WO2024119026A1 - 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
WO2024119026A1
WO2024119026A1 PCT/US2023/082002 US2023082002W WO2024119026A1 WO 2024119026 A1 WO2024119026 A1 WO 2024119026A1 US 2023082002 W US2023082002 W US 2023082002W WO 2024119026 A1 WO2024119026 A1 WO 2024119026A1
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mmol
phenyl
bis
stirred
silica gel
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PCT/US2023/082002
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French (fr)
Inventor
Jeffrey R. Hammaker
Shijun Zheng
Tissa Sajoto
Sadahiro Nakanishi
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Nitto Denko Corporation
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Publication of WO2024119026A1 publication Critical patent/WO2024119026A1/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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/022—Boron compounds without C-boron linkages
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/08—Naphthalimide dyes; Phthalimide dyes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • H10K85/322—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising boron
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/658—Organoboranes
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/1336—Illuminating devices
    • G02F1/133614—Illuminating devices using photoluminescence, e.g. phosphors illuminated by UV or blue light
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/30—Devices specially adapted for multicolour light emission
    • H10K59/38—Devices specially adapted for multicolour light emission comprising colour filters or colour changing media [CCM]

Definitions

  • 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.
  • Co-pending patent applications include at least Patent Cooperation Treaty Publication WO2022/178450, filed February 22,2022, PCT/US2022/017373; and PCT/US2022/076912, filed September 23, 2022). Therefore, there exists a need for improving performance in color conversion films, backlight units, and display devices.
  • 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 provides novel color converting dye complex with good blue light absorbance and narrow emissions bandwidths, e.g., with a full width half maximum [FWHM] of emission band of less than 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 comprising a blue light absorbing moiety; a linker complex; and a boron-dipyrromethene (BODIPY) moiety.
  • a photoluminescent complex comprising a blue light absorbing moiety; a linker complex; and a boron-dipyrromethene (BODIPY) moiety.
  • the blue light absorbing moiety is a xanthenoisoquinoline group of the general formula: where R° comprises H, an alkyl group, -CF 3 , alkoxy, or optionally substituted aryl, and R 10 comprises H, an alkyl group, -CF 3 , alkoxy, or optionally substituted aryl.
  • the dashed line comprises a covalent bond to the linker complex.
  • R 1 and R 6 and R 3 and R 4 comprise H, alkyl, cycloalkyl, alkenyl group
  • R 2 and R 5 comprise H, alkyl, cycloalkyl, a cyano (-CN) group, an alkyl ester group, or an aryl ester group
  • R 7 and R 8 comprise optionally substituted aryl, a C2-8 alkyl group; a C3-8 cycloalkyl group; an ether group having a C110 alkyl group, an ether moiety having an optionally substituted aryl group, or a C1-10 arylalkyl group.
  • the linker complex comprises an optionally substituted ester or an optionally substituted ether linker, where the linker complex covalently links the blue light absorbing moiety and the BODIPY moiety.
  • the blue light absorbing moiety absorbs light energy of a first excitation wavelength and transfers an energy to the BODIPY moiety.
  • the BODIPY moiety absorbs the energy from the blue light absorbing moiety and emits a light energy of a second higher wavelength.
  • the photoluminescent complex has an emission quantum yield greater than 80%.
  • R 7 and R 8 of the photoluminescent complex comprise optionally
  • R 7 and R 8 of the photoluminescent complex comprise an optionally substituted alkyl group, an optionally substituted cycloalkyl group, or an optionally substituted ether group comprising pentyl, 2-ethylhexyl, cyclohexyl, CH 2 -cyclohexyl, -OCH 3 , -O-(2-ethylhexyl), -OCH 2 - cyclohexyl, -OPh, or -O(CH 2 ) 3 -Ph.
  • Some embodiments include a photoluminescent complex where R 1 and R 6 comprise H, methyl, ethyl, propyl group, isopropyl, butyl, or isobutyl; and wherein R 3 and R 4 comprise H, methyl, ethyl, propyl group, isopropyl, butyl, or isobutyl.
  • R 10 of the photoluminescent complex comprises H.
  • the linker complex comprises
  • X of the photoluminescent complex is F. In other cases, X of the photoluminescent complex is CN.
  • Some embodiments of the present disclosure comprise a color conversion film comprising.
  • the color conversion film comprises a transparent substrate layer and a color conversion layer comprising a resin matrix.
  • a photoluminescent compound described herein is dispersed within the resin matrix.
  • the color conversion film of the present disclosure may comprise a singlet oxygen quencher.
  • the color conversion film may further comprise a radical scavenger.
  • Some embodiments include a method for preparing the color conversion film, comprising: dissolving an aforedescribed photoluminescent complex and a binder resin within a solvent; and applying the mixture on a surface of the transparent substrate.
  • Some embodiments include a backlight unit including a color conversion film described herein.
  • the present application provides a photoluminescent complex 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 photostability of one embodiment of a photoluminescent complex (PLC-1) as compared to a comparative example (CE-3).
  • FIG. 2 is a graph depicting the absorption and emission spectra of one embodiment of a photoluminescent complex (PLC-21).
  • FIG. 3 is a graph depicting the absorption and emission spectra of one embodiment of a photoluminescent complex (PLC-25).
  • the present disclosure is related to photoluminescent compounds and complexes for use in color conversion films, backlight units, and display devices.
  • the current disclosure describes photoluminescent complexes and their uses in color conversion films.
  • the photoluminescent complex 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.
  • the present disclosure includes a photoluminescent complex that may enhance the contrast or intensity between two colors, increasing their distinction from one another.
  • substituted 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 of the parent structure have been independently replaced by one or more substituent groups.
  • the substituent groups may be independently selected from an optionally substituted Ci- 8 alkyl, C 3 -8 alkenyl, or a C3-8 heteroalkyl.
  • alkyl moiety may be branched, straight chain (i.e., unbranched), or cyclic. In some embodiments, the alkyl moiety may have 1 to 8 carbon atoms.
  • the alkyl group of the compounds designated herein may be designated as "Ci- 8 alkyl" or similar designations.
  • Ci-8 alkyl indicates that there are 1, 2, 3, 4, 5, 6, 7, or 8 carbon atoms in the alkyl chain, i.e., the alkyl chain is methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, and any isomers thereof.
  • Chalky I includes C1-2 alkyl, C1.3 alkyl, C1-4 alkyl, C1.5 alkyl, Ci- 6 alkyl, Ci-7 alkyl, and Ci- 8 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, ethenyl, propenyl, butenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.
  • heteroalkyl refers to an alkyl group, as defined herein, in which one or more of the constituent carbon atoms have been replaced by a nitrogen, oxygen, or sulphur. Examples include but are not limited to, -CH2-O-CH3, -CH2-CH2-O-CH3, -CH2-NH-CH3, -CH2-N(CH3)-CH3, -CH2-CH2-NH-CH3, -CH2-CH2-N(CH 3 )-CH 3 , -CH2-S-CH 2 -CH 3 , -CH2-CH 2 -S(O)-CH 3 . In addition, up to two heteroatoms may be consecutive, such as, by way of example, -CH2-NH-O-CH3, etc.
  • aromatic refers to a planar ring having a delocalized n-electron system containing 4n+2 n 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 ring or ring system that contains only carbon and hydrogen and may be saturated.
  • Monocyclic hydrocarbon rings include groups having from 3 to 12 carbon atoms.
  • aryl refers to 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 group substituted with an aryl.
  • Non-limiting aralkyl groups include benzyl, phenethyl; 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. It is understood that the heteroaryl ring may have additional heteroatoms in the ring. In heteroaryls that have two or more heteroatoms, those two or more heteroatoms may be the same or different from one another. Heteroaryl groups may be optionally substituted.
  • An N-containing heteroaryl moiety refers to an aryl group in which a skeletal atom of the ring is a nitrogen atom.
  • Illustrative examples of heteroaryl groups include the following moieties: pyrrole, imidazole, etc.
  • halogen refers to fluorine, chlorine, bromine, and iodine.
  • bond refers to a chemical bond between two atoms or to two moieties when the atoms joined by the bond are considered to be part of a larger structure.
  • 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 comprises alkyl, cycloalkyl, aryl, heteroaryl (bonded through a ring carbon) or heterocyclic (bonded through a ring carbon). Any hydroxy, or carboxyl side chain on the compounds described herein may be esterified. Any suitable procedures and specific groups to make such esters may be utilized.
  • ether refers to a chemical moiety that contains an oxygen atom connected to two alkyl or aryl groups with the general formula of R-O-R', where R and R' are alkyl and/or aryl.
  • alkoxy refers to a chemical moiety that contains an oxygen atom bonded to an alkyl group that is further bonded to an alkyl or aryl group.
  • BODIPY refers to a chemical moiety with the formula:
  • the BODIPY moiety may be composed of a dipyrromethene complexed with a di-substituted boron atom (BXz), typically a BF2or a B(CN)z unit.
  • BXz di-substituted boron atom
  • B(CN)z typically a BF2or a B(CN)z unit.
  • xanthenoisoquinoline or "xanthenoisoquinoline derivative” as used herein, refers to a chemical moiety with the formula: xantheno[2,l,9-def]isoquinoline-l,3(2H)-dione.
  • the present disclosure is related to photoluminescent complexes that absorb light energy of a first wavelength and emit 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.
  • a photoluminescent complex comprises: a blue light absorbing moiety, a linker complex, and a boron-dipyrromethene (BO DI PY) moiety.
  • the blue light absorbing moiety is a xanthenoisoquinoline derivative.
  • the linker complex may covalently link the xanthenoisoquinoline derivative to the BODIPY moiety.
  • the xanthenoisoquinoline 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.
  • 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%.
  • the emission quantum yield may be greaterthan 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%.
  • 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%), 0.81 (81%), 0.82 (82%), 0.83 (83%), 0.84 (84%), 0.85 (85%), 0.86 (86%), 0.87 (87%), 0.88 (88%), 0.89 (89%), 0.9 (90%), 0.91 (91%), 0.92 (92%), 0.93 (93%), 0.94 (94%), or 0.95 (95%), and may be up to nearly 1 (100%).
  • Quantum yield measurements in film may be made by spectrophotometer, e.g., Quantaurus-QY spectrophotometer (Hamamatsu, Inc., Campbell, CA, USA).
  • the photoluminescent complex has an emission band and 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, less than or equal to about 20 nm.
  • the photoluminescent complex may have a Stokes shift that is equal to or greater than 45 nm.
  • 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 about 500 nm to about 560 nm or any number bound by this range.
  • 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 405-410 nm, about 410-415 nm, about 415-420 nm, about 420-425 nm, about 425-430 nm, about 430-435 nm, about 435-440 nm, about 440-445 nm, about 445-450 nm, about 450-455 nm, about 455-460 nm, about 460-465 nm, about 465-470 nm, or any wavelength in a range bounded by any of these values.
  • the photoluminescent complex may have an emission peak between about 500 nm and about 560 nm.
  • the emission peak may be between about 500 nm to about 515 nm, about 515 nm to about 520 nm, about 520 nm to about 525 nm, about 525 nm to about 530 nm, about 530 nm to about 535 nm, about 535 nm to about 540 nm, about 540 nm to about 545 nm, about 545 nm to about 550 nm, about 550 nm to about 555 nm, about 555 nm to about 560 nm, or any wavelength in a range bounded by any these ranges.
  • the photoluminescent complex may have an absorption peak between about 500 nm to about 520 nm, about 500 nm to about 505 nm, about 505 nm to about 510 nm, about 510 nm to about 515 nm, about 515 nm to about 520 nm, or any wavelength in a range bounded by any these ranges.
  • Some embodiments include the photoluminescent complex wherein the blue light absorbing xanthenoisoquinoline or derivative and the BODIPY moiety's spatial distance is adjusted through the linker complex, for transfer of the blue light absorbing xanthenoisoquinoline derivative's energy to the BODIPY moiety.
  • the present disclosure includes a photoluminescent complex (PLC), wherein the photoluminescent complex comprises a blue light absorbing xanthenoisoquinoline derivative, a linker complex, and a BODIPY moiety.
  • the linker complex covalently links the blue light absorbing xanthenoisoquinoline derivative and the BODIPY moiety.
  • the xanthenoisoquinoline 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 xanthenoisoquinoline 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 blue light absorbing xanthenoisoquinoline derivative, wherein the blue light absorbing xanthenoisoquinoline derivative may be of the following general formula: wherein R° and R 10 may be H, a C1-4 alkyl group (e.g. methyl, n-butyl, t-butyl, etc.), -CF3, optionally substituted aryl etc.), or -
  • R 10 is C1.4 alkyl, such as methyl, ethyl, n-propyl, isopropyl, butyl, t-butyl, etc.
  • R 10 is H.
  • R 10 is t-butyl.
  • R 10 may be an aryl moiety (e.g., unsubstituted phenyl, substituted phenyl, or optionally substituted aryl).
  • the photoluminescent complex comprises a linker complex, wherein the linker complex covalently links the blue light absorbing xanthenoisoquinoline derivative to the BODIPY moiety.
  • the linker complex may comprise a single bond between the xanthenoisoquinoline derivative and the BODIPY moiety.
  • the linker complex may comprise a substituted ester, an unsubstituted ester, a substituted ether, or an unsubstituted ether. In some embodiments, the linker complex may comprise an optionally substituted ester group.
  • the linker complex comprises a substituted ester group, wherein the
  • the linker complex may comprise an unsubstituted ester group
  • the linker complex may comprise and ether group, wherein the linker
  • the linker complex may be:
  • the linker complex may be:
  • the linker complex may be:
  • the photoluminescent complex of the current disclosure may comprise a BODIPY moiety.
  • the BODIPY moiety may have the following general formula: wherein X may be F or CN; wherein R 1 and R 6 may be independently H, a saturated or unsaturated alkyl group (e.g., a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, etc.), or an alkene group; wherein R 3 and R 4 may be independently H, a saturated or unsaturated alkyl group (e.g., a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, etc.), or an alkene group; wherein R 2 and R 5 may be independently H, alkyl, cycloalkyl, alkenyl, a cyano (-CN),
  • L may represent the linker complex comprising an optionally substituted ester or an optionally substituted ether linker.
  • the BODIPY moiety of the present disclosure may be a BODIPY moiety wherein R 1 , R 3 , R 4 and R 5 are each a methyl; R 2 and R 5 are each a substituted ester group, wherein the substituted ester group comprises a C1-C7 alkyl chain or a polyglycol chain; R 7 and R 8 are each an optionally substituted aryl, alkyl or ether; and L comprises a linker complex.
  • R 2 and R 5 may be independently In some embodiments, R 2 may be independently In some embodiments, R 2 may be independently In some embodiments, R 2 may be independently In some embodiments, R 2 may be independently In some embodiments, R 2 may be independently.
  • R 2 may
  • R 2 may
  • R 2 may
  • R 5 may b
  • R 5 may b
  • R 5 may b
  • R 5 may
  • R 7 and R 8 may be independently optionally substituted aryl.
  • the optionally substituted aryl group may be an optionally substituted phenyl group.
  • the optionally substituted benzyl group may be an unsubstituted phenyl group, an unsubstituted diphenyl group, and or a C3-12 alkyl ester group.
  • R 7 and R 8 may be independently a phenyl group, a 3,5-difluorophenyl dichlorophenyl group 3,5-di-t-butylphenyl group ( group bis-3,5-di(2- ethylhexyl) 3,5- bis((perfluorophenyl)methyl)isophthalate group (
  • R 7 and R 8 may be independently a C 2 -8 alkyl group (e.g., ethyl, pentyl,
  • a C 3.8 cycloalkyl e.g., cyclopropyl, cyclohexyl, etc.
  • an ether group having a C1-10 alkyl group e.g. -OCH3, -O-(2-ethylhexyl), O CH2-cyclohexyl,
  • the photoluminescent complex of the present disclosure may be represented by the following which are provided for purpose of illustration and are in no way to be construed as limiting:
  • 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 comprise one or more of the complexes described herein.
  • the color conversion film which may be about 1 ⁇ m to about 200 ⁇ m thick.
  • the color conversion film has a thickness of about 1 ⁇ m to about 5 ⁇ m, about 5 ⁇ m to about 10 ⁇ m, about 10 ⁇ m to about 15 ⁇ m, about 15 ⁇ m to about 20 ⁇ m, about 20 ⁇ m to about 40 ⁇ m, about 40 ⁇ m to about 80 ⁇ m, about 80 ⁇ m to about 120 ⁇ m, about 120 ⁇ m to about 160 ⁇ m about 160 ⁇ m to about 200 ⁇ m, or any thickness in a range bounded by any of these values.
  • the color conversion film may absorb light in the wavelength range of about 400 nm to about 480 nm and may emit light in the wavelength range of about 500 nm to about 560 nm.
  • the color conversion film may further comprise a transparent substrate layer.
  • the transparent substrate layer has two opposing surfaces, wherein the color conversion layer may be disposed on and in physical contact with the 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 (polymethyl acrylate), PMMA (Polymethylmethacrylate), CAB (cellulose acetate butyrate), PVC (polyvinylchloride), PET (polyethyleneterephthalate), PETG (glycol modified polyethylene terephthalate), PDMS (polydimethylsiloxane), COC (cyclo olefin copolymer), PGA (polyglycolide or polyglycolic acid), PLA (polylactic acid), PCL (polycaprolactone), PEA (polyethylene adipate), PHA (polyhydroxy alkanoate), PHBV (poly(3-hydroxybutyrate-co-3hydroxyvalerate)), PBE (polybutylene terephthalate), 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 color conversion film comprises a singlet oxygen quencher. In some embodiments the color conversion film comprises a radical scavenger.
  • 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, polyvinylphosphonic 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; cycloalkanes, such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane; alcohols, such as ethanol, propanol, butanol, amyl alcohol, hexanol, heptanol, octanol, decanol, undecanol, diacetone alcohol, and furfuryl alcohol; 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 mono
  • Some embodiments include a backlight unit, wherein the backlight unit may include the aforedescribed color conversion film.
  • inventions include a display device, wherein the 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.”
  • the photoluminescent complex may have a Stokes shift that is equal to or greater than 45 nm” should be interpreted as, for example, “In some embodiments, the photoluminescent complex will have a Stokes shift that is equal to or greater than 45 nm,” or “In some embodiments, the photoluminescent complex will not have a Stokes shift that is equal to or greater than 45 nm.”
  • Embodiment 1 A photoluminescent complex comprising: a blue light absorbing moiety; a linker complex; and a boron-dipyrromethene (BODIPY) moiety, wherein the BODIPY moiety is of the general formula: , wherein R 1 and R 6 are independently H, alkyl, cycloalkyl, or alkenyl; wherein R 3 and R 4 are independently selected from a C1-C2 alkyl; wherein R 2 and R 5 are independently selected from H, alkyl, cycloalkyl, alkenyl, a cyano (-CN), an alkyl ester (-COOCH2CH3), an aryl ester (-COOCH z Ar), or EtO 2 C; and wherein R 7 and R 8 is optionally substituted aryl; wherein the linker complex covalently links the blue light absorbing moiety and the BODIPY moiety, wherein the blue light absorbing moiety absorbs light energy of a first ex
  • Embodiment 2 The photoluminescent complex of embodiment 1, wherein the R 7 and R 8 substituted aryl is independently selected from
  • Embodiment 3 The photoluminescent complex of embodiment 1, wherein the blue light absorbing moiety is a xanthenoisoquinoline derivative.
  • Embodiment 4 The photoluminescent complex of embodiment 2, wherein the xanthenoisoquinoline derivative is of the general formula: , wherein R° is independently selected from H, C1-C3 alkyl, optional substituted aryl, or optional substituted heteroaryl.
  • Embodiment 5 The photoluminescent complex of embodiment 1, wherein the BODIPY moiety is of the general formula: , wherein R 1 and R 6 are independently selected from H, a saturated or unsaturated alkyl group, or an alkene group; wherein R 3 and R 4 are independently selected from a Ci-C 2 alkyl; wherein R 2 and R 5 are independently selected from H, alkyl, cycloalkyl, alkenyl, a cyano (-CN ), an alkyl ester (-COOCH2CH3), an aryl ester (-COOCH2Ar), or EtO 2 C; and wherein R 7 and R s is a substituted aryl.
  • R 1 and R 6 are independently selected from H, a saturated or unsaturated alkyl group, or an alkene group
  • R 3 and R 4 are independently selected from a Ci-C 2 alkyl
  • R 2 and R 5 are independently selected from H, alkyl, cycloalkyl, alken
  • Embodiment 6 The photoluminescent complex of embodiment 6, wherein R 1 , R 3 , R 4 , and R 6 are independently selected from a C1-C3 alkyl or a methyl group; wherein R 2 and R 5 are independently selected from a C1-C3 ester group or a CH3CH2CO2 ester.
  • Embodiment 7 The photoluminescent complex of embodiment 10, wherein the unsubstituted ester comprises one of the following structures:
  • Embodiment 8 The photoluminescent complex of embodiment 10, wherein the substituted
  • Embodiment 9 The photoluminescent complex of embodiment 10, wherein the unsubstituted and/or substituted ether comprises one of the following structures:
  • Embodiment 10 The photoluminescent complex as in embodiments 1, 2, 3, 4, 5, 6, 7 , 8, or 9, wherein the photoluminescent complex comprises one of the following structures:
  • Embodiment 11 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, wherein the photoluminescent compound comprises the photoluminescent complex as in embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, dispersed within the resin matrix.
  • Embodiment 12 The color conversion film of embodiment 11, further comprising a singlet oxygen quencher.
  • Embodiment 13 The color conversion film of embodiment 11, further comprising a radical scavenger.
  • Embodiment 14 The color conversion film of embodiment 11, wherein the color conversion film has a thickness of between 10 ⁇ m and 200 ⁇ m.
  • Embodiment 15 The color conversion film of embodiment 11, wherein the color conversion film absorbs light in about 400 nm to about 480 nm wavelength range and emits light in the 500 nm to about 560.
  • Embodiment 16 A method for preparing the color conversion film as in embodiments 12, 13, or 15, the method comprising: dissolving the photoluminescent complex as in embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, and a binder resin within a solvent; and applying the mixture to one of the transparent substrates opposing surfaces.
  • Embodiment 17 A backlight unit comprising the color conversion film as in embodiments 11,, 13, 14, or 15.
  • Embodiment 18 A display device including the back-light unit of embodiment 17.
  • Example 1 Comparative Examples (CE) and Photoluminescent Compounds (PLC)
  • CE-l 0.75 g of 4-hydoxyl-2,6-dimethylvenzaldehyde (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. (2.0g) was added and the mixture was stirred overnight. The next day the solution was filtered and then washed with dichloromethane resulting in a dipyrrolemethane (1.9g).
  • Comparative Example 2 (CE-2): was synthesized as described in Wakamiya, Atsushi et al. Chemistry
  • reaction mixture was stirred at room temperature to give a yellow slurry. With stirring at room temperature, added DIC (9.047 mmol, 1.41 mL). The reaction mixture was stirred at room temperature for 60 minutes, then diluted with hexanes 1:1 and loaded onto ⁇ 60g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (220g, equilibrate 0% EtOAc/hexanes, eluting 0% 2 CV -> 20% EtOAc/hexanes (22 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a yellow solid, 5.182 g (86% yield).
  • PLC-1 diethyl 10-(5'-(2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-3,3",5,5"-tetra-tert-butyl-[l,l':3',l"-terphenyl]-2'-yl)-5,5- difluoro-l,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8- dicarboxylate): A 250 mL 2N round bottom flask was charged with a stir bar and fitted with a finned condenser/gas adapter and flow control.
  • the reaction mixture was cooled to room temperature and treated with DDQ. (44 mg, 0.1914 mmol) and stirred at room temperature for 20 minutes.
  • Et3N (0.16 mL, 1.178 mmol), and BF3.OEt2 (0.22 mL, 1.767 mmol) was repeated, then the reaction mixture was stirred for one hour at 50 ° C.
  • the crude reaction mixture was evaporated in vacuo onto ⁇ 15g of flash silica gel and packed into a lloader.
  • Bis(2-ethylhexyl) 5-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)isophthalate The aryl bromide from the previous step ( ⁇ 90% purity, 5.678 g, 12.09 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(l,3,2- dioxaborolane) (3.378g, 13.30 mmol), KOAc (3.561 g, 36.28 mmol), and Pd(dppf)Cl2 (266 mg, 0.3628 mmol) were combined in dry dioxane (100 mL) and heated at 80 ° C under argon for three hours.
  • Tetrakis(2-ethylhexyl) 2'-formyl-5'-hydroxy-[l,l':3',l"-terphenyl]-3,3",5,5"-tetracarboxylate) The aryl boronate from the previous step (1845 mg, 3.572 mmol), 2,6-dibromo-4-hydroxybenzaldehyde (250 mg, 0.8931 mmol), sodium bicarbonate (450 mg, 5.359 mmol), and Pd (dppf)CI 2 (131 mg, 0.1786 mmol) were combined in THF (45 mL) and water (3 mL) and heated at 80 ° C under argon overnight.
  • PLC-3 Tetrakis(2-ethylhexyl) 5'-(2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH- xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2'-(2,8-bis(ethoxycarbonyl)-5,5-difluoro- l,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinin-10-yl)-[l,l':3',l"- terphenyl]-3,3",5,5"-tetracarboxylate: The aldehyde from the previous step (mixture, 136 mg, 0.1077 mmol), ethyl 2,4-dimethyl-lH-pyr
  • SI reaction was cooled to room temperature and treated with DDQ (26 mg, 0.1144 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with Et 3 N (0.098 mL, 0.7041 mmol), and BF 3 .OEt 2 (0.13 mL, 1.056 mmol). The addition of Et 3 N (0.098 mL, 0.7041 mmol), and BF 3 .OEt 2 (0.13 mL, 1.056 mmol)) was repeated and the reaction mixture was stirred for one hour at 50 ° C. The reaction mixture was evaporated onto ⁇ 30g of flash silica gel in vacuo and packed into a loader.
  • the reaction mixture was treated with DDQ (55 mg, 0.2428 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with Et 3 N (0.18 mL, 1.295 mmol), and BF 3 .OEt2 (0.24 mL, 1.942 mmol). The addition of EtsN (0.18 mL, 1.295 mmol), and BF3.OEt2 (0.24 mL, 1.942 mmol) was repeated and the reaction mixture was stirred for one hour at 50 ° C. The crude reaction mixture was diluted 1:1 with hexanes and loaded onto ⁇ 25g of flash silica gel packed into a loader.
  • the reaction mixture was cooled to room temperature and titrated to pH ⁇ 1 with 6N HCI solution.
  • the reaction mixture was partition between ether (150 mL), the layers separated, extracted with DCM (150 mL), the combined organic layers dried over magnesium sulfate, filtered, and evaporated to dryness in vacuo.
  • the crude product was evaporated in vacuo onto ⁇ 40g of flash silica gel and packed into a loader. Purified by flash chromatography on silica gel (120g, 0% EtOAc/hexanes (2 CV) 20% (30 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a white solid, 889 mg (75% yield).
  • the reaction mixture was treated with DDQ. (379 mg, 1.672 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with Et 3 N (0.80 mL, 5.702 mmol), and BF 3 .OEt 2 (1.06 mL, 8.552 mmol). The addition of Et 3 N (0.80 mL, 5.702 mmol), and BF 3 .OEt2 (1.06 mL, 8.552 mmol) was repeated and the reaction mixture was stirred for one hour at 50 ° C. The crude reaction mixture was evaporated in vacuo onto ⁇ 45g of flash silica gel and packed into a loader.
  • Tetrakis((perfluorophenyl)methyl) 2'-formyl-5'-hydroxy-[l,l':3',l"-terphenyl]-3,3",5,5"- tetracarboxylate The aryl boronic acid from the previous step (2678 mg, 4.106 mmol), 2,6-dibromo- 4-hydroxybenzaldehyde (460 mg, 1.642 mmol), sodium bicarbonate (828 mg, 9.854 mmol), and Pd(dppf)CI 2 (240 mg, 0.3285 mmol) were combined in THF (100 mL) and water (16 mL) and heated at 80 ° C under argon for four hours.
  • PLC-6 Tetrakis((perfluorophenyl)methyl) 5'-(2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3- dioxo-lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2'-(2,8-bis(ethoxycarbonyl)-5,5- difluoro-l,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinin-10-yl)-[l,l':3',l"- terphenyl]-3,3",5,5"-tetracarboxylate: The dipyrrole from the previous step (575 mg, 0.2493 mmol) was dissolved in dry DCE (50 mL) and treated with DDQ.
  • tert-Butyl (2-oxobutyl)carbamate tert-Butyl (2-(methoxy(methyl)amino)-2-oxoethyl)carbamate
  • Ethyl 4-ethyl-2-methyl-lH-pyrrole-3-carboxylate Ethyl acetoacetate (10.7 mL, 84.10 mmol), sodium acetate (420.5 mmol, 34.494 g) and the salt from the prior step (assume 100% yield, 42.05 mmol) were dissolved in water (300 mL) and heated at 80 0 C with stirring for four hours. The heat was turned off and the reaction mixture stirred at room temperature over the weekend. The reaction was filtered, wash with water, the crude product dissolved in DCM, separated from water, dried over magnesium sulfate, filtered, and evaporated to dryness in vacuo. Gives a brown solid, 6.859 g (90% yield).
  • Tetra-tert-butyl-4'-formyl-l-phenol (872 mg, 1.750 mmol), 2-(4-(l,3-dioxo-5,ll-bis(4- (trifluoromethyl)phenyl)-lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (1490 mg, 2.100 mmol), DMAP.pTsOH salt (52 mg, 0.1750 mmol), and DIC (0.548 mL, 3.500 mmol) were stirred in dry DCM (50 mL) at room temperature for 30 minutes.
  • PLC-7 Diethyl l,9-diethyl-5,5-difluoro-3,7-dimethyl-10-(3,3",5,5"-tetra-tert-butyl-5'-(2-(4-(l,3- dioxo-5,ll-bis(4-(trifluoromethyl)phenyl)-lH-xantheno[2,l,9-def]isoquinolin-2(3H)- yl)phenyl)acetoxy)-[l,l l :3',l"-terphenyl]-2 l -yl)-5H-4l4,5l4-dipyrrolo[l,2-c:2 l ,l l - f][l,3,2]diazaborinine-2,8-dicarboxylate: The aldehyde from the previous step (283 mg, 0.2000 mmol), Compound 1711-44 (91 mg, 0.5000 mmol), and pTsOH.H 2
  • the reaction was treated with DDQ (82 mg, 0.3600 mmol) and heating continued at 60 ° C for 30 minutes.
  • the reaction was treated with additional DDQ (82 mg, 0.3600 mmol) and heating continued at 60 ° C for another 30 minutes.
  • the reaction mixture was cooled to room temperature and treated with Et 3 N (0.22 mL, 1.600 mmol), and BF 3 .OEt 2 (0.30 mL, 2.400 mmol).
  • Et 3 N (0.22 mL, 1.600 mmol
  • BF 3 .OEt 2 0.30 mL, 2.400 mmol
  • PLC-8 Diethyl 3,7-diethyl-5,5-difluoro-l,9-dimethyl-10-(3,3",5,5"-tetra-tert-butyl-5'-(2-(4-(l,3- dioxo-5,ll-bis(4-(trifluoromethyl)phenyl)-lH-xantheno[2,l,9-def]isoquinolin-2(3H)- yl)phenyl)acetoxy)-[l,l':3',l"-terphenyl]-2'-yl)-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'- f][l,3,2]diazaborinine-2,8-dicarboxylate: 3,3",5,5"-Tetra-tert-butyl-2'-formyl-[l,l':3',l"-terphenyl]-
  • the reaction was treated with TMSCN (2.000 mmol, 0.25mL), then BF 3 .OEt 2 (0.1500 mmol, 0.019 mL). The reaction mixture was stirred at room temperature for a few minutes, then heated to 45 ° C for 120 minutes. The crude reaction mixture was poured into ⁇ 30 mL of saturated NaHCO 3 and stirred for a few minutes. The reaction was filtered through a polypropylene frit to retain water, eluting product with DCM. The eluent was evaporated to dryness in vacuo, dissolved in a small amount of DCM, and loaded onto ⁇ 15g of flash silica gel packed into a loader.
  • Ethyl 2-ethyl-4-methyl-lH-pyrrole-3-carboxylate Ethyl 3-oxopentanoate (100.0 mmol, 14.2 mL), aminoacetone hydrochloride (150.0 mmol, and 16.440 g), NaOAc (200.0 mmol, 16.406 g) were stirred in acetic acid (100 mL) and water (100 mL) at 100 °C over the weekend under argon. The reaction mixture was cooled to room temperature and most of the solvents were evaporated in vacuo. The mixture was partitioned between DCM (200 mL) and water (50 mL). The remainder of acetic acid was carefully quenched with 10% K 2 CO 3 solution.
  • the eluent was directed onto a 15g flash silica plug, eluting with DCM, then eluting with 33% acetone/DCM.
  • the solvents were evaporated to dryness in vacuo, dissolved in a small amount of DCM and loaded onto 15g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel stop at 12.0%, 13.0%, 13.6%, 14.0%, 14.5%, 15.1%, 15.5%, 16.0%, and 17.0%, isocratic at each step. Fractions containing product were evaporated to dryness in vacuo. The product was triturated with hot MeOH, cooled to room temperature, filtered off, washing with MeOH, dissolved in DCM, and evaporated to dryness.
  • PLC-11 Dimethyl 10-(5'-(2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH- xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-[l,l l :3',l"-terphenyl]-2 l -yl)-5,5-difluoro- 3,7-diisopropyl-l,9-dimethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8- dicarboxylate: The aldehyde from the previous step (0.4000 mmol, 441 mg), ethyl 2-isopropyl-4- methyl-lH-pyrrole-3-carboxylate (0.8000 mmol, 145 mg), and p
  • the reaction mixture was cooled to room temperature and DDQ (2.400 mmol, 545 mg) was added and stirred at room temperature for 10 minutes.
  • EtsN 3.200 mmol, 0.45 mL
  • BF3.OEt2 4.800 mmol, 0.59 mL
  • the addition of EtsN (3.200 mmol, 0.45 mL), and BFs.OEt? (4.800 mmol, 0.59 mL) was repeated and the reaction stirred at 70 °C for 24h.
  • the reaction mixture was cooled to room temperature and quenched with 10 mL water and stirred for 5 minutes.
  • the reaction mixture was filtered through a polypropylene frit to retain water.
  • the frit was eluted with DCM.
  • the organic eluent was evaporated to dryness in vacuo, dissolved in a small amount of DCM and loaded onto 15g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (120g, 0% acetone/hexanes (2 CV) -> 20% (5 CV), stopping gradient at 0.3%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, and 1.1%).
  • Fractions containing product were evaporated to dryness in vacuo.
  • the product was triturated with MeOH, filtered off, washed with MeOH, dissolved in DCM, and evaporated to dryness in vacuo. Gives an orange solid, 230 mg (39% yield).
  • PLC-12 Diethyl 10-(5'-(2-(4-(l,3-dioxo-5,ll-bis(4-(trifluoromethyl)phenyl)-lH-xantheno[2,l,9- def]75soquinoline-2(3H)-yl)phenyl)acetoxy)-[l,l':3’,l"-terphenyl]-2'-yl)-3,7-diethyl-5,5-difluoro- l,9-dimethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8-dicarboxylate: 2'-Formyl-
  • the reaction mixture was cooled to room temperature and treated with DDQ (0.4500 mmol, 102 mg) and stirred at room temperature for 10 minutes.
  • the reaction mixture was treated with EtgN (2.400 mmol, 0.33 mL), and BF3.OEt2 3.600 mmol, 0.44 mL) were added to the reaction.
  • the addition of EtgN (2.400 mmol, 0.33 mL), and BFa.OEtz 3.600 mmol, 0.44 mL) was repeated and the reaction stirred at 50 ° C for one hour.
  • the reaction mixture was cooled to room temperature and quenched with 10 mL water and stirred for 5 minutes.
  • the reaction mixture was filtered through a polypropylene frit to retain water.
  • the frit was eluted with DCM.
  • the organic eluent was evaporated to dryness in vacuo, dissolved in a small amount of DCM and loaded onto ⁇ 45g of flash silica gel packed into a loader.
  • Purified by flash chromatography on silica gel 120g, 0% acetone/hexanes (2 CV) -> 50% (5 CV), stopping gradient at 12.0%, then 13.0%, 13.6%, 14.0%, 14.5%, 14.9%, 15.1%, 15.5%, 16.0%, and 17.0%.
  • Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 205 mg (50% yield).
  • the reaction mixture was cooled to room temperature and treated with DDQ (0.9000 mmol, 204 mg) and stirred at room temperature for 10 minutes.
  • the reaction mixture was treated with Et 3 N (2.400 mmol, 0.33 mL), and BF 3 .OEt 2 3.600 mmol, 0.44 mL) were added to the reaction.
  • the addition of Et 3 N (2.400 mmol, 0.33 mL), and BF 3 .OEt 2 3.600 mmol, 0.44 mL) was repeated and the reaction stirred at 50 ° C for one hour.
  • the reaction mixture was cooled to room temperature and quenched with 10 mL water and stirred for 5 minutes.
  • the reaction mixture was filtered through a polypropylene frit to retain water.
  • the frit was eluted with DCM.
  • the organic eluent was evaporated to dryness in vacuo, dissolved in a small amount of DCM and loaded onto ⁇ 45g of flash silica gel packed into a loader.
  • Purified by flash chromatography on silica gel 80g, 0% stopping gradient at 11.1%, 12.5%, 13.4%, 14.5%, 15.5%, and 16.5%.
  • Fractions containing product were evaporated to dryness in vacuo.
  • Repurified load ontol5g of flash silica gel packed into a loader), 40g, 0% EtOAc/hexanes (2 CV) 35% (5 CV), stopping gradient at 21.6%, 22.1%, and 22.5%.
  • the reaction mixture was cooled to room temperature and treated with DDQ (0.6000 mmol, 136 mg) and stirred at room temperature for 10 minutes.
  • the reaction mixture was treated with Et 3 N (2.400 mmol, 0.33 mL), and BF 3 .OEt 2 3.600 mmol, 0.44 mL) were added to the reaction.
  • the addition of Et 3 N (2.400 mmol, 0.33 mL), and BF 3 .OEt2 3.600 mmol, 0.44 mL) was repeated and the reaction stirred at 50 °C for one hour.
  • the reaction mixture was cooled to room temperature and quenched with 10 mL water and stirred for 5 minutes.
  • the reaction mixture was filtered through a polypropylene frit to retain water.
  • the reaction mixture was cooled to room temperature and treated with DDQ (1.800 mmol, 409 mg) and stirred at room temperature for 10 minutes.
  • the reaction mixture was treated with Et 3 N (2.400 mmol, 0.33 mL), and BF3.OEt2 3.600 mmol, 0.44 mL) were added to the reaction.
  • the addition of Et 3 N (2.400 mmol, 0.33 mL), and BF3.OEt2 3.600 mmol, 0.44 mL) was repeated and the reaction stirred at 50 ° C for one hour.
  • the reaction mixture was cooled to room temperature and quenched with 10 mL water and stirred for 5 minutes.
  • the reaction mixture was filtered through a polypropylene frit to retain water.
  • Ethyl 2-butyl-4-methyl-lH-pyrrole-3-carboxylate Ethyl 3-oxoheptanoate (20.00 mmol, 3.55 mL) and aminoacetone hydrochloride (40.00 mmol, 4.384 g) were combined in water (100 mL) and 200 pf ethanol (50 ml) and heated to 80 °C for 300 minutes.
  • the crude reaction mixture was extracted with DCM (3 X 100 mL), dried over magnesium sulfate, filtered, and evaporated to dryness. The crude mixture was dissolved in DCM and loaded onto ⁇ 40g of flash silica gel packed into a loader.
  • the reaction mixture was cooled to room temperature and DDQ (1.800 mmol, 409 mg) was added and stirred at room temperature for 10 minutes.
  • EtsN (2.400 mmol, 0.33 mL), and BF3.OEt2 3.600 mmol, 0.44 mL) were added to the reaction.
  • EtsN (2.400 mmol, 0.33 mL), and BF3.OEt23.600 mmol, 0.44 mL) was repeated and the reaction stirred at 50 °C for 30 minutes.
  • the reaction mixture was cooled to room temperature and quenched with 10 mL water and stirred for 5 minutes
  • the reaction mixture was filtered through a polypropylene frit to retain water. The frit was eluted with DCM.
  • Ethyl 2-isobutyl-4-methyl-lH-pyrrole-3-carboxylate Ethyl 5-methyl-3-oxohexanoate (20.00 mmol, 3.56 mL) and aminoacetone hydrochloride (40.00 mmol, 4.384 g) were combined in water (100 mL) and 200 pf ethanol (50 ml) and heated to 80 °C for 300 minutes. The crude reaction mixture was extracted with DCM (3 X 100 mL), dried over magnesium sulfate, filtered, and evaporated to dryness. The crude mixture was dissolved in DCM and loaded onto ⁇ 40g of flash silica gel packed into a loader.
  • the reaction mixture was cooled to room temperature and treated with DDQ. (1.800 mmol, 409 mg) and stirred at room temperature for 10 minutes.
  • the reaction mixture was treated with Et 3 N (2.400 mmol, 0.33 mL), and BF 3 .OEt2 3.600 mmol, 0.44 mL) were added to the reaction.
  • the addition of Et 3 N (2.400 mmol, 0.33 mL), and BF 3 .OEt2 3.600 mmol, 0.44 mL) was repeated and the reaction stirred at 50 °C for one hour.
  • the reaction mixture was cooled to room temperature and quenched with 10 mL water and stirred for 5 minutes.
  • the reaction mixture was filtered through a polypropylene frit to retain water.
  • the reaction mixture was cooled to room temperature and DDQ. (0.6000 mmol, 136 mg) was added and stirred at room temperature for 10 minutes.
  • Et 3 N (2.400 mmol, 0.33 mL), and BF 3 .OEt 2 3.600 mmol, 0.44 mL) were added to the reaction.
  • Et 3 N (2.400 mmol, 0.33 mL), and BF 3 .OEt 2 3.600 mmol, 0.44 mL
  • the reaction mixture was cooled to room temperature and quenched with 10 mL water and stirred for 5 minutes.
  • the reaction mixture was filtered through a polypropylene frit to retain water.
  • Quinolin-6-ylmethyl 2,4-dimethyl-lH-pyrrole-3-carboxylate Quinolin-6-ylmethanol (15.00 mmol, 2388 mg), 2,4-dimethyl-lH-pyrrole-3-carboxylic acid (45.00 mmol, 6264 mg), and DMAP.pTsOH salt (45.00 mmol, 13.247 g) were stirred in dry DMF (40 mL) heated to 100 °C under argon atmosphere. To the reaction was added EDC.HCI (90.00 mmol, 17.203 g), rinsed down by 10 mL dry DMF. The reaction mixture was heated to 130 ° C and stirred for 60 minutes. The reaction was cooled to room temperature and evaporated to dryness in vacuo.
  • the reaction was treated with DDQ. (0.5000 mmol, 114 mg) and stirred for 10 minutes.
  • Et 3 N 2.000 mmol, 0.28 mL
  • BF 3 .OEt 2 3.000 mmol, 0.37 mL
  • the reaction mixture was cooled to room temperature and quenched with 10 mL water and stirred for 5 minutes.
  • the reaction mixture was filtered through a polypropylene frit to retain water. The frit was eluted with DCM.
  • the organic eluent was evaporated to dryness in vacuo, dissolved in a small amount of DCM and loaded onto 15g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (120g, 0% acetone/hexane (2 CV) -> 30% (5 CV), stopping gradient at 12.0%, 13.0%, and 14.0%. Fractions containing product were evaporated to dryness in vacuo. The product was triturated with MeOH/water, filtered, washed with MeOH/water, dissolved in DCM, and evaporated to dryness in vacuo. Gives an orange solid, 188 mg (42% yield).
  • Photoluminescent Compound PLC-20 2-(9H-Carbazol-9-yl)ethyl 2,4-dimethyl-lH-pyrrole-3-carboxylate: 2-(9H-Carbazol-9-yl)ethan-l-ol (15.00 mmol, 2388 mg), 2,4-dimethyl-lH-pyrrole-3-carboxylic acid (45.00 mmol, 6264 mg), and DMAP.pTsOH salt (45.00 mmol, 13.247 g) were stirred in dry DMF (40 mL) heated to 100 °C under argon atmosphere. To the reaction was added EDC.HCI (90.00 mmol, 17.203 g), rinsed down by 10 mL dry DMF.
  • PLC-20 (Bis(2-(9H-carbazol-9-yl)ethyl) 5,5-difluoro-l,3,7,9-tetramethyl-10-(3,3",5,5"-tetra-tert- butyl-5'-(2-(4-(l,3-dioxo-5,ll-bis(4-(trifluoromethyl)phenyl)-lH-xantheno[2,l,9-def]isoquinolin- 2(3H)-yl)phenyl)acetoxy)-[l,l':3',l"-terphenyl]-2'-yl)-5H-4l4,5l4-dipyrrolo[l,2-c:2 l ,l l - f][l,3,2]diazaborinine-2,8-dicarboxylate: 3,3",5,5"-Tetra-tert-butyl-2'-formyl-[l,l':3',l"-
  • the reaction was treated with DDQ. (0.5000 mmol, 114 mg) and stirred for 10 minutes.
  • Et 3 N 2.000 mmol, 0.28 mL
  • BF 3 .OEt 2 3.000 mmol, 0.37 mL
  • the reaction mixture was cooled to room temperature and quenched with 10 mL water and stirred for 5 minutes.
  • the reaction mixture was filtered through a polypropylene frit to retain water. The frit was eluted with DCM.
  • the organic eluent was evaporated to dryness in vacuo, dissolved in a small amount of DCM and loaded onto 15g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (120g, 0% acetone/hexane (2 CV) -> 15% (5 CV), stopping gradient at 4.9%, back to 4.4%. Fractions containing product were evaporated to dryness in vacuo. The product was triturated with MeOH/water, filtered, washed with MeOH/water, dissolved in DCM, and evaporated to dryness in vacuo. Gives an orange solid, 304 mg (65% yield).
  • the reaction mixture was treated with DDQ. (68 mg, 0.3000 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with Et 3 N (0.22 mL, 1.600 mmol), and BF 3 .OEt 2 (0.30 mL, 2.400 mmol). The addition of Et 3 N (0.22 mL, 1.600 mmol), and BF 3 .OEt 2 (0.30 mL, 2.400 mmol) was repeated and the reaction mixture was stirred for one hour at 50 °C. The crude reaction mixture was evaporated in vacuo onto ⁇ 30g of flash silica gel and packed into a loader.
  • the reaction mixture was diluted with DCM (to 100 mL) and washed with 6N HCI (50 mL), 10% potassium carbonate solution (50 mL), dried over magnesium sulfate, filtered, and evaporated to dryness.
  • the crude product was dissolved in hexanes and loaded onto ⁇ 40g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (120g, 0% EtOAc/hexanes (2 CV) -> 10% (20 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a light yellow oil, 2.533 g (77% yield).
  • reaction mixture was stirred at 0 °C for five minutes, then the cooling bath was removed and the reaction mixture stirred at room temperature overnight.
  • the reaction mixture was cooled to -78 ° C and treated dropwise with dry DMF (5.8 mL, 75.07 mmol).
  • the reaction mixture was stirred at -78 ° C for a few minutes, then the cooling bath was removed and the reaction allowed to warm to room temperature with stirring.
  • the stirring was continued for one hour, then the reaction mixture was quenched with sat. NH4CI solution (150 mL) and partitioned with ether (200 mL). The layers were separated and the aqueous layer was extracted with ether (100 mL).
  • the reaction mixture was treated with DDQ. (331 mg, 1.459 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with EtsN (0.96 mL, 6.865 mmol), and BF3.OEt2 (0.87 mL, 7.061 mmol). The addition of EtsN (0.96 mL, 6.865 mmol), and BF3.OEt2 (0.87 mL, 7.061 mmol) was repeated and the reaction mixture was stirred for one hour at 50 °C. The crude reaction mixture was evaporated onto ⁇ 40g of flash silica gel in vacuo.
  • 3,5-Bis(3-phenylpropoxy)phenol Benzene-l,3,5-triol (7.567 g, 60.00 mmol), (3- bromopropyl)benzene (18.2 mL, 120.0 mmol), and potassium carbonate (16.585 g, 120.0 mmol) were stirred in dry DMF (50 mL) under argon at 50 °C for three hours. The reaction was cooled to room temperature and partitioned between water (200 mL) and ether (200 mL). The reaction was carefully titrated to pH ⁇ 6.5 with 6N HCI, then the layers were separated.
  • the reaction mixture was treated with DDQ. (347 mg, 1.527 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with Et 3 N (0.95 mL, 6.785 mmol), and BF 3 .OEt 2 (1.25 mL, 10.18 mmol). The addition of Et 3 N (0.95 mL, 6.785 mmol), and BF 3 .OEt 2 (1.25 mL, 10.18 mmol) was repeated and the reaction mixture was stirred for one hour at 50 °C. The crude reaction mixture was evaporated in vacuo onto ⁇ 40g of flash silica gel and packed into a loader.
  • 2,6-Bis(cyclohexylmethoxy)-4-hydroxybenzaldehyde 3,5-Bis(cyclohexylmethoxy)phenol (3.150 g, 9.891 mmol) was dissolved in dry DCM (6 mL) under argon and stirred at room temperature. The reaction mixture was treated with POCI 3 (1.84 mL, 3.033 mmol) and stirred for five minutes at room temperature, then cooled to 0 °C and treated dropwise with dry DMF (0.92 mL, 11.87 mmol). The reaction mixture was stirred at 0 °C for one hour, then the contents of the reaction dumped into ⁇ 100 mL of crushed ice, rinsing with a small amount of acetone.
  • the reaction mixture was titrated to pH ⁇ 6- 7 with 10% potassium carbonate solution, then extracted with DCM (100 mL, 2 X 50 mL). The combined organic layers were dried over magnesium sulfate, filtered, and evaporated to dryness in vacuo.
  • the crude product was diluted with a small amount of DCM and loaded onto ⁇ 50g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (120g, 0% EtOAc/hexanes (2 CV) -> 100% EtOAc (15 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives 175 mg (5.1% yield).
  • the reaction mixture was treated with DDQ (912 mg, 4.017 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with Et 3 N (2.5 mL, 17.85 mmol), and BF 3 .OEt 2 (3.31 mL, 26.78 mmol). The addition of Et 3 N (2.5 mL, 17.85 mmol), and BF 3 .OEt2 (3.31 mL, 26.78 mmol) was repeated and the reaction mixture was stirred for one hour at 50 °C. The crude reaction mixture was cooled to room temperature and evaporated onto ⁇ 55g of flash silica gel in vacuo.
  • 2,6-Bis(2-ethylhexyl)-4-hydroxybenzaldehyde (380 mg, 1.358 mmol) was dissolved in dry THF (25 mL) and treated with Pd(dppf)CI2 (199 mg, 0.2716 mmol) and stirred under argon at room temperature. The solution was sparged with argon, then (2- ethylhexyl)zinc(ll) bromide (0.5M in THF, 16.3 mL, 8.148 mm) was added and the reaction mixture stirred at room temperature for five minutes. The reaction mixture was heated at 40 °C overnight.
  • the reaction mixture was cooled to room temperature and treated with DDQ. (275 mg, 1.212 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with Et 3 N (0.80 mL, 5.702 mmol), and BF 3 .OEt 2 (1.06 mL, 8.552 mmol). The addition of Et 3 N (0.80 mL, 5.702 mmol), and BF 3 .OEt 2 (1.06 mL, 8.552 mmol) was repeated and the reaction mixture was stirred for one hour at 50 " C. The reaction mixture was evaporated onto ⁇ 45g of flash silica gel and evaporated to dryness in vacuo.
  • reaction mixture was cooled to room temperature, then quenched with sat NH 4 CI solution (50 mL), followed 6N HCI (25 mL).
  • the reaction mixture was extracted with ethyl acetate (100 mL, 3 X 50 mL).
  • the combined organic layers were dried over magnesium sulfate, filtered, and evaporated to dryness in vacuo.
  • the crude product was evaporated onto ⁇ 40g of flash silica gel in vacuo and packed into a loader. Purified by flash chromatography on silica gel (120g, 0% acetone/hexanes (2 CV) 40% (20 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives an off-white solid, 120 mg (30% yield).
  • the reaction mixture was treated with DDQ. (60 mg, 0.2642 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with Et 3 N (0.20 mL, 1.409 mmol), and BF 3 .OEt 2 (0.26 mL, 2.114 mmol). The addition of Et 3 N (0.20 mL, 1.409 mmol), and BF 3 .OEt 2 (0.26 mL, 2.114 mmol) was repeated and the reaction mixture was stirred for one hour at 50 °C. The crude reaction mixture was evaporated onto ⁇ 30g of flash silica gel in vacuo.
  • 2,6-Bis(cyclohexylmethyl)-4-hydroxybenzaldehyde 2,6-Dibrorrio-4-hydroxybenzaldehyde (1120 mg, 4.000 mmol) and Pd(dppf)CI 2 (585 mg, 0.8000 mmol) were combined in dry THF (50 mL) and stirred at room temperature under argon. The reaction mixture was sparged thoroughly with argon, then (cyclohexylmethyl)zinc(ll) bromide (0.5M in THF, 32.0 mL, 16.00 mmol) was added and the reaction mixture further sparged with argon. The reaction mixture was stirred at room temperature for five minutes, then heated to 40 °C overnight.
  • reaction mixture was cooled to room temperature and partitioned between water (100 mL) and ether (100 mL). The layers were separated and the aqueous layer was extracted with ether (100 mL). The combined organic layers were dried over magnesium sulfate, filtered, and evaporated to dryness in vacuo.
  • the crude reaction mixture was evaporated onto ⁇ 20 g of flash silica gel in vacuo and packed into a loader. Purified by flash chromatography on silica gel (0% EtOAc/hexanes (2 CV) -> 20% (15 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives an off-white solid, 833 mg (66% yield).
  • the reaction mixture was treated with DDQ. (513 mg, 2.262 mmol) and stirred at room temperature for 30 minutes. Additional DDQ (86 mg, 0.3371 mmol) was added twice at fifteen and 30 minutes, then the reaction mixture stirred for an additional 30 minutes.
  • the reaction was then treated with Et 3 N (1.4 mL, 10.05 mmol), and BF 3 .OEt 2 (1.87 mL, 15.08 mmol). The addition of Et 3 N (1.4 mL, 10.05 mmol), and BF 3 .OEt 2 (1.87 mL, 15.08 mmol) was repeated and the reaction mixture was stirred for one hour at 50 °C.
  • 2,6-Dicyclohexyl-4-hydroxybenzaldehyde 1,6-Dibromo-4-hydroxybenzaldehyde (1120 mg, 4.000 mmol) and PDFdppfJCh (585 mg, 0.8000 mmol) were combined in dry THF (50 mL) and stirred at room temperature under argon. The reaction mixture was sparged thoroughly with argon, then cyclohexylzinc(ll) bromide (0.5M in THF, 32.0 mL, 16.00 mmol) was added and the reaction mixture further sparged with argon. The reaction mixture was stirred at room temperature for five minutes, then heated to 40 °C overnight. The reaction mixture was heated at 80 °C for six hours, then cooled to room temperature.
  • the reaction mixture was treated with DDQ. (106 mg, 0.4686 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with Et 3 N (0.29 mL, 2.083 mmol), and BF 3 .OEt 2 (0.39 mL, 3.124 mmol). The addition of Et 3 N (0.29 mL, 2.083 mmol), and BF 3 .OEt 2 (0.39 mL, 3.124 mmol) was repeated and the reaction mixture was stirred for one hour at 50 °C. The crude reaction mixture was evaporated onto ⁇ 25g of flash silica gel in vacuo and packed into a loader.
  • PLC-31 Diethyl 10-(4-(2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dicyclohexylphenyl)-5,5-difluoro-3,7-dimethyl-5H- 4l4,5l4-dipyrrolo[l,2-c:2',r-f][l,3,2]diazaborinine-2,8-dicarboxylate: 3,5-Dicyclohexyl-4- formylphenyl-2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)pheny
  • 2,6-Dibromo-4-(methoxymethoxy)benzaldehyde 2,6-Dibromo-4-hydroxybenzaldehyde (5.598 g, 20.00 mmol) and potassium carbonate (5528 mg, 40.00 mmol) were combined in dry THF (100 mL) and stirred under argon. To the flask was added MOM-CI (1.97 mL, 26.00 mmol). The reaction mixture was stirred at room temperature overnight. The crude reaction mixture was evaporated in vacuo onto ⁇ 60g of flash silica gel and packed into a loader.
  • the reaction mixture was treated with DDQ. (230 mg, 1.014 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with Et 3 N (0.63 mL, 4.508 mmol), and BF3.OEt2 (0.83 mL, 6.763 mmol). The addition of Et 3 N (0.63 mL, 4.508 mmol), and BF 3 .OEt2 (0.83 mL, 6.763 mmol) was repeated and the reaction mixture was stirred for one hour at 50 ° C. The crude reaction mixture was evaporated in vacuo onto ⁇ 60g of flash silica gel and packed into a loader.
  • reaction was stirred room temperature for a few minutes, then heated to 45 °C for 60 minutes.
  • the reaction mixture was poured into ⁇ 30 mL of saturated NaHCO 3 and stirred for a few minutes.
  • the reaction was filtered through a polypropylene frit to retain water, eluting product with DCM.
  • the eluent was evaporated to dryness in vacuo, dissolved in a small amount of DCM, and loaded onto ⁇ 15g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (80g, 0% acetone/hexane (2 CV) 35% (5 CV), stopping gradient at 26.6%. Fractions containing product were evaporated to dryness in vacuo.
  • PLC-34 Dimethyl 10-(4-(2-(4-(l,3-dioxo-5,ll-bis(4-(trifluoromethyl)phenyl)-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dimethoxyphenyl)-5,5-difluoro-3,7-diisopropyl-l,9- dimethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8-dicarboxylate: The aldehyde from the previous step (0.4000 mmol, 404 mg), ethyl 2-isopropy-4-methyl-lH-pyrrole-3-carboxylate (0.8000 mmol, 145 mg), and PTSOH.H2O (0.08000 mmol) were stirred in dry DCE (25
  • EtsN (3.200 mmol, 0.45 mL), and BFs.0Et2 (4.800 mmol, 0.59 mL) were added to the reaction.
  • the addition of EtsN (3.200 mmol, 0.45 mL), and BF3.OEt2 (4.800 mmol, 0.59 mL) was repeated and the reaction stirred at 65 °C for 8 hours, then stirred at room temperature overnight.
  • the reaction was quenched with 5 mL of water and stirred for a few minutes, then filtered through a polypropylene frit to retain water. The frit was eluted with DCM.
  • the eluent was directed onto a 15g flash silica plug, eluting with DCM, then eluting with 33% acetone/DCM.
  • the solvents were evaporated to dryness in vacuo, dissolved in a small amount of DCM and loaded onto 15g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (120g, 0% EtOAc/DCM 20% (5 CV), stop at 4.0% eluting isocratic. Fractions containing product were evaporated to dryness in vacuo. The product was triturated with hot MeOH, cooled to room temperature, filtered off, washing with MeOH, dissolved in DCM, and evaporated to dryness in vacuo.
  • PLC-35 Dimethyl 10-(4-(2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dimethoxyphenyl)-5,5-dicyano-3,7-diisopropyl-l,9- dimethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8-dicarboxylate: PLC-34 (0.1500 mmol, 210 mg), TMSCN (1.500 mmol, 0.19 mL), and BF 3 .OEt 2 (0.2250 mmol, 0.028 mL) were stirred in dry DCE (10 mL) under argon at room temperature for a few minutes, then heated to
  • Example 2 Procedure to measure optical properties of sharp emitter chromophores
  • 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 (DI) water, rinsed with fresh DI water, and sonicated for about 1 hour. The glass was then soaked in isopropanol (I PA) 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.
  • DI detergent and deionized
  • I PA isopropanol
  • PMMA poly(methyl methacrylate) resin in spectroscopy grade toluene
  • the 1-inch X 1-inch sample was inserted into a Shimadzu, UV-3600 UV-VIS- NIR spectrophotometer (Shimadzu Instruments, Inc., Columbia, MD, USA) to measure absorption spectrum.
  • the fluorescence spectrum (emission spectrum) of a 1-inch X 1-inch film sample prepared as described above was determined using a Fluorologmax spectrofluorometer (Horiba Scientific, Edison, NJ, USA). Both 390nm and 450nm wavelengths were chosen as excitation wavelength.
  • the quantum yields of spin-coated samples as described above were determined using a Hamamatsu C11347 Absolute PL quantum yield spectrometer (Hamamatsu Inc., Campbell CA, USA). A 0.5"x 0.5" size film was taken out from glass substrate for QY measurement. Wavelengths were scanned every 30 nm from 390 nm to 450 nm (as excitation wavelengths). The QY at 450 nm are reported in Table 1.

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Abstract

The present disclosure relates to novel photoluminescent complex comprising a BODIPY moiety covalently bonded to a blue light absorbing moiety, 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
Inventors: Jeffrey R. Hammaker, Shijun Zheng, Tissa Sajoto, and Sadahiro Nakanishi
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. Provisional Patent Application No. 63/385,812, filed on December 2, 2022, and U.S. Provisional Patent Application No. 63/504,158, filed on May 24, 2023.
BACKGROUND
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 has increased. Current light emitting diodes (LEDs) are obtained by a blue light source exciting a green phosphor, a red phosphor or a yellow phosphor to obtain a white light source. However, the full width half maximum (FWHM) of the emission peak of the current green and red phosphors are quite large usually greater than 40 nm, resulting in the green and red color spectrums overlapping and rendering colors that are not fully distinguishable from one another. 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. Co-pending patent applications include at least Patent Cooperation Treaty Publication WO2022/178450, filed February 22,2022, PCT/US2022/017373; and PCT/US2022/076912, filed September 23, 2022). Therefore, there exists a need for improving performance in color conversion films, backlight units, and display devices.
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 provides novel color converting dye complex with good blue light absorbance and narrow emissions bandwidths, e.g., with a full width half maximum [FWHM] of emission band of less than 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 comprising a blue light absorbing moiety; a linker complex; and a boron-dipyrromethene (BODIPY) moiety.
In some embodiments, the blue light absorbing moiety is a xanthenoisoquinoline group of the general formula:
Figure imgf000004_0001
where R° comprises H, an alkyl group, -CF3, alkoxy, or optionally substituted aryl, and R10 comprises H, an alkyl group, -CF3, alkoxy, or optionally substituted aryl. In some examples, the dashed line comprises a covalent bond to the linker complex.
Some embodiments include a BODIPY moiety of the general formula:
Figure imgf000005_0001
, where X comprises F or CN, R1 and R6 and R3 and R4 comprise H, alkyl, cycloalkyl, alkenyl group, R2 and R5 comprise H, alkyl, cycloalkyl, a cyano (-CN) group, an alkyl ester group, or an aryl ester group; and R7 and R8 comprise optionally substituted aryl, a C2-8 alkyl group; a C3-8 cycloalkyl group; an ether group having a C110 alkyl group, an ether moiety having an optionally substituted aryl group, or a C1-10 arylalkyl group.
In some embodiments, the linker complex comprises an optionally substituted ester or an optionally substituted ether linker, where the linker complex covalently links the blue light absorbing moiety and the BODIPY moiety.
In other embodiments, the blue light absorbing moiety absorbs light energy of a first excitation wavelength and transfers an energy to the BODIPY moiety. In some examples, the BODIPY moiety absorbs the energy from the blue light absorbing moiety 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 examples, wherein R7 and R8 of the photoluminescent complex comprise optionally
Figure imgf000005_0002
In other examples, R7 and R8 of the photoluminescent complex comprise an optionally substituted alkyl group, an optionally substituted cycloalkyl group, or an optionally substituted ether group comprising pentyl, 2-ethylhexyl, cyclohexyl, CH2-cyclohexyl, -OCH3, -O-(2-ethylhexyl), -OCH2- cyclohexyl, -OPh, or -O(CH2)3-Ph.
Some embodiments include a photoluminescent complex where R1 and R6 comprise H, methyl, ethyl, propyl group, isopropyl, butyl, or isobutyl; and wherein R3 and R4 comprise H, methyl, ethyl, propyl group, isopropyl, butyl, or isobutyl.
Other embodiments include a photoluminescent complex where R2 and R5 comprise -
Figure imgf000006_0001
In other examples, R10 of the photoluminescent complex comprises H.
In some embodiments of the photoluminescent complex, the linker complex comprises
Figure imgf000006_0002
In some examples, X of the photoluminescent complex is F. In other cases, X of the photoluminescent complex is CN.
Some embodiments of the present disclosure comprise a color conversion film comprising. In some examples, the color conversion film comprises a transparent substrate layer and a color conversion layer comprising a resin matrix. In some embodiments, a photoluminescent compound described herein is dispersed within the resin matrix. In some embodiments, the color conversion film of the present disclosure may comprise a singlet oxygen quencher. In some embodiments, the color conversion film may further comprise a radical scavenger.
Some embodiments include a method for preparing the color conversion film, comprising: dissolving an aforedescribed photoluminescent complex and a binder resin within a solvent; and applying the mixture on a surface of the transparent substrate.
Some embodiments include a backlight unit including a color conversion film described herein.
Other embodiments include a display device including the backlight unit described herein.
The present application provides a photoluminescent complex 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 photostability of one embodiment of a photoluminescent complex (PLC-1) as compared to a comparative example (CE-3).
FIG. 2 is a graph depicting the absorption and emission spectra of one embodiment of a photoluminescent complex (PLC-21).
FIG. 3 is a graph depicting the absorption and emission spectra of one embodiment of a photoluminescent complex (PLC-25).
DETAILED DESCRIPTION
The present disclosure is related to photoluminescent compounds and complexes for use in color conversion films, backlight units, and display devices.
The current disclosure describes photoluminescent complexes and their uses in color conversion films. The photoluminescent complex 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. The present disclosure includes 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 of the parent structure have been independently replaced by one or more substituent groups. In one or more forms, the substituent groups may be independently selected from an optionally substituted Ci-8 alkyl, C3-8 alkenyl, or a C3-8 heteroalkyl.
An alkyl moiety may be branched, straight chain (i.e., unbranched), or cyclic. In some embodiments, the alkyl moiety may have 1 to 8 carbon atoms. The alkyl group of the compounds designated herein may be designated as "Ci-8 alkyl" or similar designations. By way of example only, "Ci-8 alkyl" indicates that there are 1, 2, 3, 4, 5, 6, 7, or 8 carbon atoms in the alkyl chain, i.e., the alkyl chain is methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, and any isomers thereof. Thus, Chalky I includes C1-2 alkyl, C1.3 alkyl, C1-4 alkyl, C1.5 alkyl, Ci-6 alkyl, Ci-7 alkyl, and Ci-8 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, ethenyl, propenyl, butenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.
The term "heteroalkyl" as used herein refers to an alkyl group, as defined herein, in which one or more of the constituent carbon atoms have been replaced by a nitrogen, oxygen, or sulphur. Examples include but are not limited to, -CH2-O-CH3, -CH2-CH2-O-CH3, -CH2-NH-CH3, -CH2-N(CH3)-CH3, -CH2-CH2-NH-CH3, -CH2-CH2-N(CH3)-CH3, -CH2-S-CH2-CH3, -CH2-CH2-S(O)-CH3. In addition, up to two heteroatoms may be consecutive, such as, by way of example, -CH2-NH-O-CH3, etc.
The term "aromatic" refers to a planar ring having a delocalized n-electron system containing 4n+2 n 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 ring or ring system that contains only carbon and hydrogen and may be saturated. Monocyclic hydrocarbon rings include groups having from 3 to 12 carbon atoms.
The term "aryl" as used herein refers to 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 group substituted with an aryl. Non-limiting aralkyl groups include benzyl, phenethyl; 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. It is understood that the heteroaryl ring may have additional heteroatoms in the ring. In heteroaryls that have two or more heteroatoms, those two or more heteroatoms may be the same or different from one another. Heteroaryl groups may be optionally substituted. An N-containing heteroaryl moiety refers to an aryl group in which a skeletal atom of the ring is a nitrogen atom. Illustrative examples of heteroaryl groups include the following moieties: pyrrole, imidazole, etc.
The term "halogen" as used herein refers to fluorine, chlorine, bromine, and iodine.
The term "bond", "bonded", "direct bond", "single bond", or "covalent bond" as used herein refers to a chemical bond between two atoms or to two moieties when the atoms joined by the bond are considered to be part of a larger structure.
The term "moiety" as used herein refers to a specific segment or functional group of a molecule. Chemical moieties are often recognized chemical entities embedded in or appended to a molecule.
The term "cyano" or "nitrile" as used herein refers to any organic compound that contains a - CN functional group.
The term "ester" refers to a chemical moiety with the formula -COOR, where R comprises alkyl, cycloalkyl, aryl, heteroaryl (bonded through a ring carbon) or heterocyclic (bonded through a ring carbon). Any hydroxy, or carboxyl side chain on the compounds described herein may be esterified. Any suitable procedures and specific groups to make such esters may be utilized.
As used herein the term "ether" refers to a chemical moiety that contains an oxygen atom connected to two alkyl or aryl groups with the general formula of R-O-R', where R and R' are alkyl and/or aryl. Similarly, the term "alkoxy" refers to a chemical moiety that contains an oxygen atom bonded to an alkyl group that is further bonded to an alkyl or aryl group.
As used herein the term "ketone" refers to the chemical moiety that contains a carbonyl group (a carbon-oxygen double bond) connected to two alkyl or aryl groups with the general formula of RC(=O)R', where R and R' are alkyl and/or aryl.
The term "BODIPY", as used herein, refers to a chemical moiety with the formula:
Figure imgf000009_0001
The BODIPY moiety may be composed of a dipyrromethene complexed with a di-substituted boron atom (BXz), typically a BF2or a B(CN)z unit. The IUPAC name for the BODIPY core (i.e., without any substituents, and without the aryl group opposite the BX2 group, wherein X=F) is 4,4-difluoro-4- bora-3a,4a-diaza-s-indacene.
The term "xanthenoisoquinoline" or "xanthenoisoquinoline derivative" as used herein, refers to a chemical moiety with the formula:
Figure imgf000010_0001
xantheno[2,l,9-def]isoquinoline-l,3(2H)-dione.
The present disclosure is related to photoluminescent complexes that absorb light energy of a first wavelength and emit 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, a photoluminescent complex comprises: a blue light absorbing moiety, a linker complex, and a boron-dipyrromethene (BO DI PY) moiety. In some embodiments, the blue light absorbing moiety is a xanthenoisoquinoline derivative. In some embodiments, the linker complex may covalently link the xanthenoisoquinoline derivative to the BODIPY moiety. In some embodiments, the xanthenoisoquinoline 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 xanthenoisoquinoline derivative to the BODIPY moiety occurs through a Forster resonance energy transfer (FRET). This belief is due to the absorbance/emission spectra of the photoluminescent complexes where there are two major absorption bands, one at the blue light absorption band (xanthenoisoquinoline derivative) and one at the BODIPY absorption band, and only one emission band located at the BODIPY moieties emission wavelength (see FIGS. 2 and 3).
In some embodiments, the photoluminescent complex may have a high emission quantum yield. In some embodiments, the emission quantum yield may be greater than 50%, 60%, 70%, 80%, or 90%. In some embodiments, the emission quantum yield may be greaterthan 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%. 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%), 0.81 (81%), 0.82 (82%), 0.83 (83%), 0.84 (84%), 0.85 (85%), 0.86 (86%), 0.87 (87%), 0.88 (88%), 0.89 (89%), 0.9 (90%), 0.91 (91%), 0.92 (92%), 0.93 (93%), 0.94 (94%), or 0.95 (95%), and may be up to nearly 1 (100%). Quantum yield measurements in film may be made by spectrophotometer, e.g., Quantaurus-QY spectrophotometer (Hamamatsu, Inc., Campbell, CA, USA).
In some embodiments, the photoluminescent complex has an emission band and 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, 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 45 nm. As used herein, the term "Stokes shift" means the distance between the excitation peak of the blue light absorbing moiety and the emission peak of the BODIPY moiety.
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 about 500 nm to about 560 nm or any number bound by this range.
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 embodiment, the peak absorption may be between about 400 nm to about 405 nm, about 405-410 nm, about 410-415 nm, about 415-420 nm, about 420-425 nm, about 425-430 nm, about 430-435 nm, about 435-440 nm, about 440-445 nm, about 445-450 nm, about 450-455 nm, about 455-460 nm, about 460-465 nm, about 465-470 nm, or any wavelength in a range bounded by any of these values.
In some embodiments, the photoluminescent complex may have an emission peak between about 500 nm and about 560 nm. In some embodiments, the emission peak may be between about 500 nm to about 515 nm, about 515 nm to about 520 nm, about 520 nm to about 525 nm, about 525 nm to about 530 nm, about 530 nm to about 535 nm, about 535 nm to about 540 nm, about 540 nm to about 545 nm, about 545 nm to about 550 nm, about 550 nm to about 555 nm, about 555 nm to about 560 nm, or any wavelength in a range bounded by any these ranges. In some embodiments, the photoluminescent complex may have an absorption peak between about 500 nm to about 520 nm, about 500 nm to about 505 nm, about 505 nm to about 510 nm, about 510 nm to about 515 nm, about 515 nm to about 520 nm, or any wavelength in a range bounded by any these ranges.
Some embodiments include the photoluminescent complex wherein the blue light absorbing xanthenoisoquinoline or derivative and the BODIPY moiety's spatial distance is adjusted through the linker complex, for transfer of the blue light absorbing xanthenoisoquinoline derivative's energy to the BODIPY moiety.
The present disclosure includes a photoluminescent complex (PLC), wherein the photoluminescent complex comprises a blue light absorbing xanthenoisoquinoline derivative, a linker complex, and a BODIPY moiety. The linker complex covalently links the blue light absorbing xanthenoisoquinoline derivative and the BODIPY moiety. In some embodiments, the xanthenoisoquinoline 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 xanthenoisoquinoline 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 blue light absorbing xanthenoisoquinoline derivative, wherein the blue light absorbing xanthenoisoquinoline derivative may be of the following general formula:
Figure imgf000012_0001
wherein R° and R10 may be H, a C1-4 alkyl group (e.g. methyl, n-butyl, t-butyl, etc.), -CF3, optionally substituted aryl
Figure imgf000012_0002
etc.), or -
(OCH2CH2)n-OCH3, wherein n is 1, 2, 3, or 4, or alkoxy, and wherein the dashed line represents the connection point of the xanthenoisoquinoline moiety to the linker complex. In some embodiments, R10 is C1.4 alkyl, such as methyl, ethyl, n-propyl, isopropyl, butyl, t-butyl, etc. In some examples, R10 is H. In some embodiments, R10 is t-butyl. In other embodiments, R10 may be an aryl moiety (e.g., unsubstituted phenyl, substituted phenyl, or optionally substituted aryl).
In some embodiments, the photoluminescent complex comprises a linker complex, wherein the linker complex covalently links the blue light absorbing xanthenoisoquinoline derivative to the BODIPY moiety. In some embodiments, the linker complex may comprise a single bond between the xanthenoisoquinoline derivative and the BODIPY moiety.
In some embodiments, the linker complex may comprise a substituted ester, an unsubstituted ester, a substituted ether, or an unsubstituted ether. In some embodiments, the linker complex may comprise an optionally substituted ester group.
In some embodiments, the linker complex comprises a substituted ester group, wherein the
Figure imgf000013_0001
In some embodiments, the linker complex may comprise an unsubstituted ester group,
Figure imgf000013_0002
In some embodiments, the linker complex may comprise and ether group, wherein the linker
Figure imgf000013_0003
Figure imgf000014_0001
In some embodiments, the linker complex may be:
Figure imgf000014_0002
In some embodiments, the linker complex may be:
Figure imgf000014_0003
Figure imgf000014_0004
Figure imgf000015_0003
In some embodiments, the linker complex may be:
Figure imgf000015_0001
The photoluminescent complex of the current disclosure may comprise a BODIPY moiety.
The BODIPY moiety may have the following general formula:
Figure imgf000015_0002
wherein X may be F or CN; wherein R1 and R6 may be independently H, a saturated or unsaturated alkyl group (e.g., a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, etc.), or an alkene group; wherein R3 and R4 may be independently H, a saturated or unsaturated alkyl group (e.g., a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, etc.), or an alkene group; wherein R2 and R5 may be independently H, alkyl, cycloalkyl, alkenyl, a cyano (-CN), an alkyl ester (e.g., ethyl ester, 2-ethyl-hexyl ester, 2,2,2-trifluoroeethyl ester, a glycol ester, etc.), or an aryl ester (e.g., a phenyl ester (-C(O)OCH2Ph), etc.); wherein R7 and R8 independently be optionally substituted aryl (e.g., phenyl, 3,5- bistrifluoromethylphenyl, 3,5-bis-t-butylphenyl, 3,5-bisfluorophenyl, 3,5-bischlorophenyl, biphenyl, etc.), C1-8 a Ikyl (e.g., ethyl, pentyl, 2-ethylhexyl, CH2-cyclohexyl, etc.), a C3.8 cycloalkyl (e.g., cyclopropyl, cyclohexyl, etc.), an ether group having a Ci-io alkyl group (e.g. -OCH3, -O-(2-ethylhexyl), OCH2- cyclohexyl, etc.), an ether moiety having an optionally substituted aryl group (e.g., -OPh), or a Ci-io arylalkyl group (e.g. -O(CH2)3-Ph, etc.); and wherein L may represent the linker complex comprising an optionally substituted ester or an optionally substituted ether linker.
In some embodiments, the BODIPY moiety of the present disclosure may be a BODIPY moiety wherein R1, R3, R4and R5 are each a methyl; R2 and R5 are each a substituted ester group, wherein the substituted ester group comprises a C1-C7 alkyl chain or a polyglycol chain; R7 and R8 are each an optionally substituted aryl, alkyl or ether; and L comprises a linker complex.
O
In some embodiments, R2 and R5 may be independently
Figure imgf000016_0001
Figure imgf000016_0002
In some embodiments, R2 may
Figure imgf000017_0001
In some embodiments, R2 may
Figure imgf000017_0002
In some embodiments, R2 may
Figure imgf000017_0003
In some embodiments,
Figure imgf000017_0004
In some embodiments,
Figure imgf000017_0005
In some embodiments, R2 may
Figure imgf000017_0006
In some embodiments, R5 may b
Figure imgf000017_0007
In some embodiments, R5 may b
Figure imgf000017_0008
In some embodiments, R5 may b
Figure imgf000017_0009
Figure imgf000018_0001
In some embodiments, R5 may
Figure imgf000018_0002
In some embodiments, R7 and R8 may be independently optionally substituted aryl. In some embodiments, the optionally substituted aryl group may be an optionally substituted phenyl group.
In some embodiments, the optionally substituted benzyl group may be an unsubstituted phenyl group, an unsubstituted diphenyl group, and or a C3-12 alkyl ester group.
In some embodiments, R7 and R8 may be independently a phenyl group, a 3,5-difluorophenyl dichlorophenyl group
Figure imgf000018_0003
3,5-di-t-butylphenyl group (
Figure imgf000018_0004
group
Figure imgf000018_0005
bis-3,5-di(2- ethylhexyl)
Figure imgf000019_0001
3,5- bis((perfluorophenyl)methyl)isophthalate group (
Figure imgf000019_0002
In some embodiments, R7 and R8 may be independently a C2-8 alkyl group (e.g., ethyl, pentyl,
2-ethylhexyl, CH2-cyclohexyl, etc.), a C3.8 cycloalkyl (e.g., cyclopropyl, cyclohexyl, etc.), an ether group having a C1-10 alkyl group (e.g. -OCH3, -O-(2-ethylhexyl), O CH2-cyclohexyl, etc.), an ether moiety having an optionally substituted aryl group (e.g., -OPh), or a C1-10 arylalkyl group (e.g. -O(CH2)3-Ph, etc.);.
The photoluminescent complex of the present disclosure may be represented by the following which are provided for purpose of illustration and are in no way to be construed as limiting:
Figure imgf000019_0003
Figure imgf000020_0001
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000023_0001
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
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 comprise one or more of the complexes described herein.
Some embodiments include the color conversion film which may be about 1 μm to about 200 μm thick. In some embodiments, the color conversion film has a thickness of about 1 μm to about 5 μm, about 5 μm to about 10 μm, about 10 μm to about 15 μm, about 15 μm to about 20 μm, about 20 μm to about 40 μm, about 40 μm to about 80 μm, about 80 μm to about 120 μm, about 120 μm to about 160 μm about 160 μm to about 200 μm, or any thickness in a range bounded by any of these values. In some embodiments, the color conversion film may absorb light in the wavelength range of about 400 nm to about 480 nm and may emit light in the wavelength range of about 500 nm to about 560 nm.
In some embodiments, the color conversion film may further comprise a transparent substrate layer. The transparent substrate layer has two opposing surfaces, wherein the color conversion layer may be disposed on and in physical contact with the 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 (polymethyl acrylate), PMMA (Polymethylmethacrylate), CAB (cellulose acetate butyrate), PVC (polyvinylchloride), PET (polyethyleneterephthalate), PETG (glycol modified polyethylene terephthalate), PDMS (polydimethylsiloxane), COC (cyclo olefin copolymer), PGA (polyglycolide or polyglycolic acid), PLA (polylactic acid), PCL (polycaprolactone), PEA (polyethylene adipate), PHA (polyhydroxy alkanoate), PHBV (poly(3-hydroxybutyrate-co-3hydroxyvalerate)), PBE (polybutylene terephthalate), PTT (polytrimethylene terephthalate). Any of the aforedescribed , alone or in combination, may comprise the transparent substrate layer.
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. In some examples, 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.
In some embodiments, the color conversion film comprises a singlet oxygen quencher. In some embodiments the color conversion film comprises a radical scavenger.
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, polyvinylphosphonic 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.
In some embodiments, 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; cycloalkanes, such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane; alcohols, such as ethanol, propanol, butanol, amyl alcohol, hexanol, heptanol, octanol, decanol, undecanol, diacetone alcohol, and furfuryl alcohol; Cellosolves™, such as Methyl Cellosolve™, Ethyl Cellosolve™, Butyl Cellosolve™, Methyl Cellosolve™ acetate, and Ethyl Cellosolve™ acetate; propylene glycol and its derivatives, such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, and dipropylene glycol dimethyl ether; ketones, such as acetone, methyl amyl ketone, cyclohexanone, and acetophenone; ethers, such as dioxane and tetrahydrofuran; esters, such as butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate, ethyl 2-hydroxybutyrate, ethyl acetoacetate, methyl lactate, ethyl lactate, and methyl 3-methoxypropionate; halogenated hydrocarbons, such as chloroform, methylene chloride, and tetrachloroethane; aromatic hydrocarbons, such as benzene, toluene, xylene, and cresol; and highly polar solvents, 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 include a display device, wherein 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."
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 "In some embodiments, the photoluminescent complex may have a Stokes shift that is equal to or greater than 45 nm" should be interpreted as, for example, "In some embodiments, the photoluminescent complex will have a Stokes shift that is equal to or greater than 45 nm," or "In some embodiments, the photoluminescent complex will not have a Stokes shift that is equal to or greater than 45 nm."
The terms "a," "an," "the" and similar referents used in the context of describing the present disclosure (especially in the context of the following embodiments) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The use of any and all examples, or representative language (e.g., "such as") provided herein is intended merely to better illuminate the present disclosure and does not pose a limitation on the scope of any embodiments. No language in the specification should be construed as indicating any non-embodied element essential to the practice of the present disclosure.
Groupings of alternative elements or embodiments disclosed herein are not to be construed as limitations. Each group member may be referred to and embodied individually or in any combination with other members of the group or other elements found herein. It is anticipated that one or more members of a group may be included in, or deleted from, a group for reasons of convenience and/or patentability. When any such inclusion or deletion occurs, the specification is deemed to contain the group as modified thus fulfilling the written description of all Markush groups used in the appended embodiments.
Certain embodiments include the best mode known to the inventors for carrying out the present disclosure. Of course, variations on these embodiments, will become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventor expects skilled artisans to employ such variations as appropriate, and the inventors intend for the present disclosure to be practiced otherwise than specifically described herein. Accordingly, the embodiments include all modifications and equivalents of the subject matter recited in the embodiments as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is contemplated unless otherwise indicated herein or otherwise clearly contradicted by context. In closing, it is to be understood that the embodiments disclosed herein are illustrative of the principles of the embodiments. Other modifications that may be employed are within the scope of the embodiments. Thus, by way of example, but not of limitation, alternative embodiments may be 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 moiety; a linker complex; and a boron-dipyrromethene (BODIPY) moiety, wherein the BODIPY moiety is of the general formula:
Figure imgf000040_0001
, wherein R1 and R6 are independently H, alkyl, cycloalkyl, or alkenyl; wherein R3 and R4 are independently selected from a C1-C2 alkyl; wherein R2 and R5 are independently selected from H, alkyl, cycloalkyl, alkenyl, a cyano (-CN), an alkyl ester (-COOCH2CH3), an aryl ester (-COOCHzAr), or EtO2C; and wherein R7 and R8 is optionally substituted aryl; wherein the linker complex covalently links the blue light absorbing moiety and the BODIPY moiety, wherein the blue light absorbing moiety 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 blue light absorbing moiety 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 photoluminescent complex of embodiment 1, wherein the R7 and R8 substituted aryl is independently selected from
Figure imgf000041_0001
Figure imgf000041_0002
Embodiment 3 The photoluminescent complex of embodiment 1, wherein the blue light absorbing moiety is a xanthenoisoquinoline derivative.
Embodiment 4 The photoluminescent complex of embodiment 2, wherein the xanthenoisoquinoline derivative is of the general formula:
Figure imgf000041_0003
, wherein R° is independently selected from H, C1-C3 alkyl, optional substituted aryl, or optional substituted heteroaryl.
Embodiment 5 The photoluminescent complex of embodiment 1, wherein the BODIPY moiety is of the general formula:
Figure imgf000042_0001
, wherein R1 and R6 are independently selected from H, a saturated or unsaturated alkyl group, or an alkene group; wherein R3 and R4 are independently selected from a Ci-C2 alkyl; wherein R2 and R5 are independently selected from H, alkyl, cycloalkyl, alkenyl, a cyano (-CN ), an alkyl ester (-COOCH2CH3), an aryl ester (-COOCH2Ar), or EtO2C; and wherein R7 and Rs is a substituted aryl.
Embodiment 6 The photoluminescent complex of embodiment 6, wherein R1, R3, R4, and R6 are independently selected from a C1-C3 alkyl or a methyl group; wherein R2 and R5 are independently selected from a C1-C3 ester group or a CH3CH2CO2 ester.
Embodiment 7 The photoluminescent complex of embodiment 10, wherein the unsubstituted ester comprises one of the following structures:
Figure imgf000042_0002
Figure imgf000042_0003
Embodiment 8 The photoluminescent complex of embodiment 10, wherein the substituted
Figure imgf000042_0004
Embodiment 9 The photoluminescent complex of embodiment 10, wherein the unsubstituted and/or substituted ether comprises one of the following structures:
Figure imgf000042_0005
Figure imgf000043_0001
Embodiment 10 The photoluminescent complex as in embodiments 1, 2, 3, 4, 5, 6, 7 , 8, or 9, wherein the photoluminescent complex comprises one of the following structures:
Figure imgf000043_0002
Figure imgf000044_0001
Figure imgf000045_0001
Embodiment 11 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, wherein the photoluminescent compound comprises the photoluminescent complex as in embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, dispersed within the resin matrix.
Embodiment 12 The color conversion film of embodiment 11, further comprising a singlet oxygen quencher.
Embodiment 13 The color conversion film of embodiment 11, further comprising a radical scavenger.
Embodiment 14 The color conversion film of embodiment 11, wherein the color conversion film has a thickness of between 10 μm and 200 μm.
Embodiment 15 The color conversion film of embodiment 11, wherein the color conversion film absorbs light in about 400 nm to about 480 nm wavelength range and emits light in the 500 nm to about 560. Embodiment 16 A method for preparing the color conversion film as in embodiments 12, 13, or 15, the method comprising: dissolving the photoluminescent complex as in embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, and a binder resin within a solvent; and applying the mixture to one of the transparent substrates opposing surfaces.
Embodiment 17 A backlight unit comprising the color conversion film as in embodiments 11,, 13, 14, or 15.
Embodiment 18 A display device including the back-light unit of embodiment 17.
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 - Comparative Examples (CE) and Photoluminescent Compounds (PLC)
Comparative Example 1 (CE-1)
Figure imgf000047_0001
Dipyrrolemethane CE-1
CE-l: 0.75 g of 4-hydoxyl-2,6-dimethylvenzaldehyde (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. (2.0g) was added and the mixture was stirred overnight. The next day the solution was filtered and then washed with dichloromethane resulting in a dipyrrolemethane (1.9g). Next, 1.0 g of dipyrrolemethane was dissolved in 60 mL of THF. 5 mL of trimethylamine was added to the solution and then degassed for 10 minutes. After degassing, 5 mL of trifluoroboron-diethylether was added slowly followed by heating for 30 minutes at 70 °C. The resulting solution was loaded on a silica gel and purified by flash chromatography using dichloromethane as the eluent. The desired fraction was collected and dried under reduced pressure to yield 0.9 g or an orange solid (76% yield). LCMS (APCI+): calculated for C21H24BF2N2O (M+H) = 369; found: 369. XH NMR (400 MHz, Chloroform-d) 5 6.64 (s, 2H), 5.97 (s, 2H), 4.73 (s, 1H), 2.56 (s, 6H), 2.09 (s, 6H), 1.43 (s, 6H).
Comparative Example 2 (CE-2): was synthesized as described in Wakamiya, Atsushi et al. Chemistry
Leters, 37(10), 1094-1095; 2008
Comparative Example 3 (CE-3): was synthesized as below:
Figure imgf000048_0001
Compound CE-3.1 (6-(2-nitrophenoxy)-lH,3H-benzo[de]isochromene-l, 3-dione):
A mixture of 2-nitrophenol (6.6 g, 48 mmol), KOH powder (2.4 g, 43 mmol) was mixed and stirred under vacuum for 30 min, then copper powder (0.4 g) was added, followed by 100 mt anhydrous DMF. The mixture was stirred for 5 min, then 4-chloronaphthalic anhydride (5.1g, 22 mmol) was added. The whole was degassed then heated at reflux for 1.5 hr. After cooled to room temperature, lOOmL 20% hydrochloric acid was added dropwise into the resulted reaction mixture, which was allowed to sit for 2 hrs. The precipitate was collected by filtration, then was dried under vacuum overnight to give yellow brown solid (4.6g). It was further purified by stirred in refluxing acetic acid (50 mL) for 1 hr, then cooled to room temperature. Filtration and dried in air gave a yellow solid (3.0g, in 41% yield). Confirmed by LCMS (APCI): calcd for CisHioNOe (M+H): 336.0; Found: 336. :H NMR (400 MHz, Chloroform-d) δ 8.80 (dd, J = 8.5, 1.2 Hz, 1H), 8.72 (dd, J = 7.3, 1.2 Hz, 1H), 8.50 (d, J = 8.2 Hz, 1H), 8.19 (dd, J = 8.2, 1.7 Hz, 1H), 7.90 (dd, J = 8.5, 7.3 Hz, 1H), 7.79 (td, J = 7.9, 1.7 Hz, 1H), 7.54 (td, J = 8.0, 1.3 Hz, 1H), 7.39 (dd, J = 8.3, 1.2 Hz, 1H), 6.89 (d, J = 8.2 Hz, 1H).
Compound CE-3.2 (6-(2-aminophenoxy)-lH,3H-benzo[de]isochromene-l, 3-dione):
A mixture of Compound CE-3.1 (2.0 g, 6 mmol) and iron powder (<10 p.M, 0.91 g, 16 mmol) in acetic acid (75 mL) was heated to reflux for 30 min. The resulting solution was poured into water (220mL). The resulted precipitate was collected by filtration and washed with water and dried thoroughly in air then under vacuum to afford a yellow solid (1.65 g, in 90% yield). Confirmed by LCMS (APCI): calcd for Ci8Hi2NO4 (M+H): 306.1; Found: 306.
Compound CE-3.3 (lH,3H-isochromeno[6,5,4-mna]xanthene-l,3-dione):
Compound CE-3.3 (1.5 g, 4.9 mmol), was dispersed in acetic acid (35 mL) and cooled to 0 ^C. While being stirred, precooled hydrochloric acid (3mL, 37 mmol) was added, then sodium nitrite solution (3.29g, 46 mmol) in 12 mL water was added dropwise at 0 °C. The whole was stirred for one hour at 0 -C, then was transferred into additional funnel, and dropped into a refluxed copper sulfate solution (5.08g, 20 mmol, in 50 mL water) over one hour period. After cooling to room temperature, the precipitate was collected by filtration, washed with water and acetone, then dried in air, then in vacuum to give a yellow solid (0.92g, in 65% yield). Confirmed by LCMS (APCI): Calcd for CisHsC^ (M-): 288.0; Found: 288.
Compound CE-3.4 (5,ll-dibromo-lH,3H-isochromeno[6,5,4-mna]xanthene-l,3-dione):
A 2L 2N round bottom flask was charged with a stir bar and fitted with a long-finned condenser. To the flask was added Compound CE-1.1 (34.688 mmol, 10.00 g), followed by ortho-dichlorobenzene (1000 mL). The reaction mixture was stirred at room temperature and Bn (416.26 mmol, 21.3 mL) was added. The second neck was stoppered, and the reaction mixture was heated with an aluminum heat block at 75 °C open to air over the weekend. The reaction mixture was cooled to room temperature and a solid was filtered off. The filtrate was diluted with hexanes (~20% of volume) and a second precipitate was filtered off. Both of these precipitates were dried in vacuo at 100 °C. Orangish solids, 10.866 g total (69.9% yield). Both had similar LCMS and NMR. MS (APCI): calculated for Chemical Formula: Ci8H5Br2O4 (M+H) = 445; found: 445.
Figure imgf000049_0001
NMR (400 MHz, TCE) δ 9.47 (dd, J = 8.4, 1.5 Hz, 1H), 8.76 (d, J = 14.2 Hz, 2H), 7.72 - 7.63 (m, 1H), 7.56 (dd, J = 8.3, 1.4 Hz, 1H), 7.46 (ddd, J = 8.5, 6.7, 1.9 Hz, 1H).
Compound CE-3.5 (2-(4-(5,ll-dibromo-l,3-dioxo-lH-xantheno[2,l,9-def]isoquinolin-2(3H)- yl)phenyl)acetic acid):
A 100 mL 2N round bottom flask was charged with a stir bar and fitted with a finned condenser/gas adapter and flow control. The system was flushed with argon. To the flask was added Compound CE- 3.4 (7.000 mmol, 3.136 g), 2-(4-aminophenyl)acetic acid (14.00 mmol, 2.117 g), DMAP (2.100 mmol, 257 mg), and anhydrous DMF (65 mL). The reaction mixture was heated in an aluminum block set to 160 °C for 5 hours. The crude reaction mixture was cooled to 0 °C and quenched with 6N HCI (~5 mL) and diluted with water (up to ~350 mL). The precipitate was filtered off, washing with water. The product was dried by suction and used without further purification in the next reactions. Assume 100% yield. MS (APCI): calculated for Chemical Formula: C26Hi3Br2NO5 (M+H) = 578; found: 578. Compound CE-3.8:
A mixture of ethyl 2,4-dimethyl-lH-pyrrole-3-carboxylate (1.0g, 6.0 mmol), 4-hydroxy-2,6- dimethylbenzaldehyde (0.449g, 3.0 mmol) and p-toluenesulfonic acid (p-TsOH) (50 mg, 0.29mmol) in 50 mL dichloroethane (DCE) was degassed and stirred at room temperature overnight. Liquid chromatography-Mass spectroscopy (LCMS) analysis shows that reaction completed with main leak of m/e+ = 467. To the mixture obtained above, 2,3-Dichloro-5,6-dicyano-l,4-benzoquinone (DDQ.) (0.817g, 3.6 mmol) was added and the whole was stirred at room temperature for 30 min. LCMS analysis indicates that reaction completed with main peak of m/e+ = 465. With ice-batch cooling, to the mixture obtained above, triethylamine (1.7 mL, 12 mmol) and BF3-d iethy I ether (2.2 mL, 18 mmol) was added, and the resulting mixture was stirred at 50 C for one hour. Additional ImL triethylamine and ImL BF3-diethyl ether were added, and the whole was heated for additional one hour. LCMS analysis indicates that all dipyrrolemethine 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% to 30% ethyl acetate). The desired fraction was collected. After removal of solvents, the desired product was obtained as orange solid (1.0g, in 65% yield). 1H NMR (400 MHz, Chloroform-d) δ 6.68 (s, 2H), 4.29 (q, J = 7.1 Hz, 4H), 2.84 (s, 6H), 2.05 (s, 6H), 1.34 (t, J = 7.1 Hz, 6H). LCMS (APCI+): calculated for C27H32BF2N2O5 (M+H) = 513.2; Found: 513.
Compound CE-3.6 (2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetic acid):
A 250 mL 2N round bottom flask was charged with a stir bar and fitted with a finned condenser/gas adapter and flow control. The system was flushed with argon. To the flask was added Compound CE- 3.5 (3.500 mmol, 2.034 g), (3,5-bis(trifluoromethyl)phenyl)boronic acid (14.00 mmol, 3.611), K2CO3 (19.25 mmol, 2.661 g), THF (60 mL), DMF (12 mL), and water (6 mL). The reaction mixture was stirred under argon at room temperature for a few minutes, then Pd(dppf)CI2 (0.0245 mmol, 179 mg) was added. The headspace was flushed with argon for a minute, then the flow control was closed. The reaction mixture was stirred and heated in an aluminum heat block at 80 °C for three hours. The crude reaction mixture was evaporated to dryness in vacuo, taken up in DCM, and evaporated in vacuo onto ~35 g of flash silica gel. Purified by flash chromatography on silica gel (220g, equilibrate 0% EtOAc/DCM, eluting 0% (10 CV) -> 15.3% EtOAc/DCM (15.3 CV) -» 40% EtOAc/DCM (10 CV) -> isocratic 40% EtOAc/DCM). EtOAc contains 0.1% v/vTFA. Gives a brownish-yellow solid, 1.710 g (57.6% yield). MS (APCI): calculated for Chemical Formula: C^HigFuNOs (M+H) = 846; found: 846. XH NMR (400 MHz, DMSO) δ 12.45 (s, 1H), 8.62 (s, 1H), 8.52 (d, J = 1.7 Hz, 2H), 8.36 (s, 1H), 8.30 (s, 1H), 8.26 (d, J = 1.6 Hz, 2H), 8.24 (s, 1H), 7.50 (ddd, J = 8.5, 7.2, 1.5 Hz, 1H), 7.46 - 7.38 (m, 2H), 7.37 - 7.27 (m, 2H), 7.14 (dd, J = 8.3, 1.2 Hz, 1H), 6.98 (ddd, J = 8.4, 7.2, 1.3 Hz, 1H), 6.85 (dd, J = 8.3, 1.5 Hz, 1H), 3.69 (s, 2H).
Compound CE-3.7 (diethyl 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):
A mixture of ethyl 2,4-dimethyl-lH-pyrrole-3-carboxylate (1.0g, 6.0 mmol), 4-hydroxy-2,6- dimethylbenzaldehyde (0.449 g, 3.0 mmol) and tosylic acid (50 mg, 0.29mmol) in 50 mL 1,2- dichloroethane was degassed and stirred at room temperature overnight. LCMS analysis shows that one main peak with m/e+ = 467.
To the resulting solution, DDQ (0.817g, 3.6 mmol) was added then stirred for 30 min at room temperature. LCMS analysis shows that all starting material was converted to desired product with m/e+ =465.
With ice-bath cooling, 1.7 mL triethylamine and 2.2 mL BF3-diethyl ether were added sequentially to the mixture from step 2. The whole was heated at 50 SC for one hour. LCMS analysis shows ~30% conversion. To the mixture, additional ImL triethylamine and 1 mL BF3-diethyl ether was added, the whole was heated at 50 -C for additional one hour. LCMS analysis shows that all stating materials were converted to desired BODIPY product with m/e+ = 513, m/e- = 512. The reaction mixture was submitted directly to silica gel and purified by flash chromatography using eluents of hexanes/ethyl acetate (0% -> 30% ethyl acetate). The main desired peak was collected, and removal of solvents gave an orange solid (1.0 g, in 65% yield). LCMS (APCI): calculated for C27H32BF2N2O5 (M+H): 513.2; Found: 513. 1H NMR (400 MHz, Chloroform-d) δ 7.26 (s, 3H), 6.68 (s, 2H), 4.29 (q, J = 7.1 Hz, 4H), 2.84 (s, 6H), 2.05 (s, 6H), 1.34 (t, J = 7.1 Hz, 6H).
Compound CE-3 (diethyl 10-(4-(2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH- xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dimethylphenyl)-5,5-difluoro-l,3,7,9- tetramethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8-dicarboxylate):
Compound CE-3.6 (0.113 mmol, 80 mg), Compound CE-3.7 (diethyl 5,5-difluoro-10-(4- hydroxy-2,6-dimethylphenyl)-l,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'- f][l,3,2]diazaborinine-2,8-dicarboxylate) (0.0750 mmol, 38 mg), and DMAP.pTsOH salt (0.150 mmol, 44 mg) were placed in a 40 mL screw cap vial with a stir bar. To the vial was added dry DCM (10 mL) and the mixture was stirred to get a solution. To the vial was added DIC (0.263 mmol, 0.41 mL). The reaction was capped and stirred at room temperature overnight. The crude reaction mixture was diluted with hexanes and loaded onto ~20g of flash silica gel in a loader. Purified by flash chromatography on silica gel (120g, equilibrate 0% EtOAc/hexanes, eluting 0% (2 CV)
Figure imgf000051_0001
50% EtOAc/hexanes (30 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 70 mg (78% yield). MS (APCI): calculated for Chemical Formula: CesH+eBFsNsOg (M+H) = 1176; found: 1176. XH NM R (400 MHz, TCE) δ 8.71 (s, 1H), 8.48 (s, 1H), 7.95 - 7.80 (m, 6H), 7.66 (t, J =
8.4 Hz, 4H), 7.47 - 7.35 (m, 3H), 7.31 (dd, J = 8.3, 1.3 Hz, 1H), 7.10 (dd, J = 8.4, 1.5 Hz, 1H), 7.05 (s, 2H),
6.96 (ddd, J = 8.4, 7.1, 1.4 Hz, 1H), 4.28 (q, J = 7.1 Hz, 4H), 4.02 (s, 2H), 2.84 (s, 6H), 2.15 (s, 6H), 1.73
(s, 6H), 1.34 (t, J = 7.1 Hz, 6H).
Comparative Example 4 (CE-4)
Figure imgf000052_0001
Diethyl 10-(4-(2-(4-(l,3-dioxo-5,ll-bis(4-(trifluoromethyl)phenyl)-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dimethylphenyl)-5,5-difluoro-l,3,7,9-tetramethyl-5H-
4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8-dicarboxylate:
Diethyl 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 (0.3000 mmol, 154 mg), 2-(4-(l,3-dioxo-5,ll-bis(4-
(trifluoromethyl)phenyl)-lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (0.3600 mmol, 255 mg), DMAP.pTsOH salt (0.03000 mmol, 9 mg) and DIC (0.6000 mmol, 0.094 mL) were stirred in dry DCM (10 mL) at room temperature for one hour. The crude reaction was loaded onto
~30g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (120g, 0%
EtOAc/DCM (2 CV) -> isocratic steps to 3.8% EtOAc/DCM, then isocratic to elute product). Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 304 mg (84% yield).
MS (APCI): calculated for Chemical Formula: CeyHsoBFglXhOg (M+H) = 1204; found: 1204. JH NM R (400
MHz, TCE) δ 8.71 (s, 1H), 8.48 (s, 1H), 7.91 (d, J = 8.2 Hz, 2H), 7.89 - 7.82 (m, 4H), 7.72 - 7.63 (m, 4H),
7.48 - 7.37 (m, 3H), 7.31 (dd, J = 8.3, 1.3 Hz, 1H), 7.10 (dd, J = 8.3, 1.5 Hz, 1H), 7.05 (s, 2H), 6.96 (ddd,
J = 8.4, 7.1, 1.3 Hz, 1H), 4.29 (q, J = 7.1 Hz, 4H), 4.02 (s, 2H), 2.84 (s, 6H), 2.16 (s, 6H), 1.74 (s, 6H), 1.34
(t, J = 7.1 Hz, 6H).
Photoluminescent Compound PLC-1:
Figure imgf000053_0001
Compound PLC-1.1 ((3,5-dibromophenoxy)triethylsilane): A 500 mL 2N round bottom flask was charged with a stir bar and fitted with a gas adapter and septum. The flask was placed in a Dewar bowl. The flask was flushed with argon. To the flask was added 3,5-dibromophenol (100.0 mmol, 25.190g), imidazole (300.0 mmol, 20.430 g), and dry DCM (200 mL). The mixture was stirred to get a solution at room temperature, then cooled to 0 ° C with an ice-water bath. To the flask was added chlorotriethylsilane (150.0 mmol, 25.2 mL) via syringe with stirring at 0 ° C. The reaction was stirred at 0 ° C for 50 minutes, then partitioned with water (200 mL). The layers were separated, and the water layer extracted with DCM (50 mL). The combined organic layers were dried over MgSCU, filtered and evaporated to dryness in vacuo. The mixture was diluted with hexanes and loaded onto a loader containing 60g of flash silica gel. Purified by flash chromatography on silica gel (220g, equilibrate and elute 100% hexanes). Fractions containing product were evaporated to dryness in vacuo. Gives a colorless oil, 27.811 g (76% yield). MS (APCI): calculated for Chemical Formula: CizHigBrzOSi (M+H) = 365; found: 365. JH NMR (400 MHz, TCE) δ 7.28 (t, J = 1.7 Hz, 1H), 6.96 (d, J = 1.6 Hz, 2H), 1.10 - 0.95 (m, 9H), 0.75 (qd, J = 7.7, 0.9 Hz, 6H).
Compound PLC-1.2 (2,6-dibromo-4-hydroxybenzaldehyde): A 250 mL 2N round bottom flask was charged with a stir bar and fitted with a gas adapter and septum. The flask was placed in a Dewar bowl. The flask was flushed with argon. Weighed out Compound 1.1 (30.00 mmol, 10.985 g) and azeotroped from toluene. Compound 1.1 was transferred under argon to the reaction flask, then dry THF was added (130 mL) and the reaction mixture was stirred to get a homogeneous solution at room temperature. The reaction mixture was cooled to -78 ° C (dry ice/acetone). The system was purged of oxygen by vacuum/backfilling argon cycles (3X). A solution of LDA in THF/hexanes (1.0M, 60.00 mmol, 60.0 mL) was added with vigorous stirring over a few minutes. The solution was stirred at -78 ° C for 70 minutes, then anhydrous DM F (150.0 mmol, 11.6 mL) was added via syringe and stirred for 60 minutes at -78 ° C. The reaction mixture was dumped cold into 400 mL of sat. NH4CI solution with stirring. The solution was extracted with EtOAc (100 mL) and the layers separated. The aqueous layer was acidified to pH ~1 using excess 6N HCI to get an off-white ppt. The organic layer was extracted with 100 mL sat. NH4CI, then twice with 10% K2CO3 (100 mL). These aqueous extracts were also added to the acidified water, maintaining pH ~1. The resulting precipitate was filtered off, then dried in a vacuum oven at 90 0 C overnight. Gives an off-white/grey precipitate, 6.665 g (79% yield). MS (APCI): calculated for Chemical Formula:
Figure imgf000054_0001
(M+H) = 281; found: 281. XH NMR (400 MHz, Acetone) 6
10.14 (s, 1H), 7.24 (s, 2H).
Compound PLC-1.3 (3,3",5,5"-tetra-tert-butyl-5'-hydroxy-[l,l':3',l"-terphenyl]-2l-carbaldehyde): A 500 mL 2N round bottom flask was charged with a stir bar and fitted with a finned condenser/gas adapter and flow control. The system was flushed with argon. To the flask was added Compound 1.2 (5.500 mmol, 1.540 g), (3,5-di-tert-butylphenyl)boronic acid (22.00 mmol, 5.150g), NaHCOs (33.00 mmol, 2.772 g), Pd (dppfJCk (1.100 mmol, 805 mg), dry THF (270 mL), and water (9 mL). The heat block was set to 80 ° C and the reaction mixture stirred at this temperature overnight. The reaction mixture was evaporated onto 60g of flash silica gel and placed into a loader. Purified by flash chromatography on silica gel (220g, equilibrate 0% EtOAc/hexanes, eluting 0% (2 CV) -> 30% EtOAc/hexanes (20 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a light yellow solid, 2.256 g (82% yield). MS (APCI): calculated for Chemical Formula: C35H46O2 (M+H) = 499; found: 499. XH NMR (400 MHz, TCE) 5 9.80 (s, 1H), 7.42 (t, J = 1.8 Hz, 2H), 7.15 (d, J = 1.8 Hz, 4H), 6.87 (s, 2H), 1.35 (s, 36H).
Compound PLC-1.4 (3,3",5,5"-tetra-tert-butyl-2'-formyl-[l,l':3',l"-terphenyl]-5'-yl 2-(4-(5,ll- bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9-def]isoquinolin-2(3H)- yl)phenyl)acetate): A 40 mL screw-cap vial was charged with a stir bar, Compound 1.3 (4.523 mmol, 2256 mg), (2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetic acid (CE-3.6) (5.428 mmol, 4.590 g), DMAP.pTsOH salt (4.523 mmol, 1332 mg), and dry DCM (20 mL). The reaction mixture was stirred at room temperature to give a yellow slurry. With stirring at room temperature, added DIC (9.047 mmol, 1.41 mL). The reaction mixture was stirred at room temperature for 60 minutes, then diluted with hexanes 1:1 and loaded onto ~60g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (220g, equilibrate 0% EtOAc/hexanes, eluting 0% 2 CV -> 20% EtOAc/hexanes (22 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a yellow solid, 5.182 g (86% yield). MS (APCI): calculated for Chemical Formula: C77H63F12NO6 (M+H) = 1326; found: 1326. JH NMR (400 MHz, TCE) 6 9.89 (s, 1H), 8.75 (s, 1H), 8.50 (s, 1H), 8.29 - 8.24 (m, 2H), 8.07 (s, 1H), 8.05 - 7.97 (m, 3H), 7.67 - 7.60 (m, 2H), 7.49 (ddd, J = 8.6, 6.1, 2.6 Hz, 1H), 7.43 (t, J = 1.8 Hz, 2H), 7.38 (d, J = 8.4 Hz, 2H), 7.31 - 7.25 (m, 1H), 7.23 (s, 2H), 7.17 (d, J = 1.8 Hz, 4H), 7.05 - 6.96 (m, 2H), 4.07 (s, 2H), 1.36 (s, 36H).
PLC-1 (diethyl 10-(5'-(2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-3,3",5,5"-tetra-tert-butyl-[l,l':3',l"-terphenyl]-2'-yl)-5,5- difluoro-l,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8- dicarboxylate): A 250 mL 2N round bottom flask was charged with a stir bar and fitted with a finned condenser/gas adapter and flow control. The system was flushed with argon. To the flask was added Compound 1.4 (1.000 mmol, 1.326 g), ethyl 2,4-dimethyl-lH-pyrrole-3-carboxylate (2.100 mmol, 351 mg), and dry DCE (100 mL). The reaction mixture was stirred vigorously at room temperature for 30 seconds, then pTsOH.H2O (0.2000 mmol, 38 mg) was added. The reaction mixture was stirred under argon at room temperature for 19 hours, then DDQ was added (1.300 mmol, 295 mg), followed by dry DCE (5 mL). The mixture was stirred for 30 minutes at room temperature, then more DDQ. (0.5000 mmol, 114 mg) was added, followed by dry DCE (5 mL). After stirring for another 30 minutes, the oxidation was complete. To the reaction was added Et3N (8.000 mmol, 1.1 mL) and BFg.OEtz (12.00 mmol, 1.5 mL). After 1 minute, repeated the addition of Et3N (8.000 mmol, 1.1 mL) and BFg.OEtz (12.00 mmol, 1.5 mL) was repeated. The reaction mixture was stirred at 50 ° C for 50 minutes, then the reaction mixture was evaporated onto 25g of flash silica gel in vacuo (bath = 60 ° C) and this silica placed in a loader. Purified by flash chromatography on silica gel (330 g, equilibrate 0% acetone/hexanes, eluting 0% (2 CV) -> 20% acetone/hexanes (15 CV)). Fractions containing product were evaporated to dryness in vacuo. Repurified by loading directly onto a 220g column using 10% DCM/hexanes (dry load), eluting 0%
Figure imgf000055_0001
0.2% EtOAc/DCM (2 CV)-> isocratic 0.2% EtOAc/DCM. Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 870 mg (52% yield). MS (APCI): calculated for Chemical Formula: CgsH84BFi4N3O9 (M+H) = 1689; found: 1689. 1H NMR (400 MHz, TCE) δ 8.75 (s, 1H), 8.50 (s, 1H), 8.26 (s, 2H), 8.07 (s, 1H), 8.02 (s, 3H), 7.66 (d, J = 8.3 Hz, 2H), 7.53 - 7.44 (m, 1H), 7.43 - 7.34 (m, 4H), 7.27 (d, J = 8.1 Hz, 1H), 7.21 (t, J = 1.8 Hz, 2H), 7.04 - 6.91 (m, 6H), 4.24 (q, J = 7.1 Hz, 4H), 4.10 (s, 2H), 2.62 (s, 6H), 2.00 (s, 6H), 1.30 (t, J = 7.1 Hz, 6H), 1.12 (s, 36H).
Photoluminescent Compound PLC-2:
Figure imgf000056_0001
5"-Hydroxy-[l,l':4',l":3",l"l:4'",l""-quinquephenyl]-2"-carbaldehyde: 2,6-dibromo-4- hydroxybenzaldehyde (500 mg, 1786 mmol), [l,l'-biphenyl]-4-ylboronic acid (1415 mg, 7.144 mmol), sodium bicarbonate (900 mg, 10.72 mmol), and Pd (dppf)Ck were combined in THF (90 mL) and water (6 mL) under argon and heated at 80 ° C for 6 hours. The crude reaction mixture was evaporated onto ~50g of flash silica gel in vacuo and packed into a loader. Purified by flash chromatography on silica gel (120g, 0% acetone/hexanes (2 CV) -> 30% (15 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives 1308 mg (172% yield). Unknown what the impurity is. Taken to next step without further purification. MS (APCI): calculated for Chemical Formula: C31H22O2 (M+H) = 427; found: 427.
2"-Formyl-[l,l':4',l":3",l"':4"',l""-quinquephenyl]-5"-yl 2-(4-(5,ll-bis(3,5- bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetate): The phenol from the first step (50% w/w, 86 mg, 0.1000 mmol), 2-(4-(5,ll-bis(3,5- bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (101 mg, 0.120 mmol), DMAP.pTsOH salt (59 mg, 0.2000 mmol), and DIC (0.125 mL, 0.8000 mmol) were combined in dry DCM (10 mL) and stirred in a capped vial at room temperature for 20 minutes. The crude reaction mixture was evaporated onto ~10g of flash silica gel in vacuo and packed into a loader. Purified by flash chromatography on silica gel (80g, 0% acetone/hexane (2 CV)
Figure imgf000057_0001
40% acetone/hexane (15 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a yellow solid, containing some of the starting hydroxy-aldehyde (~36% by NMR) and desired product (~64% by NMR). MS (APCI): calculated for Chemical Formula: C73H39F12NO6 (M+H) = 1254; found: 1254. Take to next step without further purification.
PLC-2 Diethyl 10-(5"-(2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-[l,l':4',l":3",l"':4"',l""-quinquephenyl]-2"-yl)-5,5- difluoro-l,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8- dicarboxylate): The aldehyde from the previous step (mixture, ~0.1473 mmol, 109 mg), ethyl 2,4- dimethyl-lH-pyrrole-3-carboxylate (59 mg, 0.3534 mmol), and pTsOH.H2O (6 mg, 0.02945 mmol) were combined in dry DCE (20 mL) and stirred under argon at 50 ° C for 2 hours. The reaction mixture was cooled to room temperature and treated with DDQ. (44 mg, 0.1914 mmol) and stirred at room temperature for 20 minutes. Added EtgN (0.16 mL, 1.178 mmol), and BFs.OEtz (0.22 mL, 1.767 mmol). The addition of Et3N (0.16 mL, 1.178 mmol), and BF3.OEt2 (0.22 mL, 1.767 mmol) was repeated, then the reaction mixture was stirred for one hour at 50 ° C. The crude reaction mixture was evaporated in vacuo onto ~15g of flash silica gel and packed into a lloader. Purified by flash chromatography on silica gel (120g, 0.1% EtOAc/DCM (4 CV) -> 0.5% (15 CV) -> 3% (30 CV), step gradient). Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 21 mg (23% yield). MS (APCI): calculated for Chemical Formula: CgiHeoBFuNgOg (M+H) = 1616; found: 1616. 1H NMR (400 MHz, TCE) δ 8.76 (s, 1H), 8.50 (s, 1H), 8.07 (s, 1H), 8.05 - 8.00 (m, 3H), 7.67 (d, J = 8.4 Hz, 2H), 7.63 - 7.56 (m, 4H), 7.53 (d, J = 8.3 Hz, 4H), 7.51 - 7.46 (m, 1H), 7.45 (s, 3H), 7.43 - 7.39 (m, 5H), 7.38 - 7.31 (m, 2H), 7.28 (dd, J = 8.6, 2.3 Hz, 5H), 7.07 - 6.94 (m, 2H), 4.25 (q, J = 7.1 Hz, 4H), 4.10 (s, 2H), 2.71 (s, 6H), 2.01 (s, 6H), 1.33 (t, J = 7.1 Hz, 6H).
Photoluminescent Compound PLC-3:
Figure imgf000058_0001
Bis(2-ethylhexyl) 5-bromoisophthalate: 5-bromoisophthalic acid (5.00 g, 20.41 mmol), 2-ethylhexan- l-ol (20 mL), and pTsOH.FbO (388 mg, 2.041 mmol) were combined in toluene (150 mL) and DMSO (10 mL) and refluxed under a Dean-Stark trap to remove water for 24 hours. The reaction was cooled to room temperature and evaporated onto ~60g of flash silica gel in vacuo. Purified by flash chromatography on silica gel (220g, 0% acetone/hexanes (2 CV) -> 20% (10 CV)). Did not separate well. Evaporate to dryness in vacuo and repeat purification sequence. Fractions containing product were evaporated to dryness in vacuo. Gives 5.679 g (59% yield). MS (APCI): calculated for Chemical Formula: C24H37BrO4 (M+H) = 469; found: 469. ~90% purity by NMR. Take to next step without further purification.
Bis(2-ethylhexyl) 5-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)isophthalate: The aryl bromide from the previous step (~90% purity, 5.678 g, 12.09 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(l,3,2- dioxaborolane) (3.378g, 13.30 mmol), KOAc (3.561 g, 36.28 mmol), and Pd(dppf)Cl2 (266 mg, 0.3628 mmol) were combined in dry dioxane (100 mL) and heated at 80 ° C under argon for three hours. The reaction mixture was cooled to room temperature and evaporated onto ~60g of flash silica gel in vacuo. Purified by flash chromatography on silica gel (220g, 0% EtOAc/hexanes (2 CV)
Figure imgf000059_0001
20% (25 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives 5.479 g (88% yield). MS (APCI): calculated for Chemical Formula: CsoHigBOe (M+H) = 517; found: 517. 1H NMR (400 MHz, TCE) 6 8.69 (t, J = 1.8 Hz, 1H), 8.59 (d, J = 1.7 Hz, 2H), 4.28 (d, J = 5.8 Hz, 4H), 1.75 (hept, J = 6.3 Hz, 2H), 1.55 - 1.29 (m, 28H), 0.96 (t, J = 7.5 Hz, 6H), 0.94 - 0.89 (m, 6H).
Tetrakis(2-ethylhexyl) 2'-formyl-5'-hydroxy-[l,l':3',l"-terphenyl]-3,3",5,5"-tetracarboxylate): The aryl boronate from the previous step (1845 mg, 3.572 mmol), 2,6-dibromo-4-hydroxybenzaldehyde (250 mg, 0.8931 mmol), sodium bicarbonate (450 mg, 5.359 mmol), and Pd (dppf)CI2 (131 mg, 0.1786 mmol) were combined in THF (45 mL) and water (3 mL) and heated at 80 ° C under argon overnight. The reaction mixture was cooled to room temperature and evaporated onto ~50g of flash silica gel in vacuo. Purified by flash chromatography on silica gel (220g, 0% acetone/hexanes (2 CV) -> 15% (20.5 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives 645 mg (80% yield). MS (APCI): calculated for Chemical Formula: CssHysOio (M+H) = 900; found: 900. 1H NMR (400 MHz, TCE) 6 9.71 (s, 1H), 8.70 (t, J = 1.6 Hz, 2H), 8.21 (d, J = 1.6 Hz, 4H), 6.91 (s, 2H), 6.77 (s, 1H), 4.43 - 4.16 (m, 8H), 1.75 (q, J = 6.4 Hz, 4H), 1.58 - 1.20 (m, 32H), 0.96 (t, J = 7.5 Hz, 12H), 0.93 - 0.87 (m, 12H).
Tetrakis(2-ethylhexyl) 5'-(2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH- xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2'-formyl-[l,l':3',l"-terphenyl]-3,3",5,5"- tetracarboxylate): The phenol from the previous step (99 mg, 0.1100 mmol), 2-(4-(5,ll-bis(3,5- bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (121 mg, 0.1430 mmol, DMAP.pTsOH salt (65 mg, 0.2200 mmol), and DIC (0.069 mL, 0.440 mmol) were combined in dry DCM (10 mL) and stirred at room temperature for 30 minutes. The crude reaction mixture was diluted 1:1 with hexane and loaded onto ~20g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (120g, 0% acetone/hexanes (2 CV) -> 30% (20 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a yellow solid, 118 mg (62% yield). Product co-elutes with unreacted 1677-079. Take to next step without further purification. MS (APCI): calculated for Chemical Formula: C97H95F12NO14 (M+H) = 1727; found: 1727.
PLC-3 Tetrakis(2-ethylhexyl) 5'-(2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH- xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2'-(2,8-bis(ethoxycarbonyl)-5,5-difluoro- l,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinin-10-yl)-[l,l':3',l"- terphenyl]-3,3",5,5"-tetracarboxylate: The aldehyde from the previous step (mixture, 136 mg, 0.1077 mmol), ethyl 2,4-dimethyl-lH-pyrrole-3-carboxylate (35 mg, 0.2112 mmol), and PTSOH.H2O (3.3 mg, 0.01760 mmol) were combined in dry DCE (25 mL) and reacted at 50 0 C under argon overnight. The
SI reaction was cooled to room temperature and treated with DDQ (26 mg, 0.1144 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with Et3N (0.098 mL, 0.7041 mmol), and BF3.OEt2 (0.13 mL, 1.056 mmol). The addition of Et3N (0.098 mL, 0.7041 mmol), and BF3.OEt2 (0.13 mL, 1.056 mmol)) was repeated and the reaction mixture was stirred for one hour at 50 ° C. The reaction mixture was evaporated onto ~30g of flash silica gel in vacuo and packed into a loader. Purified by flash chromatography on silica gel (120g, 0% EtOAc/hexanes
Figure imgf000060_0001
20% (20 CV) -> 30% (5 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 55 mg (38% yield). 1H NMR (400 MHz, TCE) δ 8.75 (s, 1H), 8.54 (t, J = 1.5 Hz, 2H), 8.50 (s, 1H), 8.26 (d, J = 1.7 Hz, 2H), 8.04 (dd, J = 16.2, 1.6 Hz, 8H), 7.69 - 7.62 (m, 2H), 7.52 (s, 2H), 7.49 (ddd, J = 8.6, 6.3, 3.0 Hz, 1H), 7.42 - 7.37 (m, 2H), 7.30 - 7.25 (m, 1H), 7.03 - 6.96 (m, 2H), 4.23 (q, J = 7.0 Hz, 4H), 4.20 - 4.10 (m, 8H), 4.10 (s, 2H), 2.68 (s, 6H), 1.96 (s, 6H), 1.65 - 1.57 (m, 4H), 1.43 - 1.16 (m, 38H), 0.88 (t, J = 7.3 Hz, 24H).
Photoluminescent Compound PLC-4:
Figure imgf000060_0002
5"-Hydroxy-[l,l':3',l":3",l"':3"',l""-quinquephenyl]-2"-carbaldehyde: 2,6-dibromo-4- hydroxybenzaldehyde (250 mg, 0.8931 mmol), [l,l'-biphenyl]-3-ylboronic acid (707 mg, 3.572 mmol), sodium bicarbonate (450 mg, 5.359 mmol), and Pd(dppf)CI2 (131 mg, 0.1786 mmol) were combined in THF (45 mL) and water (3 mt) and stirred at 80 ° C under argon for five hours. The reaction mixture was cooled to room temperature and evaporated onto ~25g of flash silica gel in vacuo and packed into a loader. Purified by flash chromatography on silica gel (120g, 0% acetone/hexanes (2 CV)
Figure imgf000061_0001
30% (15 CV)). Gives 315 mg (83% yield). MS (APCI): calculated for Chemical Formula: C31H22O2 (M+H) = 427; found: 427. 1H NMR (400 M Hz, Acetone) δ 9.89 (s, 1H), 9.48 (s, 1H), 7.75 - 7.67 (m, 8H), 7.54 (td, J = 7.5, 1.0 Hz, 2H), 7.51 - 7.44 (m, 4H), 7.43 - 7.34 (m, 4H), 6.97 (s, 2H).
2"-Formyl-[l,l':3',l":3",l"':3"',l""-quinquephenyl]-5"-yl 2-(4-(5,ll-bis(3,5- bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetate:
The phenol from the previous step (64 mg, 0.1500 mmol), 2-(4-(5,ll-bis(3,5- bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (178 mg, 0.2100 mmol), DMAP.pTsOH salt (88 mg, 0.3000 mmol), and DIC (0.094 mmol, 0.6000 mmol) were stirred in dry DCM (10 mL) at room temperature for 30 minutes. The crude product was diluted 1:1 with hexanes and loaded onto ~20g of flash silica gel packed in a loader. Purified by flash chromatography on silica gel (120g, 0% acetone/hexanes (2 CV) 40% (15 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives 204 mg of a yellow solid (109% yield). Wet with solvent. Take to next step. MS (APCI): calculated for Chemical Formula: C73H39F12NO6 (M+H) = 1254; found: 1254. 1H NMR (400 MHz, TCE) δ 9.98 (s, 1H), 8.74 (s, 1H), 8.49 (s, 1H), 8.26 (s, 2H), 8.17 - 7.91 (m, 4H), 7.82 - 7.19 (m, 26H), 6.99 (s, 2H), 4.05 (s, 2H).
PLC-4 Diethyl 10-(5"-(2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-[l,l':3',l":3",l"':3"',l""-quinquephenyl]-2"-yl)-5,5- difluoro-l,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8- dicarboxylate: The aldehyde from the previous step (203 mg, 0.1619 mmol), ethyl 2,4-dimethyl-lH- pyrrole-3-carboxylate (62 mg, 0.3723 mmol), and pTsOH.HzO (6 mg, 0.03237 mmol) were combined in dry DCE (25 mL) and stirred at room temperature under argon for one hour. The reaction mixture was treated with DDQ (55 mg, 0.2428 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with Et3N (0.18 mL, 1.295 mmol), and BF3.OEt2 (0.24 mL, 1.942 mmol). The addition of EtsN (0.18 mL, 1.295 mmol), and BF3.OEt2 (0.24 mL, 1.942 mmol) was repeated and the reaction mixture was stirred for one hour at 50 ° C. The crude reaction mixture was diluted 1:1 with hexanes and loaded onto ~25g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (120g, 0% EtOAc/DCM (2 CV) -> 0.5% (10 CV) -> 3% (25 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 51 mg (20% yield). MS (APCI): calculated for Chemical Formula: C91H60BF14N3O9 (M+H) = 1616; found: 1616. 1H NMR (400 MHz, TCE) δ 8.75 (s, 1H), 8.50 (s, 1H), 8.30 - 8.21 (m, 2H), 8.07 (s, 1H), 8.05 - 7.98 (m, 3H), 7.72 - 7.61 (m, 2H), 7.55 - 7.45 (m, 5H), 7.44 - 7.20 (m, 20H), 7.07 - 6.94 (m, 2H), 4.24 (q, J = 7.1 Hz, 4H), 4.08 (s, 2H), 2.76 (s, 6H), 2.01 (s, 6H), 1.32 (t, J = 7.1 Hz, 6H). Photoluminescent Compound PLC-5:
Figure imgf000062_0001
5'-Hydroxy-3,3",5,5"-tetrakis(trifluoromethyl)-[l,r:3',l"-terphenyl]-2'-carbaldehyde: 2,6-dibromo- 4-hydroxybenzaldehyde (560 mg, 2.000 mmol), (3,5-bis(trifluoromethyl)phenyl)boronic acid (1032 mg, 4.000 mmol), sodium bicarbonate (1008 mg, 12.00 mmol), and Pd (d ppf )CI2 (293 mg, 0.4000 mmol) were combined in dry THF (90 mL) and water (6 mL) and stirred at 80 ° C under argon for two hours. The reaction mixture was cooled to room temperature and titrated to pH ~1 with 6N HCI solution. The reaction mixture was partition between ether (150 mL), the layers separated, extracted with DCM (150 mL), the combined organic layers dried over magnesium sulfate, filtered, and evaporated to dryness in vacuo. The crude product was evaporated in vacuo onto ~40g of flash silica gel and packed into a loader. Purified by flash chromatography on silica gel (120g, 0% EtOAc/hexanes (2 CV)
Figure imgf000062_0002
20% (30 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a white solid, 889 mg (75% yield). MS (APCI): calculated for Chemical Formula: C23H10F12O2 (M+H) = 547; found: 547. 1H NMR (400 MHz, Acetone) δ 9.82 (s, 1H), 9.74 (s, 1H), 8.12 - 8.10 (m, 2H), 8.09 (s, 4H), 7.06 (s, 2H).
2l-Formyl-3,3",5,5"-tetrakis(trifluoromethyl)-[l,l':3l,l"-terphenyl]-5'-yl 2-(4-(5,ll-bis(3,5- bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: The phenol from the previous step (889 mg, 1.028 mmol), 2-(4-(5,ll-bis(3,5- bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (1651 mg, 1.953 mmol), DMAP.pTsOH salt (48 mg, 0.1628 mmol), and DIC (0.51 mL, 3.255 mmol) were stirred in dry DCM (15 mL) at room temperature for 30 minutes. The crude reaction mixture was diluted 1:1 with hexanes and loaded onto a loader packed with ~50g of flash silica gel. Purified by flash chromatography on silica gel (220g, 0% EtOAc/toluene (2 CV) -> 10% (15 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a yellow solid, 1351 mg (60% yield). MS (APCI): calculated for Chemical Formula: C65H27F24NO6 (M+H) = 1374; found: 1374. 1H NMR (400 MHz, Acetone) 5 9.92 (s, 1H), 8.73 (s, 1H), 8.55 (d, J = 1.6 Hz, 2H), 8.49 (s, 1H), 8.30 (d, J = 1.7 Hz, 2H), 8.23 (dq, J = 1.8, 0.9 Hz, 1H), 8.21 - 8.18 (m, 1H), 8.17 - 8.13 (m, 4H), 8.13 (dt, J = 2.5, 1.1 Hz, 2H), 4.15 (s, 2H).
Diethyl 10-(5'-(2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-3,3",5,5"-tetrakis(trifluoromethyl)-[l,l':3',l"-terphenyl]- 2'-yl)-5,5-difluoro-l,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8- dicarboxylate: The aldehyde from the previous step (1351 mg, 0.9833 mmol), ethyl 2,4-dimethyl-lH- pyrrole-3-carboxylate (378 mg, 2.262 mmol), and PTSOH.H2O (19 mg, 0.09833 mmol) were stirred in dry DCE (50 mL) under argon overnight at room temperature. The reaction mixture was treated with DDQ. (379 mg, 1.672 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with Et3N (0.80 mL, 5.702 mmol), and BF3.OEt2 (1.06 mL, 8.552 mmol). The addition of Et3N (0.80 mL, 5.702 mmol), and BF3.OEt2 (1.06 mL, 8.552 mmol) was repeated and the reaction mixture was stirred for one hour at 50 ° C. The crude reaction mixture was evaporated in vacuo onto ~45g of flash silica gel and packed into a loader. Purified by flash chromatography on silica gel (220g, 0% EtOAc/DCM isocratic). Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 763 mg (45% yield). MS (APCI): calculated for Chemical Formula: CS3H48BF26N3O9 (M+H) = 1736; found: 1736. 1H NM R (400 MHz, TCE) δ 8.75 (s, 1H), 8.50 (s, 1H), 8.26 (d, J = 1.6 Hz, 2H), 8.08 (s, 1H), 8.06 - 7.91 (m, 3H), 7.79 (s, 2H), 7.71 - 7.64 (m, 2H), 7.64 - 7.60 (m, 4H), 7.57 (s, 2H), 7.49 (ddd, J = 8.5, 6.1, 2.5 Hz, 1H), 7.45 - 7.36 (m, 2H), 7.28 (dd, J = 8.0, 1.1 Hz, 1H), 7.07 - 6.94 (m, 2H), 4.28 (q, J = 7.1 Hz, 4H), 4.11 (s, 2H), 2.69 (s, 6H), 1.93 (s, 6H), 1.33 (t, J = 7.1 Hz, 6H).
Photoluminescent Compound PLC-6:
Figure imgf000064_0001
Bis((perfluorophenyl)methyl) 5-bromoisophthalate: 5-bromoisophthalic acid (1960 mg, 8.000 mmol), (perfluorophenyl)methanol (6.339 g, 32.00 mmol), DMAP.pTsOH salt (1177 mg, 4.000 mmol), and DIC (3.76 mL, 24.00 mmol) were combined in dry THF (50 mL) and stirred at room temperature under argon overnight. The crude reaction mixture was evaporated in vacuo onto ~60g of flash silica gel and packed into a loader. Purified by flash chromatography on silica gel (220g, 50% DCM/hexanes (2 CV) -> 100% DCM (10 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives 2.748 g (57% yield). MS (APCI): calculated for Chemical Formula: C22H7BrF10O4 (M+H) = 605; found: 605. 1H NMR (400 MHz, CD2CI2) δ 8.54 (t, J = 1.5 Hz, 1H), 8.33 (d, J = 1.6 Hz, 2H), 5.47 (t, J = 1.6 Hz, 5H).
Bis((perfluorophenyl)methyl) 5-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)isophthalate: The aryl bromide from the previous step (2.7634 g, 4.417 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(l,3,2- dioxaborolane) (1458 mg, 5.742 mmol), KOAc (1300 mg, 13.25 mmol), and Pd(dppf)CI2 (102 mg, 0.2208 mmol) were combined in dry dioxane (100 mL) under argon and heated at 80 ° C for two hours. The crude reaction mixture was evaporated onto ~60g of flash silica gel in vacuo and packed into a loader. Purified by flash chromatography on silica gel (120g, 50% DCM/hexanes (2 CV)
Figure imgf000065_0001
100% DCM isocratic DCM)). Fractions containing product were evaporated to dryness in vacuo. Gives 2.680 g (93% yield). MS (APCI): calculated for Chemical Formula: C28H19BF10O6 (M+H) = 653; found: 653. 1H NMR (400 MHz, CD2CI2) δ 8.67 (t, J = 1.8 Hz, 1H), 8.54 (d, J = 1.8 Hz, 2H), 5.47 (t, J = 1.6 Hz, 6H), 1.23 (s, 12H).
Tetrakis((perfluorophenyl)methyl) 2'-formyl-5'-hydroxy-[l,l':3',l"-terphenyl]-3,3",5,5"- tetracarboxylate: The aryl boronic acid from the previous step (2678 mg, 4.106 mmol), 2,6-dibromo- 4-hydroxybenzaldehyde (460 mg, 1.642 mmol), sodium bicarbonate (828 mg, 9.854 mmol), and Pd(dppf)CI2 (240 mg, 0.3285 mmol) were combined in THF (100 mL) and water (16 mL) and heated at 80 ° C under argon for four hours. The crude reaction mixture was evaporated onto ~60g of flash silica gel and packed into a loader. Purified by flash chromatography on silica gel (120g, 75% DCM/hexanes (2 CV) -> 100% DCM (10 CV)
Figure imgf000065_0002
isocratic DCM)). Fractions containing product were evaporated to dryness in vacuo. Gives 1.477 g (77% yield). MS (APCI): calculated for Chemical Formula: CsiHigFzoOio (M+H) = 1171; found: 1171. 1H NMR (400 MHz, CD2CI2) δ 9.63 (s, 1H), 8.67 - 8.57 (m, 5H), 6.84 (s, 2H), 5.48 (d, J = 1.5 Hz, 8H).
Tetrakis((perfluorophenyl)methyl) 5'-(2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH- xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2'-formyl-[l,ll:3',l"-terphenyl]-3,3",5,5"- tetracarboxylate: The phenol from the previous step (1470 mg, 1.256 mmol), -(4-(5,ll-bis(3,5- bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (1275 mg, 1.508 mmol), DMAP.pTsOH salt (37 mg, 0.1256 mmol), and DIC (0.393 mL, 2.511 mmol) were stirred in dry DCM (20 mL) at room temperature for 60 minutes. The crude reaction mixture was loaded onto ~50g of flash silica gel packed in a loader. Purified by flash chromatography on silica gel (120g, 0% EtOAc/DCM (2 CV)
Figure imgf000066_0001
3% (15 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a yellow solid, 1.317 g (53% yield). MS (APCI): calculated for Chemical Formula: C93H35F32NO14 (M+H) = 1998; found: 1998. NMR is messy, but correct compound. Take to next step as-is.
Tetrakis((perfluorophenyl)methyl) 5'-(2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH- xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2'-(bis(4-(ethoxycarbonyl)-3,5-dimethyl- lH-pyrrol-2-yl)methyl)-[l,l':3',l"-terphenyl]-3,3",5,5"-tetracarboxylate: The aldehyde from the previous step (1.315 g, 0.6581 mmol), ethyl 2,4-dimethyl-lH-pyrrole-3-carboxylate (275 mg, 1.646 mmol), and pTsOH.H2O (13 mg, 0.06581 mmol) were stirred in dry DCE (50 mL) under argon for two hours at room temperature. The crude reaction mixture was evaporated onto ~40g of flash silica gel in vacuo and packed into a loader. Purified by flash chromatography on silica gel (120g, 0% EtOAc/DCM (2 CV) -> 4% (15 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a yellow solid, 577 mg (38% yield). Take to next step as-is.
PLC-6 Tetrakis((perfluorophenyl)methyl) 5'-(2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3- dioxo-lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2'-(2,8-bis(ethoxycarbonyl)-5,5- difluoro-l,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinin-10-yl)-[l,l':3',l"- terphenyl]-3,3",5,5"-tetracarboxylate: The dipyrrole from the previous step (575 mg, 0.2493 mmol) was dissolved in dry DCE (50 mL) and treated with DDQ. (79 mg, 0.3490 mmol) and stirred at room temperature for one hour. The reaction was then treated with Et3N (0.28 mL, 1.994 mmol), and BFs.OEtz (0.37 mL, 2.991 mmol). The addition of EtsN (0.28 mL, 1.994 mmol), and BF3.OEt2 (0.37 mL, 2.991 mmol) was repeated and the reaction mixture was stirred for one hour at 50 ° C. The crude reaction mixture was evaporated onto ~40 g of flash silica gel in vacuo and packed into a loader. Purified by flash chromatography on silica gel (120g, 0% EtOAc/DCM (2 CV) -> 25% (25 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 126 mg (53% yield). 1H NMR (400 MHz, CD2CI2) 5 8.78 (s, 1H), 8.53 (s, 1H), 8.46 (t, J = 1.6 Hz, 2H), 8.31 (d, J = 1.7 Hz, 2H), 8.08 (t, J = 1.8 Hz, 5H), 8.06 - 8.03 (m, 3H), 7.66 - 7.59 (m, 2H), 7.52 (s, 2H), 7.47 (ddd, J = 8.6, 7.0, 1.7 Hz, 1H), 7.40 - 7.33 (m, 2H), 7.27 (dd, J = 8.3, 1.3 Hz, 1H), 7.03 (dd, J = 8.3, 1.7 Hz, 1H), 6.97 (ddd, J = 8.3, 7.0, 1.3 Hz, 1H), 5.36 (d, J = 1.4 Hz, 8H), 4.24 (q, J = 7.1 Hz, 4H), 4.09 (s, 2H), 2.62 (s, 6H), 1.91 (s, 6H), 1.30 (t, J = 7.1 Hz, 6H).
Photoluminescent Compound PLC-7:
Figure imgf000067_0001
tert-Butyl (2-oxobutyl)carbamate: tert-Butyl (2-(methoxy(methyl)amino)-2-oxoethyl)carbamate
(10.915 g, 50.00 mmol) was dissolved in dryTHF (200 mL) under argon and cooled to O ° C. The reaction mixture was treated with ethylmagnesium bromide (3M in ether, 50.0 mL, 150.0 mmol) over a period of about five minutes with stirring. The cooling bath was removed and the reaction mixture stirred at room temperature for six hours. Quenched with ethyl acetate (~15 mL), then partitioned with saturated ammonium chloride (~100 mL) and ethyl acetate (200 mL). The combined organic layers were washed with water (100 mL), brine (25 mL), dried over magnesium sulfate, filtered, and evaporated to dryness in vacuo. The crude product was taken up in hexanes and loaded onto ~50g of flash silica gel packed in a loader. Purified by flash chromatography on silica gel (220g, 0% EtOAc/hexanes
Figure imgf000067_0002
30% (15 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a light yellow liquid, 7 .879 g (84% yield). MS (APCI): calculated for Chemical Formula: C9H17NO3 (M+H) = 188; found: 188. 1H NMR (400 MHz, TCE) 5 5.18 (s, 1H), 4.00 (d, J = 5.0 Hz, 2H), 2.44 (q, J = 7.4 Hz, 2H), 1.44 (s, 9H), 1.10 (t, J = 7.4 Hz, 3H).
2-Oxobutan-l-aminium chloride: The carbamate from the previous step (7.873 g, 42.05 mmol) was dissolved in 200 proof ethanol (50 mL) and treated with 12 N HCI solution (50 mL) with stirring at room temperature. The reaction mixture outgasses for a minute or two, then was stirred at room temperature for 30 minutes. The reaction mixture was evaporated to dryness and taken immediately to the next step. MS (APCI): calculated for Chemical Formula: C4H9NO (M+H) = 88; found: 88 (free base).
Ethyl 4-ethyl-2-methyl-lH-pyrrole-3-carboxylate: Ethyl acetoacetate (10.7 mL, 84.10 mmol), sodium acetate (420.5 mmol, 34.494 g) and the salt from the prior step (assume 100% yield, 42.05 mmol) were dissolved in water (300 mL) and heated at 80 0 C with stirring for four hours. The heat was turned off and the reaction mixture stirred at room temperature over the weekend. The reaction was filtered, wash with water, the crude product dissolved in DCM, separated from water, dried over magnesium sulfate, filtered, and evaporated to dryness in vacuo. Gives a brown solid, 6.859 g (90% yield). MS (APCI): calculated for Chemical Formula: C10H15NO2 (M+H) = 182; found: 182. 1H NMR (400 MHz, TCE) 6 8.16 (s, 1H), 6.39 (dt, J = 2.3, 1.1 Hz, 1H), 4.26 (q, J = 7.1 Hz, 2H), 2.71 (qd, J = 7.4, 1.1 Hz, 2H), 2.49 (s, 3H), 1.35 (t, J = 7.1 Hz, 3H), 1.19 (t, J = 7.4 Hz, 3H). Compound is pure with no need for column chromatography.
3,3",5,5"-Tetra-tert-butyl-2'-formyl-[l,l':3',l"-terphenyl]-5'-yl 2-(4-(l,3-dioxo-5,ll-bis(4-
(trifluoromethyl)phenyl)-lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: 3, 3", 5,5"-
Tetra-tert-butyl-4'-formyl-l-phenol (872 mg, 1.750 mmol), 2-(4-(l,3-dioxo-5,ll-bis(4- (trifluoromethyl)phenyl)-lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (1490 mg, 2.100 mmol), DMAP.pTsOH salt (52 mg, 0.1750 mmol), and DIC (0.548 mL, 3.500 mmol) were stirred in dry DCM (50 mL) at room temperature for 30 minutes. The crude reaction mixture was evaporated onto ~30 g of flash silica gel in vacuo and packed into a loader. Purified by flash chromatography on silica gel (120g, 0% EtOAc/hexanes (2 CV)
Figure imgf000068_0001
20% (30 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a yellow solid, 2058 mg (99% yield). MS (APCI): calculated for Chemical Formula: CysHesFsNOg (M+H) = 1190; found: 1190. 1H NMR (400 MHz, TCE) δ 9.89 (s, 1H), 8.70 (s, 1H), 8.47 (s, 1H), 7.96 - 7.80 (m, 7H), 7.73 - 7.59 (m, 5H), 7.47 - 7.35 (m, 6H), 7.31 (dd, J = 8.3, 1.4 Hz, 1H), 7.24 (s, 2H), 7.17 (d, J = 1.7 Hz, 4H), 7.10 (dd, J = 8.3, 1.5 Hz, 1H), 6.96 (ddd, J = 8.5, 6.4, 1.3 Hz, 1H), 4.08 (s, 2H), 1.36 (s, 36H).
PLC-7 Diethyl l,9-diethyl-5,5-difluoro-3,7-dimethyl-10-(3,3",5,5"-tetra-tert-butyl-5'-(2-(4-(l,3- dioxo-5,ll-bis(4-(trifluoromethyl)phenyl)-lH-xantheno[2,l,9-def]isoquinolin-2(3H)- yl)phenyl)acetoxy)-[l,ll:3',l"-terphenyl]-2l-yl)-5H-4l4,5l4-dipyrrolo[l,2-c:2l,ll- f][l,3,2]diazaborinine-2,8-dicarboxylate: The aldehyde from the previous step (283 mg, 0.2000 mmol), Compound 1711-44 (91 mg, 0.5000 mmol), and pTsOH.H2O (4 mg, 0.02000 mmol) were stirred in dry DCE (20 mt) under argon at 60 ° C for three hours. The reaction was treated with DDQ (82 mg, 0.3600 mmol) and heating continued at 60 ° C for 30 minutes. The reaction was treated with additional DDQ (82 mg, 0.3600 mmol) and heating continued at 60 ° C for another 30 minutes. The reaction mixture was cooled to room temperature and treated with Et3N (0.22 mL, 1.600 mmol), and BF3.OEt2 (0.30 mL, 2.400 mmol). The addition of Et3N (0.22 mL, 1.600 mmol), and BF3.OEt2 (0.30 mL, 2.400 mmol) was repeated and the reaction mixture was stirred for one hour at 50 0 C. The crude reaction mixture was evaporated in vacuo onto ~40g of flash silica gel and packed into a loader. Purified by flash chromatography on silica gel (120g, 100% toluene/hexanes with EtOAc modifier, 0% -> 1% -> 2% isocratic step gradients)). Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 64 mg (20% yield). MS (APCI): calculated for Chemical Formula: CgsHgoBFshHOg (M+H) = 1581; found: 1581. 1H NMR (400 MHz, TCE) 5 8.48 (s, 1H), 7.91 (d, J = 8.3 Hz, 2H), 7.89 - 7.80 (m, 4H), 7.68 (dd, J = 8.2, 4.0 Hz, 4H), 7.47 - 7.37 (m, 5H), 7.31 (dd, J = 8.3, 1.4 Hz, 1H), 7.22 (t, J = 1.7 Hz, 2H), 7.13 - 7.04 (m, 5H), 6.96 (ddd, J = 8.5, 7.1, 1.4 Hz, 1H), 4.24 (q, J = 7.1 Hz, 4H), 4.12 (s, 2H), 2.64 (s, 6H), 2.36 (q, J = 7.3 Hz, 4H), 1.30 (t, J = 7.2 Hz, 6H), 1.14 (s, 36H), 0.89 (t, J = 7.3 Hz, 6H).
Photoluminescent Compound PLC-8:
Figure imgf000069_0001
PLC-8 Diethyl 3,7-diethyl-5,5-difluoro-l,9-dimethyl-10-(3,3",5,5"-tetra-tert-butyl-5'-(2-(4-(l,3- dioxo-5,ll-bis(4-(trifluoromethyl)phenyl)-lH-xantheno[2,l,9-def]isoquinolin-2(3H)- yl)phenyl)acetoxy)-[l,l':3',l"-terphenyl]-2'-yl)-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'- f][l,3,2]diazaborinine-2,8-dicarboxylate: 3,3",5,5"-Tetra-tert-butyl-2'-formyl-[l,l':3',l"-terphenyl]-
5'-yl 2-(4-(l,3-dioxo-5,ll-bis(4-(trifluoromethyl)phenyl)-lH-xantheno[2,l,9-def]isoquinolin-2(3H)- yl)phenyl)acetate (0.2000 mmol, 238 mg), ethyl 2-ethyl-4-methyl-lH— pyrrole-3-carboxylate (0.5000 mmol, 91 mg), and pTsOH.H2O (0.02000 mmol, 4 mg) were stirred in dry DCE (20 mL) at 50 ° C under argon for 90 minutes, then cooled to room temperature and treated with DDQ. (0.3600 mmol, 82 mg) and stirred at room temperature for ten minutes. The reaction mixture was treated with Et3N (1.600 mmol, 0.22 mL), and BF3.OEt2 2.400 mmol, 0.30 mL) were added to the reaction. The addition of Et3N (1.600 mmol, 0.22 mL), and BF3.OEt2 2.400 mmol, 0.30 mL) was repeated and the reaction stirred at 50 ° C for 60 minutes. The reaction mixture was cooled to room temperature and evaporated onto ~35g of flash silica gel in vacuo and packed into a loader. Purified by flash chromatography on silica gel (120g, 0% acetone/hexane (2 CV)
Figure imgf000070_0001
10% (60 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 174 mg (55% yield). MS (APCI): calculated for Chemical Formula: C9sH90BFsN3O9 (M+H) = 1581; found: 1581. 1H NMR (400 MHz, TCE) δ 8.70 (s, 1H), 8.47 (s, 1H), 7.98 - 7.82 (m, 7H), 7.67 (d, J = 8.0 Hz, 4H), 7.49 - 7.35 (m, 6H), 7.31 (dd, J = 8.3, 1.3 Hz, 1H), 7.21 (t, J = 1.8 Hz, 2H), 7.10 (dd, J = 8.3, 1.5 Hz, 1H), 7.01 - 6.90 (m, 5H), 4.25 (q, J = 7.1 Hz, 4H), 4.11 (s, 2H), 3.13 - 2.98 (m, 4H), 2.02 (s, 6H), 1.31 (t, J = 7.1 Hz, 6H), 1.12 (s, 42H).
Photoluminescent Compound PLC-9:
Figure imgf000070_0002
PLC-9 Diethyl 10-(5'-(2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-3,3",5,5"-tetra-tert-butyl-[l,r:3',l"-terphenyl]-2'-yl)-5,5- dicyano- 1,3,7, 9-tetramethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',r-f][l, 3, 2]diazaborinine-2, 8- dicarboxylate: Diethyl 10-(5'-(2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH- xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-3,3",5,5"-tetra-tert-butyl-[l,l':3',l"- terphenyl]-2'-yl)-5,5-d if luoro-l,3,7,9-tetramethyl-5 H-4l4,5l4-dipyrrolo[l,2-c:2',l f][l,3,2]diazaborinine-2,8-dicarboxylate (0.07936 mmol, 134 mg) was dissolved in dry DCE (10 mL) and stirred at room temperature under argon. The reaction was treated with TMSCN (2.000 mmol, 0.25mL), then BF3.OEt2 (0.1500 mmol, 0.019 mL). The reaction mixture was stirred at room temperature for a few minutes, then heated to 45 ° C for 120 minutes. The crude reaction mixture was poured into ~30 mL of saturated NaHCO3 and stirred for a few minutes. The reaction was filtered through a polypropylene frit to retain water, eluting product with DCM. The eluent was evaporated to dryness in vacuo, dissolved in a small amount of DCM, and loaded onto ~15g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (80g, 0% acetone/hexanes (2 CV) -> 20% (5 CV), stopping gradient at 7.6%, 7.9%, 8.1%, and 8.4%. Fractions containing product were evaporated to dryness in vacuo, triturated with 80% MeOH/water, filtered, washed with 80% MeOH/water, dissolved in DCM, and evaporated to dryness in vacuo. Gives an orange solid, 121 mg (90% yield). MS (APCI): calculated for Chemical Formula: C97H84BF12N5O9 (M+H) = 1703; found: 1703. 1H NMR (400 MHz, TCE) δ 8.75 (s, 1H), 8.50 (s, 1H), 8.27 (d, J = 1.7 Hz, 2H), 8.08 (s, 1H), 8.06 - 7.96 (m, 3H), 7.72 - 7.61 (m, 2H), 7.49 (ddd, J = 8.5, 6.1, 2.6 Hz, 1H), 7.43 - 7.36 (m, 4H), 7.31 - 7.26 (m, 1H), 7.25 (t, J = 1.8 Hz, 2H), 7.04 - 6.95 (m, 2H), 6.89 (d, J = 1.8 Hz, 4H), 4.31 (q, J = 7.1 Hz, 4H), 4.09 (s, 2H), 2.81 (s, 6H), 2.10 (s, 6H), 1.34 (t, J = 7.1 Hz, 6H), 1.13 (s, 36H).
Photoluminescent Compound PLC-10:
Figure imgf000072_0001
Ethyl 2-ethyl-4-methyl-lH-pyrrole-3-carboxylate: Ethyl 3-oxopentanoate (100.0 mmol, 14.2 mL), aminoacetone hydrochloride (150.0 mmol, and 16.440 g), NaOAc (200.0 mmol, 16.406 g) were stirred in acetic acid (100 mL) and water (100 mL) at 100 °C over the weekend under argon. The reaction mixture was cooled to room temperature and most of the solvents were evaporated in vacuo. The mixture was partitioned between DCM (200 mL) and water (50 mL). The remainder of acetic acid was carefully quenched with 10% K2CO3 solution. The layers were separated, the aqueous layer was extracted 2 X 50 mL DCM, the combined organic layers were dried over magnesium sulfate, filtered, and evaporated to dryness in vacuo. The crude material was dissolved in a small amount of DCM and loaded onto ~50g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel
Figure imgf000073_0001
15% (15 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a light yellow oil, 7.985 g (44% yield). MS (APCI): calculated for Chemical Formula: C10H15NO2 (M+H) = 182; found: 182.
Diethyl 10-(5'-(2-(4-(l,3-dioxo-5,ll-bis(4-(trifluoromethyl)phenyl)-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-[l,l':3',l"-terphenyl]-2'-yl)-5,5-difluoro-l,3,7,9- tetramethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8-dicarboxylate: 2'-Formyl-
[l,l':3',l"-terphenyl]-5,-yl 2-(4-(l,3-dioxo-5,ll-bis(4-(trifluoromethyl)phenyl)-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetate (0.3000 mmol, 290 mg), the pyrrole from the previous step (0.6300 mmol, 114 mg), and pTsOH.H2O (0.06000 mmol, 11 mg) were stirred in dry DCE (20 mL) at 40 °C under argon for 60 minutes. The reaction was cooled to room temperature and DDQ. (0.4500 mmol, 102 mg) was added and stirred at room temperature for 10 minutes. Et3N (2.400 mmol, 0.33 mL), and BF3.OEt2 (3.600 mmol, 0.44 mL) were added to the reaction. The addition of Et3N (2.400 mmol, 0.33 mL), and BF3.OEt2 (3.600 mmol, 0.44 mL) was repeated and the reaction stirred at 50 ° C for 30 minutes. The reaction mixture was cooled to room temperature and quenched with 5 mL water and stirred for a few minutes, then filtered through a polypropylene frit to retain water. The frit was eluted with DCM. The eluent was directed onto a 15g flash silica plug, eluting with DCM, then eluting with 33% acetone/DCM. The solvents were evaporated to dryness in vacuo, dissolved in a small amount of DCM and loaded onto 15g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel
Figure imgf000073_0002
stop at 12.0%, 13.0%, 13.6%, 14.0%, 14.5%, 15.1%, 15.5%, 16.0%, and 17.0%, isocratic at each step. Fractions containing product were evaporated to dryness in vacuo. The product was triturated with hot MeOH, cooled to room temperature, filtered off, washing with MeOH, dissolved in DCM, and evaporated to dryness. Gives an orange solid, 205 mg (50% yield). MS (APCI): calculated for Chemical Formula: C77H54BF8N3O9 (M+H) = 1328; found: 1328. 1H NMR (400 MHz, TCE) δ 8.71 (s, 1H), 8.48 (s, 1H), 7.94 - 7.82 (m, 5H), 7.67 (dd, J = 8.3, 3.6 Hz, 3H), 7.46 - 7.37 (m, 5H), 7.31 (dd, J = 8.3, 1.3 Hz, 1H), 7.23 (dt, J = 5.3, 3.0 Hz, 5H), 7.20 - 7.14 (m, 4H), 7.10 (dd, J = 8.3, 1.5 Hz, 1H), 6.96 (ddd, J = 8.4, 7.2, 1.4 Hz, 1H), 4.27 (q, J = 7.1 Hz, 4H), 4.08 (s, 2H), 3.11 (q, J = 7.3 Hz, 4H), 1.97 (s, 6H), 1.34 (t, J = 7.1 Hz, 6H), 1.20 (t, J = 7.3 Hz, 6H).
PLC-10 Diethyl 5,5-dicyano-10-(5'-(2-(4-(l,3-dioxo-5,ll-bis(4-(trifluoromethyl)phenyl)-lH- xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-[l,l':3',l"-terphenyl]-2'-yl)-l,3,7,9- tetramethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8-dicarboxylate: The difluoropyrrole from the previous step (0.07500 mmol, 102 mg), TMSCN (0.7500 mmol, 0.094 mL), and BF3.OEt2 (0.1125 mmol, 0.014 mL) were stirred in dry DCE (10 mL) at RT under argon for 5 minutes. The temperature was increased to 45 ° C for 120 minutes, then at room temperature overnight. The crude reaction mixture was poured into 30 mL of sat. NaHCCh solution and stirred for 5 minutes, then filtered through a polypropylene frit to retain water. The frit was eluted with DCM. The organic eluent was evaporated to dryness in vacuo, dissolved in a small amount of DCM and loaded onto 15g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (80g, 0% acetone/hexane (2 CV) -> 10% (5 CV), stop at 1.0%, then to 1.3%, isocratic at each step. Fractions containing product were evaporated to dryness in vacuo. The product was triturated with hot MeOH, cooled to room temperature, filtered, washed with MeOH, dissolved in DCM, and evaporated to dryness in vacuo. Gives an orange solid, 64 mg (62% yield). MS (APCI): calculated for Chemical Formula: CsiHssBFsNsOg (M+H) = 1370; found: 1370. 1H NMR (400 MHz, TCE) δ 8.70 (s, 1H), 8.47 (s, 1H), 7.91 (d, J = 8.3 Hz, 2H), 7.89 - 7.81 (m, 4H), 7.70 - 7.63 (m, 4H), 7.47 - 7.36 (m, 5H), 7.31 (dd, J = 8.4, 1.3 Hz, 1H), 7.26 (p, J = 3.7 Hz, 6H), 7.18 - 7.12 (m, 4H), 7.09 (dd, J = 8.4, 1.5 Hz, 1H), 6.96 (ddd, J = 8.4, 7.2, 1.4 Hz, 1H), 4.30 (q, J = 7.1 Hz, 4H), 4.08 (s, 2H), 3.26 (q, J = 7.2 Hz, 4H), 1.99 (s, 6H), 1.36 (t, J = 7.1 Hz, 6H), 1.31 (t, J = 7.3 Hz, 6H).
Photoluminescent Compound PLC-12:
Figure imgf000075_0001
5'-Hydroxy-[l,ll:3',l"-terphenyl]-2'-carbaldehyde: 2,6-dibromo-4-hydroxybenzaldehyde (20.00 mmol, 5598 mg), phenylboronic acid (80.00 mmol, 9754 mg), sodium bicarbonate (120.0 mmol,
10.081 g), and Pd (dppfJCL (4.000 mmol, 2927 mg) were combined in THF (150 mL) and water (12 mL) and heated to 75 ° C under argon for three hours. The reaction mixture was cooled and most of the THF evaporated in vacuo. The crude mixture was suspended in acetone and evaporated onto ~50g of flash silica gel and packed into a loader. Purified by flash chromatography on silica gel (220g, 0% acetone/hexanes (2 CV) -> 40% (15 CV)). Fractions containing product were evaporated to dryness in vacuo, then triturated with 50:50 MeOH:water. The product was filtered off, washed with 50% MeOH/water, and dried at 80 ° C under vacuum. Gives a whitish solid, 4348 mg (79% yield). MS (APCI): calculated for Chemical Formula: C19H14O2 (M+H) = 275 found: 275. 1H NMR (400 MHz, Acetone) 6
9.77 (s, 1H), 7.51 - 7.27 (m, 10H), 6.85 (s, 2H).
2'-Formyl-[l,l':3',l"-terphenyl]-5'-yl 2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH- xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: The aldehyde from the previous step (1.500 mmol, 411 mg), 2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9- def] isoquinolin-2(3H)-yl)phenyl)acetic acid (1.650 mmol, 1395 mg), DMAP.pTsOH salt (0.1500 mmol, 44 mg), and EDC.HCI (2.500 mmol, 719 mg were stirred in dry DCE (20 mL) for one hour. The reaction mixture was loaded onto ~40g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (120g, Acetone/DCM (2 CV) 20% (5 CV), stopping gradient at 1.8%). Fractions containing product were evaporated to dryness in vacuo. Gives a yellow solid, 1183 mg (72% yield). MS (APCI): calculated for Chemical Formula: CeiHsiFizNOe (M+H) = 1102 found: 1102. 1H NMR (400 MHz, TCE) 6 9.87 (s, 1H), 8.75 (s, 1H), 8.50 (s, 1H), 8.27 (d, J = 1.6 Hz, 2H), 8.07 (s, 1H), 8.05 - 8.00 (m, 3H), 7.65 - 7.57 (m, 2H), 7.52 - 7.34 (m, 13H), 7.31 - 7.26 (m, 1H), 7.22 (s, 2H), 7.08 - 6.91 (m, 2H), 4.04 (s, 2H).
PLC-11 Dimethyl 10-(5'-(2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH- xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-[l,ll:3',l"-terphenyl]-2l-yl)-5,5-difluoro- 3,7-diisopropyl-l,9-dimethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8- dicarboxylate: The aldehyde from the previous step (0.4000 mmol, 441 mg), ethyl 2-isopropyl-4- methyl-lH-pyrrole-3-carboxylate (0.8000 mmol, 145 mg), and pTsOH.HzO (0.08000 mmol, 15 mg) were stirred at 35 °C under argon in dry DCE (25 mL) overnight. The reaction mixture was cooled to room temperature and DDQ (2.400 mmol, 545 mg) was added and stirred at room temperature for 10 minutes. To the reaction was added EtsN (3.200 mmol, 0.45 mL), and BF3.OEt2 (4.800 mmol, 0.59 mL) were added to the reaction. The addition of EtsN (3.200 mmol, 0.45 mL), and BFs.OEt? (4.800 mmol, 0.59 mL) was repeated and the reaction stirred at 70 °C for 24h. The reaction mixture was cooled to room temperature and quenched with 10 mL water and stirred for 5 minutes. The reaction mixture was filtered through a polypropylene frit to retain water. The frit was eluted with DCM. The organic eluent was evaporated to dryness in vacuo, dissolved in a small amount of DCM and loaded onto 15g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (120g, 0% acetone/hexanes (2 CV) -> 20% (5 CV), stopping gradient at 0.3%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, and 1.1%). Fractions containing product were evaporated to dryness in vacuo. The product was triturated with MeOH, filtered off, washed with MeOH, dissolved in DCM, and evaporated to dryness in vacuo. Gives an orange solid, 230 mg (39% yield). MS (APCI): calculated for Chemical Formula: C77H50BCI4F8N3O9 (M+H) = 1464 found: 1464. 1H NMR (400 M Hz, TCE) δ 8.70 (s, 1H), 8.47 (s, 1H), 7.91 (d, J = 8.3 Hz, 2H), 7.88 - 7.82 (m, 4H), 1J1. - 7.64 (m, 4H), 7.47 - 7.37 (m, 4H), 7.31 (dd, J = 8.3, 1.4 Hz, 1H), 7.10 (dd, J = 8.4, 1.5 Hz, 1H), 7.05 (d, J = 1.8 Hz, 4H), 6.96 (ddd, J = 8.4, 7.1, 1.3 Hz, 1H), 4.28 (q, J = 7.1 Hz, 4H), 4.08 (s, 2H), 2.76 (s, 6H), 1.90 (s, 7H), 1.35 (t, J = 7.1 Hz, 6H).
Photoluminescent Compound PLC-12:
Figure imgf000077_0001
PLC-12 Diethyl 10-(5'-(2-(4-(l,3-dioxo-5,ll-bis(4-(trifluoromethyl)phenyl)-lH-xantheno[2,l,9- def]75soquinoline-2(3H)-yl)phenyl)acetoxy)-[l,l':3’,l"-terphenyl]-2'-yl)-3,7-diethyl-5,5-difluoro- l,9-dimethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8-dicarboxylate: 2'-Formyl-
[l,l,:3',l"-terphenyl]-5'-yl 2-(4-(l,3-dioxo-5,ll-bis(4-(trifluoromethyl)phenyl)-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetate (0.3000 mmol, 290 mg), ethyl 2-ethyl-4-methyl-lH-pyrrole-3- carboxylate (0.6300 mmol, 114 mg), and pTsOH.FhO (0.06000 mmol, 11 mg) were stirred in dry DCE (20 mL) at 40 ° C under argon for one hour. The reaction mixture was cooled to room temperature and treated with DDQ (0.4500 mmol, 102 mg) and stirred at room temperature for 10 minutes. The reaction mixture was treated with EtgN (2.400 mmol, 0.33 mL), and BF3.OEt2 3.600 mmol, 0.44 mL) were added to the reaction. The addition of EtgN (2.400 mmol, 0.33 mL), and BFa.OEtz 3.600 mmol, 0.44 mL) was repeated and the reaction stirred at 50 ° C for one hour. The reaction mixture was cooled to room temperature and quenched with 10 mL water and stirred for 5 minutes. The reaction mixture was filtered through a polypropylene frit to retain water. The frit was eluted with DCM. The organic eluent was evaporated to dryness in vacuo, dissolved in a small amount of DCM and loaded onto ~45g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (120g, 0% acetone/hexanes (2 CV) -> 50% (5 CV), stopping gradient at 12.0%, then 13.0%, 13.6%, 14.0%, 14.5%, 14.9%, 15.1%, 15.5%, 16.0%, and 17.0%. Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 205 mg (50% yield). MS (APCI): calculated for Chemical Formula: CygHssBFgNaOg (M+H) = 1356 found: 1356. 1H NMR (400 MHz, TCE) δ 8.71 (s, 1H), 8.48 (s, 1H), 7.94 - 7.82 (m, 5H), 7.67 (dd, J = 8.3, 3.6 Hz, 3H), 7.46 - 7.37 (m, 5H), 7.31 (dd, J = 8.3, 1.3 Hz, 1H), 7.23 (dt, J = 5.3, 3.0 Hz, 5H), 7.20 - 7.14 (m, 4H), 7.10 (dd, J = 8.3, 1.5 Hz, 1H), 6.96 (ddd, J = 8.4, 7.2, 1.4 Hz, 1H), 4.27 (q, J = 7.1 Hz, 4H), 4.08 (s, 2H), 3.11 (q, J = 7.3 Hz, 4H), 1.97 (s, 6H), 1.34 (t, J = 7.1 Hz, 6H), 1.20 (t,
J = 7.3 Hz, 6H).
Photoluminescent Compound PLC-13:
Figure imgf000078_0001
PLC-13 Diethyl 3,7-dibutyl-10-(5'-(2-(4-(l,3-dioxo-5,ll-bis(4-(trifluoromethyl)phenyl)-lH- xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-[l,l':3',l"-terphenyl]-2'-yl)-5,5-difluoro- l,9-dimethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8-dicarboxylate: 2' Formyl- [l,l':3',l"-terphenyl]-5'-yl 2-(4-(l,3-dioxo-5,ll-bis(4-(trifluoromethyl)phenyl)-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetate (0.3000 mmol, 290 mg), ethyl 2-butyl-4-methyl-lH-pyrrole-3- carboxylate (0.6300 mmol, 132 mg), and pTsOH.H2O (0.06000 mmol, 11 mg) were stirred in dry DCE (25 mL) under argon at 40 ° C for 3 hours. The reaction mixture was cooled to room temperature and treated with DDQ (0.9000 mmol, 204 mg) and stirred at room temperature for 10 minutes. The reaction mixture was treated with Et3N (2.400 mmol, 0.33 mL), and BF3.OEt2 3.600 mmol, 0.44 mL) were added to the reaction. The addition of Et3N (2.400 mmol, 0.33 mL), and BF3.OEt2 3.600 mmol, 0.44 mL) was repeated and the reaction stirred at 50 ° C for one hour. The reaction mixture was cooled to room temperature and quenched with 10 mL water and stirred for 5 minutes. The reaction mixture was filtered through a polypropylene frit to retain water. The frit was eluted with DCM. The organic eluent was evaporated to dryness in vacuo, dissolved in a small amount of DCM and loaded onto ~45g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (80g, 0%
Figure imgf000078_0002
stopping gradient at 11.1%, 12.5%, 13.4%, 14.5%, 15.5%, and 16.5%. Fractions containing product were evaporated to dryness in vacuo. Repurified (load ontol5g of flash silica gel packed into a loader), 40g, 0% EtOAc/hexanes (2 CV)
Figure imgf000079_0001
35% (5 CV), stopping gradient at 21.6%, 22.1%, and 22.5%. Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 143 mg (34% yield). MS (APCI): calculated for Chemical Formula: CssHesBFsNsOg (M+H) = 1413 found: 1413. 1H NM R (400 MHz, TCE) δ 8.62 (s, 1H), 8.39 (s, 1H), 7.82 (d, J = 8.3 Hz, 2H), 7.80 - 7.71 (m, 4H), 7.58 (dd, J = 8.3, 3.7 Hz, 4H), 7.38 - 7.26 (m, 5H), 7.22 (dd, J = 8.3, 1.3 Hz, 1H), 7.17 - 7.05 (m, 10H), 7.01 (dd, J = 8.4, 1.5 Hz, 1H), 6.87 (ddd, J = 8.4, 7.1, 1.4 Hz, 1H), 4.17 (q, J = 7.1 Hz, 4H), 3.99 (s, 2H), 2.99 (t, J = 7.8 Hz, 4H), 1.86 (s, 6H), 1.44 (h, J = 6.2 Hz, 4H), 1.27 (dt, J = 16.7, 7.2 Hz, 10H), 0.83 (t, J = 7.3 Hz, 6H).
Photoluminescent Compound PLC-14:
Figure imgf000079_0002
PLC-14 Diethyl 10-(5'-(2-(4-(l,3-dioxo-5,ll-bis(4-(trifluoromethyl)phenyl)-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-3,3",5,5"-tetrafluoro-[l,ll:3',l"-terphenyl]-2'-yl)-5,5- difluoro-l,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8- dicarboxylate: 3,3",5,5"-Tetrafluoro-2'-formyl-[l,l':3',l"-terphenyl]-5'-yl 2-(4-(l,3-dioxo-5,ll-bis(4- (trifluoromethyl)phenyl)-lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetate (0.3000 mmol, 311 mg), ethyl 2,4-dimethyl-lH-pyrrole-3-carboxylate (0.6300 mmol, 105 mg), and pTsOH.H2O (0.06000 mmol, 11 mg) were stirred in dry DCE (25 mL) under argon at 40 °C for 3 hours. The reaction mixture was cooled to room temperature and treated with DDQ (0.6000 mmol, 136 mg) and stirred at room temperature for 10 minutes. The reaction mixture was treated with Et3N (2.400 mmol, 0.33 mL), and BF3.OEt23.600 mmol, 0.44 mL) were added to the reaction. The addition of Et3N (2.400 mmol, 0.33 mL), and BF3.OEt2 3.600 mmol, 0.44 mL) was repeated and the reaction stirred at 50 °C for one hour. The reaction mixture was cooled to room temperature and quenched with 10 mL water and stirred for 5 minutes. The reaction mixture was filtered through a polypropylene frit to retain water. The frit was eluted with DCM. The organic eluent was evaporated to dryness in vacuo, dissolved in a small amount of DCM and loaded onto 15g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (40g, 0% acetone/hexanes (2 CV) -> 25% (5 CV), stop gradient at 13.5%, 14.0%, 14.5%, and 14.9%. Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 241 mg (57% yield). MS (APCI): calculated for Chemical Formula: C77H54BF8N3O9 (M+H) = 1328 found: 1328. 1H NM R (400 MHz, TCE) δ 8.70 (s, 1H), 8.47 (s, 1H), 7.91 (d, J = 8.3 Hz, 2H), 7.88 - 7.81 (m, 4H), 7.73 - 7.63 (m, 4H), 7.47 - 7.37 (m, 5H), 7.31 (dd, J = 8.3, 1.3 Hz, 1H), 7.10 (dd, J = 8.4, 1.5 Hz, 1H), 6.96 (ddd, J = 8.4, 7.1, 1.4 Hz, 1H), 6.74 (dddd, J = 18.0, 8.6, 4.8, 2.3 Hz, 6H), 4.27 (q, J = 7.1 Hz, 4H), 4.08 (s, 2H), 2.75 (s, 6H), 1.91 (s, 6H), 1.35 (t, J = 7.1 Hz, 6H).
Photoluminescent Compound PLC-15:
Figure imgf000080_0001
PLC-15 Diethyl 10-(5'-(2-(4-(l,3-dioxo-5,ll-bis(4-(trifluoromethyl)phenyl)-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-3,3",5,5"-tetrafluoro-[l,l':3',l"-terphenyl]-2'-yl)-3,7- diethyl-5, 5-difluoro-l, 9-dimethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',r-f][l, 3, 2]diazaborinine-2, 8- dicarboxylate: 3,3",5,5"-Tetrafluoro-2'-formyl-[l,l':3,,l"-terphenyl]-5,-yl 2-(4-(l,3-dioxo-5,ll-bis(4- (trifluoromethyl)phenyl)-lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetate (0.3000 mmol, 311 mg), ethyl 2-ethyl-4-methyl-lH-pyrrole-3-carboxylate (0.6300 mmol, 114 mg), and pTsOH.HzO (0.06000 mmol, 11 mg) were stirred in dry DCE (25 ml) under argon at 40 ° C for 3 hours. The reaction mixture was cooled to room temperature and treated with DDQ (1.800 mmol, 409 mg) and stirred at room temperature for 10 minutes. The reaction mixture was treated with Et3N (2.400 mmol, 0.33 mL), and BF3.OEt2 3.600 mmol, 0.44 mL) were added to the reaction. The addition of Et3N (2.400 mmol, 0.33 mL), and BF3.OEt2 3.600 mmol, 0.44 mL) was repeated and the reaction stirred at 50 ° C for one hour. The reaction mixture was cooled to room temperature and quenched with 10 mL water and stirred for 5 minutes. The reaction mixture was filtered through a polypropylene frit to retain water. The frit was eluted with DCM. The organic eluent was evaporated to dryness in vacuo, dissolved in a small amount of DCM and loaded onto 15g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (40g, 0% acetone/DCM (2 CV) -> 25% (5 CV), stop gradient at 14.3%, 14.5%, and 14.8%. Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 266 mg (62% yield). MS (APCI): calculated for Chemical Formula: CygHssBFsNsOg (M+H) = 1356 found: 1356. 1H NMR (400 MHz, TCE) δ 8.71 (s, 1H), 8.48 (s, 1H), 7.91 (d, J = 8.3 Hz, 2H), 7.89 - 7.80 (m, 4H), 7.67 (d, J = 8.1 Hz, 4H), 7.49 - 7.35 (m, 5H), 7.31 (dd, J = 8.3, 1.3 Hz, 1H), 7.10 (dd, J = 8.4, 1.5 Hz, 1H), 6.96 (ddd, J = 8.4, 7.1, 1.4 Hz, 1H), 6.81 - 6.63 (m, 6H), 4.28 (q, J = 7.1 Hz, 4H), 4.08 (s, 2H), 3.16 (q, J = 7.3 Hz, 4H), 1.91 (s, 6H), 1.35 (t, J = 7.1 Hz, 6H), 1.25 (t, J = 8.1 Hz, 10H).
Photoluminescent Compound PLC-16:
Figure imgf000082_0001
Ethyl 2-butyl-4-methyl-lH-pyrrole-3-carboxylate: Ethyl 3-oxoheptanoate (20.00 mmol, 3.55 mL) and aminoacetone hydrochloride (40.00 mmol, 4.384 g) were combined in water (100 mL) and 200 pf ethanol (50 ml) and heated to 80 °C for 300 minutes. The crude reaction mixture was extracted with DCM (3 X 100 mL), dried over magnesium sulfate, filtered, and evaporated to dryness. The crude mixture was dissolved in DCM and loaded onto ~40g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (120g, 0% EtOAc/DCM (2 CV) 2% (20 CV)). Fractions containing product were evaporate to dryness. Gives a waxy brownish solid, 2.485g (59% yield). MS (APCI): calculated for Chemical Formula: Ci2HigNO2 (M+H) = 210; found: 210. 1H NMR (400 MHz, TCE) δ 8.06 (s, 1H), 6.39 (dd, J = 2.3, 1.2 Hz, 1H), 4.25 (q, J = 7.1 Hz, 2H), 2.97 - 2.75 (m, 2H), 2.24 (d, J = 1.1 Hz, 3H), 1.71 - 1.51 (m, 2H), 1.35 (t, J = 7.1 Hz, 5H), 0.94 (t, J = 7.3 Hz, 3H). 3,3",5,5"-tetrafluoro-5'-hydroxy-[l,l':3',l"-terphenyl]-2'-carbaldehyde: 2,6-dibromo-4- hydroxybenzaldehyde (10.00 mmol, 2800 mg), (3,5-difluorophenyl)boronic acid (40.00 mmol, 6316 mg), sodium bicarbonate (60.00 mmol, 5041 mg), and Pd(dppf)CI2 (2.000 mmol, 1464 mg) were combined in THF (150 mL) and water (14 ml_) and heated to 75 ° C under argon for one hour. The reaction mixture was cooled and most of the THF evaporated in vacuo. The crude mixture was suspended in acetone and evaporated onto ~50g of flash silica gel and packed into a loader. Purified by flash chromatography on silica gel (120g, 0% acetone/hexanes (2 CV) -> 40% (10 CV)). Fractions containing product were evaporated to dryness in vacuo, then triturated with 90:10 MeOH:water. The product was filtered off, washed with 10% MeOH/water, and dried at 80 ° C under vacuum. Gives a whitish solid, 3.167 g (92% yield). MS (APCI): calculated for Chemical Formula: C19H10F4O2 (M+H) = 347 found: 347. 1H NMR (400 MHz, DMSO) 8 10.92 (s, 1H), 9.64 (s, 1H), 7.28 (tt, J = 9.4, 2.3 Hz, 2H), 7.19 - 7.09 (m, 4H), 6.79 (s, 2H).
3,3",5,5"-Tetrafluoro-2'-formyl-[l,l':3',l"-terphenyl]-5'-yl 2-(4-(l,3-dioxo-5,ll-bis(4-
(trifluoromethyl)phenyl)-lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: The phenol from the previous step (4.000 mmol, 1385 mg), 2-(4-(l,3-dioxo-5,ll-bis(4-(trifluoromethyl)phenyl)- lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (4.800 mmol, 3406 mg), DMAP.pTsOH salt (0.4000 mmol, 118 mg), and EDC.HCI (8.000 mmol, 1534 mg were stirred in a capped vial in dry DCM (35 mL) for one hour. The reaction mixture was loaded onto ~40g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (120g, EtOAc/DCM (2 CV) -> 20% (5 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a yellow solid, 4137 mg (100% yield). MS (APCI): calculated for Chemical Formula: C59H29F10NO6 (M+H) = 1038 found: 1038. 1H NMR (400 MHz, TCE) δ 9.87 (s, 1H), 8.70 (s, 1H), 8.47 (s, 1H), 7.96 - 7.81 (m, 6H), 7.67 (d, J = 8.0 Hz, 2H), 7.65 - 7.58 (m, 2H), 7.43 (ddd, J = 8.6, 7.1, 1.5 Hz, 1H), 7.40 - 7.35 (m, 2H), 7.31 (dd, J = 8.3, 1.3 Hz, 1H), 7.26 (s, 2H), 7.10 (dd, J = 8.3, 1.5 Hz, 1H), 7.01 - 6.87 (m, 7H), 4.04 (s, 2H).
PLC-16 Diethyl 3,7-dibutyl-10-(5'-(2-(4-(l,3-dioxo-5,ll-bis(4-(trifluoromethyl)phenyl)-lH- xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-3,3",5,5"-tetrafluoro-[l,l':3',l"- terphenyl]-2'-yl)-5,5-difluoro-l,9-dimethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine- 2,8-dicarboxylate): The aldehyde from the previous step (0.3000 mmol, 311 mg), ethyl 2-butyl-4- methyl-lH-pyrrole-3-carboxylate (0.6300 mmol, 132 mg), and pTsOH.H2O (0.06000 mmol, 11 mg) were stirred at 40 °C under argon in dry DCE (25 mL) overnight. The reaction mixture was cooled to room temperature and DDQ (1.800 mmol, 409 mg) was added and stirred at room temperature for 10 minutes. To the reaction was added EtsN (2.400 mmol, 0.33 mL), and BF3.OEt2 3.600 mmol, 0.44 mL) were added to the reaction. The addition of EtsN (2.400 mmol, 0.33 mL), and BF3.OEt23.600 mmol, 0.44 mL) was repeated and the reaction stirred at 50 °C for 30 minutes. The reaction mixture was cooled to room temperature and quenched with 10 mL water and stirred for 5 minutes The reaction mixture was filtered through a polypropylene frit to retain water. The frit was eluted with DCM. The organic eluent was evaporated to dryness in vacuo, dissolved in a small amount of DCM and loaded onto 15g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (80g, 0% acetone/hexanes (2 CV) -> 25% (5 CV), stopping gradient at 13.5%. Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 60 mg (14% yield). MS (APCI): calculated for Chemical Formula: CsaHezBFuNjOg (M+H) = 1484 found: 1484. 1H NMR (400 MHz, TCE) δ 8.70 (s, 1H), 8.47 (s, 1H), 7.91 (d, J = 8.3 Hz, 2H), 7.89 - 7.81 (m, 4H), 7.67 (d, J = 8.1 Hz, 4H), 7.50 - 7.38 (m, 5H), 7.31 (dd, J = 8.3, 1.3 Hz, 1H), 7.10 (dd, J = 8.4, 1.5 Hz, 1H), 6.96 (ddd, J = 8.4, 7.1, 1.4 Hz, 1H), 6.81 - 6.62 (m, 6H), 4.28 (q, J = 7.1 Hz, 4H), 4.08 (s, 2H), 3.13 (t, J = 7.9 Hz, 4H), 1.90 (s, 6H), 1.63 - 1.51 (m, 4H), 1.41 (q, J = 7.5 Hz, 4H), 1.35 (t, J = 7.1 Hz, 6H), 0.94 (t, J = 7.3 Hz, 6H).
Photoluminescent Compound PLC-17:
Figure imgf000084_0001
Ethyl 2-isobutyl-4-methyl-lH-pyrrole-3-carboxylate: Ethyl 5-methyl-3-oxohexanoate (20.00 mmol, 3.56 mL) and aminoacetone hydrochloride (40.00 mmol, 4.384 g) were combined in water (100 mL) and 200 pf ethanol (50 ml) and heated to 80 °C for 300 minutes. The crude reaction mixture was extracted with DCM (3 X 100 mL), dried over magnesium sulfate, filtered, and evaporated to dryness. The crude mixture was dissolved in DCM and loaded onto ~40g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (120g, 0% EtOAc/DCM (2 CV)
Figure imgf000084_0002
2% (20 CV)). Fractions containing product were evaporate to dryness. Gives a thick yellow liquid, 1750mg (42% yield). MS (APCI): calculated for Chemical Formula: C12H19NO2 ( M+H ) = 210; found: 210. 1H NMR (400 MHz, TCE) 6 7.98 (s, 1H), 6.40 (dd, J = 2.3, 1.1 Hz, 1H), 4.24 (q, J = 7.1 Hz, 2H), 2.74 (d, J = 7.2 Hz, 2H), 2.24 (d, J = 1.1 Hz, 3H), 1.94 (dh, J = 13.8, 6.9 Hz, 1H), 1.35 (t, J = 7.1 Hz, 3H), 0.92 (d, J = 6.7 Hz, 6H).
PLC-17 Diethyl 10-(5'-(2-(4-(l,3-dioxo-5,ll-bis(4-(trifluoromethyl)phenyl)-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-3,3",5,5"-tetrafluoro-[l,l':3',l"-terphenyl]-2'-yl)-5,5- difluoro-3,7-diisobutyl-l,9-dimethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8- dicarboxylate: 3,3",5,5"-Tetrafluoro-5'-hydroxy-[l,l':3',l"-terphenyl]-2'-carbaldehyde (0.3000 mmol, 311 mg), the pyrrole from the previous step (0.6300 mmol, 132 mg), and pTsOH.H2O (0.06000 mmol, 11 mg) were stirred in dry DCE (25 mL) under argon at 40 °C for 3 hours. The reaction mixture was cooled to room temperature and treated with DDQ. (1.800 mmol, 409 mg) and stirred at room temperature for 10 minutes. The reaction mixture was treated with Et3N (2.400 mmol, 0.33 mL), and BF3.OEt2 3.600 mmol, 0.44 mL) were added to the reaction. The addition of Et3N (2.400 mmol, 0.33 mL), and BF3.OEt2 3.600 mmol, 0.44 mL) was repeated and the reaction stirred at 50 °C for one hour. The reaction mixture was cooled to room temperature and quenched with 10 mL water and stirred for 5 minutes. The reaction mixture was filtered through a polypropylene frit to retain water. The frit was eluted with DCM. The organic eluent was evaporated to dryness in vacuo, dissolved in a small amount of DCM and loaded onto 15g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (40g, 0% acetone/hexanes (2 CV) -> 25% (5 CV), stopping gradient at 13.6% and 14.0%. Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 118 mg (27% yield). MS (APCI): calculated for Chemical Formula: C83H62BFi2N3O9 (M+H) = 1484 found: 1484. 1H NMR (400 MHz, TCE) δ 8.70 (s, 1H), 8.47 (s, 1H), 7.91 (d, J = 8.3 Hz, 2H), 7.89 - 7.82 (m, 4H), 7.71 - 7.61 (m, 4H), 7.46 (s, 2H), 7.44 - 7.37 (m, 3H), 7.31 (dd, J = 8.3, 1.3 Hz, 1H), 7.10 (dd, J = 8.3, 1.5 Hz, 1H), 6.96 (ddd, J = 8.4, 7.1, 1.4 Hz, 1H), 6.72 (dd, J = 6.7, 3.0 Hz, 6H), 4.26 (q, J = 7.1 Hz, 4H), 4.08 (s, 2H), 3.08 (d, J = 7.5 Hz, 4H), 1.87 (s, 6H), 1.34 (t, J = 7.1 Hz, 6H), 0.85 (d, J = 6.7 Hz, 12H).
Photoluminescent Compound PLC-18:
Figure imgf000086_0001
3,3",5,5"-Tetrachloro-5'-hydroxy-[l,l':3',l"-terphenyl]-2'-carbaldehyde: 2,6-Dibromo-4- hydroxybenzaldehyde (5.00 mmol, 1400 mg), (3,5-dichlorophenyl)boronic acid (20.00 mmol, 3816 mg), sodium bicarbonate (30.00 mmol, 2520 mg), and Pd(dppf)CI2 (1.000 mmol, 732 mg) were combined in THF (120 mL) and water (11 mL) and heated to 75 °C under argon for one hour. The reaction mixture was cooled and most of the THF evaporated in vacuo. The crude mixture was suspended in acetone and evaporated onto ~50g of flash silica gel and packed into a loader. Purified by flash chromatography on silica gel (120g, 0% acetone/hexanes (2 CV) -> 40% (10 CV)). Fractions containing product were evaporated to dryness in vacuo, then triturated with 90:10 MeOH:water. The product was filtered off, washed with 10% MeOH/water, and dried at 80 ° C under vacuum. Gives a whitish solid, 1926 g (94% yield). MS (APCI): calculated for Chemical Formula: C19H10CI4O2 (M+H) = 411 found: 411. 1H NMR (400 MHz, DMSO) δ 10.93 (s, 1H), 9.60 (s, 1H), 7.65 (t, J = 2.0 Hz, 2H), 7.48 (d, J =
1.9 Hz, 4H), 6.79 (s, 2H).
3,3",5,5"-Tetrachloro-2'-formyl-[l,l':3',l"-terphenyl]-5'-yl 2-(4-(l,3-dioxo-5,ll-bis(4-
(trifluoromethyl)phenyl)-lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: The phenol from the previous step (2.000 mmol, 824 mg), 2-(4-(l,3-dioxo-5,ll-bis(4-(trifluoromethyl)phenyl)-lH- xantheno[2,l,9-def] isoq uinolin-2(3H)-yl)phenyl)acetic acid (2.400 mmol, 1703 mg), DMAP.pTsOH salt (0.2000 mmol, 59 mg), and EDC.HCI (4.000 mmol, 767 mg were stirred in dry DCM (50 mL) for one hour. The reaction mixture was loaded onto ~40g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (120g, EtOAc/DCM (2 CV) -> 40% (10 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a yellow solid, 2054 mg (93% yield). MS (APCI): calculated for Chemical Formula: C59H29CI4F6NO6 (M+H) = 1102 found: 1102. 1H NMR (400 MHz, TCE) 6 8.71 (s, 1H), 8.48 (s, 1H), 7.95 - 7.81 (m, 6H), 7.70 - 7.62 (m, 4H), 7.48 - 7.38 (m, 3H), 7.31 (dd, J = 8.3, 1.3 Hz, 1H), 7.10 (dd, J = 8.4, 1.5 Hz, 1H), 6.96 (ddd, J = 8.4, 7.1, 1.4 Hz, 1H), 6.60 (s, 2H), 4.05 (s, 2H), 3.77 (s, 6H), 2.72 (s, 6H), 1.78 (s, 6H).
PLC-18 Diethyl 5,5-difluoro-l,3,7,9-tetramethyl-10-(3,3",5,5"-tetrachloro-5'-(2-(4-(l,3-dioxo-5,ll- bis(4-(trifluoromethyl)phenyl)-lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)- [l,l':3',l"-terphenyl]-2'-yl)-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8- dicarboxylate: The aldehyde from the previous step (0.3000 mmol, 331 mg), ethyl 2,4-dimethyl-lH- pyrrole-3-carboxylate (0.6300 mmol, 105 mg), and pTsOH.H2O (0.06000 mmol, 11 mg) were stirred at 40 °C under argon in dry DCE (25 mL) overnight. The reaction mixture was cooled to room temperature and DDQ. (0.6000 mmol, 136 mg) was added and stirred at room temperature for 10 minutes. To the reaction was added Et3N (2.400 mmol, 0.33 mL), and BF3.OEt2 3.600 mmol, 0.44 mL) were added to the reaction. The addition of Et3N (2.400 mmol, 0.33 mL), and BF3.OEt2 3.600 mmol, 0.44 mL) was repeated and the reaction stirred at 50 °C for 30 minutes. The reaction mixture was cooled to room temperature and quenched with 10 mL water and stirred for 5 minutes. The reaction mixture was filtered through a polypropylene frit to retain water. The frit was eluted with DCM. The organic eluent was evaporated to dryness in vacuo, dissolved in a small amount of DCM and loaded onto 15g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (40g, 0% acetone/hexanes (2 CV) -> 25% (5 CV), stopping gradient at 14.3% and 14.4%. Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 304 mg (69% yield). MS (APCI): calculated for Chemical Formula: C77H50BCI4F8N3O9 (M+H) = 1464 found: 1464. 1H NMR (400 MHz, TCE) δ 8.70 (s, 1H), 8.47 (s, 1H), 7.91 (d, J = 8.3 Hz, 2H), 7.88 - 7.82 (m, 4H), 7.72 - 7.64 (m, 4H), 7.47 - 7.37 (m, 4H), 7.31 (dd, J = 8.3, 1.4 Hz, 1H), 7.10 (dd, J = 8.4, 1.5 Hz, 1H), 7.05 (d, J = 1.8 Hz, 4H), 6.96 (ddd, J = 8.4, 7.1, 1.3 Hz, 1H), 4.28 (q, J = 7.1 Hz, 4H), 4.08 (s, 2H), 2.76 (s, 6H), 1.90 (s, 7H), 1.35 (t, J = 7.1 Hz, 6H).
Photoluminescent Compound PLC-19:
Figure imgf000088_0001
Quinolin-6-ylmethyl 2,4-dimethyl-lH-pyrrole-3-carboxylate: Quinolin-6-ylmethanol (15.00 mmol, 2388 mg), 2,4-dimethyl-lH-pyrrole-3-carboxylic acid (45.00 mmol, 6264 mg), and DMAP.pTsOH salt (45.00 mmol, 13.247 g) were stirred in dry DMF (40 mL) heated to 100 °C under argon atmosphere. To the reaction was added EDC.HCI (90.00 mmol, 17.203 g), rinsed down by 10 mL dry DMF. The reaction mixture was heated to 130 ° C and stirred for 60 minutes. The reaction was cooled to room temperature and evaporated to dryness in vacuo. The residue was taken up in some acetone and evaporated onto ~40g of flash silica gel in vacuo and packed into a loader. Purified by flash chromatography on silica gel (220g, 0% EtOAc/toluene (2 CV)
Figure imgf000088_0002
50% (25 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a light brown solid, 2370 mg (56% yield). MS (APCI): calculated for Chemical Formula: C17H16N2O2 (M+H) = 281 found: 281. 1H NMR (400 MHz, DMSO) δ 10.96 (s, 1H), 8.90 (dd, J = 4.2, 1.8 Hz, 1H), 8.38 (ddd, J = 8.4, 1.7, 0.8 Hz, 1H), 8.04 (d, J = 8.7 Hz, 1H), 7.99 (d, J = 1.9 Hz, 1H), 7.80 (dd, J = 8.7, 2.0 Hz, 1H), 7.54 (dd, J = 8.3, 4.2 Hz, 1H), 6.42 (dd, J = 2.3, 1.2 Hz, 1H), 5.39 (s, 2H), 2.38 (s, 3H), 2.13 (d, J = 1.1 Hz, 3H).
PLC-19 Bis(quinolin-6-ylmethyl) 5,5-difluoro-l,3,7,9-tetramethyl-10-(3,3",5,5"-tetra-tert-butyl-5'- (2-(4-(l,3-dioxo-5,ll-bis(4-(trifluoromethyl)phenyl)-lH-xantheno[2,l,9-def]isoquinolin-2(3H)- yl)phenyl)acetoxy)-[l,ll:3',l"-terphenyl]-2l-yl)-5H-4l4,5l4-dipyrrolo[l,2-c:2l,ll- f][l,3,2]diazaborinine-2,8-dicarboxylate: 3,3",5,5"-Tetra-tert-butyl-2'-formyl-[l,l':3,,l"-terphenyl]- S'-yl 2-(4-(l,3-dioxo-5,ll-bis(4-(trifluoromethyl)phenyl)-lH-xantheno[2,l,9-def]isoquinolin-2(3H)- yl)phenyl)acetate (0.2500 mmol, 298 mg), the pyrrole from the previous step (0.5000 mmol, 140 mg), and pTsOH.H2O (1.000 mmol, 190 mg) were stirred in dry DCE (15 mL) at 65 °C for 60 minutes, then cooled to room temperature. The reaction was treated with DDQ. (0.5000 mmol, 114 mg) and stirred for 10 minutes. To the reaction was added Et3N (2.000 mmol, 0.28 mL), and BF3.OEt2 (3.000 mmol, 0.37 mL) were added to the reaction. The addition of Et3N (2.000 mmol, 0.28 mL), and BF3.OEt2 (3.000 mmol, 0.37 mL) was repeated and the reaction stirred at 65 °C for 60 minutes. The reaction mixture was cooled to room temperature and quenched with 10 mL water and stirred for 5 minutes. The reaction mixture was filtered through a polypropylene frit to retain water. The frit was eluted with DCM. The organic eluent was evaporated to dryness in vacuo, dissolved in a small amount of DCM and loaded onto 15g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (120g, 0% acetone/hexane (2 CV) -> 30% (5 CV), stopping gradient at 12.0%, 13.0%, and 14.0%. Fractions containing product were evaporated to dryness in vacuo. The product was triturated with MeOH/water, filtered, washed with MeOH/water, dissolved in DCM, and evaporated to dryness in vacuo. Gives an orange solid, 188 mg (42% yield). MS (APCI): calculated for Chemical Formula: C109H92BF8N5O9 (M+H) = 1779 found: 1779. 1H NM R (400 MHz, TCE) δ 8.92 (dd, J = 4.3, 1.7 Hz, 2H), 8.70 (s, 1H), 8.47 (s, 1H), 8.20 - 8.14 (m, 2H), 8.10 (d, J = 8.7 Hz, 2H), 7.94 - 7.82 (m, 6H), 7.81 (d, J = 1.9 Hz, 2H), 7.72 - 7.62 (m, 6H), 7.47 - 7.35 (m, 7H), 7.31 (dd, J = 8.4, 1.3 Hz, 1H), 7.18 (t, J = 1.7 Hz, 2H), 7.09 (dd, J = 8.5, 1.6 Hz, 1H), 6.99 - 6.93 (m, 1H), 6.91 (d, J = 1.8 Hz, 4H), 5.44 (s, 4H), 4.08 (s, 2H), 2.64 (s, 6H), 2.01 (s, 6H), 1.06 (s, 36H).
Photoluminescent Compound PLC-20:
Figure imgf000089_0001
2-(9H-Carbazol-9-yl)ethyl 2,4-dimethyl-lH-pyrrole-3-carboxylate: 2-(9H-Carbazol-9-yl)ethan-l-ol (15.00 mmol, 2388 mg), 2,4-dimethyl-lH-pyrrole-3-carboxylic acid (45.00 mmol, 6264 mg), and DMAP.pTsOH salt (45.00 mmol, 13.247 g) were stirred in dry DMF (40 mL) heated to 100 °C under argon atmosphere. To the reaction was added EDC.HCI (90.00 mmol, 17.203 g), rinsed down by 10 mL dry DMF. The reaction mixture was heated to 130 °C and stirred for 60 minutes. The reaction was quenched with water (15 mL) and cooled to room temperature, then evaporated to dryness in vacuo. The residue was taken up in some acetone and evaporated onto ~40g of flash silica gel in vacuo and packed into a loader. Purified by flash chromatography on silica gel (330g, 0% EtOAc/toluene (2 CV)
30% (15 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a light brown solid, 1322 mg (27% yield). MS (APCI): calculated for Chemical Formula: C21H20N2O2 (M+H) = 333 found: 333. 1H NMR (400 MHz, TCE) 8 8.11 (dt, J = 7.7, 1.0 Hz, 2H), 7.95 (s, 1H), 7.58 - 7.40 (m, 4H), 7.27 (ddd, J = 7.9, 6.1, 2.0 Hz, 2H), 6.34 (dd, J = 2.4, 1.2 Hz, 1H), 4.76 - 4.53 (m, 4H), 2.26 (s, 3H), 2.11 (d, J = 1.1 Hz, 3H).
PLC-20 (Bis(2-(9H-carbazol-9-yl)ethyl) 5,5-difluoro-l,3,7,9-tetramethyl-10-(3,3",5,5"-tetra-tert- butyl-5'-(2-(4-(l,3-dioxo-5,ll-bis(4-(trifluoromethyl)phenyl)-lH-xantheno[2,l,9-def]isoquinolin- 2(3H)-yl)phenyl)acetoxy)-[l,l':3',l"-terphenyl]-2'-yl)-5H-4l4,5l4-dipyrrolo[l,2-c:2l,ll- f][l,3,2]diazaborinine-2,8-dicarboxylate: 3,3",5,5"-Tetra-tert-butyl-2'-formyl-[l,l':3',l"-terphenyl]- S'-yl 2-(4-(l,3-dioxo-5,ll-bis(4-(trifluoromethyl)phenyl)-lH-xantheno[2,l,9-def]isoquinolin-2(3H)- yl)phenyl)acetate (0.2500 mmol, 298 mg), the pyrrole from the previous step (0.5000 mmol, 166 mg), and pTsOH.H2O (1.000 mmol, 190 mg) were stirred in dry DCE (15 mL) at 65 °C for 60 minutes, then cooled to room temperature. The reaction was treated with DDQ. (0.5000 mmol, 114 mg) and stirred for 10 minutes. To the reaction was added Et3N (2.000 mmol, 0.28 mL), and BF3.OEt2 (3.000 mmol, 0.37 mL) were added to the reaction. The addition of Et3N (2.000 mmol, 0.28 mL), and BF3.OEt2 (3.000 mmol, 0.37 mL) was repeated and the reaction stirred at 65 °C for 60 minutes. The reaction mixture was cooled to room temperature and quenched with 10 mL water and stirred for 5 minutes. The reaction mixture was filtered through a polypropylene frit to retain water. The frit was eluted with DCM. The organic eluent was evaporated to dryness in vacuo, dissolved in a small amount of DCM and loaded onto 15g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (120g, 0% acetone/hexane (2 CV) -> 15% (5 CV), stopping gradient at 4.9%, back to 4.4%. Fractions containing product were evaporated to dryness in vacuo. The product was triturated with MeOH/water, filtered, washed with MeOH/water, dissolved in DCM, and evaporated to dryness in vacuo. Gives an orange solid, 304 mg (65% yield). MS (APCI): calculated for Chemical Formula: C117H100BF8N5O9 (M+H) = 1883 found: 1883. 1H NMR (400 MHz, TCE) δ 8.70 (s, 1H), 8.47 (s, 1H), 8.09 (d, J = 7.7 Hz, 4H), 7.91 (d, J = 8.3 Hz, 2H), 7.89 - 7.80 (m, 4H), 7.76 - 7.62 (m, 4H), 7.46 - 7.34 (m, 13H), 7.31 (dd, J = 8.3, 1.3 Hz, 1H), 7.23 (ddd, J = 8.9, 4.4, 2.0 Hz, 6H), 7.10 (dd, J = 8.4, 1.5 Hz, 1H), 7.00 -
6.95 (m, 1H), 6.93 (d, J = 1.8 Hz, 4H), 4.59 (s, 8H), 4.15 (s, 2H), 2.25 (s, 6H), 1.93 (s, 6H), 1.09 (s, 36H).
Photoluminescent Compound PLC-21:
Figure imgf000091_0001
4-Formyl-3,5-dimethoxyphenyl-2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH- xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: 4-Hydroxy-2,6-dimethoxybenzaldehyde (364 mg, 2.000 mmol), 2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetic acid (1860 mmol, 2.200 mmol), DMAP.pTsOH salt, and DIC (0.47 mL, 3.000 mmol) were stirred in dry DCM (10 mL) at room temperature for 30 minutes. The crude reaction mixture was evaporated in vacuo onto ~30g of flash silica gel and packed into a loader. Purified by flash chromatography on silica gel (120g, 5% acetone/hexanes (2 CV)
Figure imgf000091_0002
40% (20 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a yellow solid, 2367 mg (117% yield). NM R shows it co-elutes with some of the by-product N-acylurea. Take to next step as-is. MS (APCI): calculated for Chemical Formula: C51H27F12NO8 (M+H) = 1010; found: 1010. 1H NMR (400 MHz, TCE) δ 10.39 (s, 1H), 8.75 (s, 1H), 8.50 (s, 1H), 8.27 (d, J = 1.7 Hz, 2H), 8.05 - 8.00 (m, 3H), 7.67 - 7.60 (m, 2 H ), 7.49 (ddd, J = 8.6, 6.3, 2.5 Hz, 1H), 7.42 - 7.37 (m, 2H), 7.30 - 7.25 (m, 1H), 7.04 - 6.93 (m, 2H), 6.43 (s, 2H), 4.03 (s, 2H), 3.90 (s, 6H).
PLC-21 Diethyl 10-(4-(2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dimethoxyphenyl)-5,5-difluoro-l,3,7,9-tetramethyl- 5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8-dicarboxylate: 4-Formyl-3,5- dimethoxyphenyl-2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetate (~80% pure, 252 mg, 0.2000 mmol), ethyl 2,4-dimethyl-lH- pyrrole-3-carboxylate (77 mg, 0.4600 mmol), and pTsOH.H2O (8 mg, 0.04000 mmol) were stirred in dry DCE (30 mL) at room temperature under argon overnight at room temperature. The reaction mixture was treated with DDQ. (68 mg, 0.3000 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with Et3N (0.22 mL, 1.600 mmol), and BF3.OEt2 (0.30 mL, 2.400 mmol). The addition of Et3N (0.22 mL, 1.600 mmol), and BF3.OEt2 (0.30 mL, 2.400 mmol) was repeated and the reaction mixture was stirred for one hour at 50 °C. The crude reaction mixture was evaporated in vacuo onto ~30g of flash silica gel and packed into a loader. Purified by flash chromatography on silica gel (120g, 0% acetone/hexanes (2 CV) 35% (15 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 178 mg (65% yield). MS (APCI): calculated for Chemical Formula: CegHasBFuNsOn (M+H) = 1372; found: 1372. 1H NMR (400 MHz, TCE) 8 8.76 (s, 1H), 8.51 (s, 1H), 8.30 - 8.24 (m, 2H), 8.08 (s, 1H), 8.06 - 7.98 (m, 3H), 7.66 (d, J = 8.4 Hz, 2H), 7.49 (ddd, J = 8.5, 6.3, 2.4 Hz, 1H), 7.41 (d, J = 8.3 Hz, 2H), 7.31 - 7.25 (m, 1H), 7.06 - 6.94 (m, 2H), 6.56 (s, 2H), 4.05 (s, 2H), 3.75 (s, 6H), 2.81 (s, 6H), 1.88 (s, 6H), 1.34 (t, J = 7.1 Hz, 6H).
Photoluminescent Compound PLC-22:
Figure imgf000093_0001
3,5-Bis((2-ethylhexyl)oxy)phenol: Benzene-l,3,5-triol (7.567 g, 60.00 mmol), 3-
(bromomethyl)heptane (16.0 mL, 90.00 mmol), and potassium carbonate (12.439g, 90.00 mmol) were stirred in dry DMF (50 mL) at 70 °C under argon overnight. The reaction mixture was cooled to room temperature an partitioned between water (200 mL) and ether (200 mL). The reaction was carefully titrated to pH ~5 with 6N HCI, then the layers were separated. The aqueous layer was extracted with ether (2 X 100 mL), the combined organic layers dried over magnesium sulfate, filtered, and evaporated to dryness. The crude reaction mixture was evaporated in vacuo onto ~40g of flash silica gel and packed into a loader. Purified by flash chromatography on silica gel (0% EtOAc/hexanes (2 CV)
10% (15 CV)). Fractions containing product were evaporated to dryness to give a light yellow oil, 3.407g (16% yield). MS (APCI): calculated for Chemical Formula: C22H38O3 (M+H) = 351; found: 351. 1H NMR (400 MHz, CDCI3) δ 6.07 (s, 1H), 6.00 (d, J = 2.0 Hz, 2H), 3.78 (dd, J = 5.8, 1.4 Hz, 4H), 1.69 (hept, J = 6.1 Hz, 2H), 1.55 - 1.34 (m, 8H), 0.95 - 0.85 (m, 12H).
(3,5-Bis((2-ethylhexyl)oxy)phenoxy)triisopropylsilane: 3,5-Bis((2-ethylhexyl)oxy)phenol (3.407 g, 9.719 mmol), TIPS-CI (4.2 mL, 19.44 mmol), and imidazole (1.655 g, 24.30 mmol) were stirred in dry DCM (25 mL) under argon at 0 °C and allowed to warm up slowly over the weekend. The reaction mixture was diluted with DCM (to 100 mL) and washed with 6N HCI (50 mL), 10% potassium carbonate solution (50 mL), dried over magnesium sulfate, filtered, and evaporated to dryness. The crude product was dissolved in hexanes and loaded onto ~40g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (120g, 0% EtOAc/hexanes (2 CV) -> 10% (20 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a light yellow oil, 2.533 g (77% yield). MS (APCI): calculated for Chemical Formula: CsiHssOsSi (M+H) = 507; found: 507. 1H NMR (400 MHz, CDCI3) δ 6.08 (t, J = 2.2 Hz, 1H), 6.04 (d, J = 2.1 Hz, 2H), 3.77 (dd, J = 5.8, 1.1 Hz, 4H), 1.69 (p, J = 6.1 Hz, 2H), 1.52 - 1.21 (m, 16H), 1.11 (d, J = 7.2 Hz, 18H), 0.95 - 0.87 (m, 12H).
2.6-Bis((2-ethylhexyl)oxy)-4-((triisopropylsilyl)oxy)benzaldehyde: (3,5-Bis((2- ethylhexyl)oxy)phenoxy)triisopropylsilane (3.805 g, 7.507 mmol) and TMEDA (6.4 mL, 30.03 mmol) were combined in dry THF (50 mL) under argon and stirred at 0 °C for five minutes. The reaction mixture was treated dropwise with nBuLi solution (1.6M in hex, 23.5 mL, 37.53 mmol). The reaction mixture was stirred at 0 °C for five minutes, then the cooling bath was removed and the reaction mixture stirred at room temperature overnight. The reaction mixture was cooled to -78 ° C and treated dropwise with dry DMF (5.8 mL, 75.07 mmol). The reaction mixture was stirred at -78 ° C for a few minutes, then the cooling bath was removed and the reaction allowed to warm to room temperature with stirring. The stirring was continued for one hour, then the reaction mixture was quenched with sat. NH4CI solution (150 mL) and partitioned with ether (200 mL). The layers were separated and the aqueous layer was extracted with ether (100 mL). The combined organic layers were dried over magnesium sulfate, filtered, and evaporated to dryness in vacuo. The crude product was diluted with hexanes and loaded onto a loader packed with ~45g of flash silica gel. Purified by flash chromatography on silica gel (0% EtOAc/hexanes (2 CV) -> 20% (20 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives 3.543 g (88% yield). MS (APCI): calculated for Chemical Formula: C32H58O4Si (M+H) = 535; found: 535. 1H NMR (400 MHz, CDCI3) δ 10.37 (s, 1H), 6.02 (s, 2H), 3.85 (dd, J = 5.6, 2.3 Hz, 4H), 1.75 (h, J = 6.0 Hz, 3H), 1.59 - 1.36 (m, 16H), 1.13 (d, J = 7.2 Hz, 18H), 0.96 - 0.86 (m, 12H).
2.6-Bis((2-ethylhexyl)oxy)-4-hydroxybenzaldehyde: 2,6-Bis((2-ethylhexyl)oxy)-4-
((triisopropylsilyl)oxy)benzaldehyde (3.543 g, 6.624 mmol) was dissolved in dry THF (50 mL) and stirred at 0 °C under argon. The reaction mixture was treated dropwise with TBAF (1.0 M/THF, 7.3 mL, 7.300 mmol) and the reaction stirred at 0 ° C for 30 minutes. The reaction was quenched with sat. NH4CI solution (100 mL) and titrated to pH ~8 with 6N HCI solution. The reaction mixture was partitioned with 200 mL ether and the layers separated. Extracted the aqueous layer with ether (100 mL), dried the combined organic layers over magnesium sulfate, filtered, and evaporated to dryness in vacuo. The crude product was dissolved in hexanes and loaded onto a loader packed with ~40g of flash silica gel. Purified by flash chromatography on silica gel (120g, 0% EtOAc/hexanes (2 CV) -> 20% (20 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives 1.742 g (70% yield). MS (APCI): calculated for Chemical Formula: C23H38O4 (M+H) = 379; found: 379. 1H NMR (400 MHz, Acetone) δ 10.37 (s, 1H), 6.16 (s, 2H), 3.92 (dd, J = 5.4, 0.6 Hz, 4H), 1.74 (h, J = 6.0 Hz, 2H), 1.64 - 1.42 (m, 8H), 1.40 - 1.27 (m, 8H), 1.01 - 0.86 (m, 12H).
3,5-Bis((2-ethylhexyl)oxy)-4-formylphenyl-2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo- lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: 2,6-Bis((2-ethylhexyl)oxy)-4- hydroxybenzaldehyde (379 mg, 1.000 mmol), 2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3- dioxo-lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (1015 mg, 1.200 mmol), DMAP.pTsOH salt (147 mg, 0.5000 mmol), and DIC (0.31 mL, 2.000 mmol) were stirred in dry DCM (20 mL) at room temperature for 30 minutes. The crude reaction mixture was diluted 1:1 with hexanes and loaded onto a loader packed with ~50g of flash silica gel. Purified by flash chromatography on silica gel (120g, 0% EtOAc/hexanes (2 CV) -> 20% (30 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a yellow solid, 1.035 g (86% yield). MS (APCI): calculated for Chemical Formula: CgsHssFuNOg (M+H) = 1206; found: 1206. 1H NMR (400 MHz, Acetone) δ 10.47 (s, 1H), 8.77 (s, 1H), 8.61 - 8.56 (m, 2H), 8.52 (s, 1H), 8.36 - 8.32 (m, 2H), 8.24 (s, 1H), 8.20 (s, 1H), 7.63 - 7.57 (m, 2H), 7.55 (ddd, J = 8.5, 7.2, 1.5 Hz, 1H), 7.47 - 7.40 (m, 2H), 7.30 (dd, J = 8.3, 1.3 Hz, 1H), 7.13 (dd, J = 8.3, 1.5 Hz, 1H), 7.03 (ddd, J = 8.4, 7.2, 1.3 Hz, 1H), 6.58 (s, 2H), 4.07 (s, 2H), 3.98 (d, J = 5.4 Hz, 4H), 1.77 (hept, J = 6.2 Hz, 2H), 1.63 - 1.40 (m, 8H), 1.40 - 1.26 (m, 8H), 0.93 (t, J = 7.5 Hz, 6H), 0.91 - 0.86 (m, 6H).
PLC-22 Diethyl 10-(4-(2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-bis((2-ethylhexyl)oxy)phenyl)-5,5-difluoro-l,3,7,9- tetramethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',ll-f][l,3,2]diazaborinine-2,8-dicarboxylate: 3,5-Bis((2- ethylhexyl)oxy)-4-formylphenyl-2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH- xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetate (1035 mg, 0.8581 mmol), ethyl 2,4-dimethyl- lH-pyrrole-3-carboxylate (316 mg, 1.888 mmol), and pTsOH.H2O (16 mg, 0.08581 mmol) were stirred in dry DCE (25 mL) under argon for one hour at room temperature. The reaction mixture was treated with DDQ. (331 mg, 1.459 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with EtsN (0.96 mL, 6.865 mmol), and BF3.OEt2 (0.87 mL, 7.061 mmol). The addition of EtsN (0.96 mL, 6.865 mmol), and BF3.OEt2 (0.87 mL, 7.061 mmol) was repeated and the reaction mixture was stirred for one hour at 50 °C. The crude reaction mixture was evaporated onto ~40g of flash silica gel in vacuo. Purified by flash chromatography on silica gel (120g, 0% EtOAc/hexanes (2 CV) -> 25% (30 CV)). Fractions containing product were evaporated to dryness in vacuo. The purification was repeated to remove minor impurities. Gives an orange solid, 1.122 g (83% yield). MS (APCI): calculated for Chemical Formula: C83H76BF14N3O11 (M+H) = 1569; found: 1569. 1H NMR (400 MHz, Acetone) 5 8.77 (s, 1H), 8.60 - 8.54 (m, 2H), 8.52 (s, 1H), 8.36 - 8.30 (m, 2H), 8.24 (tt, J = 1.8, 0.9 Hz, 1H), 8.20 (td, J = 1.7, 0.9 Hz, 1H), 7.66 - 7.57 (m, 2H), 7.54 (ddd, J = 8.5, 7.2, 1.5 Hz, 1H), 7.48 - 7.41 (m, 2H), 7.29 (dd, J = 8.3, 1.3 Hz, 1H), 7.13 (dd, J = 8.4, 1.5 Hz, 1H), 7.02 (ddd, J = 8.4, 7.1, 1.3 Hz, 1H), 4.28 (q, J = 7.1 Hz, 4H), 4.10 (s, 2H), 3.96 (dd, J = 9.3, 4.9 Hz, 2H), 3.89 (dd, J = 9.2, 5.9 Hz, 2H), 2.79 (s, 6H), 1.99 - 1.93 (m, 6H), 1.51 (q, J = 5.9 Hz, 2H), 1.33 (t, J = 7.1 Hz, 6H), 1.25 - 1.16 (m, 4H), 1.16 - 1.01 (m, 12H), 0.78 - 0.67 (m, 12H).
Photoluminescent Compound PLC-23:
Figure imgf000097_0001
3,5-Bis(3-phenylpropoxy)phenol: Benzene-l,3,5-triol (7.567 g, 60.00 mmol), (3- bromopropyl)benzene (18.2 mL, 120.0 mmol), and potassium carbonate (16.585 g, 120.0 mmol) were stirred in dry DMF (50 mL) under argon at 50 °C for three hours. The reaction was cooled to room temperature and partitioned between water (200 mL) and ether (200 mL). The reaction was carefully titrated to pH ~6.5 with 6N HCI, then the layers were separated. The aqueous layer was extracted with ether (2 X 100 mL), the combined organic layers were dried over magnesium sulfate, filtered, and evaporated to dryness in vacuo. The crude reaction mixture was diluted with ether and loaded onto ~45g of flash silica gel packed in a loader. Purified by flash chromatography on silica gel (220g, 0% EtOAc/hexanes
Figure imgf000097_0002
25% (20 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a waxy, off-white solid, 5.775 g (27% yield). MS (APCI): calculated for Chemical Formula: C24H26O3 (M+H) = 363; found: 363. 1H NMR (400 MHz, CD2CI2) 8 7.34 - 7.25 (m, 4H), 7.25 - 7.14 (m, 6H), 6.05 (q, J = 1.9 Hz, 1H), 5.99 (t, J = 1.7 Hz, 2H), 4.93 (d, J = 1.3 Hz, 1H), 3.91 (t, J = 6.3 Hz, 4H), 2.78 (t, J = 7.7 Hz, 4H), 2.13 - 2.02 (m, 4H).
4-Hydroxy-2,6-bis(3-phenylpropoxy)benzaldehyde: 3,5-Bis(3-phenylpropoxy)phenol (5.770 g, 15.92 mmol) was dissolved in dry DCM (5 mL) and treated with POCI3 (3.0 mL, 31.84 mmol) under argon at room temperature. The reaction mixture was stirred for ten minutes, then cooled to 0 °C and treated with dry DMF (1.84 mL, 23.88 mmol) dropwise with stirring. The reaction mixture was stirred at 0 0 C and allowed to warm slowly to room temperature overnight. The reaction mixture was quenched with crushed ice, then diluted with water to ~100 mL. The reaction was carefully quenched with 10% aqueous potassium carbonate solution to pH ~6. The reaction mixture was partitioned with DCM (100 mL) and the layers separated. The aqueous layer was extracted with DCM (2 X 100 mL), the combined organic layers dried over magnesium sulfate, filtered, and evaporated to dryness. The crude product was diluted with ether and loaded onto ~50g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (220g, 0% EtOAc/hexanes (2 CV)
Figure imgf000098_0001
20% (20 CV) -> 50% (0 CV) isocratic 50%)). Fractions containing product were evaporated to dryness in vacuo. Gives 1.341 g (22% yield). MS (APCI): calculated for Chemical Formula: C25H26O4 (M+H) = 391; found: 391. Compound is a 1:1 mixture with an inseparable by-product. Take to next step as-is.
4-Formyl-3,5-bis(3-phenylpropoxy)phenyl 2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo- lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: 4-Hydroxy-2,6-bis(3- phenylpropoxy)benzaldehyde (mixture, 391 mg, 1.000 mmol), 2-(4-(5,ll-bis(3,5- bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (1015 mg, 1.200 mmol), DMAP.pTsOH salt (29 mg, 0.1000 mmol), and DIC (0.313 mL, 2.000 mmol) were stirred in dry DCM (15 mL) at room temperature for 30 minutes. The crude reaction mixture was diluted 1:1 with hexanes and loaded onto a loader packed with ~50g of flash silica gel. Purified by flash chromatography on silica gel (120g, 0% EtOAc/hexanes (2 CV) -> 10% (20 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a yellow solid, 1034 mg (85% yield). MS (APCI): calculated for Chemical Formula: C67H43F12NO8 (M+H) = 1218; found: 1218. 1H NMR (400 MHz, CD2CI2) 6 10.49 (s, 1H), 8.77 (s, 1H), 8.53 (s, 1H), 8.30 (dd, J = 1.7, 0.9 Hz, 2H), 8.09 (tt, J = 1.5, 0.7 Hz, 1H), 8.05 (dd, J = 1.9, 0.9 Hz, 3H), 7.61 - 7.55 (m, 2H), 7.47 (ddd, J = 8.5, 7.0, 1.7 Hz, 1H), 7.39 - 7.33 (m, 2H), 7.33 - 7.14 (m, 12H), 7.05 - 6.93 (m, 2H), 6.38 (s, 2H), 4.02 (t, J = 6.2 Hz, 4H), 3.99 (s, 2H), 2.85 (dd, J = 8.3, 6.8 Hz, 4H), 2.19 - 2.08 (m, 4H).
PLC-23 Diethyl 10-(4-(2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-bis(3-phenylpropoxy)phenyl)-5,5-difluoro-l,3,7,9- tetramethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8-dicarboxylate: 4-Formyl-3,5-bis(3-phenylpropoxy)phenyl 2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo- lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetate (1033 mg, 0.8481 mmol), ethyl 2,4- dimethyl-lH-pyrrole-3-carboxylate (326 mg, 1.951 mmol), and pTsOH.H2O (16 mg, 0.08481 mmol) were stirred in dry DCE (25 mL) under argon for one hour at room temperature. The reaction mixture was treated with DDQ. (347 mg, 1.527 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with Et3N (0.95 mL, 6.785 mmol), and BF3.OEt2 (1.25 mL, 10.18 mmol). The addition of Et3N (0.95 mL, 6.785 mmol), and BF3.OEt2 (1.25 mL, 10.18 mmol) was repeated and the reaction mixture was stirred for one hour at 50 °C. The crude reaction mixture was evaporated in vacuo onto ~40g of flash silica gel and packed into a loader. Purified by flash chromatography on silica gel (220g, 0% EtOAc/DCM (2 CV) -> 1% (20 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 533 mg (40% yield). MS (APCI): calculated for Chemical Formula: C85H64BFI4N3OII (M+H) = 1580; found: 1580. 1H NM R (400 MHz, CD2CI2) δ 8.78 (s, 1H), 8.53 (s, 1H), 8.31 (t, J = 1.1 Hz, 2H), 8.09 (td, J = 1.8, 0.9 Hz, 1H), 8.05 (dt, J = 1.9, 0.9 Hz, 3H), 7.64 - 7.58 (m, 2H), 7.47 (ddd, J = 8.5, 7.0, 1.7 Hz, 1H), 7.40 - 7.34 (m, 2H), 7.27 (dd, J = 8.3, 1.2 Hz, 1H), 7.23 - 7.16 (m, 4H), 7.15 - 7.09 (m, 2H), 7.02 (dd, J = 8.4, 1.7 Hz, 1H), 7.00 - 6.93 (m, 5H), 6.51 (s, 2H), 4.25 (q, J = 7.1 Hz, 4H), 4.02 (s, 2H), 3.93 (t, J = 6.0 Hz, 4H), 2.80 (s, 6H), 2.45 (dd, J = 8.5, 6.7 Hz, 4H), 1.94 - 1.84 (m, 4H), 1.30 (t, J = 7.1 Hz, 6H).
Photoluminescent Compound PLC-24:
Figure imgf000100_0001
3,5-Bis(cyclohexylmethoxy)phenol: Benzene-l,3,5-triol (15.763 g, 125.0 mmol),
(bromomethyl)cyclohexane (21.8 mL, 156.3 mmol), and potassium carbonate (34.553 g, 250.0 mmol) were combined in dry DCM (100 mL) and heated at 70 °C under argon overnight. The reaction mixture was cooled to room temperature, diluted with water (200 mL) and extracted with ether (3 X 125 mL). The combined organic layers were washed with water (200 mL), dried over magnesium sulfate, filtered, and evaporated to dryness in vacuo. The crude reaction mixture was evaporated onto ~50g of flash silica gel in vacuo and packed into a loader. Purified by flash chromatography on silica gel (330g, 0% EtOAc/hexanes (2 CV) 25% (10 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives 3.157 g (7.9% yield). MS (APCI): calculated for Chemical Formula: C20H30O3 (M+H) = 319; found: 319. 1H NMR (400 MHz, TCE) δ 6.07 (t, J = 2.1 Hz, 1H), 3.69 (d, J = 6.3 Hz, 4H), 1.92 - 1.65 (m, 10H), 1.42 - 1.10 (m, 9H), 0.96 - 0.76 (m, 2H). 2,6-Bis(cyclohexylmethoxy)-4-hydroxybenzaldehyde: 3,5-Bis(cyclohexylmethoxy)phenol (3.150 g, 9.891 mmol) was dissolved in dry DCM (6 mL) under argon and stirred at room temperature. The reaction mixture was treated with POCI3 (1.84 mL, 3.033 mmol) and stirred for five minutes at room temperature, then cooled to 0 °C and treated dropwise with dry DMF (0.92 mL, 11.87 mmol). The reaction mixture was stirred at 0 °C for one hour, then the contents of the reaction dumped into ~100 mL of crushed ice, rinsing with a small amount of acetone. The reaction mixture was titrated to pH ~6- 7 with 10% potassium carbonate solution, then extracted with DCM (100 mL, 2 X 50 mL). The combined organic layers were dried over magnesium sulfate, filtered, and evaporated to dryness in vacuo. The crude product was diluted with a small amount of DCM and loaded onto ~50g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (120g, 0% EtOAc/hexanes (2 CV) -> 100% EtOAc (15 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives 175 mg (5.1% yield). MS (APCI): calculated for Chemical Formula: C21H30O4 (M+H) = 347; found: 347. 1H NMR (400 MHz, TCE) δ 10.32 (s, 1H), 6.02 (s, 2H), 3.76 (d, J = 6.0 Hz, 4H), 1.96 - 1.81 (m, 7H), 1.80 - 1.62 (m, 9H), 1.40 - 1.15 (m, 8H), 1.13 - 0.94 (m, 5H).
3,5-Bis(cyclohexylmethoxy)-4-formylphenyl 2-(4-(l,3-dioxo-5,ll-bis(4-(trifluoromethyl)phenyl)-lH- xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: 2,6-Bis(cyclohexylmethoxy)-4- hydroxybenzaldehyde (175 mg, 0.5051 mmol), 2-(4-(l,3-dioxo-5,ll-bis(4-(trifluoromethyl)phenyl)- lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (430 mg, 0.6061 mmol), DMAP.pTsOH salt (15 mg, 0.05051 mmol), and DIC (0.158 mL, 1.010 mmol) were stirred in dry DCM (10 mL) at room temperature for 30 minutes. The crude reaction mixture was loaded onto ~45g of flash silica gel packed into a loader by dissolving in DCM. Purified by flash chromatography on silica gel (120g, 0% EtOAc/DCM (2 CV) -> 5% (10 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a yellow solid, 449 mg (86% yield). MS (APCI): calculated for Chemical Formula: CGiH4gFsNO8 (M+H) = 1038; found: 1038. 1H NMR (400 MHz, TCE) 5 10.44 (s, 1H), 8.71 (s, 1H), 8.48 (s, 1H), 7.95 -
7.81 (m, 6H), 7.72 - 7.58 (m, 4H), 7.48 - 7.36 (m, 3H), 7.31 (dd, J = 8.3, 1.3 Hz, 1H), 7.10 (dd, J = 8.3, 1.5 Hz, 1H), 6.96 (ddd, J = 8.4, 7.1, 1.3 Hz, 1H), 6.37 (s, 2H), 4.02 (s, 2H), 3.81 (d, J = 5.9 Hz, 4H), 1.92 -
1.82 (m, 6H), 1.79 - 1.51 (m, 7H), 1.45 - 0.96 (m, 10H).
PLC-24 Diethyl 10-(2,6-bis(cyclohexylmethoxy)-4-(2-(4-(l,3-dioxo-5,ll-bis(4-
(trifluoromethyl)phenyl)-lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)phenyl)-5,5- difluoro-l,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8- dicarboxylate: 3,5-Bis(cyclohexylmethoxy)-4-formylphenyl-2-(4-(l,3-dioxo-5,ll-bis(4-
(trifluoromethyl)phenyl)-lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetate (445 mg, 0.4287 mmol), ethyl 2,4-dimethyl-lH-pyrrole-3-carboxylate (179 mg, 1.072 mmol), and PTSOH.H2O (8 mg, 0.04287 mmol) were stirred in dry DCE (25 mL) under argon for one hour at room temperature. The reaction mixture was treated with DDQ. (175 mg, 0.7716 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with Et3N (0.48 mL, 3.430 mmol), and BF3.OEt2 (.64 mL, 5.144 mmol). The addition of Et3N (0.48 mL, 3.430 mmol), and BF3.OEt2 (.64 mL, 5.144 mmol) was repeated and the reaction mixture was stirred for one hour at 50 °C. The crude reaction mixture was evaporated onto ~50g of flash silica gel in vacuo and packed into a loader. Purified by flash chromatography on silica gel (120g, 100% hexanes/toluene, EtOAc modifier, 0.1% -> 1% -> 2%
Figure imgf000102_0001
3% step gradients). Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 446 mg (74% yield). MS (APCI): calculated for Chemical Formula: CygHyoBFsNsOii (M+H) = 1401; found: 1401. 1H NMR (400 MHz, TCE) 5 10.44 (s, 1H), 8.71 (s, 1H), 8.48 (s, 1H), 7.95 - 7.81 (m, 6H), 7.72 - 7.58 (m, 4H), 7.48 - 7.36 (m, 3H), 7.31 (dd, J = 8.3, 1.3 Hz, 1H), 7.10 (dd, J = 8.3, 1.5 Hz, 1H), 6.96 (ddd, J = 8.4, 7.1, 1.3 Hz, 1H), 6.37 (s, 2H), 4.02 (s, 2H), 3.81 (d, J = 5.9 Hz, 4H), 1.92 - 1.82 (m, 6H), 1.79
- 1.51 (m, 7H), 1.45 - 0.96 (m, 10H).
Photoluminescent Compound PLC-25:
Figure imgf000102_0002
4-Formyl-3,5-dimethoxyphenyl-2-(4-(l,3-Dioxo-5,ll-bis(4-(trifluoromethyl)phenyl)-lH- xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: 4-Hydroxy-2,6-dimethoxybenzaldehyde (456 mg, 2.500 mmol), 2-(4-(l,3-dioxo-5,ll-bis(4-(trifluoromethyl)phenyl)-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetic acid (2129 mg, 3.000 mmol), DMAP.pTsOH salt (74 mg, 0.2500 mmol), and DIC (0.783 mL, 5.000 mmol) were stirred in dry DCM (30 mL) at room temperature for 30 minutes. The crude reaction mixture was loaded onto ~50g of flash silica gel packed in a loader. Purified by flash chromatography on silica gel (120g, 0% EtOAc/DCM (2 CV) -> 15% (20 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a yellow solid, 1956 mg (90% yield). MS (APCI): calculated for Chemical Formula: C49H29F6NO8 (M+H) = 874; found: 874. 1H NMR (400 MHz, TCE) δ 10.39 (s, 1H), 8.71 (s, 1H), 8.48 (s, 1H), 7.95 - 7.82 (m, 6H), 7.71 - 7.59 (m, 4H), 7.47 - 7.37 (m, 3H), 7.31 (dd, J = 8.3, 1.3 Hz, 1H), 7.10 (dd, J = 8.3, 1.5 Hz, 1H), 6.96 (ddd, J = 8.4, 7.2, 1.4 Hz, 1H), 6.44 (s, 2H), 4.04 (s, 2H), 3.90 (s, 6H).
PLC-25 Diethyl 10-(4-(2-(4-(l,3-dioxo-5,ll-bis(4-(trifluoromethyl)phenyl)-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dimethoxyphenyl)-5,5-difluoro-l,3,7,9-tetramethyl- 5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8-dicarboxylate:
4-Formyl-3,5-dimethoxyphenyl-2-(4-(l,3-dioxo-5,ll-bis(4-(trifluoromethyl)phenyl)-lH- xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetate (1950 mg, 2.232 mmol), ethyl 2,4-dimethyl- lH-pyrrole-3-carboxylate (933 mg, 5.579 mmol), and PTSOH.H2O (43 mg, 0.2232 mmol) were stirred in dry DCE (100 mL) under argon for one hour at room temperature. The reaction mixture was treated with DDQ (912 mg, 4.017 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with Et3N (2.5 mL, 17.85 mmol), and BF3.OEt2 (3.31 mL, 26.78 mmol). The addition of Et3N (2.5 mL, 17.85 mmol), and BF3.OEt2 (3.31 mL, 26.78 mmol) was repeated and the reaction mixture was stirred for one hour at 50 °C. The crude reaction mixture was cooled to room temperature and evaporated onto ~55g of flash silica gel in vacuo. Purified by flash chromatography on silica gel (120g, 100% tol/hexanes, EtOAc modifier, 2% -> 4% step gradients). Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 2080 mg (75% yield). MS (APCI): calculated for Chemical Formula: C67HsaBF8N30ii (M+H) = 1236; found: 1236. 1H NMR (400 MHz, TCE) δ 8.62 (s, 1H), 8.39 (s, 1H), 7.87 - 7.72 (m, 6H), 7.58 (dd, J = 8.4, 2.3 Hz, 4H), 7.40 - 7.29 (m, 3H), 7.22 (dd, J = 8.2, 1.4 Hz, 1H), 7.01 (dd, J = 8.3, 1.6 Hz, 1H), 6.87 (ddd, J = 8.4, 7.1, 1.4 Hz, 1H), 4.20 (q, J = 7.1 Hz, 4H), 3.96 (s, 2H), 3.67 (s, 6H), 2.73 (s, 6H), 1.80 (s, 6H), 1.26 (t, J = 7.1 Hz, 6H).
Photoluminescent Compound PLC-26 :
Figure imgf000104_0001
2,6-Bis(2-ethylhexyl)-4-hydroxybenzaldehyde: 2,6-Dibromo-4-hydroxybenzaldehyde (380 mg, 1.358 mmol) was dissolved in dry THF (25 mL) and treated with Pd(dppf)CI2 (199 mg, 0.2716 mmol) and stirred under argon at room temperature. The solution was sparged with argon, then (2- ethylhexyl)zinc(ll) bromide (0.5M in THF, 16.3 mL, 8.148 mm) was added and the reaction mixture stirred at room temperature for five minutes. The reaction mixture was heated at 40 °C overnight. The reaction mixture was cooled to room temperature and quenched with sat. NH4CI solution (100 mL) and extracted with ethyl acetate (100 mL, 2 X 50 mL). The combined organic layers were dried over magnesium sulfate, filtered, and evaporated to dryness. The crude product was evaporated onto ~40g of flash silica gel in vacuo and packed into a loader. Purified by flash chromatography on silica gel (120g, 0% EtOAc/hexanes (2 CV) -> 30% (20 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives an off-white solid, 247 mg (52% yield). MS (APCI): calculated for Chemical Formula: C23H38O2 (M+H) = 347; found: 347. 1H NMR (400 MHz, Acetone) δ 10.41 (s, 1H), 6.62 (s, 2H), 2.89 (dt, J = 7.3, 5.1 Hz, 4H), 1.54 (p, J = 6.5 Hz, 2H), 1.39 - 1.13 (m, 16H), 0.92 - 0.80 (m, 12H).
3,5-Bis(2-ethylhexyl)-4-formylphenyl 2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH- xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: 2,6-Bis(2-ethylhexyl)-4- hydroxybenzaldehyde (247 mg, 0.7127 mmol), 2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3- dioxo-lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (723 mg, 0.8553 mmol), DMAP.pTsOH salt (21 mg, 0.07127 mmol), and DIC (0.223 mL, 1.425 mmol) were stirred in dry DCM (10 mL) at room temperature for 30 minutes. The crude reaction mixture was diluted 1:1 with hexanes and loaded onto a loader packed with ~50g of flash silica gel. Purified by flash chromatography on silica gel (120g, 0% EtOAc/hexanes (2 CV) -> 20% (30 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a yellow solid, 841 mg (100% yield). MS (APCI): calculated for Chemical Formula: CssHssFuNOs (M+H) = 1174; found: 1174. 1H NMR (400 MHz, Acetone) δ 10.55 (s, 1H), 8.77 (s, 1H), 8.59 (d, J = 1.6 Hz, 2H), 8.53 (s, 1H), 8.35 (d, J = 1.6 Hz, 2H), 8.24 (s, 1H), 8.20 (s, 1H), 7.61 (d, J = 8.3 Hz, 3H), 7.55 (ddd, J = 8.5, 7.2, 1.5 Hz, 1H), 7.46 - 7.41 (m, 2H), 7.31 (dd, J = 8.3, 1.3 Hz, 1H), 7.14 (dd, J = 8.4, 1.5 Hz, 1H), 7.07 - 6.98 (m, 3H), 4.09 (s, 2H), 2.94 (dt, J = 7.2, 2.5 Hz, 4H), 1.54 (q, J = 6.2 Hz, 2H), 1.40 - 1.22 (m, 16H), 0.86 (q, J = 7.0 Hz, 12H).
PLC-26 Diethyl 10-(4-(2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-bis(2-ethylhexyl)phenyl)-5,5-difluoro-l,3,7,9- tetramethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8-dicarboxylate): 3,5-Bis(2- ethylhexyl)-4-formylphenyl-2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH- xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetate (837 mg, 0.7127 mmol), ethyl 2,4-dimethyl- lH-pyrrole-3-carboxylate (274 mg, 1.639 mmol), and pTsOH.H2O (14 mg, 0.07127 mmol) were stirred in dry DCE (25 mL) under argon overnight at 50 ° C. The reaction mixture was cooled to room temperature and treated with DDQ. (275 mg, 1.212 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with Et3N (0.80 mL, 5.702 mmol), and BF3.OEt2 (1.06 mL, 8.552 mmol). The addition of Et3N (0.80 mL, 5.702 mmol), and BF3.OEt2 (1.06 mL, 8.552 mmol) was repeated and the reaction mixture was stirred for one hour at 50 " C. The reaction mixture was evaporated onto ~45g of flash silica gel and evaporated to dryness in vacuo. Purified by flash chromatography on silica gel (120g, 0% EtOAc/toluene (2 CV) -> 2% (30 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 419 mg (38% yield). MS (APCI): calculated for Chemical Formula: C83H76BFi4N3O9 (M+H) = 1537; found: 1537. 1H NMR (400 M Hz, Acetone) δ 8.76 (s, 1H), 8.59 - 8.56 (m, 2H), 8.52 (s, 1H), 8.34 (d, J = 1.7 Hz, 2H), 8.24 (dq, J = 1.9, 1.0 Hz, 1H), 8.20 (td, J = 1.7, 0.9 Hz, 1H), 7.68 - 7.59 (m, 2H), 7.54 (ddd, J = 8.5, 7.2, 1.6 Hz, 1H), 7.50 - 7.42 (m, 2H), 7.29 (dd, J = 8.3, 1.2 Hz, 1H), 7.17 (s, 2H), 7.12 (dd, J = 8.3, 1.5 Hz, 1H), 7.02 (ddd, J = 8.4, 7.1, 1.3 Hz, 1H), 4.28 (q, J = 7.1 Hz, 4H), 4.12 (d, J = 2.0 Hz, 2H), 2.82 (s, 6H), 2.56 - 2.36 (m, 4H), 1.78 (t, J = 2.2 Hz, 6H), 1.38 - 0.91 (m, 22H), 0.83 - 0.75 (m, 6H), 0.73 - 0.61 (m, 6H).
Photoluminescent Compound PLC-27:
Figure imgf000106_0001
2,6-Dicyclopropyl-4-hydroxybenzaldehyde: Zinc chloride (2726 mg, 20.00 mmol) was heated under vacuum at 150 ° C for one hour, then cooled under argon atmosphere to room temperature. To this salt was added dry THF (100 mL), followed by cyclopropyl magnesium bromide solution (1.0 M in 2- methylTHF, 20.0 mL, stirring at room temperature overnight. To the flask was added Pd(dppf)Ck (293 mg, 0.4000 mmol), followed by 2,6-dibromo-4-hydroxybenzaldehyde (560 mg, 2.000 mmol) and the reaction mixture stirred under argon at 40 °C for four hours. The reaction mixture was cooled to room temperature, then quenched with sat NH4CI solution (50 mL), followed 6N HCI (25 mL). The reaction mixture was extracted with ethyl acetate (100 mL, 3 X 50 mL). The combined organic layers were dried over magnesium sulfate, filtered, and evaporated to dryness in vacuo. The crude product was evaporated onto ~40g of flash silica gel in vacuo and packed into a loader. Purified by flash chromatography on silica gel (120g, 0% acetone/hexanes (2 CV) 40% (20 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives an off-white solid, 120 mg (30% yield). MS (APCI): calculated for Chemical Formula: C13H14O2 (M+H) = 203; found: 203. 1H NMR (400 MHz, TCE) δ 10.87 (s, 1H), 6.40 (s, 2H), 2.60 (tt, J = 8.4, 5.4 Hz, 2H), 1.09 - 0.95 (m, 4H), 0.71 (dd, J = 5.5, 1.8 Hz, 4H). 3,5-Dicyclopropyl-4-formylphenyl-2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH- xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: 2,6-Dicyclopropyl-4-hydroxybenzaldehyde (119 mg, 0.5884 mmol), 2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetic acid (647 mg, 0.7649 mmol), DMAP.pTsOH salt (173 mg, 0.5884 mmol), and DIC (0.66 mL, 1.177 mmol) were stirred in dry DCM (10 mL) at room temperature for 30 minutes. The reaction mixture was diluted 1:1 with hexanes and loaded onto a loader packed with ~45g of flash silica gel. Purified by flash chromatography on silica gel (0% acetone/hexanes (2 CV) -> 40% (20 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a yellow solid, 252 mg (42% yield). MS (APCI): calculated for Chemical Formula: C55H31F12NO6 (M+H) = 1030; found: 1030. 1H NMR (400 MHz, TCE) δ 10.96 (s, 1H), 8.76 (s, 1H), 8.51 (s, 1H), 8.27 (s, 5H), 8.07 (s, 2H), 8.03 (s, 6H), 7.61 (d, J = 8.0 Hz, 4H), 7.49 (t, J = 7.7 Hz, 2H), 7.38 (d, J = 8.1 Hz, 4H), 7.28 (d, J = 8.2 Hz, 2H), 7.00 (d, J = 6.1 Hz, 4H), 6.74 (s, 2H), 4.00 (s, 2H), 2.53 (td, J = 8.7, 4.4 Hz, 2H), 1.05 (dt, J = 10.9, 3.1 Hz, 4H), 0.81 - 0.67 (m, 4H).
PLC-27 Diethyl 10-(4-(2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dicyclopropylphenyl)-5,5-difluoro-l, 3,7,9- tetramethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8-dicarboxylate: 3,5-
Dicyclopropyl-4-formylphenyl-2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH- xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetate (251 mg, 0.2075 mmol), ethyl 2,4-dimethyl- lH-pyrrole-3-carboxylate (80 mg, 0.4772 mmol), and pTsOH.H2O (4 mg, 0.02075 mmol) were stirred in dry DCE (25 mL) under argon overnight at room temperature. The reaction mixture was treated with DDQ. (240 mg, 1.059 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with Et3N (0.66 mL, 4.701 mmol), and BF3.OEt2 (0.87 mL, 7.061 mmol). The addition of Et3N (0.66 mL, 4.701 mmol), and BF3.OEt2 (0.87 mL, 7.061 mmol) was repeated and the reaction mixture was stirred for one hour at 50 °C. The reaction mixture was cooled to room temperature and evaporated in vacuo onto ~35g of flash silica gel. Purified by flash chromatography on silica gel (120g, 0% EtOAc/hexanes (2
Figure imgf000107_0001
35% (20 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 127 mg (44% yield). MS (APCI): calculated for Chemical Formula: C73H52BF14N3O9 (M+H) = 1392; found: 1392. 1H NMR (400 MHz, Acetone) δ 8.77 (s, 1H), 8.63 - 8.57 (m, 2H), 8.53 (s, 1H), 8.38 - 8.32 (m, 2H), 8.26 - 8.22 (m, 1H), 8.22 - 8.18 (m, 1H), 7.64 - 7.58 (m, 2H), 7.54 (ddd, J = 8.5, 7.2, 1.5 Hz, 1H), 7.47 - 7.39 (m, 2H), 7.30 (dd, J = 8.3, 1.2 Hz, 1H), 7.13 (dd, J = 8.3, 1.5 Hz, 1H), 7.02 (ddd, J = 8.4, 7.2, 1.3 Hz, 1H), 6.73 (s, 2H), 4.29 (q, J = 7.1 Hz, 4H), 4.07 (s, 2H), 2.81 (s, 6H), 1.86 (s, 6H), 1.73 (tt, J = 8.3, 5.1 Hz, 2H), 1.34 (t, J = 7.1 Hz, 6H), 0.90 - 0.80 (m, 4H), 0.74 - 0.64 (m, 4H).
Photoluminescent Compound PLC-30:
Figure imgf000108_0001
4-Hydroxy-2,6-dipentylbenzaldehyde: 2,6-Dibromo-4-hydroxybenzaldehyde (190 mg, 0.6788 mmol), pentylboronic acid (630 mg, 5.430 mmol), Pd(dppf)Ch (99 mg, 0.1358 mmol), and cesium carbonate (885 mg, 2.715 mmol) were combined in THF (10 mL) and water (1 mL) in a 30 mL microwave vial. The vial was sealed and heated for two hours at 130 °C in a microwave synthesizer. The crude reaction mixture was evaporated onto ~30g of flash silica gel in vacuo and packed into a loader. Purified by flash chromatography on silica gel (120g, 0% acetone/hexanes (2 CV) -> 40% (20 CV)). Fractions containing product were evaporated to dryness in vacuo. Compound was not pure by NMR, but was taken to the next step as-is. MS (APCI): calculated for Chemical Formula: C15H22O2 (M+H) = 235; found:
235.
4-Formyl-3,5-dipentylphenyl-2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH- xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: 4-Hydroxy-2,6-dipentylbenzaldehyde (75 mg, 0.2859 mmol), 2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9- def]isoquino0lin-2(3H)-yl)phenyl)acetic acid (483 mg, 0.5719 mmol), DMAP.pTsOH salt (84 mg, 0.2859 mmol), and DIC (0.134 ml_, 0.8575 mmol) were combined in dry DCM (10 mL) and stirred at room temperature for 30 minutes. The crude reaction mixture was evaporated in vacuo onto ~25g of flash silica gel in vacuo and packed into a loader. Purified by flash chromatography on silica gel (120g, 0% acetone/hexanes (2 CV) -> 30% (25 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a yellow solid, 193 mg (62% yield). MS (APCI): calculated for Chemical Formula: C57H39FI2NO6 (M+H) = 1062; found: 1062. 1H NMR (400 MHz, TCE) 5 10.49 (s, 1H), 8.76 (s, 1H), 8.51 (s, 1H), 8.27 (d, J = 1.5 Hz, 2H), 8.07 (s, 1H), 8.03 (s, 3H), 7.62 (d, J = 8.3 Hz, 2H), 7.49 (ddd, J = 8.5, 6.1, 2.5 Hz, 1H), 7.39 (d, J = 8.2 Hz, 2H), 7.28 (d, J = 8.2 Hz, 1H), 6.93 (s, 2H), 4.01 (s, 2H), 3.01 - 2.79 (m, 4H), 1.65 - 1.45 (m, 4H), 1.50 - 1.30 (m, 8H), 1.03 - 0.81 (m, 6H).
PLC-28 Diethyl 10-(4-(2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dipentylphenyl)-5,5-difluoro-l,3,7,9-tetramethyl-5H- 4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8-dicarboxylate: 4-Formyl-3,5-dipentylphenyl- 2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9-def]isoquinolin-2(3H)- yl)phenyl)acetate (192 mg, 0.1762 mmol), ethyl 2,4-dimethyl-lH-pyrrole-3-carboxylate (65 mg, 0.3875 mmol), and pTsOH.H2O (3.3 mg, 0.01762 mmol) were combined in dry DCE (15 mL) and stirred at room temperature under argon overnight. The reaction mixture was treated with DDQ. (60 mg, 0.2642 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with Et3N (0.20 mL, 1.409 mmol), and BF3.OEt2 (0.26 mL, 2.114 mmol). The addition of Et3N (0.20 mL, 1.409 mmol), and BF3.OEt2 (0.26 mL, 2.114 mmol) was repeated and the reaction mixture was stirred for one hour at 50 °C. The crude reaction mixture was evaporated onto ~30g of flash silica gel in vacuo. Purified by flash chromatography on silica gel (120g, 0% acetone/hexanes (2 CV) -> 30% (25 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 166 mg (65% yield). MS (APCI): calculated for Chemical Formula: CysHeaBF^IXbOg (M+H) = 1424; found: 1424. 1H NMR (400 MHz, TCE) δ 8.76 (s, 1H), 8.51 (s, 1H), 8.27 (s, 2H), 8.08 (s, 1H), 8.03 (d, J = 1.8 Hz, 3H), 7.66 (d, J = 8.4 Hz, 2H), 7.49 (ddd, J = 8.5, 6.2, 2.5 Hz, 1H), 7.44 - 7.35 (m, 2H), 7.28 (d, J = 8.2 Hz, 1H), 7.08 (s, 2H), 7.06 - 6.92 (m, 2H), 4.27 (q, J = 7.1 Hz, 4H), 4.05 (s, 2H), 2.85 (s, 6H), 2.50 - 2.27 (m, 4H), 1.71 (s, 6H), 1.57 - 1.42 (m, 4H), 1.33 (t, J = 7.1 Hz, 6H), 1.25 - 1.11 (m, 8H), 0.83 - 0.73 (m, 6H).
Photoluminescent Compound PLC-29:
Figure imgf000110_0001
2,6-Bis(cyclohexylmethyl)-4-hydroxybenzaldehyde: 2,6-Dibrorrio-4-hydroxybenzaldehyde (1120 mg, 4.000 mmol) and Pd(dppf)CI2 (585 mg, 0.8000 mmol) were combined in dry THF (50 mL) and stirred at room temperature under argon. The reaction mixture was sparged thoroughly with argon, then (cyclohexylmethyl)zinc(ll) bromide (0.5M in THF, 32.0 mL, 16.00 mmol) was added and the reaction mixture further sparged with argon. The reaction mixture was stirred at room temperature for five minutes, then heated to 40 °C overnight. The reaction mixture was cooled to room temperature and partitioned between water (100 mL) and ether (100 mL). The layers were separated and the aqueous layer was extracted with ether (100 mL). The combined organic layers were dried over magnesium sulfate, filtered, and evaporated to dryness in vacuo. The crude reaction mixture was evaporated onto ~20 g of flash silica gel in vacuo and packed into a loader. Purified by flash chromatography on silica gel (0% EtOAc/hexanes (2 CV) -> 20% (15 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives an off-white solid, 833 mg (66% yield). MS (APCI): calculated for Chemical Formula: C2iH3o02 (M+H) = 315; found: 315. 1H NMR (400 MHz, CD2CI2) δ 10.38 (s, 1H), 6.51 (s, 2H), 5.45 (s, 1H), 2.80 (d, J = 7.0 Hz, 4H), 1.75 - 1.56 (m, 10H), 1.47 (ddtd, J = 13.5, 10.5, 7.0, 3.4 Hz, 2H), 1.22 - 1.08 (m, 6H), 1.06 - 0.91 (m, 4H). 3,5-Bis(cyclohexylmethyl)-4-formylphenyl-2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo- lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: 2,6-Bis(cyclohexylmethyl)-4- hydroxybenzaldehyde (409 mg, 1.300 mmol), 2-(4-(5, ll-bis(3,5-bis(trifluoromethyl)pheny l)-l,3- dioxo-lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (1319 mg, 1.560 mmol), DMAP.pTsOH salt (38 mg, 0.1300 mmol), and DIC (0.407 mL, 2.600 mmol) were stirred in dry DCM (10 mL) at room temperature for 30 minutes. The crude reaction mixture was diluted with 3 parts hexanes and loaded onto ~45g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (120g, isocratic DCM). Fractions containing product were evaporated to dryness in vacuo. Gives a yellow solid, 1436 mg (97% yield). MS (APCI): calculated for Chemical Formula: C63H47F12NO6 (M+H) = 1142; found: 1142. 1H NMR (400 MHz, CD2CI2) δ 10.49 (s, 1H), 8.78 (s, 1H), 8.53 (s, 1H), 8.31 (dd, J = 1.7, 0.9 Hz, 2H), 8.13 - 8.07 (m, 1H), 8.05 (t, J = 2.0 Hz, 3H), 7.63 - 7.56 (m, 2H), 7.47 (ddd, J = 8.5, 7.0, 1.7 Hz, 1H), 7.41 - 7.33 (m, 2H), 7.26 (dd, J = 8.3, 1.2 Hz, 1H), 7.01 (dd, J = 8.3, 1.5 Hz, 1H), 6.97 (ddd, J = 8.3, 7.0, 1.3 Hz, 1H), 6.89 (s, 2H), 4.02 (s, 2H), 1.77 - 1.58 (m, 10H), 1.48 (dtd, J = 10.7, 7.4, 3.6 Hz, 2H), 1.25 - 1.10 (m, 6H), 0.99 (qd, J = 10.5, 5.6 Hz, 4H).
PLC-29 Diethyl 10-(4-(2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-bis(cyclohexylmethyl)phenyl)-5,5-difluoro-l,3,7,9- tetramethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8-dicarboxylate: 3,5-
Bis(cyclohexylmethyl)-4-formylphenyl-2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH- xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetate (1435 mg, 1.257 mmol), ethyl 2,4-dimethyl- lH-pyrrole-3-carboxylate (483 mg, 2.890 mmol), and pTsOH.H2O (24 mg, 0.1257 mmol) were stirred in dry DCE (30 mL) under argon for one hour at room temperature. The reaction mixture was treated with DDQ. (513 mg, 2.262 mmol) and stirred at room temperature for 30 minutes. Additional DDQ (86 mg, 0.3371 mmol) was added twice at fifteen and 30 minutes, then the reaction mixture stirred for an additional 30 minutes. The reaction was then treated with Et3N (1.4 mL, 10.05 mmol), and BF3.OEt2 (1.87 mL, 15.08 mmol). The addition of Et3N (1.4 mL, 10.05 mmol), and BF3.OEt2 (1.87 mL, 15.08 mmol) was repeated and the reaction mixture was stirred for one hour at 50 °C. The reaction mixture was cooled to room temperature and evaporated in vacuo onto ~30g of flash silica gel and packed into a loader. Purified by flash chromatography on silica gel (220g, 0% EtOAc/DCM (2 CV) -> 3.5% (20 CV) -> isocratic 3.5%). Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 1182 mg (63% yield). MS (APCI): calculated for Chemical Formula: CgiHesBFuNsOg (M+H) = 1504; found: 1504. 1H NMR (400 MHz, Acetone) δ 8.77 (s, 1H), 8.59 (d, J = 1.7 Hz, 2H), 8.53 (s, 1H), 8.37 - 8.31 (m, 2H), 8.24 (td, J = 1.7, 0.9 Hz, 1H), 8.20 (td, J = 1.7, 0.9 Hz, 1H), 7.68 - 7.59 (m, 2H), 7.55 (ddd, J = 8.5, 7.2, 1.5 Hz, 1H), 7.48 - 7.42 (m, 2H), 7.30 (dd, J = 8.3, 1.2 Hz, 1H), 7.17 (s, 2H), 7.14 (dd, J = 8.3, 1.5 Hz, 1H), 7.03 (ddd, J = 8.4, 7.2, 1.3 Hz, 1H), 4.28 (q, J = 7.1 Hz, 4H), 4.12 (s, 2H), 2.82 (s, 6H), 2.39 (d, J = 7.0 Hz, 4H), 1.76 (s, 6H), 1.67 - 1.52 (m, 10H), 1.53 - 1.41 (m, 2H), 1.33 (t, J = 7.1 Hz, 6H), 1.08
(d, J = 6.7 Hz, 6H).
Photoluminescent Compound PLC-30:
Figure imgf000112_0001
2,6-Dicyclohexyl-4-hydroxybenzaldehyde: 2,6-Dibromo-4-hydroxybenzaldehyde (1120 mg, 4.000 mmol) and PdfdppfJCh (585 mg, 0.8000 mmol) were combined in dry THF (50 mL) and stirred at room temperature under argon. The reaction mixture was sparged thoroughly with argon, then cyclohexylzinc(ll) bromide (0.5M in THF, 32.0 mL, 16.00 mmol) was added and the reaction mixture further sparged with argon. The reaction mixture was stirred at room temperature for five minutes, then heated to 40 °C overnight. The reaction mixture was heated at 80 °C for six hours, then cooled to room temperature. The crude reaction mixture was evaporated onto ~50g of flash silica gel in vacuo and packed into a loader. Purified by flash chromatography on silica gel (120g, 0% EtOAc/hexanes (2
Figure imgf000112_0002
3,5-Dicyclohexyl-4-formylphenyl-2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH- xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: 2,6-Dicyclohexyl-4-hydroxybenzaldehyde (93 mg, 0.3247 mmol), 2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetic acid (329 mg, 0.3896 mmol), DMAP.pTsOH salt (10 mg, 0.03896 mmol), and DIC (0.102 mL, 0.6494 mmol) were stirred in dry DCM (5 mL) at room temperature for 30 minutes. The crude reaction mixture was diluted 2:1 with hexanes and loaded onto ~30g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (120g, isocratic DCM). Fractions containing product were evaporated to dryness in vacuo. Gives a yellow solid, 291 mg (80% yield). MS (APCI): calculated for Chemical Formula: Cg^F^NOg (M+H) = 1114; found: 1114. 1H NMR (400 MHz, Acetone) δ 10.66 (s, 1H), 8.76 (s, 1H), 8.58 (d, J = 1.7 Hz, 2H), 8.52 (s, 1H), 8.33 (d, J = 1.7 Hz, 2H), 8.24 (dd, J = 1.8, 0.9 Hz, 1H), 8.20 (dq, J = 2.0, 0.9 Hz, 1H), 7.65 - 7.57 (m, 2H), 7.54 (ddd, J = 8.5, 7.2, 1.5 Hz, 1H), 7.47 - 7.41 (m, 2H), 7.29 (dd, J = 8.3, 1.2 Hz, 1H), 7.16 - 7.07 (m, 3H), 7.02 (ddd, J = 8.4, 7.1, 1.3 Hz, 1H), 4.09 (s, 2H), 3.21 (ddd, J = 11.2, 8.2, 2.8 Hz, 2H), 1.87 - 1.77 (m, 8H), 1.77 - 1.68 (m, 2H),
I.54 - 1.40 (m, 8H), 1.36 - 1.23 (m, 2H).
PLC-30 Diethyl 10-(4-(2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dicyclohexylphenyl)-5,5-difluoro-l,3,7,9-tetramethyl- 5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8-dicarboxylate: 3,5-Dicyclohexyl-4- formylphenyl-2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetate (290 mg, 0.2603 mmol), ethyl 2,4-dimethyl-lH-pyrrole-3- carboxylate (100 mg, 0.5987 mmol), and pTsOH.H2O (5 mg, 0.02603mmol) were stirred in dry DCE (30 mL) under argon for one hour at room temperature. The reaction mixture was treated with DDQ. (106 mg, 0.4686 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with Et3N (0.29 mL, 2.083 mmol), and BF3.OEt2 (0.39 mL, 3.124 mmol). The addition of Et3N (0.29 mL, 2.083 mmol), and BF3.OEt2 (0.39 mL, 3.124 mmol) was repeated and the reaction mixture was stirred for one hour at 50 °C. The crude reaction mixture was evaporated onto ~25g of flash silica gel in vacuo and packed into a loader. Purified by flash chromatography on silica gel (220g, 0% EtOAc/DCM (2 CV)
Figure imgf000113_0001
isocratic 3.5%). Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 302 mg (79% yield). MS (APCI): calculated for Chemical Formula: C7gHg4BFi4N30g (M+H) = 1476; found: 1476. 1H NMR (400 MHz, CD2CI2) δ 8.78 (s, 1H), 8.53 (s, 1H), 8.32 - 8.29 (m, 2H), 8.09 (dq, J = 1.8, 0.9 Hz, 1H), 8.05 (dd, J = 4.1, 1.8 Hz, 3H), 7.66 - 7.60 (m, 2H), 7.47 (ddd, J = 8.5, 7.0, 1.7 Hz, 1H), 7.41 - 7.34 (m, 2H), 7.26 (dd, J = 8.3, 1.3 Hz, 1H), 7.15 (s, 2H), 7.02 (dd, J = 8.4, 1.7 Hz, 1H), 6.97 (ddd, J = 8.3, 7.0, 1.3 Hz, 1H), 4.26 (q, J = 7.1 Hz, 4H), 4.04 (s, 2H), 2.83 (s, 6H), 2.42 (tt, J =
II.8, 3.4 Hz, 2H), 1.72 (s, 6H), 1.70 - 1.54 (m, 10H), 1.48 - 1.34 (m, 4H), 1.32 (t, J = 7.1 Hz, 6H), 1.26 - 1.02 (m, 6H).
Ill Photoluminescent Compound PLC-31:
Figure imgf000114_0001
PLC-31 Diethyl 10-(4-(2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dicyclohexylphenyl)-5,5-difluoro-3,7-dimethyl-5H- 4l4,5l4-dipyrrolo[l,2-c:2',r-f][l,3,2]diazaborinine-2,8-dicarboxylate: 3,5-Dicyclohexyl-4- formylphenyl-2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetate (501 mg, 0.450 mmol), ethyl 2-methyl-lH-pyrrole-3- carboxylate (173 mg, 1.125 mmol), and pTsOH.^O (9 mg, 0.045 mmol) were stirred in dry DCE (30 mL) under argon at 70 °C overnight. The reaction was cooled to room temperature and was treated with DDQ. (184 mg, 0.80 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with EtsN (0.50 mL, 3.600 mmol), and BFs.OEt? (0.67 mL, 5.400 mmol). The addition of EtaN (0.50 mL, 3.600 mmol), and BFs.OEtz (0.67 mL, 5.400 mmol) was repeated and the reaction mixture was stirred for one hour at 50 °C. The crude reaction mixture was evaporated in vacuo onto ~50g of flash silica gel and packed into a loader. Purified by flash chromatography on silica gel (120g,
Figure imgf000114_0002
5% (10 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives an orange solid, 393 mg (60% yield). MS (APCI): calculated for Chemical Formula: C77H60BF14N3O9 (M+H) = 1448; found: 1448. 1H NMR (400 MHz, Acetone) δ 8.76 (s, 1H), 8.58 - 8.55 (m, 2H), 8.52 (s, 1H), 8.34 - 8.30 (m, 2H), 8.24 (dq, J = 1.9, 0.9 Hz, 1H), 8.20 (td, J = 1.7, 0.9 Hz, 1H), 7.69 - 7.61 (m, 2H), 7.53 (ddd, J = 8.5, 7.2, 1.5 Hz, 1H), 7.49 - 7.42 (m, 2H), 7.28 (dd, J = 8.3, 1.3 Hz, 1H), 7.23 (s, 2H), 7.11 (dd, J = 6.8, 1.5 Hz, 3H), 7.01 (ddd, J = 8.4, 7.2, 1.3 Hz, 1H), 4.23 (q, J = 7.1 Hz, 4H), 4.13 (s, 2H), 2.90 (s, 6H), 2.42 - 2.27 (m, 2H), 1.72 - 1.42 (m, 14H), 1.27 (q, J = 7.0 Hz, 8H), 1.00 (qt, J = 13.8, 3.9 Hz, 2H).
Photoluminescent Compound PLC-32:
Figure imgf000115_0001
2,6-Dibromo-4-(methoxymethoxy)benzaldehyde: 2,6-Dibromo-4-hydroxybenzaldehyde (5.598 g, 20.00 mmol) and potassium carbonate (5528 mg, 40.00 mmol) were combined in dry THF (100 mL) and stirred under argon. To the flask was added MOM-CI (1.97 mL, 26.00 mmol). The reaction mixture was stirred at room temperature overnight. The crude reaction mixture was evaporated in vacuo onto ~60g of flash silica gel and packed into a loader. Purified by flash chromatography on silica gel (220g, 25% DCM/hexane (0.5 CV) 100% DCM (0 CV) -> isocratic DCM)). Fractions containing product were evaporated to dryness in vacuo. Gives an off-white solid, 5.677 g (88% yield). MS (APCI): calculated for Chemical Formula: CgHgBrzOs (M+H) = 323; found: 323.
4-(Methoxymethoxy)-2,6-diphenoxybenzaldehyde: 2,6-Dibromo-4-(methoxymethoxy)benzaldehyde (324 mg, 1.000 mmol), phenol (376 mg, 4.000 mmol), N,N-dimethylglycine (7 mg, 0.07000 mmol), cesium carbonate (1955 mg, 6.000 mmol), and Cui (6 mg, 0.03000 mmol) were combined in dioxane (3 mL) in a microwave vial. The reaction was sparged with argon for 30 minutes, then the vial cap was crimped on and the vial heated in a heat block at 100 °C for six hours. The crude reaction mixture was evaporated in vacuo onto ~40g of flash silica gel and packed into a loader. Purified by flash chromatography on silica gel (120g, 0% EtOAc/hexanes (2 CV) -> 100% EtOAc (20 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives an orange oil that slowly solidifies, 247 mg (71% yield). MS (APCI): calculated for Chemical Formula: CziHisOs (M+H) = 351; found: 351. 1H NMR (400 MHz, CD2CI2) δ 10.41 (s, 1H), 7.45 - 7.36 (m, 4H), 7.19 (ddt, J = 8.6, 7.7, 1.1 Hz, 2H), 7.13 - 7.04 (m, 4H), 6.25 (s, 2H), 5.00 (s, 2H), 3.35 (s, 3H).
4-Hydroxy-2,6-diphenoxybenzaldehyde: 4-(Methoxymethoxy)-2,6-diphenoxybenzaldehyde (247 mg, 0.7050 mmol) and 1,4-dimethoxybenzene (195 mg, 1.410 mmol) were dissolved in DCM (5 mL) and stirred at room temperature. To the solution was added TFA (5 mL) and the solution stirred at room temperature for 30 minutes. The crude reaction mixture was diluted 1:1 with hexanes and loaded onto a loader packed with ~50g of flash silica gel. Purified by flash chromatography on silica gel (120g, 0% EtOAc/hexane (2 CV) -> 100% EtOAc (20 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives an off-white solid, 194 mg (90% yield). MS (APCI): calculated for Chemical Formula: C19H14O4 (M+H) = 307; found: 307. 1H NMR (400 MHz, CD2CI2) δ 10.38 (s, 1H), 7.46 - 7.36 (m, 4H), 7.24 - 7.16 (m, 2H), 7.12 - 7.04 (m, 4H), 5.98 (s, 2H), 5.95 (s, 1H).
4-Formyl-3,5-diphenoxyphenyl-2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH- xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: 4-Hydroxy-2,6-diphenoxybenzaldehyde
(192 mg, 0.6268 mmol), 2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetic acid (636 mg, 0.7522 mmol), DMAP.pTsOH salt (18 mg, 0.06268 mmol), and DIC (0.196 mL, 1.254 mmol) were stirred in dry DCM (10 mL) at room temperature for 30 minutes. The crude reaction mixture was loaded onto a loader packed with ~40g of flash silica gel. Purified by flash chromatography on silica gel (120g, 0% EtOAc/DCM (2 CV) -> 10% (30 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a yellow solid, 642 mg (90% yield). MS (APCI): calculated for Chemical Formula: CeiHsiFizNOs (M+H) = 1134; found: 1134. 1H NMR (400 MHz, CD2CI2) 8 10.54 (s, 1H), 8.76 (s, 1H), 8.51 (s, 1H), 8.33 - 8.25 (m, 2H), 8.12 - 8.08 (m, 1H), 8.05 (d, J =
1.7 Hz, 3H), 7.56 - 7.37 (m, 8H), 7.32 - 7.26 (m, 3H), 7.23 (ddt, J = 8.5, 7.3, 1.1 Hz, 3H), 7.02 (dd, J =
8.3. 1.7 Hz, 1H), 6.97 (ddd, J = 8.3, 7.0, 1.3 Hz, 1H), 6.43 (s, 2H), 3.87 (s, 2H).
PLC-32 Diethyl 10-(4-(2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-diphenoxyphenyl)-5,5-difluoro-l,3,7,9-tetramethyl- 5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8-dicarboxylate: 4-Formyl-3,5- diphenoxyphenyl-2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetate (639 mg, 0.5635 mmol), ethyl 2,4-dimethyl-lH-pyrrole-3- carboxylate (236 mg, 1.409 mmol), and pTsOH.HzO (11 mg, 0.05635 mmol) were stirred in dry DCE (50 mL) under argon for one hour at room temperature. The reaction mixture was treated with DDQ. (230 mg, 1.014 mmol) and stirred at room temperature for 30 minutes. The reaction was then treated with Et3N (0.63 mL, 4.508 mmol), and BF3.OEt2 (0.83 mL, 6.763 mmol). The addition of Et3N (0.63 mL, 4.508 mmol), and BF3.OEt2 (0.83 mL, 6.763 mmol) was repeated and the reaction mixture was stirred for one hour at 50 ° C. The crude reaction mixture was evaporated in vacuo onto ~60g of flash silica gel and packed into a loader. Purified by flash chromatography on silica gel (220g, 0% EtOAc/DCM (2 CV) -> 3% (20 CV) -> isocratic 3%). Gives an orange solid, 598 mg (71% yield). MS (APCI): calculated for Chemical Formula: C79H52BF14N3O11 (M+H) = 1496; found: 1496. 1H NMR (400 M Hz, Acetone) 6 8.75 (s, 1H), 8.59 - 8.56 (m, 2H), 8.51 (s, 1H), 8.36 - 8.33 (m, 2H), 8.26 - 8.22 (m, 1H), 8.22 - 8.18 (m, 1H), 7.54 (ddd, J = 8.5, 7.2, 1.5 Hz, 1H), 7.50 - 7.40 (m, 6H), 7.39 - 7.33 (m, 2H), 7.30 (dd, J = 8.3, 1.3 Hz, 1H), ~1.T1 - 7.19 (m, 2H), 7.16 - 7.06 (m, 5H), 7.02 (ddd, J = 8.4, 7.2, 1.3 Hz, 1H), 6.52 (s, 2H), 4.32 (q, J = 7.1 Hz, 4H), 3.99 (s, 2H), 2.79 (s, 6H), 2.27 (s, 6H), 1.37 (t, J = 7.1 Hz, 6H).
Photoluminescent Compound PLC-33:
Figure imgf000117_0001
PLC-33 Diethyl 5,5-dicyano-10-(4-(2-(4-(l,3-dioxo-5,ll-bis(4-(trifluoromethyl)phenyl)-lH- xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dimethoxyphenyl)-l, 3,7,9- tetramethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8-dicarboxylate: Diethyl 10-(4- (2-(4-(l,3-dioxo-5,ll-bis(4-(trifluoromethyl)phenyl)-lH-xantheno[2,l,9-def]isoquinolin-2(3H)- yl)phenyl)acetoxy)-2,6-dimethoxyphenyl)-5,5-difluoro-l,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[l,2- c:2',l'-f][l,3,2]diazaborinine-2,8-dicarboxylate (0.1000 mmol, 124 mg) was dissolved in dry DCE (10 mL) and treated with TMSCN (2.000 mmol, 0.250 mL), and BF3.OEt2 (0.1500 mmol, 0.019 mL). The reaction was stirred room temperature for a few minutes, then heated to 45 °C for 60 minutes. The reaction mixture was poured into ~30 mL of saturated NaHCO3 and stirred for a few minutes. The reaction was filtered through a polypropylene frit to retain water, eluting product with DCM. The eluent was evaporated to dryness in vacuo, dissolved in a small amount of DCM, and loaded onto ~15g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (80g, 0% acetone/hexane (2 CV)
Figure imgf000118_0001
35% (5 CV), stopping gradient at 26.6%. Fractions containing product were evaporated to dryness in vacuo. The product was triturated with MeOH/water, filtered, washed with MeOH/water, dissolved in DCM, and evaporated to dryness in vacuo. Gives an orange solid, 121 mg (97% yield). MS (APCI): calculated for Chemical Formula: CeaHsoBFeNsOn (M+H) = 1250; found: 1250. 1H NMR (400 MHz, TCE) δ 8.71 (s, 1H), 8.48 (s, 1H), 7.91 (d, J = 8.3 Hz, 2H), 7.89 - 7.82 (m, 4H), 7.67 (dd, J = 8.3, 2.5 Hz, 4H), 7.47 - 7.38 (m, 3H), 7.31 (dd, J = 8.4, 1.3 Hz, 1H), 7.10 (dd, J = 8.3, 1.5 Hz, 1H), 6.96 (ddd, J = 8.4, 7.1, 1.4 Hz, 1H), 6.58 (s, 2H), 4.32 (q, J = 7.1 Hz, 4H), 4.05 (s, 2H), 3.76 (s, 6H), 3.01 (s, 6H), 1.92 (s, 6H), 1.37 (t, J = 7.1 Hz, 6H).
Photoluminescent Compound PLC-34:
Figure imgf000118_0002
4-Formyl-3,5-dimethoxyphenyl 2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH- xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetate): 2-(4-(5,ll-bis(3,5- bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (2.750 mmol, 2325 mg), 4-hydroxy-2,6-dimethoxybenzaldehyde (2.500 mmol, 455 mg), DMAP.pTsOH salt (0.2500 mmol, 74 mg), and EDC.HCI (5.000 mmol, 986 mg) were stirred in dry DCE (30 mL) in a vial for 60 minutes at room temperature. The crude reaction mixture was loaded onto ~45g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (120g, 0% EtOAc/DCM (2 CV) -> 30% (10 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a yellow solid, 2061 mg (82% yield). MS (APCI): calculated for Chemical Formula: C51H27F12NO8 (M+H) = 1010; found: 1010. 1H NM R (400 M Hz, Acetone) δ 10.38 (s, 1H), 8.76 (s, 1H), 8.60 - 8.56 (m, 2H), 8.51 (s, 1H), 8.33 (d, J = 1.7 Hz, 2H), 8.24 (s, 1H), 8.22 - 8.18 (m, 1H), 7.60 (d, J = 8.4 Hz, 2H), 7.54 (ddd, J = 8.5, 7.2, 1.5 Hz, 1H), 7.48 - 7.40 (m, 2H), 7.28 (dd, J = 8.3, 1.3 Hz, 1H), 7.11 (dd, J = 8.3, 1.5 Hz, 1H), 7.02 (ddd, J = 8.3, 7.1, 1.3 Hz, 1H), 6.61 (s, 2H), 4.09 (s, 2H), 3.87 (s, 6H).
PLC-34 Dimethyl 10-(4-(2-(4-(l,3-dioxo-5,ll-bis(4-(trifluoromethyl)phenyl)-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dimethoxyphenyl)-5,5-difluoro-3,7-diisopropyl-l,9- dimethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8-dicarboxylate: The aldehyde from the previous step (0.4000 mmol, 404 mg), ethyl 2-isopropy-4-methyl-lH-pyrrole-3-carboxylate (0.8000 mmol, 145 mg), and PTSOH.H2O (0.08000 mmol) were stirred in dry DCE (25 mL) at room temperature under argon for 30 minutes, then DDQ was added (0.8000 mmol, 182 mg) and stirred for 5 minutes. EtsN (3.200 mmol, 0.45 mL), and BFs.0Et2 (4.800 mmol, 0.59 mL) were added to the reaction. The addition of EtsN (3.200 mmol, 0.45 mL), and BF3.OEt2 (4.800 mmol, 0.59 mL) was repeated and the reaction stirred at 65 °C for 8 hours, then stirred at room temperature overnight. The reaction was quenched with 5 mL of water and stirred for a few minutes, then filtered through a polypropylene frit to retain water. The frit was eluted with DCM. The eluent was directed onto a 15g flash silica plug, eluting with DCM, then eluting with 33% acetone/DCM. The solvents were evaporated to dryness in vacuo, dissolved in a small amount of DCM and loaded onto 15g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (120g, 0% EtOAc/DCM
Figure imgf000119_0001
20% (5 CV), stop at 4.0% eluting isocratic. Fractions containing product were evaporated to dryness in vacuo. The product was triturated with hot MeOH, cooled to room temperature, filtered off, washing with MeOH, dissolved in DCM, and evaporated to dryness in vacuo. Gives an orange solid, 447 mg (80% yield). MS (APCI): calculated for Chemical Formula: C69H54BF8N3O11 (M+H) = 1264; found: 1264. 1H NMR (400 MHz, TCE) δ 8.67 (s, 1H), 8.42 (s, 1H), 8.18 (d, J = 1.6 Hz, 2H), 7.99 (s, 1H), 7.94 (t, J = 2.3 Hz, 3H), 7.63 - 7.52 (m, 2H), 7.40 (ddd, J = 8.5, 6.3, 2.4 Hz, 1H), 7.36 - 7.24 (m, 2H), 7.22 - 7.15 (m, 1H), 7.00 - 6.80 (m, 2H), 6.46 (s, 2H), 3.96 (s, 2H), 3.74 (s, 8H), 3.68 (s, 6H), 1.31 (d, J = 7.0 Hz, 12H).
Photoluminescent Compound PLC-35:
Figure imgf000120_0001
PLC-35 Dimethyl 10-(4-(2-(4-(5,ll-bis(3,5-bis(trifluoromethyl)phenyl)-l,3-dioxo-lH-xantheno[2,l,9- def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dimethoxyphenyl)-5,5-dicyano-3,7-diisopropyl-l,9- dimethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8-dicarboxylate: PLC-34 (0.1500 mmol, 210 mg), TMSCN (1.500 mmol, 0.19 mL), and BF3.OEt2 (0.2250 mmol, 0.028 mL) were stirred in dry DCE (10 mL) under argon at room temperature for a few minutes, then heated to 45 °C for 60 minutes, then room temperature overnight. The crude reaction mixture was poured into 30 mL of sat. NaHCO3 solution and stirred for 5 minutes, then filtered through a polypropylene frit to retain water. The frit was eluted with DCM. The organic eluent was evaporated to dryness in vacuo, dissolved in a small amount of DCM and loaded onto 15g of flash silica gel packed into a loader. Purified by flash chromatography on silica gel (80g, 0% acetone/DCM (2 CV)
Figure imgf000120_0002
5% (5 CV), stop at 1.1%, 1.4%, 1.6%, 1.8%, 2.2%, 2.4%, isocratic at each step. Fractions containing product were evaporated to dryness in vacuo. The product was triturated with hot MeOH, cooled to room temperature, filtered off, washed with MeOH, dissolved in DCM, and evaporated to dryness in vacuo. Gives an orange solid, 157 mg (74% yield). MS (APCI): calculated for Chemical Formula: C73H52BF12N5O11 (M+H) = 1414; found: 1414. 1H NMR (400 MHz, TCE) δ 8.76 (s, 1H), 8.51 (s, 1H), 8.27 (d, J = 1.6 Hz, 2H), 8.08 (s, 1H), 8.06 - 8.00 (m, 3H), 7.69 - 7.62 (m, 2H), 7.49 (ddd, J = 8.6, 6.3, 2.3 Hz, 1H), 7.44 - 7.36 (m, 2H), 7.32 - 7.25 (m, 1H), 7.00 (dd, J = 6.6, 1.5 Hz, 2H), 6.55 (s, 2H), 3.91 - 3.80 (m, 8H), 3.78 (s, 6H), 1.74 (s, 6H), 1.53 (d, J = 6.8 Hz, 12H).
Example 2: Procedure to measure optical properties of sharp emitter chromophores
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 (DI) water, rinsed with fresh DI water, and sonicated for about 1 hour. The glass was then soaked in isopropanol (I PA) and sonicated for about 1 hour. The glass substrate was then soaked in acetone and sonicated for about 1 hour. The glass was then removed from the acetone bath and dried with nitrogen gas at room temperature.
A 25 wt% solution of poly(methyl methacrylate) (PMMA) resin in spectroscopy grade toluene was prepared. The prepared PMMA polymer was stirred at 50 °C until PMMA was fully dissolved. [PMMA] CAS: 9011-14-7; [Toluene] CAS: 108-88-3.
In a 20 mL vial, 2 mg of chromophore was added into the PMMA solution to make a 2.0 x 10’3 M solution [PMMA volume was calculated using the formula:
Figure imgf000121_0001
Mw L then dye mixed well by Vortex for about 5 min and sonicated for about 60 minutes. The PMMA/Compound solution was then spin coated onto a prepared glass substrate at 1000 RPM for 20 s. The spin-coated samples were baked in an oven at 150 °C for 5 minutes to evaporate the remaining solvent.
The 1-inch X 1-inch sample was inserted into a Shimadzu, UV-3600 UV-VIS- NIR spectrophotometer (Shimadzu Instruments, Inc., Columbia, MD, USA) to measure absorption spectrum.
The fluorescence spectrum (emission spectrum) of a 1-inch X 1-inch film sample prepared as described above was determined using a Fluorologmax spectrofluorometer (Horiba Scientific, Edison, NJ, USA). Both 390nm and 450nm wavelengths were chosen as excitation wavelength.
The quantum yields of spin-coated samples as described above were determined using a Hamamatsu C11347 Absolute PL quantum yield spectrometer (Hamamatsu Inc., Campbell CA, USA). A 0.5"x 0.5" size film was taken out from glass substrate for QY measurement. Wavelengths were scanned every 30 nm from 390 nm to 450 nm (as excitation wavelengths). The QY at 450 nm are reported in Table 1.
The optical properties of the spin-coated films (absorbance peak wavelength, emission peak wavelength, FWHM, and quantum yield) are shown in Table 1, below.
Table 1. Optical Properties of Chromophores in PMMA
Figure imgf000121_0002
Figure imgf000122_0001
Figure imgf000123_0001
Figure imgf000124_0001
Figure imgf000125_0001
Figure imgf000126_0001
Figure imgf000127_0001
Figure imgf000128_0001
Figure imgf000129_0001
Figure imgf000130_0001
Figure imgf000131_0001
Figure imgf000132_0001
Figure imgf000133_0001
Figure imgf000134_0001
Figure imgf000135_0001
Figure imgf000136_0001
Figure imgf000137_0001
Example 3: Photostability
Photostability of the chromophores were tested by exposing the 1-inch X 1-inch sample on 40 mW/cm2 Blue LEDs (CREE, Durham, North Carolina, USA). The samples were monitored daily (the first 2-3 days) then weekly for absorbance, emission, and QY following same procedures written above. The chromophore's photo durability is quantified by the decrease in Absorbance (Abs%). Changes in QY%, Emission properties are also monitored. Photostability measurements continued until absorbance decayed to less than 50% Absorbance. Photostability data of PLC-1 as compared to CE-3 is provided in FIG. 1. This graph exhibits the improved photostability of current PLC-1 relative to CE-
3.

Claims

1. A photoluminescent complex comprising: a blue light absorbing moiety; a linker complex; and a boron-dipyrromethene (BODIPY) moiety; wherein the blue light absorbing moiety is a xanthenoisoquinoline group of the general formula:
Figure imgf000138_0001
wherein each R° is independently H, alkyl, -CF3, alkoxy, or optionally substituted aryl; wherein R10 is H, alkyl, -CF3, alkoxy, or optionally substituted aryl; wherein the dashed line is a covalent bond to the linker complex; wherein the BODIPY moiety is of the general formula:
Figure imgf000138_0002
wherein X is F or CN; wherein R1 and R6are independently H or alkyl; wherein R3 and R4 are independently H or alkyl; wherein R2 and R5 are independently H, alkyl, cycloalkyl, -CN, an alkyl ester group, or an aryl ester group; wherein R7 and R8 are independently optionally substituted aryl, Ci.s alkyl; C3.s cycloalkyl; an ether group having a Ci-io alkyl group, an ether moiety having an optionally substituted aryl group, or a Ci-io arylalkyl group; wherein the linker complex comprises an optionally substituted ester or an optionally substituted ether linker; wherein the linker complex covalently links the blue light absorbing moiety and the BODIPY moiety, wherein the blue light absorbing moiety absorbs light energy of a first excitation wavelength and transfers an energy to the BODIPY moiety, wherein the BODIPY moiety absorbs the energy from the blue light absorbing moiety 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 R7 and R8 are -CH2CH(CH2CH3)(CH2)3CH3, cyclopropyl, cyclohexyl, n-pentyl, -CH2-cyclohexyl, -OCH2-cyclohexyl, -O(CH2)3Ph,
Figure imgf000139_0001
3. The photoluminescent complex of claim 1, wherein R7 and Rs are independently optionally substituted alkyl, optionally substituted cycloalkyl, or an optionally substituted ether group comprising pentyl, 2-ethylhexyl, cyclohexyl, CH2-cyclohexyl, -OCH3, -O-(2-ethylhexyl), -OCH2- cyclohexyl, -OPh, or -O(CH2)3-Ph.
4. The photoluminescent complex of claim 1, 2, or 3, wherein R1 and R6 are independently H, methyl, ethyl, propyl group, isopropyl, butyl, or isobutyl; and wherein R3 and R4are independently H, methyl, ethyl, propyl, isopropyl, butyl, or isobutyl.
5. The photoluminescent complex of claim 1, 2, 3, or 4, wherein R2 and R5 comprise -C(O)OMe,
Figure imgf000140_0001
6. The photoluminescent complex of claim 1, 2, 3, 4, or 5, wherein R° comprises
Figure imgf000140_0002
,
Figure imgf000140_0003
wherein R10 comprises H.
7. The photoluminescent complex of claim 1, 2, 3, 4, 5, or 6, wherein the linker complex comprises
Figure imgf000140_0004
8. The photoluminescent complex of claim 1, 2, 3, 4, 5, 6, or 7 , wherein X is F.
9. The photoluminescent complex of claim 1, 2, 3, 4, 5, 6, or 7 , wherein X is CN.
10. The photoluminescent complex of claim 1, 2, 3, 4, 5, 6, 7, 8, or 9, wherein the photoluminescent complex comprises one of the following structures:
Figure imgf000141_0001
Figure imgf000142_0001
Figure imgf000143_0001
Figure imgf000144_0001
Figure imgf000145_0001
Figure imgf000146_0001
Figure imgf000147_0001
Figure imgf000148_0001
Figure imgf000149_0001
Figure imgf000150_0001
Figure imgf000151_0001
Figure imgf000152_0001
Figure imgf000153_0001
Figure imgf000154_0001
Figure imgf000155_0001
Figure imgf000156_0001
Figure imgf000157_0001
Figure imgf000158_0001
11. 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, wherein the photoluminescent compound comprises the photoluminescent complex of claim 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, dispersed within the resin matrix.
12. The color conversion film of claim 11, further comprising a singlet oxygen quencher.
13. The color conversion film of claim 11, further comprising a radical scavenger.
14. The color conversion film of claim 11, wherein the color conversion film has a thickness of between about 1 μm and about 200 μm.
15. The color conversion film of claim 11, wherein the color conversion film absorbs light in about
400 nm to about 480 nm wavelength range and emits light in the 500 nm to about 560 wavelength range.
16. A method for preparing the color conversion film of claim 11, 12, 13, 14 or 15, comprising: dissolving the photoluminescent complex of claim 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, and a binder resin within a solvent; and applying the mixture to a surface of the transparent substrate.
17. A backlight unit comprising the color conversion film of claim 11, 12, 13, 14, or 15.
18. A display device including the back-light unit of claim 17.
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Publication number Priority date Publication date Assignee Title
WO2022178450A1 (en) 2021-02-22 2022-08-25 Nitto Denko Corporation Boron-containing cyclic emissive compounds and color conversion film containing the same
WO2023158976A1 (en) * 2022-02-18 2023-08-24 Nitto Denko Corporation Boron-containing cyclic emissive compounds and color conversion film containing the same
WO2023158977A1 (en) * 2022-02-18 2023-08-24 Nitto Denko Corporation Boron-containing cyclic emissive compounds and color conversion film containing the same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022178450A1 (en) 2021-02-22 2022-08-25 Nitto Denko Corporation Boron-containing cyclic emissive compounds and color conversion film containing the same
WO2023158976A1 (en) * 2022-02-18 2023-08-24 Nitto Denko Corporation Boron-containing cyclic emissive compounds and color conversion film containing the same
WO2023158977A1 (en) * 2022-02-18 2023-08-24 Nitto Denko Corporation Boron-containing cyclic emissive compounds and color conversion film containing the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WAKAMIYA, ATSUSHI ET AL., CHEMISTRY LETTERS, vol. 37, no. 10, 2008, pages 1094 - 1095

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