Boron-containing cyclic emissive compounds and color conversion film containing the same

Abstract

The present disclosure generally relates to photoluminescent complexes, and to color conversion films including the same as well as their use in backlight units and display devices. In one form, a photoluminescent complex includes a boron-dipyrromethene (BODIPY) moiety covalently bonded to a blue light absorbing moiety.

Description

BORON-CONTAINING CYCLIC EMISSIVE COMPOUNDS AND COLOR CONVERSION FILM CONTAINING THE SAMEInventors: Jeffrey R. Hammaker and Shijun ZhengCROSS-REFERENCE TO RELATED APPLICATIONSThis application claims priority to U.S. Provisional Application No. 63 / 604,239, filed November 30, 2023, which is incorporated by reference in its entirety.BACKGROUNDIn color reproduction, the gamut, or color gamut, is a certain complete subset of colors available on a device such as a television or monitor. By way of example, a wide-gamut color space has been achieved by using three pure spectral primary colors (red, green and blue) and was developed to provide a broader color gamut and offer a more realistic representation of visible colors viewed through a display. However, the portrayal of more vibrant colors by a display may be possible if a device could provide a wider color gamut.As high-definition large screen displays become more common, the demand for higher performance, slimmer and highly functional displays has increased. Current light emitting diodes (LEDs) are obtained by a blue light source exciting a green phosphor, a red phosphor, or a yellow phosphor to obtain a white light source. However, the full width half maximum (FWHM) of the emission peak of the current green and red phosphors are quite large, usually greater than 40 nm, resulting in the green and red color spectrums overlapping and rendering colors that are not fully distinguishable from one another. In particular, this overlap leads to poor color rendition and the deterioration of the color gamut.To correct the deterioration in the color gamut, methods have been developed using films containing quantum dots in combination with LEDs. However, some quantum dots, such as cadmium-based quantum dots, are extremely toxic and are banned from use in many countries due to health safety issues. Further, non- cadmium-based quantum dots have a very low efficiency in converting blue LED light to green and red light. Quantum dots also require expensive encapsulating processes for protection against moisture and oxygen. The cost of using quantum dots is alsohigh because of the difficulties in controlling size uniformity during the production process.In view of the foregoing, there exists a need for additional contributions in this area of technology.SUMMARYPhotoluminescent complexes described herein may be used to improve the contrast between distinguishable colors in televisions, computer monitors, smart devices and other devices that utilize color displays. The photoluminescent complexes described herein provide a color converting dye complex with good blue light absorbance and narrow emissions bandwidths, e.g., with a full width half maximum (FWHM) of emission band of less than about 40 nm. In some forms, a photoluminescent complex may absorb light of a first wavelength and emit light of a second wavelength where the second wavelength is higher than the first wavelength. In some forms, photoluminescent complexes described herein may be utilized with a color conversion film for use in light emitting apparatuses. The color conversion film may exhibit reduced color deterioration by reducing overlap within the color spectrum which results in high quality color rendition.In one embodiment, a photoluminescent complex includes a blue light absorbing moiety, a linker complex which may be a substituted ester, an unsubstituted ester, a substituted ether, or an unsubstituted ether, and a boron-dipyrromethene (BODIPY) moiety. In some forms, the blue light absorbing moiety is a xanthenoisoquinoline derivative. In some forms, the linker complex may covalently link the xanthenoisoquinoline derivative to the BODIPY moiety. In some forms, the xanthenoisoquinoline derivative may absorb light of a first excitation wavelength and transfer energy to the BODIPY moiety, and the BODIPY moiety may absorb the energy from the xanthenoisoquinoline derivative and emit light of a second excitation wavelength which is greater than the first excitation wavelength.In some forms, one or more of the photoluminescent complexes described herein may exhibit an emission quantum yield greater than 80%. In some forms, the photoluminescent complex may exhibit an emission band with a full width half maximum (FWHM) of up to 40 nm.In some forms, one or more of the photoluminescent complexes described herein may have a Stokes shift, e.g., the difference between the excitation peak of the blue light absorbing moiety and the emission peak of the BODIPY moiety, of equal to or greater than 45 nm. In some forms where the blue light absorbing moiety is a xanthenoisoquinoline derivative, the xanthenoisoquinoline derivative may be according to the following general formula:, where each R11is independently selected from hydrogen(H), a C1-C3 alkyl, an optionally substituted aryl, and an optionally substituted heteroaryl.In some forms, the BODIPY moiety may be according to the following general formula:In other forms, the BODIPY moiety may be according to following general formula:In one or more of these forms, , each X may be independently selected from 0, NH, and N-CH2, R1and R6may be independently selected from hydrogen, a saturated or unsaturated alkyl group, e.g., methyl, isopropyl or isobutyl, an aryl group, and an alkene group, R3and R4may independently be a C1-C2 alkyl, R2and R5may be independently selected from hydrogen, an alkyl, a cyano (-CN), -C(=O)- (OCH2CH2)n-OCH3(wherein n is 1 , 2, 3, or 4), an alkyl ester (e.g., -COOCH2CH3), and an aryl ester (-COOCH2Ar), and R7and R8may be independently selected from a C1- C3 alkyl group and an optionally substituted aryl group. In some forms where each X is N-CH2, the -CH2groups are linked to each other. In some forms, R2and / or R5mayindependently selected from a C1-C3 alkyl, such as a methyl group or isopropyl group, and an isobutyl group, and R2and R5may independently be a C1-C3 ester.In some forms, L may have one of the following structures:In one embodiment, a color conversion film includes a color conversion layer including a resin matrix, and a photoluminescent complex described herein is dispersed within the resin matrix. In some forms, the color conversion film may have a thickness between 1 pm to about 200 pm. In some forms, the color conversion film may absorb blue light in a wavelength range of about 400 nm to about 480 nm and emit light in a wavelength range of about 500 nm to about 560 nm wavelength range. In other forms, the color conversion film may absorb blue light in a wavelength range of about 400 nm to about 480 nm range and emit light in a 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.In some forms, a color conversion film as disclosed herein may also include a singlet oxygen quencher and / or a radical scavenger.In another embodiment, a method for preparing a color conversion film includes dissolving a photoluminescent complex as described herein and a binder resin within a solvent, and applying the mixture on a surface of a transparent substrate.In yet another embodiment, a backlight unit includes a color conversion film as described herein. In still another embodiment, a display device includes a backlight unit as described herein.In some aspects, photoluminescent complexes described herein may exhibit excellent color gamut and luminescent properties. Methods for manufacturing color conversion films using a photoluminescent complex as described herein, and a backlight unit including the color conversion film are also provided. These and other embodiments are described in greater detail below.DETAILED DESCRIPTIONThe present disclosure is related to photoluminescent compounds and complexes for use in color conversion films, backlight units, and display devices, amongst other possibilities. The photoluminescent complexes described herein may be used to improve and enhance the transmission of one or more desired emissive bandwidths within a color conversion film. In some forms, the photoluminescent complex may enhance the transmission of a desired first emissive bandwidth and decrease the transmission of a second emissive bandwidth. For example, a color conversion film may enhance the contrast or intensity between two or more colors, increasing the distinction from one another. In some aspects, a photoluminescent complex as described herein may enhance the contrast or intensity between two colors, increasing their distinction from one another.As used herein, when a compound or chemical structure is referred to as being “substituted” it may include one or more substituents. By way of example, a substituted group may be derived from the unsubstituted parent structure where one or more hydrogen atoms on the parent structure have been independently replaced by one or more substituent groups. In one or more forms, the substituent groups may be independently selected from an optionally substituted alkyl, alkenyl, and a C3-C7 heteroalkyl.An alkyl moiety referenced herein may be branched, straight chain (i.e., unbranched), or cyclic. In some embodiments, the alkyl moiety may have 1 to 8 carbonatoms. The alkyl group of the compounds designated herein may be designated as “ C1-C8 alkyl” or similar designations. By way of example only, “ C1-C8 alkyl” indicates that there are 1 , 2, 3, 4, 5, 6, 7, or 8 carbon atoms in the alkyl chain, i.e., the alkyl chain may be methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, and any isomers thereof. Thus, a 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. Alkyl groups can be substituted or unsubstituted. Typical alkyl groups include, but are in no way limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, hexyl, ethenyl, propenyl, butenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.The term “heteroalkyl” as used herein refers to an alkyl group, as defined herein, in which one or more of the constituent carbon atoms have been replaced by a nitrogen, oxygen, or sulphur. 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. In addition, up to two heteroatoms may be consecutive, such as, by way of example, -CH2-NH-O-CH3.The term “aromatic” as used herein refers to a planar ring having a delocalized TT-electron system containing 4n+2 IT electrons, where n is an integer. Aromatic rings can be formed from five, six, seven, eight, nine, or more than nine atoms. Aromatic rings may be optionally substituted. The term “aromatic” includes both a carbocyclic aryl (e.g., phenyl) and a heterocyclic aryl (or “heteroaryl” or heteroaromatic”) group (e.g., pyridine). The term includes monocyclic or fused-ring polycyclic (i.e., rings which share adjacent pairs of carbon atoms) groups.The term “aryl” as used herein refers to an aromatic ring where each of the atoms forming the ring is a carbon atom. Aryl rings may be formed by 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, naphthalenyl, and phenanthrenyl.The term “heteroaryl” as used herein refers to an aryl group that includes one or more ring heteroatoms selected from nitrogen, oxygen, and sulfur, where the heteroaryl group has from 4 to 10 atoms in its ring system. It is understood that the heteroaryl ring can have additional heteroatoms in the ring. In heteroaryls that have two or more heteroatoms, those two or more heteroatoms can be the same or differentfrom one another. Heteroaryls may be optionally substituted. An N-containing heteroaryl moiety refers to an aryl group in which a skeletal atom of the ring is a nitrogen atom. Non-limiting examples of heteroaryl groups include pyrrole and imidazole moieties.The term “halogen” as used herein refers to fluorine, chlorine, bromine, and iodine.The term “bond”, “bonded”, “direct bond” or “single bond” as used herein refers to a chemical bond between two atoms or to two moieties when the atoms joined by the bond are considered to be part of a larger structure.The term “moiety” as used herein refers to a specific segment or functional group of a molecule. Chemical moieties are often recognized chemical entities embedded in or appended to a molecule.The term “cyano” or “nitrile” as used herein refers to any organic compound that contains a -CN functional group.The term “ester” refers to a chemical moiety with the formula -COOR, where R is an alkyl, cycloalkyl, aryl, heteroaryl (bonded through a ring carbon) or heterocyclic (bonded through a ring carbon). Any hydroxy, or carboxyl side chain on the compounds described herein can be esterified. Any suitable procedures and specific groups to make such esters may be utilized.As used herein the term “ether” refers to a chemical moiety that contains an oxygen atom connected to two alkyl or aryl groups with the general formula of R-O-R’, where R and R’ are an alkyl and / or aryl. Similarly, the term “alkoxy” refers to a chemical moiety that contains an oxygen atom bonded to an alkyl group that is further bonded to an alkyl or aryl group.As used herein the term “ketone” refers to the chemical moiety that contains a carbonyl group (a carbon-oxygen double bond) connected to two alkyl or aryl groups with the general formula of RC(=O)R’, where R and R’ are an alkyl and / or aryl.The term “BODIPY” as used herein, refers to a chemical moiety according to Formula (I) or Formula (II):(Formula I);di-substituted boron atom, such as a BF2 unit. The IIIPAC name for the BODIPY core (i.e., without any substituents) is 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene. The term “xanthenoisoquinoline” or “xanthenoisoquinoline derivative” as used herein, refers to a chemical moiety according to the following formula:. One non-limiting example includes 1 H-xantheno[2,1 ,9- def]isoquinoline-1 ,3(2H)-dione.In one aspect, the present disclosure relates to photoluminescent complexes that absorb light energy of a first wavelength and emit light energy in a second wavelength which is higher than the first wavelength. In one form, a photoluminescent complex may include an absorbing luminescent moiety and an emitting luminescent moiety that are coupled through a linker such that their distance is adjusted for the absorbing luminescent moiety to transfer its energy to the acceptor luminescent moiety where the acceptor luminescent moiety then emits energy at a second wavelength that is larger than the absorbed first wavelength.In one embodiment, a photoluminescent complex includes a blue light absorbing moiety, a linker complex, and a boron-dipyrromethene (BODIPY) moiety. In some forms, the blue light absorbing moiety is a xanthenoisoquinoline derivative and the linker complex may covalently link the xanthenoisoquinoline derivative to the BODIPY moiety. In some forms, the xanthenoisoquinoline derivative absorbs light of a first excitation wavelength and transfers energy to the BODIPY moiety, and the BODIPY moiety then emits a light energy of a second wavelength where the light energy of the second wavelength is higher than the first wavelength.While not intending to be bound by any particular theory, it is believed that energy transfer from the excited xanthenoisoquinoline derivative to the BODIPY moiety occurs through a Forster resonance energy transfer (FRET). This belief is due to the absorbance / emission spectra of the photoluminescent complexes where there are two major absorption bands, one at the blue light absorption band (xanthenoisoquinoline derivative) and one at the BODIPY absorption band, and only one emission band located at the BODIPY moieties emission wavelength.In some forms, a photoluminescent complex described herein may exhibit a high emission quantum yield. For example, in some forms, the emission quantum yield may be greater than about 50%, about 60%, about 70%, about 80%, or about90%. In some forms, the emission quantum yield may be greater than about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, or about 95%. Emission quantum yield can be measured by dividing the number of photons emitted by the number of photons absorbed, which is equivalent to the emission efficiency of the luminescent moiety. In some forms, the absorbing luminescent moiety may 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 may be up to nearly 1 (100%). Quantum yield measurements in film can be determined with a spectrophotometer such as a Quantaurus-QY spectrophotometer (Hamamatsu, Inc., Campbell, CA, USA).In some forms, a photoluminescent complex described herein may include an emission band having a full width half maximum (FWHM) of less than about 40 nm. The FWHM is the width of the emission band in nanometers at the emission intensity that is half of the maximum emission intensity for the band. In some forms, a photoluminescent complex described herein may include an emission band FWHM value that is less than or equal to about 35 nm, less than or equal to about 30 nm, less than or equal about 25 nm, or less than or equal to about 20 nm.In some forms, a photoluminescent complex described herein may have a Stokes shift that is 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 moiety and the emission peak of the BODIPY moiety.In some forms, a photoluminescent complex described herein may have a tunable emission wavelength. For example, by substituting in different substituents to the BODIPY moiety the emission wavelength can be tuned between about 500 nm to about 560 nm or any number bound by this range.In some forms, the blue light absorbing moiety can have a peak absorption maximum between about 400 nm to about 480 nm wavelength. In some embodiment, the peak absorption maximum of the blue light absorbing moiety may be between about 400 nm to about 405 nm, about 405 to about410 nm, about 410 to about 415 nm, about 415 to about 420 nm, about 420 to about 425 nm, about 425 to about 430nm, about 430 to about 435 nm, about 435 to about440 nm, about 440 to about 445 nm, about 445 to about 450 nm, about 450 to about 455 nm, about 455 to about 460 nm, about 460 to about465 nm, about 465 to about 470 nm, about 470 to about 475 nm, about 475 to about 480 nm, or any wavelength in a range bounded by any of these values.In some forms, a photoluminescent complex described herein may have an emission peak between about 500 nm to about 560 nm. In some embodiments, the emission peak may be between about 500 nm to about 515 nm, about 515 nm to about 520 nm, about 520 nm to about 525 nm, about 525 nm to about 530 nm, about 530 nm to about 535 nm, about 535 nm to about 540 nm, about 540 nm to about 545 nm, about 545 nm to about 550 nm, about 550 nm to about 555 nm, about 555 nm to about 560 nm, or any wavelength in a range bounded by any these ranges.In some forms of a photoluminescent complex the spatial distance of the blue light absorbing xanthenoisoquinoline or derivative and the BODIPY moiety is adjusted through the linker complex for transfer of the blue light absorbing xanthenoisoquinoline derivative’s energy to the BODIPY moiety.In one embodiment a photoluminescent complex (PLC) includes a blue light absorbing xanthenoisoquinoline derivative, a linker complex, and a BODIPY moiety. The linker complex covalently links the blue light absorbing xanthenoisoquinoline derivative and the BODIPY moiety. In some forms, the xanthenoisoquinoline derivative absorbs light energy of a first excitation wavelength and transfers an energy to the BODIPY moiety, and the BODIPY moiety absorbs the energy from the xanthenoisoquinoline derivative and emits a light energy of a second higher wavelength. In some forms, the photoluminescent complex exhibits an emission quantum yield greater than 80%.Some embodiments disclosed herein may include a blue light absorbing xanthenoisoquinoline derivative which may be of the following general formula:where R11and R12may independently be a hydrogen H, a C1-C4 alkyl group (e.g., methyl, n-butyl, t-butyl, etc.), a trifluoromethyl group, an optionally substituted aryl group, e.g.,wherein n is 1 , 2, 3, or4, an optionally substituted heteroaryl, or an alkoxy group. In some forms, R12 is a hydrogen, C1-4 alkyl, such as methyl, ethyl, n-propyl, isopropyl, butyl, or t-butyl. In some forms, R12 is t-butyl.In some forms, R12 may be an unsubstituted phenyl,In some forms, a photoluminescent complex may include a linker complex (L) which covalently links the blue light absorbing xanthenoisoquinoline derivative to theBODIPY moiety. In some embodiments, the linker complex may include a single bond between the xanthenoisoquinoline derivative and the BODIPY moiety.In some forms, the linker complex may be a substituted ester, an unsubstituted ester, a substituted ether, or an unsubstituted ether, just to provide a few non-limiting examples. In some embodiments, the linker complex may be an optionally substituted ester group.In some embodiments, the linker complex be a substituted ester group andIn some embodiments, the linker complex may be an unsubstituted ester groupand have one of the following structures: o , oIn some embodiments, the linker complex may be:In some embodiments, the linker complex may be:In some embodiments, the linker complex may be:In some embodiments, the linker complex may be:In some embodiments, the linker complex may be: -O(CH2)6-In some embodiments, the linker complex may be:In some embodiments, the linker complex may be:In some embodiments, the linker complex may be:In some embodiments, the linker complex may be:In some embodiments, the linker complex may be:In someIn someThe BODIPY moiety included in a photoluminescent complex described herein may be according to Formula I or Formula II:saturated or unsaturated alkyl group such as a methyl group, n-propyl, isopropyl group, n-butyl group, or isobutyl group; where R3may be a C1-C2 alkyl such as a methyl group and R4may be a C1-C2 alkyl such as a methyl group; where R2and R5may be independently selected from a hydrogen, a saturated alkyl, an unsaturated alkyl, a cyano (-CN), an alkyl ester (e.g., ethyl ester, 2-ethyl-hexyl ester, 2,2,2-trifluoroeethyl ester, a glycol ester), and an aryl ester (e.g., a phenyl ester (-COOCH2Ph)); where R7and R8may be independently selected from a C1-C3 alkyl group and an optionally substituted aryl group; where each X may be independently selected from 0, NH, and N-CH2; and where L may represent a linker complex including an optionally substituted ester or an optionally substituted ether linker. In some embodiments, L may be selectedIn some embodiments, the compound may be according to the following:where each R11is independently selected from hydrogen (H), a C1-C3 alkyl, an optionally substituted aryl, and an optionally substituted heteroaryl and the other substituents are as previously defined.In some forms, a BODIPY moiety described herein may be a BODIPY moiety where R1, R3, R4and R6are each a methyl; R2and R5are each a substituted ester group, where the substituted ester group is a C1-C7 alkyl chain or a polyglycol chain; R7and R8are each a methyl; and L is a linker complex. In some embodiments, a BODIPY moiety of the present disclosure may be aBODIPY moiety wherein R1and R6may be a C1-C3 alkyl, e.g., methyl and / or isopropyl.In some embodiments, R2and R5may independently be one,In some forms, R2isIn some forms,In some forms, R2isIn some forms,In some forms,In some forms, R7and R8may be an optionally substituted phenyl group. In some forms, R7and R8may independently be one of an unsubstituted benzyl group and an unsubstituted diphenyl group.In some embodiments, R7and R8may independently be selected from a methyl, , o meta-diphenyl group) and(2-ethylhexyl acetyl group).The photoluminescent complex of the present disclosure may be represented by the following which are provided for purpose of illustration and are in no way to be construed as limiting:Chemical Formula: C85H62BF12N3O13 Exact Mass: 1571.42Molecular Weight: 1572.23(PLC-5),Chemical Formula: C81H54BF12N3O13 Exact Mass: 1515.36Molecular Weight: 1516.12(PLC-6),In one embodiment, a photoluminescent complex includes a blue light absorbing xanthenoisoquinoline derivative. In some forms, the blue light absorbing xanthenoisoquinoline derivative may include an organic lumiphore. In some forms, the xanthenoisoquinoline derivative may have a maximum absorbance of light in the range 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 in a range that is bounded by any of these values. In some forms, the photoluminescent complex may have an absorbance maximum peak of about 450 nm. In other forms, the blue light absorbing xanthenoisoquinoline derivative may have a maximum peak absorbance of about 405 nm. In still other forms, the blue light absorbing xanthenoisoquinoline derivative may have a maximum peak absorbance of about 480 nm.In one embodiment a color conversion film includes a color conversion layer which includes a resin matrix and at least one photoluminescent complex described herein dispersed within the resin matrix.In some forms, the color conversion film may include a thickness of about 1 pm to about 200 pm. In some forms, the color conversion film has a thickness of about 1 pm to about 5 pm, about 5 pm to about 10 pm, about 10 pm to about 15 pm, about 15 pm to about 20 pm, about 20 pm to about 40 pm, about 40 pm to about 80 pm, about 80 pm to about 120 pm, about 120 pm to about 160 pm, about 160 pm to about 200 pm, or any thickness in a range bounded by any value above.In some forms, the color conversion film may absorb light in a wavelength range of about 400 nm to about 480 nm and may emit light in the wavelength range of about 500 nm to about 560 nm.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 and in physical contact with the surface(s) of the transparent layer that will be adjacent to a light emitting source. The transparent substrate is not particularly limited and the transparent substrate may include one or more of PE (polyethylene), PP (polypropylene), PEN (polyethylene naphthalate), PC (polycarbonate), PMA (polymethyl acrylate), PMMA (Polymethylmethacrylate), CAB (cellulose acetate butyrate), PVC (polyvinylchloride), PET (polyethyleneterephthalate), PETG (glycol modified polyethylene terephthalate), PDMS (polydimethylsiloxane), COC (cyclo olefin copolymer), PGA (polyglycolide or polyglycolic acid), PLA (polylactic acid), PCL (polycaprolactone), PEA (polyethylene adipate), PHA (polyhydroxy alkanoate), PHBV (poly(3-hydroxybutyrate-co- 3hydroxyvalerate)), PBE (polybutylene terephthalate), and PTT (polytrimethylene terephthalate), just to provide a few non-limiting examples.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 without the color conversion film disposed thereon may be adjacent to a light source. In some forms, the substrate may function as a support during the preparation of the color conversion film. The type of substrates used are not particularly limited,and the material and / or thickness is not limited, as long as it is transparent and capable of functioning as a support.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 radical scavenger.In one embodiment a method for preparing the color conversion film includes dissolving a photoluminescent compound as described herein and a binder resin within a solvent, and applying the mixture to the surface of a transparent substrate.Examples of the binder resin which may be used with the photoluminescent complex(es) include resins such as acrylic resins, polycarbonate resins, ethylene-vinyl alcohol copolymer resins, ethylene-vinyl acetate copolymer resins and saponification products thereof, AS resins, polyester resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins, polyvinylphosphonic acid (PVPA), polystyrene resins, phenolic resins, phenoxy resins, polysulfone, nylon, cellulosic resins, and cellulose acetate resins. In one or more forms, the binder resin may be a polyester resin and / or acrylic resin.In some forms, the solvent which can be used for dissolving or dispersing a photoluminescent complex and the resin may include an alkane, such as butane, pentane, hexane, heptane, and octane; cycloalkanes, such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane; alcohols, such as ethanol, propanol, butanol, amyl alcohol, hexanol, heptanol, octanol, decanol, undecanol, diacetone alcohol, and furfuryl alcohol; Cellosolves™, such as Methyl Cellosolve™, Ethyl Cellosolve™, Butyl Cellosolve™, Methyl Cellosolve™ acetate, and Ethyl Cellosolve™ acetate; propylene glycol and its derivatives, such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, and dipropylene glycol dimethyl ether; ketones, such as acetone, methyl amyl ketone, cyclohexanone, and acetophenone; ethers, such as dioxane and 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, methylene chloride, and tetrachloroethane; aromatic hydrocarbons, such as benzene, toluene, xylene, andcresol; and highly polar solvents, such as dimethyl formamide, dimethyl acetamide, and N-methylpyrrolidone.In another embodiment a backlight unit may include a color conversion film described herein. In still another embodiment a display device may include a backlight unit as described herein.EXAMPLESIt has been discovered that embodiments of the photoluminescent complexes described herein have improved performance as compared to other forms of dyes used in color conversion films. These benefits are further demonstrated by the following examples, which are intended to be illustrative of the disclosure only but are not intended to limit the scope or underlying principles in any way.Example 1.1 Comparative example 1 (CE-1)CE-1 : 0.75 g of 4-hydoxyl-2,6-dimethylvenzaldehyde (5 mmol) and 1.04 g of 2,4-dimethylpyrrole (11 mmol) were dissolved in 100 mL of anhydrous dichloromethane. The solution was degassed for 30 minutes. Then one drop of trifluoroacetic acid was added. The solution was stirred overnight under argon gas atmosphere at room temperature. To the resulting solution, DDQ (2.0g) was added and the mixture was stirred overnight. The next day the solution was filtered and then washed with dichloromethane resulting in a dipyrrolemethane (1.9g). Next, 1.0 g of dipyrrolemethane was dissolved in 60 mL of THF. 5 mL of trimethylamine was added to the solution and then degassed for 10 minutes. After degassing, 5 mL of trifluoroboron-diethylether was added slowly followed by heating for 30 minutes at 70 °C. The resulting solution was loaded on a silica gel and purified by flash chromatography using dichloromethane as the eluent. The desired fraction was collected and dried under reduced pressure to yield 0.9 g of an orange solid (76% yield). LCMS (APCI+): calculated for C21H24BF2N2O (M+H) = 369; found: 369.1H NMR (400 MHz, Chloroform-d) δ 6.64 (s, 2H), 5.97 (s, 2H), 4.73 (s, 1 H), 2.56 (s, 6H), 2.09 (s, 6H), 1.43 (s, 6H).Example 1.2 Comparative Example 2 (CE-2): involved the synthesis as described in Wakamiya, Atsushi et al. Chemistry Letters, 37(10), 1094-1095; 2008Example 1.3 Comparative Example 2 (CE-3):Synthesis procedure for Compound CE-3Compound CE3.2 (6-(2-aminophenoxy)-1 H,3H-benzo[de]isochromene-1 ,3- dione):A mixture of Compound CE-3.1 (2.0g, 6 mmol) and iron powder (<10um, 0.91 g, 16 mmol) in acetic acid (75 mL) was heated to reflux for 30 min. The resulting solution was poured into water (220m L). The resulting precipitate was collected by filtration and washed with water and dried thoroughly in air then under vacuum to afford a yellow solid (1.65g, in 90% yield). Confirmed by LCMS (APCI): calcd for C18H12NO4 (M+H): 306.1 ; Found: 306.Compound CE-3.3 (1 H,3H-isochromeno[6,5,4-mna]xanthene-1 ,3-dione):Compound CE-3.3 (1.5g, 4.9mmol) was dispersed in acetic acid (35mL) and cooled to 0 °C. While being stirred, precooled hydrochloric acid (3mL, 37 mmol) was added, then sodium nitrite solution (3.29g, 46 mmol) in 12 mL water was added dropwise at 0 °C. The whole was stirred for one hour at 0 °C, then transferred into an additional funnel, and dropped into a refluxed copper sulfate solution (5.08g, 20 mmol, in 50 mL water) over a one-hour period. After cooling to room temperature, the precipitate was collected by filtration, washed with water and acetone, then dried in air, and then in vacuum to give a yellow solid (0.92g, in 65% yield). Confirmed by LCMS (APCI): Calcd for C18H8O4(M-): 288.0; Found: 288.Compound CE-3.4 (5,11-dibromo-1 H,3H-isochromeno[6,5,4-mna]xanthene-1,3- dione):

[0001] A 2L 2N round bottom flask was charged with a stir bar and fitted with a long-finned condenser. To the flask was added Compound CE-1.1 (34.688 mmol, 10.00 g), followed by ortho-dichlorobenzene (1000 mL). The reaction mixture was stirred at room temperature and Br2 (416.26 mmol, 21.3 mL) was added. The second neck was stoppered, and the reaction mixture was heated with an aluminum heat block at 75 °C open to ambient air over the weekend. The reaction mixture was cooled to room temperature and a solid was filtered off. The filtrate was diluted with hexanes (~20% of volume) and a second precipitate was filtered off. Both of these precipitates were dried in vacuo at 100 °C. Orangish solids, 10.866 g total (69.9% yield). Both had similar LCMS and NMR. MS (APCI): calculated for Chemical Formula: C18H6Br2O4(M+H) = 445; found: 445.1H NMR (400 MHz, TCE) δ 9.47 (dd, J = 8.4, 1.5 Hz, 1 H),8.76 (d, J = 14.2 Hz, 2H), 7.72 - 7.63 (m, 1 H), 7.56 (dd, J = 8.3, 1.4 Hz, 1 H), 7.46 (ddd, J = 8.5, 6.7, 1.9 Hz, 1 H).Compound CE-3.5 (2-(4-(5,11-dibromo-1,3-dioxo-1 H-xantheno[2,1,9- def]isoquinolin-2(3H)-yl)phenyl)acetic acid):

[0002] A 100 mL 2N round bottom flask was charged with a stir bar and fitted with a finned condenser / gas adapter and flow control. The system was flushed with argon. To the flask was added 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). 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 and quenched with 6N HCI (~5 mL) and diluted with water (up to ~350 mL). The precipitate was filtered off, washing with water. The product was dried by suction and used without further purification in the next reactions. Assume 100% yield. MS (APCI): calculated for Chemical Formula: C26Hi3Br2NO5(M+H) = 578; found: 578.Compound CE-3.8:

[0003] A mixture of ethyl 2,4-dimethyl-1 H-pyrrole-3-carboxylate (1.0g, 6.0 mmol), 4-hydroxy-2,6-dimethylbenzaldehyde (0.449g, 3.0 mmol) and p- toluenesulfonic acid (p-TsOH) (50 mg, 0.29mmol) in 50 mL dichloroethane (DCE) was degassed and stirred at room temperature overnight. Liquid chromatography-Mass spectroscopy (LCMS) analysis shows that reaction completed with main peak of m / e+ = 467. To the mixture obtained above, 2,3-Dichloro-5,6-dicyano-1 ,4-benzoquinone (DDQ) (0.817g, 3.6 mmol) was added and the whole was stirred at room temperature for 30 min. LCMS analysis indicates that the reaction completed with a main peak of m / e+ = 465. With ice-batch cooling, to the mixture obtained above, triethylamine (1.7 mL, 12 mmol) and BF3-diethyl ether (2.2 mL, 18 mmol) were added, and the resulting mixture was stirred at 50 °C for one hour. An additional 1 mL triethylamine and 1 mL BF3-diethyl ether were added, and the whole was heated for an additional hour. LCMS analysis indicates that all dipyrrolemethine starting material was converted to BODIPY product with m / e+ = 513. After being cooled to room temperature, the reaction mixture was submitted to silica gel and purified by flash chromatography using eluents of hexanes / ethyl acetate (0% to 30% ethyl acetate). The desired fraction was collected.After removal of solvents, the desired product was obtained as an orange solid (1 ,0g, in 65% yield). 1 H NMR (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+): calculated for C27H32BF2N2O5 (M+H) = 513.2; Found: 513.Compound CE-3.6 (2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H- xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid):

[0001] A 250 mL 2N round bottom flask was charged with a stir bar and fitted with a finned condenser / gas adapter and flow control. The system was flushed with argon. To the flask was added Compound CE-3.5 (3.500 mmol, 2.034 g), (3,5- bis(trifluoromethyl)phenyl)boronic acid (14.00 mmol, 3.611 ), K2CO3 (19.25 mmol, 2.661 g), THF (60 mL), DMF (12 mL), and water (6 mL). The reaction mixture was stirred under argon at room temperature for a few minutes, then Pd(dppf)Cl2 (0.0245 mmol, 179 mg) was added. The headspace was flushed with argon for a minute, then the flow control was closed. The reaction mixture was stirred and heated in an aluminum heat block at 80 °C for three hours. The crude reaction mixture was evaporated to dryness in vacuo, taken up in DCM, and evaporated in vacuo onto ~35 g of flash silica gel. Purified by flash chromatography on silica gel (220g, equilibrateGives a brownish-yellow solid, 1.710 g (57.6% yield). MS (APCI): calculated for Chemical Formula: C42H19F12NO5 (M+H) = 846; found: 846.1H NMR (400 MHz, DMSO) δ 12.45 (s, 1 H), 8.62 (s, 1 H), 8.52 (d, J = 1.7 Hz, 2H), 8.36 (s, 1 H), 8.30 (s, 1 H), 8.26 (d, J = 1 .6 Hz, 2H), 8.24 (s, 1 H), 7.50 (ddd, J = 8.5, 7.2, 1 .5 Hz, 1 H), 7.46 - 7.38 (m, 2H), 7.37 - 7.27 (m, 2H), 7.14 (dd, J = 8.3, 1 .2 Hz, 1 H), 6.98 (ddd, J = 8.4, 7.2, 1 .3 Hz, 1 H), 6.85 (dd, J = 8.3, 1 .5 Hz, 1 H), 3.69 (s, 2H).Compound CE3.8 (6-(2-nitrophenoxy)-1 H,3H-benzo[de]isochromene-1 ,3-dione):A mixture of 2-nitrophenol (6.6g, 48 mmol), KOH powder (2.4g, 43 mmol) was mixed and stirred under vacuum for 30 min, then copper powder (0.4 g) was added, followed by 100 mL of anhydrous DMF. The mixture was stirred for 5 min, then 4- chloronaphthalic anhydride (5.1 g, 22 mmol) was added. The whole was degassed and then heated at reflux for 1.5 hr. After being cooled to room temperature, 100 mL of 20% hydrochloric acid was added dropwise into the resulting reaction mixture, which was allowed to sit for 2 hrs. The precipitate was collected by filtration, and then dried under vacuum overnight to give a yellow brown solid (4.6g). It was further purified by stirring in refluxing acetic acid (50 mL) for 1 hr, and then cooled to room temperature. Filtration and drying in air gave a yellow solid (3.0g, in 41 % yield). Confirmed by LCMS (APCI): calcd for C18H10NO6(M+H): 336.0; Found: 336.1H NMR (400 MHz, Chloroform-d) δ 8.80 (dd, J = 8.5, 1 .2 Hz, 1 H), 8.72 (dd, J = 7.3, 1 .2 Hz, 1 H), 8.50 (d, J = 8.2 Hz, 1 H), 8.19 (dd, J = 8.2, 1.7 Hz, 1 H), 7.90 (dd, J = 8.5, 7.3 Hz, 1 H), 7.79 (td, J = 7.9, 1 .7 Hz, 1 H), 7.54 (td, J = 8.0, 1 .3 Hz, 1 H), 7.39 (dd, J = 8.3, 1 .2 Hz, 1 H), 6.89 (d, J = 8.2 Hz, 1 H).Compound CE-3.7Compound CE-3.7 (diethyl 5,5-difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-1 ,3,7,9- tetramethyl-5H-4l4,5l4-dipyrrolo[1 , 2-c: 2' , 1 '-f][ 1 ,3,2]diazaborinine-2,8-dicarboxylate):A mixture of ethyl 2,4-dimethyl-1 H-pyrrole-3-carboxylate (1.0g, 6.0 mmol), 4- hydroxy-2,6-dimethylbenzaldehyde (0.449 g, 3.0 mmol) and tosylic acid (50 mg, 0.29mmol) in 50 mL 1 ,2-dichloroethane was degassed and stirred at room temperature overnight. LCMS analysis shows that one main peak with m / e+ = 467.To the resulting solution, DDQ (0.817g, 3.6 mmol) was added then stirred for 30 min at room temperature. LCMS analysis shows that all starting material was converted to the desired product with m / e+ =465.With ice-bath cooling, 1.7 mL triethylamine and 2.2 mL BF3-diethyl ether were added sequentially to the mixture from step 2. The whole was heated at 50 °C for one hour. LCMS analysis shows ~30% conversion. To the mixture, an additional 1 mL triethylamine and 1 mL BF3-diethyl ether were added, and the whole was heated at 50 °C for an additional hour. LCMS analysis shows that all stating materials were converted to the desired BODIPY product with m / e+ = 513, m / e- = 512. The reaction mixture was submitted directly to silica gel and purified by flash chromatography using eluents of hexanes / ethyl acetate (0%30% ethyl acetate). The main desired peak was collected, and removal of solvents gave an orange solid (1.0 g, in 65% yield). LCMS (APCI): calculated for C27H32BF2N2O5 (M+H): 513.2; Found: 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).Compound CE-3 (diethyl 10-(4-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)- 1,3-dioxo-1 H-xantheno[2,1,9-def]isoquinolin-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-dicarboxylate):Compound CE-3.6 (0.113 mmol, 80 mg), Compound CE-3.7 (diethyl 5,5- difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-1 ,3,7,9-tetramethyl-5H-4l4,5l4- dipyrrolo[1 ,2-c:2',1 '-f][1 ,3,2]diazaborinine-2,8-dicarboxylate) (0.0750 mmol, 38 mg), and DMAP.pTsOH salt (0.150 mmol, 44 mg) were placed in a 40 mL screw cap vial with a stir bar. To the vial was added dry DCM (10 mL) and the mixture was stirred to get a solution. To the vial was added DIC (0.263 mmol, 0.41 mL). The reaction was capped and stirred at room temperature overnight. The crude reaction mixture was diluted with hexanes and loaded onto ~20g of flash silica gel in a loader. The mixture was purified by flash chromatography on silica gel (120g, equilibrate 0% EtOAc / hexanes, eluting 0% (2 CV) 50% EtOAc / hexanes (30 CV)). Fractions containing product were evaporated to dryness in vacuo to give an orange solid, 70 mg (78% yield). MS (APCI): calculated for Chemical Formula: C65H46BF8N3O9 (M+H) = 1176; found: 1176.1H NMR (400 MHz, TCE) δ 8.71 (s, 1 H), 8.48 (s, 1 H), 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, 1 H), 7.10 (dd, J = 8.4, 1.5 Hz, 1 H), 7.05 (s, 2H), 6.96 (ddd, J = 8.4, 7.1 , 1.4 Hz, 1 H), 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).Compound PLC-1 :Compound PLC 1.1 (4-formyl-3,5-dimethylphenyl acetate): 4-hydroxy-2,6- dimethylbenzaldehyde (50.00 mmol, 7505 mg) and DMAP (100.0 mmol, 12.220 g) were combined in dry DCM (100 mL) and stirred under argon at room temperature. To the reaction was added acetic anhydride (75.00 mmol, 7.1 mL). The reaction was stirred for 15 minutes at room temperature, then quenched with a few drops of acetic acid. The reaction mixture was reduced in volume in vacuo and loaded onto ~60g of flash silica gel packed into a loader. The mixture was purified by flash chromatography on silica gel (120g, 0% EtOAc / hex (2 CV)15% (10 CV)). Fractions containing product were evaporated to dryness in vacuo to give a colorless oil, 4.890 g (51 % yield). MS (APCI): calculated for Chemical Formula: C11 H12O3 (M+H) = 193; found: 193. 1 H NMR (400 MHz, TCE) δ 10.55 (s, 1 H), 6.87 (s, 2H), 2.62 (s, 6H), 2.32 (s, 3H).Compound PLC-1.2 (diethyl 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- dicarboxylate): Compound PLC-1.1 (17.75 mmol, 3412 mg), ethyl 2,4-dimethyl-1 H- pyrrole-3-carboxylate (35.50 mmol, 5936 mg), and pTsOH.H2O (1.775 mmol, 338 mg) were stirred in dry DCE (100 mL) under argon at 40 °C for 90 minutes and then cooled to room temperature. DDQ (26.63 mmol, 6044 mg) was added and stirred for 10 minutes. To the reaction was added Et3N (71.01 mmol, 9.90 mL) and BF3.OEt2 (106.5 mmol, 13.1 mL). The addition of Et3N (71.01 mmol, 9.90 mL) and BF3.OEt2 (106.5 mmol, 13.1 mL) was repeated and the reaction stirred at 50 °C for 30 minutes. The reaction mixture was cooled to room temperature and quenched with 50 mL of waterand stirred for 5 minutes. The reaction mixture was filtered through a polypropylene frit to retain water. The frit was eluted with DCM. The organic eluent was evaporated onto 50g of flash silica gel in vacuo and packed into a loader. The mixture was purified by flash chromatography on silica gel (330g, 0% EtOAc / DCM (2 CV)10% (5 CV), stopping gradient at 4.0%, then 6.2%). Fractions containing the product were evaporated to dryness in vacuo, triturated with hot MeOH, adding water while hot to ~50%, cooled to room temperature, and filtered off the precipitate, washing with 50% MeOH / water. The product was dried in vacuo to give an orange solid, 6528 mg (66% yield). MS (APCI): calculated for Chemical Formula: C29H33BF2N2O6 (M-H) = 555 found: 555. 1 H 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).Compound PLC-1 (diethyl 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-dicarboxylate): Compound PLC-1.2, as described above, (0.5000 mmol, 277 mg) and trimethylsilyl (Z)-2,2,2-trifluoro-N- (trimethylsilyl)acetimidate (10.00 mmol, 2.7 mL) were stirred at room temperature in dry DCE (10 mL), then treated 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 HCI and stirred for 5 minutes, then filtered through a polypropylene frit to retain water, eluting DCM. The reaction mixture was evaporated to dryness in vacuo, diluted with a small amount of DCM, and loaded onto ~40g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (80g, 0% EtOAc / DCM (25% (10 CV), stopping gradient at 5.0%, then 5.2%, isocratic at each step). Fractions containing product were evaporated to dryness in vacuo to give an orange solid, 38 mg (10% yield). MS (APCI): calculated for Chemical Formula: C33H35BF6N4O8 (M-H) = 741 found: 741. 1 H NMR (400 MHz, CDCI3) 7.37 (s, δ 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).Compound PLC-2:Compound PLC-2 (diethyl 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-dicarboxylate) Compound PLC-1.2 (0.5000 mmol, 277 mg) and trimethylsilyl 2,2,2-trifluoroacetate (5.000 mmol, 0.86 mL) were stirred in dry DCE (10 mL) at room temperature under argon. The reaction mixture was treated with BF3.OEt2 (0.7500 mmol, 0.093 mL) and stirred at room temperature for 1 minute, then heated to 45 °C for 3 hours. The reaction mixture was cooled to room temperature and poured into ~30 mL of saturated sodium bicarbonate solution and stirred for 5 minutes.The reaction mixture was filtered through a polypropylene frit to retain water, eluting DCM. The reaction mixture was evaporated to dryness in vacuo, diluted with a small amount of DCM, and loaded onto ~40g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (120g, 0% acetone / DCM (2 CV)25% (5 CV), stopping gradient at 0.9%, 1.5%, 1.9%, and 2.0%, isocratic at each step). Fractions containing product were evaporated to dryness in vacuo to gives an orange solid, 198 mg (53% yield). MS (APCI): calculated for Chemical Formula: C33H33BF6N2O10 (M-H) = 743 found: 743.Synthesis of PLC-4:Compound PLC-4.1 ((3,5-dibromophenoxy)triethylsilane): A 500 mL 2N round bottom flask was charged with a stir bar and fitted with a gas adapter and septum. The flask was placed in a Dewar bowl. The flask was flushed with argon. To the flask was added 3,5-dibromophenol (100.0 mmol, 25.190g), imidazole (300.0 mmol, 20.430 g), and dry DCM (200 mL). The mixture was stirred to get a solution at room temperature, then cooled to 0 °C with an ice-water bath. To the flask was added chlorotriethylsilane (150.0 mmol, 25.2 mL) via syringe with stirring at 0 °C. The reaction was stirred at 0 °C for 50 minutes, then partitioned with water (200 mL). The layers were separated, and the water layer extracted with DCM (50 mL). The combined organic layers were dried over MgSO4, filtered and evaporated to dryness in vacuo. The mixture was diluted with hexanes and loaded onto a loader containing 60g of flash silica gel. Purified by flash chromatography on silica gel (220g, equilibrate and elute 100% hexanes). Fractions containing product were evaporated to dryness in vacuo to give a colorless oil, 27.811 g (76% yield). MS (APCI): calculated for Chemical Formula: C12Hi8Br2OSi (M+H) = 365; found: 365.1H NMR (400 MHz, TCE) 7.28 δ (t, J = 1.7 Hz, 1 H), 6.96 (d, J = 1 .6 Hz, 2H), 1.10 - 0.95 (m, 9H), 0.75 (qd, J = 7.7, 0.9 Hz, 6H).Compound PLC-4.2 (2,6-dibromo-4-hydroxybenzaldehyde) A 250 mL 2N round bottom flask was charged with a stir bar and fitted with a gas adapter and septum. The flask was placed in a Dewar bowl. The flask was flushed with argon. Compound PLC-4.1 (30.00 mmol, 10.985 g) and azeotroped were weighed out from toluene. Compound PLC-4.1 was transferred under argon to the reaction flask, then dry THF was added (130 mL) and the reaction mixture was stirred to get a homogeneous solution at room temperature. The reaction mixture was cooled to -78 °C (dry ice / acetone). The system was purged of oxygen by vacuum / backfilling argon cycles (3X). A solution of LDA in THF / hexanes (1 ,0M, 60.00 mmol, 60.0 mL) was added with vigorous stirring over a few minutes. The solution was stirred at -78 °C for 70 minutes, then anhydrous DMF (150.0 mmol, 11 .6 mL) was added via syringe and stirred for 60 minutes at -78 °C. The reaction mixture was dumped cold into 400 mL of sat. NH4CI solution with stirring. The solution was extracted with EtOAc (100 mL) and the layers separated. The aqueous layer was acidified to pH ~1 using excess 6N HCI to get an off-white ppt. The organic layer was extracted with 100 mL sat. NH4CI, then twice with 10% K2CO3 (100 mL). These aqueous extracts were also added to the acidified water, maintaining a pH of ~1. The resulting precipitate was filtered off, then dried in a vacuum oven at 90 °C overnight to give an off-white / grey precipitate, 6.665 g (79% yield). MS (APCI): calculated for Chemical Formula: C7H4Br2O2 (M+H) = 281 ; found: 281.1H NMR (400 MHz, Acetone) δ 10.14 (s, 1 H), 7.24 (s, 2H).Compound PLC-4.3] (3,3",5,5"-tetra-tert-butyl-5'-hydroxy-[1,1,:3,,1"-terphenyl]- 2'-carbaldehyde): A 500 mL 2N round bottom flask was charged with a stir bar and fitted with a finned condenser / gas adapter and flow control. The system was flushed with argon. To the flask was added Compound PLC4.2 (5.500 mmol, 1.540 g), (3,5- di-tert-butylphenyl)boronic acid (22.00 mmol, 5.150g), NaHCO3(33.00 mmol, 2.772 g), Pd(dppf)CL (1 .100 mmol, 805 mg), dry THF (270 mL), and water (9 mL). The heat block was set to 80 °C and the reaction mixture stirred at this temperature overnight. The reaction mixture was evaporated onto 60g of flash silica gel and placed into a loader. Purified by flash chromatography on silica gel (220g, equilibrate 0% EtAc / hexanes, eluting 0% (2 CV)30% EtOAc / hexanes (20 CV)). Fractions containing product were evaporated to dryness in vacuo to give a light yellow solid, 2.256 g (82% yield). MS (APCI): calculated for Chemical Formula: C35H46O2 (M+H) = 499; found: 499.1H NMR (400 MHz, TCE) δ 9.80 (s, 1 H), 7.42 (t, J = 1 .8 Hz, 2H), 7.15 (d, J = 1.8 Hz, 4H), 6.87 (s, 2H), 1.35 (s, 36H).Compound PLC-4.4 (3,3",5,5"-tetra-tert-butyl-2,-formyl-[1,T:3,,1"-terphenyl]-5'- yl 2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1 H-xantheno[2,1,9- def]isoquinolin-2(3H)-yl)phenyl)acetate) A 40 mL screw-cap vial was charged with 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-1 H-xantheno[2,1 ,9-def]isoquinolin-2(3H)- yl)phenyl)acetic acid (from outside vendor) (5.428 mmol, 4.590 g), DMAP.pTsOH salt (4.523 mmol, 1332 mg), and dry DCM (20 mL). The reaction mixture was stirred at room temperature to give a yellow slurry. With stirring at room temperature, DIC (9.047 mmol, 1.41 mL) was added. The reaction mixture was stirred at room temperature for 60 minutes, then diluted with hexanes 1 :1 and loaded onto ~60g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (220g, equilibrate 0% EtOAc / hexanes, eluting 0% 2 CV -> 20% EtOAc / hexanes (22 CV)). Fractions containing product were evaporated to dryness in vacuo to give a yellow solid, 5.182 g (86% yield). MS (APCI): calculated for Chemical Formula: C77H63F12NO6 (M+H) = 1326; found: 1326.1H NMR (400 MHz, TCE) δ 9.89 (s, 1 H), 8.75 (s, 1 H), 8.50 (s, 1 H), 8.29 - 8.24 (m, 2H), 8.07 (s, 1 H), 8.05 - 7.97 (m, 3H), 7.67 - 7.60 (m, 2H), 7.49 (ddd, J = 8.6, 6.1 , 2.6 Hz, 1 H), 7.43 (t, J = 1 .8 Hz, 2H), 7.38 (d, J = 8.4 Hz, 2H), 7.31 - 7.25 (m, 1 H), 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).Compound PLC-4.5 (diethyl 10-(5'-(2-(4-(5,11 -bis(3,5- bis(trifluoromethyl)phenyl)-1,3-dioxo-1 H-xantheno[2,1,9-def]isoquinolin-2(3H)- yl)phenyl)acetoxy)-3,3",5,5"-tetra-tert-butyl-[1,T: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-dicarboxylate): A 250 mL 2N round bottom flask was charged with a stir bar and fitted with a finned condenser / gas adapter and flow control. The system was flushed with argon. To the flask was added Compound PLC-4.4 (1.000 mmol, 1.326 g), ethyl 2,4-dimethyl-1 H-pyrrole-3-carboxylate (2.100 mmol, 351 mg), and dry DCE (100 mL). The reaction mixture was stirred vigorously at room temperature for 30 seconds, then pTsOH.H2O (0.2000 mmol, 38 mg) was added. The reaction mixture was stirred under argon at room temperature for 19 hours, then DDQ was added (1 .300 mmol, 295 mg), followed by dry DCE (5 mL). The mixture was stirred for 30 minutes at room temperature, then more DDQ (0.5000 mmol, 114 mg) wasadded, followed by dry DCE (5 mL). After stirring for another 30 minutes, the oxidation was complete. To the reaction was added Et3N (8.000 mmol, 1.1 mL) and BF3.OEt2 (12.00 mmol, 1.5 mL). After 1 minute, the addition of Et3N (8.000 mmol, 1.1 mL) and BF3.OEt2 (12.00 mmol, 1.5 mL) was repeated. The reaction mixture was stirred at 50 °C for 50 minutes, then the reaction mixture was evaporated onto 25g of flash silica gel in vacuo (bath = 60 °C) and this silica placed in a loader. Purified by flash chromatography on silica gel (330 g, equilibrate 0% acetone / hexanes, eluting 0% (2 CV) 20% acetone / hexanes (15 CV)). Fractions containing product were evaporated to dryness in vacuo. Repurified by loading directly onto a 220g column using 10% DCM / hexanes (dry load), eluting 0% EtOAc / DCM (2 CV) 0.2% EtOAc / DCM (2 CV)-> isocratic 0.2% EtOAc / DCM. Fractions containing product were evaporated to dryness in vacuo to give an orange solid, 870 mg (52% yield). MS (APCI): calculated for Chemical Formula: C95H84BF14N3O9 (M+H) = 1689; found: 1689. 1 H NMR (400 MHz, TCE) δ 8.75 (s, 1 H), 8.50 (s, 1 H), 8.26 (s, 2H), 8.07 (s, 1 H), 8.02 (s, 3H), 7.66 (d, J = 8.3 Hz, 2H), 7.53 - 7.44 (m, 1 H), 7.43 - 7.34 (m, 4H), 7.27 (d, J = 8.1 Hz, 1 H), 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).Compound PLC-4 (diethyl 10-(5'-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)- 1,3-dioxo-1 H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-3,3",5,5"- tetra-tert-butyl-[1,T: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- dicarboxylate): Compound PLC-4.5 (0.2500 mmol, 422 mg), trimethylsilyl 2,2,2- trifluoroacetate (5.000 mmol, 086 mL) and BF3.OEt2 (0.3750 mmol, 0.046 mL) were stirred in dry DCE (10 mL) at room temperature for 1 minute, then heated to 45 °C overnight. The reaction mixture was poured into ~30 mL of saturated sodium bicarbonate solution and stirred for 5 minutes, then filtered through a polypropylene frit to retain water, eluting with DCM. The eluent was evaporated to dryness in vacuo, dissolved in a little DCM, and loaded onto ~15g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (80g, 0% acetone / hexanes (2 CV)10% (5 CV), stopping gradient at 1.2%, then 5.0%. Fractions containing product were evaporated to dryness in vacuo to give an orange solid, 165 mg (35% yield). MS (APCI): calculated for Chemical Formula: C99H84BF18N3O13 (M-H) = 1876 found: 1876. 1 H NMR (400 MHz, TCE) 8 δ.75 (s, 1 H), 8.50 (s, 1 H), 8.26 (d, J = 1.6 Hz, 2H), 8.07 (s, 1 H), 8.06 - 7.99 (m, 3H), 7.66 - 7.61 (m, 2H), 7.49 (ddd, J = 8.5, 6.2, 2.5 Hz, 1 H), 7.42 - 7.36 (m, 2H), 7.33 (s, 2H), 7.30 - 7.25 (m, 1 H), 7.23 (t, J = 1 .8 Hz, 2H), 7.05 - 6.94 (m, 2H), 6.83 (d, J = 1.8 Hz, 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).PLC-9:PLC-9 (diethyl 10-(5'-(2-(4-(1 ,3-dioxo-5,11 -bis(4-(trifluoromethyl)phenyl)-1 H- xantheno[2,1,9-def]isoquinolin-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-dicarboxylate) PLC-9.1 (0.2367 mmol, 321 mg) was dissolved in dry DCE (10 mL) and stirred at room temperature under argon. To the reaction was added trimethylsilyl 2,2,2-trifluoroacetate (4.734 mmol, 0.82 mL), followed by BF3.OEt2 (0.3351 mmol, 0.044 mL). The reaction was stirred at room temperature for 1 minute, then heated to 45 °C for three hours. The reaction was poured into ~30 mL of saturated sodium bicarbonate solution and stirred for 5 minutes, then filtered through a polypropylene frit to retain water, eluting with DCM. The combined organic layers were evaporated to dryness, taken up in a small volume of DCM, and loaded onto ~15g of flash silica packed into a loader. Purified by flash chromatography on silica gel (80g, 0% EtOAc / toluene (2 CV)10% (10 CV), stopping at 3.0%, isocratic). Fractions containing product were evaporated to dryness in vacuo, taken up in hot methanol, diluted with some water, cooled to room temperature, and filtered off, washing 90% methanol / water. The product was dissolved in DCM and evaporated to dryness. Gives an orange solid, 178 mg (49% yield). MS (APCI): calculated for Chemical Formula: C83H58BF12N3O13 (M+H) = 1544 found: 1544.1 H NMR (400 MHz, TCE) 6 8.69 (s, 1 H), 8.46 (s, 1 H), 7.94 (d, J = 7.8 Hz, 2H), 7.90 (d, J = 8.4 Hz, 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, 1 H), 7.27 (dd, J = 8.8, 2.4 Hz, 2H), 7.22 - 7.14 (m, 1 H), 7.13 - 7.07 (m, 3H), 7.00 - 6.91 (m, 1 H), 4.02 (s, 2H), 3.01 (s, 6H), 2.26 (s, 6H), 1.91 (s, 6H).PLC-10:PLC-10 (dimethyl 10-(4-(2-(4-(1 ,3-dioxo-5,11 -bis(4-(trifluoromethyl)phenyl)-1 H- xantheno[2,1,9-def]isoquinolin-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-dicarboxylate) PLC-10.1 (0.6000 mmol, 739 mg) was stirred in dry DCE (15 mL) under argon at room temperature. To the reaction was added trimethylsilyl 2,2,2-trifluoroacetate (12.00 mmol, 2.07 mL) and BF3.OEt2 (1.800 mmol, 0.22 mL) and the reaction heated to 50 ° C for one hour. The reaction mixture was poured into ~40 mL of saturated sodium bicarbonate solution and stirred for five minutes. The reaction was filtered through a polypropylene frit to retain water, eluting with DCM. The eluent was evaporated to dryness in vacuo, dissolved in a small volume of DCM, and loaded onto ~15g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (120g, 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). Fractions containing product were evaporated to dryness in vacuo. The product was triturated with hot methanol, diluted ~1 :1 with water, cooled to room temperature, filtered off, washing with ~1 :1 methanokwater, dissolved in DCM, dried over magnesium sulfate, filtered off, evaporated to dryness in vacuo. Gives an orange solid, 608 mg (71 % yield). MS (APCI): calculated for Chemical Formula: C73H54BF12N3O13 (M+H) = 1420 found: 1420. 1 H NMR (400 MHz, TCE) δ 8.71 (s, 1 H), 8.48 (s, 1 H), 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, 1 H), 7.10 (dd, J = 8.3, 1.5 Hz, 1 H), 7.07 (s, 2H), 6.96 (ddd, J = 8.4, 7.1 , 1.3 Hz, 1 H), 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).PLC-11:PLC-11.1 PLC-11PLC-11 (dimethyl 10-(5'-(2-(4-(1 ,3-dioxo-5,11 -bis(4-(trifluoromethyl)phenyl)-1 H- xantheno[2,1,9-def]isoquinolin-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-dicarboxylate): PLC-11.1 (0.1897 mmol, 283 mg), trimethylsilyl 2,2,2- trifluoroacetate (3.793 mmol, 0.66 mL), and BF3.OEt2 (0.5690 mmol, 0.070 mL) were stirred in dry DCE (15 mL) at room temperature for a few minutes, then heated to 500C for one hour, then cooled to room temperature. The mixture was quenched with saturated sodium bicarbonate solution (~30 mL), stirring for ~10 minutes, then filtering through a polypropylene frit to retain water, eluting with DCM. The DCM was evaporated to dryness in vacuo, dissolved in a small volume of DCM, loaded onto ~15g of flash silica gel packed into a loader. Purified by flash chromatography on silica gelstopping at 0.1 %, and 1.2%, isocratic at each step). Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 148 mg (47% yield). 1 H NMR (400 MHz, TCE) 8.70 δ (s, 1 H), 8.47 (s, 1 H), 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, 1.3 Hz, 1 H), 7.10 (dd, J = 8.4, 1.5 Hz, 1 H), 7.01 - 6.92 (m, 1 H), 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): calculated for Chemical Formula: C85H56BF18N3O13 (M+H) = 1680; found: 1680.PLC-12:PLC-12 (dimethyl 10-(5'-(2-(4-(1 ,3-dioxo-5,11 -bis(4-(trifluoromethyl)phenyl)-1 H- xantheno[2,1,9-def]isoquinolin-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 (0.3960mmol, 537 mg), trimethylsilyl 2,2,2-trifluoroacetate (7.920 mmol, 1 .4 mL) and BF3.OEt2(1.188 mmol, 0.15 mL) were stirred in dry DCE (15 mL) under argon at room temperature for a few minutes, then heated to 50 ° C for 90 minutes, then room temperature overnight. The reaction mixture was quenched with saturated sodium bicarbonate solution (~30 mL), stirring for ~10 minutes, then filtering through a polypropylene frit to retain water, eluting with DCM. The DCM was evaporated to dryness in vacuo, dissolved in a small volume of DCM, loaded onto ~15g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (120g, 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). Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 329 mg (54% yield). 1 H NMR (400 MHz, TCE) δ 8.71 (s, 1 H), 8.48 (s, 1 H), 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, 1 H), 6.96 (ddd, J = 8.4, 7.1 , 1.4 Hz, 1 H), 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): calculated forChemical Formula: C83H58BF12N3O13 (M+H) = 1544; found: 1544.PLC-13:PLC-13.1 CF£F3PLC-13PLC-13 (dimethyl 10-(4-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo- 1 H-xantheno[2,1,9-def]isoquinolin-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-dicarboxylate) PLC- 13.1 (0.3000 mmol, 420 mg), trimethylsilyl 2,2,2-trifluoroacetate (6.000 mmol, 1.0 mL) and BF3.OEt2 (1.2 mmol, 0.15 mL) were stirred in dry DCE (15 mL) under argon at room temperature for a few minutes, then heated to 45 ° C for 4 hours, then cooled to room temperature and quenched with saturated sodium bicarbonate solution (~30 mL), stirring for ~10 minutes, then filtering through a polypropylene frit to retain water, eluting with DCM. The DCM was evaporated to dryness in vacuo, dissolved in a small volume of DCM, loaded onto ~15g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (80g, 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 %. Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 80 mg (17% yield). 1 H NMR (400 MHz, TCE) δ 8.76 (s, 1 H), 8.51 (s, 1 H), 8.27 (d, J = 1.7 Hz, 2H), 8.08 (s, 1 H), 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, 1 H), 7.44 - 7.37 (m, 2H), 7.33 - 7.20 (m, 1 H), 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): calculated for Chemical Formula: C75H52BF18N3O15 (M+H) = 1588; found: 1588.PLC-14:PLC-14.1CFpF3PLC-14PLC-14 (dimethyl 10-(4-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo- 1 H-xantheno[2,1,9-def]isoquinolin-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-dicarboxylate) PLC- 14.1 (0.3000 mmol, 420 mg), trimethylsilyl 2,2,2-trifluoroacetate (6.000 mmol, 1.0 mL) and BF3.OEt2 (1.2 mmol, 0.15 mL) were stirred in dry DCE (15 mL) under argon at room temperature for a few minutes, then heated to 45 °C for 4 hours, then cooled to room temperature and quenched with saturated sodium bicarbonate solution (~30 mL), stirring for ~10 minutes, then filtering through a polypropylene frit to retain water, eluting with DCM. The DCM was evaporated to dryness in vacuo, dissolved in a small volume of DCM, loaded onto ~15g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (80g, 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 %. Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 80 mg (17% yield). 1 H NMR (400 MHz, TCE) δ 8.76 (s, 1 H), 8.51 (s, 1 H), 8.27 (d, J = 1.7 Hz, 2H), 8.08 (s, 1 H), 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, 1 H), 7.44 - 7.37 (m, 2H), 7.33 - 7.20 (m, 1 H), 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): calculated for Chemical Formula: C75H52BF18N3O15 (M+H) = 1588; found: 1588.PLC-15:PLC-15 (dimethyl 10-(5'-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo- 1 H-xantheno[2,1,9-def]isoquinolin-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), trimethylsilyl 2,2,2-trifluoroacetate (31.14 mmol, 5.4 mL) and BF3.OEt2 (3.114 mmol, 0.38 mL) were stirred in dry DCE (40 mL) under argon at room temperature for a few minutes, then heated to 50 °C for three hours, then cooled to room temperature and loaded onto ~15g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (120g, 80% toluene / hexanes (2100% toluenestopping at 0.1 %, 1.0%, 1.5%, and 1.8%, isocratic at each step). Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 965 mg (37% yield). 1 H NMR (400 MHz, TCE) δ 8.76 (s, 1 H), 8.50 (s, 1 H), 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, 1 H), 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): calculated for Chemical Formula: C85H56BF18N3O13 (M+H) = 1680; found: 1680. PLC-16:PLC-16.1 (ethyl 2-cyclobutyl-4-methyl-1 H-pyrrole-3-carboxylate): ethyl 3- cyclobutyl-3-oxopropanoate (50.00 mmol, 7.76 mL), 1 -aminoacetone hydrochloride (75.00 mmol, 8220 mg), and NaOAc (250.0 mmol, 20.508 g) were stirred in HOAc (28.6 mL) and water (100 mL) at 100 ° C overnight. The reaction mixture was cooled to room temperature and evaporated mostly to dryness in vacuo, extracted with DCM (450 mL, 2 X 50 mL), dried over magnesium sulfate, filtered, and evaporated to dryness in vacuo. The crude product was taken up in DCM and evaporated onto ~50g of flash silica gel in vacuo, packed into a loader, and purified by flash chromatography on silica gelFractions containing product were evaporated to dryness in vacuo. Gives a red-brown, waxy solid, 6840 mg (66% yield). 1 H NMR (400 MHz, DMSO) 10.8 δ9 (s, 1 H), 6.43 (dq, J = 2.1 , 1.0 Hz, 1 H), 4.18 - 4.00 (m, 3H), 2.25 - 2.03 (m, 7H), 1.98 - 1.81 (m,1 H), 1.80 - 1.68 (m, 1 H), 1.25 (t, J = 7.1 Hz, 3H). MS (APCI): calculated for Chemical Formula: C12H17NO2 (M+H) = 208; found: 208.PLC-16.3 (diethyl 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- dicarboxylate): 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 in dry DCE (30 mL) at 40 °C under argon for 4 hours, then cooled to room temperature. To the reaction was added DDQ (2.500 mmol, 566 mg), washing down 5 mL DCE. The reaction mixture was stirred at room temperature for 10 minutes, then the reaction mixture was treated with Et3N (8.000 mmol, 1.1 mL), and BF3.OEt2 (12.000 mmol, 1.5 mL) were 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 stirred at 65 °C for 40 minutes, then cooled to room temperature. The reaction mixture was quenched with water (~10 mL), stirred for ~10 minutes, then filtered through a polypropylene frit to retain water, eluting DCM. The DCM was evaporated to dryness in vacuo, dissolved in a small volume of DCM, and loaded onto ~15g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (80g, 0% acetone / hexanes (2 CV)15% (5 CV), stopping at 6.4%, isocratic). Fractions containing product were evaporated to dryness, triturated with methanol, dissolved in DCM, and evaporated to dryness in vacuo. Gives an orange solid, 428 mg (67% yield). 1 H 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): calculated for Chemical Formula: C35H41 BF2N2O6 (M+H) = 635; found: 635.PLC-16 (diethyl 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-dicarboxylate): PLC-16.3 (0.5153 mmol, 327 mg), trimethylsilyl 2,2,2-trifluoroacetate (10.31 mmol, 1.8 mL) and BF3.OEt2 (1.546 mmol, 0.198 mL) were stirred in dry DCE (10 mL) at room temperature under argon for 40 minutes, then quenched with saturated sodium bicarbonate solution (~30 mL) and stirred for about 10 minutes, then filtered through a polypropylene frit to retain water, eluting DCM. The DCM was evaporated to dryness, taken up in a small volume of DCM, and loaded onto ~15g of flash silica gel packed into a loader. Purified by flashchromatography on silica gel (80g, 0% acetone / hexanes (2 CV)15% (10 CV), stopping at 2.5%, and 2.6%, isocratic at each step). Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 350 mg (83% yield). 1 H 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): calculated for Chemical Formula: C39H41BF6N2O10 (M+H) = 823; found: 823.PLC-17:PLC-17.2 (5,-hydroxy-[1,1,:3,,1,,-terphenyl]-2,2",3,3",4,4",5,5",6,6"-d10-2'- carbaldehyde): PLC-17.1 (10.05 mmol, 2813 mg), (phenyl-d5)boronic acid (40.20 mmol, 5105 mg), NaHCO3(60.30 mmol, 5065 mg), and Pd(dppf)Cl2 (2.010 mmol, 1471 mg) were stirred under argon in dry THF (100 mL) and water (15 mL) at 85 ° C for 2 hours, then the reaction mixture cooled to room temperature. The mixture was dilute to ~400 mL with water and acidified with 6N HCI solution to pH ~1 . The resulting precipitate was filtered off, washed with water, dissolved in DCM, filtered through apolypropylene frit to retain water, eluting DCM, and evaporated to dryness in vacuo. The crude material was taken up in DCM and loaded onto ~45g of flash silica gel in a loader. Purified by flash chromatography on silica gel (220g, 0% acetone / hexanes (2 CV) 5% (10 CV), stopping at 1.5%, isocratic). Fractions containing product were evaporated to dryness in vacuo. Gives an off-white solid, 2399 mg (84% yield). 1 H NMR (400 MHz, DMSO) δ 10.69 (s, 1 H), 9.65 (s, 1 H), 6.74 (s, 2H). MS (APCI): calculated for Chemical Formula: C19H4D10O2 (M+H) = 285; found: 285.PLC-17.3 (2'-formy l-[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-1 H-xantheno[2,1 ,9- def]isoquinolin-2(3H)-yl)phenyl)acetate) PLC-17.2 (0.7000 mmol, 199 mg), 2-(4- (5, 1 1 -bis(3,5-bis(trifluoromethyl)phenyl)-1 ,3-dioxo-1 H-xantheno[2, 1 ,9-def]isoquinolin- 2(3H)-yl)phenyl)acetic acid (WuXi, 0.7700 mmol, 651 mg), DMAP.pTsOH salt (0.07000 mmol, 21 mg), and EDC.HCI (1 .400 mmol, 268 mg) were stirred in dry DCE (20 mL) at room temperature for one hour, then loaded onto ~45g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (120g, 0%stop at 0.1 %, 0.5%, and 1.2%, isocratic at each step). Fractions containing product were evaporated to dryness in vacuo. Gives a yellow solid, 741 mg (95% yield). 1 H NMR (400 MHz, TCE) 9.87 δ (s, 1 H), 8.75 (s, 1 H), 8.50 (s, 1 H), 8.27 (d, J = 1.7 Hz, 2H), 8.07 (s, 1 H), 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, 1 H), 7.41 - 7.34 (m, 2H), 7.32 - 7.25 (m, 1 H), 7.23 (s, 2H), 7.05 - 6.95 (m, 2H), 4.04 (s, 2H). MS (APCI): calculated for Chemical Formula: C61 H21 D10F12NO6 (M+H) = 1112; found: 1112.PLC-17.5 (dimethyl 10-(5'-(2-(4-(5,11 -bis(3,5-bis(trifluoromethyl)phenyl)-1 ,3- dioxo-1 H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-[1,T: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- dicarboxylate): PLC-17.3 (0.5000 mmol, 556 mg), PLC-17.4 (1.050 mmol, 190 mg), and pTsOH.H2O (0.01000 mmol, 19 mg) were stirred in dry DCE (20 mL) under argon at 50 °C for 90 minutes, then cooled to room temperature. To the reaction was added DDQ (1 .000 mmol, 227 mg), rinsing down 5 mL DCE. The reaction mixture was stirred at room temperature for 20 minutes, then then the reaction mixture was treated with Et3N (4.000 mmol, 0.56 mL), and BF3.OEt2 (6.000 mmol, 0.74 mL) were added to thereaction. The addition of Et3N (4.000 mmol, 0.56 mL), and BF3.OEt2 (6.000 mmol, 0.74 mL) was repeated and the reaction stirred at 75 ° C for 2 hours. The reaction mixture was cooled to room temperature and quenched with ~30 mL of saturated sodium bicarbonate solution and stirred for 10 minutes. Filtered through a polypropylene frit to retain water, eluting DCM. The DCM was evaporated to dryness in vacuo, dissolved in a small volume of DCM, and loaded onto ~45g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (0% acetone / DCM (2 CV) 3% (10 CV), stop at 0.1 %). Fractions containing product were evaporated to dryness in vacuo. NMR shows it is not pure and several more attempts at purification do not result in pure material. Take to next step as-is.PLC-17 (dimethyl 10-(5'-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo- 1 H-xantheno[2,1,9-def]isoquinolin-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-dicarboxylate): Impure PLC-17.5 (0.2097 mmol, 315 mg, estimated), trimethylsilyl 2,2,2-trifluoroacetate (4.194 mmol, 0.72 mL) and BF3.OEt2 (0.6291 mmol, 0.077 mL) were stirred in dry DCE (10 mL) at room temperature under argon for a few minutes, then heated to 50 ° C for 3 hours, then cooled to room temperature and quenched with ~30 mL of saturated sodium bicarbonate solution, and stirred for ~10 minutes. The mixture was filtered through a polypropylene frit to retain water, eluting with DCM. The DCM was evaporated to dryness in vacuo, taken up in a small volume of DCM, loaded onto ~15g of flash silica gel packed into a loader, and purified by flash chromatography on silica gel (80g, acetone / hexanes (2 CV)20% (10 CV), stop at 9.5%, 10.0%, 10.5%, 11.0%, isocratic at each step). Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 198 mg (56% yield). 1 H NMR (400 MHz, TCE) δ 8.76 (s, 1 H), 8.50 (s, 1 H), 8.27 (d, J = 1.7 Hz, 2H), 8.07 (s, 1 H), 8.05 - 7.99 (m, 3H), 7.69 - 7.61 (m, 2H), 7.49 (ddd, J = 8.5, 6.1 , 2.6 Hz, 1 H), 7.41 (s, 2H), 7.41 - 7.37 (m, 2H), 7.31 - 7.25 (m, 1 H), 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): calculated for Chemical Formula: C85H46D10BF18N3O13 (M+H) = 1690; found: 1690.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 in dry THF (120 mL) and water (20 mL) under argon at 80 ° C for 30 minutes, then cooled to room temperature. The THF was evaporated in vacuo, the mixture diluted with DCM, filtered through a polypropylene frit to retain water, eluting DCM, to the DCM added ~45g of flash silica gel, the DCM evaporated to dryness in vacuo, the silica packed into a loader, and purified by flash chromatography on silica gel (330g, 0% DCM / hexanes (2 CV)25% (10 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a light yellow solid, 11166 mg (95% yield). MS (APCI): calculated for Chemical Formula: C22H12F6(M+H) 391 ; found: 391. 1 H NMR (400 MHz, TCE) δ 8.62 (s, 1 H), 8.13 (d, J = 1.1 Hz, 1 H), 8.12 - 8.09 (m, 2H), 7.96 (d, J = 1.7 Hz, 2H), 7.60 - 7.39 (m, 6H).PLC-18.2 (9-(3,5-bis(trifluoromethyl)phenyl)-1 O-bromoanthracene): PLC-18.1 (28.60 mmol, 11165 mg), NBS (34.32 mmol, 6110 mg), and dry DCE (150 mL) were stirred at room temperature under argon for 90 minutes, then heated to 50 ° C for 30 minutes. The reaction mixture was cooled to room temperature, the DCE evaporated in vacuo (water bath at RT), and the resulting solids washed with water. The residue was taken up into methanol, stirred for ~10 minutes, then filtered off, washing MeOH. Dried by suction. Gives a light yellow solid, 8082 mg (60% yield). MS (APCI): calculated for Chemical Formula: C22Hu BrFe (M+H) 469; found: 469. 1 H NMR (400 MHz, TCE) δ 8.66 (dt, J = 8.9, 1 .0 Hz, 2H), 8.12 (s, 1 H), 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).PLC-18.3 ((4-( 10-(3,5-bis(trifluoromethyl)phenyl)anthracen-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 in dry THF (120 mL) and water (20 mL) under argon at 80 ° C for 30 minutes, then cooled to room temperature. The THF was evaporated in vacuo, DCM added, the mixture filtered through a polypropylene frit to retain water, eluting DCM, ~45g of flash silica gel was added to the DCM, and the DCM evaporated to dryness in vacuo and packed into a loader. Purified by flash chromatography on silica gel (220g, 0% EtOAc / DCM (2 CV) 25% (10 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a light yellow solid, 3014 mg (94% yield). MS (APCI): calculated for Chemical Formula: C29H16F8O (M+H) δ33; found: 533. 1 H NMR (400 MHz, DMSO) δ 8.39 (td, J = 1.8, 0.9 Hz, 1 H), 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, 1 H), 4.70 (d, J = 5.7 Hz, 2H).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 in dry DMF (30 mL) under argon at 100 °C for 30 minutes, then cooled to room temperature. The reaction was diluted with water (~300 mL) to precipitate the product, the productfiltered off, washing with water, the damp precipitate dissolved in DCM, filtered through polypropylene to retain water, eluting DCM, to the DCM was added ~45g of flash silica gel, the DCM evaporated to dryness in vacuo, the silica packed into a loader, and purified by flash chromatography on silica gel (220g, 100% DCM isocratic). Fractions containing product were evaporated to dryness in vacuo. Gives a light yellow solid, 3039 mg (98% yield). MS (APCI): calculated for Chemical Formula: C29H15CIF8 (M+H) 551 ; found: 551. 1 H NMR (400 MHz, DMSO) δ 8.40 (tt, J = 1.8, 0.9 Hz, 1 H), 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).PLC-18.5 (4-(10-(3,5-bis(trifluoromethyl)phenyl)anthracen-9-yl)-2,6- difluorobenzyl 2-isopropyl-4-methyl-1 H-pyrrole-3-carboxylate): PLC-18.4 (2.413 mmol, 13298 mg), 2-isopropyl-4-methyl-1 H-pyrrole-3-carboxylic acid (WuXi AppTech, 3.619 mmol, 605 mg), and potassium carbonate (4.825 mmol, 667 mg) were stirred in dry DMF (25 mL) at 1000C under argon for 30 minutes, then cooled to room temperature. The product was precipitated by adding water (~300 mL), the product filtered off, washed with water, dissolved in DCM, filtered through polypropylene to retain water, eluting DCM, add ~45g of flash silica gel to the DCM, the DCM evaporated in vacuo, the silica gel packed into a loader, and purified by flash chromatography on silica gel (120g, 0% EtOAc / DCM5% (15 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a light yellow solid, 1549 mg (94% yield). MS (APCI): calculated for Chemical Formula: C38H27F8NO2 (M+H) 682; found: 682. 1 H NMR (400 MHz, DMSO) 10.90 δ (s, 1 H), 8.43 - 8.29 (m, 1 H), 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, 1 H), 5.45 (s, 2H), 3.70 (p, J = 7.1 Hz, 1 H), 2.15 (d, J = 1.1 Hz, 3H), 1.19 (d, J = 7.0 Hz, 6H).PLC-18.7 (bis(4-(10-(3,5-bis(trifluoromethyl)phenyl)anthracen-9-yl)-2,6- difluorobenzyl) 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- dicarboxylate): 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 in dry DCE (25 mL) at 65 °C for 90 minutes, the reaction cooled to room temperature and treated with DDQ (1.703 mmol, 387 mg), stirred at room temperature for 10 minutes, at which point the oxidationwas done, treated with triethylamine (9.084 mmol, 1 .3 mL), BF3.OEt2(13.63 mmol, 1 .7 mL), the triethylamine (9.084 mmol, 1.3 mL), BF3.OEt2(13.63 mmol, 1.7 mL) were repeated, and the mixture heated to 65 ° C for 30 minutes. The reaction mixture was cooled to room temperature, quenched with 30 mL of saturated sodium bicarbonate solution, stirred for ~10 minutes, filtered through a polypropylene frit to retain water, eluting DCM, the DCM was evaporated to dryness, the residue taken up in a small volume of DCM, loaded onto ~45g of flash silica gel packed into a loader, and purified by flash chromatography on silica gel (120g, 0% EtOAc / hexanes (2 CV) 20% (10 CV), stopping at 8.0%, isocratic). Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 1093 mg (61 % yield). MS (APCI): calculated for Chemical Formula: C87H61 BF18N2O6 (M+H) 1583; found: 1583. 1 H 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).PLC-18 (bis(4-(10-(3,5-bis(trifluoromethyl)phenyl)anthracen-9-yl)-2,6- difluorobenzyl) 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-dicarboxylate): 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 in dry DCE (10 mL) at 45 °C under argon for two hours. The mixture was cooled to room temperature and quenched with saturated sodium bicarbonate solution (40 mL), stirred for 10 minutes, filtered through a polypropylene frit to retain water, eluting DCM. The DCM was evaporated in vacuo, the residue taken up in a small amount of DCM, loaded onto ~40g of flash silica gel in a loader, and purified by flash chromatography on silica gel (120g, 0% EtOAc / hexanes (2 CV) 10% (10 CV), stop at 8.1 %, 8.5%, isocratic at each step). Fractions containing product were evaporated to dryness, the residue triturated with methanol, filtered off the ppt, dried in vacuo. Gives an orange solid, 275 mg (45% yield). MS (APCI): calculated for Chemical Formula: C91H61BF22N2O10 (M+H) 1771 ; found: 1771. 1 H 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, 3.2 Hz, 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).Compound: N,N'-(ethane-1,2-diyl)bis(2,2,2-trifluoroacetamide): To a solution of ethylenediamine (1.209 g, 20 mmol) in 10 mL diethyl ether, was added a solution of trifluoroacetic anhydride (6.14 mL, 44 mmol) in 10 mL diethyl ether slowly at 0 °C. the mixture was stirred at room temperature for 30 min, white precipitate formed. Filtration, washing with diethyl ether (10 mL x 2), then dried in air, a white solid was obtained (4.97 g, in 98.7% yield). LCMS (APCI-): Calcd for C6H5F6N2O2 (M-H): 251 .03; found: 251 .1H NMR (400 MHz, MeOD) δ 3.46 (s, 4H).PLC-19: To a solution of BODIPY compound PLC-19.1 (90 mg, 0.16 mmol) in 5 mL anhydrous DCE, was added 1 M BCI3 solution in toluene (0.3 mL, 0.3 mmol). The reaction mixture was stirred at room temperature for one hour, then, triethylamine (0.17 mL, 1.26 mmol) was added, followed by addition of the 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, then acetic anhydride (0.2 mL, 2 mmol) was added, and the resulted mixture was stirred at 60 °C for 4 hours. The reaction mixture was worked up with DCM, washed with brine, the organic phase was collected and dried over MgSO4, loaded on silica gel, purified by flash chromatography using eluents of hexanes / DCM(0% DCM to 100% DCM to 10% EA in DCM). The peak with m / e- = 766 was collected. Removal of the solvents gave an orange solid (5 mg, in 4% yield).LCMS (APCI-): Calcd for C35H37BF6N4O8 = 766.26; Found: 766.1H NMR (400 MHz, CDCI3) 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).Example 2: Procedure to measure optical properties of sharp emitter chromophoresA glass substrate was prepared in substantially the following manner. A 1.1 mm thick glass substrate measuring 1 -inch X 1 -inch was cut to size. The glass substrate was then washed with detergent and deionized (DI) water, rinsed with fresh DI water, and sonicated for about 1 hour. The glass was then soaked in isopropanol (IPA) and sonicated for about 1 hour. The glass substrate was then soaked in acetone and sonicated for about 1 hour. The glass was then removed from the acetone bath and dried with nitrogen gas at room temperature.A 25 wt% solution of Poly(methyl methacrylate) (PMMA) resin in spectroscopy grade Toluene was prepared. The prepared PMMA polymer was stirred at 50 °C until the PMMA was fully dissolved. [PMMA] CAS: 9011 -14-7; [Toluene] CAS: 108-88-3.In a 20 mL vial, 2 mg of chromophore was added into the PMMA solution to make a 2.0 x 10-3M solution [PMMA volume was calculated using the formula: VPMMA then mixed well by Vortex for about 5 min and sonicated forabout 60 minutes. The PMMA / Compound solution was then spin coated onto a prepared glass substrate at 1000 RPM for 20s. The spin-coated samples were baked in an oven at 150 °C for 5 minutes to evaporate the remaining solvent.The 1 -inch X 1 -inch sample was inserted into a Shimadzu, UV-3600 UV-VIS- NIR spectrophotometer (Shimadzu Instruments, Inc., Columbia, MD, USA) to measure absorption spectrum.The fluorescence spectrum (emission spectrum) of a 1 -inch X 1 -inch film sample prepared as described above was determined using a Fluorologmax spectrofluorometer (Horiba Scientific, Edison, NJ, USA). Both 390 nm and 450 nm wavelengths were chosen as the excitation wavelength.The quantum yields of spin-coated samples as described above were determined using a Hamamatsu C11347 Absolute PL quantum yield spectrometer (Hamamatsu Inc., Campbell CA, USA). A 0.5”x 0.5” size film was taken out from glass substrate for QY measurement. Wavelengths were scanned every 30 nm from 390 nm to 450 nm (as excitation wavelengths). The QY at 450 nm are reported in Table 1 .The optical properties of the spin-coated films (absorbance peak wavelength, FWHM, and quantum yield) are shown in Table 1 , below.Table 1. Optical Properties of Chromophores in PMMAExample 3: Photostability5 Photostability of the chromophores were tested by exposing the 1 -inch X 1 -inch sample on 40 mW / cm2 Blue LEDs (CREE, Durham, North Carolina, USA). The samples were monitored daily and (the first 2-3 days) then weekly for absorbance, emission, and QY following the same procedures described above. Thechromophore’s photo durability is quantified by the decrease in absorbance (Abs%) and changes in QY%, and emission properties are also monitored. Photostability measurements continued until absorbance decayed to less than 50% absorbance. Photostability data of PLC-4 as compared to PLC-4.5 is provided in Table 2 which exhibits the improved photostability of PLC-4 relative to PLC-4.5.Unless otherwise indicated, all numbers expressing quantities of ingredients, properties, such as, molecular weight, reaction conditions, and so forth used in the specification and embodiments are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and attached embodiments are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, and not as an attempt to limit the application of the doctrine of equivalents. To the scope of the embodiments, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.For the processes and / or methods disclosed, the functions performed in the processes and methods may be implemented in differing order, as may be indicated by context. Furthermore, the outlined steps and operations are only provided as examples and some of the steps and operations may be optional, combined into fewer steps and operations, or expanded into additional steps and operations.This disclosure may sometimes illustrate different components contained within, or connected with, different other components. Such depicted architectures are merely examples, and many other architectures can be implemented which achieve the same or similar functionality.The terms used in this disclosure and in the appended embodiments, (e.g., bodies of the appended embodiments) are generally intended as “open” terms (e.g., the term “including” should be interpreted as “including, but not limited to,” the term “having” should be interpreted as “having at least,” the term “includes” should be interpreted as “includes, but not limited to,” etc.). In addition, if a specific number of elements is introduced, this may be interpreted to mean at least the recited number, as may be indicated by context (e.g., the bare recitation of “two recitations,” without other modifiers, means at least two recitations of two or more recitations). As used in this disclosure, any disjunctive word and / or phrase presenting two or more alternativeterms should be understood to contemplate the possibilities of including one of the terms, either of the terms, or both terms. For example, the phase “A or B”: will be understood to include the possibilities of “A” or “B” or “A and B.”The terms “a,” “an,” “the” and similar referents used in the context of describing the present disclosure (especially in the context of the following embodiments) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The use of any and all examples, or representative language (e.g., “such as”) provided herein is intended merely to better illuminate the present disclosure and does not pose a limitation on the scope of any embodiments. No language in the specification should be construed as indicating any non-embodied element essential to the practice of the present disclosure.Groupings of alternative elements or embodiments disclosed herein are not to be construed as limitations. Each group member may be referred to and embodied individually or in any combination with other members of the group or other elements found herein. It is anticipated that one or more members of a group may be included in, or deleted from, a group for reasons of convenience and / or patentability. When any such inclusion or deletion occurs, the specification is deemed to contain the group as modified thus fulfilling the written description of all Markush groups used in the appended embodiments.Certain embodiments include the best mode known to the inventors for carrying out the present disclosure. Of course, variations on these embodiments, will become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventor expects skilled artisans to employ such variations as appropriate, and the inventors intend for the present disclosure to be practiced otherwise than specifically described herein. Accordingly, the embodiments include all modifications and equivalents of the subject matter recited in the embodiments as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is contemplated unless otherwise indicated herein or otherwise clearly contradicted by context. In closing, it is to be understood that the embodiments disclosed herein are illustrative of the principles of the embodiments. Other modifications that may be employed are within the scope of the embodiments. Thus, by way of example, but not of limitation, alternative embodiments may be utilizedin accordance with the teachings herein. Accordingly, the embodiments are not limited to the embodiments precisely as shown and described.

Claims

CLAIMSWhat is claimed is:1 . A photoluminescent complex, comprising: a boron-dipyrromethene (BODIPY) moiety according to the following formula:wherein each X is independently selected from 0, NH, and N-CH2, wherein each of R1and R6is independently selected from hydrogen, a saturated or unsaturated alkyl group, an aryl group and an alkene group; wherein R3is a C1-C2 alkyl and R4is a C1-C2 alkyl; wherein each of R2and R5is independently selected from hydrogen, a saturated alkyl, an unsaturated alkyl, a cyano (-CN), -C(=O)-(OCH2CH2)n-OCH3(wherein n is 1 , 2, 3, or 4), an alkyl ester, and an aryl ester (-C00CH2Ar); wherein each of R7and R8is independently selected from a C1-C3 alkyl group and an optionally substituted aryl group; wherein the BODIPY moiety has the property 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 wherein the photoluminescent complex exhibits an emission quantum yield greater than 80%.

2. A photoluminescent complex, comprising: a blue light absorbing moiety; a linker complex (L); and a boron-dipyrromethene (BODIPY) moiety according to the following formula:wherein each of R1and R6is independently selected from hydrogen, a saturated or unsaturated alkyl group, an aryl group and an alkene group; wherein R3is a C1-C2 alkyl and R4is a C1-C2 alkyl; wherein each of R2and R5is independently selected from hydrogen, a saturated alkyl, an unsaturated alkyl, a cyano (-CN), an alkyl ester, and an aryl ester (-COOCH2Ar); wherein each of R7and R8is independently selected from a C1-C3 alkyl group and an optionally substituted aryl group; wherein each X is independently selected from 0, NH and N-CH2; wherein the linker complex covalently links the blue light absorbing moiety and the BODIPY moiety; wherein light energy of a first excitation wavelength is absorbable by the blue light absorbing moiety, energy from the blue light absorbing moiety is absorbable by the BODIPY moiety, and light energy of a second wavelength greater than the first wavelength is emittable by the BODIPY moiety; and wherein the photoluminescent complex exhibits an emission quantum yield greater than 80%.

3. The photoluminescent complex of claim 1 or 2, wherein each of R7and R8is4. The photoluminescent complex of claim 2, wherein the blue light absorbing moiety is a xanthenoisoquinoline derivative.

5. The photoluminescent complex of claim 4, wherein the xanthenoisoquinoline derivative is according to the following formula:wherein each R11is independently selected from hydrogen, a C1-C3 alkyl, an optionally substituted aryl, and an optionally substituted heteroaryl.

6. The photoluminescent complex of claim 2, wherein R2and R5are independently selected from hydrogen, a saturated alkyl, an unsaturated alkyl, a cyano (-CN), an alkyl ester, and an aryl ester (-COOCH2Ar), and wherein each of R7and R8is a substituted aryl.

7. The photoluminescent complex of claim 6, wherein each of R1and R6is independently selected from a C1-C3 alkyl and an isobutyl group, and each of R2and R5is independently a C1-C3 ester.

8. The photoluminescent complex of claim 2, wherein L represents one of the9. The photoluminescent complex of claim 2, wherein L represents one of the11 . The photoluminescent complex of claim 1 , wherein the BODIPY moiety has one of the following structures:Chemical Formula: C37H41BF6N2O10Exact Mass: 798.28 Molecular Weight: 798.54(PLC-3),12. The photoluminescent complex of any one of claims 2, 4, 5, 6, 7, 8, 9 or 10, comprising one of the following structures:(PLC-4),Chemical Formula: C85H62BF12N3O13 Exact Mass: 1571.42 Molecular Weight: 1572.23(PLC-5),Chemical Formula: C81H54BF12N3O13 Exact Mass: 1515.36Molecular Weight: 1516.12(PLC-6),13. A color conversion film, comprising: a transparent substrate layer; a color conversion layer including a resin matrix; and a photoluminescent complex according to any one of claims 1-12 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 radical scavenger.

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

17. The color conversion film of claim 13, comprising the property of absorbing light in a wavelength range of about 400 nm to about 480 nm and emitting light in a 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: dissolving a photoluminescent complex according to any one of claims 1-12 and a binder resin in a solvent; and applying the mixture onto a surface of the transparent substrate layer.

19. A backlight unit, comprising a color conversion film according to any one of claims 13-17.

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

Images