CN112939888A - Star-shaped D-A type conjugated molecule and synthetic method and application thereof - Google Patents
Star-shaped D-A type conjugated molecule and synthetic method and application thereof Download PDFInfo
- Publication number
- CN112939888A CN112939888A CN202110233862.9A CN202110233862A CN112939888A CN 112939888 A CN112939888 A CN 112939888A CN 202110233862 A CN202110233862 A CN 202110233862A CN 112939888 A CN112939888 A CN 112939888A
- Authority
- CN
- China
- Prior art keywords
- star
- solution
- shaped
- conjugated molecule
- reaction
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
- 238000010189 synthetic method Methods 0.000 title claims description 7
- 239000000243 solution Substances 0.000 claims abstract description 88
- 239000002904 solvent Substances 0.000 claims abstract description 42
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000126 substance Substances 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000004065 semiconductor Substances 0.000 claims abstract description 15
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000005693 optoelectronics Effects 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims abstract description 8
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001412 amines Chemical class 0.000 claims abstract description 6
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229950000688 phenothiazine Drugs 0.000 claims abstract description 5
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims abstract description 4
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 90
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 80
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 59
- 238000006243 chemical reaction Methods 0.000 claims description 57
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 51
- 238000003756 stirring Methods 0.000 claims description 45
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 41
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 40
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 38
- FKASFBLJDCHBNZ-UHFFFAOYSA-N 1,3,4-oxadiazole Chemical compound C1=NN=CO1 FKASFBLJDCHBNZ-UHFFFAOYSA-N 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000000926 separation method Methods 0.000 claims description 16
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 15
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 14
- LMPDKTVEQHXQKW-UHFFFAOYSA-N methyl 4-(n-phenylanilino)benzoate Chemical compound C1=CC(C(=O)OC)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 LMPDKTVEQHXQKW-UHFFFAOYSA-N 0.000 claims description 14
- 238000003786 synthesis reaction Methods 0.000 claims description 14
- UESSERYYFWCTBU-UHFFFAOYSA-N 4-(n-phenylanilino)benzaldehyde Chemical compound C1=CC(C=O)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 UESSERYYFWCTBU-UHFFFAOYSA-N 0.000 claims description 13
- 239000012286 potassium permanganate Substances 0.000 claims description 13
- JJTJBQLJXNJTPY-UHFFFAOYSA-N C1(=CC=CC=C1)N(C1=CC=CC=C1)C1=CC=C(C(=O)NN)C=C1 Chemical compound C1(=CC=CC=C1)N(C1=CC=CC=C1)C1=CC=C(C(=O)NN)C=C1 JJTJBQLJXNJTPY-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 11
- 239000005457 ice water Substances 0.000 claims description 11
- 238000000746 purification Methods 0.000 claims description 11
- XUDQSFMBCQRHAX-UHFFFAOYSA-N 4-(n-phenylanilino)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 XUDQSFMBCQRHAX-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000001953 recrystallisation Methods 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 9
- 239000007791 liquid phase Substances 0.000 claims description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000002274 desiccant Substances 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- -1 4-diphenylaminobenzoyl Chemical group 0.000 claims 5
- DGWFDTKFTGTOAF-UHFFFAOYSA-N P.Cl.Cl.Cl Chemical compound P.Cl.Cl.Cl DGWFDTKFTGTOAF-UHFFFAOYSA-N 0.000 claims 1
- 238000005401 electroluminescence Methods 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 238000012546 transfer Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 5
- 238000000295 emission spectrum Methods 0.000 abstract description 5
- 238000013461 design Methods 0.000 abstract description 4
- 238000002347 injection Methods 0.000 abstract description 4
- 239000007924 injection Substances 0.000 abstract description 4
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 4
- 238000001308 synthesis method Methods 0.000 abstract description 4
- 229920000620 organic polymer Polymers 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 38
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 26
- 238000001914 filtration Methods 0.000 description 22
- 239000000843 powder Substances 0.000 description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- 239000007983 Tris buffer Substances 0.000 description 18
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 12
- 239000012153 distilled water Substances 0.000 description 12
- 229940095102 methyl benzoate Drugs 0.000 description 11
- 239000005711 Benzoic acid Substances 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- 238000005303 weighing Methods 0.000 description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 7
- 238000002189 fluorescence spectrum Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 6
- 239000002798 polar solvent Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 230000002535 lyotropic effect Effects 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N DMSO-d6 Substances [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- LSWNGFUXDNRWSN-UHFFFAOYSA-N O1C=NN=C1.C1=CC=CC=C1 Chemical compound O1C=NN=C1.C1=CC=CC=C1 LSWNGFUXDNRWSN-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- JSEQNGYLWKBMJI-UHFFFAOYSA-N 9,9-dimethyl-10h-acridine Chemical group C1=CC=C2C(C)(C)C3=CC=CC=C3NC2=C1 JSEQNGYLWKBMJI-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
- C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D271/10—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles
- C07D271/107—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles with two aryl or substituted aryl radicals attached in positions 2 and 5
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D419/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen, oxygen, and sulfur atoms as the only ring hetero atoms
- C07D419/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen, oxygen, and sulfur atoms as the only ring hetero atoms containing three or more hetero rings
-
- 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
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
- H10K85/6565—Oxadiazole compounds
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- 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
- C09K2211/1007—Non-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
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
-
- 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
- C09K2211/1048—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with oxygen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Electromagnetism (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
本发明公开了一种星形D‑A型共轭分子及其合成方法与应用，属于功能有机高分子材料技术领域。该星形D‑A型共轭分子的化学结构式为：
The invention discloses a star-shaped D-A type conjugated molecule, a synthesis method and application thereof, and belongs to the technical field of functional organic polymer materials. The chemical structural formula of the star-shaped D-A conjugated molecule is:
Description
Technical Field
The invention relates to the technical field of functional organic polymer materials, in particular to a star-shaped D-A type conjugated molecule and a synthetic method and application thereof.
Background
A molecular system with a D-A type structure is one of the hot spots of the research of the organic solar cell material at present, the synthesis and structural diversity of D-A type compounds, and the luminescent properties of D-A type molecules corresponding to different configurations and substituent types are obviously different.
In view of this, the inventors have specifically proposed a novel compound having a D-A type structure with good light-emitting properties.
Disclosure of Invention
One of the objects of the present invention consists in providing a completely new star-shaped conjugated molecule of the D-A type.
Another object of the present invention is to provide a method for synthesizing the star-shaped D-A type conjugated molecule.
It is a further object of the present invention to provide an organic semiconductor material comprising the star-shaped D-A type conjugated molecule described above.
The fourth object of the present invention is to provide an organic optoelectronic device whose material is prepared to include the above star-shaped D-A type conjugated molecule or organic semiconductor material.
The application can be realized as follows:
in a first aspect, the present application provides a star-shaped D-a type conjugated molecule having the chemical formula:
r is selected from diphenylamine, imidazole and derivatives thereof, carbazole and derivatives thereof,Any one of phenoxazine, phenothiazine, acridine and amine; wherein, 1,3, 4-oxadiazole is used as an electron acceptor, and R is used as an electron donor.
In an alternative embodiment, R is diphenylamine and the star D-a conjugated molecule has the formula:
in a second aspect, the present application provides a method for synthesizing a star-shaped D-a type conjugated molecule as in the previous embodiments, comprising the steps of: synthesizing star-shaped D-A type conjugated molecules according to the chemical structural formula.
In an alternative embodiment, when the electron donor in the star D-a type conjugated molecule is diphenylamine and the electron acceptor is 1,3, 4-oxadiazole, the step of synthesizing the star D-a type conjugated molecule comprises: reacting a solution of 4-dianilinobenzoyl hydrazine with 1,3, 5-benzenetricarbonyl chloride, reacting the resulting reaction product with phosphorus oxychloride, followed by recrystallization.
In an alternative embodiment, a solution of 4-dianilinobenzoyl hydrazine is reacted with 1,3, 5-benzenetricarbonyl chloride at 10-30 ℃ for 30-40 h.
In an alternative embodiment, the mass ratio of 4-diphenylaminobenzoyl hydrazine to 1,3, 5-benzenetricarboxylic acid chloride is 0.9: 0.1-0.3.
In an alternative embodiment, the solvent in the solution of 4-dianilinobenzoyl hydrazine comprises tetrahydrofuran.
In an alternative embodiment, 4-dianilinobenzoyl hydrazine is used in a ratio to tetrahydrofuran of 0.9g to 45-55 mL.
In an alternative embodiment, the method further comprises the steps of performing primary drying, methanol purification and secondary drying on a reaction product obtained after the reaction of the solution of the 4-dianilinobenzoyl hydrazine and the 1,3, 5-benzene trimethyl acyl chloride before the reaction with the phosphorus oxychloride.
In an alternative embodiment, the reaction product of the reaction of the solution of 4-dianilinobenzoyl hydrazine and 1,3, 5-benzene tricarboxy chloride and phosphorus oxychloride are heated and stirred for reflux reaction for 35-45 h.
In an alternative embodiment, the ratio of 4-diphenylaminobenzoyl hydrazine to phosphorus oxychloride used is 0.9g:40-60 mL.
In an alternative embodiment, the recrystallization process uses a mixture of ethanol and tetrahydrofuran as the solvent.
In an optional embodiment, before recrystallization, the method further comprises the steps of cooling the solution obtained after the reaction with the phosphorus oxychloride, adding the cooled solution into ice water, stirring for 0.5-1.5h, and carrying out solid-liquid separation to obtain a liquid phase.
In an alternative embodiment, the 4-dianilinobenzoyl hydrazine is obtained by: reacting the solution of 4-diphenylamine methyl benzoate with hydrazine hydrate, and cooling for crystallization.
In an alternative embodiment, the solvent in the solution of methyl 4-diphenylaminobenzoate comprises ethanol.
In an alternative embodiment, the ratio of methyl 4-diphenylaminobenzoate to ethanol is 3g:40-50 mL.
In an alternative embodiment, the ratio of methyl 4-diphenylaminobenzoate to hydrazine hydrate is 3g:45-55 mL.
In an alternative embodiment, the reaction of the solution of methyl 4-diphenylaminobenzoate with hydrazine hydrate is carried out under reflux with heating and stirring for 35-45 h.
In an alternative embodiment, methyl 4-diphenylaminobenzoate is obtained by: mixing the mixture of methanol and tetrahydrofuran with 4-diphenylamine-benzoic acid, reacting with thionyl chloride under the condition of ice-water bath, extracting with dichloromethane, performing liquid-liquid separation, and separating and purifying the separated lower-layer filtrate.
In an alternative embodiment, the ratio of the amount of the mixture of methanol and tetrahydrofuran to 4-diphenylaminobenzoic acid is 40-60mL:3g, and the volume ratio of methanol to tetrahydrofuran in the mixture of methanol and tetrahydrofuran is 1:5 to 1:4.
In an alternative embodiment, the ratio of 4-diphenylaminobenzoic acid to thionyl chloride is 3g:4-6 mL.
In an alternative embodiment, the reaction with thionyl chloride is carried out under heating and stirring conditions for 8 to 12h under reflux.
In an alternative embodiment, the desiccant used in the water removal process comprises anhydrous magnesium sulfate.
In an alternative embodiment, the separation and purification adopts a column chromatography mode, and a developing agent used for the separation and purification is a mixed solution of dichloromethane and petroleum ether in a volume ratio of 4:1-5: 1.
In an alternative embodiment, 4-diphenylaminobenzoic acid is obtained by: reacting the solution of 4-diphenylamine benzaldehyde with potassium permanganate, removing the organic solvent, carrying out solid-liquid separation, and adding dilute hydrochloric acid into the separated liquid phase to obtain a precipitate.
In an alternative embodiment, the solvent in the solution of 4-diphenylaminobenzaldehyde is a mixture of acetone and water.
In an alternative embodiment, the amount ratio of the mixture of acetone and water to 4-diphenylaminobenzaldehyde is 40-60mL:5g, and the volume ratio of acetone to water in the mixture of acetone and water is 4:1-5: 1.
In an alternative embodiment, the ratio of 4-diphenylaminobenzaldehyde to potassium permanganate is 5g:7 to 7.5 g.
In an alternative embodiment, the reaction of the solution of 4-diphenylaminobenzaldehyde with potassium permanganate is carried out under heating and stirring for 6 to 10 hours under reflux.
In alternative embodiments, the concentration of dilute hydrochloric acid is 8 to 12 vt%.
In a third aspect, the present application provides an organic semiconductor material comprising a star-shaped D-a type conjugated molecule as in the previous embodiments.
In a fourth aspect, the present invention provides an organic opto-electronic device fabricated from a material comprising the star D-a type conjugated molecule of the previous embodiment or the organic semiconducting material of the previous embodiment.
In alternative embodiments, the organic optoelectronic device comprises an organic electroluminescent device, a fluorescent sensor, or a solar cell.
In an alternative embodiment, the organic electroluminescent device comprises an organic light emitting diode.
In alternative embodiments, the organic light emitting diode comprises an ultraviolet or visible OLED.
The beneficial effect of this application includes:
the star-shaped D-A conjugated molecule provided by the application plays a role in improving electron injection balance and electron transfer rate by introducing oxadiazole electron-withdrawing groups, and simultaneously, charge transfer effects on branches are superposed by star-shaped molecule design, so that the intramolecular charge transfer property is improved. The molecule shows strong blue emission in non-polar solution and strong ultraviolet and visible emission in solid state. In addition, the emission spectrum of the molecule in the solution can generate larger red shift along with the increase of the polarity of the solvent, shows obvious lyotropic discoloration property, can be used as an organic semiconductor material and is suitable for preparing organic photoelectric devices, such as organic electroluminescent devices, fluorescent sensors or solar cells. In addition, the synthesis method of the star-shaped D-A type conjugated molecule is simple and easy to operate.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a chart showing an infrared absorption spectrum at room temperature of 1,3, 5-tris { [ 4-4-diphenylamino ]1,3, 4-oxadiazole } benzene obtained in example 1;
FIG. 2 is a drawing showing 1,3, 5-tris { [ 4-4-dianilino ] amine obtained in example 1]1,3, 4-oxadiazole benzene in DMSO-d6Medium nuclear magnetic resonance hydrogen spectrum (300 MHz);
FIG. 3 is a fluorescence emission spectrum of a solid powder of 1,3, 5-tris { [ 4-4-diphenylamino ]1,3, 4-oxadiazole } benzene in the test example;
FIG. 4 is a photograph of 1,3, 5-tris { [ 4-4-diphenylamino ]1,3, 4-oxadiazole } benzene in a different polar solvent (under a 365nm ultraviolet lamp) in the test example;
FIG. 5 is a normalized UV-visible absorption and fluorescence emission spectra of 1,3, 5-tris { [ 4-4-dianilino ]1,3, 4-oxadiazole } benzene in different polar solvents in the experimental examples.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The star-shaped D-a type conjugated molecule provided by the present application, and the synthesis method and application thereof are specifically described below.
The present application proposes star-shaped D-A type conjugated molecules which integrate an electron donor and an electron acceptor. The chemical structural formula of the star-shaped D-A type conjugated molecule is as follows:
r is selected from any one of diphenylamine, imidazole and derivatives thereof, carbazole and derivatives thereof, phenoxazine, phenothiazine, acridine and amine; wherein, 1,3, 4-oxadiazole is used as an electron acceptor, and R is used as an electron donor.
The 1,3, 4-oxadiazole ring in the star-shaped D-A type conjugated molecule has good thermal stability, chemical stability and good electron accepting capability, can form a good pi-conjugated structure by being connected with an aromatic ring, and can well adjust the electronic structure and the photoelectric property of the material.
In some alternative embodiments, the electron donor in the star D-a conjugated molecule is diphenylamine, the electron acceptor is 1,3, 4-oxadiazole, and the chemical structure of the star D-a conjugated molecule is:
this material is referred to as 1,3, 5-tris { [ 4-4-dianilino ]]1,3, 4-oxadiazole benzene.
In other alternative embodiments, the electron donor in the star D-a conjugated molecule is imidazole, the electron acceptor is 1,3, 4-oxadiazole, and the chemical structure of the star D-a conjugated molecule is:
in other alternative embodiments, the electron donor in the star D-a conjugated molecule is 9-carbazole, the electron acceptor is 1,3, 4-oxadiazole, and the chemical structure of the star D-a conjugated molecule is:
in other alternative embodiments, the electron donor in the star D-a conjugated molecule is 3, 6-dimethyl-9-carbazole, the electron acceptor is 1,3, 4-oxadiazole, and the chemical structure of the star D-a conjugated molecule is:
in other alternative embodiments, the electron donor in the star D-a conjugated molecule is 3, 6-di-tert-butyl 9-carbazole, the electron acceptor is 1,3, 4-oxadiazole, and the chemical structure of the star D-a conjugated molecule is:
in other alternative embodiments, the electron donor in the star-shaped conjugated molecule of type D-a is 1,3,6, 8-tetramethyl-9-carbazole, the electron acceptor is 1,3, 4-oxadiazole, and the star-shaped conjugated molecule of type D-a has the chemical formula:
in other alternative embodiments, the electron donor in the star D-A conjugated molecule is N3,N3,N6,N6The-tetraphenyl-9-carbazole-3, 6-diamine has an electron acceptor of 1,3, 4-oxadiazole, and the star D-A type conjugated molecule has the chemical structural formula:
in other alternative embodiments, the electron donor in the star D-a conjugated molecule is N, N-diphenyl-9-carbazol-3-amine, the electron acceptor is 1,3, 4-oxadiazole, and the chemical structure of the star D-a conjugated molecule is:
in other alternative embodiments, the electron donor in the star D-a conjugated molecule is 10-phenoxazine, the electron acceptor is 1,3, 4-oxadiazole, and the chemical structure of the star D-a conjugated molecule is:
in other alternative embodiments, the electron donor in the star D-a conjugated molecule is 5, 10-dihydrophenoxazine, the electron acceptor is 1,3, 4-oxadiazole, and the chemical structure of the star D-a conjugated molecule is:
in other alternative embodiments, the electron donor in the star D-a conjugated molecule is phenothiazine, the electron acceptor is 1,3, 4-oxadiazole, and the chemical structure of the star D-a conjugated molecule is:
in other alternative embodiments, the electron donor in the star D-A conjugated molecule is 9,9 dimethyl-9, 10 dihydroacridine, the electron acceptor is 1,3, 4-oxadiazole, and the chemical structure of the star D-A conjugated molecule is:
in other alternative embodiments, the electron donor in the star D-a conjugated molecule is bis- (4- (tri-butyl) phenyl) amine, the electron acceptor is 1,3, 4-oxadiazole, and the chemical structure of the star D-a conjugated molecule is:
in other alternative embodiments, the electron donor in the star D-a conjugated molecule is N1- (4- (diphenylamine) phenyl) -N4N 4-diphenylbenzene-1, 4-diamine, the electron acceptor is 1,3, 4-oxadiazole, and the chemical structure of the star D-a conjugated molecule is:
in addition, the above structural formulae may be correspondingly adjusted according to the different substituents included in the present application.
The star-shaped D-A type conjugated molecule plays a role in improving electron injection balance and electron transfer rate by introducing an oxadiazole electron-withdrawing group, and simultaneously, charge transfer effects on branches are superposed by star-shaped molecule design, so that the intramolecular charge transfer property is improved. The molecule shows strong blue emission in non-polar solution and strong ultraviolet and visible emission in solid state. In addition, the emission spectrum of the molecule in the solution is greatly red-shifted along with the increase of the polarity of the solvent, and obvious lyotropic discoloration property is shown.
Correspondingly, the application also provides a synthesis method of the star-shaped D-A type conjugated molecule, which comprises the following steps: the electron donor and the electron acceptor are integrated to form a star-shaped D-a type conjugated molecule.
By way of example, when the electron donor in the star-shaped D-a type conjugated molecule is diphenylamine and the electron acceptor is 1,3, 4-oxadiazole, the step of synthesizing the star-shaped D-a type conjugated molecule may include: reacting a solution of 4-dianilinobenzoyl hydrazine with 1,3, 5-benzenetricarbonyl chloride, reacting the resulting reaction product with phosphorus oxychloride, followed by recrystallization.
Wherein the reaction of the solution of 4-dianilinobenzoyl hydrazine with 1,3, 5-benzenetricarbonyl chloride may be carried out at 10 to 30 deg.C (understood as room temperature) for 30 to 40 hours, preferably 30 hours. The mass ratio of 4-diphenylaminobenzoyl hydrazine to 1,3, 5-benzenetricarboxylic acid chloride may be 0.9:0.1-0.3, preferably 0.9: 0.2.
In an alternative embodiment, the solvent in the solution of 4-dianilinobenzoyl hydrazine may be, for example, tetrahydrofuran. The amount ratio of 4-dianilinobenzoyl hydrazine to tetrahydrofuran may be 0.9g:45 to 55mL, preferably 0.9g:50 mL.
Further, before the reaction with phosphorus oxychloride, the method also comprises the steps of carrying out primary drying, methanol purification and secondary drying on a reaction product obtained after the reaction of the solution of p-4-diphenylaminobenzoyl hydrazine and 1,3, 5-benzene tricarboxychloride. For reference, the first drying may be to dry the solvent to dryness using a vacuum rotary evaporator to obtain a green product. The second drying can be carried out in a drying mode. The powder obtained after the second drying reacts with the phosphorus oxychloride.
In an alternative embodiment, the reaction product of the reaction of the solution of 4-dianilinobenzoyl hydrazine with 1,3, 5-benzenetricarbonyl chloride (which is understood to be the powder obtained after the second drying) and phosphorus oxychloride can be reacted under heating and stirring for 35 to 45 hours, preferably 40 hours, under reflux. The mixing sequence of the two substances is preferably that the powder obtained after the second drying is added to the phosphorus oxychloride. The ratio of 4-diphenylaminobenzoyl hydrazine to phosphorus oxychloride used may be, for example, 0.9g:40 to 60mL, preferably 0.9g:50 mL.
In an alternative embodiment, the recrystallization process uses a mixture of ethanol and tetrahydrofuran as the solvent. It is worth mentioning that before recrystallization, the method further comprises the steps of cooling (to room temperature) the solution obtained after the reaction with the phosphorus oxychloride, then adding (slowly dropping) ice water, stirring for 0.5-1.5h, preferably 1h, and carrying out solid-liquid separation to obtain a liquid phase. The liquid phase is used for recrystallization purification with the mixed solution of ethanol and tetrahydrofuran.
In an alternative embodiment, the 4-diphenylaminobenzoyl hydrazine used above may be obtained by the following steps: reacting the solution of 4-diphenylamine methyl benzoate with hydrazine hydrate, and cooling for crystallization.
The solvent in the solution of methyl 4-diphenylaminobenzoate may include, for example, ethanol, and may further include methanol. When the solvent is ethanol, the using amount ratio of the methyl 4-diphenylamine benzoate to the ethanol is 3g:40-50mL, and preferably 3g:45 mL.
The dosage ratio of the 4-diphenylamine methyl benzoate to the hydrazine hydrate can be 3g:45-55mL, and preferably 3g:50 mL. The reaction of the solution of 4-diphenylamine methyl benzoate and hydrazine hydrate can be carried out under heating and stirring for 35-45h, preferably 40h, under reflux. The mixing sequence of the solution of 4-diphenylaminobenzoic acid methyl ester and hydrazine hydrate is preferably to add hydrazine hydrate to the solution of 4-diphenylaminobenzoic acid methyl ester.
After the reaction is completed, cooling the reaction solution to room temperature, separating out flaky crystals, filtering, and washing with methanol to obtain a flaky crystal product 4-diphenylamine-benzoyl hydrazine with high purity.
In an alternative embodiment, the methyl 4-diphenylaminobenzoate used as described above may be obtained by: mixing the mixture of methanol and tetrahydrofuran with 4-diphenylamine-benzoic acid, reacting with thionyl chloride under the condition of ice-water bath, extracting with dichloromethane, performing liquid-liquid separation, and separating and purifying the separated lower-layer filtrate.
Wherein, the dosage ratio of the mixture of methanol and tetrahydrofuran and 4-diphenylamine-benzoic acid can be 40-60mL:3g, and preferably 50mL:3 g. The volume ratio of methanol to tetrahydrofuran in the mixture of methanol and tetrahydrofuran may be from 1:5 to 1:4, preferably 1: 4.5.
The amount ratio of 4-diphenylaminobenzoic acid to thionyl chloride may be 3g:4-6mL, preferably 3g:5 mL. For convenience of understanding, a mixed system of a mixture of methanol and tetrahydrofuran and 4-diphenylaminobenzoic acid is defined as a first reaction solution in the present application. The reaction of the first reaction solution with thionyl chloride may be a reflux reaction under heating with stirring for 8 to 12 hours, preferably 10 hours. The order of mixing the first reaction solution and thionyl chloride is preferably to add thionyl chloride slowly to the first reaction solution, stir for 1 hour, and then heat, stir and reflux.
And after the first reaction solution completely reacts with thionyl chloride, cooling the second reaction solution obtained after the reaction to room temperature, adding a proper amount of distilled water into the second reaction solution, stirring, then extracting with dichloromethane, separating liquid, and taking the lower layer liquid. Adding a proper amount of drying agent (used for removing water) into the lower layer liquid, stirring and absorbing water. The drying agent used for the water removal may be anhydrous magnesium sulfate, and may be anhydrous barium sulfate or the like.
Removing water, performing solid-liquid separation (such as filtration), and separating and purifying the filtrate. For reference, column chromatography may be used for separation and purification, and the developing solvent used for separation and purification may be a mixed solution of dichloromethane and petroleum ether in a volume ratio of 4:1 to 5:1 (preferably 4.5: 1).
After separation and purification, the solvent is removed by a vacuum rotary evaporator to obtain an oily product, namely 4-diphenylamine methyl benzoate.
In an alternative embodiment, the 4-diphenylaminobenzoic acid used above may be obtained by: reacting the solution of 4-diphenylamine benzaldehyde with potassium permanganate, removing the organic solvent, carrying out solid-liquid separation, and adding dilute hydrochloric acid into the separated liquid phase to obtain a precipitate.
Wherein, the solvent in the solution of the 4-diphenylamine benzaldehyde can be a mixed solution of acetone and water. The amount ratio of the mixture of acetone and water to 4-diphenylaminobenzaldehyde may be 40-60mL:5g, preferably 50mL:5 g. The volume ratio of acetone to water in the mixture of acetone and water may be 4:1 to 5:1, such as 4.5: 1.
The ratio of 4-diphenylaminobenzaldehyde to potassium permanganate may be 5g:7 to 7.5g, such as 5g:7.23g, of both. The mixing sequence of the 4-diphenylaminobenzaldehyde solution and the potassium permanganate powder is preferably to slowly add the potassium permanganate powder to the 4-diphenylaminobenzaldehyde solution under stirring, followed by reflux reaction under heating and stirring for 6 to 10 hours, preferably 8 hours.
After the reaction is completed, cooling the reaction solution to room temperature, evaporating the solvent by using a vacuum rotary evaporator, adding a proper amount of distilled water, carrying out solid-liquid separation (filtration), adding a plurality of drops of dilute hydrochloric acid into the obtained filtrate, stirring, generating white flocculent precipitate, filtering, washing the white flocculent precipitate with distilled water, carrying out suction filtration, and drying to obtain white powder 4-diphenylamine-benzoic acid.
The concentration of the dilute hydrochloric acid used may, by reference, be between 8 and 12 vt%, preferably 10 vt%.
In summary, the synthetic route of the star-shaped D-a conjugated molecule using diphenylamine as an electron donor and 1,3, 4-oxadiazole as an electron acceptor in the present application can be summarized as follows:
the method has the advantages of simple operation, easily controlled process and high yield.
Further, the application provides the application of the star-shaped D-A type conjugated molecule, for example, the star-shaped D-A type conjugated molecule can be used as an organic semiconductor material, and can also be used for preparing organic photoelectric devices, such as organic electroluminescent devices, fluorescent sensors or solar cells. In particular, it can be used for the preparation of organic light emitting diodes, such as ultraviolet or visible OLEDs, and the like.
The theoretical supports for its application include: the D-A type organic conjugated molecule has the advantages of easy regulation and control of spectrum, strong stability, high response speed and the like, and has strong interaction with a polar solvent, so that the D-A type organic conjugated molecule can generate a lyotropic color change behavior in solvents with different polarities and shows the sensitivity to the polarity of the solvent. When different D-A structure organic molecules are selected as the emitting layer of the OLED, different brightness can be generated. Meanwhile, the lower HOMO-LUMO energy level of the D-A type molecules is beneficial to capturing electrons, and the device performance of the organic light-emitting diode is improved. When the D-A molecule is applied to an organic fluorescent sensor, the structure and the photoelectric property of the D-A molecule can be regulated and controlled through molecular engineering, so that the D-A molecule has extremely high sensitivity to the change of the surrounding environment, and the corresponding change of a spectrum can be caused by the slight change of the external environment, thereby being an excellent material for preparing the fluorescent sensor. The D, A structure can be used as a recognition group or a part of the recognition group, and when the recognition group is combined with a guest, charge transfer occurs in molecules, so that the fluorescence spectrum is changed.
Accordingly, the present application also provides an organic semiconductor material comprising a star-shaped D-a type conjugated molecule as in the previous embodiments. It is understood that the organic semiconductor material may contain other substances used in organic semiconductors in addition to the star-shaped D-A type conjugated molecule referred to in this application.
The present invention also provides an organic opto-electronic device prepared from a material comprising the star-shaped D-a type conjugated molecule according to the previous embodiment or the organic semiconducting material according to the previous embodiment.
In alternative embodiments, the organic optoelectronic device comprises an organic electroluminescent device, a fluorescent sensor, or a solar cell. The organic electroluminescent device includes an organic light emitting diode, and the organic light emitting diode includes an ultraviolet or visible OLED.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
This example provides a method for synthesizing 1,3, 5-tris { [ 4-4-diphenylamino ]1,3, 4-oxadiazole } benzene, which comprises the following steps:
(1) synthesis of 4-diphenylamine-benzoic acid
Weighing 5g of 4-diphenylamine benzaldehyde, and pouring into a conical flask; to this, 50mL of a mixture of acetone and water (4.5: 1 by volume) was added; potassium permanganate powder (7.23 g) was slowly added with stirring, followed by heating with stirring and refluxing for 8 hours. After the reaction is completed, firstly cooling the solution to room temperature, and evaporating the solvent to dryness by using a vacuum rotary evaporator; then adding a proper amount of distilled water into the mixture, and filtering the mixture; adding a plurality of drops of 10 vt% diluted hydrochloric acid into the obtained filtrate, stirring, generating white flocculent precipitate, and filtering; and washing the white precipitate with distilled water for several times, filtering, and drying to obtain white powder.
(2) Synthesis of 4-diphenylamine methyl benzoate
Weighing 3g of 4-diphenylamine-benzoic acid synthesized in the previous step, and pouring into a 150mL conical flask; to this was added 50mL of a mixed solution of methanol and tetrahydrofuran (methanol: tetrahydrofuran ═ 1: 4.5); under the condition of an ice-water bath, 5mL of thionyl chloride was slowly injected thereinto, stirred for 1 hour, heated, and refluxed with stirring for 10 hours. After the reaction is completed, firstly cooling the solution to room temperature, adding a proper amount of distilled water into the solution and stirring the solution; then extracting and separating by using dichloromethane to take the lower layer liquid, adding a proper amount of anhydrous magnesium sulfate, stirring, absorbing water and filtering; separating and purifying the obtained filtrate by column chromatography (the developing solvent is a mixed solution of dichloromethane and petroleum ether, and the volume ratio is 4.5: 1); the solvent was then spun dry using a vacuum rotary evaporator to give the product as an oil.
(3) Synthesis of 4-diphenylamino benzoyl hydrazine
Dissolving the 4-diphenylamine-methyl benzoate obtained in the last step in 45mL of ethanol; 50mL of hydrazine hydrate was added thereto, and the reaction was refluxed for 40 hours with heating and stirring. After the reaction is completed, firstly cooling the solution to room temperature, and separating out flaky crystals; filtration and washing with methanol several times gave the product as plate crystals.
(4) Synthesis of 1,3, 5-tris { [ 4-4-diphenylamino ]1,3, 4-oxadiazole } benzene
Weighing 0.9g of 4-diphenylamine-benzoyl hydrazine synthesized in the previous step, and pouring the weighed 4-diphenylamine-benzoyl hydrazine into a conical flask filled with 50mL of tetrahydrofuran; then, 0.2g of 1,3, 5-benzenetricarboxylic acid chloride was added thereto, and the reaction was stirred at normal temperature for 30 hours. After the reaction is finished, evaporating the solvent to dryness by utilizing a vacuum rotary evaporator to obtain a green product, purifying by using methanol, and drying. The resulting powder was then poured into a conical flask containing 50mL of phosphorus oxychloride, heated with stirring and refluxed for 40 hours. After the reaction is finished, cooling the solution to room temperature, slowly dropping the solution into ice water, stirring for 1 hour, filtering, and recrystallizing and purifying by using a mixed solvent of ethanol and tetrahydrofuran to obtain a final product.
The obtained final product was subjected to infrared absorption spectroscopy and nuclear magnetic resonance hydrogen spectroscopy, and the results are shown in fig. 1 and 2, and the specific data are as follows:
FT-IR(KBr，cm-1)：3440，3060，3044，1589，1489，1426，1326，1281，1171，1080，1021，1007，985，889，839，780，753，694，621，521，476。
1H NMR(300MHz,DMSO-d6)：8.66(s，3H)，7.92(s，6H)，7.38(m，12H)，7.24-7.10(m，18H)，6.95(d，6H)。
it can be thus demonstrated that the final product obtained in this example has the structure:
example 2
This example provides a method for synthesizing 1,3, 5-tris { [ 4-4-diphenylamino ]1,3, 4-oxadiazole } benzene, which comprises the following steps:
(1) synthesis of 4-diphenylamine-benzoic acid
Weighing 5g of 4-diphenylamine benzaldehyde, and pouring into a conical flask; to this, 40mL of a mixture of acetone and water (4: 1 by volume) was added; under stirring, 7g of potassium permanganate powder was slowly added, followed by heating, stirring, and refluxing for 6 hours. After the reaction is completed, firstly cooling the solution to room temperature, and evaporating the solvent to dryness by using a vacuum rotary evaporator; then adding a proper amount of distilled water into the mixture, and filtering the mixture; adding a plurality of drops of 8 vt% diluted hydrochloric acid into the obtained filtrate, stirring, generating white flocculent precipitate, and filtering; and washing the white precipitate with distilled water for several times, filtering, and drying to obtain white powder.
(2) Synthesis of 4-diphenylamine methyl benzoate
Weighing 3g of 4-diphenylamine-benzoic acid synthesized in the previous step, and pouring into a 150mL conical flask; to this was added 40mL of a mixed solution of methanol and tetrahydrofuran (methanol: tetrahydrofuran ═ 1: 4); under the condition of an ice-water bath, 4mL of thionyl chloride was slowly injected thereinto, stirred for 1 hour, heated, and refluxed with stirring for 8 hours. After the reaction is completed, firstly cooling the solution to room temperature, adding a proper amount of distilled water into the solution and stirring the solution; then extracting and separating by using dichloromethane to take the lower layer liquid, adding a proper amount of anhydrous magnesium sulfate, stirring, absorbing water and filtering; separating and purifying the obtained filtrate by column chromatography (the developing solvent is a mixed solution of dichloromethane and petroleum ether, and the volume ratio is 4: 1); the solvent was then spun dry using a vacuum rotary evaporator to give the product as an oil.
(3) Synthesis of 4-diphenylamino benzoyl hydrazine
Dissolving the 4-diphenylamine methyl benzoate obtained in the last step into 40mL of ethanol; to this was added 45mL of hydrazine hydrate, and the reaction was refluxed with heating for 35 hours. After the reaction is completed, firstly cooling the solution to room temperature, and separating out flaky crystals; filtration and washing with methanol several times gave the product as plate crystals.
(4) Synthesis of 1,3, 5-tris { [ 4-4-diphenylamino ]1,3, 4-oxadiazole } benzene
Weighing 0.9g of 4-diphenylamine-benzoyl hydrazine synthesized in the previous step, and pouring the weighed 4-diphenylamine-benzoyl hydrazine into a conical flask filled with 45mL of tetrahydrofuran; then, 0.1g of 1,3, 5-benzenetricarboxylic acid chloride was added thereto, and the reaction was stirred at normal temperature for 35 hours. After the reaction is finished, evaporating the solvent to dryness by utilizing a vacuum rotary evaporator to obtain a green product, purifying by using methanol, and drying. The resulting powder was poured into a conical flask containing 45mL of phosphorus oxychloride, heated with stirring and refluxed for 35 hours. After the reaction is finished, cooling the solution to room temperature, slowly dropping the solution into ice water, stirring for 1 hour, filtering, and recrystallizing and purifying by using a mixed solvent of ethanol and tetrahydrofuran to obtain a final product.
Example 3
This example provides a method for synthesizing 1,3, 5-tris { [ 4-4-diphenylamino ]1,3, 4-oxadiazole } benzene, which comprises the following steps:
(1) synthesis of 4-diphenylamine-benzoic acid
Weighing 5g of 4-diphenylamine benzaldehyde, and pouring into a conical flask; 60mL of a mixture of acetone and water (volume ratio: 5:1) was added thereto; potassium permanganate powder (7.5 g) was slowly added with stirring, followed by heating with stirring and refluxing for 10 hours. After the reaction is completed, firstly cooling the solution to room temperature, and evaporating the solvent to dryness by using a vacuum rotary evaporator; then adding a proper amount of distilled water into the mixture, and filtering the mixture; adding a plurality of drops of 12 vt% diluted hydrochloric acid into the obtained filtrate, stirring, generating white flocculent precipitate, and filtering; and washing the white precipitate with distilled water for several times, filtering, and drying to obtain white powder.
(2) Synthesis of 4-diphenylamine methyl benzoate
Weighing 3g of 4-diphenylamine-benzoic acid synthesized in the previous step, and pouring into a 150mL conical flask; to this, 60mL of a mixed solution of methanol and tetrahydrofuran (methanol: tetrahydrofuran ═ 1:5) was added; under the condition of an ice-water bath, 6mL of thionyl chloride was slowly injected thereinto, stirred for 1 hour, heated, and refluxed with stirring for 12 hours. After the reaction is completed, firstly cooling the solution to room temperature, adding a proper amount of distilled water into the solution and stirring the solution; then extracting and separating by using dichloromethane to take the lower layer liquid, adding a proper amount of anhydrous magnesium sulfate, stirring, absorbing water and filtering; separating and purifying the obtained filtrate by column chromatography (the developing solvent is a mixed solution of dichloromethane and petroleum ether, and the volume ratio is 5: 1); the solvent was then spun dry using a vacuum rotary evaporator to give the product as an oil.
(3) Synthesis of 4-diphenylamino benzoyl hydrazine
Dissolving the 4-diphenylamine-methyl benzoate obtained in the last step into 50mL of ethanol; 55mL of hydrazine hydrate was added thereto, and the reaction was refluxed with heating for 45 hours. After the reaction is completed, firstly cooling the solution to room temperature, and separating out flaky crystals; filtration and washing with methanol several times gave the product as plate crystals.
(4) Synthesis of 1,3, 5-tris { [ 4-4-diphenylamino ]1,3, 4-oxadiazole } benzene
Weighing 0.9g of 4-diphenylamine-benzoyl hydrazine synthesized in the previous step, and pouring the weighed 4-diphenylamine-benzoyl hydrazine into a conical flask filled with 55mL of tetrahydrofuran; then, 0.3g of 1,3, 5-benzenetricarboxylic acid chloride was added thereto, and the reaction was stirred at normal temperature for 40 hours. After the reaction is finished, evaporating the solvent to dryness by utilizing a vacuum rotary evaporator to obtain a green product, purifying by using methanol, and drying. The resulting powder was then poured into a conical flask containing 55mL of phosphorus oxychloride, heated with stirring and refluxed for 45 hours. After the reaction is finished, cooling the solution to room temperature, slowly dropping the solution into ice water, stirring for 1 hour, filtering, and recrystallizing and purifying by using a mixed solvent of ethanol and tetrahydrofuran to obtain a final product.
Test examples
1,3, 5-tris { [ 4-4-dianilino ] obtained in example 1]1,3, 4-oxadiazole benzene was used as an example, and to investigate the light-emitting property of the molecule, we tested the emission spectrum of the molecule in different states, and observed the solid and dilute solutions under an ultraviolet lamp, and the results are shown in fig. 3 to 5. Wherein, FIG. 3 is fluorescence emission spectrum of solid powder, the inner diagram is solid powder photo under 365nm ultraviolet lamp, FIG. 4 is molecule under 365nm ultraviolet lamp in different polar solvent (10)-4M), FIG. 5 shows the molecule in different polar solvents (including cyclohexane, chloroform, ethyl acetate, tetrahydrofuran, dichloromethane, ethanol and acetonitrile) at 5X 10-6M) normalized uv-vis absorption and fluorescence emission spectra.
FIG. 3 shows: the maximum emission wavelength of the solid powder of 1,3, 5-tris { [ 4-4-diphenylamino ]1,3, 4-oxadiazole } benzene was 366nm (in the ultraviolet region), but it also showed a strong emission over a long range of the visible region and exhibited a bright yellow color under an ultraviolet lamp.
FIG. 4 shows: 1,3, 5-tris { [ 4-4-dianilino { []The 1,3, 4-oxadiazole benzene molecule shows a very strong lyotropic effect. Specifically, the method comprises the following steps: 1,3, 5-tris { [ 4-4-dianilino { []Solutions of 1,3, 4-oxadiazole benzene molecules in different polarities (10)-4M), a distinctly different color was exhibited under an ultraviolet lamp (λ 365 nm). As can be seen from the figure, the color in Cyclohexane (CHEX) solution is blue; the color gradually changed from Chloroform (CHL), Ethyl Acetate (EA), Tetrahydrofuran (THF) to Dichloromethane (DCM) solution to green; the color in Ethanol (ETO) and Acetonitrile (ACN) solutions was orange-yellow. It can be seen that the luminescence behavior of the molecule is significantly different in different solvents, and different brightnesses can be produced.
FIG. 5 shows: the 1,3, 5-tris { [ 4-4-diphenylamino ]1,3, 4-oxadiazole } benzene molecule has two absorption peaks in cyclohexane solvent at 301nm and 391nm, respectively, a maximum emission in cyclohexane of 409nm, and a bright blue color under an ultraviolet lamp. Thus, the substance can be used for manufacturing ultraviolet and visible OLED devices and the like.
The detailed photophysical data of fig. 5 is shown in table 1. In cyclohexane, the molecule has two strong absorption peaks at 301nm and 391 nm. The change of the polarity of the solvent has little influence on the number and the peak type of the strong absorption peaks of the ultraviolet-visible absorption spectrum of the molecule, and the maximum absorption peak is between 383-396 nm.
In nonpolar cyclohexane, the maximum emission peak of molecular fluorescence is 405nm, and a shoulder peak is present at 422 nm. This shoulder is caused by the vibrational fine structure of the molecule. As the polarity of the solvent increases, the position of the maximum emission peak of the molecule is also significantly red-shifted. In chloroform, the position of the maximum emission peak was 462 nm; in ethyl acetate and tetrahydrofuran, the positions of the maximum emission peaks are 472nm and 478nm, respectively; in dichloromethane, the position of the maximum emission peak is 482 nm; in ethanol, the maximum emission peak position is 520 nm; in acetonitrile, the position of the maximum emission peak is 524 nm. In the solution from nonpolar cyclohexane to high-polarity acetonitrile, 119nm red shift occurs at the position of the maximum emission peak of the molecule, which indicates that the molecule has intramolecular charge transfer property and the fluorescence spectrum shows obvious change. These changes indicate that the molecule has strong sensitivity to the polarity of the solution, and can be used for the manufacture of fluorescence sensors and the like.
TABLE 1 molecules in solvents of different polarity (5X 10)-6M) photophysical data.
Comparative example
This comparative example provides a compound having the following chemical structures with electron donor and electron acceptor being diphenylamine and oxadiazole groups, respectively:
the photophysical properties of this material were as follows: the maximum absorption peak positions in chloroform, tetrahydrofuran and dimethyl sulfoxide are 385nm, 391nm and 406nm, and the ultraviolet absorption spectrum change in different polar solvents is small. The maximum fluorescence emission peak positions in the three solvents are 560nm, 595nm and 598nm respectively, and the red shift is 38 nm.
In addition, the fluorescence spectrum of the star-shaped D-A type conjugated molecule 1,3, 5-tris { [ 4-4-diphenylamino ]1,3, 4-oxadiazole } benzene in the chloroform and acetonitrile solvent is red-shifted by 62nm, the red-shift degree is large, and the charge transfer capacity is high in the example 1 of the application.
Therefore, the star-shaped D-A type conjugated molecule provided by the application is beneficial to improving the intramolecular charge transfer capability and obtaining excellent luminescent properties.
In summary, the oxadiazole electron-withdrawing group is introduced into the star-shaped D-a conjugated molecule, so that the effects of improving electron injection balance and electron transfer rate are achieved, and meanwhile, through the design of the star-shaped molecule, charge transfer effects on branches are superposed, and the intramolecular charge transfer property is improved. The molecule shows strong blue emission in non-polar solution and strong ultraviolet and visible emission in solid state. In addition, the emission spectrum of the molecule in the solution can generate larger red shift along with the increase of the polarity of the solvent, shows obvious lyotropic discoloration property, can be used as an organic semiconductor material and is suitable for preparing organic photoelectric devices, such as organic electroluminescent devices, fluorescent sensors or solar cells.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110233862.9A CN112939888A (en) | 2021-03-03 | 2021-03-03 | Star-shaped D-A type conjugated molecule and synthetic method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110233862.9A CN112939888A (en) | 2021-03-03 | 2021-03-03 | Star-shaped D-A type conjugated molecule and synthetic method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112939888A true CN112939888A (en) | 2021-06-11 |
Family
ID=76247353
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110233862.9A Pending CN112939888A (en) | 2021-03-03 | 2021-03-03 | Star-shaped D-A type conjugated molecule and synthetic method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112939888A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5420288A (en) * | 1992-04-14 | 1995-05-30 | Ricoh Company, Ltd. | Electroluminescent device comprising oxadiazole compounds luminescent material, oxadiazole compounds for the device, and method of producing oxadiazole compounds |
| JPH08245954A (en) * | 1995-03-08 | 1996-09-24 | Ricoh Co Ltd | Electroluminescent element |
| JP2000264880A (en) * | 1999-03-16 | 2000-09-26 | Sharp Corp | Oxadiazole derivative, its production and organic electroluminescence element made of the same |
| CN102827086A (en) * | 2012-08-03 | 2012-12-19 | 浙江理工大学 | Preparation method for 4-chloro-6,7-bis(2-methoxyethoxy)quinazoline |
| CN107056717A (en) * | 2017-03-14 | 2017-08-18 | 吉林大学 | D A type organic fluorescence small molecule materials and its application in ferric ion detection |
-
2021
- 2021-03-03 CN CN202110233862.9A patent/CN112939888A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5420288A (en) * | 1992-04-14 | 1995-05-30 | Ricoh Company, Ltd. | Electroluminescent device comprising oxadiazole compounds luminescent material, oxadiazole compounds for the device, and method of producing oxadiazole compounds |
| JPH08245954A (en) * | 1995-03-08 | 1996-09-24 | Ricoh Co Ltd | Electroluminescent element |
| JP2000264880A (en) * | 1999-03-16 | 2000-09-26 | Sharp Corp | Oxadiazole derivative, its production and organic electroluminescence element made of the same |
| CN102827086A (en) * | 2012-08-03 | 2012-12-19 | 浙江理工大学 | Preparation method for 4-chloro-6,7-bis(2-methoxyethoxy)quinazoline |
| CN107056717A (en) * | 2017-03-14 | 2017-08-18 | 吉林大学 | D A type organic fluorescence small molecule materials and its application in ferric ion detection |
Non-Patent Citations (3)
| Title |
|---|
| XUEHAN HE，等: "Soluble bipolar star-shaped molecule as highly stable and efficient blue light emitter", 《RSC ADVANCES》, 19 January 2015 (2015-01-19), pages 15400 * |
| 张明龙，等: "新型噁二唑有机电致发光小分子光电性质研究", 《光子学报》, 30 June 2003 (2003-06-30), pages 672 - 675 * |
| 李德江，等: "2-苯基-5-芳基-1,3,4-噁二唑的合成与表征", 《合成化学》, 31 December 2004 (2004-12-31), pages 2 - 1 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tao et al. | Synthesis and characterization of efficient luminescent materials based on 2, 1, 3-benzothiadiazole with carbazole moieties | |
| Zhu et al. | Branched triphenylamine luminophores: aggregation-induced fluorescence emission, and tunable near-infrared solid-state fluorescence characteristics via external mechanical stimuli | |
| Huang et al. | Enhancement of the excited-state intramolecular proton transfer process to produce all-powerful DSE molecules for bridging the gap between ACQ and AIE | |
| Szłapa et al. | Simple donor–π–acceptor derivatives exhibiting aggregation-induced emission characteristics for use as emitting layer in OLED | |
| CN109337676B (en) | Deep blue photo-thermal activation delayed fluorescence material and application thereof | |
| CN113896677A (en) | Reversible force photochromic material with aggregation-induced emission property and preparation method thereof | |
| CN109369652B (en) | Blue light thermal activation delayed fluorescent material and application thereof | |
| Xue et al. | Mechanochromic luminescence from N, O-Chelated diphenylborinates | |
| Liu et al. | ACQ-to-AIE transformation by regioisomerization of rofecoxib derivatives for developing novel mechanochromic and acidochromic materials | |
| CN107382982B (en) | Dicyanomethylene-4H-pyran derivatives and preparation methods and uses thereof | |
| Lian et al. | Dibenzthiophene and carbazole modified dicyanoethylene derivative exhibiting aggregation-induced emission enhancement and mechanochromic luminescence | |
| Zhang et al. | Unique mechanofluorochromism and reversible multicolor switching of triphenylamine-functionalized sulfonyl hydrazone derivatives | |
| Hu et al. | Synthesis and fluorescence emission properties of 1, 3, 6, 8-tetraarylpyrenes | |
| CN113493445B (en) | Imidazolyl spiro derivative with aggregation-induced emission property and application thereof | |
| CN113387905A (en) | Organic room temperature phosphorescent material, preparation method and application | |
| Meng et al. | Chiral binaphthylamine based emitters with donor-acceptor structures: Facile synthesis and circularly polarized luminescence | |
| CN107384374B (en) | A kind of aggregation-induced emission and mechanical cause enhancing luminescent material and preparation method | |
| Li et al. | Acceptor-density engineering of push-pull typed carbazole derivatives for improving luminescent efficiency and mechanoresponsive luminescence | |
| CN102633610B (en) | 'Vertically' unsymmetrical spirobifluorene compound derived from conversion of methyl on fluorene loop and preparation method and application thereof | |
| CN110627776B (en) | Synthesis and Photoelectric Properties of Carbazole-Based Room-temperature Phosphorescent Materials Containing S/Se/Te Heavy Atoms | |
| CN110117235B (en) | Compound with aggregation-induced light emission and mechanochromism characteristics and preparation method and application thereof | |
| CN112939888A (en) | Star-shaped D-A type conjugated molecule and synthetic method and application thereof | |
| Yu et al. | Solvent-induced MultiStimuli-Responsive properties of cyano-substituted Oligo (p-phenylene vinylene) derivatives | |
| CN114276334B (en) | Carbazole alkylation aromatic heterocyclic derivative and preparation method thereof | |
| CN115611826A (en) | Phenothiazine derivative, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |