CN109678907A - A kind of metal platinum (II) complex of the phenyl-phenyl containing bridging-carbazole structure unit and its application - Google Patents
A kind of metal platinum (II) complex of the phenyl-phenyl containing bridging-carbazole structure unit and its application Download PDFInfo
- Publication number
- CN109678907A CN109678907A CN201811646306.9A CN201811646306A CN109678907A CN 109678907 A CN109678907 A CN 109678907A CN 201811646306 A CN201811646306 A CN 201811646306A CN 109678907 A CN109678907 A CN 109678907A
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- Prior art keywords
- base
- group
- phenyl
- complex
- amino
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 55
- 239000002184 metal Substances 0.000 title claims abstract description 53
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 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 title claims abstract description 22
- 125000001424 substituent group Chemical group 0.000 claims abstract description 32
- -1 nitro, cyano, amino Chemical group 0.000 claims description 135
- 125000000217 alkyl group Chemical group 0.000 claims description 108
- 125000001072 heteroaryl group Chemical group 0.000 claims description 83
- 125000003118 aryl group Chemical group 0.000 claims description 62
- 125000003368 amide group Chemical group 0.000 claims description 58
- 125000003342 alkenyl group Chemical group 0.000 claims description 53
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 50
- 125000000304 alkynyl group Chemical group 0.000 claims description 48
- 229910052736 halogen Inorganic materials 0.000 claims description 47
- 125000003545 alkoxy group Chemical group 0.000 claims description 45
- 150000002367 halogens Chemical class 0.000 claims description 45
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 42
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 39
- 229910021529 ammonia Inorganic materials 0.000 claims description 38
- 229910052739 hydrogen Inorganic materials 0.000 claims description 37
- 239000001257 hydrogen Substances 0.000 claims description 37
- 125000000623 heterocyclic group Chemical group 0.000 claims description 36
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 33
- 125000004104 aryloxy group Chemical group 0.000 claims description 31
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 31
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 31
- 125000004185 ester group Chemical group 0.000 claims description 31
- 150000002527 isonitriles Chemical class 0.000 claims description 31
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 31
- 238000006116 polymerization reaction Methods 0.000 claims description 31
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 31
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 31
- 125000004414 alkyl thio group Chemical group 0.000 claims description 30
- 125000004466 alkoxycarbonylamino group Chemical group 0.000 claims description 29
- 125000005162 aryl oxy carbonyl amino group Chemical group 0.000 claims description 29
- 125000004442 acylamino group Chemical group 0.000 claims description 28
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 26
- 229910052805 deuterium Inorganic materials 0.000 claims description 26
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims description 26
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 25
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 238000006467 substitution reaction Methods 0.000 claims description 12
- 125000003226 pyrazolyl group Chemical group 0.000 claims description 9
- 125000001590 germanediyl group Chemical group [H][Ge]([H])(*)* 0.000 claims description 8
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 229910052701 rubidium Inorganic materials 0.000 claims description 6
- XMIJDTGORVPYLW-UHFFFAOYSA-N [SiH2] Chemical compound [SiH2] XMIJDTGORVPYLW-UHFFFAOYSA-N 0.000 claims description 5
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 229910018162 SeO2 Inorganic materials 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- JQQSUOJIMKJQHS-UHFFFAOYSA-N pentaphenyl group Chemical group C1=CC=CC2=CC3=CC=C4C=C5C=CC=CC5=CC4=C3C=C12 JQQSUOJIMKJQHS-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 4
- 239000000463 material Substances 0.000 abstract description 27
- 239000003446 ligand Substances 0.000 abstract description 20
- 230000008901 benefit Effects 0.000 abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 120
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 85
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 57
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 51
- 229910052757 nitrogen Inorganic materials 0.000 description 45
- 150000001875 compounds Chemical class 0.000 description 41
- 239000002904 solvent Substances 0.000 description 39
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N DMSO-d6 Substances [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 34
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 34
- 238000000034 method Methods 0.000 description 32
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 31
- 238000006243 chemical reaction Methods 0.000 description 30
- 230000015572 biosynthetic process Effects 0.000 description 26
- 229910052697 platinum Inorganic materials 0.000 description 26
- 238000003786 synthesis reaction Methods 0.000 description 26
- 239000012074 organic phase Substances 0.000 description 24
- 238000005160 1H NMR spectroscopy Methods 0.000 description 22
- 239000003480 eluent Substances 0.000 description 21
- 150000003254 radicals Chemical class 0.000 description 21
- 238000010898 silica gel chromatography Methods 0.000 description 21
- 238000011068 loading method Methods 0.000 description 20
- 239000007832 Na2SO4 Substances 0.000 description 19
- 229910052799 carbon Inorganic materials 0.000 description 19
- 229910052938 sodium sulfate Inorganic materials 0.000 description 19
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 238000000295 emission spectrum Methods 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- 239000003208 petroleum Substances 0.000 description 13
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 13
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 10
- 238000005292 vacuum distillation Methods 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 125000004429 atom Chemical group 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 8
- 238000004770 highest occupied molecular orbital Methods 0.000 description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 150000004696 coordination complex Chemical class 0.000 description 7
- 230000003111 delayed effect Effects 0.000 description 7
- 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 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000001721 carbon Chemical group 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 125000005842 heteroatom Chemical group 0.000 description 6
- 239000011368 organic material Substances 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 238000010791 quenching Methods 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 6
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 5
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 description 5
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 5
- 150000002576 ketones Chemical class 0.000 description 5
- 230000031700 light absorption Effects 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 4
- 239000003550 marker Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 125000006574 non-aromatic ring group Chemical group 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- RZEMXCXZMMENMI-UHFFFAOYSA-N 1,2-diphenyl-9h-carbazole Chemical group C1=CC=CC=C1C1=CC=C(C=2C(=CC=CC=2)N2)C2=C1C1=CC=CC=C1 RZEMXCXZMMENMI-UHFFFAOYSA-N 0.000 description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910020427 K2PtCl4 Inorganic materials 0.000 description 3
- SIOXPEMLGUPBBT-UHFFFAOYSA-N Picolinic acid Natural products OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000005347 biaryls Chemical group 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 125000004366 heterocycloalkenyl group Chemical group 0.000 description 3
- 125000004415 heterocyclylalkyl group Chemical group 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 3
- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 0.000 description 3
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 3
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 3
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 0 CC(C)(C)C1=CCN(*2(c(c3c(cc4)c(cccc5)c5[n]33)c4O4)/N=C(\C)/C(c(cc5)c(C6(C)C)cc5-c5ccccc5)=C6Nc5c2c4ccc5)C3=C1 Chemical compound CC(C)(C)C1=CCN(*2(c(c3c(cc4)c(cccc5)c5[n]33)c4O4)/N=C(\C)/C(c(cc5)c(C6(C)C)cc5-c5ccccc5)=C6Nc5c2c4ccc5)C3=C1 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- BXKSGDDGASLCQF-UHFFFAOYSA-N [N].C1COCCO1 Chemical compound [N].C1COCCO1 BXKSGDDGASLCQF-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000002015 acyclic group Chemical group 0.000 description 2
- 125000003282 alkyl amino group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000003851 azoles Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000021615 conjugation Effects 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
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000004663 dialkyl amino group Chemical group 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 230000026030 halogenation Effects 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- SBOJXQVPLKSXOG-UHFFFAOYSA-N o-amino-hydroxylamine Chemical compound NON SBOJXQVPLKSXOG-UHFFFAOYSA-N 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 125000002971 oxazolyl group Chemical group 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 150000003057 platinum Chemical class 0.000 description 2
- NDBYXKQCPYUOMI-UHFFFAOYSA-N platinum(4+) Chemical compound [Pt+4] NDBYXKQCPYUOMI-UHFFFAOYSA-N 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000003217 pyrazoles Chemical class 0.000 description 2
- 239000012925 reference material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OOMZKLJLVGQZGV-UHFFFAOYSA-N (2,5-dimethylphenyl)boronic acid Chemical compound CC1=CC=C(C)C(B(O)O)=C1 OOMZKLJLVGQZGV-UHFFFAOYSA-N 0.000 description 1
- NSJVYHOPHZMZPN-UHFFFAOYSA-N (2-methylphenyl)boronic acid Chemical compound CC1=CC=CC=C1B(O)O NSJVYHOPHZMZPN-UHFFFAOYSA-N 0.000 description 1
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- 150000005070 1,2,3-oxadiazoles Chemical class 0.000 description 1
- 125000004511 1,2,3-thiadiazolyl group Chemical group 0.000 description 1
- 125000001399 1,2,3-triazolyl group Chemical class N1N=NC(=C1)* 0.000 description 1
- HTJMXYRLEDBSLT-UHFFFAOYSA-N 1,2,4,5-tetrazine Chemical compound C1=NN=CN=N1 HTJMXYRLEDBSLT-UHFFFAOYSA-N 0.000 description 1
- 125000004517 1,2,5-thiadiazolyl group Chemical group 0.000 description 1
- 150000000182 1,3,5-triazines Chemical class 0.000 description 1
- DVQWNQBEUKXONL-UHFFFAOYSA-N 1-iodo-2-methoxybenzene Chemical compound COC1=CC=CC=C1I DVQWNQBEUKXONL-UHFFFAOYSA-N 0.000 description 1
- FBTOLQFRGURPJH-UHFFFAOYSA-N 1-phenyl-9h-carbazole Chemical compound C1=CC=CC=C1C1=CC=CC2=C1NC1=CC=CC=C12 FBTOLQFRGURPJH-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- XRXMNWGCKISMOH-UHFFFAOYSA-N 2-bromobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1Br XRXMNWGCKISMOH-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- OEDUIFSDODUDRK-UHFFFAOYSA-N 5-phenyl-1h-pyrazole Chemical compound N1N=CC=C1C1=CC=CC=C1 OEDUIFSDODUDRK-UHFFFAOYSA-N 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 229910004749 OS(O)2 Inorganic materials 0.000 description 1
- 244000131316 Panax pseudoginseng Species 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- TZRXHJWUDPFEEY-UHFFFAOYSA-N Pentaerythritol Tetranitrate Chemical compound [O-][N+](=O)OCC(CO[N+]([O-])=O)(CO[N+]([O-])=O)CO[N+]([O-])=O TZRXHJWUDPFEEY-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical class C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- DPOPAJRDYZGTIR-UHFFFAOYSA-N Tetrazine Chemical compound C1=CN=NN=N1 DPOPAJRDYZGTIR-UHFFFAOYSA-N 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000003678 cyclohexadienyl group Chemical group C1(=CC=CCC1)* 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 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
- 125000006547 cyclononyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- ZPWOOKQUDFIEIX-UHFFFAOYSA-N cyclooctyne Chemical compound C1CCCC#CCC1 ZPWOOKQUDFIEIX-UHFFFAOYSA-N 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000002012 dioxanes Chemical class 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000002024 ethyl acetate extract Substances 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002244 furazanes Chemical class 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000000589 high-performance liquid chromatography-mass spectrometry Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 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
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 125000002463 lignoceryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([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
- SFDJOSRHYKHMOK-UHFFFAOYSA-N nitramide Chemical compound N[N+]([O-])=O SFDJOSRHYKHMOK-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- ZAOCWQZQPKGTRN-UHFFFAOYSA-N nitrous acid;sodium Chemical compound [Na].ON=O ZAOCWQZQPKGTRN-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008707 rearrangement 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
- 239000010801 sewage sludge Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 125000005017 substituted alkenyl group Chemical group 0.000 description 1
- 125000005415 substituted alkoxy group Chemical group 0.000 description 1
- 125000005346 substituted cycloalkyl group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 238000001429 visible spectrum 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0086—Platinum 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
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/346—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising platinum
-
- 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
- H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
-
- 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
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
Abstract
The present invention provides a kind of phenyl-phenyl containing bridging-carbazole structure unit metal platinum (II) complex and its application.Metal platinum (II) complex has structure shown in logical formula (I).Luminescent material provided by the present invention, the structure of substituent group regulates and controls the photophysics property of four ring gear metal platinum (II) complexs in the structure and regulation ligand by adjusting the ligand around metal center, has the advantages that stability height and high-efficient；It the numerous areas such as shows and illuminates in OLED and has broad application prospects.
Description
[technical field]
The present invention relates to technical field of organic luminescence materials, and in particular to a kind of phenyl-phenyl containing bridging-carbazole knot
Four ring gear metal platinum (II) complex phosphorescences and delayed fluorescence of structure unit or pure phosphorescent light-emitting materials and its application.
[background technique]
The compound that can absorb and/or emit light is applicable to various optics and electroluminescent device, comprising: light absorption
Device, solar energy Sensitive Apparatus and light-sensitive device, Organic Light Emitting Diode (OLED), light emitting devices, or light can either be carried out
It absorbs and is able to carry out light emitting and the device as the marker (marker) for biologic applications again.It is many research oneself be dedicated to
It was found that and optimizing for the organic material used in optics and electroluminescent device and organo metallic material.In general, the field
In research aim at many targets, including absorb and the improvement of emission effciency and the improvement of working ability.
Good blue light emitting material is very rare in luminous organic material, and blue-light device stablizes not good enough, relatively red green phosphorescence
Material, blue emitting phosphor material lowest triplet state energy level are higher, it is meant that the stability of phosphor material is even more important in blue-light device.
In general, the variation of chemical structure will affect the electronic structure of compound, its optical property is thus influenced (for example, hair
Penetrate and absorption spectrum), therefore, changing chemical structure can make compound have specific transmitting or absorption characteristic.In addition, changing
The optical property for closing object can also be adjusted by changing the ligand of structure centre.For example, with electron substituent group or inhaling electricity
The compound of the ligand of sub- substituent group usually shows different optical properties, including different transmittings and absorption spectrum.
Since the multiple tooth type platinum metal complex of phosphorescence can utilize the singlet and triplet excitons of electroexcitation simultaneously, obtain
The internal quantum for obtaining 100%, so that these complexs can be used as the alternative luminescent material of OLEDs.In general, multiple tooth type platinum
The ligand of metal complex includes luminophore and auxiliary group.If introducing conjugation group, such as by aromatic ring substituents or miscellaneous original
Sub- substituent group etc. is introduced into light emitting molecule, highest molecule occupied orbital (the Highest Occupied of luminescent material
Molecular, HOMO) and minimum molecule unoccupied orbital (Lowest Unoccupied Molecular, LUMO) energy grade meeting quilt
Change, meanwhile, further adjust the energy gaps between HOMO track and LUMO track, the adjustable multiple tooth type platinum of phosphorescence
Complex emission spectrum property, it is wider or narrower such as to make its, or makes its blue shift.Thus it can meet in light emitting and absorb application
The demand of middle performance improvement.
Although document many reports existing to divalent Cyclometalated platinum (II) metal complex phosphor material, for containing
Then there is not been reported for the phenyl-phenyl of bridging-carbazole structure unit four ring gear metal platinum (II) complex.
[summary of the invention]
The purpose of the present invention is to provide a kind of four ring gear metal of the phenyl-phenyl containing bridging-carbazole structure unit
Platinum (II) complex, the type complex can be used as the luminescent material in OLED device.The present invention lead to the link group by phenyl ring and
Pyrazole ring is chained up, and can effectively reduce phenyl-pyrazole dihedral angle, is allowed to tend to zero degree, conjugated degree each other is big
Width is promoted, and can effectively be adjusted the triplet of Cyclometalated platinum (II) complex, is allowed to be greatly lowered；Platinum ion simultaneously
Strong Effect of Spin-orbit Coupling, so that complex room temperature spectrum is issued the delayed fluorescence of blue shift, therefore available based on this design
The small material of triplet realizes blue light emitting, provides strong solution to stablize the development of Nan dian Yao.In addition, this
Eka-platinium (II) complex also has molecular rigidity height, the good advantage of stability；Metal platinum (II) complex is applied to shine
In device, the operating time of luminous efficiency and device can be improved, OLED show and illuminate etc. numerous areas have it is wide
Application prospect.
Technical scheme is as follows: in a first aspect, embodiments of the present invention provide a kind of benzene containing bridging
Base-phenyl-carbazole structure unit metal platinum (II) complex, metal platinum (II) complex have shown in logical formula (I)
Structure
Wherein:
The link group X is selected from CH2、CHD、CD2、CR100R101、SiH2、SiHD、SiD2、SiR102R103、GeH2、Ge HD、
GeD2、GeR104R105；
A is selected from O, S, CH2、CHD、CD2、CR200R201, C=O, SiR202R203、GeH2、GeR204R205、NH、ND、NR206、
PH、PD、PR207、R208P=O, AsR209、R210As=O, S=O, SO2, Se, Se=O, SeO2、BH、BD、BR211、R212Bi=O,
BiH, BiD or BiR213；
Ra、Rb、Rc、Rd、Re、RfAnd RgIt is each independently selected from hydrogen, deuterium, aryl, naphthenic base, cycloalkenyl, heterocycle, heteroaryl
Base, alkyl, alkenyl, alkynyl, halogen, hydroxyl, sulfydryl, nitro, cyano, amino, list or dialkyl amido, list or ammonia diaryl
Base, alkoxy, aryloxy group, halogenated alkyl, ester group, itrile group, isonitrile base, heteroaryl, alkoxy carbonyl, acylamino-, alkoxy carbonyl
Base amino, aryloxycarbonylamino, sulfuryl amino, sulfamoyl, carbamoyl, alkylthio group, sulfinyl, urea groups, phosphorus
Amide groups, imido grpup, sulfo group, carboxyl, diazanyl, silicyl, substituted silicyl, polymerization group, or combinations thereof；Ra、
Rb、Rc、Rd、Re、RfAnd RgSubstitution mode each independently represent for it is monosubstituted, disubstituted, three replace, four replace or without taking
Generation, two adjacent substituent groups can form condensed ring；
S indicates that the integer of 0-5, m, n integer independent for indicating 0-4, o indicate that the integer of 0-2, p, r are respectively independent
Expression 0-3 integer, q indicate 0-1 integer；
The R100、R101、R102、R103、R104、R105、R200、R201、R202、R203、R204、R205、R206、R207、R208、R209、
R210、R211、R212、R213Be each independently selected from aryl, naphthenic base, cycloalkenyl, heterocycle, heteroaryl, alkyl, alkenyl, alkynyl,
Halogen, hydroxyl, sulfydryl, nitro, cyano, amino, list or dialkyl amido, list or ammonia diaryl base, alkoxy, aryloxy group, halogen
Substituted alkyl, ester group, itrile group, isonitrile base, heteroaryl, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino, aryloxycarbonyl ammonia
Base, sulfuryl amino, sulfamoyl, carbamoyl, alkylthio group, sulfinyl, urea groups, phosphinylidyne amido, imido grpup, sulfo group,
Carboxyl, diazanyl, silicyl, substituted silicyl, polymerization group, or combinations thereof；Wherein two adjacent substituent groups can
To form condensed ring；
The Ar1For the phenyl being connected with pyrazolyl, the Ar2For with Ar1Connected phenyl, the α are Ar1With pyrazoles
The dihedral angle of base, the β are Ar1With Ar2Dihedral angle.
Optionally, metal platinum (II) complex has structure shown in logical formula (II), (III):
Wherein, R1、R2、R3、R4、R5、R6、R7、R8、R9、R10And R11It is each independently hydrogen, deuterium, aryl, naphthenic base, ring
Alkenyl, heterocycle, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, sulfydryl, nitro, cyano, amino, list or dialkyl amino
Base, list or ammonia diaryl base, alkoxy, aryloxy group, halogenated alkyl, ester group, itrile group, isonitrile base, heteroaryl, alkoxy carbonyl,
Acylamino-, alkoxycarbonyl amino, aryloxycarbonylamino, sulfuryl amino, sulfamoyl, carbamoyl, alkylthio group, Asia
Sulfonyl, urea groups, phosphinylidyne amido, imido grpup, sulfo group, carboxyl, diazanyl, silicyl, substituted silicyl, polymerization base
Group, or combinations thereof；The adjacent R1、R2、R3、R4、R5、R6、R7、R8、R9、R10And R11It can connect to form condensed ring.
Optionally, metal platinum (II) complex has structure shown in logical formula (IV), (V):
Wherein, R1、R2、R3、R4、R5、R6、R7、R8、R9、R10And R11Be each independently selected from hydrogen, deuterium, aryl, naphthenic base,
Cycloalkenyl, heterocycle, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, sulfydryl, nitro, cyano, amino, list or dialkyl group
Amino, list or ammonia diaryl base, alkoxy, aryloxy group, halogenated alkyl, ester group, itrile group, isonitrile base, heteroaryl, alkoxy carbonyl
Base, acylamino-, alkoxycarbonyl amino, aryloxycarbonylamino, sulfuryl amino, sulfamoyl, carbamoyl, alkane sulphur
Base, sulfinyl, urea groups, phosphinylidyne amido, imido grpup, sulfo group, carboxyl, diazanyl, silicyl, substituted silicyl, polymerization
Group, or combinations thereof；The adjacent R1、R2、R3、R4、R5、R6、R7、R8、R9、R10And R11It can connect to form condensed ring.
Optionally, the R1、R2、R3、R4、R5、R6、R7、R8、R9、R10And R11Be each independently selected from hydrogen, methyl, ethyl,
Propyl, butyl, amyl, hexyl, heptyl, octyl, phenyl, tolyl, ethylbenzene, propyl phenyl, butylbenzene base, penta phenyl, own phenyl,
Heptan phenyl or pungent phenyl.
Optionally, metal platinum (II) complex has one of following structure:
The metal of the above-mentioned phenyl-phenyl containing bridging-carbazole structure unit provided by embodiments of the present invention
Platinum (II) complex has neutral charge.
Embodiments of the present invention also provide the metal platinum of the above-mentioned phenyl-phenyl containing bridging-carbazole structure unit
(II) application of the complex in electroluminescent device.
In addition, embodiments of the present invention also provide a kind of device, the device includes as described above containing bridging
Phenyl-phenyl-carbazole structure unit metal platinum (II) complex.
Optionally, the device is full-color display, photovoltaic device, light-emitting display device, Organic Light Emitting Diode or phosphorus
Light Organic Light Emitting Diode.
Optionally, in the device provided by embodiments of the present invention, including at least one cathode, at least one anode
With at least one layer of luminescent layer, at least one layer in the luminescent layer includes phenyl-phenyl-carbazole containing bridging as described above
Metal platinum (II) complex of structural unit.
The beneficial effects of the present invention are: first, passing through the link group for phenyl Ar1It is chained up with pyrazolyl, it can be with
Effectively reduce phenyl Ar1Pyrazoles dihedral angle α, is allowed to tend to zero degree, enhances the rigidity of molecule；Second, passing through regulation phenyl Ar1-
Phenyl Ar2Phenyl Ar is adjusted in dihedral angle β1Phenyl Ar2Between conjugated degree, and then the luminosity of material is carried out high
Effect ground is adjusted.If phenyl Ar2Ortho position without non-hydrogen substituent, steric hindrance is smaller, is allowed to and phenyl Ar1Conjugated degree is larger, ring gold
The triplet for belonging to platinum (II) complex reduces；The strong Effect of Spin-orbit Coupling of platinum ion simultaneously, also makes complex
The delayed fluorescence of room temperature spectrum sending blue shift；If in phenyl Ar2Ortho position introduce non-hydrogen substituent, steric hindrance increase, be allowed to
Phenyl Ar1Conjugated degree greatly reduces, and the triplet of Cyclometalated platinum (II) complex increases, and can be directly used as blue emitting phosphor
Material.The inventors discovered that no matter phenyl Ar in the compounds of this invention2Ortho position whether have non-hydrogen substituent, may be implemented
Blue-light-emitting provides strong solution to stablize the development of Nan dian Yao, the numerous areas tool such as shows and illuminate in OLED
Have broad application prospects.
[Detailed description of the invention]
Fig. 1 is Room temperature emission spectra of the metal platinum complex Pt3 of the present invention in dichloromethane solution and in 2- methyl four
77K emission spectrum in hydrogen furans；
Fig. 2 is Room temperature emission spectra of the metal platinum complex Pt14 of the present invention in dichloromethane solution and in 2- methyl four
77K emission spectrum in hydrogen furans；
Fig. 3 is Room temperature emission spectra of the metal platinum complex Pt31 of the present invention in dichloromethane solution and in 2- methyl four
77K emission spectrum in hydrogen furans；
Fig. 4 is HOMO-1, HOMO, LUMO and LUMO+1 orbit distribution of metal platinum complex Pt3 of the present invention；
Fig. 5 is HOMO-1, HOMO, LUMO and LUMO+1 orbit distribution of metal platinum complex Pt31 of the present invention；
Fig. 6 is HOMO-1, HOMO, LUMO and LUMO+1 orbit distribution of metal platinum complex Pt32 of the present invention；
Fig. 7 is HOMO-1, HOMO, LUMO and LUMO+1 orbit distribution of metal platinum complex Pt33 of the present invention；
Fig. 8 is the normalization luminescent spectrum of metal platinum complex Pt3 of the present invention and reference material.
It should be pointed out that general remark and following detailed description above is all only exemplary and explanatory, no
With limited.
[specific embodiment]
The invention will be further described with embodiment with reference to the accompanying drawing.
Before disclosing and describing the compound of the present invention, device and/or method, it should be appreciated that they are not limited to specifically
Synthetic method (otherwise can also point out), or specific reagent (otherwise can also point out), because this can certainly change
's.It should also be appreciated that term used in the present invention is only for the purpose of description specific aspect, and it is not intended to be limitation.Although
It can be used in the practice or test with those of present invention description similar or of equal value any method and material, be described below
Illustrative method and material.
Term " optional " used in the present invention or " optionally " mean the event then described or situation can with or
Do not occur, and the description include the case where the event or happen and it not there is a situation where.
Disclose the component that can be used for preparing composition of the present invention, and the method to be used to disclose in the present invention
In composition itself.These and other substance is disclosed in the present invention, and be should be understood that work as and disclosed the group of these substances
Conjunction, subset, interaction, group, etc., and cannot specifically disclose that each of these compounds are various individually and total combination and to be set
When the specific ginseng reference changed, each is specifically expected in the present invention and describes.For example, if being disclosed and discussed specific
Compound, and many modifications that can be carried out to many molecules comprising the compound are discussed, then specifically expected should
The various and every kind of combination and displacement of compound, and the modification can be can be carried out, otherwise can in addition specifically it point out on the contrary.
Therefore, if the example of molecule A, B and C and molecule D, E and F and combination molecule A-D are disclosed, then being
Make each not record individually, it is also considered that disclose it is each individually and generally expected meaning combination, A-E, A-F, B-D,
B-E, B-F, C-D, C-E and C-F.Similarly, any subset or these combination are also disclosed.Thus, for example, it should it examines
Worry discloses group A-E, B-F and C-E.These ideas are suitable for the invention all aspects, including but not limited to prepare and make
In the step of the method for the composition.Therefore, it is able to carry out if there is various other steps, it should be appreciated that these are another
The combination that outer step is respectively capable of specific embodiment in this way or embodiment carries out.
The connection atom that the present invention uses can connect two groups, for example, N and C group.The connection atom can be optional
Ground (if valence link permission) has the chemical part of other attachments.For example, on the one hand, oxygen will not have any other chemistry
Group attachment, has been satisfied because being once bonded to two atoms (for example, N or C) valence link.On the contrary, when carbon is connection atom
When, two other chemical parts can be attached to the carbon atom.Suitable chemical part includes but is not limited to hydrogen, hydroxyl, alkane
Base, alkoxy ,=O, halogen, nitro, amine, amide, mercapto, aryl, heteroaryl, naphthenic base and heterocycle.
Terminology used in the present invention " cyclic structure " or similar terms refer to any cyclic annular chemical structure comprising but it is unlimited
In aryl, heteroaryl, naphthenic base, cycloalkenyl, heterocycle, Cabbeen and N- heterocycle carbine.
The substituent group of " substituted " the expected all permissions comprising organic compound of terminology used in the present invention.In wide side
Face, the substituent group of permission include acyclic and cyclic annular, branching and non-branching, carbocyclic ring the and heterocycle of organic compound, and
Aromatics and non-aromatic substituents.Those of illustrative substituent group includes, for example, be described below.For suitable organic compound
For object, the substituent group of permission can be one or more, same or different.For the purposes of the present invention, hetero atom (example
Such as nitrogen) can have hydrogen substituent group and/or organic compound of the present invention any permission substituent group, it is miscellaneous to meet this
The valence link of atom.The disclosure is not intended to carry out any restrictions with the substituent group that organic compound allows in any way.Equally,
Term " substitution " or " substitution has " include the valences that Implicit Conditions are the permission that this substitution meets substituted atom He the substituent group
Key and the substitution cause stable compound (for example, (such as by rearrangement, cyclisation, cancellation etc.) will not be converted spontaneously
Compound).It is also contemplated that in some aspects, unless clearly pointing out on the contrary, otherwise, individual substituent group can be further
It is optionally to replace (that is, being further substituted or unsubstituted).
When defining various terms, " R1”、“R2”、“R3" and " R4" it is used as total symbol in the present invention to indicate various
Specific substituent group.These symbols can be any substituent group, be not limited to those of present disclosure, and work as them in one kind
In the case of when being limited to certain substituent groups, they can be limited to some other substituent groups in other cases.
Terminology used in the present invention " alkyl " is the alkyl of the saturation of branching or nonbranched 1 to 24 carbon atom, example
Such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-amyl, newly
Amyl, hexyl, heptyl, half base, nonyl, decyl, dodecyl, myristyl, cetyl, eicosyl, tetracosyl
Deng.The alkyl can be cyclic annular or acyclic.The alkyl can be branching or non-branching.The alkyl can also be substituted or unsubstituted
's.For example, the alkyl may replace one or more groups, the alkyl including but not limited to of the present invention optionally replaced,
Naphthenic base, alkoxy, amino, ether, halogen, hydroxyl, nitro, silicyl, sulphur-oxo (Sulfo-OXO) or mercapto.It is " low
Grade alkyl " group is the alkyl containing 1 to 6 (such as 1 to 4) carbon atom.
Throughout the specification, " alkyl " is commonly used in while referring to unsubstituted alkyl and replace alkyl；But replace alkane
Base is also specifically referred to by determining the specific substituent group on alkyl in the present invention.For example, term " alkyl of halogenation "
Or " halogenated alkyl " specifically refers to replace one or more halogens (for example, fluorine, chlorine, bromine or iodine) alkyl.Term
" alkoxyalkyl " specifically refers to replace the alkyl for having one or more alkoxies, as described below.Term " alkyl amino " tool
Refer to body that substitution has the alkyl of one or more amino, as described below, etc..When in oneainstance use " alkyl " and another
When in one situation using specific nomenclature such as " alkylol ", it is not intended to imply that the term " alkyl " does not refer to specific art simultaneously
Language such as " alkylol ".
This practice is also used for other groups of the present invention.That is, when term such as " naphthenic base " while referring to unsubstituted
When with substituted cycloalkyl moiety, in addition which can specifically determine in the present invention；For example, the ring specifically replaced
Alkyl can be described as such as " alkyl-cycloalkyl ".Similar, substituted alkoxy can be particularly referred to as such as " alkoxy of halogenation ",
Specific substituted alkenyl can be such as " enol " etc..Similarly, using total term such as " naphthenic base " and specific nomenclature such as " alkane
The practice of basic ring alkyl " is not intended to imply total term not simultaneously comprising the concrete term.
Terminology used in the present invention " naphthenic base " is the non-aromatic ring based on carbon being made of at least three carbon atoms.Cycloalkanes
The example of base includes but is not limited to cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, cyclononyl, etc..Term " Heterocyclylalkyl " is one
Class naphthenic base as defined above, and be included in the meaning of term " naphthenic base ", wherein at least one ring carbon atom is by miscellaneous original
Son is such as, but not limited to nitrogen, oxygen, and sulphur or phosphorus replace.The naphthenic base and Heterocyclylalkyl can be substituted or unsubstituted.The naphthenic base
It may replace one or more groups with Heterocyclylalkyl, alkyl including but not limited to as described in the present invention, naphthenic base, alcoxyl
Base, amino, ether, halogen, hydroxyl, nitro, silicyl, sulphur-oxo (sulfo-oxo) or mercapto.
Term " polyolefin group " its used for this invention be used to refer to generation containing two or more CH2It group and is connected to
Other same part." polyolefin group " can be expressed as-(CH2)a, wherein " a " is integer 2 to 500.
Term " alkoxy " and " alkoxy base ", it is used for this invention to be used to refer to for the alkane being bonded by ether linker
Base or naphthenic base；That is, " alkoxy " may be defined as-OR1, wherein R1It is alkyl or cycloalkyl as defined above." alkoxy "
Polymer comprising the alkoxy just described；That is, alkoxy can be polyethers such as-OR1-OR2Or-OR1-(OR2)a-OR3,
Wherein " a " is integer 1 to 200, and R1、R2And R3It is each independently alkyl, naphthenic base or combinations thereof.
Terminology used in the present invention " alkenyl " is the alkyl of 2 to 24 carbon atoms, and structural formula contains at least one carbon-to-carbon
Double bond.Dissymmetrical structure such as (R1R2) C=C (R3R4) it is intended to encompass E and Z isomers.This can be estimated in structural formula of the invention
In, wherein there are unsymmetrical alkenes or it can be explicitly indicated that by keysym C=C.The alkenyl may replace one or more
Group, alkyl including but not limited to of the present invention, naphthenic base, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl radical, aryl,
Heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azido, nitro, silicyl, sulfenyl-oxo (sulfo-
) or mercapto oxo.
Terminology used in the present invention " cycloalkenyl " is the non-aromatic ring based on carbon, is made of at least three carbon atom, and
And contain at least one carbon-carbon double bond, that is, C=C.The example of cycloalkenyl includes but is not limited to cyclopropanyl, cyclobutane base, ring penta
Alkenyl, cyclopentadienyl group, cyclohexenyl group, cyclohexadienyl, norbornene (norbornenyl), etc..Term " heterocycloalkenyl "
It is a kind of cycloalkenyl as defined above, and is included in the meaning of term " cycloalkenyl ", wherein at least one carbon of the ring is former
Son is such as, but not limited to nitrogen, oxygen, sulphur or phosphorus with hetero atom and replaces.Cycloalkenyl and heterocycloalkenyl can be substituted or unsubstituted.It should
Cycloalkenyl and heterocycloalkenyl may replace one or more groups, alkyl including but not limited to of the present invention, naphthenic base, alkane
Oxygroup, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl radical, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, nitrine
Base, nitro, silicyl, sulfenyl-oxo (sulfo-oxo) or mercapto.
Terminology used in the present invention " alkynyl " is the alkyl with 2 to 24 carbon atoms, has and contains at least one carbon-
The structural formula of three key of carbon.Alkynyl can be it is unsubstituted or replace and have one or more group, the group includes but unlimited
In alkyl of the present invention, naphthenic base, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl radical, aryl, heteroaryl, aldehyde, amino,
Carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azido, nitro, silicyl, sulfenyl-oxo (sulfo-oxo) or mercapto.
Terminology used in the present invention " cycloalkynyl radical " is the non-aromatic ring based on carbon, it includes at least seven carbon atoms and is contained
There is at least one carbon-carbon triple bond.The example of cycloalkynyl radical includes but is not limited to cycloheptyl alkynyl, cyclooctyne base, cyclonoyne base etc..Term
" heterocycle alkynyl " is a type of cycloalkenyl as defined above, and is included in the meaning of term " cycloalkynyl radical ", wherein
At least one of the carbon atom of the ring is substituted by hetero atom, and the hetero atom is such as, but not limited to nitrogen, oxygen, sulphur or phosphorus.
Cycloalkynyl radical and heterocycle alkynyl can be substituted or unsubstituted.Cycloalkynyl radical and heterocycle alkynyl may replace one or more group,
The group includes but is not limited to alkyl of the present invention, naphthenic base, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl radical, virtue
Base, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxyl, ketone, azido, nitro, silicyl, sulfenyl-oxo
(sulfo-oxo) or mercapto.
Terminology used in the present invention " aryl " is the group containing any aromatic group based on carbon, the virtue based on carbon
Race's group includes but is not limited to benzene, naphthalene, phenyl, biphenyl, phenoxy group benzene etc..Term " aryl " also includes " heteroaryl ", is determined
Justice is the group containing aromatic group, and there is the aromatic group at least one to introduce the hetero atom in the ring of aromatic group.It is miscellaneous
The example of atom includes but is not limited to nitrogen, oxygen, sulphur and phosphorus.Equally, (it is also included within term " aryl " to term " non-heteroaryl "
In) group containing aromatic group is defined, the aromatic group is free of hetero atom.Aryl can be substituted or unsubstituted.Virtue
Base may replace one or more group, and the group includes but is not limited to alkyl of the present invention, naphthenic base, alcoxyl
Base, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl radical, aryl, heteroaryl, aldehyde group, amino, carboxylic acid group, ester group, ether group, halogen
Element, hydroxyl, ketone groups, azido, nitro, silicyl, sulphur-oxo group or sulfydryl.Term " biaryl (biaryl) "
It is certain types of aryl and is included in the definition of " aryl ".Biaryl refers to combined through bridged ring structure
Two aryl, as in naphthalene, or two aryl being keyed through one or more carbon-to-carbon, as in biphenyl.
Terminology used in the present invention " aldehyde " is indicated by formula-C (O) H.Throughout the specification, " C (O) " is carbonyl (that is, C
=O) shorthand.
Terminology used in the present invention " amine " or " amino " pass through formula-NR1R2It indicates, wherein R1And R2Can it is independent from hydrogen,
It is selected in alkyl, naphthenic base, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl radical, aryl or heteroaryl.
Terminology used in the present invention " alkyl amino " indicates that wherein alkyl is as described herein by formula-NH (- alkyl).
Representative example includes but is not limited to methylamino, ethylamino, propylcarbamic, isopropylamino, butylamino, isobutyl group ammonia
Base, (sec-butyl) amino, (tert-butyl) amino, pentyl amino, isoamylamino, (tertiary pentyl) amino, hexylamino etc..
Terminology used in the present invention " dialkyl amido " passes through formula-N (alkyl)2It indicates, wherein alkyl is as described herein.
Representative example includes but is not limited to dimethylamino, diethylamino, dipropylamino, diisopropylaminoethyl, dibutylamine
Base, diisobutylamino, two (sec-butyl) amino, two (tert-butyl) amino, dipentylamino, diisoamyl amino, two (uncle penta
Base) amino, dihexyl amino, N- ethyl-N-methylamino, N- methyl-N-propylamino, N- ethyl-N- propylcarbamic etc..
Terminology used in the present invention " carboxylic acid " is indicated by formula-C (O) OH.
Terminology used in the present invention " ester " passes through formula-OC (O) R1Or-C (O) OR1It indicates, wherein R1 can be institute of the present invention
Alkyl, naphthenic base, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl radical, aryl or the heteroaryl stated.Terminology used in the present invention is " poly-
Ester " passes through formula-(R1O(O)C-R2-C(O)O)aOr-(R1O(O)C-R2-OC(O))aIt indicates, wherein R1And R2It can independently be
Alkyl, naphthenic base, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl radical, aryl or heteroaryl of the present invention and " a " be 1 to
500 integer.The compound and there are at least two hydroxyls that term " polyester " is used to describe by at least two carboxyls
The group that reaction between compound generates.
Terminology used in the present invention " ether " passes through formula R1OR2It indicates, wherein R1And R2Alkane of the present invention can independently be
Base, naphthenic base, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl radical, aryl or heteroaryl.Terminology used in the present invention " polyethers " passes through
Formula-(R1O-R2O)aIt indicates, wherein R1And R2Alkyl of the present invention, naphthenic base, alkenyl, cycloalkenyl, alkynes can independently be
The integer that base, cycloalkynyl radical, aryl or heteroaryl and " a " are 1 to 500.The example of polyether group include polyethylene glycol oxide,
Polypropylene oxide and polyoxybutylene.
Terminology used in the present invention " halogen " refers to halogens fluorine, chlorine, bromine and iodine.
Terminology used in the present invention " heterocycle " refers to monocycle and polycyclic non-aromatic ring system, and the present invention uses
" heteroaryl " refers to monocycle and polycyclic aromatics ring system: at least one of its ring members are not carbon.The term includes nitrogen
Azetidinyl, dioxanes base, furyl, imidazole radicals, isothiazolyl, isoxazolyl, morpholinyl, oxazolyl including 1,2,3-
Oxadiazoles base, 1,2,5- oxadiazoles bases and 1, the oxazolyls of 3,4- oxadiazoles bases, piperazinyl, piperidyl, pyrazinyl, pyrazolyl,
Pyridazinyl, pyridyl group, pyrimidine radicals, pyrrole radicals, pyrrolidinyl, tetrahydrofuran base, THP trtrahydropyranyl including 1,2,4,5- tetrazine bases
Tetrazine base including 1,2,3,4- tetrazole radicals and 1, the tetrazole radical of 2,4,5- tetrazole radicals including 1,2,3- thiadiazolyl groups, 1,2,5-
Thiadiazolyl group and 1, thiadiazolyl group, thiazolyl, thienyl including the 1,3,5-triazines base and 1 of 3,4- thiadiazolyl groups, 2,4- triazines
The triazine radical including 1,2,3-triazoles base and 1 of base, the triazolyl etc. of 3,4- triazolyls.
Terminology used in the present invention " hydroxyl " is indicated by formula-OH.
Terminology used in the present invention " ketone " passes through formula R1C(O)R2It indicates, wherein R1And R2It can independently be of the present invention
Alkyl, naphthenic base, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl radical, aryl or heteroaryl.
Terminology used in the present invention " azido " passes through formula-N3It indicates.
Terminology used in the present invention " nitro " passes through formula-NO2It indicates.
Terminology used in the present invention " nitrile " is indicated by formula-CN.
Terminology used in the present invention " silicyl " passes through formula-SiR1R2R3It indicates, wherein R1、R2And R3It can independently be
Hydrogen perhaps alkyl of the present invention, naphthenic base, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl radical, aryl or heteroaryl.
Terminology used in the present invention " sulphur-oxo group " passes through formula-S (O) R1、-S(O)2R1、-OS(O)2R1Or-OS (O)2OR1It indicates, wherein R1Can be hydrogen or alkyl of the present invention, naphthenic base, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl radical, aryl,
Or heteroaryl.Throughout the specification, " S (O) " is the shorthand of S=O.Terminology used in the present invention " sulfonyl " refers to
Pass through formula-S (O)2R1Sulphur-oxo group of expression, wherein R1Can for alkyl, naphthenic base, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl radical,
Aryl or heteroaryl.Terminology used in the present invention " sulfone " passes through formula R1S(O)2R2It indicates, wherein R1And R2This can independently be
Invention alkyl, naphthenic base, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl radical, aryl or the heteroaryl.The art that the present invention uses
Language " sulfoxide " passes through formula R1S(O)R2It indicates, wherein R1And R2Alkyl of the present invention, naphthenic base, alkenyl, ring can independently be
Alkenyl, alkynyl, cycloalkynyl radical, aryl or heteroaryl.
Terminology used in the present invention " sulfydryl " is indicated by formula-SH
" the R that the present invention uses1”、“R2”、“R3”、“Rn" (wherein n be integer) can independently have above-named group
In one or more.For example, if R1For straight chained alkyl, then a hydrogen atom of alkyl can be optionally substituted with hydroxyl,
Alkoxy, alkyl, halogen etc..Depending on the group of selection, the first group be may be incorporated in the second group, or selectively,
First group, which can be hung, is connected to the second group.For example, amino may be incorporated in alkyl for phrase " wrapping amino-containing alkyl "
Main chain in.Selectively, amino can be connected to the main chain of alkyl.The property of selected group may determine whether that the first group is embedded in
Or it is connected to the second group.
Compound of the present invention contains " optionally replacing " part.In general, term " substituted " (no matter be in front
It is no that there are term " optional ") mean the substituent group substitution that one or more hydrogen for the part pointed out is suitble to.Unless separately making
Illustrate, otherwise " optionally replacing " group that can may replace position in each of group has suitable substituent group, and when in office
When more than one position may replace the substituent group for having more than one selected from specified group in the structure what is provided, in each position
Substituent group can be same or different.It is contemplated by the invention that substituent group combination preferably form stable or chemically feasibleization
Close those of object.In some aspects, unless clearly opposite instruction, otherwise also covers, each substituent group can further appoint
Choosing is substituted (that is, be further substituted with or unsubstituted).
The structure of compound can be indicated by following formula:
It is understood to be equal to following formula:
Wherein n is usually integer.That is, RnIt is understood to mean five individual substituent Rsa(1)、Ra(2)、Ra(3)、Ra(4)、Ra (5)." individual substituent group " refers to that each R substituent can be limited independently.For example, if in a situation Ra(m)For halogen,
So in this case Ra(n)It is not necessarily halogen.
R is referred to for several times in disclosed by the invention and description chemical structure and part1、R2、R3、R4、R5、R6Deng.It is saying
R in bright book1、R2、R3、R4、R5、R6Deng any description be respectively suitable for reference R1、R2、R3、R4、R5、R6Deng any structure or
Person part, unless otherwise mentioned.
Due to many reasons, become more more and more urgent using the opto-electronic device of organic material.For manufacturing this device
Many materials it is relatively cheap, therefore organic photoelectric device have inorganic device cost advantage potentiality.In addition, organic material
Inherent characteristic, such as their flexibility, the special applications such as manufacture that them can be made to be very suitable on a flexible substrate.
The example of organic optoelectronic device includes organic luminescent device (OLED), organic photoelectric transistor, organic photovoltaic battery and organic
Photodetector.For OLED, organic material may have the feature performance benefit better than conventional material.For example, organic luminous layer is sent out
The wavelength of light can usually be tuned with dopant appropriate.
Exciton decays to ground state from singlet excited to generate and shine immediately, is fluorescence.If exciton is from triple excitations
It is luminous to generate that state decays to ground state, this is phosphorescence.Since heavy metal atom is strong between singlet and triplet excited states
Quantum geometrical phase, effectively enhance be between pass through (ISC), so phosphorescent metal complex (such as platinum complex) is rendered
Its potentiality for utilizing singlet and triplet excitons simultaneously out, realize 100% internal quantum.Therefore, phosphorescent metal cooperates
Object is the good selection of the dopant in the emission layer of organic luminescent device (OLED), and in academic and industrial circle
Obtain great concern.In the past decade, many achievements are had been achieved for, so as to cause the profitable of the technology
Commercialization, for example, OLED has been used for smart phone, the sophisticated display of TV and digital camera.
However, so far, blue electroluminescent devices are still field most challenging in the technology, blue device
Stability be the big problem of one.It has been proved that the selection of material of main part is extremely important to the stability of blue device.But
Triplet excited state (T1) minimum energy of blue emitting material is very high, it means that the triple of the material of main part of blue device swash
Sending out state (T1) minimum energy should be higher.This causes the exploitation difficulty of the material of main part of blue equipment to increase.
Metal complex of the invention can be customized or be tuned to be desired to have the specific of particular transmission or absorption characteristic
Using.It can be adjusted by changing the structure of the ligand around metal center or changing the structure of the fluorescent illuminant on ligand
The optical property of metal complex disclosed by the invention.For example, in transmitting and absorption spectrum, matching with electron substituent group
The metal complex or electron-withdrawing substituent of body can usually show different optical properties.It can be by modifying fluorescence radiation
Conjugation group on body and ligand adjusts the color of metal complex.
The transmitting of complex of the invention can be adjusted for example by changing ligand or fluorescent illuminant structure, such as from
Ultraviolet light is to near-infrared.Fluorescent illuminant is one group of atom in organic molecule, and energy can be absorbed to generate singlet state and swash
State is sent out, substance exciton decays rapidly to generate and shine immediately.On the one hand, complex of the invention can provide most of visible spectrum
Transmitting.In specific example, complex of the invention can shine in the wavelength band of visible light or near infrared light.It is another
Aspect, complex of the invention have improved stability and efficiency relative to traditional transmitting complex.In addition, of the invention
Complex can be used as such as biologic applications, anticancer agent, and emitter in Organic Light Emitting Diode (OLED) or combinations thereof shines
Label.On the other hand, complex of the invention can be used for luminescent device, such as compact fluorescent lamp (CFL), light emitting diode
(LED), incandescent lamp and combinations thereof.
Disclosed herein is compounds or compound complex comprising platinum.Term compound or complex are interchangeable in the present invention
It uses.In addition, compound disclosed herein has neutral charge.
Compound disclosed herein can show desired property and have can be by selecting suitable ligand tune
The transmitting of section and/or absorption spectrum.On the other hand, the present invention can exclude any one or more ofization specifically described herein
Close object, structure or part thereof.
Compound disclosed herein is suitable for various optics and electro-optical device, and including but not limited to light absorption fills
It sets, such as solar energy and photosensitive device, Organic Light Emitting Diode (OLEDs), light emitting devices or light absorption and hair can be compatible with
The device penetrated and the marker as biologic applications.
As described above, disclosed compound is platinum complex.Meanwhile compound disclosed herein can be used as OLED application
Material of main part, such as full-color display.
Compound disclosed herein can be used for various applications.As luminescent material, which can be used for organic light emission two
Pole pipe (OLED), light emitting device and display and other luminescent devices.
In addition, the compound in the present invention is for can be improved in luminescent device (such as OLEDs) relative to traditional material
The operating time of luminous efficiency and device.
A variety of method preparations can be used in the compound of the present invention, described in embodiment including but not limited to provided herein
Those of.
Compound disclosed herein can be the fluorescence and/or phosphorescent emitters of delay.On the one hand, chemical combination disclosed herein
Object can be the fluorescent emitter of delay.On the one hand, compound disclosed herein can be phosphorescent emitters.On the other hand, originally
Compound disclosed in text can be delayed fluorescence emitter and phosphorescent emitters.
The present invention is related to luminous organic material, includes four flute profile metals of phenyl ring-carbazole and its derivative in the patent
Platinum complex, the type complex can be used as phosphorescent light-emitting materials in OLED device, for improving efficiency and the service life of device.
A kind of four ring gears gold of the phenyl-phenyl containing bridging-carbazole structure unit disclosed in the embodiment of the present invention
Belong to platinum (II) complex, tetravalent metal platinum (II) complex has structure shown in logical formula (I):
Wherein:
The link group X is selected from CH2、CHD、CD2、CR100R101、SiH2、SiHD、SiD2、SiR102R103、GeH2、Ge HD、
GeD2、GeR104R105；
A is selected from O, S, CH2、CHD、CD2、CR200R201, C=O, SiR202R203、GeH2、GeR204R205、NH、ND、NR206、
PH、PD、PR207、R208P=O, AsR209、R210As=O, S=O, SO2, Se, Se=O, SeO2、BH、BD、BR211、R212Bi=O,
BiH, BiD or BiR213；
Ra、Rb、Rc、Rd、Re、RfAnd RgIt is each independently selected from hydrogen, deuterium, aryl, naphthenic base, cycloalkenyl, heterocycle, heteroaryl
Base, alkyl, alkenyl, alkynyl, halogen, hydroxyl, sulfydryl, nitro, cyano, amino, list or dialkyl amido, list or ammonia diaryl
Base, alkoxy, aryloxy group, halogenated alkyl, ester group, itrile group, isonitrile base, heteroaryl, alkoxy carbonyl, acylamino-, alkoxy carbonyl
Base amino, aryloxycarbonylamino, sulfuryl amino, sulfamoyl, carbamoyl, alkylthio group, sulfinyl, urea groups, phosphorus
Amide groups, imido grpup, sulfo group, carboxyl, diazanyl, silicyl, substituted silicyl, polymerization group, or combinations thereof；Ra、
Rb、Rc、Rd、Re、RfAnd RgSubstitution mode each independently represent for it is monosubstituted, disubstituted, three replace, four replace or without taking
Generation, two adjacent substituent groups can form condensed ring；
S indicates that the integer of 0-5, m, n integer independent for indicating 0-4, o indicate that the integer of 0-2, p, r are respectively independent
Expression 0-3 integer, q indicate 0-1 integer；
The R100、R101、R102、R103、R104、R105、R200、R201、R202、R203、R204、R205、R206、R207、R208、R209、
R210、R211、R212、R213Be each independently selected from aryl, naphthenic base, cycloalkenyl, heterocycle, heteroaryl, alkyl, alkenyl, alkynyl,
Halogen, hydroxyl, sulfydryl, nitro, cyano, amino, list or dialkyl amido, list or ammonia diaryl base, alkoxy, aryloxy group, halogen
Substituted alkyl, ester group, itrile group, isonitrile base, heteroaryl, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino, aryloxycarbonyl ammonia
Base, sulfuryl amino, sulfamoyl, carbamoyl, alkylthio group, sulfinyl, urea groups, phosphinylidyne amido, imido grpup, sulfo group,
Carboxyl, diazanyl, silicyl, substituted silicyl, polymerization group, or combinations thereof；Wherein two adjacent substituent groups can
To form condensed ring；
The Ar1For the phenyl being connected with pyrazolyl, the Ar2For with Ar1Connected phenyl, the α are Ar1With pyrazoles
The dihedral angle of base, the β are Ar1With Ar2Dihedral angle.
Optionally, metal platinum (II) complex has structure shown in logical formula (II), (III):
Wherein, R1、R2、R3、R4、R5、R6、R7、R8、R9、R10And R11It is each independently hydrogen, deuterium, aryl, naphthenic base, ring
Alkenyl, heterocycle, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, sulfydryl, nitro, cyano, amino, list or dialkyl amino
Base, list or ammonia diaryl base, alkoxy, aryloxy group, halogenated alkyl, ester group, itrile group, isonitrile base, heteroaryl, alkoxy carbonyl,
Acylamino-, alkoxycarbonyl amino, aryloxycarbonylamino, sulfuryl amino, sulfamoyl, carbamoyl, alkylthio group, Asia
Sulfonyl, urea groups, phosphinylidyne amido, imido grpup, sulfo group, carboxyl, diazanyl, silicyl, substituted silicyl, polymerization base
Group, or combinations thereof；The adjacent R1、R2、R3、R4、R5、R6、R7、R8、R9、R10And R11It can connect to form condensed ring.
Optionally, metal platinum (II) complex has structure shown in logical formula (IV), (V):
Wherein, lead to formula (IV), the R in (V)1、R2、R3、R4、R5、R6、R7、R8、R9、R10And R11It is each independently hydrogen, first
Base, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, phenyl, tolyl, ethylbenzene, propyl phenyl, butylbenzene base, penta benzene
Base, own phenyl, phenyl in heptan or pungent phenyl.
Four ring gears of the above-mentioned phenyl-phenyl containing bridging-carbazole structure unit provided by embodiments of the present invention
Metal platinum (II) complex has neutral charge.
Embodiments of the present invention also provide the four ring gears gold of the above-mentioned phenyl-phenyl containing bridging-carbazole structure unit
Belong to application of platinum (II) complex in electroluminescent device.
In addition, embodiments of the present invention also provide a kind of device, including phenyl-benzene described above containing bridging
Base-carbazole structure unit four ring gear metal platinum (II) complex.
Optionally, the device is full-color display.
Optionally, the device is photovoltaic device.
Optionally, the device is light-emitting display device.
Optionally, the device is Organic Light Emitting Diode.
Optionally, the device is pure phosphorescence or phosphorescence and delayed fluorescence Organic Light Emitting Diode.
Optionally, four ring gear metal platinum (II) the complexs warp of the phenyl-phenyl containing the bridging-carbazole structure unit
Being selected as in device environment has 100% internal quantum.
Optionally, in the device provided by embodiments of the present invention, including at least one cathode, at least one anode
With at least one layer of luminescent layer, at least one layer in luminescent layer includes phenyl-phenyl-carbazole structure described above containing bridging
Four ring gear metal platinum (II) complexs of unit.
1) X group
Wherein X can be from CH2,CHD,CD2,CR100R101,SiH2,SiHD,SiD2,SiR102R103,GeH2,Ge HD,GeD2
Or GeR104R105Middle selection；The R100、R101、R102、R103、R104、R105It each independently represents as aryl, naphthenic base, cyclenes
Base, heterocycle, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, sulfydryl, nitro, cyano, amino, list or dialkyl amido,
List or ammonia diaryl base, alkoxy, aryloxy group, halogenated alkyl, ester group, itrile group, isonitrile base, heteroaryl, alkoxy carbonyl, acyl ammonia
Base, alkoxycarbonyl amino, aryloxycarbonylamino, sulfuryl amino, sulfamoyl, carbamoyl, alkylthio group, sulfenyl
Base, urea groups, phosphinylidyne amido, imido grpup, sulfo group, carboxyl, diazanyl, silicyl, substituted silicyl, polymerization group or
A combination thereof；
On the other hand, X is C (CH3)2；
On the other hand, X be C (nBu)2；
On the other hand, X CH2；
On the other hand, X CR100R101；
On the other hand, X is Si (CH3)2；
On the other hand, X be Si (nBu)2；
On the other hand, X SiH2；
On the other hand, X SiPh2；
On the other hand, X SiR100R101。
2) A group
Wherein A can be O, S, CH2,CHD,CD2,CR200R201, C=O, SiR202R203,GeH2,GeR204R205,NH,ND,
NR206,PH,PD,PR207,R208P=O, AsR209,R210As=O, S=O, SO2, Se, Se=O, SeO2,BH,BD,BR211,R212Bi
=O, BiH, BiD, or BiR213；The R200、R201、R202、R203、R204、R205、R206、R207、R208、R209、R210、R211、R212、
R213Each independently represent for aryl, naphthenic base, cycloalkenyl, heterocycle, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl,
Sulfydryl, nitro, cyano, amino, list or dialkyl amido, list or ammonia diaryl base, alkoxy, aryloxy group, halogenated alkyl, ester
Base, itrile group, isonitrile base, heteroaryl, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino, aryloxycarbonylamino, sulfonyl
Amino, sulfamoyl, carbamoyl, alkylthio group, sulfinyl, urea groups, phosphinylidyne amido, imido grpup, sulfo group, carboxyl, diazanyl,
Silicyl, substituted silicyl, polymerization group, or combinations thereof；
On the other hand, A O；
On the other hand, A S；
On the other hand, A CR200R201；
On the other hand, A NR206；
On the other hand, A R208P=O；
On the other hand, A PR207；
On the other hand, A BR211；
Furthermore A SiR202R203。
3) R group
Wherein, RaIn the presence of another aspect RaIt is not present.
On the one hand, RaIt is monosubstituted, another aspect, RaIt is disubstituted；On the other hand, RaIt is three substitutions；Furthermore RaIt is four
Replace；
R simultaneouslyaFrom hydrogen, deuterium, aryl, naphthenic base, cycloalkenyl, heterocycle, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl
Base, sulfydryl, nitro, cyano, amino, list or dialkyl amido, list or ammonia diaryl base, alkoxy, aryloxy group, halogenated alkyl,
Ester group, itrile group, isonitrile base, heteroaryl, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino, aryloxycarbonylamino, sulphonyl
Base amino, sulfamoyl, carbamoyl, alkylthio group, sulfinyl, urea groups, phosphinylidyne amido, imido grpup, sulfo group, carboxyl, hydrazine
Base, substituted silicyl, polymerization group, or combinations thereof in select.
Wherein, RbIn the presence of another aspect RbIt is not present.
On the one hand, RbIt is monosubstituted, another aspect, RbIt is disubstituted；On the other hand, RbIt is three substitutions；Furthermore RbIt is four
Replace；
R simultaneouslybFrom hydrogen, deuterium, aryl, naphthenic base, cycloalkenyl, heterocycle, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl
Base, sulfydryl, nitro, cyano, amino, list or dialkyl amido, list or ammonia diaryl base, alkoxy, aryloxy group, halogenated alkyl,
Ester group, itrile group, isonitrile base, heteroaryl, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino, aryloxycarbonylamino, sulphonyl
Base amino, sulfamoyl, carbamoyl, alkylthio group, sulfinyl, urea groups, phosphinylidyne amido, imido grpup, sulfo group, carboxyl, hydrazine
Base, substituted silicyl, polymerization group, or combinations thereof in select.
Wherein, RcIn the presence of another aspect RcIt is not present.
On the one hand, RcIt is monosubstituted, another aspect, RcIt is disubstituted；On the other hand, RcIt is three substitutions；Furthermore RcIt is four
Replace；
R simultaneouslycFrom hydrogen, deuterium, aryl, naphthenic base, cycloalkenyl, heterocycle, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl
Base, sulfydryl, nitro, cyano, amino, list or dialkyl amido, list or ammonia diaryl base, alkoxy, aryloxy group, halogenated alkyl,
Ester group, itrile group, isonitrile base, heteroaryl, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino, aryloxycarbonylamino, sulphonyl
Base amino, sulfamoyl, carbamoyl, alkylthio group, sulfinyl, urea groups, phosphinylidyne amido, imido grpup, sulfo group, carboxyl, hydrazine
Base, substituted silicyl, polymerization group, or combinations thereof in select.
Wherein, RdIn the presence of another aspect RdIt is not present.
On the one hand, RdIt is monosubstituted, another aspect, RdIt is disubstituted；
R simultaneouslydFrom hydrogen, deuterium, aryl, naphthenic base, cycloalkenyl, heterocycle, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl
Base, sulfydryl, nitro, cyano, amino, list or dialkyl amido, list or ammonia diaryl base, alkoxy, aryloxy group, halogenated alkyl,
Ester group, itrile group, isonitrile base, heteroaryl, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino, aryloxycarbonylamino, sulphonyl
Base amino, sulfamoyl, carbamoyl, alkylthio group, sulfinyl, urea groups, phosphinylidyne amido, imido grpup, sulfo group, carboxyl, hydrazine
Base, substituted silicyl, polymerization group, or combinations thereof in select.
Wherein, ReIn the presence of another aspect ReIt is not present.
On the one hand, ReIt is monosubstituted, another aspect, ReIt is disubstituted；
R simultaneouslyeFrom hydrogen, deuterium, aryl, naphthenic base, cycloalkenyl, heterocycle, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl
Base, sulfydryl, nitro, cyano, amino, list or dialkyl amido, list or ammonia diaryl base, alkoxy, aryloxy group, halogenated alkyl,
Ester group, itrile group, isonitrile base, heteroaryl, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino, aryloxycarbonylamino, sulphonyl
Base amino, sulfamoyl, carbamoyl, alkylthio group, sulfinyl, urea groups, phosphinylidyne amido, imido grpup, sulfo group, carboxyl, hydrazine
Base, substituted silicyl, polymerization group, or combinations thereof in select.
Wherein, RfIn the presence of another aspect RfIt is not present.
On the one hand, RfIt is monosubstituted, another aspect, RfIt is disubstituted；
R simultaneouslyfFrom hydrogen, deuterium, aryl, naphthenic base, cycloalkenyl, heterocycle, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl
Base, sulfydryl, nitro, cyano, amino, list or dialkyl amido, list or ammonia diaryl base, alkoxy, aryloxy group, halogenated alkyl,
Ester group, itrile group, isonitrile base, heteroaryl, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino, aryloxycarbonylamino, sulphonyl
Base amino, sulfamoyl, carbamoyl, alkylthio group, sulfinyl, urea groups, phosphinylidyne amido, imido grpup, sulfo group, carboxyl, hydrazine
Base, substituted silicyl, polymerization group, or combinations thereof in select.
Wherein, RgIn the presence of another aspect RgIt is not present.
On the one hand, RgIt is monosubstituted, another aspect, RgIt is disubstituted；
R simultaneouslygFrom hydrogen, deuterium, aryl, naphthenic base, cycloalkenyl, heterocycle, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl
Base, sulfydryl, nitro, cyano, amino, list or dialkyl amido, list or ammonia diaryl base, alkoxy, aryloxy group, halogenated alkyl,
Ester group, itrile group, isonitrile base, heteroaryl, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino, aryloxycarbonylamino, sulphonyl
Base amino, sulfamoyl, carbamoyl, alkylthio group, sulfinyl, urea groups, phosphinylidyne amido, imido grpup, sulfo group, carboxyl, hydrazine
Base, substituted silicyl, polymerization group, or combinations thereof in select.
Wherein, R1In the presence of another aspect R1It is not present.
On the one hand, R1It is monosubstituted, another aspect, R1It is disubstituted；
R simultaneously1From hydrogen, deuterium, aryl, naphthenic base, cycloalkenyl, heterocycle, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl
Base, sulfydryl, nitro, cyano, amino, list or dialkyl amido, list or ammonia diaryl base, alkoxy, aryloxy group, halogenated alkyl,
Ester group, itrile group, isonitrile base, heteroaryl, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino, aryloxycarbonylamino, sulphonyl
Base amino, sulfamoyl, carbamoyl, alkylthio group, sulfinyl, urea groups, phosphinylidyne amido, imido grpup, sulfo group, carboxyl, hydrazine
Base, substituted silicyl, polymerization group, or combinations thereof in select.
Wherein, R2In the presence of another aspect R2It is not present.
On the one hand, R2It is monosubstituted, another aspect, R2It is disubstituted；
R simultaneously2From hydrogen, deuterium, aryl, naphthenic base, cycloalkenyl, heterocycle, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl
Base, sulfydryl, nitro, cyano, amino, list or dialkyl amido, list or ammonia diaryl base, alkoxy, aryloxy group, halogenated alkyl,
Ester group, itrile group, isonitrile base, heteroaryl, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino, aryloxycarbonylamino, sulphonyl
Base amino, sulfamoyl, carbamoyl, alkylthio group, sulfinyl, urea groups, phosphinylidyne amido, imido grpup, sulfo group, carboxyl, hydrazine
Base, substituted silicyl, polymerization group, or combinations thereof in select.
Wherein, R3In the presence of another aspect R3It is not present.
On the one hand, R3It is monosubstituted, another aspect, R3It is disubstituted；
R simultaneously3From hydrogen, deuterium, aryl, naphthenic base, cycloalkenyl, heterocycle, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl
Base, sulfydryl, nitro, cyano, amino, list or dialkyl amido, list or ammonia diaryl base, alkoxy, aryloxy group, halogenated alkyl,
Ester group, itrile group, isonitrile base, heteroaryl, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino, aryloxycarbonylamino, sulphonyl
Base amino, sulfamoyl, carbamoyl, alkylthio group, sulfinyl, urea groups, phosphinylidyne amido, imido grpup, sulfo group, carboxyl, hydrazine
Base, substituted silicyl, polymerization group, or combinations thereof in select.
Wherein, R4In the presence of another aspect R4It is not present.
On the one hand, R4It is monosubstituted, another aspect, R4It is disubstituted；
R simultaneously4From hydrogen, deuterium, aryl, naphthenic base, cycloalkenyl, heterocycle, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl
Base, sulfydryl, nitro, cyano, amino, list or dialkyl amido, list or ammonia diaryl base, alkoxy, aryloxy group, halogenated alkyl,
Ester group, itrile group, isonitrile base, heteroaryl, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino, aryloxycarbonylamino, sulphonyl
Base amino, sulfamoyl, carbamoyl, alkylthio group, sulfinyl, urea groups, phosphinylidyne amido, imido grpup, sulfo group, carboxyl, hydrazine
Base, substituted silicyl, polymerization group, or combinations thereof in select.
Wherein, R5In the presence of another aspect R5It is not present.
On the one hand, R5It is monosubstituted, another aspect, R5It is disubstituted；
R simultaneously5From hydrogen, deuterium, aryl, naphthenic base, cycloalkenyl, heterocycle, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl
Base, sulfydryl, nitro, cyano, amino, list or dialkyl amido, list or ammonia diaryl base, alkoxy, aryloxy group, halogenated alkyl,
Ester group, itrile group, isonitrile base, heteroaryl, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino, aryloxycarbonylamino, sulphonyl
Base amino, sulfamoyl, carbamoyl, alkylthio group, sulfinyl, urea groups, phosphinylidyne amido, imido grpup, sulfo group, carboxyl, hydrazine
Base, substituted silicyl, polymerization group, or combinations thereof in select.
Wherein, R6In the presence of another aspect R6It is not present.
On the one hand, R6It is monosubstituted, another aspect, R6It is disubstituted；
R simultaneously6From hydrogen, deuterium, aryl, naphthenic base, cycloalkenyl, heterocycle, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl
Base, sulfydryl, nitro, cyano, amino, list or dialkyl amido, list or ammonia diaryl base, alkoxy, aryloxy group, halogenated alkyl,
Ester group, itrile group, isonitrile base, heteroaryl, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino, aryloxycarbonylamino, sulphonyl
Base amino, sulfamoyl, carbamoyl, alkylthio group, sulfinyl, urea groups, phosphinylidyne amido, imido grpup, sulfo group, carboxyl, hydrazine
Base, substituted silicyl, polymerization group, or combinations thereof in select.
Wherein, R7In the presence of another aspect R7It is not present.
On the one hand, R7It is monosubstituted, another aspect, R7It is disubstituted；
R simultaneously7From hydrogen, deuterium, aryl, naphthenic base, cycloalkenyl, heterocycle, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl
Base, sulfydryl, nitro, cyano, amino, list or dialkyl amido, list or ammonia diaryl base, alkoxy, aryloxy group, halogenated alkyl,
Ester group, itrile group, isonitrile base, heteroaryl, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino, aryloxycarbonylamino, sulphonyl
Base amino, sulfamoyl, carbamoyl, alkylthio group, sulfinyl, urea groups, phosphinylidyne amido, imido grpup, sulfo group, carboxyl, hydrazine
Base, substituted silicyl, polymerization group, or combinations thereof in select.
Wherein, R8In the presence of another aspect R8It is not present.
On the one hand, R8It is monosubstituted, another aspect, R8It is disubstituted；
R simultaneously8From hydrogen, deuterium, aryl, naphthenic base, cycloalkenyl, heterocycle, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl
Base, sulfydryl, nitro, cyano, amino, list or dialkyl amido, list or ammonia diaryl base, alkoxy, aryloxy group, halogenated alkyl,
Ester group, itrile group, isonitrile base, heteroaryl, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino, aryloxycarbonylamino, sulphonyl
Base amino, sulfamoyl, carbamoyl, alkylthio group, sulfinyl, urea groups, phosphinylidyne amido, imido grpup, sulfo group, carboxyl, hydrazine
Base, substituted silicyl, polymerization group, or combinations thereof in select.
Wherein, R9In the presence of another aspect R9It is not present.
On the one hand, R9It is monosubstituted, another aspect, R9It is disubstituted；
R simultaneously9From hydrogen, deuterium, aryl, naphthenic base, cycloalkenyl, heterocycle, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl
Base, sulfydryl, nitro, cyano, amino, list or dialkyl amido, list or ammonia diaryl base, alkoxy, aryloxy group, halogenated alkyl,
Ester group, itrile group, isonitrile base, heteroaryl, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino, aryloxycarbonylamino, sulphonyl
Base amino, sulfamoyl, carbamoyl, alkylthio group, sulfinyl, urea groups, phosphinylidyne amido, imido grpup, sulfo group, carboxyl, hydrazine
Base, substituted silicyl, polymerization group, or combinations thereof in select.
Wherein, R10In the presence of another aspect R10It is not present.
On the one hand, R10It is monosubstituted, another aspect, R10It is disubstituted；
R simultaneously10From hydrogen, deuterium, aryl, naphthenic base, cycloalkenyl, heterocycle, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl
Base, sulfydryl, nitro, cyano, amino, list or dialkyl amido, list or ammonia diaryl base, alkoxy, aryloxy group, halogenated alkyl,
Ester group, itrile group, isonitrile base, heteroaryl, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino, aryloxycarbonylamino, sulphonyl
Base amino, sulfamoyl, carbamoyl, alkylthio group, sulfinyl, urea groups, phosphinylidyne amido, imido grpup, sulfo group, carboxyl, hydrazine
Base, substituted silicyl, polymerization group, or combinations thereof in select.
Wherein, R11In the presence of another aspect R11It is not present.
On the one hand, R11It is monosubstituted, another aspect, R11It is disubstituted；
R simultaneously11From hydrogen, deuterium, aryl, naphthenic base, cycloalkenyl, heterocycle, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl
Base, sulfydryl, nitro, cyano, amino, list or dialkyl amido, list or ammonia diaryl base, alkoxy, aryloxy group, halogenated alkyl,
Ester group, itrile group, isonitrile base, heteroaryl, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino, aryloxycarbonylamino, sulphonyl
Base amino, sulfamoyl, carbamoyl, alkylthio group, sulfinyl, urea groups, phosphinylidyne amido, imido grpup, sulfo group, carboxyl, hydrazine
Base, substituted silicyl, polymerization group, or combinations thereof in select.
Exemplary compounds
On the one hand, four ring gears of any phenyl-phenyl containing the bridging-carbazole structure unit reported for the present invention
Metal platinum (II) complex may include one or more following structure.In addition, metal platinum (II) complex also may include
Other structures or part are no longer specifically specially enumerated herein, meanwhile, the protection scope of present invention is not limited to that patent
In cited structure and part.
In an embodiment of the present invention, provided Cyclometalated platinum (IV) complex containing tetradentate ligands has neutral electricity
Lotus.
In an embodiment of the present invention, Cyclometalated platinum (IV) complex containing tetradentate ligands is additionally provided in electroluminescent
Application in device.It is also disclosed in the embodiment of the present invention including the device of one or more in compound disclosed herein,
Including full-color display, photovoltaic device, light-emitting display device, Organic Light Emitting Diode, phosphorescence Organic Light Emitting Diode etc..In device
In part environment, four ring gear metal platinum (II) complex of the phenyl-phenyl containing bridging-carbazole structure unit has in 100%
Portion's quantum efficiency.
Compound disclosed in embodiments of the present invention is suitable for various optics and electro-optical device, including but not
It is limited to light absorption device as solar energy and photo sensitive device, Organic Light Emitting Diode (OLEDs), light emitting devices or existing
Light absorption has the device of photoemissivity and the marker as biologic applications again.
Compound provided by embodiments of the present invention can be in the luminescent device of one kind such as OLED etc, device
Including at least one cathode, at least one anode and at least one layer of luminescent layer, at least one layer in the luminescent layer includes above-mentioned
The four ring gear metal platinum complexes based on phenyl carbazole.Specifically, luminescent device may include being sequentially depositing the sun to be formed
Pole, hole transmission layer, luminescent layer, electron transfer layer and cathode.Its hole-transporting layer, luminescent layer, electron transfer layer are to have
Machine layer, anode and cathode be electrically connected.
Synthetic example
Example below in relation to compound synthesis, ingredient, article, device or method is to provide to the sector field
One general method is not meant to limit the protection scope of the patent for data (quantity, the temperature mentioned in patent
Deng) guarantee as far as possible accurately, it is also possible to can have some errors.Unless otherwise indicated, otherwise weighing all is to separate weighing,
Temperature is DEG C or room temperature, pressure are close to normal pressure.
The preparation method of noval chemical compound is provided in following examples, but the preparation of such compound is not only restricted to this side
Method.In the professional skill field, since the compound protected in this patent is easy to modify preparation, preparation can
To use following cited method or adopt with other methods.Following example is only used as embodiment, is not limited to
The protection scope of the patent.Temperature, catalyst, concentration, reactant and reaction process can change, for different anti-
Object is answered, different condition is selected to prepare the compound.
1H NMR(500MHz)、13C NMR (126MHz) spectrum is surveyed on ANANCE III (500M) type nuclear magnetic resonance chemical analyser
It is fixed；Unless otherwise instructed, nuclear-magnetism uses DMSO-d6Or the CDCl containing 0.1%TMS3Solvent is made, wherein1If H H NMR spectroscopy with
CDCl3When making solvent, using TMS (δ=0.00ppm) as internal standard；With DMSO-d6When making solvent, with TMS (δ=0.00ppm) or
The residual peak DMSO (δ=2.50ppm) or residual water peak (δ=3.33ppm) do internal standard.13In C H NMR spectroscopy, with CDCl3(δ=
77.00ppm) or DMSO-d6(δ=39.52ppm) is used as internal standard.HPLC-MS Agilent 6210TOF LC/MS type mass spectrum
It is measured on instrument；HRMS spectrum measures on Agilent6210TOF LC/MS type sewage sludge instrument.1H H NMR spectroscopy
In diagram data: s=singlet, singlet；D=doublet, doublet；T=triplet, triplet；Q=quartet, four
Weight peak；P=quintet, quintet；M=multiplet, multiplet；Br=broad, broad peak.
Synthetic route
Universal synthesis method is as follows:
Wherein, it when the link group A is O in ligand, can be synthesized by following route:
Wherein, it when the link group A is NR in ligand, can be synthesized by following route:
Wherein, B-Br, B-OH and B-NR used in above-mentioned route can be synthesized by following route:
On the other hand, it can be synthesized by following route for leading to the A-II-OH segment of A-OH in formula (II):
On the other hand, it can be synthesized by following route for leading to the A-IV-OH segment of A-OH in formula (IV):
In addition, matching if the pyrazoles unit in the above structure is changed to other heterocycles also and can refer to the above route progress tetravalence platinum
Close being synthetically prepared for object.
Embodiment 1: platinum complex Pt3 can be synthesized by following route:
The synthesis of intermediate 1: 2- bromine click is sequentially added into the dry there-necked flask of the 100mL with magnetic rotor and condenser pipe
Azoles (7.38g, 30mmol, 1.0 equivalent), cuprous iodide (113.8mg, 0.3mmol, 0.01 equivalent), 1- methylimidazole
(49.26mg, 0.6mmol, 0.02 equivalent), tert-butyl alcohol lithium (4.84g, 60mmol, 2.0 equivalent).It substitutes nitrogen three times, then uses
The bromo- 4- tert .-butylpyridine of 2- (7.71g, 36mmol, 1.2 equivalent) is added in syringe, 1- methylimidazole (49.3mg, 0.6mmol,
0.02 equivalent), 50mL toluene, oil bath temperature rises to 130 DEG C and reacts 24 hours.It is cooled to room temperature, is evaporated under reduced pressure, remove solvent,
Then dry method loading carries out separating-purifying using silica gel column chromatography column, and eluent is petrol ether/ethyl acetate=20:1,
Obtain white solid 11.31g, yield 99%.1H NMR(500MHz,DMSO-d6):δ1.39(s,9H),7.45–7.56(m,
3H), 7.37 (t, J=7.5Hz, 1H), 7.72 (d, J=8.4Hz, 2H), 7.94 (d, J=1.5Hz, 1H), 8.23 (d, J=
8.0Hz, 1H), 8.27-8.31 (m, 1H), 8.66 (d, J=5.0Hz, 1H).
The synthesis of intermediate 2: 4- bromine pyrrole is sequentially added into the dry there-necked flask of the 100mL with magnetic rotor and condenser pipe
Azoles (3.67g, 25.0mmol, 1.0 equivalent), cuprous iodide (476.1mg, 2.5mmol, 0.1 equivalent), L-PROLINE
(575.6mg, 5.0mmol, 0.2 equivalent), K2CO3(10.36g, 90.0mmol, 3.0 equivalent).It substitutes nitrogen three times, then uses needle
Cylinder is added, iodanisol (7.02g, 30mmol, 1.2 equivalent), solvent DMSO (30mL), and oil bath temperature rises to 110 DEG C of reactions 2
It.It is cooled to room temperature, is extracted three times using ethyl acetate and water, merge organic phase, use Na2SO4Dry organic phase, then
Filtering, washs filter cake with ethyl acetate, is evaporated under reduced pressure, and removes solvent, and dry method loading is divided using silica gel column chromatography column
From purification, eluent is petrol ether/ethyl acetate=20:1, obtains oily liquids 5.66g, yield 89%.It is directly used in next
Step reaction.
The synthesis of intermediate 3: connection boric acid is sequentially added into the dry there-necked flask of the 250mL with magnetic rotor and condenser pipe
Pinacol ester (5.37g, 23.3mmol, 1.1 equivalent), [1,1 '-bis- (diphenylphosphine) ferrocene] palladium chloride methylene chloride network
Close object (PdCl2(dppf)·CH2Cl2) (519.4mg, 0.64mmol, 0.03 equivalent), potassium acetate (6.30g, 63.6mmol, 3.0
Equivalent).It substitutes nitrogen three times, intermediate 2 (5.37g, 21.2mmol, 1.0 equivalent) then is added with syringe, solvent DMSO
(30mL), oil bath temperature rise to 80 DEG C and react 3 days.It is cooled to room temperature, and was carried out after being diluted with ethyl acetate with Buchner funnel
Filter, washs filter cake with ethyl acetate.And extracted three times with ethyl acetate and water, merge organic phase, uses anhydrous Na2SO4It is dry
It is organic, it filters, vacuum distillation, removes solvent, dry method loading carries out separating-purifying, eluent using silica gel column chromatography column
For petrol ether/ethyl acetate=20:1, white solid 3.59g, yield 57% are obtained.1H NMR(500MHz,DMSO-d6):δ
1.29 (s, 12H), 3.83 (s, 3H), 6.88 (ddd, J=8.5,2.5,1.0Hz, 1H), 7.37 (t, J=8.0Hz, 1H),
7.47-7.50(m,2H),7.85(s,1H),8.78(s,1H)。
The synthesis of intermediate 4: 2- ammonia is sequentially added into the dry there-necked flask of the 500mL with magnetic rotor and condenser pipe
The bromo- benzoic acid of base -4- (21.60g, 100mmol), methanol (300mL), 98%H2SO4(80mL), oil bath temperature rise to 70 DEG C instead
It answers 2 days.It is cooled to room temperature, and is neutralized to 6-7 with NaOH, be then extracted with ethyl acetate three times, use anhydrous Na2SO4Drying is organic
Then phase filters, vacuum distillation removes solvent, and poor solvent hexane is then added, and recrystallizes 2 times, then uses Buchner funnel
Mixture is filtered, product 4 is obtained, is white solid 17.98g, yield 78%.It is directly used in and reacts in next step.
The synthesis of intermediate 5: intermediate is sequentially added into the dry there-necked flask of the 100mL with magnetic rotor and condenser pipe
4 (6.90g, 30mmol, 1.0 equivalents), phenyl boric acid (3.84g, 31.5mmol, 1.05 equivalent), tetrakis triphenylphosphine palladium (Pd
(PPh3)4) (1.04g, 0.9mmol, 0.03 equivalent), K2CO3(8.29g, 60mmol, 2.0 equivalent), substitutes nitrogen three times, in nitrogen
1,4- dioxane (30mL) and H are added under gas shielded2O(15mL).Oil bath temperature rises to 100 DEG C and is stirred to react 6.0 hours, cold
But three times with the extraction of 30mL ethyl acetate anhydrous Na is used to room temperature2SO4Dry organic phase, is then filtered, and is evaporated under reduced pressure, and is removed
Solvent, dry method loading carry out separating-purifying using silica gel column chromatography column, and eluent is petrol ether/ethyl acetate=20:1,
Obtain white solid 4.81g, yield 76%.1H NMR(500MHz,CDCl3)δ3.92(s,3H),5.80(s,2H),6.77(d,J
=8.5Hz, 1H), 7.27-7.33 (m, 1H), 7.40-7.45 (m, 2H), 7.55-7.59 (m, 3H), 8.15 (d, J=2.5Hz,
1H)。
The synthesis of intermediate 6: intermediate is sequentially added into the dry there-necked flask of the 250mL with magnetic rotor and condenser pipe
5 (4.46g, 19.7mmol, 1.0 equivalents), H2O (20mL), HCl (8mL), and be stirred at room temperature 2 hours.Then by nitrous acid
Sodium (NaNO2) (1.49g, 21.6mmol, 1.1 equivalent) be dissolved into 3mL water and be slowly dropped in reaction system 0 DEG C of stirring 1.0
Hour, finally potassium iodide (KI) (3.91g, 23.6mmol, 1.2 equivalent) is dissolved into 3mL water, is slowly dropped at 0 DEG C
Reaction system, and slowly restore to room temperature reaction 5.0 hours.Reaction terminates, and sodium thiosulfate (Na is added2S2O3) quenching reaction,
And be extracted with ethyl acetate three times, merge organic phase, uses anhydrous Na2SO4Dry organic phase, is then filtered, and is evaporated under reduced pressure, and is removed
Solvent, dry method loading carry out separating-purifying using silica gel column chromatography column, and eluent is petroleum ether, obtains red oil
Matter 2.35g, yield 35%.1H NMR(500MHz,CDCl3)δ3.98(s,3H),7.38–7.42(m,2H),7.46-7.49(m,
2H), 7.59 (s, 1H), 7.597-7.603 (m, 1H), 8.04 (d, J=2.5Hz, 1H), 8.07 (d, J=8.0Hz, 1H).
The synthesis of intermediate 7: intermediate is sequentially added into the dry there-necked flask of the 100mL with magnetic rotor and condenser pipe
6 (4.06g, 12.0mmol, 1.0 equivalents), intermediate 3 (3.64g, 12mmol, 1.0 equivalent), Pd (PPh3)4(694.5mg,
0.6mmol, 0.05 equivalent), potassium carbonate (K2CO3) (3.32g, 24.4mmol, 2.0 equivalent), it substitutes nitrogen three times, is protected in nitrogen
Shield is lower to be added 1,4- dioxane (25mL) and H2O(10mL).Oil bath temperature rises to 100 DEG C and is stirred to react 12 hours, is cooled to
Room temperature is extracted with ethyl acetate (30mL × 3), uses anhydrous Na2SO4Dry organic phase, is filtered using funnel, is evaporated under reduced pressure,
Remove solvent, dry method loading, using silica gel column chromatography column carry out separating-purifying, eluent be petrol ether/ethyl acetate=
20:1 obtains light yellow oil 1.65g, yield 36%.1H NMR(500MHz,DMSO-d6)δ3.83(s,3H),3.86(s,
3H), 6.91-6.93 (m, 1H), 7.42-7.478 (m, 2H), 7.481-7.53 (m, 4H), 7.73 (d, J=8.0Hz, 1H),
7.76 (d, J=7.5Hz, 2H), 7.85 (s, 1H), 7.92 (dd, J=8.0,2.0Hz, 1H), 8.00 (d, J=2.0Hz, 1H),
8.79(s,1H)。
The synthesis of intermediate 8: intermediate is sequentially added into the dry there-necked flask of the 100mL with magnetic rotor and condenser pipe
7 (1.68g, 4.3mmol, 1.0 equivalents), substitute nitrogen three times, and methyl-magnesium-bromide (MeMgBr) then is added under nitrogen protection
(26.6mL, 26.6mmol, 6.2 equivalent) stirs 3 days in 40 DEG C of reactions.Ammonium chloride quenching reaction is added, is extracted with ethyl acetate
Three times, anhydrous Na is used2SO4Dry organic phase, is then filtered, and is evaporated under reduced pressure, and solvent, dry method loading, using silica gel column chromatography are removed
Chromatographic column carries out separating-purifying, and eluent is petroleum ether: ethyl acetate=10:1 obtains light yellow oil 1.41g, yield
85%.1H NMR(500MHz,DMSO-d6)δ1.43(s,6H),3.85(s,3H),5.14(s,1H),6.91–6.87(m,1H),
7.27 (d, J=7.5Hz, 1H), 7.37-7.44 (m, 2H), 7.46-7.48 (m, 2H), 7.48-7.52 (m, 2H), 7.54 (dd, J
=8.0,2.0Hz, 1H), 7.70 (dd, J=8.0,1.0Hz, 2H), 8.03 (d, J=2.0Hz, 1H), 7.84 (s, 1H), 8.61
(s,1H)。
The synthesis of intermediate 9: intermediate 8 is added into the dry there-necked flask of the 100mL with magnetic rotor and condenser pipe
(1.42g, 3.7mmol, 1.0 equivalent), substitutes nitrogen three times, HBr (48%) (10mL) then is added under nitrogen protection, acetic acid
(5mL) is stirred 3 days in 120 DEG C of reactions, is cooled to room temperature, and then vacuum distillation removes solvent, adds 20mL water, is used in combination
It is 6-7 that NaOH aqueous solution, which is neutralized to PH, is then extracted three times with ethyl acetate, merges organic phase, use anhydrous Na2SO4It is dry
It is dry, it then filters, is evaporated under reduced pressure, remove solvent, dry method loading carries out separating-purifying, elution using silica gel column chromatography column
Agent is petroleum ether: ethyl acetate=5:1, obtains white solid 628.1mg, yield 47%.1H NMR(500MHz,DMSO-d6)δ
1.52 (s, 6H), 6.88 (ddd, J=8.5,2.5,1.0Hz, 1H), 7.02-7.08 (m, 2H), 7.33-7.40 (m, 2H), 7.47
(t, J=8.0Hz, 2H), 7.70-7.73 (m, 2H), 7.54-7.60 (m, 2H), 7.78 (d, J=1.5Hz, 1H), 7.87 (s,
1H),9.99(s,1H)。
The synthesis of ligand 3: intermediate 9 is sequentially added into the dry there-necked flask of the 100mL with magnetic rotor and condenser pipe
(628.1mg, 1.8mmol, 1.0 equivalent), intermediate 1 (743.5mg, 1.9mmol, 1.1 equivalent), cuprous iodide (33.9mg,
0.17mmol, 0.01 equivalent), 2- pyridine carboxylic acid (44mg, 0.36mmol, 0.02 equivalent), K3PO4(755.7mg,3.56mmol,
2.0 equivalents).It substitutes nitrogen three times, solvent DMSO (10mL) then is added under nitrogen protection, it is small in 120 DEG C of reaction stirrings 24
When, it is cooled to room temperature, is extracted three times with 30mL ethyl acetate and water, use anhydrous Na2SO4Dry organic phase, is then filtered, and is depressurized
Distillation removes solvent, and dry method loading carries out separating-purifying using silica gel column chromatography column, and eluent is petroleum ether/acetic acid second
Ester=10:1 obtains white solid 694.0mg, yield 60%.1H NMR(500MHz,DMSO-d6)δ1.31(s,9H),1.34
(s, 6H), 7.19 (dd, J=8.5,2.0Hz, 1H), 7.23 (t, J=2.0Hz, 1H), 7.27 (dd, J=8.0,1.5Hz, 1H),
7.32-7.37 (m, 2H), 7.44-7.49 (m, 6H), 7.52 (d, J=8.0Hz, 1H), 7.55 (dd, J=8.0,2.0Hz, 1H),
7.62 (t, J=8.0Hz, 1H), 7.68 (dd, J=7.0,1.5Hz, 4H), 7.76 (d, J=8.5Hz, 1H), 7.86 (s, 1H),
8.25 (d, J=7.5Hz, 1H), 8.33 (d, J=8.5Hz, 1H), 8.58 (d, J=5.5Hz, 1H).
The synthesis of Pt3: successively add ligand 1 into the dry there-necked flask of the 100mL with magnetic rotor and condenser pipe
(330.0mg, 0.5mmol, 1.0 equivalent), normal-butyl ammonium bromide (nBu4NBr) (16.4mg, 0.05mmol, 0.01 equivalent), tetrachloro
Potassium platinate (K2PtCl4) (232.8mg, 0.56mmol, 1.1 equivalent), it substitutes nitrogen three times, solvent acetic acid is then added
(30mL), after nitrogen is bubbled 30 minutes, reaction mixture first first stirs 15 hours in room temperature, then stirs 2 days at 110 DEG C.
Reaction mixture is cooled to room temperature, and vacuum distillation removes solvent, and gained crude product is passed through silica gel column chromatogram separating purification, eluent
(petroleum ether/methylene chloride=5:1), obtains yellow solid 91.0mg, yield 21%.1H NMR(500MHz,DMSO-d6)δ1.41
(s, 9H), 1.90 (s, 6H), 7.04 (d, J=8.0Hz, 1H), 7.23 (d, J=8.0Hz, 1H), 7.36-7.45 (m, 3H),
7.48-7.55 (m, 3H), 7.57 (dd, J=6.5,2.0Hz, 1H), 7.61 (d, J=7.5Hz, 1H), 7.69 (dd, J=7.5,
1.5Hz, 1H), 7.73-7.81 (m, 3H), 7.89 (d, J=8.5Hz, 1H), 7.97 (d, J=1.5Hz, 1H), 8.12 (d, J=
8.0Hz, 1H), 8.19 (t, J=2.0Hz, 2H), 8.50 (s, 1H), 9.24 (d, J=6.5Hz, 1H).
Attached drawing 1 is Room temperature emission spectra and 2- of the platinum complex Pt3 in dichloromethane solution in specific embodiment
Low temperature (77K) emission spectrum in methyltetrahydrofuran.Thus complex Pt3 is in the comparison diagram of room temperature and 77K it is found that its 77K
T1→S0Radiation peak at about 472nm, triplet is about 2.63eV；And the emission peak at its room temperature spectrum about 476nm
For T1→S0Radiation peak, be phosphorescent emissions peak；And the main emission peak at about 448nm is dark blue light emitting peak, is S1→S0Spoke
Peak is penetrated, is delayed fluorescence emission peak.The molecule of the low triplet of success realizes day blue light emitting.
As shown in figure 8, passing through the link group for phenyl Ar1After being chained up with pyrazolyl, 449nm can be greatly improved
Locate the intensity of delayed fluorescence, is more than 1.5 times of reference material molecule, to keep the blue light coloration of luminescent material Pt3 higher.
Embodiment 2: platinum complex Pt14 can be synthesized by following route:
The synthesis of intermediate 10: centre is sequentially added into the dry there-necked flask of the 100mL with magnetic rotor and condenser pipe
Body 4 (6.90g, 30mmol, 1.0 equivalent), 2,5- dimethylphenyl boronic acid (3.84g, 31.5mmol, 1.05 equivalent), Pd (PPh3)4
(1.04g, 0.9mmol, 0.03 equivalent), K2CO3(8.29g, 60mmol, 2.0 equivalent), substitutes nitrogen three times, under nitrogen protection
1,4- dioxane (30mL) and H is added2O(15mL).Oil bath temperature rises to 100 DEG C and is stirred to react 6.0 hours, is cooled to room
Temperature three times with the extraction of 30mL ethyl acetate uses anhydrous Na2SO4Dry organic phase, is then filtered, and is evaporated under reduced pressure, and solvent is removed, and is done
Method loading carries out separating-purifying using silica gel column chromatography column, and eluent is petrol ether/ethyl acetate=20:1, is obtained white
Color solid 5.29g, yield 69%.It is directly used in and reacts in next step.
The synthesis of intermediate 11: centre is sequentially added into the dry there-necked flask of the 250mL with magnetic rotor and condenser pipe
Body 10 (4.96g, 19.6mmol, 1.0 equivalent), H2O (20mL), HCl (8mL), and 2h is stirred at room temperature.Then by NaNO2
(1.47g, 21.6mmol, 1.1 equivalent), which is dissolved into 3mL water, is slowly dropped to 0 DEG C stirring 1.0 hours in reaction system, finally
KI (3.87g, 23.6mmol, 1.2 equivalent) is dissolved into 3mL water, reaction system is slowly dropped at 0 DEG C, and slowly extensive
Multiple extremely room temperature reaction 5.0 hours.Reaction terminates, and sodium thiosulfate (Na is added2S2O3) quenching reaction, and be extracted with ethyl acetate
Three times, merge organic phase, use anhydrous Na2SO4Dry organic phase, is then filtered, and is evaporated under reduced pressure, and solvent is removed, and dry method loading is adopted
Separating-purifying is carried out with silica gel column chromatography column, eluent is pure petroleum ether, obtains Red oil substance 4.95g, yield
69%.1H NMR(500MHz,CDCl3) δ 2.04 (s, 6H), 3.94 (s, 3H), 6.99 (dd, J=8.0,2.0Hz, 1H), 7.13
(t, J=3.5Hz, 2H), 7.20 (t, J=8.0Hz 1H), 7.65 (d, J=2.0Hz, 1H), 8.07 (d, J=8.0Hz, 1H).
The synthesis of intermediate 12: centre is sequentially added into the dry there-necked flask of the 100mL with magnetic rotor and condenser pipe
Body 11 (2.13g, 5.8mmol, 1.0 equivalent), intermediate 3 (1.74g, 5.8mmol, 1.0 equivalent), Pd (PPh3)4(335.7mg,
0.3mmol, 0.05 equivalent), K2CO3(1.61g, 11.6mmol, 2.0 equivalent), substitutes nitrogen three times, is added under nitrogen protection
1,4- dioxane (20mL) and H2O(10mL).Oil bath temperature rises to 100 DEG C and is stirred to react 12 hours, is cooled to room temperature, and uses
30mL ethyl acetate extracts three times, uses anhydrous Na2SO4Dry organic phase, is then filtered, and is evaporated under reduced pressure, removing solvent, in dry method
Sample carries out separating-purifying using silica gel column chromatography column, and eluent is petrol ether/ethyl acetate=20:1, is obtained light yellow
Grease 2.19g, yield 40%.1H NMR(500MHz,DMSO-d6)δ2.03(s,6H),3.78(s,3H),3.86(s,3H),
6.89–6.94(m,1H),7.14–7.18(m,2H),7.19–7.23(m,1H),7.40–7.46(m,2H),7.47–7.51(m,
3H), 7.70 (d, J=8.0Hz, 1H), 7.87-7.88 (m, 1H), 8.79 (d, J=0.5Hz, 1H).
The synthesis of intermediate 13: centre is sequentially added into the dry there-necked flask of the 100mL with magnetic rotor and condenser pipe
Body 12 (1.74g, 4.1mmol, 1.0 equivalent), substitutes nitrogen three times, then under nitrogen protection be added MeMgBr (25.4mL,
25.4mmol, 6.2 equivalents), it is stirred 3 days in 40 DEG C of reactions.NH is added4Cl quenching reaction is extracted with ethyl acetate three times, with nothing
Water Na2SO4Dry organic phase, is then filtered, and is evaporated under reduced pressure, and removes solvent, dry method loading, using silica gel column chromatography column into
Row separating-purifying, eluent are petroleum ether: ethyl acetate=10:1, obtain light yellow oil 1.35g, yield 80%.1H
NMR(500MHz,DMSO-d6)δ1.41(s,6H),2.04(s,6H),3.85(s,3H),5.03(s,1H),6.86–6.91(m,
1H), 7.04 (dd, J=8.0,2.0Hz, 1H), 7.12-7.20 (m, 3H), 7.26 (d, J=7.5Hz, 1H), 7.38-7.44 (m,
1H),7.46–7.50(m,3H),7.88(s,1H),8.68(s,1H)。
The synthesis of intermediate 14: intermediate 13 is added into the dry there-necked flask of the 100mL with magnetic rotor and condenser pipe
(1.20g, 2.9mmol, 1.0 equivalent), substitutes nitrogen three times, and 48% HBr (10mL), HAOc are then added under nitrogen protection
(5mL) is stirred 3 days in 120 DEG C of reactions, is cooled to room temperature, and then vacuum distillation removes solvent, adds 20mL water, is used in combination
It is 6-7 that NaOH aqueous solution, which is neutralized to pH, is then extracted three times with ethyl acetate, merges organic phase, use anhydrous Na2SO4It is dry
It is dry, it then filters, is evaporated under reduced pressure, remove solvent, dry method loading carries out separating-purifying, elution using silica gel column chromatography column
Agent is petroleum ether: ethyl acetate=: 5:1 obtains white solid 938.2mg, yield 84%.1H NMR(500MHz,DMSO-d6)δ
1.47(s,6H),2.02(s,6H),6.84–6.90(m,1H),6.99–7.08(m,3H),7.10–7.19(m,3H),7.26(t,
J=4.0Hz, 1H), 7.37 (t, J=8.0Hz, 1H), 7.47-7.59 (m, 1H), 7.86 (d, J=5.5Hz, 1H), 9.96 (s,
1H)。
The synthesis of ligand 14: intermediate is sequentially added into the dry there-necked flask of the 100mL with magnetic rotor and condenser pipe
14 (938.2mg, 2.5mmol, 1.0 equivalents), intermediate 1 (1.10g, 2.7mmol, 1.1 equivalent), cuprous iodide (47.0mg,
0.25mmol, 0.01 equivalent), 2- pyridine carboxylic acid (60.9mg, 0.50mmol, 0.02 equivalent), K3PO4(1.05g,4.9mmol,
2.0 equivalents).It substitutes nitrogen three times, solvent dimethyl sulfoxide (10mL) then is added under nitrogen protection, is stirred in 120 DEG C of reactions
It mixes 24 hours, is cooled to room temperature, extracted three times with 30mL ethyl acetate and water, use anhydrous Na2SO4Organic phase is dried, then mistake
Filter, vacuum distillation remove solvent, and dry method loading carries out separating-purifying using silica gel column chromatography column, and eluent is petroleum
Ether/ethyl acetate=10:1 obtains white solid 914.4mg, yield 55%.1H NMR(500MHz,DMSO-d6)δ1.28(s,
15H), 1.98 (s, 6H), 6.99 (dd, J=7.5,1.5Hz, 1H), 7.09-7.14 (m, 2H), 7.14-7.17 (m, 2H), 7.18
(m, 1H), 7.22 (t, J=2.0Hz, 1H), 7.26 (dd, J=7.5,2.0Hz, 1H), 7.34 (t, J=7.0Hz, 1H), 7.42-
7.48 (m, 4H), 7.50 (d, J=7.5Hz, 1H), 7.61 (t, J=8.0Hz, 1H), 7.67 (d, J=1.5Hz, 1H), 7.74
(d, J=8.0Hz, 1H), 7.85 (s, 1H), 8.24 (d, J=7.5Hz, 1H), 8.32 (d, J=8.0Hz, 1H), 8.56 (d, J=
5.0Hz,1H)。
The synthesis of Pt14: successively add ligand L 14 into the dry there-necked flask of the 100mL with magnetic rotor and condenser pipe
(500.0mg, 0.74mmol, 1.0 equivalent),nBu4NBr (23.7mg, 0.07mmol, 0.01 equivalent), K2PtCl4(337.8mg,
0.82mmol, 1.1 equivalents), it substitutes nitrogen three times, solvent acetic acid (40mL) then is added, after nitrogen is bubbled 30 minutes, reaction
Mixture first first stirs 10 hours in room temperature, then stirs 2 days at 110 DEG C.Reaction mixture is cooled to room temperature, vacuum distillation
Solvent is removed, by gained crude product by silica gel column chromatogram separating purification, eluent (petroleum ether/methylene chloride=5:1) obtains yellow
Solid 385.1mg, yield 60%.1H NMR(500MHz,DMSO-d6)δ1.41(s,9H),1.85(s,6H),2.06(s,6H),
7.03 (d, J=8.0Hz, 1H), 7.12-7.21 (m, 4H), 7.23 (d, J=8.0Hz, 1H), 7.36 (t, J=8.0Hz, 1H),
7.42 (t, J=7.5Hz, 1H), 7.47 (d, J=1.0Hz, 1H), 7.50-7.55 (m, 1H), 7.55-7.62 (m, 2H), 7.75
(d, J=7.5Hz, 1H), 7.89 (d, J=8.0Hz, 1H), 8.12 (d, J=8.0Hz, 1H), 8.19 (t, J=2.0Hz, 2H),
8.49 (s, 1H), 9.24 (d, J=6.0Hz, 1H).
Attached drawing 2 is Room temperature emission spectra and 2- of the platinum complex Pt14 in dichloromethane solution in specific embodiment
Low temperature (77K) emission spectrum in methyltetrahydrofuran.The T of its 77K1→S0Radiation peak at 441nm and room temperature 447nm
Main emission peak is T1→S0Radiation, be deep blue emitting phosphor；This example illustrates phenyl Ar2Ortho position introduce two methyl, meeting
The dihedral angle between phenyl-phenyl is significantly increased, conjugated degree is allowed to and is greatly lowered, triplet is promoted to 2.81eV.
Implementing 3. platinum complex Pt31 of example can be synthesized by following route:
The synthesis of intermediate 15: centre is sequentially added into the dry there-necked flask of the 100mL with magnetic rotor and condenser pipe
Body 4 (5.75g, 25mmol, 1.0equiv), 2- methylphenylboronic acid (3.60g, 26.3mmol, 1.05equiv), Pd (PPh3)4
(866.7mg,0.75mmol,0.03equiv),K2CO3(6.91g, 50mmol, 2.0equiv) substitutes nitrogen three times, in nitrogen
Protection is lower to be added 1,4- dioxane (25mL) and H2O(10mL).Oil bath temperature rises to 100 DEG C and is stirred to react 6.0h, is cooled to
Room temperature, three times with the extraction of 30mL ethyl acetate, organic phase is dry with anhydrous Na 2SO4, then filters, and is evaporated under reduced pressure, and removes molten
Agent, dry method loading carry out separating-purifying using silica gel column chromatography column, and eluent is petrol ether/ethyl acetate=20:1, is obtained
To white solid 4.71g, yield 78%.1H NMR(500MHz,CDCl3):δ2.28(s,3H),3.86(s,3H),5.75(s,
2H), 6.71 (d, J=8.5Hz, 1H), 7.14-7.33 (m, 5H), 7.84 (d, J=2.0Hz, 1H).
The synthesis of intermediate 16: centre is sequentially added into the dry there-necked flask of the 250mL with magnetic rotor and condenser pipe
Body 15 (4.71g, 19.5mmol, 1.0equiv), H2O (20mL), HCl (8mL), and 2h is stirred at room temperature.Then by NaNO2
(1.48g, 21.5mmol, 1.1equiv), which is dissolved into 3mL water, is slowly dropped to 0 DEG C of stirring 1.0h in reaction system, finally will
KI (3.89g, 23.4mmol, 1.2equiv) is dissolved into 3mL water, reaction system is slowly dropped at 0 DEG C, and slowly restore
To room temperature reaction 5.0h.Reaction terminates, and Na is added2S2O3Quenching reaction, and be extracted with ethyl acetate three times, merge organic phase, uses
Anhydrous Na2SO4Dry organic phase, is then filtered, and is evaporated under reduced pressure, and solvent, dry method loading, using silica gel column chromatography column are removed
Separating-purifying is carried out, eluent is petroleum ether, obtains Red oil substance 4.52g, yield 65%.1H NMR(500MHz,
CDCl3) δ 2.25 (s, 3H), 3.93 (s, 3H), 7.12 (dd, J=8.0,2.0Hz, 1H), 7.19 (d, J=7.0Hz, 1H),
7.22-7.31 (m, 3H), 7.77 (d, J=2.0Hz, 1H), 8.02 (d, J=8.0Hz, 1H).
The synthesis of intermediate 17: centre is sequentially added into the dry there-necked flask of the 100mL with magnetic rotor and condenser pipe
Body 16 (2.97g, 8.4mmol, 1.0equiv), intermediate 3 (2.78g, 9.3mmol, 1.0equiv), Pd (PPh3)4
(487.1mg,0.42mmol,0.05equiv),K2CO3(2.33g, 16.8mmol, 2.0equiv) substitutes nitrogen three times, in nitrogen
1,4- dioxane (15mL) and H are added under gas shielded2O(5mL).Oil bath temperature rises to 100 DEG C and is stirred to react 2 days, is cooled to
Room temperature is extracted with ethyl acetate (30mLX 3), uses anhydrous Na2SO4Dry organic phase, is filtered using funnel, is evaporated under reduced pressure,
Remove solvent, dry method loading, using silica gel column chromatography column carry out separating-purifying, eluent be petrol ether/ethyl acetate=
10:1 obtains light yellow oil 1.91g, yield 57%.1H NMR(500MHz,CDCl3)δ2.32(s,3H),3.83(s,
3H),3.89(s,3H),6.84-6.86(m,1H),7.23–7.32(m,5H),7.33–7.40(m,2H),7.46–7.54(m,
2H), 7.76 (d, J=1.5Hz, 1H), 7.84 (s, 1H), 8.14 (d, J=0.5Hz, 1H).
The synthesis of intermediate 18: centre is sequentially added into the dry there-necked flask of the 100mL with magnetic rotor and condenser pipe
Body 17 (1.91g, 5.0mmol, 1.0equiv), substitutes nitrogen three times, then under nitrogen protection be added MeMgBr (31.2mL,
31.2mmol, 6.2equiv), it is stirred 3 days in 40 DEG C of reactions.NH is added4Cl quenching reaction is extracted with ethyl acetate three times, uses
Anhydrous Na2SO4Dry organic phase, is then filtered, and is evaporated under reduced pressure, and solvent, dry method loading, using silica gel column chromatography column are removed
Separating-purifying is carried out, eluent is petroleum ether: ethyl acetate=10:1, obtains light yellow oil 1.69g, yield 84%.1H
NMR(500MHz,DMSO-d6)δ2.30(s,3H),3.34(s,6H),3.85(s,3H),5.08(s,1H),8.65(s,1H),
6.87-6.89(m,1H),7.20–7.35(m,6H),7.38–7.44(m,1H),7.44–7.52(m,2H),7.70(s,1H),
7.87(s,1H)。
The synthesis of intermediate 19: intermediate 8 is added into the dry there-necked flask of the 100mL with magnetic rotor and condenser pipe
(1.68g, 4.2mmol, 1.0equiv) substitutes nitrogen three times, HBr (48%) (100mL) then is added under nitrogen protection, vinegar
Sour (5mL) is stirred 3 days in 120 DEG C of reactions, is cooled to room temperature, and then vacuum distillation removes solvent, adds 20mL water, is used in combination
Na2CO3It neutralizes no bubble to generate, is then extracted three times with ethyl acetate, merge organic phase, use anhydrous Na2SO4It is dry
It is dry, it then filters, is evaporated under reduced pressure, remove solvent, dry method loading carries out separating-purifying, elution using silica gel column chromatography column
Agent is ethyl acetate/methanol=20:1, obtains white solid 1.23g, yield 79%.It is directly used in and reacts in next step.
The synthesis of ligand L 31: intermediate is sequentially added into the dry there-necked flask of the 100mL with magnetic rotor and condenser pipe
19 (1.23g, 3.4mmol, 1.0equiv), intermediate 1 (1.40g, 3.7mmol, 1.1equiv), cuprous iodide (63.9mg,
0.34mmol, 0.01equiv), 2- pyridine carboxylic acid (82.73mg, 0.67mmol, 0.02equiv), K3PO4(1.43mg,
6.7mmol,2.0equiv).It substitutes nitrogen three times, solvent DMSO (15mL) then is added under nitrogen protection, reacted at 115 DEG C
Stirring for 24 hours, is cooled to room temperature, and is first diluted, is then filtered using Buchner funnel, using 100mL second with 30mL ethyl acetate
Acetoacetic ester carries out washing filter cake, organic to be added to the extraction of 30mL water three times, finally uses anhydrous Na2SO4Dry organic phase, filters out
Na2SO4, vacuum distillation, removing solvent, dry method loading, using silica gel column chromatography column progress separating-purifying, eluent is stone
Oily ether/ethyl acetate=10:1, obtains white solid 475.0mg, yield 21%.1H NMR(500MHz,DMSO-d6)δ1.28
(s, 9H), 1.30 (s, 6H), 2.24 (s, 3H), 7.16-7.30 (m, 8H), 7.34 (dd, J=10.5,1.5Hz, 2H), 7.41-
7.50 (m, 5H), 7.61 (t, J=8.0Hz, 1H), 7.67 (d, J=1.5Hz, 1H), 7.74 (d, J=8..5Hz, 1H), 7.85
(s, 1H), 8.24 (d, J=7.5Hz, 1H), 8.31 (d, J=8.5Hz, 1H), 8.56 (d, J=5.5Hz, 1H).
The synthesis of Pt31: successively add ligand 1 into the dry there-necked flask of the 100mL with magnetic rotor and condenser pipe
(400.0mg,0.6mmol,1.0equiv),nBu4NBr(19.3mg,0.06mmol,0.01equiv),K2PtCl4(274.7mg,
0.66mmol, 1.1equiv), it substitutes nitrogen three times, solvent acetic acid (30mL) then is added, after nitrogen is bubbled 30 minutes, reaction
Mixture first first stirs 15 hours in room temperature, then stirs 3 days at 110 DEG C.Reaction mixture is cooled to room temperature, vacuum distillation
Solvent is removed, by gained crude product by silica gel column chromatogram separating purification, eluent (petroleum ether/methylene chloride=4:1) obtains yellow
Solid 194.9mg, yield 38%.1H NMR(500MHz,DMSO-d6)δ1.41(s,9H),1.86(s,6H),2.32(s,3H),
7.03 (d, J=8.0Hz, 1H), 7.22 (d, J=8.0Hz, 1H), 7.27-7.32 (m, 3H), 7.32-7.36 (m, 2H), 7.38
(d, J=8.0Hz, 1H), 7.42 (t, J=7.5Hz, 1H), 7.52 (t, J=7.0Hz, 1H), 7.55-7.61 (m, 2H), 7.66
(s, 1H), 7.74 (d, J=8.0Hz, 1H), 7.89 (d, J=8.5Hz, 1H), 8.12 (d, J=8.5Hz, 1H), 8.18 (d, J=
7.5Hz, 2H), 8.50 (s, 1H), 9.23 (d, J=6.5Hz, 1H).
Fig. 3 is Room temperature emission spectra of the platinum complex Pt31 in dichloromethane solution and in 2- methyltetrahydrofuran
77K emission spectrum.
Platinum complex Pt14 and platinum complex Pt31, emission spectrum relative comparison object, blue spectral shift 1-2nm, tool
There is more blue dark blue smooth feature.
The embodiment of the present invention compound, no matter phenyl Ar2Ortho position whether contain non-hydrogen substituent, can be realized depth
Blue-light-emitting.
4- attached drawing 7 with reference to the accompanying drawings, it can be seen that the energy level of several platinum complexes is distributed no difference, these are matched
Closing object has closely similar ground HOMO, LUMO performance.Phenyl Ar in the compounds of this invention2Ortho position whether have non-hydrogen substituent,
Its influence for HOMO, LUMO performance is unconspicuous.
Above-described is only embodiments of the present invention, it should be noted here that for those of ordinary skill in the art
For, without departing from the concept of the premise of the invention, improvement can also be made, but these belong to protection model of the invention
It encloses.
Claims (10)
1. a kind of metal platinum (II) complex of the phenyl-phenyl containing bridging-carbazole structure unit, which is characterized in that described
Metal platinum (II) complex has structure shown in logical formula (I)
Wherein:
The link group X is selected from CH2、CHD、CD2、CR100R101、SiH2、SiHD、SiD2、SiR102R103、GeH2、Ge HD、GeD2、
GeR104R105；
A is selected from O, S, CH2、CHD、CD2、CR200R201, C=O, SiR202R203、GeH2、GeR204R205、NH、ND、NR206、PH、PD、
PR207、R208P=O, AsR209、R210As=O, S=O, SO2, Se, Se=O, SeO2、BH、BD、BR211、R212Bi=O, BiH,
BiD or BiR213；
Ra、Rb、Rc、Rd、Re、RfAnd RgIt is each independently selected from hydrogen, deuterium, aryl, naphthenic base, cycloalkenyl, heterocycle, heteroaryl, alkane
Base, alkenyl, alkynyl, halogen, hydroxyl, sulfydryl, nitro, cyano, amino, list or dialkyl amido, list or ammonia diaryl base, alcoxyl
Base, aryloxy group, halogenated alkyl, ester group, itrile group, isonitrile base, heteroaryl, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino,
Aryloxycarbonylamino, sulfuryl amino, sulfamoyl, carbamoyl, alkylthio group, sulfinyl, urea groups, phosphinylidyne amido,
Imido grpup, sulfo group, carboxyl, diazanyl, silicyl, substituted silicyl, polymerization group, or combinations thereof；Ra、Rb、Rc、Rd、
Re、RfAnd RgSubstitution mode each independently represent for it is monosubstituted, disubstituted, three replace, four replace or it is unsubstituted, it is adjacent
Two substituent groups can form condensed ring；
S indicates that the integer of 0-5, m, n integer independent for indicating 0-4, o indicate the integer of 0-2, p, r table independent
Show that the integer of 0-3, q indicate the integer of 0-1；
The R100、R101、R102、R103、R104、R105、R200、R201、R202、R203、R204、R205、R206、R207、R208、R209、R210、
R211、R212、R213It is each independently selected from aryl, naphthenic base, cycloalkenyl, heterocycle, heteroaryl, alkyl, alkenyl, alkynyl, halogen
It is element, hydroxyl, sulfydryl, nitro, cyano, amino, list or dialkyl amido, list or ammonia diaryl base, alkoxy, aryloxy group, halogenated
Alkyl, ester group, itrile group, isonitrile base, heteroaryl, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino, aryloxycarbonylamino,
Sulfuryl amino, sulfamoyl, carbamoyl, alkylthio group, sulfinyl, urea groups, phosphinylidyne amido, imido grpup, sulfo group, carboxylic
Base, diazanyl, silicyl, substituted silicyl, polymerization group, or combinations thereof；Wherein two adjacent substituent groups can be with
Form condensed ring；
The Ar1For the phenyl being connected with pyrazolyl, the Ar2For with Ar1Connected phenyl, the α are Ar1With the two of pyrazolyl
Face angle, the β are Ar1With Ar2Dihedral angle.
2. metal platinum (II) complex of the phenyl-phenyl containing bridging-carbazole structure unit according to claim 1,
It is characterized by: metal platinum (II) complex has structure shown in logical formula (II), (III):
Wherein, R1、R2、R3、R4、R5、R6、R7、R8、R9、R10And R11Be each independently hydrogen, deuterium, aryl, naphthenic base, cycloalkenyl,
Heterocycle, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, sulfydryl, nitro, cyano, amino, list or dialkyl amido, list
Or ammonia diaryl base, alkoxy, aryloxy group, halogenated alkyl, ester group, itrile group, isonitrile base, heteroaryl, alkoxy carbonyl, acyl ammonia
Base, alkoxycarbonyl amino, aryloxycarbonylamino, sulfuryl amino, sulfamoyl, carbamoyl, alkylthio group, sulfenyl
Base, urea groups, phosphinylidyne amido, imido grpup, sulfo group, carboxyl, diazanyl, silicyl, substituted silicyl, polymerization group or
A combination thereof；The adjacent R1、R2、R3、R4、R5、R6、R7、R8、R9、R10And R11It can connect to form condensed ring.
3. metal platinum (II) complex of the phenyl-phenyl containing bridging-carbazole structure unit according to claim 1,
It is characterized by: metal platinum (II) complex has structure shown in logical formula (IV), (V):
Wherein, R1、R2、R3、R4、R5、R6、R7、R8、R9、R10And R11It is each independently selected from hydrogen, deuterium, aryl, naphthenic base, cyclenes
Base, heterocycle, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, sulfydryl, nitro, cyano, amino, list or dialkyl amido,
List or ammonia diaryl base, alkoxy, aryloxy group, halogenated alkyl, ester group, itrile group, isonitrile base, heteroaryl, alkoxy carbonyl, acyl ammonia
Base, alkoxycarbonyl amino, aryloxycarbonylamino, sulfuryl amino, sulfamoyl, carbamoyl, alkylthio group, sulfenyl
Base, urea groups, phosphinylidyne amido, imido grpup, sulfo group, carboxyl, diazanyl, silicyl, substituted silicyl, polymerization group or
A combination thereof；The adjacent R1、R2、R3、R4、R5、R6、R7、R8、R9、R10And R11It can connect to form condensed ring.
4. metal platinum (II) complex of the phenyl-phenyl containing bridging-carbazole structure unit according to claim 3,
It is characterized by: the R1、R2、R3、R4、R5、R6、R7、R8、R9、R10And R11It is each independently selected from hydrogen, methyl, ethyl, third
Base, butyl, amyl, hexyl, heptyl, octyl, phenyl, tolyl, ethylbenzene, propyl phenyl, butylbenzene base, penta phenyl, own phenyl, heptan
Phenyl or pungent phenyl.
5. metal platinum (II) complex of the phenyl-phenyl containing bridging-carbazole structure unit according to claim 1,
It is characterized by: metal platinum (II) complex has one of following structure:
6. the metal platinum (II) of the phenyl-phenyl containing bridging-carbazole structure unit according to claim 1-5
Complex, it is characterised in that: metal platinum (II) complex has neutral charge.
7. the metal platinum (II) of the phenyl-phenyl containing bridging-carbazole structure unit of any of claims 1-5 is matched
Close application of the object in electroluminescent device.
8. a kind of device, which is characterized in that the device includes the benzene according to any one of claims 1 to 5 containing bridging
Base-phenyl-carbazole structure unit metal platinum (II) complex.
9. device according to claim 8, which is characterized in that the device is full-color display, photovoltaic device, shining shows
Show device, Organic Light Emitting Diode or phosphorescence Organic Light Emitting Diode.
10. device according to claim 8, which is characterized in that including at least one cathode, at least one anode and at least
One layer of luminescent layer, at least one layer in the luminescent layer include the benzene described in any one of claims 1 to 5 containing bridging
Base-phenyl-carbazole structure unit metal platinum (II) complex.
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| US20150194616A1 (en) * | 2014-01-07 | 2015-07-09 | Jian Li | Tetradentate Platinum And Palladium Complex Emitters Containing Phenyl-Pyrazole And Its Analogues |
| CN108276449A (en) * | 2018-01-30 | 2018-07-13 | 瑞声光电科技(常州)有限公司 | Four ring gear metal platinum complexes, preparation method and application containing the disubstituted pyrazoles of 4- aryl -3,5- |
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| US20150194616A1 (en) * | 2014-01-07 | 2015-07-09 | Jian Li | Tetradentate Platinum And Palladium Complex Emitters Containing Phenyl-Pyrazole And Its Analogues |
| CN108276449A (en) * | 2018-01-30 | 2018-07-13 | 瑞声光电科技(常州)有限公司 | Four ring gear metal platinum complexes, preparation method and application containing the disubstituted pyrazoles of 4- aryl -3,5- |
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