CN104292270A - Blue-light organic electrophosphorescent material iridium metal complex, preparation method thereof and organic electroluminescent device - Google Patents
Blue-light organic electrophosphorescent material iridium metal complex, preparation method thereof and organic electroluminescent device Download PDFInfo
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- CN104292270A CN104292270A CN201310300593.9A CN201310300593A CN104292270A CN 104292270 A CN104292270 A CN 104292270A CN 201310300593 A CN201310300593 A CN 201310300593A CN 104292270 A CN104292270 A CN 104292270A
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- metal complexes
- blue light
- light organic
- iridium metal
- iridium
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- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 78
- 239000000463 material Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- -1 iridium metal complex Chemical class 0.000 title abstract description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 64
- 238000006243 chemical reaction Methods 0.000 claims description 63
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- 229910052751 metal Inorganic materials 0.000 claims description 60
- 239000002184 metal Substances 0.000 claims description 60
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 46
- 239000007787 solid Substances 0.000 claims description 44
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 36
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 30
- 239000012153 distilled water Substances 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 30
- 239000012046 mixed solvent Substances 0.000 claims description 29
- 238000005401 electroluminescence Methods 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 26
- 239000012043 crude product Substances 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 22
- 239000000460 chlorine Substances 0.000 claims description 19
- 229910052801 chlorine Inorganic materials 0.000 claims description 19
- 230000004044 response Effects 0.000 claims description 19
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 18
- 125000004122 cyclic group Chemical group 0.000 claims description 17
- 238000010992 reflux Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 229910052763 palladium Inorganic materials 0.000 claims description 13
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 13
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 12
- 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 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 10
- 230000006837 decompression Effects 0.000 claims description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000001953 recrystallisation Methods 0.000 claims description 10
- 238000010898 silica gel chromatography Methods 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 9
- 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 9
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 235000015320 potassium carbonate Nutrition 0.000 claims description 6
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 abstract description 9
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003446 ligand Substances 0.000 abstract description 8
- 125000003545 alkoxy group Chemical group 0.000 abstract description 6
- 125000000714 pyrimidinyl group Chemical group 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 abstract 2
- 238000007385 chemical modification Methods 0.000 abstract 1
- 239000003086 colorant Substances 0.000 abstract 1
- 239000002585 base Substances 0.000 description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 44
- 229910052757 nitrogen Inorganic materials 0.000 description 38
- 230000015572 biosynthetic process Effects 0.000 description 32
- 238000003786 synthesis reaction Methods 0.000 description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- 239000007788 liquid Substances 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 16
- 239000007795 chemical reaction product Substances 0.000 description 16
- 238000004458 analytical method Methods 0.000 description 14
- 238000001819 mass spectrum Methods 0.000 description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 9
- 210000002659 acromion Anatomy 0.000 description 8
- 229960001701 chloroform Drugs 0.000 description 8
- 239000011368 organic material Substances 0.000 description 8
- 238000011160 research Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 150000003230 pyrimidines Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000005429 oxyalkyl group Chemical group 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Chemical compound C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 2
- DIVZFUBWFAOMCW-UHFFFAOYSA-N 4-n-(3-methylphenyl)-1-n,1-n-bis[4-(n-(3-methylphenyl)anilino)phenyl]-4-n-phenylbenzene-1,4-diamine Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 DIVZFUBWFAOMCW-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 230000005622 photoelectricity Effects 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
- 238000010791 quenching Methods 0.000 description 2
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000003335 steric effect Effects 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- OBBXILSUQUPBJQ-UHFFFAOYSA-N 2-bromo-4-hexoxypyrimidine Chemical compound BrC1=NC=CC(=N1)OCCCCCC OBBXILSUQUPBJQ-UHFFFAOYSA-N 0.000 description 1
- FUTVFKDRMZATOI-UHFFFAOYSA-N 2-bromo-4-icosylpyrimidine Chemical compound BrC1=NC=CC(=N1)CCCCCCCCCCCCCCCCCCCC FUTVFKDRMZATOI-UHFFFAOYSA-N 0.000 description 1
- IOYXGOFBYREEHR-UHFFFAOYSA-N 2-bromo-5-icosylpyrimidine Chemical compound BrC1=NC=C(C=N1)CCCCCCCCCCCCCCCCCCCC IOYXGOFBYREEHR-UHFFFAOYSA-N 0.000 description 1
- AQXNNEIFLPMDQR-UHFFFAOYSA-N 2-bromo-5-tert-butylpyrimidine Chemical class CC(C)(C)C1=CN=C(Br)N=C1 AQXNNEIFLPMDQR-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 235000012736 patent blue V Nutrition 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1074—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses a blue-light organic electrophosphorescent material iridium metal complex, a preparation method thereof and an organic electroluminescent device. The material has a following structure formula, wherein R is a hydrogen atom, an alkyl group with a carbon atom number being 1-20 or an alkoxy group with a carbon atom number being 1-20. In the blue-light organic electrophosphorescent material iridium metal complex, 2-(2',6'-difluoropyridine-4'-yl)pyrimidine is a cyclometal ligand major structure and 5-(2'-pyridyl)-1,2,3,4-tetrazole as an auxiliary ligand. In the invention, the blue-light organic electrophosphorescent material iridium metal complex is synthesized and adjustment of colors from the material can be achieved through chemical modification of introducing an alkyl chain or an alkoxy chain to the pyrimidine ring of the cyclometal ligand, thereby obtaining a high-color-purity blue light.
Description
Technical field
The present invention relates to electroluminescent organic material, particularly relate to a kind of iridium metal complexes of blue light organic phosphorescent electroluminescent materials and preparation method thereof and organic electroluminescence device.
Background technology
Organic electroluminescent refers to that organic materials is under electric field action, electric energy is converted into a kind of luminescence phenomenon of luminous energy.Make to stay cool to the research of organic electroluminescent due to reasons such as the driving voltage of organic electroluminescence device are too high, luminous efficiency is very low in early days.Until 1987, the human hairs such as the Tang of Kodak understand with oxine aluminium (Alq
3) be luminescent material, make the high-quality thin film of even compact with aromatic diamine, obtained low-work voltage, high brightness, high efficiency organic electroluminescence device, open the new prelude to electroluminescent organic material research.But owing to being subject to the restriction of spin statistics theory, the theoretical internal quantum efficiency limit of fluorescent material is only 25%, how makes full use of all the other phosphorescence of 75% and realize higher luminous efficiency and become hot research direction in after this this field.1997, Forrest etc. found electrophosphorescence phenomenon, and the internal quantum efficiency of electroluminescent organic material breaches the restriction of 25%, makes the research of electroluminescent organic material enter another new period.
In research subsequently, the title complex of small molecules doping type transition metal has become the research emphasis of people, as the title complex of iridium, ruthenium, platinum etc.The advantage of this kind of title complex is that they can obtain very high emitted energy from the triplet state of self, and wherein metal iridium (III) compound, due to good stability, in building-up process, reaction conditions is gentle, and there is very high electroluminescent properties, in research process subsequently, account for dominant position always.
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 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.The blue light organic phosphorescent electroluminescent materials that current report is maximum, over-all properties is best is two (4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic closes iridium (FIrpic), although people have carried out various optimization to FIrpic class OLED structure, device performance have also been obtained very large raising, but the maximum weakness of FIrpic is exactly sent out blue light is sky blue, blue light color purity is not good enough, the CIE of each OLED made is (0.13 ~ 0.17,0.29 ~ 0.39) change between, very large gap is had between this and standard blue light CIE (0.137,0.084).Therefore, the blue phosphorescent organic electroluminescent material developing high color purity becomes the megatrend expanding blue light material research field.
Summary of the invention
Based on the problems referred to above, problem to be solved by this invention is to provide a kind of iridium metal complexes of blue light organic phosphorescent electroluminescent materials.
A kind of iridium metal complexes of blue light organic phosphorescent electroluminescent materials, general structure is as follows:
Wherein, R is hydrogen atom, C
1~ C
20alkyl or C
1~ C
20alkoxyl group.
A preparation method for iridium metal complexes of blue light organic phosphorescent electroluminescent materials, comprises the steps:
(1), under protection of inert gas, by structural formula be
compd A and structural formula be
compd B be dissolved in the first organic solvent containing catalyzer and alkali, obtain reaction solution, described reaction solution carries out Suzuki linked reaction 6 ~ 12h at 85 ~ 100 DEG C of temperature, and after question response stops, separating-purifying reaction solution, obtaining structural formula is
cyclic metal complexes; Wherein, the mol ratio of described compd A and compd B is 1:1 ~ 1:1.5; R is hydrogen atom, C
1~ C
20alkyl or C
1~ C
20alkoxyl group;
(2), under protection of inert gas, be that 2:1 ~ 4:1 is dissolved in the mixed solvent that cellosolvo and water formed with mol ratio by described cyclic metal complexes and three hydrated iridium trichloride, heating mixed solvent is to reflux state stirring reaction 22 ~ 25h; Be cooled to room temperature, separating-purifying, obtaining structural formula is
chlorine bridge dipolymer; R is hydrogen atom, C
1~ C
20alkyl or C
1~ C
20alkoxyl group;
(3), under protection of inert gas, by described chlorine bridge dipolymer and structural formula be
compound C be that in the second organic solvent of being dissolved in containing sodium methylate or sodium ethylate of 1:2 ~ 1:3, obtain mixing solutions, heating mixing solutions to 40 ~ 84 DEG C, stirring reaction 8 ~ 20h, is cooled to room temperature, separating-purifying, obtains structural formula to be with mol ratio
iridium metal complexes of blue light organic phosphorescent electroluminescent materials; R is hydrogen atom, C
1~ C
20alkyl or C
1~ C
20alkoxyl group.
Preferably, described first organic solvent is toluene or dimethyl formamide (DMF).
Preferably, described alkali is sodium carbonate (Na
2cO
3) or salt of wormwood (K
2cO
3), the mol ratio of described alkali and compd A is 1:1 ~ 3:1.
Preferably, described catalyzer is that four (triphenylphosphines) close palladium (Pd (PPh
3)
4) or dichloro two (triphenyl phosphorus) close palladium (Pd (PPh
3)
2cl
2), the mol ratio of described catalyzer and compd A is 0.02:1 ~ 0.05:1.
Preferably, the volumetric molar concentration of described compd A in reaction solution is 0.1 ~ 0.2mol/L.
Preferably, the volumetric molar concentration in the mixed solvent that formed at cellosolvo and water of described three hydrated iridium trichloride is 0.017 ~ 0.05mol/L.
Preferably, described cellosolvo and water volume ratio are 3:1.
Preferably, described second organic solvent is 1,2-ethylene dichloride, trichloromethane or methylene dichloride.
Preferably, the mol ratio of described sodium methylate or sodium ethylate and described chlorine bridge dipolymer is 8:1 ~ 12:1.
Preferably, the volumetric molar concentration of described chlorine bridge dipolymer in mixing solutions is 0.01 ~ 0.02mol/L.
Preferably, the separating-purifying of described cyclic metal complexes comprises:
After question response stops being chilled to room temperature, dichloromethane extraction, separatory, be washed to neutrality, with anhydrous magnesium sulfate drying; Filter, filtrate decompression steams solvent and obtains crude product, and the mixed solution formed with ethyl acetate and normal hexane is separated for elutriant carries out silica gel column chromatography, obtains described cyclic metal complexes after drying.
More preferably, the volume ratio of described ethyl acetate and normal hexane is 1:4 ~ 1:10.
Preferably, described rare gas element is nitrogen or argon gas.
Preferably, the separating-purifying of described chlorine bridge dipolymer comprises:
After question response stopping is chilled to room temperature, rotates and steam except partial solvent, add appropriate distilled water, filter and obtain solid, solid uses distilled water, methanol wash successively, obtains described chlorine bridge dipolymer after drying.
Preferably, the separating-purifying of described iridium metal complexes of blue light organic phosphorescent electroluminescent materials comprises:
After question response stops being chilled to room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, has solid to separate out; Collecting by filtration crude product, crude product uses deionized water, methanol wash for several times successively, after the mixed solvent recrystallization that methylene dichloride and dehydrated alcohol are formed, obtain iridium metal complexes of blue light organic phosphorescent electroluminescent materials.
Blue light organic phosphorescent electroluminescent materials metal iridium complex provided by the invention is cyclic metal complexes agent structure with 2-(2', 6'-difluoro pyridine-4'-base) pyrimidine, with 5-(2'-pyridyl)-pyrrotriazole for assistant ligand.On main part, on the pyrimidine ring of planar rigidity and pyridine ring, the C-F key of low vibrational frequency is conducive to reducing nonradiative transition probability, improves the luminous efficiency of material; The introducing of alkyl or alkoxyl group on pyrimidine ring, on the one hand, the electro mass-energy of giving of alkyl or alkoxyl group regulates blue light emitting wavelength, in addition on the one hand, the alkyl chain of different lengths or oxyalkyl chain are conducive to increasing its solvability in organic solvent, and produce certain space steric effect, thus reduce the direct effect between atoms metal, reduce the self-quenching phenomenon of triplet exciton; On pyridine ring, the fluorine-based and introducing that is high field intensity assistant ligand 5-(2'-pyridyl)-pyrrotriazole of strong electron-withdrawing group group can improve luminescent properties, is beneficial to evaporation, increases film-forming type and improves the stability of device.
A kind of organic electroluminescence device, comprise luminescent layer, adulterate in described luminescent layer iridium metal complexes of blue light organic phosphorescent electroluminescent materials, and general structure is as follows:
Wherein, R is hydrogen atom, C
1~ C
20alkyl or C
1~ C
20alkoxyl group.
Containing above-mentioned blue light organic phosphorescent electroluminescent materials metal iridium complex in the luminescent layer of organic electroluminescence device of the present invention, material of main part in this compound and organic electroluminescence device luminescent layer has good consistency, can be widely used in and prepare blue light or white-light phosphor photoelectricity electroluminescence device.Organic electroluminescence device of the present invention is due to the organic electromechanical phosphorescent material metal iridium complex containing transmitting blue light wavelength in luminescent layer, thus it has the advantage launching blue light with high color purity and good device performance.
Accompanying drawing explanation
Fig. 1 is the preparation flow schematic diagram of the iridium metal complexes of blue light organic phosphorescent electroluminescent materials of an embodiment;
Fig. 2 is the utilizing emitted light spectrogram of iridium metal complexes of blue light organic phosphorescent electroluminescent materials obtained in embodiment 1;
Fig. 3 is the structural representation of organic electroluminescence device obtained in Application Example.
Embodiment
The invention reside in and select with 2-(2', 6'-difluoro pyridine-4'-base) pyrimidine or derivatives thereof is cyclic metal complexes, with 5-(2'-pyridyl)-1,2,3,4-tetrazolium is assistant ligand, synthesizes a kind of iridium metal complexes of blue light organic phosphorescent electroluminescent materials, and by realizing the adjustment to material emission color to the chemically modified pyrimidine ring of cyclic metal complexes being introduced alkyl chain or oxyalkyl chain, thus obtain the more blue phosphorescent emissions of emission wavelength.The object of the present invention is to provide so a kind of blue light organic phosphorescent material iridium metal complex and preparation thereof and organic electroluminescence device.
The general structure of iridium metal complexes of blue light organic phosphorescent electroluminescent materials of the present invention is as follows:
Wherein, R is hydrogen atom, C
1~ C
20alkyl or C
1~ C
20alkoxyl group, the structural formula of described cyclic metal complexes is specially:
or
n=1～20。
Refer to Fig. 1, the preparation method of above-mentioned iridium metal complexes of blue light organic phosphorescent electroluminescent materials, comprises the steps:
Under S1, protection of inert gas, by structural formula be
compd A and structural formula be
compd B be dissolved in the first organic solvent containing catalyzer and alkali, obtain reaction solution, described reaction solution carries out Suzuki linked reaction 6 ~ 12h at 85 ~ 100 DEG C of temperature, and after question response stops, separating-purifying reaction solution, obtaining structural formula is
cyclic metal complexes; Wherein, the mol ratio of described compd A and compd B is 1:1 ~ 1:1.5; R is hydrogen atom, C
1~ C
20alkyl or C
1~ C
20alkoxyl group; Reaction formula is:
Under S2, protection of inert gas, be that 2:1 ~ 4:1 is dissolved in the mixed solvent that cellosolvo and water formed with mol ratio by described cyclic metal complexes and three hydrated iridium trichloride, heating mixed solvent is to reflux state stirring reaction 22 ~ 25h; Be cooled to room temperature, separating-purifying, obtaining structural formula is
chlorine bridge dipolymer; R is hydrogen atom, C
1~ C
20alkyl or C
1~ C
20alkoxyl group, reaction formula is:
Under S3, protection of inert gas, by described chlorine bridge dipolymer and structural formula be
compound C be that in the second organic solvent of being dissolved in containing sodium methylate or sodium ethylate of 1:2 ~ 1:3, obtain mixing solutions, heating mixing solutions to 40 ~ 84 DEG C, stirring reaction 8 ~ 20h, is cooled to room temperature, separating-purifying, obtains structural formula to be with mol ratio
iridium metal complexes of blue light organic phosphorescent electroluminescent materials; R is hydrogen atom, C
1~ C
20alkyl or C
1~ C
20alkoxyl group, reaction formula is:
Preferably, described first organic solvent is toluene or dimethyl formamide (DMF).
Preferably, described alkali is sodium carbonate (Na
2cO
3) or salt of wormwood (K
2cO
3), the mol ratio of described alkali and compd A is 1:1 ~ 3:1.
Preferably, described catalyzer is that four (triphenylphosphines) close palladium (Pd (PPh
3)
4) or dichloro two (triphenyl phosphorus) close palladium (Pd (PPh
3)
2cl
2), the mol ratio of described catalyzer and compd A is 0.02:1 ~ 0.05:1.
Preferably, the volumetric molar concentration of described compd A in reaction solution is 0.1 ~ 0.2mol/L.
Preferably, the volumetric molar concentration in the mixed solvent that formed at cellosolvo and water of described three hydrated iridium trichloride is 0.017 ~ 0.05mol/L.
Preferably, described cellosolvo and water volume ratio are 3:1.
Preferably, described second organic solvent is 1,2-ethylene dichloride, trichloromethane or methylene dichloride.
Preferably, the mol ratio of described sodium methylate or sodium ethylate and described chlorine bridge dipolymer is 8:1 ~ 12:1.
Preferably, the volumetric molar concentration of described chlorine bridge dipolymer in mixing solutions is 0.01 ~ 0.02mol/L.
Preferably, described rare gas element is nitrogen or argon gas.
Preferably, the separating-purifying of described cyclic metal complexes comprises:
After question response stops being chilled to room temperature, dichloromethane extraction, separatory, be washed to neutrality, with anhydrous magnesium sulfate drying; Filter, filtrate decompression steams solvent and obtains crude product, and the mixed solution formed with ethyl acetate and normal hexane is separated for elutriant carries out silica gel column chromatography, obtains described cyclic metal complexes after drying.
More preferably, the volume ratio of described ethyl acetate and normal hexane is 1:4 ~ 1:10.
Preferably, the separating-purifying of described chlorine bridge dipolymer comprises:
After question response stopping is chilled to room temperature, rotates and steam except partial solvent, add appropriate distilled water, filter and obtain solid, solid uses distilled water, methanol wash successively, obtains described chlorine bridge dipolymer after drying.
Preferably, the separating-purifying of described iridium metal complexes of blue light organic phosphorescent electroluminescent materials comprises:
After question response stops being chilled to room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, has solid to separate out; Collecting by filtration crude product, crude product uses deionized water, methanol wash for several times successively, after the mixed solvent recrystallization that methylene dichloride and dehydrated alcohol are formed, obtain iridium metal complexes of blue light organic phosphorescent electroluminescent materials.
Blue light organic phosphorescent electroluminescent materials metal iridium complex provided by the invention is cyclic metal complexes agent structure with 2-(2', 6'-difluoro pyridine-4'-base) pyrimidine, with 5-(2'-pyridyl)-pyrrotriazole for assistant ligand.On main part, on the pyrimidine ring of planar rigidity and pyridine ring, the C-F key of low vibrational frequency is conducive to reducing nonradiative transition probability, improves the luminous efficiency of material; The introducing of alkyl or alkoxyl group on pyrimidine ring, on the one hand, the electro mass-energy of giving of alkyl or alkoxyl group regulates blue light emitting wavelength, in addition on the one hand, the alkyl chain of different lengths or oxyalkyl chain are conducive to increasing its solvability in organic solvent, and produce certain space steric effect, thus reduce the direct effect between atoms metal, reduce the self-quenching phenomenon of triplet exciton; On pyridine ring, the fluorine-based and introducing that is high field intensity assistant ligand 5-(2'-pyridyl)-pyrrotriazole of strong electron-withdrawing group group can improve luminescent properties, is beneficial to evaporation, increases film-forming type and improves the stability of device.
In addition, there is a need to provide a kind of blue light organic phosphorescent electroluminescent materials metal iridium complex organic electroluminescence device.
A kind of organic electroluminescence device, comprise luminescent layer, adulterate in described luminescent layer iridium metal complexes of blue light organic phosphorescent electroluminescent materials, and general structure is as follows:
Wherein, R is hydrogen atom, C
1~ C
20alkyl or C
1~ C
20alkoxyl group.
Containing above-mentioned blue light organic phosphorescent electroluminescent materials metal iridium complex in the luminescent layer of organic electroluminescence device of the present invention, material of main part in this compound and organic electroluminescence device luminescent layer has good consistency, can be widely used in and prepare blue light or white-light phosphor photoelectricity electroluminescence device.Organic electroluminescence device of the present invention is due to the organic electromechanical phosphorescent material metal iridium complex containing transmitting blue light wavelength in luminescent layer, thus it has the advantage launching blue light with high color purity and good device performance.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1: title complex two (2-(2', 6'-difluoro pyridine-4'-base) pyrimidine-N, C
3') (5-(2'-pyridyl)-pyrrotriazole) close the synthesis of iridium
(1) synthesis of 2-(2', 6'-difluoro pyridine-4'-base) pyrimidine
Under nitrogen protection; by 1.59g (10mmol) 2-bromo pyrimi piperidine (A1), 1.91g (12mmol) 2; 6-difluoro pyridine-4-boric acid (B) and 0.58g (0.5mmol) four (triphenyl phosphorus) closes palladium and is dissolved in 40mL toluene, drips the aqueous solution forming reactions liquid of 20mL containing 2.76g (20mmol) salt of wormwood subsequently.Heating, stirring reaction 6h under 100 DEG C of state of temperatures.After question response liquid cooling to room temperature, dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying.Filter, filtrate decompression steams solvent and obtains crude product.Be that the ethyl acetate of 1:10 is separated for elutriant carries out silica gel column chromatography with normal hexane with volume ratio, after drying solid 1.18g, yield is 61.1%.
Structural Identification:
Mass spectrum (MS m/z): 193.0 (M
+);
Ultimate analysis: C
9h
5f
2n
3;
Theoretical value: C, 55.96; H, 2.61; F, 19.67; N, 21.75;
Measured value: C, 55.91; H, 2.68; F, 19.62; N, 21.79.
(2) part be 2-(2', 6'-difluoro pyridine-4'-base) pyrimidine containing the dimeric synthesis of iridium dichloro
Under nitrogen protection; by 0.36g (1mmol) three hydrated iridium trichloride; 0.48g (2.5mmol) 2-(2'; 6'-difluoro pyridine-4'-base) pyrimidine is dissolved in cellosolvo that 20mL volume ratio is 3:1 and the mixed solvent that water is formed, stirring reaction 24h under heating mixed solvent to reflux state.After being chilled to room temperature, rotating and steam except partial solvent, add appropriate distilled water, filter.Solid uses distilled water, methanol wash successively, and obtain solids 0.37g after drying, yield is 60.5%.Dipolymer, without the need to further purification, can directly drop in next step reaction.
(3) title complex two (2-(2', 6'-difluoro pyridine-4'-base) pyrimidine-N, C
3') (5-(2'-pyridyl)-pyrrotriazole) close the synthesis of iridium
Under nitrogen protection; be 2-(2' by 0.61g (0.5mmol) main part; 6'-difluoro pyridine-4'-base) pyrimidine containing iridium dichloro dimer and 0.18g (1.2mmol) 5-(2'-pyridyl)-1; 2; 3; 4-tetrazolium (Compound C) is dissolved in 15mL trichloromethane, and drip the chloroform soln formation mixing solutions of 10mL containing 0.27g (5mmol) sodium methylate subsequently, stirring heating mixing solutions is warming up to 62 DEG C of reflux states reaction 15h.Naturally, after being chilled to room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, has solid to separate out.Filter, collect crude product, solid uses deionized water, methanol wash for several times successively, and obtain 0.40g pure products through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 55.3%.
Structural Identification:
Mass spectrum (MS m/z): 723.1 (M
+);
Ultimate analysis: C
24h
12f
4irN
11;
Theoretical value: C, 39.89; H, 1.67; F, 10.52; Ir, 26.60; N, 21.32;
Measured value: C, 39.83; H, 1.75; F, 10.47; Ir, 26.67; N, 21.28.
Fig. 2 is the utilizing emitted light spectrogram of the blue light organic phosphorescent electroluminescent materials metal iridium complex that the embodiment of the present invention 1 obtains.As shown in Figure 2, transverse axis is wavelength (Wavelength, unit nm), and the longitudinal axis is normalized luminous intensity (Normalized PL intensity), and end product is CH at 298K temperature
2cl
2solution (~ 10
-6the maximum emission peak of the emmission spectrum M), at 455nm place, has an acromion at 487nm place simultaneously, can be used as the preparation field that blue light electroluminescent material is widely used in organic electroluminescence device.
In addition, concentration is 10
-6the CH of M end product
2cl
2solution at 298K temperature, with concentration for ~ 10
-6the CH of the FIrpic of M
2cl
2solution is standard (Φ
pL=0.26) Φ of end product, is recorded
pL=0.28, the iridium electroluminescent organic material that contains of visible the present embodiment has higher luminous quantum efficiency.
Embodiment 2: title complex two (2-(2', 6'-difluoro pyridine-4'-base)-5-methylpyrimidine-N, C
3') (5-(2'-pyridyl)-pyrrotriazole) close the synthesis of iridium
(1) synthesis of 2-(2', 6'-difluoro pyridine-4'-base)-5-methylpyrimidine
Under nitrogen protection; bromo-for 1.73g (10mmol) 2-5-methylpyrimidine (A2), 1.76g (10mmol) B and 0.28g (0.4mmol) dichloro two (triphenyl phosphorus) are closed palladium and be dissolved in 50mL DMF, drips the aqueous solution forming reactions liquid of 25mL containing 3.18g (30mmol) sodium carbonate subsequently.Stirring reaction 8h under reacting by heating liquid to 90 DEG C state of temperature.After question response liquid cooling to room temperature, dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying.Filter, filtrate decompression steams solvent and obtains crude product.Be that the ethyl acetate of 1:6 is separated for elutriant carries out silica gel column chromatography with normal hexane with volume ratio, after drying solid 1.08g, yield is 52.1%.
Structural Identification:
Mass spectrum (MS m/z): 207.1 (M
+);
Ultimate analysis: C
10h
7f
2n
3;
Theoretical value: C, 57.97; H, 3.41; F, 18.34; N, 20.28;
Measured value: C, 57.88; H, 3.53; F, 18.28; N, 20.31.
(2) part be 2-(2', 6'-difluoro pyridine-4'-base)-5-methylpyrimidine containing the dimeric synthesis of iridium dichloro
Under nitrogen protection; by 0.36g (1mmol) three hydrated iridium trichloride; 0.45g (2mmol) 2-(2'; 6'-difluoro pyridine-4'-base)-5-methylpyrimidine is dissolved in cellosolvo that 20mL volume ratio is 3:1 and the mixed solvent that water is formed, stirring reaction 22h under heating mixed solvent to reflux state.After being chilled to room temperature, rotating and steam except partial solvent, add appropriate distilled water, filter.Solid uses distilled water, methanol wash successively, and obtain solids 0.34g after drying, yield is 53.1%.Dipolymer, without the need to further purification, can directly drop in next step reaction.
(3) title complex two (2-(2', 6'-difluoro pyridine-4'-base)-5-methylpyrimidine-N, C
3') (5-(2'-pyridyl)-pyrrotriazole) close the synthesis of iridium
Under nitrogen protection; be 2-(2' by 0.64g (0.5mmol) main part; 6'-difluoro pyridine-3'-base)-5-methylpyrimidine be dissolved in 20mL methylene dichloride containing iridium dichloro dimer and 0.15g (1mmol) Compound C; drip the dichloromethane solution formation mixing solutions of 10mL containing 0.27g (4mmol) sodium ethylate subsequently, stirring heating is warming up to 40 DEG C of reflux states reaction 20h.Naturally, after being chilled to room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, has solid to separate out.Filter, collect crude product, solid uses deionized water, methanol wash for several times successively, and obtain 0.30g pure products through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 40.0%.
Structural Identification:
Mass spectrum (MS m/z): 751.1 (M
+);
Ultimate analysis: C
26h
16f
4irN
11;
Theoretical value: C, 41.60; H, 2.15; F, 10.12; Ir, 25.61; N, 20.52;
Measured value: C, 41.66; H, 2.10; F, 10.07; Ir, 25.66; N, 20.51.
End product is CH at 298K temperature
2cl
2solution (~ 10
-6the maximum emission peak of the emmission spectrum M), at 453nm place, has an acromion at 487nm place, with the CH of the FIrpic of same concentrations simultaneously
2cl
2solution is standard (Φ
pL=0.26) Φ of end product, is recorded
pL=0.17, the iridium electroluminescent organic material that contains of visible the present embodiment has higher luminous quantum efficiency, can be used as the preparation field that blue light electroluminescent material is widely used in organic electroluminescence device.
Embodiment 3: title complex two (2-(2', 6'-difluoro pyridine-4'-base)-5-t-butyl pyrimidines-N, C
3') (5-(2'-pyridyl)-pyrrotriazole) close the synthesis of iridium
(1) synthesis of 2-(2', 6'-difluoro pyridine-4'-base)-5-t-butyl pyrimidines
Under nitrogen protection; two to 2.15g (10mmol) 2-bromo-5-t-butyl pyrimidines (A3), 2.22g (14mmol) compd B and 0.21g (0.3mmol) chlorine two (triphenyl phosphorus) is closed palladium to be dissolved in 35mL DMF, drips the aqueous solution forming reactions liquid of 15mL containing 1.06g (10mmol) sodium carbonate subsequently.Stirring reaction 10h under reacting by heating liquid to 85 DEG C state.After question response liquid cooling to room temperature, dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying.Filter, filtrate decompression steams solvent and obtains crude product.Be that the ethyl acetate of 1:5 is separated for elutriant carries out silica gel column chromatography with normal hexane with volume ratio, after drying solid 0.87g, yield is 34.9%.
Structural Identification:
Mass spectrum (MS m/z): 249.1 (M
+);
Ultimate analysis: C
13h
13f
2n
3;
Theoretical value: C, 62.64; H, 5.26; F, 15.24; N, 16.86;
Measured value: C, 62.71; H, 5.18; F, 15.27; N, 16.84.
(2) part be 2-(2', 6'-difluoro pyridine-4'-base)-5-t-butyl pyrimidines containing the dimeric synthesis of iridium dichloro
Under nitrogen protection; by 0.36g (1mmol) three hydrated iridium trichloride and 0.75g (3mmol) 2-(2'; 6'-difluoro pyridine-4'-base)-5-t-butyl pyrimidines is dissolved in cellosolvo that 20mL volume ratio is 3:1 and the mixed solvent that water is formed, stirring reaction 24h at reflux.After being chilled to room temperature, rotating and steam except partial solvent, add appropriate distilled water, filter.Solid uses distilled water, methanol wash successively, and obtain solids 0.16g after drying, yield is 22.1%.Dipolymer, without the need to further purification, can directly drop in next step reaction.
(3) title complex two (2-(2', 6'-difluoro pyridine-4'-base)-5-t-butyl pyrimidines-N, C
3') (5-(2'-pyridyl)-pyrrotriazole) close the synthesis of iridium
Under nitrogen protection; be 2-(2' by 0.58g (0.4mmol) main part; 6'-difluoro pyridine-4'-base)-5-t-butyl pyrimidines be dissolved in 20mL trichloromethane containing iridium dichloro dimer and 0.15g (1mmol) Compound C; drip the chloroform soln of 10mL containing 0.33g (4.8mmol) sodium ethylate subsequently, stirring heating is warming up to 62 DEG C of reflux state reaction 12h.Naturally, after being chilled to room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, has solid to separate out.Filter, collect crude product, solid uses deionized water, methanol wash for several times successively, and obtain 0.23g pure products through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 34.4%.
Structural Identification:
Mass spectrum (MS m/z): 835.2 (M
+);
Ultimate analysis: C
32h
28f
4irN
11;
Theoretical value: C, 46.04; H, 3.38; F, 9.10; Ir, 23.02; N, 18.46;
Measured value: C, 46.11; H, 3.28; F, 9.17; Ir, 23.04; N, 18.40.
End product is CH at 298K temperature
2cl
2solution (~ 10
-6the maximum emission peak of the emmission spectrum M), at 473nm place, has an acromion at 506nm place, with the CH of the FIrpic of same concentrations simultaneously
2cl
2solution is standard (Φ
pL=0.26) Φ of end product, is recorded
pL=0.18.
Embodiment 4: title complex two (2-(2', 6'-difluoro pyridine-4'-base)-4-eicosyl pyrimidine-N, C
2') (5-(2'-pyridyl)-pyrrotriazole) close the synthesis of iridium
(1) synthesis of 2-(2', 6'-difluoro pyridine-4'-base)-4-eicosyl pyrimidine
Under nitrogen protection; 2.20g (5mmol) 2-bromo-4-eicosyl pyrimidine (A4), 1.19g (7.5mmol) compd B and 0.12g (0.1mmol) four (triphenyl phosphorus) close palladium and are dissolved in 35mL toluene, drip the aqueous solution of 15mL containing 1.73g (12.5mmol) salt of wormwood subsequently in reaction system.Be heated to stirring reaction 12h under 85 DEG C of state of temperatures.After question response liquid cooling to room temperature, dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying.Filter, filtrate decompression steams solvent and obtains crude product.Be that the ethyl acetate of 1:8 is separated for elutriant carries out silica gel column chromatography with normal hexane with volume ratio, after drying solid 0.52g, yield is 22.0%.
Structural Identification:
Mass spectrum (MS m/z): 473.4 (M
+);
Ultimate analysis: C
29h
45f
2n
3;
Theoretical value: C, 73.53; H, 9.58; F, 8.02; N, 8.87;
Measured value: C, 73.44; H, 9.66; F, 8.06; N, 8.84.
(2) part be 2-(2', 6'-difluoro pyridine-4'-base)-4-eicosyl pyrimidine containing the dimeric synthesis of iridium dichloro
Under nitrogen protection; by 0.18g (0.5mmol) three hydrated iridium trichloride; 0.98g (2mmol) 2-(2'; 3'; 4'-trifluorophenyl)-4-eicosyl pyrimidine is dissolved in cellosolvo that 10mL volume ratio is 3:1 and the mixed solvent that water is formed, stirring reaction mixed solvent 25h at reflux.After being chilled to room temperature, rotating and steam except partial solvent, add appropriate distilled water, filter.Solid uses distilled water, methanol wash successively, and obtain solids 0.09g after drying, yield is 15.3%.Dipolymer, without the need to further purification, can directly drop in next step reaction.
(3) title complex two (2-(2', 6'-difluoro pyridine-4'-base)-4-eicosyl pyrimidine-N, C
3') (5-(2'-pyridyl)-pyrrotriazole) close the synthesis of iridium
Under nitrogen protection; be 2-(2' by 0.705g (0.3mmol) main part; 6'-difluoro pyridine-4'-base)-4-eicosyl pyrimidine be dissolved in 20mL1 containing iridium dichloro dimer and 0.13g (0.9mmol) Compound C; in 2-ethylene dichloride; drip 10mL subsequently containing 1 of 0.16g (3mmol) sodium methylate; 2-dichloroethane solution forms mixing solutions, and stirring heating mixing solutions is warming up to 84 DEG C of reflux state reaction 10h.Naturally, after being chilled to room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, has solid to separate out.Filter, collect crude product, solid uses deionized water, methanol wash for several times successively, and obtain 0.05g pure products through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 9.7%.
Structural Identification:
Mass spectrum (MS m/z): 1283.7 (M
+);
Ultimate analysis: C
64h
92f
4irN
11;
Theoretical value: C, 59.88; H, 7.22; F, 5.92; Ir, 14.97; N, 12.00;
Measured value: C, 59.82; H, 7.31; F, 5.88; Ir, 14.95; N, 12.04.
End product is CH at 298K temperature
2cl
2solution (~ 10
-6the maximum emission peak of the emmission spectrum M), at 485nm place, has an acromion at 518nm place, with the CH of the FIrpic of same concentrations simultaneously
2cl
2solution is standard (Φ
pL=0.26) Φ of end product, is recorded
pL=0.08.
Embodiment 5: title complex two (2-(2', 6'-difluoro pyridine-4'-base)-5-methoxy pyrimidine-N, C
3') (5-(2'-pyridyl)-pyrrotriazole) close the synthesis of iridium
(1) synthesis of 2-(2', 6'-difluoro pyridine-4'-base)-5-methoxy pyrimidine
Under nitrogen protection; bromo-for 1.89g (10mmol) 2-5-methoxy pyrimidine (A5), 1.91g (12mmol) compd B and 0.58g (0.5mmol) four (triphenyl phosphorus) are closed palladium to be dissolved in 35mL toluene, drips the aqueous solution forming reactions liquid of 15mL containing 2.76g (20mmol) salt of wormwood subsequently in reaction system.Stirring reaction 10h under reacting by heating liquid to 100 DEG C state of temperature.After question response liquid cooling to room temperature, dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying.Filter, filtrate decompression steams solvent and obtains crude product.Be that the ethyl acetate of 1:5 is separated for elutriant carries out silica gel column chromatography with normal hexane with volume ratio, after drying solid 1.14g, yield is 51.1%.
Structural Identification:
Mass spectrum (MS m/z): 223.1 (M
+);
Ultimate analysis: C
10h
7f
2n
3o;
Theoretical value: C, 53.82; H, 3.16; F, 17.03; N, 18.83; O, 7.17;
Measured value: C, 53.86; H, 3.07; F, 17.07; N, 18.77; O, 7.22.
(2) part be 2-(2', 6'-difluoro pyridine-4'-base)-5-methoxy pyrimidine containing the dimeric synthesis of iridium dichloro
Under nitrogen protection; by 0.70g (2mmol) three hydrated iridium trichloride; 0.89g (4mmol) 2-(2'; 6'-difluoro pyridine-4'-base)-5-methoxy pyrimidine is dissolved in cellosolvo that 40mL volume ratio is 3:1 and the mixed solvent that water is formed, stirring reaction 24h under heating mixed solvent to reflux state.After being chilled to room temperature, rotating and steam except partial solvent, add appropriate distilled water, filter.Solid uses distilled water, methanol wash successively, and obtain solids 0.54g after drying, yield is 40.2%.Dipolymer, without the need to further purification, can directly drop in next step reaction.
(3) title complex two (2-(2', 6'-difluoro pyridine-4'-base)-5-methoxy pyrimidine-N, C
3') (5-(2'-pyridyl)-pyrrotriazole) close the synthesis of iridium
Under nitrogen protection; be 2-(2' by 0.67g (0.5mmol) main part; 6'-difluoro pyridine-4'-base)-5-methoxy pyrimidine containing iridium dichloro dimer and 0.18g (1.25mmol) 5-(2'-pyridyl)-1; 2; 3; 4-tetrazolium is dissolved in 15mL1; in 2-ethylene dichloride; drip 10mL subsequently containing 1 of 0.27g (5mmol) sodium methylate; 2-dichloroethane solution forms mixed solution, and stirring heating mixed solution is warming up to 84 DEG C of reflux state reaction 8h.Naturally, after being chilled to room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, has solid to separate out.Filter, collect crude product, solid uses deionized water, methanol wash for several times successively, and obtain 0.29g pure products through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 37.0%.
Structural Identification:
Mass spectrum (MS m/z): 783.1 (M
+);
Ultimate analysis: C
26h
16f
4irN
11o
2;
Theoretical value: C, 39.90; H, 2.06; F, 9.71; Ir, 24.56; N, 19.69; O, 4.09;
Measured value: C, 39.96; H, 2.03; F, 9.75; Ir, 24.44; N, 19.75; O, 4.07.
End product is CH at 298K temperature
2cl
2solution (~ 10
-6the maximum emission peak of the emmission spectrum M), at 454nm place, has an acromion at 485nm place simultaneously, can be used as the preparation field that blue light electroluminescent material is widely used in organic electroluminescence device.
In addition, 10
-6the CH of M end product
2cl
2solution at 298K temperature, with concentration for ~ 10
-6the CH of the FIrpic of M
2cl
2solution is standard (Φ
pL=0.26) Φ of end product, is recorded
pL=0.18, the iridium electroluminescent organic material that contains of visible the present embodiment has higher luminous quantum efficiency.
Embodiment 6: title complex two (2-(2', 6'-difluoro pyridine-4'-base)-4-hexyloxy pyrimidine-N, C
3') (5-(2'-pyridyl)-pyrrotriazole) close the synthesis of iridium
(1) synthesis of 2-(2', 6'-difluoro pyridine-4'-base)-4-hexyloxy pyrimidine
Under nitrogen protection; two to 2.59g (10mmol) 2-bromo-4-hexyloxy pyrimidine (A6), 1.59g (10mmol) compd B and 0.21g (0.3mmol) chlorine two (triphenyl phosphorus) is closed palladium to be dissolved in 40mLDMF, drips the aqueous solution forming reactions liquid of 20mL containing 1.06g (10mmol) sodium carbonate subsequently in reaction system.Stirring reaction 8h under reacting by heating liquid to 90 DEG C state.After question response liquid cooling to room temperature, dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying.Filter, filtrate decompression steams solvent and obtains crude product.Be that the ethyl acetate of 1:4 is separated for elutriant carries out silica gel column chromatography with normal hexane with volume ratio, after drying solid 1.06g, yield is 40.9%.
Structural Identification:
Mass spectrum (MS m/z): 293.1 (M
+);
Ultimate analysis: C
15h
17f
2n
3o;
Theoretical value: C, 61.42; H, 5.84; F, 12.95; N, 14.33; O, 5.45;
Measured value: C, 61.33; H, 5.93; F, 12.92; N, 14.37; O, 5.44.
(2) part be 2-(2', 6'-difluoro pyridine-4'-base)-4-hexyloxy pyrimidine containing the dimeric synthesis of iridium dichloro
Under nitrogen protection; by 0.36g (1mmol) three hydrated iridium trichloride and 0.93g (3mmol) 2-(2'; 6'-difluoro pyridine-4' base)-4-hexyloxy pyrimidine is dissolved in the mixed solvent that 25mL2-ethoxy ethanol and water (3:1) formed, and is uniformly mixed solvent reaction 24h at reflux.After being chilled to room temperature, rotating and steam except partial solvent, add appropriate distilled water, filter.Solid uses distilled water, methanol wash successively, and obtain solids 0.15g after drying, yield is 18.5%.Dipolymer, without the need to further purification, can directly drop in next step reaction.
(3) title complex two (2-(2', 6'-difluoro pyridine-4'-base)-4-hexyloxy pyrimidine-N, C
3') (5-(2'-pyridyl)-pyrrotriazole) close the synthesis of iridium
Under nitrogen protection; be 2-(2' by 0.65g (0.4mmol) main part; 6'-difluoro pyridine-4'-base)-4-hexyloxy pyrimidine be dissolved in 15mL methylene dichloride containing iridium dichloro dimer and 0.12g (0.8mmol) Compound C; drip the dichloromethane solution formation mixed solution of 10mL containing 0.22g (3.2mmol) sodium ethylate subsequently, stirring heating mixed solution is warming up to 40 DEG C of reflux states reaction 20h.Naturally, after being chilled to room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, has solid to separate out.Filter, collect crude product, solid uses deionized water, methanol wash for several times successively, and obtain 0.16g pure products through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 21.7%.
Structural Identification:
Mass spectrum (MS m/z): 923.3 (M
+)
Ultimate analysis: C
36h
36f
4irN
11o
2
Theoretical value: C, 46.85; H, 3.93; F, 8.23; Ir, 20.83; N, 16.69; O, 3.47;
Measured value: C, 46.81; H, 3.98; F, 8.15; Ir, 20.92; N, 16.65; O, 3.49.
End product is CH at 298K temperature
2cl
2solution (~ 10
-6the maximum emission peak of the emmission spectrum M), at 478nm place, has an acromion at 510nm place, with the CH of the FIrpic of same concentrations simultaneously
2cl
2solution is standard (Φ
pL=0.26) Φ of end product, is recorded
pL=0.11.
Embodiment 7: title complex two (2-(2', 6'-difluoro pyridine-4'-base)-5-eicosane oxygen yl pyrimidines-N, C
3') (5-(2'-pyridyl)-pyrrotriazole) close the synthesis of iridium
(1) synthesis of 2-(2', 6'-difluoro pyridine-4'-base)-5-eicosane oxygen yl pyrimidines
Under nitrogen protection; 2.28g (5mmol) 2-bromo-5-eicosyl pyrimidine (A7), 1.19g (7.5mmol) compd B and 0.23g (0.2mmol) four (triphenyl phosphorus) are closed palladium to be dissolved in 35mL toluene, drips the aqueous solution forming reactions liquid of 15mL containing 1.59g (15mmol) sodium carbonate subsequently in reaction system.Stirring reaction 6h under reacting by heating liquid to 85 DEG C state of temperature.After question response liquid cooling to room temperature, dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying.Filter, filtrate decompression steams solvent and obtains crude product.Be that the ethyl acetate of 1:7 is separated for elutriant carries out silica gel column chromatography with normal hexane with volume ratio, after drying solid 0.32g, yield is 13.1%.
Structural Identification:
Mass spectrum (MS m/z): 489.3 (M
+);
Ultimate analysis: C
29h
45f
2n
3o;
Theoretical value: C, 71.13; H, 9.26; F, 7.76; N, 8.58; O, 3.27;
Measured value: C, 71.17; H, 9.21; F, 7.82; N, 8.52; O, 3.28.
(2) part be 2-(2', 6'-difluoro pyridine-4'-base)-5-eicosane oxygen yl pyrimidines containing the dimeric synthesis of iridium dichloro
Under nitrogen protection; by 0.18g (0.5mmol) three hydrated iridium trichloride; 0.98g (2mmol) 2-(2'; 6'-difluoro pyridine-4'-base)-5-eicosane oxygen yl pyrimidines is dissolved in cellosolvo that 30mL volume ratio is 3:1 and the mixed solution that water is formed, stirring reaction 24h at reflux.After being chilled to room temperature, rotating and steam except partial solvent, add appropriate distilled water, filter.Solid uses distilled water, methanol wash successively, and obtain solids 0.08g after drying, yield is 13.3%.Dipolymer, without the need to further purification, can directly drop in next step reaction.
(3) title complex two (2-(2', 6'-difluoro pyridine-4'-base)-5-eicosane oxygen yl pyrimidines-N, C
3') (5-(2'-pyridyl)-pyrrotriazole) close the synthesis of iridium
Under nitrogen protection; be 2-(2' by 0.72g (0.3mmol) main part; 6'-difluoro pyridine-3'-base)-5-eicosane oxygen yl pyrimidines be dissolved in 20mL trichloromethane containing iridium dichloro dimer and 0.13g (0.9mmol) Compound C; drip the chloroform soln formation mixed solution of 10mL containing 0.19g (3.6mmol) sodium methylate subsequently, stirring heating mixed solution is warming up to 62 DEG C of reflux states reaction 15h.Naturally, after being chilled to room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, has solid to separate out.Filter, collect crude product, solid uses deionized water, methanol wash for several times successively, and obtain 0.06g pure products through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 7.6%.
Structural Identification:
Mass spectrum (MS m/z): 1315.7 (M
+);
Ultimate analysis: C
64h
92f
4irN
11o
2;
Theoretical value: C, 58.42; H, 7.05; F, 5.78; Ir, 14.61; N, 11.71; O, 2.43;
Measured value: C, 58.45; H, 7.01; F, 5.85; Ir, 14.53; N, 11.76; O, 2.40.
End product is CH at 298K temperature
2cl
2solution (~ 10
-6the maximum emission peak of the emmission spectrum M), at 486nm place, has an acromion at 520nm place, with the CH of the FIrpic of same concentrations simultaneously
2cl
2solution is standard (Φ
pL=0.26) Φ of end product, is recorded
pL=0.06.
Application Example
The present embodiment is organic electroluminescence device, and it is with the title complex that embodiment 1 is obtained two (2-(2', 6'-difluoro pyridine-4-base)-5-methoxy pyrimidine-N, C
3') (5-(2'-pyridyl)-pyrrotriazole) close iridium (representing using M1) as luminescent layer doping guest materials; Structural formula is:
As shown in Figure 3, the structure of organic electroluminescence device 300 comprises the transparent anode 301, hole injection layer 302, hole transmission layer 303, electronic barrier layer 304, luminescent layer 305, hole blocking layer 306, electron transfer layer 307, electron injection buffer layer 308, the negative electrode 309 that stack gradually.
The preparation technology of this organic electroluminescence device:
It is 200nm that a glass-based plate deposits a layer thickness, square resistance is that the tin indium oxide (ITO) of 10 Ω/ is as transparent anode 301, on anode 301, the m-MTDATA(4 that a layer thickness is 40nm is prepared successively by vacuum evaporation, 4 ', 4 ' '-three (N-3-methylphenyl-N-phenyl is amino) triphenylamine) hole-injecting material is as hole injection layer 302, a layer thickness is the NPB(N of 20nm, N '-bis-(1-naphthyl)-N, N '-diphenylbenzidine) hole mobile material is as hole transmission layer 303, a layer thickness is the mCP(1 of 10nm, two (9-carbazyl) benzene of 3-) electron-blocking materials is as electronic barrier layer 304, a layer thickness be 30nm be that the mCP mixing and doping material of 7%M1 is as luminescent layer 305 doped with massfraction, on this luminescent layer 305, vacuum evaporation a layer thickness is successively the BCP(2 of 10nm again, 9-dimethyl-4, 7-phenylbenzene-phenanthrolene) material is as hole blocking layer 306, thickness is that the Alq3 (three (oxine) aluminium) of 35nm is as electron transfer layer 307, thickness is that the LiF of 1nm is as electron injection buffer layer 308, the last vacuum plating of employing on the buffer layer techniques of deposition thickness is the metal A l of 120nm, as the negative electrode 309 of device.Therefore, the structure of this organic electroluminescence device is: ITO/m-MTDATA/NPB/mCP/mCP:M1/BCP/Alq3/LiF/Al; Wherein, mCP:M1 represents that M1 is doped in mCP, and slash "/" represents laminate structure.
Current versus brightness-the voltage characteristic of above-mentioned organic electroluminescence device is tested by Keithley source measuring system (Keithley2400Sourcemeter), with French its electroluminescent spectrum of JY company SPEX CCD3000 spectrometer measurement, all measurements all complete in atmosphere at room temperature.The maximum emission wavelength of the electroluminescent spectrum of device is positioned at 460nm, has an acromion at 491nm place, and maximum current efficiency is 13.4cd/A, and maximum external quantum efficiency is 5.8%.
Should be understood that, the above-mentioned statement for present pre-ferred embodiments is comparatively detailed, and therefore can not think the restriction to scope of patent protection of the present invention, scope of patent protection of the present invention should be as the criterion with claims.
Claims (10)
1. an iridium metal complexes of blue light organic phosphorescent electroluminescent materials, is characterized in that, general structure is as follows:
Wherein, R is hydrogen atom, C
1~ C
20alkyl or C
1~ C
20alkoxyl group.
2. a preparation method for iridium metal complexes of blue light organic phosphorescent electroluminescent materials, is characterized in that, comprises the steps:
(1), under protection of inert gas, by structural formula be
compd A and structural formula be
compd B be dissolved in the first organic solvent containing catalyzer and alkali, obtain reaction solution, described reaction solution carries out Suzuki linked reaction 6 ~ 12h at 85 ~ 100 DEG C of temperature, and after question response stops, separating-purifying reaction solution, obtaining structural formula is
cyclic metal complexes; Wherein, the mol ratio of described compd A and compd B is 1:1 ~ 1:1.5; R is hydrogen atom, C
1~ C
20alkyl or C
1~ C
20alkoxyl group;
(2), under protection of inert gas, be that 2:1 ~ 4:1 is dissolved in the mixed solvent that cellosolvo and water formed with mol ratio by described cyclic metal complexes and three hydrated iridium trichloride, heating mixed solvent is to reflux state stirring reaction 22 ~ 25h; Be cooled to room temperature, separating-purifying, obtaining structural formula is
chlorine bridge dipolymer; R is hydrogen atom, C
1~ C
20alkyl or C
1~ C
20alkoxyl group;
(3), under protection of inert gas, by described chlorine bridge dipolymer and structural formula be
compound C be that in the second organic solvent of being dissolved in containing sodium methylate or sodium ethylate of 1:2 ~ 1:3, obtain mixing solutions, heating mixing solutions to 40 ~ 84 DEG C, stirring reaction 8 ~ 20h, is cooled to room temperature, separating-purifying, obtains structural formula to be with mol ratio
iridium metal complexes of blue light organic phosphorescent electroluminescent materials; R is hydrogen atom, C
1~ C
20alkyl or C
1~ C
20alkoxyl group.
3. the preparation method of iridium metal complexes of blue light organic phosphorescent electroluminescent materials according to claim 2, is characterized in that, described alkali is sodium carbonate or salt of wormwood, and the mol ratio of alkali and compd A is 1:1 ~ 3:1.
4. the preparation method of iridium metal complexes of blue light organic phosphorescent electroluminescent materials according to claim 2, it is characterized in that, described catalyzer is that four (triphenylphosphines) close palladium or dichloro two (triphenyl phosphorus) closes palladium, and the mol ratio of described catalyzer and compd A is 0.02:1 ~ 0.05:1.
5. the preparation method of iridium metal complexes of blue light organic phosphorescent electroluminescent materials according to claim 2, is characterized in that, the volumetric molar concentration of described compd A in reaction solution is 0.1 ~ 0.2mol/L.
6. the preparation method of iridium metal complexes of blue light organic phosphorescent electroluminescent materials according to claim 2, is characterized in that, the volumetric molar concentration of described chlorine bridge dipolymer in mixing solutions is 0.01 ~ 0.02mol/L.
7. the preparation method of iridium metal complexes of blue light organic phosphorescent electroluminescent materials according to claim 2, is characterized in that, the separating-purifying of described cyclic metal complexes comprises:
After question response stops being chilled to room temperature, dichloromethane extraction, separatory, be washed to neutrality, with anhydrous magnesium sulfate drying; Filter, filtrate decompression steams solvent and obtains crude product, and the mixed solution formed with ethyl acetate and normal hexane is separated for elutriant carries out silica gel column chromatography, obtains described cyclic metal complexes after drying.
8. the preparation method of iridium metal complexes of blue light organic phosphorescent electroluminescent materials according to claim 2, is characterized in that, the separating-purifying of described chlorine bridge dipolymer comprises:
After question response stopping is chilled to room temperature, rotates and steam except partial solvent, add appropriate distilled water, filter and obtain solid, solid uses distilled water, methanol wash successively, obtains described chlorine bridge dipolymer after drying.
9. the preparation method of iridium metal complexes of blue light organic phosphorescent electroluminescent materials according to claim 2, is characterized in that, the separating-purifying of described iridium metal complexes of blue light organic phosphorescent electroluminescent materials comprises:
After question response stops being chilled to room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, has solid to separate out; Collecting by filtration crude product, crude product uses deionized water, methanol wash for several times successively, after the mixed solvent recrystallization that methylene dichloride and dehydrated alcohol are formed, obtain iridium metal complexes of blue light organic phosphorescent electroluminescent materials.
10. an organic electroluminescence device, comprises luminescent layer, it is characterized in that, adulterate in described luminescent layer iridium metal complexes of blue light organic phosphorescent electroluminescent materials, and general structure is as follows:
Wherein, R is hydrogen atom, C
1~ C
20alkyl or C
1~ C
20alkoxyl group.
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