WO2021188392A1 - Boron-containing cyclic emissive compounds and color conversion film containing the same - Google Patents

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

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Publication number
WO2021188392A1
WO2021188392A1 PCT/US2021/022254 US2021022254W WO2021188392A1 WO 2021188392 A1 WO2021188392 A1 WO 2021188392A1 US 2021022254 W US2021022254 W US 2021022254W WO 2021188392 A1 WO2021188392 A1 WO 2021188392A1
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mmol
methyl
group
compound
color conversion
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PCT/US2021/022254
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French (fr)
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Shijun Zheng
Jeffrey R. HAMMAKER
Hiep Luu
Jan SASKA
Peng Wang
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Nitto Denko Corporation
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Priority to KR1020227029779A priority Critical patent/KR20220130792A/en
Priority to CN202180022646.8A priority patent/CN115298286A/en
Priority to JP2022555944A priority patent/JP7415034B2/en
Publication of WO2021188392A1 publication Critical patent/WO2021188392A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502—Wavelength conversion materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1022—Heterocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C09K2211/1055—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with other heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom

Definitions

  • the present disclosure is related to compounds for use in color conversion films, backlight units, and display apparatus including the same.
  • the gamut In color reproduction the gamut, or color gamut, is a certain complete subset of colors available on a device such as a television or monitor.
  • a device such as a television or monitor.
  • RGB Red Green Blue
  • RGB Red Green Blue
  • a wide-gamut color space achieved by using pure spectral primary colors was developed to provide a broader color gamut and offer a more realistic representation of visible colors viewed through a display. It is believed that a device which could provide a wider gamut could enable the display to portray more vibrant colors.
  • LEDs Current light emitting diodes
  • FWHM full width half maximum
  • quantum dots are extremely toxic and are banned from use in many countries due to health safety issues.
  • non-cadmium-based quantum dots have a very low efficiency in converting blue LED light to green and red light.
  • quantum dots require expensive encapsulating processes for protection against moisture and oxygen.
  • the cost of using quantum dots is high, because of the difficulties in controlling size uniformity during the production process.
  • Photoluminescent complexes described herein may be used to improve the contrast between distinguishable colors in televisions, computer monitors, smart devices and any other device that utilizes color displays.
  • the photoluminescent complexes of the present disclosure provide novel color converting dye complexes with good blue light absorbance and narrow emissions bandwidths, with the full width half maximum [FWHM] of emission band of less than 40 nm.
  • a photoluminescent complex absorbs light of a first wavelength and emits light of a second higher wavelength than the first wavelength.
  • the photoluminescent complexes disclosed herein may be utilized with a color conversion film for use in light emitting apparatuses.
  • the color conversion film of the present disclosure reduced color deterioration by reducing overlap within the color spectrum resulting in high quality color rendition.
  • Some embodiments include a photoluminescent complex, wherein the photoluminescent complex may comprise: a blue light absorbing moiety: a linker group comprising a substituted ester; and a boron-dipyrromethene (BODIPY) moiety.
  • the blue light absorbing moiety may comprise a naphthalic acid derivative.
  • the linker group may covalently link the naphthalic acid derivative to the BODIPY moiety.
  • the naphthalic acid derivative absorbs light of a first excitation wavelength and transfers an energy to the BODIPY moiety.
  • the BODIPY moiety absorbs the energy from the naphthalic acid derivative and emits a light energy of a second higher wavelength.
  • the photoluminescent complex has an emission quantum yield greater than 80%.
  • the photoluminescent complex may have an emission band with a full width half maximum [FWHM] of up to 40 nm.
  • the photoluminescent complex may have a Stokes shift, the difference between the excitation peak of the blue light absorbing moiety and the emission peak of the BODIPY moiety, of equal to or greater than 45 nm.
  • the naphthalic acid derivative may be of the following general formula:
  • X may be a substituted nitrogen (NR 9 ). In some embodiments,
  • X may be oxygen (O).
  • n may be an integer of 0 or 1.
  • R 9 may be selected from H, a substituted aryl, a substituted aryl linker, or a substituted ester linker.
  • R 10 may be selected from H, methyl, a direct bond to an adjacent phenyl ring forming a carbazole, or a substituted ester linker, and R 11 may be H or methyl.
  • Some embodiments include a photoluminescent complex, comprising: a blue light absorbing naphthalic acid derivative; a boron-dipyrromethene (BODIPY) moiety; and a linker group, wherein the linker group covalently links the naphthalic acid derivative to the BODIPY moiety; wherein the blue light absorbing naphthalic acid derivative is represented by the formula: wherein X is NR 9 or O; wherein R 9 is H, a substituted aryl, or the linker group; wherein n is 0 or 1; wherein R 10 is H, methyl, a direct bond to an adjacent phenyl ring forming a carbazole, or the linker group; wherein R 11 is H, or methyl; wherein the linker group is a substituted ester group, or a substituted aralkyl group; wherein the naphthalic acid derivative absorbs light energy of a first excitation wavelength and transfers an energy to the BODIPY mo
  • the color conversion film may comprise: a color conversion layer; wherein the color conversion layer includes a resin matrix; and at least one photoluminescent complex, as described herein, dispersed within the resin matrix.
  • the color conversion film may have a thickness between 1 pm to about 200 pm.
  • the color conversion film of the present disclosure may absorb blue light in the 400 nm to about 480 nm range and emit light in the 510 nm to about 560 nm wavelength range.
  • Another embodiment describes a color conversion film that may absorb blue light in the 400 nm to about 480 nm range and emit light in the 575 nm to about 645 nm wavelength range.
  • the color conversion film may further comprise a transparent substrate layer.
  • the transparent substrate layer comprises two opposing surfaces, wherein the color conversion layer is disposed on one of the opposing surfaces.
  • Some embodiments include a method for preparing the color conversion film, the method comprises: dissolving at least one of the aforedescribed photoluminescent complex and a binder resin within a solvent; and applying the mixture on one of the transparent substrates opposing surfaces.
  • Some embodiments include a backlight unit including a color conversion film described herein.
  • Some embodiments include a display device including the backlight unit described herein.
  • the present application provides a photoluminescent complex's having excellent color gamut and luminescent properties, a method for manufacturing color conversion films using the photoluminescent complexes, and a backlight unit including the color conversion film.
  • FIG. 1 is a graph depicting the absorption and emission spectra of one embodiment of a photoluminescent complex.
  • FIG. 2 is a graph depicting the absorption and emission spectra of one embodiment of a photoluminescent complex.
  • the current disclosure describes photoluminescent complexes and their uses in color conversion films.
  • the photoluminescent complexes may be used to improve and enhance the transmission of one or more desired emissive bandwidths within a color conversion film.
  • the photoluminescent complex may both enhance the transmission of a desired first emissive bandwidth and decrease the transmission of a second emissive bandwidth.
  • a color conversion film may enhance the contrast or intensity between two or more colors, increasing the distinction from one another.
  • a photoluminescent complex that may enhance the contrast or intensity between two colors, increasing their distinction from one another.
  • substituted group is derived from the unsubstituted parent structure wherein one or more hydrogen atoms on the parent structure have been independently replaced by one or more substituent groups.
  • a substituent group may have one or more substituent groups on the parent group structure. In one or more forms, the substituent groups may be independently selected from an optionally substituted alkyl, alkenyl, or a C3-C7 heteroalkyl.
  • alkyl group refers to a hydrocarbon group having no carbon- carbon double or triple bonds.
  • An alkyl moiety, an alkene moiety, or an alkyne moiety may be branched, straight chain, or cyclic.
  • the alkyl moiety may have 1 to 6 carbon atoms (whether it appears herein, a numerical range such as “1 to 6” refers to each integer in the given range: e.g., "1 to 6 carbon atoms” means that the alkyl group may have 1 carbon atom, 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbon atoms, or 6 carbon atoms, although the present definition also covers the occurrence of the term "alkyl” where no numerical range is designated.
  • the alkyl group of the compounds designated herein may be designated as "C -C alkyl" or similar designations.
  • C -C alkyl indicates that there are one to six carbon atoms in the alkyl chain, i.e., the alkyl chain is selected from among methyl, ethyl, propyl, iso propyl, n-butyl, iso-butyl, sec-butyl, t-butyl, etc.
  • C 1 -C 6 alkyl includes C 1 -C 2 alkyl, C 1 -C 3 alkyl, C 1 -C 4 alkyl, C 1 -C 5 alkyl.
  • Alkyl groups may be substituted or unsubstituted.
  • Typical alkyl groups include, but are in no way limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.
  • Typical alkene groups include, but are not limited to, ethenyl, propenyl, butenyl, etc.
  • aromatic refers to a planar ring having a delocalized p-electron system containing 4n+2 p electrons, where n is an integer. Aromatic rings may be formed from five, six, seven, eight, nine, or more than nine atoms. Aromatic rings may be optionally substituted.
  • aromatic includes both carbocyclic aryl (e.g., phenyl) and heterocyclic aryl (or “heteroaryl” or heteroaromatic") group (e.g., pyridine).
  • the term includes monocyclic or fused-ring polycyclic (i.e., rings which share adjacent pairs of carbon atoms) groups.
  • hydrocarbon ring refers to a monocyclic or polycyclic radial that contains only carbon and hydrogen.
  • the hydrocarbon ring may be saturated or unsaturated.
  • Monocyclic hydrocarbon rings may have from 3 to 12 carbon atoms.
  • Illustrative examples of monocyclic groups include the following moieties: and the like.
  • Illustrative examples of polycyclic groups include the following moieties:
  • aryl as used herein means an aromatic ring wherein each of the atoms forming the ring is a carbon atom.
  • Aryl rings may be formed by five, six, seven, eight, or more than eight carbon atoms.
  • Aryl groups may be substituted or unsubstituted. Examples of aryl groups include, but are not limited to phenyl, naphthalenyl, phenanthrenyl, etc.
  • aralkyl refers to an alkyl radical, as defined herein, substituted with an aryl, as defined herein.
  • Non-limiting aralkyl groups include benzyl, 2-phenethyl, 3-phenylpropyl; and the like.
  • heteroaryl refers to an aryl group that includes one or more ring heteroatoms selected from nitrogen, oxygen and sulfur, wherein the heteroaryl group has from 4 to 10 atoms in its ring system and with the proviso that the ring of the group does not contain two adjacent oxygen or sulfur atoms. It is understood that the heteroaryl ring can have additional heteroatoms in the ring. In heteroaryl rings that have two or more heteroatoms, those two or more heteroatoms may be the same or different from one another. Heteroaryl rings may be optionally substituted.
  • An N-containing heteroaryl moiety refers to an aryl group in which at least one of the skeletal atoms of the ring is a nitrogen atom.
  • Illustrative examples of heteroaryl groups include the following moieties: pyrrole, imidazole, pyridine, etc.
  • halogen as used herein means fluorine, chlorine, bromine, and iodine.
  • bond means a chemical bond between two atoms or to two moieties when the atoms joined by the bond are considered to be part of a larger structure.
  • moiety refers to a specific segment or functional group of a molecule. Chemical moieties are often recognized chemical entities embedded in or appended to a molecule.
  • cyano or "nitrile” as used herein refers to any organic compound that contains a -CN functional group.
  • esters refers to a chemical moiety with the formula -COOR, where R is selected from among alkyl, cycloalkyl, aryl, heteroaryl (bonded through a ring carbon) and heterocyclic (bonded through a ring carbon). Any hydroxy, or carboxyl side chain on the compounds described herein may be esterified. Such esters may be prepared by any suitable method which may readily be found in reference sources.
  • ether refers to a chemical moiety that contains an oxygen atom connected to two alkyl or aryl groups with the general formula of R-O-R', where the term alkyl and aryl is as defined herein.
  • BODIPY refers to a chemical moiety with the formula:
  • the BODIPY moiety may be composed or dipyrromethene complexed with a di- substituted boron atom, typically a BF2 unit.
  • the lUPAC name for the BODIPY core is 4,4- difluoro-4-bora-3a,4a-diaza-s-indacene.
  • naphthalic acid or “naphthalic acid derivative” as used herein, refers to a chemical moiety with the formula:
  • the color conversion film may further comprise a transparent substrate layer
  • the statement “the color conversion film may further comprise a transparent substrate layer” should be interpreted as, for example, “In some embodiments the color conversion film further comprises a transparent substrate layer,” or “In some embodiments, the color conversion film does not further comprise a transparent substrate layer.”
  • the present disclosure related to photoluminescent complexes that absorb light energy of first wavelength emits light energy in a second higher wavelength.
  • the photoluminescent complex of the present disclosure comprises an absorbing luminescent moiety and an emitting luminescent moiety that are coupled through a linker such that their distance is adjusted for the absorbing luminescent moiety to transfer its energy to the acceptor luminescent moiety, wherein the acceptor luminescent moiety then emits out at a second wavelength that is larger than the absorbed first wavelength.
  • the photoluminescent complex comprises: a blue light absorbing naphthalic acid derivative; a linker group; and a boron-dipyrromethene (BODIPY) moiety.
  • the linker group may covalently link the naphthalic acid derivative to the BODIPY moiety.
  • the naphthalic acid derivative absorbs light of a first excitation wavelength and transfers energy to the BODIPY moiety, the BODIPY moiety then emits a 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 naphthalic acid derivative to the BODIPY moiety occurs through a Forster resonance energy transfer (FRET).
  • FRET Forster resonance energy transfer
  • the photoluminescent complex may have a high emission quantum yield.
  • the emission quantum yield may be greater than 50%, 60%, 70 %, 80%, or 90%, up to 100%.
  • 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%, up to 100%, 50-60%, 60-70%, 70-80%, 80-90%, 90-100%.
  • 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 luminescent moiety.
  • the absorbing luminescent moiety may have an emission quantum yield greater than 80%.
  • the quantum yield may be greater than 0.8 (80%), greater than 0.81 (81%), greater than 0.82 (82%), greater than 0.83 (83%), greater than 0.84 (84%), greaterthan 0.85 (85%), greaterthan 0.86 (86%), greaterthan 0.87 (87%), greaterthan 0.88 (88%), greater than 0.89 (89%), greater than 0.9 (90%), greater than 0.91 (91%), greater than 0.92 (92%), greater than 0.93 (93%), greaterthan 0.94 (94%), or greater than 0.95 (95%).
  • Quantum yield measurements in film may be made by spectrophotometer, e.g., Quantaurus- QY spectrophotometer (Flumamatsu, Inc., Campbell, CA, USA).
  • the photoluminescent complex has an emission band, the emission band may have a full width half maximum (FWHM) of less than 40 nm.
  • the FWHM is the width of the emission band in nanometers at the emission intensity that is half of the maximum emission intensity for the band.
  • the photoluminescent complex has an emission band FWHM value that is less than or equal to about 35 nm, less than or equal to about 30 nm, less than or equal about 25 nm, or less than or equal to about 20 nm.
  • the photoluminescent complex may have a Stokes shift that is equal to or greater than 45nm.
  • Stokes shift means the distance between the excitation peak of the blue light absorbing moiety and the emission peak of the BODIPY moiety.
  • the photoluminescent complex of the current disclosure may have a tunable emission wavelength.
  • the emission wavelength may be tuned between 510 nm to about 560 nm or between about 610 nm to about 645 nm, or about any wavelength in a range bounded by any of these values.
  • the blue light absorbing moiety may have a peak absorption maximum between about 400 nm to about 470 nm wavelength.
  • the peak absorption may 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 about any wavelength in a range bounded by
  • the photoluminescent complex may have an emission peak between 510 nm and 560 nm.
  • the emission peak may be between about 510 nm to about 515 nm, about 515 nm to about 520 nm, about 520 nm to about 525 nm, about 525 nm to about 530 nm, about 530 nm to about 535 nm, about 535 nm to about 540 nm, about 540 nm to about 545 nm, about 545 nm to about 550 nm, about 550 nm to about 555 nm, about 555 nm to about 560 nm, or about any wavelength in a range bounded by any of these values.
  • the photoluminescent complex may have an emission peak between 610 nm to 645 nm.
  • the emission peak may be between 610 nm to about 615 nm, about 615 nm to about 620 nm, about 620 nm to about 625 nm, about 625 nm to about 630 nm, about 630 nm to about 635 nm, about 635 nm to about 640 nm, about 640 nm to about 645 nm, or about any wavelength in a range bounded by any of these values.
  • inventions include the photoluminescent complex wherein the blue light absorbing naphthalic acid derivative and the BODIPY moiety's spatial distance is tuned through the linker group, for transfer of the blue light absorbing naphthalic acid derivative's energy to the BODIPY moiety.
  • the present disclosure describes a photoluminescent complex, wherein the photoluminescent complex may comprise a blue light absorbing naphthalic acid derivative, a linker group and a BODIPY moiety.
  • the linker group covalently links the blue light absorbing naphthalic acid derivative to the BODIPY moiety.
  • the naphthalic acid derivative absorbs light energy of a first excitation wavelength and transfers an energy to the BODIPY moiety, wherein the BODIPY moiety absorbs the energy from the naphthalic acid derivative and emits a light energy of a second higher wavelength, and wherein the photoluminescent complex has an emission quantum yield greater than 80%.
  • a blue light absorbing naphthalic acid derivative wherein the blue light absorbing naphthalic acid derivative may be of the following general formula: wherein X may be NR 9 or O; n is 0 or 1; R 9 is H, a substituted aryl, a substituted aryl linker, or a substituted ester linker; R 10 is H, a methyl, a direct bond to an adjacent phenyl ring forming a carbazole, or a substituted ester linker; and R 11 is a H or a methyl.
  • X is NR 9 . In some embodiments, X is O.
  • n is 0. In some embodiments, n is 1. In some embodiments, R 9 is a substituted H. In some embodiments, R 9 is a substituted phenyl. In some embodiments, R 9 is the linker group.
  • R 10 is methyl. In some embodiments, R 10 is H. In some embodiments, R 10 is the linkergroup. In some embodiments, R 10 is a direct bond to an adjacent phenyl ring forming a carbazole.
  • R 11 is methyl. In some embodiments, R 11 is H.
  • X may be NR 9 , n may be 0, R 9 may be a substituted ester linker, R 10 may be H, and R 11 may be H.
  • X may be a NR 9 , n may be 1, R 9 may be a substituted ester linker, R 10 may be H, and R 11 may be H.
  • X may be a NR 9
  • n may be 1
  • R 9 may be a substituted ester linker
  • R 10 may be methyl
  • R 11 may be methyl
  • X may be a NR 9
  • n may be 1
  • R 9 may be a substituted ester linker
  • R 10 may be a direct bond to an adjacent phenyl ring forming a carbazole
  • R 11 may be H.
  • X may be a NR 9
  • n may be 0,
  • R 9 may be a substituted aryl
  • R 10 may be a substituted ester linker
  • R 11 may be H.
  • X may be a NR 9 , n may be 1, R 9 may be an aralkyl linker, R 10 may be H, and R 11 may be H.
  • X may be a O , n may be 1, R 10 may be a substituted ester linker, and R 11 may be H.
  • R 9 is a substituted aryl, wherein the substituted aryl may be Those of skill in the art will also recognize that the R 10 and R 11 substituents may be substituted at any position of their respective phenyl rings. While the structural formulae provided herein may depict one of many possible regioisomers, it will be understood that these structures are illustrative only, and that the present disclosure is not limited to any particular isomeric state, and any and all possible regioisomeric states of naphthalic acid derivatives are intended to fall within the scope of the present disclosure.
  • the linker group covalently links the blue absorbing naphthalic acid derivative with the BODIPY moiety.
  • the linker group may be varied to adjust the spatial distance between the blue light absorbing naphthalic acid derivative and the BODIPY moiety. By optimizing the spatial distance between the naphthalic acid derivative and the BODIPY moiety, the quantum yield may be tuned.
  • L may represent the linker group.
  • the linker group may comprise a substituted ester linker.
  • the substituted ester linker may comprise one of the
  • the linker group may comprise a substituted aralkyl linker.
  • the photoluminescent complex of the current disclosure may comprise a BODIPY moiety.
  • the BODIPY moiety may have the following chemical formula;
  • R 1 and R 6 are independently a hydrogen (H), an alkyl group, an alkene group, or an alkyne group;
  • R 3 and R 4 are independently a H or a C 1 -C 2 alkyl
  • R 2 and R 5 are independently a hydrogen (H), an alkyl group, an alkene group, an alkyne group, a cyano (-CN), an ester (-COOCH 2 CH 3 ), or an aryl ester (-COOCh ⁇ Ar);
  • R 2 and R 3 may link together to form an additional monocyclic hydrocarbon ring structure, or a polycyclic hydrocarbon ring structure;
  • R 4 and R 5 may link together to form an additional monocyclic hydrocarbon ring structure, or a polycyclic hydrocarbon ring structure;
  • G 7 may be an aralkyl linker, or a substituted aryl moiety of the structure:
  • R 7 and R 8 are independently a H, a methyl, a fluoride, a chloride, or an alkoxy group
  • L represents the linker group
  • R 1 is methyl. In some embodiments, R 1 is H. In some embodiments, R 3 is methyl. In some embodiments, R 3 is H. In some embodiments, R 4 is methyl. In some embodiments, R 4 is H. In some embodiments, R 6 is methyl. In some embodiments, R 6 is H. In some embodiments, R 1 , R 3 , R 4 , and R 6 are methyl.
  • R 2 is a cyano. In some embodiments, R 2 is an alkyl ester or an aryl ester. In some embodiments, R 2 is an aryl ester. In some embodiments, R 2 is an alkyl ester.
  • R 5 is a cyano. In some embodiments, R 5 is an alkyl ester or an aryl ester. In some embodiments, R 5 is an aryl ester. In some embodiments, R 5 is an alkyl ester.
  • R 2 and R 5 are a cyano. In some embodiments, R 2 and R 5 are an alkyl ester or an aryl ester. In some embodiments, R 2 and R 5 are an aryl ester. In some embodiments, R 2 and R 5 are an alkyl ester.
  • R 1 and R 2 link together to form a polycyclic hydrocarbon ring structure.
  • R 5 and R 6 link together to form a polycyclic hydrocarbon ring structure.
  • R 7 is H, a methyl, a halogen, or a methoxy group. In some embodiments, R 7 is a methyl, a fluoride, a chloride or a methoxy group. In some embodiments, R 7 is methyl.
  • R 8 is H, a methyl, a halogen, or a methoxy group. In some embodiments, R 8 is a methyl, a fluoride, a chloride or a methoxy group. In some embodiments, R 8 is methyl.
  • R 7 and R 8 are H, a methyl, a halogen, or a methoxy group. In some embodiments, R 7 and R 8 are independently a methyl, a fluoride, a chloride or a methoxy group. In some embodiments, R 7 and R 8 are methyl.
  • the BODIPY moiety of the present disclosure may be a BODIPY moiety wherein R 1 , R 3 , R 4 and R 6 are each a methyl; R 2 and R 5 are a cyano group; R 7 and R 8 are each a methyl; and G 7 comprises a substituted aryl moiety comprising a substituted ester linker.
  • the BODIPY moiety of the present disclosure may be a BODIPY moiety wherein R 1 , R 3 , R 4 and R 6 are each a methyl; R 2 and R 5 are a substituted ester group, wherein the substituted ester group contains an alkyl chain; R 7 and R 8 are each a methyl; and G 7 comprises a substituted aryl moiety comprising a substituted ester linker.
  • R 1 , R 3 , R 4 and R 6 are each a methyl;
  • R 2 and R 5 are a substituted ester group, wherein the substituted ester group contains an aryl group;
  • R 7 and R 8 are each selected from a methyl, a fluoride, a chloride, or an alkoxy group; and
  • G 7 comprises a substituted aryl moiety comprising a substituted ester linker.
  • R 1 and R 2 may link together to form polycyclic hydrocarbon ring structure;
  • R 3 and R 4 are methyl;
  • R 5 and R 6 may link together to form a polycyclic hydrocarbon ring structure;
  • R 7 and R 8 may be selected from a H, a methyl, or an alkoxy group; and
  • G 7 comprises a substituted aryl moiety comprising a substituted ester linker.
  • R 2 and R 5 may be a substituted ester wherein the substituted ester is an aryl ester.
  • the aryl ester may be the following structure:
  • R 2 and R 5 may be a substituted ester wherein the substituted ester is an alkyl ester.
  • the alkyl ester may be of the following structure:
  • the photoluminescent complex of the current disclosure may comprise a BODIPY moiety.
  • the BODIPY moiety may have the following chemical formula: wherein R 1 and R 2 may link together to form an additional monocyclic hydrocarbon ring structure or a polycyclic hydrocarbon ring structure;
  • R 3 and R 4 may be H; R 5 and R 6 may link together to form an additional monocyclic hydrocarbon ring structure or a polycyclic hydrocarbon ring structure;
  • R 7 and R 8 may be independently a H, a halogen, a methyl, or an alkoxy group
  • L represents the linker group comprising a substituted ester linker.
  • R 1 and R 2 may link together to form an additional monocyclic hydrocarbon ring structure, or polycyclic hydrocarbon ring structure.
  • the structure may be selected from the following: [cyclobutane], [cyclopentane],
  • the structure may be selected from the following: [bicyclooctane], [bicyclopentane],
  • R 5 and R 6 may link together to form an additional monocyclic hydrocarbon ring structure, or polycyclic hydrocarbon ring structure.
  • the structure may be selected from the following: [cyclobutane], [cyclopentane], [cyclohexane], [cycloheptane], [cyclooctane],
  • R 5 and R 6 are linked together to form a polycyclic hydrocarbon ring structure, the structure may be selected from the following:
  • the distance separating the blue light absorbing naphthalic acid derivative and the BODIPY moiety may be about 8 A or greater.
  • the linker group may maintain the desired distance between the blue light absorbing naphthalic acid derivative and the BODIPY moiety.
  • the photoluminescent complex comprises a linker group, wherein the linker group covalently links the blue light absorbing naphthalic acid derivative to the BODIPY moiety.
  • the linker group may comprise an optionally substituted C -C ester group.
  • the linker group may be selected from among one of the following:
  • the BODIPY moiety may have the following chemical formula: wherein L' may be an aralkyl linker. In some examples, the aralkyl linker may be
  • the photoluminescent complex of the present disclosure may be represented by the following which are provided for the purpose of illustration and are in no way to be construed as limiting:
  • a photoluminescent complex comprises a blue light absorbing naphthalic acid derivative.
  • the blue light absorbing naphthalic acid derivative may comprise an organic lumiphore.
  • the naphthalic acid derivative may have a maximum absorbance in the light in 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 about any wavelength in a range bounded by any of these values.
  • the photoluminescent complex may have an absorbance maximum peak of about 450 nm.
  • the blue light absorbing naphthalic acid derivative may have a maximum peak absorbance of about 405 nm.
  • the blue light absorbing naphthalic acid derivative may have a maximum peak absorbance of about 480 nm.
  • Some embodiments include a color conversion film, wherein the color conversion film comprises: a color conversion layer wherein the color conversion layer includes a resin matrix and photoluminescent complexes, described above, dispersed within the resin matrix.
  • the color conversion film may be described as comprising one or more of the complexes described herein.
  • the color conversion film may be about 1 pm to about 200 pm thick, about 1 pm to about 5 pm, about 5 pm to about 10 pm, about 10 pm to about 15 pm, about 15 pm to about 20 pm, about 20 pm to about 40 pm, about 40 pm to about 80 pm, about 80 pm to about 120 pm, about 120 pm to about 160 pm about 160 pm to about 200 pm thick, or about any thickness in a range bounded by any of these values.
  • the color conversion film may absorb light in the 400 nm to about 480 nm wavelength and may emit light in the range of about 510 nm to about 560 nm and/or about 610 nm to about 645 nm. In other embodiments, color conversion film may emit light in the 510 nm to about 560 nm range, the 610 nm to about 645 nm range, or any combination thereof.
  • the color conversion film may further comprise a transparent substrate layer.
  • the transparent substrate layer may have two opposing surfaces, wherein the color conversion layer may be disposed on and in physical contact with the surfaces of the transparent layer that will be adjacent to a light emitting source.
  • the transparent substrate is not particularly limited and one skilled in the art would be able to choose a transparent substrate from those used in the art.
  • transparent substrates include PE (polyethylene), PP (polypropylene), PEN (polyethylene naphthalate), PC (polycarbonate), PMA (polymethylacrylate), PMMA (Polymethylmethacrylate), CAB (cellulose acetate butyrate), PVC (polyvinylchloride), PET (polyethyleneterephthalate), PETG (glycol modified polyethylene terephthalate), PDMS (polydimethylsiloxane), COC (cyclo olefin copolymer), PGA (polyglycolide or polyglycolic acid), PLA (polylactic acid), PCL (polycaprolactone), PEA (polyethylene adipate), PHA (polyhydroxy alkanoate), PHBV (poly(3- hydroxybutyrate-co-3hydroxyvalerate)), PBE (polybutylene terephthalate), PTT (polytrimethylene terephthalate). Any of the afor
  • the transparent substrate may have two opposing surfaces.
  • the color conversion film may be disposed on and in physical contact with one of the opposing surfaces.
  • the side of the transparent substrates without color conversion film disposed thereon may be adjacent to a light source.
  • the substrate may function as a support during the preparation of the color conversion film.
  • the type of substrates used are not particularly limited, and the material and/or thickness is not limited, as long as it is transparent and capable of functioning as a support. A person skilled in the art could determine which material and thickness to use as a supporting substrate.
  • Some embodiments include a method for preparing the color conversion film, wherein the method comprises: dissolving a photoluminescent compound, described herein, and a binder resin within a solvent; and applying the mixture on to the surface of the transparent substrate.
  • the binder resin which may be used with the photoluminescent complex(s) includes resins such as acrylic resins, polycarbonate resins, ethylene-vinyl alcohol copolymer resins, ethylene-vinyl acetate copolymer resins and saponification products thereof, AS resins, polyester resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins, polyvinyl phosphonic acid (PVPA), polystyrene resins, phenolic resins, phenoxy resins, polysulfone, nylon, cellulosic resins, and cellulose acetate resins.
  • the binder resin may be a polyester resin and/or acrylic resin.
  • the solvent which may be used for dissolving or dispersing the complex and the resin may include an alkane, such as butane, pentane, hexane, heptane, and octane; a cycloalkane, such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane; an alcohol, such as ethanol, propanol, butanol, amyl alcohol, hexanol, heptanol, octanol, decanol, undecanol, diacetone alcohol, and furfuryl alcohol; CellosolvesTM, such as Methyl CellosolveTM, Ethyl CellosolveTM, Butyl CellosolveTM, Methyl CellosolveTM acetate, and Ethyl CellosolveTM acetate; propylene glycol and its derivatives, such as propylene glycol monomethyl ether
  • Some embodiments include a backlight unit, wherein the backlight unit may include the aforedescribed color conversion film.
  • a display device may include the backlight unit described hereinto.
  • This disclosure may sometimes illustrate different components contained within, or connected with, different other components. Such depicted architectures are merely examples, and many other architectures may be implemented which achieve the same or similar functionality.
  • any disjunctive word and/or phrase presenting two or more alternative terms should be understood to contemplate the possibilities of including one of the terms, either of the terms, or both terms.
  • the phase "A or B” will be understood to include the possibilities of "A” or "B” or “A and B.”
  • a photoluminescent complex comprising:
  • Embodiment 2 The naphthalic acid derivative of embodiment 1, wherein X is N, n is 0, R 9 is substituted ester linker, R 10 is H, and R 11 is H.
  • Embodiment 3 The naphthalic acid derivative of embodiment 1, wherein X is N, n is 1, R 9 is substituted ester linker, R 10 is H, and R 11 is H.
  • Embodiment 4 The naphthalic acid derivative of embodiment 1, wherein X is N, n is 1, R 9 is substituted ester linker, R 10 is methyl, and R 11 is methyl.
  • Embodiment 5 The naphthalic acid derivative of embodiment 1, wherein X is N, n is 1,
  • R 9 is substituted ester linker
  • R 10 is a direct bond to an adjacent phenyl ring forming a carbazole
  • R 11 is H.
  • Embodiment 6 The naphthalic acid derivative of embodiment 1, wherein X is N, n is 0, R 9 is a substituted aryl, R 10 is substituted ester linker, and R 11 is H.
  • Embodiment 7 The naphthalic acid derivative of embodiment 1, wherein X is O, n is 1,
  • R 9 is H
  • R 10 is substituted ester linker
  • R 11 is H
  • Embodiment 8 The naphthalic acid derivative of embodiment 6, wherein the substituted aryl is selected from one of the following structures:
  • Embodiment 9 The photoluminescent complex of embodiment 1 wherein the BODIPY moiety is of the general formula:
  • R 1 and R 6 are independently selected from a hydrogen (H), an alkyl group, an alkene group, or an alkyne group;
  • R 3 and R 4 are independently selected form a H or a C1-C2 alkyl
  • R 2 and R 5 are independently selected from a hydrogen (H), an alkyl group, an alkene group, an alkyne group, a cyano (-CN), an ester (-COOCH2CH3), or an aryl ester (-COOCH 2 Ar);
  • R 2 and R 3 may link together to form an additional monocyclic hydrocarbon ring structure, or a polycyclic hydrocarbon ring structure;
  • R 4 and R 5 may link together to form an additional monocyclic hydrocarbon ring structure, or a polycyclic hydrocarbon ring structure;
  • R 7 and R 8 may be independently selected from a H, a methyl, a fluoride, a chloride, or an alkoxy group and
  • L represents the linker group comprising a substituted ester linker.
  • Embodiment 10 The BODIPY moiety of embodiment 9, wherein R 1 , R 3 , R 4 , and R 6 are methyl, R 2 and R 5 are selected from a substituted ester, R 7 and R 8 are methyl and L is a linker group.
  • Embodiment 11 The BODIPY moiety of embodiment 9, wherein R 1 , R 3 , R 4 , and R 6 are methyl, R 2 and R 5 are a cyano, R 7 and R 8 are methyl and L is a linker group.
  • Embodiment 12 The BODIPY moiety of embodiment 9, wherein R 1 , R 3 , R 4 , and R 6 are methyl, R 2 and R 5 are an aryl ester, R 7 and R 8 are selected from a methyl, a fluoride, a chloride or an ether group, and L is a linker group.
  • Embodiment 13 The photoluminescent complex of embodiment 1 wherein the BODIPY moiety is of the general formula:
  • R 1 and R 2 link together to form an additional polycyclic hydrocarbon ring structure
  • R 3 and R 4 are methyl
  • R 5 and R 6 link together to form an additional polycyclic hydrocarbon ring structure
  • R 7 and R 8 may be independently selected from a H, a methyl or an alkoxy group
  • L represents the linker group comprising a substituted ester linker.
  • Embodiment 14 The BODIPY moiety of embodiment 13, wherein R 1 and R 2 link together to form a hydrocarbon ring structure, R 3 and R 4 , are methyl, R 5 and R 6 may link together to form a polycyclic hydrocarbon ring structure, R 7 and R 8 is selected from a H, a methyl, or an ether group, and L is a linker group.
  • Embodiment 15 The photoluminescent complex of embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, and 14, wherein the substituted ester of the linker group is selected from one if the following structures:
  • Embodiment 16 The photoluminescent complex of embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, and 14, wherein the linkergroup may comprise a substituted aryl linker, where.
  • the substituted alkyl linker may be
  • Embodiment 17 The photoluminescent complex of embodiments 1, 2, 3, 4, 5, 6, 1 , 8, 9, 10, 11, 12, 13, and 14, wherein the complex is selected from any one of the following structures:
  • Embodiment 18 A color conversion film comprising: a transparent substrate layer; a color conversion layer, wherein the color conversion layer includes a resin matrix, and at least one photoluminescent complex, wherein the at least one photoluminescent compound is comprised the photoluminescent compound of embodiments, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14, dispersed within the resin matrix.
  • Embodiment 19 The color conversion film of embodiment 18, further comprising a singlet oxygen quencher.
  • Embodiment 20 The color conversion film of embodiment 18, further comprising a radical scavenger.
  • Embodiment 21 The color conversion film of embodiment 18, wherein the film has a thickness of between 10 pm and 200 pm.
  • Embodiment 22 The color conversion film of embodiment 17, wherein the film absorbs light in about 400 nm to about 480 nm wavelength range and emits light in the 510 nm to about 560 and in the 575 nm to about 645 nm wavelength range.
  • Embodiment 23 A method for preparing the color conversion film of embodiments 18, 19, 20, and 21 the method comprising: dissolving the photoluminescent complex of embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, and 14, and a binder resin within a solvent; and applying the mixture to one of the transparent substrates opposing surfaces.
  • Embodiment 24 A backlight unit including the color conversion film of embodiment 18, 19, 20, 21, or 22.
  • Embodiment 25 A display device including the back-light unit of embodiment 24.
  • CE-1 0.75 g of 4-hydoxyl-2,6-dimethylbenzaldehyde (5 mmol) and 1.04 g of 2,4- dimethylpyrrole (11 mmol) was dissolved in 100 mL of anhydrous dichloromethane. The solution was degassed for 30 minutes. Then one drop of trifluoroacetic acid was added. The solution was stirred overnight under argon gas atmosphere at room temperature. To the resulting solution, DDQ (2.0 g) was added and the mixture was stirred overnight. The next day the solution was filtered and then washed with dichloromethane resulting in a dipyrrolemethane (1.9 g).
  • Example 1.2 Comparative Example 2 was synthesized as described in Wakamiya, Atsushi et ai Chemistry Letters, 37(10), 1094-1095; 2008
  • Compound 1.2 A mixture of compound 1.1 (1.0 g, 2.45 mmol), N,N'-diphenylamine (0.62 g, 3.7 mmol), Pd(dppf)Cl2 (0.15 g, 0.2 mmol) and sodium f-butoxide (0.36 g, 3.7 mmol) in anhydrous toluene (25 mL) was degassed and heated at 110 °C overnight. The resulting mixture was loaded on silica gel, and purified by flash chromatography using eluents of dichloromethane/hexanes (0% - 90% dichloromethane). The main orange colorfraction was collected and 0.6 g orange solid was obtained after removal of solvents (in 50% yield).
  • PLC-1 A mixture of compound 1.4 (40 mg, 0.067 mmol), dibenzyl 5,5-difluoro-10-(4- hyd roxy-2, 6-dimethyl phenyl)-l, 3,7, 9-tetra methyl-5H-4 ⁇ 4 ⁇ 5 ⁇ 4 -dipyrrolo[l, 2-c:2',l'- f][l,3,2]diazaborinine-2,8-dicarboxylate] (38 mg, 0.06 mmol), DMAP/TsOH salt (29 mg, 0.1 mmol), and DIC (30 mg, (0.2 mmol) in dichloromethane (5 mL) was stirred at r.t. overnight.
  • PLC-3 A mixture of compound 3.4 (72 mg, 0.136 mmol), compound 3.5 [dibenzyl 5,5- dif luoro-10-(4-hyd roxy-2, 6-dimethyl phenyl)-l, 3,7, 9-tetra methyl-5H-4A 4 , 5A 4 -dipyrrolo[l, 2- c:2',l'-/][l,3,2]diazaborinine-2,8-dicarboxylate] (64 mg, 0.1 mmol), DMAP/p-TsOH salt (59 mg, 0.2 mmol) and DIC (63 mg, 0.5 mmol) in DCM (5 mL) was stirred at r.t. overnight.
  • Compound PLC-4 The mixture of compound 4.1 (50 mg, 0.076 mmol), dibenzyl 5,5- difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-l,3,7,9-tetramethyl-5H-4 ⁇ 4 ,5 ⁇ 4 -dipyrrolo[l,2- c:2',l'-f][l,3,2]diazaborinine-2,8-dicarboxylate) (40 mg, 0.063 mmol), DMAP/p-TsOH salt (60mg, 0.2 mmol), DIC (63 mg, 0.5 mmol) in 2mL DCM, was stirred at r.t. overnight.
  • Compound 5.2 A mixture of compound 5,1 (1.0 g, 2,29 mmoi), N,N'-diphenylamine (0.62 g, 3.7 mmol), Pd(dppf)Ci2 (0.15 g, 0.2 mmol), and sodium f-butoxide (0.36 g, 3.8 mmoi) in anhydrous toluene (25mL) was degassed and heated at 110 Q C overnight. The resulting mixture was loaded on silica gel and purified by flash chromatography using eluents of hexanes/DCM (0% 20% DCM). The desired fraction were collected and removal of solvents gave a solid (0.75 g, in 62% yield). LCMS (APC!: calcd for C36H33N2O2 (M+H): 525; found: 525.
  • PLC-5 A mixture of compound 5.3.1 (62 mg, 0.1 mmol), Compound 3.5 [dibenzyl 5,5- difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-l,3,7,9-tetramethyl-5H-4A 4 ,5A 4 -dipyrrolo[l,2- c:2',l'-/][l,3,2]diazaborinine-2,8-dicarboxylate] (57 mg, 0.09 mmol), DIC (63 mg, 0.5 mmol), DMAP/p-TsOH salt (60 mg, 0.2 mmol) in DCM (5 mL) was stirred at r.t. overnight.
  • Compound 7.1 A mixture of 4-bromo-l,8-naphthalic anhydride (2.78 g, 10 mmol), gamma-aminobutyric acid t-butyl ester hydrochloride (2.35 g, 12 mmol), triethylamine (1,21 g, 12 mmol) in 60 mL ethanol was heated at reflux under argon overnight. The mixture was allowed to cool down to r.t. and stand for 4 hrs. Filtration and washing with methanol, following by drying with air gave a light yellow solid as desired product (3.48 g, in 83% yield).
  • Compound 7.2 A mixture of compound 7.1 (1.0 g, 2.4 mmol), N,N'-diphenylamine (0.62 g, 3.7 mmol), Pd(dppf)Cl 2 (0.15 g, 0. 2mmol), sodium f-butoxide (0.36 g, 3.7 mmol) in anhydrous toluene (25 mL) was degassed and heated at 110 Q C overnight.
  • PLC-7 A mixture of compound 7.3 (50 mg, 0.11 mmol), dibenzyl 5,5-difluoro-10-(4- hyd roxy-2, 6-dimethyl phenyl)-l, 3,7, 9-tetra methyl-5H-4 ⁇ 4 , 5 ⁇ 4 -dipyrrolo[l, 2-c:2',l'- f][l,3,2]diazaborinine-2,8-dicarboxylate) (64 mg, 0.1 mol), DMAP/p-TsOH salt (59 mg, 0.2 mmol), DIC (63 mg, 0.5 mmol) in DCM (5 mL) was stirred at r.t.
  • PLC-8 A mixture of compound 8.2 (36 mg, 0.068 mmol), Compound 3.5 (38 mg, 0.06 mmol), DMAP/p-TsOH salt (59 mg, 0.2 mmol) and DIC (63 mg, 0.5 mmol) in DCM (5 mL), was stirred at r.t. overnight. The resulting mixture was submitted to flash chromatography purification using eluents of DCM/ethyl acetate (0% - 5% ethyl acetate). The desired fraction was collected and concentrated under reduced pressure. The solid was further purified by reprecipitation in DCM/methanol to give an orange solid (50 mg, in 73% yield).
  • PLC-9 A mixture of compound 9.2 (72 mg, 0.11 mmol), compound 3.5 (50 mg, 0.079 mmol), DAMP/p-TsOH salt (60 mg, 0.2 mmol), DIC (63 mg, 0.5 mmol) in DCM (5 mL) was stirred at r.t. overnight. The resulting mixture was submitted to flash chromatography purification using eluents of DCM/ethyl acetate (0% - 5% ethyl acetate). The main fraction was collected, and removal of solvents gave an orange solid (88 mg, in 91% yield). LCMS (APCI): calcd for C 77 H 63 BF 2 N 4 O 8 (M-): 1220; found: 1220.
  • PLC-11 A mixture of Compound 11.1 [potassium 4-(4-(l,3-dioxo-6-(9-phenyl-9H- carbazol-3-yl)-1H-benzo[de]isoquinolin-2(3H)-yl)phenyl)butanoate] (70 mg, 0.11 mmol), Compound 3.5 [dibenzyl 5,5-difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-l,3,7,9- tetramethyl-5H-4 ⁇ 4 ,5 ⁇ 4 -dipyrrolo[l,2-c:2',1-f][l,3,2]diazabormine-2,8-dicarboxylate] (50 mg, 0.079 mmol), DAMP/p-TsOH salt (60 mg, 0.2 mmol), DIC (63 mg, 0.5 mmol) in DCM (5 mL) was stirred at r.t.
  • reaction mixture was stirred for further 15 min after the addition was completed before being cooled to r.t. and partitioned between 6 M HCI (100 mL) and EtOAc (100 mL). The aqueous layer was extracted with EtOAc (3 x 100 mL), the combined organics washed with 1 M aqueous NaOH (3 x 200 mL), dried (MgS04) and concentrated under reduced pressure. Re-precipitation from EtOH gave 505 mg of compound 13.1 (21% yield) as a colorless solid.
  • Triethylamine (1.29 mmol, 180 pL) was added and the mixture was stirred at 0 °C for 5 min before BF -OEt (1.94 mmol, 239 pL) was added and the stirring was continued at rt for further 15 min.
  • the reaction mixture was diluted with EtOAc (30.0 mL), washed with 1M HCI (3 x 30.0 mL) and saturated aqueous solution of NaCI (30.0 mL), dried (MgSO 4) and concentrated under reduced pressure. Flash chromatography
  • PLC-14 A mixture of compound 14.4 [4-(4-(6-(4-(diphenylamino)phenyl)-l,3-dioxo- 1H-benzo[de]isoquinolin-2(3H)-yl)-3,5-dimethylphenoxy)butanoic acid] (30 mg, 0.046 mmol), compound 3.5 [dibenzyl 5,5-difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-l,3,7,9- tetramethyl-5H-4 ⁇ 4 ,5 ⁇ 4 -dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8-dicarboxylate] (25 mg, 0.04 mmol), DAMP/p-TsOH salt (40 mg, 0.14 mmol), DIC (50 mg, 0.4 mmol) in DCM (4 mL) was stirred at r.t.
  • PLC-15 To a mixture of ethyl 2-methyl-lH-pyrrole-3-carboxylate (61 mg, 0.4 mmol), compound 13.3 [4-formyl-3,5-dimethylphenyl 4-(4-(6-(4-(diphenylamino)phenyl)-l,3-dioxo- lH-benzo[de]isoquinolin-2(3H)-yl)phenyl)butanoate] (100 mg, 0.136 mmol), MgS04 (120 mg, 1.0 mmol) in dichloroethane (5 mL), was added 3 drops TFA, then heated at 65 °C for 3 days.
  • PLC-16 (T-4)-[2-[(4,5-Dihydro-3-methyl-2H-benz[g]indol-2-ylidene-K/ ⁇ /)( 3,5- dimethyl-4-((4-(6-(4-(diphenylamino)phenyl)-l,3-dioxo-lH-benzo[tfe]isoquinolin-2(3H)- yl)phenyl)butanoate)phenyl)methyl]-4,5-dihydro-3-methyl-lH-benz[g]indolato- kL/Jdifluoroboron): A mixture of compound 9.2 (0.120 mmol, 77 mg), compound 20.3 (vide infra) (0.100 mmol, 54 mg), DAMP/p-TsOH salt (60 mg, 0.2 mmol), DIC (63 mg, 0.5 mmol) in DCM (5 mL) was stirred at r.t.
  • reaction mixture was heated to 100 °C for 70 min and then to 160 °C for40 min, before it was cooled to r.t. and poured into water (500 mL). The precipitate was collected by vacuum filtration and washed with water (100 mL) to give compound 17.2 (352 mg, 20%) as a light blue powder.
  • reaction mixture was diluted with EtOAc (5.00 mL), washed with 1M HCI (3 x 5.00 mL) and saturated aqueous solution of NaCI (5.00 mL), dried (MgS0 4 ) and concentrated under reduced pressure.
  • Example 2.22 PLC-22 Compound 22.1 [Dibenzyl 10-(2,6-difluoro-4-hydroxyphenyl)-5,5-difluoro-l,3,7,9- tetramethyl-5H-4 ⁇ 4 ,5 ⁇ 4 -dipyrrolo[l,2- C :2',1-f][l,3,2]diazaborinine-2,8-dicarboxylate]: To a solution of benzyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (1.05 mmol, 241 mg) and 2,6- difluoro-4-hydroxybenzaldehyde (0.500 mmol, 79 mg) in CH2CI2 (10.0 mL) was added pTsOHH 2 O (0.050 mmol, 6 mg) and the reaction mixture was stirred at r.t.
  • PLC-26 A mixture of compound 26.1 (100 mg, 0.195 mmol), compound 13.3.2 [4-(4- (6-(4-(diphenylamino)phenyl)-l,3-dioxo-lH-benzo[de]isoquinolin-2(3H)-yl)phenyl)butanoic acid] (132 mg, 0.22 mmol), DIC (0.1 mL, 0.63 mmol) and DMAP/p-TsOH (118 mg, 0.4 mmol) in DCM (6mL) was stirred at room temperature overnight, then loaded on silica gel, and purified by flash chromatography using eluents of DCM/ethyl acetate (0% - 5% ethyl acetate).
  • Example 2.27 PLC-27 l,4,5,6-Tetrahydrobenzo[6,7]cyclohepta[l,2-b]pyrrole (Compound 27.1) To a solution of 1- benzosuberone (10.0 mmol, 1.46 mL) in 3:1, HhO/EtOH (32.5 mL) at r.t. were added NH2- OH-HCI (15.0 mmol, 1.04 g) and sodium acetate (25.0 mmol, 2.05 g) and the reaction mixture was stirred at 95 °C for 1 h.
  • Triethylamine (1.20 mmol, 166 m ⁇ ) was added, the mixture was stirred at r.t. for 1 h before BF -OEt (1.80 mmol, 222 pL) was added and the mixture was stirred at r.t. for 3.5 h. It was then diluted with EtOAc (30.0 mL), washed with 3 M HCI (3 x 30.0 mL), dried (MgS ) and concentrated under reduced pressure. Flash chromatography (3:2 hexanes/EtOAc, then 1:1 toluene/CFhCh) gave 13 mg of PLC-28 (7% yield) as a purple solid.
  • PLC-29 A mixture of 3,5-dichloro-4-(19,19-difluoro-6,7,ll,12,13,19-hexahydro-5H-18l4,19l4- benzo[3',4']cyclohepta[l',2':4,5]pyrrolo[l,2-c]benzo[3',4']cyclohepta[l',2':4,5]pyrrolo[2,l- f][l,3,2]diazaborinin-9-yl)phenol (Compound 29.1, 29 mg, 0.0495 mmol), 4-(4-(6-(4- (diphenylamino)phenyl)-l,3-dioxo-lH-benzo[de]isoquinolin-2(3H)-yl)phenyl) butanoic acid (Compound 13.3.2, 48 mg, 0.08 mmol), DIC (0.1 mL, 0.63 mmol), DMAP/TsOH salt (29 mg,
  • a glass substrate was prepared in substantially the following manner. A 1.1 mm thick glass substrate measuring 1-inch X 1-inch was cut to size. The glass substrate was then washed with detergent and deionized (Dl) water, rinsed with fresh Dl water, and sonicated for about 1 hour. The glass was then soaked in isopropanol (IPA) and sonicated for about 1 hour. The glass substrate was then soaked in acetone and sonicated for about 1 hour. The glass was then removed from the acetone bath and dried with nitrogen gas at room temperature.
  • Dl detergent and deionized
  • IPA isopropanol
  • the 20% PMMA solution prepared above (4g) was added to 3 mg of the photoluminescent complex made as described above in a sealed container and mixed for about 30 minutes.
  • the PMMA/lumiphore solution was then spin coated onto a prepared glass substrate at 1000 RPM for 20 s and then 500 RPM for 5 s.
  • the resulting wet coating had a thickness of about 10 pm.
  • the samples were covered with aluminum foil before spin coating to protect them from exposure to light. Three samples each were prepared in this manner for each for Emission/FWHM and quantum yield.
  • the spin coated samples were baked in a vacuum oven at 80 °C for 3 hours to evaporate the remaining solvent.
  • the 1-inch X 1-inch sample was inserted into a Shimadzu, UV-3600 UV-VIS- NIR spectrophotometer (Shimadzu Instruments, Inc., Columbia, MD, USA). All device operations were performed inside a nitrogen-filled glove-box.
  • the resulting absorption/emission spectrum for PC-8 is shown in FIG.l, while the resulting absorption/emission spectrum for PC- 33 is shown in FIG. 2.
  • the fluorescence spectrum of a 1-inch X 1-inch film sample prepared as described above was determined using a Fluorolog spectrofluorometer (Horiba Scientific, Edison, NJ, USA) with the excitation wavelength set at the respective maximum absorbance wavelength. The maximum emission and FWHM are shown in Table 1.

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Abstract

The present disclosure relates to novel photoluminescent complex comprising a BODIPY moiety covalently bonded to a blue light absorbing naphthalic acid derivative, and a color conversion film, a back-light unit using the same.

Description

BORON-CONTAINING CYCLIC EMISSIVE COMPOUNDS AND COLOR CONVERSION FILM
CONTAINING THE SAME CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. Provisional Application No. 62/992,761, filed March 20, 2020, which is incorporated by reference herein in its entirety.
FIELD
The present disclosure is related to compounds for use in color conversion films, backlight units, and display apparatus including the same.
BACKGROUND
In color reproduction the gamut, or color gamut, is a certain complete subset of colors available on a device such as a television or monitor. For example, Adobe™ Red Green Blue (RGB), a wide-gamut color space achieved by using pure spectral primary colors, was developed to provide a broader color gamut and offer a more realistic representation of visible colors viewed through a display. It is believed that a device which could provide a wider gamut could enable the display to portray more vibrant colors.
As high-definition large screen displays become more common, the demand for higher performance, slimmer and highly functional displays have increased. Current light emitting diodes (LEDs) are obtained by a blue light source exciting a green phosphor, a red phosphor, or a yellow phosphor to obtain a white light source. However, the full width half maximum (FWHM) of the emission peak of the current green and red phosphors are quite large, usually greater than 40 nm, resulting in the green and red color spectru ms overlapping and rendering colors that are not fully distinguishable from one another. This overlap leads to poor color rendition and the deterioration of the color gamut.
To correct the deterioration in the color gamut, methods have been developed using films containing quantum dots in combination with LEDs. However, there are problems with the use of quantum dots. First, cadmium-based quantum dots are extremely toxic and are banned from use in many countries due to health safety issues. Second, non-cadmium-based quantum dots have a very low efficiency in converting blue LED light to green and red light. Thirdly, quantum dots require expensive encapsulating processes for protection against moisture and oxygen. Lastly, the cost of using quantum dots is high, because of the difficulties in controlling size uniformity during the production process. SUMMARY
Photoluminescent complexes described herein may be used to improve the contrast between distinguishable colors in televisions, computer monitors, smart devices and any other device that utilizes color displays. The photoluminescent complexes of the present disclosure provide novel color converting dye complexes with good blue light absorbance and narrow emissions bandwidths, with the full width half maximum [FWHM] of emission band of less than 40 nm. In some embodiments, a photoluminescent complex absorbs light of a first wavelength and emits light of a second higher wavelength than the first wavelength. The photoluminescent complexes disclosed herein may be utilized with a color conversion film for use in light emitting apparatuses. The color conversion film of the present disclosure reduced color deterioration by reducing overlap within the color spectrum resulting in high quality color rendition.
Some embodiments include a photoluminescent complex, wherein the photoluminescent complex may comprise: a blue light absorbing moiety: a linker group comprising a substituted ester; and a boron-dipyrromethene (BODIPY) moiety. In some embodiments, the blue light absorbing moiety may comprise a naphthalic acid derivative. In some embodiments, the linker group may covalently link the naphthalic acid derivative to the BODIPY moiety. In some embodiments, the naphthalic acid derivative absorbs light of a first excitation wavelength and transfers an energy to the BODIPY moiety. In some embodiments, the BODIPY moiety absorbs the energy from the naphthalic acid derivative and emits a light energy of a second higher wavelength. In some embodiments, the photoluminescent complex has an emission quantum yield greater than 80%.
In some embodiments, the photoluminescent complex may have an emission band with a full width half maximum [FWHM] of up to 40 nm. In some embodiments, the photoluminescent complex may have a Stokes shift, the difference between the excitation peak of the blue light absorbing moiety and the emission peak of the BODIPY moiety, of equal to or greater than 45 nm.
In some embodiments, the naphthalic acid derivative may be of the following general formula:
Figure imgf000004_0001
In some embodiments, X may be a substituted nitrogen (NR9). In some embodiments,
X may be oxygen (O). In some embodiments, n may be an integer of 0 or 1. In some embodiments, R9 may be selected from H, a substituted aryl, a substituted aryl linker, or a substituted ester linker. In some embodiments, R10 may be selected from H, methyl, a direct bond to an adjacent phenyl ring forming a carbazole, or a substituted ester linker, and R11 may be H or methyl.
Some embodiments include a photoluminescent complex, comprising: a blue light absorbing naphthalic acid derivative; a boron-dipyrromethene (BODIPY) moiety; and a linker group, wherein the linker group covalently links the naphthalic acid derivative to the BODIPY moiety; wherein the blue light absorbing naphthalic acid derivative is represented by the formula:
Figure imgf000004_0002
wherein X is NR9 or O; wherein R9 is H, a substituted aryl, or the linker group; wherein n is 0 or 1; wherein R10 is H, methyl, a direct bond to an adjacent phenyl ring forming a carbazole, or the linker group; wherein R11 is H, or methyl; wherein the linker group is a substituted ester group, or a substituted aralkyl group; wherein the naphthalic acid derivative absorbs light energy of a first excitation wavelength and transfers an energy to the BODIPY moiety, wherein the BODIPY moiety absorbs the energy from the naphthalic acid derivative and emits a light energy of a second higher wavelength; and wherein the photoluminescent complex has an emission quantum yield greater than 80%.
Some embodiments include a color conversion film, wherein the color conversion film may comprise: a color conversion layer; wherein the color conversion layer includes a resin matrix; and at least one photoluminescent complex, as described herein, dispersed within the resin matrix. In some embodiments, the color conversion film may have a thickness between 1 pm to about 200 pm. In some embodiments, the color conversion film of the present disclosure may absorb blue light in the 400 nm to about 480 nm range and emit light in the 510 nm to about 560 nm wavelength range. Another embodiment describes a color conversion film that may absorb blue light in the 400 nm to about 480 nm range and emit light in the 575 nm to about 645 nm wavelength range. In some embodiments, the color conversion film may further comprise a transparent substrate layer. In some embodiments, the transparent substrate layer comprises two opposing surfaces, wherein the color conversion layer is disposed on one of the opposing surfaces.
Some embodiments include a method for preparing the color conversion film, the method comprises: dissolving at least one of the aforedescribed photoluminescent complex and a binder resin within a solvent; and applying the mixture on one of the transparent substrates opposing surfaces.
Some embodiments include a backlight unit including a color conversion film described herein.
Some embodiments include a display device including the backlight unit described herein.
The present application provides a photoluminescent complex's having excellent color gamut and luminescent properties, a method for manufacturing color conversion films using the photoluminescent complexes, and a backlight unit including the color conversion film. These and other embodiments are described in greater detail below. BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a graph depicting the absorption and emission spectra of one embodiment of a photoluminescent complex.
FIG. 2 is a graph depicting the absorption and emission spectra of one embodiment of a photoluminescent complex.
DETAILED DESCRIPTION
The current disclosure describes photoluminescent complexes and their uses in color conversion films. The photoluminescent complexes may be used to improve and enhance the transmission of one or more desired emissive bandwidths within a color conversion film. In some embodiments, the photoluminescent complex may both enhance the transmission of a desired first emissive bandwidth and decrease the transmission of a second emissive bandwidth. For example, a color conversion film may enhance the contrast or intensity between two or more colors, increasing the distinction from one another. In some embodiments, a photoluminescent complex that may enhance the contrast or intensity between two colors, increasing their distinction from one another.
As used herein, when a compound or chemical structure is referred to as being "substituted," it may include one or more substituents. A substituted group is derived from the unsubstituted parent structure wherein one or more hydrogen atoms on the parent structure have been independently replaced by one or more substituent groups. A substituent group may have one or more substituent groups on the parent group structure. In one or more forms, the substituent groups may be independently selected from an optionally substituted alkyl, alkenyl, or a C3-C7 heteroalkyl.
The term "alkyl" group as used herein refers to a hydrocarbon group having no carbon- carbon double or triple bonds. An "alkene" moiety refers to a hydrocarbon group that has at least one carbon-carbon double bond (-C=C-) and an "alkyne" moiety refers to a group that has at least one carbon-carbon triple bond (-CºC-). An alkyl moiety, an alkene moiety, or an alkyne moiety may be branched, straight chain, or cyclic.
The alkyl moiety may have 1 to 6 carbon atoms (whether it appears herein, a numerical range such as "1 to 6" refers to each integer in the given range: e.g., "1 to 6 carbon atoms" means that the alkyl group may have 1 carbon atom, 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbon atoms, or 6 carbon atoms, although the present definition also covers the occurrence of the term "alkyl" where no numerical range is designated. The alkyl group of the compounds designated herein may be designated as "C -C alkyl" or similar designations. By way of example only, "C -C alkyl" indicates that there are one to six carbon atoms in the alkyl chain, i.e., the alkyl chain is selected from among methyl, ethyl, propyl, iso propyl, n-butyl, iso-butyl, sec-butyl, t-butyl, etc. Thus, C1-C6 alkyl includes C1-C2 alkyl, C1-C3 alkyl, C1-C4 alkyl, C1-C5 alkyl. Alkyl groups may be substituted or unsubstituted. Typical alkyl groups include, but are in no way limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.
Typical alkene groups include, but are not limited to, ethenyl, propenyl, butenyl, etc.
The term "aromatic" refers to a planar ring having a delocalized p-electron system containing 4n+2 p electrons, where n is an integer. Aromatic rings may be formed from five, six, seven, eight, nine, or more than nine atoms. Aromatic rings may be optionally substituted. The term "aromatic" includes both carbocyclic aryl (e.g., phenyl) and heterocyclic aryl (or "heteroaryl" or heteroaromatic") group (e.g., pyridine). The term includes monocyclic or fused-ring polycyclic (i.e., rings which share adjacent pairs of carbon atoms) groups.
The term "hydrocarbon ring" refers to a monocyclic or polycyclic radial that contains only carbon and hydrogen. The hydrocarbon ring may be saturated or unsaturated. Monocyclic hydrocarbon rings may have from 3 to 12 carbon atoms. Illustrative examples of monocyclic groups include the following moieties:
Figure imgf000007_0001
and the like. Illustrative examples of polycyclic groups include the
Figure imgf000007_0002
following moieties:
Figure imgf000008_0001
[decahydronaphthalene],
Figure imgf000008_0003
[octahydropentalene],
Figure imgf000008_0002
Figure imgf000008_0004
The term "aryl" as used herein means an aromatic ring wherein each of the atoms forming the ring is a carbon atom. Aryl rings may be formed by five, six, seven, eight, or more than eight carbon atoms. Aryl groups may be substituted or unsubstituted. Examples of aryl groups include, but are not limited to phenyl, naphthalenyl, phenanthrenyl, etc.
The term "aralkyl" refers to an alkyl radical, as defined herein, substituted with an aryl, as defined herein. Non-limiting aralkyl groups include benzyl, 2-phenethyl, 3-phenylpropyl; and the like.
The term "heteroaryl" refers to an aryl group that includes one or more ring heteroatoms selected from nitrogen, oxygen and sulfur, wherein the heteroaryl group has from 4 to 10 atoms in its ring system and with the proviso that the ring of the group does not contain two adjacent oxygen or sulfur atoms. It is understood that the heteroaryl ring can have additional heteroatoms in the ring. In heteroaryl rings that have two or more heteroatoms, those two or more heteroatoms may be the same or different from one another. Heteroaryl rings may be optionally substituted. An N-containing heteroaryl moiety refers to an aryl group in which at least one of the skeletal atoms of the ring is a nitrogen atom. Illustrative examples of heteroaryl groups include the following moieties: pyrrole, imidazole, pyridine, etc. The term "halogen" as used herein means fluorine, chlorine, bromine, and iodine.
The term "bond", "bonded", "direct bond" or "single bond" as used herein means a chemical bond between two atoms or to two moieties when the atoms joined by the bond are considered to be part of a larger structure.
The term "moiety" as used herein refers to a specific segment or functional group of a molecule. Chemical moieties are often recognized chemical entities embedded in or appended to a molecule.
The term "cyano" or "nitrile" as used herein refers to any organic compound that contains a -CN functional group.
The term "ester" refers to a chemical moiety with the formula -COOR, where R is selected from among alkyl, cycloalkyl, aryl, heteroaryl (bonded through a ring carbon) and heterocyclic (bonded through a ring carbon). Any hydroxy, or carboxyl side chain on the compounds described herein may be esterified. Such esters may be prepared by any suitable method which may readily be found in reference sources.
As used herein the term "ether" refers to a chemical moiety that contains an oxygen atom connected to two alkyl or aryl groups with the general formula of R-O-R', where the term alkyl and aryl is as defined herein.
As used herein the term "ketone" refers to the chemical moiety that contains a carbonyl group (a carbon-oxygen double bond) connected to two alkyl or aryl groups with the general formula of RC(=0)R', wherein the term alkyl and aryl is as defined herein. The term "BODIPY" as used herein, refers to a chemical moiety with the formula:
Figure imgf000010_0001
The BODIPY moiety may be composed or dipyrromethene complexed with a di- substituted boron atom, typically a BF2 unit. The lUPAC name for the BODIPY core is 4,4- difluoro-4-bora-3a,4a-diaza-s-indacene. The term "naphthalic acid" or "naphthalic acid derivative" as used herein, refers to a chemical moiety with the formula:
Figure imgf000010_0002
Use of the term "may" or "may be" should be construed as shorthand for "is" or "is not" or, alternatively, "does" or "does not" or "will" or "will not," etc. For example, the statement "the color conversion film may further comprise a transparent substrate layer" should be interpreted as, for example, "In some embodiments the color conversion film further comprises a transparent substrate layer," or "In some embodiments, the color conversion film does not further comprise a transparent substrate layer."
The present disclosure related to photoluminescent complexes that absorb light energy of first wavelength emits light energy in a second higher wavelength. The photoluminescent complex of the present disclosure comprises an absorbing luminescent moiety and an emitting luminescent moiety that are coupled through a linker such that their distance is adjusted for the absorbing luminescent moiety to transfer its energy to the acceptor luminescent moiety, wherein the acceptor luminescent moiety then emits out at a second wavelength that is larger than the absorbed first wavelength. In some embodiments, the photoluminescent complex comprises: a blue light absorbing naphthalic acid derivative; a linker group; and a boron-dipyrromethene (BODIPY) moiety. In some embodiments, the linker group may covalently link the naphthalic acid derivative to the BODIPY moiety. In some embodiments, the naphthalic acid derivative absorbs light of a first excitation wavelength and transfers energy to the BODIPY moiety, the BODIPY moiety then emits a 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 naphthalic acid derivative to the BODIPY moiety occurs through a Forster resonance energy transfer (FRET). This belief is due to the absorbance/emission spectra of the photoluminescent complexes where there are two major absorption bands, one at the blue light absorption band (naphthalic acid derivative) and one at the BODIPY absorption band, and only one emission band located at the BODIPY moieties emission wavelength (see FIGS. 1 and 2).
In an embodiment, the photoluminescent complex may have a high emission quantum yield. In some embodiments, the emission quantum yield may be greater than 50%, 60%, 70 %, 80%, or 90%, up to 100%. 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%, up to 100%, 50-60%, 60-70%, 70-80%, 80-90%, 90-100%. 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 luminescent moiety. In some embodiments, the absorbing luminescent moiety, may have an emission quantum yield greater than 80%. In some embodiments, the quantum yield may be greater than 0.8 (80%), greater than 0.81 (81%), greater than 0.82 (82%), greater than 0.83 (83%), greater than 0.84 (84%), greaterthan 0.85 (85%), greaterthan 0.86 (86%), greaterthan 0.87 (87%), greaterthan 0.88 (88%), greater than 0.89 (89%), greater than 0.9 (90%), greater than 0.91 (91%), greater than 0.92 (92%), greater than 0.93 (93%), greaterthan 0.94 (94%), or greater than 0.95 (95%). Quantum yield measurements in film may be made by spectrophotometer, e.g., Quantaurus- QY spectrophotometer (Flumamatsu, Inc., Campbell, CA, USA).
In some embodiments, the photoluminescent complex has an emission band, the emission band may have a full width half maximum (FWHM) of less than 40 nm. The FWHM is the width of the emission band in nanometers at the emission intensity that is half of the maximum emission intensity for the band. In some embodiments, the photoluminescent complex has an emission band FWHM value that is less than or equal to about 35 nm, less than or equal to about 30 nm, less than or equal about 25 nm, or less than or equal to about 20 nm.
In some embodiments, the photoluminescent complex may have a Stokes shift that is equal to or greater than 45nm. As used herein the term "Stokes shift" means the distance between the excitation peak of the blue light absorbing moiety and the emission peak of the BODIPY moiety.
The photoluminescent complex of the current disclosure may have a tunable emission wavelength. By substituting in different substituents to the BODIPY moiety the emission wavelength may be tuned between 510 nm to about 560 nm or between about 610 nm to about 645 nm, or about any wavelength in a range bounded by any of these values.
In some embodiments, the blue light absorbing moiety may have a peak absorption maximum between about 400 nm to about 470 nm wavelength. In some embodiments, the peak absorption may 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 about any wavelength in a range bounded by any of these values.
In some embodiments, the photoluminescent complex may have an emission peak between 510 nm and 560 nm. In some embodiments, the emission peak may be between about 510 nm to about 515 nm, about 515 nm to about 520 nm, about 520 nm to about 525 nm, about 525 nm to about 530 nm, about 530 nm to about 535 nm, about 535 nm to about 540 nm, about 540 nm to about 545 nm, about 545 nm to about 550 nm, about 550 nm to about 555 nm, about 555 nm to about 560 nm, or about any wavelength in a range bounded by any of these values.
In another embodiment, the photoluminescent complex may have an emission peak between 610 nm to 645 nm. In some embodiments, the emission peak may be between 610 nm to about 615 nm, about 615 nm to about 620 nm, about 620 nm to about 625 nm, about 625 nm to about 630 nm, about 630 nm to about 635 nm, about 635 nm to about 640 nm, about 640 nm to about 645 nm, or about any wavelength in a range bounded by any of these values.
Other embodiments include the photoluminescent complex wherein the blue light absorbing naphthalic acid derivative and the BODIPY moiety's spatial distance is tuned through the linker group, for transfer of the blue light absorbing naphthalic acid derivative's energy to the BODIPY moiety.
The present disclosure describes a photoluminescent complex, wherein the photoluminescent complex may comprise a blue light absorbing naphthalic acid derivative, a linker group and a BODIPY moiety. The linker group covalently links the blue light absorbing naphthalic acid derivative to the BODIPY moiety. In some embodiments, the naphthalic acid derivative absorbs light energy of a first excitation wavelength and transfers an energy to the BODIPY moiety, wherein the BODIPY moiety absorbs the energy from the naphthalic acid derivative and emits a light energy of a second higher wavelength, and wherein the photoluminescent complex has an emission quantum yield greater than 80%. Some embodiments included a blue light absorbing naphthalic acid derivative, wherein the blue light absorbing naphthalic acid derivative may be of the following general formula:
Figure imgf000013_0001
wherein X may be NR9 or O; n is 0 or 1; R9 is H, a substituted aryl, a substituted aryl linker, or a substituted ester linker; R10 is H, a methyl, a direct bond to an adjacent phenyl ring forming a carbazole, or a substituted ester linker; and R11 is a H or a methyl.
In some embodiments X is NR9. In some embodiments, X is O.
In some embodiments, n is 0. In some embodiments, n is 1. In some embodiments, R9 is a substituted H. In some embodiments, R9 is a substituted phenyl. In some embodiments, R9 is the linker group.
In some embodiments, R10 is methyl. In some embodiments, R10 is H. In some embodiments, R10 is the linkergroup. In some embodiments, R10 is a direct bond to an adjacent phenyl ring forming a carbazole.
In some embodiments, R11 is methyl. In some embodiments, R11 is H.
In some embodiments, X may be NR9, n may be 0, R9 may be a substituted ester linker, R10 may be H, and R11 may be H.
In some embodiments, X may be a NR9, n may be 1, R9 may be a substituted ester linker, R10 may be H, and R11 may be H.
In some embodiments, X may be a NR9, n may be 1, R9 may be a substituted ester linker, R10 may be methyl, and R11 may be methyl.
In some embodiments, X may be a NR9, n may be 1, R9 may be a substituted ester linker, R10 may be a direct bond to an adjacent phenyl ring forming a carbazole, and R11 may be H.
In some embodiments, X may be a NR9, n may be 0, R9 may be a substituted aryl, R10 may be a substituted ester linker, and R11 may be H.
In some embodiments, X may be a NR9, n may be 1, R9 may be an aralkyl linker, R10 may be H, and R11 may be H. In some embodiments, X may be a O , n may be 1, R10 may be a substituted ester linker, and R11 may be H.
In some embodiments, R9 is a substituted aryl, wherein the substituted aryl may be
Figure imgf000014_0001
Those of skill in the art will also recognize that the R10 and R11 substituents may be substituted at any position of their respective phenyl rings. While the structural formulae provided herein may depict one of many possible regioisomers, it will be understood that these structures are illustrative only, and that the present disclosure is not limited to any particular isomeric state, and any and all possible regioisomeric states of naphthalic acid derivatives are intended to fall within the scope of the present disclosure.
In some embodiments, the linker group covalently links the blue absorbing naphthalic acid derivative with the BODIPY moiety. The linker group may be varied to adjust the spatial distance between the blue light absorbing naphthalic acid derivative and the BODIPY moiety. By optimizing the spatial distance between the naphthalic acid derivative and the BODIPY moiety, the quantum yield may be tuned.
In some embodiments, L may represent the linker group. The linker group may comprise a substituted ester linker. The substituted ester linker may comprise one of the
Figure imgf000015_0001
In some embodiments, the linker group may comprise a substituted aralkyl linker. In
Figure imgf000015_0002
The photoluminescent complex of the current disclosure may comprise a BODIPY moiety. The BODIPY moiety may have the following chemical formula;
Figure imgf000016_0001
wherein R1 and R6are independently a hydrogen (H), an alkyl group, an alkene group, or an alkyne group;
R3 and R4 are independently a H or a C1-C2 alkyl; R2 and R5, are independently a hydrogen (H), an alkyl group, an alkene group, an alkyne group, a cyano (-CN), an ester (-COOCH2CH3), or an aryl ester (-COOCh^Ar);
R2 and R3 may link together to form an additional monocyclic hydrocarbon ring structure, or a polycyclic hydrocarbon ring structure;
R4 and R5 may link together to form an additional monocyclic hydrocarbon ring structure, or a polycyclic hydrocarbon ring structure;
G7 may be an aralkyl linker, or a substituted aryl moiety of the structure:
Figure imgf000016_0002
R7 and R8 are independently a H, a methyl, a fluoride, a chloride, or an alkoxy group
(such as methoxy); and L represents the linker group.
In some embodiments, R1 is methyl. In some embodiments, R1 is H. In some embodiments, R3 is methyl. In some embodiments, R3 is H. In some embodiments, R4 is methyl. In some embodiments, R4 is H. In some embodiments, R6 is methyl. In some embodiments, R6 is H. In some embodiments, R1, R3, R4, and R6 are methyl.
In some embodiments, R2 is a cyano. In some embodiments, R2 is an alkyl ester or an aryl ester. In some embodiments, R2 is an aryl ester. In some embodiments, R2 is an alkyl ester.
In some embodiments, R5 is a cyano. In some embodiments, R5 is an alkyl ester or an aryl ester. In some embodiments, R5 is an aryl ester. In some embodiments, R5 is an alkyl ester.
In some embodiments, R2 and R5 are a cyano. In some embodiments, R2 and R5 are an alkyl ester or an aryl ester. In some embodiments, R2 and R5 are an aryl ester. In some embodiments, R2 and R5 are an alkyl ester.
In some embodiments, R1 and R2 link together to form a polycyclic hydrocarbon ring structure.
In some embodiments, R5 and R6 link together to form a polycyclic hydrocarbon ring structure.
In some embodiments, R7 is H, a methyl, a halogen, or a methoxy group. In some embodiments, R7 is a methyl, a fluoride, a chloride or a methoxy group. In some embodiments, R7 is methyl.
In some embodiments, R8 is H, a methyl, a halogen, or a methoxy group. In some embodiments, R8 is a methyl, a fluoride, a chloride or a methoxy group. In some embodiments, R8 is methyl.
In some embodiments, R7 and R8 are H, a methyl, a halogen, or a methoxy group. In some embodiments, R7 and R8 are independently a methyl, a fluoride, a chloride or a methoxy group. In some embodiments, R7 and R8 are methyl.
The BODIPY moiety of the present disclosure may be a BODIPY moiety wherein R1, R3, R4and R6 are each a methyl; R2 and R5 are a cyano group; R7 and R8 are each a methyl; and G7 comprises a substituted aryl moiety comprising a substituted ester linker. In some embodiments, the BODIPY moiety of the present disclosure may be a BODIPY moiety wherein R1, R3, R4 and R6 are each a methyl; R2 and R5 are a substituted ester group, wherein the substituted ester group contains an alkyl chain; R7 and R8 are each a methyl; and G7 comprises a substituted aryl moiety comprising a substituted ester linker. In some embodiments, R1, R3, R4and R6 are each a methyl; R2 and R5 are a substituted ester group, wherein the substituted ester group contains an aryl group; R7 and R8 are each selected from a methyl, a fluoride, a chloride, or an alkoxy group; and G7 comprises a substituted aryl moiety comprising a substituted ester linker. In some embodiments, R1 and R2 may link together to form polycyclic hydrocarbon ring structure; R3 and R4 are methyl; R5 and R6 may link together to form a polycyclic hydrocarbon ring structure; R7and R8 may be selected from a H, a methyl, or an alkoxy group; and G7 comprises a substituted aryl moiety comprising a substituted ester linker.
In some embodiments, R2 and R5 may be a substituted ester wherein the substituted ester is an aryl ester. The aryl ester may be the following structure:
Figure imgf000018_0001
In some embodiments, R2 and R5 may be a substituted ester wherein the substituted ester is an alkyl ester. The alkyl ester may be of the following structure:
Figure imgf000018_0002
The photoluminescent complex of the current disclosure may comprise a BODIPY moiety. The BODIPY moiety may have the following chemical formula:
Figure imgf000018_0003
wherein R1 and R2 may link together to form an additional monocyclic hydrocarbon ring structure or a polycyclic hydrocarbon ring structure;
R3 and R4 may be H; R5 and R6 may link together to form an additional monocyclic hydrocarbon ring structure or a polycyclic hydrocarbon ring structure;
R7 and R8 may be independently a H, a halogen, a methyl, or an alkoxy group; and
L represents the linker group comprising a substituted ester linker.
In some embodiments, R1 and R2 may link together to form an additional monocyclic hydrocarbon ring structure, or polycyclic hydrocarbon ring structure. In embodiments, where R1 and R2 are linked together to form a monocyclic hydrocarbon ring structure, the structure may be selected from the following:
Figure imgf000019_0003
[cyclobutane],
Figure imgf000019_0002
[cyclopentane],
Figure imgf000019_0001
[cyclohexane],
Figure imgf000019_0004
[cycloheptane],
Figure imgf000019_0006
[cyclooctane],
Figure imgf000019_0005
[cyclohexene],
Figure imgf000019_0008
, , [cyclopentene],
Figure imgf000019_0007
[cyclohexa-1, 3-diene], or
Figure imgf000019_0009
[cyclododecane]. In some embodiments, where R1 and R2 are linked together to form a polycyclic hydrocarbon ring structure, the structure may be selected from the following:
Figure imgf000019_0011
[bicyclooctane],
Figure imgf000019_0012
[bicyclopentane],
Figure imgf000019_0010
[bicycloheptane],
Figure imgf000019_0014
{bicyclo[4.1.0] heptane],
Figure imgf000019_0013
5s bicyclo[3.3.1]nonane],
Figure imgf000019_0015
[decahydronaphthalene],
Figure imgf000019_0016
[octahydropentalene],
Figure imgf000020_0004
[octahydroindene],
Figure imgf000020_0002
Figure imgf000020_0001
[hexahydroindene],
Figure imgf000020_0003
[1,2,3,4-tetrahydronaphthalene],
Figure imgf000020_0005
[2,3-dihydro-1H-indene],
Figure imgf000020_0006
[l,l-dimethyl-2,3-dihydro-1H-indene], or
Figure imgf000020_0007
[l,2,3,3a-tetrahydropentalene]. In some embodiments, R5 and R6 may link together to form an additional monocyclic hydrocarbon ring structure, or polycyclic hydrocarbon ring structure. In some embodiments, where R5 and R6 are linked together to form a monocyclic hydrocarbon ring structure, the structure may be selected from the following: [cyclobutane],
Figure imgf000020_0009
[cyclopentane],
Figure imgf000020_0008
Figure imgf000020_0015
[cyclohexane],
Figure imgf000020_0013
[cycloheptane],
Figure imgf000020_0012
[cyclooctane],
Figure imgf000020_0010
[cyclohexene],
Figure imgf000020_0016
[cyclohexa-l,4diene],
Figure imgf000020_0014
[cyclopentene],
Figure imgf000020_0011
[cyclohexa-
1,3, diene], or
Figure imgf000020_0017
[cyclododecane]. In some embodiments, where R5 and R6 are linked together to form a polycyclic hydrocarbon ring structure, the structure may be selected from the following:
Figure imgf000020_0018
Figure imgf000020_0019
Figure imgf000020_0020
Figure imgf000021_0002
Figure imgf000021_0003
Figure imgf000021_0006
Figure imgf000021_0004
Figure imgf000021_0007
Figure imgf000021_0005
Figure imgf000021_0008
Figure imgf000021_0010
Figure imgf000021_0009
Figure imgf000021_0011
In some embodiments, the distance separating the blue light absorbing naphthalic acid derivative and the BODIPY moiety may be about 8 A or greater. The linker group may maintain the desired distance between the blue light absorbing naphthalic acid derivative and the BODIPY moiety.
In some embodiments, the photoluminescent complex comprises a linker group, wherein the linker group covalently links the blue light absorbing naphthalic acid derivative to the BODIPY moiety. In some embodiments, the linker group may comprise an optionally substituted C -C ester group. When the linker group comprises a substituted ester group, the linker group may be selected from among one of the following:
Figure imgf000021_0001
Figure imgf000022_0001
In some embodiments, the BODIPY moiety may have the following chemical formula:
Figure imgf000022_0002
wherein L' may be an aralkyl linker. In some examples, the aralkyl linker may be
Figure imgf000022_0003
The photoluminescent complex of the present disclosure may be represented by the following which are provided for the purpose of illustration and are in no way to be construed as limiting:
Figure imgf000023_0001
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000026_0001
Figure imgf000027_0001
In some embodiments, a photoluminescent complex comprises a blue light absorbing naphthalic acid derivative. The blue light absorbing naphthalic acid derivative may comprise an organic lumiphore. In some embodiments, the naphthalic acid derivative may have a maximum absorbance in the light in 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 about any wavelength in a range bounded by any of these values. In some embodiments, the photoluminescent complex may have an absorbance maximum peak of about 450 nm. In other embodiments, the blue light absorbing naphthalic acid derivative may have a maximum peak absorbance of about 405 nm. In still other embodiments, the blue light absorbing naphthalic acid derivative may have a maximum peak absorbance of about 480 nm.
Some embodiments include a color conversion film, wherein the color conversion film comprises: a color conversion layer wherein the color conversion layer includes a resin matrix and photoluminescent complexes, described above, dispersed within the resin matrix. In some embodiments the color conversion film may be described as comprising one or more of the complexes described herein.
In some embodiments, the color conversion film may be about 1 pm to about 200 pm thick, about 1 pm to about 5 pm, about 5 pm to about 10 pm, about 10 pm to about 15 pm, about 15 pm to about 20 pm, about 20 pm to about 40 pm, about 40 pm to about 80 pm, about 80 pm to about 120 pm, about 120 pm to about 160 pm about 160 pm to about 200 pm thick, or about any thickness in a range bounded by any of these values.
In some embodiments, the color conversion film may absorb light in the 400 nm to about 480 nm wavelength and may emit light in the range of about 510 nm to about 560 nm and/or about 610 nm to about 645 nm. In other embodiments, color conversion film may emit light in the 510 nm to about 560 nm range, the 610 nm to about 645 nm range, or any combination thereof.
In some embodiments, the color conversion film may further comprise a transparent substrate layer. The transparent substrate layer may have two opposing surfaces, wherein the color conversion layer may be disposed on and in physical contact with the surfaces of the transparent layer that will be adjacent to a light emitting source. The transparent substrate is not particularly limited and one skilled in the art would be able to choose a transparent substrate from those used in the art. Some non-limiting examples of transparent substrates include PE (polyethylene), PP (polypropylene), PEN (polyethylene naphthalate), PC (polycarbonate), PMA (polymethylacrylate), PMMA (Polymethylmethacrylate), CAB (cellulose acetate butyrate), PVC (polyvinylchloride), PET (polyethyleneterephthalate), PETG (glycol modified polyethylene terephthalate), PDMS (polydimethylsiloxane), COC (cyclo olefin copolymer), PGA (polyglycolide or polyglycolic acid), PLA (polylactic acid), PCL (polycaprolactone), PEA (polyethylene adipate), PHA (polyhydroxy alkanoate), PHBV (poly(3- hydroxybutyrate-co-3hydroxyvalerate)), PBE (polybutylene terephthalate), PTT (polytrimethylene terephthalate). Any of the aforedescribed resins may be corresponding/respective monomers and/or polymers.
In some embodiments, the transparent substrate may have two opposing surfaces. In some embodiments, the color conversion film may be disposed on and in physical contact with one of the opposing surfaces. In some embodiments, the side of the transparent substrates without color conversion film disposed thereon, may be adjacent to a light source. The substrate may function as a support during the preparation of the color conversion film. The type of substrates used are not particularly limited, and the material and/or thickness is not limited, as long as it is transparent and capable of functioning as a support. A person skilled in the art could determine which material and thickness to use as a supporting substrate.
Some embodiments include a method for preparing the color conversion film, wherein the method comprises: dissolving a photoluminescent compound, described herein, and a binder resin within a solvent; and applying the mixture on to the surface of the transparent substrate.
The binder resin which may be used with the photoluminescent complex(s) includes resins such as acrylic resins, polycarbonate resins, ethylene-vinyl alcohol copolymer resins, ethylene-vinyl acetate copolymer resins and saponification products thereof, AS resins, polyester resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins, polyvinyl phosphonic acid (PVPA), polystyrene resins, phenolic resins, phenoxy resins, polysulfone, nylon, cellulosic resins, and cellulose acetate resins. In some embodiments, the binder resin may be a polyester resin and/or acrylic resin.
The solvent which may be used for dissolving or dispersing the complex and the resin may include an alkane, such as butane, pentane, hexane, heptane, and octane; a cycloalkane, such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane; an alcohol, such as ethanol, propanol, butanol, amyl alcohol, hexanol, heptanol, octanol, decanol, undecanol, diacetone alcohol, and furfuryl alcohol; Cellosolves™, such as Methyl Cellosolve™, Ethyl Cellosolve™, Butyl Cellosolve™, Methyl Cellosolve™ acetate, and Ethyl Cellosolve™ acetate; propylene glycol and its derivatives, such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, and dipropylene glycol dimethyl ether; a ketone, such as acetone, methyl amyl ketone, cyclohexanone, and acetophenone; an ether, such as dioxane and tetrahydrofuran; an ester, 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; a halogenated hydrocarbon, such as chloroform, methylene chloride, and tetrachloroethane; an aromatic hydrocarbon, such as benzene, toluene, xylene, and cresol; and/or a highly polar solvent, such as dimethyl formamide, dimethyl acetamide, and N-methylpyrrolidone.
Some embodiments include a backlight unit, wherein the backlight unit may include the aforedescribed color conversion film.
Other embodiments may describe a display device; the device may include the backlight unit described hereinto.
Unless otherwise indicated, all numbers expressing quantities of ingredients, properties, such as, molecular weight, reaction conditions, and so forth used in the specification and embodiments are to be understood as being modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and attached embodiments are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, and not as an attempt to limit the application of the doctrine of equivalents. To the scope of the embodiments, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
For the processes and/or methods disclosed, the functions performed in the processes and methods may be implemented in differing order, as may be indicated by context. Furthermore, the outlined steps and operations are only provided as examples and some of the steps and operations may be optional, combined into fewer steps and operations, or expanded into additional steps and operations.
This disclosure may sometimes illustrate different components contained within, or connected with, different other components. Such depicted architectures are merely examples, and many other architectures may be implemented which achieve the same or similar functionality.
The terms used in this disclosure and in the appended embodiments, (e.g., bodies of the appended embodiments) are generally intended as "open" terms (e.g., the term "including" should be interpreted as "including, but not limited to," the term "having" should be interpreted as "having at least," the term "includes" should be interpreted as "includes, but not limited to," etc.). In addition, if a specific number of elements is introduced, this may be interpreted to mean at least the recited number, as may be indicated by context (e.g., the bare recitation of "two recitations," without other modifiers, means at least two recitations of two or more recitations). As used in this disclosure, any disjunctive word and/or phrase presenting two or more alternative terms should be understood to contemplate the possibilities of including one of the terms, either of the terms, or both terms. For example, the phase "A or B": will be understood to include the possibilities of "A" or "B" or "A and B."
The terms "a," "an," "the" and similar referents used in the context of describing the present disclosure (especially in the context of the following embodiments) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The use of any and all examples, or representative language (e.g., "such as") provided herein is intended merely to better illuminate the present disclosure and does not pose a limitation on the scope of any embodiments. No language in the specification should be construed as indicating any non-embodied element essential to the practice of the present disclosure.
Groupings of alternative elements or embodiments disclosed herein are not to be construed as limitations. Each group member may be referred to and embodied individually or in any combination with other members of the group or other elements found herein. It is anticipated that one or more members of a group may be included in, or deleted from, a group for reasons of convenience and/or patentability. When any such inclusion or deletion occurs, the specification is deemed to contain the group as modified thus fulfilling the written description of all Markush groups used in the appended embodiments.
Certain embodiments are described herein, including the best mode known to the inventors for carrying out the present disclosure. Of course, variations on these described embodiments, will become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventor expects skilled artisans to employ such variations as appropriate, and the inventors intend for the present disclosure to be practiced otherwise than specifically described herein. Accordingly, the embodiments include all modifications and equivalents of the subject matter recited in the embodiments as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is contemplated unless otherwise indicated herein or otherwise clearly contradicted by context. In closing, it is to be understood that the embodiments disclosed herein are illustrative of the principles of the embodiments. Other modifications that may be employed are within the scope of the embodiments. Thus, by way of example, but not of limitation, alternative embodiments may be utilized in accordance with the teachings herein. Accordingly, the embodiments are not limited to the embodiments precisely as shown and described.
EMBODIMENTS Embodiment 1 A photoluminescent complex comprising:
A blue light absorbing naphthalic acid derivative of general formula:
Figure imgf000032_0001
wherein X is NR9 or O, n is an integer of 0 or 1, R9 is selected from H, a substituted aryl, a substituted aryl linker or a substituted ester linker, R10 is selected from a H, a methyl, a direct bond to an adjacent phenyl ring forming a carbazole, or a substituted ester linker, and R11 is a H or a methyl; a linker group, wherein the linker group is a substituted ester; and a boron-dipyrromethene (BODIPY) moiety; wherein the linker group covalently links the naphthalic acid derivative to the BODIPY moiety, wherein the naphthalic acid derivative absorbs light energy of a first excitation wavelength and transfers an energy to the BODIPY moiety, wherein the BODIPY moiety absorbs the energy from the naphthalic acid derivative and emits a light energy of a second higher wavelength, and wherein the photoluminescent complex has an emission quantum yield greater than 80%.
Embodiment 2 The naphthalic acid derivative of embodiment 1, wherein X is N, n is 0, R9 is substituted ester linker, R10 is H, and R11 is H.
Embodiment 3 The naphthalic acid derivative of embodiment 1, wherein X is N, n is 1, R9 is substituted ester linker, R10 is H, and R11 is H.
Embodiment 4 The naphthalic acid derivative of embodiment 1, wherein X is N, n is 1, R9 is substituted ester linker, R10 is methyl, and R11 is methyl. Embodiment 5 The naphthalic acid derivative of embodiment 1, wherein X is N, n is 1,
R9 is substituted ester linker, R10 is a direct bond to an adjacent phenyl ring forming a carbazole, and R11 is H.
Embodiment 6 The naphthalic acid derivative of embodiment 1, wherein X is N, n is 0, R9 is a substituted aryl, R10 is substituted ester linker, and R11 is H. Embodiment 7 The naphthalic acid derivative of embodiment 1, wherein X is O, n is 1,
R9 is H, R10 is substituted ester linker, and R11 is H.
Embodiment 8 The naphthalic acid derivative of embodiment 6, wherein the substituted aryl is selected from one of the following structures:
Figure imgf000033_0001
Embodiment 9 The photoluminescent complex of embodiment 1 wherein the BODIPY moiety is of the general formula:
Figure imgf000034_0001
wherein R1 and R6 are independently selected from a hydrogen (H), an alkyl group, an alkene group, or an alkyne group;
R3 and R4 are independently selected form a H or a C1-C2 alkyl; R2 and R5, are independently selected from a hydrogen (H), an alkyl group, an alkene group, an alkyne group, a cyano (-CN), an ester (-COOCH2CH3), or an aryl ester (-COOCH2Ar);
R2 and R3 may link together to form an additional monocyclic hydrocarbon ring structure, or a polycyclic hydrocarbon ring structure;
R4 and R5 may link together to form an additional monocyclic hydrocarbon ring structure, or a polycyclic hydrocarbon ring structure;
R7 and R8 may be independently selected from a H, a methyl, a fluoride, a chloride, or an alkoxy group and
L represents the linker group comprising a substituted ester linker.
Embodiment 10 The BODIPY moiety of embodiment 9, wherein R1, R3, R4, and R6 are methyl, R2 and R5 are selected from a substituted ester, R7 and R8 are methyl and L is a linker group.
Embodiment 11 The BODIPY moiety of embodiment 9, wherein R1, R3, R4, and R6 are methyl, R2 and R5 are a cyano, R7 and R8 are methyl and L is a linker group.
Embodiment 12 The BODIPY moiety of embodiment 9, wherein R1, R3, R4, and R6 are methyl, R2 and R5 are an aryl ester, R7 and R8 are selected from a methyl, a fluoride, a chloride or an ether group, and L is a linker group. Embodiment 13 The photoluminescent complex of embodiment 1 wherein the BODIPY moiety is of the general formula:
Figure imgf000035_0001
R1 and R2 link together to form an additional polycyclic hydrocarbon ring structure;
R3 and R4 are methyl;
R5 and R6 link together to form an additional polycyclic hydrocarbon ring structure;
R7 and R8 may be independently selected from a H, a methyl or an alkoxy group; and
L represents the linker group comprising a substituted ester linker.
Embodiment 14 The BODIPY moiety of embodiment 13, wherein R1 and R2 link together to form a hydrocarbon ring structure, R3 and R4, are methyl, R5 and R6 may link together to form a polycyclic hydrocarbon ring structure, R7 and R8 is selected from a H, a methyl, or an ether group, and L is a linker group.
Embodiment 15 The photoluminescent complex of embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, and 14, wherein the substituted ester of the linker group is selected from one if the following structures:
Figure imgf000035_0002
Figure imgf000036_0001
Embodiment 16 The photoluminescent complex of embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, and 14, wherein the linkergroup may comprise a substituted aryl linker, where. In some embodiments, the substituted alkyl linker may be
Figure imgf000036_0003
Embodiment 17 The photoluminescent complex of embodiments 1, 2, 3, 4, 5, 6, 1 , 8, 9, 10, 11, 12, 13, and 14, wherein the complex is selected from any one of the following structures:
Figure imgf000036_0002
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001
Embodiment 18 A color conversion film comprising: a transparent substrate layer; a color conversion layer, wherein the color conversion layer includes a resin matrix, and at least one photoluminescent complex, wherein the at least one photoluminescent compound is comprised the photoluminescent compound of embodiments, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14, dispersed within the resin matrix.
Embodiment 19 The color conversion film of embodiment 18, further comprising a singlet oxygen quencher.
Embodiment 20 The color conversion film of embodiment 18, further comprising a radical scavenger. Embodiment 21 The color conversion film of embodiment 18, wherein the film has a thickness of between 10 pm and 200 pm.
Embodiment 22 The color conversion film of embodiment 17, wherein the film absorbs light in about 400 nm to about 480 nm wavelength range and emits light in the 510 nm to about 560 and in the 575 nm to about 645 nm wavelength range.
Embodiment 23 A method for preparing the color conversion film of embodiments 18, 19, 20, and 21 the method comprising: dissolving the photoluminescent complex of embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, and 14, and a binder resin within a solvent; and applying the mixture to one of the transparent substrates opposing surfaces.
Embodiment 24 A backlight unit including the color conversion film of embodiment 18, 19, 20, 21, or 22.
Embodiment 25 A display device including the back-light unit of embodiment 24.
EXAMPLES
It has been discovered that embodiments of the photoluminescent complexes described herein have improved performance as compared to other forms of dyes used in color conversion films. These benefits are further demonstrated by the following examples, which are intended to be illustrative of the disclosure only but are not intended to limit the scope or underlying principles in any way.
Example 1.1 Comparative example 1 (CE-1):
CE-1: 0.75 g of 4-hydoxyl-2,6-dimethylbenzaldehyde (5 mmol) and 1.04 g of 2,4- dimethylpyrrole (11 mmol) was dissolved in 100 mL of anhydrous dichloromethane. The solution was degassed for 30 minutes. Then one drop of trifluoroacetic acid was added. The solution was stirred overnight under argon gas atmosphere at room temperature. To the resulting solution, DDQ (2.0 g) was added and the mixture was stirred overnight. The next day the solution was filtered and then washed with dichloromethane resulting in a dipyrrolemethane (1.9 g). Next, 1.0 g of dipyrrolemethane was dissolved in 60 mL of THF. 5 mL of trimethylamine was added to the solution and then degassed for 10 minutes. After degassing, 5 mL of trifluoroboron-diethylether was added slowly followed by heating for 30 minutes at 70° C. The resulting solution was loaded on a silica gel and purified by flash chromatography using dichloromethane as the eluent. The desired fraction was collected and dried under reduced pressure to yield 0.9 g of an orange solid (76% yield). LCMS (APCI+): calculated for C21H24BF2N2O (M+H) = 369; found: 369. 1H NMR (400 MHz, Chloroform-d) d 6.64 (s, 2H), 5.97 (s, 2H), 4.73 (s, 1H), 2.56 (s, 6H), 2.09 (s, 6H), 1.43 (s, 6H). Example 1.2 Comparative Example 2 (CE-2): was synthesized as described in Wakamiya, Atsushi et ai Chemistry Letters, 37(10), 1094-1095; 2008
Example 2: Synthesis of Photoluminescent Complexes:
Example 2.1: PLC-1
Figure imgf000043_0001
PLC-1
Compound 1.1: A mixture of 4-bromo-l,8-naphthalic anhydride (5.5 g, 20 mmol), 4- butyl-aniline (3.58 g, 25 mmol) in ethanol (20 mL) was degassed and heated at reflux overnight (16hr). After cooling to r.t., the mixture was filtered and the solid was washed with methanol, dried with air to give an off-white solid (7.48 g, in 92% yield). LCMS (APCI-): calcd for C22Hi8BrN02 (M-): 408; found: 408.
Compound 1.2: A mixture of compound 1.1 (1.0 g, 2.45 mmol), N,N'-diphenylamine (0.62 g, 3.7 mmol), Pd(dppf)Cl2 (0.15 g, 0.2 mmol) and sodium f-butoxide (0.36 g, 3.7 mmol) in anhydrous toluene (25 mL) was degassed and heated at 110 °C overnight. The resulting mixture was loaded on silica gel, and purified by flash chromatography using eluents of dichloromethane/hexanes (0% - 90% dichloromethane). The main orange colorfraction was collected and 0.6 g orange solid was obtained after removal of solvents (in 50% yield). LCMS (APCI): calcd for C34H28N2O2 (M-): 496; Found: 496. *H NMR (400 MHz, TCE) d 8.48 - 8.37 (m, 2H), 8.15 (dd, J = 8.6, 1.2 Hz, 1H), 7.46 (dd, J = 8.6, 7.2 Hz, 1H), 7.31 (dd, J = 8.2, 6.6 Hz, 3H), 7.25 - 7.17 (m, 4H), 7.16 - 7.10 (m, 2H), 7.06 - 6.95 (m, 6H), 2.69 - 2.60 (m, 2H), 1.67 - 1.55 (m, 2H), 1.36 (dt, J = 14.8, 7.3 Hz, 2H), 0.86 (dt, 7 = 24.8, 7.3 Hz, 3H).
Compound 1.3 and 1.4: To the solution of compound 1.2 (200 mg, 0.40 mmol) and methyl 4-chloro-4-oxobutyrate (120 mg, 0.8 mmol) in 10 mL dichloroethane, was added 0.8 mL of 1.0M ZnCl2 solution in diethyl ether. The whole was degassed for 30min, then heated at 66 °C overnight. After cooled to r.t., the mixture was dissolved in 100 mL dichloromethane, washed with aqueous NH4CI solution, then brine. The organic phase was collected and dried over Na2SC>4, loaded on silica gel, and purified by flash chromatography using eluents of dichloromethane/ethyl acetate (0% - 100% Ethyl acetate). The desired fraction (the most polar one) was collected, and an orange solid was obtained after removal of solvents (100 mg, in 42% yield). LCMS (APCI): calcd for C38H31N2O5 (M-H): 595; found: 595.
PLC-1: A mixture of compound 1.4 (40 mg, 0.067 mmol), dibenzyl 5,5-difluoro-10-(4- hyd roxy-2, 6-dimethyl phenyl)-l, 3,7, 9-tetra methyl-5H-4λ4λ 5λ4-dipyrrolo[l, 2-c:2',l'- f][l,3,2]diazaborinine-2,8-dicarboxylate] (38 mg, 0.06 mmol), DMAP/TsOH salt (29 mg, 0.1 mmol), and DIC (30 mg, (0.2 mmol) in dichloromethane (5 mL) was stirred at r.t. overnight. The resulting mixture was loaded on silica gel and purified by flash chromatography using eluents of DCM/ethyl acetate (0% → 30% ethyl acetate). The desired fraction was collected, and an orange solid was obtained after removal of solvents (5 mg, in 7% yield). LCMS (APCI): calcd for C75H65BF2N4O9 (M-): 1214: found: 1214. Example 2.2: PLC-2
Figure imgf000045_0001
Compound 2.1 [5,5-difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-l,3,7,9-tetramethyl- 5H-4λ4,5λ4-dipyrrolo[l,2-c:2',l'-/][l,3,2]diazaborinine-2,8-dicarbonitrile]: Compound 2.1 was synthesis as described in US Provisional Patent Application 62/986,462. PLC-2: A mixture of compound 1.4 (40 mg, 0.067 mmol), 5,5-difluoro-10-(4-hydroxy-
2, 6-dimethyl phenyl)-l, 3,7, 9-tetramethyl-5H-4λ4, 5λ4-dipyrrolo[l, 2-c:2',l'- /][l,3,2]diazaborinine-2,8-dicarbonitrile (25 mg, 0.06 mmol), DMAP/p-TsOH salt (30 mg, 0.1 mmol), and DIC (30 mg, 0.24 mmol) in DCM (5 mL) was stirred at r.t. overnight. The resulting mixture was loaded on silica gel and purified by flash chromatography using eluents of DCM/ethyl acetate (0% - 35% ethyl acetate). The desired fraction as collected, and an orange solid was obtained after removal of solvents (5 mg, in 8% yield). LCMS (APCI): calcd for C61H51BF2N6O5 (M-): 996; found: 996. 1H NMR (400 MHz, Chloroform-d) d 8.66 - 8.58 (m, 2H), 8.19 (dd, J = 8.6, 1.1 Hz, 1H), 7.93 - 7.85 (m, 2H), 7.61 (dd, J = 8.5, 7.2 Hz, 1H), 7.52 (d, J = 7.9 Hz, 1H), 7.36 (dt, J = 8.4, 3.7 Hz, 4H), 7.25 - 7.14 (m, 6H), 7.09 - 7.04 (m, 2H), 7.01 - 6.93 (m, 2H), 3.37 (t, J = 6.3 Hz, 2H), 3.00 (t, J = 6.2 Hz, 2H), 2.73 (s, 6H), 2.69 (d, J = 7.8 Hz, 2H), 2.12
(d, J = 0.8 Hz, 6H), 1.73 - 1.64 (m, 2H), 1.62 (s, 6H), 1.47 - 1.35 (m, 2H), 0.96 (t, 3H).
Example 2.3: PLC-3
Figure imgf000046_0001
Compound 3.1: A mixture of compound 1.1 (816 mg, 2 mmol), (4- (diphenylamino)phenyl)boronic acid (580 mg, 2 mmol), Pd(PPh3)4 (115 mg, 0.1 mmol), K2CO3 (414 mg, 3 mmol) in dioxane/water (10 mL/2 mL) was degassed and heated at 100 °C overnight. After cooled to r.t., yellow precipitate forms. The solid was collected after filtration and washing with water, methanol and drying with vacuum. The solid was dissolved in DCM and further purified by flash chromatography using eluents of DCM/hexanes (0% - 80% DCM). The main orange fraction were collected and a yellow solid was obtained after removal of solvents (1.0 g, in 87.4% yield). LCMS (APCI): calcd for C40H33N2O2 (M+H): 573; found: 573. Compound 3.2: To the mixture of compound 3.1 (458 mg, 0.8 mmol), methyl 4-chloro-
4-oxobutyrate (240 mg, 1.6 mmol) in 20mL DCE was added 1.0M ZnC in diethyl ether (1.0 mL, 1.0 mmol). The whole was degassed then heated at 50 °C overnight under argon atmosphere. After cooled to r.t., the mixture was worked up with DCM/water. The organic phase was collected and dried over MgSC , concentrated and loaded on silica gel, then purified by flash chromatography using eluents of DCM/ethyl acetate (0% - 8% ethyl acetate). The desired fraction was collected, and removal solvents gave desired product as orange solid (0.30 g, in 50% yield). LCMS (APCI): calcd for C45H39N2O5 (M+H): 687; found: 687. Compound 3.3: To a solution of compound 3.2 in DCM/TFA (10 mL/4 mL), was added triethylsilane (1.5 g, 13 mmol) in 10 portions over 10 hrs. After removal of solvents, the remaining oily solid was redissolved in 10 mL DCM, and purified by flash chromatography using eluents of hexanes/ethyl acetate (0% - 20% ethyl acetate). The main fraction was collected and removal of solvents gave an orange solid (0.23 g, in 78% yield). LCMS (APCI): calcd for C45H40N2O4 (M-): 672; found: 672. *H NMR (400 MHz, TCE) d 8.59 - 8.52 (m, 2H), 8.43 (dd, J = 8.7, 1.1 Hz, 1H), 7.70 (t, J = 7.6 Hz, 2H), 7.32 (d, J = 8.1 Hz, 4H), 7.25 (dd, J = 8.4, 7.2 Hz, 2H), 7.18 - 7.09 (m, 6H), 7.07 (s, 4H), 7.01 (t, J = 7.3 Hz, 1H), 3.59 (s, 3H), 2.65 (t, J = 7.8 Hz, 2H), 2.56 (t, J = 7.5 Hz, 2H), 2.29 (q, J = 7.0, 6.6 Hz, 2H), 1.89 (p, J = 7.4 Hz, 2H), 1.36 (h, J = 7.5 Hz, 2H), 0.90 (t, J = 7.3 Hz, 3H).
Compound 3.4: To a mixture of 3.3 (0.23 g, 0.34 mol) in 1-butanol (8 mL), was added 5M KOH aqueous solution (0.7 mL, 3.4 mmol), the whole was heated at 90 °C for 1 hour. The reaction mixture was concentrated to lmL under reduced pressure, then diluted with 10 mL methanol, and dropped into 20 mL IN HCI aqueous solution. Orange precipitate forms, the solid was collected by filtration and washed with water, dried in vacuum to give a 180 mg red solid (in quantitative yield). LCMS (APCI): calcd for C34H25NO5 (M-): 527; found: 527.
Figure imgf000047_0001
Figure imgf000047_0002
Compound 3.5 (dibenzyl 5,5-difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-l,3,7,9- tetramethyl-5H-4λ4,5λ4-dipyrrolo[l,2-c:2', -f][l,3,2]diazaborinine-2,8-dicarboxylatel: To 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 in an ice water bath to about 10 °C. Sodium nitrite (18 g, 262 mmol) was added over 1 h while the temperature was kept under 15 °C. The cold bath was removed, and the mixture was stirred for 3.5 h at room temperature. The un soluble material was filtered off to give a crude solution of oxime, which was used without further purification in the next step. Next, 50 g of zinc dust (0.76 mol) was added portion wise to a mixture of 13.7 mL (79 mmol) benzyl-3-oxobutyrate and 100 mL of acetic acid. The resulting mixture was stirred in an oil bath and heated to 60 °C. The cured tert-butyl-2- (hydroxyimino-3-oxobutanoate solution was added slowly. The temperature was then increased 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 yield benzyl 2,4-dimehtyl-1H-pyrrole-3- carboxylate, which was recrystallized from MeOH as a white solid, gained 15 g, yield 65% based on benzyl 3-xobutyrate. 1H NMR (400 MHz, CDCI3): 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).
Next, in a 25 mL vial, a mixture of 1 g (4.36 mmol) of benzyl 2,4-dimethyl-1H-pyrrole-
3-carboxylate, 0.524 g (4.36 mmol) of MgSO4, was dissolved in 8 mL of anhydrous DCE and stirred at room temperature in the presence of argon gas, for 15 min. 0.327 g of 2,6 dimethyl
4-hydroxybenzaldehyde (2.18 mmol) was added in small portions; the vial was closed with a Teflon cap. The resulting mixture was continued to purge with argon for 15 min and TFA (3 drops, a catalytic amount) was added. The reaction mixture was stirred at 65 °C for 16 h. TLC and LCMS showed starting materials were consumed. To the crude product, 0.544 g (2.398 mmol) of DDQ was added in one portion. The resulting mixture was stirred at room temperature for ½ h. TLC and LCMS showed the starting materials were consumed. The resulting mixture was filtered through a short path of celite; the filtrate was concentrated to dryness, the residue was re-dissolved into 50 mL of DCE stirred with trimethylamine (1.4 mL, 19 mmol) at room temperature for 15 min then cooled to 0 °C. 3 mL of BF3-OEt2 (18.36 mmol) was added slowly. The resulting mixture was stirred at room temperature for ½ h then heated to 86 °C for 45 min. The reaction mixture was then diluted with 150 mL of CHCI3, and quenched with 50 mL brine. The organic layers were separated and dried over MgSC>4, and the solvents were removed by rotary evaporation. The residue was chromatographed on a column of silica gel using CH2Cl/EtOAc as eluent to afford a 1 g pure dibenzyl 5,5-difluoro-10- (4-hyd roxy-2, 6-dimethyl phenyl)-l, 3, 7, 9-tetramethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',r- f][l,3,2]diazaborinine-2,8-dicarboxylate), as a red orange solid, 72% yield based on 2,6 dimethyl-4-hydroxybenzaldehyde. LCMS (ARC!-}, calcd M- for C 37 H 5635 ,?0¾ : 636.26; found: 636, *H NMR (400 MHz, Chloroform-d) d 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).
PLC-3: A mixture of compound 3.4 (72 mg, 0.136 mmol), compound 3.5 [dibenzyl 5,5- dif luoro-10-(4-hyd roxy-2, 6-dimethyl phenyl)-l, 3,7, 9-tetra methyl-5H-4A4, 5A4-dipyrrolo[l, 2- c:2',l'-/][l,3,2]diazaborinine-2,8-dicarboxylate] (64 mg, 0.1 mmol), DMAP/p-TsOH salt (59 mg, 0.2 mmol) and DIC (63 mg, 0.5 mmol) in DCM (5 mL) was stirred at r.t. overnight. The resulting mixture was purified by flash chromatography using eluents of DCM/ethyl acetate (0% -> 5%). The desired fraction was collected and concentrated, the solid was further purified by reprecipitation in DCM/methanol to give an orange solid (70 mg, in 61% yield). LCMS (APCI): calcd for C71H58BF2N3O9 (M-): 1146; found: 1146.
Example 2.4: PLC-4
Figure imgf000050_0001
Compound 4.1: A solution of compound 3.4 (95 mg, 0.18 mmol), 4-butyla niline (30 mg, 0.2 mmol) in 3 mL ethanol was heated at 85 °C overnight. To the resulting solution was added 0.1 mL 35% aqueous HCI solution and mixture was cooled to room temperature. Filtration and drying in air gave a light yellow solid (90 mg, in 76% yield). LCMS (APCI): calcd for C44H38N2O4 (M-): 658; found: 658. *H NMR (400 MHz, Chloroform-d) d 8.70 - 8.63 (m, 2H), 8.46 (dd, J = 8.5, 1.2 Hz, 1H), 7.75 (dd, J = 9.3, 7.5 Hz, 2H), 7.40 (d, J = 2.0 Hz, 1H), 7.39 - 7.27 (m, 5H), 7.26 - 7.17 (m, 6H), 7.15 (s, 4H), 7.13 - 7.05 (m, 1H), 2.75 - 2.64 (m, 4H), 2.43 (t, J = 7.4 Hz, 2H), 2.00 (p, J = 7.5 Hz, 2H), 1.68 (p, J = 7.6 Hz, 2H), 1.42 (h, J = 7.3 Hz, 2H), 0.96 (t, J =
7.3 Hz, 3H). Compound PLC-4: The mixture of compound 4.1 (50 mg, 0.076 mmol), dibenzyl 5,5- difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-l,3,7,9-tetramethyl-5H-4λ4,5λ4-dipyrrolo[l,2- c:2',l'-f][l,3,2]diazaborinine-2,8-dicarboxylate) (40 mg, 0.063 mmol), DMAP/p-TsOH salt (60mg, 0.2 mmol), DIC (63 mg, 0.5 mmol) in 2mL DCM, was stirred at r.t. overnight. The resulting mixture was purified by flash chromatography using eluents of DCM/ethyl acetate (0% → 5%). The desired fraction was collected and concentrated, further purified by reprecipitation in DCM/methanol to give an orange solid (66 mg, in 82% yield). LCMA (APCI): calcd for C H BF N O (M-): 1277; found: 1277.
Example 2.5: PLC-5
Figure imgf000051_0001
Compound 5.1: A mixture of 4-bromo-l,8-naphthalic anhydride (2.5 g, 9 mmol), 2,5- diisopropanylaniline (5 mL, 27 mmol) in 30 mL propionic acid was heated to reflux under argon atmosphere overnight. The resulting mixture was cooled to r.t., then filtration, washing with methanol and drying in air gave a white solid (3.9 g, in 99% yield). LCMS (APCI): calcd for C24H22BrN02 (M-): 435; Found: 435 *H NMR (400 MHz) d 8.64 - 8.54 (m, 2H), 8.36 (d, J = 7.8
Hz, 1H), 8.04 (d, J = 7.8 Hz, 1H), 7.84 (dd, J = 8.5, 7.3 Hz, 1H), 7.39 (t, J = 7.7 Hz, 1H), 7.23 (d, J = 7.7 Hz, 2H), 2.59 (p, J = 6.8 Hz, 2H), 1.04 (d, J = 6.9 Hz, 12H). Compound 5.2: A mixture of compound 5,1 (1.0 g, 2,29 mmoi), N,N'-diphenylamine (0.62 g, 3.7 mmol), Pd(dppf)Ci2 (0.15 g, 0.2 mmol), and sodium f-butoxide (0.36 g, 3.8 mmoi) in anhydrous toluene (25mL) was degassed and heated at 110 QC overnight. The resulting mixture was loaded on silica gel and purified by flash chromatography using eluents of hexanes/DCM (0% 20% DCM). The desired fraction were collected and removal of solvents gave a solid (0.75 g, in 62% yield). LCMS (APC!): calcd for C36H33N2O2 (M+H): 525; found: 525.
Compound 5.3.1 and 5.3.2: To a solution of compound 5.2 (0.4 g, 0.76 mmol) in DCE (20 mL), was added methyl 4-chloro-4-oxobutyrate (0.24 g, 1.6 mmol) and 1.0M ZnCh solution in diethyl ether (1.0 mL, 1.0 mmol). The resulting mixture was degassed and heated at 50 QC overnight, then submitted to flash chromatography purification using eluents of hexanes/DCM (50% -> 100% DCM) and DCM/ethyl acetate (0% -> 60% ethyl acetate). Two desired fractions were collected, the less polar fraction is concentrated to give a red solid, which was characterized as ester compound 5.3.1 (250 mg, in 52% yield). LCMS (APCI): calcd for C41H39N2O5 (M+H): 639; found: 639. The most polar fraction was concentrated to give another red solid, which is characterized as acid, Compound 5.3.2 (62 mg, in 12.6% yield). LCMS (APCI): calcd for C40H36N2O5 (M-): 624; found: 624.
PLC-5: A mixture of compound 5.3.1 (62 mg, 0.1 mmol), Compound 3.5 [dibenzyl 5,5- difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-l,3,7,9-tetramethyl-5H-4A4,5A4-dipyrrolo[l,2- c:2',l'-/][l,3,2]diazaborinine-2,8-dicarboxylate] (57 mg, 0.09 mmol), DIC (63 mg, 0.5 mmol), DMAP/p-TsOH salt (60 mg, 0.2 mmol) in DCM (5 mL) was stirred at r.t. overnight. The resulting mixture was submitted for flash chromatography purification using eluents of hexanes/ethyl acetate (0% -> 30% ethyl acetate). The desired fraction was collected and concentrated to give a yellow solid (30 mg, in 27% yield). LCMS (APCI): calcd for C77H69BF2N4O9 (M+): 1242; found: 1242. *H NMR (400 MHz, ) d 8.56 - 8.46 (m, 2H), 8.14 (d, J = 8.8 Hz, 1H), 7.81 (d, J = 8.8 Hz, 2H), 7.62 - 7.53 (m, 1H), 7.47 (d, J = 8.0 Hz, 1H), 7.39 (t, J = 7.8 Hz, 1H), 7.32 - 7.21 (m,
14H), 7.16 (d, J = 7.6 Hz, 3H), 6.93 (d, J = 7.9 Hz, 4H), 5.18 (s, 4H), 3.27 (s, 2H), 2.91 (s, 2H), 2.74 (s, 6H), 2.65 (t, J = 6.8 Hz, 2H), 2.03 (s, 6H), 1.62 (s, 6H), 1.07 (d, J = 6.8 Hz, 12H).
Example 2.6: PLC-6
Figure imgf000053_0001
PLC-6 ((7-4)-[2-[(4,5-Dihydro-3-methyl-2H-benz[g]indol-2-ylidene-K/\/)( 3,5- dimethyl-4-(4-((2-(2,6-diisopropylphenyl)-l,3-dioxo-2,3-dihydro-lH-benzo[de]isoquinolin- 6-yl) phenyl)methyl]-4,5-dihydro-3-methyl-1H-benz[g]indolato-K/\/]difluoroboron): A mixture of 4-(4-((2-(2,6-diisopropylphenyl)-l,3-dioxo-2,3-dihydro-lH-benzo[de]isoquinolin- 6-yl)(phenyl)amino)phenyl)-4-oxobutanoic acid (0.050 mmol, 31 mg), Compound 20.3 (vide infra) (0.055 mmol, 30 mg), DAMP/p-TsOH salt (60 mg, 0.2 mmol), DIC (63 mg, 0.5 mmol) in DCM (5 mL) was stirred at r.t. overnight. The resulting mixture was submitted to flash chromatography purification using eluents of DCM/ethyl acetate (0% - 5% ethyl acetate). The crude product was purified by flash chromatography on silica gel (60% toluene/hexanes (2 CV) → 100% toluene (isocratic)). Fractions containing product were evaporated to dryness to give 37 mg (64% yield). MS (APCI): calculated for Chemical Formula: C75H65BF2N4O5 (M-) = 1150 found: 1150. *H NMR (400 MHz, tetrachloroethane-d2) d 8.76 (d, J = 8.1 Hz, 2H), 8.60 (dd, J = 7.3, 1.1 Hz, 1H), 8.59 (d, J = 7.9 Hz, 1H), 8.24 (dd, J = 8.6, 1.2 Hz, 1H), 7.92 (d, J = 8.9 Hz, 2H), 7.66 (dd, J = 8.4, 7.4 Hz, 1H), 7.56 (d, J = 7.9 Hz, 1H), 7.48 (t, J = 7.8 Hz, 1H), 7.46 - 7.37 (m, 4H), 7.37 - 7.28 (m, 6H), 7.27 - 7.22 (m, 3H), 7.03 (d,J = 9.1 Hz, 2H), 7.02 (s, 2H), 3.38 (t, J = 6.2 Hz, 2H), 3.03 (t, J = 6.2 Hz, 2H), 2.91 (t, J = 7.0 Hz, 4H), 2.74 (hept, J = 6.8 Hz, 2H), 2.56 (t, J = 1.1 Hz, 2H), 2.23 (s, 6H), 1.40 (s, 6H), 1.17 (d, J = 6.8 Hz, 12H).
Example 2.7: PLC-7
Figure imgf000054_0001
Compound 7.1: A mixture of 4-bromo-l,8-naphthalic anhydride (2.78 g, 10 mmol), gamma-aminobutyric acid t-butyl ester hydrochloride (2.35 g, 12 mmol), triethylamine (1,21 g, 12 mmol) in 60 mL ethanol was heated at reflux under argon overnight. The mixture was allowed to cool down to r.t. and stand for 4 hrs. Filtration and washing with methanol, following by drying with air gave a light yellow solid as desired product (3.48 g, in 83% yield). LCMS (APCI): ca!cd for C20H2oBrN04 (M+): 418; found: 418.1H NMR (400 MHz, Chloroform-d) d 8.68 (dd, J = 7.3, 1.2 Hz, 1H), 8.59 (dd, J = 8.5, 1.2 Hz, 1H), 8.43 (d, J = 7.8 Hz, 1H), 8.06 (d, J = 7.9 Hz, 1H), 7.87 (dd, J = 8.5, 7.3 Hz, 1H), 4.25 (dd, J = 7.7, 6.8 Hz, 2H), 2.38 (t, J = 7.5 Hz, 2H), 2.06 (p, J = 7.4 Hz, 2H), 1.44 (s, 9H).
Compound 7.2: A mixture of compound 7.1 (1.0 g, 2.4 mmol), N,N'-diphenylamine (0.62 g, 3.7 mmol), Pd(dppf)Cl2 (0.15 g, 0. 2mmol), sodium f-butoxide (0.36 g, 3.7 mmol) in anhydrous toluene (25 mL) was degassed and heated at 110 QC overnight. After cooling to r.t., the reaction mixture was diluted with 100 mL DCM, the solid was filtered off, the solution was concentrated to 25 mL, then submitted to column chromatography purification using eluents of DCM/ethyl acetate (0% → 5% ethyl acetate). The orange fraction were collected and the solvents was removed under reduced pressure to give an orange solid (0.65 g, in 53% yield). LCMS (APCI): calcd for C32H31N2O4 (M+H): 507; found: 507. 1H NMR (400 MHz, Chloroform-d) d 8.58 - 8.49 (m, 4H), 8.20 (dd, J = 8.6, 1.2 Hz, 2H), 7.51 (dd, J = 8.5, 7.3 Hz, 2H), 7.39 (d, J = 8.0 Hz, 2H), 7.32 - 7.23 (m, 8H), 7.13 - 7.07 (m, 3H), 7.07 - 7.01 (m, 8H), 4.30 - 4.22 (m, 4H), 4.14 (q, J = 7.2 Hz, 1H), 2.38 (dd, J = 8.0, 7.2 Hz, 4H), 2.13 - 2.01 (m, 5H), 1.28 (t, J = 7.1 Hz, 2H). Compound 7.3: A solution of compound 7.2 (0.65 g) in DCM/TFA (10 mL/10 mL) was stirred at r.t. overnight, then the solvents was removed under reduced pressure. The resulting oily solid was redissolved in 20 mL methanol, then the solution was dropped into water (100 mL) while stirring. The resulting precipitate was filtered and dried in air to give an orange solid (0.45 g, in 78% yield). LCMS (APCI): calcd for C28H23N2O4 (M+H): 451; found: 451.^ NMR (400 MHz, Chloroform-d) d 8.59 - 8.49 (m, 2H), 8.21 (dd, J = 8.5, 1.1 Hz, 1H), 7.52 (dd, J = 8.5, 7.2 Hz, 1H), 7.40 (d, J = 8.0 Hz, 1H), 7.33 - 7.24 (m, 4H), 7.14 - 7.02 (m, 6H), 4.30 (t, J = 6.9 Hz, 2H), 2.51 (t, J = 1A Hz, 2H), 2.14 (p, J = 1.1 Hz, 2H).
PLC-7: A mixture of compound 7.3 (50 mg, 0.11 mmol), dibenzyl 5,5-difluoro-10-(4- hyd roxy-2, 6-dimethyl phenyl)-l, 3,7, 9-tetra methyl-5H-4λ4, 5λ4-dipyrrolo[l, 2-c:2',l'- f][l,3,2]diazaborinine-2,8-dicarboxylate) (64 mg, 0.1 mol), DMAP/p-TsOH salt (59 mg, 0.2 mmol), DIC (63 mg, 0.5 mmol) in DCM (5 mL) was stirred at r.t. overnight, then submitted for flash chromatography purification using eluents of DCM/ethyl acetate (0% - 10% ethyl acetate). The desired fraction was collected, and removal of solvents gave an orange solid (75 mg, in 70% yield). LCMS (APCI): calcd for C65H55BF2N4O8 (M-): 1068; found: 1068.^ NMR (400 MHz, TCE) d 8.57 - 8.37 (m, 2H), 8.15 (dd, J = 8.6, 1.2 Hz, 1H), 7.48 (dd, J = 8.6, 7.3 Hz, 1H), 7.38 - 7.28 (m, 11H), 7.23 (dd, J = 8.4, 7.3 Hz, 4H), 7.09 - 6.93 (m, 8H), 5.23 (s, 4H), 4.27 (t, J = 7.0 Hz, 2H), 2.79 (s, 6H), 2.69 (t, J = 7.3 Hz, 2H), 2.17 (t, J = 1.1 Hz, 2H), 2.07 (s, 6H), 1.66 (s, 6H).
Example 2.8: PLC-8
Figure imgf000056_0001
Compound 8.1: A mixture of compound 7.1 (1.0 g, 2.4 mmol), (4-
(diphenylamino)phenyl)boronic acid (0.69 g, 2.4 mmol), Pd(PPh3)4 (115 mg, 0.1 mmol), K2CO3 (0.48 g, 3.5 mmol) in dioxane/water (10 mL/2 mL) was degassed, then heated at 80 QC overnight under argon. The resulting mixture was diluted with 50 mL toluene, washed with brine, dried over Na2S04, then the solvents was removed under reduced pressure. The resulting oily solid was dissolved in 10 mL DCM, then submitted to flash chromatography purification using eluents of hexanes/ethyl acetate (0% - 15% ethyl acetate). The desired fraction was collected, and removal of solvents gave a yellow-orange solid (1.28 g, in 91.5% yield). LCMS (APCI): calcd for C38H35N2O4 (M+H): 583; Found: 583. *H NMR (400 MHz, TCE) d 8.62 - 8.54 (m, 2H), 8.40 (dd, J = 8.5, 1.2 Hz, 1H), 7.71 (dt, J = 7.3, 4.1 Hz, 2H), 7.39 - 7.32 (m, 2H), 7.32 - 7.25 (m, 4H), 7.22 - 7.14 (m, 6H), 7.11 - 7.02 (m, 2H), 4.18 (t, J = 7.2 Hz, 2H), 2.33 (t, J = 7.6 Hz, 2H), 1.99 (p, J = 7.5 Hz, 2H), 1.39 (s, 9H). Compound 8.2: A solution of compound 8.1 (50 mg) in DCM/TFA (1 mL/1 mL) was stirred at r.t. overnight. After removal of solvent, the residue solid was dissolved in 2 mL methanol, then dropped into water (5 mL). the precipitate was collected by filtration and washing with water and drying in air (36 mg, in 78% yield). LCMS (APCI): calcd for C34H27N2O4 (M+H): 527; found: 527.
PLC-8: A mixture of compound 8.2 (36 mg, 0.068 mmol), Compound 3.5 (38 mg, 0.06 mmol), DMAP/p-TsOH salt (59 mg, 0.2 mmol) and DIC (63 mg, 0.5 mmol) in DCM (5 mL), was stirred at r.t. overnight. The resulting mixture was submitted to flash chromatography purification using eluents of DCM/ethyl acetate (0% - 5% ethyl acetate). The desired fraction was collected and concentrated under reduced pressure. The solid was further purified by reprecipitation in DCM/methanol to give an orange solid (50 mg, in 73% yield). LCMS (APCI): calcd for C71H60BF2N4O8 (M+H): 1145; found: 1145. *H NMR (400 MHz, TCE) d 8.56 (dd, J= 7.5, 3.2 Hz, 2H), 8.38 (d, J = 8.5 Hz, 1H), 7.67 (dt, J = 8.1, 4.1 Hz, 2H), 7.33 - 7.21 (m, 16H), 7.18 - 7.10 (m, 6H), 7.04 (q, J = 8.1, 7.3 Hz, 2H), 6.88 (s, 2H), 5.18 (s, 4H), 4.26 (t, J = 6.9 Hz, 2H), 2.74 (s, 6H), 2.66 (t, J = 7.2 Hz, 2H), 2.22 - 2.10 (m, 2H), 2.01 (s, 6H), 1.60 (s, 6H).
Example 2.9: PLC-9
Figure imgf000057_0001
Compound 9.1: A mixture of 4-(4-aminophenyl)butanoic acid (3.3 g, 18 mmol), 4- bromo-l,8-naphthalic anhydride (4.43 g, 16 mmol), in ethanol (80 mL) was heated to reflux overnight. After cooled to r.t, the mixture was filtered and washed with ethanol, drying with air to give a light yellow solid (6.2 g, in 88% yield). LCMS (APCI): calcd for C22Hi7BrNC>4 (M+H): 438; found: 438. *H NMR (400 MHz, Chloroform-d) d 8.70 (dd, J = 7.3, 1.2 Hz, 1H), 8.63 (dd, J = 8.5, 1.2 Hz, 1H), 8.45 (d, J = 7.9 Hz, 1H), 8.08 (d, J = 7.9 Hz, 1H), 7.88 (dd, J = 8.5, 7.3 Hz, 1H), 7.42 - 7.34 (m, 2H), 7.27 - 7.19 (m, 2H), 2.78 (t, J = 7.6 Hz, 2H), 2.44 (t, J = 7.3 Hz, 2H), 2.11 - 1.99 (m, 2H). Compound 9.2: A mixture of compound 9.1 (1.0 g, 2.3 mmol), (4-
(diphenylamino)phenyl)boronic acid (0.69 g, 2.4 mmol), Pd(PPh3)4 (115 mg, 0.1 mmol), K2CO3 (0.48 g, 3.5 mmol) in ethanol/water (20 mL/1 mL) was degassed and heated at 80 QC overnight. The resulting mixture was filtered and washed with ethanol and dried in air to give a solid (1.80 g, quantitative yield). LCMS (APCI): calcd for C40H29N2O4 (M-K): 602; found: 602. *H NMR (400 MHz, TCE) d 8.24 (d, J = 22.7 Hz, 2H), 8.10 (d, J = 8.2 Hz, 1H), 7.33 (s, 3H), 7.25 (d, J = 7.8 Hz, 3H), 7.20 - 7.07 (m, 7H), 7.06 - 6.91 (m, 17H), 2.61 (bs, 2H), 2.19 (bs, 2H), 1.89 (bs, 2H).
PLC-9: A mixture of compound 9.2 (72 mg, 0.11 mmol), compound 3.5 (50 mg, 0.079 mmol), DAMP/p-TsOH salt (60 mg, 0.2 mmol), DIC (63 mg, 0.5 mmol) in DCM (5 mL) was stirred at r.t. overnight. The resulting mixture was submitted to flash chromatography purification using eluents of DCM/ethyl acetate (0% - 5% ethyl acetate). The main fraction was collected, and removal of solvents gave an orange solid (88 mg, in 91% yield). LCMS (APCI): calcd for C77H63BF2N4O8 (M-): 1220; found: 1220. *H NMR (400 MHz, TCE) d 8.60 - 8.53 (m, 2H), 8.43 (dd, J = 8.5, 1.2 Hz, 1H), 7.76 - 7.67 (m, 2H), 7.38 (d, J = 8.1 Hz, 2H), 7.36 - 7.25 (m, 14H), 7.25 - 7.19 (m, 4H), 7.19 - 7.12 (m, 6H), 7.04 (t, J = 7.4 Hz, 2H), 6.92 (s, 2H),
5.19 (s, 4H), 2.81 (t, J = 7.5 Hz, 2H), 2.75 (s, 6H), 2.61 (t, J = 7.4 Hz, 2H), 2.10 (t, J = 7.5 Hz, 2H), 2.05 (s, 6H), 1.64 (s, 6H).
Example 2.10: PLC-10
Figure imgf000059_0001
Compound10.1:A mixtureofcompound 9.2 (0.64g, 1 mmol),gamma-aminobutyric acidt-butylesterhydrochloride(0.196g,1mmol),DIC(0.252g,2mmol),DMAP/p-TsOHsalt (0.44g, 1.5 mmol) in DCM (20 mL),wasstirred at r.t, overnight.The resultingmixturewas submittedtoflash chromatographypurification usingeluentsof DCM/ethyl acetate(0% 50%ethylacetate).Thedesiredcompoundwasobtainedafterremovalofsolventsasorange- yellowsolid(0.74g,in100%yield).LCMS(APCi):calcdforC48H45N3O5 (M+H):744;Found:744. Compound10.2:Toasolutionofcompound10.1(0.74g,1mmo!)inDCM(10ml)was addedTFA(10mL),Thesolutionwasstirredatr.t.overnight,thenthesolventswereremoved underreduced pressure.Totheresiduesolid,50mLmethanolwasaddedandstirredfor10 min toform a suspension. The mixture wasfiltered and washed with methanol togive a yellowsolid(0.67g,in97%yield).LCMS(APCl):calcdforC44H38N3O(M+H):688;found:688, 1H NMR(400 MHz,TCE )d8.60-8.52 (m,2H),8.43 (dd,J=8.6, 1.2 Hz, 1H),7.75-7.67(m, 2H),7.32(dt,J=7.6,2.9Hz,4H),7.26(dd,J=8.5,7.2Hz,4H),7.21-7.10(m,8H),7.10-6.99 (m,2H),3.25(q,J=6.2 Hz,2H),2.71(t,J=7.2 Hz,2H),2.34-2.26(m,2H),2.19(t,J=7.5 Hz, 2H), 1.99(q,J=7.2Hz,2H),1.76(p,J=6.5 Hz,2H). PLC-10: A mixture of compound 10.2 (50 mg, 0.073 mmoi), compound 3.5 (40 mg,
0.063 mmol), DIC (63 mg, 0.5 mmol), DMAP/p-TsOH salt (60 mg, 0.2 mmol) in DCM (5 mL), was stirred at r.t. overnight. The resulting mixture was submitted to purification by flash chromatography using eluents of DCM/ethyl acetate (0% → 30% ethyl acetate). The desired fraction was collected, and removal of solvents gave a red solid (60 mg, in 73% yield. LCMS (APCI): calcd for C81H70BF2N5O9 (M-): 1305; found: 1305. 1H NMR (400 MHz, TCE) d 8.59 - 8.51 (m, 2H), 8.46 - 8.39 (m, 1H), 7.71 (t, J = 7.2 Hz, 2H), 7.37 - 7.22 (m, 18H), 7.21 - 7.12 (m, 8H), 7.08 - 6.99 (m, 2H), 6.90 (s, 2H), 5.54 (t, J = 5.9 Hz, 1H), 5.18 (s, 4H), 3.30 (q, J = 6.6 Hz, 2H), 2.74 (s, 6H), 2.70 (d, J = 7.4 Hz, 2H), 2.55 (t, J = 7.3 Hz, 2H), 2.18 (t, J = 7.4 Hz, 2H), 2.03 (s, 6H), 1.98 (t, J = 7.5 Hz, 2H), 1.88 (p, J = 6.9 Hz, 2H), 1.63 (s, 6H).
Example 2.11: PLC-11
Figure imgf000060_0001
Compound 11.1 [Potassium 4-(4-(l,3-dioxo-6-(9-phenyl-9H-carbazol-3-yl)-1H- benzo[de]isoquinolin-2(3H)-yl)phenyl)butanoate]: A mixture of Compound 9.1 (1.0 g, 2.5 mmol), (9-phenyl-9H-carbazol-3-yl)boronic acid (0.69 g, 2.4 mmol), Pd(PPh3 )4 (0.15 g, 0.1 mmol) and potassium carbonate (0.4 8g, 3.5 mmol) in ethanol/water (20 mL/1 mL) was degassed, then heated at 90 °C overnight. The resulting mixture was filtered, the solid was washed with methanol then dried in air to give a yellow solid (1.5 g in quantitative yield). LCMS (APCI): calcd for C40H28N2O4 (M-K+H): 600; found: 600.
PLC-11: A mixture of Compound 11.1 [potassium 4-(4-(l,3-dioxo-6-(9-phenyl-9H- carbazol-3-yl)-1H-benzo[de]isoquinolin-2(3H)-yl)phenyl)butanoate] (70 mg, 0.11 mmol), Compound 3.5 [dibenzyl 5,5-difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-l,3,7,9- tetramethyl-5H-4λ4,5λ4-dipyrrolo[l,2-c:2',1-f][l,3,2]diazabormine-2,8-dicarboxylate] (50 mg, 0.079 mmol), DAMP/p-TsOH salt (60 mg, 0.2 mmol), DIC (63 mg, 0.5 mmol) in DCM (5 mL) was stirred at r.t. overnight. The resulting mixture was submitted to flash chromatography purification using eluents of DCM/ethyl acetate (0% → 10% ethyl acetate). The main fraction was collected, and removal of solvents gave an orange solid (80 mg, in 83% yield). LCMS (APCI):calcd for C77H61BF2N4O8 (M-): 1218; Found: 1218. 1H NMR (400 MHz, d2-TCE) d 8.66 - 8.56 (m, 2H), 8.48 - 8.39 (m, 1H), 8.24 (d, J = 1.4 Hz, 1H), 8.12 (d, J = 7.7 Hz, 1H), 7.83 (d, J = 7.5 Hz, 1H), 7.75 - 7.66 (m, 1H), 7.65 - 7.57 (m, 4H), 7.57 - 7.52 (m, 2H), 7.52 - 7.36 (m, 5H), 7.34 - 7.21 (m, 13H), 6.93 (s, 2H), 5.19 (s, 4H), 2.82 (t, J = 7.6 Hz, 2H), 2.75 (s, 6H), 2.62 (t, J =
7.5 Hz, 2H), 2.15 - 2.07 (m, 2H), 2.05 (s, 6H), 1.65 (s, 6H).
Example 2.12: PLC-12
Figure imgf000061_0001
Compound 12.1 [Methyl 4-(4-(6-bromo-l,3-dioxo-1H-benzo[de]isoquinolin-2(3H)- yl)phenyl)butanoate]: A solution of Compound 9.1 (0.50 g, 1.1 mmol) in 10 mL anhydrous methanol with 0.25 mL 96% sulfuric acid was heated at 80 °C for 6 hrs. After cooled to r.t., the mixture was filtered and solid was washed with methanol and dried in air to give a white solid (0.54 g, in quantitative yield). 1H NMR (400 MHz, Chloroform-d) d 8.71 (dd, J = 7.3, 1.1 Hz, 1H), 8.64 (dd, J = 8.5, 1.2 Hz, 1H), 8.46 (d, J = 7.9 Hz, 1H), 8.09 (d, J = 7.8 Hz, 1H), 7.89 (dd, J = 8.5, 7.3 Hz, 1H), 7.40 - 7.33 (m, 2H), 7.26 - 7.19 (m, 2H), 3.69 (s, 3H), 2.79 - 2.71 (m, 2H), 2.41 (t, J = 7.4 Hz, 2H), 2.04 (p, J = 7.4 Hz, 2H).
Compound 12.2 [Methyl 4-(4-(6-(diphenylamino)-l,3-dioxo-1H-benzo[de]isoquinolin- 2(3H)-yl)phenyl)butanoate]: A mixture of compound 12.1 [methyl 4-(4-(6-bromo-l,3-dioxo- 1H-benzo[de]isoquinolin-2(3H)-yl)phenyl)butanoate] (0.45 g, 1 mmol), diphenylamine (0.27g, 1.6 mmol), Pd(dppf)Cl2 (0.07 3g, 0.1 mmol) and sodium ferf-butoxide (0.31 g, 3.1 mmol) in anhydrous toluene (10 ML) was degassed then heated at 110 °C overnight. After cooling to r.t., the mixture was poured into 100 mL DCM, and stirred for 5 min, then precipitated was filtered off, and the filtrate was concentrated to 5 mL, then loaded on silica gel column for purification using eluents of DCM/ethyl acetate (0% -> 5% ethyl acetate). The desired fraction was collected, and removal of solvent gave a solid (100 mg, in 18.5%). LCMS (APCI): calcd for C35H28N2O4 (M+): 540; found 540.
Compound 12.3 [4-(4-(6-(diphenylamino)-l,3-dioxo-1H-benzo[de]isoquinolin-2(3H)- yl)phenyl)butanoic acid]: To a solution of Compound 12.2 [methyl 4-(4-(6-(diphenylamino)- l,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl)phenyl)butanoate] (100 mg, 0.18 mmol) in 10 mL THF, was added 5 mL 10N HCI aqueous solution. The mixture was heated at 90 Q °C for one hour then the solvent was removed under reduced pressure. The remaining was reprecipitated in methanol/water to give a red solid (35 mg, in 40% yield. LCMS (APCI): calcd for C34H27N2O4
(M+H): 527; found: 527. PLC-12: A mixture of compound 12.3 [4-(4-(6-(diphenylamino)-l,3-dioxo-lH- benzo[de]isoquinolin-2(3H)-yl)phenyl)butanoic acid] (35 mg, 0.066mmol), Compound 3.5 [dibenzyl 5,5-difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-l,3,7,9-tetramethyl-5H-4λ4,5λ4- dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8-dicarboxylate] (35 mg, 0.055mmol), DAMP/p- TsOH salt (40 mg, 0.14 mmol), DIC (50 mg, 0.4 mmol) in DCM (5 mL) was stirred at r.t. overnight. The resulting mixture was purified by flash chromatography (silica gel) using eluents of DCM/ethyl acetate (0% → 10% ethyl acetate). The desired fraction was collected, concentrated and precipitated with methanol to give an orange solid (44 mg, in 70% yield).
LCMS (APCI): calcd for C71H59BF2N4O8 (M-): 1144; found: 1144. Example 2.13: PLC-13
Figure imgf000063_0001
Compound 13.1 [Ethyl 3-methyl-l,4-dihydroindeno[l,2-b>]pyrrole-2-carboxylate]: To a mixture of 1-indanone (30.0 mmol, 3.96 g), Zn granules - 20 mesh (50.0 mmol, 3.27 g) and sodium propionate (5.00 mmol, 480 mg) in valeric acid (20.0 mL) at 180 °C was added a solution of ethyl 2-(hydroxyimino)-3-oxobutanoate (10.0 mmol, 1.59 g) in valeric acid (10.0 mL) via a syringe pump over 1 h. The reaction mixture was stirred for further 15 min after the addition was completed before being cooled to r.t. and partitioned between 6 M HCI (100 mL) and EtOAc (100 mL). The aqueous layer was extracted with EtOAc (3 x 100 mL), the combined organics washed with 1 M aqueous NaOH (3 x 200 mL), dried (MgS04) and concentrated under reduced pressure. Re-precipitation from EtOH gave 505 mg of compound 13.1 (21% yield) as a colorless solid. 1H NMR (400 MHz, Chloroform-d) d 9.05 (br s, 1H), 7.48 (dt, J = 7.5, 1.1 Hz, 1H), 7.44 (dt, J = 7.5, 1.0 Hz, 1H), 7.30 (td, J = 7.5, 1.0 Hz, 1H), 7.19 (td, J = 7.5, 1.1 Hz, 1H),
4.37 (q, J = 7.1 Hz, 2H), 3.49 (s, 2H), 2.42 (s, 3H), 1.40 (t, J = 7.1 Hz, 3H).
Compound 13.2 [3-Methyl-l,4-dihydroindeno[l,2-b ]pyrrole]: To a suspension of Compound 13.1 (0.1.61 mmol, 388 mg) and sodium hydroxide (4.82 mmol, 193 mg) in ethylene glycol (16 mL) was added water (500 μL) and the reaction mixture was stirred at 150 °C for 1 h. It was then cooled to r.t. and 1.0 M aqueous solution of NH4CI (50.0 mL) was added. The precipitate was isolated by vacuum filtration and air-dried to give 264 mg of compound
13.2 (97% yield) as a purple solid. 1H NMR (400 MHz, Acetonitrile-d3) d 9.17 (br s, 1H), 7.42 (d, J = 1A Hz, 1H), 7.35 (d, J = 7.5 Hz, 1H), 7.22 (dd, J = 7.4, 7.5 Hz, 1H), 7.03 (ddd, J = 7.5, 7.5,
1.2 Hz, 1H), 6.61 (dd, J = 2.3, 1.1 Hz, 1H), 3.38 (s, 2H), 2.11 (s, 3H). Compound 13.3 [4-formyl-3,5-dimethylphenyl 4-(4-(6-(4-(diphenylamino)phenyl)- l,3-dioxo-1H-benzo[d e]isoquinolin-2(3H)-yl)phenyl)butanoate] synthesis:
Figure imgf000064_0001
Compound 13.3.1 [4-(4-(6-bromo-l,3-dioxo-1H-benzo[de]isoquinolin-2(3H)- yl)phenyl)butanoic acid]: To a solution of 6-bromo-1H,3H-benzo[de]isochromene-l,3-dione (18.4 mmol, 3.30 g) in EtOH (200 proof, 80.0 mL) was added 4-(4-aminophenyl)butanoic acid (16.0 mmol, 4.43 g) and the reaction mixture was heated to reflux for 16 h. It was then cooled to r.t., diluted with EtOH (200 proof, 50.0 mL), filtered and washed with more EtOH (200 proof, 100 mL) and hexanes (100 mL) to give 5.02 g of Compound 13.3.1 (72% yield) as an off- white solid. 1H NMR (400 MHz, DMSO-d6) d 12.15 (s, 1H), 8.63 - 8.55 (m, 2H), 8.34 (d, J = 7.8 Hz, 1H), 8.25 (d, J = 7.9 Hz, 1H), 8.03 (dd, J = 8.5, 7.3 Hz, 1H), 7.34 (d, J = 8.3 Hz, 2H), 7.29 (d, J = 8.2 Hz, 2H), 2.68 (t, J = 7.3 Hz, 2H), 2.29 (t, J = 7.3 Hz, 2H), 1.87 (p, J = 7.5 Hz, 2H); 13C NMR (101 MHz, DMSO-d6) d 174.3, 163.3, 163.2, 141.8, 133.5, 132.7, 131.6, 131.4, 131.0, 130.0,
129.2, 128.9, 128.8, 128.8, 128.7, 123.4, 122.7, 34.1, 33.2, 26.3.
Compound 13.3.2 [4-(4-(6-(4-(diphenylamino)phenyl)-l,3-dioxo-1H- benzo[d e]isoquinolin-2(3H)-yl)phenyl)butanoic acid]: To a suspension of compound 13.3.1 (11.2 mmol, 4.93 g) and K2C03 (16.8 mmol, 2.32 g) in 20:1 EtOH/H20 (115 mL) under Ar atmosphere were added Pd(PPh3)4 (0.562 mmol, 649 mg) and (4- (diphenylamino)phenyl)boronic acid (11.8 mmol, 3.41 g) and the reaction mixture was stirred at 80 °C for 16 h. It was then filtered and washed with EtOH (200 proof, 200 mL). The filter cake was partitioned between 1 M HCI (300 mL) and CH2CI2 (300 mL) and the mixture was extracted with CH2CI2 (3 x 300 mL). The combined organics were dried (MgSO4 and concentrated under reduced pressure to give 6.50 g of compound 13.3.2 (96% yield) as an orange/red solid. 1H NMR (400 MHz, Chloroform-d) d 8.67 (dd, J = 7.5, 2.5 Hz, 2H), 8.47 (d, J = 8.5 Hz, 1H), 7.79 - 7.71 (m, 2H), 7.42 - 7.36 (m, 4H), 7.33 (apparent t, J = 7.8 Hz, 4H), 7.28 - 7.19 (m, 8H), 7.10 (apparent t, J = 7.3 Hz, 2H), 2.79 (t, J = 7.6 Hz, 2H), 2.46 (t, J = 7.3 Hz, 2H), 2.06 (apparent p, J = 7.6 Hz, 2H); 13C NMR (101 MHz, Chloroform-d) d 177.9, 164.6, 148.4,
147.3, 147.1, 141.8, 133.3, 133.2, 131.8, 131.6, 131.3, 130.8, 130.2, 129.5, 129.5, 128.5, 127.7, 126.7, 125.0, 123.6, 123.0, 122.5, 34.8, 33.1, 26.0.
Compound 13.3 [4-formyl-3,5-dimethylphenyl 4-(4-(6-(4-(diphenylamino)phenyl)- l,3-dioxo-1H-benzo[d e]isoquinolin-2(3H)-yl)phenyl)butanoate]: To a solution of 4-hydroxy- 2,6-dimethylbenzaldehyde (5.97 mmol, 897 mg), compound 13.3.2 (4.98 mmol, 3.00 g) and DMAP-pTsOH salt (9.96 mmol, 2.93 g) in anhydrous CH2CI2 (25.0 mL) was added DIC (29.9 mmol, 4.68 mL) and the reaction was stirred at r.t. for 80 min. It was then filtered through celite and concentrated under reduced pressure. Flash chromatography (toluene -> 9:1, toluene/EtOAc) gave 3.05 g of compound 13.3 (83% yield) as a yellow solid. 1H NMR (400 MHz, Chloroform-d) d 10.57 (s, 1H), 8.70 - 8.64 (m, 2H), 8.48 (dd, J = 8.5, 1.2 Hz, 1H), 7.76 (dd, J = 9.1, 7.4 Hz, 2H), 7.44 - 7.37 (m, 4H), 7.37 - 7.26 (m, 6H), 7.25 - 7.19 (m, 6H), 7.14 - 7.08 (m, 2H), 6.87 (s, 2H), 2.85 (t, J = 7.6 Hz, 2H), 2.69 - 2.59 (m, 8H), 2.16 (p, J = 7.5 Hz, 2H);
13C NMR (101 MHz, Chloroform-d) d 192.3, 171.4, 164.6, 164.4, 148.4, 147.3, 147.2, 143.6, 141.5, 133.5, 133.2, 131.8, 131.6, 131.3, 130.8, 130.2, 130.1, 129.5, 129.5, 129.2, 128.6, 127.7, 126.7, 125.0, 123.7, 123.0, 122.6, 122.4, 121.3, 34.7, 33.6, 26.1, 20.7.
PLC-13 [4-(6,6-difluoro-13,15-dimethyl-12,16-dihydro-6H-5λ4,6λ4- indeno[2',l,:4,5]pyrrolo[l,2-c]indeno[2,,l,:4,5]pyrrolo[2,1-f|[l,3,2]diazaborinin-14-yl)-3,5- dimethylphenyl 4-(4-(6-(4-(diphenylamino)phenyl)-l,3-dioxo-1H-benzo[de ]isoquinolin-
2(3H)-yl)phenyl)butanoate]: To a solution of compound 13.2 (0.473 mmol, 80.0 mg), and pTsOH-H2O (0.005 mmol, 1.00 mg) in anhydrous DCE (5.00 mL) at r.t. under argon atmosphere was added compound 13.3 (0.215 mmol, 158 mg). The reaction mixture was stirred at r.t. for 2.5 h, then it was cooled to 0 °C, p-chloranil (0.215 mmol, 53.0 mg) was added in one portion and the stirring was continued for 15 min. Triethylamine (1.29 mmol, 180 pL) was added and the mixture was stirred at 0 °C for 5 min before BF -OEt (1.94 mmol, 239 pL) was added and the stirring was continued at rt for further 15 min. The reaction mixture was diluted with EtOAc (30.0 mL), washed with 1M HCI (3 x 30.0 mL) and saturated aqueous solution of NaCI (30.0 mL), dried (MgSO4) and concentrated under reduced pressure. Flash chromatography
(7:3, hexanes/EtOAc) gave 125 mg of PLC-13 (53% yield) as a dark purple powder. 1H NMR (400 MHz, Chloroform-d) d 8.71 - 8.65 (m, 2H), 8.48 (dd, J = 8.6, 1.2 Hz, 1H), 8.39 (d, J = 7.8 Hz, 2H), 777 (dd,J = 9.3, 7.5 Hz, 2H), 7.50 -7.27 (m, 16H), 7.25 - 7.19 (m, 6H), 7.14 - 7.08 (m, 2H), 6.99 (s, 2H), 3.53 (s, 4H), 2.89 (t, J = 7.5 Hz, 2H), 2.69 (t, J = 7.4 Hz, 2H), 2.27 (s, 6H), 2.20 (tt, J = 7.5, 7.4 Hz, 2H), 1.52 (s, 6H).
Example 2.14: PLC-14
Figure imgf000067_0001
Compound 14.1 [6-bromo-2-(4-hydroxy-2,6-dimethylphenyl)-1H- benzo[de]isoquinoline-l,3(2H)-dione]: A mixture of 4-bromo-l,8-naphthalic anhydride (1.0 g, 3.6 mmol), 4-amino-3,5-dimethylphenol (1.37 g, 10 mmol) in 10 mL 1-butanol was degassed then heated at 150 °C overnight. After cooled to r.t., the mixture was filtered, washed with methanol and dried in air to give an off-white solid (1.4 g, in 98% yield). LCMS (APCI): calcd for C2oHi5BrN03 (M+H): 396; Found: 396. 1H NMR (400 MHz, Chloroform-d) d 8.71 (d, J = 8.0 Hz, 1H), 8.47 (d, J = 9.1 Hz, 1H), 8.23 - 8.06 (m, 1H), 7.93 (d, J = 7.6 Hz, 1H), 7.42 - 7.32 (m, 1H), 6.74 - 6.67 (m, 2H), 2.18 - 2.13 (m, 1H), 2.12 - 2.02 (s, 6H). Compound 14.2 [6-(4-(diphenylamino)phenyl)-2-(4-hydroxy-2,6-dimethylphenyl)-1H- benzo[de]isoquinoline-l,3(2H)-dione]: A mixture of compound 14.1 [6-bromo-2-(4-hydroxy- 2,6-dimethylphenyl)-1H-benzo[de]isoquinoline-l,3(2H)-dione] (0.98 g, 2.47 mmol), (4- (diphenylamino)phenyl)boronic acid (0.722 g, 2.5 mmol), Pd(PPh3)4 (115 mg, 0.1 mmol), K2CO3 (0.48g , 2.5 mmol) in ethanol/water (20 mL/2 mL) was degassed and heated at 80 °C overnight. After cooling to r.t., the mixture was filtered, washed with ethanol, dried in air to give an orange solid (1.4 g, quantitative yield). LCMS (APCI): calcd for C38H29N2O3 (M+H): 561; found: 561. 1H NMR (400 MHz, ) d 8.59 - 8.52 (m, 2H), 8.40 (dd, J = 8.4, 1.2 Hz, 1H), 7.69 (t, J = 7.8 Hz, 2H), 7.34 - 7.19 (m, 6H), 7.16 - 7.09 (m, 6H), 7.00 (t, J = 7.3 Hz, 2H), 6.60 (s, 2H), 2.43 (s, 1H), 1.95 (s, 6H).
Compound 14.3 [Ethyl 4-(4-(6-(4-(diphenylamino)phenyl)-l,3-dioxo-1H- benzo[de]isoquinolin-2(3H)-yl)-3,5-dimethylphenoxy)butanoate]: A mixture of compound 14.2 [6-(4-(diphenylamino)phenyl)-2-(4-hydroxy-2,6-dimethylphenyl)-1H- benzo[de]isoquinoline-l,3(2H)-dione] (3.9 g, 0.7 mmol), ethyl 4-bromobutanoate (0.156 g, 0.8 mmol) and potassium carbonate (0.207g , 1.5 mmol) in DMF (3 mL) was degassed then heated at 60 °C overnight. The resulting mixture was worked up with ethyl acetate/brine. The organic phase was collected, dried over MgSC , loaded on silica gel and purified by flash chromatography using eluents of hexanes/ethyl acetate (0% - 40% ethyl acetate). The yellow fractions were collected, and removal of solvents give yellow a solid (0.22 g, in 47% yield). LCMS (APCI): calcd for C44H39N2O5: 675; found: 675.
Compound 14.4 [4-(4-(6-(4-(diphenylamino)phenyl)-l,3-dioxo-1H- benzo[de]isoquinolin-2(3H)-yl)-3,5-dimethylphenoxy)butanoic acid]: To a solution of compound 14.3 [ethyl 4-(4-(6-(4-(diphenylamino)phenyl)-l,3-dioxo-1H- benzo[de]isoquinolin-2(3H)-yl)-3,5-dimethylphenoxy)butanoate] (0.22 g, 0.326 mmol) in 1- butanol/l,4-dioxane (10 mL/5 mL) was added 0.2 mL 5M KOH aqueous solution. The mixture was heated at 60 °C for 1 hr, then concentrated to 1 mL, and added into 10 mL water. To the mixture, 1 mL 6N HCI solution was added, the precipitate was filtered and dried in air to give a solid (200 mg, in 95% yield). LCMS (APCI): calcd for C42H35N2O5 (M+H): 647; found: 647.
PLC-14: A mixture of compound 14.4 [4-(4-(6-(4-(diphenylamino)phenyl)-l,3-dioxo- 1H-benzo[de]isoquinolin-2(3H)-yl)-3,5-dimethylphenoxy)butanoic acid] (30 mg, 0.046 mmol), compound 3.5 [dibenzyl 5,5-difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-l,3,7,9- tetramethyl-5H-4λ4,5λ4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8-dicarboxylate] (25 mg, 0.04 mmol), DAMP/p-TsOH salt (40 mg, 0.14 mmol), DIC (50 mg, 0.4 mmol) in DCM (4 mL) was stirred at r.t. overnight. The resulting mixture was purified by flash chromatography (silica gel) using eluents of DCM/ethyl acetate (0% → 10% ethyl acetate). The desired fraction was collected, concentrated and precipitated with methanol to give an orange solid (41 mg, in 81% yield). LCMS (APCI): calcd for C79H67BF2N4O9 (M-): 1264; found: 1264. *H NMR (400 MHz, d2-TCE) d 8.59 (dd, J = 7.4, 4.5 Hz, 2H), 8.43 (d, J = 8.5 Hz, 1H), 7.71 (t, J = 7.8 Hz, 2H), 7.36 - 7.22 (m, 16H), 7.19 - 7.12 (m, 6H), 7.04 (t, J = 7.3 Hz, 2H), 6.94 (s, 2H), 6.75 (s, 2H), 5.19 (s, 4H), 4.09 (t, J = 5.8 Hz, 2H), 2.79 (d, J = 1.1 Hz, 2H), 2.74 (s, 6H), 2.29 - 2.13 (m, 2H), 2.05 (s, 6H), 2.03 (s, 6H), 1.64 (s, 6H). Example 2.15: PLC-15
Figure imgf000069_0001
PLC-15: To a mixture of ethyl 2-methyl-lH-pyrrole-3-carboxylate (61 mg, 0.4 mmol), compound 13.3 [4-formyl-3,5-dimethylphenyl 4-(4-(6-(4-(diphenylamino)phenyl)-l,3-dioxo- lH-benzo[de]isoquinolin-2(3H)-yl)phenyl)butanoate] (100 mg, 0.136 mmol), MgS04 (120 mg, 1.0 mmol) in dichloroethane (5 mL), was added 3 drops TFA, then heated at 65 °C for 3 days.
To the resulting mixture, was added triethylamine (0.13 mL, 0.9 mmol), BF3-etherate (0.09 mL, 0.5 mmol), then heated at 60 °C for 30min. After cooled to rt., the mixture was loaded on silica gel, and purified by flash chromatography using eluents of DCM/Ethyl acetate (0% - 10% ethyl acetate). The main fraction was collected, and removal of solvents gave an orange- red solid (40 mg, in 27% overall yield). LCMS (APCI): calcd for C65H55BF2N4O8 (M-): 1068; found: 1068. *H NMR (400 MHz, d2-TCE) d 8.60 - 8.53 (m, 2H), 8.43 (dd, J = 8.6, 1.2 Hz, 1H), 7.75 - 7.67 (m, 2H), 7.39 (d, J = 8.3 Hz, 2H), 7.36 - 7.30 (m, 2H), 7.24 (dt, J = 13.8, 8.1 Hz, 6H), 7.15 (d, J = 8.6 Hz, 6H), 7.08 - 6.99 (m, 4H), 6.91 (s, 2H), 4.17 (q, J = 7.1 Hz, 4H), 2.84 (s, 6H), 2.80 (m, 2H), 2.65 (t, J = 1A Hz, 2H), 2.13 (m, 2H), 2.08 (s, 6H), 1.24 (t, J = 7.1 Hz, 6H). Example 2.16: PLC-16
Figure imgf000070_0001
PLC-16 ((T-4)-[2-[(4,5-Dihydro-3-methyl-2H-benz[g]indol-2-ylidene-K/\/)( 3,5- dimethyl-4-((4-(6-(4-(diphenylamino)phenyl)-l,3-dioxo-lH-benzo[tfe]isoquinolin-2(3H)- yl)phenyl)butanoate)phenyl)methyl]-4,5-dihydro-3-methyl-lH-benz[g]indolato- kL/Jdifluoroboron): A mixture of compound 9.2 (0.120 mmol, 77 mg), compound 20.3 (vide infra) (0.100 mmol, 54 mg), DAMP/p-TsOH salt (60 mg, 0.2 mmol), DIC (63 mg, 0.5 mmol) in DCM (5 mL) was stirred at r.t. overnight. The resulting mixture was submitted to flash chromatography purification using eluents of DCM/ethyl acetate (0% -> 5% ethyl acetate). The crude product was purified by flash chromatography on silica gel (100% toluene (2 CV) -> 10% EtOAc/toluene (15 CV)). Fractions containing product were evaporated to dryness to give 100 mg (89% yield). MS (APCI): calculated for Chemical Formula: C75H59BF2N4O4 (M-) = 1128; found: 1128. *H NMR (400 MHz, tetrachloroethane-d2) d 8.77 (d, J = 8.1 Hz, 2H), 8.66 (dd, J = 7.3, 1.2 Hz, 1H), 8.65 (d, J = 7.6 Hz, 1H), 8.52 (dd, J = 8.6, 1.2 Hz, 1H), 7.81 (t, J = 7.2 Hz, 1H), 7.79 (d, J = 7.3 Hz, 1H), 7.52 - 7.46 (m, 2H), 7.46 - 7.40 (m, 4H), 7.34 (tdd, J = 8.5, 6.7, 4.7 Hz, 10H), 7.27 - 7.22 (m, 6H), 7.13 (tt, J = 7.3, 1.2 Hz, 2H), 7.01 (s, 2H), 2.92 (t, J = 7.2 Hz, 6H), 2.73 (t, J = 7.5 Hz, 2H), 2.57 (t, J = 7.0 Hz, 4H), 2.29 - 2.15 (m, 8H), 1.42 (s, 6H).
Example 2.17: PLC-17
O
Figure imgf000071_0001
Compound 17.1 [Ethyl 3-methyl-4,5-dihydro-lH-benzo[g]indole-2-carboxylate]: To a mixture of 1-tetralone (3.00 mmol, 403 pL), Zn granules - 20 mesh (5.00 mmol, 327 mg) and sodium propionate (0.50 mmol, 48 mg) in valeric acid (2.00 mL) at 180 °C was added a solution of ethyl 2-(hydroxyimino)-3-oxobutanoate (1.00 mmol, 159 mg) in valeric acid (1.00 mL) via a syringe pump over 1 h. The reaction mixture was stirred for further 15 min after the addition was completed before being cooled to r.t. and partitioned between 6 M HCI (10.0 mL) and EtOAc (10.0 mL). The aqueous layer was extracted with EtOAc (3 x 10.0 mL), the combined organics washed with 1 m aqueous NaOH (3 x 20.0 mL), dried (MgSCU) and concentrated under reduced pressure. Flash chromatography (19:1, hexanes/EtOAc -> 9:1, hexanes/EtOAc) gave 134 mg of compound 17.1 (52% yield) as a colorless solid. 1H NMR (400 MHz, Chloroform-d) d 8.99 (br s, 1H), 7.34 - 7.30 (m, 1H), 7.25 - 7.20 (m, 2H), 7.17 - 7.13 (m, 1H), 4.35 (q, J = 7.1 Hz, 2H), 2.94 (t, J = 7.5 Hz, 2H), 2.69 - 2.62 (m, 2H), 2.30 (s, 3H), 1.39 (t, J = l.l Hz, 3H).
Compound 17.2 [3-Methyl-4,5-dihydro-lH-benzo[g]indole]: To a solution of compound 17.1 [ethyl 3-methyl-4,5-dihydro-lH-benzo[g]indole-2-carboxylate] (2.48 g, 9.71 mmol) in ethylene glycol (100 mL) in a 250 mL two-neck flask equipped with a finned condenser and gas adapter under argon atmosphere was added KOH (9.71 mL, 48.6 mmol of a 5.0M aq. solution). The reaction mixture was heated to 100 °C for 70 min and then to 160 °C for40 min, before it was cooled to r.t. and poured into water (500 mL). The precipitate was collected by vacuum filtration and washed with water (100 mL) to give compound 17.2 (352 mg, 20%) as a light blue powder.
The filtrate was acidified to pH = 3 with TFA, the precipitate was collected by vacuum filtration, washed with water (100 mL) and dissolved in CH2CI2 (100 mL) under argon atmosphere. TFA (1.00 mL) was added and the reaction mixture was stirred at r.t. for 15 min. Volatiles were removed under reduced pressure and the residue was diluted with MeOH (2.00 mL). Precipitation was induced by addition of water (100 mL) and the precipitate was collected by vacuum filtration and washed with water (50.0 mL) to give compound 17.2 (306 mg, 17%) as a blue powder. 1H NMR (400 MHz, Acetonitrile-ds) d 9.16 (br s, 1H), 7.24 (dd, J = 7.5, 1.3 Hz, 1H), 7.16 (ddd, J = 8.7, 7.4, 1.8 Hz, 2H), 7.00 (ddd, J = 7.5, 7.4, 1.3 Hz, 1H), 6.52 (dd, J = 2.5, 1.1 Hz, 1H), 2.87 (t, J = 7.6 Hz, 2H), 2.59 (dd, J = 8.5, 6.7 Hz, 2H), 2.00 (d, J = 0.9 Hz, 3H).
Compound 17.3 [(T-4)-[2-[(4,5-dihydro-3-methyl-2H-benz[g]indol-2-ylidene-K/V)-(4'- hydroxyphenyl)methyl]-4,5-dihydro-3-methyl-lH-benz[g]indolato-K/V]difluoroboron]: To a solution of compound 17.2 [3-methyl-4,5-dihydro-1H-benzo[g]indole] (652 mg, 3.55 mmol) and 4-hydroxybenzaldehyde (216 mg, 1.77 mmol) in anhydrous 1,2-dichloroethane (35.0 mL) at r.t. under argon atmosphere was added TFA (35.0 μ L). The reaction mixture was stirred at r.t. for 70 min, cooled to 0 °C and p-chloranil (435 mg, 1.77 mmol) was added in one portion and the stirring was continued for 15 min. Triethyla mine (1.48 mL, 10.6 mmol) was added and the mixture was warmed up to r.t. over 10 min before BF3-OEt2 (1.96 mL, 15.9 mmol) was added and the stirring was continued for 75 min. More triethylamine (1.48 mL, 10.6 mmol) and BF3-OEt2 (1.96 mL, 15.9 mmol) were added, the mixture was stirred for further 75 min and all volatiles were removed under reduced pressure. The residue was diluted with EtOAc (100 mL), washed with 1M HCI (2 x 100 mL) and 6M HCI (100 mL), dried (MgSC^) and concentrated under reduced pressure. Flash chromatography (CH2CI2) gave compound 17.3 (130 mg, 17%) as a dark blue/green powder. 1H NMR (400 MHz,) d 8.65 (d, J = 8.0 Hz, 2H), 7.34 (apparent td, J = 7.6, 1.7 Hz, 2H), 7.28 - 7.16 (m, 6H), 6.95 - 6.90 (m, 2H), 4.96 (d, J = 1.2 Hz, 1H), 2.80 (dd, J = 8.3, 5.9 Hz, 4H), 2.47 (dd, J = 8.3, 5.9 Hz, 4H), 1.35 (s, 6H).
PLC-17 [(7-4)-[2-[(4,5-dihydro-3-methyl-2H-benz[g]indol-2-ylidene-K/\/)-(4'-(4-(4-(6- (4-(diphenylamino)phenyl)-l,3-dioxo-lH-benzo[de]isoquinolin-2(3H)-yl)phenyl)butanoxy) phenyl)methyl]-4,5-dihydro-3-methyl-lH-benz[g]indolato-K/\/]difluoroboron]: To a solution of compound 17.3 [(T-4)-[2-[(4,5-dihydro-3-methyl-2H-benz[g]indol-2-ylidene-K/V)-(4'- hydroxyphenyl)methyl]-4,5-dihydro-3-methyl-lH-benz[g]indolato-K/V]difluoroboron] (52 mg, 0.100 mmol), compound 9.2 [potassium 4-(4-(6-(4-(diphenylamino)phenyl)-l,3-dioxo- lH-benzo[de]isoquinolin-2(3H)-yl)phenyl)butanoate] (77 mg, 0.120 mmol), and DMAP-pTsOH salt (59 mg, 0.200 mmol) in anhydrous 1,2-dichloroethane (10.0 mL) at r.t. under argon atmosphere was added DIC (94.0 pL, 0.600 mmol) and the reaction mixture was stirred at r.t. for 2 h and then at 50 °C for 1 h, cooled to r.t. and diluted with 1:1 hexanes/toluene (10.0 mL). The resulting mixture was purified by flash chromatography (toluene -> 9:1 toluene/EtOAc) to give PLC-17 (103 mg, 94%) as a dark purple powder. 1H NMR (400 MHz,) d 8.67 (d, J = 8.1 Hz, 2H), 8.58 (dd, J = 7.4, 4.9 Hz, 2H), 8.44 (d, J = 8.5 Hz, 1H), 7.72 (apparent t, J = 7.3 Hz, 2H), 7.43 - 7.14 (m, 27H), 7.04 (apparent t, J = 7.3 Hz, 2H), 2.91 - 2.76 (m, 6H), 2.68 (t, J = 7.4 Hz, 2H), 2.48 (t, J = 6.9 Hz, 4H), 2.15 (apparent p, J = 7.5 Hz, 2H), 1.36 (s, 6H).
Example 2.18: PLC-18
Figure imgf000074_0001
Compound 18.1 [3,3-Dimethyl-2,3-dihydro-1H-inden-l-one]: A solution of 3- methylcrotonic acid (19.0 mmol, 1.90 g) in benzene (10.0 mL) was slowly added to AICI3 (57.0 mmol, 7.60 g) in a 100 mL round-bottom flask. The resulting mixture was heated to reflux for 5 h, cooled to 0 °C, quenched with 1M HCI (50.0 mL) and extracted with EtOAc (3 x 50.0 mL).
The combined organics were washed with a saturated aqueous solution of NaHCO3 (3 x 100 mL) and saturated aqueous solution of NaCI (100 mL), dried (MgSO4) and concentrated under reduced pressure. Flash chromatography (9:1, hexanes/EtOAc) gave 2.62 g of compound 18.1 (86% yield) as an orange oil.1H NMR (400 MHz, Chloroform-d) d 7.72 - 7.67 (m, 1H), 7.65 - 7.57 (m, 1H), 7.53 - 7.47 (m, 1H), 7.39 - 7.32 (m, 1H), 2.60 - 2.58 (m, 2H), 1.47 - 1.36 (m, 6H);
13C NMR (101 MHz, Chloroform-d) d 205.7, 163.7, 135.1, 134.8, 127.2, 123.4, 123.2, 52.8, 38.4, 29.8.
Compound 18.2 [Ethyl 3,4,4-trimethyl-l,4-dihydroindeno[1,2-b]pyrrole-2- carboxylate]: To a mixture of compound 18.1 (3.00 mmol, 481 mg), Zn granules - 20 mesh (5.00 mmol, 327 mg) and sodium propionate (0.50 mmol, 48 mg) in valeric acid (2.00 mL) at
180 °C was added a solution of ethyl 2-(hydroxyimino)-3-oxobutanoate (1.00 mmol, 159 mg) in valeric acid (1.00 mL) via a syringe pump over 1 h. The reaction mixture was stirred for further 15 min after the addition was completed before being cooled to r.t. and partitioned between 6 M HCI (10.0 mL) and EtOAc (10.0 mL). The aqueous layer was extracted with EtOAc (3 x 10.0 mL), the combined organics washed with 1 m aqueous NaOH (3 x 20.0 mL), dried (MgSC^) and concentrated under reduced pressure. Flash chromatography (19:1, hexanes/EtOAc → 9:1, hexanes/EtOAc) gave 81 mg of compound 18.2 (31% yield) as a colorless solid. 1H NMR (400 MHz, Chloroform-d) d 9.19 (s, 1H), 7.40 - 7.34 (m, 2H), 7.27 - 7.18 (m, 2H), 4.38 (q, J = 7.1 Hz, 2H), 2.47 (s, 3H), 1.51 (s, 6H), 1.40 (t, J = l.l Hz, 3H).
Compound 18.3 [3,4,4-Trimethyl-l,4-dihydroindeno[l,2-6]pyrrole]: To a suspension of compound 18.2 (0.149 mmol, 42 mg) and sodium hydroxide (0.446 mmol, 18.0 mg) in ethylene glycol (1.50 mL) was added water (50.0 pL) and the reaction mixture was stirred at 150 °C for 1 h. It was then cooled to r.t. and 1.0 M aqueous solution of NH4CI (5.00 mL) was added. The mixture was extracted with CH2CI2 (3 x 10.0 mL) to give 29 mg of compound 18.3 (99% yield) as a purple solid. 1H NMR (400 MHz, Chloroform-d) d 7.97 (br s, 1H), 7.30 (dt, J = 7.3, 0.9 Hz, 1H), 7.21 - 7.14 (m, 2H), 7.07 (ddd, J = 7.4, 5.4, 3.3 Hz, 1H), 6.57 (dd, J = 2.2, 1.1 Hz, 1H), 2.20 (d, J = 1.0 Hz, 3H), 1.50 (s, 6H).
PLC-18 [4-(6,6-Difluoro-12,12,13,15,16,16-hexamethyl-12,16-dihydro-6H-5λ4,6λ4- indeno[2',l':4,5]pyrrolo[l,2-c]indeno[2',l':4,5]pyrrolo[2,l-/|[l,3,2]diazaborinin-14-yl)-3,5- dimethylphenyl 4-(4-(6-(4-(diphenylamino)phenyl)-l,3-dioxo-1H-benzo[d e]isoquinolin- 2(3H)-yl)phenyl)butanoate]: To a solution of compound 18.3 (0.061 mmol, 12.0 mg), and pTsOH2 O (1 crystal) in anhydrous CH2CI2 (0.60 mL) at r.t. under argon atmosphere was added compound 13.3 (0.033 mmol, 25.0 mg). The reaction mixture was stirred at r.t. for 1 h, then it was cooled to 0 °C, p-chloranil (0.031 mmol, 8.00 mg) was added in one portion and the stirring was continued for 15 min. Triethylamine (0.186 mmol, 26.0 pL) was added and the mixture was warmed up to r.t. over 10 min before BF3-OEt2 (0.279 mmol, 34.0 pL) was added and the stirring was continued for further 30 min. The reaction mixture was diluted with EtOAc (5.00 mL), washed with 1M HCI (3 x 5.00 mL) and saturated aqueous solution of NaCI (5.00 mL), dried (MgS04) and concentrated under reduced pressure. Flash chromatography (toluene → 19:1, toluene/EtOAc) gave 14.0 mg of PLC-18 (39% yield) as a dark purple powder d 1H NMR (400 MHz, Chloroform-d) d 8.68 (dd, J = 7.4, 2.5 Hz, 2H), 8.48 (d, J = 8.5 Hz, 1H), 8.31 (d, J = 7.4 Hz, 2H), 7.80 - 7.72 (m, 2H), 7.47 - 7.28 (m, 16H), 7.25 - 7.20 (m, 6H), 7.11 (apparent t, J = 7.3 Hz, 2H), 6.97 (s, 2H), 2.88 (t, J = 7.5 Hz, 2H), 2.69 (t, 7 = 7.4 Hz, 2H), 2.28 (s, 6H), 2.19 (apparent p, 7 = 7.5 Hz, 2H), 1.54 (s, 6H), 1.50 (s, 12H).
Example 2.19: PLC-19
Figure imgf000076_0001
Compound 19.1 [4-Formyl-3,5-dimethoxyphenyl 4-(4-(6-(4-(diphenylamino)phenyl)- l,3-dioxo-lH-benzo[c/e]isoquinolin-2(3H)-yl)phenyl)butanoate]: To a solution of 2,6- dimethoxy-4-hydroxybenzaldehyde (1.00 mmol, 182 mg), compound 13.3.2(1.10 mmol, 662 mg) and DMAP-pTsOH salt (1.00 mmol, 294 mg) in CH2CI2 (5.00 mL) was added DIC (6.00 mmol, 939 pL) and the reaction mixture was stirred at r.t. for 20 h. It was then filtered through celite and concentrated under reduced pressure. Flash chromatography (4:1, toluene/EtOAc) gave 643 mg of compound 19.1 (84% yield) as a bright orange solid. 1H NMR (400 MHz, Chloroform-d) d 10.44 (s, 1H), 8.71 - 8.64 (m, 2H), 8.48 (dd, J = 8.5, 1.2 Hz, 1H), 7.81 - 7.72 (m, 2H), 7.44 - 7.37 (m, 4H), 7.36 - 7.27 (m, 6H), 7.25 - 7.20 (m, 6H), 7.13 - 7.08 (m, 2H), 6.39 (s, 2H), 3.90 (s, 6H), 2.85 (t, J = 7.5 Hz, 2H), 2.67 (t, J = 7.6 Hz, 2H), 2.17 (apparent p, J = 7.6 Hz, 2H).
PLC-19 [(T-4)-[2-[(4,5-dihydro-3-methyl-2H-benz[g]indol-2-ylidene-K/V)-(2',6'- dimethoxy-4'-(4-(4-(6-(4-(diphenylamino)phenyl)-l,3-dioxo-lH-benzo[c/e]isoquinolin- 2(3H)-yl)phenyl)butanoxy)phenyl)methyl]-4,5-dihydro-3-methyl-lH-benz[g]indolato- kL/Jdifluoroboron]: To a solution of 3-methyl-4,5-dihydro-lH-benzo[g]indole (0.210 mmol, 39 mg) and compound 19.1 (0.100 mmol, 77 mg) in CH2CI2 (2.10 mL) was added pTsOH-H2O (0.010 mmol, 1.20 mg) and the reaction mixture was stirred at r.t. for 1 h. It was then cooled to 0 °C, p-chloranil (0.100 mmol, 25mg) was added and the mixture was stirred at 0 °C for 15 min. Triethylamine (0.600 mmol, 83 pL) was added, the mixture was stirred at 0 °C for 15 min before BF3-OEt2 (0.900 mmol, 111 pL) was added and the mixture was stirred at r.t. for 45 min. More triethylamine (0.600 mmol, 83 pL) and, after 5 min stirring at r.t., BF3-OEt2 (0.900 mmol, 111 pL) were added and the mixture was stirred at r.t. for further 1 h. It was then diluted with EtOAc (10.0 mL), washed with 3 M HCI (3 x 10.0 mL), dried (MgSO4) and concentrated under reduced pressure. Flash chromatography (toluene → 19:1, toluene/EtOAc) gave 97 mg of PLC-19 (84% yield) as a dark blue/purple solid. 1H NMR (400 MHz, Chloroform-d) d 8.83 (d, J = 8.1 Hz, 2H), 8.71 - 8.66 (m, 2H), 8.49 (dd, J = 8.5, 1.2 Hz, 1H), 7.80 - 7.74 (m, 2H), 7.47 - 7.27 (m, 13H), 7.25 - 7.19 (m, 9H), 7.11 (apparent td, J = 7.3, 1.2 Hz, 2H), 6.52 (s, 2H), 3.77 (s, 6H), 2.94 - 2.84 (m, 6H), 2.71 (t, J = 7.5 Hz, 2H), 2.59 - 2.50 (m, 4H), 2.21 (apparent p, J = 7.6 Hz, 2H), 1.55 (s, 6H). Example 2.20: PLC-20
Figure imgf000077_0001
Figure imgf000078_0001
Figure imgf000078_0002
Compound 20.1 (ethyl 3-methyl-4,5-dihydro-lH-benzo[g]indole-2-carboxylate): A
250 mL 2 neck round bottomed flask was charged with a stir bar and placed in a heat block. To this flask was added 1-tetralone (100.0 mmol, 14.620 g) and sodium propionate (100.0 mmol, 9.610 g), followed by acetic acid (50 mL). The reaction was heated to 145 °C with stirring open to air. A 40 mL screw cap vial was charged with ethyl 2-(hydroxyimino)-3- oxobutanoate (2.50 mmol, 398 mg) and Zn (dust, < 10 um) (12.5 mmol, 818 mg). These materials were slurried in acetic acid (12.5 mL) and added to the stirred reaction containing the ketone in portions over a period of about 5 minutes. This process was repeated three times for a total of 10.0 mmol 2-(hydroxyimino)-3-oxobutanoate and 50.0 mmol Zn dust. The reaction was stirred at 145 °C for 2.5 hours, then cooled to room temperature. The reaction was quenched by pouring into water (600 mL) with stirring. The volume was brought up to 900 mL with water, then extracted with dichloromethane (4 X 160 mL). The combined organic layers were washed with water (100 mL), brine (100 mL), dried over MgSC>4, filtered, and evaporated to dryness. Most of the excess 1-tetralone was removed on high vacuum with heating. The crude product was purified by flash chromatography on silica gel (5% EtOAc/hexanes (1 CV) - 20% EtOAc/hexanes (10 CV). Fractions containing product were evaporated to dryness to give 1.417 g (55% yield). MS (APCI): calculated for Chemical Formula: C16H17NO2 (M + H) = 256; found: 256. *H NMR (400 MHz) d 8.98 (s, 1H), 7.35 - 7.31 (m, 1H), 7.27 - 7.21 (m, 2H), 7.20 - 7.15 (m, 1H), 4.34 (q, J = 7.1 Hz, 2H), 2.99 - 2.92 (m, 2H), 2.70 - 2.64 (m, 2H), 2.31 (s, 3H), 1.39 (t, J = 7.1 Hz, 3H).
Compound 20.2 (3-methyl-4,5-dihydro-1H-benzo[g]indole): A 250 mL 2 neck round bottom flask was charged with a stir bar and fitted with a finned condenser and a gas adapter. The flask was flushed with argon and compound 20.1 (5.01 mmol, 1.278 g) was added to the flask, followed by ethylene glycol (50 mL). To the reaction mixture was added KOH (5.0M in H2O, 25.03 mmol, 5.01 mL). The reaction was stoppered and heated in a heat block at 100 °C for 90 minutes under argon. The solution becomes homogenous with heating. The temperature was increased to 160 °C for 30 minutes, then cooled to 100 °C. The reaction was quenched by pouring into stirred water (300 mL). This was brought up to a total volume of 500 mL with water, then it was acidified with a solution of 2.5 M acetic acid/2.5 M NaOAc (20 mL). The pH was reduced to ~3.5 with TFA. The resulting purple solid was filtered off, dried, and purified by flash chromatography on silica gel (5% EtOAc/hexanes (1 CV) → 20% EtOAc/hexanes (10 CV)). Fractions containing product were evaporated to dryness to give 767 mg (84% yield). MS (APCI): calculated for Chemical Formula: C13H13N (M + H) = 184 found: 184. 1H NMR (400 MHz, Acetonitrile-d3) d 9.15 (s, 1H), 7.24 (d, J = 7.5 Hz, 1H), 7.20 - 7.13 (m, 2H), 7.00 (td, J = 7.4, 1.4 Hz, 1H), 6.52 (dd, J = 2.3, 0.9 Hz, 1H), 2.90 - 2.83 (m, 2H), 2.62 - 2.55 (m, 2H), 2.00 (s, 3H).
Compound 20.3 ((T-4)-[2-[(4,5-Dihydro-3-methyl-2H-benz[g]indol-2-ylidene-KN )( 3,5-dimethyl-4-hydroxyphenyl)methyl]-4,5-dihydro-3-methyl-1H-benz[g]indolato- KN ]difluoroboron): Compound 9.3 was synthesized from compound 20.2 (3.97 mmol, 728 mg) and 4-hydroxy-2,6-dimethylbenzaldehyde (2.02 mmol, 304 mg) in a manner similar to Compound 3.2. The crude product was purified by flash chromatography on silica gel (100% toluene (2 CV) → 10% EtOAc/toluene (10 CV)). Fractions containing product were evaporated to give 563 mg (52% yield for 3 steps from pyrrole). MS (APCI): calculated for Chemical Formula: C35H31BF2N2O (M + H) = 544 found: 544. 1H NMR (400 MHz, DMSO-d6) d 9.61 (s, 1H), 8.62 (d, J = 7.9 Hz, 2H), 7.45 - 7.38 (m, 2H), 7.38 - 7.34 (m, 4H), 6.68 (s, 2H), 2.91 - 2.83 (m, 4H), 2.58 - 2.52 (m, 4H), 2.04 (s, 6H), 1.41 (s, 6H).
PLC-20 [(T-4)-[2-[(4,5-dihydro-3-methyl-2H-benz[g]indol-2-ylidene-KN )-(2',6'- dimethyl-4'-(4-(4-(6-(4-(di-p-tolylamino)phenyl)-l,3-dioxo-1H-benzo[de]isoquinolin-2(3H)- yl)phenyl)butanoxy)phenyl)methyl]-4,5-dihydro-3-methyl-1H-benz[g]indolato- kN]Jdifluoroboron]: To a solution of compound 20.3 (0.032 mmol, 17 mg), compound 24.3 (vide infra, 0.033 mmol, 21 mg) and DMAP-pTsOH salt (0.032 mmol, 9 mg) in CH2CI2 (0.30 mL) was added DIC (0.192 mmol, 30 μL) and the reaction mixture was stirred at r.t. for 2 h. It was then filtered through celite and concentrated under reduced pressure. Flash chromatography (toluene → 19:1, toluene/EtOAc) followed by re-precipitation from toluene/hexanes gave 13 mg of PLC-20 (35% yield) as a blue solid. 1H NMR (400 MHz, Dichloromethane-^) d 8.80 - 8.71 (m, 2H), 8.65 - 8.60 (m, 2H), 8.50 (d, J = 8.7 Hz, 1H), 7.80 - 7.73 (m, 2H), 7.48 - 7.25 (m, 13H), 7.19 - 7.05 (m, 9H), 7.01 (s, 2H), 2.98 - 2.86 (m, 6H), 2.71 (t, J = 7.4 Hz, 2H), 2.57 (s, 4H), 2.34 (br s, 6H), 2.24 (s, 6H), 2.23 - 2.17 (m, 2H), 1.42 (s, 6H).
Example 2.21: PLC-21
Figure imgf000080_0001
PLC-21 Dibenzyl 10-(4-((4-(4-(6-(4-(diphenylamino)phenyl)-l,3-dioxo-1H- benzo[d e]isoquinolin-2(3H)-yl)phenyl)butanoyl)oxy)-2,6-dimethylphenyl)-5,5-difluoro- l,3,7,9-tetramethyl-5H-4λ4,5λ4-dipyrrolo[l,2-c:2',l,-f][l,3,2]diazaborinine-2,8- dicarboxylate (1575-46): To a solution of compound 3.5 [dibenzyl 5,5-difluoro-10-(4- hyd roxy-2, 6-dimethyl phenyl)-l, 3, 7, 9-tetramethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',r- f][l,3,2]diazaborinine-2,8-dicarboxylate] (1.18 mmol, 750 mg), compound 13.3.2 (1.30 mmol, 780 mg) and DMAP-pTsOH salt (2.36 mmol, 694 mg) in anhydrous CH2CI2 (6.00 mL) was added DIC (7.08 mmol, 1.11 mL) and the reaction mixture was stirred at r.t. for 16 h. It was then filtered through celite and concentrated under reduced pressure. Flash chromatography (7:3, hexanes/EtOAc → 3:2, hexanes/EtOAc) gave 1.10 g of PLC-21 (76% yield) as an orange solid. 1 H NMR (400 MHz, Chloroform-d) d 8.68 (dd, J = 7.2, 2.4 Hz, 2H), 8.48 (d, J = 8.5 Hz, 1H), 777 (dd, J = 9.3, 7.4 Hz, 2H), 7.44 - 7.27 (m, 20H), 7.24 - 7.20 (m, 6H), 7.11 (t, J = 7.3 Hz, 2H), 6.97 (s, 2H), 5.27 (s, 4H), 2.85 (d, J = 13.9 Hz, 8H), 2.67 (t, J = 7.4 Hz, 2H), 2.22 - 2.06 (m, 8H), 1.72 (s, 6H); 19 F NMR (376 MHz, Chloroform-d) d -142.72 - -143.09 (m); 13C NMR (101 MHz, Chloroform-d) d 171.5, 164.0, 159.9, 148.4, 147.3, 147.2, 146.9, 136.7, 135.8, 131.6, 131.3, 130.8, 129.5, 128.6, 128.4, 128.3, 127.8, 126.7, 125.1, 123.7, 122.5, 121.8, 121.3, 66.2, 34.8, 33.6, 26.1, 19.7, 15.1, 12.6.
Example 2.22: PLC-22
Figure imgf000081_0001
Compound 22.1 [Dibenzyl 10-(2,6-difluoro-4-hydroxyphenyl)-5,5-difluoro-l,3,7,9- tetramethyl-5H-4λ4,5λ4-dipyrrolo[l,2-C:2',1-f][l,3,2]diazaborinine-2,8-dicarboxylate]: To a solution of benzyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (1.05 mmol, 241 mg) and 2,6- difluoro-4-hydroxybenzaldehyde (0.500 mmol, 79 mg) in CH2CI2 (10.0 mL) was added pTsOHH2O (0.050 mmol, 6 mg) and the reaction mixture was stirred at r.t. for 45 min. It was then cooled to 0 °C, DDQ (0.600 mmol, 136 mg) was added and the mixture was stirred at r.t. for 1 h. Triethylamine (3.00 mmol, 417 μL) was added, the mixture was stirred at 0 °C for 10 min before BF3-OEt2 (4.50 mmol, 555 μL) was added and the mixture was stirred at r.t. for 2 h. More triethylamine (3.00 mmol, 417 μL) and, after 5 min stirring at r.t., BF3-OEt2 (4.50 mmol, 555 μL) were added and the mixture was stirred at r.t. for further 1 h. It was then diluted with EtOAc (30.0 mL), washed with 3 M HCI (3 x 30.0 mL), dried (MgSO4) and concentrated under reduced pressure. Flash chromatography (9:1, toluene/EtOAc) gave 175 mg of compound 22.1 (54% yield) as an orange solid. 1H NMR (400 MHz, Chloroform-d) d 7.41 - 7.30 (m, 10H), 6.59 - 6.53 (m, 2H), 5.30 (s, 4H), 2.82 (s, 6H), 1.92 (s, 6H).
PLC-22 [Dibenzyl 10-(4-((4-(4-(6-(4-(diphenylamino)phenyl)-l,3-dioxo-1H- benzo[d e]isoquinolin-2(3H)-yl)phenyl)butanoyl)oxy)-2,6-difluorophenyl)-5,5-difluoro- l,3,7,9-tetramethyl-5H-4λ4,5λ4-dipyrrolo[l,2-c:2',l,-f|[l,3,2]diazaborinine-2,8- dicarboxylate]: To a solution of compound 22.1 (0.078 mmol, 50 mg), compound 13.3.2 (0.085 mmol, 51 mg) and DMAP-pTsOH salt (0.078 mmol, 23 mg) in CH2CI2 (0.50 mL) was added DIC (0.468 mmol, 73 μL) and the reaction mixture was stirred at r.t. for 1 h. It was then filtered through celite and concentrated under reduced pressure. Flash chromatography (19:1, toluene/EtOAc) gave 78 mg of PLC-22 (82% yield) as a maroon solid. 1H NMR (400 MHz, Chloroform-d) d 8.68 (dd, J = 7.4, 2.5 Hz, 2H), 8.48 (dd, J = 8.5, 1.2 Hz, 1H), 7.76 (dd, J = 9.1, 7.6 Hz, 2H), 7.44 - 7.27 (m, 20H), 7.25 - 7.19 (m, 6H), 7.11 (apparent t, J = 7.4 Hz, 2H), 6.98 (d, J = 7.6 Hz, 2H), 5.28 (s, 4H), 2.89 - 2.81 (m, 8H), 2.68 (t, J = 7.4 Hz, 2H), 2.18 (apparent p, J = 7.5 Hz, 2H), 1.92 (s, 6H).
Example 2.23: PLC-23
Figure imgf000082_0001
Compound 23.1 [Dibenzyl 10-(2,6-dichloro-4-hydroxyphenyl)-5,5-difluoro-l,3,7,9- tetramethyl-5H-4λ4,5λ4-dipyrrolo[l,2-c:2',1-f][1,3,2]diazaborinine-2,8-dicarboxylate]: To a solution of benzyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (1.05 mmol, 241 mg) and 2,6- difluoro-4-hydroxybenzaldehyde (0.500 mmol, 96 mg) in CH2CI2 (10.0 mL) was added pTsOH H20 (0.050 mmol, 6 mg) and the reaction mixture was stirred at r.t. for 1.5 h. DDQ (0.600 mmol, 136 mg) was added and the mixture was stirred at r.t. for 2 h. Triethylamine (3.00 mmol, 417 μL) was then added, the mixture was stirred at r.t. for 30 min before BF3-OEt2
(4.50 mmol, 555 pL) was added and the mixture was stirred at r.t. for 1 h. It was then diluted with EtOAc (30.0 mL), washed with 3 M HCI (3 x 30.0 mL), dried (MgSO4) and concentrated under reduced pressure. Flash chromatography (toluene→ 19:1, toluene/EtOAc) gave 211 mg of compound 23.1 (62% yield) as an orange solid. 1H NMR (400 MHz, Chloroform-d) d 7.42 - 7.30 (m, 10H), 6.98 (s, 2H), 5.29 (s, 4H), 2.83 (s, 6H), 1.84 (s, 6H).
PLC-23 [Dibenzyl 10-(4-((4-(4-(6-(4-(diphenylamino)phenyl)-l,3-dioxo-1H- benzo[d e]isoquinolin-2(3H)-yl)phenyl)butanoyl)oxy)-2,6-difluorophenyl)-5,5-difluoro- l,3,7,9-tetramethyl-5H-4λ4,5λ4-dipyrrolo[l,2-c:2',l'-f|[l,3,2]diazaborinine-2,8- dicarboxylate]: To a solution of compound 23.1 (0.074 mmol, 50 mg), compound 13.3.2 (0.081 mmol, 49 mg) and DMAP-pTsOH salt (0.074 mmol, 22 mg) in CH2CI2 (0.40 mL) was added DIC (0.296 mmol, 46 pL) and the reaction mixture was stirred at r.t. for 1 h. It was then filtered through celite and concentrated under reduced pressure. Flash chromatography (toluene→ 19:1, toluene/EtOAc) gave 70 mg of PLC-23 (75% yield) as an orange/red solid. 1H NMR (400 MHz, Chloroform-d) d 8.71 - 8.65 (m, 2H), 8.48 (dd, J = 8.6, 1.2 Hz, 1H), 7.76 (dd, J = 9.1, 7.4 Hz, 2H), 7.44 - 7.27 (m, 21H), 7.25 - 7.18 (m, 6H), 7.15 - 7.08 (m, 2H), 5.28 (s, 4H),
2.89 - 2.78 (m, 8H), 2.68 (t, J = 7.4 Hz, 2H), 2.17 (apparent p, J = 7.5 Hz, 2H), 1.84 (s, 6H); 19F NMR (376 MHz, Chloroform-d) d -142.60 - -142.96 (m).
Example 2.24: PLC-24
Figure imgf000084_0001
Compound 24.1 [4-Bromo-N ,N -di-p-tolylaniline]: To a solution of di-p-tolylamine (1.00 mmol, 197 mg), l-bromo-4-iodobenzene (1.10 mmol, 311 mg), Pd(OAc)2 (0.010 mmol, 2.24 mg) and Xantphos (0.010 mmol, 5.78 mg) in toluene (1.50 mL) was added sodium tert- butoxide (1.20 mmol, 115 mg) and the reaction mixture was heated to reflux for 24 h. The reaction was quenched with water (10.0 mL) and the mixture was extracted with CH2CI2 (3 x 10.0 mL). The combined organics were dried (MgSO4) and concentrated under reduced pressure. Flash chromatography (19:1, hexanes/EtOAc) gave 114 mg of compound 24.1 (32% yield) as a colorless solid. 1H NMR (400 MHz, Chloroform-dd d 7.27 (dd, J = 7.6, 1.5 Hz, 1H), 7.06 (d, J = 8.3 Hz, 2H), 6.99 - 6.94 (m, 2H), 6.91 - 6.86 (m, 1H), 2.31 (s, 3H); 13C NMR (101
MHz, Chloroform-d) d 147.4, 144.9, 132.9, 131.9, 130.0, 124.7, 123.9, 113.6, 20.8.
Compound 24.2 [4-Methyl-N -(4-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2- yl)phenyl)-N -(p-tolyl)aniline]: To a solution of compound 24.1 (0.207 mmol, 73 mg), bis(pinacolato)diboron (0.228 mmol, 58 mg) and potassium acetate (0.621 mmol, 61 mg) in dioxane (2.00 mL) was added PdCl(dppf) (0.006 mmol, 5.00 mg) and the reaction mixture was stirred at 80 °C for 3 h and then at r.t. for 14 h. The reaction was quenched with 1.0 M aqueous NH4CI (10.0 mL) and the mixture was extracted with CH2CI2 (3 x 10.0 mL). The combined organics were dried (MgSC^) and concentrated under reduced pressure. Flash chromatography (19:1, hexanes/EtOAc) gave 57 mg of compound 24.2 (69% yield) as a colorless oil. 1H NMR (400 MHz, Chloroform-d) d 7.68 - 7.61 (m, 2H), 7.08 (dd, J = 8.4, 2.3 Hz, 4H), 7.00 (ddd, J = 14.1, 8.4, 2.8 Hz, 6H), 2.33 (s, 6H), 1.34 (s, 12H).
Compound 24.3 [4-(4-(6-(4-(Di-p-tolylamino)phenyl)-l,3-dioxo-1H- benzo[d e]isoquinolin-2(3H)-yl)phenyl)butanoic acid]: To a solution of compound 24.2 (0.143 mmol, 57 mg), compound 13.3.1 (0.136 mmol, 60 mg) and K2CO3 (0.204 mmol, 28 mg) in 20:1 v/v EtOH/H20 (1.50 mL) was added Pd(PPh3)4 (0.007 mmol, 8 mg) and the reaction mixture was stirred at 80 °C for 16 h. It was then partitioned between 1 M HCI (20.0 mL) and CH2CI2 (20.0 mL) and extracted with CH2CI2 (3 x 20.0 mL). The combined organics were dried (MgSO4) and concentrated under reduced pressure. Flash chromatography (1:1, hexanes/EtOAc → EtOAc) gave 62 mg of compound 24.3 (72% yield) as an orange powder. 1H NMR (400 MHz, Chloroform-d) d 8.66 (dd, J = 7.4, 3.7 Hz, 2H), 8.47 (d, J = 8.5 Hz, 1H), 7.78 - 7.71 (m, 2H), 7.37 (dd, J = 10.4, 8.3 Hz, 4H), 7.26 (d, J = 8.1 Hz, 5H), 7.19 - 7.06 (m, 10H), 2.79 (t, J = 7.6 Hz, 2H), 2.46 (t, J = 7.3 Hz, 2H), 2.35 (s, 6H), 2.12 - 2.01 (m, 4H).
PLC-24 Dibenzyl 10-(4-((4-(4-(6-(4-(di-p-tolylamino)phenyl)-l,3-dioxo-1H- benzo[de]isoquinolin-2(3H)-yl)phenyl)butanoyl)oxy)-2,6-dimethylphenyl)-5,5-difluoro- l,3,7,9-tetramethyl-5H-4λ4,5λ4-dipyrrolo[l,2-c:2',l,-f|[l,3,2]diazaborinine-2,8- dicarboxylate: To a solution of compound 3.5 [dibenzyl 5,5-difluoro-10-(4-hydroxy-2,6- dimethylphenyl)-l,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine- 2,8-dicarboxylate] (0.052 mmol, 33 mg), compound 24.3 (0.048 mmol, 30 mg) and DMAP-pTsOH salt (0.096 mmol, 28 mg) in CH2CI2 (0.52 mL) was added DIC (0.288 mmol, 45 μL) and the reaction mixture was stirred at r.t. for 1 h. It was then filtered through celite and concentrated under reduced pressure. Flash chromatography (toluene → 19:1, toluene/EtOAc) followed by re-precipitation from toluene/hexanes gave 24 mg of PLC-24 (40% yield) as an orange solid. 1H NMR (400 MHz, Chloroform-d→ d 8.70 - 8.63 (m, 2H), 8.49 (dd, J = 8.6, 1.2 Hz, 1H), 7.79 - 7.72 (m, 2H), 7.46 - 7.26 (m, 16H), 7.19 - 7.09 (m, 10H), 6.97 (s, 2H), 5.27 (s, 4H), 2.92 - 2.78 (m, 8H), 2.67 (t, J = 7.4 Hz, 2H), 2.35 (s, 6H), 2.22 - 2.08 (m, 8H), 1.72 (s, 6H).
Example 2.25: PLC-25
Figure imgf000086_0001
PLC-25 [Dibenzyl 10-(4-((4-(4-(6-(4-(diphenylamino)phenyl)-l,3-dioxo-1H- benzo[d e]isoquinolin-2(3H)-yl)phenyl)butanoyl)oxy)-2,6-dimethoxyphenyl)-5,5-difluoro- l,3,7,9-tetramethyl-5H-4λ4,5λ4-dipyrrolo[l,2-c:2',l'-/|[l,3,2]diazaborinine-2,8- dicarboxylate]: To a solution of benzyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (0.210 mmol, 48 mg) and compound 19.1 (0.100 mmol, 77 mg) in CH2CI2 (2.10 mL) was added pTsOH-H2O (0.010 mmol, 1.20 mg) and the reaction mixture was stirred at r.t. for 1 h. DDQ (0.120 mmol, 27 mg) was then added and the mixture was stirred at r.t. for 2 h. Triethylamine (0.600 mmol, 83 pL) was added, the mixture was stirred at r.t. for 30 min before BF3-OEt2 (0.900 mmol, 111 pL) was added and the mixture was stirred at r.t. for 1 h. More triethylamine (0.300 mmol, 42 pL) and, after 10 min stirring at r.t., BF3-OEt2 (0.450 mmol, 55 pL) were added and the mixture was stirred at r.t. for further 3 h. It was then diluted with EtOAc (15.0 mL), washed with 3 M HCI (3 x 15.0 mL), dried (MgSC ) and concentrated under reduced pressure. Flash chromatography (toluene → 19:1, toluene/EtOAc) gave 60 mg of PLC-25 (48% yield) as an orange solid. *H NMR (400 MHz, Chloroform-d) d 8.68 (dd, J = 7.4, 2.6 Hz, 2H), 8.48 (d ,J = 8.5 Hz, 1H), 777 (dd, J = 9.3, 7.4 Hz, 2H), 7.45 - 7.28 (m, 19H), 7.25 - 7.18 (m, 6H), 7.11 (apparent t, J = 7.3 Hz, 2H), 6.49 (s, 2H), 5.27 (s, 4H), 3.71 (s, 6H), 2.87 (t, J = 7.5 Hz, 2H), 2.81 (s, 6H), 2.68 (t, J = 7.5 Hz, 2H), 2.18 (apparent p, J = 7.5 Hz, 2H), 1.87 (s, 6H); 19F NMR (376 MHz, Chloroform-d) d -142.70 - -143.10 (m). Example 2.26: PLC-26
Figure imgf000087_0001
Compound 26.1:
1st step: A mixture of ethyl 2,4-dimethyl-lH-pyrrole-3-carboxylate (1.0 g, 6.0 mmol), 4- hydroxy-2,6-dimethylbenzaldehyde (0.449 g, 3.0 mmol) and p-TsOH (50 mg, 0.29 mmol) in 50 mL DCE was degassed and stirred at room temperature overnight. LCMS analysis shows that reaction completed with main leak of m/e+=467.
2nd step: To the mixture obtained above, DDQ (0.817 g, 3.6 mmol) was added and the whole was stirred at room temperature for 30 min. LCMS analysis indicates that reaction completed with main peak of m/e+ = 465. 3rd step: With ice-batch cooling, to the mixture obtained above, triethylamine (1.7 mL, 19 mmol) and BF -diethyl ether (2.2 mL, 18 mmol) was added, and the resulting mixture was stirred at 50 C for one hour. Additional 1 mL triethylamine and 1 mL BF -diethyl ether were added, and the whole was heated for additional one hour. LCMS analysis indicates that all dipyrrolemethane starting material was converted to BODIPY product with m/e+ = 513. After cooled to room temperature, the reaction mixture was submitted to silica gel and purified by flash chromatography using eluents of hexanes/ethyl acetate (0% - 30% ethyl acetate). The desired fraction was collected. After removal of solvents, the desired product was obtained as orange solid (1.0 g, in 65% yield). 1H NMR (400 MHz, Chloroform-d) d 6.68 (s, 2H), 4.29 (q, J = 7.1 Hz, 4H), 2.84 (s, 6H), 2.05 (s, 6H), 1.34 (t, J = 7.1 Hz, 6H). LCMS (APCI+): calcd for C27H32BF2N2O5 (M+H) = 513.2; Found: 513.
PLC-26: A mixture of compound 26.1 (100 mg, 0.195 mmol), compound 13.3.2 [4-(4- (6-(4-(diphenylamino)phenyl)-l,3-dioxo-lH-benzo[de]isoquinolin-2(3H)-yl)phenyl)butanoic acid] (132 mg, 0.22 mmol), DIC (0.1 mL, 0.63 mmol) and DMAP/p-TsOH (118 mg, 0.4 mmol) in DCM (6mL) was stirred at room temperature overnight, then loaded on silica gel, and purified by flash chromatography using eluents of DCM/ethyl acetate (0% - 5% ethyl acetate). The desired main orange color faction was collected. After removal of solvents, the resulting solid was reprecipitated in DCM/MeOH. The desired product PLC-26 was obtained after filtration and dried in air as orange solid (145 mg, 68% yield). 1H NMR (400 MHz, d2-TCE) d 8.56 (dd, J = 7 A, 4.7 Hz, 2H), 8.43 (d, J = 8.3 Hz, 1H), 7.79 - 7.64 (m, 2H), 7.41 - 7.18 (m, 10H), 7.18 - 7.12 (m, 6H), 7.03 (t, J = 7.3 Hz, 2H), 6.93 (s, 2H), 4.19 (q, J = 1.1 Hz, 4H), 2.81 (t,
J = 7.6 Hz, 2H), 2.75 (s, 6H), 2.62 (t, J = 7.4 Hz, 2H), 2.11 (t, J = 7.5 Hz, 2H), 2.06 (s, 6H), 1.65 (s, 6H), 1.25 (t, J = 1.1 Hz, 6H). LCMS (APCI-): calcd for C67H59BF2N4O8 (M-) = 1096.4; Found: 1096.
Example 2.27: PLC-27
Figure imgf000088_0001
l,4,5,6-Tetrahydrobenzo[6,7]cyclohepta[l,2-b]pyrrole (Compound 27.1) To a solution of 1- benzosuberone (10.0 mmol, 1.46 mL) in 3:1, HhO/EtOH (32.5 mL) at r.t. were added NH2- OH-HCI (15.0 mmol, 1.04 g) and sodium acetate (25.0 mmol, 2.05 g) and the reaction mixture was stirred at 95 °C for 1 h. It was then cooled to r.t., filtered, washed with water (150 mL) and lyophilized for 16 h to give 1.64 g of 6,7,8,9-tetrahydro-5H-benzo[7]annulen-5-one oxime (94% yield) as a colorless solid which was used in the subsequent synthetic step without further purification.
To a solution of 6,7,8,9-tetrahydro-5H-benzo[7]annulen-5-one oxime (5.71 mmol, 1.00 g) in DMSO (9.00 mL) at r.t. was added KOH (17.1 mmol, 959 mg) and the reaction mixture was heated to 140 °C before 1,2-dichloroethane (11.4 mmol, 897 pL) in DMSO (2.00 mL) was added over 3 h via a syringe pump. The mixture was then cooled to r.t., quenched with 1M aqueous NH4CI solution (30.0 mL) and extracted with CH2CI2 (3 x 30.0 mL). The combined organics were dried (MgS04) and concentrated under reduced pressure. Flash chromatography (hexanes -> 9:1, hexanes/EtOAc) gave 262 mg of compound 27.1 (25% yield) as a yellow solid. 1H NMR (400 MHz, Chloroform-d) d 8.18 (br s, 1H), 7.34 (dd, J = 7.8, 1.3 Hz, 1H), 7.25 - 7.19 (m, 1H), 7.16 (dd, J = 7.6, 1.6 Hz, 1H), 7.13 - 7.07 (m, 1H), 6.84 (t, J = 2.8 Hz, 1H), 6.17 (t, J = 2.8 Hz, 1H), 2.91 (t, J = 6.8 Hz, 2H), 2.86 - 2.80 (m, 2H), 2.07 - 1.98 (m, 2H); 13C NMR (101 MHz, Chloroform-d) d 140.4, 131.8, 129.3, 126.8, 125.9, 125.2, 123.2, 121.8, 118.3, 111.1, 34.9, 27.8, 26.7.
4-(19,19-Difluoro-6,7,ll,12,13,19-hexahydro-5H-18X4,19X4- benzolB'^'lcycloheptair^'^SlpyrroloIl^-clbenzolB'^'lcycloheptair^'^Slpyrrolo^,!- ][l,3,2]diazaborinin-9-yl)-3,5-difluorophenol (Compound 27.2)
To a solution of compound 27.1 (1.36 mmol, 250 mg) and 2,6-difluoro-4- hydorxybenzaldehyde (0.650 mmol, 103 mg) in CH2CI2 (13.5 mL) was added pTsOH-^O (0.065 mmol, 8 mg) and the reaction mixture was stirred at r.t. for 1 h. DDQ (0.780 mmol, 177 mg) was then added and the mixture was stirred at r.t. for 1 h. Triethylamine (3.90 mmol, 542 pL) was added, the mixture was stirred at r.t. for 1 h before BF3-OEt2 (5.85 mmol, 722 pL) was added and the mixture was stirred at r.t. for 1 h. More triethylamine (3.90 mmol, 542 pL and, after 30 min stirring at r.t., BF3-OEt2 (5.85 mmol, 722 pL) were added and the mixture was stirred at r.t. for further 1 h. It was then diluted with EtOAc (30.0 mL), washed with 3 M HCI (3 x 30.0 mL), dried (MgS04) and concentrated under reduced pressure. Flash chromatography (toluene → 19:1, toluene/EtOAc) gave 149 mg of compound 17.2 (42% yield) as a blue solid. 1H NMR (400 MHz, DMSO-d6) d 7.73 (d, J = 7.4 Hz, 1H), 7.31 - 7.14 (m, 4H), 6.71 (s, 1H), 6.62 (d, J = 10.0 Hz, 1H), 2.47 - 2.40 (m, 2H), 2.28 - 2.04 (m, 2H), 1.90 - 1.83 (m, 3H).
4-(19,19-difluoro-6,7,ll,12,13,19-hexahydro-5H-18λ4,19λ4- benzo[3'4']cyclohepta[.14 '2 5]>.pyrrolo[12^, -c]benzo[3'4']cyclohepta[1245] pyrrolo^,!- /][l,3,2]diazaborinin-9-yl)-3,5-difluorophenyl 4-(4-(6-(4-(diphenylamino)phenyl)-l,3-dioxo- lH-benzo[c/e]isoquinolin-2(3H)-yl)phenyl)butanoate (PLC-27) To a solution of compound 27.2 (0.091 mmol, 50 mg), compound 13.3.2 (0.099 mmol, 60 mg) and DMAP-pTsOH salt (0.091 mmol, 27 mg) in CH2CI2 (0.50 mL) was added DIC (0.364 mmol, 57 pL) and the reaction mixture was stirred at r.t. for 1 h. It was then filtered through celite and concentrated under reduced pressure. Flash chromatography (toluene) gave 78 mg of PLC-27 (76% yield) as a dark purple solid. 1H NMR (400 MHz, Chloroform-d) d 8.68 - 8.57 (m, 2H), 8.41 (dd, J = 8.5, 1.2 Hz, 1H), 8.08 - 7.88 (m, 2H), 7.72 - 7.64 (m, 2H), 7.39 - 7.30 (m, 4H),
7.29 - 7.22 (m, 8H), 7.18 - 7.13 (m, 6H), 7.06 - 7.01 (m, 2H), 6.89 (d, J = 7.9 Hz, 2H), 6.51 (s, 2H), 2.85 - 2.77 (m, 2H), 2.65 (t, J = 7.4 Hz, 2H), 2.56 (t, J = 6.8 Hz, 4H), 2.35 - 2.18 (m, 4H), 2.18 - 2.09 (m, 2H), 2.01 - 1.91 (m, 4H), 1.22 - 1.13 (m, 4H).
Example 2.28: PLC-28
Figure imgf000091_0001
4-(4-(6-(4-(Diphenylamino)phenyl)-l,3-dioxo-1H-benzo[d e]isoquinolin-2(3H)- yl)phenyl)butanoyl chloride (Compound 28.1)
To a suspension of compound 13.3.2 (0.500 mmol, 300 mg) in CH2CI2 (2.50 mL) was added DMF (1 drop) and oxalyl chloride (1.00 mmol, 86 μL) and the reaction mixture was stirred at r.t. for 2.5 h. All volatiles were removed under reduced pressure to give 315 mg of compound 28.1 (>99% yield) as a yellow/brown solid. The material was of sufficient purity to use directly in the subsequent synthetic step. 1H NMR (400 MHz, Methylene Chloride-^) d 8.63 (dd, J = 7.5, 1.6 Hz, 2H), 8.49 (dd, J = 8.6, 1.2 Hz, 1H), 7.80 - 7.73 (m, 2H), 7.45 - 7.29 (m, 9H), 7.29 - 7.16 (m, 9H), 7.13 - 7.06 (m, 2H), 3.03 (t, J = 7.2 Hz, 2H), 2.84 - 2.76 (m, 3H), 2.17 - 2.09 (m,
2H); 13C NMR (101 MHz, Methylene Chloride-d2) d 174.3, 165.0, 164.8, 149.0, 148.0, 147.7, 141.7, 134.7, 133.7, 132.6, 131.8, 131.5, 131.4, 130.8, 130.0, 129.9, 129.8, 129.4, 129.3, 128.3, 127.3, 125.6, 124.2, 123.7, 123.1, 122.0, 47.0, 34.6, 27.1.
2-(4-(3-(6,6-difluoro-13,15-dimethyl-12,16-dihydro-6H-5λ4,6λ4- indeno[2',l,:4,5]pyrrolo[l,2-c]indeno[2,,l,:4,5]pyrrolo[2,l-f|[l,3,2]diazaborinin-14- yl)propyl)phenyl)-6-(4-(diphenylamino)phenyl)-lH-benzo[d e]isoquinoline-l,3(2H)-dione
(PLC-28)
To a solution of compound 28.1 (0.200 mmol, 124 mg) in DCE (2.20 mL) was added a solution of 3-methyl-l,4-dihydroindeno[l,2-fa]pyrrole (0.440 mmol, 74 mg) in DCE (2.20 mL) at r.t. and the reaction mixture was heated to reflux for 16 h after which it was cooled to r.t..
Triethylamine (1.20 mmol, 166 mί) was added, the mixture was stirred at r.t. for 1 h before BF -OEt (1.80 mmol, 222 pL) was added and the mixture was stirred at r.t. for 3.5 h. It was then diluted with EtOAc (30.0 mL), washed with 3 M HCI (3 x 30.0 mL), dried (MgS ) and concentrated under reduced pressure. Flash chromatography (3:2 hexanes/EtOAc, then 1:1 toluene/CFhCh) gave 13 mg of PLC-28 (7% yield) as a purple solid. 1FI NMR (400 MFIz, Methylene Chloride-d2) d 8.6 (d, J = 7.5 Hz, 2H), 8.5 (d, J = 8.5 Hz, 1H), 8.3 (d, J = 7.7 Hz, 2H), 7.8 - 7.7 (m, 2H), 7.5 (d, J = 7.6 Hz, 2H), 7.5 - 7.4 (m, 6H), 7.4 - 7.3 (m, 10H), 7.2 - 7.2 (m, 6H), 7.1 - 7.1 (m, 2H), 3.6 (s, 2H), 3.2 - 3.1 (m, 2H), 3.0 (t, J = 7.2 Hz, 2H), 2.4 (s, 6H), 2.2 - 2.1 (m, 2H).
Example 2.29: PLC-29
Figure imgf000092_0001
3,5-Dichloro-4-(19,19-difluoro-6,7,ll,12,13,19-hexahydro-5H-18l4,19l4- benzolS'^'lcycloheptall'^'^SlpyrroloIl^-clbenzolSVl'lcycloheptair^'^Slpyrrolo^,!- f][l,3,2]diazaborinin-9-yl)phenol (Compound 29.1):
A 100 mL 2-neck round bottomed flask was fitted with an air condenser and a stir bar. To the flask, compound l,4,5,6-tetrahydrobenzo[6,7]cyclohepta[l,2-b]pyrrole (Compound 27.1, 220 mg, 1.20 mmol) and 4-hydroxy-2,6-dichlorobenzaldehyde (115 mg, 0.61 mmol) were added, followed by anhydrous dichloroethane (15 ml). The reaction mixture was sparged with Argon for 30 minutes, then trifluoracetic acid (TFA) (3 drops) was added. The reaction solution was heated up to 40 °C overnight. After the reaction was cooled down to 0 °C in an ice-water bath, p-chloranil (200 mg, 0.81 mmol) was added. The reaction was kept at 0 °C for 20 minutes. Then BF3-OEt2 (0.8 mL, 6.5 mmol) and EtsN (0.5 mL, 3.6 mmol) were added at 0 °C. The reaction mixture was heated up to 50 °C for 1 hour. The reaction mixture was loaded with silica gel and purified by flash chromatography, using hexane in DCM (0-70%) as an eluant to provide the pure BODIPY Compound 29.1 as a brown golden solid, 115 mg, in 33% yield. MS (APCI): calculated for C33H24BCI2F2N2O ([M-H]+) = 584; found: 584. *H NMR (400 MHz, CDCI3) 8.09 (dd, J = 4.0 Hz, 2.0 Hz, 2H), 7.32 (dddd, J = 13.2 Hz, 7.2 Hz, 7.2 Hz, 2.0 Hz, 4H), 7.22 (dd, J = 6.4 Hz, 2.0 Hz, 2H), 6.99 (s, 2H), 6.43 (s, 2H)c, 5.77 (bs, 1H), 2.63 (dd, J = 6.8 Hz, 6.8 Hz, 4H), 2.32 (bs, 4H), 2.03 (ddd, J = 14.0 Hz, 6.8 Hz, 6.8 Hz, 4H).
PLC-29 A mixture of 3,5-dichloro-4-(19,19-difluoro-6,7,ll,12,13,19-hexahydro-5H-18l4,19l4- benzo[3',4']cyclohepta[l',2':4,5]pyrrolo[l,2-c]benzo[3',4']cyclohepta[l',2':4,5]pyrrolo[2,l- f][l,3,2]diazaborinin-9-yl)phenol (Compound 29.1, 29 mg, 0.0495 mmol), 4-(4-(6-(4- (diphenylamino)phenyl)-l,3-dioxo-lH-benzo[de]isoquinolin-2(3H)-yl)phenyl) butanoic acid (Compound 13.3.2, 48 mg, 0.08 mmol), DIC (0.1 mL, 0.63 mmol), DMAP/TsOH salt (29 mg, 0.1 mmol) in anhydrous dichloromethane (5 mL) was stirred at room temperature for 48 hr. The resulted mixture was loaded on silica gel and purified by flash chromatography using eluents of hexanes/dichloromethane (40% - 100% dichloromethane). The desired fraction was collected. After removal of solvents and washed with methanol, a dark red solid was obtained after filtration and dried in air (PLC-29, 43 mg, in 74% yield). LCMS (APCI): calcd for C73H53BCI2F2N4O4: 1168.3; found: 1168. *H NMR (400 MHz, TCE-d2) d 8.60 - 8.53 (m, 2H), 8.43 (dd, J = 8.6, 1.1 Hz, 1H), 7.97 (t, J = 4.6 Hz, 2H), 7.76 - 7.68 (m, 2H), 7.39 (d, J = 8.2 Hz, 2H), 7.36 - 7.19 (m, 16H), 7.15 (d, J = 8.0 Hz, 6H), 7.03 (t, J = 7.3 Hz, 2H), 6.40 (s, 2H), 2.83 (t, J = 7.5 Hz, 2H), 2.68 (t, J = 7.4 Hz, 2H), 2.60 - 2.50 (m, 4H), 2.24 (bs, 4H), 2.14 (q, J = 7.6 Hz, 2H), 1.96 (t, J = 7.1 Hz, 4H).
Example 3 Fabrication of a Color Conversion Film
A glass substrate was prepared in substantially the following manner. A 1.1 mm thick glass substrate measuring 1-inch X 1-inch was cut to size. The glass substrate was then washed with detergent and deionized (Dl) water, rinsed with fresh Dl water, and sonicated for about 1 hour. The glass was then soaked in isopropanol (IPA) and sonicated for about 1 hour. The glass substrate was then soaked in acetone and sonicated for about 1 hour. The glass was then removed from the acetone bath and dried with nitrogen gas at room temperature.
A 20 wt% solution of Poly(methylmethacrylate) (PMMA) (average M.W. 120,000 by GPC from MilliporeSigma, Burlington, MA, USA) copolymer in cyclopentanone (99.9% pure) was prepared. The prepared copolymer was stirred overnight at 40 °C. [PMMA] CAS: 9011- 14-7; [Cyclopentanone] CAS: 120-92-3
The 20% PMMA solution prepared above (4g) was added to 3 mg of the photoluminescent complex made as described above in a sealed container and mixed for about 30 minutes. The PMMA/lumiphore solution was then spin coated onto a prepared glass substrate at 1000 RPM for 20 s and then 500 RPM for 5 s. The resulting wet coating had a thickness of about 10 pm. the samples were covered with aluminum foil before spin coating to protect them from exposure to light. Three samples each were prepared in this manner for each for Emission/FWHM and quantum yield. The spin coated samples were baked in a vacuum oven at 80 °C for 3 hours to evaporate the remaining solvent. The 1-inch X 1-inch sample was inserted into a Shimadzu, UV-3600 UV-VIS- NIR spectrophotometer (Shimadzu Instruments, Inc., Columbia, MD, USA). All device operations were performed inside a nitrogen-filled glove-box. The resulting absorption/emission spectrum for PC-8 is shown in FIG.l, while the resulting absorption/emission spectrum for PC- 33 is shown in FIG. 2. The fluorescence spectrum of a 1-inch X 1-inch film sample prepared as described above was determined using a Fluorolog spectrofluorometer (Horiba Scientific, Edison, NJ, USA) with the excitation wavelength set at the respective maximum absorbance wavelength. The maximum emission and FWHM are shown in Table 1.
The quantum yield of a 1-inch X 1-inch sample prepared as described above were determined using a Quantarus-QY spectrophotometer (Hamamatsu Inc., Campbell CA, USA) was excited at the respective maximum absorbance wavelength. The results are reported in Table 1.
The results of the film characterization (absorbance peak wavelength, FWHM, and quantum yield) are shown in Table 1 below.
Figure imgf000095_0001
Figure imgf000096_0001
Figure imgf000097_0001
Figure imgf000098_0001
Figure imgf000099_0001
Figure imgf000100_0001
Figure imgf000101_0001
Figure imgf000102_0001

Claims

CLAIMS What is claimed is:
1. A photoluminescent complex, comprising: a blue light absorbing naphthalic acid derivative; a boron-dipyrromethene (BODIPY) moiety; and a linker group, wherein the linker group covalently links the naphthalic acid derivative to the BODIPY moiety; wherein the blue light absorbing naphthalic acid derivative is represented by the formula:
Figure imgf000103_0001
wherein X is NR9 or O; wherein R9 is H, a substituted aryl, or the linker group; wherein n is 0 or 1; wherein R10 is H, methyl, a direct bond to an adjacent phenyl ring forming a carbazole, or the linker group; wherein R11 is H, or methyl; wherein the linker group is a substituted ester group, or a substituted aralkyl group; wherein the naphthalic acid derivative absorbs light energy of a first excitation wavelength and transfers an energy to the BODIPY moiety, wherein the BODIPY moiety absorbs the energy from the naphthalic acid derivative and emits a light energy of a second higher wavelength; and wherein the photoluminescent complex has an emission quantum yield greater than
80%.
2. The photoluminescent complex of claim 1 wherein the BODIPY moiety is represented by the formula:
Figure imgf000104_0001
wherein R1 and R6 are independently H, an alkyl group, an alkene group, or an alkyne group; wherein R3 and R4 are independently H or a C1-C2 alkyl; wherein R2 and R5, are independently H, an alkyl group, an alkene group, an alkyne group, a cyano (-CN), an alkyl ester, or an aryl ester; wherein R1 and R2 may link togetherto form an additional monocyclic hydrocarbon ring structure, or a polycyclic hydrocarbon ring structure; wherein R5 and R6 may link togetherto form an additional monocyclic hydrocarbon ring structure, or a polycyclic hydrocarbon ring structure; wherein G7 is L or:
Figure imgf000104_0002
wherein R7 and R8 are independently a H, a methyl, a fluoride, a chloride, or an alkoxy group; and wherein L represents the linker group .
3. The photoluminescent complex of claim 1 or 2, wherein X is NR9, n is 0, R9 is a substituted aryl, R10 is substituted ester linker, and R11 is H.
4. The photoluminescent complex of claim 3, wherein R9 is
Figure imgf000105_0002
Figure imgf000105_0001
5. The photoluminescent complex of claim 1, wherein X is NR9, n is 0 or 1, R9 is the linker group, R10 is H, and R11 is H.
6. The photoluminescent complex of claim 1, wherein X is NR9, n is 0 or 1, R9 is the linker group, R10 is methyl, and R11 is methyl.
7. The photoluminescent complex of claim 1, wherein X is NR9, n is 1, R9 is the linker group, R10 is a direct bond to an adjacent phenyl ring forming a carbazole, and R11 is H.
8. The photoluminescent complex of claim 1, wherein X is O , n is 1, R10 is the linker group, and R11 is H.
9. The photoluminescent complex of claim 2, wherein R1, R3, R4, and R6 are methyl, R2 and R5 are an alkyl ester or an aryl ester, R7 and R8 are methyl, and L is the linker group.
10. The photoluminescent complex of claim 2, wherein R1, R3, R4, and R6 are methyl, R2 and R5 are a cyano, R7 and R8 are methyl and L is the linker group.
11. The photoluminescent complex of claim 2, wherein R1, R3, R4, and R6 are methyl, R2 and R5 are an aryl ester, R7 and R8 are independently a methyl, a fluoride, a chloride or a methoxy group, and L is the linker group.
12. The photoluminescent complex of claim 2, wherein R1 and R2 link together to form a polycyclic hydrocarbon ring structure, R3 and R4, are H or methyl, R5 and R6 link together to form a polycyclic hydrocarbon ring structure, R7 and R8 are H, a methyl, a halogen, or a methoxy group, and L is the linker group.
13. The photoluminescent complex of claim 1, 2, 3, 4, 5, 6, 7 , 8, 9, 10, 11, or 12, wherein
Figure imgf000106_0001
14. The photoluminescent complex of claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, wherein
Figure imgf000106_0002
15. The photoluminescent complex of claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14, wherein the complex is one of the following structures:
Figure imgf000106_0003
Figure imgf000107_0001
Figure imgf000108_0001
Figure imgf000109_0001
Figure imgf000110_0001
16. A color conversion film comprising: a transparent substrate layer; a color conversion layer, wherein the color conversion layer includes a resin matrix, and a photoluminescent complex of claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15, dispersed within the resin matrix.
17. The color conversion film of claim 16, further comprising a singlet oxygen quencher or a radical scavenger.
18. The color conversion film of claim 16 or 17, wherein the film has a thickness of between 10 pm and 200 pm.
19. The color conversion film of claim 16, 17, or 18, wherein the film absorbs light in about 400 nm to about 480 nm wavelength range and emits light in the 510 nm to about 560 nm wavelength range, or in the 575 nm to about 645 nm wavelength range.
20. A backlight unit including the color conversion film of claim 16, 17, 18, or 19.
21. A display device including the back-light unit of claim 20.
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CN105017300A (en) * 2015-06-30 2015-11-04 东南大学 Perylene diimide-borofluoride dipyrrolidine fluorescent dendrimer and preparation method and application thereof
CN105440065A (en) * 2015-11-11 2016-03-30 东南大学 Naphthalimide-boron dipyrromethene (NP-BODIPY) fluorescence molecules as well as preparation method and application thereof

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CN115850234A (en) * 2021-11-23 2023-03-28 厦门大学 N-phenyl-1, 8-naphthalimide derivative and preparation method and application thereof
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