CN109678906B - Metal platinum (II) complex containing double-bridged phenyl-pyrazole structural unit and application thereof - Google Patents
Metal platinum (II) complex containing double-bridged phenyl-pyrazole structural unit and application thereof Download PDFInfo
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- CN109678906B CN109678906B CN201811646211.7A CN201811646211A CN109678906B CN 109678906 B CN109678906 B CN 109678906B CN 201811646211 A CN201811646211 A CN 201811646211A CN 109678906 B CN109678906 B CN 109678906B
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- alkyl
- complex
- platinum
- cycloalkyl
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 39
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000002184 metal Substances 0.000 title claims abstract description 36
- OEDUIFSDODUDRK-UHFFFAOYSA-N 5-phenyl-1h-pyrazole Chemical compound N1N=CC=C1C1=CC=CC=C1 OEDUIFSDODUDRK-UHFFFAOYSA-N 0.000 title claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 74
- 125000003118 aryl group Chemical group 0.000 claims description 62
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 59
- 229910052739 hydrogen Inorganic materials 0.000 claims description 32
- 239000001257 hydrogen Substances 0.000 claims description 32
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 27
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 26
- 229910052805 deuterium Inorganic materials 0.000 claims description 26
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- 125000005647 linker group Chemical group 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 32
- 125000001424 substituent group Chemical group 0.000 abstract description 32
- 239000003446 ligand Substances 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 15
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 238000005286 illumination Methods 0.000 abstract description 3
- 230000001276 controlling effect Effects 0.000 abstract description 2
- FBTOLQFRGURPJH-UHFFFAOYSA-N 1-phenyl-9h-carbazole Chemical compound C1=CC=CC=C1C1=CC=CC2=C1NC1=CC=CC=C12 FBTOLQFRGURPJH-UHFFFAOYSA-N 0.000 abstract 1
- -1 platinum (II) metal complex Chemical class 0.000 description 176
- 125000001072 heteroaryl group Chemical group 0.000 description 71
- 125000000392 cycloalkenyl group Chemical group 0.000 description 49
- 125000003545 alkoxy group Chemical group 0.000 description 44
- 150000001875 compounds Chemical class 0.000 description 44
- 125000003342 alkenyl group Chemical group 0.000 description 43
- 125000000304 alkynyl group Chemical group 0.000 description 43
- 229910052736 halogen Inorganic materials 0.000 description 39
- 150000002367 halogens Chemical class 0.000 description 39
- 150000002148 esters Chemical class 0.000 description 31
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- 125000000623 heterocyclic group Chemical group 0.000 description 30
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 29
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 125000004663 dialkyl amino group Chemical group 0.000 description 26
- 125000001188 haloalkyl group Chemical group 0.000 description 26
- 150000002825 nitriles Chemical class 0.000 description 26
- 125000005162 aryl oxy carbonyl amino group Chemical group 0.000 description 25
- 125000004104 aryloxy group Chemical group 0.000 description 25
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 25
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 25
- 125000004986 diarylamino group Chemical group 0.000 description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 25
- 150000002527 isonitriles Chemical class 0.000 description 25
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 25
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 24
- 125000004466 alkoxycarbonylamino group Chemical group 0.000 description 24
- 125000004414 alkyl thio group Chemical group 0.000 description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 22
- 125000003396 thiol group Chemical class [H]S* 0.000 description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 19
- 125000001841 imino group Chemical group [H]N=* 0.000 description 19
- 150000001408 amides Chemical class 0.000 description 17
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 238000006467 substitution reaction Methods 0.000 description 14
- 239000010410 layer Substances 0.000 description 13
- 238000000295 emission spectrum Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 11
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 10
- 125000003368 amide group Chemical group 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 125000005842 heteroatom Chemical group 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 7
- 125000004429 atom Chemical group 0.000 description 7
- 230000003111 delayed effect Effects 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 125000000464 thioxo group Chemical group S=* 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 230000005281 excited state Effects 0.000 description 6
- 125000001590 germanediyl group Chemical group [H][Ge]([H])(*)* 0.000 description 6
- 238000004770 highest occupied molecular orbital Methods 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 238000010898 silica gel chromatography Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- XMIJDTGORVPYLW-UHFFFAOYSA-N [SiH2] Chemical compound [SiH2] XMIJDTGORVPYLW-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 239000012634 fragment Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000001748 luminescence spectrum Methods 0.000 description 4
- 230000007935 neutral effect Effects 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 229910018162 SeO2 Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 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 3
- 125000004366 heterocycloalkenyl group Chemical group 0.000 description 3
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 3
- 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 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 150000002466 imines Chemical class 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 229920000412 polyarylene Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 125000003226 pyrazolyl group Chemical group 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 3
- 125000000547 substituted alkyl group Chemical group 0.000 description 3
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 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
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 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
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 description 2
- 125000005233 alkylalcohol group Chemical group 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 150000005347 biaryls Chemical group 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
- SXGBREZGMJVYRL-UHFFFAOYSA-N butan-1-amine;hydrobromide Chemical compound [Br-].CCCC[NH3+] SXGBREZGMJVYRL-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 2
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- SBOJXQVPLKSXOG-UHFFFAOYSA-N o-amino-hydroxylamine Chemical compound NON SBOJXQVPLKSXOG-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 238000013086 organic photovoltaic Methods 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 2
- 150000003057 platinum Chemical class 0.000 description 2
- NDBYXKQCPYUOMI-UHFFFAOYSA-N platinum(4+) Chemical class [Pt+4] NDBYXKQCPYUOMI-UHFFFAOYSA-N 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 125000005346 substituted cycloalkyl group Chemical group 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 125000001113 thiadiazolyl group Chemical group 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- 125000004502 1,2,3-oxadiazolyl group Chemical group 0.000 description 1
- 125000004511 1,2,3-thiadiazolyl group Chemical group 0.000 description 1
- 125000001399 1,2,3-triazolyl group Chemical group N1N=NC(=C1)* 0.000 description 1
- 125000004506 1,2,5-oxadiazolyl group Chemical group 0.000 description 1
- 125000004517 1,2,5-thiadiazolyl group Chemical group 0.000 description 1
- 125000001781 1,3,4-oxadiazolyl group Chemical group 0.000 description 1
- 125000004520 1,3,4-thiadiazolyl group Chemical group 0.000 description 1
- 125000003363 1,3,5-triazinyl group Chemical group N1=C(N=CN=C1)* 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- XJWFZVYQZJUUIY-UHFFFAOYSA-N 4-bromo-1-(3-methoxyphenyl)pyrazole Chemical compound COC1=CC=CC(N2N=CC(Br)=C2)=C1 XJWFZVYQZJUUIY-UHFFFAOYSA-N 0.000 description 1
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 description 1
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910004749 OS(O)2 Inorganic materials 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910019029 PtCl4 Inorganic materials 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 239000007864 aqueous solution 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
- 125000000732 arylene group Chemical group 0.000 description 1
- 125000002393 azetidinyl group Chemical group 0.000 description 1
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- UNXISIRQWPTTSN-UHFFFAOYSA-N boron;2,3-dimethylbutane-2,3-diol Chemical compound [B].[B].CC(C)(O)C(C)(C)O UNXISIRQWPTTSN-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling 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
- 230000008859 change Effects 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 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
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- 238000004020 luminiscence type Methods 0.000 description 1
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
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Abstract
The invention provides a metal platinum (II) complex containing a double-bridged phenyl-carbazole structural unit and application thereof. The metal platinum (II) complex has a structure represented by the general formula (I). The luminescent material provided by the invention regulates and controls the photophysical properties of the tetradentate ring metal platinum (II) complex by regulating the structure of the ligand surrounding the metal center and regulating and controlling the structure of the substituent group on the ligand, and has the advantages of high stability and high efficiency; the method has wide application prospect in various fields such as OLED display and illumination.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of organic luminescent materials, in particular to a metal platinum (II) complex phosphorescence and delayed fluorescence or pure phosphorescence luminescent material containing a double-bridged phenyl-pyrazole structural unit and application thereof.
[ background of the invention ]
Compounds capable of absorbing and/or emitting light are suitable for use in a variety of optical and electroluminescent devices, including: light absorbing, solar and photosensitive devices, Organic Light Emitting Diodes (OLEDs), light emitting devices, or devices capable of both light absorption and light emission and as markers (markers) for biological applications. Much research has been devoted to the discovery and optimization of organic and organometallic materials for use in optical and electroluminescent devices. In general, research in this field is aimed at achieving a number of goals, including improvements in absorption and emission efficiencies, and improvements in processing capabilities.
Good blue light emitting materials in the organic light emitting materials are rare, the stability of a blue light device is not good enough, and compared with red and green phosphorescent materials, the lowest triplet state energy level of the blue light phosphorescent materials is higher, which means that the stability of the phosphorescent materials in the blue light device is more important.
Typically, a change in chemical structure affects the electronic structure of a compound, thereby affecting its optical properties (e.g., emission and absorption spectra), and thus, changing the chemical structure can cause the compound to have particular emission or absorption characteristics. In addition, the optical properties of the compounds can also be modulated by changing the ligands at the structural center. For example, compounds bearing ligands with electron donating or electron withdrawing substituents often exhibit different optical properties, including different emission and absorption spectra.
Because the phosphorescent multidentate platinum metal complexes can simultaneously utilize singlet excitons and triplet excitons which are electrically excited, 100% of internal quantum efficiency is obtained, and the complexes can be used as alternative luminescent materials of OLEDs. In general, the ligand of the multidentate platinum metal complex includes a luminescent group and an auxiliary group. If a conjugated group is introduced, for example, an aromatic ring substituent or a heteroatom substituent or the like is introduced into a luminescent molecule, the energy levels of the Highest Molecular occupied orbital (HOMO) and the Lowest Molecular Unoccupied orbital (LUMO) of the luminescent material can be changed, and at the same time, the energy level gap between the HOMO orbital and the LUMO orbital can be further adjusted, so that the emission spectrum property of the phosphorescent multidentate platinum metal complex can be adjusted, for example, the emission spectrum property can be made wider or narrower, or the emission spectrum property can be blue-shifted. Thereby meeting the need for improved performance in light emitting and absorbing applications.
Although the literature has many reports on divalent cyclometalated platinum (II) metal complex phosphorescent materials, no report is found on the metal platinum (II) complex containing a double-bridged phenyl-pyrazole structural unit.
[ summary of the invention ]
The invention aims to provide a metal platinum (II) complex containing a double-bridged phenyl-pyrazole structural unit, and the complex can be used as a luminescent material in an OLED device. The luminescent material provided by the invention regulates and controls the photophysical properties of the tetradentate ring metal platinum (II) complex by regulating the structure of the ligand surrounding the metal center and regulating and controlling the structure of the substituent group on the ligand, and has the advantages of high stability and high efficiency; the method has wide application prospect in various fields such as OLED display and illumination.
The technical scheme of the invention is as follows: providing a metal platinum (II) complex comprising a bis-bridged phenyl-pyrazole structural unit, the metal platinum (II) complex having a structure represented by general formula (I):
wherein:
linking group X1And X2Exist simultaneously; wherein X1And X2May each be independently selected from CH2、CHD、CD2、CR100R101、SiH2、SiHD、SiD2、SiR102R103、GeH2、Ge HD、GeD2、GeR104R105；
A is selected from O, S, CH2、CHD、CD2、CR200R201、C=O、SiR202R203、GeH2、GeR204R205、NH、ND、NR206、PH、PD、PR207、R208P=O、AsR209、R210As=O、S=O、SO2、Se、Se=O、SeO2、BH、BD、BR211、R212Bi = O, BiH, BiD, or BiR213；
Ra、Rb、Rc、Rd、Re、RfAnd RgEach independently selected from the group consisting of hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxy, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imine, sulfo, carboxyl, hydrazino, silyl, substituted silyl, poly (arylene ether), poly (arylene), and poly (arylene), poly (arylene) or (arylene) sA polymeric group, or a combination thereof;
Ra、Rb、Rc、Rd、Re、Rfand RgThe substitution modes of (A) are respectively and independently represented as mono-substitution, di-substitution, tri-substitution, tetra-substitution or non-substitution, and two adjacent substituents can form a condensed ring;
m, n, s, each independently represent an integer of 0 to 4, o, r each independently represent an integer of 0 to 2, p represents an integer of 0 to 3, q represents an integer of 0 to 1;
the R is100、R101、R102、R103、R104、R105、R200、R201、R202、R203、R204、R205、R206、R207、R208、R209、R210、R211、R212、R213Each independently selected from aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxy, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amide, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxy, hydrazino, silyl, substituted silyl, polymeric group, or a combination thereof; wherein two adjacent substituents may form a fused ring.
Optionally, the metal platinum (II) complex has a structure represented by general formula (II), (III), (IV), (V):
wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10And R11Each independently selected from hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxy, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imine, sulfo, carboxyl, hydrazine, silyl, substituted silyl, polymeric group, or a combination thereof; adjacent said R1、R2、R3、R4、R5、R6、R7、R8、R9、R10And R11May be joined to form a fused ring.
Alternatively, in the structures represented by the general formulae (II), (III), (IV) and (V), R is8、R9、R10And R11Each independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, or octylphenyl; the R is2、R3Each independently selected from hydrogen or methyl.
Alternatively, in the structures represented by the general formulae (II), (III), (IV) and (V), R isa、Rb、Rc、Rd、Re、RfAnd RgEach independently selected from hydrogen, deuterium, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, butoxy.
Alternatively, the metal platinum (II) complex containing a bis-bridged phenyl-pyrazole building block has the structure of one of:
embodiments of the present invention provide that the above-described metal platinum (II) complexes containing a bis-bridged phenyl-pyrazole building block have a neutral charge.
Embodiments of the present invention also provide for the use of the above-described platinum (II) metal complexes containing a bis-bridged phenyl-pyrazole building block in electroluminescent devices.
Furthermore, embodiments of the present invention also provide a device comprising a metal platinum (II) complex comprising a bis-bridged phenyl-pyrazole building block as described above.
Optionally, the device is a full color display, a photovoltaic device, a light emitting display device, an organic light emitting diode, a phosphorescent organic light emitting diode.
Alternatively, there is provided in an embodiment of the present invention a device comprising at least one cathode, at least one anode and at least one light emitting layer, at least one of said light emitting layers comprising a metal platinum (II) complex comprising a doubly bridged phenyl-pyrazole building block as described above.
The invention has the beneficial effects that: according to the invention, two benzene rings and a pyrazole ring are linked through a linking group, so that the dihedral angle of phenyl-phenyl and the dihedral angle of phenyl-pyrazole can be effectively reduced to approach zero, the conjugation degree between the dihedral angle of phenyl-pyrazole and the dihedral angle of phenyl-pyrazole is greatly improved, and the triplet state energy level of the metal platinum (II) complex is greatly reduced; meanwhile, the strong spin-orbit coupling effect of the platinum metal ions enables the complex to emit blue-shifted delayed fluorescence at room temperature spectrum, so that blue light can be emitted by a material with small triplet state energy level based on the design, a powerful solution is provided for the development of stable blue light OLED, and the method has wide application prospects in various fields such as OLED display and illumination.
[ description of the drawings ]
FIG. 1 is a room temperature emission spectrum of a platinum (II) metal complex Pt3 of the present invention in a methylene chloride solution and a 77K emission spectrum in 2-methyltetrahydrofuran;
FIG. 2 is a distribution of HOMO-1, HOMO, LUMO and LUMO +1 orbitals of a platinum (II) metal complex Pt3 according to the present invention;
FIG. 3 is a distribution of HOMO-1, HOMO, LUMO and LUMO +1 orbitals of a platinum (II) metal complex Pt31 according to the present invention;
FIG. 4 is a distribution of HOMO-1, HOMO, LUMO and LUMO +1 orbitals of a platinum (II) metal complex Pt32 according to the present invention;
FIG. 5 is a distribution of HOMO-1, HOMO, LUMO and LUMO +1 orbitals of a platinum (II) metal complex Pt33 according to the present invention.
FIG. 6 is a normalized luminescence spectrum of a platinum (II) metal complex Pt3 of the present invention and a control.
[ detailed description ] embodiments
The invention is further described with reference to the following figures and embodiments.
The disclosure may be understood more readily by reference to the following detailed description and the examples included therein.
Before the present compounds, devices, and/or methods are disclosed and described, it is to be understood that they are not limited to the particular synthetic methods (otherwise specified), or to the particular reagents (otherwise specified), as such can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing, the exemplary methods and materials are described below.
As used herein, the terms "optionally," "optionally," mean that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.
Disclosed are components useful in preparing the compositions described herein, as well as the compositions themselves to be used in the methods disclosed herein. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each various individual and collective combinations and permutation of these compounds may not be specifically disclosed, each is specifically contemplated and described herein. For example, if a particular compound is disclosed and discussed, and a number of modifications that can be made to a number of molecules comprising the compound are discussed, then various and each combination and permutation of the compound are specifically contemplated and may be made, otherwise specifically indicated to the contrary. Thus, if a class of molecules A, B, and C are disclosed as well as a class of molecules D, E, and F, and an example of a combination molecule A-D is disclosed, then even if each is not individually recited, it is contemplated that each individually and collectively contemplated combination of meanings, A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F, will be disclosed. Likewise, any subset or combination of these is also disclosed. Thus, for example, it is contemplated that subgroups A-E, B-F, and C-E are disclosed. These concepts are applicable to all aspects of the invention, including but not limited to the steps of the methods of making and using the compositions. Thus, if there are a variety of additional steps that can be performed it is understood that each of these additional steps can be performed with a specific embodiment or combination of embodiments of the method.
The linking atom used in the present invention can link two groups, for example, N and C groups. The linking atom can optionally (if valency permits) have other chemical moieties attached. For example, in one aspect, oxygen does not have any other chemical group attached because once bonded to two atoms (e.g., N or C) valences have been satisfied. Conversely, when carbon is a linking atom, two additional chemical moieties can be attached to the carbon atom. Suitable chemical moieties include, but are not limited to, hydrogen, hydroxyl, alkyl, alkoxy, = O, halogen, nitro, amine, amide, thiol, aryl, heteroaryl, cycloalkyl, and heterocyclyl.
The term "cyclic structure" or similar terms as used herein refers to any cyclic chemical structure including, but not limited to, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclyl, carbene, and N-heterocyclic carbene.
The term "substituted" as used herein is intended to encompass all permissible substituents of organic compounds. In a broad aspect, permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, and aromatic and nonaromatic substituents of organic compounds. Illustrative substituents include, for example, those described below. The permissible substituents can be one or more, identical or different for suitable organic compounds. For the purposes of the present invention, a heteroatom (e.g. nitrogen) can have a hydrogen substituent and/or any permissible substituents of organic compounds described herein which satisfy the valences of the heteroatom. The present disclosure is not intended to be limited in any way by the permissible substituents of organic compounds. Likewise, the term "substituted" or "substituted with" includes the implicit proviso that such substitution is consistent with the atom being substituted and the allowed valence of the substituent, and that the substitution results in a stable compound (e.g., a compound that does not spontaneously undergo transformation (e.g., by rearrangement, cyclization, elimination, etc.)). It is also contemplated that, in certain aspects, individual substituents can be further optionally substituted (i.e., further substituted or unsubstituted), unless explicitly stated to the contrary.
In defining the terms, "R1”、“R2”、“R3"and" R4"used as a general symbol in the present invention denotes various specific substituents. These symbols can be any substituent, are not limited to those disclosed herein, and when they are defined as certain substituents in one instance, they can be defined as some other substituents in other instances.
The term "alkyl" as used herein is a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, half-yl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and the like. The alkyl group may be cyclic or acyclic. The alkyl group may be branched or unbranched. The alkyl group may also be substituted or unsubstituted. For example, the alkyl group may be substituted with one or more groups including, but not limited to, optionally substituted alkyl, cycloalkyl, alkoxy, amino, ether, halogen, hydroxy, nitro, silyl, Sulfo-OXO (Sulfo-OXO), or thiol as described herein. A "lower alkyl" group is an alkyl group containing 1 to 6 (e.g., 1 to 4) carbon atoms.
Throughout the specification, "alkyl" is generally used to refer to both unsubstituted alkyl and substituted alkyl; however, substituted alkyl groups are also specifically mentioned in the present invention by identifying specific substituents on the alkyl group. For example, the term "halogenated alkyl" or "haloalkyl" specifically refers to an alkyl substituted with one or more halogens (e.g., fluorine, chlorine, bromine, or iodine). The term "alkoxyalkyl" specifically refers to an alkyl group substituted with one or more alkoxy groups, as described below. The term "alkylamino" specifically refers to an alkyl group substituted with one or more amino groups, as described below, and the like. When "alkyl" is used in one instance and a specific term such as "alkyl alcohol" is used in another instance, it is not meant to imply that the term "alkyl" does not refer to the specific term such as "alkyl alcohol" or the like at the same time.
This practice is also applicable to the other groups described in the present invention. That is, when a term such as "cycloalkyl" refers to both unsubstituted and substituted cycloalkyl moieties, the substituted moiety may be otherwise specifically identified in the present invention; for example, a specifically substituted cycloalkyl group can be referred to as, for example, "alkylcycloalkyl". Similarly, a substituted alkoxy group may be specifically referred to as, for example, "halogenated alkoxy", and a specific substituted alkenyl group may be, for example, "enol" and the like. Likewise, practice of using general terms such as "cycloalkyl" and specific terms such as "alkylcycloalkyl" is not intended to imply that the general terms do not also encompass the specific terms.
The term "cycloalkyl" as used herein is a non-aromatic carbon-based ring made up of at least three carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclononyl, and the like. The term "heterocycloalkyl" is a class of cycloalkyl groups as defined above and is included within the meaning of the term "cycloalkyl" in which at least one ring carbon atom is substituted with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. The cycloalkyl and heterocycloalkyl groups can be substituted or unsubstituted. The cycloalkyl and heterocycloalkyl groups may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, amino, ether, halogen, hydroxy, nitro, silyl, sulfo-oxo, or thiol groups as described herein.
The term "polyalkylene group" as used herein refers to a group containing two or more CH2Groups and other moieties that are the same are attached. "polyolefin group" can be represented by- (CH)2)a-, wherein "a" is an integer of 2 to 500.
The terms "alkoxy" and "alkoxy group," as used herein, refer to an alkyl or cycloalkyl group bonded through an ether linkage; that is, "alkoxy" may be defined as-OR1Wherein R is1Is alkyl or cycloalkyl as defined above. "alkoxy" also includes polymers of the alkoxy groups just described; that is, the alkoxy group may be a polyether such as-OR1-OR2OR-OR1- (OR2)a-OR3Wherein "a" is an integer of 1 to 200, and R1、R2And R3Each independently is an alkyl group, a cycloalkyl group, or a combination thereof.
The term "alkenyl" as used herein is a hydrocarbon group of 2 to 24 carbon atoms, the structural formula of which contains at least one carbon-carbon double bond. Asymmetric structures such as (R)1R2)C=C(R3R4) Intended to include both the E and Z isomers. This may be presumed in the structural formulae of the present invention, in which an asymmetric olefin is present, or it may be represented by a bond symbolC = C is explicitly indicated. The alkenyl group may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxy, ketone, azido, nitro, silyl, thio-oxo (sulfo-oxo), or thiol as described herein.
The term "cycloalkenyl" as used herein is a non-aromatic carbon-based ring, consisting of at least 3 carbon atoms and containing at least one carbon-carbon double bond, i.e., C = C. Examples of cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, norbornenyl, and the like. The term "heterocycloalkenyl" is a type of cycloalkenyl group as defined above, and is included within the meaning of the term "cycloalkenyl", where at least one carbon atom of the ring is substituted with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. Cycloalkenyl and heterocycloalkenyl groups can be substituted or unsubstituted. The cycloalkenyl and heterocycloalkenyl groups may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxy, ketone, azido, nitro, silyl, thio-oxo (sulfo-oxo), or thiol groups as described herein.
The term "alkynyl" as used herein is a hydrocarbon group having 2 to 24 carbon atoms and having a structural formula containing at least one carbon-carbon triple bond. Alkynyl groups can be unsubstituted or substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxy, ketone, azido, nitro, silyl, thio-oxo (sulfo-oxo), or thiol groups as described herein.
The term "cycloalkynyl" as used herein is a non-aromatic, carbon-based ring containing at least seven carbon atoms and containing at least one carbon-carbon triple bond. Examples of cycloalkynyl include, but are not limited to, cycloheptynyl, cyclooctynyl, cyclononynyl, and the like. The term "heterocycloalkynyl" is a type of cycloalkenyl group as defined above and is included within the meaning of the term "cycloalkynyl" wherein at least one of the carbon atoms of the ring is replaced with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. Cycloalkynyl and heterocycloalkynyl can be substituted or unsubstituted. Cycloalkynyl and heterocycloalkynyl may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxy, ketone, azido, nitro, silyl, thio-oxo (sulfo-oxo), or thiol as described herein.
The term "aryl" as used herein is a group containing any carbon-based aromatic group including, but not limited to, benzene, naphthalene, phenyl, biphenyl, phenoxybenzene, and the like. The term "aryl" also includes "heteroaryl," which is defined as a group containing an aromatic group having at least one heteroatom incorporated into the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Likewise, the term "non-heteroaryl" (which is also included in the term "aryl") defines a group that contains an aromatic group, which does not contain heteroatoms. The aryl group may be substituted or unsubstituted. The aryl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde groups, amino, carboxylic acid groups, ester groups, ether groups, halogens, hydroxyl, ketone groups, azido, nitro, silyl, thio-oxo groups, or mercapto groups as described herein. The term "biaryl" is a specific type of aryl group and is included in the definition of "aryl". Biaryl refers to two aryl groups joined together via a double bridged ring structure, as in naphthalene, or two aryl groups connected via one or more carbon-carbon bonds, as in biphenyl.
The term "aldehyde" as used herein is represented by the formula-C (O) H. Throughout the specification, "C (O)" is a shorthand form of carbonyl (i.e., C = O).
The term "amine" or "amino" as used herein is defined by the formula-NR1R2Is represented by the formula (I) in which R1And R2Can be independently selected from hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl.
The term "alkylamino" as used herein is represented by the formula-NH (-alkyl), wherein alkyl is as described herein. Representative examples include, but are not limited to, methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, (sec-butyl) amino, (tert-butyl) amino, pentylamino, isopentylamino, (tert-pentyl) amino, hexylamino, and the like.
The term "dialkylamino" as used herein is defined by the formula-N (alkyl)2Wherein alkyl is as described herein. Representative examples include, but are not limited to, dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, diisobutylamino, di (sec-butyl) amino, di (tert-butyl) amino, dipentylamino, diisopentylamino, di (tert-pentyl) amino, dihexylamino, N-ethyl-N-methylamino, N-methyl-N-propylamino, N-ethyl-N-propylamino, and the like.
The term "carboxylic acid" as used herein is represented by the formula-C (O) OH.
The term "ester" as used herein is defined by the formula-OC (O) R1OR-C (O) OR1Is represented by the formula (I) in which R1May be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. The term "polyester" as used herein is represented by the formula- (R)1O(O)C-R2-C(O)O)a-or- (R)1O(O)C-R2-OC(O))a-represents wherein R1And R2May independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group described herein and "a" is an integer from 1 to 500. The term "polyester" is used to describe a polyester prepared by reacting a compound having at least two carboxyl groups with a compound having at least two carboxyl groupsA group resulting from a reaction between compounds of at least two hydroxyl groups.
The term "ether" as used herein is defined by the formula R1OR2Is represented by the formula (I) in which R1And R2May independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. The term "polyether" as used herein is of the formula- (R)1O-R2O)a-represents wherein R1And R2May independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group described herein and "a" is an integer from 1 to 500. Examples of polyether groups include polyethylene oxide, polypropylene oxide, and polybutylene oxide.
The term "halogen" as used herein refers to the halogens fluorine, chlorine, bromine, and iodine.
The term "heterocyclyl" as used herein refers to monocyclic and polycyclic non-aromatic ring systems, and "heteroaryl" as used herein refers to monocyclic and polycyclic aromatic ring systems: wherein at least one of the ring members is not carbon. The term includes azetidinyl, dioxanyl, furanyl, imidazolyl, isothiazolyl, isoxazolyl, morpholinyl, oxazolyl including 1, 2, 3-oxadiazolyl, 1, 2, 5-oxadiazolyl and 1, 3, 4-oxadiazolyl, piperazinyl, piperidinyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridinyl, pyrimidinyl, pyrrolyl, pyrrolidinyl, tetrahydrofuryl, tetrahydropyranyl, tetrazinyl including 1, 2, 4, 5-tetrazinyl, tetrazolyl including 1, 2, 3, 4-tetrazolyl and 1, 2, 4, 5-tetrazolyl, thiadiazolyl including 1, 2, 3-thiadiazolyl, 1, 2, 5-thiadiazolyl and 1, 3, 4-thiadiazolyl, thiazolyl, thienyl, thiadiazolyl including 1, 3, 5-triazinyl and 1, triazinyl groups of 2, 4-triazinyl groups, triazolyl groups including 1, 2, 3-triazolyl groups and 1, 3, 4-triazolyl groups, and the like.
The term "hydroxy" as used herein is represented by the formula-OH.
The term "ketone" as used herein is defined by the formula R1C(O)R2Is represented by the formula (I) in which R1And R2Can be independentIs an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.
The term "azido" as used herein is of the formula-N3And (4) showing.
The term "nitro" as used herein is of the formula-NO2And (4) showing.
The term "nitrile" as used herein is represented by the formula-CN.
The term "silyl" as used herein, is defined by the formula-SiR1R2R3Is represented by the formula (I) in which R1、R2And R3And may independently be hydrogen or an alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.
The term "thio-oxo" as used herein is defined by the formula-S (O) R1、-S(O)2R1、 -OS(O)2R1or-OS (O)2OR1Is represented by the formula (I) in which R1May be hydrogen or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. Throughout the specification, "S (O)" is a shorthand form of S = O. The term "sulfonyl", as used herein, refers to a compound of the formula-S (O)2R1A thio-oxo group of the formula, wherein R1Can be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl. The term "sulfone" as used herein is defined by the formula R1S(O)2R2Is represented by the formula (I) in which R1And R2May independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. The term "sulfoxide" as used herein is defined by the formula R1S(O)R2Is represented by the formula (I) in which R1And R2May independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.
The term "mercapto" as used herein is represented by the formula-SH
"R" used in the present invention1”、“R2”、“R3”、“Rn"(wherein n is an integer) may independently have one or more of the groups listed above. For example, if R1Being a straight chain alkyl, then one hydrogen atom of the alkyl group may be optionally substituted with hydroxyl, alkoxy, alkyl, halogen, and the like. Depending on the group selected, the first group may be incorporated within the second group, or alternatively, the first group may be pendent, i.e., attached, to the second group. For example, for the phrase "alkyl group comprising an amino group," the amino group can be incorporated within the backbone of the alkyl group. Alternatively, the amino group may be attached to the backbone of the alkyl group. The nature of the selected group will determine whether the first group is intercalated or attached to the second group.
The compounds of the present invention may contain "optionally substituted" moieties. Generally, the term "substituted" (whether or not the term "optionally" is present above) means that one or more hydrogens of the indicated moiety are replaced with a suitable substituent. Unless otherwise specified, an "optionally substituted" group may have suitable substituents at each substitutable position of the group, and when more than one position may be substituted with more than one substituent selected from a specified group in any given structure, the substituents at each position may be the same or different. The combinations of substituents contemplated by the present invention are preferably those that form stable or chemically feasible compounds. In certain aspects, it is also contemplated that each substituent may be further optionally substituted (i.e., further substituted or unsubstituted), unless clearly indicated to the contrary.
The structure of the compound can be represented by the following formula:
it is understood to be equivalent to the following formula:
where n is typically an integer. Namely, RnIs managedIs solved to represent five separate substituents Ra(1)、Ra(2)、Ra(3)、Ra(4)、Ra (5). By "individual substituents" is meant that each R substituent can be independently defined. For example, if in one instance Ra(m)Is halogen, then in this case Ra(n)Not necessarily halogen.
R is referred to several times in the chemical structures and parts disclosed and described in this specification1、R2、R3、R4、R5、R6And the like. In the specification, R1、R2、R3、R4、R5、R6Etc. are each applicable to the citation of R1、R2、R3、R4、R5、R6Etc., unless otherwise specified.
Optoelectronic devices using organic materials are becoming more and more stringent for a number of reasons. Many of the materials used to make such devices are relatively inexpensive, and therefore organic photovoltaic devices have the potential for cost advantages of inorganic devices. Furthermore, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on flexible substrates. Examples of organic optoelectronic devices include Organic Light Emitting Devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, organic materials may have performance advantages over conventional materials. For example, the wavelength at which the organic light-emitting layer emits light can generally be tuned with appropriate dopants.
The excitons decay from the singlet excited state to the ground state to generate instant luminescence, which is fluorescence. If excitons decay from the triplet excited state to the ground state to generate light emission, it is phosphorescence. Phosphorescent metal complexes (e.g., platinum complexes) have shown their potential to utilize both singlet and triplet excitons, achieving 100% internal quantum efficiency, due to the strong spin-orbit coupling of heavy metal atoms between singlet and triplet excited states, effectively enhancing intersystem crossing (ISC). Accordingly, phosphorescent metal complexes are a good choice of dopants in the emissive layer of Organic Light Emitting Devices (OLEDs) and have gained great attention in both academic and industrial fields. Over the last decade, much effort has been made to bring profitable commercialization of this technology, for example, OLEDs have been used for advanced displays for smart phones, televisions and digital cameras.
However, blue electroluminescent devices remain the most challenging area in the art to date, and stability of blue devices is a big problem. The choice of host material has proven to be very important for the stability of blue devices. However, the triplet excited state (T1) lowest energy of the blue light emitting material is very high, which means that the triplet excited state (T1) lowest energy of the host material of the blue device should be higher. This results in increased difficulty in developing the host material for blue devices.
The metal complexes of the present invention can be tailored or tuned to specific applications where specific emission or absorption characteristics are desired. Can be adjusted by changing the structure of the ligand around the metal center or by changing the structure of the fluorescent luminophore on the ligand. The optical properties of the disclosed metal complexes. For example, metal complexes or electron-withdrawing substituents of ligands having electron-donating substituents may generally exhibit different optical properties in the emission and absorption spectra. The color of the metal complex can be adjusted by modifying the fluorescent emitter and the conjugated group on the ligand.
The emission of the complexes of the invention can be modulated, for example, by changing the ligand or fluorescent emitter structure, for example from ultraviolet to near infrared. Fluorescent emitters are a group of atoms in an organic molecule that can absorb energy to produce a singlet excited state, which rapidly decays to produce instant light emission. In one aspect, the complexes of the invention can provide emission in a large portion of the visible spectrum. In a specific example, the complex of the present invention can emit light in the wavelength band of visible light or near infrared light. On the other hand, the complexes of the invention have improved stability and efficiency relative to conventional emissive complexes. In addition, the complexes of the invention may be used as luminescent labels, for example, for biological applications, anticancer agents, emitters in Organic Light Emitting Diodes (OLEDs), or combinations thereof. In another aspect, the complexes of the present invention can be used in light emitting devices, such as Compact Fluorescent Lamps (CFLs), Light Emitting Diodes (LEDs), incandescent lamps, and combinations thereof.
Disclosed herein are platinum-containing compounds or complex complexes. The terms compound or complex are used interchangeably herein. In addition, the compounds disclosed herein have a neutral charge.
The compounds disclosed herein may exhibit desirable properties and have emission and/or absorption spectra that can be tailored by selection of appropriate ligands. In another aspect, the invention can exclude any one or more of the compounds, structures, or portions thereof specifically recited herein.
The compounds disclosed herein are suitable for use in a wide variety of optical and electro-optical devices, including but not limited to light absorbing devices, such as solar and photosensitive devices, Organic Light Emitting Diodes (OLEDs), light emitting devices or devices capable of compatible light absorption and emission and as labels for biological applications.
As mentioned above, the disclosed compounds are platinum complexes. At the same time, the compounds disclosed herein can be used as host materials for OLED applications, such as full color displays.
The compounds disclosed herein are useful in a variety of applications. As a light-emitting material, the compound is useful for organic light-emitting diodes (OLEDs), light-emitting devices and displays, and other light-emitting devices.
In addition, the compounds of the present invention are used in light emitting devices (e.g., OLEDs) to improve the luminous efficiency and the operation time of the devices, relative to conventional materials.
The compounds of the present invention may be prepared using a variety of methods, including but not limited to those described in the examples provided herein.
The compounds disclosed herein may be delayed fluorescence and/or phosphorescence emitters. In one aspect, the compounds disclosed herein can be delayed fluorescence emitters. In one aspect, the compounds disclosed herein can be phosphorescent emitters. In another aspect, the compounds disclosed herein can be delayed fluorescence emitters and phosphorescence emitters.
The invention relates to an organic luminescent material, which comprises a tetradentate metal platinum (II) complex of benzene ring-pyrazole and derivatives thereof, and the tetradentate metal platinum (II) complex can be used as a phosphorescent luminescent material in an OLED device and is used for improving the efficiency and the service life of the device.
Disclosed in embodiments of the present invention is a platinum (II) complex with a bis-bridged phenyl-pyrazole structural unit, the tetravalent platinum (II) complex having a structure represented by formula (I):
wherein:
linking group X1And X2Exist simultaneously; wherein X1And X2May each be independently selected from CH2、CHD、CD2、CR100R101、SiH2、SiHD、SiD2、SiR102R103、GeH2、Ge HD、GeD2、GeR104R105；
A is selected from O, S, CH2、CHD、CD2、CR200R201、C=O、SiR202R203、GeH2、GeR204R205、NH、ND、NR206、PH、PD、PR207、R208P=O、AsR209、R210As=O、S=O、SO2、Se、Se=O、SeO2、BH、BD、BR211、R212Bi = O, BiH, BiD, or BiR213；
Ra、Rb、Rc、Rd、Re、RfAnd RgEach independently selected from the group consisting of hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxy, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxy, and the likeAminocarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, silyl, substituted silyl, polymeric group, or a combination thereof;
Ra、Rb、Rc、Rd、Re、Rfand RgThe substitution modes of (A) are respectively and independently represented as mono-substitution, di-substitution, tri-substitution, tetra-substitution or non-substitution, and two adjacent substituents can form a condensed ring;
m, n, s, each independently represent an integer of 0 to 4, o, r each independently represent an integer of 0 to 2, p represents an integer of 0 to 3, q represents an integer of 0 to 1;
the R is100、R101、R102、R103、R104、R105、R200、R201、R202、R203、R204、R205、R206、R207、R208、R209、R210、R211、R212、R213Each independently selected from aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxy, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amide, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxy, hydrazino, silyl, substituted silyl, polymeric group, or a combination thereof; wherein two adjacent substituents may form a fused ring.
Optionally, the complex represented by formula (I) further has a structure represented by formula (II), (III), (IV), (V):
wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10And R11Each independently selected from hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxy, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imine, sulfo, carboxyl, hydrazine, silyl, substituted silyl, polymeric group, or a combination thereof; adjacent said R1、R2、R3、R4、R5、R6、R7、R8、R9、R10And R11May be joined to form a fused ring.
Optionally, the R is8、R9、R10And R11Each independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, or octylphenyl; the R is2、R3Each independently selected from hydrogen or methyl.
Optionally, the R isa、Rb、Rc、Rd、Re、RfAnd RgEach independently selected from hydrogen, deuterium, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, butoxy.
Embodiments of the present invention provide that the above-described metal platinum (II) complexes containing a bis-bridged phenyl-pyrazole building block have a neutral charge.
Embodiments of the present invention also provide the use of the above-described platinum (II) metal complexes containing a bis-bridged phenyl-pyrazole building block in electroluminescent devices.
Further, embodiments of the present invention also provide a device comprising a metal platinum (II) complex comprising a bis-bridged phenyl-pyrazole building block as described above.
Optionally, the device is a full color display.
Optionally, the device is a photovoltaic device.
Optionally, the device is a light emitting display device.
Optionally, the device is an organic light emitting diode.
Optionally, the device is a purely phosphorescent or phosphorescent and delayed fluorescence organic light emitting diode.
Alternatively, the metal platinum (II) complex containing a double-bridged phenyl-pyrazole building block is selected to have 100% internal quantum efficiency in a device environment.
Alternatively, there is provided in an embodiment of the invention a device comprising at least one cathode, at least one anode and at least one light emitting layer, at least one of the light emitting layers comprising a metal platinum (II) complex comprising a doubly bridged phenyl-pyrazole building block as described above.
For formula I described in the present invention, its cluster may be defined in the description below.
1) X group
Wherein X1And X2Can be selected from CH2, CHD, CD2, CR100R101, SiH2, SiHD, SiD2, SiR102R103, GeH2, Ge HD, GeD2Or GeR104R105Selecting;
on the other hand, X1Is C (CH)3)2，X2Is C (CH)3)2；
On the other hand, X1Is C (nBu)2，X2Is C (nBu)2；
On the other hand, X1Is CH2，X2Is CH2；
On the other hand, X1Is CR100R101，X2Is CR100R101；
On the other hand, X1Is Si (CH)3)2，X2Is Si (CH)3)2；
On the other hand, X1Is Si: (nBu)2，X2Is Si: (nBu)2；
On the other hand, X1Is SiH2，X2Is SiH2；
On the other hand, X1Is SiPh2，X2Is SiPh2；
On the other hand, X1Is SiR100R101，X2Is SiR100R101。
2) Group A
Wherein A may be O, S, CH2, CHD, CD2, CR100R101, C=O, SiR102R103, GeH2, GeR104R105, NH, ND, NR106, PH, PD, PR107, R108P=O, AsR109, R110As=O, S=O, SO2, Se, Se=O, SeO2, BH, BD, BR111, R112Bi=O, BiH, BiD, or BiR113(ii) a The R is100、R101、R102、R103、R104、R105、R106、R107、R108、R109、R110、R111、R112、R113Each independently represents aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxy, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, heteroaryl, or the like,Haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxy, hydrazino, silyl, substituted silyl, polymeric group, or a combination thereof;
in one aspect, A is O;
in another aspect, A is S;
in another aspect, A is CR100R101；
In another aspect, A is NR106；
In another aspect, A is R108P=O；
In another aspect, A is PR107；
In another aspect, A is BR111；
Further, A is SiR102R103。
3) R group
Wherein R isa Present, on the other hand RaIs absent.
In one aspect, RaIs monosubstituted, on the other hand, RaIs disubstituted; in another aspect, RaIs a trisubstituted radical; further, RaIs tetra-substituted;
while R isaSelected from hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amide, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, substituted silyl, polymeric group, or a combination thereof.
Wherein R isbPresent, on the other hand RbIs absent.
In one aspect, RbIs monosubstituted, on the other hand, RbIs disubstituted; in another aspect, RbIs a trisubstituted radical; further, RbIs tetra-substituted;
while R isbSelected from hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amide, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, substituted silyl, polymeric group, or a combination thereof.
Wherein R iscPresent, on the other hand RcIs absent.
In one aspect, RcIs monosubstituted, on the other hand, RcIs disubstituted; in another aspect, RcIs a trisubstituted radical; further, RcIs tetra-substituted;
while R iscSelected from hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amide, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, substituted silyl, polymeric group, or a combination thereof.
Wherein R isdPresent, on the other hand RdIs absent.
In one aspect, RdIs monosubstituted, on the other hand, RdIs disubstituted;
while R isdFrom hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl,Heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxy, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxy, hydrazino, substituted silyl, polymeric groups, or combinations thereof.
Wherein R isePresent, on the other hand ReIs absent. .
In one aspect, ReIs monosubstituted, on the other hand, ReIs disubstituted;
while R iseSelected from hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amide, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, substituted silyl, polymeric group, or a combination thereof.
Wherein R isfPresent, on the other hand RfIs absent. .
In one aspect, RfIs monosubstituted, on the other hand, RfIs disubstituted;
while R isfFrom hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxy, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthioA group selected from the group consisting of a sulfinyl group, a ureido group, a phosphoramidyl group, an imino group, a sulfo group, a carboxyl group, a hydrazino group, a substituted silyl group, a polymeric group, or a combination thereof.
Wherein R isgPresent, on the other hand RgIs absent. .
In one aspect, RgIs monosubstituted, on the other hand, RgIs disubstituted;
while R isgSelected from hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amide, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, substituted silyl, polymeric group, or a combination thereof.
Wherein R is1Present, on the other hand R1Is absent.
In one aspect, R1Is monosubstituted, on the other hand, R1Is disubstituted;
while R is1Selected from hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amide, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, substituted silyl, polymeric group, or a combination thereof.
Wherein R is2Present, on the other hand R2Is absent.
In one aspect, R2Is monosubstituted, on the other hand, R2Is disubstituted;
while R is2Selected from hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amide, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, substituted silyl, polymeric group, or a combination thereof.
Wherein R is3Present, on the other hand R3Is absent.
In one aspect, R3Is monosubstituted, on the other hand, R3Is disubstituted;
while R is3Selected from hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amide, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, substituted silyl, polymeric group, or a combination thereof.
Wherein R is4Present, on the other hand R4Is absent.
In one aspect, R4Is monosubstituted, on the other hand, R4Is disubstituted;
while R is4From hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxy, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxyAminocarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, substituted silyl, polymeric group, or combinations thereof.
Wherein R is5Present, on the other hand R5Is absent. .
In one aspect, R5Is monosubstituted, on the other hand, R5Is disubstituted;
while R is5Selected from hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amide, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, substituted silyl, polymeric group, or a combination thereof.
Wherein R is6Present, on the other hand R6Is absent.
In one aspect, R6Is monosubstituted, on the other hand, R6Is disubstituted;
while R is6Selected from hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amide, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, substituted silyl, polymeric group, or a combination thereof.
Wherein R is7Exist, on the other handR7Is absent.
In one aspect, R7Is monosubstituted, on the other hand, R7Is disubstituted;
while R is7Selected from hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amide, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, substituted silyl, polymeric group, or a combination thereof.
Wherein R is8Present, on the other hand R8Is absent.
While R is8Selected from hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amide, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, substituted silyl, polymeric group, or a combination thereof.
Wherein R is9Present, on the other hand R9Is absent.
In one aspect, R9Is monosubstituted, on the other hand, R9Is disubstituted;
while R is9From hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxy, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroarylSelected from alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxy, hydrazino, substituted silyl, polymeric group, or combinations thereof.
Wherein R is10Present, on the other hand R10Is absent.
In one aspect, R10Is monosubstituted, on the other hand, R10Is disubstituted;
while R is10Selected from hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amide, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, substituted silyl, polymeric group, or a combination thereof.
Wherein R is11Present, on the other hand R11Is absent. .
In one aspect, R11Is monosubstituted, on the other hand, R11Is disubstituted;
while R is11Selected from hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxyl, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amide, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, substituted silyl, polymeric group, or a combination thereof.
Exemplary Compounds
In one aspect, any of the metal platinum (II) complexes reported for the present invention containing a bis-bridged phenyl-pyrazole building block may comprise one or more of the following structures. In addition, the metal platinum (II) complex may also include other structures or moieties not specifically enumerated herein, and the scope of the present invention is not limited to the structures and moieties enumerated in this patent.
In embodiments of the present invention, cyclometalated platinum (IV) complexes containing tetradentate ligands are provided having neutral charges.
In embodiments of the present invention, there is also provided the use of cyclometalated platinum (IV) complexes comprising tetradentate ligands in electroluminescent devices. Also disclosed in embodiments of the invention are devices, including full color displays, photovoltaic devices, light emitting display devices, organic light emitting diodes, phosphorescent organic light emitting diodes, and the like, comprising one or more of the compounds disclosed herein. In a device environment, a metal platinum (II) complex containing a double-bridged phenyl-pyrazole building block has 100% internal quantum efficiency.
The disclosed compounds are suitable for use in a variety of optical and electro-optical devices, including but not limited to light absorbing devices such as solar and light sensitive devices, Organic Light Emitting Diodes (OLEDs), light emitting devices or devices having both light absorbing and light emitting capabilities, and as labels for biological applications.
The compounds provided by embodiments of the present invention may be used in a light emitting device, such as an OLED, comprising at least one cathode, at least one anode and at least one light emitting layer, at least one of which comprises the above-described phenylpyrazole-based tetradentate cyclometalated platinum (II) complex. Specifically, the light emitting device may include an anode, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode, which are sequentially deposited. The hole transport layer, the luminescent layer and the electron transport layer are all organic layers, and the anode and the cathode are electrically connected.
Synthetic examples
The following examples of compound syntheses, compositions, articles, devices, or methods are intended to provide a general approach to the industry and are not intended to limit the scope of protection of this patent. The data mentioned in the patent (quantity, temperature, etc.) are as accurate as possible, but some errors may also be present. Unless otherwise indicated, the weighing was carried out separately, at ambient temperature, or at a pressure close to ambient.
The following examples provide methods for the preparation of the novel compounds, but the preparation of such compounds is not limited to this method. In this area of expertise, the compounds protected in this patent can be prepared by the methods listed below or by other methods, since they are easy to modify. The following examples are given by way of example only and are not intended to limit the scope of the patent. The temperature, catalyst, concentration, reactants, and course of reaction can all be varied to select different conditions for the preparation of the compound for different reactants.
1H NMR（500 MHz）、13C NMR (126 MHz) spectra were determined on an ANANCE III (500M) model NMR spectrometer; unless otherwise specified, nuclear magnetism is induced by DMSO-d 6 Or CDCl containing 0.1% TMS3 As a solvent, wherein1H NMR spectrum if CDCl3As solvent, TMS (δ = 0.00 ppm) was used as internal standard; by DMSO-d 6 As solventsTMS (δ = 0.00 ppm) or residual DMSO peak (δ = 2.50 ppm) or residual water peak (δ = 3.33 ppm) were used as internal standards.13In the C NMR spectrum, as CDCl3(delta = 77.00 ppm) or DMSO- d 6 (δ = 39.52 ppm) as an internal standard. Measuring on an HPLC-MS Agilent 6210 TOF LC/MS type mass spectrometer; HRMS spectra were determined on an Agilent 6210 TOF LC/MS liquid chromatography-time of flight mass spectrometer.1H NMR spectrum data: s = singlelet, single peak; d = doublet, doublet; t = triplet, triplet; q = quartz, quartet; p = quintet, quintet; m = multiplex, multiplet; br = broad, broad peak.
Synthetic route
The general synthetic method is as follows:
wherein, when the linking group A in the ligand is O, it can be synthesized according to the following route:
or
Wherein, when the linking group a in the ligand is NR, it can be synthesized by the following route:
Wherein, the B-Br, B-OH and B-NR used in the above route can be synthesized according to the following route:
on the other hand, the A-II-OH fragment for A-OH in formula (II) can be synthesized by the following route:
on the other hand, the A-II-OH fragment for A-OH in formula (III) can be synthesized by the following route:
on the other hand, the A-IV-OH fragment for A-OH in formula (IV) can be synthesized by the following route:
on the other hand, the A-V-OH fragment for A-OH in formula (V) can be synthesized by the following route:
in addition, if the pyrazole unit in the above structure is replaced by other heterocyclic ring, the synthesis of the tetravalent platinum complex can also be carried out with reference to the above route.
Example 1: the platinum complex Pt3 can be synthesized by the following route:
synthesis of boronic ester intermediate 2: to a 100mL dry three-necked flask equipped with a magnetic rotor and a condenser tube were added pinacol diboron (5.37 g, 23.3 mmol, 1.1 eq), [1, 1' -bis (diphenylphosphino) ferrocene]Palladium dichloride dichloromethane complex (PdCl)2(dppf).CH2Cl2) (519.4 mg, 0.64 mmol, 0.03 eq), potassium acetate (6.30 g, 63.6 mmol, 3.0 eq). Nitrogen was purged three times, then 1- (3-methoxyphenyl) -4-bromopyrazole 1 (5.37 g, 21.2 mmol, 1.0 eq) dimethyl sulfoxide (40 mL) was added. Then placed in an oil bath at 80 ℃ for 3 days. Cooling to room temperature, adding 80 mL of ethyl acetate for dilution, performing suction filtration, adding 80 mL of water, separating liquid, extracting the water phase with ethyl acetate for three times, combining the organic phases, drying the organic phases with anhydrous sodium sulfate, filtering, distilling under reduced pressure to remove the solvent, separating and purifying the obtained crude product by silica gel column chromatography, and eluting with an eluent (petroleum ether/ethyl acetate = 10: 1-3: 1) to obtain 3.59 g of colorless liquid with the yield of 57%.
1H NMR (500 MHz, DMSO-d 6 ): δ 1.29 (s, 12H), 3.83 (s, 3H), 6.88 (ddd, J = 8.5, 2.5, 1.0 Hz, 1H), 7.37 (t, J = 8.0 Hz, 1H), 7.47-7.50 (m, 2H), 7.85 (s, 1H), 8.78 (s, 1H)。
Synthesis of bromide intermediate 3: to a 100mL dry three-necked flask equipped with a magnetic rotor and a condenser were added diethyl 2, 5-dibromoterephthalate (3.80 g, 10.0 mmol, 1.0 eq), phenylboronic acid (1.21 g, 10.0 mmol, 1.0 eq), tetrakis (triphenylphosphine) palladium (Pd (PPh)3)4）（570 mg, 0.5 mmol, 0.05 eq）, Na2CO3(2.12 g, 20 mmol, 2.0 eq). Nitrogen was purged three times, followed by addition of toluene (60.0 mL), ethanol (20.0 mL). After bubbling nitrogen for 20 minutes, the mixture was placed in a 90 ℃ oil bath and reacted for 36 hours. Cooling to room temperature, distilling under reduced pressure to remove solvent, separating and purifying the crude product by silica gel column chromatography, eluting with eluent (A)Petroleum ether/dichloromethane = 3: 1-1: 1), yielding 256 mg of 3 white solid in 7% yield.
1H NMR (500 MHz, DMSO-d 6 ): δ0.97 (t, J = 7.5 Hz, 3H), 1.32 (t, J = 7.0 Hz, 3H), 4.07 (q, J = 7.5 Hz, 2H), 4.35 (q, J = 7.5 Hz, 2H), 7.32 (dd, J = 8.0, 2.0 Hz, 2H),7.43-7.45 (m, 3H), 7.74 (s, 1H), 8.04 (s, 1H)。
Synthesis of intermediate 4: to a 100mL dry three-necked flask with a magnetic rotor and condenser was added 3 (227.8 mg, 0.74 mmol, 1.0 eq), tetrakis (triphenylphosphine) palladium (Pd (PPh) in that order3)4) (42.8 mg, 0.037 mmol, 0.03 eq), potassium carbonate (K)2CO3) (306.4 mg, 2.22 mmol, 3.0 eq). Nitrogen was purged three times, then 2 (331.6 mg, 1.1 mmol, 1.5 eq), toluene (8.0 mL), ethanol (2.0 mL) and water (2.0 mL) were added. Nitrogen was then bubbled for 25 minutes and the mixture was placed in a 100 ℃ oil bath for 3 days. Cooling to room temperature, distilling under reduced pressure to remove the solvent, adding 10.0 mL of water and 40 mL of ethyl acetate to dilute the separated liquid, extracting the aqueous phase with ethyl acetate three times, combining the organic phases, drying over anhydrous sodium sulfate, filtering, distilling under reduced pressure to remove the solvent, separating and purifying the obtained crude product by silica gel column chromatography, eluting with petroleum ether/ethyl acetate = 20: 1-2: 1) to obtain 197.4 mg of 4 white solid with a yield of 58%.
1H NMR (500 MHz, DMSO-d 6 ): δ0.96 (t, J = 7.5 Hz, 3H), 1.20 (t, J = 7.0 Hz, 3H), 3.85 (s, 3H), 4.08 (q, J = 8.0 Hz, 2H), 4.28 (q, J = 8.0 Hz, 2H), 6.92 (ddd, J = 8.0, 2.5, 0.5 Hz, 1H), 7.25-7.37 (m, 2H), 7.41-7.50 (m, 6H), 7.73 (s, 1H), 7.87 (d, J = 0.5 Hz, 1H) , 7.92 (s, 1H), 8.88 (d, J = 0.5 Hz, 1H)。
Synthesis of intermediate 5: 4 (197.0 mg, 0.42 mmol, 1.0 eq) was added to the dry reaction tube with a magnetic rotor. The nitrogen was purged three times, then 5 mL of methylmagnesium bromide (MeMgBr) (600.0 mg (1M), 5.03 mmol, 12.0 eq) in tetrahydrofuran was added and the mixture was reacted in an oil bath at 40 ℃ for 3 days. Cooling to room temperature, distilling under reduced pressure to remove the solvent, adding ethyl acetate for dilution, then adding an ammonium chloride aqueous solution for washing, separating, extracting the aqueous phase with ethyl acetate for three times, combining the organic phases, drying with anhydrous sodium sulfate, filtering, distilling under reduced pressure to remove the solvent, separating and purifying the obtained crude product by silica gel column chromatography, eluting with a eluent (petroleum ether/ethyl acetate = 5: 1-3: 1) to obtain 83.5 mg of 5-white solid with the yield of 53%.
1H NMR (500 MHz, DMSO-d 6 ): δ1.22 (s, 6H), 1.35 (s, 6H), 3.85 (s, 3H), 4.88 (s, 1H), 4.97 (s, 1H), 6.88-6.91 (m, 1H), 7.28-7.30 (m, 2H), 7.33-7.48 (m, 7H), 7.59 (s, 1H), 7.81 (s, 1H), 8.60 (s, 1H)。
Synthesis of intermediate 6: 5 (83.5 mg, 0.22 mmol), concentrated hydrobromic acid (HBr) (40.0 mL, 48% strength) and acetic acid (5.0 mL) were charged to a single neck flask with a magnetic stirrer and condenser and refluxed at 120 ℃ for 3 days. Then, the mixture was allowed to cool naturally to room temperature, the organic solvent was distilled off under reduced pressure, and the resulting mixture was neutralized with a sodium hydrogencarbonate solution until no bubbles were generated. The ethyl acetate extraction, anhydrous sodium sulfate drying, filtration, filtrate vacuum concentration target product white solid 39.3 mg, yield 46%, directly used in the next reaction.
Synthesis of ligand 3: 6210.0 mg, 0.53mmol, 1.0 eq), 2-bromo-9- (4-tert-butylpyridin-2-yl) -9 were added sequentially to a dry reaction tube with a magnetic rotorHCarbazole (2-bromo-9- (4- (tert-butyl) pyridine-2-yl) -9H-carbozole, (Br-Cab-Py-tBu) (242.7 mg, 0.64 mmol, 1.2 eq), cuprous iodide (6.5 mg, 0.053 mmol, 0.10 eq), 2-picolinic acid (13.0 mg, 0.11 mmol, 0.20 eq), potassium phosphate (236.3 mg, 1.11 mmol, 2.1 eq). Nitrogen was purged three times, and then solvent dimethylsulfoxide (6.0 mL) was added. The reaction mixture was then stirred at 120 ℃ for 3 days. Cooling to room temperature, diluting with water and dichloromethane, separating, extracting the aqueous phase with dichloromethane for 3 times, combining the organic phases, and drying over anhydrous sodium sulfate.Filtration was carried out, the solvent was removed from the filtrate by distillation under the reduced pressure, and the obtained crude product was separated and purified by silica gel column chromatography and eluted with petroleum ether/ethyl acetate = 5:1 to obtain 237.2 mg of a white solid in a yield of 65%.
1H NMR (500 MHz, DMSO-d 6): δ1.30 (s, 9H), 1.32 (s, 6H), 1.44 (s, 6H), 7.19 (dd, J = 8.5, 1.5 Hz, 1H), 7.22 (t, J = 2.0 Hz, 1H), 7.24-7.27 (m, 2H), 7.32 (td, J = 7.5, 1.0 Hz, 1H), 7.33-7.36 (m, 1H), 7.42-7.48 (m, 4H), 7.51 (d, J = 7.0 Hz, 1H), 7.607 (s, 1H), 7.613 (t, J = 8.5 Hz, 1H), 7.69 (d, J = 1.0 Hz, 1H), 7.75-7.79 (m, 2H), 7.84 (s, 1H), 7.85 (s, 1H), 8.25 (d, J = 8.5 Hz, 1H), 8.32 (d, J = 8.5 Hz, 1H), 8.58 (d, J = 5.0 Hz, 1H)。
Synthesis of platinum (II) metal compound Pt 3: to a 100mL three-necked flask equipped with a magnetic rotor and condenser was added ligand 3 (227.2 mg, 0.33 mmol, 1.0 eq) and potassium tetrachloroplatinate (K)2PtCl4) (150.23 mg, 0.36 mmol, 1.1 eq.) and n-butylammonium bromide (nBu4NBr) (10.6 mg, 0.03 mmol, 0.1 eq). Nitrogen was purged three times, and then solvent acetic acid (30 mL) was added. The reaction mixture was stirred at room temperature for 10 hours and then at 110 ℃ for 3 days. The reaction mixture was cooled to room temperature, the solvent was removed by distillation under the reduced pressure, and the resulting crude product was purified by silica gel column chromatography with an eluent (petroleum ether/dichloromethane = 2:1-1: 1) to give 159.5 mg of a yellow solid in 55% yield. The thermal decomposition temperature of Pt3 was 342.80 ℃.
1H NMR (500 MHz, DMSO-d 6): δ1.41 (s, 9H), 1.50 (s, 6H), 1.90 (s, 6H), 7.03 (d, J = 8.0 Hz, 1H), 7.22 (d, J = 8.0 Hz, 1H), 7.22 (td, J = 7.5, 1.0 Hz, 1H), 7.36-7.43 (m, 3H), 7.50-7.53 (m, 4H), 7.87-7.91 (m, 3H), 8.13 (s, 1H), 8.14 (d, J = 7.0 Hz, 1H), 8.17 (d, J = 7.5 Hz, 1H), 8.20 (d, J = 2.0 Hz, 1H), 8.47 (s, 1H), 9.24 (d, J = 6.0 Hz, 1H)。
The platinum complex Pt3 was also confirmed by X-ray single crystal diffraction analysis. The room temperature and low temperature (77K) emission spectra of the platinum complex Pt3 are shown in figure 1.
FIG. 1 shows the room-temperature emission spectrum of Pt3 as a platinum complex in methylene chloride solution and the 77K emission spectrum in 2-methyltetrahydrofuran solution. As can be seen from the comparison of the Pt3 complex at room temperature and 77K, the T of 77K is1→S0The radiation peak of (1) is at about 474nm, the triplet level is about 2.62eV, and the whole molecule is a green phosphorescent material; and an emission peak at about 476nm of the room temperature spectrum is T1→S0Is phosphorescence; and a deep blue light emission peak at about 448nm of S1→S0The radiation peak of (1) is delayed fluorescence, and the whole molecule is a sky blue phosphorescent material. The resultant molecules with low triplet state energy level can realize blue light emission.
FIG. 6 is a normalized luminescence spectrum of the platinum complex Pt3 and a control. The reduction in triplet state of the platinum complex Pt3 was evident compared to the luminescence spectrum of the control. The spectrum of the wave band 500-550nm is a low triplet part of the platinum complex Pt3 and a contrast, the ratio of the spectral intensity of the wave band of the complex Pt3 to the main peak intensity is obviously higher than the intensity ratio of the wave band of the contrast, which indicates that more low triplet components exist in the luminescence spectrum of the complex Pt3, and the reduction of the triplet is obvious.
Fig. 2 to 5 are energy level profiles of Pt3, Pt31, Pt32 and Pt33 respectively, and it can be seen that there is no significant difference in the energy level profiles of several platinum complexes, indicating that these complexes perform very similarly.
While the foregoing is directed to embodiments of the present invention, it will be understood by those skilled in the art that various changes may be made without departing from the spirit and scope of the invention.
Claims (6)
1. A tetradentate ring metal platinum (II) complex containing a bis-bridged phenyl-pyrazole structural unit, wherein the tetradentate ring metal platinum (II) complex has a structure represented by the general formula (I):
wherein:
linking group X1And X2Exist simultaneously; wherein X1And X2Each independently is CH2, CHD, CD2, CR100R101；
A is O;
Ra、Rb、Rc、Rd、Re、Rfand RgEach independently hydrogen, deuterium, cycloalkyl, alkyl, or a combination thereof;
m, n, s, each independently represent an integer of 0 to 4, o, r each independently represent an integer of 0 to 2, p represents an integer of 0 to 3, q represents an integer of 0 to 1;
the R is100、R101Each independently is aryl, cycloalkyl, alkyl, or a combination thereof.
2. The tetradentate ring metal platinum (II) complex with a bis-bridged phenyl-pyrazole building block according to claim 1, characterized in that the platinum complex has the structure shown in general formula (II), (III), (IV), (V):
wherein A is O; r1、R2、R3、R4、R5、R6、R7、R8、R9、R10And R11Each independently hydrogen, deuterium, cycloalkyl, alkyl, or a combination thereof.
3. Use of the tetradentate cyclometalated platinum (II) complexes containing doubly bridged phenyl-pyrazole building blocks as claimed in any of claims 1 to 2 in electroluminescent devices.
4. A device comprising a tetradentate cyclometallated platinum (II) complex containing a bis-bridged phenyl-pyrazole building block according to any of claims 1 to 2.
5. The device of claim 4, wherein the device is a photovoltaic device, a light emitting display device.
6. The device according to claim 4, comprising at least one cathode, at least one anode and at least one light emitting layer, at least one of said light emitting layers comprising a tetradentate cyclometalated platinum (II) complex comprising a bis-bridged phenyl-pyrazole building block according to any one of claims 1 to 2.
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