Boron-containing cyclic luminescent compound and color conversion film containing same

Abstract

The present invention relates to a novel photoluminescent composite comprising a BODIPY moiety covalently bonded to a blue light absorbing moiety, and a color conversion film and a backlight unit using the same.

Description

[0001] Inventors: Jeffrey R. Hammock, Shijun Zheng, Tingsha Yao, and Sadahiro Nakanishi

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS

[0003] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 385,812, filed on December 2, 2022, and U.S. Provisional Patent Application No. 63 / 504,158, filed on May 24, 2023. Background Art

[0004] In color reproduction, a gamut or color gamut is a complete subset of the colors available on a device such as a television or monitor. For example, Adobe has developed TM Red Green Blue (RGB), a wide gamut color space achieved by using pure spectral primary colors to provide a wider color gamut and provide a more realistic representation of visible colors viewed through a display. It is believed that devices that can provide a wider color gamut can enable displays to depict more vivid colors.

[0005] As high-definition, large-screen displays become increasingly common, the demand for higher-performance, thinner, and more functional displays is increasing. Current light-emitting diodes (LEDs) are produced by emitting blue light that excites green, red, or yellow phosphors to produce a white light source. However, the full width at half maximum (FWHM) of the emission peaks of current green and red phosphors is quite large, typically greater than 40 nm, causing the green and red spectra to overlap and appear indistinguishable from each other. This overlap results in poor color rendering and a degraded color gamut.

[0006] In order to correct the degradation of the color gamut, methods have been developed using a combination of films containing quantum dots and LEDs. However, there are problems with the use of quantum dots. First, cadmium-based quantum dots are extremely toxic and are banned in many countries due to health and safety issues. Second, non-cadmium-based quantum dots are extremely inefficient in converting blue LED light into green and red light. Third, quantum dots require expensive encapsulation processes for protection from moisture and oxygen. Finally, the cost of using quantum dots is high due to difficulties in controlling size uniformity during the manufacturing process. Co-pending patent applications include at least Patent Cooperation Treaty Publication No. WO2022 / 178450 filed on February 22, 2022; PCT US2022 / 017373; and PCT / US2022 / 076912 filed on September 23, 2022.

[0007] Therefore, there is a need to improve the performance of color conversion films, backlight units, and display devices. Summary of the Invention

[0008] The photoluminescent composites described herein can be used to improve the contrast between distinguishable colors in televisions, computer monitors, smart devices, and any other device utilizing a color display. The photoluminescent composites of the present invention provide novel color-converting dye composites with good blue light absorption and a narrow emission bandwidth, for example, an emission band with a full width at half maximum (FWHM) of less than 40 nm. In some embodiments, the photoluminescent composite absorbs light at a first wavelength and emits light at a second wavelength that is higher than the first wavelength. The photoluminescent composites disclosed herein can be used with color-conversion films for use in light-emitting devices. The color-conversion films of the present invention reduce color degradation by reducing overlap within the color spectrum, thereby producing high-quality color rendering.

[0009] Some embodiments include a photoluminescent complex comprising a blue light absorbing moiety; a linker complex; and a boron-dipyrromethene (BODIPY) moiety.

[0010] In some embodiments, the blue light absorbing moiety is a xantheneisoquinoline group of the following general formula:

[0011] where R 0 Contains H, alkyl, -CF3, alkoxy or optionally substituted aryl, and R 10 Contains H, alkyl, -CF3, alkoxy, or optionally substituted aryl. In some embodiments, the dashed line comprises a covalent bond to the linker complex.

[0012] Some embodiments include a BODIPY moiety of the following formula:

[0013]

[0014] Where X contains F or CN, R 1 and R 6 and R 3 and R 4 Contains H, alkyl, cycloalkyl, alkenyl, R 2 and R 5 contains H, alkyl, cycloalkyl, cyano (-CN), alkyl ester or aryl ester; and R 7 and R 8 Contains optionally substituted aryl, C 2-8 Alkyl; C 3-8 Cycloalkyl; having C 1-10 an ether group of an alkyl group, an ether moiety having an optionally substituted aryl group, a C 1-10 Arylalkyl.

[0015] In some embodiments, the linker complex comprises an optionally substituted ester or optionally substituted ether linker, wherein the linker complex covalently links the blue light absorbing moiety and the BODIPY moiety.

[0016] In other embodiments, the blue-absorbing moiety absorbs light energy at a first excitation wavelength and transfers the energy to the BODIPY moiety. In some embodiments, the BODIPY moiety absorbs energy from the blue-absorbing moiety and emits light energy at a second, higher wavelength.

[0017] In some embodiments, the emission quantum yield of the photoluminescent complex is greater than 80%.

[0018] In some embodiments, wherein R of the photoluminescent complex 7 and R 8 Contains optionally substituted aryl groups such as phenyl,

[0019] In other embodiments, the R 7 and R 8 Contains optionally substituted alkyl, optionally substituted cycloalkyl or optionally substituted ether, including pentyl, 2-ethylhexyl, cyclohexyl, CH2-cyclohexyl, -OCH3, -O-(2-ethylhexyl), -OCH2-cyclohexyl, -OPh or -O(CH2)3-Ph.

[0020] Some embodiments include photoluminescent compositions wherein R 1 and R 6 contains H, methyl, ethyl, propyl, isopropyl, butyl or isobutyl; and wherein R 3 and R 4 Contains H, methyl, ethyl, propyl, isopropyl, butyl or isobutyl.

[0021] Other embodiments include photoluminescent composites wherein R 2 and R 5 Contains -C(O)OMe,

[0022]

[0023] In some embodiments, R of the photoluminescent complex 0 Include

[0024] In other embodiments, the R 10 Contains H.

[0025] In some embodiments of the photoluminescent complex, the linker complex comprises

[0026] In some embodiments, X of the photoluminescent complex is F. In other cases, X of the photoluminescent complex is CN.

[0027] Some embodiments of the present invention include color conversion films. In some embodiments, the color conversion film includes a transparent substrate layer and a color conversion layer including a resin matrix. In some embodiments, the photoluminescent compounds described herein are dispersed within the resin matrix.

[0028] In some embodiments, the color conversion film of the present invention may include a singlet oxygen quencher. In some embodiments, the color conversion film may further include a free radical scavenger.

[0029] Some embodiments include a method for preparing a color conversion film, the method comprising: dissolving the above-described photoluminescent composite and a binder resin in a solvent; and applying the mixture on a surface of a transparent substrate.

[0030] Some embodiments include backlight units containing the color conversion films described herein.

[0031] Other embodiments include display devices including the backlight units described herein.

[0032] The present application provides a photoluminescent composite having excellent color gamut and luminescence characteristics, a method for manufacturing a color conversion film using the photoluminescent composite, and a backlight unit including the color conversion film. These and other embodiments are described in more detail below. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 Graph depicting the photostability of one embodiment of a photoluminescent composite (PLC-1) compared to a comparative example (CE-3).

[0034] Figure 2 is a graph depicting the absorption and emission spectra of one embodiment of a photoluminescent composite (PLC-21).

[0035] Figure 3 is a graph depicting the absorption and emission spectra of one embodiment of a photoluminescent composite (PLC-25).

[0036] Implementation Method

[0037] The present invention relates to photoluminescent compounds and composites for color conversion films, backlight units and display devices.

[0038] This disclosure describes photoluminescent composites and their use in color conversion films. The photoluminescent composites can be used to improve and enhance the transmission of one or more desired emission bandwidths within a color conversion film. In some embodiments, the photoluminescent composites can both enhance the transmission of a first desired emission bandwidth and reduce the transmission of a second emission bandwidth. For example, a color conversion film can enhance the contrast or intensity between two or more colors, thereby increasing their distinction. The present disclosure includes a photoluminescent composite that can enhance the contrast or intensity between two colors, thereby increasing their distinction.

[0039] As used herein, when a compound or chemical structure is referred to as "substituted," it may include one or more substituents. A substituted group is derived from an unsubstituted parent structure wherein one or more hydrogen atoms of the parent structure have been independently replaced with one or more substituents. In one or more forms, the substituents may be independently selected from optionally substituted C 1-8 Alkyl, C 3-8 Alkenyl or C 3-8 Heteroalkyl.

[0040] The alkyl moiety may be branched, linear (ie, unbranched), or cyclic. In some embodiments, the alkyl moiety may have from 1 to 8 carbon atoms. The alkyl group of the compounds specified herein may be designated as "C 1-8 Alkyl" or similar designations. By way of example only, "C 1-8 "Alkyl" indicates the presence of 1, 2, 3, 4, 5, 6, 7 or 8 carbon atoms in the alkyl chain, i.e., the alkyl chain is methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl and any isomers thereof. Thus, C 1-8 Alkyl groups include C 1-2 Alkyl, C 1-3 Alkyl, C 1-4 Alkyl, C 1-5 Alkyl, C 1-6 Alkyl, C 1-7 Alkyl and C 1-8 Alkyl. The alkyl group may be substituted or unsubstituted. Typical alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, ethenyl, propenyl, butenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

[0041] As used herein, the term "heteroalkyl" refers to an alkyl group as defined herein in which one or more of the constituent carbon atoms has been replaced by nitrogen, oxygen, or sulfur. Examples include, but are not limited to, -CH2-O-CH3, -CH2-CH2-O-CH3, -CH2-NH-CH3, -CH2-N(CH3)-CH3, -CH2-CH2-NH-CH3, -CH2-CH2-N(CH3)-CH3, -CH2-S-CH2-CH3, -CH2-CH2-S(O)-CH3. In addition, up to two heteroatoms may be adjacent, such as (by way of example) -CH2-NH-O-CH3, etc.

[0042] The term "aromatic" refers to a planar ring having a delocalized π-electron system containing 4n+2 π electrons, where n is an integer. An aromatic ring may be formed by five, six, seven, eight, nine, or more than nine atoms. An aromatic ring may be optionally substituted. The term "aromatic" includes both carbocyclic aryl groups (e.g., phenyl) and heterocyclic aryl groups (or "heteroaryl" or "heteroaromatic") (e.g., pyridine). The term includes monocyclic or fused-ring polycyclic (i.e., rings that share adjacent pairs of carbon atoms) groups.

[0043] The term "hydrocarbon ring" refers to a monocyclic or polycyclic ring or ring system containing only carbon and hydrogen and which may be saturated. Monocyclic hydrocarbon rings include groups having 3 to 12 carbon atoms.

[0044] As used herein, the term "aryl" refers to an aromatic ring in which the atoms forming the ring are each carbon atoms. The aryl ring can be formed by five, six, seven, eight, or more than eight carbon atoms. The aryl group can be substituted or unsubstituted. Examples of aryl groups include, but are not limited to, phenyl, naphthyl, phenanthrenyl, and the like.

[0045] The term "aralkyl" refers to an alkyl group substituted with an aryl group. Non-limiting examples of aralkyl groups include benzyl, phenethyl, and the like.

[0046] The term "heteroaryl" refers to an aryl group that includes one or more ring heteroatoms selected from nitrogen, oxygen, and sulfur, wherein the heteroaryl group has 4 to 10 atoms in its ring system. It is understood that the heteroaryl ring may have additional heteroatoms in the ring. In heteroaryl groups having two or more heteroatoms, those two or more heteroatoms may be the same or different from each other. The heteroaryl group may be optionally substituted. An N-containing heteroaryl moiety refers to an aryl group in which the backbone atom of the ring is a nitrogen atom. Illustrative examples of heteroaryl groups include the following: pyrrole, imidazole, and the like.

[0047] As used herein, the term "halogen" refers to fluorine, chlorine, bromine, and iodine.

[0048] As used herein, the terms "bond," "bonding," "direct bond," "single bond," or "covalent bond" refer to a chemical bond between two atoms, or to a chemical bond between two moieties when the atoms joined by the bond are considered part of a larger structure.

[0049] As used herein, the term "moiety" refers to a specific segment or functional group of a molecule.A chemical moiety is a generally recognized chemical entity embedded in or attached to a molecule.

[0050] As used herein, the term "cyano" or "nitrile" refers to any organic compound containing a -CN functional group.

[0051] The term "ester" refers to a chemical moiety having the formula -COOR, where R comprises an alkyl, cycloalkyl, aryl, heteroaryl (bonded through a ring carbon), or heterocycle (bonded through a ring carbon). Any hydroxy or carboxyl side chain on the compounds described herein may be esterified. Such esters may be prepared using any suitable procedure and particular groups.

[0052] As used herein, the term "ether" refers to a chemical moiety containing an oxygen atom bonded to two alkyl or aryl groups, having the general formula RO-R', where R and R' are alkyl and / or aryl groups. Similarly, the term "alkoxy" refers to a chemical moiety containing an oxygen atom bonded to an alkyl group, which is further bonded to an alkyl or aryl group.

[0053] As used herein, the term "ketone" refers to a chemical moiety containing a carbonyl group (carbon-oxygen double bond) attached to two alkyl or aryl groups, having the general formula RC(=O)R', where R and R' are alkyl and / or aryl groups.

[0054] As used herein, the term "BODIPY" refers to a chemical moiety having the formula:

[0055]

[0056] The BODIPY moiety can be composed of a dipyrromethene group complexed with a disubstituted boron atom (BX2), typically a BF2 or B(CN)2 unit. The IUPAC name for the BODIPY core (i.e., devoid of any substituents and lacking an aromatic group opposite the BX2 group, where X = F) is 4,4-difluoro-4-boron-3a,4a-diaza-s-indacene.

[0057] As used herein, the term "xanthenoisoquinoline" or "xanthenoisoquinoline derivative" refers to a chemical moiety having the following formula:

[0058] For example, 1H-xanthen[2,1,9-def]isoquinoline-1,3(2H)-dione.

[0059] The present invention relates to a photoluminescent complex that absorbs light energy at a first wavelength and emits light energy at a second, higher wavelength. The photoluminescent complex of the present invention comprises an absorbing luminescent moiety and an emitting luminescent moiety coupled by a linker such that their distance is adjusted so that the absorbing luminescent moiety transfers its energy to an acceptor luminescent moiety, wherein the acceptor luminescent moiety then emits light at a second wavelength greater than the absorbed first wavelength.

[0060] In some embodiments, the photoluminescent complex comprises a blue light-absorbing moiety, a linker complex, and a boron-dipyrromethene (BODIPY) moiety. In some embodiments, the blue light-absorbing moiety is a xantheneisoquinoline derivative. In some embodiments, the linker complex covalently links the xantheneisoquinoline derivative to the BODIPY moiety. In some embodiments, the xantheneisoquinoline derivative absorbs light at a first excitation wavelength and transfers energy to the BODIPY moiety, which then emits light energy at a second wavelength, wherein the second wavelength has a higher light energy than the first wavelength.

[0061] It is believed that energy transfer from the excited xanthenisolquinoline derivative to the BODIPY moiety occurs via Resonance energy transfer (FRET) occurs. This observation is based on the absorption / emission spectrum of the photoluminescent complex, in which there are two major absorption bands, one at the blue absorption band (xanthene isoquinoline derivative) and one at the BODIPY absorption band, and only one emission band, which is located at the emission wavelength of the BODIPY part (see Figures 2 to 3 ).

[0062] In some embodiments, the photoluminescent composite can have a high emission quantum yield. In some embodiments, the emission quantum yield can be greater than 50%, 60%, 70%, 80%, or 90%. In some embodiments, the emission quantum yield can be greater than 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%. The emission quantum yield can be measured by dividing the number of photons emitted by the number of photons absorbed, which is equal to the emission efficiency of the light-emitting moiety. In some embodiments, the emission quantum yield of the absorbing light-emitting moiety can be greater than 80%. In some embodiments, the quantum yield can be greater than 0.8 (80%), 0.81 (81%), 0.82 (82%), 0.83 (83%), 0.84 (84%), 0.85 (85%), 0.86 (86%), 0.87 (87%), 0.88 (88%), 0.89 (89%), 0.9 (90%), 0.91 (91%), 0.92 (92%), 0.93 (93%), 0.94 (94%), 0.95 (95%), and can be as high as nearly 1 (100%). Quantum yield measurements in films can be performed by a spectrophotometer, such as a Quantaurus-QY spectrophotometer (Hamamatsu, Inc., Campbell, CA, USA).

[0063] In some embodiments, the photoluminescent composite has an emission band, and the emission band may have a full width at half maximum (FWHM) of less than 40 nm. FWHM refers to the width of an emission band when its emission intensity is half the maximum emission intensity of the band, measured in nanometers. In some embodiments, the photoluminescent composite has an emission band FWHM value of less than or equal to about 35 nm, less than or equal to about 30 nm, less than or equal to about 25 nm, or less than or equal to about 20 nm.

[0064] In some embodiments, the photoluminescent composite can have a Stokes shift equal to or greater than 45 nm. As used herein, the term "Stokes shift" refers to the distance between the excitation peak of the blue light absorbing moiety and the emission peak of the BODIPY moiety.

[0065] The photoluminescent composite of the present invention can have an adjustable emission wavelength. By substituting different substituents on the BODIPY moiety, the emission wavelength can be adjusted to about 500 nm to about 560 nm or any value defined by the range.

[0066] In some embodiments, the blue light absorbing portion can have a peak absorption maximum between wavelengths of about 400 nm and about 470 nm. In some embodiments, the absorption peak can be between about 400 nm and about 405 nm, about 405-410 nm, about 410-415 nm, about 415-420 nm, about 420-425 nm, about 425-430 nm, about 430-435 nm, about 435-440 nm, about 440-445 nm, about 445-450 nm, about 450-455 nm, about 455-460 nm, about 460-465 nm, about 465-470 nm, or any wavelength within a range bounded by any of these values.

[0067] In some embodiments, the photoluminescent composite can have an emission peak between about 500 nm and about 560 nm. In some embodiments, the emission peak can be between about 500 nm and about 515 nm, about 515 nm and about 520 nm, about 520 nm and about 525 nm, about 525 nm and about 530 nm, about 530 nm and about 535 nm, about 535 nm and about 540 nm, about 540 nm and about 545 nm, about 545 nm and about 550 nm, about 550 nm and about 555 nm, about 555 nm and about 560 nm, or any wavelength within a range bounded by any of these ranges.

[0068] In some embodiments, the photoluminescent composite can have an absorption peak between about 500 nm to about 520 nm, about 500 nm to about 505 nm, about 505 nm to about 510 nm, about 510 nm to about 515 nm, about 515 nm to about 520 nm, or any wavelength within a range bounded by any of these ranges.

[0069] Some embodiments include a photoluminescent complex wherein the spatial distance between a blue-light-absorbing xantheneisoquinoline or a derivative thereof and a BODIPY moiety is modulated by a linker complex to transfer energy of the blue-light-absorbing xantheneisoquinoline derivative to the BODIPY moiety.

[0070] The present invention includes a photoluminescent complex (PLC), wherein the photoluminescent complex comprises a blue-light-absorbing xantheneisoquinoline derivative, a linker complex, and a BODIPY moiety. The linker complex covalently links the blue-light-absorbing xantheneisoquinoline derivative and the BODIPY moiety. In some embodiments, the xantheneisoquinoline derivative absorbs light energy at a first excitation wavelength and transfers the energy to the BODIPY moiety, wherein the BODIPY moiety absorbs the energy from the xantheneisoquinoline derivative and emits light energy at a second, higher wavelength, and wherein the photoluminescent complex has an emission quantum yield greater than 80%.

[0071] Some embodiments include a blue light absorbing xantheneisoquinoline derivative, wherein the blue light absorbing xantheneisoquinoline derivative may have the following general formula:

[0072]

[0073] where R 0 and R 10 Can be H, C 1-4 Alkyl (e.g., methyl, n-butyl, tert-butyl, etc.), -CF3, optionally substituted aryl (e.g., etc.) or -(OCH2CH2) n -OCH3, wherein n is 1, 2, 3 or 4, or is alkoxy, and wherein the dotted line represents the point of attachment of the xanthenisolquinoline moiety to the linker complex.

[0074] In some embodiments, R 10 C 1-4 Alkyl, such as methyl, ethyl, n-propyl, isopropyl, butyl, tert-butyl, etc. In some embodiments, R 10 is H. In some embodiments, R 10 In other embodiments, R 10 It can be an aryl moiety (eg, unsubstituted phenyl, substituted phenyl, or optionally substituted aryl).

[0075] In some embodiments, the photoluminescent complex comprises a linker complex, wherein the linker complex covalently links the blue light-absorbing xantheneisoquinoline derivative to the BODIPY moiety. In some embodiments, the linker complex can comprise a single bond between the xantheneisoquinoline derivative and the BODIPY moiety.

[0076] In some embodiments, the linker complex can comprise a substituted ester, an unsubstituted ester, a substituted ether, or an unsubstituted ether. In some embodiments, the linker complex can comprise an optionally substituted ester group.

[0077] In some embodiments, the linker complex comprises a substituted ester group, wherein the linker complex can have the following structure:

[0078] In some embodiments, the linker complex can comprise an unsubstituted ester group, wherein the linker complex can have the following structure: In some embodiments, the linker complex may comprise an ether group, wherein the linker complex may have the following structure:

[0079]

[0080] In some embodiments, the linker complex can be:

[0081]

[0082] In some embodiments, the linker complex can be:

[0083]

[0084] In some embodiments, the linker complex can be:

[0085]

[0086] In some embodiments, the linker complex can be:

[0087]

[0088] In some embodiments, the linker complex can be:

[0089]

[0090] In some embodiments, the linker complex can be:

[0091]

[0092] In some embodiments, the linker complex can be:

[0093]

[0094] In some embodiments, the linker complex can be:

[0095]

[0096] In some embodiments, the linker complex can be:

[0097]

[0098] In some embodiments, the linker complex can be:

[0099]

[0100] In some embodiments, the linker complex can be:

[0101]

[0102] In some embodiments, the linker complex can be:

[0103]

[0104] In some embodiments, the linker complex can be:

[0105]

[0106] In some embodiments, the linker complex can be:

[0107]

[0108] The photoluminescent composite of the present invention may comprise a BODIPY moiety. The BODIPY moiety may have the following general formula:

[0109]

[0110] Wherein X can be F or CN;

[0111] where R 1 and R 6 may independently be H, a saturated or unsaturated alkyl group (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, etc.), or an alkene group;

[0112] where R 3 and R 4 may independently be H, a saturated or unsaturated alkyl group (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, etc.), or an alkene group;

[0113] where R 2 and R 5 may independently be H, alkyl, cycloalkyl, alkenyl, cyano (-CN), alkyl ester (e.g., ethyl ester, 2-ethyl-hexyl ester, 2,2,2-trifluoroethyl ester, glycol ester, etc.), or aryl ester (e.g., phenyl ester (-C(O)OCH2Ph));

[0114] where R 7 and R 8 are independently optionally substituted aryl (eg, phenyl, 3,5-bistrifluoromethylphenyl, 3,5-bis-tert-butylphenyl, 3,5-difluorophenyl, 3,5-dichlorophenyl, biphenyl, etc.), C 1-8 Alkyl (e.g., ethyl, pentyl, 2-ethylhexyl, CH2-cyclohexyl, etc.), C 3-8 Cycloalkyl (e.g., cyclopropyl, cyclohexyl, etc.), having C 1-10 an ether group of an alkyl group (e.g., -OCH3, -O-(2-ethylhexyl), OCH2-cyclohexyl, etc.), an ether moiety having an optionally substituted aryl group (e.g., -OPh), or C 1-10 Arylalkyl (e.g., -O(CH2)3-Ph, etc.); and

[0115] wherein L may represent a linker complex comprising an optionally substituted ester or an optionally substituted ether linker.

[0116] In some embodiments, a BODIPY moiety of the present invention may be a BODIPY moiety wherein R 1 、R 3 、R 4 and R 6 Each is a methyl group; R 2 and R 5 Each is a substituted ester group, wherein the substituted ester group comprises a C1-C7 alkyl chain or a polyglycol chain; R 7 and R 8 Each is optionally substituted aryl, alkyl, or ether; and L comprises a linker complex.

[0117] In some embodiments, R 2 and R 5 Can be independently

[0118] In some embodiments, R 2 Can

[0119]

[0120] In some embodiments, R 2 Can

[0121]

[0122] In some embodiments, R 2 Can

[0123]

[0124] In some embodiments, R 2 Can

[0125]

[0126] In some embodiments, R 2 Can

[0127] In some embodiments, R 2 Can

[0128] In some embodiments, R 2 Can

[0129] In some embodiments, R 5Can

[0130] In some embodiments, R 5 Can

[0131] In some embodiments, R 5 Can

[0132] In some embodiments, R 5 Can

[0133] In some embodiments, R 5 Can

[0134] In some embodiments, R 5 Can

[0135]

[0136] In some embodiments, R 5 Can

[0137]

[0138] In some embodiments, R 7 and R 8 and R and R are independently optionally substituted aryl. In some embodiments, the optionally substituted aryl may be optionally substituted phenyl. In some embodiments, the optionally substituted benzyl may be unsubstituted phenyl, unsubstituted biphenyl and / or C 3-12 Alkyl ester group.

[0139] In some embodiments, R 7 and R 8 can be independently phenyl, 3,5-difluorophenyl 3,5-Dichlorophenyl 3,5-di-tert-butylphenyl Biphenyl (e.g. ), 5-isophthalic acid bis-3,5-di(2-ethylhexyl) ester group or 3,5-bis((perfluorophenyl)methyl)isophthalate

[0140] In some embodiments, R 7 and R 8 Can be independently C 2-8 Alkyl (e.g., ethyl, pentyl, 2-ethylhexyl, CH2-cyclohexyl, etc.), C 3-8Cycloalkyl (e.g., cyclopropyl, cyclohexyl, etc.), having C 1-10 an ether group of an alkyl group (e.g., -OCH3, -O-(2-ethylhexyl), OCH2-cyclohexyl, etc.), an ether moiety having an optionally substituted aryl group (e.g., -OPh), or C 1-10 Arylalkyl (e.g., -O(CH2)3-Ph, etc.).

[0141] The photoluminescent composite of the present invention can be represented by the following, which is provided for illustrative purposes and should in no way be construed as limiting:

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154]

[0155]

[0156]

[0157]

[0158]

[0159]

[0160] Some embodiments include a color conversion film, wherein the color conversion film comprises: a color conversion layer, wherein the color conversion layer comprises a resin matrix and a photoluminescent composite described above dispersed within the resin matrix. In some embodiments, the color conversion film may comprise one or more of the composites described herein.

[0161] Some embodiments include color conversion films that can be from about 1 μm to about 200 μm thick. In some embodiments, the color conversion film has a thickness of from about 1 μm to about 5 μm, from about 5 μm to about 10 μm, from about 10 μm to about 15 μm, from about 15 μm to about 20 μm, from about 20 μm to about 40 μm, from about 40 μm to about 80 μm, from about 80 μm to about 120 μm, from about 120 μm to about 160 μm, from about 160 μm to about 200 μm, or any thickness within a range bounded by any of these values.

[0162] In some implementations, the color conversion film can absorb light within a wavelength range of about 400 nm to about 480 nm and can emit light within a wavelength range of about 500 nm to about 560 nm.

[0163] In some embodiments, the color conversion film may further include a transparent substrate layer. The transparent substrate layer has two opposing surfaces, wherein the color conversion layer may be disposed on the surface of the transparent layer that will be adjacent to the light source and in physical contact with these surfaces. The transparent substrate is not particularly limited, and those skilled in the art will be able to select from those used in the art. Some non-limiting examples of transparent substrates include PE (polyethylene), PP (polypropylene), PEN (polyethylene naphthalate), PC (polycarbonate), PMA (polymethacrylate), PMMA (polymethyl methacrylate), CAB (cellulose acetate butyrate), PVC (polyvinyl chloride), PET (polyethylene terephthalate), PETG (glycol-modified polyethylene terephthalate), PDMS (polydimethylsiloxane), COC (cyclic olefin copolymer), PGA (polyglycolide or polyglycolic acid), PLA (polylactic acid), PCL (polycaprolactone), PEA (polyethylene adipate), PHA (polyhydroxyalkanoate), PHBV (poly(3-hydroxybutyrate-co-3-hydroxyvalerate)), PBE (polybutylene terephthalate), and PTT (polytrimethylene terephthalate). Any of the above (alone or in combination) may comprise a transparent substrate layer.

[0164] In some embodiments, the transparent substrate may have two opposing surfaces. In some embodiments, the color conversion film may be disposed on and in physical contact with one of the opposing surfaces. In some embodiments, the side of the transparent substrate not having the color conversion film disposed thereon may be adjacent to the light source. In some embodiments, the substrate may serve as a support during the preparation of the color conversion film. The type of substrate used is not particularly limited, and the material and / or thickness are not limited, as long as it is transparent and capable of serving as a support. Those skilled in the art can determine the material and thickness of the supporting substrate to use.

[0165] Some embodiments include a method for preparing a color conversion film, wherein the method includes: dissolving a photoluminescent compound described herein and a binder resin in a solvent; and applying the mixture to a surface of a transparent substrate.

[0166] In some embodiments, the color conversion film comprises a singlet oxygen quencher.In some embodiments, the color conversion film comprises a free radical scavenger.

[0167] Binder resins that can be used with one or more photoluminescent composites 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, polysulfones, nylon, cellulose resins, and cellulose acetate resins. In some embodiments, the binder resin may be a polyester resin and / or an acrylic resin.

[0168] In some embodiments, solvents that can be used to dissolve or disperse the composite and resin may include: alkanes such as butane, pentane, hexane, heptane, and octane; cycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane; alcohols such as ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, decanol, undecanol, diacetone alcohol, and furfuryl alcohol; cellosolves TM (Cellosolve TM ), such as methyl cellosolve TM , ethyl cellosolve TM , butyl cellosolve TM , methyl cellosolve TM Acetate and ethyl cellosolve TMAcetates; 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, dichloromethane and tetrachloroethane; aromatic hydrocarbons such as benzene, toluene, xylene and cresol; and highly polar solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone.

[0169] Some embodiments include a backlight unit, wherein the backlight unit may include the above-described color conversion film.

[0170] Other embodiments include display devices, where the device may include a backlight unit as described herein.

[0171] Unless otherwise indicated, all numbers representing the quantity, characteristics (such as molecular weight), reaction conditions, etc. of the expression components used in this specification and the embodiments should be understood to be modified by the term "about" in all cases. Therefore, unless otherwise indicated, the numerical parameters set forth in this specification and the attached embodiments are approximate values, which may vary depending on the desired characteristics sought to be obtained. At least, no attempt should be made to limit the application of the doctrine of equivalents. For the scope of the embodiments, each numerical parameter should at least be understood according to the number of reported significant figures and by applying general rounding techniques.

[0172] For the disclosed procedures and / or methods, the functions performed in the procedures and methods may be implemented in a different order, as may be indicated by the context. In addition, the steps and operations outlined are provided as examples only, and some steps and operations may be optional, combined into fewer steps and operations, or expanded into additional steps and operations.

[0173] The present disclosure may sometimes illustrate different components contained within or connected to other different components. Such depicted architectures are merely examples, and many other architectures can be implemented to achieve the same or similar functionality.

[0174] The terms used in this disclosure and the accompanying embodiments (e.g., the main body of the accompanying embodiments) are generally intended to be "open" terms (e.g., the term "including" should be interpreted as "including but not limited to," the term "having" should be interpreted as "having at least," the term "includes" should be interpreted as "including but not limited to," etc.). In addition, if a specific number of elements is introduced, this can be interpreted to mean at least the recited number, as can be indicated by the context (e.g., the basic recitation of "two statements" without other modifiers refers to at least two recitations of the two or more statements). As used in this disclosure, any disjunctive word and / or phrase presenting two or more alternative terms should be understood to encompass the possibility of including one of these terms, any one of these terms, or both of these terms. For example, the phrase "A or B" should be understood to include the possibility of "A" or "B," or "A and B."

[0175] Use of the terms "may" or "may be" should be considered as shorthand for "is" or "is not" or "does" or "does not" or "will" or "will not", etc. For example, the statement "In some embodiments, the photoluminescent composite may have a Stoke's shift equal to or greater than 45 nm" should be interpreted as, for example, "In some embodiments, the photoluminescent composite will have a Stoke's shift equal to or greater than 45 nm" or "In some embodiments, the photoluminescent composite will not have a Stoke's shift equal to or greater than 45 nm."

[0176] Unless otherwise indicated herein or clearly contradicted by context, the terms "a," "an," "the," and similar designators used in the context of describing the present invention (especially in the context of the following embodiments) are to be construed to encompass both the singular and the plural. The use of any and all examples or representative language (e.g., "such as") provided herein is intended merely to better illustrate the present invention and does not limit the scope of any embodiment. No language in this specification should be construed as indicating any non-embodied element as essential to the practice of the present invention.

[0177] The grouping of alternative elements or embodiments disclosed herein should not be construed as limiting. Each group member may be referred to and embodied individually or in any combination with other members of the group or other elements found herein. It is contemplated that one or more members of a group may be included in or 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 modified group, and therefore satisfies the written description of all Markush groups used in the accompanying embodiments.

[0178] Certain embodiments include the best mode known to the inventor for carrying out the present invention. Of course, variations of these embodiments will become apparent to those skilled in the art after reading the foregoing description. The inventor anticipates that those skilled in the art will adopt such variations when appropriate, and the inventor intends to implement the present invention in a manner different from that specifically described herein. Therefore, the embodiments include all modifications and equivalents of the subject matter described in the embodiments permitted by applicable law. In addition, unless otherwise indicated herein or otherwise clearly contradictory to the context, any combination of the elements described above in all possible variations thereof is encompassed. In short, it should be understood that the embodiments disclosed herein illustrate the principles of the embodiments. Other modifications that can be adopted are within the scope of the embodiments. Therefore, by way of example, but not limitation, alternative embodiments can be utilized according to the teachings herein. Therefore, the embodiments are not strictly limited to the embodiments as shown and described.

[0179] Implementation Plan

[0180] Embodiment 1 A photoluminescent composite comprising:

[0181] The part that absorbs blue light;

[0182] a linker complex; and

[0183] A boron-dipyrromethene (BODIPY) moiety, wherein the BODIPY moiety has the following general formula:

[0184]

[0185] where R 1 and R 6 are independently H, alkyl, cycloalkyl or alkenyl; wherein R 3 and R 4 are independently selected from C1-C2 alkyl; wherein R 2 and R 5 are independently selected from H, alkyl, cycloalkyl, alkenyl, cyano (-CN), alkyl ester (-COOCH2CH3), aryl ester (-COOCH2Ar) or EtO2C; and wherein R 7 and R 8 is optionally substituted aryl;

[0186] wherein the linker complex covalently links the blue-light-absorbing moiety and the BODIPY moiety, wherein the blue-light-absorbing moiety absorbs light energy at a first excitation wavelength and transfers the energy to the BODIPY moiety, wherein the BODIPY moiety absorbs energy from the blue-light-absorbing moiety and emits light energy at a second, higher wavelength, and wherein the photoluminescent complex has an emission quantum yield greater than 80%.

[0187] Embodiment 2: The photoluminescent composite according to embodiment 1, wherein R 7 and R 8 The substituted aryl groups are independently selected from

[0188] Embodiment 3: The photoluminescent composite according to embodiment 1, wherein the blue light absorbing moiety is a xantheneisoquinoline derivative.

[0189] Embodiment 4 The photoluminescent composite according to embodiment 2, wherein the xanthene isoquinoline derivative has the following general formula:

[0190]

[0191] where R 0 independently selected from H, C1-C3 alkyl, optionally substituted aryl or optionally substituted heteroaryl.

[0192] Embodiment 5 The photoluminescent composite according to embodiment 1, wherein the BODIPY moiety has the following general formula:

[0193]

[0194] where R 1 and R 6 are independently selected from H, saturated or unsaturated alkyl, or olefin; wherein R 3 and R 4 are independently selected from C1-C2 alkyl; wherein R 2 and R 5 are independently selected from H, alkyl, cycloalkyl, alkenyl, cyano (-CN), alkyl ester (-COOCH2CH3), aryl ester (-COOCH2Ar) or EtO2C; and wherein R 7 and R 8 is a substituted aryl group.

[0195] Embodiment 6 The photoluminescent composite according to embodiment 6, wherein R 1 、R 3 、R 4 and R 6 are independently selected from C1-C3 alkyl or methyl; wherein R 2 and R 5 Independently selected from C1-C3 ester group or CH3CH2CO2 ester.

[0196] Embodiment 7 The photoluminescent composite of embodiment 10, wherein the unsubstituted ester comprises one of the following structures:

[0197] Embodiment 8 is a photoluminescent composite of embodiment 10, wherein the substituted ester comprises one of the following structures:

[0198] Embodiment 9 The photoluminescent composite of embodiment 10, wherein the unsubstituted and / or substituted ether comprises one of the following structures:

[0199] Embodiment 10: A photoluminescent composite as described in embodiment 1, 2, 3, 4, 5, 6, 7, 8 or 9, wherein the photoluminescent composite comprises one of the following structures:

[0200]

[0201]

[0202]

[0203] Embodiment 11 A color conversion film comprising:

[0204] a transparent substrate layer;

[0205] a color conversion layer, wherein the color conversion layer comprises a resin matrix; and

[0206] The photoluminescent composite comprises the photoluminescent composite of embodiment 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 dispersed in the resin matrix.

[0207] Embodiment 12: The color conversion film according to embodiment 11, further comprising a singlet oxygen quencher.

[0208] Embodiment 13: The color conversion film according to embodiment 11, further comprising a radical scavenger.

[0209] Embodiment 14: The color conversion film according to Embodiment 11, wherein the color conversion film has a thickness of 10 μm to 200 μm.

[0210] Embodiment 15. The color conversion film of embodiment 11, wherein the color conversion film absorbs light in a wavelength range of about 400 nm to about 480 nm and emits light in a wavelength range of 500 nm to about 560 nm.

[0211] Embodiment 16 A method for preparing a color conversion film as described in Embodiment 12, 13, 14 or 15, the method comprising:

[0212] dissolving the photoluminescent composite as described in Embodiment 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 and a binder resin in a solvent; and

[0213] The mixture is applied to one of the opposing surfaces of the transparent substrate.

[0214] Embodiment 17: A backlight unit comprising the color conversion film as described in Embodiment 11, 12, 13, 14 or 15.

[0215] Embodiment 18: A display device including the backlight unit of embodiment 17. Example

[0216] It has been found that embodiments of the photoluminescent composites described herein have improved properties compared to other forms of dyes used in color conversion films. These benefits are further demonstrated by the following examples, which are intended merely to illustrate the invention and are not intended to limit the scope or underlying principles in any way.

[0217] Example 1 - Comparative Example (CE) and Photoluminescent Compound (PLC)

[0218] Comparative Example 1 (CE-1)

[0219]

[0220] CE-1: 0.75 g of 4-hydroxy-2,6-dimethylbenzaldehyde (5 mmol) and 1.04 g of 2,4-dimethylpyrrole (11 mmol) were dissolved in 100 mL of anhydrous dichloromethane. The solution was degassed for 30 minutes. One drop of trifluoroacetic acid was then added. The solution was stirred at room temperature overnight under an argon atmosphere. DDQ (2.0 g) was added to the resulting solution, and the mixture was stirred overnight. The next day, the solution was filtered and then washed with dichloromethane to obtain dipyrromethene (1.9 g). Next, 1.0 g of dipyrromethene 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 trifluoroborane-diethyl ether was slowly added, followed by heating at 70 ° C for 30 minutes. The resulting solution was loaded on silica gel and purified by flash chromatography using dichloromethane as eluent. The desired fractions were collected and dried under reduced pressure to give 0.9 g of an orange solid (76% yield). LCMS (APCI+): C 21 H 24 Calcd. for BF2N2O (M+H) = 369; found: 369. 1H NMR (400 MHz, CHLOROFORM-d) δ 6.64 (s, 2H), 5.97 (s, 2H), 4.73 (s, 1H), 2.56 (s, 6H), 2.09 (s, 6H), 1.43 (s, 6H).

[0221] Comparative Example 2 (CE-2): synthesized as described in Wakamiya, Atsushi et al. Chemistry Letters, 37(10), 1094-1095; 2008.

[0222] Comparative Example 3 (CE-3): Synthesized as follows:

[0223]

[0224] Compound CE-3.1 (6-(2-nitrophenoxy)-1H,3H-benzo[de]isochromene-1,3-dione):

[0225] A mixture of 2-nitrophenol (6.6 g, 48 mmol) and KOH powder (2.4 g, 43 mmol) was mixed and stirred under vacuum for 30 min, followed by the addition of copper powder (0.4 g) and subsequently 100 mL of anhydrous DMF. The mixture was stirred for 5 min, followed by the addition of 4-chloronaphthalene dicarboxylic anhydride (5.1 g, 22 mmol). The whole was degassed and then heated under reflux for 1.5 hours. After cooling to room temperature, 100 mL of 20% hydrochloric acid was added dropwise to the resulting reaction mixture and allowed to stand for 2 hours. The precipitate was collected by filtration and then dried overnight under vacuum to obtain a yellow-brown solid (4.6 g). It was further purified by stirring in refluxing acetic acid (50 mL) for 1 hour, followed by cooling to room temperature. Filtered and dried in air to obtain a yellow solid (3.0 g, 41% yield). Confirmed by LCMS (APCI): C 18 H 10 Calculated for NO6 (M+H): 336.0; found: 336. 1 H NMR (400MHz, chloroform-d) δ8.80(dd,J=8.5,1.2Hz,1H),8.72(dd,J=7.3,1.2Hz,1H),8.50(d,J=8.2Hz,1H),8.19(dd,J=8.2,1.7Hz,1H),7.9 0(dd,J=8.5,7.3Hz,1H),7.79(td,J=7.9,1.7Hz,1H),7.54(td,J=8.0,1.3Hz,1H),7.39(dd,J=8.3,1.2Hz,1H),6.89(d,J=8.2Hz,1H).

[0226] Compound CE-3.2 (6-(2-aminophenoxy)-1H,3H-benzo[de]isochromene-1,3-dione):

[0227] A mixture of compound CE-3.1 (2.0 g, 6 mmol) and iron powder (<10 μM, 0.91 g, 16 mmol) in acetic acid (75 mL) was heated to reflux for 30 min. The resulting solution was poured into water (220 mL). The resulting precipitate was collected by filtration, washed with water, and dried thoroughly in air and then under vacuum to give a yellow solid (1.65 g, 90% yield). LCMS (APCI) confirmed: C 18 H 12 Calculated value for NO4 (M+H): 306.1; found: 306.

[0228] Compound CE-3.3 (1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione):

[0229] Compound CE-3.3 (1.5 g, 4.9 mmol) was dispersed in acetic acid (35 mL) and cooled to 0°C. While stirring, pre-cooled hydrochloric acid (3 mL, 37 mmol) was added, followed by the dropwise addition of a solution of sodium nitrite (3.29 g, 46 mmol) in 12 mL of water at 0°C. The whole was stirred at 0°C for one hour, then transferred to another funnel and added dropwise to a refluxing copper sulfate solution (5.08 g, 20 mmol in 50 mL of 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 dried in vacuo to give a yellow solid (0.92 g, 65% yield). Confirmed by LCMS (APCI): C 18 Calculated value for H8O4 (M-): 288.0; found value: 288.

[0230] Compound CE-3.4 (5,11-dibromo-1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione):

[0231] A 2L 2N round-bottom flask was charged with a stirring bar and equipped with a long-fin condenser. Compound CE-1.1 (34.688 mmol, 10.00 g) was added to the flask, followed by o-dichlorobenzene (1000 mL). The reaction mixture was stirred at room temperature and Br2 (416.26 mmol, 21.3 mL) was added. The second neck was plugged, and the reaction mixture was heated at 75 ° C with an aluminum heating block exposed to air over the weekend. The reaction mixture was cooled to room temperature and the solid was filtered out. The filtrate was diluted with hexane (~20% volume), and the second precipitate was filtered out. These two precipitates were dried in vacuo at 100 ° C. Orange-yellow solid, a total of 10.866 g (69.9% yield). Both have similar LCMS and NMR. MS (APCI): Chemical formula C 18 Calcd. for H6Br2O4 (M+H) = 445; found: 445. 1 H NMR (400MHz, TCE) δ9.47 (dd, J = 8.4, 1.5 Hz, 1H), 8.76 (d, J = 14.2 Hz, 2H), 7.72-7.63 (m, 1H), 7.56 (dd, J = 8.3, 1.4 Hz, 1H), 7.46 (ddd, J = 8.5, 6.7, 1.9 Hz, 1H).

[0232] Compound CE-3.5 (2-(4-(5,11-dibromo-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid):

[0233] A 100 mL 2N round-bottom flask was charged with a stirring bar and equipped with a fin condenser / gas adapter and a flow controller. The system was flushed with argon. Compound CE-3.4 (7.000 mmol, 3.136 g), 2-(4-aminophenyl)acetic acid (14.00 mmol, 2.117 g), DMAP (2.100 mmol, 257 mg) and anhydrous DMF (65 mL) were added to the flask. The reaction mixture was heated in an aluminum block set to 160° C. for 5 hours. The crude reaction mixture was cooled to 0° C. and quenched with 6N HCl (~5 mL) and diluted with water (up to ~350 mL). The precipitate was filtered off and washed with water. The product was dried by suction and used in subsequent reactions without further purification. 100% yield was assumed. MS (APCI): Chemical Formula C 26 H 13 Calculated for Br2NO5 (M+H) = 578; found: 578.

[0234] Compound CE-3.8:

[0235] A mixture of ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (1.0 g, 6.0 mmol), 4-hydroxy-2,6-dimethylbenzaldehyde (0.449 g, 3.0 mmol), and p-toluenesulfonic acid (p-TsOH) (50 mg, 0.29 mmol) in 50 mL of dichloroethane (DCE) was degassed and stirred at room temperature overnight. Liquid chromatography-mass spectrometry (LCMS) analysis indicated the reaction was complete, with the major peak being m / e+ = 467. To the mixture obtained above was added 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (0.817 g, 3.6 mmol), and the mixture was stirred at room temperature for 30 min. LCMS analysis indicated the reaction was complete, with the major peak being m / e+ = 465. To the mixture obtained above, triethylamine (1.7 mL, 12 mmol) and BF3-diethyl ether (2.2 mL, 18 mmol) were added under ice-bath cooling, and the resulting mixture was stirred at 50°C for one hour. An additional 1 mL of triethylamine and 1 mL of BF3-diethyl ether were added, and the whole was heated for another hour. LCMS analysis indicated that all the dipyrrolidine starting material was converted to the BODIPY product with m / e+ = 513. After cooling to room temperature, the reaction mixture was loaded onto silica gel and purified by flash chromatography using hexane / ethyl acetate (0% to 30% ethyl acetate) as eluent. The desired fractions were collected. After removal of the solvent, the desired product (1.0 g, 65% yield) was obtained as an orange solid. 1 H NMR (400MHz, chloroform-d) δ6.68 (s, 2H), 4.29 (q, J = 7.1Hz, 4H), 2.84 (s, 6H), 2.05 (s, 6H), 1.34 (t, J = 7.1Hz, 6H). LCMS(APCI+):C 27 H 32 Calcd. for BF2N2O5 (M+H) = 513.2; found: 513.

[0236] 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):

[0237] A 250 mL 2N round-bottom flask was equipped with a stir bar and fitted with a finned condenser / gas adapter and flow controller. The system was flushed with argon. To a flask was added compound CE-3.5 (3.500 mmol, 2.034 g), (3,5-bis(trifluoromethyl)phenyl)boronic acid (14.00 mmol, 3.61 1), K2CO3 (19.25 mmol, 2.661 g), THF (60 mL), DMF (12 mL) and water (6 mL). The reaction mixture was stirred at room temperature under argon for several minutes before the addition of Pd(dppf)Cl2 (0.0245 mmol, 179 mg). The headspace was flushed with argon for one minute before the flow controller was turned off. The reaction mixture was stirred and heated in an aluminum heating block at 80°C for three hours. The crude reaction mixture was evaporated to dryness in vacuo, dissolved in DCM and evaporated in vacuo onto ~35 g flash silica gel. The product was purified by flash chromatography on silica gel (220 g, equilibrated with 0% EtOAc / DCM, eluting at 0% (10 CV) → 15.3% EtOAc / DCM (15.3 CV) → 40% EtOAc / DCM (10 CV) → isocratic 40% EtOAc / DCM) purification. EtOAc contained 0.1% v / v TFA. A brown solid was obtained, 1.710 g (57.6% yield). MS (APCI): Chemical formula C 42 H 19 F 12 Calculated for NO5 (M+H) = 846; found: 846. 1 H NMR (400MHz, DMSO) δ12.45 (s, 1H), 8.62 (s, 1H), 8.52 (d, J = 1.7Hz, 2H), 8.36 (s ,1H),8.30(s,1H),8.26(d,J=1.6Hz,2H),8.24(s,1H),7.50(ddd,J=8.5,7.2, 1.5Hz,1H),7.46-7.38(m,2H),7.37-7.27(m,2H),7.14(dd,J=8.3,1.2Hz,1H) ,6.98(ddd,J=8.4,7.2,1.3Hz,1H),6.85(dd,J=8.3,1.5Hz,1H),3.69(s,2H).

[0238] Compound CE-3.7 (5,5-difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-1,3,7,9-tetramethyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylic acid diethyl ester):

[0239] A mixture of ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (1.0 g, 6.0 mmol), 4-hydroxy-2,6-dimethylbenzaldehyde (0.449 g, 3.0 mmol) and p-toluenesulfonic acid (50 mg, 0.29 mmol) in 50 mL of 1,2-dichloroethane was degassed and stirred at room temperature overnight. LCMS analysis showed one major peak of m / e+ = 467.

[0240] To the resulting solution was added DDQ (0.817 g, 3.6 mmol), followed by stirring at room temperature for 30 min. LCMS analysis showed that all starting material was converted to the desired product with m / e+=465.

[0241] Under ice bath cooling, 1.7 mL of triethylamine and 2.2 mL of BF3-diethyl ether were added sequentially to the mixture from step 2. The whole was heated at 50°C for one hour. LCMS analysis showed ~30% conversion. An additional 1 mL of triethylamine and 1 mL of BF3-diethyl ether were added to the mixture, and the whole was heated at 50°C for another hour. LCMS analysis showed that all starting materials were converted to the desired BODIPY product with m / e+=513, m / e-=512. The reaction mixture was directly loaded onto silica gel and purified by flash chromatography using an eluent of hexane / ethyl acetate (0%→30% ethyl acetate). The desired main peak was collected and the solvent was removed to give an orange solid (1.0 g, 65% yield). LCMS (APCI): C 27 H 32 Calculated for BF2N2O5 (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).

[0242] Compound CE-3 (10-(4-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dimethylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylic acid diethyl ester):

[0243] 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-414,514-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. Dry DCM (10 mL) was added to the vial and the mixture was stirred to give a solution. DIC (0.263 mmol, 0.41 mL) was added to the vial. The reaction was capped and stirred at room temperature overnight. The crude reaction mixture was diluted with hexanes and loaded onto ~20 g of flash silica gel in a loader. Purify by flash chromatography on silica gel (120 g, equilibration 0% EtOAc / hexane, elution 0% (2 CV) → 50% EtOAc / hexane (30 CV)). The fractions containing the product were evaporated to dryness in vacuo. An orange solid was obtained, 70 mg (78% yield). MS (APCI): Formula C 65 H 46 Calculated for BF8N3O9 (M+H) = 1176; found: 1176. 1 H NMR(400MHz,TCE)δ8.71(s,1H),8.48(s,1H),7.95-7.80(m,6H),7.66(t,J=8 .4Hz,4H),7.47-7.35(m,3H),7.31(dd,J=8.3,1.3Hz,1H),7.10(dd,J=8.4,1. 5Hz,1H),7.05(s,2H),6.96(ddd,J=8.4,7.1,1.4Hz,1H),4.28(q,J=7.1Hz,4H ), 4.02 (s, 2H), 2.84 (s, 6H), 2.15 (s, 6H), 1.73 (s, 6H), 1.34 (t, J = 7.1Hz, 6H).

[0244] Comparative Example 4 (CE-4)

[0245]

[0246] 10-(4-(2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dimethylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylic acid diethyl ester:

[0247] Diethyl 5,5-difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-1,3,7,9-tetramethyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylate (0.3000 mmol, 154 mg), 2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (0.3600 mmol, 255 mg), DMAP.pTsOH salt (0.03000 mmol, 9 mg) and DIC (0.6000 mmol, 0.094 mL) were stirred in anhydrous DCM (10 mL) at room temperature for one hour. The crude reaction was loaded onto ~30 g of flash silica gel packed in a loader. Purification was performed by flash chromatography on silica gel (120 g, 0% EtOAc / DCM (2 CV) → isocratic step to 3.8% EtOAc / DCM, followed by isocratic elution of the product). The fractions containing the product were evaporated to dryness in vacuo. An orange solid was obtained, 304 mg (84% yield). MS (APCI): Formula C 67 H 50 Calculated for BF8N3O9 (M+H) = 1204; found: 1204. 1 H NMR(400MHz,TCE)δ8.71(s,1H),8.48(s,1H),7.91(d,J=8.2Hz,2H),7.89-7.82(m ,4H),7.72-7.63(m,4H),7.48-7.37(m,3H),7.31(dd,J=8.3,1.3Hz,1H),7.10(dd, J=8.3,1.5Hz,1H),7.05(s,2H),6.96(ddd,J=8.4,7.1,1.3Hz,1H),4.29(q,J=7.1H z, 4H), 4.02 (s, 2H), 2.84 (s, 6H), 2.16 (s, 6H), 1.74 (s, 6H), 1.34 (t, J = 7.1Hz, 6H).

[0248] Photoluminescent compound PLC-1:

[0249]

[0250] Compound PLC-1.1 ((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. 3,5-Dibromophenol (100.0 mmol, 25.190 g), imidazole (300.0 mmol, 20.430 g), and anhydrous DCM (200 mL) were added to the flask. The mixture was stirred at room temperature to obtain a solution, which was then cooled to 0°C with an ice-water bath. Chlorotriethylsilane (150.0 mmol, 25.2 mL) was added to the flask via a 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 aqueous layer was 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 hexane and loaded onto a loader containing 60 g of flash silica gel. Purification was performed by flash chromatography on silica gel (220 g, balance and elution 100% hexane). The fractions containing the product were evaporated to dryness in vacuo. A colorless oil was obtained, 27.811 g (76% yield). MS (APCI): Formula C 12 H 18 Calcd. for Br2OSi (M+H) = 365; found: 365. 1 H NMR (400MHz, TCE) δ7.28 (t, J = 1.7Hz, 1H), 6.96 (d, J = 1.6Hz, 2H), 1.10-0.95 (m, 9H), 0.75 (qd, J = 7.7, 0.9Hz, 6H).

[0251] Compound PLC-1.2 (2,6-dibromo-4-hydroxybenzaldehyde): A 250 mL 2N round-bottom flask was charged with a stirring bar and equipped with a gas adapter and a septum. The flask was placed in a Dewar bowl. The flask was flushed with argon. Compound 1.1 (30.00 mmol, 10.985 g) was weighed out and azeotroped from toluene. Compound 1.1 was transferred to a reaction flask under argon, followed by addition of anhydrous THF (130 mL), and the reaction mixture was stirred at room temperature to obtain a homogeneous solution. The reaction mixture was cooled to -78 ° C (dry ice / acetone). Oxygen in the system was purged by vacuum / backfill argon cycles (3 ×). Over a few minutes, a solution of LDA in THF / hexane (1.0 M, 60.00 mmol, 60.0 mL) was added under vigorous stirring. The solution was stirred at -78°C for 70 minutes, followed by the addition of anhydrous DMF (150.0 mmol, 11.6 mL) via syringe and stirring at -78°C for 60 minutes. The reaction mixture was cold poured into 400 mL of saturated NH4Cl solution with stirring. The solution was extracted with EtOAc (100 mL), and the layers were separated. The aqueous layer was acidified to pH ~1 using excess 6N HCl, yielding an off-white precipitate. The organic layer was extracted with 100 mL of saturated NH4Cl, followed by two extractions with 10% K2CO3 (100 mL). These aqueous extracts were also added to acidified water, maintaining pH ~1. The resulting precipitate was filtered and then dried in a vacuum oven at 90°C overnight. An off-white / grey precipitate was obtained, yielding 6.665 g (79% yield). MS (APCI): Calcd. for the chemical formula C7H4Br2O2 (M+H) = 281; Found: 281. 1 H NMR (400 MHz, acetone) δ 10.14 (s, 1H), 7.24 (s, 2H).

[0252] Compound PLC-1.3 (3,3",5,5"-tetra-tert-butyl-5'-hydroxy-[1,1':3',1"-terphenyl]-2'-carbaldehyde): A 500 mL 2N round-bottom flask was equipped with a stirring bar and equipped with a finned condenser / gas adapter and a flow controller. The system was flushed with argon. Compound 1.2 (5.500 mmol, 1.540 g) and (3,5-di-tert-butylphenyl)boronic acid (22.00 mmol, 5.150 g) were added to the flask. ), NaHCO3 (33.00 mmol, 2.772 g), Pd(dppf)Cl2 (1.100 mmol, 805 mg), anhydrous THF (270 mL) and water (9 mL). The heating block was set to 80°C and the reaction mixture was stirred at this temperature overnight. The reaction mixture was evaporated onto 60 g of flash silica gel and placed in a loader. Purification was performed by flash chromatography on silica gel (220 g, equilibrated with 0% EtOAc / hexane, eluted with 0% (2CV) → 30% EtOAc / hexane (20CV)). The fractions containing the product were evaporated to dryness in vacuo. A light yellow solid was obtained, 2.256 g (82% yield). MS (APCI): Formula C 35 H 46 Calcd. for O2 (M+H) = 499; found: 499. 1 H NMR (400MHz, TCE) δ9.80 (s, 1H), 7.42 (t, J = 1.8Hz, 2H), 7.15 (d, J = 1.8Hz, 4H), 6.87 (s, 2H), 1.35 (s, 36H).

[0253] Compound PLC-1.4 (2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xanthen[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate 3,3",5,5"-tetra-tert-butyl-2'-formyl-[1,1':3',1"-terphenyl]-5'-yl ester): A 40 mL screw cap vial was charged with a stir bar, compound 1.3 (4.523 mmol, 2256 mg), (2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xanthen[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate 3,3",5,5"-tetra-tert-butyl-2'-formyl-[1,1':3',1"-terphenyl]-5'-yl ester) [2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (CE-3.6) (5.428mmol, 4.590g), DMAP.pTsOH salt (4.523mmol, 1332mg) and anhydrous DCM (20mL). The reaction mixture was stirred at room temperature to give a yellow slurry. DIC (9.047mmol, 1.41mL) was added under stirring at room temperature. The reaction mixture was stirred at room temperature for 60 minutes, then diluted 1:1 with hexane and loaded onto ~60g flash silica gel loaded in a loader. Purified by silica gel flash chromatography (220g, equilibration 0% EtOAc / hexane, elution 0% 2CV→20% EtOAc / hexane (22CV)). The fractions containing the product were evaporated to dryness in vacuo. A yellow solid was obtained, 5.182g (86% yield). MS (APCI): Chemical formula C 77 H 63 F 12 Calculated for NO6 (M+H) = 1326; found: 1326. 1 H NMR(400MHz,TCE)δ9.89(s,1H),8.75(s,1H),8.50(s,1H),8.29-8.24(m,2H), 8.07(s,1H),8.05-7.97(m,3H),7.67-7.60(m,2H),7.49(ddd,J=8.6,6.1,2.6 Hz,1H),7.43(t,J=1.8Hz,2H),7.38(d,J=8.4Hz,2H),7.31-7.25(m,1H),7.23 (s,2H),7.17(d,J=1.8Hz,4H),7.05-6.96(m,2H),4.07(s,2H),1.36(s,36H).

[0254] PLC-1 (10-(5'-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-3,3",5,5"-tetra-tert-butyl-[1,1':3',1"-terphenyl]-2'-yl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylic acid diethyl ester): Add 250 mL of A 2N round-bottom flask was charged with a stirring bar and equipped with a fin condenser / gas adapter and a flow controller. The system was flushed with argon. Compound 1.4 (1.000 mmol, 1.326 g), ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (2.100 mmol, 351 mg) and anhydrous DCE (100 mL) were added to the flask. The reaction mixture was vigorously stirred at room temperature for 30 seconds, followed by the addition of pTsOH.H2O (0.2000 mmol, 38 mg). The reaction mixture was stirred at room temperature under argon for 19 hours, followed by the addition of DDQ (1.300 mmol, 295 mg) and anhydrous DCE (5 mL). The mixture was stirred at room temperature for 30 minutes, followed by the addition of DDQ (0.5000 mmol, 114 mg) and anhydrous DCE (5 mL). After stirring for another 30 minutes, the oxidation was complete. To the reaction was added Et3N (8.000mmol, 1.1mL) and BF3.OEt2 (12.00mmol, 1.5mL). After 1 minute, the addition of Et3N (8.000mmol, 1.1mL) was repeated, and the addition of BF3.OEt2 (12.00mmol, 1.5mL) was repeated. The reaction mixture was stirred at 50°C for 50 minutes, then the reaction mixture was evaporated in vacuo onto 25g flash silica gel (bath = 60°C), and this silica was placed in a loader. Purification was performed by silica gel flash chromatography (330g, balance 0% acetone / hexanes, elution 0% (2CV) → 20% acetone / hexanes (15CV)). The fractions containing the product were evaporated in vacuo to dryness. The product was purified by direct loading onto a 220g column using 10% DCM / hexane (dry loading), eluting 0% EtOAc / DCM (2CV) → 0.2% EtOAc / DCM (2CV) → isocratic 0.2% EtOAc / DCM for repurification. The fractions containing the product were evaporated to dryness in vacuo. An orange solid was obtained, 870 mg (52% yield). MS (APCI): Formula C 95 H 84 BF 14 Calculated for N3O9 (M+H) = 1689; found: 1689. 1H NMR(400MHz,TCE)δ8.75(s,1H),8.50(s,1H),8.26(s,2H),8.07(s,1H),8.02 (s,3H),7.66(d,J=8.3Hz,2H),7.53-7.44(m,1H),7.43-7.34(m,4H),7.27(d, J=8.1Hz,1H),7.21(t,J=1.8Hz,2H),7.04-6.91(m,6H),4.24(q,J=7.1Hz,4H) ,4.10(s,2H),2.62(s,6H),2.00(s,6H),1.30(t,J=7.1Hz,6H),1.12(s,36H).

[0255] Photoluminescent compound PLC-2:

[0256]

[0257] 5"-Hydroxy-[1,1':4',1":3",1"':4"',1""-pentaphenyl]-2"-carbaldehyde: 2,6-Dibromo-4-hydroxybenzaldehyde (500 mg, 1786 mmol), [1,1'-biphenyl]-4-ylboronic acid (1415 mg, 7.144 mmol), sodium bicarbonate (900 mg, 10.72 mmol), and Pd(dppf)Cl2 were combined in THF (90 mL) and water (6 mL) under argon and heated at 80°C for 6 hours. The crude reaction mixture was evaporated in vacuo onto ~50 g flash silica gel and loaded into a cartridge. Purification was performed by silica gel flash chromatography (120 g, 0% acetone / hexanes (2 CV) → 30% (15 CV)). Fractions containing the product were evaporated to dryness in vacuo. 1308 mg (172% yield) was obtained. The identity of the impurity is unknown. It was used in the next step without further purification. MS (APCI): Chemical formula C 31 H 22 Calcd. for O2 (M+H) = 427; found: 427.

[0258] 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 2″-formyl-[1,1′:4′,1″:3″,1″′:4″′,1″″-pentaphenyl]-5″-yl ester): Phenol from the first step (50% w / w, 86 mg, 0.1000 mmol), 2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate were added to a 1% ethanol solution (10% w / w, 86 mg, 0.1000 mmol) and 1% ethanol (10% w / w, 86 mg, 0.1000 mmol). ,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (101 mg, 0.120 mmol), DMAP.pTsOH salt (59 mg, 0.2000 mmol) and DIC (0.125 mL, 0.8000 mmol) were combined in anhydrous DCM (10 mL) in a capped vial and stirred for 20 minutes. The crude reaction mixture was evaporated in vacuo onto ~10 g flash silica gel and loaded into a cartridge. Purification was performed by silica gel flash chromatography (80 g, 0% acetone / hexanes (2 CV) → 40% acetone / hexanes (15 CV)). The fractions containing the product were evaporated to dryness in vacuo. A yellow solid was obtained containing some starting hydroxy-aldehyde (~36% by NMR) and the desired product (~64% by NMR). MS (APCI): Chemical formula C 73 H 39 F 12 Calcd. for NO6 (M+H) = 1254; found: 1254. Used in the next step without further purification.

[0259] PLC-2 10-(5"-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-[1,1':4',1":3",1"':4"',1""-pentaphenyl]-2"-yl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2' [1,1'-f][1,3,2]diazaborinine-2,8-dicarboxylic acid diethyl ester): Under argon, the aldehyde from the previous step (mixture, -0.1473 mmol, 109 mg), ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (59 mg, 0.3534 mmol), and pTsOH.HO (6 mg, 0.02945 mmol) were combined in anhydrous DCE (20 mL) at 50° C. and stirred for 2 hours. The reaction mixture was cooled to room temperature and treated with DDQ (44 mg, 0.1914 mmol) and stirred at room temperature for 20 minutes. EtN (0.16 mL, 1.178 mmol) and BF.OEt (0.22 mL, 1.767 mmol) were added. Repeat the addition of Et3N (0.16 mL, 1.178 mmol) and BF3.OEt2 (0.22 mL, 1.767 mmol), then stir the reaction mixture at 50 ° C for one hour. The crude reaction mixture was evaporated in vacuo onto ~15 g flash silica gel and loaded into a loader. Purified by silica gel flash chromatography (120 g, 0.1% EtOAc / DCM (4CV) → 0.5% (15CV) → 3% (30CV, step gradient). The fractions containing the product were evaporated to dryness in vacuo. An orange solid was obtained, 21 mg (23% yield). MS (APCI): Chemical formula C 91 H 60 BF 14 Calculated for N3O9 (M+H) = 1616; found: 1616. 1H NMR(400MHz,TCE)δ8.76(s,1H),8.50(s,1H),8.07(s,1H),8.05-8.00(m,3H),7.67(d, J=8.4Hz,2H),7.63-7.56(m,4H),7.53(d,J=8.3Hz,4H),7.51-7.46(m,1H),7.45(s,3H ),7.43-7.39(m,5H),7.38-7.31(m,2H),7.28(dd,J=8.6,2.3Hz,5H),7.07-6.94(m,2H ), 4.25 (q, J = 7.1Hz, 4H), 4.10 (s, 2H), 2.71 (s, 6H), 2.01 (s, 6H), 1.33 (t, J = 7.1Hz, 6H).

[0260] Photoluminescent compound PLC-3:

[0261]

[0262] 5-Bromoisophthalic acid bis(2-ethylhexyl ester): 5-Bromoisophthalic acid (5.00 g, 20.41 mmol), 2-ethylhexan-1-ol (20 mL) and pTsOH.H2O (388 mg, 2.041 mmol) were combined in toluene (150 mL) and DMSO (10 mL) and refluxed in a Dean-Stark trap to remove water for 24 hours. The reaction was cooled to room temperature and evaporated in vacuo onto ~60 g flash silica gel. Purified by silica gel flash chromatography (220 g, 0% acetone / hexane (2CV) → 20% (10CV)). Not fully isolated. Evaporate to dryness in vacuo and repeat the purification sequence. The fractions containing the product were evaporated in vacuo to dryness. 5.679 g (59% yield) were obtained. MS (APCI): Formula C 24 H 37 Calcd. for BrO4 (M+H) = 469; found: 469. ~90% pure by NMR. Used in the next step without further purification.

[0263]

[00146] Bis(2-ethylhexyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)isophthalate: The aryl bromide from the previous step (-90% purity, 5.678 g, 12.09 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bis(1,3,2-dioxaborolan) (3.378 g, 13.30 mmol), KOAc (3.561 g, 36.28 mmol), and Pd(dppf)Cl (266 mg, 0.3628 mmol) were combined in anhydrous dioxane (100 mL) and heated at 80°C under argon for three hours. The reaction mixture was cooled to room temperature and evaporated in vacuo onto -60 g flash silica gel. Purify by flash chromatography on silica gel (220 g, 0% EtOAc / hexane (2 CV) → 20% (25 CV)). The fractions containing the product were evaporated to dryness in vacuo. 5.479 g (88% yield) were obtained. MS (APCI): Formula C 30 H 49 Calcd. for BO6 (M+H) = 517; found: 517. 1 H NMR(400MHz,TCE)δ8.69(t,J=1.8Hz,1H),8.59(d,J=1.7Hz,2H),4.28(d,J=5.8Hz,4H), 1.75(hept,J=6.3Hz,2H),1.55-1.29(m,28H),0.96(t,J=7.5Hz,6H),0.94-0.89(m,6H).

[0264] Tetrakis(2-ethylhexyl)-2'-formyl-5'-hydroxy-[1,1':3',1"-terphenyl]-3,3",5,5"-tetracarboxylate: The aryl borate from the previous step (1845 mg, 3.572 mmol), 2,6-dibromo-4-hydroxybenzaldehyde (250 mg, 0.8931 mmol), sodium bicarbonate (450 mg, 5.359 mmol) and Pd(dppf)Cl2 (131 mg, 0.1 786mmol) were combined in THF (45mL) and water (3mL) and heated at 80°C overnight under argon. The reaction mixture was cooled to room temperature and evaporated in vacuo onto ~50g flash silica gel. Purified by silica gel flash chromatography (220g, 0% acetone / hexane (2CV)→15% (20.5CV)). The fractions containing the product were evaporated to dryness in vacuo. 645mg (80% yield) were obtained. MS (APCI): Chemical formula C 55 H 78 O 10 Calcd. (M+H) = 900; found: 900. 1H NMR(400MHz,TCE)δ9.71(s,1H),8.70(t,J=1.6Hz,2H),8.21(d,J=1.6Hz,4H),6.91(s,2H),6.77(s,1H),4 .43-4.16(m,8H),1.75(q,J=6.4Hz,4H),1.58-1.20(m,32H),0.96(t,J=7.5Hz,12H),0.93-0.87(m,12H).

[0265] Tetrakis(2-ethylhexyl)-5'-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2'-formyl-[1,1':3',1"-terphenyl]-3,3",5,5"-tetracarboxylate: Phenol from the previous step (99 mg, 0.1100 mmol), 2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2'-formyl-[1,1':3',1"-terphenyl]-3,3",5,5"-tetracarboxylate were added to a 1% ethanol solution (140 mg, 0.1430 mmol) and 4% ethanol (150 mg, 0.1430 mmol). mmol, DMAP.pTsOH salt (65 mg, 0.2200 mmol) and DIC (0.069 mL, 0.440 mmol) were combined in anhydrous DCM (10 mL) and stirred for 30 minutes. The crude reaction mixture was diluted with hexane 1: 1 and loaded onto ~20 g flash silica gel loaded in a loader. Purified by silica gel flash chromatography (120 g, 0% acetone / hexane (2CV) → 30% (20CV)). The fraction containing the product was evaporated to dryness in vacuo. A yellow solid was obtained, 118 mg (62% yield). The product was co-eluted with unreacted 1677-079. It was used in the next step without further purification. MS (APCI): Chemical Formula C 97 H 95 F 12 NO 14 Calcd. (M+H) = 1727; found: 1727.

[0266] PLC-3 5'-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2'-(2,8-bis(ethoxycarbonyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1 Tetrakis(2-ethylhexyl)-[1,3,2]diazaborin-10-yl)-[1,1':3',1"-terphenyl]-3,3",5,5"-tetracarboxylate: The aldehyde from the previous step (mixture, 136 mg, 0.1077 mmol), ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (35 mg, 0.2112 mmol) and pTsOH were added. .H2O (3.3 mg, 0.01760 mmol) was combined in anhydrous DCE (25 mL) and reacted at 50 ° C overnight under argon. The reaction was cooled to room temperature and treated with DDQ (26 mg, 0.1144 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with Et3N (0.098 mL, 0.7041 mmol) and BF3.OEt2 (0.13 mL, 1.056 mmol). The addition of Et3N (0.098 mL, 0.7041 mmol) and BF3.OEt2 (0.13 mL, 1.056 mmol) was repeated and the reaction mixture was stirred at 50 ° C for one hour. The reaction mixture was evaporated in vacuo onto ~30 g flash silica gel and loaded into a loader. The product was purified by flash chromatography on silica gel (120 g, 0% The product was purified by evaporation of the product in vacuo to dryness using EtOAc / hexane (2 CV) → 5% (5 CV) → 20% (20 CV) → 30% (5 CV). The product-containing fractions were evaporated to dryness in vacuo to afford an orange solid, 55 mg (38% yield). 1 H NMR(400MHz,TCE)δ8.75(s,1H),8.54(t,J=1.5Hz,2H),8.50(s,1H),8.26(d,J=1.7Hz,2H),8.04( dd,J=16.2,1.6Hz,8H),7.69-7.62(m,2H),7.52(s,2H),7.49(ddd,J=8.6,6.3,3.0Hz,1H),7.42-7 .37(m,2H),7.30-7.25(m,1H),7.03-6.96(m,2H),4.23(q,J=7.0Hz,4H),4.20-4.10(m,8H),4.10 (s,2H),2.68(s,6H),1.96(s,6H),1.65-1.57(m,4H),1.43-1.16(m,38H),0.88(t,J=7.3Hz,24H).

[0267] Photoluminescent compound PLC-4:

[0268]

[0269] 5"-Hydroxy-[1,1':3',1":3",1"':3"',1""-pentaphenyl]-2"-carbaldehyde: 2,6-Dibromo-4-hydroxybenzaldehyde (250 mg, 0.8931 mmol), [1,1'-biphenyl]-3-ylboronic acid (707 mg, 3.572 mmol), sodium bicarbonate (450 mg, 5.359 mmol), and Pd(dppf)Cl (131 mg, 0.1786 mmol) were combined in THF (45 mL) and water (3 mL) under argon at 80°C and stirred for five hours. The reaction mixture was cooled to room temperature and evaporated in vacuo onto ~25 g flash silica gel and loaded into a cartridge. Purification was by silica gel flash chromatography (120 g, 0% acetone / hexanes (2 CV) → 30% (15 CV)). Obtained 315 mg (83% yield). MS (APCI): Chemical formula C 31 H 22 Calcd. for O2 (M+H) = 427; found: 427. 1 H NMR (400 MHz, acetone) δ 9.89 (s, 1H), 9.48 (s, 1H), 7.75-7.67 (m, 8H), 7.54 (td, J=7.5, 1.0 Hz, 2H), 7.51-7.44 (m, 4H), 7.43-7.34 (m, 4H), 6.97 (s, 2H).

[0270] 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 2″-formyl-[1,1′:3′,1″:3″,1″′:3″′,1″″-pentaphenyl]-5″-yl ester: The phenol from the previous step (64 mg, 0.1500 mmol), 2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate were added to a 1% ethanol solution (10% ethanol) and 1% ethanol. 1-Bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xanthen[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (178 mg, 0.2100 mmol), DMAP.pTsOH salt (88 mg, 0.3000 mmol) and DIC (0.094 mmol, 0.6000 mmol) were stirred in anhydrous DCM (10 mL) for 30 minutes. The crude product was diluted 1:1 with hexane and loaded onto ~20 g flash silica gel packed in a loader. Purification was performed by silica gel flash chromatography (120 g, 0% acetone / hexane (2CV) → 40% (15CV)). The fractions containing the product were evaporated to dryness in vacuo. 204 mg of a yellow solid was obtained (109% yield). Moisten with solvent. Used in the next step. MS (APCI): Chemical formula C 73 H 39 F 12 Calculated for NO6 (M+H) = 1254; found: 1254. 1 H NMR (400MHz, TCE) δ9.98(s,1H),8.74(s,1H),8.49(s,1H),8.26(s,2H),8.17-7.91(m,4H),7.82-7.19(m,26H),6.99(s,2H),4.05(s,2H).

[0271] PLC-4 10-(5"-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-[1,1':3',1":3",1"':3"',1""-pentaphenyl]-2"-yl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c Diethyl 2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate: Under argon, the aldehyde from the previous step (203 mg, 0.1619 mmol), ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (62 mg, 0.3723 mmol), and pTsOH.HO (6 mg, 0.03237 mmol) were combined in anhydrous DCE (25 mL) and stirred at room temperature for one hour. The reaction mixture was treated with DDQ (55 mg, 0.2428 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with EtN (0.18 mL, 1.295 mmol) and BF.OEt (0.24 mL, 1.942 mmol). Repeat Et3N (0.18mL, 1.295mmol) and BF3.OEt2 (0.24mL, 1.942mmol), and stir the reaction mixture at 50°C for one hour. The crude reaction mixture was diluted with hexane 1:1 and loaded onto ~25g flash silica gel loaded in a loader. Purified by silica gel flash chromatography (120g, 0% EtOAc / DCM (2CV)→0.5% (10CV)→3% (25CV)). The fractions containing the product were evaporated to dryness in vacuo. An orange solid was obtained, 51mg (20% yield). MS (APCI): Chemical formula C 91 H 60 BF 14 Calculated for N3O9 (M+H) = 1616; found: 1616. 1 HNMR(400MHz,TCE)δ8.75(s,1H),8.50(s,1H),8.30-8.21(m,2H),8.07(s,1H),8.05-7.98(m,3H),7.72-7.61(m,2H),7.55-7.45(m ,5H),7.44-7.20(m,20H),7.07-6.94(m,2H),4.24(q,J=7.1Hz,4H),4.08(s,2H),2.76(s,6H),2.01(s,6H),1.32(t,J=7.1Hz,6H).

[0272] Photoluminescent compound PLC-5:

[0273]

[0274] 5'-Hydroxy-3,3",5,5"-tetrakis(trifluoromethyl)-[1,1':3',1"-terphenyl]-2'-carbaldehyde: Under argon, 2,6-dibromo-4-hydroxybenzaldehyde (560 mg, 2.000 mmol), (3,5-bis(trifluoromethyl)phenyl)boronic acid (1032 mg, 4.000 mmol), sodium bicarbonate (1008 mg, 12.00 mmol) and Pd(dppf)Cl (293 mg, 0.4000 mmol) were combined in anhydrous THF (90 mL) and water (6 mL) at 80° C. and stirred for two hours. The reaction mixture was cooled to room temperature and eluted with 6N The HCl solution was titrated to pH ~ 1. The reaction mixture was partitioned between diethyl ether (150 mL), the layers were separated, extracted with DCM (150 mL), the combined organic layers were dried over magnesium sulfate, filtered and evaporated to dryness in vacuo. The crude product was evaporated in vacuo onto ~ 40 g flash silica gel and loaded into a loader. Purified by flash chromatography on silica gel (120 g, 0% EtOAc / hexane (2CV) → 20% (30CV)). The fractions containing the product were evaporated to dryness in vacuo. A white solid was obtained, 889 mg (75% yield). MS (APCI): Chemical formula C 23 H 10 F 12 Calcd. for O2 (M+H) = 547; found: 547. 1 H NMR (400 MHz, acetone) δ 9.82 (s, 1H), 9.74 (s, 1H), 8.12-8.10 (m, 2H), 8.09 (s, 4H), 7.06 (s, 2H).

[0275] 2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate 2'-formyl-3,3",5,5"-tetrakis(trifluoromethyl)-[1,1':3',1"-terphenyl]-5'-yl ester: The phenol from the previous step (889 mg, 1.028 mmol), 2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate were added to a 1% ethanol solution of 4% ethanol and 1% ethanol. -dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (1651 mg, 1.953 mmol), DMAP.pTsOH salt (48 mg, 0.1628 mmol) and DIC (0.51 mL, 3.255 mmol) were stirred in anhydrous DCM (15 mL) for 30 minutes. The crude reaction mixture was diluted 1:1 with hexane and loaded onto a cartridge filled with ~50 g flash silica gel. Purification was performed by silica gel flash chromatography (220 g, 0% EtOAc / toluene (2CV) → 10% (15CV)). The fractions containing the product were evaporated to dryness in vacuo. A yellow solid was obtained, 1351 mg (60% yield). MS (APCI): Formula C 65 H 27 F 24 Calculated for NO6 (M+H) = 1374; found: 1374. 1 H NMR (400MHz, acetone) δ9.92(s,1H),8.73(s,1H),8.55(d,J=1.6Hz,2H),8.49(s,1H),8.30(d,J=1.7Hz,2H),8. 23(dq,J=1.8,0.9Hz,1H),8.21-8.18(m,1H),8.17-8.13(m,4H),8.13(dt,J=2.5,1.1Hz,2H),4.15(s,2H).

[0276] 10-(5'-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-3,3",5,5"-tetrakis(trifluoromethyl)-[1,1':3',1"-terphenyl]-2'-yl)-5,5-difluoro-1,3,7 ,9-Tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylic acid diethyl ester: Under argon at room temperature, the aldehyde from the previous step (1351 mg, 0.9833 mmol), 2,4-dimethyl-1H-pyrrole-3-carboxylic acid ethyl ester (378 mg, 2.262 3-[ ... The product was purified by isocratic EtOAc / DCM extraction. The fractions containing the product were evaporated to dryness in vacuo to give an orange solid, 763 mg (45% yield). MS (APCI): Chemical formula C 83 H 48 BF 26 Calculated for N3O9 (M+H) = 1736; found: 1736. 1 H NMR(400MHz,TCE)δ8.75(s,1H),8.50(s,1H),8.26(d,J=1.6Hz,2H),8.08(s,1H),8.06- 7.91(m,3H),7.79(s,2H),7.71-7.64(m,2H),7.64-7.60(m,4H),7.57(s,2H),7.49(ddd, J=8.5,6.1,2.5Hz,1H),7.45-7.36(m,2H),7.28(dd,J=8.0,1.1Hz,1H),7.07-6.94(m,2 H), 4.28 (q, J = 7.1Hz, 4H), 4.11 (s, 2H), 2.69 (s, 6H), 1.93 (s, 6H), 1.33 (t, J = 7.1Hz, 6H).

[0277] Photoluminescent compound PLC-6:

[0278]

[0279] Bis((perfluorophenyl)methyl)-5-bromoisophthalate: Under argon, 5-bromoisophthalic acid (1960 mg, 8.000 mmol), (perfluorophenyl)methanol (6.339 g, 32.00 mmol), DMAP.pTsOH salt (1177 mg, 4.000 mmol) and DIC (3.76 mL, 24.00 mmol) were combined in anhydrous THF (50 mL) and stirred overnight at room temperature. The crude reaction mixture was evaporated in vacuo onto ~60 g flash silica gel and loaded into a loader. Purification was performed by silica gel flash chromatography (220 g, 50% DCM / hexane (2CV) → 100% DCM (10CV)). The fractions containing the product were evaporated to dryness in vacuo. 2.748 g (57% yield) was obtained. MS (APCI): Formula C 22 H7BrF 10 Calcd. for O4 (M+H) = 605; found: 605. 1 HNMR (400MHz, CD2Cl2) δ8.54 (t, J = 1.5 Hz, 1H), 8.33 (d, J = 1.6 Hz, 2H), 5.47 (t, J = 1.6 Hz, 5H).

[0280]

[00146] Bis(perfluorophenyl)methyl 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)isophthalate: The aryl bromide from the previous step (2.7634 g, 4.417 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bis(1,3,2-dioxaborolan) (1458 mg, 5.742 mmol), KOAc (1300 mg, 13.25 mmol), and Pd(dppf)Cl (102 mg, 0.2208 mmol) were combined in anhydrous dioxane (100 mL) under argon and heated at 80°C for two hours. The crude reaction mixture was evaporated in vacuo onto ~60 g flash silica gel and charged to a cartridge. Purify by flash chromatography on silica gel (120 g, 50% DCM / hexane (2 CV) → 100% DCM (10 CV) → isocratic DCM). The fractions containing the product were evaporated to dryness in vacuo. 2.680 g (93% yield) were obtained. MS (APCI): Formula C 28 H 19 BF 10 Calcd. for O6 (M+H) = 653; found: 653. 1H NMR (400MHz, CD2Cl2) δ8.67 (t, J = 1.8 Hz, 1H), 8.54 (d, J = 1.8 Hz, 2H), 5.47 (t, J = 1.6 Hz, 6H), 1.23 (s, 12H).

[0281]

[0146] Tetrakis(perfluorophenyl)methyl 2'-formyl-5'-hydroxy-[1,1':3',1"-terphenyl]-3,3",5,5"-tetracarboxylate: The arylboronic acid from the previous step (2678 mg, 4.106 mmol), 2,6-dibromo-4-hydroxybenzaldehyde (460 mg, 1.642 mmol), sodium bicarbonate (828 mg, 9.854 mmol), and Pd(dppf)Cl (240 mg, 0.3285 mmol) were combined in THF (100 mL) and water (16 mL) and heated at 80°C under argon for four hours. The crude reaction mixture was evaporated onto ~60 g flash silica gel and loaded into a cartridge. The product was purified by silica gel flash chromatography (120 g, 75% DCM / hexanes (2 CV) → 100% DCM (10CV) → isocratic DCM)) was purified. The fractions containing the product were evaporated to dryness in vacuo. 1.477 g (77% yield) was obtained. MS (APCI): Chemical formula C 51 H 18 F 20 O 10 Calcd. (M+H) = 1171; found: 1171. 1 H NMR (400MHz, CD2Cl2) δ9.63 (s, 1H), 8.67-8.57 (m, 5H), 6.84 (s, 2H), 5.48 (d, J = 1.5Hz, 8H).

[0282] Tetrakis(perfluorophenyl)methyl 5'-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2'-formyl-[1,1':3',1"-terphenyl]-3,3",5,5"-tetracarboxylate): Phenol from the previous step (1470 mg, 1.256 mmol), 5'-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2'-formyl-[1,1':3',1"-terphenyl]-3,3",5,5"-tetracarboxylate were added to the 1% ethanol (1470 mg, 1.256 mmol) and 1% ethanol (10% ethanol). )phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (1275 mg, 1.508 mmol), DMAP.pTsOH salt (37 mg, 0.1256 mmol) and DIC (0.393 mL, 2.511 mmol) were stirred in anhydrous DCM (20 mL) for 60 minutes. The crude reaction mixture was loaded onto ~50 g flash silica gel packed in a loader. Purification was performed by silica gel flash chromatography (120 g, 0% EtOAc / DCM (2CV) → 1% (5CV) → 3% (15CV)). The fractions containing the product were evaporated to dryness in vacuo. A yellow solid was obtained, 1.317 g (53% yield). MS (APCI): Chemical formula C 93 H 35 F 32 NO 14 Calcd. (M+H) = 1998; Found: 1998. NMR was confused but correct compound. Used as is in the next step.

[0283] Tetrakis(perfluorophenyl)methyl 5'-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2'-(bis(4-(ethoxycarbonyl)-3,5-dimethyl-1H-pyrrol-2-yl)methyl)-[1,1':3',1"-terphenyl]-3,3",5,5"-tetracarboxylate): under argon, at room temperature The aldehyde from the previous step (1.315 g, 0.6581 mmol), ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (275 mg, 1.646 mmol), and pTsOH.HO (13 mg, 0.06581 mmol) were stirred in anhydrous DCE (50 mL) at room temperature for two hours. The crude reaction mixture was evaporated in vacuo onto ~40 g flash silica gel and loaded into a cartridge. Purification was performed by silica gel flash chromatography (120 g, 0% EtOAc / DCM (2 CV) → 4% (15 CV)). The fractions containing the product were evaporated to dryness in vacuo. A yellow solid was obtained, 577 mg (38% yield). This was used as is in the next step.

[0284] PLC-6 Tetrakis(perfluorophenyl)methyl 5'-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2'-(2,8-bis(ethoxycarbonyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-10-yl)-[1,1':3',1"-terphenyl]-3,3",5,5"-tetracarboxylate: The dipyrrole (575 mg, 0.2493 mm Hg) from the previous step was added. ol) was dissolved in anhydrous DCE (50 mL) and treated with DDQ (79 mg, 0.3490 mmol) and stirred at room temperature for one hour. The reaction was then treated with Et3N (0.28 mL, 1.994 mmol) and BF3.OEt2 (0.37 mL, 2.991 mmol). The addition of Et3N (0.28 mL, 1.994 mmol) and BF3.OEt2 (0.37 mL, 2.991 mmol) was repeated, and the reaction mixture was stirred at 50°C for one hour. The crude reaction mixture was evaporated in vacuo onto ~40 g flash silica gel and loaded into a loader. Purification was performed by silica gel flash chromatography (120 g, 0% EtOAc / DCM (2 CV) → 25% (25 CV)). The fractions containing the product were evaporated to dryness in vacuo. An orange solid was obtained, 126 mg (53% yield). 1 H NMR (400MHz, CD2Cl2) δ8.78(s,1H),8.53(s,1H),8.46(t,J=1.6Hz,2H),8.31(d,J=1.7Hz,2H),8.08(t,J= 1.8Hz,5H),8.06-8.03(m,3H),7.66-7.59(m,2H),7.52(s,2H),7.47(ddd,J=8.6,7.0,1.7Hz,1H),7.40-7 .33(m,2H),7.27(dd,J=8.3,1.3Hz,1H),7.03(dd,J=8.3,1.7Hz,1H),6.97(ddd,J=8.3,7.0,1.3Hz,1H),5 .36(d,J=1.4Hz,8H),4.24(q,J=7.1Hz,4H),4.09(s,2H),2.62(s,6H),1.91(s,6H),1.30(t,J=7.1Hz,6H).

[0285] Photoluminescent compound PLC-7:

[0286]

[0287] tert-Butyl (2-oxobutyl)carbamate: tert-Butyl (2-(methoxy(methyl)amino)-2-oxoethyl)carbamate (10.915 g, 50.00 mmol) was dissolved in anhydrous THF (200 mL) under argon and cooled to 0°C. With stirring, the reaction mixture was treated with ethylmagnesium bromide (3M in diethyl ether, 50.0 mL, 150.0 mmol) over a period of about five minutes. The cooling bath was removed and the reaction mixture was stirred at room temperature for an additional six hours. It was quenched with ethyl acetate (~15 mL) and then partitioned with saturated ammonium chloride (~100 mL) and ethyl acetate (200 mL). The combined organic layers were washed with water (100 mL), brine (25 mL), dried over magnesium sulfate, filtered and evaporated to dryness in vacuo. The crude product was dissolved in hexane and loaded onto ~50 g of flash silica gel packed in a loader. Purify by flash chromatography on silica gel (220 g, 0% EtOAc / hexane (2 CV) → 30% (15 CV)). The fractions containing the product were evaporated to dryness in vacuo. A pale yellow liquid was obtained, 7.879 g (84% yield). MS (APCI): Chemical formula: C9H 17 Calculated for NO3 (M+H) = 188; found: 188. 1 H NMR (400MHz, TCE) δ5.18 (s, 1H), 4.00 (d, J = 5.0Hz, 2H), 2.44 (q, J = 7.4Hz, 2H), 1.44 (s, 9H), 1.10 (t, J = 7.4Hz, 3H).

[0288] 2-Oxobutan-1-aminium chloride: The carbamate from the previous step (7.873 g, 42.05 mmol) was dissolved in 200 proof ethanol (50 mL) and treated with 12 N HCl solution (50 mL) at room temperature with stirring. The reaction mixture was allowed to outgas for one or two minutes, then stirred at room temperature for 30 minutes. The reaction mixture was evaporated to dryness and used immediately in the next step. MS (APCI): Calcd. for CHNO (M+H) = 88; Found: 88 (free base).

[0289] 4-Ethyl-2-methyl-1H-pyrrole-3-carboxylic acid ethyl ester: Ethyl acetoacetate (10.7 mL, 84.10 mmol), sodium acetate (420.5 mmol, 34.494 g) and the salt from the previous step (assuming 100% yield, 42.05 mmol) were dissolved in water (300 mL) and heated at 80° C. with stirring for four hours. The heat was turned off and the reaction mixture was stirred at room temperature over the weekend. The reaction was filtered, washed with water, and the crude product was dissolved in DCM, separated from the water, dried over magnesium sulfate, filtered and evaporated to dryness in vacuo. A brown solid was obtained, 6.859 g (90% yield). MS (APCI): Formula C 10 H 15 Calculated for NO2 (M+H) = 182; found: 182. 1 H NMR (400 MHz, TCE) δ 8.16 (s, 1H), 6.39 (dt, J = 2.3, 1.1 Hz, 1H), 4.26 (q, J = 7.1 Hz, 2H), 2.71 (qd, J = 7.4, 1.1 Hz, 2H), 2.49 (s, 3H), 1.35 (t, J = 7.1 Hz, 3H), 1.19 (t, J = 7.4 Hz, 3H). The compound was pure and no column chromatography was required.

[0290] 2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate 3,3",5,5"-tetra-tert-butyl-2'-formyl-[1,1':3',1"-terphenyl]-5'-yl ester: 3,3",5,5"-tetra-tert-butyl-4'-formyl-1-phenol (872 mg, 1.750 mmol), 2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate were added to the 1% ethanol. 4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (1490 mg, 2.100 mmol), DMAP.pTsOH salt (52 mg, 0.1750 mmol) and DIC (0.548 mL, 3.500 mmol) were stirred in anhydrous DCM (50 mL) for 30 minutes. The crude reaction mixture was evaporated in vacuo onto ~30 g flash silica gel and loaded into a carrier. Purification was performed by silica gel flash chromatography (120 g, 0% EtOAc / hexane (2 CV) → 20% (30 CV)). The fractions containing the product were evaporated to dryness in vacuo. A yellow solid was obtained, 2058 mg (99% yield). MS (APCI): Formula C 75 H 65 Calculated for F6NO6 (M+H) = 1190; found: 1190. 1H NMR(400MHz,TCE)δ9.89(s,1H),8.70(s,1H),8.47(s,1H),7.96-7.80(m,7H),7.73-7.59(m,5H),7.47-7.35(m,6H),7.31(dd,J=8.3,1. 4Hz, 1H), 7.24 (s, 2H), 7.17 (d, J = 1.7Hz, 4H), 7.10 (dd, J = 8.3, 1.5Hz, 1H), 6.96 (ddd, J = 8.5, 6.4, 1.3Hz, 1H), 4.08 (s, 2H), 1.36 (s, 36H).

[0291] PLC-7 1,9-diethyl-5,5-difluoro-3,7-dimethyl-10-(3,3",5,5"-tetra-tert-butyl-5'-(2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-[1,1':3',1"-terphenyl]-2'-yl)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1 '-f][1,3,2]diazaborin-2,8-dicarboxylic acid diethyl ester: Under argon, the aldehyde from the previous step (283 mg, 0.2000 mmol), compound 1711-44 (91 mg, 0.5000 mmol) and pTsOH.H2O (4 mg, 0.02000 mmol) were stirred in anhydrous DCE (20 mL) at 60°C for three hours. The reaction was concentrated with DDQ (82 mg, 0.3600 mmol). ) and continued heating at 60 ° C for 30 minutes. The reaction was treated with additional DDQ (82 mg, 0.3600 mmol) and continued heating at 60 ° C for another 30 minutes. The reaction mixture was cooled to room temperature and treated with Et3N (0.22 mL, 1.600 mmol) and BF3.OEt2 (0.30 mL, 2.400 mmol). Repeat Et3N (0.22 mL, 1.600 mmol) and BF3.OEt2 (0.30 mL, 2.400 mmol). L, 2.400 mmol) was added and the reaction mixture was stirred at 50 ° C for one hour. The crude reaction mixture was evaporated in vacuo onto ~40 g flash silica gel and loaded into a loader. Purified by silica gel flash chromatography (120 g, 100% toluene / hexane + EtOAc modifier, 0% → 1% → 2% isocratic step gradient). The fractions containing the product were evaporated to dryness in vacuo. An orange solid was obtained, 64 mg (20% yield). MS (APCI): Chemical formula C 95 H 90 Calculated for BF8N3O9 (M+H) = 1581; found: 1581. 1H NMR(400MHz,TCE)δ8.48(s,1H),7.91(d,J=8.3Hz,2H),7.89-7.80(m,4H),7.68(dd,J=8.2 ,4.0Hz,4H),7.47-7.37(m,5H),7.31(dd,J=8.3,1.4Hz,1H),7.22(t,J=1.7Hz,2H),7.13- 7.04(m,5H),6.96(ddd,J=8.5,7.1,1.4Hz,1H),4.24(q,J=7.1Hz,4H),4.12(s,2H),2.64( s, 6H), 2.36 (q, J = 7.3Hz, 4H), 1.30 (t, J = 7.2Hz, 6H), 1.14 (s, 36H), 0.89 (t, J = 7.3Hz, 6H).

[0292] Photoluminescent compound PLC-8:

[0293]

[0294] PLC-8 3,7-diethyl-5,5-difluoro-1,9-dimethyl-10-(3,3",5,5"-tetra-tert-butyl-5'-(2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-[1,1':3',1"-terphenyl]-2'-yl)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylic acid diethyl ester: 2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-[1,1':3',1"-terphenyl]-2'-yl)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylate was added under argon at 50°C.

[0147] A mixture of 3,3',5,5'-tetra-tert-butyl-2'-formyl-[1,1':3',1'-terphenyl]-5'-yl (1,2-dimethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate (0.2000 mmol, 238 mg), ethyl 2-ethyl-4-methyl-1H-pyrrole-3-carboxylate (0.5000 mmol, 91 mg) and pTsOH.HO (0.02000 mmol, 4 mg) was stirred in anhydrous DCE (20 mL) for 90 minutes, then cooled to room temperature and treated with DDQ (0.3600 mmol, 82 mg) and stirred at room temperature for ten minutes. The reaction mixture was treated with Et3N (1.600 mmol, 0.22 mL) and BF3.OEt2 (2.400 mmol, 0.30 mL) was added to the reaction. The addition of Et3N (1.600 mmol, 0.22 mL) and BF3.OEt2 (2.400 mmol, 0.30 mL) was repeated and the reaction was stirred at 50°C for 60 minutes. The reaction mixture was cooled to room temperature and evaporated in vacuo onto ~35 g flash silica gel and loaded into a cartridge. Purified by silica gel flash chromatography (120 g, 0% acetone / hexanes (2CV) → 10% (60CV)). The fractions containing the product were evaporated in vacuo to dryness. An orange solid was obtained, 174 mg (55% yield). MS (APCI): Formula C 95 H 90 Calculated for BF8N3O9 (M+H) = 1581; found: 1581. 1H NMR (400MHz, TCE) δ8.70 (s, 1H), 8.47 (s, 1H), 7.98-7.82 (m, 7H), 7.67 (d, J = 8. 0Hz,4H),7.49-7.35(m,6H),7.31(dd,J=8.3,1.3Hz,1H),7.21(t,J=1.8Hz,2H ),7.10(dd,J=8.3,1.5Hz,1H),7.01-6.90(m,5H),4.25(q,J=7.1Hz,4H),4.11 (s,2H),3.13-2.98(m,4H),2.02(s,6H),1.31(t,J=7.1Hz,6H),1.12(s,42H).

[0295] Photoluminescent compound PLC-9:

[0296]

[0297] PLC-9 10-(5'-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xanthen[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-3,3",5,5"-tetra-tert-butyl-[1,1':3',1"-terphenyl]-2'-yl)-5,5-dicyano-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylic acid diethyl ester: 10-(5'-(2-(4-(5,11-bis(3 ,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xanthen[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-3,3″,5,5″-tetra-tert-butyl-[1,1′:3′,1″-terphenyl]-2′-yl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2′,1′-f][1,3,2]diazaborinine-2,8-dicarboxylic acid diethyl ester (0.07936 mmol, 134 mg) was dissolved in anhydrous DCE (10 mL) and stirred at room temperature under argon. The reaction mixture was stirred for a few minutes at room temperature, then heated to 45 ° C for 120 minutes. The crude reaction mixture was poured into 30 mL of saturated NaHCO and stirred for a few minutes. The reaction mixture was filtered through a polypropylene frit to retain water and the product was eluted with DCM. The eluent was evaporated to dryness in a vacuum, dissolved in a small amount of DCM, and loaded onto the 15 g flash silica gel that was loaded into the loader. Purification by flash chromatography on silica gel (80 g, 0% acetone / hexanes (2CV) → 20% (5CV), gradient ending at 7.6%, 7.9%, 8.1%, and 8.4%). Fractions containing product were evaporated to dryness in vacuo, triturated with 80% MeOH / water, filtered, washed with 80% MeOH / water, dissolved in DCM, and evaporated to dryness in vacuo. Obtained an orange solid, 121 mg (90% yield). MS (APCI): Formula C 97 H 84 BF 12 Calculated for N5O9 (M+H) = 1703; found: 1703. 1H NMR(400MHz,TCE)δ8.75(s,1H),8.50(s,1H),8.27(d,J=1.7Hz,2H),8.08(s,1H),8.06-7 .96(m,3H),7.72-7.61(m,2H),7.49(ddd,J=8.5,6.1,2.6Hz,1H),7.43-7.36(m,4H),7.31 -7.26(m,1H),7.25(t,J=1.8Hz,2H),7.04-6.95(m,2H),6.89(d,J=1.8Hz,4H),4.31(q,J =7.1Hz,4H),4.09(s,2H),2.81(s,6H),2.10(s,6H),1.34(t,J=7.1Hz,6H),1.13(s,36H).

[0298] Photoluminescent compound PLC-10:

[0299]

[0300] Ethyl 2-ethyl-4-methyl-1H-pyrrole-3-carboxylate: Ethyl 3-oxopentanoate (100.0 mmol, 14.2 mL), aminoacetone hydrochloride (150.0 mmol, 16.440 g), and NaOAc (200.0 mmol, 16.406 g) were stirred in acetic acid (100 mL) and water (100 mL) under argon at 100° C. over the weekend. The reaction mixture was cooled to room temperature, and most of the solvent was evaporated in vacuo. The reaction mixture was partitioned between DCM (200 mL) and water (50 mL). The remaining acetic acid was carefully quenched with 10% KCO solution. The layers were separated, and the aqueous layer was extracted with 2×50 mL of DCM. The combined organic layers were dried over magnesium sulfate, filtered, and evaporated to dryness in vacuo. The crude material was dissolved in a small amount of DCM and loaded onto ~50 g of flash silica gel packed in a cartridge. Purify by flash chromatography on silica gel (120 g, 0% EtOAc / hexane (2 CV) → 15% (15 CV)). The fractions containing the product were evaporated to dryness in vacuo. A pale yellow oil was obtained, 7.985 g (44% yield). MS (APCI): Formula C 10 H 15 Calculated for NO2 (M+H) = 182; found: 182.

[0301] 10-(5'-(2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-[1,1':3',1"-terphenyl]-2'-yl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylic acid diethyl ester: Under argon, at 40°C, 2

[0266] 2'-Formyl-[1,1':3',1"-terphenyl]-5'-yl-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate (0.3000 mmol, 290 mg), pyrrole from the previous step (0.6300 mmol, 114 mg), and pTsOH.HO (0.06000 mmol, 11 mg) were stirred in anhydrous DCE (20 mL) for 60 minutes. The reaction was cooled to room temperature, and DDQ (0.4500 mmol, 102 mg) was added and stirred at room temperature for 10 minutes. EtN (2.400 mmol, 0.33 mL) and BF.OEt (3.600 mmol, 0.44 mL) were added to the reaction. The addition of Et3N (2.400 mmol, 0.33 mL) and BF3.OEt2 (3.600 mmol, 0.44 mL) was repeated, and the reaction was stirred at 50°C for 30 minutes. The reaction mixture was cooled to room temperature and quenched with 5 mL of water and stirred for several minutes, then filtered through a polypropylene frit to retain the water. The frit was eluted with DCM. The eluent was directed to a 15 g plug of flash silica and eluted with DCM, followed by 33% acetone / DCM. The solvent was evaporated to dryness in vacuo, dissolved in a small amount of DCM, and loaded onto 15 g of flash silica packed in a loader. Purification by flash chromatography on silica gel (80 g, 0% acetone / hexanes (2CV) → 50% (5CV), stopping at 12.0%, 13.0%, 13.6%, 14.0%, 14.5%, 15.1%, 15.5%, 16.0% and 17.0%, isocratic at each step. Fractions containing product were evaporated to dryness in vacuo. The product was triturated with hot MeOH, cooled to room temperature, filtered off, washed with MeOH, dissolved in DCM and evaporated to dryness. Obtained as an orange solid, 205 mg (50% yield). MS (APCI): Formula C 77 H 54 Calculated for BF8N3O9 (M+H) = 1328; found: 1328. 1H NMR(400MHz,TCE)δ8.71(s,1H),8.48(s,1H),7.94-7.82(m,5H),7.67(dd,J=8.3,3.6Hz,3H) ,7.46-7.37(m,5H),7.31(dd,J=8.3,1.3Hz,1H),7.23(dt,J=5.3,3.0Hz,5H),7.20-7.14(m, 4H),7.10(dd,J=8.3,1.5Hz,1H),6.96(ddd,J=8.4,7.2,1.4Hz,1H),4.27(q,J=7.1Hz,4H),4 .08(s,2H),3.11(q,J=7.3Hz,4H),1.97(s,6H),1.34(t,J=7.1Hz,6H),1.20(t,J=7.3Hz,6H).

[0302] PLC-10 5,5-Dicyano-10-(5'-(2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-[1,1':3',1"-terphenyl]-2'-yl)-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2 ',1'-f][1,3,2]diazaborin-2,8-dicarboxylic acid diethyl ester: Difluoropyrrole from the previous step (0.07500 mmol, 102 mg), TMSCN (0.7500 mmol, 0.094 mL) and BF3.OEt2 (0.1125 mmol, 0.014 mL) were stirred in anhydrous DCE (10 mL) under argon at room temperature. Continue for 5 minutes. The temperature was raised to 45°C for 120 minutes, then at room temperature overnight. The crude reaction mixture was poured into 30mL of saturated NaHCO3 and stirred for 5 minutes, then filtered through a polypropylene glass frit to retain water. The glass frit was eluted with DCM. The organic eluent was evaporated to dryness in a vacuum, dissolved in a small amount of DCM and loaded onto 15g of flash silica gel loaded into a loader. Purified by flash chromatography on silica gel (80g, 0% acetone / hexane (2CV) → 10% (5CV), stopping at 1.0%, then to 1.3%, isocratic at each step. The fractions containing the product were evaporated to dryness in a vacuum. The product was ground with hot MeOH, cooled to room temperature, filtered, washed with MeOH, dissolved in DCM, and evaporated to dryness in a vacuum. An orange solid was obtained, 64mg (62% yield). MS (APCI): Chemical Formula C 81 H 58 Calculated for BF6N5O9 (M+H) = 1370; found: 1370. 1HNMR(400MHz,TCE)δ8.70(s,1H),8.47(s,1H),7.91(d,J=8.3Hz,2H),7.89-7.81(m,4H),7.70- 7.63(m,4H),7.47-7.36(m,5H),7.31(dd,J=8.4,1.3Hz,1H),7.26(p,J=3.7Hz,6H),7.18-7.12 (m,4H),7.09(dd,J=8.4,1.5Hz,1H),6.96(ddd,J=8.4,7.2,1.4Hz,1H),4.30(q,J=7.1Hz,4H), 4.08(s,2H),3.26(q,J=7.2Hz,4H),1.99(s,6H),1.36(t,J=7.1Hz,6H),1.31(t,J=7.3Hz,6H).

[0303] Photoluminescent compound PLC-12:

[0304]

[0305] 5'-Hydroxy-[1,1':3',1"-terphenyl]-2'-carbaldehyde: Combine 2,6-dibromo-4-hydroxybenzaldehyde (20.00 mmol, 5598 mg), phenylboronic acid (80.00 mmol, 9754 mg), sodium bicarbonate (120.0 mmol, 10.081 g) and Pd(dppf)Cl2 (4.000 mmol, 2927 mg) in THF (150 mL) and water (12 mL). , and heated to 75 ° C for three hours under argon. The reaction mixture was cooled and most of the THF was evaporated in vacuo. The crude mixture was suspended in acetone and evaporated onto ~50g flash silica gel and loaded into a loader. Purified by silica gel flash chromatography (220g, 0% acetone / hexane (2CV)→40% (15CV)). The fraction containing the product was evaporated to dryness in vacuo and then ground with 50:50MeOH: water. The product was filtered off, washed with 50% MeOH / water, and dried at 80 ° C under vacuum. A slightly white solid was obtained, 4348mg (79% yield). MS (APCI): Chemical Formula C 19 H 14 Calculated for O2 (M+H) = 275; found: 275. 1 H NMR (400 MHz, acetone) δ 9.77 (s, 1H), 7.51-7.27 (m, 10H), 6.85 (s, 2H).

[0306] 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 2'-formyl-[1,1':3',1"-terphenyl]-5'-yl ester: The aldehyde from the previous step (1.500 mmol, 411 mg), 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 (1.650 mmol, 1395 mg), DMAP.pTsOH salt (0.1500 mmol, 44 mg) and EDC.HCl (2.500 mmol, 719 mg) were stirred in anhydrous DCE (20 mL) for one hour. The reaction mixture was loaded onto ~40 g of flash silica gel packed in a loader. Purification was performed by silica gel flash chromatography (120 g, acetone / DCM (2 CV) → 20% (5 CV), gradient stopped at 1.8%). The fractions containing the product were evaporated to dryness in vacuo. A yellow solid was obtained, 1183 mg (72% yield). MS (APCI): Formula C 61 H 31 F 12 Calculated value for NO6 (M+H) = 1102; found: 1102. 1 H NMR(400MHz,TCE)δ9.87(s,1H),8.75(s,1H),8.50(s,1H),8.27(d,J=1.6Hz,2H),8.07(s,1H),8.05-8.00(m, 3H),7.65-7.57(m,2H),7.52-7.34(m,13H),7.31-7.26(m,1H),7.22(s,2H),7.08-6.91(m,2H),4.04(s,2H).

[0307] PLC-11 10-(5'-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-[1,1':3',1"-terphenyl]-2'-yl)-5,5-difluoro-3,7-diisopropyl-1,9-dimethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylic acid dimethyl ester: under argon, at 3 The aldehyde from the previous step (0.4000 mmol, 441 mg), ethyl 2-isopropyl-4-methyl-1H-pyrrole-3-carboxylate (0.8000 mmol, 145 mg) and pTsOH.H2O (0.08000 mmol, 15 mg) were stirred in anhydrous DCE (25 mL) at 5°C overnight. The reaction mixture was cooled to room temperature and DDQ (2.400 mmol, 545 mg) was added and stirred at room temperature for 10 minutes. Et3N (3.200 mmol, 0.45 mL) was added to the reaction. ), and BF3.OEt2 (4.800mmol, 0.59mL) was added to the reaction. The addition of Et3N (3.200mmol, 0.45mL) and BF3.OEt2 (4.800mmol, 0.59mL) was repeated, and the reaction was stirred at 70°C for 24h. The reaction mixture was cooled to room temperature and quenched with 10mL of water and stirred for 5 minutes. The reaction mixture was filtered through a polypropylene glass frit to retain water. The glass frit was eluted with DCM. The organic eluent was evaporated to dryness in vacuo, dissolved in a small amount of DCM and charged Load onto 15 g of flash silica gel packed in a loader. Purify by flash chromatography on silica gel (120 g, 0% acetone / hexane (2 CV) → 20% (5 CV), gradient ending at 0.3%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0% and 1.1%). The fractions containing the product were evaporated to dryness in vacuo. The product was triturated with MeOH, filtered off, washed with MeOH, dissolved in DCM and evaporated to dryness in vacuo. An orange solid was obtained, 230 mg (39% yield). MS (APCI): Formula C 77 H 50 Calculated for BCl4F8N3O9 (M+H) = 1464; found: 1464. 1H NMR(400MHz,TCE)δ8.70(s,1H),8.47(s,1H),7.91(d,J=8.3Hz,2H),7.88-7.82(m ,4H),7.72-7.64(m,4H),7.47-7.37(m,4H),7.31(dd,J=8.3,1.4Hz,1H),7.10(dd ,J=8.4,1.5Hz,1H),7.05(d,J=1.8Hz,4H),6.96(ddd,J=8.4,7.1,1.3Hz,1H),4.2 8(q,J=7.1Hz,4H),4.08(s,2H),2.76(s,6H),1.90(s,7H),1.35(t,J=7.1Hz,6H).

[0308] Photoluminescent compound PLC-12:

[0309]

[0310] PLC-12 10-(5'-(2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]75isoquinolin-2(3H)-yl)phenyl)acetoxy)-[1,1':3',1"-terphenyl]-2'-yl)-3,7-diethyl-5,5-difluoro-1,9-dimethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylic acid diethyl ester: 2-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]75isoquinolin-2(3H)-yl)phenyl)acetoxy)-[1,1':3',1"-terphenyl]-2'-yl 2'-Formyl-[1,1':3',1"-terphenyl]-5'-yl-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate (0.3000 mmol, 290 mg), ethyl 2-ethyl-4-methyl-1H-pyrrole-3-carboxylate (0.6300 mmol, 114 mg) and pTsOH.HO (0.06000 mmol, 11 mg) were stirred in anhydrous DCE (20 mL) for one hour. The reaction mixture was cooled to room temperature and treated with DDQ (0.4500 mmol, 102 mg) and stirred at room temperature for 10 minutes. The reaction mixture was treated with Et3N (2.400 mmol, 0.33 mL) and BF3.OEt2 (3.600 mmol, 0.44 mL) was added to the reaction. The addition of Et3N (2.400 mmol, 0.33 mL) and BF3.OEt2 (3.600 mmol, 0.44 mL) was repeated and the reaction was stirred at 50°C for one hour. The reaction mixture was cooled to room temperature and quenched with 10 mL of water and 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 to dryness in vacuo, dissolved in a small amount of DCM and loaded onto ~45 g of flash silica gel loaded in a loader. Purification was performed by flash chromatography on silica gel (120 g, 0% acetone / hexanes (2 CV) → 50% (5 CV), gradient ending at 12.0%, followed by gradient ending at 13.0%, 13.6%, 14.0%, 14.5%, 14.9%, 15.1%, 15.5%, 16.0% and 17.0%). Fractions containing product were evaporated to dryness in vacuo. An orange solid was obtained, 205 mg (50% yield). MS (APCI): Formula C 79 H 58 Calculated for BF8N3O9 (M+H) = 1356; found: 1356. 1H NMR(400MHz,TCE)δ8.71(s,1H),8.48(s,1H),7.94-7.82(m,5H),7.67(dd,J=8.3,3.6Hz,3H) ,7.46-7.37(m,5H),7.31(dd,J=8.3,1.3Hz,1H),7.23(dt,J=5.3,3.0Hz,5H),7.20-7.14(m, 4H),7.10(dd,J=8.3,1.5Hz,1H),6.96(ddd,J=8.4,7.2,1.4Hz,1H),4.27(q,J=7.1Hz,4H),4 .08(s,2H),3.11(q,J=7.3Hz,4H),1.97(s,6H),1.34(t,J=7.1Hz,6H),1.20(t,J=7.3Hz,6H).

[0311] Photoluminescent compound PLC-13:

[0312]

[0313] PLC-13 3,7-dibutyl-10-(5'-(2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-[1,1':3',1"-terphenyl]-2'-yl)-5,5-difluoro-1,9-dimethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylic acid diethyl ester: 2-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-[1,1':3',1"-terphenyl]-2'-yl]-5,5-difluoro-1,9-dimethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylate was added under argon at 40°C. 2'-Formyl-[1,1':3',1"-terphenyl]-5'-yl (1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate (0.3000 mmol, 290 mg), ethyl 2-butyl-4-methyl-1H-pyrrole-3-carboxylate (0.6300 mmol, 132 mg) and pTsOH.HO (0.06000 mmol, 11 mg) were stirred in anhydrous DCE (25 mL) for 3 h. The reaction mixture was cooled to room temperature and treated with DDQ (0.9000 mmol, 204 mg) and stirred at room temperature for 10 min. The reaction mixture was treated with Et3N (2.400 mmol, 0.33 mL) and BF3.OEt2 (3.600 mmol, 0.44 mL) was added to the reaction. The addition of Et3N (2.400 mmol, 0.33 mL) and BF3.OEt2 (3.600 mmol, 0.44 mL) was repeated and the reaction was stirred at 50°C for one hour. The reaction mixture was cooled to room temperature and quenched with 10 mL of water and 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 to dryness in vacuo, dissolved in a small amount of DCM and loaded onto ~45 g of flash silica gel loaded in a loader. Purify by flash chromatography on silica gel (80 g, 0% acetone / hexanes (2CV) → 25% (5CV), gradient ending at 11.1%, 12.5%, 13.4%, 14.5%, 15.5% and 16.5%. Fractions containing product are evaporated to dryness in vacuo. Repurify (load onto 15 g flash silica gel packed in a cartridge), 40 g, 0% EtOAc / hexanes (2CV) → 35% (5CV), gradient ending at 21.6%, 22.1% and 22.5%. Fractions containing product are evaporated to dryness in vacuo. Obtained an orange solid, 143 mg (34% yield). MS (APCI): Formula C 83 H 66 Calculated for BF8N3O9 (M+H) = 1413; found: 1413. 1H NMR(400MHz,TCE)δ8.62(s,1H),8.39(s,1H),7.82(d,J=8.3Hz,2H),7.80-7.71(m,4H),7.58(dd,J =8.3,3.7Hz,4H),7.38-7.26(m,5H),7.22(dd,J=8.3,1.3Hz,1H),7.17-7.05(m,10H),7.01(dd,J=8 .4,1.5Hz,1H),6.87(ddd,J=8.4,7.1,1.4Hz,1H),4.17(q,J=7.1Hz,4H),3.99(s,2H),2.99(t,J=7. 8Hz, 4H), 1.86 (s, 6H), 1.44 (h, J = 6.2Hz, 4H), 1.27 (dt, J = 16.7, 7.2Hz, 10H), 0.83 (t, J = 7.3Hz, 6H).

[0314] Photoluminescent compound PLC-14:

[0315]

[0316] PLC-14 10-(5'-(2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-3,3",5,5"-tetrafluoro-[1,1':3',1"-terphenyl]-2'-yl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylic acid diethyl ester: 2-(4-( 1,3-Dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate, 3,3″,5,5″-tetrafluoro-2′-formyl-[1,1′:3′,1″-terphenyl]-5′-yl ester (0.3000 mmol, 311 mg), ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (0.6300 mmol, 105 mg) and pTsOH.HO (0.06000 mmol, 11 mg) were stirred in anhydrous DCE (25 mL) for 3 hours. The reaction mixture was cooled to room temperature and treated with DDQ (0.6000 mmol, 136 mg) and stirred at room temperature for 10 minutes. The reaction mixture was treated with Et3N (2.400 mmol, 0.33 mL) and BF3.OEt2 (3.600 mmol, 0.44 mL) was added to the reaction. The addition of Et3N (2.400 mmol, 0.33 mL) and BF3.OEt2 (3.600 mmol, 0.44 mL) was repeated and the reaction was stirred at 50°C for one hour. The reaction mixture was cooled to room temperature and quenched with 10 mL of water and 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 to dryness in vacuo, dissolved in a small amount of DCM and loaded onto 15 g of flash silica gel loaded in a loader. Purification was performed by flash chromatography on silica gel (40 g, 0% acetone / hexane (2 CV) → 25% (5 CV), gradient ending at 13.5%, 14.0%, 14.5% and 14.9%). Fractions containing product were evaporated to dryness in vacuo. An orange solid was obtained, 241 mg (57% yield). MS (APCI): Formula C 77 H 54 Calculated for BF8N3O9 (M+H) = 1328; found: 1328. 1H NMR(400MHz,TCE)δ8.70(s,1H),8.47(s,1H),7.91(d,J=8.3Hz,2H),7.88-7.81(m,4H) ,7.73-7.63(m,4H),7.47-7.37(m,5H),7.31(dd,J=8.3,1.3Hz,1H),7.10(dd,J=8.4,1 .5Hz,1H),6.96(dddd,J=8.4,7.1,1.4Hz,1H),6.74(dddd,J=18.0,8.6,4.8,2.3Hz,6H) ,4.27(q,J=7.1Hz,4H),4.08(s,2H),2.75(s,6H),1.91(s,6H),1.35(t,J=7.1Hz,6H).

[0317] Photoluminescent compound PLC-15:

[0318]

[0319] PLC-15 10-(5'-(2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-3,3",5,5"-tetrafluoro-[1,1':3',1"-terphenyl]-2'-yl)-3,7-diethyl-5,5-difluoro-1,9-dimethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylic acid diethyl ester: 2-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-3,3",5,5"-tetrafluoro-[1,1':3',1"-terphenyl]-2'-yl 3,3″,5,5″-tetrafluoro-2′-formyl-[1,1′:3′,1″-terphenyl]-5′-yl (1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate (0.3000 mmol, 311 mg), ethyl 2-ethyl-4-methyl-1H-pyrrole-3-carboxylate (0.6300 mmol, 114 mg) and pTsOH.HO (0.06000 mmol, 11 mg) were stirred in anhydrous DCE (25 mL) for 3 hours. The reaction mixture was cooled to room temperature and treated with DDQ (1.800 mmol, 409 mg) and stirred at room temperature for 10 minutes. The reaction mixture was treated with Et3N (2.400 mmol, 0.33 mL) and BF3.OEt2 (3.600 mmol, 0.44 mL) was added to the reaction. The addition of Et3N (2.400 mmol, 0.33 mL) and BF3.OEt2 (3.600 mmol, 0.44 mL) was repeated and the reaction was stirred at 50°C for one hour. The reaction mixture was cooled to room temperature and quenched with 10 mL of water and 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 to dryness in vacuo, dissolved in a small amount of DCM and loaded onto 15 g of flash silica gel loaded in a loader. Purification was performed by flash chromatography on silica gel (40 g, 0% acetone / DCM (2CV) → 25% (5CV), gradient ending at 14.3%, 14.5% and 14.8%). Fractions containing product were evaporated to dryness in vacuo. An orange solid was obtained, 266 mg (62% yield). MS (APCI): Formula C 79 H 58 Calculated for BF8N3O9 (M+H) = 1356; found: 1356. 1H NMR (400MHz, TCE) δ8.71 (s, 1H), 8.48 (s, 1H), 7.91 (d, J = 8.3Hz, 2H), 7.89-7.80 (m, 4H), 7. 67(d,J=8.1Hz,4H),7.49-7.35(m,5H),7.31(dd,J=8.3,1.3Hz,1H),7.10(dd,J=8.4,1.5H z,1H),6.96(ddd,J=8.4,7.1,1.4Hz,1H),6.81-6.63(m,6H),4.28(q,J=7.1Hz,4H),4.08( s, 2H), 3.16 (q, J = 7.3Hz, 4H), 1.91 (s, 6H), 1.35 (t, J = 7.1Hz, 6H), 1.25 (t, J = 8.1Hz, 10H).

[0320] Photoluminescent compound PLC-16:

[0321]

[0322] 2-Butyl-4-methyl-1H-pyrrole-3-carboxylic acid ethyl ester: Ethyl 3-oxoheptanoate (20.00 mmol, 3.55 mL) and aminoacetone hydrochloride (40.00 mmol, 4.384 g) were combined in water (100 mL) and 200 proof ethanol (50 ml) and heated to 80 ° C for 300 minutes. The crude reaction mixture was extracted with DCM (3×100 mL), dried over magnesium sulfate, filtered, and evaporated to dryness. The crude mixture was dissolved in DCM and loaded onto ~40 g flash silica gel loaded in a loader. Purified by silica gel flash chromatography (120 g, 0% EtOAc / DCM (2CV)→2% (20CV)). The fractions containing the product were evaporated to dryness. A waxy slightly brown solid was obtained, 2.485 g (59% yield). MS (APCI): Chemical formula C 12 H 19 Calculated for NO2 (M+H) = 210; found: 210. 1 H NMR(400MHz,TCE)δ8.06(s,1H),6.39(dd,J=2.3,1.2Hz,1H),4.25(q,J=7.1Hz,2H),2.97-2.75 (m,2H),2.24(d,J=1.1Hz,3H),1.71-1.51(m,2H),1.35(t,J=7.1Hz,5H),0.94(t,J=7.3Hz,3H).

[0323] 3,3",5,5"-tetrafluoro-5'-hydroxy-[1,1':3',1"-terphenyl]-2'-carbaldehyde: 2,6-dibromo-4-hydroxybenzaldehyde (10.00 mmol, 2800 mg), (3,5-difluorophenyl)boronic acid (40.00 mmol, 6316 mg), sodium bicarbonate (60.00 mmol, 5041 mg) and Pd(dppf)Cl2 (2.000 mmol, 1464 mg) were combined in THF (150 mL) ) and water (14 mL) and heated to 75 ° C for one hour under argon. The reaction mixture was cooled and most of the THF was evaporated in vacuo. The crude mixture was suspended in acetone and evaporated onto ~50 g flash silica gel and loaded into a loader. Purified by flash chromatography on silica gel (120 g, 0% acetone / hexane (2CV) → 40% (10CV)). The fractions containing the product were evaporated to dryness in vacuo and then triturated with 90:10 MeOH: water. The product was filtered off, washed with 10% MeOH / water, and dried at 80 ° C under vacuum. A slightly white solid was obtained, 3.167 g (92% yield). MS (APCI): Chemical Formula C 19 H 10 Calculated for F4O2 (M+H) = 347; found: 347. 1 H NMR (400MHz, DMSO) δ10.92 (s, 1H), 9.64 (s, 1H), 7.28 (tt, J = 9.4, 2.3Hz, 2H), 7.19-7.09 (m, 4H), 6.79 (s, 2H).

[0324] 2-(4-(1,3-Dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid 3,3″,5,5″-tetrafluoro-2′-formyl-[1,1′:3′,1″-terphenyl]-5′-yl ester: The phenol from the previous step (4.000 mmol, 1385 mg), 2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (4.800 mm Hg) were added. ol, 3406 mg), DMAP.pTsOH salt (0.4000 mmol, 118 mg) and EDC.HCl (8.000 mmol, 1534 mg) were stirred in anhydrous DCM (35 mL) in a capped vial for one hour. The reaction mixture was loaded onto ~40 g flash silica gel loaded in a loader. Purification was performed by silica gel flash chromatography (120 g, EtOAc / DCM (2 CV) → 20% (5 CV)). The fractions containing the product were evaporated to dryness in vacuo. A yellow solid was obtained, 4137 mg (100% yield). MS (APCI): Chemical formula C 59 H 29 F 10 Calculated for NO6 (M+H) = 1038; found: 1038. 1 H NMR(400MHz,TCE)δ9.87(s,1H),8.70(s,1H),8.47(s,1H),7.96-7.81(m,6H),7.67(d,J=8.0Hz,2H),7.65-7.58(m,2H),7.43(ddd,J=8.6, 7.1,1.5Hz,1H),7.40-7.35(m,2H),7.31(dd,J=8.3,1.3Hz,1H),7.26(s,2H),7.10(dd,J=8.3,1.5Hz,1H),7.01-6.87(m,7H),4.04(s,2H).

[0325] PLC-16 3,7-Dibutyl-10-(5'-(2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-3,3",5,5"-tetrafluoro-[1,1':3',1"-terphenyl]-2'-yl)-5,5-difluoro-1,9-dimethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazolyl (Diethyl boroline-2,8-dicarboxylate): The aldehyde from the previous step (0.3000 mmol, 311 mg), ethyl 2-butyl-4-methyl-1H-pyrrole-3-carboxylate (0.6300 mmol, 132 mg) and pTsOH.H2O (0.06000 mmol, 11 mg) were stirred in anhydrous DCE (25 mL) under argon at 40° C. overnight. The reaction mixture was cooled to room temperature and DDQ (1.800 mmol, 409 mg) was added. ) and stirred at room temperature for 10 minutes. Et3N (2.400 mmol, 0.33 mL) was added to the reaction, and BF3.OEt2 (3.600 mmol, 0.44 mL) was added to the reaction. The addition of Et3N (2.400 mmol, 0.33 mL) and BF3.OEt2 (3.600 mmol, 0.44 mL) was repeated, and the reaction was stirred at 50 ° C for 30 minutes. The reaction mixture was cooled to room temperature and quenched with 10 mL of water and 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 to dryness in vacuo, dissolved in a small amount of DCM and loaded onto 15 g of flash silica gel loaded into a loader. Purified by flash chromatography on silica gel (80 g, 0% acetone / hexane (2CV) → 25% (5CV), stopping the gradient at 13.5%. The fractions containing the product were evaporated to dryness in vacuo. An orange solid was obtained, 60 mg (14% yield). MS (APCI): Formula C 83 H 62 BF 12 Calculated for N3O9 (M+H) = 1484; found: 1484. 1H NMR(400MHz,TCE)δ8.70(s,1H),8.47(s,1H),7.91(d,J=8.3Hz,2H),7.89-7.81(m,4H),7.67(d,J=8 .1Hz, 4H), 7.50-7.38 (m, 5H), 7.31 (dd, J=8.3, 1.3Hz, 1H), 7.10 (dd, J=8.4, 1.5Hz, 1H), 6.96 (ddd, J= 8.4,7.1,1.4Hz,1H),6.81-6.62(m,6H),4.28(q,J=7.1Hz,4H),4.08(s,2H),3.13(t,J=7.9Hz,4H), 1.90(s,6H),1.63-1.51(m,4H),1.41(q,J=7.5Hz,4H),1.35(t,J=7.1Hz,6H),0.94(t,J=7.3Hz,6H).

[0326] Photoluminescent compound PLC-17:

[0327]

[0328] 2-Isobutyl-4-methyl-1H-pyrrole-3-carboxylic acid ethyl ester: 5-methyl-3-oxohexanoic acid ethyl ester (20.00mmol, 3.56mL) and aminoacetone hydrochloride (40.00mmol, 4.384g) were combined in water (100mL) and 200proof ethanol (50ml) and heated to 80 °C for 300 minutes. The crude reaction mixture was extracted with DCM (3×100mL), dried over magnesium sulfate, filtered, and evaporated to dryness. The crude mixture was dissolved in DCM and loaded onto ~40g flash silica gel loaded in a loader. Purified by silica gel flash chromatography (120g, 0% EtOAc / DCM (2CV)→2% (20CV)). The fractions containing the product were evaporated to dryness. A thick yellow liquid was obtained, 1750mg (42% yield). MS (APCI): Chemical formula C 12 H 19 Calculated for NO2 (M+H) = 210; found: 210. 1 H NMR(400MHz,TCE)δ7.98(s,1H),6.40(dd,J=2.3,1.1Hz,1H),4.24(q,J=7.1Hz,2H),2.74(d,J=7.2Hz, 2H), 2.24 (d, J = 1.1Hz, 3H), 1.94 (dh, J = 13.8, 6.9Hz, 1H), 1.35 (t, J = 7.1Hz, 3H), 0.92 (d, J = 6.7Hz, 6H).

[0329] PLC-17 10-(5'-(2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-3,3",5,5"-tetrafluoro-[1,1':3',1"-terphenyl]-2'-yl)-5,5-difluoro-3,7-diisobutyl-1,9-dimethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1 ,3,2] diethyl diazaborin-2,8-dicarboxylate: 3,3",5,5"-tetrafluoro-5'-hydroxy-[1,1':3',1"-terphenyl]-2'-carbaldehyde (0.3000 mmol, 311 mg), pyrrole from the previous step (0.6300 mmol, 132 mg) and pTsOH.H2O (0.06000 mmol, 11 mg) were stirred in anhydrous DCE (25 mL) under argon at 40°C for 3 hours. The reaction mixture was cooled to room temperature and treated with DDQ (1.800 mmol, 409 mg) and stirred at room temperature for 10 minutes. The reaction mixture was treated with Et3N (2.400 mmol, 0.33 mL) and BF3.OEt2 (3.600 mmol, 0.44 mL) was added to the reaction. The addition of Et3N (2.400mmol, 0.33mL) and BF3.OEt2 (3.600mmol, 0.44mL) was repeated and the reaction was stirred at 50°C for one hour. The reaction mixture was cooled to room temperature and quenched with 10mL of water and 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 to dryness in vacuo, dissolved in a small amount of DCM and loaded onto 15g of flash silica gel loaded into a loader. Purified by flash chromatography on silica gel (40g, 0% acetone / hexane (2CV) → 25% (5CV), terminating the gradient at 13.6% and 14.0%. The fractions containing the product were evaporated to dryness in vacuo. An orange solid was obtained, 118mg (27% yield). MS (APCI): Chemical formula C 83 H 62 BF 12 Calculated for N3O9 (M+H) = 1484; found: 1484. 1H NMR(400MHz,TCE)δ8.70(s,1H),8.47(s,1H),7.91(d,J=8.3Hz,2H),7.89-7.82(m,4H),7.71-7 .61(m,4H),7.46(s,2H),7.44-7.37(m,3H),7.31(dd,J=8.3,1.3Hz,1H),7.10(dd,J=8.3,1.5H z,1H),6.96(ddd,J=8.4,7.1,1.4Hz,1H),6.72(dd,J=6.7,3.0Hz,6H),4.26(q,J=7.1Hz,4H),4 .08(s,2H),3.08(d,J=7.5Hz,4H),1.87(s,6H),1.34(t,J=7.1Hz,6H),0.85(d,J=6.7Hz,12H).

[0330] Photoluminescent compound PLC-18:

[0331]

[0332] 3,3",5,5"-Tetrachloro-5'-hydroxy-[1,1':3',1"-terphenyl]-2'-carbaldehyde: Combine 2,6-dibromo-4-hydroxybenzaldehyde (5.00 mmol, 1400 mg), (3,5-dichlorophenyl)boronic acid (20.00 mmol, 3816 mg), sodium bicarbonate (30.00 mmol, 2520 mg) and Pd(dppf)Cl2 (1.000 mmol, 732 mg) in THF (120 mL). and water (11 mL) and heated to 75 ° C for one hour under argon. The reaction mixture was cooled and most of the THF was evaporated in vacuo. The crude mixture was suspended in acetone and evaporated onto ~50g flash silica gel and loaded into a loader. Purified by flash chromatography on silica gel (120g, 0% acetone / hexane (2CV)→40% (10CV)). The fraction containing the product was evaporated to dryness in vacuo and then ground with 90:10MeOH: water. The product was filtered off, washed with 10% MeOH / water, and dried at 80 ° C under vacuum. A slightly white solid was obtained, 1926g (94% yield). MS (APCI): Chemical Formula C 19 H 10 Calculated for Cl4O2 (M+H) = 411; found: 411. 1 H NMR (400MHz, DMSO) δ10.93 (s, 1H), 9.60 (s, 1H), 7.65 (t, J = 2.0Hz, 2H), 7.48 (d, J = 1.9Hz, 4H), 6.79 (s, 2H).

[0333] 2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid 3,3",5,5"-tetrachloro-2'-formyl-[1,1':3',1"-terphenyl]-5'-yl ester: Phenol from the previous step (2.000 mmol, 824 mg), 2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (2.40 0mmol, 1703mg), DMAP.pTsOH salt (0.2000mmol, 59mg) and EDC.HCl (4.000mmol, 767mg) were stirred in anhydrous DCM (50mL) for one hour. The reaction mixture was loaded onto ~40g flash silica gel loaded in a loader. Purification was performed by silica gel flash chromatography (120g, EtOAc / DCM (2CV)→40% (10CV)). The fractions containing the product were evaporated to dryness in vacuo. A yellow solid was obtained, 2054mg (93% yield). MS (APCI): Chemical formula C 59 H 29 Calculated value for Cl4F6NO6 (M+H) = 1102; found value: 1102. 1 HNMR(400MHz,TCE)δ8.71(s,1H),8.48(s,1H),7.95-7.81(m,6H),7.70-7.62(m,4H),7.48-7.38(m,3H),7.31(dd,J=8.3,1.3Hz,1H ),7.10(dd,J=8.4,1.5Hz,1H),6.96(ddd,J=8.4,7.1,1.4Hz,1H),6.60(s,2H),4.05(s,2H),3.77(s,6H),2.72(s,6H),1.78(s,6H).

[0334] PLC-18 5,5-Difluoro-1,3,7,9-tetramethyl-10-(3,3",5,5"-tetrachloro-5'-(2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-[1,1':3',1"-terphenyl]-2'-yl)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborone Diethyl hexene-2,8-dicarboxylate: The aldehyde from the previous step (0.3000 mmol, 331 mg), ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (0.6300 mmol, 105 mg) and pTsOH.H2O (0.06000 mmol, 11 mg) were stirred in anhydrous DCE (25 mL) under argon at 40° C. overnight. The reaction mixture was cooled to room temperature, and DDQ (0.6000 mmol, 136 mg) was added and stirred at room temperature. The reaction was stirred at 50 ° C for 10 minutes. Et3N (2.400mmol, 0.33mL) was added to the reaction, and BF3.OEt2 (3.600mmol, 0.44mL) was added to the reaction. The addition of Et3N (2.400mmol, 0.33mL) and BF3.OEt2 (3.600mmol, 0.44mL) was repeated, and the reaction was stirred at 50 ° C for 30 minutes. The reaction mixture was cooled to room temperature and quenched with 10mL of water and stirred for 5 minutes. The reaction mixture was filtered through an propylene frit to retain water. The frit was eluted with DCM. The organic eluent was evaporated to dryness in vacuo, dissolved in a small amount of DCM and loaded onto 15 g of flash silica gel packed in a loader. Purified by flash chromatography on silica gel (40 g, 0% acetone / hexane (2CV) → 25% (5CV), stopping the gradient at 14.3% and 14.4%. The fractions containing the product were evaporated to dryness in vacuo. An orange solid was obtained, 304 mg (69% yield). MS (APCI): Formula C 77 H 50 Calculated for BCl4F8N3O9 (M+H) = 1464; found: 1464. 1H NMR(400MHz,TCE)δ8.70(s,1H),8.47(s,1H),7.91(d,J=8.3Hz,2H),7.88-7.82(m ,4H),7.72-7.64(m,4H),7.47-7.37(m,4H),7.31(dd,J=8.3,1.4Hz,1H),7.10(dd ,J=8.4,1.5Hz,1H),7.05(d,J=1.8Hz,4H),6.96(ddd,J=8.4,7.1,1.3Hz,1H),4.2 8(q,J=7.1Hz,4H),4.08(s,2H),2.76(s,6H),1.90(s,7H),1.35(t,J=7.1Hz,6H).

[0335] Photoluminescent compound PLC-19:

[0336]

[0337] Quinolin-6-ylmethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate: Under argon, quinolin-6-ylmethanol (15.00 mmol, 2388 mg), 2,4-dimethyl-1H-pyrrole-3-carboxylic acid (45.00 mmol, 6264 mg), and DMAP.pTsOH salt (45.00 mmol, 13.247 g) were stirred in anhydrous DMF (40 mL) heated to 100°C. EDC.HCl (90.00 mmol, 17.203 g) was added to the reaction, which was rinsed with 10 mL of anhydrous DMF. The reaction mixture was heated to 130°C and stirred for 60 minutes. The reaction was cooled to room temperature and evaporated to dryness in vacuo. The residue was dissolved in some acetone and evaporated in vacuo onto ~40 g of flash silica gel and loaded into a cartridge. Purify by flash chromatography on silica gel (220 g, 0% EtOAc / toluene (2 CV) → 50% (25 CV)). The fractions containing the product were evaporated to dryness in vacuo. A light brown solid was obtained, 2370 mg (56% yield). MS (APCI): Formula C 17 H 16 Calculated for N2O2 (M+H) = 281; found: 281. 1H NMR(400MHz,DMSO)δ10.96(s,1H),8.90(dd,J=4.2,1.8Hz,1H),8.38(ddd,J=8.4,1.7,0.8Hz,1H),8.04(d,J=8.7Hz,1H),7.99(d,J=1.9Hz,1H),7.80(dd,J=8.7,2.0Hz,1H),7.54(dd,J=8.3,4.2Hz,1H),6.42(dd,J=2.3,1.2Hz,1H),5.39(s,2H),2.38(s,3H),2.13(d,J=1.1Hz,3H)。

[0338] PLC-19 5,5-difluoro-1,3,7,9-tetramethyl-10-(3,3",5,5"-tetra-tert-butyl-5'-(2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-[1,1':3',1"-terphenyl]-2'-yl)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylic acid bis(quinolin-6-ylmethyl ester): 2-(

[0266] 3,3",5,5"-tetra-tert-butyl-2'-formyl-[1,1':3',1"-terphenyl]-5'-yl 4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate (0.2500 mmol, 298 mg), pyrrole from the previous step (0.5000 mmol, 140 mg), and pTsOH.HO (1.000 mmol, 190 mg) were stirred in anhydrous DCE (15 mL) for 60 minutes and then cooled to room temperature. The reaction was treated with DDQ (0.5000 mmol, 114 mg) and stirred for 10 minutes. To the reaction was added Et3N (2.000 mmol, 0.28 mL) and BF3.OEt2 (3.000 mmol, 0.37 mL). The addition of Et3N (2.000 mmol, 0.28 mL) and BF3.OEt2 (3.000 mmol, 0.37 mL) was repeated and the reaction was stirred at 65°C for 60 minutes. The reaction mixture was cooled to room temperature and quenched with 10 mL of water and 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 to dryness in vacuo, dissolved in a small amount of DCM and loaded onto 15 g of flash silica gel loaded in a loader. Purification by flash chromatography on silica gel (120 g, 0% acetone / hexanes (2CV) → 30% (5CV), gradient ending at 12.0%, 13.0%, and 14.0%). Fractions containing product were evaporated to dryness in vacuo. The product was triturated with MeOH / water, filtered, washed with MeOH / water, dissolved in DCM, and evaporated to dryness in vacuo. An orange solid was obtained, 188 mg (42% yield). MS (APCI): Formula C 109 H 92 Calculated for BF8N5O9 (M+H) = 1779; found: 1779. 1H NMR(400MHz,TCE)δ8.92(dd,J=4.3,1.7Hz,2H),8.70(s,1H),8.47(s,1H),8.20-8.14(m,2H),8. 10(d,J=8.7Hz,2H),7.94-7.82(m,6H),7.81(d,J=1.9Hz,2H),7.72-7.62(m,6H),7.47-7.35(m,7 H),7.31(dd,J=8.4,1.3Hz,1H),7.18(t,J=1.7Hz,2H),7.09(dd,J=8.5,1.6Hz,1H),6.99-6.93( m, 1H), 6.91 (d, J = 1.8Hz, 4H), 5.44 (s, 4H), 4.08 (s, 2H), 2.64 (s, 6H), 2.01 (s, 6H), 1.06 (s, 36H).

[0339] Photoluminescent compound PLC-20:

[0340]

[0341] 2-(9H-carbazol-9-yl)ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate: Under an argon atmosphere, 2-(9H-carbazol-9-yl)ethan-1-ol (15.00 mmol, 2388 mg), 2,4-dimethyl-1H-pyrrole-3-carboxylic acid (45.00 mmol, 6264 mg), and DMAP.pTsOH salt (45.00 mmol, 13.247 g) were stirred in anhydrous DMF (40 mL) heated to 100°C. EDC.HCl (90.00 mmol, 17.203 g) was added to the reaction, which was rinsed with 10 mL of anhydrous DMF. The reaction mixture was heated to 130°C and stirred for 60 minutes. The reaction was quenched with water (15 mL), cooled to room temperature, and then evaporated to dryness in vacuo. The residue was dissolved in some acetone and evaporated in vacuo onto ~40 g flash silica gel and loaded into a loader. Purified by flash chromatography on silica gel (330 g, 0% EtOAc / toluene (2 CV) → 30% (15 CV)). The fractions containing the product were evaporated to dryness in vacuo. A light brown solid was obtained, 1322 mg (27% yield). MS (APCI): Formula C 21 H 20 Calculated for N2O2 (M+H) = 333; found: 333. 1H NMR(400MHz,TCE)δ8.11(dt,J=7.7,1.0Hz,2H),7.95(s,1H),7.58-7.40(m,4H),7.27(ddd,J=7.9,6.1,2.0Hz,2H),6.34(dd,J=2.4,1.2Hz,1H),4.76-4.53(m,4H),2.26(s,3H),2.11(d,J=1.1Hz,3H)。

[0342] PLC-20 5,5-difluoro-1,3,7,9-tetramethyl-10-(3,3",5,5"-tetra-tert-butyl-5'-(2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-[1,1':3',1"-terphenyl]-2'-yl)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylic acid (bis(2-(9H-carbazol-9-yl)ethyl ester): at 65°C, 3,3″,5,5″-tetra-tert-butyl-2′-formyl-[1,1′:3′,1″-terphenyl]-5′-yl 2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate (0.2500 mmol, 298 mg), pyrrole from the previous step (0.5000 mmol, 166 mg) and pTsOH.HO (1.000 mmol, 190 mg) were stirred in anhydrous DCE (15 mL) for 60 min and then cooled to room temperature. . The reaction was treated with DDQ (0.5000 mmol, 114 mg) and stirred for 10 minutes. Et3N (2.000 mmol, 0.28 mL) was added to the reaction, and BF3.OEt2 (3.000 mmol, 0.37 mL) was added to the reaction. The addition of Et3N (2.000 mmol, 0.28 mL) and BF3.OEt2 (3.000 mmol, 0.37 mL) was repeated, and the reaction was stirred at 65 ° C for 60 minutes. The reaction mixture was cooled to room temperature and quenched with 10 mL of water and stirred for 5 minutes. The reaction was filtered through a polypropylene glass frit. The mixture was stirred to retain water. The glass frit was eluted with DCM. The organic eluent was evaporated to dryness in vacuo, dissolved in a small amount of DCM and loaded onto 15g of flash silica gel packed in a loader. Purified by flash chromatography on silica gel (120g, 0% acetone / hexane (2CV) → 15% (5CV), stopping the gradient at 4.9%, returning to 4.4%. The fractions containing the product were evaporated to dryness in vacuo. The product was triturated with MeOH / water, filtered, washed with MeOH / water, dissolved in DCM, and evaporated to dryness in vacuo. An orange solid was obtained, 304mg (65% yield). MS (APCI): Chemical formula C 117 H 100 Calculated for BF8N5O9 (M+H) = 1883; found: 1883. 1H NMR(400MHz,TCE)δ8.70(s,1H),8.47(s,1H),8.09(d,J=7.7Hz,4H),7.91(d,J=8.3Hz,2 H),7.89-7.80(m,4H),7.76-7.62(m,4H),7.46-7.34(m,13H),7.31(dd,J=8.3,1.3Hz,1 H),7.23(ddd,J=8.9,4.4,2.0Hz,6H),7.10(dd,J=8.4,1.5Hz,1H),7.00-6.95(m,1H),6 .93(d,J=1.8Hz,4H),4.59(s,8H),4.15(s,2H),2.25(s,6H),1.93(s,6H),1.09(s,36H).

[0343] Photoluminescent compound PLC-21:

[0344]

[0345]

[0266] 4-Formyl-3,5-dimethoxyphenyl-2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: 4-Hydroxy-2,6-dimethoxybenzaldehyde (364 mg, 2.000 mmol), 2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (1860 mmol, 2.200 mmol), DMAP.pTsOH salt and DIC (0.47 mL, 3.000 mmol) were stirred in anhydrous DCM (10 mL) at room temperature for 30 min. The crude reaction mixture was evaporated in vacuo onto ~30 g flash silica gel and loaded into a loader. Purified by flash chromatography on silica gel (120 g, 5% acetone / hexane (2 CV) → 40% (20 CV)). The fractions containing the product were evaporated to dryness in vacuo. A yellow solid was obtained, 2367 mg (117% yield). NMR showed that it co-eluted with some by-product N-acylurea. It was used as is in the next step. MS (APCI): Chemical formula C 51 H 27 F 12 Calculated for NO8 (M+H) = 1010; found: 1010. 1H NMR(400MHz,TCE)δ10.39(s,1H),8.75(s,1H),8.50(s,1H),8.27(d,J=1.7Hz,2H),8.05-8.00(m,3H),7.67-7.60(m,2H),7.49 (ddd,J=8.6,6.3,2.5Hz,1H),7.42-7.37(m,2H),7.30-7.25(m,1H),7.04-6.93(m,2H),6.43(s,2H),4.03(s,2H),3.90(s,6H).

[0346] PLC-21 10-(4-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dimethoxyphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylic acid diethyl ester: 4-formyl-3-nitropropene was reacted with 4-nitropropene at room temperature under argon. ,5-dimethoxyphenyl-2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate (~80% pure, 252 mg, 0.2000 mmol), ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (77 mg, 0.4600 mmol) and pTsOH.HO (8 mg, 0.04000 mmol) were stirred in anhydrous DCE (30 mL) overnight. The reaction mixture was treated with DDQ (68 mg, 0.3000 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with EtN (0.22 mL, 1.600 mmol) and BF.OEt (0.30 mL, 2.400 mmol). The addition of Et3N (0.22 mL, 1.600 mmol) and BF3.OEt2 (0.30 mL, 2.400 mmol) was repeated, and the reaction mixture was stirred at 50°C for one hour. The crude reaction mixture was evaporated in vacuo onto ~30 g flash silica gel and loaded into a loader. Purified by flash chromatography on silica gel (120 g, 0% acetone / hexane (2CV) → 35% (15CV)). The fractions containing the product were evaporated to dryness in vacuo. An orange solid was obtained, 178 mg (65% yield). MS (APCI): Formula C 69 H 48 BF 14 N3O 11 Calcd. (M+H) = 1372; found: 1372.1 H NMR(400MHz,TCE)δ8.76(s,1H),8.51(s,1H),8.30-8.24(m,2H),8.08(s,1H ),8.06-7.98(m,3H),7.66(d,J=8.4Hz,2H),7.49(ddd,J=8.5,6.3,2.4Hz,1H ),7.41(d,J=8.3Hz,2H),7.31-7.25(m,1H),7.06-6.94(m,2H),6.56(s,2H) ,4.05(s,2H),3.75(s,6H),2.81(s,6H),1.88(s,6H),1.34(t,J=7.1Hz,6H).

[0347] Photoluminescent compound PLC-22:

[0348]

[0349] 3,5-Bis((2-ethylhexyl)oxy)phenol: Benzene-1,3,5-triol (7.567 g, 60.00 mmol), 3-(bromomethyl)heptane (16.0 mL, 90.00 mmol), and potassium carbonate (12.439 g, 90.00 mmol) were stirred in anhydrous DMF (50 mL) under argon at 70°C overnight. The reaction mixture was cooled to room temperature and partitioned between water (200 mL) and diethyl ether (200 mL). The reaction was carefully titrated with 6N HCl to pH ~5, and the layers were separated. The aqueous layer was extracted with diethyl ether (2 x 100 mL), and the combined organic layers were dried over magnesium sulfate, filtered, and evaporated to dryness. The crude reaction mixture was evaporated in vacuo onto ~40 g of flash silica gel and loaded into a cartridge. Purification was performed by flash chromatography on silica gel (0% EtOAc / hexane (2CV) → 10% (15CV)). The fractions containing the product were evaporated to dryness to give a pale yellow oil, 3.407 g (16% yield). MS (APCI): Formula C 22 H 38 Calculated for O3 (M+H) = 351; found: 351. 1 H NMR (400MHz, CDCl3) δ6.07 (s, 1H), 6.00 (d, J = 2.0Hz, 2H), 3.78 (dd, J = 5.8, 1.4Hz, 4H), 1.69 (hept, J = 6.1Hz, 2H), 1.55-1.34 (m, 8H), 0.95-0.85 (m, 12H).

[0350] (3,5-Bis((2-ethylhexyl)oxy)phenoxy)triisopropylsilane: 3,5-Bis((2-ethylhexyl)oxy)phenol (3.407 g, 9.719 mmol), TIPS-Cl (4.2 mL, 19.44 mmol), and imidazole (1.655 g, 24.30 mmol) were stirred in anhydrous DCM (25 mL) under argon at 0°C and allowed to warm slowly over the weekend. The reaction mixture was diluted with DCM (to 100 mL), washed with 6N HCl (50 mL), 10% potassium carbonate solution (50 mL), dried over magnesium sulfate, filtered, and evaporated to dryness. The crude product was dissolved in hexanes and loaded onto ~40 g flash silica gel packed in a cartridge. Purification was performed by silica gel flash chromatography (120 g, 0% EtOAc / hexanes (2 CV) → 10% (20 CV)). The fractions containing the product were evaporated to dryness in vacuo to give a pale yellow oil, 2.533 g (77% yield). MS (APCI): Formula C 31 H 58 Calculated value for O3Si (M+H) = 507; found: 507. 1 H NMR (400MHz, CDCl3) δ6.08(t,J=2.2Hz,1H),6.04(d,J=2.1Hz,2H),3.77(dd,J=5.8,1.1Hz, 4H), 1.69 (p, J = 6.1Hz, 2H), 1.52-1.21 (m, 16H), 1.11 (d, J = 7.2Hz, 18H), 0.95-0.87 (m, 12H).

[0351] 2,6-Bis((2-ethylhexyl)oxy)-4-((triisopropylsilyl)oxy)benzaldehyde: Under argon, (3,5-bis((2-ethylhexyl)oxy)phenoxy)triisopropylsilane (3.805 g, 7.507 mmol) and TMEDA (6.4 mL, 30.03 mmol) were combined in anhydrous THF (50 mL) and stirred at 0°C for five minutes. The reaction mixture was treated dropwise with nBuLi solution (1.6 M in hexanes, 23.5 mL, 37.53 mmol). The reaction mixture was stirred at 0°C for five minutes, then the cooling bath was removed and the reaction mixture was stirred at room temperature overnight. The reaction mixture was cooled to -78°C and treated dropwise with anhydrous DMF (5.8 mL, 75.07 mmol). The reaction mixture was stirred at -78°C for several minutes, then the cooling bath was removed and the reaction was allowed to warm to room temperature with stirring. Stirring was continued for one hour, after which the reaction mixture was quenched with saturated NH4Cl solution (150 mL) and partitioned with ether (200 mL). The layers were separated, and the aqueous layer was extracted with ether (100 mL). The combined organic layers were dried over magnesium sulfate, filtered, and evaporated to dryness in a vacuum. The crude product was diluted with hexane and loaded onto a loader filled with ~45 g flash silica gel. Purified by flash chromatography on silica gel (0% EtOAc / hexane (2CV) → 20% (20CV)). The fractions containing the product were evaporated to dryness in a vacuum. 3.543 g (88% yield) were obtained. MS (APCI): Chemical Formula C 32 H 58 Calculated value for O4Si(M+H)=535; found value: 535. 1 H NMR (400MHz, CDCl3) δ10.37 (s, 1H), 6.02 (s, 2H), 3.85 (dd, J = 5.6, 2.3Hz, 4H), 1.75 (h, J = 6.0Hz, 3H), 1.59-1.36 (m, 16H), 1.13 (d, J = 7.2Hz, 18H), 0.96-0.86 (m, 12H).

[0352] 2,6-Bis((2-ethylhexyl)oxy)-4-hydroxybenzaldehyde: 2,6-Bis((2-ethylhexyl)oxy)-4-((triisopropylsilyl)oxy)benzaldehyde (3.543 g, 6.624 mmol) was dissolved in anhydrous THF (50 mL) and stirred at 0 °C under argon. The reaction mixture was treated dropwise with TBAF (1.0 M / THF, 7.3 mL, 7.300 mmol), and the reaction was stirred at 0 °C for 30 minutes. The reaction was quenched with saturated NH4Cl solution (100 mL) and titrated to pH ~8 with 6N HCl solution. The reaction mixture was partitioned with 200 mL of diethyl ether, and the layers were separated. The aqueous layer was extracted with diethyl ether (100 mL), and the combined organic layers were dried over magnesium sulfate, filtered, and evaporated to dryness in vacuo. The crude product was dissolved in hexane and loaded onto a cartridge filled with ~40 g of flash silica gel. Purification was performed by flash chromatography on silica gel (120 g, 0% EtOAc / hexane (2 CV) → 20% (20 CV)). The fractions containing the product were evaporated to dryness in vacuo. 1.742 g (70% yield) was obtained. MS (APCI): Formula C 23 H 38 Calcd. for O4 (M+H) = 379; found: 379. 1 H NMR (400 MHz, acetone) δ 10.37 (s, 1H), 6.16 (s, 2H), 3.92 (dd, J = 5.4, 0.6 Hz, 4H), 1.74 (h, J = 6.0 Hz, 2H), 1.64-1.42 (m, 8H), 1.40-1.27 (m, 8H), 1.01-0.86 (m, 12H).

[0353] 3,5-bis((2-ethylhexyl)oxy)-4-formylphenyl-2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: 2,6-bis((2-ethylhexyl)oxy)-4-hydroxybenzaldehyde (379 mg, 1.000 mmol), 2-(4-(5 ,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xanthen[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (1015 mg, 1.200 mmol), DMAP.pTsOH salt (147 mg, 0.5000 mmol) and DIC (0.31 mL, 2.000 mmol) were stirred in anhydrous DCM (20 mL) for 30 minutes. The crude reaction mixture was diluted 1:1 with hexane and loaded onto a loader filled with ~50 g flash silica gel. Purified by silica gel flash chromatography (120 g, 0% EtOAc / hexane (2CV) → 20% (30CV)). The fractions containing the product were evaporated to dryness in vacuo. A yellow solid was obtained, 1.035 g (86% yield). MS (APCI): Chemical formula C 65 H 55 F 12 Calculated value for NO8 (M+H) = 1206; found: 1206. 1 H NMR (400 MHz, acetone) δ 10.47 (s, 1H), 8.77 (s, 1H), 8.61-8.56 (m, 2H), 8.52 (s, 1H), 8.36-8.32 (m, 2H), 8.24 (s, 1H), 8.20 (s, 1H), 7.63-7.57 (m, 2H), 7.55 (ddd, J = 8.5, 7.2, 1.5 Hz, 1H), 7.47-7.40 (m, 2H), 7.30 (dd, J = 8.3, 1.3 Hz, 1 H),7.13(dd,J=8.3,1.5Hz,1H),7.03(ddd,J=8.4,7.2,1.3Hz,1H),6.58(s,2H),4.07(s,2H),3.98(d,J=5.4Hz, 4H), 1.77 (hept, J=6.2Hz, 2H), 1.63-1.40 (m, 8H), 1.40-1.26 (m, 8H), 0.93 (t, J=7.5Hz, 6H), 0.91-0.86 (m, 6H).

[0354] PLC-22 10-(4-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-bis((2-ethylhexyl)oxy)phenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylic acid diethyl ester: 3,5-bis((

[0147] A mixture of 2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate (1035 mg, 0.8581 mmol), ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (316 mg, 1.888 mmol), and pTsOH.HO (16 mg, 0.08581 mmol) was stirred in anhydrous DCE (25 mL) for one hour. The reaction mixture was treated with DDQ (331 mg, 1.459 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with EtN (0.96 mL, 6.865 mmol) and BF.OEt (0.87 mL, 7.061 mmol). The addition of Et3N (0.96 mL, 6.865 mmol) and BF3.OEt2 (0.87 mL, 7.061 mmol) was repeated, and the reaction mixture was stirred at 50°C for one hour. The crude reaction mixture was evaporated in vacuo onto ~40 g flash silica gel. Purified by flash chromatography on silica gel (120 g, 0% EtOAc / hexane (2CV) → 25% (30CV)). The fractions containing the product were evaporated to dryness in vacuo. Repeat the purification to remove a small amount of impurities. An orange solid was obtained, 1.122 g (83% yield). MS (APCI): Formula C 83 H 76 BF 14 N3O 11 Calcd. (M+H) = 1569; found: 1569. 1H NMR (400MHz, acetone) δ8.77(s,1H),8.60-8.54(m,2H),8.52(s,1H),8.36-8.30(m,2H),8.24(tt,J=1.8,0.9Hz,1H),8.20(td,J=1.7,0.9Hz ,1H),7.66-7.57(m,2H),7.54(ddd,J=8.5,7.2,1.5Hz,1H),7.48-7.41(m,2H),7.29(dd,J=8.3,1.3Hz,1H),7.13(dd,J=8.4,1.5Hz,1H ),7.02(ddd,J=8.4,7.1,1.3Hz,1H),4.28(q,J=7.1Hz,4H),4.10(s,2H),3.96(dd,J=9.3,4.9Hz,2H),3.89(dd,J=9.2,5.9Hz,2H),2.7 9(s,6H),1.99-1.93(m,6H),1.51(q,J=5.9Hz,2H),1.33(t,J=7.1Hz,6H),1.25-1.16(m,4H),1.16-1.01(m,12H),0.78-0.67(m,12H).

[0355] Photoluminescent compound PLC-23:

[0356]

[0357] 3,5-Bis(3-phenylpropoxy)phenol: Benzene-1,3,5-triol (7.567 g, 60.00 mmol), (3-bromopropyl)benzene (18.2 mL, 120.0 mmol), and potassium carbonate (16.585 g, 120.0 mmol) were stirred in anhydrous DMF (50 mL) under argon at 50°C for three hours. The reaction was cooled to room temperature and partitioned between water (200 mL) and diethyl ether (200 mL). The reaction was carefully titrated with 6N HCl to pH ~6.5, and the layers were separated. The aqueous layer was extracted with diethyl ether (2 x 100 mL), and the combined organic layers were dried over magnesium sulfate, filtered, and evaporated to dryness in vacuo. The crude reaction mixture was diluted with diethyl ether and loaded onto ~45 g of flash silica gel packed in a cartridge. Purify by flash chromatography on silica gel (220 g, 0% EtOAc / hexane (2 CV) → 25% (20 CV)). The fractions containing the product were evaporated to dryness in vacuo. A waxy off-white solid was obtained, 5.775 g (27% yield). MS (APCI): Formula C 24 H 26Calculated value for O3 (M+H) = 363; found: 363. 1H NMR (400 MHz, CD2Cl2) δ 7.34-7.25 (m, 4H), 7.25-7.14 (m, 6H), 6.05 (q, J = 1.9 Hz, 1H), 5.99 (t, J = 1.7 Hz, 2H), 4.93 (d, J = 1.3 Hz, 1H), 3.91 (t, J = 6.3 Hz, 4H), 2.78 (t, J = 7.7 Hz, 4H), 2.13-2.02 (m, 4H).

[0358] 4-Hydroxy-2,6-bis(3-phenylpropoxy)benzaldehyde: 3,5-bis(3-phenylpropoxy)phenol (5.770 g, 15.92 mmol) was dissolved in anhydrous DCM (5 mL) and treated with POCl3 (3.0 mL, 31.84 mmol) at room temperature under argon. The reaction mixture was stirred for ten minutes, then cooled to 0°C and treated dropwise with anhydrous DMF (1.84 mL, 23.88 mmol) with stirring. The reaction mixture was stirred at 0°C and allowed to slowly warm to room temperature overnight. The reaction mixture was quenched with crushed ice and then diluted with water to ~100 mL. The reaction was carefully quenched with 10% aqueous potassium carbonate solution to pH ~6. The reaction mixture was partitioned with DCM (100 mL) and the layers were separated. The aqueous layer was extracted with DCM (2×100 mL), and the combined organic layers were dried over magnesium sulfate, filtered and evaporated to dryness. The crude product was diluted with ether and loaded onto ~50 g of flash silica gel packed in a loader. Purification was performed by flash chromatography on silica gel (220 g, 0% EtOAc / hexane (2 CV) → 20% (20 CV) → 50% (0 CV) → isocratic 50%). The fractions containing the product were evaporated to dryness in vacuo. 1.341 g (22% yield) was obtained. MS (APCI): Formula C 25 H 26 Calcd. for O4 (M+H) = 391; Found: 391. The compound was a 1:1 mixture with an inseparable by-product and was used as such in the next step.

[0359] 4-Formyl-3,5-bis(3-phenylpropoxy)phenyl 2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: 4-Hydroxy-2,6-bis(3-phenylpropoxy)benzaldehyde (mixture, 391 mg, 1.000 mmol), 2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate were added to the mixture. 1-Bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (1015 mg, 1.200 mmol), DMAP.pTsOH salt (29 mg, 0.1000 mmol) and DIC (0.313 mL, 2.000 mmol) were stirred in anhydrous DCM (15 mL) for 30 minutes. The crude reaction mixture was diluted 1:1 with hexane and loaded onto a cartridge filled with ~50 g flash silica gel. Purification was performed by silica gel flash chromatography (120 g, 0% EtOAc / hexane (2CV) → 10% (20CV)). The fractions containing the product were evaporated to dryness in vacuo. A yellow solid was obtained, 1034 mg (85% yield). MS (APCI): Formula C 67 H 43 F 12 Calculated value for NO8 (M+H) = 1218; found: 1218. 1 H NMR (400MHz, CD2Cl2) δ10.49(s,1H),8.77(s,1H),8.53(s,1H),8.30(dd,J=1.7,0.9Hz,2H ),8.09(tt,J=1.5,0.7Hz,1H),8.05(dd,J=1.9,0.9Hz,3H),7.61-7.55(m,2H),7.47(ddd, J=8.5,7.0,1.7Hz,1H),7.39-7.33(m,2H),7.33-7.14(m,12H),7.05-6.93(m,2H),6.38(s ,2H),4.02(t,J=6.2Hz,4H),3.99(s,2H),2.85(dd,J=8.3,6.8Hz,4H),2.19-2.08(m,4H).

[0360] PLC-23 10-(4-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xanthen[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-bis(3-phenylpropoxy)phenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylic acid diethyl ester:

[0361] 4-Formyl-3,5-bis(3-phenylpropoxy)phenyl 2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate (1033 mg, 0.8481 mmol), ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (326 mg, 1.951 mmol) and pTsOH.HO (16 mg, 0.08481 mmol) were stirred in anhydrous DCE (25 mL) under argon at room temperature for one hour. The reaction mixture was treated with DDQ (347 mg, 1.527 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with Et3N (0.95mL, 6.785mmol) and BF3.OEt2 (1.25mL, 10.18mmol). The addition of Et3N (0.95mL, 6.785mmol) and BF3.OEt2 (1.25mL, 10.18mmol) was repeated, and the reaction mixture was stirred at 50°C for one hour. The crude reaction mixture was evaporated in vacuo onto ~40g flash silica gel and loaded into a loader. Purified by silica gel flash chromatography (220g, 0% EtOAc / DCM (2CV)→1% (20CV)). The fractions containing the product were evaporated to dryness in vacuo. An orange solid was obtained, 533mg (40% yield). MS (APCI): Chemical formula C 85 H 64 BF 14 N3O 11 Calcd. (M+H) = 1580; found: 1580. 1H NMR (400MHz, CD2Cl2) δ8.78(s,1H),8.53(s,1H),8.31(t,J=1.1Hz,2H),8.09(td,J=1.8,0.9Hz,1H),8.05(dt,J=1.9, 0.9Hz,3H),7.64-7.58(m,2H),7.47(ddd,J=8.5,7.0,1.7Hz,1H),7.40-7.34(m,2H),7.27(dd,J=8.3,1.2Hz,1H),7.23 -7.16(m,4H),7.15-7.09(m,2H),7.02(dd,J=8.4,1.7Hz,1H),7.00-6.93(m,5H),6.51(s,2H),4.25(q,J=7.1Hz,4H),4 .02(s,2H),3.93(t,J=6.0Hz,4H),2.80(s,6H),2.45(dd,J=8.5,6.7Hz,4H),1.94-1.84(m,4H),1.30(t,J=7.1Hz,6H).

[0362] Photoluminescent compound PLC-24:

[0363]

[0364] 3,5-Bis(cyclohexylmethoxy)phenol: Benzene-1,3,5-triol (15.763 g, 125.0 mmol), (bromomethyl)cyclohexane (21.8 mL, 156.3 mmol), and potassium carbonate (34.553 g, 250.0 mmol) were combined in anhydrous DCM (100 mL) and heated at 70°C overnight under argon. The reaction mixture was cooled to room temperature, diluted with water (200 mL), and extracted with diethyl ether (3 x 125 mL). The combined organic layers were washed with water (200 mL), dried over magnesium sulfate, filtered, and evaporated to dryness in vacuo. The crude reaction mixture was evaporated in vacuo onto ~50 g flash silica gel and loaded into a cartridge. Purification was performed by silica gel flash chromatography (330 g, 0% EtOAc / hexane (2 CV) → 25% (10 CV)). Fractions containing the product were evaporated to dryness in vacuo. Obtained 3.157 g (7.9% yield). MS (APCI): Chemical formula C 20 H 30 Calcd. for O3 (M+H) = 319; found: 319. 1H NMR (400MHz, TCE) δ6.07 (t, J = 2.1 Hz, 1H), 3.69 (d, J = 6.3 Hz, 4H), 1.92-1.65 (m, 10H), 1.42-1.10 (m, 9H), 0.96-0.76 (m, 2H).

[0365] 2,6-Bis(cyclohexylmethoxy)-4-hydroxybenzaldehyde: Under argon, 3,5-bis(cyclohexylmethoxy)phenol (3.150 g, 9.891 mmol) was dissolved in anhydrous DCM (6 mL) and stirred at room temperature. The reaction mixture was treated with POCl (1.84 mL, 3.033 mmol) and stirred at room temperature for five minutes, then cooled to 0°C and treated dropwise with anhydrous DMF (0.92 mL, 11.87 mmol). The reaction mixture was stirred at 0°C for one hour, then the contents of the reaction were poured into ~100 mL of crushed ice and rinsed with a small amount of acetone. The reaction mixture was titrated with 10% potassium carbonate solution to a pH of ~6-7, then extracted with DCM (100 mL, 2 x 50 mL). The combined organic layers were dried over magnesium sulfate, filtered, and evaporated to dryness in vacuo. The crude product was diluted with a small amount of DCM and loaded onto ~50 g of flash silica gel packed in a loader. Purification was performed by flash chromatography on silica gel (120 g, 0% EtOAc / hexane (2 CV) → 100% EtOAc (15 CV)). The fractions containing the product were evaporated to dryness in vacuo. 175 mg (5.1% yield) was obtained. MS (APCI): Formula C 21 H 30 Calcd. for O4 (M+H) = 347; found: 347. 1 H NMR (400MHz, TCE) δ10.32 (s, 1H), 6.02 (s, 2H), 3.76 (d, J = 6.0Hz, 4H), 1.96-1.81 (m, 7H), 1.80-1.62 (m, 9H), 1.40-1.15 (m, 8H), 1.13-0.94 (m, 5H).

[0366] 2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: 2,6-bis(cyclohexylmethoxy)-4-hydroxybenzaldehyde (175 mg, 0.5051 mmol), 2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate were added to the mixture at room temperature. 1-H-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (430 mg, 0.6061 mmol), DMAP.pTsOH salt (15 mg, 0.05051 mmol) and DIC (0.158 mL, 1.010 mmol) were stirred in anhydrous DCM (10 mL) for 30 minutes. The crude reaction mixture was loaded onto ~45 g flash silica gel packed in a loader by dissolving in DCM. Purification was performed by silica gel flash chromatography (120 g, 0% EtOAc / DCM (2CV) → 5% (10CV)). The fractions containing the product were evaporated to dryness in vacuo. A yellow solid was obtained, 449 mg (86% yield). MS (APCI): Chemical formula C 61 H 49 Calculated for F6NO8 (M+H) = 1038; found: 1038. 1 H NMR(400MHz,TCE)δ10.44(s,1H),8.71(s,1H),8.48(s,1H),7.95-7.81(m,6H), 7.72-7.58(m,4H),7.48-7.36(m,3H),7.31(dd,J=8.3,1.3Hz,1H),7.10(dd,J= 8.3,1.5Hz,1H),6.96(ddd,J=8.4,7.1,1.3Hz,1H),6.37(s,2H),4.02(s,2H),3 .81(d,J=5.9Hz,4H),1.92-1.82(m,6H),1.79-1.51(m,7H),1.45-0.96(m,10H).

[0367] PLC-24 10-(2,6-bis(cyclohexylmethoxy)-4-(2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)phenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylic acid diethyl ester: 3,5-bis(cyclohexylmethoxy)-4-(2-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)phenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylate was reacted under argon at room temperature.

[0147] A mixture of 4-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate (445 mg, 0.4287 mmol), ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (179 mg, 1.072 mmol), and pTsOH.HO (8 mg, 0.04287 mmol) was stirred in anhydrous DCE (25 mL) for one hour. The reaction mixture was treated with DDQ (175 mg, 0.7716 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with EtN (0.48 mL, 3.430 mmol) and BF.OEt (0.64 mL, 5.144 mmol). The addition of Et3N (0.48 mL, 3.430 mmol) and BF3.OEt2 (0.64 mL, 5.144 mmol) was repeated, and the reaction mixture was stirred at 50°C for one hour. The crude reaction mixture was evaporated in vacuo onto ~50 g flash silica gel and loaded into a loader. Purified by flash chromatography on silica gel (120 g, 100% hexane / toluene, EtOAc modifier, 0.1%→1%→2%→3% step gradient). The fractions containing the product were evaporated to dryness in vacuo. An orange solid was obtained, 446 mg (74% yield). MS (APCI): Formula C 79 H 70 BF8N3O 11 Calcd. (M+H) = 1401; found: 1401. 1H NMR(400MHz,TCE)δ10.44(s,1H),8.71(s,1H),8.48(s,1H),7.95-7.81(m,6H), 7.72-7.58(m,4H),7.48-7.36(m,3H),7.31(dd,J=8.3,1.3Hz,1H),7.10(dd,J= 8.3,1.5Hz,1H),6.96(ddd,J=8.4,7.1,1.3Hz,1H),6.37(s,2H),4.02(s,2H),3 .81(d,J=5.9Hz,4H),1.92-1.82(m,6H),1.79-1.51(m,7H),1.45-0.96(m,10H).

[0368] Photoluminescent compound PLC-25:

[0369]

[0370]

[0266] 4-Formyl-3,5-dimethoxyphenyl-2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: 4-Hydroxy-2,6-dimethoxybenzaldehyde (456 mg, 2.500 mmol), 2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (2129 mg, 3.000 mmol), DMAP.pTsOH salt (74 mg, 0.2500 mmol) and DIC (0.783 mL, 5.000 mmol) were stirred in anhydrous DCM (30 mL) at room temperature for 30 min. The crude reaction mixture was loaded onto ~50 g of flash silica gel loaded in a loader. Purification was performed by flash chromatography on silica gel (120 g, 0% EtOAc / DCM (2 CV) → 15% (20 CV)). The fractions containing the product were evaporated to dryness in vacuo. A yellow solid was obtained, 1956 mg (90% yield). MS (APCI): Formula C 49 H 29 Calcd. for F6NO8 (M+H) = 874; found: 874. 1H NMR(400MHz,TCE)δ10.39(s,1H),8.71(s,1H),8.48(s,1H),7.95-7.82(m,6H),7.71-7.59(m,4H),7.47-7.37(m,3H),7.31(d d,J=8.3,1.3Hz,1H),7.10(dd,J=8.3,1.5Hz,1H),6.96(ddd,J=8.4,7.2,1.4Hz,1H),6.44(s,2H),4.04(s,2H),3.90(s,6H).

[0371] PLC-25 10-(4-(2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xanthen[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dimethoxyphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylic acid diethyl ester:

[0372] 4-Formyl-3,5-dimethoxyphenyl-2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate (1950 mg, 2.232 mmol), ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (933 mg, 5.579 mmol), and pTsOH.HO (43 mg, 0.2232 mmol) were stirred in anhydrous DCE (100 mL) under argon at room temperature for one hour. The reaction mixture was treated with DDQ (912 mg, 4.017 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with Et3N (2.5mL, 17.85mmol) and BF3.OEt2 (3.31mL, 26.78mmol). The addition of Et3N (2.5mL, 17.85mmol) and BF3.OEt2 (3.31mL, 26.78mmol) was repeated, and the reaction mixture was stirred at 50°C for one hour. The crude reaction mixture was cooled to room temperature and evaporated in vacuo onto ~55g flash silica gel. Purified by silica gel flash chromatography (120g, 100% toluene / hexane, EtOAc modifier, 2%→4% step gradient). The fractions containing the product were evaporated to dryness in vacuo. An orange solid was obtained, 2080mg (75% yield). MS (APCI): Chemical Formula C 67 H 50 BF8N3O 11Calcd. (M+H) = 1236; found: 1236. 1 H NMR(400MHz,TCE)δ8.62(s,1H),8.39(s,1H),7.87-7.72(m,6H),7.58(dd,J =8.4,2.3Hz,4H),7.40-7.29(m,3H),7.22(dd,J=8.2,1.4Hz,1H),7.01(dd, J=8.3,1.6Hz,1H),6.87(ddd,J=8.4,7.1,1.4Hz,1H),4.20(q,J=7.1Hz,4H) ,3.96(s,2H),3.67(s,6H),2.73(s,6H),1.80(s,6H),1.26(t,J=7.1Hz,6H).

[0373] Photoluminescent compound PLC-26:

[0374]

[0375] 2,6-Bis(2-ethylhexyl)-4-hydroxybenzaldehyde: 2,6-Dibromo-4-hydroxybenzaldehyde (380 mg, 1.358 mmol) was dissolved in anhydrous THF (25 mL) and treated with Pd(dppf)Cl2 (199 mg, 0.2716 mmol) and stirred at room temperature under argon. The solution was sparged with argon, followed by the addition of (2-ethylhexyl)zinc(II) bromide (0.5 M in THF, 16.3 mL, 8.148 mm), and the reaction mixture was stirred at room temperature for five minutes. The reaction mixture was heated at 40°C overnight. The reaction mixture was cooled to room temperature and quenched with saturated NH4Cl solution (100 mL) and extracted with ethyl acetate (100 mL, 2 x 50 mL). The combined organic layers were dried over magnesium sulfate, filtered, and evaporated to dryness. The crude product was evaporated in vacuo onto ~40 g flash silica gel and loaded into a cartridge. Purify by flash chromatography on silica gel (120 g, 0% EtOAc / hexane (2 CV) → 30% (20 CV)). The fractions containing the product were evaporated to dryness in vacuo. An off-white solid was obtained, 247 mg (52% yield). MS (APCI): Formula C 23 H 38 Calcd. for O2 (M+H) = 347; found: 347. 1 H NMR (400 MHz, acetone) δ 10.41 (s, 1H), 6.62 (s, 2H), 2.89 (dt, J = 7.3, 5.1 Hz, 4H), 1.54 (p, J = 6.5 Hz, 2H), 1.39-1.13 (m, 16H), 0.92-0.80 (m, 12H).

[0376] 2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: 2,6-bis(2-ethylhexyl)-4-hydroxybenzaldehyde (247 mg, 0.7127 mmol), 2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate were added to the mixture. (3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (723 mg, 0.8553 mmol), DMAP.pTsOH salt (21 mg, 0.07127 mmol) and DIC (0.223 mL, 1.425 mmol) were stirred in anhydrous DCM (10 mL) for 30 minutes. The crude reaction mixture was diluted 1:1 with hexane and loaded onto a cartridge filled with ~50 g flash silica gel. Purification was performed by silica gel flash chromatography (120 g, 0% EtOAc / hexane (2CV) → 20% (30CV)). The fractions containing the product were evaporated to dryness in vacuo. A yellow solid was obtained, 841 mg (100% yield). MS (APCI): Formula C 65 H 55 F 12 Calculated for NO6 (M+H) = 1174; found: 1174. 1 H NMR (400 MHz, acetone) δ 10.55 (s, 1H), 8.77 (s, 1H), 8.59 (d, J = 1.6 Hz, 2H), 8.53 (s, 1H), 8.35 (d, J = 1.6 Hz, 2H), 8.24 (s, 1H), 8.20 (s, 1H), 7.61 (d, J = 8.3 Hz, 3H), 7.55 (ddd, J = 8.5, 7.2, 1.5 Hz, 1H), 7.46-7. 41(m,2H),7.31(dd,J=8.3,1.3Hz,1H),7.14(dd,J=8.4,1.5Hz,1H),7.07-6.98(m,3H),4.09(s,2H ), 2.94 (dt, J = 7.2, 2.5Hz, 4H), 1.54 (q, J = 6.2Hz, 2H), 1.40-1.22 (m, 16H), 0.86 (q, J = 7.0Hz, 12H).

[0377] PLC-26 10-(4-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-bis(2-ethylhexyl)phenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylic acid diethyl ester): Under argon, 3,5- Bis(2-ethylhexyl)-4-formylphenyl-2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate (837 mg, 0.7127 mmol), ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (274 mg, 1.639 mmol) and pTsOH.HO (14 mg, 0.07127 mmol) were stirred in anhydrous DCE (25 mL) overnight. The reaction mixture was cooled to room temperature and treated with DDQ (275 mg, 1.212 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with Et3N (0.80 mL, 5.702 mmol) and BF3.OEt2 (1.06 mL, 8.552 mmol). The addition of Et3N (0.80 mL, 5.702 mmol) and BF3.OEt2 (1.06 mL, 8.552 mmol) was repeated, and the reaction mixture was stirred at 50°C for one hour. The reaction mixture was evaporated onto ~45 g flash silica gel and evaporated to dryness in vacuo. Purified by flash chromatography on silica gel (120 g, 0% EtOAc / toluene (2CV) → 2% (30CV)). The fractions containing the product were evaporated to dryness in vacuo. An orange solid was obtained, 419 mg (38% yield). MS (APCI): Formula C 83 H 76 BF 14 Calculated for N3O9 (M+H) = 1537; found: 1537. 1H NMR (400 MHz, acetone) δ 8.76 (s, 1H), 8.59-8.56 (m, 2H), 8.52 (s, 1H), 8.34 (d, J = 1.7 Hz, 2H), 8.24 (dq, J = 1.9, 1.0 Hz, 1H), 8.20 (td, J = 1.7, 0.9 Hz, 1H), 7.68-7.59 (m, 2H), 7.54 (ddd, J = 8.5, 7.2, 1.6 Hz, 1H), 7.50-7.42 (m, 2H), 7.29 (dd, J = 8.3, 1.2 Hz, 1H),7.17(s,2H),7.12(dd,J=8.3,1.5Hz,1H),7.02(ddd,J=8.4,7.1,1.3Hz,1H),4.28(q,J=7.1Hz,4H),4.12(d,J=2.0H z,2H),2.82(s,6H),2.56-2.36(m,4H),1.78(t,J=2.2Hz,6H),1.38-0.91(m,22H),0.83-0.75(m,6H),0.73-0.61(m,6H).

[0378] Photoluminescent compound PLC-27:

[0379]

[0380] 2,6-Dicyclopropyl-4-hydroxybenzaldehyde: Zinc chloride (2726 mg, 20.00 mmol) was heated at 150°C under vacuum for one hour, then cooled to room temperature under an argon atmosphere. To the salt was added anhydrous THF (100 mL), followed by a solution of cyclopropylmagnesium bromide (1.0 M in 2-methylTHF, 20.0 mL) and stirred overnight at room temperature. Pd(dppf)Cl2 (293 mg, 0.4000 mmol) was added to the flask, followed by 2,6-dibromo-4-hydroxybenzaldehyde (560 mg, 2.000 mmol), and the reaction mixture was stirred at 40°C under argon for four hours. The reaction mixture was cooled to room temperature, then treated with saturated NH4Cl solution (50 mL), followed by 6N The mixture was quenched with HCl (25 mL). The reaction mixture was extracted with ethyl acetate (100 mL, 3×50 mL). The combined organic layers were dried over magnesium sulfate, filtered, and evaporated to dryness in vacuo. The crude product was evaporated in vacuo onto ~40 g flash silica gel and loaded into a loader. Purified by flash chromatography on silica gel (120 g, 0% acetone / hexane (2CV) → 40% (20CV)). The fractions containing the product were evaporated to dryness in vacuo. An off-white solid was obtained, 120 mg (30% yield). MS (APCI): Chemical Formula C 13 H 14Calculated for O2 (M+H) = 203; found: 203. 1 H NMR (400MHz, TCE) δ10.87 (s, 1H), 6.40 (s, 2H), 2.60 (tt, J = 8.4, 5.4Hz, 2H), 1.09-0.95 (m, 4H), 0.71 (dd, J = 5.5, 1.8Hz, 4H).

[0381] 3,5-Dicyclopropyl-4-formylphenyl-2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: 2,6-dicyclopropyl-4-hydroxybenzaldehyde (119 mg, 0.5884 mmol), 2-(4-(5,11-bis(3,5 -bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xanthen[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (647 mg, 0.7649 mmol), DMAP.pTsOH salt (173 mg, 0.5884 mmol) and DIC (0.66 mL, 1.177 mmol) were stirred in anhydrous DCM (10 mL) for 30 minutes. The reaction mixture was diluted 1:1 with hexane and loaded onto a cartridge filled with ~45 g flash silica gel. Purification was performed by silica gel flash chromatography (0% acetone / hexane (2CV) → 40% (20CV)). The fractions containing the product were evaporated to dryness in vacuo. A yellow solid was obtained, 252 mg (42% yield). MS (APCI): Chemical formula C 55 H 31 F 12 Calculated for NO6 (M+H) = 1030; found: 1030. 1 H NMR(400MHz,TCE)δ10.96(s,1H),8.76(s,1H),8.51(s,1H),8.27(s,5H),8.07( s,2H),8.03(s,6H),7.61(d,J=8.0Hz,4H),7.49(t,J=7.7Hz,2H),7.38(d,J=8. 1Hz,4H),7.28(d,J=8.2Hz,2H),7.00(d,J=6.1Hz,4H),6.74(s,2H),4.00(s,2H ), 2.53 (td, J = 8.7, 4.4Hz, 2H), 1.05 (dt, J = 10.9, 3.1Hz, 4H), 0.81-0.67 (m, 4H).

[0382] PLC-27 10-(4-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dicyclopropylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylic acid diethyl ester: 3,5- Dicyclopropyl-4-formylphenyl-2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate (251 mg, 0.2075 mmol), ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (80 mg, 0.4772 mmol), and pTsOH.HO (4 mg, 0.02075 mmol) were stirred in anhydrous DCE (25 mL) overnight. The reaction mixture was treated with DDQ (240 mg, 1.059 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with EtN (0.66 mL, 4.701 mmol) and BF.OEt (0.87 mL, 7.061 mmol). The addition of Et3N (0.66 mL, 4.701 mmol) and BF3.OEt2 (0.87 mL, 7.061 mmol) was repeated, and the reaction mixture was stirred at 50°C for one hour. The reaction mixture was cooled to room temperature and evaporated in vacuo onto ~35 g flash silica gel. Purified by flash chromatography on silica gel (120 g, 0% EtOAc / hexane (2CV) → 35% (20CV)). The fractions containing the product were evaporated to dryness in vacuo. An orange solid was obtained, 127 mg (44% yield). MS (APCI): Formula C 73 H 52 BF 14 Calculated for N3O9 (M+H) = 1392; found: 1392. 1H NMR (400 MHz, acetone) δ 8.77 (s, 1H), 8.63-8.57 (m, 2H), 8.53 (s, 1H), 8.38-8.32 (m, 2H), 8.26-8.22 (m, 1H), 8.22-8.18 (m, 1H), 7.64-7.58 (m, 2H), 7.54 (ddd, J = 8.5, 7.2, 1.5 Hz, 1H), 7.47-7.39 (m, 2H), 7.30 (dd, J = 8.3, 1.2 Hz, 1H), 7. 13(dd,J=8.3,1.5Hz,1H),7.02(ddd,J=8.4,7.2,1.3Hz,1H),6.73(s,2H),4.29(q,J=7.1Hz,4H),4.07(s,2H),2. 81(s,6H),1.86(s,6H),1.73(tt,J=8.3,5.1Hz,2H),1.34(t,J=7.1Hz,6H),0.90-0.80(m,4H),0.74-0.64(m,4H).

[0383] Photoluminescent compound PLC-30:

[0384]

[0385] 4-Hydroxy-2,6-dipentylbenzaldehyde: 2,6-dibromo-4-hydroxybenzaldehyde (190 mg, 0.6788 mmol), pentylboronic acid (630 mg, 5.430 mmol), Pd(dppf)Cl2 (99 mg, 0.1358 mmol) and cesium carbonate (885 mg, 2.715 mmol) were combined in THF (10 mL) and water (1 mL) in a 30 mL microwave vial. The vial was sealed and heated at 130 ° C for two hours in a microwave synthesizer. The crude reaction mixture was evaporated in vacuo onto ~30 g flash silica gel and loaded into a loader. Purified by silica gel flash chromatography (120 g, 0% acetone / hexane (2CV) → 40% (20CV)). The fractions containing the product were evaporated to dryness in vacuo. The compound was impure (by NMR), but was used as is in the next step. MS (APCI): Chemical formula C 15 H 22 Calculated for O2 (M+H) = 235; found: 235.

[0386] 4-Formyl-3,5-dipentylphenyl-2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: 4-hydroxy-2,6-dipentylbenzaldehyde (75 mg, 0.2859 mmol), 2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate were added to the mixture at room temperature. (Trifluoromethyl)phenyl)-1,3-dioxo-1H-xanthen[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (483 mg, 0.5719 mmol), DMAP.pTsOH salt (84 mg, 0.2859 mmol) and DIC (0.134 mL, 0.8575 mmol) were combined in anhydrous DCM (10 mL) and stirred for 30 minutes. The crude reaction mixture was evaporated in vacuo onto ~25 g flash silica gel and loaded into a loader. Purification was performed by silica gel flash chromatography (120 g, 0% acetone / hexane (2CV) → 30% (25CV)). The fractions containing the product were evaporated to dryness in vacuo. A yellow solid was obtained, 193 mg (62% yield). MS (APCI): Chemical formula C 57 H 39 F 12 Calculated value for NO6 (M+H) = 1062; found: 1062. 1 H NMR(400MHz,TCE)δ10.49(s,1H),8.76(s,1H),8.51(s,1H),8.27(d,J=1.5Hz, 2H),8.07(s,1H),8.03(s,3H),7.62(d,J=8.3Hz,2H),7.49(ddd,J=8.5,6.1,2. 5Hz,1H),7.39(d,J=8.2Hz,2H),7.28(d,J=8.2Hz,1H),6.93(s,2H),4.01(s,2H ),3.01-2.79(m,4H),1.65-1.45(m,4H),1.50-1.30(m,8H),1.03-0.81(m,6H).

[0387] PLC-28 10-(4-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dipentylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylic acid diethyl ester: 4-formyl-3-nitropropene was reacted with 4-nitropropene at room temperature under argon. ,5-dipentylphenyl-2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate (192 mg, 0.1762 mmol), ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (65 mg, 0.3875 mmol) and pTsOH.HO (3.3 mg, 0.01762 mmol) were combined in anhydrous DCE (15 mL) and stirred overnight. The reaction mixture was treated with DDQ (60 mg, 0.2642 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with EtN (0.20 mL, 1.409 mmol) and BF.OEt (0.26 mL, 2.114 mmol). The addition of Et3N (0.20 mL, 1.409 mmol) and BF3.OEt2 (0.26 mL, 2.114 mmol) was repeated, and the reaction mixture was stirred at 50°C for one hour. The crude reaction mixture was evaporated in vacuo onto ~30 g flash silica gel. Purification was performed by flash chromatography on silica gel (120 g, 0% acetone / hexane (2CV) → 30% (25CV)). The fractions containing the product were evaporated to dryness in vacuo. An orange solid was obtained, 166 mg (65% yield). MS (APCI): Formula C 75 H 60 BF 14 Calculated for N3O9 (M+H) = 1424; found: 1424. 1H NMR(400MHz,TCE)δ8.76(s,1H),8.51(s,1H),8.27(s,2H),8.08(s,1H),8.03(d,J=1.8Hz,3H),7. 66(d,J=8.4Hz,2H),7.49(ddd,J=8.5,6.2,2.5Hz,1H),7.44-7.35(m,2H),7.28(d,J=8.2Hz,1H), 7.08(s,2H),7.06-6.92(m,2H),4.27(q,J=7.1Hz,4H),4.05(s,2H),2.85(s,6H),2.50-2.27(m,4 H), 1.71 (s, 6H), 1.57-1.42 (m, 4H), 1.33 (t, J = 7.1Hz, 6H), 1.25-1.11 (m, 8H), 0.83-0.73 (m, 6H).

[0388] Photoluminescent compound PLC-29:

[0389]

[0390] 2,6-Bis(cyclohexylmethyl)-4-hydroxybenzaldehyde: 2,6-Dibromo-4-hydroxybenzaldehyde (1120 mg, 4.000 mmol) and Pd(dppf)Cl2 (585 mg, 0.8000 mmol) were combined in anhydrous THF (50 mL) under argon and stirred at room temperature. The reaction mixture was bubbled thoroughly with argon, followed by the addition of (cyclohexylmethyl)zinc(II) bromide (0.5 M in THF, 32.0 mL, 16.00 mmol) and further bubbled with argon. The reaction mixture was stirred at room temperature for five minutes, then heated to 40°C overnight. The reaction mixture was cooled to room temperature and partitioned between water (100 mL) and diethyl ether (100 mL). The layers were separated, and the aqueous layer was extracted with diethyl ether (100 mL). The combined organic layers were dried over magnesium sulfate, filtered, and evaporated to dryness in vacuo. The crude reaction mixture was evaporated in vacuo onto ~20 g flash silica gel and loaded into a loader. Purified by flash chromatography on silica gel (0% EtOAc / hexane (2 CV) → 20% (15 CV)). The fractions containing the product were evaporated to dryness in vacuo. An off-white solid was obtained, 833 mg (66% yield). MS (APCI): Formula C 21 H 30 Calculated for O2 (M+H) = 315; found: 315. 1H NMR (400MHz, CD2Cl2) δ10.38(s,1H),6.51(s,2H),5.45(s,1H),2.80(d,J=7.0Hz,4H),1.75-1 .56(m,10H),1.47(ddtd,J=13.5,10.5,7.0,3.4Hz,2H),1.22-1.08(m,6H),1.06-0.91(m,4H).

[0391] 3,5-bis(cyclohexylmethyl)-4-formylphenyl-2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: 2,6-bis(cyclohexylmethyl)-4-hydroxybenzaldehyde (409 mg, 1.300 mmol), 2-(4-(5,11-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate were added to the mixture at room temperature. (3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xanthen[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (1319 mg, 1.560 mmol), DMAP.pTsOH salt (38 mg, 0.1300 mmol) and DIC (0.407 mL, 2.600 mmol) were stirred in anhydrous DCM (10 mL) for 30 minutes. The crude reaction mixture was diluted with 3 portions of hexane and loaded onto ~45 g flash silica gel packed in a loader. Purification was performed by silica gel flash chromatography (120 g, isocratic DCM). The fractions containing the product were evaporated to dryness in vacuo. A yellow solid was obtained, 1436 mg (97% yield). MS (APCI): Formula C 63 H 47 F 12 Calculated for NO6 (M+H) = 1142; found: 1142. 1H NMR(400MHz,CD2Cl2)δ10.49(s,1H),8.78(s,1H),8.53(s,1H),8.31(dd,J=1.7,0.9Hz,2H),8.13-8.07(m,1H),8.05(t,J=2.0Hz,3H),7.63-7.56(m,2H),7.47(ddd,J=8.5,7.0,1.7Hz,1H),7.41-7.33(m,2H),7.26(dd,J=8.3,1.2Hz,1H),7.01(dd,J=8.3,1.5Hz,1H),6.97(ddd,J=8.3,7.0,1.3Hz,1H),6.89(s,2H),4.02(s,2H),1.77-1.58(m,10H),1.48(dtd,J=10.7,7.4,3.6Hz,2H),1.25-1.10(m,6H),0.99(qd,J=10.5,5.6Hz,4H)。

[0392] PLC-29 10-(4-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-bis(cyclohexylmethyl)phenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylic acid diethyl ester: 3,5-bis(trifluoromethyl)phenyl was reacted with 1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-bis(cyclohexylmethyl)phenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylate under argon at room temperature.

[00145] 1,4-Dimethyl-1,4-difluoro-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate (1435 mg, 1.257 mmol), ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (483 mg, 2.890 mmol), and pTsOH.HO (24 mg, 0.1257 mmol) were stirred in anhydrous DCE (30 mL) for one hour. The reaction mixture was treated with DDQ (513 mg, 2.262 mmol) and stirred at room temperature for 30 minutes. Additional DDQ (86 mg, 0.3371 mmol) was added twice at 15 and 30 minutes, and the reaction mixture was then stirred for an additional 30 minutes. The reaction was then treated with Et3N (1.4 mL, 10.05 mmol) and BF3.OEt2 (1.87 mL, 15.08 mmol). The addition of Et3N (1.4 mL, 10.05 mmol) and BF3.OEt2 (1.87 mL, 15.08 mmol) was repeated, and the reaction mixture was stirred at 50°C for one hour. The reaction mixture was cooled to room temperature and evaporated in vacuo onto ~30 g flash silica gel and loaded into a loader. Purified by silica gel flash chromatography (220 g, 0% EtOAc / DCM (2CV) → 3.5% (20CV) → isocratic 3.5%). The fractions containing the product were evaporated to dryness in vacuo. An orange solid was obtained, 1182 mg (63% yield). MS (APCI): Chemical formula C 81 H 68 BF 14 Calculated for N3O9 (M+H) = 1504; found: 1504. 1H NMR (400MHz, acetone) δ8.77(s,1H),8.59(d,J=1.7Hz,2H),8.53(s,1H),8.37-8.31(m,2H),8.24(td,J=1.7,0.9Hz,1H),8.20(t d,J=1.7,0.9Hz,1H),7.68-7.59(m,2H),7.55(ddd,J=8.5,7.2,1.5Hz,1H),7.48-7.42(m,2H),7.30(dd,J=8.3,1.2Hz,1H), 7.17(s,2H),7.14(dd,J=8.3,1.5Hz,1H),7.03(ddd,J=8.4,7.2,1.3Hz,1H),4.28(q,J=7.1Hz,4H),4.12(s,2H),2.82(s,6H ), 2.39 (d, J = 7.0Hz, 4H), 1.76 (s, 6H), 1.67-1.52 (m, 10H), 1.53-1.41 (m, 2H), 1.33 (t, J = 7.1Hz, 6H), 1.08 (d, J = 6.7Hz, 6H).

[0393] Photoluminescent compound PLC-30:

[0394]

[0395] 2,6-Dicyclohexyl-4-hydroxybenzaldehyde: Under argon, 2,6-dibromo-4-hydroxybenzaldehyde (1120 mg, 4.000 mmol) and Pd(dppf)Cl2 (585 mg, 0.8000 mmol) were combined in anhydrous THF (50 mL) and stirred at room temperature. The reaction mixture was bubbled thoroughly with argon, followed by the addition of cyclohexylzinc(II) bromide (0.5 M in THF, 32.0 mL, 16.00 mmol) and further bubbled with argon. The reaction mixture was stirred at room temperature for five minutes, then heated to 40°C overnight. The reaction mixture was heated at 80°C for six hours, then cooled to room temperature. The crude reaction mixture was evaporated in vacuo onto ~50 g of flash silica gel and loaded into a cartridge. Purification was performed by silica gel flash chromatography (120 g, 0% EtOAc / hexane (2 CV) → 20% (15 CV)). The fractions containing the product were evaporated to dryness in vacuo to give an off-white solid, 94 mg (8.2% yield). MS (APCI): Formula C 19 H 26 Calcd. for O2 (M+H) = 287; found: 287. 1H NMR (400 MHz, acetone) δ 10.53 (s, 1H), 8.78 (s, 1H), 6.76 (s, 2H), 3.45-3.29 (m, 2H), 1.89-1.66 (m, 10H), 1.56-1.36 (m, 8H), 1.36-1.18 (m, 2H).

[0396] 3,5-Dicyclohexyl-4-formylphenyl-2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: 2,6-dicyclohexyl-4-hydroxybenzaldehyde (93 mg, 0.3247 mmol), 2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate were added to the mixture at room temperature. bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xanthen[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (329 mg, 0.3896 mmol), DMAP.pTsOH salt (10 mg, 0.03896 mmol) and DIC (0.102 mL, 0.6494 mmol) were stirred in anhydrous DCM (5 mL) for 30 minutes. The crude reaction mixture was diluted 2:1 with hexane and loaded onto ~30 g flash silica gel packed in a loader. Purification was performed by silica gel flash chromatography (120 g, isocratic DCM). The fractions containing the product were evaporated to dryness in vacuo. A yellow solid was obtained, 291 mg (80% yield). MS (APCI): Chemical formula C 61 H 43 F 12 Calculated for NO6 (M+H) = 1114; found: 1114. 1 H NMR (400 MHz, acetone) δ 10.66 (s, 1H), 8.76 (s, 1H), 8.58 (d, J = 1.7 Hz, 2H), 8.52 (s, 1H), 8.33 (d, J = 1.7 Hz, 2H), 8.24 (dd, J = 1.8, 0.9 Hz, 1H), 8.20 (dq, J = 2.0, 0.9 Hz, 1H), 7.65-7.57 (m, 2H), 7.54 (ddd, J = 8.5, 7.2, 1.5 Hz, 1H), 7.47- 7.41(m,2H),7.29(dd,J=8.3,1.2Hz,1H),7.16-7.07(m,3H),7.02(ddd,J=8.4,7.1,1.3Hz,1H),4.09(s,2H),3 .21(ddd,J=11.2,8.2,2.8Hz,2H),1.87-1.77(m,8H),1.77-1.68(m,2H),1.54-1.40(m,8H),1.36-1.23(m,2H).

[0397] PLC-30 10-(4-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xanthen[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dicyclohexylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylic acid diethyl ester: 3,5-dicyclohexylphenyl was reacted with 1,3-dioxo-1H-xanthen[2,1,9-def]isoquinolin-2(3H)-yl)phenylacetoxy)-2,6-dicyclohexylphenyl Hexyl-4-formylphenyl-2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate (290 mg, 0.2603 mmol), ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (100 mg, 0.5987 mmol), and pTsOH.HO (5 mg, 0.02603 mmol) were stirred in anhydrous DCE (30 mL) for one hour. The reaction mixture was treated with DDQ (106 mg, 0.4686 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with EtN (0.29 mL, 2.083 mmol) and BF.OEt (0.39 mL, 3.124 mmol). The addition of Et3N (0.29 mL, 2.083 mmol) and BF3.OEt2 (0.39 mL, 3.124 mmol) was repeated, and the reaction mixture was stirred at 50°C for one hour. The crude reaction mixture was evaporated in vacuo onto ~25 g flash silica gel and loaded into a loader. Purified by silica gel flash chromatography (220 g, 0% EtOAc / DCM (2CV) → 3.5% (20CV) → isocratic 3.5%). The fractions containing the product were evaporated to dryness in vacuo. An orange solid was obtained, 302 mg (79% yield). MS (APCI): Formula C 79 H 64 BF 14 Calculated for N3O9 (M+H) = 1476; found: 1476. 1HNMR(400MHz,CD2Cl2)δ8.78(s,1H),8.53(s,1H),8.32-8.29(m,2H),8.09(dq,J=1.8,0.9Hz,1H),8.05(dd,J=4.1,1.8H z,3H),7.66-7.60(m,2H),7.47(ddd,J=8.5,7.0,1.7Hz,1H),7.41-7.34(m,2H),7.26(dd,J=8.3,1.3Hz,1H),7.15(s,2H ),7.02(dd,J=8.4,1.7Hz,1H),6.97(ddd,J=8.3,7.0,1.3Hz,1H),4.26(q,J=7.1Hz,4H),4.04(s,2H),2.83(s,6H),2.42 (tt,J=11.8,3.4Hz,2H),1.72(s,6H),1.70-1.54(m,10H),1.48-1.34(m,4H),1.32(t,J=7.1Hz,6H),1.26-1.02(m,6H).

[0398] Photoluminescent compound PLC-31:

[0399]

[0400] PLC-31 10-(4-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dicyclohexylphenyl)-5,5-difluoro-3,7-dimethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylic acid diethyl ester: 3,5-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dicyclohexylphenyl 1-Dicyclohexyl-4-formylphenyl-2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate (501 mg, 0.450 mmol), ethyl 2-methyl-1H-pyrrole-3-carboxylate (173 mg, 1.125 mmol), and pTsOH.HO (9 mg, 0.045 mmol) were stirred in anhydrous DCE (30 mL) overnight. The reaction was cooled to room temperature and treated with DDQ (184 mg, 0.80 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with EtN (0.50 mL, 3.600 mmol) and BF.OEt (0.67 mL, 5.400 mmol). The addition of Et3N (0.50 mL, 3.600 mmol) and BF3.OEt2 (0.67 mL, 5.400 mmol) was repeated, and the reaction mixture was stirred at 50°C for one hour. The crude reaction mixture was evaporated in vacuo onto approximately 50 g of flash silica gel and loaded into a loader. Purified by silica gel flash chromatography (120 g, 0% EtOAc / toluene (2CV) → 0.1% (3CV) → 0.2% (3CV) → 0.3% (3CV) → 0.4% (3CV) → 0.5% (3CV) → 5% (10CV)). The fractions containing the product were evaporated to dryness in vacuo. An orange solid was obtained, 393 mg (60% yield). MS (APCI): Formula C 77 H 60 BF 14 Calculated for N3O9 (M+H) = 1448; found: 1448. 1H NMR (400MHz, acetone) δ8.76 (s, 1H), 8.58-8.55 (m, 2H), 8.52 (s, 1H), 8.34-8.30 (m, 2H), 8.24 (dq, J = 1.9, 0.9Hz, 1H), 8.2 0(td,J=1.7,0.9Hz,1H),7.69-7.61(m,2H),7.53(ddd,J=8.5,7.2,1.5Hz,1H),7.49-7.42(m,2H),7.28(dd,J=8.3, 1.3Hz,1H),7.23(s,2H),7.11(dd,J=6.8,1.5Hz,3H),7.01(ddd,J=8.4,7.2,1.3Hz,1H),4.23(q,J=7.1Hz,4H),4.1 3(s,2H),2.90(s,6H),2.42-2.27(m,2H),1.72-1.42(m,14H),1.27(q,J=7.0Hz,8H),1.00(qt,J=13.8,3.9Hz,2H).

[0401] Photoluminescent compound PLC-32:

[0402]

[0403] 2,6-dibromo-4-(methoxymethoxy)benzaldehyde: Under argon, 2,6-dibromo-4-hydroxybenzaldehyde (5.598g, 20.00mmol) and potassium carbonate (5528mg, 40.00mmol) were combined in anhydrous THF (100mL) and stirred. MOM-Cl (1.97mL, 26.00mmol) was added to the flask. The reaction mixture was stirred at room temperature overnight. The crude reaction mixture was evaporated in vacuo onto ~60g flash silica gel and loaded into a loader. Purified by silica gel flash chromatography (220g, 25% DCM / hexane (0.5CV) → 100% DCM (0CV) → isocratic DCM)). The fraction containing the product was evaporated to dryness in vacuo. An off-white solid was obtained, 5.677g (88% yield). MS (APCI): calculated value for chemical formula C9H8Br2O3 (M+H) = 323; found value: 323.

[0404] 4-(Methoxymethoxy)-2,6-diphenoxybenzaldehyde: 2,6-Dibromo-4-(methoxymethoxy)benzaldehyde (324 mg, 1.000 mmol), phenol (376 mg, 4.000 mmol), N,N-dimethylglycine (7 mg, 0.07000 mmol), cesium carbonate (1955 mg, 6.000 mmol), and CuI (6 mg, 0.03000 mmol) were combined in dioxane (3 mL) in a microwave vial. The reaction was sparged with argon for 30 minutes, then the vial cap was securely secured and heated in a heating block at 100°C for six hours. The crude reaction mixture was evaporated in vacuo onto ~40 g of flash silica gel and loaded into a cartridge. Purification was performed by silica gel flash chromatography (120 g, 0% EtOAc / hexanes (2 CV) → 100% EtOAc (20 CV)). The fractions containing the product were evaporated to dryness in vacuo. A slowly solidifying orange oil was obtained, 247 mg (71% yield). MS (APCI): Formula C 21 H 18 Calcd. for O5 (M+H) = 351; found: 351. 1 H NMR (400MHz, CD2Cl2) δ10.41 (s, 1H), 7.45-7.36 (m, 4H), 7.19 (ddt, J = 8.6, 7.7, 1.1Hz, 2H), 7.13-7.04 (m, 4H), 6.25 (s, 2H), 5.00 (s, 2H), 3.35 (s, 3H).

[0405] 4-Hydroxy-2,6-diphenoxybenzaldehyde: 4-(methoxymethoxy)-2,6-diphenoxybenzaldehyde (247 mg, 0.7050 mmol) and 1,4-dimethoxybenzene (195 mg, 1.410 mmol) were dissolved in DCM (5 mL) and stirred at room temperature. TFA (5 mL) was added to the solution, and the solution was stirred at room temperature for 30 minutes. The crude reaction mixture was diluted 1:1 with hexane and loaded onto a loader filled with ~50 g flash silica gel. Purified by silica gel flash chromatography (120 g, 0% EtOAc / hexane (2CV) → 100% EtOAc (20CV)). The fractions containing the product were evaporated to dryness in vacuo. An off-white solid was obtained, 194 mg (90% yield). MS (APCI): Chemical formula C 19 H 14 Calcd. for O4 (M+H) = 307; found: 307. 1H NMR (400MHz, CD2Cl2) δ10.38(s,1H),7.46-7.36(m,4H),7.24-7.16(m,2H),7.12-7.04(m,4H),5.98(s,2H),5.95(s,1H).

[0406] 4-Formyl-3,5-diphenoxyphenyl-2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: 4-Hydroxy-2,6-diphenoxybenzaldehyde (192 mg, 0.6268 mmol), 2-(4-(5,11-bis(3,5 -bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (636 mg, 0.7522 mmol), DMAP.pTsOH salt (18 mg, 0.06268 mmol) and DIC (0.196 mL, 1.254 mmol) were stirred in anhydrous DCM (10 mL) for 30 minutes. The crude reaction mixture was loaded onto a carrier filled with ~40 g flash silica gel. Purification was performed by silica gel flash chromatography (120 g, 0% EtOAc / DCM (2CV) → 10% (30CV)). The fractions containing the product were evaporated to dryness in vacuo. A yellow solid was obtained, 642 mg (90% yield). MS (APCI): Chemical formula C 61 H 31 F 12 Calculated for NO8 (M+H) = 1134; found: 1134. 1 HNMR (400MHz, CD2Cl2) δ10.54(s,1H),8.76(s,1H),8.51(s,1H),8.33-8.25(m,2H),8.12-8.08(m,1H),8.05(d,J=1.7Hz,3H),7.56-7.37(m,8H) ,7.32-7.26(m,3H),7.23(ddt,J=8.5,7.3,1.1Hz,3H),7.02(dd,J=8.3,1.7Hz,1H),6.97(ddd,J=8.3,7.0,1.3Hz,1H),6.43(s,2H),3.87(s,2H).

[0407] PLC-32 10-(4-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-diphenoxyphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylic acid diethyl ester: 4-formyl- 3,5-Diphenoxyphenyl-2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate (639 mg, 0.5635 mmol), ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (236 mg, 1.409 mmol), and pTsOH.HO (11 mg, 0.05635 mmol) were stirred in anhydrous DCE (50 mL) for one hour. The reaction mixture was treated with DDQ (230 mg, 1.014 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with EtN (0.63 mL, 4.508 mmol) and BF.OEt (0.83 mL, 6.763 mmol). The addition of Et3N (0.63 mL, 4.508 mmol) and BF3.OEt2 (0.83 mL, 6.763 mmol) was repeated, and the reaction mixture was stirred at 50°C for one hour. The crude reaction mixture was evaporated in vacuo onto ~60 g flash silica gel and loaded into a loader. Purification was performed by silica gel flash chromatography (220 g, 0% EtOAc / DCM (2CV) → 3% (20CV) → isocratic 3%). An orange solid was obtained, 598 mg (71% yield). MS (APCI): Formula C 79 H 52 BF 14 N3O 11 Calcd. (M+H) = 1496; found: 1496. 1H NMR (400 MHz, acetone) δ 8.75 (s, 1H), 8.59-8.56 (m, 2H), 8.51 (s, 1H), 8.36-8.33 (m, 2H), 8.26-8.22 (m, 1H), 8.22-8.18 (m, 1H), 7.54 (ddd, J = 8.5, 7.2, 1.5 Hz, 1H), 7.50-7.40 (m, 6H), 7.39-7.33 (m, 2H), 7. 30(dd,J=8.3,1.3Hz,1H),7.27-7.19(m,2H),7.16-7.06(m,5H),7.02(ddd,J=8.4,7.2,1.3Hz,1H) ,6.52(s,2H),4.32(q,J=7.1Hz,4H),3.99(s,2H),2.79(s,6H),2.27(s,6H),1.37(t,J=7.1Hz,6H).

[0408] Photoluminescent compound PLC-33:

[0409]

[0410] PLC-33 5,5-Dicyano-10-(4-(2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dimethoxyphenyl)-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylic acid diethyl ester: 10-(4-(2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dimethoxyphenyl)-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylic acid diethyl ester Diethyl (2,1,9-def)isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dimethoxyphenyl)-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 (0.1000 mmol, 124 mg) was dissolved in anhydrous DCE (10 mL) and treated with TMSCN (2.000 mmol, 0.250 mL) and BF3.OEt2 (0.1500 mmol, 0.019 mL). The reaction was stirred at room temperature for several minutes and then heated to 45°C for 60 minutes. The reaction mixture was poured into ~30 mL of saturated NaHCO3 and stirred for several minutes. The reaction was filtered through a polypropylene frit to retain the water and the product was eluted with DCM. The eluent was evaporated to dryness in vacuo, dissolved in a small amount of DCM, and loaded onto ~15 g of flash silica gel packed in a loader. Purified by flash chromatography on silica gel (80 g, 0% acetone / hexanes (2CV) → 35% (5CV), gradient stopped at 26.6%. Fractions containing the product were evaporated to dryness in vacuo. The product was triturated with MeOH / water, filtered, washed with MeOH / water, dissolved in DCM, and evaporated to dryness in vacuo. An orange solid was obtained, 121 mg (97% yield). MS (APCI): Formula C 69 H 50 BF6N5O 11 Calcd. (M+H) = 1250; found: 1250. 1H NMR(400MHz,TCE)δ8.71(s,1H),8.48(s,1H),7.91(d,J=8.3Hz,2H),7.89-7.82(m,4 H),7.67(dd,J=8.3,2.5Hz,4H),7.47-7.38(m,3H),7.31(dd,J=8.4,1.3Hz,1H),7.10 (dd,J=8.3,1.5Hz,1H),6.96(ddd,J=8.4,7.1,1.4Hz,1H),6.58(s,2H),4.32(q,J=7. 1Hz, 4H), 4.05 (s, 2H), 3.76 (s, 6H), 3.01 (s, 6H), 1.92 (s, 6H), 1.37 (t, J = 7.1Hz, 6H).

[0411] Photoluminescent compound PLC-34:

[0412]

[0413] 2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: 2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate was stirred at room temperature for 2 h. quinolin-2(3H)-yl)phenyl)acetic acid (2.750 mmol, 2325 mg), 4-hydroxy-2,6-dimethoxybenzaldehyde (2.500 mmol, 455 mg), DMAP.pTsOH salt (0.2500 mmol, 74 mg) and EDC.HCl (5.000 mmol, 986 mg) were stirred in anhydrous DCE (30 mL) in a vial for 60 minutes. The crude reaction mixture was loaded onto ~45 g flash silica gel loaded in a loader. Purification was performed by silica gel flash chromatography (120 g, 0% EtOAc / DCM (2CV) → 30% (10CV)). The fractions containing the product were evaporated to dryness in vacuo. A yellow solid was obtained, 2061 mg (82% yield). MS (APCI): Chemical formula C 51 H 27 F 12 Calculated for NO8 (M+H) = 1010; found: 1010. 11H NMR (400 MHz, acetone) δ 10.38 (s, 1H), 8.76 (s, 1H), 8.60 - 8.56 (m, 2H), 8.51 (s, 1H), 8.33 (d, J = 1.7 Hz, 2H), 8.24 (s, 1H), 8.22 - 8.18 (m, 1H), 7.60 (d, J = 8.4 Hz, 2H), 7.54 (ddd, J = 8.5, 7.2, 1.5 Hz, 1H), 7.48 - 7.40 (m, 2H), 7.28 (dd, J = 8.3, 1.3 Hz, 1H), 7.11 (dd, J = 8.3, 1.5 Hz, 1H), 7.02 (ddd, J = 8.3, 7.1, 1.3 Hz, 1H), 6.61 (s, 2H), 4.09 (s, 2H), 3.87 (s, 6H).

[0414] PLC-34 10-(4-(2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dimethoxyphenyl)-5,5-difluoro-3,7-diisopropyl-1,9-dimethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-

[00145] Dimethyl diformate: Under argon, the aldehyde from the previous step (0.4000 mmol, 404 mg), ethyl 2-isopropyl-4-methyl-1H-pyrrole-3-carboxylate (0.8000 mmol, 145 mg), and pTsOH.HO (0.08000 mmol) were stirred in anhydrous DCE (25 mL) at room temperature for 30 minutes, followed by the addition of DDQ (0.8000 mmol, 182 mg) and stirring for 5 minutes. EtN (3.200 mmol, 0.45 mL) and BF.OEt (4.800 mmol, 0.59 mL) were added to the reaction. The addition of EtN (3.200 mmol, 0.45 mL) and BF.OEt (4.800 mmol, 0.59 mL) was repeated, and the reaction was stirred at 65°C for 8 hours, then at room temperature overnight. The reactants were quenched with 5 mL of water and stirred for a few minutes, then filtered through a polypropylene frit to retain water. The frit was eluted with DCM. The eluent was directed to a 15 g flash silica plug, eluted with DCM, then eluted with 33% acetone / DCM. The solvent was evaporated to dryness in a vacuum, dissolved in a small amount of DCM and loaded onto a 15 g flash silica gel loaded into a loader. Purified by flash chromatography on silica gel (120 g, 0% EtOAc / DCM (2CV) → 20% (5CV), eluting isocratically at 4.0%. The fractions containing the product were evaporated to dryness in a vacuum. The product was triturated with hot MeOH, cooled to room temperature, filtered off, washed with MeOH, dissolved in DCM, and evaporated to dryness in a vacuum. An orange solid was obtained, 447 mg (80% yield). MS (APCI): Chemical Formula C 69 H 54 BF8N3O 11 Calcd. (M+H) = 1264; found: 1264. 1H NMR(400MHz,TCE)δ8.67(s,1H),8.42(s,1H),8.18(d,J=1.6Hz,2H),7.99(s,1H),7.94(t,J=2.3Hz,3H),7.63-7.52(m,2H),7.40(ddd,J=8.5,6.3, 2.4Hz,1H),7.36-7.24(m,2H),7.22-7.15(m,1H),7.00-6.80(m,2H),6.4 6(s,2H),3.96(s,2H),3.74(s,8H),3.68(s,6H),1.31(d,J=7.0Hz,12H).

[0415] Photoluminescent compound PLC-35:

[0416]

[0417] PLC-35 10-(4-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dimethoxyphenyl)-5,5-dicyano-3,7-diisopropyl-1,9-dimethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3, 2] Dimethyl diazaborin-2,8-dicarboxylate: PLC-34 (0.1500 mmol, 210 mg), TMSCN (1.500 mmol, 0.19 mL) and BF3.OEt2 (0.2250 mmol, 0.028 mL) were stirred in anhydrous DCE (10 mL) under argon at room temperature for several minutes, then heated to 45 ° C for 60 minutes, and then left at room temperature overnight. The crude reaction mixture was poured into 30 mL of saturated NaHCO3 and stirred for 5 minutes, then filtered through a polypropylene frit to retain water. The frit was eluted with DCM. The organic eluent was evaporated to dryness in vacuo, dissolved in a small amount of DCM and loaded onto 15 g of flash silica gel loaded in a loader. Purification by flash chromatography on silica gel (80 g, 0% acetone / DCM (2CV) → 5% (5CV), stopping at 1.1%, 1.4%, 1.6%, 1.8%, 2.2%, 2.4%, isocratic in each step. Fractions containing product were evaporated to dryness in vacuo. The product was triturated with hot MeOH, cooled to room temperature, filtered off, washed with MeOH, dissolved in DCM, and evaporated to dryness in vacuo. An orange solid was obtained, 157 mg (74% yield). MS (APCI): Formula C 73 H 52 BF 12 N5O 11Calcd. (M+H) = 1414; found: 1414. 1 HNMR(400MHz,TCE)δ8.76(s,1H),8.51(s,1H),8.27(d,J=1.6Hz,2H),8.08( s,1H),8.06-8.00(m,3H),7.69-7.62(m,2H),7.49(ddd,J=8.6,6.3,2.3Hz,1 H),7.44-7.36(m,2H),7.32-7.25(m,1H),7.00(dd,J=6.6,1.5Hz,2H),6.55( s, 2H), 3.91-3.80 (m, 8H), 3.78 (s, 6H), 1.74 (s, 6H), 1.53 (d, J = 6.8Hz, 12H).

[0418] Example 2: Procedure for measuring the optical properties of sharp emitter chromophores

[0419] A glass substrate was prepared in essentially the following manner. A 1.1 mm thick glass substrate was cut into 1 inch x 1 inch dimensions. The glass substrate was then washed with detergent and deionized (DI) water, rinsed with fresh DI water, and sonicated for approximately 1 hour. The glass substrate was then immersed in isopropyl alcohol (IPA) and sonicated for approximately 1 hour. The glass substrate was then immersed in acetone and sonicated for approximately 1 hour. The glass substrate was then removed from the acetone bath and dried with nitrogen at room temperature.

[0420] Prepare a 25 wt% solution of poly(methyl methacrylate) (PMMA) resin in spectroscopic grade toluene. Stir the prepared PMMA polymer at 50°C until the PMMA is completely dissolved. [PMMA] CAS: 9011-14-7; [Toluene] CAS: 108-88-3.

[0421] In a 20 mL vial, 2 mg of chromophore was added to the PMMA solution to prepare 2.0 × 10 -3 The volume of PMMA solution was calculated using the following formula: The mixture was then thoroughly mixed by vortexing for approximately 5 min and sonicated for approximately 60 min. The PMMA / compound solution was then spin-coated onto the prepared glass substrate at 1000 RPM for 20 s. The spin-coated sample was baked in an oven at 150° C. for 5 minutes to evaporate the remaining solvent.

[0422] A 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 the absorption spectrum.

[0423] Fluorescence spectra (emission spectra) of 1 inch x 1 inch film samples prepared as described above were measured using a Fluorologmax spectrofluorometer (Horiba Scientific, Edison, NJ, USA). Wavelengths of 390 nm and 450 nm were selected as excitation wavelengths.

[0424] The quantum yields of the spin-coated samples described above were measured using a Hamamatsu C11347 Absolute PL Quantum Yield Spectrometer (Hamamatsu Inc., Campbell, CA, USA). A 0.5" x 0.5" film was removed from the glass substrate for QY measurement. The wavelength was scanned every 30 nm from 390 nm to 450 nm (as the excitation wavelength). The QY at 450 nm is reported in Table 1.

[0425] The optical properties (absorption peak wavelength, emission peak wavelength, FWHM and quantum yield) of the spin-coated films are shown in Table 1 below.

[0426] Table 1. Optical properties of chromophores in PMMA

[0427]

[0428]

[0429]

[0430]

[0431]

[0432]

[0433]

[0434]

[0435]

[0436]

[0437]

[0438]

[0439]

[0440]

[0441]

[0442]

[0443] Example 3: Light stability

[0444] By exposing a 1 inch × 1 inch sample to 40 mW / cm 2 The photostability of the chromophore was tested using a blue LED (CREE, Durham, North Carolina, USA). Following the same procedure as above, the absorption, emission, and QY of the sample were monitored daily for the first 2-3 days, followed by weekly monitoring. The photostability of the chromophore was quantified by the decrease in absorption (Abs%). Changes in QY%, emission characteristics, were also monitored. Photostability measurements were continued until the absorption decayed to less than 50% absorption. Figure 1 Photostability data for PLC-1 compared to CE-3 are provided in Figure 1. This figure shows the improved photostability of PLC-1 of the present invention relative to CE-3.

Claims

1. A photoluminescent composite comprising: The part that absorbs blue light; linker complex; and boron-dipyrromethene (BODIPY) moiety; The blue light absorbing portion is a xanthene isoquinoline group of the following general formula: Among them, each R 0 is independently H, alkyl, -CF3, alkoxy or optionally substituted aryl; where R 10 is H, alkyl, -CF3, alkoxy or optionally substituted aryl; Wherein the dotted line is the covalent bond with the linker complex; wherein the BODIPY moiety has the following general formula: Wherein X is F or CN; where R 1 and R 6 are independently H or alkyl; where R 3 and R 4 are independently H or alkyl; where R 2 and R 5 are independently H, alkyl, cycloalkyl, -CN, alkylester, or arylester; where R 7 and R 8 are independently optionally substituted aryl, C 1-8 Alkyl; C 3-8 Cycloalkyl; having C 1-10 an ether group of an alkyl group, an ether moiety having an optionally substituted aryl group, or a C 1-10 Arylalkyl; wherein the linker complex comprises an optionally substituted ester or an optionally substituted ether linker; wherein the linker complex covalently links the blue-light-absorbing moiety and the BODIPY moiety, wherein the blue-light-absorbing moiety absorbs light energy at a first excitation wavelength and transfers the energy to the BODIPY moiety, wherein the BODIPY moiety absorbs energy from the blue-light-absorbing moiety and emits light energy at a second, higher wavelength, and wherein the photoluminescent complex has an emission quantum yield greater than 80%.

2. The photoluminescent composite according to claim 1, wherein R 7 and R 8 -CH2CH(CH2CH3)(CH2)3CH3, cyclopropyl, cyclohexyl, n-pentyl, -CH2-cyclohexyl, -OCH2-cyclohexyl, -O(CH2)3Ph, -OCH2CH(CH2CH3)CH2CH2CH2CH3, phenyl, -OCH3, -O-phenyl, 3. The photoluminescent composite according to claim 1, wherein R 7 and R 8 is independently optionally substituted alkyl, optionally substituted cycloalkyl or optionally substituted ether, including pentyl, 2-ethylhexyl, cyclohexyl, CH2-cyclohexyl, -OCH3, -O-(2-ethylhexyl), -OCH2-cyclohexyl, -OPh or -O(CH2)3-Ph.

4. The photoluminescent composite of claim 1, 2 or 3, wherein R 1 and R 6 are independently H, methyl, ethyl, propyl, isopropyl, butyl or isobutyl; and wherein R 3 and R 4 is independently H, methyl, ethyl, propyl, isopropyl, butyl or isobutyl.

5. The photoluminescent composite according to claim 1, 2, 3 or 4, wherein R 2 and R 5 Contains -C(O)OMe, 6. The photoluminescent composite according to claim 1, 2, 3, 4 or 5, wherein R 0 Include And R 10 Contains H.

7. The photoluminescent complex of claim 1, 2, 3, 4, 5 or 6, wherein the linker complex comprises 8. The photoluminescent composite of claim 1, 2, 3, 4, 5, 6 or 7, wherein X is F.

9. The photoluminescent composite of claim 1, 2, 3, 4, 5, 6 or 7, wherein X is CN.

10. The photoluminescent composite of claim 1, 2, 3, 4, 5, 6, 7, 8, or 9, wherein the photoluminescent composite comprises one of the following structures: or 11. A color conversion film comprising: a transparent substrate layer; a color conversion layer, wherein the color conversion layer comprises a resin matrix; and The photoluminescent composite comprises the photoluminescent composite of claim 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 dispersed in the resin matrix. 12 . The color conversion film of claim 11 , further comprising a singlet oxygen quencher.

13. The color conversion film of claim 11, further comprising a radical scavenger.

14. The color conversion film of claim 11, wherein the color conversion film has a thickness of about 1 μm to about 200 μm.

15. The color conversion film of claim 11, wherein the color conversion film absorbs light in a wavelength range of about 400 nm to about 480 nm and emits light in a wavelength range of 500 nm to about 560 nm.

16. A method for preparing the color conversion film according to claim 11, 12, 13, 14 or 15, comprising: dissolving the photoluminescent composite according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 and a binder resin in a solvent; and The mixture is applied to the surface of a transparent substrate.

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

18. A display device comprising the backlight unit according to claim 17.

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