WO2016138077A1 - Élément de capteur de gaz - Google Patents

Élément de capteur de gaz Download PDF

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Publication number
WO2016138077A1
WO2016138077A1 PCT/US2016/019259 US2016019259W WO2016138077A1 WO 2016138077 A1 WO2016138077 A1 WO 2016138077A1 US 2016019259 W US2016019259 W US 2016019259W WO 2016138077 A1 WO2016138077 A1 WO 2016138077A1
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Prior art keywords
optionally substituted
sensor element
oxygen sensor
oxygen
layer
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Shijun Zheng
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Nitto Denko Corp
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Nitto Denko Corp
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
    • G01N31/223—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators for investigating presence of specific gases or aerosols
    • G01N31/225—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators for investigating presence of specific gases or aerosols for oxygen, e.g. including dissolved oxygen

Definitions

  • Some embodiments relate to improved gas, e.g. , oxygen sensors. Some embodiments relate to sensor materials incorporating carbazolyl benzenes.
  • the sensors of the present application may be used in the packaging industry and in particular in areas where integrity of the package is of particular interest.
  • packages include food packaging in general, and specifically of food exports, particularly of high margin foods e.g. certain fish/shellfish, bulk food ingredients, wine, beer, long term food storage as required for emergency aid and military operations, in the catering industry, pharmaceutical industry and in the packaging of medical disposables, surgical instruments and pediatric products as well as in any sectors that required a clean room manufacturing or assembly environment.
  • the sensors may also be used in situations the atmosphere is important to the product, such as protective atmospheres for art conservation or gas- sensitive, limited-life products such as DVDs.
  • Other applications include monitoring of water quality, in-line production monitoring and in biofermentation reactors.
  • Another instrument used to check for leak detection uses noninvasive methods. This involves placing the package into a pressure chamber and checking for leaks using carbon dioxide. It has the advantage of being nondestructive but is time-consuming and would not easily be incorporated into a production line. (e.g. PBI-Dansensor Pack Check). Thus there is a need for a simple and reversible optical sensor system for the detection of oxygen.
  • the present embodiments include a gas sensor for use in packaging applications, as well as methods related to the gas sensor.
  • Some embodiments include a gas sensor, e.g., oxygen sensor, element comprising an emissive compound represented by Formula 1 :
  • Formula 1 wherein is H, -CF 3 , optionally substituted phenyl, optionally substituted phenylethynyl, optionally substituted naphthyl, optionally substituted carbazolyl, optionally substituted pyridinyl, or optionally substituted pyrimidinyl;
  • R 2 is -CN or - CF 3;
  • R 3 and R 4 are independently optionally substituted carbazolyl, optionally substituted phenyl, or optionally substituted benzocarbazolyl; and R 5 and R 6 are independently optionally substituted carbazolyl, optionally substituted phenyl, or optionally substituted benzocarbazolyl.
  • Some embodiments include a method of detecting an oxygen- containing analyte in a sample comprising contacting the sample with a compound described herein; and detecting the presence or absence of blue emissions from the sample, wherein the presence of blue emissions indicates the absence of oxygen in the sample.
  • the method can further comprise measuring the amount of blue emission in the sample and correlating the amount of blue emission from the sample with a concentration of the oxygen in the sample.
  • Some embodiments include a method for determining the presence of oxygen in a sealed cavity comprising forming a first layer comprising the described compounds, wherein the compound has a first and second form, the first and second chemical forms having different visual characteristics; forming the second layer adjacent to the first layer and isolating the first layer from contact with the ambient environment, wherein the presence of an unacceptable level of oxygen contacting the first layer causes a color change of the first layer.
  • Some embodiments include a colorimetric indicating film comprising a first layer first layer comprising the described compounds.
  • the film further comprises polymethylmethacrylate.
  • the film further comprises a second layer, wherein the first and second layers are adjacent to each other, and wherein the first and second layers define an internal cavity therein, and wherein the first layer is a first color in an oxygen deficient atmosphere and a second color in an oxygen present atmosphere.
  • FIG. 1 depicts singlet (S1 ) and triplet (T1 ) energy levels.
  • FIG. 2 is a schematic of an embodiment of a film described herein.
  • FIG. 3 is a schematic of an embodiment of a film described herein.
  • FIG. 4 is a schematic of an embodiment of a film described herein.
  • FIG. 5 is a schematic of an embodiment of a film described herein.
  • FIG. 6 is a comparative photograph of embodiments exposed and not exposed to a triplet quenching material, e.g., 0 2 .
  • FIG. 7 is a plot presenting the emissive intensities of an embodiment versus emissive wavelengths for EM-8.
  • FIG. 8 is a plot presenting the emissive intensities of a film embodiment versus varying triplet quenching material, 0 2 , concentrations.
  • FIG. 9 is a plot presenting the emissive intensities of a film embodiment versus varying triplet quenching material, 0 2 , concentrations.
  • optionally substituted group refers to a group that may be substituted or unsubstituted, such as alkyl, naphthyl, carbazolyl, benzocarbazolyl, phenoxazolyl, phenothiazolyl, phenazolyl, etc.
  • 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 substituted group may have one or more substituent groups on the parent group structure.
  • some substituent groups may include optionally substituted alkyl, -O-alkyl (e.g.
  • -OCH 3 -OC 2 H 5 , -OC 3 H 7 , -OC 4 H 9 , etc.
  • -S- alkyl e.g. -SCH 3 , -SC 2 H 5 , -SC 3 H 7 , -SC 4 H 9 , etc.
  • R' and R" are independently H or optionally substituted alkyl, -OH, -SH, -CN, -NO 2 , -CF 3 , phenyl, diphenyl amine, acenaphtyl, naphthyl, benzocarbazolyl, phenoxazolyl, phenothiazolyl, phenazolyl, phenylnaphthylamine, carbazolyl, F, CI, Br, or I.
  • a substituent is described as "optionally substituted,” that substituent can be substituted with the above substituents.
  • Optionally substituted alkyl includes its common meaning in the field and includes unsubstituted alkyl and substituted alkyl.
  • the substituted alkyl refers to substituted alkyl where one or more H atoms are replaced by one or more substituent groups, such as -O-alkyl (e.g. -OCH 3 , -OC 2 H 5 , -OC 3 H 7 , -OC 4 H 9 , etc.), - S-alkyl (e.g.
  • -SCH 3 , -SC 2 H 5 , -SC 3 H 7 , -SC 4 H 9 , etc.
  • -NR'R" where R' and R" are independently H or alkyl
  • R' and R" are independently H or alkyl
  • -OH -SH
  • -CN -N0 2
  • F CI
  • Br Br
  • I CI
  • alkyl-CN alkylthiol
  • fluoroalkyl includes its common meaning in the field and includes alkyl having one or more fluorine substituents.
  • Ci- 6 F 1-13 fluoroalkyl refers to fluoroalkyl having 1 -6 carbon atoms and 1 -13 fluorine atoms.
  • perfluoroalkyl refers to fluoroalkyl with a formula C n F 2n +i for a linear or branched structure, e.g., CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , C 5 Fn , C 6 F 13 , etc., or C n F 2n -i for a cyclic structure, e.g., cyclic C 3 F 5 , cyclic C 4 F 7 , cyclic CsF 9 , cyclic CeFn , etc.
  • Ci -3 perfluoroalkyl refers to CF 3 , C 2 F 5 , and C 3 F 7 isomers.
  • Aryl refers to an aromatic substituent that may be a single ring or multiple rings.
  • the aromatic rings of the aryl group may each and optionally contain heteroatoms, for example, as in pyridine, pyrazine, pyrimidine, carbazolyl or imidazole.
  • the aryl group can be optionally substituted with one or more aryl group substituents which can be the same or different, where "aryl group substituent" includes alkyl, aryl, arylalkyl, hydroxy, alkoxyl, aryloxy, arylalkoxyl, carboxy, -CN, acyl, halo, nitro, alkoxycarbonyl, aryloxycarbonyl, arylalkoxycarbonyl, acyloxyl, acylamino, aroylamino, carbamoyl, alkylhalide, alkylcarbamoyl, dialkylcarbamoyl, arylthio, alkylthio, alkylene, boronic acid, and -NRR', where R and R' can be each independently hydrogen, alkyl, aryl and -alkyl-aryl.
  • naphthyl includes, but is not limited to the ring systems:
  • BCbz benzocarbazolyl
  • phenoxazinyl refers to:
  • phenothiazolyl refers to:
  • phenazolyl refers to:
  • diphenylamine refers to:
  • phenylnaphthylamine refers to:
  • phenylethynyl refers to:
  • Some embodiments include a gas sensing, e.g., oxygen sensing, element comprising a compound represented by Formula 1 :
  • FM is H, -CF 3 , optionally substituted phenyl, optionally substituted phenylethynyl, optionally substituted naphthyl, optionally substituted carbazolyl, optionally substituted pyridinyl, or optionally substituted pyrimidinyl.
  • F is H.
  • F is -CF 3 .
  • F is CN.
  • FM is optionally substituted phenyl, such as phenyl having 0, 1 , 2, or 3 substituents (e.g. substituents having a molecular weight less than 100 Da, including CH 3 , C 2 H 5 , F, CI, Br, CF 3 , CN, COH, COCH 3 , OCH 3 , etc.).
  • FM is optionally substituted pyndinyl, such as pyndinyl having 0, 1 , or 2 substituents (e.g.
  • F is optionally substituted pyrimidinyl, such as pyrimidinyl having 0 substituents or 1 substituent (e.g. a substituent having a molecular weight less than 100 Da, including CH 3 , C 2 H 5 , F, CI, Br, CF 3 , CN, COH, COCH 3 , OCH 3 , etc.).
  • F is optionally substituted pyrimidinyl, such as pyrimidinyl having 0 substituents or 1 substituent (e.g. a substituent having a molecular weight less than 100 Da, including CH 3 , C 2 H 5 , F, CI, Br, CF 3 , CN, COH, COCH 3 , OCH 3 , etc.).
  • F is optionally substituted naphthyl, such as naphthyl having 0, 1 , 2, or 3 substituents (e.g. substituents having a molecular weight less than 100 Da, including CH 3 , C 2 H 5 , F, CI, Br, CF 3 , CN, COH, COCH 3 , OCH 3 , etc.).
  • F is optionally substituted carbazolyl, such as carbazolyl having 0, 1 , 2, 3, or 4 substituents (e.g.
  • substituents having a molecular weight less than 200 Da such as Ci -6 alkyl, F, CI, Br, CF 3 , CN, COH, COCH 3 , OCH 3 , phenyl, etc.).
  • FM is optionally substituted phenylethynyl, such as phenylethynyl having 0, 1 , 2, or 3 substituents (e.g. substituents having a molecular weight less than 100 Da, including CH 3 , C2H5, F, CI, Br, CF 3 , CN, COH, COCH 3 , OCH 3 , etc.).
  • substituents having a molecular weight less than 100 Da including CH 3 , C2H5, F, CI, Br, CF 3 , CN, COH, COCH 3 , OCH 3 , etc.
  • R 2 is -CN or -CF 3 .
  • R 3 is optionally substituted carbazolyl such as carbazolyl having 0, 1 , 2, 3, or 4 substituents (e.g.
  • substituents having a molecular weight less than 300 Da such as C 1 - 12 alkyl, such as CH 3 , C 2 alkyl, C 3 alkyl, C 3 cycloalkyl, C 4 alkyl, C 4 cycloalkyl, C 5 alkyl, C 5 cycloalkyl, C 6 alkyl, C 6 cycloalkyl, etc.; F; CI; Br; CF 3 ; CN; COH; -CO-alkyl, such as -COCH 3 , -COC 2 H 5 , - COC 3 H 7 , -COC 4 H 9 , etc; -O-alkyl, such as -OCH 3 , -OC 2 H 5 , -OC 3 H 7 , -OC 4 H 9 , etc.; optionally substituted -CO-phenyl; optionally substituted -O-phenyl; optionally substituted phenyl; optionally substituted -O-phenyl; optional
  • substituents having a molecular weight less than 100 Da including CH 3 , C 2 H 5 , F, CI, Br, CF 3 , CN, COH, COCH 3 , OCH 3 , etc.); or optionally substituted benzocarbazolyl such as benzocarbazolyl having 0, 1 , 2, 3, or 4 substituents (e.g.
  • substituents having a molecular weight less than 300 Da such as Ci-i 2 alkyl, such as CH 3 , C 2 alkyl, C 3 alkyl, C 3 cycloalkyl, C 4 alkyl, C 4 cycloalkyl, C 5 alkyl, C 5 cycloalkyl, C 6 alkyl, C 6 cycloalkyl, etc.; F; CI; Br; CF 3 ; CN; COH; -CO-alkyl, such as -COCH 3 , -COC 2 H 5 , -COC 3 H 7 , -COC 4 H 9 , etc; -O-alkyl, such as -OCH 3 , -OC 2 H 5 , -OC 3 H 7 , -OC 4 H 9 , etc.; optionally substituted -CO-phenyl; optionally substituted -O-phenyl; optionally substituted phenyl; optionally substituted -O-phenyl; optionally
  • R 3 is
  • R 4 is optionally substituted carbazolyl such as carbazolyl having 0, 1 , 2, 3, or 4 substituents (e.g. substituents having a molecular weight less than 300 Da, such as C 1 - 12 alkyl, such as CH 3 , C 2 alkyl, C 3 alkyl, C 3 cycloalkyl, C 4 alkyl, C 4 cycloalkyl, C 5 alkyl, C 5 cycloalkyl, C 6 alkyl, C 6 cycloalkyl, etc.; F; CI; Br; CF 3 ; CN; COH; -CO-alkyl, such as -COCH 3 , -COC 2 H 5 , - COC 3 H 7 , -COC 4 H 9 , etc; -O-alkyl, such as -OCH 3 , -OC 2 H 5 , -OC 3 H 7 , -OC 4 H 9 , etc.; optionally
  • substituents having a molecular weight less than 100 Da including CH 3 , C 2 H 5 , F, CI, Br, CF 3 , CN, COH, COCH 3 , OCH 3 , etc.); or optionally substituted benzocarbazolyl, such as benzocarbazolyl having 0, 1 , 2, 3, or 4 substituents (e.g.
  • substituents having a molecular weight less than 300 Da such as Ci-i 2 alkyl, such as CH 3 , C 2 alkyl, C 3 alkyl, C 3 cycloalkyl, C 4 alkyl, C 4 cycloalkyl, C 5 alkyl, C 5 cycloalkyl, C 6 alkyl, C 6 cycloalkyl, etc.; F; CI; Br; CF 3 ; CN; COH; -CO-alkyl, such as -COCH 3 , -COC 2 H 5 , -COC 3 H 7 , -COC 4 H 9 , etc; -O-alkyl, such as -OCH 3 , -OC 2 H 5 , -OC 3 H 7 , -OC 4 H 9 , etc.; optionally substituted -CO-phenyl; optionally substituted -O-phenyl; optionally substituted phenyl; optionally substituted -O-phenyl; optionally
  • R 5 is optionally substituted carbazolyl, optionally substituted phenyl, or optionally substituted benzocarbazolyl.
  • R 5 is optionally substituted carbazolyl, such as carbazolyl having 0, 1 , 2, 3, or 4 substituents (e.g.
  • substituents having a molecular weight less than 300 Da such as C1-12 alkyl, such as CH 3 , C2 alkyl, C3 alkyl, C3 cycloalkyl, C 4 alkyl, C 4 cycloalkyl, C 5 alkyl, C 5 cycloalkyl, C 6 alkyl, C 6 cycloalkyl, etc.; F; CI; Br; CF 3 ; CN; COH; -CO-alkyl, such as -COCH 3 , -COC 2 H 5 , -COC 3 H 7 , -COC 4 H 9 , etc; -O-alkyl, such as -OCH 3 , -OC2H5, -OC 3 H 7 , -OC 4 H 9 , etc.; optionally substituted -CO-phenyl; optionally substituted -O-phenyl; optionally substituted phenyl; optionally substituted diphenylamino; optionally substituted carbazo
  • R 5 is optionally substituted phenyl, such as phenyl having 0, 1 , 2, or 3 substituents (e.g. substituents having a molecular weight less than 100 Da, including CH 3 , C 2 H 5 , F, CI, Br, CF 3 , CN, COH, COCH 3 , OCH 3 , etc.)
  • substituents e.g. substituents having a molecular weight less than 100 Da, including CH 3 , C 2 H 5 , F, CI, Br, CF 3 , CN, COH, COCH 3 , OCH 3 , etc.
  • R 5 is optionally substituted benzocarbazolyl, such as benzocarbazolyl having 0, 1 , 2, 3, or 4 substituents (e.g. substituents having a molecular weight less than 300 Da, such as C1-12 alkyl, such as CH 3 , C 2 alkyl, C 3 alkyl, C 3 cycloalkyl, C 4 alkyl, C 4 cycloalkyl, C 5 alkyl, C 5 cycloalkyl, C 6 alkyl, C 6 cycloalkyl, etc.; F; CI; Br; CF 3 ; CN; COH; -CO-alkyl, such as -COCH 3 , -COC 2 H 5 , - COC 3 H 7 , -COC 4 H 9 , etc; -O-alkyl, such as -OCH 3 , -OC 2 H 5 , -OC 3 H 7 , -OC 4 H 9 , etc
  • R 5 and R 6 is
  • R 6 is optionally substituted carbazolyl, optionally substituted phenyl, or optionally substituted benzocarbazolyl.
  • R 6 is optionally substituted carbazolyl, such as carbazolyl having 0, 1 , 2, 3, or 4 substituents (e.g. substituents having a molecular weight less than 300 Da, such as C1-12 alkyl, such as CH 3 , C 2 alkyl, C 3 alkyl, C 3 cycloalkyl, C 4 alkyl, C 4 cycloalkyl, C 5 alkyl, C 5 cycloalkyl, C 6 alkyl, C 6 cycloalkyl, etc.; F; CI; Br; CF 3 ; CN; COH; -CO-alkyl, such as -COCH 3 , -COC 2 H 5 , - COC 3 H 7 , -COC 4 H 9 , etc; -O-alkyl, such as -OCH 3 , -OC 2 H 5 , -OC 3 H 7 , -OC 4 H 9 , etc.; optionally substituted
  • R 6 is optionally substituted phenyl, such as phenyl having 0, 1 , 2, or 3 substituents (e.g. substituents having a molecular weight less than 100 Da, including CH 3 , C 2 H 5 , F, CI, Br, CF 3 , CN, COH, COCH 3 , OCH 3 , etc.).
  • substituents having a molecular weight less than 100 Da, including CH 3 , C 2 H 5 , F, CI, Br, CF 3 , CN, COH, COCH 3 , OCH 3 , etc.
  • R 6 is optionally substituted benzocarbazolyl, such as benzocarbazolyl having 0, 1 , 2, 3, or 4 substituents (e.g. substituents having a molecular weight less than 300 Da, such as C1-12 alkyl, such as CH 3 , C2 alkyl, C 3 alkyl, C 3 cycloalkyl, C 4 alkyl, C 4 cycloalkyl, C 5 alkyl, C 5 cycloalkyl, C 6 alkyl, C 6 cycloalkyl, etc.; F; CI; Br; CF 3 ; CN; COH; -CO-alkyl, such as -COCH 3 , -COC 2 H 5 , - COC 3 H 7 , -COC 4 H 9 , etc; -O-alkyl, such as -OCH 3 , -OC 2 H 5 , -OC 3 H 7 , -OC 4 H 9 , etc
  • R 5 and R 6 are independently
  • R 3 , R 4 , R 5 and R 6 are the same. In some embodiments, R 3 and R 4 are the same. In some embodiments R 5 and R 6 are the same.
  • the compound can be represented by Formula 2:
  • R 7 can independently be an optionally substituted arylene group, an optionally substituted carbazolyl group; and R 8 can be hydrogen, an alkyl group, an optionally substituted phenyl and/or an optionally substituted carbazolyl.
  • R 7 can be :
  • R 8 can be:
  • the compound can be represented by Formula 3:
  • R 9 is an optionally substituted aryl or an optionally substituted heteroaryl group; and wherein, R 10 is an electron donor heteroaryl group, e.g., an optionally substituted heteroaryl.
  • R 9 can be an electron acceptor group.
  • R 9 can be an electron acceptor aryl group and/or an electron acceptor heteroaryl group.
  • R 9 can be selected from an optionally substituted phenyl, optionally substituted phenylacetylene, optionally substituted naphthalene, optionally substituted acenaphthylene, optionally substituted pyridinyl and/or optionally substituted pyrimidinyl.
  • R 10 can be an optionally substituted carbazolyl, an optionally substituted benzocarbazolyl, an optionally substituted phenoxazolyl, an optionally substituted phenothiazolyl and/or an optionally substituted phenazolyl.
  • the compound can be represented by Formula 4:
  • Rn can be an optionally substituted aryl and/or an optionally substituted heteroaryl; and wherein Cbz can be an optionally substituted carbazolyl.
  • the compound can be represented by Formula 5:
  • Ri 2 can be an optionally substituted aryl and/or an optionally substituted heteroaryl; and wherein BCbz can be an optionally substituted benzocarbazolyl.
  • a compound for use in emissive elements of organic light emitting devices the compound being represented by Formula 6:
  • R 13 can be an optionally substituted phenyl, optionally substituted phenylacetylene, optionally substituted naphthalene, and/or optionally substituted acenaphthylene.
  • the compound can be represented by Formula 7:
  • R 14 is selected from is selected from optionally substituted phenyl, optionally substituted phenylacetylene, optionally substituted naphthalene, and optionally substituted acenaphthylene.
  • the compound is an emissive compound.
  • the compound can be used in emissive elements of organic light emitting devices.
  • R 9 , Rn , R 12 , R13 and/or R 14 can be an optionally substituted aryl and/or heteroaryl. In some embodiments, R 9 , Rn , R 12 , R13 and/or R 14 can be an unsubstituted aryl. In some embodiments, R 9 , Rn , R 12 , R13 and/or R 14 can be a mono-substituted aryl. In some embodiments, R 9 , Rn , R 12 , R13 and/or R 14 can be di-substituted aryl.
  • R 9 , Rn , R 12 , R 13 and/or R 14 can be an unsubstituted heteroaryl. In some embodiments, R 9 , Rn , R 12 , R 13 and/or R 14 can be a mono-substituted heteroaryl. In some embodiments, R 9 , R11 , R12, Ri 3 and/or R 14 can be a di-substituted heteroaryl.
  • R9, R11 , R12, Ri3 and/or R 14 can bean optionally substituted phenyl, optionally substituted phenylacetylene, optionally substituted naphthalene, optionally substituted acenaphthylene, an optionally substituted pyrimidinyl and/or an optionally substituted pyridinyl.
  • the optionally substituted aryl and/or heteroaryl can be:
  • Rn, and/or an optionally substituted electron donor heteroaryl e.g., Cbz
  • Cbz an optionally substituted electron donor heteroaryl
  • Rn and/or an optionally substituted BCbz can be selected from:
  • R 15 is an electron acceptor compound selected from an optionally substituted phenyl, optionally substituted pyridinyl and optionally substituted pyrimidinyl; and wherein, R 16 is an electron donor compound selected from an optionally substituted carbazolyl, an optionally substituted benzocarbazolyl, an optionally substituted phenoxazolyl, an optionally substituted phenothiazolyl and an optionally substituted phenazolyl.
  • Some embodiments include a compound selected from optionally (4'r,6'r)-5'-(4-cyanophenyl)-4',6'-bis(3,6-diphenyl-9H-carbazol-9-yl)-[1 , 1 ':3',1 "- terphenyl]-2',4,4"-tricarbonitrile (Emitting Compound 1 [EM-25]), (4'R,6'R)-4',6'- bis(7H-benzo[c]carbazol-7-yl)-5'-(4-cyanophenyl)-[1 , 1 ':3', 1 "-terphenyl]-2',4,4"- tricarbonitrile [EM-26]), (4'R,6'R)-4',6'-bis(5H-benzo[b]carbazol-5-yl)-5'-(4- cyanophenyl)-[1 ,r:3',1 "-terphenyl]-2',4,4"-tricarbonitrile (
  • the compound can be at least one of :
  • the chemical compounds can be at least those TADF compounds described in United States Provisional Patent Application Nos. 61/821 ,597, filed May 9, 2013; 61/917,876, filed December 18, 2013 [PCT/US2014/037572, filed 09-May-2014, WO2014/183080, published on November 13, 2014, Appendix A]; 61/897,657, filed October 30, 2013 [PCT/US2014/63207, filed October 30, 2014, Appendix B], and/or 62/013,416, filed June 17, 2014 [Appendix C], which are incorporated by reference in their entireties for their disclosure of TADF compounds and attached as appendices A, B and C, respectively.
  • the chemical compounds can be at least those having a AS1 - T1 ⁇ 0.1 .
  • a method of detecting a gas, e.g., oxygen, in a sample comprising contacting the sample with a TADF compound described herein; and detecting the presence or absence of colored emissions from the sample, wherein the presence of colored emissions indicates the presence of an analyte in the sample.
  • the analyte can be a triplet state quencher (TSQ).
  • TSQ triplet state quencher
  • the analyte can be 0 2 .
  • the compound can be EM-8, and the colored emission can be light blue (emissive ⁇ about 500 nm).
  • the analyte can be 0 2 .
  • the method further comprises measuring the amount of blue emission in the sample and correlating the amount of blue emission from the sample with a concentration of the oxygen in the sample.
  • An oxygen sensor element comprising a compound described herein may be configured to detect about 0.1 %, about 0.2%, about 0.5%, about 1 %, about 2%, about 8%, or about 12% or higher 0 2 by volume in an atmosphere that comes into contact with the oxygen sensor element.
  • an oxygen sensor may be configured to change color, or otherwise indicate, when an atmosphere in contact with the oxygen sensor, has an oxygen content that increases so it reaches 0.1 % 0 2 by volume to alert the user that the contents may no longer be good.
  • the oxygen sensor may be within a packaging layer, such as a wrapper or film.
  • the packaging layer may act as a barrier to the passage of oxygen.
  • the packaging layer may impair the passage of oxygen through the packaging layer.
  • an oxygen sensor inside the packaging layer may detect when the packaging layer fails by detecting an increase in oxygen content within the packaging.
  • the sample can be contacted with a coated substrate comprising the chemical compound. In some embodiments, the sample can be contacted with a porous substrate and the chemical compound.
  • the compounds described herein can have a first vibrational or energy state having a first color and a second vibrational or energy state having a second color. In some embodiments, the compounds can have a reversible color change from the first energy state to the second energy state.
  • the term color includes no color or clear.
  • the excitation/irradiation of a compound can change the energy state or level of the compound from a ground state energy level (S 0 ) to an unstable excited state energy level (Si).
  • the excited compound can return to the ground state energy level upon releasing a photon.
  • the excited compound could also non-radiatively pass to a triplet state, or conversely a triplet transitions to a singlet, that process is known as intersystem crossing (ISC).
  • ISC intersystem crossing
  • the probability of ISC occurring can be more favorable when the vibrational/energy states/levels (Si , Ti) of the two excited states overlap and/or when the differences between the vibrational/energy states/levels of the two excited states are minimal, since little or no energy must be gained or lost in the transition.
  • the S1 and T1 values can be determined by dissolving a sample, e.g., 2 mg, in 1 ml_ of 2-methyltetrahydrofuran (2-MeTHF) and transferring the resulting solution into a quartz tube.
  • the quartz tube containing the sample can then be frozen (77K) by liquid nitrogen prior to measurement.
  • ⁇ S1 -T1 can be less than 0.5, 0.25, 0.1 , 0.05, and /or 0.01 eV, facilitating the ISC between the singlet excited state (S1 ) and the triplet state (T1 ). See Table 1 :
  • the excited compound e.g., excited EM-8
  • emissive ⁇ about 500 nm.
  • the triplet state quenching can be effected by the presence of oxygen.
  • the 0 2 % present in the atmosphere or in contact with the chromophore sufficient to effect the quenching can be at least 0.1 %, 0.2%, 0.5%, 1 .0%, 2.0%, 8%, and/or 12% 0 2 in the contacting atmosphere.
  • the chromophore or material, upon being exposed to TSQ compound, therefore appears substantially colorless or clear.
  • the chromophore can reversibly change color, that is, removal of the TSQ gas will return the color to the chromophore solution/composite.
  • the chromophore can be a compound that has a first and a second coloration depending upon the singlet, triplet and/or ground state. In some embodiments, the chromophore emits a colored light due to the absence of a triplet state quenching material in contact or communication with the chromophore. In some embodiments, the chromophore does not emit a colored light, e.g., it is colorless, in the presence of a triplet state quenching material, e.g., 0 2 .
  • the device can comprise an optical sensor, comprising an indicator system.
  • the indicator system can comprise a compound that exists in at least first and second different forms depending on a concentration of an analyte, wherein the different forms can be distinguished based on their respective first and second emissions at a specified wavelength.
  • the indicator system can comprise a compound that exists in at least first and second different forms depending on a concentration of an analyte, wherein the different forms can be distinguished based on their respective first and second photonic emissions.
  • the first and second photonic emissions are characterized by first and second light intensities.
  • the binding or presence of a triplet state quencher causes an apparent optical change in the apparent emission by the chromophore related to a concentration of the analyte.
  • the senor can be a colorimetric sensor.
  • the sensor can comprises gas sensor tubes.
  • the gas detector tubes may be used to determine the concentration of at least oxygen gas in a sample gas.
  • the gas detector tubes can comprise any or all of the chemical compounds described herein within a transparent tube.
  • the gas detector tubes comprise a porous solid with pathways that allow gas to flow through the porous solid from an inlet of the gas detector tube to an outlet of the gas detector tube or the chemical reagent can be on the surface of a porous solid substrate.
  • the chemical compound/the material within the tube can change color when the compound is placed in contact with the chemical reagent, e.g., triplet state quenching material ("colorimetric reaction"), typically the chemical reagent and the target gases will react resulting in the color change.
  • the target gases are involved in the colorimetric reaction with the chemical reagent until the target gases are depleted from the sampled gas.
  • Many reagents for use in gas detector tubes are known and applicable to embodiments of the gas detector tubes.
  • a sample is typically drawn through the gas detector tubes by a sampling pump.
  • Common sample pumps include hand-held piston pumps or bellows pump that are capable of accurately and repeatedly drawing a known volume of air.
  • Embodiments of the gas detector tubes of the invention may be read either electronically by an electronic gas detector tube reader or visually by a user by a simple comparison of color scales.
  • the colorimetric sensor can comprise gas sensor coated substrates.
  • the gas sensor coated substrates may be used to determine the concentration of at least oxygen gas in a sample gas.
  • the gas detector coated substrates can typically comprise a matrix and any or all of the chemical compounds described disposed within the matrix.
  • the coated substrate can be woven material (natural or manufactured fabrics), non-woven material (e.g., glass fiber, paper, etc.).
  • the matrix can comprise a substantially transparent polymer.
  • the substantially transparent polymer can be selected from poly(methylmethacrylate) (PMMA), polyethylene (PE), polyethylene terephthalate (PET), vinylidene chloride and/or polycarbonate (PC).
  • the polyethylene film can be low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), and/or high density polyethylene (HDPE).
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • MDPE medium density polyethylene
  • HDPE high density polyethylene
  • the density of the PE can be between 0.900, 0.910, 0.920, 0.930 gm/cm 3 to about 0.94, 0.95, 0.96, 0.97, 0.98 gm/cm 3 or any combination the aforementioned densities.
  • a detector e.g., a photodetector
  • Optical filters can be placed between the sensor and the detector for wavelength selection.
  • Other optical components may also be utilized, e.g., mirrors, collimating and/or focusing lenses, beam splitters, etc.
  • Optical fibers can be used to deliver selected wavelengths to the sensor and to deliver the fluorescence emission from the sensor to the detector.
  • the light source and the detector may be controlled by electronic control and/or the outputs from the photodetectors can be analyzed by additional electronics, e.g., a computer.
  • a film can be used to detect the presence of oxygen.
  • the film can comprise the compounds described herein.
  • the film further comprises a substantially transparent polymer.
  • the substantially transparent polymer can be selected from poly(methylmethacrylate) (PMMA), polyethylene (PE), polyethylene terephthalate (PET), vinylidene chloride and/or polycarbonate (PC).
  • the polyethylene film can be low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), and/or high density polyethylene (HDPE).
  • the density of the PE can be between 0.900, 0.910, 0.920, 0.930 gm/cm 3 to about 0.94, 0.95, 0.96, 0.97, 0.98 gm/cm 3 or any combination the aforementioned densities.
  • the film 10 can comprise a first layer 120 and second layer 122, the first layer comprising the any of the compounds described herein.
  • a first layer 120 can be disposed adjacent to a second layer 122.
  • the plural layer film 1 10 can define a cavity 124 therein and/or surround a target material, the first layer disposed within the interior of the defined cavity, such that presence of oxygen, e.g., passing through the first and or second layer or generated within the cavity 124, contacts the first layer and colorimetrically shifts the color from a first color to a second color.
  • the first color can be about
  • film can comprise a first layer 120 and second layer 122, the first layer comprising any of the compounds described herein.
  • a first layer 120 can be disposed between or adjacent to a second layer 122 and/or third layer 126.
  • the plural layer film 1 10 can define a cavity 124 therein and/or surround a target material, the first layer disposed within the interior of the defined cavity, such that presence of oxygen, e.g., passing through the second and or third layers or generated within the cavity 124, contacts the first layer and colorimetrically shifts the color from a first color to a second color.
  • Embodiment 1 An oxygen sensor element comprising an emissive compound represented by Formula 1 :
  • F is H, -CF 3 , optionally substituted phenyl, optionally substituted phenylethynyl, optionally substituted naphthyl, optionally substituted carbazolyl, optionally substituted pyridinyl, or optionally substituted pyrimidinyl;
  • R 2 is -CN or -CF 3;
  • R 3 and R 4 are independently optionally substituted carbazolyl, optionally substituted phenyl, or optionally substituted benzocarbazolyl;
  • R 5 and R 6 are independently optionally substituted carbazolyl, optionally substituted phenyl, or optionally substituted benzocarbazolyl.
  • Embodiment 2 The oxygen sensor element of embodiment 1 , wherein R ⁇ is optionally substituted phenyl.
  • Embodiment 3 The oxygen sensor element of embodiment 1 , wherein R ⁇ is H.
  • Embodiment 4 The oxygen sensor element of embodiment 1 , wherein R ⁇ is optionally substituted pyridinyl.
  • Embodiment 5 The oxygen sensor element of embodiment 1 , wherein R ⁇ is optionally substituted pyrimidinyl.
  • Embodiment 6 The oxygen sensor element of embodiment 1 , wherein Ri is optionally substituted naphthyl.
  • Embodiment 7 The oxygen sensor element of embodiment 1 , wherein R ⁇ is optionally substituted carbazolyl.
  • Embodiment 8 The oxygen sensor element of embodiment 1 , wherein R ⁇ is optionally substituted phenylethynyl.
  • Embodiment 9 The oxygen sensor element of embodiment 1 , wherein R ⁇ is -CF 3 .
  • Embodiment 10 The oxygen sensor element of embodiment 1 , wherein R ⁇ is CN.
  • Embodiment 11 The oxygen sensor element of embodiment 1 , 2, 3, 4, 5, 6, 7, 8, 9, or 10, wherein R 2 is -CN.
  • Embodiment 12 The oxygen sensor element of embodiment 1 , 2, 3, 4, 5, 6, 7, 8, 9, or 10, wherein R 2 is -CF 3 .
  • Embodiment 13 The oxygen sensor element of embodiment 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , or 12, wherein R 3 is optionally substituted carbazolyl.
  • Embodiment 14 The oxygen sensor element of embodiment 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , or 12, wherein R 3 is optionally substituted benzocarbazolyl.
  • Embodiment 15 The oxygen sensor element of embodiment 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, or 14, wherein R 4 is optionally substituted carbazolyl.
  • Embodiment 16 The oxygen sensor element of embodiment 13, wherein R 4 is optionally substituted carbazolyl.
  • Embodiment 17 The oxygen sensor element of embodiment 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, or 13, wherein R 4 is optionally substituted benzocarbazolyl.
  • Embodiment 18 The oxygen sensor element of embodiment 14, wherein R 4 is optionally substituted benzocarbazolyl.
  • Embodiment 19 The oxygen sensor element of embodiment 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 17, or 18, wherein R 5 is optionally substituted carbazolyl.
  • Embodiment 20 The oxygen sensor element of embodiment 16, wherein R 5 is optionally substituted carbazolyl.
  • Embodiment 21 The oxygen sensor element of embodiment 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, or 17, wherein R 5 is optionally substituted phenyl.
  • Embodiment 22 The oxygen sensor element of embodiment 18, wherein R 5 is optionally substituted phenyl.
  • Embodiment 23 The oxygen sensor element of embodiment 16, wherein R 5 is optionally substituted phenyl.
  • Embodiment 24 The oxygen sensor element of embodiment 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, or 17, wherein R 5 is optionally substituted benzocarbazolyl.
  • Embodiment 25 The oxygen sensor element of embodiment 18, wherein R 5 is optionally substituted benzocarbazolyl.
  • Embodiment 26 The oxygen sensor element of embodiment 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 21 , 22, 23, 24, or 25, wherein R 6 is optionally substituted carbazolyl.
  • Embodiment 27 The oxygen sensor element of embodiment 19, wherein R 6 is optionally substituted carbazolyl.
  • Embodiment 28 The oxygen sensor element of embodiment 20, wherein R 6 is optionally substituted carbazolyl.
  • Embodiment 29 The oxygen sensor element of embodiment 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 19, 20, 21 , 24, or 25, wherein R 6 is optionally substituted phenyl.
  • Embodiment 30 The oxygen sensor element of embodiment 18, wherein R 6 is optionally substituted phenyl.
  • Embodiment 31 The oxygen sensor element of embodiment 22, wherein R 6 is optionally substituted phenyl.
  • Embodiment 32 The oxygen sensor element of embodiment 23, wherein R 6 is optionally substituted phenyl.
  • Embodiment 33 The oxygen sensor element of embodiment 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, or 24, wherein R 6 is optionally substituted benzocarbazolyl.
  • Embodiment 34 The oxygen sensor element of embodiment 18Error! Reference source not found., wherein R 6 is optionally substituted benzocarbazolyl.
  • Embodiment 35 The oxygen sensor element of embodiment 25, wherein R 6 is optionally substituted benzocarbazolyl.
  • Embodiment 36 The oxygen sensor element of embodiment 1 wherein Ri i
  • Embodiment 37 The oxygen sensor element of embodiment 1 wherein the emissive compound is:
  • Embodiment 38 The oxygen sensor element of embodiment 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 , 32, 33, 34, 35, 36, or 37, which is configured to detect an oxygen level of 0.5% by volume or less in an atmosphere that comes into contact with the oxygen sensor element.
  • Embodiment 39 A package containing the oxygen sensor element of embodiment 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 , 32, 33, 34, 35, 36, 37, or 38, wherein the oxygen sensor element is within a packaging layer, wherein the packaging layer is a barrier to the passage of oxygen through the barrier to come into contact with the oxygen sensor element.
  • Embodiment 40 A method of detecting an oxygen-containing analyte in a sample comprising contacting the sample with the oxygen sensor element of embodiment 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 , 32, 33, 34, 35, 36, 37, or 39; and detecting the presence or absence of blue emissions from the sample, wherein the presence of blue emissions indicates the absence of oxygen in the sample.
  • Embodiment 41 The method of embodiment 40, further comprising measuring the amount of blue emission in the sample and correlating the amount of blue emission from the sample with a concentration of the oxygen in the sample.
  • Embodiment 42 A method for determining the presence of oxygen in a sealed cavity, the method comprising:
  • Embodiment 43 A colorimetric indicating film comprising a first layer, the first layer comprising the oxygen sensor element of embodiment 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 , 32, 33, 34, 35, 36, 37, or 38.
  • Embodiment 44 The film of embodiment 43, wherein the film further comprises polymethylmethacrylate.
  • Embodiment 45 The film of embodiment 44, further comprising a second layer, wherein the first and second layers are adjacent to each other, and wherein the first and second layers define an internal cavity therein, and wherein the first layer is a first color in an oxygen deficient atmosphere and a second color in an oxygen present atmosphere.
  • EM-8 To a solution of 2,3,5,6-tetrafluro-4-(4'-cyanophenyl)- benzonitrile (Compound 1 ) (0.277 g, 1 mmol), 9H-carbazole (0.835 g, 5 mmol) in THF (25 mL) was added sodium hydride (60% in mineral oil, 0.2 g, 5 mmol) at about 0 °C and stirred for about 30 min.
  • Photoluminescence (PL) spectra were recorded on a FluoroMax-3 fluorescence spectrophotometer (Horiba Jobin Yvon, Edison, New Jersey, USA) .
  • 2- Methyltetrahydrofuran (2-MeTHF) (Aldrich, spectroscopic grade) was used as received.
  • 2 M (2mg of sample/1 ml_ of 2-MeTHF) was prepared and then transferred to quartz tube prior to measurement. Then, the sample was frozen by liquid nitrogen at 77K. Fluorescent emission spectrum was recorded and the highest-energy vibronic band was determined to calculate singlet (S1 ) energy level.
  • Phosphorescent emission spectrum was recorded and the highest-energy vibronic band was determined to calculate triplet (T1 ) energy level.
  • Table 1 The results are shown in Table 1 .
  • EM-8 air 0.0025 gm of EM-8 prepared as described in Example 1 above, was dissolved in 10 ml of toluene at room temperature under an ambient atmosphere (EM-8 air). After 1 ml of toluene without the EM-8 air was blanked in a 3 ml quartz cuvette and placed in a HORIBA Jobin Yvon Fluorometer (HORIBA Instruments, Irvine, CA, USA), 1 ml EM-8 air / toluene solution was placed in a 3 ml quartz cuvette, placed in a HORIBA Jobin Yvon Fluorometer and the emission of the EM-8 air solution was determined over 350 nm to about 650 nm visible light. The results are shown in FIG. 7.
  • Another sample (EM-8 N 2 ) was prepared in a manner similar to that described immediately above, except that the sample after preparation under ambient air conditions, the sample was degassed under N 2 gas for about 10 minutes. A visual comparison of the samples showed that the EM-8 N 2 sample had a blue tinge while the EM-8 air sample was clear and colorless. A 1 ml EM-8 air solution sample was tested in the same manner described above. The results are shown in FIG.7. The EM-8 N 2 sample had an emission of about 1 10000, while the EM-8 air sample had an emission of less than 2000.
  • the coated glass slide were placed inside a sealed glass container (250 ml), and the sealed glass container was filled with 12% 0 2 , 8% 0 2 , 2% 0 2 , 1 % 0 2 , 0.5% 0 2 , N 2 only, respectively.
  • the emission of the respective containers was determined on a HORIBA Jobin Yvon Fluorometer for each coated glass slide between about 350 nm to about 600 nm visible light. The results are shown in FIG. 8.
  • the emissive intensity under N 2 (no 0 2 ) l 0 /l emissive intensity of slides under various oxygen atmospheres described above were determined and plotted as shown in FIG. 9, which shows a substantially linear functional relationship between l 0 /l from about 1 % 0 2 to 12% 0 2 .

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Abstract

L'invention concerne un procédé pour détecter la présence d'un gaz et/ou un élément de capteur le réalisant. Dans certains modes de réalisation, l'élément de capteur comprend au moins un composé de la Formule 2 : dans lequel R7 peut être indépendamment un groupe arylène éventuellement substitué, un groupe carbazolyle éventuellement substitué; et R8 peut être de l'hydrogène, un phényle éventuellement substitué et/ou un carbazolyle éventuellement substitué.
PCT/US2016/019259 2015-02-24 2016-02-24 Élément de capteur de gaz Ceased WO2016138077A1 (fr)

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Cited By (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017115834A1 (fr) * 2015-12-28 2017-07-06 株式会社Ｋｙｕｌｕｘ Composé, matériau électroluminescent et élément électroluminescent organique
JP2018070586A (ja) * 2016-08-25 2018-05-10 サイノラ ゲゼルシャフト ミット ベシュレンクテル ハフツング 特に有機光電子デバイスに使用するための有機分子
CN108586318A (zh) * 2018-01-16 2018-09-28 东南大学 一种可溶液加工的热激活延迟荧光材料及其制备方法
WO2018237389A1 (fr) * 2017-06-23 2018-12-27 Kyulux Inc. Composition de matière destinée à être utilisée dans des diodes électroluminescentes organiques
WO2019046734A1 (fr) * 2017-09-01 2019-03-07 Kyulux, Inc. Composition de matière destinée à être utilisée dans des diodes électroluminescentes organiques
CN109890938A (zh) * 2016-11-14 2019-06-14 默克专利有限公司 具有受体基团和供体基团的化合物
WO2019190248A1 (fr) * 2018-03-28 2019-10-03 주식회사 엘지화학 Composé et diode électroluminescente organique le comprenant
JP2019533739A (ja) * 2017-05-04 2019-11-21 サイノラ ゲゼルシャフト ミット ベシュレンクテル ハフツング 有機分子、特に光電子デバイスに用いる有機分子
US10547014B2 (en) 2017-06-23 2020-01-28 Kyulux, Inc. Composition of matter for use in organic light-emitting diodes
WO2020022378A1 (fr) * 2018-07-27 2020-01-30 出光興産株式会社 Composé, matériau pour élément électroluminescent organique, élément électroluminescent organique, et dispositif électronique
CN110799625A (zh) * 2017-06-27 2020-02-14 辛诺拉有限公司 特别用于光电器件的有机分子
JP2020031162A (ja) * 2018-08-23 2020-02-27 国立大学法人九州大学 有機エレクトロルミネッセンス素子
WO2020050127A1 (fr) 2018-09-05 2020-03-12 国立大学法人九州大学 Dérivé de benzonitrile, matériau électroluminescent et élément électroluminescent l'utilisant
WO2020085446A1 (fr) * 2018-10-25 2020-04-30 出光興産株式会社 Composé, matériau pour élément électroluminescent organique, élément électroluminescent organique et appareil électronique
US10644249B2 (en) 2017-12-22 2020-05-05 Kyulux, Inc. Composition of matter for use in organic light-emitting diodes
US10892425B1 (en) 2017-03-03 2021-01-12 Kyulux, Inc. Composition of matter for use in organic light-emitting diodes
CN112409240A (zh) * 2020-11-20 2021-02-26 清华大学 一种有机化合物及其应用及采用该化合物的有机电致发光器
CN112409241A (zh) * 2020-11-27 2021-02-26 清华大学 一种有机化合物及其应用及采用该化合物的有机电致发光器
US11038118B2 (en) 2015-12-28 2021-06-15 Kyulux, Inc. Compound, light-emitting material, and organic light-emitting device
US11069860B2 (en) 2017-08-21 2021-07-20 Kyulux, Inc. Composition of matter for use in organic light-emitting diodes
US11104669B2 (en) 2018-02-02 2021-08-31 Kyulux, Inc. Composition of matter for use in organic light-emitting diodes
US11283027B1 (en) 2017-03-03 2022-03-22 Kyulux, Inc. Composition of matter for use in organic light-emitting diodes
CN114685359A (zh) * 2020-12-30 2022-07-01 北京鼎材科技有限公司 一种化合物及其应用、包含其的有机电致发光器件
CN114685353A (zh) * 2020-12-28 2022-07-01 北京鼎材科技有限公司 用于有机发光器件的有机化合物、有机电致发光器件
US11424417B2 (en) 2018-11-16 2022-08-23 Samsung Display Co., Ltd. Organic electroluminescence device and compound for organic electroluminescence device
US11444250B2 (en) 2017-12-05 2022-09-13 Kyulux, Inc. Composition of matter for use in organic light-emitting diodes
US11498914B2 (en) 2018-03-30 2022-11-15 Kyulux, Inc. Composition of matter for use in organic light-emitting diodes
US11542260B2 (en) 2018-01-31 2023-01-03 Kyulux, Inc. Composition of matter for use in organic light-emitting diodes
CN115677673A (zh) * 2021-07-23 2023-02-03 北京鼎材科技有限公司 嘧啶取代苯甲腈类有机化合物及其应用、有机电致发光器件
US11575088B2 (en) 2017-12-22 2023-02-07 Kyulux, Inc. Composition of matter for use in organic light-emitting diodes
US11608333B2 (en) 2018-03-20 2023-03-21 Kyulux, Inc. Composition of matter for use in organic light-emitting diodes
CN116003310A (zh) * 2022-11-29 2023-04-25 清华大学 一种有机化合物及采用该化合物的有机电致发光器
US11778904B2 (en) 2018-05-09 2023-10-03 Kyulux, Inc. Composition of matter for use in organic light-emitting diodes
KR20240021221A (ko) * 2021-06-10 2024-02-16 이데미쓰 고산 가부시키가이샤 화합물, 유기 일렉트로루미네센스 소자용 재료, 유기 일렉트로루미네센스 소자 및 전자 기기
US11985893B2 (en) 2019-11-08 2024-05-14 Samsung Display Co., Ltd. Organic electroluminescence device and aromatic compound for organic electroluminescence device

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014183080A1 (fr) * 2013-05-09 2014-11-13 Nitto Denko Corporation Composés émissifs pour dispositifs émettant de la lumière
WO2015066354A1 (fr) * 2013-10-30 2015-05-07 Nitto Denko Corporation Composés luminescents pour dispositifs luminescents

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014183080A1 (fr) * 2013-05-09 2014-11-13 Nitto Denko Corporation Composés émissifs pour dispositifs émettant de la lumière
WO2015066354A1 (fr) * 2013-10-30 2015-05-07 Nitto Denko Corporation Composés luminescents pour dispositifs luminescents

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HIROKI UOYAMA ET AL: "Highly efficient organic light-emitting diodes from delayed fluorescence", NATURE, vol. 492, no. 7428, 12 December 2012 (2012-12-12), pages 234 - 238, XP055048388, ISSN: 0028-0836, DOI: 10.1038/nature11687 *
RYOICHI ISHIMATSU ET AL: "Solvent Effect on Thermally Activated Delayed Fluorescence by 1,2,3,5-Tetrakis(carbazol-9-yl)-4,6-dicyanobenzene", THE JOURNAL OF PHYSICAL CHEMISTRY A, vol. 117, no. 27, 12 June 2013 (2013-06-12), pages 5607 - 5612, XP055122928, ISSN: 1089-5639, DOI: 10.1021/jp404120s *

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US11038118B2 (en) 2015-12-28 2021-06-15 Kyulux, Inc. Compound, light-emitting material, and organic light-emitting device
WO2017115834A1 (fr) * 2015-12-28 2017-07-06 株式会社Ｋｙｕｌｕｘ Composé, matériau électroluminescent et élément électroluminescent organique
JP2018070586A (ja) * 2016-08-25 2018-05-10 サイノラ ゲゼルシャフト ミット ベシュレンクテル ハフツング 特に有機光電子デバイスに使用するための有機分子
KR102585418B1 (ko) * 2016-11-14 2023-10-05 메르크 파텐트 게엠베하 수용체 기 및 공여체 기를 갖는 화합물
US11711976B2 (en) 2016-11-14 2023-07-25 Merck Patent Gmbh Compounds with an acceptor and a donor group
CN109890938A (zh) * 2016-11-14 2019-06-14 默克专利有限公司 具有受体基团和供体基团的化合物
KR20190085041A (ko) * 2016-11-14 2019-07-17 메르크 파텐트 게엠베하 수용체 기 및 공여체 기를 갖는 화합물
US10892425B1 (en) 2017-03-03 2021-01-12 Kyulux, Inc. Composition of matter for use in organic light-emitting diodes
US11283027B1 (en) 2017-03-03 2022-03-22 Kyulux, Inc. Composition of matter for use in organic light-emitting diodes
JP2019533739A (ja) * 2017-05-04 2019-11-21 サイノラ ゲゼルシャフト ミット ベシュレンクテル ハフツング 有機分子、特に光電子デバイスに用いる有機分子
US10981930B2 (en) 2017-05-04 2021-04-20 Cynora Gmbh Organic molecules for use in optoelectronic devices
KR102577834B1 (ko) * 2017-06-23 2023-09-12 가부시키가이샤 큐럭스 유기 발광 다이오드에 이용되는 조성물
KR20200019694A (ko) * 2017-06-23 2020-02-24 가부시키가이샤 큐럭스 유기 발광 다이오드에 이용되는 조성물
US10547014B2 (en) 2017-06-23 2020-01-28 Kyulux, Inc. Composition of matter for use in organic light-emitting diodes
US11638390B2 (en) 2017-06-23 2023-04-25 Kyulux, Inc. Composition of matter for use in organic light-emitting diodes
CN110914378A (zh) * 2017-06-23 2020-03-24 九州有机光材股份有限公司 用于有机发光二极管中的组合物
WO2018237389A1 (fr) * 2017-06-23 2018-12-27 Kyulux Inc. Composition de matière destinée à être utilisée dans des diodes électroluminescentes organiques
JP7226806B2 (ja) 2017-06-23 2023-02-21 株式会社Kyulux 有機発光ダイオードに用いられる組成物
JP2020525438A (ja) * 2017-06-23 2020-08-27 株式会社Ｋｙｕｌｕｘ 有機発光ダイオードに用いられる組成物
CN110799625A (zh) * 2017-06-27 2020-02-14 辛诺拉有限公司 特别用于光电器件的有机分子
CN110799625B (zh) * 2017-06-27 2021-12-14 辛诺拉有限公司 特别用于光电器件的有机分子
US11069860B2 (en) 2017-08-21 2021-07-20 Kyulux, Inc. Composition of matter for use in organic light-emitting diodes
WO2019046734A1 (fr) * 2017-09-01 2019-03-07 Kyulux, Inc. Composition de matière destinée à être utilisée dans des diodes électroluminescentes organiques
US11849634B2 (en) 2017-09-01 2023-12-19 Kyulux, Inc. Composition of matter for use in organic light- emitting diodes
US11444250B2 (en) 2017-12-05 2022-09-13 Kyulux, Inc. Composition of matter for use in organic light-emitting diodes
US11575088B2 (en) 2017-12-22 2023-02-07 Kyulux, Inc. Composition of matter for use in organic light-emitting diodes
US10644249B2 (en) 2017-12-22 2020-05-05 Kyulux, Inc. Composition of matter for use in organic light-emitting diodes
CN108586318A (zh) * 2018-01-16 2018-09-28 东南大学 一种可溶液加工的热激活延迟荧光材料及其制备方法
CN108586318B (zh) * 2018-01-16 2020-09-18 东南大学 一种可溶液加工的热激活延迟荧光材料及其制备方法
US11542260B2 (en) 2018-01-31 2023-01-03 Kyulux, Inc. Composition of matter for use in organic light-emitting diodes
US11104669B2 (en) 2018-02-02 2021-08-31 Kyulux, Inc. Composition of matter for use in organic light-emitting diodes
US11608333B2 (en) 2018-03-20 2023-03-21 Kyulux, Inc. Composition of matter for use in organic light-emitting diodes
CN111051284A (zh) * 2018-03-28 2020-04-21 株式会社Lg化学 化合物及包含其的有机发光器件
CN111051284B (zh) * 2018-03-28 2023-04-18 株式会社Lg化学 化合物及包含其的有机发光器件
KR20190113681A (ko) * 2018-03-28 2019-10-08 주식회사 엘지화학 화합물 및 이를 포함하는 유기 발광 소자
KR102187989B1 (ko) 2018-03-28 2020-12-07 주식회사 엘지화학 화합물 및 이를 포함하는 유기 발광 소자
WO2019190248A1 (fr) * 2018-03-28 2019-10-03 주식회사 엘지화학 Composé et diode électroluminescente organique le comprenant
US11498914B2 (en) 2018-03-30 2022-11-15 Kyulux, Inc. Composition of matter for use in organic light-emitting diodes
US11778904B2 (en) 2018-05-09 2023-10-03 Kyulux, Inc. Composition of matter for use in organic light-emitting diodes
KR20210038406A (ko) * 2018-07-27 2021-04-07 이데미쓰 고산 가부시키가이샤 화합물, 유기 일렉트로루미네센스 소자용 재료, 유기 일렉트로루미네센스 소자, 및 전자 기기
KR102739331B1 (ko) 2018-07-27 2024-12-05 이데미쓰 고산 가부시키가이샤 화합물, 유기 일렉트로루미네센스 소자용 재료, 유기 일렉트로루미네센스 소자, 및 전자 기기
CN111372918B (zh) * 2018-07-27 2023-09-05 出光兴产株式会社 化合物、用于有机电致发光元件的材料、有机电致发光元件以及电子设备
US11482681B2 (en) 2018-07-27 2022-10-25 Idemitsu Kosan Co., Ltd. Compound, material for organic electroluminescence element, organic electroluminescence element, and electronic device
WO2020022378A1 (fr) * 2018-07-27 2020-01-30 出光興産株式会社 Composé, matériau pour élément électroluminescent organique, élément électroluminescent organique, et dispositif électronique
JP7252959B2 (ja) 2018-07-27 2023-04-05 出光興産株式会社 化合物、有機エレクトロルミネッセンス素子用材料、有機エレクトロルミネッセンス素子、および電子機器
CN111372918A (zh) * 2018-07-27 2020-07-03 出光兴产株式会社 化合物、用于有机电致发光元件的材料、有机电致发光元件以及电子设备
JPWO2020022378A1 (ja) * 2018-07-27 2021-08-26 出光興産株式会社 化合物、有機エレクトロルミネッセンス素子用材料、有機エレクトロルミネッセンス素子、および電子機器
JP7325731B2 (ja) 2018-08-23 2023-08-15 国立大学法人九州大学 有機エレクトロルミネッセンス素子
JP2020031162A (ja) * 2018-08-23 2020-02-27 国立大学法人九州大学 有機エレクトロルミネッセンス素子
US12089494B2 (en) 2018-08-23 2024-09-10 Kyushu University, National University Corporation Organic electroluminescence element
TWI719618B (zh) * 2018-09-05 2021-02-21 國立大學法人九州大學 苯甲腈衍生物、發光材料及使用其之發光元件
JP7184263B2 (ja) 2018-09-05 2022-12-06 国立大学法人九州大学 ベンゾニトリル誘導体、発光材料およびそれを用いた発光素子
KR20210039418A (ko) 2018-09-05 2021-04-09 고쿠리쓰다이가쿠호진 규슈다이가쿠 벤조니트릴 유도체, 발광 재료 및 그것을 사용한 발광 소자
WO2020050127A1 (fr) 2018-09-05 2020-03-12 国立大学法人九州大学 Dérivé de benzonitrile, matériau électroluminescent et élément électroluminescent l'utilisant
US12122768B2 (en) 2018-09-05 2024-10-22 Kyushu University, National University Corporation Benzonitrile derivative, light-emitting material, and light-emitting element using same
EP3848352A4 (fr) * 2018-09-05 2022-06-01 Kyushu University, National University Corporation Dérivé de benzonitrile, matériau électroluminescent et élément électroluminescent l'utilisant
CN112638874A (zh) * 2018-09-05 2021-04-09 国立大学法人九州大学 苯甲腈衍生物、发光材料和使用该发光材料的发光元件
JPWO2020050127A1 (ja) * 2018-09-05 2021-08-26 国立大学法人九州大学 ベンゾニトリル誘導体、発光材料およびそれを用いた発光素子
WO2020085446A1 (fr) * 2018-10-25 2020-04-30 出光興産株式会社 Composé, matériau pour élément électroluminescent organique, élément électroluminescent organique et appareil électronique
US12274168B2 (en) 2018-10-25 2025-04-08 Idemitsu Kosan Co., Ltd. Compound, material for organic electroluminescent element, organic electroluminescent element, and electronic appliance
US11424417B2 (en) 2018-11-16 2022-08-23 Samsung Display Co., Ltd. Organic electroluminescence device and compound for organic electroluminescence device
US11985893B2 (en) 2019-11-08 2024-05-14 Samsung Display Co., Ltd. Organic electroluminescence device and aromatic compound for organic electroluminescence device
CN112409240A (zh) * 2020-11-20 2021-02-26 清华大学 一种有机化合物及其应用及采用该化合物的有机电致发光器
CN112409241A (zh) * 2020-11-27 2021-02-26 清华大学 一种有机化合物及其应用及采用该化合物的有机电致发光器
CN114685353A (zh) * 2020-12-28 2022-07-01 北京鼎材科技有限公司 用于有机发光器件的有机化合物、有机电致发光器件
CN114685353B (zh) * 2020-12-28 2025-04-08 北京鼎材科技有限公司 用于有机发光器件的有机化合物、有机电致发光器件
CN114685359A (zh) * 2020-12-30 2022-07-01 北京鼎材科技有限公司 一种化合物及其应用、包含其的有机电致发光器件
CN114685359B (zh) * 2020-12-30 2025-04-11 北京鼎材科技有限公司 一种化合物及其应用、包含其的有机电致发光器件
KR20240021221A (ko) * 2021-06-10 2024-02-16 이데미쓰 고산 가부시키가이샤 화합물, 유기 일렉트로루미네센스 소자용 재료, 유기 일렉트로루미네센스 소자 및 전자 기기
KR102746267B1 (ko) 2021-06-10 2024-12-23 이데미쓰 고산 가부시키가이샤 화합물, 유기 일렉트로루미네센스 소자용 재료, 유기 일렉트로루미네센스 소자 및 전자 기기
CN115677673A (zh) * 2021-07-23 2023-02-03 北京鼎材科技有限公司 嘧啶取代苯甲腈类有机化合物及其应用、有机电致发光器件
CN116003310A (zh) * 2022-11-29 2023-04-25 清华大学 一种有机化合物及采用该化合物的有机电致发光器
CN116003310B (zh) * 2022-11-29 2025-07-01 清华大学 一种有机化合物及采用该化合物的有机电致发光器

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