CN112940040A - 一种四齿铂(ii)配合物的制备及应用 - Google Patents
一种四齿铂(ii)配合物的制备及应用 Download PDFInfo
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- CN112940040A CN112940040A CN201911268943.1A CN201911268943A CN112940040A CN 112940040 A CN112940040 A CN 112940040A CN 201911268943 A CN201911268943 A CN 201911268943A CN 112940040 A CN112940040 A CN 112940040A
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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 34
- 125000003118 aryl group Chemical group 0.000 claims description 24
- 125000001072 heteroaryl group Chemical group 0.000 claims description 23
- 125000004429 atom Chemical group 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 229910052731 fluorine Inorganic materials 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- 239000003446 ligand Substances 0.000 claims description 11
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 125000005266 diarylamine group Chemical group 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 7
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 6
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- -1 cyano, carboxyl Chemical group 0.000 claims description 6
- 229910052805 deuterium Inorganic materials 0.000 claims description 6
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 claims description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 5
- 125000002252 acyl group Chemical group 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 125000004076 pyridyl group Chemical group 0.000 claims description 5
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 claims description 4
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 4
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 claims description 3
- 125000004442 acylamino group Chemical group 0.000 claims description 3
- 125000004423 acyloxy group Chemical group 0.000 claims description 3
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- 238000010520 demethylation reaction Methods 0.000 claims description 3
- 125000004986 diarylamino group Chemical group 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 3
- 125000005504 styryl group Chemical group 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910019029 PtCl4 Inorganic materials 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 230000009920 chelation Effects 0.000 claims description 2
- 230000017858 demethylation Effects 0.000 claims description 2
- 239000002019 doping agent Substances 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 7
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical group C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims 1
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000010791 quenching Methods 0.000 abstract description 2
- 230000000171 quenching effect Effects 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- 150000001875 compounds Chemical class 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000002390 rotary evaporation Methods 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 7
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000000605 extraction Methods 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-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
- 229940125773 compound 10 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
- 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 3
- 239000013212 metal-organic material Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- 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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-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
- 229940125782 compound 2 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 150000004696 coordination complex Chemical class 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
- 238000001704 evaporation Methods 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
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 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
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 2
- CAMRHYBKQTWSCM-UHFFFAOYSA-N oxocyanamide Chemical compound O=NC#N CAMRHYBKQTWSCM-UHFFFAOYSA-N 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 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
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- WDBQJSCPCGTAFG-QHCPKHFHSA-N 4,4-difluoro-N-[(1S)-3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-pyridin-3-ylpropyl]cyclohexane-1-carboxamide Chemical compound FC1(CCC(CC1)C(=O)N[C@@H](CCN1CCC(CC1)N1C(=NN=C1C)C(C)C)C=1C=NC=CC=1)F WDBQJSCPCGTAFG-QHCPKHFHSA-N 0.000 description 1
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-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
- 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
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 125000004062 acenaphthenyl group Chemical group C1(CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- RFRXIWQYSOIBDI-UHFFFAOYSA-N benzarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC=C(O)C=C1 RFRXIWQYSOIBDI-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- WCZVZNOTHYJIEI-UHFFFAOYSA-N cinnoline Chemical compound N1=NC=CC2=CC=CC=C21 WCZVZNOTHYJIEI-UHFFFAOYSA-N 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125797 compound 12 Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
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Abstract
Description
技术领域
本发明涉及一种新型的四齿铂(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)又称为有机电激光显示、有机发光半导体,由美籍华裔科学家邓青云(Ching W.Tang)教授于1987年在柯达公司实验室中发现(Appl.Phys.Lett.1987,51,913)。相对于传统的的LCD(Liquid CrystalDisplay,液晶显示)显示技术,OLED显示技术因其具有自发光、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,其中,开发新型OLED材料一直是OLED技术研究的重点与难点。
与基于无机材料的LED(Light-Emitting Diode,发光二极管)相比,基于有机材料的OLED具有许多不可替代的优越性能,主要原因在于:(1)有机材料容易在任何基板上成膜,可以制成超薄平板显示面板;(2)有机分子结构可以经过分子设计来调控材料的发光性能,易于修饰和改造;(3)有机发光材料的荧光量子效率高,几乎达到100%;(4)基于无机材料的LED是点光源,而基于有机材料的OLED面板则可以制备面光源;(5)有机电致发光的OLED器件驱动电压比较低,而无机LED驱动电压一般较高。
当前OLED材料中,作为发光层掺杂起光子发射作用的主要是过渡金属类磷光材料,其中研究较多的是基于铱(III)和铂(II)配合物类。一般而言,二齿配体与三价铱形成的金属配合物呈八面体配位结构,铱原子处于八面体中心与二齿配体螯合配位。铱(III)配合物的八面体配位结构使其具分子具有较强的立体性,避免配合物分子之间互相堆叠,在制备OLED器件过程中,高浓度掺杂时不易形成激基缔合物发光。但是,对于一些非对称二齿配体,铱(III)配合物可能会产生异构体,会因为配体配位取向不同而存在面式和经式两种结构,导致铱(III)配合物分离难度提升以及目标铱(III)配合物的产率降低。
在铱(III)配合物磷光材料不断突破的同时,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,常见的配体主要分为二齿,三齿和四齿配体。与二齿或者三齿配体相比,四齿配体铂(II)配合物具有以下优点:
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,尤其是香港大学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(Chem.Sci.2016,7,1653)。
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,易形成激基缔合物等,降低OLED器件的性能。
发明内容
本申请提供一种基于四齿配体类新型Pt(II)配合物,其呈绿光发射并作为绿光磷光OLED材料应用于OLED器件中。这类新型Pt(II)配合物具有ONCN螯合配位模型,并在分子骨架上具有螺环结构,这种结构大大增强了分子的立体性,有利于减弱分子间的相互作用,避免配合物分子堆叠,抑制激基缔合物的形成,提高OLED器件的效率和寿命。
本发明所涉及的新型的四齿铂(II)配合物金属有机材料,具有如下式所示的结构:
其中R1-R21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原子的硅烷基、含1-30个C原子的饱和烷基、含2-20个C原子的不饱和烷基、取代的或未取代的含5-30个C原子的芳基、取代的或未取代的含5-30个C原子的杂芳基、或者相邻R1-R21相互通过共价键连接成环,其中取代为被卤素,氘、C1-C20烷基、氰基取代,所述杂芳基中杂原子为N、O、S中的一个或多个。
优选:其中R1-R21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、被卤素或一个或多个C1-C4烷基取代的或未取代的含5-20个C原子的芳基、被卤素或一个或多个C1-C4烷基取代的或未取代的含5-20个C原子的杂芳基、或者相邻R1-R21相互通过共价键连接成环,所述卤素为F,Cl,Br。
优选:其中R1-R21的21个基团中,其中有0-3个基团独立的表示为二芳胺基、被卤素或1至3个C1-C4烷基取代的或未取代的含5-10个C原子的芳基、被卤素或1至3个C1-C4烷基取代的或未取代的含5-10个C原子的含N杂芳基;其它的基团独立的表示为氢或含1-8个C原子的饱和烷基,所述卤素为F,Cl。
优选:其中所述R1-R21的21个基团中,其中有0-3个基团独立的表示为二苯胺基、苯基、吡啶基、咔唑基,其它基团独立的表示为氢、氟或者1-4个C原子的饱和烷基。
其中R1’-R6’独立的选自氢、卤素、二芳胺基、含1-10个C原子的饱和烷基、被卤素或一个或多个C1-C4烷基取代的或未取代的含5-20个C原子的芳基、被卤素或一个或多个C1-C4烷基取代的或未取代杂的含5-20个C原子的芳基、或者相邻R1’-R6’相互通过共价键连接成环,所述卤素为F,Cl,Br,所述杂芳基中杂原子为N、O、S中的任一一种。
优选:其中R1’-R6’的6个基团中,其中有0-3个基团独立的表示为二芳胺基、被卤素或1至3个C1-C4烷基取代的或未取代的含5-10个C原子的芳基、被卤素或1至3个C1-C4烷基取代的或未取代的含5-10个C原子的杂芳基;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’-R6’的6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。
上述配合物的前体,如下式所示:
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,甲基和叔丁基的取代基,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,初始底物S1与S2经Suzuki-Miyaura偶联反应得到底物S3,S3与S4经Buchwald–Hartwig偶联反应得到底物S5,S5与S6经Buchwald–Hartwig偶联反应得到底物S7,S7在吡啶盐酸盐作用下高温加热脱甲基得到S8,S8与K2PtCl4螯合反应即得到目标铂(II)配合物TM。
本发明中化合物合成中涉及的初始底物,中间体和溶剂等试剂均购自安耐吉,百灵威,阿拉丁等本领域技术人员熟知的供应商。
实施例1:
化合物3的合成:取20.0g(0.10mol)化合物1,19.8g(0.125mol)化合物2,四(三苯基膦)钯3.46g(0.03eq.,3.0mmol),碳酸钾27.6g(2.0eq.,0.20mol)于烧瓶中,加入210mL二氧六环,60mL水在氮气保护下加热回流反应8小时。停止反应后,冷却至室温旋蒸除去溶剂,加入适量水和乙酸乙酯萃取,收集有机相并干燥,旋蒸除去溶剂后使用快速硅胶色谱柱(流动相正己烷/乙酸乙酯=10:1)分离再重结晶得到20.0g目标产物化合物3,产率85%,纯度99.9%。
化合物5的合成:取11.7g(50mmol)化合物3,9.3g(50mmol)化合物4,醋酸钯450mg(0.04eq.,2mmol),三叔丁基膦0.40g(0.08eq.,4mmol),叔丁醇钾11.22g(2.0eq.,0.10mol)于烧瓶中,加入200mL甲苯,在氮气保护下加热回流反应8小时。停止反应后,冷却至室温旋蒸除去溶剂,加入适量水和乙酸乙酯萃取,收集有机相并干燥,旋蒸除去溶剂后使用快速硅胶色谱柱(流动相正己烷/乙酸乙酯=15:1)分离再重结晶得到23.83g目标产物化合物5,产率88%,纯度99.9%。
化合物7的合成:取4.9g(20mmol)化合物5,7.9g(20mmol)化合物6,醋酸钯225mg(0.02eq.,1mmol),三叔丁基膦0.20g(0.04eq.,2mmol),叔丁醇钾4.5g(2.0eq.,0.04mol)于烧瓶中,加入100mL甲苯,在氮气保护下加热回流反应8小时。停止反应后,冷却至室温旋蒸除去溶剂,加入适量水和乙酸乙酯萃取,收集有机相并干燥,旋蒸除去溶剂后使用快速硅胶色谱柱(流动相正己烷/乙酸乙酯=10:1)分离再重结晶得到8.9g目标产物化合物7,产率75%,纯度99.9%。
化合物8的合成:取5.9g(10mmol)化合物7,吡啶盐酸盐50g,在氮气保护下加热至200℃反应8小时。停止反应后,加入适量水和乙酸乙酯萃取,收集有机相并干燥,旋蒸除去溶剂后使用快速硅胶色谱柱(流动相正己烷/乙酸乙酯=15:1)分离,再使用甲醇重结晶得到目标产物化合物8 5.0g,产率86%,纯度99.9%。质谱(ESI-)([M-H]-)C41H27N3O理论值:576.22;实测值:576.21。
化合物Pt-1的合成:取1.15g(2.0mmol)化合物8,160mg四丁基溴化铵(0.25eq.,0.5mmol)和四氯铂酸钾930mg(1.2eq.,2.4mmol),溶于50mL乙酸中,抽真空通入氮气置换数次,搅拌加热至130℃反应12hrs。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,使用使用快速硅胶色谱柱(流动相正己烷/二氯甲烷=10:1)分离,再使用甲醇重结晶,将得到的粗品真空升华得到红色固体616mg,总产率40%,纯度99.95%。质谱(ESI-)([M+H]-)C41H25N3OPt理论值:771.16;实测值:771.19。
实施例2:
Pt-2制备方法与Pt-1的合成路线相同,唯一区别是使用化合物9替代化合物4。化合物9的分子式如下所示:
实施例3:
Pt-3制备方法与Pt-1的合成路线相同,唯一区别是使用化合物9替代化合物4,化合物10代替化合物6。化合物10的分子式如下所示:
实施例4:
Pt-12制备方法与Pt-1的合成路线相同,唯一区别是,化合物11代替化合物2,化合物12代替化合物4,化合物10代替化合物6。化合物11的分子式如下所示:
下面是本发明化合物的应用实例。
ITO/TAPC(70nm)/TCTA:Pt(II)(40nm)/TmPyPb(30nm)/LiF(1nm)/Al(90nm)
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)(10Ω/sq)玻璃基板进行超声清洗,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70nm的空穴传输层(HTL)材料TAPC。
然后蒸发厚度为40nm的发光层材料(EML)TCTA,其中掺杂10%质量分数的铂(II)配合物。
然后蒸发厚度为30nm的电子传输层(ETL)材料TmPyPb。
然后蒸发厚度为1nm的LiF为电子注入层(EIL)。
最后蒸发厚度为90nm的Al作为阴极并完成器件封装。见图1所示。
依次制备器件STD、器件1、器件2、器件3、器件4,器件的结构和制作方法完全相同,区别在于依次使用铂(II)配合物STD、Pt-1、Pt-2、Pt-3、Pt-12作为发光层中的掺杂剂。其中,参比材料STD为经典的具有ONCN配位结构的绿光材料。
器件对比结果如表1所示,以器件STD的性能为基准;-表示数据持平,--表示相对基准性能降低了5%以上,+表示相对基准性能提升了5%,++表示相对基准性能提升了10%
器件1 | 器件2 | 器件3 | 器件4 | |
最大外量子效率 | + | + | ++ | ++ |
100nit下的外量子效率 | + | + | + | ++ |
启亮电压 | -- | - | - | - |
100nit下的电流效率 | + | + | + | ++ |
由上表所示,基于本发明铂(II)配合物所制备的有机电致发光器件的性能相对于基准器件具有不同程度的性能提升。这类新型Pt(II)配合物分子立体性强,分子间的相互作用弱,避免了配合物分子之间互相堆叠,极大抑制了激基缔合物的形成,从而提高OLED器件的效率。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,所涉及的新型四齿铂(II)配合物金属有机材料具有较大的应用价值。
Claims (12)
2.根据权利要求1所述的配合物,其中R1-R21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、被卤素或一个或多个C1-C4烷基取代的或未取代的含5-20个C原子的芳基、被卤素或一个或多个C1-C4烷基取代的或未取代的含5-20个C原子的杂芳基、或者相邻R1-R21相互通过共价键连接成环,所述卤素为F,Cl,Br。
3.根据权利要求2所述的配合物,其中R1-R21的21个基团中,其中有0-3个基团独立的表示为二芳胺基、被卤素或1至3个C1-C4烷基取代的或未取代的含5-10个C原子的芳基、被卤素或1至3个C1-C4烷基取代的或未取代的含5-10个C原子的含N杂芳基;其它的基团独立的表示为氢或含1-8个C原子的饱和烷基,所述卤素为F,Cl。
4.根据权利要求3所述的配合物,其中所述R1-R21的21个基团中,其中有0-3个基团独立的表示为二苯胺基、苯基、吡啶基、咔唑基,其它基团独立的表示为氢、氟或者1-4个C原子的饱和烷基。
6.根据权利要求5所述的配合物,其中R1’-R6’的6个基团中,其中有0-3个基团独立的表示为二芳胺基、被卤素或1至3个C1-C4烷基取代的或未取代的含5-10个C原子的芳基、被卤素或1至3个C1-C4烷基取代的或未取代的含5-10个C原子的杂芳基;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。
7.根据权利要求1所述的配合物,其中R1’-R6’的6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1-8任一所述配合物在OLED发光器件中的应用。
12.根据权利要求9所述的应用,所述权利要求1-8任一所述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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