WO2023049828A1 - Composés émissifs cycliques contenant du bore et film de conversion de couleur contenant ceux-ci - Google Patents

Composés émissifs cycliques contenant du bore et film de conversion de couleur contenant ceux-ci Download PDF

Info

Publication number
WO2023049828A1
WO2023049828A1 PCT/US2022/076912 US2022076912W WO2023049828A1 WO 2023049828 A1 WO2023049828 A1 WO 2023049828A1 US 2022076912 W US2022076912 W US 2022076912W WO 2023049828 A1 WO2023049828 A1 WO 2023049828A1
Authority
WO
WIPO (PCT)
Prior art keywords
mmol
plc
compound
dcm
added
Prior art date
Application number
PCT/US2022/076912
Other languages
English (en)
Inventor
Shijun Zheng
Jeffrey R. Hammaker
Xinliang DING
Peng Wang
Jie Cai
Hiep Luu
Tissa Sajoto
Original Assignee
Nitto Denko Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nitto Denko Corporation filed Critical Nitto Denko Corporation
Priority to CN202280036055.0A priority Critical patent/CN117396580A/zh
Priority to KR1020237039185A priority patent/KR20240065040A/ko
Publication of WO2023049828A1 publication Critical patent/WO2023049828A1/fr

Links

Classifications

    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/41—Organic pigments; Organic dyes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/55—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1022—Heterocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C09K2211/1055—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with other heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms
    • 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
    • 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
    • H01L33/507—Wavelength conversion elements the elements being in intimate contact with parts other than the semiconductor body or integrated with parts other than the semiconductor body

Definitions

  • LEDs Current light emitting diodes
  • a blue light source exciting a green phosphor, a red phosphor, or a yellow phosphor to obtain a white light source.
  • FWHM full width half maximum
  • the full width half maximum (FWHM) of the emission peak of the current green and red phosphors are quite large, usually greater than 40 nm, resulting in the green and red color spectrums overlapping and rendering colors that are not fully distinguishable from one another. This overlap leads to poor color rendition and the deterioration of the color gamut.
  • methods have been developed using films containing quantum dots in combination with LEDs.
  • quantum dots suffer from a variety of shortcomings including toxicity, low efficiency, expensive encapsulating processes and size uniformity.
  • Photoluminescent complexes described herein may be used to improve the contrast between distinguishable colors in televisions, computer monitors, smart devices, and any other device that utilize color displays.
  • Photoluminescent complexes of the present disclosure include a color converting dye complex 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, longer wavelength than the first wavelength.
  • the photoluminescent complexes disclosed herein can be utilized with a color conversion film for use in light emitting apparatuses.
  • the color conversion film of the present disclosure reduced color deterioration by reducing overlap within the color spectrum, resulting in high quality color rendition.
  • Some embodiments include a photoluminescent complex, wherein the photoluminescent complex may comprise: a blue light absorbing naphthalimide derivative; a linker complex comprising an unsubstituted ester, substituted ester, unsubstituted ether, or substituted ether; and a ring-locked boron-dipyrromethene (BODIPY) moiety.
  • the linker complex may covalently link the naphthalimide derivative to the ring-locked BODIPY moiety.
  • the ring-locked BODIPY moiety absorbs the energy of a first excitation wavelength from the naphthalimide derivative and emits a light energy of a second higher wavelength.
  • the photoluminescent complex has an emission quantum yield greater than 80%.
  • the photoluminescent complex can have an emission band with a full width half maximum [FWHM] of up to 40 nm.
  • the photoluminescent complex can have a Stokes shift, the difference between the excitation peak of the blue light absorbing moiety and the emission peak of the BODIPY moiety, of equal to or greater than 45 nm.
  • a color conversion film wherein the color conversion film may comprise: a transparent substrate layer; a color conversion layer, wherein the color conversion layer includes a resin matrix; and at least one photoluminescent complex, as described herein, dispersed within the resin matrix.
  • the color conversion film may have a thickness between 1 ⁇ m to about 200 ⁇ m.
  • the color conversion film of the present disclosure can absorb blue light in the 400 nm to about 480 nm range and emit light in the 510 nm to about 560 nm wavelength range.
  • Another embodiment includes a color conversion film that can absorb blue light in the 400 nm to about 480 nm range and emit light in the 580 nm to about 670 nm wavelength range.
  • the color conversion film can further comprise a transparent substrate layer.
  • the transparent substrate layer may comprise of two opposing surfaces, wherein the color conversion layer is disposed on one of the opposing surfaces.
  • the color conversion film may further comprise a singlet oxygen quencher.
  • the color conversion film may further comprise a radical scavenger.
  • Many embodiments include a method for preparing the color conversion film, the method comprising: dissolving a photoluminescent complex, as described herein, and a binder resin within a solvent; and applying the mixture on one of the opposing surfaces of the transparent substrate.
  • Some embodiments include a backlight unit including a color conversion film described herein.
  • FIG.1 is a graph depicting the absorption and emission spectra of one embodiment of a photoluminescent complex (PLC-1).
  • FIG.2 is a graph depicting the absorption and emission spectra of one embodiment of a photoluminescent complex (PLC-2).
  • FIG.3 is a graph depicting the absorption and emission spectra of one embodiment of a photoluminescent complex (PLC-3).
  • the current disclosure is related to photoluminescent complexes for use in color conversion films, backlight units, and display devices including the same.
  • 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 can both enhance the transmission of a desired first emissive bandwidth and decrease the transmission of a second emissive bandwidth.
  • the present disclosure describes a photoluminescent complex that can enhance the contrast or intensity between two colors, increasing their distinction from one another.
  • BODIPY boron-dipyrromethene
  • BODIPY complexes may have a narrow FWHM, high fluorescent efficiency, stability to both moisture and oxygen, and low production cost.
  • Current BODPY strategies have some shortcomings, such as low absorption of blue LED light, e.g., 450 nm, resulting in inefficient conversion of blue LED light to green and red light, and broad FWHM when used in color converting films.
  • the BODIPY compounds disclosed herein overcome these limitations.
  • the compound or chemical structure when referred to as being “substituted”, the compound or structure may include one or more substituents.
  • a substituted group is derived from the unsubstituted parent structure wherein one or more hydrogen atoms on the parent structure have been independently replaced by one or more substituent groups.
  • the substituent groups may independently be F, Cl, Br, I, C 0-7 H 1-15 O 1-2 N 0-2 , C 0-7 H 1-15 O 0-2 N 1-2 , optionally substituted alkyl (including unsubstituted alkyl, such as methyl, ethyl, C3 alkyl, C4 alkyl, etc., fluoroalkyl, e.g. CF3, etc.), alkenyl, or a C3-7 heteroalkyl.
  • alkyl group refers to a hydrocarbon group that is free of double or triple carbon-carbon bonds, and includes linear, branched, or cyclic alkyl.
  • alkyne moiety refers to a group that has at least one carbon-carbon triple bond (-C ⁇ C-), and includes linear, branched, or cyclic alkyne moieties.
  • the alkyl moiety may have 1 to 6 carbon atoms (whether it appears herein, a numerical range such as “1 to 6” refers to each integer in the given range: e.g., “1 to 6 carbon atoms” meaning that the alkyl group may have 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc., up to and including 6 carbon atoms, although the present definition also covers the occurrence of the term “alkyl” where no numerical range is designated.
  • the alkyl group of the compound designated herein may be designated as “C1-6 alkyl” or similar designations.
  • C 1-6 alkyl indicates that there are 1 to 6 carbon atoms in the alkyl chain, i.e., the alkyl chain is methyl, ethyl, propyl, isopropyl, n- butyl, iso-butyl, sec-butyl, or t-butyl, etc.
  • C1-6 alkyl includes, for example, C1-2 alkyl, C3-4 alkyl, C 4-5 alkyl, or C 5-6 alkyl.
  • Alkyl groups can 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.
  • Typical alkene groups include, but are not limited to, ethenyl, propenyl, butenyl, etc.
  • heteroalkyl refers to an alkyl group, as defined herein, in which one or more of the constituent carbon and/or hydrogen atoms have been replaced by a nitrogen, oxygen, or sulfur. Examples include, but are not limited to, -CH2-O-CH3, -CH2- CH2- O-CH 3 , - CH 2 -N(CH 3 )-CH 3 , - CH 2 -CH 2 -NH-CH 3 , - CH 2 -CH 2 -N(CH 3 )-CH 3 , - CH 2 -S- CH 2 -CH 3 , - CH 2 -NH- O-CH 3 , etc.
  • aromatic refers to a planar ring having a delocalized ⁇ -electron system containing 4n+2 ⁇ electrons, where n is an integer. Aromatic rings can be formed from five, six, seven, eight, nine, or more than nine atoms. Aromatic rings can be optionally substituted.
  • aromatic includes both carbocyclic aryl (e.g., phenyl) and heterocyclic aryl (or “heteroaryl” or “heteroaromatic”) group (e.g., pyridine).
  • the term includes monocyclic or fused-ring polycyclic (i.e., rings which share adjacent pairs of carbon atoms) groups.
  • hydrocarbon ring refers to a monocyclic or polycyclic ring system that contains only carbon and hydrogen and may be saturated.
  • Monocyclic carbon rings include groups having from 3 to 12 carbon atoms.
  • Illustrative examples of monocyclic groups include the following moieties:
  • Illustrative examples of polycyclic groups include the following moieties: [bicycloheptane], [bicycloheptane], , ,
  • aryl as used herein means an aromatic ring wherein each of the atoms forming the ring is a carbon atom.
  • Aryl rings can be formed by five, six, seven, eight, or more than eight carbon atoms.
  • Aryl groups can be substituted or unsubstituted. Examples of aryl groups include, but are not limited to, phenyl, naphthalenyl, phenanthrenyl, etc.
  • heteroaryl refers to an aryl group that includes one or more ring heteroatoms selected from nitrogen, oxygen, sulfur, or a combination thereof, wherein the heteroaryl group has from 4 to 10 atoms in its ring system and with the proviso that the ring of the group does not contain two adjacent nitrogen, oxygen or sulfur atoms. It is understood that the heteroaryl ring can have additional heteroatoms in the ring. In heteroaryls that have two or more heteroatoms, those two or more heteroatoms can be the same or different from one another. Heteroaryls can be optionally substituted.
  • 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 as used herein means fluorine, chlorine, bromine, and iodine.
  • bond”, “bonded”, “direct bond” or “single bond” as used herein means a chemical bond between two atoms.
  • 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.
  • ester refers to a chemical moiety with the formula -COOR, where R is alkyl, cycloalkyl, aryl, heteroaryl (bonded through a ring carbon) or heterocyclic (bonded through a ring carbon). Any hydroxy, or carboxyl side chain on the compounds described herein can be esterified. The procedures and specific groups to make such ester may be any suitable method and can readily be found in reference sources.
  • ether refers to a chemical moiety that contains an oxygen atom connected to two alkyl or aryl groups with the general formula of R-O-R’, where the term alkyl and aryl is as defined herein.
  • ring-locked refers to a chemical structure wherein one or more series of atoms in a compound are connected to form a ring.
  • Rings may vary in size from three to many atoms (e.g., aromatic, carbocyclic rings).
  • BODIPY refers to a chemical moiety with the formula:
  • the BODIPY may be composed of dipyrromethene complexed with a di-substituted boron atom, typically a BF2 unit.
  • the IUPAC name for the BODIPY is 4,4-difluoro-4-bora-3a,4a-diaza- s-indacene.
  • naphthalimide or “naphthalimide derivative” as used herein, refers to a chemical moiety with the formula: .
  • the present disclosure related to photoluminescent complexes that absorb light energy of first wavelength and emit light energy in a second higher wavelength.
  • the photoluminescent complex of the present disclosure comprises an absorbing luminescent moiety and an emitting luminescent moiety that are coupled through a linker such that their distance is adjusted for the absorbing luminescent moiety to transfer its energy to the acceptor luminescent moiety, wherein the acceptor luminescent moiety then emits out at a second wavelength that is larger than the absorbing first wavelength.
  • Some embodiments include a photoluminescent complex.
  • the complex comprises: a blue light absorbing donor chromophore, wherein the donor chromophore comprises a naphthalimide derivative; a linker complex; and a ring-locked boron-dipyrromethene (BODIPY) moiety.
  • the linker complex can covalently link the naphthalimide derivative to the ring-locked BODIPY moiety.
  • the naphthalimide derivative absorbs light of a first excitation wavelength and transfers energy to the ring-locked BODIPY moiety, wherein the ring-locked BODIPY moiety then emits a light energy of a second wavelength.
  • the photoluminescent complex can have a high emission quantum yield. In some embodiments, the emission quantum yield can be greater than 50%, 60%, 70%, 80%, and/or 90%.
  • the emission quantum yield can be greater than 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95%.
  • Emission quantum yield can be measured by dividing the number of photons emitted by the number of photons absorbed, which is equivalent to the emission efficiency of the luminescent moiety.
  • the absorbing luminescent moiety may have an emission quantum yield greater than 80%.
  • the quantum yield can be greater than 0.8 (80%), 0.81 (81%), 0.82 (82%), 0.83 (83%), 0.84 (84%), 0.85 (85%), 0.86 (86%), 0.87 (87%), 0.88 (88%), 0.89 (89%), 0.9 (90%), 0.91 (91%), 0.92 (92%), 0.93 (93%), 0.94 (94%), 0.95 (95%), 0.96 (96%), 0.97 (97%), 0.98 (98%), and may be up to nearly 100%.
  • Quantum measurements in film can be made by spectrophotometer, e.g., Quantaurus-QY spectrophotometer (Hamamatsu, Inc., Campbell, CA, USA).
  • the photoluminescent complex has an emission band, wherein the emission band may have a full width half maximum (FWHM) of less than 40 nm.
  • the FWHM is the width of the emission band in nanometers at the emission intensity that is half of the maximum emission intensity for the band.
  • the photoluminescent complex has an emission band FWHM value that is less than or equal to about 35 nm, less than or equal to about 30 nm, less than or equal about 25 nm, or less than or equal to about 20 nm.
  • the FWHM is about 40 nm to about 35 nm, about 35 nm to about 30 nm, about 30 nm to about 25 nm, about 25 nm to about 20 nm, or less than about 20 nm.
  • the photoluminescent complex can have a Stokes shift that is equal to or greater than 45 nm.
  • Stokes shift means the distance between the excitation peak of the blue light absorbing moiety and the emission peak of the BODIPY moiety. In some embodiments, the Stokes shift is at least 45 nm.
  • the Stokes shift of photoluminescent complex can be about 45-50 nm, about 50-55 nm, about 55-60 nm, about 60-65 nm, about 65-70 nm, about 70-75 nm, about 75-80 nm, about 80-85 nm, about 85-90 nm, about 90-95 nm, about 95-100 nm, or greater than about 100 nm, or any number in a range bounded by any of these values.
  • the blue light absorbing moiety can have a peak absorption maximum between about 400 nm to about 480 nm wavelength.
  • the peak absorption wavelength may be between about 400 nm to about 405 nm, about 405-410 nm, about 410-415 nm, about 415-420 nm, about 420-425 nm, about 425-430 nm, about 430- 435 nm, about 435-440 nm, about 440-445 nm, about 445-450 nm, about 450-455 nm, about 455-460 nm, about 460-465 nm, about 465-470 nm, about 470-475 nm, about 475-480 nm or any wavelength in a range bounded by any of these values.
  • the blue light absorbing moiety can have red/orange absorption with a peak absorption maximum between about 580 nm to about 650 nm wavelength.
  • the peak absorption can be in the range of about 580 to about 585 nm, about 585-590 nm, about 590-595 nm, about 595-600 nm, about 600-605 nm, about 605-610 nm, about 610-615 nm, about 615-620 nm, about 620-625 nm, about 625-630 nm, about 630-635 nm, about 635-640 nm, about 640-645 nm, about 645-650 nm, or any wavelength in a range bounded by any of these values.
  • the photoluminescent complex can have an emission peak between about 590 nm and about 660 nm.
  • the emission peak can be between about 590 nm to about 595 nm, about 595-600 nm, about 600-605 nm, about 605- 610 nm, about 610-615 nm, about 615-620 nm, about 620-625 nm, about 625-630 nm, about 630-635 nm, about 635-640 nm, about 640-645 nm, about 645-650 nm, about 650-655 nm, about 655-660 nm, or any wavelength in a range bounded by any of these values.
  • photoluminescent complexes wherein the blue light absorbing naphthalimide derivative and the BODIPY moiety’s spatial distance is adjusted through the linker complex for improved transfer of the blue light absorbing naphthalimide derivative’s energy to the BODIPY moiety.
  • the present disclosure describes a photoluminescent complex (PLC), comprising a blue light absorbing naphthalimide derivative, a linker complex, and a ring-locked BODIPY moiety.
  • the linker complex covalently links the blue light absorbing naphthalimide derivative and the ring-locked BODIPY moiety.
  • the naphthalimide derivative absorbs light energy of a first excitation wavelength and transfers an energy to the ring-locked BODIPY moiety, wherein the ring-locked BODIPY moiety absorbs the energy from the naphthalimide derivative and emits a light energy of a second higher wavelength.
  • the photoluminescent complex has an emission quantum yield greater than 80%.
  • the linker complex covalently links the blue absorbing naphthalimide derivative with the ring-locked BODIPY moiety.
  • the linker complex can be tuned to adjust the spatial distance between the blue light absorbing naphthalimide derivative and the ring-locked BODIPY moiety.
  • the quantum yield may be tuned.
  • the distance separating the blue light absorbing naphthalimide derivative and the ring-locked BODIPY moiety can be about 8 ⁇ or less.
  • the linker complex can maintain a distance between the blue light absorbing naphthalimide derivative and the ring-locked BODIPY moiety.
  • the photoluminescent complex comprises a linker complex (L), wherein the linker complex covalently links the blue light absorbing naphthalimide derivative to the ring-locked BODIPY moiety.
  • the linker complex can comprise a single bond between the naphthalimide derivative and the ring-locked BODIPY moiety.
  • the linker complex may comprise an unsubstituted ester, a substituted ester, an unsubstituted ether, or a substituted ether.
  • the linker complex can comprise an optically substituted C 2-7 ester group.
  • Some examples include a linker complex comprising a substituted ester group, wherein the linker complex can be selected from among one of the following structures: r
  • the linker complex may comprise an unsubstituted ester group. When the linker complex comprises an unsubstituted ester group, the linker complex
  • the linker complex may comprise a unsubstituted and/or substituted ether.
  • the linker complex comprises a unsubstituted and/or substituted
  • the photoluminescent complex of the current disclosure can comprise a ring-locked BODIPY moiety.
  • the ring-locked BODIPY moiety can have the following general formula:
  • R1 and R2 may be a H or a C1-3 alkyl. In some embodiments, R1 and R2 may be a substituted aryl moiety, wherein the substituents on the aryl moiety may be a C 1-6 alkyl. In some embodiments, R 3 and R 4 may be a H, F, Br, or -CF3. In some embodiments, R5 and R6 may be a H, halide, e.g., -F, -Cl and / or - Br, a C1-C3 alkyl group, e.g., -CH3, a C1-C3 alkoxy, e.g., -OCH3.
  • X may be an C 1 -C 3 alkyl group, e.g., -CH 2 -; -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, or a spiro-cycloalkane group.
  • R1 is H.
  • R1 is C1-3 alkyl.
  • R 2 is H.
  • R2 is C1-3 alkyl.
  • R 1 and R 2 are H.
  • R1 and R2 are C1-3 alkyl.
  • R1 is a substituted aryl moiety, e.g., phenyl, wherein the substituents on the aryl moiety, e.g., phenyl, may be a C 1-6 alkyl.
  • R 2 is a substituted aryl moiety, e.g., phenyl, wherein the substituents on the aryl moiety, e.g., phenyl, may be a C1-6 alkyl.
  • R 1 and R 2 are substituted aryl moieties, e.g., phenyl, wherein the substituents on the aryl moiety, e.g., phenyl, may be a C1-6 alkyl.
  • R3 is H. In some embodiments, R 3 is F. In some embodiments, R3 is Br. In some embodiments, R3 is -CF3. In some embodiments, R 4 is H. In some embodiments, R 4 is F. In some embodiments, R4 is Br. In some embodiments, R4 is -CF3. In some embodiments, R 3 and R 4 are H. In some embodiments, R3 and R4 are F. In some embodiments, R3 and R4 are Br.
  • R 3 and R 4 are -CF 3 .
  • R5 is H. In some embodiments, R5 is -F. In some embodiments, R 5 is -Cl. In some embodiments, R5 is -Br. In some embodiments, R5 is a C1-C3 alkyl group. In some embodiments, R 5 is -CH 3 . In some embodiments, R5 is a C1-C3 alkoxy. In some embodiments, R 5 is -OCH 3 .
  • R 6 is H. In some embodiments, R6 is -F. In some embodiments, R 6 is -Cl. In some embodiments, R 6 is -Br.
  • R6 is a C1-C3 alkyl group. In some embodiments, R 6 is -CH 3 . In some embodiments, R 6 is a C 1 -C 3 alkoxy. In some embodiments, R6 is -OCH3. In some embodiments, R 5 and R 6 are H. In some embodiments, R5 and R6 are -F. In some embodiments, R5 and R6 are -Cl. In some embodiments, R 5 and R 6 are -Br. In some embodiments, R5 and R6 are a C1-C3 alkyl group. In some embodiments, R5 and R6 are -CH3. In some embodiments, R 5 and R 6 are a C 1 -C 3 alkoxy.
  • R5 and R6 are -OCH3. In some embodiments, R 5 and R 6 may be a H, -CH 3 , Cl, F, or OCH 3 .
  • X is a C1-C3 alkyl group. In some embodiments, X is -CH2. In some embodiments, X is -CH 2 CH 2 -. In some embodiments, X is -CH2CH2CH2-. In some embodiments, X is a spiro-cycloalkane group.
  • L is an unsubstituted ester. In some embodiments, L is a substituted ester. In some embodiments, L is an unsubstituted ether.
  • L is a substituted ether.
  • Many embodiments include a blue light absorbing naphthalimide derivative (Z), wherein the blue light absorbing naphthalimide derivative may be of the following general formula: wherein Y may be an oxygen (O) or a sulfur (S).
  • R7 and /or R8 may be a hydrogen (H), a substituted or unsubstituted aryl, or a - CF 3 .
  • R 9 may be a H, a substituted or unsubstituted aryl, a C 1 - 5 alkylaryl, a substituted or unsubstituted arylcarboxylic acid (such as p-CO2-t-Bu-phenyl), or there is no substitution for R9.
  • Y is oxygen (O).
  • Y is sulfur (S).
  • R7 is H.
  • R 7 is a substituted aryl.
  • R7 is unsubstituted aryl.
  • R7 is -CF3.
  • R 8 is H.
  • R8 is a substituted aryl.
  • R8 is unsubstituted aryl. In some embodiments, R 8 is -CF 3 . In some embodiments, R7 and R8 are H. In some embodiments, R7 and R8 are substituted aryl. In some embodiments, R 7 and R 8 are unsubstituted aryl. In some embodiments, R7 and R8 are -CF3. In some embodiments, R9 is H. In some embodiments, R 9 is substituted aryl. In some embodiments, R9 is unsubstituted aryl. In some embodiments, R9 is C1-5 alkylaryl. In some embodiments, R 9 is a substituted arylcarboxylic acid.
  • R9 is an unsubstituted arylcarboxylic acid. In some embodiments, R 9 is p-CO 2 -t-Bu-phenyl.
  • the photoluminescent complex of the present disclosure may be represented by the following structures which are provided for purpose of illustration only, and are in no way to be construed as limiting:
  • the photoluminescent complex comprises a blue light absorbing naphthalimide derivative.
  • the blue light absorbing naphthalimide derivative can comprise an organic lumiphore.
  • the blue light absorbing moiety can have a peak absorption maximum between about 400 nm to about 480 nm wavelength. In some embodiments, the peak absorption can be at least about 400 nm, 410 nm, 420 nm, 430 nm, 440 nm, 450 nm, or 460 nm.
  • the peak absorption can be less than about 410 nm, 420 nm, 430 nm, 440 nm, 450 nm, and 460 nm, 470 nm, or 480 nm.
  • the photoluminescent complex can have an absorbance maximum peak of about 450 nm.
  • the blue light absorbing naphthalimide derivative can have a maximum peak absorbance of about 410 nm and a lowest max absorbance peak of about 400 nm. Still, in many embodiments, the blue light absorbing naphthalimide derivative can have a maximum peak absorbance of about 480 nm.
  • Some embodiments include a color conversion film, wherein the color conversion film comprises: a color conversion layer wherein the color conversion layer includes a resin matrix and a photoluminescent complex described above, dispersed within the resin matrix.
  • the color conversion film can comprise one or more of the photoluminescent complexes described herein.
  • Some embodiments include the color conversion film which may be about 1 ⁇ m to about 200 ⁇ m thick.
  • the color conversion film can be described as being about 1 ⁇ m to about 5 ⁇ m thick, about 5 ⁇ m to about 10 ⁇ m thick, about 10 ⁇ m to about 15 ⁇ m thick, about 15 ⁇ m to about 20 ⁇ m thick, about 20 ⁇ m to about 40 ⁇ m thick, about 40 ⁇ m to about 80 ⁇ m thick, about 80 ⁇ m to about 120 ⁇ m thick, about 120 ⁇ m to about 160 ⁇ m thick, about 160 ⁇ m to about 200 ⁇ m thick, or any thickness bounded by the ranged above.
  • the color conversion film can absorb light in the range of about 400 nm to about 480 nm wavelength and can emit light in the range of about 590 nm to about 660 nm.
  • the color conversion film can further comprise a transparent substrate layer.
  • the transparent substrate layer has two opposing surfaces, wherein the color conversion layer can be disposed on and in physical contact with the surfaces of the transparent layer that will be adjacent to a light emitting source.
  • the transparent substrate is not particularly limited and one skilled in the art would be able to choose a transparent substrate from those used in the art.
  • transparent substrates include PE (polyethylene), PP (polypropylene), PEN (polyethylene naphthalate), PC (polycarbonate), PMA (polymethylacrylate), PMMA (polymethylmethacrylate), CAB (cellulose acetate butyrate), PVC (polyvinylchloride), PET (polyethyleneterephthalate), PETG (glycol modified polyethylene terephthalate), PDMS (polydimethylsiloxane), COC (cyclo olefin copolymer), PGA (polyglycolide or polyglycolic acid), PLA (polyactic acid), PCL (polycaprolactone), PEA (polyethylene adipate), PHA (polyhydroxy alkanoate), PHBV (poly(3- hydroxybutyrate-co-3-hydroxyvalerate)), PBE (polybutylene terephthalate), PTT (polytrimethylene terephthalate).
  • PE polyethylene
  • PP
  • the transparent substrate may have two opposing surfaces.
  • the color conversion film may be disposed on and in physical contact with one of the opposing surfaces.
  • the side of the transparent substrates without color conversion film disposed thereon may be adjacent to a light source.
  • the substrate may function as a support during the preparation of the material of the color conversion film.
  • the type of substrates used are not particularly limited, and the material and/or thickness is not limited, as long as it is transparent and capable of functioning as a support. A person skilled in the art could determine which material and thickness to use as a supporting substrate.
  • Some embodiments include a method for preparing the color conversion film, wherein the method comprises: dissolving a photoluminescent compound described herein, and a binder resin within a solvent; and applying the mixture on to the surface of a transparent substrate.
  • the binder resin which may be used with the photoluminescent complex(es) includes resins, such as acrylic reins, polycarbonate resins, ethylene-vinyl alcohol copolymer resins, ethylene-vinyl acetate copolymer resins, and saponification products thereof, AS resins, polyester resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins, polyvinylphosphonic acid (PVPA), polystyrene resins, phenolic resins, phenoxy resins, polysulfone, nylon, cellulosic resins, and cellulose acetate resins.
  • resins such as acrylic reins, polycarbonate resins, ethylene-vinyl alcohol copolymer
  • the binder resin can be a polyester resin and/or acrylic resin.
  • the solvent which may be used for dissolving or dispersing the complex and the resin may include an alkane, such as butane, pentane, hexane, heptane, and octane; cycloalkanes, such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane; alcohols, such as ethanol, propanol, butanol, amyl alcohol, hexanol, heptanol, octanol, decanol, undecanol, diacetone alcohol, and furfuryl alcohol; Cellosolves TM , such as Methyl Cellosolve TM , Ethyl Cellosolve TM , Butyl Cellosolve TM , Methyl Cellosolve TM acetate, and Ethyl Cello
  • Some embodiments include a backlight unit.
  • the backlight unit may include the aforementioned color conversion film comprising the photoluminescent complex(es) described herein.
  • Other embodiments may include a display device, wherein the device may include the backlight unit described herein.
  • each numerical parameter should at least be construed in light of the number of reported significant digits and by applying conventional and ordinary rounding techniques.
  • the functions performed in the process and methods may be implemented in differing order, as may be indicated by context.
  • 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, other different components. Such depicted architectures are merely examples, and many other architectures can be implemented to achieve the same or similar functionality.
  • any disjunctive word and/or phrase presenting two or more alternative terms should be understood to contemplate the possibilities of including one of those terms, either of the terms, or both terms.
  • the phrase “A or B” will be understood to include the possibilities of “A” or “B” or “A and B”.
  • the phrase “A and/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 are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context.
  • a photoluminescent complex comprising: a blue light absorbing donor chromophore, wherein the donor chromophore comprises a naphthalimide derivative; a linker complex; and a ring-locked boron-dipyrromethene (BODIPY) moiety; wherein the linker complex covalently links the donor chromophore with the naphthalimide derivative and the ring-locked BODIPY moiety, wherein the naphthalimide derivative absorbs blue light energy of a first excitation wavelength and transfers an energy to the ring-locked BODIPY moiety, wherein the ring-locked BODIPY moiety absorbs the energy from the naphthalimide derivative and emits a light energy of a second higher wavelength, and wherein the photoluminescent complex has an emission quantum yield greater than 80%.
  • Embodiment 2 The photoluminescent complex of embodiment 1, wherein the naphthalimide derivative of the donor chromophore is of the general formula: wherein Y is selected from a oxygen (O) or a sulfur (S); wherein R7 and R8 are independently selected from a hydrogen (H), a substituted or unsubstituted aryl, or a - CF 3 ; and wherein R 9 is independently selected from a hydrogen (H), a substituted or unsubstituted aryl, a C1-C5 alkyl, or there is no substitution for R9.
  • the photoluminescent complex of embodiment 1, wherein the ring-locked BODIPY moiety is of the general formula: wherein R 1 and R 2 are independently selected from a H or a C1-C3 alkyl; wherein R3 and R4 are independently selected from a H, F, Br, -CF3, or a bonding connecting to L—Z; wherein R5 and R6 are independently selected from a H, C1-C3 alkyl group, halide, or C 1 -C 3 alkoxy; and wherein X is independently selected from a C 1 -C 3 alkyl group, - CH2CH2-, -CH2CH2CH2-, or a spiro-cychloalkane group.
  • Embodiment 5. The photoluminescent complex of embodiment 3, wherein Z is a donor chromophore comprising the naphthalimide derivative.
  • Embodiment 6. The photoluminescent complex as in embodiments 1 or 4, wherein the linker complex is a unsubstituted ester; wherein the unsubstituted ester comprises one of the following .
  • Embodiment 8 The photoluminescent complex as in embodiments 1 or 4, wherein the linker complex is a unsubstituted and/or substituted ether; wherein the unsubstituted and/or substituted ether comprises one of the following structures: , , r .
  • Embodiment 10 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 complex is comprised of the photoluminescent complexes as in embodiments 1, 2, 3, 4, 5, 6, 7, 8, or 9 dispersed within the resin matrix.
  • Embodiment 11 The color conversion film of embodiment 10, further comprising a singlet oxygen quencher.
  • Embodiment 12 The color conversion film of embodiment 10, further comprising a radical scavenger.
  • Embodiment 13 The color conversion film of embodiment 10, wherein the film has a thickness between 10 ⁇ m and 200 ⁇ m.
  • Embodiment 15 A method for preparing the color conversion film as in embodiments 10, 11, 12, 13, or 14, the method comprising: dissolving the photoluminescent complexes as in embodiments 1, 2, 3, 4, 5, 6, 7, 8, or 9, and a binder resin within a solvent; and applying the mixture to one of the transparent substrates opposing surfaces.
  • Embodiment 16. A backlight unit including the color conversion film as in embodiments 10, 11, 12, 13, or 14.
  • a display device including the backlight unit of embodiment 16.
  • Ex-1 A mixture of 1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione (100mg, 0.347 mmol), 2-(4-aminophenyl)acetic acid (135mg, 0.9 mmol) in 5mL DMF was heated at 165 oC for 2 hrs in microwave reactor. After cooled to 50 oC, to the resulted solution, 1.5 mL acetone was added dropwise to form yellow precipitate, which was collected by filtration and washed with acetone, dried in air to give a yellow solid (88mg, in 61% yield).
  • Ex-3.1 To a mixture of compound Ex-1.3 (290mg, 1.0mmol) in ortho-dichlorobenzene (30mL), was added bromine (1.98g, 12 mmol). The mixture was heated at 75 oC for 30 hrs. After cooled to room temperature, the solid was collected by filtration, dried in air to give 290mg yellow solid as desired product. The filtrate was loaded on silica gel and purified by flash chromatography using eluents of hexanes/dichloromethane (50% ⁇ 100% dichloromethane). The desired fraction was collected and removal of solvents to give 110mg yellow solid. Total product of 400 mg was obtained in 89.7% yield.
  • Ex-3.2 A mixture of compound Ex-3.1 (190mg, 0.426mmol), 4-(4- aminophenyl)butanoic acid (180 mg, 0.64 mmol), 4-(N,N-dimethylamino)-pyridine (4 mg) in anhydrous N,N-dimethylformamide (DMF) (4mL) was heated at 165 oC for 2.5 hrs. After the mixture was cooled to room temperature and let stand overnight, the solid was collected by filtration, which was washed with acetone and dried in vacuum oven at 90 oC for 1hr to give a yellow solid (220mg, in 84.5% yield).
  • Ex-3 A mixture of compound Ex-3.2 (100 mg, 0.165 mmol), (3,5- bis(trifluoromethyl)phenyl)boronic acid (170 mg, 0.66 mmol), Pd(dppf)Cl2 (20 mg, 0.027 mmol) and potassium carbonate (138 mg, 1 mmol) in THF/water (5 mL/0.5 mL) was degassed then heated at 80 oC for 2hrs. After cooled to room temperature, the precipitate was collected by filtration, washed with acetone, then dried in vacuum oven at 90 oC for 2hrs. A yellow solid was obtained (142mg, in 94% yield).
  • Ex-4.1 A mixture of 4-bromo-1,8-naphthalic anhydride (2.77 g, 10 mmol), 4-bromo-2- nitrophenol (3.27 g, 15 mmol) was degassed under vacuum for 30 min, then anhydrous NMP (50 mL) was added, followed by addition of sodium hydroxide (0.2 g, 5 mmol) and copper powder (0.318 g, 5 mmol). The mixture was sparged with argon for 20 min, then heated at 180 oC overnight under argon atmosphere. After the mixture is cooled down to room temperature, to the solution, 50 mL 20% hydrochloride acid aqueous solution was added dropwise, then added 50 mL water.
  • Ex-4 A mixture of compound Ex-4.4 (385 mg, 0.729 mmol), phenylboronic acid (178 mg, 1.45 mmol), Pd(dppf)Cl2 (36 mg, 0.05 mmol), potassium carbonate (276 mg, 2 mmol) in cosolvents of THF/DMF/water (20L/4mL/2mL) was degassed, then heated at 80 oC for overnight. The mixture was worked up with 200 mL ethyl acetate and 50 mL 0.6 N hydrochloric acid aqueous solution. The aqueous phase was extracted with ethyl acetate (100 mL x 2).
  • Example 5 (Ex-5) Ex-5: A mixture of compound Ex-4.4 (385 mg, 0.729 mmol), 3,5-bis- (trifluoromethyl)phenylboronic acid (374 mg, 1.45 mmol), Pd(dppf)Cl2 (36 mg, 0.05 mmol), potassium carbonate (276 mg, 2 mmol) in cosolvents of THF/DMF/water (20L/4mL/2mL) was degassed, then heated at 80 oC for overnight. The mixture was worked up with 200 mL ethyl acetate and 50 mL 0.6 N hydrochloric acid aqueous solution. The aqueous phase was extracted with ethyl acetate (100 mL x 2).
  • Example 6 (Ex-6) Ex-6: A mixture of 1H,3H-thioxantheno[2,1,9-def]isochromene-1,3-dione (458 mg, 1.5 mmol), 4-(4-aminophenyl)butanoic acid (537 mg, 3 mmol) and DMAP (14mg, 0.11 mmol) in 10 mL DMF was heated at 165 oC for 2.5 hrs in microwave reactor. The resulted solution was dropped into 60 mL acetone while stirring.
  • Example 7 (Ex-7.3): Ex-7.2 – General Synthesis Procedure of compound Ex-7.2, (E)-6,7,8,9-tetrahydro- 5H-benzo[7]annulen-5-one oxime: A mixture of compound Ex-7.1 (10.0 g, 62.0 mmol), NH 2 OH•HCl (6.50 g, 93.0 mmol) and NaOAc (12.7 g, 155.0 mmol) in EtOH/H 2 O (45 mL/150 mL) was placed into a 500 mL two-neck round-bottom flask with a reflux condenser.
  • Example 9 Synthesis of Photoluminescent Complexes (PLC): The following examples are synthesis procedures of many embodiments of the RL- naphthalimide-BODIPY, as described herein: Synthesis of PLC-1: General Procedure of compound PLC-1.3: A 100 mL 2 neck round bottomed flask was fitted with an air condenser and a stir bar.
  • DDQ 381.4 mg, 1.68 mmol
  • Et 3 N 1.2 mL, 8.40 mmol
  • BF3•OEt2 2.1 mL, 12.6 mmol
  • the reaction mixture was kept at room temperature for another hour.
  • the reaction mixture was loaded with silica gel and purified by flash chromatography, using DCM in hexane (0-80-90%) as an eluant to provide the pure BODIPY PLC-16.3 as a blue golden solid, 279.0 mg, 36% yield.
  • DDQ 392.4 mg, 1.74 mmol
  • Et3N 1.2 mL, 8.64 mmol
  • BF 3 •OEt 2 1.6 mL, 12.96 mmol
  • the reaction mixture was kept at room temperature for another hour.
  • the reaction mixture was loaded with silica gel and purified by flash chromatography, using DCM in hexane (0-80-90%) as an eluant to provide the pure BODIPY PLC-17.3 as a brown golden solid, 211.0 mg, 28% yield.
  • Compound PLC-26.1 (6-(4-(tert-butyl)-2-nitrophenoxy)-1H,3H- benzo[de]isochromene-1,3-dione): A 1L 2N round-bottom flask was charged with a stir bar and placed in an aluminum heat block. The flask was fitted with a finned condenser, gas adapter, and flow control. The flask was flushed with argon.
  • Compound PLC-26.2 (6-(2-amino-4-(tert-butyl)phenoxy)-1H,3H- benzo[de]isochromene-1,3-dione): A 250 mL 2N round bottom flask was charged with a stir bar and fitted with a finned condenser, gas adapter, and flow control. The flask was placed in an aluminum heat block. The flask was flushed with argon.
  • Compound PLC-26.3 (9-(tert-butyl)-1H,3H-isochromeno[6,5,4-mna]xanthene-1,3- dione): A 40 mL vial was charged with NaNO 2 (30.0 mmol, 2.070 g), water (10 mL), and a stir bar. The vial was placed in an ice-water bath and stirred to dissolve. A 100 mL round bottom flask was charged with a stir bar and compound PLC-26.2 (4.00 mmol, 1.446 g), hydrochloric acid (37%) (20.0 mmol, 12.1M, 1.65 mL), and glacial acetic acid (30 mL).
  • the copper (II) solution was placed in an aluminum heat block and the temperature set to 130 °C.
  • the diazo solution was transferred to the dropping funnel.
  • the reaction was stirred at max RPM and the diazo solution was added dropwise over a period of about 20 minutes.
  • the resulting solution was stirred at 130 °C for 2 minutes, then removed from the heat block and stirred at room temperature overnight.
  • the precipitate was filtered off, washing with water.
  • the crude precipitate was dried, then dissolved and evaporated in vacuo onto silica gel.
  • Compound PLC-26.4 (4-(4-(9-(tert-butyl)-1,3-dioxo-1H-xantheno[2,1,9- def]isoquinolin-2(3H)-yl)phenyl)butanoic acid): A 100 mL 2N RBF was charged with a stir bar and fitted with a finned condenser, gas adapter, and flow control valve. The flask was flushed with argon and charged with compound PLC-26.3 (1.525 mmol, 525 mg), 4-(4-aminophenyl) butanoic acid (3.05 mmol, 546 mg), and DMAP (0.1113 mmol, 14 mg).
  • the vial was capped and stirred at room temperature 4.5 hours.
  • the reaction mixture was diluted with hexanes (to ⁇ 35 mL) and loaded onto a solid load cartridge ( ⁇ 20g SiO2).
  • the reaction mixture was purified by column chromatography on silica gel (120g, equilibrate 100% toluene, eluting 100% (5 CV) ⁇ 5% EtOAc/toluene (30 CV)). Fractions containing product were evaporated to dryness and re-purified by flash chromatography on silica gel (solid load, 120g column, equilibrate 40% DCM/hexanes, eluting 40% (2 CV) ⁇ 100% DCM (10 CV) ⁇ isocratic DCM until compound fully elutes)).
  • PLC-39.2 was synthesized from PLC-37.1 (2.531 mmol, 1.038 g), (4-(trifluoromethyl)phenyl)boronic acid (5.062 mmol, 961 mg), K 2 CO 3 (6.960 mmol, 962 mg), and Pd(dppf)Cl 2 (0.177 mmol, 130 mg) in THF/DMF/H2O (60 mL/12 mL/6 mL) at 80 °C for 30 minutes in a manner similar to PLC-36.7.
  • the flask was fitted with a finned condenser/gas adapter, stopper and flow control valve. The system was flushed with argon. To the flask was added PLC-37.4 (0.075 mmol, 49 mg) and Ex- 7.3 – 1,4,5,6-tetrahydrobenzo[6,7]cyclohepta[1,2-b]pyrrole (0.1575 mmol, 29 mg), followed by anhydrous DCM (20 mL). Under argon atmosphere, the reaction mixture was sparged with nitrogen for 10 minutes. A couple of small granules of pTsOH.H2O were gathered onto the end of a spatula and these were dipped in the reaction mixture.
  • the crude BODIPY was loaded onto flash silica gel directly (25 g). Purified by flash chromatography on silica gel (80g, solid load, equilibrate 80% DCM/hexanes, eluting 80% DCM/hexanes (2 CV) ⁇ 100 DCM/hexanes (5 CV) ⁇ isocratic 100% DCM/hexanes ( ⁇ 25 CV) ⁇ 100% DCM/hexanes/0.5% EtOAc modifier ( ⁇ 10 CV)). Product elutes as a broad peak. Fractions containing product were evaporated to dryness in vacuo. Gives a dark red solid, 89 mg (quantitative yield).
  • PLC-38.2 (2-(3-hydroxypropyl)-9-(4-(trifluoromethyl) phenyl)-1H- xantheno [2,1,9-def] isoquinoline-1,3(2H)-dione): PLC-38.1 (1.06 g, 2.5 mmol, 1eq) was suspended in DMF (10 ml), H 2 O (5 ml), added 4-trifluoromethyl) benzene boronic acid (0.949 g, 5.0 mmol, 2 eq), K 2 CO 3 (0.691 g, 5.0 mmol, 2eq), Pd(dppf)Cl 2 ⁇ DCM (40.8 mg, 0.05 mmol, o 0.02eq).
  • Compound 39.1 A mixture of compound Ex-4.4 (649 mg, 1.23 mmol), 4- (trifluoromethyl)phenylboronic acid (467 mg, 2.46 mmol), Pd(dppf)Cl2 (45 mg, 0.06 mmol), potassium carbonate (345 mg, 2.5 mmol) in cosolvents of THF/DMF/water (30mL/6mL/3mL) was degassed, then heated at 80 oC for overnight. The mixture was worked up with 300mL ethyl acetate and 50 mL 0.6 N hydrochloric acid aqueous solution. The aqueous phase was extracted with ethyl acetate (150 mL x 3).
  • Compound 40 A mixture of compound PLC-40.2 (50 mg, 0.082 mmol), PLC-1.3 (58.5 mg, 0.10 mmol), K2CO3 (20.7 mg, 0.15 mmol) in anhydrous DMF, was sonicated for 3 minutes, then heated at 75 oC for 5 hours under argon atmosphere. The resulted mixture was diluted with 100 mL DCM, washed with 0.1N HCl aqueous solution (50 mL x 2), dried over MgSO4, concentrated to 50 mL then loaded on silica gel, and purified by flash chromatography using eluents of DCM/EA (0% ⁇ 5% EA).
  • the reaction mixture was heated up to 165 oC and the reaction has been kept at this temperature for 2 hrs. TLC and LCMS showed the completion of the reaction.
  • the reaction was cooled down to 50 oC.
  • the solution was poured into a pre-chilled acetone (100 ml) solution with ice-water batch. The mixture has been kept at this temperature for 2 hours and then has been kept at room temperature overnight. The precipitate was collected by filtration.
  • the solid was washed by H2O (150 ml) and further dried in a vacuum oven at 100 oC for 3 hours to provide PLC-42.1 as a brown solid for the next step without further purification.805.0 mg, 48% yield.
  • the mixture has been sonicated at room temperature for 2 minutes. Then it was warmed up to 75 oC and has been kept stirring at this temperature for 4 hours. TLC (50% EtOAc in Hexane) showed the completion of the reaction.
  • the reaction mixture was purified by silica gel flash chromatography using EtOAc in DCM (0-3%) as an eluant to provide pure compound PLC-43 as a dark purple solid, 91.0 mg, 81% yield.
  • Step 1 A mixture of Ex-4.3 (0.735 g, 2.0 mmol, 1.0 eq) and 3-amino-1-ethanol (0.732 g, 12.0 mmol, 6.0 eq) was placed in 20 mL vial with and sealed a septum cap. The resulting mixture was stirred over a period of 45 minutes at 160 °C. After cooling to RT, the reaction was stirred with MeOH (10 mL) at RT for 15 minutes then filtered.
  • Step 2 At RT, the crude product of above step was mixed with DMF (5 ml), H2O (0.5 ml), (bis-3,5 trifluoromethyl) benzene boronic acid (1.031 g, 4.0 mmol, 2 eq), K2CO3 (0.553g, 4.0 mmol, 2eq), Pd(dppf)Cl2 ⁇ DCM (32.66 mg, 0.04 mmol, 0.02eq) was Vac- Fill Argon cycle 3 times, stirred & heated at 80 °C 45 minutes, the mixture became sticky, added 5 ml DMF, continued stirring at 80 °C further 15 minutes.
  • Compound PLC-47.2 (2-(6-hydroxyhexyl)-9-(4-(trifluoromethyl)phenyl)-1H- xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): Compound PLC-47.1 (assume 100% yield, 6.534 mmol, 3.047 g), (4-(trifluoromethyl)phenyl)boronic acid (13.068 mmol, 2.482 g), K2CO3 (17.969 mmol, 2483 mg), and Pd(dppf)Cl2 (0.4574 mmol, 335 mg) in THF (120 mL)/DMF (24 mL)/H2O 12 mL) at 80 ° C were combined in a method similar to the above methods.
  • Compound PLC-47.3 (2-(6-bromohexyl)-9-(4-(trifluoromethyl)phenyl)-1H- xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): A 250 mL 2N RBF was charged with a stir bar and fitted with a gas adapter/finned condenser and a flow control. To the flask was added Compound PLC-47.2 (2.239 mmol, 1.190 g), followed by 48% HBr/H2O (30 mL). The heat block was set to 130 ° C and the reaction mixture stirred at this temperature for 3 hours.
  • Compound PLC-47.4 (2,6-dichloro-4-((6-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H- xantheno[2,1,9-def]isoquinolin-2(3H)-yl)hexyl)oxy)benzaldehyde):
  • Compound PLC-47.4 was synthesized from Compound PLC-47.3 (0.200 mmol, 119 mg), 2,6-dichloro-4- hydroxybenzaldehyde (0.300 mmol, 57 mg), and K2CO3 (0.260 mmol, 36 mg) in dry DMF (10 mL) in a manner similar to Compound 34.4.
  • the crude compound was dissolved in DCM and loaded onto ⁇ 5g silica gel in a loader. Purified by flash chromatography on silica gel (80g, solid load, equilibrate 70% DCM/hexanes, eluting 70% (2 CV) to 100% DCM/hexanes (5 CV) ⁇ isocratic 100% DCM/hexanes (5 CV) to 0% EtOAc/DCM (0 CV) to isocratic 0% EtOAc/DCM (5 CV) ⁇ 10% EtOAc/DCM (20 CV)). Fractions containing product were evaporated to dryness in vacuo. Gives a yellow solid, 113 mg, (60% yield).
  • Compound PLC-47 (2-(6-(3,5-dichloro-4-(19,19-difluoro-6,7,11,12,13,19-hexahydro- 5H-18l4,19l4-benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[1,2- c]benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[2,1-f][1,3,2]diazaborinin-9-yl)phenoxy)hexyl)-9-(4- (trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): Compound PLC-47 was synthesized from Compound PLC-47.4 (0.1164 mmol, 82 mg), 1,4,5,6- tetrahydrobenzo[6,7]cyclohepta[1,2-b]pyrrole
  • the crude reaction mixture was diluted with ⁇ 25% hexanes, then loaded onto ⁇ 15g silica gel in a loader. Purified by flash chromatography on silica gel (80g, solid load, equilibrate 70% DCM/hexanes, eluting 70% (2 CV) to 100% DCM/hexanes (5 CV) isocratic 100% DCM/hexanes (5 CV) 0.5% EtOAc modifier of 100% DCM/hexanes (isocratic). Fractions containing product were evaporated to dryness in vacuo. Gives a deep red solid, 79 mg (62% yield).
  • Compound PLC-48.2 (tert-butyl 4-(2-(3-(3,5-dichloro-4-formylphenoxy)propyl)-1,3- dioxo-2,3-dihydro-1H-xantheno[2,1,9-def]isoquinolin-9-yl)benzoate): Compound PLC-48.2 was synthesized from Compound PLC-48.1 (0.1471 mmol), 2,6-dichloro-4- hydroxybenzaldehyde (0.441 mmol, 84 mg), and K2CO3 (0.4120 mmol, 57 mg) in dry DMF (10 mL) in a manner similar to the procedures above. The crude reaction was diluted with crushed ice ( ⁇ 50g).
  • Compound PLC-48 (tert-butyl 4-(2-(3-(3,5-dichloro-4-(19,19-difluoro-6,7,11,12,13,19- hexahydro-5H-18l4,19l4-benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[1,2- c]benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[2,1-f][1,3,2]diazaborinin-9-yl)phenoxy)propyl)-1,3- dioxo-2,3-dihydro-1H-xantheno[2,1,9-def]isoquinolin-9-yl)benzoate): Compound PLC-48 was synthesized from Compound PLC-48.2 (0.1471 mmol, 102 mg), 1,4,5,6- tetrahydrobenzo[6,7]cyclohepta[1,
  • Compound PLC-49.1 (9-(4-butylphenyl)-2-(3-hydroxypropyl)-1H-xantheno[2,1,9- def]isoquinoline-1,3(2H)-dione): Compound PLC-49.1 was synthesized from Compound PLC- 38.1 (1.500 mmol, 636 mg), (4-butylphenyl)boronic acid (3.00 mmol, 534 mg), K2CO3 (4.125 mmol, 570 mg), and Pd(dppf)Cl2 (0.105 mmol, 77 mg) in THF (30 mL)/DMF (6 mL)/water (3 mL) at 80 ° C in a manner similar to the procedures above.
  • Compound PLC-49.3 (4-(3-(9-(4-butylphenyl)-1,3-dioxo-1H-xantheno[2,1,9- def]isoquinolin-2(3H)-yl)propoxy)-2,6-dichlorobenzaldehyde): Compound PLC-49.3 was synthesized from PLC-49.2 (0.122 mg, 77 mg), ), 2,6-dichloro-4-hydroxybenzaldehyde (0.366 mmol, 70 mg), and K2CO3 (0.341 mmol, 47 mg) in dry DMF (10 mL) in a manner similar to the procedures described above.
  • Compound PLC-50.1 (2-(3-hydroxypropyl)-9-(4-(pentyloxy)phenyl)-1H- xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): Compound PLC-50.1 was synthesized from Compound PLC-38.1 (1.500 mmol, 6360mg), (4-(pentyloxy)phenyl)boronic acid (3.00 mmol, 624 mg), K2CO3 (4.125 mmol, 570 mg), and Pd(dppf)Cl2 (0.105 mmol, 77 mg) in THF (30 mL)/DMF (6 mL)/water (3 mL) at 80 ° C in a manner similar to the above procedures..
  • Compound PLC-50.2 (3-(1,3-dioxo-9-(4-(pentyloxy)phenyl)-1H-xantheno[2,1,9- def]isoquinolin-2(3H)-yl)propyl 4-methylbenzenesulfonate): Compound PLC-50.2 was synthesized from Compound PLC-50.1 (1.550 mmol, 787 mg), 4-methylbenzenesulfonic anhydride (6.202 mmol, 2024 mg), and Et3N (6.977 mmol, 0.97 mL) in dry DCE (20 mL) at 90 ° C in a manner similar to Compound 46.2 The crude product was loaded onto ⁇ 65g of silica gel in a loader.
  • Compound PLC-50.3 (2,6-dichloro-4-(3-(1,3-dioxo-9-(4-(pentyloxy)phenyl)-1H- xantheno[2,1,9-def]isoquinolin-2(3H)-yl)propoxy)benzaldehyde): Compound PLC-50.3 was synthesized from Compound PLC-50.2 (0.180 mmol, 119 mg), 2,6-dichloro-4- hydroxybenzaldehyde (0.539 mmol, 103 mg), and K2CO3 (0.503 mmol, 70 mg) in dry DMF (10 mL) in a manner similar to the procedures described above.
  • Compound PLC-50 (2-(3-(3,5-dichloro-4-(19,19-difluoro-6,7,11,12,13,19-hexahydro- 5H-18l4,19l4-benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[1,2-3 c]benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[2,1-f][1,3,2]diazaborinin-9-yl)phenoxy)propyl)-9- (4-(pentyloxy)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): Compound 48 was synthesized from Compound PLC-50.3 (0.150 mmol, 102 mg), 1,4,5,6- tetrahydrobenzo[6,7]cyclohepta[1,2-b]pyrrole (Ex-7.3, 0.3
  • Compound PLC-51.1 (6-(2-amino-4-(tert-butyl)phenoxy)-2-(3-hydroxypropyl)-1H- benzo[de]isoquinoline-1,3(2H)-dione): A 100 mL 2N round bottom flask was placed in an aluminum heat block and charged with a stir bar. The flask was fitted with a finned condenser/gas adapter and flow control valve. The system was flushed with argon.
  • Compound PLC-51.2 (9-(tert-butyl)-2-(3-hydroxypropyl)-1H-xantheno[2,1,9- def]isoquinoline-1,3(2H)-dione): A 40 mL vial was charged with a stir bar. To the vial was added NaNO2 (11.291 mmol, 779 mg) and water (4 mL). The vial was stirred in an ice-water bath at 0 ° C. A separate 40 mL vial was also charged with a stir bar. To this vial was added Compound PLC-51.1 (1.505 mmol, 630 mg), acetic acid (12 mL), and con. HCl (7.527 mmol, mL).
  • the vial was stirred at room temperature for a few minutes, then placed in a ice-water bath and stirred at 0 ° C for one minute.
  • the aqueous solution of NaNO2 was added to this vial over a period of 10 minutes with stirring at 0 ° C.
  • the diazo solution was stirred at 0 ° C for one hour.
  • a 250 mL 2N round bottom flask was fitted with a finned condenser, and addition funnel, and a stir bar.
  • CuSO4.5H2O (10.237 mmol, 2.556 g) and water (35 mL). The solution was stirred at room temperature.
  • the copper sulfate solution was heated to 130 ° C (heat block temperature).
  • the diazo solution was transferred to the addition funnel and added to the reaction mixture with high-speed stirring over a period of about 15 minutes.
  • the reaction mixture was stirred for an additional minute, then placed in a room temperature water bath. Once the reaction had cooled to room temperature, the product was isolated by filtration.
  • the crude product was a mixture of the desired alcohol and the acetate ester.
  • the crude product was dispersed in methanol and treated with excess K2CO3 at 60 ° C to cleave the ester.
  • the reaction was diluted with water, the product filtered off, washing with water.
  • Compound PLC-51 (9-(tert-butyl)-2-(3-(3,5-dichloro-4-(19,19-difluoro- 6,7,11,12,13,19-hexahydro-5H-18l4,19l4-benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[1,2- c]benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[2,1-f][1,3,2]diazaborinin-9-yl)phenoxy)propyl)-1H- xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): Compound PLC-51 was synthesized from Compound PLC-51.3 (0.391 mmol, 148 mg), 3,5-dichloro-4-(19,19-difluoro-6,7,11,12,13,19- hexahydro-5H-18
  • the reaction mixture was stirred at room temperature and Br2 (416.26 mmol, 21.3 mL) was added.
  • the second neck was stoppered and the reaction mixture was heated with an aluminum heat block at 75 ° C open to air over the weekend.
  • the reaction mixture was cooled to room temperature and a solid was filtered off.
  • the filtrate was diluted with hexanes ( ⁇ 20% of volume) and a second precipitate was filtered off. Both of these precipitates were dried in vacuo at 100 ° C. Orangish solids, 10.866 g total (69.9% yield). Both had similar LCMS and NMR.
  • Compound PLC-52.2 (2-(4-(5,11-dibromo-1,3-dioxo-1H-xantheno[2,1,9- def]isoquinolin-2(3H)-yl)phenyl)acetic acid): Compound PLC-52.2 was synthesized from PLC- 52.1 (7.000 mmol, 3.136 g), 2-(4-aminophenyl)acetic acid (14.00 mmol, 2.117 g), and DMAP (2.100 mmol, 257 mg) in anhydrous DMF (65 mL) at 160 ° C in a manner similar to the procedures described above.
  • Compound PLC-52.3 (2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H- xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid): Compound PLC-52.3 was synthesized from Compound PLC-52.2 (3.500 mmol, 2.034 g), (4- (trifluoromethyl)phenyl)boronic acid (14.00 mmol, 2.659 g), K2CO3 (19.25 mmol, 2.661 g), and Pd(dppf)Cl2 (0.0245 mmol, 179 mg) in THF (/60 mL), DMF (12 mL), and water (6 mL) with heating at 80 ° C under argon atmosphere overnight.
  • Compound PLC-52.5 A mixture of Compound PLC-52.4 (54 mg, 0.039 mmol), 4-n- butylphenylbonoric acid (42 mg, 0.236 mmol), Pd(PPh3)4 (14 mg, 0.012 mmol) and potassium carbonate (32 mg, 0.236 mmol) in THF/DMF/water (10mL/2mL/1mL) was degassed and heated at 80 C for 6 hours.
  • Compound PLC-52 A mixture of Compound PLC-52.5 (10 mg, 0.012 mmol), (2-(4-(1,3- dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)- yl)phenyl)acetic acid) (16 mg, 0.022 mmol), DMAP/TsOH (5 mg, 0.017 mmol), DIC (0.05 mL, 0.31 mmol) in 5 mL anhydrous DCM was stirred at room temperature overnight.
  • Compound PLC-53.1 (9-( 6-(2-amino-4-(tert-butyl)phenoxy)-2-(2-hydroxyethyl)-1H- benzo[de]isoquinoline-1,3(2H)-dione): Compound PLC-53.1 was synthesized from PLC-26.2 (8.827 mmol, 3.190 g), ethanolamine (17.65 mmol, 1.066 mL), and DMAP (2.648 mmol, 324 mg), followed by 200 proof ethanol (70 mL) in a manner similar to the procedures described above. The crude precipitate was filtered off, dissolved in acetone, and evaporated to dryness in vacuo. Gives a brown-yellow solid, 2.777 g (78% yield).
  • Compound PLC-53.2 (9-(tert-butyl)-2-(2-hydroxyethyl)-1H-xantheno[2,1,9- def]isoquinoline-1,3(2H)-dione): Compound PLC-53.2 was synthesized from Compound PLC- 53.1 (6.863 mmol, 2.776 g), NaNO2 (51.475 mmol, 3.552 g), conc. HCl (34.317 mmol, 2.83 mL), and CuSO4.5H2O (46.67 mmol, 11.653 g) in a manner similar to the procedures described above. The crude product was ⁇ 10% acetate ester. It was cleaved with K2CO3 in the same manner as described above.
  • Compound PLC-53.3 (4-(2-(9-(tert-butyl)-1,3-dioxo-1H-xantheno[2,1,9- def]isoquinolin-2(3H)-yl)ethoxy)-2,6-dichlorobenzaldehyde): Compound PLC-53.2 (0.200 mmol, 78 mg) and 2,6-dichloro-4-hydroxybenzaldehyde (0.260 mmol, 50 mg) were added to a 40 mL screw-cap vial, followed by dry DCE (10 mL) and a stir bar.
  • the reaction mixture was stirred at room temperature and DEAD (0.300 mmol, 0.137 mL) and PPh3 (0.300 mmol, 79 mg) were added. The reaction mixture was stirred at room temperature for 60 minutes. Additional DEAD 0.100 mmol, 0.046 mL) and PPh3 (0.100 mmol, 26 mg) were added and stirring continued at room temperature overnight.
  • the crude reaction mixture was loaded onto ⁇ 20g of silica gel in a loader. Purified by flash chromatography on silica gel (80g, solid load, equilibrate 0% EtOAc/DCM, eluting 0% (2 CV) to 10% EtOAc/DCM (15 CV)).
  • Compound PLC-53 (9-(tert-butyl)-2-(2-(4-(19,19-difluoro-6,7,11,12,13,19-hexahydro- 5H-18l4,19l4-benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[1,2- c]benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[2,1-f][1,3,2]diazaborinin-9-yl)-3,5- dimethylphenoxy)ethyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): Compound PLC- 53 was synthesized from Compound 53.3 (0.186 mmol, 104 mg), 1,4,5,6- tetrahydrobenzo[6,7]cyclohepta[1,2-b]pyrrole (Ex-7.3, 0.371 mmol,
  • Example 10 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 (DI) water, rinsed with fresh DI water, and sonicated for about 1 hour. The glass was then soaked in isopropanol (IPA) and sonicated for about 1 hour. The glass substrate was then soaked in acetone and sonicated for about 1 hour. The glass was then removed from the acetone bath and dried with nitrogen gas at room temperature. A 20 wt% solution of Poly(methylmethacrylate) (PMMA) (average M.W.
  • DI detergent and deionized
  • IPA isopropanol
  • 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 PLC-1 is shown in FIG.1
  • the resulting absorption/emission spectrum for PLC-2 is shown in FIG.2
  • the resulting absorption/emission spectrum for PLC-3 is shown in FIG. 3.
  • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Optical Filters (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

La présente divulgation concerne des cellules de levure qui sont génétiquement modifiées pour réduire leur propension à dégrader certains produits chimiques de plateforme, tels que l'acide acrylique, ainsi que des procédés de préparation et d'utilisation de telles cellules de levure pour la production d'acide acrylique et d'autres composés.
PCT/US2022/076912 2021-09-27 2022-09-23 Composés émissifs cycliques contenant du bore et film de conversion de couleur contenant ceux-ci WO2023049828A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN202280036055.0A CN117396580A (zh) 2021-09-27 2022-09-23 含硼环状发光化合物和包含该化合物的色彩转换膜
KR1020237039185A KR20240065040A (ko) 2021-09-27 2022-09-23 보론 함유 환상 발광 화합물 및 이를 함유하는 색 변환 필름

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US202163248863P 2021-09-27 2021-09-27
US63/248,863 2021-09-27
US202163278944P 2021-11-12 2021-11-12
US63/278,944 2021-11-12

Publications (1)

Publication Number Publication Date
WO2023049828A1 true WO2023049828A1 (fr) 2023-03-30

Family

ID=84331527

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2022/076912 WO2023049828A1 (fr) 2021-09-27 2022-09-23 Composés émissifs cycliques contenant du bore et film de conversion de couleur contenant ceux-ci

Country Status (3)

Country Link
KR (1) KR20240065040A (fr)
TW (1) TW202330556A (fr)
WO (1) WO2023049828A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3505592A1 (fr) * 2016-08-23 2019-07-03 FUJIFILM Corporation Particules électroluminescentes et composé
WO2020053124A1 (fr) * 2018-09-11 2020-03-19 Basf Se Récepteur comprenant un collecteur luminescent pour la communication optique de données
US20210010051A1 (en) * 2017-08-28 2021-01-14 Shizuoka Prefecture Public University Corporation Detection method and detection probe for colibactin and colibactin-producing bacteria
WO2021026402A1 (fr) * 2019-08-07 2021-02-11 Abbott Laboratories Composés chimioluminescents pour le multiplexage

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3505592A1 (fr) * 2016-08-23 2019-07-03 FUJIFILM Corporation Particules électroluminescentes et composé
US20210010051A1 (en) * 2017-08-28 2021-01-14 Shizuoka Prefecture Public University Corporation Detection method and detection probe for colibactin and colibactin-producing bacteria
WO2020053124A1 (fr) * 2018-09-11 2020-03-19 Basf Se Récepteur comprenant un collecteur luminescent pour la communication optique de données
WO2021026402A1 (fr) * 2019-08-07 2021-02-11 Abbott Laboratories Composés chimioluminescents pour le multiplexage

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
XIAONENG CUI ET AL: "Perylene-Derived Triplet Acceptors with Optimized Excited State Energy Levels for Triplet?Triplet Annihilation Assisted Upconversion", THE JOURNAL OF ORGANIC CHEMISTRY, vol. 79, no. 5, 21 February 2014 (2014-02-21), pages 2038 - 2048, XP055476678, ISSN: 0022-3263, DOI: 10.1021/jo402718e *

Also Published As

Publication number Publication date
KR20240065040A (ko) 2024-05-14
TW202330556A (zh) 2023-08-01

Similar Documents

Publication Publication Date Title
TW201708229A (zh) 氰化苯并呫噸及苯并噻噸化合物
JP2016534100A (ja) シアノ化されたナフタレンベンゾイミダゾール化合物
Jung et al. White light-emitting diodes using thermally and photochemically stable fluorescent silica nanoparticles as color-converters
JP7461466B2 (ja) ホウ素窒素化合物、有機電界発光組成物及びそれを含む有機電界発光素子
Vaz et al. Aggregation-induced emission enhancement in halochalcones
JP7415034B2 (ja) 含ホウ素環式放出性化合物及びそれを含む色変換フィルム
WO2022178450A1 (fr) Composés émissifs cycliques contenant du bore et film de conversion de couleur le contenant
WO2022178427A1 (fr) Composés émissifs cycliques contenant du bore et film de conversion de couleur les contenant
WO2023049828A1 (fr) Composés émissifs cycliques contenant du bore et film de conversion de couleur contenant ceux-ci
CN111116470A (zh) 聚集态诱导室温磷光橙红色电致发光化合物及其制备方法和应用
JP7415016B2 (ja) 含ホウ素環式放出性化合物、及び該化合物を含む色変換フィルム
TW202142676A (zh) 改良式波長轉換膜
He et al. An efficient 2-linked carbazolyl β-diketonate europium (III) complex as red phosphor applied in LED
JP7458498B2 (ja) 含ホウ素環式放出化合物及びそれを含む色変換フィルム
WO2023158977A1 (fr) Composés émissifs cycliques contenant du bore et film de conversion de couleur les contenant
CN117396580A (zh) 含硼环状发光化合物和包含该化合物的色彩转换膜
WO2023158976A1 (fr) Composés émissifs cycliques contenant du bore et film de conversion de couleur les contenant
WO2024081802A1 (fr) Film de conversion de longueur d'onde et dispositif d'affichage le comprenant
Luridiana et al. Synthesis and characterization of a new triazine-based NUV-blue excitable material for phosphor-converted LED technologies
ITMI20102116A1 (it) Composto o miscela di composti fotoluminescenti
WO2023158509A2 (fr) Film de conversion de longueur d'onde et dispositif d'affichage le comprenant
CN117063288A (zh) 含硼环状发光化合物和包含该含硼环状发光化合物的色彩转换膜
CN116003476A (zh) 一种环金属钯二聚物及其制备方法和应用
CN113861150A (zh) 基于香豆素衍生物的有机发光材料及其制备方法和应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22801937

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 202280036055.0

Country of ref document: CN