling, triethylamine (1.7 mL, 12 mmol) and BF3-diethyl ether (2.2 mL, 18 mmol) were added to the resulting mixture, and the mixture was stirred at 50 °C for one hour. Another 1 mL of triethylamine and 1 mL of BF3-diethyl ether were added, and all reactants were heated for another hour. LCMS analysis indicated that all dipyrrolemethine starting materials were converted to the BODIPY product, with m / e+ = 513. After cooling to room temperature, the reaction mixture was loaded onto silica gel and purified by rapid chromatography using hexane / ethyl acetate eluent (0% to 30% ethyl acetate). The desired fraction was collected. After removal of the solvent, the desired product (1.0 g, 65% yield) was obtained as an orange solid. 1 HNMR (400 MHz, chloroform-d) δ 6.68 (s, 2H), 4.29 (q, J = 7.1 Hz, 4H), 2.84 (s, 6H), 2.05 (s, 6H), 1.34 (t, J = 7.1 Hz, 6H). LCMS (APCI+):C 27 H 32 The calculated value of BF2N2O5(M+H) is 513.2; the measured value is 513.

[0106] Compound CE-3.6 (2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xanthonro[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)acetic acid): To a 250 mL 2N round-bottom flask, attach a stir bar and install a long-finned condenser / gas adapter and flow controller. Purge the system with argon. Add compound CE-3.5 (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) to the flask. Stir the reaction mixture under argon at room temperature for several minutes, then add Pd(dppf)Cl₂ (0.0245 mmol, 179 mg). Purge the headspace with argon for one minute, then turn off the flow controller. Heat the reaction mixture with stirring in an aluminum heating block at 80 °C for three hours. Evaporate the crude reaction mixture to dryness under vacuum, dissolve it in DCM, and evaporate it under vacuum to approximately 35 g of rapid silica gel. Purified on silica gel by rapid chromatography (220 g, equilibrated with 0% EtOAc / DCM, and precipitated with 0% (10 CV)). 15.3% EtOAc / DCM (15.3 CV) 40% EtOAc / DCM (10 CV) (Eluted isocratically with 40% EtOAc / DCM). EtOAc contained 0.1% v / v TFA. 1.710 g of a brownish-yellow solid was given (57.6% yield). MS (APCI): Chemical formula: C 42 H 19 F 12 The calculated value of NO5(M+H) is 846; the measured value is also 846. 1 H NMR (400 MHz, DMSO) δ 12.45 (s, 1H), 8.62 (s, 1H), 8.52 (d, J = 1.7 Hz, 2H), 8.36 (s, 1H), 8.30 (s, 1H), 8.26 (d, J = 1.6 Hz, 2H), 8.24 (s, 1H), 7.50 (ddd, J = 8.5,7.2, 1.5 Hz, 1H), 7.46 - 7.38 (m, 2H), 7.37 - 7.27 (m, 2H), 7.14 (dd, J =8.3, 1.2 Hz, 1H), 6.98 (ddd, J = 8.4, 7.2, 1.3 Hz, 1H), 6.85 (dd, J = 8.3,1.5 Hz, 1H), 3.69 (s, 2H).

[0107] Compound CE3.8 (6-(2-nitrophenoxy)-1H,3H-benzo[de]isochromene-1,3-dione): A mixture of 2-nitrophenol (6.6 g, 48 mmol) and KOH powder (2.4 g, 43 mmol) was stirred under vacuum for 30 minutes, followed by the addition of copper powder (0.4 g) and then 100 mL of anhydrous DMF. The mixture was stirred for 5 minutes, followed by the addition of 4-chloronaphthalenedicarboxylic anhydride (5.1 g, 22 mmol). All reactants were degassed, and the mixture was 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, and the mixture was allowed to stand for 2 hours. The precipitate was collected by filtration and then dried under vacuum overnight to give a yellowish-brown solid (4.6 g). This solid was further purified by stirring in refluxed acetic acid (50 mL) for 1 hour, followed by cooling to room temperature. The solid was filtered and dried in air to give a yellow solid (3.0 g, 41% yield). The concentration was confirmed by LCMS (APCI): C 18 H 10 Calculated value of NO6(M+H): 336.0; Measured value: 336. 1 H NMR (400 MHz, chloroform-d) δ 8.80 (dd, J = 8.5, 1.2 Hz, 1H), 8.72 (dd, J = 7.3, 1.2Hz, 1H), 8.50 (d, J = 8.2 Hz, 1H), 8.19 (dd, J = 8.2, 1.7 Hz, 1H), 7.90 (dd,J = 8.5, 7.3 Hz, 1H), 7.79 (td, J = 7.9, 1.7 Hz, 1H), 7.54 (td, J = 8.0, 1.3Hz, 1H), 7.39 (dd, J = 8.3, 1.2 Hz, 1H), 6.89 (d, J = 8.2 Hz, 1H).

[0108] Compound CE-3.7 Compound CE-3.7 (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-dicarboxylic acid diethyl ester): A mixture of ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (1.0 g, 6.0 mmol), 4-hydroxy-2,6-dimethylbenzaldehyde (0.449 g, 3.0 mmol), and p-toluenesulfonic acid (50 mg, 0.29 mmol) in 50 mL of 1,2-dichloroethane was degassed and stirred overnight at room temperature. LCMS analysis showed a major peak at m / e+ = 467.

[0109] DDQ (0.817 g, 3.6 mmol) was added to the resulting solution, followed by stirring at room temperature for 30 minutes. LCMS analysis showed that all starting materials were converted to the desired product, with m / e+ = 465.

[0110] Under ice bath cooling, 1.7 mL of triethylamine and 2.2 mL of BF3-diethyl ether were added sequentially to the mixture from step 2. All reactants were heated at 50°C for one hour. LCMS analysis showed a conversion of approximately 30%. Another 1 mL of triethylamine and 1 mL of BF3-diethyl ether were added to the mixture, and all reactants were heated again at 50°C for one hour. LCMS analysis showed that all materials were converted to the desired BODIPY product, with m / e+ = 513 and m / e- = 512. The reaction mixture was directly loaded onto silica gel and analyzed by rapid chromatography using hexane / ethyl acetate (0%) as the eluent. Purified with 30% ethyl acetate. The main desired peak was collected, and the solvent was removed to give an orange solid (1.0 g, 65% yield). LCMS (APCI): C27H32BF2N2O5 (M+H) calculated value: 513.2; found value: 513. 1 H NMR (400 MHz, chloroform-d) δ 7.26 (s, 3H), 6.68 (s, 2H), 4.29 (q, J = 7.1 Hz, 4H), 2.84 (s, 6H), 2.05 (s, 6H), 1.34 (t, J = 7.1 Hz, 6H).

[0111] Compound CE-3 (10-(4-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xanthonro[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)acetoxy)-2,6-dimethylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylic acid diethyl ester): Compound CE-3.6 (0.113 mmol, 80 mg), compound CE-3.7 (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-dicarboxylic acid diethyl ester) (0.0750 mmol, 38 mg), and DMAP·pTsOH salt (0.150 mmol, 44 mg) were placed in a 40 mL screw-cap vial equipped with a stir bar. Anhydrous 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 mixture was capped and stirred overnight at room temperature. The crude reaction mixture was diluted with hexane and loaded onto approximately 20 g of rapid silica gel in a loader. The mixture was purified on silica gel by rapid chromatography (120 g, equilibrated with 0% EtOAc / hexane, with 0% (2 CV)). 50% EtOAc / hexane (30 CV) elution). The fraction containing the product was evaporated to dryness under vacuum to give 70 mg (78% yield) of orange solid. MS (APCI): Chemical formula: C 65 H 46 The calculated value of BF8N3O9(M+H) is 1176; the measured value is also 1176. 1 H NMR (400 MHz, TCE) δ 8.71 (s, 1H), 8.48 (s, 1H), 7.95 – 7.80 (m, 6H), 7.66 (t, J =8.4 Hz, 4H), 7.47 – 7.35 (m, 3H), 7.31 (dd, J = 8.3, 1.3 Hz, 1H), 7.10 (dd, J =8.4, 1.5 Hz, 1H), 7.05 (s, 2H), 6.96 (ddd, J = 8.4, 7.1, 1.4 Hz, 1H), 4.28 (q, J = 7.1 Hz, 4H), 4.02 (s, 2H), 2.84 (s, 6H), 2.15 (s, 6H), 1.73 (s, 6H), 1.34(t, J = 7.1 Hz, 6H).

[0112] Compound PLC-1: Compound PLC 1.1 (4-Formyl-3,5-dimethylphenylacetate): 4-Hydroxy-2,6-dimethylbenzaldehyde (50.00 mmol, 7505 mg) and DMAP (100.0 mmol, 12.220 g) were combined in anhydrous DCM (100 mL) and stirred under argon at room temperature. Acetic anhydride (75.00 mmol, 7.1 mL) was added to the reaction mixture. The reaction was stirred at room temperature for 15 min, followed by quenching with a few drops of acetic acid. The volume of the reaction mixture was reduced under vacuum and loaded onto approximately 60 g of rapid silica gel in a sampler. The mixture was purified on silica gel by rapid chromatography (120 g, 0% EtOAc / hex (2CV)). 15% (10 CV)). The fraction containing the product was evaporated to dryness under vacuum to give a colorless oil, 4.890 g (51% yield). MS (APCI): Chemical formula: C 11 H 12 Calculated value of O3(M+H) = 193; Measured value: 193. 1H NMR (400MHz, TCE) δ 10.55 (s, 1H), 6.87 (s, 2H), 2.62 (s, 6H), 2.32 (s, 3H).

[0113] Compound PLC-1.2 (10-(4-acetoxy-2,6-dimethylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylic acid diethyl ester): Compound PLC-1.1 (17.75 mmol, 3412 mg), ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (35.50 mmol, 5936 mg), and pTsOH·H2O (1.775 mmol, 338 mg) were stirred for 90 minutes at 40 °C under argon atmosphere in anhydrous DCE (100 mL), followed by cooling to room temperature. DDQ (26.63 mmol, 6044 mg) was added and stirred for 10 minutes. Et3N (71.01 mmol, 9.90 mL) and BF3·OEt2 (106.5 mmol, 13.1 mL) were added to the reaction mixture. The addition of Et3N (71.01 mmol, 9.90 mL) and BF3·OEt2 (106.5 mmol, 13.1 mL) was repeated, and the reaction was stirred at 50 °C for 30 minutes. Cool the reaction mixture to room temperature and quench it with 50 mL of water while stirring for 5 minutes. Filter the reaction mixture through a polypropylene frit filter to retain the water. Elute the filter with DCM. Evaporate the organic eluent onto a 50 g high-speed silica gel plate under vacuum and load it into a sampler. Purify the mixture on silica gel by high-speed chromatography (330 g, 0% EtOAc / DCM (2CV)). 10% (5 CV, gradient stopped at 4.0% then 6.2%). The fraction containing the product was evaporated to dryness under vacuum, ground with hot MeOH, and water was added while hot to about 50%. The mixture was cooled to room temperature, and the precipitate was filtered off and washed with 50% MeOH / water. The product was dried under vacuum to give 6528 mg of orange solid (66% yield). MS (APCI): Chemical formula: C 29 H 33 Calculated value of BF2N2O6(MH) = 555; Measured value: 555. 1H NMR (400 MHz, TCE) δ 6.99 (s, 2H), 4.28 (q, J = 7.1 Hz, 4H), 2.84 (s, 6H), 2.14 (s, 6H), 1.72 (s, 6H), 1.34 (t, J = 7.1 Hz, 6H).

[0114] Compound PLC-1 (10-(4-acetoxy-2,6-dimethylphenyl)-1,3,7,9-tetramethyl-5,5-bis(2,2,2-trifluoroacetamido))-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylic acid diethyl ester): The compound PLC-1.2 (0.5000 mmol, 277 mg) described above and trimethylsilyl (Z)-2,2,2-trifluoro-N-(trimethylsilyl)acetimidate (10.00 mmol, 2.7 mL) were stirred in anhydrous DCE (10 mL) at room temperature, followed by treatment with SnCl4 (1.0 M in DCM, 1.500 mmol, 1.5 mL). The reaction mixture was heated to 65 °C for 12 hours. The reaction mixture was poured into 15 mL of 6N HCl and stirred for 5 minutes, then filtered through a polypropylene filter to retain water, and eluted with DCM. The reaction mixture was evaporated to dryness under vacuum, diluted with a small amount of DCM, and loaded onto approximately 40 g of rapid silica gel packed in a sampler. Purification was performed on silica gel by rapid chromatography (80 g, 0% EtOAc / DCM (2 CV)). 5% (10 CV), the gradient stopped at 5.0% then 5.2%, isocratic at each step. The fraction containing the product was evaporated to dryness under vacuum to give 38 mg (10% yield) of orange solid. MS (APCI): Chemical formula: C 33 H 35 Calculated value of BF6N4O8(MH) = 741; Measured value: 741. ¹H NMR (400 MHz, CDCl3) δ 7.37 (s, 2H), 7.00 (s, 2H), 2.64 (s, 6H), 2.32 (s, 3H), 2.22 (s, 6H), 1.73 (s, 6H), 1.32 (t, J = 7.1 Hz, 6H).

[0115] Compound PLC-2: Compound PLC-2 (10-(4-acetoxy-2,6-dimethylphenyl)-1,3,7,9-tetramethyl-5,5-bis(2,2,2-trifluoroacetoxy)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylic acid diethyl ester): Compound PLC-1.2 (0.5000 mmol, 277 mg) and trimethylsilyl 2,2,2-trifluoroacetate (5.000 mmol, 0.86 mL) were stirred in anhydrous DCE (10 mL) under argon at room temperature. The reaction mixture was treated with BF3.OEt2 (0.7500 mmol, 0.093 mL) and stirred at room temperature for 1 minute, followed by heating to 45 °C for 3 hours. Cool the reaction mixture to room temperature and pour it into approximately 30 mL of saturated sodium bicarbonate solution, stirring for 5 minutes. Filter the reaction mixture through a polypropylene filter to retain water, and elute with DCM. Evaporate the reaction mixture to dryness under vacuum, dilute with a small amount of DCM, and load onto approximately 40 g of rapid silica gel in a sampler. Purify on silica gel by rapid chromatography (120 g, 0% acetone / DCM (2 CV)). 25% (5 CV), the gradient stopped at 0.9%, 1.5%, 1.9%, and 2.0%, isocratic at each step. The fraction containing the product was evaporated to dryness under vacuum to give 198 mg (53% yield) of orange solid. MS (APCI): Chemical formula: C 33 H 33 BF6N2O 10 The calculated value of (MH) is 743, and the measured value is 743.

[0116] Synthesis of PLC-4: Compound PLC-4.1 ((3,5-dibromophenoxy)triethylsilane): A stir bar was attached to a 500 mL 2N round-bottom flask, and a gas adapter and diaphragm were fitted. The flask was placed in a Dewar bowl. The flask was rinsed with argon. 3,5-Dibromophenol (100.0 mmol, 25.190 g), imidazole (300.0 mmol, 20.430 g), and anhydrous DCM (200 mL) were added to the flask. The mixture was stirred at room temperature to obtain a solution, which was then cooled to 0 °C in an ice-water bath. Triethylchlorosilane (150.0 mmol, 25.2 mL) was added to the flask via a syringe at 0 °C with stirring. The reaction was stirred at 0 °C for 50 min, followed by partitioning with water (200 mL). The layers were separated, and the aqueous layer was extracted with DCM (50 mL). The combined organic layers were dried over MgSO4, filtered, and evaporated to dryness under vacuum. The mixture was diluted with hexane and loaded onto a sampler containing 60 g of rapid silica gel. Purification was performed on silica gel by rapid chromatography (220 g, equilibrated and eluted with 100% hexane). The fraction containing the product was evaporated to dryness under vacuum to give a colorless oil, 27.811 g (76% yield). MS (APCI): Chemical formula: C 12 H 18 Calculated value of Br2OSi (M+H) = 365; Measured value: 365. 1 H NMR (400 MHz, TCE) δ 7.28 (t, J =1.7 Hz, 1H), 6.96 (d, J = 1.6 Hz, 2H), 1.10 – 0.95 (m, 9H), 0.75 (qd, J =7.7, 0.9 Hz, 6H).

[0117] Compound PLC-4.2 (2,6-dibromo-4-hydroxybenzaldehyde): A stir bar and gas adapter and diaphragm were fitted into a 250 mL 2N round-bottom flask. The flask was placed in a Dewar bowl. The flask was rinsed with argon. Compound PLC-4.1 (30.00 mmol, 10.985 g) and the azeotroped substance were weighed from toluene. Compound PLC-4.1 was transferred to the reaction flask under argon atmosphere, followed by the addition of anhydrous THF (130 mL), and the reaction mixture was stirred at room temperature to obtain a homogeneous solution. The reaction mixture was cooled to -78°C (dry ice / acetone). Oxygen in the system was purged using a vacuum / argon refill cycle (3×). LDA was added to a solution of THF / hexane (1.0 M, 60.00 mmol, 60.0 mL) over several minutes with vigorous stirring. The solution was stirred at -78°C for 70 minutes, followed by the addition of anhydrous DMF (150.0 mmol, 11.6 mL) via syringe, and stirred at -78°C for 60 minutes. While stirring, the reaction mixture was cold-poured into 400 mL of saturated NH₄Cl solution. The solution was extracted with EtOAc (100 mL), and the layers were separated. The aqueous layer was acidified to approximately pH 1 with excess 6N HCl, yielding a grayish-white ppt. The organic layer was extracted with 100 mL of saturated NH₄Cl, followed by two extractions with 10% K₂CO₃ (100 mL). These aqueous extracts were also added to the acidified water to maintain the pH at approximately 1. The resulting precipitate was filtered off and then dried overnight in a vacuum oven at 90°C, yielding a grayish-white / gray precipitate, 6.665 g (79% yield). MS (APCI): Calculated value of chemical formula: C₇H₄Br₂O₂(M+H) = 281; Found value: 281. 1 ¹H NMR (400 MHz, acetone) δ 10.14 (s, 1H), 7.24 (s, 2H).

[0118] Compound PLC-4.3] (3,3'',5,5''-tetratert-butyl-5'-hydroxy-[1,1':3',1''-terphenyl]-2'-formaldehyde): A stir bar was attached to a 500 mL 2N round-bottom flask, and a long-finned condenser / gas adapter and flow controller were fitted. The system was flushed with argon. Compound PLC4.2 (5.500 mmol, 1.540 g), (3,5-di-tert-butylphenyl)boric acid (22.00 mmol, 5.150 g), NaHCO3 (33.00 mmol, 2.772 g), Pd(dppf)Cl2 (1.100 mmol, 805 mg), anhydrous THF (270 mL), and water (9 mL) were added to the flask. The heating block was set to 80 °C, and the reaction mixture was stirred overnight at this temperature. The reaction mixture was evaporated onto 60 g of rapid silica gel and placed in a sampler. Purification was performed on silica gel by rapid chromatography (220 g, equilibrated with 0% EtOAc / hexane, with 0% (2 CV)). (Eluted with 30% EtOAc / hexane (20 CV)). The fraction containing the product was evaporated to dryness under vacuum to give 2.256 g (82% yield) of a pale yellow solid. MS (APCI): Chemical formula: C 35 H 46 Calculated value of O2(M+H) = 499; Measured value: 499. 1 H NMR (400 MHz, TCE) δ 9.80 (s, 1H), 7.42 (t, J = 1.8 Hz, 2H), 7.15 (d, J = 1.8 Hz, 4H), 6.87 (s, 2H), 1.35 (s, 36H).

[0119] Compound PLC-4.4 (2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate 3,3'',5,5''-tetra-tert-butyl-2'-formyl-[1,1':3',1''-terphenyl]-5'-yl ester) (3,3'',5,5''-tetra-tert-butyl-2'-formyl-[1,1':3',1''-terphenyl]-5'-yl 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): towards 40 A stir bar, compound PLC-4.3 (4.523 mmol, 2256 mg), (2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xanthondro[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)acetic acid (from an external supplier) (5.428 mmol, 4.590 g), DMAP·pTsOH salt (4.523 mmol, 1332 mg), and anhydrous DCM (20 mL) were placed in a 1 mL screw-cap vial. The reaction mixture was stirred at room temperature to give a yellow slurry. DIC (9.047 mmol, 1.41 mL) was added with stirring at room temperature. The reaction mixture was stirred at room temperature for 60 min, then diluted 1:1 with hexane and loaded onto approximately 60 g of rapid silica gel in a sampler. Purification was performed on silica gel by rapid chromatography (220 g, with 0%...) EtOAc / hexane equilibrium, using 0% (2 CV) (20% EtOAc / hexane (22 CV) elution). The fraction containing the product was evaporated to dryness under vacuum to give 5.182 g (86% yield) of a yellow solid. MS (APCI): Chemical formula: C 77 H 63 F 12 The calculated value of NO6(M+H) is 1326; the measured value is also 1326. 1H NMR (400 MHz, TCE) δ 9.89 (s, 1H), 8.75 (s, 1H), 8.50 (s, 1H), 8.29 – 8.24(m, 2H), 8.07 (s, 1H), 8.05 – 7.97 (m, 3H), 7.67 – 7.60 (m, 2H), 7.49 (ddd, J= 8.6, 6.1, 2.6 Hz, 1H), 7.43 (t, J = 1.8 Hz, 2H), 7.38 (d, J = 8.4 Hz, 2H),7.31 – 7.25 (m, 1H), 7.23 (s, 2H), 7.17 (d, J = 1.8 Hz, 4H), 7.05 – 6.96 (m,2H), 4.07 (s, 2H), 1.36 (s, 36H)。

[0120] Compound PLC-4.5 (10-(5'-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xanthonro[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)acetoxy)-3,3'',5,5''-tetratert-butyl-[1,1':3',1''-terphenyl]-2'-yl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylic acid diethyl ester): A stir bar was placed in a 250 mL 2N round-bottom flask, and a long-finned condenser / gas adapter and flow controller were fitted. The system was flushed with argon. Compound PLC-4.4 (1.000 mmol, 1.326 g), ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (2.100 mmol, 351 mg), and anhydrous DCE (100 mL) were added to the flask. The reaction mixture was vigorously stirred at room temperature for 30 seconds, followed by the addition of pTsOH·H₂O (0.2000 mmol, 38 mg). The reaction mixture was stirred at room temperature under argon for 19 hours, followed by the addition of DDQ (1.300 mmol, 295 mg), and then anhydrous DCE (5 mL). The mixture was stirred at room temperature for 30 minutes, followed by the addition of more DDQ (0.5000 mmol, 114 mg), and then anhydrous DCE (5 mL). After stirring for another 30 minutes, oxidation was complete. Et₃N (8.000 mmol, 1.1 mL) and BF₃·OEt₂ (12.00 mmol, 1.5 mL) were added to the reaction mixture. After 1 minute, Et3N (8.000 mmol, 1.1 mL) and BF3.OEt2 (12.00 mmol, 1.5 mL) were added repeatedly. The reaction mixture was stirred at 50 °C for 50 minutes, then evaporated under vacuum onto 25 g of rapid silica gel (bath = 60 °C), and this silica was placed in a sampler. Purification was performed on silica gel by rapid chromatography (330 g, equilibrated with 0% acetone / hexane, with 0% (2 CV)). Elution with 20% acetone / hexane (15 CV). The fraction containing the product was evaporated to dryness under vacuum. Purification was then performed again by direct loading of 10% DCM / hexane (dry loading) onto a 220 g column, followed by elution with 0% EtOAc / DCM (2 CV) → 0.2% EtOAc / DCM (2 CV) → isocratic 0.2% EtOAc / DCM. The fraction containing the product was evaporated to dryness under vacuum to give 870 mg of orange solid (52% yield). MS (APCI): Chemical formula: C 95H 84 BF 14 Calculated value of N3O9(M+H) = 1689; Measured value: 1689. ¹H NMR (400 MHz, TCE) δ 8.75 (s, 1H), 8.50 (s, 1H), 8.26 (s, 2H), 8.07 (s, 1H), 8.02 (s, 3H), 7.66 (d, J = 8.3 Hz, 2H), 7.53 – 7.44 (m, 1H), 7.43 – 7.34 (m, 4H), 7.27 (d, J = 8.1 Hz, 1H), 7.21 (t, J = 1.8 Hz, 2H), 7.04 – 6.91 (m, 6H), 4.24 (q, J = 7.1 Hz, 4H), 4.10 (s, 2H), 2.62 (s, 6H), 2.00 (s, 6H), 1.30 (t, J = 7.1 Hz, 6H), 1.12 (s, 36H).

[0121] PLC-4: Compound PLC-4 (10-(5'-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xanthonro[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)acetoxy)-3,3'',5,5''-tetratert-butyl-[1,1':3',1''-terphenyl]-2'-yl)-1,3,7,9-tetramethyl-5,5-bis(2,2,2-trifluoroacetoxy)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylic acid diethyl ester): Compound PLC-4.5 (0.2500 mmol, 422 2,2,2-trifluoroacetic acid trimethylsilyl ester (5.000 mmol, 0.86 mL) and BF3.OEt2 (0.3750 mmol, 0.046 mL) were stirred for 1 minute in anhydrous DCE (10 mL) at room temperature, followed by heating to 45°C overnight. The reaction mixture was poured into about 30 mL of saturated sodium bicarbonate solution and stirred for 5 minutes, then filtered through a polypropylene filter to retain water and eluted with DCM. The eluent was evaporated to dryness under vacuum, dissolved in a small amount of DCM, and loaded onto about 15 g of rapid silica gel packed in a sampler. Purification was performed on silica gel by rapid chromatography (80 g, 0% acetone / hexane (2 CV)). 10% (5 CV, gradient stopped at 1.2% then 5.0%). The fraction containing the product was evaporated to dryness under vacuum to give 165 mg (35% yield) of orange solid. MS (APCI): Chemical formula: C 99 H 84 BF 18 N3O 13 The calculated value for (MH) is 1876, and the measured value is also 1876. ¹H NMR (400 MHz, TCE) δ 8.75 (s, 1H), 8.50 (s, 1H), 8.26 (d, J = 1.6 Hz, 2H), 8.07 (s, 1H), 8.06 – 7.99 (m, 3H), 7.66 – 7.61 (m, 2H), 7.49 (ddd, J = 8.5, 6.2, 2.5 Hz, 1H), 7.42 – 7.36 (m, 2H), 7.33 (s, 2H), 7.30 –7.25 (m, 1H), 7.23 (t, J = 1.8 Hz, 2H), 7.05 – 6.94 (m, 2H), 6.83 (d, J = 1.8Hz, 4H), 4.28 (q, J = 7.1 Hz, 4H), 4.06 (s, 2H), 2.48 (s, 6H), 2.21 (s, 6H), 1.33 (t, J = 7.1 Hz, 6H), 1.08 (s, 36H).

[0122] PLC-9: PLC-9 (10-(5'-(2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xanthonro[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)acetoxy)-[1,1':3',1''-terphenyl]-2'-yl)-3,7-diethyl-1,9-dimethyl-5,5-bis(2,2,2-trifluoroacetoxy)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylic acid diethyl ester): PLC-9.1 (0.2367 mmol, 321 mg) was dissolved in anhydrous DCE (10 mL) and stirred under argon at room temperature. Trimethylsilyl 2,2,2-trifluoroacetate (4.734 mmol, 0.82 mL) was added to the reaction mixture, followed by BF3·OEt2 (0.3351 mmol, 0.044 mL). The reaction mixture was stirred at room temperature for 1 minute, then heated to 45°C for 3 hours. The reactants were poured into approximately 30 mL of saturated sodium bicarbonate solution and stirred for 5 minutes, then filtered through a polypropylene filter to retain water and eluted with DCM. The combined organic layers were evaporated to dryness, dissolved in a small volume of DCM, and loaded onto approximately 15 g of rapid silica in a sampler. Purification was performed on silica gel by rapid chromatography (80 g, 0% EtOAc / toluene (2 CV)). 10% (10 CV), stop at 3.0%, isocratic). The fraction containing the product was evaporated to dryness under vacuum, dissolved in hot methanol, diluted with some water, cooled to room temperature, and filtered off, washed with 90% methanol / water. The product was dissolved in DCM and evaporated to dryness. 178 mg (49% yield) of orange solid was given. MS (APCI): Chemical formula: C 83 H 58 BF 12 N3O 13The calculated value for (M+H) is 1544, and the measured value is also 1544. ¹H NMR (400 MHz, TCE) δ 8.69 (s, 1H), 8.46 (s, 1H), 7.94 (d, J = 7.8 Hz, 2H), 7.90 (d, J = 8.4Hz, 2H), 7.88 – 7.82 (m, 4H), 7.77 (d, J = 2.4 Hz, 2H), 7.69 – 7.58 (m, 8H), 7.52 (ddd, J = 8.4, 7.3, 1.3 Hz, 2H), 7.46 – 7.35 (m, 5H), 7.30 (dd, J = 8.4, 1.3 Hz, 1H), 7.27 (dd, J = 8.8, 2.4 Hz, 2H), 7.22 – 7.14 (m, 1H), 7.13 – 7.07(m, 3H), 7.00 – 6.91 (m, 1H), 4.02 (s, 2H), 3.01 (s, 6H), 2.26 (s, 6H), 1.91 (s, 6H).

[0123] PLC-10: PLC-10 (10-(4-(2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xanthonro[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)acetoxy)-2,6-dimethylphenyl)-3,7-diisopropyl-1,9-dimethyl-5,5-bis(2,2,2-trifluoroacetoxy)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylic acid dimethyl ester): PLC-10.1 (0.6000 mmol, 739 mg) was stirred in anhydrous DCE (15 mL) under argon at room temperature. Trimethylsilyl 2,2,2-trifluoroacetate (12.00 mmol, 2.07 mL) and BF3.OEt2 (1.800 mmol, 0.22 mL) were added to the reaction mixture, and the reaction was heated to 50 °C for one hour. The reaction mixture was poured into approximately 40 mL of saturated sodium bicarbonate solution and stirred for five minutes. The reaction mixture was filtered through a polypropylene filter to retain water and eluted with DCM. The eluent was evaporated to dryness under vacuum, dissolved in a small volume of DCM, and loaded onto approximately 15 g of rapid silica gel in a sampler. Purification was performed on silica gel by rapid chromatography (120 g, 0% acetone / DCM (2 CV)). 10% (10 CV), stopping at 0.4%, 0.5%, 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, 1.7%, 2.0%, 2.4%, and 2.8%, isocratic at each step). The fraction containing the product was evaporated to dryness under vacuum. The product was ground with hot methanol, diluted with water at approximately 1:1, cooled to room temperature, filtered off, washed with approximately 1:1 methanol:water, dissolved in DCM, dried over magnesium sulfate, filtered off, and evaporated to dryness under vacuum. 608 mg (71% yield) of orange solid was given. MS (APCI): Chemical formula: C 73 H 54 BF 12 N3O 13 The calculated value for (M+H) is 1420, and the measured value is also 1420. ¹H NMR (400 MHz, TCE) δ: 8.71 (s, 1H), 8.48 (s, 1H), 7.91 (d, J = 8.2 Hz, 2H), 7.89 – 7.81 (m, 4H), 7.66 (t, J = 8.1 Hz, 4H), 7.46 – 7.37 (m, 3H), 7.31 (dd, J = 8.4, 1.4 Hz, 1H), 7.10 (dd, J = 8.3, 1.5 Hz, 1H), 7.07 (s, 2H), 6.96 (ddd, J = 8.4, 7.1, 1.3 Hz, 1H), 4.02 (s, 2H), 3.81 (s, 6H), 3.67 (hept, J = 7.0 Hz, 2H), 2.24 (s, 6H), 1.60 (s, 6H), 1.31 (d, J = 7.0 Hz, 13H).

[0124] PLC-11: PLC-11 (10-(5'-(2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xanthonro[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)acetoxy)-4,4''-bis(trifluoromethyl)-[1,1':3',1''-terphenyl]-2'-yl)-3,7-diisopropyl-1,9-dimethyl-5,5-bis(2,2,2-trifluoroacetoxy)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylic acid dimethyl ester): PLC-11.1 (0.1897 mmol, 283 2,2,2-trifluoroacetic acid trimethylsilyl ester (3.793 mmol, 0.66 mL) and BF3.OEt2 (0.5690 mmol, 0.070 mL) were stirred in anhydrous DCE (15 mL) at room temperature for several minutes, followed by heating to 50 °C for one hour, and then cooling to room temperature. The mixture was quenched with saturated sodium bicarbonate solution (approximately 30 mL), stirred for approximately 10 minutes, and then filtered through a polypropylene filter to retain water, eluting with DCM. The DCM was evaporated to dryness under vacuum, dissolved in a small volume of DCM, and loaded onto approximately 15 g of rapid silica gel in a sampler. Purification was performed on silica gel by rapid chromatography (80 g, 0% acetone / DCM (2 CV)). Stop at 5% (10 CV), 0.1%, and 1.2%, isocratic at each step. The fraction containing the product was evaporated to dryness under vacuum. 148 mg of orange solid (47% yield) was given. 1H NMR (400 MHz, TCE) δ8.70 (s, 1H), 8.47 (s, 1H), 7.95 – 7.79 (m, 6H), 7.67 (dd, J = 8.4, 1.8 Hz, 4H), 7.54 (d, J = 8.1 Hz, 4H), 7.48 – 7.34 (m, 9H), 7.31 (dd, J = 8.2, 1.3Hz, 1H), 7.10 (dd, J = 8.4, 1.5 Hz, 1H), 7.01 – 6.92 (m, 1H), 4.08 (s, 2H), 3.81 (s, 6H), 3.50 (h, J = 7.5 Hz, 2H), 1.87 (s, 6H), 1.18 (d, J = 6.9 Hz, 12H). MS (APCI): Chemical formula: C 85 H 56 BF 18 N3O 13The calculated value of (M+H) is 1680; the measured value is 1680.

[0125] PLC-12: PLC-12 (10-(5'-(2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xanthonro[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)acetoxy)-[1,1':3',1''-terphenyl]-2'-yl)-3,7-diisopropyl-1,9-dimethyl-5,5-bis(2,2,2-trifluoroacetoxy)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate): PLC-12.1 (0.3960 mmol, 537 mg), 2,2,2-trifluoroacetic acid trimethylsilyl ester (7.920 mmol, 1.4 mg) The mixture of BF3.OEt2 (1.188 mmol, 0.15 mL) and BF3.OEt2 (1.188 mmol, 0.15 mL) was stirred for several minutes at room temperature under argon atmosphere in anhydrous DCE (15 mL), followed by heating to 50 °C for 90 minutes, and then incubating overnight at room temperature. The reaction mixture was quenched with saturated sodium bicarbonate solution (approximately 30 mL), stirred for approximately 10 minutes, and then filtered through a polypropylene filter to retain water, eluting with DCM. The DCM was evaporated to dryness under vacuum, dissolved in a small volume of DCM, and loaded onto approximately 15 g of rapid silica gel in a sampler. Purification was achieved on silica gel by rapid chromatography (120 g, 0% acetone / DCM (2 CV)). 5% (10 CV), stopping at 0.5%, 0.7%, 1.1%, 1.4%, 1.7%, 2.0%, 2.3%, and 2.5%, isocratic at each step. The fraction containing the product was evaporated to dryness under vacuum. 329 mg of orange solid (54% yield) was given. 1H NMR (400 MHz, TCE) δ 8.71 (s, 1H), 8.48 (s, 1H), 7.91 (d, J = 8.3 Hz, 2H), 7.88 –7.78 (m, 4H), 7.67 (dd, J = 8.2, 4.4 Hz, 4H), 7.46 – 7.36 (m, 6H), 7.35 –7.20 (m, 12H), 7.10 (dd, J = 8.3, 1.5 Hz, 1H), 6.96 (ddd, J = 8.4, 7.1, 1.4Hz, 1H), 4.08 (s, 2H), 3.78 (s, 6H), 3.53 (p, J = 7.0 Hz, 2H), 1.86 (s, 6H), 1.18 (d, J = 7.0 Hz, 12H). MS (APCI): Chemical formula: C 83 H 58 BF 12 N3O 13 The calculated value of (M+H) is 1544; the measured value is 1544.

[0126] PLC-13: PLC-13 (10-(4-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xanthonro[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)acetoxy)-2,6-dimethoxyphenyl)-3,7-diisopropyl-1,9-dimethyl-5,5-bis(2,2,2-trifluoroacetoxy)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylic acid dimethyl ester): PLC-13.1 (0.3000 mmol, 420 mg), 2,2,2-trifluoroacetic acid trimethylsilyl ester (6.000 mmol, 1.0 mL) and BF3.OEt2 (1.2 The solution (0.15 mL, mmol) was stirred for several minutes in anhydrous DCE (15 mL) under argon atmosphere at room temperature, followed by heating to 45°C for 4 hours, then cooling to room temperature and quenching with saturated sodium bicarbonate solution (approximately 30 mL), stirring for approximately 10 minutes, then filtering through a polypropylene filter to retain water, and eluting with DCM. The DCM was evaporated to dryness under vacuum, dissolved in a small volume of DCM, and loaded onto approximately 15 g of rapid silica gel in a sampler. Purification was then performed on silica gel by rapid chromatography (80 g, 0% acetone / DCM (2 CV)). 5% (10 CV), stopping at 0.4%, 0.6%, 0.8%, 1.0%, 1.2%, 1.5%, 1.8%, and 2.1%. The fraction containing the product was evaporated to dryness under vacuum. 80 mg of orange solid was given (17% yield). 1H NMR (400 MHz, TCE) δ 8.76 (s, 1H), 8.51(s, 1H), 8.27 (d, J = 1.7 Hz, 2H), 8.08 (s, 1H), 8.03 (t, J = 2.5 Hz, 3H), 7.66 (d, J = 8.3 Hz, 2H), 7.49 (ddd, J = 8.5, 6.2, 2.5 Hz, 1H), 7.44 – 7.37(m, 2H), 7.33 – 7.20 (m, 1H), 7.06 – 6.93 (m, 2H), 6.55 (s, 2H), 4.05 (s,2H), 3.82 (s, 6H), 3.79 (s, 6H), 3.65 (h, J = 7.3 Hz, 2H), 1.76 (s, 6H), 1.30 (d, J = 7.0 Hz, 12H). MS (APCI): Chemical formula: C 75 H 52 BF18 N3O 15 The calculated value of (M+H) is 1588; the measured value is 1588.

[0127] PLC-14: PLC-14 (10-(4-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xanthonro[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)acetoxy)-2,6-dimethoxyphenyl)-3,7-diisopropyl-1,9-dimethyl-5,5-bis(2,2,2-trifluoroacetoxy)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylic acid dimethyl ester): PLC-14.1 (0.3000 mmol, 420 mg), 2,2,2-trifluoroacetic acid trimethylsilyl ester (6.000 mmol, 1.0 mL) and BF3.OEt2 (1.2 The solution (0.15 mL, mmol) was stirred for several minutes in anhydrous DCE (15 mL) under argon atmosphere at room temperature, followed by heating to 45°C for 4 hours, then cooling to room temperature and quenching with saturated sodium bicarbonate solution (approximately 30 mL), stirring for approximately 10 minutes, then filtering through a polypropylene filter to retain water, and eluting with DCM. The DCM was evaporated to dryness under vacuum, dissolved in a small volume of DCM, and loaded onto approximately 15 g of rapid silica gel in a sampler. Purification was then performed on silica gel by rapid chromatography (80 g, 0% acetone / DCM (2 CV)). 5% (10 CV), stopping at 0.4%, 0.6%, 0.8%, 1.0%, 1.2%, 1.5%, 1.8%, and 2.1%. The fraction containing the product was evaporated to dryness under vacuum. 80 mg of orange solid was given (17% yield). 1H NMR (400 MHz, TCE) δ 8.76 (s, 1H), 8.51(s, 1H), 8.27 (d, J = 1.7 Hz, 2H), 8.08 (s, 1H), 8.03 (t, J = 2.5 Hz, 3H), 7.66 (d, J = 8.3 Hz, 2H), 7.49 (ddd, J = 8.5, 6.2, 2.5 Hz, 1H), 7.44 – 7.37(m, 2H), 7.33 – 7.20 (m, 1H), 7.06 – 6.93 (m, 2H), 6.55 (s, 2H), 4.05 (s,2H), 3.82 (s, 6H), 3.79 (s, 6H), 3.65 (h, J = 7.3 Hz, 2H), 1.76 (s, 6H), 1.30 (d, J = 7.0 Hz, 12H). MS (APCI): Chemical formula: C 75 H 52 BF 18 N3O 15 The calculated value of (M+H) is 1588; the measured value is 1588.

[0128] PLC-15: PLC-15 (10-(5'-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xanthonro[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)acetoxy)-[1,1':3',1''-terphenyl]-2'-yl)-3,7-diisopropyl-1,9-dimethyl-5,5-bis(2,2,2-trifluoroacetoxy)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate): PLC-15.1 (1.557 mmol, 2323 mg), 2,2,2-trifluoroacetic acid trimethylsilyl ester (31.14 mmol, 5.4 mg) BF3.OEt2 (3.114 mmol, 0.38 mL) and BF3.OEt2 (3.114 mmol, 0.38 mL) were stirred for several minutes at room temperature under argon atmosphere in anhydrous DCE (40 mL), then heated to 50 °C for three hours, followed by cooling to room temperature and loading onto approximately 15 g of rapid silica gel packed in a sampler. Purification was then performed on silica gel by rapid chromatography (120 g, 80% toluene / hexane (2 CV)). 100% Toluene (2 CV) 0% EtOAc / Toluene (0 CV) 2% (5 CV), stopping at 0.1%, 1.0%, 1.5%, and 1.8%, isocratic at each step. The fraction containing the product was evaporated to dryness under vacuum. 965 mg of orange solid (37% yield) was given. 1H NMR (400 MHz, TCE) δ 8.76 (s, 1H), 8.50 (s, 1H), 8.27 (d, J = 1.6 Hz, 2H), 7.65 (d, J = 8.3 Hz, 2H), 7.49 (ddd, J =8.5, 6.1, 2.6 Hz, 1H), 7.45 – 7.36 (m, 4H), 7.32 – 7.15 (m, 13H), 7.09 – 6.94(m, 2H), 4.08 (s, 2H), 3.78 (s, 6H), 3.53 (h, J = 6.8 Hz, 2H), 1.85 (s, 6H),1.17 (d, J = 6.9 Hz, 12H). MS (APCI): Chemical formula: C 85 H 56 BF 18 N3O 13 The calculated value of (M+H) is 1680; the measured value is 1680.

[0129] PLC-16: PLC-16.1 (Ethyl 2-cyclobutyl-4-methyl-1H-pyrrole-3-carboxylate): Ethyl 3-cyclobutyl-3-oxopropionate (50.00 mmol, 7.76 mL), 1-aminoacetone hydrochloride (75.00 mmol, 8220 mg), and NaOAc (250.0 mmol, 20.508 g) were stirred overnight at 100 °C in HOAc (28.6 mL) and water (100 mL). The reaction mixture was cooled to room temperature and evaporated to dryness under vacuum. Extraction was performed with DCM (450 mL, 2 × 50 mL), dried over magnesium sulfate, filtered, and evaporated to dryness under vacuum. The crude product was dissolved in DCM and evaporated to approximately 50 g on a rapid silica gel sampler, packed into a sampler, and purified on silica gel by rapid chromatography (330 g, 0% EtOAc / hexane (2 CV)). 50% EtOAc / hexane (15 CV)). The fraction containing the product was evaporated to dryness under vacuum. 6840 mg (66% yield) of a reddish-brown waxy solid was given. ¹H NMR (400 MHz, DMSO) δ 10.89 (s, 1H), 6.43 (dq, J = 2.1, 1.0 Hz, 1H), 4.18 – 4.00 (m, 3H), 2.25 – 2.03 (m, 7H), 1.98 – 1.81 (m, 1H), 1.80– 1.68 (m, 1H), 1.25 (t, J = 7.1 Hz, 3H). MS (APCI): Chemical formula: C 12 H 17 The calculated value of NO2(M+H) is 208; the measured value is 208.

[0130] PLC-16.3 (10-(4-acetoxy-2,6-dimethylphenyl)-3,7-dicyclobutyl-5,5-difluoro-1,9-dimethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylic acid diethyl ester): PLC-16.1 (2.000 mmol, 415 mg), PLC-16.2 (1.000 mmol, 192 mg), and pTsOH·H2O (0.2000 mmol, 38 mg) were stirred at 40 °C under argon atmosphere in an anhydrous DCE (30 mL) for 4 hours, followed by cooling to room temperature. DDQ (2.500 mmol, 566 mg) was added to the reaction mixture, and the mixture was washed with 5 mL of DCE. The reaction mixture was stirred at room temperature for 10 minutes, then treated with Et3N (8.000 mmol, 1.1 mL) and BF3.OEt2 (12.000 mmol, 1.5 mL) was added to the reaction. The addition of Et3N (8.000 mmol, 1.1 mL) and BF3.OEt2 (12.000 mmol, 1.5 mL) was repeated, and the reaction was stirred at 65 °C for 40 minutes, then cooled to room temperature. The reaction mixture was quenched with water (approximately 10 mL) and stirred for approximately 10 minutes, then filtered through a polypropylene filter to retain the water, and eluted with DCM. The DCM was evaporated to dryness under vacuum, dissolved in a small volume of DCM, and loaded onto approximately 15 g of rapid silica gel in a sampler. Purification was achieved on silica gel by rapid chromatography (80 g, 0% acetone / hexane (2 CV)). 15% (5 CV), stop at 6.4%, isocratic). The fraction containing the product was evaporated to dryness, ground with methanol, dissolved in DCM, and evaporated to dryness under vacuum. 428 mg (67% yield) of orange solid was given. ¹H NMR (400 MHz, TCE) δ 6.97 (s, 2H), 4.49–4.29 (m, 6H), 2.61 (dq, J = 11.6, 9.4 Hz, 4H), 2.48–2.26 (m, 7H), 2.14 (s, 8H), 1.98–1.83 (m, 2H), 1.53 (s, 6H), 1.38 (t, J = 7.1 Hz, 6H). MS (APCI): Chemical formula: C 35 H 41 The calculated value of BF2N2O6(M+H) is 635; the measured value is also 635.

[0131] PLC-16 (10-(4-acetoxy-2,6-dimethylphenyl)-3,7-dicyclobutyl-1,9-dimethyl-5,5-bis(2,2,2-trifluoroacetoxy)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylic acid diethyl ester): PLC-16.3 (0.5153 mmol, 327 mg), 2,2,2-trifluoroacetic acid trimethylsilyl ester (10.31 mmol, 1.8 mL) and BF3.OEt2 (1.546 mmol, 0.198 mL) were stirred for 40 minutes at room temperature in anhydrous DCE (10 mL) under argon atmosphere, followed by stirring with saturated sodium bicarbonate solution (approximately 30 mL). The solution was quenched (mL) and stirred for approximately 10 minutes, then filtered through a polypropylene filter to retain water, and eluted with DCM. The DCM was evaporated to dryness, dissolved in a small volume of DCM, and loaded onto approximately 15 g of rapid silica gel in a sampler. Purification was performed on silica gel by rapid chromatography (80 g, 0% acetone / hexane (2 CV)). 15% (10 CV), stopped at 2.5% and 2.6%, isocratic at each step). The fraction containing the product was evaporated to dryness under vacuum. 350 mg (83% yield) of orange solid was given. ¹H NMR (400 MHz, TCE) δ 7.00 (s, 2H), 4.35 (q, J = 7.1 Hz, 4H), 4.24 (p, J = 9.1 Hz, 2H), 2.70 – 2.48 (m, 4H), 2.32 (s, 3H), 2.28 – 2.06 (m, 12H), 1.93 (q, J = 9.6 Hz, 2H), 1.58 (s, 6H), 1.37 (t, J = 7.1 Hz, 6H). MS (APCI): Chemical formula: C 39 H 41 BF6N2O 10 The calculated value of (M+H) is 823; the measured value is 823.

[0132] PLC-17: PLC-17.2 (5'-hydroxy-[1,1':3',1''-terphenyl]-2,2'',3,3'',4,4'',5,5'',6,6''-d10-2'-formaldehyde): PLC-17.1 (10.05 mmol, 2813 mg), (phenyl-d5)boric acid (40.20 mmol, 5105 mg), NaHCO3 (60.30 mmol, 5065 mg), and Pd(dppf)Cl2 (2.010 mmol, 1471 mg) were stirred at 85 °C under argon in anhydrous THF (100 mL) and water (15 mL) for 2 hours, followed by cooling the reaction mixture to room temperature. The mixture was diluted with water to approximately 400 mL and acidified with 6N HCl solution to pH approximately 1. The precipitate was filtered off, washed with water, dissolved in DCM, filtered through a polypropylene filter to retain water, eluted with DCM, and evaporated to dryness under vacuum. The crude material was dissolved in DCM and loaded onto approximately 45 g of rapid silica gel in a sampler. Purification was performed on silica gel by rapid chromatography (220 g, 0% acetone / hexane (2 CV)). 5% (10 CV), stop at 1.5%, isocratic). The fraction containing the product was evaporated to dryness under vacuum. 2399 mg (84% yield) of a grayish-white solid was given. ¹H NMR (400 MHz, DMSO) δ 10.69 (s, ¹H), 9.65 (s, ¹H), 6.74 (s, 2H). MS (APCI): Chemical formula: C 19 H4D 10 Calculated value of O2(M+H) = 285; Measured value: 285.

[0133] PLC-17.3 (2'-formyl-[1,1':3',1''-terphenyl]-5'-yl-2,2'',3,3'',4,4'',5,5'',6,6''-d10 2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xanthonro[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)acetic acid): PLC-17.2 (0.7000 mmol, 199 mg), 2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xanthonro[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)acetic acid (WuXi, 0.7700 0.07000 mmol, 651 mg), DMAP·pTsOH salt (0.07000 mmol, 21 mg), and EDC·HCl (1.400 mmol, 268 mg) were stirred in anhydrous DCE (20 mL) for one hour at room temperature, and then loaded onto approximately 45 g of rapid silica gel in a sampler. Purification was achieved on silica gel by rapid chromatography (120 g, 0% acetone / DCM (2 CV)). The distillate was stopped at 5% (10 CV), 0.1%, 0.5%, and 1.2%, isocratic at each step. The fraction containing the product was evaporated to dryness under vacuum. 741 mg of a yellow solid was given (95% yield). ¹H NMR (400 MHz, TCE) δ 9.87 (s, ¹H), 8.75 (s, ¹H), 8.50 (s, ¹H), 8.27 (d, J = 1.7 Hz, 2H), 8.07 (s, ¹H), 8.03 (t, J = 2.7 Hz, 3H), 7.66 – 7.56 (m, 2H), 7.49 (ddd, J = 8.5, 6.0, 2.6 Hz, 1H), 7.41– 7.34 (m, 2H), 7.32 – 7.25 (m, 1H), 7.23 (s, 2H), 7.05 – 6.95 (m, 2H), 4.04 (s, 2H). MS (APCI): Chemical formula: C 61 H 21 D 10 F 12 The calculated value of NO6(M+H) is 1112; the measured value is 1112.

[0134] PLC-17.5 (10-(5'-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xanthonro[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)acetoxy)-[1,1':3',1''-terphenyl]-2'-yl-2,2'',3,3'',4,4'',5,5'',6,6''-d10)-5,5-difluoro-3,7-diisopropyl-1,9-dimethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylic acid dimethyl ester): PLC-17.3 (0.5000 mmol, 556 DDQ (1.000 mmol, 190 mg), PLC-17.4 (1.050 mmol, 190 mg), and pTsOH·H2O (0.01000 mmol, 19 mg) were stirred at 50 °C in anhydrous DCE (20 mL) under argon atmosphere for 90 min, followed by cooling to room temperature. DDQ (1.000 mmol, 227 mg) was added to the reaction mixture, followed by rinsing with 5 mL of DCE. The reaction mixture was stirred at room temperature for 20 min, then treated with Et3N (4.000 mmol, 0.56 mL), and BF3·OEt2 (6.000 mmol, 0.74 mL) was added to the reaction mixture. The addition of Et3N (4.000 mmol, 0.56 mL) and BF3·OEt2 (6.000 mmol, 0.74 mL) was repeated, and the reaction was stirred at 75 °C for 2 h. The reaction mixture was cooled to room temperature and quenched with approximately 30 mL of saturated sodium bicarbonate solution, and stirred for 10 minutes. The mixture was filtered through a polypropylene filter to retain water and eluted with DCM. The DCM was evaporated to dryness under vacuum, dissolved in a small volume of DCM, and loaded onto approximately 45 g of rapid silica gel in a sampler. Purification was performed on the silica gel using rapid chromatography (0% acetone / DCM (2 CV)). 3% (10 CV), stop at 0.1%. The fraction containing the product was evaporated to dryness under vacuum. NMR showed that it was not pure, and several further purification attempts did not produce pure material. It was used as is in the next step.

[0135] PLC-17 (10-(5'-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xanthonro[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)acetoxy)-[1,1':3',1''-terphenyl]-2'-yl-2,2'',3,3'',4,4'',5,5'',6,6''-d10)-3,7-diisopropyl-1,9-dimethyl-5,5-bis(2,2,2-trifluoroacetoxy)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylic acid dimethyl ester): This is used to prepare impure PLC-17.5 (0.2097 mmol, 315 mg, estimated value), 2,2,2-trifluoroacetic acid trimethylsilyl ester (4.194 mmol, 0.72 mL), and BF3.OEt2 (0.6291 mmol, 0.077 mL) were stirred for several minutes in anhydrous DCE (10 mL) under argon atmosphere at room temperature for a few minutes, followed by heating to 50 °C for 3 hours, then cooling to room temperature and quenching with approximately 30 mL of saturated sodium bicarbonate solution while stirring for approximately 10 minutes. The mixture was filtered through a polypropylene filter to retain water and eluted with DCM. The DCM was evaporated to dryness under vacuum, dissolved in a small volume of DCM, and loaded onto approximately 15 g of rapid silica gel in a sampler. The solution was purified on the silica gel by rapid chromatography (80 g, acetone / hexane (2 CV)). 20% (10 CV), stopping at 9.5%, 10.0%, 10.5%, and 11.0%, isocratic at each step. The fraction containing the product was evaporated to dryness under vacuum. 198 mg of orange solid (56% yield) was given. 1H NMR (400 MHz, TCE) δ 8.76 (s, 1H), 8.50 (s, 1H), 8.27 (d, J = 1.7 Hz, 2H), 8.07 (s, 1H), 8.05 – 7.99 (m, 3H), 7.69 – 7.61 (m, 2H), 7.49 (ddd, J = 8.5, 6.1, 2.6 Hz, 1H), 7.41 (s, 2H), 7.41 – 7.37 (m, 2H), 7.31 – 7.25 (m, 1H), 7.05 – 6.91 (m, 2H), 4.08 (s, 2H), 3.78 (s, 6H), 3.61 –3.40 (m, J = 6.9 Hz, 2H), 1.85 (s, 6H), 1.17 (d, J = 7.0 Hz, 12H). MS (APCI): Chemical formula: C85 H 46 D 10 BF 18 N3O 13 The calculated value of (M+H) is 1690; the measured value is 1690.

[0136] PLC-18: PLC-18.1 (9-(3,5-bis(trifluoromethyl)phenyl)anthracene): 9-bromoanthracene (30.00 mmol, 7713 mg), (3,5-bis(trifluoromethyl)phenyl)boronic acid (60.00 mmol, 15474 mg), potassium carbonate (90.00 mmol, 12439 mg), and Pd(dppf)Cl2 (1.500 mmol, 1098 mg) were stirred for 30 minutes at 80 °C under argon in anhydrous THF (120 mL) and water (20 mL), followed by cooling to room temperature. The THF was evaporated under vacuum, the mixture was diluted with DCM, filtered through a polypropylene filter to retain water, eluted with DCM, and approximately 45 g of rapid silica gel was added to the DCM. The DCM was evaporated to dryness under vacuum, and the silica was packed into a sampler and purified on silica gel by rapid chromatography (330 g, 0% DCM / hexane (2 CV)). 25% (10 CV)). The fraction containing the product was evaporated to dryness under vacuum. 11166 mg of a pale yellow solid (95% yield) was given. MS (APCI): Chemical formula: C 22 H 12 Calculated value of F6(M+H): 391; Measured value: 391. 1H NMR (400 MHz, TCE) δ 8.62 (s, 1H), 8.13 (d, J = 1.1 Hz, 1H), 8.12 – 8.09 (m, 2H), 7.96 (d, J = 1.7Hz, 2H), 7.60 – 7.39 (m, 6H).

[0137] PLC-18.2 (9-(3,5-bis(trifluoromethyl)phenyl)-10-bromoanthracene): PLC-18.1 (28.60 mmol, 11165 mg), NBS (34.32 mmol, 6110 mg), and anhydrous DCE (150 mL) were stirred at room temperature under argon for 90 min, followed by heating to 50 °C for 30 min. The reaction mixture was cooled to room temperature, and the DCE was evaporated under vacuum (water bath at room temperature). The resulting solid was washed with water. The residue was dissolved in methanol and stirred for about 10 min, then filtered off and washed with MeOH. The solution was dried by suction. 8082 mg (60% yield) of a pale yellow solid was given. MS (APCI): Chemical formula: C 22 H 11 Calculated value of BrF6(M+H): 469; Measured value: 469. ¹H NMR (400 MHz, TCE) δ 8.66 (dt, J = 8.9, 1.0 Hz, 2H), 8.12 (s, 1H), 7.93 (d, J = 1.7 Hz, 2H), 7.67 (ddd, J = 9.0, 6.1, 1.6 Hz, 2H), 7.55 – 7.41 (m, 4H).

[0138] PLC-18.3 ((4-(10-(3,5-bis(trifluoromethyl)phenyl)anthracene-9-yl)-2,6-difluorophenyl)methanol): PLC-18.2 (6.000 mmol, 2815 mg), (3,5-difluoro-4-(hydroxymethyl)phenyl)boronic acid (9.000 mmol, 1691 mg), potassium carbonate (18.00 mmol, 2488 mg), and Pd(dppf)Cl2 (0.3000 mmol, 220 mg) were stirred at 80 °C under argon in anhydrous THF (120 mL) and water (20 mL) for 30 minutes, followed by cooling to room temperature. THF was evaporated under vacuum, DCM was added, the mixture was filtered through a polypropylene filter to retain water, eluted with DCM, approximately 45 g of rapid silica gel was added to the DCM, and the DCM was evaporated to dryness under vacuum and loaded into a sampler. Purification was performed on silica gel by rapid chromatography (220 g, 0% EtOAc / DCM (2 CV)). 25% (10 CV)). The fraction containing the product was evaporated to dryness under vacuum. 3014 mg (94% yield) of a pale yellow solid was given. MS (APCI): Chemical formula: C 29 H 16Calculated value of F8O (M+H): 533; Measured value: 533. 1H NMR (400 MHz, DMSO) δ 8.39 (td, J = 1.8, 0.9 Hz, 1H), 8.25 – 8.16 (m, 2H), 7.67 – 7.61 (m, 2H), 7.56 – 7.49 (m, 4H), 7.49 – 7.43 (m, 2H), 7.27 – 7.18 (m, 2H), 5.44 (t, J = 5.6 Hz, 1H), 4.70 (d, J = 5.7 Hz, 2H).

[0139] PLC-18.4 (9-(3,5-bis(trifluoromethyl)phenyl)-10-(4-(chloromethyl)-3,5-difluorophenyl)anthracene): PLC-18.3 (5.601 mmol, 3014 mg) and 2-chloro-1,3-dimethylimidazolium hexafluorophosphate (7.359 mmol, 2050 mg) were stirred for 30 minutes at 100 °C under argon atmosphere in anhydrous DMF (30 mL), followed by cooling to room temperature. The reaction mixture was diluted with water (approximately 300 mL) to precipitate the product. The product was filtered off, washed with water, and the moist precipitate was dissolved in DCM. The precipitate was filtered through a polypropylene filter to retain water, eluted with DCM, and approximately 45 g of rapid silica gel was added to the DCM. The DCM was evaporated to dryness under vacuum. The silica was packed into a sampler and purified on silica gel by rapid chromatography (220 g, 100% DCM, isocratic). The fraction containing the product was evaporated to dryness under vacuum. 3039 mg of a pale yellow solid (98% yield) was given. MS (APCI): Chemical formula: C 29 H 15 Calculated value of ClF8(M+H): 551; Measured value: 551. ¹H NMR (400 MHz, DMSO) δ 8.40 (tt, J = 1.8, 0.9 Hz, 1H), 8.21 (d, J = 1.7 Hz, 2H), 7.68 – 7.59 (m, 2H), 7.58 – 7.50 (m, 4H), 7.49 – 7.43 (m, 2H), 7.39 – 7.30 (m, 2H), 4.98 (s, 2H).

[0140] PLC-18.5 (2-Isopropyl-4-methyl-1H-pyrrole-3-carboxylic acid-4-(10-(3,5-bis(trifluoromethyl)phenyl)anthracene-9-yl)-2,6-difluorobenzoate): PLC-18.4 (2.413 mmol, 13298 mg), 2-isopropyl-4-methyl-1H-pyrrole-3-carboxylic acid (WuXi AppTech, 3.619 mmol, 605 mg) and potassium carbonate (4.825 mmol, 667 mg) were stirred at 100 °C in anhydrous DMF (25 mL) under argon for 30 minutes, and then cooled to room temperature. The product was precipitated by adding water (approximately 300 mL), filtered off, washed with water, dissolved in DCM, filtered through a polypropylene filter to retain water, eluted with DCM, and approximately 45 g of rapid silica gel was added to the DCM. The DCM was evaporated under vacuum, the silica gel was loaded into a sampler, and purified on the silica gel by rapid chromatography (120 g, 0% EtOAc / DCM (2 CV)). 5% (15 CV)). The fraction containing the product was evaporated to dryness under vacuum. 1549 mg (94% yield) of a pale yellow solid was given. MS (APCI): Chemical formula: C 38 H 27 Calculated value of F8NO2(M+H): 682; Measured value: 682. ¹H NMR (400 MHz, DMSO) δ 10.90 (s, 1H), 8.43 – 8.29 (m, 1H), 8.27 – 8.15 (m, 2H), 7.64 – 7.58 (m, 2H), 7.56 – 7.49 (m, 4H), 7.49 –7.43 (m, 2H), 7.32 (d, J = 7.4 Hz, 2H), 6.54 – 6.37 (m, 1H), 5.45 (s, 2H), 3.70 (p, J = 7.1 Hz, 1H), 2.15 (d, J = 1.1 Hz, 3H), 1.19 (d, J = 7.0 Hz, 6H).

[0141] PLC-18.7 (10-(4-acetoxy-2,6-dimethylphenyl)-5,5-difluoro-3,7-diisopropyl-1,9-dimethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylic acid bis(4-(10-(3,5-bis(trifluoromethyl)phenyl)anthracene-9-yl)-2,6-difluorobenzyl) ester): PLC-18.5 (2.271 mmol, 1548 mg), PLC-18.6 (1.136 mmol, 218 mg) and pTsOH·H2O (0.2271 mmol, 43 mg) were stirred at 65 °C in anhydrous DCE (25 mL) for 90 min. The reaction was then cooled to room temperature and precipitated with DDQ (1.703). The mixture was treated with triethylamine (9.084 mmol, 387 mg) and stirred at room temperature for 10 minutes until oxidation was complete. It was then treated with triethylamine (9.084 mmol, 1.3 mL) and BF3.OEt2 (13.63 mmol, 1.7 mL), and the treatment was repeated. The mixture was heated to 65°C for 30 minutes. The reaction mixture was cooled to room temperature, quenched with 30 mL of saturated sodium bicarbonate solution, and stirred for approximately 10 minutes. It was then filtered through a polypropylene filter to retain water, eluted with DCM, evaporated to dryness, and the residue was dissolved in a small volume of DCM. The solution was loaded onto approximately 45 g of rapid silica gel in a sampler and purified on silica gel by rapid chromatography (120 g, 0% EtOAc / hexane (2 CV)). 20% (10 CV, stop at 8.0%, isocratic). The fraction containing the product was evaporated to dryness under vacuum. 1093 mg of orange solid (61% yield) was given. MS (APCI): Chemical formula: C 87 H 61 BF 18Calculated value of N₂O₆(M+H): 1583; Measured value: 1583. ¹H NMR (400 MHz, TCE) δ 8.13 (d, J = 1.7 Hz, 2H), 8.03 – 7.97 (m, 4H), 7.71 – 7.60 (m, 4H), 7.54 – 7.48 (m, 4H), 7.46 (dt, J = 6.9, 3.2 Hz, 8H), 7.14 (d, J = 7.3 Hz, 4H), 7.03 (s, 2H), 5.57 (s, 4H), 3.91 (h, J = 7.1 Hz, 2H), 2.32 (s, 3H), 2.22 (s, 6H), 1.64 (s, 6H). 1.46 (d, J = 7.0 Hz, 12H).

[0142] PLC-18 (10-(4-acetoxy-2,6-dimethylphenyl)-3,7-diisopropyl-1,9-dimethyl-5,5-bis(2,2,2-trifluoroacetoxy)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylic acid bis(4-(10-(3,5-bis(trifluoromethyl)phenyl)anthracene-9-yl)-2,6-difluorobenzyl) ester): PLC-18.7 (0.3449 mmol, 546 mg), TFAOTMS (6.897 mmol, 1.2 mL), and BF3.OEt2 (1.379 mmol, 0.17 mL) were stirred for two hours at 45 °C in anhydrous DCE (10 mL) under argon atmosphere. The mixture was cooled to room temperature and quenched with saturated sodium bicarbonate solution (40 mL), stirred for 10 minutes, filtered through a polypropylene filter to retain water, and eluted with DCM. The DCM was evaporated under vacuum, and the residue was dissolved in a small amount of DCM, loaded onto approximately 40 g of rapid silica gel in a sampler, and purified on silica gel by rapid chromatography (120 g, 0% EtOAc / hexane (2 CV)). 10% (10 CV), stopping at 8.1% and 8.5%, isocratic at each step). The fraction containing the product was evaporated to dryness, the residue was ground with methanol, the ppt was filtered off, and dried under vacuum. 275 mg of orange solid was given (45% yield). MS (APCI): Chemical formula: C 91 H 61 BF 22 N2O 10Calculated value for (M+H): 1771; Measured value: 1771. ¹H NMR (400 MHz, TCE) δ 8.13 (s, 2H), 8.00 (d, J = 1.5 Hz, 4H), 7.65 (dt, J = 6.2, 3.2 Hz, 4H), 7.54 – 7.48 (m, 4H), 7.46 (dt, J = 6.9, 3.2Hz, 8H), 7.13 (d, J = 7.2 Hz, 4H), 7.06 (s, 2H), 5.55 (s, 4H), 3.72 (p, J = 7.0 Hz, 2H), 2.31 (s, 3H), 2.29 (s, 6H), 1.67 (s, 6H). 1.37 (d, J = 7.0 Hz, 12H).

[0143] PLC-19: Compound: N,N'-(ethane-1,2-diyl)bis(2,2,2-trifluoroacetamide): At 0 °C, a solution of trifluoroacetic anhydride (6.14 mL, 44 mmol) in 10 mL of diethyl ether was slowly added to a solution of ethylenediamine (1.209 g, 20 mmol) in 10 mL of diethyl ether. The mixture was stirred at room temperature for 30 minutes, and a white precipitate formed. The precipitate was filtered, washed with diethyl ether (10 mL × 2), and then dried in air to give a white solid (4.97 g, 98.7% yield).

[0144] LCMS (APCI-): Calculated value of C6H5F6N2O2(MH): 251.03; Measured value: 251.

[0145] 1H NMR (400 MHz, MeOD) δ 3.46 (s, 4H).

[0146] PLC-19: A solution of BODIPY compound PLC-19.1 (90 mg, 0.16 mmol) in 5 mL of anhydrous DCE was added to a 1 M BCl3 solution (0.3 mL, 0.3 mmol) in toluene. The reaction mixture was stirred at room temperature for one hour, followed by the addition of triethylamine (0.17 mL, 1.26 mmol), and then the addition of compound N,N'-(ethane-1,2-diyl)bis(2,2,2-trifluoroacetamide) (118 mg, 0.47 mmol). The mixture was stirred at 60 °C for 10 hours, followed by the addition of acetic anhydride (0.2 mL, 2 mmol), and the resulting mixture was stirred at 60 °C for 4 hours. The reaction mixture was treated with DCM, washed with brine, and the organic phase was collected, dried over MgSO4, and loaded onto silica gel. Purification was performed by rapid chromatography using hexane / DCM as the eluent (0% DCM to 100% DCM to 10% EA in DCM). The peak at m / e- = 766 was collected. The solvent was removed to give an orange solid (5 mg, 4% yield).

[0147] LCMS (APCI-): C 35 H 37 The calculated value of BF6N4O8 is 766.26; the measured value is 766.

[0148] 1 H NMR (400 MHz, CDCl3) δ 6.99 (s, 2H), 4.33 – 4.24 (m, 4H), 4.13 (s,4H), 2.56 (s, 6H), 2.36 (s, 6H), 2.13 (s, 3H), 1.72 (s, 6H), 1.34 – 1.30 (m,6H).

[0149] Example 2: Procedure for measuring the optical properties of chromophores in sharp emitters The glass substrate is prepared in the following manner: A 1.1 mm thick glass substrate with dimensions of 1 inch × 1 inch is cut to a specific size. Next, the glass substrate is washed with a detergent and deionized (DI) water, rinsed with fresh DI water, and sonicated for approximately 1 hour. Then, the glass is immersed in isopropyl alcohol (IPA) and sonicated for approximately 1 hour. Next, the glass substrate is immersed in acetone and sonicated for approximately 1 hour. Finally, the glass is removed from the acetone bath and dried under nitrogen at room temperature.

[0150] Prepare a 25% by weight solution of poly(methyl methacrylate) (PMMA) resin in spectrophotometric grade toluene. Stir the prepared PMMA polymer at 50°C until the PMMA is completely dissolved. [PMMA] CAS: 9011-14-7; [Toluene] CAS: 108-88-3.

[0151] In a 20 mL vial, 2 mg of the chromophore was added to the PMMA solution to prepare 2.0 × 10⁻⁶ ppm. -3 M solution [using formula: V] PMMA (mL) = [5000 / 2× [Calculate the volume of PMMA], then mix thoroughly using a Vortex mixer for approximately 5 minutes and sonicate for approximately 60 minutes. Next, spin-coat the PMMA / compound solution onto the prepared glass substrate at 1000 RPM for 20 seconds. The spin-coated sample is then baked in an oven at 150°C for 5 minutes to evaporate any remaining solvent.

[0152] Insert a 1-inch × 1-inch sample into a Shimadzu UV-3600 UV-VIS-NIR spectrophotometer (Shimadzu Instruments, Inc., Columbia, MD, USA) to measure the absorption spectrum.

[0153] The fluorescence spectrum (emission spectrum) of the 1 inch × 1 inch membrane sample prepared as described above was determined using a Fluorologmax spectrophotometer (Horiba Scientific, Edison, NJ, USA). Both 390 nm and 450 nm wavelengths were selected as excitation wavelengths.

[0154] The quantum yield of the spin-coated samples described above was determined using a Hamamatsu C11347 Absolute PL quantum yield spectrometer (Hamamatsu Inc., Campbell CA, USA). A 0.5'' × 0.5'' film was removed from the glass substrate for QY measurements. Wavelength scans were performed at 30 nm intervals from 390 nm to 450 nm (as the excitation wavelength). The QY at 450 nm is reported in Table 1.

[0155] The optical properties (absorption peak wavelength, FWHM, and quantum yield) of the spin-coated film are shown in Table 1 below.

[0156] Table 1. Optical properties of chromophores in PMMA Example 3: Light stability By exposing a 1-inch × 1-inch sample to 40 mW / cm 2 The photostability of the chromophores was tested using a blue LED (CREE, Durham, North Carolina, USA). Following the same procedure described above, absorbance, emission, and QY of the samples were monitored daily (for the first 2-3 days) and then weekly. The photostability of the chromophores was quantified by changes in absorbance (Abs%) and QY%, and emission characteristics were also monitored. Photostability measurements continued until absorbance decayed to below 50%. Photostability data for PLC-4 compared to PLC-4.5 are provided in Table 2, demonstrating the improved photostability of PLC-4 over PLC-4.5.

[0157] Unless otherwise indicated, all numerical values ​​used in this specification and embodiments to represent the quantity, characteristics (such as molecular weight), reaction conditions, etc., of components should be understood to be modified by the term "about" in all cases. Therefore, unless indicated to the contrary, the numerical parameters set forth in this specification and the appended embodiments are approximate values ​​and may vary depending on the desired characteristics sought to be obtained. At least, no attempt should be made to limit the application of the principle of equivalence. For the scope of embodiments, each numerical parameter should be understood at least based on the number of significant figures reported and by applying general rounding techniques.

[0158] For the disclosed processes and / or methods, the functions performed in the processes and methods may be implemented in different orders, as may be indicated by the context. Furthermore, the steps and operations outlined are provided only as examples, and some steps and operations may optionally be combined into fewer steps and operations, or expanded into additional steps and operations.

[0159] This disclosure may sometimes describe different components contained within or connected to other different components. The architectures depicted are merely examples, and many other architectures that achieve the same or similar functionality may be implemented.

[0160] The terminology used in this disclosure and the appended embodiments (e.g., the body of the appended embodiments) is generally intended to be “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 “including (but not limited to)”, etc.). Additionally, where a specific number of elements is introduced, this can be interpreted as meaning at least the number stated, as may be indicated by the context (e.g., the basic description of “two narratives” without other modifiers means at least two descriptions of two or more narratives). As used in this disclosure, any separating words and / or phrases presenting two or more alternative terms should be understood to encompass the possibility of including one, any, or both of these terms. For example, the phrase “A or B” should be understood to include the possibility of including “A” or “B”, or “A and B”.

[0161] Unless otherwise indicated herein or clearly contradicted by the context, the terms “a,” “an,” “the,” and similar designations used in the context of describing this disclosure (particularly in the context of the embodiments described below) are to be construed as encompassing both the singular and plural. The use of any and all instances or representative language (e.g., “such as”) provided herein is intended only to better illustrate this disclosure and does not limit the scope of any embodiment. Nothing in this specification should be construed as indicating that any unrepresented element is necessary for practicing this disclosure.

[0162] The grouping of alternative elements or embodiments disclosed herein should not be construed as limiting. Each group member may be referred to and embodied individually or in any combination with other members of the group or other elements found herein. It is contemplated that one or more members of a group may be included in or removed from the group for convenience and / or patentability reasons. When any such inclusion or removal occurs, this specification is deemed to contain the so-called modified groups to satisfy the written description of all Markush groups used in the additional embodiments.

[0163] Some embodiments include the best mode known to the inventors for carrying out this disclosure. Of course, variations of these embodiments will become apparent to those skilled in the art upon reading the foregoing description. The inventors intend for those skilled in the art to adopt these variations where appropriate, and the inventors intend to practice this disclosure in ways other than those specifically described herein. Therefore, embodiments include all modifications and equivalents of the subject matter described in embodiments permitted by applicable law. Furthermore, unless otherwise indicated herein or otherwise clearly contradicted by the context, any combination of the elements described above with all their possible variations is covered. In summary, it should be understood that the embodiments disclosed herein illustrate the principles of embodiments. Other modifications that may be adopted are within the scope of the embodiments. Therefore, alternative embodiments may be utilized in accordance with the teachings herein by way of example rather than limitation. Thus, embodiments are not limited to those exactly shown and described.

Claims

1. A photoluminescent composite comprising: According to the boron-dipyrrole methylene (BODIPY) moiety in the following formula: ， Each X is independently selected from O, NH and N-CH2; Where R 1 and R 6 Each of them is independently selected from hydrogen, saturated or unsaturated alkyl, aryl, and alkenyl groups; Where R 3 It is a C1-C2 alkyl group and R 4 It is a C1-C2 alkyl group; Where R 2 and R 5 Each of the following is independently selected from hydrogen, saturated alkyl, unsaturated alkyl, cyano (-CN), -C(=O)-(OCH2CH2). n -OCH3 (where n is 1, 2, 3 or 4), alkyl esters and aryl esters (-COOCH2Ar); Where R 7 and R 8 Each of them is independently selected from C1-C3 alkyl groups and optionally substituted aryl groups; The BODIPY portion has the characteristic of absorbing light energy of a first wavelength and emitting light energy of a second wavelength, wherein the second wavelength is greater than the first wavelength; and The photoluminescent composite exhibits an emission quantum yield of more than 80%.

2. A photoluminescent composite comprising: The portion that absorbs blue light; Linking complex (L); and According to the boron-dipyrrole methylene (BODIPY) moiety in the following formula: ， Where R 1 and R 6 Each of them is independently selected from hydrogen, saturated or unsaturated alkyl, aryl, and alkenyl groups; Where R 3 It is a C1-C2 alkyl group and R 4 It is a C1-C2 alkyl group; Where R 2 and R 5 Each of these is independently selected from hydrogen, saturated alkyl, unsaturated alkyl, cyano (-CN), alkyl ester and aryl ester (-COOCH2Ar); Where R 7 and R 8 Each of them is independently selected from C1-C3 alkyl groups and optionally substituted aryl groups; Each X is independently selected from O, NH and N-CH2; The connecting complex covalently connects the blue light-absorbing portion to the BODIPY portion; The portion that absorbs blue light can absorb light energy of a first excitation wavelength, the portion that absorbs blue light can absorb energy from the portion that absorbs blue light, and the portion that emits light energy of a second wavelength greater than the first wavelength. and The photoluminescent composite exhibits an emission quantum yield of more than 80%.

3. The photoluminescent composite of claim 1 or 2, wherein R 7 and R 8 Each of the components is independently selected from methyl, , , , and .

4. The photoluminescent composite of claim 2, wherein the portion absorbing blue light is a xatonisoquinoline derivative.

5. The photoluminescent composite of claim 4, wherein the xanthonisoquinoline derivative is according to the following formula: ， Among them, each R 11 It is independently selected from hydrogen, C1-C3 alkyl, optionally substituted aryl, and optionally substituted heteroaryl.

6. The photoluminescent composite of claim 2, wherein R 2 and R 5 Independently selected from hydrogen, saturated alkyl, unsaturated alkyl, cyano (-CN), alkyl ester and aryl ester (-COOCH2Ar), wherein R 7 and R 8 Each of them is a substituted aryl group.

7. The photoluminescent composite of claim 6, wherein R 1 and R 6 Each of them is independently selected from C1-C3 alkyl and isobutyl groups, and R 2 and R 5 Each of them is independently a C1-C3 ester.

8. The photoluminescent composite of claim 2, wherein L represents one of the following structures: , , and .

9. The photoluminescent composite of claim 2, wherein L represents one of the following structures: , and .

10. The photoluminescent composite of claim 2, wherein L represents one of the following structures: , , , , and .

11. The photoluminescent composite of claim 1, wherein the BODIPY portion has one of the following structures: (PLC-1)、 (PLC-2)、 (PLC-3)、 (PLC-16), and (PLC-19)。 12. The photoluminescent composite of any one of claims 2, 4, 5, 6, 7, 8, 9 or 10, comprising one of the following structures: (PLC-4)、 (PLC-5)、 (PLC-6)、 (PLC-7)、 (PLC-8)、 (PLC-9)、 (PLC-10)、 (PLC-11)、 (PLC-12)、 (PLC-13)、 (PLC-14)、 (PLC-15)、 (PLC-17), and (PLC-18)。 13. A color conversion film, comprising: Transparent substrate layer; Color conversion layer, comprising a resin matrix; and The photoluminescent composite of any one of claims 1 to 12, wherein the composite is dispersed within the resin matrix.

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

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

16. The color conversion film of claim 13, having a thickness between 10 μm and 200 μm.

17. The color conversion film of claim 13, having the following characteristics: absorbing light in the wavelength range of about 400 nm to about 480 nm, and emitting light in the wavelength range of about 500 nm to about 560 nm.

18. A method for preparing a color conversion film according to any one of claims 13, 14, 15, 16 and 17, comprising: The photoluminescent composite and the binder resin of any one of claims 1 to 12 are dissolved in a solvent; and The mixture is coated onto the surface of the transparent substrate layer.

19. A backlight unit comprising the color conversion film of any one of claims 13 to 17.

20. A display device comprising the backlight unit of claim 19.

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