CN104628784A - Iridium metal complex with red-light organic electrophosphorescent material, preparation method thereof and organic electroluminescent device - Google Patents
Iridium metal complex with red-light organic electrophosphorescent material, preparation method thereof and organic electroluminescent device Download PDFInfo
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- CN104628784A CN104628784A CN201310574804.8A CN201310574804A CN104628784A CN 104628784 A CN104628784 A CN 104628784A CN 201310574804 A CN201310574804 A CN 201310574804A CN 104628784 A CN104628784 A CN 104628784A
- Authority
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- China
- Prior art keywords
- reaction
- metal complex
- iridium
- iridium metal
- methylisoquinolinium
- Prior art date
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- Pending
Links
- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 176
- 239000000463 material Substances 0.000 title claims abstract description 136
- -1 Iridium metal complex Chemical class 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims description 168
- 239000000243 solution Substances 0.000 claims description 104
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 79
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 claims description 77
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 69
- 239000012043 crude product Substances 0.000 claims description 51
- 238000003756 stirring Methods 0.000 claims description 44
- 239000003446 ligand Substances 0.000 claims description 39
- 238000001914 filtration Methods 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 26
- 238000005401 electroluminescence Methods 0.000 claims description 22
- 239000012153 distilled water Substances 0.000 claims description 21
- 239000012074 organic phase Substances 0.000 claims description 20
- 238000010898 silica gel chromatography Methods 0.000 claims description 20
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 claims description 19
- 238000010992 reflux Methods 0.000 claims description 19
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 17
- 239000012046 mixed solvent Substances 0.000 claims description 17
- 230000004044 response Effects 0.000 claims description 17
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- OMFXVFTZEKFJBZ-HJTSIMOOSA-N corticosterone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OMFXVFTZEKFJBZ-HJTSIMOOSA-N 0.000 claims description 15
- 235000019270 ammonium chloride Nutrition 0.000 claims description 14
- 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 14
- 229920006395 saturated elastomer Polymers 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000706 filtrate Substances 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 10
- 239000003480 eluent Substances 0.000 claims description 10
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- 238000000746 purification Methods 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- 230000000903 blocking effect Effects 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 8
- 239000007924 injection Substances 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 230000005540 biological transmission Effects 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 5
- 235000015320 potassium carbonate Nutrition 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 238000005342 ion exchange Methods 0.000 claims description 3
- 238000010926 purge Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 82
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 63
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 48
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 48
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 41
- 230000015572 biosynthetic process Effects 0.000 description 30
- 238000003786 synthesis reaction Methods 0.000 description 30
- 229910052757 nitrogen Inorganic materials 0.000 description 29
- 239000000203 mixture Substances 0.000 description 19
- 238000004458 analytical method Methods 0.000 description 14
- 238000001514 detection method Methods 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 14
- 238000001819 mass spectrum Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- RRXGMARSIPMMRX-UHFFFAOYSA-N 2,2,2-trifluoro-1-(4-isoquinolin-3-ylphenyl)ethanone Chemical compound FC(C(=O)C1=CC=C(C=C1)C=1N=CC2=CC=CC=C2C1)(F)F RRXGMARSIPMMRX-UHFFFAOYSA-N 0.000 description 12
- ROEWYSGUZNRZRM-UHFFFAOYSA-N 2,2,2-trifluoro-1-[4-(1-methylisoquinolin-3-yl)phenyl]ethanone Chemical compound CC1=NC(=CC2=CC=CC=C12)C3=CC=C(C=C3)C(=O)C(F)(F)F ROEWYSGUZNRZRM-UHFFFAOYSA-N 0.000 description 9
- XTIKEGGZFXJFQR-UHFFFAOYSA-N 2,2,2-trifluoro-1-[4-(4-methylisoquinolin-3-yl)phenyl]ethanone Chemical compound CC1=C(N=CC2=CC=CC=C12)C3=CC=C(C=C3)C(=O)C(F)(F)F XTIKEGGZFXJFQR-UHFFFAOYSA-N 0.000 description 9
- BLSVSCAYNYBUJC-UHFFFAOYSA-N 2,2,2-trifluoro-1-[4-(5-methylisoquinolin-3-yl)phenyl]ethanone Chemical compound CC1=C2C=C(N=CC2=CC=C1)C3=CC=C(C=C3)C(=O)C(F)(F)F BLSVSCAYNYBUJC-UHFFFAOYSA-N 0.000 description 9
- MYNBYOLSEZLXJT-UHFFFAOYSA-N 2,2,2-trifluoro-1-[4-(6-methylisoquinolin-3-yl)phenyl]ethanone Chemical compound CC1=CC2=CC(=NC=C2C=C1)C3=CC=C(C=C3)C(=O)C(F)(F)F MYNBYOLSEZLXJT-UHFFFAOYSA-N 0.000 description 9
- ARPYLRMTBRCDGU-UHFFFAOYSA-N 2,2,2-trifluoro-1-[4-(7-methylisoquinolin-3-yl)phenyl]ethanone Chemical compound CC1=CC2=CN=C(C=C2C=C1)C3=CC=C(C=C3)C(=O)C(F)(F)F ARPYLRMTBRCDGU-UHFFFAOYSA-N 0.000 description 9
- VQHKHJBYIRIHSA-UHFFFAOYSA-N 2,2,2-trifluoro-1-[4-(8-methylisoquinolin-3-yl)phenyl]ethanone Chemical compound CC1=C2C=NC(=CC2=CC=C1)C3=CC=C(C=C3)C(=O)C(F)(F)F VQHKHJBYIRIHSA-UHFFFAOYSA-N 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000000103 photoluminescence spectrum Methods 0.000 description 9
- 238000011160 research Methods 0.000 description 9
- STSCVKRWJPWALQ-UHFFFAOYSA-N TRIFLUOROACETIC ACID ETHYL ESTER Chemical compound CCOC(=O)C(F)(F)F STSCVKRWJPWALQ-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- 238000006862 quantum yield reaction Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 125000006575 electron-withdrawing group Chemical group 0.000 description 5
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 5
- 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 4
- 0 CCC(C1COC(C)C[C@](C)OC)(C(C(CC2)C3C4)C=C2C(C2CC2)N)C1(CC)C3=CC1C4CC*(CC*)CC1 Chemical compound CCC(C1COC(C)C[C@](C)OC)(C(C(CC2)C3C4)C=C2C(C2CC2)N)C1(CC)C3=CC1C4CC*(CC*)CC1 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- 125000004044 trifluoroacetyl group Chemical group FC(C(=O)*)(F)F 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 description 3
- 238000007738 vacuum evaporation Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- BFYYPRWCYPUBFV-UHFFFAOYSA-N 3-(4-bromophenyl)-1-methylisoquinoline Chemical compound CC1=NC(=CC2=CC=CC=C12)C3=CC=C(C=C3)Br BFYYPRWCYPUBFV-UHFFFAOYSA-N 0.000 description 1
- HQOKSMPRURCKBI-UHFFFAOYSA-N 3-(4-bromophenyl)-4-methylisoquinoline Chemical compound CC1=C(N=CC2=CC=CC=C12)C3=CC=C(C=C3)Br HQOKSMPRURCKBI-UHFFFAOYSA-N 0.000 description 1
- OBGRSMLDWMMFCK-UHFFFAOYSA-N 3-(4-bromophenyl)-5-methylisoquinoline Chemical compound CC1=C2C=C(N=CC2=CC=C1)C3=CC=C(C=C3)Br OBGRSMLDWMMFCK-UHFFFAOYSA-N 0.000 description 1
- PRHWWWVLXXEQHB-UHFFFAOYSA-N 3-(4-bromophenyl)-6-methylisoquinoline Chemical compound CC1=CC2=CC(=NC=C2C=C1)C3=CC=C(C=C3)Br PRHWWWVLXXEQHB-UHFFFAOYSA-N 0.000 description 1
- QRUFATBPSDOICD-UHFFFAOYSA-N 3-(4-bromophenyl)-7-methylisoquinoline Chemical compound CC1=CC2=CN=C(C=C2C=C1)C3=CC=C(C=C3)Br QRUFATBPSDOICD-UHFFFAOYSA-N 0.000 description 1
- OYBNUVAPWLKDPX-UHFFFAOYSA-N 3-(4-bromophenyl)-8-methylisoquinoline Chemical compound CC1=C2C=NC(=CC2=CC=C1)C3=CC=C(C=C3)Br OYBNUVAPWLKDPX-UHFFFAOYSA-N 0.000 description 1
- LDTGPFJEWJZVAE-UHFFFAOYSA-N 3-(4-bromophenyl)isoquinoline Chemical compound BrC1=CC=C(C=C1)C=1N=CC2=CC=CC=C2C=1 LDTGPFJEWJZVAE-UHFFFAOYSA-N 0.000 description 1
- YOZHUJDVYMRYDM-UHFFFAOYSA-N 4-(4-anilinophenyl)-3-naphthalen-1-yl-n-phenylaniline Chemical compound C=1C=C(C=2C(=CC(NC=3C=CC=CC=3)=CC=2)C=2C3=CC=CC=C3C=CC=2)C=CC=1NC1=CC=CC=C1 YOZHUJDVYMRYDM-UHFFFAOYSA-N 0.000 description 1
- DUVRRINUPADPTB-UHFFFAOYSA-N CC(C(CC1)=CCC1C1NCC(C(C)CCC2)C2C1)O Chemical compound CC(C(CC1)=CCC1C1NCC(C(C)CCC2)C2C1)O DUVRRINUPADPTB-UHFFFAOYSA-N 0.000 description 1
- ZGRNACFVGYAMAZ-UHFFFAOYSA-N CC1C(C2=CCC(C(C(F)(F)F)O)C=C2)=NCC2C=CC=CC12 Chemical compound CC1C(C2=CCC(C(C(F)(F)F)O)C=C2)=NCC2C=CC=CC12 ZGRNACFVGYAMAZ-UHFFFAOYSA-N 0.000 description 1
- GGIFUKAKLTXKLP-UHFFFAOYSA-N CCCC1[F]C1 Chemical compound CCCC1[F]C1 GGIFUKAKLTXKLP-UHFFFAOYSA-N 0.000 description 1
- IGTFFDIQYMIHCY-UHFFFAOYSA-N ClCCl.[Ir] Chemical compound ClCCl.[Ir] IGTFFDIQYMIHCY-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- DWNAAAKNLXVIRH-UHFFFAOYSA-N O=C(C(F)(F)F)c(cc1)ccc1C1=NCC(C=CCC2)C2=C1 Chemical compound O=C(C(F)(F)F)c(cc1)ccc1C1=NCC(C=CCC2)C2=C1 DWNAAAKNLXVIRH-UHFFFAOYSA-N 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-N Picolinic acid Natural products OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- POJOORKDYOPQLS-UHFFFAOYSA-L barium(2+) 5-chloro-2-[(2-hydroxynaphthalen-1-yl)diazenyl]-4-methylbenzenesulfonate Chemical class [Ba+2].C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S([O-])(=O)=O.C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S([O-])(=O)=O POJOORKDYOPQLS-UHFFFAOYSA-L 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 235000012736 patent blue V Nutrition 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 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
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-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 iridium metal complex with a red-light organic electrophosphorescent material. The iridium metal complex has the following structural formula: shown in the description, wherein R is H or methyl. The iridium metal complex with the red-light organic electrophosphorescent material has higher color purity. In addition, the invention also provides a preparation method of the iridium metal complex with the red-light organic electrophosphorescent material and an organic electroluminescent device.
Description
Technical field
The present invention relates to organic electroluminescent Material Field, particularly a kind of ruddiness organic electromechanical phosphorescent material iridium metal complex and preparation method thereof and organic electroluminescence device.
Background technology
Organic electroluminescent refers to that organic materials is under electric field action, electric energy is converted into a kind of luminescence phenomenon of luminous energy.Make to stay cool to the research of organic electroluminescent due to reasons such as the driving voltage of organic electroluminescence device are too high, luminous efficiency is very low in early days.Until 1987, the human hairs such as the Tang of Kodak understand with oxine aluminium (Alq
3) be luminescent material, make the high-quality thin film of even compact with aromatic diamine, obtained low-work voltage, high brightness, high efficiency organic electroluminescence device, open the new prelude to electroluminescent organic material research.But owing to being subject to the restriction of spin statistics theory, the theoretical internal quantum efficiency limit of fluorescent material is only 25%, how makes full use of all the other phosphorescence of 75% and realize higher luminous efficiency and become hot research direction in after this this field.1997, Forrest etc. found electrophosphorescence phenomenon, and the internal quantum efficiency of electroluminescent organic material breaches the restriction of 25%, makes the research of electroluminescent organic material enter another new period.
In research subsequently, the title complex of small molecules doping type transition metal has become the research emphasis of people, as the title complex of iridium, ruthenium, platinum etc.The advantage of this kind of title complex is that they can obtain very high emitted energy from the triplet state of self, and wherein metal iridium (III) compound, due to good stability, in building-up process, reaction conditions is gentle, and there is very high electroluminescent properties, in research process subsequently, account for dominant position always.
In order to make device obtain full-color display, generally must obtain the ruddiness of excellent performance, green glow and blue light material simultaneously.Generally speaking, the development of blue phosphor materials always lags behind ruddiness and green glow, and with regard to single from this index of purity of color, blue phosphor materials seldom can accomplish the purity of color as dark red light and dark green light so far.In order to produce gratifying white light OLED, select at present or based on the phosphor material of sky blue light, as two [2-(4', 6'-difluorophenyl) pyridine-N, C2'] (2-pyridine carboxylic acid) close iridium [FIrpic], and it is just passable that this just requires that arranged in pairs or groups red phosphorescence material will be connected to saturated red scarlet.So the ruddiness phosphorescent organic electroluminescent material developing high color purity is still a large focus of OLED research field.
Summary of the invention
Given this, be necessary the ruddiness organic electromechanical phosphorescent material iridium metal complex providing a kind of purity of color higher, the preparation method of this ruddiness organic electromechanical phosphorescent material iridium metal complex also will be provided and use the organic electroluminescence device of this ruddiness organic electromechanical phosphorescent material iridium metal complex.
A kind of ruddiness organic electromechanical phosphorescent material iridium metal complex, has following structural formula:
Wherein, R is H or methyl.
Wherein in an embodiment, the structural formula of described ruddiness organic electromechanical phosphorescent material iridium metal complex is:
A preparation method for ruddiness organic electromechanical phosphorescent material iridium metal complex, comprises the steps:
The compd A that following structural formula represents is provided,
Wherein, R is H or methyl;
Under anaerobic, described compd A and three hydrated iridium trichloride are formed the first mixing solutions for 2.2:1 ~ 3:1 is dissolved in the first solvent in molar ratio, under lucifuge condition, back flow reaction 20 hours ~ 24 hours, after filtering cleaning, obtain the crude product containing compd B, described compd B has following structural formula
Under anaerobic and anhydrous condition, described crude product, methyl ethyl diketone and alkaline catalysts containing compd B is dissolved in the second solvent and obtains the second mixing solutions, carry out ligand exchange reaction 15 hours ~ 20 hours, after separation and purification, obtain the Compound I with following structural formula
Wherein, the mol ratio of described methyl ethyl diketone and described three hydrated iridium trichloride 2:1 ~ 4:1 of being.
Wherein in an embodiment, after described back flow reaction, described filtration cleaning step is: first the reaction solution after described back flow reaction is cooled to room temperature, collecting precipitation thing after filtration, described throw out is adopted ethanol purge, after vacuum-drying, obtains the described crude product containing compd B.
Wherein in an embodiment, the temperature of described back flow reaction is the reflux temperature of described first solvent; Described first solvent is form mixed solvent by cellosolvo and water; Described in described first solvent, the volume ratio of cellosolvo and water is 3:1; The concentration of described three hydrated iridium trichloride in described first mixing solutions is 0.033mol/L ~ 0.05mol/L.
Wherein in an embodiment, the temperature of described ligand exchange reaction is the reflux temperature of the second solvent; Described second solvent is cellosolvo or 2-methyl cellosolve; The concentration of the described compd B in described second mixing solutions is 0.1mol/L ~ 0.2mol/L; Described alkaline catalysts is salt of wormwood or sodium carbonate; The molar weight of described alkaline catalysts is 3 ~ 5 times of the molar weight of described three hydrated iridium trichloride.
Wherein in an embodiment, after described ion exchange reaction, the step of described separation and purification is: after the reaction solution first obtained after described ligand exchange reaction naturally cools to room temperature, add distilled water, solid collected by filtration, use solid described in distilled water wash, then, described solid is dry in vacuum, then with dichloromethane eluant, silica gel column chromatography separation is carried out to described solid, obtain the described Compound I of purifying.
8, the preparation method of ruddiness organic electromechanical phosphorescent material iridium metal complex according to claim 3, it is characterized in that, described compd A is prepared by following steps:
The Compound C with following structural formula is provided,
Under-78 DEG C and oxygen free condition, be 1:1.1 ~ 1:1.3 in molar ratio, by described Compound C and diisopropylamino lithium stirring reaction 1 hour ~ 2 hours in organic solvent, then the organic solution of trifluoroacetyl ethyl ester is added, maintaining temperature of reaction is-78 DEG C of continuation stirring reactions 1 hour ~ 2 hours, question response temperature is warming up to 0 DEG C naturally, continue stirring reaction 0.5 hour ~ 1 hour, then add saturated aqueous ammonium chloride solution and continue reaction, after separating-purifying, obtain described compd A, wherein, the mol ratio of described trifluoroacetyl ethyl ester and described diisopropylamino lithium is 1:1.
Wherein in an embodiment, in the step obtaining described compd A, the step of described separation and purification is: make to be extracted with ethyl acetate obtain organic phase by adding the reacted reaction solution of saturated aqueous ammonium chloride solution, then organic phase described in anhydrous magnesium sulfate drying is used, again successively after filtration, concentrated filtrate, obtain crude product, the mixed solution of sherwood oil and ethyl acetate is used to carry out silica gel column chromatography separating-purifying as eluent to obtaining described crude product, obtain described compd A, wherein, the volume ratio of described sherwood oil and ethyl acetate is 3:1 ~ 5:1.
A kind of organic electroluminescence device, comprise the anode layer stacked gradually on substrate, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, electron injection buffer layer and cathode layer, it is characterized in that, the material of described luminescent layer comprises material of main part and is doped in the guest materials in described material of main part, the doping mass percent of described guest materials is 8%, and described guest materials is above-mentioned ruddiness organic electromechanical phosphorescent material iridium metal complex.
Above-mentioned ruddiness organic electromechanical phosphorescent material iridium metal complex is cyclic metal complexes agent structure with 3-(4'-trifluoroacetyl phenyl) isoquinoline 99.9, take methyl ethyl diketone as the different distribution type complex of iridium of assistant ligand, isoquinoline 99.9 ring is the choosing of the superior structural of the ring master metal part of red phosphorescence material, can ensure that material is luminous at red spectral band, thus make ruddiness organic electromechanical phosphorescent material iridium metal complex have higher purity of color.And on phenyl ring, introduce electron-withdrawing group trifluoroacetyl group, isoquinoline 99.9 ring introduces methyl, in theory emission wavelength aspect meeting blue shift, but methyl is introduced on different isoquinoline 99.9 C positions and can be produced different electronic effects, can regulate the emission wavelength of material.
Accompanying drawing explanation
Fig. 1 is preparation method's schema of the ruddiness organic electromechanical phosphorescent material iridium metal complex of an embodiment;
Fig. 2 is the structural representation of the organic electroluminescence device of an embodiment;
Fig. 3 is the dichloromethane solution (~ 10 at 298K temperature that iridium metal complex two [3-(4'-trifluoroacetyl phenyl) isoquinoline 99.9-N, C2'] (methyl ethyl diketone) prepared by embodiment 1 closes iridium
-5mol/L) the photoluminescence spectra figure in.
Embodiment
Mainly in conjunction with the drawings and the specific embodiments ruddiness organic electromechanical phosphorescent material iridium metal complex and preparation method thereof and organic electroluminescence device are described in further detail below.
The ruddiness organic electromechanical phosphorescent material iridium metal complex of one embodiment, has following structural formula:
Wherein, R is H or methyl.When R is H, the structural formula of ruddiness organic electromechanical phosphorescent material iridium metal complex is:
When R is methyl, the structural formula of ruddiness organic electromechanical phosphorescent material iridium metal complex is:
Research shows, isoquinoline 99.9 ring has been concentrated most of cloud density of the lumo energy of most of material, and the cloud density on phenyl ring can affect the HOMO energy level of material.In general, phenyl ring is introduced electron-withdrawing group can make HOMO energy level decline, isoquinoline 99.9 ring is introduced electron-donating group can make lumo energy raise, the emission wavelength meeting blue shift of material, otherwise introducing electron-donating group on phenyl ring can make HOMO energy level raise, isoquinoline 99.9 ring is introduced electron-withdrawing group can make lumo energy decline, and the emission wavelength of material can red shift.But; above-mentioned ruddiness organic electromechanical phosphorescent material iridium metal complex introduces electron-withdrawing group trifluoroacetyl group on phenyl ring; isoquinoline 99.9 ring introduces methyl; emission wavelength aspect meeting blue shift in theory; but methyl is introduced in the different C positions that methyl introduces different isoquinoline 99.9 rings and carries out chemically modified; different electronic effects can be produced, thus realize the red emission of the different wave length of ruddiness organic electromechanical phosphorescent material iridium metal complex material.And when R is methyl, can certain space steric effect be produced by the introducing of methyl, the direct effect between atoms metal can be reduced, reduce the self-quenching phenomenon of triplet exciton, improve the luminous efficiency of material.
Above-mentioned ruddiness organic electromechanical phosphorescent material iridium metal complex is cyclic metal complexes agent structure with 3-(4'-trifluoroacetyl phenyl) isoquinoline 99.9, take methyl ethyl diketone as the different distribution type iridium metal complex of assistant ligand, isoquinoline 99.9 ring is the choosing of the superior structural of the ring master metal part of red phosphorescence material, can ensure that material is luminous at red spectral band, thus make ruddiness organic electromechanical phosphorescent material iridium metal complex have higher purity of color.And on phenyl ring, introduce electron-withdrawing group trifluoroacetyl group, isoquinoline 99.9 ring introduces methyl, in theory emission wavelength aspect meeting blue shift, but methyl is introduced on different isoquinoline 99.9 C positions and can be produced different electronic effects, can regulate the emission wavelength of material.
And because Ir ordination number is comparatively large, iridium metal complex can be made to produce very strong Quantum geometrical phase, be conducive to phosphorescent emissions; D orbit splitting in Ir metal ion is comparatively large, avoids interacting with the MLCT state of title complex and reducing phosphorescent emissions efficiency; Trivalent Ir ion can form highly stable neutral molecule with part, is conducive to the device preparation of evaporation or solution processing mode.So metal iridium complex is the luminescent material of most potentiality in electromechanical phosphorescent material.
In addition, on phenyl ring, the introducing of trifluoroacetyl group is relative to hydrogen atom, can reduce molecular vibration energy, and improve luminous efficiency and the intensity of ring iridium metal complex, meanwhile, fluorine-containing stability of material is high, not easily aged deterioration, cuts the working conditions of energy withstand harsh; The introducing of assistant ligand methyl ethyl diketone, effectively can improve the evaporation performance of material, increases its film-forming properties and improves the stability of device.Manufacture craft simple and flexible of the present invention, provides excellent material to full-color display and lighting application.
As shown in Figure 1, the preparation method of the ruddiness organic electromechanical phosphorescent material iridium metal complex of an embodiment, comprises the steps:
Step S110: the compd A that following structural formula represents is provided,
Wherein, R is H or methyl.
Wherein, the structural formula of compd A is:
Wherein, in step S110, compd A is prepared by following steps:
The Compound C with following structural formula is provided,
Under-78 DEG C and oxygen free condition, be 1:1.1 ~ 1:1.3 in molar ratio by Compound C and diisopropylamino lithium stirring reaction 1 hour ~ 2 hours in organic solvent, then the organic solution of trifluoroacetyl ethyl ester is added, maintaining temperature of reaction is-78 DEG C of continuation stirring reactions 1 hour ~ 2 hours, question response temperature is warming up to 0 DEG C naturally, continue stirring reaction 0.5 hour ~ 1 hour, then add saturated aqueous ammonium chloride solution and continue reaction, after separating-purifying, obtain compd A, wherein, the mol ratio of trifluoroacetyl ethyl ester and diisopropylamino lithium is 1:1.
Wherein, oxygen free condition is protection gas condition, and protection gas is nitrogen, argon gas, helium etc.
By adding saturated aqueous ammonium chloride solution, remove the diisopropylamino lithium in reaction solution, to ensure the safety operated.
Concrete, by Compound C and diisopropylamino lithium in organic solvent before stirring reaction, first Compound C is dissolved in the organic solution that organic solvent forms Compound C, then the organic solution of Compound C is joined in the mixing solutions be made up of diisopropylamino lithium and organic solvent.Preferably, in the organic solution of Compound C, the concentration of Compound C is 0.4mol/L ~ 0.67mol/L; Preferred, the solvent in the organic solution of Compound C is tetrahydrofuran (THF).Preferably, the organic solvent organic solution of Compound C joined in the mixing solutions be made up of diisopropylamino lithium and organic solvent is tetrahydrofuran (THF).
Preferably, in the organic solution of trifluoroacetyl ethyl ester, the concentration of trifluoroacetyl ethyl ester is 0.367mol/L ~ 0.6mol/L; Preferred, the solvent in the organic solution of trifluoroacetyl ethyl ester is tetrahydrofuran (THF).
Concrete, in the step obtaining compd A, the step of separation and purification is: make to be extracted with ethyl acetate obtain organic phase by adding the reacted reaction solution of saturated aqueous ammonium chloride solution, then anhydrous magnesium sulfate drying organic phase is used, again successively after filtration, concentrated filtrate, obtain crude product, using the mixed solution of sherwood oil and ethyl acetate to carry out silica gel column chromatography separating-purifying as eluent to obtaining crude product, obtaining compd A.Wherein, the volume ratio of sherwood oil and ethyl acetate is 3:1 ~ 5:1.
Wherein, the method for concentrated filtrate is: adopt the solvent rotating and steam except in filtrate.
Step S120: under anaerobic, by compd A and three hydrated iridium trichloride (IrCl
33H
2o) the first mixing solutions is formed for 2.2:1 ~ 3:1 is dissolved in the first solvent in molar ratio, under lucifuge condition, back flow reaction 20 hours ~ 24 hours, after filtering cleaning, obtain the crude product containing compd B, compd B has following structural formula,
Wherein, in step S120, under oxygen free condition refers to protection compression ring border, protection gas is nitrogen, argon gas, helium etc.
Wherein, in step S120, the first organic solvent is for forming mixed solvent by cellosolvo and water.Preferably, in the first solvent, the volume ratio of cellosolvo and water is 3:1.
Preferably, the concentration of three hydrated iridium trichloride in the first mixing solutions is 0.033mol/L ~ 0.05mol/L.
Wherein, in step S120, after back flow reaction, the step of filtering cleaning is: first the reaction solution after back flow reaction is cooled to room temperature, collecting precipitation thing, adopts ethanol purge by throw out after filtration, after vacuum-drying, obtains the crude product containing compd B.
What prepare in step S120 is the crude product of B containing compound, without the need to further purification, is directly used in next step reaction.
Step S130: under anaerobic and anhydrous condition, crude product containing compd B, methyl ethyl diketone and alkaline catalysts are dissolved in the second solvent and form the second mixing solutions, carry out ligand exchange reaction 15 hours ~ 20 hours, after separation and purification, obtain the Compound I with following structural formula
Wherein, the mol ratio of methyl ethyl diketone and three hydrated iridium trichloride 2:1 ~ 4:1 of being.
Wherein, in step S130, under oxygen free condition refers to protection compression ring border, protection gas is nitrogen, argon gas, helium etc.
Wherein, in step S130, the temperature of ligand exchange reaction is the reflux temperature of the second solvent; Second solvent is cellosolvo or 2-methyl cellosolve; The concentration of the compd B in the second mixing solutions is 0.1mol/L ~ 0.2mol/L; Alkaline catalysts is salt of wormwood or sodium carbonate; The molar weight of alkaline catalysts is 3 ~ 5 times of the molar weight of three hydrated iridium trichloride.
Wherein, in step S130, after ion exchange reaction, the step of separation and purification is: after the reaction solution first obtained after ligand exchange reaction naturally cools to room temperature, add distilled water, solid collected by filtration, use distilled water wash solid, then, solid is dry in vacuum, then with dichloromethane eluant, silica gel column chromatography separation is carried out to solid, obtain the Compound I of purifying.
The synthetic route of the preparation of ruddiness organic electromechanical phosphorescent material iridium metal complex is:
The preparation method of above-mentioned ruddiness organic electromechanical phosphorescent material iridium metal complex, using with 3-(4'-trifluoroacetyl phenyl) isoquinoline 99.9 is cyclic metal complexes agent structure, take methyl ethyl diketone as assistant ligand, synthesize above-mentioned ruddiness organic electromechanical phosphorescent material iridium metal complex, preparation method is simple, easy operation, production cost is low, is applicable to industrialization and produces.
As shown in Figure 2, the organic electroluminescence device 200 of one embodiment, comprises the anode layer 220 stacked gradually on substrate 210, hole transmission layer 230, luminescent layer 240, hole blocking layer 250, electron transfer layer 260, electron injection buffer layer 270 and cathode layer 280.
Substrate 210 is glass.
Anode layer 220 is indium tin oxide (ITO), aluminium zinc oxide (AZO) or indium-zinc oxide (IZO).The thickness of anode layer 220 is 100 nanometers.
The material of hole transmission layer 230 can be the conventional hole mobile material in this area.In the particular embodiment, the material of hole transmission layer 230 is two (1-naphthyl)-N, the N'-diphenylbenzidine (NPB) of N, N'-.
The material of luminescent layer 240 comprises material of main part and is doped in the guest materials in material of main part, and guest materials is the ruddiness organic electromechanical phosphorescent material iridium metal complex with following structural formula:
wherein, R is H or methyl.
And the structural formula of ruddiness organic electromechanical phosphorescent material iridium metal complex is:
Wherein, the material of main part of luminescent layer 240 that can commonly use for this area of material of main part.In the present embodiment, material of main part is two carbazyl-4, the 4'-dipyridyl (CBP) of N, N'-, and wherein, the doping mass percent of guest materials is 8%.The thick end of luminescent layer 240, is preferably 30 nanometers.
The material of hole blocking layer 250 can be the conventional hole barrier materials in this area.In the present embodiment, the material of hole blocking layer 250 is 2,9-dimethyl-4,7-phenylbenzene-phenanthrolene (BCP).The thickness of hole blocking layer 250 is preferably 10 nanometers.
The material of electron transfer layer 260 can be the conventional hole barrier materials in this area.In the present embodiment, the material of electron transfer layer 260 is three (oxine) aluminium (Alq
3).The thickness of electron transfer layer 160 is preferably 20 nanometers.
The material of electron injection buffer layer 270 can be the conventional electron injection cushioning material in this area.In the present embodiment, the material of electron injection buffer layer 270 is oxine lithium (Liq).The thickness of electron injection buffer layer 270 is preferably 2 nanometers.
The material of cathode layer 280 can be the conventional cathode material in this area.In the present embodiment, the material of cathode layer 280 is aluminium (Al).The thickness of cathode layer 280 is preferably 100 nanometers.
Guest materials ruddiness organic electromechanical phosphorescent material iridium metal complex and the material of main part of the luminescent layer 240 of above-mentioned organic electroluminescence device 200 have good consistency, can be widely used in monochrome, total colouring and illumination white light parts.
Be below specific embodiment part:
Embodiment 1
The structural formula that the ruddiness organic electromechanical phosphorescent material iridium metal complex of the present embodiment two [3-(4'-trifluoroacetyl phenyl) isoquinoline 99.9-N, C2'] (methyl ethyl diketone) closes iridium is:
The synthesis that this iridium metal complex two [3-(4'-trifluoroacetyl phenyl) isoquinoline 99.9-N, C2'] (methyl ethyl diketone) closes iridium is as follows:
(1) synthesis of part 3-(4'-trifluoroacetyl phenyl) isoquinoline 99.9
At-78 DEG C of temperature, under nitrogen protection, tetrahydrofuran solution 5mL being contained 2.84g (10mmol) 3-(4'-bromophenyl) isoquinoline 99.9 joins in the mixing solutions be made up of 1.29g (12mmol) lithium diisopropyl amido and 10mL tetrahydrofuran (THF), stirring reaction 1h, then the mixing solutions of 1.43mL (12mmol) Trifluoroacetic Acid Ethyl Ester and 5mL tetrahydrofuran (THF) composition is added drop-wise to reaction system, maintaining temperature of reaction is-78 DEG C of continuation stirring reaction 1h, the temperature of question response system is warming up to 0 DEG C naturally, continue stirring reaction 0.5 hour, then add saturated aqueous ammonium chloride solution and continue reaction, make to be extracted with ethyl acetate and obtain organic phase, then anhydrous magnesium sulfate drying organic phase is used, again successively after filtration, rotate the solvent steamed except in filtrate, obtain crude product, volume ratio is used to carry out silica gel column chromatography separating-purifying as eluent to obtaining crude product for the mixed solution of 3:1 sherwood oil and ethyl acetate, obtain colourless 3-(4'-trifluoroacetyl phenyl) isoquinoline 99.9 2.17g, yield is 69.9%.
The reaction formula of synthetic ligands 3-(4'-trifluoroacetyl phenyl) isoquinoline 99.9 is as follows:
The product detection data of step (1) are as follows:
Mass spectrum (m/z): 301.1 (M++1)
Ultimate analysis: C17H10F3NO
Theoretical value: C, 67.78; H, 3.35; F, 18.92; N, 4.65; O, 5.31;
Measured value: C, 67.74; H, 3.43; F, 18.86; N, 4.68; O, 5.29.The material that the above-mentioned reaction of above data acknowledgement obtains is 3-(4'-trifluoroacetyl phenyl) isoquinoline 99.9.
(2) part 3-(4'-trifluoroacetyl phenyl) isoquinoline 99.9 containing the dimeric synthesis of iridium dichloro
Under nitrogen protection, 0.35g (1mmol) three hydrated iridium trichloride and 0.75g (2.5mmol) 3-(4'-trifluoroacetyl phenyl) isoquinoline 99.9 are dissolved in the mixed solvent of the cellosolvo that 20mL volume ratio is 3:1 and water composition, under lucifuge state, reacting by heating system is to the reflux temperature of mixed solvent, stirring reaction 20h, obtain reaction solution, after question response liquid is chilled to room temperature naturally, collecting precipitation thing after filtration, after throw out being adopted the washing with alcohol three times of 95%, vacuum is fully dry, obtain containing red part 3-(4'-trifluoroacetyl phenyl) isoquinoline 99.9 containing the dimeric crude product of iridium dichloro, this crude product need not be purified further, next step reaction can be directly used in.
Synthetic ligands 3-(4'-trifluoroacetyl phenyl) isoquinoline 99.9 containing the dimeric reaction formula of iridium dichloro as follows:
(3) iridium metal complex two [3-(4'-trifluoroacetyl phenyl) isoquinoline 99.9-N, C2'] (methyl ethyl diketone) closes the synthesis of iridium
Under nitrogen protection; obtained for step (2) the contain dimeric crude product of iridium dichloro, 0.21mL (2mmol) methyl ethyl diketone and 0.55g (4mmol) salt of wormwood containing 3-(4'-trifluoroacetyl phenyl) isoquinoline 99.9 are dissolved in 20mL2-ethoxy ethanol solvent; reacting by heating system, to the reflux temperature of cellosolvo, stirs and carries out ligand exchange reaction 15h.After the reaction solution obtained until ligand exchange reaction naturally cools to room temperature, in the appropriate distilled water of impouring, solid collected by filtration, use distilled water wash for several times, then by solid in vacuum after abundant drying, be then that elutriant carries out silica gel column chromatography separating-purifying with methylene dichloride, obtain red pure two [3-(4'-trifluoroacetyl phenyl) isoquinoline 99.9-N, C2'] (methyl ethyl diketone) close iridium 0.29g, and yield is 32.5%.
The reaction equation that iridium metal complex two [3-(4'-trifluoroacetyl phenyl) isoquinoline 99.9-N, C2'] (methyl ethyl diketone) closes iridium is:
The product detection data of step (3) are as follows:
Mass spectrum (m/z): 892.1 (M++1)
Ultimate analysis: C39H25F6IrN2O4
Theoretical value: C, 52.52; H, 2.83; F, 12.78; Ir, 21.55; N, 3.14; O, 7.18;
Measured value: C, 52.55; H, 2.78; F, 12.83; Ir, 21.51; N, 3.18; O, 7.15.The material that the above-mentioned reaction of above data acknowledgement obtains is that iridium metal complex two [3-(4'-trifluoroacetyl phenyl) isoquinoline 99.9-N, C2'] (methyl ethyl diketone) closes iridium.
As shown in Figure 3, the iridium metal complex two [3-(4'-trifluoroacetyl phenyl) isoquinoline 99.9-N, C2'] (methyl ethyl diketone) that prepared by the present embodiment closes iridium dichloromethane solution (~ 10 at 298K temperature
-5mol/L) photoluminescence spectra in, transverse axis is emission wavelength (unit is nm), and the longitudinal axis is the photoluminescence intensity after normalization method.As shown in Figure 3, two [3-(the 4'-trifluoroacetyl phenyl) isoquinoline 99.9-N of iridium metal complex, C2'] (methyl ethyl diketone) close the maximum emission peak of the photoluminescence spectra of iridium at 615nm place, can be used as ruddiness electroluminescent material, and the preparation field of organic electroluminescence device can be widely used in.
In addition, at 298K temperature, concentration is about 10
-5the title complex dichloromethane solution of mol/L, with the fac-Ir (ppy) under the same terms
3dichloromethane solution be standard (phosphorescence quantum yield Φ P=0.40), two [3-(4'-trifluoroacetyl phenyl) isoquinoline 99.9-N, C2'] (methyl ethyl diketones) that record the present embodiment close the Φ of iridium
p=0.34.
Embodiment 2
The structural formula that the ruddiness organic electromechanical phosphorescent material iridium metal complex of the present embodiment two [3-(4'-trifluoroacetyl phenyl)-1-methylisoquinolinium-N, C2'] (methyl ethyl diketone) closes iridium is:
The synthesis that this pair [3-(4'-trifluoroacetyl phenyl)-1-methylisoquinolinium-N, C2'] (methyl ethyl diketone) closes iridium is as follows:
(1) synthesis of part 3-(4'-trifluoroacetyl phenyl)-1-methylisoquinolinium
At-78 DEG C of temperature, under nitrogen protection, tetrahydrofuran solution 5mL being contained 2.98g (10mmol) 3-(4'-bromophenyl)-1-methylisoquinolinium joins in the mixing solutions be made up of 1.29g (12mmol) lithium diisopropyl amido and 10mL tetrahydrofuran (THF), stirring reaction 1h, then the mixing solutions of 1.43mL (12mmol) Trifluoroacetic Acid Ethyl Ester and 5mL tetrahydrofuran (THF) composition is added drop-wise to reaction system, maintaining temperature of reaction is-78 DEG C of continuation stirring reaction 1h, the temperature of question response system rises to 0 DEG C naturally, continue stirring reaction 0.5h, then appropriate saturated aqueous ammonium chloride is added, make to be extracted with ethyl acetate and obtain organic phase, then anhydrous magnesium sulfate drying organic phase is used, again successively after filtration, rotate the solvent steamed except in filtrate, obtain crude product, volume ratio is used to carry out silica gel column chromatography separating-purifying as eluent to obtaining crude product for the mixed solution of 5:1 sherwood oil and ethyl acetate, must without colour purity 3-(4'-trifluoroacetyl phenyl)-1-methylisoquinolinium 2.05g, yield is 65.0%.
The chemical equation of synthesis (1) part 3-(4'-trifluoroacetyl phenyl)-1-methylisoquinolinium is:
The product detection data of step (1) are as follows:
Mass spectrum (m/z): 315.1 (M++1)
Ultimate analysis: C18H12F3NO
Theoretical value: C, 68.57; H, 3.84; F, 18.08; N, 4.44; O, 5.07;
Measured value: C, 68.52; H, 3.92; F, 18.02; N, 4.48; O, 5.06.The material that the above-mentioned reaction of above data acknowledgement obtains is 3-(4'-trifluoroacetyl phenyl)-1-methylisoquinolinium.
(2) part 3-(4'-trifluoroacetyl phenyl)-1-methylisoquinolinium containing the dimeric synthesis of iridium dichloro
Under nitrogen protection, 0.35g (1mmol) three hydrated iridium trichloride and 0.69g (2.2mmol) 3-(4'-trifluoroacetyl phenyl)-1-methylisoquinolinium are dissolved in the mixed solvent of the cellosolvo that 25mL volume ratio is 3:1 and water composition, under lucifuge state, reacting by heating system is to the reflux temperature of mixed solvent, stirring reaction 24h, obtain reaction solution, after question response liquid is chilled to room temperature naturally, collecting precipitation thing after filtration, after throw out being adopted the washing with alcohol three times of 95%, vacuum is fully dry, obtain containing red part 3-(4'-trifluoroacetyl phenyl)-1-methylisoquinolinium containing the dimeric crude product of iridium dichloro, this crude product need not be purified further, next step reaction can be directly used in.
The dimeric reaction equation of iridium dichloro that contains of synthesis 3-(4'-trifluoroacetyl phenyl)-1-methylisoquinolinium is:
(3) iridium metal complex two [3-(4'-trifluoroacetyl phenyl)-1-methylisoquinolinium-N, C2'] (methyl ethyl diketone) closes the synthesis of iridium
Under nitrogen protection; the contain dimeric crude product of iridium dichloro, 0.31mL (3mmol) methyl ethyl diketone and 0.53g (5mmol) sodium carbonate of 3-(4'-trifluoroacetyl phenyl)-1-methylisoquinolinium obtained for step (2) are dissolved in the 2-methyl cellosolve solvent of 25mL; reacting by heating system, to the reflux temperature of cellosolvo, stirs and carries out ligand exchange reaction 18h.After the reaction solution obtained until ligand exchange reaction naturally cools to room temperature, in the appropriate distilled water of impouring, solid collected by filtration, use distilled water wash for several times, then by solid in vacuum after abundant drying, be then that elutriant carries out silica gel column chromatography separating-purifying with methylene dichloride, obtain red pure two [3-(4'-trifluoroacetyl phenyl)-1-methylisoquinolinium-N, C2'] (methyl ethyl diketone) close iridium 0.25g, and yield is 27.2%.
The reaction equation that iridium metal complex two [3-(4'-trifluoroacetyl phenyl)-1-methylisoquinolinium-N, C2'] (methyl ethyl diketone) closes iridium is:
The product detection data of step (3) are as follows:
Mass spectrum (m/z): 920.2 (M++1)
Ultimate analysis: C41H29F6IrN2O4
Theoretical value: C, 53.53; H, 3.18; F, 12.39; Ir, 20.90; N, 3.05; O, 6.96;
Measured value: C, 53.46; H, 3.26; F, 12.33; Ir, 20.95; N, 3.02; O, 6.98.The material that the above-mentioned reaction of above data acknowledgement obtains is that title complex two [3-(4'-trifluoroacetyl phenyl)-1-methylisoquinolinium-N, C2'] (methyl ethyl diketone) closes iridium.
The iridium metal complex prepared of the present embodiment two [3-(4'-trifluoroacetyl phenyl)-1-methylisoquinolinium-N, C2'] (methyl ethyl diketone) close iridium at 298K temperature, dichloromethane solution (~ 10
-5the maximum emission peak of the photoluminescence spectra mol/L), at 607nm place, can be used as ruddiness electroluminescent material, and can be widely used in the preparation field of organic electroluminescence device.
In addition, at 298K temperature, concentration is about 10
-5the title complex dichloromethane solution of mol/L, with the fac-Ir (ppy) under the same terms
3dichloromethane solution be standard (phosphorescence quantum yield Φ P=0.40), two [3-(4'-trifluoroacetyl phenyl) isoquinoline 99.9-N, C2'] (methyl ethyl diketones) that record the present embodiment close the Φ of iridium
p=0.21.
Embodiment 3
The structural formula that the ruddiness organic electromechanical phosphorescent material iridium metal complex of the present embodiment two [3-(4'-trifluoroacetyl phenyl)-4-methylisoquinolinium-N, C2'] (methyl ethyl diketone) closes iridium is:
The synthesis that this iridium metal complex two [3-(4'-trifluoroacetyl phenyl)-4-methylisoquinolinium-N, C2'] (methyl ethyl diketone) closes iridium is as follows:
(1) synthesis of part 3-(4'-trifluoroacetyl phenyl)-4-methylisoquinolinium
At-78 DEG C of temperature, under nitrogen protection, tetrahydrofuran solution 10mL being contained 2.98g (10mmol) 3-(4'-bromophenyl)-4-methylisoquinolinium joins in the mixing solutions be made up of 1.39g (13mmol) lithium diisopropyl amido and 10mL tetrahydrofuran (THF), stirring reaction 2h, then the mixing solutions of 1.55mL (13mmol) Trifluoroacetic Acid Ethyl Ester and 5mL tetrahydrofuran (THF) composition is added drop-wise to reaction system, maintaining temperature of reaction is-78 DEG C of continuation stirring reaction 1h, the temperature of question response system is warming up to 0 DEG C naturally, continue stirring reaction 0.8 hour, then add saturated aqueous ammonium chloride solution and continue reaction, make to be extracted with ethyl acetate and obtain organic phase, then anhydrous magnesium sulfate drying organic phase is used, again successively after filtration, rotate the solvent steamed except in filtrate, obtain crude product, the mixed solution of the sherwood oil that use volume ratio is 5:1 and ethyl acetate composition carries out silica gel column chromatography separating-purifying as eluent to obtaining crude product, obtain colourless 3-(4'-trifluoroacetyl phenyl)-4-methylisoquinolinium 2.00g, yield is 63.4%.
The reaction formula of synthetic ligands 3-(4'-trifluoroacetyl phenyl)-4-methylisoquinolinium is as follows:
The product detection data of step (1) are as follows:
Mass spectrum (m/z): 315.1 (M++1)
Ultimate analysis: C18H12F3NO
Theoretical value: C, 68.57; H, 3.84; F, 18.08; N, 4.44; O, 5.07;
Measured value: C, 68.50; H, 3.92; F, 18.05; N, 4.48; O, 5.05.The material that the above-mentioned reaction of above data acknowledgement obtains is 3-(4'-trifluoroacetyl phenyl)-4-methylisoquinolinium.
(2) part be 3-(4'-trifluoroacetyl phenyl)-4-methylisoquinolinium containing the dimeric synthesis of iridium dichloro
Under nitrogen protection, 0.35g (1mmol) three hydrated iridium trichloride and 0.94g (3mmol) 3-(4'-trifluoroacetyl phenyl)-4-methylisoquinolinium are dissolved in the mixed solvent of the cellosolvo that 30mL volume ratio is 3:1 and water composition, under lucifuge state, reacting by heating system is to the reflux temperature of mixed solvent, stirring reaction 24h, obtain reaction solution, after question response liquid is chilled to room temperature naturally, collecting precipitation thing after filtration, after throw out being adopted the washing with alcohol three times of 95%, vacuum is fully dry, obtain containing red part 3-(4'-trifluoroacetyl phenyl)-4-methylisoquinolinium containing the dimeric crude product of iridium dichloro, this crude product need not be purified further, next step reaction can be directly used in.
Synthetic ligands 3-(4'-trifluoroacetyl phenyl)-4-methylisoquinolinium containing the dimeric reaction formula of iridium dichloro as follows:
(3) iridium metal complex two [3-(4'-trifluoroacetyl phenyl)-4-methylisoquinolinium-N, C2'] (methyl ethyl diketone) closes the synthesis of iridium
Under nitrogen protection; be dissolved in 25mL2-ethoxy ethanol solvent by obtained for step (2) the contain dimeric crude product of iridium dichloro, 0.41mL (4mmol) methyl ethyl diketone and 0.53g (5mmol) sodium carbonate containing 3-(4'-trifluoroacetyl phenyl)-4-methylisoquinolinium, reacting by heating system carries out ligand exchange reaction 16h to the stirred under reflux temperature of cellosolvo.After the reaction solution obtained until ligand exchange reaction naturally cools to room temperature, in the appropriate distilled water of impouring, solid collected by filtration, use distilled water wash for several times, then by solid in vacuum after abundant drying, be then that elutriant carries out silica gel column chromatography separating-purifying with methylene dichloride, obtain red two [3-(4'-trifluoroacetyl phenyl)-4-methylisoquinolinium-N, C2'] (methyl ethyl diketone) close iridium 0.24g, and yield is 26.1%.
The reaction equation that iridium metal complex two [3-(4'-trifluoroacetyl phenyl)-4-methylisoquinolinium-N, C2'] (methyl ethyl diketone) closes iridium is:
The product detection data of step (3) are as follows:
Mass spectrum (m/z): 920.2 (M++1)
Ultimate analysis: C41H29F6IrN2O4
Theoretical value: C, 53.53; H, 3.18; F, 12.39; Ir, 20.90; N, 3.05; O, 6.96;
Measured value: C, 53.44; H, 3.25; F, 12.43; Ir, 20.87; N, 3.11; O, 6.90.The material that the above-mentioned reaction of above data acknowledgement obtains is that title complex two [3-(4'-trifluoroacetyl phenyl)-4-methylisoquinolinium-N, C2'] (methyl ethyl diketone) closes iridium.
The iridium metal complex prepared of the present embodiment two [3-(4'-trifluoroacetyl phenyl)-4-methylisoquinolinium-N, C2'] (methyl ethyl diketone) close iridium at 298K temperature, dichloromethane solution (~ 10
-5the maximum emission peak of the photoluminescence spectra mol/L), at 609nm place, can be used as ruddiness electroluminescent material, and can be widely used in the preparation field of organic electroluminescence device.
In addition, at 298K temperature, concentration is about 10
-5the title complex dichloromethane solution of mol/L, with the fac-Ir (ppy) under the same terms
3dichloromethane solution be standard (phosphorescence quantum yield Φ P=0.40), two [3-(4'-trifluoroacetyl phenyl)-4-methylisoquinolinium-N, C2'] (methyl ethyl diketones) that record the present embodiment close the Φ of iridium
p=0.20.
Embodiment 4
The structural formula that the ruddiness organic electromechanical phosphorescent material iridium metal complex of the present embodiment two [3-(4'-trifluoroacetyl phenyl)-5-methylisoquinolinium-N, C2'] (methyl ethyl diketone) closes iridium is:
The synthesis that this iridium metal complex two [3-(4'-trifluoroacetyl phenyl)-5-methylisoquinolinium-N, C2'] (methyl ethyl diketone) closes iridium is as follows:
(1) synthesis of part 3-(4'-trifluoroacetyl phenyl)-5-methylisoquinolinium
At-78 DEG C of temperature, under nitrogen protection, tetrahydrofuran solution 10mL being contained 2.98g (10mmol) 3-(4'-bromophenyl)-5-methylisoquinolinium joins in the mixing solutions be made up of 1.39g (13mmol) lithium diisopropyl amido and 10mL tetrahydrofuran (THF), stirring reaction 1.5h, then the mixing solutions of 1.55mL (13mmol) Trifluoroacetic Acid Ethyl Ester and 5mL tetrahydrofuran (THF) composition is added drop-wise to reaction system, maintaining temperature of reaction is-78 DEG C of continuation stirring reaction 1h, the temperature of question response system is warming up to 0 DEG C naturally, continue stirring reaction 0.5 hour, then add saturated aqueous ammonium chloride solution and continue reaction, make to be extracted with ethyl acetate and obtain organic phase, then anhydrous magnesium sulfate drying organic phase is used, again successively after filtration, rotate the solvent steamed except in filtrate, obtain crude product, the mixed solution of the sherwood oil that use volume ratio is 5:1 and ethyl acetate composition carries out silica gel column chromatography separating-purifying as eluent to obtaining crude product, obtain colourless 3-(4'-trifluoroacetyl phenyl)-5-methylisoquinolinium 1.92g, yield is 60.9%.
The reaction formula of synthetic ligands 3-(4'-trifluoroacetyl phenyl)-5-methylisoquinolinium is as follows:
The product detection data of step (1) are as follows:
Mass spectrum (m/z): 315.1 (M++1)
Ultimate analysis: C18H12F3NO
Theoretical value: C, 68.57; H, 3.84; F, 18.08; N, 4.44; O, 5.07;
Measured value: C, 68.54; H, 3.91; F, 18.04; N, 4.50; O, 5.01.The material that the above-mentioned reaction of above data acknowledgement obtains is 3-(4'-trifluoroacetyl phenyl)-5-methylisoquinolinium.
(2) part 3-(4'-trifluoroacetyl phenyl)-5-methylisoquinolinium containing the dimeric synthesis of iridium dichloro
Under nitrogen protection, 0.35g (1mmol) three hydrated iridium trichloride and 0.79g (2.5mmol) 3-(4'-trifluoroacetyl phenyl)-5-methylisoquinolinium are dissolved in the mixed solvent of the cellosolvo that 25mL volume ratio is 3:1 and water composition, under lucifuge state, reacting by heating system is to the reflux temperature of mixed solvent, stirring reaction 22h, obtain reaction solution, after question response liquid is chilled to room temperature naturally, collecting precipitation thing after filtration, after throw out being adopted the washing with alcohol three times of 95%, vacuum is fully dry, obtain containing 3-(4'-trifluoroacetyl phenyl)-5-methylisoquinolinium containing the dimeric crude product of iridium dichloro, this crude product need not be purified further, next step reaction can be directly used in.
Synthetic ligands 3-(4'-trifluoroacetyl phenyl)-5-methylisoquinolinium containing the dimeric reaction formula of iridium dichloro as follows:
(3) iridium metal complex two [3-(4'-trifluoroacetyl phenyl)-5-methylisoquinolinium-N, C
2'] (methyl ethyl diketone) close the synthesis of iridium
Under nitrogen protection; obtained for step (2) the contain dimeric crude product of iridium dichloro, 0.31mL (3mmol) methyl ethyl diketone and 0.41g (3mmol) salt of wormwood containing 3-(4'-trifluoroacetyl phenyl)-5-methylisoquinolinium are dissolved in the cellosolvo solvent of 20mL; reacting by heating system, to the reflux temperature of cellosolvo, stirs and carries out ligand exchange reaction 20h.After the reaction solution obtained until ligand exchange reaction naturally cools to room temperature, in the appropriate distilled water of impouring, solid collected by filtration, use distilled water wash for several times, then by solid in vacuum after abundant drying, be then that elutriant carries out silica gel column chromatography separating-purifying with methylene dichloride, obtain red pure two [3-(4'-trifluoroacetyl phenyl)-5-methylisoquinolinium-N, C2'] (methyl ethyl diketone) close iridium 0.23g, and yield is 25.0.
The reaction equation that iridium metal complex two [3-(4'-trifluoroacetyl phenyl)-5-methylisoquinolinium-N, C2'] (methyl ethyl diketone) closes iridium is:
The product detection data of step (3) are as follows:
Mass spectrum (m/z): 920.2 (M++1)
Ultimate analysis: C41H29F6IrN2O4
Theoretical value: C, 53.53; H, 3.18; F, 12.39; Ir, 20.90; N, 3.05; O, 6.96;
Measured value: C, 53.48; H, 3.24; F, 12.33; Ir, 20.97; N, 3.03; O, 6.95.The material that the above-mentioned reaction of above data acknowledgement obtains is that two [3-(4'-trifluoroacetyl phenyl)-5-methylisoquinolinium-N, C2'] (methyl ethyl diketone) closes iridium.
The iridium metal complex prepared of the present embodiment two [3-(4'-trifluoroacetyl phenyl)-5-methylisoquinolinium-N, C2'] (methyl ethyl diketone) close iridium at 298K temperature, dichloromethane solution (~ 10
-5the maximum emission peak of the photoluminescence spectra mol/L), at 611nm place, can be used as ruddiness electroluminescent material, and can be widely used in the preparation field of organic electroluminescence device.
In addition, at 298K temperature, concentration is about 10
-5the title complex dichloromethane solution of mol/L, with the fac-Ir (ppy) under the same terms
3dichloromethane solution be standard (phosphorescence quantum yield Φ P=0.40), two [3-(4'-trifluoroacetyl phenyl)-5-methylisoquinolinium-N, C2'] (methyl ethyl diketones) that record the present embodiment close the Φ of iridium
p=0.18.
Embodiment 5
Ruddiness organic electromechanical phosphorescent material two [3-(4'-trifluoroacetyl phenyl)-6-methylisoquinolinium-N, the C of the present embodiment
2'] (methyl ethyl diketone) structural formula of closing iridium is:
The synthesis that this iridium metal complex two [3-(4'-trifluoroacetyl phenyl)-6-methylisoquinolinium-N, C2'] (methyl ethyl diketone) closes iridium is as follows:
(1) synthesis of part 3-(4'-trifluoroacetyl phenyl)-6-methylisoquinolinium
At-78 DEG C of temperature, under nitrogen protection, tetrahydrofuran solution 10mL being contained 2.98g (10mmol) 3-(4'-bromophenyl)-6-methylisoquinolinium joins in the mixing solutions be made up of 1.18g (11mmol) lithium diisopropyl amido and 10mL tetrahydrofuran (THF), stirring reaction 2h, then the mixing solutions of 1.31mL (11mmol) Trifluoroacetic Acid Ethyl Ester and 10mL tetrahydrofuran (THF) composition is added drop-wise to reaction system, maintaining temperature of reaction is-78 DEG C of continuation stirring reaction 1.5h, the temperature of question response system is warming up to 0 DEG C naturally, continue stirring reaction 1 hour, then add saturated aqueous ammonium chloride solution and continue reaction, make to be extracted with ethyl acetate and obtain organic phase, then anhydrous magnesium sulfate drying organic phase is used, again successively after filtration, rotate the solvent steamed except in filtrate, , obtain crude product, the mixed solution of the sherwood oil that use volume ratio is 5:1 and ethyl acetate composition carries out silica gel column chromatography separating-purifying as eluent to obtaining crude product, obtain colourless 3-(4'-trifluoroacetyl phenyl)-6-methylisoquinolinium 1.95g, yield is 61.8%.
The reaction formula of synthetic ligands 3-(4'-trifluoroacetyl phenyl)-6-methylisoquinolinium is as follows:
The product detection data of step (1) are as follows:
Mass spectrum (m/z): 315.1 (M++1)
Ultimate analysis: C18H12F3NO
Theoretical value: C, 68.57; H, 3.84; F, 18.08; N, 4.44; O, 5.07;
Measured value: C, 68.55; H, 3.90; F, 18.02; N, 4.49; O, 5.04.The material that the above-mentioned reaction of above data acknowledgement obtains is 3-(4'-trifluoroacetyl phenyl)-6-methylisoquinolinium.
(2) part 3-(4'-trifluoroacetyl phenyl)-6-methylisoquinolinium containing the dimeric synthesis of iridium dichloro
Under nitrogen protection, 0.35g (1mmol) three hydrated iridium trichloride and 0.69g (2.2mmol) 3-(4'-trifluoroacetyl phenyl)-6-methylisoquinolinium are dissolved in the mixed solvent of the cellosolvo that 30mL volume ratio is 3:1 and water composition, under lucifuge state, reacting by heating system is to the reflux temperature of mixed solvent, stirring reaction 20h, obtain reaction solution, after question response liquid is chilled to room temperature naturally, collecting precipitation thing after filtration, after throw out being adopted the washing with alcohol three times of 95%, vacuum is fully dry, what obtain containing red part 3-(4'-trifluoroacetyl phenyl)-6-methylisoquinolinium is dimeric containing the dimeric crude product of iridium dichloro containing iridium dichloro, this crude product need not be purified further, next step reaction can be directly used in.
Synthetic ligands 3-(4'-trifluoroacetyl phenyl)-6-methylisoquinolinium containing the dimeric reaction formula of iridium dichloro as follows:
(3) iridium metal complex two [3-(4'-trifluoroacetyl phenyl)-6-methylisoquinolinium-N, C2'] (methyl ethyl diketone) closes the synthesis of iridium
Under nitrogen protection; obtained for step (2) the contain dimeric crude product of iridium dichloro, 0.41mL (4mmol) methyl ethyl diketone and 0.42g (4mmol) sodium carbonate containing 3-(4'-trifluoroacetyl phenyl)-6-methylisoquinolinium are dissolved in 25mL2-ethoxy ethanol solvent; reacting by heating system, to the reflux temperature of cellosolvo, stirs and carries out ligand exchange reaction 15h.After the reaction solution obtained until ligand exchange reaction naturally cools to room temperature, in the appropriate distilled water of impouring, solid collected by filtration, use distilled water wash for several times, then by solid in vacuum after abundant drying, be then that elutriant carries out silica gel column chromatography separating-purifying with methylene dichloride, obtain red pure two [3-(4'-trifluoroacetyl phenyl)-6-methylisoquinolinium-N, C2'] (methyl ethyl diketone) close iridium 0.20g, and yield is 21.7%.
The reaction equation that iridium metal complex two [3-(4'-trifluoroacetyl phenyl)-6-methylisoquinolinium-N, C2'] (methyl ethyl diketone) closes iridium is:
The product detection data of step (3) are as follows:
Mass spectrum (m/z): 920.2 (M++1)
Ultimate analysis: C41H29F6IrN2O4
Theoretical value: C, 53.53; H, 3.18; F, 12.39; Ir, 20.90; N, 3.05; O, 6.96;
Measured value: C, 53.47; H, 3.24; F, 12.35; Ir, 20.97; N, 3.00; O, 6.97.The material that the above-mentioned reaction of above data acknowledgement obtains is that iridium metal complex two [3-(4'-trifluoroacetyl phenyl)-6-methylisoquinolinium-N, C2'] (methyl ethyl diketone) closes iridium.
The iridium metal complex prepared of the present embodiment two [3-(4'-trifluoroacetyl phenyl)-6-methylisoquinolinium-N, C2'] (methyl ethyl diketone) close iridium at 298K temperature, dichloromethane solution (~ 10
-5the maximum emission peak of the photoluminescence spectra mol/L), at 612nm place, can be used as ruddiness electroluminescent material, and can be widely used in the preparation field of organic electroluminescence device.
In addition, at 298K temperature, concentration is about 10
-5the title complex dichloromethane solution of mol/L, with the fac-Ir (ppy) under the same terms
3dichloromethane solution be standard (phosphorescence quantum yield Φ P=0.40), two [3-(4'-trifluoroacetyl phenyl)-6-methylisoquinolinium-N, C2'] (methyl ethyl diketones) that record the present embodiment close the Φ of iridium
p=0.15.
Embodiment 6
The structural formula that the ruddiness organic electromechanical phosphorescent material iridium metal complex of the present embodiment two [3-(4'-trifluoroacetyl phenyl)-7-methylisoquinolinium-N, C2'] (methyl ethyl diketone) closes iridium is:
The synthesis that this iridium metal complex two [3-(4'-trifluoroacetyl phenyl)-7-methylisoquinolinium-N, C2'] (methyl ethyl diketone) closes iridium is as follows:
(1) synthesis of part 3-(4'-trifluoroacetyl phenyl)-7-methylisoquinolinium
At-78 DEG C of temperature, under nitrogen protection, tetrahydrofuran solution 10mL being contained 2.98g (10mmol) 3-(4'-bromophenyl)-7-methylisoquinolinium joins in the mixing solutions be made up of 1.18g (11mmol) lithium diisopropyl amido and 10mL tetrahydrofuran (THF), stirring reaction 2h, then the mixing solutions of 1.31mL (11mmol) Trifluoroacetic Acid Ethyl Ester and 10mL tetrahydrofuran (THF) composition is added drop-wise to reaction system, maintaining temperature of reaction is-78 DEG C of continuation stirring reaction 1.5h, the temperature of question response system is warming up to 0 DEG C naturally, continue stirring reaction 0.5 hour, then add saturated aqueous ammonium chloride solution and continue reaction, make to be extracted with ethyl acetate and obtain organic phase, then anhydrous magnesium sulfate drying organic phase is used, again successively after filtration, rotate the solvent steamed except in filtrate, obtain crude product, the mixed solution of the sherwood oil that use volume ratio is 5:1 and ethyl acetate composition carries out silica gel column chromatography separating-purifying as eluent to obtaining crude product, obtain colourless 3-(4'-trifluoroacetyl phenyl)-7-methylisoquinolinium 1.94g, yield is 61.5%.
The reaction formula of synthetic ligands 3-(4'-trifluoroacetyl phenyl)-7-methylisoquinolinium is as follows:
The product detection data of step (1) are as follows:
Mass spectrum (m/z): 315.1 (M++1)
Ultimate analysis: C18H12F3NO
Theoretical value: C, 68.57; H, 3.84; F, 18.08; N, 4.44; O, 5.07;
Measured value: C, 68.52; H, 3.93; F, 18.03; N, 4.47; O, 5.05.The material that the above-mentioned reaction of above data acknowledgement obtains is 3-(4'-trifluoroacetyl phenyl)-7-methylisoquinolinium.
(2) part be 3-(4'-trifluoroacetyl phenyl)-7-methylisoquinolinium containing the dimeric synthesis of iridium dichloro
Under nitrogen protection, 0.35g (1mmol) three hydrated iridium trichloride and 0.79g (2.5mmol) 3-(4'-trifluoroacetyl phenyl)-7-methylisoquinolinium are dissolved in the mixed solvent of the cellosolvo that 25mL volume ratio is 3:1 and water composition, under lucifuge state, reacting by heating system is to the reflux temperature of mixed solvent, stirring reaction 20h, obtain reaction solution, after question response liquid is chilled to room temperature naturally, collecting precipitation thing after filtration, after throw out being adopted the washing with alcohol three times of 95%, vacuum is fully dry, obtain containing red part 3-(4'-trifluoroacetyl phenyl)-7-methylisoquinolinium containing the dimeric crude product of iridium dichloro, this crude product need not be purified further, next step reaction can be directly used in.
Synthetic ligands is the as follows containing the dimeric reaction formula of iridium dichloro of 3-(4'-trifluoroacetyl phenyl)-7-methylisoquinolinium:
(3) iridium metal complex two [3-(4'-trifluoroacetyl phenyl)-7-methylisoquinolinium-N, C2'] (methyl ethyl diketone) closes the synthesis of iridium
Under nitrogen protection; obtained for step (2) the contain dimeric crude product of iridium dichloro, 0.41mL (4mmol) methyl ethyl diketone and 0.53g (5mmol) sodium carbonate containing 3-(4'-trifluoroacetyl phenyl)-7-methylisoquinolinium are dissolved in the cellosolvo solvent of 25mL; reacting by heating system, to the reflux temperature of cellosolvo, stirs and carries out ligand exchange reaction 16h.After the reaction solution obtained until ligand exchange reaction naturally cools to room temperature, in the appropriate distilled water of impouring, solid collected by filtration, use distilled water wash for several times, then by solid in vacuum after abundant drying, be then that elutriant carries out silica gel column chromatography separating-purifying with methylene dichloride, obtain red pure two [3-(4'-trifluoroacetyl phenyl)-7-methylisoquinolinium-N, C2'] (methyl ethyl diketone) close iridium 0.22g, and yield is 23.9%.
The reaction equation that iridium metal complex two [3-(4'-trifluoroacetyl phenyl)-7-methylisoquinolinium-N, C2'] (methyl ethyl diketone) closes iridium is:
The product detection data of step (3) are as follows:
Mass spectrum (m/z): 920.2 (M++1)
Ultimate analysis: C41H29F6IrN2O4
Theoretical value: C, 53.53; H, 3.18; F, 12.39; Ir, 20.90; N, 3.05; O, 6.96;
Measured value: C, 53.54; H, 3.13; F, 12.44; Ir, 20.85; N, 3.12; O, 6.92.The material that the above-mentioned reaction of above data acknowledgement obtains is that title complex two [3-(4'-trifluoroacetyl phenyl)-7-methylisoquinolinium-N, C2'] (methyl ethyl diketone) closes iridium.
The iridium metal complex prepared of the present embodiment two [3-(4'-trifluoroacetyl phenyl)-7-methylisoquinolinium-N, C2'] (methyl ethyl diketone) close iridium at 298K temperature, dichloromethane solution (~ 10
-5the maximum emission peak of the photoluminescence spectra mol/L), at 611nm place, can be used as ruddiness electroluminescent material, and can be widely used in the preparation field of organic electroluminescence device.
In addition, at 298K temperature, concentration is about 10
-5the title complex dichloromethane solution of mol/L, with the fac-Ir (ppy) under the same terms
3dichloromethane solution be standard (phosphorescence quantum yield Φ P=0.40), two [3-(4'-trifluoroacetyl phenyl)-7-methylisoquinolinium-N, C2'] (methyl ethyl diketones) that record the present embodiment close the Φ of iridium
p=0.17.
Embodiment 7
The structural formula that the ruddiness organic electromechanical phosphorescent material iridium metal complex of the present embodiment two [3-(4'-trifluoroacetyl phenyl)-8-methylisoquinolinium-N, C2'] (methyl ethyl diketone) closes iridium is:
The synthesis that this iridium metal complex two [3-(4'-trifluoroacetyl phenyl)-8-methylisoquinolinium-N, C2'] (methyl ethyl diketone) closes iridium is as follows:
(1) synthesis of part 3-(4'-trifluoroacetyl phenyl)-8-methylisoquinolinium
At-78 DEG C of temperature, under nitrogen protection, tetrahydrofuran solution 10mL being contained 2.98g (10mmol) 3-(4'-bromophenyl)-8-methylisoquinolinium joins in the mixing solutions be made up of 1.39g (13mmol) lithium diisopropyl amido and 15mL tetrahydrofuran (THF), stirring reaction 2h, then the mixing solutions of 1.55mL (13mmol) Trifluoroacetic Acid Ethyl Ester and 10mL tetrahydrofuran (THF) composition is added drop-wise to reaction system, maintaining temperature of reaction is-78 DEG C of continuation stirring reaction 2h, the temperature of question response system is warming up to 0 DEG C naturally, continue stirring reaction 0.5 hour, then add saturated aqueous ammonium chloride solution and continue reaction, make to be extracted with ethyl acetate and obtain organic phase, then anhydrous magnesium sulfate drying organic phase is used, again successively after filtration, rotate the solvent steamed except in filtrate, obtain crude product, the mixed solution of the sherwood oil that use volume ratio is 5:1 and ethyl acetate composition carries out silica gel column chromatography separating-purifying as eluent to obtaining crude product, obtain colourless 3-(4'-trifluoroacetyl phenyl)-8-methylisoquinolinium 2.00g, yield is 63.4%.
The reaction formula of synthetic ligands 3-(4'-trifluoroacetyl phenyl)-8-methylisoquinolinium is as follows:
The product detection data of step (1) are as follows:
Mass spectrum (m/z): 315.1 (M++1)
Ultimate analysis: C18H12F3NO
Theoretical value: C, 68.57; H, 3.84; F, 18.08; N, 4.44; O, 5.07;
Measured value: C, 68.53; H, 3.90; F, 18.05; N, 4.49; O, 5.03.The material that the above-mentioned reaction of above data acknowledgement obtains is 3-(4'-trifluoroacetyl phenyl)-8-methylisoquinolinium.
(2) part 3-(4'-trifluoroacetyl phenyl)-8-methylisoquinolinium containing the dimeric synthesis of iridium dichloro
Under nitrogen protection, 0.35g (1mmol) three hydrated iridium trichloride and 0.79g (2.5mmol) 3-(4'-trifluoroacetyl phenyl)-8-methylisoquinolinium are dissolved in the mixed solvent of the cellosolvo that 25mL volume ratio is 3:1 and water composition, under lucifuge state, reacting by heating system is to the reflux temperature of mixed solvent, stirring reaction 20h, obtain reaction solution, after question response liquid is chilled to room temperature naturally, collecting precipitation thing after filtration, after throw out being adopted the washing with alcohol three times of 95%, vacuum is fully dry, obtain containing red part 3-(4'-trifluoroacetyl phenyl)-8-methylisoquinolinium containing the dimeric crude product of iridium dichloro, this crude product need not be purified further, next step reaction can be directly used in.
Synthetic ligands 3-(4'-trifluoroacetyl phenyl)-8-methylisoquinolinium containing the dimeric reaction formula of iridium dichloro as follows:
(3) iridium metal complex two [3-(4'-trifluoroacetyl phenyl)-8-methylisoquinolinium-N, C2'] (methyl ethyl diketone) closes the synthesis of iridium
Under nitrogen protection; obtained for step (2) the contain dimeric crude product of iridium dichloro, 0.41mL (4mmol) methyl ethyl diketone and 0.53g (5mmol) sodium carbonate containing 3-(4'-trifluoroacetyl phenyl)-8-methylisoquinolinium are dissolved in the cellosolvo solvent of 25mL; reacting by heating system, to the reflux temperature of cellosolvo, stirs and carries out ligand exchange reaction 18h.After the reaction solution obtained until ligand exchange reaction naturally cools to room temperature, in the appropriate distilled water of impouring, solid collected by filtration, use distilled water wash for several times, then by solid in vacuum after abundant drying, be then that elutriant carries out silica gel column chromatography separating-purifying with methylene dichloride, obtain red pure two [3-(4'-trifluoroacetyl phenyl)-8-methylisoquinolinium-N, C2'] (methyl ethyl diketone) close iridium 0.23g, and yield is 25.0%.
The reaction equation that iridium metal complex two [3-(4'-trifluoroacetyl phenyl)-8-methylisoquinolinium-N, C2'] (methyl ethyl diketone) closes iridium is:
The product detection data of step (3) are as follows:
Mass spectrum (m/z): 920.2 (M++1)
Ultimate analysis: C41H29F6IrN2O4
Theoretical value: C, 53.53; H, 3.18; F, 12.39; Ir, 20.90; N, 3.05; O, 6.96;
Measured value: C, 53.58; H, 3.11; F, 12.45; Ir, 20.86; N, 3.12; O, 6.88.The material that the above-mentioned reaction of above data acknowledgement obtains is that title complex two [3-(4'-trifluoroacetyl phenyl)-8-methylisoquinolinium-N, C2'] (methyl ethyl diketone) closes iridium.
The iridium metal complex prepared of the present embodiment two [3-(4'-trifluoroacetyl phenyl)-8-methylisoquinolinium-N, C2'] (methyl ethyl diketone) close iridium at 298K temperature, dichloromethane solution (~ 10
-5the maximum emission peak of the photoluminescence spectra mol/L), at 610nm place, can be used as ruddiness electroluminescent material, and can be widely used in the preparation field of organic electroluminescence device.
In addition, at 298K temperature, concentration is about 10
-5the title complex dichloromethane solution of mol/L, with the fac-Ir (ppy) under the same terms
3dichloromethane solution be standard (phosphorescence quantum yield Φ P=0.40), two [3-(4'-trifluoroacetyl phenyl)-8-methylisoquinolinium-N, C2'] (methyl ethyl diketones) that record the present embodiment close the Φ of iridium
p=0.19.
Embodiment 8
The structure of the organic electroluminescence device of embodiment 8 is: ITO/NPB/CBP:Ir title complex/BCP/Alq
3/ Liq/Al.
The preparation of organic electroluminescence device: adopt vacuum plating techniques of deposition thickness is 100nm, square resistance is 20 Ω/mouth tin indium oxide (ITO) as transparent anode layer successively on the glass substrate that acetone, methyl alcohol, distilled water and Virahol are cleaned at one; Prepare by vacuum evaporation the N that thickness is 65nm successively on the anode layer, two (1-naphthyl)-N, N '-diphenylbenzidine (NPB) material of N'-is as hole transmission layer; Hole transmission layer is prepared the luminescent layer that thickness is 30nm, the material of luminescent layer is two [3-(4'-trifluoroacetyl phenyl) isoquinoline 99.9-N prepared by embodiment 1, C2'] (methyl ethyl diketone) close iridium doping N, the two carbazyl-4 of N'-, 4'-dipyridyl (CBP), the doping mass percent that two [3-(4'-trifluoroacetyl phenyl) isoquinoline 99.9-N, C2'] (methyl ethyl diketone) closes iridium is 8%, and luminescent layer is expressed as CBP:Ir title complex; On luminescent layer, vacuum evaporation thickness is that 2,9-dimethyl-4,7-phenylbenzene-phenanthrolene (BCP) materials of 10nm are as hole blocking layer successively; Hole blocking layer is prepared three (oxine) aluminium (Alq that thickness is 20nm
3) as electron transfer layer; Preparing thickness is on the electron transport layer that the oxine lithium (Liq) of 2nm is as electron injection buffer layer; Last vacuum evaporation thickness is on the buffer layer that the metal A l of 100nm is as cathode layer.Current versus brightness-the voltage characteristic of the organic electroluminescence device of this enforcement is tested by Keithley source measuring system (Keithley2400Sourcemeter), with French its electroluminescent spectrum of JY company SPEX CCD3000 spectrometer measurement, all measurements all complete in atmosphere at room temperature, record the maximum emission wavelength of organic electroluminescence device at 616nm place, the maximum lumen efficiency of device is 6.76lm/W, and maximum current efficiency is 7.35cd/A.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a ruddiness organic electromechanical phosphorescent material iridium metal complex, is characterized in that, has following structural formula:
Wherein, R is H or methyl.
2. ruddiness organic electromechanical phosphorescent material iridium metal complex according to claim 1, is characterized in that, the structural formula of described ruddiness organic electromechanical phosphorescent material iridium metal complex is:
3. a preparation method for ruddiness organic electromechanical phosphorescent material iridium metal complex, is characterized in that, comprises the steps:
The compd A that following structural formula represents is provided,
Wherein, R is H or methyl;
Under anaerobic, described compd A and three hydrated iridium trichloride are formed the first mixing solutions for 2.2:1 ~ 3:1 is dissolved in the first solvent in molar ratio, under lucifuge condition, back flow reaction 20 hours ~ 24 hours, after filtering cleaning, obtain the crude product containing compd B, described compd B has following structural formula
Under anaerobic and anhydrous condition, described crude product, methyl ethyl diketone and alkaline catalysts containing compd B is dissolved in the second solvent and obtains the second mixing solutions, carry out ligand exchange reaction 15 hours ~ 20 hours, after separation and purification, obtain the Compound I with following structural formula
Wherein, the mol ratio of described methyl ethyl diketone and described three hydrated iridium trichloride 2:1 ~ 4:1 of being.
4. the preparation method of ruddiness organic electromechanical phosphorescent material iridium metal complex according to claim 3, it is characterized in that, after described back flow reaction, described filtration cleaning step is: first the reaction solution after described back flow reaction is cooled to room temperature, collecting precipitation thing after filtration, described throw out is adopted ethanol purge, after vacuum-drying, obtains the described crude product containing compd B.
5. the preparation method of the ruddiness organic electromechanical phosphorescent material iridium metal complex according to claim 3 or 4, is characterized in that, the temperature of described back flow reaction is the reflux temperature of described first solvent; Described first solvent is form mixed solvent by cellosolvo and water; Described in described first solvent, the volume ratio of cellosolvo and water is 3:1; The concentration of described three hydrated iridium trichloride in described first mixing solutions is 0.033mol/L ~ 0.05mol/L.
6. the preparation method of ruddiness organic electromechanical phosphorescent material iridium metal complex according to claim 3, is characterized in that, the temperature of described ligand exchange reaction is the reflux temperature of the second solvent; Described second solvent is cellosolvo or 2-methyl cellosolve; The concentration of the described compd B in described second mixing solutions is 0.1mol/L ~ 0.2mol/L; Described alkaline catalysts is salt of wormwood or sodium carbonate; The molar weight of described alkaline catalysts is 3 ~ 5 times of the molar weight of described three hydrated iridium trichloride.
7. the preparation method of ruddiness organic electromechanical phosphorescent material iridium metal complex according to claim 3, it is characterized in that, after described ion exchange reaction, the step of described separation and purification is: after the reaction solution first obtained after described ligand exchange reaction naturally cools to room temperature, add distilled water, solid collected by filtration, use solid described in distilled water wash, then, described solid is dry in vacuum, then with dichloromethane eluant, silica gel column chromatography separation is carried out to described solid, obtain the described Compound I of purifying.
8. the preparation method of ruddiness organic electromechanical phosphorescent material iridium metal complex according to claim 3, it is characterized in that, described compd A is prepared by following steps:
The Compound C with following structural formula is provided,
Under-78 DEG C and oxygen free condition, be 1:1.1 ~ 1:1.3 in molar ratio, by described Compound C and diisopropylamino lithium stirring reaction 1 hour ~ 2 hours in organic solvent, then the organic solution of trifluoroacetyl ethyl ester is added, maintaining temperature of reaction is-78 DEG C of continuation stirring reactions 1 hour ~ 2 hours, question response temperature is warming up to 0 DEG C naturally, continue stirring reaction 0.5 hour ~ 1 hour, then add saturated aqueous ammonium chloride solution and continue reaction, after separating-purifying, obtain described compd A, wherein, the mol ratio of described trifluoroacetyl ethyl ester and described diisopropylamino lithium is 1:1.
9. the preparation method of ruddiness organic electromechanical phosphorescent material iridium metal complex according to claim 8, it is characterized in that, in the step obtaining described compd A, the step of described separation and purification is: make to be extracted with ethyl acetate obtain organic phase by adding the reacted reaction solution of saturated aqueous ammonium chloride solution, then organic phase described in anhydrous magnesium sulfate drying is used, again successively after filtration, concentrated filtrate, obtain crude product, the mixed solution of sherwood oil and ethyl acetate is used to carry out silica gel column chromatography separating-purifying as eluent to obtaining described crude product, obtain described compd A, wherein, the volume ratio of described sherwood oil and ethyl acetate is 3:1 ~ 5:1.
10. an organic electroluminescence device, comprise the anode layer stacked gradually on substrate, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, electron injection buffer layer and cathode layer, it is characterized in that, the material of described luminescent layer comprises material of main part and is doped in the guest materials in described material of main part, the doping mass percent of described guest materials is 8%, and described guest materials is the ruddiness organic electromechanical phosphorescent material iridium metal complex described in claim 1 or 2.
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