CN114437134A - Luminescent material with polycyclic ligand - Google Patents
Luminescent material with polycyclic ligand Download PDFInfo
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- CN114437134A CN114437134A CN202110348602.6A CN202110348602A CN114437134A CN 114437134 A CN114437134 A CN 114437134A CN 202110348602 A CN202110348602 A CN 202110348602A CN 114437134 A CN114437134 A CN 114437134A
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- 239000000463 material Substances 0.000 title claims abstract description 59
- 239000003446 ligand Substances 0.000 title claims abstract description 44
- 125000003367 polycyclic group Chemical group 0.000 title abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 172
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 60
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 37
- 125000004432 carbon atom Chemical group C* 0.000 claims description 460
- 125000001424 substituent group Chemical group 0.000 claims description 113
- 239000010410 layer Substances 0.000 claims description 97
- -1 phosphino groups Chemical group 0.000 claims description 91
- 125000000217 alkyl group Chemical group 0.000 claims description 79
- 125000003118 aryl group Chemical group 0.000 claims description 75
- 125000001072 heteroaryl group Chemical group 0.000 claims description 72
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 67
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 56
- 125000005104 aryl silyl group Chemical group 0.000 claims description 53
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 44
- 229910052805 deuterium Inorganic materials 0.000 claims description 44
- 229910052736 halogen Inorganic materials 0.000 claims description 41
- 150000002367 halogens Chemical class 0.000 claims description 41
- 229910052739 hydrogen Inorganic materials 0.000 claims description 34
- 239000001257 hydrogen Substances 0.000 claims description 34
- 150000002431 hydrogen Chemical class 0.000 claims description 32
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 24
- 238000006467 substitution reaction Methods 0.000 claims description 22
- 229910052760 oxygen Inorganic materials 0.000 claims description 21
- 229910052717 sulfur Inorganic materials 0.000 claims description 21
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 19
- 125000003342 alkenyl group Chemical group 0.000 claims description 16
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 16
- 125000003545 alkoxy group Chemical group 0.000 claims description 15
- 125000004104 aryloxy group Chemical group 0.000 claims description 15
- 125000002252 acyl group Chemical group 0.000 claims description 14
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 14
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 14
- 125000003277 amino group Chemical group 0.000 claims description 13
- 239000012044 organic layer Substances 0.000 claims description 13
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims description 13
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 12
- 125000004185 ester group Chemical group 0.000 claims description 12
- 125000002837 carbocyclic group Chemical group 0.000 claims description 11
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 claims description 11
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 11
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 10
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 10
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 claims description 10
- 229910052711 selenium Inorganic materials 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 9
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 8
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 8
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 8
- 229940125904 compound 1 Drugs 0.000 claims description 7
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 7
- 125000004851 cyclopentylmethyl group Chemical group C1(CCCC1)C* 0.000 claims description 7
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims description 7
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052741 iridium Inorganic materials 0.000 claims description 6
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 6
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 6
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- 229910052701 rubidium Inorganic materials 0.000 claims description 5
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 4
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 claims description 4
- WIUZHVZUGQDRHZ-UHFFFAOYSA-N [1]benzothiolo[3,2-b]pyridine Chemical compound C1=CN=C2C3=CC=CC=C3SC2=C1 WIUZHVZUGQDRHZ-UHFFFAOYSA-N 0.000 claims description 4
- DHFABSXGNHDNCO-UHFFFAOYSA-N dibenzoselenophene Chemical compound C1=CC=C2C3=CC=CC=C3[se]C2=C1 DHFABSXGNHDNCO-UHFFFAOYSA-N 0.000 claims description 4
- VVVPGLRKXQSQSZ-UHFFFAOYSA-N indolo[3,2-c]carbazole Chemical compound C1=CC=CC2=NC3=C4C5=CC=CC=C5N=C4C=CC3=C21 VVVPGLRKXQSQSZ-UHFFFAOYSA-N 0.000 claims description 4
- 229960005544 indolocarbazole Drugs 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 125000005580 triphenylene group Chemical group 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 3
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Chemical group 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 claims description 3
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- BPMFPOGUJAAYHL-UHFFFAOYSA-N 9H-Pyrido[2,3-b]indole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=N1 BPMFPOGUJAAYHL-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- HCAUQPZEWLULFJ-UHFFFAOYSA-N benzo[f]quinoline Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=N1 HCAUQPZEWLULFJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003636 chemical group Chemical group 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- UTUZBCDXWYMYGA-UHFFFAOYSA-N silafluorene Chemical compound C12=CC=CC=C2CC2=C1C=CC=[Si]2 UTUZBCDXWYMYGA-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 136
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 115
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 114
- 238000003786 synthesis reaction Methods 0.000 description 103
- 230000015572 biosynthetic process Effects 0.000 description 102
- 239000007787 solid Substances 0.000 description 78
- 238000006243 chemical reaction Methods 0.000 description 75
- 229910052757 nitrogen Inorganic materials 0.000 description 64
- 150000002503 iridium Chemical class 0.000 description 62
- 239000000243 solution Substances 0.000 description 51
- 239000000047 product Substances 0.000 description 45
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 44
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 40
- 238000001914 filtration Methods 0.000 description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 29
- 239000000203 mixture Substances 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 24
- 238000000746 purification Methods 0.000 description 24
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 23
- 229910000027 potassium carbonate Inorganic materials 0.000 description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 238000001816 cooling Methods 0.000 description 20
- 229940093475 2-ethoxyethanol Drugs 0.000 description 19
- 238000004440 column chromatography Methods 0.000 description 18
- 239000000706 filtrate Substances 0.000 description 18
- LNJXVUXPFZKMNF-UHFFFAOYSA-K iridium(3+);trichloride;trihydrate Chemical compound O.O.O.Cl[Ir](Cl)Cl LNJXVUXPFZKMNF-UHFFFAOYSA-K 0.000 description 18
- JQUCWIWWWKZNCS-LESHARBVSA-N C(C1=CC=CC=C1)(=O)NC=1SC[C@H]2[C@@](N1)(CO[C@H](C2)C)C=2SC=C(N2)NC(=O)C2=NC=C(C=C2)OC(F)F Chemical compound C(C1=CC=CC=C1)(=O)NC=1SC[C@H]2[C@@](N1)(CO[C@H](C2)C)C=2SC=C(N2)NC(=O)C2=NC=C(C=C2)OC(F)F JQUCWIWWWKZNCS-LESHARBVSA-N 0.000 description 17
- 239000012043 crude product Substances 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 13
- 230000003111 delayed effect Effects 0.000 description 11
- 238000002390 rotary evaporation Methods 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 239000000758 substrate Substances 0.000 description 10
- QCIMLTPFBSDZNO-UHFFFAOYSA-N 3,7-diethyl-3,7-dimethylnonane-4,6-dione Chemical compound CCC(C)(CC)C(=O)CC(=O)C(C)(CC)CC QCIMLTPFBSDZNO-UHFFFAOYSA-N 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 9
- 239000012074 organic phase Substances 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- 239000012065 filter cake Substances 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 238000002347 injection Methods 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 150000003384 small molecules Chemical class 0.000 description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 230000000903 blocking effect Effects 0.000 description 6
- 238000005538 encapsulation Methods 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 6
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 description 6
- 239000011669 selenium Substances 0.000 description 6
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 5
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 125000005842 heteroatom Chemical group 0.000 description 5
- 230000000670 limiting effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 5
- 238000010898 silica gel chromatography Methods 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 5
- SCJNYBYSTCRPAO-LXBQGUBHSA-N CN(C)C\C=C\C(=O)NC1=CC=C(N=C1)C(=O)N[C@@]1(C)CCC[C@H](C1)NC1=NC(C2=CNC3=CC=CC=C23)=C(Cl)C=N1 Chemical compound CN(C)C\C=C\C(=O)NC1=CC=C(N=C1)C(=O)N[C@@]1(C)CCC[C@H](C1)NC1=NC(C2=CNC3=CC=CC=C23)=C(Cl)C=N1 SCJNYBYSTCRPAO-LXBQGUBHSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000002019 doping agent Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000005525 hole transport Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 230000036961 partial effect Effects 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- VNFWTIYUKDMAOP-UHFFFAOYSA-N sphos Chemical compound COC1=CC=CC(OC)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 VNFWTIYUKDMAOP-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- YRAJNWYBUCUFBD-UHFFFAOYSA-N 2,2,6,6-tetramethylheptane-3,5-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(C)(C)C YRAJNWYBUCUFBD-UHFFFAOYSA-N 0.000 description 3
- WCJDEXKLYKVMMR-UHFFFAOYSA-N 3,7-diethyl-3-methylnonane-4,6-dione Chemical compound CCC(CC)C(=O)CC(=O)C(C)(CC)CC WCJDEXKLYKVMMR-UHFFFAOYSA-N 0.000 description 3
- GDUANFXPOZTYKS-UHFFFAOYSA-N 6-bromo-8-[(2,6-difluoro-4-methoxybenzoyl)amino]-4-oxochromene-2-carboxylic acid Chemical compound FC1=CC(OC)=CC(F)=C1C(=O)NC1=CC(Br)=CC2=C1OC(C(O)=O)=CC2=O GDUANFXPOZTYKS-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- POFVJRKJJBFPII-UHFFFAOYSA-N N-cyclopentyl-5-[2-[[5-[(4-ethylpiperazin-1-yl)methyl]pyridin-2-yl]amino]-5-fluoropyrimidin-4-yl]-4-methyl-1,3-thiazol-2-amine Chemical compound C1(CCCC1)NC=1SC(=C(N=1)C)C1=NC(=NC=C1F)NC1=NC=C(C=C1)CN1CCN(CC1)CC POFVJRKJJBFPII-UHFFFAOYSA-N 0.000 description 3
- 125000000304 alkynyl group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000000477 aza group Chemical group 0.000 description 3
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- DFBKLUNHFCTMDC-GKRDHZSOSA-N endrin Chemical compound C([C@@H]1[C@H]2[C@@]3(Cl)C(Cl)=C([C@]([C@H]22)(Cl)C3(Cl)Cl)Cl)[C@@H]2[C@H]2[C@@H]1O2 DFBKLUNHFCTMDC-GKRDHZSOSA-N 0.000 description 3
- 239000012634 fragment Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZYGAMJLTPLERBC-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid propan-2-ol Chemical compound B(O)(O)OC(C)(C)C(C)(C)O.C(C)(C)O ZYGAMJLTPLERBC-UHFFFAOYSA-N 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 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
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- 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 1
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- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Chemical group C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- XDJOIMJURHQYDW-UHFFFAOYSA-N phenalene Chemical group C1=CC(CC=C2)=C3C2=CC=CC3=C1 XDJOIMJURHQYDW-UHFFFAOYSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical compound C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 1
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- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
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- CPNGPNLZQNNVQM-UHFFFAOYSA-N pteridine Chemical compound N1=CN=CC2=NC=CN=C21 CPNGPNLZQNNVQM-UHFFFAOYSA-N 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
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- 125000005415 substituted alkoxy group Chemical group 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 125000005346 substituted cycloalkyl group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- KTQYWNARBMKMCX-UHFFFAOYSA-N tetraphenylene Chemical group C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C3=CC=CC=C3C2=C1 KTQYWNARBMKMCX-UHFFFAOYSA-N 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- KPZYAGQLBFUTMA-UHFFFAOYSA-K tripotassium;phosphate;trihydrate Chemical compound O.O.O.[K+].[K+].[K+].[O-]P([O-])([O-])=O KPZYAGQLBFUTMA-UHFFFAOYSA-K 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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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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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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Abstract
A luminescent material having a polycyclic ligand is disclosed. The luminescent material is a metal complex with polycyclic ligands, and can be used as a luminescent material in an electroluminescent device. The novel metal complexes can better adjust the luminous color of the device while keeping very narrow half-peak width, reduce the driving voltage of the device or keep low voltage level, improve the efficiency of the device, greatly improve the service life of the device and provide better device performance. An electroluminescent device and compound combinations are also disclosed.
Description
Technical Field
The present invention relates to compounds for use in organic electronic devices, such as organic light emitting devices. More particularly, it relates to a metal complex having a polycyclic ligand, and an electroluminescent device and compound combination comprising the metal complex.
Background
Organic electronic devices include, but are not limited to, the following classes: organic Light Emitting Diodes (OLEDs), organic field effect transistors (O-FETs), Organic Light Emitting Transistors (OLETs), Organic Photovoltaics (OPVs), dye-sensitized solar cells (DSSCs), organic optical detectors, organic photoreceptors, organic field effect devices (OFQDs), light emitting electrochemical cells (LECs), organic laser diodes, and organic plasma light emitting devices.
In 1987, Tang and Van Slyke of Islamic Kodak reported a two-layer organic electroluminescent device comprising an arylamine hole transport layer and a tris-8-hydroxyquinoline-aluminum layer as an electron transport layer and a light-emitting layer (Applied Physics Letters, 1987,51(12): 913-915). Upon biasing the device, green light is emitted from the device. The invention lays a foundation for the development of modern Organic Light Emitting Diodes (OLEDs). The most advanced OLEDs may comprise multiple layers, such as charge injection and transport layers, charge and exciton blocking layers, and one or more light emitting layers between the cathode and anode. Since OLEDs are a self-emissive solid state device, it offers great potential for display and lighting applications. Furthermore, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications, such as in the fabrication of flexible substrates.
OLEDs can be classified into three different types according to their light emitting mechanisms. The OLEDs of the invention by Tang and van Slyke are fluorescent OLEDs. It uses only singlet luminescence. The triplet states generated in the device are wasted through the non-radiative decay channel. Therefore, the Internal Quantum Efficiency (IQE) of fluorescent OLEDs is only 25%. This limitation hinders the commercialization of OLEDs. In 1997, Forrest and Thompson reported phosphorescent OLEDs, which use triplet emission from complex-containing heavy metals as emitters. Thus, singlet and triplet states can be harvested, achieving 100% IQE. Due to its high efficiency, the discovery and development of phosphorescent OLEDs directly contributes to the commercialization of active matrix OLEDs (amoleds). Recently, Adachi has achieved high efficiency through Thermally Activated Delayed Fluorescence (TADF) of organic compounds. These emitters have a small singlet-triplet gap, making it possible for excitons to return from the triplet state to the singlet state. In TADF devices, triplet excitons are able to generate singlet excitons through reverse intersystem crossing, resulting in high IQE.
OLEDs can also be classified into small molecule and polymer OLEDs depending on the form of the material used. Small molecule refers to any organic or organometallic material that is not a polymer. The molecular weight of small molecules can be large, as long as they have a precise structure. Dendrimers with well-defined structures are considered small molecules. The polymeric OLED comprises a conjugated polymer and a non-conjugated polymer having a pendant light-emitting group. Small molecule OLEDs can become polymer OLEDs if post-polymerization occurs during the fabrication process.
Various OLED manufacturing methods exist. Small molecule OLEDs are typically fabricated by vacuum thermal evaporation. Polymer OLEDs are fabricated by solution processes such as spin coating, ink jet printing and nozzle printing. Small molecule OLEDs can also be made by solution processes if the material can be dissolved or dispersed in a solvent.
The light emitting color of the OLED can be realized by the structural design of the light emitting material. An OLED may comprise one light emitting layer or a plurality of light emitting layers to achieve a desired spectrum. Green, yellow and red OLEDs, phosphorescent materials have been successfully commercialized. Blue phosphorescent devices still have the problems of blue unsaturation, short device lifetime, high operating voltage, and the like. Commercial full-color OLED displays typically employ a hybrid strategy using either blue fluorescent and phosphorescent yellow, or red and green. At present, the rapid decrease in efficiency of phosphorescent OLEDs at high luminance is still a problem. In addition, it is desirable to have a more saturated emission spectrum, higher efficiency and longer device lifetime.
The phosphorescent metal complex can be used as a phosphorescent doping material of a light-emitting layer and applied to the field of organic electroluminescent lighting or display.
In CN110698518A discloses
A metal complex of the structure wherein X is N or P, one of the structures in the plurality of structures disclosed being:
the inventors have investigated the improvement in properties brought about by the N, P atom bridging to the material, but have not noted the improvement in properties brought about by the reintroduction of a fused ring system at a specific position on a specific ring.
In CN110790797A discloses
A metal complex of the structure, one of which in the plurality of structures disclosed is:
the inventors have investigated the improvement in properties brought about by the O, S atom bridging to the material, but have not noted the improvement in properties brought about by the reintroduction of a fused ring system at a specific position on a specific ring.
The performance of the metal complexes developed so far in the electroluminescent device still has various defects. In order to meet the increasing demands of the industry, such as lower voltage, higher device efficiency, light emission color in a specific wavelength range, more saturated light emission color, and longer device lifetime, research and development on metal complexes are still urgently needed.
Disclosure of Invention
The present invention aims to solve at least part of the above problems by providing a series of metal complexes with polycyclic ligands. The metal complex can be used as a luminescent material in an organic electroluminescent device. The novel metal complexes can better adjust the luminous color of the device while keeping very narrow half-peak width, reduce the driving voltage of the device or keep low voltage level, improve the efficiency of the device and greatly improve the service life of the device. The novel metal complexes can provide better device performance.
According to one embodiment of the present invention, a metal complex is disclosed comprising a ligand La，LaHas a structure represented by formula 1:
wherein, ring A and ring B are each independently selected from five-membered unsaturated carbocyclic ring, aromatic ring with 6-30 carbon atoms or heteroaromatic ring with 3-30 carbon atoms;
Rithe same or different at each occurrence represents mono-, poly-, or no substitution; riiThe same or different at each occurrence represents mono-, poly-, or no substitution;
y is selected from SiRyRy，GeRyRy，NRy，PRyO, S or Se;
when two R are simultaneously presentyWhen two R are presentyMay be the same or different;
X1-X2selected from CR, identically or differently at each occurrencexOr N;
R、Ri、Rii、Rxand RyEach occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atomsA group, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, a substituted or unsubstituted amine group having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a mercapto group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;
adjacent substituents Ri、Rx、RyR and RiiCan optionally be linked to form a ring;
the metal is selected from metals having a relative atomic mass greater than 40.
According to another embodiment of the present invention, there is also disclosed an electroluminescent device comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode, the organic layer comprising a metal complex comprising a ligand La，LaHas a structure represented by formula 1:
wherein, ring A and ring B are each independently selected from five-membered unsaturated carbocyclic ring, aromatic ring with 6-30 carbon atoms or heteroaromatic ring with 3-30 carbon atoms;
Rithe same or different at each occurrence represents mono-, poly-, or no substitution; riiThe same or different at each occurrence indicates mono-, poly-, or no substitution;
y is selected from SiRyRy，GeRyRy，NRy，PRyO, S or Se;
when two R are simultaneously presentyWhen two R are presentyMay be the same or different;
X1-X2selected from CR, identically or differently at each occurrencexOr N;
R、Ri、Rii、Rxand RyEach occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl groups having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted amine groups having 0-20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;
adjacent substituents Ri、Rx、RyR and RiiCan optionally be linked to form a ring;
the metal is selected from metals having a relative atomic mass greater than 40.
According to another embodiment of the present invention, a combination of compounds is also disclosed, comprising the metal complex of the above embodiment.
The novel metal complex with polycyclic ligand disclosed by the invention can be used as a luminescent material in an electroluminescent device. The novel metal complexes can better adjust the luminous color of the device while keeping very narrow half-peak width, reduce the driving voltage of the device or keep low voltage level, improve the efficiency of the device and greatly improve the service life of the device. The novel metal complexes can provide better device performance.
Drawings
FIG. 1 is a schematic representation of an organic light emitting device that can contain the metal complexes and compound combinations disclosed herein.
FIG. 2 is a schematic representation of another organic light emitting device that may contain combinations of the metal complexes and compounds disclosed herein.
FIG. 3 is a ligand L displaying a metal complex as disclosed hereinaThe structural formula 1.
Detailed Description
OLEDs can be fabricated on a variety of substrates, such as glass, plastic, and metal. Fig. 1 schematically, but without limitation, illustrates an organic light emitting device 100. The figures are not necessarily to scale, and some of the layer structures in the figures may be omitted as desired. The device 100 may include a substrate 101, an anode 110, a hole injection layer 120, a hole transport layer 130, an electron blocking layer 140, an emissive layer 150, a hole blocking layer 160, an electron transport layer 170, an electron injection layer 180, and a cathode 190. The device 100 may be fabricated by sequentially depositing the described layers. The nature and function of the layers, as well as exemplary materials, are described in more detail in U.S. patent US7,279,704B2, columns 6-10, which is incorporated herein by reference in its entirety.
There are more instances of each of these layers. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is doped with F at a molar ratio of 50:14TCNQ m-MTDATA as disclosed in U.S. patent application publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of host materials are disclosed in U.S. patent No. 6,303,238 to Thompson et al, which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. patent application publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entirety, disclose examples of cathodes including composite cathodes having a thin layer of a metal such as Mg: Ag and an overlying layer of transparent, conductive, sputter-deposited ITO. The principles and use of barrier layers are described in more detail in U.S. patent No. 6,097,147 and U.S. patent application publication No. 2003/0230980, which are incorporated by reference in their entirety. By way of full referenceExamples of injection layers are provided in incorporated U.S. patent application publication No. 2004/0174116. A description of a protective layer may be found in U.S. patent application publication No. 2004/0174116, which is incorporated by reference in its entirety.
The above-described hierarchical structure is provided via non-limiting embodiments. The function of the OLED may be achieved by combining the various layers described above, or some layers may be omitted entirely. It may also include other layers not explicitly described. Within each layer, a single material or a mixture of materials may be used to achieve optimal performance. Any functional layer may comprise several sub-layers. For example, the light emitting layer may have two layers of different light emitting materials to achieve a desired light emission spectrum.
In one embodiment, an OLED may be described as having an "organic layer" disposed between a cathode and an anode. The organic layer may include one or more layers.
The OLED also requires an encapsulation layer, as shown in fig. 2, which is an exemplary, non-limiting illustration of an organic light emitting device 200, which differs from fig. 1 in that an encapsulation layer 102 may also be included over the cathode 190 to protect against harmful substances from the environment, such as moisture and oxygen. Any material capable of providing an encapsulation function may be used as the encapsulation layer, such as glass or a hybrid organic-inorganic layer. The encapsulation layer should be placed directly or indirectly outside the OLED device. Multilayer film encapsulation is described in U.S. patent US7,968,146B2, the entire contents of which are incorporated herein by reference.
Devices manufactured according to embodiments of the present invention may be incorporated into various consumer products having one or more electronic component modules (or units) of the device. Some examples of such consumer products include flat panel displays, monitors, medical monitors, televisions, billboards, lights for indoor or outdoor lighting and/or signaling, head-up displays, fully or partially transparent displays, flexible displays, smart phones, tablet computers, tablet handsets, wearable devices, smart watches, laptop computers, digital cameras, camcorders, viewfinders, micro-displays, 3-D displays, vehicle displays, and tail lights.
The materials and structures described herein may also be used in other organic electronic devices as previously listed.
As used herein, "top" means furthest from the substrate, and "bottom" means closest to the substrate. Where a first layer is described as being "disposed on" a second layer, the first layer is disposed farther from the substrate. Other layers may be present between the first and second layers, unless it is specified that the first layer is "in contact with" the second layer. For example, a cathode can be described as being "disposed on" an anode even though various organic layers are present between the cathode and the anode.
As used herein, "solution processable" means capable of being dissolved, dispersed or transported in and/or deposited from a liquid medium in the form of a solution or suspension.
A ligand may be referred to as "photoactive" when it is believed that the ligand directly contributes to the photoactive properties of the emissive material. A ligand may be referred to as "ancillary" when it is believed that the ligand does not contribute to the photoactive properties of the emissive material, but that the ancillary ligand may alter the properties of the photoactive ligand.
It is believed that the Internal Quantum Efficiency (IQE) of fluorescent OLEDs can be limited by delaying fluorescence beyond 25% spin statistics. Delayed fluorescence can generally be divided into two types, i.e., P-type delayed fluorescence and E-type delayed fluorescence. P-type delayed fluorescence results from triplet-triplet annihilation (TTA).
On the other hand, E-type delayed fluorescence does not depend on collision of two triplet states, but on conversion between a triplet state and a singlet excited state. Compounds capable of producing E-type delayed fluorescence need to have a very small mono-triplet gap in order to switch between energy states. Thermal energy can activate the transition from the triplet state back to the singlet state. This type of delayed fluorescence is also known as Thermally Activated Delayed Fluorescence (TADF). A significant feature of TADF is that the retardation component increases with increasing temperature. If the reverse intersystem crossing (RISC) rate is fast enough to minimize non-radiative decay from the triplet state, then the fraction of backfill singlet excited states may reach 75%. The total singlet fraction may be 100%, well in excess of 25% of the spin statistics of the electrogenerated excitons.
The delayed fluorescence characteristic of type E can be found in excited complex systems or in single compounds. Without being bound by theory, it is believed that E-type delayed fluorescence requires the light emitting material to have a small mono-triplet energy gap (Δ Ε)S-T). Organic non-metal containing donor-acceptor emissive materials may be able to achieve this. The emission of these materials is generally characterized as donor-acceptor Charge Transfer (CT) type emission. Spatial separation of HOMO from LUMO in these donor-acceptor type compounds generally results in small Δ ES-T. These states may include CT states. Generally, donor-acceptor light emitting materials are constructed by linking an electron donor moiety (e.g., an amino or carbazole derivative) to an electron acceptor moiety (e.g., a six-membered, N-containing, aromatic ring).
Definitions for substituent terms
Halogen or halide-as used herein, includes fluorine, chlorine, bromine and iodine.
Alkyl-comprises both straight and branched chain alkyl groups. The alkyl group may be an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, neopentyl, 1-methylpentyl, 2-methylpentyl, 1-pentylhexyl, 1-butylpentyl, 1-heptyloctyl, 3-methylpentyl. In addition, the alkyl group may be optionally substituted. The carbons in the alkyl chain may be substituted with other heteroatoms. Among the above, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl and neopentyl are preferable.
Cycloalkyl-as used herein, comprises a cyclic alkyl group. Preferred cycloalkyl groups are those containing 4 to 10 ring carbon atoms and include cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4, 4-dimethylcyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl and the like. In addition, the cycloalkyl group may be optionally substituted. The carbon in the ring may be substituted with other heteroatoms.
Alkenyl-as used herein, encompasses both straight and branched chain olefinic groups. Preferred alkenyl groups are those containing 2 to 15 carbon atoms. Examples of the alkenyl group include a vinyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a1, 3-butadienyl group, a 1-methylvinyl group, a styryl group, a 2, 2-diphenylvinyl group, a 1-methylallyl group, a1, 1-dimethylallyl group, a 2-methylallyl group, a 1-phenylallyl group, a 3, 3-diphenylallyl group, a1, 2-dimethylallyl group, a 1-phenyl-1-butenyl group and a 3-phenyl-1-butenyl group. In addition, alkenyl groups may be optionally substituted.
Alkynyl-as used herein, straight and branched alkynyl groups are contemplated. Preferred alkynyl groups are those containing 2 to 15 carbon atoms. In addition, alkynyl groups may be optionally substituted.
Aryl or aromatic-as used herein, non-fused and fused systems are contemplated. Preferred aryl groups are those containing from 6 to 60 carbon atoms, more preferably from 6 to 20 carbon atoms, and even more preferably from 6 to 12 carbon atoms. Examples of aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene,
perylene and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene and naphthalene. In addition, the aryl group may be optionally substituted. Examples of non-fused aryl groups include phenyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, o-tolyl, m-tolyl, p-tolyl, p- (2-phenylpropyl) phenyl, 4 '-methyldiphenyl, 4' -tert-butyl-p-terphenyl-4-yl, o-cumyl, m-cumyl, p-cumyl, 2, 3-xylyl, 3, 4-xylyl, 2, 5-xylyl, mesityl and m-quaterphenyl.
Heterocyclyl or heterocyclic-as used herein, aromatic and non-aromatic cyclic groups are contemplated. Heteroaryl also refers to heteroaryl. Preferred non-aromatic heterocyclic groups are those containing 3 to 7 ring atoms, which include at least one heteroatom such as nitrogen, oxygen and sulfur. The heterocyclic group may also be an aromatic heterocyclic group having at least one hetero atom selected from a nitrogen atom, an oxygen atom, a sulfur atom and a selenium atom.
Heteroaryl-as used herein, non-fused and fused heteroaromatic groups are contemplated which may contain 1 to 5 heteroatoms. Preferred heteroaryl groups are those containing from 3 to 30 carbon atoms, more preferably from 3 to 20 carbon atoms, more preferably from 3 to 12 carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridine indole, pyrrolopyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, bisoxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indoline, benzimidazole, indazole, indenozine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, benzofuropyridine, furobipyridine, benzothienopyridine, thienobipyridine, cinnolino, benzoselenophenopyridine, selenobenzene, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1, 2-azaborine, 1, 3-azaborine, 1, 4-azaborine, borazole, and aza analogues thereof. In addition, the heteroaryl group may be optionally substituted.
Alkoxy-is represented by-O-alkyl. Examples and preferred examples of the alkyl group are the same as those described above. Examples of the alkoxy group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentyloxy, and hexyloxy. The alkoxy group having 3 or more carbon atoms may be linear, cyclic or branched.
Aryloxy-is represented by-O-aryl or-O-heteroaryl. Examples and preferred examples of aryl and heteroaryl groups are the same as described above. Examples of the aryloxy group having 6 to 40 carbon atoms include a phenoxy group and a biphenyloxy group.
Aralkyl-as used herein, an alkyl group having an aryl substituent. In addition, the aralkyl group may be optionally substituted. Examples of the aralkyl group include benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, 2-phenylisopropyl, phenyl tert-butyl, α -naphthylmethyl, 1- α -naphthylethyl, 2- α -naphthylethyl, 1- α -naphthylisopropyl, 2- α -naphthylisopropyl, β -naphthylmethyl, 1- β -naphthylethyl, 2- β -naphthylethyl, 1- β -naphthylisopropyl, 2- β -naphthylisopropyl, p-methylbenzyl, m-methylbenzyl, o-methylbenzyl, p-chlorobenzyl, m-chlorobenzyl, o-chlorobenzyl, p-bromobenzyl, m-bromobenzyl, o-bromobenzyl, p-iodobenzyl, m-iodobenzyl, o-iodobenzyl, p-hydroxybenzyl, m-hydroxybenzyl, o-hydroxybenzyl, p-aminobenzyl, m-aminobenzyl, o-aminobenzyl, p-nitrobenzyl, m-nitrobenzyl, o-nitrobenzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-hydroxy-2-phenylisopropyl and 1-chloro-2-phenylisopropyl. Among the above, benzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl and 2-phenylisopropyl are preferable.
The term "aza" in aza-dibenzofuran, aza-dibenzothiophene, etc., means that one or more C-H groups in the corresponding aromatic moiety are replaced by a nitrogen atom. For example, azatriphenylenes include dibenzo [ f, h ] quinoxalines, dibenzo [ f, h ] quinolines, and other analogs having two or more nitrogens in the ring system. Other nitrogen analogs of the aza derivatives described above will be readily apparent to one of ordinary skill in the art, and all such analogs are intended to be encompassed by the term as described herein.
In this disclosure, unless otherwise defined, when any one of the terms in the group consisting of: substituted alkyl, substituted cycloalkyl, substituted heteroalkyl, substituted aralkyl, substituted alkoxy, substituted aryloxy, substituted alkenyl, substituted aryl, substituted heteroaryl, substituted alkylsilyl, substituted arylsilyl, substituted amine, substituted acyl, substituted carbonyl, substituted carboxylic acid, substituted ester, substituted sulfinyl, substituted sulfonyl, substituted phosphino, meaning alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, alkenyl, aryl, heteroaryl, alkylsilyl, arylsilyl, amine, acyl, carbonyl, carboxylic acid, ester, sulfinyl, sulfonyl and phosphino, any of which may be substituted by one or more groups selected from deuterium, halogen, unsubstituted alkyl having 1 to 20 carbon atoms, unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, unsubstituted heteroalkyl having 1 to 20 carbon atoms, unsubstituted aralkyl having 7 to 30 carbon atoms, unsubstituted alkoxy having 1 to 20 carbon atoms, unsubstituted aryloxy having 6 to 30 carbon atoms, unsubstituted alkenyl having 2 to 20 carbon atoms, unsubstituted aryl having 6 to 30 carbon atoms, unsubstituted heteroaryl having 3 to 30 carbon atoms, unsubstituted alkylsilyl having 3 to 20 carbon atoms, unsubstituted arylsilyl having 6 to 20 carbon atoms, unsubstituted amine group having 0 to 20 carbon atoms, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, mercapto group, sulfinyl group, sulfonyl group, phosphino group, and combinations thereof.
It will be understood that when a molecular fragment is described as a substituent or otherwise attached to another moiety, its name may be written depending on whether it is a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or depending on whether it is an entire molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of specifying substituents or linking fragments are considered to be equivalent.
In the compounds mentioned in the present disclosure, a hydrogen atom may be partially or completely replaced by deuterium. Other atoms such as carbon and nitrogen may also be replaced by their other stable isotopes. Substitution of other stable isotopes in the compounds may be preferred because it enhances the efficiency and stability of the device.
In the compounds mentioned in the present disclosure, multiple substitution means that a double substitution is included up to the range of the maximum available substitutions. When a substituent in a compound mentioned in the present disclosure represents multiple substitution (including di-substitution, tri-substitution, tetra-substitution, etc.), that is, it means that the substituent may exist at a plurality of available substitution positions on its connecting structure, and the substituent existing at each of the plurality of available substitution positions may be the same structure or different structures.
In the compounds mentioned in the present disclosure, adjacent substituents in the compounds cannot be linked to form a ring unless specifically defined, for example, adjacent substituents can be optionally linked to form a ring. In the compounds mentioned in the present disclosure, adjacent substituents can be optionally linked to form a ring, including both the case where adjacent substituents may be linked to form a ring and the case where adjacent substituents are not linked to form a ring. When adjacent substituents can optionally be joined to form a ring, the ring formed can be monocyclic or polycyclic, as well as alicyclic, heteroalicyclic, aromatic or heteroaromatic rings. In this expression, adjacent substituents may refer to substituents bonded to the same atom, substituents bonded to carbon atoms directly bonded to each other, or substituents bonded to carbon atoms further away. Preferably, adjacent substituents refer to substituents bonded to the same carbon atom as well as substituents bonded to carbon atoms directly bonded to each other.
The expression that adjacent substituents can optionally be linked to form a ring is also intended to mean that two substituents bonded to the same carbon atom are linked to each other by a chemical bond to form a ring, which can be exemplified by the following formula:
the expression that adjacent substituents can optionally be linked to form a ring is also intended to mean that two substituents bonded to carbon atoms directly bonded to each other are linked to each other by a chemical bond to form a ring, which can be exemplified by the following formula:
further, the expression that adjacent substituents can be optionally connected to form a ring is also intended to be taken to mean that, in the case where one of two substituents bonded to carbon atoms directly bonded to each other represents hydrogen, the second substituent is bonded at a position to which the hydrogen atom is bonded, thereby forming a ring. This is exemplified by the following equation:
according to one embodiment of the present invention, a metal complex is disclosed comprising a ligand La，LaHas a structure represented by formula 1:
wherein, ring A and ring B are each independently selected from five-membered unsaturated carbocyclic ring, aromatic ring with 6-30 carbon atoms or heteroaromatic ring with 3-30 carbon atoms;
Rithe same or different at each occurrence represents mono-, poly-, or no substitution; riiThe same or different at each occurrence represents mono-, poly-, or no substitution;
y is selected from SiRyRy，GeRyRy，NRy，PRyO, S or Se;
when two R are simultaneously presentyWhen two R are presentyMay be the same or different; for example, when Y is selected from SiRyRyWhen two R are presentyMay be the same or different; as another example, when Y is selected from GeRyRyWhen two R are presentyMay be the same or different;
X1-X2selected from CR, identically or differently at each occurrencexOr N;
R、Ri、Rii、Rxand RyEach occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstitutedA heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, a substituted or unsubstituted amine group having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a mercapto group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;
adjacent substituents Ri、Rx、RyR and RiiCan optionally be linked to form a ring;
the metal is selected from metals having a relative atomic mass greater than 40.
In this context, adjacent substituents Ri、Rx、RyR and RiiCan optionally be linked to form a ring, is intended to mean a group in which adjacent substituents are present, for example two substituents RiIn between, two substituents RiiIn between, two substituents RyIn between, two substituents RxOf a substituent RiAnd RxIn the substituent R and RyAnd a substituent RiiAnd R, any one or more of these substituent groups may be bonded to form a ring. Obviously, none of these substituents may be connected to each other to form a ring.
According to one embodiment of the invention, wherein the metal complex optionally comprises further ligands, which may be related to the LaOptionally linked to form a tridentate, tetradentate, pentadentate or hexadentate ligand.
According to one embodiment of the invention, ring a and ring B are each independently selected from a five-membered unsaturated carbocyclic ring, an aromatic ring having 6 to 18 carbon atoms, or a heteroaromatic ring having 3 to 18 carbon atoms.
According to one embodiment of the invention, ring a or ring B is each independently selected from a five-membered unsaturated carbocyclic ring, an aromatic ring having 6 to 18 carbon atoms, or a heteroaromatic ring having 3 to 18 carbon atoms.
According to one embodiment of the invention, ring a and ring B are each independently selected from a five-membered unsaturated carbocyclic ring, an aromatic ring having 6 to 10 carbon atoms, or a heteroaromatic ring having 3 to 10 carbon atoms.
According to one embodiment of the invention, ring a or ring B is each independently selected from a five-membered unsaturated carbocyclic ring, an aromatic ring having 6 to 10 carbon atoms, or a heteroaromatic ring having 3 to 10 carbon atoms.
According to an embodiment of the present invention, wherein said LaA structure selected from the group consisting of structures represented by any one of formulas 2 to 19 and 22 to 23:
wherein,
in the formulae 2 to 19 and 22 to 23, X1-X2Each independently selected from CRxOr N; x3-X7Each independently selected from CRiOr N; a. the1-A6Each independently selected from CRiiOr N;
z is selected, identically or differently on each occurrence, from CRiiiRiii，SiRiiiRiii，PRiiiO, S or NRiii(ii) a When two R are simultaneously presentiiiWhen two R are presentiiiThe same or different; for example, when Z is selected from CRiiiRiiiWhen two R are presentiiiThe same or different; as another example, when Z is selected from SiRiiiRiiiWhen two R are presentiiiThe same or different;
y is selected from SiRyRy，NRy，PRyO, S or Se; when two R are simultaneously presentyWhen two R are presentyMay be the same or different; for example when Y is selected from SiRyRyWhen two R are presentyMay be the same or different;
R，Ri，Rii，Rx，Riiieach occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl groups having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted amine groups having 0-20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;
adjacent substituents R, Rx，Ry，Ri，Rii，RiiiCan optionally be linked to form a ring.
In this context, the adjacent substituents R, Rx，Ry，Ri，Rii，RiiiCan optionally be linked to form a ring, is intended to mean a group in which adjacent substituents are present, for example two substituents RiIn between, two substituents RiiIn between, two substituents RxIn between, two substituents RyIn between, two substituents RiiiOf a substituent RiAnd RxOf a substituent RiiAnd RiiiIn the substituent R and RyOf R is a substituentyAnd RiiiAnd the substituents R and RiiiAny one or more of these substituent groups may be linked to form a ring. Obviously, none of these substituents may be connected to each other to form a ring.
According to an embodiment of the invention, wherein LaSelected from the group consisting of tables of formula 2, formula 9, formula 11, and formula 12The structure shown.
According to an embodiment of the invention, wherein LaSelected from the structures represented by formula 2.
According to an embodiment of the present invention, wherein, in formula 2-formula 19 and formula 22-formula 23, X1-XnAnd/or A1-AmAt least one of them is selected from N, XnCorresponding to the X1-X7The largest numerical order in any one of the formulae 2 to 19 and 22 to 23, wherein A ismCorresponds to the A1-A6The largest sequence number among any one of the formulae 2 to 19 and 22 to 23; for example, for formula 2, the XnCorresponding to the X1-X7X having the largest number in formula 25Said A ismCorresponds to the A1-A6The one with the largest sequence number A existing in formula 24I.e., in formula 2, X1-X5And/or A1-A4At least one of which is selected from N. As another example, for formula 12, the XnCorresponding to the X1-X7X having the largest number in formula 123Said A ismCorresponds to the A1-A6The one with the largest sequence number A in formula 124I.e. X in formula 121-X3And/or A1-A4At least one of which is selected from N.
According to an embodiment of the present invention, wherein, in formula 2-formula 19 and formula 22-formula 23, X1-XnAt least one of them is selected from N, XnCorresponding to the X1-X7The largest sequence number is present in any of formulae 2 to 19 and 22 to 23.
According to an embodiment of the present invention, wherein, in formula 2-formula 19 and formula 22-formula 23, X2Is N.
According to an embodiment of the present invention, wherein, in formula 2-formula 19 and formula 22-formula 23, X1-X2Each independently selected from CRx；X3-X7Each independently selected from CRi；A1-A6Each independently selected from CRii(ii) a Adjacent substituents Rx、Ri、RiiCan optionally be linked to form a ring.
In this example, the adjacent substituents Rx、Ri、RiiCan optionally be linked to form a ring, is intended to mean a group in which adjacent substituents are present, for example two substituents RiIn between, two substituents RiiIn between, two substituents RxAnd a substituent RiAnd RxAny one or more of these substituent groups may be linked to form a ring. Obviously, none of these substituents may be linked to each other to form a ring.
According to an embodiment of the present invention, wherein, in formula 2-formula 19 and formula 22-formula 23, X1-X2Each independently selected from CRx；X3-X7Each independently selected from CRi；A1-A6Each independently selected from CRii(ii) a And said R isx、Ri、RiiEach occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, cyano groups, and combinations thereof; adjacent substituents Rx、Ri、RiiCan optionally be linked to form a ring.
According to an embodiment of the present invention, wherein, in formula 2-formula 19 and formula 22-formula 23, X1-X2Each independently selected from CRx；X3-X7Each independently selected from CRi；A1-A6Each independently selected from CRii(ii) a And said R isx、Ri、RiiAt least two of which, on each occurrence, are selected, identically or differently, from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substitutedOr unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, cyano, and combinations thereof; adjacent substituents Rx、Ri、RiiCan optionally be linked to form a ring.
In this embodiment, R isx、Ri、RiiAt least two of which, on each occurrence, are selected, identically or differently, from the group of substituents mentioned, is intended to mean that the substituents consisting of two RxSubstituent, all RiSubstituents and all RiiAt least two substituents in a group of substituents, which are identical or different on each occurrence, are selected from the group of substituents.
According to an embodiment of the present invention, wherein, in formula 2-formula 19 and formula 22-formula 23, X1-X2Each independently selected from CRx；X3-X7Each independently selected from CRi；A1-A6Each independently selected from CRii(ii) a And said R isx、Ri、RiiAt least three of which, identically or differently on each occurrence, are selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, cyano groups, and combinations thereof; adjacent substituents Rx、Ri、RiiCan optionally be linked to form a ring.
In this embodiment, R isx、Ri、RiiAt least three of which, on each occurrence, are selected, identically or differently, from the group of substituents mentioned, is intended to mean that the substituents consisting of two RxSubstituent, all RiSubstituents and all RiiSubstitutionAt least three substituents in the group of substituents are selected, identically or differently on each occurrence, from the group of substituents mentioned.
According to an embodiment of the present invention, wherein, in formula 2-formula 11 and formula 22-formula 23, X4And X5Each independently selected from CRi(ii) a In formula 12-formula 19, X3Selected from the group consisting of CRi。
According to an embodiment of the present invention, wherein, in formula 2-formula 11 and formula 22-formula 23, X4Or X5Selected from the group consisting of CRi(ii) a In formula 12 to formula 19, X3Selected from the group consisting of CRi。
According to an embodiment of the present invention, wherein, in formula 2-formula 11 and formula 22-formula 23, X4And X5Each independently selected from CRi(ii) a In formula 12 to formula 19, X3Selected from the group consisting of CRi(ii) a And said R isiEach occurrence is the same or different and is selected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, cyano, or combinations thereof.
According to an embodiment of the present invention, wherein, in formula 2-formula 11 and formula 22-formula 23, X4Or X5Selected from the group consisting of CRi(ii) a In formula 12-formula 19, X3Selected from the group consisting of CRi(ii) a And said R isiEach occurrence is the same or different and is selected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, cyano, or combinations thereof.
According to an embodiment of the present invention, among them, in the formulas 2-11 and 22-typeIn 23, X4And X5Each independently selected from CRi(ii) a In formula 12-formula 19, X3Selected from the group consisting of CRi(ii) a Wherein said RiEach occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, fluoro, methyl, ethyl, isopropyl, isobutyl, tert-butyl, neopentyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, norbornyl, adamantyl, trimethylsilyl, isopropyldimethylsilyl, phenyldimethylsilyl, trifluoromethyl, cyano, phenyl, and combinations thereof.
According to an embodiment of the present invention, wherein, in formula 2-formula 11 and formula 22-formula 23, X4Or X5Selected from the group consisting of CRi(ii) a In formula 12-formula 19, X3Selected from the group consisting of CRi(ii) a Wherein said RiEach occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, fluoro, methyl, ethyl, isopropyl, isobutyl, tert-butyl, neopentyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, norbornyl, adamantyl, trimethylsilyl, isopropyldimethylsilyl, phenyldimethylsilyl, trifluoromethyl, cyano, phenyl, and combinations thereof.
According to an embodiment of the present invention, wherein, in formula 2-formula 19 and formula 22-formula 23, R is selected from hydrogen, deuterium, halogen, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, or a combination thereof.
According to an embodiment of the present invention, wherein, in formula 2-formula 19 and formula 22-formula 23, R is selected from hydrogen, deuterium, fluorine, methyl, ethyl, isopropyl, isobutyl, tert-butyl, neopentyl, cyclopentyl, cyclopentylmethyl, deuterated methyl, deuterated ethyl, deuterated isopropyl, deuterated tert-butyl, deuterated neopentyl, deuterated cyclopentyl, deuterated cyclopentylmethyl, deuterated cyclohexyl, trimethylsilyl, or a combination thereof.
According to one embodiment of the present invention, wherein, in formula 2-formula 19 and formula 22-formula 23, Y is selected from O or S.
According to one embodiment of the present invention, wherein, in formula 2-formula 19 and formula 22-formula 23, Y is selected from O.
According to one embodiment of the present invention, wherein, in formula 2-formula 19 and formula 22-formula 23, X1And X2Each independently selected from CRx。
According to an embodiment of the present invention, wherein, in formula 2-formula 19 and formula 22-formula 23, X1And X2Each independently selected from CRx(ii) a And said R isxEach occurrence is the same or different and is selected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, or combinations thereof.
According to an embodiment of the present invention, wherein, in formula 2-formula 19 and formula 22-formula 23, X1Selected from the group consisting of CRx，X2Is N.
According to an embodiment of the present invention, wherein, in formula 2-formula 19 and formula 22-formula 23, X1Selected from the group consisting of CRx，X2Is N; and said R isxEach occurrence is the same or different and is selected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, or combinations thereof.
According to one embodiment of the invention, wherein the ligand LaHas a structure represented by formula 20 or formula 21:
wherein, in the formulae 20 and 21,
y is selected from O or S;
Rx1、Rx2、Ri1、Ri2、Ri3、Rii1、Rii2、Rii3、Rii4each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, or combinations thereof;
r is selected, identically or differently on each occurrence, from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted amine groups having 0 to 20 carbon atoms, and combinations thereof.
According to one embodiment of the invention, wherein the ligand LaHas a structure represented by formula 20 or formula 21:
wherein, in the formulae 20 and 21,
y is selected from O or S;
Rx1、Rx2、Ri1、Ri2、Ri3neutralization/or Rii1、Rii2、Rii3、Rii4Is selected, identically or differently on each occurrence, from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, or a combination thereof; r is selected from the group consisting of halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, or combinations thereof.
According to one embodiment of the invention, wherein the ligand LaHas a structure represented by formula 20 or formula 21:
wherein, in the formulae 20 and 21,
y is selected from O or S;
Rx1、Rx2、Ri1、Ri2、Ri3neutralization/or Rii1、Rii2、Rii3And Rii4Is selected, identically or differently on each occurrence, from the group consisting of: a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, or a combination thereof; r is selected from substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstitutedA substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, or a combination thereof.
According to one embodiment of the invention, wherein the ligand LaHas a structure represented by formula 20 or formula 21:
wherein, in the formulae 20 and 21,
y is selected from O or S;
Ri2selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, or combinations thereof;
r is selected from the group consisting of: halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, or combinations thereof; rii1、Rii2、Rii3、Rii4Is selected, identically or differently on each occurrence, from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atomsA group, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, or a combination thereof.
According to one embodiment of the invention, wherein the ligand LaHas a structure represented by formula 20 or formula 21:
wherein, in the formulae 20 and 21,
y is selected from O or S;
Ri2selected from the group consisting of: a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, or a combination thereof;
r is selected from the group consisting of: a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, or a combination thereof; rii1、Rii2、Rii3、Rii4Is selected, identically or differently on each occurrence, from the group consisting of: a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, or a combination thereof.
According to the inventionAn embodiment of the present invention, wherein, in the formulas 20 and 21, Rii1、Rii2、Rii3Of (e.g., R)ii1Or Rii2Or Rii3) Or two (e.g. R)ii1And Rii2Or Rii2And Rii3Or Rii1And Rii3) Each occurrence, the same or different, is selected from the group consisting of: a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, or a combination thereof.
According to an embodiment of the present invention, wherein, in formula 20 and formula 21, Rx1、Rx2、Ri1、Ri2、Ri3、Rii1、Rii2、Rii3、Rii4Each occurrence of at least one of R, is selected, identically or differently, from the group consisting of: substituted or unsubstituted alkyl groups having 3 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, and combinations thereof.
In this embodiment, Rx1、Rx2、Ri1、Ri2、Ri3、Rii1、Rii2、Rii3、Rii4At least one of R, taken on each occurrence, identically or differently, is selected from said group of substituents, intended to mean: rx1、Rx2Is selected, identically or differently on each occurrence, from the group of substituents, and/or Ri1、Ri2、Ri3Is selected, identically or differently on each occurrence, from the group of substituents, and/or Rii1、Rii2、Rii3、Rii4Is selected from said group of substituents, identically or differently on each occurrence, and/or R is selected from said group of substituents.
According to one embodiment of the present invention, wherein, in the formulas 20 and 21, Ri2、Ri3、Rii1、Rii2、Rii3Each occurrence of at least one of R, is selected, identically or differently, from the group consisting of: substituted or unsubstituted alkyl groups having 3 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, and combinations thereof.
In this embodiment, Ri2、Ri3、Rii1、Rii2、Rii3At least one of R, taken on each occurrence, identically or differently, is selected from said group of substituents, intended to mean: ri2、Ri3Is selected, identically or differently on each occurrence, from the group of substituents, and/or Rii1、Rii2、Rii3Is selected, identically or differently on each occurrence, from the group of substituents, and/or R is selected from the group of substituents.
According to an embodiment of the present invention, wherein, in formula 20 and formula 21, Rx1、Rx2、Ri1、Ri2、Ri3、Rii1、Rii2、Rii3、Rii4Each occurrence of at least one of R, is selected, identically or differently, from the group consisting of: substituted or unsubstituted alkyl groups having 3 to 10 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 10 ring carbon atoms, and combinations thereof.
In this embodiment, Rx1、Rx2、Ri1、Ri2、Ri3、Rii1、Rii2、Rii3、Rii4At least one of R, taken on each occurrence, identically or differently, is selected from said group of substituents, intended to mean: rx1、Rx2Is selected, identically or differently on each occurrence, from the group of substituents, and/or Ri1、Ri2、Ri3Is selected, identically or differently on each occurrence, from the group of substituents, and/or Rii1、Rii2、Rii3、Rii4In (1)At least one is selected from said group of substituents, identically or differently on each occurrence, and/or R is selected from said group of substituents.
According to one embodiment of the present invention, wherein LaEach occurrence being selected identically or differently from La1To La1706Wherein L isa1To La1706See claim 14 for specific structure of (a).
According to an embodiment of the invention, wherein LaEach occurrence being selected identically or differently from La1To La1803Wherein L isa1To La1803See claim 14 for specific structure of (a).
According to an embodiment of the invention, wherein LaEach occurrence being selected identically or differently from La1To La1931Wherein L isa1To La1931See claim 14 for specific structure of (a).
According to an embodiment of the present invention, wherein said La1To La1931The hydrogen in the structure of (a) can be partially or completely substituted with deuterium.
According to one embodiment of the present invention, wherein the metal complex has M (L)a)m(Lb)n(Lc)qThe structure of (1);
wherein the metal M is selected from metals having a relative atomic mass greater than 40; l isa、LbAnd LcA first ligand, a second ligand and a third ligand, respectively, of the complex; m is 1,2 or 3, n is 0, 1 or 2, q is 0, 1 or 2, M + n + q is equal to the oxidation state of the metal M; when m is greater than 1, a plurality of LaThe same or different; when n is 2, two LbThe same or different; when q is 2, two LcThe same or different;
La、Lband LcOptionally linked to form a multidentate ligand; such as La、LbAnd LcOptionally linked to form a tetradentate or hexadentate ligand; l isa、LbAnd LcOr may be all unconnected so as not to form more than oneA dentate ligand;
Lband LcEach occurrence, the same or different, is selected from the group consisting of:
wherein R isa、RbAnd RcThe same or different at each occurrence indicates mono-, poly-, or no substitution;
Xbeach occurrence, the same or different, is selected from the group consisting of: o, S, Se, NRN1And CRC1RC2；
XcAnd XdEach occurrence, the same or different, is selected from the group consisting of: o, S, Se and NRN2；
Ra、Rb、Rc、RN1、RN2、RC1And RC2Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, substituted or unsubstituted amine groups having 0-20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;
wherein the adjacent substituents Ra、Rb、Rc、RN1、RN2、RC1And RC2Can optionally be linked to form a ring.
In this example, the adjacent substituents Ra、Rb、Rc、RN1、RN2、RC1And RC2Can optionally be linked to form a ring, is intended to mean a group in which adjacent substituents are present, for example two substituents RaIn between, two substituents RbIn between, two substituents RcOf a substituent RaAnd RbOf a substituent RaAnd RcOf a substituent RbAnd RcOf R is a substituentaAnd RN1Of a substituent RbAnd RN1Of a substituent RaAnd RC1Of a substituent RaAnd RC2Of R is a substituentbAnd RC1Of R is a substituentbAnd RC2Of a substituent RaAnd RN2Of a substituent RbAnd RN2And R isC1And RC2And any one or more of these substituent groups may be linked to form a ring. Obviously, none of these substituents may be linked to each other to form a ring.
In this embodiment, La、LbAnd LcCan optionally be linked to form a multidentate ligand, intended to denote La、LbAnd LcAny two or three of which can be linked to form a tetradentate or hexadentate ligand. Obviously, La、LbAnd LcOr none may be linked so as to form no polydentate ligand.
According to one embodiment of the invention, wherein the metal M is selected from Ir, Rh, Re, Os, Pt, Au or Cu.
According to one embodiment of the invention, wherein the metal M is selected from Ir, Pt or Os.
According to one embodiment of the invention, wherein the metal M is Ir.
According to an embodiment of the invention, wherein LbEach occurrence, identically or differently, is selected from the following structures:
wherein R is1–R7Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, substituted or unsubstituted amine groups having 0-20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof.
According to an embodiment of the invention, wherein LbEach occurrence, identically or differently, is selected from the following structures:
wherein R is1-R3At least one is selected from the group consisting of substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having 1 to 20 carbon atoms, or combinations thereof; and/or R4-R6At least one of which is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, or combinations thereof.
According to an embodiment of the present invention, wherein,Lbeach occurrence, identically or differently, is selected from the following structures:
wherein R is1-R3At least two of which are selected from substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having 1 to 20 carbon atoms, or combinations thereof; and/or R4-R6At least one of which is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, or combinations thereof.
According to an embodiment of the invention, wherein LbEach occurrence, identically or differently, is selected from the following structures:
wherein R is1-R3At least two of which are selected from substituted or unsubstituted alkyl groups having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having 2 to 20 carbon atoms, or combinations thereof; and/or R4-R6At least two of which are selected from substituted or unsubstituted alkyl groups having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having 2 to 20 carbon atoms, or combinations thereof.
According to an embodiment of the invention, wherein LbEach occurrence being selected identically or differently from Lb1To Lb322Group of (I) LcEach occurrence being selected identically or differently from Lc1To Lc231A group of (a); said Lb1To Lb322And Lc1To Lc231See claim 18 for specific structure of (a).
According to one embodiment of the invention, wherein the metal complex has Ir (L)a)2(Lb) Or Ir (L)a)2(Lc) Or Ir (L)a)(Lc)2The structure of (1);
wherein when the metal complex has Ir (L)a)2(Lb) In the structure of (1), LaEach occurrence being selected identically or differently from La1To La1706Any one or any two of the group consisting of, LbIs selected from the group consisting of Lb1To Lb322Any one of the group consisting of; when the metal complex has Ir (L)a)2(Lc) In the structure of (1), LaEach occurrence being selected identically or differently from La1To La1706Any one or any two of the group consisting of, LcIs selected from the group consisting of Lc1To Lc231Any one of the group consisting of; when the metal complex has Ir (L)a)(Lc)2In the structure of (1), LaIs selected from the group consisting of La1To La1706Any one of the group consisting of LcEach occurrence being selected identically or differently from Lc1-Lc231Any one or any two of the group consisting of.
According to one embodiment of the present invention, wherein the metal complex has Ir (L)a)2(Lb) Or Ir (L)a)2(Lc) Or Ir (L)a)(Lc)2The structure of (1);
wherein when the metal complex has Ir (L)a)2(Lb) In the structure of (1), LaEach occurrence being selected identically or differently from La1To La1803Any one or any two of the group consisting of, LbIs selected from the group consisting of Lb1To Lb322Any one of the group consisting of; when the metal complex has Ir (L)a)2(Lc) In the structure of (1), LaEach occurrence being selected identically or differently from La1To La1803Any one or any two of the group consisting of, LcIs selected from the group consisting of Lc1To Lc231Any one of the group consisting of; when the metal complex has Ir (L)a)(Lc)2In the structure of (1), LaIs selected from the group consisting of La1To La1803Any one of the group consisting of LcEach occurrence, identically or differently, of a group selected from Lc1-Lc231Any one or any two of the group consisting of.
According to one embodiment of the invention, wherein the metal complex has Ir (L)a)2(Lb) Or Ir (L)a)2(Lc) Or Ir (L)a)(Lc)2The structure of (1);
wherein when the metal complex has Ir (L)a)2(Lb) In the structure of (1), LaEach occurrence being selected identically or differently from La1To La1931Any one or any two of the group consisting of, LbIs selected from the group consisting of Lb1To Lb322Any one of the group consisting of; when the metal complex has Ir (L)a)2(Lc) In the structure of (1), LaEach occurrence being selected identically or differently from La1To La1931Any one or any two of the group consisting of, LcIs selected from the group consisting of Lc1To Lc231Any one of the group consisting of; when the metal complex has Ir (L)a)(Lc)2In the structure of (1), LaIs selected from the group consisting of La1To La1931Any one of the group consisting of LcEach occurrence being selected identically or differently from Lc1-Lc231Any one or any two of the group consisting of.
According to an embodiment of the present invention, wherein the metal complex is selected from the group consisting of compound 1 to compound 260; the specific structures of the compound 1 to the compound 260 are shown in claim 19.
According to an embodiment of the present invention, wherein the metal complex is selected from the group consisting of compound 1 to compound 290; the specific structures of the compound 1 to the compound 290 are shown in claim 19.
According to an embodiment of the present invention, wherein the metal complex is selected from the group consisting of compound 1 to compound 312; the specific structures of the compound 1 to the compound 312 are shown in claim 19.
According to an embodiment of the present invention, there is also disclosed an electroluminescent device, including:
an anode, a cathode, a anode and a cathode,
a cathode electrode, which is provided with a cathode,
and an organic layer disposed between the anode and the cathode, the organic layer comprising a metal complex comprising a ligand La，LaHas a structure represented by formula 1:
wherein, ring A and ring B are each independently selected from five-membered unsaturated carbocyclic ring, aromatic ring with 6-30 carbon atoms or heteroaromatic ring with 3-30 carbon atoms;
Rithe same or different at each occurrence represents mono-, poly-, or no substitution; riiThe same or different at each occurrence represents mono-, poly-, or no substitution;
y is selected from SiRyRy，GeRyRy，NRy，PRyO, S or Se;
when two R are simultaneously presentyWhen two R are presentyMay be the same or different;
X1-X2selected from CR, identically or differently at each occurrencexOr N;
R、Ri、Rii、Rxand RyEach occurrence, identically or differently, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy, amino, or amino, or amino, or amino, or amino, or amino acids, or other substituted, or other combinations thereof, or other compounds orSubstituted or unsubstituted aryloxy having from 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having from 2 to 20 carbon atoms, substituted or unsubstituted aryl having from 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having from 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having from 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having from 6 to 20 carbon atoms, substituted or unsubstituted amine having from 0 to 20 carbon atoms, acyl, carbonyl, carboxylic acid group, ester group, cyano, isocyano, mercapto, sulfinyl, sulfonyl, phosphino, and combinations thereof;
adjacent substituents Ri、Rx、RyR and RiiCan optionally be linked to form a ring;
the metal is selected from metals having a relative atomic mass greater than 40.
According to an embodiment of the present invention, in the electroluminescent device, the organic layer is a light-emitting layer, and the metal complex is a light-emitting material.
According to one embodiment of the invention, the electroluminescent device emits red light.
According to one embodiment of the invention, the electroluminescent device emits white light.
According to one embodiment of the present invention, in the electroluminescent device, the organic layer is a light-emitting layer, and the light-emitting layer further includes at least one host material.
According to an embodiment of the invention, in the electroluminescent device, the at least one host material comprises at least one chemical group selected from the group consisting of: benzene, pyridine, pyrimidine, triazine, carbazole, azacarbazole, indolocarbazole, dibenzothiophene, azadibenzothiophene, dibenzofuran, azadibenzofuran, dibenzoselenophene, triphenylene, azatriphenylene, fluorene, silafluorene, naphthalene, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene, azaphenanthrene, and combinations thereof.
According to another embodiment of the invention, the invention also discloses a compound combination which comprises a metal complex, wherein the specific structure of the metal complex is shown in any one of the embodiments.
In combination with other materials
The materials described herein for use in particular layers in an organic light emitting device may be used in combination with various other materials present in the device. Combinations of these materials are described in detail in U.S. patent application Ser. No. 0132-0161 of U.S. 2016/0359122A1, the entire contents of which are incorporated herein by reference. The materials described or referenced therein are non-limiting examples of materials that may be used in combination with the compounds disclosed herein, and one skilled in the art can readily review the literature to identify other materials that may be used in combination.
Materials described herein as being useful for particular layers in an organic light emitting device can be used in combination with a variety of other materials present in the device. For example, the light emitting dopants disclosed herein may be used in conjunction with a variety of hosts, transport layers, barrier layers, injection layers, electrodes, and other layers that may be present. Combinations of these materials are described in detail in U.S. patent application Ser. No. US2015/0349273A1, paragraph 0080-0101, the entire contents of which are incorporated herein by reference. The materials described or referenced therein are non-limiting examples of materials that may be used in combination with the compounds disclosed herein, and one skilled in the art can readily review the literature to identify other materials that may be used in combination.
In the examples of material synthesis, all reactions were carried out under nitrogen unless otherwise stated. All reaction solvents were anhydrous and used as received from commercial sources. The synthesis product is subjected to structural validation and characterization using one or more equipment conventional in the art (including, but not limited to, Bruker's nuclear magnetic resonance apparatus, Shimadzu's liquid chromatograph-mass spectrometer, gas chromatograph-mass spectrometer, differential scanning calorimeter, Shanghai prism-based fluorescence spectrophotometer, Wuhan Corset's electrochemical workstation, Anhui Beidek's sublimator, etc.) in a manner well known to those skilled in the art. In an embodiment of the device, the device characteristics are also tested using equipment conventional in the art (including, but not limited to, an evaporator manufactured by Angstrom Engineering, an optical test system manufactured by Fushida, Suzhou, an ellipsometer manufactured by Beijing Mass., etc.) in a manner well known to those skilled in the art. Since the relevant contents of the above-mentioned device usage, testing method, etc. are known to those skilled in the art, the inherent data of the sample can be obtained with certainty and without being affected, and therefore, the relevant contents are not described in detail in this patent.
Materials synthesis example:
the preparation method of the compound of the present invention is not limited, and the following compounds are typically but not limited to, and the synthetic route and the preparation method thereof are as follows:
synthesis example 1: synthesis of Compound 81
Step 1: synthesis of intermediate 2
5g of starting material 1(24.03mmol) was dissolved in 50mL of DCM, 5.39g (1.3eq, 31.24mmol) of m-CPBA (m-chloroperoxybenzoic acid) was added at RT, stirred for 24h, TLC indicated disappearance of starting material, solvent was removed in vacuo and crude intermediate 2 was used directly in the next reaction.
And 2, step: synthesis of intermediate 3
Dissolving the intermediate 2 obtained in the step 1 in 24mL of phosphorus oxychloride, heating to 100 ℃, stirring for 3h, cooling to 0 ℃, slowly adding an aqueous solution of NaOH dropwise until the pH value is 9, extracting with DCM for three times (50mL of 3), combining organic phases, washing with a saturated aqueous solution of sodium chloride, drying over anhydrous magnesium sulfate, and removing the solvent in vacuum. Column chromatography (PE: EA ═ 30:1) gave 1.98g of intermediate 3 in 34% yield over two steps.
And step 3: synthesis of intermediate 5
3g (18.96mmol) of intermediate 4 are dissolved in 30mL of anhydrous tetrahydrofuran, the temperature is reduced to-78 ℃, n-BuLi (1M, 22.75mL) (1.2eq, 22.75mmol) is slowly added dropwise under nitrogen atmosphere, the temperature is raised to room temperature after the dropwise addition is finished, and the mixture is stirred for 1 h. The temperature was reduced to-78 ℃ and 4.63g (1.3eq, 24.65mmol) of 1, 2-dibromoethane was slowly added dropwise thereto, after the addition was complete, the mixture was warmed to room temperature and stirred overnight. The reaction was quenched with saturated ammonium chloride, extracted three times with EA (40mL x 3), the organic phases combined, washed with saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate and the solvent removed in vacuo. Column chromatography (PE: EA ═ 100:1) gave 3.82g of intermediate 5 in 85% yield.
And 4, step 4: synthesis of intermediate 6
2.5g of intermediate 5(10.57mmol), 0.387g of PdCl2(dppf) (0.05eq, 0.53mmol), 1.56g of AcOK (1.5eq, 15.85mmol), 3.22g of B2Pin2(pinacol diboron) (1.2eq, 12.68mmol) was dissolved in 30mL of 1, 4-dioxane, heated to 80 ℃ and stirred overnight. Cooling to room temperature, removal of the solvent in vacuo and purification by column chromatography (PE: EA ═ 20:1) gave 2.21g of intermediate 6 as a white solid in 74% yield.
And 5: synthesis of intermediate 7
3.93g of intermediate 6(1.2eq, 13.85mmol), 2.78g of intermediate 3(1eq, 11.54mmol) and 0.387g of Pd (PPh)3)4(0.05eq，0.58mmol)、1.83g Na2CO3(1.5eq, 17.31mmol) was dissolved in 30mL of 1, 4-dioxane and 10mL of water, heated to 90 ℃ and stirred overnight. Cooling to room temperature, removal of the solvent in vacuo and purification by column chromatography (PE: EA ═ 50:1) gave 3g of intermediate 7 as a white solid in 72% yield.
Step 6: synthesis of intermediate 8
3.03g of intermediate 7(8.32mmol) are dissolved in 30mL of DCM, the temperature is reduced to 0 ℃, and BBr is slowly added dropwise under nitrogen atmosphere3Stirred for 2h, NaHCO3The reaction was quenched with aqueous solution, extracted with DCM (60mL x 3), the organic phases combined, washed with saturated aqueous sodium chloride, dried over anhydrous magnesium sulphate and the solvent removed in vacuo. Column chromatography (PE: EA ═ 4:1) gave 1.17g of intermediate 8 in 40% yield.
And 7: synthesis of intermediate 9
1.2g of intermediate 8(1eq, 3.33mmol), 24mg of CuBr (0.05eq, 0.17mmol) and 2.82g of K were added3PO4(4eq, 13.3mmol) was dissolved in 15mL of DMF, heated to 90 ℃ and stirred overnight. Cool to room temperature, dilute with water, precipitate, filter through celite, and wash the solid with 1L of DCM. Yield 0.81g of intermediate 9 was obtained in 90% yield. The resulting yellow solid intermediate 9 was recrystallized from toluene to give a solid intermediate 9 having a purity of 99.7%.
And 8: synthesis of Iridium dimer
1.2g (3eq, 4.45mmol) of intermediate 9 were dissolved in 24mL of 2-ethoxyethanol and 8mL of water at room temperature, and 523mg of IrCl was added3·3H2O (1eq, 1.48mmol), was ventilated three times at room temperature, heated to 130 ℃ and refluxed at this temperature for 24 hours, and cooled to room temperature. And (3) filtering, washing the solid with ethanol until the washing liquid is colorless, and performing suction filtration for about 15 minutes until the ethanol on the solid completely disappears to obtain 1.13g of red solid iridium dimer, wherein the yield is 99%, and the red solid iridium dimer is directly used for the next reaction without purification.
And step 9: synthesis of Compound 81
1.13g of the iridium dimer (1eq, 0.74mmol) obtained in step 8 was charged to a 100mL round-bottomed flask, and 510mg of K was added2CO3(5eq, 3.7mmol) and 0.74g of 3, 7-diethyl-3-methyl-4, 6-nonanedione (4eq, 2.96mmol) were replaced with nitrogen at room temperature three times, stirred under nitrogen for 24 hours, filtered through celite, and the solid was washed with ethanol until the wash was colorless, filtered with suction for about 15 minutes, and the ethanol adsorbed on the solid was removed. The red solid on top of the celite was dissolved in 200mL of dichloromethane with vacuum filtration, 20mL of ethanol was added to the flask, dichloromethane was removed in vacuo, the product precipitated in the remaining ethanol, filtered and the solid adsorbed ethanol was drained. Purification by silica gel column chromatography (PE: DCM ═ 10:1), dissolving the crude solid in 200mL of dichloromethane, adding 20mL of ethanol, removing dichloromethane in vacuo, precipitating the product in the remaining ethanol, filtering, and drying the ethanol adsorbed on the solid to obtain compound 81 as a red solid (mass 1.13g, yield 80%). The purity is 99.6%. The product was identified as the target product, molecular weight 954.3.
Synthesis example 2: synthesis of Compound 83
Step 1: synthesis of intermediate 11:
intermediate 10(7.6g,35.1mmol) was dissolved in 70mL of ultra-dry tetrahydrofuran, then the reaction was cooled to 0 ℃, then an n-butyllithium solution (15.5mL, 38.7mmol) was added dropwise thereto under nitrogen, the temperature was kept for 1h after completion of the dropwise addition, then isopropanol pinacol borate (iPrOBpin, 8.49g, 45.6mmol) was added thereto, the reaction was allowed to warm to room temperature for 2h after completion of the addition, and then a saturated ammonium chloride solution was added thereto to quench the reaction. Ethyl acetate was then added to the reaction, the layers were separated, the aqueous phase was extracted with ethyl acetate, the organic phases were combined, dried and spin-dried to give a crude product, which was separated by silica gel column chromatography (eluent ethyl acetate: petroleum ether: 1:50, v/v) to give the desired product, intermediate 11(4.7g, 39.1%) as a colorless oily liquid.
Step 2: synthesis of intermediate 13:
intermediate 12(3.19g,13.7mmol), intermediate 11(4.7g,13.7mmol), tetrakistriphenylphosphine palladium (0.8g, 0.69mmol), sodium carbonate (2.18g, 20.55mmol), 1, 4-dioxane (60mL) and water (15mL) were added to a 250mL round bottom flask, and the reaction was heated to 80 ℃ under nitrogen blanket and stirred overnight, cooled to room temperature after TLC indicated completion of the reaction. Ethyl acetate was then added to the reaction, the layers were separated, the aqueous phase was extracted with ethyl acetate, the organic phases were combined, dried and spin-dried to give a crude product, which was separated by silica gel column chromatography (eluent ethyl acetate: petroleum ether ═ 1:10, v/v) to give intermediate 13(3.5g, 73.0%) as a white solid as the desired product.
And 3, step 3: synthesis of intermediate 14:
intermediate 13(4.1g,10mmol) was dissolved in 20mL of ethanol, followed by the addition of 2M HCl 20mL thereto, then the reaction was heated to reflux with stirring overnight and cooled to room temperature after TLC showed completion of the reaction. Then, saturated sodium carbonate solution was added thereto to adjust the pH to neutral, and a large amount of yellow solid was precipitated in the solution, which was filtered, washed several times with water, and then drained to obtain the objective product, intermediate 14(3.3g, 93.2%) as a yellow solid.
And 4, step 4: synthesis of intermediate 15:
intermediate 14(3.3g,9.3mmol), cuprous bromide (133mg, 0.9mmol), 2,2,6, 6-tetramethylheptanedione (1.37g, 7.44mmol), cesium carbonate (7.6g, 23.25mmol) and DMF (90mL) were heated to 135 ℃ under nitrogen blanket for reaction overnight, and cooled to room temperature after TLC indicated completion of the reaction. 200mL of water was added to the reaction solution until a large amount of yellow solid precipitated out, and the solid was filtered, washed with water several times and then drained to obtain the desired product, intermediate 15(3.10g, 96%) as a yellow solid.
And 5: synthesis of intermediate 16:
intermediate 15(3.42g,10.8mmol), isobutylboronic acid (2.2g, 21.6mmol), palladium acetate (121mg, 0.54mmol), Sphos (443mg, 1.08mmol), potassium phosphate trihydrate (8.63g, 32.4mmol) and toluene (80mL) were heated to reflux under nitrogen overnight and cooled to room temperature after TLC showed completion of the reaction. The crude product was separated by silica gel column chromatography (eluent ethyl acetate: petroleum ether 1:30, v/v) to give the desired product, intermediate 16(1.8g, 49.4%), as a yellow solid.
Step 6: synthesis of iridium dimer:
a mixture of intermediate 16(1.8g, 5.3mmol), iridium trichloride trihydrate (628mg, 1.78mmol), 2-ethoxyethanol (21mL) and water (7mL) was refluxed under nitrogen for 24 hours. After cooling to room temperature, the water was carefully removed from the solution by rotary evaporation to give a solution of dimer in ethoxyethanol, which was used in the next reaction without further purification.
And 7: synthesis of Compound 83
A solution of iridium dimer, 3.7-diethyl-3-methylnonane-4, 6-dione (663mg, 2.67mmol) and potassium carbonate (1.23g, 8.9mmol) were charged into a 100mL round-bottomed flask and reacted at 60 ℃ for 24 hours under nitrogen. It was then poured into a funnel with celite, filtered and washed with ethanol. Methylene chloride was added to the resulting solid and the filtrate was collected. Ethanol was then added and the resulting solution was concentrated, but not dried. After filtration 1.1g of the product compound 83 is obtained, yield 57%. The product was further purified by column chromatography. The structure of the compound was confirmed by NMR and LC-MS to be the target product, molecular weight 1094.5.
Synthetic example 3: synthesis of Compound 64
Step 1: synthesis of intermediate 18
Intermediate 17(2.93g, 12.54mmol), intermediate 11(3.9g, 11.4mmol), Pd (dppf) Cl2(439mg, 0.6mmol) and K2CO3(4.73g, 34.2mmol) was mixed with dioxane/water (42mL/14mL), and after replacement of nitrogen, the reaction was allowed to proceed overnight at room temperature. After filtration through celite, EA was added thereto and extracted three times, the organic phases were combined, concentrated and subjected to column chromatography to give intermediate 18(3g, yield 63.7%).
Step 2: synthesis of intermediate 20
Intermediate 18(3.8g, 9.2mmol) was added to a mixture of 12N HCl (7.6mL) and MeOH (20mL) and reacted at 54 deg.C for 2 hours, after completion of the TLC check, cooled to room temperature, to which saturated NaHCO was added3The Ph of the solution was adjusted to about 7-8, extracted three times with EA, the organic phases were combined, washed with saturated aqueous sodium chloride solution and concentrated to give the crude intermediate 19, which was used directly in the next reaction without further purification. The crude intermediate 19 (2.6g, 7.2mmol), CuBr (103mg, 0.72mmol), 22,6, 6-tetramethyl-3, 5-heptanedione (1.06g, 5.76mmol) and Cs2CO3(5.87g, 18mmol) was mixed in DMF (72mL) and after displacement of nitrogen, the reaction was allowed to proceed overnight, cooled to room temperature and the product was filtered off, the filter cake was washed with appropriate amount of DMF and then EtOH and PE, and dried to give intermediate 20(1.85g, 63% over two steps).
And step 3: synthesis of intermediate 21
Intermediate 20(1.85g, 5.82mmol), isobutylboronic acid (1.19g, 11.64mmol), Pd (OAc)2(65mg, 0.29mmol), sphos (238mg, 0.58mmol) and K3PO4·3H2O (4.66g, 17.5mmol) was mixed in toluene (58mL) and the reaction refluxed at 120 ℃ under nitrogen. After the intermediate 21 was completely converted by HPLC, it was cooled to room temperature, and the reaction solution was filtered through celite, concentrated and subjected to column chromatography to give intermediate 21(1.3g of yellow solid, yield 66%).
And 4, step 4: synthesis of compound 64:
intermediate 21(825mg,2.42mmol), IrCl3·3H2O (286mg, 0.81mmol), ethoxyethanol (11.5mL) and water (3.5mL) were weighed into a 100mL single-neck flask, replaced with nitrogen, reacted at 130 ℃ under reflux for 24 hours, after the reaction cooled to room temperature, the resulting precipitate was filtered off, the filter cake was washed with ethanol and dried, and the resulting iridium dimer was reacted with 3, 7-diethyl-1, 1, 1-trifluorononane-4, 6-dione (319mg,1.2mmol), K2CO3(560mg, 4.05mmol) and ethoxyethanol (13mL) were mixed in a 100mL single-necked flask, and after replacement of nitrogen, the reaction was allowed to proceed overnight at room temperature, and after completion of the reaction was monitored by TLC, the stirring was stopped. The reaction solution was filtered through celite, the filter cake was washed with a suitable amount of EtOH, the crude product was washed with DCM into a 250mL eggplant-shaped bottle, EtOH (about 5mL) was added thereto, DCM was removed by swirling at room temperature, and a solid was seenPrecipitated, which was filtered off and washed with an appropriate amount of EtOH to give compound 64(80mg, yield 8.7%) as a product. The product was identified as the target product, molecular weight 1136.4.
Synthetic example 4: synthesis of Compound 93
Step 1: synthesis of iridium dimer:
a mixture of intermediate 22(0.76g, 1.92mmol), iridium trichloride trihydrate (226mg, 0.64mmol), 2-ethoxyethanol (7.5mL) and water (2.5mL) was refluxed under nitrogen for 24 hours. After cooling to room temperature, the water in the solution was carefully removed by rotary evaporation to give an ethoxyethanol solution of iridium dimer, which was used in the next reaction without further purification.
Step 2: synthesis of Compound 93
The iridium dimer solution in ethoxyethanol obtained in the previous step, 3.7-diethyl-3-methylnonane-4, 6-dione (450mg, 1.84mmol) and potassium carbonate (0.64g, 4.45mmol) were added to a 25mL round-bottomed flask and reacted at 50 ℃ for 24 hours under nitrogen. It was then poured into a funnel with celite, filtered and washed with ethanol. Methylene chloride was added to the resulting solid and the filtrate was collected. Ethanol was then added and the resulting solution was concentrated, but not dried. After filtration 550mg of the product compound 93 is obtained with a yield of 71%. The structure of the compound was confirmed by LC-MS to be the target product, molecular weight 1206.6.
Synthesis example 5: synthesis of Compound 117
Step 1: synthesis of iridium dimer:
intermediate 23(2.1g,5.56mmol), iridium trichloride trihydrate (494mg, 1.4mmol), ethoxyethanol (18mL) and water (6mL) were weighed into a 250mL single neck flask, nitrogen was replaced, the reaction was refluxed at 130 ℃ for 24 hours, after the reaction was cooled to room temperature, the resulting precipitate was filtered off, the filter cake was washed with ethanol and dried to obtain iridium dimer, which was used directly in the next reaction without further purification.
And 2, step: synthesis of compound 117:
the iridium dimer thus obtained was mixed with 3, 7-diethyl-3, 7-dimethyl-4, 6-nonanedione (421mg, 1.75mmol), potassium carbonate (1.94mg, 14mmol) and ethoxyethanol (24mL) in a 100mL single-necked flask, and after replacement of nitrogen, the reaction was carried out overnight at 55 ℃ while the stirring was stopped after completion of the TLC monitoring. Filtering the reaction solution by using diatomite, washing a filter cake by using a proper amount of ethanol, washing a crude product into a 250mL eggplant-shaped bottle by using dichloromethane, adding ethanol (about 5mL) into the eggplant-shaped bottle, carrying out rotary evaporation at normal temperature to remove dichloromethane, thus obtaining a solid which is separated out, filtering the solid, washing the solid by using a proper amount of ethanol, drying the solid, dissolving the solid in dichloromethane, and carrying out column chromatography after concentration to obtain a red solid compound 117(1g, the yield is 60%) with the purity of 99.4%. The structure of the compound was confirmed by LC-MS to be the target product, molecular weight 1192.6.
Synthetic example 6: synthesis of Compound 116
Step 1: synthesis of iridium dimer:
a mixture of intermediate 24(1.37g, 3.73mmol), iridium trichloride trihydrate (329mg, 0.93mmol), 2-ethoxyethanol (12mL) and water (4mL) was refluxed under nitrogen for 24 hours. After cooling to room temperature, red solid iridium dimer was obtained by filtration and used in the next reaction without further purification.
Step 2: synthesis of compound 116:
the iridium dimer obtained in the previous step, 3.7-diethyl-3, 7-dimethylnonane-4, 6-dione (430mg, 1.79mmol) and potassium carbonate (0.62g, 4.48mmol) were charged into a 50mL round-bottomed flask and reacted at 50 ℃ for 24 hours under nitrogen. It was then poured into a funnel with celite, filtered and washed with ethanol. Methylene chloride was added to the resulting solid and the filtrate was collected. Ethanol was then added and the resulting solution was concentrated, but not dried. After filtration 810mg of the product compound 116 are obtained in 82.2% yield. The structure of the compound was confirmed by LC-MS to be the target product, molecular weight 1164.5.
Synthetic example 7: synthesis of Compound 261
Step 1: synthesis of iridium dimer:
a mixture of intermediate 25(0.76g, 1.92mmol), iridium trichloride trihydrate (226mg, 0.64mmol), 2-ethoxyethanol (7.5mL) and water (2.5mL) was refluxed under nitrogen for 24 hours. After cooling to room temperature, the water in the solution was carefully removed by rotary evaporation to give an ethoxyethanol solution of iridium dimer, which was used in the next reaction without further purification.
Step 2: synthesis of compound 261:
the iridium dimer solution in ethoxyethanol obtained in the above step, 3, 7-diethyl-3, 7-dimethylnonane-4, 6-dione (450mg, 1.84mmol) and potassium carbonate (0.64g, 4.45mmol) were added to a 25mL round-bottomed flask and reacted at 50 ℃ for 24 hours under nitrogen. It was then poured into a funnel with celite, filtered and washed with ethanol. Methylene chloride was added to the resulting solid and the filtrate was collected. Ethanol was then added and the resulting solution was concentrated, but not dried. After filtration, 1.75g of product compound 261 are obtained, yield 96%. The structure of the compound was confirmed by LC-MS to be the target product, molecular weight 1220.6.
Synthesis example 8: synthesis of Compound 262
Step 1: synthesis of iridium dimer:
a mixture of intermediate 26(0.76g, 1.92mmol), iridium trichloride trihydrate (226mg, 0.64mmol), 2-ethoxyethanol (7.5mL) and water (2.5mL) was refluxed under nitrogen for 24 hours. After cooling to room temperature, the water in the solution was carefully removed by rotary evaporation to give an ethoxyethanol solution of iridium dimer, which was used in the next reaction without further purification.
Step 2: synthesis of compound 262:
the iridium dimer in ethoxyethanol solution obtained in the above step, 3.7-diethyl-1, 1, 1-trifluorononane-4, 6-dione (450mg, 1.84mmol) and potassium carbonate (0.64g, 4.45mmol) were charged in a 25mL round-bottomed flask and reacted at 50 ℃ for 24 hours under nitrogen. It was then poured into a funnel with celite, filtered and washed with ethanol. Methylene chloride was added to the resulting solid and the filtrate was collected. Ethanol was then added and the resulting solution was concentrated, but not dried. After filtration, 1.35g of the product compound 262 is obtained, with a purity of 98.86% and a yield of 92%. The structure of the compound was confirmed by LC-MS to be the target product, molecular weight 1246.5.
Synthetic example 9: synthesis of Compound 264
Step 1: synthesis of iridium dimer:
intermediate 27(800mg,2.1mmol), iridium trichloride trihydrate (250mg, 0.7mmol), ethoxyethanol (7.5mL) and water (2.5mL) were charged into a 100mL single-neck flask, nitrogen was replaced, the reaction was refluxed at 130 ℃ for 24 hours, after the reaction was cooled, the solvent was concentrated and dried by spinning to obtain an iridium dimer, which was used in the next reaction without further purification.
And 2, step: synthesis of compound 264:
adding 3, 7-diethyl-3, 7-dimethylnonane-4, 6-dione (337mg, 1.4mmol), potassium carbonate (967mg, 7mmol) and ethoxyethanol (14mL) into the iridium dimer obtained in the above step, replacing nitrogen, reacting at room temperature for 48 hours, filtering the reaction solution with diatomaceous earth, washing the filter cake with an appropriate amount of ethanol, washing the crude product with dichloromethane into a 250mL eggplant-shaped bottle, adding ethanol (about 5mL) into the bottle, removing dichloromethane by rotary evaporation at room temperature to obtain a solid, filtering out the solid, washing with an appropriate amount of ethanol again, drying, dissolving in dichloromethane, concentrating, and purifying by column chromatography to obtain compound 264(570 mg). The structure of the compound was confirmed by LC-MS to be the target product, molecular weight 1192.6.
Synthetic example 10: synthesis of Compound 263
Step 1: synthesis of iridium dimer:
a mixture of intermediate 28(0.46g, 1.28mmol), iridium trichloride trihydrate (130mg, 0.37mmol), 2-ethoxyethanol (4.5mL) and water (1.5mL) was refluxed under nitrogen for 24 hours. After cooling to room temperature, red solid iridium dimer was obtained by filtration and used in the next reaction without further purification.
Step 2: synthesis of compound 263:
the iridium dimer obtained in the previous step, 3.7-diethyl-3, 7-dimethylnonane-4, 6-dione (133mg, 0.55mmol) and potassium carbonate (0.25g, 1.84mmol) were charged into a 50mL round-bottomed flask and reacted at 40 ℃ for 24 hours under nitrogen. It was then poured into a funnel with celite, filtered and washed with ethanol. Methylene chloride was added to the resulting solid and the filtrate was collected. Ethanol was then added and the resulting solution was concentrated, but not dried. After filtration, 300mg of product compound 263 is obtained, yield 73.7%. The structure of the compound was confirmed by LC-MS to be the target product, molecular weight 1164.5.
Synthetic example 11: synthesis of Compound 266
Step 1: synthesis of iridium dimer:
a mixture of intermediate 29(1.45g, 3.42mmol), iridium trichloride trihydrate (346mg, 0.98mmol), 2-ethoxyethanol (12mL) and water (4mL) was refluxed under nitrogen for 24 hours. After cooling to room temperature, red solid iridium dimer was obtained by filtration and used in the next reaction without further purification.
Step 2: synthesis of compound 266:
the iridium dimer (0.67g, 0.31mmol), 3, 7-diethyl-3-methylnonane-4, 6-dione (0.21g, 0.94mmol) and potassium carbonate (0.43g, 3.1mmol) obtained in the previous step were dissolved in 9mL of ethoxyethanol and reacted at 40 ℃ for 24 hours under nitrogen. It was then poured into a funnel with celite, filtered and washed with ethanol. Methylene chloride was added to the resulting solid and the filtrate was collected. Ethanol was then added and the resulting solution was concentrated, but not dried. After filtration, 370mg of compound 266 were obtained in 47.3% yield. The structure of the compound was confirmed by LC-MS to be the target product, molecular weight 1262.6.
Synthetic example 12: synthesis of Compound 265
Step 1: synthesis of compound 265:
iridium dimer (0.67g, 0.31mmol), intermediate 30(0.21g, 0.94mmol) and potassium carbonate (0.43g, 3.1mmol) were dissolved in 9mL of ethoxyethanol and reacted at 40 ℃ for 24 hours under nitrogen. It was then poured into a funnel with celite, filtered and washed with ethanol. Methylene chloride was added to the resulting solid and the filtrate was collected. Ethanol was then added and the resulting solution was concentrated, but not dried. After filtration 370mg of compound 265 are obtained with a yield of 47.3%. The structure of the compound was confirmed by LC-MS to be the target product, molecular weight 1302.6.
Synthetic example 13: synthesis of Compound 267
Step 1: synthesis of iridium dimer:
a mixture of intermediate 31(0.6g, 1.68mmol), iridium trichloride trihydrate (198mg, 0.56mmol), 2-ethoxyethanol (7.5mL) and water (2.5mL) was refluxed under nitrogen for 24 hours. After cooling to room temperature, red solid iridium dimer was obtained by filtration and used in the next reaction without further purification.
And 2, step: synthesis of compound 267:
the iridium dimer obtained in the above step, 3, 7-diethyl-3, 7-dimethylnonane-4, 6-dione (270mg, 1.12mmol) and potassium carbonate (0.77g, 5.6mmol) were charged into a 25mL round-bottomed flask and reacted at 50 ℃ for 24 hours under nitrogen. It was then poured into a funnel with celite, filtered and washed with ethanol. Methylene chloride was added to the resulting solid and the filtrate was collected. Ethanol was then added and the resulting solution was concentrated, but not dried. After filtration, 0.4g of crude product is obtained, 91.6% pure, which is further purified by column chromatography to yield 0.3g of the final product compound 267 in 47% yield. The structure of the compound was confirmed by LC-MS to be the target product, molecular weight 1136.5.
Synthesis example 14: synthesis of Compound 269
Step 1: synthesis of Iridium dimer
A mixture of intermediate 32(1.5g, 4.2mmol), iridium trichloride trihydrate (427mg, 1.2mmol), 2-ethoxyethanol (12mL) and water (4mL) was refluxed under nitrogen for 24 hours. After cooling to room temperature, red solid iridium dimer was obtained by filtration and used in the next reaction without further purification.
Step 2: synthesis of Compound 269
The iridium dimer obtained in the previous step, 3, 7-diethyl-3, 7-dimethylnonane-4, 6-dione (580mg, 2.4mmol) and potassium carbonate (0.83g, 6.04mmol) were dissolved in 16mL of ethoxyethanol and reacted at 40 ℃ for 24 hours under nitrogen. It was then poured into a funnel with celite, filtered and washed with ethanol. Methylene chloride was added to the resulting solid and the filtrate was collected. Ethanol was then added and the resulting solution was concentrated, but not dried. After filtration 940mg of compound 269 are obtained in 66% yield. The structure of the compound was confirmed by LC-MS to be the target product, molecular weight 1166.5.
Synthetic example 15: synthesis of Compound 288
Step 1: synthesis of iridium dimer:
a mixture of intermediate 33(1.2g,2.93mmol), iridium trichloride trihydrate (427mg, 1.2mmol), 2-ethoxyethanol (12mL) and water (4mL) was refluxed under nitrogen for 24 hours. After cooling to room temperature, red solid iridium dimer was obtained by filtration and used in the next reaction without further purification.
Step 2: synthesis of compound 288:
the iridium dimer (0.67g, 0.31mmol) obtained in the previous step, intermediate 34(414mg, 1.76mmol) and sodium hydroxide (176mg, 4.4mmol) were dissolved in 16mL of ethoxyethanol and reacted at 40 ℃ for 24 hours under nitrogen. It was then poured into a funnel with celite, filtered and washed with ethanol. Methylene chloride was added to the resulting solid and the filtrate was collected. Ethanol was then added and the resulting solution was concentrated, but not dried. After filtration 410mg of compound 288 are obtained with a yield of 27.4%. The structure of the compound was confirmed by LC-MS to be the target product, molecular weight 1248.6.
Synthetic example 16: synthesis of Compound 273
Step 1: synthesis of iridium dimer:
a mixture of intermediate 35(1.3g, 3.54mmol), iridium trichloride trihydrate (204mg, 0.58mmol), 2-ethoxyethanol (18mL) and water (6mL) was refluxed under nitrogen for 24 hours. After cooling to room temperature, red solid iridium dimer was obtained by filtration and used in the next reaction without further purification.
Step 2: synthesis of compound 273:
the iridium dimer obtained in the above step, 3, 7-diethyl-3, 7-dimethylnonane-4, 6-dione (0.21g, 0.87mmol) and potassium carbonate (0.40g, 2.9mmol) were charged into a 100mL round-bottomed flask and reacted at 50 ℃ for 24 hours under nitrogen. It was then poured into a funnel with celite, filtered and washed with ethanol. Methylene chloride was added to the resulting solid and the filtrate was collected. Ethanol was then added and the resulting solution was concentrated, but not dried. After filtration 0.7g of crude product is obtained, which is further purified by column chromatography to yield 0.6g of compound 273 in 91% yield. The structure of the compound was confirmed by LC-MS to be the target product, molecular weight 1136.5.
Synthetic example 17: synthesis of Compound 282
Step 1: synthesis of iridium dimer:
a mixture of intermediate 36(1.77g,3.87mmol), iridium trichloride trihydrate (390mg, 1.11mmol), 2-ethoxyethanol (24mL) and water (8mL) was refluxed under nitrogen for 24 hours. After cooling to room temperature, red solid iridium dimer was obtained by filtration and used in the next reaction without further purification.
Step 2: synthesis of compound 282:
the iridium dimer obtained in the above step, 3, 7-diethyl-3, 7-dimethylnonane-4, 6-dione (0.4g, 1.66mmol) and potassium carbonate (0.77mg, 5.6mmol) were charged into a 100mL round-bottomed flask and reacted at 50 ℃ for 48 hours under nitrogen. It was then poured into a funnel with celite, filtered and washed with ethanol. Methylene chloride was added to the resulting solid and the filtrate was collected. Ethanol was then added and the resulting solution was concentrated, but not dried. After filtration, 0.7g of crude product is obtained, which is further purified by column chromatography to yield 0.25g of compound 282 in 17% yield. The structure of the compound was confirmed by LC-MS to be the target product, molecular weight 1344.6.
Synthetic example 18: synthesis of Compound 287
Step 1: synthesis of compound 287:
iridium dimer (0.94g, 0.45mmol), 3, 7-diethyl-3, 7-dimethylnonane-4, 6-dione (0.32g, 1.34mmol) and potassium carbonate (0.62mg, 4.45mmol) were dissolved in 25mL of ethoxyethanol and reacted at 40 ℃ for 24 hours under nitrogen. It was then poured into a funnel with celite, filtered and washed with ethanol. Methylene chloride was added to the resulting solid and the filtrate was collected. Ethanol was then added and the resulting solution was concentrated, but not dried. After filtration, 0.87g of compound 287 is obtained in 78% yield. The structure of the compound was confirmed by LC-MS to be the target product, molecular weight 1248.6.
Synthetic example 19: synthesis of Compound 291
Step 1: synthesis of intermediate 38
Intermediate 37(2.68g, 8.69mmol), TMEDA (1.31g, 11.3mmol) were dissolved in 80mL of ultra dry THF, the reaction was cooled to 0 deg.C, then n-butyllithium (4.2mL, 10.43mmol, 2.5M) was added slowly and after 1h of reaction at this temperature, isopropanol pinacol borate (2.102g, 11.3mmol) was added and reacted overnight, after TLC showed completion of the reaction, saturated ammonium chloride was added to quench the reaction, EA was extracted, dried, filtered and evaporated to remove the solvent to give crude product which was purified by silica gel column chromatography to give intermediate 38(3.86g, 82%).
Step 2: synthesis of intermediate 39
Intermediate 12(1.95g, 8.4mmol), intermediate 38(3.85g, 8.4mmol), Pd (PPh)3)4A mixture of (0.48g, 0.42mmol), sodium carbonate (1.34g, 12.6mmol) and 1, 4-dioxane/water (32mL/8mL) was heated to reflux under nitrogen overnight and cooled to room temperature after TLC indicated completion of the reaction. Water was added to the reaction, EA was used to extract the organic phase, which was dried, filtered and the solvent removed by rotary evaporation to give intermediate 39(3.1g, yield 70%).
And step 3: synthesis of intermediate 40
Intermediate 39(3.1g, 5.91mmol) was dissolved in 15mL ethanol, then 15mL HCl (2N) was slowly added to the reaction system, then heated to reflux, reacted for 2h, cooled to room temperature after TLC showed completion of the reaction, neutralized to neutral by addition of sodium bicarbonate solution, filtered to give crude solid, purified by column chromatography to give intermediate 40(2.75g, 99.78% yield).
And 4, step 4: synthesis of intermediate 41
Intermediate 40(2.75g, 5.9mmol), cuprous bromide (86mg, 0.6mmol), 2,2,6, 6-tetramethylheptanedione (0.88g, 4.8mmol), cesium carbonate (4.89g, 15mmol) and DMF (60mL) were heated to 135 ℃ under nitrogen blanket for reaction overnight, and cooled to room temperature after TLC indicated completion of the reaction. Water was added thereto until a large amount of yellow solid precipitated in the solution, which was filtered, washed several times with water and then dried by suction to obtain intermediate 41(2.54g, yield 99.8%) as a yellow solid.
And 5: synthesis of intermediate 42
Intermediate 41(2.54g, 5.91mmol), neopentyl boronic acid (1.37g, 11.83mmol), Pd2(dba)3(135mg，0.15mmol)，Sphos(243mg，0.59mmol)，K3PO4.3H2O (4.72g, 17.7mmol) and toluene 30mL are mixed, the system is vacuumized and nitrogen exchanged for three times, the mixture is heated to reflux and reacted overnight, TLC detects the reaction to be complete and then cooled to room temperature, solvent is removed by rotary evaporation to obtain crude product, and the crude product is purified by column chromatography to obtain intermediate 42(1.8g, yield 65%).
Step 6: synthesis of iridium dimer:
a mixture of intermediate 42(1.4g,3.0mmol), iridium trichloride trihydrate (0.35g, 1.0mmol), 2-ethoxyethanol (12mL) and water (4mL) was refluxed under nitrogen for 24 hours. After cooling to room temperature, red solid iridium dimer was obtained by filtration and used in the next reaction without further purification.
And 7: synthesis of compound 291:
the iridium dimer obtained in the previous step, 3.7-diethyl-1, 1, 1-trifluorononane-4, 6-dione (0.39g, 1.5mmol) and potassium carbonate (0.69g, 5.00mmol) were dissolved in 16mL of ethoxyethanol and reacted at 50 ℃ for 24 hours under nitrogen. It was then poured into a funnel with celite, filtered and washed with ethanol. Methylene chloride was added to the resulting solid and the filtrate was collected. Ethanol was then added and the resulting solution was concentrated, but not dried. After filtration, 0.71g of compound 291 was obtained in 41.2% yield. The structure of the compound was confirmed by LC-MS to be the target product, molecular weight 1386.7.
Synthesis example 20: synthesis of Compound 292
Step 1: synthesis of iridium dimer:
a mixture of intermediate 43(1.4g,2.92mmol), iridium trichloride trihydrate (0.34g, 0.97mmol), 2-ethoxyethanol (12mL) and water (4mL) was refluxed under nitrogen for 24 hours. After cooling to room temperature, red solid iridium dimer was obtained by filtration and used in the next reaction without further purification.
Step 2: synthesis of compound 292:
the iridium dimer obtained in the previous step, 3.7-diethyl-1, 1, 1-trifluorononane-4, 6-dione (0.38g, 1.5mmol) and potassium carbonate (0.67g, 4.85mmol) were dissolved in 16mL of ethoxyethanol and reacted at 50 ℃ for 24 hours under nitrogen. It was then poured into a funnel with celite, filtered and washed with ethanol. Methylene chloride was added to the resulting solid and the filtrate was collected. Ethanol was then added and the resulting solution was concentrated, but not dried. After filtration, 0.67g of compound 292 was obtained in 49% yield. The structure of the compound was confirmed by LC-MS to be the target product, molecular weight 1414.7.
Synthetic example 21: synthesis of Compound 293
Step 1: synthesis of compound 293:
iridium dimer (1.01g, 0.97mmol), 3,3, 7-triethylnonane-4, 6-dione (0.4g, 1.5mmol) and potassium carbonate (0.72g, 4.85mmol) were dissolved in 16mL of ethoxyethanol and reacted at 50 ℃ for 24 hours under nitrogen. It was then poured into a funnel with celite, filtered and washed with ethanol. Methylene chloride was added to the resulting solid and the filtrate was collected. Ethanol was then added and the resulting solution was concentrated, but not dried. After filtration, 0.62g of compound 293 is obtained in 45% yield. The structure of the compound was confirmed by LC-MS to be the target product, molecular weight 1388.8.
Synthetic example 22: synthesis of Compound 294
Step 1: synthesis of iridium dimer:
a mixture of intermediate 44(0.68g,1.60mmol), iridium trichloride trihydrate (0.16g, 0.45mmol), 2-ethoxyethanol (6mL) and water (2mL) was refluxed under nitrogen for 24 hours. After cooling to room temperature, red solid iridium dimer was obtained by filtration and used in the next reaction without further purification.
Step 2: synthesis of compound 294:
the iridium dimer obtained in the previous step, 3, 7-diethyl-3, 7-dimethylnonane-4, 6-dione (0.22g, 0.9mmol) and potassium carbonate (0.62g, 4.5mmol) were dissolved in 16mL of ethoxyethanol and reacted at 50 ℃ for 24 hours under nitrogen. It was then poured into a funnel with celite, filtered and washed with ethanol. Methylene chloride was added to the resulting solid and the filtrate was collected. Ethanol was then added and the resulting solution was concentrated, but not dried. After filtration, 0.42g of compound 294 is obtained in 73% yield. The structure of the compound was confirmed by LC-MS to be the target product, molecular weight 1276.7.
Synthetic example 23: synthesis of Compound 295
Step 1: synthesis of iridium dimer:
a mixture of intermediate 45(2.03g,4.93mmol), iridium trichloride trihydrate (0.48g, 1.37mmol), 2-ethoxyethanol (33mL) and water (11mL) was refluxed under nitrogen for 24 hours. After cooling to room temperature, red solid iridium dimer was obtained by filtration and used in the next reaction without further purification.
Step 2: synthesis of compound 295:
the iridium dimer obtained in the previous step, 3, 7-diethyl-1, 1, 1-trifluorononane-4, 6-dione (0.53g, 2mmol) and potassium carbonate (0.95g, 6.85mmol) were mixed with ethoxyethanol (23mL), and the mixture was reacted at room temperature for 48 hours while displacing nitrogen. The reaction solution was filtered through celite, the filter cake was washed with appropriate amount of EtOH, the crude product was washed with DCM to 250mL eggplant-shaped bottle, EtOH (about 10mL) was added thereto, DCM was removed by rotary evaporation at room temperature, solid was precipitated, the crude product was filtered and washed with appropriate amount of EtOH to obtain crude product, which was purified by column chromatography to obtain 0.1g of compound 295 with yield 5.7%. The structure of the compound was confirmed by LC-MS to be the target product, molecular weight 1278.5.
Synthetic example 24: synthesis of Compound 280
Step 1: synthesis of iridium dimer:
intermediate 46(0.15g, 0.526mmol) was dissolved in 9mL 2-ethoxyethanol and 3mL water at room temperature, and IrCl was added3·3H2O (62mg, 0.175mmol), heated to 160 ℃ in an autoclave, refluxed at this temperature for 24 hours, and cooled to room temperature. Filtering, washing the solid with ethanol until the washing liquid is colorless, and filtering to obtainTo red solid iridium dimer, which was used directly in the next reaction without purification.
Step 2: synthesis of compound 280:
the iridium dimer (0.25g, 0.157mmol) obtained in the previous step was charged to a 100mL round bottom flask, and K was added2CO3(217mg, 1.57mmol) and 3, 7-diethyl-3-methylnonane-4, 6-dione (142mg, 0.629mmol), 5mL of 2-ethoxyethanol and 5mL of DCM are added, the mixture is purged three times at room temperature, the mixture is heated to 40 ℃ and stirred for 24 hours under nitrogen. DCM was removed in vacuo, the solid was filtered through celite, the solid was washed with ethanol until the wash was colorless, and the ethanol was removed by suction filtration. The red solid on the celite was dissolved in 200mL of dichloromethane under vacuum filtration, 20mL of ethanol was added, dichloromethane was removed under vacuum, the solid precipitated, and the red solid compound 280(195mg, 0.20mmol, 63.7% yield) was filtered. The structure of the compound was confirmed by LC-MS to be the target product, molecular weight 986.3.
Synthetic example 25: comprising a ligand La1931Synthesis of the compound of (1)
Step 1: synthesis of intermediate 48
Intermediate 12(1.63g, 7.0mmol), intermediate 47(3.9g, 7.4mmol), Pd (PPh)3)4A mixture of (0.4g, 0.35mmol), sodium carbonate (1.11g, 10.5mmol) and 1, 4-dioxane/water (28mL/7mL) was heated to reflux under nitrogen overnight and cooled to room temperature after TLC indicated completion of the reaction. Water was added to the reaction, EA was used to extract the organic phase, which was dried, filtered and the solvent removed by rotary evaporation to give intermediate 48(3.2g, 76% yield).
Step 2: synthesis of intermediate 49
Intermediate 48(3.2g, 5.33mmol) was dissolved in 15mL of ethanol, then 15mL of HCl (2N) was slowly added to the reaction system, followed by heating to reflux, reaction for 2h, cooling to room temperature after TLC showed completion of the reaction, neutralized to neutral by addition of sodium bicarbonate solution, filtered to give crude solid, which was purified by column chromatography to give intermediate 49(2.65g, yield 94.5%).
And 3, step 3: synthesis of intermediate 50
Intermediate 49(2.65g, 5.0mmol), cuprous bromide (72mg, 0.5mmol), 2,2,6, 6-tetramethylheptanedione (0.74g, 4.0mmol), cesium carbonate (4.07g, 12.5mmol) and DMF (50mL) were heated to 135 ℃ under nitrogen blanket for reaction overnight, and cooled to room temperature after TLC indicated completion of the reaction. Water was added thereto until a large amount of yellow solid precipitated in the solution, which was filtered, washed several times with water and then dried by suction to give intermediate 50(2.26g, yield 92.4%) as a yellow solid.
And 4, step 4: synthesis of intermediate 51
Intermediate 50(2.26g, 4.62mmol), neopentyl boronic acid (1.07g, 9.23mmol), Pd2(dba)3(106mg，0.12mmol)，Sphos(190mg，0.46mmol)，K3PO4.3H2O (3.69g, 13.9mmol) and 30mL of toluene are mixed, the system is vacuumized, nitrogen is exchanged for three times, the mixture is heated to reflux and reacted overnight, TLC detection is carried out until the reaction is completed, the mixture is cooled to room temperature, solvent is removed by rotary evaporation to obtain a crude product, and the crude product is purified by column chromatography to obtain an intermediate 51(1.8g, yield 74%). The structure of this intermediate was confirmed by LC-MS as the target structure, molecular weight 525.3.
Starting from intermediate 51, the person skilled in the art refers to the methods of the prior art orThe method according to synthesis examples 1 to 24 was followed to obtain ligands L of the present inventiona1931The compound of (1).
It will be appreciated by those skilled in the art that the above preparation method is only an illustrative example, and that those skilled in the art can modify it to obtain other structures of the compounds of the present invention.
Device embodiments
Device example 1
First, a glass substrate, having an Indium Tin Oxide (ITO) anode 120nm thick, was cleaned and then treated with oxygen plasma and UV ozone. After treatment, the substrate was dried in a glove box to remove moisture. The substrate is then mounted on a substrate holder and loaded into a vacuum chamber. The organic layer specified below was at a vacuum of about 10-8In the case of torr, the evaporation was carried out on the ITO anode in turn by thermal vacuum evaporation at a rate of 0.2-2 a/s. Compound HI is used as Hole Injection Layer (HIL) with thickness
Compound HT as Hole Transport Layer (HTL), thickness
Compound EB1 was used as an Electron Blocking Layer (EBL), thickness
Then, the compound 81 of the present invention is doped in the host compound RH to be used as a light emitting layer (EML, 2:98) in thickness
Compound HB as Hole Blocking Layer (HBL), thickness
On HBL, a mixture of compound ET and 8-hydroxyquinoline-lithium (Liq) is deposited as an Electron Transport Layer (ETL) in thickness
Finally, depositingLiq with a thickness of 1nm was used as an electron injection layer, and 120nm of Al was deposited as a cathode. The device was then transferred back to the glove box and encapsulated with a glass lid and moisture absorber to complete the device.
Device example 2
Device example 2 was prepared in the same manner as in device example 1 except that the compound of the present invention 81 was replaced with the compound of the present invention 83 in the light emitting layer (EML).
Device example 3
Device example 3 was prepared in the same manner as in device example 1 except that the compound of the present invention 81 was replaced with the compound of the present invention 64 in the light-emitting layer (EML), the doping ratio of the compound of the present invention 64 to the compound RH was adjusted to 3:97, and the compound EB2 was replaced with the compound EB1 in the Electron Blocking Layer (EBL).
Device example 4
Device example 4 was prepared in the same manner as in device example 3 except that the compound of the present invention 93 was used instead of the compound of the present invention 64 in the light emitting layer (EML).
Device example 5
Device example 5 was prepared in the same manner as device example 3 except that the compound of the present invention 64 was replaced with the compound of the present invention 117 in the light emitting layer (EML).
Device example 6
Device example 6 was prepared in the same manner as device example 3 except that the compound of the present invention 64 was replaced with the compound of the present invention 116 in the light emitting layer (EML).
Device example 7
Device example 7 was prepared in the same manner as in device example 3 except that the compound 261 of the present invention was used instead of the compound 64 of the present invention in the light emitting layer (EML).
Device example 8
Device example 8 was prepared in the same manner as device example 3 except that the compound of the present invention 64 was replaced with the compound of the present invention 262 in the light emitting layer (EML).
Device example 9
Device example 9 was prepared in the same manner as device example 3 except that the compound 264 of the present invention was used in place of the compound 64 of the present invention in the light emitting layer (EML).
Device example 10
Device example 10 was prepared in the same manner as in device example 3 except that the compound 64 of the present invention was replaced with the compound 263 of the present invention in the light emitting layer (EML).
Device example 11
Device example 11 was prepared in the same manner as device example 3 except that the compound 64 of the present invention was replaced with the compound 266 of the present invention in the light emitting layer (EML).
Device example 12
Device example 12 was prepared in the same manner as device example 3 except that the compound 265 according to the present invention was used instead of the compound 64 according to the present invention in the light emitting layer (EML).
Device example 13
Device example 13 was prepared in the same manner as in device example 3 except that the present compound 267 was used in place of the present compound 64 in the light emitting layer (EML).
Device example 14
Device example 14 was prepared in the same manner as device example 3 except that the compound of the present invention 282 was used in place of the compound of the present invention 64 in the light emitting layer (EML).
Device example 15
Device example 15 was prepared in the same manner as device example 3 except that the present compound 64 was replaced with the present compound 273 in the light emitting layer (EML).
Device example 16
Device example 16 was prepared in the same manner as device example 3 except that the compound 294 of the present invention was used instead of the compound 64 of the present invention in the light emitting layer (EML).
Device example 17
Device example 17 was prepared in the same manner as device example 3 except that the compound 287 of the present invention was used instead of the compound 64 of the present invention in the light-emitting layer (EML).
Device example 18
Device example 18 was prepared in the same manner as in device example 3 except that the compound 291 according to the present invention was used instead of the compound 64 according to the present invention in the light emitting layer (EML).
Device example 19
Device example 19 was prepared in the same manner as device example 3 except that the compound 292 according to the present invention was used instead of the compound 64 according to the present invention in the light emitting layer (EML).
Device example 20
Device example 20 was prepared in the same manner as device example 3 except that the compound 293 of the present invention was used instead of the compound 64 of the present invention in the light emitting layer (EML).
Device example 21
Device example 21 was prepared in the same manner as in device example 3 except that the compound of the present invention 64 was replaced with the compound of the present invention 295 in the light emitting layer (EML).
Device comparative example 1
Device comparative example 1 was prepared in the same manner as in device example 1 except that the compound RD of the present invention was used in place of the compound 81 in the light emitting layer (EML).
Device comparative example 2
Device comparative example 2 was prepared in the same manner as in device example 3 except that the compound RD of the present invention was used in place of the compound 64 in the light emitting layer (EML).
The partial layer structure and thickness of the device are shown in the table below. Wherein more than one of the materials used is obtained by doping different compounds in the recited weight ratios.
TABLE 1 partial device structures of device examples and comparative examples
The structure of the materials used in the device is as follows:
the IVL and lifetime characteristics of the devices were measured at different current densities and voltages. Table 2 shows the results at 15mA/cm2CIE data, driving voltage (V), maximum emission wavelength (λ max), full width at half maximum (FWHM), and External Quantum Efficiency (EQE) of device example 1, device example 2, and device comparative example 1 measured at constant current, and at 80mA/cm2Lifetime at constant current (LT 97).
TABLE 2 device data
Discussion:
as is clear from the data shown in Table 2, the half-widths of the comparative example 1 and examples 1 and 2 were around 30nm, which was very striking. However, the maximum emission wavelength of comparative example 1 was 566nm, and in examples 1 and 2, the emission wavelength was shifted to a large red range from 606nm to 620nm by designing the molecular structure of the luminescent dopantThe requirement for different bands of red emission is satisfied. At 15mA/cm2At constant current, regardless of the voltage and the data of external quantum efficiency, example 1 and example 2 both outperformed comparative example 1, and in particular, the external quantum efficiency of example 2 was 36% higher than that of comparative example 1. According to comparative example 1 and examples 1 and 2 at 80mA/cm2The life data of LT97 under constant current were 2 hours for comparative example 1, 30 hours for example 1 and 105 hours for example 2, and it was found that the compounds disclosed in the present invention can greatly improve the device life in the electroluminescent device. From the above data analysis, it can be seen that the embodiments can effectively adjust the emission wavelength to meet the requirement of red light emission, reduce the voltage, improve the EQE, and most importantly, greatly improve the lifetime, thereby providing excellent performance, while maintaining a very narrow half-peak width.
Table 3 shows the results at 15mA/cm2CIE data, driving voltage (V), maximum emission wavelength (λ max), full width at half maximum (FWHM), and lifetime (LT97) of device example 3 measured at constant current.
TABLE 3 device data
Discussion:
as can be seen from the data shown in Table 3, by adjusting the molecular structure, the emission wavelength of example 3 was 633nm, in the deep red region, at 15mA/cm2The half-peak width of example 3 was also very narrow at 39nm and the driving voltage was relatively low at a constant current of 3.78V.
Table 4 shows the results at 15mA/cm2CIE data, drive voltage (V), and maximum emission wavelength (. lamda.) of comparative device example 2 and device examples 4 to 21 measured at constant currentmax) Full width at half maximum (FWHM) and External Quantum Efficiency (EQE), and at 80mA/cm2Lifetime at constant current (LT 97).
TABLE 4 device data
Discussion:
it can also be found from the device data in table 4 that in examples 4 to 13, the compound of the present invention successfully achieves a large red shift of the maximum emission wavelength of the device when used as a dopant of the light emitting layer, the emission wavelength is between 614nm and 623nm, and the requirement for different bands of red emission is met, while the maximum emission wavelength of comparative example 2 using the comparative compound RD is only 566nm, which completely fails to meet the requirement for the emission color of the red light device. Furthermore, at 15mA/cm2Although the half-peak widths and voltages of examples 4 to 13 were substantially equal to or slightly less than those of comparative example 2 at a constant current, it should be understood that the half-peak widths of examples 4 to 13 less than 36nm are still at a very high level in the industry, while the voltages of examples 4 to 13 are at a relatively low level in the industry, and the data of external quantum efficiencies of examples 4 to 13 are all further improved at a very high level relative to comparative example 2. Most importantly, the concentration of the compounds in examples 4-13 is 80mA/cm2The LT97 lifetime data at constant current were all improved to a very large extent (at least approximately 20 times, and at most approximately 50 times) relative to comparative example 2 (lifetime under this condition was only 3 hours, and completely failed to meet the requirements). The above comparisons again demonstrate the very excellent properties of the disclosed compounds.
It can also be found from the device data in table 4 that in examples 14 to 21, the compound of the present invention successfully achieves a large red shift of the maximum emission wavelength of the device when used as a dopant of the light emitting layer, the emission wavelength is between 607nm and 625nm, and the requirement for different wavelength bands of red emission is met, while the maximum emission wavelength of comparative example 2 using the comparative compound RD is only 566nm, which completely fails to meet the requirement for the emission color of the red device. Furthermore, at 15mA/cm2At a constant current, althoughThe half-peak widths and voltages of examples 14 to 21 were almost equal to or slightly insufficient compared to those of comparative example 2, but it should be understood that the half-peak widths of examples 14 to 21 which were less than 34nm were still at a very high level in the industry, the voltages of examples 14 to 21 were also at a relatively low level in the industry, and the data of the external quantum efficiencies of examples 14 to 21 were all maintained at a level close to that of comparative example 2 or were improved even further from that of comparative example 2. Most importantly, in examples 14 to 21, the concentration of the compound was 80mA/cm2The LT97 lifetime data at constant current were all improved by a very large amount (9 times minimum, 50 times maximum) compared to comparative example 2 (lifetime under this condition was only 3 hours, and completely failed to meet the requirements). The above comparisons again demonstrate the very excellent properties of the disclosed compounds.
Device example 22
Device example 22 was prepared in the same manner as in device example 3 except that the compound 280 according to the present invention was used in place of the compound 64 according to the present invention and the compound RH2 was used in place of the compound RH in the light-emitting layer (EML).
Device example 23
Device example 23 was prepared in the same manner as device example 22 except that the weight ratio of the compound 280 of the present invention to the host compound RH2 was adjusted to 2:98 in the light emitting layer (EML).
The partial layer structure and thickness of the device are shown in the table below. Wherein more than one of the materials used is obtained by doping different compounds in the recited weight ratios.
Table 5 partial device structures of device examples 22 and 23
The structure of the new materials used in the device is as follows:
the IVL and lifetime characteristics of the devices were measured at different current densities and voltages. Table 6 shows the results at 15mA/cm2CIE data, drive voltage (V), maximum emission wavelength (λ max), full width at half maximum (FWHM), and External Quantum Efficiency (EQE) of device examples 22 and 23 measured at constant current, and at 80mA/cm2Lifetime at constant current (LT 97).
TABLE 6 device data
As can be seen from the data in Table 6, when the compound of the present invention is used as a light emitting dopant in a device, the maximum emission wavelength of the device reaches 625nm, which satisfies the requirement of red light emission; meanwhile, the half-peak widths of examples 22 and 23 are both less than 30nm, which reaches a very striking level and can realize very saturated luminescence; in addition, the voltage of examples 22 and 23 is less than 3.5V, which is a very low voltage, and the external quantum efficiency is more than 20%, which is a relatively high device efficiency; more importantly, examples 22, 23 also had very long device lifetimes. The above data again demonstrate the very excellent properties of the disclosed compounds.
In conclusion, the disclosed compounds can effectively adjust the emission wavelength to meet the requirement of red light emission, reduce the voltage or maintain a low voltage level, improve the EQE, and most importantly, greatly improve the lifetime, in addition to maintaining a very narrow half-peak width, thereby providing excellent performance.
According to our research on the red light emitting material of the OLED, in the structure of the formula I, when the substituent R is not a hydrogen atom, the emission spectrum of the material can be well adjusted, and the external quantum efficiency of the material is improved:
however, according to our repeated studies, ligands having the formula di-structure cannot be successfully complexed with metals to form metal complexes:
unexpectedly, through the structural design, the substituent R in the formula I is designed to be a part in a merging ring, on one hand, a ligand with a corresponding structure, such as the formula 1 disclosed by the invention, can successfully perform a complex reaction with a metal to form a metal complex, and on the other hand, the device research result of related compounds shows that the metal complex with the structure disclosed by the invention has excellent device performance when being used as a luminescent material in an electroluminescent device, can effectively adjust the emission wavelength to meet the red light emission requirement, obtains a very narrow half-peak width, reduces or keeps low voltage, improves EQE, and most importantly, can greatly improve the service life, and the results further highlight the uniqueness and importance of the invention.
It should be understood that the various embodiments described herein are illustrative only and are not intended to limit the scope of the invention. Thus, the invention as claimed may include variations from the specific embodiments and preferred embodiments described herein, as will be apparent to those skilled in the art. Many of the materials and structures described herein may be substituted with other materials and structures without departing from the spirit of the present invention. It should be understood that various theories as to why the invention works are not intended to be limiting.
Claims (24)
1. A metal complex comprising a ligand La，LaHas a structure represented by formula 1:
wherein, ring A and ring B are each independently selected from five-membered unsaturated carbocyclic ring, aromatic ring with 6-30 carbon atoms or heteroaromatic ring with 3-30 carbon atoms;
Rithe same or different at each occurrence represents mono-, poly-, or no substitution; riiThe same or different at each occurrence represents mono-, poly-, or no substitution;
y is selected from SiRyRy，GeRyRy，NRy，PRyO, S or Se;
when two R are simultaneously presentyWhen two R are presentyMay be the same or different;
X1-X2selected from CR, identically or differently at each occurrencexOr N;
R、Ri、Rii、Rxand RyEach occurrence, identically or differently, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl groups having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted amine groups having 0-20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;
adjacent substituents Ri、Rx、RyR and RiiCan optionally be linked to form a ring;
the metal is selected from metals having a relative atomic mass greater than 40.
2. The metal complex of claim 1, wherein ring a and/or ring B are each independently selected from a five-membered unsaturated carbocyclic ring, an aromatic ring having 6 to 18 carbon atoms, or a heteroaromatic ring having 3 to 18 carbon atoms;
preferably, ring a and/or ring B are each independently selected from a five-membered unsaturated carbocyclic ring, an aromatic ring having 6 to 10 carbon atoms, or a heteroaromatic ring having 3 to 10 carbon atoms.
3. The metal complex of claim 1 or 2, wherein the LaA structure selected from the group consisting of structures represented by any one of formulas 2 to 19 and 22 to 23:
wherein,
in the formulae 2-19 and 22-23, X1-X2Selected from CR, identically or differently at each occurrencexOr N; x3-X7Selected from CR, identically or differently at each occurrenceiOr N; a. the1-A6Is selected, identically or differently on each occurrence, from CRiiOr N;
z is selected, identically or differently on each occurrence, from CRiiiRiii，SiRiiiRiii，PRiiiO, S or NRiii(ii) a When two R are simultaneously presentiiiWhen two R are presentiiiThe same or different;
y is selected from SiRyRy，NRy，PRyO, S or Se; when two R are simultaneously presentyWhen two R are presentyThe same or different;
R，Rx，Ry，Ri，Riiand RiiiIdentical or different at each occurrenceIs selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl groups having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted amine groups having 0-20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;
adjacent substituents R, Rx，Ry，Ri，RiiAnd RiiiCan optionally be linked to form a ring;
preferably, LaSelected from the group consisting of the structures represented by formula 2, formula 9, formula 11, and formula 12;
more preferably, LaSelected from the structures represented by formula 2.
4. The metal complex as claimed in claim 3, wherein, in the formulae 2 to 19 and 22 to 23, X1-XnAnd/or A1-AmAt least one of them is selected from N, XnCorresponding to the X1-X7The largest number among the groups represented by any of formulae 2 to 19 and 22 to 23, wherein A ismCorresponds to the A1-A6The largest sequence number among any one of the formulae 2 to 19 and 22 to 23;
preferably, in formula 2-formula 19 and formula 22-formula 23, X1-XnAt least one of them is selected from N, XnCorresponding to the X1-X7The largest sequence number among any one of the formulae 2 to 19 and 22 to 23;
more preferably, X2Is N.
5. The metal complex as claimed in claim 3, wherein, in the formulae 2 to 19 and 22 to 23, X1-X2Each independently selected from CRx；X3-X7Each independently selected from CRi；A1-A6Each independently selected from CRii(ii) a Adjacent substituents Rx、Ri、RiiCan optionally be linked to form a ring;
preferably, said R isx、Ri、RiiEach occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, cyano groups, and combinations thereof;
more preferably, said Rx、Ri、RiiAt least two or three of which, on each occurrence, are selected, identically or differently, from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, cyano groups, and combinations thereof.
6. The metal complex compound according to any one of claims 3 to 5, wherein, in formulae 2 to 11 and 22 to 23, X is4And/or X5Selected from the group consisting of CRiIn the formula 12-formula 19, X3Selected from the group consisting of CRi；
And said R isiSelected from hydrogen, identically or differently on each occurrence,deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, cyano, or a combination thereof;
preferably, said R isiEach occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, fluoro, methyl, ethyl, isopropyl, isobutyl, tert-butyl, neopentyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, norbornyl, adamantyl, trimethylsilyl, isopropyldimethylsilyl, phenyldimethylsilyl, trifluoromethyl, cyano, phenyl, and combinations thereof.
7. The metal complex according to any one of claims 3 to 6, wherein, in formulae 2 to 19 and 22 to 23, R is selected from hydrogen, deuterium, halogen, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, or a combination thereof;
preferably, said R is selected from hydrogen, deuterium, fluorine, methyl, ethyl, isopropyl, isobutyl, tert-butyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, neopentyl, deuterated methyl, deuterated ethyl, deuterated isopropyl, deuterated isobutyl, deuterated tert-butyl, deuterated cyclopentyl, deuterated cyclopentylmethyl, deuterated cyclohexyl, deuterated neopentyl, trimethylsilyl, or a combination thereof.
8. The metal complex compound according to any one of claims 3 to 7, wherein, in formula 2-formula 19 and formula 22-formula 23, Y is selected from O or S; preferably, Y is O.
9. The metal complex compound according to any one of claims 3 to 8, wherein, in the formulae 2 to 19 and 22 to 23, X is1And X2Each independently selected from CRx；
Preferably, said R isxEach occurrence is the same or different and is selected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, or combinations thereof.
10. The metal complex compound according to any one of claims 3 to 8, wherein, in the formulae 2 to 19 and 22 to 23, X is1Selected from the group consisting of CRx，X2Is N;
preferably, said R isxSelected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, or combinations thereof.
11. The metal complex of any one of claims 1 to 10, wherein the ligand LaHas a structure represented by formula 20 or formula 21:
wherein, in the formulae 20 and 21,
y is selected from O or S;
Rx1、Rx2、Ri1、Ri2、Ri3、Rii1、Rii2、Rii3、Rii4each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, and combinations thereof;
r is selected, identically or differently on each occurrence, from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted amine groups having 0 to 20 carbon atoms, and combinations thereof;
preferably, Rx1、Rx2、Ri1、Ri2、Ri3Neutralization/or Rii1、Rii2、Rii3、Rii4At least one or two of which, on each occurrence, are the same or different, are selected from deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, or combinations thereof; r is selected from the group consisting of halogen, substituted or unsubstituted alkyl groups having from 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having from 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having from 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having from 3 to 20 carbon atoms, substituted or unsubstituted alkyl groups having from 6 to 20 carbon atomsAn arylsilyl group, or a combination thereof;
more preferably, Rx1、Rx2、Ri1、Ri2、Ri3Neutralization/or Rii1、Rii2、Rii3、Rii4At least one or two of which are, identically or differently on each occurrence, selected from a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, or a combination thereof; r is selected from the group consisting of substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, or combinations thereof.
12. A metal complex according to claim 11, wherein Ri2Selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, or combinations thereof; r is selected from the group consisting of halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, or combinations thereof; rii1、Rii2、Rii3、Rii4At least one or two of which, on each occurrence, are the same or different, are selected from deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, or combinations thereof;
preferably, Ri2Selected from the group consisting of: a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, or a combination thereof; r is selected from the group consisting of substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, or combinations thereof; r isii1、Rii2、Rii3、Rii4At least one or two of which are, identically or differently on each occurrence, selected from a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, or a combination thereof.
13. The metal complex as claimed in claim 11 or 12, wherein R is represented by formula 20 and formula 21x1、Rx2、Ri1、Ri2、Ri3、Rii1、Rii2、Rii3、Rii4Each occurrence of at least one of R, is selected, identically or differently, from the group consisting of: substituted or unsubstituted alkyl groups having 3 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, and combinations thereof;
preferably, Rx1、Rx2、Ri1、Ri2、Ri3、Rii1、Rii2、Rii3、Rii4Each occurrence of at least one of R, is selected, identically or differently, from the group consisting of: substituted or unsubstituted alkyl groups having 3 to 10 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 10 ring carbon atoms, and combinations thereof.
14. A metal complex according to any one of claims 1 to 13, wherein LaEach occurrence, the same or different, is selected from the group consisting of:
wherein, in the above structure, TMS is trimethylsilyl;
wherein, optionally, the hydrogen in the above structure can be partially or fully substituted with deuterium.
15. The metal complex of any one of claims 1-14, wherein the metal complex has M (L)a)m(Lb)n(Lc)qThe structure of (1);
wherein the metal M is selected from metals having a relative atomic mass greater than 40; l isa、LbAnd LcA first ligand, a second ligand and a third ligand, respectively, of the complex; m is 1,2 or 3, n is 0, 1 or 2, q is 0, 1 or 2, M + n + q is equal to the oxidation state of the metal M; when m is greater than 1, a plurality of LaThe same or different; when n is 2, two LbThe same or different; when q is 2, two LcThe same or different;
La、Lband LcOptionally linked to form a multidentate ligand;
Lband LcEach occurrence, the same or different, is selected from the group consisting of:
wherein R isa、RbAnd RcThe same or different at each occurrence represents mono-, poly-, or no substitution;
Xbeach occurrence, the same or different, is selected from the group consisting of: o, S, Se, NRN1And CRC1RC2；
XcAnd XdEach occurrence, the same or different, is selected from the group consisting of: o, S, Se and NRN2；
Ra、Rb、Rc、RN1、RN2、RC1And RC2Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, substituted or unsubstituted amine groups having 0-20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;
wherein the adjacent substituents Ra、Rb、Rc、RN1、RN2、RC1And RC2Can optionally be linked to form a ring.
16. The metal complex of claim 15, wherein the metal M is selected from Ir, Rh, Re, Os, Pt, Au or Cu; preferably, the metal M is selected from Ir, Pt or Os; more preferably, the metal M is Ir.
17. A metal complex as claimed in claim 15 or 16 wherein LbEach occurrence, identically or differently, is selected from the following structures:
wherein R is1–R7Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, substituted or unsubstituted amine groups having 0-20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;
preferably, wherein R1-R3At least one or two of which are selected from substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having 1 to 20 carbon atoms, or combinations thereof; and/or R4-R6At least one of which is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, or combinations thereof;
more preferably, wherein R1-R3At least two of which are selected from substituted or unsubstituted alkyl groups having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having 2 to 20 carbon atoms, or combinations thereof; and/or R4-R6At least two of them are selected from substituted or unsubstituted alkyl groups having 2 to 20 carbon atoms, substituted or unsubstituted alkyl groups having 3 to 20 ring carbon atomsSubstituted or unsubstituted heteroalkyl groups having 2-20 carbon atoms, or combinations thereof.
18. The metal complex of any one of claims 15-17, wherein LbEach occurrence, the same or different, is selected from the group consisting of:
wherein L iscEach occurrence, the same or different, is selected from the group consisting of:
19. the metal complex of claim 18, wherein the metal complex has Ir (L)a)2(Lb) Or Ir (L)a)2(Lc) Or Ir (L)a)(Lc)2The structure of (1);
wherein when the metal complex has Ir (L)a)2(Lb) In the structure of (1), LaEach occurrence being selected identically or differently from La1To La1931Any one or any two of the group consisting of, LbIs selected from the group consisting of Lb1To Lb322Any one of the group consisting of; when the metal complex has Ir (L)a)2(Lc) In the structure of (1), LaEach occurrence, identically or differently, of a group selected from La1To La1931Any one or any two of the group consisting of, LcIs selected from the group consisting of Lc1To Lc231Any one of the group consisting of; when the metal complex has Ir (L)a)(Lc)2In the structure of (1), LaIs selected from the group consisting of La1To La1931Any one of the group consisting of LcEach occurrence being selected identically or differently from Lc1To Lc231Any one or any two of the group consisting of;
preferably, wherein the metal complex is selected from the group consisting of compound 1 to compound 312;
wherein the compounds 1 to 200 and 261 to 312 have Ir (L)a)2(Lb) Wherein two L areaSame, LaAnd LbEach corresponding to a structure selected from those listed in the following table:
wherein compound 201 to compound 260 have Ir (L)a)2(Lb) Wherein two L areaDifferent, LaAnd LbEach corresponding to a structure selected from those listed in the following table:
20. an electroluminescent device, comprising:
an anode, a cathode, a anode and a cathode,
a cathode electrode, which is provided with a cathode,
and an organic layer disposed between the anode and the cathode, the organic layer comprising the metal complex of any one of claims 1-19.
21. The electroluminescent device of claim 20, wherein the organic layer is a light-emitting layer and the metal complex is a light-emitting material.
22. An electroluminescent device as claimed in claim 20 or 21 in which the electroluminescent device emits red or white light.
23. The electroluminescent device of claim 21, wherein said light-emitting layer further comprises at least one host material; preferably, the at least one host material comprises at least one chemical group selected from the group consisting of: benzene, pyridine, pyrimidine, triazine, carbazole, azacarbazole, indolocarbazole, dibenzothiophene, azadibenzothiophene, dibenzofuran, azadibenzofuran, dibenzoselenophene, triphenylene, azatriphenylene, fluorene, silafluorene, naphthalene, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene, azaphenanthrene, and combinations thereof.
24. A combination of compounds comprising the metal complex of any one of claims 1-19.
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| DE102021110753.9A DE102021110753B4 (en) | 2020-04-30 | 2021-04-27 | Light-emitting material with a polycyclic ligand |
| JP2021076326A JP7278631B2 (en) | 2020-04-30 | 2021-04-28 | Emissive materials with polycyclic ligands |
| KR1020210055624A KR102652631B1 (en) | 2020-04-30 | 2021-04-29 | Light-emitting material with a polycyclic ligand |
| US17/979,546 US20230144101A1 (en) | 2020-04-30 | 2022-11-02 | Light-emitting material with a polycyclic ligand |
| JP2023072357A JP2023090828A (en) | 2020-04-30 | 2023-04-26 | Luminescent material having polycyclic ligand |
| KR1020240039587A KR20240041899A (en) | 2020-04-30 | 2024-03-22 | Light-emitting material with a polycyclic ligand |
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