CN108948095A - Four ring gear metal platinum complexes and its application based on phenyl carbazole - Google Patents
Four ring gear metal platinum complexes and its application based on phenyl carbazole Download PDFInfo
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- CN108948095A CN108948095A CN201810872326.1A CN201810872326A CN108948095A CN 108948095 A CN108948095 A CN 108948095A CN 201810872326 A CN201810872326 A CN 201810872326A CN 108948095 A CN108948095 A CN 108948095A
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- base
- amino
- alkyl
- present
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 35
- 239000002184 metal Substances 0.000 title claims abstract description 32
- FBTOLQFRGURPJH-UHFFFAOYSA-N 1-phenyl-9h-carbazole Chemical compound C1=CC=CC=C1C1=CC=CC2=C1NC1=CC=CC=C12 FBTOLQFRGURPJH-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 150000003057 platinum Chemical class 0.000 title claims abstract description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 73
- -1 nitro, cyano, amino Chemical group 0.000 claims description 57
- 125000001072 heteroaryl group Chemical group 0.000 claims description 45
- 125000003118 aryl group Chemical group 0.000 claims description 42
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 36
- 125000000304 alkynyl group Chemical group 0.000 claims description 29
- 125000003342 alkenyl group Chemical group 0.000 claims description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- 229910052736 halogen Inorganic materials 0.000 claims description 26
- 150000002367 halogens Chemical class 0.000 claims description 26
- 125000003545 alkoxy group Chemical group 0.000 claims description 25
- 125000003368 amide group Chemical group 0.000 claims description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- 125000000623 heterocyclic group Chemical group 0.000 claims description 16
- 229910021529 ammonia Inorganic materials 0.000 claims description 15
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 13
- 125000004185 ester group Chemical group 0.000 claims description 13
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 12
- 125000004442 acylamino group Chemical group 0.000 claims description 12
- 125000004414 alkyl thio group Chemical group 0.000 claims description 12
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 12
- 229910052805 deuterium Inorganic materials 0.000 claims description 12
- 150000002527 isonitriles Chemical class 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 238000006467 substitution reaction Methods 0.000 claims description 12
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 11
- 125000004466 alkoxycarbonylamino group Chemical group 0.000 claims description 10
- 125000004104 aryloxy group Chemical group 0.000 claims description 10
- 125000005162 aryl oxy carbonyl amino group Chemical group 0.000 claims description 9
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 229910052785 arsenic Inorganic materials 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 239000005864 Sulphur Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- 150000001345 alkine derivatives Chemical class 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 2
- 230000037429 base substitution Effects 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 230000003760 hair shine Effects 0.000 claims 1
- 150000002466 imines Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 30
- 125000001424 substituent group Chemical group 0.000 abstract description 27
- 239000003446 ligand Substances 0.000 abstract description 16
- 238000000295 emission spectrum Methods 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000004020 luminiscence type Methods 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 56
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 39
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 38
- 150000001875 compounds Chemical class 0.000 description 38
- 229910052799 carbon Inorganic materials 0.000 description 20
- 150000003254 radicals Chemical class 0.000 description 20
- 239000002904 solvent Substances 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000012043 crude product Substances 0.000 description 14
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 13
- 239000003480 eluent Substances 0.000 description 13
- 238000000746 purification Methods 0.000 description 13
- 239000000741 silica gel Substances 0.000 description 13
- 229910002027 silica gel Inorganic materials 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 125000004429 atom Chemical group 0.000 description 12
- 239000012074 organic phase Substances 0.000 description 12
- 239000003208 petroleum Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 238000005292 vacuum distillation Methods 0.000 description 12
- 0 CC(C)C(CC1)=CC(c2c3*(/C(/C4)=C(/Cc5c-6ccc-7c5*5c8ccccc-78)\*7c5cccc7)ccc2)=C1*3c1c4c-6ccc1 Chemical compound CC(C)C(CC1)=CC(c2c3*(/C(/C4)=C(/Cc5c-6ccc-7c5*5c8ccccc-78)\*7c5cccc7)ccc2)=C1*3c1c4c-6ccc1 0.000 description 11
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N DMSO-d6 Substances [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- 150000001721 carbon Chemical group 0.000 description 6
- 150000004696 coordination complex Chemical class 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 125000005842 heteroatom Chemical group 0.000 description 6
- 150000002475 indoles Chemical class 0.000 description 6
- 239000000243 solution Substances 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
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 5
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 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
- 239000007788 liquid Substances 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- 239000011368 organic material Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- QGZKDVFQNNGYKY-OUBTZVSYSA-N Ammonia-15N Chemical compound [15NH3] QGZKDVFQNNGYKY-OUBTZVSYSA-N 0.000 description 4
- 241000790917 Dioxys <bee> Species 0.000 description 4
- 229910020427 K2PtCl4 Inorganic materials 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
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000003550 marker Substances 0.000 description 4
- 125000006574 non-aromatic ring group Chemical group 0.000 description 4
- 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 4
- 239000011574 phosphorus Substances 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 4
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 description 3
- 229930182821 L-proline Natural products 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000005347 biaryls Chemical group 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 125000004366 heterocycloalkenyl group Chemical group 0.000 description 3
- 125000004415 heterocyclylalkyl group Chemical group 0.000 description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229960002429 proline Drugs 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- 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 2
- ZZPNDIHOQDQVNU-UHFFFAOYSA-N 2-hydroxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound CC1(C)OB(O)OC1(C)C ZZPNDIHOQDQVNU-UHFFFAOYSA-N 0.000 description 2
- 125000006275 3-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C([H])C(*)=C1[H] 0.000 description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 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
- 229910002666 PdCl2 Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000002015 acyclic group Chemical group 0.000 description 2
- 125000003282 alkyl amino group Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-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
- 230000005283 ground state Effects 0.000 description 2
- 230000026030 halogenation Effects 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- 238000004770 highest occupied molecular orbital 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
- 238000004768 lowest unoccupied molecular orbital 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
- 125000002524 organometallic group Chemical group 0.000 description 2
- 125000002971 oxazolyl group Chemical group 0.000 description 2
- 125000001820 oxy group Chemical group [*:1]O[*:2] 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
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- 238000010992 reflux Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-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
- OIRHKGBNGGSCGS-UHFFFAOYSA-N 1-bromo-2-iodobenzene Chemical compound BrC1=CC=CC=C1I OIRHKGBNGGSCGS-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical class CN1C=CN=C1 MCTWTZJPVLRJOU-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
- IMRWILPUOVGIMU-UHFFFAOYSA-N 2-bromopyridine Chemical compound BrC1=CC=CC=N1 IMRWILPUOVGIMU-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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-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
- 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
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical class [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- DPOPAJRDYZGTIR-UHFFFAOYSA-N Tetrazine Chemical compound C1=CN=NN=N1 DPOPAJRDYZGTIR-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 125000003172 aldehyde group Chemical group 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
- 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
- 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
- 230000006837 decompression Effects 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
- 230000003111 delayed effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 150000002012 dioxanes Chemical class 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
- 230000000694 effects Effects 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000005284 excitation Effects 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
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 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 description 1
- 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 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
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000005360 mashing 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- 239000012452 mother liquor Substances 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
- 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
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000013086 organic photovoltaic Methods 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
- 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
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl 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
- 238000000197 pyrolysis Methods 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
- 238000001953 recrystallisation Methods 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
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 238000010025 steaming Methods 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
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 150000003462 sulfoxides Chemical class 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
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 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
- 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
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- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The present invention relates to technical field of organic luminescence materials, a kind of four ring gear metal platinum complex luminescent materials based on phenyl carbazole and its field are provided.The four ring gears metal platinum complex has structure shown in logical formula (I).Luminescent material provided by the present invention regulates and controls the photophysics property of four ring gear metal platinum complexes by adjusting the structure of the ligand around metal center and regulating and controlling the structure of substituent group on ligand, has the advantages that emission spectrum is narrow, stability is high 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 four ring gears with improved emission spectrum
Metal platinum complex luminescent material 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.
Although the research of electrooptical material has made marked progress, such as red green phosphorescent organometallic material has been commercialized
And be applied in organic electroluminescent device OLEDs, lighting apparatus and advanced display, but currently available material is still
There are many disadvantages, including not good enough machining property, inefficient transmitting or absorption efficiency and not satisfactory stability.
In addition, good blue light emitting material is very rare, blue-light device is stablized not good enough, and the selection of material of main part is to device
Stability and efficiency have an important influence.Relatively red green phosphor material, blue emitting phosphor material lowest triplet state energy level is higher, meaning
Taste in blue-light device material of main part triplet need it is higher.Therefore, ideal material of main part is more scarce in blue-light device
It is weary.
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 luminous component, 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 keeps its red shift dynamic or blue shift.Thus can meet in light emitting and
Absorb the demand of performance improvement in application.
[summary of the invention]
The purpose of the present invention is to provide a kind of four ring gear metal platinum complexes with improved emission spectrum shine material
Material and its application.
In a first aspect, embodiments of the present invention provide a kind of four ring gear metal platinum complexes based on phenyl carbazole,
The four ring gears metal platinum complex has structure shown in general formula I:
Wherein:
V1、V2、V3And V4It is the atom being connect with Pt, is each independently selected from N atom or C atom, and V1、V2、V3、V4In
Including at least 2 N atoms；
Y1、Y2、Y3、Y4、Y5、Y6、Y7、Y8、Y9、Y10、Y11And Y12It is each independently selected from N atom or CH base；
X1And X2Expression N, B, CH, CD, CR independenta、SiH、SiD、SiRa、GeH、GeD、GeRd, P, P=O, As,
As=O, Bi or Bi=O；
Ra、Rb、RcAnd RdIt is each independently hydrogen, deuterium, aryl, naphthenic base, cycloalkenyl, heterocycle, heteroaryl, alkyl, alkene
Base, alkynyl, halogen, hydroxyl, sulfydryl, nitro, cyano, amino, list or dialkyl amido, list or ammonia diaryl base, alkoxy, virtue
Oxygroup, halogenated alkyl, ester group, itrile group, isonitrile base, heteroaryl, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino, aryloxy group
Carbonylamino, sulfuryl amino, sulfamoyl, carbamoyl, alkylthio group, sulfinyl, urea groups, phosphinylidyne amido, imido grpup,
Sulfo group, carboxyl, diazanyl, substituted silicyl, polymerization group, or combinations thereof；
R1、R2、R3、R4、R5And R6Each independently represent single base replace, it is biradical replace, three bases replace, four bases replace or
It is unsubstituted, and R1、R2、R3、R4、R5And R6Be 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, alkane
Oxygroup, aryloxy group, halogenated alkyl, ester group, itrile group, isonitrile base, heteroaryl, alkoxy carbonyl, acylamino-, alkoxy carbonyl ammonia
Base, aryloxycarbonylamino, sulfuryl amino, sulfamoyl, carbamoyl, alkylthio group, sulfinyl, urea groups, phosphamide
Base, imido grpup, sulfo group, carboxyl, diazanyl, substituted silicyl, polymerization group, or combinations thereof；And two or more are adjacent
Close R1、R2、R3、R4、R5And R6Respectively independence or selective connection it can form condensed ring.
Optionally, the four ring gear metal platinum complexes based on phenyl carbazole provided by embodiments of the present invention have such as
One of lower structure:
The above-mentioned four ring gear metal platinum complexes based on phenyl carbazole provided by embodiments of the present invention have neutrality
Charge.
Embodiments of the present invention also provide the above-mentioned four ring gear metal platinum complexes based on phenyl carbazole in electroluminescent
Application in device.
In addition, embodiments of the present invention also provide a kind of device, including four teeth described above based on phenyl carbazole
Cyclometalated platinum complexes.
Optionally, the device includes full-color display.
Optionally, the device is photovoltaic device.
Optionally, the device is light-emitting display device.
Optionally, the device includes Organic Light Emitting Diode.
Optionally, the device includes phosphorescence Organic Light Emitting Diode.
Optionally, it is to have 100% Internal Quantum effect in device environment that the four ring gears metal platinum complex is chosen
Rate.
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 that the four ring gear metal platinums described above based on phenyl carbazole are matched
Close object.
The beneficial effects of the present invention are: the present invention is by changing ligand structure and regulation ligand around metal center
On substituent structure adjust the photophysics property of metal platinum complex so that provided by the present invention be based on phenyl carbazole
Four ring gear metal platinum complexes can shine in the range of about 400nm to about 700nm, and have emission spectrum it is narrow, steady
Qualitative high and high-efficient advantage；The metal platinum complex is applied in luminescent device, luminous efficiency and device can be improved
Operating time, the numerous areas such as show and illuminate in OLED and have broad application prospects.
[Detailed description of the invention]
To describe the technical solutions in the embodiments of the present invention more clearly, make required in being described below to embodiment
Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for
For those of ordinary skill in the art, without creative efforts, it can also be obtained according to these attached drawings other
Attached drawing, in which:
Fig. 1 is Room temperature emission spectra of the platinum complex Pt 1 in dichloromethane solution in specific embodiment；
Fig. 2 is Room temperature emission spectra of the platinum complex Pt 3 in dichloromethane solution in specific embodiment；
Fig. 3 is Room temperature emission spectra of the platinum complex Pt 28 in dichloromethane solution in specific embodiment；
Fig. 4 is Room temperature emission spectra of the platinum complex Pt 29 in dichloromethane solution in specific embodiment.
The other aspects of picture are also described in picture description after picture.Advantage is by claim
In the element that particularly points out and combination and realize and obtain.It should be pointed out that general remark above and following detailed
Illustrate all to be exemplary and explanatory, not have limited.
[specific embodiment]
The disclosure can be more easily to understand by reference to following specific embodiments and embodiment wherein included.
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 ,=0, 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 condensed 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 such as institute of the present invention
It states.Representative example includes but is not limited to dimethylamino, diethylamino, dipropylamino, diisopropylaminoethyl, dibutyl
Amino, diisobutylamino, two (sec-butyl) amino, two (tert-butyl) amino, dipentylamino, diisoamyl amino, two (uncles
Amyl) 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 R1It can be hydrogen or alkyl of the present invention, naphthenic base, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl radical, virtue
Base or heteroaryl.Throughout the specification, " S (O) " is the shorthand of S=O.Terminology used in the present invention " sulfonyl "
Refer to through formula-S (O)2R1Sulphur-oxo group of expression, wherein R1It can be alkyl, naphthenic base, alkenyl, cycloalkenyl, alkynyl, ring
Alkynyl, aryl or heteroaryl.Terminology used in the present invention " sulfone " passes through formula R1S(O)2R2It indicates, wherein R1And R2It can be independently
For alkyl of the present invention, naphthenic base, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl radical, aryl or heteroaryl.The present invention uses
Term " sulfoxide " pass through formula R1S(O)R2It indicates, wherein R1And R2Alkyl of the present invention, naphthenic base, alkene can independently be
Base, cycloalkenyl, 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 Rsn(a)、Rn(b)、Rn(c)、Rn(d)、Rn (e)." individual substituent group " refers to that each R substituent can be limited independently.For example, if in a situation Rn(a)For halogen,
So in this case Rn(b)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 range of about 400nm to about 700nm.Another party
Face, complex of the invention have improved stability and efficiency relative to traditional transmitting complex.In addition, of the invention matches
Closing object can be used as such as biologic applications, anticancer agent, the luminous mark of emitter in Organic Light Emitting Diode (OLED) or combinations thereof
Note.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.
Four ring gear metal platinum complexes disclosed in the embodiment of the present invention based on phenyl carbazole have shown in logical formula (I)
Structure:
Wherein: V1、V2、V3And V4It is the atom being connect with Pt, is each independently selected from N atom or C atom, and V1、V2、
V3、V4In include at least 2 N atoms；
Y1、Y2、Y3、Y4、Y5、Y6、Y7、Y8、Y9、Y10、Y11And Y12It is each independently selected from N atom or CH base；
X1And X2Each independently represent N, B, CH, CD, CRa、SiH、SiD、SiRa、GeH、GeD、GeRd, P, P=O, As,
As=O, Bi or Bi=O；
Ra、Rb、RcAnd RdIt is each independently hydrogen, deuterium, aryl, naphthenic base, cycloalkenyl, heterocycle, heteroaryl, alkyl, alkene
Base, alkynyl, halogen, hydroxyl, sulfydryl, nitro, cyano, amino, list or dialkyl amido, list or ammonia diaryl base, alkoxy, virtue
Oxygroup, halogenated alkyl, ester group, itrile group, isonitrile base, heteroaryl, alkoxy carbonyl, acylamino-, alkoxycarbonyl amino, aryloxy group
Carbonylamino, sulfuryl amino, sulfamoyl, carbamoyl, alkylthio group, sulfinyl, urea groups, phosphinylidyne amido, imido grpup,
Sulfo group, carboxyl, diazanyl, substituted silicyl, polymerization group, or combinations thereof；
R1、R2、R3、R4、R5And R6Each independently represent single base replace, it is biradical replace, three bases replace, four bases replace or
It is unsubstituted, and R1、R2、R3、R4、R5And R6Be 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, alkane
Oxygroup, aryloxy group, halogenated alkyl, ester group, itrile group, isonitrile base, heteroaryl, alkoxy carbonyl, acylamino-, alkoxy carbonyl ammonia
Base, aryloxycarbonylamino, sulfuryl amino, sulfamoyl, carbamoyl, alkylthio group, sulfinyl, urea groups, phosphamide
Base, imido grpup, sulfo group, carboxyl, diazanyl, substituted silicyl, polymerization group, or combinations thereof；And two or more are adjacent
Close R1、R2、R3、R4、R5And R6Respective independence or the property of can choose connect to form condensed ring.
For molecular formula I described in the present invention, its realm may be defined in the following description.
1) V group
Wherein V1、V2、V3、V4It is the atom being connect with Pt, it is respectively independent, it can be N or C, wherein V1、V2、V3、V4In extremely
It less include 2 N；
On the one hand, V1And V4For N, V2And V3For C；
On the other hand, V1And V3For N, V2And V4For C；
Furthermore V1And V2For N, V3And V4For C；
2) Y group
Wherein Y1、Y2、Y3、Y4、Y5、Y6、Y7、Y8、Y9、Y10、Y11And Y12It is each independently selected from N and CH base；
Wherein Y1、Y2、Y3、Y4、Y5、Y6、Y7、Y8、Y9、Y10、Y11And Y12It is respectively independent, it can be N；
Wherein Y1、Y2、Y3、Y4、Y5、Y6、Y7、Y8、Y9、Y10、Y11And Y12It is respectively independent, it can be CH base；
4) X group
Wherein X1And X2It can be from N, B, CH, CD, CRa、SiH、SiD、SiRa、GeH、GeD、GeRd, P, P=O, As, As=
O, it is selected in Bi Bi=O group；
On the other hand, X1For N, X2For N；
On the other hand, X1For N, X2For B；
On the other hand, X1For B, X2For B；
On the other hand, X1For N, X2For CH；
On the other hand, X1For N, X2For P=O；
On the other hand, X1For N, X2For Bi=O；
On the other hand, X1For N, X2For As=O；
On the other hand, X1For CH, X2For CH；
On the other hand, X1For N, X2For CRa；
On the other hand, X1For N, X2For SiRa；
5) R group
Wherein, R1In the presence of another aspect R1It is not present.
On the one hand, R1It is monosubstituted, another aspect, R1It is disubstituted；On the other hand, R1It is three substitutions；Furthermore R1It is four
Replace；
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；On the other hand, R2It is three substitutions；Furthermore R2It is four
Replace；
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；On the other hand, R3It is three substitutions；Furthermore R3It is four
Replace；
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；
R4 is from hydrogen, deuterium, aryl, naphthenic base, cycloalkenyl, heterocycle, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl simultaneously
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.
On the one hand, R6It is monosubstituted, another aspect, R5It 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.
Exemplary compounds
On the one hand, any four ring gears metal platinum complex reported for the present invention may include under one or more
State structure.In addition, metal platinum complex also may include other structures or part, no longer specifically specially enumerate herein, meanwhile,
The protection scope of present invention is not limited to that structure and part cited in patent.
In an embodiment of the present invention, the provided four ring gear metal platinum complexes based on phenyl carbazole have neutral electricity
Lotus.
In an embodiment of the present invention, the four ring gear metal platinum complexes based on phenyl carbazole are 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, the four ring gear metal platinum complexes based on phenyl carbazole have 100% internal quantum.
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 and mistake.It unless otherwise indicated, is otherwise all to separate title
Weight, 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-MSAgilent 6210TOF LC/MS type mass spectrum
It is measured on instrument；HRMS spectrum measures on Agilent 6210TOF LC/MS type sewage sludge instrument.1H NMR
In spectral data: s=singlet, d=doublet, t=triplet, q=quartet, p=quintet, m=
Multiplet, br=broad.
Synthetic route
General synthetic procedure is as follows:
Embodiment 1
Pt 1 can be prepared according to following methods
The synthesis of 1-Br: 2- bromine carbazole is sequentially added into the drying there-necked flask with reflux condensing tube and magnetic rotor
(14.77g, 60.00mmol, 1.0eq), stannous chloride (60.0mg, 0.60mmol, 0.01eq), tert-butyl alcohol lithium (7.21g,
90.00mmol, 1.5eq), it substitutes nitrogen three times, 2- bromopyridine (8.58mL, 90.00mmol, 1.5eq) then is added, 1- methyl
Imidazoles (95.1 μ L, 1.20mmol, 0.02eq) and toluene (240mL).Reaction mixture is stirred at reflux 5.0 hours at 130 DEG C.
Saturated sodium bisulfite solution 100mL is quenched, and filtering, ethyl acetate sufficiently washs insoluble matter, separates the organic phase in mother liquor, water phase
It is extracted 3 times using 100mL ethyl acetate, merges organic phase, 50mL washing, filtering, anhydrous sodium sulfate is dry, and vacuum distillation removes
Solvent.Gained crude product is isolated and purified into (petroleum ether: methylene chloride=40mL:5mL) by recrystallization, obtains white solid
16.77g yield 87%.1H NMR(500MHz,CDCl3): δ 7.31-7.34 (m, 2H), 7.42 (dd, J=8.0,1.5Hz,
1H), 7.44-7.47 (m, 1H), 7.61 (d, J=8.5Hz, 1H), 7.77 (d, J=8.0Hz, 1H), 7.93-7.96 (m, 2H),
8.01 (d, J=1.5Hz, 1H), 8.08 (d, J=7.5Hz, 1H), 8.73 (d, J=5.0,1.5Hz, 1H)
1-B(OR)2Synthesis: to magnetic rotor dry reaction bottle in sequentially add the bromo- 9- of 2- (2- pyridine)-
9H- carbazole 1-Br (3.20g, 10.0mmol, 1.0eq), connection boric acid pinacol ester (2.60g, 11.0mmol, 1.1eq), PdCl2
(dppf).CH2Cl2(245.0mg, 0.30mmol, 0.03eq), potassium acetate (2.94g, 30.0mmol, 3.0eq).Substitute nitrogen three
It is secondary, dimethyl sulfoxide (20mL) then is added.It is subsequently placed in 80 DEG C of oil baths and reacts 3 days.It is cooled to room temperature, 200mL second is added
Acetoacetic ester dilution, filters, and 50mL water, liquid separation is added, and ethyl acetate aqueous phase extracted three times, merges organic phase, and anhydrous sodium sulfate is dry
Dry organic phase, filtering, vacuum distillation remove solvent, and gained crude product is passed through silica gel column chromatogram separating purification, eluent (petroleum
Ether/ethyl acetate=10:1-4:1), white solid is obtained, 1.0mL ethyl acetate, 20mL petroleum ether room temperature mashing 24 is then added
Hour, filter to obtain white solid 1-B (OR)2, 2.46g, yield 68%.1H NMR(500MHz,DMSO-d6):δ1.31(s,
12H), 7.33-7.36 (m, 1H), 7.49-7.54 (m, 2H), 7.65 (dd, J=8.0,1.0Hz, 1H), 7.74 (d, J=
8.0Hz, 1H), 7.79 (d, J=8.0Hz, 1H), 8.05 (s, 1H), 8.17 (td, J=8.0,2.0Hz, 1H), 8.26 (dd, J=
7.5,0.5Hz, 1H), 8.29 (d, J=7.5Hz, 1H), 8.78 (ddd, J=4.5,1.5,0.5Hz, 1H)
The synthesis of 2-Br: 9H- pyrido [2,3b] indoles is sequentially added into the dry reaction pipe with magnetic rotor
(2.52g, 15.0mmol, 1.0eq), CuI (285.7mg, 1.5mmol, 0.01eq), L-Proline (345.4mg, 3.0mmol,
0.02eq) and K2CO3(4.15g,30.0mmol,2.0eq).Substitute nitrogen three times, then be added the bromo- iodobenzene of 3- (2.40mL,
18.0mmol, 1.2eq) and solvent dimethyl sulfoxide (15mL).Reaction mixture is placed in 120 DEG C of oil baths and reacts 3.5 days.It is cooled to
Room temperature is added the dilution of 100mL ethyl acetate, suction filtered through kieselguhr, and is sufficiently cleaned with ethyl acetate, and 50mL water, liquid separation, second is added
Acetoacetic ester aqueous phase extracted three times, merges organic phase, the dry organic phase of anhydrous sodium sulfate, filtering, vacuum distillation removes solvent, by institute
Crude product is obtained by silica gel column chromatogram separating purification, eluent (petroleum ether/methylene chloride=1:1-1:2) obtains white solid 2-Br
2.78g, yield 57%.Product is directly used in the synthesis of next step.
The synthesis of L1: 9- (3- bromophenyl) -9H- pyrido [2,3b] is sequentially added to having in magnetic rotor dry reaction
Indoles 2-Br (168.9mg, 0.52mmol, 1.0eq), 2- (2- (4,4,5,5- tetramethyls -1,3,2- dioxy boron pentyl)) -9-
(2- pyridyl group) -9H- carbazole 1-B (OR)2(212.8mg, 0.57mmol, 1.1eq), Pd (PPh3)4(18.0mg,0.02mmol,
0.03eq),K2CO3(107.6mg, 0.78mmol, 1.5eq).It substitutes nitrogen three times, toluene (4.0mL) then is added, ethyl alcohol
(1.0mL) and water (1.0mL).Then drum nitrogen 15 minutes, mixture are placed in 100 DEG C of oil baths and react 3 days.It is cooled to room temperature, subtracts
Solvent is distilled off in pressure, and gained crude product is passed through silica gel column chromatogram separating purification, eluent (petrol ether/ethyl acetate=10:1-
5:1), white solid 261.2mg (ligand L 1), yield 75% are obtained.
The synthesis of Pt1: to sequentially add in magnetic rotor dry reaction pipe ligand L 1 (97.2mg, 0.20mmol,
1.0eq), K2PtCl4(91.4mg, 0.22mmol, 1.1eq),nBu4NBr (6.4mg, 0.02mmol, 0.1eq).Substitute nitrogen three
It is secondary, acetic acid (12.0mL) and water (0.4mL) is then added.After stirring 12h under room temperature, it is placed in 120 DEG C of oil baths and reacts 3 days.It is cooling
To room temperature, vacuum distillation removes solvent, and gained crude product is passed through silica gel column chromatogram separating purification, eluent (petroleum ether/dichloromethane
Alkane=3:1-1:1), obtain yellow solid 20.8mg, yield 31%.1H NMR(500MHz,DMSO-d6):δ7.08-7.11(m,
1H), 7.24-7.27 (m, 1H), 7.32-7.33 (m, 1H), 7.36-7.39 (m, 1H), 7.42 (d, J=8.0Hz, 1H), 7.47-
7.51 (m, 1H), 7.53 (dd, J=8.0,1.0Hz, 1H), 7.63-7.66 (m, 3H), 7.70-7.73 (m, 1H), 8.06 (d, J
=8.5Hz, 1H), 8.13 (dd, J=8.0,0.5Hz, 1H), 8.16-8.19 (m, 1H), 8.30 (t, J=9.0Hz, 2H), 8.48
(dd, J=7.5,0.5Hz, 1H), 8.56 (dd, J=6.0,1.5Hz, 1H), 8.89 (dd, J=6.0,1.0Hz, 1H), 9.06
(dd, J=7.5,1.5Hz, 1H) .HRMS (ESI): theoretical value C34H21N4Pt[M+H]+680.1408 experiment value 680.1411.
Embodiment 2
Pt 3 can be prepared according to following methods
1-B(OR)2The synthesis of-Me: the bromo- 9- of 2- (2- (4- picoline is sequentially added to having in magnetic rotor reaction tube
Base)) -9H- carbazole 1-Br-Me (2.0g, 5.9mmol, 1.0eq), connection boric acid pinacol ester (1.65g, 6.5mmol, 1.1eq),
PdCl2(dppf).CH2Cl2(144.5mg, 0.18mmol, 0.03eq), potassium acetate (1.74g, 17.7mmol, 3.0eq).It substitutes
Three times, dimethyl sulfoxide (10mL) then is added in nitrogen.80 DEG C of oil baths are subsequently placed to react 3 days.It is cooled to room temperature, is added
The dilution of 100mL ethyl acetate, filters, and 50mL water, liquid separation is added, and ethyl acetate aqueous phase extracted three times, merges organic phase, anhydrous sulphur
The dry organic phase of sour sodium, filtering, vacuum distillation remove solvent, and gained crude product is passed through silica gel column chromatogram separating purification, eluent
(petrol ether/ethyl acetate=10:1-5:1) obtains white solid 2.06g, yield 91%.
The synthesis of L3: to sequentially add in magnetic rotor dry reaction pipe 2- (2- (tetramethyl -1,3 4,4,5,5-,
2- dioxy boron pentyl)) -9- (2- (4- picolyl)) -9H- carbazole 1-B (OR)2-Me(192.1mg,0.50mmol,
1.0eq), 9- (3- bromophenyl) -9H- pyrido [2,3b] indoles 2-Br (177.8mg, 0.55mmol, 1.1eq), Pd (PPh3)4
(17.3mg,0.02mmol,0.03eq),K2CO3(103.5mg, 0.75mmol, 1.5eq).It substitutes nitrogen three times, first is then added
Benzene (4.0mL), ethyl alcohol (1.0mL) and water (1.0mL).Then drum nitrogen 15 minutes, mixture are placed in 100 DEG C of oil baths and react 3 days.
It is cooled to room temperature, vacuum distillation removes solvent, and gained crude product is passed through silica gel column chromatogram separating purification, eluent (petroleum ether/second
Acetoacetic ester=5:1), obtain white solid 190.2mg, yield 76%.1H NMR(500MHz,DMSO-d6):δ2.46(s.3H),
7.32-7.40 (m, 4H), 7.46-7.50 (m, 1H), 7.53 (td, J=7.0,1.0Hz, 1H), 7.59 (d, J=8.0Hz, 1H),
7.67-7.73 (m, 3H), 7.75 (t, J=8.0Hz, 1H), 7.79 (d, J=8.0Hz, 1H), 7.86 (d, J=7.5Hz, 1H),
8.01 (t, J=2.0Hz, 1H), 8.10 (d, J=1.0Hz, 1H), 8.28 (d, J=7.5Hz, 1H), 8.33 (d, J=8.0Hz,
1H), 8.35 (d, J=8.5Hz, 1H), 8.44 (dd, J=5.0,1.5Hz, 1H), 8.58 (d, J=5.0Hz, 1H), 8.67 (dd,
J=7.5,1.5Hz, 1H)
The synthesis of Pt3: to sequentially add in magnetic rotor dry reaction pipe L3 (90.0mg, 0.18mmol,
1.0eq), K2PtCl4(82.1mg, 0.20mmol, 1.1eq),nBu4NBr (6.4mg, 0.02mmol, 0.1eq).Substitute nitrogen three
It is secondary, acetic acid (10.0mL) and water (0.3mL) is then added.After stirring 10h under room temperature, it is placed in 120 DEG C of oil baths and reacts 1 day.It is cooling
To room temperature, vacuum distillation removes solvent, and gained crude product is passed through silica gel column chromatogram separating purification, eluent (petroleum ether/dichloromethane
Alkane=3:1-1:1), obtain yellow solid 29.5mg, yield 24%.HRMS (ESI): theoretical value C35H23N4Pt[M+H]+
694.1565 experiment value 680.1573.
Embodiment 3
Pt 28 can be prepared according to following methods
The synthesis of 2-Br-F: 9H- pyrido [2,3b] indoles is sequentially added into the dry reaction pipe with magnetic rotor
(5.04g, 30.00mmol, 1.0eq), CuI (571.4mg, 3.00mmol, 0.01eq), L-Proline (690.0mg,
6.00mmol, 0.02eq) and K2CO3(8.29g,60.00mmol,2.0eq).It substitutes nitrogen three times, it is bromo- that 1,3- bis- is then added
5- fluorobenzene (9.14g, 36.0mmol, 1.2eq) and solvent dimethyl sulfoxide (30mL).It is anti-that reaction mixture is placed in 120 DEG C of oil baths
It answers 1.5 days.It is cooled to room temperature, the dilution of 100mL ethyl acetate, suction filtered through kieselguhr is added, and sufficiently cleaned with ethyl acetate, is added
50mL water, liquid separation, ethyl acetate aqueous phase extracted three times, merge organic phase, the dry organic phase of anhydrous sodium sulfate, filtering, decompression steaming
Solvent is removed in distillation, by gained crude product by silica gel column chromatogram separating purification, eluent (petroleum ether/methylene chloride=4:1-2:1),
Obtain white solid 2-Br-F 3.22g, yield 31%.Product is directly used in the synthesis of next step.
The synthesis of L28: 2- (2- (4,4,5,5- tetramethyl -1,3,2- is sequentially added to having in magnetic rotor dry reaction
Dioxy boron pentyl)) -9- (2- pyridyl group) -9H- carbazole 1-B (OR)2(370.3mg, 1.00mmol, 1.0eq), (3- is bromo- by 9-
5- fluorophenyl) -9H- pyrido [2,3b] indoles 2-Br-F (374.2mg, 1.10mmol, 1.1eq), Pd (PPh3)4(57.8mg,
0.05mmol,0.05eq),K2CO3(207.0mg, 1.50mmol, 1.5eq).It substitutes nitrogen three times, toluene (8mL) then is added,
Ethyl alcohol (2.0mL) and water (2.0mL).Then drum nitrogen 15 minutes, mixture are placed in 100 DEG C of oil baths and react 3 days.It is cooled to room
Temperature, vacuum distillation remove solvent, by gained crude product by silica gel column chromatogram separating purification, eluent (petrol ether/ethyl acetate=
10:1-4:1), white solid 344.2mg (L28), yield 68% are obtained.
The synthesis of Pt28: to sequentially add in magnetic rotor dry reaction pipe ligand L 28 (50mg, 0.10mmol,
1.0eq), K2PtCl4(45.7mg, 0.11mmol, 1.1eq),nBu4NBr (3.2mg, 0.01mmol, 0.1eq).Substitute nitrogen three
It is secondary, acetic acid (6.0mL) and water (0.2mL) is then added.After being stirred for 24 hours under room temperature, it is placed in 120 DEG C of oil baths and reacts 3 days.It is cooled to
Room temperature, vacuum distillation remove solvent, and gained crude product is passed through silica gel column chromatogram separating purification, eluent (petroleum ether/methylene chloride
=3:1-0:1), obtain yellow solid 2.0mg, yield 3%.MS (ESI): theoretical value C34H21N4Pt[M-F+2H]+680.1, experiment
Value 680.5.
Embodiment 4
Pt 29 can be prepared according to following methods
2-Br-CF3Synthesis: to magnetic rotor dry reaction pipe in sequentially add 9H- pyrido [2,3b] Yin
Diindyl (5.04g, 30.00mmol, 1.0eq), CuI (571.4mg, 3.00mmol, 0.01eq), L-Proline (690.0mg,
6.00mmol, 0.02eq) and K2CO3(8.29g,60.00mmol,2.0eq).It substitutes nitrogen three times, it is bromo- that 1,3- bis- is then added
5- trifluoromethylbenzene (10.94g, 36.0mmol, 1.2eq) and solvent dimethyl sulfoxide (30mL).Reaction mixture is placed in 120 DEG C
Oil bath is reacted 1.5 days.It is cooled to room temperature, 100mL ethyl acetate is added and dilutes, suction filtered through kieselguhr, and it is sufficiently clear with ethyl acetate
It washes, 50mL water, liquid separation is added, ethyl acetate aqueous phase extracted three times, merges organic phase, and the dry organic phase of anhydrous sodium sulfate filters,
Vacuum distillation removes solvent, by gained crude product by silica gel column chromatogram separating purification, eluent (petroleum ether/methylene chloride=4:
1-2:1), white solid 2-Br-CF is obtained35.15g, yield 43%.Product is directly used in the synthesis of next step.
The synthesis of L29: 2- (2- (4,4,5,5- tetramethyl -1,3,2- is sequentially added to having in magnetic rotor dry reaction
Dioxy boron pentyl)) -9- (2- pyridyl group) -9H- carbazole 1-B (OR)2(370.3mg, 1.00mmol, 1.0eq), (3- is bromo- by 9-
5- trifluoromethyl) -9H- pyrido [2,3b] indoles 2-Br-CF3(564.0mg, 1.40mmol, 1.4eq), Pd (PPh3)4
(57.8mg,0.05mmol,0.05eq),K2CO3(207.0mg, 1.50mmol, 1.5eq).It substitutes nitrogen three times, first is then added
Benzene (8mL), ethyl alcohol (2.0mL) and water (2.0mL).Then drum nitrogen 15 minutes, mixture are placed in 100 DEG C of oil baths and react 3 days.It is cold
But to room temperature, vacuum distillation removes solvent, and gained crude product is passed through silica gel column chromatogram separating purification, eluent (petroleum ether/acetic acid
Ethyl ester=10:1-1:1), obtain white solid 345.2mg (L29), yield 62%.
The synthesis of Pt29: to sequentially add in magnetic rotor dry reaction pipe ligand L 29 (55.0mg, 0.10mmol,
1.0eq), K2PtCl4(45.7mg, 0.11mmol, 1.1eq),nBu4NBr (3.2mg, 0.01mmol, 0.1eq).Substitute nitrogen three
It is secondary, acetic acid (6.0mL) and water (0.2mL) is then added.After stirring 12h under room temperature, it is placed in 120 DEG C of oil baths and reacts 3 days.It is cooled to
Room temperature, vacuum distillation remove solvent, and gained crude product is passed through silica gel column chromatogram separating purification, eluent (petroleum ether/methylene chloride
=3:1-1:1), obtain yellow solid 54.4mg, yield 73%.MS (ESI): theoretical value C34H21N4Pt[M-CF3+2H]+680.1,
Experiment value 680.5.
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 (8)
1. a kind of four ring gear metal platinum complexes based on phenyl carbazole, which is characterized in that the four ring gears metal platinum complex
With structure shown in logical formula (I):
Wherein:
V1、V2、V3And V4It is each independently selected from N atom or C atom, and V1、V2、V3、V4In include at least 2 N atoms；
Y1、Y2、Y3、Y4、Y5、Y6、Y7、Y8、Y9、Y10、Y11And Y12It is each independently selected from N atom or CH base；
X1And X2Each independently represent N, B, CH, CD, CRa、SiH、SiD、SiRa、GeH、GeD、GeRd, P, P=O, As, As=
O, Bi or Bi=O；
Ra、Rb、RcAnd RdIt is each independently hydrogen, deuterium, aryl, naphthenic base, cycloalkenyl, heterocycle, heteroaryl, alkyl, alkenyl, alkynes
Base, 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-, alkoxycarbonyl amino, aryloxycarbonyl
Amino, sulfuryl amino, sulfamoyl, carbamoyl, alkylthio group, sulfinyl, urea groups, phosphinylidyne amido, imido grpup, sulphur
Base, carboxyl, diazanyl, substituted silicyl, polymerization group, or combinations thereof；
R1、R2、R3、R4、R5And R6Single base substitution, biradical substitution, the substitution of three bases, the substitution of four bases or nothing is each independently represented to take
Generation, and R1、R2、R3、R4、R5And R6Be 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, acylamino-, alkoxycarbonyl amino, fragrant oxygen
Base carbonylamino, sulfuryl amino, sulfamoyl, carbamoyl, alkylthio group, sulfinyl, urea groups, phosphinylidyne amido, imines
Base, sulfo group, carboxyl, diazanyl, substituted silicyl, polymerization group, or combinations thereof；And two or more neighbouring R1、
R2、R3、R4、R5And R6Respective independence or selective connection form condensed ring.
2. the four ring gear metal platinum complexes according to claim 1 based on phenyl carbazole, which is characterized in that the platinum is matched
Closing object has one of following structure:
3. the four ring gear metal platinum complexes according to claim 1 or 2 based on phenyl carbazole, which is characterized in that described
Platinum complex has neutral charge.
4. four ring gear metal platinum complex the answering in electroluminescent device of any of claims 1 or 2 based on phenyl carbazole
With.
5. a kind of device, which is characterized in that the device includes four teeth based on phenyl carbazole as claimed in claim 1 or 2
Cyclometalated platinum complexes.
6. device according to claim 5, which is characterized in that the device includes full-color display, photovoltaic device, shines
Display device, Organic Light Emitting Diode or phosphorescence Organic Light Emitting Diode.
7. device according to claim 5, which is characterized in that the four ring gear metal platinum complexes based on phenyl carbazole
There is 100% internal quantum in the device environment.
8. device according to claim 5, including at least one cathode, at least one anode and at least one layer of luminescent layer,
It is characterized in that, at least one layer in the luminescent layer includes the four ring gears gold of any of claims 1 or 2 based on phenyl carbazole
Belong to platinum complex.
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| CN201810872326.1A CN108948095B (en) | 2018-08-02 | 2018-08-02 | Tetradentate ring metal platinum complex based on phenylcarbazole and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111662336A (en) * | 2020-02-06 | 2020-09-15 | 浙江虹舞科技有限公司 | Tetradentate ring metal platinum complex phosphorescent material and organic light-emitting element |
| CN113501809A (en) * | 2021-07-13 | 2021-10-15 | 浙江工业大学 | Quaternary ring metal platinum (II) and palladium (II) complex luminescent material containing quinoline structural unit and application thereof |
| CN113801154A (en) * | 2021-10-20 | 2021-12-17 | 中钢集团南京新材料研究院有限公司 | Synthesis method of 9H-carbazole-2-boronic acid pinacol ester with C2-position of carbazole directly boronated by C-H |
| CN114805446A (en) * | 2022-04-09 | 2022-07-29 | 浙江工业大学 | Metal platinum (II) and palladium (II) complex, organic light-emitting device, and display or lighting device |
| CN115160379A (en) * | 2022-08-01 | 2022-10-11 | 浙江工业大学 | Circular polarization luminescent material, application, luminescent display device and display device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104232076A (en) * | 2013-06-10 | 2014-12-24 | 代表亚利桑那大学的亚利桑那校董会 | Phosphorescent tetradentate metal complexes having modified emission spectra |
| CN104693243A (en) * | 2013-10-14 | 2015-06-10 | 代表亚利桑那大学的亚利桑那校董事会 | Platinum complexes and devices |
| US20150194616A1 (en) * | 2014-01-07 | 2015-07-09 | Jian Li | Tetradentate Platinum And Palladium Complex Emitters Containing Phenyl-Pyrazole And Its Analogues |
-
2018
- 2018-08-02 CN CN201810872326.1A patent/CN108948095B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104232076A (en) * | 2013-06-10 | 2014-12-24 | 代表亚利桑那大学的亚利桑那校董会 | Phosphorescent tetradentate metal complexes having modified emission spectra |
| CN104693243A (en) * | 2013-10-14 | 2015-06-10 | 代表亚利桑那大学的亚利桑那校董事会 | Platinum complexes and devices |
| US20150194616A1 (en) * | 2014-01-07 | 2015-07-09 | Jian Li | Tetradentate Platinum And Palladium Complex Emitters Containing Phenyl-Pyrazole And Its Analogues |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111662336A (en) * | 2020-02-06 | 2020-09-15 | 浙江虹舞科技有限公司 | Tetradentate ring metal platinum complex phosphorescent material and organic light-emitting element |
| CN111662336B (en) * | 2020-02-06 | 2023-02-14 | 浙江虹舞科技有限公司 | Tetradentate ring metal platinum complex phosphorescent material and organic light-emitting element |
| CN113501809A (en) * | 2021-07-13 | 2021-10-15 | 浙江工业大学 | Quaternary ring metal platinum (II) and palladium (II) complex luminescent material containing quinoline structural unit and application thereof |
| CN113501809B (en) * | 2021-07-13 | 2022-07-26 | 浙江工业大学 | Quaternary ring metal platinum (II) and palladium (II) complex luminescent material containing quinoline structural unit and application thereof |
| CN113801154A (en) * | 2021-10-20 | 2021-12-17 | 中钢集团南京新材料研究院有限公司 | Synthesis method of 9H-carbazole-2-boronic acid pinacol ester with C2-position of carbazole directly boronated by C-H |
| CN113801154B (en) * | 2021-10-20 | 2024-01-26 | 中钢集团南京新材料研究院有限公司 | Synthesis method of carbazole C2-site direct C-H boronated 9H-carbazole-2-boronic acid pinacol ester |
| CN114805446A (en) * | 2022-04-09 | 2022-07-29 | 浙江工业大学 | Metal platinum (II) and palladium (II) complex, organic light-emitting device, and display or lighting device |
| CN114805446B (en) * | 2022-04-09 | 2023-08-15 | 浙江工业大学 | Platinum (II) and palladium (II) complexes, organic light-emitting devices and display or lighting devices |
| CN115160379A (en) * | 2022-08-01 | 2022-10-11 | 浙江工业大学 | Circular polarization luminescent material, application, luminescent display device and display device |
| CN115160379B (en) * | 2022-08-01 | 2024-02-02 | 浙江工业大学 | Circularly polarized luminescent material, application thereof, luminescent display device and display device |
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