CN108178767A - A kind of organic molecule luminescent material based on pyrazine receptor unit and its preparation method and application - Google Patents
A kind of organic molecule luminescent material based on pyrazine receptor unit and its preparation method and application Download PDFInfo
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- CN108178767A CN108178767A CN201810051228.1A CN201810051228A CN108178767A CN 108178767 A CN108178767 A CN 108178767A CN 201810051228 A CN201810051228 A CN 201810051228A CN 108178767 A CN108178767 A CN 108178767A
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- Prior art keywords
- pyrazine
- luminescent material
- organic molecule
- receptor unit
- molecule luminescent
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- 239000000463 material Substances 0.000 title claims abstract description 90
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Natural products C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 title claims abstract description 56
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- -1 aromatic amine compound Chemical class 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 150000004982 aromatic amines Chemical group 0.000 claims abstract description 5
- 239000000543 intermediate Substances 0.000 claims description 31
- 239000003513 alkali Substances 0.000 claims description 13
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 12
- 238000004440 column chromatography Methods 0.000 claims description 12
- VLPBEKHOQWMYTR-UHFFFAOYSA-N 2,3-dibromopyrazine Chemical class BrC1=NC=CN=C1Br VLPBEKHOQWMYTR-UHFFFAOYSA-N 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- ZOQCZTRFTARYGJ-UHFFFAOYSA-N chlorooxy(phenyl)borinic acid Chemical compound ClOB(O)C1=CC=CC=C1 ZOQCZTRFTARYGJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000007530 organic bases Chemical class 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- YUQUNWNSQDULTI-UHFFFAOYSA-N 2-bromobenzenethiol Chemical compound SC1=CC=CC=C1Br YUQUNWNSQDULTI-UHFFFAOYSA-N 0.000 claims description 2
- DLIJPAHLBJIQHE-UHFFFAOYSA-N butylphosphane Chemical group CCCCP DLIJPAHLBJIQHE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 17
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- 230000015572 biosynthetic process Effects 0.000 description 24
- 238000003786 synthesis reaction Methods 0.000 description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 23
- 238000000921 elemental analysis Methods 0.000 description 17
- 230000008859 change Effects 0.000 description 9
- ATTVYRDSOVWELU-UHFFFAOYSA-N 1-diphenylphosphoryl-2-(2-diphenylphosphorylphenoxy)benzene Chemical compound C=1C=CC=CC=1P(C=1C(=CC=CC=1)OC=1C(=CC=CC=1)P(=O)(C=1C=CC=CC=1)C=1C=CC=CC=1)(=O)C1=CC=CC=C1 ATTVYRDSOVWELU-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- CINYXYWQPZSTOT-UHFFFAOYSA-N 3-[3-[3,5-bis(3-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical compound C1=CN=CC(C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)=C1 CINYXYWQPZSTOT-UHFFFAOYSA-N 0.000 description 6
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000005401 electroluminescence Methods 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229960001866 silicon dioxide Drugs 0.000 description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 4
- CMRJNXIGRAVTPW-UHFFFAOYSA-N 2-(3,4-dichlorophenyl)-5h-imidazo[2,1-a]isoindole Chemical compound C1=C(Cl)C(Cl)=CC=C1C1=CN(CC=2C3=CC=CC=2)C3=N1 CMRJNXIGRAVTPW-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- VFUDMQLBKNMONU-UHFFFAOYSA-N 9-[4-(4-carbazol-9-ylphenyl)phenyl]carbazole Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 VFUDMQLBKNMONU-UHFFFAOYSA-N 0.000 description 1
- OSYXUHPPTNAZAK-UHFFFAOYSA-N C1(=CC=CC=C1)O.[S].BrC1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)O.[S].BrC1=CC=CC=C1 OSYXUHPPTNAZAK-UHFFFAOYSA-N 0.000 description 1
- PKINLSIXZQRXBG-UHFFFAOYSA-N C=[Br]c(nc1)cnc1Br Chemical compound C=[Br]c(nc1)cnc1Br PKINLSIXZQRXBG-UHFFFAOYSA-N 0.000 description 1
- MRPPGUYNKZRSGR-UHFFFAOYSA-N Clc(cc1)ccc1-c1nc(-c(cc2)ccc2Cl)cnc1 Chemical compound Clc(cc1)ccc1-c1nc(-c(cc2)ccc2Cl)cnc1 MRPPGUYNKZRSGR-UHFFFAOYSA-N 0.000 description 1
- YCYAJRIILVXQIK-UHFFFAOYSA-N O=P(c1ccccc1)(c1ccccc1)c(cccc1)c1Oc1ccccc1P(c1ccccc1)(C1=CCCC=C1)=O Chemical compound O=P(c1ccccc1)(c1ccccc1)c(cccc1)c1Oc1ccccc1P(c1ccccc1)(C1=CCCC=C1)=O YCYAJRIILVXQIK-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- MZYDBGLUVPLRKR-UHFFFAOYSA-N c(cc1)cc(c2ccccc22)c1[n]2-c1cc(-[n]2c3ccccc3c3c2cccc3)ccc1 Chemical compound c(cc1)cc(c2ccccc22)c1[n]2-c1cc(-[n]2c3ccccc3c3c2cccc3)ccc1 MZYDBGLUVPLRKR-UHFFFAOYSA-N 0.000 description 1
- TZMSYXZUNZXBOL-UHFFFAOYSA-N c(cc1)cc2c1Oc1ccccc1N2 Chemical compound c(cc1)cc2c1Oc1ccccc1N2 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 description 1
- NSBVOLBUJPCPFH-UHFFFAOYSA-N c(cc12)ccc1[nH]c1c2nccc1 Chemical compound c(cc12)ccc1[nH]c1c2nccc1 NSBVOLBUJPCPFH-UHFFFAOYSA-N 0.000 description 1
- AEXSSYGNGQCHNE-UHFFFAOYSA-N c(cc1c2c3cccn2)ccc1[n]3-c(nc1)cnc1-[n](c1c2cccc1)c1c2nccc1 Chemical compound c(cc1c2c3cccn2)ccc1[n]3-c(nc1)cnc1-[n](c1c2cccc1)c1c2nccc1 AEXSSYGNGQCHNE-UHFFFAOYSA-N 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010849 ion bombardment Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- ZGNPLWZYVAFUNZ-UHFFFAOYSA-N tert-butylphosphane Chemical compound CC(C)(C)P ZGNPLWZYVAFUNZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
-
- 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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- 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]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- 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
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- 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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- 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
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- 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
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
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- 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
Abstract
The invention discloses a kind of organic molecule luminescent materials based on pyrazine receptor unit, using pyrazine as receptor unit, different types of aromatic amine groups are connected in different positions, the light emitting molecule of different D A D structures is obtained, realizes the adjusting being distributed to material conjugate length, Intramolecular electron transfer intensity, the molecular size range of material and molecular energy level.The invention also discloses the preparation methods of above-mentioned organic molecule luminescent material, using pyrazine receptor unit and aromatic amine compound as key reaction raw material, by series reaction, obtain target product.The invention also discloses the applications of above-mentioned organic molecule luminescent material.The material molecule amount of the present invention determines that structure is single, and with higher decomposition temperature, by effective Intramolecular electron transfer and put forward high molecular triplet, it can overcome the problems, such as that the carrier of luminescent material is unbalanced, the stability of device, available for organic light emitting diode device.
Description
Technical field
The present invention relates to technical field of organic luminescence materials, more particularly to a kind of organic small point based on pyrazine receptor unit
Sub- luminescent material and its preparation method and application.
Background technology
Presentation of information is considered as one of three big mainstays of IT industry, development it is smooth whether directly affect people's life
Every aspect living affects expanding economy level.The yearning application of ORGANIC ELECTROLUMINESCENCE DISPLAYS technology is exactly to be
Display and illumination.ORGANIC ELECTROLUMINESCENCE DISPLAYS technology, using ultra-thin coating of organic material, passes through due to having the characteristics that self-luminous
The injection of low current causes material emission.Meanwhile it is wide with screen viewing angle using ORGANIC ELECTROLUMINESCENCE DISPLAYS technology, low energy consumption,
Manufacturing process is simple, and cost is lower, and the response time is exceedingly fast, only the one thousandth of liquid crystal display the features such as, it is wide by insider
General have an optimistic view of is also based on these unique advantages.
In an organic light emitting device, the hair used compared to common organic fluorescence luminescent device and Phosphorescent luminescent device
Luminescent material, hot activation delayed fluorescence (TADF) material is free of the precious metal atom of cost costly, and can make full use of
The unemployed triplet excitons of common fluorescent material realize the exciton utilization rate of device 100% so that the design of such material
With characterization as the research hotspot of nearest Organic Light Emitting Diode.Hot activation delayed fluorescence material can be effectively facilitated inverse system
Between alter the process of more (RISC) so as to effectively utilize triplet excitons, impart the unique photoelectric properties of these materials,
Such as the long lifetime of excited state that TADF materials are special, it is made also to show comparable application potential in other photoelectric fields.It is heavier
Want, based on the organic electroluminescence device that TADF materials are produced show can with traditional rare metal complex
The superior function that the Phosphorescent luminescent device prepared for luminescent layer compares favourably.
By exploring the design of molecular structure and the relationship of device light emitting efficiency, sum up prepare it is efficient, low roll-off have
The method of machine luminescent material can obtain extensive commercial applications for organic electro-optic device and pave the way, have particularly significant
Academic significance and huge economic value.
Invention content
In order to overcome the disadvantages mentioned above of the prior art with insufficient, the purpose of the present invention is to provide one kind to be based on pyrazine receptor
The organic molecule luminescent material of unit, molecular structure is simple, and performance is stablized, and has higher decomposition temperature, can prepare shape
The film that state and performance are stablized.
Another object of the present invention is to provide the system of the above-mentioned organic molecule luminescent material based on pyrazine receptor unit
Preparation Method, simple synthetic method are easily purified.
Another object of the present invention is the above-mentioned organic molecule luminescent material based on pyrazine receptor unit
The purpose of the present invention is achieved through the following technical solutions：
A kind of organic molecule luminescent material based on pyrazine receptor unit has the chemistry knot shown in following P1n~P5n
Any one of structure formula：
Wherein, Ar represents the aromatic amine groups of any one type in (1)~(4)：
The organic molecule luminescent material based on pyrazine receptor unit has any one of following P1~P20 institutes
The structural formula shown：
The organic molecule luminescent material based on pyrazine receptor unit, including following preparation process：
(1) any one of a~d intermediates are prepared：
(2) under the protection of inert gas, intermediate, aromatic amine prepared by step (1) are added in organic solvent
Close object, alkali and catalyst are uniformly mixed, and are heated to reflux being stirred to react, via cooling down, extracting, being spin-dried for solvent, column chromatography, obtain
The organic molecule luminescent material based on pyrazine receptor unit；
The intermediate is 1 with the molar ratio used in aromatic amine compounds:(2~2.5)；The alkali is organic base, is used
Amount and the molar ratio of aromatic amine compounds are (1.8~2.5):1.
Step (1) is described to prepare any one of a~d intermediates, specially：For intermediate a~c, in inert gas
Under protection, two halogen pyrazines of different location substitution are added in a solvent, chlorophenylboronic acid, alkali and tetrakis triphenylphosphine palladium are mixed
It closes uniform, is heated to reflux being stirred to react, via cooling down, extracting, being spin-dried for solvent, column chromatography, obtain intermediate a~c；
For intermediate d, under the protection of inert gas, 2,5-, bis- bromo-pyrazines are added in organic solvent, to bromobenzene sulphur
Phenol, alkali are uniformly mixed, and reaction is stirred at room temperature, and via cooling down, extracting, being spin-dried for solvent, column chromatography, obtain intermediate d.
The temperature of step (2) described heating reflux reaction is 90~110 DEG C, the reaction time for 12~for 24 hours.
Step (2) described aromatic amine compounds are 5- carbolines, 9,9 '-dimethyl acridinium, fenIn piperazine or phenthazine
Any one.
Step (2) catalyst is made of palladium and three tertiary butyl phosphines.
Include the following steps：
Under the protection of inert gas, add in organic solvent 2,5-, bis- bromo-pyrazines, aromatic amine compounds, alkali and
Catalyst is uniformly mixed, and is heated to reflux being stirred to react, and via cooling down, extracting, being spin-dried for solvent, column chromatography, is obtained described based on pyrrole
The organic molecule luminescent material of piperazine receptor unit；
Bis- bromo-pyrazines of 2,5- are 1 with the molar ratio used in aromatic amine compounds:(2~2.5)；The alkali is organic
The molar ratio of alkali, dosage and aromatic amine compounds is (1.8~2.5):1.
The organic molecule luminescent material based on pyrazine receptor unit, step (2) described heating reflux reaction
Temperature is 90~110 DEG C, the reaction time for 12~for 24 hours.
The organic molecule luminescent material material based on pyrazine receptor unit is applied in Organic Light Emitting Diode.
Compared with prior art, the present invention has the following advantages and beneficial effect：
(1) the obtained organic molecule luminescent material based on pyrazine receptor unit of the present invention, simple in structure, synthesis
Method is easy, and molecular weight determines, is easily purified, and synthesizes favorable reproducibility.
(2) the obtained organic molecule luminescent material based on pyrazine receptor unit of the present invention has higher decomposition temperature
Degree can prepare the film that form and performance are stablized.
(3) the obtained organic molecule luminescent material based on pyrazine receptor unit of the present invention, structure can pass through
Change the type of connection aromatic amine groups and to electrically and the adjusting of luminescent color and carrier are realized in the position of connection
The regulation and control of other photoelectricity physical properties such as transmission.
Description of the drawings
Fig. 1 is the Absorption and emission spectra of P6, P10 in toluene solution.
Fig. 2 is the Absorption and emission spectra of P7, P11 in toluene solution.
Fig. 3 is Current density-voltage-brightness relationship curve figure of organic light emitting diode device prepared by embodiment 21.
Fig. 4 is Current density-voltage-brightness relationship curve figure of organic light emitting diode device prepared by embodiment 22.
Fig. 5 is maximum external quantum efficiency-brightness relationship curve figure of organic light emitting diode device prepared by embodiment 21.
Fig. 6 is big external quantum efficiency-brightness relationship curve figure of organic light emitting diode device prepared by embodiment 22.
Fig. 7 is the electroluminescent light spectrogram of organic light emitting diode device prepared by embodiment 21.
Fig. 8 is the electroluminescent light spectrogram of organic light emitting diode device prepared by embodiment 22.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Embodiment 1
A kind of organic molecule luminescent material (P1) based on pyrazine receptor unit, specific synthesis step are shown below：
Bis- bromo-pyrazine 713.67mg (3mmol) and carboline 1.043g of 2,5- are added in the there-necked flask of 250mL
(6.2mmol) is dissolved with the toluene of 100mL, adds in sodium tert-butoxide 1.152g (12mmol) palladiums 44.8mg later
(0.2mmol), three tertiary butyl phosphine 0.6mL (1mol/L toluene solutions), is heated to 110 DEG C of back flow reaction 20h under nitrogen atmosphere.
System is cooled to room temperature after reaction, revolving removes toluene, and multiple, taking-up organic phase, rotation are extracted with dichloromethane and water
Extra dichloromethane is evaporated off, 927mg products (P1), yield 75% are obtained using silicagel column column chromatography.Molecular formula：
C26H16N6；M/Z=412.14；M/s=412.14 (100.0%), 413.15 (28.1%), 414.15 (2.7%), 413.14
(2.2%)；Elemental analysis：C,75.71；H,3.91；N,20.38.
Embodiment 2
A kind of organic molecule luminescent material (P2) based on pyrazine receptor unit, specific synthesis step are shown below：
Change the carboline in embodiment 1 the 9 of equivalent into, 9 '-dimethyl acridinium 1.298g (6.2mmol), remaining raw material
It is same as Example 1 with step, 979mg products (P2), yield 66% can be obtained.Molecular formula：C34H30N4；M/Z=
494.25；M/s=494.25 (100.0%), 495.25 (36.8%), 496.25 (3.9%), 496.25 (2.7%)；Element point
Analysis：C,82.56；H,6.11；N,11.33.
Embodiment 3
A kind of organic molecule luminescent material (P3) based on pyrazine receptor unit, specific synthesis step are shown below：
Carboline in embodiment 1 is changed into the fen of equivalentPiperazine 1.136g (6.2mmol), remaining raw material and step with
Embodiment 1 is identical, can obtain 796mg products (P3), yield 60%.Molecular formula：C28H18N4O2；M/Z=442.14；M/s=
442.14 (100.0%), 443.15 (30.3%), 444.15 (2.7%), 444.15 (1.7%)；Elemental analysis：C,76.01；
H,4.10；N,12.66；O,7.23.
Embodiment 4
A kind of organic molecule luminescent material (P4) based on pyrazine receptor unit, specific synthesis step are shown below：
Carboline in embodiment 1 changes into the phenthazine 1.235g (6.2mmol) of equivalent, remaining raw material and step with
Embodiment 1 is identical, can obtain 897mg products (P4), yield 63%.Molecular formula：C28H18N4S2；M/Z=474.10；M/s=
474.10 (100.0%), 475.10 (30.3%), 476.09 (9.0%), 477.10 (2.7%)；Elemental analysis：C,70.86；
H,3.82；N,11.81；S,13.51.
Embodiment 5
The present embodiment prepares intermediate 1 first, and specific synthesis step is shown below：
Bis- bromo-pyrazine 951.56mg (4mmol) of 2,5- are added in the there-necked flask of 250mL and to chlorophenylboronic acid 1.313g
(8.4mmol), is dissolved with the toluene of 90mL and the ethyl alcohol of 30mL, adds in the wet chemical of 2mol/L being configured later
30mL and catalyst tetra-triphenylphosphine palladium 231.2mg (0.2mmol), is heated to 80 DEG C of back flow reactions for 24 hours under nitrogen atmosphere.
System is cooled to room temperature after reaction, revolving removes toluene and ethyl alcohol, is extracted repeatedly, taken out organic with dichloromethane and water
Phase, revolving remove extra dichloromethane, 1.10g intermediates 1, yield 91% are obtained using silicagel column column chromatography.Molecular formula：
C16H10Cl2N2；M/Z=300.02；M/s=300.02 (100%), 302.02 (63.9%), 301.03 (17.3%), 303.02
(11.1%)；Elemental analysis：C,63.81；H,3.35；Cl,23.54；N,9.30.
Organic molecule luminescent material (P5) based on pyrazine receptor unit, specific synthesis step are shown below：
The intermediate 1 and carboline 706.44mg (4.2mmol) of 602.34mg (2mmol) is added in the there-necked flask of 250mL,
It is dissolved with the toluene of 100mL, adds in sodium tert-butoxide 768mg (8mmol) palladium 44.8mg (0.2mmol), three tertiary butyls later
Phosphine 0.6mL (1mol/L toluene solutions), is heated to 110 DEG C of back flow reaction 20h under nitrogen atmosphere.It is after reaction that system is cold
But to room temperature, revolving removes toluene, is extracted repeatedly with dichloromethane and water, takes out organic phase, and revolving removes extra dichloromethane
Alkane obtains 824mg products (P5), yield 73% using silicagel column column chromatography.Molecular formula：C38H24N6；M/Z=564.21；M/s=
564.21 (100.0%), 565.21 (41.1%), 566.21 (8.2%), 565.20 (2.2%)；Elemental analysis：C,80.83；
H,4.28；N,14.88.
Embodiment 6
A kind of organic molecule luminescent material (P6) based on pyrazine receptor unit, specific synthesis step are shown below：
Change the carboline in embodiment 5 into the 9 of equivalent, 9 '-dimethyl acridinium 879.02mg (4.2mmol), remaining is former
Material and step are same as Example 5, can obtain 880mg products (P6), yield 68%.Molecular formula：C46H38N4；M/Z=
646.31；M/s=646.31 (100.0%), 647.31 (49.8%), 648.32 (12.1%), 647.31 (1.5%)；Element
Analysis：C,85.42；H,5.92；N,8.66.
Embodiment 7
A kind of organic molecule luminescent material (P7) based on pyrazine receptor unit, specific synthesis step are shown below：
Carboline in embodiment 5 is changed into the fen of equivalentPiperazine 769.48mg (4.2mmol), remaining raw material and step are equal
It is same as Example 5,749mg products (P7), yield 63% can be obtained.Molecular formula：C40H26N4O2；M/Z=594.21；m/s
=594.21 (100.0%), 595.21 (43.3%), 596.21 (9.1%), 595.20 (1.5%)；Elemental analysis：C,
80.79；H,4.41；N,9.42；O,5.38.
Embodiment 8
A kind of organic molecule luminescent material (P8) based on pyrazine receptor unit, specific synthesis step are shown below：
Carboline in embodiment 5 is changed to the phenthazine 836.93mg (4.2mmol) of equivalent into, remaining raw material and step are equal
It is same as Example 5,815mg products (P8), yield 65% can be obtained.Molecular formula：C40H26N4S2；M/Z=626.16；m/s
=626.16 (100.0%), 627.16 (43.3%), 628.17 (9.1%), 628.16 (9.0%)；Elemental analysis：C,
76.65；H,4.18；N,8.94；S,10.23.
Embodiment 9
The present embodiment first prepares intermediate 2, and specific synthesis step is shown below：
2,5-, bis- bromo-pyrazines in embodiment 1 are changed into 2, the 6- dichloropyrazines 595.88mg (4mmol) of equivalent, remaining
Raw material and step are identical with preparing for centre 1, can obtain 1.02g intermediates 2, yield 85%.Molecular formula：C16H10Cl2N2；
M/Z=300.02；M/s=300.02 (100%), 302.02 (63.9%), 301.03 (17.3%), 303.02 (11.1%)；
Elemental analysis：C,63.81；H,3.35；Cl,23.54；N,9.30.
Organic molecule luminescent material (P9) based on pyrazine receptor unit, specific synthesis step are shown below：
Intermediate 1 in embodiment 5 changes into the intermediate 2 of equivalent, remaining raw material and step with 5 phase of embodiment
Together, 834mg products (P9), yield 74% can be obtained.Molecular formula：C38H24N6；M/Z=564.21；M/s=564.21
(100.0%), 565.21 (41.1%), 566.21 (8.2%), 565.20 (2.2%)；Elemental analysis：C,80.83；H,4.28；
N,14.88。
Embodiment 10
A kind of organic molecule luminescent material (P10) based on pyrazine receptor unit, specific synthesis step are shown below：
Change the carboline in embodiment 9 into the 9 of equivalent, 9 '-dimethyl acridinium 879.02mg (4.2mmol), remaining is former
Material and step are same as Example 9, can obtain 841mg products (P10), yield 65%.Molecular formula：C46H38N4；M/Z=
646.31；M/s=646.31 (100.0%), 647.31 (49.8%), 648.32 (12.1%), 647.31 (1.5%)；Element
Analysis：C,85.42；H,5.92；N,8.66.
Embodiment 11
A kind of organic molecule luminescent material (P11) based on pyrazine receptor unit, specific synthesis step are shown below：
Carboline in embodiment 9 is changed into the fen of equivalentPiperazine 769.48mg (4.2mmol), remaining raw material and step are equal
It is same as Example 9,785mg products (P11), yield 66% can be obtained.Molecular formula：C40H26N4O2；M/Z=594.21；m/s
=594.21 (100.0%), 595.21 (43.3%), 596.21 (9.1%), 595.20 (1.5%)；Elemental analysis：C,
80.79；H,4.41；N,9.42；O,5.38
Embodiment 12
A kind of organic molecule luminescent material (P12) based on pyrazine receptor unit, specific synthesis step are shown below：
Carboline in embodiment 13 is changed into the phenthazine 836.93mg (4.2mmol) of equivalent, remaining raw material and step
It is identical with embodiment 13,853mg products (P12), yield 68% can be obtained.Molecular formula：C40H26N4S2；M/Z=626.16；
M/s=626.16 (100.0%), 627.16 (43.3%), 628.17 (9.1%), 628.16 (9.0%)；Elemental analysis：C,
76.65；H,4.18；N,8.94；S,10.23.
Embodiment 13
The present embodiment prepares intermediate 3, and specific synthesis step is shown below：
2,5-, bis- bromo-pyrazines in the preparation of centre 1 are changed into 2, the 3- dichloropyrazines 595.88mg (4mmol) of equivalent,
Remaining raw material and step are identical with preparing for centre 1, can obtain 1.06g intermediates 3, yield 88%.Molecular formula：
C16H10Cl2N2；M/Z=300.02；M/s=300.02 (100%), 302.02 (63.9%), 301.03 (17.3%), 303.02
(11.1%)；Elemental analysis：C,63.81；H,3.35；Cl,23.54；N,9.30.
Organic molecule luminescent material (P13) based on pyrazine receptor unit, specific synthesis step are shown below：
Intermediate 2 in embodiment 9 changes into the intermediate 3 of equivalent, remaining raw material and step with 9 phase of embodiment
Together, 869mg products (P13), yield 77% can be obtained.Molecular formula：C38H24N6；M/Z=564.21；M/s=564.21
(100.0%), 565.21 (41.1%), 566.21 (8.2%), 565.20 (2.2%)；Elemental analysis：C,80.83；H,4.28；
N,14.88。
Embodiment 14
A kind of organic molecule luminescent material (P14) based on pyrazine receptor unit, specific synthesis step are shown below：
Change the carboline in embodiment 13 into the 9 of equivalent, 9 '-dimethyl acridinium 879.02mg (4.2mmol), remaining is former
Material and step are identical with embodiment 13, can obtain 802mg products (P10), yield 62%.Molecular formula：C46H38N4；M/Z=
646.31；M/s=646.31 (100.0%), 647.31 (49.8%), 648.32 (12.1%), 647.31 (1.5%)；Element
Analysis：C,85.42；H,5.92；N,8.66.
Embodiment 15
Organic molecule luminescent material (P15) based on pyrazine receptor unit, specific synthesis step are shown below：
Carboline in embodiment 13 is changed into the fen of equivalentPiperazine 769.48mg (4.2mmol), remaining raw material and step
It is identical with embodiment 13,770mg products (P15), yield 65% can be obtained.Molecular formula：C40H26N4O2；M/Z=594.21；
M/s=594.21 (100.0%), 595.21 (43.3%), 596.21 (9.1%), 595.20 (1.5%)；Elemental analysis：C,
80.79；H,4.41；N,9.42；O,5.38.
Embodiment 16
A kind of organic molecule luminescent material (P16) based on pyrazine receptor unit, specific synthesis step are shown below：
Carboline in embodiment 13 is changed into the phenthazine 836.93mg (4.2mmol) of equivalent, remaining raw material and step
It is identical with embodiment 13,846mg products (P16), yield 67% can be obtained.Molecular formula：C40H26N4S2；M/Z=626.16；
M/s=626.16 (100.0%), 627.16 (43.3%), 628.17 (9.1%), 628.16 (9.0%)；Elemental analysis：C,
76.65；H,4.18；N,8.94；S,10.23.
Embodiment 17
The present embodiment first prepares intermediate 4, and specific synthesis step is shown below：
Bis- bromo-pyrazine 1.189g (5mmol) of 2,5- are added in the single port bottle of 250mL and to bromo thiophenol 1.985g
(10.5mmol) is dissolved with the acetonitrile of 80mL, adds in Anhydrous potassium carbonate 2.76g (20mmol) later, 18h is stirred at room temperature.
The acetonitrile in reaction system is spin-dried for after reaction, multiple, taking-up organic phase is extracted with dichloromethane and water, revolving removing is more
Remaining dichloromethane obtains 1.64g intermediates 4, yield 72% using silicagel column column chromatography.Molecular formula：C16H10Br2N2S2；M/Z
=453.86；M/s=453.86 (100.0%), 451.87 (51.4%), 455.86 (48.6%), 454.87 (17.3%)；Member
Element analysis：C,42.31；H,2.22；Br,35.18；N,6.17；S,14.12.
Organic molecule luminescent material (P17) based on pyrazine receptor unit, specific synthesis step are shown below：
Intermediate 3 in embodiment 13 changes into the intermediate 4 of equivalent, remaining raw material and step with 13 phase of embodiment
Together, 868mg products (P17), yield 69% can be obtained.Molecular formula：C38H24N6S2；M/Z=628.15；M/s=628.15
(100.0%), 629.15 (41.1%), 630.15 (9.0%), 630.16 (8.2%)；Elemental analysis：C,72.59；H,3.85；
N,13.37；S,10.20.
Embodiment 18
Organic molecule luminescent material (P18) based on pyrazine receptor unit, specific synthesis step are shown below：
Change the carboline in embodiment 17 into the 9 of equivalent, 9 '-dimethyl acridinium 879.02mg (4.2mmol), remaining is former
Material and step are identical with embodiment 17, can obtain 825mg products (P18), yield 58%.Molecular formula：C46H38N4S2；M/Z
=710.25；M/s=710.25 (100.0%), 711.26 (49.8%), 712.26 (12.1%), 712.25 (9.0%)；Member
Element analysis：C,77.71；H,5.39；N,7.88；S,9.02.
Embodiment 19
A kind of organic molecule luminescent material (P19) based on pyrazine receptor unit, specific synthesis step are shown below：
Carboline in embodiment 17 is changed into the fen of equivalentPiperazine 769.48mg (4.2mmol), remaining raw material and step
It is identical with embodiment 17,791mg products (P19), yield 60% can be obtained.Molecular formula：C40H26N4O2S2；M/Z=
658.15；M/s=658.15 (100.0%), 659.15 (43.3%), 660.16 (9.1%), 660.15 (9.0%)；Element point
Analysis：C,72.93；H,3.98；N,8.50；O,4.86；S,9.73.
Embodiment 20
A kind of organic molecule luminescent material (P20) based on pyrazine receptor unit, specific synthesis step are shown below：
Carboline in embodiment 21 is changed into the phenthazine 836.93mg (4.2mmol) of equivalent, remaining raw material and step
It is identical with embodiment 21,857mg products (P20), yield 62% can be obtained.Molecular formula：C40H26N4S4；M/Z=690.10；
M/s=690.10 (100.0%), 691.11 (43.3%), 692.10 (18.1%), 692.11 (9.1%)；Elemental analysis：C,
69.54；H,3.79；N,8.11；S,18.56.
Embodiment 21
Using the organic molecule luminescent material (P6 and P10) based on pyrazine receptor unit of the present invention as organic light emission
The luminescent layer of diode component, the general-purpose device structure of implementation are as follows：ITO/TAPC(30nm)/mCP(10nm)/DPEPO:X
Wt%P6 or P10 (35nm)/DPEPO (10nm)/TmPyPB (40nm)/LiF (1nm)/Al (100nm).Wherein ITO is anode,
TAPC is hole injection layer, and mCP is hole transmission layer, and DPEPO is luminescent material doped body and hole blocking layer, and TmPyPB is
Electron transfer layer, LiF are electron injecting layer, and Al is cathode, X=20 or 30.
The preparation process of the organic light emitting diode device is as follows：By transparent electro-conductive glass in cleaning agent at ultrasound
Reason, then cleaned with deionized water, it is deoiled with the mixed solvent ultrasound of acetone and ethyl alcohol, is baked to removes completely under a clean environment
Moisture is removed, is handled with ultraviolet light and ozone clean, and with low energy electric ion bombardment.
The above-mentioned glass with anode ITO is placed in vacuum chamber, is evacuated to 1 × 10-5~9 × 10-3Pa, above-mentioned
On anode film withDeposition rate vapor deposition organic material layer, wherein in vapor deposition luminescent layer, by DPEPO and P6 or P10 point
It is not placed in two evaporation sources, the mixed proportion of the two is controlled by certain deposition rate.Later again withIt is heavy
Product rate vapor deposition LiF, withDeposition rate evaporating Al electrode, obtain the organic light emitting diode device of the present embodiment.
The Current density-voltage of the organic light emitting diode device of the present embodiment-brightness curve figure, maximum outer quantum effect
Respectively as shown in Fig. 3, Fig. 5, Fig. 7, basic characterize data is as shown in table 1 for rate-brightness relationship curve figure and electroluminescent light spectrogram.
Absorption and emission spectras of the P6 and P10 in toluene solution as shown in Figure 1, from photic and electroluminescent spectrum can be seen that this two
Kind material is the day blue light material for having CT features.It can be found that passing through both materials that shine from the relevant characterization data of device
That expects the device prepared opens that bright voltage is relatively low, as long as 3.0V, current density highest can reach 40mA/cm2More than.It is right
In P10, the maximum external quantum efficiency of device can also reach 12.8% level, hence it is evident that breach the maximum outer amount of conventional fluorescent material
The limitation of sub- efficiency 5%.
Table 1. is using P6 and P10 as the master data of the organic light emitting diode device of luminescent layer
Embodiment 22
Using the organic molecule luminescent material (P7 and P11) based on pyrazine receptor unit of the present invention as organic light emission
The luminescent layer of diode component, the general-purpose device structure of implementation are as follows：ITO/TAPC(40nm)/CBP:X wt%P7 or P11
(25nm)/TmPyPB (55nm)/LiF (1nm)/Al (100nm), wherein CBP be luminescent material doped body, X=3 or 6, remaining
Material is identical with embodiment 25 in the effect of the organic light emitting diode device.
The preparation process of the organic light emitting diode device in addition to during luminescent layer is deposited by DPEPO change into CBP with
Outside, remaining step is all identical with embodiment 25.
The current density of the organic light emitting diode device of the present embodiment of the organic light emitting diode device of the present embodiment-
Voltage-brightness curve graph, maximum external quantum efficiency-brightness relationship curve figure and electroluminescent light spectrogram are respectively such as Fig. 4, Fig. 6, figure
Shown in 8, basic characterize data is as shown in table 2.Absorption and emission spectras of the P7 and P11 in toluene solution is as shown in Fig. 2, from light
It causes and electroluminescent spectrum can be seen that both materials are the green light materials for having apparent CT features.From the relevant characterization number of device
It can be found that as long as the device prepared by both luminescent materials opens bright voltage also 3.2V in, the device current of P7 is close
Degree highest can reach 150mA/cm2More than, brightness is close to 10000cd/m2, the maximum external quantum efficiency of device can also reach
26% level, maximum power efficiency reach 89lm/W.Equally, also there is the outer quantum of maximum close to 16% for the device of P10
Efficiency shows that the device luminescent properties of both material preparations are all more excellent.
Table 2. is using P7 and P11 as the master data of the organic light emitting diode device of luminescent layer
Embodiment 23
Using the organic molecule luminescent material (P3 and P19) based on pyrazine receptor unit of the present invention as organic light emission
The luminescent layer of diode component, the general-purpose device structure of implementation are as follows：ITO/TAPC(20nm)/CBP:3wt%P3 or P19
(35nm)/TmPyPB (55nm)/LiF (1nm)/Al (100nm), wherein CBP is luminescent material doped body, remaining material is at this
The effect of organic light emitting diode device is identical with embodiment 25.
The preparation process of the organic light emitting diode device in addition to during luminescent layer is deposited by DPEPO change into CBP with
Outside, remaining step is all identical with embodiment 25.
Table 3. is using P3 and P19 as the master data of the organic light emitting diode device of luminescent layer
The molecular formula difference of TAPC, mCP, DPEPO, TmPyPB, CBP described in embodiment 21~23 are as follows：
It can be seen that from above-mentioned device embodiments result for using the acridine reversed greatly and fenPiperazine group is as donor
During unit, device opens bright voltage and can be maintained at 3~4V or so, even for the sulphur bridge structural molecule that conjugation interrupts, device
Maximum external quantum efficiency can be more than 5%.Simultaneously compared to acridine group, for using to electrical stronger fenPiperazine group is made
During for donor monomer, the carrier transmission performance and luminous efficiency of material all have significant improvement, and the maximum of device is outer to be measured
Sub- efficiency can be increased to 26% or so.These make luminescent layer with the organic molecule luminescent material based on pyrazine receptor unit
Organic light emitting diode device has more apparent excellent in terms of luminous efficiency compared to light emitting molecule with similar structure
Gesture.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by the embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of organic molecule luminescent material based on pyrazine receptor unit, which is characterized in that there is following P1n~P5n institutes
Any one of chemical structural formula shown：
Wherein, Ar represents the aromatic amine groups of any one type in (1)~(4)：
2. the organic molecule luminescent material according to claim 1 based on pyrazine receptor unit, which is characterized in that have
Structural formula shown in any one of following P1~P20：
3. the organic molecule luminescent material described in claim 1 based on pyrazine receptor unit, which is characterized in that including following
Preparation process：
(1) any one of a~d intermediates are prepared：
(2) under the protection of inert gas, in organic solvent add in step (1) prepare intermediate, aromatic amine compounds,
Alkali and catalyst are uniformly mixed, and are heated to reflux being stirred to react, and via cooling down, extracting, being spin-dried for solvent, column chromatography, are obtained described
Organic molecule luminescent material based on pyrazine receptor unit；
The intermediate is 1 with the molar ratio used in aromatic amine compounds:(2~2.5)；The alkali be organic base, dosage with
The molar ratio of aromatic amine compounds is (1.8~2.5):1.
4. the organic molecule luminescent material based on pyrazine receptor unit described in claim 3, which is characterized in that step (1)
Any one of preparation a~d intermediates, specially：For intermediate a~c, under the protection of inert gas, in a solvent
It adds in two halogen pyrazines of different location substitution, chlorophenylboronic acid, alkali and tetrakis triphenylphosphine palladium is uniformly mixed, be heated to reflux
It is stirred to react, via cooling down, extracting, being spin-dried for solvent, column chromatography, obtains intermediate a~c；
For intermediate d, under the protection of inert gas, 2,5-, bis- bromo-pyrazines are added in organic solvent, to bromo thiophenol, alkali
It is uniformly mixed, reaction is stirred at room temperature, via cooling down, extracting, being spin-dried for solvent, column chromatography, obtain intermediate d.
5. the organic molecule luminescent material based on pyrazine receptor unit described in claim 3, which is characterized in that step (2)
The temperature of the heating reflux reaction is 90~110 DEG C, the reaction time for 12~for 24 hours.
6. the organic molecule luminescent material based on pyrazine receptor unit described in claim 3, which is characterized in that step (2)
The aromatic amine compounds are 5- carbolines, 9,9 '-dimethyl acridinium, fenAny one in piperazine or phenthazine.
7. the organic molecule luminescent material based on pyrazine receptor unit described in claim 3, which is characterized in that step (2)
The catalyst is made of palladium and three tertiary butyl phosphines.
8. the organic molecule luminescent material described in claim 1 based on pyrazine receptor unit, which is characterized in that including following
Step：
Under the protection of inert gas, 2,5-, bis- bromo-pyrazines, aromatic amine compounds, alkali and catalysis are added in organic solvent
Agent is uniformly mixed, and is heated to reflux being stirred to react, via cooling down, extracting, being spin-dried for solvent, column chromatography, obtain it is described based on pyrazine by
The organic molecule luminescent material of body unit；
Bis- bromo-pyrazines of 2,5- are 1 with the molar ratio used in aromatic amine compounds:(2~2.5)；The alkali is organic base,
Dosage and the molar ratio of aromatic amine compounds are (1.8~2.5):1.
9. the organic molecule luminescent material according to any one of claims 8 based on pyrazine receptor unit, which is characterized in that step (2)
The temperature of the heating reflux reaction is 90~110 DEG C, the reaction time for 12~for 24 hours.
10. organic molecule luminescent material material of claim 1~2 any one of them based on pyrazine receptor unit is applied to have
In machine light emitting diode.
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| CN111217990A (en) * | 2020-01-20 | 2020-06-02 | 西安交通大学 | D-A copolymer donor material based on different substituted pyrazine acceptor units and application |
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