CN114702528A - N ^ N ^ C ^ N tetradentate platinum (II) complex containing carbazole derivatives and application thereof - Google Patents
N ^ N ^ C ^ N tetradentate platinum (II) complex containing carbazole derivatives and application thereof Download PDFInfo
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- CN114702528A CN114702528A CN202210454594.8A CN202210454594A CN114702528A CN 114702528 A CN114702528 A CN 114702528A CN 202210454594 A CN202210454594 A CN 202210454594A CN 114702528 A CN114702528 A CN 114702528A
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- platinum
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- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 title abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 38
- -1 cyano, amino Chemical group 0.000 claims description 37
- 125000003118 aryl group Chemical group 0.000 claims description 26
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 20
- 125000003545 alkoxy group Chemical group 0.000 claims description 17
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 16
- 125000001072 heteroaryl group Chemical group 0.000 claims description 16
- 229910052736 halogen Inorganic materials 0.000 claims description 14
- 150000002367 halogens Chemical class 0.000 claims description 14
- 125000003342 alkenyl group Chemical group 0.000 claims description 12
- 125000000304 alkynyl group Chemical group 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 3
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 2
- 125000004466 alkoxycarbonylamino group Chemical group 0.000 claims description 2
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 125000005162 aryl oxy carbonyl amino group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 2
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 claims description 2
- 229910052805 deuterium Inorganic materials 0.000 claims description 2
- 125000004986 diarylamino group Chemical group 0.000 claims description 2
- 150000002527 isonitriles Chemical class 0.000 claims description 2
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 125000001841 imino group Chemical group [H]N=* 0.000 claims 1
- 150000003536 tetrazoles Chemical class 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 50
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 36
- 150000001875 compounds Chemical class 0.000 description 28
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- 239000010410 layer Substances 0.000 description 26
- 125000001424 substituent group Chemical group 0.000 description 26
- 229910052757 nitrogen Inorganic materials 0.000 description 25
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 22
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 21
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 20
- 238000000034 method Methods 0.000 description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 13
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000012043 crude product Substances 0.000 description 9
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 239000003446 ligand Substances 0.000 description 8
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000003775 Density Functional Theory Methods 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 125000005842 heteroatom Chemical group 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 150000001716 carbazoles Chemical class 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 125000003396 thiol group Chemical class [H]S* 0.000 description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 6
- PAQYNMHBAJPURI-UHFFFAOYSA-N 9H-carbazole pyridine Chemical group C1=CC=NC=C1.C1=CC=C2C3=CC=CC=C3NC2=C1 PAQYNMHBAJPURI-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003480 eluent Substances 0.000 description 5
- 238000000295 emission spectrum Methods 0.000 description 5
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N DMSO-d6 Substances [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 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
- 238000004770 highest occupied molecular orbital Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 125000002837 carbocyclic group Chemical group 0.000 description 3
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 125000004366 heterocycloalkenyl group Chemical group 0.000 description 3
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 3
- 230000005525 hole transport Effects 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 125000000547 substituted alkyl group Chemical group 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 3
- 235000019798 tripotassium phosphate Nutrition 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- MYKQKWIPLZEVOW-UHFFFAOYSA-N 11h-benzo[a]carbazole Chemical compound C1=CC2=CC=CC=C2C2=C1C1=CC=CC=C1N2 MYKQKWIPLZEVOW-UHFFFAOYSA-N 0.000 description 2
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 description 2
- OYFFSPILVQLRQA-UHFFFAOYSA-N 3,6-ditert-butyl-9h-carbazole Chemical group C1=C(C(C)(C)C)C=C2C3=CC(C(C)(C)C)=CC=C3NC2=C1 OYFFSPILVQLRQA-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-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
- 125000004429 atom Chemical group 0.000 description 2
- 238000005284 basis set Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000005347 biaryls Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 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
- 125000002971 oxazolyl group Chemical group 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 229920000728 polyester Polymers 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
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 125000003373 pyrazinyl group Chemical group 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000005346 substituted cycloalkyl group Chemical group 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000001113 thiadiazolyl group Chemical group 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- 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
- FEYDZHNIIMENOB-UHFFFAOYSA-N 2,6-dibromopyridine Chemical compound BrC1=CC=CC(Br)=N1 FEYDZHNIIMENOB-UHFFFAOYSA-N 0.000 description 1
- UWDBMZOJTCSRGW-UHFFFAOYSA-N 3-pyridin-2-ylphenol Chemical compound OC1=CC=CC(C=2N=CC=CC=2)=C1 UWDBMZOJTCSRGW-UHFFFAOYSA-N 0.000 description 1
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 1
- 238000004057 DFT-B3LYP calculation Methods 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 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
- 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
- 125000002393 azetidinyl group Chemical group 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001162 cycloheptenyl group Chemical group C1(=CCCCCC1)* 0.000 description 1
- 125000003678 cyclohexadienyl group Chemical group C1(=CC=CCC1)* 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000006547 cyclononyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000298 cyclopropenyl group Chemical group [H]C1=C([H])C1([H])* 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 description 1
- 125000000532 dioxanyl group Chemical group 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
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Images
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H10K85/30—Coordination compounds
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Abstract
The invention provides an N ^ N ^ C ^ N tetradentate platinum (II) complex containing carbazole derivatives and application thereof.
Description
Technical Field
The invention relates to a novel carbazole derivative-containing N ^ N ^ C ^ N tetradentate platinum (II) complex phosphorescent material, in particular to a phosphorescent doped material used in an OLED (organic light emitting diode) luminescent device.
Background
Organic Light-Emitting diodes (OLEDs) are a new generation of full-color display and illumination technologies. The OLED is an autonomous light-emitting device, does not need a backlight source and saves energy; the driving voltage is low, the response speed is high, the resolution and the contrast are high, the visual angle is wide, and the using temperature range is wide; cheap glass can be used as a substrate, and if flexible plastic is used as the substrate, a flexible display device can be prepared; in addition, the method also has the advantages of low cost, simple production process, large-area production and the like. Therefore, the OLED has wide and huge application prospect in the aspects of high-end electronic products and aerospace; and there is also a large potential market in the area of planar solid state lighting. The design and development of light emitting materials is therefore central to the OLED field.
Early fluorescent OLED luminescent materials can only emit light by using singlet state generally, triplet excitons generated in devices can not be effectively used and return to the ground state in a non-radiative mode, and the popularization and the use of OLEDs are limited. Professor Forrest and professor Thompson in the United states of 1998 realize the phosphorescence electroluminescence phenomenon of the metal platinum organic complex molecules at room temperature; in the same year, Mashima and Chinesian in China also reported that phosphorescence electroluminescence of metal osmium complexes, which are second-generation phosphorescent materials. The ring metal complex phosphorescent material can break the triplet transition forbidden resistance due to the spin orbit coupling effect (SOC) of the heavy metal, fully utilizes all singlet and triplet excitons generated by the electric excitation, enables the maximum theoretical quantum efficiency to reach 100 percent, and promotes the commercialization process of the OLED to a great extent.
In recent years, phosphorescent OLED materials based on platinum (II) have been gradually developed and have achieved good research results. Unlike the conventional iridium (III) which forms octahedral coordination structures, platinum (II) is tetradentate, and thus complexes of planar structures are generally formed, and the ligands thereof are mainly bidentate, tridentate and tetradentate. Compared with bidentate or tridentate ligands, tetradentate ligands have the following advantages: (1) the ligand can be reacted in one step to synthesize the platinum (II) complex, which is easy to prepare and purify the platinum (II) complex; (2) no isomer is generated in the process of synthesizing the platinum (II) complex, and the structure is specific; (3) chelating and coordinating, and the structure is stable; (4) has relatively good phosphorescence emission efficiency.
Carbazole is a nitrogen-containing heterocyclic compound rich in electrons, has a large pi-conjugated rigid plane structure, and is introduced into a cyclometalated tetradentate platinum phosphorescent molecule, so that the radiation rate is favorably improved, and the luminous efficiency is further improved. The carbazole derivative has the characteristics of special rigid condensed ring structure, good hole transmission performance and the like, and is widely applied to the fields of organic photoelectric materials, dyes, medicines and the like. Meanwhile, the carbazole group is also an electron-rich group, and when the carbazole group is introduced into the structure of the platinum (II) complex, the electron-rich characteristic of the carbazole group endows the platinum (II) complex with good hole injection capability and electron transmission capability, so that electrons and holes are compounded and balanced. Meanwhile, the film forming property of the platinum (II) complex can be improved by introducing the carbazole group, and the rigid carbazole group is beneficial to reducing the self-quenching of the phosphorescent material, so that the efficiency of the device is improved.
Disclosure of Invention
In the invention, a novel Pt (II) complex with an N ^ N ^ C ^ N coordination structure based on a 3, 6-di-tert-butyl carbazole skeleton is designed. Carbazole is a nitrogen-containing heterocyclic compound containing rich electrons and has a large pi-conjugated rigid planar structure, and the unique structure enables the derivative to show a plurality of excellent photoelectric properties.
Embodiments of the present invention provide a metal platinum (II) complex containing a structural unit of a 3, 6-di-tert-butylcarbazolopyridine derivative, the complex having a structure represented by general formula (I) or (II):
wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11And R12Each independently represents hydrogen, deuterium, alkyl, haloalkyl, cycloalkyl, alkoxy, aryl, heteroaryl, aryloxy, halogen, cycloalkenyl, heterocyclyl, alkenyl, alkynyl, hydroxy, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, substituted aryl,carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxy, hydrazino, silyl, substituted silyl, and two or more adjacent R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11And R12And may be selectively linked to form a fused ring.
Further, structures having one of the following, including but not limited to the following:
in the invention, the metal platinum (II) complex containing the carbazole structural unit is used as a luminescent material and can be used for electroluminescent devices. Furthermore, the organic light emitting diode can be used for full-color displays, light emitting display devices or organic light emitting diodes. The device comprises an anode, a cathode and an intermediate organic layer, wherein the intermediate organic layer at least comprises a light-emitting layer, and the light-emitting layer contains the tetradentate platinum (II) complex with the structure as shown in the specification as a phosphorescent doping material.
The invention has the beneficial effects that:
the carbazole structure has a relatively large conjugated plane and a relatively large range of pi electrons, and thus has a relatively strong rigid structure. Meanwhile, the structure of carbazole is easy to modify, and tert-butyl is introduced into cyclometalated tetradentate platinum phosphorescent molecules, so that intermolecular accumulation can be prevented, self-quenching of phosphorescent materials can be reduced, and meanwhile, the solubility of the complex is increased, and synthesis is facilitated. The invention adjusts the photophysical properties of the metal platinum complex by changing the ligand structure around the metal center and regulating and controlling the substituent structure on the ligand. Has wide application prospect in OLED display, illumination and other fields.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without inventive efforts, wherein:
FIG. 1 is a room temperature emission spectrum of a platinum (II) complex Pt1 in a dichloromethane solution according to an embodiment;
FIG. 2 is a room temperature emission spectrum of Pt2 as a platinum (II) complex in a dichloromethane solution according to an embodiment;
FIG. 3 is a room temperature emission spectrum of Pt3 as a platinum (II) complex in a dichloromethane solution according to an embodiment;
FIG. 4 is a comparison of HOMO and LUMO orbital distributions and energy levels of Pt1, Pt2, and Pt3 calculated by Density Functional Theory (DFT);
FIG. 5 is a comparison of HOMO and LUMO orbital distributions and energy levels of Pt4, Pt5, and Pt6 calculated by Density Functional Theory (DFT);
it is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive.
Detailed Description
The present invention will be described in detail below. The following description of the constituent elements may be based on a representative embodiment or specific example of the present invention, but the present invention is not limited to such an embodiment or specific example.
The present 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 specific synthetic methods or specific reagents, as such may vary, unless otherwise specified. 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 now described.
As used in the specification and the appended claims, the singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a component" includes mixtures of two or more components.
The term "optional" or "optionally" as used herein means 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 the components that can be used to prepare 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 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. 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, each combination and permutation of the compound and the modifications that can be made are specifically contemplated unless specifically indicated to the contrary. Thus, if a class of molecules A, B and C is disclosed as well as a class of molecules D, E and F, and examples of combination molecules A-D are disclosed, then even if each is not individually recited, it is contemplated that each is individually and collectively disclosed, A-E, A-F, B-D, B-E, B-F, C-D, C-E and C-F. Likewise, any subset or combination of these is also disclosed. For example, subgroups of A-E, B-F and C-E are also disclosed. This concept applies to all aspects of the invention including, but not limited to, steps in 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 term "substituted" or similar terms as used herein includes all permissible substituents of organic compounds. Broadly, the permissible substituents include cyclic and acyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic substituents of organic compounds. For example, exemplary substituents include the following. 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 of the invention which satisfy the valences of the heteroatom. The present invention 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.)). In certain aspects, individual substituents can be further optionally substituted (i.e., further substituted or unsubstituted), unless specifically indicated to the contrary.
In defining the various terms, "R1", "R2", "R3" and "R4" are used herein as generic symbols to denote various specific substituents. These symbols can be any substituent, not limited to those disclosed herein, which when defined as certain substituents in one instance, can also be defined as some other substituents in another instance.
The term "alkyl" as used herein is a branched or unbranched saturated hydrocarbon group of 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, octyl, 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, and 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" generally refers 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, "haloalkoxy", and a specific substituted alkenyl group may be, for example, "enol", and the like. Likewise, the use of a generic term such as "cycloalkyl" and a specific term such as "alkylcycloalkyl" does not mean that the generic term does not also encompass the specific term.
The term "cycloalkyl" as used herein is a non-aromatic carbon-based ring of 3 to 30 carbon atoms consisting 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, and thiol as described herein.
The terms "alkoxy" and "alkoxy group" as used herein refer to an alkyl or cycloalkyl group of 1 to 30 carbon atoms bonded through an ether linkage; that is, "alkoxy" may be defined as — OR1, where R1 is alkyl OR cycloalkyl as defined above. "alkoxy" also includes the alkoxy polymers just described; that is, the alkoxy group can be a polyether, such as-OR 1-OR2 OR-OR 1- (OR2) a-OR3, where "a" is an integer from 1 to 500, and R1, R2, and R3 are each independently alkyl, cycloalkyl, OR a combination thereof.
The term "alkenyl" as used herein is a hydrocarbon group of 2 to 30 carbon atoms, the structural formula of which contains at least one carbon-carbon double bond. Asymmetric structures such as (R1R2) C ═ C (R3R4) include the E and Z isomers. This can be presumed in the structural formula of the present invention in which an asymmetric olefin is present, or it can be explicitly represented by the bond symbol C ═ C. 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, sulfo-oxo, or thiol as described herein.
The term "cycloalkenyl" as used herein is a non-aromatic carbon-based ring of 3 to 30 carbon atoms, 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, cycloheptenyl, 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, sulfo-oxo, or thiol as described herein.
The term "alkynyl" as used herein is a hydrocarbon group having from 2 to 30 carbon atoms and 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, or mercapto as described herein.
The term "aryl" as used herein refers to groups containing 60 carbon atoms and up of any carbon-based aromatic group, including but not limited to benzene, naphthalene, phenyl, biphenyl, phenoxybenzene, and the like. The term "heteroaryl" is defined as an aromatic-containing group that contains at least one heteroatom in the ring. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, or phosphorus. Likewise, the term "non-heteroaryl" (which is also included in the term "aryl") defines an aromatic-containing group that does not contain heteroatoms. The aryl group may be substituted or unsubstituted. The aryl 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, sulfo-oxo, or thiol 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 fused 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 represented by the formula — NR1R2, wherein R1 and R2 may 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-butylamino, tert-butylamino, pentylamino, isopentylamino, tert-pentylamino, hexylamino, and the like.
The term "dialkylamino" as used herein is represented by the formula-N (-alkyl) 2, wherein alkyl is as described herein. Representative examples include, but are not limited to, dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, diisobutylamino, di-sec-butylamino, di-tert-butylamino, dipentylamino, diisopentylamino, di-tert-pentylamino, dihexylamino, N-ethyl-N-methylamino, N-methyl-N-propylamino, N-ethyl-N-propylamino, and the like.
The term "carboxy" as used herein is represented by the formula-C (O) OH.
The term "ester" as used herein is represented by the formula-OC (O) R1 OR-C (O) OR1, wherein R1 may 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- (R1O (O) C-R2-C (O) a-or- (R1O (O) C-R2-OC (O)) a-, wherein R1 and R2 may independently be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl as described herein and "a" is an integer from 1 to 500. The term "polyester" is used to describe a group produced by the reaction between a compound having at least two carboxyl groups and a compound having at least two hydroxyl groups.
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 of no more than 60 carbon atoms: wherein at least one of the ring members is not carbon. The term includes azetidinyl, dioxanyl, furanyl, imidazolyl, isothiazolyl, isoxazolyl, morpholinyl, oxazolyl (including oxazolyl of 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 "nitro" as used herein is represented by the formula — NO 2.
The term "nitrile" as used herein is represented by the formula — CN.
The term "silyl" as used herein is represented by the formula — SiR1R2R3, wherein R1, R2, and R3 can be independently hydrogen or an alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.
The term "mercapto" as used herein is represented by the formula-SH.
As used herein, "R1", "R2", "R3", "Rn" (where n is an integer) may independently have one or more of the groups listed above. For example, if R1 is a straight chain alkyl group, 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 the first group may be pendant (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. In general, the term "substituted" (whether or not the term "optionally" is used above) means that one or more hydrogens of the designated moiety are replaced with a suitable substituent. Unless otherwise specified, an "optionally substituted" group may have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure may be substituted with more than one substituent selected from a specified group, the substituents may be the same or different at each position. The combinations of substituents contemplated by the present invention are preferably combinations that form stable or chemically feasible compounds. It is also contemplated that, in certain aspects, each substituent may be further optionally substituted (i.e., further substituted or unsubstituted), unless specifically 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. That is, Rn is understood to represent five separate substituents Rn (a), Rn (b), Rn (c), Rn (d), Rn (e). By "individual substituents" is meant that each R substituent can be independently defined. For example, if rn (a) is halogen in one instance, rn (b) need not be halogen in this instance.
R1, R2, R3, R4, R5, R6, and the like are referred to several times in the chemical structures and units disclosed and described herein. Any description of R1, R2, R3, R4, R5, R6, etc. in the specification applies to any structure or unit referenced to R1, R2, R3, R4, R5, R6, etc., respectively, unless otherwise specified.
R1, R2, R3, R4, R5, R6, and the like are referred to several times in the chemical structures and units disclosed and described herein. Any description of R1, R2, R3, R4, R5, R6, etc. in the specification applies to any structure or unit referenced to R1, R2, R3, R4, R5, R6, etc., respectively, unless otherwise specified.
The term "fused ring" as used herein means that two adjacent substituents may be fused to form a six-membered aromatic ring, a heteroaromatic ring, such as a benzene ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a m-diazacyclo ring, etc., as well as a saturated six-or seven-membered carbocyclic or carbocyclic ring, etc.
The following examples, which are merely exemplary of the present disclosure and are not intended to limit the scope thereof, provide those of ordinary skill in the art with a description of how to make and evaluate the compounds described herein and their OLED devices. Although efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), some errors and deviations should be accounted for. Unless otherwise specified, temperature is in units of ° c or at ambient temperature, and pressure is at or near atmospheric pressure.
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(500MHz)、13C NMR (126MHz) spectra were determined on an ANANCE III (500M) model NMR spectrometer; nuclear magnetism, unless otherwise specifiedWith DMSO-d6Or CDCl containing 0.1% TMS3As a solvent, wherein1H NMR spectrum if CDCl3As a solvent, TMS (δ 0.00ppm) was used as an internal standard; with DMSO-d6As a solvent, TMS (δ 0.00ppm), or residual DMSO peak (δ 2.50ppm) or residual water peak (δ 3.33ppm) was used as an internal standard.13In the C NMR spectrum, as CDCl3(delta 77.00ppm) or DMSO-d6(δ 39.52ppm) as an internal standard. Measuring on an HPLC-MS Agilent 6210TOF LC/MS type mass spectrometer; HRMS spectra were determined on an Agilent 6210TOF LC/MS liquid chromatography-time of flight mass spectrometer.1H NMR spectrum data: s is singlelet, d is doublet, t is triplet, q is quartet, p is quintet, m is multiplex, br is broad.
The synthetic route is as follows: the carbazole derivative S1 is subjected to bromination reaction to obtain a substrate S2, S2 is subjected to reaction with pinacol ester diboron to obtain a corresponding pinacol ester derivative S3, S3 and pyridine derivative S4 are subjected to Suzuki reaction to obtain L, and the L is subjected to reaction with potassium chloroplatinate to obtain a target product P.
The general formula of the synthetic route is as follows:
example 1: the platinum complex Pt1 can be synthesized by the following route:
synthesis of Compound 2: to a 250mL dry three-necked flask with a magnetic rotor and condenser was added 3, 6-di-tert-butylcarbazole 1(3.00g, 10.74mmol, 1.0 equiv.), then the nitrogen was purged three times and a solution of N-bromosuccinimide (1.90g, 10.74mmol, 1.0 equiv.) in dichloromethane (100mL) was added under nitrogen protection. The mixture was stirred at room temperature for 24 hours and showed a thin layer colorAnd (5) monitoring the spectrum until the reaction of the raw materials is finished. Then, distilling under reduced pressure to remove the solvent, separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a lotion: petroleum ether/dichloromethane ═ 30:1 to 10:1, and compound 2 was obtained as a white foamy solid (3.5 g, 91% yield).1H NMR(500MHz,DMSO):δ1.39(s,9H),1.39(s,9H),7.45(dd,J＝8.5,1.0Hz,1H),7.49(dd,J＝8.5,1.5Hz,1H),7.57(d,J＝2.0Hz,1H),8.17(d,J＝2.0Hz,1H),8.19(d,J＝1.5Hz,1H),11.10(s,1H)。
Synthesis of Compound 3: to a 100mL dry three-necked flask equipped with a magnetic rotor and condenser was added compound 2(3.50g, 9.77mmol, 1.0 equiv.), bisphenonol boronate (3.72g, 14.65mmol, 1.5 equiv.), potassium acetate (2.40g, 24.41mmol, 2.5 equiv.), palladium tetrakistriphenylphosphine dichloride (143mg, 0.20mmol, 0.02 equiv.), then nitrogen was purged three times and dioxane (50mL) was added under nitrogen blanket. The mixture was stirred in an oil bath at 90 ℃ for 12 hours and monitored by thin layer chromatography until the starting material was reacted. Then, distilling under reduced pressure to remove the solvent, separating and purifying the obtained crude product by using a silica gel chromatographic column, and eluting a eluent: petroleum ether/dichloromethane ═ 100:1 gave compound 3 as a white solid, 3.56g, yield 90%.1H NMR(400MHz,CDCl3):δ1.44(s,12H),1.46(s,9H),1.48(s,9H),7.40(d,J＝9.0Hz,1H),7.47(dd,J＝8.4,2.0Hz,1H),7.89(s,J＝2.0Hz 1H),8.08(d,J＝2.0Hz 1H),8.22(d,J＝1.5Hz 1H),8.97(s,1H)。
Synthesis of Compound 4: to a 100mL dry three-necked flask with a magnetic rotor and condenser was added intermediate 3(3.10g, 7.65mmol, 1.0 equiv.), 2, 6-dibromopyridine (2.00g, 8.41mmol, 1.1 equiv.), anhydrous potassium carbonate (2.1g, 15.30mmol, 2.0 equiv.), palladium tetratriphenylphosphine (177mg, 0.15mmol, 0.02 equiv.), then nitrogen was purged three times and dioxane H was added under nitrogen protection2O (32mL:8 mL). The mixture was stirred in a 60 ℃ oil bath for 8 hours and monitored by thin layer chromatography until the starting material was reacted. The reaction mixture is quenched by adding water, extracted three times with ethyl acetate, the organic phases are combined, dried with anhydrous sodium sulfate, then the solvent is removed by reduced pressure distillation, the obtained crude product is separated and purified by a silica gel chromatographic column, and the eluent: petroleum ether/dichloromethane ═ 30:1 to 20:1, giving compound 4, 2.00g of a white solid, yield60％。1H NMR(500MHz,CDCl3):δ1.47(s,9H),1.51(s,9H),7.41(dd,J＝7.5,0.5Hz,1H),7.49(dd,J＝8.5,1.0Hz,1H),7.53(dd,J＝8.5,1.5Hz,1H),7.67(t,J＝7.5Hz,1H),7.96(d,J＝2.0Hz,1H),8.00(d,J＝7.5Hz,1H),8.12-8.11(m,1H),8.21(d,J＝1.0Hz,1H),10.66(s,1H)。
Synthesis of compound L1: to a 50mL three-necked flask with a magnetic rotor was added compound 4(600mg, 1.38mmol, 1.0 equiv.), 2- (3-hydroxyphenyl) pyridine (300mg, 1.75mmol, 1.27 equiv.), cuprous iodide (53mg, 0.28mmol, 0.2 equiv.), 2-picolinic acid (34mg, 0.28mmol, 0.2 equiv.), tripotassium phosphate (614mg, 2.89mmol, 2.1 equiv.), then nitrogen was purged three times and dimethyl sulfoxide (10mL) was added under nitrogen protection. The mixture was stirred in an oil bath at 110 ℃ for 48 hours. After cooling to room temperature, the reaction mixture was quenched with water, extracted three times with ethyl acetate and the organic phases were combined and dried over anhydrous sodium sulfate. And (3) distilling under reduced pressure to remove the solvent, separating and purifying the obtained crude product by using a silica gel chromatographic column, and eluting the eluent: petroleum ether/ethyl acetate 10:1-3:1 gave compound L1 as a pale yellow solid, 500mg, yield 70%.1H NMR(500MHz,CDCl3):δ1.40(s,9H),1.48(s,9H),6.84(d,J＝8.5Hz,1H),7.00(d,J＝8.0Hz,1H),7.34-7.30(m,2H),7.43(dd,J＝8.0,2.5Hz,1H),7.73(t,J＝8.0Hz,1H),7.81-7.79(m,3H),7.87(t,J＝8.0Hz,1H),8.01-7.98(m,3H),8.09(d,J＝2.0Hz,1H),8.24(d,J＝7.5Hz,1H),8.74(d,J＝4.5Hz,1H),9.85(s,1H)。
Synthesis of Pt 1: to a 50mL three-necked flask equipped with a magnetic rotor and condenser was added intermediate L1(100mg, 0.19mmol, 1.0 equiv.), potassium chloroplatinate (83mg, 0.20mmol, 1.05 equiv.), n-tetrabutylammonium bromide (6.13mg, 0.019mmol, 0.1 equiv.), then nitrogen was purged three times, acetic acid (11.5mL) was added under nitrogen, and bubbling with nitrogen was carried out for 30 minutes. The mixture was stirred at room temperature for 12 hours and then in a 120 ℃ oil bath for 48 hours. Cooling to room temperature, suction filtration of the reaction mixture, washing with water, and recrystallization of the crude product from dichloromethane/ethyl acetate gave compound Pt1 as a yellow solid, 50mg, 35% yield.1H NMR(500MHz,DMSO):δ1.42(s,9H),1.46(s,9H),7.16(dd,J＝8.0,1.0Hz,1H),7.29(t,J＝7.5Hz,1H),7.43(d,J＝8.5Hz,1H),7.50(dd,J＝8.5,2.0Hz,1H),7.56-7.53(m,1H),7.58(d,J＝8.0Hz,1H),7.71(s,1H),7.77(d,J＝7.5Hz,1H),8.08(td,J＝7.5,1.5Hz,1H),8.18(d,J＝7.5Hz,1H),8.26(d,J＝2.0Hz,1H),8.41(s,1H),9.65(dd,J＝6.0,1.5Hz,1H),9.93-9.87(m,1H),11.27(s,1H)。
Example 2: the platinum complex Pt2 can be synthesized by the following route:
synthesis of compound L2: to a 50mL three-necked flask with a magnetic rotor was added intermediate 4(526mg, 1.21mmol, 1.1 equiv.), 9H- (2-pyridyl) -2-hydroxycarbazole (286mg, 1.10mmol, 1.0 equiv.), cuprous iodide (42mg, 0.22mmol, 2.0 equiv.), 2-picolinic acid (27.1mg, 0.22mmol, 0.2 equiv.), tripotassium phosphate (490mg, 2.31mmol, 2.1 equiv.), then nitrogen was purged three times and dimethyl sulfoxide (7mL) was added under nitrogen protection. The mixture was stirred in an oil bath at 110 ℃ for 48 hours. After cooling to room temperature, the reaction mixture was quenched with water, extracted three times with ethyl acetate and the organic phases were combined and dried over anhydrous sodium sulfate. And (3) distilling under reduced pressure to remove the solvent, separating and purifying the obtained crude product by using a silica gel chromatographic column, and eluting the eluent: petroleum ether/dichloromethane ═ 10:1-3:1, compound L2 was obtained as a pale yellow solid, 470mg, yield 70%.1H NMR(500MHz,CDCl3):δ1.32(s,9H),1.47(s,9H),6.15(dd,J＝8.5,0.5Hz,1H),6.84(dd,J＝8.5,2.0Hz,1H),6.98(dd,J＝8.0,1.0Hz,1H),7.24(ddd,J＝7.5,5.0,1.0Hz,1H),7.32(dd,J＝8.5,2.0Hz,1H),7.45(td,J＝7.5,1.0Hz,1H),7.55-7.51(m,2H),7.80-7.77(m,2H),7.84(dd,J＝5.0,3.0Hz,2H),7.87-7.86(m,1H),7.91(d,J＝2.0Hz,1H),7.99(d,J＝1.5Hz,1H),8.05(d,J＝2.0Hz,1H),8.25-8.23(m,1H),8.28(d,J＝8.5Hz,1H),8.66(ddd,J＝5.0,2.0,1.0Hz,1H),9.82(s,1H)。
Synthesis of Pt 2: to a 50mL three-necked flask with a magnetic rotor and condenser was added intermediate L2(200mg, 0.325mmol, 1.0 equiv.), potassium chloroplatinate (142mg, 0.342mmol, 1.05 equiv.), n-tetrabutylammonium bromide (10.5mg, 0.033mmol, 0.1 equiv.), then nitrogen was purged three times under nitrogen blanketAcetic acid (20mL) was added and the mixture was bubbled with nitrogen for 30 minutes. The mixture was stirred at room temperature for 12 hours and then in a 120 ℃ oil bath for 48 hours. Cooling to room temperature, suction filtration of the reaction mixture, washing with water, and recrystallization of the crude product from dichloromethane/ethyl acetate gave compound Pt2 as a yellow solid, 90mg, 35% yield.1H NMR(500MHz,DMSO):δ1.42(s,9H),1.48(s,9H),7.18(d,J＝8.0Hz,1H),7.29(td,J＝6.5,2.0Hz,1H),7.55-7.41(m,6H),7.70(s,1H),7.85(d,J＝8.5Hz,1H),8.12-8.07(m,3H),8.17(d,J＝8.0Hz,1H),8.26(s,1H),8.40(s,1H),9.69(s,1H),9.95-9.93(m,1H),11.31(s,1H)。
Example 3: the platinum complex Pt3 can be synthesized by the following route:
synthesis of compound L3: to a 50mL three-necked flask with a magnetic rotor was added intermediate 4(524mg, 1.20mmol, 1.1 eq), 9H- (3-methyl-2-pyridyl) -2-hydroxycarbazole (300mg, 1.10mmol, 1.0 eq), cuprous iodide (42mg, 0.22mmol, 0.2 eq), 2-picolinic acid (27mg, 0.22mmol, 0.2 eq), tripotassium phosphate (488mg, 2.30mmol, 2.1 eq), then nitrogen was purged three times and dimethyl sulfoxide (10mL) was added under nitrogen protection. The mixture was stirred in an oil bath at 110 ℃ for 48 hours. After cooling to room temperature, the reaction mixture was quenched with water, extracted three times with ethyl acetate and the organic phases were combined and dried over anhydrous sodium sulfate. And (3) distilling under reduced pressure to remove the solvent, separating and purifying the obtained crude product by using a silica gel chromatographic column, and eluting the eluent: petroleum ether/ethyl acetate 15:1-8:1 gave compound L3 as a pale yellow solid, 480mg, yield 70%.1H NMR(500MHz,CDCl3):δ1.26(s,9H),1.42(s,9H),2.33(s,3H),6.18(d,J＝8.5Hz,1H),6.77(dd,J＝8.5,2.0Hz,1H),7.15(dd,J＝5.0,3.0Hz,1H),7.22-7.21(m,1H),7.37(dd,J＝8.5,2.5Hz,1H),7.48-7.44(m,2H),7.55(td,J＝7.0,1.0Hz,1H),7.84-7.82(m,2H),8.05-8.03(m,4H),8.19(d,J＝1.5Hz,1H),8.41(d,J＝7.5Hz,1H),8.46(d,J＝5.0Hz,1H),8.52(d,J＝8.0Hz,1H),9.76(s,1H)。
Synthesis of Pt 3: to a 50mL three-necked flask equipped with a magnetic rotor and condenser was added intermediate L3(200mg, 0.32mmol, 1.0 equiv.), potassium chloroplatinate (138mg, 0.33mmol, 1.05 equiv.), n-tetrabutylammonium bromide (10.3mg, 0.032mmol, 0.1 equiv.), then nitrogen was purged three times, acetic acid (20mL) was added under nitrogen, and bubbling with nitrogen was carried out for 30 minutes. The mixture was stirred at room temperature for 12 hours and then in a 120 ℃ oil bath for 48 hours. Cooling to room temperature, suction filtration of the reaction mixture, washing with water and recrystallisation of the crude product from dichloromethane/ethyl acetate gave intermediate Pt3 as a solid 150mg in 58% yield.1H NMR(500MHz,DMSO):δ1.42(s,9H),1.48(s,9H),2.38(s,3H),7.14(dd,J＝6.0,1.5Hz,1H),7.17(d,J＝8.0Hz,1H),7.44-7.40(m,2H),7.50(dd,J＝9.0,2.5Hz,2H),7.54(d,J＝8.0Hz,2H),7.68(s,1H),7.85(d,J＝8.5Hz,1H),7.90(s,1H),8.12(d,J＝8.5Hz,1H),8.16(d,J＝8.0Hz,1H),8.26(d,J＝1.5Hz,1H),8.41(d,J＝2.0Hz,1H),9.82-9.71(m,2H),11.30(s,1H)。
Photophysical test and theoretical calculation description
Steady state emission experiments and lifetime measurements were performed on a Horiba Jobin Yvon fluolog-3 spectrometer. The Pt (II) complex was calculated theoretically using the Titan software package. Optimization of ground state (S) using Density Functional Theory (DFT)0) The geometry of the molecule. DFT calculations were performed using the B3LYP functional, with C, H, O and the N atoms using the 6-31G (d) basis set and the Pt atoms using the LANL2DZ basis set, and the results are shown in the following table and FIGS. 4-5.
As can be seen from fig. 1 to fig. 3, the platinum complexes Pt1, Pt2 and Pt3 can emit strong orange red light in a dichloromethane solution, the maximum emission wavelengths of the complexes are 558nm, 555nm and 554nm, the pyridine carbazole fragment is changed into benzopyridine in comparison with Pt2 in the case of Pt1, the emission spectrum is blue-shifted, and a methyl group is introduced to pyridine of pyridine carbazole in comparison with Pt2 in the case of Pt3, and the emission spectrum is slightly blue-shifted.
As can be seen from fig. 4, the electron distributions of the HOMO orbitals of Pt1, Pt2, and Pt3 are all concentrated on carbazole, with very close energies; comparing Pt1 with Pt2, the electrons of the LUMO track of Pt1 are distributed on the benzopyridine fragment, while the electrons of the LUMO track of Pt2 are concentrated on the pyridine of pyridine carbazole, because this part of the pyridine N atom is more electron deficient; comparing Pt2 with Pt3, Pt3 introduces a methyl group on pyridine of Pt2 pyridine carbazole, and electrons of LUMO orbital are distributed on pyridine ring of benzo carbazole, but part of electrons are transferred to pyridine ring connected with carbazole.
As can be seen from fig. 5, the electron distributions of the HOMO orbitals of Pt4, Pt5, and Pt6 are all concentrated on carbazole, with very close energies; comparing Pt4 with Pt6, the LUMO orbital of Pt4 has electrons distributed on the pyridine fragment linked to carbazole, while the LUMO orbital of Pt6 has electrons distributed on the pyridine fragment of pyridine carbazole; the LUMO orbital of Pt5 has electrons distributed on the pyridine ring of benzocarbazole, but some of the electrons are transferred to the pyridine ring attached to carbazole.
The results show that the N ^ N ^ C ^ N tetradentate platinum (II) complex containing the carbazole derivatives has excellent photophysical properties, and the photophysical properties of the metal platinum complex can be adjusted by changing the ligand structure surrounding the metal center and regulating and controlling the substituent structure on the ligand, so that the carbazole derivatives are ideal luminescent materials and can be used for preparing organic luminescent devices and the like. In a preferred embodiment of the present invention, the organic photoluminescent device has a structure in which at least a light-emitting layer is formed on a substrate, the light-emitting layer being made of the N ^ N ^ C ^ N tetradentate platinum (II) complex material containing carbazole-based derivatives of the present invention. The organic electroluminescent element has a structure in which at least an anode, a cathode, and an organic layer between the anode and the cathode are formed. The organic layer may be composed of only the light-emitting layer, or may have 1 or more organic layers other than the light-emitting layer. Examples of such other organic layers include a hole transport layer, a hole injection layer, an electron blocking layer, a hole blocking layer, an electron injection layer, an electron transport layer, and an exciton blocking layer. The hole transport layer may be a hole injection transport layer having a hole injection function, and the electron transport layer may be an electron injection transport layer having an electron injection function. The structure of the organic light-emitting element comprises 7 layers from bottom to top, and the substrate, the anode, the hole injection layer, the hole transport layer, the light-emitting layer, the electron transport layer and the cathode are sequentially represented, wherein the light-emitting layer is a mixed layer formed by doping a guest material into a host material.
Each layer of the organic light emitting device of the present invention can be formed by a method such as vacuum evaporation, sputtering, ion plating, or the like, or a wet film formation method such as spin coating, printing, or the like, and the solvent used is not particularly limited.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should all embodiments be exhaustive. And obvious variations or modifications of the invention may be made without departing from the scope of the invention.
Claims (5)
1. A tetrazole derivative-containing N ^ N ^ C ^ N type tetradentate platinum (II) complex is characterized by having a structure shown as a formula (I) or (II):
wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11And R12Each independently represents hydrogen, deuterium, alkyl, haloalkyl, cycloalkyl, alkoxy, aryl, heteroaryl, aryloxy, halogen, cycloalkenyl, heterocyclyl, alkenyl, alkynyl, hydroxy, mercaptoNitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, silyl, substituted silyl, and two or more adjacent R' s1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11And R12And may be selectively linked to form a fused ring.
2. The N ^ N ^ C ^ N type tetradentate platinum (II) complex of claim 1, characterized by having the structure of one of:
3. use of the N ^ N ^ C ^ N type tetradentate platinum (II) complexes described in claim 1 or2 as light emitting materials.
4. An organic light-emitting element characterized by having a light-emitting layer comprising the N ^ N ^ C ^ N type tetradentate platinum (II) complex according to any one of claims 1 and 2 on a substrate.
5. Use according to claim 4, wherein the organic light emitting element is an organic light emitting diode, a light emitting diode or a light emitting electrochemical cell.
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