CN110790796A - Novel organic metal iridium complex, preparation method thereof and organic electroluminescent device containing metal iridium complex - Google Patents
Novel organic metal iridium complex, preparation method thereof and organic electroluminescent device containing metal iridium complex Download PDFInfo
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- CN110790796A CN110790796A CN201911089199.9A CN201911089199A CN110790796A CN 110790796 A CN110790796 A CN 110790796A CN 201911089199 A CN201911089199 A CN 201911089199A CN 110790796 A CN110790796 A CN 110790796A
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- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 36
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 18
- 239000002184 metal Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 46
- 239000003446 ligand Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 40
- -1 cyano, carboxyl Chemical group 0.000 claims description 40
- 239000000463 material Substances 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 24
- 150000002431 hydrogen Chemical class 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 20
- 125000006746 (C1-C60) alkoxy group Chemical group 0.000 claims description 13
- 125000006818 (C3-C60) cycloalkyl group Chemical group 0.000 claims description 12
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 12
- 150000002367 halogens Chemical class 0.000 claims description 12
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000002347 injection Methods 0.000 claims description 11
- 239000007924 injection Substances 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 125000006751 (C6-C60) aryloxy group Chemical group 0.000 claims description 8
- 125000002524 organometallic group Chemical group 0.000 claims description 8
- 125000001769 aryl amino group Chemical group 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 125000006752 (C6-C60) arylthio group Chemical group 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 125000000707 boryl group Chemical group B* 0.000 claims description 6
- 230000005525 hole transport Effects 0.000 claims description 6
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Natural products CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 5
- VQGHOUODWALEFC-UHFFFAOYSA-N alpha-Phenylpyridine Natural products C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 claims description 5
- JVZRCNQLWOELDU-UHFFFAOYSA-N gamma-Phenylpyridine Natural products C1=CC=CC=C1C1=CC=NC=C1 JVZRCNQLWOELDU-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 3
- 125000003282 alkyl amino group Chemical group 0.000 claims description 3
- 230000000903 blocking effect Effects 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 150000005359 phenylpyridines Chemical class 0.000 claims description 2
- 108091008695 photoreceptors Proteins 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000002019 doping agent Substances 0.000 claims 1
- 150000003376 silicon Chemical class 0.000 claims 1
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 3
- 150000002736 metal compounds Chemical class 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 84
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 36
- 239000007787 solid Substances 0.000 description 36
- 239000002994 raw material Substances 0.000 description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- 238000012544 monitoring process Methods 0.000 description 27
- 238000012360 testing method Methods 0.000 description 26
- 239000003208 petroleum Substances 0.000 description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 21
- 238000005406 washing Methods 0.000 description 20
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical group CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 18
- 238000001816 cooling Methods 0.000 description 18
- 238000001035 drying Methods 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 18
- 239000012046 mixed solvent Substances 0.000 description 17
- 238000001308 synthesis method Methods 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 15
- 238000011010 flushing procedure Methods 0.000 description 14
- 238000000967 suction filtration Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 description 9
- 239000000741 silica gel Substances 0.000 description 9
- 229910002027 silica gel Inorganic materials 0.000 description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 description 9
- 238000004809 thin layer chromatography Methods 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- IWZSHWBGHQBIML-ZGGLMWTQSA-N (3S,8S,10R,13S,14S,17S)-17-isoquinolin-7-yl-N,N,10,13-tetramethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-amine Chemical compound CN(C)[C@H]1CC[C@]2(C)C3CC[C@@]4(C)[C@@H](CC[C@@H]4c4ccc5ccncc5c4)[C@@H]3CC=C2C1 IWZSHWBGHQBIML-ZGGLMWTQSA-N 0.000 description 5
- MPDDTAJMJCESGV-CTUHWIOQSA-M (3r,5r)-7-[2-(4-fluorophenyl)-5-[methyl-[(1r)-1-phenylethyl]carbamoyl]-4-propan-2-ylpyrazol-3-yl]-3,5-dihydroxyheptanoate Chemical compound C1([C@@H](C)N(C)C(=O)C2=NN(C(CC[C@@H](O)C[C@@H](O)CC([O-])=O)=C2C(C)C)C=2C=CC(F)=CC=2)=CC=CC=C1 MPDDTAJMJCESGV-CTUHWIOQSA-M 0.000 description 5
- IOQORVDNYPOZPL-VQTJNVASSA-N (5S,6R)-5-(4-chlorophenyl)-6-cyclopropyl-3-[6-methoxy-5-(4-methylimidazol-1-yl)pyridin-2-yl]-5,6-dihydro-2H-1,2,4-oxadiazine Chemical compound ClC1=CC=C(C=C1)[C@@H]1NC(=NO[C@@H]1C1CC1)C1=NC(=C(C=C1)N1C=NC(=C1)C)OC IOQORVDNYPOZPL-VQTJNVASSA-N 0.000 description 5
- JQUCWIWWWKZNCS-LESHARBVSA-N C(C1=CC=CC=C1)(=O)NC=1SC[C@H]2[C@@](N1)(CO[C@H](C2)C)C=2SC=C(N2)NC(=O)C2=NC=C(C=C2)OC(F)F Chemical compound C(C1=CC=CC=C1)(=O)NC=1SC[C@H]2[C@@](N1)(CO[C@H](C2)C)C=2SC=C(N2)NC(=O)C2=NC=C(C=C2)OC(F)F JQUCWIWWWKZNCS-LESHARBVSA-N 0.000 description 5
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical class [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 5
- 229940126540 compound 41 Drugs 0.000 description 5
- 229910052805 deuterium Inorganic materials 0.000 description 5
- 238000004020 luminiscence type Methods 0.000 description 5
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 5
- 125000000542 sulfonic acid group Chemical group 0.000 description 5
- VIJSPAIQWVPKQZ-BLECARSGSA-N (2s)-2-[[(2s)-2-[[(2s)-2-[[(2s)-2-[[(2s)-2-[[(2s)-2-acetamido-5-(diaminomethylideneamino)pentanoyl]amino]-4-methylpentanoyl]amino]-4,4-dimethylpentanoyl]amino]-4-methylpentanoyl]amino]propanoyl]amino]-5-(diaminomethylideneamino)pentanoic acid Chemical compound NC(=N)NCCC[C@@H](C(O)=O)NC(=O)[C@H](C)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](CC(C)(C)C)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](CCCNC(N)=N)NC(C)=O VIJSPAIQWVPKQZ-BLECARSGSA-N 0.000 description 4
- VCUXVXLUOHDHKK-UHFFFAOYSA-N 2-(2-aminopyrimidin-4-yl)-4-(2-chloro-4-methoxyphenyl)-1,3-thiazole-5-carboxamide Chemical compound ClC1=CC(OC)=CC=C1C1=C(C(N)=O)SC(C=2N=C(N)N=CC=2)=N1 VCUXVXLUOHDHKK-UHFFFAOYSA-N 0.000 description 4
- 125000004404 heteroalkyl group Chemical group 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 229940125810 compound 20 Drugs 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000005401 electroluminescence Methods 0.000 description 3
- JAXFJECJQZDFJS-XHEPKHHKSA-N gtpl8555 Chemical compound OC(=O)C[C@H](N)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](C(C)C)C(=O)N[C@@H](C(C)C)C(=O)N1CCC[C@@H]1C(=O)N[C@H](B1O[C@@]2(C)[C@H]3C[C@H](C3(C)C)C[C@H]2O1)CCC1=CC=C(F)C=C1 JAXFJECJQZDFJS-XHEPKHHKSA-N 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 125000006745 (C2-C60) alkynyl group Chemical group 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 125000005264 aryl amine group Chemical group 0.000 description 2
- 125000005110 aryl thio group Chemical group 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- VFMUXPQZKOKPOF-UHFFFAOYSA-N 2,3,7,8,12,13,17,18-octaethyl-21,23-dihydroporphyrin platinum Chemical compound [Pt].CCc1c(CC)c2cc3[nH]c(cc4nc(cc5[nH]c(cc1n2)c(CC)c5CC)c(CC)c4CC)c(CC)c3CC VFMUXPQZKOKPOF-UHFFFAOYSA-N 0.000 description 1
- 229940093475 2-ethoxyethanol Drugs 0.000 description 1
- KDOQMLIRFUVJNT-UHFFFAOYSA-N 4-n-naphthalen-2-yl-1-n,1-n-bis[4-(n-naphthalen-2-ylanilino)phenyl]-4-n-phenylbenzene-1,4-diamine Chemical compound C1=CC=CC=C1N(C=1C=C2C=CC=CC2=CC=1)C1=CC=C(N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C3C=CC=CC3=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C3C=CC=CC3=CC=2)C=C1 KDOQMLIRFUVJNT-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses a novel organic metal iridium complex, a preparation method thereof and an organic electroluminescent device containing the same, wherein the structural general formula of the novel organic metal iridium complex is as shown in the formula
Description
Technical Field
The invention relates to the technical field of organic electroluminescent diodes, in particular to a novel organic metal iridium complex, a preparation method thereof and an organic electroluminescent device containing the metal iridium complex.
Background
Organic electroluminescence (abbreviated as OLED) and related researches firstly discovered the electroluminescence phenomenon of organic compound single crystal anthracene by pope et al in 1963. Kodak in the United states of 1987 produced an amorphous device by evaporation of small organic molecules, reducing the driving voltage to within 20V. The OLED is a hole and electron dual injection type light emitting device, and directly converts electric energy into light energy of organic semiconductor material molecules. Compared with traditional display devices such as a CRT (cathode ray tube), an LCD (liquid crystal display), a PDP (plasma display panel) and the like, the OLED has all the advantages of the existing display, has unique advantages, not only has high brightness, high contrast, high definition, wide visual angle, wide color gamut and the like to realize high-quality images, but also has the characteristics of ultra-thinness, ultra-lightness, low driving voltage, low power consumption, wide temperature and the like to meet the requirements of portable equipment on portability, power saving and outdoor operation; self-luminescence, high luminous efficiency, short response time, transparency, flexibility and the like are unique characteristics of OLED display, so that the OLED display is widely researched, developed and used.
Forrest et al, the university of Princeton, 1998, found that platinum octaethylporphyrin, a phosphorescent dye, was doped into a host luminescent material to prepare a luminescent device with an external quantum efficiency of 4% and an internal quantum efficiency of 23%, thus opening up a new field of phosphorescent electroluminescence and the research on organic electrophosphorescence has been rapidly developed in the following years. The noble metal complex is used as a phosphorescent material, fully utilizes singlet excitons and triplet excitons, only utilizes the singlet excitons compared with a fluorescent material, and effectively utilizes the triplet excitons with the proportion up to 75 percent, so that the PhOLED based on the phosphorescent material realizes 100 percent of internal quantum efficiency.
In recent three years, phosphorescent materials gradually replace traditional fluorescent materials, and become hot spots for research on OLED luminescent materials. However, the synthesis process of the phosphorescent material is complex, takes a long time, and has a short lifetime, so that a more suitable light-emitting layer doping material with high performance must be selected to achieve the comprehensive characteristics of high efficiency, long lifetime, and low voltage of the device according to the current industrial application requirements of the OLED device and the photoelectric characteristic requirements of the OLED device, and therefore, further development of the phosphorescent material is urgent at present.
Disclosure of Invention
In view of the above, the present invention provides a novel iridium complex, a preparation method thereof and an organic electroluminescent device comprising the same, wherein the novel iridium complex provided by the present invention adjusts the wavelength of a compound by selecting specific heterocyclic ligand combination, and the obtained organometallic compound is used in the organic electroluminescent device, such that the device has improved luminous efficiency and long service life.
In order to achieve the purpose, the invention adopts the following technical scheme:
a novel organometallic iridium complex has a structural general formula shown in formula I:
wherein:
R1～R3each independently represents hydrogen, substituted or unsubstituted C1-C5Alkyl, substituted or unsubstituted C6-C18Aryl, substituted or unsubstituted C5-C25Heterocyclic radical, substituted or unsubstituted C6-C30Arylamino, R1～R3The same or different;
r independently represents hydrogen, hydrogen isotope, halogen, cyano, carboxyl, nitro, hydroxyl, sulfonic acid group, phosphoric acid group, boron alkyl, phosphorus oxy, arylamine group, substituted or unsubstituted silicon group, and substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C6-C60Aryl, substituted or unsubstituted C3-C60Heteroaryl, substituted or unsubstituted C3-C60Cycloalkyl, substituted or unsubstituted C1-C60Alkoxy, substituted or unsubstituted C1-C60Alkylamino, substituted or unsubstituted C6-C60Arylamino, substituted or unsubstituted C6-C60Aryloxy, substituted or unsubstituted C6-C60Arylthio, substituted or unsubstituted C6-C60Aryl silicon group;
r can be at any position of the ring;
wherein m and n are natural numbers, and m is more than or equal to 1 and less than or equal to 3, n is more than or equal to 0 and less than or equal to 2, or n is more than or equal to 1 and less than or equal to 3, and m is more than or equal to 0 and less than or equal to 2.
Preferably, when m is 2 or 3, R of the benzene ring are bonded to each other through a C-C bond, a C-N bond, a C-O bond or a C-S bond to form a five-membered ring, a six-membered ring or a seven-membered ring; when N is 2 or 3, R of the pyridine ring are bonded to each other through a C-C bond, a C-N bond, a C-O bond or a C-S bond to form a five-membered ring, a six-membered ring or a seven-membered ring.
Preferably, R1～R3Each independently represents substituted or unsubstituted C1-C5Alkyl, substituted or unsubstituted C6-C18Aryl, substituted or unsubstituted C6-C30Arylamino, R1～R3The same or different.
Preferably, R independently represents hydrogen, an isotope of hydrogen, halogen, cyano, carboxyl, nitro, hydroxyl, sulfonic acid group, boryl, phosphoxy, arylamino, substituted or unsubstituted silicon group, substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C6-C60Aryl, substituted or unsubstituted C3-C60Heteroaryl, substituted or unsubstituted C3-C60Cycloalkyl, substituted or unsubstituted C1-C60Alkoxy, substituted or unsubstituted C1-C60An alkylamino group.
Preferably, R1～R3Each independently represents substituted hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, substituted C5-C25Heterocyclyl, substituted C1-C20Alkyl, substituted C6-C60Aryl, substituted C3-C60Heteroaryl, substituted C3-C60Cycloalkyl, substituted C1-C60Alkoxy, substituted C1-C60Alkylamino, substituted C6-C60Arylamino, substituted C6-C60Aryloxy, substituted C6-C60Arylthio, substituted C6-C60Aryl silicon base, C3-C60Cycloalkyl, adamantyl, C7-C60Bicycloalkyl radical, C2-C60Alkenyl radical, C2-C60Alkynyl radical, R1～R3The same or different.
Preferably, said substituted C1-C5Alkyl, substituted C6-C18Aryl, substituted C5-C25Heterocyclyl, substituted C6-C30Arylamino, substituted C1-C20Alkyl, substituted C6-C60Aryl, substituted C3-C60Heteroaryl, substituted C3-C60Cycloalkyl, substituted C1-C60Alkoxy, substituted C1-C60Alkylamino, substituted C6-C60Arylamino, substituted C6-C60Aryloxy, substituted C6-C60Arylthio, substituted C6-C60Arylsilyl groups, substituted silyl groups in which the substituents independently represent hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxy, C1-C5Alkyl radical, C6-C18Aryl radical, C6-C18Heteroaryl group, C6-C30Arylamino, C3-C60Cycloalkyl radical, C1-C60Alkoxy, adamantyl, C7-C60Bicycloalkyl radical, C2-C60Alkenyl radical, C2-C60Alkynyl, C1-C60One or more of alkoxy, 5-membered heteroalkyl comprising one or more heteroatoms selected from N, O and S, and 6-membered heteroalkyl comprising one or more heteroatoms selected from N, O and S.
Preferably, the formula I is represented by chemical formula 1-1 to chemical formula 1-8:
wherein:
R4～R6、R9、R10represents halogen, hydrogen, deuterium, hydroxy, substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C6-C60Aryl, substituted or unsubstituted C3-C60Heterocyclyl, substituted or unsubstituted C1-C60Alkylamino, substituted or unsubstituted C6-C60An arylamino group;
R7、R8each independently represents hydrogen, deuterium, substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C6-C60Aryl, substituted or unsubstituted C3-C60Heterocyclic radical, substituted or unsubstituted C1-C60Alkylamino, substituted or unsubstituted C6-C60An arylamino group;
R11、R12each independently represents hydrogen, an isotope of hydrogen, halogen, a cyano group, a carboxyl group, a nitro group, a hydroxyl group, a sulfonic acid group, a phosphoric acid group, a boryl group, or a substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C6-C60Aryl, substituted or unsubstituted C3-C60Heteroaryl, substituted or unsubstituted C3-C60Cycloalkyl, substituted or unsubstituted C1-C60Alkoxy, substituted or unsubstituted C1-C60Alkylamino, substituted or unsubstituted C6-C60Arylamino, substituted or unsubstituted C6-C60Aryloxy, substituted or unsubstituted C6-C60An arylthio group;
preferably, said substituted C1-C20Alkyl, substituted C6-C60Aryl, substituted C3-C60Heterocyclyl, substituted C1-C60Alkylamino, substituted C6-C60Arylamino, substituted C3-C60Heteroaryl, substituted C3-C60Cycloalkyl, substituted C1-C60Alkoxy, substituted or unsubstituted C1-C60Alkylamino, substituted or unsubstituted C6-C60Arylamino, substituted C6-C60Aryloxy, substituted C6-C60The substituents in the arylthio group are independently represented by hydrogen, an isotope of hydrogen, halogen, cyano, carboxyl, nitro, hydroxyl, sulfonic acid, phosphoric acid, boryl, silyl, C1-C20Alkyl radical, C6-C60Aryl radical C3-C60Heteroaryl group, C1-C60Alkylamino radical, C6-C60Any one of arylamino groups.
Preferably, the specific structural formula of the novel organometallic iridium complex is as follows:
the invention also provides a preparation method of the novel organic metal iridium complex, which comprises the following steps:
the synthetic route of the preparation method is as follows:
s1, stirring and dissolving a boric acid compound with a general formula A-1 and a bromopyridine compound with a general formula A-2 in a solvent, sequentially adding a catalyst and an acid-binding agent, wherein the molar ratio of the boric acid compound with the general formula A-1 to the bromopyridine compound with the general formula A-2 is 1 (2-3), reacting at 80-100 ℃ under the protection of inert gas, and performing a post-treatment process after the reaction is finished to obtain the phenylpyridine compound with the general formula A;
s2, adding phenylpyridine compounds of the general formula A and iridium trichloride into a solvent, reacting under the conditions of inert gas protection and temperature of 120-140 ℃, and after the reaction is finished, performing a post-treatment process to obtain an iridium bridged ligand compound of the general formula B;
s3, adding a solvent and an acid-binding agent into an iridium bridged ligand compound shown in the general formula B and an acetylacetone compound shown in the general formula C, reacting at room temperature, and after the reaction is finished, performing a post-treatment process to obtain a target compound shown in the formula I;
wherein, in step S1, R1～R3R, m, n are as defined in any one of claims 1 to 41～R3R, m and n are as defined.
Preferably, in the step S2, the molar ratio of the phenylpyridine compound of the general formula A to the iridium trichloride is 1 (2-3).
Preferably, in the step S3, the molar ratio of the bridged ligand compound of iridium of general formula B to the acetylacetone compound of general formula C is (2-3): 1.
Preferably, in step S1, the reaction solvent is a mixed solvent of toluene, ethanol and deionized water, the reaction time is 16-24 hours, the catalyst is palladium tetratriphenylphosphine, and the acid-binding agent is potassium carbonate.
Preferably, in step S2, the reaction solvent is ethylene glycol diethyl ether or an ethylene glycol diethyl ether/water mixture, and the reaction time is 18-36 hours.
Preferably, in step S3, the reaction solvent is one or a mixture of two or more of ethylene glycol diethyl ether, 2-ethoxyethanol, 2-methoxyethyl ether and 1, 2-dichloroethane, the reaction time is 12-30 hours, and the acid-binding agent is one or a mixture of two or more of sodium carbonate and sodium hydroxide;
preferably, in step S1, the post-processing procedure is: and monitoring by TLC (thin layer chromatography) until the reaction is finished, cooling, standing for liquid separation, separating a water layer, reserving a toluene layer, washing the toluene layer once, separating the liquid, and spin-drying the toluene layer to obtain a dark solid. Passing through a silica gel column to obtain the phenylpyridine compound with the general formula A.
Preferably, in step S2, the post-processing procedure is: and (3) separating out solids after reacting for 1 hour, continuing to react for 12-24 hours, monitoring the reaction by using a point plate, cooling after the raw materials react, directly filtering to obtain yellow solids, washing by using ethanol and petroleum ether in sequence, and drying to obtain the iridium bridged ligand compound shown in the general formula B.
Preferably, in step S3, the post-processing procedure is: and (5) monitoring by a point plate, after all the raw materials are reacted, carrying out suction filtration to obtain a yellow solid, and thus obtaining the target compound shown in the formula I.
Preferably, the target product can be purified by methanol and ethylene glycol ethyl ether.
The invention also provides an organic electroluminescent device, which comprises a substrate, and an anode layer, a hole transport layer, an organic light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and a cathode layer which are sequentially evaporated on the substrate, wherein the organic light-emitting layer comprises a main material and a doping material, and the doping material is the novel organic metal iridium complex as claimed in any one of claims 1 to 4.
Preferably, the weight ratio of the host substance to the doping material is (90-95): (5-0.5).
Preferably, the thickness of the organic light emitting layer is 25 to 35 nm.
The invention further provides application of the organic electroluminescent device in a luminescent device, a solar cell, electronic paper, a photoreceptor or a thin film transistor.
According to the technical scheme, compared with the prior art, the novel metal iridium complex, the preparation method thereof and the organic electroluminescent device comprising the same have the following beneficial effects:
(1) the novel metal iridium complex provided by the invention is a series of metal complex electrophosphorescent luminescent materials with aromatic amine compounds, the wavelength of the compounds is adjusted by selecting specific heterocyclic complexes, the electroluminescent efficiency is high, the service life is long, and meanwhile, the materials are easy to prepare and purify and have very wide market prospects.
(2) The organic electroluminescent compounds according to the present invention, having a main chain with more excellent EL properties and thermal stability than conventional phosphorescent materials, provide higher quantum efficiency and lower starting voltage than conventional materials, and thus, using the compounds according to the present invention in OLED panels, further improved results can be expected in studies with medium to large-sized OLEDs.
(3) The preparation method of the iridium metal complex provided by the invention has the advantages of simple and efficient process and high purity of the prepared product.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a novel organic metal iridium complex, which has a structural general formula shown as a formula I:
wherein:
R1～R3each independently represents hydrogen, substituted or unsubstituted C1-C5Alkyl, substituted or unsubstituted C6-C18Aryl, substituted or unsubstituted C5-C25Heterocyclic radical, substituted or unsubstituted C6-C30Arylamino, R1～R3The same or different;
r independently represents hydrogen, hydrogen isotope, halogen, cyano, carboxyl, nitro, hydroxyl, sulfonic acid group, phosphoric acid group, boron alkyl, phosphorus oxy, arylamine group, substituted or unsubstituted silicon group, and substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C6-C60Aryl, substituted or unsubstituted C3-C60Heteroaryl, substituted or unsubstituted C3-C60Cycloalkyl, substituted or unsubstituted C1-C60Alkoxy, substituted or unsubstituted C1-C60Alkylamino, substituted or unsubstituted C6-C60Arylamino, substituted or unsubstituted C6-C60Aryloxy, substituted or unsubstituted C6-C60Arylthio, substituted or unsubstituted C6-C60Aryl silicon group;
r can be at any position of the ring;
wherein m and n are natural numbers, and m is more than or equal to 1 and less than or equal to 3, n is more than or equal to 0 and less than or equal to 2, or n is more than or equal to 1 and less than or equal to 3, and m is more than or equal to 0 and less than or equal to 2.
Preferably, when m is 2 or 3, R of the benzene ring are bonded to each other through a C-C bond, a C-N bond, a C-O bond or a C-S bond to form a five-membered ring, a six-membered ring or a seven-membered ring; when N is 2 or 3, R of the pyridine ring are bonded to each other through a C-C bond, a C-N bond, a C-O bond or a C-S bond to form a five-membered ring, a six-membered ring or a seven-membered ring.
Preferably, R1～R3Each independently represents substituted or unsubstituted C1-C5Alkyl, substituted or unsubstituted C6-C18Aryl, substituted or unsubstituted C6-C30Arylamino, R1～R3The same or different.
Preferably, R independently represents hydrogen, an isotope of hydrogen, halogen, cyano, carboxyl, nitro, hydroxyl, sulfonic acid group, boryl, phosphoxy, arylamino, substituted or unsubstituted silicon group, substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C6-C60Aryl, substituted or unsubstituted C3-C60Heteroaryl, substituted or unsubstituted C3-C60Cycloalkyl, substituted or unsubstituted C1-C60Alkoxy, substituted or unsubstituted C1-C60An alkylamino group.
Preferably, said substituted C1-C5Alkyl, substituted C6-C18Aryl, substituted C5-C25Heterocyclyl, substituted C6-C30Arylamino, substituted C1-C20Alkyl, substituted C6-C60Aryl, substituted C3-C60Heteroaryl, substituted C3-C60Cycloalkyl, substituted C1-C60Alkoxy, substituted C1-C60Alkylamino, substituted C6-C60Arylamino, substituted C6-C60Aryloxy, substituted C6-C60Arylthio, substituted C6-C60Arylsilyl groups, substituted silyl groups in which the substituents independently represent hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxy, C1-C5Alkyl radical, C6-C18Aryl radical, C6-C18Heteroaryl group, C6-C30Arylamino, C3-C60Cycloalkyl radical, C1-C60Alkoxy, adamantyl, C7-C60Bicycloalkyl radical, C2-C60Alkenyl radical, C2-C60Alkynyl, C1-C60One or more of alkoxy, 5-membered heteroalkyl comprising one or more heteroatoms selected from N, O and S, and 6-membered heteroalkyl comprising one or more heteroatoms selected from N, O and S.
Example 1
Synthesis of Compound 4, the structural formula is as follows:
the first step is as follows: preparation of intermediate 4-A
(1) The synthesis method of the intermediate 4-A comprises the following steps: adding a raw material 4-A-1(0.07mol) into a reactor, adding 300mL of toluene, 150mL of ethanol and 150mL of deionized water, stirring for 30 minutes under the protection of nitrogen, then respectively adding the raw material 4-A-2(0.084mol), a catalyst of tetratriphenylphosphine palladium (0.0007mol) and potassium carbonate (0.14mol), and heating to 90 ℃ for reacting for 24 hours.
(2) And (3) post-treatment process of the intermediate 4-A: TLC monitoring until the reaction is finished. Cooling, standing, separating, removing water layer, and keeping toluene layer. The toluene layer was washed once with 150mL of water, separated, dried, and spun dried to give a dark solid. Passing through a silica gel column, flushing impurity spots by using 500mL of mixed solvent of dichloromethane and petroleum ether with the volume ratio of 1:4, flushing all product spots by using 1000mL of mixed solvent of ethyl acetate and petroleum ether with the volume ratio of 3:1, and performing spin drying to obtain an intermediate 4-A, wherein the product is 18g, the yield is 80%, and the MW: theoretical value 320.13, test value: 320.12.
the second step is that: preparation of intermediate 4-B
(1) The synthesis method of the intermediate 4-B comprises the following steps: adding the product 4-A (0.05618mol) in the first step and iridium trichloride (0.02247mol) into a three-neck flask, then adding 200mL of ethylene glycol diethyl ether and 100mL of water, heating to 140 ℃ under the protection of nitrogen, and stirring for reacting for 24 hours.
(2) And (3) post-treatment process of the intermediate 4-B: and (3) separating out solids after reacting for 1 hour, continuing to react for 24 hours, performing plate counting monitoring reaction, cooling after the reaction of the raw materials is finished, performing direct suction filtration to obtain yellow solids, washing with 100mL of ethanol, washing with 100mL of petroleum ether, and drying to obtain an intermediate 4-B, wherein the intermediate is obtained by 1g of a product, the yield is 80%, and the MW: theoretical value: 1731.85, test value: 1731.84.
the third step: preparation of target Compound 4
(1) Method for synthesis of target compound 4: intermediate 4-B (0.00624mol) was placed in a three-necked flask, and 200mL of ethylene glycol diethyl ether, sodium carbonate (0.05mol), and 4-C (0.028mol) were added thereto, followed by stirring at room temperature for 24 hours.
(2) Post-treatment process of the target compound: and (3) monitoring by a point plate, after all the raw materials are reacted, carrying out suction filtration to obtain a yellow solid, namely the target compound 4, wherein 11.5g of the product is obtained, the yield is 80%, the product is purified by methanol and ethylene glycol ethyl ether, and the HPLC (high performance liquid chromatography) is 99.63%, and the MW: theoretical value: 929.27, test value: 929.28.
example 2
Synthesis of compound 19, structural formula:
the first step is as follows: synthesis of intermediate 19-A
(1) The synthesis method of the intermediate 19-A comprises the following steps: adding a raw material 19-A-1(0.049mol) into a reactor, adding 300mL of toluene, 150mL of ethanol and 150mL of deionized water, stirring for 30 minutes under the protection of nitrogen, then respectively adding the raw material 19-A-2(0.0588mol), a catalyst of tetrakistriphenylphosphine palladium (0.00049mol) and potassium carbonate (0.098mol), and heating to 90 ℃ for reacting for 24 hours.
(2) Post-treatment of intermediate 19-A: TLC monitoring until the reaction is finished. Cooling, standing, separating, removing water layer, and keeping toluene layer. The toluene layer was washed once with 150mL of water, separated, dried, and spun dried to give a dark solid. Passing through a silica gel column, washing out impurity spots by using 400mL of a mixed solvent of dichloromethane and petroleum ether with a volume ratio of 1:4, washing out all product spots by using 1200mL of a mixed solvent of ethyl acetate and petroleum ether with a volume ratio of 3:1, and performing spin drying to obtain an intermediate 19-A, wherein the product is 16.5g, the yield is 81%, and the MW: theoretical value 489.68, test value: 489.18.
the second step is that: preparation of intermediate 19-B
(1) The synthesis method of the intermediate 19-B comprises the following steps: adding the first step product 19-A (0.03mol) and iridium trichloride (0.0125mol) into a three-neck flask, then adding 150mL of ethylene glycol diethyl ether and 70mL of water, heating to 140 ℃ under the protection of nitrogen, and stirring for reacting for 24 hours.
(2) Post-treatment of intermediate 19-B: and (3) separating out solids after reacting for 1 hour, continuing to react for 24 hours, monitoring the reaction by using a point plate, cooling when the reaction of the raw materials is finished, directly filtering to obtain yellow solids, washing with 100mL of ethanol, washing with 100mL of petroleum ether, and drying to obtain an intermediate 19-B, wherein the intermediate is 11.0g of a product, the yield is 80%, and the MW: theoretical value: 2617.47, test value: 2617.37.
the third step: preparation of target Compound 19
(1) Method for synthesis of target compound 19: intermediate 19-B (0.0048mol) was placed in a three-necked flask, and 150mL of ethylene glycol diethyl ether, sodium carbonate (0.0384mol), and 19-C (0.024mol) were added thereto, followed by reaction with stirring at room temperature for 24 hours.
(2) Post-treatment process of the target compound: and (3) monitoring by a point plate, after all the raw materials are reacted, carrying out suction filtration to obtain a yellow solid, namely the target compound 19, and obtaining a product 11.0g, the yield is 90%, and the MW: theoretical value: 1331.75, test value: 1331.55.
example 3
Synthesis of compound 20, structural formula:
the first step is as follows: synthesis of intermediate 20-A
(1) The synthesis method of the intermediate 20-A comprises the following steps: adding 20-A-1(0.049mol) as a raw material into a reactor, adding 300mL of toluene, 150mL of ethanol and 150mL of deionized water, stirring for 30 minutes under the protection of nitrogen, then respectively adding 20-A-2(0.0588mol) as the raw material, palladium (0.00049mol) as a catalyst and potassium carbonate (0.098mol), and heating to 90 ℃ for reacting for 24 hours.
(2) And (3) post-treatment process of the intermediate 20-A: TLC monitoring until the reaction is finished. Cooling, standing, separating, removing water layer, and keeping toluene layer. The toluene layer was washed once with 150mL of water, separated, dried, and spun dried to give a dark solid. Passing through a silica gel column, flushing impurity spots by using 500mL of mixed solvent of dichloromethane and petroleum ether with the volume ratio of 1:4, flushing all product spots by using 1000mL of mixed solvent of ethyl acetate and petroleum ether with the volume ratio of 3:1, and performing spin drying to obtain an intermediate 4-A, wherein 14g of a product is obtained, the yield is 80%, and the MW: theoretical value 355.11, test value: 355.10.
the second step is that: preparation of intermediate 20-B
(1) The synthesis method of the intermediate 20-B comprises the following steps: adding the product 20-A (0.03mol) in the first step and iridium trichloride (0.0125mol) into a three-neck flask, then adding 150mL of ethylene glycol diethyl ether and 70mL of water, heating to 140 ℃ under the protection of nitrogen, and stirring for reacting for 24 hours.
(2) And (3) post-treatment process of the intermediate 20-B: and (3) separating out solids after reacting for 1 hour, continuing to react for 24 hours, monitoring the reaction by using a point plate, cooling when the reaction of the raw materials is finished, directly filtering to obtain yellow solids, washing with 100mL of ethanol, washing with 100mL of petroleum ether, and drying to obtain an intermediate 20-B, wherein 9.0g of a product, 80% of yield and MW: theoretical value: 1875.77, test value: 1875.76.
the third step: preparation of target Compound 4
(1) Method for synthesis of target compound 20: intermediate 20-B (0.0048mol) was placed in a three-necked flask, and 150mL of ethylene glycol diethyl ether, sodium carbonate (0.0384mol), and 20-C (0.024mol) were added thereto, followed by reaction with stirring at room temperature for 24 hours.
(2) Post-treatment process of the target compound: and (3) monitoring by a point plate, after all the raw materials are reacted, carrying out suction filtration to obtain a yellow solid, namely a target compound 4, and obtaining a product 9.0g, the yield is 90%, and the MW: theoretical value: 1002.23, test value: 1002.24.
example 4
Synthesis of Compound 41, the structural formula is as follows:
the first step is as follows: synthesis of intermediate 41-A
(1) The synthesis method of the intermediate 41-A comprises the following steps: adding a raw material 41-A-1(0.049mol) into a reactor, adding 300mL of toluene, 150mL of ethanol and 150mL of deionized water, stirring for 30 minutes under the protection of nitrogen, then respectively adding the raw material 41-A-2(0.0588mol), a catalyst of tetrakistriphenylphosphine palladium (0.00049mol) and potassium carbonate (0.098mol), and heating to 90 ℃ for reacting for 24 hours.
(2) Post-treatment of intermediate 41-A: TLC monitoring until the reaction is finished. Cooling, standing, separating, removing water layer, and keeping toluene layer. The toluene layer was washed once with 150mL of water, separated, dried, and spun dried to give a dark solid. Passing through a silica gel column, flushing impurity spots by using 500mL of mixed solvent of dichloromethane and petroleum ether with the volume ratio of 1:4, flushing all product spots by using 1000mL of mixed solvent of ethyl acetate and petroleum ether with the volume ratio of 3:1, and performing spin drying to obtain an intermediate 41-A, wherein 9.9g of a product is obtained, the yield is 80%, and the MW: theoretical 253.3, test value: 253.2.
the second step is that: preparation of intermediate 41-B
(1) The synthesis method of the intermediate 41-B comprises the following steps: adding the product 41-A (0.03mol) in the first step and iridium trichloride (0.0125mol) into a three-neck flask, then adding 150mL of ethylene glycol diethyl ether and 70mL of water, heating to 140 ℃ under the protection of nitrogen, and stirring for reacting for 24 hours.
(2) Post-treatment process of intermediate 41-B: and (3) separating out solids after reacting for 1 hour, continuing to react for 24 hours, monitoring the reaction by using a point plate, cooling when the reaction of the raw materials is finished, directly filtering to obtain yellow solids, washing with 100mL of ethanol, washing with 100mL of petroleum ether, and drying to obtain an intermediate 41-B, wherein the intermediate is obtained by obtaining a product 10.9g, the yield is 80%, and the MW: theoretical value: 1466.51, test value: 1466.48.
the third step: preparation of target Compound 41
(1) Method for synthesizing target compound 41: intermediate 41-B (0.0048mol) was placed in a three-necked flask, and 150mL of ethylene glycol diethyl ether, sodium carbonate (0.0384mol), and 41-C (0.024mol) were added thereto, followed by reaction with stirring at room temperature for 24 hours.
(2) Post-treatment process of the target compound: and (3) monitoring by a point plate, after all the raw materials are reacted, carrying out suction filtration to obtain a yellow solid, namely the target compound 41, and obtaining a product 8.0g, the yield is 90%, and the MW: theoretical value: 935.08, test value: 935.03.
example 5
Synthesis of Compound 50, the structural formula is as follows:
the first step is as follows: synthesis of intermediate 50-A
(1) The synthesis method of the intermediate 50-A comprises the following steps: adding a raw material 50-A-1(0.049mol) into a reactor, adding 300mL of toluene, 150mL of ethanol and 150mL of deionized water, stirring for 30 minutes under the protection of nitrogen, then respectively adding the raw material 50-A-2(0.0588mol), a catalyst of tetrakistriphenylphosphine palladium (0.00049mol) and potassium carbonate (0.098mol), and heating to 90 ℃ for reacting for 24 hours.
(2) Post-treatment of intermediate 50-A: TLC monitoring until the reaction is finished. Cooling, standing, separating, removing water layer, and keeping toluene layer. The toluene layer was washed once with 150mL of water, separated, dried, and spun dried to give a dark solid. Passing through a silica gel column, flushing impurity spots by using 500mL of mixed solvent of dichloromethane and petroleum ether with the volume ratio of 1:4, flushing all product spots by using 1000mL of mixed solvent of ethyl acetate and petroleum ether with the volume ratio of 3:1, and performing spin drying to obtain an intermediate 50-A, wherein 11.3g of a product is obtained, the yield is 82%, and the MW: theoretical value 281.10, test value: 281.11.
the second step is that: preparation of intermediate 50-B
(1) The synthesis method of the intermediate 50-B comprises the following steps: adding the product 50-A (0.03mol) in the first step and iridium trichloride (0.0125mol) into a three-neck flask, then adding 150mL of ethylene glycol diethyl ether and 70mL of water, heating to 140 ℃ under the protection of nitrogen, and stirring for reacting for 24 hours.
(2) Post-treatment of intermediate 50-B: and (3) separating out solids after reacting for 1 hour, continuing to react for 24 hours, monitoring the reaction by using a point plate, cooling when the reaction of the raw materials is finished, directly filtering to obtain yellow solids, washing with 100mL of ethanol, washing with 100mL of petroleum ether, and drying to obtain an intermediate 50-B, wherein 8.2g of a product is obtained, the yield is 83%, and the MW: theoretical value: 1579.77, test value: 1579.78.
the third step: preparation of target Compound 50
(1) Method for synthesis of target compound 50: intermediate 50-B (0.0048mol) was placed in a three-necked flask, and 150mL of ethylene glycol diethyl ether, sodium carbonate (0.0384mol), and 50-C (0.024mol) were added thereto, followed by reaction with stirring at room temperature for 24 hours.
(2) Post-treatment of target compound 50: and (3) monitoring by a point plate, after all the raw materials are reacted, carrying out suction filtration to obtain a yellow solid, namely a target compound 4, and obtaining a product 7.5g, the yield is 85%, and the MW: theoretical value: 916.24, test value: 916.25.
example 6
Synthesis of Compound 51, the structural formula is as follows:
the first step is as follows: synthesis of intermediate 51-A
(1) The synthesis method of the intermediate 51-A comprises the following steps: adding a raw material 51-A-1(0.049mol) into a reactor, adding 300mL of toluene, 150mL of ethanol and 150mL of deionized water, stirring for 30 minutes under the protection of nitrogen, then respectively adding 50-A-2(0.0588mol) of the raw material, a catalyst of tetratriphenylphosphine palladium (0.00049mol) and potassium carbonate (0.098mol), and heating to 90 ℃ for reacting for 24 hours.
(2) Post-treatment of intermediate 51-A: TLC monitoring until the reaction is finished. Cooling, standing, separating, removing water layer, and keeping toluene layer. The toluene layer was washed once with 150mL of water, separated, dried, and spun dried to give a dark solid. Passing through a silica gel column, flushing impurity spots by using 500mL of mixed solvent of dichloromethane and petroleum ether with the volume ratio of 1:4, flushing all product spots by using 1000mL of mixed solvent of ethyl acetate and petroleum ether with the volume ratio of 3:1, and performing spin drying to obtain an intermediate 50-A, wherein the product is 11.9g, the yield is 86%, and the MW: theoretical value 280.10, test value: 280.11.
the second step is that: preparation of intermediate 51-B
(1) The synthesis method of the intermediate 51-B comprises the following steps: adding the product 51-A (0.03mol) in the first step and iridium trichloride (0.0125mol) into a three-neck flask, then adding 150mL of ethylene glycol diethyl ether and 70mL of water, heating to 140 ℃ under the protection of nitrogen, and stirring for reacting for 24 hours.
(2) Post-treatment of intermediate 51-B: and (3) separating out solids after reacting for 1 hour, continuing to react for 24 hours, monitoring the reaction by using a point plate, cooling when the reaction of the raw materials is finished, directly filtering to obtain yellow solids, washing with 100mL of ethanol, washing with 100mL of petroleum ether, and drying to obtain an intermediate 51-B, wherein 8.6g of a product is obtained, the yield is 87%, and the MW: theoretical value: 1579.73, test value: 1579.74.
the third step: preparation of target Compound 51
(1) Method for synthesizing target compound 51: intermediate 51-B (0.0048mol) was placed in a three-necked flask, and 150mL of ethylene glycol diethyl ether, sodium carbonate (0.0384mol), and 51-C (0.024mol) were added thereto, followed by reaction with stirring at room temperature for 24 hours.
(2) Post-treatment process of the target compound: and (3) monitoring by a point plate, after all the raw materials are reacted, carrying out suction filtration to obtain a yellow solid, namely a target compound 4, and obtaining a product 8.0g, the yield is 90%, and the MW: theoretical value: 928.24, test value: 928.25.
example 7
Synthesis of Compound 64, the structural formula is as follows:
the first step is as follows: synthesis of intermediate 64-A
(1) The synthesis method of the intermediate 64-A comprises the following steps: adding a raw material 64-A-1(0.049mol) into a reactor, adding 300mL of toluene, 150mL of ethanol and 150mL of deionized water, stirring for 30 minutes under the protection of nitrogen, then respectively adding the raw material 64-A-2(0.0588mol), a catalyst of tetrakistriphenylphosphine palladium (0.00049mol) and potassium carbonate (0.098mol), and heating to 90 ℃ for reacting for 24 hours.
(2) Post-treatment of intermediate 64-A: TLC monitoring until the reaction is finished. Cooling, standing, separating, removing water layer, and keeping toluene layer. The toluene layer was washed once with 150mL of water, separated, dried, and spun dried to give a dark solid. Passing through a silica gel column, flushing impurity spots by using 500mL of mixed solvent of dichloromethane and petroleum ether with the volume ratio of 1:4, flushing all product spots by using 1000m of mixed solvent of ethyl acetate and petroleum ether with the volume ratio of 3:1, and performing spin drying to obtain an intermediate 64-A, wherein the product is 11.4g, the yield is 82%, and the MW: theoretical value 280.10, test value: 280.11.
the second step is that: preparation of intermediate 64-B
(1) The synthesis method of the intermediate 64-B comprises the following steps: adding the product 64-A (0.03mol) in the first step and iridium trichloride (0.0125mol) into a three-neck flask, then adding 150mL of ethylene glycol diethyl ether and 70mL of water, heating to 140 ℃ under the protection of nitrogen, and stirring for reacting for 24 hours.
(2) Post-treatment of intermediate 64-B: and (3) separating out solids after reacting for 1 hour, continuing to react for 24 hours, monitoring the reaction by using a point plate, cooling when the reaction of the raw materials is finished, directly filtering to obtain yellow solids, washing with 100mL of ethanol, washing with 100mL of petroleum ether, and drying to obtain an intermediate 64-B, wherein 8.5g of a product is obtained, the yield is 86%, and the MW: theoretical value: 1575.73, test value: 1575.74.
the third step: preparation of target Compound 64
(1) Method for synthesizing target compound 64: intermediate 64-B (0.0048mol) was placed in a three-necked flask, and 150mL of ethylene glycol diethyl ether, sodium carbonate (0.0384mol), and 64-C (0.024mol) were added thereto, followed by reaction with stirring at room temperature for 24 hours.
(2) Post-treatment process of the target compound: and (3) monitoring by a point plate, after all the raw materials are reacted, carrying out suction filtration to obtain a yellow solid, namely a target compound 64, and obtaining a product 7.1g, the yield is 86%, and the MW: theoretical value: 866.22, test value: 866.23.
example 8
Synthesis of Compound 77, the structural formula is as follows:
the first step is as follows: synthesis of intermediate 64-A
(1) The synthesis method of the intermediate 77-A comprises the following steps: raw material 77-A-1(0.049mol) is added into a reactor, toluene 300mL, ethanol 150mL and deionized water 150mL are stirred for 30 minutes under the protection of nitrogen, then raw material 77-A-2(0.0588mol) and catalyst tetrakistriphenylphosphine palladium (0.00049mol) and potassium carbonate (0.098mol) are respectively added, and the mixture is heated to 90 ℃ for reaction for 24 hours.
(2) Post-treatment of intermediate 64-A: TLC monitoring until the reaction is finished. Cooling, standing, separating, removing water layer, and keeping toluene layer. The toluene layer was washed once with 100mL of water, separated, dried and spun dry to give a dark solid. Passing through a silica gel column, flushing impurity spots by using 400mL of mixed solvent of dichloromethane and petroleum ether with the volume ratio of 1:5, flushing all product spots by using 8000m of mixed solvent of ethyl acetate and petroleum ether with the volume ratio of 3:1, and performing spin drying to obtain an intermediate 77-A, wherein 13.5g of a product is obtained, the yield is 80%, and the MW: theoretical value 287.45, test value: 286.5.
the second step is that: preparation of intermediate 77-B
(1) The synthesis method of the intermediate 77-B comprises the following steps: adding the first step product 77-A (0.03mol) and iridium trichloride (0.0125mol) into a three-neck flask, adding 150mL of ethylene glycol diethyl ether and 70mL of water, heating to 140 ℃ under the protection of nitrogen, and stirring for reacting for 24 hours.
(2) Post-treatment of intermediate 77-B: and (3) separating out solids after reacting for 1 hour, continuing to react for 24 hours, monitoring the reaction by using a point plate, cooling when the reaction of the raw materials is finished, directly filtering to obtain yellow solids, washing with 50mL of ethanol, then washing with 50mL of petroleum ether, and drying to obtain an intermediate 77-B, wherein 8.2g of a product, 82% of yield and MW: theoretical value: 1603.1, test value: 1602.9.
the third step: preparation of target Compound 77
(1) Method for synthesis of target compound 77: intermediate 77-B (0.0048mol) was placed in a three-necked flask, and 150mL of ethylene glycol diethyl ether, sodium carbonate (0.0384mol), and 77-C (0.024mol) were added thereto, followed by reaction with stirring at room temperature for 24 hours.
(2) Post-treatment process of the target compound: and (3) monitoring by a point plate, after all the raw materials are reacted, carrying out suction filtration to obtain a yellow solid, namely a target compound, wherein the obtained product is 7.2g, the yield is 85%, and the MW: theoretical value: 879.24, test value: 878.86.
example 9
The embodiment provides an organic electroluminescent device, which comprises a substrate, an anode layer arranged on the substrate, a hole injection layer arranged on the anode layer, a hole transport layer arranged on the hole injection layer, an organic light emitting layer arranged on the hole transport layer, an air barrier layer arranged on the organic light emitting layer, an electron transport layer arranged on the air barrier layer, an electron injection layer arranged on the electron transport layer and a cathode layer arranged on the electron injection layer.
The preparation method of the organic electroluminescent device comprises the following steps:
(1) coating with a thickness of
The ITO glass substrate is put in distilled water for cleaning for 2 times, ultrasonically cleaned for 30 minutes, repeatedly cleaned for 2 times by distilled water, ultrasonically cleaned for 10 minutes, and after the cleaning by distilled water is finished, solvents such as isopropanol, acetone, methanol and the like are ultrasonically cleaned in sequence and then dried, transferred into a plasma cleaning machine, cleaned for 5 minutes, and baked in a clean environment until the substrate is completely dried;
(2) placing the processed ITO glass substrate in an evaporator, evaporating N1- (2-naphthyl) -N4, N4-di (4- (2-naphthyl (phenyl) amino) phenyl) -N1-phenyl benzene-1, 4-diamine ("2-TNATA") on an ITO (anode) to form a hole injection layer, wherein the thickness of the evaporated layer is 60 nm; continuously evaporating NPB (nitrogen-phosphorus) on the hole injection layer film to form a hole transport layer, wherein the thickness of the evaporated film is 60 nm;
(3) continuously evaporating a layer of the compound 4 and 4, 4'-N, N' -biphenyl dicarbazole ("CBP") of the invention on the hole transport layer to be used as a light-emitting layer of the device, wherein the CBP is a main material and the compound 4 of the invention is a doping material, the weight ratio of the CBP to the doping material compound 4 is 95:5, and the thickness of the evaporated film is 30 nm;
(4) continuously evaporating BALq as a hole blocking layer on the organic light-emitting layer, wherein the thickness of the evaporated film is 10 nm; continuing to evaporate Alq3 on the air barrier layer to be used as an electron transport layer, wherein the thickness of the evaporation film is 40 nm; continuously evaporating LiF on the electron transport layer to form an electron injection layer, wherein the thickness of the evaporated film is 0.2 nm; and finally, continuously evaporating Al on the electron injection layer to form a cathode layer, wherein the thickness of the evaporated film is 150nm, and preparing the OLED-1.
Example 10
By following the same procedure as in example 9 above, substituting only compound 4 used in step (3) with compound 19, OLED-2 provided by the present invention was obtained.
Example 11
By following the same procedure as in example 9 above, substituting only compound 4 used in step (3) with compound 20, OLED-3 provided by the present invention was obtained.
Example 12
By following the same procedure as in example 9 above, substituting only compound 4 used in step (3) with compound 41, OLED-4 provided by the present invention was obtained.
Example 13
By following the same procedure as in example 9 above, substituting only compound 4 used in step (3) with compound 50, OLED-5 provided by the present invention was obtained.
Example 14
By following the same procedure as in example 9 above, substituting only compound 4 used in step (3) with compound 51, OLED-6 provided by the present invention was obtained.
Example 15
By following the same procedure as in example 9 above, substituting only compound 4 used in step (3) with compound 64, OLED-7 provided by the present invention was obtained.
Example 16
By following the same procedure as in example 9 above, substituting only compound 4 used in step (3) with compound 77, OLED-8 provided by the present invention was obtained.
Comparative example 1
Following the same procedure as in example 9 above, only Compound 4 used in step (3) was replaced with Compound Ir (ppy)3To obtain OLED-9 of comparative example.
In order to further illustrate the luminescence property of the novel metal iridium complex provided by the invention as a phosphorescent material, the performance luminescence characteristics of the devices OLED-1 to OLED-9 obtained in examples 9 to 16 and comparative example 1 were tested, and a KEITHLEY model 2400 source measuring unit and a CS-2000 spectroradiometer were used for evaluating the driving voltage, the luminescence brightness and the luminescence efficiency.
Table 1 results of testing organic electroluminescent elements in examples 9 to 16 and comparative example 1
And (4) conclusion: as can be seen from the performance test results in Table 1, the device test performance is based on the device OLED-9, each performance index of the OLED-9 is set to be 1.0, while the driving voltage of the devices OLED-1 to OLED-8 provided by the invention is 0.49-0.52 which is only half of that of the OLED-9 (comparative example 1), and the efficiency (3.8-4.3) and the service life (3.4-3.9) are 3-4 times of that of the OLED-9 (comparative example 1), so that the compound can be applied to an OLED light-emitting device, and compared with the comparative example 1, the compound has the characteristics of high efficiency, long service life, more excellent optical performance and remarkable progress.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A novel organic metal iridium complex is characterized in that the structural general formula of the novel organic metal iridium complex is shown as formula I:
wherein:
R1～R3each independently represents hydrogen, substituted or unsubstituted C1-C5Alkyl, substituted or unsubstituted C6-C18Aryl, substituted or unsubstituted C5-C25Heterocyclic radical, substituted or unsubstituted C6-C30Arylamino, R1～R3The same or different;
r independently represents hydrogen, hydrogen isotope, halogen, cyano, carboxyl, nitro, hydroxyl, sulfonic group, boryl, phosphorus oxy, arylamino, substituted or unsubstituted silicon base, substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C6-C60Aryl, substituted or unsubstituted C3-C60Heteroaryl, substituted or unsubstituted C3-C60Cycloalkyl, substituted or unsubstituted C1-C60Alkoxy, substituted or unsubstituted C1-C60Alkylamino, substituted or unsubstituted C6-C60Arylamino, substituted or unsubstituted C6-C60Aryloxy, substituted or unsubstituted C6-C60Arylthio, substituted or unsubstituted C6-C60Aryl silicon group;
r can be at any position of the ring;
wherein m and n are natural numbers, and m is more than or equal to 1 and less than or equal to 3, n is more than or equal to 0 and less than or equal to 2, or n is more than or equal to 1 and less than or equal to 3, and m is more than or equal to 0 and less than or equal to 2.
2. The novel organometallic iridium complex according to claim 1, wherein when m is 2 or 3, R' S of benzene rings are bonded to each other through a C-C bond, a C-N bond, a C-O bond or a C-S bond to form a five-membered ring, a six-membered ring or a seven-membered ring; when N is 2 or 3, R of the pyridine ring are bonded to each other through a C-C bond, a C-N bond, a C-O bond or a C-S bond to form a five-membered ring, a six-membered ring or a seven-membered ring.
3. The novel organometallic iridium complex according to claim 1, wherein R is1～R3Each independently represents substituted or unsubstituted C1-C5Alkyl, substituted or unsubstituted C6-C18Aryl, substituted or unsubstituted C6-C30Arylamino, R1～R3The same or different.
4. A novel organometallic iridium complex as claimed in claim 1, wherein R independently represents hydrogen, an isotope of hydrogen, halogen, cyano, carboxyl, nitro, hydroxyl, sulfonic acid, boryl, phosphoxy, arylamino, substituted or unsubstituted silicon group, substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C6-C60Aryl, substituted or unsubstituted C3-C60Heteroaryl, substituted or unsubstituted C3-C60Cycloalkyl, substituted or unsubstituted C1-C60Alkoxy, substituted or unsubstituted C1-C60An alkylamino group.
5. A method for producing a novel organometallic iridium complex according to any one of claims 1 to 4, characterized by comprising the steps of:
s1, stirring and dissolving a boric acid compound with a general formula A-1 and a bromopyridine compound with a general formula A-2 in a solvent, sequentially adding a catalyst and an acid-binding agent, wherein the molar ratio of the boric acid compound with the general formula A-1 to the bromopyridine compound with the general formula A-2 is 1 (2-3), reacting at 80-100 ℃ under the protection of inert gas, and performing a post-treatment process after the reaction is finished to obtain the phenylpyridine compound with the general formula A;
s2, adding phenylpyridine compounds of the general formula A and iridium trichloride into a solvent, reacting under the conditions of inert gas protection and temperature of 120-140 ℃, and after the reaction is finished, performing a post-treatment process to obtain an iridium bridged ligand compound of the general formula B;
s3, adding a solvent and an acid-binding agent into an iridium bridged ligand compound shown in the general formula B and an acetylacetone compound shown in the general formula C, reacting at room temperature, and after the reaction is finished, performing a post-treatment process to obtain a target compound shown in the formula I;
wherein, in step S1, R1～R3R, m, n are as defined in any one of claims 1 to 41～R3R, m and n are as defined.
6. The method for preparing a novel organometallic iridium complex according to claim 5, wherein in the step S2, the molar ratio of the phenylpyridine compound of the general formula A to iridium trichloride is 1 (2-3).
7. The method for producing a novel organometallic iridium complex according to claim 5, wherein in the step S3, the molar ratio of the bridged ligand compound of iridium of the general formula B to the acetylacetone-based compound of the general formula C is (2-3): 1.
8. An organic electroluminescent device, comprising a substrate, and an anode layer, a hole transport layer, an organic light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and a cathode layer which are sequentially evaporated on the substrate, wherein the organic light emitting layer comprises a host material and a doping material, and the doping material is the novel organic metal iridium complex of any one of claims 1 to 4.
9. An organic electroluminescent device according to claim 8, wherein the weight ratio of the host substance to the dopant material is (90-95): (5-0.5).
10. Use of an organic electroluminescent device according to claims 8 to 9 in a light-emitting device, a solar cell, electronic paper, a photoreceptor or a thin film transistor.
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| EP3960747A1 (en) * | 2020-08-31 | 2022-03-02 | Samsung Electronics Co., Ltd. | Organometallic compound and organic light-emitting device including the same |
| US20220089624A1 (en) * | 2020-09-22 | 2022-03-24 | Samsung Electronics Co., Ltd. | Organometallic compound, organic light-emitting device including the same, and electronic apparatus including the organic light-emitting device |
| CN114644658A (en) * | 2020-12-17 | 2022-06-21 | 乐金显示有限公司 | Organometallic compound, organic light emitting diode and organic light emitting device having the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP3960747A1 (en) * | 2020-08-31 | 2022-03-02 | Samsung Electronics Co., Ltd. | Organometallic compound and organic light-emitting device including the same |
| US12004416B2 (en) | 2020-08-31 | 2024-06-04 | Samsung Electronics Co., Ltd. | Organometallic compound and organic light-emitting device including the same |
| US20220089624A1 (en) * | 2020-09-22 | 2022-03-24 | Samsung Electronics Co., Ltd. | Organometallic compound, organic light-emitting device including the same, and electronic apparatus including the organic light-emitting device |
| CN114644658A (en) * | 2020-12-17 | 2022-06-21 | 乐金显示有限公司 | Organometallic compound, organic light emitting diode and organic light emitting device having the same |
| EP4015521A1 (en) * | 2020-12-17 | 2022-06-22 | LG Display Co., Ltd. | Organic metal compound, organic light emitting diode and organic light emitting device having the compound |
| TWI823189B (en) * | 2020-12-17 | 2023-11-21 | 南韓商樂金顯示科技股份有限公司 | Organic metal compound, and organic light emitting device having the compound |
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