CN104478941B - 二苯并‑18‑冠‑6基环金属铱配合物及其应用 - Google Patents
二苯并‑18‑冠‑6基环金属铱配合物及其应用 Download PDFInfo
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- CN104478941B CN104478941B CN201410774219.7A CN201410774219A CN104478941B CN 104478941 B CN104478941 B CN 104478941B CN 201410774219 A CN201410774219 A CN 201410774219A CN 104478941 B CN104478941 B CN 104478941B
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- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 64
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000000463 material Substances 0.000 claims abstract description 61
- 229920000642 polymer Polymers 0.000 claims abstract description 40
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000002347 injection Methods 0.000 claims abstract description 10
- 239000007924 injection Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims description 53
- 239000002184 metal Substances 0.000 claims description 53
- 239000007787 solid Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000002019 doping agent Substances 0.000 claims description 16
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 claims description 15
- 150000005360 2-phenylpyridines Chemical class 0.000 claims description 12
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical group [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 230000005611 electricity Effects 0.000 claims description 9
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 claims description 9
- 239000012043 crude product Substances 0.000 claims description 8
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 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 description 4
- 230000009471 action Effects 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 238000005893 bromination reaction Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- JVZRCNQLWOELDU-UHFFFAOYSA-N gamma-Phenylpyridine Natural products C1=CC=CC=C1C1=CC=NC=C1 JVZRCNQLWOELDU-UHFFFAOYSA-N 0.000 claims description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- YMMGRPLNZPTZBS-UHFFFAOYSA-N 2,3-dihydrothieno[2,3-b][1,4]dioxine Chemical compound O1CCOC2=C1C=CS2 YMMGRPLNZPTZBS-UHFFFAOYSA-N 0.000 claims 1
- 241001614291 Anoplistes Species 0.000 claims 1
- 238000005842 biochemical reaction Methods 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 230000000171 quenching effect Effects 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 4
- 238000004220 aggregation Methods 0.000 abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 54
- 239000010410 layer Substances 0.000 description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 23
- 238000001228 spectrum Methods 0.000 description 22
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 7
- 239000000741 silica gel Substances 0.000 description 7
- 229910002027 silica gel Inorganic materials 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 230000005526 G1 to G0 transition Effects 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- -1 alkenyl carbazole Chemical compound 0.000 description 3
- 230000008033 biological extinction Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000012538 light obscuration Methods 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 150000003222 pyridines Chemical class 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- BMQDAIUNAGXSKR-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid Chemical compound CC(C)(O)C(C)(C)OB(O)O BMQDAIUNAGXSKR-UHFFFAOYSA-N 0.000 description 1
- VFMUXPQZKOKPOF-UHFFFAOYSA-N 2,3,7,8,12,13,17,18-octaethyl-21,23-dihydroporphyrin platinum Chemical compound [Pt].CCc1c(CC)c2cc3[nH]c(cc4nc(cc5[nH]c(cc1n2)c(CC)c5CC)c(CC)c4CC)c(CC)c3CC VFMUXPQZKOKPOF-UHFFFAOYSA-N 0.000 description 1
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical class O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 241001126918 Sycon Species 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process 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
- 238000007306 functionalization reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical class [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical class [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing 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
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/10—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing aromatic rings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
-
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
本发明公开了一类含二苯并‑18‑冠‑6基环金属铱配合物电致磷光材料,及其在聚合物电致发光器件中的应用。本发明的环金属铱配合物,由于二苯并‑18‑冠‑6具有很大的空间位阻,可以有效地降低分子间的聚集,避免三重态‑三重态(T‑T)的淬灭效应。同时,二苯并‑18‑冠‑6基团具有一定的电子传输能力,可以有效地调节铱配合物的电子注入和传输能力,从而极大地提高这类材料在电致发光器件中的发光性能。本发明的环金属铱配合物可以用作绿色发光材料,应用于有机电致发光器件,为获得高效有机电致磷光材料提供了新途径。
Description
技术领域
本发明涉及有机电致发光材料领域,特别涉及一类含二苯并-18-冠-6基环金属铱配合物电致发光材料,以及该配合物在聚合物电致发光器件中的应用。
背景技术
1998年,吉林大学马於光小组首次用锇的配合物[Os(CN)2(pph3)2BPy]掺杂到聚乙烯基咔唑(PVK)中制备了磷光电致发光器件,但是因为其效率很低,未能引起关注(Synth.Met., 1998, 94, 245)。几乎同时,美国普林斯顿大学的Forrest小组和南加州大学的Thompson小组也报道了八乙基卟啉铂(PtOEP)掺杂到小分子主体材料八羟基喹啉铝(Alq3)中,获得了高效率的磷光器件,其内量子效率和外量子效率分别为23%和4%,从而开辟了一个新的有机电致发光器件研究领域(Nature, 1998, 395, 151)。电致磷光的发光机理不同于电致荧光的发光机理,前者可以同时利用三重态和单重态激子发光,内量子效率理论上可达100%,突破了荧光材料的最大内量子效率25%的理论限制(Adv. Mater., 2002, 14,701;Phys. Rev. B, 1999, 60, 14422;Chem. Soc. Rev., 2012, 41: 4797)。尤其是重金属Ir 具有很强的自旋-轨道耦合,使原本禁阻的三线态跃迁变为允许,重金属和配体之间强烈的相互作用使含有过渡金属的配合物能够使单重态和三重态得到混杂,破坏了三重态激子的对称性,衰减加快,减少瘁灭;与此同时,单重态也带有某些三重态的性质,衰减减慢,使单重态到三重态的系间窜越效率提高,从而获得高效的电致磷光(J. Am. Chem.Soc., 2001, 123, 4304;Adv. Mater., 2003, 15, 224;Chem. Mater., 2013, 25,1013)。
聚合物电致发光器件与小分子电致发光器件相比有以下优点:(1)可通过旋涂和喷墨打印制备,制作成本低;(2)易实现大面积显示(Appl. Phys. Lett., 2002, 80,2045;Nat. Commun., 2013, 4, 1971;J. Mater. Chem. C, 2014, 2, 3270)。将电致磷光材料掺杂到聚合物主体材料里面形成电致发光器件中的发光层,被认为是获得高效、可溶液加工的电致磷光器件最有效的途径之一。因此,开发发光效率高、稳定性好的聚合物电致发光器件具有十分重要的现实意义。解决这一问题最有效的方法就是开发发光性能优良的电致磷光材料及与之匹配的聚合物主体材料。
聚合物电致磷光器件存在的主要问题是:(1)有机小分子磷光材料(客体)掺杂到聚合物主体材料中,在电场作用下,容易发生磷光分子的聚集,产生相分离,导致浓度淬灭,降低器件的发光效率与寿命;(2)在高电流密度下,电致磷光器件的效率存在迅速降低的现象。为了得到高效、稳定的铱配合物磷光材料,通常将空间位阻较大的载流子基团引入到铱配合物的环金属配合物或辅助配合物上(Chem. Mater., 2011, 23, 326;Adv. Mater.,2008, 20, 774)。
为此,我们发明了一类二苯并-18-冠-6基环金属铱配合物。本发明将空间位阻极大的电子传输基团二苯并-18-冠-6引入到环金属铱配合物的主配体上,二苯并-18-冠-6的引入可以有效地抑制环金属铱配合在聚合物中的相分离和浓度淬灭,提高聚合物电致磷光器件的发光效率。
发明内容
本发明的目的是提供一类二苯并-18-冠-6基环金属铱配合物以及基于这类材料的高效聚合物电致发光器件。
本发明的二苯并-18-冠-6基环金属铱配合物磷光材料的特征是在环金属铱配合物的环金属配体苯基吡啶的苯环上引入二苯并-18-冠-6基团。这类二苯并-18-冠-6基环金属铱配合物可以是下面分子结构式中的一种:
其中R, R’为氢原子或者二苯并-18-冠-6 ,Z为二苯并-18-冠-6。
上述环金属铱配合物磷光材料包括下面任何衍生物:
环金属铱配合物(ppy)2Ir(ppycr):R为氢原子,R’为二苯并-18-冠-6;
环金属铱配合物(ppy)Ir(ppycr)2:R为二苯并-18-冠-6,R’为氢原子;
环金属铱配合物Ir(ppycr)3:R为二苯并-18-冠-6,R’为二苯并-18-冠-6;
本发明的环金属铱配合物的具体制备方法如下:
在氮气保护下,将溴化fac-三(2-苯基吡啶)铱(Ⅲ)与二苯并-18-冠-6硼酸酯在四(三苯基磷)钯为催化剂作用下,加热至90 ℃,反应24 h。冷却至室温,萃取,无水MgSO4干燥。粗产品用色谱柱分离纯化,得到黄色固体粉末。
本发明的应用在于:二苯并-18-冠-6基环金属铱配合物作为电致磷光材料可以用于制作电致发光器件,尤其是聚合物电致发光器件中。在环金属配合物中,一方面,二苯并-18-冠-6结构具有很大的空间位阻,可以有效地降低分子间的聚集,避免三重态-三重态(T-T)的淬灭效应;另一方面,二苯并-18-冠-6结构具有一定的电子传输能力,可以很好地调节铱配合物的电子注入和传输能力。因此,这类电致磷光材料用于聚合物电致磷光器件的发光层的掺杂剂,可以改善器件的发光性能,获得高效率的聚合物绿光器件。
聚合物绿光器件包括氧化铟锡导电玻璃衬底层(ITO),空穴注入层,发光层,阴极注入层和阴极层。空穴注入层为聚(3,4-亚乙二氧基噻吩)-聚(苯乙烯磺酸)(PEDOT/PSS)涂层,发光层为客体材料和主体材料的共混涂层,其中客体材料为本发明的含二苯并-18-冠-6基环金属铱配合物,其掺杂浓度为1wt%~4 wt %。主体材料为聚乙烯咔唑(PVK)和2-(4-联苯基)-5-(4-叔丁基)苯基-1,3,4-噁二唑(PBD),其中PVK与PBD的重量比例为70%:30%。阴极注入层为氟化铯涂层,阴极为金属铝。
本发明的二苯并-18-冠-6基环金属铱配合物电致磷光材料与已公开的功能化环金属铱配合物电致磷光材料相比,具有以下特点:(1)设计的基于二苯并-18-冠-6基环金属铱配合物,由于具有很大的空间位阻,可以有效地降低分子间的聚集,避免三重态-三重态(T-T)的淬灭效应;(2)二苯并-18-冠-6基团具有一定的电子传输能力,可以有效地调节铱配合物的电子注入和传输能力,从而极大地提高这类材料在电致发光器件中的发光性能,实现高效率发光。
附图说明
图1为环金属铱配合物(ppy)2Ir(ppycr)固体膜的紫外-可见光(UV)吸光光谱图。
图2为环金属铱配合物(ppy)2Ir(ppycr)固体膜的荧光发射光谱图。
图3为环金属铱配合物(ppy)Ir(ppycr)2固体膜的紫外-可见光(UV)吸光光谱图。
图4为环金属铱配合物(ppy)Ir(ppycr)2固体膜的荧光发射光谱图。
图5为环金属铱配合物Ir(ppycr)3固体膜的紫外-可见光(UV)吸光光谱图。
图6为环金属铱配合物Ir(ppycr)3固体膜的荧光发射光谱图。
图7为环金属铱配合物(ppy)2Ir(ppycr)的热分解(TG)曲线。
图8为环金属铱配合物(ppy)Ir(ppycr)2的热分解(TG)曲线。
图9为环金属铱配合物Ir(ppycr)3的热分解(TG)曲线。
图10为1%环金属铱配合物(ppy)2Ir(ppycr)-PVK-PBD聚合物器件的电致发光光谱图。
图11为2%环金属铱配合物(ppy)2Ir(ppycr)-PVK-PBD聚合物器件的电致发光光谱图。
图12为4%环金属铱配合物(ppy)2Ir(ppycr)-PVK-PBD聚合物器件的电致发光光谱图。
图13为1%环金属铱配合物(ppy)Ir(ppycr)2-PVK-PBD聚合物器件的电致发光光谱图。
图14为2%环金属铱配合物(ppy)Ir(ppycr)2-PVK-PBD聚合物器件的电致发光光谱图。
图15为4%环金属铱配合物(ppy)Ir(ppycr)2-PVK-PBD聚合物器件的电致发光光谱图。
图16为1%环金属铱配合物Ir(ppycr)3-PVK-PBD聚合物器件的电致发光光谱图。
图17为2%环金属铱配合物Ir(ppycr)3-PVK-PBD聚合物器件的电致发光光谱图。
图18为4%环金属铱配合物Ir(ppycr)3-PVK-PBD聚合物器件的电致发光光谱图。
图19为1%环金属铱配合物(ppy)2Ir(ppycr)-PVK-PBD聚合物器件的流明效率与电流密度曲线图。
图20为2%环金属铱配合物(ppy)2Ir(ppycr)-PVK-PBD聚合物器件的流明效率与电流密度曲线图。
图21为4%环金属铱配合物(ppy)2Ir(ppycr)-PVK-PBD聚合物器件的流明效率与电流密度曲线图。
图22为1%环金属铱配合物(ppy)Ir(ppycr)2-PVK-PBD聚合物器件的流明效率与电流密度曲线图。
图23为2%环金属铱配合物(ppy)Ir(ppycr)2-PVK-PBD聚合物器件的流明效率与电流密度曲线图。
图24为4%环金属铱配合物(ppy)Ir(ppycr)2-PVK-PBD聚合物器件的流明效率与电流密度曲线图。
图25为1%环金属铱配合物Ir(ppycr)3-PVK-PBD聚合物器件的流明效率与电流密度曲线图。
图26为2%环金属铱配合物Ir(ppycr)3-PVK-PBD聚合物器件的流明效率与电流密度曲线图。
图27为4%环金属铱配合物Ir(ppycr)3-PVK-PBD聚合物器件的流明效率与电流密度曲线图。
具体实施方式
下面通过具体实施例对本发明作进一步的说明,其目的在于帮助更好的理解本发明的内容,具体包括材料合成、表征与器件制备,但这些具体实施方案不以任何方式限制本发明的保护范围。
实施例1
二苯并-18-冠-6硼酸酯的合成
(1)二苯并-18-冠-6的合成
将22 g(0.2 mol)邻苯二酚,30.03 g(0.21 mol)1-氯-2-(2-氯乙氧基)乙烷和110.4 g碳酸钾置于500 mL的圆底烧瓶中,加入350 mL N,N-二甲基甲酰胺(DMF)溶液,反应加热回流,搅拌反应24 h。冷却至室温,倒入大量水中,二氯甲烷萃取3次。水洗有机层,无水硫酸镁干燥,蒸除有机溶剂。柱层析提纯(硅胶为固定相,石油醚:乙酸乙酯=4:1为洗脱剂),得到白色固体7.57 g,产率21%。1H NMR (300 MHz, CDCl3, TMS) δ (ppm): 6.88 (s, 8H),4.16~4.13 (t, J = 4.36 Hz, 8H), 3.93~3.90 (t, J = 4.35 Hz, 8H).
(2)4-溴-二苯并-18-冠-6的合成
将3.6 g(10 mmol)二苯并-18-冠-6,1.03 g溴化钠和100 mL无水乙腈加入到250mL的圆底烧瓶中,氩气氛围中,冰浴条件下滴加溶解有7.13 g(13.0 mmol)硝酸铈铵的60mL乙腈溶液,1 h滴加完毕。然后升温至室温,继续反应24 h。倒入大量去离子水中,二氯加完萃取,并用水洗,无水MgSO4干燥,用旋转蒸发仪蒸除挥发性溶剂。粗产品用硅胶色谱柱分离纯化(石油醚:乙酸乙酯=4:1为展开剂),得到白色固体3.42 g,产率78%。1H NMR (300MHz, CDCl3, TMS) δ (ppm): 6.98~6.96 (m, 2H), 6.88 (s, 8H), 6.73~6.70 (d, J =8.43 Hz, 1H), 4.16~4.13 (m, 8H), 3.93~3.90 (m, 8H).
(3)二苯并-18-冠-6硼酸酯的合成
将8.79 g(20 mmol)4-溴-二苯并-18-冠-6、7.62 g(30 mmol)双联频那醇硼酸酯、14.70 g醋酸钾和160 mL 1,4-二氧六环加入到250 mL的两口烧瓶中,氩气保护下加入516mg(0.6 mmol)1’1-双(二苯基膦)(二茂铁)二氯化钯。加热回流,反应36 h。将反应液倒入去离子水中,二氯甲烷萃取3次,合并有几层,并水洗,无水MgSO4干燥,用旋转蒸发仪蒸除挥发性溶剂。粗产品用硅胶色谱柱分离纯化(石油醚:乙酸乙酯=2:1为洗脱剂),得到6.81 g无色粘稠固体,产率70 %。1H NMR (300 MHz, CDCl3, TMS) δ (ppm): 7.39 (dd, J = 1.3, 7.9Hz, 1H), 7.28 (d, J = 1.4 Hz, 1H), 6.90~6.83 (m, 5H), 4.20~4.12 (m, 8H), 3.92~3.89 (m, 8H), 1.32 (s, 12H).
实施例2
溴化fac-三(2-苯基吡啶)合铱的合成
(1)fac-三(2-苯基吡啶)合铱(Ⅲ) [fac-Ir(ppy)3]的合成
将1.5 g(10 mmol)2-苯基吡啶,乙二醇单***21 mL和水7 mL加入到一个50 mL三口瓶中,氩气保护下迅速加入1.4 g(4.0 mmol)IrCl3•3H2O,100 ℃恒温反应20 h。冷却,有黄色固体产生,抽滤,并先后用水和少许无水乙醇洗涤,真空干燥,得黄色粉末2.42 g。产品未进行进一步分离纯化直接用于下一步反应。
在50 mL 的三口瓶中,依次加入上一步反应产物0.8 g(0.75 mmoL)、2-苯基吡啶0.62 g(4.0 mmoL)、碳酸钠424 mg (4.0 mmoL)、0.6 mL乙酰丙酮,0.6 mL三乙胺和乙二醇30 mL。氩气保护下,升温至220 ℃回流反应24 h,冷却至室温后,倒入40 mL去离子水中,二氯甲烷(30 mL×3)萃取,有机层用蒸馏水洗(30 mL×3),无水MgSO4干燥过夜,旋转蒸发仪蒸除挥发性溶剂。粗产品用色谱柱分离纯化(硅胶为固定相,石油醚/二氯甲烷=3/1为洗脱剂)。真空干燥得黄色固体fac-Ir(ppy)3(450 mg),产率46%。1H NMR (300 MHz, CDCl3,TMS) δ (ppm): 8.14~8.11 (d, J = 8.19 Hz, 1H), 7.81~7.73 (m, 2H), 7.49~7.46(d, J = 6.36 Hz, 1H), 7.14~7.10 (m, 1H), 6.82~6.77 (m, 1H), 6.71~6.62 (m,2H).
(2)二(2-苯基吡啶)-(2-(5-溴苯基)吡啶)合铱(Ⅲ) [(ppy)2Ir(ppyBr)]的合成
在一个500 mL三口瓶中加入0.5 g(0.76 mmol)fac-三(2-苯基吡啶)铱(Ⅲ)[fac-Ir(ppy)3]和300 mL二氯甲烷,缓慢滴加溶有135 mg(0.76 mmol)NBS的二氯甲烷溶液(30mL),室温下,避光反应过夜。停止反应,倒入蒸馏水中,用大量二氯甲烷萃取,无水硫酸镁干燥。蒸除大部分二氯甲烷,加入少许乙醇溶剂,有黄色固体析出,抽滤,用乙醇洗滤饼。真空干燥,得到黄色固体(ppy)2Ir(ppyBr)(0.32 g),产率57%。1H NMR (300 MHz, CDCl3, TMS)δ (ppm): 8.26~8.23 (d, J = 7.77 Hz, 1H), 8.16~8.14 (d, J = 8.1 Hz, 2H), 7.95(s, 1H), 7.82~7.75 (m, 5H), 7.49~7.36 (m, 3H), 7.19~7.14 (m, 3H), 6.89~6.80(m, 3H), 6.74~6.70 (t, 2H), 6.62~6.53 (m, 3H).
(3)(2-苯基吡啶)-二(2-(5-溴苯基)吡啶)合铱(Ⅲ) [(ppy)Ir(ppyBr)2]的合成
在一个500 mL三口瓶中加入0.45 g(0.688 mmol)fac-三(2-苯基吡啶)铱(Ⅲ)[fac-Ir(ppy)3]和300 mL二氯甲烷,缓慢滴加溶有247 mg(1.39 mmol)NBS的二氯甲烷溶液(30 mL),室温下,避光反应过夜。停止反应,倒入蒸馏水中,用大量二氯甲烷萃取,无水硫酸镁干燥。蒸除大部分二氯甲烷(剩50 mL),加入250 mL乙醇溶剂,有黄色固体析出,抽滤,用乙醇洗滤饼。真空干燥,得到黄色固体(ppy)Ir(ppyBr)2(0.35 g),产率63%。1H NMR (300MHz, CDCl3, TMS) δ (ppm): 8.26~8.23 (d, J = 7.77 Hz, 2H), 8.16~8.14 (d, J =8.1 Hz, 1H), 7.95 (s, 2H), 7.82~7.75 (m, 4H), 7.49~7.36 (m, 3H), 7.19~7.14(m, 3H), 6.89~6.80 (m, 3H), 6.74~6.70 (t, 1H), 6.62~6.53 (m, 3H).
(4)三(2-(5-溴苯基)吡啶)合铱(Ⅲ) [Ir(ppyBr)3]的合成
在一个500 mL三口瓶中加入0.5 g(0.76 mmol)fac-三(2-苯基吡啶)铱(Ⅲ)[fac-Ir(ppy)3]和300 mL二氯甲烷,缓慢滴加溶有540 mg(3.04 mmol)NBS的二氯甲烷溶液(30mL),室温下,避光反应过夜。停止反应,倒入蒸馏水中,用大量二氯甲烷萃取,无水硫酸镁干燥。蒸除大部分二氯甲烷(剩50 mL),加入250 mL乙醇溶剂,有黄色固体析出,抽滤,用乙醇洗滤饼。真空干燥,得到黄色固体Ir(ppyBr)3(0.37 g),产率69%。1H NMR (300 MHz, CDCl3,TMS) δ (ppm): 8.25~8.22 (d, J = 8.19 Hz, 3H), 7.96 (s, 3H), 7.87~7.82 (t,3H), 7.48~7.46 (d, J = 4.38 Hz, 3H), 7.22~7.18 (t, 3H), 6.90~6.87 (d, J = 8.4Hz, 3H), 6.52~6.50 (d, J = 8.13 Hz, 3H).
实施例7
二苯并-18-冠-6基团化fac-三(2-苯基吡啶)合铱的合成
(1)二(2-苯基吡啶)-(2-(5-(18-冠-6-基)苯基)吡啶)合铱(Ⅲ) [(ppy)2Ir(ppycr)]的合成
将368 mg(0.5 mmol)二(2-苯基吡啶)-(2-(5-溴苯基)吡啶)铱(Ⅲ)[(ppy)2Ir(ppyBr)],292 mg(0.6 mmol)二苯并-18-冠-6硼酸酯和20 mL 2.0 M碳酸钾水溶液,以及40mL甲苯和20 mL乙醇加入到150 mL两口瓶中,氩气保护下加入30 mg(0.025 mmol)四(三苯基磷)钯,加热至90 ℃,反应24 h。冷却至室温,反应液倒入去离子水中,二氯甲烷萃取3次,合并有机相,并用水洗。无水MgSO4干燥过夜,旋转蒸发仪蒸除挥发性溶剂。粗产品用色谱柱分离纯化(硅胶为固定相,乙酸乙酯/二氯甲烷=1/1为洗脱剂)。真空干燥得到324 mg黄色固体,产率64%。1H NMR (300 MHz, CDCl3, TMS) δ (ppm): 7.99~7.94 (d, J = 8.19 Hz,1H), 7.91~7.88 (d, J = 8.19 Hz, 2H), 7.82 (s, 1H), 7.64~7.55 (m, 9H), 7.15(s, 5H), 7.05~7.02 (m, 1H), 6.93~6.84 (m, 18H), 4.18~4.12 (m, 8H), 3.91~3.90(m,8H).13C NMR (DMSO, 75 MHz) δ (ppm): 166.73, 160.81, 160.20, 148.95, 147.51,147.24, 147.02, 144.23, 144.22, 143.65, 137.36, 137.12, 136.17, 136.05,132.42, 132.36, 129.97, 128.63, 123.92, 122.14, 122.01, 121.42, 119.95,119.17, 118.90, 114.43, 114.16, 112.70, 69.95, 69.52, 69.48, 69.36.
(ppy)2Ir(ppycr)固体膜的紫外-可见光吸光光谱见图1,固体膜的荧光发射光谱见图2,热分解曲线见图7.
(2)(2-苯基吡啶)-二(2-(5-(18-冠-6-基)苯基)吡啶)合铱(Ⅲ) [(ppy)Ir(ppycr)2]的合成
将260 mg(0.32 mmol)(2-苯基吡啶)-二(2-(5-溴苯基)吡啶)铱(Ⅲ)[(ppy)Ir(ppyBr)2],467 mg(0.96 mmol)二苯并-18-冠-6硼酸酯和15 mL 2.0 M碳酸钾水溶液,以及40 mL甲苯和15 mL乙醇加入到150 mL两口瓶中,氩气保护下加入58.3 mg(0.05 mmol)四(三苯基磷)钯,加热至90 ℃,反应36 h。冷却至室温,反应液倒入去离子水中,二氯甲烷萃取3次,合并有机相,并用水洗。无水MgSO4干燥过夜,旋转蒸发仪蒸除挥发性溶剂。粗产品用色谱柱分离纯化(硅胶为固定相,乙酸乙酯/二氯甲烷=2/1为洗脱剂)。真空干燥得到268 mg黄色固体,产率61%。1H NMR (300 MHz, CDCl3, TMS) δ (ppm): 7.98~7.95 (d, J = 8.19Hz, 2H), 7.90~7.87 (d, J = 8.19 Hz, 1H), 7.80 (s, 2H), 7.63~7.54 (m, 7H),7.13 (s, 4H), 7.06~7.03 (m, 2H), 6.94~6.85 (m, 18H), 4.19~4.13 (m, 16H), 3.92~3.91 (m,16H).13C NMR (DMSO, 75 MHz) δ (ppm): 166.72, 160.80, 160.22, 148.97,147.50, 147.20, 147.05, 144.26, 144.21, 143.66, 137.38, 137.11, 136.18,136.07, 132.40, 132.36, 129.95, 128.64, 123.95, 122.15, 122.02, 121.44,119.93, 119.19, 118.91, 114.44, 114.18, 112.72, 69.93, 69.54, 69.46, 69.38.
(ppy)Ir(ppycr)2固体膜的紫外-可见光吸光光谱见图3,固体膜的荧光发射光谱见图4,热分解曲线见图8.
(3)三(2-(5-(18-冠-6-基)苯基)吡啶)合铱(Ⅲ) [Ir(ppycr)3]的合成
将178 mg(0.2 mmol)三(2-(5-溴苯基)吡啶)铱(Ⅲ)[Ir(ppyBr)3],389 mg(0.8mmol)二苯并-18-冠-6硼酸酯和15 mL 2.0 M碳酸钾水溶液,以及40 mL甲苯和15 mL乙醇加入到150 mL两口瓶中,氩气保护下加入47 mg(0.04 mmol)四(三苯基磷)钯,加热至90 ℃,反应10 h。有固体不溶解,用注射器注入10 mL除氧的THF,继续反应36 h。冷却至室温,反应液倒入去离子水中,二氯甲烷萃取3次,合并有机相,并用水洗。无水MgSO4干燥过夜,旋转蒸发仪蒸除挥发性溶剂。粗产品用色谱柱分离纯化(硅胶为固定相,甲醇/二氯甲烷=1/10为洗脱剂)。真空干燥得到232 mg黄色固体,产率67%。1H NMR (300 MHz, CDCl3, TMS) δ (ppm):7.99~7.96 (d, J = 8.19 Hz, 3H), 7.84 (s, 3H), 7.65~7.60 (t, J = 7.74 Hz, 3H),7.56-7.55 (d, J = 4.62 Hz, 3H), 7.12~7.03 (t, J = 13.71 Hz, 9H), 6.84 (s,21H), 4.20~4.08 (m, 24H), 3.92 (s,24H).13C NMR (DMSO, 75 MHz) δ (ppm): 166.52,148.95, 147.51, 147.19, 144.22, 137.36, 136.13, 132.49, 128.69, 122.20,121.42, 119.19, 118.98, 114.36, 114.12, 112.69, 69.93, 69.55, 69.47, 69.39.
Ir(ppycr)3固体膜的紫外-可见光吸光光谱见图5,固体膜的荧光发射光谱见图6,热分解曲线见图9.
实施例8
以环金属铱配合物为掺杂材料的聚合物电致发光器件的发光性能
基于二苯并-18-冠-6基环金属铱配合物的聚合物电致发光器件的器件结构包括:氧化铟锡(ITO)导电玻璃,空穴注入层(PEDOT:PSS),发光层,阴极注入层(CsF),阴极层。发光层由客体掺杂材料和主体材料构成,其中客体材料为环金属铱配合物,主体材料为PVK和PBD组成,客体材料在主体材料中的掺杂质量百分比为1%~4%,主体材料PVK与PBD的质量比为70:30.
聚合物电致发光器件的制备:首先在ITO玻璃上旋涂一层厚度约为40 nm PEDOT:PSS作为空穴注入层,在80 ℃下真空干燥8 h。然后旋涂一层厚度为90 nm的发光层。再在发光层上蒸镀一层厚度为1.5 nm的氟化铯(CsF),最后蒸镀一层厚度为100 nm的高功函金属铝(Al)作为器件的阴极。制作得到的聚合物电致发光器件结构为:ITO/PEDOT:PSS/Emitting Layer/CsF/Al。阴极面积定义为器件有效活性面积,为0.15 cm2。用表面轮廓仪来测定各旋涂层的厚度。用Sycon Instrument公司生产的厚度/速度仪(Model STM-100)来控制氟化铯层和金属铝层的沉积速度和厚度。用Keithley 236 Source Measure Unit来测定器件的电流-电压(J-V)特性。用Oriel公司的Instaspec4CCD光栅光谱仪测定器件的电致发光光谱。用校正的硅光电二极管来测定器件的发光亮度,用积分球(IS080, Labsphere)来校准器件的外量子效率,器件用紫外固化环氧树脂和薄层玻璃封装。
以实施例7化合物(ppy)2Ir(ppycr)为掺杂材料,掺杂材料在主体材料中的质量百分比为1%,2%和4%,制作(ppy)2Ir(ppycr)-PVK-PBD电致发光器件。
当掺杂材料的质量分数为1%时:(ppy)2Ir(ppycr)-PVK-PBD电致发光器件的电致发光光谱如图10所示,电流效率与电流密度曲线如图19所示。器件的最大发射光波长为520nm,最大发光亮度为5393 cd/m2,在电流密度为1.11mA/cm2时,最大流明效率为27.0 cd/A.当掺杂材料的质量分数为2%时:(ppy)2Ir(ppycr)-PVK-PBD电致发光器件的电致发光光谱如图11所示,电流效率与电流密度曲线如图20所示。器件的最大发射光波长为520 nm,最大发光亮度为7115 cd/m2,在电流密度为3.15mA/cm2时,最大流明效率为23.6 cd/A.当掺杂材料的质量分数为4%时:(ppy)2Ir(ppycr)-PVK-PBD电致发光器件的电致发光光谱如图12所示,电流效率与电流密度曲线如图21所示。器件的最大发射光波长为520 nm,最大发光亮度为6962 cd/m2,在电流密度为9.3 mA/cm2时,最大流明效率为20.1 cd/A
以实施例7化合物(ppy)Ir(ppycr)2为掺杂材料,掺杂材料在主体材料中的质量百分比为1%,2%和4%,制作(ppy)Ir(ppycr)2-PVK-PBD电致发光器件。
(ppy)Ir(ppycr)2-PVK-PBD电致发光器件的电致发光光谱如图13所示,电流效率与电流密度曲线如图22所示。器件的最大发射光波长为522 nm,最大发光亮度为4439 cd/m2,在电流密度为2.6 mA/cm2时,最大流明效率为25.8 cd/A.当掺杂材料的质量分数为2%时:(ppy)Ir(ppycr)2-PVK-PBD电致发光器件的电致发光光谱如图14所示,电流效率与电流密度曲线如图23所示。器件的最大发射光波长为522 nm,最大发光亮度为4338 cd/m2,在电流密度为1.9 mA/cm2时,最大流明效率为21.69 cd/A.当掺杂材料的质量分数为4%时:(ppy)Ir(ppycr)2-PVK-PBD电致发光器件的电致发光光谱如图15所示,电流效率与电流密度曲线如图24所示。器件的最大发射光波长为522 nm,最大发光亮度为6667 cd/m2,在电流密度为3.2 mA/cm2时,最大流明效率为21 cd/A。
以实施例7化合物Ir(ppycr)3为掺杂材料,掺杂材料在主体材料中的质量百分比为1%,2%和4%,制作Ir(ppycr)3-PVK-PBD电致发光器件。
Ir(ppycr)3-PVK-PBD电致发光器件的电致发光光谱如图16所示,电流效率与电流密度曲线如图25所示。器件的最大发射光波长为524 nm,最大发光亮度为5757 cd/m2,在电流密度为2.75 mA/cm2时,最大流明效率为22.8 cd/A.当掺杂材料的质量分数为2%时:Ir(ppycr)3-PVK-PBD电致发光器件的电致发光光谱如图17所示,电流效率与电流密度曲线如图26所示。器件的最大发射光波长为524 nm,最大发光亮度为4293 cd/m2,在电流密度为10.2 mA/cm2时,最大流明效率为18.5 cd/A.当掺杂材料的质量分数为4%时:Ir(ppycr)3-PVK-PBD电致发光器件的电致发光光谱如图18所示,电流效率与电流密度曲线如图27所示。器件的最大发射光波长为524 nm,最大发光亮度为4156 cd/m2,在电流密度为2.8 mA/cm2时,最大流明效率为17.9 cd/A
以上仅仅是本发明的较佳实施例,根据本发明的上述构思,本领域的熟练人员还可以对此作出各种修改和变换。例如,对二苯并-18-冠-6的修饰,主体材料的改变,掺杂浓度的改变等等,类似的这些变换和修改均属于本发明的实质。
Claims (7)
1.一种二苯并-18-冠-6基环金属铱配合物,其特征在于,在环金属铱配合物的环金属配体苯基吡啶的苯环上引入二苯并-18-冠-6基团,其分子结构式为:
。
2.一种权利要求1所述二苯并-18-冠-6基环金属铱配合物的制备方法,其特征在于,在氮气保护下,将溴化fac-三(2-苯基吡啶)铱(Ⅲ)与二苯并-18-冠-6硼酸酯在四(三苯基磷)钯为催化剂作用下,加热并发生化学反应,冷却至室温,萃取,干燥。
3.根据权利要求2所述的制备方法,其特征在于,干燥后的粗产品用色谱柱分离纯化,得到黄色固体粉末。
4.根据权利要求2所述的制备方法,其特征在于,反应温度为90℃,反应时间为24-46小时。
5.一种权利要求1所述二苯并-18-冠-6基环金属铱配合物的应用,其特征在于,作为电致磷光材料用于聚合物电致磷光器件的发光层的掺杂剂。
6.一种聚合物绿光器件,包括氧化铟锡导电玻璃衬底层,空穴注入层,发光层,阴极注入层和阴极层,发光层为客体材料和主体材料的共混涂层,主体材料为聚乙烯咔唑即PVK和2-(4-联苯基)-5-(4-叔丁基)苯基-1,3,4-噁二唑即PBD,其特征在于,所述客体材料为权利要求1所述的二苯并-18-冠-6基环金属铱配合物,客体材料在主体材料中的掺杂浓度为1wt%~4 wt %。
7.根据权利要求6所述的聚合物绿光器件,其特征在于,所述空穴注入层为聚(3,4-亚乙二氧基噻吩)-聚(苯乙烯磺酸)涂层,所述PVK与PBD的重量比例为70%:30%,所述阴极注入层为氟化铯涂层,阴极层为金属铝。
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