CN110283216A - Three deuterated complex of iridium of one kind and its preparation method and application - Google Patents
Three deuterated complex of iridium of one kind and its preparation method and application Download PDFInfo
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- CN110283216A CN110283216A CN201910652756.7A CN201910652756A CN110283216A CN 110283216 A CN110283216 A CN 110283216A CN 201910652756 A CN201910652756 A CN 201910652756A CN 110283216 A CN110283216 A CN 110283216A
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- Prior art keywords
- deuterated
- iridium
- complex
- molecular formula
- alkyl
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- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 122
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 71
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- 239000000126 substance Substances 0.000 claims abstract description 6
- 230000005622 photoelectricity Effects 0.000 claims abstract description 3
- 239000003446 ligand Substances 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 31
- -1 normal-butyl Chemical group 0.000 claims description 30
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 239000000539 dimer Substances 0.000 claims description 13
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 11
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052805 deuterium Inorganic materials 0.000 claims description 10
- 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 9
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 9
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 9
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 9
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 claims description 9
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 9
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 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 5
- BVQRIWXTJZDNAE-UHFFFAOYSA-N N1=CC=CC2=CC=CC=C12.C1(=CC=CC=C1)N1CC2=CC=CC=C2C=C1 Chemical compound N1=CC=CC2=CC=CC=C12.C1(=CC=CC=C1)N1CC2=CC=CC=C2C=C1 BVQRIWXTJZDNAE-UHFFFAOYSA-N 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 238000007039 two-step reaction Methods 0.000 claims description 2
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 claims 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 claims 2
- ZMXDDKWLCZADIW-YYWVXINBSA-N N,N-dimethylformamide-d7 Chemical compound [2H]C(=O)N(C([2H])([2H])[2H])C([2H])([2H])[2H] ZMXDDKWLCZADIW-YYWVXINBSA-N 0.000 claims 2
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 claims 2
- 125000004826 2,3-dimethylpropylene group Chemical group [H]C([H])([H])C([H])([*:2])C([H])(C([H])([H])[H])C([H])([H])[*:1] 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical class CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical class OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 1
- QTBSBXVTEAMEQO-GUEYOVJQSA-N acetic acid-d4 Chemical compound [2H]OC(=O)C([2H])([2H])[2H] QTBSBXVTEAMEQO-GUEYOVJQSA-N 0.000 claims 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical class [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 24
- 238000004020 luminiscence type Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000003595 spectral effect Effects 0.000 abstract description 4
- 230000000704 physical effect Effects 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 239000013110 organic ligand Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 22
- 238000003786 synthesis reaction Methods 0.000 description 22
- 125000005594 diketone group Chemical group 0.000 description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 14
- 238000012512 characterization method Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 238000007789 sealing Methods 0.000 description 12
- 150000002503 iridium Chemical class 0.000 description 11
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 11
- 239000004926 polymethyl methacrylate Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 239000002019 doping agent Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- 238000006467 substitution reaction Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- FZFRYQHIQUEAAV-UHFFFAOYSA-N 2,8-dimethylnonane Chemical compound CC(C)CCCCCC(C)C FZFRYQHIQUEAAV-UHFFFAOYSA-N 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- FSEXLNMNADBYJU-UHFFFAOYSA-N 2-phenylquinoline Chemical compound C1=CC=CC=C1C1=CC=C(C=CC=C2)C2=N1 FSEXLNMNADBYJU-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- JVZRCNQLWOELDU-UHFFFAOYSA-N gamma-Phenylpyridine Natural products C1=CC=CC=C1C1=CC=NC=C1 JVZRCNQLWOELDU-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 238000006862 quantum yield reaction Methods 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- VDULMXJUOWIPGE-UHFFFAOYSA-N 1-phenylisoquinoline quinoline Chemical compound N1=CC=CC2=CC=CC=C12.C1(=CC=CC=C1)C1=NC=CC2=CC=CC=C12 VDULMXJUOWIPGE-UHFFFAOYSA-N 0.000 description 2
- SBPIDKODQVLBGV-UHFFFAOYSA-N 1h-imidazole;pyridine Chemical class C1=CNC=N1.C1=CC=NC=C1 SBPIDKODQVLBGV-UHFFFAOYSA-N 0.000 description 2
- IWQNSRNINVHEIV-UHFFFAOYSA-N C1(=CC=CC=C1)C1=NC=CC=C1.N1C=NC=C1 Chemical class C1(=CC=CC=C1)C1=NC=CC=C1.N1C=NC=C1 IWQNSRNINVHEIV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000005424 photoluminescence Methods 0.000 description 2
- 238000000103 photoluminescence spectrum Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- MVGWJKHATAGKOO-UHFFFAOYSA-N 1,2,3-triphenylpyridin-1-ium Chemical class C1=CC=CC=C1C1=CC=C[N+](C=2C=CC=CC=2)=C1C1=CC=CC=C1 MVGWJKHATAGKOO-UHFFFAOYSA-N 0.000 description 1
- XIBFIOFSBLXRDI-UHFFFAOYSA-N 1-(2,6-dichlorophenyl)-2-methylguanidine Chemical compound CNC(=N)NC1=C(Cl)C=CC=C1Cl XIBFIOFSBLXRDI-UHFFFAOYSA-N 0.000 description 1
- QWNCDHYYJATYOG-UHFFFAOYSA-N 2-phenylquinoxaline Chemical compound C1=CC=CC=C1C1=CN=C(C=CC=C2)C2=N1 QWNCDHYYJATYOG-UHFFFAOYSA-N 0.000 description 1
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000090 biomarker Substances 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000005053 phenanthridines Chemical class 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003216 pyrazines Chemical class 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 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 System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System 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
Abstract
Application and related photoelectricity physical property the invention discloses a kind of three deuterated complex of iridium and preparation method thereof to the compound in terms of electroluminescent material.The preparation path that is directed to and method are a kind of miscellaneous with having many advantages, such as that versatility, high efficiency and volume production cost are suitable on compound containing iridium in preparation.The present invention passes through the Organic ligand modification to Cyclometalated iridium (III) complex, the fluorescence quantum efficiency (PLQE) of luminescent material molecule can be improved, stability of the complex in luminescence process is improved, and the stability of material devices application can be further increased.Function is transformed according to the spectral signature of these molecules, chemical property and compound, very specific this kind of molecule can be used to prepare the OLED related device and application implements of high quality.
Description
Technical field
The invention belongs to technical field of electronic materials, and in particular to a kind of organometallic complex that part isotope replaces
And its preparation side and application of the complex in terms of electroluminescent utensil.
Background technique
Iridium (III) complex compound is a kind of widely used phosphorescence luminous organic material, although above-mentioned luminous organic material exists
It has been commercialized in terms of manufacture oled panel and luminaire, however these materials still have many rooms for promotion, for example reduce
Material preparation process cost, the basic photoelectric properties for improving material, promotion final products application experience quality, reduce device processing procedure
The middle mating cost of material, and improve material overall tolerability after device is integrated and in terms of.
In the prior art, (WO2015039723) discloses the synthesis of the complex of iridium of polycyclic phenylpyridine and its organic
Application in photoelectric device；US20030072964, US20070087321 disclose the Phosphorescent that phenyl isoquinolin quinoline is ligand
Material；US20080261076 disclose the Ir that 2- quinoline phenyl and 2- isoquinolin phenyl are ligand it is miscellaneous be used as with complex compound have
Machine phosphor material；US20120181511 discloses the application of the complex of iridium of the phenylchinoline of 5- substitution in the light emitting diode,
Wherein relate to diketone structureAssistant ligand phenylpyridine；CN107459535A disclose 3,4 or 5 it is mono-substituted
The synthesis of the complex of iridium of phenylpyridine and its application in organic electro-optic device, preparation method include 3,4 substitutions,
3,5 substitutions, 4,5 compounds replaced with the quinoline ligands of 3,4,5 substitutions, assistant ligand is diketone structure.
The miscellaneous of Ir that WO2013094620 discloses polysubstituted pyrazine ligand coordination is used as Phosphorescent red light material with complex compound；
Deep-red iridium complexes cyclometalated by phenanthridine derivatives for
highly efficient solution-processed organic light-emitting diodesBei Jiang,Yu
Gu, Jingjing Qin, XiaowenNing, Shaolong Gong, GuohuaXie and Chuluo Yang Journal of
The Ir that Materials Chemistry C 2016page 3492-3498 reports phenylphenanthridineand ligands is miscellaneous with phosphorescence material
Material；Highly efficient,deep-red organic light-emitting devices using energy
transfer from exciplexes Yuji Nagai,Hisahiro Sasabe,Jun Takahashi,
ANatsukiOnuma, Takashi Ito, a Satoru Ohisaab and Junji Kido report the coordination of phenyl quinoxaline
The miscellaneous compound of matching of Ir is in dark red light to the application in near-infrared material.US20080217606 be disclosed phenylchinoline be with
Body, pyridine imidazoles and phenylpyridine imidazoles are the Organic Light Emitting Diode material of assistant ligand, and content is only limitted to simply replace
Phenylquinoline ligands；It is ligand that US20080261076, which is disclosed phenyl isoquinolin quinoline, and pyridine imidazoles and phenylpyridine imidazoles are
The Organic Light Emitting Diode material of assistant ligand.
The performance of material in the application, paper Synthesis of all- can be improved in isotope substitution
deuteratedtris(2-phenylpyridine)iridium for highly stable
electrophosphorescence:the “deuterium effect”Ping Wang,Fei-Fei Wang,Yi Chen,
QiangNiu,Lei Lu,Hong-Ming Wang,Xi-Cun Gao,Bin Wei,Hong-Wei Wu,Xin Caic and
De-Chun ZouJ.Mater.Chem.C, 2013,1,4821-4825 disclosures report deuterated triphenylpyridinium complex of iridium
With more stable electroluminescence.Patent CN107200755 discloses deuterated complex and improves phosphorescent light-emitting materials performance
Scheme.Wherein, diketone structureThe complex of iridium of assistant ligand coordination, which is used as luminous organic material, has extraordinary warp
Applicability of helping and process operability, opposite research are more.Wherein forThe complex of iridium of assistant ligand coordination exists
Research (the Chemical Degradation in Organic Light-Emitting of deactivation mechanism in OLED device application
Devices:Mechanisms and Implications for the Design of New Materials,Susanna
Schmidbauer,Andreas Hohenleutner andAdv.Mater.2013,25,2114–2129)
It reportsAssistant ligand is easy to dissociate and cause complex of iridium photoelectric functional material molecular inactivation than other main ligands.
Patent CN108299510 is disclosedThe substitution ligand scheme of assistant ligand.
Replace the invention discloses a kind of selective deuteriumThe preparation method of the complex of iridium of assistant ligand coordination,
And application of the compound in terms of electroluminescent material and related photoelectricity physical property.The preparation path being directed to and side
Method replaces in preparation one kind containing deuteriumThere is versatility, high efficiency and volume production on the complex of iridium of assistant ligand coordination
The advantages that cost is suitble to.The present invention is modified by the ligand isotope of the organometallic complex in Cyclometalated iridium (III), can be with
The fluorescence quantum efficiency (PLQE) of luminescent material molecule is improved, the redox stabilization of complex in application process is improved
Property, and can explicitly further increase the stability of material devices application.According to the spectral signature of these molecules, electrochemistry
Function can be transformed with compound, very specific this kind of molecule can be used to prepare the OLED related device and applicator of high quality
Tool.
Summary of the invention
The technical problems to be solved by the present invention are: disclosing the organic iridium complex and its preparation side that three deuteriums of one kind replace
Method, three it is deuterated after complex of iridium strengthen the photoelectric conversion feature of stability in application process and the compound with
And the performance boost in terms of electroluminescent material.
In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is that: provide first stability it is more preferably high
The luminous organic metal complex of iridium of effect, has following molecular structural formula:
WhereinThe 2- phenyl isoquinolin quinoline of primary electron transition energy level effect is partially referred to, has been parent
Ligand moiety (master matches),Refer to 1, the 3 dicarbapentaborane assistant ligand parts (auxiliary to match) that three deuteriums replace, Ir3+Match at finger center
Position metal, ligand is all negative one valence, and Ir is positive trivalent.
Wherein Ra、RbIt is self-existent hydrogen atom, alkyl substituent and aryl substituent, alkyl substituent can be deuterium
Generation, the deuterated alkyl replaced containing alkyl or aryl in part, aryl substituent can be that deuterated, part is deuterated or contains
There is the aryl of alkyl or aryl substituent group.RcIt is alkyl substituent, alkyl substituent can deuterated, part be deuterated and aryl
Substituted alkyl.
The alkyl replaced herein can refer to but be not limited to straight chain or branch containing 1-6 carbon atom, this kind of alkyl can be with
Including methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tertiary butyl, n-pentyl, 1- methyl butyl, 2- methyl fourth
Base, 3- methyl butyl, 1,2- dimethyl propyl, 2,3- dimethyl propyl and 1- ethyl propyl, cyclopenta, cyclohexyl, 2- methyl-
3- amyl, 3,3- dimethyl -2- butyl etc..
In molecular formula I type molecule, Ra,RbAnd RcIt is independent from each other, represents a hydrogen atom or substituent group.
The organic metal iridium matches the molecular structural formula R of compoundcWhen determining,It can be following six kinds of structures,
It is respectively designated as molecular formula II, molecular formula III, molecular formula IV, molecular formula V, molecular formula VI and molecular formula VII.
In molecular formula II, molecular formula III, molecular formula IV, molecular formula V, molecular formula VI and molecular formula VII, each RaWith
RbIt can be individually present or be not present.
RaCan be hydrogen atom, D-atom, methyl, deuterated methyl, ethyl, deuterated ethyl, n-propyl, deuterated n-propyl,
Isopropyl, deuterated isopropyl, normal-butyl, deuterated normal-butyl, isobutyl group, deuterated isobutyl group, tertiary butyl, deuterated tertiary butyl, positive penta
Base, deuterated n-pentyl, 1- methyl butyl, deuterated 1- methyl butyl, 2- methyl butyl, deuterated 2- methyl butyl, 3- methyl butyl,
Deuterated 3- methyl butyl, 1,2- dimethyl propyl, deuterated 1,2- dimethyl propyl, 2,3- dimethyl propyl, deuterated 2,3- diformazan
Base propyl, 1- ethyl propyl, deuterated 1- ethyl propyl, cyclopenta, deuterated cyclopenta, cyclohexyl, deuterated cyclohexyl, 2- methyl-
3- amyl, deuterated 2- methyl -3- amyl, 3,3- dimethyl -2- butyl, deuterated 3,3- dimethyl -2- butyl, phenyl, phenyl, first
Base substituted-phenyl, deuterated methyl substituted-phenyl, ethyl substituted-phenyl, deuterated ethyl substituted-phenyl, propyl substituted-phenyl, deuterated third
Base substituted-phenyl, butyl substituted-phenyl, deuterated butyl substituted-phenyl, amyl substituted-phenyl, deuterated amyl substituted-phenyl, hexyl take
For phenyl, deuterated hexyl substituted-phenyl etc..
RbIt can be methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tertiary butyl, deuterated tertiary butyl, positive penta
Base, 1- methyl butyl, 2- methyl butyl, 3- methyl butyl, 1,2- dimethyl propyl, deuterated 1,2- dimethyl propyl, 2,3- bis-
Methyl-propyl, 1- ethyl propyl, cyclopenta, cyclohexyl etc.
The preparation method of above-mentioned three deuterated metal iridium complex, at least includes the following steps: by precursor substance and trivalent iridium
Dimer is prepared in reaction；The dimer and assistant ligand precursor compound and deuterated reagent pass through single step reaction or two
Step reaction, obtains compound shown in the molecular formula I；Chemical equation is as follows:
In addition, the complex of iridium the present invention also provides one kind containing three deuterated diketone assistant ligands is in electroluminescent material
The application of aspect specifically can be used for organic electronic assembly, such as organic electronic assembly, is Organic Light Emitting Diode, shines
Diode, compact fluorescent lamp, incandescent lamp, organic photovoltaic battery, organic field effect tube or light-emitting electrochemical cell.Especially
It is organic photoelectric luminescent device, is also used as biomarker or is applied in imaging technique.
The beneficial effects of the present invention are: compared with prior art, the invention discloses a kind of novel materials for electroluminescence,
Specific site introducing improves the stability of compound in main ligand, such compound, which has, at least keeps original complex (not
By deuterated) equally efficient photoelectric conversion characteristic, there is promotion in terms of light, electricity, thermal stability, as doped luminescent material
Applied to the relevant utensil of the electroluminescent device service life that utensil can be improved.The preparation path being directed to and method
Have many advantages, such as that versatility, high efficiency and volume production cost are suitble on complex of iridium of the preparation containing deuterated diketone assistant ligand.
Function is transformed according to the spectral signature and compound of these molecules, very specific this kind of molecule can be used to prepare the organic of high quality
Electroluminescent related device and application implements.
Detailed description of the invention
Fig. 1 is the OLED for using the complex of iridium of of the present invention three deuterated diketone assistant ligands as glowing material
Structure chart；
Fig. 2 is three deuterated complex Ir-44 and non-deuterated complex of iridium Ir (dmpiq)2The comparison of divm photoluminescence spectra
Figure；
Fig. 3 is by three deuterated complex Ir-44 and non-deuterated complex of iridium Ir (dmpiq)2Divm (Ir-44 (H)) is used as red
Photodoping material is prepared into the luminescent spectrum figure of device.
Fig. 4 is three deuterated complex of iridium Ir-44 and non-deuterated complex of iridium Ir (dmpiq) under room temperature2Divm is used as feux rouges
The glow current voltage change figure (4a) and voltage brightness change figure (4b) of the OLED device of dopant material preparation；
Fig. 5 is three deuterated complex of iridium Ir-44 and non-deuterated complex of iridium Ir (dmpiq) under room temperature2Divm is used as feux rouges
The glow current efficiency chart (5a) and power efficiency figure (5b) of the OLED device of dopant material preparation；
The nucleus magnetic hydrogen spectrum and non-deuterated product comparison diagram of the deuterated complex of iridium Ir-44 of Fig. 6 tri-；
Fig. 7 is the nucleus magnetic hydrogen spectrum of three deuterated complex of iridium Ir-44 structural characterizations；
Fig. 8 is the nucleus magnetic hydrogen spectrum of three deuterated complex of iridium Ir-53 structural characterizations；
Fig. 9 is the nucleus magnetic hydrogen spectrum of three deuterated complex of iridium Ir-23 structural characterizations；
The super-pressure high-efficient liquid phase analysis purity and matching Mass Spectrometer Method figure that Figure 10 is three deuterated complex of iridium Ir-44；
Figure 11 is the Mass Spectrometer Method figure of three deuterated complex of iridium Ir-53；
Figure 12 is the Mass Spectrometer Method figure of three deuterated complex of iridium Ir-59；
Figure 13 is the complex of iridium Ir (dmpiq) of three deuterated complex of iridium Ir-44 and non-deuterated diketone assistant ligand2divm
The attenuation curve of luminescence generated by light at any time；
Figure 14 is the complex of iridium Ir (dmpiq) of three deuterated complex of iridium Ir-44 and non-deuterated diketone assistant ligand2divm
The luminous attenuation curve caused at any time of the device of preparation；
Figure 15 is that Figure 15 is three deuterated complex of iridium Ir-44 and single deuterated complex of iridium Ir (dmpiq) 2divm- under room temperature
D1 is used as the luminous power efficiency chart (15a) and current efficiency figure (15b) of the OLED device of feux rouges dopant material preparation；
Figure 16 is three deuterated complex of iridium Ir-44 and single deuterated complex of iridium Ir (dmpiq)2divm-d1Luminescence generated by light is at any time
Between attenuation curve；
Figure 17 is three deuterated complex of iridium Ir-44 and single deuterated complex of iridium Ir (dmpiq)2divm-d1The device of preparation
The attenuation curve of luminous cause at any time.
Specific embodiment
In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is that: a kind of suitable technique preparation is provided
The better machine metal complex of stability has following molecular structural formula:
Formula I is equal to Chinese concept molecular formula I, similar below, such as molecular formula II, molecular formula III.
WhereinThe 2- phenyl isoquinolin quinoline ligand moiety of primary electron transition energy level effect is partially referred to
(master matches),Refer to multiple 1,3 deuterated dicarbapentaborane assistant ligand (auxiliary to match) parts, Ir3+Refer to central coordinated metal, ligand
It is all negative one valence, Ir is positive trivalent.
Wherein Ra、RbIt is self-existent hydrogen atom, alkyl substituent and aryl substituent, alkyl substituent can be deuterated
, the alkyl that part is deuterated and aryl replaces, aryl substituent can be that deuterated, part is deuterated and contains alkyl or virtue
The aryl of base substituent group.RcIt is alkyl substituent, alkyl substituent can deuterated, part is deuterated and aryl replaces alkane
Base.
This paper alkyl can refer to but be not limited to straight chain or branch containing 1-6 carbon atom, this kind of alkyl may include second
Base, n-propyl, isopropyl, normal-butyl, isobutyl group, tertiary butyl, n-pentyl, 1- methyl butyl, 2- methyl butyl, 3- methyl fourth
Base, 1,2- dimethyl propyl, 2,3- dimethyl propyl and 1- ethyl propyl, cyclopenta, cyclohexyl, 2- methyl -3- amyl, 3,3-
Dimethyl -2- butyl etc..
In Formula I type molecule, Ra,RbAnd RcIt is independent from each other and represents a hydrogen atom or substituent group.
The molecular structural formula R of the organometallic ligand compoundcWhen determining,It can be following six kinds of structures, point
It is not named as molecular formula II, molecular formula III, molecular formula IV, molecular formula V, molecular formula VI and molecular formula VII.
In molecular formula II, molecular formula III, molecular formula IV, molecular formula V, molecular formula VI and molecular formula VII, each RaWith
RbIt can be individually present or be not present.
RaCan be hydrogen atom, D-atom, methyl, deuterated methyl, ethyl, deuterated ethyl, n-propyl, deuterated n-propyl,
Isopropyl, deuterated isopropyl, normal-butyl, deuterated normal-butyl, isobutyl group, deuterated isobutyl group, tertiary butyl, deuterated tertiary butyl, positive penta
Base, deuterated n-pentyl, 1- methyl butyl, deuterated 1- methyl butyl, 2- methyl butyl, deuterated 2- methyl butyl, 3- methyl butyl,
Deuterated 3- methyl butyl, 1,2- dimethyl propyl, deuterated 1,2- dimethyl propyl, 2,3- dimethyl propyl, deuterated 2,3- diformazan
Base propyl, 1- ethyl propyl, deuterated 1- ethyl propyl, cyclopenta, deuterated cyclopenta, cyclohexyl, deuterated cyclohexyl, 2- methyl-
3- amyl, deuterated 2- methyl -3- amyl, 3,3- dimethyl -2- butyl, deuterated 3,3- dimethyl -2- butyl, phenyl, phenyl, first
Base substituted-phenyl, deuterated methyl substituted-phenyl, ethyl substituted-phenyl, deuterated ethyl substituted-phenyl, propyl substituted-phenyl, deuterated third
Base substituted-phenyl, butyl substituted-phenyl, deuterated butyl substituted-phenyl, amyl substituted-phenyl, deuterated amyl substituted-phenyl, hexyl take
For phenyl, deuterated hexyl substituted-phenyl etc..
RbIt can be methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tertiary butyl, deuterated tertiary butyl, positive penta
Base, 1- methyl butyl, 2- methyl butyl, 3- methyl butyl, 1,2- dimethyl propyl, deuterated 1,2- dimethyl propyl, 2,3- bis-
Methyl-propyl, 1- ethyl propyl, cyclopenta, cyclohexyl etc.
According to the total general molecular formula of above-mentioned molecular formula I, molecular formula II, molecular formula III, molecular formula IV, molecular formula V, molecule
Formula VI and molecular formula VII represent the one of the substitution main ligands of 2- phenyl isoquinolin quinoline of a kind of specific deuterated diketonate ligand coordination
The deuterated iridium of class matches compound-material structure.
Molecular formula I can be following molecular formula, i.e. molecular formula II, molecular formula III, molecular formula IV, molecular formula V, molecular formula
VI and molecular formula VII；Molecular formula I is not limited to molecular formula II, molecular formula III, molecular formula IV, molecular formula V, molecular formula VI and divides
Minor VII.
Molecular formula I can be following molecule Ir-1 to Ir-126；Molecular formula I is not limited to molecule Ir-1 to Ir-126.
Molecular formula II can be following molecule Ir-1 to Ir-21；Molecular formula II is not limited to molecule Ir-1 to Ir-21.
Molecular formula III can be following molecule Ir-22 to Ir-42；Molecular formula III is not limited to molecule Ir-22 to Ir-
42。
Molecular formula IV can be following molecule Ir-43 to Ir-63；Molecular formula IV is not limited to molecule Ir-43 to Ir-63.
Molecular formula V can be following molecule Ir-64 to Ir-84；Molecular formula V is not limited to molecule Ir-64 to Ir-84.
Molecular formula VI can be following molecule Ir-85 to Ir-105；Molecular formula VI is not limited to molecule Ir-85 to Ir-
105。
Molecular formula VII can be following molecule Ir-106 to Ir-126；Molecular formula VII is not limited to molecule Ir-106 to Ir-
126。
Molecule Ir (pq)2acac、Ir(dmpiq)2Divm is conventional phosphorescence light emitting molecule, and relevant experimental data is this implementation
Example molecule provides comparison and reference.Ir(pq)2acac、Ir(dmpiq)2Divm structure is as follows, wherein Ir (dmpiq)2Divm is iridium
The non-deuterated product of complex Ir-44.
Specific embodiment
The deuterated Ir-2 of embodiment 1. 3 synthesis and structural characterization
The synthesis of dimer A: 1- (3,5- 3,5-dimethylphenyl) isoquinolin (1.1g, 4.7mmol) being added into 75ml tube sealing,
Three water iridous chlorides (332.6mg, 0.9mmol), ethylene glycol ethyl ether (15mL) and water (5mL), nitrogen displacement reaction flask atmosphere.It will
Reaction system is heated to 100 DEG C, stirs 12 hours.Reaction solution is cooled to room temperature, solid is precipitated, washing, ether washing, dry
To dimer A (660mg, 45%).
The synthesis of three deuterated complex of iridium 2.Dimer A (138.3mg, 0.1mmol) is added into 15ml tube sealing, heptane-
3,5- diketone (0.1ml), sodium carbonate (53mg, 0.5mmol), ethylene glycol ethyl ether (3mL) and heavy water (0.2mL), nitrogen are bubbled three
Minute, reaction system is heated to reflux 12 hours.Reaction solution is cooled to room temperature, is filtered, filtrate was spin-dried for column (petroleum ether: acetic acid second
Ester=10:1) obtain three deuterated complex of iridium 2 (120mg, 71%).NMR(400MHz,)δ9.02-9.00(m,2H),8.26(d,J
=6.4Hz, 2H), 7.97 (s, 2H), 7.84-7.82 (m, 2H), 7.70-7.65 (m, 4H), 7.24 (d, J=6.4Hz, 2H),
6.58(s,2H),2.34(s,6H),1.82-1.72(m,1H),1.68-1.62(m,1H),1.46(s,6H),0.34-0.30(m,
6H).MS(ESI):787.6[M]+Emission peak in DCM at 629nm, FWHM=64nm, peak in PMMA at
629nm, FWHM=58nm.
The deuterated Ir-23 of embodiment 2. 3 synthesis and structural characterization
The synthesis of three deuterated complex of iridium 23.Dimer A (138.3mg, 0.1mmol) is added into 15ml tube sealing, nonane-
4,6- diketone (0.1ml), sodium carbonate (53mg, 0.5mmol), ethylene glycol ethyl ether (3mL) and heavy water (0.2mL), nitrogen are bubbled three
Minute, reaction system is heated to reflux 12 hours.Reaction solution is cooled to room temperature, is filtered, filtrate was spin-dried for column (petroleum ether: acetic acid second
Ester=10:1) obtain three deuterated complex of iridium 23 (120mg, 71%).Fig. 9 is the core of three deuterated complex of iridium Ir-23 structural characterizations
Magnetic hydrogen spectrum.By knowing that deuterated method provided by the invention realizes that corresponding deuterated product has versatility in figure.NMR
(400MHz) δ 8.98-8.96 (m, 2H), 8.23 (d, J=6.4Hz, 2H), 7.95 (s, 2H), 7.81-7.79 (m, 2H),
7.68-7.64 (m, 4H), 7.22 (d, J=6.4Hz, 2H), 6.56 (s, 2H), 2.32 (s, 6H), 1.85-1.79 (m, 1H),
1.69-1.62 (m, 1H), 1.44 (s, 6H), 0.89-0.83 (m, 2H), 0.77-0.70 (m, 2H), 0.01 (t, J=6.8Hz,
6H).MS(ESI):815.6[M]+Emission peak in DCM at 627nm, FWHM=61nm, peak in PMMA at
629nm, FWHM=58nm
The deuterated Ir-44 of embodiment 3. 3 synthesis and structural characterization
The synthesis of three deuterated complex of iridium 44.Dimer A (138.3mg, 0.1mmol) is added into 15ml tube sealing, 2,8-
Dimethylnonane -4,6- diketone (0.1ml), sodium carbonate (53mg, 0.5mmol), ethylene glycol ethyl ether (3mL) and heavy water
(0.2mL), nitrogen are bubbled three minutes, and reaction system is heated to reflux 12 hours.Reaction solution is cooled to room temperature, is filtered, filtrate is spin-dried for
It crosses column (petroleum ether: ethyl acetate=10:1) and obtains three deuterated complex of iridium 44 (120mg, 71%).Fig. 7 is three deuterated iridium cooperations
The nucleus magnetic hydrogen spectrum of object Ir-44 structural characterization.Wherein, the H on three sites shown in structure is converted to monoisotopic D
Atom, deuterated rate are 95%-100%.1H NMR (500MHz, CDCl3) δ 8.99 (d, J=7.5Hz, 2H), 8.25 (d, J=
6.0Hz, 2H), 7.96 (s, 2H), 7.82-7.80 (m, 2H), 7.70-7.65 (m, 4H), 7.23 (d, J=6.5Hz, 2H), 6.59
(s,2H),2.35(s,6H),1.82-1.78(m,1H),1.59-1.53(m,1H),1.46(s,6H),1.33-1.28(m,2H),
0.35-0.33 (m, 6H), -0.11 (d, J=6.5Hz, 6H) .MS (ESI): 844.3 [M+1]+Emission peak in DCM
At 625nm, FWHM=59nm, peak in PMMA at 629nm, FWHM=54nm.Figure 10 is three deuterated complex of iridium Ir-
44 super-pressure high-efficient liquid phase analysis purity and matching Mass Spectrometer Method figure, purity 100%.As shown in Figure 10, after deuterium replaces
Compound Ir-44 can be very good to purify, and stability is good, be easy to purify, and is suitble to batch production technique control, finally obtains high-purity
The organic photoelectrical material chemicals of electron level purity.The nucleus magnetic hydrogen spectrum and non-deuterated product pair of the deuterated complex of iridium Ir-44 of Fig. 6 tri-
Than figure.Diagram shows to be converted into hydrogen (H) atom of designated position corresponding polysubstituted using method provided by the invention
Isotope deuterium (D) atom, the deuterated rate of final products are 95-100%.
The deuterated Ir-53 of embodiment 4: three synthesis and structural characterization
The synthesis of dimer B.Into 75ml tube sealing be added 1- (3,5- 3,5-dimethylphenyl) -6- isobutyl quinoline (1.45g,
5.0mmol), three water iridous chloride (352.3mg, 1mmol), ethylene glycol ethyl ether (15mL) and water (5mL), nitrogen displacement reaction flask
Atmosphere.Reaction system is heated to 100 DEG C, is stirred 12 hours.Reaction solution is cooled to room temperature, solid is precipitated, and washing, ether is washed
It washs, is dried to obtain dimer B (660mg, 45%).
The synthesis of three deuterated complex of iridium 53.Dimer B (160.7mg, 0.1mmol) is added into 15ml tube sealing, 2,8-
Dimethylnonane -4,6- diketone (0.1ml), sodium carbonate (53mg, 0.5mmol), ethylene glycol ethyl ether (3mL) and heavy water (0.2mL),
Nitrogen is bubbled three minutes, and reaction system is heated to reflux 12 hours.Reaction solution is cooled to room temperature, was spin-dried for column (petroleum ether: acetic acid second
Ester=10:1) obtain red three deuterated complex of iridium 53 (140mg, 75%).Fig. 8 is three deuterated complex of iridium Ir-53 structural characterizations
Nucleus magnetic hydrogen spectrum.1H NMR(500MHz,CDCl3) δ 8.88 (d, J=9.0Hz, 2H), 8.20 (d, J=6.5Hz, 2H), 7.97
(s, 2H), 7.54 (s, 2H), 7.49 (d, J=8.5Hz, 2H), 7.16 (d, J=6.5Hz, 2H), 6.57 (s, 2H), 2.71 (d, J
=7.0Hz, 4H), 2.34 (s, 6H), 2.09-2.03 (m, 2H), 1.46 (s, 6H), 1.29-1.26 (m, 2H), 1.01-0.99
(m, 12H), 0.32 (d, J=7.0Hz, 6H), -0.11 (d, J=6.5Hz, 6H) .MS (ESI): 956.4 [M+1]+Emission
Peak in DCM at 619nm, FWHM=59nm, peak in PMMA at 622nm, FWHM=53nm.Figure 11 is three deuterated
The Mass Spectrometer Method figure of complex of iridium Ir-53, marginal data Ir-53 are deuterated product.
The deuterated Ir-56 of embodiment 5: three synthesis and structural characterization
The synthesis of dimer C.1- (3,5- 3,5-dimethylphenyl) -6- (p- tolyl) isoquinolin is added into 75ml tube sealing
(1.29g, 4mmol), three water iridous chlorides (282.1mg, 0.8mmol), ethylene glycol ethyl ether (15mL) and water (5mL), nitrogen is set
Change reaction flask atmosphere.Reaction system is heated to 100 DEG C, is stirred 12 hours.Reaction solution is cooled to room temperature, solid is precipitated, washing,
Ether washing, is dried to obtain dimer C (700mg, 45%).
The synthesis of three deuterated complex of iridium 56.Dimer C (174.3mg, 0.1mmol) is added into 15ml tube sealing, 2,8-
Dimethylnonane -4,6- diketone (0.1ml), sodium carbonate (53mg, 0.5mmol), ethylene glycol ethyl ether (3mL) and heavy water (0.2mL)
Nitrogen is bubbled three minutes, and reaction system is heated to reflux 12 hours.Reaction solution is cooled to room temperature, is filtered, filtrate was spin-dried for column (petroleum
Ether: ethyl acetate=10:1) obtain three deuterated complex of iridium 56 (150mg, 73%).1H NMR(500MHz,CDCl3)δ9.04(d,J
=9.0Hz, 2H), 8.26 (d, J=6.5Hz, 2H), 8.01 (s, 2H), 7.98 (s, 2H), 7.94 (d, J=9.0Hz, 2H),
7.70 (d, J=8.0Hz, 4H), 7.36 (d, J=8.0Hz, 4H), 7.26 (s, 2H), 6.60 (s, 2H), 2.47 (s, 6H), 2.36
(s, 6H), 1.83-1.80 (m, 1H), 1.59-1.56 (m, 1H), 1.49 (s, 6H), 1.37-1.34 (m, 2H), 0.37 (d, J=
7.0Hz, 6H), -0.04 (d, J=6.5Hz, 6H) .MS (ESI): 1024.4 [M+1]+Emission peak in DCM at
633nm, FWHM=59nm, peak in PMMA at 635nm, FWHM=52nm.
The deuterated Ir-59 of embodiment 6: three synthesis and structural characterization
The synthesis of dimer D.Into 75ml tube sealing be added 1- (3,5- 3,5-dimethylphenyl) -4- isobutyl quinoline (1.45g,
5.0mmol), three water iridous chloride (352.3mg, 1mmol), ethylene glycol ethyl ether (15mL) and water (5mL), nitrogen displacement reaction flask
Atmosphere.Reaction system is heated to 100 DEG C, is stirred 12 hours.Reaction solution is cooled to room temperature, solid is precipitated, and washing, ether is washed
It washs, is dried to obtain dimer D (660mg, 45%).
The synthesis of three deuterated complex of iridium 59.Dimer D (160.7mg, 0.1mmol) is added into 15ml tube sealing, 2,8-
Dimethylnonane -4,6- diketone (0.1ml), sodium carbonate (53mg, 0.5mmol), ethylene glycol ethyl ether (3mL) and heavy water (0.2mL),
Nitrogen is bubbled three minutes, and reaction system is heated to reflux 12 hours.Reaction solution is cooled to room temperature, was spin-dried for column (petroleum ether: acetic acid second
Ester=10:1) obtain red three deuterated complex of iridium 59 (140mg, 74%).1H NMR(500MHz,CDCl3) δ 8.99 (d, J=
7.5Hz, 2H), 8.11 (s, 2H), 7.96 (d, J=8.5Hz, 1H), 7.92 (s, 2H), 7.70-7.64 (m, 4H), 6.57 (s,
2H), 2.71 (d, J=7.0Hz, 4H), 2.34 (s, 6H), 2.03-1.98 (m, 2H), 1.47 (s, 6H), 1.29-1.23 (m,
4H), 0.95-0.93 (m, 12H), 0.26 (d, J=7.0Hz, 6H), -0.20 (d, J=6.5Hz, 6H) .MS (ESI): 956.4 [M
+1]+Emission peak in DCM at 626nm, FWHM=53nm, peak in PMMA at 626nm, FWHM=
49nm.Figure 12 is the Mass Spectrometer Method figure of three deuterated complex of iridium Ir-59, and marginal data Ir-59 is three deuterated products.
The deuterated Ir-62 of embodiment 7: three synthesis and structural characterization
The synthesis of dimer E.6- cyclohexyl -1- (3,5- 3,5-dimethylphenyl) isoquinolin is added into 75ml tube sealing
(1.58g, 5.0mmol), three water iridous chlorides (352.3mg, 1mmol), ethylene glycol ethyl ether (15mL) and water (5mL), nitrogen is set
Change reaction flask atmosphere.Reaction system is heated to 100 DEG C, is stirred 12 hours.Reaction solution is cooled to room temperature, solid is precipitated, washing,
Ether washing, is dried to obtain dimer E (660mg, 45%).
The synthesis of three deuterated complex of iridium 62.Dimer E (171.1mg, 0.1mmol) is added into 15ml tube sealing, 2,8-
Dimethylnonane -4,6- diketone (0.1ml), sodium carbonate (53mg, 0.5mmol), ethylene glycol ethyl ether (3mL) and heavy water (0.2mL),
Nitrogen is bubbled three minutes, and reaction system is heated to reflux 12 hours.Reaction solution is cooled to room temperature, was spin-dried for column (petroleum ether: acetic acid second
Ester=10:1) obtain red three deuterated complex of iridium 62 (150mg, 75%).1H NMR(500MHz,CDCl3) δ 8.89 (d, J=
9.0Hz, 2H), 8.19 (d, J=6.5Hz, 2H), 7.96 (s, 2H), 7.58 (s, 2H), 7.55 (d, J=8.5Hz, 2H), 7.16
(d, J=6.5Hz, 2H), 6.56 (s, 2H), 2.76-2.71 (m, 2H), 2.34 (s, 6H), 2.03-2.00 (m, 4H), 1.95-
1.93(m,4H),1.85-1.82(m,2H),1.80-1.76(m,2H),1.61-1.56(m,3H),1.53-1.48(m,4H),
1.45 (s, 6H), 1.38-1.33 (m, 2H), 1.31-1.26 (m, 2H), 0.33 (d, J=6.5Hz, 6H), -0.11 (d, J=
6.5Hz,6H).MS(ESI):1007.5[M+1]+Emission peak in DCM at 619nm, FWHM=60nm, peak
In PMMA at 619nm, FWHM=53nm.
The test of the deuterated complex of iridium material characterization of embodiment 8. 3
The optical property of the deuterated complex of iridium of the above-mentioned preparation of the present invention is compared, test method is as follows: material
Band gap magnitude (Eg) and LUMO value are measured using cyclic voltammetry (CV).Entire test process is at glove box (Lab2000, Etelux)
In CHI600D electrochemical workstation (Shanghai Chen Hua instrument company) on carry out, be as working electrode, with Ag/AgCl using Pt column
Reference electrode, Pt constitute three-electrode system for auxiliary electrode, and the medium that test process uses is the 0.1M hexafluorophosphoric acid tetrabutyl
Amine (Bu4NPF6) dimethyl amide (DMF) solution, surveyed potential is using the ferrocene of addition (Fc) as internal standard.Material
HOMO value is directly tested by Model IPS-4 Ionization Energy Measurement System and is obtained.Material
Fluorescence quantum efficiency (PLQE) is according to formula(wherein: ΦsIt is the fluorescence quantum yield of sample, ΦrIt is mark
The fluorescence quantum yield of sample, η are the refractive index of solution, AsAnd ArIt is the absorption value at the fluorescence exciting wavelength of sample and standard specimen, Is
And IrIt is the fluorescence integral area of sample and standard specimen) it is calculated using relative method.By the mark object of material and known quantum yield
It is configured to the chloroform soln of the polymethyl methacrylate (PMMA) of same concentrations, spin-coating film, in identical measurement item
Under part, ultra-violet absorption spectrum (GENESYS10S, Thermo) and fluorescence spectrum (F97pro sepectrophotofluorometer, rib light are measured
Science and technology).By formula E=h ν=1240/ λ, (wherein λ is that the fluorescence spectrum of material PMMA film originates to the photon energy (ET1) of material
The tangent line wavelength of position) it calculates.From the following table 1, it can be seen that three deuterated complex of iridium materials and non-deuterated complex of iridium phase
Than fluorescence quantum efficiency is promoted.
aIt is measured by cyclic voltammetricbThe energy of triplet statecPLQE efficiency is with Ir (PQ)2(acac) hair at 298K
One unit of value on the basis of light efficiency.
Embodiment 9.OLED device
Deuterated complex of iridium is doped in material of main part as luminescent material and is prepared into device OLED, OLED device knot
Structure is as shown in Figure 1.Wherein Cathode is cathode, EIL is electron injecting layer, ETL is electron transfer layer, HTL is hole transport
Layer, p-HIL are hole injection layer, ITO is indium oxide electrode.The complex of iridium Ir-44 conduct of deuterated diketone assistant ligand coordination
Glowing material is included in EML (in luminescent layer), and luminescent layer includes material of main part and luminescent material.By three deuterated iridium cooperations
The complex of iridium Ir (dmpiq) of object Ir-44 and non-deuterated diketone assistant ligand2Divm is applied to comparison its photism after device
The parameters such as energy.
Wherein, Fig. 2 is the complex of iridium of different intermingled dregs ratio example three deuterated complex Ir-44 and non-deuterated diketone assistant ligand
Ir(dmpiq)2Divm photoluminescence spectra comparison diagram.As shown in Figure 2, two kinds of material emission spectrum are completely the same, fluorescence spectrum
Saturation red device can be prepared into red light region.
Fig. 3 is the complex of iridium Ir of different doping ratio three deuterated complex Ir-44 and non-deuterated diketone assistant ligand
(dmpiq)2Divm is used as feux rouges dopant material and is prepared into the luminescent spectrum figure after OLED device.Under identical structure as shown in Figure 3
OLED luminescent spectrum type looks under the same test conditions it is almost the same, but luminous intensity different from, wherein containing deuterium
There is higher electroluminescent intensity at identical conditions for the OLED of product Ir-44, spectral wavelength in 625nm, compared with its
Peak value red shift in PMMA.
Fig. 4 is that the iridium of the difference deuterated complex of iridium Ir-44 of doping ratio three and non-deuterated diketone assistant ligand is matched under room temperature
It closes object Ir (dmpiq)2Divm is used as the illuminated diagram (J-V) and voltage brightness change figure of the OLED device of feux rouges dopant material preparation
(V-L), the i-v curve of the device under identical structure under the same test conditions is almost the same, and voltage brightness curve is shown
The brightness under identical voltage of the corresponding device of Ir-44 is higher.Start voltage in 3V hereinafter, illustrating its core luminescent material with non-
Often good luminescent properties and the stability in luminescence process.
Fig. 5 is that the iridium of the difference deuterated complex of iridium Ir-44 of doping ratio three and non-deuterated diketone assistant ligand is matched under room temperature
It closes object Ir (dmpiq)2Divm is used as the luminous power efficiency chart (5a) and electric current of the OLED device of feux rouges dopant material preparation
Efficiency chart (5b).From in figure, the OLED device of three deuterated complex of iridium Ir-44 preparations have more high current efficiency >
24cd/A, higher luminous efficiency > 25cd/W.
Figure 13 is the complex of iridium Ir (dmpiq) of three deuterated complex of iridium Ir-44 and non-deuterated diketone assistant ligand2divm
The attenuation curve of luminescence generated by light at any time after being prepared into OLED device as feux rouges dopant material.This attenuation test is to pass through
50mW/cm2Ultraviolet light doping 5% complex of iridium stabilization polystyrene polymeric film, and record luminescence generated by light
Intensity, finally obtain compound light-emitting decaying and the time functional relation.Figure 13 shows, three it is deuterated after complex Ir-44
Luminous intensity holding will be apparently higher than its non-deuterated material Ir (dmpiq)2Divm, photoluminescence decay it is slower, have more
Good optical stability.After illumination 400 minutes, the high 7-8% of the more non-deuterated material of luminous intensity reserving degree.
The complex of iridium Ir of Figure 14 difference doping ratio three deuterated complex of iridium Ir-44 and non-deuterated diketone assistant ligand
(dmpiq)2The attenuation curve of the device luminescence generated by light of divm preparation at any time.Device architecture be ITO/HT17:H09 (5%,
10nm)/HT17 (150nm)/PH315:RD (2%, 20nm)/ET15 (60nm)/E02 (2nm)/Al (120nm), wherein RD is represented
Mutually isostructural non-deuterated complex of iridium Ir (dmpiq) 2divm of Ir-44 and comparison.The starting electricity of electroluminescent attenuation test
Current density is 50mA/cm2.Legend shows, it is deuterated after the rate of decay of material Ir-44 device to be significantly lower than its non-deuterated material
Expect Ir (dmpiq)2Divm, electroluminescent decay slower, have better device stability.LT97@50mA/cm2Service life
Respectively 78.6 hours and 30.9 hours, the obvious excellent non-deuterium of device of the material Ir-44 preparation of deuterated diketone assistant ligand coordination
For conventional material.
Embodiment 10
The complex of iridium of three deuterated complex of iridium and non-deuterated diketone assistant ligand is prepared into device, and to its dependency number
According to being tested, test result is as follows for data comparison shown in table 2:
The test of device data correlation data is (being distinguished after non-deuterated dopant material with bracket (H)) as shown in table 2 below:
As shown in table 2, it is compared by device data, Devices Electroluminescent wavelength is mainly by Ir complex luminescence generated by light itself
Decision, under identical conditions, the efficiency of device is also consistent with the PLQE trend of Ir complex itself.Therefore, of the invention
The deuterated iridium of disclosed high PLQE can obtain high device efficiency with compound in other devices.Deuterated iridium matches compound
It is compared with non-deuterated with compound, portion of product current efficiency (CE) and external quantum efficiency (EQE) are significantly improved, such as Ir-
59 and Ir-44；The deuterated front and back of portion of product efficiency does not change significantly, such as Ir53；Three deuterated iridium are with compound and non-deuterated
It is compared with compound, the service life of all devices is significantly improved, and increase rate illustrates three deuterated iridium between 15-30%
It is used to make OLED device as luminescent material with compound and its relevant device compares its conventional non-deuterated iridium with chemical combination
Object has the advantage significantly improved service life；
The single deuterated iridium of embodiment 10 is compared with compound and three deuterated iridium with compounds property
Figure 15 is that three deuterated complex of iridium Ir-44 and single deuterated complex of iridium Ir (dmpiq) 2divm-d1 are used as under room temperature
Feux rouges dopant material preparation OLED device luminous power efficiency chart (15a) and current efficiency figure (15b), device architecture be
ITO/HT17:H09 (5%, 10nm)/HT17 (150nm)/PH315:RD (2%, 20nm)/ET15 (60nm)/E02 (2nm)/Al
(120nm), from figure, the OLED device of three deuterated complex of iridium Ir-44 preparations has more high current efficiency > 24cd/
A, higher luminous efficiency > 25cd/W, and the OLED device photostability of three deuterated complex of iridium Ir-44 preparations is more preferable, device
More efficient and device electroluminescent lifetimes are longer.
Figure 16 is three deuterated complex of iridium Ir-44 and single deuterated complex of iridium Ir (dmpiq)2divm-d1Luminescence generated by light is at any time
Between attenuation curve.Attenuation test is to pass through 50mW/cm2Ultraviolet light doping 5% complex of iridium stabilization polyphenyl second
Alkene macromolecule membrane, and the intensity of luminescence generated by light is recorded, finally obtain the functional relation of compound light-emitting decaying and time.Legend
It has been shown that, it is deuterated after the holding of material Ir-44 luminous intensity to be apparently higher than its single deuterated material Ir (dmpiq)2divm-d1, light
Photoluminescence decays slower, has better optical stability.After illumination 400 minutes, luminous intensity reserving degree wants high 7-
8%.
Figure 17 is three deuterated complex of iridium Ir-44 and single deuterated complex of iridium Ir (dmpiq)2divm-d1The device of preparation
The attenuation curve of luminous cause at any time.Device architecture is ITO/HT17:H09 (5%, 10nm)/HT17 (150nm)/PH315:RD
(2%, 20nm)/ET15 (60nm)/E02 (2nm)/Al (120nm), the initial current density of electroluminescent attenuation test are
50mA/cm2.Legend shows, it is deuterated after the rate of decay of material Ir-44 device to be significantly lower than its deuterated material Ir
(dmpiq)2divm-d1, electroluminescent decays slower, with better device stability.LT97@50mA/cm2Service life
Respectively 78.6 hours and 50 hours, the device of the material Ir-44 preparation of deuterated diketone assistant ligand coordination was substantially better than deuterated
Conventional material.
The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (9)
1. a kind of three deuterated complex of iridium, have following molecular structural formula:
WhereinThe 2- phenyl isoquinolin quinoline of primary electron transition energy level effect is partially referred to, has been the ligand of parent
Part,Refer to 1, the 3 dicarbapentaborane assistant ligand parts (auxiliary to match) that three deuteriums replace, Ir3+ refers to central coordinated metal, matches
Body is all negative one valence, and Ir is positive trivalent；
Wherein Ra、RbSelf-existent hydrogen atom, alkyl substituent and aryl substituent, alkyl substituent can be it is deuterated,
The deuterated alkyl replaced containing alkyl or aryl in part, aryl substituent can be that deuterated, part is deuterated or contains alkane
The aryl of base or aryl substituent；RcAlkyl substituent, alkyl substituent can it is deuterated, part is deuterated and aryl replaces
Alkyl.
2. a kind of three deuterated complex of iridium according to claim 1, which is characterized in that the alkyl can refer to but be not limited to straight chain
Or branch contain 1-6 carbon atom, this kind of alkyl may include methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl
Base, tertiary butyl, n-pentyl, 1- methyl butyl, 2- methyl butyl, 3- methyl butyl, 1,2- dimethyl propyl, 2,3- dimethyl propylene
Base and 1- ethyl propyl, cyclopenta, cyclohexyl, 2- methyl -3- amyl, 3,3- dimethyl -2- butyl etc..
3. three deuterated complex of iridium according to claim 1, which is characterized in that the complex of iridium molecular formula is as follows
Molecular formula II, molecular formula III, molecular formula IV, molecular formula V, molecular formula VI and molecular formula VII:
4. three deuterated complex of iridium according to claim 1, which is characterized in that molecular formula I can be following molecule Ir-1 extremely
Structure shown in Ir-126:
5. three deuterated complex of iridium according to claim 4, which is characterized in that the three deuterated complex of iridium is complex of iridium
Ir-2, Ir-23, Ir-44, Ir-53, Ir-56, Ir-59 and Ir-62, concrete structure formula are that molecular structural formula is as follows:
6. a kind of preparation method for preparing three deuterated complex of iridium described in claim 1, the following steps are included: (1) is by precursor
Matter is reacted with trivalent iridium is prepared dimer；(2) dimer passes through with assistant ligand precursor compound and deuterated reagent
Single step reaction or two-step reaction obtain compound shown in the molecular formula I；Chemical equation is as follows:
7. the preparation method of three deuterated complex of iridium according to claim 6, which is characterized in that the deuterated reagent includes deuterium
Water, deuterated DMSO, deuterated methanol, deuterated ethyl alcohol, deuterated acetic acid, deuterated formic acid, deuterated sodium formate, deuterated benzene, deuterated DMF.
8. application of the three deuterated complex of iridium in terms of electroluminescent material described in claim 1.
9. application of the three deuterated complex of iridium as electroluminescent material in photoelectricity electric appliance described in claim 1.
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| CN111961089A (en) * | 2020-09-18 | 2020-11-20 | 南京佳诺霖光电科技有限公司 | Organic metal complex and preparation method and application thereof |
| US11498937B2 (en) | 2019-05-09 | 2022-11-15 | Beijing Summer Sprout Technology Co., Ltd. | Organic luminescent material including 3-deuterium-substituted isoquinoline ligand |
| US11581498B2 (en) | 2019-05-09 | 2023-02-14 | Beijing Summer Sprout Technology Co., Ltd. | Organic luminescent material containing 6-silyl-substituted isoquinoline ligand |
| US11653559B2 (en) | 2019-05-09 | 2023-05-16 | Beijing Summer Sprout Technology Co., Ltd. | Metal complex containing a first ligand, a second ligand, and a third ligand |
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| CN109796500A (en) * | 2018-10-31 | 2019-05-24 | 冠能光电材料(深圳)有限责任公司 | It is a kind of miscellaneous with metal complex and its electroluminescent organic luminescent device application |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11498937B2 (en) | 2019-05-09 | 2022-11-15 | Beijing Summer Sprout Technology Co., Ltd. | Organic luminescent material including 3-deuterium-substituted isoquinoline ligand |
| US11581498B2 (en) | 2019-05-09 | 2023-02-14 | Beijing Summer Sprout Technology Co., Ltd. | Organic luminescent material containing 6-silyl-substituted isoquinoline ligand |
| US11653559B2 (en) | 2019-05-09 | 2023-05-16 | Beijing Summer Sprout Technology Co., Ltd. | Metal complex containing a first ligand, a second ligand, and a third ligand |
| CN111961089A (en) * | 2020-09-18 | 2020-11-20 | 南京佳诺霖光电科技有限公司 | Organic metal complex and preparation method and application thereof |
| CN111961089B (en) * | 2020-09-18 | 2023-10-31 | 南京佳诺霖光电科技有限公司 | Organometallic complex and preparation method and application thereof |
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