TWI755881B - 一種o^c^n^n型四齒鉑(ii)配合物、製備方法及其應用 - Google Patents
一種o^c^n^n型四齒鉑(ii)配合物、製備方法及其應用 Download PDFInfo
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- TWI755881B TWI755881B TW109134371A TW109134371A TWI755881B TW I755881 B TWI755881 B TW I755881B TW 109134371 A TW109134371 A TW 109134371A TW 109134371 A TW109134371 A TW 109134371A TW I755881 B TWI755881 B TW I755881B
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- halogen
- substituted
- alkyl
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- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 21
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 51
- 229910052736 halogen Inorganic materials 0.000 claims description 43
- 150000002367 halogens Chemical class 0.000 claims description 43
- 125000000217 alkyl group Chemical group 0.000 claims description 27
- 125000003118 aryl group Chemical group 0.000 claims description 24
- 125000001072 heteroaryl group Chemical group 0.000 claims description 21
- -1 cyano, carboxyl Chemical group 0.000 claims description 17
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 16
- 229910052731 fluorine Inorganic materials 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 8
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 8
- 229910052805 deuterium Inorganic materials 0.000 claims description 8
- 125000005266 diarylamine group Chemical group 0.000 claims description 8
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 8
- 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 125000005842 heteroatom Chemical group 0.000 claims description 5
- 239000003446 ligand Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 5
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 5
- 125000004209 (C1-C8) alkyl group Chemical group 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
- 125000004986 diarylamino group Chemical group 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 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
- 239000002019 doping agent Substances 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 125000004076 pyridyl group Chemical group 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 238000007641 inkjet printing Methods 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 238000002207 thermal evaporation Methods 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 7
- 238000007125 Buchwald synthesis reaction Methods 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical group 0.000 claims 1
- 230000017858 demethylation Effects 0.000 claims 1
- 238000010520 demethylation reaction Methods 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 239000013212 metal-organic material Substances 0.000 abstract description 6
- 230000006872 improvement Effects 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000021715 photosynthesis, light harvesting Effects 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- 239000010410 layer Substances 0.000 description 24
- 0 Cc(c(*)c(cc12)-c3c(*)c(*)c(*)c(O*)c3O)c1c(c(*)c(*)c(*)c1*)c1[n]2-c1c(**)c(*)c(*)c(-c2c(*)c(*)c(*)c(*)n2)n1 Chemical compound Cc(c(*)c(cc12)-c3c(*)c(*)c(*)c(O*)c3O)c1c(c(*)c(*)c(*)c1*)c1[n]2-c1c(**)c(*)c(*)c(-c2c(*)c(*)c(*)c(*)n2)n1 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 7
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000002390 rotary evaporation Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000005525 hole transport Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- NCRIDSGPLISUEU-UHFFFAOYSA-N Brc1cccc(-c2ccccn2)n1 Chemical compound Brc1cccc(-c2ccccn2)n1 NCRIDSGPLISUEU-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 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
- PJRGCJBBXGNEGD-UHFFFAOYSA-N Brc(cc1)cc2c1c1ccccc1[nH]2 Chemical compound Brc(cc1)cc2c1c1ccccc1[nH]2 PJRGCJBBXGNEGD-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
- 229910052693 Europium Inorganic materials 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-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
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 2
- XBDYBAVJXHJMNQ-UHFFFAOYSA-N Tetrahydroanthracene Natural products C1=CC=C2C=C(CCCC3)C3=CC2=C1 XBDYBAVJXHJMNQ-UHFFFAOYSA-N 0.000 description 2
- 125000004062 acenaphthenyl group Chemical group C1(CC2=CC=CC3=CC=CC1=C23)* 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 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
- 238000005401 electroluminescence Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 125000005843 halogen group Chemical group 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
- 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
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000003107 substituted aryl group Chemical group 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 2
- 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
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- 150000000183 1,3-benzoxazoles Chemical class 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical class C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DGJBHVCLGFJMEE-PKPIPKONSA-N CC(C)[C@H](C)C(C)Br Chemical compound CC(C)[C@H](C)C(C)Br DGJBHVCLGFJMEE-PKPIPKONSA-N 0.000 description 1
- LSRKLLZLZDRIBX-UHFFFAOYSA-N COc(cccc1)c1-c1ccc(c(cccc2)c2[n]2-c3cccc(-c4ccccn4)n3)c2c1 Chemical compound COc(cccc1)c1-c1ccc(c(cccc2)c2[n]2-c3cccc(-c4ccccn4)n3)c2c1 LSRKLLZLZDRIBX-UHFFFAOYSA-N 0.000 description 1
- HUXKZHPIIYMWKX-UHFFFAOYSA-N COc(cccc1)c1-c1ccc(c2ccccc2[nH]2)c2c1 Chemical compound COc(cccc1)c1-c1ccc(c2ccccc2[nH]2)c2c1 HUXKZHPIIYMWKX-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- FKBTZQDRWAGYCL-UHFFFAOYSA-N Oc1ccccc1-c1ccc(c(cccc2)c2[n]2-c3cccc(-c4ccccn4)n3)c2c1 Chemical compound Oc1ccccc1-c1ccc(c(cccc2)c2[n]2-c3cccc(-c4ccccn4)n3)c2c1 FKBTZQDRWAGYCL-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
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000008316 benzisoxazoles Chemical class 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 229940049706 benzodiazepine Drugs 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
- 230000005540 biological transmission Effects 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
- 150000001716 carbazoles Chemical class 0.000 description 1
- WCZVZNOTHYJIEI-UHFFFAOYSA-N cinnoline Chemical compound N1=NC=CC2=CC=CC=C21 WCZVZNOTHYJIEI-UHFFFAOYSA-N 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001907 coumarones Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 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
- 238000010586 diagram Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
- 150000002545 isoxazoles Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- CAMRHYBKQTWSCM-UHFFFAOYSA-N oxocyanamide Chemical compound O=NC#N CAMRHYBKQTWSCM-UHFFFAOYSA-N 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 125000001828 phenalenyl group Chemical group C1(C=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical compound C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- CPNGPNLZQNNVQM-UHFFFAOYSA-N pteridine Chemical compound N1=CN=CC2=NC=CN=C21 CPNGPNLZQNNVQM-UHFFFAOYSA-N 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 150000003252 quinoxalines Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 238000002061 vacuum sublimation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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Abstract
本發明涉及一種O^C^N^N型四齒鉑(II)配合物的製備及應用。本發明的配合物具有如下式(I)所示的結構,本發明所製備的有機電致發光器件的性能相對於基準器件具有較好的性能提升,所涉及的新型O^C^N^N四齒鉑(II)配合物金屬有機材料具有較大的應用價值。本發明所涉及的四齒鉑(II)配合物基於咔唑骨架,具有大的π-共軛剛性平面結構,能較大減少分子內旋轉和振動等非輻射能量耗散,有利於鉑(II)配合物發光效率與性能的提高。本發明所製備的O^C^N^N四齒鉑(II)配合物金屬有機材料,在有機發光二極體上具有有較大的應用價值,作為磷光摻雜材料製造高發光效率的紅光OLED器件。
Description
本發明涉及一種新型的O^C^N^N四齒鉑(II)配合物金屬有機材料,尤其是用於OLED發光器件的發光層中起紅光光子發射作用的磷光摻雜材料。
有機發光二極體(Organic Light-Emitting Diode,OLED)顯示技術為最新顯示技術,發展前景廣闊。繼CRT、LCD之後,OLED顯示技術橫空出世,其具有自發光特性,不需要背光源,可視度和亮度均高,視角廣,回應快;材料品質輕,厚度薄,具有可柔性顯示的優越性能;同時,與LCD相比,電壓需求低,元件需求少,成本低。OLED性能優越,未來將廣泛應用於智慧手機、電視、可穿戴設備和VR領域,發展前景廣闊。
有機電致發光現象早在1963年就由Pope研究小組發現,當時他們利用了兩種有機材料,分別在Ag/蒽單晶/Ag器件及NaCl/蒽單晶摻雜並四苯/NaCl器件中發現了蒽的發光和並四苯的發光。但由於蒽單晶片的厚度在微米級(10-20μm),且需要採用高達400V的直流電壓,製成單層發光器件,施加400V
電壓,觀察到了微弱的藍光,器件壽命也很短,缺乏實際運用的價值,因此未能在學術界引起廣泛的關注。
直到1987年,美國KODAK公司的C.W.Tang等人採用了蒸鍍技術,以ITO作陽極,將Diamine(75nm)作為空穴傳輸層蒸鍍在ITO玻璃上,再蒸鍍一層Alq3(60nm)作為電子傳輸層和發光層,最後再蒸上低功函數的鎂和鋁作陰極,製成了第一個具有三明治結構的OLED器件,在5V左右的電壓下,觀察到了高亮度的綠光,亮度達到了1000cd/m2,電流效率達到3cd/A,外量子效率達到1%。這項突破性的工作具有里程碑的意義,開創了有機光電研究的新紀元,為有機電致發光研究指明了方向。
在OLED材料領域,磷光類OLED發光層摻雜材料發展較為迅速與成熟,其主要是基於一些重金屬有機配合物,如銥、鉑、銪、鋨等。在重金屬配合物中,重金屬原子的存在可以產生強烈的自旋軌道耦合效應(spin-orbital coupling,SOC),使本來自旋受阻的三線態激子從最低三線態(T1)向基態(S0)輻射躍遷產生磷光,這種方法同時捕獲了三線態和單線態激子,有效利用了無法發光的三線態激子,打破了內量子效率25%的瓶頸,因此理論上其量子效率可達到100%。這使得有機電致磷光器件的性能更加優越,因此磷光材料在0LED中得到了更廣泛深入的開發和研究。通過分散在主體材料中,磷光金屬配合物呈現了非常高的外量子效率(EQE),在最近報導的摻雜的磷光OLEDs,其外量子效率超過30%。
在OLED材料領域,磷光類OLED發光層摻雜材料發展較為迅速與成熟,其主要是基於一些重金屬有機配合物,如銥、鉑、銪、鋨等。在重金屬配合物中,重金屬原子的存在可以產生強烈的自旋軌道耦合效應(spin-orbital
coupling,SOC),使本來自旋受阻的三線態激子從最低三線態(T1)向基態(S0)輻射躍遷產生磷光,這種方法同時捕獲了三線態和單線態激子,有效利用了無法發光的三線態激子,打破了內量子效率25%的瓶頸,因此理論上其量子效率可達到100%。這使得有機電致磷光器件的性能更加優越,因此磷光材料在0LED中得到了更廣泛深入的開發和研究。通過分散在主體材料中,磷光金屬配合物呈現了非常高的外量子效率(EQE),在最近報導的摻雜的磷光OLEDs,其外量子效率超過30%。
OLED技術自開發以來經歷三十多年的發展,尤其是磷光OLED效率的突破,其在商業化應用上表現出了極大的前景。近些年來,基於鉑(II)的磷光OLED材料在逐步發展並取得了較好的研究成果。由於鉑(II)配合物平面結構的特性,也導致其分子間易堆疊,易形成激基締合物等,影響OLED器件的性能,一般通過在分子上增加叔丁基等大位阻基團,增強分子的立體結構,減弱分子間的相互作用。
OLED顯示技術的發展是一項艱巨而意義重大的研究,其具有良好的特性,同時也存在使用壽命短、色彩純度差、易老化等缺點,限製了OLED技術的大規模應用。因此,設計新型的性能優異的OLED材料,尤其是發光層摻雜材料,則是OLED領域研究的重點與難點。
在本發明中,設計了一類新型的基於咔唑骨架的具有O^C^N^N配位元結構的Pt(II)配合物,其呈紅光發射,並研究了其在有機發光二極體上的
應用。咔唑是一類含有富電子的含氮雜環化合物,具有大的π-共軛剛性平面結構,這種獨特的結構使其衍生物表現出了許多優異的光電性能。
其中,R1-R17獨立的選自氫、氘、硫、鹵素、羥基、醯基、烷氧基、醯氧基、氨基、硝基、醯基氨基、氰基、羧基、苯乙烯基、氨基羰基、氨基甲醯基、苄基羰基、芳氧基、矽烷基、二芳胺基、含1-30個C原子的飽和烷基、含1-20個C原子的不飽和烷基、取代的或未取代的含6-30個C原子的芳基、取代的或未取代的含5-30個C原子的雜芳基、或者相鄰R1-R17相互通過共價鍵連接成環;所述取代為被氘、鹵素、氰基、硝基、氨基、C1-C8烷基、所取代,所述雜芳基中雜原子為N、S、O原子。
優選:其中R1-R17獨立的選自氫、鹵素、氨基、硝基、氰基、矽烷基、二芳胺基、含1-10個C原子的飽和烷基、被鹵素或一個或多個C1-C4烷基取代的或未取代的含6-20個C原子的芳基、被鹵素或一個或多個C1-C4烷基取代的或未取代的含5-20個C原子的雜芳基、或者相鄰R1-R16相互通過共價鍵連接成環,所述鹵素為F,Cl,Br。
其中R1’-R5’獨立的選自氫、鹵素、矽烷基、二芳胺基、含1-10個C原子的飽和烷基、被鹵素或一個或多個C1-C4烷基取代的或未取代的含6-20個C原子的芳基、被鹵素或一個或多個C1-C4烷基取代的或未取代的含5-20個C原子的雜芳基、或者相鄰R1 ’-R5 ’相互通過共價鍵連接成環,所述鹵素為F,Cl,Br。
優選:其中R1 ’-R5 ’的5個基團中,其中有0-3個基團獨立的表示為二芳胺基、被鹵素或1至3個C1-C4烷基取代的或未取代的含6-10個C原子的芳基、被鹵素或1至3個C1-C4烷基取代的或未取代的含5-10個C原子的雜芳基;其它的基團獨立的表示為氫、鹵素或含1-8個C原子的飽和烷基,所述鹵素為F,Cl。
優選:其中R1 ’-R5 ’的5個基團中,其中有0-3個基團獨立的表示為二苯胺基、C1-C4烷基取代或未取代的苯基、吡啶基、咔唑基,其它基團獨立的表示為氫、氟、含1-4個C原子的飽和烷基。
其中,R1-R17立的選自氫、氘、硫、鹵素、羥基、醯基、烷氧基、醯氧基、氨基、硝基、醯基氨基、氰基、羧基、苯乙烯基、氨基羰基、氨基甲醯基、苄基羰基、芳氧基、矽烷基、二芳胺基、含1-30個C原子的飽和烷基、含1-20個C原子的不飽和烷基、取代的或未取代的含6-30個C原子的芳基、取代的或未取代的含5-30個C原子的雜芳基、或者相鄰R1-R16相互通過共價鍵連接成環;所述取代為被氘、鹵素、氰基、硝基、氨基、C1-C8烷基、所取代,所述雜芳基中雜原子為N、S、O原子。
其中R1 ’-R5 ’獨立的選自氫、鹵素、矽烷基、二芳胺基、含1-10個C原子的飽和烷基、含6-20個C原子的被鹵素或一個或多個C1-C4烷基取代的或未取代芳
基、含5-20個C原子的被鹵素或一個或多個C1-C4烷基取代的或未取代雜芳基、或者相鄰R1 ’-R5 ’相互通過共價鍵連接成環,所述鹵素為F,Cl,Br。
為了本申請的目的,除非另有指明,術語鹵素、烷基、烯基、芳基、醯基、烷氧基和雜環芳族體系或雜環芳族基團可有以下含義:上述鹵素或鹵代包括氟、氯、溴和碘,優選F,Cl,Br,特別優選F或Cl,最優選F。
上述通過共價鍵連接成環、芳基、雜芳基包括具有5-30個碳原子,優選5-20個碳原子,更優選6-10個碳原子並且由一個芳環或多個稠和的芳環組成的芳基。適宜的芳基為,例如苯基,萘基,苊基(acenaphthenyl),二氫苊基(acenaphthenyl),蒽基、芴基、菲基(phenalenyl)。該芳基可為未取代的(即所有能夠取代的碳原子帶有氫原子)或在芳基的一個、多於一個或所有可取代的位置上被取代。適宜的取代基為例如鹵素,優選F、Br或Cl;烷基,優選具有1-20個,1-10個或1-8個碳原子的烷基,特別優選甲基、乙基、異丙基或叔丁基;芳基,優選可再次被取代的或是未取代C5,C6芳基或芴基;雜芳基,優選含至少一個氮原子的雜芳基,特別優選吡啶基;芳基尤其特別優選帶有選自F,甲基和叔丁基的取代基,或任選被至少一個上述取代基取代的為C5,C6芳基的芳基,C5,C6芳基特別優選帶有0、1或2個上述取代基,C5,C6芳基尤其特別優選未取代的苯基或取代的苯基,諸如聯苯基、被兩個叔丁基優選在間位取代的苯基。
含1-20個C原子的不飽和烷基,優選烯基,更優選具有一個雙鍵的烯基,特別優選具有雙鍵和1-8個碳原子的烯基。
上述烷基包括具有1-30個碳原子,優選1-10個碳原子,優選1-4個碳原子的烷基。該烷基可為支鏈或直鏈的,也可以是環形的,並且可被一個或多個雜原子,優選N、O或S間斷。而且,該烷基可被一個或多個鹵素或上述的關於芳基的取代基所取代。同樣,對於烷基而言,帶有一個或多個芳基是可能的,所有上述的芳基均適用於該目的,烷基特別優選自甲基、乙基、異丙基、正丙基、異丁基、正丁基、叔丁基、仲丁基、異戊基、環丙基、環戊基、環己基。
上述醯基是以單鍵連接至CO基團的,如本文所用的烷基。
上述烷氧基是以單鍵與氧直接相連的,如本文所用的烷基。
上述雜芳基團被理解為與芳族、C3-C8環基相關,並且還包含一個氧或硫原子或1-4個氮原子或一個氧或硫原子與最多兩個氮原子的組合,和他們的取代的以及苯並和吡啶並稠和的衍生物,例如,經由其中一個成環碳原子相連,所述雜芳基團可被一個或多個提到的關於芳基的取代基所取代。
在某些實施方案中,雜芳基可為攜帶以上獨立的含有0、1或2個取代基的五、六元芳族雜環體系。雜芳基的典型實例包括但不限於未取代的呋喃、苯並呋喃、噻吩、苯並噻吩、吡咯、吡啶、吲哚、唑、苯並唑、異唑、苯並異唑、噻唑、苯並噻唑、異噻唑、咪唑、苯並咪唑、吡唑、吲唑、四唑、喹啉、異喹啉、噠嗪、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、***、苯並***、喋啶、苯並唑、二唑、苯並吡唑、喹嗪、噌啉、酞嗪、喹唑和喹喔啉及其單-或二-取代的衍生物。在某些實施方案中,取代基為鹵代、羥基、氰基、O-C1~6烷基、C1~6烷基、羥基C1~6烷基和氨基-C1~6烷基。
上述配合物在OLED發光器件中的應用。
採用具有上述結構的鉑(II)配合物,可製造熱沉積和溶液處理的OLED器件。
包括含有一種或多種上述配合物的有機發光器件。
其中通過熱沉積在該器件中以層形式施加該配合物。
其中通過旋塗在該器件中以層形式施加該配合物。
其中通過噴墨列印在該器件中以層形式施加該配合物。
上述有機發光器件,在施加電流時該器件發射為橙紅色。
本發明中的有機金屬配合物具有高螢光量子效率,良好的熱穩定性及低淬滅常數,可以製造高發光效率、低滾降的紅光OLED器件。
10:玻璃基板
20:陽極
30:空穴傳輸層
40:發光層
50:電子傳輸層
60:電子注入層
70:陰極
圖1本發明的有機電致發光器件的結構示意圖。
下面結合實施例對本發明做進一步的詳細說明。
上述配合物的製備方法,包括如下步驟:如下所示,咔唑類衍生物S1與S2經Suzuki反應得到底物S3,S3與S4經Buchwald反應得到S5,S5在吡啶鹽酸鹽作用下脫甲基得到配體S6,S6與K2PtCl4反應即得到目標產物P。
下面結合實施例對本發明做進一步的詳細說明。
本發明中化合物合成中涉及的初始底物和溶劑均夠自安耐吉,百靈威,阿拉丁等本領域技術人員熟知的供應商。
化合物3的合成:取9.84g(40.0mmol)化合物1,6.69g化合物2(1.1eq.,44.0mmol),碳酸鉀11.04g(2.0eq.,80mmol)和Pd(PPh3)4 924mg(0.02eq.,0.8mmol),加入到三頸燒瓶中,抽真空通入氮氣置換多次,然後注入二氧六環120mL,水40mL,加熱至105℃。在氮氣保護下反應12hr後,冷卻至室溫,再加入適量水和乙酸乙酯萃取,收集有機相,無水硫酸鎂乾燥後旋蒸除去溶劑,使用正己烷/乙酸乙酯體系柱層析(流動相正己烷/乙酸乙酯=10:
1),得到白色固體10.0g,產率92%,純度99.5%。質譜(ESI+)([M-H]-)C19H14NO理論值:272.11;實測值:272.13。
化合物5的合成:取5.47g(20mmol)化合物3,5.17g(1.1eq.,22mmol)化合物4,醋酸鈀225mg(0.02eq.,1mmol),三叔丁基膦0.20g(0.04eq.,2mmol),叔丁醇鉀4.5g(2.0eq.,0.04mol)於燒瓶中,加入100mL甲苯,在氮氣保護下加熱回流反應8小時。停止反應後,冷卻至室溫旋蒸除去溶劑,加入適量水和乙酸乙酯萃取,收集有機相並乾燥,旋蒸除去溶劑後使用快速矽膠色譜柱(流動相正己烷/乙酸乙酯=10:1)分離,得到7.3g目標產物化合物5,產率85%,純度99.9%。質譜(ESI+)([M-H]-)C29H21N3O理論值:426.16;實測值:426.13。
化合物6的合成:取4.27g(10mmol)化合物5,吡啶鹽酸鹽50g,在氮氣保護下加熱至200℃反應8小時。停止反應後,加入適量水和乙酸乙酯萃取,收集有機相並乾燥,旋蒸除去溶劑後使用快速矽膠色譜柱(流動相正己烷/乙酸乙酯=15:1)分離,再使用甲醇重結晶得到目標產物化合物63.3g,產率80%,純度99.9%。質譜(ESI-)([M-H]-)C28H18N3O理論值:412.15;實測值:412.10。
化合物TM-1的合成:取2.06g(5.0mmol)化合物6,400mg四丁基溴化銨(0.25eq.,1.25mmol)和四氯鉑酸鉀2.49mg(1.2eq.,6mmol),溶於150mL乙酸中,抽真空通入氮氣置換數次,攪拌加熱至130℃反應12小時。反應結束後,冷卻旋蒸除去溶劑,再加入適量水和乙酸乙酯萃取,收集有機相,無水硫酸鎂乾燥後旋蒸除去溶劑,使用正己烷/乙酸乙酯體系柱層析,將得到的粗品真空昇華得到紅色固體1.67g,總產率55%,純度99.9%。質譜(ESI+)([M+H]+)C28H18N3OPt理論值:607.10;實測值:607.15。
下面是本發明化合物的應用實例。
ITO/TAPC(60nm)/TCTA:Pt(II)(40nm)/TmPyPb(30nm)/LiF(1nm)/Al(80nm)
器件製備方式:依次使用丙酮、乙醇和蒸餾水對透明陽極20氧化銦錫(ITO)(10Ω/sq)玻璃基板10進行超聲清洗,再用氧氣等離子處理5分鐘。
然後將ITO襯底安裝在真空氣相蒸鍍設備的襯底固定器上。在蒸鍍設備中,控製體系壓力在10-6torr。
此後,向ITO襯底上蒸發厚度為60nm的空穴傳輸層(30)材料TAPC。
然後蒸發厚度為40nm的發光層(40)材料TCTA,其中摻雜10%品質分數的鉑(II)配合物。
然後蒸發厚度為30nm的電子傳輸層(50)材料TmPyPb。
然後蒸發厚度為1nm的LiF為電子注入層(60)。
器件的結構和製作方法完全相同,區別在於依次使用有機金屬配合物P0、P1、P2、P3、P4作為發光層中的摻雜劑與摻雜濃度。其中,STD的O^N^N^O類紅光材料。
依次製備器件STD、器件1、器件2、器件3,器件的結構和製作方法完全相同,區別在於依次使用鉑(II)配合物STD、TM-1、TM-3、TM-5作為發光層中的摻雜劑。其中,參比材料STD為經典的具有ONCN配位元結構的紅光料。
器件對比結果如表1所示,以器件STD的性能為基準;-表示資料持平,--表示相對基準性能降低了5%以上,+表示相對基準性能提升了5%,++表示相對基準性能提升了10%。
其中,基於TM-1的器件1相對於基於STD的參比器件,最大外量子效率和啟亮電壓基本一致,100nit下的外量子效率和電流效率有5%左右的提升;從分子結構上看,TM-1和STD均具有一致的平面結構,但是TM-1有更大的共軛結構,使其在器件性能上相對於STD有一定程度的提升。基於TM-3的器件2相對於參比器件,啟亮電壓基本一致,但是最大外量子效率以及100nit下的外
量子效率和電流效率均有5%左右的提升。從分子結構上看,TM-3分子結構上引入2個叔丁基,一定程度上降低了分子間的聚集和堆疊,有利於器件性能提升。基於TM-5的器件3相對於參比器件,啟亮電壓基本一致,但是最大外量子效率以及100nit下的外量子效率和電流效率均有10%左右的提升;從分子結構上看,TM-3分子結構上引入4個叔丁基,極大增強了分子的立體性,大大降低了分子間相互作用,同時保持分子骨架的剛性結構和大共軛特性,因而器件效率提升最大,性能最佳。
綜上所述,本發明所製備的有機電致發光器件的性能相對於基準器件具有較好的性能提升,外量子效率,或電流效率明顯提高,所涉及的新型O^C^N^N四齒鉑(II)配合物金屬有機材料具有較大的應用價值。本發明所涉及的四齒鉑(II)配合物基於咔唑骨架,具有大的π-共軛剛性平面結構,能較大減少分子內旋轉和振動等非輻射能量耗散,有利於鉑(II)配合物發光效率與性能的提高。本發明所製備的O^C^N^N四齒鉑(II)配合物金屬有機材料,在有機發光二極體上具有有較大的應用價值,作為磷光摻雜材料製造高發光效率的紅光OLED器件。
10:玻璃基板
20:陽極
30:空穴傳輸層
40:發光層
50:電子傳輸層
60:電子注入層
70:陰極
Claims (12)
- 如請求項1所述的配合物,其中,R1-R17獨立的選自氫、鹵素、氨基、硝基、氰基、矽烷基、二芳胺基、含1-10個C原子的飽和烷基、含6-20個C原子的被鹵素或一個或多個C1-C4烷基取代的或未取代芳基、含5-20個C原子的被鹵素或一個或多個C1-C4烷基取代的或未取代雜芳基、或者相鄰R1-R16相互通過共價鍵連接成環,所述鹵素為F,Cl,Br。
- 如請求項3所述的配合物,其中,R1 ’-R5 ’的5個基團中,其中有0-3個基團獨立的表示為二芳胺基、含6-10個C原子被鹵素或1至3個C1-C4烷基取代的或未取代的芳基、含5-10個C原子的被鹵素或1至3個C1-C4烷基取代的或未取代的雜芳基;其它的基團獨立的表示為氫、鹵素或含1-8個C原子的飽和烷基,所述鹵素為F,Cl。
- 如請求項4所述的配合物,其中,R1 ’-R5 ’的5個基團中,其中有0-3個基團獨立的表示為二苯胺基、C1-C4烷基取代或未取代的苯基、吡啶基、咔唑基,其它基團獨立的表示為氫、氟、含1-4個C原子的飽和烷基。
- 一種如請求項1至6中任一項所述的配合物在OLED發光器件中的應用。
- 如請求項10所述的應用,所述請求項1至6中任一項所述的配合物採用通過熱沉積、旋塗、噴墨列印以層形式施加在OLED發光器件中。
- 如請求項10所述的應用,所述請求項1至6中任一項所述的配合物為發光層中起光子發射作用的磷光摻雜材料。
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- 2020-09-19 JP JP2022531588A patent/JP7332809B2/ja active Active
- 2020-09-19 WO PCT/CN2020/116339 patent/WO2021128982A1/zh active Application Filing
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- 2020-09-19 US US17/776,978 patent/US20220416180A1/en active Pending
- 2020-10-05 TW TW109134371A patent/TWI755881B/zh active
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JP2023503673A (ja) | 2023-01-31 |
WO2021128982A1 (zh) | 2021-07-01 |
US20220416180A1 (en) | 2022-12-29 |
CN113024606A (zh) | 2021-06-25 |
JP7332809B2 (ja) | 2023-08-23 |
DE112020004784T5 (de) | 2022-06-15 |
CN113024606B (zh) | 2023-04-18 |
KR20220065852A (ko) | 2022-05-20 |
TW202124405A (zh) | 2021-07-01 |
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