CN109956933A - A kind of organic compound containing pyridine and its application on organic electroluminescence device - Google Patents
A kind of organic compound containing pyridine and its application on organic electroluminescence device Download PDFInfo
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- CN109956933A CN109956933A CN201711342591.0A CN201711342591A CN109956933A CN 109956933 A CN109956933 A CN 109956933A CN 201711342591 A CN201711342591 A CN 201711342591A CN 109956933 A CN109956933 A CN 109956933A
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 150000002894 organic compounds Chemical class 0.000 title claims abstract description 33
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000005401 electroluminescence Methods 0.000 title claims description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 78
- 239000010410 layer Substances 0.000 claims description 89
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 238000002360 preparation method Methods 0.000 claims description 26
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000741 silica gel Substances 0.000 claims description 18
- 229910002027 silica gel Inorganic materials 0.000 claims description 18
- 229960001866 silicon dioxide Drugs 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 16
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims description 16
- 241000720974 Protium Species 0.000 claims description 16
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical group [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 claims description 16
- 229910052805 deuterium Inorganic materials 0.000 claims description 16
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 16
- 229910052722 tritium Inorganic materials 0.000 claims description 16
- 125000005843 halogen group Chemical group 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 14
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 13
- 235000011009 potassium phosphates Nutrition 0.000 claims description 13
- 239000000376 reactant Substances 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 10
- -1 Pyrimidine radicals Chemical class 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000005864 Sulphur Substances 0.000 claims description 6
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- 230000005611 electricity Effects 0.000 claims description 5
- 238000005286 illumination Methods 0.000 claims description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 5
- VIJYEGDOKCKUOL-UHFFFAOYSA-N 9-phenylcarbazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2C2=CC=CC=C21 VIJYEGDOKCKUOL-UHFFFAOYSA-N 0.000 claims description 4
- 230000000903 blocking effect Effects 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000004076 pyridyl group Chemical group 0.000 claims description 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 2
- DBMCEXFNPAOEIH-UHFFFAOYSA-N 9,9-dimethylfluorene Chemical compound C1=CC=C2C(C)(C)C3=C=CC=C[C]3C2=C1 DBMCEXFNPAOEIH-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000004653 anthracenylene group Chemical group 0.000 claims description 2
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 claims description 2
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 claims description 2
- 150000004826 dibenzofurans Chemical class 0.000 claims description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene sulfoxide Natural products C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims description 2
- 125000002541 furyl group Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims description 2
- 125000005956 isoquinolyl group Chemical group 0.000 claims description 2
- 150000002790 naphthalenes Chemical class 0.000 claims description 2
- 125000004957 naphthylene group Chemical group 0.000 claims description 2
- 150000005054 naphthyridines Chemical class 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 125000003373 pyrazinyl group Chemical group 0.000 claims description 2
- 125000002098 pyridazinyl group Chemical group 0.000 claims description 2
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- 239000002346 layers by function Substances 0.000 claims 1
- 150000003222 pyridines Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 79
- 230000004888 barrier function Effects 0.000 abstract description 9
- 238000000605 extraction Methods 0.000 abstract description 8
- 230000009477 glass transition Effects 0.000 abstract description 4
- 238000004770 highest occupied molecular orbital Methods 0.000 abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 36
- 238000012360 testing method Methods 0.000 description 30
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 25
- 238000003786 synthesis reaction Methods 0.000 description 22
- 230000015572 biosynthetic process Effects 0.000 description 21
- 238000000921 elemental analysis Methods 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 238000000746 purification Methods 0.000 description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 239000010408 film Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 8
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 238000004128 high performance liquid chromatography Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 238000007738 vacuum evaporation Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 6
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229940125904 compound 1 Drugs 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 239000011368 organic material Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- 239000003480 eluent Substances 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 4
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 4
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 4
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 4
- 235000011056 potassium acetate Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- 239000012312 sodium hydride Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- UAOUIVVJBYDFKD-XKCDOFEDSA-N (1R,9R,10S,11R,12R,15S,18S,21R)-10,11,21-trihydroxy-8,8-dimethyl-14-methylidene-4-(prop-2-enylamino)-20-oxa-5-thia-3-azahexacyclo[9.7.2.112,15.01,9.02,6.012,18]henicosa-2(6),3-dien-13-one Chemical compound C([C@@H]1[C@@H](O)[C@@]23C(C1=C)=O)C[C@H]2[C@]12C(N=C(NCC=C)S4)=C4CC(C)(C)[C@H]1[C@H](O)[C@]3(O)OC2 UAOUIVVJBYDFKD-XKCDOFEDSA-N 0.000 description 2
- YJLIKUSWRSEPSM-WGQQHEPDSA-N (2r,3r,4s,5r)-2-[6-amino-8-[(4-phenylphenyl)methylamino]purin-9-yl]-5-(hydroxymethyl)oxolane-3,4-diol Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1CNC1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](CO)[C@@H](O)[C@H]1O YJLIKUSWRSEPSM-WGQQHEPDSA-N 0.000 description 2
- UDQTXCHQKHIQMH-KYGLGHNPSA-N (3ar,5s,6s,7r,7ar)-5-(difluoromethyl)-2-(ethylamino)-5,6,7,7a-tetrahydro-3ah-pyrano[3,2-d][1,3]thiazole-6,7-diol Chemical compound S1C(NCC)=N[C@H]2[C@@H]1O[C@H](C(F)F)[C@@H](O)[C@@H]2O UDQTXCHQKHIQMH-KYGLGHNPSA-N 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 2
- PAYROHWFGZADBR-UHFFFAOYSA-N 2-[[4-amino-5-(5-iodo-4-methoxy-2-propan-2-ylphenoxy)pyrimidin-2-yl]amino]propane-1,3-diol Chemical compound C1=C(I)C(OC)=CC(C(C)C)=C1OC1=CN=C(NC(CO)CO)N=C1N PAYROHWFGZADBR-UHFFFAOYSA-N 0.000 description 2
- YSUIQYOGTINQIN-UZFYAQMZSA-N 2-amino-9-[(1S,6R,8R,9S,10R,15R,17R,18R)-8-(6-aminopurin-9-yl)-9,18-difluoro-3,12-dihydroxy-3,12-bis(sulfanylidene)-2,4,7,11,13,16-hexaoxa-3lambda5,12lambda5-diphosphatricyclo[13.2.1.06,10]octadecan-17-yl]-1H-purin-6-one Chemical compound NC1=NC2=C(N=CN2[C@@H]2O[C@@H]3COP(S)(=O)O[C@@H]4[C@@H](COP(S)(=O)O[C@@H]2[C@@H]3F)O[C@H]([C@H]4F)N2C=NC3=C2N=CN=C3N)C(=O)N1 YSUIQYOGTINQIN-UZFYAQMZSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- POFVJRKJJBFPII-UHFFFAOYSA-N N-cyclopentyl-5-[2-[[5-[(4-ethylpiperazin-1-yl)methyl]pyridin-2-yl]amino]-5-fluoropyrimidin-4-yl]-4-methyl-1,3-thiazol-2-amine Chemical compound C1(CCCC1)NC=1SC(=C(N=1)C)C1=NC(=NC=C1F)NC1=NC=C(C=C1)CN1CCN(CC1)CC POFVJRKJJBFPII-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229940125936 compound 42 Drugs 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 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 description 2
- 239000000047 product Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- QEBYEVQKHRUYPE-UHFFFAOYSA-N 2-(2-chlorophenyl)-5-[(1-methylpyrazol-3-yl)methyl]-4-[[methyl(pyridin-3-ylmethyl)amino]methyl]-1h-pyrazolo[4,3-c]pyridine-3,6-dione Chemical compound C1=CN(C)N=C1CN1C(=O)C=C2NN(C=3C(=CC=CC=3)Cl)C(=O)C2=C1CN(C)CC1=CC=CN=C1 QEBYEVQKHRUYPE-UHFFFAOYSA-N 0.000 description 1
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 1
- DQFMPTUTAAIXAN-UHFFFAOYSA-N 4,4-dimethyl-1h-imidazol-5-one Chemical compound CC1(C)NC=NC1=O DQFMPTUTAAIXAN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011982 device technology Methods 0.000 description 1
- DKHNGUNXLDCATP-UHFFFAOYSA-N dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile Chemical compound C12=NC(C#N)=C(C#N)N=C2C2=NC(C#N)=C(C#N)N=C2C2=C1N=C(C#N)C(C#N)=N2 DKHNGUNXLDCATP-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000004038 photonic crystal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
Classifications
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- 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
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
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- 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
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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]
- H10K50/14—Carrier transporting layers
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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]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting 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
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
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- H—ELECTRICITY
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- 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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- Chemical & Material Sciences (AREA)
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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
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- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The present invention relates to a kind of organic compound containing pyridine and its applications in OLED device, shown in the structure of the compounds of this invention such as general formula (1):
Description
Technical field
The present invention relates to technical field of semiconductors, more particularly, to a kind of organic compound containing pyridine and its are having
Application in organic electroluminescence devices.
Background technique
Organic electroluminescent (OLED:Organic Light Emission Diodes) device technology can both be used to make
New display product is made, production novel illumination product is can be used for, is expected to substitute existing liquid crystal display and fluorescent lighting,
Application prospect is very extensive.OLED luminescent device including electrode material film layer and is clipped in different electricity like the structure of sandwich
Organic functional material between the film layer of pole, various different function materials are overlapped mutually depending on the application collectively constitutes OLED hair together
Optical device.OLED luminescent device is as current device, when applying voltage to its two end electrodes, and passes through electric field action organic layer function
Can positive and negative charge in film layer when, positive and negative charge is further compound in luminescent layer, i.e. generation OLED electroluminescent.
Currently, OLED display technology in smart phone, applied by the fields such as tablet computer, further will also be to electricity
Depending on etc. large scales application field extension.But due between the external quantum efficiency and internal quantum efficiency of OLED there are huge spread,
Greatly restrict the development of OLED.Therefore, the light extraction efficiency for how improving OLED becomes research hotspot.Ito thin film and glass
The interface of the interface of glass substrate and glass substrate and air can be totally reflected, and be emitted to before OLED device to exterior space
Light account for about the 20% of organic material film EL total amount, it is thin that remaining about 80% light is mainly limited in organic material in the form of guided wave
In film, ito thin film and glass substrate.It can be seen that the light extraction efficiency of conventional OLED device is lower (about 20%), this is seriously constrained
The development and application of OLED.How to reduce total reflection effect in OLED device, improve optically coupling to before device to exterior space
Ratio (light extraction efficiency) cause the extensive concern of people.
Currently, realize improve OLED external quantum efficiency a kind of important method be substrate light output surface formed as fold,
The structures such as photonic crystal, lenticule display (MLA) and addition surface coating.First two structure will affect the radiation spectrum of OLED
Angular distribution, the third structure fabrication processes is complicated, and using surface coating simple process, luminous efficiency improves 30% or more,
Especially people pay close attention to.According to optical principle, when light transmission superrefraction rate is n1Substance to refractive index be n2Substance when (n1>
n2), only in arcsin (n2/n1) angle in can just be incident on refractive index be n2Substance in, absorptivity B can be with following
Formula calculate:
If n1=nGeneral OLED organic material=1.70, n2=nGlass=1.46, then 2B=0.49.Assuming that the light whole quilt propagated outward
Metal electrode reflection, then only 51% luminous energy is by the organic film of high refractive index and the waveguide of ITO layer institute, can equally calculate light from
Substrate of glass injects to transmitance when air.When therefore going out the outside of device from the light emission that organic layer issues, only about 17%
Luminous energy seen by people.Therefore, the status low for current OLED device light extraction efficiency, needs to increase in the device structure
Add one layer CPL layers, i.e. light extraction material, according to optical absorption, refraction principle, the refractive index of this surface coating material should be got over
It is high better.
Proposing high performance research to OLED luminescent device at present includes: the driving voltage for reducing device, the hair for improving device
Light efficiency, the service life for improving device etc..In order to realize OLED device performance continuous promotion, not only need from OLED device
The innovation of part structure and manufacture craft is constantly studied and is innovated with greater need for oled light sulfate ferroelectric functional material, formulates out higher performance
OLED functional material.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, the applicant provide a kind of organic compound containing pyridine and
Its application on organic electroluminescence device.The compounds of this invention contains pyridine structure, glass transition temperature with higher
With molecule thermal stability, visible regime absorb it is low, refractive index is high, be applied to OLED device CPL layer after, can effectively mention
Rise the light extraction efficiency of OLED device；And since quinoxaline, benzimidazole and benzoxazoles group have deep HOMO energy level,
Wide forbidden band (Eg) energy level can be used as hole barrier/electron transport layer materials of OLED device, and hole is stopped to be transmitted from luminescent layer
To electronic shell side, the multiplicity of hole and electronics in luminescent layer is improved, to promote the luminous efficiency of OLED device and make
Use the service life.
Technical scheme is as follows: a kind of organic compound containing pyridine, the structure of the organic compound
As shown in general formula (1):
In general formula (1), p, m, n independently be expressed as number 0,1 or 2；And m+n+p >=3；
In general formula (1), Ar1、Ar2、Ar3Independently be expressed as singly-bound, substituted or unsubstituted C6-60Arlydene contains
There are one of one or more heteroatomic substituted or unsubstituted 5~60 yuan of heteroarylidenes；The hetero atom be nitrogen, oxygen or
Sulphur；The Ar1、Ar2、Ar3It can be identical or different；
R1、R2、R3It is optionally by one or more R4Substituted or unsubstituted quinoxalinyl, by one or more R4Replace
Or unsubstituted benzimidazolyl, by one or more R4Substituted or unsubstituted benzoxazolyl；R1、R2、R3Different phases
Together；
Z is expressed as N atom or C-H identical or differently；
R4It is expressed as substituted or unsubstituted C6To C30Aryl and containing one or more heteroatomic substituted or unsubstituted
C5To C30One of heteroaryl；The hetero atom is nitrogen, oxygen or sulphur.
On the basis of above scheme, the present invention can also be improved as follows.
Preferably, a kind of organic compound containing pyridine, the R1、R2、R3Independently be expressed as general formula (2),
General formula (3), general formula (4), general formula (5), general formula (6), general formula (7), general formula (8), general formula (9), general formula (10) or general formula (11) institute
Show structure；
Wherein, the Ar4、Ar5、Ar6、Ar7、Ar8、Ar9、Ar10、Ar11、Ar12、Ar13、Ar14Being expressed as independently
Hydrogen atom, C1-10Linear or branched alkyl group, substituted or unsubstituted C6-60Aryl, containing one or more heteroatomic substitutions or
One of unsubstituted 5~60 unit's heteroaryl；The hetero atom is nitrogen, oxygen or sulphur；Ar4、Ar5、Ar6、Ar7、Ar8、Ar9、
Ar10、Ar11、Ar12、Ar13、Ar14It can be identical or different；R4 is expressed as phenyl, xenyl, naphthalene or pyridyl group；Q be 0,1 or
2。
Preferably, a kind of organic compound containing pyridine, the structure of the organic compound such as formula (I-1)~(I-
5) any shown in:
Preferably, a kind of organic compound containing pyridine, the Ar1、Ar2、Ar3Independently be expressed as C1-10
Linear or branched alkyl group, halogen atom, protium, deuterium, the substituted or unsubstituted phenylene of tritium atom；C1-10Linear or branched alkyl group,
Halogen atom, protium, deuterium, the substituted or unsubstituted naphthylene of tritium atom；C1-10Linear or branched alkyl group, halogen atom, protium, deuterium,
The substituted or unsubstituted sub- dibiphenylyl of tritium atom；Anthrylene；C1-10Linear or branched alkyl group, halogen atom, protium, deuterium, tritium are former
The substituted or unsubstituted sub-pyridyl group of son；Sub- carbazyl；Furylidene；Sub- quinolyl；Sub- naphthyridines base；Sub- dibenzofuran group；
Sub- dibenzothiophene；One of sub- 9,9- dimethyl fluorenyl or Asia N- phenyl carbazole base；
The Ar4、Ar5、Ar6、Ar7、Ar8、Ar9、Ar10、Ar11、Ar12、Ar13、Ar14Independently be expressed as C1-10Directly
Chain or branched alkyl, halogen atom, protium, deuterium, the substituted or unsubstituted phenyl of tritium atom；C1-10Linear or branched alkyl group, halogen
Atom, protium, deuterium, the substituted or unsubstituted naphthalene of tritium atom；C1-10Linear or branched alkyl group, halogen atom, protium, deuterium, tritium atom
Substituted or unsubstituted dibiphenylyl；C1-10Linear or branched alkyl group, halogen atom, protium, deuterium, tritium atom are substituted or unsubstituted
Pyridyl group；Carbazyl；Furyl；Pyrimidine radicals；Pyrazinyl；Pyridazinyl；Dibenzofurans；9,9- dimethyl fluorene；N- phenyl carbazole；
Quinolyl；One of isoquinolyl or naphthyridines base.
Preferably, a kind of organic compound containing pyridine, the concrete structure formula of the organic compound are as follows:
Any one.
The application also provides a kind of preparation method of organic compound containing pyridine, and the preparation method is related to anti-
Answer equation are as follows:
(1) it under nitrogen atmosphere, weighs raw material A and is dissolved in DMF, addAnd palladium acetate, stirring are mixed
Object is closed, adds aqueous potassium phosphate solution, it is small that the mixed solution of above-mentioned reactant is heated to reflux 5-15 under the conditions of 120-150 DEG C
When；After reaction, Jia Shui is cooled down, mixture is filtered and is dried in a vacuum drying oven, it is pure that gained residue crosses silicagel column
Change, obtains compound intermediate I；
The raw material A withMolar ratio be 1:1.0~3, the molar ratio of palladium acetate and raw material A is
The molar ratio of 0.001~0.04:1, potassium phosphate and raw material A is 1.0~4.0:1, and toluene dosage is that every gram of raw material A uses 30-
50ml toluene；
(2) it under nitrogen atmosphere, weighs intermediate compound I and is dissolved in DMF, addAnd palladium acetate, stirring
Mixture adds aqueous potassium phosphate solution, and the mixed solution of above-mentioned reactant is heated to reflux 10- under the conditions of 120-150 DEG C
24 hours；After reaction, Jia Shui is cooled down, mixture is filtered and is dried in a vacuum drying oven, gained residue crosses silica gel
Column purification obtains compound intermediate II；
The intermediate compound I withMolar ratio be 1:1.0~3, the molar ratio of palladium acetate and intermediate compound I
For 0.001~0.04:1, the molar ratio of potassium phosphate and intermediate compound I is 1.0~4.0:1, and toluene dosage is that every gram of intermediate compound I uses
10-40ml toluene；
(3) it under nitrogen atmosphere, weighs intermediate II and is dissolved in DMF, addAnd palladium acetate, it stirs
Mixture is mixed, aqueous potassium phosphate solution is added, the mixed solution of above-mentioned reactant is heated to reflux under the conditions of 120-150 DEG C
10-24 hours；After reaction, Jia Shui is cooled down, mixture is filtered and is dried in a vacuum drying oven, gained residue crosses silicon
Rubber column gel column purifying, obtains target compound；
The intermediate II withMolar ratio be 1:1.0~3, mole of palladium acetate and intermediate II
Than for 0.001~0.04:1, the molar ratio of potassium phosphate and intermediate II is 1.0~4.0:1, toluene dosage is every gram of intermediate II
Use 15-50ml toluene.
A kind of organic compound containing pyridine is applied to prepare organic electroluminescence device.
The present invention also provides a kind of organic electroluminescence device, the organic electroluminescence device includes at least one layer of function
Layer contains the organic compound containing pyridine.
Preferably, a kind of organic electroluminescence device, including hole blocking layer/electron transfer layer, the hole blocking layer/
Electron transfer layer contains the organic compound containing pyridine.
Preferably, a kind of organic electroluminescence device, including CPL layers, described CPL layers containing described containing pyridine
Organic compound.
The present invention also provides a kind of illumination or display element, the illumination or display element contain the organic electroluminescence hair
Optical device.
The present invention is beneficial to be had the technical effect that
The structure of organic compound of the invention contains quinoxaline or benzimidazole or benzoxazoles rigid radical, improves
Material structure stability；Material of the present invention contains strong electron-withdrawing pyridine, quinoxaline or benzimidazole on space structure
Or benzoxazoles group, and quinoxaline or benzimidazole or benzoxazoles group intersect and separate, and group is avoided freely to revolve
Turn, so that material density with higher, obtains higher refractive index；Meanwhile so that material of the present invention all have it is very high
Tg temperature；The vapor deposition temperature of material of the present invention under vacuum conditions is generally less than 350 DEG C, both ensure that material in volume production duration
Time evaporation material does not decompose, and reduces the heat radiation due to vapor deposition temperature to the influence of crust deformation that MASK is deposited.
Material of the present invention applies the electrons and holes transmission that device is not involved at CPL layers in OLED device, but to material
Thermal stability, membrane crystallization and optical transport (high refractive index) have very high requirement.As above analysis, pyridine, quinoxaline
Or benzimidazole or benzoxazoles are rigid radical, improve the stability of material；High Tg temperature, ensure that material in film
It is not crystallized under state；Low vapor deposition temperature is the premise that material can be applied to volume production；High refractive index is then material energy of the present invention
Applied to CPL layers of main factor.
For material of the present invention due to having deep HOMO energy level, high electron mobility can effectively stop hole or energy from hair
Photosphere is transferred to electronic shell side, so that the combined efficiency of hole and electronics in luminescent layer is improved, to promote OLED device
Luminous efficiency and service life.After the CPL layer for being applied to OLED device, the light that can effectively promote OLED device takes the present invention
Efficiency out.To sum up, compound of the present invention has good application effect and industrialization prospect in OLED luminescent device.
Detailed description of the invention
Fig. 1 is the structural schematic diagram that material cited by the present invention is applied to OLED device；
Wherein, 1, OLED device substrate, 2, anode layer, 3, hole injection layer, 4, hole transmission layer, 5, luminescent layer, 6, sky
Cave barrier layer/electron transfer layer, 7, electron injecting layer, 8, cathode layer, 9, CPL layers；
Fig. 2 is the refraction index test figure of compound 6；
Fig. 3-1 is the crystalline state for the membrane material that compound 1 is formed；
Fig. 3-2 is the crystalline state for the membrane material that well known materials CBP is formed；
Fig. 3-3 is the crystalline state for the membrane material that compound 1 is formed after testing 72 hours；
Fig. 3-4 is the crystalline state for the membrane material that CBP is formed after testing 72 hours；
Fig. 3-5 is the crystalline state for the membrane material that compound 1 is formed after testing 200 hours；
Fig. 4 is the efficiency curve diagram that device measures at different temperatures.
Specific embodiment
Embodiment 1:
IntermediateSynthesis
(1) with R1、R2Or R3For when being expressed as general formula (2) structure,
1) in there-necked flask, it is passed through nitrogen, raw material B, I-Ar is added4, sodium hydride, cuprous iodide and Phen be dissolved in
In 1,3-Dimethyl-2-imidazolidinone, it is stirred to react 30h, after reaction, adds water and is extracted with dichloromethane, organic layer is used
Anhydrous sodium sulfate is dry, and the mixture with petroleum ether and ethyl acetate is eluent elution, and column chromatographic purifying obtains intermediate M；
2) it under nitrogen atmosphere, weighs intermediate M and is dissolved in tetrahydrofuran, then by Br-Ar2-B(OH)2And four (triphenyl
Phosphine) palladium addition, mixture is stirred, unsaturated carbonate aqueous solutions of potassium is added, by the mixed solution of above-mentioned reactant in reaction temperature
It is heated to reflux at 80 DEG C 20 hours；After reaction, cooling, mixed liquor is extracted with dichloromethane, extract anhydrous sodium sulfate
It is dried, and is concentrated under reduced pressure, thickened solid is crossed into silica gel column purification, obtains compound intermediate N；
3) under nitrogen atmosphere, weigh intermediate N and be dissolved in n,N-Dimethylformamide (DMF), then will be bis- (pinacol root
Base) two boron, (1,1 '-bis- (diphenylphosphine) ferrocene) dichloro palladium (II) and potassium acetate addition, mixture is stirred, it will be above-mentioned anti-
The mixed solution of object is answered to be heated to reflux at 150 DEG C of reaction temperature 10 hours；After reaction, it cools down and filters mixture
And it is dry in vacuum drying oven.Residue obtained is crossed into silica gel column separating purification, obtains compound intermediate B；
(2) with R1、R2Or R3For when being expressed as general formula (3) structure,
1) it under nitrogen atmosphere, weighs raw material B and is dissolved in tetrahydrofuran, then by Ar5-B(OH)2And tetrakis triphenylphosphine palladium
It is added, stirs mixture, unsaturated carbonate aqueous solutions of potassium is added, by the mixed solution of above-mentioned reactant at 80 DEG C of reaction temperature
It is heated to reflux 15 hours；After reaction, cooling, mixed liquor is extracted with dichloromethane, at extract anhydrous sodium sulfate drying
Reason, and be concentrated under reduced pressure, thickened solid is crossed into silica gel column purification, obtains compound intermediate P；
2) under nitrogen atmosphere, intermediate P, I-Ar is added2- Br, sodium hydride, cuprous iodide and Phen are dissolved in 1,3-
In dimethyl-2-imidazolinone, it is stirred to react 30h, after reaction, adds water and is extracted with dichloromethane, organic layer is with anhydrous
Sodium sulphate is dry, and the mixture with petroleum ether and ethyl acetate is eluent elution, and column chromatographic purifying obtains intermediate Q；
3) under nitrogen atmosphere, weigh intermediate Q and be dissolved in n,N-Dimethylformamide (DMF), then will be bis- (pinacol root
Base) two boron, (1,1 '-bis- (diphenylphosphine) ferrocene) dichloro palladium (II) and potassium acetate addition, mixture is stirred, it will be above-mentioned anti-
The mixed solution of object is answered to be heated to reflux at 120-150 DEG C of reaction temperature 10 hours；After reaction, cooling and by mixture
It filters and dry in vacuum drying oven.Residue obtained is crossed into silica gel column separating purification, obtains compound intermediate B；
(3) with R1、R2Or R3It is expressed as general formula (4) structure,
1) under nitrogen atmosphere, raw material C, I-Ar is added7, sodium hydride, cuprous iodide and Phen be dissolved in 1,3- diformazan
In base -2- imidazolone, it is stirred to react 30h, after reaction, adds water and is extracted with dichloromethane, organic layer anhydrous slufuric acid
Sodium is dry, and the mixture with petroleum ether and ethyl acetate is eluent elution, and column chromatographic purifying obtains intermediate X；
2) it under nitrogen atmosphere, weighs intermediate X and is dissolved in tetrahydrofuran, then by Ar6-B(OH)2And four (triphenylphosphine)
Palladium is added, and stirs mixture, unsaturated carbonate aqueous solutions of potassium is added, by the mixed solution of above-mentioned reactant in 80 DEG C of reaction temperature
Under be heated to reflux 15 hours；After reaction, cooling, mixed liquor is extracted with dichloromethane, and extract is dry with anhydrous sodium sulfate
Processing, and be concentrated under reduced pressure, thickened solid is crossed into silica gel column purification, obtains compound intermediate Y；
3) it under nitrogen atmosphere, weighs intermediate Y and is dissolved in n,N-Dimethylformamide, then by Br-Ar2-B(OH)2And vinegar
Sour palladium is added, and stirs mixture, aqueous potassium phosphate solution is added, by the mixed solution of above-mentioned reactant in 150 DEG C of reaction temperature
Under be heated to reflux 24 hours；After reaction, Jia Shui is cooled down, mixture is filtered and is dried in a vacuum drying oven, gained is residual
Excess crosses silica gel column purification, obtains Compound Compound intermediate Z；
4) under nitrogen atmosphere, weigh intermediate Z and be dissolved in n,N-Dimethylformamide (DMF), then will be bis- (pinacol root
Base) two boron, (1,1 '-bis- (diphenylphosphine) ferrocene) dichloro palladium (II) and potassium acetate addition, mixture is stirred, it will be above-mentioned anti-
The mixed solution of object is answered to be heated to reflux at 150 DEG C of reaction temperature 10 hours；After reaction, it cools down and filters mixture
And it is dry in vacuum drying oven.Residue obtained is crossed into silica gel column separating purification, obtains compound intermediate B；
By taking the synthesis of intermediate B 1 as an example
(1) in 250mL there-necked flask, it is passed through nitrogen, 0.02mol raw material B1,0.03mol raw material E1,0.04mol hydrogen is added
Change sodium, 0.004mol cuprous iodide and 0.01mol Phen to be dissolved in 100ml 1,3-Dimethyl-2-imidazolidinone, stir
It mixes reaction 20-30h to add water after reaction and be extracted with dichloromethane, organic layer is dry with anhydrous sodium sulfate, uses petroleum ether
Mixture with ethyl acetate is eluent elution, and the volume ratio of petroleum ether and ethyl acetate is 1:100, column chromatography in eluent
Purifying, obtains intermediate X 1；HPLC purity 99.7%, yield 78.5%.
Elemental analysis structure (molecular formula C13H9BrN2): theoretical value C, 57.17；H,3.32；Br,29.25；N,10.26；It surveys
Examination value: C, 57.19；H,2.33；Br,29.26；N,10.32.ESI-MS(m/z)(M+): theoretical value 271.99, measured value are
272.05。
(2) in 250mL there-necked flask, it is passed through nitrogen, 0.04mol intermediate X 1 is added, the THF of 100ml, 0.05mol are former
Expect F1,0.0004mol tetrakis triphenylphosphine palladium, then 0.06mol K is added in stirring2CO3Aqueous solution (2M), is heated to 80 DEG C,
Back flow reaction 10 hours, sample contact plate, fully reacting.Natural cooling is extracted with 200ml methylene chloride, layering, extract liquor nothing
Aqueous sodium persulfate dries, filters, and filtrate revolving crosses silica gel column purification, obtains intermediate Y1, HPLC purity 99.8%, yield
88.2%.
Elemental analysis structure (molecular formula C19H13BrN2): theoretical value C, 65.35；H,3.75；Br,22.88；N,8.02；It surveys
Examination value: C, 65.44；H,3.83；Br,22.92；N,8.08.ESI-MS(m/z)(M+): theoretical value 348.03, measured value are
348.11。
(3) in 500mL there-necked flask, it is passed through nitrogen, the N that 0.05mol intermediate Y1 is dissolved in 300ml, N- diformazan is added
In base formamide (DMF), then (1,1 '-bis- (diphenylphosphines) two is luxuriant by 0.06mol bis- (pinacol foundation) two boron, 0.0005mol
Iron) dichloro palladium (II) and 0.125mol potassium acetate be added, mixture is stirred, by the mixed solution of above-mentioned reactant in reaction temperature
It is heated to reflux 10 hours at 120-150 DEG C of degree；After reaction, cool down and be added 200ml water and by mixture filtering and true
It is dry in empty baking oven.Residue obtained is crossed into silica gel column separating purification, obtains compound intermediate B1；HPLC purity
99.2%, yield 81.2%.Elemental analysis structure (molecular formula C25H25BN2O2): theoretical value C, 75.77；H,6.36；B,2.73；
N,7.07；O,8.07；Test value: C, 75.82；H,6.44；B,2.75；N,7.14；O,8.15.ESI-MS(m/z)(M+): it is theoretical
Value is 396.20, measured value 396.23.Intermediate B is prepared with the synthetic method of intermediate B 1, specific structure is as shown in table 1.
Table 1
Embodiment 2: the synthesis of compound 1:
In 250mL there-necked flask, it is passed through nitrogen, 0.01mol intermediate A 1, the DMF of 150ml, 0.03mol intermediate is added
Then 0.02mol ﹒ L is added in B2,0.0002mol palladium acetate, stirring-1 K3PO4Aqueous solution is heated to 150 DEG C, back flow reaction 24
Hour, sample contact plate, fully reacting.Natural cooling is extracted with 200ml methylene chloride, layering, and extract liquor is dry with anhydrous sodium sulfate
Dry, filtering, filtrate revolving crosses silica gel column purification, obtains intermediate 1, HPLC purity 99.2%, yield 53.6%.
Elemental analysis structure (molecular formula C16H9Cl2N6): theoretical value C, 56.16；H,2.65；N,20.47；Cl,20.72；It surveys
Examination value: C, 56.22；H,2.69；N,20.49；Cl,20.77.ESI-MS(m/z)(M+): theoretical value 341.02, measured value are
341.05。
In 250mL there-necked flask, it is passed through nitrogen, 0.01mol intermediate 1, the DMF of 150ml, 0.06mol intermediate is added
Then 0.02mol ﹒ L is added in B4,0.0002mol palladium acetate, stirring-1 K3PO4Aqueous solution is heated to 150 DEG C, back flow reaction 24
Hour, sample contact plate, fully reacting.Natural cooling is extracted with 200ml methylene chloride, layering, and extract liquor is dry with anhydrous sodium sulfate
Dry, filtering, filtrate revolving crosses silica gel column purification, obtains intermediate 1, HPLC purity 98.9%, yield 52.6%.
Elemental analysis structure (molecular formula C32H19N9): theoretical value C, 72.58；H,3.62；N,23.80；Test value: C,
72.62；H,3.69；N,23.87.ESI-MS(m/z)(M+): theoretical value 529.18, measured value 529.21.
Embodiment 3: the synthesis of compound 6:
The preparation method of compound 6 is with embodiment 2, the difference is that replacing intermediate B 2 with intermediate B 1.Element point
Analyse structure (molecular formula C38H23N9): theoretical value C, 75.36；H,3.83；N,20.81；Test value: C, 75.39；H,3.85；N,
20.85。ESI-MS(m/z)(M+): theoretical value 605.21, measured value 605.29.
Embodiment 4: the synthesis of compound 26:
The preparation method of compound 26 is with embodiment 3, the difference is that replacing intermediate B 4 with intermediate B 5.Element point
Analyse structure (molecular formula C50H31N9): theoretical value C, 79.24；H,4.12；N,16.63；Test value: C, 79.29；H,4.15；N,
16.65。ESI-MS(m/z)(M+): theoretical value 757.27, measured value 757.29.
Embodiment 5: the synthesis of compound 28:
The preparation method of compound 28 is with embodiment 3, the difference is that replacing intermediate B 4 with intermediate B 6.Element point
Analyse structure (molecular formula C62H39N9): theoretical value C, 81.83；H,4.32；N,13.85；Test value: C, 81.88；H,4.37；N,
13.87。ESI-MS(m/z)(M+): theoretical value 909.33, measured value 909.38.
Embodiment 6: the synthesis of compound 42:
The preparation method of compound 42 is with embodiment 3, the difference is that replacing intermediate B 4 with intermediate B 7.Element point
Analyse structure (molecular formula C38H23N9): theoretical value C, 75.36；H,3.83；N,20.81；Test value: C, 75.38；H,3.87；N,
20.88。ESI-MS(m/z)(M+): theoretical value 605.21, measured value 605.29.
Embodiment 7: the synthesis of compound 48:
The preparation method of compound 48 is with embodiment 3, the difference is that replacing intermediate B 4 with intermediate B 8.Element point
Analyse structure (molecular formula C50H31N9): theoretical value C, 79.24；H,4.12；N,16.63；Test value: C, 79.27；H,4.15；N,
16.66。ESI-MS(m/z)(M+): theoretical value 757.27, measured value 757.35.
Embodiment 8: the synthesis of compound 52:
The preparation method of compound 52 is with embodiment 3, the difference is that replacing intermediate B 4 with intermediate B 9.Element point
Analyse structure (molecular formula C50H31N9): theoretical value C, 79.24；H,4.12；N,16.63；Test value: C, 79.28；H,4.16；N,
16.65。ESI-MS(m/z)(M+): theoretical value 757.27, measured value 757.33.
Embodiment 9: the synthesis of compound 79:
The preparation method of compound 79 is with embodiment 3, the difference is that replacing intermediate B 4 with intermediate B 13.Element
Analyze structure (molecular formula C50H31N9): theoretical value C, 79.24；H,4.12；N,16.63；Test value: C, 79.27；H,4.13；N,
16.69。ESI-MS(m/z)(M+): theoretical value 757.27, measured value 757.35.
Embodiment 10: the synthesis of compound 87:
In 250mL there-necked flask, it is passed through nitrogen, 0.01mol intermediate A 2, the DMF of 150ml, 0.03mol intermediate is added
Then 0.02mol ﹒ L is added in B3,0.0002mol palladium acetate, stirring-1 K3PO4Aqueous solution is heated to 150 DEG C, back flow reaction 24
Hour, sample contact plate, fully reacting.Natural cooling is extracted with 200ml methylene chloride, layering, and extract liquor is dry with anhydrous sodium sulfate
Dry, filtering, filtrate revolving crosses silica gel column purification, obtains intermediate 1, HPLC purity 99.2%, yield 53.6%.
Elemental analysis structure (molecular formula C23H14Cl2N4): theoretical value C, 66.20；H,3.38；N,13.43；Cl,16.99；
Test value: C, 66.22；H,3.39；N,13.49；Cl,17.07.ESI-MS(m/z)(M+): theoretical value 416.06, measured value
It is 416.15.
In 250mL there-necked flask, it is passed through nitrogen, 0.01mol intermediate 1, the DMF of 150ml, 0.06mol intermediate is added
Then 0.02mol ﹒ L is added in B5,0.0002mol palladium acetate, stirring-1 K3PO4Aqueous solution is heated to 150 DEG C, back flow reaction 24
Hour, sample contact plate, fully reacting.Natural cooling is extracted with 200ml methylene chloride, layering, and extract liquor is dry with anhydrous sodium sulfate
Dry, filtering, filtrate revolving crosses silica gel column purification, obtains intermediate 1, HPLC purity 98.9%, yield 52.6%.
Elemental analysis structure (molecular formula C51H32N8): theoretical value C, 80.93；H,4.26；N,14.81；Test value: C,
80.97；H,4.29；N,14.85.ESI-MS(m/z)(M+): theoretical value 756.27, measured value 756.29.
Embodiment 11: the synthesis of compound 89:
The preparation method is the same as that of Example 10 for compound 89, the difference is that replacing intermediate B 5 with intermediate B 8.Element
Analyze structure (molecular formula C51H32N8): theoretical value C, 80.93；H,4.26；N,14.81；Test value: C, 80.98；H,4.27；N,
14.86。ESI-MS(m/z)(M+): theoretical value 756.27, measured value 756.32.
Embodiment 12: the synthesis of compound 98:
The preparation method is the same as that of Example 10 for compound 98, the difference is that replacing intermediate B 5 with intermediate B 11.Element
Analyze structure (molecular formula C51H32N8): theoretical value C, 80.93；H,4.26；N,14.81；Test value: C, 80.97；H,4.29；N,
14.87。ESI-MS(m/z)(M+): theoretical value 756.27, measured value 756.33.
Embodiment 13: the synthesis of compound 116:
The preparation method of compound 116, the difference is that replacing intermediate A 1 with intermediate A 3, uses B13 with embodiment 3
Replace intermediate B 4.Elemental analysis structure (molecular formula C51H32N8): theoretical value C, 80.93；H,4.26；N,14.81；Test value:
C,80.96；H,4.29；N,14.87.ESI-MS(m/z)(M+): theoretical value 756.27, measured value 756.33.
Embodiment 14: the synthesis of compound 128:
The preparation method of compound 128, the difference is that replacing intermediate A 1 with intermediate A 4, uses B5 with embodiment 3
Replace intermediate B 4.Elemental analysis structure (molecular formula C51H32N8): theoretical value C, 80.93；H,4.26；N,14.81；Test value:
C,80.97；H,4.32；N,14.88.ESI-MS(m/z)(M+): theoretical value 756.27, measured value 756.35.
Embodiment 15: the synthesis of compound 145:
The preparation method of compound 145, the difference is that replacing intermediate A 1 with intermediate A 5, uses B5 with embodiment 3
Replace intermediate B 4.Elemental analysis structure (molecular formula C51H32N8): theoretical value C, 80.93；H,4.26；N,14.81；Test value:
C,80.98；H,4.31；N,14.89.ESI-MS(m/z)(M+): theoretical value 756.27, measured value 756.34.
Embodiment 16: the synthesis of compound 149:
The preparation method of compound 149, the difference is that replacing intermediate A 1 with intermediate A 4, uses B8 with embodiment 3
Replace intermediate B 4.Elemental analysis structure (molecular formula C51H32N8): theoretical value C, 80.93；H,4.26；N,14.81；Test value:
C,80.96；H,4.33；N,14.86.ESI-MS(m/z)(M+): theoretical value 756.27, measured value 756.31.
Embodiment 17: the synthesis of compound 153:
The preparation method of compound 153, the difference is that replacing intermediate A 1 with intermediate A 2, uses B12 with embodiment 3
Replace intermediate B 4.Elemental analysis structure (molecular formula C51H32N8): theoretical value C, 80.93；H,4.26；N,14.81；Test value:
C,80.98；H,4.31；N,14.89.ESI-MS(m/z)(M+): theoretical value 756.27, measured value 756.34.
Embodiment 18: the synthesis of compound 157:
The preparation method of compound 157, the difference is that replacing intermediate A 1 with intermediate A 2, uses B5 with embodiment 3
Replace intermediate B 4.Elemental analysis structure (molecular formula C51H32N8): theoretical value C, 80.93；H,4.26；N,14.81；Test value:
C,80.95；H,4.34；N,14.86.ESI-MS(m/z)(M+): theoretical value 756.27, measured value 756.31.
Embodiment 19: the synthesis of compound 179:
The preparation method of compound 179, the difference is that replacing intermediate A 1 with intermediate A 6, uses B5 with embodiment 3
Replace intermediate B 4.Elemental analysis structure (molecular formula C52H33N7): theoretical value C, 82.63；H,4.40；N,12.97；Test value:
C,82.68；H,4.47；N,13.05.ESI-MS(m/z)(M+): theoretical value 755.28, measured value 755.32.
Embodiment 20: the synthesis of compound 197:
The preparation method of compound 197, the difference is that replacing intermediate A 1 with intermediate A 6, uses B9 with embodiment 3
Replace intermediate B 4.Elemental analysis structure (molecular formula C52H33N7): theoretical value C, 82.63；H,4.40；N,12.97；Test value:
C,82.698；H,4.45；N,13.03.ESI-MS(m/z)(M+): theoretical value 755.28, measured value 755.36.
Embodiment 21: the synthesis of compound 203:
The preparation method of compound 203, the difference is that replacing intermediate A 1 with intermediate A 2, uses B6 with embodiment 3
Replace intermediate B 4.Elemental analysis structure (molecular formula C51H32N8): theoretical value C, 80.93；H,4.26；N,14.81；Test value:
C,80.99；H,4.38；N,14.85.ESI-MS(m/z)(M+): theoretical value 756.27, measured value 756.36.
Organic compound of the invention, used as CPL layer material, has high Tg (gamma transition temperature in luminescent device
Degree) temperature and high refractive index.Hot property and refraction index test are carried out respectively to the compounds of this invention and current material, as a result such as table
Shown in 2.Wherein the refraction index test figure of compound 6 is as shown in Figure 2.
Table 2
Note: glass transition temperature Tg is by differential scanning calorimetry (DSC, German Nai Chi company DSC204F1 differential scanning calorimetry
Instrument) measurement, 10 DEG C/min of heating rate；Refractive index is surveyed by ellipsometer (U.S.'s J.A.Woollam Co. model: ALPHA-SE)
Amount, is tested as atmospheric environment.
By upper table data it is found that the materials such as CBP, Alq3 and TPBi that comparison is applied at present, organic compound of the invention
With high glass transition temperature, high refractive index, simultaneously because rigid containing pyridine, quinoxaline or benzimidazole or benzoxazoles
Property group, ensure that the thermal stability of material.Therefore, the present invention is being applied to OLED device by the organic material of core of pyridine
After the CPL layer of part, the light extraction efficiency of device can be effectively improved, and ensure that the long-life of OLED device.
Below by way of device embodiments 1~23 and device comparative example 1 OLED material that the present invention will be described in detail synthesizes in device
Application effect in part.Device embodiments 2~23 of the present invention, the device compared with device embodiments 1 of device comparative example 1
Manufacture craft it is identical, and use identical baseplate material and electrode material, the film thickness of electrode material is also kept
Unanimously, except that the CPL layer material in 2~20 pairs of devices of device embodiments converts；21~23 pairs of device embodiments
Hole barrier/electron transport layer materials of device convert, the performance test results of each embodiment obtained device such as 3 institute of table
Show.
Device embodiments 1: a kind of electroluminescent device, preparation step include: as shown in Figure 1
A) the ito anode layer 2 on transparent OLED device substrate 1 is cleaned, it is clear with deionized water, acetone, EtOH Sonicate respectively
It washes each 15 minutes, is then handled 2 minutes in plasma cleaner；
B) on ito anode layer 2, hole injection layer material HAT-CN is deposited by vacuum evaporation mode, with a thickness of 10nm,
This layer is as hole injection layer 3；
C) on hole injection layer 3, hole mobile material NPB is deposited by vacuum evaporation mode, with a thickness of 80nm, the layer
For hole transmission layer 4；
D) luminescent layer 5 is deposited on hole transmission layer 4, CBP is used as material of main part, Ir (ppy)3As doping material
Material, Ir (ppy)3Mass ratio with CBP is 1:9, with a thickness of 30nm；
E) on luminescent layer 5, electron transport material TPBI is deposited by vacuum evaporation mode, with a thickness of 40nm, this layer
Organic material is used as hole barrier/electron transfer layer 6；
F) on hole barrier/electron transfer layer 6, vacuum evaporation electron injecting layer LiF, with a thickness of 1nm, which is electricity
Sub- implanted layer 7；
G) on electron injecting layer 7, Mg:Ag/Ag layers of vacuum evaporation cathode, it is 9:1, thickness that Mg:Ag, which adulterates mass ratio,
15nm, Ag thickness 3nm, the layer are cathode layer 8；
H) on cathode layer 8, the compound 1 of CPL material embodiment of the present invention preparation is deposited by vacuum evaporation mode,
With a thickness of 50nm, this layer of organic material is used as CPL layer 9.
After the production for completing electroluminescent device according to above-mentioned steps, the current efficiency of measurement device and service life, result
It is shown in Table 3.The molecular structural formula of associated materials is as follows:
Device embodiments 2: the CPL layer material of electroluminescent device becomes the compound 6 of preparation of the embodiment of the present invention.Device
Embodiment 3: the CPL layer material of electroluminescent device becomes the compounds of this invention 26.Device embodiments 4: electroluminescent device
CPL layer material becomes the compounds of this invention 28.Device embodiments 5: the CPL layer material of electroluminescent device becomes chemical combination of the present invention
Object 42.Device embodiments 6: the CPL layer material of electroluminescent device becomes the compounds of this invention 48.Device embodiments 7: electroluminescent hair
The CPL layer material of optical device becomes the compounds of this invention 52.Device embodiments 8: the CPL layer material of electroluminescent device becomes this
Invention compound 79.Device embodiments 9: the CPL layer material of electroluminescent device becomes the compounds of this invention 87.Device embodiments
10: the CPL layer material of electroluminescent device becomes the compounds of this invention 89.Device embodiments 11: the CPL layer of electroluminescent device
Material becomes the compounds of this invention 98.Device embodiments 12: the CPL layer material of electroluminescent device becomes the compounds of this invention
116.Device embodiments 13: the CPL layer material of electroluminescent device becomes the compounds of this invention 128.Device embodiments 14: electroluminescent
The CPL layer material of luminescent device becomes the compounds of this invention 145.Device embodiments 15: the CPL layer material of electroluminescent device becomes
For the compounds of this invention 149.Device embodiments 16: the CPL layer material of electroluminescent device becomes the compounds of this invention 153.Device
Part embodiment 17: the CPL layer material of electroluminescent device becomes the compounds of this invention 157.Device embodiments 18: electroluminescent cell
The CPL layer material of part becomes the compounds of this invention 179.Device embodiments 19: the CPL layer material of electroluminescent device becomes this hair
Bright compound 197.Device embodiments 20: the CPL layer material of electroluminescent device becomes the compounds of this invention 203.Device is implemented
Example 21: hole barrier/electron transport layer materials of electroluminescent device become the compounds of this invention 42.Device embodiments 22: electricity
Hole barrier/electron transport layer materials of electroluminescence device become the compounds of this invention 48.Device embodiments 23: electroluminescent cell
Hole barrier/electron transport layer materials of part become the compounds of this invention 52.Device comparative example 1: the CPL layer of electroluminescent device
Material becomes well known materials Alq3.The detection data of gained electroluminescent device is shown in Table 3.
Table 3
It can be seen that and of the present invention shine applied to OLED by the organic compound of core of pyridine by the result of table 3
After element manufacturing, compared with device comparative example 1, light, which takes out, to be obviously improved, under same current density, device brightness and device
Efficiency is all improved, and since brightness and efficiency get a promotion, power consumption relative reduction of the OLED device in the case where determining brightness is used
Service life is also improved.
In order to illustrate material membrane phase crystallization-stable performance of the present invention, by material compound 1 of the present invention and well known materials CBP
It has carried out film and has accelerated crystallization experiment: using vacuum evaporation mode, 1 He of compound for preparing the embodiment of the present invention being deposited respectively
CBP is vaporized on alkali-free glass, and is packaged in glove box (water oxygen content < 0.1ppm), by sample after encapsulation double 85
It is placed under the conditions of (85 DEG C of temperature, humidity 85%), periodically observes material with microscope (LEICA, DM8000M, 5*10 multiplying power)
Expect the crystalline state of film, experimental result is as shown in table 4, and material surface form is as shown in Fig. 3-1 to 3-5:
Table 4
The membrane crystallization stability of the above description of test, material of the present invention is significantly larger than well known materials, is being applied to OLED device
Service life after part has beneficial effect.
Work limitation rate is also more stable at low temperature for the OLED device of further material preparation of the present invention, by device reality
It applies example 2,8,21 and device comparative example 1 and carries out efficiency test in -10~80 DEG C of sections, acquired results are as shown in table 5 and Fig. 4.
Table 5
From the data of table 5 and Fig. 4 it is found that device embodiments 2,8,21 are material of the present invention and the device that known materials are arranged in pairs or groups
Structure is compared with device comparative example 1, and not only Efficiency at Low Temperature is high, but also in temperature elevation process, efficiency is steadily increased.
To sum up, the foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (11)
1. a kind of organic compound containing pyridine, which is characterized in that the structure of the organic compound such as general formula (1) institute
Show:
In general formula (1), p, m, n independently be expressed as number 0,1 or 2；And m+n+p >=3；
In general formula (1), Ar1、Ar2、Ar3Independently be expressed as singly-bound, substituted or unsubstituted C6-60Arlydene contains one
Or one of multiple heteroatomic substituted or unsubstituted 5~60 yuan of heteroarylidenes；The hetero atom is nitrogen, oxygen or sulphur；Institute
State Ar1、Ar2、Ar3It can be identical or different；
R1、R2、R3It is optionally by one or more R4Substituted or unsubstituted quinoxalinyl, by one or more R4Replace or not
Substituted benzimidazolyl, by one or more R4Substituted or unsubstituted benzoxazolyl；R1、R2、R3It is identical when different；
Z is expressed as N atom or C-H identical or differently；
R4It is expressed as substituted or unsubstituted C6To C30Aryl and contain one or more heteroatomic substituted or unsubstituted C5Extremely
C30One of heteroaryl；The hetero atom is nitrogen, oxygen or sulphur.
2. a kind of organic compound containing pyridine according to claim 1, which is characterized in that the R1、R2、R3Point
It is not independent to be expressed as general formula (2), general formula (3), general formula (4), general formula (5), general formula (6), general formula (7), general formula (8), general formula
(9), structure shown in general formula (10) or general formula (11)；
Wherein, the Ar4、Ar5、Ar6、Ar7、Ar8、Ar9、Ar10、Ar11、Ar12、Ar13、Ar14Independently be expressed as hydrogen original
Son, C1-10Linear or branched alkyl group, substituted or unsubstituted C6-60Aryl does not take containing one or more heteroatomic substitutions or
One of 5~60 unit's heteroaryls in generation；The hetero atom is nitrogen, oxygen or sulphur；Ar4、Ar5、Ar6、Ar7、Ar8、Ar9、Ar10、
Ar11、Ar12、Ar13、Ar14It can be identical or different；R4 is expressed as phenyl, xenyl, naphthalene or pyridyl group；Q is 0,1 or 2.
3. a kind of organic compound containing pyridine according to claim 1, which is characterized in that the organic compound
Structure such as formula (I-1)~(I-5) in it is any shown in:
4. a kind of organic compound containing pyridine according to claim 2, which is characterized in that the Ar1、Ar2、Ar3
Independently be expressed as C1-10Linear or branched alkyl group, halogen atom, protium, deuterium, the substituted or unsubstituted phenylene of tritium atom；
C1-10Linear or branched alkyl group, halogen atom, protium, deuterium, the substituted or unsubstituted naphthylene of tritium atom；C1-10Linear chain or branched chain alkane
The substituted or unsubstituted sub- dibiphenylyl of base, halogen atom, protium, deuterium, tritium atom；Anthrylene；C1-10Linear or branched alkyl group, halogen
Plain atom, protium, deuterium, the substituted or unsubstituted sub-pyridyl group of tritium atom；Sub- carbazyl；Furylidene；Sub- quinolyl；Sub- naphthyridines
Base；Sub- dibenzofuran group；Sub- dibenzothiophene；One of sub- 9,9- dimethyl fluorenyl or Asia N- phenyl carbazole base；
The Ar4、Ar5、Ar6、Ar7、Ar8、Ar9、Ar10、Ar11、Ar12、Ar13、Ar14Independently be expressed as C1-10Straight chain or
Branched alkyl, halogen atom, protium, deuterium, the substituted or unsubstituted phenyl of tritium atom；C1-10Linear or branched alkyl group, halogen atom,
Protium, deuterium, the substituted or unsubstituted naphthalene of tritium atom；C1-10Linear or branched alkyl group, halogen atom, protium, deuterium, tritium atom replace or
Unsubstituted dibiphenylyl；C1-10Linear or branched alkyl group, halogen atom, protium, deuterium, the substituted or unsubstituted pyridine of tritium atom
Base；Carbazyl；Furyl；Pyrimidine radicals；Pyrazinyl；Pyridazinyl；Dibenzofurans；9,9- dimethyl fluorene；N- phenyl carbazole；Quinoline
Base；One of isoquinolyl or naphthyridines base.
5. a kind of organic compound containing pyridine according to claim 1, which is characterized in that the organic compound
Concrete structure formula are as follows:
Any one.
6. a kind of a kind of any one of Claims 1 to 5 preparation method of the organic compound containing pyridine, feature exist
In the reaction equation that the preparation method is related to are as follows:
(1) it under nitrogen atmosphere, weighs raw material A and is dissolved in DMF, addAnd palladium acetate, it is stirred
Object adds aqueous potassium phosphate solution, and it is small that the mixed solution of above-mentioned reactant is heated to reflux 5-15 under the conditions of 120-150 DEG C
When；After reaction, Jia Shui is cooled down, mixture is filtered and is dried in a vacuum drying oven, it is pure that gained residue crosses silicagel column
Change, obtains compound intermediate I；
The raw material A withMolar ratio be 1:1.0~3, the molar ratio of palladium acetate and raw material A is 0.001~
The molar ratio of 0.04:1, potassium phosphate and raw material A is 1.0~4.0:1, and toluene dosage is that every gram of raw material A uses 30-50ml toluene；
(2) it under nitrogen atmosphere, weighs intermediate compound I and is dissolved in DMF, addAnd palladium acetate, it is stirred
Object adds aqueous potassium phosphate solution, and it is small that the mixed solution of above-mentioned reactant is heated to reflux 10-24 under the conditions of 120-150 DEG C
When；After reaction, Jia Shui is cooled down, mixture is filtered and is dried in a vacuum drying oven, it is pure that gained residue crosses silicagel column
Change, obtains compound intermediate II；
The intermediate compound I withMolar ratio be 1:1.0~3, the molar ratio of palladium acetate and intermediate compound I is
The molar ratio of 0.001~0.04:1, potassium phosphate and intermediate compound I is 1.0~4.0:1, and toluene dosage is that every gram of intermediate compound I uses
10-40ml toluene；
(3) it under nitrogen atmosphere, weighs intermediate II and is dissolved in DMF, addAnd palladium acetate, stirring are mixed
Object is closed, aqueous potassium phosphate solution is added, the mixed solution of above-mentioned reactant is heated to reflux 10-24 under the conditions of 120-150 DEG C
Hour；After reaction, Jia Shui is cooled down, mixture is filtered and is dried in a vacuum drying oven, gained residue crosses silicagel column
Purifying, obtains target compound；
The intermediate II withMolar ratio be 1:1.0~3, the molar ratio of palladium acetate and intermediate II is
The molar ratio of 0.001~0.04:1, potassium phosphate and intermediate II is 1.0~4.0:1, and toluene dosage is that every gram of intermediate II uses
15-50ml toluene.
7. a kind of a kind of described in any item organic compounds containing pyridine of Claims 1 to 5 are applied to prepare Organic Electricity
Electroluminescence device.
8. a kind of organic electroluminescence device, which is characterized in that the organic electroluminescence device includes at least one layer of functional layer
Contain the described in any item organic compounds containing pyridine of claim 1-5.
9. a kind of organic electroluminescence device according to claim 8, including hole blocking layer/electron transfer layer, special
Sign is that the hole blocking layer/electron transfer layer contains described in any item the organising containing pyridine of claim 1-5
Close object.
10. a kind of organic electroluminescence device according to claim 8, including CPL layers, which is characterized in that it is CPL layers described
Contain the described in any item organic compounds containing pyridine of claim 1-5.
11. a kind of illumination or display element, which is characterized in that contain claim 8~10 any for the illumination or display element
Organic electroluminescence device described in.
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Cited By (4)
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| CN111153890A (en) * | 2020-01-15 | 2020-05-15 | 吉林奥来德光电材料股份有限公司 | Organic light-emitting material, preparation method thereof and organic electroluminescent device |
| WO2020199998A1 (en) * | 2019-03-29 | 2020-10-08 | 吉林省元合电子材料有限公司 | 1,3,5-triazine compound and composition, and application thereof |
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