CN111377970A - 一种n`n`c`n型四齿铂(ii)配合物的制备及应用 - Google Patents
一种n`n`c`n型四齿铂(ii)配合物的制备及应用 Download PDFInfo
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- CN111377970A CN111377970A CN201811626574.4A CN201811626574A CN111377970A CN 111377970 A CN111377970 A CN 111377970A CN 201811626574 A CN201811626574 A CN 201811626574A CN 111377970 A CN111377970 A CN 111377970A
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- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 16
- 229910052736 halogen Inorganic materials 0.000 claims description 40
- 150000002367 halogens Chemical class 0.000 claims description 40
- 125000000217 alkyl group Chemical group 0.000 claims description 29
- 125000003118 aryl group Chemical group 0.000 claims description 28
- 125000004429 atom Chemical group 0.000 claims description 25
- 125000001072 heteroaryl group Chemical group 0.000 claims description 18
- 229910052731 fluorine Inorganic materials 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- 239000003446 ligand Substances 0.000 claims description 11
- 229910052794 bromium Inorganic materials 0.000 claims description 9
- -1 cyano, carboxyl Chemical group 0.000 claims description 9
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 8
- 125000005266 diarylamine group Chemical group 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 6
- 125000002252 acyl group Chemical group 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 5
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 claims description 4
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 125000004442 acylamino group Chemical group 0.000 claims description 4
- 125000004423 acyloxy group Chemical group 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 4
- 229910052805 deuterium Inorganic materials 0.000 claims description 4
- 125000004986 diarylamino group Chemical group 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 150000003222 pyridines Chemical class 0.000 claims description 4
- 125000005504 styryl group Chemical group 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 239000002019 doping agent Substances 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 125000004076 pyridyl group Chemical group 0.000 claims description 3
- 238000006619 Stille reaction Methods 0.000 claims description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical group C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 2
- 238000007641 inkjet printing Methods 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 238000002207 thermal evaporation Methods 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 7
- 229910020427 K2PtCl4 Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 102
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 55
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 32
- 229910052757 nitrogen Inorganic materials 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 150000001875 compounds Chemical class 0.000 description 25
- 239000002904 solvent Substances 0.000 description 23
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 22
- 230000015572 biosynthetic process Effects 0.000 description 19
- 238000003786 synthesis reaction Methods 0.000 description 18
- 238000004440 column chromatography Methods 0.000 description 17
- 239000007787 solid Substances 0.000 description 17
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 16
- 238000001035 drying Methods 0.000 description 16
- 239000012074 organic phase Substances 0.000 description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 238000001816 cooling Methods 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- 238000002390 rotary evaporation Methods 0.000 description 11
- 238000001704 evaporation Methods 0.000 description 10
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 8
- 238000004949 mass spectrometry Methods 0.000 description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 229940126214 compound 3 Drugs 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000013212 metal-organic material Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 4
- ONBQEOIKXPHGMB-VBSBHUPXSA-N 1-[2-[(2s,3r,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]oxy-4,6-dihydroxyphenyl]-3-(4-hydroxyphenyl)propan-1-one Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=CC(O)=C1C(=O)CCC1=CC=C(O)C=C1 ONBQEOIKXPHGMB-VBSBHUPXSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 3
- XSCHRSMBECNVNS-UHFFFAOYSA-N benzopyrazine Natural products N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 3
- 229940126142 compound 16 Drugs 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000002061 vacuum sublimation Methods 0.000 description 3
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 2
- IWZSHWBGHQBIML-ZGGLMWTQSA-N (3S,8S,10R,13S,14S,17S)-17-isoquinolin-7-yl-N,N,10,13-tetramethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-amine Chemical compound CN(C)[C@H]1CC[C@]2(C)C3CC[C@@]4(C)[C@@H](CC[C@@H]4c4ccc5ccncc5c4)[C@@H]3CC=C2C1 IWZSHWBGHQBIML-ZGGLMWTQSA-N 0.000 description 2
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 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
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 2
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 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 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-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
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 150000005840 aryl radicals Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229940125758 compound 15 Drugs 0.000 description 2
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- 125000004122 cyclic group Chemical group 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 description 1
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 1
- 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 1
- UGUHFDPGDQDVGX-UHFFFAOYSA-N 1,2,3-thiadiazole Chemical compound C1=CSN=N1 UGUHFDPGDQDVGX-UHFFFAOYSA-N 0.000 description 1
- YGTAZGSLCXNBQL-UHFFFAOYSA-N 1,2,4-thiadiazole Chemical compound C=1N=CSN=1 YGTAZGSLCXNBQL-UHFFFAOYSA-N 0.000 description 1
- KTZQTRPPVKQPFO-UHFFFAOYSA-N 1,2-benzoxazole Chemical compound C1=CC=C2C=NOC2=C1 KTZQTRPPVKQPFO-UHFFFAOYSA-N 0.000 description 1
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- GDRVFDDBLLKWRI-UHFFFAOYSA-N 4H-quinolizine Chemical compound C1=CC=CN2CC=CC=C21 GDRVFDDBLLKWRI-UHFFFAOYSA-N 0.000 description 1
- MAAHYFVFZLWJDN-UHFFFAOYSA-N 9H-carbazole 1H-pyrazole Chemical class C1=CC=CC=2C3=CC=CC=C3NC12.N1N=CC=C1 MAAHYFVFZLWJDN-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229940126657 Compound 17 Drugs 0.000 description 1
- 101000687716 Drosophila melanogaster SWI/SNF-related matrix-associated actin-dependent regulator of chromatin subfamily A containing DEAD/H box 1 homolog Proteins 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 101000687741 Mus musculus SWI/SNF-related matrix-associated actin-dependent regulator of chromatin subfamily A containing DEAD/H box 1 Proteins 0.000 description 1
- NUGPIZCTELGDOS-QHCPKHFHSA-N N-[(1S)-3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-pyridin-3-ylpropyl]cyclopentanecarboxamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CC[C@@H](C=1C=NC=CC=1)NC(=O)C1CCCC1)C NUGPIZCTELGDOS-QHCPKHFHSA-N 0.000 description 1
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 1
- OPFJDXRVMFKJJO-ZHHKINOHSA-N N-{[3-(2-benzamido-4-methyl-1,3-thiazol-5-yl)-pyrazol-5-yl]carbonyl}-G-dR-G-dD-dD-dD-NH2 Chemical compound S1C(C=2NN=C(C=2)C(=O)NCC(=O)N[C@H](CCCN=C(N)N)C(=O)NCC(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(N)=O)=C(C)N=C1NC(=O)C1=CC=CC=C1 OPFJDXRVMFKJJO-ZHHKINOHSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
技术领域
本发明涉及一种新型的N^N^C^N四齿铂(II)配合物金属有机材料,尤其是用于OLED发光器件的发光层中起光子发射作用的磷光掺杂材料。
背景技术
有机发光二极管(Organic Light-Emitting Diode,OLED)由美籍华裔教授邓青云(Ching W.Tang)于1979年在实验室中发现,因其具有自发光、广视角、几乎无穷高的对比度、较低耗电、极高反应速度以及潜在的柔性可折叠等优点,一直受到广泛的关注与研究。
在OLED材料领域,磷光类OLED发光层掺杂材料发展较为迅速与成熟,其主要是基于一些重金属有机配合物,如铱、铂、铕、锇等。磷光材料在发光过程中可以充分利用单线态和三线态激子的能量,因此理论上其量子效率可达到100%,是目前业界使用比较广的发光材料。
近些年来,基于铂(II)的磷光OLED材料在逐步发展并取得了较好的研究成果。与常见的铱(III)形成八面体配位结构不同,铂(II)为四配位,因而一般形成平面结构的配合物,其配体主要分为二齿,三齿和四齿配体。
与二齿或者三齿配体相比,四齿配体具有以下优点:
1)由配体一步反应即可合成铂(II)配合物,易于铂(II)配合物的制备与纯化;
2)合成铂(II)配合物过程中无异构体生成,结构专一;
3)螯合配位,结构稳定;
4)具有相对较好的磷光发射效率。
四齿配体类铂(II)配合物因其独特的性能,吸引了较多的研究与关注,尤其是支志明院士课题组对此类配合物进行了深入的研究并取得了优异的成果。2003年,支志明等首先报道了Pt(O^N^N^O)类配合物,如式(1)中所示。2004年,支志明等报道了一系列基于席夫碱类 Pt(O^N^N^O)配合物,如式(2)中所示,其合成简单,稳定性高,并表现出了良好的红光发射,具有较好的产业化前景。支志明等陆续报道了Pt(O^N^N^O),Pt(N^N^N^N),Pt(C^N^N^C), Pt(N^C^C^N),Pt(C^C^N^N),Pt(O^C^C^O),Pt(O^N^C^N),Pt(N^C^C^C)类Pt(II)配合物,并取得了较好的成果。其中值得一提的是,Li等报道了一系列基于吡唑-咔唑类Pt(II)配合物,其性能优异,具有极高的效率与较低的滚降效应,如式(4)~(10)中所示,基于式(4) 的绿光OLED外量子效率高达25.6%。
四齿配体类铂(II)配合物表现出良好的性能同时,由于铂(II)配合物平面结构的特性,也导致其分子间易堆叠,异形成激基缔合物等,影响OLED器件的性能,如式(5)中所示,一般通过在分子上增加叔丁基等大位阻基团,增强分子的立体结构,减弱分子间的相互作用。
OLED显示技术的发展是一项艰巨而意义重大的研究,其具有良好的特性同时也存在使用寿命短、色彩纯度差、易老化等缺点,限制了OLED技术的大规模应用。因此,设计新型的性能优异的OLED材料,尤其是发光层掺杂材料,则是OLED领域研究的重点与难点。
发明内容
在本发明中,设计了一类新型的基于咔唑骨架的具有N^N^C^N配位结构的Pt(II)配合物,并研究了其在有机发光二极管上的应用。咔唑是一类含有富电子的含氮杂环化合物,具有大的π-共轭刚性平面结构,这种独特的结构使其衍生物表现出了许多优异的光电性能。
本发明所涉及的新型的N^N^C^N四齿铂(II)配合物金属有机材料,具有如下式所示的结构:
其中,R1-R16独立的选自氢、氘、硫、卤素、羟基、酰基、烷氧基、酰氧基、氨基、硝基、酰基氨基、氰基、羧基、苯乙烯基、氨基羰基、氨基甲酰基、苄基羰基、芳氧基、二芳胺基、含1-30个C原子的饱和烷基、含1-20个C原子的不饱和烷基、含5-30个C原子取代的或未取代的芳基、含5-30个C原子取代的或未取代的杂芳基、或者相邻R1-R16相互通过共价键连接成环。
优选:其中R1-R16独立的选自氢、卤素、氨基、硝基、氰基、二芳胺基、含1-10个C原子的饱和烷基、含5-20个C原子的被卤素或一个或多个C1-C4烷基取代的或未取代芳基、含5-20个C原子的被卤素或一个或多个C1-C4烷基取代的或未取代杂芳基、或者相邻R1-R16相互通过共价键连接成环,所述卤素为F,Cl,Br。
其中R1’-R5’独立的选自氢、卤素、二芳胺基、含1-10个C原子的饱和烷基、含5-20 个C原子的被卤素或一个或多个C1-C4烷基取代的或未取代芳基、含5-20个C原子的被卤素或一个或多个C1-C4烷基取代的或未取代杂芳基、或者相邻R1’-R5’相互通过共价键连接成环,所述卤素为F,Cl,Br。
优选:其中R1’-R5’的5个基团中,其中有0-3个基团独立的表示为二芳胺基、含5- 10个C原子被卤素或1至3个C1-C4烷基取代的或未取代的芳基、含5-10个C原子的被卤素或1至3个C1-C4烷基取代的或未取代的杂芳基;其它的基团独立的表示为氢、卤素或含1-8个C原子的饱和烷基,所述卤素为F,Cl。
优选:其中R1’-R5’的5个基团中,其中有0-3个基团独立的表示为二苯胺基、C1-C4 烷基取代或未取代的苯基、吡啶基、咔唑基,其它基团独立的表示为氢、氟、含1-4个C原子的饱和烷基。
上述化合物的前体,即配体,其结构式如式(12)所示:
其中,R1-R16独立的选自氢、氘、硫、卤素、羟基、酰基、烷氧基、酰氧基、氨基、硝基、酰基氨基、氰基、羧基、苯乙烯基、氨基羰基、氨基甲酰基、苄基羰基、芳氧基、二芳胺基、含1-30个C原子的饱和烷基、含1-20个C原子的不饱和烷基、含5-30个C原子取代的或未取代的芳基、含5-30个C原子取代的或未取代的杂芳基、或者相邻R1-R16相互通过共价键连接成环。
优选前体,其结构式如下所示:
其中R1’-R5’独立的选自氢、卤素、二芳胺基、含1-10个C原子的饱和烷基、含5-20 个C原子的被卤素或一个或多个C1-C4烷基取代的或未取代芳基、含5-20个C原子的被卤素或一个或多个C1-C4烷基取代的或未取代杂芳基、或者相邻R1’-R5’相互通过共价键连接成环,所述卤素为F,Cl,Br。
为了本申请的目的,除非另有指明,术语卤素、烷基、烯基、芳基、酰基、烷氧基和杂环芳族体系或杂环芳族基团可有以下含义:
上述卤素或卤代包括氟、氯、溴和碘,优选F,Cl,Br,特别优选F或Cl,最优选F。
上述通过共价键连接成环、芳基、杂芳基包括具有5-30个碳原子,优选5-20个碳原子,更优选5-10个碳原子并且由一个芳环或多个稠和的芳环组成的芳基。适宜的芳基为,例如苯基,萘基,苊基(acenaphthenyl),二氢苊基(acenaphthenyl),蒽基、芴基、菲基(phenalenyl)。该芳基可为未取代的(即所有能够取代的碳原子带有氢原子)或在芳基的一个、多于一个或所有可取代的位置上被取代。适宜的取代基为例如卤素,优选F、Br或Cl;烷基,优选具有1-20个,1-10个或1-8个碳原子的烷基,特别优选甲基、乙基、异丙基或叔丁基;芳基,优选可再次被取代的或是未取代C5,C6芳基或芴基;杂芳基,优选含至少一个氮原子的杂芳基,特别优选吡啶基;芳基尤其特别优选带有选自F和叔丁基的取代基,优选可为给定的芳基或任选被至少一个上述取代基取代的为C5,C6芳基的芳基,C5,C6芳基特别优选带有0、1或2个上述取代基,C5,C6芳基尤其特别优选未取代的苯基或取代的苯基,诸如联苯基、被两个叔丁基优选在间位取代的苯基。
含1-20个C原子的不饱和烷基,优选烯基,更优选具有一个双键的烯基,特别优选具有双键和1-8个碳原子的烯基。
上述烷基包括具有1-30个碳原子,优选1-10个碳原子,优选1-4个碳原子的烷基。该烷基可为支链或直链的,也可以是环形的,并且可被一个或多个杂原子,优选N、O或S间断。而且,该烷基可被一个或多个卤素或上述的关于芳基的取代基所取代。同样,对于烷基而言,带有一个或多个芳基是可能的,所有上述的芳基均适用于该目的,烷基特别优选自甲基、乙基、异丙基、正丙基、异丁基、正丁基、叔丁基、仲丁基、异戊基、环丙基、环戊基、环己基。
上述酰基是以单键连接至CO基团的,如本文所用的烷基。
上述烷氧基是以单键与氧直接相连的,如本文所用的烷基。
上述杂芳基团被理解为与芳族、C3-C8环基相关,并且还包含一个氧或硫原子或1-4个氮原子或一个氧或硫原子与最多两个氮原子的组合,和他们的取代的以及苯并和吡啶并稠和的衍生物,例如,经由其中一个成环碳原子相连,所述杂芳基团可被一个或多个提到的关于芳基的取代基所取代。
在某些实施方案中,杂芳基可为携带以上独立的含有0、1或2个取代基的五、六元芳族杂环体系。杂芳基的典型实例包括但不限于未取代的呋喃、苯并呋喃、噻吩、苯并噻吩、吡咯、吡啶、吲哚、唑、苯并唑、异唑、苯并异唑、噻唑、苯并噻唑、异噻唑、咪唑、苯并咪唑、吡唑、吲唑、四唑、喹啉、异喹啉、哒嗪、嘧啶、嘌呤和吡嗪、呋喃、1,2,3-二唑、1,2,3- 噻二唑、1,2,4-噻二唑、三唑、苯并三唑、喋啶、苯并唑、二唑、苯并吡唑、喹嗪、噌啉、酞嗪、喹唑和喹喔啉及其单-或二-取代的衍生物。在某些实施方案中,取代基为卤代、羟基、氰基、O-C1~6烷基、C1~6烷基、羟基C1~6烷基和氨基-C1~6烷基。
如下所示的具体实例,包括但不限于以下结构:
上述配合物在OLED发光器件中的应用。
采用具有上述结构的铂(II)配合物,可制造热沉积和溶液处理的OLED器件。
包括含有一种或多种上述配合物的有机发光器件。
其中通过热沉积在该器件中以层形式施加该配合物。
其中通过旋涂在该器件中以层形式施加该配合物。
其中通过喷墨打印在该器件中以层形式施加该配合物。
上述有机发光器件,在施加电流时该器件发射为橙红色。
本发明中的有机金属配合物具有高荧光量子效率,良好的热稳定性及低淬灭常数,可以制造高发光效率、低滚降的橙红色光OLED器件。
附图说明
图1本发明的有机电致发光器件的结构示意图。
具体实施方式
下面结合实施例对本发明做进一步的详细说明。
上述配合物的制备方法,包括如下步骤:
如下所示,咔唑类衍生物S1经溴代反应得到底物S2,S2与联硼酸频哪醇酯反应得到相应的频哪醇酯衍生物S3,S3与吡啶类衍生物S6经Suzuki反应得到S7,S7与吡啶类衍生物 S8经Suzuki反应得到S9,S9与K2PtCl4反应即得到目标产物P。其中,S6由S4与S5经Stille反应制备。
下面结合实施例对本发明做进一步的详细说明。
本发明中化合物合成中涉及的初始底物和溶剂均购自安耐吉,百灵威,阿拉丁等本领域技术人员熟知的供应商。
实施例1:
合成路线:
化合物2的合成:取11.2g(40.0mmol)化合物1,溶于600mL醋酸中,然后滴入液溴16.0 g(2.5eq.,100.0mmol),遮光反应。室温搅拌约4hr后,旋蒸除去溶剂,再加入适量水和亚硫酸氢钠溶液洗涤,乙酸乙酯萃取,收集有机相,无水硫酸镁干燥后加入适量硅胶,旋蒸除去溶剂,使用正己烷/乙酸乙酯体系柱层析,得到白色固体15.7g,产率90%,纯度99.9%。
化合物6的合成:取14.7g(40.0mmol)化合物5,34.0g化合物4(3eq.,120.0mmol)和Pd(PPh3)4 924mg(0.02eq.,0.8mmol),加入到三颈烧瓶中,抽真空通入氮气置换多次,然后注入甲苯200mL,加热至105℃。在氮气保护下反应12hr后,冷却至室温,KF溶液猝灭反应,再加入适量水和乙酸乙酯萃取,收集有机相,无水硫酸镁干燥后旋蒸除去溶剂,使用正己烷/乙酸乙酯体系柱层析,得到白色固体7.5g,产率80%,纯度99.5%。
化合物7的合成:取10.3g(20.0mmol)化合物3,4.7g(20.0mmol)化合物6,碳酸钾3.4g(1.25eq.,25mmol)和Pd(PPh3)4 462mg(0.02eq.,0.4mmol)加入到三颈烧瓶中,抽真空通入氮气置换多次,然后注入二氧六环60mL,水20mL,加热至100℃。在氮气保护下反应12hr后,冷却至室温,再加入适量水和乙酸乙酯萃取,收集有机相,无水硫酸镁干燥后旋蒸除去溶剂,使用正己烷/乙酸乙酯体系柱层析,得到白色固体7.8g,产率70%,纯度99.5%。
化合物9的合成:取5.6g(10.0mmol)化合物7,1.9g(1.2eq.,12.0mmol)化合物 8,碳酸钾1.7g(1.25eq.,12.5mmol)和Pd(PPh3)4 230mg(0.02eq.,0.2mmol)加入到三颈烧瓶中,抽真空通入氮气置换多次,然后注入二氧六环30mL,水10mL,加热至100℃。在氮气保护下反应12hr后,冷却至室温,再加入适量水和乙酸乙酯萃取,收集有机相,无水硫酸镁干燥后旋蒸除去溶剂,使用正己烷/乙酸乙酯体系柱层析,得到白色固体4.6g,产率 90%,纯度99.9%。质谱(ESI-)([M-H]-)C36H35N3理论值:508.28;实测值:508.25。
化合物P1的合成:取1.02g(2.0mmol)化合物9,160mg四丁基溴化铵(0.25eq.,0.5mmol)和四氯铂酸钾930mg(1.2eq.,2.4mmol),溶于25mL乙酸中,抽真空通入氮气置换数次,搅拌加热至130℃反应12hr。反应结束后,冷却旋蒸除去溶剂,再加入适量水和乙酸乙酯萃取,收集有机相,无水硫酸镁干燥后旋蒸除去溶剂,使用正己烷/乙酸乙酯体系柱层析,将得到的粗品真空升华得到深红色固体842mg,总产率60%,纯度99.9%。质谱(ESI-) ([M-H]-)C36H32N3Pt理论值:508.28;实测值:508.25。
实施例2:
P2的合成路线与P1基本一致,部分化合物的合成如下所示。
化合物11的合成:取15.3g(40.0mmol)化合物10,34.0g化合物4(3eq.,120.0mmol)和Pd(PPh3)4 924mg(0.02eq.,0.8mmol),加入到三颈烧瓶中,抽真空通入氮气置换多次,然后注入甲苯200mL,加热至105℃。在氮气保护下反应12hr后,冷却至室温,KF溶液猝灭反应,再加入适量水和乙酸乙酯萃取,收集有机相,无水硫酸镁干燥后旋蒸除去溶剂,使用正己烷/乙酸乙酯体系柱层析,得到白色固体8.4g,产率85%,纯度99.0%。
化合物12的合成:取10.3g(20.0mmol)化合物3,5.0g(20.0mmol)化合物11,碳酸钾3.4g(1.25eq.,25mmol)和Pd(PPh3)4 462mg(0.02eq.,0.4mmol)加入到三颈烧瓶中,抽真空通入氮气置换多次,然后注入二氧六环60mL,水20mL,加热至100℃。在氮气保护下反应12hr后,冷却至室温,再加入适量水和乙酸乙酯萃取,收集有机相,无水硫酸镁干燥后旋蒸除去溶剂,使用正己烷/乙酸乙酯体系柱层析,得到白色固体7.8g,产率68%,纯度99.5%。
化合物13的合成:取5.7g(10.0mmol)化合物7,1.9g(1.2eq.,12.0mmol)化合物 8,碳酸钾1.7g(1.25eq.,12.5mmol)和Pd(PPh3)4 230mg(0.02eq.,0.2mmol)加入到三颈烧瓶中,抽真空通入氮气置换多次,然后注入二氧六环30mL,水10mL,加热至100℃。在氮气保护下反应12hr后,冷却至室温,再加入适量水和乙酸乙酯萃取,收集有机相,无水硫酸镁干燥后旋蒸除去溶剂,使用正己烷/乙酸乙酯体系柱层析,得到白色固体4.4g,产率 85%,纯度99.9%。质谱(ESI-)([M-H]-)C37H36N3理论值:522.30;实测值:522.31。
化合物P2的合成:取1.04g(2.0mmol)化合物9,160mg四丁基溴化铵(0.25eq.,0.5mmol)和四氯铂酸钾930mg(1.2eq.,2.4mmol),溶于25mL乙酸中,抽真空通入氮气置换数次,搅拌加热至130℃反应12hr。反应结束后,冷却旋蒸除去溶剂,再加入适量水和乙酸乙酯萃取,收集有机相,无水硫酸镁干燥后旋蒸除去溶剂,使用正己烷/乙酸乙酯体系柱层析,将得到的粗品真空升华得到深红色固体716mg,总产率50%,纯度99.9%。质谱(ESI-) ([M-H]-)C37H35N3Pt理论值:716.25;实测值:716.23。
实施例3:
P3的合成路线与P1基本一致,部分化合物的合成如下所示。
化合物15的合成:取18.9g(40.0mmol)化合物14,34.0g化合物4(3eq.,120.0mmol)和Pd(PPh3)4 924mg(0.02eq.,0.8mmol),加入到三颈烧瓶中,抽真空通入氮气置换多次,然后注入甲苯200mL,加热至105℃。在氮气保护下反应12hr后,冷却至室温,KF溶液猝灭反应,再加入适量水和乙酸乙酯萃取,收集有机相,无水硫酸镁干燥后旋蒸除去溶剂,使用正己烷/乙酸乙酯体系柱层析,得到白色固体10.8g,产率80%,纯度99.0%。
化合物16的合成:取10.3g(20.0mmol)化合物3,6.8g(20.0mmol)化合物15,碳酸钾3.4g(1.25eq.,25mmol)和Pd(PPh3)4 462mg(0.02eq.,0.4mmol)加入到三颈烧瓶中,抽真空通入氮气置换多次,然后注入二氧六环60mL,水20mL,加热至100℃。在氮气保护下反应12hr后,冷却至室温,再加入适量水和乙酸乙酯萃取,收集有机相,无水硫酸镁干燥后旋蒸除去溶剂,使用正己烷/乙酸乙酯体系柱层析,得到白色固体7.9g,产率60%,纯度99.5%。
化合物17的合成:取6.6g(10.0mmol)化合物16,1.9g(1.2eq.,12.0mmol)化合物8,碳酸钾1.7g(1.25eq.,12.5mmol)和Pd(PPh3)4 230mg(0.02eq.,0.2mmol)加入到三颈烧瓶中,抽真空通入氮气置换多次,然后注入二氧六环30mL,水10mL,加热至 100℃。在氮气保护下反应12hr后,冷却至室温,再加入适量水和乙酸乙酯萃取,收集有机相,无水硫酸镁干燥后旋蒸除去溶剂,使用正己烷/乙酸乙酯体系柱层析,得到白色固体4.9 g,产率80%,纯度99.9%。质谱(ESI-)([M-H]-)C44H42N3理论值:612.35;实测值:612.33。
化合物P3的合成:取1.23g(2.0mmol)化合物9,160mg四丁基溴化铵(0.25eq.,0.5mmol)和四氯铂酸钾930mg(1.2eq.,2.4mmol),溶于25mL乙酸中,抽真空通入氮气置换数次,搅拌加热至130℃反应12hr。反应结束后,冷却旋蒸除去溶剂,再加入适量水和乙酸乙酯萃取,收集有机相,无水硫酸镁干燥后旋蒸除去溶剂,使用正己烷/乙酸乙酯体系柱层析,将得到的粗品真空升华得到深红色固体887mg,总产率55%,纯度99.9%。质谱(ESI-) ([M-H]-)C44H41N3Pt理论值:805.30;实测值:805.28。
实施例4:
化合物19的合成:取14.7g(40.0mmol)化合物5,53.2g化合物18(3eq.,120.0mmol)和Pd(PPh3)4 924mg(0.02eq.,0.8mmol),加入到三颈烧瓶中,抽真空通入氮气置换多次,然后注入甲苯200mL,加热至105℃。在氮气保护下反应12hr后,冷却至室温,KF溶液猝灭反应,再加入适量水和乙酸乙酯萃取,收集有机相,无水硫酸镁干燥后旋蒸除去溶剂,使用正己烷/乙酸乙酯体系柱层析,得到白色固体13.4g,产率85%,纯度99.0%。
化合物20的合成:取10.3g(20.0mmol)化合物3,7.9g(20.0mmol)化合物19,碳酸钾3.4g(1.25eq.,25mmol)和Pd(PPh3)4 462mg(0.02eq.,0.4mmol)加入到三颈烧瓶中,抽真空通入氮气置换多次,然后注入二氧六环60mL,水20mL,加热至100℃。在氮气保护下反应12hr后,冷却至室温,再加入适量水和乙酸乙酯萃取,收集有机相,无水硫酸镁干燥后旋蒸除去溶剂,使用正己烷/乙酸乙酯体系柱层析,得到白色固体8.9g,产率62%,纯度99.0%。
化合物21的合成:取7.2g(10.0mmol)化合物16,1.9g(1.2eq.,12.0mmol)化合物8,碳酸钾1.7g(1.25eq.,12.5mmol)和Pd(PPh3)4 230mg(0.02eq.,0.2mmol)加入到三颈烧瓶中,抽真空通入氮气置换多次,然后注入二氧六环30mL,水10mL,加热至 100℃。在氮气保护下反应12hr后,冷却至室温,再加入适量水和乙酸乙酯萃取,收集有机相,无水硫酸镁干燥后旋蒸除去溶剂,使用正己烷/乙酸乙酯体系柱层析,得到白色固体5.7 g,产率85%,纯度99.9%。质谱(ESI-)([M-H]-)C48H50N3理论值:668.41;实测值:668.39。
化合物P4的合成:取1.34g(2.0mmol)化合物9,160mg四丁基溴化铵(0.25eq.,0.5mmol)和四氯铂酸钾930mg(1.2eq.,2.4mmol),溶于25mL乙酸中,抽真空通入氮气置换数次,搅拌加热至130℃反应12hr。反应结束后,冷却旋蒸除去溶剂,再加入适量水和乙酸乙酯萃取,收集有机相,无水硫酸镁干燥后旋蒸除去溶剂,使用正己烷/乙酸乙酯体系柱层析,将得到的粗品真空升华得到深红色固体776mg,总产率45%,纯度99.9%。质谱(ESI-) ([M-H]-)C48H48N3Pt理论值:861.36;实测值:861.33。
对于实施例的Pt(II)配合物,在二氯甲烷溶液溶液中呈现出明显的橙红光发射,波长范围在617~619nm之间。如下表所示:
下面是本发明化合物的应用实例。
ITO/TAPC(60nm)/TCTA:Pt(II)(40nm)/TmPyPb(30nm)/LiF(1nm)/Al(80nm)
器件制备方式:
依次使用丙酮、乙醇和蒸馏水对透明阳极氧化铟锡(ITO,20)(10Ω/sq)玻璃基板10进行超声清洗,再用氧气等离子处理5分钟。
然后将ITO衬底安装在真空气相蒸镀设备的衬底固定器上。在蒸镀设备中,控制体系压力在10-6torr.。
此后,向ITO衬底上蒸发厚度为60nm的空穴传输层(30)材料TAPC。
然后蒸发厚度为40nm的发光层材料(40)TCTA,其中掺杂不同质量分数的铂(II)配合物掺杂剂。
然后蒸发厚度为30nm的电子传输层(50)材料TmPyPb。
然后蒸发厚度为1nm的LiF为电子注入层(60)。
最后蒸发厚度为80nm的Al作为阴极(70)并完成器件封装。见图1所示。
器件的结构和制作方法完全相同,区别在于依次使用有机金属配合物P0、P1、P2、P3、P4作为发光层中的掺杂剂与掺杂浓度。其中,Pt0为经典的O^N^N^O类红光材料。
器件对比结果下表所示:
在四齿铂(II)配合物掺杂浓度分别为4wt%,8wt%,12wt%条件下,以上述ITO/HTL-1 (60nm)/EML-1:Pt(II)(40nm)/ETL-1(30nm)/LiF(1nm)/Al(80nm)器件基本结构制备器件。以基于P0的器件性能为参考,四齿铂(II)配合物P1、P2、P3、P4的器件在启动电压Von相比P0的器件均有不同程度的降低。同时,在1000cd/A条件下,基于P1、P2、P3、P4的器件在电流效率(CE),功率效率(PE)和外量子效率(EQE)相对于基于P0的器件均有不同程度的提升,尤其是P4在电流效率(CE),功率效率(PE)和外量子效率(EQE)上提升较为明显。在四齿铂(II)配合物掺杂浓度增加时,P0的效率提升较小甚至效率有一定程度的下降,P0因为平面结构较强而增加了分子间的相互作用,降低了发光效率。P1、P2、P3、P4相对于P0有较大的位阻基团,能有效降低分子间的聚集作用,避免形成激基复合物,提高发光效率。
本发明所涉及的四齿铂(II)配合物,其配体骨架具有类卟啉的结构,配体中心空腔能与铂(II)形成较强的螯合配位,有利于提高配合物的稳定性,有利于构筑长寿命的OLED器件;同时,配体骨架具有极好的刚性结构,能较大减少分子内旋转和振动等非辐射能量耗散,有利于铂(II)配合物发光效率与性能的提高。
综上所述,本发明所制备的有机电致发光器件的性能相对于基准器件具有较好的性能提升,所涉及的新型N^N^C^N四齿铂(II)配合物金属有机材料具有较大的应用价值。本发明所制备的N^N^C^N四齿铂(II)配合物金属有机材料,在有机发光二极管上具有有较大的应用价值,作为磷光掺杂材料制造高发光效率的橙红光OLED器件。
Claims (13)
2.权利要求1所述的配合物,其中R1-R16独立的选自氢、卤素、氨基、硝基、氰基、二芳胺基、含1-10个C原子的饱和烷基、含5-20个C原子的被卤素或一个或多个C1-C4烷基取代的或未取代芳基、含5-20个C原子的被卤素或一个或多个C1-C4烷基取代的或未取代杂芳基、或者相邻R1-R16相互通过共价键连接成环,所述卤素为F,Cl,Br。
4.权利要求3所述的配合物,其中R1’-R5’的5个基团中,其中有0-3个基团独立的表示为二芳胺基、含5-10个C原子被卤素或1至3个C1-C4烷基取代的或未取代的芳基、含5-10个C原子的被卤素或1至3个C1-C4烷基取代的或未取代的杂芳基;其它的基团独立的表示为氢、卤素或含1-8个C原子的饱和烷基,所述卤素为F,Cl。
5.权利要求4所述的配合物,其中R1’-R5’的5个基团中,其中有0-3个基团独立的表示为二苯胺基、C1-C4烷基取代或未取代的苯基、吡啶基、咔唑基,其它基团独立的表示为氢、氟、含1-4个C原子的饱和烷基。
11.权利要求1-7任一配合物在OLED发光器件中的应用。
12.根据权利要求11所述的应用,所述权利要求1-7所述的任一配合物采用通过热沉积、旋涂、喷墨打印以层形式施加在OLED发光器件中。
13.根据权利要求11所述的应用,所述权利要求1-7任一配合物为发光层中起光子发射作用的磷光掺杂材料。
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