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

Abstract

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

Description

[Technical Field]

[0001] [CROSS-REFERENCE TO RELATED APPLICATIONS] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 385,812, filed December 2, 2022, and U.S. Provisional Patent Application No. 63 / 504,158, filed May 24, 2023. [Background technology]

[0002] In color reproduction, a gamut, or color gamut, is a particular complete subset of colors available on a device such as a television or monitor. For example, Adobe™ Red Green Blue (RGB), a wide-gamut color space achieved by using pure spectral primaries, was developed to provide a wider color gamut and result in a more realistic representation of visible colors viewed through a display. It is believed that devices that can provide a wider color gamut may enable displays to depict more vibrant colors.

[0003] As high-definition, large-screen displays become more common, the demand for higher-performance, thinner, and more functional displays is increasing. Current light-emitting diodes (LEDs) are obtained by exciting green, red, or yellow phosphors with a blue light source 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 very large, typically exceeding 40 nm, resulting in overlapping green and red spectra, resulting in color rendering that is completely indistinguishable from one another. This overlap leads to poor color rendering and a reduced color gamut.

[0004] To compensate for the reduced color gamut, methods have been developed to use films containing quantum dots in combination with LEDs. However, the use of quantum dots presents problems. First, cadmium-based quantum dots are highly toxic and banned in many countries due to health safety concerns. Second, non-cadmium-based quantum dots are very inefficient at converting blue LED light into green and red light. Third, quantum dots require expensive encapsulation processes to protect them from moisture and oxygen. Finally, the cost of using quantum dots is high due to the difficulty of controlling size uniformity during the manufacturing process. Co-pending patent applications include at least Patent Cooperation Treaty publications U.S. Pat. No. 6,229,492 and U.S. Pat. No. 6,229,492, filed on February 22, 2022, and U.S. Pat. No. 6,229,492, filed on September 23, 2022.

[0005] Therefore, there is a need for improved performance in color conversion films, backlight units, and display devices. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2022 / 178450 [Patent Document 2] International Application No. PCT / US2022 / 017373 [Patent Document 3] International Application No. PCT / US2022 / 076912 Summary of the Invention

[0007] The photoluminescent complexes described herein can be used to improve the contrast between distinguishable colors in televisions, computer monitors, smart devices, and any other devices that utilize color displays. The photoluminescent complexes of the present disclosure provide novel color conversion dye complexes with good blue light absorption and narrow emission bandwidths, e.g., full width at half maximum (FWHM) of the emission band less than 40 nm. In some embodiments, the photoluminescent complexes absorb light at a first wavelength and emit light at a second wavelength higher than the first wavelength. The photoluminescent complexes disclosed herein can be utilized in color conversion films for use in light-emitting devices. The color conversion films of the present disclosure reduce color degradation by reducing overlap in the color spectrum, resulting in high-quality color rendering.

[0008] Some embodiments include a photoluminescent complex that includes a blue light absorbing moiety, a linker conjugate, and a boron-dipyrromethene (BODIPY) moiety.

[0009] In some embodiments, the blue light absorbing moiety has the general formula: [ka] (In the formula, R 0 comprises H, an alkyl group, —CF3, an alkoxy, or an optionally substituted aryl; R 10 is a xanthenoisoquinoline group (including H, alkyl group, —CF 3 , alkoxy, or optionally substituted aryl). In some examples, the dashed line comprises a covalent bond to the linker conjugate.

[0010] Some embodiments have the general formula: [ka] wherein X comprises F or CN, and R 1 and R 6 and R 3 and R 4includes H, alkyl, cycloalkyl, and alkenyl groups, and R 2 and R 5 contains H, alkyl, cycloalkyl, cyano (-CN) group, alkyl ester group or aryl ester group, and R 7 and R 8 is optionally substituted aryl, C 2~8 Alkyl group, C 3~8 Cycloalkyl groups, C 1~10 an ether group having an alkyl group, an ether moiety having an optionally substituted aryl group, or C 1~10 The BODIPY moiety includes an arylalkyl group.

[0011] In some embodiments, the linker conjugate comprises an optionally substituted ester or an optionally substituted ether linker, which covalently attaches the blue light absorbing moiety to the BODIPY moiety.

[0012] In other embodiments, the blue light absorbing moiety absorbs light energy at a first excitation wavelength and transfers that energy to the BODIPY moiety, and in some instances, the BODIPY moiety absorbs energy from the blue light absorbing moiety and emits light energy at a second, longer wavelength.

[0013] In some embodiments, the photoluminescent complex has an emission quantum yield of greater than 80%.

[0014] In some instances, the R of the photoluminescent complex 7 and R 8 is optionally substituted aryl, e.g., phenyl; [ka] Includes:

[0015] In another example, the R of the photoluminescent complex 7 and R 8includes an optionally substituted alkyl group, an optionally substituted cycloalkyl group, or an optionally substituted ether group, including pentyl, 2-ethylhexyl, cyclohexyl, CH-cyclohexyl, -OCH, -O-(2-ethylhexyl), -OCH-cyclohexyl, -OPh, or -O(CH)-Ph.

[0016] Some embodiments include R 1 and R 6 contains H, methyl, ethyl, propyl, isopropyl, butyl, or isobutyl, and R 3 and R 4 includes photoluminescent complexes in which H, methyl, ethyl, propyl, isopropyl, butyl, or isobutyl.

[0017] Other embodiments include R 2 and R 5 is -C(O)OMe, [ka] The photoluminescent complex comprises:

[0018] In some embodiments, the R of the photoluminescent complex 0 teeth, [ka] Includes:

[0019] In another example, the R of the photoluminescent complex 10 contains H.

[0020] In some embodiments of the photoluminescent complex, the linker conjugate is [ka] Includes:

[0021] In some instances, X in the photoluminescent complex is F. In other instances, X in the photoluminescent complex is CN.

[0022] Some embodiments of the present disclosure include a color conversion film comprising: In some examples, the color conversion film comprises a transparent substrate layer and a color conversion layer comprising a resin matrix, in some embodiments, a photoluminescent compound as described herein dispersed within the resin matrix.

[0023] In some embodiments, the color conversion film of the present disclosure can include a singlet oxygen quencher, hi some embodiments, the color conversion film can further include a free radical scavenger.

[0024] Some embodiments include a method of making a color conversion film, the method comprising dissolving the aforementioned photoluminescent complex and a binder resin in a solvent and applying the mixture to the surface of a transparent substrate.

[0025] Some embodiments include a backlight unit comprising the color conversion film described herein.

[0026] Other embodiments include display devices comprising the backlight units described herein.

[0027] The present application provides a photoluminescent complex having excellent color gamut and luminescence properties, a method for manufacturing a color conversion film using the photoluminescent complex, and a backlight unit including the color conversion film. These and other embodiments are described in more detail below. [Brief explanation of the drawings]

[0028] [Figure 1] 1 is a graph showing the photostability of one embodiment of a photoluminescent complex (PLC-1) compared to a comparative example (CE-3). [Figure 2]1 is a graph showing the absorption and emission spectra of one embodiment of a photoluminescent complex (PLC-21). [Figure 3] 1 is a graph showing the absorption and emission spectra of one embodiment of a photoluminescent complex (PLC-25). DETAILED DESCRIPTION OF THE INVENTION

[0029] The present disclosure relates to photoluminescent compounds and complexes for use in color conversion films, backlight units, and display devices.

[0030] The present disclosure describes photoluminescent complexes and their use in color conversion films. The photoluminescent complexes can be used to improve and enhance the transmission of one or more desired emission bandwidths within the color conversion film. In some embodiments, the photoluminescent complexes can enhance the transmission of a first desired emission bandwidth while also reducing the transmission of a second desired emission bandwidth. For example, the color conversion film can enhance the contrast or intensity between two or more colors, enhancing their differentiation from one another. The present disclosure includes photoluminescent complexes that can enhance the contrast or intensity between two colors, enhancing their differentiation from one another.

[0031] As used herein, when a compound or chemical structure is referred to as "substituted," it can contain one or more substituents. A substituted group is derived from an unsubstituted parent structure, where one or more hydrogen atoms of the parent structure have been independently replaced by one or more substituents. In one or more embodiments, the substituents are independently selected from optionally substituted C 1~8 Alkyl, C 3~8 Alkenyl, or C 3~8 heteroalkyl.

[0032] The alkyl moiety can be branched, straight chain (i.e., unbranched), or cyclic. In some embodiments, the alkyl moiety can have 1 to 8 carbon atoms. The alkyl group of the compounds designated herein is defined as "C 1~8 By way of example only, "C 1~8 "Alkyl" indicates that there are 1, 2, 3, 4, 5, 6, 7, or 8 carbon atoms in the alkyl chain, i.e., the alkyl chain is methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, and any isomer thereof. Thus, C 1~8 Alkyl is 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 and alkyl. Alkyl groups can be substituted or unsubstituted. Typical alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, hexyl, ethenyl, propenyl, butenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

[0033] As used herein, the term "heteroalkyl" refers to an alkyl group, as defined herein, in which one or more member carbon atoms have 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. Additionally, up to two heteroatoms may be consecutive, such as, for example, -CH2-NH-O-CH3.

[0034] The term "aromatic" refers to a planar ring having a delocalized π-electron system containing 4n+2 (where n is an integer) π-electrons. An aromatic ring can be formed from 5, 6, 7, 8, 9, or 10 or more atoms. An aromatic ring can be optionally substituted. The term "aromatic" includes both carbocyclic aryl (e.g., phenyl) and heterocyclic aryl (i.e., "heteroaryl" or "heteroaromatic") groups (e.g., pyridine). The term includes monocyclic or fused-ring polycyclic (i.e., rings that share adjacent pairs of carbon atoms) groups.

[0035] The term "hydrocarbon ring" refers to a monocyclic or polycyclic ring or ring system containing only carbon and hydrogen and may be saturated. Monocyclic hydrocarbon rings include groups having from 3 to 12 carbon atoms.

[0036] As used herein, the term "aryl" refers to an aromatic ring in which each of the atoms forming the ring is a carbon atom. The aryl ring can be formed by 5, 6, 7, 8, or more carbon atoms. The aryl group can be substituted or unsubstituted. Examples of aryl groups include, but are not limited to, phenyl, naphthalenyl, phenanthrenyl, etc.

[0037] The term "aralkyl" refers to an alkyl group substituted with an aryl. Non-limiting aralkyl groups include benzyl, phenethyl, and the like.

[0038] The term "heteroaryl" refers to an aryl group containing one or more ring heteroatoms selected from nitrogen, oxygen, and sulfur, with heteroaryl groups having 4 to 10 atoms in their ring system. It is understood that heteroaryl rings can have additional heteroatoms within the ring. In heteroaryls having two or more heteroatoms, those two or more heteroatoms can be the same or different from one another. Heteroaryl groups can be optionally substituted. An N-containing heteroaryl moiety refers to an aryl group in which the skeletal atom of the ring is a nitrogen atom. Illustrative examples of heteroaryl groups include the following moieties: pyrrole, imidazole, etc.

[0039] As used herein, the term "halogen" refers to fluorine, chlorine, bromine, and iodine.

[0040] As used herein, the terms "bond," "bonded," "direct bond," "single bond," or "covalent bond" refer to a chemical bond between two atoms or to two moieties when the atoms joined by the bond are considered to be part of a larger structure.

[0041] The term "moiety" as used herein refers to a specific segment or functional group of a molecule. A chemical moiety is often recognized as a chemical entity embedded within or added to a molecule.

[0042] As used herein, the term "cyano" or "nitrile" refers to any organic compound containing a -CN functional group.

[0043] The term "ester" refers to a chemical moiety having the formula -COOR, where R includes an alkyl, cycloalkyl, aryl, heteroaryl (bonded through a ring carbon), or heterocyclic (bonded through a ring carbon) moiety. Any hydroxy or carboxyl side chain on the compounds described herein may be esterified. Any suitable procedure and specific groups for making such esters can be utilized.

[0044] As used herein, the term "ether" refers to a chemical moiety containing an oxygen atom connected to two alkyl or aryl groups, with the general formula RO-R', where R and R' are alkyl and / or aryl. Similarly, the term "alkoxy" refers to a chemical moiety containing an oxygen atom connected to an alkyl group, which is further connected to an alkyl or aryl group.

[0045] As used herein, the term "ketone" refers to a chemical moiety containing a carbonyl group (a carbon-oxygen double bond) connected to two alkyl or aryl groups having the general formula RC(=O)R', where R and R' are alkyl and / or aryl.

[0046] As used herein, the term "BODIPY" refers to a compound of the formula: [ka] refers to a chemical moiety having the formula:

[0047] The BODIPY moiety can consist of a dipyrromethene complexed with a disubstituted boron atom (BX2), typically a BF2 or B(CN)2 unit. The IUPAC name for the BODIPY core (i.e., unsubstituted, with no aryl group opposite the BX2 group, and X=F) is 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene.

[0048] As used herein, the term "xanthenoisoquinoline" or "xanthenoisoquinoline derivative" refers to a compound of the formula: [ka] For example, 1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione.

[0049] The present disclosure relates to photoluminescent complexes that absorb light energy at a first wavelength and emit light energy at a second, higher wavelength. The photoluminescent complexes of the present disclosure include an absorbing-emitting moiety and an emitting-emitting moiety connected via a linker, the distance between which is adjusted so that the absorbing-emitting moiety transfers its energy to an acceptor-emitting moiety, which then emits at a second wavelength greater than the absorbed first wavelength.

[0050] In some embodiments, the photoluminescent complex comprises a blue light-absorbing moiety, a linker conjugate, and a boron-dipyrromethene (BODIPY) moiety. In some embodiments, the blue light-absorbing moiety is a xanthenoisoquinoline derivative. In some embodiments, the linker conjugate can covalently attach the xanthenoisoquinoline derivative to the BODIPY moiety. In some embodiments, the xanthenoisoquinoline derivative absorbs light at a first excitation wavelength and transfers energy to the BODIPY moiety, which then emits light energy at a second wavelength, where the light energy at the second wavelength is higher than the first wavelength.

[0051] Energy transfer from the excited xanthenoisoquinoline derivative to the BODIPY moiety is thought to occur via Förster resonance energy transfer (FRET). This is supported by the absorption / emission spectrum of the photoluminescent complex, which has two major absorption bands: one in the blue light absorption band (xanthenoisoquinoline derivative) and one in the BODIPY absorption band, and only one emission band at the emission wavelength of the BODIPY moiety (see Figures 2 and 3).

[0052] In some embodiments, the photoluminescent complex may have a high emission quantum yield. In some embodiments, the emission quantum yield may be greater than 50%, 60%, 70%, 80%, or 90%. In some embodiments, the emission quantum yield may be greater than 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 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 absorbing-light-emitting moiety may have an emission quantum yield greater than 80%. In some embodiments, the quantum yield may be greater than 0.8 (80%), 0.81 (81%), 0.82 (82%), 0.83 (83%), 0.84 (84%), 0.85 (85%), 0.86 (86%), 0.87 (87%), 0.88 (88%), 0.89 (89%), 0.9 (90%), 0.91 (91%), 0.92 (92%), 0.93 (93%), 0.94 (94%), or 0.95 (95%), and may be up to near 1 (100%). Quantum yield measurements on films may be performed by a spectrophotometer, for example, a Quantaurus-QY spectrophotometer (Hamamatsu, Inc., Campbell, CA, USA).

[0053] In some embodiments, the photoluminescent complex has an emission band that can have a full width at half maximum (FWHM) of less than 40 nm. The FWHM is the width of the emission band in nanometers at an emission intensity that is half the maximum emission intensity for the band. In some embodiments, the photoluminescent complex has an emission band FWHM value of about 35 nm or less, about 30 nm or less, about 25 nm or less, or about 20 nm or less.

[0054] In some embodiments, the photoluminescent complexes may have a Stokes shift of 45 nm or greater. 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.

[0055] The photoluminescent complexes of the present disclosure can have tunable emission wavelengths: by substituting the BODIPY moiety with different substituents, the emission wavelength can be tuned to between about 500 nm and about 560 nm, or any value bounded by this range.

[0056] In some embodiments, the blue light absorbing moiety can have a peak absorption maximum between wavelengths of about 400 nm and about 470 nm, hi some embodiments, the peak absorption can be between about 400 nm and about 405 nm, about 405 nm and 410 nm, about 410 nm and 415 nm, about 415 nm and 420 nm, about 420 nm and 425 nm, about 425 nm and 430 nm, about 430 nm and 435 nm, about 435 nm and 440 nm, about 440 nm and 445 nm, about 445 nm and 450 nm, about 450 nm and 455 nm, about 455 nm and 460 nm, about 460 nm and 465 nm, about 465 nm and 470 nm, or any wavelength within a range bounded by any of these values.

[0057] In some embodiments, the photoluminescent complex may have an emission peak between about 500 nm and about 560 nm, hi some embodiments, the emission peak may be between about 500 nm and about 515 nm, about 515 nm and about 520 nm, about 520 nm and about 525 nm, about 525 nm and about 530 nm, about 530 nm and about 535 nm, about 535 nm and about 540 nm, about 540 nm and about 545 nm, about 545 nm and about 550 nm, about 550 nm and about 555 nm, about 555 nm and about 560 nm, or any wavelength within a range bounded by any of these ranges.

[0058] In some embodiments, the photoluminescent complex can have an absorption peak at any wavelength between about 500 nm and about 520 nm, about 500 nm and about 505 nm, about 505 nm and about 510 nm, about 510 nm and about 515 nm, about 515 nm and about 520 nm, or within a range bounded by any of these ranges.

[0059] Some embodiments include a photoluminescent complex, wherein the spatial distance between the blue-light absorbing xanthenoisoquinoline or derivative and the BODIPY moiety is adjusted via a linker conjugate for energy transfer of the blue-light absorbing xanthenoisoquinoline derivative to the BODIPY moiety.

[0060] The present disclosure includes a photoluminescent complex (PLC), the photoluminescent complex comprising a blue-light-absorbing xanthenoisoquinoline derivative, a linker conjugate, and a BODIPY moiety. The linker conjugate covalently bonds the blue-light-absorbing xanthenoisoquinoline derivative to the BODIPY moiety. In some embodiments, the xanthenoisoquinoline derivative absorbs light energy at a first excitation wavelength and transfers the energy to the BODIPY moiety, the BODIPY moiety absorbs energy from the xanthenoisoquinoline derivative and emits light energy at a second, higher wavelength, and the photoluminescent complex has an emission quantum yield of greater than 80%.

[0061] Some embodiments include blue light absorbing xanthenoisoquinoline derivatives, which have the following general formula: [ka] (In the formula, R 0 and R 10 is H, C 1~4 alkyl groups (e.g., methyl, n-butyl, t-butyl, etc.), -CF3, optionally substituted aryl (e.g., [ka] etc.), or -(OCH2CH2) n It may be -OCH3 (where n is 1, 2, 3, or 4), or alkoxy, and the dashed line represents the point of attachment of the xanthenoisoquinoline moiety to the linker conjugate.

[0062] In some embodiments, R 10is C such as methyl, ethyl, n-propyl, isopropyl, butyl, t-butyl, etc. 1~4 In some examples, R 10 is H. In some embodiments, R 10 is t-butyl. In other embodiments, R 10 may be an aryl moiety (eg, unsubstituted phenyl, substituted phenyl, or optionally substituted aryl).

[0063] In some embodiments, the photoluminescent complex comprises a linker conjugate that covalently attaches the blue-light-absorbing xanthenoisoquinoline derivative to the BODIPY moiety. In some embodiments, the linker conjugate can comprise a single bond between the xanthenoisoquinoline derivative and the BODIPY moiety.

[0064] In some embodiments, the linker conjugate can include a substituted ester, an unsubstituted ester, a substituted ether, or an unsubstituted ether, hi some embodiments, the linker conjugate can include an optionally substituted ester group.

[0065] In some embodiments, the linker conjugate comprises a substituted ester group, and the linker conjugate has the following structure: [ka] may have:

[0066] In some embodiments, the linker conjugate may comprise an unsubstituted ester group, and the linker conjugate has the following structure: [ka] may have:

[0067] In some embodiments, the linker conjugate comprises an ether group and the linker conjugate has the following structure: [ka] may have:

[0068] In some embodiments, the linker conjugate comprises: [ka] It could be.

[0069] In some embodiments, the linker conjugate comprises: [ka] It could be.

[0070] In some embodiments, the linker conjugate comprises: [ka] It could be.

[0071] In some embodiments, the linker conjugate comprises: [ka] It could be.

[0072] In some embodiments, the linker conjugate comprises: [ka] It could be.

[0073] In some embodiments, the linker conjugate comprises: [ka] It could be.

[0074] In some embodiments, the linker conjugate comprises: [ka] could be.

[0075] In some embodiments, the linker conjugate comprises: [ka] It could be.

[0076] In some embodiments, the linker conjugate comprises: [ka] It could be.

[0077] In some embodiments, the linker conjugate comprises: [ka] It could be.

[0078] In some embodiments, the linker conjugate comprises: [ka] It could be.

[0079] In some embodiments, the linker conjugate comprises: [ka] It could be.

[0080] In some embodiments, the linker conjugate comprises: [ka] It could be.

[0081] In some embodiments, the linker conjugate comprises: [ka] It could be.

[0082] The photoluminescent complexes of the present disclosure can include a BODIPY moiety, which has the following general formula: [ka] wherein X may be F or CN; 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; 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; R 2 and R 5 may independently be H, alkyl, cycloalkyl, alkenyl, cyano (—CN), an alkyl ester (e.g., ethyl ester, 2-ethylhexyl ester, 2,2,2-trifluoroethyl ester, glycol ester, etc.), or an aryl ester (e.g., phenyl ester (—C(O)OCHPh), etc.); R 7 and R 8 are independently optionally substituted aryl (e.g., phenyl, 3,5-bistrifluoromethylphenyl, 3,5-bis-t-butylphenyl, 3,5-bisfluorophenyl, 3,5-bischlorophenyl, biphenyl, etc.), C 1~8 Alkyl (e.g., ethyl, pentyl, 2-ethylhexyl, CH2-cyclohexyl, etc.), C 3~8 Cycloalkyl (e.g., cyclopropyl, cyclohexyl, etc.), C 1~10 ether groups having alkyl groups (e.g., -OCH3, -O-(2-ethylhexyl), OCH2-cyclohexyl, etc.), ether moieties having optionally substituted aryl groups (e.g., -OPh), or C 1~10It may be an arylalkyl group (e.g., —O(CH2)3-Ph, etc.), L may have a linker complex that includes an optionally substituted ester or an optionally substituted ether linker.

[0083] In some embodiments, the BODIPY moiety of the present disclosure is R 1 , R 3 , R 4 , and R 6 are methyl, and R 2 and R 5 are each a substituted ester group, the substituted ester group containing a C1 to C7 alkyl chain or a polyglycol chain, and R 7 and R 8 are each optionally substituted aryl, alkyl, or ether, and L may be a BODIPY moiety, including a linker complex.

[0084] In some embodiments, R 2 and R 5 is, independently, [ka] may be.

[0085] In some embodiments, R 2 teeth, [ka] may be.

[0086] In some embodiments, R 2 teeth, [ka] may be.

[0087] In some embodiments, R 2 teeth, [ka] may be.

[0088] In some embodiments, R 2 teeth, [ka] may be.

[0089] In some embodiments, R 2 teeth, [ka] may be.

[0090] In some embodiments, R 2 teeth, [ka] may be.

[0091] In some embodiments, R 2 teeth, [ka] may be.

[0092] In some embodiments, R 5 teeth, [ka] may be.

[0093] In some embodiments, R 5 teeth, [ka] may be.

[0094] In some embodiments, R 5 teeth, [ka] may be.

[0095] In some embodiments, R 5 teeth, [ka] may be.

[0096] In some embodiments, R 5 teeth, [ka] may be.

[0097] In some embodiments, R 5 teeth, [ka] may be.

[0098] In some embodiments, R 5 teeth, [ka] may be.

[0099] In some embodiments, R 7 and R 8 may independently be an optionally substituted aryl. In some embodiments, the optionally substituted aryl group may be an optionally substituted phenyl group. In some embodiments, the optionally substituted benzyl group may be an unsubstituted phenyl group, an unsubstituted diphenyl group, and / or C 3~12 It may also be an alkyl ester group.

[0100] In some embodiments, R 7 and R 8 are independently a phenyl group, a 3,5-difluorophenyl group ( [ka] ), 3,5-dichlorophenyl group ( [ka] ), 3,5-di-t-butylphenyl group ( [ka] ), biphenyl groups (e.g., [ka] ), bis-3,5-di(2-ethylhexyl) 5-isophthalate ( [ka] ), or 3,5-bis((perfluorophenyl)methyl)isophthalate group ( [ka] ) may also be used.

[0101] In some embodiments, R 7 and R 8 independently, C 2~8 Alkyl groups (e.g., ethyl, pentyl, 2-ethylhexyl, CH2-cyclohexyl, etc.), C 3~8 Cycloalkyl (e.g., cyclopropyl, cyclohexyl, etc.), C 1~10 an ether group having an alkyl group of the formula (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 It may also be an arylalkyl group (for example, -O(CH2)3-Ph, etc.).

[0102] Photoluminescent complexes of the present disclosure can be represented by the following, which is provided for illustrative purposes and is not to be construed as limiting in any way: [ka]

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[0103] Some embodiments include a color conversion film, which includes a color conversion layer including a resin matrix and a photoluminescent complex described above dispersed within the resin matrix. In some embodiments, the color conversion film may include one or more complexes described herein.

[0104] Some embodiments include color conversion films that can be about 1 μm to about 200 μm thick. In some embodiments, the color conversion film has a thickness of about 1 μm to about 5 μm, about 5 μm to about 10 μm, about 10 μm to about 15 μm, about 15 μm to about 20 μm, about 20 μm to about 40 μm, about 40 μm to about 80 μm, about 80 μm to about 120 μm, about 120 μm to about 160 μm, about 160 μm to about 200 μm, or any thickness in a range bounded by any of these values.

[0105] In some embodiments, the color conversion film can absorb light in the wavelength range of about 400 nm to about 480 nm and emit light in the wavelength range of about 500 nm to about 560 nm.

[0106] In some embodiments, the color conversion film may further include a transparent substrate layer. The transparent substrate layer has two opposing surfaces, and the color conversion layer may be disposed on the surface of the transparent layer adjacent to the light source and be in physical contact with it. The transparent substrate is not particularly limited, and a person skilled in the art would be able to select a transparent substrate from those used in the art. Some non-limiting examples of transparent substrates include PE (polyethylene), PP (polypropylene), PEN (polyethylene naphthalate), PC (polycarbonate), PMA (polymethyl acrylate), PMMA (polymethyl methacrylate), CAB (cellulose acetate butyrate), PVC (polyvinyl chloride), PET (polyethylene terephthalate), PETG (glycol-modified polyethylene terephthalate), PDMS (polydimethylsiloxane), COC (cycloolefin copolymer), PGA (polyglycolide or polyglycolic acid), PLA (polylactic acid), PCL (polycaprolactone), PEA (polyethylene adipate), PHA (polyhydroxyalkanoate), PHBV (poly(3-hydroxybutyrate-co-3-hydroxyvalerate)), PBE (polybutylene terephthalate), and PTT (polytrimethylene terephthalate). Any of the above, alone or in combination, can comprise a transparent substrate layer.

[0107] In some embodiments, the transparent substrate may have two opposing surfaces. In some embodiments, the color conversion film may be disposed on one of the opposing surfaces and be in physical contact with it. In some embodiments, the surface of the transparent substrate on which the color conversion film is not disposed may be adjacent to the light source. In some examples, the substrate may function as a support during the preparation of the color conversion film. The type of substrate used is not particularly limited, and the material and / or thickness are not limited as long as it is transparent and can function as a support. One skilled in the art would be able to determine which material and thickness to use as the support substrate.

[0108] Some embodiments include a method of making a color conversion film, the method including dissolving a photoluminescent complex described herein and a binder resin in a solvent and applying the mixture to the surface of a transparent substrate.

[0109] In some embodiments, the color conversion film comprises a singlet oxygen quencher. In some embodiments, the color conversion film comprises a free radical scavenger.

[0110] Binder resins that can be used with the photoluminescent complex(es) include acrylic resins, polycarbonate resins, ethylene-vinyl alcohol copolymer resins, ethylene-vinyl acetate copolymer resins and their saponification products, AS resins, polyester resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins, polyvinyl phosphonic acid (PVPA), polystyrene resins, phenolic resins, phenoxy resins, polysulfone, nylon, cellulose resins, and cellulose acetate resins, etc. In some embodiments, the binder resin can be a polyester resin and / or an acrylic resin.

[0111] In some embodiments, solvents that can be used to dissolve or disperse the complex and resin include alkanes such as butane, pentane, hexane, heptane, and octane; cycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane; alcohols such as ethanol, propanol, butanol, amyl alcohol, hexanol, heptanol, octanol, decanol, undecanol, diacetone alcohol, and furfuryl alcohol; Cellosolves™ such as Methyl Cellosolve™, Ethyl Cellosolve™, Butyl Cellosolve™, Methyl Cellosolve™ acetate, and Ethyl Cellosolve™. Cellosolve™ acetate, propylene glycol and its derivatives, such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, and dipropylene glycol dimethyl ether, ketones, such as acetone, methyl amyl ketone, cyclohexanone, and acetophenone, ethers, such as dioxane and tetrahydrofuran, Furans, esters such as butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate, ethyl 2-hydroxybutyrate, ethyl acetoacetate, methyl lactate, ethyl lactate, and methyl 3-methoxypropionate, halogenated hydrocarbons such as chloroform, methylene chloride, and tetrachloroethane, aromatic hydrocarbons such as benzene, toluene, xylene, and cresol, and highly polar solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone may be mentioned.

[0112] Some embodiments include a backlight unit, which may include the color conversion film described above.

[0113] Other embodiments include display devices that may include the backlight units described herein.

[0114] Unless otherwise indicated, all numbers used in the specification and embodiments expressing properties such as amounts of ingredients, molecular weights, reaction conditions, and the like, should be understood to be modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and accompanying embodiments are approximations that may vary depending upon the desired properties sought to be obtained, at least not as an attempt to limit the application of the doctrine of equivalents. Within the scope of the embodiments, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0115] For the disclosed processes and / or methods, the functions performed in the processes and methods may be implemented in various orders, as may be indicated by the context. Furthermore, the outlined steps and operations are presented by way of example only, and some steps and operations may be optional, combined into fewer steps and operations, or expanded into additional steps and operations.

[0116] This disclosure may at times describe different components contained within or associated with different other components. Such depicted configurations are merely exemplary, and many other configurations may be realized that achieve the same or similar functionality.

[0117] Generally, the terms used in this disclosure and the accompanying embodiments (e.g., the body of the accompanying embodiments) are intended as "open" terms (e.g., the term "including" should be interpreted as "including, but not limited to," the term "having" should be interpreted as "having at least," the term "includes" should be interpreted as "includes, but not limited to," etc.). Furthermore, when a specific number of elements is introduced, this may be interpreted to mean at least the recited number, as may be indicated by context (e.g., the bare recitation of "two descriptions," without other modifiers, means at least two descriptions of two or more descriptions). As used in this disclosure, any disjunctive word and / or disjunctive phrase expressing two or more alternative terms should be understood to contemplate the possibility of including one of the terms, either of the terms, or both terms. For example, the phrase "A or B" will be understood to include the possibilities of "A" or "B" or "A and B."

[0118] Use of the terms "may" or "may be" should be interpreted as abbreviations 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 complex may have a Stokes shift of 45 nm or greater" should be interpreted as, for example, "In some embodiments, the photoluminescent complex has a Stokes shift of 45 nm or greater," or "In some embodiments, the photoluminescent complex does not have a Stokes shift of 45 nm or greater."

[0119] As used in the context of describing the present disclosure (particularly in the context of the embodiments below), the terms "a," "an," "the," and similar referents should be construed to cover both the singular and the plural unless otherwise indicated herein or clearly contradicted by context. The use of any and all examples or representative language (e.g., "such as") presented herein is intended merely to better clarify the disclosure and does not pose a limitation on the scope of any embodiment. No language in the specification should be construed as indicating any non-embodied element essential to the practice of the disclosure.

[0120] Groupings of alternative elements or embodiments disclosed herein are not to be construed as limiting. Each group member may be referenced and embodied individually or in any combination with other members of the group or other elements found herein. It is anticipated that one or more members of a group may be included in, or deleted from, a group for reasons of convenience and / or patentability. When such inclusions or deletions are made, the specification is deemed to satisfy the description of all Markush groups used in the appended embodiments to include the modified group.

[0121] Certain embodiments include the best mode known to the inventors for carrying out the present disclosure. Of course, variations on these embodiments will become apparent to those skilled in the art upon reading the foregoing description. The inventors anticipate that those skilled in the art will employ such variations as appropriate, and the inventors intend for the present disclosure to be practiced otherwise than as specifically described herein. Accordingly, the embodiments include all modifications and equivalents of the subject matter described in the embodiments as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is contemplated unless otherwise indicated herein or otherwise clearly contradicted by context. Finally, it should be understood that the embodiments disclosed herein are illustrative of the principles of the embodiments. Other variations that may be employed are within the scope of the embodiments. Thus, by way of example, but not limitation, alternative embodiments may be utilized in accordance with the teachings herein. Accordingly, the embodiments are not limited to those precisely shown and described.

[0122] Embodiment Embodiment 1: A photoluminescent complex comprising: a blue light absorbing portion; a linker complex; a boron-dipyrromethene (BODIPY) moiety; wherein the BODIPY moiety comprises the general formula: [ka] (In the formula, R 1 and R 6 are independently H, alkyl, cycloalkyl, or alkenyl, and R 3 and R 4 are independently selected from C1-C2 alkyl, and R 2 and R 5 is independently selected from H, alkyl, cycloalkyl, alkenyl, cyano (-CN), alkyl ester (-COOCHCH), aryl ester (-COOCHAr), or EtOC; R 7and R 8 is optionally substituted aryl; a linker conjugate covalently linking 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, and the BODIPY moiety absorbs the energy from the blue light absorbing moiety and emits light energy at a second, longer wavelength, and wherein the photoluminescent complex has an emission quantum yield of greater than 80%.

[0123] Embodiment 2 R 7 and R 8 The substituted aryl of the formula: [ka] 2. The photoluminescent complex of embodiment 1, selected from:

[0124] Embodiment 3 The photoluminescent complex of embodiment 1, wherein the blue light absorbing moiety is a xanthenoisoquinoline derivative.

[0125] Embodiment 4: The xanthenoisoquinoline derivative has the general formula: [ka] (In the formula, R 0 are independently selected from H, C1-C3 alkyl, optionally substituted aryl, or optionally substituted heteroaryl.

[0126] Embodiment 5: The BODIPY moiety has the general formula: [ka] (In the formula, R 1 and R 6 are independently selected from H, a saturated or unsaturated alkyl group, or an alkene group; R 3 and R 4are independently selected from C1-C2 alkyl, and R 2 and R 5 is independently selected from H, alkyl, cycloalkyl, alkenyl, cyano (-CN), alkyl ester (-COOCHCH), aryl ester (-COOCHAr), or EtOC; R 7 and R 8 is a substituted aryl.

[0127] Embodiment 6 R 1 , R 3 , R 4 and R 6 are independently selected from C1-C3 alkyl or methyl groups, and R 2 and R 5 is independently selected from a C1-C3 ester group or a CH3CH2CO2 ester.

[0128] Embodiment 7: The unsubstituted ester has the following structure: [ka] 11. The photoluminescent complex of embodiment 10, comprising one of:

[0129] Embodiment 8: The substituted ester has the following structure: [ka] 11. The photoluminescent complex of embodiment 10, comprising one of:

[0130] Embodiment 9. The unsubstituted and / or substituted ether has the following structure: [ka] 11. The photoluminescent complex of embodiment 10, comprising one of:

[0131] Embodiment 10: The photoluminescent complex has the following structure: [ka] [ka] 10. The photoluminescent complex of embodiment 1, 2, 3, 4, 5, 6, 7, 8, or 9, comprising one of:

[0132] Embodiment 11: A color conversion film comprising: A transparent substrate layer; a color conversion layer including a resin matrix; a photoluminescent complex, comprising the photoluminescent complex of embodiment 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, wherein the photoluminescent compound is dispersed within the resin matrix; and Including color conversion film.

[0133] Embodiment 12. The color conversion film of embodiment 11, further comprising a singlet oxygen quencher.

[0134] Embodiment 13. The color converting film of embodiment 11, further comprising a free radical scavenger.

[0135] Embodiment 14 The color conversion film of embodiment 11, wherein said color conversion film has a thickness between 10 μm and 200 μm.

[0136] Embodiment 15 The color conversion film of embodiment 11, wherein the color conversion film absorbs light in the wavelength range of about 400 nm to about 480 nm and emits light in the wavelength range of 500 nm to about 560 nm.

[0137] Embodiment 16. A method of making the color conversion film of embodiment 12, 13, 14, or 15, comprising: Dissolving the photoluminescent complex of embodiment 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 and a binder resin in a solvent; applying the mixture to one of the opposing surfaces of a transparent substrate; A method comprising:

[0138] Embodiment 17: A backlight unit comprising the color conversion film of embodiment 11, 12, 13, 14 or 15.

[0139] Embodiment 18 A display device comprising the backlight unit of embodiment 17. [Example]

[0140] It has been discovered that embodiments of the photoluminescent complexes described herein have improved performance compared to other forms of dyes used in color conversion films. These advantages are further illustrated by the following examples, which are intended merely to illustrate the disclosure and are not intended to limit the scope or underlying principles in any way.

[0141] Example 1 - Comparative Example (CE) and Photoluminescent Compound (PLC) Comparative example 1 (CE-1) [ka]

[0142] CE-1: 0.75 g of 4-hydroxyl-2,6-dimethylbenzaldehyde (5 mmol) and 1.04 g of 2,4-dimethylpyrrole (11 mmol) were dissolved in 100 mL of anhydrous dichloromethane. The solution was degassed for 30 minutes. Next, one drop of trifluoroacetic acid was added. The solution was stirred overnight at room temperature under an argon gas 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 washed with dichloromethane to obtain dipyrrolmethane (1.9 g). Next, 1.0 g of dipyrrolmethane was dissolved in 60 mL of THF. 5 mL of trimethylamine was added to the solution, followed by degassing for 10 minutes. After degassing, 5 mL of trifluoroborane-diethyl ether was slowly added, followed by heating at 70 °C for 30 minutes. The resulting solution was loaded onto silica gel and purified by flash chromatography using dichloromethane as the eluent. The desired fractions were collected and dried under vacuum to give 0.9 g of an orange solid (76% yield). LCMS (APCI+): C 21 H 24 Calculated for BF2N2O (M+H) = 369; Found: 369. 1 H NMR (400 MHz, chloroform-d) δ 6.64 (s, 2H), 5.97 (s, 2H), 4.73 (s, 1H), 2.56 (s, 6H), 2.09 (s, 6H), 1.43 (s, 6H).

[0143] Comparative Example 2 (CE-2): Synthesized as described in Wakamiya, Atsushi et al. Chemistry Letters, 37(10), 1094-1095; 2008.

[0144] Comparative Example 3 (CE-3): Synthesized as follows: [ka]

[0145] Compound CE-3.1 (6-(2-nitrophenoxy)-1H,3H-benzo[de]isochromene-1,3-dione): A mixture of 2-nitrophenol (6.6 g, 48 mmol) and KOH powder (2.4 g, 43 mmol) was mixed and stirred under vacuum for 30 minutes, then copper powder (0.4 g) was added, followed by 100 mL of anhydrous DMF. The mixture was stirred for 5 minutes, then 4-chloronaphthalic anhydride (5.1 g, 22 mmol) was added. The whole was degassed and then heated under reflux for 1.5 hours. After cooling to room temperature, 100 mL of 20% hydrochloric acid was added dropwise to the resulting reaction mixture, which was allowed to stand for 2 hours. The precipitate was collected by filtration and then dried under vacuum overnight to give a tan solid (4.6 g). This was further purified by stirring in refluxing acetic acid (50 mL) for 1 hour and then cooling to room temperature. Filtration and air drying gave a yellow solid (3.0 g, 41% yield). LCMS (APCI) analysis confirmed: C 18 H 10 Calculated for NO6 (M+H): 336.0; Found: 336. 1 H NMR(400MHz,chloroform-d) δ 8.80(dd,J=8.5,1.2Hz,1H), 8.72(dd,J=7.3,1.2Hz,1H), 8.50(d,J=8.2Hz,1H), 8.19(dd,J=8.2,1.7Hz,1H), 7.90(dd,J=8. 5,7.3Hz,1H), 7.79(td,J=7.9,1.7Hz,1H), 7.54(td,J=8.0,1.3Hz,1H), 7.39(dd,J=8.3,1.2Hz,1H), 6.89(d,J=8.2Hz,1H).

[0146] Compound CE-3.2 (6-(2-aminophenoxy)-1H,3H-benzo[de]isochromene-1,3-dione): A mixture of compound CE-3.1 (2.0 g, 6 mmol) and iron powder (<10 μM, 0.91 g, 16 mmol) in acetic acid (75 mL) was heated to reflux for 30 minutes. The resulting solution was poured into water (220 mL). The resulting precipitate was collected by filtration, washed with water, dried thoroughly in air, and then dried under vacuum to give a yellow solid (1.65 g, 90% yield). Confirmed by LCMS (APCI): C 18 H 12Calculated for NO4 (M+H): 306.1; Found: 306.

[0147] Compound CE-3.3 (1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione): Compound CE-3.3 (1.5 g, 4.9 mmol) was dispersed in acetic acid (35 mL) and cooled to 0 °C. While stirring, pre-cooled hydrochloric acid (3 mL, 37 mmol) was added, followed by dropwise addition of 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 1 hour, then transferred to an addition funnel and added dropwise to a refluxing copper sulfate solution (5.08 g, 20 mmol) in 50 mL of water over 1 hour. After cooling to room temperature, the precipitate was collected by filtration, washed with water and acetone, and then dried in air and then in vacuo to give a yellow solid (0.92 g, 65% yield). Confirmed by LCMS (APCI): C 18 Calculated for H8O4 (M-): 288.0; Found: 288.

[0148] Compound CE-3.4 (5,11-dibromo-1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione): A 2 L 2N round-bottom flask was equipped with a stir bar and a long finned condenser. Compound CE-1.1 (34.688 mmol, 10.00 g) was added to the flask, followed by ortho-dichlorobenzene (1000 mL). The reaction mixture was stirred at room temperature, and Br2 (416.26 mmol, 21.3 mL) was added. The second neck was stoppered, and the reaction mixture was heated to 75 °C open to the atmosphere using an aluminum heat block over the weekend. The reaction mixture was cooled to room temperature, and the solid was filtered off. The filtrate was diluted with hexane (approximately 20% by volume), and a second precipitate was filtered off. Both precipitates were dried under vacuum at 100 °C. Orange-colored solid, 10.866 g total (69.9% yield). Both had similar LCMS and NMR. MS (APCI): Formula: C 18 Calculated for H6Br2O4 (M+H) = 445; Found: 445. 1H NMR(400MHz,TCE) δ 9.47(dd,J=8.4,1.5Hz,1H), 8.76(d,J=14.2Hz,2H), 7.72~7.63(m,1H), 7.56(dd,J=8.3,1.4Hz,1H), 7.46(ddd,J=8.5,6.7,1.9Hz,1H).

[0149] 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): A 100 mL 2N round-bottom flask was equipped with a stir bar, a finned condenser / gas adapter, and a flow control. 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 at 160 °C for 5 h. The crude reaction mixture was cooled to 0 °C, quenched with 6N HCl (approximately 5 mL), and diluted with water (up to approximately 350 mL). The precipitate was filtered off and washed with water. The product was dried by suction and used in the next reaction without further purification. A 100% yield is assumed. MS (APCI): Chemical Formula: C 26 H 13 Calculated for Br2NO5 (M+H) = 578; Found: 578.

[0150] Compound CE-3.8: A mixture of ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (1.0 g, 6.0 mmol), 4-hydroxy-2,6-dimethylbenzaldehyde (0.449 g, 3.0 mmol), and p-toluenesulfonic acid (p-TsOH) (50 mg, 0.29 mmol) in 50 mL of dichloroethane (DCE) was degassed and stirred overnight at room temperature. Liquid chromatography-mass spectroscopy (LCMS) analysis indicated the reaction was complete with a main peak at m / e = 467. To the mixture obtained above, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (0.817 g, 3.6 mmol) was added, and the whole was stirred at room temperature for 30 minutes. LCMS analysis indicated the reaction was complete with a main peak at m / e = 465. While cooling with an ice-batch, the mixture obtained above was added with triethylamine (1.7 mL, 12 mmol) and BF 3- Diethyl ether (2.2 mL, 18 mmol) was added, and the resulting mixture was stirred at 50° C. for 1 h. An additional 1 mL of triethylamine and 1 mL of BF3-diethyl ether were added, and the whole was heated for another 1 h. LCMS analysis showed that all of the dipyrrolmethane starting material had been 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 an eluent of hexane / ethyl acetate (0% → 30% ethyl acetate). The desired fractions were collected. After removal of the solvent, the desired product was obtained as an orange solid (1.0 g, 65% yield). 1 H NMR (400 MHz, chloroform-d) δ 6.68 (s, 2H), 4.29 (q, J = 7.1 Hz, 4H), 2.84 (s, 6H), 2.05 (s, 6H), 1.34 (t, J = 7.1 Hz, 6H). LCMS (APCI+): C 27 H 32 Calculated for BF2N2O5 (M+H) = 513.2; Found: 513.

[0151] 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): A 250 mL 2N round-bottom flask was equipped with a stir bar, a finned condenser / gas adapter, and a flow control. The system was flushed with argon. Compound CE-3.5 (3.500 mmol, 2.034 g), (3,5-bis(trifluoromethyl)phenyl)boronic acid (14.00 mmol, 3.611 g), K2CO3 (19.25 mmol, 2.661 g), THF (60 mL), DMF (12 mL), and water (6 mL) were added to the flask. The reaction mixture was stirred under argon at room temperature for several minutes, and then Pd(dppf)Cl2 (0.0245 mmol, 179 mg) was added. The headspace was flushed with argon for 1 minute, and then the flow control was closed. The reaction mixture was stirred and heated at 80 °C in an aluminum heating block for 3 hours. The crude reaction mixture was evaporated to dryness in vacuo, dissolved in DCM, and evaporated in vacuo onto approximately 35 g of flash silica gel. Purification was achieved by flash chromatography on silica gel (220 g, equilibrated 0% EtOAc / DCM, eluting 0% (10 CV) → 15.3% EtOAc / DCM (15.3 CV) → 40% EtOAc / DCM (10 CV) → isocratic 40% EtOAc / DCM). EtOAc contained 0.1% v / v TFA. 1.710 g (57.6% yield) of a brownish-yellow solid was obtained. MS (APCI): Formula: C 42 H 19 F 12 Calculated for NO5 (M+H)=846; Found: 846. 1H NMR (400 MHz, DMSO) δ 12.45(s,1H), 8.62(s,1H), 8.52(d,J=1.7Hz,2H), 8.36(s,1H), 8.30(s, 1H), 8.26(d,J=1.6Hz,2H), 8.24(s,1H), 7.50(ddd,J=8.5,7.2,1.5Hz,1H ), 7.46~7.38(m,2H), 7.37~7.27(m,2H), 7.14(dd,J=8.3,1.2Hz,1H), 6.98(ddd,J=8.4,7.2,1.3Hz,1H), 6.85(dd,J=8.3,1.5Hz,1H), 3.69(s,2H).

[0152] 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): 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 tosylic 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 main peak at m / e = 467.

[0153] To the resulting solution was added DDQ (0.817 g, 3.6 mmol), followed by stirring at room temperature for 30 minutes. LCMS analysis showed that all starting material was converted to the desired product with m / e+=465.

[0154] With 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 1 hour. LCMS analysis showed approximately 30% conversion. To this mixture, another 1 mL of triethylamine and 1 mL of BF3-diethyl ether were added, and the whole was heated at 50°C for another 1 hour. LCMS analysis showed that all of the starting material had been 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 main desired 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).

[0155] Compound CE-3 (diethyl 10-(4-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dimethylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate): Compound CE-3.6 (0.113 mmol, 80 mg), compound CE-3.7 (diethyl 5,5-difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate) (0.0750 mmol, 38 mg), and DMAP·pTsOH salt (0.150 mmol, 44 mg) were placed in a 40 mL screw-cap vial with a stir bar. Dry DCM (10 mL) was added to the vial, and the mixture was stirred to obtain a solution. DIC (0.263 mmol, 0.41 mL) was added to the vial. The reaction was capped and stirred at room temperature overnight. The crude reaction mixture was diluted with hexane and loaded onto approximately 20 g of flash silica gel in a loader. Purification was carried out by flash chromatography on silica gel (120 g, equilibrated with 0% EtOAc / hexane, eluted with 0% (2 CV) → 50% EtOAc / hexane (30 CV)). Fractions containing the product were evaporated to dryness in vacuo. 70 mg of an orange solid was obtained (78% yield). MS (APCI): Formula: C 65 H 46 Calculated for BF8N3O9 (M+H)=1176; Found: 1176. 1 H NMR (400MHz, TCE) δ 8.71(s,1H), 8.48(s,1H), 7.95~7.80(m,6H), 7.66(t,J=8.4Hz,4H), 7.4 7~7.35(m,3H), 7.31(dd,J=8.3,1.3Hz,1H), 7.10(dd,J=8.4,1.5Hz,1H), 7.05(s,2H), 6.96(ddd,J=8.4,7.1,1.4Hz,1H), 4.28(q,J=7.1Hz,4H),4. 02(s,2H), 2.84(s,6H), 2.15(s,6H), 1.73(s,6H), 1.34(t,J=7.1Hz,6H).

[0156] Comparative example 4 (CE-4) [ka]

[0157] Diethyl 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-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate: 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 (0.3000 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 dry DCM (10 mL) at room temperature for 1 h. The crude reaction mixture was loaded onto approximately 30 g of flash silica gel packed in a loader. Purification was carried out by flash chromatography on silica gel (120 g, eluting with 0% EtOAc / DCM (2 CV) → isocratic step to 3.8% EtOAc / DCM, then isocratic to elute the product). The product-containing fractions were evaporated to dryness in vacuo. 304 mg (84% yield) of an orange solid was obtained. MS (APCI): Formula: C 67 H 50 Calculated for BF8N3O9 (M+H) = 1204; Found: 1204. 1H NMR(400MHz,TCE) δ 8.71(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=7.1Hz,4H ), 4.02(s,2H), 2.84(s,6H), 2.16(s,6H), 1.74(s,6H), 1.34(t,J=7.1Hz,6H).

[0158] Photoluminescent compound PLC-1: [ka]

[0159] Compound PLC-1.1 ((3,5-dibromophenoxy)triethylsilane): A 500 mL 2N round-bottom flask was equipped with a stir bar and fitted with a gas adapter and septum. The flask was placed in a Dewar bowl. The flask was flushed with argon. To the flask was added 3,5-dibromophenol (100.0 mmol, 25.190 g), imidazole (300.0 mmol, 20.430 g), and dry DCM (200 mL). The mixture was stirred at room temperature to obtain a solution and then cooled to 0 °C in an ice-water bath. To the flask was added chlorotriethylsilane (150.0 mmol, 25.2 mL) via syringe with stirring at 0 °C. The reaction was stirred at 0 °C for 50 minutes and 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 carried out by flash chromatography on silica gel (220 g, equilibrated and eluted with 100% hexane). The product-containing fractions were evaporated to dryness in vacuo. 27.811 g (76% yield) of a colorless oil was obtained. MS (APCI): Chemical formula: C 12 H 18Calculated for Br2OSi (M+H) = 365; found: 365. 1 H NMR(400MHz,TCE) δ 7.28(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).

[0160] Compound PLC-1.2 (2,6-dibromo-4-hydroxybenzaldehyde): A 250 mL 2N round-bottom flask was equipped with a stir bar and fitted with a gas adapter and septum. The flask was placed in a Dewar bowl. The flask was flushed with argon. Compound 1.1 (30.00 mmol, 10.985 g) was weighed and azeotroped from toluene. Compound 1.1 was transferred to the reaction flask under argon, and then dry THF was added (130 mL). The reaction mixture was stirred to obtain a homogeneous solution at room temperature. The reaction mixture was cooled to -78 °C (dry ice / acetone). The system was purged of oxygen by vacuum / backfill argon cycles (3x). A solution of LDA in THF / hexane (1.0 M, 60.00 mmol, 60.0 mL) was added over several minutes with vigorous stirring. The solution was stirred at -78°C for 70 minutes, then anhydrous DMF (150.0 mmol, 11.6 mL) was added via syringe and stirred at -78°C for 60 minutes. The reaction mixture was poured cold into 400 mL of saturated NH4Cl solution with stirring. The solution was extracted with 100 mL of EtOAc, and the layers were separated. The aqueous layer was acidified to pH ≈1 using excess 6N HCl, resulting in an off-white precipitate (ppt). The organic layer was extracted with 100 mL of saturated NH4Cl and then twice with 10% K2CO3 (100 mL). These aqueous extracts were also added to acidified water to maintain a pH ≈1. The resulting precipitate was filtered and then dried overnight in a vacuum oven at 90°C. 6.665 g (79% yield) of an off-white / gray precipitate was obtained. MS (APCI): Calculated for formula C7H4Br2O2 (M+H) = 281; Found: 281. 1 H NMR (400 MHz, acetone) δ 10.14 (s, 1H), 7.24 (s, 2H).

[0161] 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 stir bar, a finned condenser / gas adapter, and a flow control. The system was flushed with argon. To the flask was added compound 1.2 (5.500 mmol, 1.540 g), (3,5-di-tert-butylphenyl)boronic acid (22.00 mmol, 5.150 g), NaHCO3 (33.00 mmol, 2.772 g), Pd(dppf)Cl2 (1.100 mmol, 805 mg), dry THF (270 mL), and water (9 mL). The heat block was set to 80 °C, and the reaction mixture 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 carried out by flash chromatography on silica gel (220 g, equilibrated with 0% EtOAc / hexane, eluted with 0% (2 CV) → 30% EtOAc / hexane (20 CV)). The product-containing fractions were evaporated to dryness in vacuo. 2.256 g (82% yield) of a pale yellow solid was obtained. MS (APCI): Chemical formula: C 35 H 46 Calculated for O2 (M+H) = 499; Found: 499. 1 H NMR(400MHz,TCE) δ 9.80(s,1H), 7.42(t,J=1.8Hz,2H), 7.15(d,J=1.8Hz,4H), 6.87(s,2H), 1.35(s,36H).

[0162] Compound PLC-1.4 (3,3'',5,5''-tetra-tert-butyl-2'-formyl-[1,1':3',1''-terphenyl]-5'-yl 2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate): In a 40 mL screw-cap vial, add compound 1.3 (4.523 mmol, 2256 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 (CE-3.6) (5.428 mmol, 4 A mixture of 0.590 g of HCl, DMAP·pTsOH salt (4.523 mmol, 1332 mg), and dry DCM (20 mL) was added with a stir bar. The reaction mixture was stirred at room temperature to give a yellow slurry. While stirring at room temperature, DIC (9.047 mmol, 1.41 mL) was added. The reaction mixture was stirred for 60 minutes at room temperature, then diluted 1:1 with hexane and loaded onto approximately 60 g of flash silica gel packed in a loader. Purification was carried out by flash chromatography on silica gel (220 g, equilibrated 0% EtOAc / hexane, eluted 0% 2 CV → 20% EtOAc / hexane (22 CV)). The product-containing fractions were evaporated to dryness in vacuo to give 5.182 g of a yellow solid (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) δ 9.89(s,1H), 8.75(s,1H), 8.50(s,1H), 8.29~8.24(m,2H), 8.07(s,1H), 8 .05~7.97(m,3H), 7.67~7.60(m,2H), 7.49(ddd,J=8.6,6.1,2.6Hz,1H), 7 .43(t,J=1.8Hz,2H), 7.38(d,J=8.4Hz,2H), 7.31~7.25(m,1H), 7.23(s,2 H), 7.17(d,J=1.8Hz,4H), 7.05~6.96(m,2H), 4.07(s,2H), 1.36(s,36H).

[0163] PLC-1 (Diethyl 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-dicarboxylate): A 250 mL 2N round-bottom flask was equipped with a stir bar, a finned condenser / gas adapter, and a flow control. The system was flushed with argon. A flask was charged with compound 1.4 (1.000 mmol, 1.326 g), ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (2.100 mmol, 351 mg), and dry DCE (100 mL). The reaction mixture was vigorously stirred at room temperature for 30 seconds, followed by the addition of pTsOH·HO (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), followed by the addition of dry DCE (5 mL). The mixture was stirred at room temperature for 30 minutes, followed by the addition of DDQ (0.5000 mmol, 114 mg), followed by the addition of dry DCE (5 mL). After stirring for an additional 30 minutes, the oxidation was complete. To the reaction mixture was added EtN (8.000 mmol, 1.1 mL) and BF·OEt (12.00 mmol, 1.5 mL). After 1 min, the addition of EtN (8.000 mmol, 1.1 mL) and BF OEt (12.00 mmol, 1.5 mL) was repeated. The reaction mixture was stirred at 50 °C for 50 min. The reaction mixture was then evaporated in vacuo (bath temperature = 60 °C) onto 25 g of flash silica gel, and the silica was placed in a loader. Purification was carried out by flash chromatography on silica gel (330 g, equilibrated with 0% acetone / hexane, eluted with 0% (2 CV) → 20% acetone / hexane (15 CV)). The product-containing fractions were evaporated to dryness in vacuo.The product was repurified by loading directly onto a 220 g column using 10% DCM / hexane (dry load) and eluting with 0% EtOAc / DCM (2 CV) → 0.2% EtOAc / DCM (2 CV) → isocratic 0.2% EtOAc / DCM. The product-containing fractions were evaporated to dryness in vacuo. 870 mg (52% yield) of an orange solid was obtained. MS (APCI): Formula: C. 95 H 84 BF 14 Calculated for N3O9 (M+H) = 1689; Found: 1689. 1 H NMR (400MHz, TCE) δ 8.75(s,1H), 8.50(s,1H), 8.26(s,2H), 8.07(s,1H), 8.02(s,3H), 7.66( d,J=8.3Hz,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), 4.1 0(s,2H), 2.62(s,6H), 2.00(s,6H), 1.30(t,J=7.1Hz,6H), 1.12(s,36H).

[0164] Photoluminescent compound PLC-2: [ka]

[0165] 5''-Hydroxy-[1,1':4',1'':3'',1''':4'',1''''-quinquephenyl]-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 h. The crude reaction mixture was evaporated in vacuo onto approximately 50 g of flash silica gel and packed into a loader. Purification was achieved by flash chromatography on silica gel (120 g, 0% acetone / hexane (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. The product was carried to the next step without further purification. MS (APCI): Chemical formula: C 31 H 22 Calculated for O2 (M+H) = 427; Found: 427.

[0166] 2″-Formyl-[1,1′:4′,1'':3′′,1′'':4′′,1′′′-quinquephenyl]-5′-yl 2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate): Phenol from the first step (50% wt / wt, 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)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 dry DCM (10 mL) and stirred at room temperature in a capped vial for 20 min. The crude reaction mixture was evaporated in vacuo onto approximately 10 g of flash silica gel and loaded onto a loader. Purification was achieved by flash chromatography on silica gel (80 g, 0% acetone / hexane (2 CV) → 40% acetone / hexane (15 CV)). Fractions containing the product were evaporated to dryness in vacuo. A yellow solid was obtained containing the starting hydroxyaldehyde (approximately 36% by NMR) and a portion of the desired product (approximately 64% by NMR). MS(APCI):Chemical formula:C 73 H 39 F 12 Calculated for NO6 (M+H) = 1254; Found: 1254. Carried on to next step without further purification.

[0167] PLC-2 Diethyl 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''''-quinquephenyl]-2''-yl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-di Pyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate: The aldehydes from the previous step (mixture, ca. 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 dry DCE (20 mL) and stirred at 50 °C under argon for 2 h. The reaction mixture was cooled to room temperature, treated with DDQ (44 mg, 0.1914 mmol), and stirred at room temperature for 20 min. EtN (0.16 mL, 1.178 mmol) and BF·OEt (0.22 mL, 1.767 mmol) were added. The addition of EtN (0.16 mL, 1.178 mmol) and BF·OEt (0.22 mL, 1.767 mmol) was repeated, and the reaction mixture was then stirred at 50° C. for 1 h. The crude reaction mixture was evaporated in vacuo onto approximately 15 g of flash silica gel and packed into a single loader. Purification was achieved by flash chromatography on silica gel (120 g, 0.1% EtOAc / DCM (4 CV) → 0.5% (15 CV) → 3% (30 CV), step gradient). The product-containing fractions were evaporated to dryness in vacuo. 21 mg (23% yield) of an orange solid was obtained. MS (APCI): Formula: C 91 H 60 BF 14 Calculated for N3O9 (M+H) = 1616; Found: 1616. 1H NMR(400MHz,TCE) δ 8.76(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).

[0168] Photoluminescent compound PLC-3: [ka]

[0169] Bis(2-ethylhexyl) 5-bromoisophthalate: 5-Bromoisophthalic acid (5.00 g, 20.41 mmol), 2-ethylhexan-1-ol (20 mL), and pTsOH·HO (388 mg, 2.041 mmol) were combined in toluene (150 mL) and DMSO (10 mL) and refluxed under a Dean-Stark trap for 24 hours to remove water. The reaction was cooled to room temperature and evaporated in vacuo onto approximately 60 g of flash silica gel. Purification by flash chromatography on silica gel (220 g, 0% acetone / hexane (2 CV) → 20% (10 CV)) failed to separate the product. The product was evaporated to dryness in vacuo and the purification sequence was repeated. The product-containing fractions were evaporated to dryness in vacuo. 5.679 g (59% yield) was obtained. MS (APCI): Chemical Formula: C 24 H 37 Calculated for BrO4 (M+H) = 469; Found: 469. Purity about 90% by NMR. Carried on to next step without further purification.

[0170] Bis(2-ethylhexyl) 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)isophthalate: The aryl bromide from the previous step (approximately 90% pure, 5.678 g, 12.09 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (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 dry dioxane (100 mL) and heated at 80 °C under argon for 3 h. The reaction mixture was cooled to room temperature and evaporated in vacuo onto approximately 60 g of flash silica gel. Purification was carried out by flash chromatography on silica gel (220 g, 0% EtOAc / hexane (2 CV) to 20% (25 CV)). Fractions containing the product were evaporated to dryness in vacuo. 5.479 g (88% yield) was obtained. MS (APCI): Formula: C 30 H 49 Calculated for BO6 (M+H)=517; Found: 517. 1 H NMR(400MHz,TCE) δ 8.69(t,J=1.8Hz,1H), 8.59(d,J=1.7Hz,2H), 4.28(d,J=5.8Hz,4H), 1.75(hep t,J=6.3Hz,2H), 1.55~1.29(m,28H), 0.96(t,J=7.5Hz,6H), 0.94~0.89(m,6H).

[0171] Tetrakis(2-ethylhexyl) 2'-formyl-5'-hydroxy-[1,1':3',1''-terphenyl]-3,3'',5,5''-tetracarboxylate: The aryl boronate 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, 0.1786 mmol) were combined in THF (45 mL) and water (3 mL) and heated at 80 °C overnight under argon. The reaction mixture was cooled to room temperature and evaporated in vacuo onto approximately 50 g of flash silica gel. Purification was achieved by flash chromatography on silica gel (220 g, 0% acetone / hexane (2 CV) → 15% (20.5 CV)). The fractions containing the product were evaporated to dryness in vacuo. 645 mg (80% yield) was obtained. MS (APCI): Chemical formula: C 55 H 78 O 10 Calculated for (M+H)=900; Found: 900. 1 H NMR(400MHz,TCE) δ 9.71(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).

[0172] 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 mm ol), 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 (121 mg, 0.1430 mmol), DMAP·pTsOH salt (65 mg, 0.2200 mmol), and DIC (0.069 mL, 0.440 mmol) were combined in dry DCM (10 mL) and stirred at room temperature for 30 min. The crude reaction mixture was diluted 1:1 with hexane and loaded onto approximately 20 g of flash silica gel packed in a loader. Purification was performed by flash chromatography on silica gel (120 g, 0% acetone / hexane (2 CV) → 30% (20 CV)). Fractions containing the product were evaporated to dryness in vacuo. 118 mg (62%) of a yellow solid was obtained. The product co-elutes with unreacted 1677-079 and was carried forward without further purification. MS (APCI): Chemical formula: C 97 H 95 F 12 NO 14 Calculated for (M+H)=1727; Found: 1727.

[0173] PLC-3 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'-(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]diazaboroyl) Nin-10-yl)-[1,1':3',1''-terphenyl]-3,3'',5,5''-tetracarboxylate: The aldehydes 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·HO (3.3 mg, 0.01760 mmol) were combined in dry DCE (25 mL) and reacted overnight at 50 °C under argon. The reaction was cooled to room temperature, treated with DDQ (26 mg, 0.1144 mmol), and stirred at room temperature for 30 min. The reaction was then treated with EtN (0.098 mL, 0.7041 mmol) and BF·OEt (0.13 mL, 1.056 mmol). The addition of EtN (0.098 mL, 0.7041 mmol) and BF OEt (0.13 mL, 1.056 mmol) was repeated, and the reaction mixture was stirred at 50 °C for 1 h. The reaction mixture was evaporated in vacuo onto approximately 30 g of flash silica gel and packed into a loader. Purification was carried out by flash chromatography on silica gel (120 g, 0% EtOAc / hexane (2 CV) → 5% (5 CV) → 20% (20 CV) → 30% (5 CV)). The product-containing fractions were evaporated to dryness in vacuo. 55 mg of an orange solid was obtained (38% yield). 1H NMR(400MHz,TCE) δ 8.75(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,2 H), 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).

[0174] Photoluminescent compound PLC-4: [ka]

[0175] 5''-Hydroxy-[1,1':3',1'':3'',1''':3''',1''''-quinquephenyl]-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)Cl2 (131 mg, 0.1786 mmol) were combined in THF (45 mL) and water (3 mL) and stirred at 80 °C under argon for 5 h. The reaction mixture was cooled to room temperature and evaporated in vacuo onto approximately 25 g of flash silica gel, which was then loaded onto a loader. Purification was achieved by flash chromatography on silica gel (120 g, 0% acetone / hexane (2 CV) → 30% (15 CV)). 315 mg (83% yield) was obtained. MS (APCI): Chemical formula: C 31 H 22 Calculated for O2 (M+H) = 427; Found: 427. 1H NMR (400MHz, acetone) δ 9.89(s,1H), 9.48(s,1H), 7.75~7.67(m,8H), 7.54(td,J=7.5,1.0Hz,2H), 7.51~7.44(m,4H), 7.43~7.34(m,4H), 6.97(s,2H).

[0176] 2''-Formyl-[1,1':3',1'':3'',1''':3''',1''''-quinquephenyl]-5''-yl 2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: 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)acetic acid (178 mg, 0.2100 mmol), DMAP·pTsOH salt (88 mg, 0.3000 mmol), and DIC (0.094 mmol, 0.6000 mmol) in dry DCM (10 mL) were stirred at room temperature for 30 min. The crude product was diluted 1:1 with hexane and loaded onto approximately 20 g of flash silica gel packed in a loader. Purification was performed by flash chromatography on silica gel (120 g, 0% acetone / hexane (2 CV) → 40% (15 CV)). Fractions containing the product were evaporated to dryness in vacuo to give 204 mg (109%) of a yellow solid, which was wetted with solvent and carried on to 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) δ 9.98(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).

[0177] PLC-4 Diethyl 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''''-quinquephenyl]-2''-yl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4,5 4-Dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate: 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 dry DCE (25 mL) and stirred at room temperature under argon for 1 h. The reaction mixture was treated with DDQ (55 mg, 0.2428 mmol) and stirred at room temperature for 30 min. The reaction was then treated with EtN (0.18 mL, 1.295 mmol) and BF·OEt (0.24 mL, 1.942 mmol). The addition of Et3N (0.18 mL, 1.295 mmol) and BF3·OEt2 (0.24 mL, 1.942 mmol) was repeated, and the reaction mixture was stirred at 50 °C for 1 h. The crude reaction mixture was diluted 1:1 with hexane and loaded onto approximately 25 g of flash silica gel packed in a loader. Purification was achieved by flash chromatography on silica gel (120 g, 0% EtOAc / DCM (2 CV) → 0.5% (10 CV) → 3% (25 CV)). Fractions containing the product were evaporated to dryness in vacuo. 51 mg (20% yield) of an orange solid was obtained. MS (APCI): Formula: C 91 H 60 BF 14 Calculated for N3O9 (M+H) = 1616; Found: 1616. 1H NMR(400MHz,TCE) δ 8.75(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), 7.4 4~7.20(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).

[0178] Photoluminescent compound PLC-5: [ka]

[0179] 5'-Hydroxy-3,3'',5,5''-tetrakis(trifluoromethyl)-[1,1':3',1''-terphenyl]-2'-carbaldehyde: 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 dry THF (90 mL) and water (6 mL) and stirred at 80 °C under argon for 2 h. The reaction mixture was cooled to room temperature and titrated to pH ∼1 with 6 N HCl solution. The reaction mixture was partitioned with ether (150 mL), the layers were separated, extracted with DCM (150 mL), and the combined organic layers were dried over magnesium sulfate, filtered, and evaporated to dryness in vacuo. The crude product was evaporated in vacuo onto approximately 40 g of flash silica gel and loaded onto a loader. Purification was carried out by flash chromatography on silica gel (120 g, 0% EtOAc / hexane (2 CV) → 20% (30 CV)). The product-containing fractions were evaporated to dryness in vacuo. 889 mg (75% yield) of a white solid was obtained. MS (APCI): Formula: C 23 H 10 F 12 Calculated for O2 (M+H) = 547; Found: 547. 1H 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).

[0180] 2'-Formyl-3,3'',5,5''-tetrakis(trifluoromethyl)-[1,1':3',1''-terphenyl]-5'-yl 2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: 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)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 dry DCM (15 mL) at room temperature for 30 min. The crude reaction mixture was diluted 1:1 with hexane and loaded onto a loader packed with approximately 50 g of flash silica gel. Purification was carried out by flash chromatography on silica gel (220 g, 0% EtOAc / toluene (2 CV) → 10% (15 CV)). Fractions containing the product were evaporated to dryness in vacuo. 1351 mg (60% yield) of a yellow solid was obtained. MS (APCI): Chemical Formula: C 65 H 27 F 24 Calculated for NO6 (M+H) = 1374; Found: 1374. 1 H NMR (400MHz, acetone) δ 9.92(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).

[0181] Diethyl 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-414, 514-Dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate: The aldehyde from the previous step (1351 mg, 0.9833 mmol), ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (378 mg, 2.262 mmol), and pTsOH·HO (19 mg, 0.09833 mmol) in dry DCE (50 mL) were stirred overnight at room temperature under argon. The reaction mixture was treated with DDQ (379 mg, 1.672 mmol) and stirred at room temperature for 30 min. The reaction was then treated with EtN (0.80 mL, 5.702 mmol) and BF·OEt (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 1 h. The crude reaction mixture was evaporated in vacuo onto approximately 45 g of flash silica gel and packed into a loader. Purification was carried out by flash chromatography on silica gel (220 g, 0% EtOAc / DCM isocratic). The product-containing fractions were evaporated to dryness in vacuo. 763 mg (45% yield) of an orange solid was obtained. MS (APCI): Formula: C 83 H 48 BF 26 Calculated for N3O9 (M+H) = 1736; Found: 1736. 1H NMR(400MHz,TCE) δ 8.75(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,2H), 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).

[0182] Photoluminescent compound PLC-6: [ka]

[0183] Bis((perfluorophenyl)methyl) 5-bromoisophthalate: 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 dry THF (50 mL) and stirred overnight at room temperature under argon. The crude reaction mixture was evaporated in vacuo onto approximately 60 g of flash silica gel and loaded onto a loader. Purification was achieved by flash chromatography on silica gel (220 g, 50% DCM / hexane (2 CV) → 100% DCM (10 CV)). Product-containing fractions were evaporated to dryness in vacuo. 2.748 g (57% yield) was obtained. MS (APCI): Chemical Formula: C 22 H7BrF 10 Calculated for O4 (M+H) = 605; Found: 605. 1 H NMR (400MHz, CD2Cl2) δ 8.54 (t, J = 1.5 Hz, 1H), 8.33 (d, J = 1.6 Hz, 2H), 5.47 (t, J = 1.6 Hz, 5H).

[0184] 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'-bi(1,3,2-dioxaborolane) (1458 mg, 5.742 mmol), KOAc (1300 mg, 13.25 mmol), and Pd(dppf)Cl (102 mg, 0.2208 mmol) were combined in dry dioxane (100 mL) under argon and heated at 80 °C for 2 h. The crude reaction mixture was evaporated in vacuo onto approximately 60 g of flash silica gel and packed into a loader. Purification was carried out by flash chromatography on silica gel (120 g, 50% DCM / hexane (2 CV) → 100% DCM (10 CV) → isocratic DCM). Fractions containing the product were evaporated to dryness in vacuo. 2.680 g (93% yield) was obtained. MS (APCI): Formula: C 28 H 19 BF 10 Calculated for O6 (M+H)=653; Found: 653. 1 H NMR (400MHz, CD2Cl2) δ 8.67(t,J=1.8Hz,1H), 8.54(d,J=1.8Hz,2H), 5.47(t,J=1.6Hz,6H), 1.23(s,12H).

[0185] 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)Cl2 (240 mg, 0.3285 mmol) were combined in THF (100 mL) and water (16 mL) and heated at 80 °C under argon for 4 h. The crude reaction mixture was evaporated onto approximately 60 g of flash silica gel and loaded onto a loader. Purification was achieved by flash chromatography on silica gel (120 g, 75% DCM / hexane (2 CV) → 100% DCM (10 CV) → isocratic DCM). 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 Calculated for (M+H)=1171; Found: 1171. 1 H NMR (400MHz, CD2Cl2) δ 9.63 (s, 1H), 8.67~8.57 (m, 5H), 6.84 (s, 2H), 5.48 (d, J = 1.5Hz, 8H).

[0186] 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, 1.25 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)acetic acid (1275 mg, 1.508 mmol), DMAP·pTsOH salt (37 mg, 0.1256 mmol), and DIC (0.393 mL, 2.511 mmol) in dry DCM (20 mL) was stirred at room temperature for 60 min. The crude reaction mixture was loaded onto approximately 50 g of flash silica gel in a loader. Purification was performed by flash chromatography on silica gel (120 g, 0% EtOAc / DCM (2 CV) → 1% (5 CV) → 3% (15 CV)). The product-containing fractions were evaporated to dryness in vacuo. 1.317 g (53%) of a yellow solid was obtained. MS(APCI):Chemical formula:C 93 H 35 F 32 NO 14 Calculated for (M+H) = 1998; Found: 1998. NMR is messy but correct compound. Carried directly to next step.

[0187] 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 [[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[(2,2,3,4,5,6,6,7,8,10,11,22,23,24,25,26,26,27,28,29,30,29,31,29,32,29,33,29,34,29,35,29,36,29,37,29,38,29,39,29,30,29,30,29,31,29,32 ...

[0188] 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-414 ,514-Dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinin-10-yl)-[1,1':3',1''-terphenyl]-3,3'',5,5''-tetracarboxylate: The dipyrrole from the previous step (575 mg, 0.2493 mmol) was dissolved in dry DCE (50 mL), treated with DDQ (79 mg, 0.3490 mmol), and stirred at room temperature for 1 h. The reaction was then treated with EtN (0.28 mL, 1.994 mmol) and BF OEt (0.37 mL, 2.991 mmol). The addition of EtN (0.28 mL, 1.994 mmol) and BF OEt (0.37 mL, 2.991 mmol) was repeated, and the reaction mixture was stirred at 50 °C for 1 h. The crude reaction mixture was evaporated in vacuo onto approximately 40 g of flash silica gel and packed into a loader. Purification was carried out by flash chromatography on silica gel (120 g, 0% EtOAc / DCM (2 CV) to 25% (25 CV)). The product-containing fractions were evaporated to dryness in vacuo. 126 mg of an orange solid was obtained (53% yield). 1H NMR (400MHz, CD2Cl2) δ 8.78(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).

[0189] フォトルミネッセンス compound PLC-7:

change

[0190] tert-Butyl (2-oxobutyl)carbamate: tert-Butyl (2-(methoxy(methyl)amino)-2-oxoethyl)carbamate (10.915 g, 50.00 mmol) was dissolved in dry THF (200 mL) under argon and cooled to 0 °C. The reaction mixture was treated with ethylmagnesium bromide (3 M in ether, 50.0 mL, 150.0 mmol) with stirring for approximately 5 minutes. The cooling bath was removed, and the reaction mixture was stirred at room temperature for 6 hours. It was quenched with ethyl acetate (approximately 15 mL) and then partitioned between saturated ammonium chloride (approximately 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 taken up in hexane and loaded onto approximately 50 g of flash silica gel packed in a loader. Purification was carried out by flash chromatography on silica gel (220 g, 0% EtOAc / hexane (2 CV) → 30% (15 CV)). Fractions containing the product were evaporated to dryness in vacuo. 7.879 g (84% yield) of a pale yellow liquid was obtained. MS (APCI): Chemical formula: CH 17 Calculated for NO3 (M+H) = 188; Found: 188. 1 H NMR(400MHz,TCE) δ 5.18(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).

[0191] 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) with stirring at room temperature. The reaction mixture was allowed to outgas for 1-2 minutes and then stirred at room temperature for 30 minutes. The reaction mixture was evaporated to dryness and immediately carried on to the next step. MS (APCI): Calculated for formula C4H9NO (M+H) = 88; Found: 88 (free base).

[0192] Ethyl 4-ethyl-2-methyl-1H-pyrrole-3-carboxylate: 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 with stirring at 80°C for 4 hours. The heat was turned off, and the reaction mixture was stirred at room temperature over the weekend. The reaction was filtered and washed with water. The crude product was dissolved in DCM, separated from the water, dried over magnesium sulfate, filtered, and evaporated to dryness in vacuo. 6.859 g (90% yield) of a brown solid was obtained. MS (APCI): Chemical 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 highly pure, eliminating the need for column chromatography.

[0193] 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: 3,3'',5,5''-tetra-tert-butyl-4'-formyl-1-phenol (872 mg, 1 A mixture of 2-(4-(1,3-dioxo-5,11-bis(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) in dry DCM (50 mL) was stirred at room temperature for 30 min. The crude reaction mixture was evaporated in vacuo onto approximately 30 g of flash silica gel and loaded onto a loader. Purification was carried out by flash chromatography on silica gel (120 g, 0% EtOAc / hexane (2 CV) → 20% (30 CV)). Fractions containing the product were evaporated to dryness in vacuo. 2058 mg (99% yield) of a yellow solid was obtained. MS (APCI): Formula: C 75 H 65 Calculated for F6NO6 (M+H) = 1190; Found: 1190. 1 H NMR(400MHz,TCE) δ 9.89(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).

[0194] PLC-7 Diethyl 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-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate: The aldehyde from the previous step (283 mg, 0.2000 mmol), compound 1711-44 (91 mg, 0.5000 mmol), and pTsOH·HO (4 mg, 0.02000 mmol) in dry DCE (20 mL) were stirred at 60 °C for 3 h under argon. The reaction was treated with DDQ (82 mg, 0.3600 mmol) and heating was continued at 60 °C for 30 min. The reaction was treated with additional DDQ (82 mg, 0.3600 mmol) and heating was continued at 60 °C for an additional 30 min. The reaction mixture was cooled to room temperature and treated with EtN (0.22 mL, 1.600 mmol) and BF·OEt (0.30 mL, 2.400 mmol). The addition of EtN (0.22 mL, 1.600 mmol) and BF·OEt (0.30 mL, 2.400 mmol) was repeated, and the reaction mixture was stirred at 50 °C for 1 h. The crude reaction mixture was evaporated in vacuo onto approximately 40 g of flash silica gel and loaded onto a loader. Purification was achieved by flash chromatography on silica gel (120 g, 100% toluene / hexane with EtOAc modifier, 0% → 1% → 2% isocratic step gradient). Fractions containing the product were evaporated to dryness in vacuo. 64 mg (20% yield) of an orange solid was obtained. MS (APCI): Formula: C 95 H 90 Calculated for BF8N3O9 (M+H)=1581; Found: 1581. 1H NMR(400MHz,TCE) δ 8.48(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,5 H), 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).

[0195] フォトルミネッセンス compound PLC-8:

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[0196] PLC-8 Diethyl 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]diazaborinine-2,8-dicarboxylate:3,3'',5,5''-tetra-tert-butyl-2'-formyl-[1,1':3',1 A mixture of [[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[[([)])]) ... The reaction mixture was treated with EtN (1.600 mmol, 0.22 mL) and BF·OEt (2.400 mmol, 0.30 mL) was added to the reaction. The addition of EtN (1.600 mmol, 0.22 mL) and BF·OEt (2.400 mmol, 0.30 mL) was repeated and the reaction was stirred at 50 °C for 60 min. The reaction mixture was cooled to room temperature and evaporated in vacuo onto approximately 35 g of flash silica gel and loaded onto a loader. Purification was achieved by flash chromatography on silica gel (120 g, 0% acetone / hexane (2 CV) → 10% (60 CV)). Fractions containing the product were evaporated to dryness in vacuo. 174 mg (55% yield) of an orange solid was obtained. MS (APCI): Formula: C 95 H 90 Calculated for BF8N3O9 (M+H)=1581; Found: 1581. 1H NMR(400MHz,TCE) δ 8.70(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(d d,J=8.3,1.5Hz,1H), 7.01~6.90(m,5H), 4.25(q,J=7.1Hz,4H), 4.11(s,2 H), 3.13~2.98(m,4H), 2.02(s,6H), 1.31(t,J=7.1Hz,6H), 1.12(s,42H).

[0197] フォトルミネッセンス compound PLC-9:

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[0198] PLC-9 Diethyl 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-dicyano-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate:diethyl 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-dicarboxylate (0.07936 mmol, 134 mg) was dissolved in dry DCE (10 mL) and stirred at room temperature under argon. The reaction was treated with TMSCN (2.000 mmol, 0.25 mL) followed by BF3·OEt2 (0.1500 mmol, 0.019 mL). The reaction mixture was stirred at room temperature for several minutes and then heated to 45 °C for 120 minutes. The crude reaction mixture was poured into approximately 30 mL of saturated NaHCO3 and stirred for several minutes. The reaction was filtered through a polypropylene frit to retain moisture, 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 approximately 15 g of flash silica gel packed in a loader. Purification was achieved by flash chromatography on 80 g silica gel (0% acetone / hexane (2 CV) → 20% (5 CV), gradient stops at 7.6%, 7.9%, 8.1%, and 8.4%). The product-containing fractions 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 to give 121 mg (90% yield) of an orange solid. MS (APCI): Formula: C 97 H 84 BF12 N5O9についての calculated value (M+H)=1703; measured value: 1703. 1 H NMR(400MHz,TCE) δ 8.75(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=7.1 Hz,4H), 4.09(s,2H), 2.81(s,6H), 2.10(s,6H), 1.34(t,J=7.1Hz,6H), 1.13(s,36H).

[0199] フォトルミネッセンス compound PLC-10:

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[0200] 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) in acetic acid (100 mL) and water (100 mL) were stirred at 100 °C under argon over the weekend. The reaction mixture was cooled to room temperature, and most of the solvent was evaporated in vacuo. The mixture was partitioned between DCM (200 mL) and water (50 mL). The remaining acetic acid was carefully quenched with 10% K2CO3 solution. The layers were separated, the aqueous layer was extracted with 2 × 50 mL DCM, and 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 approximately 50 g of flash silica gel packed in a loader. Purification was carried out by flash chromatography on silica gel (120 g, 0% EtOAc / hexane (2 CV) to 15% (15 CV)). Fractions containing the product were evaporated to dryness in vacuo. 7.985 g (44% yield) of a pale yellow oil was obtained. MS (APCI): Formula: C 10 H 15 Calculated for NO2 (M+H) = 182; Found: 182.

[0201] Diethyl 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]diazaborinine-2,8-dicarboxylate: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 (0.3000 mmol, 290 mg), the pyrrole from the previous step (0.6300 mmol, 114 mg), and pTsOH·HO (0.06000 mmol, 11 mg) in dry DCE (20 mL) were stirred at 40 °C under argon for 60 min. The reaction was cooled to room temperature, and DDQ (0.4500 mmol, 102 mg) was added and stirred at room temperature for 10 min. EtN (2.400 mmol, 0.33 mL) and BF·OEt (3.600 mmol, 0.44 mL) were added to the reaction. The addition of EtN (2.400 mmol, 0.33 mL) and BF·OEt (3.600 mmol, 0.44 mL) was repeated, and the reaction was stirred at 50 °C for 30 min. The reaction mixture was cooled to room temperature, quenched with 5 mL of water, stirred for several minutes, and then filtered through a polypropylene frit to retain moisture. The frit was eluted with DCM. The eluent was loaded onto a 15 g flash silica plug 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 gel packed in a loader. Purification was achieved by flash chromatography on silica gel (80 g, 0% acetone / hexane (2 CV) → 50% (5 CV), 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 the 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 to give 205 mg (50% yield) of an orange solid. MS (APCI): Formula: C. 77 H 54 Calculated for BF8N3O9 (M+H)=1328; Found: 1328. 1 H NMR(400MHz,TCE) δ 8.71(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).

[0202] PLC-10 Diethyl 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]diazaborinine-2,8-dicarboxylate: The 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) in dry DCE (10 mL) were stirred at room temperature under argon for 5 min. The temperature was raised to 45 °C for 120 min and then left at room temperature overnight. The crude reaction mixture was poured into 30 mL of saturated NaHCO₃ solution and stirred for 5 min, then filtered through a polypropylene frit to retain moisture. 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. Purification was by flash chromatography on silica gel (80 g, 0% acetone / hexane (2 CV) → 10% (5 CV), stopping at 1.0%, then to 1.3%, isocratic each step). Fractions containing the product were evaporated to dryness in vacuo. The product was triturated with hot MeOH, cooled to room temperature, filtered, washed with MeOH, dissolved in DCM and evaporated to dryness in vacuo. 64 mg (62% yield) of an orange solid was obtained. MS (APCI): Formula: C 81 H 58 Calculated for BF6N5O9 (M+H) = 1370; Found: 1370. 1H NMR(400MHz,TCE) δ 8.70(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).

[0203] Photoluminescent compound PLC-12: [ka]

[0204] 5'-Hydroxy-[1,1':3',1''-terphenyl]-2'-carbaldehyde: 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) were combined in THF (150 mL) and water (12 mL) and heated to 75 °C under argon for 3 h. The reaction mixture was cooled, and most of the THF was evaporated in vacuo. The crude mixture was suspended in acetone and evaporated onto approximately 50 g of flash silica gel, which was then loaded onto a loader. Purification was achieved by flash chromatography on silica gel (220 g, 0% acetone / hexane (2 CV) → 40% (15 CV)). Fractions containing the product were evaporated to dryness in vacuo and then triturated with 50:50 MeOH:water. The product was filtered off, washed with 50% MeOH / water, and dried under vacuum at 80°C. 4348 mg (79% yield) of an off-white solid was obtained. MS (APCI): Chemical Formula: C 19 H 14Calculated 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).

[0205] 2'-Formyl-[1,1':3',1''-terphenyl]-5'-yl 2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: 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 dry DCE (20 mL) for 1 h. The reaction mixture was loaded onto approximately 40 g of flash silica gel packed in a loader. Purification was carried out by flash chromatography on silica gel (120 g, acetone / DCM (2 CV) → 20% (5 CV), gradient stop at 1.8%). The product-containing fractions were evaporated to dryness in vacuo. 1183 mg (72% yield) of a yellow solid was obtained. MS (APCI): Chemical Formula: C 61 H 31 F 12 Calculated for NO6 (M+H) = 1102; Found: 1102. 1 H NMR(400MHz,TCE) δ 9.87(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).

[0206] PLC-11 Dimethyl 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]diazaborinine-2,8-dicarboxylate: 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·HO (0.08000 mmol, 15 mg) were stirred in dry DCE (25 mL) under argon at 35 °C overnight. The reaction mixture was cooled to room temperature, and DDQ (2.400 mmol, 545 mg) was added. The mixture was stirred at room temperature for 10 minutes. EtN (3.200 mmol, 0.45 mL) was added to the reaction, followed by BF·OEt (4.800 mmol, 0.59 mL). 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 70 °C for 24 h. The reaction mixture was cooled to room temperature, quenched with 10 mL of water, and stirred for 5 min. The reaction mixture was filtered through a polypropylene frit to retain moisture. 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. Purification was performed by flash chromatography on silica gel (120 g, 0% acetone / hexane (2 CV) → 20% (5 CV), gradient stops at 0.3%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, and 1.1%). The product-containing fractions 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 to give 230 mg (39% yield) of an orange solid. MS (APCI): Formula C 77 H 50 Calculated for BCl4F8N3O9 (M+H) = 1464; Found: 1464. 1H NMR(400MHz,TCE) δ 8.70(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), 4.28(q, J=7.1Hz,4H), 4.08(s,2H), 2.76(s,6H), 1.90(s,7H), 1.35(t,J=7.1Hz,6H).

[0207] フォトルミネッセンス compound PLC-12:

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[0208] PLC-12 Diethyl 10-(5'-(2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isosoquinolin-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]diazaborinine-2,8-dicarboxylate: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 (0.3000 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) in dry DCE (20 mL) were stirred at 40 °C for 1 h under argon. The reaction mixture was cooled to room temperature, treated with DDQ (0.4500 mmol, 102 mg), and stirred at room temperature for 10 min. The reaction mixture was treated with EtN (2.400 mmol, 0.33 mL), and BF·OEt (3.600 mmol, 0.44 mL) was added to the reaction. The addition of EtN (2.400 mmol, 0.33 mL) and BF·OEt (3.600 mmol, 0.44 mL) was repeated, and the reaction was stirred at 50 °C for 1 h. The reaction mixture was cooled to room temperature, quenched with 10 mL of water, and stirred for 5 min. The reaction mixture was filtered through a polypropylene frit to retain moisture. 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 approximately 45 g of flash silica gel packed in a loader. Purification was achieved by flash chromatography on silica gel (120 g, 0% acetone / hexane (2 CV) → 50% (5 CV), gradient stopping at 12.0%, then 13.0%, 13.6%, 14.0%, 14.5%, 14.9%, 15.1%, 15.5%, 16.0%, and 17.0%). Fractions containing the product were evaporated to dryness in vacuo. 205 mg of an orange solid was obtained (50% yield).MS (APCI): Chemical formula: C. 79 H 58 BF8N3O9についての calculated value (M+H)=1356; measured value: 1356. 1 H NMR(400MHz,TCE) δ 8.71(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).

[0209] フォトルミネッセンス compound PLC-13:

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[0210] PLC-13 Diethyl 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]diazaborinine-2,8-dicarboxylate: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 (0.3000 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) in dry DCE (25 mL) were stirred at 40 °C for 3 h under argon. The reaction mixture was cooled to room temperature, treated with DDQ (0.9000 mmol, 204 mg), and stirred at room temperature for 10 min. The reaction mixture was treated with EtN (2.400 mmol, 0.33 mL), and BF·OEt (3.600 mmol, 0.44 mL) was added to the reaction. The addition of EtN (2.400 mmol, 0.33 mL) and BF·OEt (3.600 mmol, 0.44 mL) was repeated, and the reaction was stirred at 50 °C for 1 h. The reaction mixture was cooled to room temperature, quenched with 10 mL of water, and stirred for 5 min. The reaction mixture was filtered through a polypropylene frit to retain moisture. 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 approximately 45 g of flash silica gel packed in a loader. Purification was performed by flash chromatography on silica gel (80 g, 0% acetone / hexane (2 CV) to 25% (5 CV), gradient stopped at 11.1%, 12.5%, 13.4%, 14.5%, 15.5%, and 16.5%). Fractions containing the product were evaporated to dryness in vacuo.Repurification (loaded onto 15 g of flash silica gel packed in a loader): 40 g, 0% EtOAc / hexane (2 CV) → 35% (5 CV), gradient stopped at 21.6%, 22.1%, and 22.5%. Product-containing fractions were evaporated to dryness in vacuo. 143 mg (34% yield) of an orange solid was obtained. MS (APCI): Formula: C. 83 H 66 Calculated for BF8N3O9 (M+H)=1413; Found: 1413. 1 H NMR(400MHz,TCE) δ 8.62(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,4 H), 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).

[0211] Photoluminescent compound PLC-14: [ka]

[0212] PLC-14 Diethyl 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]diazaborinine-2,8-dicarboxylate:3,3'',5,5''-tetrafluoro- 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 (0.3000 mmol, 311 mg), ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (0.6300 mmol, 105 mg), and pTsOH·HO (0.06000 mmol, 11 mg) in dry DCE (25 mL) were stirred at 40 °C for 3 h under argon. The reaction mixture was cooled to room temperature, treated with DDQ (0.6000 mmol, 136 mg), and stirred at room temperature for 10 min. The reaction mixture was treated with EtN (2.400 mmol, 0.33 mL), and BF·OEt (3.600 mmol, 0.44 mL) was added to the reaction. The addition of EtN (2.400 mmol, 0.33 mL) and BF·OEt (3.600 mmol, 0.44 mL) was repeated, and the reaction was stirred at 50 °C for 1 h. The reaction mixture was cooled to room temperature, quenched with 10 mL of water, and stirred for 5 min. The reaction mixture was filtered through a polypropylene frit to retain moisture. 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. Purification was carried out by flash chromatography on silica gel (40 g, 0% acetone / hexane (2 CV) → 25% (5 CV), gradient stopped at 13.5%, 14.0%, 14.5%, and 14.9%). The product-containing fractions were evaporated to dryness in vacuo. 241 mg (57% yield) of an orange solid was obtained. MS (APCI): Chemical formula: C77 H 54 Calculated for BF8N3O9 (M+H)=1328; Found: 1328. 1 H NMR(400MHz,TCE) δ 8.70(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(ddd,J=8.4,7.1,1.4Hz,1H), 6.74(dddd,J=18.0,8.6,4.8,2.3Hz,6H), 4.2 7(q,J=7.1Hz,4H), 4.08(s,2H), 2.75(s,6H), 1.91(s,6H), 1.35(t,J=7.1Hz,6H).

[0213] Photoluminescent compound PLC-15: [ka]

[0214] PLC-15 Diethyl 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]diazaborinine-2,8-dicarboxylate:3,3'',5,5''-tetrafluoro- 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 (0.3000 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) in dry DCE (25 mL) were stirred at 40 °C for 3 h under argon. The reaction mixture was cooled to room temperature, treated with DDQ (1.800 mmol, 409 mg), and stirred at room temperature for 10 min. The reaction mixture was treated with EtN (2.400 mmol, 0.33 mL), and BF·OEt (3.600 mmol, 0.44 mL) was added to the reaction. The addition of EtN (2.400 mmol, 0.33 mL) and BF·OEt (3.600 mmol, 0.44 mL) was repeated, and the reaction was stirred at 50 °C for 1 h. The reaction mixture was cooled to room temperature, quenched with 10 mL of water, and stirred for 5 min. The reaction mixture was filtered through a polypropylene frit to retain moisture. 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. Purification was carried out by flash chromatography on silica gel (40 g, 0% acetone / DCM (2 CV) → 25% (5 CV), gradient stopped at 14.3%, 14.5%, and 14.8%). The product-containing fractions were evaporated to dryness in vacuo. 266 mg (62% yield) of an orange solid was obtained. MS (APCI): Formula: C79 H 58 Calculated for BF8N3O9 (M+H)=1356; Found: 1356. 1 H NMR(400MHz,TCE) δ 8.71(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=8.4,1.5Hz,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).

[0215] Photoluminescent compound PLC-16: [ka]

[0216] Ethyl 2-butyl-4-methyl-1H-pyrrole-3-carboxylate: 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 pf ethanol (50 mL) and heated to 80° C. for 300 min. 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 approximately 40 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) → 2% (20 CV)). Fractions containing the product were evaporated to dryness. 2.485 g (59% yield) of a waxy brownish solid was obtained. MS (APCI): Chemical Formula: C 12 H 19 Calculated for NO2 (M+H) = 210; Found: 210. 1H NMR(400MHz,TCE) δ 8.06(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).

[0217] 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 under argon for 1 h. The reaction mixture was cooled and most of the THF was evaporated in vacuo. The crude mixture was suspended in acetone and evaporated onto approximately 50 g of flash silica gel and packed into a loader. Purification was achieved by flash chromatography on silica gel (120 g, 0% acetone / hexane (2 CV) → 40% (10 CV)). 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 under vacuum at 80°C. 3.167 g (92% yield) of an off-white solid was obtained. MS (APCI): Formula: C 19 H 10 Calculated for F4O2 (M+H) = 347; Found: 347. 1 H NMR (400MHz, DMSO) δ 10.92 (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).

[0218] 3,3'',5,5''-tetrafluoro-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: 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)acetate Oxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (4.800 mmol, 3406 mg), DMAP·pTsOH salt (0.4000 mmol, 118 mg), and EDC·HCl (8.000 mmol, 1534 mg) were stirred in dry DCM (35 mL) in a capped vial for 1 h. The reaction mixture was loaded onto approximately 40 g of flash silica gel packed in a loader. Purification was carried out by flash chromatography on silica gel (120 g, 2 CV EtOAc / DCM → 20% (5 CV)). The product-containing fractions were evaporated to dryness in vacuo. 4137 mg (100% yield) of a yellow solid was obtained. MS (APCI): Chemical Formula: C 59 H 29 F 10 Calculated for NO6 (M+H) = 1038; Found: 1038. 1 H NMR(400MHz,TCE) δ 9.87(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=8.6,7.1,1.5H z,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).

[0219] PLC-16 Diethyl 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-dipyrrolidone [1,2-c:2',1'-f][1,3,2]diazaborinine-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·HO (0.06000 mmol, 11 mg) were stirred in dry 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. The mixture was stirred at room temperature for 10 minutes. EtN (2.400 mmol, 0.33 mL) was added to the reaction, followed by BF·OEt (3.600 mmol, 0.44 mL). 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 min. The reaction mixture was cooled to room temperature, quenched with 10 mL of water, and stirred for 5 min. The reaction mixture was filtered through a polypropylene frit to retain moisture. 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. Purification was performed by flash chromatography on silica gel (80 g, 0% acetone / hexane (2 CV) → 25% (5 CV), gradient stop at 13.5%). The product-containing fractions were evaporated to dryness in vacuo. 60 mg of an orange solid (14% yield) was obtained. MS (APCI): Formula: C 83 H 62 BF 12 Calculated for N3O9 (M+H) = 1484; Found: 1484. 1H NMR(400MHz,TCE) δ 8.70(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), 7.5 0~7.38(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).

[0220] Photoluminescent compound PLC-17: [ka]

[0221] Ethyl 2-isobutyl-4-methyl-1H-pyrrole-3-carboxylate: Ethyl 5-methyl-3-oxohexanoate (20.00 mmol, 3.56 mL) and aminoacetone hydrochloride (40.00 mmol, 4.384 g) were combined in water (100 mL) and 200 pf ethanol (50 mL) and heated to 80° C. for 300 min. 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 approximately 40 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) → 2% (20 CV)). Fractions containing the product were evaporated to dryness. 1750 mg (42% yield) of a yellow viscous liquid was obtained. MS (APCI): Chemical Formula: C 12 H 19 Calculated for NO2 (M+H) = 210; Found: 210. 1H NMR(400MHz,TCE) δ 7.98(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)。

[0222] PLC-17 Diethyl 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]diazaborinine-2,8-dicarboxylate: 3,3'',5,5''-tetrafluoro-5'-hydroxy-[1,1':3',1''-terphenyl]-2'-carbaldehyde (0.3000 mmol, 311 mg), the pyrrole from the previous step (0.6300 mmol, 132 mg), and pTsOH·HO (0.06000 mmol, 11 mg) in dry DCE (25 mL) were stirred at 40 °C under argon for 3 h. The reaction mixture was cooled to room temperature, treated with DDQ (1.800 mmol, 409 mg), and stirred at room temperature for 10 min. The reaction mixture was treated with EtN (2.400 mmol, 0.33 mL), and BF·OEt (3.600 mmol, 0.44 mL) was added to the reaction. The addition of EtN (2.400 mmol, 0.33 mL) and BFOEt (3.600 mmol, 0.44 mL) was repeated, and the reaction was stirred at 50 °C for 1 h. The reaction mixture was cooled to room temperature, quenched with 10 mL of water, and stirred for 5 min. The reaction mixture was filtered through a polypropylene frit to retain moisture. 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. Purification was performed by flash chromatography on silica gel (40 g, 0% acetone / hexane (2 CV) → 25% (5 CV), gradient stops at 13.6% and 14.0%). The product-containing fractions were evaporated to dryness in vacuo. 118 mg (27% yield) of an orange solid was obtained. MS (APCI): Formula: C 83 H 62 BF 12 Calculated for N3O9 (M+H) = 1484; Found: 1484. 1H NMR(400MHz,TCE) δ 8.70(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=8.3,1.5Hz,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).

[0223] Photoluminescent compound PLC-18: [ka]

[0224] 3,3'',5,5''-Tetrachloro-5'-hydroxy-[1,1':3',1''-terphenyl]-2'-carbaldehyde: 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) were combined in THF (120 mL) and water (11 mL) and heated to 75 °C under argon for 1 h. The reaction mixture was cooled and most of the THF was evaporated in vacuo. The crude mixture was suspended in acetone and evaporated onto approximately 50 g of flash silica gel and packed into a loader. Purification was achieved by flash chromatography on silica gel (120 g, 0% acetone / hexane (2 CV) → 40% (10 CV)). 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 under vacuum at 80°C. 1926 g (94% yield) of an off-white solid was obtained. MS (APCI): Formula: C 19 H10 Calculated for Cl4O2 (M+H) = 411; Found: 411. 1 H NMR (400MHz, DMSO) δ 10.93(s,1H), 9.60(s,1H), 7.65(t,J=2.0Hz,2H), 7.48(d,J=1.9Hz,4H), 6.79(s,2H).

[0225] 3,3'',5,5''-tetrachloro-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: 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 (2.400 mmol, 1703 mg), DMAP·pTsOH salt (0.2000 mmol, 59 mg), and EDC·HCl (4.000 mmol, 767 mg) were stirred in dry DCM (50 mL) for 1 h. The reaction mixture was loaded onto approximately 40 g of flash silica gel packed in a loader. Purification was carried out by flash chromatography on silica gel (120 g, 2 CV EtOAc / DCM → 40% (10 CV)). The product-containing fractions were evaporated to dryness in vacuo. 2054 mg (93% yield) of a yellow solid was obtained. MS (APCI): Chemical Formula: C 59 H 29 Calculated for Cl4F6NO6 (M+H) = 1102; Found: 1102. 1 H NMR(400MHz,TCE) δ 8.71(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).

[0226] PLC-18 Diethyl 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-dipyrrolidone [1,2-c:2',1'-f][1,3,2]diazaborinine-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·HO (0.06000 mmol, 11 mg) were stirred in dry 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. The mixture was stirred at room temperature for 10 minutes. EtN (2.400 mmol, 0.33 mL) was added to the reaction, followed by BF·OEt (3.600 mmol, 0.44 mL). The addition of EtN (2.400 mmol, 0.33 mL) and BF OEt (3.600 mmol, 0.44 mL) was repeated, and the reaction was stirred at 50 °C for 30 min. The reaction mixture was cooled to room temperature, quenched with 10 mL of water, and stirred for 5 min. The reaction mixture was filtered through a polypropylene frit to retain moisture. 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. Purification was achieved by flash chromatography on silica gel (40 g, 0% acetone / hexane (2 CV) → 25% (5 CV), gradient stops at 14.3% and 14.4%). The product-containing fractions were evaporated to dryness in vacuo. 304 mg (69% yield) of an orange solid was obtained. MS (APCI): Formula: C 77 H 50 Calculated for BCl4F8N3O9 (M+H) = 1464; Found: 1464. 1H NMR(400MHz,TCE) δ 8.70(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), 4.28(q, J=7.1Hz,4H), 4.08(s,2H), 2.76(s,6H), 1.90(s,7H), 1.35(t,J=7.1Hz,6H).

[0227] Photoluminescent compound PLC-19: [ka]

[0228] Quinolin-6-ylmethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate: 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 dry DMF (40 mL) heated to 100 °C under an argon atmosphere. EDC·HCl (90.00 mmol, 17.203 g) was added to the reaction and rinsed in with 10 mL of dry DMF. The reaction mixture was heated to 130 °C and stirred for 60 min. The reaction was cooled to room temperature and evaporated to dryness in vacuo. The residue was taken up in some acetone and evaporated in vacuo to approximately 40 g of flash silica gel, which was then packed into a loader. Purification was carried out by flash chromatography on silica gel (220 g, 0% EtOAc / toluene (2 CV) → 50% (25 CV)). Fractions containing the product were evaporated to dryness in vacuo. 2370 mg (56% yield) of a light brown solid was obtained. MS (APCI): Formula C 17 H 16 Calculated for N2O2 (M+H) = 281; Found: 281. 1H NMR(400MHz,DMSO) δ 10.96(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)。

[0229] PLC-19 Bis(quinolin-6-ylmethyl)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]diazaborinine-2,8-dicarboxylate:3,3'',5 A mixture of 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), the pyrrole from the previous step (0.5000 mmol, 140 mg), and pTsOH·HO (1.000 mmol, 190 mg) in dry DCE (15 mL) was stirred at 65 °C for 60 min and then cooled to room temperature. The reaction was treated with DDQ (0.5000 mmol, 114 mg) and stirred for 10 min. EtN (2.000 mmol, 0.28 mL) was added to the reaction, followed by BF OEt (3.000 mmol, 0.37 mL). The addition of EtN (2.000 mmol, 0.28 mL) and BF OEt (3.000 mmol, 0.37 mL) was repeated, and the reaction was stirred at 65 °C for 60 min. The reaction mixture was cooled to room temperature, quenched with 10 mL of water, and stirred for 5 min. The reaction mixture was filtered through a polypropylene frit to retain moisture. 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. Purification was carried out by flash chromatography on silica gel (120 g, gradient from 0% acetone / hexane (2 CV) to 30% (5 CV), stopping at 12.0%, 13.0%, and 14.0%). 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 to give 188 mg (42% yield) of an orange solid. MS (APCI): Formula: C. 109 H 92 Calculated for BF8N5O9 (M+H)=1779; Found: 1779. 1 H NMR(400MHz,TCE) δ 8.92(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,7H), 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).

[0230] Photoluminescent compound PLC-20: [ka]

[0231] 2-(9H-Carbazol-9-yl)ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate: 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 dry DMF (40 mL) heated to 100 °C under an argon atmosphere. EDC·HCl (90.00 mmol, 17.203 g) was added to the reaction and rinsed in with 10 mL of dry 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 taken up in some acetone and evaporated in vacuo onto about 40 g of flash silica gel, which was then packed into a loader. Purification was carried out by flash chromatography on silica gel (330 g, 0% EtOAc / toluene (2 CV) → 30% (15 CV)). The product-containing fractions were evaporated to dryness in vacuo. 1322 mg (27% yield) of a light brown solid was obtained. MS (APCI): Formula: C 21 H 20 Calculated for N2O2 (M+H) = 333; Found: 333. 1 H NMR(400MHz,TCE) δ 8.11(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).

[0232] PLC-20 (bis(2-(9H-carbazol-9-yl)ethyl)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]diazaborinine-2,8-dicarboxylate: 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·H2O (1.000 The reaction mixture was stirred at 65 °C for 60 minutes, 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 The mixture was cooled to room temperature, quenched with 10 mL of water, and stirred for 5 minutes. The reaction mixture was filtered through a polypropylene frit to retain moisture. 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. Purification was achieved by flash chromatography on silica gel (120 g, 0% acetone / hexane (2 CV) → 15% (5 CV), gradient stopped at 4.9% and back to 4.4%). The product-containing fractions 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 to give 304 mg (65% yield) of an orange solid. MS (APCI): Formula: C. 117 H 100 Calculated for BF8N5O9 (M+H)=1883; Found: 1883. 1 H NMR(400MHz,TCE) δ 8.70(s,1H), 8.47(s,1H), 8.09(d,J=7.7Hz,4H), 7.91(d,J=8.3Hz,2H), 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,1H), 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).

[0233] Photoluminescent compound PLC-21: [ka]

[0234] 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 mg, 2.200 mmol), DMAP·pTsOH salt, and DIC (0.47 mL, 3.000 mmol) were stirred in dry DCM (10 mL) at room temperature for 30 minutes. The crude reaction mixture was evaporated in vacuo onto approximately 30 g of flash silica gel and packed into a loader. Purification was carried out by flash chromatography on silica gel (120 g, 5% acetone / hexane (2 CV) → 40% (20 CV)). Fractions containing the product were evaporated to dryness in vacuo. 2367 mg (117% yield) of a yellow solid was obtained. NMR showed co-elution with some of the N-acylurea by-product. This was carried on directly to the next step. MS (APCI): Chemical formula: C 51 H 27 F 12 Calculated for NO8 (M+H) = 1010; Found: 1010. 1 H NMR(400MHz,TCE) δ 10.39(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).

[0235] PLC-21 Diethyl 10-(4-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dimethoxyphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate:4-formyl-3,5-dimethoxyphenyl-2 A mixture of -(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate (approximately 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) in dry DCE (30 mL) was stirred overnight at room temperature under argon. The reaction mixture was treated with DDQ (68 mg, 0.3000 mmol) and stirred at room temperature for 30 min. 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 1 h. The crude reaction mixture was evaporated in vacuo onto approximately 30 g of flash silica gel and packed into a loader. Purification was carried out by flash chromatography on silica gel (120 g, 0% acetone / hexane (2 CV) → 35% (15 CV)). The product-containing fractions were evaporated to dryness in vacuo. 178 mg (65% yield) of an orange solid was obtained. MS (APCI): Formula: C 69 H 48 BF 14 N3O 11 Calculated for (M+H)=1372; Found: 1372. 1H NMR (400MHz, TCE) δ 8.76(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), 4.0 5(s,2H), 3.75(s,6H), 2.81(s,6H), 1.88(s,6H), 1.34(t,J=7.1Hz,6H).

[0236] Photoluminescent compound PLC-22: [ka]

[0237] 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) in dry DMF (50 mL) were stirred overnight at 70 °C under argon. The reaction mixture was cooled to room temperature and partitioned between water (200 mL) and ether (200 mL). The reaction was carefully titrated to pH ∼5 with 6 N HCl, and the layers were then separated. The aqueous layer was extracted with ether (2 × 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 onto a loader. Purification was achieved by flash chromatography on silica gel (0% EtOAc / hexanes (2 CV) → 10% (15 CV)). The product-containing fractions were evaporated to dryness to give 3.407 g (16% yield) of a pale yellow oil. MS (APCI): Chemical formula: C 22 H 38 Calculated for O3 (M+H) = 351; Found: 351. 1H NMR(400MHz,CDCl3) δ 6.07(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).

[0238] (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) in dry DCM (25 mL) were stirred under argon at 0 °C and allowed to warm slowly over the weekend. The reaction mixture was diluted with DCM (up to 100 mL), washed with 6 N HCl (50 mL), 10% potassium carbonate solution (50 mL), dried over magnesium sulfate, filtered, and evaporated to dryness. The crude product was dissolved in hexane and loaded onto approximately 40 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) → 10% (20 CV)). The fractions containing the product were evaporated to dryness in vacuo to give 2.533 g (77% yield) of a pale yellow oil. MS (APCI): Chemical formula: C 31 H 58 Calculated for O3Si (M+H) = 507; Found: 507. 1 H NMR(400MHz,CDCl3) δ 6.08(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).

[0239] 2,6-Bis((2-ethylhexyl)oxy)-4-((triisopropylsilyl)oxy)benzaldehyde: (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 dry THF (50 mL) under argon and stirred at 0° C. for 5 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 5 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 dry 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 1 h, 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 vacuo. The crude product was diluted with hexane and loaded onto a loader packed with approximately 45 g of flash silica gel. Purification was carried out by flash chromatography on silica gel (0% EtOAc / hexane (2 CV) → 20% (20 CV)). The product-containing fractions were evaporated to dryness in vacuo. 3.543 g (88% yield) was obtained. MS (APCI): Formula: C 32 H 58 Calculated for O4Si (M+H) = 535; Found: 535. 1 H NMR(400MHz,CDCl3) δ 10.37(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).

[0240] 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 dry 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 6 N HCl solution. The reaction mixture was partitioned with 200 mL of ether, and the layers were separated. The aqueous layer was extracted with 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 loader packed with approximately 40 g of flash silica gel. Purification was carried out by flash chromatography on silica gel (120 g, 0% EtOAc / hexane (2 CV) → 20% (20 CV)). The product-containing fractions were evaporated to dryness in vacuo. 1.742 g (70% yield) was obtained. MS (APCI): Chemical formula: C 23 H 38 Calculated for O4 (M+H) = 379; Found: 379. 1 H NMR (400MHz, acetone) δ 10.37(s,1H), 6.16(s,2H), 3.92(dd,J=5.4,0.6Hz,4H), 1.74(h,J=6.0Hz,2H), 1.64~1.42(m,8H), 1.40~1.27(m,8H), 1.01~0.86(m,12H).

[0241] 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-xantheno[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 dry DCM (20 mL) at room temperature for 30 min. The crude reaction mixture was diluted 1:1 with hexane and loaded onto a loader packed with approximately 50 g of flash silica gel. Purification was carried out by flash chromatography on silica gel (120 g, 0% EtOAc / hexane (2 CV) → 20% (30 CV)). Fractions containing the product were evaporated to dryness in vacuo. 1.035 g (86% yield) of a yellow solid was obtained. MS (APCI): Chemical Formula: C 65 H 55 F 12 Calculated for NO8 (M+H)=1206; Found: 1206. 1 H NMR (400MHz, 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=8.5,7.2,1.5Hz,1H), 7.47~7.40(m,2H), 7.30(dd,J=8.3,1.3Hz,1H), 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).

[0242] PLC-22 Diethyl 10-(4-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-bis((2-ethylhexyl)oxy)phenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate:3,5-bis((2-ethylhexyl)oxy) (iii)-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 (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) in dry DCE (25 mL) were stirred at room temperature under argon for 1 h. The reaction mixture was treated with DDQ (331 mg, 1.459 mmol) and stirred at room temperature for 30 min. 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 EtN (0.96 mL, 6.865 mmol) and BF·OEt (0.87 mL, 7.061 mmol) was repeated and the reaction mixture was stirred at 50 °C for 1 h. The crude reaction mixture was evaporated in vacuo onto approximately 40 g of flash silica gel. Purification was carried out by flash chromatography on silica gel (120 g, 0% EtOAc / hexane (2 CV) → 25% (30 CV)). Fractions containing the product were evaporated to dryness in vacuo. The purification was repeated to remove trace impurities. 1.122 g (83% yield) of an orange solid was obtained. MS (APCI): Formula: C 83 H 76 BF 14 N3O 11 Calculated for (M+H)=1569; Found: 1569. 1H NMR (400MHz, アセトン) δ 8.77(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), 2.79(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).

[0243] フォトルミネッセンス compound PLC-23:

change

[0244] 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) in dry DMF (50 mL) were stirred at 50 °C under argon for 3 hours. The reaction was cooled to room temperature and partitioned between water (200 mL) and ether (200 mL). The reaction was carefully titrated to pH 6.5 with 6 N HCl, and the layers were then separated. The aqueous layer was extracted with ether (2 × 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 ether and loaded onto approximately 45 g of flash silica gel packed in a loader. Purification was achieved by flash chromatography on silica gel (220 g, 0% EtOAc / hexane (2 CV) to 25% (20 CV)). Fractions containing the product were evaporated to dryness in vacuo. 5.775 g (27% yield) of a waxy off-white solid was obtained. MS (APCI): Formula C 24 H 26 Calculated for O3 (M+H) = 363; Found: 363. 1 H NMR(400MHz,CD2Cl2) δ 7.34~7.25(m,4H), 7.25~7.14(m,6H), 6.05(q,J=1.9Hz,1H), 5.99(t,J=1.7Hz,2H), 4 .93(d,J=1.3Hz,1H), 3.91(t,J=6.3Hz,4H), 2.78(t,J=7.7Hz,4H), 2.13~2.02(m,4H).

[0245] 4-Hydroxy-2,6-bis(3-phenylpropoxy)benzaldehyde: 3,5-bis(3-phenylpropoxy)phenol (5.770 g, 15.92 mmol) was dissolved in dry DCM (5 mL) and treated with POCl3 (3.0 mL, 31.84 mmol) at room temperature under argon. The reaction mixture was stirred for 10 minutes, then cooled to 0°C and treated dropwise with dry DMF (1.84 mL, 23.88 mmol) while stirring. The reaction mixture was stirred at 0°C and allowed to warm slowly to room temperature overnight. The reaction mixture was quenched with crushed ice and then diluted to approximately 100 mL with water. The reaction was carefully quenched with 10% aqueous potassium carbonate to a pH of approximately 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 approximately 50 g of flash silica gel packed in a loader. Purification was carried out by flash chromatography on silica gel (220 g, 0% EtOAc / hexane (2 CV) → 20% (20 CV) → 50% (0 CV) → isocratic 50%). The product-containing fractions were evaporated to dryness in vacuo. 1.341 g (22% yield) was obtained. MS (APCI): Formula: C 25 H 26 Calculated for O4 (M+H) = 391; Found: 391. The compound is a 1:1 mixture with an inseparable by-product. Carried forward to the next step.

[0246] 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)acetic acid (1015 mg, 1.200 mmol), DMAP·pTsOH salt (29 mg, 0.1000 mmol), and DIC (0.313 mL, 2.000 mmol) in dry DCM (15 mL) were stirred at room temperature for 30 min. The crude reaction mixture was diluted 1:1 with hexane and loaded onto a loader packed with approximately 50 g of flash silica gel. Purification was carried out by flash chromatography on silica gel (120 g, 0% EtOAc / hexane (2 CV) → 10% (20 CV)). Fractions containing the product were evaporated to dryness in vacuo. 1034 mg (85% yield) of a yellow solid was obtained. MS (APCI): Chemical Formula: C 67 H 43 F 12 Calculated for NO8 (M+H)=1218; Found: 1218. 1 H NMR(400MHz,CD2Cl2) δ 10.49(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).

[0247] PLC-23 Diethyl 10-(4-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-bis(3-phenylpropoxy)phenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate:4-formyl-3,5-bis(3-phenyl A mixture of (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) in dry DCE (25 mL) was stirred at room temperature under argon for 1 h. The reaction mixture was treated with DDQ (347 mg, 1.527 mmol) and stirred at room temperature for 30 min. The reaction was then treated with EtN (0.95 mL, 6.785 mmol) and BF·OEt (1.25 mL, 10.18 mmol). The addition of EtN (0.95 mL, 6.785 mmol) and BF·OEt (1.25 mL, 10.18 mmol) was repeated and the reaction mixture was stirred at 50 °C for 1 h. The crude reaction mixture was evaporated in vacuo onto approximately 40 g of flash silica gel and loaded onto a loader. Purification was achieved by flash chromatography on silica gel (220 g, 0% EtOAc / DCM (2 CV) → 1% (20 CV)). Fractions containing the product were evaporated to dryness in vacuo. 533 mg (40% yield) of an orange solid was obtained. MS (APCI): Formula: C 85 H 64 BF 14 N3O 11 Calculated for (M+H)=1580; Found: 1580. 1H NMR(400MHz,CD2Cl2) δ 8.78(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).

[0248] Photoluminescent compound PLC-24: [ka]

[0249] 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 dry 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 ether (3 × 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 approximately 50 g of flash silica gel and loaded onto a loader. Purification was achieved by flash chromatography on silica gel (330 g, 0% EtOAc / hexane (2 CV) → 25% (10 CV)). The product-containing fractions were evaporated to dryness in vacuo. 3.157 g (7.9% yield) was obtained. MS (APCI): Chemical formula: C 20 H 30Calculated for O3 (M+H) = 319; Found: 319. 1 H NMR(400MHz,TCE) δ 6.07(t,J=2.1Hz,1H), 3.69(d,J=6.3Hz,4H), 1.92~1.65(m,10H), 1.42~1.10(m,9H), 0.96~0.76(m,2H).

[0250] 2,6-Bis(cyclohexylmethoxy)-4-hydroxybenzaldehyde: 3,5-Bis(cyclohexylmethoxy)phenol (3.150 g, 9.891 mmol) was dissolved in dry DCM (6 mL) under argon and stirred at room temperature. The reaction mixture was treated with POCl3 (1.84 mL, 3.033 mmol), stirred at room temperature for 5 minutes, then cooled to 0 °C and treated dropwise with dry DMF (0.92 mL, 11.87 mmol). The reaction mixture was stirred at 0 °C for 1 hour, and then the contents of the reaction were poured onto approximately 100 mL of crushed ice and rinsed with a small amount of acetone. The reaction mixture was titrated to a pH of approximately 6-7 with 10% potassium carbonate solution and then extracted with DCM (100 mL, 2 × 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 approximately 50 g of flash silica gel packed in a loader. Purification was carried out by flash chromatography on silica gel (120 g, 0% EtOAc / hexane (2 CV) → 100% EtOAc (15 CV)). The product-containing fractions were evaporated to dryness in vacuo. 175 mg (5.1% yield) was obtained. MS (APCI): Formula: C 21 H 30 Calculated for O4 (M+H) = 347; Found: 347. 1 H NMR(400MHz,TCE) δ 10.32(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).

[0251] 3,5-bis(cyclohexylmethoxy)-4-formylphenyl 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)acetic acid (430 mg, 0.6061 mmol), DMAP·pTsOH salt (15 mg, 0.05051 mmol), and DIC (0.158 mL, 1.010 mmol) in dry DCM (10 mL) were stirred at room temperature for 30 min. The crude reaction mixture was loaded onto approximately 45 g of flash silica gel packed in a loader by dissolving in DCM. Purification was performed by flash chromatography on silica gel (120 g, 0% EtOAc / DCM (2 CV) → 5% (10 CV)). Fractions containing the product were evaporated to dryness in vacuo. 449 mg (86% yield) of a yellow solid was obtained. MS (APCI): Chemical Formula: C 61 H 49 Calculated for F6NO8 (M+H) = 1038; Found: 1038. 1 H NMR (400MHz, TCE) δ 10.44(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=8.3,1.5H z,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).

[0252] PLC-24 Diethyl 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]diazaborinine-2,8-dicarboxylate:3,5-bis(cyclohexylmethoxy) A mixture of 4-formylphenyl-2-(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) in dry DCE (25 mL) was stirred at room temperature under argon for 1 h. The reaction mixture was treated with DDQ (175 mg, 0.7716 mmol) and stirred at room temperature for 30 min. 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 EtN (0.48 mL, 3.430 mmol) and BF·OEt (0.64 mL, 5.144 mmol) was repeated, and the reaction mixture was stirred at 50 °C for 1 h. The crude reaction mixture was evaporated in vacuo onto approximately 50 g of flash silica gel and loaded onto a loader. Purification was achieved by flash chromatography on silica gel (120 g, 100% hexane / toluene, EtOAc modifier, 0.1% → 1% → 2% → 3% step gradient). Fractions containing the product were evaporated to dryness in vacuo. 446 mg (74% yield) of an orange solid was obtained. MS (APCI): Formula: C 79 H 70 BF8N3O 11 Calculated for (M+H)=1401; Found: 1401. 1H NMR (400MHz, TCE) δ 10.44(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=8.3,1.5H z,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).

[0253] Photoluminescent compound PLC-25: [ka]

[0254] 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) in dry DCM (30 mL) were stirred at room temperature for 30 min. The crude reaction mixture was loaded onto approximately 50 g of flash silica gel packed in a loader. Purification was carried out by flash chromatography on silica gel (120 g, 0% EtOAc / DCM (2 CV) → 15% (20 CV)). Fractions containing the product were evaporated to dryness in vacuo. 1956 mg (90% yield) of a yellow solid was obtained. MS (APCI): Chemical Formula: C 49 H 29 Calculated for F6NO8 (M+H) = 874; Found: 874. 1H NMR(400MHz,TCE) δ 10.39(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(dd,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)。

[0255] PLC-25 Diethyl 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-1,3,7,9-tetramethyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate:4-formyl-3,5-dimethoxyphenyl A mixture of 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) in dry DCE (100 mL) was stirred at room temperature under argon for 1 h. The reaction mixture was treated with DDQ (912 mg, 4.017 mmol) and stirred at room temperature for 30 min. The reaction was then treated with EtN (2.5 mL, 17.85 mmol) and BF·OEt (3.31 mL, 26.78 mmol). The addition of EtN (2.5 mL, 17.85 mmol) and BF·OEt (3.31 mL, 26.78 mmol) was repeated and the reaction mixture was stirred at 50° C. for 1 h. The crude reaction mixture was cooled to room temperature and evaporated in vacuo onto approximately 55 g of flash silica gel. Purification was achieved by flash chromatography on silica gel (120 g, 100% toluene / hexanes, EtOAc modifier, 2% to 4% step gradient). Fractions containing the product were evaporated to dryness in vacuo. 2080 mg (75% yield) of an orange solid was obtained. MS (APCI): Formula: C 67 H 50 BF8N3O 11 Calculated for (M+H)=1236; Found: 1236. 1H NMR(400MHz,TCE) δ 8.62(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).

[0256] Photoluminescent compound PLC-26: [ka]

[0257] 2,6-Bis(2-ethylhexyl)-4-hydroxybenzaldehyde: 2,6-Dibromo-4-hydroxybenzaldehyde (380 mg, 1.358 mmol) was dissolved in dry THF (25 mL), treated with Pd(dppf)Cl (199 mg, 0.2716 mmol), and stirred at room temperature under argon. The solution was sparged with argon, and then (2-ethylhexyl)zinc(II) bromide (0.5 M in THF, 16.3 mL, 8.148 mmol) was added, and the reaction mixture was stirred at room temperature for 5 minutes. The reaction mixture was heated at 40 °C overnight. The reaction mixture was cooled to room temperature, quenched with saturated NH Cl solution (100 mL), and extracted with ethyl acetate (100 mL, 2 × 50 mL). The combined organic layers were dried over magnesium sulfate, filtered, and evaporated to dryness. The crude product was evaporated in vacuo onto approximately 40 g of flash silica gel and loaded onto a loader. Purification was carried out by flash chromatography on silica gel (120 g, 0% EtOAc / hexane (2 CV) → 30% (20 CV)). Fractions containing the product were evaporated to dryness in vacuo. 247 mg (52% yield) of an off-white solid was obtained. MS (APCI): Chemical formula: C 23 H 38 Calculated for O2 (M+H) = 347; Found: 347. 1H NMR (400MHz, acetone) δ 10.41(s,1H), 6.62(s,2H), 2.89(dt,J=7.3,5.1Hz,4H), 1.54(p,J=6.5Hz,2H), 1.39~1.13(m,16H), 0.92~0.80(m,12H).

[0258] 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: 2,6-bis(2-ethylhexyl)-4-hydroxybenzaldehyde (247 mg, 0.7127 mmol), 2-(4-(5,1 1-Bis(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) in dry DCM (10 mL) were stirred at room temperature for 30 min. The crude reaction mixture was diluted 1:1 with hexane and loaded onto a loader packed with approximately 50 g of flash silica gel. Purification was performed by flash chromatography on silica gel (120 g, 0% EtOAc / hexane (2 CV) → 20% (30 CV)). Fractions containing the product were evaporated to dryness in vacuo. 841 mg (100%) of a yellow solid was obtained. MS (APCI): Chemical Formula: C 65 H 55 F 12 Calculated for NO6 (M+H) = 1174; Found: 1174. 1H NMR(400MHz、アセトン) δ 10.55(s,1H)、8.77(s,1H)、8.59(d,J=1.6Hz,2H)、8.53(s,1H)、8.35(d,J=1.6Hz,2H)、8.24(s,1H)、8.20(s,1H)、7.61(d,J=8.3Hz,3H)、7.55(ddd,J=8.5,7.2,1.5Hz,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)。

[0259] PLC-26 Diethyl 10-(4-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-bis(2-ethylhexyl)phenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate):3,5-bis(2-ethylhexyl)-4 A mixture of -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) in dry DCE (25 mL) was stirred overnight at 50 °C under argon. The reaction mixture was cooled to room temperature, treated with DDQ (275 mg, 1.212 mmol), and stirred at room temperature for 30 min. The reaction was then treated with EtN (0.80 mL, 5.702 mmol) and BF·OEt (1.06 mL, 8.552 mmol). The addition of EtN (0.80 mL, 5.702 mmol) and BF·OEt (1.06 mL, 8.552 mmol) was repeated and the reaction mixture was stirred at 50 °C for 1 h. The reaction mixture was evaporated onto approximately 45 g of flash silica gel and evaporated to dryness in vacuo. Purification was carried out by flash chromatography on silica gel (120 g, 0% EtOAc / toluene (2 CV) → 2% (30 CV)). Fractions containing the product were evaporated to dryness in vacuo. 419 mg (38% yield) of an orange solid was obtained. MS (APCI): Formula: C 83 H 76 BF 14 Calculated for N3O9 (M+H) = 1537; Found: 1537. 1H NMR (400MHz, アセトン) δ 8.76(s,1H), 8.59~8.56(m,2H), 8.52(s,1H), 8.34(d,J=1.7Hz,2H), 8.24(dq,J=1.9,1.0Hz,1H), 8.20(td,J=1.7,0 .9Hz,1H), 7.68~7.59(m,2H), 7.54(ddd,J=8.5,7.2,1.6Hz,1H), 7.50~7.42(m,2H), 7.29(dd,J=8.3,1.2Hz,1H), 7.1 7(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=2.0Hz,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).

[0260] フォトルミネッセンス compound PLC-27:

change

[0261] 2,6-Dicyclopropyl-4-hydroxybenzaldehyde: Zinc chloride (2726 mg, 20.00 mmol) was heated under vacuum at 150 °C for 1 hour and then cooled to room temperature under an argon atmosphere. Dry THF (100 mL) was added to this salt, followed by cyclopropylmagnesium bromide solution (1.0 M in 2-methyl-THF, 20.0 mL) and stirred overnight at room temperature. Pd(dppf)Cl (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 4 hours. The reaction mixture was cooled to room temperature and then quenched with saturated NH4Cl solution (50 mL) followed by 6 N 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 approximately 40 g of flash silica gel and loaded onto a loader. Purification was carried out by flash chromatography on silica gel (120 g, 0% acetone / hexane (2 CV) → 40% (20 CV)). The product-containing fractions were evaporated to dryness in vacuo. 120 mg (30% yield) of an off-white solid was obtained. MS (APCI): Chemical formula: C 13 H 14 Calculated for O2 (M+H) = 203; Found: 203. 1 H NMR (400MHz,TCE) δ 10.87(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).

[0262] 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(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate A mixture of (3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[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) in dry DCM (10 mL) was stirred at room temperature for 30 min. The reaction mixture was diluted 1:1 with hexane and loaded onto a loader packed with approximately 45 g of flash silica gel. Purification was performed by flash chromatography on silica gel (0% acetone / hexane (2 CV) → 40% (20 CV)). The product-containing fractions were evaporated to dryness in vacuo. 252 mg (42% yield) of a yellow solid was obtained. MS (APCI): Chemical Formula: C 55 H 31 F 12 Calculated for NO6 (M+H) = 1030; Found: 1030. 1 H NMR (400MHz, TCE) δ 10.96(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).

[0263] PLC-27 Diethyl 10-(4-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dicyclopropylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate:3,5-dicyclopropyl-4-formyl A mixture of 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 (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) in dry DCE (25 mL) was stirred overnight at room temperature under argon. The reaction mixture was treated with DDQ (240 mg, 1.059 mmol) and stirred at room temperature for 30 min. 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 1 h. The reaction mixture was cooled to room temperature and evaporated in vacuo onto approximately 35 g of flash silica gel. Purification was carried out by flash chromatography on silica gel (120 g, 0% EtOAc / hexane (2 CV) → 35% (20 CV)). The product-containing fractions were evaporated to dryness in vacuo. 127 mg (44% yield) of an orange solid was obtained. MS (APCI): Formula: C 73 H 52 BF 14 Calculated for N3O9 (M+H) = 1392; Found: 1392. 1H NMR (400MHz, 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=8.5,7.2,1.5Hz,1H), 7.47~7.39(m,2H), 7.30(dd,J=8.3,1.2Hz,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).

[0264] Photoluminescent compound PLC-30: [ka]

[0265] 4-Hydroxy-2,6-dipentylbenzaldehyde: 2,6-Dibromo-4-hydroxybenzaldehyde (190 mg, 0.6788 mmol), pentylboronic acid (630 mg, 5.430 mmol), Pd(dppf)Cl (99 mg, 0.1358 mmol), and cesium carbonate (885 mg, 2.715 mmol) were combined in a 30 mL microwave vial in THF (10 mL) and water (1 mL). The vial was sealed and heated in a microwave synthesizer at 130 °C for 2 h. The crude reaction mixture was evaporated in vacuo onto approximately 30 g of flash silica gel and loaded onto a loader. Purification was achieved by flash chromatography on silica gel (120 g, 0% acetone / hexane (2 CV) → 40% (20 CV)). The product-containing fractions were evaporated to dryness in vacuo. The compound was not pure by NMR but was carried forward to the next step. MS (APCI): Chemical formula: C 15 H 22 Calculated for O2 (M+H) = 235; Found: 235.

[0266] 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 (Fluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinoline(isoquinoline)-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 dry DCM (10 mL) and stirred at room temperature for 30 min. The crude reaction mixture was evaporated in vacuo onto approximately 25 g of flash silica gel and loaded onto a loader. Purification was achieved by flash chromatography on silica gel (120 g, 0% acetone / hexane (2 CV) → 30% (25 CV)). Fractions containing the product were evaporated to dryness in vacuo. 193 mg (62% yield) of a yellow solid was obtained. MS (APCI): Chemical Formula: C 57 H 39 F 12 Calculated for NO6 (M+H) = 1062; Found: 1062. 1 H NMR (400MHz, TCE) δ 10.49(s,1H), 8.76(s,1H), 8.51(s,1H), 8.27(d,J=1.5Hz,2H), 8.07(s,1 H), 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).

[0267] PLC-28 Diethyl 10-(4-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dipentylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate:4-formyl-3,5-dipentylphenyl Ethyl-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 dry DCE (15 mL) and stirred overnight at room temperature under argon. The reaction mixture was treated with DDQ (60 mg, 0.2642 mmol) and stirred at room temperature for 30 min. 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 1 h. The crude reaction mixture was evaporated in vacuo onto approximately 30 g of flash silica gel. Purification was achieved by flash chromatography on silica gel (120 g, 0% acetone / hexane (2 CV) → 30% (25 CV)). Fractions containing the product were evaporated to dryness in vacuo. 166 mg (65% yield) of an orange solid was obtained. MS (APCI): Formula: C 75 H 60 BF 14 Calculated for N3O9 (M+H) = 1424; Found: 1424. 1H NMR(400MHz,TCE) δ 8.76(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,2 H), 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,4H), 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).

[0268] フォトルミネッセンス compound PLC-29:

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[0269] 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 dry THF (50 mL) and stirred at room temperature under argon. The reaction mixture was thoroughly sparged with argon, and then (cyclohexylmethyl)zinc(II) bromide (0.5 M in THF, 32.0 mL, 16.00 mmol) was added, and the reaction mixture was further sparged with argon. The reaction mixture was stirred at room temperature for 5 minutes and then heated to 40 °C overnight. The reaction mixture was cooled to room temperature and partitioned between water (100 mL) and ether (100 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 vacuo. The crude reaction mixture was evaporated in vacuo onto approximately 20 g of flash silica gel and packed into a loader. Purification was carried out by flash chromatography on silica gel (0% EtOAc / hexane (2 CV) → 20% (15 CV)). Fractions containing the product were evaporated to dryness in vacuo to give 833 mg (66% yield) of an off-white solid. MS (APCI): Formula: C 21 H 30 Calculated for O2 (M+H) = 315; Found: 315. 1 H NMR(400MHz,CD2Cl2) δ 10.38(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).

[0270] 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(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[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) in dry DCM (10 mL) were stirred at room temperature for 30 min. The crude reaction mixture was diluted with 3 parts hexane and loaded onto approximately 45 g of flash silica gel packed in a loader. Purification was performed by flash chromatography on silica gel (120 g, isocratic DCM). Fractions containing the product were evaporated to dryness in vacuo. 1436 mg (97% yield) of a yellow solid was obtained. MS (APCI): Chemical Formula: C 63 H 47 F 12 Calculated for NO6 (M+H) = 1142; Found: 1142. 1 H NMR(400MHz,CD2Cl2) δ 10.49(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).

[0271] PLC-29 Diethyl 10-(4-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-bis(cyclohexylmethyl)phenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate: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 (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) in dry DCE (30 mL) were stirred at room temperature under argon for 1 h. The reaction mixture was treated with DDQ (513 mg, 2.262 mmol) and stirred at room temperature for 30 min. Two additional portions of DDQ (86 mg, 0.3371 mmol) were added at 15 and 30 min, and the reaction mixture was then stirred for an additional 30 min. The reaction was then treated with EtN (1.4 mL, 10.05 mmol) and BF·OEt (1.87 mL, 15.08 mmol). The addition of EtN (1.4 mL, 10.05 mmol) and BF·OEt (1.87 mL, 15.08 mmol) was repeated and the reaction mixture was stirred at 50 °C for 1 h. The reaction mixture was cooled to room temperature and evaporated in vacuo onto approximately 30 g of flash silica gel and loaded onto a loader. Purification was achieved by flash chromatography on silica gel (220 g, 0% EtOAc / DCM (2 CV) → 3.5% (20 CV) → 3.5% isocratic). The product-containing fractions were evaporated to dryness in vacuo. 1182 mg (63% yield) of an orange solid was obtained. MS (APCI): Formula: C 81 H 68 BF 14 Calculated for N3O9 (M+H) = 1504; Found: 1504. 1H NMR (400MHz, アセトン) δ 8.77(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(td,J=1.7,0.9H z,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,2 H), 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).

[0272] フォトルミネッセンス compound PLC-30:

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[0273] 2,6-Dicyclohexyl-4-hydroxybenzaldehyde: 2,6-Dibromo-4-hydroxybenzaldehyde (1120 mg, 4.000 mmol) and Pd(dppf)Cl2 (585 mg, 0.8000 mmol) were combined in dry THF (50 mL) and stirred at room temperature under argon. After the reaction mixture was thoroughly sparged with argon, cyclohexylzinc(II) bromide (0.5 M in THF, 32.0 mL, 16.00 mmol) was added, and the reaction mixture was further sparged with argon. The reaction mixture was stirred at room temperature for 5 minutes and then heated to 40 °C overnight. The reaction mixture was heated at 80 °C for 6 hours and then cooled to room temperature. The crude reaction mixture was evaporated in vacuo onto approximately 50 g of flash silica gel and packed into a loader. Purification was achieved by flash chromatography on silica gel (120 g, 0% EtOAc / hexane (2 CV) → 20% (15 CV)). The product-containing fractions were evaporated to dryness in vacuo to give 94 mg (8.2% yield) of an off-white solid. MS (APCI): Chemical formula: C 19 H 26 Calculated for O2 (M+H) = 287; Found: 287. 1 H 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).

[0274] 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( A mixture of 3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[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) in dry DCM (5 mL) was stirred at room temperature for 30 min. The crude reaction mixture was diluted 2:1 with hexane and loaded onto approximately 30 g of flash silica gel packed in a loader. Purification was performed by flash chromatography on silica gel (120 g, isocratic DCM). The product-containing fractions were evaporated to dryness in vacuo. 291 mg (80% yield) of a yellow solid was obtained. MS (APCI): Chemical Formula: C 61 H 43 F 12 Calculated for NO6 (M+H) = 1114; Found: 1114. 1 H NMR (400MHz, acetone) δ 10.66(s,1H), 8.76(s,1H), 8.58(d,J=1.7Hz,2H), 8.52(s,1H), 8.33(d,J=1.7Hz,2H), 8.24(dd,J=1.8,0. 9Hz,1H), 8.20(dq,J=2.0,0.9Hz,1H), 7.65~7.57(m,2H), 7.54(ddd,J=8.5,7.2,1.5Hz,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).

[0275] PLC-30 Diethyl 10-(4-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dicyclohexylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate:3,5-dicyclohexyl-4-formyl 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 (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) in dry DCE (30 mL) were stirred at room temperature under argon for 1 h. The reaction mixture was treated with DDQ (106 mg, 0.4686 mmol) and stirred at room temperature for 30 min. 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 1 h. The crude reaction mixture was evaporated in vacuo onto approximately 25 g of flash silica gel and packed into a loader. Purification was carried out by flash chromatography on silica gel (220 g, 0% EtOAc / DCM (2 CV) → 3.5% (20 CV) → 3.5% isocratic). The product-containing fractions were evaporated to dryness in vacuo. 302 mg (79% yield) of an orange solid was obtained. MS (APCI): Formula: C 79 H 64 BF 14 Calculated for N3O9 (M+H) = 1476; Found: 1476. 1H NMR (400MHz, CD2Cl2) δ 8.78(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=4.1,1.8Hz,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).

[0276] フォトルミネッセンス compound PLC-31:

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[0277] PLC-31 Diethyl 10-(4-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dicyclohexylphenyl)-5,5-difluoro-3,7-dimethyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate:3,5-dicyclohexyl-4-formyl 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 (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) in dry DCE (30 mL) were stirred overnight at 70 °C under argon. The reaction was cooled to room temperature, treated with DDQ (184 mg, 0.80 mmol), and stirred at room temperature for 30 min. 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 EtN (0.50 mL, 3.600 mmol) and BF·OEt (0.67 mL, 5.400 mmol) was repeated, and the reaction mixture was stirred at 50 °C for 1 h. The crude reaction mixture was evaporated in vacuo onto approximately 50 g of flash silica gel and loaded onto a loader. Purification was achieved by flash chromatography on silica gel (120 g, 0% EtOAc / toluene (2 CV) → 0.1% (3 CV) → 0.2% (3 CV) → 0.3% (3 CV) → 0.4% (3 CV) → 0.5% (3 CV) → 5% (10 CV)). Fractions containing the product were evaporated to dryness in vacuo. 393 mg (60% yield) of an orange solid was obtained. MS (APCI): Formula: C 77 H 60 BF 14 Calculated for N3O9 (M+H) = 1448; Found: 1448. 1H NMR (400MHz, acetone) δ 8.76(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), 8.20(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,1 H), 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), 4.13(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).

[0278] Photoluminescent compound PLC-32: [ka]

[0279] 2,6-Dibromo-4-(methoxymethoxy)benzaldehyde: 2,6-Dibromo-4-hydroxybenzaldehyde (5.598 g, 20.00 mmol) and potassium carbonate (5528 mg, 40.00 mmol) were combined in dry THF (100 mL) and stirred under argon. MOM-Cl (1.97 mL, 26.00 mmol) was added to the flask. The reaction mixture was stirred at room temperature overnight. The crude reaction mixture was evaporated in vacuo onto approximately 60 g of flash silica gel and loaded onto a loader. Purification was achieved by flash chromatography on silica gel (220 g, 25% DCM / hexane (0.5 CV) → 100% DCM (0 CV) → isocratic DCM). Fractions containing the product were evaporated to dryness in vacuo. 5.677 g (88% yield) of an off-white solid was obtained. MS (APCI): Calculated (M+H) for formula C9H8Br2O3 = 323; Found: 323.

[0280] 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 crimped and the vial was heated in a 100 °C heat block for 6 hours. The crude reaction mixture was evaporated in vacuo onto approximately 40 g of flash silica gel and packed into a loader. Purification was achieved by flash chromatography on silica gel (120 g, 0% EtOAc / hexane (2 CV) → 100% EtOAc (20 CV)). The product-containing fractions were evaporated to dryness in vacuo to give 247 mg (71% yield) of an orange oil that slowly solidified. MS (APCI): Chemical formula: C 21 H 18 Calculated for O5 (M+H)=351; Found: 351. 1 H NMR(400MHz,CD2Cl2) δ 10.41(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).

[0281] 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 hexanes and loaded onto a loader packed with approximately 50 g of flash silica gel. Purification was achieved by flash chromatography on silica gel (120 g, 0% EtOAc / hexane (2 CV) → 100% EtOAc (20 CV)). Fractions containing the product were evaporated to dryness in vacuo. 194 mg (90% yield) of an off-white solid was obtained. MS (APCI): Chemical Formula: C 19 H 14 Calculated for O4 (M+H) = 307; Found: 307. 1 H NMR (400MHz, CD2Cl2) δ 10.38(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).

[0282] 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 A mixture of (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) in dry DCM (10 mL) was stirred at room temperature for 30 min. The crude reaction mixture was loaded onto a loader packed with approximately 40 g of flash silica gel. Purification was carried out by flash chromatography on silica gel (120 g, 0% EtOAc / DCM (2 CV) → 10% (30 CV)). The product-containing fractions were evaporated to dryness in vacuo. 642 mg (90% yield) of a yellow solid was obtained. MS (APCI): Chemical Formula: C 61 H 31 F 12 Calculated for NO8 (M+H)=1134; Found: 1134. 1 H NMR(400MHz,CD2Cl2) δ 10.54(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).

[0283] PLC-32 Diethyl 10-(4-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-diphenoxyphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate:4-formyl-3,5-diphenoxyphenyl Nyl-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 under argon in dry DCE (50 mL) at room temperature for 1 h. The reaction mixture was treated with DDQ (230 mg, 1.014 mmol) and stirred at room temperature for 30 min. 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 EtN (0.63 mL, 4.508 mmol) and BF·OEt (0.83 mL, 6.763 mmol) was repeated and the reaction mixture was stirred at 50° C. for 1 h. The crude reaction mixture was evaporated in vacuo onto approximately 60 g of flash silica gel and loaded onto a loader. Purification was achieved by flash chromatography on silica gel (220 g, 0% EtOAc / DCM (2 CV) → 3% (20 CV) → 3% isocratic). 598 mg (71% yield) of an orange solid was obtained. MS (APCI): Formula: C 79 H 52 BF 14 N3O 11 Calculated for (M+H)=1496; Found: 1496. 1H NMR (400MHz, アセトン) 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), 8.22~8.1 8(m,1H), 7.54(ddd,J=8.5,7.2,1.5Hz,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), 6.5 2(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).

[0284] フォトルミネッセンス compound PLC-33:

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[0285] PLC-33 Diethyl 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-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate:diethyl 10-(4-(2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl) (phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dimethoxyphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate (0.1000 mmol, 124 mg) was dissolved in dry 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 approximately 30 mL of saturated NaHCO₃ and stirred for several minutes. The reaction was filtered through a polypropylene frit to retain moisture, 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 approximately 15 g of flash silica gel packed in a loader. Purification was achieved by flash chromatography on silica gel (80 g, 0% acetone / hexane (2 CV) → 35% (5 CV), gradient stop 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. 121 mg (97% yield) of an orange solid was obtained. MS (APCI): Formula: C 69 H 50 BF6N5O 11 Calculated for (M+H)=1250; Found: 1250. 1H NMR(400MHz,TCE) δ 8.71(s,1H), 8.48(s,1H), 7.91(d,J=8.3Hz,2H), 7.89~7.82(m,4H), 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).

[0286] Photoluminescent compound PLC-34: [ka]

[0287] 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):2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-de [f]isoquinolin-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 a vial with dry DCE (30 mL) at room temperature for 60 min. The crude reaction mixture was loaded onto approximately 45 g of flash silica gel packed in a loader. Purification was carried out by flash chromatography on silica gel (120 g, 0% EtOAc / DCM (2 CV) → 30% (10 CV)). The product-containing fractions were evaporated to dryness in vacuo. 2061 mg (82% yield) of a yellow solid was obtained. MS (APCI): Chemical Formula: C 51 H 27 F 12Calculated for NO8 (M+H) = 1010; Found: 1010. 1 H NMR (400MHz, acetone) δ 10.38(s,1H), 8.76(s,1H), 8.60~8.56(m,2H), 8.51(s,1H), 8.33(d,J=1.7Hz,2H ), 8.24(s,1H), 8.22~8.18(m,1H), 7.60(d,J=8.4Hz,2H), 7.54(ddd,J=8.5,7.2,1 .5Hz,1H), 7.48~7.40(m,2H), 7.28(dd,J=8.3,1.3Hz,1H), 7.11(dd,J=8.3,1.5H z,1H), 7.02(ddd,J=8.3,7.1,1.3Hz,1H), 6.61(s,2H), 4.09(s,2H), 3.87(s,6H).

[0288] PLC-34 Dimethyl 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-Dicarboxylate: 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 dry DCE (25 mL) under argon at room temperature for 30 min. DDQ (0.8000 mmol, 182 mg) was then added and stirred for 5 min. 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 h, then at room temperature overnight. The reaction was quenched with 5 mL of water, stirred for a few minutes, and then filtered through a polypropylene frit to retain moisture. The frit was eluted with DCM. The eluent was placed on 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 gel packed in a loader. Purification was achieved by flash chromatography on silica gel (120 g, eluting with 0% EtOAc / DCM (2 CV) → 20% (5 CV), stopping at 4.0%, isocratic). The product-containing fractions 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 to give 447 mg (80% yield) of an orange solid. MS (APCI): Formula C 69 H 54 BF8N3O 11 Calculated for (M+H)=1264; Found: 1264. 1H NMR(400MHz,TCE) δ 8.67(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), 6.46(s,2H), 3.96(s,2H), 3.74(s,8H), 3.68(s,6H), 1.31(d,J=7.0Hz,12H).

[0289] フォトルミネッセンス compound PLC-35:

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[0290] PLC-35 Dimethyl 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]diazaborinine-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 dry DCE (10 mL) under argon at room temperature for several minutes, then heated to 45 °C for 60 minutes, and then heated at room temperature overnight. The crude reaction mixture was poured into 30 mL of saturated NaHCO₃ solution and stirred for 5 minutes, then filtered through a polypropylene frit to retain moisture. 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. Purification was achieved by flash chromatography on silica gel (80 g, 0% acetone / DCM (2 CV) → 5% (5 CV), stopping at 1.1%, 1.4%, 1.6%, 1.8%, 2.2%, 2.4%, isocratic at each step). Fractions containing the 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. 157 mg (74% yield) of an orange solid was obtained. MS (APCI): Formula: C 73 H 52 BF 12 N5O 11 Calculated for (M+H)=1414; Found: 1414. 1H NMR (400MHz, TCE) δ 8.76(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,1H), 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).

[0291] Example 2: Procedure for measuring the optical properties of sharp-emitter chromophores The glass substrates were prepared essentially as follows: 1.1 mm thick glass substrates measuring 1 inch by 1 inch were cut to size. The glass substrates were then cleaned with detergent and deionized (DI) water, rinsed with fresh DI water, and sonicated for approximately 1 hour. The glass was then immersed in isopropanol (IPA) and sonicated for approximately 1 hour. The glass substrates were then immersed in acetone and sonicated for approximately 1 hour. The glass was then removed from the acetone bath and dried with nitrogen gas at room temperature.

[0292] A 25 wt% solution of poly(methyl methacrylate) (PMMA) resin in spectroscopic grade toluene was prepared. The PMMA polymer was stirred at 50°C until the PMMA was completely dissolved. [PMMA] CAS: 9011-14-7; [Toluene] CAS: 108-88-3.

[0293] In a 20 mL vial, 2 mg of chromophore was added to the PMMA solution to give a 2.0 × 10 -3 A solution of M was prepared [the volume of PMMA is calculated by the following formula:

number

[0294] A 1 inch × 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.

[0295] The fluorescence spectra (emission spectra) of the 1" x 1" film samples prepared as described above were measured using a Fluorologmax spectrofluorometer (Horiba Scientific, Edison, NJ, USA). Both 390 nm and 450 nm wavelengths were selected as excitation wavelengths.

[0296] The quantum yield of the above spin-coated samples was measured using a Hamamatsu C11347 Absolute PL quantum yield spectrophotometer (Hamamatsu Inc., Campbell, CA, USA). For QY measurements, films measuring 0.5 inches × 0.5 inches were cut from the glass substrate. The wavelength was scanned from 390 nm to 450 nm (as the excitation wavelength) in 30 nm increments. The QY at 450 nm is reported in Table 1.

[0297] The optical properties (absorption peak wavelength, emission peak wavelength, FWHM, and quantum yield) of the spin-coated film are shown in Table 1 below.

[0298] Table 1. Optical properties of chromophores in PMMA [Table 1] [Table 2] Table 3 Table 4 Table 5 Table 6 Table 7 Table 8 Table 9 Table 10 Table 11 Table 12 Table 13 Table 14 Table 15

[0299] Example 3: Optical stability The photostability of the chromophore was measured using a 1" x 1" sample at 40mW / cm 2 The samples were tested by exposing them to a blue LED (CREE, Durham, NC, USA). The samples were monitored daily (the first 2-3 days) and then weekly for absorption, emission, and QY following the same procedures described above. The photodurability of the chromophore is quantified by the decrease in absorption (Abs%). The QY%, change in emission characteristics, was also monitored. The photostability measurements continued until the absorption decreased below 50%. The photostability data for PLC-1 compared to CE-3 are provided in Figure 1. This graph shows that the photostability of PLC-1 of the present invention is improved compared to CE-3.

Claims

1. A photoluminescent complex comprising: a blue light absorbing portion; a linker complex; a boron-dipyrromethene (BODIPY) moiety; and Including, The blue light absorbing moiety has the general formula: 【Chemistry 1】 (In the formula, each R ０ are independently H, alkyl, or —CF ３ , alkoxy, or optionally substituted aryl; R １０ is H, alkyl, -CF ３ , alkoxy, or optionally substituted aryl; the dashed line is the covalent bond to the linker conjugate), The BODIPY moiety has the general formula: 【Chemistry 2】 wherein X is F or CN; R １ and R ６ are independently H or alkyl; R ３ and R ４ are independently H or alkyl; R ２ and R ５ are independently H, alkyl, cycloalkyl, —CN, an alkyl ester group, or an aryl ester group; R ７ and R ８ are independently optionally substituted aryl, C １～８ Alkyl, C ３～８ Cycloalkyl, C １～１０ an ether group having an alkyl group, an ether moiety having an optionally substituted aryl group, or C １～１０ arylalkyl group), the linker conjugate comprises an optionally substituted ester or an optionally substituted ether linker; a linker conjugate covalently linking 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, and the BODIPY moiety absorbs the energy from the blue light absorbing moiety and emits light energy at a second, longer wavelength, and wherein the photoluminescent complex has an emission quantum yield of greater than 80%.

2. R ７ and R ８ But -CH ２ CH (CH ２ CH ３ ) (CH ２ ) ３ CH ３ , cyclopropyl, cyclohexyl, n-pentyl, -CH ２ -cyclohexyl, -OCH ２ -cyclohexyl, -O(CH ２ ) ３ Ph, -OCH ２ CH (CH ２ CH ３ ) CH ２ CH ２ CH ２ CH ３ , phenyl, —OCH ３ , —O-phenyl, 【Transformation 3】 2. The photoluminescent complex of claim 1, wherein

3. R ７ and R ８ are independently an optionally substituted alkyl, an optionally substituted cycloalkyl, or an optionally substituted ether group, including pentyl, 2-ethylhexyl, cyclohexyl, CH ２ -cyclohexyl, -OCH ３ , —O-(2-ethylhexyl), —OCH ２ -cyclohexyl, -OPh or -O(CH ２ ) ３ The photoluminescent complex of claim 1, further comprising -Ph.

4. R １ and R ６ are independently H, methyl, ethyl, propyl, isopropyl, butyl, or isobutyl; R ３ and R ４ 10. The photoluminescent complex of claim 1, wherein is independently H, methyl, ethyl, propyl, isopropyl, butyl, or isobutyl.

5. R ２ and R ５ is -C(O)OMe, 【Chemistry 4】 2. The photoluminescent complex of claim 1, comprising:

6. R ０ but, 【Transformation 5】 and R １０ The photoluminescent complex of claim 1 , wherein comprises H.

7. the linker complex 【Transformation 6】 2. The photoluminescent complex of claim 1, comprising:

8. 2. The photoluminescent complex of claim 1, wherein X is F.

9. 2. The photoluminescent complex of claim 1, wherein X is CN.

10. The photoluminescent complex has the following structure: 【Transformation 7】 【Transformation 8】 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】 【Chemistry 14】 【Chemistry 15】 【Chemistry 16】 【Chemistry 17】 [Chemistry 18] 【Chemistry 19】 【Chemistry 20】 【Chemistry 21】 【Chemistry 22】 【Chemistry 23】 【Chemistry 24】 2. The photoluminescent complex of claim 1, comprising one of:

11. A color conversion film, A transparent substrate layer; a color conversion layer including a resin matrix; a photoluminescent complex, the photoluminescent complex comprising the photoluminescent complex of claim 1 dispersed within 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 free radical scavenger.

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

15. 12. 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 producing the color conversion film of claim 11, comprising: Dissolving the photoluminescent complex according to claim 1 and a binder resin in a solvent; applying the mixture to a surface of the transparent substrate; A method comprising:

17. A backlight unit comprising the color conversion film according to claim 11.

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

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