CN109942548A - The diphenylpyrimidin compound and its organic electroluminescent device replaced through quinoline - Google Patents
The diphenylpyrimidin compound and its organic electroluminescent device replaced through quinoline Download PDFInfo
- Publication number
- CN109942548A CN109942548A CN201711460310.1A CN201711460310A CN109942548A CN 109942548 A CN109942548 A CN 109942548A CN 201711460310 A CN201711460310 A CN 201711460310A CN 109942548 A CN109942548 A CN 109942548A
- Authority
- CN
- China
- Prior art keywords
- compound
- formula
- quinoline
- diphenylpyrimidin
- unsubstituted
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 title claims abstract description 71
- -1 diphenylpyrimidin compound Chemical class 0.000 title claims abstract description 40
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- 239000010410 layer Substances 0.000 claims description 108
- 239000012044 organic layer Substances 0.000 claims description 25
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 23
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 229910052717 sulfur Inorganic materials 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- 125000005493 quinolyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 72
- 238000003756 stirring Methods 0.000 description 51
- 239000007787 solid Substances 0.000 description 43
- 238000010438 heat treatment Methods 0.000 description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 42
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 38
- 239000008367 deionised water Substances 0.000 description 28
- 229910021641 deionized water Inorganic materials 0.000 description 28
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 26
- 230000015572 biosynthetic process Effects 0.000 description 25
- 238000003786 synthesis reaction Methods 0.000 description 24
- 239000000463 material Substances 0.000 description 23
- 238000005160 1H NMR spectroscopy Methods 0.000 description 19
- 235000019441 ethanol Nutrition 0.000 description 19
- 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 18
- 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 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 13
- 229910000027 potassium carbonate Inorganic materials 0.000 description 13
- 230000005540 biological transmission Effects 0.000 description 9
- 238000000151 deposition Methods 0.000 description 9
- ABRVLXLNVJHDRQ-UHFFFAOYSA-N [2-pyridin-3-yl-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound FC(C1=CC(=CC(=N1)C=1C=NC=CC=1)CN)(F)F ABRVLXLNVJHDRQ-UHFFFAOYSA-N 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- 238000010898 silica gel chromatography Methods 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000008021 deposition Effects 0.000 description 7
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 6
- 238000005401 electroluminescence Methods 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000011368 organic material Substances 0.000 description 5
- MZSAMHOCTRNOIZ-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-phenylaniline Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(NC2=CC=CC=C2)C=CC=1 MZSAMHOCTRNOIZ-UHFFFAOYSA-N 0.000 description 4
- ZEEBGORNQSEQBE-UHFFFAOYSA-N [2-(3-phenylphenoxy)-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound C1(=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F)C1=CC=CC=C1 ZEEBGORNQSEQBE-UHFFFAOYSA-N 0.000 description 4
- YQYBUJYBXOVWQW-UHFFFAOYSA-N [3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxyphenyl]-(3,4-dihydro-1H-isoquinolin-2-yl)methanone Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(C=CC=1)C(=O)N1CC2=CC=CC=C2CC1 YQYBUJYBXOVWQW-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- 238000004770 highest occupied molecular orbital Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 229910052705 radium Inorganic materials 0.000 description 4
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- RVPCPPWNSMAZKR-UHFFFAOYSA-N (10-phenylanthracen-9-yl)boronic acid Chemical compound C12=CC=CC=C2C(B(O)O)=C2C=CC=CC2=C1C1=CC=CC=C1 RVPCPPWNSMAZKR-UHFFFAOYSA-N 0.000 description 3
- WSNKEJIFARPOSQ-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-(1-benzothiophen-2-ylmethyl)benzamide Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(C(=O)NCC2=CC3=C(S2)C=CC=C3)C=CC=1 WSNKEJIFARPOSQ-UHFFFAOYSA-N 0.000 description 3
- AJZDHLHTTJRNQJ-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-[2-(tetrazol-1-yl)ethyl]benzamide Chemical compound N1(N=NN=C1)CCNC(C1=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F)=O AJZDHLHTTJRNQJ-UHFFFAOYSA-N 0.000 description 3
- LUBXLGUQZVKOFP-UHFFFAOYSA-N 9-phenylanthracene Chemical compound C1=CC=CC=C1C1=C(C=CC=C2)C2=CC2=CC=CC=C12 LUBXLGUQZVKOFP-UHFFFAOYSA-N 0.000 description 3
- REAYFGLASQTHKB-UHFFFAOYSA-N [2-[3-(1H-pyrazol-4-yl)phenoxy]-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound N1N=CC(=C1)C=1C=C(OC2=NC(=CC(=C2)CN)C(F)(F)F)C=CC=1 REAYFGLASQTHKB-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229960003540 oxyquinoline Drugs 0.000 description 3
- 230000005622 photoelectricity Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 238000004227 thermal cracking Methods 0.000 description 3
- WYECURVXVYPVAT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Br)C=C1 WYECURVXVYPVAT-UHFFFAOYSA-N 0.000 description 2
- HAEQAUJYNHQVHV-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-phenylbenzamide Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(C(=O)NC2=CC=CC=C2)C=CC=1 HAEQAUJYNHQVHV-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KYKQHJKIDQSMRJ-UHFFFAOYSA-N BrC=1C=C(C=O)C=CC1.BrC=1C=C(C=O)C=CC1 Chemical compound BrC=1C=C(C=O)C=CC1.BrC=1C=C(C=O)C=CC1 KYKQHJKIDQSMRJ-UHFFFAOYSA-N 0.000 description 2
- YEQFJWSISGFUNG-UHFFFAOYSA-N C1=CC=C(C=2OC3=C(C21)C=CC=C3)B(O)O.B(O)(O)O Chemical compound C1=CC=C(C=2OC3=C(C21)C=CC=C3)B(O)O.B(O)(O)O YEQFJWSISGFUNG-UHFFFAOYSA-N 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000009920 chelation Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- YWOITFUKFOYODT-UHFFFAOYSA-N methanol;sodium Chemical compound [Na].OC YWOITFUKFOYODT-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- AQBMQGDKWIPBRF-UHFFFAOYSA-N n'-hydroxypyridine-3-carboximidamide Chemical class ON=C(N)C1=CC=CN=C1 AQBMQGDKWIPBRF-UHFFFAOYSA-N 0.000 description 2
- WPVMCFLSAUMMAD-UHFFFAOYSA-N n'-hydroxypyridine-3-carboximidamide;hydrochloride Chemical compound Cl.O\N=C(/N)C1=CC=CN=C1 WPVMCFLSAUMMAD-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- LYVCVOCBPHDNLP-UHFFFAOYSA-N 3-bromobenzaldehyde;4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1.BrC1=CC=CC(C=O)=C1 LYVCVOCBPHDNLP-UHFFFAOYSA-N 0.000 description 1
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 1
- BWRMZQGIDWILAU-UHFFFAOYSA-N 4,6-diphenylpyrimidine Chemical compound C1=CC=CC=C1C1=CC(C=2C=CC=CC=2)=NC=N1 BWRMZQGIDWILAU-UHFFFAOYSA-N 0.000 description 1
- WDDLHUWVLROJLA-UHFFFAOYSA-N 9,9'-spirobi[fluorene]-2-ylboronic acid Chemical compound C12=CC=CC=C2C2=CC=CC=C2C21C1=CC=CC=C1C1=CC=C(B(O)O)C=C12 WDDLHUWVLROJLA-UHFFFAOYSA-N 0.000 description 1
- QIGVFZRPRWNVFK-UHFFFAOYSA-N BrC1=CC=C(C=O)C=C1.BrC1=CC=C(C=O)C=C1 Chemical compound BrC1=CC=C(C=O)C=C1.BrC1=CC=C(C=O)C=C1 QIGVFZRPRWNVFK-UHFFFAOYSA-N 0.000 description 1
- UZAXYKGAPIVJLR-UHFFFAOYSA-N BrC=1C=C(C=CC1)C(C)=O.BrC=1C=C(C=CC1)C(C)=O Chemical compound BrC=1C=C(C=CC1)C(C)=O.BrC=1C=C(C=CC1)C(C)=O UZAXYKGAPIVJLR-UHFFFAOYSA-N 0.000 description 1
- NPPHSTMPHHXUHQ-UHFFFAOYSA-N BrC=1C=C(C=O)C=C(C1)Br.BrC=1C=C(C=O)C=C(C1)Br Chemical compound BrC=1C=C(C=O)C=C(C1)Br.BrC=1C=C(C=O)C=C(C1)Br NPPHSTMPHHXUHQ-UHFFFAOYSA-N 0.000 description 1
- DIVWHBDQPKKSPD-UHFFFAOYSA-N C1(=CC=CC=C1)N1C(=NC2=C1C=CC=C2)C2=CC=C(C=C2)B(O)O.C2(=CC=CC=C2)OB(O)O Chemical compound C1(=CC=CC=C1)N1C(=NC2=C1C=CC=C2)C2=CC=C(C=C2)B(O)O.C2(=CC=CC=C2)OB(O)O DIVWHBDQPKKSPD-UHFFFAOYSA-N 0.000 description 1
- JUSPEIQLZXVPPN-UHFFFAOYSA-N C1=CC=C(C=2SC3=C(C21)C=CC=C3)B(O)O.B(O)(O)O Chemical compound C1=CC=C(C=2SC3=C(C21)C=CC=C3)B(O)O.B(O)(O)O JUSPEIQLZXVPPN-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241000209094 Oryza Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- TZRXHJWUDPFEEY-UHFFFAOYSA-N Pentaerythritol Tetranitrate Chemical compound [O-][N+](=O)OCC(CO[N+]([O-])=O)(CO[N+]([O-])=O)CO[N+]([O-])=O TZRXHJWUDPFEEY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QIOZCMIWAVEQPN-UHFFFAOYSA-N [10-(4-phenylphenyl)anthracen-9-yl]boronic acid Chemical compound C12=CC=CC=C2C(B(O)O)=C2C=CC=CC2=C1C(C=C1)=CC=C1C1=CC=CC=C1 QIOZCMIWAVEQPN-UHFFFAOYSA-N 0.000 description 1
- BYWBCSRCPLBDFU-CYBMUJFWSA-N [3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxyphenyl]-[(3R)-3-aminopyrrolidin-1-yl]methanone Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(C=CC=1)C(=O)N1C[C@@H](CC1)N BYWBCSRCPLBDFU-CYBMUJFWSA-N 0.000 description 1
- JWSIZPAOIFLWKM-UHFFFAOYSA-N [3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxyphenyl]-[3-(dimethylamino)-4-hydroxypyrrolidin-1-yl]methanone Chemical compound CN(C)C1CN(CC1O)C(=O)c1cccc(Oc2cc(CN)cc(n2)C(F)(F)F)c1 JWSIZPAOIFLWKM-UHFFFAOYSA-N 0.000 description 1
- LBWODEDBUKZKFS-UHFFFAOYSA-N [Li].N1=C(C(=O)O)C(C(=O)O)=CC=C1 Chemical compound [Li].N1=C(C(=O)O)C(C(=O)O)=CC=C1 LBWODEDBUKZKFS-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001964 alkaline earth metal nitrate Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000005588 carbonic acid salt group Chemical group 0.000 description 1
- AYTVLULEEPNWAX-UHFFFAOYSA-N cesium;azide Chemical compound [Cs+].[N-]=[N+]=[N-] AYTVLULEEPNWAX-UHFFFAOYSA-N 0.000 description 1
- XKXCGXSHUNVFCT-UHFFFAOYSA-N chembl3263490 Chemical class ON=C(N)C1=CC=CC=N1 XKXCGXSHUNVFCT-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003230 hygroscopic agent Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GUWHRJQTTVADPB-UHFFFAOYSA-N lithium azide Chemical compound [Li+].[N-]=[N+]=[N-] GUWHRJQTTVADPB-UHFFFAOYSA-N 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- IMKMFBIYHXBKRX-UHFFFAOYSA-M lithium;quinoline-2-carboxylate Chemical compound [Li+].C1=CC=CC2=NC(C(=O)[O-])=CC=C21 IMKMFBIYHXBKRX-UHFFFAOYSA-M 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- HUMMCEUVDBVXTQ-UHFFFAOYSA-N naphthalen-1-ylboronic acid Chemical compound C1=CC=C2C(B(O)O)=CC=CC2=C1 HUMMCEUVDBVXTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- GJAWHXHKYYXBSV-UHFFFAOYSA-N quinolinic acid Chemical compound OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Landscapes
- Electroluminescent Light Sources (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The present invention provides the diphenylpyrimidin compound of a kind of tool formula (I) structure replaced through quinoline and use the organic electroluminescent device of the compound, wherein X1、A1And n is such as the definition in specification.By the diphenylpyrimidin compound of tool formula (I) structure provided by the invention replaced through quinoline, the service life of organic electroluminescent device can be improved, improve carrier transport factor and good heat resistance is provided.
Description
Technical field
The present invention relates to a kind of material for organic electroluminescent device and use the organic electroluminescent member of the material
Part, more particularly to one kind can increase efficiency of element and extend the material in organic electroluminescent device service life and having using the material
Electro-luminescence element.
Background technique
Recently, organic electroluminescent device (OLED) is in the high density pixel display of high luminous efficiency because having longevity
The advantages such as life, high efficiency, low driving voltage, colour gamut be wide and at low cost, and there is commercial attraction, to meet organic electroluminescence hair
The application of optical element, the exploitation for its novel organic material that stresses.
Typical OLED includes at least one organic light emission (organic emissive) layer being folded between anode and cathode.
When a current is applied, anode injection hole and cathode inject electronics to one or more layers organic luminous layer, by injected holes
And electronics is respectively migrated to opposite electrification charged electrode.When electronics and hole are limited on the same molecule, " exciton is formed
(exciton) ", the exciton there is localization's electronics-the hole pair of energy state of being stimulated, by luminous mechanism, the exciton relaxation and
Emit light.To ask the charge transport ability and luminous efficiency that promote these elements, one or more layers volume is combined by luminescent layer
Outer layer body, such as electron transfer layer and/or hole transmission layer or electronic barrier layer and/or hole blocking layer.In document, fill
Dividing proves to blend another guest materials in material of main part, with lifting device performance and adjustment coloration.Be incorporated by herein with reference to
Described in US 4769292, US 5844363, US 5707745, US 6596415 and US 6465115 several OLED materials and
Apparatus structure.Card TW I582081 was applied in 2016 and obtained in 2017 to sunlight radium Optoelectronics Technology, what this patent was introduced
Electron transport material has had certain novelty and effect.
The reason of manufacture tool multi-layer film structure OLED, is comprising making the interface stability between grade electrodes and the organic layer and having
The collocation of machine material.In organic material, the mobility (mobility) in electronics and hole is significantly different, if using matching
Hole transport and electron transfer layer, hole and electronics can be efficiently transferred to the emission layer, make the electronics and sky in the emission layer
The density balance in cave increases luminous efficiency.The combination appropriate above-mentioned organic layer can promote the efficiency of element and service life.However,
Still it is difficult to find that meet the organic material of the needs of all actual displays application, particularly for vehicle display or illumination light
The organic material in source need to have the property of high temperature resistant and long-life.
Therefore, the service life of organic electroluminescent device can be significantly improved, improve carrier transport factor by needing a kind of organic material
And good heat resistance, to meet the demand of diversification application.
Summary of the invention
The purpose of the present invention is to provide it is a kind of with longer life, high carrier transport factor and heat resistance it is good for organic
The material of electroluminescent cell.
The present invention provides the diphenylpyrimidin compound of a kind of tool formula (I) structure replaced through quinoline:
Wherein, X1Indicate the C for being substituted or being unsubstituted6-30Aryl, be substituted or be unsubstituted containing selected from by N, O,
And S group in groups at least one heteroatomic C5-30Heteroaryl；
A1Indicate the C for being substituted or being unsubstituted6-36Aryl, be substituted or be unsubstituted containing selected from by N, O and S institute
Organize at least one heteroatomic C in groups5-30Heteroaryl；
X1And A1To be identical or different, and at least one is to be substituted or be unsubstituted containing selected from by N, O and S institute
Organize at least one heteroatomic C in groups5-30Heteroaryl；And
N indicates an integer of 1 or 2, and when n indicates 2, A1It is respectively identical or different.
The present invention also provides a kind of organic electroluminescent devices, include: cathode；Anode；And organic layer, between the cathode
Between anode, and the organic layer includes the diphenylpyrimidin compound replaced through quinoline of tool formula (I) structure of the invention.
According to the present invention, the diphenylpyrimidin compound replaced by tool formula (I) structure provided by the invention through quinoline,
The service life of organic electroluminescent device can be improved, improve carrier transport factor and the benefit of good heat resistance is provided.
Detailed description of the invention
Fig. 1 is the diagrammatic cross-section of an embodiment of organic electroluminescent device of the invention；
Fig. 2 is the diagrammatic cross-section of another embodiment of organic electroluminescent device of the invention；And
Fig. 3 is the diagrammatic cross-section of the another embodiment of organic electroluminescent device of the invention.
Symbol description:
100,200,300 organic electroluminescent device
110,210,310 substrate
120,220,320 anode
130,230,330 hole injection layer
140,240,340 hole transmission layer
150,250,350 luminescent layer
160,260,360 electron transfer layer
170,270,370 electron injecting layer
180,280,380 cathode
245,355 exciton barrier-layer.
Specific embodiment
Illustrate embodiments of the present invention by particular specific embodiment below, those skilled in the art can be by this explanation
The revealed content of book understands advantages of the present invention and effect easily.The present invention can also add by other different embodiments
To implement or apply, details in this specification can also be based on different perspectives and applications, disclosed not departing from
Spirit under assign different modification and change.In addition, all ranges and value are all to include and annexable herein.It falls in herein
Described in the range of any numerical value or point, such as any integer all can serve as minimum value or maximum value to export the next model
It encloses.
According to the present invention, the diphenylpyrimidin compound of a kind of tool formula (I) structure replaced through quinoline:
Wherein, X1Indicate the C for being substituted or being unsubstituted6-30Aryl, be substituted or be unsubstituted containing selected from by N, O,
And S group in groups at least one heteroatomic C5-30Heteroaryl；
A1Indicate the C for being substituted or being unsubstituted6-36Aryl, be substituted or be unsubstituted containing selected from by N, O and S institute
Organize at least one heteroatomic C in groups5-30Heteroaryl；
X1And A1To be identical or different, and at least one is to be substituted or be unsubstituted containing selected from by N, O and S institute
Organize at least one heteroatomic C in groups5-30Heteroaryl；And
N indicates an integer of 1 or 2, and when n indicates 2, A1It is respectively identical or different.
In a specific embodiment, above-mentioned tool formula (I) structure through quinoline replace diphenylpyrimidin compound, be with
Formula (I-1) structure or formula (I-2) representation:
Wherein, X1Indicate the C for being substituted or being unsubstituted6-30Aryl, be substituted or be unsubstituted containing selected from by N, O,
And S group in groups at least one heteroatomic C5-30Heteroaryl；
A1Indicate the C for being substituted or being unsubstituted6-36Aryl, be substituted or be unsubstituted containing selected from by N, O and S institute
Organize at least one heteroatomic C in groups5-30Heteroaryl；
X1And A1To be identical or different, and at least one is to be substituted or be unsubstituted containing selected from by N, O and S institute
Organize at least one heteroatomic C in groups5-30Heteroaryl；And
N indicates an integer of 1 or 2, and when n indicates 2, A1It is respectively identical or different.
The A for the diphenylpyrimidin compound of tool formula (I) structure replaced through quinoline1It is substituted or is unsubstituted
C6-36Aryl, be substituted or be unsubstituted containing selected from by N, O and S group in groups at least one heteroatomic C5-30Heteroaryl
Base the more due to the planar structure can help to molecular stacks, increase the laser propagation effect of its carrier, but its selected group carbon number
It is unsuitable excessive, avoid the formation of unnecessary crystallization.
The X for the diphenylpyrimidin compound of tool formula (I) structure replaced through quinoline1It is substituted or is unsubstituted
C6-30Aryl, be substituted or be unsubstituted containing selected from by N, O and S group in groups at least one heteroatomic C5-30Heteroaryl
Base has the function of inhibiting molecular crystalline.In a specific embodiment, X1For pyridyl group, quinolyl or naphthalene.
In another specific embodiment, the diphenylpyrimidin compound of above-mentioned tool formula (I) structure replaced through quinoline, X1
One of in groups selected from following group:
Wherein, Xr indicates hydrogen, fluorine, cyano, C1-4Alkyl or the C being unsubstituted6-18Aryl.
In a specific embodiment, A1One of in groups selected from following group:
Wherein, L indicates O or S；
Ar1To Ar6The respectively independent C for indicating hydrogen, being unsubstituted6-18Aryl；
R1To R4The respectively independent C for indicating hydrogen, being substituted or being unsubstituted6-12Aryl, R1And R2With the carbon atom being connected
C is collectively formed6-18Condensed aromatic loop system or R3And R4C is collectively formed with the carbon atom being connected6-18Condensed aromatic loop system；
And
Y1And Y2In one singly-bound and to be connected to formula (I) compound, another is hydrogen.
In a specific embodiment, when n is 1, which is shown in formula (I-3) or formula (I-4):
In a specific embodiment, when n is 2, which is shown in formula (I-5):
In another specific embodiment, when n is 2, the A1For identical structure.
Wen Zhong, " being substituted " being expressed as in " be substituted or be unsubstituted " indicate that the hydrogen in some functional group is former
Son is replaced through another atom or group (i.e. substituent group).The grade substituent groups are each independently selected from by following composed group
At least one: deuterium, halogen, C1-30Alkyl, C1-30Alkoxy, C6-30Aryl, C5-30Heteroaryl, through C6-30The C that aryl replaces5-30
Heteroaryl, benzimidazolyl, C3-30Naphthenic base, C5-7Heterocyclylalkyl, three C1-30Alkyl silyl, three C6-30Aryl silicon substrate, two C1-30
Alkyl C6-30Aryl silicon substrate, C1-30Two C of alkyl6-30Aryl silicon substrate, C2-30Alkenyl, C2-30Alkynyl, cyano, two C1-30Alkyl amine group,
Two C6-30Aryl boryl, two C1-30Alkyl boryl, C1-30Alkyl, C6-30Aryl C1-30Alkyl, C1-30Alkyl C6-30Aryl, carboxyl,
Nitro and hydroxyl.
Wen Zhong, " aryl " indicate that aryl or (Asia) aryl, the aryl refer to monocycle or condensed ring derived from aromatic hydrocarbon, including benzene
Base, xenyl, terphenyl base, naphthalene, binaphthyl, phenyl napthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzo fluorenyl, hexichol
And fluorenyl, phenanthryl, phenyl phenanthryl, anthryl, indenyl, benzo phenanthryl, pyrenyl, thick four benzene base, base,Base, naphtho- naphthalene, third
Diene closes fluorenyl etc..
Wen Zhong, " heteroaryl " indicate heteroaryl or (stretching) heteroaryl, which, which refers to, is made of N, O and S containing being selected from
The aryl of the heteroatomic ring backbone atoms of at least one of group can be monocycle system ring, such as furyl, thienyl, pyrrole radicals, miaow
Oxazolyl, oxazolyl, thiazolyl, thiadiazolyl group, isothiazolyl, isoxazolyl, oxazolyl, oxadiazoles base, triazine radical, tetrazine base,
Triazolyl, tetrazole radical, furan Xanthones base, pyridyl group, pyrazinyl, pyrimidine radicals, pyridazinyl etc., or it is thick to be condensed at least one phenyl ring
Cyclization, such as benzofuranyl, benzothienyl, isobenzofuran-base, dibenzofuran group, dibenzothiophene, benzimidazole
Base, benzothiazolyl, benzisothia oxazolyl, benzo isoxazolyl, quinolyl, isoquinolyl, cinnoline base, quinazolyl, quinoline are disliked
Quinoline base, oxazolyl, luxuriant and rich with fragrance oxazolyl, phenanthridinyl, benzo dihydro-acenaphthylene base, acridan base etc..
In a specific embodiment, aforementioned tool formula (I) structure through quinoline replace diphenylpyrimidin compound it is excellent
Embodiment is selected to be selected from table 1, but not limited to this.
Table 1
In another specific embodiment, the diphenylpyrimidin compound of above-mentioned tool formula (I) structure replaced through quinoline is
One in compound (1-10) or compound (1-11):
The diphenylpyrimidin compound replaced through quinoline of tool formula (I) structure of the invention is situated between due to its glass transition temperature
It between 98 to 165 DEG C, is preferred between 140 to 165 DEG C with glass transition temperature especially, the long-term height of automotive interior can be born
Temperature, therefore it is suitable for the organic electroluminescent device of vehicle display.
The present invention also provides a kind of organic electroluminescent devices, include: cathode；Anode；And organic layer, between the cathode
Between anode, and the organic layer includes the diphenylpyrimidin compound replaced through quinoline of tool formula (I) structure of the invention.
The organic layer of organic electroluminescent device of the invention can be electron transfer layer, electron injecting layer, luminescent layer, sky
Cave barrier layer or electronic barrier layer, and other than the organic layer, which may also include organic different from this
Layer is selected from by electron transfer layer, electron injecting layer, luminescent layer, hole blocking layer and electronic barrier layer group groups of at least one
Layer, wherein the luminescent layer also includes fluorescence or phosphorescence admixture, and respectively corresponds the material of main part of fluorescence or phosphorescence admixture.
In a specific embodiment, the diphenylpyrimidin replaced through quinoline comprising tool formula (I) structure of the invention
The organic layer for closing object is more preferably electron transfer layer, and it is with a thickness of 20 nanometers to 30 nanometers；Wherein, which can incite somebody to action
Tool formula (I) structure through quinoline replace diphenylpyrimidin compound as homogenous material, or will have formula (I) structure through quinoline
Substituted diphenylpyrimidin compound is used in combination with electrical conductivity admixture.
In another specific embodiment, which also includes N-type electrical conductivity admixture, wherein the N-type is electrical
The diphenylpyrimidin compound replaced through quinoline for conducting admixture and tool formula (I) structure of the invention generates chelation
(chelation), electronics can be made more easily to be injected into electron transfer layer from cathode, solve in the prior art because metal with
The problem of mutually separating and formed extinguishing center caused by the compatibility of electron-transport material of main part is poor, effectively increases electricity
The electron-transport efficiency of sub- transport layer.
N-type electrical conductivity admixture applied to electron transfer layer can be organic alkali metal/alkaline-earth metal nitrate, carbonic acid
Salt, phosphate or quinolinic acid.Specifically, such as lithium carbonate, oxyquinoline lithium (lithium quinolate, Liq), nitrine
Change lithium (lithium azide), rubidium carbonate, silver nitrate, barium nitrate, magnesium nitrate, zinc nitrate, cesium nitrate, cesium carbonate, cesium fluoride,
Cesium azide etc., wherein the N-type electrical conductivity admixture is preferred especially with quinolinic acid lithium.
It in a specific embodiment, is calculated with the weight of the electron transfer layer, the content of the N-type electrical conductivity admixture is
5 weight % to 50 weight %.
The structure of organic electroluminescent device of the invention will cooperate attached drawing to be illustrated.
Fig. 1 is the diagrammatic cross-section of a specific embodiment of organic electroluminescent device of the invention.Organic electroluminescent
Element 100 includes substrate 110, anode 120, hole injection layer 130, hole transmission layer 140, luminescent layer 150, electron transfer layer
160, electron injecting layer 170 and cathode 180.Organic electroluminescent device 100 can make via deposited in sequential above layers.
Fig. 2 is the diagrammatic cross-section of the another specific embodiment of organic electroluminescent device of the invention.Organic electroluminescence hair
Optical element 200 includes substrate 210, anode 220, hole injection layer 230, hole transmission layer 240, exciton barrier-layer 245, luminescent layer
250, electron transfer layer 260, electron injecting layer 270 and cathode 280 are that the exciton barrier-layer 245 is set to sky with the difference of Fig. 1
Between cave transport layer 240 and luminescent layer 250.
Fig. 3 is the diagrammatic cross-section of the still another embodiment of organic electroluminescent device of the invention.Organic electroluminescence hair
Optical element 300 includes substrate 310, anode 320, hole injection layer 330, hole transmission layer 340, luminescent layer 350, exciton barrier-layer
355, electron transfer layer 360, electron injecting layer 370 and cathode 380 are that the exciton barrier-layer 355 is set to hair with the difference of Fig. 1
Between photosphere 350 and electron transfer layer 360.
Organic electroluminescent member can be manufactured according to the inverted structure (reverse structure) of element shown in Fig. 1 to Fig. 3
Part.Increase and decrease one or more layers in the visual demand of the inverted structure such as this.
The hole injection layer, hole transmission layer, exciton barrier-layer, electron transfer layer, electron injecting layer material can
Select common used material, for example, the electron transport material for forming electron transfer layer is different from the material of luminescent layer, and it has
Hole transport ability so that hole be facilitated to migrate in electron transfer layer, and prevents the dissociation energy because of luminescent layer and electron transfer layer
Carrier accumulation caused by difference.
The diphenylpyrimidin compound replaced through quinoline of tool formula (I) structure of the invention is used for electron transfer layer, because of tool
There is the triplet energies (E higher than 2.2eVT) and good carrier transport factor, help to be promoted exciton in relaxation in luminescent layer and
Emit light.
In addition, the hole transmission layer of p-type doping illustrated in US 20170005275A1 is doped in HT3 with HT-D2,
Full content is cited in the present invention, and the patent also uses oxyquinoline lithium (Liq) as n-type doping material to be entrained in electricity
In sub- transmission material (ET3), entire contents are cited in the present invention.The cathode as illustrated in US 5703436 and US 5707745
Full content be the present invention cited in, the cathode have thin metal layer, such as: magnesium/silver (Mg:Ag), and with sputter deposition covering
The transparency conducting layer (ITO Layer) of thin metal layer.It answers on each barrier layer disclosed in US 6097147 and US 20030230980
With and principle, entire contents be the present invention cited in.Illustrated by implanted layer illustrated by US 20040174116 and accomplice
Protective layer, entire contents are cited in the present invention.
Not specified structure and material is equally applicable for the present invention, includes polymeric material as disclosed in US 5247190
Expect the organic electroluminescent device of (PLEDs), entire contents are cited in the present invention.Furthermore having with single organic layer
The organic electroluminescent device that electro-luminescence element or the storehouse as disclosed in US 5707745 are formed, entire contents are this hair
It is bright cited.
Except being particularly limited to, any proper method can be used to be formed to deposit for any layer in different embodiments.With organic
For layer, preferable method includes such as US 6013982 and the revealed thermal evaporation deposition of US 6087196 and spray printing method, whole
Content is cited in the present invention；(the organic vapor phase of organic vapor phase deposition method disclosed in US 6337102
Deposition, OVPD), entire contents are cited in the present invention；Organic vapors spray printing sedimentation disclosed in US 10/23347
(deposition by organic vapor jet printing, OVJP), entire contents are cited in the present invention.Other
Proper method includes rotary coating and the processing procedure based on solution.Processing procedure based on solution is preferably in nitrogen or inertia
It is carried out in gaseous environment.For other layers, preferable method includes thermal evaporation deposition.Preferable patterning method includes such as US
The disclosed processing procedure by masked-deposition cold welding again of 6294398 and US 6468819, and integrate spray printing or organic vapors spray printing is heavy
Long-pending and patterned processing procedure, entire contents are cited in the present invention.Certainly other methods also can be used.Material for deposition
Adjustment can be given with the deposition method of corresponding its institute spy.
The diphenylpyrimidin compound replaced through quinoline that the present invention has formula (I) structure can be with vacuum deposition or wet coating
The amorphism film applied to organic electroluminescent device is made in method.When the compound is used in any above-mentioned organic layer, exhibition
Reveal long service life and good thermal stability.
Organic electroluminescent device of the invention can be applied to single element, and structure is that array configuration or array X-Y are sat
The element at yin-yang the two poles of the earth is equipped in mark.Compared to known element, the present invention can be obviously improved the use of organic electroluminescent device
Service life and driving stability.In addition, being combined with the phosphorescence admixture in luminescent layer, organic electroluminescent device application of the invention
Better performance is able to achieve in full-color or colorful display panel and can emit white light.
Below by embodiment many properties and effect that the present invention will be described in detail.These DETAILS SECTIONExamples are merely to illustrate
Property of the invention, the present invention is not limited to illustrated in specific embodiment.
Synthesis example 1: the synthesis of compound 1-1
By 4- bromoacetophenone (4-Bromoacetophenone) (10g, 50.23mmole) and quinoline -8- boric acid
(quinolin-8-ylboronic acid) (9.12g, 52.75mmole) is placed in reactive tank, and 120 milliliters of toluene is added,
And potassium carbonate (18.05g, 130.6mmole) is dissolved in after 70 milliliters of deionized water, reactive tank is also added, while being added four
(triphenylphosphine) palladium (Pd (PPh3)4) (1.74g, 1.507mmole) and 30 milliliters of ethyl alcohol, and heating and stirring are opened, it heats
Up to 80 DEG C and react overnight.To which 300 milliliters of deionized water is added after the reaction was completed, stop stirring simultaneously after agitated 30 minutes
Standing makes its layering, after removing water layer, is purified with silica gel chromatography, is concentrated into and adds 300 milliliters of hexane analysis after thick state
Out, organic layer merged filter solid, obtained faint yellow solid A (about 8 grams).
By faint yellow solid A (10g, 40.737mmole) and 4- bromobenzaldehyde (4-bromobenzaldehyde)
(8.23g, 44.48mmole) is placed in reactive tank, and sufficiently after water removal, 230 milliliters of ethyl alcohol is added, opens stirring, and add methanol
Sodium (0.655g, 12.31mmole) is stirred at room temperature 16 hours.Thereafter, 3- pyridine amidoxim hydrochloride (3- is added
Amidinopyridinium chloride) (6.7g, 44.34mmole) and sodium hydroxide (3.22g, 80.61mmole), and chase after
30 milliliters of toluene is added, opens heating device, heating is up to 75 DEG C and reacts overnight.After having reacted, solid is filtered to take, then
With 250 milliliters of toluene heating stirring and filter solid is crossed, obtains Off-white solid B (about 5.5 grams).
By Off-white solid B (10g, 19.40mmole) and 4- dibenzofurans boric acid (dibenzo [b, d] furan-
4-ylboronic acid) (4.936g, 23.38mmole) be placed in reactive tank, 120 milliliters of toluene is added.By potassium carbonate
Reactive tank is added after being dissolved in 70 milliliters of deionized water in (9.384g, 67.9mmole), and tetrakis triphenylphosphine palladium (Pd is added
(PPh3)4) ethyl alcohol of (1.12g, 0.97mmole) and 30 milliliters opens heating and stirring, heating is until 80 DEG C and react overnight.
After having reacted, 300 milliliters of deionized water is added, stops stirring and standing after stirring 30 minutes making its layering, be filtered,
Crude product is received using soxhlet's extractor, silica gel is added using soxhlet's extractor and carries out purification by chromatography, thick state is concentrated into and is added
300 milliliters of hexane is reinforced being precipitated, and organic layer merged filter solid, and obtained Off-white solid compound 1-1 (about 5.1 grams).
Compound 1-11HNMR:
1H NMR(CDCl3,400MHz),δ10-9.9(S,1H)；9.02-8.99(m,2H)；8.85-8.82(d,1H)；
8.45-8.26(m,5H)；8.2-7.45(m,17H).
Synthesis example 2: the synthesis of compound 1-2
By reactant A (10g, 40.737mmole) and 3- bromobenzaldehyde (3-bromobenzaldehyde) (8.23g,
It 44.48mmole) is placed in reactive tank, sufficiently after water removal, 230 milliliters of ethyl alcohol is added, opens stirring, and add sodium methoxide
(0.655g, 12.31mmole) is stirred at room temperature 16 hours.Thereafter, 3- pyridine amidoxim hydrochloride (3- is added
Amidinopyridinium chloride) (6.7g, 44.34mmole) and sodium hydroxide (3.22g, 80.61mmole), and chase after
30 milliliters of toluene is added, opens heating device, heating is up to 75 DEG C and reacts overnight.After having reacted, solid is filtered to take, then
With 250 milliliters of toluene heating stirring and filter solid is crossed, obtains Off-white solid C (about 5 grams).
By Off-white solid C (10g, 19.40mmole) and 4- dibenzofurans boric acid (dibenzo [b, d] furan-
4-ylboronic acid) (4.936g, 23.38mmole) be placed in reactive tank, 120 milliliters of toluene is added.By potassium carbonate
Reactive tank is added after being dissolved in 70 milliliters of deionized water in (9.384g, 67.9mmole), and tetrakis triphenylphosphine palladium (Pd is added
(PPh3)4) ethyl alcohol of (1.12g, 0.97mmole) and 30 milliliters opens heating and stirring, heating is until 80 DEG C of reactions and overnight.
After having reacted, 300 milliliters of deionized water is added, after stirring 30 minutes, stopping stirring standing makes its layering, it is filtered,
Crude product is received, silica gel is added using soxhlet's extractor and carries out purification by chromatography, thick 300 milliliters of state addition of hexane is concentrated into and adds
Strong to be precipitated, organic layer merged filter solid, and obtained Off-white solid compound 1-2 (about 5.5 grams).
Compound 1-21HNMR:
1H NMR(CDCl3,400MHz),δ10-9.92(S,1H)；9.02-8.99(m,2H)；8.85-8.82(S,1H)；
8.85-8.7(d,1H)；8.44-8.41(d,2H)；8.39-8.36(d,1H)；8.35-7.47(m,18H).
Synthesis example 3: the synthesis of compound 1-3
By reactant C (10g, 19.4mmole) and 4- dibenzothiophenes boric acid (dibenzo [b, d] thiophen-4-
Ylboronic acid) (5.31g, 23.28mmole) be placed in reactive tank, 120 milliliters of toluene is added.By potassium carbonate
Reactive tank is added after being dissolved in 70 milliliters of deionized water in (9.38g, 67.9mmole), and tetrakis triphenylphosphine palladium (Pd is added
(PPh3)4) ethyl alcohol of (1.12g, 0.97mmole) and 30 milliliters opens heating and stirring, heating is until 80 DEG C and react overnight.
After having reacted, 300 milliliters of deionized water is added, stopping stirring standing after stirring 30 minutes makes its layering, after removing water layer,
Purified with silica gel chromatography, be concentrated into the hexane precipitation that thick state is added 300 milliliters, organic layer merged filter solid, and obtained milky white
Color solid chemical compound 1-3 (about 8 grams).
Compound 1-31HNMR:
1H NMR(CDCl3,400MHz),δ9.96-9.94(S,1H)；9.01-8.99(m,2H):8.76-8.75(d,1H)；
8.72-8.71(S,1H)；8.45-8.38(m,3H)；8.25-8.23(m,4H)；7.95-7.44(m,14H).
Synthesis example 4: the synthesis of compound 1-5
By reactant C (10g, 19.4mmole) and 4- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) phenyl boric acid (4- (1-
Phenyl-1H-benzo [d] imidazol-2-yl) phenyl) boronic acid) (7.31g, 23.28mmole) be placed in instead
Slot is answered, 120 milliliters of toluene is added.It is added instead after potassium carbonate (9.38g, 67.9mmole) is dissolved in 70 milliliters of deionized water
Slot is answered, tetrakis triphenylphosphine palladium (Pd (PPh is added3)4) ethyl alcohol of (1.12g, 0.97mmole) and 30 milliliters opens heating and stir
It mixes, heating is up to 80 DEG C and reacts overnight.After having reacted, 300 milliliters of deionized water is added and stops after stirring 30 minutes
Stirring, which is stood, makes its layering, after removing water layer, is purified with silica gel chromatography, is concentrated into the hexane analysis that thick state is added 300 milliliters
Out, organic layer merged filter solid, obtained light green solid compound 1-5 (about 7.5 grams).
Compound 1-51HNMR:
1H NMR(CDCl3,400MHz),δ9.94-9.92(S,1H)；8.99-8.98(m,3H)；8.76-8.76(m,1H)；
8.45-8.44(S,2H)；8.44-8.42(d,3H)；8.27-8.25(t,3H)；8.19-8.17(S,2H)；7.93-7.3(m,
17H).
Synthesis example 5: the synthesis of compound 1-6
By reactant C (10g, 19.40mmole) and 3- (3- pyridyl group) phenyl boric acid ((3- (pyridin-3-yl)
Phenyl) boronic acid) (4.633g, 23.28mmole) be placed in reactive tank, 120 milliliters of toluene is added.By carbonic acid
Reactive tank is added after being dissolved in 70 milliliters of deionized water in potassium (9.384g, 67.9mmole), and tetrakis triphenylphosphine palladium (Pd is added
(PPh3)4) ethyl alcohol of (1.12g, 0.97mmole) and 30 milliliters opens heating and stirring, heating is until 80 DEG C and react overnight.
After having reacted, 300 milliliters of deionized water is added, stopping stirring standing after stirring 30 minutes makes its layering, is filtered, receives
To crude product, silica gel is added using soxhlet's extractor and carries out purification by chromatography, is concentrated into the hexane reinforcement that thick state is added 300 milliliters
It is precipitated, organic layer merged filter solid, and obtained Off-white solid compound 1-6 (about 4.3 grams).
Compound 1-61HNMR:
1H NMR(CDCl3,400MHz),δ9.9-9.8(S,1H)；8.99-8.95(m,3H)；8.79-8.75(t,1H)；
8.64-8.63(d,1H)；8.54-8.51(S,1H)；8.45-8.43(d,3H)；8.26-8.25(d,2H)；8.25-8.21(d,
1H)；8.20-7.99(S,1H)；7.99-7.40(m,13H).
Synthesis example 6: the synthesis of compound 1-7
By compound A (10g, 40.737mmole) and 3,5- dibromo benzaldehyde (3,5-dibromobenzaldehyde)
(11.74g, 44.48mmole) is placed in reactive tank, and 230 milliliters of ethyl alcohol is sufficiently added after water removal, opens stirring, and add methanol
Sodium (0.655g, 12.31mmole) is stirred at room temperature 16 hours.Thereafter, 3- pyridine amidoxim salt (3- is added
Amidinopyridinium chloride) (6.7g, 44.34mmole) and sodium hydroxide (3.22g, 80.61mmole), and chase after
30 milliliters of toluene is added, opens heating device, heating is up to 75 DEG C and reacts overnight.After having reacted, solid is filtered to take, then
With 250 milliliters of toluene heating stirring and filter solid is crossed, obtains Off-white solid compound D (about 6.3 grams).
By compound D (10g, 16.83mmole) and 1- naphthalene boronic acids (1-Naphthalenylboronic acid)
(7.236g, 42.07mmole) is placed in reactive tank, and 120 milliliters of toluene is added.By potassium carbonate (18.768g, 135.8mmole)
Reactive tank is added after being dissolved in 70 milliliters of deionized water, tetrakis triphenylphosphine palladium (Pd (PPh is added3)4) (2.24g,
1.94mmole) and 30 milliliters ethyl alcohol open heating and stirring, heating until 80 DEG C reaction and it is overnight.After having reacted, it is added
300 milliliters of deionized water, after stirring 30 minutes, stopping stirring standing makes its layering, is filtered, receives crude product, uses rope
Family name's extractor is added silica gel and carries out purification by chromatography, is concentrated into the hexane reinforcement precipitation that thick state is added 300 milliliters, organic laminated
And filter solid is crossed, obtain Off-white solid compound 1-7 (about 6.5 grams).1H NMR(CDCl3,400MHz),δ9.916(d,1H),
8.95-8.98(m,2H),8.73(dd,1H),8.52(d,2H),8.42(d,2H),8.23-8.25(m,2H),8.13(d,2H),
7.98(m,4H),7.88(m,4H),7.81(d,1H),7.61-7.67(m,5H),7.51-7.56(m,4H),7.41-7.50(m,
2H).
Synthesis example 7: the synthesis of compound 1-8
By reactant C (10g, 19.40mmole) and quinoline -8- boric acid (quinolin-8-ylboronic acid)
(4.027g, 23.28mmole) is placed in reactive tank, and 120 milliliters of toluene is added.By potassium carbonate (9.384g, 67.9mmole)
Reactive tank is added after being dissolved in 70 milliliters of deionized water, tetrakis triphenylphosphine palladium (Pd (PPh is added3)4) (1.12g,
0.97mmole) and 30 milliliters of ethyl alcohol opens heating and stirring, and heating is until 80 DEG C and react overnight.After having reacted, it is added
300 milliliters of deionized water stops stirring and standing making its layering after stirring 30 minutes, is filtered and receives crude product, use rope
Family name's extractor is added silica gel and carries out purification by chromatography, is concentrated into the hexane reinforcement precipitation that thick state is added 300 milliliters, organic laminated
And filter solid is crossed, obtain Off-white solid compound 1-8 (about 5.5 grams).
Compound 1-81HNMR:
1H NMR(CDCl3,400MHz),δ9.95-9.9(S,1H)；8.99-8.98(m,3H)；8.75-8.74(d,1H)；
8.62-8.62(S,1H)；8.43-8.42(d,2H)；8.41-8.37(d,1H)；8.27-8.27(m,3H)；7.92-7.4(m,
13H).
Synthesis example 8: the synthesis of compound 1-10
By reactant C (10g, 19.4mmole) and (- 9 base of 10- phenylanthracene)-boric acid ((10-phenylanthracen-9-
Yl) boronic acid) (6.36g, 21.32mmole) be placed in reactive tank, 120 milliliters of toluene is added.By potassium carbonate
Reactive tank is added after being dissolved in 70 milliliters of deionized water in (9.38g, 67.9mmole), and tetrakis triphenylphosphine palladium (Pd is added
(PPh3)4) ethyl alcohol of (0.67g, 0.582mmole) and 30 milliliters opens heating and stirring, heating is until 80 DEG C and reaction overnight.
After having reacted, 300 milliliters of deionized water is added, stopping stirring standing after stirring 30 minutes makes its layering, after removing water layer,
Purified with silica gel chromatography, be concentrated into the hexane precipitation that thick state is added 300 milliliters, organic layer merged filter solid, and obtained yellowish
Color solid chemical compound 1-10 (about 3.2 grams).
Compound 1-101HNMR:
1H NMR(CDCl3,400MHz),δ9.95-9.93(S,1H)；8.97-8.96(m,2H)；8.74-8.72(m,1H)；
8.58-8.56(d,1H)；8.56-8.54(m,3H)；8.45-8.43(m,2H)；7.93-7.66(m,22H).
Synthesis example 9: the synthesis of compound 1-11
By reactant C and (10- [1,1'- biphenyl] -4- base -9- anthryl)-boric acid (10- ([1,1'-biphenyl] -4-
Yl) anthracen-9-yl) boronic acid (10.89g, 29.1mmole) is placed in reactive tank, 120 milliliters of toluene is added.
Potassium carbonate (9.38g, 67.9mmole) is dissolved in after 70 milliliters of deionized water, reactive tank is added, tetrakis triphenylphosphine palladium is added
(Pd(PPh3)4) ethyl alcohol of (0.56g, 0.485mmole) and 30 milliliters opens heating and stirring, heating is until 80 DEG C.Wait react
After complete, 300 milliliters of deionized water is added, stopping stirring standing after stirring 30 minutes makes its layering, after removing water layer, uses silica gel
Purification by chromatography, is concentrated into the hexane precipitation that thick state is added 300 milliliters, and organic layer merged filter solid, and obtained faint yellow solid
Compound 1-11 (about 4.4 grams).
Compound 1-111HNMR:
1H NMR(CDCl3,400MHz),δ9.95-9.92(S,1H)；8.95-8.93(m,2H)；8.7-8.6(m,1H)；
8.58-8.56(d,1H)；8.56-8.54(m,3H)；8.420-8.402(m,2H)；7.904-7.26(m,26H).
Synthesis example 10: the synthesis of compound 1-15
By reactant C (10g, 19.4mmole) and 9,9'- spiral shell, two fluorenes -2- ylboronic acid (9,9'-spirobi [fluoren] -
2-ylboronic acid) (8.386g, 23.2mmole) be placed in reactive tank, 120 milliliters of toluene is added.By potassium carbonate
Reactive tank is added after being dissolved in 70 milliliters of deionized water in (9.38g, 67.9mmole), and tetrakis triphenylphosphine palladium (Pd is added
(PPh3)4) ethyl alcohol of (0.672g, 0.582mmole) and 30 milliliters opens heating and stirring, heating is until 80 DEG C and overnight anti-
It answers.After having reacted, 300 milliliters of deionized water is added, stopping stirring standing after stirring 30 minutes makes its layering, removes water layer
Afterwards, purified with silica gel chromatography, be concentrated into the hexane precipitation that thick state is added 300 milliliters, organic layer merged filter solid, and obtained newborn
Compound as white solid 1-15 (about 7.2 grams).
Compound 1-151HNMR:
1H NMR(CDCl3,400MHz),δ9.8-9.7(s,1H)；8.97-8.96(m,1H)；8.74-8.73(m,1H)；
8.58-8.57(d,1H)；8.4-8.35(m,3H)；8.3-8.25(m,1H)；8.17-8.15(m,1H)；8.1-8.07(s,1H)；
7.94-7.39(m,17H)；7.17-7.1(t,3H)；7.03-7.01(s,1H)；6.81-6.78(d,2H),6.5-6.4(s,
1H).
Synthesis example 11: the synthesis of compound 1-22
By 3'- bromoacetophenone (3'-Bromoacetophenone) (10g, 50.23mmole) and quinoline -8- boric acid
(quinolin-8-ylboronic acid) (9.12g, 52.75mmole) is placed in reactive tank, and 120 milliliters of toluene is added.It will
Reactive tank is added after being dissolved in 70 milliliters of deionized water in potassium carbonate (18.05g, 130.6mmole), and tetrakis triphenylphosphine palladium is added
(Pd(PPh3)4) ethyl alcohol of (1.74g, 1.507mmole) and 30 milliliters opens heating and stirring, heating is until 80 DEG C of reactions and anti-
It answers overnight.After having reacted, 300 milliliters of deionized water is added, stopping stirring standing after stirring 30 minutes makes its layering, removes
After water layer, purified with silica gel chromatography, be concentrated into thick, obtains weak yellow liquid compound E (about 5.5 grams).
By compound E (10g, 40.737mmole) and 3- bromobenzaldehyde (3-bromobenzaldehyde) (8.23g,
It 44.48mmole) is placed in reactive tank, 230 milliliters of ethyl alcohol is sufficiently added after water removal, opens stirring, and add sodium methoxide
(0.655g, 12.31mmole) is stirred at room temperature 16 hours.Thereafter, 3- pyridine amidoxim salt (3- is added
Amidinopyridinium chloride) (6.7g, 44.34mmole) and sodium hydroxide (3.22g, 80.61mmole), and chase after
30 milliliters of toluene is added, opens heating device, heating is up to 75 DEG C and reacts overnight.After having reacted, then with 250 milliliters
Toluene heating stirring simultaneously crosses filter solid, obtains Off-white solid compound F (about 4.5 grams).
By compound F (10g, 19.4mmole) and (- 9 base of 10- phenylanthracene)-boric acid ((10-phenylanthracen-9-
Yl) boronic acid) (6.36g, 21.32mmole) be placed in reactive tank, 120 milliliters of toluene is added.By potassium carbonate
Reactive tank is added after being dissolved in 70 milliliters of deionized water in (9.38g, 67.9mmole), and tetrakis triphenylphosphine palladium (Pd is added
(PPh3)4) ethyl alcohol of (0.67g, 0.582mmole) and 30 milliliters opens heating and stirring, heating is until 80 DEG C and reaction overnight.
After having reacted, 300 milliliters of deionized water is added, stopping stirring standing after stirring 30 minutes makes its layering, after removing water layer,
Purified with silica gel chromatography, be concentrated into the hexane precipitation that thick state is added 300 milliliters, organic layer merged filter solid, and obtained yellowish
Color solid chemical compound 1-22 (about 3 grams).
Synthesis example 12: the synthesis of compound 1-23
By compound A (10g, 40.737mmole) and 3- bromobenzaldehyde (4-bromobenzaldehyde) (8.23g,
It 44.48mmole) is placed in reactive tank, 230 milliliters of ethyl alcohol is sufficiently added after water removal, opens stirring, and add sodium methoxide
(0.655g, 12.31mmole) is stirred at room temperature 16 hours.Thereafter, 2- pyridine amidoxim salt (2- is added
Amidinopyridinium chloride) (6.7g, 44.34mmole) and sodium hydroxide (3.22g, 80.61mmole), and chase after
30 milliliters of toluene is added, opens heating device, heating is up to 75 DEG C and reacts overnight.After having reacted, solid is filtered to take, then
With 250 milliliters of toluene heating stirring and filter solid is crossed, obtains Off-white solid compound G (about 3.8 grams).
By compound G (10g, 19.4mmole) and (- 9 base of 10- phenylanthracene)-boric acid ((10-phenylanthracen-9-
Yl) boronic acid) (6.36g, 21.32mmole) be placed in reactive tank, 120 milliliters of toluene is added.By potassium carbonate
Reactive tank is added after being dissolved in 70 milliliters of deionized water in (9.38g, 67.9mmole), and tetrakis triphenylphosphine palladium (Pd is added
(PPh3)4) ethyl alcohol of (0.67g, 0.582mmole) and 30 milliliters opens heating and stirring, heating is until 80 DEG C and reaction overnight.
After having reacted, 300 milliliters of deionized water is added, stopping stirring standing after stirring 30 minutes makes its layering, after removing water layer,
Purified with silica gel chromatography, be concentrated into the hexane precipitation that thick state is added 300 milliliters, organic layer merged filter solid, and obtained yellowish
Color solid chemical compound 1-23 (about 3.3 grams).
The physics value of above-mentioned material is shown in table 2.The measuring method of each physics value is as follows.
(1) thermal cracking temperature (Td)
It is measured using thermogravimetric analyzer (Perkin Elmer, TGA 8000), under normal pressure and tool nitrogen atmosphere, with
20 DEG C/min of programmed rate measures the thermal cracking property of compound obtained, and weight is decreased to starting weight
95% temperature be thermal cracking temperature (Td)。
(2) glass transition temperature (Tg)
Use differential scanning calorimetry instrument (DSC；Perkin Elmer, DSC 8000) with 20 DEG C/min of temperature programming
Rate measures compound obtained.
(3) the energy rank value of highest occupied molecular orbital (HOMO)
In addition, filminess is made in compound, under atmosphere using Photoelectron Spectrophotometer (Riken Keiki,
Surface Analyzer) its ionization potential numerical value is measured, it is that HOMO can rank value after its numerical value is further converted.
(4) the energy rank value of lowest unoccupied molecular orbital (LUMO)
The film of above compound is measured into its suction with UV/VIS spectrophotometer (Perkin Elmer, Lambda 20)
The boundary value (onset) for receiving wavelength, by the value it is converted edge energy, by edge energy and HOMO can rank numerical value subtract each other to get
LUMO can rank.
(5) triplet energies value (ET)
Using measuring luminescent spectrum under Fluorescence Spectrometer (Perkin Elmer, LS 55) Yu Wendu 77K, then via calculating,
E can be obtainedT。
Table 2
Embodiment 1: the manufacture of organic electroluminescent device
Deposition system is loaded into substrate before use, first carrying out degreasing with solvent and ultraviolet and ozone cleaning base plate.Later, will
Substrate is sent to vacuum deposition chamber, deposits all layers in the top of substrate.According to each series of strata shown in Fig. 2 by the vapor deposition boat that heats
(boat) about 10-6The vacuum degree deposited in sequential of support:
A) hole injection layer, includes the HTM doped with 9%p type electrical conductivity admixture, wherein the p-type by 20 nanometers of thickness
Electrical conductivity admixture is purchased from Shanghai Han Feng Chemical Co., Ltd., and the HTM is purchased from Merck&Co., Inc.；
B) hole transmission layer, 170 nanometers of thickness, HTM；
C) exciton barrier-layer, 10 nanometers of thickness, HT (preparation of sunlight radium photoelectricity)；
D) luminescent layer, includes the EBH doped with 4% volume ratio BD by 25 nanometers of thickness, wherein BD and EBH is sunlight radium photoelectricity
Preparation；
E) electron transfer layer, 25 nanometers of thickness, oxyquinoline lithium (Liq, sunlight radium photoelectricity comprising compound 1-1 and doping
Preparation), volume ratio 1:1；
F) electron injecting layer, 0.5 nanometer of thickness, lithium fluoride (LiF)；And
G) cathode, about 180 nanometers of thickness, include A1.
Component structure can indicate such as: (10 receive ITO/HTM:p type electrical conductivity admixture (20 nanometers)/HTM (170 nanometers)/HT
Rice)/EBH:BD (25 nanometers)/compound 1-1:Liq (25 nanometers)/LiF (0.5 nanometer)/Al (180 nanometers).
After deposition forms above layers, which is sent in drying box, immediately with UV curable epoxy
Resin and glass cover-plate containing hygroscopic agent are packaged.The organic electroluminescent device has 9 square millimeters of light emitting region.
Embodiment 2 to 7: the manufacture of organic electroluminescent device
Except the compound 1-1 of electron transfer layer in embodiment 1 is distinctly replaced into compound 1-2,1-3,1-5,1-10,1-
11 and 1-15, the layer structure of embodiment 2, embodiment 3, embodiment 4, embodiment 5, embodiment 6 and embodiment 7 such as embodiment 1.
Comparing embodiment 1: the manufacture of organic electroluminescent device
By organic electroluminescent device manufacture at the layer structure of structure similar embodiment 1, in addition to electronics in embodiment 1 is passed
The compound 1-1 of defeated layer is replaced into compound EET09, which can indicate such as: ITO/HTM:p
Dopant (20 nanometers)/HTM (170 nanometers)/HT (10 nanometers)/EBH:BD (25 nanometers)/(25 receive compound EET09:Liq
Rice)/LiF (0.5 nanometer)/Al (180 nanometers).
Wherein, compound EET09 is as described in JP 2011003793A.
The Electroluminescence Properties of organic electroluminescent device made of above-mentioned use constant current supply (KEITHLEY
2400Source Meter, made by Keithley Instruments, Inc., Cleveland, Ohio) and photometer
(PHOTO RESEARCH SpectraScan PR 650,made by Photo Research,Inc.,Chatsworth,
Calif. its luminosity) is measured at room temperature, and (standard value is on the basis of the organic electroluminescent device of comparing embodiment
1) value for, driving it voltage, luminous efficiency and LT95 is shown in table 3.Wherein, the definition of LT95 value is that luminance level is down to phase
Time consumed by level for the 95% of original intensity, service life or stabilization as assessment organic electroluminescent device
The measurement standard of property.
Table 3
| Electron transfer layer compound | Vd | Luminous efficiency | Component life LT95 | |
| Comparing embodiment 1 | EET09:Liq | 1 | 1 | 1 |
| Embodiment 1 | Compound 1-1:Liq | +0.88V | - 3.4% | -- |
| Embodiment 2 | Compound 1-2:Liq | +0.76V | - 9.5% | >+100% |
| Embodiment 3 | Compound 1-3:Liq | +0.49V | - 0.8% | + 50% |
| Embodiment 4 | Compound 1-5:Liq | +0.97V | - 15% | >+100% |
| Embodiment 5 | Compound 1-10:Liq | +0.21V | + 7.7% | >+100% |
| Embodiment 6 | Compound 1-11:Liq | +0.40V | + 6.9% | + 67% |
| Embodiment 7 | Compound 1-15:Liq | +0.98V | + 15% | + 3% |
As described above, in acceptable driving voltage and the loss range of luminous efficiency, it is seen that include tool of the invention
The organic electroluminescent device of the diphenylpyrimidin compound replaced through quinoline of formula (I) structure shows good heat resistance and significant
Improve its service life, therefore, organic electroluminescent device of the invention is suitable for the application fields such as vehicle display, and has
High technological value.
Above-described embodiment is only to be illustrated, and is not intended to limit the present invention.Anyone skilled in the art can be
Without prejudice under spirit and scope of the invention, modifications and changes are made to the above embodiments.Therefore, rights protection model of the invention
It encloses and is defined by claims appended hereto, as long as not influencing effect of the invention and implementing purpose, this should be covered by
In public technology content.
Claims (13)
1. the diphenylpyrimidin compound of a kind of tool formula (I) structure replaced through quinoline:
In formula, X1Indicate the C for being substituted or being unsubstituted6-30Aryl, be substituted or be unsubstituted containing selected from by N, O and S
Organize at least one heteroatomic C in groups5-30Heteroaryl；
A1Indicate the C for being substituted or being unsubstituted6-36Aryl, be substituted or be unsubstituted containing selected from being made of N, O and S
At least one heteroatomic C in group5-30Heteroaryl；
X1And A1To be identical or different, and at least one is is substituted or is unsubstituted containing selected from being made of N, O and S
At least one heteroatomic C in group5-30Heteroaryl；And
N indicates an integer of 1 or 2, and when n indicates 2, A1It is respectively identical or different.
2. the diphenylpyrimidin compound replaced through quinoline of tool formula (I) structure as described in claim 1, with formula (I-1) knot
Structure or formula (I-2) representation:
In formula, X1Indicate the C for being substituted or being unsubstituted6-30Aryl, be substituted or be unsubstituted containing selected from by N, O and S
Organize at least one heteroatomic C in groups5-30Heteroaryl；
A1Indicate the C for being substituted or being unsubstituted6-36Aryl, be substituted or be unsubstituted containing selected from being made of N, O and S
At least one heteroatomic C in group5-30Heteroaryl；
X1And A1To be identical or different, and at least one is is substituted or is unsubstituted containing selected from being made of N, O and S
At least one heteroatomic C in group5-30Heteroaryl；And
N indicates an integer of 1 or 2, and when n indicates 2, A1It is respectively identical or different.
3. the diphenylpyrimidin compound replaced through quinoline of tool formula (I) structure as described in claim 1, which is characterized in that X1
For pyridyl group, quinolyl or naphthalene.
4. the diphenylpyrimidin compound replaced through quinoline of tool formula (I) structure as claimed in claim 2, X1Selected from following institute
Group is one of in groups:
In formula, Xr indicates hydrogen, fluorine, cyano, C1-4Alkyl or the C being unsubstituted6-18Aryl.
5. the diphenylpyrimidin compound replaced through quinoline of tool formula (I) structure as described in claim 1, which is characterized in that A1
One of in groups selected from following group:
In formula, L indicates O or S；
Ar1To Ar6The respectively independent C for indicating hydrogen, being unsubstituted6-18Aryl；
R1To R4The respectively independent C for indicating hydrogen, being substituted or being unsubstituted6-12Aryl, R1And R2It is common with the carbon atom being connected
Form C6-18Condensed aromatic loop system or R3And R4C is collectively formed with the carbon atom being connected6-18Condensed aromatic loop system；And
Y1And Y2One singly-bound and to be connected to formula (I) compound, another is hydrogen.
6. the diphenylpyrimidin compound replaced through quinoline of tool formula (I) structure as claimed in claim 5, which is characterized in that
The C being unsubstituted6-18Aryl is phenyl, and the C being unsubstituted6-12Aryl is phenyl.
7. the diphenylpyrimidin compound replaced through quinoline of tool formula (I) structure as described in claim 1, which is characterized in that
When n is 1, which is shown in formula (I-3) or formula (I-4):
8. the diphenylpyrimidin compound replaced through quinoline of tool formula (I) structure as described in claim 1 is compound (1-
Or one of compound (1-11) 10):
9. the diphenylpyrimidin compound replaced through quinoline of tool formula (I) structure as described in claim 1, which is characterized in that
When n is 2, which is shown in formula (I-5):
10. the diphenylpyrimidin compound replaced through quinoline of tool formula (I) structure as claimed in claim 9, which is characterized in that
A1For identical structure.
11. a kind of organic electroluminescent device, includes:
Cathode；
Anode；And
Organic layer, between the cathode and anode, and the organic layer includes tool formula (I) structure as described in claim 1
The diphenylpyrimidin compound replaced through quinoline.
12. organic electroluminescent device as claimed in claim 11, which is characterized in that the organic layer is electron transfer layer, and
It is with a thickness of 20 nanometers to 30 nanometers.
13. organic electroluminescent device as claimed in claim 12, which is characterized in that the electron transfer layer also includes N-type electricity
Property conduction admixture, and the content of the N-type electrical conductivity admixture be 0 weight % to 50 weight %.
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|---|---|---|---|---|
| CN103380508A (en) * | 2011-11-22 | 2013-10-30 | 出光兴产株式会社 | Aromatic heterocyclic derivative, material for organic electroluminescent element, and organic electroluminescent element |
| CN107112427A (en) * | 2014-11-14 | 2017-08-29 | 保土谷化学工业株式会社 | Organic electroluminescence device |
| WO2017179809A1 (en) * | 2016-04-11 | 2017-10-19 | 주식회사 두산 | Organic light-emitting compound and organic electroluminescent element using same |
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| KR101288557B1 (en) * | 2008-12-24 | 2013-07-22 | 제일모직주식회사 | Novel compound for organic photoelectric device and organic photoelectric device including the same |
| EP2452997A4 (en) * | 2009-07-10 | 2013-10-09 | Cheil Ind Inc | Compound for an organic photoelectric element, and an organic photoelectric element comprising the same |
| TW201434827A (en) * | 2012-12-17 | 2014-09-16 | Tosoh Corp | Pyrimidine compound, and organic electroluminescent element containing same |
| EP3156402B1 (en) * | 2014-06-11 | 2021-11-10 | Hodogaya Chemical Co., Ltd. | Pyrimidine derivative and organic electroluminescent element |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103380508A (en) * | 2011-11-22 | 2013-10-30 | 出光兴产株式会社 | Aromatic heterocyclic derivative, material for organic electroluminescent element, and organic electroluminescent element |
| CN107112427A (en) * | 2014-11-14 | 2017-08-29 | 保土谷化学工业株式会社 | Organic electroluminescence device |
| WO2017179809A1 (en) * | 2016-04-11 | 2017-10-19 | 주식회사 두산 | Organic light-emitting compound and organic electroluminescent element using same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112745285A (en) * | 2019-10-31 | 2021-05-04 | 昱镭光电科技股份有限公司 | Aminodibenzofuran compound and organic electroluminescent device thereof |
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| TWI630260B (en) | 2018-07-21 |
| TW201928006A (en) | 2019-07-16 |
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