CN114560891A - Iridium complex containing fused indole and quinoline structure and electroluminescent device - Google Patents
Iridium complex containing fused indole and quinoline structure and electroluminescent device Download PDFInfo
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- CN114560891A CN114560891A CN202210299899.6A CN202210299899A CN114560891A CN 114560891 A CN114560891 A CN 114560891A CN 202210299899 A CN202210299899 A CN 202210299899A CN 114560891 A CN114560891 A CN 114560891A
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- Prior art keywords
- substituted
- unsubstituted
- chain alkyl
- heteroaryl
- theoretical
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- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 title claims abstract description 66
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 title claims abstract description 33
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 31
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 title claims abstract description 31
- 125000000217 alkyl group Chemical group 0.000 claims description 45
- -1 heteroaryl ether Chemical compound 0.000 claims description 32
- 125000001072 heteroaryl group Chemical group 0.000 claims description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- 229910052710 silicon Inorganic materials 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 229910052732 germanium Inorganic materials 0.000 claims description 17
- 125000005842 heteroatom Chemical group 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims description 17
- 229910052711 selenium Inorganic materials 0.000 claims description 17
- 229910052717 sulfur Inorganic materials 0.000 claims description 17
- 239000010409 thin film Substances 0.000 claims description 16
- 125000006749 (C6-C60) aryl group Chemical group 0.000 claims description 12
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 10
- 125000004414 alkyl thio group Chemical group 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 5
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 5
- 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 5
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 5
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000008378 aryl ethers Chemical class 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 2
- 125000002541 furyl group Chemical group 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 150000004756 silanes Chemical class 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims 1
- TVCXVUHHCUYLGX-UHFFFAOYSA-N 2-Methylpyrrole Chemical group CC1=CC=CN1 TVCXVUHHCUYLGX-UHFFFAOYSA-N 0.000 claims 1
- 150000004982 aromatic amines Chemical class 0.000 claims 1
- 125000000168 pyrrolyl group Chemical group 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 216
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 161
- 239000011159 matrix material Substances 0.000 description 118
- 238000012360 testing method Methods 0.000 description 118
- 238000001269 time-of-flight mass spectrometry Methods 0.000 description 117
- 238000000921 elemental analysis Methods 0.000 description 116
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 114
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 96
- 239000000047 product Substances 0.000 description 96
- 239000012074 organic phase Substances 0.000 description 95
- 238000006243 chemical reaction Methods 0.000 description 89
- 239000012300 argon atmosphere Substances 0.000 description 85
- 239000010410 layer Substances 0.000 description 84
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 64
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 60
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 59
- 239000000203 mixture Substances 0.000 description 58
- 239000002904 solvent Substances 0.000 description 58
- 229910052786 argon Inorganic materials 0.000 description 57
- 239000012043 crude product Substances 0.000 description 57
- 238000000926 separation method Methods 0.000 description 55
- 239000000243 solution Substances 0.000 description 55
- 150000001875 compounds Chemical class 0.000 description 53
- 229910000027 potassium carbonate Inorganic materials 0.000 description 48
- 238000001914 filtration Methods 0.000 description 46
- 239000003446 ligand Substances 0.000 description 44
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 39
- 239000000463 material Substances 0.000 description 34
- 239000003921 oil Substances 0.000 description 33
- 238000001816 cooling Methods 0.000 description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 31
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 30
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 30
- 238000000605 extraction Methods 0.000 description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 26
- 238000010438 heat treatment Methods 0.000 description 24
- 238000002156 mixing Methods 0.000 description 23
- 239000000126 substance Substances 0.000 description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- LNJXVUXPFZKMNF-UHFFFAOYSA-K iridium(3+);trichloride;trihydrate Chemical compound O.O.O.Cl[Ir](Cl)Cl LNJXVUXPFZKMNF-UHFFFAOYSA-K 0.000 description 20
- 238000000746 purification Methods 0.000 description 20
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 18
- 238000001035 drying Methods 0.000 description 18
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 16
- 238000004440 column chromatography Methods 0.000 description 16
- 238000010992 reflux Methods 0.000 description 16
- 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 15
- IPWKHHSGDUIRAH-UHFFFAOYSA-N bis(pinacolato)diboron Chemical compound O1C(C)(C)C(C)(C)OB1B1OC(C)(C)C(C)(C)O1 IPWKHHSGDUIRAH-UHFFFAOYSA-N 0.000 description 15
- 238000011049 filling Methods 0.000 description 15
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 15
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 15
- 238000005086 pumping Methods 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 14
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- FCDNEESKPPIAJZ-UHFFFAOYSA-N bis[3,5-di(carbazol-9-yl)phenyl]-diphenylsilane Chemical compound C1=CC=CC=C1[Si](C=1C=C(C=C(C=1)N1C2=CC=CC=C2C2=CC=CC=C21)N1C2=CC=CC=C2C2=CC=CC=C21)(C=1C=C(C=C(C=1)N1C2=CC=CC=C2C2=CC=CC=C21)N1C2=CC=CC=C2C2=CC=CC=C21)C1=CC=CC=C1 FCDNEESKPPIAJZ-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 230000000903 blocking effect Effects 0.000 description 8
- 229960000583 acetic acid Drugs 0.000 description 7
- 239000012362 glacial acetic acid Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- BXXLTVBTDZXPTN-UHFFFAOYSA-N methyl 2-iodobenzoate Chemical compound COC(=O)C1=CC=CC=C1I BXXLTVBTDZXPTN-UHFFFAOYSA-N 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 6
- 239000012258 stirred mixture Substances 0.000 description 6
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 6
- TXBFHHYSJNVGBX-UHFFFAOYSA-N (4-diphenylphosphorylphenyl)-triphenylsilane Chemical compound C=1C=CC=CC=1P(C=1C=CC(=CC=1)[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)(=O)C1=CC=CC=C1 TXBFHHYSJNVGBX-UHFFFAOYSA-N 0.000 description 5
- CINYXYWQPZSTOT-UHFFFAOYSA-N 3-[3-[3,5-bis(3-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical compound C1=CN=CC(C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)=C1 CINYXYWQPZSTOT-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 150000004696 coordination complex Chemical class 0.000 description 4
- 125000001033 ether group Chemical group 0.000 description 4
- 230000005525 hole transport Effects 0.000 description 4
- 125000001041 indolyl group Chemical group 0.000 description 4
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- OIRHKGBNGGSCGS-UHFFFAOYSA-N 1-bromo-2-iodobenzene Chemical compound BrC1=CC=CC=C1I OIRHKGBNGGSCGS-UHFFFAOYSA-N 0.000 description 3
- PKXHXOTZMFCXSH-UHFFFAOYSA-N 3,3-dimethylbut-1-ene Chemical compound CC(C)(C)C=C PKXHXOTZMFCXSH-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- ANRQGKOBLBYXFM-UHFFFAOYSA-M phenylmagnesium bromide Chemical compound Br[Mg]C1=CC=CC=C1 ANRQGKOBLBYXFM-UHFFFAOYSA-M 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- KBVDUUXRXJTAJC-UHFFFAOYSA-N 2,5-dibromothiophene Chemical compound BrC1=CC=C(Br)S1 KBVDUUXRXJTAJC-UHFFFAOYSA-N 0.000 description 2
- 125000001313 C5-C10 heteroaryl group Chemical group 0.000 description 2
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000005264 aryl amine group Chemical group 0.000 description 2
- 125000005013 aryl ether group Chemical group 0.000 description 2
- 238000010224 classification analysis Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 150000002503 iridium Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007645 offset printing Methods 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- 238000003809 water extraction Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- ATWLRNODAYAMQS-UHFFFAOYSA-N 1,1-dibromopropane Chemical compound CCC(Br)Br ATWLRNODAYAMQS-UHFFFAOYSA-N 0.000 description 1
- QENIALCDPFDFHX-UHFFFAOYSA-N 1,4-dibromo-2,5-dimethylbenzene Chemical compound CC1=CC(Br)=C(C)C=C1Br QENIALCDPFDFHX-UHFFFAOYSA-N 0.000 description 1
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 description 1
- CZYAFTZIQWCKOI-UHFFFAOYSA-N 1,5-dibromonaphthalene Chemical compound C1=CC=C2C(Br)=CC=CC2=C1Br CZYAFTZIQWCKOI-UHFFFAOYSA-N 0.000 description 1
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- YAWIAFUBXXPJMQ-UHFFFAOYSA-N 1-bromo-4-(4-bromophenoxy)benzene Chemical compound C1=CC(Br)=CC=C1OC1=CC=C(Br)C=C1 YAWIAFUBXXPJMQ-UHFFFAOYSA-N 0.000 description 1
- ZFGCKZCEDNBNMV-UHFFFAOYSA-N 2,8-dibromodibenzothiophene 5,5-dioxide Chemical compound BrC1=CC=C2S(=O)(=O)C3=CC=C(Br)C=C3C2=C1 ZFGCKZCEDNBNMV-UHFFFAOYSA-N 0.000 description 1
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 1
- 238000010146 3D printing Methods 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZRRPXZNSRJSDTM-UHFFFAOYSA-N IC1=C(C=CC=C1)CS(=O)CC1=C(C=CC=C1)I Chemical compound IC1=C(C=CC=C1)CS(=O)CC1=C(C=CC=C1)I ZRRPXZNSRJSDTM-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- YCITZMJNBYYMJO-UHFFFAOYSA-N chloro(diphenyl)silicon Chemical compound C=1C=CC=CC=1[Si](Cl)C1=CC=CC=C1 YCITZMJNBYYMJO-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000001194 electroluminescence spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 125000003784 fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical compound N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
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Abstract
The invention provides an iridium complex containing fused indole and quinoline structures, which has a structure shown in a formula I-1 or a formula I-2. The iridium complex containing the fused indole and quinoline structure provided by the invention can be used as a luminescent layer to be applied to an organic electroluminescent device, so that the luminescent efficiency and the service life of the device are greatly improved.
Description
Technical Field
The invention relates to the technical field of organic luminescent materials, in particular to an iridium complex containing fused indole and quinoline structures and an electroluminescent device.
Background
Organic Light Emitting Devices (OLEDs), which have characteristics of rich colors, thin thickness, wide viewing angle, fast response, and the ability to fabricate flexible devices, are considered to be the next generation of flat panel display and solid illumination technologies with the greatest prospects for development.
OLEDs are generally composed of an ITO anode, a Hole injection layer (TIL), a Hole Transport Layer (HTL), an Emission Layer (EL), a Hole Blocking Layer (HBL), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL), and a cathode, and 1 to 2 organic layers may be omitted as needed, and an Exciton (exiton) is formed by combining a Hole (Hole) injected from a positive electrode and a negative electrode on an organic thin film and an Electron (Electron), and emits light by releasing energy in the form of light emission when the Exciton returns from an excited state to a stable ground state.
Due to the limitation of the spin quantum statistical law, the traditional fluorescent material can only utilize singlet excitons accounting for 25% of the total excitons in the electroluminescent process, and the rest 75% of the triplet excitons are inactivated by means of non-radiative transition, so that the maximum value of the Internal Quantum Efficiency (IQE) of the device is 25%. The phosphorescent metal complex can convert triplet excitons into photons by utilizing the spin-orbit coupling effect of heavy metal atoms, so that the utilization of the triplet excitons is realized, and the internal quantum efficiency of 100% is realized, but the path faces the problem that the phosphorescent metal complex is expensive.
Therefore, how to develop a phosphorescent metal complex material with high and stable light emitting efficiency through reasonable chemical structure design has become one of the problems to be solved by many prospective researchers in the field.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an iridium complex containing fused indole and quinoline structures and an electroluminescent device, where the iridium complex has the advantages of high and stable light-emitting efficiency as a novel phosphorescent metal complex, and after being used in an organic electroluminescent device, the light-emitting efficiency and lifetime of the device are greatly improved.
The invention provides an iridium complex containing fused indole and quinoline structures, which has a structure shown in a formula I-1 or a formula I-2:
wherein Z is1Is C and Z2Is N, or Z1Is N and Z2Is C;
wherein X is selected from a single bond, -C (R)11R12)-、-C＝O-、-Si(R11R12)-、-N(R11)-、-PO(R11)-、-P(R11)＝O-、-B(R11)-、-O-、-S-、-Se-、-S＝O-、-SO2-any of; the R is11And R12Each independently selected from H, D, C1-C30 straight chain alkyl, C1-C30 branched chain alkyl, C3-C30 naphthenic base, C6-C60 aryl or C5-C60 heteroaryl, wherein hetero atoms of the heteroaryl are independently selected from one or more of Si, Ge, N, P, O, S and Se;
R1～R10is independently selected fromH、D、F、Cl、Br、I、-CN、-NO2、-CF3、-OH、-SH、-NH2The aryl group comprises C1-C30 straight-chain alkyl or deuterated straight-chain alkyl, C1-C30 branched-chain alkyl, C3-C30 cycloalkyl, C1-C30 alkoxy, C1-C30 alkylthio, C6-C60 aryl, C6-C60 aryl ether, C5-C60 heteroaryl or C5-C60 heteroaryl ether, wherein hetero atoms of the heteroaryl or the heteroaryl ether are independently selected from one or more of Si, Ge, N, P, O, S and Se;
m1～m10independently selected from integers of 0 to 4;
denotes the connection position.
Preferably, said R is11And R12Each independently selected from H, D, C1-C10 straight chain alkyl, C1-C10 branched chain alkyl, C3-C12 naphthenic base, C6-C12 aryl or C5-C12 heteroaryl, wherein hetero atoms of the heteroaryl are independently selected from one or more of Si, Ge, N, P, O, S and Se; more preferably, R is11And R12Each independently selected from H, D, C1-C6 straight chain alkyl, C1-C6 branched chain alkyl, C3-C6 naphthenic base, C6-C10 aryl or C5-C10 heteroaryl, wherein hetero atoms of the heteroaryl are independently selected from one or more of Si, Ge, N, P, O, S and Se; further preferably, R is11And R12Each independently selected from H, D, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or phenyl.
Preferably, said R is1～R10Independently selected from H, D, F, Cl, Br, I, -CN, -NO2、-CF3、-OH、-SH、-NH2Straight chain alkyl or deuterated straight chain alkyl of C1-C10, branched chain alkyl or deuterated branched chain alkyl of C1-C10, substituted or unsubstituted cycloalkyl of C3-C12, substituted or unsubstituted alkoxy of C1-C10, substituted or unsubstituted alkylthio of C1-C10, substituted or unsubstituted aryl of C6-C12, substituted or unsubstituted aryl ether of C6-C12, substituted or unsubstituted heteroaryl of C5-C12, substituted or unsubstituted heteroaryl of C6-C12C5-C12 heteroaryl ether, substituted or unsubstituted C6-C12 arylamine, C1-C10 straight chain alkyl or branched chain alkyl substituted carbonyl, wherein hetero atoms of the heteroaryl or the heteroaryl ether are independently selected from one or more of Si, Ge, N, P, O, S and Se; more preferably, R is1～R10Independently selected from H, D, F, Cl, Br, I, -CN, -NO2、-CF3、-OH、-SH、-NH2Linear or deuterated linear hydrocarbon group of C1-C6, branched or deuterated branched hydrocarbon group of C1-C6, cycloalkyl group of substituted or unsubstituted C3-C6, alkoxy group of substituted or unsubstituted C1-C6, alkylthio group of substituted or unsubstituted C1-C6, aryl group of substituted or unsubstituted C6-C10, aryl ether group of substituted or unsubstituted C6-C10, heteroaryl group of substituted or unsubstituted C5-C10, heteroaryl ether group of substituted or unsubstituted C5-C10, arylamine group of substituted or unsubstituted C6-C12, and carbonyl group substituted by linear or branched hydrocarbon group of C1-C6, wherein hetero atoms of the heteroaryl or heteroaryl ether group are independently selected from one or more of Si, Ge, N, P, O, S and Se; further preferably, R is1～R10Independently selected from H, D, F, Cl, Br, I, -CN, -NO2、-CF3、-OH、-SH、-NH2Methyl, ethyl, N-propyl, isopropyl, N-butyl, isobutyl, tert-butyl, N-pentyl, N-hexyl, deuterated methyl, deuterated ethyl, deuterated N-propyl, deuterated isopropyl, deuterated N-butyl, deuterated isobutyl, deuterated tert-butyl, trifluoromethyl, fluoroethyl, fluoro-N-propyl, fluoroisopropyl, fluoro-N-butyl, fluoroisobutyl, fluoro-tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, biphenyl, methoxy, ethoxy, propoxy, methylthio, ethylthio, propylthio, acetyl, N-dimethylamino, furyl, methylfuryl, thienyl, methylthio, pyrrolyl, methylpyrrole or carbazolyl.
Preferably, X is selected from any of the following structures:
R11and R12Each independently selected from H, D, C1-C30 straight chain alkyl, C1-C30 branched chain alkyl, C3-C30 naphthenic base, C6-C60 aryl or C5-C60 heteroaryl, wherein hetero atoms of the heteroaryl are independently selected from one or more of Si, Ge, N, P, O, S and Se; and R in X411And R12May form a ring with a silicon atom.
X1 represents a single bond; the single bond in X2 to X13 represents a connecting bond.
More preferably, R is11And R12Each independently selected from H, D, C1-C6 straight chain alkyl, C1-C6 branched chain alkyl, C3-C6 naphthenic base, C6-C10 aryl or C5-C10 heteroaryl, wherein hetero atoms of the heteroaryl are independently selected from one or more of Si, Ge, N, P, O, S and Se; further preferably, R is11And R12Each independently selected from H, D, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or phenyl. More preferably, R is11And R12Is methyl or phenyl.
R in X411And R12And a silicon atom, X4 is the following structure:
according to a preferred embodiment of the present invention, the
Selected from any of the following structures:
p and q are independently selected from integers of 0-8, and r is selected from integers of 1-8;
R13～R14is independently selected fromH、D、F、Cl、Br、I、-CN、-NO2、-CF3、-OH、-SH、-NH2Linear or deuterated linear hydrocarbon group of C1-C30, branched or deuterated branched hydrocarbon group of C1-C30, cycloalkyl group of substituted or unsubstituted C3-C30, alkoxy group of substituted or unsubstituted C1-C30, alkylthio group of substituted or unsubstituted C1-C30, aryl group of substituted or unsubstituted C6-C60, aryl ether group of substituted or unsubstituted C6-C60, heteroaryl group of substituted or unsubstituted C5-C60, heteroaryl ether group of substituted or unsubstituted C5-C60, arylamine group of substituted or unsubstituted C6-C60, and carbonyl group substituted by linear or branched hydrocarbon group of C1-C30, wherein hetero atoms of the heteroaryl or heteroaryl ether group are independently selected from one or more of Si, Ge, N, P, O, S and Se;
m11an integer selected from 0 to 4;
denotes the connection position.
Preferably, the iridium complex containing fused indole and quinoline structures has the structures shown in formulas (I-1-1) to (I-2-25):
the invention also provides application of the iridium complex containing the fused indole and quinoline structure as a luminescent material.
Specifically, the invention provides an organic electroluminescent device, which comprises an anode, a cathode and an organic thin film layer positioned between the anode and the cathode; the organic thin film layer comprises the iridium complex containing the fused indole and quinoline structure.
The structure of the organic electroluminescent device is not particularly limited by the present invention, and may be a conventional organic electroluminescent device well known to those skilled in the art, and those skilled in the art can select and adjust the structure according to the application, quality and product requirements, and the structure of the organic electroluminescent device of the present invention preferably includes: a substrate; an anode disposed on the substrate; an organic thin film layer disposed on the anode; and a cathode disposed on the organic thin film layer.
The thickness of the substrate is preferably 0.3-0.7 mm, and more preferably 0.4-0.6 mm; the choice of the substrate is not particularly limited by the present invention, and may be a substrate of a conventional organic electroluminescent device well known to those skilled in the art, which may be selected and adjusted according to the application, quality requirements and product requirements, and in the present invention, the substrate is preferably glass or plastic.
According to the invention, the anode is preferably a material susceptible to hole injection, more preferably a conductive metal or conductive metal oxide, and even more preferably indium tin oxide.
The organic thin film layer can be one layer or multiple layers, and at least one layer is a light-emitting layer; in the present invention, the organic thin film layer preferably includes a light emitting layer; the light-emitting layer preferably includes the iridium complex containing fused indole and quinoline structures described above. The iridium complex with the thick indole and quinoline structure provided by the invention can be used as a luminescent material to directly form an organic electroluminescent layer.
The cathode is preferably a metal including, but not limited to, calcium, magnesium, barium, aluminum, and silver, preferably aluminum.
In order to improve the performance and efficiency of the device, the organic thin film layer between the anode and the light emitting layer preferably further includes one or more of a hole injection layer, a hole transport layer, and an electron blocking layer. The organic thin film layer between the light emitting layer and the cathode preferably further includes one or more of a hole blocking layer and an electron injection layer and an electron transport layer. The materials and thicknesses of the hole injection layer, the hole transport layer, the electron blocking layer, the organic electroluminescent layer, the hole blocking layer, the electron injection layer, and the electron transport layer are not particularly limited in the present invention, and may be selected and adjusted according to materials and thicknesses well known to those skilled in the art. The present invention is not particularly limited in the preparation processes of the electrode, the hole injection layer, the hole transport layer, the electron blocking layer, the organic electroluminescent layer, the hole blocking layer, the electron injection layer and the electron transport layer, and is preferably prepared by a process of vacuum evaporation, solution spin coating, solution blade coating, inkjet printing, offset printing and stereolithography.
The preparation method of the organic electroluminescent device is not particularly limited, and the preparation method can be carried out according to the following steps: forming an anode on the substrate; forming one or more organic thin film layers including a light emitting layer on the anode; forming a cathode on the organic thin film layer;
the light-emitting layer comprises one or more iridium complexes containing fused indole and quinoline structures.
The structure and material of the organic electroluminescent device in the preparation method, and the corresponding preferred principle, and the corresponding material and structure in the organic electroluminescent device, and the corresponding preferred principle may be corresponding, and are not described in detail herein.
The present invention first forms an anode on a substrate, and the present invention does not specifically limit the manner of forming the anode, and may be performed according to a method known to those skilled in the art. The present invention is not particularly limited in the form of the light-emitting layer and the organic thin film layer below and above the light-emitting layer, and the organic thin film layer can be formed on the anode by vacuum evaporation, solution spin coating, solution blade coating, inkjet printing, offset printing, or three-dimensional printing. After the organic layer is formed, a cathode is prepared on the surface thereof, and the cathode formation method is not particularly limited in the present invention, and is preferably a method well known to those skilled in the art, including but not limited to vacuum deposition.
Compared with the prior art, the iridium complex containing the fused indole and quinoline structure has the structure shown in the formula I-1 or the formula I-2. The iridium complex containing the fused indole and quinoline structure provided by the invention can be used as a luminescent layer to be applied to an organic electroluminescent device, so that the luminescent efficiency and the service life of the device are greatly improved.
Detailed Description
In order to further illustrate the present invention, the iridium complex containing fused indole and quinoline structures and the electroluminescent device provided by the present invention are described in detail below with reference to the examples.
Example 1
The chemical structure and the synthetic route of I-1-1 are as follows:
in a 1000mL two-necked flask under argon atmosphere, 1-1(17.25g, 50mmol), cuprous iodide (0.85g, 5mmol), copper powder (12.5g, 200mmol) and potassium carbonate (27.5g, 200mmol) were weighed, 250mL of o-dichlorobenzene (o-DCB), 40mL of methyl o-iodobenzoate (250mmol) were added, the temperature was raised to 220 ℃ and the mixture was stirred under argon atmosphere for 50 hours, then cooled to room temperature, extracted with dichloromethane and water, the organic phase was separated, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product 1-2(4.0g, yield: 13%) was obtained by column separation. Elemental analysis Structure (C)40H27N3O4): theoretical value C, 78.29; h, 4.43; n, 6.85; test value C, 78.30; h, 4.40; and N, 6.80. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 613.20; experimental value 613.2 (M)+)。
Under argon atmosphere, 1-2(6.0g, 10mmol) was added to a 500mL two-necked flask, 90mL tetrahydrofuran was introduced, stirred at room temperature, 100mL (100mmol) of methylmagnesium bromide was added dropwise, the temperature was raised to 80 ℃ to react for 12 hours, then cooled to room temperature, ethyl acetate and water were added to extract, the organic phase was separated, dried over anhydrous sodium sulfate was added, the solvent was removed from the organic phase obtained by filtration, and the product 1-3(1.0g, yield: 33%) was obtained by column separation. Elemental analysis Structure (C)42H35N3O2): theoretical value C, 82.19; h, 5.75; n, 6.85; test value C, 82.41; h, 5.70; and N, 6.90. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 613.27; experimental value 613.3 (M)+)。
In a 500mL single-neck flask, 1-3(0.61g, 1mmol) was weighed under argon atmosphere, 20mL of glacial acetic acid was added, 3mL of concentrated hydrochloric acid was added, heating was performed to 130 ℃ and reaction was performed for 4 hours, then cooling was performed to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product 1-4(0.3g, 51%) was obtained by column separation. Elemental analysis Structure (C)42H31N3): theoretical value C, 87.32; h, 5.41; n,7.27 test value C, 87.30; h, 5.40; and N, 7.30. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 577.25; experimental value 577.3 (M)+)。
Ligand 1-5(1.62g, 5.73mmol), iridium trichloride trihydrate (0.92g, 2.6mmol), ethylene glycol monoethyl ether 30ml and water 10ml were added to a round bottom flask under an argon atmosphere, and the system was refluxed at elevated temperature for 24 hours. After the reaction is finished, water is added to precipitate the product, and the product is filtered and dried. The crude products 1-6 were used in the next reaction without purification.
The crude product, ligand acetylacetone (0.39g, 3.9mmol), sodium carbonate (0.82g, 7.8mmol), and ethylene glycol ethyl ether (30ml) were added to a two-neck flask under an argon atmosphere, and the mixture was refluxed at an elevated temperature for 20 hours. Poured into water, extracted and column chromatographed to give the products 1-7(1.66g, 74.6% yield). Elemental analysis Structure (C)35H25Br2IrN2O2): theoretical value C, 49.02; h, 2.94; n,3.27 test value C, 49.08; h, 2.92; and N, 3.22. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 855.99; experimental value 856.0 (M)+)。
In a 50mL single-neck flask, under argon atmosphere, 1-4(2.4g,4mmol), 1-7(0.86mg, 1mmol), Pd were weighed2(dba)3(0.091g，0.1mmol)，t-Bu3PHBF4(0.09g, 0.3mmol), t-BuONa (0.29g,3mmol), 20mL of toluene was introduced, heated to 110 ℃ and reacted for 4 hours, followed by cooling to room temperatureAfter extraction with dichloromethane and water, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the filtered organic phase, and the product 1-1-1(1.15g, 62%) was obtained by column separation. Elemental analysis Structure (C)119H85IrN8O2): theoretical value C, 77.21; h, 4.63; n, 6.05; test value C, 77.25; h, 4.61; and N, 6.01. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 1850.64; experimental value 1850.6 (M)+)。
Example 2
The chemical structure and synthetic route of I-1-23 are as follows:
a mixture of 1-2(0.85g), ethanol (30mL), water (30mL) and NaOH was heated at 100 ℃ for 3 hours. After cooling to room temperature, dilute hydrochloric acid was added to the mixture until a white solid appeared. The suspension is filtered off, the solid is washed with water and the resulting solid is heated with a mixture of polyphosphoric acids at 180 ℃ for 4 hours. After cooling to room temperature, the mixture was poured into hot water. After cooling to room temperature, the mixture was then extracted with dichloromethane and washed with water. The organic phase obtained by filtration was freed of the solvent, and the column was isolated to give the product 2-1(0.48g, yield: 63%). Elemental analysis Structure (C)38H19N3O2): theoretical value C, 83.05; h, 3.48; n, 6.35; test value C, 83.01; h, 3.41; n, 6.33. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 549.15; experimental value 549.2 (M)+)。
A100 ml round-bottomed flask equipped with a reflux condenser was charged with 2-1(0.77g, 1.4mmol), 4, 4' -dibromodiphenyl ether (1.38g, 4.2mmol), cuprous iodide (0.02g, 0.14mmol) and potassium carbonate (0.57g, 4.2mmol), DMI 20 ml; filling argon, then pumping air, and continuously ventilating for three times; heating to 160 ℃ and reacting for 24 h. Cooling to room temperature, adding dilute hydrochloric acid and 300ml of dichloromethane for extraction, stirring for 1-2 hours, filtering to remove the catalyst, washing with water for three times, drying the organic phase with anhydrous sodium sulfate, removing the solvent under reduced pressure, and performing column separation to obtain a sample 2-2(0.60g, 54.2%). Yuan-Yuan (Chinese character)Structure of elemental analysis (C)50H26BrN3O3): theoretical value C, 75.38; h, 3.29; n, 5.27; test value C, 75.31; h, 3.21; and N, 5.31. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 795.12; experimental value 795.1 (M)+)。
2-2(0.8g, 1.0mmol) was added to a single-neck flask, and bis (pinacolato) diboron (0.76g, 2.0mmol), Pd (dppf) Cl was added to the flask in a glove box2(0.08g, 0.1mmol) and KOAc (0.19g, 2.0mmol), 30mL dry DMF under argon, and stirred in an oil bath at 80 ℃ for 24h, the solution turns black. The reaction solution was poured into water, filtered with suction, and the crude product was subjected to column separation to give 2-3(0.54g, 64.3%) of the product. Elemental analysis Structure (C)56H38BN3O5): theoretical value C, 79.72; h, 4.54; n, 4.98; test value C, 79.71; h, 4.50; and N, 4.91. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 843.29; experimental value 843.3 (M)+)。
Ligand 2-4(1.85g, 5.73mmol), iridium trichloride trihydrate (0.92g, 2.6mmol), ethylene glycol monoethyl ether 30ml and water 10ml were added to a round bottom flask under an argon atmosphere, and the system was refluxed at elevated temperature to react for 24 hours. After the reaction, water is added to precipitate the product, which is then filtered and dried. The crude products 2-5 were used directly in the next reaction without purification.
The crude product, ligand 2-6(0.61g, 3.9mmol), potassium carbonate (0.82g, 7.8mmol) and ethylene glycol ethyl ether (30ml) were added to a two-neck flask under an argon atmosphere, and the mixture was refluxed at an elevated temperature for 20 hours. Poured into water, extracted and column chromatographed to give 2-7(1.73g, 67.1% yield). Elemental analysis Structure (C)43H35Br2IrN4O2): theoretical value C, 52.07; h, 3.56; n,5.65 test value C, 52.08; h, 3.52; n, 5.62. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 990.08; experimental value 990.1 (M)+)。
2-3(2.02g, 2.4mmol), 2-7(0.94g, 1mmol), Pd were added to a two-necked flask2(dba)3(0.05g, 0.05mmol), s-phos (0.04g, 0.1mmol) and Aliquat 336(10mg), 20ml of dried formazan was added under argonBenzene and 1.5ml of a 2M aqueous potassium carbonate solution were stirred in an oil bath at 100 ℃ for 12 h. The reaction was poured into water, extracted with dichloromethane, concentrated, and column isolated to give the product 1-2-23(1.27g, 56.0%). Elemental analysis Structure (C)143H87IrN10O8): theoretical value C, 75.81; h, 3.87; n,6.18, test value C, 75.76; h, 3.81; and N, 6.11. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 2264.63; experimental value 2264.6 (M)+)。
Example 3
The chemical structure and synthetic route of I-1-25 are as follows:
in a 100mL two-necked flask under an argon atmosphere, 1-1(3.45g, 10mmol), 3-1(12g, 50mmol), cuprous iodide (190mg, 1mmol), copper powder (2.5g, 40mmol) and potassium carbonate (5.5g, 40mmol) were weighed, 50mL of o-dichlorobenzene (o-DCB) was added, the temperature was raised to 220 ℃ and the mixture was stirred under an argon atmosphere for 50 hours, then cooled to room temperature, extracted with dichloromethane and water, the organic phase was separated, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product 3-2(0.67g, yield: 10%) was obtained by column separation. Elemental analysis Structure (C)44H35N3O4): theoretical value C, 78.90; h, 5.27; n, 6.27; test value C, 78.93; h, 5.21; and N, 6.21. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 669.26; experimental value 669.3 (M)+)。
Intermediate 3-2(0.67g, 1mmol) and CF3SO3H was added to a 100mL two-necked flask. The mixture was stirred at room temperature for 24 hours and then for 30 minutes with a mixture of water and pyridine (8: 1 by volume). The stirred mixture was cooled to room temperature, extracted with dichloromethane, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The obtained residue was separated by column to obtain intermediate 3-3(0.14g, yield: 26%). Elemental analysis Structure (C)36H19N3O2): theoretical value C, 82.27; h, 3.64; n, 8.00; test valueC, 82.21; h, 3.61; and N, 7.91. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 525.15; experimental value 525.2 (M)+)。
A100 ml round bottom flask was equipped with a reflux condenser and charged with 3-3(0.74g, 1.4mmol), 2, 5-dimethyl-1, 4 dibromobenzene (1.1g, 4.2mmol), cuprous iodide (0.02g, 0.14mmol) and potassium carbonate (0.57g, 4.2mmol), DMI 20 ml; filling argon, then pumping air, and continuously ventilating for three times; heating to 160 ℃ and reacting for 24 h. Cooling to room temperature, adding dilute hydrochloric acid and 300ml dichloromethane for extraction, stirring for 1-2 hours, filtering to remove the catalyst, washing with water three times, drying the organic phase with anhydrous sodium sulfate, removing the solvent under reduced pressure, and separating by a column to obtain a sample 3-4(0.66g, 67%). Elemental analysis Structure (C)44H26BrN3O2): theoretical value C, 74.58; h, 3.70; n, 5.93; test value C, 74.52; h, 3.79; and N, 5.81. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 707.12; experimental value 707.1 (M)+)。
3-4(0.7g, 1.0mmol) was added to a single-neck flask, and bis (pinacolato) diboron (0.76g, 2.0mmol), Pd (dppf) Cl was added to the flask in a glove box2(0.08g, 0.1mmol) and KOAc (0.19g, 2.0mmol), 30mL dry DMF under argon, and stirred in an oil bath at 80 ℃ for 24h, the solution turns black. The reaction solution was poured into water, filtered with suction, and the crude product was subjected to column separation to give 3-5(0.58g, 76.4%) of the product. Elemental analysis Structure (C)50H38BN3O4): theoretical value C, 79.47; h, 5.07; n, 5.56; test value C, 79.41; h, 5.01; n, 5.51. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 755.30; experimental value 755.3 (M)+)。
Ligand 3-6(2.06g, 5.73mmol), iridium trichloride trihydrate (0.92g, 2.6mmol), ethylene glycol monoethyl ether 30ml and water 10ml are added into a round bottom flask under argon atmosphere, and the system is refluxed at elevated temperature and reacted for 24 hours. After the reaction, water is added to precipitate the product, which is then filtered and dried. The crude products 3-7 were used in the next reaction without purification.
The crude product, ligand 3-8(0.61g, 3.9mmol), carbon were added to a two-necked flask under an argon atmospherePotassium (0.82g, 7.8mmol) and ethylene glycol ethyl ether (30ml) were refluxed at elevated temperature for 20 hours. Poured into water, extracted and subjected to column chromatography to obtain the product 3-9(1.61g, 58.3% yield). Elemental analysis Structure (C)51H41Br2IrN2O2): theoretical value C, 57.47; h, 3.88; n,2.63 test value C, 57.41; h, 3.82; and N, 2.62. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 1064.12; experimental value 1064.1 (M)+)。
A two-neck flask was charged with 3-5(1.81g, 2.4mmol), 3-9(0.73g, 1mmol), Pd2(dba)3(0.10g, 0.10mmol), s-phos (0.08g, 0.2mmol) and Aliquat 336(10mg), 20ml of dry toluene and 3ml of 2M aqueous potassium carbonate solution were added under argon and stirred in an oil bath at 100 ℃ for 12 h. The reaction solution was poured into water, extracted with dichloromethane, concentrated, and column-separated to give the product 1-1-25(1.17g, 54.3%). Elemental analysis Structure (C)139H93IrN8O6): theoretical value C, 77.17; h, 4.33; n,5.18, test value C, 77.11; h, 4.28; and N, 5.12. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 2162.68; experimental value 2162.7 (M)+)。
Example 4
The chemical structure and synthetic route of I-1-34 are as follows:
in a 1000mL two-necked flask under argon atmosphere, 4-1(12.8g, 50mmol), cuprous iodide (0.85g, 5mmol), copper powder (12.5g, 200mmol) and potassium carbonate (27.5g, 200mmol) were weighed, 250mL of o-dichlorobenzene (o-DCB), 20mL of methyl o-iodobenzoate (250mmol) were added, the temperature was raised to 220 ℃ and the mixture was stirred under argon protection for 50 hours, then cooled to room temperature, extracted with dichloromethane and water, the organic phase was separated, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the column was isolated to obtain 4-2(10.02g, yield: 51.4%). Elemental analysis Structure (C)26H18N2O2): theoretical value C, 79.98; h, 4.65; n, 7.17; test value C79.90; h, 4.60; and N, 7.11. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 390.14; experimental value 390.1 (M)+)。
A mixture of 4-2(0.39g), ethanol (30mL), water (30mL) and NaOH was heated at 100 ℃ for 3 hours. After cooling to room temperature, dilute hydrochloric acid was added to the mixture until a white solid appeared. The suspension is filtered off, the solid is washed with water and the resulting solid is heated with a mixture of polyphosphoric acids at 180 ℃ for 4 hours. After cooling to room temperature, the mixture was poured into hot water. After cooling to room temperature, the mixture was then extracted with dichloromethane and washed with water. The organic phase obtained by filtration was freed of the solvent, and the column was isolated to give the product 4-3(0.20g, yield: 56.0%). Elemental analysis Structure (C)25H14N2O): theoretical value C, 83.78; h, 3.94; n, 7.82; test value C, 83.71; h, 3.91; and N, 7.86. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 358.11; experimental value 358.1 (M)+)。
A100 ml round-bottomed flask was equipped with a reflux condenser and charged with 4-3(0.50g, 1.4mmol), 4-4(1.4g, 4.2mmol), cuprous iodide (0.02g, 0.14mmol) and potassium carbonate (0.57g, 4.2mmol), DMI 20 ml; filling argon, then pumping air, and continuously ventilating for three times; heating to 160 ℃ and reacting for 24 h. Cooling to room temperature, adding dilute hydrochloric acid and 300ml dichloromethane for extraction, stirring for 1-2 hours, filtering to remove the catalyst, washing with water three times, drying the organic phase with anhydrous sodium sulfate, removing the solvent under reduced pressure, and separating by a column to obtain 4-5(0.57g, 67%) samples. Elemental analysis Structure (C)39H23BrN2O): theoretical value C, 76.10; h, 3.77; n, 4.55; test value C, 76.12; h, 3.79; n, 4.51. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 614.10; experimental value 614.1 (M)+)。
4-5(0.6g, 1.0mmol) was added to a single-neck flask, which was placed in a glove box, and bis (pinacolato) diboron (0.76g, 2.0mmol), Pd (dppf) Cl was added2(0.08g, 0.1mmol) and KOAc (0.19g, 2.0mmol), 30mL dry DMF under argon, and stirred in an oil bath at 80 ℃ for 24h, the solution turns black. The reaction solution was poured into water, filtered with suction, and the crude product was subjected to column separation to give 4-6(0.51g, 76.4%) as a product. Element classificationAnalysis structure (C)45H35BrN2O3): theoretical value C, 81.57; h, 5.32; n, 4.23; test value C, 81.51; h, 5.39; n, 4.21. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 662.27; experimental value 662.3 (M)+)。
Ligand 4-7(1.80g, 5.73mmol), iridium trichloride trihydrate (0.92g, 2.6mmol), ethylene glycol monoethyl ether 30ml and water 10ml were added to a round bottom flask under an argon atmosphere, and the system was refluxed at elevated temperature for 24 hours. After the reaction, water is added to precipitate the product, which is then filtered and dried. The crude products 4-8 were used in the next reaction without purification.
The crude product, ligand acetylacetone (0.39g, 3.9mmol), potassium carbonate (0.82g, 7.8mmol), and ethylene glycol ethyl ether (30ml) were added to a two-neck flask under an argon atmosphere, and the mixture was refluxed at an elevated temperature for 20 hours. Poured into water, extracted and subjected to column chromatography to obtain 4-9(1.43g, 58.3% yield). Elemental analysis Structure (C)39H31Br2F2IrN2O2): theoretical value C, 49.32; h, 3.29; n,2.95 test value C, 49.31; h, 3.22; n, 2.92. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 948.03; experimental value 948.0 (M)+)。
4-6(1.59g, 2.4mmol), 4-9(0.95g, 1mmol), Pd were added to a two-necked flask2(dba)3(0.10g, 0.10mmol), s-phos (0.08g, 0.2mmol) and Aliquat 336(10mg), 20ml of dry toluene and 3ml of 2M aqueous potassium carbonate solution were added under argon and stirred in an oil bath at 100 ℃ for 12 h. The reaction solution was poured into water, extracted with dichloromethane, concentrated, and column-separated to give the product 1-1-34(1.77g, 51.2%). Elemental analysis Structure (C)117H77F2IrN6O4): theoretical value C, 75.51; h, 4.17; n,4.52, test value C, 75.41; h, 4.18; n, 4.62. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 1860.56; experimental value 1860.6 (M)+)。
Example 5
The chemical structure and synthetic route of I-1-37 are as follows:
in a 1000mL two-necked flask under argon atmosphere, 5-1(12.8g, 50mmol), cuprous iodide (0.85g, 5mmol), copper powder (12.5g, 200mmol) and potassium carbonate (27.5g, 200mmol) were weighed, 250mL of o-dichlorobenzene (o-DCB), 20mL of methyl o-iodobenzoate (250mmol) were added, the temperature was raised to 220 ℃ and the mixture was stirred under argon atmosphere for 50 hours, then cooled to room temperature, extracted with dichloromethane and water, the organic phase was separated, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product 5-2 was obtained by column separation (6.68g, yield: 34.3%). Elemental analysis Structure (C)26H18N2O2): theoretical value C, 79.98; h, 4.65; n, 7.17; test value C, 79.90; h, 4.60; and N, 7.11. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 390.14; experimental value 390.1 (M)+)。
In a 500mL two-necked flask, 5-2(3.90g, 10mmol) was added under argon atmosphere, 90mL of tetrahydrofuran was introduced, stirred at room temperature, then 40mL (40mmol) of methylmagnesium bromide was added dropwise, warmed to 80 ℃ for reaction for 12 hours, then cooled to room temperature, extracted with ethyl acetate and water, the organic phase was separated, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product 5-3 was obtained by column separation (1.76g, yield: 45.0%). Elemental analysis Structure (C)27H22N2O): theoretical value C, 83.05; h, 5.68; n, 7.17; test value C, 83.01; h, 5.70; and N, 7.12. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 390.17; experimental value 390.2 (M)+)。
In a 500mL single-neck flask, 5-3(0.78g, 2mmol) was weighed under argon atmosphere, 50mL of glacial acetic acid was added, 5mL of concentrated hydrochloric acid was added, heating was carried out to 130 ℃ and reaction was carried out for 4 hours, then cooling was carried out to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product 5-4(0.59g, 79.3%) was obtained by column separation. Elemental analysis Structure (C)27H20N2): theoretical value C, 87.07; h, 5.41; n,7.52 test value C, 87.01; h5.36; and N, 7.50. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 372.16; experimental value 372.2 (M)+)。
A100 ml round bottom flask was equipped with a reflux condenser and charged with 5-4(0.73g, 1.4mmol), 1, 5-dibromonaphthalene (1.19g, 4.2mmol), cuprous iodide (0.02g, 0.14mmol) and potassium carbonate (0.57g, 4.2mmol), DMI 20 ml; filling argon, then pumping air, and continuously ventilating for three times; heating to 160 ℃ and reacting for 24 h. Cooling to room temperature, adding dilute hydrochloric acid and 300ml of dichloromethane for extraction, stirring for 1-2 hours, filtering to remove the catalyst, washing with water for three times, drying the organic phase with anhydrous sodium sulfate, removing the solvent under reduced pressure, and performing column separation to obtain 5-5(0.47g, 58.1%) samples. Elemental analysis Structure (C)37H25BrN2): theoretical value C, 76.95; h, 4.36; n, 4.85; test value C, 76.90; h, 4.31; and N, 4.88. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 576.12; experimental value 576.1 (M)+)。
5-5(0.58g, 1.0mmol) was charged into a single-neck flask, and bis (pinacolato) diboron (0.76g, 2.0mmol), Pd (dppf) Cl was added to the flask in a glove box2(0.08g, 0.1mmol) and KOAc (0.19g, 2.0mmol), 30mL dry DMF under argon, and stirred in an oil bath at 80 ℃ for 24h, the solution turns black. The reaction solution was poured into water, filtered under suction, and the crude product was subjected to column separation to give 5-6(0.48g, 76.1%) of the product. Elemental analysis Structure (C)43H37BN2O2): theoretical value C, 82.69; h, 5.97; n, 4.49; test value C, 82.60; h, 5.91; n, 4.41. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 624.29; experimental value 624.3 (M)+)。
Ligand 5-7(1.78g, 5.73mmol), iridium trichloride trihydrate (0.92g, 2.6mmol), ethylene glycol monoethyl ether 30ml and water 10ml were added to a round-bottomed flask under an argon atmosphere, and the system was refluxed at elevated temperature to react for 24 hours. After the reaction is finished, water is added to precipitate the product, and the product is filtered and dried. The crude products 5-8 were used in the next reaction without purification.
The crude product, ligand 5-9(0.69g, 3.9mmol), potassium carbonate (0.82g, 7.8mmol), ethylene glycol, was added to a two-necked flask under an argon atmosphere30ml of alcohol ether, heating the system to reflux, and reacting for 20 hours. Poured into water, extracted and subjected to column chromatography to obtain 5-10(1.60g, yield 62.3%). Elemental analysis Structure (C)45H37Br2IrN2O2): theoretical value C, 54.60; h, 3.77; n,2.83 test value C, 54.51; h, 3.72; and N, 2.82. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 988.09; experimental value 988.1 (M)+)。
A two-neck flask is added with 5-6(1.50g, 2.4mmol), 5-10(0.99g, 1mmol) and Pd2(dba)3(0.10g, 0.10mmol), s-phos (0.08g, 0.2mmol) and Aliquat 336(10mg), 20ml of dry toluene and 3ml of 2M aqueous potassium carbonate solution were added under argon and stirred in an oil bath at 100 ℃ for 12 h. The reaction solution was poured into water, extracted with dichloromethane, concentrated, and column-separated to give the product 1-1-37(0.94g, 51.8%). Elemental analysis Structure (C)119H87F2IrN6O2): theoretical value C, 78.31; h, 4.80; n,4.60, test value C, 78.41; h, 4.78; n, 4.62. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 1824.65; experimental value 1824.7 (M)+)。
Example 6
The chemical structure and the synthetic route of I-2-3 are as follows:
in a 100mL two-necked flask under argon atmosphere, 6-1(2.56g, 10mmol), 6-2(3.2g, 10mmol), cuprous iodide (190mg, 1mmol), copper powder (2.5g, 40mmol) and potassium carbonate (5.5g, 40mmol) were weighed, 50mL of o-dichlorobenzene (o-DCB) was added, the temperature was raised to 220 ℃ and the mixture was stirred under argon atmosphere for 50 hours, then cooled to room temperature, extracted with dichloromethane and water, the organic phase was separated, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the column was isolated to obtain 6-3(0.72g, yield: 16%). Elemental analysis Structure (C)29H26N2OS): theoretical value C, 77.30; h, 5.82; n, 6.22; test value C, 77.20; h, 5.80; and N, 6.25. Matrix-assisted laser desorption-flightTheoretical value of time mass spectrometry (MALDI-TOF-MS) 450.18; experimental value 450.2 (M)+)。
Intermediate 6-3(0.45g, 1mmol) and CF3SO3H was added to a 100mL two-necked flask. The mixture was stirred at room temperature for 24 hours and then for 30 minutes with a mixture of water and pyridine (8: 1 by volume). The stirred mixture was cooled to room temperature, extracted with dichloromethane, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The obtained residue was separated by column to obtain intermediate 6-4(0.25g, yield: 60%). Elemental analysis Structure (C)28H22N2S): theoretical value C, 80.35; h, 5.30; n, 6.69; test value C, 80.33; h, 5.21; and N, 6.60. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 418.15; experimental value 418.2 (M)+)。
Ligand 6-5(1.87g, 5.73mmol), iridium trichloride trihydrate (0.92g, 2.6mmol), ethylene glycol monoethyl ether 30ml and water 10ml were added to a round-bottomed flask under an argon atmosphere, and the system was refluxed at elevated temperature to react for 24 hours. After the reaction, water is added to precipitate the product, which is then filtered and dried. The crude products 6-6 were used in the next reaction without purification.
The crude product, ligand acetylacetone (0.39g, 3.9mmol), potassium carbonate (0.82g, 7.8mmol), and ethylene glycol ethyl ether (30ml) were added to a two-neck flask under an argon atmosphere, and the mixture was refluxed at an elevated temperature for 20 hours. Poured into water, extracted and column chromatographed to give 6-7(1.52g, 62.2% yield). Elemental analysis Structure (C)39H33Br2IrN2O4): theoretical value C, 49.53; h, 3.52; n,2.96 test value C, 49.51; h, 3.61; and N, 2.92. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 944.04; experimental value 944.0 (M)+)。
A two-neck flask was charged with 6-4(1.50g, 2.4mmol), 6-7(0.99g, 1mmol), Pd2(dba)3(0.10g, 0.10mmol), s-phos (0.08g, 0.2mmol), t-BuONa (0.29g,3mmol), and Aliquat 336(10mg) were added to 20ml of dry toluene under argon and stirred in an oil bath at 100 ℃ for 12 h. Pouring the reaction solution into water, extracting with dichloromethane, concentrating, and separating with column to obtain product 1-2-3(0.86g, 53.2%). Elemental analysis Structure (C)95H75F2IrN6O4S2): theoretical value C, 70.39; h, 4.66; n,5.18, test value C, 70.41; h, 4.68; and N, 5.12. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 1620.49; experimental value 1620.5 (M)+)。
Example 7
The chemical structure and the synthetic route of I-2-4 are as follows:
in a 100mL two-necked flask under an argon atmosphere, 1-1(3.45g, 10mmol), cuprous iodide (190mg, 1mmol), copper powder (2.5g, 40mmol) and potassium carbonate (5.5g, 40mmol) were weighed, 50mL of o-dichlorobenzene (o-DCB), 8mL of methyl 4-t-butyl o-iodobenzoate 7-1(50mmol) were added, the temperature was raised to 220 ℃ and stirred under an argon atmosphere for 50 hours, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried with anhydrous sodium sulfate, the solvent was removed from the filtered organic phase, and the product 7-2(0.9g, yield: 12%) was obtained by column separation. Elemental analysis Structure (C)48H43N3O4): theoretical value C, 79.42; h, 5.97; n, 5.79; test value C, 79.30; h, 5.80; and N, 5.80. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical value 725.33; experimental value 725.3 (M)+)。
In a 100mL two-necked flask under an argon atmosphere, 7-2(1.4g, 2mmol) was added, 18mL of tetrahydrofuran was introduced, stirred at room temperature, then 20mL (20mmol) of phenylmagnesium bromide was added dropwise, the temperature was raised to 80 ℃ to react for 12 hours, then cooled to room temperature, ethyl acetate and water were added to extract, the organic phase was separated, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product 7-3 was obtained by column separation (0.64g, yield: 33%). Elemental analysis Structure (C)70H59N3O2): theoretical value C, 86.30; h, 6.10; n, 4.31; test value C, 86.31; h, 6.10; and N, 4.30. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 973.46; experimental value 973.5(M+)。
In a 100mL single-neck flask, 7-3(0.97g, 1mmol) was weighed under argon atmosphere, 20mL of glacial acetic acid was added, 3mL of concentrated hydrochloric acid was added, heating was carried out to 130 ℃ and reaction was carried out for 4 hours, then cooling was carried out to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product 7-4(0.40g, 43%) was obtained by column separation. Elemental analysis Structure (C)70H55N3): theoretical value C, 89.61; h, 5.91; n, 4.48; test value C, 89.60; h, 5.90; and N, 4.50. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 937.44; experimental value 937.4 (M)+)。
In a 100mL three-necked flask, 7-4(1.87g, 2mmol), dibromopropane (0.8g, 4mmol) and anhydrous potassium carbonate (0.6g, 4mmol) were charged under an argon atmosphere, and 20mL of DMF was taken and added to the flask, and the temperature was raised to 120 ℃ to react for 20 hours. The reaction mixture was cooled to room temperature, poured into water and extracted with dichloromethane to separate the organic phase. Dried by adding anhydrous sodium sulfate, the organic phase obtained by filtration was freed of the solvent, and the crude product was column-separated to obtain the product 7-5(1.37g, yield: 65.0%). Elemental analysis Structure (C)73H60BrN3): theoretical value C, 82.78; h, 5.71; n,3.97, test value C, 82.71; h, 5.62; and N, 3.98. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 1057.40; experimental value 1057.4 (M)+)。
Ligand 7-6(1.98g, 5.73mmol), iridium trichloride trihydrate (0.92g, 2.6mmol), ethylene glycol monoethyl ether 30ml and water 10ml were added to a round bottom flask under an argon atmosphere, and the system was refluxed at elevated temperature for 24 hours. After the reaction, water is added to precipitate the product, which is then filtered and dried. The crude products 7-7 were used in the next reaction without purification.
The crude product, ligand 7-8(0.83g, 3.9mmol), potassium carbonate (0.82g, 7.8mmol) and ethylene glycol ethyl ether (30ml) were added to a two-neck flask under argon atmosphere, and the mixture was refluxed at elevated temperature for 20 hours. Poured into water, extracted and subjected to column chromatography to obtain 7-9(1.74g, yield 61.2%). Elemental analysis Structure (C)57H59IrN2O4S2): theoretical value C, 62.67; h, 5.44; n,2.56 test value C, 62.61; h, 5.47; and N, 2.52. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 1092.35; experimental value 1092.4 (M)+)。
In a 100mL three-necked flask, 7-9(1.09g, 1mmol), 7-5(2.10g, 2mmol) and anhydrous potassium carbonate (0.6g, 4mmol) were charged under an argon atmosphere, 20mL of DMF was taken and the flask was heated to 120 ℃ to react for 20 hours. The reaction mixture was cooled to room temperature, poured into water and extracted with dichloromethane to separate the organic phase. Dried by adding anhydrous sodium sulfate, the organic phase obtained by filtration was freed of the solvent, and the crude product was column-separated to give the product 1-2-4(1.30g, yield: 42.8%). Elemental analysis Structure (C)203H177IrN8O4S2): theoretical value C, 79.97; h, 5.85; n,3.68, test value C, 79.91; h, 5.82; and N, 3.62. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 3047.30; experimental value 3047.3 (M)+)。
Example 8
The chemical structure and the synthetic route of I-2-5 are as follows:
in a 1000mL two-necked flask under argon atmosphere, 8-1(12.8g, 50mmol), 8-2(14.2g, 50mmol), cuprous iodide (0.85g, 5mmol), copper powder (12.5g, 200mmol) and potassium carbonate (27.5g, 200mmol) were weighed, 250mL of o-dichlorobenzene (o-DCB) was added, the temperature was raised to 220 ℃ and the mixture was stirred under argon atmosphere for 50 hours, then cooled to room temperature, extracted with dichloromethane and water, the organic phase was separated, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product 8-3(8.95g, yield: 38.9%) was obtained by column separation. Elemental analysis Structure (C)31H28N2O2): theoretical value C, 80.84; h, 6.13; n, 6.08; test value C, 80.81; h, 6.08; and N, 6.02. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 460.22; experimental value 460.2 (M)+)。
Intermediate 8-3(0.46g, 1 mmo)l) and CF3SO3H was added to a 100mL two-necked flask. The mixture was stirred at room temperature for 24 hours and then for 30 minutes with a mixture of water and pyridine (8: 1 by volume). The stirred mixture was cooled to room temperature, extracted with dichloromethane, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The obtained residue was separated by column to obtain intermediate 8-4(0.13g, yield: 31.2%). Elemental analysis Structure (C)28H22N2O): theoretical value C, 83.56; h, 5.51; n, 6.96; test value C, 83.51; h, 5.51; and N, 6.95. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 402.17; experimental value 402.2 (M)+)。
Ligand 8-5(0.98g, 3mmol) and t-BuONa (0.29g,3mmol) in DMSO-D6(5mL) were reacted at 80 ℃ for 12h by D2After quenching with O (10mL), the extract was filtered through celite. The solvent was evaporated to dryness to afford ligand 8-6(0.76g, 75.6%). Elemental analysis Structure (C)18H7D9BrN): theoretical value C, 64.48; h, 7.51; n,4.18 test value C, 64.41; h, 7.48; n, 4.11. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 334.10; experimental value 334.1 (M)+)。
Ligand 8-6(1.78g, 5.73mmol), iridium trichloride trihydrate (0.92g, 2.6mmol), ethylene glycol monoethyl ether 30ml and water 10ml were added to a round bottom flask under an argon atmosphere, and the system was refluxed at elevated temperature for 24 hours. After the reaction, water is added to precipitate the product, which is then filtered and dried. The crude products 8-7 were used in the next reaction without purification.
The crude product, ligand acetylacetone (0.83g, 3.9mmol), potassium carbonate (0.82g, 7.8mmol), and ethylene glycol ethyl ether (30ml) were added to a two-neck flask under an argon atmosphere, and the mixture was refluxed at an elevated temperature for 20 hours. Poured into water, extracted and subjected to column chromatography to obtain 8-9(1.48g, yield 62.2%). Elemental analysis Structure (C)49H35D18Br2IrN2O2): theoretical value C, 54.90; h, 6.67; n,2.61 test value C, 54.93; h, 6.61; and N, 2.69. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 1070.32; experimental value 1070.3 (M)+)。
A two-neck flask was charged with 8-4(0.96g, 2.4mmol), 8-9(0.99g, 1mmol), Pd2(dba)3(0.10g, 0.10mmol), s-phos (0.08g, 0.2mmol), t-BuONa (0.29g,3mmol), and Aliquat 336(10mg) were added to 20ml of dry toluene under argon and stirred in an oil bath at 100 ℃ for 12 h. The reaction solution was poured into water, extracted with dichloromethane, concentrated, and column-separated to give the product 1-2-5(0.77g, 48.2%). Elemental analysis Structure (C)97H61D18IrN6O4): theoretical value C, 72.68; h, 6.10; n,5.24, test value C, 72.61; h, 6.18; and N, 5.22. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 1602.69; experimental value 1602.7 (M)+)。
Example 9
The chemical structure and the synthetic route of I-1-12 are as follows:
adding 1-2(1.2g, 2mmol) into a 100mL two-neck flask under argon atmosphere, introducing 18mL tetrahydrofuran, stirring at room temperature, then dropwise adding 20mL (20mmol) of phenylmagnesium bromide, heating to 80 ℃, reacting for 12h, then cooling to room temperature, adding ethyl acetate and water for extraction, separating an organic phase, adding anhydrous sodium sulfate for drying, removing the solvent from the organic phase obtained by filtration, and carrying out column separation to obtain a product 9-1(0.70g, yield: 41%), and an elemental analysis structure (C)62H43N3O2): theoretical value C, 86.39; h, 5.03; n, 4.87; test value C, 86.41; h, 5.10; and N, 4.90. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 861.34; experimental value 861.3 (M)+)。
In a 100mL single-neck flask, 9-1(0.86g, 1mmol) was weighed under argon atmosphere, 20mL of glacial acetic acid was added, 3mL of concentrated hydrochloric acid was added, the mixture was heated to 130 ℃ and reacted for 4 hours, then cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product 9-2(0.6g, 73%) was obtained by column separation. Element classificationAnalysis structure (C)62H39N3): theoretical value C, 90.15; h, 4.76; n, 5.09; test value C, 90.10; h, 4.78; and N, 5.10. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 825.31; experimental value 825.3 (M)+)。
A100 ml round-bottomed flask was equipped with a reflux condenser, and 9-2(1.16g, 1.4mmol), 2, 8-dibromodibenzothiophene 5, 5-dioxide (1.56g, 4.2mmol), cuprous iodide (0.02g, 0.14mmol) and potassium carbonate (0.57g, 4.2mmol), DMI 20ml were added; filling argon, then pumping air, and continuously ventilating for three times; heating to 160 ℃ and reacting for 24 h. Cooling to room temperature, adding dilute hydrochloric acid and 300ml of dichloromethane for extraction, stirring for 1-2 hours, filtering to remove the catalyst, washing with water for three times, drying the organic phase with anhydrous sodium sulfate, removing the solvent under reduced pressure, and performing column separation to obtain a sample 9-3(0.58g, 36.8%). Elemental analysis Structure (C)74H44BrN3O2S): theoretical value C, 79.42; h, 3.96; n, 3.75; test value C, 79.31; h, 3.91; and N, 3.68. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 1117.23; experimental value 1117.2 (M)+)。
9-3(1.11g, 1.0mmol) was charged into a single-neck flask, and bis (pinacolato) diboron (0.76g, 2.0mmol), Pd (dppf) Cl was added to the flask2(0.08g, 0.1mmol) and KOAc (0.19g, 2.0mmol), 30mL dry DMF under argon, and stirred in an oil bath at 80 ℃ for 24h, the solution turns black. The reaction solution was poured into water, filtered off with suction, and the crude product was isolated by column chromatography to give product 9-4(0.77g, 66.1%). Elemental analysis Structure (C)80H56BN3O4S): theoretical value C, 82.39; h, 4.84; n, 3.60; test value C, 82.30; h, 4.80; n, 3.51. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 1165.41; experimental value 1165.4 (M)+)。
Ligand 9-5(1.90g, 5.73mmol), iridium trichloride trihydrate (0.92g, 2.6mmol), ethylene glycol monoethyl ether 30ml and water 10ml were added to a round-bottomed flask under an argon atmosphere, and the system was refluxed at elevated temperature to react for 24 hours. After the reaction, water is added to precipitate the product, which is then filtered and dried. The crude product 9-6 was used in the next reaction without purification.
The crude product, ligand acetylacetone (0.39g, 3.9mmol), potassium carbonate (0.82g, 7.8mmol), and ethylene glycol ethyl ether (30ml) were added to a two-neck flask under an argon atmosphere, and the mixture was refluxed at an elevated temperature for 20 hours. Poured into water, extracted and subjected to column chromatography to obtain 9-7(1.29g, yield 52.2%). Elemental analysis Structure (C)37H27Br2F2IrN2O4): theoretical value C, 46.60; h, 2.85; n,2.94 test value C, 46.63; h, 2.81; and N, 2.99. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 951.99; experimental value 952.0 (M)+)。
9-4(2.80g, 2.4mmol), 9-7(0.95g, 1mmol), Pd were added to a two-necked flask2(dba)3(0.10g, 0.10mmol), s-phos (0.08g, 0.2mmol) and Aliquat 336(10mg), 20ml of dry toluene and 3ml of 2M aqueous potassium carbonate solution were added under argon and stirred in an oil bath at 100 ℃ for 12 h. The reaction solution was poured into water, extracted with dichloromethane, concentrated, and column-separated to give the product 1-1-12(1.47g, 51.3%). Elemental analysis Structure (C)185H115F2IrN8O8S2): theoretical value C, 77.36; h, 4.04; n,3.90, test value C, 77.31; h, 4.08; and N, 3.81. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 2870.79; experimental value 2870.8 (M)+)。
Example 10
The chemical structure and the synthetic route of I-1-13 are as follows:
a100 ml round-bottomed flask was equipped with a reflux condenser, and 2-1(0.77g, 1.4mmol), 2-7-dibromo-9, 9-dimethylfluorene 10-1(1.47g, 4.2mmol), copper iodide (0.02g, 0.14mmol), potassium carbonate (0.57g, 4.2mmol), and DMI 20ml were added; filling argon, then pumping air, and continuously ventilating for three times; heating to 160 ℃ and reacting for 24 h. Cooling to room temperature, adding dilute hydrochloric acid and 300ml of dichloromethane for extraction, stirring for 1-2 hours, filtering to remove the catalyst, washing with water for three times, and drying the organic phase with anhydrous sodium sulfateAfter that, the solvent was removed under reduced pressure, and the column was separated to obtain sample 10-2(0.67g, 58.2%). Elemental analysis Structure (C)53H30BrN3O2): theoretical value C, 77.56; h, 3.68; n, 5.12; test value C, 77.51; h, 3.61; n, 5.11. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 819.15; experimental value 819.2 (M)+)。
10-2(0.82g, 1.0mmol) was charged into a single-neck flask, and bis (pinacolato) diboron (0.76g, 2.0mmol), Pd (dppf) Cl was added to the flask2(0.08g, 0.1mmol) and KOAc (0.19g, 2.0mmol), 30mL dry DMF under argon, and stirred in an oil bath at 80 ℃ for 24h, the solution turns black. The reaction solution was poured into water, filtered with suction, and the crude product was subjected to column separation to give 10-3(0.53g, 61.3%) as a product. Elemental analysis Structure (C)59H42BN3O4): theoretical value C, 81.66; h, 4.88; n, 4.84; test value C, 81.61; h, 4.80; and N, 4.81. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 867.33; experimental value 867.3 (M)+)。
Ligand 10-4(2.67g, 5.73mmol), iridium trichloride trihydrate (0.92g, 2.6mmol), ethylene glycol monoethyl ether 30ml and water 10ml were added to a round-bottomed flask under an argon atmosphere, and the system was refluxed at elevated temperature to react for 24 hours. After the reaction, water is added to precipitate the product, which is then filtered and dried. The crude product 10-5 was used in the next reaction without purification.
The crude product, ligand acetylacetone (0.39g, 3.9mmol), potassium carbonate (0.82g, 7.8mmol), and ethylene glycol ethyl ether (30ml) were added to a two-neck flask under an argon atmosphere, and the mixture was refluxed at an elevated temperature for 20 hours. Poured into water, extracted and column chromatographed to give the product 10-6(1.73g, 54.8% yield). Elemental analysis Structure (C)59H37Br2F2IrN4O2): theoretical value C, 57.90; h, 3.05; n,4.58 test value C, 57.93; h, 3.01; and N, 4.59. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 1222.09; experimental value 1222.1 (M)+)。
10-3(2.08g, 2.4mmol), 10-6(0.95g, 1mmol) and Pd were added to a two-necked flask2(dba)3(0.10g, 0.10mmol), s-phos (0.08g, 0.2mmol) and Aliquat 336(10mg), 20ml of dry toluene and 3ml of 2M aqueous potassium carbonate solution were added under argon and stirred in an oil bath at 100 ℃ for 12 h. The reaction solution was poured into water, extracted with dichloromethane, concentrated, and column-separated to give the product 1-1-13(1.08g, 42.3%). Elemental analysis Structure (C)165H97F2IrN10O6): theoretical value C, 77.84; h, 3.84; n,5.50, test value C, 77.81; h, 3.88; n, 5.51. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 2544.72; experimental value 2544.7 (M)+)。
Example 11
The chemical structure and the synthetic route of I-2-7 are as follows:
in a 100mL two-necked flask under an argon atmosphere, 11-1(2.56g, 10mmol), 2-bromoiodobenzene (2.81g, 10mmol), cuprous iodide (190mg, 1mmol), copper powder (2.5g, 40mmol) and potassium carbonate (5.5g, 40mmol) were weighed, 50mL of o-dichlorobenzene (o-DCB) was added, the temperature was raised to 220 ℃ and the mixture was stirred under an argon atmosphere for 50 hours, then cooled to room temperature, extracted with dichloromethane and water, the organic phase was separated, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the column was isolated to obtain product 11-2(1.72g, yield: 42%). Elemental analysis Structure (C)24H15BrN2): theoretical value C, 70.09; h, 3.68; n, 6.81; test value C, 70.01; h, 3.62; and N, 6.87. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 410.04; experimental value 410.0 (M)+)。
In a 100mL two-necked flask, under argon, 11-2(0.41g, 1mmol) was added, 20mL of anhydrous Tetrahydrofuran (THF) was added, and the apparatus was placed in a-78 deg.C dry ice/acetone bath to cool for 15 min. 5mL (2mmol) of n-hexane solution of n-butyllithium was measured out by syringe, and added dropwise to a reaction flask, reacted at-78 ℃ for 1 hour, then added 11-3 to the reaction system, and allowed to warm to room temperature for 12 hours. Then cooled to room temperature, and dichloromethane was addedAnd water extraction, separation of an organic phase, drying with anhydrous sodium sulfate, removal of the solvent from the filtered organic phase, and column separation to obtain the product 11-4(0.30g, yield: 59%). Elemental analysis Structure (C)36H24N2Si): theoretical value C, 84.34; h, 4.72; n, 5.46; test value C, 84.39; h, 4.65; and N, 5.41. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 512.17; experimental value 512.2 (M)+)。
In a 100mL two-necked flask, under an argon atmosphere, 11-4(0.51g, 1mmol), 3, 3-dimethyl-1-butene (0.64mL, 5mmol), RhCl (PPh)3)3(0.0092mg, 0.01mmol), 20mL of 1, 4-dioxane was added, and the mixture was heated to 135 ℃ to react for 24 hours. Then cooled to room temperature, extracted with dichloromethane and water, the organic phase was separated, dried with anhydrous sodium sulfate, the solvent was removed from the filtered organic phase, and the product 11-5(0.38g, 74%) was obtained by column separation. Elemental analysis Structure (C)36H22N2Si): theoretical value C, 84.67; h, 4.34; n, 5.49; test value C, 84.61; h, 4.30; n, 5.41. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 510.16; experimental value 510.2 (M)+)。
A100 ml round bottom flask was equipped with a reflux condenser and charged with 11-5(0.80g, 1.4mmol), 11-6(1.96g, 4.2mmol), cuprous iodide (0.02g, 0.14mmol) and potassium carbonate (0.57g, 4.2mmol), DMI 20 ml; filling argon, then pumping air, and continuously ventilating for three times; heating to 160 ℃ and reacting for 24 h. Cooling to room temperature, adding dilute hydrochloric acid and 300ml of dichloromethane for extraction, stirring for 1-2 hours, filtering to remove the catalyst, washing with water for three times, drying the organic phase with anhydrous sodium sulfate, removing the solvent under reduced pressure, and performing column separation to obtain a sample 11-7(0.46g, 37.2%). Elemental analysis Structure (C)57H34BrN5Si): theoretical value C, 76.33; h, 3.82; n, 7.81; test value C, 76.31; h, 3.86; and N, 7.88. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 895.18; experimental value 895.2 (M)+)。
11-7(0.90g, 1.0mmol) was added to a single-neck flask, and bis (pinacolato) diboron (0.76g, 2.0mmol), Pd (dppf) Cl were added to the flask in a glove box2(0.08g，0.1mmol)KOAc (0.19g, 2.0mmol), 30mL dry DMF under argon, and stirred in an oil bath at 80 ℃ for 24h, the solution turns black. The reaction solution was poured into water, filtered with suction, and the crude product was subjected to column separation to give 11-8(0.59g, 63.1%) as a product. Elemental analysis Structure (C)63H46BN5O2Si): theoretical value C, 80.16; h, 4.91; n, 7.42; test value C, 80.10; h, 4.98; and N, 7.39. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 943.35; experimental value 943.4 (M)+)。
Ligand 11-9(2.07g, 5.73mmol), iridium trichloride trihydrate (0.92g, 2.6mmol), ethylene glycol monoethyl ether 30ml and water 10ml were added to a round bottom flask under an argon atmosphere, and the system was refluxed at elevated temperature to react for 24 hours. After the reaction, water is added to precipitate the product, which is then filtered and dried. The crude product 11-10 was used in the next reaction without purification.
The crude product, ligand 11-11(0.68g, 3.9mmol), potassium carbonate (0.82g, 7.8mmol) and ethylene glycol ethyl ether (30ml) were added to a two-neck flask under argon atmosphere, and the mixture was refluxed at an elevated temperature for 20 hours. Poured into water, extracted and subjected to column chromatography to obtain the product 11-12(1.27g, yield 44.8%). Elemental analysis Structure (C)53H41Br2IrN2O2): theoretical value C, 58.40; h, 3.79; n,2.57 test value C, 58.30; h, 3.71; and N, 2.59. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 1088.12; experimental value 1088.1 (M)+)。
A two-neck flask was charged with 11-8(2.26g, 2.4mmol), 11-12(1.09g, 1mmol), Pd2(dba)3(0.10g, 0.10mmol), s-phos (0.08g, 0.2mmol) and Aliquat 336(10mg), 20ml of dry toluene and 3ml of 2M aqueous potassium carbonate solution were added under argon and stirred in an oil bath at 100 ℃ for 12 h. The reaction solution was poured into water, extracted with dichloromethane, concentrated, and column-separated to give the product 1-2-7(0.95g, 37.3%). Elemental analysis Structure (C)167H109IrN12O2Si2): theoretical value C, 78.23; h, 4.28; n,6.56, test value C, 78.21; h, 4.21; n, 6.51. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 2562.80; experimental value 2562.8 (M)+)。
Example 12
The chemical structure and the synthetic route of I-2-8 are as follows:
in a 1000mL two-necked flask under argon atmosphere, 12-1(12.8g, 50mmol), 12-2(11.35g, 50mmol), cuprous iodide (0.85g, 5mmol), copper powder (12.5g, 200mmol) and potassium carbonate (27.5g, 200mmol) were weighed, 250mL of o-dichlorobenzene (o-DCB) was added, the temperature was raised to 220 ℃ and the mixture was stirred under argon atmosphere for 50 hours, then cooled to room temperature, extracted with dichloromethane and water, the organic phase was separated, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product 12-3 was obtained by column separation (7.86g, yield: 38.9%). Elemental analysis Structure (C)27H20N2O2): theoretical value C, 80.18; h, 4.98; n, 6.93; test value C, 80.11; h, 4.93; and N, 6.98. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 404.15; experimental value 404.2 (M)+)。
Intermediate 12-3(0.40g, 1mmol) and CF3SO3H was added to a 100mL two-necked flask. The mixture was stirred at room temperature for 24 hours and then for 30 minutes with a mixture of water and pyridine (8: 1 by volume). The stirred mixture was cooled to room temperature, extracted with dichloromethane, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The obtained residue was separated by column to obtain intermediate 12-4(0.11g, yield: 32.2%). Elemental analysis Structure (C)24H14N2O): theoretical value C, 83.22; h, 4.07; n, 8.09; test value C, 83.28; h, 4.01; and N, 8.15. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 346.11; experimental value 346.1 (M)+)。
A100 ml round bottom flask was equipped with a reflux condenser and charged with 12-4(0.48g, 1.4mmol), 12-5(2.07g, 4.2mmol), cuprous iodide (0.02g, 0.14mmol) and potassium carbonate (0.57g, 4.2mmol), DMI 20 ml; filling argon, then pumping air, and continuously ventilating for three times; the mixture is heated to 160 ℃,and reacting for 24 hours. Cooling to room temperature, adding dilute hydrochloric acid and 300ml of dichloromethane for extraction, stirring for 1-2 hours, filtering to remove the catalyst, washing with water three times, drying the organic phase with anhydrous sodium sulfate, removing the solvent under reduced pressure, and performing column separation to obtain 12-6(0.67g, 62.3%) of a sample. Elemental analysis Structure (C)48H31BrN2OSi): theoretical value C, 77.88; h, 4.11; n, 3.69; test value C, 77.80; h, 4.19; and N, 3.68. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 758.14; experimental value 758.1 (M)+)。
12-6(0.76g, 1.0mmol) was charged into a single-neck flask, and bis (pinacolato) diboron (0.76g, 2.0mmol), Pd (dppf) Cl was added to the flask2(0.08g, 0.1mmol) and KOAc (0.19g, 2.0mmol), 30mL dry DMF under argon, and stirred in an oil bath at 80 ℃ for 24h, the solution turns black. The reaction solution was poured into water, filtered with suction, and the crude product was subjected to column separation to give 12-7(0.55g, 68.6%) as a product. Elemental analysis Structure (C)54H43BN2O3Si): theoretical value C, 80.39; h, 5.37; n, 3.47; test value C, 80.31; h, 5.38; and N, 3.42. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 806.31; experimental value 806.3 (M)+)。
Ligand 12-8(1.78g, 5.73mmol), iridium trichloride trihydrate (0.92g, 2.6mmol), ethylene glycol monoethyl ether 30ml and water 10ml were added to a round bottom flask under an argon atmosphere, and the system was refluxed at elevated temperature to react for 24 hours. After the reaction, water is added to precipitate the product, which is then filtered and dried. The crude product 12-9 was used in the next reaction without purification.
The crude product, ligand 12-10(0.72g, 3.9mmol), potassium carbonate (0.82g, 7.8mmol) and ethylene glycol ethyl ether (30ml) were added to a two-neck flask under argon atmosphere, and the mixture was refluxed at elevated temperature for 20 hours. Poured into water, extracted and subjected to column chromatography to obtain the product 12-11(1.11g, yield 42.8%). Elemental analysis Structure (C)45H45Br2IrN2O2): theoretical value C, 54.16; h, 4.55; n,2.81 test value C, 54.11; h, 4.51; n, 2.79. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 996.15; experimental value 996.2 (M)+)。
A two-neck flask was charged with 12-7(1.93g, 2.4mmol), 12-11(0.99g, 1mmol), Pd2(dba)3(0.10g, 0.10mmol), s-phos (0.08g, 0.2mmol) and Aliquat 336(10mg), 20ml of dry toluene and 3ml of 2M aqueous potassium carbonate solution were added under argon and stirred in an oil bath at 100 ℃ for 12 h. The reaction was poured into water, extracted with dichloromethane, concentrated and column isolated to give the product 1-2-8(0.84g, 38.3%). Elemental analysis Structure (C)141H107IrN6O4Si2): theoretical value C, 77.06; h, 4.91; n,3.82, test value C, 77.01; h, 4.89; and N, 3.81. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 2196.75; experimental value 2196.8 (M)+)。
Example 13
The chemical structure and the synthetic route of I-2-9 are as follows:
in a 1000mL two-necked flask under argon atmosphere, 13-1(12.8g, 50mmol), 13-2(10.8g, 50mmol), cuprous iodide, (0.85g, 5mmol), copper powder (12.5g, 200mmol) and potassium carbonate (27.5g, 200mmol) were weighed, 250mL of o-dichlorobenzene (o-DCB) was added, the temperature was raised to 220 ℃ and the mixture was stirred under argon atmosphere for 50 hours, then cooled to room temperature, extracted with dichloromethane and water, the organic phase was separated, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product 13-3(8.39g, yield: 42.6%) was obtained by column separation. Elemental analysis Structure (C)25H18N2OS): theoretical value C, 76.12; h, 4.60; n, 7.10; test value C, 76.19; h, 4.51; and N, 7.19. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 394.11; experimental value 394.1 (M)+)。
Intermediate 13-3(0.40g, 1mmol) and CF3SO3H was added to a 100mL two-necked flask. The mixture was stirred at room temperature for 24 hours and then for 30 minutes with a mixture of water and pyridine (8: 1 by volume). The stirred mixture was cooled to room temperature and extracted with dichloromethaneExtracted, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The obtained residue was separated by column to obtain intermediate 13-4(0.11g, yield: 36.2%). Elemental analysis Structure (C)24H14N2S): theoretical value C, 79.53; h, 3.89; n, 7.73; test value C, 79.58; h, 3.81; n, 7.79. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 362.09; experimental value 362.1 (M)+)。
A100 ml round-bottom flask was equipped with a reflux condenser, and 13-4(0.51g, 1.4mmol), 2, 5-dibromothiophene (1.01g, 4.2mmol), cuprous iodide (0.02g, 0.14mmol), potassium carbonate (0.57g, 4.2mmol), and DMI 20ml were added; filling argon, then pumping air, and continuously ventilating for three times; heating to 160 ℃ and reacting for 24 h. Cooling to room temperature, adding dilute hydrochloric acid and 300ml dichloromethane for extraction, stirring for 1-2 hours, filtering to remove the catalyst, washing with water three times, drying the organic phase with anhydrous sodium sulfate, removing the solvent under reduced pressure, and separating by a column to obtain 13-5(0.42g, 57.8%) of a sample. Elemental analysis Structure (C)28H15BrN2S2): theoretical value C, 64.25; h, 3.89; n, 7.73; test value C, 64.31; h, 3.95; and N, 7.71. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 521.99; experimental value 522.0 (M)+)。
13-5(0.52g, 1.0mmol) was charged into a single-neck flask, and bis (pinacolato) diboron (0.76g, 2.0mmol), Pd (dppf) Cl was added to the flask in a glove box2(0.08g, 0.1mmol) and KOAc (0.19g, 2.0mmol), 30mL dry DMF under argon, and stirred in an oil bath at 80 ℃ for 24h, the solution turns black. The reaction solution was poured into water, filtered off with suction, and the crude product was isolated by column chromatography to give 13-6(0.36g, 63.1%). Elemental analysis Structure (C)34H27BN2O2S2): theoretical value C, 71.58; h, 4.77; n, 4.91; test value C, 71.51; h, 4.70; and N, 4.83. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 570.16; experimental value 570.2 (M)+)。
Ligand 13-7(2.49g, 5.73mmol), iridium trichloride trihydrate (0.92g, 2.6mmol), ethylene glycol monoethyl ether 30ml and water 10ml were added to a round-bottomed flask under an argon atmosphere, and the system was refluxed at elevated temperature to react for 24 hours. After the reaction, water is added to precipitate the product, which is then filtered and dried. The crude product 13-8 was used in the next reaction without purification.
The crude product, ligand 13-9(0.67g, 3.9mmol), sodium carbonate (0.82g, 7.8mmol) and ethylene glycol ethyl ether (30ml) were added to a two-neck flask under an argon atmosphere, and the mixture was refluxed at an elevated temperature for 20 hours. Poured into water, extracted and subjected to column chromatography to obtain the product 12-11(1.21g, 37.8% yield). Elemental analysis Structure (C)65H45Br2IrN2O2): theoretical value C, 63.06; h, 3.66; n,2.26 test value C, 63.01; h, 3.61; and N, 2.29. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 1236.15; experimental value 1236.2 (M)+)。
13-6(1.37g, 2.4mmol), 13-10(1.24g, 1mmol) and Pd were added into a two-neck flask2(dba)3(0.10g, 0.10mmol), s-phos (0.08g, 0.2mmol) and Aliquat 336(10mg), 20ml of dry toluene and 3ml of 2M aqueous potassium carbonate solution were added under argon and stirred in an oil bath at 100 ℃ for 12 h. The reaction solution was poured into water, extracted with dichloromethane, concentrated, and column-separated to give the product 1-2-9(0.67g, 34.3%). Elemental analysis Structure (C)121H75IrN6O2S4): theoretical value C, 73.94; h, 3.85; n,4.28, test value C, 73.85; h, 3.89; n, 4.21. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 1964.45; experimental value 1964.5 (M)+)。
Example 14
The chemical structure and the synthetic route of I-2-10 are as follows:
in a 1000mL two-necked flask under argon atmosphere 14-1(12.8g, 50mmol), cuprous iodide (0.85g, 5mmol), copper powder (12.5g, 200mmol) and potassium carbonate (27.5g, 200mmol) were weighed, 250mL of o-dichlorobenzene (o-DCB), 20mL of methyl o-iodobenzoate (250mmol) were added, the temperature was raised to 220 deg.C, stirring was carried out for 50 hours under argon protection, then cooling was carried out to room temperature, and dichloro was addedMethane and water extraction, separation of the organic phase, drying with anhydrous sodium sulfate, removal of the solvent from the filtered organic phase, and column separation to give 14-2(7.58g, yield: 38.9%). Elemental analysis Structure (C)26H18N2O2): theoretical value C, 79.98; h, 4.65; n, 7.17; test value C, 79.90; h, 4.60; and N, 7.11. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 390.14; experimental value 390.1 (M)+)。
14-2(3.90g, 10mmol) was added to a 500mL two-necked flask under an argon atmosphere, 90mL of tetrahydrofuran was introduced, stirred at room temperature, then 40mL (40mmol) of methylmagnesium bromide was added dropwise, warmed to 80 ℃ for reaction for 12 hours, then cooled to room temperature, extracted with ethyl acetate and water, the organic phase was separated, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product 14-3(2.04g, yield: 52.3%) was obtained by column separation. Elemental analysis Structure (C)27H22N2O): theoretical value C, 83.05; h, 5.68; n, 7.17; test value C, 83.01; h, 5.70; and N, 7.12. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 390.17; experimental value 390.2 (M)+)。
14-3(0.78g, 2mmol) was weighed in a 500mL single-neck flask under argon atmosphere, 50mL glacial acetic acid was added, 5mL concentrated hydrochloric acid was added, heating was carried out to 130 ℃ and reaction was carried out for 4 hours, then cooling was carried out to room temperature, methylene chloride and water were added for extraction, the organic phase was separated, anhydrous sodium sulfate was added for drying, the solvent was removed from the organic phase obtained by filtration, and the product 14-4(0.48g, 65.1%) was obtained by column separation. Elemental analysis Structure (C)27H20N2): theoretical value C, 87.07; h, 5.41; n,7.52 test value C, 87.01; h, 5.36; and N, 7.50. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 372.16; experimental value 372.2 (M)+)。
A100 ml round bottom flask was equipped with a reflux condenser and charged with 14-4(0.73g, 1.4mmol), 14-5(1.47g, 4.2mmol), cuprous iodide (0.02g, 0.14mmol) and potassium carbonate (0.57g, 4.2mmol), DMI 20 ml; filling argon, then pumping air, and continuously ventilating for three times; heating to 160 ℃ and reacting for 24 h. Cooling to room temperature, adding dilute hydrochloric acid and dichloromethane 300ml for extraction, stirringAfter 1 to 2 hours, the catalyst was removed by filtration, washed three times with water, and the organic phase was dried over anhydrous sodium sulfate, the solvent was removed under reduced pressure, and the column separation yielded 14-6(0.56g, 62.3%) as a sample. Elemental analysis Structure (C)42H33BrN2): theoretical value C, 78.13; h, 5.15; n, 4.34; test value C, 78.10; h, 5.11; and N, 4.38. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 644.18; experimental value 644.2 (M)+)。
14-6(0.69g, 1.0mmol) was charged into a single-neck flask, and bis (pinacolato) diboron (0.76g, 2.0mmol), Pd (dppf) Cl was added to the flask2(0.08g, 0.1mmol) and KOAc (0.19g, 2.0mmol), 30mL dry DMF under argon, and stirred in an oil bath at 80 ℃ for 24h, the solution turns black. The reaction solution was poured into water, filtered with suction, and the crude product was subjected to column separation to give 14-7(0.47g, 68.6%) as a product. Elemental analysis Structure (C)48H45BN2O2): theoretical value C, 83.23; h, 6.55; n, 4.04; test value C, 83.28; h, 6.58; and N, 4.01. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 692.36; experimental value 692.4 (M)+)。
Ligand 14-8(2.14g, 5.73mmol), iridium trichloride trihydrate (0.92g, 2.6mmol), ethylene glycol monoethyl ether 30ml and water 10ml were added to a round-bottomed flask under an argon atmosphere, and the system was refluxed at elevated temperature to react for 24 hours. After the reaction, water is added to precipitate the product, which is then filtered and dried. The crude product 14-9 was used in the next reaction without purification.
The crude product, ligand 14-10(0.50g, 3.9mmol), potassium carbonate (0.82g, 7.8mmol) and ethylene glycol ethyl ether (30ml) were added to a two-neck flask under argon atmosphere, and the mixture was refluxed at elevated temperature for 20 hours. Poured into water, extracted and subjected to column chromatography to obtain 14-11(1.02g, yield 36.8%). Elemental analysis Structure (C)51H41Br2IrN2O2): theoretical value C, 57.47; h, 3.88; n,2.63 test value C, 57.41; h, 3.81; and N, 2.69. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 1064.12; experimental value 1064.1 (M)+)。
A two-neck flask was charged with 14-7(1.66g, 2.4mmol)，14-11(1.06g，1mmol)，Pd2(dba)3(0.10g, 0.10mmol), s-phos (0.08g, 0.2mmol) and Aliquat 336(10mg), 20ml of dry toluene and 3ml of 2M aqueous potassium carbonate solution were added under argon and stirred in an oil bath at 100 ℃ for 12 h. The reaction solution was poured into water, extracted with dichloromethane, concentrated, and column-separated to give the product 1-2-10(0.73g, 36.1%). Elemental analysis Structure (C)135H107IrN6O2): theoretical value C, 79.58; h, 5.29; n,4.12, test value C, 79.51; h, 5.21; n, 4.21. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 2036.81; experimental value 2036.8 (M)+)。
Example 15
The chemical structure and synthetic route of I-1-17 are as follows:
in a 100mL two-necked flask under argon atmosphere, 1-1(3.45g, 10mmol), 2-bromoiodobenzene (14.1g, 50mmol), cuprous iodide (190mg, 1mmol), copper powder (2.5g, 40mmol) and potassium carbonate (5.5g, 40mmol) were weighed, 50mL of o-dichlorobenzene (o-DCB) was added, the temperature was raised to 220 ℃ and the mixture was stirred under argon for 50 hours, then cooled to room temperature, extracted with dichloromethane and water, the organic phase was separated, dried with anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the column was isolated to obtain 15-1(0.92g, yield: 14%). Elemental analysis Structure (C)36H21Br2N3): theoretical value C, 65.98; h, 3.23; n, 6.41; test value C, 65.91; h, 3.21; n, 6.37. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 655.39; experimental value 655.4 (M)+)。
In a 100mL two-necked flask, under argon, 15-1(0.66g, 1mmol) was added, 20mL of anhydrous Tetrahydrofuran (THF) was added, and the apparatus was placed in a-78 deg.C dry ice/acetone bath to cool for 15 min. Measuring 5mL (2mmol) n-hexane solution of n-butyllithium by using a syringe, dropwise adding the n-hexane solution into a reaction bottle, reacting at-78 ℃ for 1 hour, adding diphenylchlorosilane into the reaction system, and raising the temperature toThe reaction was carried out at room temperature for 12 hours. Then, it was cooled to room temperature, extracted with dichloromethane and water, the organic phase was separated, dried by adding anhydrous sodium sulfate, the solvent was removed from the filtered organic phase, and the product 15-2 was obtained by column separation (0.52g, yield: 60%). Elemental analysis Structure (C)60H43N3Si2): theoretical value C, 83.58; h, 5.03; n, 4.87; test value C, 83.51; h, 5.08; and N, 4.81. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 861.30; experimental value 861.3 (M)+)。
In a 100mL two-necked flask, under an argon atmosphere, 15-2(0.83g, 1mmol), 3, 3-dimethyl-1-butene (0.64mL, 5mmol), RhCl (PPh)3)3(0.0092mg, 0.01mmol), 20mL of 1, 4-dioxane was added, and the mixture was heated to 135 ℃ to react for 24 hours. Then cooled to room temperature, extracted with dichloromethane and water, the organic phase was separated, dried with anhydrous sodium sulfate, the solvent was removed from the filtered organic phase, and the product 15-3(0.72g, 84%) was obtained by column separation. Elemental analysis Structure (C)60H39N3Si2): theoretical value C, 83.98; h, 4.58; n, 4.90; test value C, 84.01; h, 4.60; and N, 4.80. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 857.27; experimental value 857.3 (M)+)
A500 ml round bottom flask was equipped with a reflux condenser and charged with 15-3(3.60g, 4.2mmol), p-dibromobenzene (3.9g, 16.6mmol), cuprous iodide (0.08g, 0.42mmol) and potassium carbonate (1.72g, 12.4mmol), DMI 30 ml; filling argon, then pumping air, and continuously ventilating for three times; heating to 160 ℃ and reacting for 24 h. Cooling to room temperature, adding dilute hydrochloric acid and 300ml of dichloromethane for extraction, stirring for 1-2 hours, filtering to remove the catalyst, washing with water for three times, drying the organic phase with anhydrous sodium sulfate, removing the solvent under reduced pressure, and performing column separation to obtain a sample 15-4(3.06g, 72%). Elemental analysis Structure (C)66H42BrN3Si2): theoretical value C, 78.24; h, 4.18; n, 4.15; test value C, 78.20; h, 4.10; and N, 4.23. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 1011.21; experimental value 1011.2 (M)+)。
15-4(3.0g, 3.0mmol) was added to a single-neck flask,put into a glove box and added with bis (pinacolato) diboron (1.51g, 6.0mmol), Pd (dppf) Cl2(0.24g, 0.3mmol) and KOAc (0.58g, 6.0mmol), 50mL dry DMF under argon, and stirred in an oil bath at 80 ℃ for 24h, the solution turns black. The reaction solution was poured into water, filtered with suction, and the crude product was subjected to column separation to give 15-5(2.78g, 87.5%) product. Elemental analysis Structure (C)72H54BN3O2Si2): theoretical value C, 81.57; h, 5.13; n, 3.96; test value C, 81.52; h, 5.08; n, 3.92. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 1059.38; experimental value 1059.4 (M)+)。
Ligand 15-6(1.86g, 5.73mmol), iridium trichloride trihydrate (0.92g, 2.6mmol), ethylene glycol monoethyl ether 30ml and water 10ml were added to a round bottom flask under an argon atmosphere, and the system was refluxed at elevated temperature to react for 24 hours. After the reaction, water is added to precipitate the product, which is then filtered and dried. The crude product 15-7 was used in the next reaction without purification.
The crude product, ligand 15-8(0.87g, 3.9mmol), potassium carbonate (0.82g, 7.8mmol) and ethylene glycol ethyl ether (30ml) were added to a two-neck flask under argon atmosphere, and the mixture was refluxed at elevated temperature for 20 hours. Poured into water, extracted and subjected to column chromatography to obtain 15-9(0.88g, yield 32.8%). Elemental analysis Structure (C)51H41Br2IrN2O2): theoretical value C, 57.47; h, 3.88; n,2.63 test value C, 57.38; h, 3.81; and N, 2.69. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 1064.1; experimental value 1064.1 (M)+)。
A two-neck flask is added with 15-5(2.54g, 2.4mmol), 15-9(1.04g, 1mmol) and Pd2(dba)3(0.10g, 0.10mmol), s-phos (0.08g, 0.2mmol) and Aliquat 336(10mg), 20ml of dry toluene and 3ml of 2M aqueous potassium carbonate solution were added under argon and stirred in an oil bath at 100 ℃ for 12 h. The reaction solution was poured into water, extracted with dichloromethane, concentrated, and column-separated to give the product 1-1-17(0.94g, 34.1%). Elemental analysis Structure (C)183H125IrN8O2Si4): theoretical value C, 79.28; h, 4.54; n,4.04, test value C,79.21(ii) a H, 4.51; and N, 4.01. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 2770.86; experimental value 2770.9 (M)+)。
Example 16
The chemical structure and the synthetic route of I-1-20 are as follows:
in a 100mL two-necked flask under argon atmosphere, 16-1(2.56g, 10mmol), o-iodobenzyl sulfoxide (12g, 50mmol), cuprous iodide (190mg, 1mmol), copper powder (2.5g, 40mmol) and potassium carbonate (5.5g, 40mmol) were weighed, 50mL of o-dichlorobenzene (o-DCB) was added, the temperature was raised to 220 ℃ and the mixture was stirred under argon atmosphere for 50 hours, then cooled to room temperature, extracted with dichloromethane and water, the organic phase was separated, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the column was isolated to obtain 16-2(0.43g, yield: 11%). Elemental analysis Structure (C)25H18N2OS): theoretical value C, 76.12; h, 4.60; n, 7.10; test value C, 76.10; h, 4.50; and N, 7.05. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 394.11; experimental value 394.1 (M)+)。
Intermediate 16-2(0.39g, 1mmol) and CF3SO3H was added to a 100mL two-necked flask. The mixture was stirred at room temperature for 24 hours and then for 30 minutes with a mixture of water and pyridine (8: 1 by volume). The stirred mixture was cooled to room temperature, extracted with dichloromethane, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The obtained residue was separated by column to obtain intermediate 16-3(0.22g, yield: 60%). Elemental analysis Structure (C)24H14N2S): theoretical value C, 79.53; h, 3.89; n, 7.73; test value C, 79.63; h, 3.83; and N, 7.70. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 362.09; experimental value 362.1 (M)+)。
Compound 16-3(0.36g, 1mmol), m-chloroperoxybenzoic acid was dissolved in 20mL of dichloromethane, stirred at room temperature for 24h, and then poured into cold water. The precipitate was collected by vacuum filtration, washed with water, and dried in a vacuum oven to give 16-4(0.24g, yield: 60%). Elemental analysis Structure (C)24H14N2O2S): theoretical value C, 73.08; h, 3.58; n, 7.73; test value C, 73.00; h, 3.50; n, 7.78. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 362.09; experimental value 362.1 (M)+)。
A100 ml round bottom flask was equipped with a reflux condenser and charged with 16-4(0.51g, 1.4mmol), 16-5(1.82g, 4.2mmol), cuprous iodide (0.02g, 0.14mmol) and potassium carbonate (0.57g, 4.2mmol), DMI 20 ml; filling argon, then pumping air, and continuously ventilating for three times; heating to 160 ℃ and reacting for 24 h. Cooling to room temperature, adding dilute hydrochloric acid and 300ml of dichloromethane for extraction, stirring for 1-2 hours, filtering to remove the catalyst, washing with water for three times, drying the organic phase with anhydrous sodium sulfate, removing the solvent under reduced pressure, and performing column separation to obtain a sample 16-6(0.39g, 37.2%). Elemental analysis Structure (C)42H26BrN2O3PS): theoretical value C, 67.30; h, 3.50; n, 3.74; test value C, 67.40; h, 3.51; n, 3.78. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 748.06; experimental value 748.1 (M)+)。
16-6(0.75g, 1.0mmol) was charged into a single-neck flask, and bis (pinacolato) diboron (0.76g, 2.0mmol), Pd (dppf) Cl was added to the flask in a glove box2(0.08g, 0.1mmol) and KOAc (0.19g, 2.0mmol), 30mL dry DMF under argon, and stirred in an oil bath at 80 ℃ for 24h, the solution turns black. The reaction solution was poured into water, filtered with suction, and the crude product was subjected to column separation to give 16-7(0.50g, 63.1%) as a product. Elemental analysis Structure (C)48H38BN2O5PS): theoretical value C, 72.37; h, 4.81; n, 3.52; test value C, 72.31; h, 4.88; n, 3.51. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 796.23; experimental value 796.2 (M)+)。
Ligand 16-8(2.0g, 5.73mmol), iridium trichloride trihydrate (0.92g, 2.6mmol), ethylene glycol monoethyl ether 30ml and water 10ml were added to a round bottom flask under an argon atmosphere, and the system was refluxed at elevated temperature to react for 24 hours. After the reaction, water is added to precipitate the product, which is then filtered and dried. The crude product 16-9 was used in the next reaction without purification.
Under argon atmosphere, the crude product, ligand 16-10(0.61g, 3.9mmol), potassium carbonate (0.82g, 7.8mmol) and ethylene glycol ethyl ether (30ml) were added to a two-neck flask, and the mixture was refluxed at an elevated temperature for 20 hours. Poured into water, extracted and column chromatographed to give 16-11(1.05g, 38.8% yield). Elemental analysis Structure (C)47H37Br2IrN2O4): theoretical value C, 53.98; h, 3.57; n,2.68 test value C, 53.91; h, 3.51; and N, 2.69. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 1044.07; experimental value 1044.1 (M)+)。
A two-neck flask was charged with 16-7(1.91g, 2.4mmol), 16-11(1.04g, 1mmol), Pd2(dba)3(0.10g, 0.10mmol), s-phos (0.08g, 0.2mmol) and Aliquat 336(10mg), 20ml of dry toluene and 3ml of 2M aqueous potassium carbonate solution were added under argon and stirred in an oil bath at 100 ℃ for 12 h. The reaction solution was poured into water, extracted with dichloromethane, concentrated, and column-separated to give the product 1-1-20(0.63g, 28.1%). Elemental analysis Structure (C)131H89IrN6O10P2S2): theoretical value C, 70.70; h, 4.03; n,3.78, test value C, 70.61; h, 4.01; and N, 3.72. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 2224.52; experimental value 2224.5 (M)+)。
Example 17
The chemical structure and the synthetic route of I-1-30 are as follows:
weighing 17-1(12.8g, 50mmol), cuprous iodide (0.85g, 5mmol), copper powder (12.5g, 200mmol) and potassium carbonate (27.5g, 200mmol) in a 1000mL two-necked flask under argon atmosphere, adding 250mL of o-dichlorobenzene (o-DCB), 20mL of methyl o-iodobenzoate (250mmol), heating to 220 ℃, stirring under argon for 50 hours, then cooling to room temperature, adding dichloromethane and water for extraction, separating the organic phase, addingDried over anhydrous sodium sulfate, the organic phase obtained by filtration was freed of the solvent, and the product 17-2 was obtained by column separation (6.47g, yield: 33.2%). Elemental analysis Structure (C)26H18N2O2): theoretical value C, 79.98; h, 4.65; n, 7.17; test value C, 79.90; h, 4.60; and N, 7.11. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 390.14; experimental value 390.1 (M)+)。
17-2(3.90g, 10mmol) was added to a 500mL two-necked flask under an argon atmosphere, 90mL of tetrahydrofuran was introduced, stirred at room temperature, then 40mL (40mmol) of methylmagnesium bromide was added dropwise, warmed to 80 ℃ for reaction for 12 hours, then cooled to room temperature, extracted with ethyl acetate and water, the organic phase was separated, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product 17-3 was obtained by column separation (1.88g, yield: 48.3%). Elemental analysis Structure (C)27H22N2O): theoretical value C, 83.05; h, 5.68; n, 7.17; test value C, 83.01; h, 5.70; and N, 7.12. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 390.17; experimental value 390.2 (M)+)。
In a 500mL single-neck flask, 17-3(0.78g, 2mmol) was weighed under argon atmosphere, 50mL of glacial acetic acid was added, 5mL of concentrated hydrochloric acid was added, heating was carried out to 130 ℃ and reaction was carried out for 4 hours, then cooling was carried out to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product 17-4(0.53g, 71.1%) was obtained by column separation. Elemental analysis Structure (C)27H20N2): theoretical value C, 87.07; h, 5.41; n,7.52 test value C, 87.01; h, 5.36; and N, 7.50. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 372.16; experimental value 372.2 (M)+)。
A100 ml round-bottom flask was equipped with a reflux condenser, and 17-4(0.73g, 1.4mmol), 2, 5-dibromothiophene (1.01g, 4.2mmol), cuprous iodide (0.02g, 0.14mmol), and potassium carbonate (0.57g, 4.2mmol), DMI 20ml were added; filling argon, then pumping air, and continuously ventilating for three times; heating to 160 ℃ and reacting for 24 h. Cooling to room temperature, adding dilute hydrochloric acid and 300ml of dichloromethane for extraction, stirring for 1-2 hours, filtering to remove catalysisThe reagent was washed three times with water, and after the organic phase was dried over anhydrous sodium sulfate, the solvent was removed under reduced pressure, and the column was separated to obtain sample 17-5(0.43g, 57.8%). Elemental analysis Structure (C)31H21BrN2S): theoretical value C, 69.79; h, 3.97; n, 5.25; test value C, 69.82; h, 4.01; n, 5.21. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 532.06; experimental value 532.1 (M)+)。
17-5(0.53g, 1.0mmol) was charged into a single-neck flask, and bis (pinacolato) diboron (0.76g, 2.0mmol), Pd (dppf) Cl was added to the flask in a glove box2(0.08g, 0.1mmol) and KOAc (0.19g, 2.0mmol), 30mL dry DMF under argon, and stirred in an oil bath at 80 ℃ for 24h, the solution turns black. The reaction was poured into water, filtered off with suction and the crude product was isolated on a column to give 17-6(0.37g, 63.1%). Elemental analysis Structure (C)37H33BN2O2S): theoretical value C, 76.55; h, 5.73; n, 4.83; test value C, 76.50; h, 5.72; and N, 4.81. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 580.24; experimental value 580.2 (M)+)。
Ligand 17-7(2.58g, 5.73mmol), iridium trichloride trihydrate (0.92g, 2.6mmol), ethylene glycol monoethyl ether 30ml and water 10ml were added to a round-bottomed flask under an argon atmosphere, and the system was refluxed at elevated temperature to react for 24 hours. After the reaction, water is added to precipitate the product, which is then filtered and dried. The crude product 17-8 was used in the next reaction without purification.
The crude product, ligand 17-9(0.83g, 3.9mmol), potassium carbonate (0.82g, 7.8mmol) and ethylene glycol ethyl ether (30ml) were added to a two-neck flask under an argon atmosphere, and the mixture was refluxed at an elevated temperature for 20 hours. Poured into water, extracted and subjected to column chromatography to obtain 17-10(1.29g, 38.1% yield). Elemental analysis Structure (C)67H55Br2F4IrN4O2): theoretical value C, 58.47; h, 4.03; n,4.07 test value C, 58.42; h, 4.11; and N, 4.09. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 1374.23; experimental value 1374.2 (M)+)。
A two-neck flask was charged with 17-6(1.39g, 2.4mmol), 17-10(1.3 mmol)0g，1mmol)，Pd2(dba)3(0.10g, 0.10mmol), s-phos (0.08g, 0.2mmol) and Aliquat 336(10mg), 20ml of dry toluene and 3ml of 2M aqueous potassium carbonate solution were added under argon and stirred in an oil bath at 100 ℃ for 12 h. The reaction solution was poured into water, extracted with dichloromethane, concentrated, and column-separated to give the product 1-1-30(0.62g, 29.1%). Elemental analysis Structure (C)129H97F4IrN8O2S2): theoretical value C, 72.96; h, 4.60; n,5.28, test value C, 72.91; h, 4.51; and N, 5.22. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 2122.67; experimental value 2122.7 (M)+)。
Example 18
The chemical structure and the synthetic route of I-2-12 are as follows:
in a 100mL two-necked flask under argon atmosphere, 18-1(2.56g, 10mmol), 2-bromoiodobenzene (2.81g, 10mmol), cuprous iodide (190mg, 1mmol), copper powder (2.5g, 40mmol) and potassium carbonate (5.5g, 40mmol) were weighed, 50mL of o-dichlorobenzene (o-DCB) was added, the temperature was raised to 220 ℃ and the mixture was stirred under argon atmosphere for 50 hours, then cooled to room temperature, extracted with dichloromethane and water, the organic phase was separated, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the product 18-2 was obtained by column separation (1.72g, yield: 42%). Elemental analysis Structure (C)24H15BrN2): theoretical value C, 70.09; h, 3.68; n, 6.81; test value C, 70.01; h, 3.62; and N, 6.87. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 410.04; experimental value 410.0 (M)+)。
18-2(0.41g, 1mmol) was added to a 100mL two-necked flask under argon, 20mL of anhydrous Tetrahydrofuran (THF) was added, and the apparatus was placed in a-78 deg.C dry ice/acetone bath and cooled for 15 min. Measuring 5mL (2mmol) n-hexane solution of n-butyllithium by a syringe, dropwise adding the n-hexane solution into a reaction bottle, reacting at-78 ℃ for 1 hour, adding 18-3 into the reaction system, and reacting at room temperature for 12 hours. Then, it was cooled to room temperature, extracted with dichloromethane and water, the organic phase was separated, dried by adding anhydrous sodium sulfate, the solvent was removed from the filtered organic phase, and the product 18-4(0.30g, yield: 59%) was obtained by column separation. Elemental analysis Structure (C)36H24N2Si): theoretical value C, 84.34; h, 4.72; n, 5.46; test value C, 84.39; h, 4.65; n, 5.41. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 512.17; experimental value 512.2 (M)+)。
In a 100mL two-necked flask under an argon atmosphere, 18-4(0.51g, 1mmol), 3, 3-dimethyl-1-butene (0.64mL, 5mmol), RhCl (PPh)3)3(0.0092mg, 0.01mmol), 20mL of 1, 4-dioxane was added, and the mixture was heated to 135 ℃ to react for 24 hours. Then cooled to room temperature, extracted with dichloromethane and water, the organic phase was separated, dried with anhydrous sodium sulfate, the solvent was removed from the filtered organic phase, and the product 18-5(0.38g, 74%) was obtained by column separation. Elemental analysis Structure (C)36H22N2Si): theoretical value C, 84.67; h, 4.34; n, 5.49; test value C, 84.61; h, 4.30; n, 5.41. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 510.16; experimental value 510.2 (M)+)
A100 ml round-bottomed flask was equipped with a reflux condenser and charged with 18-5(0.80g, 1.4mmol), 18-6(1.96g, 4.2mmol), cuprous iodide (0.02g, 0.14mmol) and potassium carbonate (0.57g, 4.2mmol), DMI 20 ml; filling argon, then pumping air, and continuously ventilating for three times; heating to 160 ℃ and reacting for 24 h. Cooling to room temperature, adding dilute hydrochloric acid and 300ml of dichloromethane for extraction, stirring for 1-2 hours, filtering to remove the catalyst, washing with water for three times, drying the organic phase with anhydrous sodium sulfate, removing the solvent under reduced pressure, and performing column separation to obtain 18-7(0.46g, 37.2%) of a sample. Elemental analysis Structure (C)57H34BrN5Si): theoretical value C, 76.33; h, 3.82; n, 7.81; test value C, 76.31; h, 3.86; and N, 7.88. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 895.18; experimental value 895.2 (M)+)。
18-7(0.90g, 1.0mmol) was added to a single-neck flask, which was placed in a glove box and bis (pinacolato) diboron (0.76g, 2.0mmol) was added，Pd(dppf)Cl2(0.08g, 0.1mmol) and KOAc (0.19g, 2.0mmol), 30mL dry DMF under argon, and stirred in an oil bath at 80 ℃ for 24h, the solution turns black. The reaction solution was poured into water, filtered with suction, and the crude product was subjected to column separation to give 18-8(0.59g, 63.1%) as a product. Elemental analysis Structure (C)63H46BN5O2Si): theoretical value C, 80.16; h, 4.91; n, 7.42; test value C, 80.10; h, 4.98; and N, 7.39. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 943.35; experimental value 943.4 (M)+)。
Ligand 18-9(1.79g, 5.73mmol), iridium trichloride trihydrate (0.92g, 2.6mmol), ethylene glycol monoethyl ether 30ml and water 10ml were added to a round bottom flask under an argon atmosphere, and the system was refluxed at elevated temperature to react for 24 hours. After the reaction, water is added to precipitate the product, which is then filtered and dried. The crude product 18-10 was used in the next reaction without purification.
The crude product, ligand 18-11(0.88g, 3.9mmol), sodium carbonate (0.82g, 7.8mmol) and ethylene glycol ethyl ether (30ml) were added to a two-neck flask under an argon atmosphere, and the mixture was refluxed at an elevated temperature for 20 hours. Poured into water, extracted and subjected to column chromatography to obtain 18-12(0.82g, yield 32.1%). Elemental analysis Structure (C)48H51Br2IrN2O2): theoretical value C, 55.44; h, 4.94; n,2.69 test value C, 55.41; h, 4.91; n, 2.79. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 1038.2; experimental value 1038.2 (M)+)。
18-8(2.26g, 2.4mmol), 18-12(0.98g, 1mmol) and Pd were added into a two-neck flask2(dba)3(0.10g, 0.10mmol), s-phos (0.08g, 0.2mmol) and Aliquat 336(10mg), 20ml of dry toluene and 3ml of 2M aqueous potassium carbonate solution were added under argon and stirred in an oil bath at 100 ℃ for 12 h. The reaction solution was poured into water, extracted with dichloromethane, concentrated, and column-separated to give the product 1-2-12(0.73g, 29.1%). Elemental analysis Structure (C)162H119IrN12O2Si2): theoretical value C, 77.39; h, 4.77; n,6.69, test value C, 77.31; h, 4.71; and N, 6.62. Matrix-assisted laser desorption-time-of-flight mass spectrometry (MALDI-TO)F-MS) theoretical value 2512.87; experimental value 2512.9 (M)+)。
Example 19
The chemical structure and the synthetic route of I-2-16 are as follows:
a100 ml round bottom flask was equipped with a reflux condenser and charged with 19-1(1.16g, 1.4mmol), 19-2(1.56g, 4.2mmol), cuprous iodide (0.02g, 0.14mmol) and potassium carbonate (0.57g, 4.2mmol), DMI 20 ml; filling argon, then pumping air, and continuously ventilating for three times; heating to 160 ℃ and reacting for 24 h. Cooling to room temperature, adding dilute hydrochloric acid and 300ml of dichloromethane for extraction, stirring for 1-2 hours, filtering to remove the catalyst, washing with water for three times, drying the organic phase with anhydrous sodium sulfate, removing the solvent under reduced pressure, and performing column separation to obtain a sample 19-3(0.58g, 36.8%). Elemental analysis Structure (C)74H46BrN3O2S): theoretical value C, 79.42; h, 3.96; n, 3.75; test value C, 79.31; h, 3.91; and N, 3.68. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 1119.25; experimental value 1119.3 (M)+)。
19-3(1.11g, 1.0mmol) was charged into a single-neck flask, and bis (pinacolato) diboron (0.76g, 2.0mmol), Pd (dppf) Cl was added to the flask2(0.08g, 0.1mmol) and KOAc (0.19g, 2.0mmol), 30mL dry DMF under argon, and stirred in an oil bath at 80 ℃ for 24h, the solution turns black. The reaction was poured into water, filtered off with suction and the crude product was isolated on a column to give 19-4(0.77g, 66.1%). Elemental analysis Structure (C)80H56BN3O4S): theoretical value C, 82.39; h, 4.84; n, 3.60; test value C, 82.30; h, 4.80; n, 3.51. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 1167.42; experimental value 1167.4 (M)+)。
Ligand 19-5(2.09g, 5.73mmol), iridium trichloride trihydrate (0.92g, 2.6mmol), ethylene glycol monoethyl ether 30ml and water 10ml were added to a round bottom flask under an argon atmosphere, and the system was refluxed at elevated temperature for 24 hours. After the reaction, water is added to precipitate the product, which is then filtered and dried. The crude product 19-6 was used in the next reaction without purification.
The crude product, ligand 19-7(0.88g, 3.9mmol), sodium carbonate (0.82g, 7.8mmol) and ethylene glycol ethyl ether (30ml) were added to a two-neck flask under an argon atmosphere, and the mixture was refluxed at an elevated temperature for 20 hours. Poured into water, extracted and column chromatographed to give 19-8(0.80g, 32.1% yield). Elemental analysis Structure (C)52H47Br2IrN2O2S2): theoretical value C, 54.40; h, 4.13; n,2.44 test value C, 54.32; h, 4.11; and N, 2.49. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 1146.1; experimental value 1146.1 (M)+)。
A two-neck flask was charged with 19-4(2.69g, 2.4mmol), 19-7(1.09g, 1mmol), Pd2(dba)3(0.10g, 0.10mmol), s-phos (0.08g, 0.2mmol) and Aliquat 336(10mg), 20ml of dry toluene and 3ml of 2M aqueous potassium carbonate solution were added under argon and stirred in an oil bath at 100 ℃ for 12 h. The reaction solution was poured into water, extracted with dichloromethane, concentrated, and column-separated to give the product 1-2-16(0.89g, 28.1%). Elemental analysis Structure (C)200H139IrN8O6S4): theoretical value C, 78.23; h, 4.56; n,3.65, test value C, 78.31; h, 4.51; and N, 3.62. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 3068.93; experimental value 3068.9 (M)+)。
Example 20
The chemical structure and the synthetic route of I-2-17 are as follows:
in a 1000mL two-necked flask under argon atmosphere, weighing 20-1(12.8g, 50mmol), cuprous iodide (0.85g, 5mmol), copper powder (12.5g, 200mmol) and potassium carbonate (27.5g, 200mmol), adding 250mL of o-dichlorobenzene (o-DCB), 20mL of methyl o-iodobenzoate (250mmol), heating to 220 ℃, stirring under argon for 50 hours, then cooling to room temperature, adding dichloromethane and water for extraction,the organic phase was separated, dried by adding anhydrous sodium sulfate, the solvent was removed from the filtered organic phase, and the product 20-2 was obtained by column separation (7.76g, yield: 39.8%). Elemental analysis Structure (C)26H18N2O2): theoretical value C, 79.98; h, 4.65; n, 7.17; test value C, 79.90; h, 4.60; and N, 7.11. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 390.14; experimental value 390.1 (M)+)。
20-2(3.90g, 10mmol) was added to a 500mL two-necked flask under argon atmosphere, 90mL of tetrahydrofuran was introduced, and stirred at room temperature, then 40mL (40mmol) of phenylmagnesium bromide was added dropwise, the temperature was raised to 80 ℃ to react for 12 hours, then cooled to room temperature, ethyl acetate and water were added to extract, the organic phase was separated, dried over anhydrous sodium sulfate was added, the solvent was removed from the organic phase obtained by filtration, and the product 20-3(2.62g, yield: 52.3%) was obtained by column separation. Elemental analysis Structure (C)37H26N2O): theoretical value C, 86.20; h, 5.02; n, 5.58; test value C, 86.11; h, 5.00; n, 5.51. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 501.20; experimental value 501.2 (M)+)。
In a 500mL single-neck flask, 20-3(1.0g, 2mmol) was weighed under argon atmosphere, 50mL of glacial acetic acid was added, 5mL of concentrated hydrochloric acid was added, heating was carried out to 130 ℃ and reaction was carried out for 4 hours, then cooling was carried out to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, anhydrous sodium sulfate was added for drying, the solvent was removed from the organic phase obtained by filtration, and the product 20-4(0.81g, 81.3%) was obtained by column separation. Elemental analysis Structure (C)37H24N2): theoretical value C, 89.49; h, 4.87; n,5.64 test value C, 89.41; h, 4.86; and N, 5.60. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 496.19; experimental value 496.2 (M)+)。
Ligand 20-5(1.06g, 3mmol) and t-BuONa (0.29g,3mmol) in DMSO-D6(5mL) were reacted at 80 ℃ for 12h by D2After quenching with O (10mL), the extract was filtered through celite. The solvent was evaporated to dryness to afford ligand 20-6(0.79g, 72.6%). Elemental analysis Structure (C)20H8D12BrN): theoretical value C, 65.57; h, 8.80; n,3.82 testingValue C, 65.51; h, 8.88; and N, 3.81. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 365.15; experimental value 365.2 (M)+)。
Ligand 20-6(2.09g, 5.73mmol), iridium trichloride trihydrate (0.92g, 2.6mmol), ethylene glycol monoethyl ether 30ml and water 10ml are added into a round-bottomed flask under an argon atmosphere, and the system is refluxed for 24 hours under a temperature rise. After the reaction, water is added to precipitate the product, which is then filtered and dried. The crude products 20-7 were used directly in the next reaction without purification.
Under argon atmosphere, the crude product, ligand acetylacetone (0.39g, 3.9mmol), potassium carbonate (0.82g, 7.8mmol) and ethylene glycol ethyl ether (30ml) are added into a two-neck flask, and the mixture is refluxed for 20 hours at a heated system. Poured into water, extracted and subjected to column chromatography to obtain 20-8(1.22g, 46.1% yield). Elemental analysis Structure (C)45H21D24Br2IrN2O2): theoretical value C, 52.88; h, 6.80; n,2.74 test value C, 52.92; h, 6.85; n, 2.79. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 1020.30; experimental value 1020.3 (M)+)。
20-4(1.19g, 2.4mmol), 20-8(1.02g, 1mmol) and Pd were added into a two-neck flask2(dba)3(0.10g, 0.10mmol), s-phos (0.08g, 0.2mmol), t-BuONa (0.29g,3mmol) and Aliquat 336(10mg) were added to 20ml of dry toluene under argon and stirred in an oil bath at 100 ℃ for 12 h. The reaction solution was poured into water, extracted with dichloromethane, concentrated, and column-separated to give the product 1-2-17(1.01g, 54.1%). Elemental analysis Structure (C)120H70D24IrN6O2): theoretical value C, 77.14; h, 6.36; n,4.50, test value C, 77.11; h, 6.41; n, 4.52. Matrix-assisted laser desorption-time of flight mass spectrometry (MALDI-TOF-MS) theoretical 1867.86; experimental value 1867.9 (M)+)。
Device embodiment: examples 21 to 43
As device embodiments, the present invention provides two types of device structures (device structure a and device structure B) for preparing an organic electroluminescent device:
the device structure a is: PSS (40 nm)/iridium complex containing fused indole and quinoline structures (30nm)/TSPO1(8nm)/TmPyPB (30nm)/LiF (0.8nm)/Al (100 nm).
The steps of preparing the device by adopting the device structure A are as follows: poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT: PSS) was spin-coated on Indium Tin Oxide (ITO) supported on a glass substrate, annealed at 120 ℃ for 30 minutes, followed by spin-coating a toluene solution containing iridium complexes with fused indole and quinoline structures at 1500rpm for 1 minute and annealing at 80 ℃ for 30 minutes, and then at 4X 10-4Sequentially depositing TSPO1, TmPyPB and a LiF/Al cathode under Pa vacuum degree to obtain the organic electroluminescent device, wherein TSPO1 and TmPyPB are respectively used as a hole blocking layer and an electron transport layer, and the structural formulas of the layers are as follows:
the device structure B is: PSS (40 nm)/blend (mass ratio of 1:9) (30nm)/TSPO1(8nm)/TmPyPB (42nm)/LiF (1nm)/Al (100nm) of the iridium complex containing fused indole and quinoline structure and SiMCP2 serving as a main material.
The steps of preparing the device by adopting the device structure B are as follows: poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT: PSS) was spin-coated on indium tin oxide supported on a glass substrate, annealed at 120 ℃ for 30 minutes, and then spin-coated with an iridium complex containing fused indole and quinoline structures and simpp 2 at a rotation speed of 1500rpm in a mass ratio of 1:9 the mixed toluene solution was annealed at 80 ℃ for 30 minutes for 1 minute, and then at 4X 10-4Sequentially depositing TSPO1, TmPyPB and a LiF/Al cathode under the vacuum degree of Pa to obtain the organic electroluminescent device, wherein the structural formula of a main material SiMCP2 is shown as follows:
example 21
The compound of formula I-1-1 obtained in example 1 was used as an object, and the compound of formula I-1-1 was directly used as an organic light-emitting layer, and an organic electroluminescent device was prepared using the structure described in "device Structure A".
Example 22
Using the compound of the formula I-1-12 obtained in example 9 as an object, the compound of the formula I-1-12 was used directly as an organic light-emitting layer, and an organic electroluminescent device was prepared using the structure described in "device Structure A".
Example 23
The compound of the formula I-2-12 obtained in example 18 was used as an object, and the compound of the formula I-2-12 was directly used as an organic light-emitting layer, and an organic electroluminescent device was produced using the structure described in "device Structure A".
Example 24
To prepare the compound of formula I-1-1 obtained in example 1, the compound of formula I-1-1 and SiMCP2 are mixed in a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 25
To compound the formula I-1-23 obtained in example 2, a compound of the formula I-1-23 was mixed with simpp 2 in a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 26
To prepare the compound of formula I-1-25 obtained in example 3, a compound of formula I-1-25 is mixed with SiMCP2 in a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 27
To compound of formula I-1-34 obtained in example 4, a compound of formula I-1-34 was mixed with SiMCP2 at a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 28
To prepare the compound of formula I-1-37 obtained in example 5, the compound of formula I-1-37 was mixed with SiMCP2 at a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 29
To prepare the compound of formula 1-2-3 obtained in example 6, a compound of formula 1-2-3 is mixed with sipep 2 in a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 30
To the compound of formula 1-2-4 obtained in example 7, a compound of formula 1-2-4 was mixed with simpp 2 at a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 31
To prepare the compound of formula 1-2-5 obtained in example 8, a compound of formula 1-2-5 was mixed with simpp 2 at a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 32
To proceed with the compound of formula I-1-12 obtained in example 9, a compound of formula I-1-12 was mixed with SiMCP2 in a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 33
To prepare the compound of formula 1-1-13 obtained in example 10, a compound of formula 1-1-13 was mixed with simpp 2 at a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 34
To compound the formula 1-2-7 obtained in example 11, a compound of the formula 1-2-7 was mixed with simpp 2 at a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 35
To compound of formula I-2-8 obtained in example 12, a compound of formula I-2-8 was mixed with simpp 2 in a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 36
To proceed with the compound of formula I-2-9 obtained in example 13, a compound of formula I-2-9 was mixed with sipep 2 in a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 37
To proceed with the compound of formula I-2-10 obtained in example 14, a compound of formula I-2-10 was mixed with SiMCP2 at a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 38
To compound of formula I-1-17 obtained in example 15, a compound of formula I-1-17 was mixed with simpp 2 in a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 39
To compound of formula I-1-20 obtained in example 16, a compound of formula I-1-20 was mixed with simpp 2 in a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 40
To compound of formula I-1-30 obtained in example 17, a compound of formula I-1-30 was mixed with simpp 2 in a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
EXAMPLE 41
To proceed with the compound of formula I-2-12 obtained in example 18, a compound of formula I-2-12 was mixed with SiMCP2 at a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 42
To compound of formula I-2-16 obtained in example 19, a compound of formula I-2-16 was mixed with simpp 2 in a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Example 43
To compound of formula I-2-17 obtained in example 20, a compound of formula I-2-17 was mixed with simpp 2 in a mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Comparative example 1
With a compound Ir (pq) not containing fused indole structure2(acac) As a subject of implementation, Ir (pq)2(acac) was directly used as an organic light-emitting layer, and an organic electroluminescent device was prepared using the structure described in "device Structure A".
Comparative example 2
With a compound not containing fused indole structure Ir (piq)2(acac) As a subject of implementation, Ir (piq)2(acac) was directly used as an organic light-emitting layer, and an organic electroluminescent device was prepared using the structure described in "device Structure A".
Comparative example 3
With no fused indole structure, Ir (piql)2(acac) As a subject of implementation, Ir (piql)2(acac) was directly used as an organic light-emitting layer, and an organic electroluminescent device was prepared using the structure described in "device Structure A".
Comparative example 4
With a compound Ir (pq) not containing fused indole structure2(acac) As a subject of implementation, Ir (pq)2(acac) and SiMCP2 according to the mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Comparative example 5
With a compound not containing fused indole structure Ir (piq)2(acac) As a subject of implementation, Ir (piq)2(acac) and SiMCP2 according to the mass ratio of 1: and 9, mixing the materials to be used as an organic light-emitting layer, and preparing the organic electroluminescent device by using the structure of the device structure B.
Comparative example 6
With no fused indole structure, Ir (piql)2(acac) As a subject of implementation, Ir (piql)2(acac) and SiMCP2 according to the mass ratio of 1:9 as an organic light emitting layer by mixing the above-mentioned materials, using the structure described in "device Structure BAnd preparing the organic electroluminescent device.
In the above comparative examples 1 to 6, the compound Ir (pq)2(acac),Ir(piq)2(acac) and Ir (piql)2The chemical structure of (acac) is as follows:
the organic electroluminescent devices obtained in device examples 21 to 43 and comparative examples 1 to 6 were subjected to performance tests, and the results are shown in table 1.
TABLE 1 Properties of organic electroluminescent devices obtained in examples 21 to 43 and comparative examples 1 to 6
Note: in Table 1, the ON voltage is 1cd m in luminance-2The driving voltage of the time device; the maximum external quantum efficiency is obtained according to the current-voltage curve and the electroluminescence spectrum of the device by the calculation method described in the literature (Jpn.J.appl.Phys.2001,40, L783); the device lifetime is the time required for the luminance to decrease to 95% of the initial luminance.
As can be seen from the test results in Table 1, the doped and undoped solution-processed organic electroluminescent devices prepared from the iridium complex containing the fused indole and quinoline structures provided by the invention and the comparative compound Ir (pq)2(acac),Ir(piq)2(acac) and Ir (piql)2(acac) as a light-emitting layer, the light-emitting efficiency and the device lifetime were significantly improved.
The foregoing examples are provided to facilitate an understanding of the principles of the invention and their core concepts, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that approximate the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. An iridium complex containing fused indole and quinoline structures has a structure shown in a formula I-1 or a formula I-2:
wherein Z is1Is C and Z2Is N, or Z1Is N and Z2Is C;
wherein X is selected from a single bond, -C (R)11R12)-、-C＝O-、-Si(R11R12)-、-N(R11)-、-PO(R11)-、-P(R11)＝O-、-B(R11)-、-O-、-S-、-Se-、-S＝O-、-SO2-any of; the R is11And R12Each independently selected from H, D,C1-C30 straight chain alkyl, C1-C30 branched chain alkyl, C3-C30 naphthenic base, C6-C60 aryl or C5-C60 heteroaryl, wherein hetero atoms of the heteroaryl are independently selected from one or more of Si, Ge, N, P, O, S and Se;
R1～R10independently selected from H, D, F, Cl, Br, I, -CN, -NO2、-CF3、-OH、-SH、-NH2The aryl group comprises C1-C30 straight-chain alkyl or deuterated straight-chain alkyl, C1-C30 branched-chain alkyl, C3-C30 cycloalkyl, C1-C30 alkoxy, C1-C30 alkylthio, C6-C60 aryl, C6-C60 aryl ether, C5-C60 heteroaryl or C5-C60 heteroaryl ether, wherein hetero atoms of the heteroaryl or the heteroaryl ether are independently selected from one or more of Si, Ge, N, P, O, S and Se;
m1～m10independently selected from integers of 0 to 4;
denotes the connection position.
2. The iridium complex containing fused indole and quinoline structures according to claim 1, wherein R is11And R12Each independently selected from H, D, C1-C10 straight chain alkyl, C1-C10 branched chain alkyl, C3-C12 naphthenic base, C6-C12 aryl or C5-C12 heteroaryl, and the heteroatom of the heteroarylIndependently selected from one or more of Si, Ge, N, P, O, S and Se;
R1～R10independently selected from H, D, F, Cl, Br, I, -CN, -NO2、-CF3、-OH、-SH、-NH2The aromatic amine is characterized by comprising C1-C10 straight-chain alkyl or deuterated straight-chain alkyl, C1-C10 branched-chain alkyl or deuterated branched-chain alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C1-C10 alkylthio, substituted or unsubstituted C6-C12 aryl, substituted or unsubstituted C6-C12 aryl ether, substituted or unsubstituted C5-C12 heteroaryl, substituted or unsubstituted C5-C12 heteroaryl ether, substituted or unsubstituted C6-C12 arylamine, and C1-C10 straight-chain alkyl or branched-chain alkyl substituted carbonyl, wherein hetero atoms of the heteroaryl or hetero aryl ether are independently selected from one or more of Si, Ge, N, P, O, S and Se.
3. The iridium complex containing fused indole and quinoline structures according to claim 1, wherein R is11And R12Each independently selected from H, D, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or phenyl.
4. The iridium complex containing fused indole and quinoline structures according to claim 1, wherein R is1～R10Independently selected from H, D, F, Cl, Br, I, -CN, -NO2、-CF3、-OH、-SH、-NH2Methyl, ethyl, N-propyl, isopropyl, N-butyl, isobutyl, tert-butyl, N-pentyl, N-hexyl, deuterated methyl, deuterated ethyl, deuterated N-propyl, deuterated isopropyl, deuterated N-butyl, deuterated isobutyl, deuterated tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, biphenyl, methoxy, ethoxy, propoxy, methylthio, ethylthio, propylthio, acetyl, N-dimethylamino, furyl, methylfuryl, thienyl, methylthioA phenyl group, a pyrrolyl group, a methylpyrrole group or a carbazolyl group.
5. The iridium complex containing fused indole and quinoline structures according to claim 1, wherein X is selected from any one of the following structures:
R11and R12Each independently selected from H, D, C1-C30 straight chain alkyl, C1-C30 branched chain alkyl, C3-C30 naphthenic base, C6-C60 aryl or C5-C60 heteroaryl, wherein hetero atoms of the heteroaryl are independently selected from one or more of Si, Ge, N, P, O, S and Se; and R in X411And R12May form a ring with a silicon atom.
6. The iridium complex with fused indole and quinoline structure according to claim 1, wherein the iridium complex is characterized in that
Selected from any of the following structures:
p and q are independently selected from integers of 0-8, and r is selected from integers of 1-8;
R13～R14independently selected from H, D, F, Cl, Br, I, -CN, -NO2、-CF3、-OH、-SH、-NH2Straight chain alkyl or deuterated straight chain alkyl of C1-C30, branched chain alkyl or deuterated branched chain alkyl of C1-C30, substituted or unsubstituted cycloalkyl of C3-C30, substituted or unsubstituted alkoxy of C1-C30, substituted or unsubstituted alkylthio of C1-C30, substituted or unsubstituted aryl of C6-C60, substituted or unsubstituted aryl ether of C6-C60, substituted or unsubstituted heteroaryl of C5-C60, substituted or unsubstituted alkyl, substituted or unsubstituted aryl ether of C3626, and the like,Substituted or unsubstituted C5-C60 heteroaryl ether, substituted or unsubstituted C6-C60 arylamine, and C1-C30 straight chain alkyl or branched chain alkyl substituted carbonyl, wherein hetero atoms of the heteroaryl or the heteroaryl ether are independently selected from one or more of Si, Ge, N, P, O, S and Se;
m11an integer selected from 0 to 4;
denotes the connection position.
7. The iridium complex containing fused indole and quinoline structures according to claim 1, which has the structures represented by the formulae (I-1-1) to (I-2-25):
8. the use of the iridium complex containing fused indole and quinoline structures according to any one of claims 1 to 7 as a light-emitting layer of an organic electroluminescent device.
9. An organic electroluminescent device comprising an anode, a cathode and an organic thin film layer between the anode and the cathode; the organic thin film layer comprises the iridium complex containing the fused indole and quinoline structure according to any one of claims 1 to 7.
10. The organic electroluminescent device according to claim 9, wherein the organic thin film layer comprises a light emitting layer; the light-emitting layer comprises the iridium complex containing the fused indole and quinoline structure according to any one of claims 1 to 7.
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| CN1696137A (en) * | 2005-04-30 | 2005-11-16 | 中国科学院长春应用化学研究所 | Complexes of red light iridium by using nitrogen heterocycles in quinoline as ligand, and application |
| KR20100047466A (en) * | 2008-10-29 | 2010-05-10 | 다우어드밴스드디스플레이머티리얼 유한회사 | Novel compounds for electronic material and organic electronic device using the same |
| CN107501336A (en) * | 2017-09-12 | 2017-12-22 | 武汉大学 | A kind of organic red phosphorescent iridium complex and preparation method thereof and the application in organic electroluminescence device |
| CN111039986A (en) * | 2019-11-25 | 2020-04-21 | 吉林奥来德光电材料股份有限公司 | Iridium metal complex for red light electroluminescent material, preparation method thereof and organic electroluminescent device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1696137A (en) * | 2005-04-30 | 2005-11-16 | 中国科学院长春应用化学研究所 | Complexes of red light iridium by using nitrogen heterocycles in quinoline as ligand, and application |
| KR20100047466A (en) * | 2008-10-29 | 2010-05-10 | 다우어드밴스드디스플레이머티리얼 유한회사 | Novel compounds for electronic material and organic electronic device using the same |
| CN107501336A (en) * | 2017-09-12 | 2017-12-22 | 武汉大学 | A kind of organic red phosphorescent iridium complex and preparation method thereof and the application in organic electroluminescence device |
| CN111039986A (en) * | 2019-11-25 | 2020-04-21 | 吉林奥来德光电材料股份有限公司 | Iridium metal complex for red light electroluminescent material, preparation method thereof and organic electroluminescent device |
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