WO2021146380A1 - 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
WO2021146380A1
WO2021146380A1 PCT/US2021/013375 US2021013375W WO2021146380A1 WO 2021146380 A1 WO2021146380 A1 WO 2021146380A1 US 2021013375 W US2021013375 W US 2021013375W WO 2021146380 A1 WO2021146380 A1 WO 2021146380A1
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mmol
color conversion
added
mixture
wavelength
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PCT/US2021/013375
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French (fr)
Inventor
Shijun Zheng
Jeffrey R. Hammaker
Hiep Luu
Stanislaw Rachwal
Jan SASKA
Jie Cai
Peng Wang
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Nitto Denko Corporation
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Priority to JP2022543068A priority Critical patent/JP7415016B2/en
Priority to KR1020227024542A priority patent/KR20220116256A/en
Priority to CN202180009558.4A priority patent/CN115003778A/en
Publication of WO2021146380A1 publication Critical patent/WO2021146380A1/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
    • C07F5/022—Boron compounds without C-boron linkages
    • 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
    • G02F1/133602—Direct backlight
    • G02F1/133609—Direct backlight including means for improving the color mixing, e.g. white
    • 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
    • G02F1/133621—Illuminating devices providing coloured light
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502—Wavelength conversion materials
    • 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
    • H10K59/80—Constructional details
    • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
    • 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
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene

Definitions

  • the present disclosure related to compounds for use in color conversion film, and a backlight unit, and a display apparatus including the same.
  • the gamut In color reproduction the gamut, or color gamut, is a certain complete subset of colors available on a device such as a television or monitor.
  • a device such as a television or monitor.
  • RGB Red Green Blue
  • RGB Red Green Blue
  • a wide-gamut color space achieved by using pure spectral primary colors was developed to provide a broader color gamut and offer a more realistic representation of visible colors viewed through a display. It is believed that a device which could provide a wider gamut could enable the display to portray more vibrant colors.
  • LEDs Current light emitting diode
  • FWHM full width half maximum
  • the emission peak of the current green and red phosphors are quite lager, 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.
  • methods have been developed using films containing quantum dots in combination with LEDs.
  • quantum dots there are problems with the use of quantum dots.
  • cadmium-based 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 into green and red light.
  • quantum dots require expensive encapsulating processes for protection against moisture and oxygen.
  • the cost of using quantum dots is high due to the difficulties in controlling size uniformity during the production process.
  • a novel approach to address the issues presented with the use of quantum dots, involves the use of a boron-dipyrromethene (BODIPY) compounds as the emissive materials to replace the quantum dots.
  • BODIPY boron-dipyrromethene
  • Photoluminescent compounds described herein may be used to improve the contrast between distinguishable colors in televisions, computer monitors, smart devices and any other devices that utilize color displays.
  • the photoluminescent complexes of the present disclosure provide novel color converting complexes with good blue light absorbance and narrow emissions bandwidths, with the full width half maximum [FWHM] of emission band of less than 40 nm.
  • a photoluminescent complex absorbs light of a first wavelength and emits light of a second higher wavelength than the first wavelength.
  • the photoluminescent complexes disclosed herein may be utilized with a color conversion film for use in light emitting apparatuses.
  • the color conversion film of the present disclosure reduced color deterioration by reduced overlap within the color spectrum resulting in high quality color rendition.
  • Some embodiments include a photoluminescent complex comprising: a donor chromophore; an acceptor chromophore; and a linker complex.
  • Some photoluminescent complexes are represented by Formula I:
  • the donor chromophore, or D absorbs light in the blue light wavelength and emits an excitation energy.
  • the donor chromophore may comprise a perylene derivative of the following formula:
  • R 8 , R 10 and R 11 may be selected from a H or a -CF 3 .
  • R 9 is H.
  • the acceptor chromophore, or A emits light in the red light wavelength.
  • the acceptor chromophore may comprise a BODIPY derivative of the following formula:
  • R' is independently H, -CH 3 , F, orCF 3 ;
  • R" is-H, ora bond connecting to L— D;
  • R 1 and R 2 are independently H or -CH 3 ;
  • R 3 and R 4 are independently H, F, Br, -CF 3 , phenyl optionally substituted with 1 or 2 -CH 3 , -F, -CF 3 , or -L—D groups;
  • the acceptor chromophore absorbs the excitation energy emitted by the donor chromophore wherein the acceptor chromophore then emits a second wavelength of light which is a higher wavelength of light than the blue light wavelength. In some embodiments, the acceptor chromophore emits light in the red light wavelength.
  • the linker complex links the donor chromophore and the acceptor chromophore.
  • the photoluminescent complex has an emission quantum yield greater than 80%. In some embodiments, the photoluminescent complex may have an emission band with a full width half maximum [FWHM] of up to 40 nm.
  • the photoluminescent complex may have a Stokes shift, the difference between the excitation peak of the blue light absorbing moiety and the excitation of the BODIPY moiety, of equal to or greater than 45 nm.
  • the color conversion film may comprise: a transparent substrate layer; and a color conversion layer.
  • the color conversion layer may comprise a resin matrix and at least one photoluminescent complex dispersed within the resin matrix.
  • the color conversion film may comprise a thickness between 1 pm to about 200 pm.
  • the color conversion film may comprise a singlet oxygen scavenger.
  • the color conversion film may comprise a radical scavenger.
  • Another embodiment includes a color conversion film that may absorb blue light in the 400 nm to about 480 nm range and emit red light in the 575 nm to about 650 nm wavelength range.
  • the color conversion film may further comprise a transparent substrate layer.
  • Some embodiments include a color conversion film that has a photostability of at least 80% after being exposed to blue light at a peak wavelength of 465 nm for 165 hours.
  • Other embodiments include a color conversion film that has a photostability of at least 75% after being exposed to blue light at a peak wavelength of 465 nm for 330 hours.
  • the transparent substrate layer of the color conversion film comprises two opposing surfaces, wherein the color conversion layer is disposed on one of the opposing surfaces.
  • Some embodiments include a method for preparing the color conversion film, the method comprises: dissolving a resin matrix and a photoluminescent complex within a solvent; and applying the mixture on one of the transparent substrates opposing surfaces.
  • Some embodiments include a backlight unit including the herein aforedescribed color conversion film.
  • Some embodiments describe a display device including the backlight unit described hereupon.
  • FIG. 1 is a graph depicting the absorption and emission spectra of one embodiment of a photoluminescent complex.
  • FIG. 2 is a graph depicting the absorption and emission spectra of one embodiment of a photoluminescent complex.
  • the current disclosure describes a photoluminescent complex 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.
  • 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.
  • Some embodiments include a photoluminescent complex that may enhance the contrast or intensity between two colors, increasing their distinction form one another.
  • the term “may” should be construed as shorthand for "is” or “is not” or, alternatively “does” or “does not” or “will” or “will not.”
  • the statement “the alkyl group may be substituted” should be interpreted as, for example, “In some embodiments, the alkyl group is substituted. In some embodiments, the alkyl group is not substituted.”
  • the statement “the photoluminescent complex may enhance the contrast” should be interpreted as, for example, "In some embodiments, the photoluminescent complex of the present disclosure does enhance the contrast.
  • the photoluminescent complex of the present disclosure does not enhance the contrast.
  • the statement "the color conversion film may further comprise a second photoluminescent complex” should be interpreted as, for example, "In some embodiments, the color conversion film will further comprise a second photoluminescent complex. In some embodiments, the color conversion film will not further comprise a second photoluminescent complex.”
  • a compound or chemical structure is referred to as being
  • substituted it includes one or more substituents.
  • a substituted group is derived from the unsubstituted parent structure wherein one or more hydrogen atoms on the parent structure have been independently replaced by one or more substituent groups.
  • a substituent group may have one or more substituent groups on the parent group structure. In one or more forms, the substituent groups may be independently selected from an optionally substituted alkyl or alkenyl, or a C 3- C 7 heteroalkyl
  • alkyl group refers to a hydrocarbon group with no double or triple bonds.
  • An "alkene moiety refers to a group that has at least one carbon-carbon double bond and an “alkyne” moiety refers to a group that has at least one carbon-carbon triple bond.
  • An alkyl, alkene, or alkyne moiety may be straight chain, branched or cyclic.
  • the alkyl moiety may have 1 to 6 carbon atoms (wherever it appears herein, a numerical range such as “1 to 6” refers to each integer in the given range: e.g., "1 to 6 carbon atoms” means that the alkyl group may have 1, 2, 3, 4, 5, or 6 carbon atoms, although the present definition also covers the occurrence of the term "alkyl” where no numerical range is designate.
  • the alkyl group of the compounds designated herein may be designated as “C 1- C 6 alkyl” or similar designations.
  • C 1- C 6 alkyl indicates that there are one to six carbon atoms in the alkyl chain, i.e., the alkyl chain is selected from among methyl, ethyl, propyl, iso- proly, n-butyl, iso-butyl, sec-butyl, and t-butyl.
  • C 1 -C 6 alkyl includes C 1 -C 2 alkyl, C 1 -C 3 alkyl, C 1 -C 4 alkyl, C 1 -C 5 alkyl.
  • Alkyl groups may be substituted or unsubstituted.
  • Typical alkyl groups include, but are in no way limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, hexyl, ethenyl, propenyl, butenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.
  • heteroalkyl refers an alkyl group, as defined herein, in which one or more of the constituent carbon atoms have been replaced by a heteroatom.
  • heteroalkyl groups ae an "alkoxy” which, as used herein, refers alkyl-O- (e.g., methoxy, ethoxy, etc.).
  • heteroatom refers to a nitrogen (N), oxygen (O), or sulphur (S).
  • aromatic refers to a planar ring having a delocalized p-electron system containing 4n+2 p electrons, where n is an integer. Aromatic rings may be formed from e.g. five, six, seven, eight, nine, or more than nine atoms. Aromatics may be optionally substituted.
  • aromatic includes both carbocyclic aryl (e.g., phenyl) and heterocyclic aryl (or “heteroaryl” or heteroaromatic") group (e.g., pyridine).
  • the term includes monocyclic or fused- ring polycyclic (i.e., rings which share adjacent pairs of carbon atoms) groups.
  • hydrocarbon ring refers to a monocyclic or polycyclic radial that contains only carbon and hydrogen, and may be saturated, partially saturated, or fully saturated monocyclic hydrocarbon rings include groups having from 3 to 12 carbon atoms.
  • monocyclic groups include the following moieties:
  • polycyclic groups include the following moieties:
  • aryl as used herein means an aromatic ring wherein each of the atoms forming the ring is a carbon atom.
  • Aryl groups may be substituted or unsubstituted. Examples of aryl groups include, but are not limited to phenyl, naphthalenyl, phenanthrenyl, naphthacenyl, fluorenyl, pyrenyl, etc.
  • heteroaryl refers to an aryl group that include 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. Heteroaryls may be optionally substituted.
  • An N-containing heteroaryl moiety refers to an aryl group in which at least one of the skeletal atoms of the ring is a nitrogen atom
  • heteroaryl groups include the following moieties: pyrrole, imidazole etc.
  • halogen means fluoro, chloro, bromo, and iodo.
  • bond means a chemical bond between two atoms, 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.
  • ether refers to a chemical moiety that contains an oxygen atom connected to two alkyl or aryl groups with the general formula of R-O-R', where the term alkyl and aryl is as defined herein.
  • BODIPY or “BODIPY derivative” as used herein, refers to a chemical moiety
  • BODIPY may be composed or dipyrromethene complexed with a disubstituted boron atom, typically a BF2 unit.
  • the lUPAC name for the BODIPY general core structure is 4,4-difluoro- 4-bora-3a,4a-diaza-s-indacene.
  • perylene or “perylene derivative”: refers to a chemical moiety with the
  • the present disclosure includes photoluminescent complexes that absorb light energy of a first wavelength and emits light energy in a second higher wavelength.
  • the photoluminescent complex of the present disclosure may comprise a donor chromophore, wherein the donor chromophore may absorb blue light (400 to 480 nm wavelength) and release an excitation energy in response thereto; an acceptor chromophore which may comprise boron-dipyrromethene (BODIPY) derivative that may absorb the excitation energy released from the donor chromophore, wherein the acceptor chromophore may then emit a second wavelength of light, the second wavelength of light may be higher wavelength of light than the blue light wavelength; and a linker complex which may link the donor chromophore and the acceptor chromophore together.
  • BODIPY boron-dipyrromethene
  • the photoluminescent complexes describe herein may be incorporated into a color conversion film, greatly increasing the discernibility between colors in the Red Green Blue (RGB) gambit, resulting in increased contrast and higher quality color rendition.
  • the photoluminescent complex comprise a donor chromophore, an acceptor chromophore and a linker complex.
  • the donor chromophore and the acceptor chromophore are connected, creating a spatial relationship which is accomplished with the linker complex.
  • the donor chromophore may absorb light in the blue light wavelength and then release an excitation energy.
  • the acceptor chromophore may absorb the excitation energy, released by the donor chromophore, and then the acceptor chromophore may emit a second wavelength of light, wherein the second wavelength of light may be higher wavelength of light than blue light. In some embodiments, the acceptor chromophore emits red light. It is believed that energy transfer from the donor chromophore to the acceptor chromophore occurs through a forster resonance energy transfer (FRET).
  • FRET forster resonance energy transfer
  • the photoluminescent complex may be represented by Formula I: A— (L— D)I-3, meaning that there may be 1, 2, or 3 L— D groups attached to acceptor chromophore A, such as in Formulas IA, IB, and 1C shown below: wherein A is an acceptor chromophore, L is a linker complex, and D is a donor chromophore.
  • the donor chromophore (D) may comprise a perylene derivative of the following formula;
  • R 8 , R 10 and R 11 may be hydrogen (H) or trifluoromethyl (CF 3 ).
  • R 9 is H.
  • R 8 is H.
  • R 8 is CF 3 .
  • R 10 is H.
  • R 10 is CF 3 .
  • R 11 is H.
  • R 11 is CF 3 .
  • R 8 , R 10 and R 11 are H.
  • R 8 , R 10 and R 11 are CF 3 .
  • Some embodiments include a photoluminescent complex wherein the photoluminescent complex comprises a donor chromophore which absorbs light in the blue light wavelength.
  • the donor chromophore may have a maximum blue light absorbance in the range of 400 nm to about 480 nm, about 400 nm to about 410 nm, about 410 nm to about 420 nm, about 420 nm to about 430 nm, about 430 nm to about 440 nm, about 440 nm to about 450 nm, about 450 nm to about 460 nm, about 460 nm to about 470 nm, to about 470 nm to about 480 nm, or any wavelength that is bounded by these ranges.
  • the photoluminescent complex may have an absorbance maximum peak of about 450 nm.
  • the donor chromophore may have a maximum peak absorbance of about 405 nm.
  • the donor chromophore may have an absorbance maximum peak of about 480 nm.
  • the acceptor chromophore (A) may comprise a boron dipyrromethene (BODIPY) derivative.
  • BODIPY derivative may be of the general formula: With respect to any relevant structural representation, such as Formula III, each R' is H, a methyl group (-CH 3 ), F, or CF 3 .
  • one R' is H.
  • both R' are H.
  • one R' is CH 3 .
  • both R' are CH 3 .
  • R is -H, or a bond connecting to L— D, wherein L is a linker and D is a donor chromophore.
  • R 1 and R 2 are independently H or a methyl (-CH 3 ).
  • R 1 is H.
  • R 1 is CH 3 .
  • R 2 is H.
  • R 2 is CH 3 .
  • both R 1 and R 2 are H.
  • both R 1 and R 2 are CH 3 .
  • R 3 and R 4 are independently H, F, Br, or -CF 3 , phenyl optionally substituted with 1 or 2 -CH 3 , -F, -CF 3 , or -L— D groups, wherein L is a linker and D is a donor chromophore.
  • R 3 is H.
  • R 3 is F.
  • R 3 is phenyl, such as unsubstituted phenyl.
  • R 3 is phenyl substituted with -L— D.
  • R 4 is H.
  • R 4 is F.
  • R 4 is phenyl, such as unsubstituted phenyl. In some embodiments, R 4 is phenyl substituted with -L— D. In some embodiments, R 3 and R 4 are H. In some embodiments, R 3 and R 4 are F. In some embodiments, R 3 and R 4 are phenyl, such as unsubstituted phenyl. In some embodiments, R 3 and R 4 are phenyl substituted with -L— D.
  • X is a bridging group connecting the phenylaryl ring with a pyrrole ring, such as alkyl, including a -C x H 2x -, wherein x is 1, 2, 3, 4, etc., e.g.
  • X is -CH 2 CH 2 -.
  • X is -CH 2 CH 2 CH 2 -. In some embodiments, where X is a spiro-cycloalkane group the spiro-cycloalkane group may comprise a spiro-cyclopentane.
  • the BODIPY moeity, or A may be:
  • the photoluminescent complex comprises a linker complex, or L, wherein the linker complex covalently links the blue light absorbing moiety (A) to the BODIPY emitting moiety (D).
  • the linker complex may comprise a single bond between the blue light absorbing moiety and the BODIPY moiety.
  • the linker complex may comprise a substituted or unsubstituted ester group.
  • the photoluminescent complex emits red light.
  • L is a linker complex comprising an optionally substituted C 2- C 7 ester It is believed that the ester linker groups help with increasing distance between the perylene blue light absorbing moiety and the BODIPY moiety creating a through space energy transfer (FRET), ratherthan a trough bond energy transfer, resulting in a quantum yield of greater than 70% for the photoluminescent complex.
  • 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%; and may be up to or approach 100%.
  • the emission quantum yield may be greater than 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%; and may be up to or approach 100%. In some embodiments, the emission quantum yield may be greater than 80% and may be up to 100%. Emission quantum yield may be measured by dividing the number of photons emitted by the number of photons absorbed, which is equivalent to the emission efficiency of the luminescent moiety. In some embodiments, the absorbing luminescent moiety, may have an emission quantum yield greater than 75% and may be up to 100%. In some embodiments, the quantum yield may be greater than 0.75 (75%), 0.76 (76%), 0.77 (77%), 0.78 (78%), 0.79 (79%), 0.8 (80%), 0.81 (81%), 0.82 (82%), 0.83 (83%), 0.84 (84%),
  • the photoluminescent complex has an emission band, the emission band may have a full width half maximum (FWHM) of less than 40 nm.
  • the FWHM is the width of the emission band in nanometers at the emission intensity that is half of the maximum emission intensity for the band.
  • the photoluminescent complex has an emission band FWHM value that is less than or equal to about 35 nm, less than or equal to about 30 nm, less than or equal about 25 nm, 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 and up to 100 nm, up to 200 nm, or up to 300 nm.
  • Stokes shift means the distance between the excitation peak of the donor chromophore and the emission peak of the acceptor chromophore.
  • the photoluminescent complex of the current disclosure may have a tunable emission wavelength.
  • the emission wavelength may be tuned between 575 nm to about 650 nm or any number bound by this range.
  • the donor chromophore may have a peak absorption maximum between about 400 nm to about 480 nm wavelength.
  • the peak absorption may be between about 400 nm to about 405 nm, about 405 nm to about 410 nm, about 410 nm to about 415 nm, about 415 nm to about 420 nm, about 420 nm to about 425 nm, about 425 nm to about 430 nm, about 430 nm to about 435 nm, about 435 nm, to about 440 nm, about 440 nm to about 445 nm, about 445 nm, to about 450 nm, about 450 nm to about 455 nm, about 455 nm to about 460 nm, about 460 nm to about 465 nm, about 465 nm to about 470 nm, about 470 nm to about 480
  • the photoluminescent complex may have an emission peak between about 575 nm to about 650 nm wavelength.
  • the emission peak may be between 575 nm to about 580 nm, about 580 nm to about 585 nm, about 585 nm to about 590 nm, about 590 nm to about 595 nm, about 595 nm to about 600 nm, about 600 nm to about 605 nm, about 605 nm to about 610 nm, about 610 nm to about 615 nm, about 615 nm to about 620 nm, about 620 nm to about 625 nm, about 625 nm to about 630 nm, about 630 nm to about 635 nm, about 635 nm to about 640 nm, about 640 nm to about 645 nm, about 645 nm to about 650 nm, or any range b
  • the photoluminescent complex wherein the donor chromophore and the acceptor chromophore's spatial distance is optimized through the linker complex, for transfer of the blue light absorbing moiety's emitted energy to the BODIPY derivative luminescent moiety.
  • the blue light absorbing moiety may be a perylene derivative of the formula I: With respect to the perylene derivative of formula II, the perylene may comprise a perylene wherein R 8 , R 10 and R 11 may be selected from a hydrogen (H) or a trifluoromethyl (CF 3 ). In some embodiments, R 9 is H.
  • Photo-stability (or durability) of organic compounds and complexes is a very common issue. Photo-stability of organic photoluminescent complexes is mostly due to the photo- oxidation process. It is believed that the addition of electron-withdrawing groups, otherwise called electron-accepting groups, to the reactive sites on the perylene structure, the electron- accepting groups draw electrons by an induction effect or resonance effect from the atomic groups on the photoluminescent complex resulting in a lower HOMO/LUMO energy level which is unfavorable for the photo-oxidation of the photoluminescent complex.
  • electron-withdrawing groups otherwise called electron-accepting groups
  • the electron-accepting may comprise cyano groups (-CN), fluorine containing alkyl groups, such as, trifluoromethyl groups (-CF 3 ), or a fluorine containing aryl group, such as a 4- (trifluoromethyl)benzene group, because such groups are less likely to be chemically decomposed.
  • cyano groups -CN
  • fluorine containing alkyl groups such as, trifluoromethyl groups (-CF 3 )
  • a fluorine containing aryl group such as a 4- (trifluoromethyl)benzene group
  • the perylene derivative may be linked to a second boron- dipyrromethene (BODIPY) derivative acceptor luminescent moiety.
  • BODIPY boron- dipyrromethene
  • a linker complex and the second absorbing luminescent complex may be covalently bonded to formula I.
  • the ratio between the blue light absorbing moiety and the BODIPY moiety may be 1:1. In some embodiments, the ratio between the blue light absorbing moiety and the BODIPY moiety may be 2:1. In some embodiments, the ratio between the blue light absorbing moiety and the BODIPY moiety may be 3:1.
  • the photoluminescent complex comprises a structure shown below.
  • Some embodiments include a color conversion film comprising a transparent substrate layer, and a color conversion layer, wherein the color conversion layer includes a resin matrix and at least one photoluminescent complex, wherein the at least one photoluminescent complex comprises the photoluminescent complex described herein above dispersed within the resin matrix.
  • the color conversion film may be described as comprising one or more of the photoluminescent complexes described herein.
  • the color conversion film may comprise a photoluminescent complex with an absorbance in the 400 nm to 480 nm light wavelength and an emission in the 510 nm to 560 nm light wavelength.
  • the color conversion film may comprise a photoluminescent complex with an absorbance in the 400 nm to 480 nm light wavelength and an emission in the 575 nm to 650 nm light wavelength.
  • the color conversion film may 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 (polymethylacrylate), PMMA (Polymethylmethacrylate), CAB (cellulose acetate butyrate), PVC (polyvinylchloride), PET (polyethyleneterephthalate), PETG (glycol modified polyethylene terephthalate), PDMS (polydimethylsilozane), COC (cyclo olefin copolymer), PGA (polyglycolide or polyglycolic acid), PLA (polylactic acid), PCL (polycaprolactone), PEA (polyethylene adipate), PHA (polyhedroxy alkanoate), PHBV (poly(3-hydroxybutyrate-co-3hydroxyvalerate)), PBE (polybutylene terephthalate), and PTT (polytrimethylene terephthalate). Any of the following transparent substrates include
  • the transparent substrate may have two opposing surfaces.
  • the color conversion film may be disposed on and in physical contact 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 color conversion film, wherein the film comprises a color conversion layer.
  • the color conversion layer may comprise a resin matrix, and a photoluminescent complex (such as those described herein), dissolved with a solvent.
  • the resin matrix forms a continuous phase and may comprise materials possessing exceptional mold processability, heat resistance and transparency.
  • the resin matrix material may comprise a polymer.
  • polymers used for color conversion films include, but are not limited to poly(meth)acrylic based materials, such as for example, polymethyl methacrylate (PMMA), polycarbonate (PC) based materials, Polystyrene (PS) based materials, polyarylene (PAR) based materials, polyurethane based materials, styrene-acryonitrile (SAN) based materials, and polyvinylidene fluoride (PVDF) based materials to name a few.
  • PMMA polymethyl methacrylate
  • PC polycarbonate
  • PS Polystyrene
  • PAR polyarylene
  • PVDF polyvinylidene fluoride
  • 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 monomethyl ether,
  • the color conversion film may further comprise a second photoluminescent complex, wherein the second complex was an absorbance within the 400 nm to 470 nm light wavelength and an emission within the 510 nm to 560 nm light wavelength.
  • the color conversion film may further comprise a photoluminescent complex with an absorbance in the 400 nm to 480 nm light wavelength and an emission in the 575 nm to 650 nm light wavelength.
  • the color conversion film further comprises additives.
  • Additives may be used for preventing deterioration of the photoluminescent complex and enhancing the durability, i.e., suppression of reduction of the light emission intensity over time.
  • LA-57 is an effective additive.
  • the color conversion film further comprises a singlet oxygen quencher.
  • the singlet oxygen quencher is a material that traps and inactivates singlet oxygen resulting from the activation of oxygen molecules due to light energy. Co-presence of a singlet oxygen quencher in the composition makes it possible to prevent singlet oxygen from deteriorating the photoluminescent complex.
  • Singlet oxygen is known to result from the occurrence of electron and energy exchange between the perylene or the BODIPY structure and an oxygen molecule in a ground state.
  • the photoluminescent complex is excited by an excitation light and emits light with a wavelength different from the excitation light, whereby converting light of one wavelength to a second higher wavelength.
  • the probability of the generation of oxygen singlets due to the interactions between the resulting excited species and the oxygen molecules present in the composition, increases.
  • the probability of the photoluminescent complexes colliding with the singlet oxygen species increases, resulting in the deterioration of photoluminescent complexes.
  • singlet oxygen quenchers include nickel additives, such as, nickel chloride, nickel (II) bis(acetylacetonate) (Ni(acac)2, Millipore Sigma, Burlington, MA USA), nickel carbonate, etc.
  • the color conversion film may further comprise a radical scavenger.
  • the radical scavenger may comprise 1,4- diazabicyclo[2.22.]octane (DABCO, Millipore Sigma, Burlington, MA USA).
  • the additives may comprise a hindered light stabilizer.
  • Hindered light stabilizers may comprise tertiary amines.
  • tertiary amine include tetrakis(2,2,6,6-tetra-methyl-4-piperidyl)l,2,3,4,-butanetetracarboxylate (STAB LA-57, Adeka Corporation, Arakawa, Tokyo, Japan), l,2,2,6,6-pentamethyl-4-piperidyl methacrylate (STAB LA-81, Adeka), 2,2,6,6-tetramethyl-4-piperidyl methacrylate (STAB LA-87, Adeka), trimethylamine, N,N-diethylaniline, 1,2,2,6,6-pentamethylpiperidine, bis(l, 2,2,6, 6-pentamethyl- 4-piperidyl)sebacate, etc.
  • the color conversion film may be about 1 pm to about 200 pm thick.
  • the color conversion film has a thickness that is about 1 pm to about 5 pm, about 5 pm to about 10 pm, about 10 pm to about 15 pm, about 15 pm to about 20 pm, about 20 pm to about 40 pm, about 40 pm to about 80 pm, about 80 pm to about 120 pm, about 120 pm to about 160 pm, about 160 pm to about 200 pm, about 10 pm, or any thickness bounded by the ranges above.
  • the color conversion film may absorb light in the 400 nm to about 480 nm wavelength range and may emit light in the range of about 575 nm to about 650 nm. In some embodiments, the color conversion film may absorb light in the 400 nm to 480 nm wavelength range and may emit light in the range of 510 nm to about 560 nm. In still other embodiments, the color conversion film may absorb light in the 400 nm to about 480 nm range and may emit light in two higher wavelengths, the 510 nm to about 560 nm wavelength range and the 575 nm to about 650 nm wavelength range or any combinations thereof.
  • Some embodiments include a method for preparing the color conversion film, the method comprises: dissolving a resin matrix, and at least one photoluminescent complex, wherein the at least one photoluminescent complex is described herein above, within a solvent; and applying the mixture on to the surface of the transparent substrate.
  • the method for preparing the color conversion film further comprises dissolving a second photoluminescent complex with an excitation wavelength of 400 nm to about 480 nm and an emission wavelength of 510 nm to about 560 nm.
  • the second photoluminescent complex has an excitation wavelength of 400 nm to about 480 nm and an emission wavelength of 575 nm to about 560 nm
  • the method further comprises dissolving a radical scavenger within the solvent.
  • the radical scavenger may be l,4-diazabicyclo[2.22.]octane (DABCO, Millipore Sigma).
  • the method further comprises dissolving a singlet oxygen quencher within the solvent.
  • Some embodiments include a back-light unit; the back-light unit may include the aforedescribed color conversion film.
  • Some embodiments include color conversion films with high photo stability.
  • the absorption at peak absorption wavelength is measured before and after the color conversion film is exposed to LED light for 165 h, 330 h and 500 h respectively, as measured by UV-vis 3600 (Shimadzu), and the absorption remaining (measured after each exposure time period) divided by absorption before exposure indicates the photo stability of the color conversion film.
  • the photo stability is at least 80%, at least 82%, at least 85%, at least 90%, or at least 93%, and may approach 100% after 165 hours of exposure.
  • the photo stability is at least 75%, at least 77%, at least 80%, at least 85%, at least 90%, or at least 91%, and may approach 100%, after 330 hours of exposure.
  • 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 exemplary, and many other architectures may be implemented which achieve the same or similar functionality.
  • Embodiment 1 A photoluminescent complex comprising: a donor chromophore, wherein the donor chromophore absorbs light in the blue light wavelength and emits an excitation energy in response thereto, wherein the donor chromophore comprises a perylene derivative of the following formula; wherein R 8 , R 10 and R 11 are selected from a H, or a CF 3 , and wherein R 9 is H; an acceptor chromophore, comprising a boron-dipyrromethene (BODIPY) derivative wherein the acceptor chromophore absorbs the excitation energy emitted by the donor chromophore wherein the acceptor chromophore then emits a second wavelength of light which is a higher wavelength of light than the blue light wavelength; and a linker complex for linking the donor chromophore and the acceptor chromophore; and wherein the photoluniminescent complex has an emission quantum yield greater than 80%.
  • R" is -H, or a bond connecting to L— D;
  • R 1 and R 2 is independently selected from a H or a methyl (-CH 3 );
  • R 3 and R 4 are independently H, F, Br, or -CF 3 , phenyl optionally substituted with 1 or 2 -CH 3 , -F, - CF 3 , or -L— D groups;
  • Ar is an aryl or a heteroaryl group
  • L is a linker complex comprising an optionally substituted C 4 -C 7 ester or a C 3 -C 5 keto ester; and D is a donor chromophore.
  • Embodiment 3 The photoluminescent complex of embodiment 1, wherein when X forms the spiro-cycloalkane group is a spiro-cyclopentane.
  • Embodiment 4 The photoluminescent complex of embodiment 1, wherein when X forms the spiro-polycyclic group the spiro-polycyclic group is a spiro-fluorene.
  • Embodiment 5 The photoluminescent complex of embodiments 1, 2, 3, and 4, wherein the C4-C7 ester linkers are of the general formulas: Embodiment 6.
  • Embodiment 7 The photoluminescent complex of embodiments 1, 2, 3, 4, 5 and 6, wherein the photoluminescent complex is selected from one of the following structures:
  • a color conversion film comprising: a transparent substrate layer; a color conversion layer, wherein the color conversion layer includes a resin matrix, and at least one photoluminescent complex, wherein the at least one photoluminescent compound is comprised the photoluminescent compound of embodiments, 1, 2, 3, 4, 5, 6, and 7, dispersed within the resin matrix.
  • Embodiment 9 The color conversion film of embodiment 8, further comprising a singlet oxygen quencher.
  • Embodiment 10 The color conversion film of embodiment 8, further comprising a radical scavenger.
  • Embodiment 11 The color conversion film of embodiment 8, wherein the film has a thickness of between 10 pm to about 200 pm.
  • Embodiment 12 The color conversion film of embodiment 8, wherein the film absorbs blue light in the 400 nm to 480 nm wavelength range and emits a red light in the 575 nm to 645 nm wavelength.
  • Embodiment 13 The color conversion film of embodiment 8, further comprising a photoluminescent complex with an absorbance in the 400 nm to 480 nm light wavelength and an emission in the 510 nm to 560 nm light wavelength.
  • Embodiment 14 A method for preparing the color conversion film of embodiment 8, 9, 10, 11, 12, and 13, the method comprising: dissolving a resin matrix, and at least one photoluminescent complex, wherein the at least one photoluminescent complex is described in embodiments 1, 2, 3, 4, 5, 6, and 7, within a solvent; and applying the mixture on to the surface of the transparent substrate.
  • Embodiment 15 The method of embodiment 14, further comprising dissolving a photoluminescent complex with an absorbance in the range of 400 nm to 480 nm and an emission in the 510 nm to 560 nm wavelength range.
  • Embodiment 16 The method of embodiment 14, further comprising dissolving a radical scavenger within the solvent.
  • Embodiment 17 The method of embodiment 14, further comprising dissolving a singlet oxygen quencher within the solvent.
  • Embodiment 18 A backlight unit including the color conversion film of embodiment 8.
  • Embodiment 19 A display device including the backlight unit of embodiment 18. EXAMPLES
  • CE-1 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. The next day the solution was filtered and then washed with dichloromethane resulting in a dipyrrolemethane. Next, 1.0 g of dipyrrolemethane was dissolved in 60 mL of TNF.
  • Example 1.2 Comparative Example 2 was synthesis as described in Wakamiya, Atsushi et al. Chemistry Letters, 37(10), 1094-1095; 2008
  • the flask was stoppered and stirred at room temperature for 1 minute, then heated to 110 °C in a heat block for 1 hour. More KOH (85% purity, 300 mmol, 16.833 g) was added to the flask and the temperature of the heat block was raised to 140 °C. Anhydrous dichloroethane (200 mmol, 15.8 mL) was diluted to a total volume of 40 mL with anhydrous DMSO. This solution was transferred to a 50 mL syringe and added to the reaction mixture over a period of 30 minutes with very vigorous stirring at 140 °C.
  • a finned condenser was added to the reaction flask and the reaction was heated and stirred in a heat block for 24 hours at 50 °C.
  • the reaction was cooled to 0 °C in an ice-water bath and p-chloranil (2.61 mmol, 641 mg) was added with stirring.
  • the reaction was stirred at 0 °C for 20 minutes, at which point the oxidation was complete.
  • To the reaction was added BF 3 .0Et 2 (58.4 mmol, 7.2 mL) and triethylamine (34.9 mmol, 4.9 mL) and the mixture stirred at 0 °C for 30 minutes, then the ice- water bath was removed and the reaction stirred at room temperature for three days.
  • the reaction was then heated to 60 °C in a heat block for 6 hours.
  • the reaction mixture was evaporated to dryness and purified by flash chromatography on silica gel (100% hexanes (1 CV) 10% EtOAc/hexanes (0 CV) ® ⁇ 50% EtOAc/hexanes (8 CV) ® ⁇ 60% EtOAc/hexanes (0 CV) ® ⁇ 60% EtOAc/hexanes (2 CV)).
  • Most of the product elutes pure and some co-elutes with an impurity.
  • RLE-3 was synthesized in a manner similar to RLE-2 using Compound 3.2 (0.100 mmol, 67 mg) and 4-(perylen-3-yl)butanoic acid (0.150 mmol, 51 mg) at room temperature overnight.
  • the compound was purified by flash chromatography on silica gel (100% DCM (1 CV) 10%
  • Step-1 To a solution of t-butyl 3-oxobutanoate (10 mL) in 20 mL HOAc with ice batch cooling, NaN02 (4.5 g) was added slowly while keeping the temperature of reaction mixture between 5- 10 °C. After addition, the whole was stirred at room temperature for one hour, then an additional
  • Step-2 1-tetralone (8.8 g) was dissolved in 100 mL HOAc with 10 g NaOAc, and the mixture was heated at 100 °C. To the mixture, the oxime solution from step-1 was added dropwise with simultaneously addition of Zinc dust slowly. After addition of both oxime and zinc, the whole was heated at 110 °C for one hours, then cooled to 70 °C and poured into ice-water (1.8 L). The mixture was allowed to stand overnight, then the solid was collected by filtration, which was purified by flash chromatography (silica gel) using eluents of dichloromethane/hexanes (0% 40%).
  • dichloroethane was added to dissolve the resulting product.
  • chloranile 65 mg
  • BF 3 -ether 0.5 mL
  • trimethylamine 0.5 mL
  • the organic phase was collected, dried over MgSCU, loaded on silica gel and purified by flash chromatography using eluents of dichloromethane/hexanes (0% 80%).
  • RLE-4 To a mixture of compound 4.2 (6 mg, 0.012 mmol), 4-(perylen-3-yl)butanoic acid (6 mg, 0.015 mmol), DMAP/p-TsOH salt (6 mg, 0.02 mmol) in dichloromethane (3 mL), was added to a solution of DIC (10 mg) in lmL dichloromethane. The mixture was stirred overnight at room temperature, then loaded on silica gel and purified by flash chromatography using eluents of dichloromethane/hexanes (0% 50%). The desired red emitter fraction was collected, after removal of solvents, the desired product was obtained as a dark green solid (3 mg, 33% yield).
  • reaction mixture was stirred under argon in a heating block at 110 °C overnight. The next morning, added more potassium carbonate (4.86 mmol, 672 mg) and Pd(PPh 3 ) 4 (0.0711 mmol, 82 mg) and heating continued at 110 °C for another 24 hours.
  • the reaction mixture was cooled to room temperature, diluted with water (100 mL) and extracted with ether (3 X 50 mL). The combined organic layers were washed with water (3 X 25 mL), brine (25 mL), dried over MgSCU, filtered and evaporated to dryness. Purified by flash chromatography on silica gel (10% DCM/hexanes (1 CV) 50% DCM/hexanes (10 CV).
  • reaction mixture was cooled to 0 °C with an ice-water bath and p-chloranil (0.655 mmol, 161 mg) was added with stirring.
  • the reaction was stirred at 0 °C for 20 minutes, at which point the oxidation was complete.
  • BF 3 .0Et 2 14.67 mmol, 1.8 mL
  • triethylamine 8.78 mmol, 1.2 mL
  • RLE-5 (4-(6 , ,6'-difluoro-6 , H-5 , l4,6 , l4-dispiro[cyclopentane-l,12 , -indeno[2 , ,l , :4,5]pyrrolo[l,2- c]indeno[2',l , :4,5]pyrrolo[2,l-f][l,3,2]diazaborinine-16 , ,l"-cyclopentan]-14 , -yl)-3,5- dimethylphenyl 4-(perylen-3-yl)butanoate): A 40 mL screw cap vial was charged with a stir bar, Compound 2.5 (0.100 mmol, 60 mg), 4-(perylen-3-yl)butanoic acid (0.150 mmol, 51 mg), and DMAP:pTsOH 1:1 salt (0.200 mmol, 59 mg).
  • Compound 6.2 A mixture of compound 8 (0.22 g, 1.2 mmol), 4-hydroxyl-2,5- dimethylbenzaldehyde (0.09ng, 0.6 mmol) in dichloroethane with one drop of TFA was degassed for 30 min, then heated at 40 °C overnight. After cooled to room temperature, with ice-water batch cooling, chloranil (0.2 g) was added, and the mixture was stirred for 20 min. Then BF 3 -ether (0.8 mL) and trimethylamine (0.5 mL) were added. The mixture was heated at 50 °C for two hours, then loaded on silica gel and purified by flash chromatography using eluents of dichloromethane/hexanes (10% 90%).
  • Step 2 To the solution prepared above, was added a solution of 1-benzosuberone (3.2g) in 25 mL acetic acid, followed by addition of zinc dust (11.25 g) portion wise. The resulting mixture was stirred at 75 °C for one hour, then the mixture was cooled to r.t., then added 10 mL water, and stand for one hour. The solid was filtered off, and the filtrate was poured into 100 mL water and stand overnight. The resulting solid was collected by filtration, and redissolved in dichloromethane and loaded on silica gel to be purified by flash chromatography using eluents of dichloromethane/hexanes (0% 90%). The desired product was collected as 2nd faction.
  • RLE-7 A mixture of compound 7.2 (5 mg, 0.01 mmol), 4-(perylen-3-yl)butanoic acid (5 mg, 0.015 mmol), DMAP/p-TsOH salt (6 mg, 0.02 mmol), and DIC (10 mg) in 2 mL dichloromethane was stirred at room temperature overnight, then loaded on silica gel and purified by flash chromatography using eluents of dichloromethane/hexanes (0% 35%). The orange-red fraction was collected, and removal of solvents gave a solid (3mg, in 35% yield).
  • Step 1 In 1 L two neck flash equipped with magnetic stirring bar, powder dispenser funnel, a yellow suspension mixture of perylene (5.22 g, 20.68 mmol) in DCM anhydrous (500 mL) was stirred and bubbled with Argon 15 minutes on a cooling ice + water bath; methyl 4- ⁇ 4,12b- dihydroperyien-3-yl) butanoate (3.425 g, 22.75 mmol) was added slowly via syringe and needle. Cooling bath was removed to allow the mixture stirring at RT for 15 minutes. The mixture was cooled again with ice+ water bath; AICI3 (3.3 g, 24.74 mmol) was added in small portion via the powder dispenser funnel.
  • the resulting dark purple color mixture was stirred at RT for 16 hours under the protection of Argon. TIC and LCMS shown starting materials were almost consumed.
  • the reaction mixture was diluted with 500 ml DCM then poured to ice+ water 150 ml water, organic layer was separated, dried with MgSO 4 , concentrated, to the volume of 100 ml; SiO ? (100 g) was added to THE solution mixture to absorb the product then load on to column (330 g), eluting withl Hexanes/ DCM (100:0) (0:100) gained 1.25 g of desired product.
  • Step 2 In a 250 mL RB, a yellow mixture of the product of above step (4.24 g, 11.58 mmol) in DCM anhydrous (100 mL) was stirred and bubbled with Argon 15 minutes on a cooling ice+ water bath; TFA (25 ml) was added slowly. Cooling bath was removed to allow the mixture stirring at room temperature for 15 minutes.; triethyl silane (15 mL) was added in at once. The resulting dark color mixture was stirred at room temperature for 16 hours under the protection of Argon. TLC and LCMS shown starting materials were consumed. The reaction mixture was diluted with 200 ml DCM then put on rotavapor. TFA and DCM were concentrated.
  • RLE-8 ((T-4)-[2-[(4,5-dihydro-8-bromo-2H-benz[g]indol-2-ylidene- k/V)-(3,5-dimethyl-4-(-((4- (4,9,10-tris(trifluoromethyl)perylen-3-yl)butanoyl)oxy)phenyl)methyl]-4,5-dihydro-lH- benz[g]indolato- k/V]difluoroboron): Was synthesized from Compound 6.2 (described supra) [2- [(4,5-dihydro-8-bromo-2H-benz[g]indol-2-ylidene-k/V)-(3,5-dimethyl-4-hydroxyphenyl)methyl]- 4,5-dihydro-lH-benz[g]indolato-k/V]difluoroboron (0.100 mmol, 52 mg) and ((4,9,10
  • RLE-9 ((T-4)-[2-[(4,5-Dihydro-3-methyl-2H-benz[g]indol-2-ylidene-K/V)(3,5-dimethyl-4--((4-)
  • RLE-9 was synthesized from Compound 9.3 (0.116 mmol, 63 mg) and (4,9,10-tris(trifluoromethyl)perylen-3-yl) butanoic acid (0.116 mmol, 63 mg) in a manner similar to Compound 2 (described supra).
  • Compound 11.1 (4-formyl-3,5-dimethylphenyl 4-(perylen-3-yl)butanoate): Compound 11.1 was synthesized from 4-hydroxy-2,6-dimethylbenzaldehyde (1.89 mmol, 284 mg) and 4-(perylen-3- yl)butanoic acid (0.946 mmol, 320 mg) in a manner similar to RLE-2. The crude product was purified by flash chromatography on silica gel (100% toluene, (5 CV) 10% EtOAc/toluene (10
  • Compound RLE-11 ((T-4)-[2-[(4,5-dihydro-8-fluoro-2H-benz[g]indol-2-ylidene-K/V) ( 3,5- dimethYl-4-(4-(perYlen-3-Yl)butanoate) phenyl)methyl]-4,5-dihydro-8-fluoro-1H-benz[g] indolato-K/V]difluoro-boron): Compound RLE-11 was synthesized from Compound 21.2 (200 pmol), Compound 11.1 (105 mitioI, 49.4 mg), p-chloranil (100 umol, 24.5 mg), triethylamine (600 umol, 84 uL), and BF 3 .0Et 2 in a manner similar to Compound 21.
  • the reaction flask was placed in an aluminum heat block and pre-heated to 160 ° C.
  • the solution of ethyl acetoacetate- 2-oxime was added via syringe pump over a period of 60 minutes.
  • Crude LCMS indicates product and dehydrohalogenated product as well as unreacted starting material and dehydrohalogenated starting material.
  • the crude reaction mixture was cooled to room temperature, then diluted with EtOAc (200 mL).
  • the reaction mixture was transferred to a separatory funnel and washed with water (1 X 200 mL, 1 X 100 mL), IN NaOH in water (2 X 50 mL), and brine (50 mL).
  • the organic layer was dried over MgSCU, filtered, and concentrated to an oil.
  • Triethylamine (3.41 mmol, 474 ⁇ L) was added, the mixture was stirred at r.t. for 30 min before BF 3 -OEt 2 (5.11 mmol, 631 ⁇ L) was added and the mixture was stirred at r.t. for 1 h. It was then diluted with EtOAc (50.0 mL), washed with 3 M HCI (3 x 50.0 mL), dried (MgSO 4 ) and concentrated under reduced pressure. Flash chromatography (4:1, toluene/hexanes ⁇ 9:1, toluene/hexanes) gave 105 mg of RLE-15 (18% yield) as a dark blue/purple solid.
  • Compound 15.4C (4-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)phenyl 3-(perylen-3- yl)propanoate): Compound 42.3 was synthesized from Compound 42.2 (1.67 mmol, 543 mg) and 4-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)phenol (2.51 mmol, 553 mg) A 40 mL screw cap vial was flushed with argon and charged with Compound 42.2 (1.67 mmol, 543 mg), 4-(4, 4,5,5- tetramethyl-l,3,2-dioxaborolan-2-yl)phenol (2.51 mmol, 553 mg), DMAP (0.214 mmol, 26 mg), pTsOH.H 2 O (0.193 mmol, 36 mg) and a stir bar.
  • K/V]difluoroboron (approx. 2:1 ratio) as a dark blue/purple solid which was used in the subsequent synthetic step without further purification.
  • a glass substrate was prepared in substantially the following manner. A 1.1 mm thick glass substrate measuring 1-inch X 1-inch was cut to size. The glass substrate was then washed with detergent and deionized (Dl) water, rinsed with fresh Dl water, and sonicated for about 1 hour. The glass was then soaked in isopropanol (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.
  • Dl detergent and deionized
  • I PA isopropanol
  • PMMA poly(methylmethacrylate)
  • CAS poly(methylmethacrylate) copolymer in cyclopentanone (99.9% pure)
  • the prepared copolymer was stirred overnight at 40 °C.
  • the 20% PMMA solution prepared above (4 g) was added to 3 mg of the photoluminescent complex made as described above in a sealed container and mixed for about 30 minutes.
  • the PMMA/lumiphore solution was then spin coated onto a prepared glass substrate at 1000 RPM for 20 s and then 500 RPM for 5 s.
  • the resulting wet coating had a thickness of about 10 pm.
  • the samples were covered with aluminum foil before spin coating to protect them from exposure to light. Three samples each were prepared in this manner for each for Emission/FWHM and quantum yield.
  • the spin coated samples were baked in a vacuum oven at 80 °C for 3 hours to evaporate the remaining solvent.
  • the 1-inch X 1-inch sample was inserted into a Shimadzu, UV-3600 UV-VIS- NIR spectrophotometer (Shimadzu Instruments, Inc., Columbia, MD, USA). All device operations were performed inside a nitrogen-filled glove-box.
  • the resulting absorption/emission spectrum for PC-8 is shown in FIG.l, while the resulting absorption/emission spectrum for PC-33 is shown in FIG. 2.
  • the fluorescence spectrum of a 1-inch X 1-inch film sample prepared as described above was determined using a Fluorolog spectrofluorometer (Horiba Scientific, Edison, NJ, USA) with the excitation wavelength set at the respective maximum absorbance wavelength.
  • the maximum emission and FWHM are shown in Table 1.
  • PMMA film with dye concentration 2x10 -3 M is used to evaluate photo stability of film.
  • PMMA film used for stability is same film used for all optical property measurement, which was provided before.
  • 90.0 ml of cyclopentanone were added to 30.0 g of polymethylmethacrylate (PMMA) polymer (Milipore-Sigma, St. Louis, MO, USA), and stirred for several days at 50 °C.
  • PMMA polymethylmethacrylate
  • the resulting substrate solution was cast on a pre-cleaned (washed with soap and water) glass substrate (1 inch by 1 inch by 1 inch) by a casting machine set at casting blade clearance of 200 microns.
  • the casted film was kept under cover for 30 minutes after casting for an additional 30 minutes.
  • the casted glass surface was then placed on a hot plate and baked at 120 °C for about 20 minutes.
  • Blue LED light (vendor: inspired LED) with emission peak at 465nm was used as light source.
  • Blue LED strip was place in a 1 ''x 12" size U channel, a commercial diffuser film (vendor unknown) was place on top of the U channel in order to give uniform light distribution. Film with size G'cG' was place on top of diffuser. Average irradiance at film is approximately 1.5mW/cm 2 . Setup is at ambient environment.
  • Absorption at peak absorption wavelength is measured before and after film been exposure to LED light 165h, 330h and 500h respectively.
  • Film absorption is measured by UV- vis 3600 (Shimadzu) Absorption remaining measured after each exposure time period divided by absorption before exposure indicates the photo stability of film.
  • Additive (LA-57) amount is 0.2 wt%.
  • LA-57 purchased from vendor: Adeka, Ni(AcAc)2, DABCO both purchased from sigma Aldrich
  • 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.”

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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: Shijun Zheng, Jeffrey R. Hammaker, Hiep Luu, Stanislaw Rachwal, Jan Saska, Jie Cai, and Peng Wang
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. Provisional Application No. 62/962,626, filed January 17, 2020, and U.S. Provisional Application No. 63/008,284 filed April 10, 2020, which are incorporated by reference herein in their entirety.
FIELD
The present disclosure related to compounds for use in color conversion film, and a backlight unit, and a display apparatus including the same.
BACKGROUND
In color reproduction the gamut, or color gamut, is a certain complete subset of colors available on a device such as a television or monitor. For example, Adobe™ Red Green Blue (RGB), a wide-gamut color space achieved by using pure spectral primary colors, was developed to provide a broader color gamut and offer a more realistic representation of visible colors viewed through a display. It is believed that a device which could provide a wider gamut could enable the display to portray more vibrant colors.
As high-definition large screen displays become more common, the demand for higher performance, slimmer and highly functional displays have increased. Current light emitting diode (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 lager, 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 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 into green and red light. Third, quantum dots require expensive encapsulating processes for protection against moisture and oxygen. Lastly, the cost of using quantum dots is high due to the difficulties in controlling size uniformity during the production process.
A novel approach, to address the issues presented with the use of quantum dots, involves the use of a boron-dipyrromethene (BODIPY) compounds as the emissive materials to replace the quantum dots.
SUMMARY
Photoluminescent compounds described herein may be used to improve the contrast between distinguishable colors in televisions, computer monitors, smart devices and any other devices that utilize color displays. The photoluminescent complexes of the present disclosure provide novel color converting complexes with good blue light absorbance and narrow emissions bandwidths, with the full width half maximum [FWHM] of emission band of less than 40 nm. In some embodiments, a photoluminescent complex absorbs light of a first wavelength and emits light of a second higher wavelength than the first wavelength. The photoluminescent complexes disclosed herein may be utilized with a color conversion film for use in light emitting apparatuses. The color conversion film of the present disclosure reduced color deterioration by reduced overlap within the color spectrum resulting in high quality color rendition.
Some embodiments include a photoluminescent complex comprising: a donor chromophore; an acceptor chromophore; and a linker complex. Some photoluminescent complexes are represented by Formula I:
A— (L— D)1-3 [Formula I], In some embodiments, the donor chromophore, or D, absorbs light in the blue light wavelength and emits an excitation energy. The donor chromophore may comprise a perylene derivative of the following formula:
Figure imgf000005_0001
In some embodiments, R8, R10 and R11 may be selected from a H or a -CF3. In some embodiments, R9 is H.
In some embodiments, the acceptor chromophore, or A, emits light in the red light wavelength. The acceptor chromophore may comprise a BODIPY derivative of the following formula:
Figure imgf000005_0002
In some embodiments, R' is independently H, -CH3, F, orCF3; R" is-H, ora bond connecting to L— D; R1 and R2 are independently H or -CH3; R3 and R4 are independently H, F, Br, -CF3, phenyl optionally substituted with 1 or 2 -CH3, -F, -CF3, or -L—D groups; X is -CH2-, -CH2CH2-, -CH2CH2CH2- , -C(Ra)2-, -CHC(Ra)-, -C(=0)-, -0-, -S-, -C(Ar)2- -C(CH2Ar)2-, a spiro-cycloalkane group, or an aromatic spiro-polycyclic group, wherein Ra is a C1-C4 alkyl and wherein Ar is an aryl group or a heteroaryl group; and L is an optionally substituted C4-C7 ester or a C3-C5 keto ester.
In some embodiments, the acceptor chromophore absorbs the excitation energy emitted by the donor chromophore wherein the acceptor chromophore then emits a second wavelength of light which is a higher wavelength of light than the blue light wavelength. In some embodiments, the acceptor chromophore emits light in the red light wavelength. The linker complex links the donor chromophore and the acceptor chromophore.
In some embodiments, the photoluminescent complex has an emission quantum yield greater than 80%. In some embodiments, the photoluminescent complex may have an emission band with a full width half maximum [FWHM] of up to 40 nm.
In some embodiments, the photoluminescent complex may have a Stokes shift, the difference between the excitation peak of the blue light absorbing moiety and the excitation of the BODIPY moiety, of equal to or greater than 45 nm. Some embodiments include a color conversion film, the color conversion film may comprise: a transparent substrate layer; and a color conversion layer. In some embodiments, the color conversion layer may comprise a resin matrix and at least one photoluminescent complex dispersed within the resin matrix. In some embodiments, the color conversion film may comprise a thickness between 1 pm to about 200 pm. In other embodiments, the color conversion film may comprise a singlet oxygen scavenger. In some examples, the color conversion film may comprise a radical scavenger. Another embodiment includes a color conversion film that may absorb blue light in the 400 nm to about 480 nm range and emit red light in the 575 nm to about 650 nm wavelength range. In some embodiments, the color conversion film may further comprise a transparent substrate layer. Some embodiments include a color conversion film that has a photostability of at least 80% after being exposed to blue light at a peak wavelength of 465 nm for 165 hours. Other embodiments include a color conversion film that has a photostability of at least 75% after being exposed to blue light at a peak wavelength of 465 nm for 330 hours. In some embodiments, the transparent substrate layer of the color conversion film comprises two opposing surfaces, wherein the color conversion layer is disposed on one of the opposing surfaces.
Some embodiments include a method for preparing the color conversion film, the method comprises: dissolving a resin matrix and a photoluminescent complex within a solvent; and applying the mixture on one of the transparent substrates opposing surfaces.
Some embodiments include a backlight unit including the herein aforedescribed color conversion film.
Some embodiments, describe a display device including the backlight unit described hereupon.
These and other embodiments are described in greater detail below.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a graph depicting the absorption and emission spectra of one embodiment of a photoluminescent complex. FIG. 2 is a graph depicting the absorption and emission spectra of one embodiment of a photoluminescent complex.
DETAILED DESCRIPTION
The current disclosure describes a photoluminescent complex 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 an embodiment, the photoluminescent complex may both enhance the transmission of a desired first emissive bandwidth and decrease the transmission of a second emissive bandwidth. 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. Some embodiments include a photoluminescent complex that may enhance the contrast or intensity between two colors, increasing their distinction form one another.
Use of the term "may" should be construed as shorthand for "is" or "is not" or, alternatively "does" or "does not" or "will" or "will not." For example, the statement "the alkyl group may be substituted" should be interpreted as, for example, "In some embodiments, the alkyl group is substituted. In some embodiments, the alkyl group is not substituted." In another example, the statement "the photoluminescent complex may enhance the contrast" should be interpreted as, for example, "In some embodiments, the photoluminescent complex of the present disclosure does enhance the contrast. In some embodiments, the photoluminescent complex of the present disclosure does not enhance the contrast." In another example, the statement "the color conversion film may further comprise a second photoluminescent complex" should be interpreted as, for example, "In some embodiments, the color conversion film will further comprise a second photoluminescent complex. In some embodiments, the color conversion film will not further comprise a second photoluminescent complex." As used herein, when a compound or chemical structure is referred to as being
"substituted" it includes one or more substituents. A substituted group is derived from the unsubstituted parent structure wherein one or more hydrogen atoms on the parent structure have been independently replaced by one or more substituent groups. A substituent group may have one or more substituent groups on the parent group structure. In one or more forms, the substituent groups may be independently selected from an optionally substituted alkyl or alkenyl, or a C3-C7 heteroalkyl
The term "alkyl" group as used herein refers to a hydrocarbon group with no double or triple bonds. An "alkene moiety refers to a group that has at least one carbon-carbon double bond and an "alkyne" moiety refers to a group that has at least one carbon-carbon triple bond. An alkyl, alkene, or alkyne moiety may be straight chain, branched or cyclic.
The alkyl moiety may have 1 to 6 carbon atoms (wherever it appears herein, a numerical range such as "1 to 6" refers to each integer in the given range: e.g., "1 to 6 carbon atoms" means that the alkyl group may have 1, 2, 3, 4, 5, or 6 carbon atoms, although the present definition also covers the occurrence of the term "alkyl" where no numerical range is designate. The alkyl group of the compounds designated herein may be designated as “C1-C6 alkyl" or similar designations. By way of example only, “C1-C6 alkyl" indicates that there are one to six carbon atoms in the alkyl chain, i.e., the alkyl chain is selected from among methyl, ethyl, propyl, iso- proly, n-butyl, iso-butyl, sec-butyl, and t-butyl. Thus C1-C6 alkyl includes C1-C2 alkyl, C1-C3 alkyl, C1-C4 alkyl, C1-C5 alkyl. Alkyl groups may be substituted or unsubstituted. Typical alkyl groups include, but are in no way limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, hexyl, ethenyl, propenyl, butenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.
The term "heteroalkyl" as used herein refers an alkyl group, as defined herein, in which one or more of the constituent carbon atoms have been replaced by a heteroatom. Examples of heteroalkyl groups ae an "alkoxy" which, as used herein, refers alkyl-O- (e.g., methoxy, ethoxy, etc.).
The term "heteroatom" as used herein refers to a nitrogen (N), oxygen (O), or sulphur (S).
The term "aromatic" refers to a planar ring having a delocalized p-electron system containing 4n+2 p electrons, where n is an integer. Aromatic rings may be formed from e.g. five, six, seven, eight, nine, or more than nine atoms. Aromatics may be optionally substituted. The term "aromatic" includes both carbocyclic aryl (e.g., phenyl) and heterocyclic aryl (or "heteroaryl" or heteroaromatic") group (e.g., pyridine). The term includes monocyclic or fused- ring polycyclic (i.e., rings which share adjacent pairs of carbon atoms) groups.
The term "hydrocarbon ring" refers to a monocyclic or polycyclic radial that contains only carbon and hydrogen, and may be saturated, partially saturated, or fully saturated monocyclic hydrocarbon rings include groups having from 3 to 12 carbon atoms. Illustrative examples of monocyclic groups include the following moieties:
Figure imgf000009_0001
, and the like. Illustrative examples polycyclic groups include the following moieties:
Figure imgf000010_0001
The term "aryl" as used herein means an aromatic ring wherein each of the atoms forming the ring is a carbon atom. Aryl groups may be substituted or unsubstituted. Examples of aryl groups include, but are not limited to phenyl, naphthalenyl, phenanthrenyl, naphthacenyl, fluorenyl, pyrenyl, etc.
The term "heteroaryl" refers to an aryl group that include 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. Heteroaryls may be optionally substituted. An N-containing heteroaryl moiety refers to an aryl group in which at least one of the skeletal atoms of the ring is a nitrogen atom Illustrative examples of heteroaryl groups include the following moieties: pyrrole, imidazole etc.
The term "halogen" are used herein means fluoro, chloro, bromo, and iodo. The term "bond", "bonded", "direct bond" or "single bond" as used herein means a chemical bond between two atoms, 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 -C(=0)0R, where R is selected from among alkyl, cycloalkyl, aryl, heteroaryl (bonded through a ring carbon) and heteroalicyclic (bonded through a ring carbon). Any hydroxy, or carboxyl side chain on the compounds described herein may be esterified. The procedures and specific groups to make such ester are known to those skilled in the art and may readily be found in reference sources.
As used herein the term "ether" refers to a chemical moiety that contains an oxygen atom connected to two alkyl or aryl groups with the general formula of R-O-R', where the term alkyl and aryl is as defined herein.
As used herein the term "ketone" refers to the chemical moiety that contains a carbonyl group (C=0) connected to two alkyl or aryl groups with the general formula of RC(=0)R', wherein the term alkyl and aryl is as defined herein. The term "BODIPY" or "BODIPY derivative" as used herein, refers to a chemical moiety
Figure imgf000012_0002
BODIPY may be composed or dipyrromethene complexed with a disubstituted boron atom, typically a BF2 unit. The lUPAC name for the BODIPY general core structure is 4,4-difluoro- 4-bora-3a,4a-diaza-s-indacene.
The term "perylene" or "perylene derivative": refers to a chemical moiety with the
Figure imgf000012_0001
The present disclosure includes photoluminescent complexes that absorb light energy of a first wavelength and emits light energy in a second higher wavelength. The photoluminescent complex of the present disclosure may comprise a donor chromophore, wherein the donor chromophore may absorb blue light (400 to 480 nm wavelength) and release an excitation energy in response thereto; an acceptor chromophore which may comprise boron-dipyrromethene (BODIPY) derivative that may absorb the excitation energy released from the donor chromophore, wherein the acceptor chromophore may then emit a second wavelength of light, the second wavelength of light may be higher wavelength of light than the blue light wavelength; and a linker complex which may link the donor chromophore and the acceptor chromophore together. The photoluminescent complexes describe herein may be incorporated into a color conversion film, greatly increasing the discernibility between colors in the Red Green Blue (RGB) gambit, resulting in increased contrast and higher quality color rendition. In some embodiments, the photoluminescent complex comprise a donor chromophore, an acceptor chromophore and a linker complex. The donor chromophore and the acceptor chromophore are connected, creating a spatial relationship which is accomplished with the linker complex. In some embodiments, the donor chromophore may absorb light in the blue light wavelength and then release an excitation energy. The acceptor chromophore may absorb the excitation energy, released by the donor chromophore, and then the acceptor chromophore may emit a second wavelength of light, wherein the second wavelength of light may be higher wavelength of light than blue light. In some embodiments, the acceptor chromophore emits red light. It is believed that energy transfer from the donor chromophore to the acceptor chromophore occurs through a forster resonance energy transfer (FRET).
The photoluminescent complex may be represented by Formula I: A— (L— D)I-3, meaning that there may be 1, 2, or 3 L— D groups attached to acceptor chromophore A, such as in Formulas IA, IB, and 1C shown below:
Figure imgf000013_0001
wherein A is an acceptor chromophore, L is a linker complex, and D is a donor chromophore.
I In some embodiments, the donor chromophore (D) may comprise a perylene derivative of the following formula;
Figure imgf000013_0002
In some embodiments, R8, R10 and R11 may be hydrogen (H) or trifluoromethyl (CF3). In some embodiments, R9 is H. In some embodiments, R8 is H. In some embodiments, R8 is CF3. In some embodiments, R10 is H. In some embodiments, R10 is CF3. In some embodiments, R11 is H. In some embodiments, R11 is CF3. In some embodiments, R8, R10 and R11 are H. In some embodiments, R8, R10 and R11 are CF3.
Some embodiments include a photoluminescent complex wherein the photoluminescent complex comprises a donor chromophore which absorbs light in the blue light wavelength. In some embodiments, the donor chromophore may have a maximum blue light absorbance in the range of 400 nm to about 480 nm, about 400 nm to about 410 nm, about 410 nm to about 420 nm, about 420 nm to about 430 nm, about 430 nm to about 440 nm, about 440 nm to about 450 nm, about 450 nm to about 460 nm, about 460 nm to about 470 nm, to about 470 nm to about 480 nm, or any wavelength that is bounded by these ranges. In some embodiments, the photoluminescent complex may have an absorbance maximum peak of about 450 nm. In other embodiments, the donor chromophore may have a maximum peak absorbance of about 405 nm. In still other embodiments, the donor chromophore may have an absorbance maximum peak of about 480 nm.
In some embodiments, the acceptor chromophore (A) may comprise a boron dipyrromethene (BODIPY) derivative. The BODIPY derivative may be of the general formula:
Figure imgf000014_0001
With respect to any relevant structural representation, such as Formula III, each R' is H, a methyl group (-CH3), F, or CF3. In some embodiments, one R' is H. In some embodiments, both R' are H. In some embodiments, one R' is CH3. In some embodiments, both R' are CH3.
With respect to any relevant structural representation, such as Formula III, R” is -H, or a bond connecting to L— D, wherein L is a linker and D is a donor chromophore.
With respect to any relevant structural representation, such as Formula III, R1 and R2 are independently H or a methyl (-CH3). In some embodiments, R1 is H. In some embodiments, R1 is CH3. In some embodiments, R2 is H. In some embodiments, R2 is CH3. In some embodiments, both R1 and R2are H. In some embodiments, both R1 and R2 are CH3. With respect to any relevant structural representation, such as Formula III, R3 and R4 are independently H, F, Br, or -CF3, phenyl optionally substituted with 1 or 2 -CH3, -F, -CF3, or -L— D groups, wherein L is a linker and D is a donor chromophore. In some embodiments, R3 is H. In some embodiments, R3 is F. In some embodiments, R3 is phenyl, such as unsubstituted phenyl. In some embodiments, R3 is phenyl substituted with -L— D. In some embodiments, R4 is H. In some embodiments, R4 is F. In some embodiments, R4 is phenyl, such as unsubstituted phenyl. In some embodiments, R4 is phenyl substituted with -L— D. In some embodiments, R3 and R4 are H. In some embodiments, R3 and R4 are F. In some embodiments, R3 and R4 are phenyl, such as unsubstituted phenyl. In some embodiments, R3 and R4 are phenyl substituted with -L— D.
With respect to any relevant structural representation, such as Formula III, X is a bridging group connecting the phenylaryl ring with a pyrrole ring, such as alkyl, including a -CxH2x-, wherein x is 1, 2, 3, 4, etc., e.g. -CH2-, -C2H4, -CH2CH2CH2-; -C(Ra)2-; -CH2C(Ra)2_; -C(=O)-; -O-; -S-; -C(Ar)2-; - C(CH2Ar)2-; a spiro-cycloalkane group; or an aromatic spiro-polycyclic group, wherein Ra is a Ci- C4 alkyl, and wherein Ar is an aryl or a heteroaryl group. In some embodiments, X is -CH2CH2-.
In some embodiments, X is -CH2CH2CH2-. In some embodiments,
Figure imgf000015_0001
In some embodiments, where X is a spiro-cycloalkane group the spiro-cycloalkane group may comprise a spiro-cyclopentane.
In some embodiments, the BODIPY moeity, or A, may be:
Figure imgf000016_0001
Figure imgf000017_0001
In some embodiments, the photoluminescent complex comprises a linker complex, or L, wherein the linker complex covalently links the blue light absorbing moiety (A) to the BODIPY emitting moiety (D). In some embodiments, the linker complex may comprise a single bond between the blue light absorbing moiety and the BODIPY moiety. In other embodiments, the linker complex may comprise a substituted or unsubstituted ester group. In some embodiments, the photoluminescent complex emits red light.
With respect to any relevant structural representation, such as Formula I, Formula IA, Formula IB, or Formula 1C, L is a linker complex comprising an optionally substituted C2-C7 ester
Figure imgf000017_0002
It is believed that the ester linker groups help with increasing distance between the perylene blue light absorbing moiety and the BODIPY moiety creating a through space energy transfer (FRET), ratherthan a trough bond energy transfer, resulting in a quantum yield of greater than 70% for the photoluminescent complex. In an embodiment, the photoluminescent complex may have a high emission quantum yield. In some embodiments, the emission quantum yield may be greater than 50%, 60%, 70%, 80%, or 90%; and may be up to or approach 100%. In some embodiments, the emission quantum yield may be greater than 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%; and may be up to or approach 100%. In some embodiments, the emission quantum yield may be greater than 80% and may be up to 100%. Emission quantum yield may be measured by dividing the number of photons emitted by the number of photons absorbed, which is equivalent to the emission efficiency of the luminescent moiety. In some embodiments, the absorbing luminescent moiety, may have an emission quantum yield greater than 75% and may be up to 100%. In some embodiments, the quantum yield may be greater than 0.75 (75%), 0.76 (76%), 0.77 (77%), 0.78 (78%), 0.79 (79%), 0.8 (80%), 0.81 (81%), 0.82 (82%), 0.83 (83%), 0.84 (84%),
0.85 (85%), 0.86 (86%), 0.87 (87%), 0.88 (88%), 0.89 (89%), 0.9 (90%), 0.91 (91%), 0.92 (92%), 0.93 (93%), 0.94 (94%), and /or 0.95 (95%); and may be up to or approach 1 (100%). Quantum yield measurements in film may be made by spectrophotometer, e.g., Quantaurus-QY spectrophotometer (Humamatsu, Inc., Campbell, CA, USA). In some embodiments, the photoluminescent complex has an emission band, the emission band may have a full width half maximum (FWHM) of less than 40 nm. The FWHM is the width of the emission band in nanometers at the emission intensity that is half of the maximum emission intensity for the band. In some embodiments, the photoluminescent complex has an emission band FWHM value that is less than or equal to about 35 nm, less than or equal to about 30 nm, less than or equal about 25 nm, 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 and up to 100 nm, up to 200 nm, or up to 300 nm. As used herein the term "Stokes shift" means the distance between the excitation peak of the donor chromophore and the emission peak of the acceptor chromophore.
The photoluminescent complex of the current disclosure may have a tunable emission wavelength. By substituting in different substituents to the BODIPY moiety, for the acceptor chromophore, the emission wavelength may be tuned between 575 nm to about 650 nm or any number bound by this range.
In some embodiments, the donor chromophore may have a peak absorption maximum between about 400 nm to about 480 nm wavelength. In some embodiment, the peak absorption may be between about 400 nm to about 405 nm, about 405 nm to about 410 nm, about 410 nm to about 415 nm, about 415 nm to about 420 nm, about 420 nm to about 425 nm, about 425 nm to about 430 nm, about 430 nm to about 435 nm, about 435 nm, to about 440 nm, about 440 nm to about 445 nm, about 445 nm, to about 450 nm, about 450 nm to about 455 nm, about 455 nm to about 460 nm, about 460 nm to about 465 nm, about 465 nm to about 470 nm, about 470 nm to about 480 nm, and any number that is bound by these ranges.
In some embodiments, the photoluminescent complex may have an emission peak between about 575 nm to about 650 nm wavelength. In some embodiments, the emission peak may be between 575 nm to about 580 nm, about 580 nm to about 585 nm, about 585 nm to about 590 nm, about 590 nm to about 595 nm, about 595 nm to about 600 nm, about 600 nm to about 605 nm, about 605 nm to about 610 nm, about 610 nm to about 615 nm, about 615 nm to about 620 nm, about 620 nm to about 625 nm, about 625 nm to about 630 nm, about 630 nm to about 635 nm, about 635 nm to about 640 nm, about 640 nm to about 645 nm, about 645 nm to about 650 nm, or any range bounded by any of these values.
Other embodiments include the photoluminescent complex wherein the donor chromophore and the acceptor chromophore's spatial distance is optimized through the linker complex, for transfer of the blue light absorbing moiety's emitted energy to the BODIPY derivative luminescent moiety. In some embodiments, the blue light absorbing moiety may be a perylene derivative of the formula I:
Figure imgf000020_0001
With respect to the perylene derivative of formula II, the perylene may comprise a perylene wherein R8, R10 and R11 may be selected from a hydrogen (H) or a trifluoromethyl (CF3). In some embodiments, R9 is H.
Photo-stability (or durability) of organic compounds and complexes is a very common issue. Photo-stability of organic photoluminescent complexes is mostly due to the photo- oxidation process. It is believed that the addition of electron-withdrawing groups, otherwise called electron-accepting groups, to the reactive sites on the perylene structure, the electron- accepting groups draw electrons by an induction effect or resonance effect from the atomic groups on the photoluminescent complex resulting in a lower HOMO/LUMO energy level which is unfavorable for the photo-oxidation of the photoluminescent complex. The electron-accepting may comprise cyano groups (-CN), fluorine containing alkyl groups, such as, trifluoromethyl groups (-CF3), or a fluorine containing aryl group, such as a 4- (trifluoromethyl)benzene group, because such groups are less likely to be chemically decomposed.
In some embodiments, the perylene derivative may be linked to a second boron- dipyrromethene (BODIPY) derivative acceptor luminescent moiety. In some embodiments, a linker complex and the second absorbing luminescent complex may be covalently bonded to formula I.
In some embodiments, the ratio between the blue light absorbing moiety and the BODIPY moiety may be 1:1. In some embodiments, the ratio between the blue light absorbing moiety and the BODIPY moiety may be 2:1. In some embodiments, the ratio between the blue light absorbing moiety and the BODIPY moiety may be 3:1.
In some embodiments, the photoluminescent complex comprises a structure shown below.
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000023_0001
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000026_0001
Some embodiments include a color conversion film comprising a transparent substrate layer, and a color conversion layer, wherein the color conversion layer includes a resin matrix and at least one photoluminescent complex, wherein the at least one photoluminescent complex comprises the photoluminescent complex described herein above dispersed within the resin matrix. In some embodiments, the color conversion film may be described as comprising one or more of the photoluminescent complexes described herein. In some embodiments, the color conversion film may comprise a photoluminescent complex with an absorbance in the 400 nm to 480 nm light wavelength and an emission in the 510 nm to 560 nm light wavelength. In some embodiments, the color conversion film may comprise a photoluminescent complex with an absorbance in the 400 nm to 480 nm light wavelength and an emission in the 575 nm to 650 nm light wavelength.
In some embodiments, the color conversion film may 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 (polymethylacrylate), PMMA (Polymethylmethacrylate), CAB (cellulose acetate butyrate), PVC (polyvinylchloride), PET (polyethyleneterephthalate), PETG (glycol modified polyethylene terephthalate), PDMS (polydimethylsilozane), COC (cyclo olefin copolymer), PGA (polyglycolide or polyglycolic acid), PLA (polylactic acid), PCL (polycaprolactone), PEA (polyethylene adipate), PHA (polyhedroxy alkanoate), PHBV (poly(3-hydroxybutyrate-co-3hydroxyvalerate)), PBE (polybutylene terephthalate), and PTT (polytrimethylene terephthalate). Any of the aforedescribed resins may be corresponding/respective monomers and/or polymers.
In some embodiments, the transparent substrate may have two opposing surfaces. In some embodiments, the color conversion film may be disposed on and in physical contact one of the opposing surfaces. In some embodiments, the side of the transparent substrates without color conversion film disposed thereon may be adjacent to a light source. The substrate may function as a support during the preparation of the color conversion film. The type of substrates used are not particularly limited, and the material and/or thickness is not limited, as long as it is transparent and capable of functioning as a support. A person skilled in the art could determine which material and thickness to use as a supporting substrate. Some embodiments include a color conversion film, wherein the film comprises a color conversion layer. The color conversion layer may comprise a resin matrix, and a photoluminescent complex (such as those described herein), dissolved with a solvent.
The resin matrix forms a continuous phase and may comprise materials possessing exceptional mold processability, heat resistance and transparency. The resin matrix material may comprise a polymer. Some non-limiting examples of polymers used for color conversion films include, but are not limited to poly(meth)acrylic based materials, such as for example, polymethyl methacrylate (PMMA), polycarbonate (PC) based materials, Polystyrene (PS) based materials, polyarylene (PAR) based materials, polyurethane based materials, styrene-acryonitrile (SAN) based materials, and polyvinylidene fluoride (PVDF) based materials to name a few. The resin matrix is not limiting and one skilled in the art would be able to choose which polymer material would work for their application.
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. In some embodiments, the color conversion film may further comprise a second photoluminescent complex, wherein the second complex was an absorbance within the 400 nm to 470 nm light wavelength and an emission within the 510 nm to 560 nm light wavelength. In some embodiments, the color conversion film may further comprise a photoluminescent complex with an absorbance in the 400 nm to 480 nm light wavelength and an emission in the 575 nm to 650 nm light wavelength.
In some embodiments, the color conversion film further comprises additives. Additives may be used for preventing deterioration of the photoluminescent complex and enhancing the durability, i.e., suppression of reduction of the light emission intensity over time. In some embodiments, LA-57 is an effective additive.
In some embodiments, the color conversion film further comprises a singlet oxygen quencher. The singlet oxygen quencher is a material that traps and inactivates singlet oxygen resulting from the activation of oxygen molecules due to light energy. Co-presence of a singlet oxygen quencher in the composition makes it possible to prevent singlet oxygen from deteriorating the photoluminescent complex.
Singlet oxygen is known to result from the occurrence of electron and energy exchange between the perylene or the BODIPY structure and an oxygen molecule in a ground state. In the color conversion films of the present disclosure, the photoluminescent complex is excited by an excitation light and emits light with a wavelength different from the excitation light, whereby converting light of one wavelength to a second higher wavelength. With each cycle of excitation- light emission the probability of the generation of oxygen singlets, due to the interactions between the resulting excited species and the oxygen molecules present in the composition, increases. The probability of the photoluminescent complexes colliding with the singlet oxygen species increases, resulting in the deterioration of photoluminescent complexes. Some non- limiting examples singlet oxygen quenchers include nickel additives, such as, nickel chloride, nickel (II) bis(acetylacetonate) (Ni(acac)2, Millipore Sigma, Burlington, MA USA), nickel carbonate, etc. In some embodiments, the color conversion film may further comprise a radical scavenger. In some embodiments, the radical scavenger may comprise 1,4- diazabicyclo[2.22.]octane (DABCO, Millipore Sigma, Burlington, MA USA).
In some embodiments, the additives may comprise a hindered light stabilizer. Hindered light stabilizers may comprise tertiary amines. Some non-limiting examples of tertiary amine include tetrakis(2,2,6,6-tetra-methyl-4-piperidyl)l,2,3,4,-butanetetracarboxylate (STAB LA-57, Adeka Corporation, Arakawa, Tokyo, Japan), l,2,2,6,6-pentamethyl-4-piperidyl methacrylate (STAB LA-81, Adeka), 2,2,6,6-tetramethyl-4-piperidyl methacrylate (STAB LA-87, Adeka), trimethylamine, N,N-diethylaniline, 1,2,2,6,6-pentamethylpiperidine, bis(l, 2,2,6, 6-pentamethyl- 4-piperidyl)sebacate, etc.
The color conversion film may be about 1 pm to about 200 pm thick. In some embodiments, the color conversion film has a thickness that is about 1 pm to about 5 pm, about 5 pm to about 10 pm, about 10 pm to about 15 pm, about 15 pm to about 20 pm, about 20 pm to about 40 pm, about 40 pm to about 80 pm, about 80 pm to about 120 pm, about 120 pm to about 160 pm, about 160 pm to about 200 pm, about 10 pm, or any thickness bounded by the ranges above.
In some embodiments, the color conversion film may absorb light in the 400 nm to about 480 nm wavelength range and may emit light in the range of about 575 nm to about 650 nm. In some embodiments, the color conversion film may absorb light in the 400 nm to 480 nm wavelength range and may emit light in the range of 510 nm to about 560 nm. In still other embodiments, the color conversion film may absorb light in the 400 nm to about 480 nm range and may emit light in two higher wavelengths, the 510 nm to about 560 nm wavelength range and the 575 nm to about 650 nm wavelength range or any combinations thereof.
Some embodiments include a method for preparing the color conversion film, the method comprises: dissolving a resin matrix, and at least one photoluminescent complex, wherein the at least one photoluminescent complex is described herein above, within a solvent; and applying the mixture on to the surface of the transparent substrate. In some embodiments, the method for preparing the color conversion film further comprises dissolving a second photoluminescent complex with an excitation wavelength of 400 nm to about 480 nm and an emission wavelength of 510 nm to about 560 nm. In some embodiments, the second photoluminescent complex has an excitation wavelength of 400 nm to about 480 nm and an emission wavelength of 575 nm to about 560 nm
In some embodiments, the method further comprises dissolving a radical scavenger within the solvent. The radical scavenger may be l,4-diazabicyclo[2.22.]octane (DABCO, Millipore Sigma).
In some embodiments, the method further comprises dissolving a singlet oxygen quencher within the solvent.
Some embodiments include a back-light unit; the back-light unit may include the aforedescribed color conversion film.
Some embodiments include color conversion films with high photo stability. In some examples, the absorption at peak absorption wavelength is measured before and after the color conversion film is exposed to LED light for 165 h, 330 h and 500 h respectively, as measured by UV-vis 3600 (Shimadzu), and the absorption remaining (measured after each exposure time period) divided by absorption before exposure indicates the photo stability of the color conversion film. In some embodiments, the photo stability is at least 80%, at least 82%, at least 85%, at least 90%, or at least 93%, and may approach 100% after 165 hours of exposure. In other embodiments, the photo stability is at least 75%, at least 77%, at least 80%, at least 85%, at least 90%, or at least 91%, and may approach 100%, after 330 hours of exposure.
Other embodiments, may describe a display device, the device may include the backlight unit described hereinto.
Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions, and so forth used in the specification and embodiments are to be understood as being modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and attached embodiments are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, and not as an attempt to limit the application of the doctrine of equivalents. To the scope of the embodiments, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
For the processes and/or methods disclosed, the functions performed in the processes and methods may be implemented in differing order, as may be indicated by context. Furthermore, the outlined steps and operations are only provided as examples and some of the steps and operations may be optional, combined into fewer steps and operations, or expanded into additional steps and operations.
This disclosure may sometimes illustrate different components contained within, or connected with, different other components. Such depicted architectures are merely exemplary, and many other architectures may be implemented which achieve the same or similar functionality.
EMBODIMENTS
Embodiment 1. A photoluminescent complex comprising: a donor chromophore, wherein the donor chromophore absorbs light in the blue light wavelength and emits an excitation energy in response thereto, wherein the donor chromophore comprises a perylene derivative of the following formula;
Figure imgf000032_0001
wherein R8, R10 and R11 are selected from a H, or a CF3, and wherein R9 is H; an acceptor chromophore, comprising a boron-dipyrromethene (BODIPY) derivative wherein the acceptor chromophore absorbs the excitation energy emitted by the donor chromophore wherein the acceptor chromophore then emits a second wavelength of light which is a higher wavelength of light than the blue light wavelength; and a linker complex for linking the donor chromophore and the acceptor chromophore; and wherein the photoluniminescent complex has an emission quantum yield greater than 80%. Embodiment 2. The photoluminescent complex of embodiment 1, wherein the BODIPY derivative is of the general formula:
Figure imgf000033_0001
wherein R' is independently H, a methyl group (-CH3), a F, or CF3;
R" is -H, or a bond connecting to L— D; R1 and R2 is independently selected from a H or a methyl (-CH3);
R3 and R4 are independently H, F, Br, or -CF3, phenyl optionally substituted with 1 or 2 -CH3, -F, - CF3, or -L— D groups;
X is a bridging group connecting the phenylaryl ring with a pyrrole ring; wherein X is -CH2-, - CH2CH2-, -CH2CH2CH2-, -C(Ra)2-, -CHC(Ra)2-, -C(=0)-, -0-, -S-, -C(Ar)2- -C(CH2Ar)2-, a spiro- cycloalkane group, or an aromatic spiro-polycyclic group, wherein Ra is a C1-C4 alkyl and wherein
Ar is an aryl or a heteroaryl group;
L is a linker complex comprising an optionally substituted C4-C7 ester or a C3-C5 keto ester; and D is a donor chromophore.
Embodiment 3. The photoluminescent complex of embodiment 1, wherein when X forms the spiro-cycloalkane group is a spiro-cyclopentane.
Embodiment 4. The photoluminescent complex of embodiment 1, wherein when X forms the spiro-polycyclic group the spiro-polycyclic group is a spiro-fluorene.
Embodiment 5. The photoluminescent complex of embodiments 1, 2, 3, and 4, wherein the C4-C7 ester linkers are of the general formulas:
Figure imgf000034_0001
Embodiment 6. The photoluminescent complex of embodiments 1, 2, 3, and 4, wherein the C3-C5 keto ester linkers are of the general formulas:
Figure imgf000034_0002
Embodiment 7. The photoluminescent complex of embodiments 1, 2, 3, 4, 5 and 6, wherein the photoluminescent complex is selected from one of the following structures:
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Embodiment s. A color conversion film comprising: a transparent substrate layer; a color conversion layer, wherein the color conversion layer includes a resin matrix, and at least one photoluminescent complex, wherein the at least one photoluminescent compound is comprised the photoluminescent compound of embodiments, 1, 2, 3, 4, 5, 6, and 7, dispersed within the resin matrix.
Embodiment 9. The color conversion film of embodiment 8, further comprising a singlet oxygen quencher.
Embodiment 10. The color conversion film of embodiment 8, further comprising a radical scavenger. Embodiment 11. The color conversion film of embodiment 8, wherein the film has a thickness of between 10 pm to about 200 pm.
Embodiment 12. The color conversion film of embodiment 8, wherein the film absorbs blue light in the 400 nm to 480 nm wavelength range and emits a red light in the 575 nm to 645 nm wavelength.
Embodiment 13. The color conversion film of embodiment 8, further comprising a photoluminescent complex with an absorbance in the 400 nm to 480 nm light wavelength and an emission in the 510 nm to 560 nm light wavelength.
Embodiment 14. A method for preparing the color conversion film of embodiment 8, 9, 10, 11, 12, and 13, the method comprising: dissolving a resin matrix, and at least one photoluminescent complex, wherein the at least one photoluminescent complex is described in embodiments 1, 2, 3, 4, 5, 6, and 7, within a solvent; and applying the mixture on to the surface of the transparent substrate. Embodiment 15. The method of embodiment 14, further comprising dissolving a photoluminescent complex with an absorbance in the range of 400 nm to 480 nm and an emission in the 510 nm to 560 nm wavelength range.
Embodiment 16. The method of embodiment 14, further comprising dissolving a radical scavenger within the solvent. Embodiment 17. The method of embodiment 14, further comprising dissolving a singlet oxygen quencher within the solvent.
Embodiment 18. A backlight unit including the color conversion film of embodiment 8.
Embodiment 19. A display device including the backlight unit of embodiment 18. EXAMPLES
The following are examples of methods used to prepare and use the photoluminescent complexes described herein.
Example 1.1 Comparative example 1 (CE-1):
Figure imgf000041_0002
CE-1: 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. The next day the solution was filtered and then washed with dichloromethane resulting in a dipyrrolemethane. Next, 1.0 g of dipyrrolemethane was dissolved in 60 mL of TNF. 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.
Figure imgf000041_0001
NMR (400 MHz, Chloroform-d) d 6.64 (s, 2H), 5.97 (s, 2H), 4.73 (s, 1H), 2.56 (s, 6H), 2.09 (s, 6H), 1.43 (s, 6H).
Example 1.2 Comparative Example 2 (CE-2): was synthesis as described in Wakamiya, Atsushi et al. Chemistry Letters, 37(10), 1094-1095; 2008
Example 2. Synthesis of Photoluminescent Complex:
Example 2.1: RLE-1
Figure imgf000042_0001
Compound 1 (4,5-dihydro-lH-benzo[g]indole): A mixture of DMSO (50 mL), KOH (3.36 g) and NH20H.HCI (4.17 g) was stirred at room temperature for 30 min, then 1-tetralone (7.3 g) in DMSO (25 mL) was added. The mixture was stirred at 70 °C for additional 30 min. Then KOH (8.41 g) was added and the resulting mixture was heated to 140 °C, and a solution of 1,2-dichloroethane (9.9 g) in DMSO (25 mL) was added dropwise over 4 hours. After cooled to room temperature, the solution was poured into 200 mL saturated NH4CI solution, and the solution was extracted with ethyl acetate (200 mL x 3). The organic phase was collected and dried over Na2S04, concentrated to 10 mL, then diluted with 10 mL dichloromethane and 50 mL hexanes. The solution was submitted to flash chromatography (silica gel) using the eluents of dichloromethane/hexanes (0% 30%), and the second main fraction was collected. After removal of solvents under reduced pressure, light yellow solid was obtained as the desired product (3.5 g, in 41% yield). LCMS (APCI+): Calcd for C12H12N (M+H): 170; found 170. Compound 1.1 (4-(bis(4,5-dihydro-lH-benzo[g]indol-2-yl)methyl)-3,5-dimethylphenol): A mixture of 4,5-dihydro-lH-benzo[g]indole (0.34 g, 2 mmol), 4-hydroxyl-2,5- dimethylbenzaldehyde (0.15 g, 1 mmol) with one drop of trifluoroacetic acid in 1,2- dichloroethane (20 mL) was degassed for 10 min, then stirred at 30 °C for 20 hr. After cooled to room temperature, the mixture was filtered, and the solid was collected as desired product (0.2 g, in 43% yield). LCMS (APCI+): calculated for C33H31N2O (M+H): 471; found: 471.
Compound 1.2: To a solution of compound 1.1 (200 mg, 0.42 mmol) in 20 mL dichloromethane was added chloranil (100 mg, 0.45 mmol) at 0 °C with ice-water bath cooling. The mixture was stirred for 20 min. Then to the resulting mixture, 0.5 mL trimethylamine was added, followed by addition of 0.8 mL BF3-ether. The whole was stirred at room temperature overnight, then was loaded on silica gel and purified by flash chromatography using eluents of dichloromethane/hexanes (0% 80%). The desired red-emitting fraction was collected. After removal of solvents, a metallic dark red solid was obtained (150 mg, in 72% yield). LCMS (APCI+): calculated for C33H28BF2N2O (M+H): 517; found: 517. Compound 1.3 (5-oxo-5-(perylen-3-yl)pentanoic acid): A 3L 2 neck round bottomed flask was charged with a stir bar and flushed thoroughly with argon. AICI3 (34.7 mmol, 4.624 g) was added to the flask, followed by anhydrous dichloromethane (600 mL). The reaction mixture was cooled to 0 °C with an ice-water bath and methyl 5-chloro-5-oxopentanoate (30.4 mmol, 5.00 g) was added via syringe with stirring under argon. This mixture was stirred at 0 °C for one hour, then perylene (28.9 mmol, 7.300 g) was added with stirring. The cooling bath was removed, and the reaction mixture was stirred at room temperature for two hours. The flask was fitted with a finned air condenser and heated in a heating block set at 45 °C with stirring overnight under argon. The reaction mixture was cooled to room temperature and quenched with the addition of crushed ice (600 mL, loosely packed). To this mixture was added aqueous 6N HCI (100 mL). Stirring was continued until all ice had melted. The layers were separated, and the aqueous layer was extracted with DCM (2 X 200 mL). The combined organic layers were dried over MgSCU, filtered, and concentrated in vacuo. The crude reaction was purified by flash chromatography on silica gel (100% DCM (3 CV) -> 5% EtOAc/DCM (10 CV)). The fractions containing product were collected and concentrated in vacuo to give 3.810 g, 35% yield. MS (APCI): calculated for C26H20O3 (M + H) = 381; found: 381.
Next, a 250 mL 2 neck round bottomed flask was charged with a stir bar and flushed with argon. To this flask was added methyl 5-oxo-5-(perylen-3-yl)pentanoate (3.00 mmol, 1.141 g) and KOH (30.0 mmol, 1.683 g), followed by ethanol (200 proof, 200 mL). The flask was fitted with a finned air condenser and heated in a heat block at 95 0 C under argon with stirring for two hours. The reaction mixture was cooled to room temperature and diluted with water (to 500 mL total volume) in an Erlenmeyer flask and quenched with aqueous 6N HCI (5 mL). The resulting precipitate was collected and concentrated in vacuo to give 1.013 g (92% yield). MS (APCI): calculated for C25H18O3 (M - H) = 365; found: 365.
RLE-1: To a solution of compound 1.2 (52 mg, 0.1 mmol), perylene compound 1.3 [5-oxo-5- 9perylen-3-yl)pentanoic acid] (48 mg, 0.13 mmol), DMAP (25 mg, 0.2 mmol), p-TsOH (34 mg, 0.18 mmol) in dichloromethane (7 mL) was added a solution of DIC (63 mg, 0.5 mmol) in 1 mL dichloromethane. The whole was stirred at room temperature overnight, then submitted to purification by flash chromatography (silica gel) using eluents of dichloromethane/hexanes (0% 80%). The desired fraction was collected, after removal of solvents, a dark green solid was obtained (70 mg, in 81% yield). LCMS (APCI+): calculated for C58H44BF2N2O3 (M+H): 865; found: 865. XH NMR (400 MHz, Methylene Chloride-*) d 8.66 (d, J = 8.0 Hz, 2H), 8.50 (d, J = 8.6 Hz, 1H), 8.25 - 8.16 (m, 4H), 7.89 (d, J = 8.0 Hz, 1H), 7.69 (dd, J = 17.5, 8.1 Hz, 2H), 7.54 (dd, J = 8.6, 7.6 Hz, 1H), 7.46 (td, J = 7.8, 2.5 Hz, 2H), 7.36 (td, J = 7.6, 1.7 Hz, 2H), 7.27 - 7.18 (m, 4H), 6.86 (s, 2H), 6.27 (s, 2H), 3.17 (t, J = 7.1 Hz, 2H), 2.83 (dd, J = 8.3, 5.9 Hz, 4H), 2.70 (t, J = 7.3 Hz, 2H), 2.57 (dd, J = 8.3, 5.8 Hz, 4H), 2.20 (q, J = 7.2 Hz, 2H), 2.14 (s, 6H).
Example 2.2 RLE 2:
Figure imgf000045_0001
Figure imgf000045_0002
RLE-2: To a solution of compound 1.2 (52 mg, 0.1 mmol), 4-(perylen-3-yl)butanoic acid (44 mg, 0.13 mmol), DMAP (25 mg, 0.2 mmol), p-TsOH (34 mg, 0.18 mmol) in dichloromethane (7 mL) was added to a solution of DIC (63 mg, 0.5 mmol) in 1 mL dichloromethane. The whole was stirred at room temperature overnight, then submitted to purification by flash chromatography (silica gel) using eluents of dichloromethane/hexanes (0% 70%). The desired fraction was collected, after removal of solvents, a dark green solid was obtained (80 mg, in 95.6% yield). LCMS (APCI+): calcd for C57H44BF2N2O2 (M+H): 837; found: 837. XH NMR (400 MHz, Methylene Chloride-*) d 8.79 (d, J = 8.0 Hz, 2H), 8.34 - 8.20 (m, 4H), 8.04 (d, J = 8.4 Hz, 1H), 7.74 (dd, J = 8.2, 4.9 Hz, 2H), 7.66 - 7.45 (m, 6H), 7.40 (dd, J = 7.4, 1.2 Hz, 1H), 7.38 - 7.31 (m, 3H), 6.94 (s, 2H), 6.39 (s, 2H),
3.24 (dd, J = 8.6, 6.7 Hz, 2H), 2.96 (dd, J = 8.3, 5.9 Hz, 4H), 2.78 (t, J = 7.2 Hz, 2H), 2.70 (dd, J = 8.3, 5.9 Hz, 4H), 2.30 (dt, J = 9.1, 7.2 Hz, 2H), 2.24 (s, 6H).
Example 2.3 RLE-3:
Figure imgf000046_0001
Compound 3.1 (8-bromo-4,5-dihydro-lH-benzo[g]indole): A 250 mL 2 neck round bottom flask was fitted with a finned condenser, stir bar, and gas adapter. The flask was flushed with argon and KOH (85% purity, 60.0 mmol, 4.106 g) and NH2OH.HCI (60.0 mmol, 4.169 g) were added to the flask, immediately followed by anhydrous DMSO (5 mL). This mixture was stirred at room temperature under argon for 5 minutes, then 7-bromo-3,4-dihydronaphthalen-l(2H)-one (50.0 mmol, 11.255 g) was added. The flask was stoppered and stirred at room temperature for 1 minute, then heated to 110 °C in a heat block for 1 hour. More KOH (85% purity, 300 mmol, 16.833 g) was added to the flask and the temperature of the heat block was raised to 140 °C. Anhydrous dichloroethane (200 mmol, 15.8 mL) was diluted to a total volume of 40 mL with anhydrous DMSO. This solution was transferred to a 50 mL syringe and added to the reaction mixture over a period of 30 minutes with very vigorous stirring at 140 °C. More of the dichloroethane/DMSO solution was made and an additional 10 mL of this mixture was added via syringe pump over an additional 30 minutes. The reaction mixture was cooled to 0 °C in an ice- water bath and was quenched with saturated aqueous ammonium chloride (100 mL). This mixture was diluted with water (400 mL) and extracted with ether (250 mL) and ethyl acetate (100 mL). The 2-phase mixture was stirred vigorously at room temperature, then filtered through a pad of celite to remove solids. The aqueous layer was extracted with ether (2 X 200 mL). The combined organic layers were washed with water (5 X 50 mL), brine (50 mL), dried over MgSCU, filtered, and evaporated to dryness. The crude mixture was purified by flash chromatography on silica gel (100% hexanes (1 CV) ®· 10% DCM/hexanes (1 CV) ®· 30% DCM/hexanes (9 CV)). Repurified product fractions on silica gel (100% hexanes (1 CV) 1% EtOAc/hexanes 0 CV) 10% EtOAc/hexanes (9 CV)). Product fractions were collected and rotovaped to give 4.507 g, 36% yield. Major impurities include the N-vinyl product and two O-linked, ethylene-bridged oximes. MS (APCI): calculated for Ci2Hi0BrN (M + H) = 248; found: 248.
Compound 3.2 ((T-4)-[2-[(4,5-dihydro-8-bromo-2H-benz[g]indol-2-ylidene-K/V)-(3,5-dimethyl- 4-hydroxyphenyl)methyl]-4,5-dihydro-lH-benz[g]indolato- K/V]difluoroboron): A 250 mL 2 neck round bottomed flask was fitted with a gas adapter and a stir bar. The flask was flushed with argon and Compound 3.1 (5.21 mmol, 1.293 g) and 4-hydroxy-2,6-dimethylbenzaldehyde (2.66 mmol, 399 mg) were added to the flask, followed by anhydrous dichloroethane (50 mL). The reaction mixture was sparged with argon for 30 minutes, then TFA (0.1% v/v, 50 uL) was added via syringe. The reaction mixture was sparged with argon for an additional 15 minutes, then the reaction mixture was stirred under argon at room temperature for 1 hour. A finned condenser was added to the reaction flask and the reaction was heated and stirred in a heat block for 24 hours at 50 °C. The reaction was cooled to 0 °C in an ice-water bath and p-chloranil (2.61 mmol, 641 mg) was added with stirring. The reaction was stirred at 0 °C for 20 minutes, at which point the oxidation was complete. To the reaction was added BF3.0Et2 (58.4 mmol, 7.2 mL) and triethylamine (34.9 mmol, 4.9 mL) and the mixture stirred at 0 °C for 30 minutes, then the ice- water bath was removed and the reaction stirred at room temperature for three days. The reaction was then heated to 60 °C in a heat block for 6 hours. The reaction mixture was evaporated to dryness and purified by flash chromatography on silica gel (100% hexanes (1 CV) 10% EtOAc/hexanes (0 CV) ®· 50% EtOAc/hexanes (8 CV) ®· 60% EtOAc/hexanes (0 CV) ®· 60% EtOAc/hexanes (2 CV)). Most of the product elutes pure and some co-elutes with an impurity. The impure fractions were collected, evaporated, and repurified by flash chromatography on silica gel (100% hex (2 CV) ®· 20% EtOAc/hexanes (0 CV) ®· 50% EtOAc/hexanes (10 CV). Pure fractions from both columns were combined and evaporated to dryness to give product, 1170 mg, 67% yield. MS (APCI): calculated for C33H25BBr2F2N2O (M ) = 672; found: 672. 1H NMR (400 MHz, Chloroform-d) d 9.01 (d, J = 2.0 Hz, 2H), 7.43 (dd, J = 8.1, 2.0 Hz, 2H), 7.12 (d, J = 8.1 Hz, 2H), 6.63 (s, 2H), 6.34 (s, 2H), 2.85 (dd, J = 8.3, 5.9 Hz, 4H), 2.65 (dd, J = 8.4, 5.8 Hz, 4H), 2.17 (s, 6H).
RLE-3 ((T-4)-[2-[(4,5-dihydro-8-bromo-2H-benz[g]indol-2-ylidene- K/V)-(3,5-dimethyl-4-
(perylen-3-yl)butanoate)phenyl)methyl]-4,5-dihydro-lH-benz[g]indolato- K/V]difluoroboron):
RLE-3 was synthesized in a manner similar to RLE-2 using Compound 3.2 (0.100 mmol, 67 mg) and 4-(perylen-3-yl)butanoic acid (0.150 mmol, 51 mg) at room temperature overnight. The compound was purified by flash chromatography on silica gel (100% DCM (1 CV)
Figure imgf000048_0001
10%
EtOAc/DCM (10 CV)). The product fractions were collected and evaporated to dryness to give 95 mg, 95% yield. MS (APCI): calculated for C57H41BBr2F2N2O2 (M ) = 992; found: 992. 1H NMR (400 MHz, Chloroform-d) δ 9.01 (d, J = 1.3 Hz, 1H), 8.27 - 8.15 (m, 4H), 7.97 (d, J = 8.4 Hz, 1H), 7.68 (dd, J = 8.1, 4.7 Hz, 2H), 7.56 (t, J = 8.0 Hz, 1H), 7.48 (td, J = 7.8, 1.7 Hz, 2H), 7.46 - 7.39 (m, 3H),
7.12 (d, J = 8.1 Hz, 2H), 6.87 (s, 2H), 6.33 (s, 2H), 3.21 (t, J = 7.6 Hz, 2H), 2.85 (t, J = 7.1 Hz, 3H),
2.74 (t, J = 7.1 Hz, 2H), 2.65 (t, J = 7.1 Hz, 2H), 2.27 (p, J = 7.2 Hz, 2H), 2.19 (s, 6H).
Example 2.4 RLE-4:
Figure imgf000049_0001
Compound 4.1 (tert-Butyl 3-methyl-4,5-dihydro-lH-benzo[g]indole-2-carboxylate):
Step-1: To a solution of t-butyl 3-oxobutanoate (10 mL) in 20 mL HOAc with ice batch cooling, NaN02 (4.5 g) was added slowly while keeping the temperature of reaction mixture between 5- 10 °C. After addition, the whole was stirred at room temperature for one hour, then an additional
20 mL HOAc was added, and the resulting oxime solution was used for step 2 without further purification.
Step-2: 1-tetralone (8.8 g) was dissolved in 100 mL HOAc with 10 g NaOAc, and the mixture was heated at 100 °C. To the mixture, the oxime solution from step-1 was added dropwise with simultaneously addition of Zinc dust slowly. After addition of both oxime and zinc, the whole was heated at 110 °C for one hours, then cooled to 70 °C and poured into ice-water (1.8 L). The mixture was allowed to stand overnight, then the solid was collected by filtration, which was purified by flash chromatography (silica gel) using eluents of dichloromethane/hexanes (0% 40%). The 4th fraction is collected and removal of solvent give the desired product as white solid (0.15 g, in 1% yield). LCMS (APCI+): calcd for C18H22NO2 (M+H): 284; found: 284. Compound 4.2: To a solution of compound 4.1 (150 mg, 0.53 mmol) in dichloroethane (5 mL) was added 1 mL trifluoroacetic acid. The solution was degassed for 10 min, then stirred at room temperature for one hour. To the resulting solution, 4-hydroxylbenzaldehyde (30 mg) was added, and the solution was stirred overnight to form dipyrrole-methane. After removal of solvent under reduced pressure, 6 mL dichloroethane was added to dissolve the resulting product. To the solution, chloranile (65 mg) was added with ice-water batch cooling, and stirred for one hour. Then BF3-ether (0.5 mL) and trimethylamine (0.5 mL) was added and the mixture was stirred at room temperature overnight, then worked up with IN HCI (50 mL), and extracted with dichloromethane. The organic phase was collected, dried over MgSCU, loaded on silica gel and purified by flash chromatography using eluents of dichloromethane/hexanes (0% 80%). The desired red emitting fraction was collected, and removal of solvents to give desired product as a solid (6 mg, in 5% yield). LCMS (APCI+): calcd for C33H28BF2N2O (M+H): 517; found 517.
RLE-4: To a mixture of compound 4.2 (6 mg, 0.012 mmol), 4-(perylen-3-yl)butanoic acid (6 mg, 0.015 mmol), DMAP/p-TsOH salt (6 mg, 0.02 mmol) in dichloromethane (3 mL), was added to a solution of DIC (10 mg) in lmL dichloromethane. The mixture was stirred overnight at room temperature, then loaded on silica gel and purified by flash chromatography using eluents of dichloromethane/hexanes (0%
Figure imgf000050_0001
50%). The desired red emitter fraction was collected, after removal of solvents, the desired product was obtained as a dark green solid (3 mg, 33% yield). LCMS (APCI+): calcd for: C57H44BF2N2O2 (M+H): 836; Found: 836. 1H NMR (400 MHz, Methylene Chloride-c/2) δ 8.73 (d, J = 8.0 Hz, 2H), 8.30 - 8.16 (m, 4H), 8.00 (dd, J = 8.4, 1.0 Hz, 2H), 7.70 (dd, J = 8.1, 4.9 Hz, 2H), 7.62 - 7.37 (m, 8H), 7.37 - 7.24 (m, 6H), 3.25 - 3.17 (m, 2H), 2.89 (t, J = 7.0 Hz, 4H), 2.76 (t, J = 7.2 Hz, 2H), 2.55 (t, J = 7.1 Hz, 4H), 2.32 - 2.20 (m, 2H), 1.40 (s, 6H).
Example 2.5 RLE-5
Figure imgf000051_0001
Compound 5.1 (l-(2-bromophenyl)cyclopentan-l-ol): An oven-dried 250 mL 2 neck round bottom flask was fitted with a gas adapter and a stir bar and flushed with argon. The flask was sealed with a septum and charged with magnesium turnings (145 mmol, 3.525 g) and anhydrous THF (100 mL) via syringe. An oven-dried 100 mL 2 neck round bottom flask was fitted with a gas adapter and flushed with argon. This flask was sealed with a septum and charged with anhydrous THF (60 mL). To the 100 mL flask was added 1,5-dibromopentane (70.0 mmol, 8.30 mL). The 250 mL flask was cooled in an ice-water bath at 0 °C and the solution of 1,5-dibromopentane was added via syringe with vigorous stirring over 5 minutes. The ice-water bath was removed and replaced with a room temperature water bath and the reaction mixture stirred at room temperature. The reaction became slightly turbid as it was stirred at room temperature for 4 hours. A 1000 mL 2 neck round bottom flask was fitted with a gas adapter and a stir bar and flushed with argon. The second neck was sealed with a septum and added anhydrous THF (60 mL). To this flask was added ethyl 2-bromobenzoate (50.0 mmol, 7.94 mL) with stirring at room temperature. This flask was cooled to 0 °C in an ice-water bath and the solution of the bis- Grignard reagent was added via cannula over ~5 minutes with vigorous stirring. The reaction mixture was stirred at 0 °C for 15 minutes, then at room temperature for 3 hours. The reaction mixture was cooled to 0 °C and quenched with saturated ammonium chloride solution (50 mL). The reaction mixture was further diluted with water (500 mL) and extracted with ethyl acetate (3 X 150 mL). The combined organic layers were washed with brine (150 mL), dried over MgSCU, filtered, and concentrated by rotary evaporation to a light yellow oil. This oil was sufficiently pure for the next step. Gives 11.145 g (92% yield). MS (APCI): calculated for C11H13BrO (M + H) = 241; found: 241.
Compound 5.2 (3-(l-(2-bromophenyl)cyclopentyl)-l-tosyl-lH-pyrrole/ 2-(l-(2- bromophenyl)cyclopentyl)-l-tosyl-lH-pyrrole): A 250 mL 2 neck round bottom flask was charged with a stir bar and fitted with a gas adapter. The flask was flushed with argon and l-(2- bromophenyl)cyclopentan-l-ol (10.0 mmol, 2.412 g) was added to the flask. Added anhydrous dichloromethane (100 mL) and added 1-tosyl-lH-pyrrole (11.0 mmol, 2.434 g) with stirring at room temperature. To the stirred mixture was added aluminum chloride (11.5 mmol, 1.533 g) in one portion. The reaction was stirred at room temperature under argon overnight. The reaction was quenched with water (30 mL) with vigorous stirring. The layers were separated and the aqueous layer was extracted with dichloromethane (3 X 25 mL). The combined organic layers were washed with brine (25 mL), dried over MgSCU, filtered, and evaporated to dryness. The crude product was purified by flash chromatography on silica gel (100% hexanes (1 CV)
Figure imgf000052_0001
15% EtOAc/hexanes (10 CV)). The two possible isomers elute as a single peak on silica gel and also co- elute with unreacted 1-tosyl-lH-pyrrole, 1.311 g. Estimated ~1.05 g of product by 1H NMR, 23% yield. This mixture was submitted to the next step without further purification. MS (APCI): calculated for C22H22BrNO2S (M + H) = 444; found: 444. Compound 5.3 (2-(l-(2-bromophenyl)cyclopentyl)-l-tosyl-lH-pyrrole): A 40 mL screw cap vial was charged with a stir bar. To this vial was added the mixture from Compound 2.2 (estimated 2.37 mmol, 1.05 g). The vial was flushed with argon. To this vial was added potassium carbonate (4.86 mmol, 672 mg), Pd(PPh3)4 (0.0711 mmol, 82 mg), and anhydrous dimethylformamide (6 mL). The vial was purged of oxygen by vacuum/backfill argon cycles (3 X). The reaction mixture was stirred under argon in a heating block at 110 °C overnight. The next morning, added more potassium carbonate (4.86 mmol, 672 mg) and Pd(PPh3)4 (0.0711 mmol, 82 mg) and heating continued at 110 °C for another 24 hours. The reaction mixture was cooled to room temperature, diluted with water (100 mL) and extracted with ether (3 X 50 mL). The combined organic layers were washed with water (3 X 25 mL), brine (25 mL), dried over MgSCU, filtered and evaporated to dryness. Purified by flash chromatography on silica gel (10% DCM/hexanes (1 CV)
Figure imgf000053_0001
50% DCM/hexanes (10 CV). The desired product co-elutes with 1-tosyl-lH-pyrrole, estimated yield by 1H NMR 549 mg, 64% yield. The mixture of the desired isomer and the 1-tosyl-lH-pyrrole was taken to the next step without further purification. MS (APCI): calculated for C22H21NO2S (M + H) = 364; found: 364.
Compound 5.4 (l'H-spiro[cyclopentane-l,4'-indeno[l,2-b]pyrrole]): A 100 mL 2 neck round bottomed flask was charged with a stir bar and fitted with a finned condenser and a gas adapter. The flask was flushed with argon and the mixture from Compound 2.3 (estimated 1.8 mmol, 819 mg mixture) was added, followed by tetrahydrofuran (BHT-inhibited, 50 mL) and methanol (15 mL). To the flask was added KOH (18.0 mmol, 1.01 g). The second neck was stoppered and the flask placed in a heat block. The reaction mixture was stirred under argon at 65 °C for 12 hours. The solvents were evaporated and the residue dispersed into saturated ammonium chloride (25 mL) and water (100 mL).The product was filtered off, dried, and purified by flash chromatography on silica gel (100% hexanes (1 CV)
Figure imgf000053_0002
20% EtOAc/hexanes (10 CV). Fractions containing product were dried by rotary evaporation to give 279 mg (74% yield), free of any contaminants. MS (APCI): calculated for C15H15N (M + H) = 210; found: 210. 1H NMR (400 MHz, Chloroform-d) δ 8.24 (s, 1H), 7.33 (dt, J = 7.5, 1.0 Hz, 1H), 7.24 - 7.17 (m, 2H), 7.08 (td, J = 7.2, 1.7 Hz, 1H), 6.81 (t, J = 2.5 Hz, 1H), 6.19 (dd, J = 2.7, 1.8 Hz, 1H), 2.16 - 2.02 (m, 6H), 1.89 - 1.74 (m, 2H). Compound 5.5 (4-(6',6'-difluoro-6'H-5|4,6'|4-dispiroIcyclopentane-1,12'- indeno[2,,1,:4,5]pyrrolo[l,2-c]indeno[2,,l,:4,5]pyrrolo[2,1-f][l,3,2]diazaborinine-16,,1"- cyclopentan]-14'-yl)-3,5-dimethylphenol): A 250 mL 2 neck round bottom flask was fitted with a finned condenser, stir bar, and a gas adapter. The flask was flushed with argon and Compound 2.4 (1.31 mmol, 275 mg) and 4-hydroxy-2,6-dimethylbenzaldehyde (0.683 mmol, 103 mg) were added, followed by anhydrous dichloroethane (50 mL). The solution was stirred and sparged with argon for 30 minutes, then trifluoroacetic acid (0.1% v/v, 50 uL) was added via syringe and the argon sparge continued for another 10 minutes. The sparge needle was removed and the reaction mixture stirred overnight at room temperature under argon. The next morning, the reaction mixture was cooled to 0 °C with an ice-water bath and p-chloranil (0.655 mmol, 161 mg) was added with stirring. The reaction was stirred at 0 °C for 20 minutes, at which point the oxidation was complete. To the reaction was added BF3.0Et2 (14.67 mmol, 1.8 mL) and triethylamine (8.78 mmol, 1.2 mL) and the mixture stirred at 0 °C and slowly warmed to room temperature over 4 hours. The water bath was removed and replaced by a heating block and the reaction heated at 40 °C for 6 hours. The reaction mixture was evaporated to dryness and treated with methanol (10 mL) and water (200 mL). The precipitate was stirred for 30 minutes at room temperature, then filtered off, washing with water. The precipitate was dried and purified by flash chromatography on silica gel (100% DCM (4 CV) ®· 5% EtOAc/DCM (5 CV) ®· 5% EtOAc/DCM. The column was eluted until the tailing product had eluted). Gives 314 mg, 85% yield. MS (APCI): calculated for C39H35BF2N2O (M ) = 596; found: 596.
RLE-5: (4-(6,,6'-difluoro-6,H-5,l4,6,l4-dispiro[cyclopentane-l,12,-indeno[2,,l,:4,5]pyrrolo[l,2- c]indeno[2',l,:4,5]pyrrolo[2,l-f][l,3,2]diazaborinine-16,,l"-cyclopentan]-14,-yl)-3,5- dimethylphenyl 4-(perylen-3-yl)butanoate): A 40 mL screw cap vial was charged with a stir bar, Compound 2.5 (0.100 mmol, 60 mg), 4-(perylen-3-yl)butanoic acid (0.150 mmol, 51 mg), and DMAP:pTsOH 1:1 salt (0.200 mmol, 59 mg). The vial was flushed with argon and anhydrous dichloromethane (20 mL) was added. Diisopropylcarbodiimide (0.300 mmol, 47 uL) was added and the reaction was stirred under argon at room temperature overnight. The next morning, added anhydrous tetrahydrofuran (10 mL) and sonicated for 30 seconds. Added an additional portion of 4-(perylen-3-yl)butanoic acid (0.150 mmol, 51 mg) and stirred at 50 °C under argon overnight. The solvents were evaporated and the product purified by flash chromatography on silica gel (100% hexanes (1 CV) 5% EtOAc/hexanes (0 CV) 40% EtOAc/hexanes (10 CV)). The product fractions were evaporated and purified a second time (100% hexanes (1 CV) 10% EtOAc/hexanes (0 CV) 30% EtOAc/hexanes (10 CV). Fractions containing pure product were evaporated to give 42 mg (52% yield). MS (APCI): calculated for C63H51BF2N2O2 (M ) = 915; found: 915.
Figure imgf000055_0001
Compound 6.1 (l,4,5,6-tetrahydrobenzo[6,7]cyclohepta[l,2-b]pyrrole): A mixture of KOH (1.35 g), NH2OH.HCI (1.67 g) in 10 mL DMSO was degassed , and stirred at r.t. for 30 min. To the mixture,
1-benzosuberone (3.2 g) in 10 mL DMSO was added. The resulting mixture was stirred at 70 °C for 30 min. Then KOH (2.0 g) was added and the mixture was heated to 140 °C, and a solution of 1,2-dichloroethane (2.38 g) in DMSO (10 mL) was added dropwise over one hour. After cooled to room temperature, the solution was poured into saturated NH4CI solution (100 mL). The solution was extracted with ethyl acetate (100 mL x 3). The organic phase was dried over Na2S04, loaded on silica gel and purified by flash chromatography using eluents of dichloromethane/hexanes (0% 30%). The 2nd main fraction was collected as the desired product, after removal of solvent, a white solid was obtained (0.22 g, in 8.5% yield). LCMS (APCI+): calculated for C13H14N (M+H): 184; found: 184.
Compound 6.2: A mixture of compound 8 (0.22 g, 1.2 mmol), 4-hydroxyl-2,5- dimethylbenzaldehyde (0.09ng, 0.6 mmol) in dichloroethane with one drop of TFA was degassed for 30 min, then heated at 40 °C overnight. After cooled to room temperature, with ice-water batch cooling, chloranil (0.2 g) was added, and the mixture was stirred for 20 min. Then BF3-ether (0.8 mL) and trimethylamine (0.5 mL) were added. The mixture was heated at 50 °C for two hours, then loaded on silica gel and purified by flash chromatography using eluents of dichloromethane/hexanes (10%
Figure imgf000056_0001
90%). The desired product was obtained after removal of solvents (54 mg, in 16% yield). LCMS (APCIl): calculated for C35H30BF2N2O (M-H): 543; Found: 543. RLE-6: To a mixture of compound 9 (54 mg, 0.1 mmol), 4-(perylen-3-yl)butanoic acid compound 5 (50 mg, 0.15 mmol), DMAP/p-TsOH salt (60mg, 0.2 mmol) in 7 mL dichloromethane, was added a solution of DIC (60 mg, 0.5 mmol) in 1 mL dichloromethane. The mixture was stirred at room temperature overnight, then loaded on silica gel, purified by flash chromatography using eluents of dichloromethane/hexanes (10%
Figure imgf000056_0002
70%). The desired fraction was collected, removal of solvent gave a solid (75 mg, in 87% yield). LCMS (APCI-): calcd for C59H47BF2N2O2 (M-): 864; found: 864. 1H NMR (400 MHz, Methylene Chloride-d2) δ 8.35 - 8.21 (m, 4H), 8.05 (d, J = 8.7 Hz, 2H), 7.74 (dd, J = 8.1, 5.0 Hz, 2H), 7.67 - 7.59 (m, 1H), 7.59 - 7.46 (m, 3H), 7.38 (td, J = 6.0, 5.5, 3.5 Hz, 4H), 7.33 (q, J = 5.1, 4.4 Hz, 2H), 6.96 (s, 2H), 6.47 (s, 2H), 5.37 (s, 15H), 3.29 - 3.21 (m, 2H), 2.79 (t, J = 7.2 Hz, 2H), 2.66 (t, J = 6.8 Hz, 4H), 2.32 (d, J = 7.3 Hz, 3H), 2.29 (s, 6H), 2.07 (p, J = 7.0 Hz, 4H).
Example 2.7 RLE-7
Figure imgf000057_0001
Compound 7.1: (tert-butyl 3-methyl-l,4,5,6-tetrahydrobenzo[6,7]cyclohepta[l,2-b]pyrrole-2- carboxylate): Step 1. T-butyl 3-oxobutanoate (10 mL) was dissolved in acetic acid (20 mL), and the solution was cooled with ice bath. To the solution, sodium nitrite (4.5 g) was added in portion while kept the mixture under 10 °C. After one hour, the ice batch was removed, and the mixture was allowed to warm up to r.t. and stirred for one hour to form oxime solution.
Step 2. To the solution prepared above, was added a solution of 1-benzosuberone (3.2g) in 25 mL acetic acid, followed by addition of zinc dust (11.25 g) portion wise. The resulting mixture was stirred at 75 °C for one hour, then the mixture was cooled to r.t., then added 10 mL water, and stand for one hour. The solid was filtered off, and the filtrate was poured into 100 mL water and stand overnight. The resulting solid was collected by filtration, and redissolved in dichloromethane and loaded on silica gel to be purified by flash chromatography using eluents of dichloromethane/hexanes (0% 90%). The desired product was collected as 2nd faction.
After removal of solvents, a white solid was obtained (0.15 g, in 2.5% yield). LCMS (APCI+): calculated for C19H24NO2 (M+H): 298; Found: 298. Compound 7.2: Compound 7.1 (50 mg, 0.168 mmol) was dissolve in 1.5 mLTFA. The solution was degassed for 10 min while stirring. LCMS indicated all of compound 7.1 was decorboxylated to desired pyrrole. To the mixture, 3 mL dichloroethane was added, followed by 10 mg 4- hydroxylbenzaldehyde. The mixture was degassed for 10 min and stirred overnight. LCMS indicated main product was dipyrrolemethane product. To the mixture, chloranil (20 mg, 0.084 mmol) was added at 0 °C, and stirred for 10 min. Then 0.4 mL BF3-ether and lmLtrimethylamine was added, and the resulting mixture was stirred at room temperature overnight, then loaded on silica gel and purified by flash chromatography using eluents of dichloromethane/hexanes (0% 80%). The desired product was obtained after removal of solvents (5 mg, in 12% yield). LCMS (APCI-): calculated for C35H30BF2N2O (M-H): 543; found: 543.
RLE-7: A mixture of compound 7.2 (5 mg, 0.01 mmol), 4-(perylen-3-yl)butanoic acid (5 mg, 0.015 mmol), DMAP/p-TsOH salt (6 mg, 0.02 mmol), and DIC (10 mg) in 2 mL dichloromethane was stirred at room temperature overnight, then loaded on silica gel and purified by flash chromatography using eluents of dichloromethane/hexanes (0% 35%). The orange-red fraction was collected, and removal of solvents gave a solid (3mg, in 35% yield). LCMS (APCI-): calculated for C59H47BF2N2O2 (M-): 864; Found: 864.
Figure imgf000058_0001
Figure imgf000059_0001
Step 1: In 1 L two neck flash equipped with magnetic stirring bar, powder dispenser funnel, a yellow suspension mixture of perylene (5.22 g, 20.68 mmol) in DCM anhydrous (500 mL) was stirred and bubbled with Argon 15 minutes on a cooling ice + water bath; methyl 4-{4,12b- dihydroperyien-3-yl) butanoate (3.425 g, 22.75 mmol) was added slowly via syringe and needle. Cooling bath was removed to allow the mixture stirring at RT for 15 minutes. The mixture was cooled again with ice+ water bath; AICI3 (3.3 g, 24.74 mmol) was added in small portion via the powder dispenser funnel. The resulting dark purple color mixture was stirred at RT for 16 hours under the protection of Argon. TIC and LCMS shown starting materials were almost consumed. The reaction mixture was diluted with 500 ml DCM then poured to ice+ water 150 ml water, organic layer was separated, dried with MgSO4 , concentrated, to the volume of 100 ml; SiO? (100 g) was added to THE solution mixture to absorb the product then load on to column (330 g), eluting withl Hexanes/ DCM (100:0) (0:100) gained 1.25 g of desired product. The product from column chromatography and the solid product from filtering were combined and re- crystallize by Hexanes: EtAco (9:1), gained 4.24 g yellow solid, yield 56%. LCMS (APCI+), calcd for Formula: C25H18O3; found: 366,: 1H NMR (400 MHz, Chloroform-d) δ 8.57 (dd, J = 8.6, 1.0 Hz, 1H), 8.30 - 8.17 (m, 4H), 7.97 (d, J = 8.1 Hz, 1H), 7.78 (d, J = 8.1 Hz, 1H), 7.73 (d, J = 8.1 Hz, 1H), 7.64 - 7.48 (m, 3H), 3.75 (s, 3H), 3.41 (t, J = 6.5 Hz, 2H), 2.86 (t, J = 6.5 Hz, 2H).
Step 2: In a 250 mL RB, a yellow mixture of the product of above step (4.24 g, 11.58 mmol) in DCM anhydrous (100 mL) was stirred and bubbled with Argon 15 minutes on a cooling ice+ water bath; TFA (25 ml) was added slowly. Cooling bath was removed to allow the mixture stirring at room temperature for 15 minutes.; triethyl silane (15 mL) was added in at once. The resulting dark color mixture was stirred at room temperature for 16 hours under the protection of Argon. TLC and LCMS shown starting materials were consumed. The reaction mixture was diluted with 200 ml DCM then put on rotavapor. TFA and DCM were concentrated. The residue was re- dissolved into DCM (50 ml) and the mixture was concentrated to dryness. The dark color crude product was loaded onto SiG2 column, eluting withl Hexanes/ Et.AcO (95:5) gained 4.00 g of yellow solid product, yield 98%. LCMS (APCk), calcd for Formula: C25H20O2; found: 352.
Figure imgf000060_0001
A solution mixture of compound methyl 4-(4;12h-dihydroperyien-3-yl) butanoate (1.00 g, 4.36 mmol) and MSS {1.9 g, 10,9 mmol). in anhydrous DCM (45 rnl) was stirred at room temperature and purged with Argon for 15 minutes, then DMF anhydrous (5 ml) was added. The resulting mixture was stirred at room temperature for 3 hours; TIC and LCMS shown starting materials were consumed. 20 ml water and 50 ml DCM were added, organic layer was washed several times with water, dried with MgSO4, concentrated. The crude product was purified by SiCb column chromatography, eluting withl Hexanes/ EtAcG (95:5) gained 1.25 g of a mixture of two isomers of dibromo peryiene derivatives, yield 56%,
LCMS (APG-T-), calcd for Formula: C25H18Br2O2; found: 510. Methyl 4-(4,9,10-tribromoperylen-3-yl) butanoate / methyl 4-(4,10-dibromo-4,12b- dihydroperylen-3-yl) butanoate / methyl 4-(5,9,10-tribromoperylen-3-yl) butanoate
Figure imgf000061_0001
A mixture of compound methyl 4-(4,12b-dihydroperylen-3-yl) butanoate (1.00 g, 2.837 mmol, leq), in anhydrous DCM (20 ml) was placed in a two necks flask and kept in dark. The mixture was purged with Argon for 15 minutes, and MBS (1.767g, 9.929 mmol, 3.5 eq) was added in small portions then stirred at room temperature for 15 min. DMF anhydrous (10 ml) was added. The resulting mixture was stirred at room temperature under protection of Argon for 4 hours. TIC and LCMS shown starting materials were consumed. 25 ml water was added, organic layer was separated; the water layer was re-extracted with Ethyl acetate, washed several times with water, dried with MgSO4, concentrated. The crude product was purified by SiCb column chromatography, eluting with Hexanes/ DCM (9:1) to (1:4) gained 0.655 g of a mixture of three isomers of tribromoperyiene derivatives: dibromoperylene derivatives: tetrabromoperylene derivatives (7:1:0.5). The products were carried next step without further purification. Yield 38%.
LCMS (APQ÷), calculated for Formula: C25H17Br3O2, found: 589.
Figure imgf000062_0001
One isomer drawn for illustration. Real reaction is a mixture of brominated isomers for starting material and trifluoromethylated isomers for the product
Set up a 100 mL 2-neck round-bottomed flask. Added a stir bar, finned condenser, and a gas adapter. The flask and condenser were flushed with argon. With stirring under argon protection, added Cul (10.0 eq, 13.6 mmol, 2.586 g) to the flask. The brominated perylene isomers (1.0 eq, 1.36 mmol, 800 mg) were dissolved in 5 mL anhydrous DMA under an argon atmosphere and transferred to the flask via syringe. The vial was rinsed with dry DMA (2 X 5 mL) under argon atmosphere and these DMA aliquots were also added to the reaction flask. Another 15 mL of anhydrous DMA was added to the reaction flask (total DMA = 30 mL). Methyl 2-(fluorosulfonyl)- 2,2-difluoroacetate (10.0 eq, 13.6 mmol, 2.609 g, 1.509 g/mL, 1.73 mL) was added to the flask via syringe and the second neck was sealed with a glass stopper. The mixture was stirred and heated with a heat block set to 160 °C. After 2 hours, LCMS indicated the reaction was about 90% complete. Cul (5.0 eq, 6.80 mmol, 1295 mg) and methyl 2-(fluorosulfonyl)-2,2-difluoroacetate (5.0 eq, 6.80 mmol, 1306 mg, 1.509 g/mL, 0.866 mL) were added and the reaction stirred for 2 hours at 160 °C, then at room temperature overnight. The reaction mixture was worked up by pouring into 700 mL of stirred water, washing the reaction flask with water and a small amount of methanol. The volume was adjusted to 900 mL with water and the suspension was filtered through a thin layer of Celite (slow filtration) and the cake was washed with water. The wet cake and filter paper were broken up and stirred first in acetone (20 mL), then DCM (500 mL) was added with stirring. The organic layer was filtered through a second thin pad of Celite, transferred to a separator funnel and separated from water, dried over MgSCU, filtered, and concentrated to dryness. The mixture was purified by flash chromatography (First wavelength = 300 nm, 2nd wavelength = 440 nm, 220 g column, equilibrate 50% toluene/hexanes, dissolve and load in 2:1 hexanes:toluene, eluting 50% (1 CV)
Figure imgf000063_0001
100% toluene (10 CV). Desired fractions showed strong UV peak at 440 nm.
Fractions were grouped into early-eluting mixture, middle peak, and later-eluting fractions. Early- eluting fractions were traces of mixed Br/CF3 isomers and were discarded. The middle peak was mostly tri-CF3-isomers, 204 mg (26.9% yield). Later-eluting fractions = di-CF3, tri-CF3, and tetra- CF3 mixed isomers, 75 mg (10% yield).
Two isomers were isolated as pure compound; NMR and LCMS determines two structures which were shown below:
Figure imgf000063_0002
1H NMR (400 MHz, Chloroform-d) δ 8.35-8.28(m, 4H), 8.09 (d, J = 8.12 Hz, 2H), 8.08 (d, J = 8.08 Hz, 1H), 7.68 (d, J = 7.96 Hz, 1H)), 3.66 (s, 3H), 3.24 (t, J = 7.64 Hz, 2H), 2.36 (t, J = 7.44 Hz, 2H), 1.92 (q, J = 7.44 Hz, 2H).
Figure imgf000064_0001
1H NMR (400 MHz, Chloroform-d) δ 8.28 (d, J = 7.73 Hz, 1H), 8.23 (d, J = 7.4 Hz, 1H), 8.18 (d, J = 8.5 Hz, 1H)), 8.12-8.06 (m, 3H), 7.79 (t, J = 7.92 Hz, 1H), 7.73 (s,lH), 3.72 (s, 3H), 3.2 (t, J = 7.64 Hz, 2H), 2.5 (t, J = 7.44 Hz, 2H), 2.15 (q, J = 7.44 Hz, 2H).
Figure imgf000064_0002
The mixture of methyl 4-(4,9,10-tris(trifluoromethyi)peryien-3-yl) hutanoate (40 mg, 0.0718 mmol), 5M KOH aq.soln. (0.143 ml, 0.718 mmol), THF (2 ml), MeOH (0.5 mi) was stirred at 65 °C for 6 hours. After cooling to 0 °C the mixture was acidified with 6N MCI aq. sole, to pH=4-5, then poured to water; extracted with DCM, dried MgSO4 concentrated to dryness, gained 38 mg red color solid product, 98% yield. The product was used next step without further purification.
LCMS (APCI-F), ca!cd for Formula: C27H15F9O2, Found: 542.40
RLE-8: ((T-4)-[2-[(4,5-dihydro-8-bromo-2H-benz[g]indol-2-ylidene- k/V)-(3,5-dimethyl-4-(-((4- (4,9,10-tris(trifluoromethyl)perylen-3-yl)butanoyl)oxy)phenyl)methyl]-4,5-dihydro-lH- benz[g]indolato- k/V]difluoroboron): Was synthesized from Compound 6.2 (described supra) [2- [(4,5-dihydro-8-bromo-2H-benz[g]indol-2-ylidene-k/V)-(3,5-dimethyl-4-hydroxyphenyl)methyl]- 4,5-dihydro-lH-benz[g]indolato-k/V]difluoroboron (0.100 mmol, 52 mg) and ((4,9,10- trifluoromethyl)peryen-3-yl) butanoic acid) (0.100 mmol, 55 mg. The crude product was purified by flash chromatography on silica gel (80% toluene/hexanes (1 CV)
Figure imgf000065_0001
100% toluene (5 CV)). Fractions containing product were evaporated to dryness to give 77 mg (74% yield). MS (APCI): calculated for Chemical Formula: C60H40BF11N2O2 (M-) = 1040; found: 1040.
Figure imgf000065_0002
Compound 9.1 (ethyl 3-methyl-4,5-dihydro-lH-benzo[g]indole-2-carboxylate): A 250 mL 2 neck round bottomed flask was charged with a stir bar and placed in a heat block. To this flask was added 1-tetralone (100.0 mmol, 14.620 g) and sodium propionate (100.0 mmol, 9.610 g), followed by acetic acid (50 mL). The reaction was heated to 145 °C with stirring open to air. A 40 mL screw cap vial was charged with ethyl 2-(hydroxyimino)-3-oxobutanoate (2.50 mmol, 398 mg) and Zn (dust, < 10 urn) (12.5 mmol, 818 mg). These materials were slurried in acetic acid (12.5 mL) and added to the stirred reaction containing the ketone in portions over a period of about 5 minutes. This process was repeated three times for a total of 10.0 mmol 2-(hydroxyimino)-3- oxobutanoate and 50.0 mmol Zn dust. The reaction was stirred at 145 °C for 2.5 hours, then cooled to room temperature. The reaction was quenched by pouring into water (600 mL) with stirring. The volume was brought up to 900 mL with water, then extracted with dichloromethane (4 X 160 mL). The combined organic layers were washed with water (100 mL), brine (100 mL), dried over MgSCU, filtered, and evaporated to dryness. Most of the excess 1-tetralone was removed on high vacuum with heating. The crude product was purified by flash chromatography on silica gel (5% EtOAc/hexanes (1 CV)
Figure imgf000066_0001
20% EtOAc/hexanes (10 CV). Fractions containing product were evaporated to dryness to give 1.417 g (55% yield). MS (APCI): calculated for Chemical Formula: CI6HI7NO2 (M + H) = 256; found: 256. 1H NMR (400 MHz) d 8.98 (s, 1H), 7.35 - 7.31 (m, 1H), 7.27 - 7.21 (m, 2H), 7.20 - 7.15 (m, 1H), 4.34 (q, J = 7.1 Hz, 2H), 2.99 - 2.92 (m, 2H), 2.70 - 2.64 (m, 2H), 2.31 (s, 3H), 1.39 (t, J = 7.1 Hz, 3H).
Compound 9.2 (3-methyl-4,5-dihydro-lH-benzo[g]indole): A 250 mL 2 neck round bottom flask was charged with a stir bar and fitted with a finned condenser and a gas adapter. The flask was flushed with argon and Compound 9.1 (5.01 mmol, 1.278 g) was added to the flask, followed by ethylene glycol (50 mL). To the reaction mixture was added KOH (5.0M in H20, 25.03 mmol, 5.01 mL). The reaction was stoppered and heated in a heat block at 100 ° C for 90 minutes under argon. The solution becomes homogenous with heating. The temperature was increased to 160 °C for 30 minutes, then cooled to 100 °C. The reaction was quenched by pouring into stirred water (300 mL). This was brought up to a total volume of 500 mL with water, then it was acidified with a solution of 2.5 M acetic acid/2.5 M NaOAc (20 mL). The pH was reduced to ~3.5 with TFA. The resulting purple solid was filtered off, dried, and purified by flash chromatography on silica gel (5% EtOAc/hexanes (1 CV)
Figure imgf000066_0002
20% EtOAc/hexanes (10 CV)). Fractions containing product were evaporated to dryness to give 767 mg (84% yield). MS (APCI): calculated for Chemical Formula: C13H13N (M + H) = 184 found: 184. 1H NMR (400 MHz, Acetonitrile-d3) δ 9.15 (s, 1H), 7.24 (d, J = 7.5 Hz, 1H), 7.20 - 7.13 (m, 2H), 7.00 (td, J = 7.4, 1.4 Hz, 1H), 6.52 (dd, J = 2.3, 0.9 Hz, 1H), 2.90 - 2.83 (m, 2H), 2.62 - 2.55 (m, 2H), 2.00 (s, 3H). Compound 9.3 ((T-4)-[2-[(4,5-Dihydro-3-methyl-2H-benz[g]indol-2-ylidene-K/V)( 3,5-dimethyl- 4-hydroxyphenyl)methyl]-4,5-dihydro-3-methyl-lH-benz[g]indolato-K/V]difluoroboron):
Compound 9.3 was synthesized from Compound 9.2 (3.97 mmol, 728 mg) and 4-hydroxy-2,6- dimethylbenzaldehyde (2.02 mmol, 304 mg) in a manner similar to Compound 3.2. The crude product was purified by flash chromatography on silica gel (100% toluene (2 CV)
Figure imgf000067_0001
10% EtOAc/toluene (10 CV)). Fractions containing product were evaporated to give 563 mg (52% yield for 3 steps from pyrrole). MS (APCI): calculated for Chemical Formula: C35H31BF2N2O (M + H) = 544 found: 544. 1H NMR (400 MHz, DMSO-d6) δ 9.61 (s, 1H), 8.62 (d, J = 7.9 Hz, 2H), 7.45 - 7.38 (m, 2H), 7.38 - 7.34 (m, 4H), 6.68 (s, 2H), 2.91 - 2.83 (m, 4H), 2.58 - 2.52 (m, 4H), 2.04 (s, 6H), 1.41 (s, 6H).
RLE-9: ((T-4)-[2-[(4,5-Dihydro-3-methyl-2H-benz[g]indol-2-ylidene-K/V)(3,5-dimethyl-4--((4-
(4,9,10-tris(trifluoromethyl)perylen-3-yl)butanoyl)oxy)phenyl)methyl]-4,5-dihydro-3-methyl- lH-benz[g]indolato-K/V]difluoroboron): RLE-9 was synthesized from Compound 9.3 (0.116 mmol, 63 mg) and (4,9,10-tris(trifluoromethyl)perylen-3-yl) butanoic acid (0.116 mmol, 63 mg) in a manner similar to Compound 2 (described supra). The crude product was purified by flash chromatography on silica gel (60% toluene/hexanes (2 CV) 100% toluene (isocratic)). Fractions containing product (as a mixture of isomers) were evaporated to dryness to give 84 mg (68% yield). MS (APCI): calculated for Chemical Formula: C62H44BF11N2O2 (M-) = 1068 found: 1068
Example 2.10 RLE-10
Figure imgf000068_0001
Compound 10.1: To a solution of 3-methyl-4,5-dihydro-l/-/-benzo[g]indole (3.55 mmol, 652 mg) and 4-hydroxybenzaldehyde (1.77 mmol, 216 mg) in anhydrous 1,2-dichloroethane (35.0 mL) at room temperatiure under argon atmosphere was added TFA (35.0 μL). The reaction mixture was stirred at room temperature for 70 min, cooled to 0 °C and p-chloranil (1.77 mmol, 435 mg) was added in one portion and the stirring was continued for 15 min. Triethylamine (10.6 mmol, 1.48 mL) was added and the mixture was warmed up to r.t. over 10 min before BF3-OEt2 (15.9 mmol, 1.96 mL) was added and the stirring was continued for 75 min. More triethylamine (10.6 mmol, 1.48 mL) and BF3-OEt2 (15.9 mmol, 1.96 mL) were added, the mixture was stirred for further 75 min and all volatiles were removed under reduced pressure. The residue was diluted with EtOAc (100 mL), washed with 1M HCI (2 x 100 mL) and 6M HCI (100 mL), dried (MgSO4) and concentrated under reduced pressure. Flash chromatography (CH2CI2) gave 130 mg of 10.1 (17% yield) as a dark blue/green powder. 1H NMR (400 MHz, TCE-d2) δ 8.74 (d, J = 8.0 Hz, 2H), 7.43 (ddd, J = 8.5, 8.0, 1.7 Hz, 2H), 7.39 - 7.24 (m, 6H), 7.02 (d, J = 8.5 Hz, 2H), 5.05 (s, 1H), 2.89 (dd, J = 8.3, 5.9 Hz, 4H), 2.56 (dd, J = 8.3, 5.9 Hz, 4H), 1.44 (s, 6H). RLE- 10: (T-4)-[2-[(4,5-dihydro-8-bromo-2H-benz[g]indol-2-ylidene-K/V)-(4'-(4-
(tris(trifluoromethyl)perylen-3-yl)butanoxy) phenyl)methyl]-4,5-dihydro-lH-benz[g]indolato- K/V]difluoroboron: To a solution of 10.1 (0.080 mmol, 41 mg), 4-(tris(trifluoromethyl)perylen-3- yl)butanoic acid (0.084 mmol, 46 mg) and DMAP-pTsOH salt (0.160 mmol, 47 mg) in anhydrous 1,2-dichloroethane (10.0 mL) at room temperature under argon atmosphere was added DIC (0.480 mmol, 75.0 μL) and the reaction mixture was stirred at room temperature for 2 h and then at 50 °C for 1 h. The mixture was then cooled to room temperature, more 4- (tris(trifluoromethyl)perylen-3-yl)butanoic acid (0.055 mmol, 30 mg) was added and the stirring was continued for 16 h. The mixture was diluted with hexanes (6.00 mL) and purified by flash chromatography (9:1 hexanes/CH2CI2 -> 3:7 hexanes/CH2CI2) to give 73.7 mg of RLE-10 (89% yield) as a dark purple powder.
1H NMR (400 MHz, TCE-d2) d 8.76 (d, J = 8.1 Hz, 2H), 8.37 - 7.68 (m, 9H), 7.49 - 7.39 (m, 4H), 7.39 - 7.28 (m, 6H), 3.49 - 3.30 (m, 2H), 2.99 - 2.77 (m, 5H), 2.77 - 2.67 (m, 1H), 2.61 - 2.49 (m, 4H), 2.40 - 2.26 (m, 1H), 2.20 - 2.08 (m, 1H), 1.42 (d, J = 7.6 Hz, 6H).
Example 2.11 Compound RLE-11
Figure imgf000070_0002
Compound 11.1 (4-formyl-3,5-dimethylphenyl 4-(perylen-3-yl)butanoate): Compound 11.1 was synthesized from 4-hydroxy-2,6-dimethylbenzaldehyde (1.89 mmol, 284 mg) and 4-(perylen-3- yl)butanoic acid (0.946 mmol, 320 mg) in a manner similar to RLE-2. The crude product was purified by flash chromatography on silica gel (100% toluene, (5 CV)
Figure imgf000070_0001
10% EtOAc/toluene (10
CV). Fractions containing product were evaporated to dryness. Gives 296 mg (66.5% yield) of an orange solid. MS (APCI): calculated for Chemical Formula: C33H26O3 (M-) = 470 found: 470. 1H NMR (400 MHz, TCE-d2) δ 10.52 (s, 1H), 8.25 (d, J = 7.5 Hz, 1H), 8.23 - 8.17 (m, 2H), 8.16 (d, J = 7.8 Hz, 1H), 7.94 (d, J = 8.4 Hz, 1H), 7.72 (d, J = 5.1 Hz, 1H), 7.70 (d, J = 5.1 Hz, 1H), 7.57 (t, J = 8.0 Hz, 1H), 7.51 (t, J = 7.8 Hz, 1H), 7.51 (t, J = 7.8 Hz, 1H), 7.40 (d, J = 7.7 Hz, 1H), 6.84 (s, 2H), 3.17
(t, J = 7.6 Hz, 2H), 2.72 (t, J = 7.2 Hz, 2H), 2.58 (s, 6H), 2.23 (p, J = 7.3 Hz, 2H).
Compound RLE-11 ((T-4)-[2-[(4,5-dihydro-8-fluoro-2H-benz[g]indol-2-ylidene-K/V) ( 3,5- dimethYl-4-(4-(perYlen-3-Yl)butanoate) phenyl)methyl]-4,5-dihydro-8-fluoro-1H-benz[g] indolato-K/V]difluoro-boron): Compound RLE-11 was synthesized from Compound 21.2 (200 pmol), Compound 11.1 (105 mitioI, 49.4 mg), p-chloranil (100 umol, 24.5 mg), triethylamine (600 umol, 84 uL), and BF3.0Et2 in a manner similar to Compound 21. The crude product was purified by flash chromatography on silica gel (100% toluene isocratic). Fractions containing product were evaporated to dryness. Gives 74 mg (82% yield, based on Compound 21.2). MS (APCI): calculated for Chemical Formula: C58H45BF4N2O2 (M-) = 888 found: 888.
Figure imgf000071_0001
Ethyl 3-methyl-l,4-dihydroindeno[l,2-£>]pyrrole-2-carboxylate (12.1)
To a mixture of 1-indanone (30.0 mmol, 3.96 g), Zn granules - 20 mesh (50.0 mmol, 3.27 g) and sodium propionate (5.00 mmol, 480 mg) in valeric acid (20.0 mL) at 180 °C was added a solution of ethyl 2-(hydroxyimino)-3-oxobutanoate (10.0 mmol, 1.59 g) in valeric acid (10.0 mL) via a syringe pump over 1 h. The reaction mixture was stirred for further 15 min after the addition was completed before being cooled to r.t. and partitioned between 6 M HCI (100 mL) and EtOAc (100 mL). The aqueous layer was extracted with EtOAc (3 x 100 mL), the combined organics washed with 1 m aqueous NaOH (3 x 200 mL), dried (MgS04) and concentrated under reduced pressure. Re-precipitation from EtOH gave 505 mg of Compound 12.1 (21% yield) as a colorless solid. XH NMR (400 MHz, Chloroform-d) δ 9.05 (br s, 1H), 7.48 (dt, J = 7.5, 1.1 Hz, 1H), 7.44 (dt, J = 7.5, 1.0 Hz, 1H), 7.30 (td, J = 7.5, 1.0 Hz, 1H), 7.19 (td, J = 7.5, 1.1 Hz, 1H), 4.37 (q, J = 7.1 Hz, 2H), 3.49 (s, 2H), 2.42 (s, 3H), 1.40 (t, J = 7.1 Hz, 3H).
3-Methyl-l,4-dihydroindeno[l,2-b]pyrrole (Compound 12.2)
To a suspension of Compound 12.1 (0.1.61 mmol, 388 mg) and sodium hydroxide (4.82 mmol, 193 mg) in ethylene glycol (16 mL) was added water (500 μL) and the reaction mixture was stirred at 150 °C for 1 h. It was then cooled to r.t. and 1.0 M aqueous solution of NH4CI (50.0 mL) was added. The precipitate was isolated by vacuum filtration and air-dried to give 264 mg of Compound 12.2 (97% yield) as a purple solid.
1H NMR (400 MHz, Acetonitrile-d3) δ 9.17 (br s, 1H), 7.42 (d, J = 7.4 Hz, 1H), 7.35 (d, J = 7.5 Hz, 1H), 7.22 (dd, J = 7.4, 7.5 Hz, 1H), 7.03 (ddd, J = 7.5, 7.5, 1.2 Hz, 1H), 6.61 (dd, J = 2.3, 1.1 Hz, 1H), 3.38 (s, 2H), 2.11 (s, 3H).
4-(6,6-Difluoro-13,15-dimethyl-12,16-dihydro-6H-5l4,6l4-indeno[2',l,:4,5]pyrrolo[l,2- c]indeno[2',l':4,5]pyrrolo[2,l-f][l,3,2]diazaborinin-14-yl)-3,5-dimethylphenyl 4-(perylen-3- yl)butanoate (RLE-12)
To a solution of Compound 12.2 (0.467 mmol, 79.0 mg), and pTsOH-H20 (0.005 mmol, 1.00 mg) in anhydrous 1,2-dichloroethane (5.00 mL) at r.t. under argon atmosphere was added Compound 12.3 (0.212 mmol, 100 mg). The reaction mixture was stirred at r.t. for 3 h, then it was cooled to 0 °C, p-chloranil (0.212 mmol, 52.0 mg) was added in one portion and the stirring was continued for 15 min. Triethylamine (1.27 mmol, 177 μL) was added and the mixture was warmed up to r.t. over 10 min before BF3-OEt2 (1.91 mmol, 235 μL) was added and the stirring was continued for further 30 min. The reaction mixture was diluted with EtOAc (30.0 mL), washed with 1M HCI (3 x 30.0 mL) and saturated aqueous solution of NaCI (30.0 mL), dried (MgSO4) and concentrated under reduced pressure. Flash chromatography (toluene) gave 96.0 mg of RLE-12 (54% yield) as a dark purple powder.
1H NMR (400 MHz, Chloroform-d) δ 8.39 (d, J = 7.8 Hz, 2H), 8.27 - 8.13 (m, 4H), 7.96 (d, J = 8.4 Hz, 1H), 7.68 (dd, J = 8.1, 4.3 Hz, 2H), 7.56 (t, J = 7.9 Hz, 1H), 7.51 - 7.44 (m, 6H), 7.41 (d, J = 7.7 Hz, 1H), 7.38 - 7.33 (m, 2H), 6.92 (s, 2H), 3.51 (s, 4H), 3.21 (t, J = 7.5 Hz, 2H), 2.73 (t, J = 7.1 Hz, 2H), 2.22 (s, 8H), 1.47 (s, 6H).
Figure imgf000073_0001
To a solution of 12.2 (0.086 mmol, 15.0 mg), and pTsOH-H20 (1 crystal) in anhydrous CH2CI2 (0.90 mL) at r.t. under argon atmosphere was added 13.1 (0.039 mmol, 26.0 mg). The reaction mixture was stirred at r.t. for 1 h, then it was cooled to 0 °C, p-chloranil (0.039 mmol, 10.0 mg) was added in one portion and the stirring was continued for 15 min. Triethylamine (0.234 mmol, 33.0 μL) was added and the mixture was warmed up to r.t. over 10 min before BF3-OEt2 (0.351 mmol, 43.0 μL) was added and the stirring was continued for further 30 min. The reaction mixture was diluted with EtOAc (5.00 mL), washed with 1M HCI (3 x 5.00 mL) and saturated aqueous solution of NaCI (5.00 mL), dried (MgSCU) and concentrated under reduced pressure. Flash chromatography (toluene) gave 16.0 mg of RLE-13(38% yield) as a dark purple/green powder.
1H NMR (400 MHz, Chloroform-d) δ 8.40 (d, J = 7.9 Hz, 2H), 8.34 - 7.62 (m, 8H), 7.53 - 7.42 (m, 4H), 7.36 (apparent t, J = 7.5 Hz, 2H), 7.02 - 6.93 (m, 2H), 3.52 (s, 4H), 3.41 - 3.31 (m, 2H), 2.85 -
2.74 (m, 2H), 2.37 - 2.22 (m, 8H), 1.52 (s, 6H).
Example 2.14 RLE-14
Figure imgf000074_0001
3,3-Dimethyl-2,3-dihydro-lH-inden-l-one (RLE-14.1)
A solution of 3-methylcrotonic acid (19.0 mmol, 1.90 g) in benzene (10.0 mL) was slowly added to AICU (57.0 mmol, 7.60 g) in a 100 mL round-bottom flask. The resulting mixture was heated to reflux for 5 h, cooled to 0 °C, quenched with 1M HCI (50.0 mL) and extected with EtOAc (3 x 50.0 mL). The combined organics were washed with a saturated aqueous solution of NaHCCh (3 x 100 mL) and saturated aqueous solution of NaCI (100 mL), dried (MgSC ) and concentrated under reduced pressure. Flash chromatography (9:1, hexanes/EtOAc) gave 2.62 g of 14.1 (86% yield) as an orange oil. 1H NMR (400 MHz, Chloroform-d) δ 7.72 - 7.67 (m, 1H), 7.65 - 7.57 (m, 1H), 7.53 - 7.47 (m, 1H), 7.39 - 7.32 (m, 1H), 2.60 - 2.58 (m, 2H), 1.47 - 1.36 (m, 6H); 13C NMR (101 MHz, Chloroform-d) d 205.7, 163.7, 135.1, 134.8, 127.2, 123.4, 123.2, 52.8, 38.4, 29.8.
Ethyl 3,4,4-trimethyl-l,4-dihydroindeno[l,2-b]pyrrole-2-carboxylate (14.2)
To a mixture of 14.1 (3.12 mmol, 500 mg), Zn granules - 20 mesh (15.6 mmol, 1.02 g) and sodium propionate (1.56 mmol, 150 mg) in valeric acid (12.5 mL) at 180 °C was added a solution of ethyl 2-(hydroxyimino)-3-oxobutanoate (4.68 mmol, 750 mg) in valeric acid (2.50 mL) via a syringe pump over 1 h. The reaction mixture was stirred for further 15 min after the addition was completed before being cooled to r.t. and partitioned between 6 M HCI (25.0 mL) and EtOAc (25.0 mL). The aqueous layer was extracted with EtOAc (3 x 25.0 mL), the combined organics dried (MgS04) and concentrated under educed pressure. Flash chromatography (9:1, hexanes/EtOAc) gave 42 mg of 14.2 (5% yield) as a colorless solid.
XH NMR (400 MHz, Chloroform-d) δ 9.19 (s, 1H), 7.40 - 7.34 (m, 2H), 7.27 - 7.18 (m, 2H), 4.38 (q, J = 7.1 Hz, 2H), 2.47 (s, 3H), 1.51 (s, 6H), 1.40 (t, J = 7.1 Hz, 3H).
3,4,4-Trimethyl-l,4-dihydroindeno[l,2-b ]pyrrole (14.3)
To a suspension of 14.2 (0.149 mmol, 42 mg) and sodium hydroxide (0.446 mmol, 18.0 mg) in ethylene glycol (1.50 mL) was added water (50.0 μL) and the reaction mixture was stirred at 150 °C for 1 h. It was then cooled to r.t. and 1.0 M aqueous solution of NH4CI (5.00 mL) was added. The mixture was extracted with CH2CI2 (3 x 10.0 mL) to give 29 mg of 12.2 (99% yield) as a purple solid.
1H NMR (400 MHz, Chloroform-d) δ 7.97 (br s, 1H), 7.30 (dt, J = 7.3, 0.9 Hz, 1H), 7.21 - 7.14 (m, 2H), 7.07 (ddd, J = 7.4, 5.4, 3.3 Hz, 1H), 6.57 (dd, J = 2.2, 1.1 Hz, 1H), 2.20 (d, J = 1.0 Hz, 3H), 1.50 (s, 6H).
4-(6,6-Difluoro-12,12,13,15,16,16-hexamethyl-12,16-dihydro-6H-5λ4,6λ4- indeno[2',l':4,5]pyrrolo[l,2-c]indeno[2,,l,:4,5]pyrrolo[2,l-/|[l,3,2]diazaborinin-14-yl)-3,5- dimethylphenyl 4-(tris(trifluoromethyl)perylen-3-yl)butanoate (RLE-14)
To a solution of 14.3 (0.071 mmol, 14.0 mg), and pTsOH-H20 (1 crystal) in anhydrous CH2CI2 (0.70 mL) at r.t. under argon atmosphere was added 13.1 (0.039 mmol, 26.0 mg). The reaction mixture was stirred at r.t. for 1 h, then it was cooled to 0 °C, p-chloranil (0.036 mmol, 9.00 mg) was added in one portion and the stirring was continued for 15 min. Triethylamine (0.216 mmol, 30.0 μL) was added and the mixture was warmed up to r.t. over 10 min before BF3-OEt2 (0.324 mmol, 40.0 μL) was added and the stirring was continued for further 30 min. The reaction mixture was diluted with EtOAc (5.00 mL), washed with 1M HCI (3 x 5.00 mL) and saturated aqueous solution of NaCI (5.00 mL), dried (MgS04) and concentrated under reduced pressure. Flash chromatography (1:1 hexanes/toluene -> toluene) gave 8.00 mg of RLE-14 (21% yield) as a dark purple/green powder. 1H NMR (400 MHz, Chloroform-d) d 8.34 - 7.62 (m, 10H), 7.46 - 7.33 (m, 6H), 7.01 - 6.92 (m, 2H), 3.42 - 3.31 (m, 2H), 2.79 (dt, J = 13.9, 7.0 Hz, 2H), 2.36 - 2.23 (m, 8H), 1.53 (s, 6H), 1.50 (s, 12H).
Figure imgf000076_0001
Compound 15.1 (ethyl 7-bromo-3-methyl-4,5-dihydro-lH-benzo[g]indole-2-carboxylate): To a
250 mL 2 neck round bottom flask was added a stir bar, 6-bromo-3,4-dihydronaphthalen-l(2H)- one (20.0 mmol, 4.502 g), sodium propionate (5.00 mmol, 480 mg), and Zn (granules, 10-20 mesh, 50.0 mmol, 3.270 g). The flask was fitted with a finned condenser and a gas adapter. The flask was flushed with argon and propionic acid (20 mL) was added. A solution of ethyl acetoacetate- 2-oxime (10.0 mmol, 1.591 g) was prepared in propionic acid (10 mL). The reaction flask was placed in an aluminum heat block and pre-heated to 160 ° C. The solution of ethyl acetoacetate- 2-oxime was added via syringe pump over a period of 60 minutes. Crude LCMS indicates product and dehydrohalogenated product as well as unreacted starting material and dehydrohalogenated starting material. The crude reaction mixture was cooled to room temperature, then diluted with EtOAc (200 mL). The reaction mixture was transferred to a separatory funnel and washed with water (1 X 200 mL, 1 X 100 mL), IN NaOH in water (2 X 50 mL), and brine (50 mL). The organic layer was dried over MgSCU, filtered, and concentrated to an oil. This oil was diluted with hexanes (50 mL) and allowed to stand overnight at room temperature. The resulting crystals were filtered off, washing with hexanes. The mother liquor was evaporated to dryness and purified by flash chromatography on silica gel (100% hexanes (2 CV) 10% EtOAc/hexanes (20 CV)). Fractions containing product were evaporated to dryness. The product purified from silica gel was combined with the crystals to give pure product. XH NMR indicates two pyrrole-Me groups in a ~1:2 ratio. LCMS shows the major product to be the dehydrohalogenated product. Gives 1.077 g (~38.2% yield, based on blended MW with ratio from 1H NMR). Both are inseparable on silica gel. Used in the next step without further purification. MS (APCI): calculated for Chemical Formula: Ci6Hi6BrN02 (M+H) = 334 found: 334. MS (APCI): calculated for Chemical Formula: CI6HI7N02 (M+H) = 256 found: 256. 1H NMR (400 MHz, TCE-d2) d 9.00 (s, 1H), 7.41 - 7.12 (m, 3.7H), 4.34 (q, J = 7.1 Hz, 2H), 3.00 - 2.88 (m, 2H), 2.72 - 2.59 (m, 2H), 2.31 (s, 2H, H-isomer), 2.30 (s, 1H, Br-isomer), 1.39 (td, J = 7.1, 1.2 Hz, 3H).
Figure imgf000077_0001
3-Methyl-4,5-dihydro-lH-benzo[g]indole and 7-bromo-3-methyl-4,5-dihydro-lH- benzo[g]indole (15.2)
To a mixture of ethyl 3-methyl-4,5-dihydro-l/-/-benzo[g]indole-2-carboxylate and ethyl 7-bromo- 3-methyl-4,5-dihydro-l/-/-benzo[g]indole-2-carboxylate (about 2:1 ratio, 2.87 mmol, 812 mg) in 30:1 ethylene glycol/H20 (25.0 mL) was added sodium hydroxide (7.29 mmol, 120 mg) and the mixture was stirred at 150 °C for 4 h. It was then cooled to r.t., quenched with 1M aqueous NH4CI (150 mL) and the pH was adjusted to pH = 3 with 6M HCI. The precipitate was collected by vacuum filtration and lyophilized for 16 h to give 639 mg of an inseparable mixture of 3-methyl-4,5- dihydro-l/-/-benzo[g]indole and 7-bromo-3-methyl-4,5-dihydro-l/-/-benzo[g]indole (about 2:1 ratio, quantitative yield) which was used in the subsequent synthetic step without further purification.
(7-4)-[2-[(4,5-dihydro-3-methyl-7-bromo-2H-benz[g]indol-2-ylidene-K/\/)-(2',6'-dimethyl-4'-(4- (perylenyl)butanoxy)phenyl)methyl]-4,5-dihydro-3-methyl-7-bromo-lH-benz[g]indolato- K/V]difluoroboron (RLE-15)
To a mixture of 3-methyl-4,5-dihydro-l/-/-benzo[g]indole and 7-bromo-3-methyl-4,5-dihydro-l/-/- benzo[g]indole prepared as described above (300 mg, approx. 1.42 mmol) in CH2CI2 (14.0 mL) was added 15.3(0.568 mmol, 267 mg) and pTsOH-H2O (0.057 mmol, 7.00 mg) and the reaction mixture was stirred at r.t. for 2 h. Chloranil (0.568 mmol, 140 mg) was then added and the mixture was stirred at r.t. for 15 min. Triethylamine (3.41 mmol, 474 μL) was added, the mixture was stirred at r.t. for 30 min before BF3-OEt2 (5.11 mmol, 631 μL) was added and the mixture was stirred at r.t. for 1 h. It was then diluted with EtOAc (50.0 mL), washed with 3 M HCI (3 x 50.0 mL), dried (MgSO4) and concentrated under reduced pressure. Flash chromatography (4:1, toluene/hexanes → 9:1, toluene/hexanes) gave 105 mg of RLE-15 (18% yield) as a dark blue/purple solid.
1H NMR (400 MHz, Chloroform-d) δ 8.78 (d, J = 8.1 Hz, 1H), 8.66 (d, J = 8.8 Hz, 1H), 8.27 - 8.13 (m, 4H), 7.96 (d, J = 8.4 Hz, 1H), 7.68 (dd, J = 8.1, 4.4 Hz, 2H), 7.59 - 7.37 (m, 7H), 7.31 (apparent t, J = 7.4 Hz, 1H), 6.90 (s, 2H), 3.21 (t, J = 7.5 Hz, 2H), 2.94 - 2.81 (m, 4H), 2.72 (t, J = 7.2 Hz, 2H), 2.57 - 2.48 (m, 4H), 2.33 - 2.22 (m, 2H), 2.18 (s, 6H), 1.35 (d, J = 3.1 Hz, 6H). Example RLE-16
Synthesis of 16.1:
Figure imgf000079_0001
Compound 15.4A (methyl 3-oxo-3-(perylen-3-yl)propanoate): A 500 mL 3 neck round bottom flask was charged with a stir bar and flushed with argon. To this flask was added AICI3 (9.52 mmol, 1.27 g, followed by anhydrous dichloromethane (160 mL). The solution was stirred at room temperature and methyl 3-chloro-3-oxopropanoate (8.30 mmol, 0.890 mL) was added, followed by perylene (7.92 mmol, 1.99 g). The reaction was stirred at room temperature under argon overnight. The following morning, the flask was fitted with a finned air condenser and heated with a heat block to 45 0 C and stirred at this temperature over the weekend under argon. Added another portion of methyl 3-chloro-3-oxopropanoate (8.30 mmol, 0.890 mL) and continued stirring at 450 C under argon overnight. The reaction was quenched by the addition of water (100 mL) and aqueous 6N HCI (100 mL) and diluted with dichloromethane (100 mL). The layers were separated (emulsion) and the water layer extracted with DCM (2 X 200 mL, emulsion), then DCM (4 X 100 mL). The organic layers were dried with MgSO4, filtered, and concentrated in vacuo. The product was purified by flash chromatography on silica gel (100% DCM (3 CV) → 1% EtOAc/DCM (0 CV) ®· 1% EtOAc/DCM (3 CV) ®· 10% EtOAc/DCM (8 CV)) to give product, 1.905 g (68% yield).
MS (APCI): calculated for C24H16O3 (M + H) = 353; found: 353.
Compound 15.4B (3-(perylen-3-yl)propanoic acid): Compound 42.1 (3.10 mmol, 1.091 g) was reduced with triethylsilane and saponified in a manner similar to Compound 41.1. The resulting acid had very poor solubility and required hot THF to dissolve in reasonable volumes. Gives 682 mg (68% yield over 2 steps). MS (APCI): calculated for C23H16O2 (M - H) = 323; found: 323. Compound 15.4C (4-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)phenyl 3-(perylen-3- yl)propanoate): Compound 42.3 was synthesized from Compound 42.2 (1.67 mmol, 543 mg) and 4-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)phenol (2.51 mmol, 553 mg) A 40 mL screw cap vial was flushed with argon and charged with Compound 42.2 (1.67 mmol, 543 mg), 4-(4, 4,5,5- tetramethyl-l,3,2-dioxaborolan-2-yl)phenol (2.51 mmol, 553 mg), DMAP (0.214 mmol, 26 mg), pTsOH.H2O (0.193 mmol, 36 mg) and a stir bar. The vial was sealed with a screw-cap septum, anhydrous DCM (4 mL) was added and the mixture stirred to effect solution. To the stirred reaction was added DIC (0.642 mmol, 0.100 mL) and the mixture stirred under argon overnight. The reaction mixture was diluted with ethyl acetate (150 mL) and extracted with aqueous 3N HCI (25 mL). The organic layer was washed with aqueous saturated sodium bicarbonate (25 mL), brine (15 mL), dried over MgSCU, filtered and concentrated in vacuo. This material was purified by flash chromatography on silica gel (100% DCM (3 CV) 1% EtOAc/DCM (0 CV) 10% EtOAc/DCM (10 CV)). to give product after purification by flash chromatography on silica gel, 434 mg (49% yield). MS (APCI): calculated for C35H31BO4 (M - H) = 525; found: 525.
(T-4)-[2-[(4,5-dihydro-3-methyl-7-((4-(perylenyl)butanoxy)phenyl)methyl-2H-benz[g]indol-2- ylidene-K/V)-(2',6'-dimethyl-4'-(4-(perylenyl)butanoxy)phenyl)methyl]-4,5-dihydro-3-methyl- 7-((4-(perylenyl)butanoxy)phenyl)methyl-lH-benz[g]indolato-K/V]difluoroboron (RLE-16)
To a solution of RLE-15 (0.049 mmol, 50.0 mg) and 15.4 (0.107 mmol, 58.0 mg) in 6:3:1, THF/toluene/water (1.00 mL) was added PdChidppf) (0.002 mmol, 1.80 mg) and K2CO3 (0.147 mmol, 20.0 mg) and the reaction mixture was heated to reflux for 16 h before it was cooled to r.t. and quenched with 1 M HCI (6.00 mL). The mixture was extracted with CH2CI2 (3 x 5.00 mL), the combined organics dried (MgSCU) and concentrated under reduced pressure. Flash chromatography (toluene -> 49:1, toluene/EtOAc) gave 26.0 mg of RLE-16 (31% yield) as a blue solid.
1H NMR (400 MHz, Methylene Chloride-d2) δ 8.79 (dd, J = 18.7, 8.3 Hz, 2H), 8.30 - 8.13 (m, 8H), 8.00 (d, J = 8.4 Hz, 2H), 7.83 - 7.38 (m, 18H), 7.37 - 7.05 (m, 6H), 6.92 (s, 2H), 3.21 (td, J = 7.8, 4.6 Hz, 4H), 2.98 (t, J = 7.0 Hz, 2H), 2.91 (t, J = 7.1 Hz, 2H), 2.78 - 2.70 (m, 4H), 2.58 (dt, J = 15.1, 7.0 Hz, 4H), 2.35 - 2.11 (m, 10H), 1.38 (d, J = 2.7 Hz, 6H).
Figure imgf000081_0001
(7-4)-[2-[(4,5-dihydro-3-methyl-2H-benz[g]indol-2-ylidene-K/\/)-(2',6'-dimethylphenyl)methyl]- 4,5-dihydro-3-methyl-1H-benz[g]indolato-K/V]difluoroboron and (T-4)-[2-[(4,5-dihydro-3- methyl-7-bromo-2H-benz[g]indol-2-ylidene-K/V)-(2',6'-dimethylphenyl)methyl]-4,5-dihydro-3- methyl-7-bromo-1H-benz[g]indolato-K/V]difluoroboron (17.2)
To a mixture of 3-methyl-4,5-dihydro-1H-benzo[g]indole and 7-bromo-3-methyl-4,5-dihydro-l/-/- benzo[g]indole prepared as described above (248 mg, approx. 1.17 mmol) and pTsOH-H2O (0.039 mmol, 5.00 mg) in CH2CI2 (10.0 mL) was added 2,6-dimethylbenzaldehyde (0.391 mmol, 52 mg) in CH2CI2 (2.00 mL) and the reaction mixture was stirred at r.t. for 1 h. Chloranil (0.391 mmol, 96.0 mg) was then added and the mixture was stirred at r.t. for 20 min.Triethylamine (2.34 mmol, 326 μL) was added, the mixture was stirred at r.t. for 30 min before BF3-OEt2 (3.52 mmol, 434 μL) was added and the mixture was stirred at r.t. for 1 h. More triethylamine (1.17 mmol, 163 μL) and, after 10 min stirring at r.t., BF3-OEt2 (1.76 mmol, 217 μL) were added and the mixture was stirred at r.t. for further 30 min. It was then diluted with EtOAc (50.0 mL), washed with 3 M HCI (3 x 50.0 mL), dried (MgSO4) and concentrated under reduced pressure. Flash chromatography (1:1, toluene/hexanes) gave 133 mg of (T-4)-[2-[(4,5-dihydro-3-methyl-2/-/-benz[g]indol-2- ylidene-K/V)-(2',6'-dimethylphenyl)methyl]-4,5-dihydro-3-methyl-l/-/-benz[g]indolato- K/V]difluoroboron and (7"-4)-[2-[(4,5-dihydro-3-methyl-7-bromo-2/-/-benz[g]indol-2-ylidene-K/V)- (2',6'-dimethylphenyl)methyl]-4,5-dihydro-3-methyl-7-bromo-1H-benz[g]indolato-
K/V]difluoroboron (approx. 2:1 ratio) as a dark blue/purple solid which was used in the subsequent synthetic step without further purification.
(T-4)-[2-[(4,5-dihydro-3-methyl-7-((4-(perylenyl)butanoxy)phenyl)methyl-2H-benz[g]indol-2- ylidene-K/V)-(2',6'-dimethylphenyl)methyl]-4,5-dihydro-3-methyl-7-((4- (perylenyl)butanoxy)phenyl)methyl-lH-benz[g]indolato-K/V]difluoroboron (RLE-17)
To a solution of a mixture of (7"-4)-[2-[(4,5-dihydro-3-methyl-7-bromo-2/-/-benz[g]indol-2-ylidene- K/V)-(2',6'-dimethylphenyl)methyl]-4,5-dihydro-3-methyl-7-bromo-1H-benz[g]indolato- K/V]difluoroboron (133 mg, approx. 0.194 mmol) prepared as described above and 17.3 (0.426 mmol, 230 mg) in 6:3:1, THF/toluene/water (4.00 mL) was added PdChfdppf) (0.010 mmol, 7.00 mg) and K2CO3 (0.582 mmol, 80.0 mg) and the reaction mixture was heated to reflux for 16 h before it was cooled to r.t. and quenched with 1 M HCI (10.0 mL). The mixture was extracted with CH2CI2 (3 x 10.0 mL), the combined organics dried (MgSCU) and concentrated under reduced pressure. Flash chromatography (4:1, toluene/hexanes -> toluene) gave 51.0 mg of RLE-17 (10% overall yield) as a dark blue/purple solid. 1H NMR (400 MHz, Methylene Chloride-d2) δ 8.90 - 8.71 (m, 2H), 8.30 - 8.16 (m, 3H), 8.04 - 7.97 (m, 1H), 7.80 - 7.63 (m, 4H), 7.60 - 7.40 (m, 5H), 7.36 - 7.26 (m, 2H), 7.25 - 7.15 (m, 3H), 3.20 (t, J = 7.7 Hz, 2H), 3.09 - 2.84 (m, 4H), 2.75 (t, J = 7.2 Hz, 2H), 2.70 - 2.45 (m, 4H), 2.33 - 2.11 (m, 8H), 1.36 (s, 6H).
Example 2.18 RLE-18
Figure imgf000083_0001
l,4,5,6-Tetrahydrobenzo[6,7]cyclohepta[l,2-b]pyrrole (18.1)
To a solution of 1-benzosuberone (10.0 mmol, 1.46 mL) in 3:1, H2O/Et0H (32.5 mL) at r.t. were added NH2OH.HCI (15.0 mmol, 1.04 g) and sodium acetate (25.0 mmol, 2.05 g) and the reaction mixture was stirred at 95 °C for 1 h. It was then cooled to r.t., filtered, washed with water (150 mL) and lyophilized for 16 h to give 1.64 g of 6,7,8,9-tetrahydro-5H-benzo[7]annulen-5-one oxime (94% yield) as a colorless solid which was used in the subsequent synthetic step without further purification.
To a solution of 6,7,8,9-tetrahydro-5H-benzo[7]annulen-5-one oxime (5.71 mmol, 1.00 g) in DMSO (9.00 mL) at r.t. was added KOH (17.1 mmol, 959 mg) and the reaction mixture was heated to 140 °C before 1,2-dichloroethane (11.4 mmol, 897 μL) in DMSO (2.00 mL) was added over 3 h via a syringe pump. The mixture was then cooled to r.t., quenched with 1M aqueous NH4CI solution (30.0 mL) and extracted with CH2CI2 (3 x 30.0 mL). The combined organics were dried (MgSO4) and concentrated under reduced pressure. Flash chromatography (hexanes → 9:1, hexanes/EtOAc) gave 262 mg of compound 18.1 (25% yield) as a yellow solid.
1H NMR (400 MHz, Chloroform-d) δ 8.18 (br s, 1H), 7.34 (dd, J = 7.8, 1.3 Hz, 1H), 7.25 - 7.19 (m, 1H), 7.16 (dd, J = 7.6, 1.6 Hz, 1H), 7.13 - 7.07 (m, 1H), 6.84 (t, J = 2.8 Hz, 1H), 6.17 (t, J = 2.8 Hz, 1H), 2.91 (t, J = 6.8 Hz, 2H), 2.86 - 2.80 (m, 2H), 2.07 - 1.98 (m, 2H); 13C NMR (101 MHz, Chloroform-d) δ 140.4, 131.8, 129.3, 126.8, 125.9, 125.2, 123.2, 121.8, 118.3, 111.1, 34.9, 27.8, 26.7. 4-(19,19-Difluoro-6,7,ll,12,13,19-hexahydro-5H-18A4,19A4- benzol3'4']cyclohepta[1'2'5]pyrrolo[1,2-c]benzo[3'4']cyclohepta[1'2'4 ,5]pyrrolo[2,1- f][l,3,2]diazaborinin-9-yl)-3,5-difluorophenol (18.2)
To a solution of compound 18.1 (1.36 mmol, 250 mg) and 2,6-difluoro-4-hydroxybenzaldehyde (0.650 mmol, 103 mg) in CH2CI2 (13.5 mL) was added pTsOH-H2O (0.065 mmol, 8 mg) and the reaction mixture was stirred at r.t. for 1 h. DDQ (0.780 mmol, 177 mg) was then added and the mixture was stirred at r.t. for 1 h. Triethylamine (3.90 mmol, 542 μL) was added, the mixture was stirred at r.t. for 1 h before BF3-OEt2 (5.85 mmol, 722 μL) was added and the mixture was stirred at r.t. for 1 h. More triethylamine (3.90 mmol, 542 μL and, after 30 min stirring at r.t., BF3-OEt2 (5.85 mmol, 722 μL) were added and the mixture was stirred at r.t. for further 1 h. It was then diluted with EtOAc (30.0 mL), washed with 3 M HCI (3 x 30.0 mL), dried (MgSO4) and concentrated under reduced pressure. Flash chromatography (toluene -> 19:1, toluene/EtOAc) gave 149 mg of compound 18.2 (42% yield) as a blue solid.
1H NMR (400 MHz, DMSO-d6) δ 7.73 (d, J = 7.4 Hz, 1H), 7.31 - 7.14 (m, 4H), 6.71 (s, 1H), 6.62 (d, J = 10.0 Hz, 1H), 2.47 - 2.40 (m, 2H), 2.28 - 2.04 (m, 2H), 1.90 - 1.83 (m, 3H).
Figure imgf000084_0001
4-(19,19-Difluoro-6,7,ll,12,13,19-hexahydro-5H-18λ4,19λ4- benzo[3,,4,]cyclohepta[l,,2,:4,5]pyrrolo[l,2-c]benzo[3',4,]cyclohepta[l,,2,:4,5]pyrrolo[2,l- f][l,3,2]diazaborinin-9-yl)-3,5-difluorophenyl-4-(tris(trifluoromethyl)perylen-3-yl)butanoate (RLE-18)
To a solution of compound 18.2 (0.091 mmol, 50 mg), 4-(4,9,10-tris(trifluoromethyl)perylen-3- yl)butanoic acid (0.099 mmol, 54 mg) and DMAP-pTsOH salt (0.091 mmol, 27 mg) in CH2CI2 (0.50 mL) was added DIC (0.364 mmol, 57 μL) and the reaction mixture was stirred at r.t. for 1 h. It was then filtered through celite and concentrated under reduced pressure. Flash chromatography (4:1, toluene/hexanes → toluene) gave 77 mg of RLE- 18 (78% yield) as a dark purple solid.
1H NMR (400 MHz, Chloroform-d) δ 8.28 - 8.01 (m, 7H), 7.85 - 7.77 (m, 1H), 7.37 - 7.28 (m, 4H), 7.25 - 7.12 (m, 4H), 7.01 - 6.89 (m, 2H), 6.59 - 6.51 (m, 2H), 3.44 - 3.31 (m, 2H), 2.92 - 2.78 (m,
2H), 2.67 - 2.56 (m, 4H), 2.41 - 2.21 (m, 6H), 2.08 - 1.99 (m, 4H).
Example 2.19 RLE-19
Figure imgf000085_0001
3,5-Dichloro-4-formylphenyl 4-(tris(trifluoromethyl)perylen-3-yl)butanoate (19.1)
To a solution of 2,6-dichloro-4-hydroxybenzaldehyde (0.335 mmol, 64 mg), 4- (tris(trifluoromethyl)perylen-3-yl)butanoic acid (0.369 mmol, 200 mg) and DMAP-pTsOH salt (0.034 mmol, 10 mg) in CH2CI2 (1.68 mL) was added DIC (1.34 mmol, 210 μL) and the reaction mixture was stirred at r.t. for 2 h. It was then filtered through celite and concentrated under reduced pressure. Flash chromatography (toluene) gave 187 mg of compound 19.1 (78% yield) as a yellow solid. 1H NMR (400 MHz, Chloroform-d) δ 10.50 - 10.33 (m, 1H), 8.48 - 7.50 (m, 8H), 7.19 - 7.14 (m, 2H), 3.45 - 3.25 (m, 2H), 2.83 - 2.59 (m, 2H), 2.33 - 2.03 (m, 2H).
3,5-Dichloro-4-(19,19-difluoro-6,7,ll,12,13,19-hexahydro-5H-18λ4,19λ4- benzo[3'4']cyclohepta[1'2'i4,5]pyrroloI[1,2-c]benzo[3'4'lcyclohepta[1'2'.4,5]pyrrol[2,1 - /][l,3,2]diazaborinin-9-yl)phenyl 4-(tris(trifluoromethyl)perylen-3-yl)butanoate (RLE-19)
To a solution of compound 19.1 (0.461 mmol, 84 mg) and compound 18.1 (0.210 mmol, 150 mg) in CH2CI2 (4.50 mL) was added pTsOH-H20 (0.021 mmol, 3 mg) and the reaction mixture was stirred at r.t. for 1 h. DDQ (0.252 mmol, 57 mg) was then added and the mixture was stirred at r.t. for 1 h. Triethylamine (1.26 mmol, 175 μL) was added, the mixture was stirred at r.t. for 1 h before BF3-OEt2 (1.89 mmol, 233 μL) was added and the mixture was stirred at r.t. for 2 h. It was then diluted with EtOAc (30.0 mL), washed with 3 M HCI (3 x 30.0 mL), dried (MgSCU) and concentrated under reduced pressure. Flash chromatography (4:1 toluene/hexanes -> toluene) gave 106 mg of RLE-19 (45% yield) as a purple solid.
1H NMR (400 MHz, Methylene Chloride-d2) δ 8.61 - 7.60 (m, 10H), 7.39 - 7.11 (m, 8H), 6.54 - 6.40 (m, 2H), 3.46 - 3.30 (m, 2H), 2.90 - 2.55 (m, 6H), 2.39 - 2.09 (m, 6H), 2.08 - 1.94 (m, 4H).
Example 2.20 RLE-20
Figure imgf000086_0001
4-(Tris(trifluoromethyl)perylen-3-yl)butanoyl chloride (20.1)
To a solution of 4-(tris(trifluoromethyl)perylen-3-yl)butanoic acid (0.500 mmol, 271 mg) in CH2CI2 (2.50 mL) was added DMF (1 drop) and oxalyl chloride (1.00 mmol, 86 μL) and the reaction mixture was stirred at r.t. for 1.5 h. All volatiles were removed under reduced pressure to give 252 mg of compound 20.1 (90% yield) as a yellow/brown solid. The material was of sufficient purity to use directly in the subsequent synthetic step.
6,6-Difluoro-13,15-dimethyl-14-(3-(4,9,10-tris(trifluoromethyl)perylen-3-yl)propyl)-12,16- dihydro-6H-5λ4,6λ4-indeno[2',1:4,5]pyrrolo[l,2-c]indeno[2',1:4,5]pyrrolo[2,l- /][l,3,2]diazaborinine (RLE-20)
To a solution of compound 20.1 (0.250 mmol, 140 mg) in CH2CI2 (0.50 mL) was added a solution of 3-methyl-l,4-dihydroindeno[l,2-b]pyrrole (0.550 mmol, 93 mg) in CH2CI2 (0.75 mL) at r.t. and the reaction mixture was stirred at r.t. for 2 h after which a second portion of 3-methyl-l,4- dihydroindeno[l,2-b] pyrrole (0.270 mmol, 45 mg) was added and the mixture stirred for further 1 h. Triethylamine (1.50 mmol, 208 μL) was added, the mixture was stirred at r.t. for 30 min before BF3-OEt2 (2.25 mmol, 278 μL) was added and the mixture was stirred at r.t. for 16 h. It was then diluted with EtOAc (10.0 mL), washed with 3 M HCI (3 x 10.0 mL), dried (MgSO4) and concentrated under reduced pressure. Flash chromatography (7:3 hexanes/toluene -> toluene) gave 29 mg of RLE-20 (13% yield) as a purple solid.
Example 3 Fabrication of Filter Layer
A glass substrate was prepared in substantially the following manner. A 1.1 mm thick glass substrate measuring 1-inch X 1-inch was cut to size. The glass substrate was then washed with detergent and deionized (Dl) water, rinsed with fresh Dl water, and sonicated for about 1 hour. The glass was then soaked in isopropanol (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 20 wt% solution of poly(methylmethacrylate) (PMMA) (average M.W. 120,000 by GPC from MilliporeSigma, Burlington, MA, USA) copolymer in cyclopentanone (99.9% pure) was prepared. The prepared copolymer was stirred overnight at 40 °C. [PMMA] CAS: 9011-14-7; [Cyclopentanone] CAS: 120-92-3 The 20% PMMA solution prepared above (4 g) was added to 3 mg of the photoluminescent complex made as described above in a sealed container and mixed for about 30 minutes. The PMMA/lumiphore solution was then spin coated onto a prepared glass substrate at 1000 RPM for 20 s and then 500 RPM for 5 s. The resulting wet coating had a thickness of about 10 pm. the samples were covered with aluminum foil before spin coating to protect them from exposure to light. Three samples each were prepared in this manner for each for Emission/FWHM and quantum yield. The spin coated samples were baked in a vacuum oven at 80 °C for 3 hours to evaporate the remaining solvent.
The 1-inch X 1-inch sample was inserted into a Shimadzu, UV-3600 UV-VIS- NIR spectrophotometer (Shimadzu Instruments, Inc., Columbia, MD, USA). All device operations were performed inside a nitrogen-filled glove-box. The resulting absorption/emission spectrum for PC-8 is shown in FIG.l, while the resulting absorption/emission spectrum for PC-33 is shown in FIG. 2.
The fluorescence spectrum of a 1-inch X 1-inch film sample prepared as described above was determined using a Fluorolog spectrofluorometer (Horiba Scientific, Edison, NJ, USA) with the excitation wavelength set at the respective maximum absorbance wavelength. The maximum emission and FWHM are shown in Table 1.
The quantum yield of a 1-inch X 1-inch sample prepared as described above were determined using a Quantarus-QY spectrophotometer (Hamamatsu Inc., Campbell CA, USA) was excited at the respective maximum absorbance wavelength. The results are reported in Table 1.
The results of the film characterization (absorbance peak wavelength, FWHM, and quantum yield) are shown in Table 1 below. Table 1.
Figure imgf000089_0001
Figure imgf000090_0001
Figure imgf000091_0001
Figure imgf000092_0001
Figure imgf000093_0001
Figure imgf000094_0001
PhotoStability test Procedure:
PMMA film with dye concentration 2x10-3M is used to evaluate photo stability of film. PMMA film used for stability is same film used for all optical property measurement, which was provided before. 90.0 ml of cyclopentanone were added to 30.0 g of polymethylmethacrylate (PMMA) polymer (Milipore-Sigma, St. Louis, MO, USA), and stirred for several days at 50 °C. The resulting substrate solution was cast on a pre-cleaned (washed with soap and water) glass substrate (1 inch by 1 inch by 1 inch) by a casting machine set at casting blade clearance of 200 microns. The casted film was kept under cover for 30 minutes after casting for an additional 30 minutes. The casted glass surface was then placed on a hot plate and baked at 120 °C for about 20 minutes.
Blue LED light (vendor: inspired LED) with emission peak at 465nm was used as light source. Blue LED strip was place in a 1 ''x 12" size U channel, a commercial diffuser film (vendor unknown) was place on top of the U channel in order to give uniform light distribution. Film with size G'cG' was place on top of diffuser. Average irradiance at film is approximately 1.5mW/cm2. Setup is at ambient environment.
Absorption at peak absorption wavelength is measured before and after film been exposure to LED light 165h, 330h and 500h respectively. Film absorption is measured by UV- vis 3600 (Shimadzu) Absorption remaining measured after each exposure time period divided by absorption before exposure indicates the photo stability of film.
Additive (LA-57) amount is 0.2 wt%.
Depends on 20% PMMA solution amount. If X ml PMMA solution is used to make dye solution. 0.4X mg additive was weighed and added into a 10ml vial. 100 microliter Toluene was added to dissolve additive, then solution containing additive was added to PMMA dye solution. Sonicate for 10 minutes.
(LA-57, purchased from vendor: Adeka, Ni(AcAc)2, DABCO both purchased from sigma Aldrich)
Figure imgf000095_0001
The results are depicted in the Table below:
Figure imgf000095_0002
Figure imgf000096_0001
The terms used in this disclosure and in the appended embodiments, (e.g., bodies of the appended embodiments) are generally intended as "open" terms (e.g., the term "including" should be interpreted as "including, but not limited to," the term "having" should be interpreted as "having at least," the term "includes" should be interpreted as "includes, but not limited to," etc.). In addition, if a specific number of elements is introduced, this may be interpreted to mean at least the recited number, as may be indicated by context (e.g., the bare recitation of "two recitations/' without other modifiers, means at least two recitations of two or more recitations). As used in this disclosure, any disjunctive word and/or phrase presenting two or more alternative terms should be understood to contemplate the possibilities of including one of the terms, either of the terms, or both terms. For example, the phase "A or B": will be understood to include the possibilities of "A" or "B" or "A and B."
The terms "a," "an," "the" and similar referents used in the context of describing the present disclosure (especially in the context of the following embodiments) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., "such as") provided herein is intended merely to better illuminate the present disclosure and does not pose a limitation on the scope of any embodiments. No language in the specification should be construed as indicating any non-embodied element essential to the practice of the present disclosure.
Groupings of alternative elements or embodiments disclosed herein are not to be construed as limitations. Each group member may be referred to and embodied individually or in any combination with other members of the group or other elements found herein. It is anticipated that one or more members of a group may be included in, or deleted from, a group for reasons of convenience and/or patentability. When any such inclusion or deletion occurs, the specification is deemed to contain the group as modified thus fulfilling the written description of all Markush groups used in the appended embodiments.
Certain embodiments are described herein, including the best mode known to the inventors for carrying out the present disclosure. Of course, variations on these described embodiments, will become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventor expects skilled artisans to employ such variations as appropriate, and the inventors intend for the present disclosure to be practiced otherwise than specifically described herein. Accordingly, the embodiments include all modifications and equivalents of the subject matter recited in the embodiments as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is contemplated unless otherwise indicated herein or otherwise clearly contradicted by context. In closing, it is to be understood that the embodiments disclosed herein are illustrative of the principles of the embodiments. Other modifications that may be employed are within the scope of the embodiments. Thus, by way of example, but not of limitation, alternative embodiments may be utilized in accordance with the teachings herein. Accordingly, the embodiments are not limited to the embodiments precisely as shown and described.

Claims

CLAIMS What is claimed is:
1. A photoluminescent complex comprising represented by a formula:
A — (L — D)1-3, wherein each D is a donor chromophore, wherein the donor chromophore absorbs light having a first wavelength in the blue light range and releases an excitation energy in response thereto, wherein the donor chromophore is:
Figure imgf000099_0001
wherein R8, R10 and R11 are independently H or CF3; wherein A is an acceptor chromophore, comprising a boron-dipyrromethene (BODIPY) derivative, wherein the acceptor chromophore absorbs the excitation energy released by the donor chromophore wherein the acceptor chromophore then emits a light of second wavelength that is longer than the first wavelength; and each L is a linker; and wherein the photoluminescent complex has an emission quantum yield greater than 80%.
2. The photoluminescent complex of claim 1, wherein:
A is:
Figure imgf000100_0001
wherein each R' is independently H, -CH3, F, or CF3;
R" is -H, or a bond connecting to L— D;
R1 and R2 are independently H or -CH3;
R3 and R4 are independently H, F, Br, -CF3, phenyl optionally substituted with 1 or 2 - CH3, -F, -CF3, or a bond connecting to L— D;
X is -CH2-, -CH2CH2-, -CH2CH2CH2-, -C(Ra)2-7 -CHC(Ra)-, -C(=O)-, -O-, -S-, -C(Ar)2- - C(CH2Ar)2-, a spiro-cycloalkane group, or an aromatic spiro-polycyclic group, wherein Ra is a C1-C4 alkyl and wherein Ar is an aryl group or a heteroaryl group; wherein at least one of R", R3 or R4 are a bond connecting to L— D; and
L is an optionally substituted C4-C7 ester or a C3-C5 keto ester.
3. The photoluminescent complex of claim 1 or 2, wherein when X is a spiro-cyclopentane.
4. The photoluminescent complex of claim 1, 2, or 3, wherein L is:
Figure imgf000100_0002
5. The photoluminescent complex of claim 1, 2, 3, wherein L is:
Figure imgf000101_0001
6. The photoluminescent complex of claim 1, 2, 3, 4, or 5, wherein the photoluminescent complex is:
Figure imgf000101_0002
Figure imgf000102_0001
Figure imgf000103_0001
Figure imgf000104_0001
Figure imgf000105_0001
7. A color conversion film comprising: a transparent substrate layer; and a color conversion layer, wherein the color conversion layer includes a resin matrix, and the photoluminescent complex of claim 1, 2, 3, 4, 5, or 6 dispersed within the resin matrix.
8. The color conversion film of claim 7, further comprising a singlet oxygen quencher.
9. The color conversion film of claim 7, further comprising a radical scavenger.
10. The color conversion film of claim 7, wherein the film has a thickness of between about 1 pm to about 200 pm.
11. The color conversion film of claim 7 , wherein the film absorbs blue light having a wavelength of 400 nm to 480 nm and emits red light having a wavelength of 575 nm to 650 nm.
12. The color conversion film of claim 11, wherein the film emits red light having a wavelength of 600 nm to 650 nm.
13. The color conversion film of claim 7, 8, 9, 10, 11, or 12, wherein the film has a photostability of at least 80% after being exposed to blue light at a peak wavelength of 465 nm for 165 hours.
14. The color conversion film of claim 7, 8, 9, 10, 11, 12, or 13, wherein the film has a photostability of at least 75% after being exposed to blue light at a peak wavelength of 465 nm for 330 hours.
15. A method for preparing the color conversion film of claim 7, 8, 9, 10, 11, 12, 13, or 14, comprising: applying a mixture onto the surface of a transparent substrate; wherein the mixture comprises a resin matrix and a photoluminescent complex of claim 1, 2, 3, 4, 5, or 6 dissolved within a solvent.
16. The method of claim 15, wherein the photoluminescent complex has an absorbance with a wavelength in the range of 400 nm to 480 nm, and an emission having a wavelength in the range of 575 nm to 650 nm.
17. The method of claim 15, wherein the mixture further comprises a radical scavenger that is dissolved within the solvent.
18. The method of claim 15, wherein the mixture further comprises a singlet oxygen quencher that is dissolved within the solvent.
19. A backlight unit comprising the color conversion film of claim 7, 8 ,9, 10, 11, 12, 13, or 14.
20. A display device comprising the backlight unit of claim 19.
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