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

Abstract

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

Description

Technical Field

[0001] The present disclosure relates to a photoluminescent compound for use in a color conversion film, a backlight unit, and a display device including the color conversion film and the backlight unit. Background Art

[0002] In color reproduction, a gamut (or color gamut) is a specific complete subset of the colors available on a device such as a television or monitor. TM Red, Green, and Blue (RGB) to provide a wider color gamut and provide a truer representation of the visible colors viewed through a display, the Adobe TM RGB is a color space with a wide color gamut achieved by using pure spectral primary colors. It is believed that devices that can provide a wider color gamut may enable displays to depict more vivid colors.

[0003] As high-definition large-screen displays become increasingly popular, the demand for higher performance, thinner and more powerful displays is also growing. Current light-emitting diodes (LEDs) are obtained by exciting green phosphors, red phosphors or yellow phosphors by a blue light source to obtain a white light source. However, the full width half maximum (FWHM) of the emission peaks of current green phosphors and red phosphors is very large, usually greater than 40nm, resulting in overlapping of the green spectrum and the red spectrum and making it impossible to fully distinguish each color from each other. This overlap can lead to poor color performance and color gamut degradation.

[0004] To correct for color gamut degradation, methods have been developed that use a combination of films containing quantum dots and LEDs. However, there are problems with the use of quantum dots. First, cadmium-based quantum dots are extremely toxic and are banned in many countries due to health safety issues. Second, non-cadmium-based quantum dots are very inefficient in converting blue LED light into green and red light. Third, quantum dots require expensive packaging processes to protect against moisture and oxygen. Finally, the cost of using quantum dots is high because size uniformity is difficult to control during the production process. Summary of the invention

[0005] The photoluminescent compounds described herein can be used to improve the contrast between distinguishable colors in televisions, computer monitors, smart devices, and many other devices that utilize color displays. The photoluminescent composites disclosed herein provide novel color conversion composites having good blue light absorbance and narrow emission bandwidth, wherein the full width at half maximum [FWHM] of the emission band is less than 40 nm. In some embodiments, the photoluminescent composite absorbs light of a first wavelength and emits light of a second wavelength higher than the first wavelength. The photoluminescent composites disclosed herein can be used with color conversion films for use in light emitting devices. The color conversion films disclosed herein reduce color degradation by reducing overlap within the color spectrum, resulting in high quality color performance.

[0006] Some embodiments include a photoluminescent complex, wherein the photoluminescent complex may include: a blue light absorbing moiety; a linker moiety; and a boron dipyrromethene (BODIPY) moiety. In some embodiments, the blue light absorbing moiety may include an optionally substituted perylene. In some embodiments, the linker moiety may covalently link the optionally substituted perylene to the BODIPY moiety. In some embodiments, the optionally substituted perylene absorbs light at a first excitation wavelength and transfers energy to the BODIPY moiety. In some embodiments, the BODIPY moiety absorbs energy from the optionally substituted perylene and emits light energy at a second, higher wavelength. In some embodiments, the emission quantum yield of the photoluminescent complex is greater than 80%.

[0007] In some embodiments, the photoluminescent composite can have an emission band having a full width at half maximum [FWHM] of at most 40 nm.

[0008] In some embodiments, the photoluminescent composite can have a difference between the excitation peak of the blue light absorbing moiety and the emission peak of the BODIPY moiety that is equal to or greater than 45 nm.

[0009] In some embodiments, the molar ratio between the blue light absorbing moiety and the BODIPY moiety can be 1: 1, 2: 1, 3: 1, or 1: 2. In some embodiments, the photoluminescent composite can be described by Formula 1a:

[0010] ZLE [Formula 1a].

[0011] In other embodiments, the photoluminescent composite can be described by Formula 1b:

[0012] ZLELZ [Formula 1b].

[0013] In other embodiments, the photoluminescent composite can be described by Formula 1c:

[0014] ELZLE [Formula 1c];

[0015] In other embodiments, the photoluminescent composite can be described by Formula 1d:

[0016]

[0017] Wherein Z represents a blue light absorbing moiety, L represents a linker, and E represents a BODIPY moiety. In some embodiments, the blue light absorbing moiety, the linker moiety, and the BODIPY moiety can be selected from the specific structures described herein. In some embodiments, the boron dipyrromethene (BODIPY) derivative can be substituted or unsubstituted. In some embodiments, the ratio between the blue light absorbing moiety and the BODIPY moiety can be 1:1, 2:1, 3:1, or 1:2.

[0018] Some embodiments include a color conversion film, wherein the color conversion film may include: a color conversion layer, wherein the color conversion layer includes a resin matrix and at least one photoluminescent composite described herein dispersed in the resin matrix. In some embodiments, the thickness of the color conversion film may be between about 1 μm and about 200 μm. In some embodiments, the color conversion film of the present disclosure may absorb blue light in a wavelength range of about 400 nm to about 480 nm and emit light in a wavelength range of about 510 nm to about 560 nm. Another embodiment includes a color conversion film that absorbs blue light in a wavelength range of about 400 nm to about 480 nm and emits light in a wavelength range of about 575 nm to about 645 nm. In some embodiments, the color conversion film may also include a transparent substrate layer. In some embodiments, the transparent substrate layer includes two opposing surfaces, wherein the color conversion layer is disposed on one of the opposing surfaces.

[0019] Some embodiments include a method of preparing the color conversion film, wherein the method includes: dissolving at least one photoluminescent composite described herein and a binder resin in a solvent; and applying the mixture on one of opposite surfaces of a transparent substrate.

[0020] Some embodiments include a backlight unit including the color conversion film described herein.

[0021] Some embodiments include a display device including the backlight unit described herein.

[0022] The present application provides a photoluminescent composite having excellent color gamut and luminescent properties, a method of manufacturing a color conversion film using the photoluminescent composite, and a backlight unit including the color conversion film. These and other embodiments are described in more detail below. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 is a graph depicting the absorption and emission spectra of one embodiment of a photoluminescent composite.

[0024] Figure 2 is a graph depicting the absorption and emission spectra of one embodiment of a photoluminescent composite.

[0025] Figure 3 is a graph depicting the absorption and emission spectra of one embodiment of a photoluminescent composite.

[0026] Figure 4 is a graph depicting the absorption and emission spectra of one embodiment of a photoluminescent composite. DETAILED DESCRIPTION

[0027] A novel approach to solving the problems presented when using quantum dots involves using boron dipyrromethene (BODIPY) compounds as luminescent materials instead of quantum dots. BODIPY is selected due to its narrow FWHM, high fluorescence efficiency, stability to moisture and oxygen, and low production cost. However, BODIPY materials may have some defects, such as very low absorption of blue LED light, such as 450nm, resulting in inefficient conversion of blue LED light to green and red light. Another drawback of current BODIPY compounds is that the FWHM tends to be wide when used in color conversion films.

[0028] The present disclosure describes a photoluminescent composite and the use of the composite in a color conversion film. The photoluminescent composite can be used to improve and enhance the transmission of one or more desired emission bandwidths in a color conversion film. In some embodiments, the photoluminescent composite can enhance the transmission of a desired first emission bandwidth and reduce the transmission of a second emission bandwidth. For example, the color conversion film can enhance the contrast or intensity between two or more colors, thereby increasing the distinction between them. The present disclosure includes a photoluminescent composite that can enhance the contrast or intensity between two colors, thereby increasing their distinction from each other.

[0029] As used herein, when a compound or chemical structure is referred to as optionally substituted, the compound or chemical structure may be unsubstituted or may be substituted, meaning that the compound or chemical structure may include one or more substituents. A substituted group is related to an unsubstituted parent structure in that one or more hydrogen atoms on the parent structure have been independently replaced by one or more substituents. A substituent may have one or more substituents on the parent group structure. In one or more forms, the substituents may independently be F, Cl, Br, I, C 0-7 H 1-15 O 1-2 N 0-2 , C0-7 H 1-15 O 0-2 N 1-2 , optionally substituted alkyl (including unsubstituted alkyl (e.g. methyl, ethyl, C3 alkyl, C4 alkyl, etc.), fluorinated alkyl (e.g. CF3, etc.)), alkenyl, or C3-C7 heteroalkyl.

[0030] As used herein, the term "alkyl" refers to an aliphatic hydrocarbon group that does not contain any C=C or C≡C moieties. The alkyl moiety may be branched, straight-chain or cyclic.

[0031] The alkyl moiety may have 1 to 6 carbon atoms. Where a numerical range is present herein, the numerical range (e.g., "1 to 6") refers to each integer within the given range. For example, "1 to 6 carbon atoms" refers to an alkyl group that may have 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc., up to and including 6 carbon atoms, but the definition also encompasses the appearance of the term "alkyl" without a specified numerical range. The alkyl group of the compound specified herein may be referred to as a "C1-C6 alkyl" or a similar name. For example only, "C1-C6 alkyl" means that there are one to six carbon atoms in the alkyl chain, i.e., the alkyl chain is selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. Therefore, C1-C6 alkyl includes C1-C2 alkyl, C1-C3 alkyl, C1-C4 alkyl, C1-C5 alkyl. Alkyl may be substituted or unsubstituted. Typical alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

[0032] An "olefin moiety" refers to a group having at least one carbon-carbon double bond (-C=C-), such as propenyl or butenyl, while an "alkyne" moiety refers to a group having at least one carbon-carbon triple bond (-C≡C-).

[0033] As used herein, the term "heteroalkyl" refers to an alkyl group as defined herein in which one or more of the constituent carbon atoms have been replaced by nitrogen, oxygen, sulfur, or halogen (e.g., F). Examples include, but are not limited to, -CH2-O-CH3, -CH2-CH2-O-CH3, -CH2-NH-CH3, -CH2-N(CH3)-CH3, -CH2-CH2-NH-CH3, -CH2-CH2-N(CH3)-CH3, -CH2-S-CH2-CH3, -CH2-CH2-S(O)-CH3. In addition, up to two heteroatoms may be consecutive, such as, for example, -CH2-NH-O-CH3, etc.

[0034] The term "aromatic" refers to a planar ring with a delocalized π electron system containing 4n+2 π electrons, where n is an integer. The aromatic ring can be formed by five, six, seven, eight, nine or more atoms. Aromatic compounds can be optionally substituted. The term "aromatic" includes carbocyclic aromatic (e.g., phenyl) and heterocyclic aromatic (or "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 group that contains only carbon and hydrogen atoms and may be saturated. Monocyclic hydrocarbon rings include groups having 3 to 12 carbon atoms. Illustrative examples of monocyclic groups include the following:

[0036] Etc. Illustrative examples of polycyclic groups include the following moieties:

[0037] [Bicyclooctane], [Dicyclopentane] [Bicycloheptane], [Bicycloheptane], [Bicyclodecane], [Decalin], [octahydrocyclopentadiene], [Octahedralin], [Hexahydroindene], [1,2,3,4-Tetrahydronaphthalene], [2,3-Dihydro-1H-indene] [1,2,3,3a-Tetrahydropentadiene], etc.

[0038] The term "aryl" as used herein refers to an aromatic ring in which each atom forming the ring is a carbon atom. The aromatic ring can be formed by five, six, seven, eight or more carbon atoms. The aryl group can be substituted or unsubstituted. Examples of aryl groups include, but are not limited to, phenyl, naphthyl, phenanthrenyl, etc.

[0039] The term "heteroaryl" refers to an aryl group including one or more ring heteroatoms (e.g., nitrogen, oxygen, and sulfur), wherein the heteroaryl group has 4 to 10 atoms in its ring system, provided that the ring of the group does not contain two adjacent nitrogen, oxygen, or sulfur atoms. It should be understood that the heteroaryl ring may have additional heteroatoms in the ring. In heteroaryl groups having two or more heteroatoms, the two or more heteroatoms may be the same or different from each other. The heteroaryl group may be optionally substituted. The N-containing heteroaryl moiety refers to an aryl group in which at least one skeletal atom of the ring is a nitrogen atom. Illustrative examples of heteroaryl groups include the following: pyrrole, imidazole, etc.

[0040] The term "halogen" as used herein refers to fluorine, chlorine, bromine and iodine.

[0041] As used herein, the terms "bond," "bonded," "direct bond," or "single bond" refer to a chemical bond between two atoms or to two moieties when the atoms connected by the bond are considered part of a larger structure.

[0042] As used herein, the term "moiety" refers to a specific segment or functional group of a molecule.

[0043] As used herein, the term "cyano" or "nitrile" refers to any organic compound containing a -CN functional group.

[0044] The term "ester" refers to a chemical moiety having the formula -COOR, where R is selected from alkyl, cycloalkyl, aryl, heteroaryl (bonded through a ring carbon), and heterocycle (bonded through a ring carbon). Any hydroxy or carboxyl side chain on the compounds described herein may be esterified. The procedures and specific groups for preparing such esters are known to those skilled in the art and can be readily found in reference sources.

[0045] As used herein, the term "ether" refers to a chemical moiety comprising an oxygen atom attached to: two alkyl groups: two aryl groups; or one alkyl group and one aryl group; wherein the general formula is RO-R', wherein the terms alkyl and aryl are as defined herein.

[0046] As used herein, the term "ketone" refers to a chemical moiety comprising a carbonyl group (carbon-oxygen double bond) attached to: two alkyl groups; two aryl groups; or one alkyl group and one aryl group; wherein the general formula is RC(=O)R', wherein the terms alkyl and aryl are as defined herein.

[0047] As used herein, the term "BODIPY" refers to a chemical moiety having the formula:

[0048]

[0049] BODIPY can be composed of a dipyrromethene group complexed with a disubstituted boron atom (usually a BF2 unit). The IUPAC name of the BODIPY core is 4,4-difluoro-4-bora-3a,4a-diaza-s-indazine.

[0050] In some embodiments, the optionally substituted perylene includes:

[0051]

[0052] The present disclosure relates to photoluminescent compounds that absorb light energy at a first wavelength and emit light energy at a second, higher wavelength. The photoluminescent compounds of the present disclosure comprise an absorbing luminescent moiety and an emitting luminescent moiety connected by a linker such that their distance is optimized for the absorbing luminescent moiety to transfer its energy to an acceptor luminescent moiety, wherein the acceptor luminescent moiety then emits energy at a second wavelength greater than the absorbed first wavelength. In some embodiments, the photoluminescent compound can be described by Formula 1a:

[0053] ZLE [Formula 1a].

[0054] In other embodiments, the photoluminescent composite can be described by Formula 1b:

[0055] ZLELZ [Formula 1b].

[0056] In other embodiments, the photoluminescent composite can be described by Formula 1c:

[0057] ELZLE [Formula 1c].

[0058] In other embodiments, the photoluminescent composite can be described by Formula 1d:

[0059]

[0060] Wherein Z represents a blue light absorbing moiety, L represents a linker, and E represents an emitting moiety. In some embodiments, the perylene absorbing moiety, the linker, and the BODIPY emitting moiety are selected from the specific structures described herein. The photoluminescent composites described herein can be incorporated into color conversion films to greatly improve the distinguishability between colors in the red, green, and blue (RGB) color domain, resulting in increased contrast and higher color rendering quality.

[0061] Some photoluminescent complexes include: a blue light absorbing portion; a linker portion; and a boron dipyrromethene (BODIPY) portion. In some embodiments, the linker portion can covalently link the blue light absorbing portion to the BODIPY portion. In some embodiments, the blue light absorbing portion can be selected from optionally substituted perylenes. In some embodiments, the optionally substituted perylene that absorbs blue light is represented as Z in Formulas 1a-1d. In some embodiments, the luminescent BODIPY portion is represented as E in Formulas 1a-1d. In some embodiments, the blue light absorbing portion absorbs light of a first excitation wavelength and transfers energy to the BODIPY portion, which then emits light energy of a second wavelength, wherein the light energy of the second wavelength is higher than the first wavelength. It is believed that energy transfer from the excited blue light absorbing portion to the BODIPY portion occurs through Forster resonance energy transfer (FRET). This idea is due to the absorption / emission spectrum of the photoluminescent composite, in which there are two main absorption bands, one at the absorption band of the blue light absorbing moiety and one at the absorption band of BODIPY, and only one emission band located at the emission wavelength of the BODIPY moiety (see Figure 1 and Figure 2 ).

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

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

[0064] In some embodiments, the difference between the excitation peak of the blue light absorbing moiety of the photoluminescent composite and the emission peak of the BODIPY moiety is at least 45 nm. In some embodiments, the difference between the excitation peak of the blue light absorbing moiety of the photoluminescent composite and the emission peak of the BODIPY moiety may be from about 45 nm to about 50 nm, from about 50 nm to about 55 nm, from about 55 nm to about 60 nm, from about 60 nm to about 65 nm, from about 65 nm to about 70 nm, from about 70 nm to about 75 nm, from about 75 nm to about 80 nm, from about 80 nm to about 85 nm, from about 85 nm to about 90 nm, from about 90 nm to about 95 nm, from about 95 nm to about 100 nm, or greater than about 100 nm, or any number bounded by this range.

[0065] The photoluminescent composites disclosed herein can have tunable emission wavelengths. By modifying the substituents of the BODIPY moiety, the emission wavelength can be tuned between 510 nm and about 560 nm, between about 610 nm and about 645 nm, or to any number within the range defined by any of these values.

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

[0067] In some embodiments, the photoluminescent composite may have an emission peak between 510 nm and 560 nm. In some embodiments, the emission peak may be between about 510 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 number within a range defined by any of these values.

[0068] In another embodiment, the photoluminescent composite may have an emission peak between 610 nm and 645 nm. In some embodiments, the emission peak may be between 610 nm and about 615 nm, about 615 nm and about 620 nm, about 620 nm and about 625 nm, about 625 nm and about 630 nm, about 630 nm and about 635 nm, about 635 nm and about 640 nm, about 640 nm and about 645 nm, or any number within a range defined by any of these values.

[0069] Other embodiments include photoluminescent composites wherein the spatial distance between the blue light absorbing moiety and the BODIPY derivative luminescent moiety is optimized by a linker moiety for transferring the energy of the blue light absorbing moiety to be transferred to the BODIPY derivative luminescent moiety.

[0070] The photoluminescent composite of the present disclosure may include a BODIPY moiety. The BODIPY moiety may have the following chemical formula 2:

[0071]

[0072] Where R 1 and R 6 independently H or C 1-6 H 3-13 O 0-2 (For example, C 1-6 Alkyl, including methyl, C2 alkyl, C3 alkyl, C4 alkyl, etc.; or ester, such as alkenoic acid alkyl ester, such as -CH=CHCO2CH2CH3); R 3 and R 4 are independently H, or C1-C5 alkyl; R 2 and R 5 R is selected from H, C1-C5 alkyl, cyano, arylalkynyl, aryl ester, alkyl ester or carboxylate groups attached to the linker moiety; 2 and R 3 can be linked together to form additional monocyclic hydrocarbon ring structures or polycyclic hydrocarbon ring structures; R4 and R 5 can be linked together to form additional monocyclic hydrocarbon ring structures or polycyclic hydrocarbon ring structures; R 7 X1 and X2 are independently selected from halogen groups.

[0073] In some embodiments, R 1 and R 6 Can be H.

[0074] In some embodiments, R 1 and R 6 It can be a C1-C4 branched or straight chain alkyl. 1 and R 6 In some embodiments, R 1 and R 6 It may be ethyl.

[0075] In some embodiments, R 1 and R 6 In some embodiments, the alkenyl ester may be vinyl crotonate.

[0076] In some embodiments, R 2 and R 5 Can be H.

[0077] In some embodiments, R 2 and R 5 It may be a nitrile group.

[0078] In some embodiments, R 2 and R 5 In some embodiments, the arylalkynyl group may be 1-propynylbenzene.

[0079] In some embodiments, R 2 and R 5 In some embodiments, the aryl ester may be a benzyl ester.

[0080] In some embodiments, R 2 and R 5 In some embodiments, the alkyl ester may be an ethyl ester.

[0081] In some embodiments, R 2 and R 3 can be linked together to form additional monocyclic hydrocarbon ring structures or polycyclic hydrocarbon ring structures. 2 and R 3 When linked together to form a monocyclic hydrocarbon ring structure, the structure may be selected from the following: [Cyclobutane] [Cyclopentane] [Cyclohexane] [Cycloheptane] [Cyclooctane] [Hexene ring], [Cyclohexa-1,4-diene] [Cyclopentene] [cyclohexa-1,3-diene], or [Cyclododecane]. In some embodiments, in R 2 and R 3 When linked together to form a polycyclic hydrocarbon ring structure, the structure may be selected from the following: [Bicyclooctane], [Dicyclopentane] [Bicycloheptane], [Bicyclo[4.1.0]heptane], [1s,5s bicyclo[3.3.1]nonane], [Decalin], [octahydrocyclopentadiene], [Octahedralin], [Hexahydroindene], [1,2,3,4-Tetrahydronaphthalene], [2,3-dihydro-1H-indene], or [1,2,3,3a-Tetrahydropentalene].

[0082] In some embodiments, R 4 and R 5 can be linked together to form additional monocyclic hydrocarbon ring structures or polycyclic hydrocarbon ring structures. 4 and R 5 When linked together to form a monocyclic hydrocarbon ring structure, the structure may be selected from the following: [Cyclobutane] [Cyclopentane] [Cyclohexane] [Cycloheptane] [Cyclooctane] [Hexene ring], [Cyclohexa-1,4-diene] [Cyclopentene] [cyclohexa-1,3-diene], or [Cyclododecane]. In some embodiments, in R 4 and R 5 When linked together to form a polycyclic hydrocarbon ring structure, the structure may be selected from the following: [Bicyclooctane], [Dicyclopentane] [Bicycloheptane], [Bicyclo[4.1.0]heptane], [1s,5s bicyclo[3.3.1]nonane], [Decalin], [octahydrocyclopentadiene], [Octahedralin], [Hexahydroindene], [1,2,3,4-Tetrahydronaphthalene], [2,3-dihydro-1H-indene], or [1,2,3,3a-Tetrahydropentalene].

[0083] In some embodiments, R 7 is selected from a direct bond to the linker moiety or an aryl group. When the aryl group is substituted, the substituents may be selected from: methyl, dimethyl, trimethyl, fluoro, difluoro, trifluoro, chloro, dichloro, trichloro, methoxy, dimethoxy, or trimethoxy. It is believed that by 7 By incorporating any of the above substituents on the phenyl group, the BODPIY structure becomes more rigid to prevent flexibility within the structure, thereby resulting in a higher quantum yield. In some embodiments, the aryl group is selected from phenyl or biphenyl. In some embodiments, R 7 is a phenyl group or a biphenyl group selected from the following structures:

[0084]

[0085] In some embodiments, R 7 is a phenyl group or a biphenyl group located between BODIPY and the linker moiety, wherein the phenyl group or the biphenyl group is selected from the following structures:

[0086] In some embodiments, the distance separating the blue light absorbing portion from the BODIPY portion may be about The linker moiety can maintain the distance between the blue light absorbing moiety and the BODIPY moiety.

[0087] In some embodiments, the photoluminescent complex comprises a linker moiety, also referred to herein as L, wherein the linker moiety covalently links the blue light absorbing moiety (optionally substituted perylene) to the BODIPY moiety. In some embodiments, the linker moiety may comprise a single bond between the optionally substituted perylene and the BODIPY moiety. In some embodiments, the linker moiety may comprise an optionally substituted C2-C7 ester group. When the linker group comprises an optionally substituted C2-C7 ester group, the linker moiety (L) may be selected from one of the following:

[0088] In other embodiments, the linker moiety (L) may comprise an unsubstituted C2-C6 ether group. When the linker moiety comprises an unsubstituted C2-C6 ether group, the linker moiety may be selected from one of the following:

[0089] In some embodiments, R 2 and R 5 In some embodiments, R 2 and R 5 Can be a carboxylate group bonded to a linker moiety. 2 and R 5 Can In some embodiments, R 2 and R 5 Can wherein Ph is phenyl. In some embodiments, R 2 and R 5 Can be a carboxylate group bonded to a linker moiety In some embodiments, when R 2 and R 5 When it is a carboxylate group, 2 and / or R 5 The bonded linker moiety may be

[0090] In some embodiments, the photoluminescent composite comprises a blue light absorbing portion. The blue light absorbing portion may comprise an organic luminophore. In some embodiments, the absorbing luminescent portion may have a maximum absorbance for light at any wavelength within the range of 400 nm to about 480 nm, about 400 nm to about 410 nm, about 410 nm to about 420 nm, about 420 nm to about 430 nm, about 430 nm to about 440 nm, about 440 nm to about 450 nm, about 450 nm to about 460 nm, about 460 nm to about 470 nm, about 470 nm to about 480 nm, or within the range defined by any of these values. In some embodiments, the photoluminescent composite may have a maximum absorption peak of about 450 nm. In other embodiments, the blue light absorbing portion may have a maximum absorption peak of about 405 nm. In other embodiments, the blue light absorbing portion may have a maximum absorption peak of about 480 nm.

[0091] In some embodiments, the blue light absorbing moiety can be an optionally substituted perylene as shown in Formula 3:

[0092]

[0093] In some embodiments, R 8 , R 9 , R 11 and R 12 It can be selected from H, a bond to L3, a straight-chain C1-C6 alkyl group, a branched C3-C6 alkyl group, a cyano group (-CN), a trifluoromethyl group (-CF3) or a 4-(trifluoromethyl)phenyl group. 9 When it is H, CN or CF3, then R 10 is H. When R 9 When it is 4-(trifluoromethyl)phenyl, then R 10 It can be H or a direct bond to the 4-(trifluoromethyl)phenyl group to form a bridged substituted aromatic group, wherein the substituted bridged aromatic group forms (trifluoromethyl)indeno[1,2,3-cd]perylene.

[0094] In some embodiments, R 8 , R 9 , R 11 and R 12 Can be independently a bulky group, such as a bulky alkyl group, such as a bulky C 3-6 It is believed that by utilizing one or more bulky groups in the substituents attached to the perylene, π-π double bonds can be prevented from stacking within other photoluminescent composites and with other photoluminescent composites when mixed in a mixture. It is believed that by preventing π-π double bond stacking, the photoluminescent composite maintains the distance between the blue light absorbing moiety and the BODIPY moiety, thereby preventing any detrimental optical effects caused by π-π double bond stacking. Bulky groups (e.g., bulky C 3-6 Some non-limiting examples of alkyl) include, but are not limited to, the following structures shown below:

[0095] or

[0096] In other embodiments, R 8 , R 9 , R 11 and R 12 may be independently cyano (-CN), trifluoromethyl (-CF3) or 4-(trifluoromethyl)phenyl. 8 , R 9 , R 11 and R 12The addition of a cyano group, a trifluoromethyl group or a 4-(trifluoromethyl)phenyl group at any of the positions helps to increase the photostability of the photoluminescent complex. The photostability (or durability) of organic compounds and complexes is a very common problem. The poor photostability of organic photoluminescent complexes is mainly due to the photooxidation process. It is believed that the addition of electron withdrawing groups (also called electron accepting groups) to the reactive sites on the perylene structure attracts electrons from the atomic groups on the photoluminescent complex through an inductive effect or a resonance effect, thereby resulting in a lower HOMO / LUMO energy level, which is unfavorable for the photooxidation of the photoluminescent complex.

[0097] Although any suitable electron withdrawing group can be used, cyano (-CN), fluorinated alkyl groups (e.g., trifluoromethyl (-CF3)), or fluorinated aryl groups (e.g., 4-(trifluoromethyl)phenyl) may provide improved stability compared to other types of electron withdrawing groups.

[0098] Those skilled in the art will also recognize that the perylene can be substituted at any position during the reaction process. Although the structural formulas provided herein depict one of many possible positional isomers, it should be understood that these structures are merely illustrative and the present disclosure is not limited to any particular isomer, and any and all possible positional isomers of substituted perylenes are intended to fall within the scope of the present disclosure.

[0099] In some embodiments, the optionally substituted perylene may be attached to a second boron dipyrromethene (BODIPY) moiety. In some embodiments, the linker moiety and the second absorbing BODIPY moiety may be covalently attached. In other embodiments, the BODIPY moiety may be covalently attached to two or more blue light absorbing moieties. In some embodiments, the ratio between the blue light absorbing moiety and the BODIPY moiety may be 1:1. In another embodiment, the ratio between the blue light absorbing moiety and the BODIPY moiety may be 2:1. In another embodiment, the ratio between the blue light absorbing moiety and the BODIPY moiety may be 3:1. In yet another embodiment, the ratio between the blue light absorbing moiety and the BODIPY moiety may be 1:2.

[0100] In some embodiments, the photoluminescent complex is represented by Formula A or B:

[0101]

[0102]

[0103] With respect to formula A or B, R as described herein with respect to any other formula 1 , R 3 , R 4 , R 8The descriptions of X1 and X2 also apply to Formula A.

[0104] About formula A or B, G 2 is H, C1-C5 alkyl, CN, arylalkynyl, aryl ester, alkyl ester, or -C(=O)O-(CH2)4-OC(=O)-(CH2)3-Z 1 In addition, G 2 This article may be aimed at R 2 or Z 1 -L1-R 2 - any one of the groups described above.

[0105] About formula A or B, G 5 is H, C1-C5 alkyl, CN, arylalkynyl, aryl ester, alkyl ester, or -C(=O)O-(CH2)4-OC(=O)-(CH2)3-Z 2 In addition, G 5 This article may be aimed at R 5 or -R 5 -L2-Z 2 Any of the groups described above.

[0106] About formula A or B, G 7 is an optionally substituted aryl group, -L3-Z 3 、-Ar-L3-Z 3 、-L3-Z 3 -L3-, or -Ar-L3-Z 3 -L3-Ar-, wherein Ar is an optionally substituted aryl group. 7 This article may be aimed at R 7 or -R 7 -L3-Z 3 Any of the groups described above.

[0107] With respect to Formula A, Formula B, or another formula or structural representation depicting L3, L3 is a single bond, or a linker moiety comprising a -C(=O)O- or -O- group. Additionally, L3 can be any of the groups described herein for L3 depicted in any other formula or other structural representation.

[0108] With respect to Formula A, Formula B, or another formula or structural representation depicting X1 and X2, X1 and X2 are independently F, Cl, Br, or I. Additionally, X1 or X2 can be any of the groups described herein for X1 or X2 depicted in any other formula or other structural representation.

[0109] About formula A, formula B or description Z 1 , Z 2 and Z 3 Another formula or structure representation of Z1 , Z 2 and Z 3 Independently for:

[0110] Where R 8 , R 9 , R 11 and R 12 is independently H, a bond to L1, L2 or L3, a branched C4-C5 alkyl, CN, CF3 or 4-(trifluoromethyl)phenyl; wherein: R 9 When R is H, branched C4-C5 alkyl, CN, F or CF3, 10 is H; when R 9 When it is 4-(trifluoromethyl)phenyl, R 10 is H or forms a direct bond to 4-(trifluoromethyl)phenyl, thereby forming (trifluoromethyl)indeno[1,2,3-cd]perylene. 1 , Z 2 or Z 3 may be any Z depicted herein in any other formula or other structural representation. 1 , Z 2 or Z 3 Any of the groups described above.

[0111] In one embodiment of the present specification, the complex represented by Formula 1a ZLE [Formula 1a] can be represented by Chemical Formula 4: [Formula 4],

[0112] In formula 4, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 The definitions of X1, X2 are the same as those described in Chemical Formula 2. L3 represents the same as described above for R in this article 7 The linker moiety. 3 represents the blue light absorbing part represented by Chemical Formula 3, and Z 3 The definitions / parameters of are the same as those of Chemical Formula 3 described herein above.

[0113] In one embodiment of the present specification, the complex represented by Formula 1a, ZLE may be represented by Chemical Formula 5:

[0114]

[0115] In Formula 5, R 1, R 2 , R 3 , R 4 , R 6 , R 7 The definitions of X1, X2 are the same as those described in Formula 2. 5 is a carboxylate group covalently bonded to L2. L2 represents the same as described above for R 5 The linker moiety. 2 represents the blue light absorbing part represented by Formula 3, and Z 2 The definitions / parameters of are the same as those of Formula 3 described above herein.

[0116] In another embodiment of the present specification, the complex represented by Formula 1bZ-LELZ [Formula 1b] may be represented by Chemical Formula 6:

[0117] In formula 6, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 The definitions of R7 and X1 are the same as those described in Formula 2. 2 is a carboxylate group covalently bonded to L1. 5 is a carboxylate group covalently bonded to L2. L1 and L2 each represent a linker moiety and are the same as those described above for R 2 and R 5 The linking base parts are the same. 1 and Z 2 represents the blue light absorbing part represented by Formula 3, and Z 1 and Z 2 The definitions / parameters of are the same as those of Formula 3 described herein above.

[0118] In one embodiment of the present specification, the complex represented by Formula 1d:

[0119] It can be expressed by formula 7:

[0120]

[0121] In formula 7, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7The definitions of X1, X2 are the same as those described in Formula 2. L3 represents the same as that described herein for R 7 The linker portion. 2 is a carboxylate group covalently bonded to L1. 5 is a carboxylate group covalently bonded to L2. L1 and L2 each represent a linker moiety and are the same as those described above for R 2 and R 5 The linking base parts are the same. 1 , Z 2 and Z 3 Each represents the blue light absorbing part of Formula 3, and Z 1 , Z 2 and Z 3 The definitions / parameters of are the same as those of Formula 3 described herein above.

[0122] The photoluminescent composites of Formulas 1a, 1b, 1c and 1d may be represented by the following examples, but the present disclosure is not limited to these examples:

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139] and / or

[0140] Some embodiments include a color conversion film, wherein the color conversion film includes: a color conversion layer, wherein the color conversion layer includes a resin matrix and a photoluminescent composite as described above dispersed in the resin matrix. In some embodiments, the color conversion film can be described as comprising one or more of the photoluminescent composites described herein.

[0141] Some embodiments include a color conversion film that can be about 1 μm to about 200 μm thick. In some embodiments, the color conversion film can have a thickness of about 1-5 μm, about 5-10 μm, about 10-15 μm, about 15-20 μm, about 20-40 μm, about 40-80 μm, about 80-120 μm, about 120-160 μm, about 160-200 μm, or about 1-2 μm, about 2-3 μm, about 3-4 μm, about 4-6 μm, about 5-7 μm, about 6-8 μm, about 7-9 μm, about 8-9 μm, about 9-10 μm, about 11-12 μm, about 13-14 μm, about 15-16 μm, about 17-18 μm, about 19-20 μm, about 21-23 μm, about 22-24 μm, about 25-26-27 μm, about 26-28 μm, about 27-29 μm, about 28-30 μm, about 29-30 μm, about 30-30 μm, about 31-31 μm, about 32-33 μm, about 33-34 μm, about 35-36 μm, about 37-38 μm, about 39-40 μm, about 38-39 μm, about 39-40 μm, about 39-50 μm, about 30-31 μm, about 31-32 μm, about 33-35 μm, about 35-36 μm, about 37-38 μm, about 39-40 μm, about 38-39 μm, about 39-40 μm, about 38 5μm, about 5-6μm, about 6-7μm, about 7-8μm, about 8-9μm, about 9-10μm, about 10-11μm, about 11-12μm, about 12-13μm, about 13-14μm, about 14-15μm, about 15-16μm, about 16-17μm, about 17-18μm, about 18-19μm, about 19-20 170-180μm, about 180-190μm, about 190-200μm, or about 10μm, about 20μm, about 30μm, about 40μm thick, or any thickness within the range defined by any of these values.

[0142] In some embodiments, the color conversion film can absorb light having a wavelength of 400 nm to about 480 nm, and can emit light in the range of about 510 nm to about 560 nm and about 610 nm to about 645 nm. In other embodiments, the color conversion film can emit light in the range of 510 nm to about 560 nm, the range of 610 nm to about 645 nm, or any combination thereof.

[0143] In some embodiments, the color conversion film may further include a transparent substrate layer. The transparent substrate layer has two opposing surfaces, wherein the color conversion layer may be disposed on and in physical contact with the surface of the transparent layer that will be adjacent to the light source. There is no particular limitation on the transparent substrate, and a person skilled in the art will be able to select the 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 (ethylene glycol-modified polyethylene terephthalate), PDMS (polydimethylsiloxane), COC (cyclic olefin copolymer), PGA (polyglycolide or polyglycolic acid), PLA (polylactic acid), PCL (polycaprolactone), PEA (polyethylene adipate), PHA (polyhydroxyalkanoate), PHBV (poly (3-hydroxybutyrate-co-3-hydroxyvalerate)), PBE (polybutylene terephthalate), PTT (polytrimethylene terephthalate). Any of the above resins may be corresponding / corresponding monomers and / or polymers.

[0144] In some embodiments, the transparent substrate may have two opposing surfaces. In some embodiments, the color conversion film may be disposed on one of the opposing surfaces and in physical contact with the surface. In some embodiments, the side of the transparent substrate on which the color conversion film is not disposed may be adjacent to the light source. The substrate may be used as a support during the preparation of the color conversion film. There is no particular restriction on the type of substrate used, and there is no restriction on the material and / or thickness, as long as the substrate is transparent and can be used as a support. Those skilled in the art can determine which material and thickness to use as a supporting substrate.

[0145] Some embodiments include a method for preparing a color conversion film, wherein the method includes: dissolving the photoluminescent compound described herein and a binder resin in a solvent; and applying the mixture to a surface of a transparent substrate.

[0146] Binder resins that can be used with the photoluminescent composite include, for example, the following resins: acrylic resins, polycarbonate resins, ethylene-vinyl alcohol copolymer resins, ethylene-vinyl acetate copolymer resins and saponification products thereof, AS resins, polyester resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins, polyvinyl phosphonic acid (PVPA), polystyrene resins, phenolic resins, phenoxy resins, polysulfones, nylons, cellulose resins, and cellulose acetate resins. In some embodiments, the binder resin may be a polyester resin and / or an acrylic resin. In some embodiments, the term "resin" is equivalent to the term "polymer resin" or "polymer".

[0147] Solvents that can be used to dissolve or disperse the composite and resin may include alkanes such as butane, pentane, hexane, heptane, and octane; cycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane; alcohols such as ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, decanol, undecanol, diacetone alcohol, and furfuryl alcohol; Cellosolves TM , such as Methyl Cellosolve TM , Ethyl Cellosolve TM , Butyl Cellosolve TM , Methyl Cellosolve TM Acetate and Ethyl Cellosolve TM Acetates; propylene glycol and its derivatives, such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate and dipropylene glycol dimethyl ether; ketones, such as acetone, methyl amyl ketone, cyclohexanone, and acetophenone; ethers, such as dioxane and tetrahydrofuran; esters, such as butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate, ethyl 2-hydroxybutyrate, ethyl acetoacetate, methyl lactate, ethyl lactate and methyl 3-methoxypropionate; halogenated hydrocarbons, such as chloroform, dichloromethane and tetrachloroethane; aromatic hydrocarbons, such as benzene, toluene, xylene and cresol; and high polar solvents, such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone.

[0148] Some embodiments include a backlight unit, wherein the backlight unit may include the above-described color conversion film.

[0149] Other embodiments may include a display device, wherein the device may include a backlight unit described herein.

[0150] Unless otherwise stated, all numerals used in the specification and embodiments to represent the amount of components, properties (such as molecular weight), reaction conditions, etc. should be understood to be modified by the term "about" in all cases. Therefore, unless otherwise indicated, the numerical parameters listed in the specification and the attached embodiments are approximate values, which can be changed according to the desired properties sought to be obtained. In any case, it is not intended to limit the application of the principle of equivalents. For the scope of the embodiment, each numerical parameter should at least be interpreted according to the reported significant figures and by applying ordinary rounding techniques.

[0151] For the disclosed processes and / or methods, the functions performed in the processes and methods may be implemented in different orders, as indicated by the context. In addition, the steps and operations outlined are provided only as examples, and some of the steps and operations may be optional, combined into fewer steps and operations, or expanded into additional steps and operations.

[0152] The disclosure may sometimes illustrate different components contained within or connected to different other components. Such depicted architectures are merely examples, and many other architectures may be implemented that achieve the same or similar functionality.

[0153] The terms used in this disclosure and the accompanying embodiments (e.g., the main body of the accompanying embodiments) are generally intended to be "open" terms (e.g., the term "including" should be interpreted as "including but not limited to", the term "having" should be interpreted as "having at least", the term "comprising" should be interpreted as "including but not limited to", etc.). In addition, if a specific number of elements is introduced, this can be interpreted as including at least the recited number, as can be indicated by the context (e.g., the expression of "two recited items" without other modifiers means at least two of the two or more recited items). As used in this disclosure, transitional words and / or phrases presenting two or more optional items should be understood to consider the possibility of including one of these items, any one of these items, or all of these items. For example, the phrase "A or B": should be understood to include the possibility of "A or B" or "A and B".

[0154] Unless otherwise indicated herein or clearly contradictory to the context, the terms "a", "the" and similar indicators or the absence of quantifiers used in the context of describing the present disclosure (especially in the context of the following embodiments) should be interpreted as covering both the singular and the plural. The use of any and all examples, or related language (such as "for example") provided herein is intended only to better illustrate the present disclosure, rather than to limit the scope of any embodiment. No language in the specification should be interpreted as indicating that any unembodied element is essential to the practice of the present disclosure.

[0155] The grouping of alternative elements or embodiments disclosed herein should not be construed as limiting. Each group member may be referred to and embodied individually or in any combination with other members in the group or other elements found herein. It is contemplated that one or more members in the group may be included in the group or deleted from the group for convenience and / or patentability reasons. When any such inclusion or deletion occurs, this specification is deemed to include the modified group, thereby satisfying the written description of all Markush groups used in the attached embodiments.

[0156] Certain embodiments are described herein, including the best mode known to the inventors for implementing the present disclosure. Of course, variations of the embodiments described will become apparent to those of ordinary skill in the art after reading the foregoing description. The inventors hope that the skilled person will appropriately adopt such variations, and the inventors hope to practice the present disclosure in a manner different from that specifically described herein. Therefore, the embodiments include all modifications and equivalents of the subject matter described in the embodiments as permitted by applicable law. In addition, unless otherwise specified herein or clearly contradictory to the context, any combination of all possible variations of the above elements is contemplated. Finally, it should be understood that the embodiments disclosed herein are illustrations of the principles of the embodiments. Other modifications that may be adopted are within the scope of the embodiments. Therefore, by way of example and not limitation, alternative embodiments may be utilized according to the teachings herein. Therefore, the embodiments are not limited to the embodiments precisely as shown and described. DETAILED DESCRIPTION

[0158] Embodiment 1 A photoluminescent composite, comprising:

[0159] a blue light absorbing moiety, wherein the blue light absorbing moiety comprises an optionally substituted perylene;

[0160] a linker moiety; and

[0161] boron dipyrromethene (BODIPY) moiety;

[0162] wherein the linker moiety covalently links the optionally substituted perylene and the BODIPY moiety, wherein the optionally substituted perylene absorbs light energy at a first excitation wavelength and transfers the energy to the BODIPY moiety, wherein the BODIPY moiety absorbs the energy from the optionally substituted perylene and emits light energy at a second, higher wavelength, and wherein the photoluminescent complex has an emission quantum yield greater than 80%.

[0163] Embodiment 2 The photoluminescent composite according to embodiment 1, wherein the emission band has a full width at half maximum (FWHM) of at most 40 nm.

[0164] Embodiment 3 The photoluminescent composite according to embodiment 1, wherein the photoluminescent composite has a Stokes shift equal to or greater than 45 nm, the Stokes shift being the distance between the excitation peak of the blue light absorbing portion and the emission peak of the BODIPY portion.

[0165] Embodiment 4 The photoluminescent composite according to embodiment 1, wherein the composite has a maximum absorbance of about 400 nm to about 480 nm.

[0166] Embodiment 5 The photoluminescent composite according to embodiment 1, wherein the BODIPY portion has the following general formula:

[0167]

[0168] Where R 1 and R 6 are independently H, alkyl or alkenyl ester;

[0169] R 3 and R 4 are independently H or C1-C5 alkyl;

[0170] R 2 and R 5 are independently H, C1-C5 alkyl, cyano, arylalkynyl, and alkyl ester, alkyl ester forming part of the linker, or aryl ester;

[0171] R 2 and R 3 may be linked together to form additional monocyclic hydrocarbon ring structures or polycyclic hydrocarbon ring structures;

[0172] R 4 and R 5 may be linked together to form additional monocyclic hydrocarbon ring structures or polycyclic hydrocarbon ring structures;

[0173] R 7 is selected from a direct bond to the linker moiety, or an aryl group;

[0174] X1 and X2 are independently selected from halogen groups.

[0175] Embodiment 6 The photoluminescent composite according to embodiment 5, wherein R 7 Selected from:

[0176] Direct bond to the linker moiety,

[0177] Embodiment 7 The photoluminescent composite according to embodiment 1, wherein the linker moiety is selected from: a single bond, an ester group, or an ether group.

[0178] Embodiment 8 The photoluminescent composite according to embodiment 7, wherein the ester group is selected from:

[0179] Embodiment 9 The photoluminescent composite according to embodiment 7, wherein the ether group is:

[0180] Embodiment 10 The photoluminescent composite according to embodiment 1, wherein the optionally substituted perylene is represented by the following general formula:

[0181]

[0182] Where R 8 , R 9 , R 11 and R 12 can be selected from H, branched C4-C5 alkyl, cyano (CN), trifluoromethyl (CF3) or 4-(trifluoromethyl)phenyl, and when R 9 When R is H, branched C4-C5 alkyl, CN, F or CF3, 10 is H, but when R 9 When it is 4-(trifluoromethyl)phenyl, then R 10 is H or forms a direct bond to 4-(trifluoromethyl)phenyl, thereby forming a bridged substituted aromatic group, wherein the substituted bridged aromatic group forms (trifluoromethyl)indeno[1,2,3-cd]perylene.

[0183] Embodiment 11 The perylene according to embodiment 10, wherein the branched C4-C5 alkyl group is selected from one of the following: (tert-butyl), (sec-butyl), (isobutyl), (neopentyl), or (tert-amyl).

[0184] Embodiment 12 The photoluminescent composite according to embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 and 11, wherein the ratio between the blue light absorbing moiety and the BODIPY moiety is 1:1, 2:1, 3:1, or 1:2.

[0185] Embodiment 13 The photoluminescent composite according to embodiment 1, wherein the photoluminescent composite is represented by the following chemical formula [4]:

[0186]

[0187] In chemical formula 4,

[0188] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , X1, X2 and L are defined the same as those in Embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 and 11,

[0189] Z is selected from the group consisting of optionally substituted perylenes according to embodiments 10 and 11.

[0190] Embodiment 14: The photoluminescent composite according to embodiment 1, wherein the photoluminescent composite is represented by the following Chemical Formula 6:

[0191]

[0192] In Chemical Formula 6,

[0193] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , X1, X2 and L are the same as those in Embodiments 1, 2, 3, 4, 5, 6, 7, 8 and 9;

[0194] L1 and L2 are the same as or independent of each other and are selected from: a single bond, a substituted or unsubstituted ester group, or a substituted or unsubstituted ether group; and

[0195] Z 1 and Z 2 is selected from the optionally substituted perylenes according to embodiments 10 and 11.

[0196] Embodiment 15 The photoluminescent composite according to embodiment 1, wherein the photoluminescent composite is represented by the following general formula 7:

[0197]

[0198] In general formula 7,

[0199] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , X1, X2, L1, L2 and L3 are defined the same as those in Embodiments 1, 2, 3, 4, 5, 6, 7, 8 and 9; and

[0200] Z 1 , Z 2 and Z 3 is selected from the optionally substituted perylenes according to embodiments 10 and 11.

[0201] Embodiment 16 The photoluminescent composite according to embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 and 16, wherein the distance between the BODIPY moiety and the optionally substituted perylene is about or larger.

[0202] Embodiment 17 A color conversion film, the color conversion film comprising:

[0203] A color conversion layer, wherein the color conversion layer comprises a resin matrix; and the photoluminescent composite according to embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 and 15, the photoluminescent composite being dispersed in the resin matrix.

[0204] Embodiment 18 The color conversion film of embodiment 17, wherein the film has a thickness between 1 μm and about 200 μm.

[0205] Embodiment 19 The color conversion film of embodiment 17, wherein the film absorbs light in a wavelength range of about 400 nm to about 480 nm and emits light in a wavelength range of about 510 nm to about 560 nm.

[0206] Embodiment 20 The color conversion film according to embodiment 17, wherein the film absorbs light in a wavelength range of about 400 nm to about 480 nm and emits light in a wavelength range of about 575 nm to about 645 nm.

[0207] Embodiment 21: According to the color conversion film of Embodiment 17, the color conversion film further includes a transparent substrate layer, wherein the transparent substrate layer includes two opposite surfaces, and the color conversion layer is disposed on one of the opposite surfaces.

[0208] Embodiment 22 A method for preparing the color conversion film according to embodiments 17, 18, 19, 20 and 21, the method comprising:

[0209] dissolving the photoluminescent composite according to embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 and 15 and a binder resin in a solvent; and

[0210] The mixture is applied to one of the opposing surfaces of the transparent substrate.

[0211] Embodiment 23: A backlight unit comprising the color conversion film according to Embodiments 17, 18, 19, 20, and 21.

[0212] Embodiment 24: A display device comprising the backlight unit according to Embodiment 23.

[0213] Example

[0214] Embodiments of the photoluminescent composites described herein have been found to have improved performance compared to other forms of dyes used in color conversion films. These benefits are further demonstrated by the following examples, which are intended to illustrate the disclosure only and are not intended to limit the scope or underlying principles in any way.

[0215] Example 1.1 Comparative Example 1 (CE-1):

[0216]

[0217] CE-1: 0.75g of 4-hydroxy-2,6-dimethylbenzaldehyde (5mmol) and 1.04g of 2,4-dimethylpyrrole (11mmol) were dissolved in 100mL of anhydrous dichloromethane. The solution was degassed for 30 minutes. Then a drop of trifluoroacetic acid was added. The solution was stirred overnight at room temperature under an argon atmosphere. DDQ (2.0g) was added to the resulting solution, and the mixture was stirred overnight. The solution was filtered the next day and then washed with dichloromethane to obtain dipyrromethene (1.9g). Next, 1.0g of dipyrromethene was dissolved in 60mL of THF. 5mL of triethylamine was added to the solution, which was then degassed for 10 minutes. After degassing, 5mL of trifluoroboron-diethyl ether was slowly added and then heated at 70°C for 30 minutes. The resulting solution was loaded onto silica gel and purified by flash chromatography using dichloromethane as an eluent. The desired fractions were collected and dried under reduced pressure to give 0.9 g of an orange solid (76% yield). LCMS (APCI+): C 21 H 24 Calculated for BF2N2O (M+H) = 369; found: 369. 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).

[0218] Example 1.2: Comparative Example 2 (CE-2): Synthesized according to the description of Wakamiya, Atsushi et al., Chemistry Letters, 37(10), 1094-1095; 2008

[0219] Example 2: Synthesis of photoluminescent composites:

[0220] Example 2.1: PC-1

[0221]

[0222] Compound 1.1 was synthesized according to the following literature procedure: European Journal of Organic Chemistry (2008), (16), 2705-2713.

[0223] Compound 1.2 [3,10-dibromoperylene]: Perylene (4.00 g, 16.00 mmol) and N-bromosuccinimide (7.12 g, 40.0 mmol) were dissolved in a 1 L flask with 400 mL of dichloromethane and a magnetic stir bar. The solution was then stirred at room temperature for 24 h. The solution was evaporated to dryness under vacuum to give a solid. The solid was continuously extracted with chloroform for 8 h to remove any unreacted perylene. A yellow solid was obtained with a yield of 90% (5.9 g). In LCMS (APCI+): C 20 H 20 The calculated value of Br2 is: 407.9; the measured value is: 408.

[0224] Compound 1.3 [3,10-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)perylene)]: A mixture of compound 1.2 [3,10-dibromoperylene] (4.10 g, 10 mmol), bispinacolatodiboron (5.60 g, 22 mmol), potassium acetate (2.94 g, 30 mmol) and Pd(dppf)Cl2 (0.7 g, 1 mmol) was dried under vacuum and then dissolved in anhydrous 1,4-dioxane (100 mL). The mixture was degassed and then heated at 90°C under argon for 2 days. After the mixture was cooled to room temperature, it was loaded onto silica gel and purified by flash chromatography. The eluent used was dichloromethane / hexane (0-20%). 2.0 g (40% yield) of an orange solid, 3,10-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)perylene) was obtained.

[0225] PC-1: BODIPY compound 1.1 (500 mg, 1.1 mmol), 3,10-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)perylene), compound 1.3 (220 mg, 0.44 mmol), potassium carbonate (0.138 g, 1 mmol) and Pd(PPh3)4 (58 mg, 0.05 mmol) were mixed in a 250 mL flask with 25 mL 1,4-dioxane. The mixture was heated at 100 °C and degassed overnight. Next, the mixture was cooled to room temperature and filtered to give an orange solid. The orange solid was collected and further purified by flash chromatography using hexane / dichloromethane (1:0.2 to 1:1) as the eluent. After removal of the solvent, PC-1 was obtained as a reddish solid (190 mg, 43% yield). 1 H NMR (400MHz, chloroform-d) δ8.32(q,J=6.8Hz,2H),7.77(d,J=8.4Hz,1H),7.67(d,J=7.7Hz,2H),7.57- 7.48(m,2H),7.45(d,J=7.6Hz,2H),2.57(s,6H),2.36(q,J=7.5Hz,4H),1.03(t,J=7.5Hz,6H).

[0226] Example 2.2: PC-2

[0227]

[0228] Compound 2.1: 4-bromo-2,6-dimethylbenzaldehyde (1.06 g, 5 mmol) and 2,4-dimethylpyrrole (1.04 g, 11 mmol) were dissolved in anhydrous dichloromethane (100 mL). The solution was degassed for 30 min, and then a drop of trifluoroacetic acid was added. The resulting solution was stirred at room temperature overnight under argon. The resulting solution was cooled at 0 ° C in an ice bath. Once cooled, DDQ (1.5 g) was added (the solution immediately turned red). The solution was stirred overnight. The next day, the solution was purified by flash chromatography using hexane / ethyl acetate (8: 1) and 0.1% trimethylamine as eluent. The desired orange fractions were collected and dried under reduced pressure to give a yellow-orange solid (1.5 g, yield 78%). LCMS (APCI+): C 21 H 24 Calculated for BrN2 (M+H) = 383; found: 383.

[0229] Compound 2.2 [BODIPY]: 3.7 mL of trimethylamine was added to a solution of dipyrromethane, compound 2.1 (1.5 g, 3.9 mmol) in 50 mL of anhydrous toluene. The resulting solution was degassed for 10 min. Next, trifluoroborane-diethyl ether (5.3 mL) was slowly added with stirring. The resulting solution was stirred at 70°C for 30 min, then poured into ethyl acetate (200 mL) and washed with brine. The organic phase was collected, dried over Na2SO4, concentrated to 30 mL under reduced pressure, and then subjected to flash chromatography using dichloromethane / hexane (0%→70%) as eluent. The desired fractions were collected and dried under reduced pressure to give an orange solid (1.55 g, 92% yield). LCMS (APCI+): C 21 H 23 Calculated for BBrF2N2 (M+H) = 431; found: 431.

[0230] PC-2: Diboronate, compound 1.3 (116 mg, 0.23 mmol), BODIPY, compound 2.2 (200 mg, 0.46 mmol), Cs2CO3 (227 mg, 0.7 mmol) and Pd(PPh3)4 (14 mg, 0.012 mmol) were mixed together in 1,4-dioxane (10 mL). The solution was degassed and heated at 100°C for 4 h. The solution was purified by flash chromatography using dichloromethane / hexane (0%→88%) as eluent. The desired fractions were collected and dried under reduced pressure to give an orange solid (68 mg, yield 31%). LCMS (APCI+): C 62 H 54 Calculated value for B2F4N4 = 952; Found: 952. 1 H NMR (400 MHz, CHLOROFORM-d) δ 8.29 (t, J = 5.6 Hz, 1H), 7.73 (d, J = 8.4 Hz, 1H), 7.50 (dd, J = 8.1, 4.2 Hz, 1H), 7.33 (s, 1H), 7.26 (s, 3H), 6.05 (s, 1H), 2.60 (s, 3H), 2.26 (s, 3H).

[0231] Example 2.3: PC-3

[0232]

[0233] PC-3: A mixture of compound 1.1 (270 mg, 0.59 mmol), 4,4,5,5-tetramethyl-2-(3-perylene)-1,3,2-dioxaborolane (302 mg, 0.8 mmol), potassium carbonate (98 mg, 1 mmol) and Pd(PPh3)4 (58 mg, 0.05 mmol) was dissolved in 1,4-dioxane (10 mL). The solution was degassed and heated at 100°C for 6 hours. The resulting mixture was subjected to flash chromatography using dichloromethane / hexane (0→60%) as eluent for purification. The desired fractions were collected and dried under reduced pressure to give an orange solid (50 mg, yield 14%). LCMS (APCI+): C 43 H 38 Calculated for BF2N2 (M+H) = 631; found 631.

[0234] Example 2.4: PC-4

[0235]

[0236] Compound 4.1: 2.0 g of perylene (7.94 mmol) was added to 100 mL of o-dichlorobenzene. The solution was stirred at 70 ° C for 20 min until the perylene was completely dissolved. The solution was then cooled to 0 ° C and 1.05 g of anhydrous AlCl3 (7.94 mmol) was added. Next, 11 mL of tert-butyl chloride was slowly added to the solution. The resulting mixture was warmed to room temperature and stirred overnight. The entire mixture was poured into dichloromethane (400 mL), washed with water, brine, dried over Na2SO4, concentrated to 100 mL, and passed through a silica gel column with hexane / dichloromethane (1:1 v / v) as the eluent. The main fractions were collected and concentrated to 100 mL. Next, 2.85 g of NBS (16 mmol) was added to the solution and stirred at room temperature for 18 h. The resulting mixture was poured into water, the organic phase was separated and washed with brine, and then concentrated to 10 mL via vacuum distillation. To the concentrated solution was added 50 mL of isopropanol and 100 mL of methanol under stirring. After stirring for 5 min, the mixture was filtered to give the desired product, compound 4.1, as a yellow-brown solid (3.0 g, yield 80%).

[0237] Compound 4.2: 2.33 g of compound 4.1 (5 mmol), 4.06 g of diboron bispinacol ester (16 mmol), 2.9 g of potassium acetate (30 mmol) and 0.44 g of Pd (dppf) Cl2 (0.6 mmol) were added to a 500 mL flask containing 100 mL of anhydrous dioxane, and the resulting solution was degassed for 30 min and then heated at 90 ° C overnight under argon. The resulting mixture was poured into ethyl acetate (200 mL) and then washed with brine. The organic phase was collected and dried over Na2SO4, then loaded onto silica gel and purified by flash chromatography using dichloromethane / hexane (0% → 30%) as eluent. The desired fractions were collected and dried under reduced pressure to give a yellow solid (1.7 g, 60% yield).

[0238] PC-4: A mixture of compound 2.2 (0.388 g, 0.9 mmol), diboronate compound 4.2 (0.224 g, 0.4 mmol), potassium carbonate (0.138 g, 1 mmol) and Pd(PPh3)4 (58 mg, 0.05 mmol) in 1,4-dioxane (25 mL) was degassed for 30 min and then heated at 100°C for 2 days. After cooling to room temperature, the mixture was diluted with 100 mL of dichloromethane and then loaded onto silica gel and purified by flash chromatography using dichloromethane / hexane (0%→40%) as the eluent. The desired fractions were collected and dried under reduced pressure to give a red solid (100 mg, yield 25%). LCMS (APCI+): C 66 H 63 Calculated value of B2F4N4 = 1009; Found: 1009. 1 H NMR (400MHz, chloroform-d) δ8.34-8.19(m,4H),7.77-7.69(m,2H),7.54-7.44(m,4H) ),7.36-7.30(m,4H),6.04(s,4H),2.60(s,12H),2.26(s,12H),1.39(s,9H).

[0239] Example 2.5: PC-5

[0240]

[0241] PC-5: A mixture of BODIPY compound 2.2 (108 mg, 0.25 mmol), 2-(8,11-di-tert-butylperylene-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (120 mg, 0.23 mmol, purchased from TCI chemicals), potassium carbonate (55 mg, 0.4 mmol) and Pd(PPh3)4 (30 mg, 0.02 mmol) was dried under vacuum for 90 min, and then 1,4-dioxane (8 mL) was added and degassed for 30 min. The solution was heated at 100°C for 40 h and then purified by flash chromatography using dichloromethane / hexane (0→20%) as the eluent. The desired fractions were collected and dried under reduced pressure to give an orange solid (100 mg, yield 61%). LCMS (APCI+): C 49 H 50 Calculated for BF2N2 (M+H) = 715; found: 715. 1 H NMR (400 MHz, CHLOROFORM-d) δ 8.30-8.23 (m, 3H), 7.73-7.63 (m, 3H), 7.50-7.41 (m, 2H), 7.31 (m, 2H), 7.26 (s, 1H), 6.04 (s, 2H), 2.60 (s, 6H), 2.25 (s, 6H), 1.57 (s, 6H), 1.49 (s, 18H).

[0242] Example 2.6: PC-6

[0243]

[0244] Compound 6.1 (perylene-3-carboxaldehyde): 0.75 mL of POCl3 was added to a suspension of perylene (1.0 g, 3.96 mmol) in 2 mL of anhydrous DMF and 2 mL of anhydrous o-dichlorobenzene. The resulting solution was then heated at 100 ° C overnight. The next morning, the solution was cooled in an ice bath for 1 hour. Next, the solution was neutralized with 5 mL of a 10% NaOAc aqueous solution. Once neutralized, the solution was filtered. After filtration, the solid was collected and dried in a vacuum oven for 3 hours. After drying, the solid was redissolved in 250 mL of dichloromethane, loaded onto silica gel, and purified by flash chromatography using dichloromethane / hexane (10% → 50%) as an eluent. The desired fractions were collected and dried under reduced pressure to give an orange solid (0.80 g, 72.2% yield). 1HNMR (400 MHz, CHLOROFORM-d) δ10.34 (s, 1H), 9.20 (d, J = 8.5 Hz, 1H), 8.38-8.27 (m, 4H), 7.97 (d, J = 7.9 Hz, 1H), 7.83 (d, J = 8.1 Hz, 1H), 7.80-7.68 (m, 2H), 7.56 (td, J = 7.8, 4.2 Hz, 2H).

[0245] Compound 6.2 (3-hydroxymethylperylene): 1.5 mL of a 2.0 M solution of LiBH4 in THF was added to a solution of perylene-3-carboxaldehyde (0.65 g) in 50 mL of THF. The resulting solution was stirred at room temperature overnight under argon. The next day, the solution was diluted with dichloromethane (200 mL), washed with aqueous NH4Cl and brine. The organic phase was collected and concentrated under reduced pressure to give a yellow solid (0.50 g, 77% yield). 1 H NMR (400 MHz, CHLOROFORM-d) δ 8.21 (ddd, J = 15.4, 12.8, 7.6 Hz, 4H), 7.97 (d, J = 8.4 Hz, 1H), 7.70 (d, J = 8.1 Hz, 2H), 7.61-7.52 (m, 2H), 7.49 (t, J = 7.9 Hz, 2H), 5.11 (s, 2H).

[0246] Compound 6.3 (3-bromomethylperylene): 2.5 mL of a 1 M solution of PBr3 in dichloromethane was added to a suspension of 0.5 g of 3-hydroxymethylperylene (compound 6.2) in 50 mL of dichloroethane. The reaction mixture was heated at 80°C for 2 hours under argon. The solution was evaporated under reduced pressure at room temperature and the residue was stirred with 40 mL of MeOH to precipitate the bromide. The mixture was filtered to give 3-bromomethylperylene (compound 10) as an orange solid (0.55 g, 90% yield). 1 H NMR (400MHz, CDCl3): δ=8.28-8.13(m,4H,),7.90(d,1H,J=7.9Hz),7.74(d,2H,J =8.0Hz), 7.64 (t, 1H, J = 7.9Hz), 7.56 (d, 1H, J = 7.6Hz), 7.51 (m, 2H), 4.95 (s, 2H).

[0247] Compound 6.4: A solution of 4-hydroxy-2,6-dimethylbenzaldehyde (0.75 g, 5 mmol) and 2,4-dimethylpyrrole (1.04 g, 11 mmol) in 100 mL of anhydrous dichloromethane was degassed for 30 min, and then a drop of trifluoroacetic acid was added. The solution was stirred at room temperature overnight under argon. DDQ (2.0 g, 8.8 mmol) was added to the resulting solution and stirred at room temperature overnight. The resulting mixture was filtered and washed thoroughly with dichloromethane to give a brown solid as the desired compound 6.4 (1.6 g, 100% yield). LCMS (APCI+): C 21 H 25 Calculated for N2O (M+H) = 321; found 321.

[0248] Compound 6.5: 5 mL of trimethylamine was added to a solution of dipyrromethane, compound 6.4 (1.0 g) in 60 mL of THF. The solution was degassed for 10 min, and then trifluoroborane-diethyl ether (5 mL) was slowly added. Next, the solution was heated at 70°C for 30 min. The resulting solution was subjected to flash chromatography (silica gel) using dichloromethane as eluent. The desired fractions were collected and dried under reduced pressure to give an orange solid (0.9 g, yield 76%). 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).

[0249] PC-6: A solution of compound 6.5 (180 mg, 0.49 mmol), compound 6.3 [3-bromomethylperylene] (172 mg, 0.5 mol), anhydrous potassium carbonate (138 mg, 1 mmol) in anhydrous DMF / o-dichlorobenzene (5 mL / 5 mL) was stirred overnight at 60 ° C under argon. The resulting solution was loaded on silica gel and purified by flash chromatography using dichloromethane / hexane (0→35%) as eluent. The desired fractions were collected and dried under reduced pressure to give an orange solid (60 mg, yield 20%). LCMS (APCI+): C 42 H 36 Calculated for BF2N2O (M+H) = 633; ​​found 633. 1H NMR (400MHz, chloroform-d) δ8.22(ddd,J=16.0,13.8,7.6Hz,4H),7.88(d,J=8.4Hz,1H),7.71(d,J=8.1Hz,2H),7.62(d,J=7.7Hz,1H) ,7.57(t,J=7.9Hz,1H),7.50(t,J=7.8Hz,2H),6.87(s,2H),5.98(s,2H),5.44(s,2H),2.56(s,6H),2.13(s,6H),1.46(s,6H).

[0250] Example 2.7 PC-7:

[0251]

[0252] Compound 7.1: 1 mL of trifluoroborane-diethyl ether was added to a solution of glutaric anhydride (420 mg, 3.68 mmol) and 2,4-dimethylpyrrole (0.6 g, 6.3 mmol) in anhydrous THF (25 mL). The solution was then degassed for 30 min and then heated at 70 ° C for 12 hours. Next, the solution was cooled to room temperature, 2.5 g of trimethylamine and 2.5 g of trifluoroborane-diethyl ether were added to the solution in sequence, and heated at 50 ° C for 4 hours. After 4 hours, the solution was washed with NH4Cl aqueous solution and extracted with dichloromethane (100 mL×2). The organic phase was dried over Na2SO4 and loaded onto silica gel for purification by flash chromatography using ethyl acetate / hexane (0%→40%) as the eluent. The desired fractions were collected and dried under reduced pressure to give compound 13 (150 mg, yield 12%) as a red solid. LCMS (APCI+): C 38 H 34 Calculated for BF2N2O2 (M+H) = 599; found: 599. 1 H NMR (400 MHz, CHLOROFORM-d) δ 6.06 (s, 2H), 3.08-2.99 (m, 2H), 2.55 (t, J=8.8 Hz, 2H), 2.52 (s, 6H), 2.43 (s, 6H), 1.97 (m, 2H).

[0253] PC-7: A mixture of compound 7.1 (80 mg, 0.24 mmol), compound 6.2 [3-hydroxymethylperylene] (68 mg, 0.24 mmol), DCC (62 mg, 0.3 mmol) and DMAP (100 mg, 0.82 mmol) in THF (8 mL) was stirred at room temperature overnight under argon. The solution was loaded on silica gel and purified by flash chromatography using dichloromethane / hexane (1:1) → dichloromethane / ethyl acetate (1:1) as eluent. The desired fractions were collected and dried under reduced pressure to give PC-7 (50 mg, yield 30%) as an orange solid. LCMS (APCI-): C 38 H 32 Calculated value for BF2N2O2(M-)=597; found value is 597. 1 H NMR (400MHz, chloroform-d) δ8.29-8.15(m,4H),7.84(d,J=8.3Hz,1H),7.72(dd,J=7.9,2.7Hz,2H),7.54(dt,J=23.6,7.8Hz,4 H), 6.03 (s, 2H), 5.55 (s, 2H), 3.05-2.96 (m, 2H), 2.58 (t, J = 7.2Hz, 2H), 2.50 (s, 6H), 2.38 (s, 6H), 2.03-1.95 (m, 2H).

[0254] Example 2.8 PC-8:

[0255]

[0256] Compound 8.1 (methyl 4-oxo-4-(perylene-3-yl)butanoate): Under nitrogen atmosphere, 1.34 g AlCl3 (10.00 mmol) was added to a mixture of 1.04 mL 4-chloro-4-oxobutanoate (8.45 mmol) in 160 mL of anhydrous DCM in a powder dispersion funnel in small portions at 0°C over 15 minutes. The resulting solution was stirred at 0°C for 1 hour. Subsequently, a solution of 2.00 g of perylene (7.9 mmol) in anhydrous DCM was added dropwise to the solution while the temperature was maintained at 0°C. The resulting dark purple solution was stirred at room temperature overnight under a nitrogen atmosphere. The next day, the solution was poured into a solution of 75 mL ice water, 5 mL 6N HCl aqueous solution and 150 mL DCM. The organic layer was separated; the aqueous layer was re-extracted with ethyl acetate (100 ml). The organic layers were combined, dried over MgSO4 and concentrated. The residue was loaded onto a silica gel column. Chromatography with DCM gave 1.8 g of orange solid product in 62% yield. LCMS (APCI+): C 25 H 19Calculated value of O3 = 367; Found: 367.

[0257] Compound 8.2 (4-(perylene-3-yl)butyric acid): 3.4 g of compound 8.1 [methyl 4-oxo-4-(perylene-3-yl)butyrate] (9.28 mmol), 2.7 mL of 98% monohydrate hydrazine (53 mmol) in 30 mL of diethylene glycol were placed in a pressure bottle and stirred at room temperature. 3.91 g of KOH (powder) (69.8 mmol) was added to the solution. The resulting solution was stirred at 80°C for 15 minutes, then heated to 140°C and bubbled with a slow stream of argon for 2 hours. The pressure bottle was sealed with a septum, the argon atmosphere was maintained with a balloon and the temperature was raised to 190°C. The solution was then stirred for 16 hours while maintaining a temperature of 190°C. Next, the solution was cooled to room temperature, diluted with 300 mL of water, and passed through diatomaceous earth; the resulting filtrate was acidified with 6N HCl. The green solid was collected by filtration and washed with water. The green solid product was dried in a vacuum oven, 3.0 g, 95% yield. LCMS (APCI+): C 24 H 19 Calculated for O2 (M+H) = 339; found: 339. 1 H NMR(400MHz,DMSO-d6)δ11.57(s,1H),8.35( δδ ,J=10.9,7.4Hz,2H),8.28( δδ ,J=12.2,7.5Hz,2H),7.98( δ ,J=8.5Hz,1H),7.76(t,J=7.5Hz,2H),7.61-7.50(m,2H),7.54-7.47(m,1H),7.38( δδ ,J=7.9,3.4Hz,1H),3.49( δ ,J=5.2Hz,1H),3.43(q,J=6.2,5.2Hz,1H),3.01( δδ ,J=9.0,6.6Hz,2H),2.36(t,J=7.2Hz,2H),1.91(p,J=7.4Hz,2H).

[0258] PC-8: Under nitrogen atmosphere, 412.6 mg of DCC (2.00 mmol) was added to a solution containing 369 mg of BODIPY compound 6.5 (1.00 mmol), 406 mg of compound 8.2 [4-(perylene-3-yl)butyric acid] (1.2 mmol), and 242 mg of DMAP (2.00 mmol) in 10 mL of anhydrous THF. The resulting solution was stirred at room temperature for 16 hours. Next, water was added, followed by 150 mL of ethyl acetate. The solution was passed through diatomaceous earth. The organic layer was separated and concentrated. The crude product was purified by silica gel column chromatography using hexane: ethyl acetate (9:1) as the eluent to give 510 mg of a reddish-orange solid product with a yield of 74%. LCMS (APCI+): C 45 H 40 Calculated for BF2N2O2 (M+H) = 689; found: 689. 1 H NMR(400MHz, chloroform-d)δ8.23(δ,J=7.5Hz,1H),8.23-8.12(m,3H),7.94(δ,J=8.4Hz, 1H),7.68(δδ,J=8.1,5.0Hz,2H),7.54(t,J=8.0Hz,1H),7.48(tδ,J=7.8,2.6Hz, 2H),7.39(δ,J=7.7Hz,1H),6.87(s,2H),5.97(s,2H),3.19(t,J=7.6Hz,2H),2.7 0(t,J=7.2Hz,2H),2.56(s,6H),2.25(p,J=7.3Hz,2H),2.12(s,6H),1.39(s,6H).

[0259] Example 2.9 PC-9:

[0260]

[0261] Compound 9.1 (tert-butyl (E)-3-(perylene-3-yl)acrylate): Under the protection of an argon atmosphere, 4.55 mL of 1 M potassium tert-butoxide (t-BuOK) / THF (4.55 mmol) was added dropwise to a suspension of 2.09 g of tert-butoxycarbonylmethyltriphenylphosphonium bromide (4.55 mmol) in 5 mL of anhydrous THF at 0°C. The resulting solution was stirred at 0°C for 15 min. Next, a solution of 0.981 g of compound 6.1 [perylene-3-carboxaldehyde] (3.5 mmol) in 100 mL of anhydrous THF was added. The resulting mixture was stirred at room temperature overnight. The solution was treated with water and DCM. The crude product was purified by SiO2 column chromatography using hexane:DCM as the eluent to obtain 1.13 g of an orange solid product with a yield of 85%. LCMS (APCI+): C27 H 23 Calculated for O2 (M+H) = 379; found: 379. 1 H NMR (400MHz, chloroform-d) δ8.30 (δ, J=15.7Hz, 1H), 8.15 (δδδ, J=17.6, 13.0, 7.8Hz, 4H), 7.99 (δ, J=8.5Hz, 1H), 7.69 (δ, J=8.0Hz, 1H) ,7.64(δδ,J=8.1,5.0Hz,2H),7.51(t,J=8.0Hz,1H),7.47(t,J=8.1Hz,2H),6.42(δ,J=15.7Hz,1H),3.43(s,1H),1.52(s,9H).

[0262] Compound 9.2 (tert-butyl (E)-3-(perylene-3-yl)acrylate): A solution of 168 mg of compound 9.1 [tert-butyl (E)-3-(perylene-3-yl)acrylate] (0.433 mmol) and 20 mg of Pd / C 10% w / w in 5 mL of THF:MeOH (9:1) was hydrogenated for 5 hours under 65 psi H2 atmosphere using a Parr Shaker. Next, the solution was filtered through celite and concentrated under reduced pressure to give 152 mg of a yellow solid product with a yield of 90%. LCMS (APCI+): C 27 H 25 Calculated for O2 (M+H) = 381; found: 381. 1 H NMR (400MHz, chloroform-d) δ8.28-8.12(m,4H),7.90(δ,J=8.4Hz,1H),7.70(δδ,J=8.1,5.3Hz,2H),7.57(δ,J=8.0H z,1H),7.54-7.45(m,2H),7.40(δ,J=7.7Hz,1H),3.35(δ,J=8,0Hz,2H),2.71(δ,J=8.0Hz,2H),1.4(s,9H).

[0263] Compound 9.3 (3-(Perylene-3-yl)propionic acid): 10 mL of TFA was added to a solution of 1.52 g of compound 9.2 [tert-butyl (E)-3-(Perylene-3-yl)acrylate] (4 mmol) in 50 mL of DCM. The solution was stirred at room temperature for 2 hours. Next, the solvent and TFA were removed under reduced pressure. The crude solid product was washed with hexane to give 1.26 g of a yellow-green solid product with a yield of 97%. LCMS (APCI+): C 23 H 17 Calculated for O2 (M+H) = 325; found: 325. 1H NMR(400MHz, DMSO-d6)δ12.24(s,1H),8.35(δδδ,J=28.2,13.1,7.6Hz,4H),7.94(δ,J=8.4Hz,1H),7.78(t,J=7.2Hz,2H) ,7.61(t,J=7.9Hz,1H),7.54(tδ,J=7.8,3.5Hz,2H),7.43(δ,J=7.7Hz,1H),3.26(t,J=7.7Hz,2H),2.67(t,J=7.6Hz,2H).

[0264] PC-9: Under nitrogen atmosphere, 24.2 mg of DCC (0.2 mmol) was added to a solution of 32 mg of compound 6.5 [4-(5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinin-10-yl)-3,5-dimethylphenol] (0.1 mmol), 37 mg of compound 9.3 [3-(perylene-3-yl)propionic acid] (0.1 mmol), 24.2 mg of DMAP (0.2 mmol) and 5.0 mL of anhydrous DMF. The resulting solution was stirred at room temperature for 16 hours. Water was added, followed by 50 mL of DCM. The solution was passed through celite. The organic layer was separated and concentrated. The crude product was purified by silica gel column chromatography using hexane:DCM as eluent to give 30 mg of orange-red solid product with a yield of 45%. LCMS (APCI+): C 44 H 38 Calculated for BF2N2O2 (M+H) = 675; found: 675. 1 H NMR (400MHz, chloroform-d) δ8.31-8.16(m,2H),7.93(δ,J=8.4Hz,0H),7.72(δδ,J=8.1,4.3Hz,1H),7.63-7.49(m,1H),7.53-7.4 5(m,1H),6.89(s,1H),6.00(s,1H),3.53(t,J=7.8Hz,1H),3.06(t,J=7.8Hz,1H),2.58(s,6H),2.16(s,6H),1.43(s,6H).

[0265] Example 2.10 PC-10:

[0266]

[0267] Compound 10.1 (2,5-di-tert-butylperylene): Under nitrogen atmosphere, 5 g of perylene (19.81 mmol) was dissolved in 300 ml of anhydrous o-dichlorobenzene in a three-necked round-bottom flask. The resulting yellow solution was cooled to 0 ° C. 2.64 g of AlCl3 (19.81 mmol) was added in small portions via a powder distribution funnel over 45 minutes, followed by dropwise addition of 50 mL of tert-butyl chloride (458 mmol). The resulting green solution was stirred at room temperature for 24 hours. The reaction mixture was poured into 100 mL of ice water. The organic layer was separated and concentrated to dryness using a rotary evaporator, wherein the water bath of the rotary evaporator was set to 70 ° C. The residue was redispersed in 450 mL of hot hexane. The yellow solution was cooled and left overnight at room temperature. The insoluble material was filtered and detected by LCMS as a tetrabutyl analog (M+H=477). The filtrate was a mixture of di-tert-butylperylene and tri-tert-butylperylene, which was loaded onto a silica gel column. Chromatographic separation was performed using hexane:EtOAc (9:1) to obtain 3.75 g of a light yellow solid product, 2,5-di-tert-butylperylene, with a yield of 52%. 28 H 29 LCMS (APCI+) calcd. for (M+H)=365; found: 365. 1 H NMR (400 MHz, CHLOROFORM-d) δ 8.30-8.21 (m, 4H), 7.72-7.63 (m, 4H), 7.50 (t, J=7.8 Hz, 2H), 1.50 (s, 18H).

[0268] Compound 10.2 (8,11-di-tert-butylperylene-3-carboxaldehyde): Under nitrogen atmosphere, 3.75 g of compound 10.1 [2,5-di-tert-butylperylene] (10.28 mmol) and 5.1 mL of anhydrous DMF (66.95 mmol) were dissolved in 5.1 ml of anhydrous o-dichlorobenzene in a three-necked round-bottom flask. The resulting yellow mixture was bubbled with argon for 15 min. The resulting mixture was stirred at 100° C. for 15 minutes. 1.9 mL of POCl3 (20.6 mmol) was added dropwise through a dropping funnel over 1 hour while the solution was maintained at 100° C. The resulting deep red solution was stirred at 100° C. for 24 hours. Next, the solution was cooled to room temperature, and 100 mL of a dilute aqueous sodium acetate solution was added while stirring at 0° C. Once the solution was completely mixed, the solution was allowed to stand at 0° C. for 3 hours. The dark liquid solution was decanted; the remaining viscous dark oil was taken up in dichloromethane (DCM) and then washed with water. The organic layer was separated and concentrated. The residue was loaded onto a silica gel column. Chromatography was performed using hexane:DCM (9:1) as eluent. The fractions containing the desired product were collected, evaporated, and then recrystallized from hexane to give 0.58 g of orange-red solid product with a yield of 14.3%. LCMS (APCI+): C29 H 29 Calcd. for O(M+H)=393; found: 393. 1 H NMR (400MHz, DMSO-d6)δ10.35(s,1H),9.11(δ,J=8.4Hz,1H),8.73(δ,J=7.9Hz,1H),8.67(δ,J=7.7Hz,1H),8.57(δ,J=1.7Hz ,1H),8.50(δ,J=1.7Hz,1H),8.17(δ,J=7.8Hz,1H),7.92(s,1H),7.85(s,1H),7.78(t,J=8.0Hz,1H),1.47(δ,J=4.4Hz,18H).

[0269] Compound 10.3 (tert-butyl (E) -3- (8,11-di-tert-butylperylene-3-yl) acrylate): Under argon protection, 0.305 mL of 1M potassium tert-butoxide (t-BuOK) / THF (0.305 mmol) was added dropwise to a suspension of 140 mg of tert-butyloxycarbonylmethyltriphenylphosphonium bromide (0.305 mmol) in 2 mL of anhydrous THF at 0°C. The resulting solution was stirred at 0°C for 1 hour. Next, a solution containing 100 mg of compound 10.2 [8,11-di-tert-butylperylene-3-carboxaldehyde] (0.254 mmol) in 1.0 mL of anhydrous THF was added while maintaining the temperature at 0°C. The resulting solution was stirred at 65°C overnight. The reaction solution was treated with water and ethyl acetate, and the crude product was purified by SiO2 column chromatography using hexane: DCM as the eluent to give 110 mg of an orange solid product with a yield of 88%. LCMS (APCI+): C 35 H 39 Calculated for O2 (M+H) = 491; found: 491. 1H NMR (400MHz, chloroform-d) δ8.38(d,J=15.7Hz,1H),8.28(t,J=5.8Hz,3H),8.21(d,J=8.0Hz,1H),8.05(d,J=8.4Hz,1H),7.7 6(d,J=8.0Hz,1H),7.67(d,J=6.6Hz,2H),7.58(t,J=7.9Hz,1H),6.48(d,J=15.8Hz,1H),1.59(s,9H),1.48(s,18H). Compound 10.4 (3-(8,11-di-tert-butylperylene-3-yl)propanoic acid): A solution containing 110 mg of compound 10.3 [tert-butyl (E)-3-(8,11-di-tert-butylperylene-3-yl)acrylate] (0.224 mmol) and 10 mg of Pd / C 10% w / w dissolved in EtOAc:MeOH (9:1) was stirred at room temperature for 2 hours under H2 atmosphere. The solution was filtered through celite and concentrated under reduced pressure to give 110 mg of yellow solid product with a yield of 98%. LCMS (M+H) = 493. Next, 110 mg of the yellow solid product was dissolved in 5.0 mL of DCM. Once the solid product was completely dissolved, 1.0 mL of TFA was added and stirred at room temperature for 2 hours. DCM and TFA were removed under reduced pressure. The crude solid product was washed with hexane to give 36 mg of yellow-green solid product with a yield of 97%. LCMS (APCI+): C 31 H 33 Calculated for O2 (M+H) = 437; found: 437. 1 H NMR (400MHz, chloroform-d) δ8.25(t,J=9.2Hz,3H),8.16(d,J=7.7Hz,1H),7.85(d,J=8.4Hz,1H),7.63(d,J=4.5Hz,2 H), 7.55 (t, J = 8.0Hz, 1H), 7.39 (d, J = 7.7Hz, 1H), 3.40 (t, J = 7.9Hz, 2H), 2.85 (t, J = 7.9Hz, 2H), 1.47 (s, 18H).

[0270] PC-10: Under nitrogen atmosphere, 30.53 mg DCC (0.148 mmol) was added to a solution containing 27 mg compound 6.5 [4-(5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-10-yl)-3,5-dimethylphenol] (0.074 mmol), 17.9 mg compound 10.4 [3-(8,11-di-tert-butylperylene-3-yl)propionic acid] (0.1 mmol), and 17.9 mg DMAP (0.148 mmol) dissolved in 5.0 mL of anhydrous THF. The resulting solution was stirred at room temperature for 16 hours. Water was added, followed by 50 mL of ethyl acetate. The resulting solution was passed through celite. The organic layer was separated and concentrated. The crude product was purified by silica gel column chromatography using hexane:DCM (9:1) as eluent. 43 mg of orange-red solid product was obtained with a yield of 73%. LCMS (APCI+): C 52 H 54 Calculated for BF2N2O2 (M+H) = 787; found: 787. 1 HNMR (400MHz, chloroform-d) δ8.31-8.16(m,2H),8.19(δ,J=7.6Hz,1H),7.89(δ,J =8.4Hz,1H),7.64(s,1H),7.63(s,1H),7.57(t,J=7.9Hz,1H),7.45(δ,J=7 .7Hz,1H),6.85(s,2H),5.97(s,2H),3.51(t,J=7.8Hz,2H),3.04(t,J=7.8 Hz,2H),2.56(s,6H),2.13(s,6H),1.48(s,9H),1.47(s,9H),1.40(s,6H).

[0271] Example 2.11 PC-11:

[0272]

[0273] Compound 11.1 (ethyl (E)-5-(8,11-di-tert-butylperylene-3-yl)pent-4-enoate): Under argon atmosphere, 1.82 mg of 1M potassium tert-butoxide (t-BuOK) / THF (1.82 mmol) was added dropwise to a suspension containing 832 mg of (4-ethoxy-4-oxobutyl)triphenylphosphonium bromide (1.82 mmol) dissolved in 5 mL of anhydrous THF at 0°C. The resulting solution was stirred at 0°C for 1 hour. Next, a suspension of 550 mg of compound 10.1 [8,11-di-tert-butylperylene-3-carboxaldehyde] (1.4 mmol) dissolved in 20 mL of anhydrous THF was added while maintaining the temperature at 0°C. The resulting solution was stirred at 65°C overnight. The solution was treated with water and ethyl acetate the next day. The crude product was purified by SiO2 column chromatography using hexane:DCM as eluent to give 230 mg of orange solid product in 33% yield. LCMS (APCI+): C 35 H 39 Calculated for O2 (M+H) = 491; found: 491.

[0274] Compound 11.2 (5-(8,11-di-tert-butylperylene-3-yl)pentanoic acid): A solution containing 230 mg of compound 11.1 [(E)-5-(8,11-di-tert-butylperylene-3-yl)pent-4-enoic acid ethyl ester] (0.468 mmol) and 10 mg of Pd / C 10% w / w in 15 mL EtOAc:MeOH (9:1) was stirred at room temperature for 2 hours under H2 atmosphere. The solution was filtered through celite and concentrated under reduced pressure to give 230 mg of a yellow solid product with a yield of 100%. LCMS (APCI+): C 35 H 41 Calculated for O2 (M+H) = 493; found: 493.

[0275] Next, 5.0 mL of THF and 2 mL of 4M KOH aqueous solution were added to 230 mg of the yellow solid product and stirred at room temperature for 16 hours. The solution was acidified with HCl 6N aqueous solution. Then, ethyl acetate was added, the organic layer was separated, dried over MgSO4 and concentrated. The solvent was removed under reduced pressure. The crude solid product was washed with hexane to obtain 176 mg of a yellow-green solid product with a yield of 81%. The product can be used in the next step without further purification. LCMS (APCI+): C 33 H 37 Calculated for O2 (M+H) = 465; found: 465.

[0276] PC-11: Under nitrogen protection, 25.17 mg of DCC (0.122 mmol) was added to a solution containing 22.5 mg of compound 6.5 [4-(5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinylcyclohexene-10-yl)-3,5-dimethylphenol] (0.061 mmol), 25 mg of compound 11.2 [5-(8,11-di-tert-butylperylene-3-yl)pentanoic acid] (0.067 mmol), and 14.78 mg of DMAP (0.122 mmol) dissolved in 2.0 mL of anhydrous THF. The resulting solution was stirred at room temperature for 16 hours. Water was added, followed by 50 mL of ethyl acetate. The solution was passed through celite. The organic layer was separated and concentrated. The crude product was purified by silica gel column chromatography using hexane:DCM (9:1) as eluent to give 15 mg of orange-red solid product with a yield of 25%. LCMS (APCI+): C 54 H 58 Calculated for BF2N2O2 (M+H) = 815; found: 815. 1 H NMR (400MHz, chloroform-d) δ8.26(t,J=7.6Hz,3H),8.18(δ,J=7.6Hz,1H),7.90(δ,J=8.4Hz,1 H),7.65(δ,J=5.5Hz,2H),7.55(t,J=7.9Hz,1H),7.39(δ,J=7.6Hz,1H),6.89(s,2H),5 .99(s,2H),3.13(t,J=7.8Hz,3H),2.66(t,J=7.8Hz,3H),2.58(s,6H),2.15(s,6H),1. 93(t,J=7.8Hz,2H),1.50(s,18H),1.42(s,6H),1.22-1.03(m,2H),0.92-0.89(m,2H).

[0277] Example 2.12 PC-12:

[0278]

[0279] Compound 12.1 (methyl 4-(8,11-di-tert-butylperylene-3-yl)-4-oxobutanoate): Under nitrogen atmosphere, 2.63 g AlCl3 (19.97 mmol) was added to a suspension of 2.45 mL methyl 4-chloro-4-oxobutanoate (19.97 mmol) in 175 mL anhydrous DCM in small portions at 0°C over 15 minutes via a powder dispersion funnel. The resulting solution was stirred at 0°C for 1 hour. Then, a solution of 5.77 g of compound 10.1 [2,5-di-tert-butylperylene] (15.85 mmol) dissolved in anhydrous DCM was added dropwise while keeping the temperature at 0°C. The resulting dark purple solution was stirred at room temperature overnight under a nitrogen atmosphere. The next day, the solution was poured into a mixture of 150 mL ice water and 300 mL DCM. The organic layer was separated; the aqueous layer was re-extracted with 100 mL ethyl acetate. The organic layers were combined, dried over MgSO4 and concentrated. The residue was loaded onto a silica gel column. Chromatography was performed using hexane:ethyl acetate (9:1) as the eluent to give 2.7 g of an orange solid product with a yield of 35%. LCMS (APCI+): C 33 H 35 Calculated value for O3 (M+H) = 479; found: 479; 1H NMR (400 MHz, CHLOROFORM-d) δ 8.58 (d, J = 8.6 Hz, 1H), 8.34-8.27 (m, 3H), 8.23 ​​(d, J = 8.0 Hz, 1H), 7.98 (d, J = 7.9 Hz, 1H), 7.73 (s, 1H), 7.68 (s, 1H), 7.60 (t, J = 8.0 Hz, 1H), 3.75 (s, 3H), 3.41 (t, J = 6.5 Hz, 2H), 2.86 (t, J = 6.6 Hz, 2H), 1.49 (d, J = 3.5 Hz, 18H).

[0280] Compound 12.2 (4-(8,11-di-tert-butylperylene-3-yl)butanoic acid): 470.5 mg of compound 12.1 [methyl 4-(8,11-di-tert-butylperylene-3-yl)-4-oxobutanoate] (0.983 mmol) and 150 μL of 98% hydrazine monohydrate (2.949 mmol) dissolved in 2 mL of diethylene glycol were placed in a microwave vial and stirred at room temperature. 275 mg of KOH (powder) (4.91 mmol) was added to the solution and stirred at 80°C for 15 min. The solution was then heated to 140°C and bubbled with a slow stream of argon for 2 hours. The vial containing the solution was sealed with a septum, the argon atmosphere was maintained with a balloon and the temperature was raised to 190°C. The resulting solution was stirred for 16 hours while the temperature was maintained at 190°C. The solution was then cooled to room temperature, diluted with 20 mL of water, and acidified with 6N HCl. The resulting green solid was collected by filtration and purified by SiO2 column chromatography using DCM:EtOAc (1:1) as eluent to give 110 mg of green solid product in 88% yield. LCMS (APCI+): C 32 H 35 Calculated value for O2 (M+H) = 451; found: 451; 1 H NMR (400 MHz, CHLOROFORM-d) δ 8.27-8.19 (m, 3H), 8.15 (d, J = 7.7 Hz, 1H), 7.88 (d, J = 8.4 Hz, 1H), 7.62 (d, J = 5.2 Hz, 2H), 7.53 (t, J = 8.0 Hz, 1H), 7.34 (d, J = 7.7 Hz, 1H), 5.30 (s, 1H), 3.09 (t, J = 7.7 Hz, 2H), 2.48 (t, J = 7.2 Hz, 2H), 2.11 (p, J = 7.4 Hz, 2H), 1.47 (s, 18H).

[0281] PC-12: Under nitrogen atmosphere, 74.27 mg of DCC (0.36 mmol) was added to a solution containing 66 mg of compound 6.5 [4-(5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinyl-10-yl)-3,5-dimethylphenol] (0.18 mmol), 100 mg of compound 12.2 [4-(8,11-di-tert-butylperylene-3-yl)butanoic acid] (0.22 mmol), and 43.6 mg of DMAP (0.36 mmol) dissolved in 2.0 mL of anhydrous THF. The resulting solution was stirred at room temperature for 16 hours. Water was added, followed by 50 mL of ethyl acetate. The solution was then passed through celite. The organic layer was separated and concentrated. The crude product was purified by silica gel column chromatography using hexane:ethyl acetate (9:1) as the eluent to obtain 43 mg of orange-red solid product with a yield of 24%. LCMS (APCI+): C 53 H 56 Calculated for BF2N2O2 (M+H) = 801; found: 801. 1 H NMR (400MHz, chloroform-d) δ8.26(δ,J=7.4Hz,1H),8.24(s,1H),8.22(s,1H),8.18(δ,J=7.7Hz ,1H),7.93(δ,J=8.3Hz,1H),7.63(s,1H),7.62(s,1H),7.53(t,J=7.9Hz,1H),7.4(δ,J =7.4Hz,1H),6.85(s,2H),5.96(s,2H),3.18(t,J=7.3Hz,2H),2.69(t,J=7.4Hz,2H),2 .55(s,6H),2.25(t,J=7.4Hz,2H),2.1(s,6H),1.48(s,9H),1.47(s,9H),1.38(s,6H).

[0282] Example 2.13 PC-13:

[0283]

[0284] Compound 13.1: Prepare a solution of 3.0 g of 3-ethyl-2,4-dimethyl-1H-pyrrole (5.42 g, 44 mmol), 4-hydroxy-2,6-dimethylbenzaldehyde (20 mmol) in 300 mL of anhydrous dichloromethane. The solution was purged with N2 for 30 minutes and TFA (3 drops) was added. The resulting solution was stirred at room temperature for 16 hours. TFA and solvent were removed under reduced pressure. The crude product was used in the previous step without further purification. LCMS (APCI+): C 25H 35 Calculated for N2O (M+H) = 379; found: 379.

[0285] Compound 13.2: 8 g of DDQ (35.2 mmol) was added to the crude compound 13.1 [4-((4-ethyl-3,5-dimethyl-1H-pyrrol-2-yl)(4-ethyl-3,5-dimethyl-2H-pyrrol-2-yl)methyl)-3,5-dimethylphenol] and dissolved in 300 mL of anhydrous DCM. The resulting mixture was stirred at room temperature for 1 hour. The dark solution was loaded onto a silica gel column using CH2Cl2 / EtOAc as eluent to give 7.53 g of compound 13.2 (99% yield for two steps). LCMS (APCI+): C 25 H 33 Calculated for N2O (M+H) = 377; found: 377.

[0286] Compound 13.3: To a solution of 7.53 g of compound 13.2 [(Z)-4-((4-ethyl-3,5-dimethyl-1H-pyrrol-2-yl)(4-ethyl-3,5-dimethyl-2H-pyrrol-2-ylidene)methyl)-3,5-dimethylphenol] (20.0 mmol) dissolved in 300 ml of anhydrous toluene was added 16.72 mL of triethylamine (120 mmol) followed by 24.68 mL of BF3 etherate (200 mmol). The reaction solution was stirred at room temperature for 16 hours and then heated to 70°C for 1 hour. Next, the solution was cooled to room temperature and 50 mL of NaOH (1 M) was added. The layers were separated. The aqueous layer was neutralized with 4N HCl and extracted with EtOAc. The combined organic layers were dried over MgSO4 and the solvent was removed. The residue was chromatographed on a silica gel column using CH2Cl2 / EtOAc as eluent to give pure compound 13.3 (1.70 g, 20%). LCMS (APCI+): C 25 H 32 Calculated for BF2N2O (M+H) = 325; found: 325. 1 H NMR (400MHz, chloroform-d) δ6.56 (s, 2H), 4.77 (s, 0H), 2.46 (s, 6H), 2.24 (q, J = 7.6Hz, 4H), 2.01 (s, 6H), 1.27 (s, 6H), 0.92 (t, J = 7.5Hz, 6H).

[0287] PC-13: Under nitrogen atmosphere, 89.3 mg of DCC (0.433 mmol) was added to a solution containing 123 mg of compound 13.3 [4-(2,8-diethyl-5.5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'f][1,3,2]diazaborinyl-10-yl)-3,5-dimethylphenol] (0.289 mmol), 112 mg of compound 9.3 [3-(perylene-3-yl)propionic acid] (0.346 mmol), and 52.4 mg of DMAP (0.433 mmol) dissolved in 5.0 mL of anhydrous THF. The resulting solution was stirred at room temperature for 16 hours. Water was added, followed by 50 mL of DCM (50 ml). The mixture was passed through celite. The organic layer was separated and concentrated. The crude product was purified by silica gel column chromatography using hexane:DCM as eluent to give 95 mg of orange-red solid product with a yield of 45%. LCMS (APCI+): C 48 H 47 Calculated value for BF2N2O2 (M+H) = 732; Found: 732; 1 H NMR (400MHz, chloroform-d) δ8.31-8.16(m,4H),7.94(δ,J=8.4Hz,1H),7.72(δδ,J=8.1,4.4Hz,2H),7.59(t,J=7.92Hz,3H),7.53-7.45(m,3H),6.88 (s,2H),3.54(t,J=7.8Hz,2H),3.07(t,J=7.8Hz,2H),2.56(s,6H),2.33(q,J=7.5Hz,4H),2.15(s,6H),1.34(s,6H),1.01(t,J=7.5Hz,6H).

[0288] Example 2.14 PC-14:

[0289]

[0290] PC-14: Under nitrogen atmosphere, 212.5 mg of DCC (1.03 mmol) was added to a solution containing 175 mg of compound 13.3 [4-(2,8-diethyl-5,5-difluoro-1,3,7,9-tetramethyl-5H-414,514-dipyrrolo[1,2-c:2',1'f][1,3,2]diazaborinylcyclohexene-10-yl)-3,5-dimethylphenol] (412 mmol), 167 mg of compound 8.2 [4-(4-perylene-3-yl)butanoic acid] (0.494 mmol), and 124.8 mg of DMAP (1.03 mmol) dissolved in 15.0 mL of anhydrous THF. The resulting solution was stirred at room temperature for 16 hours. Water was added, followed by 150 mL of ethyl acetate. The solution was passed through celite. The organic layer was separated and concentrated. The crude product was purified by silica gel column chromatography using hexane:DCM as eluent to give 130 mg of orange-red solid product with a yield of 42%. LCMS (APCI+): C 49 H 49 Calculated for BF2N2O2 (M+H) = 746; found: 746. 1 H NMR (400MHz, chloroform-d) δ8.20-8.05(m,4H),7.88(δ,J=8.5Hz,1H),7.61(dd,J=8.1,5.0Hz,2H) ,7.48(t,J=8.0Hz,1H),7.41(td,J=7.9,2.4Hz,2H),7.33(δ,J=7.6Hz,1H),6.78(s,2H),5. 23(s,1H),3.42(s,2H),3.12(t,J=7.6Hz,2H),2.63(t,J=7.2Hz,2H),2.46(s,6H),2.20(δ θ,J=21.4,7.4Hz,6H),2.03(s,6H),1.47-1.42(m,3H),1.23(s,6H),0.92(t,J=7.5Hz,6H).

[0291] Example 2.15 PC-15:

[0292]

[0293] Compound 15.1 (cyano-2,4-dimethylpyrrole) was prepared using a four (4) step process.

[0294] Step 1: 7.6 mL of 25% HBr / AcOH was slowly added to 19.76 g of solid Boc-Gly-n-MeOMeA (90.4 mmol). The solution was stirred at room temperature for 45 min. Then, 200 mL of diethyl ether was added to the solution to obtain a white precipitate. The precipitate was filtered to obtain 18.03 g of glycine N'-methoxy-N'-formamide hydrobromide with a yield of 100%. LCMS (M+H): 119. 1 HNMR(DMSO-δ6)δ8.04(3H,s),3.9(s,2H),3.72(s,3H),3.17(s,3H).

[0295] Step 2: A solution containing 14.85 g of 3-aminocrotononitrile (180.8 mmol) and 17.95 g of glycine N'-methoxy-N'-methylamide hydrobromide (90.4 mmol) dissolved in 1 L of anhydrous ethanol was stirred at room temperature under an argon atmosphere for 16 hours. The resulting solution was concentrated in vacuo to a volume of 50 ml. The solid residue was washed with 40 mL of cold EtOH to give 16.71 g of a white solid. The solid was used in step 3 without further purification. LCMS (M+H) 184. 1 H NMR(DMSO-δ6)δ6.9(bs,1H),3.89(s,2H),3.78(s,1H),3.7(s,3H),3.12(s,3H),2.03(s,3H)

[0296] Step 3: Under nitrogen atmosphere, at -10 ° C, to a solution containing 3.82g of the white powder of step 2 (21.2mmol) dissolved in 150mL of anhydrous THF, 7.5mL of 3.0M MeMgBr in Et2O solution (1.1 equivalents) was added. The solution was stirred for 50min. Then, 15mL of 3.0M MeMgBr in Et2O solution (2.1 equivalents) was added under nitrogen atmosphere at -10 ° C and stirred for another 2 hours. After this, the solution was quenched with 200mL of water and extracted with AcOEt. The organic layer was washed with brine and dried over Na2SO4. Filtered and evaporated in vacuo. The product was a yellow solid, which was used in step 4 without further purification.

[0297] Step 4: To a slurry containing 2.67 g of the yellow solid from step 3 (19.3 mmol) in 75 mL of EtOH was added 273 mg of NaOEt (4.01 mmol, 0.2 eq.). The slurry was stirred at room temperature for 30 min. Next, the solution was evaporated in vacuo and the residue was dissolved in 100 mL of water and extracted with AcOEt. The organic layer was washed with brine and dried over MgSO4. Filtered, evaporated in vacuo, and the filtrate was purified by flash chromatography on silica gel (n-hexane:AcOEt 3:1 was the eluent). 2.09 g (90%) of cyano-2,4-dimethylpyrrole was obtained as a white solid. LCMS (APCI+): Calculated for C7H9N2 (M+H) = 121; Found: 121. 1 H NMR(CDCl3)δ8.06(bs,1H),6.37(1H,s),2.37(s,3H),2.13(s,3H)),3.74(1H,s),2.10(3H,s),2.02(3H,s).

[0298] Compound 15.2 ((Z)-5-((4-cyano-3,5-dimethyl-2H-pyrrole-2-ylidene)-(4-hydroxy-2,6-dimethylphenyl)methyl)-2,4-dimethyl-1H-pyrrole-3-carbonitrile) was synthesized using a two (2) step process:

[0299] Step 1: Under argon atmosphere, 1.12 g of 4-hydroxy-2,6-dimethylbenzaldehyde (7.49 mmol) was dissolved in 85 mL of dichloromethane / EtOH (9:1). 1.8 g of 2,4-dimethyl-1H-pyrrole-3-carbonitrile (14.98 mmol) was added. Then, the solution was purged with nitrogen for 30 minutes, and TFA (5 drops) was added. The reaction mixture was stirred at room temperature for 16 hours. TFA and solvent were removed under reduced pressure. The crude product was used in step 2 without further purification. LCMS (M+H=373).

[0300] Step 2: 8 g of DDQ (35.2 mmol) was added to a solution containing the crude product of step 1 dissolved in 50 mL CHCl3 and 5 mL EtOH. The solution was stirred at room temperature for 1 hour. The solvent was removed under reduced pressure. The dark residue was redissolved in 50 mL CHCl3 and passed through a silica gel short column using CH2Cl2 / EtOAc (1:1) as eluent to give 2.35 g of off-white solid. The total yield of the two steps was 85%. LCMS (APCI+): C 23 H 23 Calculated for N4O (M+H) = 371; found: 371.

[0301] Compound 15.3 (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]diazaborinyl-2,8-dicarbonitrile): To a solution of 2.35 g of compound 15.2 [(Z)-5-((4-cyano-3,5-dimethyl-2H-pyrrole-2-ylidene)-(4-hydroxy-2,6-dimethylphenyl)methyl)-2,4-dimethyl-1H-pyrrole-3-carbonitrile] (6.38 mmol) in 50 mL of anhydrous toluene was added 8 mL of triethylamine (52.2 mmol) followed by 10 mL of BF3 etherate (81 mmol). The solution was stirred at room temperature for 16 hours and then heated at 80°C for 1 hour. Next, the solution was cooled to room temperature and 25 mL of aqueous NaOH (1 M) was added to form an aqueous layer, which was separated. The aqueous layer was neutralized with 4N HCl aqueous solution and then extracted with EtOAc. The combined organic layers were dried over MgSO4 and the solvent was removed. The residue was chromatographed on a silica gel column using hexane / EtOAc (1:1) as eluent to give 1.05 g of product (39% yield). LCMS (APCI+): C 23 H 22 Calculated for BF2N4O (M+H) = 419; found: 419. 1 H NMR (400 MHz, CHLOROFORM-d) δ 6.73 (s, 2H), 2.73 (s, 6H), 2.05 (s, 6H), 1.64 (s, 6H).

[0302] PC-15: Under nitrogen atmosphere, 82.5 mg of DCC (0.4 mmol) was added to a solution containing 83.6 mg of compound 15.3 [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]diazaborohexene cyclo-2,8-dicarbonitrile (0.2 mmol), 81.1 mg of 4-(perylene-3-yl)butyric acid, compound 8.2 (0.24 mmol), and 48.4 mg of DMAP (0.4 mmol) dissolved in 4.0 mL of anhydrous THF. The solution was stirred at room temperature for 16 hours. Water was added, followed by 50 mL of ethyl acetate. The solution was passed through celite. The organic layer was separated and concentrated. The crude product was purified by silica gel column chromatography using hexane:EtOAc as eluent to give 45 mg of light yellow solid product with a yield of 30%. LCMS (APCI+): C 47 H 38Calculated for BF2N4O2 (M+H) = 739; found: 739. 1 H NMR (400MHz, chloroform-d) δ8.24 (δ, J = 7.5Hz, 1H), 8.24-8.12 (m, 3H), 7.94 (δ, J = 8. 4Hz,1H),7.68(δδ,J=8.2,3.5Hz,2H),7.55(t,J=7.9Hz,1H),7.48(t,J=7.3 Hz,2H),7.40(δ,J=7.7Hz,1H),6.88(s,2H),3.20(t,J=7.4Hz,2H),2.72(s, 6H), 2.70 (δ, J=7.1Hz, 1H), 2.28 (p, J=7.2Hz, 2H), 2.02 (s, 6H), 1.57 (s, 6H).

[0303] Example 2.16 PC-16:

[0304]

[0305] PC-16: Under nitrogen atmosphere, 41.26 mg of DCC (0.2 mmol) was added to a solution containing 41.8 mg of compound 15.3 [5,5-difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-1,3,7,9-tetramethyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarbonitrile] (0.1 mmol), 59.8 mg of compound 12.2 (4-(8,11-di-tert-butylperylene-3-yl)butanoic acid) (0.132 mmol), and 24.33 mg of DMAP (0.2 mmol) dissolved in 4.0 mL of anhydrous THF. The solution was stirred at room temperature for 16 hours. Water was added, followed by 50 mL of ethyl acetate. The solution was passed through celite. The organic layer was separated and concentrated. The crude product was purified by silica gel column chromatography using hexane:EtOAc as eluent to give 15 mg of orange-red solid product with a yield of 17%. LCMS (APCI+): C 55 H 53 Calculated for BF2N4O2 (M+H) = 850; found: 850. 1H NMR (400MHz, chloroform-d)δ8.24(q,J=8.5,7.1Hz,3H),8.17(δ,J=7.8Hz,1H),7.91(δ,J=8.4Hz,1H),7.63(δ,J=2.2Hz,2H),7.55(t,J=7.9Hz,1H),7.39(δ,J =7.8Hz,1H),6.89(s,2H),3.20(t,J=7.4Hz,2H),2.72(s,6H),2.70(t,J=7 .4Hz,2H),2.28(h,J=7.4Hz,2H),2.04(s,6H),1.56(s,6H),1.47(s,18H).

[0306] Example 2.17PC-17:

[0307]

[0308] Compound 17.1 ((1R,2R,3R,4S)-2-chloro-3-tosylbicyclo[2.2.1]heptane): Step 1: Norbornene (34.368 g, 365.0 mmol), sodium 4-methylbenzenesulfinate (108 g, 606.0 mmol), water (400 ml) and DCM (400 ml) were added to a 3 L two-necked round bottom flask with an oversized stir bar. While the mixture was stirred vigorously, iodine (92.7 g, 365 mmol) was added in portions, causing the color to fade to orange or yellow, and then more iodine was added (6 portions in 10 minutes). The two-phase mixture was stirred overnight at room temperature while protecting from light with aluminum foil. The next day, 400 mL of DCM and 400 mL of saturated NaHCO3 were added to the yellow emulsion and stirred vigorously for 10 minutes until distinct separated layers formed. The aqueous layer was extracted twice with 150 mL of DCM, the organic layers were combined, washed with 50 mL of saturated aqueous NaHSO, enough water was added to separate the layers, and then washed with 50 mL of brine. The combined organic layers were dried over NaSO, filtered, and concentrated on a rotary evaporator (water bath 60° C.) to give a waxy light yellow solid.

[0309] Step 2: Add 300 mL of toluene to the waxy light yellow product of step 1. Stir the mixture and then heat in a H2O bath until an iodosulfonate emulsion is formed. Transfer the iodosulfonate emulsion to a 3L two-necked round-bottom flask. Rinse the slurry remaining in the previous flask with anhydrous toluene (total volume of about 1 L). Cool the suspension to 0°C and add 54 mL (365 mmol) of DBU via a syringe under vigorous stirring. Monitor the reaction by LCMS and TLC.

[0310] When the reaction is complete, the precipitate is filtered and washed with toluene. The filter cake is dissolved in DCM / ethyl acetate and then washed with 1N HCl aqueous solution. Next, the organic layers are combined, dried over NaSO4, filtered, and concentrated to dryness. The resulting solid is then redissolved in hot ethyl acetate and hexane is added. The resulting solution is slowly cooled to room temperature. The crystals are filtered out and washed with hexane to give 63 g of light yellow crystals with a yield of 88%. The crystals are of sufficient purity to be used in the next step of 1521-64. LCMS (APCI+): C 14 H 16 Calculated value of O2S (M+H) = 249; Found: 249

[0311] Compound 17.2 ((4S,7R)-1-methyl-4,5,6,7-tetrahydro-2H-4,7-methyleneisoindole):

[0312]

[0313] Step 1: Under nitrogen atmosphere, a solution containing 60% NaH dispersed in 2.45 g (60.82 mmol) of paraffin liquid was placed in a 250 ml round bottom flask, and 50 mL of anhydrous THF was added; the suspension was cooled to 0°C. A mixture of 6.04 g of compound 17.1 [2-tosylbicyclo[2.2.1]hept-2-ene] (24.32 mmol) and 6.87 g of ethyl 2-isocyanatoacetate (60.82 mmol) in 50 mL of anhydrous THF was added dropwise to the suspension while maintaining the temperature at 0°C. The resulting mixture was stirred for another hour while maintaining the temperature at 0°C. After stirring for 1 hour, the cooling ice bath was removed, and the mixture was stirred for another 16 hours at room temperature under nitrogen atmosphere. After 16 hours, 2 mL of ethanol was added to quench the reaction. After quenching, 250 mL of ethyl acetate was added to the mixture, and the pH was adjusted to 5-4 with 3N HCl aqueous solution. The organic layer was separated, the aqueous layer was re-extracted with 100 ml of ethyl acetate, and the resulting organic layer was separated. The organic layers were combined, washed with water, dried over MgSO4 and concentrated. Hexane was added to the crude solid product for recrystallization to obtain 4.75 g of (4S,7R)-4,5,6,7-tetrahydro-2H-4,7-methyleneisoindole-1-carboxylic acid ethyl ester (100% yield), which was used in the next step without further purification. LCMS (APCI+): C 12 H 15 Calculated value for NO2 (M+H) = 206; Found: 206; 1H NMR (400MHz, chloroform-d) δ8.33(s,1H),6.52(δ,J=2.3Hz,1H),4.29(q,J=7.1Hz,2H),3.58(s,1H),3.28(s,1H),1 .96-1.87(m,2H),1.86(δδ,J=12.5,5.1Hz,2H),1.35(td,J=7.1,1.5Hz,3H),1.17(dq,J=17.6,10.0Hz,2H).

[0314] Step 2: A mixture of 0.734 g of (4S, 7R)-4,5,6,7-tetrahydro-2H-4,7-methyleneisoindole-1-carboxylic acid ethyl ester (4.991 mmol) in 15 mL of anhydrous THF was carefully added to a stirred slurry mixture of 36.5 mL of 2M LAH / THF (73.07 mmol) at 0°C under an argon atmosphere. Next, the reaction mixture was refluxed and stirred for 2 hours. The reaction was quenched by carefully adding MeOH at -15°C and then poured into ice water. The pH was adjusted to 6-7; 250 mL of ethyl acetate was added and the mixture was stirred for 30 minutes. The organic layer and the aqueous layer were left at room temperature overnight. The organic layer was separated and dried over MgSO4 and concentrated to a volume of 10 mL; 50 mL of hexane was added. The off-white solid was collected by suction filtration and washed with 40 mL of hexane to obtain 1.71 g of a white solid. The white solid was used in the next step without further purification. LCMS (APCI+): C 10 H 13 Calculated value of N(M+H)=148; Found: 148; 1 H NMR (400 MHz, CHLOROFORM-d) δ 7.19-7.14 (m, 1H), 6.24 (s, 1H), 3.23 (s, 1H), 3.20 (s, 1H), 2.19 (δ, J = 1.5 Hz, 3H), 1.87-1.74 (m, 2H), 1.60 (δ, J = 8.5 Hz, 2H), 1.19 (dt, J = 7.8, 2.1 Hz, 2H).

[0315] Compound 17.3: 4-((1S,4R,10R,13S)-7,7-difluoro-5,9-dimethyl-1,3,4,7,10,11,12,13-octahydro-2H-614,714-1,4:10,13-dimethylbridged [1,3,2]diazaborinylcyclo[4,3-a:6,1-a']diisoindol-14-yl)phenol

[0316]

[0317] Step 1: A solution of 0.734 g of compound 17.2 [(4S,7R)-1-methyl-4,5,6,7-tetrahydro-2H-4,7-methyleneisoindole] (4.991 mmol), 0.29 g of 4-hydroxybenzaldehyde (2.43 mmol) in 15 mL of anhydrous toluene was purged with argon for 15 minutes. Once purged, 2.0 mg (catalytic amount) of pTSA was added, followed by 1 mL of EtOH. The mixture was stirred at room temperature for 2 days. TLC and LCMS showed that the starting material had been consumed. The crude product was used in situ in the next step without further purification.

[0318] Step 2: 1.7 g DDQ (7.49 mmol) was added to the above step. The resulting mixture was stirred at room temperature for 2 hours. TLC and LCMS showed that the starting material had been consumed. The reaction mixture was filtered through diatomaceous earth. The diatomaceous earth was washed with 250 mL DCM. All filtrates were combined and concentrated. The crude product was used in the next step without further purification.

[0319] Step 3: The above crude product was redissolved in DCM (50 ml), cooled to 0°C, and then stirred with triethylamine (10.43 mL, 74.86 mmol) for 15 minutes, followed by the addition of 9.23 mL of BF3 etherate (74.86 mmol). The resulting reaction mixture was stirred at room temperature for 16 hours, then heated at 70°C for 1 hour, and then cooled at room temperature. Next, 5.0 mL of 1 N NaOH aqueous solution was added, and the layers were separated. The aqueous layer was neutralized with 1 N HCl and then re-extracted with ethyl acetate. The combined organic layers were dried over MgSO4 and the solvent was removed by rotary evaporation. The residue was chromatographed on a silica gel column using CHCl2 / EtOAc as eluent to give 0.12 g of the pure title product as an orange-red solid (11.0% yield). LCMS (APCI+): for formula C 27 H 27 Calculated value of BF2N2O; Found: 445, 1 H NMR (400 MHz, CHLOROFORM-d) δ 7.38 (s, 1H), 7.29-7.22 (m, 2H), 6.93 (, J = 8.1 Hz, 2H), 3.19 (s, 1H), 3.18 (s, 1H), 2.53 (s, 6H), 2.49-1.78 (m, 4H), 1.73-1.64 (m, 4H), 1.43-1.32 (m, 4H).

[0320] Compound PC-17:

[0321]

[0322] Under nitrogen atmosphere, a mixture of 29.9 mg of DCC (29.9 mg, 0.145 mmol) in anhydrous THF (0.5 mL) was added dropwise to compound 17.3 [4-((1S,4R,10R,13S)-7,7-difluoro-5,9-dimethyl-1,3,4,7,10,11,12,13-octahydro-2H-614,714-1,4:10,13-dimethylbridged] 1,3,2]diazaborinylcyclo[4,3-a:6,1-a']diisoindol-14-yl)phenol] (54 mg, 0.121 mmol), compound 12.2 (4-(8,11-di-tert-butylperylene-3-yl)butanoic acid) (54.5 mg, 0.121 mmol), DMAP (47.5 mg, 0.392 mmol) in anhydrous THF (2.0 ml). The resulting mixture was stirred at room temperature for 16. Water was added, followed by DCM (50 ml). The mixture was passed through diatomaceous earth. The organic layer was separated and concentrated. The crude product was purified by silica gel column chromatography with hexane:DCM as the eluent to give 70 mg of an orange-red solid product with a yield of 65%. LCMS (APCI+): C 48 H 47 Calculated value for BF2N2O2 (M+H) = 877; Found: 877, 1 HNMR (400 MHz, chloroform-d) δ8.27-8.23 (m, 3H), 8.19 (d, J = 7.7 Hz, 1H), 7.93 (d, J = 8.4 Hz, 1H), 7.63 (s, 1H), 7.62 (s, 1H), 7.54 (q, J = 9.4, 8.7 Hz, 2H), 7.41 (δ, J = 8.1, 4.6 Hz, 2H), 7.21 (δ, J = 7.6 Hz,2H),3.19(δ,J=11.5Hz,4H),2.75(t,J=7.2Hz,2H),2.53(s,6H),2.43-2.41(m,2H),2.2 9(q,J=7.6Hz,2H),1.8-1,7(m,2H),1.48(s,18H),1.39(d,J=8.7Hz,2H),1.26-1.06(m,4H).

[0323] Example 2.18 PC-18:

[0324]

[0325] Compound 17.1 (4-(8,11-di-tert-butylperylene-3-yl)butanoic acid 4-(5,5-difluoro-2,8-diiodo-1,3,7,9-tetramethyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-10-yl)-3,5-dimethylphenyl ester): Under nitrogen protection, a solution mixture of 21.01 g of N-iodosuccinimide (0.0993 mmol) in 1 mL of DCM was added dropwise to a mixture of 37.4 g of PC-12 (0.046 mmol) in 3 mL of anhydrous DCM / DMF (1:1) (v / v) at room temperature over 15 minutes. The resulting mixture was stirred at room temperature for 1 hour under argon atmosphere. The mixture was poured into 2 mL of water. The organic layer was separated, and the aqueous layer was re-extracted with 10 mL of ethyl acetate. Then, the organic layers were combined, dried over MgSO4, and concentrated. The crude product was used in the next step without further purification. LCMS (APCI+): C 53 H 53 Calculated value for BF2I2N2O2 (M+H) = 1053; found: 1053.

[0326] Compound PC-18 (4-(8,11-di-tert-butylperylene-3-yl)butyric acid 4-(5,5-difluoro-1,3,7,9-tetramethyl-2,8-bis(phenylethynyl)-5H-4-14,5-14-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-10-yl)-3,5-dimethylphenyl ester): A mixture of 48.4 mg of compound 17.1 (0.046 mmol), 1.75 mg of CuI (0.0092 mmol) and 2 mL of PdCl2(PPh3)2 in anhydrous toluene was bubbled with argon at room temperature for 15 minutes. 140.98 mg of phenylacetylene (1.38 mmol) was added, and then 1.6 mL of triethylamine (11.5 mmol) was added to the mixture. Then, the resulting mixture was stirred at 35°C for 2.5 hours. The mixture was diluted with 2.0 mL of water and then extracted into 10 mL of ethyl acetate. The organic layer was separated, dried over MgSO4, concentrated and purified by SiO2 column chromatography using hexane:ethyl acetate (9:1) as eluent. 5 mg of dark red solid product was obtained with a yield of 10%. LCMS (APCI+): C 69 H 63 Calculated value for BF2N2O2 (M+H) = 1002; found: 1002.

[0327] Example 2.19 PC-19:

[0328]

[0329] 5-Oxo-5-(perylene-3-yl)pentanoic acid DCC.DMAP.THF

[0330] PC-19: Under nitrogen atmosphere, a mixture of 87.07 mg DCC (0.422 mmol) dissolved in 1 mL of anhydrous THF was added dropwise to a mixture of 77.7 mg of compound 6.5 (0.211 mmol), 77.3 mg of 5-oxo-5-(perylene-3-yl)pentanoic acid (0.211 mmol) and 51.13 mg of DMAP (0.422 mmol) dissolved in 4.0 mL of anhydrous THF. The resulting mixture was stirred at room temperature for 16 hours. Then, 1 mL of water was added, followed by 15 mL of DCM. The mixture was passed through diatomaceous earth. The organic layer was separated and concentrated. The crude product was purified by silica gel column chromatography using hexane: DCM as an eluent. 102 mg of an orange-red solid product was obtained with a yield of 65%. LCMS (APCI+): calculated for C46H39BF2N2O3 (M+H) = 717; found: 717. 1 H NMR(400MHz, chloroform-d)δ8.60(δ,J=8.5Hz,1H),8.32-8.23(m,3H),8.20(d,J=8.0Hz,1H), 7.94(d,J=8.0Hz,1H),7.78(δ,J=8.1Hz,1H),7.73(δ,J=8.1Hz,1H),7.66-7.57(m,1H) ,7.53(t,J=7.8Hz,2H),6.92(s,2H),5.97(s,2H),5.30(s,2H),3.26(t,J=7.1Hz,2H) ,2.77(t,J=7.2Hz,2H),2.56(s,6H),2.29(p,J=7.1Hz,2H),2.14(s,6H),1.41(s,6H).

[0331] Example 2.20 PC-20:

[0332]

[0333] Compound 4-(8,11-di-tert-butylperylene-3-yl)-4-oxobutanoic acid: To a suspension mixture of 500 mg of compound 12.1 and 50 mL of MeOH was added 0.5 g of KOH (8.93 mmol). The mixture was stirred at 65 ° C for 3 hours. Then, the mixture was cooled to 0 ° C and acidified with 15 mL of 2N HCl aqueous solution. A light brown solid was precipitated. The crude product was collected by filtration and air-dried to obtain 490 mg. The product was used in the next step without further purification. LCMS (APCI+): C 32 H 32Calculated for O3 (M+H) = 467; found: 467.

[0334] PC-20: Under nitrogen atmosphere, a mixture of 68.91 mg of DCC (0.334 mmol) in 1 mL of anhydrous THF was added dropwise to a mixture of 61.49 mg of compound 6.5 (0.167 mmol), 77.59 mg of 4-(8,11-di-tert-butylperylene-3-yl)-4-oxobutanoic acid (0.167 mmol) and 40.47 mg of DMAP (0.334 mmol) dissolved in 4 mL of anhydrous THF. The resulting mixture was stirred at room temperature for 16 hours. 1 mL of water was added, followed by 15 mL of DCM. The mixture was passed through diatomaceous earth. The organic layer was separated and concentrated. The crude product was purified by silica gel column chromatography using hexane:DCM as eluent. 78 mg of orange-red solid product was obtained with a yield of 57%. LCMS (APCI+): C 52 H 53 Calculated value for BF2N2O3 (M+H) = 816; Found: 816, 1 HNMR(400MHz, chloroform-d)δ8.65(d,J=8.5Hz,1H),8.35-8.28(m,3H),8.24(δ,J=8.0H z,1H),8.03(δ,J=8.0Hz,1H),7.74(δ,J=1.7Hz,1H),7.69(δ,J=1.6Hz,1H),7.62 (δδ,J=8.6,7.6Hz,1H),6.98(s,2H),5.97(s,2H),3.54(t,J=6.3Hz,2H),3.10( t,J=6.3Hz,2H),2.56(s,6H),2.15(s,6H),1.49(d,J=3.1Hz,18H),1.42(s,6H).

[0335] Example 2.21 PC-21:

[0336]

[0337] Compound 21.1 ((E)-3-nitrohex-3-ene): A stirring bar was added to a 1-liter round-bottom flask and flushed with argon. Basic alumina (160 g), anhydrous dichloromethane (400 mL), propionaldehyde (400 mmol, 28.7 mL) and 1-nitropropane (400 mmol, 35.6 mL) were added to the flask. The flask was equipped with a long fin air condenser and placed in an oil bath at 45°C. The mixture was stirred for 3 days under an argon atmosphere and then cooled to room temperature. The reaction mixture was filtered and the filter cake was washed with dichloromethane. The filtrate was concentrated to a yellow oil by rotary evaporation. The material was purified by flash chromatography on silica gel using 10% ethyl acetate / hexanes to give 12.19 g of a yellow oil (23.6% yield). 1 H NMR (400 MHz, CHLOROFORM-d) δ 7.05 (t, J = 7.9 Hz, 1H), 2.61 (q, J = 7.4 Hz, 2H), 2.25 (p, J = 7.7 Hz, 2H), 1.12 (td, J = 7.5, 4.6 Hz, 6H).

[0338] Compound 21.2 (3,4-diethyl-1H-pyrrole-2-carboxylic acid ethyl ester): A stirring bar was added to a 250 mL round bottom flask and flushed with argon. Ethyl isocyanoacetate (38.7 mmol, 4.38 g) and (E)-3-nitrohex-3-ene (38.7 mmol, 5.00 g) were added to the flask. Anhydrous THF (50 mL) was added via a syringe, and DBU (38.7 mmol, 5.8 mL) was then added dropwise over 30 seconds with stirring (exothermic reaction occurred). The reaction was stirred at room temperature overnight. The reaction mixture was diluted with dichloromethane (200 mL) and partitioned with brine (200 mL). The layers were separated, the aqueous layer was extracted with dichloromethane (50 mL), and the combined organic layers were dried over MgSO4. The filtrate was concentrated by rotary evaporation to give the crude product. This material was purified by flash chromatography on silica gel using an ethyl acetate / hexanes gradient (5%→30% over 10 CV). 5.00 g, 66% yield. 1 H NMR (400MHz, chloroform-d) δ8.73(s,1H),6.67(d,J=2.9Hz,1H),4.31(q,J=7.1Hz,2H),2.75(q,J=7.5Hz ,2H),2.45(q,J=7.6Hz,2H),1.35(t,J=7.1Hz,3H),1.19(t,J=7.5Hz,3H),1.14(t,J=7.5Hz,3H).

[0339] Compound 21.3 (5,5'-(phenylmethylene)bis(3,4-diethyl-1H-pyrrole-2-carboxylic acid diethyl ester)): A stirring bar was added to a 500 mL round bottom flask and flushed with argon. Tetra(n-butyl)ammonium bromide (0.858 mmol, 277 mg), p-toluenesulfonic acid monohydrate (6.13 mmol, 1166 mg), and compound 21.2 (61.3 mmol, 11.96 g) were added to the flask. Anhydrous dichloromethane (200 mL) was added followed by benzaldehyde (36.8 mmol, 3.7 mL). The flask was sealed and stirred at room temperature overnight under argon. The crude reaction mixture was partitioned with saturated aqueous sodium bicarbonate solution (100 mL). The layers were separated and the organic layer was dried over MgSO4, filtered, and concentrated by rotary evaporation. The crude product was purified by flash chromatography using a dichloromethane / ethyl acetate gradient (1%→4%→10%) to give 14.1 g (96% yield). MS (APCI): C 29 H 38 Calculated for N2O4 (MH) = 477; found = 477. 1 H NMR (400MHz, chloroform-d) δ8.24(s,2H),7.40–7.30(m,3H),7.12(d,J=7.0Hz,2H),5.57(s,1H),4.28(q,J=7.1Hz,4H),2 .74(q,J=7.4Hz,4H), 2.32(q,J=7.5Hz,4H), 1.33(t,J=7.1Hz,6H), 1.17(t,J=7.4Hz,6H), 0.92(t,J=7.5Hz,6H).

[0340] Compound 21.4 (1,2,8,9-tetraethyl-5,5-difluoro-3,7-diiodo-10-phenyl 5H-4',5'-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinyl ring): A stirring bar was added to a 1 L round bottom flask. NaOH (6.00 g) and water (30 mL) were added to the flask. The mixture was stirred to obtain a solution, and the flask was flushed with argon. Compound 21.3 (29.4 mmol, 14.09 g) was added to the reaction flask, followed by ethanol (200 proof, 300 mL). The flask was equipped with a finned air condenser and heated in an oil bath at 90 °C under an argon atmosphere. After heating overnight, the reaction mixture was cooled to room temperature and transferred to a 1 L conical flask. While stirring in an ice-water bath, the pH was adjusted to 4 with 6N HCl aqueous solution. The mixture was diluted with water to a total volume of 1L, and the precipitate was collected via suction filtration. The moist precipitate was placed in a 3L 2-neck round-bottom flask, and a stirring rod was added to the flask. The flask was flushed with argon. A solution of sodium bicarbonate (188.2mmol, 15.81g) was prepared in water (300mL), and the solution was added to a reaction flask. Methanol (900mL) was added under stirring to obtain a solution. Under an argon atmosphere, iodine (58.8mmol, 14.92g) was added to the flask under vigorous stirring. The reaction mixture was stirred at room temperature overnight. The precipitated intermediate was filtered out and washed with water. The product was then dried at 50°C in a vacuum oven. The dried precipitate was dissolved in anhydrous dichloromethane (500mL) in a 1L 2-neck round-bottom flask purged with argon equipped with a stirring rod. The flask was sealed with a septum and cooled to -10°C (water-ice / methanol bath) under an argon atmosphere. BF3.OEt2 (571.2mmol, 70.5mL) was added to the flask by syringe under vigorous stirring. The flask was equipped with a dropping funnel, and anhydrous triethylamine (331.5mmol, 46.2mL) was placed in the dropping funnel. Triethylamine was added dropwise within 5 minutes under vigorous stirring. The cooling bath was removed, and the reaction mixture was stirred under an argon atmosphere and warmed to room temperature. The reaction was stirred overnight. The reaction was quenched by adding 1N HCl aqueous solution (200mL). The layers were separated, and the organic layer was washed with 1N HCl aqueous solution (200mL), saturated sodium bicarbonate aqueous solution (3×200mL) and brine (200mL) in turn. The organic layer was dried over MgSO4, filtered, and concentrated by rotary evaporation. Methanol was added to the crude purple-black liquid. The mixture was concentrated to dryness on diatomaceous earth and then purified by flash chromatography using a hexane / toluene gradient (80% toluene / hexane → 100% toluene). 640 mg (yield from compound 1.3: 4.0%) of a slightly red metallic solid was obtained. MS (APCI): C23 H 25 Calculated for BF2I2N2(MH) = 631; found = 631. 1 H NMR (400MHz, chloroform-d) δ7.58-7.48(m,1H),7.49-7.37(m,4H),2.35(q,J=7.7Hz,4H),2.34(q,J=7.5Hz,4H),1.18(t,J=7.5Hz,6H),1.06(t,J=7.5Hz,6H).

[0341] PC-21 (1,2,8,9-tetraethyl-5,5-difluoro-3,7,10-triphenyl-5H-4,14,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinyl ring): A 250 mL 2-necked round bottom flask was charged with a stirring bar and equipped with a reflux condenser and flushed with argon. Compound 21.4 (1.01 mmol, 640 mg), Pd(dppf)Cl2 (0.067 mmol, 49 mg) and phenylboronic acid (5.05 mmol, 616 mg) were added to the flask. Inhibitor-free THF (20 mL) and toluene (20 mL) were added, followed by 1.0 M aqueous K2CO3 solution (5.05 mmol, 5.05 mL). The flask was purged of oxygen by three cycles of vacuum / backfilling with argon. The flask was heated in an oil bath at 70°C for four hours. Additional portions of phenylboronic acid (5.05 mmol, 616 mg) and aqueous K2CO3 (5.05 mL) were added and the reaction was heated at 70°C for an additional 2 hours. The reaction mixture was cooled to room temperature and partitioned with ethyl acetate (150 mL). The mixture was washed with saturated aqueous sodium bicarbonate (3×25 mL) and brine (25 mL). The reaction mixture was dried over MgSO4, filtered, and concentrated to dryness on a rotary evaporator. The crude product was purified by flash chromatography using an ethyl acetate / hexane gradient (30% ethyl acetate / hexane (1CV) → 100% ethyl acetate / hexane (10CV)). The fractions containing the product were concentrated in vacuo and triturated with methanol to remove co-eluted impurities. 159 mg (30% yield) was obtained. MS (APCI): C 35 H 35 Calculated for BF2N2(MH) = 531; found = 531. 1 H NMR (400MHz, chloroform-d) δ7.58-7.40(m,9H),7.39-7.29(m,6H),2.17(q,J=7.4Hz,4H),1.66(q,J=7.4Hz,4H),0.80(t,J=7.5Hz,6H),0.73(t,J=7.4Hz,6H).

[0342] Example 2.22 PC-22:

[0343]

[0344] PC-22 (3,7-bis(4-ethoxyphenyl)-1,2,8,9-tetraethyl-5,5-difluoro-10-phenyl-5H-4,14,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinyl ring): This compound was synthesized from compound 21.4 in a similar manner to PC-21 using 4-ethoxyphenylboronic acid. MS (APCI): C 39 H 43 Calculated for BF2N2O2 (MH) = 619; found = 619. 1 H NMR (400MHz, chloroform-d) δ7.49-7.38(m,5H),7.31(d,J=8.7Hz,4H),6.80(d,J=8.7Hz,4H),3.96(q,J=7.0Hz,4H),2. 12(q,J=7.5Hz,4H), 1.57(q,J=7.4Hz,4H), 1.34(t,J=7.0Hz,6H), 0.74(t,J=7.5Hz,6H), 0.65(t,J=7.4Hz,6H).

[0345] Example 2.23 PC-23:

[0346]

[0347] PC-23: A 25 mL 2-necked round bottom flask was charged with compound 21.4 (0.286 mmol, 180 mg), CuI (0.014 mmol, 2.7 mg), Pd(OAc)2 (0.014 mmol, 3.2 mg), triphenylphosphine (0.003 mmol, 7.5 mg) and a stirring bar. The flask was flushed with argon. Anhydrous triethylamine (1 mL) and anhydrous DMF (1 mL) were added to the flask. The sealed flask was placed in an oil bath at 80°C and stirred at this temperature overnight. The cooled reaction mixture was diluted with 1N HCl aqueous solution (50 mL) and extracted with ether (3×40 mL). The combined organic layers were washed with water (3×40 mL) and brine (40 mL), then dried over MgSO4, filtered and concentrated in vacuo. The material was purified by flash chromatography (toluene / hexane gradient, 70% toluene / hexane→100% toluene (3CV)→100% toluene). 69 mg (41% yield) were obtained. MS (APCI): C 39 H 35 Calculated for BF2N2(MH) = 579; found = 579.1 H NMR (400MHz, chloroform-d) δ7.73-7.66(m,4H),7.55-7.42(m,5H),7.41-7.36(m,6H),2.50( q,J=7.5Hz,4H), 1.62(q,J=7.4Hz,4H), 1.20(t,J=7.5Hz,6H), 0.69(t,J=7.4Hz,6H).

[0348] Example 2.24 PC-24:

[0349]

[0350] Compound 24.1 (1-((2-iodocyclohexyl)sulfonyl)-4-methylbenzene): A stirring bar and dichloromethane (80 mL) were added to a 500 mL round bottom flask. To the flask were added hexene ring (73.1 mmol, 7.4 mL), sodium p-toluenesulfonate (121.3 mmol, 21.62 g), and water (80 mL). The biphasic mixture was stirred very vigorously and iodine (73.1 mmol, 18.55 g) was added in portions over 10 minutes, causing the color to fade to light yellow before the next portion was added. The mixture was stirred at room temperature for 4 hours. The reaction mixture was diluted with dichloromethane (80 mL). The mixture was partitioned with saturated aqueous sodium bicarbonate solution (100 mL), and the layers were separated. The organic layer was washed with saturated aqueous sodium bisulfite solution (10 mL) and brine (10 mL). The organic layer was dried over MgSO4, filtered, and concentrated in vacuo to give a colorless oil which quickly turned black and was used immediately in the next step.

[0351] Compound 24.2 (1-(Cyclohex-1-ene-1-ylsulfonyl)-4-methylbenzene): Compound 24.1 (73.1 mmol) from the previous step was diluted in anhydrous toluene (200 mL) in a 250 mL round-bottom flask equipped with a stirring bar. DBU (73.1 mmol, 10.8 mL) was added to the flask over 1 minute with vigorous stirring. A precipitate was formed. After 30 minutes, the precipitate was filtered off and washed with toluene. The combined organic layers were extracted with 1N aqueous HCl solution (20 mL), water (20 mL), saturated aqueous sodium bicarbonate solution (40 mL), and brine (40 mL). The organic layer was dried over MgSO4, filtered, and concentrated in vacuo. The crude product was pure enough for subsequent reactions. 14.46 g (84% yield) was obtained. 1H NMR (400 MHz, CHLOROFORM-d) δ 7.76 (d, J = 8.3 Hz, 2H), 7.34 (d, J = 8.0 Hz, 2H), 7.08-7.01 (m, 1H), 2.45 (s, 3H), 2.27 (dp, J = 8.5, 3.0, 2.5 Hz, 2H), 2.18 (tq, J = 6.3, 2.2 Hz, 2H), 1.73-1.62 (m, 2H), 1.62-1.54 (m, 4H).

[0352] Compound 24.3 (ethyl 4,5,6,7-tetrahydro-2H-isoindole-1-carboxylate): A 1 L 2-necked round bottom flask was equipped with an addition funnel and a stirring bar was added. The flask was thoroughly flushed with argon and sodium hydride (95%, 153 mmol, 3.672 g) was added to the flask followed by anhydrous THF (125 mL). A solution of compound 24.2 (61.2 mmol, 14.46 g) and ethyl isocyanoacetate (153 mmol, 16.7 mL) in anhydrous THF (125 mL) was added to the addition funnel. The reaction flask was placed in an ice-water bath and the solution was added dropwise over 15 minutes with vigorous stirring. The reaction mixture was stirred at 0°C for 2 hours and then the cooling bath was removed. The reaction mixture was stirred under argon for 80 hours and then the reaction was quenched by the addition of methanol (30 mL). Saturated aqueous sodium bicarbonate solution (30 mL) was added and the volatiles were removed on a rotary evaporator. The residue is distributed with ethyl acetate (125mL), brine (30mL) and water (100mL). Each layer is separated. The aqueous layer is extracted with dichloromethane (50mL), and the combined organic layer is washed with brine (50mL). The organic layer is dried over MgSO4, filtered, and concentrated in vacuo. The crude product is purified by flash chromatography using ethyl acetate / hexane gradient (15% ethyl acetate / hexane (1CV) → 30% ethyl acetate / hexane (10CV)). 7.74g waxy white solid (66% yield) is obtained. 1 H NMR (400 MHz, CHLOROFORM-d) δ 8.75 (s, 1H), 6.64 (d, J = 2.9 Hz, 1H), 4.29 (q, J = 7.1 Hz, 2H), 2.81 (t, J = 6.0 Hz, 2H), 2.54 (t, J = 5.8 Hz, 2H), 1.80-1.67 (m, 4H), 1.34 (t, J = 7.1 Hz, 3H).

[0353] Compound 24.4 (3,3'-(phenylmethylene)bis(4,5,6,7-tetrahydro-2H-isoindole-1-carboxylic acid diethyl ester)): Compound 24.3 (40.2 mmol, 7.76 g) was subjected to a procedure similar to that of compound 21.3 to isolate 9.30 g of the product (98% yield) after flash chromatography. MS (APCI): C 29 H 34 Calculated for N2O4 (MH) = 473; found = 473. 1 H NMR (400 MHz, CHLOROFORM-d) δ 7.37-7.27 (m, 3H), 7.11 (d, J = 6.9 Hz, 2H), 5.39 (s, 1H), 4.24 (q, J = 7.1 Hz, 4H), 2.79 (t, J = 6.1 Hz, 4H), 2.25-2.10 (m, 4H), 1.77-1.61 (m, 8H), 1.31 (t, J = 7.1 Hz, 6H).

[0354] Compound 24.5 (7,7-difluoro-5,9-diiodo-14-phenyl-1,3,4,7,10,11,12,13-octahydro-2H-6-14,7-14-[1,3,2]diazaborolinacyclo[4,3-a:6,1-a']diisoindole): Compound 24.4 (15.4 mmol, 7.30 g) was subjected to a procedure similar to that of (E)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)ethyl acrylate. 2.12 g (22% yield) was obtained. MS (APCI): C 23 H 21 Calculated for BF2I2N2(MH) = 627; found = 627. 1 H NMR (400 MHz, CHLOROFORM-d) δ 7.49 (dd, J = 5.0, 2.0 Hz, 3H), 7.29-7.21 (m, 2H), 2.30 (t, J = 6.3 Hz, 4H), 1.65-1.50 (m, 8H), 1.46-1.33 (m, 4H).

[0355] PC-24 (5,9-bis(3,3-dimethylbut-1-yn-1-yl)-7,7-difluoro-14-phenyl-1,3,4,7,10,11,12,13-octahydro-2H-6',7'-[1,3,2]diazaborolino[4,3-a:6,1-a']diisoindole): Compound 24.5 (0.200 mmol, 126 mg), Pd(PPh3)2Cl2 (0.020 mmol, 14.0 mg), CuI (0.060 mmol, 11.4 mg) and a stirring bar were charged into a vial. Diisopropylamine (2 mL) and toluene (2 mL) were added to the vial. The vial was sealed with a septum and purged of oxygen by vacuum / backfilling with argon cycles (three times). The vial was heated at 60°C for 1 minute, then tert-butylacetylene (6.00 mmol, 736 uL) was added via syringe. The reaction was heated at 60°C overnight. Similar workup and purification of compound 3 gave 81 mg of product (75% yield). MS (APCI): C 35 H 39 Calculated for BF2N2(MH) = 535; found = 535. 1 H NMR (400 MHz, CHLOROFORM-d) δ 7.49-7.40 (m, 3H), 7.25-7.17 (m, 2H), 2.40 (t, J=6.3 Hz, 4H), 1.66-1.48 (m, 8H), 1.45-1.31 (m, 22H).

[0356] Example 2.25 PC-25:

[0357]

[0358] PC-25 (7,7-difluoro-5,9-di(hex-1-yn-1-yl)-14-phenyl-1,3,4,7,10,11,12,13-octahydro-2H-614,714-[1,3,2]diazaborinylcyclo[4,3-a:6,1-a']diisoindole): PC-25 was synthesized from compound 24.5 (0.200 mmol, 126 mg) and 1-hexyne in a similar manner to PC-24 to give 43 mg (40% yield). MS (APCI): C 35 H 39 Calculated for BF2N2(MH) = 535; found = 535. 1H NMR(400MHz,THF-d8)δ7.42-7.35(m,3H),7.24-7.17(m,2H),2.47(t,J=6.8Hz,4H) ,2.33-2.25(m,4H),1.59-1.40(m,16H),1.34-1.23(m,4H),0.86(t,J=7.2Hz,6H).

[0359] Example 2.26 PC-26:

[0360]

[0361] PC-26 (7,7-difluoro-14-phenyl-1,3,4,7,10,11,12,13-octahydro-2H-6,14,714-[1,3,2]diazaborolinacyclo[4,3-a:6,1-a']diisoindole-5,9-dicarboxylic acid diethyl ester): A stirring bar was added to a 1-liter 3-necked round bottom flask and flushed with argon. Compound 24.4 (19.00 mmol, 9.00 g) and anhydrous dichloromethane (380 mL) were added to the flask. The flask was equipped with an addition funnel. DDQ (22.8 mmol, 5.176 g) and anhydrous THF (380 mL) were charged to the addition funnel. The reaction flask was cooled in an ice-water bath and the DDQ solution was added dropwise over a period of 20 minutes with vigorous stirring. Once LCMS showed complete oxidation, anhydrous triethylamine (114mmol, 15.9mL) was added via a syringe at 0°C under stirring, followed by BF3.OEt2 (190mmol, 23.5mL). The mixture was stirred and slowly warmed to room temperature within 2 hours. The water bath was removed, and the addition funnel was removed and replaced with a finned air condenser. The reaction was heated in an oil bath at 40°C overnight. After 16 hours, the temperature of the oil bath was raised to 50°C for 24 hours, and then raised to 60°C for 10 hours. The reaction mixture was stirred at room temperature for another 72 hours. Volatiles were removed by rotary evaporation, and the residue was dissolved in ethyl acetate (600mL). The organic layer was washed with 2N HCl aqueous solution (2×300mL) and brine (100mL). The organic layer was dried over MgSO4, filtered and evaporated in vacuo. The crude product was purified by flash chromatography using an ethyl acetate / hexane gradient (20% ethyl acetate / hexane (1CV) → 60% ethyl acetate / hexane (5CV)). The product fractions were collected and evaporated to dryness. The material was triturated with 1:1 DCM:hexane (300 mL) and the white solid was removed by filtration. The DCM was evaporated and the solid product was collected by filtration. 5.978 g (61% yield) was obtained. MS (APCI): C 29 H 31Calculated for BF2N2O4(MH) = 519; found = 519. 1 H NMR (400 MHz, CHLOROFORM-d) δ 7.55-7.49 (m, 3H), 7.25-7.20 (m, 2H), 4.44 (q, J = 7.1 Hz, 4H), 2.57 (t, J = 6.3 Hz, 4H), 1.70-1.48 (m, 8H), 1.47-1.34 (m, 10H).

[0362] Example 2.27 PC-27:

[0363]

[0364] Compound 27.1 (3,3'-((2,6-dimethylphenyl)methylene)bis(4,5,6,7-tetrahydro-2H-isoindole-1-carboxylic acid) diethyl ester): Compound 24.3 (30.0 mmol, 5.798 g) was reacted with 2,6-dimethylbenzaldehyde (18.0 mmol, 2.41 mL) in a manner similar to compound 24.4, except that the reaction was heated to 40 °C until the reaction was complete. After purification by flash chromatography on silica gel, 6.978 g of the product was isolated with a yield of 93%. MS (APCI): C 31 H 38 Calculated value for N2O4(MH)=501; found=501. 1 H NMR (400MHz, chloroform-d) δ8.26 (s, 2H), 7.16-7.08 (m, 1H), 7.04 (d, J = 7.5Hz, 2H), 5.73 (s, 1H), 4.31-4.19 (m, 4H), 2.7 9(t,J=5.8Hz,4H),2.23-2.11(m,2H),2.04(s,6H),2.01-1.86(m,2H),1.80-1.58(m,8H),1.32(t,J=7.1Hz,6H).

[0365] Compound 27.2 (14-(2,6-dimethylphenyl)-7,7-difluoro-5,9-diiodo-1,3,4,7,10,11,12,13-octahydro-2H-6-14,7-14-[1,3,2]diazaborinylcyclo[4,3-a:6,1-a']diisoindole): Compound 27.2 was synthesized in a manner similar to compound 24.4. In several steps and after purification by flash chromatography on silica gel, 2.45 g (40% yield) was obtained from compound 27.1 (9.34 mmol, 4.17 g). MS (APCI): C 25 H 25Calculated for BF2I2N2(MH) = 655; found = 655. 1 H NMR (400 MHz, CHLOROFORM-d) δ 7.31-7.22 (m, 1H), 7.12 (d, J = 7.5 Hz, 2H), 2.31 (t, J = 6.3 Hz, 4H), 1.65-1.56 (m, 4H), 1.52-1.46 (m, 4H), 1.46-1.37 (m, 4H).

[0366] PC-27 (14-(2,6-dimethylphenyl)-7,7-difluoro-5,9-bis(phenylethynyl)-1,3,4,7,10,11,12,13-octahydro-2H-614,714-[1,3,2]diazaborolino[4,3-a:6,1-a']diisoindole): PC-27 was synthesized from compound 27.2 (0.200 mmol, 131 mg) in a similar manner to compound 25 using triethylamine (3 mL) and toluene (3 mL) as solvents at 60 °C to give 48 mg (40% yield) after flash chromatography. MS (APCI): C 41 H 35 Calculated for BF2N2(MH) = 603; found = 603. 1 H NMR (400MHz, chloroform-d) δ7.71-7.64(m,1H),7.41-7.34(m,2H),7.30-7.23(m,1H),7.21-7.10(m,4H ), 2.55 (t, J = 6.2Hz, 4H), 2.15 (s, 6H), 1.68-1.59 (m, 4H), 1.59-1.52 (m, 4H), 1.51-1.43 (m, 4H).

[0367] Example 2.28 PC-28:

[0368]

[0369] PC-28 (5,9-bis((E)-3,3-dimethylbut-1-en-1-yl)-14-(2,6-dimethylphenyl)-7,7-difluoro-1,3,4,7,10,11,12,13-octahydro-2H-614,714-[1,3,2]diazaborolinacyclo[4,3-a:6,1-a']diisoindole): PC-28 was synthesized from compound 27.2 (0.200 mmol, 131 mg) and (E)-(3,3-dimethylbut-1-en-1-yl)boronic acid (1.00 mmol, 128 mg) in a similar manner to compound 21 to give 54 mg (yield 47%). MS (APCI): C 37 H 47Calculated for BF2N2(MH) = 567; found = 567. 1 H NMR (400MHz, chloroform-d) δ7.26-7.15(m,1H),7.12-7.01(m,4H),6.41(d,J=16.7Hz,2H),2.55(t,J=6 .2Hz,4H),2.12(s,6H),1.66-1.55(m,4H),1.55-1.48(m,4H),1.47-1.37(m,4H),1.18(s,18H).

[0370] Example 2.29 PC-29:

[0371]

[0372] Compound 29.1 (ethyl (E)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)acrylate): An oven-dried 250 mL 2-neck round bottom flask and a stir bar were cooled to room temperature under argon. Anhydrous THF (30 mL) was added to the flask followed by CuCl (1.8 mmol, 178 mg), NaOtBu (3.6 mmol, 346 mg) and xantphos (1.8 mmol, 1.042 g). The reaction was stirred at room temperature for 3 hours and then 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bis(1,3,2-dioxaborolan) (66.0 mmol, 16.757 g) was added followed by an additional aliquot of anhydrous THF (30 mL). The reaction mixture was stirred at room temperature for 15 minutes, then ethyl propiolate (60.0 mmol, 6.0 mL) was added, followed by anhydrous methanol (120 mmol, 4.85 mL). Stirring was continued at room temperature under argon. 1 The reaction was monitored by H NMR (loss of alkyne CH) for about 24 hours. The reaction mixture was filtered to remove insoluble material. The filtrate was concentrated in vacuo to give an oil which was purified by flash chromatography (ethyl acetate / hexane gradient, 100% hexane (1CV) → 40% ethyl acetate / hexane (5CV) → 70% ethyl acetate / hexane (2CV)). The fractions containing the product were collected and concentrated in vacuo to give a light yellow oil, 10.557 g (80% yield). 1 H NMR (400 MHz, CHLOROFORM-d) δ 6.77 (d, J = 18.2 Hz, 1H), 6.63 (d, J = 18.2 Hz, 1H), 4.21 (q, J = 7.1 Hz, 2H), 1.32-1.25 (m, 15H).

[0373] PC-29 (3,3'-(7,7-difluoro-14-phenyl-1,3,4,7,10,11,12,13-octahydro-2H-6',7'-[1,3,2]diazaborolinacyclo[4,3-a:6,1-a']diisoindole-5,9-diyl)(2E,2'E)-diethyl diacrylate): PC-29 was synthesized from compound 24.5 (0.200 mmol, 131 mg) and compound 29.1 (1000 μmol, 226 mg) at 50 °C in a manner similar to PC-28 to give 99 mg (87% yield). MS (APCI): C 33 H 35 Calculated for BF2N2O4(MH) = 571; found = 571. 1 H NMR (400 MHz, CHLOROFORM-d) δ 8.21 (d, J = 16.4 Hz, 2H), 7.59-7.42 (m, 3H), 7.30-7.22 (m, 2H), 6.48 (d, J = 16.4 Hz, 2H), 4.31 (q, J = 7.1 Hz, 4H), 2.59 (t, J = 6.3 Hz, 4H), 1.72-1.57 (m, 8H), 1.47-1.40 (m, 4H), 1.37 (t, J = 7.1 Hz, 6H).

[0374] Example 2.30 PC-30:

[0375]

[0376] Compound 30.1 (tert-butyl (E)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)acrylate): Compound 30.1 was synthesized from tert-butyl propiolate (30.0 mmol, 4.12 mL) in a manner similar to compound 29.1 to afford 4.547 g (60% yield) as a waxy white solid. 1 H NMR (400 MHz, CHLOROFORM-d) δ 6.68 (d, J = 18.2 Hz, 1H), 6.57 (d, J = 18.2 Hz, 1H), 1.48 (s, 9H), 1.28 (s, 12H).

[0377] PC-30 (3,3'-(7,7-difluoro-14-phenyl-1,3,4,7,10,11,12,13-octahydro-2H-6',7'-[1,3,2]diazaborolinacyclo[4,3-a:6,1-a']diisoindole-5,9-diyl)(2E,2'E)-ditert-butyl diacrylate): PC-30 was synthesized from compound 24.5 (0.167 mmol, 105 mg) and compound 30.1 (0.418 mmol, 106 mg) at 50°C in a manner similar to compound 29 to give 61 mg (58% yield). MS (APCI): C 37 H 43 Calculated for BF2N2O4(MH) = 627; found = 627. 1 H NMR (400 MHz, CHLOROFORM-d) δ 8.13 (d, J = 16.4 Hz, 2H), 7.56-7.46 (m, 3H), 7.32-7.21 (m, 2H), 6.40 (d, J = 16.4 Hz, 2H), 2.58 (t, J = 6.3 Hz, 4H), 1.69-1.57 (m, 8H), 1.55 (s, 18H), 1.47-1.34 (m, 4H).

[0378] Example 2.31 PC-31:

[0379]

[0380] Compound 31.1 (methyl 4-oxo-4-(perylene-3-yl)butanoate): A solution of methyl 4-chloro-4-oxobutanoate (8.45 mmol, 1.04 mL) in anhydrous dichloromethane (160 mL) was cooled to 0° C. under nitrogen. The solution was treated with AlCl (10.00 mmol, 1.34 g) in small portions via a powder dispersing funnel over 15 minutes. The solution was stirred at 0° C. for 1 hour, and then a solution of perylene (7.9 mmol, 2.00 g) in anhydrous DCM was added dropwise to the reaction mixture under stirring at 0° C. The resulting dark purple solution was stirred at room temperature for 24 hours under nitrogen. The reaction mixture was added to a mixture of ice-cold water (75 mL), 6N HCl aqueous solution (5 mL) and dichloromethane (150 mL). The layers were separated, and the aqueous layer was extracted with ethyl acetate (100 mL). The combined organic layers were dried over MgSO4, filtered, and concentrated in vacuo. The product was purified by flash chromatography using dichloromethane eluent to give 1.8 g of an orange solid (62% yield). MS (APCI): C 25 H 19 Calculated for O3 (M+H) = 367; found; 367.

[0381] Compound 31.2 (4-(perylene-3-yl)butanoic acid): To a solution of compound 31.1 (9.28 mmol, 3.4 g) in ethylene glycol (30 mL) in a pressure bottle was added 98% hydrazine hydrate (53 mmol, 2.7 mL). To the mixture was added powdered KOH (69.8 mmol, 3.91 g). The resulting mixture was stirred at 80°C for 15 minutes, then heated to 140°C and argon was bubbled in via slow bubbling for 2 hours. The argon atmosphere was maintained with a balloon, and the reaction was heated at 190°C for 16 hours. The reaction mixture was cooled to room temperature and diluted with water. The reaction mixture was filtered through celite, and the filtrate was acidified with 6N aqueous HCl. The green solid was collected by filtration and washed with water. The resulting solid was dried in a vacuum oven to give 3.0 g (95% yield). MS (APCI): C 25 H 19 Calculated for O3 (M+H) = 339; found: 339. 1 H NMR (400MHz, DMSO-d6) δ12.03(s,1H),8.38(d,J=7.6Hz,1H),8.35(d,J=7.5Hz,1H) ,8.32(d,J=7.6Hz,1H),8.29(d,J=7.8Hz,1H),7.99(d,J=8.4Hz,1H),7.77(t,J=7.4 Hz,2H),7.59(t,J=7.9Hz,1H),7.54(t,J=7.8Hz,1H),7.53(t,J=7.8Hz,1H),7.40(d ,J=7.7Hz,1H),3.02(t,J=7.6Hz,2H),2.37(t,J=7.2Hz,2H),1.91(d,J=7.3Hz,2H).

[0382] Compound 31.3 (3,3'-((4-bromo-2,6-dimethylphenyl)methylene)bis(4,5,6,7-tetrahydro-2H-isoindole-1-carboxylic acid diethyl ester)): Compound 31.3 was synthesized from compound 24.3 (13.36 mmol, 2.582 g) and 4-bromo-2,6-dimethylbenzaldehyde (8.02 mmol, 1.708 g) in a manner similar to the synthesis of compound 24.4, and refluxed at 50°C for a long time to drive the reaction to completion. After purification by flash chromatography on silica gel, 3.63 g (94% yield) was obtained. MS (APCI): C 31 H 37 Calculated for BrN2O4 (MH) = 579; found = 579. 1H NMR (400 MHz, methylene chloride-d2) δ 8.33 (s, 2H), 7.23 (s, 2H), 5.70 (s, 1H), 4.27-4.12 (m, 4H), 2.85-2.69 (m, 4H), 2.22-2.07 (m, 2H), 2.02 (s, 6H), 2.01-1.88 (m, 2H), 1.82-1.57 (m, 8H), 1.29 (t, J = 7.1 Hz, 6H).

[0383] Compound 31.4 (14-(4-bromo-2,6-dimethylphenyl)-7,7-difluoro-5,9-diiodo-1,3,4,7,10,11,12,13-octahydro-2H-614,714-[1,3,2]diazaborinylcyclo[4,3-a:6,1-a']diisoindole): Compound 31.4 was synthesized from compound 31.3 (6.25 mmol, 3.63 g) in a similar manner to compound 27.2 to give 3.294 g (72% yield). MS (APCI): C 25 H 24 Calculated for BBrF2I2N2(MH) = 733; found = 733.

[0384] Compound 31.5 (3,3'-(14-(4-bromo-2,6-dimethylphenyl)-7,7-difluoro-1,3,4,7,10,11,12,13-octahydro-2H-614,714-[1,3,2]diazaborolinacyclo[4,3-a:6,1-a']diisoindole-5,9-diyl)(2E,2'E)-diethyl diacrylate): Compound 31.5 was synthesized from compound 31.4 (0.200 mmol, 147 mg) and compound 29.1 (0.440 mmol, 99 mg) in a manner similar to PC-29 to give 117 mg of product (86% yield). MS (APCI): C 35 H 38 B Br Calculated for F2N2O4(MH) = 677; found = 677. 1 H NMR (400MHz, chloroform-d) δ8.20(d,J=16.4Hz,2H),7.34(s,2H),6.48(d,J=16.4Hz,2H),4.31(q,J=7.1Hz,4 H), 2.60 (t, J = 6.1Hz, 4H), 2.12 (s, 6H), 1.73-1.56 (m, 8H), 1.54-1.46 (m, 4H), 1.37 (t, J = 7.1Hz, 6H).

[0385] Compound 31.6 (3,3'-(7,7-difluoro-14-(2'-hydroxy-3,5-dimethyl-[1,1'-biphenyl]-4-yl)-1,3,4,7,10,11,12,13-octahydro-2H-6',7'-[1,3,2]diazaborolinacyclo[4,3-a:6,1-a']diisoindole-5,9-diyl)(2E,2'E)-diethyl diacrylate): Compound 31.6 was synthesized from compound 31.5 (0.144 mmol, 98 mg) and 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol (0.720 mmol, 159 mg) in a manner similar to that used for compound 31.5, except that the temperature was increased to 80°C to provide reaction at the bromine atom. After flash chromatography, 73 mg (73% yield) of the product was isolated. MS (APCI): C 41 H 43 Calculated for BF2N2O5 (MH) = 691; found = 691. 1 H NMR (400MHz, chloroform-d) δ8.22(d,J=16.4Hz,2H),7.36-7.27(m,4H),7.08-6.95(m,2H),6.50(d,J=16.4Hz,2H),4.32 (q,J=7.1Hz,4H),2.66-2.56(m,4H),2.20(s,6H),1.74-1.60(m,8H),1.54-1.44(m,4H),1.37(t,J=7.1Hz,6H).

[0386] PC-31 (3,3'-(14-(3,5-dimethyl-2'-((4-(perylene-3-yl)butanoyl)oxy)-[1,1'-biphenyl]-4-yl)-7,7-difluoro-1,3,4,7,10,11,12,13-octahydro-2H-6',7'-[1,3,2]diazaborolino[4,3-a:6,1-a']diisoindole-5,9-diyl)(2E,2'E)-diethyl diacrylate): A 40 mL screw cap vial was charged with compound 31.6 (0.091 mmol, 63 mg), compound 31.2 (0.109 mmol, 37 mg), DMAP (0.182 mmol, 22 mg) and a stir bar. The vial was sealed with a screw cap septum and flushed with argon. Anhydrous THF (6 mL) was added to the vial followed by DCC (0.182 mmol, 38 mg). After stirring overnight at room temperature under argon, water (35 mL) was added and the resulting precipitate was filtered off and washed with water. The wet precipitate was dissolved in DCM, separated from the water, dried over MgSO4, filtered and concentrated in vacuo. The product was purified by flash chromatography using an ethyl acetate / DCM gradient (100% DCM (1CV) → 10% ethyl acetate / DCM (10CV)). The fractions containing the product were concentrated in vacuo to give 62 mg (67% yield). MS (APCI): C 65 H 59 Calculated value for BF2N2O6(MH)=1011; found value=1011. 1 H NMR (400MHz, chloroform-d) δ8.24-8.14(m,4H),8.11(d,J=7.5Hz,1H),8.07(d,J=7.7Hz,1H),7.82(d, J=8.4Hz,1H),7.67(d,J=8.3Hz,1H),7.66(d,J=8.4Hz,1H),7.53-7.27(m,7H),7.15(d,J=7.9H z,1H),6.39(d,J=16.4Hz,2H),4.33(q,J=7.1Hz,4H),3.09(t,J=7.5Hz,2H),2.53-2.42(m,6H) ,2.13(s,6H),2.17-2.06(m,2H),1.59-1.45(m,4H),1.38(t,J=7.1Hz,6H),1.35-1.22(m,8H).

[0387] Example 2.32 PC-32:

[0388]

[0389] Compound 32.1 (3,3'-(7,7-difluoro-14-(3'-hydroxy-3,5-dimethyl-[1,1'-biphenyl]-4-yl)-1,3,4,7,10,11,12,13-octahydro-2H-614,714-[1,3,2]diazaborolinacyclo[4,3-a:6,1-a']diisoindole-5,9-diyl)(2E,2'E)-diethyl diacrylate): Compound 32.1 was synthesized from compound 31.5 (0.200 mmol, 136 mg) and 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol (1.00 mmol, 220 mg) in a similar manner to compound 31.6 to give 92 mg (66% yield). MS (APCI): C 41 H 43 Calculated for BF2N2O5 (MH) = 691; found = 691.

[0390] PC-32(3,3'-(14-(3,5-dimethyl-3'-((4-(perylene-3-yl)butanoyl)oxy)-[1,1'-biphenyl]-4-yl)-7,7-difluoro-1,3,4,7,10,11,12,13-octahydro-2H-614,714-[1,3,2]diazaborinylcyclo[4,3-a:6,1-a']diisoindole-5,9-diyl)(2E,2'E)-dipropane PC-32 was synthesized from compound 32.1 (0.050 mmol, 35 mg) and compound 31.2 (0.060 mmol, 20 mg) in a similar manner to PC-31, except that 2-chloro-1,3-dimethyl-4,5-dihydro-1H-imidazol-3-ium hexafluorophosphate (0.100 mmol, 28 mg) was used as a coupling agent to give 13.0 mg of the product (26% yield). MS (APCI): C 65 H 59 Calculated value for BF2N2O6(MH)=1011; found value=1011.

[0391] Example 2.33 PC-33:

[0392]

[0393] Compound 33.1 (3,3'-(7,7-difluoro-14-(4'-hydroxy-3,5-dimethyl-[1,1'-biphenyl]-4-yl)-1,3,4,7,10,11,12,13-octahydro-2H-614,714-[1,3,2]diazaborolinacyclo[4,3-a:6,1-a']diisoindole-5,9-diyl)(2E,2'E)-diethyl diacrylate): Compound 33.1 was synthesized in the same manner as compound 32.1 to give 73 mg of the product (53% yield). MS (APCI): C 41 H 43 Calculated for BF2N2O5 (MH) = 691; found = 691.

[0394] PC-33 (3,3'-(14-(3,5-dimethyl-4'-((4-(perylene-3-yl)butanoyl)oxy)-[1,1'-biphenyl]-4-yl)-7,7-difluoro-1,3,4,7,10,11,12,13-octahydro-2H-61,714-[1,3,2]diazaborolinacyclo[4,3-a:6,1-a']diisoindole-5,9-diyl)(2E,2'E)-diethyl diacrylate): PC-33 was synthesized from compound 33.1 (0.094 mmol, 65 mg) in the same manner as PC-32 to give 34 mg (yield 36%) of the product. MS (APCI): C 65 H 59 Calculated value for BF2N2O6(MH)=1011; found value=1011.

[0395] Example 2.34 PC-34:

[0396]

[0397] Compound 34.1 (2,5-di-tert-butylperylene): A three-necked flask was flushed with nitrogen and a stirring bar was added. Anhydrous o-dichlorobenzene (300 mL) was added to the flask, followed by perylene (19.81 mmol, 5.00 g). The reaction was cooled to 0 ° C in an ice-water bath. AlCl3 (19.81 mmol, 2.64 g) was added in batches via a powder distribution funnel over a period of 45 minutes, followed by dropwise addition of tert-butyl chloride (458 mmol, 50 mL). The cooling bath was removed and the reaction was stirred at room temperature for 24 hours. The reaction was quenched by pouring into 100 mL of ice-cold water. The organic layer was separated and concentrated to dryness on a rotary evaporator. The residue was dispersed in hot hexane (450 mL) and then cooled overnight at room temperature. The precipitate was collected by filtration. The precipitate was purified by flash chromatography on silica gel using ethyl acetate / hexane as eluent (1:9) to give the product 3.75 g (52% yield). MS (APCI): C 28 H 29 Calculated for (M+H)=365; found: 365. 1 H NMR (400 MHz, CHLOROFORM-d) δ 8.30-8.21 (m, 4H), 7.72-7.63 (m, 4H), 7.50 (t, J=7.8 Hz, 2H), 1.50 (s, 18H).

[0398] Compound 34.2 (methyl 4-(8,11-di-tert-butylperylene-3-yl)-4-oxobutanoate): Compound 34.2 was synthesized from compound 34.1 (15.85 mmol, 5.77 g) in a manner similar to compound 31.1 to give 2.7 g (35% yield). MS (APCI): C 33 H 35 Calculated for O3 (M+H) = 479; found: 479. 1 H NMR (400MHz, chloroform-d) δ8.58(d,J=8.6Hz,1H),8.33-8.28(m,3H),8.23(d,J=8.0Hz,1H),7.98(d,J=7.9Hz,1H),7.73(s,1H), 7.68(s,1H),7.60(t,J=8.0Hz,1H),3.75(s,3H),3.41(t,J=6.5Hz,2H),2.86(t,J=6.6Hz,2H),1.49(s,9H),1.48(s,9H).

[0399] Compound 34.3 (4-(8,11-di-tert-butylperylene-3-yl)butanoic acid): Compound 34.3 was synthesized from compound 34.2 (0.983 mmol, 471 mg) in a manner similar to compound 31.2 to give 110 mg (25% yield). MS (APCI): C 32 H 35 Calculated for O2 (M+H) = 451; found: 451. 1 H NMR (400MHz, chloroform-d) δ8.27-8.20(m,3H),8.15(d,J=7.7Hz,1H),7.88(d,J=8.4Hz,1H),7.63(s,1H),7.62(s,1H),7.53(t, J=8.0Hz, 1H), 7.34 (d, J=7.6Hz, 1H), 3.09 (t, J=7.7Hz, 2H), 2.48 (t, J=7.2Hz, 2H), 2.11 (p, J=6.9Hz, 2H), 1.47 (s, 18H).

[0400] PC-34 (3,3'-(14-(3'-((4-(8,11-di-tert-butylperylene-3-yl)butanoyl)oxy)-3,5-dimethyl-[1,1'-biphenyl]-4-yl)-7,7-difluoro-1,3,4,7,10,11,12,13-octahydro-2H-6',7'-[1,3,2]diazaborolinacyclo[4,3-a:6,1-a']diisoindole-5,9-diyl)(2E,2'E)-diethyl diacrylate): PC-34 was synthesized from compound 32.1 (0.060 mmol, 42 mg) and compound 34.3 (0.072 mmol, 32 mg) in a similar manner to PC-32 to give 36 mg of the product (53% yield). MS (APCI): C 73 H 75 Calculated value for BF2N2O6(MH)=1123; found: 1123.

[0401] Example 2.35 PC-35:

[0402]

[0403] Compound 35.1 (3,3'-((4-bromophenyl)methylene)bis(4,5,6,7-tetrahydro-2H-isoindole-1-carboxylic acid diethyl ester)): Compound 35.1 was synthesized from compound 24.3 (10.0 mmol, 1.933 g) and 4-bromobenzaldehyde (6.00 mmol, 1110 mg) in a similar manner to compound 24.4. The reaction mixture was evaporated to dryness and the residue was saponified without further purification. MS (APCI): C 29H 33 Calculated for BrN2O4(MH) = 551; found: 551.

[0404] Compound 35.2 (14-(4-bromophenyl)-7,7-difluoro-5,9-diiodo-1,3,4,7,10,11,12,13-octahydro-2H-6-14,7-14-[1,3,2]diazaborolino[4,3-a:6,1-a']diisoindole): The crude mixture from compound 35.1 (assumed to be 5.0 mmol) was treated in a similar manner to compound 24.5 to give 1.888 g of the product after several steps (64% yield from compound 24.3). MS (APCI): C 23 H 20 Calculated for BBrF2I2N2(MH)=705; found: 705.

[0405] Compound 35.3 (3,3'-(14-(4-bromophenyl)-7,7-difluoro-1,3,4,7,10,11,12,13-octahydro-2H-614,714-[1,3,2]diazaborolinacyclo[4,3-a:6,1-a']diisoindole-5,9-diyl)(2E,2'E)-diethyl diacrylate): Compound 35.3 was synthesized from compound 35.2 (0.500 mmol, 353 mg) in a similar manner to compound 29 to give 178 mg of the product (55% yield). MS (APCI): C 33 H 34 Calculated for BBrF2N2O4 (MH) = 649; found: 649.

[0406] Compound 35.4 (3,3'-(7,7-difluoro-14-(4'-hydroxy-[1,1'-biphenyl]-4-yl)-1,3,4,7,10,11,12,13-octahydro-2H-614,714-[1,3,2]diazaborolinacyclo[4,3-a:6,1-a']diisoindole-5,9-diyl)(2E,2'E)-diethyl diacrylate): Compound 35.4 was synthesized from compound 35.3 (0.263 mmol, 171 mg) in a similar manner to compound 32.1 to give 158 mg of the product (90% yield). MS (APCI): C 39 H 39 Calculated value for BF2N2O5 (MH) = 663; found: 663.

[0407] PC-35 (3,3'-(7,7-difluoro-14-(4'-((4-(perylene-3-yl)butanoyl)oxy)-[1,1'-biphenyl]-4-yl)-1,3,4,7,10,11,12,13-octahydro-2H-6',7'-[1,3,2]diazaborolino[4,3-a:6,1-a']diisoindole-5,9-diyl)(2E,2'E)-diethyl diacrylate): A 40 mL screw-cap vial was flushed with argon and charged with compound 35.4 (0.107 mmol, 71 mg), compound 31.2 (0.214 mmol, 72 mg), DMAP (0.214 mmol, 26 mg), pTsOH.H2O (0.193 mmol, 36 mg) and a stir bar. The vial was sealed with a screw cap septum, anhydrous DCM (4 mL) was added, and the mixture was stirred to form a solution. DIC (0.642 mmol, 0.100 mL) was added to the stirred reaction, and the mixture was stirred overnight under argon. The reaction mixture was diluted with ethyl acetate (150 mL) and extracted with 3N HCl aqueous solution (25 mL). The organic layer was washed with saturated sodium bicarbonate aqueous solution (25 mL), brine (15 mL), dried over MgSO4, filtered and concentrated in vacuo. The material was purified by flash chromatography on silica gel (100% DCM (3CV) → 1% EtOAc / DCM (0CV) → 10% EtOAc / DCM (10CV)). 84 mg (80% yield) was obtained. MS (APCI): C 63 H 55 Calculated for BF2N2O6 (MH) = 983; Found: 983.

[0408] Example 2.36 PC-36:

[0409]

[0410] PC-36 (3,3'-(14-(3,5-dimethyl-4'-((4-(perylene-3-yl)butanoyl)oxy)-[1,1'-biphenyl]-4-yl)-7,7-difluoro-1,3,4,7,10,11,12,13-octahydro-2H-614,714-[1,3,2]diazaborolinacyclo[4,3-a:6,1-a']diisoindole-5,9-diyl)(2E,2'E)-diethyl diacrylate): Synthesized in a similar manner to compound 35 from compound 33.1 (0.077 mmol, 51 m) and compound 31.2 to give 60 mg (yield 79%). MS (APCI): C 65 H 59 Calculated value for BF2N2O6(MH)=1011; found: 1011.

[0411] Example 2.37 PC-37:

[0412]

[0413] PC-37 (3,3'-(14-(4'-((4-(8,11-di-tert-butylperylene-3-yl)butanoyl)oxy)-3,5-dimethyl-[1,1'-biphenyl]-4-yl)-7,7-difluoro-1,3,4,7,10,11,12,13-octahydro-2H-614,714-[1,3,2]diazaborolinacyclo[4,3-a:6,1-a']diisoindole-5,9-diyl)(2E,2'E)-diethyl diacrylate): PC-37 was synthesized from compound 33.1 (0.060 mmol, 42 mg) and compound 34.3 (0.072 mmol, 33 mg) in a similar manner to compound 35 to give 61 mg (90% yield). MS (APCI): C 73 H 75 Calculated value for BF2N2O6(MH)=1023; found: 1023.

[0414] Example 21.38 PC-38:

[0415]

[0416] Compound 38.1 (2-tosylbicyclo[2.2.1]hept-2-ene): Compound 38.1 was synthesized from norbornene (365 mmol, 34.368 g), sodium p-toluenesulfonate (606 mmol, 108 g) and iodine (365 mmol, 92.7 g) in a similar manner to compound 24.2, 82.16 g after crystallization and flash purification on silica gel, yield 91%. MS (APCI): C 14 H 16 Calculated value of O2S (MH) = 247; Found: 247.

[0417] Compound 38.2 (ethyl 4,5,6,7-tetrahydro-2H-4,7-methyleneisoindole-1-carboxylate): Compound 38.2 was synthesized from compound 38.1 (90.0 mmol, 22.351 g) in a similar manner to compound 24.3 to afford 15.798 g (yield 86%) after purification by flash chromatography on silica gel. MS (APCI): C 12 H 15 Calculated value of NO2(MH)=204; found: 204.

[0418] Compound 38.3 (3,3'-((4-bromophenyl)methylene)bis(4,5,6,7-tetrahydro-2H-4,7-methyleneisoindole-1-carboxylic acid diethyl ester)): Compound 38.3 was synthesized from compound 38.2 (20.0 mmol, 4.105 g) and 4-bromobenzaldehyde (12.0 mmol, 2.220 g) in a similar manner to compound 31.3. The reaction was heated at 50°C under an argon atmosphere and monitored by LCMS until the reaction was complete. The crude product was isolated by evaporation and used in the next step without further purification. MS (APCI): C 31 H 33 Calculated value for BrN2O4(MH)=575: Found: 575.

[0419] Compound 38.4 (14-(4-bromophenyl)-7,7-difluoro-5,9-diiodo-1,3,4,7,10,11,12,13-octahydro-2H-614,714-1,4:10,13-dimethano[1,3,2]diazaborinylcyclo[4,3-a:6,1-a']diisoindole): Compound 38.4 was synthesized from the crude reaction product (compound 38.3, assumed to be 10.0 mmol) in a similar manner to compound 35.2 to give 4.138 g (57% yield). MS (APCI): C 25 H 20 Calculated for BBrF2I2N2(MH)=729; found: 729.

[0420] Compound 38.5 (3,3'-(14-(4-bromophenyl)-7,7-difluoro-1,3,4,7,10,11,12,13-octahydro-2H-614,714-1,4:10,13-dimethano[1,3,2]diazaborolina[4,3-a:6,1-a']diisoindole-5,9-diyl)(2E,2'E)-diethyl diacrylate): Compound 38.5 was synthesized from compound 38.4 (1.00 mmol, 731 mg) in a similar manner to compound 35.3 to give 272 mg (40% yield). MS (APCI): C 41 H 39 Calculated for BF2N2O5 (MH) = 687; found: 687.

[0421] Compound 38.6 (4-(perylene-3-yl)butanoic acid 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl ester): Compound 38.6 was synthesized from compound 31.2 and 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol in a similar manner to compound 37. MS (APCI): C36 H 33 Calculated value of BO4(MH)=539; found: 539.

[0422] PC-38 (3,3'-(7,7-difluoro-14-(4'-((4-(perylene-3-yl)butanoyl)oxy)-[1,1'-biphenyl]-4-yl)-1,3,4,7,10,11,12,13-octahydro-2H-614,714-1,4:10,13-dimethylbridge[1,3,2]diazaborinylcyclo[4,3-a:6,1-a']diisoindole-5,9-diyl)(2E,2'E)-diethyl diacrylate): PC-38 was synthesized from compound 38.5 (0.100 mmol, 68 mg) and compound 38.6 (0.150 mmol, 81 mg) in a similar manner to compound 35.4 to give the product in quantitative yield. MS (APCI): C 65 H 55 Calculated value for BF2N2O6(MH)=1007; found: 1007.

[0423] Example 2.39PC-39:

[0424]

[0425] Compound 39.1 (1-(cyclopent-1-ene-1-ylsulfonyl)-4-methylbenzene): Compound 39.1 was synthesized from cyclopentene (365 mmol, 32.3 mL), sodium p-toluenesulfonate (606 mmol, 108 g) and iodine (365 mmol, 92.7 mmol) in a similar manner to compound 38.1 to give 66.47 g (82% yield) of the product after crystallization. MS (APCI): C 12 H 14 Calculated value of O2S(MH)=221; found value: 221.

[0426] Compound 39.2 (ethyl 2,4,5,6-tetrahydrocyclopentyl[c]pyrrole-1-carboxylate): Compound 39.2 was synthesized from compound 39.1 (90.0 mmol, 20.0 g) in a similar manner to compound 38.2 to give 11.560 g (72% yield) of the product after flash chromatography on silica gel. MS (APCI): C 10 H 13 Calculated value of NO2(MH)=178; Found: 178.

[0427] Compound 39.3 (3,3'-((4-bromo-2,6-dimethylphenyl)methylene)bis(2,4,5,6-tetrahydrocyclopentyl[c]pyrrole-1-carboxylic acid diethyl ester)): Compound 39.3 was synthesized from compound 39.2 (10.0 mmol, 1.792 g) and 2,6-dimethyl-4-bromobenzaldehyde (6.00 mmol, 1.279 g) in a similar manner to compound 38.3. The crude product was purified by flash chromatography on silica gel (100% DCM (1CV) → 5% EtOAc / DCM (5CV) → 15% EtOAc / DCM (5CV)) to give 2.310 g (84% yield). MS (APCI): C 29 H 33 Calculated for BrN2O4(MH) = 551; found: 551.

[0428] Compound 39.4 (12-(4-bromo-2,6-dimethylphenyl)-6,6-difluoro-4,8-diiodo-2,3,6,9,10,11-hexahydro-1H-5l4,6l4-cyclopentyl[3,4]pyrrolo[1,2-c]cyclopentyl[3,4]pyrrolo[2,1-f][1,3,2]diazaborinene ring): Compound 39.4 was synthesized from compound 22.3 (4.17 mmol, 2.310 g) in a similar manner to compound 38.4 to give the product 1.522 g (52% yield) after purification by flash chromatography on silica gel. MS (APCI): C 23 H 20 Calculated for BBrF2I2N2(MH)=705; found: 705.

[0429] Compound 39.5 (3,3'-(12-(4-bromo-2,6-dimethylphenyl)-6,6-difluoro-2,3,6,9,10,11-hexahydro-1H-5',6'-cyclopentyl[3,4]pyrrolo[1,2-c]cyclopentyl[3,4]pyrrolo[2,1-f][1,3,2]diazaborinylcyclo-4,8-diyl)(2E,2'E)-diethyl diacrylate): Compound 39.5 was synthesized from compound 39.4 (0.500 mmol, 353 mg) in a similar manner to compound 38.5 to afford 66 mg (20% yield) of the product after flash chromatography on silica gel. MS (APCI): C 33 H 34 Calculated for BBrF2N2O4 (MH) = 649; found: 649.

[0430] Compound 39.6 (3,3'-(6,6-difluoro-12-(4'-hydroxy-3,5-dimethyl-[1,1'-biphenyl]-4-yl)-2,3,6,9,10,11-hexahydro-1H-5l4,6l4-cyclopentyl[3,4]pyrrolo[1,2-c]cyclopentyl[3,4]pyrrolo[2,1-f][1,3,2]diazaborin-4,8-diyl) Compound 39.6 was synthesized from compound 39.5 (0.077 mmol, 50 mg) and 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol (0.538 mmol, 118 mg) in a similar manner to compound 35.4 to afford the product in quantitative yield after flash chromatography on silica gel. MS (APCI): C 39 H 39 Calculated value for BF2N2O5 (MH) = 663; found: 663.

[0431] PC-39 (3,3'-(12-(3,5-dimethyl-4'-((4-(perylene-3-yl)butanoyl)oxy)-[1,1'-biphenyl]-4-yl)-6,6-difluoro-2,3,6,9,10,11-hexahydro-1H-5',6'-cyclopentyl[3,4]pyrrolo[1,2-c]cyclopentyl[3,4]pyrrolo[2,1-f][1,3,2]diazaborolin-4,8-diyl)(2E,2'E)-diethyl diacrylate): PC-39 was synthesized from compound 39.6 (0.077 mmol, 51 mg) and compound 31.2 (0.538 mmol, 182 mg) in a manner similar to compound 38.6, and the product 60 mg (yield 79%) was obtained after flash chromatography purification on silica gel. MS (APCI): C 63 H 55 Calculated for BF2N2O6 (MH) = 983; Found: 983.

[0432] Example 2.40 PC-40:

[0433]

[0434] Compound 40.1 (5-oxo-5-(perylene-3-yl)pentanoic acid methyl ester): A stirring bar was added to a 3L 2-necked round bottom flask and thoroughly flushed with argon. AlCl3 (34.7mmol, 4.624g) was added to the flask, followed by anhydrous dichloromethane (600mL). The reaction mixture was cooled to 0°C with an ice-water bath, and 5-chloro-5-oxopentanoic acid methyl ester (30.4mmol, 5.00g) was added via a syringe under stirring with argon. The mixture was stirred at 0°C for 1 hour, followed by the addition of perylene (28.9mmol, 7.300g) under stirring. The cooling bath was removed, and the reaction mixture was stirred at room temperature for 2 hours. The flask was equipped with a finned air condenser and heated in a heating block set at 45°C while stirring overnight under argon. The reaction mixture was cooled to room temperature and quenched by the addition of crushed ice (600mL, loosely packed). To the mixture was added 6N aqueous HCl (100 mL). Stirring was continued until all ice melted. The layers were separated and the aqueous layer was extracted with DCM (2×200 mL). The combined organic layers were dried over MgSO4, filtered, and concentrated in vacuo. The crude reaction was purified by flash chromatography on silica gel (100% DCM (3CV) → 5% EtOAc / DCM (10CV)). The fractions containing the product were collected and concentrated in vacuo to give 3.810 g, 35% yield. MS (APCI): C 26 H 20 Calculated for O3 (M+H) = 381; found: 381.

[0435] Compound 40.2 (5-oxo-5-(perylene-3-yl)pentanoic acid): A stirring bar was added to a 250 mL 2-necked round bottom flask and flushed with argon. Compound 40.1 (3.00 mmol, 1.141 g) and KOH (30.0 mmol, 1.683 g) were added to the flask, followed by ethanol (200 proof, 200 mL). The flask was equipped with a finned air condenser and heated in a heating block at 95° C. under argon with stirring for two hours. The reaction mixture was cooled to room temperature and diluted with water in a conical flask (to a total volume of 500 mL) and quenched with 6N aqueous HCl (5 mL). The resulting precipitate was collected and concentrated in vacuo to give 1.013 g (92% yield). MS (APCI): C 25 H 18 Calculated value of O3(MH)=365, found value: 365.

[0436] PC-40 (3,3'-(14-(3,5-dimethyl-4'-((5-oxo-5-(perylene-3-yl)pentanoyl)oxy)-[1,1'-biphenyl]-4-yl)-7,7-difluoro-1,3,4,7,10,11,12,13-octahydro-2H-6',7'-[1,3,2]diazaborinylcyclo[4,3-a:6,1-a']diisoindole-5,9-diyl)(2E,2'E)-diethyl diacrylate): PC-40 was synthesized from compound 40.2 (0.400 mmol, 147 mg) and compound 33.1 (0.100 mmol, 69 mg) in a similar manner to compound 39 to give 67 mg of the product (64% yield) after flash chromatography on silica gel. MS (APCI): C 66 H 59 Calculated value for BF2N2O7 (MH) = 1039; found: 1039.

[0437] Example 2.41 PC-41:

[0438]

[0439] Compound 41.1 (5-(Perylene-3-yl)pentanoic acid): A 40 mL screw cap vial was charged with compound 40.1 (3.00 mmol, 1.141 g) and a stirring bar. The vial was flushed with argon. Trifluoroacetic acid (10 mL) and anhydrous dichloromethane (10 mL) were added to the vial. The vial was sealed with a screw cap septum and triethylsilane (6.6 mmol, 1.05 mL) was added under stirring. The reaction was stirred at room temperature under argon for three days, at which time the reduction was found to be complete by LCMS. The reaction mixture was concentrated in vacuo and azeotroped with toluene to remove residual trifluoroacetic acid. The crude ester was saponified in a similar manner to compound 40.2 to give 1.025 g of precipitated product (97% yield). MS (APCI): C 25 H 20 Calculated value for O2 (MH) = 351; found: 351.

[0440] Compound 41.2 (4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl 5-(perylene-3-yl)pentanoate): Compound 41.1 (1.45 mmol, 512 mg) and 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol (2.18 mmol, 480 mg) were esterified in a similar manner to PC-40 to give 614 mg of the product (76% yield) after flash chromatography on silica gel. MS (APCI): C 37 H 35Calculated value of BO4(MH)=553; found: 553.

[0441] PC-41 (3,3'-(14-(3,5-dimethyl-4'-((5-(perylene-3-yl)pentanoyl)oxy)-[1,1'-biphenyl]-4-yl)-7,7-difluoro-1,3,4,7,10,11,12,13-octahydro-2H-6',7'-[1,3,2]diazaborolinacyclo[4,3-a:6,1-a']diisoindole-5,9-diyl)(2E,2'E)-diethyl diacrylate): PC-41 was synthesized from compound 41.2 (0.150 mmol, 83 mg) and compound 31.3 (0.100 mmol, 68 mg) in a similar manner to compound 38 to give 46 mg of the product (45% yield) after purification by flash chromatography on silica gel. MS (APCI): C 66 H 61 Calculated value for BF2N2O6 (MH) = 1025; found: 1025.

[0442] Example 2.42 PC-42:

[0443]

[0444] Compound 42.1 (3-oxo-3-(perylene-3-yl)propionic acid methyl ester): A stirring bar was added to a 500 mL 3-neck round bottom flask and flushed with argon. AlCl3 (9.52 mmol, 1.27 g) was added to the flask, followed by anhydrous dichloromethane (160 mL). The solution was stirred at room temperature, and 3-chloro-3-oxopropionic acid methyl ester (8.30 mmol, 0.890 mL) was added, followed by perylene (7.92 mmol, 1.99 g). The reaction was stirred at room temperature under argon overnight. The next morning, the flask was equipped with a finned air condenser and heated to 45 ° C with a heating block, and stirred at this temperature under argon for the entire weekend. Another portion of 3-chloro-3-oxopropionic acid methyl ester (8.30 mmol, 0.890 mL) was added, and stirring was continued overnight at 45 ° C under argon. The reaction was quenched by the addition of water (100 mL) and 6N aqueous HCl (100 mL) and diluted with dichloromethane (100 mL). The layers were separated (emulsion) and the aqueous layer was extracted with DCM (2×200 mL, emulsion) and then with DCM (4×100 mL). The organic layer was dried over MgSO4, filtered and concentrated in vacuo. The product was purified by flash chromatography on silica gel (100% DCM (3CV) → 1% EtOAc / DCM (0CV) → 1% EtOAc / DCM (3CV) → 10% EtOAc / DCM (8CV)) to give 1.905 g of product (68% yield). MS (APCI): C 24 H 16 Calculated for O3 (M+H) = 353; found: 353.

[0445] Compound 42.2 (3-(Perylene-3-yl)propanoic acid): Compound 42.1 (3.10 mmol, 1.091 g) was reduced with triethylsilane and saponified in a similar manner to compound 41.1. The resulting acid has very poor solubility and requires hot THF to dissolve in a reasonable volume. 682 mg (68% yield for 2 steps) was obtained. MS (APCI): C 23 H 16 Calculated value for O2 (MH) = 323; found: 323.

[0446] Compound 42.3 (4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl 3-(perylene-3-yl)propanoate): Compound 42.3 was synthesized from compound 42.2 (1.67 mmol, 543 mg) and 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol (2.51 mmol, 553 mg) in a similar manner to compound 41.2 to give 434 mg of the product (49% yield) after flash chromatography on silica gel. MS (APCI): C 35 H 31 Calculated value of BO4(MH)=525; found: 525.

[0447] PC-42 (3,3'-(14-(3,5-dimethyl-4'-((3-(perylene-3-yl)propanoyl)oxy)-[1,1'-biphenyl]-4-yl)-7,7-difluoro-1,3,4,7,10,11,12,13-octahydro-2H-614,714-[1,3,2]diazaborolinacyclo[4,3-a:6,1-a']diisoindole-5,9-diyl)(2E,2'E)-diethyl diacrylate): PC-42 was synthesized from compound 42.3 (0.150 mmol, 79 mg) and compound 31.3 (0.100 mmol, 68 mg) in a similar manner to compound 41 to give 81 mg of the product (81% yield) after flash chromatography on silica gel. MS (APCI): C 64 H 57 Calculated for BF2N2O6 (MH) = 997; found: 997.

[0448] Example 2.43PC-43:

[0449]

[0450] Compound 43.1 ((E)-1-toluenesulfonylcyclododec-1-ene): Compound 43.1 was synthesized from E / Z-cyclododecene (150 mmol, 28.7 mL), sodium p-toluenesulfonate (249 mmol, 44.37 g) and iodine (150 mmol, 38.070 g) in a similar manner to compound 39.1 to give the product (xxx g) after crystallization and purification by flash chromatography on silica gel. MS (APCI): C 19 H 28 Calculated value of O2S (MH) = 319; found value: 319.

[0451] Compound 43.2 (ethyl 4,5,6,7,8,9,10,11,12,13-decahydro-2H-cyclododecyl[c]pyrrole-1-carboxylate): Compound 43.2 was synthesized from compound 43.1 (45.0 mmol, 14.423 g) in a similar manner to compound 39.2 to give 10.441 g of the product (84% yield) after flash chromatography on silica gel. MS (APCI): C 17 H 27 Calculated value of NO2(MH)=276; Found: 276.

[0452] Compound 43.3 (,3'-((4-bromo-2-methylphenyl)methylene)bis(4,5,6,7,8,9,10,11,12,13-decahydro-2H-cyclododecyl[c]pyrrole-1-carboxylic acid diethyl ester)): Compound 43.3 was synthesized from compound 26.2 (15.0 mmol, 4.161 g) and 2-methyl-4-bromobenzaldehyde (9.0 mmol, 1.791 g) in a similar manner to compound 39.3 to give a crude product which was used in the next step without further purification. MS (APCI): C 42 H 59 Calculated for BrN2O4(MH) = 733; found: 733.

[0453] Compound 43.4 (26-(4-bromo-2-methylphenyl)-13,13-difluoro-11,15-diiodo-1,3,4,5,6,7,8,9,10,13,16,17,18,19,20,21,22,23,24,25-icosahydro-2H-1214,1314-cyclododecyl[3,4]pyrrolo[1,2-c]cyclododecyl[3,4]pyrrolo[2,1-f][1,3,2]diazaborinine ring): Compound 43.4 was synthesized from crude compound 43.3 (assumed to be 7.50 mmol) to give 844 mg of the desired product (13% yield) in several steps and after purification by flash chromatography. MS (APCI): C 36 H 46 Calculated for BBrF2I2N2(MH)=887; Found: 887.

[0454] Compound 43.5 (3,3'-(26-(4-bromo-2-methylphenyl)-13,13-difluoro-1,3,4,5,6,7,8,9,10,13,16,17,18,19,20,21,22,23,24,25-icosahydro-2H-12'4,13'4-cyclododecyl[3,4]pyrrolo[1,2-c]cyclododecyl[3,4]pyrrolo[2,1-f][1,3,2]diazaborincyclo-11,15-diyl)(2E,2'E)-diethyl diacrylate): Compound 43.5 was synthesized from compound 43.4 (0.949 mmol, 844 mg) in a similar manner to compound 39.5 to give 279 mg of the product (35% yield) after purification by flash chromatography on silica gel. MS (APCI): C 46 H 60 Calculated value for BBrF2N2O4(MH)=831; found: 831.

[0455] Compound 43.6 (3,3'-(13,13-difluoro-26-(4'-hydroxy-3-methyl-[1,1'-biphenyl]-4-yl)-1,3,4,5,6,7,8,9,10,13,16,17,18,19,20,21,22,23,24,25-icosahydro-2H-1214,1314-cyclododecyl[3,4]pyrrolo[1,2-c]cyclododecyl[3,4]pyrrolo[2,1-f][1,3,2] Diazaborin-11,15-diyl)(2E,2'E)-diethyl diacrylate): Compound 43.6 was synthesized from compound 43.5 (0.335 mmol, 279 mg) and 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol (1.004 mmol, 221 mg) in a similar manner to compound 39.6 to give 229 mg of the product (81% yield) after flash chromatography on silica gel. MS (APCI): C 52 H 65 Calculated for BF2N2O5 (MH) = 845; found: 845.

[0456] PC-43 (3,3'-(13,13-difluoro-26-(3-methyl-4'-((5-oxo-5-(perylene-3-yl)pentanoyl)oxy)-[1,1'-biphenyl]-4-yl)-1,3,4,5,6,7,8,9,10,13,16,17,18,19,20,21,22,23,24,25-icosahydro-2H-1214,1314-cyclododecyl[3,4]pyrrolo[1,2-c] Cyclododecyl[3,4]pyrrolo[2,1-f][1,3,2]diazaborinylcyclo-11,15-diyl)(2E,2'E)-diethyl diacrylate): PC-43 was synthesized from compound 43.6 (0.100 mmol, 85 mg) and compound 40.2 (0.130 mmol, 48 mg) in a similar manner to compound 39 to give 93 mg of the product (77% yield) after flash chromatography purification on silica gel. MS (APCI): C 77 H 81 Calculated value for BF2N2O7 (MH) = 1193; found: 1193.

[0457] Example 2.44 PC-44:

[0458]

[0459] Methyl 4-(4,9,10-tribromoperylene-3-yl)butyrate / Methyl 4-(4,10-dibromo-4,12b-dihydroperylene-3-yl)butyrate / Methyl 4-(5,9,10-tribromoperylene-3-yl)butyrate:

[0460]

[0461] A mixture of 4-(4,12b-dihydroperylene-3-yl)butyric acid methyl ester (1.00 g, 2.837 mmol, 1 equivalent) in anhydrous chloroform (20 mL) was placed in a two-necked flask and kept in the dark. The mixture was purged with argon for 15 minutes, and NBS (1.767 g, 9.929 mmol, 3.5 equivalents) was added in multiple small portions and then stirred at room temperature for 15 min. Anhydrous DMF (10 mL) was added. The resulting mixture was stirred at room temperature for 4 hours under argon protection. TLC and LCMS showed that the raw material had been consumed. 25 mL of water was added, and the organic layer was separated; the aqueous layer was re-extracted with ethyl acetate, washed with water several times, dried over MgSO4 and concentrated. The crude product was purified by SiO2 column chromatography, eluting with hexane / DCM (9:1) to (1:4) to give 0.655 g of a mixture of three isomers (tribromoperylene derivative, dibromoperylene derivative and tetrabromoperylene derivative (7:1:05)). The product was used without further purification. Yield 38%. LCMS (APCI+): Formula C25 H 17 Calculated for Br3O2; found: 589.

[0462] Compound 44.1 (methyl 4-(4,7,10-tris(4-(trifluoromethyl)phenyl)perylene-3-yl)butanoate): A 250 mL 2-necked round bottom flask was charged with a stir bar and equipped with a finned condenser and a gas adapter. The flask was flushed with argon. To the flask was added methyl 4-(4,7,10-tribromoperylene-3-yl)butanoate (0.849 mmol, 500 mg) (mixture of isomers) and (4-(trifluoromethyl)phenyl)boric acid (5.94 mmol, 1128 mg), n-butanol (20 mL), toluene (6 mL), and water (6 mL). The flask was heated to 45 °C in a heating block and bubbled with argon for 30 minutes. (4-(Diphenylamino)phenyl)boronic acid (13.8mmol, 3.994g), sodium carbonate (37.68mmol, 3.994g) and Pd(PPh3)4 (0.628mmol, 726mg) were then added while bubbling with argon. The flask was stopped and the heating block temperature was raised to 80°C under an argon atmosphere. Stir and heat at this temperature overnight. The reaction mixture was worked up and purified by flash chromatography on silica gel (100% hexane (1CV) → 30% toluene / hexane (0CV) → 100% toluene (10CV)). The crude product was purified by flash chromatography on silica gel (40% 100% hexane (1CV) → 40% DCM / hexane (0CV) → 100% DCM (10CV)). The fractions containing the product were evaporated to dryness to give 540mg (81% yield) of a mixture of isomers. MS (APCI): Formula C 46 H 29 Calculated value for F9O2(M-)=784, found: 784.

[0463] Compound 44.1.1 (methyl 4-(10-(trifluoromethyl)-4,7-bis(4-(trifluoromethyl)phenyl)indeno[1,2,3-cd]perylene-3-yl)butanoate): A stir bar was added to a 300 mL beaker. Methyl (4-(4,7,10-tris(4-(trifluoromethyl)phenyl)perylene-3-yl)butanoate) (0.688 mmol, 540 mg) was added followed by toluene (250 mL) and p-chloroaniline (0.688 mmol, 169 mg). The reaction mixture was stirred open to air and irradiated with a 465 nm LED array (commercially available light strip) for 24 hours. The solvent was evaporated to dryness and the reaction mixture was purified by flash chromatography on silica gel (100% hexanes (1 CV) → 75% toluene / hexanes (0CV) → 100% toluene (10CV)). The fractions containing the product were evaporated to dryness to give 118 mg (22% yield) of a mixture of isomers. MS (APCI): Chemical formula C 46 H 27 Calculated value of F9O2(M-)=782, found value: 782.

[0464] Compound 44.1.2 (4-(10-(trifluoromethyl)-4,7-bis(4-(trifluoromethyl)phenyl)indeno[1,2,3-cd]perylene-3-yl)butanoic acid): A 250 mL 2-necked round bottom flask was charged with a stir bar and equipped with a finned condenser and a gas adapter. The flask was flushed with argon. To the flask was added (methyl 4-(10-(trifluoromethyl)-4,7-bis(4-(trifluoromethyl)phenyl)indeno[1,2,3-cd]perylene-3-yl)butanoate) (0.151 mmol, 118 mg) followed by n-butanol (100 mL) followed by KOH (5.0 M in water, 1.740 mmol, 0.350 mL). The flask was stoppered and heated with stirring in a heating block at 115 °C overnight under argon. The reaction mixture was cooled to room temperature and water (10 mL) was added. Trifluoroacetic acid was added until the pH was about 1. The reaction was evaporated to dryness. The dichloromethane soluble portion was evaporated to dryness at 100°C to give the product in quantitative yield. The crude precipitate was isolated in quantitative yield and used in the next step without further purification. MS (APCI): Chemical formula C 45 H 25 Calculated value of F9O2(M-)=768, found value: 768.

[0465]

[0466] Compound 44.2 (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]diazaborolin-2,8-dicarboxylic acid dibenzyl ester): In a 250-mL round-bottom flask, 40 mL (241 mmol) of tert-butyl 3-oxobutanoate was dissolved in 80 mL of acetic acid. The mixture was cooled to about 10°C in an ice-water bath. Sodium nitrite (18 g, 262 mmol) was added over 1 h while keeping the temperature below 15°C. The cooling bath was removed and the mixture was stirred at room temperature for 3.5 h. The insoluble material was filtered off to give a crude solution of the oxime, which was used in the next step without further purification. Next, 50 g of zinc powder (0.76 mol) was added in batches to a mixture of 13.7 mL (79 mmol) of benzyl 3-oxobutyrate and 100 mL of acetic acid. The resulting mixture was stirred and heated to 60 ° C in an oil bath. A crude solution of tert-butyl 2-(hydroxyimino-3-oxobutyrate was slowly added. The temperature was then raised to 75 ° C and stirred for 1 h. Next, the reaction mixture was poured into water (4 L). The precipitate was collected and filtered to give 2,4-dimethyl-1H-pyrrole-3-carboxylic acid benzyl ester, which was recrystallized from MeOH as a white solid to give 15 g, with a yield of 65% based on benzyl 3-oxobutyrate. 1 H NMR (400MHz, CDCl3): 8.88 (br, s, 1H, NH), 7.47-7.33 (m, 5H, C=CH), 5.29 (s, 2H, CH2), 2.53, 2.48 (2s, 6H, 2CH3), 1.56 (s, 9H, 3CH3).

[0467] Next, in a 25 mL vial, a mixture of 1 g (4.36 mmol) of 2,4-dimethyl-1H-pyrrole-3-carboxylic acid benzyl ester and 0.524 g (4.36 mmol) of MgSO4 was dissolved in 8 mL of anhydrous DCE and stirred at room temperature for 15 min in the presence of argon. 0.327 g of 2,6-dimethyl 4-hydroxybenzaldehyde (2.18 mmol) was added in small portions; finally, the mixture was closed with a Teflon cap. The resulting mixture was further purged with argon for 15 min, and TFA (3 drops, catalytic amount) was added. The reaction mixture was stirred at 65 ° C for 16 h. TLC and LCMS showed that the starting material had been consumed. 0.544 g (2.398 mmol) of DDQ was added to the crude product in one portion. The resulting mixture was stirred at room temperature for 1 / 2 h. TLC and LCMS showed that the starting material was consumed. The resulting mixture was filtered through short path diatomaceous earth; the filtrate was concentrated to dryness, the residue was redissolved in 50 mL DCE, stirred with trimethylamine (1.4 mL, 19 mmol) for 15 min at room temperature, and then cooled to 0 ° C. 3 mL of BF3 (18.36 mmol) was slowly added. The resulting mixture was stirred at room temperature for 1 / 2 h and heated to 86 ° C for 45 min. The reaction mixture was then diluted with 150 mL of CHCl3 and quenched with 50 mL of brine. The organic layer was separated and dried over MgSO4, the solvent was removed and rotary evaporated. The residue was chromatographed on a silica gel column using CH2Cl2 / EtOAc as eluent to give 1 g of pure 5,5-difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-1,3,7,9-tetramethyl-5H-4-(1,4,5-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylic acid dibenzyl ester) as an orange-red solid in a yield of 72% based on 2,6-dimethyl 4-hydroxybenzaldehyde. LCMS (APCI-) for C 37 H 35 Calculated value of M- for BF2N2O5: 636.26; found value: 636. 1 H NMR (400 MHz, CHLOROFORM-d) δ 7.42-7.28 (m, 4H), 6.66 (d, J = 0.7 Hz, 1H), 5.29 (d, J = 11.3 Hz, 2H), 2.82 (s, 3H), 2.04 (d, J = 5.4 Hz, 3H), 1.72 (s, 3H).

[0468] PC-44 (10-(2,6-dimethyl-4-((4-(8-(trifluoromethyl)-11,14-bis(4-(trifluoromethyl)phenyl)indeno[1,2,3-cd]perylene-1-yl)butanoyl)oxy)phenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylic acid dibenzyl ester): prepared from compound 44.2 [5,5-difluoro-10- (4-hydroxy-2,6-dimethylphenyl)-1,3,7,9-tetramethyl-5H-4,14,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinylcyclo-2,8-dinitrile] (0.055 mmol, 35 mg) and compound 44.1.2 [4-(10-(trifluoromethyl)-4,7-bis(4-(trifluoromethyl)phenyl)indeno[1,2,3-cd]perylene-3-yl)butanoic acid] (0.050 mmol, 38 mg). The crude product was purified by flash chromatography on silica gel (100% DCM (1CV) → 10% EtOAc / DCM (10CV)). The fractions containing the product were evaporated to give A. To a 40 mL screw cap vial was added a stir bar, 5,5-difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-1,3,7,9-tetramethyl-5H-4,14,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarbonitrile (0.055 mmol, 35 mg), 4-(10-(trifluoromethyl)-4,7-bis(4-(trifluoromethyl)phenyl)indeno[1,2,3-cd]perylene-3-yl)butanoic acid (0.050 mmol, 38 mg), and DMAP:pTsOH 1:1 salt (0.200 mmol, 59 mg). The vial was flushed with argon and anhydrous dichloromethane (20 mL) was added. Add diisopropylcarbodiimide (0.300mmol, 47uL), and the reaction was stirred at room temperature overnight under argon. In the morning of the second day, anhydrous tetrahydrofuran (10mL) was added and ultrasonicated for 30 seconds. Add additional 4-(perylene-3-yl)butanoic acid (0.150mmol, 51mg), and stir at 50 ℃ overnight under argon. The solvent is evaporated to dryness, and the product is purified by flash chromatography (100% hexane (1CV) → 5% EtOAc / hexane (0CV) → 40% EtOAc / hexane (10CV)) on silica gel. The product containing fractions were evaporated to dryness and subjected to further purification by flash chromatography on silica gel (100% hexanes (1CV) → 10% EtOAc / hexanes (0CV) → 30% EtOAc / hexanes (10CV). The product containing fractions were evaporated to dryness to give 47 mg (68% yield) of a mixture of isomers.MS (APCI): for chemical formula C. 82 H 58 BF 11 Calculated value of N2O6(M-)=1386, found value 1386.

[0469] Example 2.45 PC-45:

[0470]

[0471] Ethyl 2,2-difluoro-2-(perylene-3-yl)acetate: A 40 mL screw cap vial was charged with a stirring bar and fitted with a screw cap septum. The vial was flushed with argon and anhydrous dichloromethane (10 mL) was added followed by ethyl 2-oxo-2-(perylene-3-yl)acetate (1.0 mmol, 352 mg). The reaction was stirred at room temperature and diethyl sulfide trifluoride (2.5 mmol, 0.328 mL) was added via a pipette. The vial was sealed and stirred at room temperature overnight under argon. The reaction was then heated to 4 °C and stirred for 6 hours. Deoxo-Fluor (2.5 mmol, 0.461 mL) was added to the reaction mixture and stirred at 40 °C for three hours. Additional Deoxo-Fluor (2.5 mmol, 0.461 mL) was added and stirred at 40 °C overnight under argon. The crude reaction mixture was purified by flash chromatography on silica gel (50% DCM / hexane (2CV) → 100% DCM (8CV)). The fractions containing the product were evaporated to dryness to give 350 mg with a yield of 94%. MS (APCI): for formula C 24 H 16 Calculated value for F2O2(M-)=374; found: 374. 1 H NMR(400MHz,THF-d8)δ8.41-8.36(m,3H),8.35(dd,J=7.6,1.1Hz,1H),8.01(dq,J=8.3,1.5Hz,1H),7.85(d,J=8.1Hz,1H),7.78(dd,J=13.3 ,8.0Hz,2H),7.59(dd,J=8.6,7.6Hz,1H),7.53(d,J=5.1Hz,1H),7.53(dd,J=15.6,5.1Hz,1H),4.28(q,J=7.1Hz,2H),1.20(t,J=7.1Hz,3H).

[0472] 2,2-Difluoro-2-(perylene-3-yl)acetic acid: A 40 mL screw cap vial was charged with a stirring bar and fitted with a screw cap septum. The vial was flushed with argon and ethyl 2,2-difluoro-2-(perylene-3-yl)acetate (0.500 mmol, 187 mg) was added followed by anhydrous THF (20 mL). KOH (5.0 M in H2O, 2.50 mmol, 0.5 mL) was added with stirring, the vial was sealed, and the reaction was heated in a heating block at 50 °C under argon. After heating at 50 °C overnight, the reaction was cooled to room temperature and quenched by adding excess trifluoroacetic acid to a pH of 1-2. The reaction mixture was diluted with water (200 mL) and the precipitated product was filtered off and washed with water. The product was dissolved in tetrahydrofuran and evaporated to dryness to give a quantitative yield of the product, which was contaminated with salts. The material was used in the next step without further purification. MS (APCI), for chemical formula C 22 H 12 Calculated value for F2O2(M-)=346; found: 346.

[0473] PC-45: 10-(4-(2,2-difluoro-2-(perylene-3-yl)acetoxy)-2,6-dimethylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4-14,5-14-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylic acid dibenzyl ester: Place a stir bar, 2,2-difluoro-2-(perylene-3-yl)acetoxy, and 1,3,7,9-tetramethyl-5H-4-14,5-14-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylate in a 40 mL screw cap vial. -yl)acetic acid (0.100mmol, 64mg) and compound 44.2 [5,5-difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-1,3,7,9-tetramethyl-5H-4',5'-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinyl-2,8-dicarboxylic acid dibenzyl ester] (0.130mmol, 45mg) and DMAP:pTsOH 1:1 salt (0.200mmol, 59mg). The vial was flushed with argon and anhydrous dichloromethane (20mL) was added. Diisopropylcarbodiimide (0.300mmol, 47uL) was added and the reaction was stirred at room temperature under argon overnight. The next morning, anhydrous tetrahydrofuran (10mL) was added and sonicated for 30 seconds. An additional portion of 4-(perylene-3-yl)butanoic acid (0.150 mmol, 51 mg) was added and stirred overnight at 50°C under argon. The solvent was evaporated to dryness and the product was purified by flash chromatography on silica gel (100% hexanes (1CV) → 5% EtOAc / hexanes (0CV) → 40% EtOAc / hexanes (10CV)). The fractions containing the product were evaporated to dryness and subjected to further purification by flash chromatography on silica gel (100% hexanes (1CV) → 10% EtOAc / hexanes (0CV) → 30% EtOAc / hexanes (10CV). The fractions containing the product were evaporated to dryness to give 45 mg (47% yield). MS (APCI), formula C 59 H 45 Calculated value for BF4N2O6 (M-) = 964; found: 964. 1 H NMR (400MHz, chloroform-d) δ8.34-8.28(m,3H),8.28-8.25(m,1H),8.10(d,J=8.5Hz,1H),7.99(d,J=8.0Hz,1H),7.77(dd,J=13.2,8.1Hz,2H),7.66 (dd,J=8.6,7.6Hz,1H),7.55(td,J=7.8,3.3Hz,2H),7.37-7.29(m,10H),6.89(s,2H),5.24(s,4H),2.80(s,6H),2.07(s,6H),1.63(s,6H).

[0474] Example 2.46 PC-46:

[0475]

[0476] Methyl 4-(4,9,10-tris(trifluoromethyl)perylene-3-yl)butanoate: A 40 mL screw cap vial was charged with a stir bar and fitted with a screw cap septum. The vial was flushed with argon. To the vial was added methyl 4-(4,9,10-tribromoperylene-3-yl)butanoate (mixture of isomers (0.496 mmol, 292 mg)), CuI (4.96 mmol, 944 mg) and then anhydrous dimethylacetamide (10 mL). With stirring at room temperature, methyl 2,2-difluoro-2-(fluorosulfonyl)acetate (4.96 mmol, 0.631 mL) was added via a syringe at room temperature. The reaction was placed in a heating block set at 160 °C and stirred for 3 hours. Additional portions of CuI (4.96 mmol, 944 mg) and methyl 2,2-difluoro-2-(fluorosulfonyl)acetate (4.96 mmol, 0.631 mL) were added and the reaction was stirred for another hour. The reaction mixture was cooled to room temperature and diluted with water to a total volume of 100 mL. The product was filtered off and washed with water. The precipitate was dried and washed with dichloromethane until the dichloromethane was colorless. The combined organic washes were evaporated to dryness and purified by flash chromatography on silica gel (50% toluene / hexane (1CV) → 100% toluene (10CV)). The fractions containing the desired product (as a mixture of isomers) were evaporated to dryness to give 90 mg (33% yield). MS (APCI): Chemical formula C 28 H 17 Calculated value for F9O2(M-)=556; found: 556.

[0477] Compound 46.1: 4-(4,9,10-Tris(trifluoromethyl)perylene-3-yl)butanoic acid: A stirring bar was added to a 250 mL 2-necked round bottom flask and flushed with argon. To the flask were added 4-(4,9,10-tris(trifluoromethyl)perylene-3-yl)butanoic acid (3.00 mmol, 1.141 g) and KOH (30.0 mmol, 1.683 g) followed by ethanol (200 proof, 200 mL). The flask was equipped with a finned air condenser and heated with stirring in a heating block at 95 °C under argon for two hours. The reaction mixture was cooled to room temperature and diluted with water in a conical flask (to a total volume of 500 mL) and quenched with 6N aqueous HCl (5 mL). The resulting precipitate was collected and concentrated in vacuo to give the crude precipitate in quantitative yield. MS (APCI): Chemical formula C 27 H 15 Calculated value for F9O2(M-)=542; found: 542.

[0478] PC-46 (10-(2,6-dimethyl-4-((4-(4,9,10-tris(trifluoromethyl)perylene-3-yl)butanoyl)oxy)phenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4,14,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylic acid dibenzyl ester): Add a stir bar to a 40 mL screw cap vial. Compound 46.1 [4-(4,9,10-tris(trifluoromethyl)perylene-3-yl)butanoic acid] (0.164mmol, 89mg) and compound 44.2 [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]diazaborinyl-2,8-dicarboxylic acid dibenzyl ester] and DMAP:pTsOH 1:1 salt (0.200mmol, 59mg). The vial was flushed with argon and anhydrous dichloromethane (20mL) was added. Diisopropylcarbodiimide (0.300mmol, 47uL) was added and the reaction was stirred at room temperature under argon overnight. The next morning, anhydrous tetrahydrofuran (10mL) was added and sonicated for 30 seconds. An additional portion of 4-(perylene-3-yl)butanoic acid (0.150 mmol, 51 mg) was added and stirred at 50°C overnight under argon. The crude product was purified by flash chromatography on silica gel (100% toluene (2CV) → 10% EtOAc / toluene (10CV)). The fractions containing the product (as a mixture of isomers) were evaporated to dryness to give 128 mg (67% yield). MS (APCI): Formula C 64 H 48 BF 11 Calculated value for N2O6(M-) = 1160; found: 1160.

[0479] Example 2.47 PC-47:

[0480]

[0481] Methyl 4-(9,10-bis(trifluoromethyl)perylene-3-yl)butanoate: Note: Only one isomer is depicted for illustration. Actual reaction of the brominated isomer of the starting material and the trifluoromethylated isomer of the product. Set up a 100 mL 2-neck round bottom flask with a stir bar, finned condenser, and gas adapter. The flask and condenser were flushed with argon. While stirring under argon, 10 equivalents (13.6 mmol, 2.586 g) of CuI were added to the flask. 1 equivalent of the brominated perylene isomer (1.36 mmol, 800 mg) was dissolved in 5 mL of anhydrous DMA under argon and transferred to the flask via a syringe. The vial was rinsed with anhydrous DMA (2×5 mL) under argon, and these DMA aliquots were also added to the reaction flask. An additional 15 mL of anhydrous DMA was added to the reaction flask (total DMA=30 mL). 2-(Fluorosulfonyl)-2,2-difluoroacetic acid methyl ester (10 eq., 13.6 mmol, 2.609 g, 1.509 g / mL, 1.73 mL) was added to the flask via a syringe and the second neck was sealed with a glass stopper. The mixture was stirred and heated with a heating block set at 160°C. After 2 hours, LCMS indicated that the reaction was about 90% complete. 1295 mg of CuI (5.0 eq., 6.80 mmol) and 1306 mg of 2-(Fluorosulfonyl)-2,2-difluoroacetic acid methyl ester (5.0 eq., 6.80 mmol, 1.509 g / mL, 0.866 mL) were added to the reaction, stirred at 160°C for 2 hours, and then left at room temperature overnight. The reaction mixture was treated by pouring the reaction mixture into 700 mL of stirred water and washing the reaction flask with water and a small amount of methanol. With water, volume is adjusted to 900mL, and suspension is filtered through diatomite thin layer (slow filtration), and filter cake is washed with water.Wet filter cake and filter paper are broken, and first stirred in 20mL acetone, then 500mL DCM is added in the mixture while stirring.Organic layer is filtered through the second diatomite thin pad, transferred in separating funnel and separated with water, through MgSO4 drying, filtered and concentrated to dryness.Mixture is purified by flash chromatography (first wavelength=300nm, second wavelength=440nm), 220g post, balanced with 50% toluene / hexane, dissolved and loaded in hexane: toluene (2:1), eluted with 50% (1CV) → 100% toluene (10CV).Required fraction shows strong ultraviolet peak at 440nm.

[0482] The fractions are grouped into a mixture of early eluting, an intermediate peak and a late eluting fraction. The early eluting fraction is a trace of mixed Br / CF3 isomers, and is discarded. The intermediate peak is mainly three kinds of CF3 isomers, which is 204mg (26.0% yield). The late eluting fraction is two kinds of CF3, three kinds of CF3 and four kinds of CF3 mixed isomers, which is 75mg (10% yield).

[0483] 4-(9,10-bis(trifluoromethyl)perylene-3-yl)butyric acid: 4-(9,10-bis(trifluoromethyl)perylene-3-yl)butyric acid methyl ester (0.084mmol, 41mg) was added to a 100mL 2-necked round-bottom flask and suspended in anhydrous ethanol (80mL). The flask was equipped with a finned reflux condenser and flushed with argon. The reaction mixture was treated with potassium hydroxide (12.7mmol, 713mg) and heated to 80°C and stirred at this temperature under argon for 6 hours. The reaction was cooled to room temperature and the reaction mixture was evaporated to dryness. After acidification, the crude product was purified by C 18 The fractions were evaporated to dryness to give 40 mg (100% yield). The material was used without further purification. MS (APCI): Chemical formula C 26 H 16 F6O2(M - ) calculated value = 474; measured value: 474.

[0484] PC-47 (10-(4-((4-(9,10-bis(trifluoromethyl)perylene-3-yl)butanoyl)oxy)-2,6-dimethylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4,14,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylic acid dibenzyl ester): Place a stirring bar, 4-(9,10-bis(trifluoromethyl)perylene-3-yl)butanoyl)oxy)-2,6-dimethylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4,14,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylate in a 40 mL screw-top bottle. The reaction mixture was stirred at room temperature overnight. The mixture was stirred at room temperature for 30 minutes ... An additional portion of 4-(perylene-3-yl)butanoic acid (0.150 mmol, 51 mg) was added and stirred at 50°C overnight under argon. The solvent was evaporated to dryness and the product was purified by flash chromatography on silica gel (100% hexanes (1CV) → 5% EtOAc / hexanes (0CV) → 40% EtOAc / hexanes (10CV)). The fractions containing the product were evaporated to dryness and subjected to further purification by flash chromatography on silica gel (100% hexanes (1CV) → 10% EtOAc / hexanes (0CV) → 30% EtOAc / hexanes (10CV). The fractions containing the product were evaporated to dryness to give 72 mg (yield 78%). MS (APCI): Formula C 63 H 49 BF8N2O6(M - ) calculated value = 1092; measured value: 1092.

[0485] Example 2.48 PC-48:

[0486]

[0487] 2-Oxo-2-(perylene-3-yl)ethyl acetate: A stirring bar was added to a 100 mL 2-neck round bottom flask and flushed with argon. AlCl3 (15.0 mmol, 2.00 g) was added to the flask followed by anhydrous dichloroethane (150 mL). The solution was stirred at room temperature and 2-chloro-2-oxoethyl acetate (12.0 mmol, 1.34 mL) was added followed by perylene (10.0 mmol, 2.523 g). More anhydrous dichloroethane (50 mL) was added and the reaction was stirred at room temperature under argon for two hours. The reaction was quenched by adding water (100 mL) and 6N HCl aqueous solution (50 mL) under vigorous stirring. The layers were separated and the aqueous layer was extracted with DCM (3 x 25 mL). The organic layer was dried over MgSO4, filtered, and evaporated to dryness. The product was purified by flash chromatography on silica gel (60% DCM / hexanes (2CV)→100% DCM (8CV)→100% DCM). The fractions containing the product were evaporated to dryness to give 3.323 g (94% yield). MS (APCI): C 24 H 16 Calculated for O3 (M+H) = 353; found: 353.

[0488] Ethyl 2-(perylene-3-yl)acetate: Ethyl 2-oxo-2-(perylene-3-yl)acetate (3.00mmol, 1057mg) and a stirring bar were placed in a 40mL screw cap vial. The vial was flushed with argon. Anhydrous dichloromethane (10mL) and trifluoroacetic acid (10mL) were added to the vial. The vial was sealed with a screw cap septum and triethylsilane (6.6mmol, 1.05mL) was added under stirring. The reaction was stirred at room temperature under argon for 4 hours, at which time the reduction was found to be complete by LCMS. The reaction mixture was evaporated to dryness and azeotroped with toluene to remove residual trifluoroacetic acid. The reaction mixture was purified by flash chromatography on silica gel (60% DCM / hexane (2CV) → 100% DCM (8CV) → 100% DCM). The fraction containing the product was evaporated to dryness to give 433mg (43% yield). MS (APCI): C 24 H 18 Calculated value for O2 (MH) = 337; found: 337.

[0489] 2-(Perylene-3-yl)acetic acid: To a 100 mL 2-necked round bottom flask was added ethyl 2-(perylene-3-yl)acetate (1.27 mmol, 430 mg) and suspended in anhydrous ethanol (80 mL). The flask was equipped with a finned reflux condenser and flushed with argon. The reaction mixture was treated with potassium hydroxide (12.7 mmol, 713 mg) and heated to 95 ° C and stirred at this temperature under argon for 6 hours. The reaction was cooled to room temperature and the reaction mixture was evaporated to dryness. The crude product was dispersed in water (250 mL) and acidified to a pH of about 1 with 6N HCl. The product was centrifuged, washed with water, and dried in vacuo. The crude product was isolated with salt contamination but of sufficient purity to proceed to the next step. The yield was assumed to be quantitative.

[0490] 2-(Perylene-3-yl)acetic acid 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl ester: A 40 mL screw cap vial was charged with a stir bar and flushed with argon. To the vial was added crude 2-(perylene-3-yl)acetic acid from the previous step (assumed to be 1.27 mmol, 394 mg), 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-4-yl)phenol (1.91 mmol, 419 mg), DMAP (2.54 mmol, 310 mg) and p-toluenesulfonic acid monohydrate (2.29 mmol, 434 mg). Anhydrous dichloromethane (30 mL) was added to the vial and the reaction mixture was stirred and then treated with diisopropylcarbodiimide (6.35 mmol, 994 uL). The vial was sealed with a screw cap septum and stirred overnight at room temperature under argon. The volume was reduced to about 5 mL by rotary evaporation and the mixture was directly loaded onto a prepared silica gel column and eluted (100% DCM (5CV) → 5% EtOAc / DCM (10CV)). The fractions containing the product fractions were evaporated to dryness to give 422 mg (65% yield). MS (APCI): C 34 H 29 Calculated value of BO4(MH)=511; found value: 511.

[0491] PC-48 3,3'-(14-(3,5-dimethyl-4'-(2-(perylene-3-yl)acetoxy)-[1,1'-biphenyl]-4-yl)-7,7-difluoro-1,3,4,7,10,11,12,13-octahydro-2H-614,714-[1,3,2]diazaborolina[4,3-a:6,1-a']diisoindole-5,9-diyl)(2E,2'E)-diacrylate: A 40 mL screw cap vial was charged with 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl 2-(perylene-3-yl)acetate (0.150 mmol, 7 7 mg), 3,3'-(14-(4-bromo-2,6-dimethylphenyl)-7,7-difluoro-1,3,4,7,10,11,12,13-octahydro-2H-6',7'-[1,3,2]diazaborolinacyclo[4,3-a:6,1-a']diisoindole-5,9-diyl)(2E,2'E)-diethyl diacrylate (see synthesis of PC-32 above) (0.100 mmol, 68 mg) and Pd(dppf)Cl2 (0.015 mmol, 11 mg) were then charged with K2CO3 (1.0 M in H2O, 0.150 mmol, 0.15 mL). The vial was sealed with a screw cap septum and bubbled with argon for 30 min. The reaction mixture was heated at 85°C overnight. The crude mixture was evaporated to dryness, dispersed in dichloromethane, and purified on silica gel (100% DCM (1CV) → 10% EtOAc / DCM (10CV)). The fractions containing the product were evaporated to dryness and purified a second time by flash chromatography on silica gel (20% EtOAc / hexanes (2CV) → 60% EtOAc / hexanes (15CV). The fractions containing the product were evaporated to dryness to give 24 mg, a yield of 32%. MS (APCI): C 63 H 55 Calculated for BF2N2O6 (MH) = 983; Found: 983.

[0492] Example 2.49 PC-49:

[0493]

[0494] Methyl 4-(dicyanoperylene-3-yl)butyrate:

[0495]

[0496] Under argon atmosphere, 356 mg (1.01 mmol) of dibromoperylene intermediate (described in Example 2.44 above), a mixture of positional isomers, 142 mg (0.245 mmol) of xanthene (xantphos), 45 mg (0.253 mmol) of PdCl2, 285 mg (2.427 mmol) of Zn (CN)2 in degassed anhydrous DMA were placed in a 50 mL vial, stirred at room temperature and bubbled with argon for 15 min. 0.348 mL (2.04 mmol) of DIEA was added. The vial was closed with a Teflon cap and stirred at 85 ° C for 48 h. After cooling to room temperature, the dark insoluble material was poured into 50 mL of water, extracted into 150 mL of DCM, and the organic layer was separated, dried over MgSO4 and concentrated. The crude product was loaded onto a SiO2 column and eluted with DCM:hexane (1:1) and then DCM only to obtain 240 mg of a brown solid (a mixture of three isomers of dicyanoperylene derivatives) in 59% yield. LCMS (APCI+): Formula C 27 H 19 Calculated value of M+H of N2O2: 403.13; Found: 403

[0497] 4-(Dicyanoperylene-3-yl)butanoic acid:

[0498]

[0499] To a mixture of 138 mg (0.343 mmol) of methyl 4-(dicyanoperylene-3-yl)butanoate was added 0.5 mL (2.5 mmol) of 5N KOH aqueous solution, 3 mL of THF, 0.5 mL of MeOH, and 0.5 mL of DCM. The resulting mixture was stirred at room temperature for 16 h, and LCMS showed the desired compound. 0.6 mL of 6N HCl aqueous solution (3.6 mmol) was slowly added to acidify the mixture. The resulting mixture was concentrated to a volume of 1 mL. 10 mL of DCM was added; the mixture was washed with water (2 mL×2). The organic layer was separated, dried over MgSO4 and concentrated to dryness to give 120 mg of a brown solid with a yield of 90%. LCMS (APCI-): Formula C 26 H 16 M of N2O2 - Calculated value: 388.12; Measured value: 388

[0500] PC-49: 10-(4-((4-(4,9-dicyanoperylene-3-yl)butanoyl)oxy)-2,6-dimethylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4,14,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylic acid dibenzyl ester: 4-(4,9-dicyanoperylene-3-yl)butanoic acid (120 mg, 0.308 mmol) was added to the mixture. 1), a mixture of compound 44.2 [5,5-difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-1,3,7,9-tetramethyl-5H-4-14,5-14-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinyl-2,8-dicarboxylic acid dibenzyl ester] (196 mg, 0.308 mmol) and anhydrous DCE (4 ml) was placed in a vial and bubbled with argon for 15 minutes at room temperature. DMAP-pTSA salt (39.04 mg, 0.012 mmol) was added and the vial was sealed with a polytetrafluoroethylene cap. DIC (192.25 mg, 0.616 mmol) was added via a syringe. The resulting reaction mixture was stirred at room temperature for 16 hours under an argon atmosphere. TLC and LCMS showed that the reaction was complete. The reaction was concentrated to dryness. The residue was stirred with toluene (15 mL) for 10 minutes, and the precipitate was filtered and washed with 10 mL toluene. The filtrate and washings were collected and concentrated to a volume of 10 mL. The toluene solution of the crude product was injected into a 24 g SiO2 column. Flash column chromatography was performed by eluting with toluene: ethyl acetate (95:5) to (9:1) to obtain 257 mg of an orange solid with a yield of 82%. LCMS (APCI-): Compound C 63 H 49 M of BF2N4O6 - Calculated value: 1006.37; Measured value: 1006

[0501] Example 2.50 PC-50:

[0502]

[0503] Compound 50.1 (1-methyl-2,4,5,6-tetrahydrocyclopentyl[c]pyrrole): To LiAlH4 (2.07 mmol, 827 μL of a 2.5 M solution in THF) at 0°C was slowly added a solution of ethyl 2,4,5,6-tetrahydrocyclopenta[c]pyrrole-1-carboxylate (0.686 mmol, 123 mg) in THF (3.00 mL). The reaction mixture was heated to room temperature and then heated to reflux for 1 h. The reaction mixture was then cooled to room temperature, saturated aqueous potassium sodium tartrate (10.0 mL) and CH2Cl2 (10.0 mL) were added, and the mixture was stirred at room temperature for 16 h and then extracted with CH2Cl2 (3×10.0 mL). The combined organics were dried (MgSO4) and concentrated under reduced pressure. Flash chromatography gave 44 mg of compound 50.1 as a yellow oil (53% yield). 1 H NMR (400 MHz, chloroform-d) δ 7.56 (br s, 1H), 6.30 (s, 1H), 2.63 (t, J = 7.1 Hz, 2H), 2.54 (t, J = 7.1 Hz, 2H), 2.31 (apparent p, J = 7.2 Hz, 2H), 2.19 (s, 3H); 13 C NMR (101 MHz, chloroform-d) δ 130.5, 127.0, 118.3, 106.8, 31.8, 25.1, 24.0, 11.9.

[0504] Compound 50.2 (4-(4,9,10-tris(trifluoromethyl)perylene-3-yl)butanoic acid 4-formyl-3,5-dimethylphenyl ester): Compound 50.2 was synthesized from 4-(4,9,10-tris(trifluoromethyl)perylene-3-yl)butanoic acid (1.438 mmol, 780 mg) and 4-hydroxy-2,6-dimethylbenzaldehyde (2.157 mmol, 324 mg) in a similar manner to compound 42.3. The crude product was purified by flash chromatography on silica gel (isocratic toluene). Fractions containing the product (as a mixture of isomers) were evaporated to dryness to give 765 mg (78.9%). MS (APCI): Formula C 36 H 23 Calculated value for F9O3(M-)=674; found: 674. 1 HNMR(400MHz,)δ10.54(s,1H),8.44-7.58(m,8H),6.93-6.81(m,2H),3.4 2-3.25(m,2H),2.85-2.72(m,2H),2.67-2.56(m,6H),2.38-2.20(m,2H).

[0505] PC-50 (4-(4,9,10-tris(trifluoromethyl)perylene-3-yl)butanoic acid 4-(6,6-difluoro-4,8-dimethyl-2,3,6,9,10,11-hexahydro-1H-5λ 4 ,6λ 4 -cyclopenta[3,4]pyrrolo[1,2-c]cyclopenta[3,4]pyrrolo[2,1-f][1,3,2]diazaborin-12-yl)-3,5-dimethylphenyl ester): To a solution of compound 50.1 (0.182 mmol, 22.0 mg) and pTsOH·H2O (0.009 mmol, 1.00 mg) in anhydrous CH2Cl2 (1.80 mL) was added compound 50.2 (0.083 mmol, 56.0 mg) at room temperature under argon atmosphere. The reaction mixture was stirred at room temperature for 2.5 h, then cooled to 0°C, p-tetrachlorobenzoquinone (0.083 mmol, 21.0 mg) was added in one portion, and stirring was continued for 15 min. Triethylamine (0.495 mmol, 69.0 μL) was added and the mixture was heated to room temperature over 10 minutes, then BF3·OEt2 (0.750 mmol, 92.0 μL) was added and stirring continued for another 45 min. The reaction mixture was diluted with EtOAc (5.00 mL), washed with 1M HCl (3×5.00 mL) and saturated aqueous NaCl (5.00 mL), dried (MgSO4) and concentrated under reduced pressure. Flash chromatography (1:1 hexane / CH2Cl2) gave 27.0 mg of PC-50 (35% yield) as an orange powder. 1 H NMR (400 MHz, CHLOROFORM-d) δ 8.42-7.55 (m, 8H), 6.95-6.78 (m, 2H), 3.46-3.27 (m, 2H), 2.82-2.60 (m, 2H), 2.59-2.36 (m, 10H), 2.36-2.24 (m, 2H), 2.24-2.00 (m, 11H), 1.96-1.83 (m, 4H).

[0506] Example 2.51 PC-51:

[0507]

[0508] PC-51 (4-(4,9,10-tris(trifluoromethyl)perylene-3-yl)butyric acid 4-(2,8-diethyl-5,5-difluoro-1,3,7,9-tetramethyl-5H-4-14,5-14-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-10-yl)-3,5-dimethylphenyl ester): Compound 46.1 [4-(4,9,10-tris(trifluoromethyl)perylene-3-yl)butyric acid] (77.5 mg, A mixture of 4-(2,8-diethyl-5,5-difluoro-1,3,7,9-tetramethyl-5H-4',5'-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinylcyclohexene-10-yl)-3,5-dimethylphenol dicarboxylate] (61.0 mg, 0.143 mmol) and anhydrous DCE (5 mL) was placed in a vial and bubbled with argon for 15 minutes at room temperature. DMAP-pTSA salt (89.25 mg, 0.286 mmol) was added and the vial was sealed with a Teflon cap. DIC (0.109 mL, 0.286 mmol) was added via a syringe and needle. The resulting reaction mixture was stirred at room temperature for 2 hours under an argon atmosphere. TLC and LCMS showed that the reaction was complete. The reactant was loaded onto a silica gel column and eluted with toluene:ethyl acetate (9:1) to obtain 117 mg of an orange-red substance with a yield of 86%. LCMS (APCI-): Formula C 52 H 44 BF 11 M of N2O2 - Calculated value: 948.33; measured value: 948.

[0509] Example 2.52 PC-52:

[0510]

[0511] PC-52: A mixture of ethyl 2-methyl-1H-pyrrole-3-carboxylate (100 mg, 0.65 mmol), compound 50.2 [4-(4,9,10-tris(trifluoromethyl)perylene-3-yl)butanoate 4-formyl-3,5-dimethylphenyl ester] (100 mg, 0.146 mmol) in 5 mL of dichloroethane was heated at 65° C. for 3 days with 120 mg of MgSO4 and 3 drops of TFA. After cooling with an ice bath, DDQ (35 mg, 0.15 mmol) was added to the mixture and stirred for 10 min, followed by the addition of triethylamine (0.13 mL, 0.9 mmol) and BF3-ether (0.09 mL, 0.5 mmol). The mixture was heated at 60°C for 60 min, then another batch of triethylamine (0.13 mL, 0.9 mmol) and BF3-ether (0.09 mL, 0.5 mmol) were added, and the mixture was heated for another 30 min. The resulting mixture was fed to a silica gel column and purified by flash chromatography using an eluent of DCM / ethyl acetate (0%→10% ethyl acetate). The main fractions were collected and the solvent was removed under reduced pressure to give an orange-red solid PC-52 (90 mg, 60% yield). LCMS (APCI): C 52 H 40 BF 11 Calculated value of N2O6(M-): 1008.2; found value: 1008. 1 H NMR (400 MHz, TCE-d2) δ 8.48-7.48 (m, 8H), 6.99 (two singlets, 2H), 6.92-6.83 (m, 2H), 4.29-4.10 (m, 4H), 3.27 (s, 2H), 2.84 (s, 6H), 2.79-2.47 (m, 2H), 2.33-2.14 (m, 2H), 2.06 (two singlets, 6H), 1.23 (m, 6H).

[0512] Example 2.53 PC-53:

[0513]

[0514] Compound 53.1 [10-(2,6-difluoro-4-hydroxyphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4λ 4 ,5λ 4-Dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinyl-2,8-dicarboxylate]: To a solution of 2,4-dimethyl-1H-pyrrole-3-carboxylic acid benzyl ester (1.05 mmol, 241 mg) and 2,6-difluoro-4-hydroxybenzaldehyde (0.500 mmol, 79 mg) in CH2Cl2 (10.0 mL) was added pTsOH·H2O (0.050 mmol, 6 mg), and the reaction mixture was stirred at room temperature for 45 min. It was then cooled to 0°C, DDQ (0.600 mmol, 136 mg) was added, and the mixture was stirred at room temperature for 1 h. Triethylamine (3.00 mmol, 417 μL) was added, the mixture was stirred at 0°C for 10 min, and then BF3·OEt2 (4.50 mmol, 555 μL) was added, and the mixture was stirred at room temperature for 2 h. More triethylamine (3.00 mmol, 417 μL) was added, and after stirring at room temperature for 5 min, BF3·OEt2 (4.50 mmol, 555 μL) was added, and the mixture was stirred at room temperature for another 1 h. The mixture was then diluted with EtOAc (30.0 mL), washed with 3M HCl (3×30.0 mL), dried (MgSO4) and concentrated under reduced pressure. Flash chromatography (9:1, toluene / EtOAc) gave 175 mg of compound 53.1 (54% yield) as an orange solid. 1 H NMR (400 MHz, CHLOROFORM-d) δ 7.41-7.30 (m, 10H), 6.59-6.53 (m, 2H), 5.30 (s, 4H), 2.82 (s, 6H), 1.92 (s, 6H).

[0515] PC-53[10-(2,6-difluoro-4-((4-(tris(trifluoromethyl)perylene-3-yl)butanoyl)oxy)phenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4λ 4 ,5λ 4 -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinyl-2,8-dicarboxylic acid dibenzyl ester]): DIC (0.312 mmol, 49.0 μL) was added to a solution of compound 53.1 (0.078 mmol, 50.0 mg), compound 46.1 (0.085 mmol, 46.0 mg) and DMAP·pTsOH salt (0.078 mmol, 23.0 mg) in CH2Cl2 (0.50 mL), and the reaction mixture was stirred at room temperature for 3 h. The reaction mixture was then filtered through celite and concentrated under reduced pressure. Flash chromatography (4:1 hexane / EtOAc → 3:2 hexane / EtOAc) gave 46.0 mg of PC-53 as an orange / red solid (51% yield).1 H NMR (400 MHz, CHLOROFORM-d) δ 8.34-7.73 (m, 8H), 7.42-7.28 (m, 10H), 7.02-6.89 (m, 2H), 5.31-5.23 (m, 4H), 3.43-3.29 (m, 2H), 2.87-2.73 (m, 8H), 2.37-2.24 (m, 2H), 1.97-1.83 (m, 6H).

[0516] Example 2.54 PC-54:

[0517]

[0518] Compound 54.1 [10-(2,6-dichloro-4-hydroxyphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4λ 4 ,5λ 4 -Dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinyl-2,8-dicarboxylate]: To a solution of 2,4-dimethyl-1H-pyrrole-3-carboxylic acid benzyl ester (1.05 mmol, 241 mg) and 2,6-difluoro-4-hydroxybenzaldehyde (0.500 mmol, 96 mg) in CH2Cl2 (10.0 mL) was added pTsOH·H2O (0.050 mmol, 6 mg), and the reaction mixture was stirred at room temperature for 1.5 h. DDQ (0.600 mmol, 136 mg) was added, and the mixture was stirred at room temperature for 2 h. Triethylamine (3.00 mmol, 417 μL) was then added, and the mixture was stirred at room temperature for 30 min, and then BF3·OEt2 (4.50 mmol, 555 μL) was added, and the mixture was stirred at room temperature for 1 h. The mixture was then diluted with EtOAc (30.0 mL), washed with 3M HCl (3 x 30.0 mL), dried (MgSO4) and concentrated under reduced pressure. Flash chromatography (toluene→19:1, toluene / EtOAc) afforded 211 mg of compound 54.1 (62% yield) as an orange solid. 1 H NMR (400 MHz, CHLOROFORM-d) δ 7.42-7.30 (m, 10H), 6.98 (s, 2H), 5.29 (s, 4H), 2.83 (s, 6H), 1.84 (s, 6H).

[0519] PC-54[10-(2,6-dichloro-4-((4-(tris(trifluoromethyl)perylene-3-yl)butanoyl)oxy)phenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4λ 4 ,5λ 4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinyl-2,8-dicarboxylate]: To a solution of compound 54.1 (0.074 mmol, 50.0 mg), compound 46.1 (0.081 mmol, 44.0 mg) and DMAP·pTsOH salt (0.074 mmol, 23.0 mg) in CH2Cl2 (0.50 mL) was added DIC (0.312 mmol, 49.0 μL) and the reaction mixture was stirred at room temperature for 3 h. The reaction mixture was then filtered through celite and concentrated under reduced pressure. Flash chromatography (toluene→19:1, toluene / EtOAc) gave 78.0 mg of PC-54 (88% yield) as an orange / red solid. 1 H NMR (400 MHz, CHLOROFORM-d) δ 8.37-7.71 (m, 8H), 7.39-7.29 (m, 10H), 5.32-5.23 (m, 4H), 3.42-3.29 (m, 2H), 2.89-2.69 (m, 8H), 2.39-2.20 (m, 2H), 1.91-1.76 (m, 6H).

[0520] Example 2.55 PC-55:

[0521]

[0522] Compound 55.1 [4-(tris(trifluoromethyl)perylene-3-yl)butanoic acid 4-formyl-3,5-dimethoxyphenyl ester]: To a solution of 2,6-dimethoxy-4-hydroxybenzaldehyde (0.246 mmol, 45.0 mg), compound 46.1 (0.369 mmol, 200 mg) and DMAP·pTsOH salt (0.246 mmol, 72.0 mg) in CH2Cl2 (1.25 mL) was added DIC (0.984 mmol, 154 μL), and the reaction mixture was stirred at room temperature for 1.5 h. The reaction mixture was then filtered through celite and concentrated under reduced pressure. Flash chromatography (19:1, toluene / EtOAc→9:1, toluene / EtOAc) gave 149 mg of compound 55.1 (86% yield) as an orange solid. 1 H NMR (400 MHz, CHLOROFORM-d) δ 10.51-10.36 (m, 1H), 8.34-7.60 (m, 8H), 6.45-6.26 (m, 2H), 4.03-3.76 (m, 6H), 3.43-3.29 (m, 2H), 2.82-2.61 (m, 2H), 2.34-2.06 (m, 2H).

[0523] PC-55[10-(2,6-dimethoxy-4-((4-(tris(trifluoromethyl)perylene-3-yl)butanoyl)oxy)phenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4λ 4 ,5λ 4 [1,2-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinyl-2,8-dicarboxylic acid dibenzyl ester]: To a solution of 2,4-dimethyl-1H-pyrrole-3-carboxylic acid benzyl ester (0.311 mmol, 71.0 mg) and compound 55.1 (0.142 mmol, 100 mg) in CH2Cl2 (3.00 mL) was added pTsOH·H2O (0.014 mmol, 1.70 mg), and the reaction mixture was stirred at room temperature for 1.5 h. DDQ (0.170 mmol, 39 mg) was then added, and the mixture was stirred at room temperature for 1 h. Triethylamine (0.852 mmol, 118 μL) was added, and the mixture was stirred at room temperature for 30 min, and then BF3·OEt2 (1.28 mmol, 158 μL) was added, and the mixture was stirred at room temperature for 75 min. The mixture was then diluted with EtOAc (20.0 mL), washed with 3M HCl (3 x 20.0 mL), dried (MgSO4) and concentrated under reduced pressure. Flash chromatography (toluene→19:1, toluene / EtOAc) afforded 74.0 mg of PC-55 (44% yield) as an orange solid. 1 H NMR (400 MHz, CHLOROFORM-d) δ 8.35-7.64 (m, 8H), 7.40-7.27 (m, 10H), 6.52-6.44 (m, 2H), 5.29-5.23 (m, 4H), 3.73-3.63 (m, 6H), 3.45-3.29 (m, 2H), 2.84-2.63 (m, 8H), 2.36-2.23 (m, 2H), 1.90-1.81 (m, 6H).

[0524] Example 2.56 PC-56:

[0525]

[0526] Compound 56.1 (2,4-dimethyl-1H-pyrrole-3-carboxylic acid): Benzyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (5.0 mmol, 1146 mg), 10% Pd / C (wet, 500 mg) and a stirring bar were charged into a 500 mL pear-shaped flask. EtOAc (100 mL) and ethanol (200 proof, 20 mL) were added to the flask. The flask was sealed with a septum and the headspace was evacuated under stirring at room temperature. The atmosphere was replaced with hydrogen from a balloon. The vacuum / backfill H2 procedure was repeated two more times, and the flask was then stirred under a hydrogen balloon atmosphere for 3 hours at room temperature. LCMS indicated that the starting material had been completely consumed. The reaction flask was flushed with argon, and the reaction mixture was filtered through a pad of celite. The solvent was evaporated to dryness to give the product in pure form. 696 mg (100% yield) was obtained. MS (APCI): calculated value for chemical formula C7H9NO2 (M+H) = 140, found value: 140. 1 H NMR(400MHz,TCE-d2)δ11.07(br s,1H),8.06(br s,1H),6.41(s,1H),2.52(s,3H),2.26(s,3H).

[0527] Compound 56.2 (4-hydroxybutyl 4-(perylene-3-yl)butanoate): Compound 56.2 was synthesized from 4-(perylene-3-yl)butanoic acid (1.0 mmol, 338 mg), 1,4-butanediol (50.0 mmol) and DMAP (0.200 mmol, 59 mg) in 4.42 mL of anhydrous THF (50 mL) and anhydrous DCM (50 mL) in a 40 mL screw cap vial with a stirring bar. Diisopropylcarbodiimide (0.300 mmol, 47 uL) was added and the reaction was stirred at room temperature under argon overnight. The next morning, anhydrous tetrahydrofuran (10 mL) was added and sonicated for 30 seconds. The crude product was purified by flash chromatography on silica gel (10% EtOAc / DM (1 CV) → 40% EtOAc / DCM (20 CV)). The fractions containing the product were evaporated to dryness to give a yellow solid. Obtained 374 mg (91.0% yield). MS (APCI): Chemical formula C 28 H 26 Calculated value of O3(M-)=410, found value: 410. 1H NMR (400MHz, TCE-d2) δ8.24(d,J=7.5Hz,1H),8.20(d,J=7.7Hz,1H),8.18(d,J=7.7Hz,1H),8.14(d,J=7.7Hz,1H ),7.92(d,J=8.5Hz,1H),7.71(d,J=5.9Hz,1H),7.69(d,J=5.9Hz,1H),7.56(t,J=7.9Hz,1H),7.51(t,J=7.8Hz,1 H),7.50(t,J=7.8Hz,1H),7.37(d,J=7.7Hz,1H),4.12(t,J=6.5Hz,2H),3.65(q,J=6.0Hz,2H),3.07(t,J=7.7Hz ,2H),2.46(t,J=7.3Hz,2H),2.10(p,J=7.4Hz,2H),1.78-1.67(m,2H),1.67-1.58(m,2H),1.34(t,J=5.3Hz,1H).

[0528] Compound 56.3 (2,4-dimethyl-1H-pyrrole-3-carboxylic acid 4-((4-(perylene-3-yl)butanoyl)oxy)butyl ester): A 40 mL screw cap vial was charged with a stir bar, compound 56.1 (600 μmol, 84 mg) and compound 56.2 (500 μmol, 205 mg) and DMAP:pTsOH 1:1 salt (0.200 mmol, 59 mg). The vial was flushed with argon and anhydrous dichloromethane (20 mL) was added. Diisopropylcarbodiimide (0.300 mmol, 47 uL) was added and the reaction was stirred at room temperature under argon overnight. The next morning, anhydrous tetrahydrofuran (10 mL) was added and sonicated for 30 seconds. An additional portion of 4-(perylene-3-yl)butanoic acid (0.150 mmol, 51 mg) was added and stirred at 50 °C under argon overnight. To bring the reaction closer to completion, the reaction was heated to 50°C and more compound 56.1 (2 x 600 μmol, 84 mg) was added. The conversion reached a plateau, so the crude product was purified by flash chromatography on silica gel (100% DCM (1CV) → 10% EtOAc / DCM (10CV)). The fractions containing the product were evaporated to dryness to give a pale yellow solid. 158 mg (59.4% yield) was obtained. MS (APCI): Formula C 35 H 33 Calculated value of NO4(M-)=531, found value: 531. 1H NMR(400MHz,TCE-d2)δ8.23(dd,J=7.6,0.7Hz,1H),8.20(dd,J=7.7,1.0Hz,1H),8.17(dd,J=7.7,1.0Hz,1H),8.14(d,J=7.7Hz,1H),7.94(s,1H),7.92(d,J=8.5Hz,1H),7.71(d,J=5.8Hz,1H),7.69(d,J=5.7Hz,1H),7.57(d,J=7.7Hz,1H),7.55(d,J=7.6Hz,1H),7.51(t,J=7.6Hz,1H),7.50(t,J=7.8Hz,1H),7.36(d,J=7.7Hz,1H),6.36(dd,J=2.3,1.2Hz,1H),4.28-4.20(m,2H),4.19-4.11(m,2H),3.12-3.04(m,2H),2.46(t,J=7.3Hz,2H),2.46(s,3H),2.22(d,J=1.1Hz,3H),2.10(p,J=7.4Hz,2H),1.85-1.76(m,4H)。

[0529] PC-56 [10-(2,6-dimethylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4,14,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinyl-2,8-dicarboxylic acid bis(4-((4-(perylene-3-yl)butanoyl)oxy)butyl ester]: A 40 mL screw-cap vial was equipped with a screw-cap septum and a stirring bar. Compound 56.3 (150 μmol, 80 mg) and 2,6-dimethylbenzaldehyde (82.5 μmol, 11.1 mg), pTsOH.H2O (15 μmol, 3 mg) were dissolved in anhydrous DCM (5 mL). The reaction mixture was bubbled with argon for 5 minutes, then DDQ (97.5 μmol, 22 mg) was added. The reaction was stirred at room temperature overnight under argon. The next morning, DDQ (97.5 μmol, 22 mg) was added and stirred at room temperature for 20 minutes. Triethylamine (450 μmol, 63 uL) and BF3.OEt2 (675 μmol, 83 uL) were added to the reaction and stirred for 30, then additional triethylamine (450 μmol, 63 uL) and BF3.OEt2 (675 μmol, 83 uL) were added. The reaction was stirred at room temperature for 4 hours, then diluted with EtOAc (50 mL), and washed with 1.25 N The crude product was purified by flash chromatography on silica gel (36% EtOAc / hexane (1.1CV) → 56% EtOAc / hexane (3.1CV), then isocratic 56% EtOAc / hexane). The fractions containing the product were evaporated to dryness to give an orange solid, which was then dried in a vacuum oven at 50°C overnight. 46 mg (50.0% yield based on pyrrole) was obtained. MS (APCI): Chemical formula C 79 H 71 Calculated value for BF2N2O8(M-)=1224, found: 1224. 11H NMR (400 MHz, chloroform-d) δ 8.22 - 8.19 (m, 2H), 8.18 (dd, J = 7.7, 0.8 Hz, 2H), 8.15 (dd, J = 7.6, 0.9 Hz, 2H), 8.11 (d, J = 7.7 Hz, 2H), 7.89 (dd, J = 8.4, 0.7 Hz, 2H), 7.67 (d, J = 5.3 Hz, 2H), 7.65 (d, J = 5.3 Hz, 2H), 7.52 (d, J = 7.6 Hz, 1H), 7.50 (d, J = 7.6 Hz, 1H), 7.49 - 7.42 (m, 2H), 7.50 - 7.41 (m, 2H), 7.32 (d, J = 7.7 Hz, 2H), 7.25 (dd, J = 8.1, 7.1 Hz, 1H), 7.11 (d, J = 7.5 Hz, 2H), 4.25 (t, J = 6.0 Hz, 4H), 4.12 (t, J = 6.0 Hz, 4H), 3.06 (dd, J = 8.7, 6.7 Hz, 4H), 2.85 (s, 6H), 2.43 (t, J = 7.3 Hz, 4H), 2.15 - 2.06 (m, 4H), 2.07 (s, 6H), 1.83 - 1.69 (m, 8H), 1.64 (s, 6H).

[0530] Example 2.57 PC-57:

[0531]

[0532] Compound 57.1 [(4-(perylene-3-yl)butanoic acid 4-formyl-3,5-dimethylphenyl ester)]: Compound 22.1 was synthesized from 4-hydroxy-2,6-dimethylbenzaldehyde (1.89 mmol, 284 mg) and 4-(perylene-3-yl)butanoic acid (0.946 mmol, 320 mg) in a similar manner to compound 2. A 40 mL screw cap vial was charged with a stir bar, 4-hydroxy-2,6-dimethylbenzaldehyde (1.89 mmol, 284 mg) and 4-(perylene-3-yl)butanoic acid (0.946 mmol, 320 mg) and DMAP:pTsOH 1:1 salt (0.200 mmol, 59 mg). The vial was flushed with argon and anhydrous dichloromethane (20 mL) was added. Diisopropylcarbodiimide (0.300mmol, 47uL) was added and the reaction was stirred at room temperature overnight under argon. The next morning, anhydrous tetrahydrofuran (10mL) was added and sonicated for 30 seconds. An additional portion of 4-(perylene-3-yl)butyric acid (0.150mmol, 51mg) was added and stirred at 50°C overnight under argon. The crude product was purified by flash chromatography on silica gel (100% toluene (5CV) → 10% EtOAc / toluene (10CV)). The fractions containing the product were evaporated to dryness. 296mg (66.5% yield) of an orange solid was obtained. MS (APCI): Chemical formula C 33 H 26 Calculated value of O3(M-)=470, found: 470. 1 H NMR(400MHz,TCE-d2)δ10.52(s,1H),8.25(d,J=7.5Hz,1H),8.23-8.17(m,2H),8.16(d,J =7.8Hz,1H),7.94(d,J=8.4Hz,1H),7.72(d,J=5.1Hz,1H),7.70(d,J=5.1Hz,1H),7.57(t ,J=8.0Hz,1H),7.51(t,J=7.8Hz,1H),7.51(t,J=7.8Hz,1H),7.40(d,J=7.7Hz,1H),6.84 (s, 2H), 3.17 (t, J = 7.6Hz, 2H), 2.72 (t, J = 7.2Hz, 2H), 2.58 (s, 6H), 2.23 (p, J = 7.3Hz, 2H).

[0533] PC-57 [10-(2,6-dimethyl-4-((4-(perylene-3-yl)butyryl)oxy)phenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4-14,5-14-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinyl-2,8-dicarboxylic acid bis(4-((4-(perylene-3-yl)butyryl)oxy)butyl ester]: prepared in a manner similar to PC-56 from compound 56.3 (13 PC-57 was synthesized from 1,4-dihydro-1,4-dihydro-2-nitropropene (2,4-dihydro-1,4-dihydro-2-nitropropene) (0 μmol, 69.3 mg) and compound 57.1 (65.2 μmol, 30.7 mg) by adding 6 equivalents of triethylamine and 9 equivalents of BF3.OEt2 twice. The crude reaction mixture was treated in the same manner as PC-56. The crude product was purified by flash chromatography on silica gel (36% EtOAc / hexane (1.1 CV) → 60% EtOAc / hexane (4 CV) → 60% isocratic). The product eluted with the impurities. The fractions containing the product were evaporated to dryness and purified again by flash chromatography on silica gel (100% toluene (1CV) → 10% EtOAc / toluene (10CV)). There were still some impurities eluting. The fractions containing the product were evaporated to dryness and purified again by flash chromatography on silica gel (100% DCM (1CV) → 1% EtOAc / DCM (1CV), isocratic 1% EtOAc / DCM (1CV) → 2% EtOAc / DCM (1CV) EtOAc / DCM (0CV) → isocratic 2% EtOAc / DCM (3CV) → 4% EtOAc / DCM (0CV) → isocratic 4% EtOAc / DCM (1CV) → 6% EtOAc / DCM (0CV) → 6% isocratic until the compound is eluted). The fractions containing pure PC-57 were evaporated to dryness to give an orange solid. 13 mg (yield based on pyrrole is 12.7%). MS (APCI): Chemical formula C 103 H 87 BF2N2O 10 Calculated value of (M-)=1560, found value:1560. 1H NMR (400MHz, chloroform-d) δ8.19-8.05(m,12H),7.90-7.84(m,3H),7.65(d,J=5.5Hz,3H),7.63(d,J=5.3Hz,3H),7.46 (dtd,J=19.4,7.8,2.8Hz,9H),7.33(d,J=7.7Hz,1H),7.29(d,J=7.7Hz,2H),6.88(s,2H),4.26(t,J=6.0Hz,4H) ,4.12(t,J=5.9Hz,4H),3.13(t,J=7.6Hz,2H),3.04(dd,J=8.7,6.7Hz,4H),2.85(s,6H),2.66(t,J=7.2Hz,2H) ,2.43(t,J=7.3Hz,4H),2.21(p,J=7.3Hz,2H),2.15-2.06(m,4H),2.04(s,6H),1.83-1.70(m,7H),1.69(s,6H).

[0534] Example 3: Manufacturing a color conversion film

[0535] The glass substrate was prepared substantially as follows. A 1.1 mm thick glass substrate was cut into a measurement size of 1 inch by 1 inch. The glass substrate was then washed with detergent and deionized (DI) water, rinsed with fresh DI water, and sonicated for about 1 hour. The glass was then immersed in isopropyl alcohol (IPA) and sonicated for about 1 hour. The glass substrate was then immersed in acetone and sonicated for about 1 hour. The glass was then removed from the acetone bath and dried with nitrogen at room temperature.

[0536] A 20 wt% solution of poly(methyl methacrylate) (PMMA) (average molecular weight of 120,000 as measured by GPC purchased from MilliporeSigma, Burlington, MA, USA) copolymer in cyclopentanone (99.9% purity) was prepared. The prepared copolymer was stirred at 40°C overnight. [PMMA] CAS: 9011-14-7; [cyclopentanone] CAS: 120-92-3

[0537] The 20% PMMA solution (4 g) prepared above was added to 3 mg of the photoluminescent composite prepared as described above in a sealed container and mixed for about 30 minutes. The PMMA / phosphor solution was then spin-coated onto the prepared glass substrate at 1000 RPM for 20 seconds and then spin-coated onto the prepared glass substrate at 500 RPM for 5 seconds. The thickness of the resulting wet coating was about 10 μm. Any suitable coating thickness can be used, such as about 10-20 μm, about 20-30 μm, about 30-40 μm, about 40-50 μm, about 50-60 μm, about 20-40 μm, about 40 μm-80 μm, about 20 μm, about 30 μm, or about 40 μm. Prior to spin coating, the sample was covered with aluminum foil to prevent the sample from being exposed to light. Three samples were prepared in this manner for each of emission / FWHM and quantum yield, respectively. The spin-coated samples were baked in a vacuum oven at 80°C for 3 hours to evaporate the residual solvent.

[0538] The 1 inch x 1 inch sample was inserted into a Shimadzu, UV-3600 UV-VIS-NIR spectrophotometer (Shimadzu Instruments, Inc., Columbia, MD, USA). All equipment operations were performed in a nitrogen-filled glove box. The resulting absorption / emission spectra of PC-8 are shown in Figure 2. Figure 1 As shown, the final absorption / emission spectrum of PC-33 is as follows Figure 2 As shown, PC-46 Figure 3 As shown, PC-56 Figure 4 shown.

[0539] Fluorescence spectra of 1 inch x 1 inch film samples prepared as described above were measured using a Fluorolog spectrofluorometer (Horiba Scientific, Edison, NJ, USA) with the excitation wavelength set to the corresponding maximum absorption wavelength. The maximum emission and FWHM are shown in Table 1.

[0540] The quantum yield of the 1 inch x 1 inch samples prepared as described above was determined using a Quantarus-QY spectrophotometer (Hamamatsu Inc., Campbell CA, USA) excited at the corresponding maximum absorption wavelength. The results are recorded in Table 1.

[0541] The results of the film characterization (absorption peak wavelength, FWHM and quantum yield) are shown in Table 1 below.

[0542] Example 4: Photostability

[0543] The photostability of the photoluminescent composite was performed on 1 inch x 1 inch samples; comprising PMMA as described above. The photoluminescent composite was individually plated at 2 x 10 -3 The concentration of M will be included with the PMMA film sample. The sample was then exposed to a blue LED light source (Inspired LED, Tempe, AZ, USA) with an emission wavelength of 465 nm at room temperature. The blue LED light was incorporated into a 1 inch × 12 inch U-shaped channel, and a commercial diffuser was placed on top of the U-shaped channel to provide uniform light distribution. The 1 inch × 1 inch sample was placed on top of the diffuser. The average irradiance at the sample was 1.5 mW / cm 2 .

[0544] The absorption at the peak absorption wavelength was measured before and after the film was exposed to LED light for 165h, 330h and 500h respectively. The absorption of the samples was measured using a UV-vis 3600 (Shimadzu Manufacturing Company, Kyoto, Japan). The light stability was measured by dividing the absorption remaining after exposure by the absorption before the exposure time. The results are shown in Table 2 below.

[0545] Table 1.

[0546]

[0547]

[0548]

[0549]

[0550]

[0551]

[0552]

[0553]

[0554]

[0555]

[0556]

[0557]

[0558] Table 2.

[0559]

[0560]

Claims

1. A photoluminescent composite, comprising: a blue light absorbing moiety, wherein the blue light absorbing moiety comprises an optionally substituted perylene; a first linker moiety covalently linking the optionally substituted perylene and the boron dipyrromethene (BODIPY) moiety; wherein the optionally substituted perylene absorbs light energy at a first excitation wavelength and transfers a portion of the absorbed light energy to the BODIPY moiety; wherein the BODIPY moiety emits a portion of the transferred energy in the form of light energy of a second, higher wavelength; and wherein the emission quantum yield of the photoluminescent composite is greater than 80%, The photoluminescent composite is represented by the following formula: Where R 1 and R 6 are independently H, methyl or vinyl crotonate; G 2 is H, C1-C5 alkyl, CN, arylalkynyl, alkyl ester or -C(=O)O-(CH2)4-OC(=O)-(CH2)3-Z 1 ; R 3 and R 4 are independently H or C1-C5 alkyl; G 5 is -C(=O)O-(CH2)4-OC(=O)-(CH2)3-Z 2 ; G 2 and R 3 may be linked together to form additional monocyclic hydrocarbon ring structures or polycyclic hydrocarbon ring structures; R 4 and G 5 may be linked together to form additional monocyclic hydrocarbon ring structures or polycyclic hydrocarbon ring structures; G 7 -L3-Z 3 、-Ar-L3-Z 3 、-L3-Z 3 -L3-, or -Ar-L3-Z 3 -L3-Ar-, wherein Ar is an aryl group optionally substituted by methyl, F, Cl, methoxy; L3 is a single bond, or a linker moiety containing an -O- group; X1 and X2 are independently F, Cl, Br or I; and Z 1 , Z 2 and Z 3 Independently for: Where R 8 , R 9 , R 11 and R 12 is independently H, branched C4-C5 alkyl, CN, CF3, or 4-(trifluoromethyl)phenyl; When R 9 When R is H, branched C4-C5 alkyl, CN or CF3, 10 is H; When R 9 When it is 4-(trifluoromethyl)phenyl, R 10 is H or forms a direct bond to the 4-(trifluoromethyl)phenyl group, thereby forming (trifluoromethyl)indeno[1,2,3-cd]perylene.

2. The photoluminescent composite according to claim 1, wherein L3 is a linker moiety containing a -C(=O)O- group. 3 . The photoluminescent composite according to claim 1 , having an emission band having a full width at half maximum (FWHM) of at most 40 nm.

4. The photoluminescent composite of claim 1, wherein the difference between the excitation peak of the blue light absorbing moiety and the emission peak of the BODIPY moiety is at least 45 nm. The photoluminescent composite according to claim 1 , wherein the maximum absorbance of the composite is 400 nm to 480 nm.

6. The photoluminescent composite according to claim 1, wherein G 7 -L3-Z 3 Or-Ar-L3-Z 3 , wherein Ar is an aryl group optionally substituted by methyl, F, Cl, or methoxy.

7. The photoluminescent composite according to claim 1, wherein L3 is:

8. The photoluminescent composite according to claim 1, wherein G 2 for 9. The photoluminescent composite according to claim 1, wherein R 8 , R 9 , R 11 or R 12 for:

10. A color conversion film, comprising: A color conversion layer, wherein the color conversion layer comprises a resin matrix, and the photoluminescent composite according to claim 1 is dispersed in the resin matrix. 11 . The color conversion film of claim 10 , wherein the thickness of the film is between 1 μm and 200 μm. 12 . The color conversion film according to claim 10 , wherein the film absorbs light in the wavelength range of 400 nm to 480 nm and emits light in the wavelength range of 510 nm to 560 nm.

13. The color conversion film according to claim 10 or 11, wherein the film absorbs light in the wavelength range of 400 nm to 480 nm and emits light in the wavelength range of 575 nm to 645 nm.

14. The color conversion film according to claim 10 or 11, further comprising: A transparent substrate layer, wherein the transparent substrate layer includes two opposing surfaces, and wherein the color conversion film is disposed on one of the opposing surfaces. 15 . A backlight unit comprising the color conversion film according to claim 10 or 11 . 16 . A display device comprising the backlight unit according to claim 15 .

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