CN109400654A - 一种2-(苯磺酰基)苯乙酮衍生物为辅助配体的铱配合物 - Google Patents
一种2-(苯磺酰基)苯乙酮衍生物为辅助配体的铱配合物 Download PDFInfo
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- CN109400654A CN109400654A CN201711230061.7A CN201711230061A CN109400654A CN 109400654 A CN109400654 A CN 109400654A CN 201711230061 A CN201711230061 A CN 201711230061A CN 109400654 A CN109400654 A CN 109400654A
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- pyridine
- iridium
- ligand
- tfmppy
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- 239000003446 ligand Substances 0.000 title claims abstract description 54
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims description 13
- 229910052741 iridium Inorganic materials 0.000 title claims description 12
- DREVPGKOIZVPQV-UHFFFAOYSA-N 2-(benzenesulfonyl)-1-phenylethanone Chemical compound C=1C=CC=CC=1C(=O)CS(=O)(=O)C1=CC=CC=C1 DREVPGKOIZVPQV-UHFFFAOYSA-N 0.000 title abstract description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 32
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 16
- SSABEFIRGJISFH-UHFFFAOYSA-N 2-(2,4-difluorophenyl)pyridine Chemical compound FC1=CC(F)=CC=C1C1=CC=CC=N1 SSABEFIRGJISFH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000012360 testing method Methods 0.000 claims abstract description 7
- KGZSSIFFYUBVOX-UHFFFAOYSA-N 2-[4-(trifluoromethyl)phenyl]pyridine Chemical compound C1=CC(C(F)(F)F)=CC=C1C1=CC=CC=N1 KGZSSIFFYUBVOX-UHFFFAOYSA-N 0.000 claims abstract description 6
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 6
- 230000005284 excitation Effects 0.000 claims abstract description 5
- WWYNBPHOMYEYOQ-UHFFFAOYSA-N 2-[2-fluoro-4-(trifluoromethyl)phenyl]pyridine Chemical compound FC1=CC(C(F)(F)F)=CC=C1C1=CC=CC=N1 WWYNBPHOMYEYOQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 39
- 239000007787 solid Substances 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 11
- 239000000460 chlorine Substances 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003292 glue Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- 229960001866 silicon dioxide Drugs 0.000 claims description 5
- 235000002991 Coptis groenlandica Nutrition 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 3
- IMRWILPUOVGIMU-UHFFFAOYSA-N 2-bromopyridine Chemical compound BrC1=CC=CC=N1 IMRWILPUOVGIMU-UHFFFAOYSA-N 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 claims description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 2
- 238000010410 dusting Methods 0.000 claims description 2
- 238000005538 encapsulation Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000006210 lotion Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000012044 organic layer Substances 0.000 claims description 2
- 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 claims description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 2
- 239000011265 semifinished product Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- MJRFDVWKTFJAPF-UHFFFAOYSA-K trichloroiridium;hydrate Chemical compound O.Cl[Ir](Cl)Cl MJRFDVWKTFJAPF-UHFFFAOYSA-K 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 3
- 241000218202 Coptis Species 0.000 claims 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 235000019441 ethanol Nutrition 0.000 claims 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims 2
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 claims 1
- 239000010426 asphalt Substances 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 239000005416 organic matter Substances 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 4
- 125000001424 substituent group Chemical group 0.000 abstract description 3
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 108010007100 Pulmonary Surfactant-Associated Protein A Proteins 0.000 abstract 2
- 102100027773 Pulmonary surfactant-associated protein A2 Human genes 0.000 abstract 2
- 108010066082 tartrate-sensitive acid phosphatase Proteins 0.000 abstract 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 38
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- -1 2- benzothiophene pyridine Chemical compound 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 7
- 238000000295 emission spectrum Methods 0.000 description 7
- RFQXSRPFYWMUDV-UHFFFAOYSA-N 2-(4-methylphenyl)sulfonyl-1-phenylethanone Chemical compound C1=CC(C)=CC=C1S(=O)(=O)CC(=O)C1=CC=CC=C1 RFQXSRPFYWMUDV-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 238000006392 deoxygenation reaction Methods 0.000 description 6
- 238000004020 luminiscence type Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- UEMGWPRHOOEKTA-UHFFFAOYSA-N 1,3-difluorobenzene Chemical compound FC1=CC=CC(F)=C1 UEMGWPRHOOEKTA-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 2
- 244000247747 Coptis groenlandica Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000005424 photoluminescence Methods 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- YBRXHRWLEFCFEG-UHFFFAOYSA-N 1-(benzenesulfonyl)-4-methylbenzene Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C1=CC=CC=C1 YBRXHRWLEFCFEG-UHFFFAOYSA-N 0.000 description 1
- 150000005360 2-phenylpyridines Chemical class 0.000 description 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical class CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000040710 Chela Species 0.000 description 1
- 238000003775 Density Functional Theory Methods 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 101100264172 Oryza sativa subsp. japonica XIAO gene Proteins 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000002796 luminescence method Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- RHFUXPCCELGMFC-UHFFFAOYSA-N n-(6-cyano-3-hydroxy-2,2-dimethyl-3,4-dihydrochromen-4-yl)-n-phenylmethoxyacetamide Chemical compound OC1C(C)(C)OC2=CC=C(C#N)C=C2C1N(C(=O)C)OCC1=CC=CC=C1 RHFUXPCCELGMFC-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- ORFSSYGWXNGVFB-UHFFFAOYSA-N sodium 4-amino-6-[[4-[4-[(8-amino-1-hydroxy-5,7-disulfonaphthalen-2-yl)diazenyl]-3-methoxyphenyl]-2-methoxyphenyl]diazenyl]-5-hydroxynaphthalene-1,3-disulfonic acid Chemical compound COC1=C(C=CC(=C1)C2=CC(=C(C=C2)N=NC3=C(C4=C(C=C3)C(=CC(=C4N)S(=O)(=O)O)S(=O)(=O)O)O)OC)N=NC5=C(C6=C(C=C5)C(=CC(=C6N)S(=O)(=O)O)S(=O)(=O)O)O.[Na+] ORFSSYGWXNGVFB-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002211 ultraviolet spectrum 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 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
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
Abstract
一种铱(III)配合物,共有9个,其特征是:它们的主配体是2‑(2,4‑二氟苯基)吡啶(2‑(2,4‑difluorophenyl)pyridine,dfppy)、2‑(4‑三氟甲基苯基)吡啶(2‑(4‑trifluoromethylphenyl)pyridine,tfmppy)、2‑(2‑氟‑4‑三氟甲基苯基)吡啶(2‑(2‑fluoro‑4‑trifluoromethylphenyl)pyridine,ftfmppy),辅助配体为以2‑(苯磺酰基)苯乙酮衍生物,它们有如下结构式:其中R、R’和R1取代基的定义选自各配合物的六组之一。将配合物的粉末用于制作发光二极管,并测试了二极管的发光性能。二极管的最大发射波长在511‑543nm,发光效率在1.3‑5.6lm·W‑1,其中(tfmppy)2Ir(PSAP)、(ftfmppy)2Ir(PSAP)、(tfmppy)2Ir(TSAP)、(ftfmppy)2Ir(TSAP)四种配合物都具有较高的色纯度,因此可作为绿光组分用于白光LED的制作。本发明公开了配合物的结构、合成方法和有机光致发光器件的结构及制法。
Description
发明领域
本发明涉及铱(III)配合物,也涉及有机光致及电致发光器件。
背景技术
重金属配合物由于金属中心原子强的自旋耦合作用,使原本禁阻的三重态到单重态的辐射跃迁转为允许,从而可同时收获单重态和三重态激子,使得内量子效率可能达到100%。其中,IrIII配合物[参见:(a)DONG M K,KANG J W,PARK J W,et al.Adv.Mater.,2010,20(10):2003;(b)CHEN Z Q,BIAN Z Q,HUANG C H Adv.Mater., 2010,22(13):1534;(c)XIAO L,CHEN Z,QU B,et al.Adv.Mater.,2011,23(8):926;(d) RAI V K,NISHIURA M,TAKIMOTO M,et al.Inorg.Chem.,2012,51(2):822;(e)MONTI F,KESSLER F,DELGADO M,etal.Inorg.Chem.,2013,52(18):10292;(f)LEE S,KIM S O, SHIN H,etal.J.Am.Chem.Soc.,2013,135(38):14321;(g)KIM J B,HAN S H,YANG K, etal.Chem.Comm.,2015,51(1):58;(h)SAHIN C,GOREN A,VARLIKLI C.J.Organomet. Chem.,2014,772-773:68;(i)LIU X,ZHANG S,JIN Y M,et al.J.Organomet.Chem., 2015,785:11.]由于具有好的热稳定性,短的激发态寿命,高的发光效率,以及发光颜色易调节等优势[参见:LAMANSKY S,DJUROVICH P,MURPHY D,et al.J.Am. Chem.Soc.,2001,123:4304.],成为有机磷光材料的研究热点,是一类重要的有机电致和光致发光材料。
常见IrIII配合物从结构上看分为三类:Ir(C^N)3型、Ir(C^N)2(L^X)型以及 Ir(C^N)2(N^N)离子型配合物。虽然fac-Ir(C^N)3表现出好的光物理性质,但是合成条件苛刻,所以目前常常用带有辅助配体(LX)的结构为Ir(C^N)2(L^X)的铱配合物来代替,这里C^N为芳联氮杂芳环类主配体,如2-苯基吡啶(ppy),苯联异喹啉 (piq),2-苯并噻吩吡啶(Btp)等,L^X是双齿辅助配体例如:乙酰丙酮(acac),吡啶甲酸(pic)[参见:(a)YOU Y,PARK SY.J.Am.Chem.Soc.,2005,127(36):12438; (b)TAO Y,YANG C,QIN J.Cheminform,2011,42(35):2943.]等。根据密度泛函理论计算,分子的最高占轨道(HOMO)基本集中在中心金属铱上,而最低空轨道(LUMO) 通常位于环金属化的分子轨道上。虽然大多数辅助配体对最低激发态没有直接的贡献,它们可以通过控制金属Ir的d(t2g)轨道能级来控制HOMO的轨道能级,进而影响配合物的激发态。因此,IrIII配合物的光物理性质和载流子迁移率可以通过环金属化和辅助配体上的取代基进行调节。
基于上述原因并参考我们以往的工作[参见:(a)M.Y.Teng,S.Zhang,S.W. Jiang,et al.Dyes Pigment 2014,105,105.;(b)M.Y.Teng,S.Zhang,S.W.Jiang,et al.Appl.Phys.Lett.2012,100,073303.],本发明设计了一类6个新型的IrIII配合物,以强吸电子基团-F和-CF3取代的2-苯基吡啶衍生物:2-(2,4-二氟苯基)吡啶 (2-(2,4-difluorophenyl)pyridine,dfppy)、2-(4-三氟甲基苯基)吡啶 (2-(4-trifluoromethylphenyl)pyridine,tfmppy)、2-(2-氟-4-三氟甲基苯基)吡啶 (2-(2-fluoro-4-trifluoromethylphenyl)pyridine,ftfmppy)为主配体,以及以S=O和C=O 螯合位点的2-(苯磺酰基)苯乙酮(2-(phenylsulfonyl)acetophenone,PSAP)、2-(对甲苯磺酰基)苯乙酮(2-(p-toluenesulfonyl)acetophenone,TSAP)为辅助配体的六种新型IrIII配合物,并对它们的结构,电化学性能和光学性能进行了表征。在主配体中引入氟可以增加电荷迁移率有利于电荷注入和传输平衡,C-F键的振动频率较低,可以降低无辐射失活的速率,并且三氟甲基的体积较大,能减少分子堆积和抑制自身猝灭[参见:ZHU M,ZOU J,HU S,etal.J.Mater.Chem.,2011,22(2): 361.]。强极性的O=S键作为螯合配体的引入可以缩短配合物的激发态寿命,不仅可以避免T-T湮灭,还能并提高材料的电子迁移率,对降低器件的效率衰减具有很大的改善作用,同时强配位能力的羰基的引入,还可以提高配合物的稳定性,使器件具有较高的寿命。此外,与对称性辅助配体相比,非对称的2-(苯磺酰基) 苯乙酮衍生物会有更好的电子活性以及化学修饰性,更利于用来制备多种性能各异的IrIII配合物磷光材料。
发明内容
本发明的内容是提供6个含有2-(2,4-二氟苯基)吡啶、2-(4-三氟甲基苯基)吡啶、2-(2-氟-4-三氟甲基苯基)吡啶为主配体,2-(苯磺酰基)苯乙酮、2- (对甲苯磺酰基)苯乙酮为辅助配体的铱配合物和以其为发光中心的有机光致发光器件及其制备方法。
本发明的技术方案如下:
(1)一种铱(III)配合物,共有6个,其特征是:它们的主配体是2-(2,4-二氟苯基)吡啶、2-(4-三氟甲基苯基)吡啶、2-(2-氟-4-三氟甲基苯基)吡啶,辅助配体为2-(苯磺酰基)苯乙酮、2-(对甲苯磺酰基)苯乙酮,它们有如下结构式:
(2)一种制备上述配合物的辅助配体和铱(III)配合物的方法,包括下列步骤:
称取1mmol氯桥配合物和2.5mmol2-(苯磺酰基)苯乙酮衍生物(n:n=1:2.5) 混合于50mL三颈烧瓶,再加入2.5mmol无水碳酸钠,用N,N-二甲基甲酰胺使氯桥配合物完全溶解,氮气保护下加热回流24h。反应结束后减压蒸馏蒸除溶剂,用硅胶柱(二氯甲烷:甲醇)纯化,得到纯的产品。
本发明的铱配合物都是发光非常好的蓝光和绿色发光材料,其中以2-(2,4- 二氟苯基)吡啶为主配体的两个配合物(dfppy)2Ir(PSAP)与(dfppy)2Ir(TSAP)发蓝光,而其它四个配合物发绿光。它们可用于电致及光致发光器件中的发光中心,是电子传输性能和发光性能较好的发光层。
用1HNMR、13CNMR、高分辨质谱、红外、紫外和发射光谱表征并证实了这些铱配合物的结构,检测所用仪器为BrukerTENSOR27红外光谱仪、Bruker公司 500MHz核磁共振波谱仪、Bruker公司micrOTOF II质谱仪、上海美谱达UV-3100 紫外可见分光光度计、HitachiF-4600荧光分光光度计。
(3)配合物为发光中心的光致发光器件,其结构和用的材料的结构如下:
用固晶胶把InGaN芯片粘在支架上,在烘箱中150℃烘烤1小时,将胶水烤干,使芯片与支架粘连接在一起;将芯片的正负极分别与支架碗杯的正负极用金线相连接,使芯片与支架焊接在一起,形成导电回路;将道康宁AB胶与铱配合物固体粉末按1:1比例混合均匀后加入已焊接好金线的支架碗杯中,再次放入烘箱中在150℃恒温固化1小时;用胶水(环氧树脂)将已固晶、焊线和涂粉的半成品封装起来;将环氧树脂固化充分,同时将LED热老化;将整片的支架切割成单颗材料;对经过封装和老化试验的LED进行光电参数测试。其中裸管在5V电压,20mA电流下的效率为1.0lm·W-1。从效率来看,基于这些配合物的光致发光二极管的发光效率在1.3-5.6lm·W-1之间,色纯度在20.9-83.5%之间,材料性能处于较好水平。器件的优良性能表明这种配合物在有机光致发光器件的制备中具有应用价值。
附图说明
图1:六种配合物在除氧的二氯甲烷溶液中的发射光谱;
图2:六种配合物固体粉末状态时的发射光谱;
图3:六种配合物在除氧的二氯甲烷溶液中的UV-Vis吸收光谱;
图4:六种配合物制成LED器件时的发射光谱;
图5:六种配合物制成LED器件时的发光照片;
具体实施方式
本发明的配合物可按照如下方程式进行合成:
注:其中作为主配体的苯联吡啶衍生物配体是按照文献的方法制备[参见: GROOTD D,WAAL B F M D,REEK J N H,et al.J.Am.Chem.Soc.,2001,123(35):8453],作为辅助配体的2-(苯磺酰基)苯乙酮、2-(对甲苯磺酰基)苯乙酮从北京百灵威科技有限公司购得。目标配合物GIr-GIr12是我们用改进的合成方法制备的。红外光谱由Bruker TENSOR27红外光谱仪测定;核磁共振数据由Bruker公司500 MHz核磁共振波谱仪测定(TMS内标,CDCl3及d6-DMSO做溶剂);质谱数据由 Bruker公司micrOTOF II质谱仪测定;紫外吸收光谱数据由上海美谱达UV-3100 紫外可见分光光度计测得;荧光光谱数据由Hitachi F-4600荧光分光光度计测得。循环伏安图由上海华辰电化学工作站测得。其中Ag/Ag+作为参比电极,铂盘电极为工作电极,铂丝电极为辅助电极。用除氧的二氯甲烷作溶剂,二茂铁作为内标,扫描速度为100mV·S-1,扫描范围为-1.8至1.8V,0.1mol·L-1的四丁基六氟磷酸铵作为支持电解质。LED发光性能由虹谱HPS2000高精度快速光谱分析系统测得。
实施例一:主配体苯联吡啶的衍生物dfppy、tfmppy和ftfmppy的合成称量20mmol溴吡啶与24mmol苯硼酸(n:n=1:1.2)在250mL圆底烧瓶中混合,再加入0.6mmol四(三苯基膦)钯(Pd(PPh3)4)作为催化剂。用90mL甲苯, 30mL无水乙醇,30mL碳酸钠(2mol/L)(v:v:v=3:1:1)的混合溶液做溶剂[15]。在氮气保护下加热回流24h。反应结束后冷却至室温,过滤除去固体,用二氯甲烷将有机层萃取出来,重复三次,用饱和NaCl溶液洗剂萃取得到的有机物,将适量无水Na2SO4固体放入装有样品的锥形瓶中,干燥5h后蒸除溶剂,用硅胶柱 (PE:EA=20:1)提纯,得到纯的产品。
2-(2,4-二氟苯基)吡啶(2-(2,4-difluorophenyl)pyridine,dfppy):无色液体3.52g,产率92.1%。1H NMR(500MHz,CDCl3)δ8.74(dt,J=4.8,1.3Hz, 1H),8.03(td,J=8.8,6.7Hz,1H),7.81-7.73(m,2H),7.32-7.25(m,1H),7.09-7.00(m, 1H),6.94(ddd,J=11.3,8.8,2.5Hz,1H).
2-(4-三氟甲基苯基)吡啶((2-(4-trifluoromethylphenyl)pyridine,tfmppy):白色固体4.31g,产率:96.5%。1H NMR(500MHz,CDCl3)δ8.76(d,J=4.4 Hz,1H),8.14(d,J=8.1Hz,2H),7.82(m,2H),7.76(d,J=8.2Hz,2H),7.3 5-7.31(m,1H).
2-(2-氟-4-三氟甲基苯基)吡啶((2-(2-fluoro-4-trifluoromethylphenyl)pyridine, ftfmppy):无色液体4.39g,产率90.6%。1H NMR(500MHz,CDCl3)δ8.75(dt,J=4.6,1.4Hz,1H),8.07(td,J=8.5,6.9Hz,1H),7.44–7.35(m,3H),7.28(m,1H),6.90(m,1H).
实施例二:氯桥配合物的合成
将4mmol水合氯化铱与19mmol主配体(n:n=1:4.75)混合于25mL烧瓶中,加12mL乙二醇乙醚和水(v:v=3:1)混合,氮气保护下加热回流24h。反应结束后冷却,抽滤取固体,并用水和乙醇洗涤,得到黄色氯桥配合物,干燥,待用。
实施例三:目标配合物的合成
称取1mmol氯桥配合物和2.5mmol2-(苯磺酰基)苯乙酮衍生物(n:n=1:2.5) 混合于50mL三颈烧瓶,再加入2.5mmol无水碳酸钠,用N,N-二甲基甲酰胺使氯桥配合物完全溶解,氮气保护下加热回流24h。反应结束后减压蒸馏蒸除溶剂,用硅胶柱(二氯甲烷:甲醇)纯化,得到纯的产品。
[2-(2,4-二氟苯基)吡啶]铱[2-(苯磺酰基)苯乙酮](([2-(2,4-difluorophenyl)pyridine]2Ir[2-(phenylsulfonyl)acetophenone],(dfppy)2Ir(PSAP)):淡黄色固体0.30g,产率:18.2%。1H NMR(500MHz,DMSO)δ10.56(s,2H),8.00(t,J=7.8Hz,2H),7.75(d,J=8.7Hz,2H),7.58(t,J=6.5Hz,2H),7.03(t,J=7.2Hz,2H),6.78(t,J=7.7Hz, 4H),6.52(d,J=7.6Hz,4H),6.46–6.33(m,2H),5.76(s,1H),5.17(dd,J=8.3,2.0Hz, 2H).13CNMR(125MHz,DMSO)δ98.3,113.1,113.3,121.4,122.9,125.7,126.8, 127.5,128.1,128.8,139.2,149.2,154.2,158.9,160.9,162.7,163.9,165.9.IR(KBr v/cm-1)3108,3066,2920,2857,1605,1585,1487,1432,1404,1383,1300,1215, 1223,1160,1126,1112,1070,1028,987,854,785,756,695,583,527.MS(ESI-TOF) Calcd:832.10[M+].Found:m/z573.0550[M+-PSAP].
[2-(4-三氟甲基苯基)吡啶]铱[2-(苯磺酰基)苯乙酮] (([2-(4-trifluoromethyl-phenyl)pyridine]2Ir[2-(phenylsulfonyl)acetophenone], (tfmppy)2Ir(PSAP)):黄绿色固体0.39g,产率:21.9%。1H NMR(500MHz,DMSO)δ 10.54(d,J=4.3Hz,2H),8.02(t,J=7.6Hz,2H),7.85(d,J=8.0Hz,2H),7.64(t,J=6.5 Hz,2H),7.32(d,J=8.1Hz,2H),6.95(t,J=7.3Hz,2H),6.86(d,J=7.9Hz,2H),6.69(t, J=7.6Hz,4H),6.49(d,J=7.6Hz,4H),5.91(s,2H),5.76(s,1H).13C NMR(125MHz, DMSO)δ97.0,118.7,120.6,123.4,123.9,125.6,125.9,126.8,127.0,128.1,128.4, 138.7,147.8,153.9,166.1.IR(KBrv/cm-1)3122,3080,2920,2857,1620,1612,1571, 1494,1439,1383,1320,1279,1251,1167,1126,1070,1028,1014,994,889,826, 785,750,695,604,520.MS(ESI-TOF)Calcd:896.11[M+].Found:m/z637.0667 [M+-PSAP].
[2-(2-氟-4-三氟甲基苯基)吡啶]铱[2-(苯磺酰基)苯乙酮] ([2-(2-fluoro-4-trifluoromethylphenyl)pyridine]2Ir[2-(phenylsulfonyl)acetophenone], (ftfmppy)2Ir(PSAP)):黄绿色固体0.38g,产率:20.5%。1H NMR(500MHz,DMSO) δ10.77(s,1H),8.15-8.07(m,1H),7.91(d,J=8.6Hz,1H),7.74(t,J=6.7Hz,1H),6.98 (t,J=7.2Hz,1H),6.71(t,J=7.7Hz,3H),6.43(d,J=7.5Hz,2H),5.76(s,1H),5.71(s, 2H).13CNMR(125MHz,DMSO)δ107.0,122.3,122.8,124.1,124.3,125.6,125.9, 126.8,128.1,128.7,134.6,139.5,149.1,154.6,158.0,160.1,163.3.IR(KBr v/cm-1) 3101,3059,2927,2857,1647,1612,1571,1487,1404,1327,1288,1209,1153,1084, 1028,924,875,854,785,757,709,688,583,513.MS(ESI-TOF)Calcd:928.09[M+]. Found:m/z673.0497[M+-PSAP].
[2-(2,4-二氟苯基)吡啶]铱[2-(对甲苯磺酰基)苯乙酮](([2-(2,4-difluorophenyl) pyridine]2Ir[2-(p-toluenesulfonyl)acetophenone],(dfppy)2Ir(TSAP)):黄绿色固体 0.31g,产率:18.5%。1H NMR(500MHz,DMSO)δ10.51(s,2H),8.00(t,J=7.7Hz, 2H),7.75(d,J=8.5Hz,2H),7.55(d,J=6.3Hz,2H),6.56(d,J=7.9Hz,4H),6.39(d,J= 7.8Hz,7H)5.76(s,1H),5.15(dd,J=8.3,2.0Hz,2H),2.10(s,3H).13C NMR(DMSO,125MHz)δ24.8,100.0,102.0,117.3,117.4,126.4,129.1,129.6,130.8,131.4,133.8,141.9,500MHz,DMSO143.5,148.0,157.4,163.1,165.0,168.3.IR(KBr v/cm-1)3108, 3065,2924,2852,1612,1603,1571,1486,1434,1398,1251,1221,1163,1136,1119, 1038,972,862,811,752,708,642,590.MS(ESI-TOF)Calcd:846.12[M+].Found:m/z 573.0533[M+-TSAP].
[2-(4-三氟甲基苯基)吡啶]铱[2-(对甲苯磺酰基)苯乙酮] (([2-(4-trifluoromethylphenyl)pyridine]2Ir[2-(p-toluenesulfonyl)acetophenone],(tfmppy)2Ir(TSAP)):黄绿色固体0.41g,理论产量为1.79g,产率:22.8%。C39H27N2F6IrO3S1H NMR(500MHz,DMSO)δ10.46(d,J=4.5Hz,2H),8.00(t,J=8.0 Hz,2H),7.87(d,J=7.7Hz,2H),7.58(t,J=6.5Hz,2H),7.37(d,J=6.8Hz,2H,6.87(s, 2H),6.62-6.29(m,7H),5.87(s,2H),5.76(s,1H),5.33(t,J=4.8Hz,2H),2.5(s,3H). 13C NMR(125MHz,DMSO)δ24.7,119.0,119.6,122.8,123.1,123.8,124.9,125.4, 127.5,127.7,129.7,129.9,138.0,139.4,146.6,153.8,169.9.IR(KBr v/cm-1)3122, 3081,2920,2864,1647,1612,1571,1487,1439,1332,1258,1160.MS(ESI-TOF) Calcd:910.13[M+].Found:m/z637.0666[M+-TSAP].
[2-(2-氟-4-三氟甲基苯基)吡啶]铱[2-(对甲苯磺酰基)苯乙酮] (([2-(2-fluoro-4-tr-ifluoromethylphenyl)pyridine]2Ir[2-(p-toluenesulfonyl)acetophenone],(ftfmppy)2Ir(TSAP)):黄绿色固体0.37g,产率:19.8%1H NMR(500 MHz,DMSO)δ10.68(d,J=5.3Hz,1H),8.12(t,J=7.7Hz,1H),7.92(d,J=8.6Hz,1H), 7.73(t,J=6.6Hz,1H),6.77(d,J=12.5Hz,1H),6.50(d,J=8.0Hz,2H),6.30(d,J=8.0 Hz,2H),5.66(s,1H),4.14(q,J=5.2Hz,2H),2.12(s,3H).13C NMR(125MHz,DMSO) δ24.3,110.8,111.1,125.7,126.7,127.8,127.9,128.0,129.1,131.6,137.8,142.6, 143.9,148.1,157.9,160.3,162.1,164.2167.5,167.6.IR(KBr v/cm-1)3108,3066, 2920,2843,1612,1571,1494,1460,1411,1376,1293,1216,1181,1160,1035,1014, 931,882,861,806,792,764,709,639,583,513.MS(ESI-TOF)Calcd:946.11[M+]. Found:m/z673.0494[M+-TSAP].
实施例四:本发明的配合物的发射光谱和其他表征
配合物在二氯甲烷溶液中的发射波长显示(见附图1),PSAP和TSAP为辅助配体的铱配合物的最大发射波长位于479-495nm,当主配体相同时,有-CH3取代的TSAP为辅助配体与PSAP为辅助配体的配合物相比,(dfppy)2Ir(PSAP)与 (dfppy)2Ir(TSAP)、(tfmppy)2Ir(PSAP)与(tfmppy)2Ir(TSAP)、(tfmppy)2Ir(PSAP)与 (tfmppy)2Ir(TSAP)最大发射波长红移1-9nm。与Ir(dfppy)3相比配合物 (dfppy)2Ir(PSAP)和(dfppy)2Ir(TSAP)的发射波长分别蓝移23nm和22nm,与 Ir(tfmppy)3 [18]相比(tfmppy)2Ir(PSAP)和(tfmppy)2Ir(TSAP)的发射波长分别蓝移32nm 和23nm,与我们合成的Ir(ftfmppy)3相比(ftfmppy)2Ir(PSAP)和(ftfmppy)2Ir(TSAP) 的发射波长蓝移22nm和21nm,这样移动表明辅助配体PSAP和TSAP对配合物的发射波长具有调节作用。值得一提的是(dfppy)2Ir(PSAP)与(dfppy)2Ir(TSAP)均有两个发射峰,其中一个在450nm,另一个在480nm处。而同样以dfppy为主配体的FIrpic与FIr6,前者的最大发射峰在470nm和494nm,后者的最大发生峰在 460nm处。相较于这两种著名的蓝色磷光材料,我们合成得到的这两个材料的发射光谱更接近纯蓝光。我们推测这是由于磺酰基团更强的吸电子能力所致。从固体发射光谱中可以看出(见附图2),该类配合物的固体最大发射波长位于 479-503nm,与相同主配体的其他配合物相比以2-(苯磺酰基)苯乙酮衍生物为辅助配体的配合物的固体和溶液的最大发射波长的差别很小,相差最大的不到 10nm,这表明新合成的配合物在固态下的p-p堆积相互较小,辅助配体对配合物发光波长的调节作用。将配合物溶于二氯甲烷中(10-4M)、除氧,或直接以粉末状固体在HitachiF-4600光谱仪分别测定其溶液及固体发射光谱。
测试结果可以发现,六个配合物中除(dfppy)2Ir(PSAP)和(dfppy)2Ir(TSAP)在蓝光区域,其余化合物在蓝绿光区域。经过计算得到配合物的发光量子产率在 13.2-51.1%,当辅助配体相同时,主配体中有-CF3取代的配合物表现出较高的磷光量子产率,这表明了强吸电子基团的引入有利于提高配合物的发光效率。与 Ir(dfppy)3 [17]相比配合物(dfppy)2Ir(DSAP)和(dfppy)2Ir(TSAP)的量子效率相对较小,与 Ir(tfmppy)3 [18]相比(tfmppy)2Ir(DSAP)和(tfmppy)2Ir(TSAP)的量子效率分别提高46.2%和47.5%,与我们合成的Ir(ftfmppy)3相比((ftfmppy)2Ir(DSAP)和(ftfmppy)2Ir(TSAP) 的量子效率分别提高44.2%和44%,由此可得辅助配体DSAP和TSAP的引入很大程度提高了配合物的发光效率。
由紫外-可见光谱图可以看出(见附图3),六个配合物的吸收光谱形状相似,只有吸收峰的位置有微小的变化,这样的变化是由配体中的取代基的不同引起的。在二氯甲烷溶液中配合物都出现三个明显的吸收峰,其中波长小于360nm的吸收峰由主配体间单线态的跃迁引起,波长大于360nm的吸收峰由金属和配体间的电荷转移态跃迁(1MLCT,3MLCT)所致,这也表明了中心金属铱具有强的自旋轨道耦合,实现了单重态与多重态的混合,这对提高配合物的发光效率有着重要意义。将配合物溶于二氯甲烷中(10-4M)、除氧,在上海美谱达UV-3100紫外可见分光光度计测定其吸收光谱。
表1 以PSAP和TSAP为辅助配体的配合物的光物理性质
取二茂铁的真空HOMO能级为-4.5eV,通过比较测得的配合物与二茂铁的 C-V曲线氧化电位相对值得到各个配合物的HOMO能级,再结合其紫外-可见吸收光谱,计算得到分子的HOMO/LUMO能级,配合物的电化学性质测试结果如表2所示。由测试结果可以看出与其他配合物相比以dfppy为主配体的 (dfppy)2Ir(PSAP)和(dfppy)2Ir(TSAP)的LUMO能级较高,这是由于-F的吸电子能力比 -CF3的相对较弱,而配合物的LUMO能级由主配体提供,对配合物的LUMO能级降低得较少,致使分子能隙变宽,发射波长蓝移。当主配体相同时,不同的辅助配体的配合物他们的分子能级也存在差异。与(dfppy)2Ir(PSAP)相比, (dfppy)2Ir(TSAP)的能隙减小0.02eV,与(tfmppy)2Ir(PSAP)相比,(tfmppy)2Ir(TSAP) 的能隙减小0.09eV,与(ftfmppy)2Ir(PSAP)相比,(ftfmppy)2Ir(TSAP)的能隙减小0.15 eV,这样的微小变化可以解释为辅助配体TSAP中苯环对位上的-CH3引起的。这表明了辅助配体上有不同的取代基会影响配合物电化学性质。循环伏安图由上海华辰电化学工作站测得。其中Ag/Ag+作为参比电极,铂盘电极为工作电极,铂丝电极为辅助电极。用除氧的二氯甲烷作溶剂,二茂铁作为内标,扫描速度为100 mV·S-1,扫描范围为-1.8至1.8V,0.1mol·L-1的四丁基六氟磷酸铵作为支持电解质。
表2 以PSAP和TSAP为辅助配体的配合物的电化学性质
以目标配合物制备得到光致发光二极管的发射光谱(见附图4),和发光性能测试结果(见附图4)所示,目标配合物最大光致发光波长位于507-543nm 之间,配合物的最大发射波长主要受主配体影响,而辅助配体对配合物的最大发射波长影响较小。其中以dfppy为主配体的配合物最大发射波长较短属于蓝绿光发射,其它配合物主要在绿光区。同时,这些配合物的光致发光谱图与其固体发射光谱相似,这是由于制备发光二极管使用了纯的配合物固体粉末,没有对粉末进行掺杂的缘故。从效率来看,基于这些配合物的光致发光二极管的发光效率在 1.3-5.6lm·W-1之间,色纯度在20.9-83.5%之间。该结果与配合物的内量子产率相符合,发光颜色偏绿光的配合物制备的光致发光二极管发光效率较高。光致发光二极管发光性能由虹谱HPS2000高精度快速光谱分析系统测得。
表3 基于目标配合物的光致发光二极管的发光性能
Claims (3)
1.一种铱(III)配合物,共有6个,其特征是:它们的主配体是2-(2,4-二氟苯基)吡啶(2-(2,4-difluorophenyl)pyridine,dfppy)、2-(4-三氟甲基苯基)吡啶(2-(4-trifluoromethylphenyl)pyridine,tfmppy)、2-(2-氟-4-三氟甲基苯基)吡啶(2-(2-fluoro-4-trifluoromethylphenyl)pyridine,ftfmppy),辅助配体为以2-(苯磺酰基)苯乙酮衍生物,它们有如下结构式:
2.一种制备权利要求1所述的铱(III)配合物的方法,其特征是它包括下列步骤:
步骤1.主配体的合成
在无水无氧条件下,称量20mmol溴吡啶与24mmol苯硼酸(n:n=1:1.2)在250mL圆底烧瓶中混合,再加入0.6mmol四(三苯基膦)钯(Pd(PPh3)4)作为催化剂。用90mL甲苯,30mL无水乙醇,30mL碳酸钠(2mol/L)(v:v:v=3:1:1)的混合溶液做溶剂[15]。在氮气保护下加热回流24小时。反应结束后冷却至室温,过滤除去固体,用二氯甲烷将有机层萃取出来,重复三次,用饱和NaCl溶液洗剂萃取得到的有机物,将适量无水Na2SO4固体放入装有样品的锥形瓶中,干燥5小时后蒸除溶剂,用硅胶柱(PE:EA=20:1)提纯,得到纯的产品dfppy,tfmppy,ftfmppy。
步骤2.氯桥配合物的合成
将4mmol水合氯化铱与19mmol主配体(n:n=1:4.75)混合于25mL烧瓶中,加12mL乙二醇乙醚和水(v:v=3:1)混合,氮气保护下加热回流24小时。反应结束后冷却,抽滤取固体,并用水和乙醇洗涤,得到黄色氯桥配合物,干燥,待用。
步骤3.磷光配合物的合成
称取1mmol氯桥配合物和2.5mmol2-(苯磺酰基)苯乙酮衍生物(n:n=1:2.5)混合于50mL三颈烧瓶,再加入2.5mmol无水碳酸钠,用N,N-二甲基甲酰胺使氯桥配合物完全溶解,氮气保护下加热回流24小时。反应结束后减压蒸馏蒸除溶剂,用硅胶柱(二氯甲烷:甲醇)纯化,得到纯的产品。
3.权利要求1所述的铱(III)配合物在制备有机光致发光器件中的应用。
用固晶胶把InGaN芯片粘在支架上,在烘箱中150℃烘烤1小时,将胶水烤干,使芯片与支架粘连接在一起;将芯片的正负极分别与支架碗杯的正负极用金线相连接,使芯片与支架焊接在一起,形成导电回路;将道康宁AB胶与铱配合物固体粉末按一定比例混合均匀后加入已焊接好金线的支架碗杯中,再次放入烘箱中在150℃恒温固化1小时;用胶水(环氧树脂)将已固晶、焊线和涂粉的半成品封装起来;将环氧树脂固化充分,同时将LED热老化;将整片的支架切割成单颗材料;对经过封装和老化试验的LED进行光电参数测试。从效率来看,基于这些配合物的光致发光二极管的发光效率在1.3-5.6lm·W-1之间,色纯度在20.9-83.5%之间。
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