CN104662025A - Novel thieno-indole derivative and organic electroluminescent element using said derivative - Google Patents
Novel thieno-indole derivative and organic electroluminescent element using said derivative Download PDFInfo
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- CN104662025A CN104662025A CN201380047944.8A CN201380047944A CN104662025A CN 104662025 A CN104662025 A CN 104662025A CN 201380047944 A CN201380047944 A CN 201380047944A CN 104662025 A CN104662025 A CN 104662025A
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- CN
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- Prior art keywords
- thieno
- indole derivatives
- layer
- carbonatoms
- general formula
- Prior art date
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- KWQMJXZUGBNSOY-UHFFFAOYSA-N 1h-thieno[2,3-g]indole Chemical class C1=C2SC=CC2=C2NC=CC2=C1 KWQMJXZUGBNSOY-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 238000002347 injection Methods 0.000 claims abstract description 32
- 239000007924 injection Substances 0.000 claims abstract description 32
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 239000010410 layer Substances 0.000 claims description 118
- 125000004432 carbon atom Chemical group C* 0.000 claims description 37
- 230000005540 biological transmission Effects 0.000 claims description 35
- 238000005401 electroluminescence Methods 0.000 claims description 16
- 239000012044 organic layer Substances 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 125000003545 alkoxy group Chemical group 0.000 claims description 13
- 230000004888 barrier function Effects 0.000 claims description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 12
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 10
- 125000004104 aryloxy group Chemical group 0.000 claims description 9
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 9
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 125000004429 atom Chemical group 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 7
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 125000001153 fluoro group Chemical group F* 0.000 claims description 7
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 7
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 54
- 150000001875 compounds Chemical class 0.000 abstract description 48
- 230000000903 blocking effect Effects 0.000 abstract description 14
- 239000010409 thin film Substances 0.000 abstract description 7
- 230000005525 hole transport Effects 0.000 abstract description 4
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 abstract 1
- -1 aromatic amines compound Chemical class 0.000 description 42
- 239000002585 base Substances 0.000 description 36
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 125000003118 aryl group Chemical group 0.000 description 15
- 239000010408 film Substances 0.000 description 13
- 230000027756 respiratory electron transport chain Effects 0.000 description 12
- 229940125773 compound 10 Drugs 0.000 description 10
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 10
- 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 10
- 150000003254 radicals Chemical class 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 239000004327 boric acid Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000004020 luminiscence type Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 125000001246 bromo group Chemical group Br* 0.000 description 5
- 150000001716 carbazoles Chemical group 0.000 description 5
- 238000010276 construction Methods 0.000 description 5
- 150000004696 coordination complex Chemical class 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthene Chemical compound C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 5
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000007670 refining Methods 0.000 description 5
- 229930192474 thiophene Natural products 0.000 description 5
- WGFNXGPBPIJYLI-UHFFFAOYSA-N 2,6-difluoro-3-[(3-fluorophenyl)sulfonylamino]-n-(3-methoxy-1h-pyrazolo[3,4-b]pyridin-5-yl)benzamide Chemical compound C1=C2C(OC)=NNC2=NC=C1NC(=O)C(C=1F)=C(F)C=CC=1NS(=O)(=O)C1=CC=CC(F)=C1 WGFNXGPBPIJYLI-UHFFFAOYSA-N 0.000 description 4
- LNUFLCYMSVYYNW-ZPJMAFJPSA-N [(2r,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[[(3s,5s,8r,9s,10s,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-3-yl]oxy]-4,5-disulfo Chemical compound O([C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1C[C@@H]2CC[C@H]3[C@@H]4CC[C@@H]([C@]4(CC[C@@H]3[C@@]2(C)CC1)C)[C@H](C)CCCC(C)C)[C@H]1O[C@H](COS(O)(=O)=O)[C@@H](OS(O)(=O)=O)[C@H](OS(O)(=O)=O)[C@H]1OS(O)(=O)=O LNUFLCYMSVYYNW-ZPJMAFJPSA-N 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 229940054051 antipsychotic indole derivative Drugs 0.000 description 4
- 150000004982 aromatic amines Chemical class 0.000 description 4
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 4
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 4
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical group C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 125000001302 tertiary amino group Chemical group 0.000 description 4
- 125000001544 thienyl group Chemical group 0.000 description 4
- 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 description 3
- 229940126062 Compound A Drugs 0.000 description 3
- 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 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 3
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 3
- 238000005893 bromination reaction Methods 0.000 description 3
- OMFXVFTZEKFJBZ-HJTSIMOOSA-N corticosterone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OMFXVFTZEKFJBZ-HJTSIMOOSA-N 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 3
- 125000002541 furyl group Chemical group 0.000 description 3
- 125000001072 heteroaryl group Chemical group 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 3
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 3
- 150000004322 quinolinols Chemical class 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 150000003513 tertiary aromatic amines Chemical group 0.000 description 3
- 150000003577 thiophenes Chemical class 0.000 description 3
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- VVCMGAUPZIKYTH-VGHSCWAPSA-N 2-acetyloxybenzoic acid;[(2s,3r)-4-(dimethylamino)-3-methyl-1,2-diphenylbutan-2-yl] propanoate;1,3,7-trimethylpurine-2,6-dione Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O.CN1C(=O)N(C)C(=O)C2=C1N=CN2C.C([C@](OC(=O)CC)([C@H](C)CN(C)C)C=1C=CC=CC=1)C1=CC=CC=C1 VVCMGAUPZIKYTH-VGHSCWAPSA-N 0.000 description 2
- ZZPNDIHOQDQVNU-UHFFFAOYSA-N 2-hydroxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound CC1(C)OB(O)OC1(C)C ZZPNDIHOQDQVNU-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- JQUCWIWWWKZNCS-LESHARBVSA-N C(C1=CC=CC=C1)(=O)NC=1SC[C@H]2[C@@](N1)(CO[C@H](C2)C)C=2SC=C(N2)NC(=O)C2=NC=C(C=C2)OC(F)F Chemical compound C(C1=CC=CC=C1)(=O)NC=1SC[C@H]2[C@@](N1)(CO[C@H](C2)C)C=2SC=C(N2)NC(=O)C2=NC=C(C=C2)OC(F)F JQUCWIWWWKZNCS-LESHARBVSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 description 2
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003609 aryl vinyl group Chemical group 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 125000004623 carbolinyl group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000006880 cross-coupling reaction Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002475 indoles Chemical class 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
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- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
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- 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
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 125000005561 phenanthryl group Chemical group 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 2
- 125000003226 pyrazolyl group Chemical group 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 125000001725 pyrenyl group Chemical group 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 150000003921 pyrrolotriazines Chemical class 0.000 description 2
- 125000005493 quinolyl group Chemical group 0.000 description 2
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 2
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
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- 239000011593 sulfur Substances 0.000 description 2
- WGLLSSPDPJPLOR-UHFFFAOYSA-N tetramethylethylene Natural products CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 description 2
- 125000005259 triarylamine group Chemical group 0.000 description 2
- 150000003852 triazoles Chemical class 0.000 description 2
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 239000003205 fragrance Substances 0.000 description 1
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- 230000009477 glass transition Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
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- 238000005304 joining Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
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- 239000000203 mixture Substances 0.000 description 1
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000005186 naphthyloxy group Chemical group C1(=CC=CC2=CC=CC=C12)O* 0.000 description 1
- 150000005054 naphthyridines Chemical class 0.000 description 1
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000007978 oxazole derivatives Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 150000005041 phenanthrolines Chemical class 0.000 description 1
- BOTNYLSAWDQNEX-UHFFFAOYSA-N phenoxymethylbenzene Chemical compound C=1C=CC=CC=1COC1=CC=CC=C1 BOTNYLSAWDQNEX-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 208000007578 phototoxic dermatitis Diseases 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 150000003220 pyrenes Chemical class 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 150000003252 quinoxalines Chemical class 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical class [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- YYMBJDOZVAITBP-UHFFFAOYSA-N rubrene Chemical compound C1=CC=CC=C1C(C1=C(C=2C=CC=CC=2)C2=CC=CC=C2C(C=2C=CC=CC=2)=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 YYMBJDOZVAITBP-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003967 siloles Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- JLAVCPKULITDHO-UHFFFAOYSA-N tetraphenylsilane Chemical compound C1=CC=CC=C1[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 JLAVCPKULITDHO-UHFFFAOYSA-N 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 150000007979 thiazole derivatives Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- DETFWTCLAIIJRZ-UHFFFAOYSA-N triphenyl-(4-triphenylsilylphenyl)silane Chemical compound C1=CC=CC=C1[Si](C=1C=CC(=CC=1)[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 DETFWTCLAIIJRZ-UHFFFAOYSA-N 0.000 description 1
- 125000006617 triphenylamine group Chemical group 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
- H10K50/155—Hole transporting layers comprising dopants
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/18—Carrier blocking layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/18—Carrier blocking layers
- H10K50/181—Electron blocking layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract
This thieno-indole derivative is represented by general formula (1). In general formula (1), Ar1 is an aromatic hydrocarbon group, at least one of X1 and X2 is a group having an aromatic tertiary amino structure, and the other groups can be hydrogen atoms. This compound has, in connection with an aromatic tertiary amino structure being introduced to a thieno-indole ring structure, (A) good hole injection characteristics, (B) high hole mobility, (C) excellent electron blocking capability, (D) stable thin film state, and (E) excellent heat resistance; and is useful as a hole transport material to be used in organic electroluminescent elements.
Description
Technical field
The present invention relates to the novel cpd (thieno-indole derivatives) being suitable for organic electroluminescence device and the organic electroluminescence device possessing the organic layer comprising this compound, described organic electroluminescence device is the selfluminous element being suitable for various display unit.
Background technology
Organic electroluminescence device (hereinafter sometimes referred to organic EL device) is self-luminosity device, therefore becomes clear than liquid crystal device and visual excellence, can show clearly, so carried out positive research to it.
In 1987, the C.W.Tang of Eastman Kodak Company etc. by developing the stepped construction device of various functional distribution to each material, thus will use the organic EL device of organic materials to drop into practical application.This stepped construction device be by can transmission electronic fluor with can the aromatic amines compound of transporting holes stacked and forms, by it will be made in two kinds of charge injections to the layer of fluor luminous, can with the voltage of below 10V acquisition 1000cd/m
2above high brightness.
Up to now, many improvement have been carried out in order to the practical of organic EL device.Such as, by further for various effect sectionalization is disposed with the electroluminescent device of anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, negative electrode on substrate, thus high-level efficiency and weather resistance is achieved.
In addition, in order to improve luminous efficiency further, attempting utilizing triplet exciton, have studied the utilization of phosphorescent emitter.
Further, also developed the device utilizing the luminescence brought by thermal activities delayed fluorescence (TADF).In 2011, the Anda of Kyushu University etc. by employ thermal activities delayed fluorescence material device and achieve 5.3% external quantum efficiency (such as with reference to non-patent literature 1).
Luminescent layer also can be made by doping fluorescent body in the charge-transporting compound being commonly called material of main part, phosphorescent emitter.The each characteristic such as efficiency, weather resistance of selection to this device of the organic materials in organic EL device makes a big impact.
In organic EL device, combine again luminescent layer from the electric charge of two electrode injections and realize luminescence, but importantly how efficiently hole, these two kinds of electric charges of electronics being received in luminescent layer.Such as, by improving hole injection, improving injecting the electronic blocking stopped from the electronics of negative electrode, thus improve hole and the probability that electronics is combined again, be enclosed in the exciton generated in luminescent layer further, can high-luminous-efficiency be obtained thus.Therefore, the effect that hole mobile material plays is important, is seeking the hole mobile material that hole injection is high, hole mobility large, electronic blocking is high and then high to the weather resistance of electronics.
In addition, about the life-span of device, the thermotolerance of material, amorphism are also important.For the material that thermotolerance is low, due to the heat generated during device drive, even if also can thermolysis be caused at low temperatures, material degradation.For the material that amorphism is low, even if the crystallization of film also can be caused at short notice, device degradation.Therefore, for the character that material requirements thermotolerance is high, amorphism is good used.
As the hole mobile material used in organic EL device, there will be a known N, N '-phenylbenzene-N, N '-two (Alpha-Naphthyl) p-diaminodiphenyl (later referred to as NPD), various aromatic amine derivative (such as with reference to patent documentation 1 and patent documentation 2).
NPD has good cavity transmission ability, but the second-order transition temperature (Tg) of index as thermotolerance is low to moderate 96 DEG C, causes the reduction (such as with reference to non-patent literature 2) of device property under the high temperature conditions because of crystallization.
In addition, in patent documentation 1, aromatic amine derivative described in patent documentation 2, the mobility that there is hole is 10
-3cm
2the compound of the excellent mobility of/more than Vs, but because electronic blocking is insufficient, thus a part for electronics is through luminescent layer, can not expect the raising etc. of luminous efficiency, in order to realize more high efficiency, pursuit electronic blocking is higher, film is more stable and the material that thermotolerance is high.
As the compound improving the characteristic such as thermotolerance, hole injection, propose in patent documentation 3 and 4 represent by following formula, there is the aromatic amine compound A of substituted thiophene diindyl structure and there is the aromatic amine compound B of substituted carbazole structure.
In addition, Patent Document 5 discloses the aromatic amine compound C with substituted thiophene diindyl structure shown in following formula, propose as organic transistor due to its mobility and stability.
But, for compd A and B being used for the device of hole injection layer or hole transmission layer, although luminous efficiencies etc. are improved, but can't say it is sufficient, in addition, lower voltage, current efficiency can not say it is sufficient, and seeking can the compound of high-luminous-efficiency further.
In addition, still there is not the example substituted thiophene diindyl derivative of Compound C and so on being used for organic EL device, not yet confirm for its validity yet.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 8-48656 publication
Patent documentation 2: Japanese Patent No. 3194657 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2010-205815 publication
Patent documentation 4:WO2008/62636 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2010-205982 publication
Non-patent literature
Non-patent literature 1:Appl.Phys.Let., 98,083302 (2011)
Non-patent literature 2: organic EL discussion third time regular meeting pre-original text collection 13rd ~ 14 pages (2006)
Summary of the invention
the problem that invention will solve
Therefore, the object of the invention is to, novel organic compound is provided, it can be suitably used as the material of organic electroluminescence device for making high-level efficiency, high-durability, the injection in hole/transmission performance is excellent, have electron-blocking capability, and stability under filminess is high and then thermotolerance is also excellent.
Other object of the present invention is, provides the organic electroluminescence device possessing the organic layer comprising above-mentioned organic compound.
for the scheme of dealing with problems
The present inventor etc. are conceived to aromatic nitrile base structure has high hole injection/transmittability, thieno-indole ring structures has electronic blocking and then this part-structure has thermotolerance, thin film stability is good, design has the various compound of thieno-indole ring structures and carries out chemosynthesis, this compound is used to manufacture experimently various organic electroluminescence device, deeply carry out the evaluating characteristics of device, found that, high-level efficiency and excellent weather resistance can be obtained, thus complete the present invention.
According to the present invention, provide the thieno-indole derivatives shown in following general formula (1).
In formula,
Ar
1represent aromatic hydrocarbyl or aromatic heterocycle,
R
1~ R
4be respectively hydrogen atom, D atom, fluorine atom, chlorine atom, cyano group, nitro, the alkyl of carbonatoms 1 ~ 6, the cycloalkyl of carbonatoms 5 ~ 10, the thiazolinyl of carbonatoms 2 ~ 6, the alkoxyl group of carbonatoms 1 ~ 6, the cycloalkyloxy of carbonatoms 5 ~ 10, aromatic hydrocarbyl, aromatic heterocycle or aryloxy, R
1~ R
3can via singly-bound, optionally there is substituent methylene radical, Sauerstoffatom or sulphur atom and bond together and form ring,
X
1and X
2under at least any one condition for 1 valency group shown in following structural formula (2), be respectively hydrogen atom, D atom, fluorine atom, chlorine atom, cyano group, nitro, the alkyl of carbonatoms 1 ~ 6, the cycloalkyl of carbonatoms 5 ~ 10, the thiazolinyl of carbonatoms 2 ~ 6, the alkoxyl group of carbonatoms 1 ~ 6, the cycloalkyloxy of carbonatoms 5 ~ 10, aromatic hydrocarbyl, aromatic heterocycle or aryloxy or 1 valency group shown in following structural formula (2).
In formula,
A
1represent the aromatic hydrocarbyl of divalent, the aromatic heterocycle of divalent or singly-bound,
Ar
2and Ar
3represent aromatic hydrocarbyl or aromatic heterocycle respectively, Ar
2with Ar
3can via singly-bound, optionally there is substituent methylene radical, Sauerstoffatom or sulphur atom and bond together and form ring, A
1during aromatic hydrocarbyl for divalent, A
1with Ar
2can via singly-bound, optionally there is substituent methylene radical, Sauerstoffatom or sulphur atom and bond together and form ring.
According to the present invention, provide organic electroluminescence devices in addition, it is characterized in that, have in pair of electrodes and the organic electroluminescence device of at least one deck organic layer that clamps therebetween,
At least 1 layer of aforementioned organic layer comprises aforementioned thieno-indole derivatives.
And then, in organic EL device of the present invention, as the aforementioned organic layer comprising thieno-indole derivatives, such as, there is hole transmission layer, electronic barrier layer, hole injection layer or luminescent layer.
the effect of invention
Being novel compound with the thieno-indole derivatives that aforementioned formula (1) represents, by having imported the structure of the tertiary amino of aromatic series (the fragrant race of di-substituted aryl is amino) in thieno-indole ring, there is characteristic as following.
(A) injection properties in hole is good.
(B) mobility in hole is large.
(C) electron-blocking capability is excellent.
(D) filminess is stablized.
(E) excellent heat resistance.
Therefore, thieno-indole derivatives of the present invention is useful as the hole transport ability material used in organic EL device, and filminess is stablized, therefore, especially be used as the organic layer arranged in organic EL device, following such characteristic can be given to organic EL device.
(F) luminous efficiency, electrical efficiency are high.
(G) luminous starting voltage is low.
(H) practical driving voltage is low.
(I) device lifetime long (display high-durability).
Such as, use thieno-indole derivatives of the present invention and define that the injection/mobility in the hole of the organic EL device of hole injection layer and/or hole transmission layer is fast, electronic blocking is high and high to the stability of electronics, therefore, it is possible to be enclosed in generate in luminescent layer exciton, improve probability that hole is combined with electronics again further, can high-luminous-efficiency be obtained, and driving voltage reduction, the raising of weather resistance can be realized.
In addition, in the organic EL device with the electronic barrier layer employing thieno-indole derivatives of the present invention, by the electron-blocking capability of excellence and excellent hole transport ability, have high-luminous-efficiency and driving voltage is low, electric current patience improves, maximum luminousing brightness is improved.
And then, thieno-indole derivatives of the present invention is compared with current material, also there is hole transport ability excellence and this characteristic of band gap length, therefore, it is possible to be used as the material of main part of luminescent layer, the fluorescent illuminant such as making it support to be called as hotchpotch, phosphorescent emitter, to be used as luminescent layer, can to reduce the driving voltage of organic EL device, improve luminous efficiency.
Especially, among thieno-indole derivatives of the present invention, the A especially in structural formula (2)
1with Ar
2as shown in aftermentioned embodiment 3 and 4, not only second-order transition temperature is high, thin film stability is excellent to define the type (such as compound 18 described later etc.) of ring, and work function also large, cavity transmission ability is good especially.
Like this, thieno-indole derivatives of the present invention is exceedingly useful as the constituent material of the hole injection layer of organic EL device, hole transmission layer, electronic barrier layer or luminescent layer, electron-blocking capability is excellent, filminess is stable, excellent heat resistance, can improve luminous efficiency and electrical efficiency, the practical driving voltage of reduction of organic EL device, reduces luminous starting voltage, improve weather resistance.
Accompanying drawing explanation
Fig. 1 is the compound (compound 10) of embodiment 1
1h-NMR spectrogram.
Fig. 2 is the compound (compound 18) of embodiment 2
1h-NMR spectrogram.
Fig. 3 is the figure of an example of the Rotating fields that organic EL device is shown.
Embodiment
Thieno-indole derivatives of the present invention following general formula (1) represents, has and be bonded with at least one tertiary amino (-NAr of aromatic series shown in aftermentioned structural formula (2) on thieno-indole ring
2ar
3) structure.
< group Ar
1>
In above-mentioned general formula (1), be bonded to the Ar of the nitrogen-atoms of thieno-indole ring
1represent aromatic hydrocarbyl or aromatic heterocycle.Described aromatic hydrocarbyl or aromatic heterocycle can have single ring architecture, also can have fused polycyclic ring structure.
As the example of these aromatic groups, phenyl, xenyl, terphenyl, naphthyl, anthryl, phenanthryl, fluorenyl, indenyl, pyrenyl, perylene base, fluoranthene base, benzo phenanthryl, pyridyl, furyl, pyrryl, thienyl, quinolyl, isoquinolyl, benzofuryl, benzothienyl, indyl, carbazyl, benzoxazolyl, benzothiazolyl, quinoxalinyl, benzimidazolyl-, pyrazolyl, dibenzofuran group, dibenzothiophene base and carbolinyl etc. can be listed.
In addition, in above-mentioned aromatic group, as aromatic heterocycle, be preferably the sulfur-containing aromatic heterocyclic radicals such as thienyl, benzothienyl, benzothiazolyl, dibenzothiophene base; Furyl, benzofuryl, benzoxazolyl, dibenzofuran group etc. are containing oxygen aromatic heterocycle.
Above-mentioned aromatic series base optionally has substituting group.As these substituting groups, D atom can be listed; Cyano group; Nitro; The halogen atoms such as fluorine atom, chlorine atom, bromine atoms, atomic iodine; The straight-chain of the carbonatomss 1 ~ 6 such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, n-hexyl or branched alkyl; The straight-chain of the carbonatomss 1 ~ 6 such as methoxyl group, oxyethyl group, propoxy-or branched alkoxyl group; The thiazolinyl such as vinyl, allyl group; The aryloxy such as phenoxy group, tolyloxy; The alkoxy aryls such as benzyloxy, benzene oxyethyl group; The aromatic hydrocarbyls such as phenyl, xenyl, terphenyl, naphthyl, anthryl, phenanthryl, fluorenyl, indenyl, pyrenyl, perylene base, fluoranthene base, benzo phenanthryl; The aromatic heterocycles such as pyridyl, thienyl, furyl, pyrryl, quinolyl, isoquinolyl, benzofuryl, benzothienyl, indyl, carbazyl, benzoxazolyl, benzothiazolyl, quinoxalinyl, benzimidazolyl-, pyrazolyl, dibenzofuran group, dibenzothiophene base, carbolinyl; The aryl vinyl such as styryl, naphthalene vinyl; The acyl group such as ethanoyl, benzoyl etc.
In addition, these substituting groups optionally have substituting group further, as its substituting group, can list and aforementioned Ar
1the substituting group that the substituting group that can have is identical.
< radicals R
1~ R
4>
In above-mentioned general formula (1), R
1~ R
4represent the cycloalkyloxy of the alkoxyl group of the thiazolinyl of the cycloalkyl of the alkyl of hydrogen atom, D atom, fluorine atom, chlorine atom, cyano group, nitro, carbonatoms 1 ~ 6, carbonatoms 5 ~ 10, carbonatoms 2 ~ 6, carbonatoms 1 ~ 6, carbonatoms 5 ~ 10, aromatic hydrocarbyl, aromatic heterocycle or aryloxy respectively.
Above-mentioned R
1~ R
4in, as the concrete example of the thiazolinyl of the cycloalkyl of the alkyl of carbonatoms 1 ~ 6, carbonatoms 5 ~ 10, carbonatoms 2 ~ 6, the alkoxyl group of carbonatoms 1 ~ 6, the cycloalkyloxy of carbonatoms 5 ~ 10, following group can be listed.In addition, abovementioned alkyl, thiazolinyl, alkoxyl group can be straight-chain, also can be branched.
Alkyl:
Methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, n-hexyl etc.
Cycloalkyl:
Cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl etc.
Thiazolinyl:
Vinyl, allyl group, pseudoallyl, crotyl etc.
Alkoxyl group:
Methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, tert.-butoxy, n-pentyloxy, positive hexyloxy, cyclopentyloxy etc.
Cycloalkyloxy:
Cyclohexyloxy, ring oxygen in heptan base, ring octyloxy, 1-Buddha's warrior attendant alkoxyl group, 2-Buddha's warrior attendant alkoxyl group etc.
Abovementioned alkyl, cycloalkyl, thiazolinyl, alkoxyl group and cycloalkyloxy also optionally have substituting group further.As this substituting group, with above-mentioned Ar
1the substituting group that shown aromatic group can have identical (wherein, except alkyl, aryl vinyl and acyl group).
Above-mentioned R
1~ R
4in aromatic hydrocarbyl, aromatic heterocycle be also and aforementioned Ar
1in the identical group of illustrative substituting group, among aromatic heterocycle, be preferably the sulfur-containing aromatic heterocyclic radicals such as thienyl, benzothienyl, benzothiazolyl, dibenzothiophene base.
Above-mentioned R
1~ R
4shown aromatic hydrocarbyl and aromatic heterocycle optionally have substituting group further.
As this substituting group, except above-mentioned Ar
1outside the substituting group that shown aromatic group can have, also trifluoromethyl can be listed; The aralkyl such as benzyl, menaphthyl, styroyl; The dialkyl amido such as dimethylamino, diethylin; The disubstituted amido that diphenyl amino, dinaphthyl amino etc. be instead of by aromatic hydrocarbyl; Two aryl alkyl aminos such as dibenzyl amino, Diphenethyl are amino; The disubstituted amido that two pridylamino, two Thenvlamino etc. be instead of by aromatic heterocycle; Diallyl amino waits dialkylamino; Be selected from the disubstituted amido that 2 kinds of substituting groups in alkyl, aromatic hydrocarbyl, aralkyl, aromatic heterocycle or thiazolinyl instead of.
As above-mentioned R
1~ R
4in aryloxy, phenoxy group, biphenylyloxy, terphenyl oxygen base, naphthyloxy, anthracene oxygen base, luxuriant and rich with fragrance oxygen base, fluorenes oxygen base, indenes oxygen base, pyrene oxygen Ji, perylene oxygen base etc. can be listed.
These aryloxy also optionally have substituting group, as this substituting group, can list and above-mentioned Ar
1the substituting group that the substituting group of shown aromatic group is identical.
Above-mentioned R
1~ R
4among, R
1~ R
3, its substituting group can bond together via singly-bound, methylene radical (optionally having the substituting groups such as methyl), Sauerstoffatom or sulphur atom and form ring.
< radicals X
1and X
2>
In above-mentioned general formula (1), X
1and X
2be respectively hydrogen atom, D atom, fluorine atom, chlorine atom, cyano group, nitro, the alkyl of carbonatoms 1 ~ 6, the cycloalkyl of carbonatoms 5 ~ 10, the thiazolinyl of carbonatoms 2 ~ 6, the alkoxyl group of carbonatoms 1 ~ 6, the cycloalkyloxy of carbonatoms 5 ~ 10, aromatic hydrocarbyl, aromatic heterocycle or aryloxy or 1 valency group, at least X shown in following structural formula (2)
1and X
2in any one be the 1 valency group (there is the group of tertiary amino structure) shown in following structural formula (2).
Group A
1:
In structure above (2), A
1represent aromatic heterocycle (remove 2 hydrogen atoms from aromatic hydrocarbons and heteroaromatic and obtain group) or the singly-bound of the aromatic hydrocarbyl of divalent, divalent.
The concrete example of the aromatic hydrocarbons ring had as above-mentioned divalent group and the ring structure of heteroaromatic, can exemplify following ring.
Aromatic hydrocarbons ring:
Benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, anthracene, acenaphthene, fluorenes, phenanthrene, indenes, pyrene.
Heteroaromatic:
Pyridine, pyrimidine, triazine, pyrroles, furans, thiophene, quinoline, isoquinoline 99.9, cumarone, thionaphthene, indoline, carbazole, carboline, benzoxazole, benzothiazole, quinoxaline, benzoglyoxaline, pyrazoles, diphenylene-oxide, dibenzothiophene, naphthyridines, phenanthroline, acridine.
In the present invention, be preferably divalent aromatic hydrocarbyl, it is particularly suitable that have the divalent aromatic hydrocarbyl of phenyl ring.
In addition, A
1shown divalent aromatic hydrocarbyl and aromatic heterocycle optionally have substituting group further, as this substituting group, can list and aforementioned Ar
1the substituting group that the substituting group that can have is identical.
And then the aromatic hydrocarbyl of above-mentioned divalent also can via optionally having substituent methylene radical, Sauerstoffatom, sulphur atom or the singly-bounds such as alkyl and aftermentioned group Ar
2bonding and form ring.Especially, the aromatic hydrocarbyl of divalent and group Ar
2bonding and form ring time, thin film stability is excellent, shows cavity transmission ability excellent especially simultaneously.As such ring, carbazole ring is representative.
Group Ar
2and Ar
3:
In structure above (2), Ar
2and Ar
3represent aromatic hydrocarbyl and aromatic heterocycle.
As the concrete example of such aromatic group (aromatic hydrocarbyl and aromatic heterocycle), the Ar with aforementioned formula (1) can be listed
1identical group.
In addition, Ar
2with Ar
3also can bond together via optionally having substituent methylene radical, Sauerstoffatom, sulphur atom or the singly-bounds such as alkyl and jointly form ring with the nitrogen-atoms of amino.
And then, A
1with Ar
2exist with the form of group independent of each other, but at A
1during aromatic hydrocarbyl for divalent, A
1with Ar
2also can bond together via singly-bound, methylene radical, Sauerstoffatom or sulphur atom and form ring.
The concrete example > of < thieno-indole derivatives
Thieno-indole derivatives of the present invention shown in above-mentioned general formula (1) has and stems from radicals X
1or X
2tertiary the amino structure (-NAr of aromatic series
2ar
3), itself and radicals X
1and X
2structure be classified as accordingly: only radicals X
2there is type (category-A), the only radicals X of structure shown in structural formula (2)
1there is type (category-B) and the radicals X of structure shown in structural formula (2)
1with X
2both all have type (C class) this three class of structure shown in structural formula (2).
The thieno-indole derivatives of category-A:
This compound following general formula (1-1) represents.
In formula,
Ar
1, R
1~ R
4, X
1, A
1, Ar
2and Ar
3(wherein, X as shown in aforementioned formula (1) and structural formula (2)
1in do not comprise the group shown in structural formula (2)).
In the present invention, among the category-A thieno-indole derivatives shown in above-mentioned general formula (1-1), 2 (adjacent carbonss of sulphur atom) being preferably the compound shown in following general formula (1a), i.e. thieno-indole ring are bonded with tertiary the amino structure (-NAr of band aromatic series
2ar
3) the compound of group.
In formula,
Ar
1~ Ar
3, R
1~ R
4, A
1and X
1as shown in aforementioned formula (1-1).
In such category-A thieno-indole derivatives, A
1with Ar
2bonding and the compound (such as latter compounds 17-19,36-38,50,55,60) defining ring is particularly suitable from the viewpoint of thin film stability, cavity transmission ability.
The thieno-indole derivatives of category-B:
This compound following general formula (1-2) represents.
In formula,
Ar
1, R
1~ R
4, X
2, A
1, Ar
2and Ar
3(wherein, X as shown in aforementioned formula (1) and structural formula (2)
2in do not comprise the group shown in structural formula (2)).
In the present invention, among the thieno-indole derivatives shown in above-mentioned general formula (1-2), 7 that are preferably the compound shown in following general formula (1b), i.e. thieno-indole ring are bonded with tertiary the amino structure (-NAr of band aromatic series
1ar
2) the compound of group.
In formula,
Ar
1~ Ar
3, R
1~ R
4, A
1and X
2as shown in aforementioned formula (1-2).
In addition, in the thieno-indole derivatives of this category-B, A
1with Ar
2bonding and the compound (such as latter compounds 42,54) defining ring is particularly suitable from the viewpoint of thin film stability, cavity transmission ability.
The thieno-indole derivatives of C class:
Radicals X in the type
1and X
2both all becomes the group (having the group of the tertiary amino structure of aromatic series) shown in structural formula (2), represents with following general formula (1-3).
In formula,
Ar
1~ Ar
3, R
1~ R
4and A
1as shown in aforementioned formula (1) and structural formula (2).
Herein, multiple A
1, Ar
2, Ar
3can be the same or different each other.
In the present invention, among the thieno-indole derivatives of the C class shown in above-mentioned general formula (1-3), preferably there is tertiary the amino structure (-NAr of aromatic series
2ar
3) group bonding in the structure of 2 (adjacent carbonss of sulphur atom) of thieno-indole ring and 7, specifically, be preferably the thieno-indole derivatives shown in following general formula (1c).
In formula,
Ar
1~ Ar
3, R
1~ R
4and A
1as shown in aforementioned formula (1-3).
In addition, in the thieno-indole derivatives of this C class, A
1with Ar
2bonding and when defining ring (such as latter compounds 16), be particularly suitable from the viewpoint of thin film stability, cavity transmission ability.
The synthesis > of < thieno-indole derivatives
Thieno-indole derivatives of the present invention is novel compound, such as, can operate as follows to synthesize.
First, the nitrogen-atoms being used in 4 as starting raw material is imported with aryl and corresponding with general formula (1) there is radicals R
1~ R
4thieno-indoles, utilize bromine, N-bromination succimide etc. to carry out bromination to this thieno-indoles, thus synthesis prescribed position (want and radicals X
1or X
2the position of bonding) be imported with the bromine substituent of bromine.Herein, by changing reagent, the condition of bromination, the different bromine substituent of the position of substitution, di-substituted can be obtained.
And then, prepare by the halogen substituents of triaryl amine and tetramethyl ethylene ketone borine, the various boric acid joining the Reactive Synthesis of boric acid pinacol ester etc. or boric acid ester (such as with reference to J.Org.Chem., 60,7508 (1995)).There is the cross-coupling reactions such as Suzuki coupling (such as with reference to Chem.Rev. by making the bromine substituent of this boric acid or boric acid ester and above-mentioned thieno-indoles, 95,2457 (1995)), thieno-indole derivatives of the present invention can be synthesized.
In addition, react with the bromine substituent of above-mentioned thieno-indoles by making tetramethyl ethylene ketone borine, connection boric acid pinacol ester etc., can synthesize and the corresponding boric acid of thieno-indole derivatives of general formula (1) or boric acid ester, make the halogen substituents of this boric acid or boric acid ester and triaryl amine that the cross-coupling reactions such as Suzuki coupling occur, thus also can synthesize thieno-indole derivatives of the present invention.
In addition, the refining of these compounds can be undertaken by refining, the refining with adsorbents based on silica gel, gac, atlapulgite etc., the recrystallize based on solvent, crystallization etc. based on column chromatography.The identification and utilization NMR of compound analyzes and carries out.
The suitable examples > of < thieno-indole derivatives
Among thieno-indole derivatives shown in above-mentioned general formula (1), the concrete example of preferred compound is shown as follows, the present invention is not limited to these compounds.
The thieno-indole derivatives of the invention described above can form compared with existing known hole mobile material second-order transition temperature (Tg), fusing point is higher, thermotolerance is more excellent film, stably can keep filminess.In addition, the blocking capability of electronics is high, and such as to use thieno-indole derivatives of the present invention to form thickness be 100nm evaporation layer also, when measuring work function, shows high value.
In thieno-indole derivatives of the present invention, category-A shows the most excellent performance as organic EL device material.
< organic EL device >
Possess and use the thieno-indole derivatives of the invention described above and the organic EL device of organic layer that formed has structure such as shown in Fig. 3.
That is, glass substrate 1 (transparent resin substrate etc. are transparency carrier) is provided with transparent anode 2, hole injection layer 3, hole transmission layer 4, luminescent layer 5, electron transfer layer 6, electron injecting layer 7 and negative electrode 8.
In any case, the organic EL device can applying thieno-indole derivatives of the present invention is not limited to above-mentioned Rotating fields, can arrange electronic barrier layer, between luminescent layer 5 and electron transfer layer 6, arrange hole blocking layer etc. between hole transmission layer 4 and luminescent layer 5.In addition, the simple Rotating fields eliminating electron injecting layer 7, hole injection layer 3 etc. can be made.Such as, in above-mentioned multilayered structure, also can omit several layer.Such as can also make the simple Rotating fields being provided with anode 2, hole transmission layer 3, luminescent layer 5, electron transfer layer 6 and negative electrode 8 on substrate 1.
That is, thieno-indole derivatives of the present invention can be suitably used as the formation material of the organic layer (such as hole injection layer 3, hole transmission layer 4, not shown electronic barrier layer or luminescent layer 5) arranged between above-mentioned anode 2 and negative electrode 8.
In above-mentioned organic EL device, transparent anode 2 is formed with per se known electrode materials, by being formed on substrate 1 transparency carriers such as () glass substrates by the large electrode materials evaporation of work function of ITO, gold and so on.
In addition, as the hole injection layer 3 arranged on transparent anode 2, the thieno-indole derivatives of the invention described above can be used to be formed, in addition, existing known material, such as following material can also be used to be formed.
Take copper phthalocyanine as the porphyrin compound of representative;
Star-like triphenylamine derivative;
The materials such as the various triphenylamine tetramers;
The Receptor heterogeneous ring compound of six cyano group azepine benzophenanthrenes and so on;
The macromolecular material of application type, such as poly-(3,4-ethylene dioxythiophene) (PEDOT), poly-(styrene sulfonate) (PSS) etc.
Use the formation of the layer (film) of above-mentioned materials except vapour deposition method, the known method such as spin-coating method, ink jet method etc. can also be utilized to carry out film forming.
The hole transmission layer 4 that above-mentioned hole injection layer 3 is arranged can use aforementioned thieno-indole derivatives of the present invention to be formed, and following such existing known hole mobile material also can be used to be formed.
Benzidine derivative, such as,
N, N '-phenylbenzene-N, N '-two (tolyl) p-diaminodiphenyl (hereinafter referred to as TPD);
N, N '-phenylbenzene-N, N '-two (Alpha-Naphthyl) p-diaminodiphenyl (hereinafter referred to as NPD);
N, N, N ', N '-tetrad phenyl p-diaminodiphenyl;
Amine system derivative
Two [4-(two-4-toluinos) phenyl] hexanaphthene (hereinafter referred to as TAPC) of 1,1-;
Various triphenylamine tripolymer and the tetramer;
Also be used as the above-mentioned application type macromolecular material of hole injection layer purposes.
The compound of this hole transmission layer can individually film forming, also can mix two or more and carry out film forming.In addition, the multilayer film that such layer is laminated to form multiple layer, and is made hole transmission layer by one or more that can also use above-claimed cpd.
In addition, also can make the layer having hole injection layer 3 and hole transmission layer 4 concurrently, this hole injection/transport layer can use the macromolecular materials such as PEDOT to be formed by being coated with.
In addition, in hole transmission layer 4 (hole injection layer 3 too), further P in this layer of normally used material also can be used to be doped with the product of tribromo phenyl chlordene ammonium antimonate etc.In addition, the macromolecular compound etc. with TPD basic framework can be used to form hole transmission layer 4 (or hole injection layer 3).
And then, the electronic barrier layer (can be arranged between luminescent layer 5 and hole transmission layer 3) be not illustrated can use the thieno-indole derivatives of the present invention with electronic blocking effect to be formed, and the compound etc. that also can use known electronic blocking compound, such as carbazole derivative, have triphenyl-silyl and have a tertiary aromatic amine structure is formed.Carbazole derivative is as follows with the concrete example of the compound with tertiary aromatic amine structure.
< carbazole derivative >
4,4 ', 4 "-three (N-carbazyl) triphenylamine (hereinafter referred to as TCTA);
Two [4-(carbazole-9-base) phenyl] fluorenes of 9,9-;
Two (carbazole-9-base) benzene (hereinafter referred to as mCP) of 1,3-;
Two (4-carbazole-9-base phenyl) diamantane (hereinafter referred to as Ad-Cz) of 2,2-;
< has the compound > of tertiary aromatic amine structure
9-[4-(carbazole-9-base) phenyl]-9-[4-(triphenyl-silyl) phenyl]-9H-fluorenes.
Can to use in thieno-benzazolyl compounds of the present invention, known hole mobile material as described above independent one kind or two or more is formed for electronic barrier layer, also one or more in these hole mobile materials can be used to form multiple layer, and the multilayer film of this layer through being laminated is made electronic barrier layer.
As the luminescent layer 5 of organic EL device, except using with Alq
3outside metal complex for the quinolinol derivative of representative, the luminescent material such as the various metal complexs of zinc, beryllium, aluminium etc., anthracene derivant, double styrene benzene derivative, pyrene derivatives, oxazole derivative, poly-phenylene vinylene (ppv) derivative can also be used to be formed.
In addition, luminescent layer 5 also can be made up of material of main part and dopant material.
As material of main part now, except thieno-indole derivatives of the present invention, on the basis of above-mentioned luminescent material, thiazole derivative, benzimidizole derivatives, poly-diakyl fluorene derivatives etc. can also be used.
As dopant material, quinacridone, tonka bean camphor, rubrene, perylene and their derivative, 1-benzopyran derivatives, Rhodamine Derivatives, aminostyrl derivative etc. can be used.
Such luminescent layer 5 also can be made the one kind or two or more individual layer employed in each luminescent material and form, and can also make the multilayered structure be laminated by multiple layer.
And then, as luminescent material, phosphorescent light-emitting materials also can be used to form luminescent layer 5.
As phosphorescent light-emitting materials, the phosphorescent emitter of the metal complex of iridium, platinum etc. can be used.Such as can use Ir (ppy)
3deng blue phosphorescent twinkler, the Btp such as blue phosphorescent twinkler, FIrpic, FIr6
2the red phosphorescent twinklers etc. such as Ir (acac), these phosphorescent light-emitting materials are entrained in the material of main part of hole injection/transporting, the material of main part of electron-transporting uses.
As the material of main part of hole injection/transporting, the carbazole derivative etc. such as thieno-indole derivatives of the present invention, 4,4 '-two (N-carbazyl) biphenyl (later referred to as CBP), TCTA, mCP can be used.
In addition, as the material of main part of electron-transporting, can use two (triphenyl-silyl) benzene (later referred to as UGH2), 2,2 '; 2 "-(1,3,5-phenylene)-three (1-phenyl-1H-benzoglyoxaline) (later referred to as TPBI) etc.
In addition, in material of main part, Doping Phosphorus photosensitiveness luminescent material is in order to avoid concentration quenching, is preferably adulterated by common evaporation relative to the overall scope with 1 ~ 30 % by weight of luminescent layer.
In addition, as luminescent material, also can use in aforementioned non-patent literature 1 and disclose the material that such CDCB derivative (such as PIC-TRZ, CC2TA, PXZ-TRZ, 4CzIPN) etc. launches delayed fluorescence.
The hole blocking layer (not shown in Fig. 3) that can be arranged between luminescent layer 5 and electron transfer layer 6 can use the per se known compound with hole barrier effect to be formed.
As this example with the known compound of hole barrier effect, except the metal complex of the quinolinol derivative such as the phenanthroline derivatives such as bathocuproine (later referred to as BCP), two (2-methyl-oxine)-4-phenylphenol aluminium (III) (later referred to as BAlq), also can list various rare earth complex, triazole derivative, pyrrolotriazine derivatives, oxadiazole derivative etc.
These materials also may be used for the electron transfer layer 6 forming the following stated, and then can also be used for this hole blocking layer and electron transfer layer 6.
This hole blocking layer also can make the stepped construction of single or multiple lift, each layer use above-mentioned have in the compound of hole barrier effect one kind or two or more come film forming.
Electron transfer layer 6 use per se known electron-transporting compound, such as with Alq
3, Balq is that the metal complex of the quinolinol derivative of representative and various metal complex, triazole derivative, pyrrolotriazine derivatives, oxadiazole derivative, thiadiazoles derivative, carbodiimide derivative, quinoxaline derivatives, phenanthroline derivative, Silole derivative etc. are formed.
This electron transfer layer 6 also can make the stepped construction of single or multiple lift, each layer use in above-mentioned electron-transporting compound one kind or two or more come film forming.
And then electron injecting layer 7 also can use the metal oxides such as alkaline earth salt, aluminum oxide etc. such as per se known material, the such as an alkali metal salt such as lithium fluoride, cesium fluoride, magnesium fluoride to be formed.
As the negative electrode 8 of organic EL device, alloy lower for the work function of electrode materials low for the work function of aluminium and so on, magnesium silver alloys, magnesium indium alloy, aluminum magnesium alloy and so on can be used as electrode materials.
Use thieno-indole derivatives of the present invention define the luminous efficiency of the organic EL device of at least one deck (such as hole injection layer 3, hole transmission layer 4, electronic barrier layer or luminescent layer 5) in organic layer and low, the luminous starting voltage of high, the practical driving voltage of electrical efficiency also low, there is extremely excellent weather resistance.
Embodiment
Below, illustrate the present invention by embodiment, but the present invention is not limited to following examples.
< embodiment 1>
The synthesis (synthesis of compound 10) of two (biphenyl-4-base)-[4-{4-(biphenyl-4-base) thieno-[3,2-b] indoles-2-base } phenyl] amine
By bromo-for 2-4-(biphenyl-4-base) thieno-[3,2-b] indoles 11.3g, two (biphenyl-4-base)-{ 4-(4,4,5,5-tetramethyl--[1,3,2] dioxaborinate-2-base) phenyl amine 16.7g, toluene/ethanol (4/1, v/v) mixed solvent 130ml, 2M wet chemical 21ml be added in the reaction vessel having carried out nitrogen replacement, the nitrogen ventilated 30 minutes in ultrasonic wave limit is irradiated on limit.
Then, add tetrakis triphenylphosphine palladium 0.67g and heat, return stirring 27.5 hours.Letting cool to room temperature, after adding methyl alcohol 100ml, taking separated out rough thing by filtering.
This rough thing is added in toluene 500ml, is heated to 80 DEG C and dissolve, use silica gel 19g to carry out refining with adsorbents.After under reduced pressure concentrating, mixed solvent based on toluene/ethanol carries out partial crystallization, carries out backflow cleaning based on ethanol, thus obtain the yellow powder 17.6g (yield 87%) of two (biphenyl-4-base)-[4-{4-(biphenyl-4-base) thieno-[3,2-b] indoles-2-base } phenyl] amine (compound 10).
For the yellow powder of gained, NMR is used to identify structure.Will
1h-NMR measurement result is shown in Fig. 1.
1h-NMR (THF-d
8) in detect the signal of following 36 hydrogen.
δ(ppm)＝7.93(2H)
7.82-7.60(16H)
7.54-7.38(8H)
7.30-7.19(10H)
< embodiment 2>
3-{4-(9,9-dimethyl-9H-fluorenes-2-base) thieno-[3,2-b] indoles-2-base } synthesis (synthesis of compound 18) of-9-phenyl carbazole
By bromo-for 2-4-(9,9-dimethyl-9H-fluorenes-2-base) thieno-[3,2-b] indoles 14.7g, (9-phenyl-9H-carbazole-3-base) boric acid 10.9g, toluene/ethanol (4/1, v/v) mixed solvent 190ml, 2M wet chemical 25ml be added in the reaction vessel having carried out nitrogen replacement, the nitrogen ventilated 30 minutes in ultrasonic wave limit is irradiated on limit.
Then, add tetrakis triphenylphosphine palladium 0.76g and heat, return stirring 5.5 hours.Let cool to room temperature, carry out separatory operation and after taking organic layer, utilize anhydrous magnesium sulfate to dewater, under reduced pressure concentrating, thus obtain rough thing.
After this rough thing column chromatography (carrier: silica gel, elutriant: heptane/toluene) is refining, the mixed solvent of toluene and methanol is used to repeat partial crystallization, thus obtain 3-{4-(9,9-dimethyl-9H-fluorenes-2-base) thieno-[3,2-b] indoles-2-base } the yellow-white powder 15.3g (yield 76%) of-9-phenyl carbazole (compound 18).
For gained yellow-white powder, NMR is used to identify structure.Will
1h-NMR measurement result is shown in Fig. 2.
1the signal of following 30 hydrogen is detected in H-NMR (DMSO-d6).
δ(ppm)＝8.72(1H)
8.36(1H)
8.12(1H)
7.99-7.90(2H)
7.89-7.80(2H)
7.74-7.52(8H)
7.50-7.22(9H)
1.62(6H)
< embodiment 3>
(mensuration of second-order transition temperature)
About the thieno-indole derivatives obtained in embodiment 1 and 2, highly sensitive differential scanning calorimeter (Bruker AXS K.K. system, DSC3100S) is utilized to obtain fusing point and second-order transition temperature.
Its result is as follows.
Melting point glass transition temperature
The compound of embodiment 1 264 DEG C 130 DEG C
The compound of embodiment 2 242 DEG C 129 DEG C
Illustrate thus: thieno-indole derivatives has the second-order transition temperature of more than 100 DEG C, filminess is stablized.
< embodiment 4>
Use the thieno-indole derivatives obtained in embodiment 1 and 2, make the vapor-deposited film of thickness 100nm on an ito substrate, utilize ionization potential determinator (Sumitomo Heavy Industries, Ltd, PYS-202) to measure work function.
Work function
The compound 5.55eV of embodiment 1
The compound 5.72eV of embodiment 2
From the above results: compared with the work function 5.54eV had with the common hole mobile material such as NPD, TPD, the energy level that thieno-indole derivatives display of the present invention is applicable to, has good cavity transmission ability.
< embodiment 5>
(evaluating characteristics of organic EL device)
The organic EL device of structure shown in construction drawing 3, it possesses the hole transmission layer using the thieno-indole derivatives (compound 10) obtained in embodiment 1 to be formed.
Specifically, after film forming being had the glass substrate 1 organic solvent cleaning of the ITO of thickness 150nm, clean surface is carried out by oxygen plasma treatment.Thereafter, this glass substrate with ITO electrode to be arranged in vacuum evaporation plating machine and to be decompressed to below 0.001Pa, using the compound 63 of following structural formula in this condition, be formed with the hole injection layer 3 of thickness 20nm in the mode covering transparent anode 2.
The thieno-indole derivatives (compound 10) that the hole injection layer 3 formed operating like this obtains in evaporation embodiment 1, thus the hole transmission layer 4 forming thickness 40nm.
This hole transmission layer 4 uses compound 64 and the compound 65 of following structural formula, with evaporation rate ratio for compound 64: the evaporation rate of compound 65=5:95 carries out binary evaporation, defines the luminescent layer 5 of thickness 30nm.
Then, Alq is used
3, above-mentioned luminescent layer 5 is formed the electron transfer layer 6 of thickness 30nm.
And then, use lithium fluoride, above-mentioned electron transfer layer 6 is formed the electron injecting layer 7 of thickness 0.5nm.
Finally, the mode AM aluminum metallization reaching 150nm with thickness, to form negative electrode 8, obtains the organic EL device of structure shown in Fig. 3.
The organic EL device made for above-mentioned such operation, in an atmosphere, applies volts DS under normal temperature, the measurement result of the characteristics of luminescence is now summed up and is shown in table 1.
< comparative example 1>
Except using the compd A of following structural formula to replace the thieno-indole derivatives (compound 10) of embodiment 1 to be formed except the hole transmission layer 4 of thickness 40nm, identically operate to make organic EL device with embodiment 5.
The organic EL device obtained for operating like this, operation measures the characteristics of luminescence similarly to Example 5, its result is merged and is shown in table 1.
< comparative example 2>
The thieno-indole derivatives (compound 10) of embodiment 1 is replaced to be formed except the hole transmission layer 4 of thickness 40nm except using the compd B of following structural formula, organic EL device is made with complete same operation of embodiment 5, for gained organic EL device, operation measures the characteristics of luminescence similarly to Example 5, its result is merged and is shown in table 1.
< comparative example 3>
The thieno-indole derivatives of embodiment 1 (compound 10) is replaced to be formed except the hole transmission layer 4 of thickness 40nm except using the compound 66 of following structural formula, organic EL device is made with complete same operation of embodiment 5, for gained organic EL device, operation measures the characteristics of luminescence similarly to Example 5, its result is merged and is shown in table 1.
[table 1]
As shown in table 1, be 10mA/cm about circulating current density
2electric current time driving voltage, relative to employ compd A organic EL device 5.18V and employ the 5.62V of organic EL device of compd B, the voltage employing the organic EL device of the compound (compound 10) of embodiment 1 is low to moderate 4.78V.
In addition, about electrical efficiency, relative to employ compd A organic EL device 5.20lm/W, employ the 5.06lm/W of the organic EL device of compd B and employ the 5.06lm/W of organic EL device of compound 66, the organic EL device employing the compound (compound 10) of embodiment 1 is significantly increased to 6.06lm/W.
From above result clearly: the organic EL device employing thieno-indole derivatives of the present invention as compared to the organic EL device employing well known materials and aforesaid compound A with B and aforesaid compound 66 reduction of the raising that also can realize electrical efficiency, practical driving voltage.
In addition, about the organic EL device obtained in embodiment 5 and comparative example 1 ~ 3, measure luminous starting voltage, its result is shown as follows.
From this result: compared with employing the organic EL device of thieno-indole derivatives of the present invention (compound 10), use the luminous starting voltage of the organic EL device of aforesaid compound A and B and aforesaid compound 66 high respectively.
utilizability in industry
The cavity transmission ability with the compound of thieno-indole derivatives of the present invention is high, electron-blocking capability is excellent, filminess is stablized, and is therefore excellent as organic EL device compound.By using this compound to make organic EL device, high-luminous-efficiency and electrical efficiency can be obtained, and practical driving voltage can be reduced, can weather resistance be improved.Such as can launch in the purposes of family's appliances, illumination.
description of reference numerals
1: glass substrate
2: transparent anode
3: hole injection layer
4: hole transmission layer
5: luminescent layer
6: electron transfer layer
7: electron injecting layer
8: negative electrode
Claims (15)
1. the thieno-indole derivatives shown in following general formula (1):
In formula,
Ar
1represent aromatic hydrocarbyl or aromatic heterocycle,
R
1~ R
4be respectively hydrogen atom, D atom, fluorine atom, chlorine atom, cyano group, nitro, the alkyl of carbonatoms 1 ~ 6, the cycloalkyl of carbonatoms 5 ~ 10, the thiazolinyl of carbonatoms 2 ~ 6, the alkoxyl group of carbonatoms 1 ~ 6, the cycloalkyloxy of carbonatoms 5 ~ 10, aromatic hydrocarbyl, aromatic heterocycle or aryloxy, R
1~ R
3can via singly-bound, optionally there is substituent methylene radical, Sauerstoffatom or sulphur atom and bond together and form ring,
X
1and X
2under at least any one condition for 1 valency group shown in following structural formula (2), be respectively hydrogen atom, D atom, fluorine atom, chlorine atom, cyano group, nitro, the alkyl of carbonatoms 1 ~ 6, the cycloalkyl of carbonatoms 5 ~ 10, the thiazolinyl of carbonatoms 2 ~ 6, the alkoxyl group of carbonatoms 1 ~ 6, the cycloalkyloxy of carbonatoms 5 ~ 10, aromatic hydrocarbyl, aromatic heterocycle or aryloxy or 1 valency group shown in following structural formula (2):
In formula,
A
1represent the aromatic hydrocarbyl of divalent, the aromatic heterocycle of divalent or singly-bound,
Ar
2and Ar
3represent aromatic hydrocarbyl or aromatic heterocycle respectively, Ar
2with Ar
3can via singly-bound, optionally there is substituent methylene radical, Sauerstoffatom or sulphur atom and bond together and form ring, A
1during aromatic hydrocarbyl for divalent, A
1with Ar
2can via singly-bound, optionally there is substituent methylene radical, Sauerstoffatom or sulphur atom and bond together and form ring.
2. thieno-indole derivatives according to claim 1, wherein, in described structural formula (2), A
1with Ar
2define ring.
3. thieno-indole derivatives according to claim 2, wherein, by A
1with Ar
2the described ring formed is carbazole ring.
4. thieno-indole derivatives according to claim 1, wherein, in described general formula (1), X
1and X
2among only X
2for the group shown in described structural formula (2).
5. thieno-indole derivatives according to claim 4, it represents with following general formula (1a):
In formula,
Ar
1~ Ar
3, R
1~ R
4, A
1and X
1as described in as described in general formula (1) and structural formula (2).
6. thieno-indole derivatives according to claim 5, wherein, in described general formula (1a), A
1with Ar
2define ring.
7. thieno-indole derivatives according to claim 1, wherein, in described general formula (1), X
1and X
2among only X
1for the group shown in described structural formula (2).
8. thieno-indole derivatives according to claim 7, it represents with following general formula (1b):
In formula,
Ar
1~ Ar
3, R
1~ R
4, X
2and A
1as described in general formula (1) and as described in as described in structural formula (2).
9. thieno-indole derivatives according to claim 1, wherein, in described general formula (1), X
1with X
2both are the group shown in described structural formula (2).
10. thieno-indole derivatives according to claim 9, it represents with following general formula (1c):
In formula, Ar
1~ Ar
3, R
1~ R
4and A
1as described in general formula (1) and as described in as described in structural formula (2), multiple A
1, Ar
2, Ar
3can be the same or different each other.
11. 1 kinds of organic electroluminescence devices, is characterized in that, have in pair of electrodes and the organic electroluminescence device of at least one deck organic layer that clamps therebetween,
At least 1 layer of described organic layer comprises thieno-indole derivatives according to claim 1.
12. organic electroluminescence devices according to claim 11, wherein, described in comprise thieno-indole derivatives organic layer be hole transmission layer.
13. organic electroluminescence devices according to claim 11, wherein, described in comprise thieno-indole derivatives organic layer be electronic barrier layer.
14. organic electroluminescence devices according to claim 11, wherein, described in comprise thieno-indole derivatives organic layer be hole injection layer.
15. organic electroluminescence devices according to claim 11, wherein, described in comprise thieno-indole derivatives organic layer be luminescent layer.
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| US11404648B2 (en) | 2018-07-27 | 2022-08-02 | Wuhan Tianma Microelectronics Co., Ltd | Aromatic heterocyclic compound and organic light-emitting display device |
| CN115961298A (en) * | 2022-12-31 | 2023-04-14 | 广西师范大学 | Electrochemical mediated vinylaniline and alcohol synthesis 2,3-dialkoxy substituted indoline compound, synthesis method and application |
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| JP5356863B2 (en) * | 2009-03-04 | 2013-12-04 | 山本化成株式会社 | Organic transistor |
| JP5417039B2 (en) * | 2009-05-25 | 2014-02-12 | 出光興産株式会社 | Indole derivatives and organic thin film solar cells using the same |
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| US11404648B2 (en) | 2018-07-27 | 2022-08-02 | Wuhan Tianma Microelectronics Co., Ltd | Aromatic heterocyclic compound and organic light-emitting display device |
| CN115961298A (en) * | 2022-12-31 | 2023-04-14 | 广西师范大学 | Electrochemical mediated vinylaniline and alcohol synthesis 2,3-dialkoxy substituted indoline compound, synthesis method and application |
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| Publication number | Publication date |
|---|---|
| JP2014074073A (en) | 2014-04-24 |
| JPWO2014042006A1 (en) | 2016-08-18 |
| TW201418259A (en) | 2014-05-16 |
| WO2014042006A1 (en) | 2014-03-20 |
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Application publication date: 20150527 |