WO2022262309A1 - 一种有机金属铱化合物及其应用 - Google Patents
一种有机金属铱化合物及其应用 Download PDFInfo
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- WO2022262309A1 WO2022262309A1 PCT/CN2022/078119 CN2022078119W WO2022262309A1 WO 2022262309 A1 WO2022262309 A1 WO 2022262309A1 CN 2022078119 W CN2022078119 W CN 2022078119W WO 2022262309 A1 WO2022262309 A1 WO 2022262309A1
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- WIPO (PCT)
- Prior art keywords
- substituted
- unsubstituted
- alkyl
- compound
- deuterium
- Prior art date
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- -1 Organometallic iridium compound Chemical class 0.000 title claims abstract description 56
- 239000002019 doping agent Substances 0.000 claims abstract description 7
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 37
- 229910052805 deuterium Inorganic materials 0.000 claims description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims description 35
- 239000001257 hydrogen Substances 0.000 claims description 35
- 229910052757 nitrogen Inorganic materials 0.000 claims description 31
- 239000003446 ligand Substances 0.000 claims description 30
- 238000006467 substitution reaction Methods 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 27
- 150000002431 hydrogen Chemical class 0.000 claims description 25
- 229910052736 halogen Inorganic materials 0.000 claims description 24
- 150000002367 halogens Chemical class 0.000 claims description 24
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 21
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 20
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 19
- 125000003118 aryl group Chemical group 0.000 claims description 19
- 125000005104 aryl silyl group Chemical group 0.000 claims description 18
- 125000001072 heteroaryl group Chemical group 0.000 claims description 17
- 229910052731 fluorine Inorganic materials 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 12
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 10
- 125000005842 heteroatom Chemical group 0.000 claims description 10
- 150000002825 nitriles Chemical class 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 125000005865 C2-C10alkynyl group Chemical group 0.000 claims description 9
- 150000002527 isonitriles Chemical class 0.000 claims description 9
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- 125000002723 alicyclic group Chemical group 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 2
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 3
- 239000011737 fluorine Substances 0.000 claims 3
- 150000001875 compounds Chemical class 0.000 abstract description 159
- 238000000859 sublimation Methods 0.000 abstract description 17
- 230000008022 sublimation Effects 0.000 abstract description 17
- 230000003287 optical effect Effects 0.000 abstract description 4
- 229920001621 AMOLED Polymers 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 description 133
- 238000003786 synthesis reaction Methods 0.000 description 132
- 238000000746 purification Methods 0.000 description 76
- 239000002994 raw material Substances 0.000 description 56
- 238000000034 method Methods 0.000 description 52
- 238000001819 mass spectrum Methods 0.000 description 46
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 35
- 239000007787 solid Substances 0.000 description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000005481 NMR spectroscopy Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 239000010408 film Substances 0.000 description 11
- 229940125773 compound 10 Drugs 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000012074 organic phase Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229940125782 compound 2 Drugs 0.000 description 5
- 238000005401 electroluminescence Methods 0.000 description 5
- 238000012544 monitoring process Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 125000004987 dibenzofuryl group Chemical group C1(=CC=CC=2OC3=C(C21)C=CC=C3)* 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000008204 material by function Substances 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 101100457453 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) MNL1 gene Proteins 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-LIDOUZCJSA-N ethanol-d6 Chemical compound [2H]OC([2H])([2H])C([2H])([2H])[2H] LFQSCWFLJHTTHZ-LIDOUZCJSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002503 iridium Chemical class 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 125000004306 triazinyl group Chemical group 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- UAOUIVVJBYDFKD-XKCDOFEDSA-N (1R,9R,10S,11R,12R,15S,18S,21R)-10,11,21-trihydroxy-8,8-dimethyl-14-methylidene-4-(prop-2-enylamino)-20-oxa-5-thia-3-azahexacyclo[9.7.2.112,15.01,9.02,6.012,18]henicosa-2(6),3-dien-13-one Chemical compound C([C@@H]1[C@@H](O)[C@@]23C(C1=C)=O)C[C@H]2[C@]12C(N=C(NCC=C)S4)=C4CC(C)(C)[C@H]1[C@H](O)[C@]3(O)OC2 UAOUIVVJBYDFKD-XKCDOFEDSA-N 0.000 description 1
- GLGNXYJARSMNGJ-VKTIVEEGSA-N (1s,2s,3r,4r)-3-[[5-chloro-2-[(1-ethyl-6-methoxy-2-oxo-4,5-dihydro-3h-1-benzazepin-7-yl)amino]pyrimidin-4-yl]amino]bicyclo[2.2.1]hept-5-ene-2-carboxamide Chemical compound CCN1C(=O)CCCC2=C(OC)C(NC=3N=C(C(=CN=3)Cl)N[C@H]3[C@H]([C@@]4([H])C[C@@]3(C=C4)[H])C(N)=O)=CC=C21 GLGNXYJARSMNGJ-VKTIVEEGSA-N 0.000 description 1
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 1
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 1
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 1
- IWZSHWBGHQBIML-ZGGLMWTQSA-N (3S,8S,10R,13S,14S,17S)-17-isoquinolin-7-yl-N,N,10,13-tetramethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-amine Chemical compound CN(C)[C@H]1CC[C@]2(C)C3CC[C@@]4(C)[C@@H](CC[C@@H]4c4ccc5ccncc5c4)[C@@H]3CC=C2C1 IWZSHWBGHQBIML-ZGGLMWTQSA-N 0.000 description 1
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 description 1
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ONBQEOIKXPHGMB-VBSBHUPXSA-N 1-[2-[(2s,3r,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]oxy-4,6-dihydroxyphenyl]-3-(4-hydroxyphenyl)propan-1-one Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=CC(O)=C1C(=O)CCC1=CC=C(O)C=C1 ONBQEOIKXPHGMB-VBSBHUPXSA-N 0.000 description 1
- 125000004134 1-norbornyl group Chemical group [H]C1([H])C([H])([H])C2(*)C([H])([H])C([H])([H])C1([H])C2([H])[H] 0.000 description 1
- TVTJUIAKQFIXCE-HUKYDQBMSA-N 2-amino-9-[(2R,3S,4S,5R)-4-fluoro-3-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-7-prop-2-ynyl-1H-purine-6,8-dione Chemical compound NC=1NC(C=2N(C(N(C=2N=1)[C@@H]1O[C@@H]([C@H]([C@H]1O)F)CO)=O)CC#C)=O TVTJUIAKQFIXCE-HUKYDQBMSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 125000004135 2-norbornyl group Chemical group [H]C1([H])C([H])([H])C2([H])C([H])([H])C1([H])C([H])([H])C2([H])* 0.000 description 1
- QBWKPGNFQQJGFY-QLFBSQMISA-N 3-[(1r)-1-[(2r,6s)-2,6-dimethylmorpholin-4-yl]ethyl]-n-[6-methyl-3-(1h-pyrazol-4-yl)imidazo[1,2-a]pyrazin-8-yl]-1,2-thiazol-5-amine Chemical compound N1([C@H](C)C2=NSC(NC=3C4=NC=C(N4C=C(C)N=3)C3=CNN=C3)=C2)C[C@H](C)O[C@H](C)C1 QBWKPGNFQQJGFY-QLFBSQMISA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical group COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- OPFJDXRVMFKJJO-ZHHKINOHSA-N N-{[3-(2-benzamido-4-methyl-1,3-thiazol-5-yl)-pyrazol-5-yl]carbonyl}-G-dR-G-dD-dD-dD-NH2 Chemical compound S1C(C=2NN=C(C=2)C(=O)NCC(=O)N[C@H](CCCN=C(N)N)C(=O)NCC(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(N)=O)=C(C)N=C1NC(=O)C1=CC=CC=C1 OPFJDXRVMFKJJO-ZHHKINOHSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- LJOOWESTVASNOG-UFJKPHDISA-N [(1s,3r,4ar,7s,8s,8as)-3-hydroxy-8-[2-[(4r)-4-hydroxy-6-oxooxan-2-yl]ethyl]-7-methyl-1,2,3,4,4a,7,8,8a-octahydronaphthalen-1-yl] (2s)-2-methylbutanoate Chemical compound C([C@H]1[C@@H](C)C=C[C@H]2C[C@@H](O)C[C@@H]([C@H]12)OC(=O)[C@@H](C)CC)CC1C[C@@H](O)CC(=O)O1 LJOOWESTVASNOG-UFJKPHDISA-N 0.000 description 1
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 125000003670 adamantan-2-yl group Chemical group [H]C1([H])C(C2([H])[H])([H])C([H])([H])C3([H])C([*])([H])C1([H])C([H])([H])C2([H])C3([H])[H] 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
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- 125000005605 benzo group Chemical group 0.000 description 1
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
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- KGNDCEVUMONOKF-UGPLYTSKSA-N benzyl n-[(2r)-1-[(2s,4r)-2-[[(2s)-6-amino-1-(1,3-benzoxazol-2-yl)-1,1-dihydroxyhexan-2-yl]carbamoyl]-4-[(4-methylphenyl)methoxy]pyrrolidin-1-yl]-1-oxo-4-phenylbutan-2-yl]carbamate Chemical compound C1=CC(C)=CC=C1CO[C@H]1CN(C(=O)[C@@H](CCC=2C=CC=CC=2)NC(=O)OCC=2C=CC=CC=2)[C@H](C(=O)N[C@@H](CCCCN)C(O)(O)C=2OC3=CC=CC=C3N=2)C1 KGNDCEVUMONOKF-UGPLYTSKSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- CZKMPDNXOGQMFW-UHFFFAOYSA-N chloro(triethyl)germane Chemical compound CC[Ge](Cl)(CC)CC CZKMPDNXOGQMFW-UHFFFAOYSA-N 0.000 description 1
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- 229940125904 compound 1 Drugs 0.000 description 1
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- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
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- 125000005299 dibenzofluorenyl group Chemical group C1(=CC=CC2=C3C(=C4C=5C=CC=CC5CC4=C21)C=CC=C3)* 0.000 description 1
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- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical group CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000003914 fluoranthenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC=C4C1=C23)* 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 125000003838 furazanyl group Chemical group 0.000 description 1
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- 238000002523 gelfiltration Methods 0.000 description 1
- JAXFJECJQZDFJS-XHEPKHHKSA-N gtpl8555 Chemical compound OC(=O)C[C@H](N)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](C(C)C)C(=O)N[C@@H](C(C)C)C(=O)N1CCC[C@@H]1C(=O)N[C@H](B1O[C@@]2(C)[C@H]3C[C@H](C3(C)C)C[C@H]2O1)CCC1=CC=C(F)C=C1 JAXFJECJQZDFJS-XHEPKHHKSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
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- 125000002883 imidazolyl group Chemical group 0.000 description 1
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- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
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- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000005968 oxazolinyl group Chemical group 0.000 description 1
- 125000004934 phenanthridinyl group Chemical group C1(=CC=CC2=NC=C3C=CC=CC3=C12)* 0.000 description 1
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- 235000011056 potassium acetate Nutrition 0.000 description 1
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- 125000003373 pyrazinyl group Chemical group 0.000 description 1
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- 238000006862 quantum yield reaction Methods 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
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- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
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- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
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- 239000011592 zinc chloride Substances 0.000 description 1
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Images
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- 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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Definitions
- the invention relates to the technical field of organic electroluminescence, in particular to an organic luminescent material suitable for organic electroluminescence devices, in particular to an organometallic iridium compound and its application in organic electroluminescence devices.
- OLEDs organic electroluminescent devices
- the basic structure of an OLED device is a thin film of organic functional materials with various functions mixed between metal electrodes, like a sandwich structure. Driven by current, holes and electrons are injected from the cathode and anode, holes and electrons respectively After moving for a certain distance, the light-emitting layer is recombined and released in the form of light or heat, thereby producing the light emission of the OLED.
- organic functional materials are the core components of organic electroluminescent devices, and their thermal stability, photochemical stability, electrochemical stability, quantum yield, film formation stability, crystallinity, color saturation, etc. major factor in device performance.
- organic functional materials include fluorescent materials and phosphorescent materials.
- the fluorescent material is usually an organic small molecule material, and generally only 25% of the singlet state can be used to emit light, so the luminous efficiency is relatively low. Due to the spin-orbit coupling effect caused by the heavy atom effect, phosphorescent materials can use 75% of the energy of triplet excitons in addition to 25% of the singlet state, so the luminous efficiency can be improved.
- phosphorescent materials started relatively late, and the thermal stability, lifetime, and color saturation of materials need to be improved. This is a challenging subject.
- Various organometallic iridium compounds have been developed as phosphorescent materials. For example, Chou et al.
- patent literature CN107892702 discloses a class of Iridium-based and platinum-based complexes of ligands, but the working voltage, device luminous efficiency and color purity of such materials need to be further improved;
- patent document KR101630317 discloses a class of Iridium complexes, where for However, this type of material also has problems such as high device voltage, low current efficiency, and insufficient chromatographic purity that need to be improved;
- patent document KR10069600 discloses a class of naphthyl bis-isoquinoline iridium complexes This type of material also has problems such as high device voltage, low current efficiency, and insufficient chromatographic purity that need to be improved;
- patent document CN110041372 discloses a class of However, the device voltage of this type of compound is high, the current efficiency is low, the emission wavelength is too large, and it is not in the visible light region of the human eye, so it is not suitable for the display technology field; compound However, the color saturation of this type of material is about 0.
- the present invention provides a high-performance organic electroluminescence device and an organometallic iridium compound material capable of realizing such an organic electroluminescence device.
- the organometallic iridium compound of the present invention has the general formula of Ir(La)(Lb)(Lc), wherein La is the structure shown in formula (1), and Lb is the structure shown in formula (2).
- the iridium complex provided by the invention has the advantages of high optical and electrical stability, low sublimation temperature, narrow emission half-maximum width, high color saturation, high luminous efficiency, long device life and the like, and can be used in organic electroluminescent devices. Especially as a red light-emitting dopant, it has the possibility of being applied to the AMOLED industry, especially for display, lighting and automobile taillights.
- a kind of organometallic iridium compound has the general formula of Ir(La)(Lb)(Lc), wherein La is the structure shown in formula (1),
- X 1 is N or CR 1
- X 2 is N or CR 2
- X 3 is N or CR 3
- X 4 is N or CR 4
- X 5 is N or CR 5 ;
- R 1 -R 5 are independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C2-C17 hetero Aryl, substituted or unsubstituted tri-C1-C10 alkyl silyl, substituted or unsubstituted tri-C6-C12 aryl silyl, substituted or unsubstituted di-C1-C10 alkyl-C6-C30 aryl silyl , a substituted or unsubstituted C1-C10 alkyl,
- At most one of X 1 -X 5 is N, and when X 1 -X 5 is CR 1 -CR 5 , at least one of R 1 -R 5 is not H;
- R 6 -R 9 are independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, and R 6 is not hydrogen, deuterium ,halogen;
- heteroalkyl and heteroaryl contain at least one O, N or S heteroatom;
- substitution is substituted by deuterium, F, Cl, Br, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkyl substituted amino, nitrile, isonitrile or phosphino, wherein
- the above-mentioned substitutions range from a single substitution to a maximum number of substitutions;
- Lb is the structure shown in formula (2)
- the dotted line position represents the position connected with metal Ir;
- Ra-Rg is independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C10 hetero Alkyl, substituted or unsubstituted C3-C20 heterocycloalkyl, or Ra, Rb, Rc are connected in pairs to form an aliphatic ring, and Re, Rf, Rg are connected in pairs to form an aliphatic ring;
- heteroalkyl and heterocycloalkyl contain at least one O, N or S heteroatom;
- substitution is an amino group, cyano group, nitrile, Substituted by isonitrile or phosphino;
- Lc is a monoanionic bidentate ligand, and Lc and Lb are not the same and are not OO ligands;
- Lc and La are the same or different, and the difference is that the core structure is different or the core structure is the same but the substituent is different or the core structure is the same and the substituent is the same but the position of the substituent is different.
- R 1 -R 5 are independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C2-C17 hetero Aryl, substituted or unsubstituted tri-C1-C10 alkyl silyl, substituted or unsubstituted tri-C6-C12 aryl silyl, substituted or unsubstituted di-C1-C10 alkyl-C6-C30 aryl silyl , a substituted or unsubstituted C1-C10 alkyl,
- R 6 -R 9 are independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, and R 6 is not hydrogen, deuterium ,halogen;
- heteroalkyl and heteroaryl contain at least one O, N or S heteroatom;
- substitution is substituted by deuterium, F, Cl, Br, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkyl substituted amino, nitrile, isonitrile or phosphino, wherein the Substitutions range from single to maximum number of substitutions.
- R 6 is substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C10 cycloalkyl.
- R 6 is substituted or unsubstituted methyl, substituted or unsubstituted isopropyl, substituted or unsubstituted cyclopentyl; the substitution is deuterium, F, Cl or Br replaced.
- R 7 is hydrogen, deuterium or halogen.
- R 8 and R 9 are not hydrogen.
- R 8 and R 9 are hydrogen.
- R 8 and R 9 are substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C10 cycloalkyl.
- R 2 is substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, R 1 , R 3 -R 5 are independently selected from hydrogen.
- R 10 -R 17 are independently selected from hydrogen, deuterium, halogen, cyano, hydroxyl, amino, amino, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 heteroalkane substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C18 aryl, substituted or Unsubstituted C2-C17 heteroaryl, substituted or unsubstituted tri-C1-C10 alkylsilyl, substituted or unsubstituted tri-C6-C12 arylsilyl, substituted or unsubstituted di-C1-C10 alkyl- C6-C30 aryl silyl, substituted or unsubstituted C1-C
- R 14 -R 17 are not hydrogen
- At least one group of two adjacent groups in R 10 -R 13 can form an aromatic ring as shown in the following formula (5);
- the dotted line represents the position connected with the pyridine ring
- R 18 -R 21 are independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C2-C17 hetero Aryl, substituted or unsubstituted tri-C1-C10 alkyl silyl, substituted or unsubstituted tri-C6-C12 aryl silyl, substituted or unsubstituted di-C1-C10 alkyl-C6-C30 aryl silyl , a substituted or unsubstituted C1-C10 alkyl,
- heteroalkyl and heteroaryl contain at least one O, N or S heteroatom;
- substitution is substituted by deuterium, F, Cl, Br, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkyl substituted amino, nitrile, isonitrile or phosphino, wherein the Substitutions range from single to maximum number of substitutions.
- organometallic iridium compound wherein La is preferably one of the following structural formulas, or the corresponding partial or complete deuteration or fluorination,
- organometallic iridium compound wherein Lb is preferably one of the following structural formulas, or the corresponding partial or complete deuterated or fluorinated,
- organometallic iridium compound wherein Lc is preferably one of the following structural formulas, or the corresponding partial or complete deuterated or fluorinated,
- Another object of the present invention is to provide an OLED phosphorescent material containing the above compound.
- Another object of the present invention is to provide an OLED device containing the above compound.
- the material of the invention not only has the advantages of high optical and electrical stability, low sublimation temperature, narrow emission half-peak width, high color saturation, high luminous efficiency, long device life and the like.
- the material of the invention can convert the triplet excited state into light, so the luminous efficiency of the organic electroluminescent device can be improved, thereby reducing energy consumption.
- a red light-emitting dopant it has the possibility of being applied to the AMOLED industry.
- Fig. 1 is the HNMR spectrogram of compound Ir(La002) 2 (Lb005) of the present invention in deuterated chloroform solution,
- Fig. 2 is the ultraviolet absorption spectrum and emission spectrum of compound Ir(La002) 2 (Lb005) of the present invention in dichloromethane solution,
- Fig. 3 is the 1HNMR spectrogram of compound Ir(La003) 2 (Lb005) of the present invention in deuterated chloroform solution,
- Fig. 4 is the ultraviolet absorption spectrum and emission spectrum of compound Ir(La003) 2 (Lb005) of the present invention in dichloromethane solution,
- Fig. 5 is the 1HNMR spectrogram of compound Ir(La007) 2 (Lb005) of the present invention in deuterated chloroform solution,
- Fig. 6 is the ultraviolet absorption spectrum and emission spectrum of compound Ir(La007) 2 (Lb005) of the present invention in dichloromethane solution,
- Fig. 7 is the 1HNMR spectrogram of ligand La002 of the present invention in deuterated chloroform solution
- Fig. 8 is the 1HNMR spectrogram of ligand La003 of the present invention in deuterated chloroform solution
- Fig. 9 is the 1HNMR spectrum of the ligand La007 of the present invention in deuterated chloroform solution.
- the compound of the present invention a kind of organometallic iridium compound, has the general formula of Ir(La)(Lb)(Lc), wherein La is the structure shown in formula (1),
- X 1 is N or CR 1
- X 2 is N or CR 2
- X 3 is N or CR 3
- X 4 is N or CR 4
- X 5 is N or CR 5 ;
- R 1 -R 5 are independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C2-C17 hetero Aryl, substituted or unsubstituted tri-C1-C10 alkyl silyl, substituted or unsubstituted tri-C6-C12 aryl silyl, substituted or unsubstituted di-C1-C10 alkyl-C6-C30 aryl silyl , a substituted or unsubstituted C1-C10 alkyl,
- At most one of X 1 -X 5 is N, and when X 1 -X 5 is CR 1 -CR 5 , at least one of R 1 -R 5 is not H;
- R 6 -R 9 are independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, and R 6 is not hydrogen, deuterium ,halogen;
- heteroalkyl and heteroaryl contain at least one O, N or S heteroatom;
- the substitution is deuterium, F, Cl, Br, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkyl substituted amine, nitrile, isonitrile, phosphino, wherein the substitution is Single substitution to maximum number of substitutions.
- Lb is the structure shown in formula (2)
- the dotted line position represents the position connected with metal Ir;
- Ra-Rg is independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C10 hetero Alkyl, substituted or unsubstituted C3-C20 heterocycloalkyl;
- heteroalkyl and heterocycloalkyl contain at least one O, N or S heteroatom;
- substitution is deuterium, F, Cl, Br, C1-C4 alkyl, C1-C4 alkoxy, C3-C6 cycloalkyl, C1-C4 alkyl substituted amino, cyano, nitrile, iso Nitrile, phosphino;
- Ra, Rb, and Rc can be connected in pairs to form an aliphatic ring structure, and Re, Rf, and Rg can also be connected in pairs to form an aliphatic ring;
- Lc is a monoanionic bidentate ligand, and Lc and Lb are not the same and are not OO ligands;
- Lc and La are the same or different, and the difference is that the core structure is different or the core structure is the same but the substituents are different or the core structure is the same and the substituents are the same but the positions of the substituents are different;
- La, Lb, and Lc can be connected in pairs or in threes to form multidentate ligands.
- carbon number a to b in the expression “substituted or unsubstituted X group with carbon number a to b" represents the carbon number when the X group is unsubstituted, The carbon number of the substituent when the X group is substituted is not included.
- the C1-C10 alkyl group is a straight-chain or branched-chain alkyl group, specifically methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl , tert-butyl, n-pentyl and its isomers, n-hexyl and its isomers, n-heptyl and its isomers, n-octyl and its isomers, n-nonyl and its isomers, n- Decyl and its isomers, etc., preferably methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, more preferably propyl, isopropyl, Isobutyl, sec-butyl, tert-butyl.
- C3-C20 cycloalkyl examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl
- An alkyl group and the like are preferably cyclopentyl and cyclohexyl.
- C2-C10 alkenyl examples include vinyl, propenyl, allyl, 1-butadienyl, 2-butadienyl, 1-hexatrienyl, 2-hexatrienyl, 3 -hexatrienyl, etc., preferably propenyl and allyl.
- the C1-C10 heteroalkyl group is a straight-chain or branched-chain alkyl group, cycloalkyl group, etc. containing atoms other than carbon and hydrogen, such as mercaptomethylmethane group, methoxymethane group, ethyl Oxymethyl group, tert-butoxymethane group, N,N-dimethylmethane group, epoxybutyl group, epoxypentyl group, epoxyhexyl group, etc., preferably methoxymethyl group, ring Oxypentyl.
- aryl group examples include phenyl, naphthyl, anthracenyl, phenanthryl, naphthacene, pyrenyl, chrysyl, benzo[c]phenanthryl, benzo[g]chryl, fluorenyl, Benzofluorenyl, dibenzofluorenyl, biphenyl, terphenyl, quaterphenyl, fluoranthenyl, etc., preferably phenyl and naphthyl.
- heteroaryl examples include pyrrolyl, pyrazinyl, pyridyl, pyrimidinyl, triazinyl, indolyl, isoindolyl, imidazolyl, furyl, benzofuryl, isophenyl Dibenzofuryl, dibenzofuryl, dibenzothienyl, azadibenzofuryl, azadibenzothienyl, diazadibenzofuryl, diazadibenzothienyl, Quinolinyl, isoquinolinyl, quinoxalinyl, carbazolyl, phenanthridinyl, acridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenoxazinyl, oxazolinyl, Oxadiazolyl, furazanyl, thienyl, benzothienyl, dihydroacridinyl, azacar
- dimer Ir(La004)-1 (8.64g, 9.77mmol, 1.0eq) and dichloromethane (650ml) into a 3L three-necked flask, stir to dissolve.
- Silver trifluoromethanesulfonate (5.02g, 19.54mmol, 2.0eq) was dissolved in methanol (510ml), then added to the original reaction bottle solution, vacuum replaced 3 times, and the mixture was stirred under N2 protection at room temperature for 16 Hour. Then, the reaction liquid was filtered through diatomaceous earth, the filter residue was rinsed with dichloromethane (150ml), and the filtrate was spin-dried to obtain compound Ir(La004)-2 (7.3g, 70.32%). The obtained compound was directly used in the next step without purification.
- a 50mm*50mm*1.0mm glass substrate with an ITO (100nm) transparent electrode was ultrasonically cleaned in ethanol for 10 minutes, dried at 150°C and then treated with N 2 Plasma for 30 minutes. Install the washed glass substrate on the substrate holder of the vacuum evaporation device. First, the compound HATCN is evaporated on the side of the transparent electrode line to cover the transparent electrode to form a thin film with a film thickness of 5nm.
- the hetero compound (comparative compound X, compound AX of the present invention) has a film thickness of 30 nm, and the ratio of host material to dopant material is 90%:10%.
- An ETL film (25nm) and a LiQ film (1nm) were evaporated sequentially on the light-emitting layer, and finally a layer of metal Al (100nm) was evaporated as an electrode.
- the organic electroluminescent device using the compound of the present invention as a dopant has superior performance in terms of driving voltage, luminous efficiency and device life compared with the comparative compound.
- the compound of the present invention compared to the comparative complex 6, the compound of the present invention surprisingly exhibits more saturated luminescent properties under the conditions of reducing the conjugation and electron-pushing properties of the HOMO energy level, and the deeper The red emission wavelength provides improved device life, with an increase of more than 10%.
- the change of the connection method brings more blue-shifted emission, thereby improving better luminous efficiency.
- the compound of the present invention has the advantages of high optical and electrical stability, low sublimation temperature, narrow emission half-maximum width, high color saturation, high luminous efficiency, long device life, etc., and can be used in organic electroluminescent devices. Especially as a red light-emitting dopant, it has the possibility of being applied to the OLED industry.
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Abstract
本发明涉及一种有机金属铱化合物及其应用。所述有机金属铱化合物具有Ir(La)(Lb)(Lc)的通式,其中La为式(1)所示的结构,Lb为式(2)所示的结构。本发明提供的化合物具有光、电稳定性高,升华温度低,发射半峰宽窄,色饱和度高,发光效率高,器件寿命长等优点,可用于有机电致发光器件中。特别是作为红色发光掺杂体,具有应用于AMOLED产业的可能,特别是用于显示、照明和汽车尾灯。
Description
本发明涉及有机电致发光技术领域,尤其涉及一种适合有机电致发光器件的有机发光材料,特别涉及一种有机金属铱化合物及其在有机电致发光器件上的应用。
目前,作为新一代显示技术的有机电致发光器件(OLED)在显示和照明技术方面都获得了越来越多的关注,应用前景十分广泛。但是,和市场应用要求相比,OLED器件的发光效率、驱动电压、使用寿命等性能还需要继续加强和改进。
一般来说,OLED器件基本结构为在金属电极中间夹杂各种不同功能的有机功能材料薄膜,犹如一个三明治的结构,在电流的驱动下,从阴阳两极分别注入空穴和电子,空穴和电子在移动一段距离后,在发光层得到复合,并以光或热的形式进行释放,从而产生了OLED的发光。然而,有机功能材料是有机电致发光器件的核心组成部分,材料的热稳定性、光化学稳定性、电化学稳定性、量子产率、成膜稳定性、结晶性、色饱和度等都是影响器件性能表现的主要因素。
一般地,有机功能材料包括荧光材料和磷光材料。荧光材料通常为有机小分子材料,一般只能利用25%单重态发光,所以发光效率比较低。而磷光材料由于重原子效应引起地自旋轨道耦合作用,除了利用25%单重态之外,还可以利用75%三重态激子的能量,所以发光效率可以得到提升。但是相较于荧光材料,磷光材料起步较晚,且材料的热稳定性、寿命、色饱和度等都有待提升,这是一个具有挑战性的课题。现已经有人开发各种有机金属铱化合物作为磷光材料。例如Chou等2005年发表非专利文献(Inorg.Chem.2005,44,5677-5685)公开了
所示的铱基络合物作为红色发光材料,但是,这两个材料的发光效率很低且工作电压非常高,需要进一步改善;Wu等2020年发表非专利文献(Dalton.Trans.2020,49,15633-15645)公开了
所示的铂 基络合物作为红色发光材料,同样,该类材料的发光效率很低且工作电压非常高,而且发射峰有多个肩峰,不利于器件的色谱纯度和效率提升,需要进一步得到改进;专利文献CN107892702公开了一类以
为配体的铱基、铂基配合物,但是该类材料的工作电压、器件发光效率和色纯度都需要得到进一步改善;专利文献KR101630317公开了一类
铱络合物,其中
为
但是该类材料同样存在器件电压高、电流效率低,色谱纯度不足等问题需要得到改善;专利文献KR10069600公开了一类萘基联异喹啉铱络合物
该类材料也存在器件电压高、电流效率低,色谱纯度不足等问题需要得到改善;专利文献CN110041372公开了一类
但是该类化合物的器件电压高、电流效率低,发射波长太大,不处于人眼可见光区域,不太适合显示技术领域;专利文献CN111377969公开了一类二苯并呋喃联异喹啉的铱络合物
但是该类材料的色饱和度为CIE(x,y)为0.68,0.32左右,有待进一步改善。
发明内容
本发明为了解决上述缺陷,提供一种高性能的有机电致发光器件及可实现这样的有机电致发光器件的有机金属铱化合物材料。
本发明的有机金属铱化合物,具有Ir(La)(Lb)(Lc)的通式,其中La为式(1)所示的结构,Lb为式(2)所示的结构。本发明提供的铱络合物具有光、电稳定性高,升华温度低,发射半峰宽窄,色饱和度高,发光效率高,器件寿命长等优点,可用于有机电致发光器件中。特别是作为红色发光掺杂体,具有应用于AMOLED产业的可能,特别是用于显示、照明和汽车尾灯。
一种有机金属铱化合物,具有Ir(La)(Lb)(Lc)的通式,其中La为式(1)所示的结构,
其中,虚线表示与金属Ir连接的位置;
其中,X
1为N或CR
1,X
2为N或CR
2,X
3为N或CR
3,X
4为N或CR
4,X
5为N或CR
5;
其中,R
1-R
5独立地选自氢、氘、卤素、氰基、取代的或未取代的C1-C10烷基、取代的或未取代的C1-C10杂烷基、取代的或未取代的C3-C20环烷基、取代或未取代的C2-C10烯基、取代或未取代的C2-C10炔基、取代或未取代的C6-C18芳基、取代或未取代的C2-C17杂芳基、取代或未取代的三C1-C10烷基硅基、取代或未取代的三C6-C12芳基硅基、取代或未取代的二C1-C10烷基一C6-C30芳基硅基、取代或未取代的一C1-C10烷基二C6-C30芳基硅基、或者R
1-R
5两个相邻的基团之间相互连接形成脂环族环或芳香族环;
其中,X
1-X
5至多之一为N,且当X
1-X
5为CR
1-CR
5时,其中R
1-R
5至少之一不为H;
其中,R
6-R
9独立地选自氢、氘、卤素、取代的或未取代的C1-C10烷基、取代的或未取代的C3-C20环烷基,且R
6不为氢、氘、卤素;
其中,所述杂烷基和杂芳基中至少含有一个O、N或S杂原子;
其中,所述取代为被氘、F、Cl、Br、C1-C6烷基、C3-C6环烷基、C1-C6烷基取代的胺基、腈、异腈或膦基所取代,其中所述取代为单取代到最大数目取代;
其中Lb为式(2)所示的结构,
其中,虚线位置表示与金属Ir连接的位置;
其中,Ra-Rg独立地选自氢、氘、卤素、取代的或未取代的C1-C10烷基、取代的或未取代的C3-C20环烷基、取代的或未取代的C1-C10杂烷基、取代的或未取代的C3-C20杂环烷基、或者Ra、Rb、Rc之间两两连接以形成脂肪环,Re、Rf、Rg之间两两连接以形成脂肪环;
其中,所述杂烷基和杂环烷基中至少含有一个O、N或S杂原子;
其中,所述取代为被氘、F、Cl、Br、C1-C4烷基、C1-C4烷氧基、C3-C6环烷基、C1-C4 烷基取代的胺基、氰基、腈、异腈或膦基所取代;
其中,Lc均为单阴离子型双齿配体,Lc与Lb不相同且不为OO型配体;
其中,Lc与La相同或不相同,所述不相同为母核结构不相同或母核结构相同但取代基不同或母核结构相同取代基相同但取代基位置不相同。
优选:其中La为式(3)所示的结构,
其中,虚线表示与金属Ir连接的位置;
其中,R
1-R
5独立地选自氢、氘、卤素、氰基、取代的或未取代的C1-C10烷基、取代的或未取代的C1-C10杂烷基、取代的或未取代的C3-C20环烷基、取代或未取代的C2-C10烯基、取代或未取代的C2-C10炔基、取代或未取代的C6-C18芳基、取代或未取代的C2-C17杂芳基、取代或未取代的三C1-C10烷基硅基、取代或未取代的三C6-C12芳基硅基、取代或未取代的二C1-C10烷基一C6-C30芳基硅基、取代或未取代的一C1-C10烷基二C6-C30芳基硅基、或者R
1-R
5两个相邻的基团之间相互连接形成脂环族环或芳香族环,其中R
1-R
5至少之一不为H;
其中,R
6-R
9独立地选自氢、氘、卤素、取代的或未取代的C1-C10烷基、取代的或未取代的C3-C20环烷基,且R
6不为氢、氘、卤素;
其中,所述杂烷基和杂芳基中至少含有一个O、N或S杂原子;
其中,所述取代为被氘、F、Cl、Br、C1-C6烷基、C3-C6环烷基、C1-C6烷基取代的胺基、腈、异腈或膦基取代,其中所述取代为单取代到最大数目取代。
优选:其中式(3)中,R
6为取代的或未取代的C1-C6烷基、取代的或未取代的C3-C10环烷基。
进一步优选:其中式(3)中,R
6为取代或未取代的甲基、取代或未取代的异丙基、取代或未取代的环戊基;所述取代为被氘、F、Cl或Br所取代。
优选:R
7为氢、氘或卤素。
其中R
8、R
9至少之一不为氢。优选:其中R
8、R
9都不为氢。
进一步优选:其中R
8、R
9至少之一为取代的或未取代的C1-C6烷基、取代的或未取代的C3-C10环烷基。
其中式(3)中,其中R
2和/或R
5不为氢。
优选:其中式(3)中,其中R
2为取代的或未取代的C1-C6烷基、取代的或未取代的C3-C10环烷基,R
1、R
3-R
5独立地选自氢。
优选:其中Lc与La不相同。
进一步优选:其中Lc为式(4)所示的结构,
其中,虚线表示与金属Ir连接的位置;
其中,R
10-R
17独立地选自氢、氘、卤素、氰基、羟基、氨基、胺基、取代的或未取代的C1-C10烷基、取代的或未取代的C1-C10杂烷基、取代的或未取代的C3-C20环烷基、取代或未取代的C2-C10烯基、取代或未取代的C2-C10炔基、取代或未取代的C6-C18芳基、取代或未取代的C2-C17杂芳基、取代或未取代的三C1-C10烷基硅基、取代或未取代的三C6-C12芳基硅基、取代或未取代的二C1-C10烷基一C6-C30芳基硅基、取代或未取代的一C1-C10烷基二C6-C30芳基硅基;
其中,R
14-R
17中至少两个不为氢;
其中,R
10-R
13中至少一组两个相邻的基团之间可形成如下式(5)所示芳香族环;
式(5)中
其中,虚线表示与吡啶环连接的位置;
其中,R
18-R
21独立地选自氢、氘、卤素、氰基、取代的或未取代的C1-C10烷基、取代的或未取代的C1-C10杂烷基、取代的或未取代的C3-C20环烷基、取代或未取代的C2-C10烯基、取代或未取代的C2-C10炔基、取代或未取代的C6-C18芳基、取代或未取代的C2-C17杂芳基、取代或未取代的三C1-C10烷基硅基、取代或未取代的三C6-C12芳基硅基、取代或未取代的二C1-C10烷基一C6-C30芳基硅基、取代或未取代的一C1-C10烷基二C6-C30芳基硅基、或者R
18-R
21两个相邻的基团之间相互连接形成脂环族环或芳香族环;
其中,所述杂烷基和杂芳基中至少含有一个O、N或S杂原子;
其中,所述取代为被氘、F、Cl、Br、C1-C6烷基、C3-C6环烷基、C1-C6烷基取代的胺基、腈、异腈或膦基取代,其中所述取代为单取代到最大数目取代。
作为优选的有机金属铱化合物,其中La优选为以下结构式之一,或者对应的部分或完全氘代或者氟代,
作为优选的有机金属铱化合物,其中Lb优选为以下结构式之一,或者对应的部分或完全氘代或者氟代,
作为优选的有机金属铱化合物,其中Lc优选为以下结构式之一,或者对应的部分或完全氘代或者氟代,
本发明的目的之一还在于提供一种含有上述化合物的OLED磷光材料。
本发明的目的之一还在于提供一种含有上述化合物的OLED器件。
本发明的材料不但具有光、电稳定性高,升华温度低,发射半峰宽窄,色饱和度高,发光效率高,器件寿命长等优点。本发明的材料作为磷光材料,可以将三重激发态转换成光,所以能够提高有机电致发光器件的发光效率,从而降低能耗。特别是作为红色发光掺杂体,具有应用于AMOLED产业的可能。
图1是本发明的化合物Ir(La002)
2(Lb005)在氘代氯仿溶液中的1HNMR谱图,
图2是本发明的化合物Ir(La002)
2(Lb005)在二氯甲烷溶液中的紫外吸收光谱以及发射光谱,
图3是本发明的化合物Ir(La003)
2(Lb005)在氘代氯仿溶液中的1HNMR谱图,
图4是本发明的化合物Ir(La003)
2(Lb005)在二氯甲烷溶液中的紫外吸收光谱以及发射光谱,
图5是本发明的化合物Ir(La007)
2(Lb005)在氘代氯仿溶液中的1HNMR谱图,
图6是本发明的化合物Ir(La007)
2(Lb005)在二氯甲烷溶液中的紫外吸收光谱以及发射光谱,
图7是本发明的配体La002在氘代氯仿溶液中的1HNMR谱图,
图8是本发明的配体La003在氘代氯仿溶液中的1HNMR谱图,
图9是本发明的配体La007在氘代氯仿溶液中的1HNMR谱图。
本发明的化合物,一种有机金属铱化合物,具有Ir(La)(Lb)(Lc)的通式,其中La为式(1)所示的结构,
其中,虚线表示与金属Ir连接的位置;
其中,X
1为N或CR
1,X
2为N或CR
2,X
3为N或CR
3,X
4为N或CR
4,X
5为N或CR
5;
其中,R
1-R
5独立地选自氢、氘、卤素、氰基、取代的或未取代的C1-C10烷基、取代的或未取代的C1-C10杂烷基、取代的或未取代的C3-C20环烷基、取代或未取代的C2-C10烯基、取代或未取代的C2-C10炔基、取代或未取代的C6-C18芳基、取代或未取代的C2-C17杂芳基、取代或未取代的三C1-C10烷基硅基、取代或未取代的三C6-C12芳基硅基、取代或未取代的二C1-C10烷基一C6-C30芳基硅基、取代或未取代的一C1-C10烷基二C6-C30芳基硅基、或者R
1-R
5两个相邻的基团之间可以相互连接形成脂环族环或芳香族环状结构;
其中,X
1-X
5至多之一为N,且当X
1-X
5为CR
1-CR
5时,其中R
1-R
5至少之一不为H;
其中,R
6-R
9独立地选自氢、氘、卤素、取代的或未取代的C1-C10烷基、取代的或未取代的C3-C20环烷基,且R
6不为氢、氘、卤素;
其中,所述杂烷基和杂芳基中至少含有一个O、N或S杂原子;
其中,所述取代为氘、F、Cl、Br、C1-C6烷基、C3-C6环烷基、C1-C6烷基取代的胺基、腈、异腈、膦基,其中所述取代为单取代到最大数目取代。
其中Lb为式(2)所示的结构,
其中,虚线位置表示与金属Ir连接的位置;
其中,Ra-Rg独立地选自氢、氘、卤素、取代的或未取代的C1-C10烷基、取代的或未取代的C3-C20环烷基、取代的或未取代的C1-C10杂烷基、取代的或未取代的C3-C20杂环烷基;
其中,所述杂烷基和杂环烷基中至少含有一个O、N或S杂原子;
其中,所述取代为氘、F、Cl、Br、C1-C4烷基、C1-C4烷氧基、C3-C6环烷基、C1-C4烷基取代的胺基、氰基、腈、异腈、膦基;
其中,Ra、Rb、Rc之间可以两两连接以形成脂肪环状结构,Re、Rf、Rg之间也可以两两连接以形成脂肪环;
其中,Lc均为单阴离子型双齿配体,Lc与Lb不相同且不为OO型配体;
其中,Lc与La相同或不相同,所述不相同为母核结构不相同或母核结构相同但取代基不同或母核结构相同取代基相同但取代基位置不相同;
其中,La、Lb、Lc可以两两或三者相互连接形成多齿配体。
式(1)-式(5)中,在所述取代基为2个以上的情况下,多个取代基可以分别相同也可以不同。
以下,对于式(1)-式(5)所表示的化合物的各基团的例子进行说明。
需要说明的是,本说明书中,“取代或未取代的碳数a~b的X基”这一表述中的“碳数a~b”表示的是X基未取代的情况下的碳数,不包括X基被取代时的取代基的碳数。
作为C1~C10的烷基,为直链状或支链状的烷基,具体来说,为甲基、乙基、丙基、、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基及其异构体、正己基及其异构体、正庚基及其异构体、正辛基及其异构体、正壬基及其异构体、正癸基及其异构体等,优选为甲基、乙基、丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基,更优选为丙基、异丙基、异丁基、仲丁基、叔丁基。
作为C3~C20的环烷基,可举出环丙基、环丁基、环戊基、环己基、1-金刚烷基、2-金刚烷基、1-降冰片烷基、2-降冰片烷基等,优选为环戊基、环己基。
作为C2~C10的烯基,可举出乙烯基、丙烯基、烯丙基、1-丁二烯基、2-丁二烯基、1- 己三烯基、2-己三烯基、3-己三烯基等,优选为丙烯基、烯丙基。
作为C1-C10杂烷基,为含有除碳氢以外的原子构成的直链状或支链状的烷基、环烷基等,可举出巯甲基甲烷基、甲氧基甲烷基、乙氧基甲烷基、叔丁氧基甲烷基、N,N-二甲基甲烷基、环氧丁烷基、环氧戊烷基、环氧己烷基等,优选为甲氧基甲烷基、环氧戊烷基。
作为芳基的具体例,为苯基、萘基、蒽基、菲基、并四苯基、芘基、屈基、苯并[c]菲基、苯并[g]屈基、芴基、苯并芴基、二苯并芴基、联苯基、三联苯基、四联苯基、荧蒽基等,优选为苯基、萘基。
作为杂芳基的具体例,可举出吡咯基、吡嗪基、吡啶基、嘧啶基、三嗪基、吲哚基、异吲哚基、咪唑基、呋喃基、苯并呋喃基、异苯并呋喃基、二苯并呋喃基、二苯并噻吩基、氮杂二苯并呋喃基、氮杂二苯并噻吩基、二氮杂二苯并呋喃基、二氮杂二苯并噻吩基、喹啉基、异喹啉基、喹喔啉基、咔唑基、菲啶基、吖啶基、菲咯啉基、吩嗪基、吩噻嗪基、吩噁嗪基、噁唑啉基、噁二唑基、呋咱基、噻吩基、苯并噻吩基、二氢吖啶基、氮杂咔唑基、二氮杂咔唑基、喹唑啉基等,优选为吡啶基、嘧啶基、三嗪基、二苯并呋喃基、二苯并噻吩基、氮杂二苯并呋喃基、氮杂二苯并噻吩基、二氮杂二苯并呋喃基、二氮杂二苯并噻吩基、咔唑基、氮杂咔唑基、二氮杂咔唑基。
下述实施例仅仅是为了便于理解技术发明,不应视为本发明的具体限制。
本发明中的化合物合成中涉及的原物料和溶剂等均购自于Alfa、Acros等本领域技术人员熟知的供应商。
配体La002的合成:
中间体2的合成:
将化合物1(27.85g,0.13mol,1.0eq)、联硼酸频那醇酯(67.02g,0.26mol,2.0eq)、Pd(dppf)Cl
2(9.66g,0.013mol,0.1eq)、醋酸钾(25.90g,0.26mol,2.0)、1,4-二氧六环(350ml)加入到1L的三口烧瓶中,抽真空氮气置换3次,在氮气保护下,100℃搅拌2小时。TLC监控,原料1反应完全。冷却到室温,减压浓缩除去有机溶剂,加入二氯甲烷和去离子水萃取, 旋干后进行柱层析分离(洗脱剂为乙酸乙酯:正己烷=1:20),浓缩后得淡黄色固体,加3V(90mL)正己烷打浆,70℃下搅拌15min后溶清,停掉加热后继续搅拌2h,抽滤,滤饼干燥得到白色固体为中间体2(19.86g,收率:58.3%),质谱:259.14(M+H)
配体La002的合成:
将中间体3(17.00g,0.08mol,1.0eq)、中间体2(23.47g,0.09mol,1.1eq)、Pd(PPh
3)
4(4.78g,0.004mol,0.05eq)、碳酸钠(17.52g,0.16mol,2.00eq)、1,4-二氧六环(255ml)、去离子水(85ml)加入到1L的三口烧瓶中,抽真空氮气置换3次,在氮气保护下,90℃搅拌3小时。TLC监控,原料3反应完全。冷却到室温,减压浓缩除去有机溶剂,加入二氯甲烷和去离子水萃取,旋干后进行柱层析分离(洗脱剂为乙酸乙酯:正己烷=1:25),浓缩后得到浅黄色糖状固体为化合物La002(21.48g,收率:86.23%),质谱:302.38(M+H)
化合物Ir(La002)
2(Lb005)的合成:
化合物Ir(La002)-1的合成:
将化合物La002(12.30g,40.81mmol,3.5eq)、IrCl
3.3H
2O(4.11g,11.66mmol,1.0eq)置于一个500ml的单口圆底烧瓶中,加入乙二醇乙醚(120ml)及去离子水(40ml),真空置换3次,混合液于N
2保护作用下,110℃搅拌24小时。冷却到室温后,,浓缩除去溶剂,加入DCM溶解滤硅胶,滤液使用去离子水洗涤,浓缩有机相得到暗红色油状物为化合物Ir(La002)-1(9.33g,96.56%)。得到的化合物不经进一步纯化直接使用于下一步。
化合物Ir(La002)
2(Lb005)的合成:
将化合物Ir(La002)-1(6.56g,7.92mmol,1.0eq)、Lb005(8.41g,39.59mmol,5.0eq)、碳酸钠(8.39g,79.19mmol,10.0eq)置于一个250ml的单口圆底烧瓶中,加入乙二醇乙醚(66ml),真空置换3次,混合液于N
2保护作用下,50℃搅拌24小时,TLC监控Ir(La002)-1反应完全。冷却到室温后,加入132ml甲醇室温打浆2h,抽滤,滤饼使用二氯甲烷(100ml)溶解滤硅胶,滤液加入去离子水(120ml)洗涤,分液,收集有机相浓缩,干燥得到暗红色固体,采用DMF/MeCN(30V/20V)重结晶两次得到暗红色固体为化合物Ir(La002)
2(Lb005)(2.65g, 收率:33.32%)。将2.65克Ir(La002)
2(Lb005)粗品升华纯化后得到升华纯Ir(La002)
2(Lb005)(1.52g,收率:57.35%)。质谱:1005.28(M+H)。
1H NMR(400MHz,CDCl
3)δ8.87(d,J=8.9Hz,2H),8.21(d,J=6.4Hz,2H),7.59(s,2H),7.53(d,J=8.9Hz,2H),7.39(d,J=2.1Hz,2H),7.23(d,J=6.4Hz,2H),7.02(s,2H),6.66(d,J=2.1Hz,2H),4.76(s,1H),3.14(dt,J=13.5,6.7Hz,2H),1.54(dd,J=12.1,3.8Hz,8H),1.40(dd,J=6.9,2.7Hz,11H),1.33–1.12(m,3H),1.14–1.02(m,2H),0.75(dd,J=16.9,9.6Hz,4H),0.45(t,J=7.4Hz,6H),-0.20(t,J=7.4Hz,6H).
配体La003的合成:
参照化合物La002的合成和纯化方法,只需要将对应的原物料变更即可,得到目标化合物La003,质谱:316.16(M+H)。
化合物Ir(La003)
2(Lb005)的合成:
化合物Ir(La003)-1的合成:
参照化合物Ir(Lb002)-1的合成和纯化方法,将对应的原物料变更即可,得到化合物Ir(La003)-1不经纯化直接使用于下一步。
化合物Ir(La003)
2(Lb005)的合成:
参照化合物Ir(La002)
2(Lb005)的合成和纯化方法,只需要将对应的原物料变更即可,得到红色固体为化合物Ir(La003)
2(Lb005)(2.31g,收率:32.57%)。将2.31克Ir Ir(La003)
2(Lb005)粗品升华纯化后得到升华纯Ir(La003)
2(Lb005)(1.21g,收率:52.38%),质谱:1033.44(M+H)
1H NMR(400MHz,CDCl
3)δ8.85(d,J=8.7Hz,2H),8.21(d,J=6.4Hz, 2H),7.53(s,2H),7.45(d,J=8.8Hz,2H),7.38(d,J=2.1Hz,2H),7.21(d,J=6.3Hz,2H),7.01(s,2H),6.66(d,J=2.1Hz,2H),4.77(s,1H),2.70(p,J=13.4Hz,4H),2.14–2.01(m,2H),1.66–1.39(m,10H),1.33–1.16(m,3H),1.04(ddd,J=15.7,10.9,6.1Hz,12H),0.88(t,J=7.4Hz,2H),0.77(dd,J=14.7,7.7Hz,3H),0.44(t,J=7.4Hz,5H),-0.20(t,J=7.3Hz,5H).
配体La004的合成:
参照化合物La002的合成和纯化方法,只需要将对应的原物料变更即可,得到目标化合物La004,质谱:330.43(M+H)。
化合物Ir(La004)
2(Lb005)的合成:
化合物Ir(La004)-1的合成:
参照化合物Ir(Lb002)-1的合成和纯化方法,将对应的原物料变更即可,得到化合物Ir(La004)-1不经纯化直接使用于下一步。
化合物Ir(La004)
2(Lb005)的合成:
参照化合物Ir(La002)
2(Lb005)的合成和纯化方法,只需要将对应的原物料变更即可,得到红色固体为化合物Ir(La004)
2(Lb005)(1.89g,收率:36.21%)。将1.89克Ir Ir(La004)
2(Lb005)粗品升华纯化后得到升华纯Ir(La004)
2(Lb005)(1.02g,收率:53.96%),质谱:1061.39(M+H)。
1H NMR(400MHz,CDCl
3)δ8.86(d,J=8.7Hz,2H),8.22(d,J=6.4Hz,2H),7.53(s,2H),7.45(d,J=8.8Hz,2H),7.38(d,J=2.1Hz,2H),7.21(d,J=6.3Hz,2H),7.01(s,2H),6.66(d,J=2.1Hz,2H),4.77(s,1H),2.70(p,J=13.4Hz,4H),1.66–1.39(m,10H),1.33–1.16(m,3H),1.04(m,18H),0.88(t,J=7.4Hz,2H),0.77(dd,J=14.7,7.7Hz,3H),0.44(t,J= 7.4Hz,5H),-0.15(t,J=7.3Hz,5H).
配体La007的合成:
参照化合物La002的合成和纯化方法,只需要将对应的原物料变更即可,得到目标化合物La007,质谱:328.42(M+H)。
化合物Ir(La007)
2(Lb005)的合成:
化合物Ir(La007)-1的合成:
参照化合物Ir(La002)-1的合成和纯化方法,只需要将对应的原物料变更即可,得到化合物Ir(La007)-1不经纯化直接使用于下一步。
化合物Ir(La007)
2(Lb005)的合成:
参照化合物Ir(La002)
2(Lb005)的合成和纯化方法,只需要将对应的原物料变更即可,得到暗红色固体为化合物Ir(La007)
2(Lb005)(2.66g,收率:35.20%)。将2.66克Ir Ir(La007)
2(Lb005)粗品升华纯化后得到升华纯Ir(La007)
2(Lb005)(1.63g,收率:61.27%),质谱:1057.44(M+H)。
1H NMR(400MHz,CDCl
3)δ8.86(d,J=8.8Hz,2H),8.20(d,J=6.4Hz,2H),7.60(s,2H),7.54(d,J=9.0Hz,2H),7.38(d,J=2.1Hz,2H),7.21(d,J=6.4Hz,2H),7.01(s,2H),6.66(d,J=2.1Hz,2H),4.76(s,1H),3.37–3.07(m,2H),2.19(s,4H),1.84(d,J=51.8Hz,11H),1.62–1.44(m,9H),1.24(dd,J=14.9,7.6Hz,3H),1.16–0.97(m,2H),0.75(dd,J=16.5,8.4Hz,4H),0.45(t,J=7.4Hz,5H),-0.19(t,J=7.4Hz,5H).
配体La011的合成:
参照化合物La002的合成和纯化方法,只需要将对应的原物料变更即可,得到目标化合物La011,质谱:370.5(M+H)。
化合物Ir(La011)
2(Lb007)的合成:
化合物Ir(La011)-1的合成:
参照化合物Ir(La002)-1的合成和纯化方法,只需要将对应的原物料变更即可,得到化合物Ir(La011)-1不经纯化直接使用于下一步。
化合物Ir(La011)
2(Lb007)的合成:
参照化合物Ir(La002)
2(Lb005)的合成和纯化方法,只需要将对应的原物料变更即可,得到暗红色固体为化合物Ir(La011)
2(Lb007)(2.11g,收率:34.91%)。将2.11克Ir Ir(La011)
2(Lb007)粗品升华纯化后得到升华纯Ir(La011)
2(Lb007)(0.95g,收率:45.02%),质谱:1069.57(M+H)。
1H NMR(400MHz,CDCl
3)δ8.86(d,J=8.7Hz,2H),8.22(d,J=6.4Hz,2H),7.53(s,2H),7.45(d,J=8.8Hz,2H),7.38(d,J=2.1Hz,2H),7.21(d,J=6.3Hz,2H),7.01(s,2H),6.66(d,J=2.1Hz,2H),2.22(m,2H),1.55(m,6H),1.47(m,16H),1.33–1.16(m,8H),1.03(m,12H),0.89(m,12H),0.77(s,6H)。
化合物Ir(La003)
2(Lb006)的合成:
化合物Ir(La003)
2(Lb006)的合成:
参照化合物Ir(La002)
2(Lb005)的合成和纯化方法,只需要将对应的原物料变更即可,得到暗红色固体为化合物Ir(La003)
2(Lb006)(1.97g,收率:31.70%)。将1.97克Ir Ir(La003)
2(Lb006)粗品升华纯化后得到升华纯Ir(La003)
2(Lb006)(1.11g,收率:56.34%),质谱:1047.34(M+H)。
1H NMR(400MHz,CDCl
3)δ8.85(d,J=8.7Hz,2H),8.21(d,J=6.4Hz,2H),7.53(s,2H),7.45(d,J=8.8Hz,2H),7.38(d,J=2.1Hz,2H),7.21(d,J=6.3Hz,2H),7.01(s,2H),6.66(d,J=2.1Hz,2H),2.70(p,J=13.4Hz,4H),2.14–2.01(m,2H),1.88(s,3H),1.66–1.39(m,10H),1.33–1.16(m,3H),1.04(ddd,J=15.7,10.9,6.1Hz,12H),0.88(t,J=7.4Hz,2H),0.77(dd,J=14.7,7.7Hz,3H),0.44(t,J=7.4Hz,5H),-0.20(t,J=7.3Hz,5H).
配体La039的合成:
中间体10的合成:
在一个1L三口瓶中,加入化合物8(18.5g,86.01mmol,1.0eq)、化合物9(19.97g,94.61mmol,1.1eq)、二甲基亚砜(277ml),在室温下搅拌均匀后,缓慢滴加氢氧化钾水溶液(5.79g,103.2mmol,1.2eq,去离子水为150ml),滴加完毕,反应升温至120℃加热16小时。TLC监控,原料8反应完全。冷却到室温,加入乙酸乙酯(250ml)多次萃取反应液,有机相再加入去离子水水洗2次(100ml/次),分液收集有机相,浓缩后得淡黄色油状物化合物10(24.3g,81.83%),直接进行下步反应。质谱:346.2(M+H)。
中间体11的合成:
在一个1L三口瓶中,加入化合物10(20.0g,57.93mmol,1.0eq)、多聚磷酸(100g)、氯苯(250ml),反应升温至回流16小时。TLC监控,原料10基本反应完全。冷却到室温,加入乙酸乙酯(300ml)萃取反应液,所得有机相加入5%的碳酸氢钠溶液(250ml)进行洗涤3次,再进行分液,有机相浓缩后,进行柱层析分离(洗脱剂正己烷),得白色固体化合物11(6.87g,46.82%)。质谱:254.13(M+H)。
中间体12的合成:
参照化合物2的合成和纯化方法,只需要将对应的原物料变更即可,得到目标化合物12,质谱:301.22(M+H)。
配体La039的合成:
参照化合物La002的合成和纯化方法,只需要将对应的原物料变更即可,得到目标化合物La039,质谱:358.49(M+H)。
化合物Ir(La039)
2(Lb006)的合成:
化合物Ir(La039)-1的合成:
参照化合物Ir(La002)-1的合成和纯化方法,只需要将对应的原物料变更即可,得到化合物Ir(La039)-1不经纯化直接使用于下一步。
化合物Ir(La039)
2(Lb006)的合成:
参照化合物Ir(La002)
2(Lb005)的合成和纯化方法,只需要将对应的原物料变更即可,得到暗红色固体为化合物Ir(La039)
2(Lb006)(2.73g,收率:41.72%)。将2.73克Ir Ir(La039)
2(Lb006)粗品升华纯化后得到升华纯Ir(La039)
2(Lb006)(1.22g,收率:44.68%),质谱:1031.52(M+H)。
1H NMR(400MHz,CDCl
3)δ8.87(d,J=8.8Hz,2H),8.22(d,J=6.4Hz,2H),7.60(s,2H),7.54(d,J=9.0Hz,2H),7.38(d,J=2.1Hz,2H),7.21(d,J=6.4Hz,2H),7.01(s, 2H),2.87(m,2H),2.43(m,4H),2.25(s,6H),1.87(s,3H),1.82(m,2H),1.24(m,18H),1.06–0.76(m,28H).
配体La087的合成:
中间体14的合成:
参照化合物10的合成和纯化方法,只需要将对应的原物料变更即可,得到目标化合物14,质谱:318.22(M+H)。
中间体15的合成:
参照化合物10的合成和纯化方法,只需要将对应的原物料变更即可,得到目标化合物15,质谱:226.08(M+H)。
中间体16的合成:
参照化合物2的合成和纯化方法,只需要将对应的原物料变更即可,得到目标化合物16,质谱:273.15(M+H)。
中间体17的合成:
参照化合物La002的合成和纯化方法,只需要将对应的原物料变更即可,得到目标化合物中间体17,质谱:330.43(M+H)。
配体La087的合成:
取1L单口瓶,投入中间体17(9.5g,28.84mmol,1.0eq),60%的氢化钠(3.46g,86.51mmol,3.0eq),氘代乙醇(100ml)。真空、氮气置换三次,在氮气保护下加热至75℃,反应16h。反应降至室温。加入重水(40mL)搅拌析出固体,过滤收集固体。粗品进行硅胶柱 层析分离(洗脱剂:乙酸乙酯/正己烷=1/30),所得淡黄色固体化合物La087(5.98g,收率62.4%)。
化合物Ir(La087)
2(Lb006)的合成:
化合物Ir(La087)-1的合成:
参照化合物Ir(La002)-1的合成和纯化方法,只需要将对应的原物料变更即可,得到化合物Ir(La087)-1不经纯化直接使用于下一步。
化合物Ir(La087)
2(Lb006)的合成:
参照化合物Ir(La002)
2(Lb005)的合成和纯化方法,只需要将对应的原物料变更即可,得到暗红色固体为化合物Ir(La087)
2(Lb006)(1.68g,收率:31.61%)。将1.68克Ir Ir(La087)
2(Lb006)粗品升华纯化后得到升华纯Ir(La087)
2(Lb006)(0.84g,收率:50.0%),质谱:1081.53(M+H)。
1H NMR(400MHz,CDCl
3)δ8.84(d,J=8.7Hz,2H),8.19(d,J=6.4Hz,2H),7.53(s,2H),7.45(d,J=8.8Hz,2H),7.38(d,J=2.1Hz,2H),7.22(d,J=6.3Hz,2H),7.02(s,2H),2.71(p,J=13.4Hz,4H),2.14–2.01(m,2H),1.88(s,3H),1.66–1.39(m,10H),1.33–1.16(m,3H),1.04(ddd,J=15.7,10.9,6.1Hz,12H),0.88(t,J=7.4Hz,2H),0.77(dd,J=14.7,7.7Hz,3H),0.44(t,J=7.4Hz,5H),-0.20(t,J=7.3Hz,5H).
配体La099的合成:
中间体19的合成:
参照化合物10的合成和纯化方法,只需要将对应的原物料变更即可,得到目标化合物19,质谱:332.25(M+H)。
中间体20的合成:
参照化合物10的合成和纯化方法,只需要将对应的原物料变更即可,得到目标化合物20,质谱:240.11(M+H)。
中间体21的合成:
参照化合物2的合成和纯化方法,只需要将对应的原物料变更即可,得到目标化合物21,质谱:287.17(M+H)。
配体La099的合成:
参照化合物La002的合成和纯化方法,只需要将对应的原物料变更即可,得到目标化合物La099,质谱:344.46(M+H)。
化合物Ir(La099)
2(Lb006)的合成:
化合物Ir(La099)-1的合成:
参照化合物Ir(La002)-1的合成和纯化方法,只需要将对应的原物料变更即可,得到化合物Ir(La099)-1不经纯化直接使用于下一步。
化合物Ir(La099)
2(Lb006)的合成:
参照化合物Ir(La002)
2(Lb005)的合成和纯化方法,只需要将对应的原物料变更即可,得到暗红色固体为化合物Ir(La099)
2(Lb006)(1.89g,收率:33.67%)。将1.89克Ir Ir(La099)
2(Lb006)粗品升华纯化后得到升华纯Ir(La099)
2(Lb006)(1.09g,收率:57.67%), 质谱:1103.47(M+H)。
1H NMR(400MHz,CDCl
3)δ8.85(d,J=8.8Hz,2H),8.20(d,J=6.4Hz,2H),7.60(s,2H),7.54(d,J=9.0Hz,2H),7.38(d,J=2.1Hz,2H),7.21(d,J=6.4Hz,2H),2.43(s,4H),2.30(d,J=40.0Hz,12H),2.02(s,6H),1.87(s,3H),1.85–1.77(m,2H),1.27(m,8H),1.01(m,4H),0.91(m,22H).
配体La111的合成:
中间体23的合成:
参照化合物10的合成和纯化方法,只需要将对应的原物料变更即可,得到目标化合物23,质谱:360.3(M+H)。
中间体24的合成:
参照化合物10的合成和纯化方法,只需要将对应的原物料变更即可,得到目标化合物24,质谱:267.16(M+H)。
中间体25的合成:
参照化合物2的合成和纯化方法,只需要将对应的原物料变更即可,得到目标化合物25,质谱:315.23(M+H)。
配体La111的合成:
参照化合物La002的合成和纯化方法,只需要将对应的原物料变更即可,得到目标化合物La111,质谱:386.54(M+H)。
化合物Ir(La111)
2(Lb006)的合成:
化合物Ir(La111)-1的合成:
参照化合物Ir(La002)-1的合成和纯化方法,只需要将对应的原物料变更即可,得到化合物Ir(La111)-1不经纯化直接使用于下一步。
化合物Ir(La111)
2(Lb006)的合成:
参照化合物Ir(La002)
2(Lb005)的合成和纯化方法,只需要将对应的原物料变更即可,得到暗红色固体为化合物Ir(La111)
2(Lb006)(1.59g,收率:30.87%)。将1.59克Ir(La111)
2(Lb006)粗品升华纯化后得到升华纯Ir(La111)
2(Lb006)(0.87g,收率:54.71%),质谱:1187.63(M+H)。
1H NMR(400MHz,CDCl
3)δ8.23(d,J=6.4Hz,2H),7.61(s,2H),7.55(d,J=9.0Hz,2H),7.39(d,J=2.1Hz,2H),7.212(d,J=6.4Hz,2H),2.69(s,6H),2.43(m,4H),2.34(s,6H),2.02(s,6H),1.87(s,3H),1.82(m,2H),1.27(m,6H),1.19(m,12H),1.07–0.90(m,18H),0.87(m,12H).
配体La123的合成:
中间体27的合成:
参照化合物10的合成和纯化方法,只需要将对应的原物料变更即可,得到目标化合物 27,质谱:386.34(M+H)。
中间体28的合成:
参照化合物10的合成和纯化方法,只需要将对应的原物料变更即可,得到目标化合物28,质谱:294.20(M+H)。
中间体29的合成:
参照化合物2的合成和纯化方法,只需要将对应的原物料变更即可,得到目标化合物29,质谱:341.26(M+H)。
配体La123的合成:
参照化合物La002的合成和纯化方法,只需要将对应的原物料变更即可,得到目标化合物La123,质谱:398.55(M+H)。
化合物Ir(La123)
2(Lb006)的合成:
化合物Ir(La123)-1的合成:
参照化合物Ir(La002)-1的合成和纯化方法,只需要将对应的原物料变更即可,得到化合物Ir(La123)-1不经纯化直接使用于下一步。
化合物Ir(La123)
2(Lb006)的合成:
参照化合物Ir(La002)
2(Lb005)的合成和纯化方法,只需要将对应的原物料变更即可,得到暗红色固体为化合物Ir(La123)
2(Lb006)(1.76g,收率:30.87%)。将1.76克Ir(La123)
2(Lb006)粗品升华纯化后得到升华纯Ir(La123)
2(Lb006)(1.04g,收率:61.17%),质谱:1121.65(M+H)。
1H NMR(400MHz,CDCl
3)δ8.87(d,J=8.8Hz,2H),8.23(d,J=6.4Hz,2H),7.62(s,2H),7.55(d,J=9.0Hz,2H),7.39(d,J=2.1Hz,2H),7.23(d,J=6.4Hz,2H),2.43(m,4H),2.30(m,12H),1.99–1.56(m,21H),1.27(m,6H),1.10–0.81(m,30H).
配体Lc002的合成:
参照化合物La002的合成和纯化方法,只需要将对应的原物料变更即可,得到目标化合物Lc002,质谱:276.39(M+H)。
化合物Ir(La004)(Lb005)(Lc002)的合成:
化合物Ir(La004)-2的合成
在一个3L的三口烧瓶中加入二聚体Ir(La004)-1(8.64g,9.77mmol,1.0eq)和二氯甲烷(650ml)中,搅拌溶解。将三氟甲磺酸银(5.02g,19.54mmol,2.0eq)溶解于甲醇(510ml),再加入到原反应瓶溶液中,真空置换3次,混合液于N
2保护作用下,室温搅拌16小时。然后将反应液进行硅藻土过滤,用二氯甲烷(150ml)淋洗滤渣,将滤液旋干得到化合物Ir(La004)-2(7.3g,70.32%)。得到的化合物不经纯化直接使用于下一步。
化合物Ir(La004)
2(Lc002)的合成
将化合物Ir(La004)-2(6.8g,6.4mmol,1.0eq)、Lc002(4.41g,16.0mmol,2.5eq)加入到250ml的三口烧瓶中,加入乙醇(70ml),真空置换3次,在N
2保护作用下,搅拌回流16 小时。冷却到室温后进行过滤,收集固体用二氯甲烷(150ml)溶解,进行硅胶过滤,再用二氯甲烷(50ml)淋洗滤饼,滤液旋干后,采用四氢呋喃/甲醇重结晶2次(产品:四氢呋喃:甲醇=1:5:10),干燥得到化合物Ir(La004)
2(Lc002)(2.92g,40.62%)。质谱:1124.45(M+H)。
化合物Ir(La004)
2(Lc002)-1的合成
将化合物Ir(La004)
2(Lc002)(5.9g,5.25mmol,1.0eq)、氯化锌(35.79g,262.5mmol,50eq)置于一个1L的单口烧瓶中,加入1,2二氯乙烷(360ml),真空置换3次,于N
2保护作用下,搅拌回流反应18小时。TLC点板监控原料Ir(La004)
2(Lc002)基本反应完全,冷却到室温后,加入去离子水(150ml)洗涤3次,滤液旋干得到化合物Ir(La004)
2(Lc002)-1(3.71g,83.40%)。得到的化合物不经纯化直接使用于下一步。
化合物Ir(La004)(Lb005)(Lc002)的合成
将化合物Ir(La004)
2(Lc002)-1(3.7g,4.37mmol,1.0eq)、Lb005(4.64g,21.58mmol,5.0eq)、碳酸钠(4.63g,43.71mmol,10.0eq)置于一个250ml的单口圆底烧瓶中,加入乙二醇乙醚(55ml),真空置换3次,混合液于N
2保护作用下,50℃搅拌24小时,TLC监控Ir(La004)
2(Lc002)-1反应完全。冷却到室温后,加入110ml甲醇室温打浆2h,抽滤,滤饼使用二氯甲烷(80ml)溶解滤硅胶,滤液加入去离子水(60ml)洗涤,分液,收集有机相浓缩,干燥得到暗红色固体,采用DMF/MeCN(30V/20V)重结晶两次得到暗红色固体为化合物Ir(La004)(Lb005)(Lc002)(1.64g,收率:37.33%)。将1.64克Ir(La004)(Lb005)(Lc002)粗品升华纯化后得到升华纯Ir(La004)(Lb005)(Lc002)(0.79g,收率:48.17%)。质谱:1007.34(M+H)。
1H NMR(400MHz,CDCl
3)δ8.86(m,1H),8.23(d,J=6.4Hz,2H),8.07(m,2H),7.78(d,J=5.0Hz,2H),7.61(m,2H),7.49(d,J=20.0Hz,2H),6.92(m,2H),6.76(m,2H),4.77(s,1H),2.87(s,1H),2.36(m,12H),1.43–1.12(m,14H),1.10–0.75(m,24H).
配体Lc004的合成:
参照化合物La002的合成和纯化方法,只需要将对应的原物料变更即可,得到目标化合物Lc004,质谱:290.41(M+H)。
化合物Ir(La004)(Lb005)(Lc004)的合成:
化合物Ir(La004)
2(Lc004)的合成:
参照化合物Ir(La004)
2(Lc002)的合成和纯化方法,只需要将对应的原物料变更即可,得到目标化合物Ir(La004)
2(Lc004),质谱:1138.48(M+H)。
化合物Ir(La004)
2(Lc004)-1的合成:
参照化合物Ir(La004)
2(Lc002)-1的合成和纯化方法,只需要将对应的原物料变更即可,得到目标化合物Ir(La004)
2(Lc004)-1,不经纯化直接使用于下一步。
化合物Ir(La004)(Lb005)(Lc004)的合成:
参照化合物Ir(La004)(Lb005)(Lc002)的合成和纯化方法,只需要将对应的原物料变更即可,得到暗红色固体为化合物Ir(La004)(Lb005)(Lc004)(1.48g,收率:36.61%)。将1.48克Ir(La004)(Lb005)(Lc004)粗品升华纯化后得到升华纯Ir(La004)(Lb005)(Lc004)(0.78g,收率:52.70%),质谱:1121.37(M+H)。
1H NMR(400MHz,CDCl
3)δ8.85(m,1H),8.23(d,J=6.4Hz,2H),8.07(m,2H),7.78(d,J=5.0Hz,2H),7.61(m,2H),7.50(d,J=20.0Hz,2H),6.90(m,2H),6.76(m,2H),4.77(s,1H),2.43(s,4H),2.32(m,9H),1.82(m,1H),1.27(m,8H),1.01(m,5H),0.97–0.80(m,24H).
配体Lc006的合成:
参照化合物La002的合成和纯化方法,只需要将对应的原物料变更即可,得到目标化合物Lc006,质谱:302.42(M+H)。
化合物Ir(La004)(Lb005)(Lc006)的合成:
化合物Ir(La004)
2(Lc006)的合成:
参照化合物Ir(La004)
2(Lc002)的合成和纯化方法,只需要将对应的原物料变更即可,得到目标化合物Ir(La004)
2(Lc006),质谱:1150.48(M+H)。
化合物Ir(La004)
2(Lc006)-1的合成:
参照化合物Ir(La004)
2(Lc002)-1的合成和纯化方法,只需要将对应的原物料变更即可,得到目标化合物Ir(La004)
2(Lc006)-1,不经纯化直接使用于下一步。
化合物Ir(La004)(Lb005)(Lc006)的合成:
参照化合物Ir(La004)(Lb005)(Lc002)的合成和纯化方法,只需要将对应的原物料变更即可,得到暗红色固体为化合物Ir(La004)(Lb005)(Lc006)(1.87g,收率:38.98%)。将1.87克Ir(La004)(Lb005)(Lc006)粗品升华纯化后得到升华纯Ir(La004)(Lb005)(Lc006)(1.03g,收率:55.08%),质谱:1133.38(M+H)。
1H NMR(400MHz,CDCl
3)δ8.86(d,1H),8.23(d,J=6.4Hz,2H),8.07(m,2H),7.78(d,J=5.0Hz,2H),7.61(m,2H),7.50(d,J=20.0Hz,2H),6.90(m,2H),6.76(m,2H),4.78(s,1H),2.44(s,2H),2.32(d,J=15.0Hz,9H),1.88(m,3H),1.76(m,2H),1.66(m,4H),1.27(m,8H),1.01(m,5H),0.90(m,18H).
应用例:有机电致发光器件的制作
将50mm*50mm*1.0mm的具有ITO(100nm)透明电极的玻璃基板在乙醇中超声清洗10分钟,再150度烘干后经过N
2Plasma处理30分钟。将洗涤后的玻璃基板安装在真空蒸镀装置的基板支架上,首先再有透明电极线一侧的面上按照覆盖透明电极的方式蒸镀化合物HATCN,形成膜厚为5nm的薄膜,紧接着蒸镀一层HTM1形成膜厚为60nm的薄膜,再在HTM1薄膜上蒸镀一层HTM2形成膜厚为10nm的薄膜,然后,在HTM2膜层上再采用共蒸镀的模式蒸镀主体材料和掺杂化合物(对比化合物X、本发明的化合物AX),膜厚为30nm,主体材料和掺杂材料比例为90%:10%。在发光层上再依次蒸镀ETL膜层(25nm)LiQ膜层(1nm),最后蒸镀一层金属Al(100nm)作为电极。
评价:
将上述器件进行器件性能测试,在各实施例和比较例中,使用恒定电流电源(Keithley 2400),使用固定的电流密度流过发光元件,使用分光辐射计(CS 2000)测试发光波谱。同时测定电压值以及测试亮度为初始亮度的90%的时间(LT90)。结果如下:
由上面表格中的数据对比可知,使用本发明的化合物作为掺杂剂的有机电致发光器件,相较于对比化合物在驱动电压、发光效率、器件寿命都表现出更加优越的性能。特别是,本发明的化合物相对于对比络合物6来说,令人惊讶地,在减小HOMO能级的共轭及推电子性的条件下,器件表现出更加饱和的发光性能,更深的红色发射波长,并提供了改善的器件寿命,提升度10%以上;相对于对比例2,连接方式的变换,带来了更蓝移的发射,从而提高了更好的发光效率。
上述结果表明本发明的化合物具有光、电稳定性高,升华温度低,发射半峰宽窄,色饱和度高,发光效率高,器件寿命长等优点,可用于有机电致发光器件中。特别是作为红色发光掺杂体,具有应用于OLED产业的可能。
Claims (17)
- 一种有机金属铱化合物,具有Ir(La)(Lb)(Lc)的通式,其中La为式(1)所示的结构,其中,虚线表示与金属Ir连接的位置;其中,X 1为N或CR 1,X 2为N或CR 2,X 3为N或CR 3,X 4为N或CR 4,X 5为N或CR 5;其中,R 1-R 5独立地选自氢、氘、卤素、氰基、取代的或未取代的C1-C10烷基、取代的或未取代的C1-C10杂烷基、取代的或未取代的C3-C20环烷基、取代或未取代的C2-C10烯基、取代或未取代的C2-C10炔基、取代或未取代的C6-C18芳基、取代或未取代的C2-C17杂芳基、取代或未取代的三C1-C10烷基硅基、取代或未取代的三C6-C12芳基硅基、取代或未取代的二C1-C10烷基一C6-C30芳基硅基、取代或未取代的一C1-C10烷基二C6-C30芳基硅基、或者R 1-R 5两个相邻的基团之间相互连接形成脂环族环或芳香族环;其中,X 1-X 5至多之一为N,且当X 1-X 5为CR 1-CR 5时,其中R 1-R 5至少之一不为H;其中,R 6-R 9独立地选自氢、氘、卤素、取代的或未取代的C1-C10烷基、取代的或未取代的C3-C20环烷基,且R 6不为氢、氘、卤素;其中,所述杂烷基和杂芳基中至少含有一个O、N或S杂原子;其中,所述取代为被氘、F、Cl、Br、C1-C6烷基、C3-C6环烷基、C1-C6烷基取代的胺基、腈、异腈或膦基所取代,其中所述取代为单取代到最大数目取代;其中Lb为式(2)所示的结构,其中,虚线位置表示与金属Ir连接的位置;其中,Ra-Rg独立地选自氢、氘、卤素、取代的或未取代的C1-C10烷基、取代的或未取代的C3-C20环烷基、取代的或未取代的C1-C10杂烷基、取代的或未取代的C3-C20杂环烷基、或者Ra、Rb、Rc之间两两连接以形成脂肪环,Re、Rf、Rg之间两两连接以形成脂肪环;其中,所述杂烷基和杂环烷基中至少含有一个O、N或S杂原子;其中,所述取代为被氘、F、Cl、Br、C1-C4烷基、C1-C4烷氧基、C3-C6环烷基、C1-C4烷基取代的胺基、氰基、腈、异腈或膦基所取代;其中,Lc均为单阴离子型双齿配体,Lc与Lb不相同且不为OO型配体;其中,Lc与La相同或不相同,所述不相同为母核结构不相同或母核结构相同但取代基不同或母核结构相同取代基相同但取代基位置不相同。
- 根据权利要求1所述的有机金属铱化合物,其中La为式(3)所示的结构,其中,虚线表示与金属Ir连接的位置;其中,R 1-R 5独立地选自氢、氘、卤素、氰基、取代的或未取代的C1-C10烷基、取代的或未取代的C1-C10杂烷基、取代的或未取代的C3-C20环烷基、取代或未取代的C2-C10烯基、取代或未取代的C2-C10炔基、取代或未取代的C6-C18芳基、取代或未取代的C2-C17杂芳基、取代或未取代的三C1-C10烷基硅基、取代或未取代的三C6-C12芳基硅基、取代或未取代的二C1-C10烷基一C6-C30芳基硅基、取代或未取代的一C1-C10烷基二C6-C30芳基硅基、或者R 1-R 5两个相邻的基团之间相互连接形成脂环族环或芳香族环,其中R 1-R 5至少之一不为H;其中,R 6-R 9独立地选自氢、氘、卤素、取代的或未取代的C1-C10烷基、取代的或未取代的C3-C20环烷基,且R 6不为氢、氘、卤素;其中,所述杂烷基和杂芳基中至少含有一个O、N或S杂原子;其中,所述取代为被氘、F、Cl、Br、C1-C6烷基、C3-C6环烷基、C1-C6烷基取代的胺基、腈、异腈或膦基取代,其中所述取代为单取代到最大数目取代。
- 根据权利要求2所述的有机金属铱化合物,其中式(3)中,R 6为取代的或未取代的C1-C6烷基、取代的或未取代的C3-C10环烷基。
- 根据权利要求3所述的有机金属铱化合物,其中式(3)中,R 6为取代或未取代的甲基、取代或未取代的异丙基、取代或未取代的环戊基;所述取代为被氘、F、Cl或Br所取代。
- 根据权利要求4所述的有机金属铱化合物,其中式(3)中,R 7为氢、氘或卤素。
- 根据权利要求2所述的有机金属铱化合物,其中R 8、R 9至少之一不为氢。
- 根据权利要求6所述的有机金属铱化合物,其中R 8、R 9都不为氢。
- 根据权利要求7所述的有机金属铱化合物,其中R 8、R 9至少之一为取代的或未取代的 C1-C6烷基、取代的或未取代的C3-C10环烷基。
- 根据权利要求2所述的有机金属铱化合物,其中式(3)中,其中R 2和/或R 5不为氢。
- 根据权利要求9所述的有机金属铱化合物,其中式(3)中,其中R 2为取代的或未取代的C1-C6烷基、取代的或未取代的C3-C10环烷基,R 1、R 3-R 5独立地选自氢。
- 根据权利要求2所述的有机金属铱化合物,其中Lc与La不相同。
- 根据权利要求11所述的有机金属铱化合物,其中Lc为式(4)所示的结构,其中,虚线表示与金属Ir连接的位置;其中,R 10-R 17独立地选自氢、氘、卤素、氰基、羟基、氨基、胺基、取代的或未取代的C1-C10烷基、取代的或未取代的C1-C10杂烷基、取代的或未取代的C3-C20环烷基、取代或未取代的C2-C10烯基、取代或未取代的C2-C10炔基、取代或未取代的C6-C18芳基、取代或未取代的C2-C17杂芳基、取代或未取代的三C1-C10烷基硅基、取代或未取代的三C6-C12芳基硅基、取代或未取代的二C1-C10烷基一C6-C30芳基硅基、取代或未取代的一C1-C10烷基二C6-C30芳基硅基;其中,R 14-R 17中至少两个不为氢;其中,R 10-R 13中至少一组两个相邻的基团之间可形成如下式(5)所示芳香族环;式(5)中其中,虚线表示与吡啶环连接的位置;其中,R 18-R 21独立地选自氢、氘、卤素、氰基、取代的或未取代的C1-C10烷基、取代的或未取代的C1-C10杂烷基、取代的或未取代的C3-C20环烷基、取代或未取代的C2-C10烯基、取代或未取代的C2-C10炔基、取代或未取代的C6-C18芳基、取代或未取代的C2-C17杂芳基、取代或未取代的三C1-C10烷基硅基、取代或未取代的三C6-C12芳基硅基、取代或未取代的二C1-C10烷基一C6-C30芳基硅基、取代或未取代的一C1-C10烷基二C6-C30芳基硅基、或者R 18-R 21两个相邻的基团之间相互连接形成脂环族环或芳香族环;其中,所述杂烷基和杂芳基中至少含有一个O、N或S杂原子;其中,所述取代为被氘、F、Cl、Br、C1-C6烷基、C3-C6环烷基、C1-C6烷基取代的胺基、腈、异腈或膦基取代,其中所述取代为单取代到最大数目取代。
- 权利要求1-15任一所述有机金属铱化合物在有机电致发光器件中的应用。
- 权利要求16所述的应用,为权利要求1-15任一所述有机金属铱化合物作为有机电致发光器件中发光层中的红色发光掺杂材料。
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CN107892702A (zh) * | 2016-10-03 | 2018-04-10 | 环球展览公司 | 有机电致发光材料与装置 |
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