CN104418905A - Organic iridium metal complex and preparation method and application thereof - Google Patents
Organic iridium metal complex and preparation method and application thereof Download PDFInfo
- Publication number
- CN104418905A CN104418905A CN201310367804.0A CN201310367804A CN104418905A CN 104418905 A CN104418905 A CN 104418905A CN 201310367804 A CN201310367804 A CN 201310367804A CN 104418905 A CN104418905 A CN 104418905A
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- CN
- China
- Prior art keywords
- metal complex
- iridium metal
- organic
- reaction
- organic iridium
- Prior art date
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- Pending
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- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 160
- -1 iridium metal complex Chemical class 0.000 title claims abstract description 128
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000000460 chlorine Substances 0.000 claims abstract description 35
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 35
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 29
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims description 91
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 57
- 150000003233 pyrroles Chemical class 0.000 claims description 57
- 239000000463 material Substances 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 32
- 239000012153 distilled water Substances 0.000 claims description 30
- 239000007810 chemical reaction solvent Substances 0.000 claims description 20
- 229910052763 palladium Inorganic materials 0.000 claims description 20
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 claims description 19
- 239000011734 sodium Substances 0.000 claims description 19
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 19
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 16
- 239000004327 boric acid Substances 0.000 claims description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 15
- 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 15
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 13
- 230000036571 hydration Effects 0.000 claims description 13
- 238000006703 hydration reaction Methods 0.000 claims description 13
- 229910052708 sodium Inorganic materials 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000005401 electroluminescence Methods 0.000 claims description 11
- 125000002524 organometallic group Chemical group 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 229960001701 chloroform Drugs 0.000 claims description 6
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- CWYDOHLKWBWYDZ-UHFFFAOYSA-N [O].C(CCCCC)OCCCCCCCCCCCCCCCCCCCC Chemical compound [O].C(CCCCC)OCCCCCCCCCCCCCCCCCCCC CWYDOHLKWBWYDZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical group CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 14
- 239000002184 metal Substances 0.000 abstract description 14
- 239000003446 ligand Substances 0.000 abstract description 8
- 238000004020 luminiscence type Methods 0.000 abstract description 4
- 229920001222 biopolymer Polymers 0.000 abstract 2
- UZFYVBCXALBYAJ-UHFFFAOYSA-N 2-fluoro-5-pyrimidin-2-ylbenzonitrile Chemical compound C1=C(C#N)C(F)=CC=C1C1=NC=CC=N1 UZFYVBCXALBYAJ-UHFFFAOYSA-N 0.000 abstract 1
- 150000002503 iridium Chemical class 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 description 58
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 54
- 239000010410 layer Substances 0.000 description 51
- 239000007787 solid Substances 0.000 description 42
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 39
- 239000000047 product Substances 0.000 description 31
- 239000002904 solvent Substances 0.000 description 30
- 238000001035 drying Methods 0.000 description 29
- 230000015572 biosynthetic process Effects 0.000 description 28
- 238000003786 synthesis reaction Methods 0.000 description 28
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- 238000003756 stirring Methods 0.000 description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 21
- 238000004458 analytical method Methods 0.000 description 21
- 238000001819 mass spectrum Methods 0.000 description 18
- 239000012043 crude product Substances 0.000 description 15
- 238000010992 reflux Methods 0.000 description 15
- 239000007788 liquid Substances 0.000 description 14
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 10
- 210000002659 acromion Anatomy 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 239000012046 mixed solvent Substances 0.000 description 10
- 230000004044 response Effects 0.000 description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 230000006837 decompression Effects 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000000605 extraction Methods 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 238000001953 recrystallisation Methods 0.000 description 9
- 238000010898 silica gel chromatography Methods 0.000 description 9
- 238000010189 synthetic method Methods 0.000 description 9
- 238000010792 warming Methods 0.000 description 9
- 238000005859 coupling reaction Methods 0.000 description 8
- 229960004132 diethyl ether Drugs 0.000 description 8
- 238000011160 research Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 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 description 7
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 229960000935 dehydrated alcohol Drugs 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 235000015320 potassium carbonate Nutrition 0.000 description 6
- 150000003230 pyrimidines Chemical class 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 230000003335 steric effect Effects 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011368 organic material Substances 0.000 description 5
- 125000000714 pyrimidinyl group Chemical group 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 125000004093 cyano group Chemical group *C#N 0.000 description 4
- 125000006575 electron-withdrawing group Chemical group 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000027756 respiratory electron transport chain Effects 0.000 description 4
- 238000004611 spectroscopical analysis Methods 0.000 description 4
- 0 *c(c(*)n1)c(*)nc1Br Chemical compound *c(c(*)n1)c(*)nc1Br 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 125000003963 dichloro group Chemical group Cl* 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 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 3
- DIVZFUBWFAOMCW-UHFFFAOYSA-N 4-n-(3-methylphenyl)-1-n,1-n-bis[4-(n-(3-methylphenyl)anilino)phenyl]-4-n-phenylbenzene-1,4-diamine Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 DIVZFUBWFAOMCW-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-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
- 239000011737 fluorine Substances 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 239000002346 layers by function Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical group [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- GNYSCXATUGEYET-UHFFFAOYSA-N 2,4,5-trimethylpyrimidine Chemical compound CC1=NC=C(C)C(C)=N1 GNYSCXATUGEYET-UHFFFAOYSA-N 0.000 description 1
- HBIXGSINRBEQRE-UHFFFAOYSA-N 2-bromo-4,5,6-trimethylpyrimidine Chemical compound Cc1nc(Br)nc(C)c1C HBIXGSINRBEQRE-UHFFFAOYSA-N 0.000 description 1
- JKYRQFSEYHIXIZ-UHFFFAOYSA-N 2-bromo-4,5-dimethylpyrimidine Chemical compound CC1=CN=C(Br)N=C1C JKYRQFSEYHIXIZ-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
- LSBIUXKNVUBKRI-UHFFFAOYSA-N 4,6-dimethylpyrimidine Chemical compound CC1=CC(C)=NC=N1 LSBIUXKNVUBKRI-UHFFFAOYSA-N 0.000 description 1
- MBPCKEZNJVJYTC-UHFFFAOYSA-N 4-[4-(n-phenylanilino)phenyl]aniline Chemical compound C1=CC(N)=CC=C1C1=CC=C(N(C=2C=CC=CC=2)C=2C=CC=CC=2)C=C1 MBPCKEZNJVJYTC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000007812 deficiency 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
- 238000010586 diagram Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000012360 testing method Methods 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
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
Landscapes
- 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
The invention discloses an organic iridium metal complex and a preparation method and an application thereof. A molecular structure general formula of the organic iridium metal complex is shown in (I), wherein, R1, R2, R3 in (I) are the same or different H, alkyl or alkoxy. The preparation method comprises the steps of preparing a chlorine bridge biopolymer and using the chlorine bridge biopolymer to prepare the organic iridium metal complex with the structure general formula (I). The above organic iridium metal complex takes 2-(3'-cyan-4'-fluorophenyl)pyrimidine as a main structure of an iridium metal ligand, and the organic iridium metal complex has high blue light purity and luminescence efficiency.
Description
Technical field
The invention belongs to organic electromechanical phosphorescent material technical field, relate to a kind of organic iridium metal complex and its preparation method and application specifically.
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 (Alq3) for luminescent material, the high-quality thin film of even compact is made with aromatic diamine, obtain 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.
So far, constantly deeply, but there is bottleneck problem to the research of organic electromechanical phosphorescent material iridium metal complex in people in the efficiency decay etc. of the illuminant colour purity of blue emitting phosphor material, luminous efficiency and device.Its major cause be the title complex of existing iridium metals ion on the one hand due to cyclic metal complexes agent structure itself, have impact on the luminescence of phosphor material; On the other hand, easily there is direct effect between the atoms metal in the title complex of metal ion and cause the generation of the self-quenching phenomenon of triplet exciton, thus having had a strong impact on the electroluminescent properties of phosphorescent light-emitting materials.Therefore, the blue phosphorescent organic electroluminescent material how developing high color purity and luminous efficiency becomes the technical barrier expanded blue light material and apply in electroluminescent device.
Summary of the invention
The object of the invention is to the above-mentioned deficiency overcoming prior art, a kind of organic iridium metal complex is newly provided, to solve existing organic iridium metal complex blue light color purity and the not high technical problem of luminous efficiency.
Another object of the present invention is to provide a kind of productive rate high, the organic iridium metal complex preparation method be easy to operate and control.
Another object of the present invention is the application providing above-mentioned organic iridium metal complex.
In order to realize foregoing invention object, technical scheme of the present invention is as follows:
A kind of organic iridium metal complex, its general formula of molecular structure is following (I):
In formula, R
1, R
2, R
3identical or not identical is H, alkyl or alkoxyl group.
And a kind of preparation method of organic iridium metal complex, comprises the steps:
The compd A of following structural formula general formula is provided:
In the environment of anaerobic, described compd A and hydrated iridium trichloride or hydration chlorine sub-iridium acid sodium are carried out thermal backflow reaction in reaction solvent, generate the chlorine bridge dipolymer B of following structural formula general formula:
In the environment of anaerobic, by described chlorine bridge dipolymer B and 2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles carries out thermal backflow reaction under carbonate, sodium methylate and/or sodium ethylate catalyst action and in the reaction solvent of 84 ~ 135 DEG C, purifying, obtains organic iridium metal complex of following general formula of molecular structure (I):
Wherein, the R in compd A, B and general structure (I)
1, R
2, R
3identical or not identical is H, alkyl or alkoxyl group.
And above-mentioned organic iridium metal complex is as the application of blue electrophosphorescence material in organic electroluminescence device, EL cold light film or electrochemical cell luminescent device.
Above-mentioned organic iridium metal complex is cyclic metal complexes agent structure with 2-(3'-cyano group-4'-fluorophenyl) pyrimidine, and with 2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles is assistant ligand, gives the high blue light color purity of this organic iridium metal complex and luminous efficiency.Wherein, pyrimidine group on 2-(3'-cyano group-4'-fluorophenyl) the main part of pyrimidine is conducive to the lumo energy improving this organic iridium metal complex, on phenyl ring, two strong electron-withdrawing group F bases and cyano group are conducive to the HOMO energy level reducing this organic iridium metal complex, make the effective blue shift of material emission wavelength; When the R substituent group on pyrimidine ring is for alkyl or alkoxyl group, the alkyl of this introducing or alkoxyl group on the one hand its electro mass-energy of giving obtain satisfied blue light emitting wavelength, on the one hand the different lengths carbochain of alkyl or alkoxyl group is conducive to increasing its solvability in organic solvent in addition, and produce certain space steric effect, thus the direct effect between atoms metal can be stoped, significantly reduce the self-quenching phenomenon of triplet exciton; Strong electron-withdrawing group fluorine-based, the cyano group of group and high field intensity assistant ligand 2 on phenyl ring, the introducing of 4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles can also improve luminescent properties, be beneficial to evaporation, increase film-forming properties and improve the stability of device.
Above-mentioned organic iridium metal complex preparation method only needs 2-3 to walk the reaction of ripe type, and target product is easily deducted a percentage, and productive rate is high, and its reaction is easy to operate and control, and is suitable for suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the schema of the organic iridium metal complex preparation method of the embodiment of the present invention;
Fig. 2 is two (2-(the fluoro-5'-cyano-phenyl of 4'-) pyrimidine-N, C prepared by embodiment 1
2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close the spectroscopic analysis figure of iridium metal complex;
Fig. 3 is two (2-(the fluoro-5'-cyano-phenyl of 4'-)-5-methoxy pyrimidine-N, C prepared by embodiment 5
2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close the spectroscopic analysis figure of iridium metal complex;
Fig. 4 is two (2-(the fluoro-5'-cyano-phenyl of 4'-) pyrimidine-N, the C that prepare with embodiment 1
2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close the OLED structure schematic diagram that iridium metal complex is electroluminescent organic material.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The invention provides and a kind ofly have blue light color purity and the high organic iridium metal complex of luminous efficiency, its general formula of molecular structure is following (I):
Particularly, the R in (I) formula
1, R
2, R
3identical or not identical is H, alkyl or alkoxyl group.Therefore, this general formula of molecular structure (I) organic iridium metal complex at least has following several molecular structural formula:
Ra, Rb, Rc in above-mentioned I 1 to I 7 molecular structural formula are identical or not identical alkyl or alkoxyl group.
Lead in organic iridium metal complex of formula I at said structure, on pyrimidine ring, the introducing of alkyl or alkoxyl group mainly has the effect of following aspect:
1. it has to electronic property, makes the emission wavelength blue shift of this organic iridium metal complex, obtains satisfied blue light emitting wavelength;
2. increase the branch arm of this organic iridium metal complex, thus increase the three-dimensional space steric effect of this organic iridium metal complex, stop the interaction between molecule and accumulation, effectively suppress organic iridium metal complex crystallinity, improve organic iridium metal complex solvability and film forming properties;
3., simultaneously due to the introducing of alkyl or alkoxyl group, add the three-dimensional space steric effect of this organic iridium metal complex, effectively reduce the interatomic direct effect of iridium metals, thus significantly reduce the self-quenching phenomenon of triplet exciton.
Therefore, in order to make organic iridium metal complex in above-described embodiment, there is more excellent three-dimensional space steric effect, as the preferred embodiments of the present invention, this organic iridium metal complex is preferably organic iridium metal complex of above-mentioned I 3 to I 7, be more preferably organic iridium metal complex that molecular structural formula is I 7, namely said structure leads to the R in organic iridium metal complex of formula I
1, R
2, R
3be alkyl or alkoxy base.
In further preferred embodiment, the alkyl representated by Ra, Rb, Rc in this above-mentioned I 1 to I 7 molecular structural formula or alkoxyl group are C
1~ C
20straight or branched alkyl or alkoxy base.
In a particular embodiment, be also the preferred embodiment of the invention, when Ra, Rb, Rc are alkyl group, the alkyl group in the various embodiments described above is methyl (-CH
3), the tertiary butyl (-C (CH
3)
3), one or both or three kinds in n-hexyl, NSC 62789 base; When Ra, Rb, Rc are alkoxy base, the alkoxy base in the various embodiments described above is at least one in methoxyl group, hexyloxy, eicosane oxygen base.
Thus, organic iridium metal complex of above-mentioned general formula of molecular structure (I) is cyclic metal complexes agent structure with 2-(3'-cyano group-4'-fluorophenyl) pyrimidine, and with 2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles is assistant ligand, gives the high blue light color purity of this organic iridium metal complex and luminous efficiency.Wherein, pyrimidine group on 2-(3'-cyano group-4'-fluorophenyl) the main part of pyrimidine is conducive to the lumo energy improving this organic iridium metal complex, on phenyl ring, two strong electron-withdrawing group F bases and cyano group are conducive to the HOMO energy level reducing this organic iridium metal complex, make the effective blue shift of material emission wavelength, the concrete organic iridium metal complex utilizing emitted light spectrogram as Examples below 1 preparation; When the R substituent group on pyrimidine ring is for alkyl or alkoxyl group, the electro mass-energy of giving of the alkyl of this introducing or alkoxyl group one side alkyl or alkoxyl group obtains satisfied blue light emitting wavelength, on the one hand the different lengths carbochain of alkyl or alkoxyl group is conducive to increasing its solvability in organic solvent in addition, and produce certain space steric effect, thus the direct effect between atoms metal can be stoped, significantly reduce the self-quenching phenomenon of triplet exciton; In addition, by the selection to alkyl or alkoxy substituent group, the space steric effect of this organic iridium metal complex and solvent borne and film-forming properties can be improved further.Therefore, strong electron-withdrawing group fluorine-based, the cyano group of group and high field intensity assistant ligand 2 on phenyl ring, the introducing of 4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles can also improve luminescent properties, is beneficial to evaporation, increases film-forming type and improves the stability of device.
Correspondingly, the embodiment of the present invention additionally provides the method that one may be used for the organic iridium metal complex preparing above-mentioned general formula of molecular structure (I), and its preparation method flow process as shown in Figure 1.This organic iridium metal complex preparation method comprises the steps:
S01., the compd A of following structural formula general formula is provided;
S02. compd A is utilized to prepare chlorine bridge dipolymer B: in the environment of anaerobic, the compd A provided in step S01 and hydrated iridium trichloride or hydration chlorine sub-iridium acid sodium are carried out thermal backflow reaction in reaction solvent, generate the chlorine bridge dipolymer B of following structural formula general formula:
S03. by chlorine bridge dipolymer B and 2, 4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles carries out organic iridium metal complex that ligand exchange reaction prepares general formula of molecular structure (I): in the environment of anaerobic, by the chlorine bridge dipolymer B and 2 prepared in step S02, 4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles is at carbonate, thermal backflow reaction (i.e. ligand exchange reaction) is carried out under sodium methylate and/or sodium ethylate catalyst action in the reaction solvent of 84 ~ 135 DEG C, purifying, obtain organic iridium metal complex of following general formula of molecular structure (I):
Particularly, in above-mentioned steps S01, the R in compd A molecular structural formula
1, R
2, R
3identical or not identical is H, alkyl or alkoxyl group.Due to the ring master metal ligand structure that compd A is the organic iridium metal complex of above-described embodiment.Therefore, compd A at least has 7 kinds of structural formulas of (I 1) to (I 7) be similar to as organic iridium metal complex of above-mentioned general formula of molecular structure (I), in order to save length, does not repeat them here.
As preferred embodiment, above-claimed cpd A can be prepared as follows:
In anaerobic, alkaline environment and organo-metallic palladium catalyst, under organic solvent existent condition, the Compound C of following structural formula general formula and 3-cyano group-4-fluorobenzoic boric acid are carried out purifying after Suzuki linked reaction,
Particularly, to carry out the chemical equation of Suzuki linked reaction as follows for this Compound C and 3-cyano group-4-fluorobenzoic boric acid:
Wherein, the R in Compound C
1, R
2, R
3identical or not identical is H, alkyl or alkoxyl group, and it can be directly commercial or be prepared acquisition according to vitochemical ultimate principle.
In this Suzuki linked reaction, the condition of this Suzuki coupled reaction can directly be arranged according to the condition of the Suzuki coupled reaction of existing routine.In order to improve the Suzuki coupled reaction speed between Compound Compound C and 3-cyano group-4-fluorobenzoic boric acid, improve the productive rate of compd A, in a preferred embodiment, the condition setting of this Suzuki coupled reaction is: temperature is 85 ~ 100 DEG C, and the reaction times is 6 ~ 12 hours.
In addition, the consumption of the reactant compound C in this Suzuki linked reaction and 3-cyano group-4-fluorobenzoic boric acid can directly add according to ratio in both chemical equation.In order to impel the Suzuki coupled reaction speed between Compound C and 3-cyano group-4-fluorobenzoic boric acid, improve the productive rate of compd A, in a preferred embodiment, the mol ratio of reactant compound C and 3-cyano group-4-fluorobenzoic boric acid consumption is 1:(1 ~ 1.5).In another preferred embodiment, the concentration of this Compound C in reaction solvent is 0.1 ~ 0.2mol/L.In a particular embodiment, this reaction solvent can select the solvent that Suzuki coupled reaction is conventional, in a preferred embodiment, this reaction solvent is the mixed solvent of volume ratio close to 2:1 of organic solvent and water, wherein, this organic solvent can be dimethyl formamide (DMF), toluene etc.
Organo-metallic palladium catalyst in this Suzuki linked reaction, in further preferred embodiment, this organic palladium catalyzer is tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chloride, at least one of three (dibenzalacetone) two in palladium.In another preferred embodiment, the mole dosage of this organo-metallic palladium catalyst and 2 ~ 5% of Compound C mole dosage.
As further preferred embodiment, this organo-metallic palladium catalyst is tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chloride, at least one of three (dibenzalacetone) two in palladium, and 2 ~ 5% of the mole dosage of organo-metallic palladium catalyst and Compound C mole dosage.
As in another preferred embodiment, the condition setting of this Suzuki coupled reaction is: temperature is 85 ~ 100 DEG C, and the reaction times is 6 ~ 12 hours, the mole dosage of organo-metallic palladium catalyst and 2 ~ 5% of Compound C mole dosage.
Above-mentioned each preferred embodiment can improve Suzuki coupled reaction speed further, improves the productive rate of compd A simultaneously.
Alkaline environment in this Suzuki linked reaction ensure that carrying out smoothly of Suzuki linked reaction, and wherein, alkaline environment can be provided, as Cs by the basic cpd that Suzuki linked reaction is conventional
2cO
3, K
2cO
3, Na
2cO
3in one or more mixture, its addition is 1 ~ 3 times of Compound C mole dosage.
Purification process through Suzuki linked reaction products therefrom can operate according to the method for Examples below 1.
In above-mentioned steps S02, hydrated iridium trichloride can be expressed as IrCl
3xH
2o, hydration chlorine sub-iridium acid sodium can be expressed as Na
3irCl
6xH
2o, wherein, x value is preferably 1 ~ 3.Therefore, IrCl
3xH
2o can be IrCl
33H
2o, Na
3irCl
6xH
2o can be Na
3irCl
63H
2o.Certainly, x can also be other values, and like this, hydrated iridium trichloride, hydration chlorine sub-iridium acid sodium also can also be other hydrates.
The temperature of the thermal backflow reaction in this step S02 is determined according to the boiling nature of selected reaction solvent.And this reaction solvent is preferably the mixture of 2-methyl cellosolve, cellosolvo, methylene dichloride, trichloromethane at least one or 2-methyl cellosolve, cellosolvo, methylene dichloride, trichloromethane at least one and distilled water.Be more preferably the mixture of cellosolvo and distilled water.Therefore, the temperature that in this step S02, thermal backflow is reacted is preferably the temperature during thermal backflow of this preferred reaction solvent, and at this preferred thermal backflow temperature, the time of thermal backflow reaction is preferably 20 ~ 30 hours.Certainly, this reaction solvent also can select other alcohol derivate solvent, can also select other organic solvents, therefore, temperature, the time of this step thermal backflow reaction can also be other temperature, time, and when temperature is relatively low, the thermal backflow time can correspondingly extend.
Oxygen-free environment in this step S02 can be vacuum or be full of rare gas element to realize.Realize oxygen-free environment more easily realize owing to being full of rare gas element, therefore, be preferably full of rare gas element to realize oxygen-free environment, this rare gas element is the conventional rare gas element of the art, such as argon gas etc.This oxygen-free environment ensure that the stable of reactant, improves the yield of chlorine bridge dipolymer B.
The chemical equation that compd A in this step S02 and hydrated iridium trichloride or hydration chlorine sub-iridium acid sodium react through thermal backflow is as follows:
Therefore, in above-mentioned steps S02, compd A is 2:1 with the mole dosage ratio of hydrated iridium trichloride or hydration chlorine sub-iridium acid sodium theory, therefore, in order to allow hydrated iridium trichloride or the abundant complete reaction of the sub-iridium acid sodium of hydration chlorine, then compd A is preferably >=2:1 with the mole dosage ratio of iridous chloride or hydration chlorine sub-iridium acid sodium, is preferably (2 ~ 4): 1.Wherein, the concentration range of this iridic compound in reaction solvent is preferably 0.1 ~ 0.2mmol/L.Certainly, compd A also can be allowed fully to react, therefore, compd A is preferably≤2:1 with the mole dosage ratio of hydrated iridium trichloride or hydration chlorine sub-iridium acid sodium.
After the thermal backflow cyclization of step S02, reacted product carried out filter, after purifying and drying treatment, obtain pure compd B.The method of this purifying can be undertaken by the purification process of Examples below 1.
Because the compd B of preparation contains compd A cyclic metal complexes agent structure, again because compd A at least exists 7 kinds of structural formulas mentioned above, therefore compd B equally at least has the 7 kinds of structural formulas be similar to as this compd A, in order to save length, does not repeat them here.
In above-mentioned steps S03, chlorine bridge dipolymer B and 2, the temperature of 4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles's thermal backflow reaction is determined according to the boiling nature of selected reaction solvent, and the temperature of its back flow reaction is preferably 84 ~ 135 DEG C.Therefore, this reaction solvent is preferably at least one in cellosolvo, 2-methyl cellosolve, 1,2-ethylene dichloride, methylene dichloride, trichloromethane.Therefore, the temperature that in this step S03, thermal backflow is reacted is preferably the temperature during thermal backflow of this preferred reaction solvent.The time of thermal backflow reaction is relevant with the temperature of thermal response, and in order to make reactant fully react, time as relatively low in temperature, the thermal backflow time can correspondingly extend.In a preferred embodiment, at this preferred thermal backflow temperature, the time of thermal backflow reaction is preferably 6 ~ 10 hours.
The chemical equation that chlorine bridge dipolymer B in this step S03 and 2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles heat is reacted through thermal backflow is as follows:
Therefore, in above-mentioned steps S03 2, the mole dosage of 4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles and compd B theory is than being 2:1, in order to make the abundant complete reaction of compd B, 2, the mole dosage of 4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles and compd B, than being preferably >=2:1, is preferably (2 ~ 4): 1.Wherein, the concentration of compd B in reaction solvent is preferably 0.01 ~ 0.02mol/L.
In addition, in order to improve the efficiency of thermal backflow reaction in this step S03, improve the yield of target product, in a preferred embodiment, sodium methylate and/or sodium ethylate catalyzer are (8 ~ 12) with the mole dosage ratio of chlorine bridge dipolymer B: 1.
In further preferred embodiment, carbonate, sodium methylate and/or sodium ethylate catalyzer are (8 ~ 12) with the mole dosage ratio of chlorine bridge dipolymer B: 1, the mole dosage of 2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles and chlorine bridge dipolymer B is than being (3 ~ 2): 1.In a particular embodiment, this carbonate can be salt of wormwood, sodium carbonate etc.
Oxygen-free environment in this step S03 can be vacuum or be full of rare gas element to realize.Realize oxygen-free environment more easily realize owing to being full of rare gas element, therefore, be preferably full of rare gas element to realize oxygen-free environment, this rare gas element is the conventional rare gas element of the art, such as argon gas etc.This oxygen-free environment ensure that the stable of reactant, improves the yield of reaction product.
After the thermal backflow cyclization of step S03, reacted product carried out filter, after purifying and drying treatment, obtain organic iridium metal complex of pure general formula of molecular structure (I).The method of this purifying can be carried out according to the purification process of Examples below 1.
Reactant only need be carried out thermal backflow and react by above-mentioned organic iridium metal complex preparation method, and the one-tenth ripening reaction only needing 2-3 to walk is without the need to special equipment and environmental requirement, and its preparation method technique is simple, productive rate is high, and mild condition, be easy to operate and control, be suitable for suitability for industrialized production.
Have as above-mentioned high blue light color purity and luminous efficiency just because of the organic iridium metal complex of above-described embodiment, and by the group in cyclic metal complexes agent structure if alkyl or alkoxy base are to the adjustment of emission wavelength, its solubleness, good film-forming property, self-quenching phenomenon incidence is low, there is charge transport properties simultaneously good, therefore, this organic iridium metal complex can as the application of blue electrophosphorescence material in organic electroluminescence device, EL cold light film or electrochemical cell luminescent device.In application process, can using organic for embodiment of the present invention iridium metal complex as luminescent layer or with other luminescent material compound uses, prepare and there is stable luminescence, and the electroluminescent device that luminous efficiency is high.
Particularly, when the organic iridium metal complex of above-described embodiment as blue electrophosphorescence at organic electroluminescence device (organic electroluminescent LED, during application OLED), this organic electroluminescence device comprises substrate layer, the first electrode layer, organic function layer and the second electrode lay.Wherein, organic function layer comprises the hole transmission layer of stacked setting, at least one luminescent layer and electron transfer layer, and the luminescent material of this luminescent layer contains the organic iridium metal complex of above-described embodiment.
Certainly, the organic function layer of this organic electroluminescence device can also comprise the functional layers such as hole injection layer, electron injecting layer, hole blocking layer, electronic barrier layer, and this functional layer is conveniently stacked to be arranged.Containing the organic iridium metal complex of above-described embodiment in the luminescent layer of this organic electroluminescence device, the material selection material known in this field of other each Rotating fields, its preparation method also can according to the existing method preparation in this area.
Particularly, when the organic iridium metal complex of above-described embodiment is as the application of blue electrophosphorescence material in electrochemical cell luminescent device, this electrochemical cell luminescent device comprises anode, negative electrode and is arranged at least one luminescent layer between this anode, negative electrode, and the luminescent material of this luminescent layer contains the organic iridium metal complex of above-described embodiment.Wherein, containing the organic iridium metal complex of above-described embodiment in the luminescent layer of this electrochemical cell luminescent device, the material selection material known in this field of anode, negative electrode, its preparation method also can according to the existing method preparation in this area.
Now in conjunction with the embodiments, the present invention is further elaborated.
Embodiment 1
Two (2-(the fluoro-5'-cyano-phenyl of 4'-) pyrimidine-N, C
2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close iridium metal complex and synthetic method thereof:
(1) synthesis of 2-(3'-cyano group-4'-fluorophenyl) pyrimidine:
Under nitrogen protection, 1.59g (10mmol) 2-bromo pyrimi piperidine, 1.98g (12mmol) 3-cyano group-4-fluorobenzoic boric acid and 0.58g (0.5mmol) four (triphenyl phosphorus) close palladium and are dissolved in 40mL toluene, drip the aqueous solution of 20mL containing 2.76g (20mmol) salt of wormwood 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 1/6 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 1.31g, yield is 65.8%; Its chemical equation is as follows:
2-(3'-cyano group-4'-fluorophenyl) pyrimidine product is carried out the result of Structural Identification:
Mass spectrum (MS m/z): 199.0 (M
+); Ultimate analysis: C11H6FN3; Theoretical value: C, 66.33; H, 3.04; F, 9.54; N, 21.10; Measured value: C, 66.37; H, 3.02; F, 9.50; N, 21.11.The material that the above-mentioned reaction of this data acknowledgement obtains is 2-(3'-cyano group-4'-fluorophenyl) pyrimidine.
(2) part be 2-(3'-cyano group-4'-fluorophenyl) pyrimidine containing the dimeric synthesis of iridium dichloro:
Under nitrogen protection, 0.36g (1mmol) three hydrated iridium trichloride, it is in the cellosolvo/water mixed liquid of 3:1 that 0.50g (2.5mmol) 2-(3'-cyano group-4'-fluorophenyl) pyrimidine is dissolved in 20mL volume ratio, 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 0.39g after drying, yield is 62.5%; Its chemical equation is as follows:
(3) two (2-(the fluoro-5'-cyano-phenyl of 4'-) pyrimidine-N, C
2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close the synthesis of iridium metal complex:
Under nitrogen protection, 0.62g (0.5mmol) part be 2-(3'-cyano group-4'-fluorophenyl) pyrimidine containing iridium dichloro dimer and 0.34g (1.2mmol) 2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles and 0.53g (5mmol) sodium carbonate are dissolved in 25mL2-ethoxy ethanol solvent, and stirring heating is warming up to 135 DEG C of reflux state reaction 6h; Naturally, after being chilled to room temperature, appropriate distilled water precipitating is added; Filter, collecting precipitation, solid uses deionized water, washed with diethylether successively, and obtain 0.34g pure products through methylene dichloride and anhydrous methanol mixed solvent recrystallization, yield is 39.2%; Its chemical equation is as follows:
Product is carried out the result of Structural Identification:
Mass spectrum (MS m/z): 868.1 (M
+); Ultimate analysis: C33H15F8IrN8; Theoretical value: C, 45.68; H, 1.74; F, 17.52; Ir, 22.15; N, 12.91; Measured value: C, 45.62; H, 1.82; F, 17.47; Ir, 22.19; N, 12.90.The material that the above-mentioned reaction of this data acknowledgement obtains is two (2-(the fluoro-5'-cyano-phenyl of 4'-) pyrimidine-N, C
2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close iridium metal complex.
Embodiment 2
Two (2-(the fluoro-5'-cyano-phenyl of 4'-)-5-methylpyrimidine-N, C
2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close iridium metal complex and synthetic method thereof:
(1) synthesis of 2-(3'-cyano group-4'-fluorophenyl)-5-methylpyrimidine:
Under nitrogen protection, the bromo-5-methylpyrimidine of 1.73g (10mmol) 2-, 1.65g (10mmol) 3-cyano group-4-fluorobenzoic boric acid and 0.28g (0.4mmol) dichloro two (triphenyl phosphorus) close palladium and are dissolved in 50mL DMF, drip the aqueous solution of 25mL containing 3.18g (30mmol) sodium carbonate 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 1/8 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 1.17g, yield is 54.9%; Product is carried out the result of Structural Identification:
Mass spectrum (MS m/z): 213.1 (M
+); Ultimate analysis: C12H8FN3; Theoretical value: C, 67.60; H, 3.78; F, 8.91; N, 19.71; Measured value: C, 67.66; H, 3.74; F, 8.88; N, 19.72.The material that the above-mentioned reaction of this data acknowledgement obtains is 2-(3'-cyano group-4'-fluorophenyl)-5-methylpyrimidine.
(2) part be 2-(3'-cyano group-4'-fluorophenyl)-5-methylpyrimidine containing the dimeric synthesis of iridium dichloro:
Under nitrogen protection, 0.36g (1mmol) three hydrated iridium trichloride, it is in the cellosolvo/water mixed liquid of 3:1 that 0.43g (2mmol) 2-(3'-cyano group-4'-fluorophenyl)-5-methylpyrimidine is dissolved in 20mL volume ratio, 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 0.36g after drying, yield is 55.2%;
(3) two (2-(the fluoro-5'-cyano-phenyl of 4'-)-5-methylpyrimidine-N, C
2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close the synthesis of iridium metal complex:
Under nitrogen protection, 0.65g (0.5mmol) part be 2-(3'-cyano group-4'-fluorophenyl)-5-methylpyrimidine containing iridium dichloro dimer, 0.28g (1mmol) 2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles and 0.55g (4mmol) salt of wormwood are dissolved in 30mL2-methyl cellosolve, and stirring heating is warming up to 100 DEG C of state of temperature reaction 8h; Naturally after being chilled to room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, has solid to separate out; Filter, collect crude product, solid uses deionized water, washed with diethylether for several times successively, and obtain 0.28g pure products through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 31.2%; Product is carried out the result of Structural Identification:
Mass spectrum (MS m/z): 896.1 (M
+); Ultimate analysis: C35H19F8IrN8; Theoretical value: C, 46.93; H, 2.14; F, 16.97; Ir, 21.46; N, 12.51; Measured value: C, 46.97; H, 2.08; F, 17.02; Ir, 21.40; N, 12.53.The material that the above-mentioned reaction of above data acknowledgement obtains is two (2-(the fluoro-5'-cyano-phenyl of 4'-)-5-methylpyrimidine-N, C
2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close iridium metal complex.
Embodiment 3
Two (2-(the fluoro-5'-cyano-phenyl of 4'-)-5-t-butyl pyrimidines-N, C
2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close iridium metal complex and synthetic method thereof:
(1) synthesis of 2-(3'-cyano group-4'-fluorophenyl)-5-t-butyl pyrimidines:
Under nitrogen protection; 2.15g (10mmol) 2-bromo-5-t-butyl pyrimidines, 2.22g (14mmol) 3-cyano group-4-fluorobenzoic boric acid and the two chlorine two (triphenyl phosphorus) of 0.21g (0.3mmol) are closed palladium and are dissolved in 35mL DMF, drip the aqueous solution of 15mL containing 1.06g (10mmol) sodium carbonate 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 1/8 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 1.17g, yield is 45.8%; Product is carried out the result of Structural Identification:
Mass spectrum (MS m/z): 255.1 (M
+); Ultimate analysis: C15H14FN3; Theoretical value: C, 70.57; H, 5.53; F, 7.44; N, 16.46; Measured value: C, 70.53; H, 5.58; F, 7.42; N, 16.47.The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(3'-cyano group-4'-fluorophenyl)-5-t-butyl pyrimidines.
(2) part be 2-(3'-cyano group-4'-fluorophenyl)-5-t-butyl pyrimidines containing the dimeric synthesis of iridium dichloro:
Under nitrogen protection, the Na of 1mmol
3irCl
63H
2o and 0.76g (3mmol) 2-(3'-cyano group-4'-fluorophenyl)-5-t-butyl pyrimidines is dissolved in 20mL2-ethoxy ethanol/water (3/1) mixed solution, 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 0.29g after drying, yield is 38.4%;
(3) two (2-(the fluoro-5'-cyano-phenyl of 4'-)-5-t-butyl pyrimidines-N, C
2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close the synthesis of iridium metal complex:
Under nitrogen protection, 0.59g (0.4mmol) part be 2-(3'-cyano group-4'-fluorophenyl)-5-t-butyl pyrimidines containing iridium dichloro dimer, 0.28g (1mmol) 2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles and 0.51g (4.8mmol) sodium carbonate are dissolved in 30mL2-ethoxy ethanol, and stirring heating reacts 9h under being warming up to 90 DEG C of state of temperatures; Naturally after being chilled to room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, has solid to separate out; Filter, collect crude product, solid uses deionized water, washed with diethylether for several times successively, and obtain 0.16g pure products through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 20.4%; Product is carried out the result of Structural Identification:
Mass spectrum (MS m/z): 980.2 (M
+); Ultimate analysis: C41H31F8IrN8; Theoretical value: C, 50.25; H, 3.19; F, 15.51; Ir, 19.62; N, 11.43; Measured value: C, 50.21; H, 3.15; F, 15.44; Ir, 19.68; N, 11.42.The material that the above-mentioned reaction of above data acknowledgement obtains is two (2-(the fluoro-5'-cyano-phenyl of 4'-)-5-t-butyl pyrimidines-N, C
2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close iridium metal complex.
Embodiment 4
Two (2-(the fluoro-5'-cyano-phenyl of 4'-)-4-eicosyl pyrimidine-N, C
2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close iridium metal complex and synthetic method thereof:
(1) synthesis of 2-(3'-cyano group-4'-fluorophenyl)-4-eicosyl pyrimidine:
Under nitrogen protection, 2.20g (5mmol) 2-bromo-4-eicosyl pyrimidine, 1.19g (7.5mmol) 3-cyano group-4-fluorobenzoic boric acid and 0.12g (0.1mmol) four (triphenyl phosphorus) close palladium and are dissolved in 35mL toluene, drip the aqueous solution of 15mL containing 1.73g (12.5mmol) salt of wormwood 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 1/5 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 0.72g, yield is 30.0%; Product is carried out the result of Structural Identification:
Mass spectrum (MS m/z): 479.4 (M
+); Ultimate analysis: C31H46FN3; Theoretical value: C, 77.62; H, 9.67; F, 3.96; N, 8.76; Measured value: C, 77.67; H, 9.61; F, 3.97; N, 8.75.The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(3'-cyano group-4'-fluorophenyl)-4-eicosyl pyrimidine.
(2) part be 2-(3'-cyano group-4'-fluorophenyl)-4-eicosyl pyrimidine containing the dimeric synthesis of iridium dichloro:
Under nitrogen protection, 0.18g (0.5mmol) three hydrated iridium trichloride, 0.96g (2mmol) 2-(3'-cyano group-4'-fluorophenyl)-4-eicosyl pyrimidine is dissolved in 10mL2-ethoxy ethanol/water (3/1) mixed solution, 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 0.11g after drying, yield is 20.5%; Dipolymer, without the need to further purification, can directly drop in next step reaction.
(3) two (2-(the fluoro-5'-cyano-phenyl of 4'-)-4-eicosyl pyrimidine-N, C
2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close the synthesis of iridium metal complex:
Under nitrogen protection, 0.64g (0.3mmol) part be 2-(3'-cyano group-4'-fluorophenyl)-4-eicosyl pyrimidine containing iridium dichloro dimer, 0.25g (0.9mmol) 2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles and 0.16g (3mmol) sodium methylate are dissolved in 30mL1, in 2-ethylene dichloride, stirring heating is warming up to 84 DEG C of reflux state reaction 10h; Naturally after being chilled to room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, has solid to separate out; Filter, collect crude product, solid uses deionized water, washed with diethylether for several times successively, and obtain 0.08g pure products through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 9.3%; Product is carried out the result of Structural Identification:
Mass spectrum (MS m/z): 1428.7 (M
+); Ultimate analysis: C73H95F8IrN8; Theoretical value: C, 61.37; H, 6.70; F, 10.64; Ir, 13.45; N, 7.84; Measured value: C, 61.33; H, 6.76; F, 10.62; Ir, 13.41; N, 7.88.The material that the above-mentioned reaction of above data acknowledgement obtains is title complex two (2-(the fluoro-5'-cyano-phenyl of 4'-)-4-eicosyl pyrimidine-N, C
2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close the synthesis of iridium metal complex.
Embodiment 5
Two (2-(the fluoro-5'-cyano-phenyl of 4'-)-5-methoxy pyrimidine-N, C
2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close iridium metal complex and synthetic method thereof:
(1) synthesis of 2-(3'-cyano group-4'-fluorophenyl)-5-methoxy pyrimidine:
Under nitrogen protection, the bromo-5-methoxy pyrimidine of 1.89g (10mmol) 2-, 1.65g (12mmol) 3-cyano group-4-fluorobenzoic boric acid and 0.58g (0.5mmol) four (triphenyl phosphorus) close palladium and are dissolved in 35mL DMF, drip the aqueous solution of 15mL containing 2.76g (20mmol) salt of wormwood 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 1/7 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 1.14g, yield is 49.7%; Its chemical equation is as follows:
Product is carried out the result of Structural Identification:
Mass spectrum (MS m/z): 229.1 (M
+); Ultimate analysis: C12H8FN3O; Theoretical value: C, 62.88; H, 3.52; F, 8.29; N, 18.33; O, 6.98; Measured value: C, 62.84; H, 3.57; F, 8.25; N, 18.38; O, 6.96.The material that the above-mentioned reaction of this data acknowledgement obtains is 2-(3'-cyano group-4'-fluorophenyl)-5-methoxy pyrimidine.
(2) part be 2-(3'-cyano group-4'-fluorophenyl)-5-methoxy pyrimidine containing the dimeric synthesis of iridium dichloro:
Under nitrogen protection, the Na of 1mmol
3irCl
63H
2it is in the cellosolvo/water mixed liquid of 3:1 that O, 0.46g (2mmol) 2-(3'-cyano group-4'-fluorophenyl)-5-methoxy pyrimidine is dissolved in 20mL volume ratio, 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 0.33g after drying, yield is 47.2%; Dipolymer, without the need to further purification, can directly drop in next step reaction; Its chemical equation is as follows:
(3) two (2-(the fluoro-5'-cyano-phenyl of 4'-)-5-methoxy pyrimidine-N, C
2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close the synthesis of iridium metal complex:
Under nitrogen protection, 0.68g (0.5mmol) main part be 2-(3'-cyano group-4'-fluorophenyl)-5-methoxy pyrimidine containing iridium dichloro dimer, 0.35g (1.25mmol) 2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles and 0.27g (5mmol) sodium methylate are dissolved in 25mL1, in 2-ethylene dichloride, stirring heating is warming up to 84 DEG C of reflux state reaction 8h; Naturally after being chilled to room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, has solid to separate out; Filter, collect crude product, solid uses deionized water, methanol wash for several times successively, and obtain 0.27g pure products through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 29.1%; Its chemical equation is as follows:
Product is carried out the result of Structural Identification:
Mass spectrum (MS m/z): 928.1 (M
+); Ultimate analysis: C35H19F8IrN8O2; Theoretical value: C, 45.31; H, 2.06; F, 16.38; Ir, 20.72; N, 12.08; O, 3.45; Measured value: C, 45.35; H, 2.10; F, 16.28; Ir, 20.75; N, 12.06; O, 3.46.The material that the above-mentioned reaction of this data acknowledgement obtains is two (2-(the fluoro-5'-cyano-phenyl of 4'-)-5-methoxy pyrimidine-N, C
2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close iridium metal complex.
Embodiment 6
Two (2-(the fluoro-5'-cyano-phenyl of 4'-)-4-hexyloxy pyrimidine-N, C
2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close iridium metal complex and synthetic method thereof:
(1) synthesis of 2-(3'-cyano group-4'-fluorophenyl)-4-hexyloxy pyrimidine:
Under nitrogen protection, 2.59g (10mmol) 2-bromo-4-hexyloxy pyrimidine, 1.65g (10mmol) 3-cyano group-4-fluorobenzoic boric acid and the two chlorine two (triphenyl phosphorus) of 0.21g (0.3mmol) are closed palladium and are dissolved in 40mLDMF, drip the aqueous solution of 20mL containing 1.06g (10mmol) sodium carbonate subsequently in reaction system; Be heated to stirring reaction 10h under 80 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 1/10 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 1.19g, yield is 39.8%; Product is carried out the result of Structural Identification:
Mass spectrum (MS m/z): 299.1 (M
+); Ultimate analysis: C17H18FN3O; Theoretical value: C, 68.21; H, 6.06; F, 6.35; N, 14.04; O, 5.34; Measured value: C, 68.27; H, 6.01; F, 6.39; N, 14.02; O, 5.31.The material that the above-mentioned reaction of this data acknowledgement obtains is 2-(3'-cyano group-4'-fluorophenyl)-4-hexyloxy pyrimidine.
(2) part be 2-(3'-cyano group-4'-fluorophenyl)-4-hexyloxy pyrimidine containing the dimeric synthesis of iridium dichloro:
Under nitrogen protection, 0.36g (1mmol) three hydrated iridium trichloride and 0.76g (3mmol) 2-(3'-cyano group-4'-fluorophenyl)-4-hexyloxy pyrimidine are dissolved in 25mL2-ethoxy ethanol/water (3/1) mixed solution, 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 0.27g after drying, yield is 32.7%; Dipolymer, without the need to further purification, can directly drop in next step reaction;
(3) two (2-(the fluoro-5'-cyano-phenyl of 4'-)-4-hexyloxy pyrimidine-N, C
2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close the synthesis of iridium metal complex:
Under nitrogen protection, 0.66g (0.4mmol) main part be 2-(3'-cyano group-4'-fluorophenyl)-4-hexyloxy pyrimidine containing iridium dichloro dimer, 0.22g (0.8mmol) 2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles and 0.34g (3.2mmol) sodium carbonate are dissolved in 25mL2-ethoxy ethanol, and stirring heating is warming up to 135 DEG C of reflux state reaction 5h; Naturally after being chilled to room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, has solid to separate out; Filter, collect crude product, solid uses deionized water, washed with diethylether for several times successively, and obtain 0.15g pure products through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 17.6%; Product is carried out the result of Structural Identification:
Mass spectrum (MS m/z): 1068.3 (M+); Ultimate analysis: C45H39F8IrN8O2; Theoretical value: C, 50.60; H, 3.68; F, 14.23; Ir, 18.00; N, 10.49; O, 3.00; Measured value: C, 50.66; H, 3.64; F, 14.18; Ir, 18.05; N, 10.46; O, 3.01.The material that the above-mentioned reaction of above data acknowledgement obtains is two (2-(the fluoro-5'-cyano-phenyl of 4'-)-4-hexyloxy pyrimidine-N, C
2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close iridium metal complex.
Embodiment 7
Two (2-(the fluoro-5'-cyano-phenyl of 4'-)-5-eicosane oxygen yl pyrimidines-N, C
2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close iridium metal complex and synthetic method thereof:
(1) synthesis of 2-(3'-cyano group-4'-fluorophenyl)-5-eicosane oxygen yl pyrimidines:
Under nitrogen protection, 2.28g (5mmol) 2-bromo-5-eicosane oxygen yl pyrimidines, 1.24g (7.5mmol) 3-cyano group-4-fluorobenzoic boric acid and 0.23g (0.2mmol) four (triphenyl phosphorus) close palladium and are dissolved in 35mL toluene, drip the aqueous solution of 15mL containing 1.59g (15mmol) sodium carbonate 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 1/5 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 0.54g, yield is 21.8%; Product is carried out the result of Structural Identification:
Mass spectrum (MS m/z): 495.4 (M+); Ultimate analysis: C31H46FN3O; Theoretical value: C, 75.11; H, 9.35; F, 3.83; N, 8.48; O, 3.23; Measured value: C, 75.16; H, 9.31; F, 3.86; N, 8.42; O, 3.25.The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(3'-cyano group-4'-fluorophenyl)-5-eicosane oxygen yl pyrimidines.
(2) part be 2-(3'-cyano group-4'-fluorophenyl)-5-eicosane oxygen yl pyrimidines containing the dimeric synthesis of iridium dichloro:
Under nitrogen protection, 0.18g (0.5mmol) three hydrated iridium trichloride, 0.99g (2mmol) 2-(3'-cyano group-4'-fluorophenyl)-5-eicosane oxygen yl pyrimidines is dissolved in 10mL2-ethoxy ethanol/water (3/1) mixed solution, 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 0.09g after drying, yield is 14.8%.Dipolymer, without the need to further purification, can directly drop in next step reaction;
(3) two (2-(the fluoro-5'-cyano-phenyl of 4'-)-5-eicosane oxygen yl pyrimidines-N, C
2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close the synthesis of iridium metal complex:
Under nitrogen protection, 0.73g (0.3mmol) main part be 2-(3'-cyano group-4'-fluorophenyl)-5-eicosane oxygen yl pyrimidines containing iridium dichloro dimer, 0.25g (0.9mmol) 2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles and 0.50g (3.6mmol) salt of wormwood are dissolved in 30mL2-methyl cellosolve, and stirring heating is warming up to 100 DEG C of state of temperature reaction 6h; Naturally after being chilled to room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, has solid to separate out; Filter, collect crude product, solid uses deionized water, washed with diethylether for several times successively, and obtain 0.07g pure products through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 8.0%; Product is carried out the result of Structural Identification:
Mass spectrum (MS m/z): 1460.7 (M
+); Ultimate analysis: C73H95F8IrN8O2; Theoretical value: C, 60.02; H, 6.55; F, 10.40; Ir, 13.16; N, 7.67; O, 2.19; Measured value: C, 60.11; H, 6.52; F, 10.33; Ir, 13.19; N, 7.64; O, 2.21.The material that the above-mentioned reaction of above data acknowledgement obtains is two (2-(the fluoro-5'-cyano-phenyl of 4'-)-5-eicosane oxygen yl pyrimidines-N, C
2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close iridium metal complex.
Embodiment 8
Two (2-(the fluoro-5'-cyano-phenyl of 4'-)-4,5-dimethyl pyrimidine-N, C
2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close iridium metal complex and synthetic method thereof:
(1) 2-(3'-cyano group-4'-fluorophenyl)-4,5 ?the synthesis of dimethyl pyrimidine:
Under nitrogen protection, 1.87g (10mmol) 2-bromo-4,5-dimethyl pyrimidine, 1.65g (10mmol) 3-cyano group-4-fluorobenzoic boric acid and 0.28g (0.4mmol) dichloro two (triphenyl phosphorus) close palladium and are dissolved in 50mL DMF, drip the aqueous solution of 25mL containing 3.18g (30mmol) sodium carbonate 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 1/8 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 1.14g, yield is 50.2%; Product is carried out the result of Structural Identification:
Mass spectrum (MS m/z): 227.1 (M
+); Ultimate analysis: C13H10FN3; Theoretical value: C, 68.71; H, 4.44; F, 8.36; N, 18.49; Measured value: C, 68.76; H, 4.41; F, 8.32; N, 18.51.The material that the above-mentioned reaction of this data acknowledgement obtains is 2-(3'-cyano group-4'-fluorophenyl)-4,5-dimethyl pyrimidines.
(2) part be 2-(3'-cyano group-4'-fluorophenyl)-4,5-dimethyl pyrimidines containing the dimeric synthesis of iridium dichloro:
Under nitrogen protection, 0.36g (1mmol) three hydrated iridium trichloride, 0.45g (2mmol) 2-(3'-cyano group-4'-fluorophenyl)-4, it is in the cellosolvo/water mixed liquid of 3:1 that 5-dimethyl pyrimidine is dissolved in 20mL volume ratio, 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 0.34g after drying, yield is 50.0%;
(3) two (2-(the fluoro-5'-cyano-phenyl of 4'-)-4,5-dimethyl pyrimidine-N, C
2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close the synthesis of iridium metal complex:
Under nitrogen protection, 0.68g (0.5mmol) part is 2-(3'-cyano group-4'-fluorophenyl)-4,5-dimethyl pyrimidine containing iridium dichloro dimer and 0.34g (1.2mmol) 2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles and 0.53g (5mmol) sodium carbonate are dissolved in 25mL2-ethoxy ethanol solvent, and stirring heating is warming up to 135 DEG C of reflux state reaction 6h; Naturally, after being chilled to room temperature, appropriate distilled water precipitating is added; Filter, collecting precipitation, solid uses deionized water, washed with diethylether successively, and obtain 0.27g pure products through methylene dichloride and anhydrous methanol mixed solvent recrystallization, yield is 29.2%; Its chemical equation is as follows:
Product is carried out the result of Structural Identification:
Mass spectrum (MS m/z): 924.2 (M
+); Ultimate analysis: C37H23F8IrN8; Theoretical value: C, 48.10; H, 2.51; F, 16.45; Ir, 20.81; N, 12.13; Measured value: C, 48.16; H, 2.44; F, 16.48; Ir, 20.77; N, 12.15.The material that the above-mentioned reaction of this data acknowledgement obtains is two (2-(the fluoro-5'-cyano-phenyl of 4'-)-4,5-dimethyl pyrimidine-N, C
2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close iridium metal complex.
Embodiment 9
Two (2-(the fluoro-5'-cyano-phenyl of 4'-)-4,5,6-trimethylpyrimidine-N, C
2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close iridium metal complex and synthetic method thereof:
(1) 2-(3'-cyano group-4'-fluorophenyl)-4,5,6 ?the synthesis of trimethylpyrimidine:
Under nitrogen protection, 2.01g (10mmol) 2-bromo-4,5,6-trimethylpyrimidine, 1.65g (10mmol) 3-cyano group-4-fluorobenzoic boric acid and 0.28g (0.4mmol) dichloro two (triphenyl phosphorus) close palladium and are dissolved in 50mL DMF, drip the aqueous solution of 25mL containing 3.18g (30mmol) sodium carbonate 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 1/8 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 0.96g, yield is 39.8%; Product is carried out the result of Structural Identification:
Mass spectrum (MS m/z): 241.1 (M
+); Ultimate analysis: C14H12FN3; Theoretical value: C, 69.70; H, 5.01; F, 7.87; N, 17.42; Measured value: C, 69.74; H, 5.03; F, 7.80; N, 17.43.The material that the above-mentioned reaction of this data acknowledgement obtains is 2-(3'-cyano group-4'-fluorophenyl)-4,5,6-trimethylpyrimidine.
(2) part be 2-(3'-cyano group-4'-fluorophenyl)-4,5,6-trimethylpyrimidine containing the dimeric synthesis of iridium dichloro:
Under nitrogen protection, 0.36g (1mmol) three hydrated iridium trichloride, 0.48g (2mmol) 2-(3'-cyano group-4'-fluorophenyl)-4,5, it is in the cellosolvo/water mixed liquid of 3:1 that 6-trimethylpyrimidine is dissolved in 20mL volume ratio, 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 0.28g after drying, yield is 39.5%;
(3) two (2-(the fluoro-5'-cyano-phenyl of 4'-)-4,5,6-trimethylpyrimidine-N, C
2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close the synthesis of iridium metal complex:
Under nitrogen protection, 0.71g (0.5mmol) part is 2-(3'-cyano group-4'-fluorophenyl)-4,5,6-trimethylpyrimidine containing iridium dichloro dimer and 0.34g (1.2mmol) 2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles and 0.53g (5mmol) sodium carbonate are dissolved in 25mL2-ethoxy ethanol solvent, and stirring heating is warming up to 135 DEG C of reflux state reaction 6h; Naturally, after being chilled to room temperature, appropriate distilled water precipitating is added; Filter, collecting precipitation, solid uses deionized water, washed with diethylether successively, and obtain 0.21g pure products through methylene dichloride and anhydrous methanol mixed solvent recrystallization, yield is 22.1%; Its chemical equation is as follows:
Product is carried out the result of Structural Identification:
Mass spectrum (MS m/z): 952.2 (M
+); Ultimate analysis: C39H27F8IrN8; Theoretical value: C, 49.21; H, 2.86; F, 15.97; Ir, 20.19; N, 11.77; Measured value: C, 49.25; H, 2.80; F, 15.96; Ir, 20.25; N, 11.74.The material that the above-mentioned reaction of this data acknowledgement obtains is two (2-(the fluoro-5'-cyano-phenyl of 4'-)-4,5,6-trimethylpyrimidine-N, C
2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close iridium metal complex.
Comparison example 1
Direct acquisition organic electromechanical phosphorescent material two [2-(4', 6'-difluorophenyl) pyridine-N, C
2'] (2-pyridinecarboxylic) close iridium (FIrpic), plays structure as follows:
Performance test:
The organic iridium metal complex prepare above-described embodiment 1 ~ 9 and existing organic iridium metal complex FIrpic of comparison example 1 carry out spectroscopic analysis and luminous quantum efficiency mensuration, and testing method is as follows:
Spectroscopic analysis: the organic iridium metal complex prepared by above-described embodiment 1 ~ 9 respectively compound concentration is 10
-6the CH of M
2c
l2solution, then carries out emmission spectrometric analysis respectively at 298K temperature.
Luminous quantum efficiency measure: by above-described embodiment 1 ~ 9 prepare organic iridium metal complex and comparison example 1 in existing organic iridium metal complex FIrpic respectively compound concentration be 10
-6the CH of M
2c
l2solution, then carries out luminous quantum efficiency mensuration.
The result that emmission spectrometric analysis and luminous quantum efficiency record is as following table 1:
Table 1
Wherein, organic iridium metal complex prepared by above-described embodiment 1 ~ 9 is carrying out in emmission spectrometric analysis respectively, organic iridium metal complex in embodiment 1 has an acromion at 488nm place simultaneously, organic iridium metal complex in embodiment 2 has an acromion at 487nm place simultaneously, organic iridium metal complex in embodiment 3 has an acromion at 491nm place simultaneously, organic iridium metal complex in embodiment 4 has an acromion at 507nm place simultaneously, organic iridium metal complex in embodiment 5 has an acromion at 487nm place simultaneously, organic iridium metal complex in embodiment 6 has an acromion at 500nm place simultaneously, organic iridium metal complex in embodiment 7 has an acromion at 510nm place simultaneously, organic iridium metal complex in embodiment 8 has an acromion at 494nm place simultaneously, organic iridium metal complex in embodiment 9 has an acromion at 502nm place simultaneously.In addition, the emmission spectrum of organic iridium metal complex prepared by embodiment 1 as shown in Figure 2, the emmission spectrum of organic iridium metal complex prepared by embodiment 5 as shown in Figure 3, in Fig. 2,3, transverse axis is emission wavelength (unit nm), and the longitudinal axis is the photoluminescence intensity (a.u.) after normalization method.
Can be found out by table 1 and Fig. 2,3, organic iridium metal complex that the organic iridium metal complex of the embodiment of the present invention is prepared as above-described embodiment 1 ~ 9 is compared with existing organic iridium metal complex, its blue light purity of launching is high, there is higher luminous quantum efficiency, its luminous efficiency is high, therefore, can be used as blue light electroluminescent material to be widely used in technical field of organic electroluminescence.
Application Example 1
Containing organic iridium metal complex organic electroluminescence device (OLED) prepared by embodiment 1 and preparation method thereof:
As shown in Figure 4, it comprises the glass substrate 1, anode layer 2, hole injection layer 31, hole transmission layer 32, electronic barrier layer 33, luminescent layer 34, hole blocking layer 35, electron transfer layer 36, electron injection buffer layer 37 and the cathode layer 4 that stack gradually combination to the structure of this OLED.Wherein, hole injection layer 31, hole transmission layer 32, electronic barrier layer 33, luminescent layer 34, hole blocking layer 35, electron transfer layer 36, electron injection buffer layer 37 form organic function layer 3, two (2-(the fluoro-5'-cyano-phenyl of 4'-) pyrimidine-N, C prepared by the embodiment 1 containing 7wt% in this luminescent layer 34
2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close iridium metal complex.Its concrete structure the following is Ir title complex (30nm)/BCP (10nm)/Alq3 (35nm)/LiF (1nm)/Al (120nm) prepared by glass/ITO (100nm)/m-MTDATA (40nm)/NPB (20nm)/mCP (10nm)/mCP:7wt% embodiment 1.
This OLED preparation method is as follows: a glass substrate 1 depositing a layer thickness is 200nm, square resistance is that the tin indium oxide (ITO) of 10 ~ 20 Ω/mouth is as transparent anode 2, on anode 301, the m-MTDATA(4 that a layer thickness is 40nm is prepared successively by vacuum evaporation, 4', 4''-tri-(N-3-methylphenyl-N-phenyl is amino) triphenylamine) hole-injecting material is as hole injection layer 31, a layer thickness is the NPB(N of 20nm, two (1-the naphthyl)-N of N'-, N'-diphenylbenzidine) hole mobile material is as hole transmission layer 32, a layer thickness is the mCP(1 of 10nm, two (9-carbazyl) benzene of 3-) electron-blocking materials is two (2-(the fluoro-5'-cyano-phenyl of the 4'-) pyrimidine-N prepared doped with 7wt% embodiment 1 of 30nm as electronic barrier layer 33 and a layer thickness, C
2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles) close the mCP of iridium as luminescent layer 34, on this luminescent layer 34, vacuum evaporation a layer thickness is successively the BCP(2 of 10nm again, 9-dimethyl-4,7-phenylbenzene-phenanthrolene) material be the Alq3 (three (oxine) aluminium) of 35nm as hole blocking layer 35, thickness is that the LiF of 1nm is as electron injection buffer layer 37 as electron transfer layer 36, thickness, the last vacuum plating of employing on the buffer layer techniques of deposition thickness is the metal A l of 120nm, as the negative electrode 4 of device.
Know through performance test, the maximum emission wavelength of the electroluminescent spectrum of this device is positioned at 466nm, has an acromion at 488nm place, and the maximum lumen efficiency of device is 8.2lm/W, and maximum external quantum efficiency is 9.0%.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. an organic iridium metal complex, its general formula of molecular structure is following (I):
In formula, R
1, R
2, R
3identical or not identical is H, alkyl or alkoxyl group.
2. organic iridium metal complex according to claim 1, is characterized in that: described alkyl or alkoxyl group are C
1~ C
20straight or branched alkyl or alkoxyl group.
3. organic iridium metal complex according to claim 1 and 2, is characterized in that: described alkyl is at least one in methyl, the tertiary butyl, n-hexyl, NSC 62789 base;
Described alkoxyl group is at least one in methoxyl group, hexyloxy, eicosane oxygen base.
4. a preparation method for organic iridium metal complex, comprises the steps:
The compd A of following structural formula general formula is provided:
In the environment of anaerobic, described compd A and hydrated iridium trichloride or hydration chlorine sub-iridium acid sodium are carried out thermal backflow reaction in reaction solvent, generate the chlorine bridge dipolymer B of following structural formula general formula:
In the environment of anaerobic, by described chlorine bridge dipolymer B and 2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles carries out thermal backflow reaction under carbonate, sodium methylate and/or sodium ethylate catalyst action and in the reaction solvent of 84 ~ 135 DEG C, purifying, obtains organic iridium metal complex of following general formula of molecular structure (I):
Wherein, the R in compd A, B and general structure (I)
1, R
2, R
3identical or not identical is H, alkyl or alkoxyl group.
5. the preparation method of organic iridium metal complex according to claim 4, it is characterized in that: in the step that compd A and hydrated iridium trichloride or the thermal backflow of hydration chlorine sub-iridium acid sodium reacts, the mole dosage of described compd A and hydrated iridium trichloride or hydration chlorine sub-iridium acid sodium is than being (2 ~ 4): 1.
6. the preparation method of organic iridium metal complex according to claim 4, it is characterized in that: at described chlorine bridge dipolymer B and 2, in the step of 4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles's thermal backflow reaction, the mole dosage of described catalyzer and chlorine bridge dipolymer B is than being (8 ~ 12): 1; And/or the mole dosage of described 2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles and chlorine bridge dipolymer B is than being (2 ~ 3): 1.
7. the preparation method of the organic iridium metal complex according to any one of claim 4 ~ 6, it is characterized in that: in the step that described compd A and hydrated iridium trichloride or the thermal backflow of hydration chlorine sub-iridium acid sodium react, described reaction solvent is the mixture of 2-methyl cellosolve, cellosolvo, methylene dichloride, trichloromethane at least one or 2-methyl cellosolve, cellosolvo, methylene dichloride, trichloromethane at least one and distilled water; And/or,
Described chlorine bridge dipolymer B and 2, in the step of 4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles's thermal backflow reaction, described reaction solvent is at least one in cellosolvo, 2-methyl cellosolve, 1,2-ethylene dichloride, methylene dichloride, trichloromethane.
8. the preparation method of the organic iridium metal complex according to any one of claim 4 ~ 6, is characterized in that, the preparation method of described compd A is as follows:
In anaerobic, alkaline environment and organo-metallic palladium catalyst, under organic solvent existent condition, the Compound C of following structural formula general formula and 3-cyano group-4-fluorobenzoic boric acid are carried out purifying after Suzuki linked reaction,
Wherein, the R in Compound C
1, R
2, R
3identical or not identical is H, alkyl or alkoxyl group.
9. the preparation method of organic iridium metal complex according to claim 8, is characterized in that: the temperature of described Suzuki linked reaction is 85 ~ 100 DEG C, and the time is 6 ~ 12h; And/or,
The mole dosage of described organo-metallic palladium catalyst is 2 ~ 5% of Compound C mole dosage.
10. the organic iridium metal complex as described in as arbitrary in claims 1 to 3 is as the application of blue electrophosphorescence material in organic electroluminescence device, EL cold light film or electrochemical cell luminescent device.
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