CN104418910A - Organic blue light electrophosphorescent material, preparation method thereof and organic electroluminescent device - Google Patents
Organic blue light electrophosphorescent material, preparation method thereof and organic electroluminescent device Download PDFInfo
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- CN104418910A CN104418910A CN201310395541.4A CN201310395541A CN104418910A CN 104418910 A CN104418910 A CN 104418910A CN 201310395541 A CN201310395541 A CN 201310395541A CN 104418910 A CN104418910 A CN 104418910A
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- Prior art keywords
- blue light
- electroluminescent materials
- phosphorescent electroluminescent
- light organic
- organic phosphorescent
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- 239000000463 material Substances 0.000 title claims abstract description 95
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- 239000002184 metal Substances 0.000 claims abstract description 33
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 26
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 23
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims description 91
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 53
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 30
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 30
- 239000012043 crude product Substances 0.000 claims description 30
- 239000012153 distilled water Substances 0.000 claims description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 24
- 238000005401 electroluminescence Methods 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 22
- 239000000460 chlorine Substances 0.000 claims description 22
- 229910052801 chlorine Inorganic materials 0.000 claims description 22
- 230000004044 response Effects 0.000 claims description 22
- 125000004122 cyclic group Chemical group 0.000 claims description 19
- 239000012046 mixed solvent Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 13
- 229910052763 palladium Inorganic materials 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 13
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 13
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 12
- 239000011541 reaction mixture Substances 0.000 claims description 12
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 12
- 230000001681 protective effect Effects 0.000 claims description 11
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
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- 238000000605 extraction Methods 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 10
- 238000001953 recrystallisation Methods 0.000 claims description 10
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- OMFXVFTZEKFJBZ-HJTSIMOOSA-N corticosterone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OMFXVFTZEKFJBZ-HJTSIMOOSA-N 0.000 claims description 6
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 6
- 229960004756 ethanol Drugs 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 abstract description 57
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 abstract description 40
- 239000003446 ligand Substances 0.000 abstract description 11
- 125000000714 pyrimidinyl group Chemical group 0.000 abstract description 6
- TXXZKLBZLRLJON-UHFFFAOYSA-N 2-[3,5-difluoro-4-(trifluoromethyl)phenyl]pyridine Chemical compound FC=1C=C(C=C(C1C(F)(F)F)F)C1=NC=CC=C1 TXXZKLBZLRLJON-UHFFFAOYSA-N 0.000 abstract 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 46
- 230000015572 biosynthetic process Effects 0.000 description 28
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 21
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- 235000015320 potassium carbonate Nutrition 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
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- 238000011160 research Methods 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- SYOANZBNGDEJFH-UHFFFAOYSA-N 2,5-dihydro-1h-triazole Chemical compound C1NNN=C1 SYOANZBNGDEJFH-UHFFFAOYSA-N 0.000 description 8
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 8
- 210000002659 acromion Anatomy 0.000 description 8
- 239000011368 organic material Substances 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
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- 238000000746 purification Methods 0.000 description 7
- MFMNSNLMFVABMQ-UHFFFAOYSA-N B(O)O.FC1=CC=C(C=C1)C(F)(F)F Chemical compound B(O)O.FC1=CC=C(C=C1)C(F)(F)F MFMNSNLMFVABMQ-UHFFFAOYSA-N 0.000 description 6
- 0 C*c1cc(F)c(*)c(F)c1 Chemical compound C*c1cc(F)c(*)c(F)c1 0.000 description 6
- 125000006575 electron-withdrawing group Chemical group 0.000 description 6
- 150000003230 pyrimidines Chemical class 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- -1 iridium (III) compound Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 description 3
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- CINYXYWQPZSTOT-UHFFFAOYSA-N 3-[3-[3,5-bis(3-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical compound C1=CN=CC(C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)=C1 CINYXYWQPZSTOT-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 241001025261 Neoraja caerulea Species 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
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- 238000000151 deposition Methods 0.000 description 2
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- 239000000539 dimer Substances 0.000 description 2
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
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- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000003335 steric effect Effects 0.000 description 2
- YMMGRPLNZPTZBS-UHFFFAOYSA-N 2,3-dihydrothieno[2,3-b][1,4]dioxine Chemical compound O1CCOC2=C1C=CS2 YMMGRPLNZPTZBS-UHFFFAOYSA-N 0.000 description 1
- OBBXILSUQUPBJQ-UHFFFAOYSA-N 2-bromo-4-hexoxypyrimidine Chemical compound BrC1=NC=CC(=N1)OCCCCCC OBBXILSUQUPBJQ-UHFFFAOYSA-N 0.000 description 1
- FUTVFKDRMZATOI-UHFFFAOYSA-N 2-bromo-4-icosylpyrimidine Chemical compound BrC1=NC=CC(=N1)CCCCCCCCCCCCCCCCCCCC FUTVFKDRMZATOI-UHFFFAOYSA-N 0.000 description 1
- DPZWHUYAABAFKP-UHFFFAOYSA-N 2-bromo-5-methoxypyrimidine Chemical compound COC1=CN=C(Br)N=C1 DPZWHUYAABAFKP-UHFFFAOYSA-N 0.000 description 1
- KYCGEJNZMHUBMX-UHFFFAOYSA-N 2-bromo-5-methylpyrimidine Chemical compound CC1=CN=C(Br)N=C1 KYCGEJNZMHUBMX-UHFFFAOYSA-N 0.000 description 1
- AQXNNEIFLPMDQR-UHFFFAOYSA-N 2-bromo-5-tert-butylpyrimidine Chemical class CC(C)(C)C1=CN=C(Br)N=C1 AQXNNEIFLPMDQR-UHFFFAOYSA-N 0.000 description 1
- GNUYWXZHCXBVGI-UHFFFAOYSA-N B(O)O.FC=1C=CC=C(C1)C(F)(F)F Chemical compound B(O)O.FC=1C=CC=C(C1)C(F)(F)F GNUYWXZHCXBVGI-UHFFFAOYSA-N 0.000 description 1
- NGHUEGICNJISJK-UHFFFAOYSA-N CC(C)(C)C1=CN=C(c2cc(F)c(C(F)(F)F)c(F)c2)NC1 Chemical compound CC(C)(C)C1=CN=C(c2cc(F)c(C(F)(F)F)c(F)c2)NC1 NGHUEGICNJISJK-UHFFFAOYSA-N 0.000 description 1
- HKHRHBCOOOMMHC-WRGJJRIXSA-N CC/N=C(\N=C/C(C(C)(C)C)=C)/Br Chemical compound CC/N=C(\N=C/C(C(C)(C)C)=C)/Br HKHRHBCOOOMMHC-WRGJJRIXSA-N 0.000 description 1
- DNOYXLMEFCAWMA-UHFFFAOYSA-N CCC1NNC(c2ncccc2)=C1 Chemical compound CCC1NNC(c2ncccc2)=C1 DNOYXLMEFCAWMA-UHFFFAOYSA-N 0.000 description 1
- BXEHKPFJYWHRDI-UHFFFAOYSA-N FC(C1C(F)(F)F)C=C(C2N=CCCN2)C=C1F Chemical compound FC(C1C(F)(F)F)C=C(C2N=CCCN2)C=C1F BXEHKPFJYWHRDI-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000005429 oxyalkyl group Chemical group 0.000 description 1
- 235000012736 patent blue V Nutrition 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- NZCRJKRKKOLAOJ-XRCRFVBUSA-N rifaximin Chemical compound OC1=C(C(O)=C2C)C3=C4N=C5C=C(C)C=CN5C4=C1NC(=O)\C(C)=C/C=C/[C@H](C)[C@H](O)[C@@H](C)[C@@H](O)[C@@H](C)[C@H](OC(C)=O)[C@H](C)[C@@H](OC)\C=C\O[C@@]1(C)OC2=C3C1=O NZCRJKRKKOLAOJ-XRCRFVBUSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000007738 vacuum evaporation 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
- 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
-
- 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
-
- 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
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- 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
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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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
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses an organic blue light electrophosphorescent material with the structural formula as shown in the figure p, wherein r is a hydrogen atom, c1-c20 alkyl or c1-c20 alkoxy. The organic blue light electrophosphorescent material disclosed by the invention is an organic blue light electrophosphorescent hetero-coordinated metal iridium complex synthesized by taking 2-(3', 5'-difluoro-4'-trifluoromethylphenyl)pyridine as a cyclometalated ligand and 4-(pyridyl-2'-yl)-1, 2, 3-triazole as an auxiliary ligand, and the color of light emitted by the organic blue light electrophosphorescent material is regulated through chemical modification on an alkyl chain or an alkoxy chain introduced to a pyrimidine ring of the cyclometalated ligand, so that phosphorescent emission at high light emitting efficiency is realized. The invention also provides a preparation method of the organic blue light electrophosphorescent material and application of the organic blue light electrophosphorescent material to an organic electroluminescent device.
Description
Technical field
The present invention relates to field of organic electroluminescent materials, be specifically related to a kind of blue light organic phosphorescent electroluminescent materials and preparation method thereof and organic electroluminescence device.
Background technology
Organic electroluminescent refers to that organic materials is under electric field action, electric energy is converted into a kind of luminescence phenomenon of luminous energy.Make to stay cool to the research of organic electroluminescent due to reasons such as the driving voltage of organic electroluminescence device are too high, luminous efficiency is very low in early days.Until 1987, the human hairs such as the Tang of Kodak understand with oxine aluminium (Alq
3) be luminescent material, make the high-quality thin film of even compact with aromatic diamine, obtained low-work voltage, high brightness, high efficiency organic electroluminescence device, open the new prelude to electroluminescent organic material research.But owing to being subject to the restriction of spin statistics theory, the theoretical internal quantum efficiency limit of fluorescent material is only 25%, how makes full use of all the other phosphorescence of 75% and realize higher luminous efficiency and become hot research direction in after this this field.1997, Forrest etc. found electrophosphorescence phenomenon, and the internal quantum efficiency of electroluminescent organic material breaches the restriction of 25%, makes the research of electroluminescent organic material enter another new period.
In research subsequently, the title complex of small molecules doping type transition metal has become the research emphasis of people, as the title complex of iridium, ruthenium, platinum etc.The advantage of this kind of title complex is that they can obtain very high emitted energy from the triplet state of self, and wherein metal iridium (III) compound, due to good stability, in building-up process, reaction conditions is gentle, and there is very high electroluminescent properties, in research process subsequently, account for dominant position always.And in order to make device obtain full-color display, generally must obtain the ruddiness of excellent performance, green glow and blue light material simultaneously.Compare with green light material with ruddiness, the development of blue light material is more delayed comparatively speaking, the breakthrough point that the efficiency improving blue light material has just become people to study with purity of color.
The people such as Holmes R J, Forrest S R, at App.Phys.Lett., disclose two [2-(4', 6'-difluorophenyl) pyridine-N, C in 2003,82 (15): 2422-2424 articles
2 '] (2-pyridinecarboxylic) close iridium (FIrpic), be at present report at most, be also the best blue light organic phosphorescent electroluminescent materials of over-all properties, structural formula is as follows:
Although people have carried out various optimization to FIrpic class OLED structure, device performance have also been obtained very large raising, but the maximum weakness of FIrpic is exactly sent out blue light is sky blue, blue light color purity is not good enough, the CIE of each OLED made is (0.13 ~ 0.17,0.29 ~ 0.39) change between, between this and standard blue light CIE (0.137,0.084), have very large gap.
2008, Taiwan National Tsing Hua University Zheng Jianhong teaches at Adv.Funct.Mater.2008, disclose with 4-(pyridine-2 '-Ji)-1 in 18:485-491. article, 2,3-triazole is the two [2-(4' of iridium metal complexes of blue light organic phosphorescent electroluminescent materials of assistant ligand, 6'-difluorophenyl) pyridine-N, C
2'] [4-(pyridine-2 '-Ji)-1,2,3-triazoles] close iridium (FIrpytz).In dichloromethane solution, the maximum emission wavelength of FIrpic is positioned at 472nm, and CIE is (0.14,0.29), and the maximum emission wavelength of FIrpytz is blue shifted to 460nm, and CIE is (0.15,0.23), and blue light color purity is improved.The introducing of high field intensity assistant ligand 4-(pyridine-2 '-Ji)-1,2,3-triazoles is the blue shift emission wavelength of material effectively, and blue light color purity is higher, becomes one of first-selected assistant ligand of different distribution type blue phosphorescent complex of iridium luminescent material.
Realize the raising containing iridium complex phosphorescence material molecule illuminant colour purity, i.e. effective blue shift of luminescent spectrum, the most frequently used method on phenyl ring, introduces electron-withdrawing group to reduce HOMO energy level, except F-, and strong electrophilic group trifluoromethyl CF
3-replacement also can play similar effect.The Young-Inn Kim teach problem group of Busan, Korea national university in 2013 is at document Journal of Organometallic Chemistry2013, a kind of novel blue light phosphor material-bis-(2-(3 ' rolled into a ball by strong electron-withdrawing group in trifluoromethyl introducing ring master metal part is reported in 724:244-250., 5 '-two fluoro-4 '-trifluoromethyl) pyridine-N, C
2') (2-pyridinecarboxylic) close iridium ((dfpmpyCF
3)
2irpic), the maximum emission wavelength of its blue emitting phosphor device PHOLEDs made is blue shifted to 464nm.Not through optimised devices structure, (dfpmpyCF
3)
2the maximum emission wavelength of Irpic blue-light device is blue shifted to 469 ~ 472nm, and the maximum external quantum efficiency of device is 7.53%, and maximum current efficiency is 16.86cd/A.Facts have proved, in the main part of phosphor material complex of iridium, introduce strong electron-withdrawing substituent-trifluoromethyl becomes one of effective ways obtaining novel blue light with high color purity phosphor material.
The research of people to organic electromechanical phosphorescent material iridium metal complex is being goed deep into always, but there is bottleneck problem in the efficiency decay etc. of the illuminant colour purity of blue emitting phosphor material, luminous efficiency and device.Therefore, the blue phosphorescent organic electroluminescent material developing high color purity becomes the megatrend expanding blue light material research field.
Summary of the invention
Based on the problems referred to above, the invention provides a kind of blue-ray organic electroluminescent material, this material has good blue light luminous efficiency and good processing characteristics.Present invention also offers the preparation method of this blue-ray organic electroluminescent material and the application in organic electroluminescence device thereof.
First aspect, the invention provides a kind of blue light organic phosphorescent electroluminescent materials, and its general structure is as shown in P:
Wherein, R is hydrogen atom, C
1~ C
20alkyl or alkoxyl group.
Second aspect, the invention provides a kind of preparation method of blue light organic phosphorescent electroluminescent materials, comprises the steps:
(1), under protective gas existent condition, by structural formula be
compd A and structural formula be
compd B and catalyzer be dissolved in the first organic solvent, then obtain reaction solution with the aqueous solution of alkali, described reaction solution carries out Suzuki linked reaction 6 ~ 12h at 85 ~ 100 DEG C of temperature, after question response stops, separating-purifying reaction solution, obtaining structural formula is
cyclic metal complexes; Wherein, the mol ratio of compd A and compd B is 1:1.1 ~ 1:1.5; Wherein, R is hydrogen atom, C
1~ C
20alkyl or alkoxyl group;
(2), under protective gas existent condition, be that 2.2:1 ~ 3:1 is dissolved in the mixed solvent that cellosolvo and water formed with mol ratio by described cyclic metal complexes and three hydrated iridium trichloride, heating mixed solvent is to reflux state stirring reaction 22 ~ 25h; Be cooled to room temperature, separating-purifying, obtaining structural formula is
chlorine bridge dipolymer; Wherein, R is hydrogen atom, C
1~ C
20alkyl or alkoxyl group;
(3), under protective gas existent condition, by described chlorine bridge dipolymer and structural formula be
compound C be in the second organic solvent of being dissolved in containing alkali of 1:2.2 ~ 1:3 with mol ratio, obtain reaction mixture, reacting by heating mixed solution to 100 ~ 135 DEG C, stirring and refluxing reaction 8 ~ 15h, be cooled to room temperature, separating-purifying, obtaining structural formula is
blue light organic phosphorescent electroluminescent materials; Wherein, R is hydrogen atom, C
1~ C
20alkyl or alkoxyl group.
Preferably, the first organic solvent described in step (1) is toluene or dimethyl formamide (DMF).
Preferably, the alkali in described step (1) and (3) is sodium carbonate (Na
2cO
3) or salt of wormwood (K
2cO
3), the mol ratio of described alkali and compd A is 1:1 ~ 3:1, and described alkali and the dimeric mol ratio of chlorine bridge are 5:1 ~ 6:1.
Preferably, catalyzer described in step (1) is that four (triphenylphosphines) close palladium (Pd (PPh
3)
4) or dichloro two (triphenyl phosphorus) close palladium (Pd (PPh
3)
2cl
2), the mol ratio of described catalyzer and compd A is 0.03:1 ~ 0.05:1.
Preferably, described in step (1), the volumetric molar concentration of compd A in reaction solution is 0.1 ~ 0.2mol/L.
Preferably, the volumetric molar concentration in the mixed solvent that formed at cellosolvo and water of three hydrated iridium trichloride described in step (2) is 0.02 ~ 0.05mol/L.
Preferably, described in step (2), the volume ratio of cellosolvo and water is 3:1.
Preferably, described in step (3), the second organic solvent is 2-methyl cellosolve or cellosolvo.
Preferably, described in step (3), the mol ratio of chlorine bridge dimer and Compound C is 1:2.2 ~ 1:3.
Preferably, the concentration range of chlorine bridge dipolymer described in step (3) in reaction mixture is 0.01 ~ 0.02mol/L.
Preferably, described in step (1), the separating-purifying of cyclic metal complexes comprises:
After question response stops being cooled to room temperature, dichloromethane extraction, separatory, be washed to neutrality, with anhydrous magnesium sulfate drying; Filter, filtrate decompression steams solvent and obtains crude product, and the mixed solution formed with ethyl acetate and normal hexane is separated for elutriant carries out silica gel column chromatography, obtains described cyclic metal complexes after drying.
More preferably, the volume ratio of described ethyl acetate and normal hexane is 1:1 ~ 5:1.
Preferably, described in step (1) ~ (3), protective gas is nitrogen, argon gas or helium.
Preferably, described in step (2), the separating and purifying method of chlorine bridge dipolymer is:
Question response stop be cooled to room temperature after, the throw out in collecting by filtration reaction mixture, throw out uses ethanol, n-hexane successively, after vacuum-drying described chlorine bridge dipolymer or,
After question response stopping is cooled to room temperature, rotates and steam except partial solvent, add appropriate distilled water, filter and obtain solid, solid uses distilled water, methanol wash successively, obtains described chlorine bridge dipolymer after drying.
Preferably, described in step (3), the separating-purifying of blue light organic phosphorescent electroluminescent materials comprises:
After question response stops being cooled to room temperature, in reaction solution, the appropriate distilled water of impouring, has solid to separate out; Collecting by filtration crude product, uses deionized water, methyl alcohol, washed with diethylether for several times successively; Crude product obtains blue light organic phosphorescent electroluminescent materials after the mixed solvent recrystallization that methylene dichloride and dehydrated alcohol are formed.
This kind of blue light organic phosphorescent electroluminescent materials feature provided by the invention is with 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl) pyrimidine is cyclic metal complexes agent structure, with 4-(pyridine-2 '-Ji)-1,2,3-triazole is the different distribution type metal iridium complex of assistant ligand.Pyrimidyl on cyclic metal complexes is conducive to the lumo energy improving material, and on phenyl ring, strong electron-withdrawing group two F bases and trifluoromethyl are conducive to the HOMO energy level reducing material, make the effective blue shift of material emission wavelength; The difference alkyl of the straight or branched formula of different lengths or alkoxyl group being introduced pyrimidine ring replaces on position, the electro mass-energy of giving of alkyl or alkoxyl group obtains satisfied blue light emitting wavelength on the one hand, on the one hand the alkyl chain of different lengths is conducive to increasing its solvability in organic solvent in addition, and branch chain type alkyl or alkoxyl group can produce certain space steric effect, thus the direct effect between minimizing atoms metal, reduce the self-quenching phenomenon of triplet exciton; In addition, the introducing of strong electron-withdrawing group fluorine-based, the trifluoromethyl of group and assistant ligand 4-on phenyl ring (pyridine-2 '-Ji)-1,2,3-triazoles can also improve luminescent properties, is beneficial to evaporation, increases film-forming type and improves the stability of device.
The third aspect, the invention provides a kind of organic electroluminescence device, comprises luminescent layer, and doped with blue light organic phosphorescent electroluminescent materials in described luminescent layer, described blue light organic phosphorescent electroluminescent materials general structure is as shown in P:
Wherein, R is hydrogen atom, C
1~ C
20alkyl or alkoxyl group.
Containing above-mentioned blue light organic phosphorescent electroluminescent materials metal iridium complex in the luminescent layer of organic electroluminescence device of the present invention, material of main part in this compound and organic electroluminescence device luminescent layer has good consistency, can be widely used in and prepare blue light or white-light phosphor photoelectricity electroluminescence device.Organic electroluminescence device of the present invention is due to the organic electromechanical phosphorescent material metal iridium complex containing transmitting blue light wavelength in luminescent layer, thus it has the advantage launching high purity blue light and good device performance.
Accompanying drawing explanation
Fig. 1 is the preparation flow schematic diagram of the blue light organic phosphorescent electroluminescent materials of an embodiment;
Fig. 2 is the utilizing emitted light spectrogram of electroluminescent organic material in embodiment 1;
Fig. 3 is the structural representation of organic electroluminescence device in embodiment 8.
Embodiment
Blue light organic phosphorescent electroluminescent materials provided by the invention, with 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl) pyrimidine is cyclic metal complexes, with 4-(pyridine-2 '-Ji)-1,2,3-triazole is assistant ligand, synthesize the different distribution type title complex of a kind of blue light organic phosphorescent electroluminescent materials iridium metals, and realize the adjustment to material emission color by the chemically modified introducing alkyl or oxyalkyl chain on the pyrimidine ring of cyclic metal complexes, thus obtain the phosphorescent emissions of high-luminous-efficiency.
The general structure of blue light organic phosphorescent electroluminescent materials provided by the invention is as shown in P:
Wherein, R is hydrogen atom, C
1~ C
20alkyl or alkoxyl group, the structural formula of described cyclic metal complexes is:
Fig. 1 is the preparation flow schematic diagram of the blue light organic phosphorescent electroluminescent materials of an embodiment.Refer to Fig. 1, the preparation method of above-mentioned blue light organic phosphorescent electroluminescent materials, comprises the steps:
Under S1, protective gas existent condition, by structural formula be
compd A and structural formula be
compd B and catalyzer be dissolved in the first organic solvent, then obtain reaction solution with the aqueous solution of alkali, described reaction solution carries out Suzuki linked reaction 6 ~ 12h at 85 ~ 100 DEG C of temperature, after question response stops, separating-purifying reaction solution, obtaining structural formula is
cyclic metal complexes; Wherein, the mol ratio of compd A and compd B is 1:1.1 ~ 1:1.5; Wherein, R is hydrogen atom, C
1~ C
20alkyl or alkoxyl group; Reaction formula is:
Under S2, protective gas existent condition, be that 2.2:1 ~ 3:1 is dissolved in the mixed solvent that cellosolvo and water formed with mol ratio by described cyclic metal complexes and three hydrated iridium trichloride, heating mixed solvent is to reflux state stirring reaction 22 ~ 25h; Be cooled to room temperature, separating-purifying, obtaining structural formula is
chlorine bridge dipolymer; Wherein, R is hydrogen atom, C
1~ C
20alkyl or alkoxyl group; Reaction formula is:
Under S3, protective gas existent condition, by described chlorine bridge dipolymer and structural formula be
compound C be in the second organic solvent of being dissolved in containing alkali of 1:2.2 ~ 1:3 with mol ratio, obtain reaction mixture, reacting by heating mixed solution to 100 ~ 135 DEG C, stirring and refluxing reaction 8 ~ 15h, be cooled to room temperature, separating-purifying, obtaining structural formula is
blue light organic phosphorescent electroluminescent materials; Wherein, R is hydrogen atom, C
1~ C
20alkyl or alkoxyl group; Reaction formula is:
Preferably, the first organic solvent described in step S1 is toluene or dimethyl formamide (DMF).
Preferably, the alkali in described step S1 and S3 is sodium carbonate (Na
2cO
3) or salt of wormwood (K
2cO
3), the mol ratio of described alkali and compd A is 1:1 ~ 3:1, and described alkali and the dimeric mol ratio of chlorine bridge are 5:1 ~ 6:1.
Preferably, catalyzer described in step S1 is that four (triphenylphosphines) close palladium (Pd (PPh
3)
4) or dichloro two (triphenyl phosphorus) close palladium (Pd (PPh
3)
2cl
2), the mol ratio of described catalyzer and compd A is 0.03:1 ~ 0.05:1.
Preferably, the volumetric molar concentration of compd A described in step S1 in reaction solution is 0.1 ~ 0.2mol/L.
Preferably, the volumetric molar concentration in the mixed solvent that formed at cellosolvo and water of three hydrated iridium trichloride described in step S2 is 0.02 ~ 0.05mol/L.
Preferably, the volume ratio of cellosolvo described in step S2 and water is 3:1.
Preferably, the second organic solvent described in step S3 is 2-methyl cellosolve or cellosolvo.
Preferably, the mol ratio of the bridge dimer of chlorine described in step S3 and Compound C is 1:2.2 ~ 1:3.
Preferably, the concentration range of the bridge of chlorine described in step S3 dipolymer in reaction mixture is 0.01 ~ 0.02mol/L.
Preferably, the separating-purifying of cyclic metal complexes described in step S1 comprises:
After question response stops being cooled to room temperature, dichloromethane extraction, separatory, be washed to neutrality, with anhydrous magnesium sulfate drying; Filter, filtrate decompression steams solvent and obtains crude product, and the mixed solution formed with ethyl acetate and normal hexane is separated for elutriant carries out silica gel column chromatography, obtains described cyclic metal complexes after drying.
More preferably, the volume ratio of described ethyl acetate and normal hexane is 1:1 ~ 5:1.
Preferably, protective gas described in step S1 ~ S3 is nitrogen, argon gas or helium.
Preferably, the separating and purifying method of the bridge of chlorine described in step S2 dipolymer is:
Question response stop be cooled to room temperature after, the throw out in collecting by filtration reaction mixture, throw out uses ethanol, n-hexane successively, after vacuum-drying described chlorine bridge dipolymer or,
After question response stopping is cooled to room temperature, rotates and steam except partial solvent, add appropriate distilled water, filter and obtain solid, solid uses distilled water, methanol wash successively, obtains described chlorine bridge dipolymer after drying.
Preferably, the separating-purifying of blue light organic phosphorescent electroluminescent materials described in step S3 comprises:
After question response stops being cooled to room temperature, in reaction solution, the appropriate distilled water of impouring, has solid to separate out; Collecting by filtration crude product, uses deionized water, methyl alcohol, washed with diethylether for several times successively; Crude product obtains blue light organic phosphorescent electroluminescent materials after the mixed solvent recrystallization that methylene dichloride and dehydrated alcohol are formed.
This kind of blue light organic phosphorescent electroluminescent materials feature provided by the invention is with 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl) pyrimidine is cyclic metal complexes agent structure, with 4-(pyridine-2 '-Ji)-1,2,3-triazole is the different distribution type metal iridium complex of assistant ligand.Pyrimidyl on cyclic metal complexes is conducive to the lumo energy improving material, and on phenyl ring, strong electron-withdrawing group two F bases and trifluoromethyl are conducive to the HOMO energy level reducing material, make the effective blue shift of material emission wavelength; The difference alkyl of the straight or branched formula of different lengths or alkoxyl group being introduced pyrimidine ring replaces on position, the electro mass-energy of giving of alkyl or alkoxyl group obtains satisfied blue light emitting wavelength on the one hand, on the one hand the alkyl chain of different lengths is conducive to increasing its solvability in organic solvent in addition, and branch chain type alkyl or alkoxyl group can produce certain space steric effect, thus the direct effect between minimizing atoms metal, reduce the self-quenching phenomenon of triplet exciton; In addition, the introducing of strong electron-withdrawing group fluorine-based, the trifluoromethyl of group and assistant ligand 4-on phenyl ring (pyridine-2 '-Ji)-1,2,3-triazoles can also improve luminescent properties, is beneficial to evaporation, increases film-forming type and improves the stability of device.
A kind of organic electroluminescence device, comprise luminescent layer, doped with blue light organic phosphorescent electroluminescent materials in described luminescent layer, described blue light organic phosphorescent electroluminescent materials general structure is as shown in P:
Wherein, R is hydrogen atom, C
1~ C
20alkyl or alkoxyl group.
Containing above-mentioned blue light organic phosphorescent electroluminescent materials metal iridium complex in the luminescent layer of organic electroluminescence device of the present invention, material of main part in this compound and organic electroluminescence device luminescent layer has good consistency, can be widely used in and prepare blue light or white-light phosphor photoelectricity electroluminescence device.Organic electroluminescence device of the present invention is due to the organic electromechanical phosphorescent material metal iridium complex containing transmitting blue light wavelength in luminescent layer, thus it has the advantage launching high purity blue light and good device performance.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1: title complex two (2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl) pyrimidine-N, C
2') (4-(pyridine-2 '-Ji)-1,2,3-triazoles) close the synthesis of iridium
(1) synthesis of 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl) pyrimidine
Under nitrogen protection; 1.59g (10mmol) 2-bromo pyrimi piperidine, 2.71g (12mmol) 3; the fluoro-4-trifluoromethylbenzene boronic acid of 5-bis-and 0.58g (0.5mmol) four (triphenyl phosphorus) close palladium and are dissolved in 40mL toluene, stir 10min.The aqueous solution of 20mL containing 2.76g (20mmol) salt of wormwood is dripped subsequently in reaction system.Heating, stirring reaction 6h under 100 DEG C of state of temperatures.After question response liquid cooling to room temperature, dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying.Filter, filtrate decompression steams solvent and obtains crude product.With volume ratio be 1/1 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 1.14g, yield is 43.8%.
Structural Identification:
Mass spectrum (MS m/z): 260.0 (M
+)
Ultimate analysis: C
11h
5f
5n
2
Theoretical value: C, 50.78; H, 1.94; F, 36.51; N, 10.77;
Measured value: C, 50.74; H, 1.99; F, 36.53; N, 10.74.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl) pyrimidine.
(2) part be 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl) pyrimidine containing the dimeric synthesis of iridium dichloro
Under nitrogen protection; 0.71g (2mmol) three hydrated iridium trichloride and 1.82g (7mmol) 2-(3 '; 5 '-two fluoro-4 '-trifluoromethyl) to be dissolved in 60mL volume ratio be in the cellosolvo/water mixed liquid of 3:1 to pyrimidine, is heated to stirring reaction 24h under reflux state.Be chilled to the throw out in collecting by filtration reaction mixture after room temperature, ethanol, n-hexane successively, after vacuum-drying solids 0.74g, yield is 49.6%.Dipolymer, without the need to further purification, can directly drop in next step reaction.
(3) title complex two (2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl) pyrimidine-N, C
2') (4-(pyridine-2 '-Ji)-1,2,3-triazoles) close the synthesis of iridium
Under nitrogen protection; 0.75g (0.5mmol) part is 2-(3 '; 5 '-two fluoro-4 '-trifluoromethyl) pyrimidine containing iridium dichloro dimer; 0.22g (1.5mmol) 4-(pyridine-2 '-Ji)-1; 2,3-triazole and 0.41g (3mmol) salt of wormwood are dissolved in 25mL2-ethoxy ethanol.Stirring reaction mixed solution is heated to 100 DEG C of reaction 15h.Naturally, after being chilled to room temperature, in reaction solution, the appropriate distilled water of impouring, has solid to separate out.Collect crude product, use deionized water, methyl alcohol, washed with diethylether for several times successively.Crude product is through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, and obtain pure 0.47g pure products after drying, yield is 54.9%.
Structural Identification:
Mass spectrum (MS m/z): 856.1 (M
+)
Ultimate analysis: C
29h
13f
10irN
8
Theoretical value: C, 40.71; H, 1.53; F, 22.20; Ir, 22.46; N, 13.10;
Measured value: C, 40.64; H, 1.62; F, 22.16; Ir, 22.49; N, 13.09.
The material that the above-mentioned reaction of above data acknowledgement obtains is title complex two (2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl) pyrimidine-N, C
2') (4-(pyridine-2 '-Ji)-1,2,3-triazoles) close iridium.
Fig. 2 is the utilizing emitted light spectrogram of electroluminescent organic material in embodiment 1.As shown in Figure 2, transverse axis is luminous (unit nm), and the longitudinal axis is normalized photoluminescence intensity, and end product is CH at 298K temperature
2cl
2solution (~ 10
-5the maximum emission peak of the emmission spectrum M), at 470nm place, has an acromion at 494nm place simultaneously, can be used as the preparation field that blue light electroluminescent material is widely used in organic electroluminescence device.
In addition, 10
-5the CH of M end product
2cl
2solution at 298K temperature, with concentration for ~ 10
-5the Ir (ppy) of M
3cH
2cl
2solution is standard (Φ
pL=0.40) Φ of end product, is recorded
pL=0.13, the iridium electroluminescent organic material that contains of visible the present embodiment has higher luminous quantum efficiency.
Embodiment 2: title complex two (2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-methylpyrimidine-N, C
2') (4-(pyridine-2 '-Ji)-1,2,3-triazoles) close the synthesis of iridium
(1) synthesis of 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-methylpyrimidine
Under nitrogen protection; the bromo-5-methylpyrimidine of 1.73g (10mmol) 2-, 2.48g (11mmol) 3; the fluoro-4-trifluoromethylbenzene boronic acid of 5-bis-and 0.28g (0.4mmol) dichloro two (triphenyl phosphorus) close palladium and are dissolved in 50mL DMF, stir 10min.The aqueous solution of 25mL containing 3.18g (30mmol) sodium carbonate is dripped subsequently in reaction system.Be heated to stirring reaction 8h under 90 DEG C of state of temperatures.After question response liquid cooling to room temperature, dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying.Filter, filtrate decompression steams solvent and obtains crude product.With volume ratio be 2/1 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 0.82g, yield is 29.9%.
Structural Identification:
Mass spectrum (MS m/z): 274.0 (M
+)
Ultimate analysis: C
12h
7f
5n
2
Theoretical value: C, 52.57; H, 2.57; F, 34.64; N, 10.22;
Measured value: C, 52.53; H, 2.63; F, 34.56; N, 10.28.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-methylpyrimidine.
(2) part be 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-methylpyrimidine containing the dimeric synthesis of iridium dichloro
Under nitrogen protection; 0.71g (2mmol) three hydrated iridium trichloride; 1.64g (6mmol) 2-(3 '; 5 '-two fluoro-4 '-trifluoromethyl) to be dissolved in 50mL volume ratio be in the cellosolvo/water mixed liquid of 3:1 to-4-methylpyrimidine, is heated to stirring reaction 22h under reflux state.Be chilled to the throw out in collecting by filtration reaction mixture after room temperature, ethanol, n-hexane successively, after vacuum-drying solids 0.59g, yield is 38.1%.Dipolymer, without the need to further purification, can directly drop in next step reaction.
(3) title complex two (2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-methylpyrimidine-N, C
2') (4-(pyridine-2 '-Ji)-1,2,3-triazoles) close the synthesis of iridium
Under nitrogen protection; 0.77g (0.5mmol) part is 2-(3 '; 5 '-two fluoro-4 '-trifluoromethyl)-5-methylpyrimidine containing iridium dichloro dimer; 0.18g (1.25mmol) 4-(pyridine-2 '-Ji)-1; 2,3-triazole and 0.41g (3mmol) sodium carbonate are dissolved in 30mL2-ethoxy ethanol.Stirring reaction mixed solution is heated to 135 DEG C of back flow reaction 8h.Naturally, after being chilled to room temperature, in reaction solution, the appropriate distilled water of impouring, has solid to separate out.Collect crude product, use deionized water, methyl alcohol, washed with diethylether for several times successively.Crude product is through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, and obtain pure 0.36g pure products after drying, yield is 40.7%.
Structural Identification:
Mass spectrum (MS m/z): 884.1 (M
+)
Ultimate analysis: C
31h
17f
10irN
8
Theoretical value: C, 42.13; H, 1.94; F, 21.50; Ir, 21.75; N, 12.68;
Measured value: C, 42.15; H, 1.96; F, 21.47; Ir, 21.71; N, 12.71.
The material that the above-mentioned reaction of above data acknowledgement obtains is title complex two (2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-methylpyrimidine-N, C
2') (4-(pyridine-2 '-Ji)-1,2,3-triazoles) close iridium.
End product is CH at 298K temperature
2cl
2solution (~ 10
-5the maximum emission peak of the emmission spectrum M), at 467nm place, has an acromion at 491nm place, with the Ir of same concentrations (ppy) simultaneously
3cH
2cl
2solution is standard (Φ
pL=0.40) Φ of end product, is recorded
pL=0.06, the iridium electroluminescent organic material that contains of visible the present embodiment has higher luminous quantum efficiency, can be used as the preparation field that blue light electroluminescent material is widely used in organic electroluminescence device.
Embodiment 3: title complex two (2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-t-butyl pyrimidines-N, C
2') (4-(pyridine-2 '-Ji)-1,2,3-triazoles) close the synthesis of iridium
(1) synthesis of 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-t-butyl pyrimidines
Under nitrogen protection; the bromo-5-t-butyl pyrimidines of 2.15g (10mmol) 2-, 3.39g (15mmol) 3; the fluoro-4-trifluoromethylbenzene boronic acid of 5-bis-and 0.21g (0.3mmol) dichloro two (triphenyl phosphorus) close palladium and are dissolved in 35mL DMF, stir 10min.The aqueous solution of 15mL containing 1.38g (10mmol) salt of wormwood is dripped subsequently in reaction system.Be heated to stirring reaction 10h under 85 DEG C of states.After question response liquid cooling to room temperature, dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying.Filter, filtrate decompression steams solvent and obtains crude product.With volume ratio be 3/1 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 0.47g, yield is 14.9%.
Structural Identification:
Mass spectrum (MS m/z): 316.1 (M
+)
Ultimate analysis: C
15h
13f
5n
2
Theoretical value: C, 56.96; H, 4.14; F, 30.04; N, 8.86;
Measured value: C, 56.92; H, 4.20; F, 30.00; N, 8.88.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-t-butyl pyrimidines.
(2) part be 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-t-butyl pyrimidines containing the dimeric synthesis of iridium dichloro
Under nitrogen protection; 0.35g (1mmol) three hydrated iridium trichloride and 0.70g (2.2mmol) 2-(3 '; 5 '-two fluoro-4 '-trifluoromethyl) to be dissolved in 20mL volume ratio be in the cellosolvo/water mixed liquid of 3:1 to-5-t-butyl pyrimidines, stirring reaction 24h at reflux.Be chilled to the throw out in collecting by filtration reaction mixture after room temperature, ethanol, n-hexane successively, after vacuum-drying solids 0.22g, yield is 25.6%.Dipolymer, without the need to further purification, can directly drop in next step reaction.
(3) title complex two (2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-t-butyl pyrimidines-N, C
2') (4-(pyridine-2 '-Ji)-1,2,3-triazoles) close the synthesis of iridium
Under nitrogen protection; 0.69g (0.4mmol) part is 2-(3 '; 5 '-two fluoro-4 '-trifluoromethyl)-5-t-butyl pyrimidines containing iridium dichloro dimer; 0.13g (0.88mmol) 4-(pyridine-2 '-Ji)-1; 2,3-triazole and 0.28g (2mmol) salt of wormwood are dissolved in 20mL2-methyl cellosolve.Stirring reaction mixed solution is heated to 125 DEG C of back flow reaction 10h.Naturally, after being chilled to room temperature, in reaction solution, the appropriate distilled water of impouring, has solid to separate out.Collect crude product, use deionized water, methyl alcohol, washed with diethylether for several times successively.Crude product is through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, and obtain pure 0.17g pure products after drying, yield is 22.0%.
Structural Identification:
Mass spectrum (MS m/z): 968.2 (M
+)
Ultimate analysis: C
37h
29f
10irN
8
Theoretical value: C, 45.91; H, 3.02; F, 19.63; Ir, 19.86; N, 11.58;
Measured value: C, 45.87; H, 3.08; F, 19.55; Ir, 19.93; N, 11.57.
The material that the above-mentioned reaction of above data acknowledgement obtains is title complex two (2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-t-butyl pyrimidines-N, C
2') (4-(pyridine-2 '-Ji)-1,2,3-triazoles) close iridium.
End product is CH at 298K temperature
2cl
2solution (~ 10
-5the maximum emission peak of the emmission spectrum M), at 474nm place, has an acromion at 498nm place, with the Ir of same concentrations (ppy) simultaneously
3cH
2cl
2solution is standard (Φ
pL=0.40) Φ of end product, is recorded
pL=0.10.
Embodiment 4: title complex two (2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-4-eicosyl pyrimidine-N, C
2') (4-(pyridine-2 '-Ji)-1,2,3-triazoles) close the synthesis of iridium
(1) synthesis of 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-4-eicosyl pyrimidine
Under nitrogen protection; 2.20g (5mmol) 2-bromo-4-eicosyl pyrimidine, 1.36g (6mmol) 2; the fluoro-3-trifluoromethylbenzene boronic acid of 4-bis-and 0.23g (0.2mmol) four (triphenyl phosphorus) close palladium and are dissolved in 35mL toluene, stir 10min.The aqueous solution of 15mL containing 1.38g (10mmol) salt of wormwood is dripped subsequently in reaction system.Be heated to stirring reaction 12h under 85 DEG C of state of temperatures.After question response liquid cooling to room temperature, dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying.Filter, filtrate decompression steams solvent and obtains crude product.With volume ratio be 4/1 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 0.54g, yield is 20.0%.
Structural Identification:
Mass spectrum (MS m/z): 540.4 (M
+)
Ultimate analysis: C
31h
45f
5n
2
Theoretical value: C, 68.86; H, 8.39; F, 17.57; N, 5.18;
Measured value: C, 68.83; H, 8.45; F, 17.51; N, 5.21.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-4-eicosyl pyrimidine.
(2) part be 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-4-eicosyl pyrimidine containing the dimeric synthesis of iridium dichloro
Under nitrogen protection; 0.18g (0.5mmol) three hydrated iridium trichloride; 0.81g (1.5mmol) 2-(3 '; 5 '-two fluoro-4 '-trifluoromethyl) to be dissolved in 25mL volume ratio be in the cellosolvo/water mixed liquid of 3:1 to-4-eicosyl pyrimidine, stirring reaction 25h at reflux.After being chilled to room temperature, rotating and steam except partial solvent, add appropriate distilled water, filter.Solid uses distilled water, methanol wash successively, and obtain solids 0.10g after drying, yield is 15.3%.Dipolymer, without the need to further purification, can directly drop in next step reaction.
(3) title complex two (2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-4-eicosyl pyrimidine-N, C
2') (4-(pyridine-2 '-Ji)-1,2,3-triazoles) close the synthesis of iridium
Under nitrogen protection; 0.78g (0.3mmol) part is 2-(3 '; 5 '-two fluoro-4 '-trifluoromethyl)-4-eicosyl pyrimidine containing iridium dichloro dimer; 0.13g (0.9mmol) 4-(pyridine-2 '-Ji)-1; 2,3-triazole and 0.16g (1.5mmol) sodium carbonate are dissolved in 30mL2-methyl cellosolve.Stirring reaction mixed solution is heated to 100 DEG C of back flow reaction 15h.Naturally, after being chilled to room temperature, in reaction solution, the appropriate distilled water of impouring, has solid to separate out.Collect crude product, use deionized water, methyl alcohol, washed with diethylether for several times successively.Crude product is through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, and obtain pure 0.12g pure products after drying, yield is 14.1%.
Structural Identification:
Mass spectrum (MS m/z): 1416.7 (M
+)
Ultimate analysis: C
69h
93f
10irN
8
Theoretical value: C, 58.50; H, 6.62; F, 13.41; Ir, 13.57; N, 7.91;
Measured value: C, 58.56; H, 6.54; F, 13.37; Ir, 13.63; N, 7.90.
The material that the above-mentioned reaction of above data acknowledgement obtains is title complex two (2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-4-eicosyl pyrimidine-N, C
2') (4-(pyridine-2 '-Ji)-1,2,3-triazoles) close iridium.
End product is CH at 298K temperature
2cl
2solution (~ 10
-5the maximum emission peak of the emmission spectrum M), at 493nm place, has an acromion at 516nm place, with the Ir of same concentrations (ppy) simultaneously
3cH
2cl
2solution is standard (Φ
pL=0.40) Φ of end product, is recorded
pL=0.007.
Embodiment 5: title complex two (2-(the fluoro-3'-trifluoromethyl of 4', 6'-bis-)-5-methoxy pyrimidine-N, C
2') (4-(pyridine-2 '-Ji)-1,2,3-triazoles) close the synthesis of iridium
(1) synthesis of 2-(3 ' 5 '-two fluoro-4 '-trifluoromethyl)-5-methoxy pyrimidine
Under nitrogen protection; the bromo-5-methoxy pyrimidine of 1.89g (10mmol) 2-, 2.71g (12mmol) 3; the fluoro-4-trifluoromethylbenzene boronic acid of 5-bis-and 0.58g (0.5mmol) four (triphenyl phosphorus) close palladium and are dissolved in 40mL toluene, continue to stir 10min.The aqueous solution of 20mL containing 2.76g (20mmol) salt of wormwood is dripped subsequently in reaction system.Be heated to stirring reaction 6h under 100 DEG C of state of temperatures.After question response liquid cooling to room temperature, dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying.Filter, filtrate decompression steams solvent and obtains crude product.With volume ratio be 2/1 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 1.10g, yield is 37.9%.
Structural Identification:
Mass spectrum (MS m/z): 290.0 (M
+)
Ultimate analysis: C
12h
7f
5n
2o
Theoretical value: C, 49.67; H, 2.43; F, 32.73; N, 9.65; O, 5.51;
Measured value: C, 49.61; H, 2.52; F, 32.65; N, 9.73; O, 5.49.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-methoxy pyrimidine.
(2) part be 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-methoxy pyrimidine containing the dimeric synthesis of iridium dichloro
Under nitrogen protection; 0.71g (2mmol) three hydrated iridium trichloride; 1.74g (6mmol) 2-(3 '; 5 '-two fluoro-4 '-trifluoromethyl) to be dissolved in 50mL volume ratio be in the cellosolvo/water mixed liquid of 3:1 to-5-methoxy pyrimidine, is heated to stirring reaction 24h under reflux state.After being chilled to room temperature, rotating and steam except partial solvent, add appropriate distilled water, filter.Solid uses distilled water, methanol wash successively, and obtain solids 0.64g after drying, yield is 39.7%.Dipolymer, without the need to further purification, can directly drop in next step reaction.
(3) title complex two (2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-methoxy pyrimidine-N, C
2') (4-(pyridine-2 '-Ji)-1,2,3-triazoles) close the synthesis of iridium
Under nitrogen protection; 0.81g (0.5mmol) part is 2-(3 '; 5 '-two fluoro-4 '-trifluoromethyl)-5-methoxy pyrimidine containing iridium dichloro dimer; 0.22g (1.5mmol) 4-(pyridine-2 '-Ji)-1; 2,3-triazole and 0.41g (3mmol) salt of wormwood are dissolved in 25mL2-ethoxy ethanol.Stirring reaction mixed solution is heated to 100 DEG C of reaction 15h.Naturally, after being chilled to room temperature, in reaction solution, the appropriate distilled water of impouring, has solid to separate out.Collect crude product, use deionized water, methyl alcohol, washed with diethylether for several times successively.Crude product is through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, and obtain pure 0.35g pure products after drying, yield is 38.2%.
Structural Identification:
Mass spectrum (MS m/z): 916.1 (M
+)
Ultimate analysis: C
31h
17f
10irN
8o
2
Theoretical value: C, 40.66; H, 1.87; F, 20.75; Ir, 20.99; N, 12.24; O, 3.49;
Measured value: C, 40.62; H, 1.93; F, 20.70; Ir, 20.95; N, 12.33; O, 3.47.
The material that the above-mentioned reaction of above data acknowledgement obtains is title complex two (2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-methoxy pyrimidine-N, C
2') (4-(pyridine-2 '-Ji)-1,2,3-triazoles) close iridium.
End product is CH at 298K temperature
2cl
2solution (~ 10
-5the maximum emission peak of the emmission spectrum M), at 465nm place, has an acromion at 490nm place, with the Ir of same concentrations (ppy) simultaneously
3cH
2cl
2solution is standard (Φ
pL=0.40) Φ of end product, is recorded
pL=0.05.
Embodiment 6: title complex two (2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-4-hexyloxy pyrimidine-N, C
2') (4-(pyridine-2 '-Ji)-1,2,3-triazoles) close the synthesis of iridium
(1) synthesis of 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-4-hexyloxy pyrimidine
Under nitrogen protection; 2.59g (10mmol) 2-bromo-4-hexyloxy pyrimidine, 3.39g (15mmol) 3; the fluoro-4-trifluoromethylbenzene boronic acid of 5-bis-and 0.21g (0.3mmol) dichloro two (triphenyl phosphorus) close palladium and are dissolved in 40mL DMF, stir 10min.The aqueous solution of 20mL containing 1.38g (10mmol) salt of wormwood is dripped subsequently in reaction system.Be heated to stirring reaction 10h under 85 DEG C of states.After question response liquid cooling to room temperature, dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying.Filter, filtrate decompression steams solvent and obtains crude product.With volume ratio be 4/1 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 0.79g, yield is 21.9%.
Structural Identification:
Mass spectrum (MS m/z): 360.1 (M
+)
Ultimate analysis: C
17h
17f
5n
2o
Theoretical value: C, 56.67; H, 4.76; F, 26.36; N, 7.77; O, 4.44;
Measured value: C, 56.63; H, 4.83; F, 26.31; N, 7.84; O, 4.39.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-4-hexyloxy pyrimidine.
(2) part be 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-4-hexyloxy pyrimidine containing the dimeric synthesis of iridium dichloro
Under nitrogen protection; 0.35g (1mmol) three hydrated iridium trichloride and 0.79g (2.2mmol) 2-(3 '; 5 '-two fluoro-4 '-trifluoromethyl) to be dissolved in 20mL volume ratio be in the cellosolvo/water mixed liquid of 3:1 to-4-hexyloxy pyrimidine, stirring reaction 24h at reflux.After being chilled to room temperature, rotating and steam except partial solvent, add appropriate distilled water, filter.Solid uses distilled water, methanol wash successively, and obtain solids 0.31g after drying, yield is 32.8%.Dipolymer, without the need to further purification, can directly drop in next step reaction.
(3) title complex two (2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-4-hexyloxy pyrimidine-N, C
2') (4-(pyridine-2 '-Ji)-1,2,3-triazoles) close the synthesis of iridium
Under nitrogen protection; 0.76g (0.4mmol) part is 2-(3 '; 5 '-two fluoro-4 '-trifluoromethyl)-4-hexyloxy pyrimidine containing iridium dichloro dimer; 0.13g (0.88mmol) 4-(pyridine-2 '-Ji)-1; 2,3-triazole and 0.28g (2mmol) salt of wormwood are dissolved in 30mL2-methyl cellosolve.Stirring reaction mixed solution is heated to 125 DEG C of back flow reaction 10h.Naturally, after being chilled to room temperature, in reaction solution, the appropriate distilled water of impouring, has solid to separate out.Collect crude product, use deionized water, methyl alcohol, washed with diethylether for several times successively.Crude product is through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, and obtain pure 0.13g pure products after drying, yield is 15.4%.
Structural Identification:
Mass spectrum (MS m/z): 1056.2 (M
+)
Ultimate analysis: C
41h
37f
10irN
8o
2
Theoretical value: C, 46.63; H, 3.53; F, 17.99; Ir, 18.20; N, 10.61; O, 3.03;
Measured value: C, 46.57; H, 3.59; F, 17.94; Ir, 18.27; N, 10.55; O, 3.08.
The material that the above-mentioned reaction of above data acknowledgement obtains is title complex two (2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-4-hexyloxy pyrimidine-N, C
2') (4-(pyridine-2 '-Ji)-1,2,3-triazoles) close iridium.
End product is CH at 298K temperature
2cl
2solution (~ 10
-5the maximum emission peak of the emmission spectrum M), at 479nm place, has an acromion at 503nm place, with the Ir of same concentrations (ppy) simultaneously
3cH
2cl
2solution is standard (Φ
pL=0.40) Φ of end product, is recorded
pL=0.01.
Embodiment 7: title complex two (2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-eicosane oxygen yl pyrimidines-N, C
2') (4-(pyridine-2 '-Ji)-1,2,3-triazoles) close the synthesis of iridium
(1) synthesis of 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-eicosane oxygen yl pyrimidines
Under nitrogen protection; 2.28g (5mmol) 2-bromo-5-eicosane oxygen yl pyrimidines, 1.36g (6mmol) 3; the fluoro-4-trifluoromethylbenzene boronic acid of 5-bis-and 0.23g (0.2mmol) four (triphenyl phosphorus) close palladium and are dissolved in 35mL toluene, stir 10min.The aqueous solution of 15mL containing 1.38g (10mmol) salt of wormwood is dripped subsequently in reaction system.Be heated to stirring reaction 12h under 85 DEG C of state of temperatures.After question response liquid cooling to room temperature, dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying.Filter, filtrate decompression steams solvent and obtains crude product.With volume ratio be 5/1 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 0.50g, yield is 18.0%.
Structural Identification:
Mass spectrum (MS m/z): 556.4 (M
+)
Ultimate analysis: C
31h
45f
5n
2o
Theoretical value: C, 66.88; H, 8.15; F, 17.06; N, 5.03; O, 2.87;
Measured value: C, 66.83; H, 8.24; F, 17.04; N, 5.06; O, 2.83.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-eicosane oxygen yl pyrimidines.
(2) part be 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-eicosane oxygen yl pyrimidines containing the dimeric synthesis of iridium dichloro
Under nitrogen protection; 0.18g (0.5mmol) three hydrated iridium trichloride; 0.84g (1.5mmol) 2-(3 '; 5 '-two fluoro-4 '-trifluoromethyl) to be dissolved in 25mL volume ratio be in the cellosolvo/water mixed liquid of 3:1 to-5-eicosane oxygen yl pyrimidines, stirring reaction 25h at reflux.After being chilled to room temperature, rotating and steam except partial solvent, add appropriate distilled water, filter.Solid uses distilled water, methanol wash successively, and obtain solids 0.10g after drying, yield is 14.9%.Dipolymer, without the need to further purification, can directly drop in next step reaction.
(3) title complex two (2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-eicosane oxygen yl pyrimidines-N, C
2') (4-(pyridine-2 '-Ji)-1,2,3-triazoles) close the synthesis of iridium
Under nitrogen protection; 0.81g (0.3mmol) part is 2-(3 '; 5 '-two fluoro-4 '-trifluoromethyl)-5-eicosane oxygen yl pyrimidines containing iridium dichloro dimer; 0.13g (0.9mmol) 4-(pyridine-2 '-Ji)-1; 2,3-triazole and 0.16g (1.5mmol) sodium carbonate are dissolved in 30mL2-methyl cellosolve.Stirring reaction mixed solution is heated to 100 DEG C of back flow reaction 12h.Naturally, after being chilled to room temperature, in reaction solution, the appropriate distilled water of impouring, has solid to separate out.Collect crude product, use deionized water, methyl alcohol, washed with diethylether for several times successively.Crude product is through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, and obtain pure 0.08g pure products after drying, yield is 9.2%.
Structural Identification:
Mass spectrum (MS m/z): 1448.7 (M
+)
Ultimate analysis: C
69h
93f
10irN
8o
2
Theoretical value: C, 57.20; H, 6.47; F, 13.11; Ir, 13.27; N, 7.73; O, 2.21;
Measured value: C, 57.25; H, 6.41; F, 13.16; Ir, 13.21; N, 7.78; O, 2.19.
The material that the above-mentioned reaction of above data acknowledgement obtains is title complex two (2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-eicosane oxygen yl pyrimidines-N, C
2') (4-(pyridine-2 '-Ji)-1,2,3-triazoles) close iridium.
End product is CH at 298K temperature
2cl
2solution (~ 10
-5the maximum emission peak of the emmission spectrum M), at 500nm place, has an acromion at 524nm place, with the Ir of same concentrations (ppy) simultaneously
3cH
2cl
2solution is standard (Φ
pL=0.40) Φ of end product, is recorded
pL=0.003.
Embodiment 8:
Fig. 3 is the structural representation of organic electroluminescence device in embodiment 8.With the title complex that embodiment 1 is obtained two (2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl) pyrimidine-N, C
2') (4-(pyridine-2 '-Ji)-1,2,3-triazoles) close the organic electroluminescence device of iridium as luminescent layer doping object, structure as shown in Figure 3:
This device is followed successively by ITO (100nm)/PEDOT:PSS (40nm)/PVK:12wt%Ir title complex (50nm)/TmPyPB (20nm)/LiF (1nm)/Al (120nm), namely on the glass-based plate of pre-washing and UV-ozone process, depositing a layer thickness at one is 100nm, square resistance is that the tin indium oxide (ITO) of 10 ~ 20 Ω/mouth is as transparent anode 301, then on anode 301, spin coating a layer thickness is the PEDOT:PSS (poly-3 of 40nm, 4-ethylenedioxy thiophene/poly styrene sulfonate) hole-injecting material is as hole injection layer 302, 10min is toasted at 120 DEG C of temperature in nitrogen atmosphere, chlorobenzene solution spin coating a layer thickness is two (2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl) pyrimidine-N, the C that prepare doped with 12wt% embodiment 1 of 50nm
2') (4-(pyridine-2 '-Ji)-1,2,3-triazoles) close the PVK (Polyvinyl carbazole) of iridium as luminescent layer 303, then on this luminescent layer 303 spin coating a layer thickness be TmPyPB (1,3,5-tri-(the m-pyridin-3-yl phenyl) benzene) material of 20nm as electron transfer layer 304,80 DEG C of anneal 60min, last 5 × 10
-8in Torr vacuum evaporation a layer thickness be the LiF of 1nm as electron injection buffer layer 305, adopt vacuum plating techniques of deposition thickness to be the metal A l of 120nm on the buffer layer, as the negative electrode 306 of device.
Current versus brightness-the voltage characteristic of above-mentioned organic electroluminescence device is tested by Keithley source measuring system (Keithley2400Sourcemeter), with French its electroluminescent spectrum of JY company SPEX CCD3000 spectrometer measurement, all measurements all complete in atmosphere at room temperature, record the maximum emission wavelength of organic electroluminescence device at 475nm place, an acromion is had at 502nm place, the maximum external quantum efficiency of device is 4.3%, and maximum lumen efficiency is 3.8lm/W.
Should be understood that, the above-mentioned statement for present pre-ferred embodiments is comparatively detailed, and therefore can not think the restriction to scope of patent protection of the present invention, scope of patent protection of the present invention should be as the criterion with claims.
Claims (10)
1. a blue light organic phosphorescent electroluminescent materials, is characterized in that, the general structure of described blue light organic phosphorescent electroluminescent materials is as shown in P:
Wherein, R is hydrogen atom, C
1~ C
20alkyl or alkoxyl group.
2. a preparation method for blue light organic phosphorescent electroluminescent materials, is characterized in that, comprises the steps:
(1), under protective gas existent condition, by structural formula be
compd A and structural formula be
compd B and catalyzer be dissolved in the first organic solvent, then obtain reaction solution with the aqueous solution of alkali, described reaction solution carries out Suzuki linked reaction 6 ~ 12h at 85 ~ 100 DEG C of temperature, after question response stops, separating-purifying reaction solution, obtaining structural formula is
cyclic metal complexes; Wherein, the mol ratio of compd A and compd B is 1:1.1 ~ 1:1.5; Wherein, R is hydrogen atom, C
1~ C
20alkyl or alkoxyl group;
(2), under protective gas existent condition, be that 2.2:1 ~ 3:1 is dissolved in the mixed solvent that cellosolvo and water formed with mol ratio by described cyclic metal complexes and three hydrated iridium trichloride, heating mixed solvent is to reflux state stirring reaction 22 ~ 25h; Be cooled to room temperature, separating-purifying, obtaining structural formula is
chlorine bridge dipolymer; Wherein, R is hydrogen atom, C
1~ C
20alkyl or alkoxyl group;
(3), under protective gas existent condition, by described chlorine bridge dipolymer and structural formula be
compound C be in the second organic solvent of being dissolved in containing alkali of 1:2.2 ~ 1:3 with mol ratio, obtain reaction mixture, reacting by heating mixed solution to 100 ~ 135 DEG C, stirring and refluxing reaction 8 ~ 15h, be cooled to room temperature, separating-purifying, obtaining structural formula is
blue light organic phosphorescent electroluminescent materials; Wherein, R is hydrogen atom, C
1~ C
20alkyl or alkoxyl group.
3. the preparation method of blue light organic phosphorescent electroluminescent materials according to claim 2, it is characterized in that, catalyzer described in step (1) is that four (triphenylphosphines) close palladium or dichloro two (triphenyl phosphorus) closes palladium, and the mol ratio of described catalyzer and compd A is 0.03:1 ~ 0.05:1.
4. the preparation method of blue light organic phosphorescent electroluminescent materials according to claim 2, is characterized in that, described in step (1), the volumetric molar concentration of compd A in reaction solution is 0.1 ~ 0.2mol/L.
5. the preparation method of blue light organic phosphorescent electroluminescent materials according to claim 2, is characterized in that, described in step (3), the second organic solvent is 2-methyl cellosolve or cellosolvo.
6. the preparation method of blue light organic phosphorescent electroluminescent materials according to claim 2, is characterized in that, the concentration range of chlorine bridge dipolymer described in step (3) in reaction mixture is 0.01 ~ 0.02mol/L.
7. the preparation method of blue light organic phosphorescent electroluminescent materials according to claim 2, is characterized in that, described in step (1), the separating-purifying of cyclic metal complexes comprises:
After question response stops being cooled to room temperature, dichloromethane extraction, separatory, be washed to neutrality, with anhydrous magnesium sulfate drying; Filter, filtrate decompression steams solvent and obtains crude product, and the mixed solution formed with ethyl acetate and normal hexane is separated for elutriant carries out silica gel column chromatography, obtains described cyclic metal complexes after drying.
8. the preparation method of blue light organic phosphorescent electroluminescent materials according to claim 2, is characterized in that, described in step (2), the separating and purifying method of chlorine bridge dipolymer is:
Question response stop be cooled to room temperature after, the throw out in collecting by filtration reaction mixture, throw out uses ethanol, n-hexane successively, after vacuum-drying described chlorine bridge dipolymer or,
After question response stopping is cooled to room temperature, rotates and steam except partial solvent, add appropriate distilled water, filter and obtain solid, solid uses distilled water, methanol wash successively, obtains described chlorine bridge dipolymer after drying.
9. the preparation method of blue light organic phosphorescent electroluminescent materials according to claim 2, is characterized in that, described in step (3), the separating-purifying of blue light organic phosphorescent electroluminescent materials comprises:
After question response stops being cooled to room temperature, in reaction solution, the appropriate distilled water of impouring, has solid to separate out; Collecting by filtration crude product, uses deionized water, methyl alcohol, washed with diethylether for several times successively; Crude product obtains blue light organic phosphorescent electroluminescent materials after the mixed solvent recrystallization that methylene dichloride and dehydrated alcohol are formed.
10. an organic electroluminescence device, comprises luminescent layer, it is characterized in that, doped with blue light organic phosphorescent electroluminescent materials in described luminescent layer, described blue light organic phosphorescent electroluminescent materials general structure is as shown in P:
Wherein, R is hydrogen atom, C
1~ C
20alkyl or alkoxyl group.
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