CN115873590A - 一种有机材料组合物及其应用 - Google Patents
一种有机材料组合物及其应用 Download PDFInfo
- Publication number
- CN115873590A CN115873590A CN202111128530.0A CN202111128530A CN115873590A CN 115873590 A CN115873590 A CN 115873590A CN 202111128530 A CN202111128530 A CN 202111128530A CN 115873590 A CN115873590 A CN 115873590A
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- China
- Prior art keywords
- substituted
- unsubstituted
- group
- phenyl
- ring
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 28
- 239000011368 organic material Substances 0.000 title claims abstract description 25
- -1 anthracyl Chemical group 0.000 claims description 82
- 239000000463 material Substances 0.000 claims description 56
- 239000010410 layer Substances 0.000 claims description 51
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 50
- 150000001875 compounds Chemical class 0.000 claims description 31
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 25
- 125000003118 aryl group Chemical group 0.000 claims description 23
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical group [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 21
- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 21
- 229910052805 deuterium Inorganic materials 0.000 claims description 21
- 125000001624 naphthyl group Chemical group 0.000 claims description 20
- 238000002347 injection Methods 0.000 claims description 18
- 239000007924 injection Substances 0.000 claims description 18
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 17
- 229910052736 halogen Inorganic materials 0.000 claims description 17
- 150000002367 halogens Chemical group 0.000 claims description 17
- 125000001072 heteroaryl group Chemical group 0.000 claims description 17
- 239000004305 biphenyl Substances 0.000 claims description 14
- 235000010290 biphenyl Nutrition 0.000 claims description 14
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 14
- 150000002431 hydrogen Chemical group 0.000 claims description 14
- 125000004076 pyridyl group Chemical class 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 12
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 11
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 230000005525 hole transport Effects 0.000 claims description 10
- 239000012044 organic layer Substances 0.000 claims description 10
- 125000002178 anthracenyl group Chemical class C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 claims description 8
- 125000004104 aryloxy group Chemical group 0.000 claims description 8
- 125000005878 benzonaphthofuranyl group Chemical class 0.000 claims description 8
- 125000005509 dibenzothiophenyl group Chemical class 0.000 claims description 8
- 125000000732 arylene group Chemical group 0.000 claims description 7
- 125000005549 heteroarylene group Chemical group 0.000 claims description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- 125000004475 heteroaralkyl group Chemical group 0.000 claims description 6
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 6
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 6
- 125000005561 phenanthryl group Chemical group 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- 125000004434 sulfur atom Chemical group 0.000 claims description 5
- 125000000739 C2-C30 alkenyl group Chemical group 0.000 claims description 4
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims description 4
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 4
- 239000002019 doping agent Substances 0.000 claims description 4
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 4
- 125000004957 naphthylene group Chemical group 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 125000001792 phenanthrenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 claims description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 4
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000001041 indolyl group Chemical group 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 125000006749 (C6-C60) aryl group Chemical group 0.000 claims description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical group C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 claims description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical group C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims description 2
- HIYWOHBEPVGIQN-UHFFFAOYSA-N 1h-benzo[g]indole Chemical group C1=CC=CC2=C(NC=C3)C3=CC=C21 HIYWOHBEPVGIQN-UHFFFAOYSA-N 0.000 claims description 2
- MOWKTPHUWHQZSC-UHFFFAOYSA-N 3h-naphtho[1,2-g]indole Chemical group C1=CC=C2C3=CC=C4C=CNC4=C3C=CC2=C1 MOWKTPHUWHQZSC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001555 benzenes Chemical group 0.000 claims description 2
- MFMVRILBADIIJO-UHFFFAOYSA-N benzo[e][1]benzofuran Chemical group C1=CC=C2C(C=CO3)=C3C=CC2=C1 MFMVRILBADIIJO-UHFFFAOYSA-N 0.000 claims description 2
- LJOLGGXHRVADAA-UHFFFAOYSA-N benzo[e][1]benzothiole Chemical group C1=CC=C2C(C=CS3)=C3C=CC2=C1 LJOLGGXHRVADAA-UHFFFAOYSA-N 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000004988 dibenzothienyl group Chemical class C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 claims description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 2
- 125000006836 terphenylene group Chemical group 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical class N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 claims 1
- 239000004973 liquid crystal related substance Substances 0.000 claims 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- 230000015572 biosynthetic process Effects 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 9
- 229910052801 chlorine Inorganic materials 0.000 description 9
- 229910001868 water Inorganic materials 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000012043 crude product Substances 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 238000004440 column chromatography Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000903 blocking effect Effects 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 229940125904 compound 1 Drugs 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000000872 buffer Substances 0.000 description 4
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical group C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000002971 oxazolyl group Chemical group 0.000 description 3
- 125000000714 pyrimidinyl group Chemical group 0.000 description 3
- 125000003003 spiro group Chemical group 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000003960 triphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12)* 0.000 description 3
- AJOAHIKYBSZIEV-UHFFFAOYSA-N 2-bromo-4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C(Br)=C1 AJOAHIKYBSZIEV-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 101001121408 Homo sapiens L-amino-acid oxidase Proteins 0.000 description 2
- 102100026388 L-amino-acid oxidase Human genes 0.000 description 2
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 2
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 2
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- 238000010549 co-Evaporation Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- IYYZUPMFVPLQIF-ALWQSETLSA-N dibenzothiophene Chemical group C1=CC=CC=2[34S]C3=C(C=21)C=CC=C3 IYYZUPMFVPLQIF-ALWQSETLSA-N 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene sulfoxide Chemical group C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 239000002346 layers by function Substances 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 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
- 238000011056 performance test Methods 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 125000003373 pyrazinyl group Chemical group 0.000 description 2
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 2
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000000335 thiazolyl group Chemical group 0.000 description 2
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 2
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- IIISHLMCTDMUHH-UHFFFAOYSA-N 2-bromo-5-chlorobenzaldehyde Chemical compound ClC1=CC=C(Br)C(C=O)=C1 IIISHLMCTDMUHH-UHFFFAOYSA-N 0.000 description 1
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 description 1
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 1
- CHFHJZQNRFZRNY-UHFFFAOYSA-N 4-[tert-butyl-(1,1-dichloro-2-methylpropan-2-yl)phosphanyl]-N,N-dimethylaniline Chemical compound ClC(C(C)(C)P(C1=CC=C(C=C1)N(C)C)C(C)(C)C)Cl CHFHJZQNRFZRNY-UHFFFAOYSA-N 0.000 description 1
- ZVDSWJQOVVRVKE-UHFFFAOYSA-N 4-chloro-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzaldehyde Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC(Cl)=CC=C1C=O ZVDSWJQOVVRVKE-UHFFFAOYSA-N 0.000 description 1
- JSGQMZRCRXFFKM-UHFFFAOYSA-N 5-chloro-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzaldehyde Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C(Cl)C=C1C=O JSGQMZRCRXFFKM-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 241000720974 Protium Species 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004604 benzisothiazolyl group Chemical group S1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 125000004603 benzisoxazolyl group Chemical group O1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 125000002047 benzodioxolyl group Chemical group O1OC(C2=C1C=CC=C2)* 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000005874 benzothiadiazolyl group Chemical group 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 125000000259 cinnolinyl group Chemical group N1=NC(=CC2=CC=CC=C12)* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229940125773 compound 10 Drugs 0.000 description 1
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical compound [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000001977 isobenzofuranyl group Chemical group C=1(OC=C2C=CC=CC12)* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- SJFNDMHZXCUXSA-UHFFFAOYSA-M methoxymethyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(COC)C1=CC=CC=C1 SJFNDMHZXCUXSA-UHFFFAOYSA-M 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000002894 organic compounds Chemical group 0.000 description 1
- 125000001715 oxadiazolyl group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000004934 phenanthridinyl group Chemical group C1(=CC=CC2=NC=C3C=CC=CC3=C12)* 0.000 description 1
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000005247 tetrazinyl group Chemical group N1=NN=NC(=C1)* 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical group OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 229910052722 tritium Inorganic materials 0.000 description 1
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Abstract
本发明提供一种有机材料组合物及其应用,所述有机材料组合物通过所含化合物之间的配合使得作为有机功能层材料时,器件具有较低的驱动电压,较高的电流效率和较高的寿命。
Description
技术领域
本发明属于有机电致发光技术领域,涉及一种有机材料组合物及其应用。
背景技术
有机发光二极管(organic light emitting diode,OLED)近来由于对平板显示器的需求增加而引起关注。有机OLED装置的有机层可以包含空穴注入层、空穴传输层、空穴辅助层、发光辅助层、电子阻挡层、发光层(含有主体材料和掺杂剂材料)、电子缓冲层、空穴阻挡层、电子传输层、电子注入层等。可以取决于它们的功能将有机层中使用的材料分为空穴注入材料、空穴传输材料、空穴辅助材料、发光辅助材料、电子阻挡材料、发光材料、电子缓冲材料、空穴阻挡材料、电子传输材料、电子注入材料等。在有机OLED装置中,通过施加电压将来自阳极的空穴和来自阴极的电子注入到发光层中,并且通过空穴和电子的再结合产生具有高能量的激子。有机发光化合物通过能量移动到激发态并由当有机发光化合物从激发态返回到基态时的能量发射光。
OLED发光性能最重要的因素是发光材料,发光材料需要具有较高的量子效率、较高的电子迁移率和较高的空穴迁移率,且发光材料需均匀、稳定。因此,在本领域,对于发光材料的开发极其重要。
发明内容
针对现有技术的不足,本发明的目的在于提供一种有机材料组合物及其应用。
为达此目的,本发明采用以下技术方案:
一方面,本发明提供一种有机材料组合物,所述有机材料组合物包含至少一种式1所示结构的化合物和至少一种式2所示结构的化合物,
其中,R选自氢、氘、卤素、氰基、取代或未取代的C1-C30烷基、取代或未取代的C3-C30环烷基、取代或未取代的C6-C30芳基、取代或未取代的C3-C30杂芳基,
R1选自-L1Ar1,R2选自-L2Ar2,R3选自-L3Ar3,R4选自-L4Ar4,
L1-L4各自独立选自连接键、取代或未取代的C6-C30的亚芳基、取代或未取代的C3-C30的亚杂芳基,
Ar1-Ar4各自独立选自选自氢、氘、卤素、氰基、取代或未取代的C3-C60的杂芳基;
Ar10选自取代或未取代的C6-C60芳基、取代或未取代的C3-C60的杂芳基,
L10选自连接键、取代或未取代的C6-C30的亚芳基、取代或未取代的C3-C30的亚杂芳基,
R10-R17各自独立选自氢、氘、卤素、氰基、取代或未取代的C1-C30烷基、其中一个或多个亚甲基以O原子或S原子不相邻的方式被-O-或-S-取代的C1-C30烷基、取代或未取代的C2-C30烯基、其中一个或多个亚甲基以O原子或S原子不相邻的方式被-O-或-S-取代的C2-C30烯基、取代或未取代的C7-C30芳烷基、取代或未取代的C6-C30芳基、取代或未取代的C3-C30杂芳基、取代或未取代的C4-C30杂芳烷基、取代或未取代的C3-C30环烷基、取代或未取代的C3-C30杂环烷基、取代或未取代的C3-C30环烯基、取代或未取代的C1-C30烷氧基、取代或未取代的C6-C30芳氧基,
R10-R17各自独立存在或相邻二至四者连接成环A,所述环A为取代或未取代的C6-C30的芳环、取代或未取代的C3-C30的杂芳环。
X1选自N或CRX1,X2选自N或CRX2,X3选自N或CRX3,X4选自N或CRX4,X5选自N或CRX5,
RX1-RX5各自独立选自氢、氘、氰基、取代或未取代的C1-C30烷基、取代或未取代的C3-C30环烷基、取代或未取代的C6-C30的芳基、取代或未取代的C3-C30的杂芳基,RX1-RX5各自独立存在,或相邻两者连接成环,所述环为苯环;
优选地,X1选自N,X2选自N,X3选自CRX3,X4选自CRX4,X5选自CRX5;
优选地,X1选自N,X3选自N,X2选自CRX2,X4选自CRX4,X5选自CRX5;
优选地,X1选自N,X2选自N,X3选自N,X4选自CRX4,X5选自CRX5;
优选地,式1中,所述RX1-RX5各自独立选自氢、氘、取代或未取代的如下基团:苯基、联苯基、三联苯基、萘基、菲基、蒽基、苯基取代萘基、萘基取代苯基、吡啶基、连吡啶基、二苯并呋喃基、二苯并噻吩基、咔唑基、咔唑基取代苯基、二甲基芴基、二苯基芴基、螺二芴基、二苯并呋喃取代苯基、二苯并噻吩取代苯基、二甲基芴基取代苯基、苯并咔唑基、苯并萘并呋喃基、苯并萘并噻吩基。
优选地,式1中,所述R1、R2、R3、R4至少一项选自氢;
优选地,所述R1、R2、R3、R4至少两项选自氢;
优选地,所述R1、R2、R3、R4中三项选自氢;
优选地,所述R2选自L2Ar2,R1、R3、R4均选自氢;
优选地,所述R3选自L3Ar3,R1、R2、R4均选自氢;
优选地,所述R选自取代或未取代的如下基团:苯基、联苯基。
优选地,L1-L4各自独立选自连接键、取代或未取代的如下基团:亚苯基、亚萘基、亚联苯基、亚三联苯基。
优选地,式1所示结构的化合物选自如下所述化合物,
其中D代表氘。
优选地,式2中,所述环A为取代或未取代的苯环;
优选地,式2所示结构的化合物为具有如下任一种结构的化合物:
优选地,所述环A为取代或未取代的茚环、吲哚环、苯并呋喃环、萘并呋喃环、苯并噻吩环、萘并噻吩环、苯并吲哚环、萘并吲哚环;
Y选自O,S,CRY5RY6、NLY7RY7,
RY1、RY2、RY3、RY4各自独立选自氢、氘、卤素、氰基、取代或未取代的C1-C30烷基、其中一个或多个亚甲基以O原子或S原子不相邻的方式被-O-或-S-取代的C1-C30烷基、取代或未取代的C7-C30芳烷基、取代或未取代的C6-C30芳基、取代或未取代的C3-C30杂芳基、取代或未取代的C4-C30杂芳烷基、取代或未取代的C3-C30环烷基、取代或未取代的C3-C30杂环烷基、取代或未取代的C3-C30环烯基、取代或未取代的C1-C30烷氧基、取代或未取代的C6-C30芳氧基,
RY1、RY2、RY3、RY4各自独立存在或相邻两者连接成苯环或萘环,
RY5、RY6各自独立选自取代或未取代的C1-C30烷基、取代或未取代的C6-C30芳基,
RY7选自取代或未取代的C1-C30烷基、取代或未取代的C7-C30芳烷基、取代或未取代的C6-C30芳基、取代或未取代的C3-C30杂芳基、取代或未取代的C4-C30杂芳烷基、取代或未取代的C3-C30环烷基、取代或未取代的C3-C30杂环烷基、取代或未取代的C6-C30芳氧基,
LY7连接键、取代或未取代的C6-C30的亚芳基、取代或未取代的C3-C30的亚杂芳基;
优选地,式2所示结构的化合物为具有如下任一种结构的化合物:
优选地,Ar10、RY7各自独立选自取代或未取代的如下基团:苯基、联苯基、三联苯基、萘基、苯基取代萘基、萘基取代苯基、蒽基、菲基、苯并菲基、吡啶基、二苯并呋喃基、二苯并噻吩基、咔唑基、苯基取代咔唑基、吡啶基取代咔唑基、萘基取代咔唑基、联苯基取代咔唑基、二苯并呋喃取代苯基、二苯并噻吩取代苯基、二甲基芴基、二苯基取代芴基、螺二芴基、苯并萘并呋喃基、苯并萘并噻吩基、苯并咔唑基、二苯并咔唑基;
优选地,R10-R17、RY1-RY4各自独立选自氢、氘、苯基、联苯基、三联苯基、萘基、苯基取代萘基、萘基取代苯基、蒽基、菲基、苯并菲基、吡啶基、二苯并呋喃基、二苯并噻吩基、二苯并呋喃取代苯基、二苯并噻吩取代苯基、二甲基芴基、二苯基取代芴基、螺二芴基、苯并萘并呋喃基、苯并萘并噻吩基,R10-R17、RY1-RY4各自独立存在或相邻两者连接形成苯环或萘环;
优选地,RY5、RY6各自独立选自甲基、苯基,或RY5、RY6连接形成芴基;
优选地,L10、LY7各自独立选自连接键、亚苯基、亚联苯基、亚萘基;
其中波浪线代表基团的连接位点。
在本发明中,如上所述基团带有取代基时,所述取代基各自独立选自氘、卤素、氰基、硝基、未取代或R'取代的C1~C4直链或支链烷基、未取代或R'取代的C6~C20芳基、未取代或R'取代的C3~C20杂芳基、C6~C20芳胺基;R'选自氘、卤素、氰基或硝基。
优选地,所述芳基选自苯基、联苯基、三联苯基、萘基、蒽基、菲基、苯并菲基、萘基取代苯基、二甲基芴基、二苯基取代芴基或螺二芴基;
优选地,所述杂芳基选自吡啶基、二苯并呋喃基、二苯并噻吩基、咔唑基、苯基取代咔唑基、吡啶基取代咔唑基、萘基取代咔唑基、联苯基取代咔唑基、二苯并呋喃取代苯基、二苯并噻吩取代苯基、苯并萘并呋喃基、苯并萘并噻吩基、苯并咔唑基或二苯并咔唑基;
优选地,所述烷基选自甲基、乙基、丙基、叔丁基、环己烷基或金刚烷基。
优选地,式2所示结构的化合物选自如下化合物:
优选地,所述有机材料组合物中式1所示结构的化合物与式2所示结构的化合物的重量比为1:9-9:1,例如1:9、2:8、3:7、4:6、5:5、6:4、7:3、8:2或9:1等,优选2:8-8:2,更优选3:7-7:3,进一步优选4:6-6:4。
如在本发明中所用,术语“有机电致发光材料”指可用于有机电致发光元件中并且可以包含至少一种化合物的材料。如有需要,有机电致发光材料可以包含在构成有机电致发光元件的任何层中。例如,有机电致发光材料可以是空穴注入材料、空穴传输材料、电子阻挡材料、发光辅助材料、发光层材料(包含主体材料和掺杂材料)、电子缓冲材料、空穴阻挡材料、电子传输材料、电子注入材料等。
如在本发明中所用,术语“卤素”可以包括氟、氯、溴或碘。
如在本发明所用,术语“C1-C30烷基”是指衍生自具有1至30个碳原子的直链或支链饱和烃的单价取代基,其实例包括但不限于甲基、乙基、丙基、异丁基、仲丁基、叔丁基、戊基、异戊基和己基。
如在本发明所用,术语“C3-C30环烷基”是指衍生自具有1至30个环主链碳原子的单环烃或多环烃,所述环烷烃可包括环丙基、环丁基、金刚烷基等。
本发明中芳基、亚芳基包括单环、多环或稠环芳基,所述环之间可以被短的非芳族单元间断,并且可以包含螺结构,包括但不限于苯基、联苯基、三联苯基、萘基、菲基、蒽基、芴基、螺二芴基等。
本发明中杂芳基、亚杂芳基包括单环、多环或稠环杂芳基,所述环之间可以被短的非芳族单元间断,所述杂原子包括氮、氧、硫。包括但不限于呋喃基、苯硫基、吡咯基、咪唑基、吡唑基、噻唑基、噻二唑基、异噻唑基、异噁唑基、噁唑基、噁二唑基、三嗪基、四嗪基、三唑基、四唑基、呋吖基、吡啶基、吡嗪基、嘧啶基、哒嗪基、苯并呋喃基、苯并噻吩基、异苯并呋喃基、二苯并呋喃基、二苯并噻吩基、苯并咪唑基、苯并噻唑基、苯并异噻唑基、苯并异噁唑基、苯并噁唑基、异吲哚基、吲哚基、吲唑基、苯并噻二唑基、喹啉基、异喹啉基、噌啉基、喹唑啉基、喹喔啉基、咔唑基、吩噁嗪基、吩噻嗪基、菲啶基、苯并间二氧杂环戊烯基、二氢吖啶基,及其衍生物等。
优选地,所述芳基选自苯基、联苯基、三联苯基、萘基、蒽基、菲基、9,9'-二甲基芴基、9,9'-二苯基芴基或螺二芴基。
优选地,所述杂芳基选自二苯并呋喃基、二苯并噻吩基、咔唑基、三嗪基、吡啶基、嘧啶基、咪唑基、噁唑基、噻唑基、苯并咪唑基、苯并噁唑基、苯并噻唑基、萘并咪唑基、萘并噁唑基、萘并噻唑基、菲并咪唑基、菲并噁唑基、菲并噻唑基、喹喔啉基、喹唑啉基、吲哚并咔唑基、吲哚并芴基、苯并噻吩并吡嗪基、苯并噻吩并嘧啶基、苯并呋喃并吡嗪基、苯并呋喃并嘧啶基、吲哚并吡嗪基、吲哚并嘧啶基、茚并吡嗪基、茚并嘧啶基、螺(芴-9,1'-茚)并吡嗪基、螺(芴-9,1'-茚)并嘧啶基、苯并呋喃并咔唑基或苯并噻吩并咔唑基。
如在本发明所用,术语“C6-C30芳氧基”是指由ZO-表示的单价取代基,其中Z表示具有6至30个碳原子的芳基。这种芳氧基的实例包括但不限于苯氧基、萘氧基、二苯氧基等。
如在本发明所用,术语“C1-C30烷氧基”是指由Z’O-表示的单价取代基,其中Z’表示具有1至30个碳原子的烷基。
如在本发明所用,术语“取代的”是指与化合物中的氢原子被另一取代基取代。该位置不限于特定位置,只要该位置上的氢能够被取代基取代即可。当出现两个或两个以上取代基时,两个或两个以上取代基可以相同或不同。
如在本发明所用,除非另有说明,氢原子包括氕、氘和氚。
本发明中“相邻两个基团连接成环”是指处于同一环或相邻环中相邻位置的2个取代基之间可以通过化学键相互连接成环,本发明对具体的连接成环方式不做限定(举例通过单键连接、通过苯环连接、通过萘环连接、通过稠和、通过稠和、通过稠和、通过稠和、通过稠和;其中表示稠和位置),如下文涉及相同的描述时,具有相同的意义
在本发明中,基团的限定中限定了碳原子数的范围,其碳原子数为所限定范围内的任一整数,例如C6-C60芳基,代表芳基的碳原子数可以是6-60所包含的范围内的任意整数,例如6、8、10、15、20、30、35、40、45、50、55或60等。
在本发明中,所述各个位置取代的有机化合物通过如下合成路线来制备:
另一方面,本发明提供了一种有机电致发光材料,所述有机电致发光材料包括如上所述的有机材料组合物。
另一方面,本发明提供了如上所述的有机材料组合物或有机电致发光材料在制备光学器件中的应用;
优选地,所述光学器件包括有机电致发光器件、有机场效应晶体管、有机薄膜晶体管、有机发光晶体管、有机集成电路、有机太阳能电池、有机场淬灭器件、发光电化学电池、有机激光二极管或有机光感受器中任意一种。
另一方面,本发明提供了一种有机电致发光器件,所述有机电致发光器件包括阳极和阴极,和设置在阳极和阴极间的有机层,所述有机层包括如上所述的有机材料组合物或有机电致发光材料。
优选地,所述有机层包括从阳极侧到阴极侧依次层叠设置的空穴注入层、空穴传输层、发光层、电子传输层和电子注入层;
优选地,所述发光层的材料包含主体材料和客体材料,所述主体材料包含如上所述的有机材料组合物或有机电致发光材料。
优选地,所述客体材料包括磷光掺杂剂,所述磷光掺杂剂包括含过渡金属的配合物。
另一方面,本发明提供一种有机电致发光设备,所述有机电致发光设备包括如上所述的有机电致发光器件。
相对于现有技术,本发明具有以下有益效果:
本发明的有机材料组合物通过至少一种式(1)所示结构的化合物和至少一种式(2)所示结构的化合物的配合,能提高主体材料的电子传输特性,进一步提高电子和空穴结合率,从而提高有机电致发光二极管的发光效率,延长使用寿命。
附图说明
图1为本发明应用例提供的有机电致发光器件的结构示意图,其中1为阳极,2为空穴注入层,3为空穴传输层,4为发光层,5为电子传输层,6为电子注入层,7为阴极。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了,所述实施例仅仅是帮助理解本发明,不应视为对本发明的具体限制。
制备实施例
1B的合成:25毫升三颈瓶中投入1A(10mmol),硝基苯(10mmol),氢氧化钾(22mmol)和硫氰酸亚铜(1mmol),无水四氢呋喃(10毫升),氮气置换三次,氮气保护下加热至90摄氏度,48小时后反应结束,加水淬灭,体系用乙酸乙酯萃取,旋转蒸发除去有机溶剂。粗产物用柱层析分离(乙酸乙酯:正己烷(体积比1:50)),得1B(1.34克,产率49%)。
1B’的合成:50毫升三颈瓶中投入2-溴-4-氯苯甲醛(10mmol)、联硼酸频那醇酯(12mmol),乙酸钾(100mmol),[1,1'-双(二苯基膦基)二茂铁]二氯化钯(0.2mmol),1,-二氧六环(25毫升),氮气置换,氮气保护下加热至100摄氏度,反应结束后加水淬灭,用二氯甲烷萃取,粗产物用柱层析分离(二氯甲烷:正己烷(体积比1:50)),得1B’(1.7克,产率64%)
1C的合成:50毫升三颈瓶中投入1B(10mmol),1B’(10mmol)、碳酸氢纳(20mmol),四三苯基膦钯(0.2mmol),四氢呋喃(20毫升),水(10毫升),氮气置换,氮气保护下加热至60摄氏度过夜反应。反应结束后,加水淬灭,二氯甲烷萃取,旋转蒸发除去有机溶剂,粗产物用柱层析分离(乙酸乙酯:正己烷(体积比1:50)),得1C(3.06克,产率92%)。
1D的合成:50毫升三颈瓶中,投入1C(10mmol),(甲氧基甲基)三苯基氯化膦(20mmol),四氢呋喃(10毫升),温度降至0摄氏度,将叔丁醇钾(2mmol)溶于5毫升四氢呋喃中,氮气置换,在氮气保护下,0摄氏度条件下滴加叔丁醇钾溶液,滴加完成后,搅拌反应半小时。反应结束后,加水淬灭,二氯甲烷萃取,旋转蒸发除去有机溶剂,粗产物用柱层析分离(乙酸乙酯:正己烷(体积比1:50)),得1D(1.8克,产率50%)。
1E的合成:25毫升三颈瓶中,投入1E(1mmol),六氟异丙醇(5毫升),降温至0摄氏度,氮气置换,氮气保护下滴加三氟甲磺酸(1毫升),继续搅拌反应半小时,粗产物用柱层析分离(乙酸乙酯:正己烷(体积比1:50)),得1E(0.24克,产率73%)。
1F的合成:50毫升三颈圆底瓶中,投入1E(10mmol),联硼酸频那醇酯(12mmol),乙酸钠(20mmol)、三(二亚苄基丙酮)二钯(0.5mmol)和2-双环己基膦-2',6'-二甲氧基联苯(1.5mmol),再加入1,4-二氧六环(20毫升),氮气置换三次。在氮气保护的条件下,加热至100℃反应,反应结束后,加水淬灭,二氯甲烷萃取,旋转蒸发除去有机溶剂,粗产物用柱层析分离(乙酸乙酯:正己烷(体积比1:50)),得1F(3.24克,产率77%)。
化合物1的合成:取100毫升三颈圆底瓶并放入搅拌子与上接回流管,干燥后充入氮气,分别加入1F(10mmol),1G(10mmol,CAS1689576-03-1),碳酸氢钠(23mmol)、四三苯基膦钯(0.5mmol)、二氯二叔丁基-(4-二甲基氨基苯基)磷钯(0.5mmol)、甲苯(25毫升)、乙醇(7毫升)和水(7毫升),氮气置换三次。在氮气保护的条件下,升温至80℃反应8小时,反应结束后经乙酸乙酯萃取,所得到的萃取液依序加入硫酸镁干燥、过滤及旋干;粗产物以层析纯化(乙酸乙酯:正己烷(体积比1:10)),得化合物1(4.13克,产率69%)。
元素分析:C41H26N6理论值:C,81.71;H,4.35;N,13.94;实测值:C,81.78;H,4.33;N,13.89;HRMS(ESI)m/z[M+H]+:理论值:602.22;实测值:603.40。
1B”的合成:同1B’的合成,区别在于用2-溴-5-氯苯甲醛替代2-溴-4-氯苯甲醛,得1B”(1.60克,产率60%)。
10C的合成:同1C的合成,区别在于用4-氯-2醛基苯硼酸频那醇酯替代5-氯-2醛基苯硼酸频那醇酯,得10C(2.13克,产率64%)。
10D的合成:同1D的合成,区别在于用10C替代1C,得10D(3.21克,产率89%)。
10E的合成:同1E的合成,区别在于用10D替代1D,得10E(0.16克,产率48%)。
10F的合成:同1F的合成,区别在于用10E替代1E,得10F(4.00克,产率95%)。
10的合成:同化合物1的合成,区别在于用10F替代1F,10G替代1G,得化合物10(4.70克,产率78%)。
元素分析:C41H26N6理论值:C,81.71;H,4.35;N,13.94;实测值:C,81.73;H,4.37;N,13.90;HRMS(ESI)m/z(M+):理论值:602.22;实测值:603.29。
通过表1中的原料1和原料2为原料,参照如上所述方法制备得到相应产物如表1中所示,产物的结构表征数据如表2所示。
表1
表2
1’的合成:在25毫升的三颈烧瓶中,通入氮气,加入1'-A(1mmol)、化合物1'-B(1mmol)、叔丁醇钠(2mmol)、三(二亚苄基丙酮)二钯(0)(0.02mmol),50%三叔丁基膦溶液(0.1mmol)和甲苯8mL,然后回流搅拌。反应结束后冷却至室温,用乙酸乙酯和H2O萃取有机层。萃取的有机层经MgSO4干燥,并过滤。将滤液减压浓缩,粗产物用柱层析分离(乙酸乙酯:正己烷(体积比1:50)),得化合物1'(0.40克,收率:62%)。
元素分析:C48H31N3理论值:C,88.72;H,4.81;N,6.47;实测值:C,88.76;H,4.79;N,6.45;HRMS(ESI)m/z[M+H]+:理论值:649.25;实测值:650.33。
通过表3中的原料1和原料2为原料,参照如上所述方法制备得到相应产物如表3中所示,产物的结构表征数据如表4所示。
表3
表4
应用实施例
提供一种有机电致发光器件,结构如图1所示,其具有以下层结构:基底(氧化铟锡(ITO,作为阳极1)涂层玻璃基板)/空穴注入层2(HIL)/空穴传输层3(HTL)/发光层4(EML)/电子传输层5(ETL)/电子注入层6(EIL),且最后是阴极7。
制造OLED所需的材料如下:
上述有机电致发光器件的制备包括如下步骤:
(1)基板清理:将涂布了透明ITO的玻璃基板在水性清洗剂(所述水性清洗剂的成分及浓度:乙二醇类溶剂≤10wt%,三乙醇胺≤1wt%)中超声处理,在去离子水中冲洗,在丙酮:乙醇混合溶剂(体积比1:1)中超声除油,在洁净环境下烘烤至完全除去水份,然后用紫外光和臭氧清洗。
(2)蒸镀有机发光功能层:
把上述带有阳极层的玻璃基板置于真空腔内,抽真空至1×10-6至2×10-4Pa,在上述阳极层膜上真空蒸镀NDP-9与HT的混合物,其中NDP-9与HT的质量比为3:97,作为空穴注入层,蒸镀厚度为10nm;
在空穴注入层上蒸镀空穴传输层,蒸镀膜厚为80nm;
在空穴传输层上蒸镀发光层,具体制备方法为:以共蒸的方式真空蒸镀发光主体材料(所用材料见表5)和客体材料,蒸镀总膜厚为30nm;
在电子缓冲层上蒸镀一层电子传输层,具体制备方法为:以共蒸的方式真空蒸镀BPhen和LiQ,蒸镀总膜厚为30nm;
在电子传输层上真空蒸镀一层电子注入层,蒸镀总膜厚为1nm;
在电子注入层上蒸镀Al,蒸镀总膜厚为80nm。
器件中各层及其材料以及厚度等参数如表5所示。
表5
器件性能测试:
仪器:器件的电流、电压、亮度、发光光谱等特性采用PR650光谱扫描亮度计和Keithley K 2400数字源表系统同步测试;
光电特性测试条件:电流密度为10mA/cm2。
寿命测试:电流密度为50mA/cm2,器件亮度下降至原始亮度的98%时记录时间(以小时计)。
器件性能测试结果如表6所示:
表6
由表6可以看出,单一主体化合物的电子和空穴传输能力不同,采用有机材料组合物,能提高电子的传输特性,进一步提高电子和空穴结合率,从而提高有机电致发光二极管的发光效率,延长使用寿命。所述有机材料组合物作为有机功能层材料时,能够使得器件具有较低的驱动电压(3.90V以下),较高的电流效率(18Cd/A以上)和较高的寿命(45h以上)。
申请人声明,本发明通过上述实施例来说明本发明的有机材料组合物及其应用,但本发明并不局限于上述实施例,即不意味着本发明必须依赖上述实施例才能实施。所属技术领域的技术人员应该明了,对本发明的任何改进,对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等,均落在本发明的保护范围和公开范围之内。
Claims (10)
1.一种有机材料组合物,所述有机材料组合物包含至少一种式1所示结构的化合物和至少一种式2所示结构的化合物,
其中,R选自氢、氘、卤素、氰基、取代或未取代的C1-C30烷基、取代或未取代的C3-C30环烷基、取代或未取代的C6-C30芳基、取代或未取代的C3-C30杂芳基,
R1选自-L1Ar1,R2选自-L2Ar2,R3选自-L3Ar3,R4选自-L4Ar4,
L1-L4各自独立选自连接键、取代或未取代的C6-C30的亚芳基、取代或未取代的C3-C30的亚杂芳基,
Ar1-Ar4各自独立选自选自氢、氘、卤素、氰基、取代或未取代的C3-C60的杂芳基;
Ar10选自取代或未取代的C6-C60芳基、取代或未取代的C3-C60的杂芳基,
L10选自连接键、取代或未取代的C6-C30的亚芳基、取代或未取代的C3-C30的亚杂芳基,
R10-R17各自独立选自氢、氘、卤素、氰基、取代或未取代的C1-C30烷基、其中一个或多个亚甲基以O原子或S原子不相邻的方式被-O-或-S-取代的C1-C30烷基、取代或未取代的C2-C30烯基、其中一个或多个亚甲基以O原子或S原子不相邻的方式被-O-或-S-取代的C2-C30烯基、取代或未取代的C7-C30芳烷基、取代或未取代的C6-C30芳基、取代或未取代的C3-C30杂芳基、取代或未取代的C4-C30杂芳烷基、取代或未取代的C3-C30环烷基、取代或未取代的C3-C30杂环烷基、取代或未取代的C3-C30环烯基、取代或未取代的C1-C30烷氧基、取代或未取代的C6-C30芳氧基,
R10-R17各自独立存在或相邻二至四者连接成环A,所述环A为取代或未取代的C6-C30的芳环、取代或未取代的C3-C30的杂芳环。
X1选自N或CRX1,X2选自N或CRX2,X3选自N或CRX3,X4选自N或CRX4,X5选自N或CRX5,
RX1-RX5各自独立选自氢、氘、氰基、取代或未取代的C1-C30烷基、取代或未取代的C3-C30环烷基、取代或未取代的C6-C30的芳基、取代或未取代的C3-C30的杂芳基,RX1-RX5各自独立存在,或相邻两者连接成环,所述环为苯环;
优选地,X1选自N,X2选自N,X3选自CRX3,X4选自CRX4,X5选自CRX5;
优选地,X1选自N,X3选自N,X2选自CRX2,X4选自CRX4,X5选自CRX5;
优选地,X1选自N,X2选自N,X3选自N,X4选自CRX4,X5选自CRX5。
优选地,式1中,所述RX1-RX5各自独立选自氢、氘、取代或未取代的如下基团:苯基、联苯基、三联苯基、萘基、菲基、蒽基、苯基取代萘基、萘基取代苯基、吡啶基、连吡啶基、二苯并呋喃基、二苯并噻吩基、咔唑基、咔唑基取代苯基、二甲基芴基、二苯基芴基、螺二芴基、二苯并呋喃取代苯基、二苯并噻吩取代苯基、二甲基芴基取代苯基、苯并咔唑基、苯并萘并呋喃基、苯并萘并噻吩基;
优选地,式1中,所述R1、R2、R3、R4至少一项选自氢;
优选地,所述R1、R2、R3、R4至少两项选自氢;
优选地,所述R1、R2、R3、R4中三项选自氢;
优选地,所述R2选自L2Ar2,R1、R3、R4均选自氢;
优选地,所述R3选自L3Ar3,R1、R2、R4均选自氢;
优选地,所述R选自取代或未取代的如下基团:苯基、联苯基;
优选地,L1-L4各自独立选自连接键、取代或未取代的如下基团:亚苯基、亚萘基、亚联苯基、亚三联苯基。
5.根据权利要求1-4中任一项所述的有机材料组合物,其特征在于,式2中,所述环A为取代或未取代的苯环;
优选地,式2所示结构的化合物为具有如下任一种结构的化合物:
优选地,所述环A为取代或未取代的茚环、吲哚环、苯并呋喃环、萘并呋喃环、苯并噻吩环、萘并噻吩环、苯并吲哚环、萘并吲哚环;
Y选自O,S,CRY5RY6、NLY7RY7,
RY1、RY2、RY3、RY4各自独立选自氢、氘、卤素、氰基、取代或未取代的C1-C30烷基、其中一个或多个亚甲基以O原子或S原子不相邻的方式被-O-或-S-取代的C1-C30烷基、取代或未取代的C7-C30芳烷基、取代或未取代的C6-C30芳基、取代或未取代的C3-C30杂芳基、取代或未取代的C4-C30杂芳烷基、取代或未取代的C3-C30环烷基、取代或未取代的C3-C30杂环烷基、取代或未取代的C3-C30环烯基、取代或未取代的C1-C30烷氧基、取代或未取代的C6-C30芳氧基,
RY1、RY2、RY3、RY4各自独立存在或相邻两者连接成苯环或萘环,
RY5、RY6各自独立选自取代或未取代的C1-C30烷基、取代或未取代的C6-C30芳基,
RY7选自取代或未取代的C1-C30烷基、取代或未取代的C7-C30芳烷基、取代或未取代的C6-C30芳基、取代或未取代的C3-C30杂芳基、取代或未取代的C4-C30杂芳烷基、取代或未取代的C3-C30环烷基、取代或未取代的C3-C30杂环烷基、取代或未取代的C6-C30芳氧基,
LY7连接键、取代或未取代的C6-C30的亚芳基、取代或未取代的C3-C30的亚杂芳基。
6.根据权利要求1-5中任一项所述的有机材料组合物,其特征在于,式2所示结构的化合物为具有如下任一种结构的化合物:
优选地,Ar10、RY7各自独立选自取代或未取代的如下基团:苯基、联苯基、三联苯基、萘基、苯基取代萘基、萘基取代苯基、蒽基、菲基、苯并菲基、吡啶基、二苯并呋喃基、二苯并噻吩基、咔唑基、苯基取代咔唑基、吡啶基取代咔唑基、萘基取代咔唑基、联苯基取代咔唑基、二苯并呋喃取代苯基、二苯并噻吩取代苯基、二甲基芴基、二苯基取代芴基、螺二芴基、苯并萘并呋喃基、苯并萘并噻吩基、苯并咔唑基、二苯并咔唑基;
优选地,R10-R17、RY1-RY4各自独立选自氢、氘、苯基、联苯基、三联苯基、萘基、苯基取代萘基、萘基取代苯基、蒽基、菲基、苯并菲基、吡啶基、二苯并呋喃基、二苯并噻吩基、二苯并呋喃取代苯基、二苯并噻吩取代苯基、二甲基芴基、二苯基取代芴基、螺二芴基、苯并萘并呋喃基、苯并萘并噻吩基,R10-R17、RY1-RY4各自独立存在或相邻两者连接形成苯环或萘环;
优选地,RY5、RY6各自独立选自甲基、苯基,或RY5、RY6连接形成芴基;
优选地,L10、LY7各自独立选自连接键、亚苯基、亚联苯基、亚萘基;
其中波浪线代表基团的连接位点。
优选地,所述基团带有取代基时,所述取代基各自独立选自氘、卤素、氰基、硝基、未取代或R'取代的C1~C4直链或支链烷基、未取代或R'取代的C6~C20芳基、未取代或R'取代的C3~C20杂芳基、C6~C20芳胺基;R'选自氘、卤素、氰基或硝基;
优选地,所述芳基选自苯基、联苯基、三联苯基、萘基、蒽基、菲基、苯并菲基、萘基取代苯基、二甲基芴基、二苯基取代芴基或螺二芴基;
优选地,所述杂芳基选自吡啶基、二苯并呋喃基、二苯并噻吩基、咔唑基、苯基取代咔唑基、吡啶基取代咔唑基、萘基取代咔唑基、联苯基取代咔唑基、二苯并呋喃取代苯基、二苯并噻吩取代苯基、苯并萘并呋喃基、苯并萘并噻吩基、苯并咔唑基或二苯并咔唑基;
优选地,所述烷基选自甲基、乙基、丙基、叔丁基、环己烷基或金刚烷基;
优选地,式2所示结构的化合物选自如下化合物:
优选地,所述式1所示结构的化合物和式2所示结构的化合物的重量比为1:9-9:1,优选2:8-8:2,更优选地3:7-7:3,进一步优选4:6-6:4。
7.一种有机电致发光材料,其特征在于,所述有机电致发光材料包括如权利要求1-6中任一项所述的有机材料组合物。
8.根据权利要求1-6中任一项所述的有机材料组合物或权利要求7所述的有机电致发光材料在制备光学器件中的应用。
9.一种有机电致发光器件,其特征在于,所述有机电致发光器件包括阳极和阴极,和设置在阳极和阴极间的有机层,所述有机层包括如权利要求1-6中任一项所述的有机材料组合物或如权利要求7所述的有机电致发光材料;
优选地,所述有机层包括从阳极侧到阴极侧依次层叠设置的空穴注入层、空穴传输层、发光层、电子传输层和电子注入层;
优选地,所述发光层的材料包含主体材料和客体材料,所述主体材料包含如权利要求1-6中任一项所述的有机材料组合物或如权利要求7所述的有机电致发光材料;
优选地,所述客体材料包括磷光掺杂剂,所述磷光掺杂剂包括含过渡金属的配合物。
10.一种有机电致发光设备,其特征在于,所述有机电致发光设备包括如权利要求9所述的有机电致发光器件。
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| CN117143102A (zh) * | 2023-07-13 | 2023-12-01 | 长春海谱润斯科技股份有限公司 | 一种稠合环并吲哚并咔唑化合物及其有机电致发光器件 |
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| US20230134923A1 (en) | 2023-05-04 |
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| JP2023048144A (ja) | 2023-04-06 |
| DE102022124379A1 (de) | 2023-03-30 |
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