CN114213439A - Heterocyclic compound and organic electroluminescent device thereof - Google Patents
Heterocyclic compound and organic electroluminescent device thereof Download PDFInfo
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- CN114213439A CN114213439A CN202111551673.2A CN202111551673A CN114213439A CN 114213439 A CN114213439 A CN 114213439A CN 202111551673 A CN202111551673 A CN 202111551673A CN 114213439 A CN114213439 A CN 114213439A
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- substituted
- fluoro
- cyano
- nitro
- methyl
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- 150000002391 heterocyclic compounds Chemical class 0.000 title claims abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 17
- -1 nitro, cyano, methyl Chemical group 0.000 claims description 67
- 125000001153 fluoro group Chemical group F* 0.000 claims description 32
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 18
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 18
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 4
- 239000012044 organic layer Substances 0.000 claims 3
- 239000010410 layer Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 106
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 8
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052796 boron Inorganic materials 0.000 abstract description 6
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 4
- 150000004982 aromatic amines Chemical class 0.000 abstract description 3
- 230000005611 electricity Effects 0.000 abstract 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 30
- 238000000034 method Methods 0.000 description 30
- 230000015572 biosynthetic process Effects 0.000 description 28
- 238000003786 synthesis reaction Methods 0.000 description 28
- 150000001412 amines Chemical class 0.000 description 17
- UZVGSSNIUNSOFA-UHFFFAOYSA-N dibenzofuran-1-carboxylic acid Chemical compound O1C2=CC=CC=C2C2=C1C=CC=C2C(=O)O UZVGSSNIUNSOFA-UHFFFAOYSA-N 0.000 description 16
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- 230000005311 nuclear magnetism Effects 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 5
- CTPUUDQIXKUAMO-UHFFFAOYSA-N 1-bromo-3-iodobenzene Chemical compound BrC1=CC=CC(I)=C1 CTPUUDQIXKUAMO-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- 238000010438 heat treatment Methods 0.000 description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229940125797 compound 12 Drugs 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229950000688 phenothiazine Drugs 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel 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
- 239000000758 substrate Substances 0.000 description 2
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- UAOUIVVJBYDFKD-XKCDOFEDSA-N (1R,9R,10S,11R,12R,15S,18S,21R)-10,11,21-trihydroxy-8,8-dimethyl-14-methylidene-4-(prop-2-enylamino)-20-oxa-5-thia-3-azahexacyclo[9.7.2.112,15.01,9.02,6.012,18]henicosa-2(6),3-dien-13-one Chemical compound C([C@@H]1[C@@H](O)[C@@]23C(C1=C)=O)C[C@H]2[C@]12C(N=C(NCC=C)S4)=C4CC(C)(C)[C@H]1[C@H](O)[C@]3(O)OC2 UAOUIVVJBYDFKD-XKCDOFEDSA-N 0.000 description 1
- IUSARDYWEPUTPN-OZBXUNDUSA-N (2r)-n-[(2s,3r)-4-[[(4s)-6-(2,2-dimethylpropyl)spiro[3,4-dihydropyrano[2,3-b]pyridine-2,1'-cyclobutane]-4-yl]amino]-3-hydroxy-1-[3-(1,3-thiazol-2-yl)phenyl]butan-2-yl]-2-methoxypropanamide Chemical compound C([C@H](NC(=O)[C@@H](C)OC)[C@H](O)CN[C@@H]1C2=CC(CC(C)(C)C)=CN=C2OC2(CCC2)C1)C(C=1)=CC=CC=1C1=NC=CS1 IUSARDYWEPUTPN-OZBXUNDUSA-N 0.000 description 1
- 239000001211 (E)-4-phenylbut-3-en-2-one Substances 0.000 description 1
- 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 1
- KKHFRAFPESRGGD-UHFFFAOYSA-N 1,3-dimethyl-7-[3-(n-methylanilino)propyl]purine-2,6-dione Chemical compound C1=NC=2N(C)C(=O)N(C)C(=O)C=2N1CCCN(C)C1=CC=CC=C1 KKHFRAFPESRGGD-UHFFFAOYSA-N 0.000 description 1
- JGGSOWGJMBNDHS-UHFFFAOYSA-N 10-phenyl-5h-phenazine Chemical compound C12=CC=CC=C2NC2=CC=CC=C2N1C1=CC=CC=C1 JGGSOWGJMBNDHS-UHFFFAOYSA-N 0.000 description 1
- BAVDQTXFZOWKQO-UHFFFAOYSA-N 10h-thieno[2,3-a]carbazole Chemical compound C1=CC=C2NC3=C(SC=C4)C4=CC=C3C2=C1 BAVDQTXFZOWKQO-UHFFFAOYSA-N 0.000 description 1
- MRPZLXMWCIWOGP-UHFFFAOYSA-N 2,3-dimethyl-n-phenylaniline Chemical compound CC1=CC=CC(NC=2C=CC=CC=2)=C1C MRPZLXMWCIWOGP-UHFFFAOYSA-N 0.000 description 1
- VCUXVXLUOHDHKK-UHFFFAOYSA-N 2-(2-aminopyrimidin-4-yl)-4-(2-chloro-4-methoxyphenyl)-1,3-thiazole-5-carboxamide Chemical compound ClC1=CC(OC)=CC=C1C1=C(C(N)=O)SC(C=2N=C(N)N=CC=2)=N1 VCUXVXLUOHDHKK-UHFFFAOYSA-N 0.000 description 1
- QEBYEVQKHRUYPE-UHFFFAOYSA-N 2-(2-chlorophenyl)-5-[(1-methylpyrazol-3-yl)methyl]-4-[[methyl(pyridin-3-ylmethyl)amino]methyl]-1h-pyrazolo[4,3-c]pyridine-3,6-dione Chemical compound C1=CN(C)N=C1CN1C(=O)C=C2NN(C=3C(=CC=CC=3)Cl)C(=O)C2=C1CN(C)CC1=CC=CN=C1 QEBYEVQKHRUYPE-UHFFFAOYSA-N 0.000 description 1
- FMKGJQHNYMWDFJ-CVEARBPZSA-N 2-[[4-(2,2-difluoropropoxy)pyrimidin-5-yl]methylamino]-4-[[(1R,4S)-4-hydroxy-3,3-dimethylcyclohexyl]amino]pyrimidine-5-carbonitrile Chemical compound FC(COC1=NC=NC=C1CNC1=NC=C(C(=N1)N[C@H]1CC([C@H](CC1)O)(C)C)C#N)(C)F FMKGJQHNYMWDFJ-CVEARBPZSA-N 0.000 description 1
- LFOIDLOIBZFWDO-UHFFFAOYSA-N 2-methoxy-6-[6-methoxy-4-[(3-phenylmethoxyphenyl)methoxy]-1-benzofuran-2-yl]imidazo[2,1-b][1,3,4]thiadiazole Chemical compound N1=C2SC(OC)=NN2C=C1C(OC1=CC(OC)=C2)=CC1=C2OCC(C=1)=CC=CC=1OCC1=CC=CC=C1 LFOIDLOIBZFWDO-UHFFFAOYSA-N 0.000 description 1
- OYFFSPILVQLRQA-UHFFFAOYSA-N 3,6-ditert-butyl-9h-carbazole Chemical group C1=C(C(C)(C)C)C=C2C3=CC(C(C)(C)C)=CC=C3NC2=C1 OYFFSPILVQLRQA-UHFFFAOYSA-N 0.000 description 1
- ILXRGGHJJFVULA-UHFFFAOYSA-N 3,7-diphenyl-10h-phenoxazine Chemical group C=1C=C2NC3=CC=C(C=4C=CC=CC=4)C=C3OC2=CC=1C1=CC=CC=C1 ILXRGGHJJFVULA-UHFFFAOYSA-N 0.000 description 1
- CINYXYWQPZSTOT-UHFFFAOYSA-N 3-[3-[3,5-bis(3-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical compound C1=CN=CC(C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)=C1 CINYXYWQPZSTOT-UHFFFAOYSA-N 0.000 description 1
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 1
- MINMDCMSHDBHKG-UHFFFAOYSA-N 4-[4-[[6-methoxy-2-(2-methoxyimidazo[2,1-b][1,3,4]thiadiazol-6-yl)-1-benzofuran-4-yl]oxymethyl]-5-methyl-1,3-thiazol-2-yl]morpholine Chemical compound N1=C2SC(OC)=NN2C=C1C(OC1=CC(OC)=C2)=CC1=C2OCC(=C(S1)C)N=C1N1CCOCC1 MINMDCMSHDBHKG-UHFFFAOYSA-N 0.000 description 1
- RSIWALKZYXPAGW-NSHDSACASA-N 6-(3-fluorophenyl)-3-methyl-7-[(1s)-1-(7h-purin-6-ylamino)ethyl]-[1,3]thiazolo[3,2-a]pyrimidin-5-one Chemical compound C=1([C@@H](NC=2C=3N=CNC=3N=CN=2)C)N=C2SC=C(C)N2C(=O)C=1C1=CC=CC(F)=C1 RSIWALKZYXPAGW-NSHDSACASA-N 0.000 description 1
- VIZUPBYFLORCRA-UHFFFAOYSA-N 9,10-dinaphthalen-2-ylanthracene Chemical compound C12=CC=CC=C2C(C2=CC3=CC=CC=C3C=C2)=C(C=CC=C2)C2=C1C1=CC=C(C=CC=C2)C2=C1 VIZUPBYFLORCRA-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- OJRUSAPKCPIVBY-KQYNXXCUSA-N C1=NC2=C(N=C(N=C2N1[C@H]3[C@@H]([C@@H]([C@H](O3)COP(=O)(CP(=O)(O)O)O)O)O)I)N Chemical compound C1=NC2=C(N=C(N=C2N1[C@H]3[C@@H]([C@@H]([C@H](O3)COP(=O)(CP(=O)(O)O)O)O)O)I)N OJRUSAPKCPIVBY-KQYNXXCUSA-N 0.000 description 1
- UHNRLQRZRNKOKU-UHFFFAOYSA-N CCN(CC1=NC2=C(N1)C1=CC=C(C=C1N=C2N)C1=NNC=C1)C(C)=O Chemical compound CCN(CC1=NC2=C(N1)C1=CC=C(C=C1N=C2N)C1=NNC=C1)C(C)=O UHNRLQRZRNKOKU-UHFFFAOYSA-N 0.000 description 1
- QNVMWAUNCPPLOZ-UHFFFAOYSA-N N-(4-tert-butylphenyl)dibenzofuran-3-amine Chemical group CC(C)(C)c1ccc(Nc2ccc3c(c2)oc2ccccc32)cc1 QNVMWAUNCPPLOZ-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229940125758 compound 15 Drugs 0.000 description 1
- 229940125810 compound 20 Drugs 0.000 description 1
- 229940125807 compound 37 Drugs 0.000 description 1
- 229940127113 compound 57 Drugs 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- JAXFJECJQZDFJS-XHEPKHHKSA-N gtpl8555 Chemical compound OC(=O)C[C@H](N)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](C(C)C)C(=O)N[C@@H](C(C)C)C(=O)N1CCC[C@@H]1C(=O)N[C@H](B1O[C@@]2(C)[C@H]3C[C@H](C3(C)C)C[C@H]2O1)CCC1=CC=C(F)C=C1 JAXFJECJQZDFJS-XHEPKHHKSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ZTLUNQYQSIQSFK-UHFFFAOYSA-N n-[4-(4-aminophenyl)phenyl]naphthalen-1-amine Chemical compound C1=CC(N)=CC=C1C(C=C1)=CC=C1NC1=CC=CC2=CC=CC=C12 ZTLUNQYQSIQSFK-UHFFFAOYSA-N 0.000 description 1
- YGBMCLDVRUGXOV-UHFFFAOYSA-N n-[6-[6-chloro-5-[(4-fluorophenyl)sulfonylamino]pyridin-3-yl]-1,3-benzothiazol-2-yl]acetamide Chemical compound C1=C2SC(NC(=O)C)=NC2=CC=C1C(C=1)=CN=C(Cl)C=1NS(=O)(=O)C1=CC=C(F)C=C1 YGBMCLDVRUGXOV-UHFFFAOYSA-N 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
-
- 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
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
-
- C—CHEMISTRY; METALLURGY
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Abstract
The invention relates to a heterocyclic compound and an organic electroluminescent device thereof, wherein the compound is formed by bonding boron with a dibenzo-hexatomic heterocycle as a core and bonding with group nitrogen such as arylamine, carbazole and the like, and has both electricity supply and electricity receiving properties.
Description
Technical Field
The invention relates to the field of photoelectric materials, in particular to a heterocyclic compound and an organic electroluminescent device thereof.
Background
Organic Light Emitting Diodes (OLEDs) have the advantages of high brightness, fast response, wide viewing angle, flexibility and the like, are widely applied to the field of display panels of products such as novel lighting lamps, smart phones and tablet computers, and as the applications of OLEDs are continuously promoted, people pay more attention to the research on core luminescent materials.
OLED light-emitting materials can be largely classified into three types according to the light-emitting mechanism. The first is a pure fluorescent material, capable of handling only 25% of singlet excitons. The second class is heavy metal phosphorescent materials, and due to the strong spin coupling effect of heavy metals, singlet excitons can be converted to triplet excitons through intersystem crossing (ISC), thereby achieving 100% internal quantum efficiency. However, heavy metal phosphorescent materials are expensive, toxic, and less stable, and the third is Thermally Activated Delayed Fluorescence (TADF), when the difference between the single and triple exciton energy levels of the molecule is Δ ESTSmaller, molecules can achieve a triplet to singlet state (T) upon excitation by thermal energy1-S1) The reverse intersystem transition (RISC) of the TADF structure forms singlet exciton radiation luminescence, thereby realizing 100 percent of internal quantum efficiency, and the TADF material has low cost and high efficiency and plays an important role in the industry.
Since boron atoms have an empty p-orbit and thus have electron-deficient properties, a series of TADF materials with improved properties can be obtained by utilizing the pz orbit of electron-deficient boron to conjugate with the pi-orbit of an organic conjugated system, which is a design hotspot of the current TADF new material system, however, no organic boron semiconductor luminescent material has the properties capable of meeting the industrial requirements so far, and therefore, in order to meet the increasing vigorous demands of industrial production, the research and development of boron-based materials with better comprehensive properties is urgently needed.
Disclosure of Invention
Aiming at the development trend of industrial technology and aiming at industrialization on the basis of the prior art, the invention aims to develop a novel heterocyclic compound containing boron atoms and nitrogen atoms, and the novel heterocyclic compound is applied to an organic electroluminescent device so as to reduce the driving voltage of the device, improve the luminous performance of the device and prolong the service life of the device.
The invention provides a heterocyclic compound, which has a structural general formula shown in formula 1:
wherein,
is represented by empty or a single bond or-X0-，X0Selected from O, S, N (R)4)、C(R5)(R6)，
Q1 is a group represented by the following formula 2:
R7and R8Or R8And R9Is a group bonded to the above formula 1, R7-R9Wherein the group not bound to formula 1 is hydrogen;
X1、X2each independently selected from O, S, N (R)10)、C(R11)(R12)，X1、X2Are the same or different from each other;
q2 is C6-30A carbocyclic group of2-30A heterocyclic group of (a);
R1-R3are the same or different from each other and are each independently selected from hydrogen, fluoro, nitro, cyano, C1-20Alkyl of (C)1-20Alkoxy group of (C)3-20Cycloalkyl of, C2-20Heterocycloalkyl of (A), C6-30Aryl of (C)3-30Heteroaryl of (A), C6-30Aryloxy group of (A), C6-30Arylthio of, R1Is singly bound to formula 1, R2And R3Respectively connected with single bonds of formula 1 or combined into rings;
R4-R6、R10-R12are the same or different from each other and are each independently selected from C1-20Alkyl of (C)6-30Aryl group of (1).
Further, R4-R6Each independently selected from methyl, phenyl unsubstituted or substituted by fluoro, nitro, cyano, methyl, tert-butyl.
Further, R10-R12Each independently selected from methyl, phenyl unsubstituted or substituted by fluoro, nitro, cyano, methyl, tert-butyl.
Further, Q2 is represented by one of formulas A1-A4:
wherein, X3、X4、X5Each independently selected from O, S, N (R)19)、C(R20)(R21)，X3、X4、X5Are the same or different from each other;
R13-R18each independently selected from hydrogen, fluoro, nitro, cyano, C1-6Unsubstituted or substituted by fluoro, nitro, cyano, C1-6Phenyl substituted by alkyl, unsubstituted or substituted by fluoro, nitro, cyano, C1-6Alkyl-substituted biphenylyl unsubstituted or substituted by fluoro, nitro, cyano, C1-6Alkyl, phenyl-substituted naphthyl, unsubstituted or substituted by fluoro, nitro, cyano, C1-6Alkyl, phenyl-substituted dibenzofuranyl, unsubstituted or substituted by fluoro, nitro, cyano, C1-6Alkyl, phenyl-substituted dibenzothienyl, unsubstituted or substituted by fluoro, nitro, cyano, C1-6Alkyl, phenyl-substituted fluorenyl, unsubstituted or substituted by fluoro, nitro, cyano, C1-6Alkyl, phenyl-substituted carbazolyl, R13-R18Are the same or different from each other;
R19-R21identical or different from each other, each independently selected from methyl, phenyl unsubstituted or substituted by fluoro, nitro, cyano, methyl, tert-butyl.
Further, a1 is further expressed as:
a2 is further expressed as:
a3 is further expressed as:
a4 is further expressed as:
further, R1Independently hydrogen, or a group represented by B1-B3:
wherein, X6Selected from O, S, N (R)22)、C(R23)(R24)，R22-R24Identical or different from each other, each independently selected from methyl, phenyl unsubstituted or substituted by fluoro, nitro, cyano, methyl, tert-butyl.
Further, R2And R3Each independently of the others is hydrogen, fluoro, nitro, cyano, methyl, tert-butyl, phenyl unsubstituted or substituted by fluoro, nitro, cyano, methyl, tert-butyl, or a group represented by C1,
wherein, X7Selected from O, S, N (R)25)、C(R26)(R27)，R25-R27Each independently selected from methyl, phenyl unsubstituted or substituted by fluoro, nitro, cyano, methyl, tert-butyl.
Further, the heterocyclic compound represented by the formula (1) is selected from the following structural formulas:
the heterocyclic compound provided by the invention contains a dibenzohexatomic heterocycle with an electron-deficient boron bonded bond, is bonded with group ring nitrogen such as arylamine and carbazole which supply electrons, has bipolar characteristics of both electric property and power supply property, and can form a stable luminescent material by adjusting the electric property of the compound supplied/received by the dibenzohexatomic heterocycle; multiple resonance can be generated between N atoms and B atoms in the compound, so that the highest occupied molecular orbital HOMO and the lowest unoccupied molecular orbital LOMO in a molecule are separated, and the compound shows TADF (TADF) characteristics; the compound takes a multi-element condensed structure formed by bonding boron with a dibenzo-hexatomic heterocycle as a main body, has stronger rigidity, and can effectively reduce the loss of non-radiative transition of excited molecules caused by vibration relaxation, thereby obtaining higher luminous efficacy.
Detailed Description
It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
Synthesis example 1: synthesis of Compound (12)
After adding 35mmol,9.90g of m-bromoiodobenzene, 30mmol,5.08g of diphenylamine, 60mmol,5.76g of sodium tert-butoxide, 0.15mmol,0.14g of dipalladium tris-benzylidene acetone, 0.15mmol,0.04g of tri-tert-butylphosphine tetrafluoroborate and 100mL of toluene into a reactor, stirring and mixing the mixture thoroughly, heating and refluxing the mixture under the protection of nitrogen, monitoring the completion of the reaction in the liquid phase, cooling the mixture to room temperature, adding 3-chloro-bis (dibenzo [ b, e ] [1,4] dioxin-2-yl) amine (30mmol,12.47g) into the reactor, stirring and mixing the mixture thoroughly, continuing heating and refluxing the reaction under the protection of nitrogen, monitoring the completion of the reaction in the liquid phase, cooling the mixture to room temperature, extracting the reaction solution with a mixture of water and dichloromethane, drying the organic phase magnesium sulfate, concentrating the dried mixture, purifying and separating the mixture in a silica gel column with a mixed solvent of 1:10 dichloromethane and petroleum ether, thus, 12.06g of the compound represented by the following chemical formula (12a) was obtained in a yield of 61%;
dissolving the compound (10mmol,6.59g) represented by the formula (12a) in 50mL of tert-butyl benzene solution in a reactor, cooling the reaction solution to-40 ℃, slowly adding 32.5mL of 2.5M N-hexane tert-butyl lithium solution dropwise under the protection of nitrogen, stirring for 0.5-2h while maintaining the temperature, adding boron tribromide (15mmol,3.76g), heating the reaction solution to room temperature, stirring for 0.5-2h, cooling the reaction solution to 0 ℃, adding N, N-diisopropylethylamine (10mmol,1.29g), heating to 120 ℃ for reflux reaction, monitoring the completion of the reaction in a liquid phase, cooling to room temperature, quenching the reaction solution with acetic acid, extracting the reaction solution with a mixture of water and dichloromethane, drying an organic phase magnesium sulfate, concentrating, purifying and separating in a silica gel column with a mixed solvent of 1:10 dichloromethane and petroleum ether, thereby obtaining 2.09g of the compound represented by the following formula (12), the yield is 33%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 632.4762; nuclear magnetism δ (ppm) is 8.82(1H), 8.19(1H), 7.78(2H), 7.69(1H), 7.47(1H), 7.35(2H), 7.29(1H), 7.21(1H), 7.11(6H), 6.98-7.04(5H), 6.87(1H), 6.72(1H), 6.45(1H), 6.24 (1H).
Synthesis example 2: synthesis of Compound (15)
The procedure of example 1 was repeated except for substituting m-bromoiodobenzene with 10- (3-bromo-5-iodobenzene) -10 h-phenoxazine (35mmol,16.24g), diphenylamine with 4,4' -dicyanodianiline (30mmol,6.58g) and 3-chloro-bis (dibenzo [ b, e ] [1,4] dioxin-2-yl) amine with 2-chloro-N-phenylphenoxathiin-3-amine (30mmol,9.77g), to give 13.45g of the compound represented by the following formula (15a) in 56% yield;
the same procedures used in example 1 were repeated except for replacing the compound represented by (12a) in example 1 with 8.00g of the compound represented by (15a) described in example 1 to give 2.32g of the compound represented by the following formula (14) in a yield of 30%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 773.6815; nuclear magnetism δ (ppm) is 8.52(1H), 8.33(1H), 7.82(2H), 7.57(1H), 7.48(3H), 7.39(1H), 7.28(3H), 7.19(3H), 7.05(1H), 6.96(2H), 6.89(2H), 6.83(1H), 6.77(2H), 6.70(1H), 6.58(2H), 5.58(1H), 5.51 (1H).
Synthetic example 3: synthesis of Compound (20)
The procedure of example 1 was repeated except for replacing the diphenylamine in example 1 with dimethyldiphenylamine (30mmol,5.92g) and replacing the 3-chloro-bis (dibenzo [ b, e ] [1,4] dioxin-2-yl) amine with 3-chloro-N-mesitylene-9, 9,10, 10-tetramethyl-9, 10-dihydroheteroanthracen-2-amine (30mmol,12.12g), to give 13.57g of the compound represented by the following formula (20a) in a yield of 67%;
the same procedures used in example 1 were repeated except for replacing the compound represented by (12a) in example 1 with 6.75g of the compound represented by (20a) above to give 2.34g of the compound represented by the following formula (20) in a yield of 36%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 648.7067; nuclear magnetism δ (ppm) is 8.37(1H), 8.25(1H), 8.11(1H), 7.67(2H), 7.54(1H), 7.42(2H), 7.31(1H), 7.23(3H), 7.04(2H), 6.83(2H), 6.24(1H), 6.15(1H), 2.26(3H), 2.31(3H), 2.19(9H), 1.78 (12H).
Synthetic example 4: synthesis of Compound (28)
The procedure of example 1 was repeated except for replacing diphenylamine with 9-hydrogen-carbazole (30mmol,5.02g) and replacing 3-chloro-bis (dibenzo [ b, e ] [1,4] dioxin-2-yl) amine with N- ([1,1' -biphenyl ] -4-yl) -2-chloro-9, 9-dimethyl-9-hydro-xanthen-3-amine (30mmol,12.36g), thereby obtaining 12.35g of a compound represented by the following chemical formula (28a) in a yield of 63%;
the same procedures used in example 1 were repeated except for replacing the compound represented by (12a) in example 1 with 6.53g of the compound represented by (28a) described in example 1 to give 2.13g of the compound represented by the following formula (28) in a yield of 34%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 626.5608; nuclear magnetism δ (ppm) is 8.65(1H), 8.37(1H), 8.18(1H), 8.02(1H), 7.93(1H), 7.75(2H), 7.64(1H), 7.56(3H), 7.38-7.47(6H), 7.31(3H), 7.22(1H), 7.10(1H), 7.01(1H), 6.82(1H), 6.63(1H), 1.79 (6H).
Synthesis example 5: synthesis of Compound (37)
The procedure of example 1 was repeated except for replacing m-bromoiodobenzene with 3-bromo-5-iodo-N, N-diphenylaniline (35mmol,15.75g), diphenylamine with 3, 6-dimethyl-9-hydro-carbazole (30mmol,5.86g) and 3-chloro-bis (dibenzo [ b, e ] [1,4] dioxin-2-yl) amine with 3-chloro-N-phenylthianthrene-2-amine (30mmol,10.26g) in example 1 to give 14.01g of the compound represented by the following formula (37a) in a yield of 60%;
the same procedures used in example 1 were repeated except for replacing the compound represented by (12a) in example 1 with 7.78g of the compound represented by (37a) described in example 1 to give 2.41g of the compound represented by the following formula (37) in a yield of 32%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 751.7762; nuclear magnetic δ (ppm) is 9.07(1H), 8.68(1H), 8.53(1H), 8.19(1H), 7.92(1H), 7.74(2H), 7.63(1H), 7.47(4H), 7.35(2H), 7.22(2H), 7.14(3H), 7.05(4H), 6.94(2H), 6.72(1H), 5.26(1H), 5.14(1H), 2.38(3H), 2.29 (3H).
Synthetic example 6: synthesis of Compound (43)
The diphenylamine in example 1 was replaced with 12-hydro-benzo [4,5] thieno [2,3-a ] carbazole (30mmol,8.20g) and 3-chloro-bis (dibenzo [ b, e ] [1,4] dioxin-2-yl) amine was replaced with 3-chloro-9, 9-dimethyl-N- (4-nitrophenyl) -9-hydro-thiaanthracen-2-amine (30mmol,11.91g), and the other synthetic procedures were the same as in example 1, whereby 11.16g of the compound represented by the following chemical formula (43a) was obtained in a yield of 50%;
the same procedures used in example 1 were repeated except for replacing the compound represented by (12a) in example 1 with 7.44g of the compound represented by (43a) above, thereby obtaining 2.66g of a compound represented by the following formula (43) in a yield of 37%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 717.6625; nuclear magnetism δ (ppm) is 9.12(1H), 8.89(1H), 8.62(1H), 8.53(1H), 8.47(1H), 8.25(2H), 8.17(1H), 8.11(1H), 8.02(1H), 7.86(1H), 7.75(1H), 7.63(1H), 7.48(3H), 7.39(1H), 7.26(1H), 7.11(1H), 6.90(1H), 6.82(1H), 6.76(1H), 1.79 (6H).
Synthetic example 7: synthesis of Compound (54)
The procedure of example 1 was repeated except for substituting m-bromoiodobenzene with 9- (3-bromo-5-iodophenyl) -hydrogen-carbazole (35mmol,15.68g), substituting diphenylamine with 10-hydro-phenothiazine (30mmol,5.98g), and substituting 3-chloro-bis (dibenzo [ b, e ] [1,4] dioxin-2-yl) amine with 3-chloro-9, 9,10, 10-tetramethyl-N- (p-tolyl) -9, 10-dihydroanthracene-2-amine (30mmol,11.27g), and obtaining 14.42g of the compound represented by the following formula (54a) in a yield of 59%;
the same procedures used in example 1 were repeated except for replacing the compound represented by (12a) in example 1 with 8.14g of the compound represented by (54a) above to give 2.60g of the compound represented by the following formula (54) in a yield of 33%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 787.8354; nuclear magnetism δ (ppm) is 8.37(1H), 8.22(2H), 8.10(1H), 7.95(1H), 7.82(1H), 7.75(2H), 7.62(2H), 7.50(2H), 7.37(2H), 7.24(2H), 7.16(3H), 7.10(1H), 6.98(3H), 6.74(1H), 6.67(1H), 6.54(1H), 6.45(1H), 2.26(3H), 1.79 (12H).
Synthesis example 8: synthesis of Compound (57)
The diphenylamine in example 1 was replaced with 3, 7-diphenyl-10 h-phenoxazine (30mmol,10.06g), 3-chloro-bis (dibenzo [ b, e ] [1,4] dioxin-2-yl) amine was replaced with 3-chloro-N-phenyldibenzo [ b, e ] [1,4] dioxin-2-amine (30mmol,9.29g), and the other synthetic procedures were the same as in example 1, whereby 13.59g of the compound represented by the following formula (57a) was obtained in a yield of 63%;
the same procedures used in example 1 were repeated except for replacing the compound represented by (12a) in example 1 with 7.19g of the compound represented by (57a) described in this example to give 2.15g of the compound represented by the following formula (57) in a yield of 31%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 692.5783; nuclear magnetism δ (ppm) is 8.28(1H), 8.11(1H), 7.92(4H), 7.75(2H), 7.63(1H), 7.52(5H), 7.41(1H), 7.34(1H), 7.29(3H), 7.20(2H), 7.11(2H), 7.02(2H), 6.88(1H), 6.72(1H), 6.21(1H), 6.14 (1H).
Synthetic example 9: synthesis of Compound (62)
The diphenylamine in example 1 was replaced with 3, 7-difluoro-10-hydro-phenothiazine (30mmol,2.35g) and 3-chloro-bis (dibenzo [ b, e ] [1,4] dioxin-2-yl) amine was replaced with N- ([1,1' -biphenyl ] -4-yl) -3-chlorophenoxazin-2-amine (30mmol,12.05g), and the other synthesis procedures were the same as in example 1, whereby 13.87g of the compound represented by the following formula (62a) was obtained in 65% yield;
the same procedures used in example 1 were repeated except for replacing the compound represented by (12a) in example 1 with 7.11g of the compound represented by (62a) above to give 2.40g of the compound represented by the following formula (62) in a yield of 35%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 684.5895; nuclear magnetism δ (ppm) is 8.34(1H), 8.18(1H), 8.05(1H), 7.72(3H), 7.56(2H), 7.47(2H), 7.39(1H), 7.31(3H), 7.23(1H), 7.16(1H), 7.04(1H), 6.93(1H), 6.85(2H), 6.69(1H), 6.42(1H), 6.34 (1H).
Synthetic example 10: synthesis Compound (67)
The procedure of example 1 was otherwise the same except for replacing 3-chloro-bis (dibenzo [ b, e ] [1,4] dioxin-2-yl) amine in example 1 with 2-chloro-N-phenylthianthren-1-amine (30mmol,10.26g), whereby 10.53g of a compound represented by the following formula (67a) was obtained in a yield of 60%;
the same procedures used in example 1 were repeated except for replacing the compound represented by (12a) in example 1 with 5.85g of the compound represented by (67a) above, thereby obtaining 2.12g of the compound represented by the following formula (67) in a yield of 38%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 558.5189; nuclear magnetism δ (ppm) is 8.75(1H), 8.42(1H), 7.78(4H), 7.69(1H), 7.44(1H), 7.38(2H), 7.29(5H), 7.17(2H), 7.06(1H), 6.87(1H), 7.70(2H), 6.16 (2H).
Synthetic example 11: synthesis of Compound (77)
The diphenylamine in example 1 was replaced with N- (4- (tert-butyl) phenyl) dibenzofuran-3-amine (30mmol,9.46g) and 3-chloro-bis (dibenzo [ b, e ] [1,4] dioxin-2-yl) amine was replaced with 3-chloro-N, 10-diphenyl-10 h-thiophenazine-4-amine (30mmol,12.03g), and the other synthesis procedures were the same as in example 1, whereby 13.04g of the compound represented by the following formula (77a) was obtained in 55% yield;
the same procedures used in example 1 were repeated except for replacing the compound represented by (12a) in example 1 with 7.90g of the compound represented by (77a) above to give 2.52g of the compound represented by the following formula (77) in a yield of 33%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 763.7703; nuclear magnetism δ (ppm) is 8.52(1H), 8.21(1H), 8.05(1H), 7.81(4H), 7.72(1H), 7.57(1H), 7.46(1H), 7.38(3H), 7.22-7..31(5H), 7.16(1H), 7.09(2H), 6.98(3H), 6.89(1H), 6.70(2H), 6.21(2H), 1.35 (9H).
Synthetic example 12: synthesis of Compound (82)
The procedure of example 1 was repeated except for substituting diphenylamine in example 1 with bis ([1,1' -biphenyl ] -4-yl) amine (30mmol,9.64g) and substituting 3-chloro-bis (dibenzo [ b, e ] [1,4] dioxin-2-yl) amine with 3-chloro-N- (4-fluorophenyl) phenoxathiin-4-amine (30mmol,10.31g), thereby obtaining 12.64g of a compound represented by the following formula (82a) in a yield of 57%;
the same procedure as in example 1 was repeated except for replacing the compound represented by (12a) in example 1 with 2.57g of the compound represented by (82a) in the present example to obtain g of a compound represented by the following formula (82) in a yield of 36%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 712.6526; nuclear magnetism δ (ppm) is 8.92(1H), 8.76(1H), 8.15(1H), 7.94(1H), 7.76(4H), 7.65(1H), 7.56(2H), 7.45(4H), 7.39(1H), 7.31(3H), 7.26(1H), 7.19(3H), 7.11(1H), 7.04(2H), 6.95(1H), 6.82(1H), 6.22(1H), 6.17 (1H).
Synthetic example 13: synthesis of Compound (87)
The diphenylamine in example 1 was replaced with 9-hydro-carbazole (30mmol,5.02g), 3-chloro-bis (dibenzo [ b, e ] [1,4] dioxin-2-yl) amine was replaced with 2-chloro-N- (naphthalen-2-yl) dibenzo [ b, e ] [1,4] dioxin-1-amine (30mmol,10.79g), and the other synthesis procedures were the same as in example 1, whereby 10.64g of the compound represented by the following formula (87a) was obtained in a yield of 59%;
the same procedures used in example 1 were repeated except for replacing the compound represented by (12a) in example 1 with 6.01g of the compound represented by (87a) described in this example to give 2.18g of the compound represented by the following formula (87) in a yield of 38%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 574.4408; nuclear magnetism δ (ppm) is 8.67(1H), 8.32(1H), 8.18(1H), 8.06(1H), 7.98(1H), 7.87(1H), 7.70(1H), 7.44-7.54(4H), 7.38(2H), 7.31(1H), 7.20(1H), 7.11(3H), 7.04(2H), 6.77(1H), 6.69(1H), 6.54 (1H).
Synthesis example 14: synthesis of Compound (104)
The diphenylamine in example 1 was replaced with 3, 6-di-tert-butyl-9 h-carbazole (30mmol,8.38g), 3-chloro-di (dibenzo [ b, e ] [1,4] dioxin-2-yl) amine was replaced with 4- ((2-chlorophenoxain-1-yl) amino) cyanobenzene (30mmol,10.52g), and the other synthetic procedures were the same as in example 1, whereby 11.62g of the compound represented by the following chemical formula (104a) was obtained with a yield of 55%;
the same procedures used in example 1 were repeated except for replacing the compound represented by (12a) in example 1 with 7.04g of the compound represented by (104a) described in this example, whereby 2.30g of the compound represented by the following formula (104) was obtained in a yield of 34%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 677.6768; nuclear magnetism δ (ppm) is 9.12(1H), 8.79(1H), 8.22(1H), 8.13(1H), 7.87(1H), 7.76(1H), 7.69(2H), 7.61(2H), 7.54(1H), 7.47(1H), 7.42(1H), 7.29(1H), 7.22(1H), 7.13(1H), 7.02(1H), 6.69(1H), 1.47(9H), 1.44 (9H).
Synthetic example 15: synthesis of Compound (112)
The procedure of example 1 was repeated except for substituting diphenylamine in example 1 with 5-phenyl-5, 10-dihydrophenazine (30mmol,7.75g), and 3-chloro-bis (dibenzo [ b, e ] [1,4] dioxin-2-yl) amine with 3-chloro-N- (4-fluorophenyl) phenoxathiin-4-amine (30mmol,10.31g), to give 11.77g of a compound represented by the following formula (112a) in a yield of 58%;
the same procedures used in example 1 were repeated except for replacing the compound represented by (12a) in example 1 with 6.76g of the compound represented by (112a) in this example to give 1.95g of the compound represented by the following formula (112) in a yield of 30%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 649.5479; nuclear magnetism δ (ppm) is 8.92(1H), 8.11(1H), 7.78(2H), 7.71(1H), 7.47(1H), 7.35(2H), 7.21-7.28(5H), 7.16(1H), 7.11(2H), 7.03(1H), 6.97(2H), 6.89(1H), 6.81(1H), 6.76(1H), 6.68(1H), 6.21(1H), 6.14 (1H).
Synthetic example 16: synthesis of Compound (125)
The diphenylamine in example 1 was replaced with 10-hydro-phenoxazine-3, 7-dicyanobenzene (30mmol,7.00g), and 3-chloro-bis (dibenzo [ b, e ] [1,4] dioxin-2-yl) amine was replaced with 2-chloro-N- (naphthalen-2-yl) thianthren-1-amine (30mmol,11.76g), and the other synthesis procedures were the same as in example 1, whereby 10.70g of the compound represented by the following formula (125a) was obtained in 51% yield;
the same procedures used in example 1 were repeated except for replacing the compound represented by (12a) in example 1 with 7.00g of the compound represented by (125a) described in this example to give 2.35g of the compound represented by the following formula (125) in a yield of 35%;
the compound obtained was analyzed and found to have the following results: mass spectrometer MALDI-TOF-MS (m/z) 672.5913; nuclear magnetism δ (ppm) is 8.51(1H), 8.42(1H), 8.04(1H), 7.96(1H), 7.85(1H), 7.71(1H), 7.54(1H), 7.49(1H), 7.42(1H), 7.33-7.38(4H), 7.28(1H), 7.17(2H), 7.11(1H), 7.02(1H), 6.77(1H), 6.25(1H), 6.17 (1H).
Device example 1
And (3) sequentially ultrasonically cleaning the glass substrate with the 50nm ITO transparent film for 10min by using acetone, isopropanol and deionized water, drying for 2h in vacuum at 105 ℃, then washing for 15min by using UV ozone, and conveying the ITO glass substrate to a vacuum evaporation machine.
Vacuum evaporating 4,4' -tris [ 2-naphthyl (phenyl) amino ] triphenylamine (2T-NATA) on the surface of the side on which the ITO film is formed to form a 10nm thick hole injection layer;
next, on the above hole injection layer, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB) was vacuum-evaporated to form a 60nm thick hole transport layer;
next, on the above hole transport layer, 9, 10-bis (2-naphthyl) Anthracene (ADN) (95 wt% as a light emitting host material) and the compound 12 prepared in the above synthesis example 1(5 wt% as a light emitting guest material) were co-vacuum evaporated to form a light emitting layer with a thickness of 20 nm;
next, 3'- [5' - [3- (3-pyridyl) phenyl ] [1,1':3',1 '-terphenyl ] -3, 3' -diyl ] bipyridine (TmPyPB) was vacuum-evaporated on the above light-emitting layer to form an electron transporting layer having a thickness of 15 nm;
next, on the above electron transport layer, lithium fluoride (LiF) was vacuum-evaporated to form an electron injection layer having a thickness of 1nm
Finally, magnesium aluminum alloy (Mg/Al) is vacuum evaporated on the electron injection layer to form a cathode with a diameter of 100 nm.
Device example 2 to device example 16
An organic electroluminescent device was prepared in the same manner as in device example 1, except that compound 15, compound 20, compound 28, compound 37, compound 43, compound 54, compound 57, compound 62, compound 67, compound 77, compound 82, compound 87, compound 104, compound 112, compound 125 were used instead of compound 12 prepared in synthesis example 1 described above, respectively.
Comparative device example 17 and comparative device example 18
An organic electroluminescent device was produced in the same manner as in device example 1, except that 4,4 '-bis (9-ethyl-3-carbazolevinyl) -1,1' -biphenyl (BCzVBi) and the following compound a-1 were used instead of compound 12 produced in synthesis example 1, respectively;
the organic electroluminescent devices prepared in the above device examples were subjected to performance tests, and the results are shown in table 1:
TABLE 1
As can be seen from the data in table 1 above, the compound provided by the present invention, which is formed by bonding boron-bonded dibenzo-six-membered heterocycle as a core and is bonded with group ring nitrogen such as arylamine and carbazole, has a conjugated planar structure with stronger rigidity due to the adjustment of the electrical supply and the electrical receiving of the dibenzo-six-membered heterocycle on the compound, so that the compound material realizes highly efficient and stable TADF luminescence characteristics.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A heterocyclic compound has a structural general formula shown in formula 1:
wherein,
is represented by empty or a single bond or-X0-, said X0Selected from O, S, N (R)4)、C(R5)(R6)，
Q1 is a group represented by the following formula 2:
R7and R8Or R8And R9Is a group bonded to the above formula 1, R7-R9Wherein the group not bound to formula 1 is hydrogen;
X1、X2are respectively independentIs selected from O, S, N (R)10)、C(R11)(R12)，X1、X2Are the same or different from each other;
q2 is C6-30A carbocyclic group of2-30A heterocyclic group of (a);
R1-R3are the same or different from each other and are each independently selected from hydrogen, fluoro, nitro, cyano, C1-20Alkyl of (C)1-20Alkoxy group of (C)3-20Cycloalkyl of, C2-20Heterocycloalkyl of (A), C6-30Aryl of (C)3-30Heteroaryl of (A), C6-30Aryloxy group of (A), C6-30Arylthio of, R1Is singly bound to formula 1, R2And R3Respectively connected with single bonds of formula 1 or combined into rings;
R4-R6、R10-R12are the same or different from each other and are each independently selected from C1-20Alkyl of (C)6-30Aryl group of (1).
2. The heterocyclic compound according to claim 1, wherein R is4-R6Each independently selected from methyl, phenyl unsubstituted or substituted by fluoro, nitro, cyano, methyl, tert-butyl.
3. The heterocyclic compound according to claim 1, wherein R is10-R12Each independently selected from methyl, phenyl unsubstituted or substituted by fluoro, nitro, cyano, methyl, tert-butyl.
4. The heterocyclic compound according to claim 1, wherein Q2 is represented by one of formulae a1-a 4:
wherein, X3、X4、X5Each independently selected from O, S, N (R)19)、C(R20)(R21)，X3、X4、X5Are the same or different from each other;
R13-R18each independently selected from hydrogen, fluoro, nitro, cyano, C1-6Unsubstituted or substituted by fluoro, nitro, cyano, C1-6Phenyl substituted by alkyl, unsubstituted or substituted by fluoro, nitro, cyano, C1-6Alkyl-substituted biphenylyl unsubstituted or substituted by fluoro, nitro, cyano, C1-6Alkyl, phenyl-substituted naphthyl, unsubstituted or substituted by fluoro, nitro, cyano, C1-6Alkyl, phenyl-substituted dibenzofuranyl, unsubstituted or substituted by fluoro, nitro, cyano, C1-6Alkyl, phenyl-substituted dibenzothienyl, unsubstituted or substituted by fluoro, nitro, cyano, C1-6Alkyl, phenyl-substituted fluorenyl, unsubstituted or substituted by fluoro, nitro, cyano, C1-6Alkyl, phenyl-substituted carbazolyl, R13-R18Are the same or different from each other;
R19-R21identical or different from each other, each independently selected from methyl, phenyl unsubstituted or substituted by fluoro, nitro, cyano, methyl, tert-butyl.
5. A heterocyclic compound according to claim 4, characterized in that said A1 is further represented by:
the a2 is further expressed as:
the a3 is further expressed as:
the a4 is further expressed as:
6. the heterocyclic compound according to claim 1, wherein R is1Independently hydrogen, or a group represented by B1-B3:
wherein, X6Selected from O, S, N (R)22)、C(R23)(R24)，R22-R24Identical or different from each other, each independently selected from methyl, phenyl unsubstituted or substituted by fluoro, nitro, cyano, methyl, tert-butyl.
7. The heterocyclic compound according to claim 1, wherein R is2And R3Each independently of the others is hydrogen, fluoro, nitro, cyano, methyl, tert-butyl, phenyl unsubstituted or substituted by fluoro, nitro, cyano, methyl, tert-butyl, or a group represented by C1,
wherein, X7Selected from O, S, N (R)25)、C(R26)(R27)，R25-R27Each independently selected from methyl, phenyl unsubstituted or substituted by fluoro, nitro, cyano, methyl, tert-butyl.
8. A heterocyclic compound according to claim 1, characterized in that the heterocyclic compound is selected from the following structural formulae:
9. an organic electroluminescent device mainly comprises a cathode, an anode and an organic layer between the two electrodes, and is characterized in that: the organic layer between the two electrodes comprises a heterocyclic compound according to any of claims 1 to 8.
10. The organic electroluminescent device according to claim 9, wherein the organic layer between the two electrodes comprises a light-emitting layer composed of a light-emitting host and a light-emitting guest comprising the heterocyclic compound according to any one of claims 1 to 8.
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| KR20190037176A (en) * | 2017-09-28 | 2019-04-05 | 주식회사 엘지화학 | Compound and organic light emitting device comprising same |
| CN110943176A (en) * | 2018-09-21 | 2020-03-31 | 三星显示有限公司 | Organic light emitting device and apparatus including the same |
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| WO2021107737A1 (en) * | 2019-11-29 | 2021-06-03 | 주식회사 엘지화학 | Organic light-emitting element |
| CN113727985A (en) * | 2019-09-10 | 2021-11-30 | 株式会社Lg化学 | Compound and organic light emitting device including the same |
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| CN107417715A (en) * | 2017-07-14 | 2017-12-01 | 瑞声科技（南京）有限公司 | A kind of electroluminescent organic material and its luminescent device |
| KR20190037176A (en) * | 2017-09-28 | 2019-04-05 | 주식회사 엘지화학 | Compound and organic light emitting device comprising same |
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