CN104418911A - Organic blue light electrophosphorescent metal iridium complex, preparation method thereof and organic electroluminescent device - Google Patents
Organic blue light electrophosphorescent metal iridium complex, preparation method thereof and organic electroluminescent device Download PDFInfo
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- CN104418911A CN104418911A CN201310395551.8A CN201310395551A CN104418911A CN 104418911 A CN104418911 A CN 104418911A CN 201310395551 A CN201310395551 A CN 201310395551A CN 104418911 A CN104418911 A CN 104418911A
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- blue light
- metal complexes
- electroluminescent materials
- iridium
- light organic
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- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 78
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 67
- 239000002184 metal Substances 0.000 title claims abstract description 67
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 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 62
- 239000000463 material Substances 0.000 claims description 62
- 238000006243 chemical reaction Methods 0.000 claims description 59
- 239000000243 solution Substances 0.000 claims description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 51
- 239000007787 solid Substances 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- 238000003756 stirring Methods 0.000 claims description 34
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 33
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 27
- 238000005401 electroluminescence Methods 0.000 claims description 26
- 239000012153 distilled water Substances 0.000 claims description 24
- 239000012046 mixed solvent Substances 0.000 claims description 24
- 239000012043 crude product Substances 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 23
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 230000004044 response Effects 0.000 claims description 22
- 239000000460 chlorine Substances 0.000 claims description 19
- 229910052801 chlorine Inorganic materials 0.000 claims description 19
- 125000004122 cyclic group Chemical group 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000010992 reflux Methods 0.000 claims description 17
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 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 11
- 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
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 11
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 10
- 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
- 239000003960 organic solvent Substances 0.000 claims description 10
- 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 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
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 9
- 235000015320 potassium carbonate Nutrition 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 8
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 6
- 229960004756 ethanol Drugs 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 abstract description 11
- 125000003545 alkoxy group Chemical group 0.000 abstract description 8
- 239000003446 ligand Substances 0.000 abstract description 8
- 125000000714 pyrimidinyl group Chemical group 0.000 abstract description 6
- TXXZKLBZLRLJON-UHFFFAOYSA-N 2-[3,5-difluoro-4-(trifluoromethyl)phenyl]pyridine Chemical compound FC=1C=C(C=C(C1C(F)(F)F)F)C1=NC=CC=C1 TXXZKLBZLRLJON-UHFFFAOYSA-N 0.000 abstract 1
- 238000007385 chemical modification Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 43
- 229910052757 nitrogen Inorganic materials 0.000 description 37
- 230000015572 biosynthetic process Effects 0.000 description 33
- 238000003786 synthesis reaction Methods 0.000 description 28
- 239000007788 liquid Substances 0.000 description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 15
- 239000007795 chemical reaction product Substances 0.000 description 15
- 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 10
- 210000002659 acromion Anatomy 0.000 description 8
- 238000011160 research Methods 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 0 CC*[*@](C=CC)C=*(CC)CC([C@](C(C)C(N)=C1*C)C=C1N)=C(C)*C Chemical compound CC*[*@](C=CC)C=*(CC)CC([C@](C(C)C(N)=C1*C)C=C1N)=C(C)*C 0.000 description 7
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229960001701 chloroform Drugs 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000011368 organic material Substances 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 5
- 150000003230 pyrimidines Chemical class 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 125000006575 electron-withdrawing group Chemical group 0.000 description 4
- -1 iridium (III) compound Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 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
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- CINYXYWQPZSTOT-UHFFFAOYSA-N 3-[3-[3,5-bis(3-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical compound C1=CN=CC(C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)=C1 CINYXYWQPZSTOT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 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
- 238000010791 quenching Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000003335 steric effect Effects 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 1
- YMMGRPLNZPTZBS-UHFFFAOYSA-N 2,3-dihydrothieno[2,3-b][1,4]dioxine Chemical compound O1CCOC2=C1C=CS2 YMMGRPLNZPTZBS-UHFFFAOYSA-N 0.000 description 1
- OBBXILSUQUPBJQ-UHFFFAOYSA-N 2-bromo-4-hexoxypyrimidine Chemical compound BrC1=NC=CC(=N1)OCCCCCC OBBXILSUQUPBJQ-UHFFFAOYSA-N 0.000 description 1
- FUTVFKDRMZATOI-UHFFFAOYSA-N 2-bromo-4-icosylpyrimidine Chemical compound BrC1=NC=CC(=N1)CCCCCCCCCCCCCCCCCCCC FUTVFKDRMZATOI-UHFFFAOYSA-N 0.000 description 1
- MFMNSNLMFVABMQ-UHFFFAOYSA-N B(O)O.FC1=CC=C(C=C1)C(F)(F)F Chemical compound B(O)O.FC1=CC=C(C=C1)C(F)(F)F MFMNSNLMFVABMQ-UHFFFAOYSA-N 0.000 description 1
- GWHFQNLSANHOEI-XYOKQWHBSA-N CC(C/C=C(\c1ncccc1)/N)C(C(F)(F)F)=C(C)C Chemical compound CC(C/C=C(\c1ncccc1)/N)C(C(F)(F)F)=C(C)C GWHFQNLSANHOEI-XYOKQWHBSA-N 0.000 description 1
- UNKZATKOYTYVEI-UHFFFAOYSA-N CCc1cnc(-c2cc(F)c(C(F)(F)F)c(F)c2)nc1 Chemical compound CCc1cnc(-c2cc(F)c(C(F)(F)F)c(F)c2)nc1 UNKZATKOYTYVEI-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000151 deposition Methods 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
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000005429 oxyalkyl group Chemical group 0.000 description 1
- 235000012736 patent blue V Nutrition 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 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
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- 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 provides an organic blue light electrophosphorescent metal iridium complex, a preparation method thereof and an organic electroluminescent device. The organic blue light electrophosphorescent metal iridium complex has the structural general formula as shown in the specification, wherein r is a hydrogen atom, c1-c20 alkyl or c1-c20 alkoxy. The organic blue light electrophosphorescent metal iridium complex is synthesized by taking 2-(3', 5'-difluoro-4'-trifluoromethylphenyl)pyridine as a cyclometalated ligand and 3-trifluoromethyl-5-(2'-pyridyl)-1, 2, 4-triazole as an auxiliary ligand, and the color of light emitted by the organic blue light electrophosphorescent metal iridium complex is regulated through chemical modification on an alkyl chain or an alkoxy chain introduced to a pyrimidine ring of the cyclometalated ligand, so that blue light with high color purity is obtained.
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 2.2:1 ~ 3:1 is dissolved in the mixed solvent that cellosolvo and water formed with mol ratio by described cyclic metal complexes and three hydrated iridium trichloride, heating mixed solvent is to reflux state stirring reaction 22 ~ 25h; Be cooled to room temperature, separating-purifying, obtaining structural formula is
chlorine bridge dipolymer; 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 in step (1), 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, catalyzer described in step (1) is that four (triphenylphosphines) close palladium (Pd (PPh
3)
4) or dichloro two (triphenyl phosphorus) close palladium (Pd (PPh
3)
2cl
2), the mol ratio of described catalyzer and compd A is 0.03:1 ~ 0.05:1.
Preferably, described in step (1), the volumetric molar concentration of compd A in reaction solution is 0.1 ~ 0.2mol/L.
Preferably, the volumetric molar concentration of chlorine bridge dipolymer described in step (3) in mixing solutions is 0.01 ~ 0.02mol/L.
Preferably, described in step (1), the separating-purifying of 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.
Preferably, described in step (2), the separating-purifying of chlorine bridge dipolymer comprises:
After question response stops being chilled to room temperature, filter and obtain solid, solid uses ethanol, n-hexane successively, obtains described chlorine bridge dipolymer after vacuum-drying, or
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, described in step (3), the separating-purifying of 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 with 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl) pyrimidine is cyclic metal complexes agent structure, with 3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole for assistant ligand.Pyrimidyl on cyclic metal complexes is conducive to the lumo energy improving material, and on phenyl ring, strong electron-withdrawing group two F bases and trifluoromethyl are conducive to the HOMO energy level reducing material, make the effective blue shift of material emission wavelength; The introducing of alkyl or alkoxyl group on pyrimidine ring, the electro mass-energy of giving of alkyl or alkoxyl group obtains satisfied blue light emitting wavelength on the one hand, on the one hand the alkyl chain of different lengths is conducive to increasing its solvability in organic solvent in addition, and branch chain type alkyl or alkoxyl group can produce certain space steric effect, thus the direct effect between minimizing atoms metal, reduce the self-quenching phenomenon of triplet exciton; In addition, on phenyl ring, the introducing of strong electron-withdrawing group fluorine-based, the trifluoromethyl of group and assistant ligand 3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole can also improve luminescent properties, is beneficial to evaporation, increases film-forming type and improves the stability of device.
A kind of organic electroluminescence device, comprise luminescent layer, 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-(3 ', 5 '-two fluoro-4 '-trifluoromethyl) pyrimidine is cyclic metal complexes, with 3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole is assistant ligand, synthesize 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 higher blue light of purity of color.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:
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 2.2:1 ~ 3:1 is dissolved in the mixed solvent that cellosolvo and water formed with mol ratio by described cyclic metal complexes and three hydrated iridium trichloride, heating mixed solvent is to reflux state stirring reaction 22 ~ 25h; Be cooled to room temperature, separating-purifying, obtaining structural formula is
chlorine bridge dipolymer; 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, the first organic solvent described in step (1) is toluene or dimethyl formamide (DMF).
Preferably, described in step (1), 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, catalyzer described in step (1) is that four (triphenylphosphines) close palladium (Pd (PPh
3)
4) or dichloro two (triphenyl phosphorus) close palladium (Pd (PPh
3)
2cl
2), the mol ratio of described catalyzer and compd A is 0.03:1 ~ 0.05:1.
Preferably, described in step (1), the volumetric molar concentration of compd A in reaction solution is 0.1 ~ 0.2mol/L.
Preferably, the volumetric molar concentration in the mixed solvent that formed at cellosolvo and water of three hydrated iridium trichloride described in step (2) is 0.02 ~ 0.05mol/L.
Preferably, described cellosolvo and water volume ratio are 3:1.
Preferably, described in step (3), the second organic solvent is 1,2-ethylene dichloride, trichloromethane or methylene dichloride.
Preferably, the mol ratio of sodium methylate described in step (3) or sodium ethylate and described chlorine bridge dipolymer is 8:1 ~ 12:1.
Preferably, the volumetric molar concentration of chlorine bridge dipolymer described in step (3) in mixing solutions is 0.0067 ~ 0.02mol/L.
Preferably, described rare gas element is nitrogen or argon gas.
Preferably, described in step (1), the separating-purifying of 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 1:1 ~ 5:1.
Preferably, described in step (2), the separating-purifying of chlorine bridge dipolymer is:
After question response stops being chilled to room temperature, filter and obtain solid, solid uses ethanol, n-hexane successively, obtains described chlorine bridge dipolymer after vacuum-drying, or
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, described in step (3), the separating-purifying of 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 with 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl) pyrimidine is cyclic metal complexes agent structure, with 3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole for assistant ligand.Pyrimidyl on cyclic metal complexes is conducive to the lumo energy improving material, and on phenyl ring, strong electron-withdrawing group two F bases and trifluoromethyl are conducive to the HOMO energy level reducing material, make the effective blue shift of material emission wavelength; The introducing of alkyl or alkoxyl group on pyrimidine ring, the electro mass-energy of giving of alkyl or alkoxyl group obtains satisfied blue light emitting wavelength on the one hand, on the one hand the alkyl chain of different lengths is conducive to increasing its solvability in organic solvent in addition, and branch chain type alkyl or alkoxyl group can produce certain space steric effect, thus the direct effect between minimizing atoms metal, reduce the self-quenching phenomenon of triplet exciton; In addition, on phenyl ring, the introducing of strong electron-withdrawing group fluorine-based, the trifluoromethyl of group and assistant ligand 3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole can also 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-(3 ', 5 '-two fluoro-4 '-trifluoromethyl) pyrimidine-N, C
2') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close the synthesis of iridium
(1) synthesis of 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl) pyrimidine
Under nitrogen protection; by 1.59g (10mmol) 2-bromo pyrimi piperidine (A1), 2.71g (12mmol) 3; the fluoro-4-trifluoromethylbenzene boronic acid (B) of 5-bis-and 0.58g (0.5mmol) four (triphenyl phosphorus) close palladium and are dissolved in 40mL toluene, stir 10min.Drip 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 1:1 is separated for elutriant carries out silica gel column chromatography with the mixed solution that normal hexane is formed with volume ratio, after drying solid 1.14g, yield is 43.8%.
Structural Identification:
Mass spectrum (MS m/z): 260.0 (M
+);
Ultimate analysis: C
11h
5f
5n
2;
Theoretical value: C, 50.78; H, 1.94; F, 36.51; N, 10.77;
Measured value: C, 50.74; H, 1.99; F, 36.53; N, 10.74.
(2) part be 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl) pyrimidine containing the dimeric synthesis of iridium dichloro
Under nitrogen protection; by 0.71g (2mmol) three hydrated iridium trichloride and 1.3g (5mmol) 2-(3 '; 5 '-two fluoro-4 '-trifluoromethyl) pyrimidine is dissolved in cellosolvo that 60mL volume ratio is 3:1 and the mixed solvent that water is formed, and is heated to stirring reaction 24h under reflux state.Be chilled to the throw out in collecting by filtration reaction mixture after room temperature, ethanol, n-hexane successively, after vacuum-drying solids 0.74g, yield is 49.6%.
(3) title complex two (2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl) pyrimidine-N, C
2') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close the synthesis of iridium
Under nitrogen protection; be 2-(3 ' by 0.75g (0.5mmol) part; 5 '-two fluoro-4 '-trifluoromethyl) pyrimidine containing iridium dichloro dimer and 0.26g (1.2mmol) 3-trifluoromethyl-5-(2'-pyridyl)-1; 2; 4-triazole (Compound C) is in 15mL trichloromethane; 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 state 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 0.37g pure products through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 40.0%.
Structural Identification:
Mass spectrum (MS m/z): 924.1 (M
+);
Ultimate analysis: C
30h
12f
13irN
8;
Theoretical value: C, 39.01; H, 1.31; F, 26.74; Ir, 20.81; N, 12.13;
Measured value: C, 39.05; H, 1.27; F, 26.82; Ir, 20.76; N, 12.10.
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 luminous (unit nm), and the longitudinal axis is normalized photoluminescence intensity, and end product is CH at 298K temperature
2cl
2solution (~ 10
-5the maximum emission peak of the emmission spectrum M), at 470nm place, has an acromion at 493nm place simultaneously, can be used as the preparation field that blue light electroluminescent material is widely used in organic electroluminescence device.
In addition, 10
-5the CH of M end product
2cl
2solution at 298K temperature, with concentration for ~ 10
-5the Ir (ppy) of M
3cH
2cl
2solution is standard (Φ
pL=0.40) Φ of end product, is recorded
pL=0.12, the iridium electroluminescent organic material that contains of visible the present embodiment has higher luminous quantum efficiency.
Embodiment 2: title complex two (2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-methylpyrimidine-N, C
2') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close the synthesis of iridium
(1) synthesis of 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-methylpyrimidine
Under nitrogen protection; bromo-for 1.73g (10mmol) 2-5-methylpyrimidine (A2), 2.48g (11mmol) B and 0.28g (0.4mmol) dichloro two (triphenyl phosphorus) are closed palladium and be dissolved in 50mL DMF, stirs 10min.The aqueous solution forming reactions liquid of 25mL containing 3.18g (30mmol) sodium carbonate is dripped subsequently in reaction system.Be heated to stirring reaction 8h under 90 DEG C of state of temperatures.After question response liquid cooling to room temperature, dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying.Filter, filtrate decompression steams solvent and obtains crude product.Be that the ethyl acetate of 2:1 is separated for elutriant carries out silica gel column chromatography with the mixed solution that normal hexane is formed with volume ratio, after drying solid 0.82g, yield is 29.9%.
Structural Identification:
Mass spectrum (MS m/z): 274.0 (M
+);
Ultimate analysis: C
12h
7f
5n
2;
Theoretical value: C, 52.57; H, 2.57; F, 34.64; N, 10.22;
Measured value: C, 52.53; H, 2.63; F, 34.56; N, 10.28.
(2) part be 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-methylpyrimidine containing the dimeric synthesis of iridium dichloro
Under nitrogen protection; by 0.71g (2mmol) three hydrated iridium trichloride; 1.64g (6mmol) 2-(3 '; 5 '-two fluoro-4 '-trifluoromethyl)-4-methylpyrimidine is dissolved in cellosolvo that 50mL volume ratio is 3:1 and the mixed solvent that water is formed, and is heated to stirring reaction 22h under reflux state.Be chilled to the throw out in collecting by filtration reaction mixture after room temperature, ethanol, n-hexane successively, after vacuum-drying solids 0.59g, yield is 38.1%.
(3) title complex two (2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-t-butyl pyrimidines-N, C
2') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close the synthesis of iridium
Under nitrogen protection; be 2-(3 ' by 0.77g (0.5mmol) part; 5 '-two fluoro-4 '-trifluoromethyl)-5-methylpyrimidine be dissolved in 20mL methylene dichloride containing iridium dichloro dimer and 0.21g (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 0.28g pure products through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 29.4%.
Structural Identification:
Mass spectrum (MS m/z): 952.1 (M
+);
Ultimate analysis: C
32h
16f
13irN
8;
Theoretical value: C, 40.38; H, 1.69; F, 25.95; Ir, 20.20; N, 11.77;
Measured value: C, 40.35; H, 1.76; F, 25.91; Ir, 20.27; N, 11.71.
End product is CH at 298K temperature
2cl
2solution (~ 10
-5the maximum emission peak of the emmission spectrum M), at 469nm place, has an acromion at 491nm place, with the Ir of same concentrations (ppy) simultaneously
3cH
2cl
2solution is standard (Φ
pL=0.40) Φ of end product, is recorded
pL=0.07, the iridium electroluminescent organic material that contains of visible the present embodiment has higher luminous quantum efficiency, can be used as the preparation field that blue light electroluminescent material is widely used in organic electroluminescence device.
Embodiment 3: title complex two (2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-t-butyl pyrimidines-N, C
2') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close the synthesis of iridium
(1) synthesis of 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-t-butyl pyrimidines
Under nitrogen protection; bromo-for 2.15g (10mmol) 2-5-t-butyl pyrimidines (A3), 3.39g (15mmol) compd B and 0.21g (0.3mmol) dichloro two (triphenyl phosphorus) are closed palladium to be dissolved in 35mL DMF, stirs 10min.The aqueous solution forming reactions liquid of 15mL containing 1.38g (10mmol) salt of wormwood is dripped subsequently in reaction system.Be heated to stirring reaction 10h under 85 DEG C of states.After question response liquid cooling to room temperature, dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying.Filter, filtrate decompression steams solvent and obtains crude product.Be that the ethyl acetate of 3:1 is separated for elutriant carries out silica gel column chromatography with the mixing solutions that normal hexane is formed with volume ratio, after drying solid 0.47g, yield is 14.9%.
Structural Identification:
Mass spectrum (MS m/z): 316.1 (M
+);
Ultimate analysis: C
15h
13f
5n
2;
Theoretical value: C, 56.96; H, 4.14; F, 30.04; N, 8.86;
Measured value: C, 56.92; H, 4.20; F, 30.00; N, 8.88.
(2) part be 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-t-butyl pyrimidines containing the dimeric synthesis of iridium dichloro
Under nitrogen protection; by 0.35g (1mmol) three hydrated iridium trichloride and 0.70g (2.2mmol) 2-(3 '; 5 '-two fluoro-4 '-trifluoromethyl)-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.Be chilled to the throw out in collecting by filtration reaction mixture after room temperature, ethanol, n-hexane successively, after vacuum-drying solids 0.22g, yield is 25.6%.
(3) title complex two (2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-t-butyl pyrimidines-N, C
2') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close the synthesis of iridium
Under nitrogen protection; be 2-(3 ' by 0.86g (0.5mmol) part; 5 '-two fluoro-4 '-trifluoromethyl)-5-t-butyl pyrimidines be dissolved in 25mL trichloromethane containing iridium dichloro dimer and 0.27g (1.25mmol) Compound C; drip the chloroform soln formation mixing solutions of 15mL containing 0.41g (6mmol) sodium ethylate subsequently, stirring heating mixing solutions is warming up to 62 DEG C of reflux states 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 0.18g pure products through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 17.4%.
Structural Identification:
Mass spectrum (MS m/z): 1036.2 (M
+);
Ultimate analysis: C
38h
28f
13irN
8;
Theoretical value: C, 44.06; H, 2.72; F, 23.84; Ir, 18.56; N, 10.82;
Measured value: C, 44.02; H, 2.78; F, 23.80; Ir, 18.59; N, 10.81.
End product is CH at 298K temperature
2cl
2solution (~ 10
-5the maximum emission peak of the emmission spectrum M), at 473nm place, has an acromion at 496nm place, with the Ir of same concentrations (ppy) simultaneously
3cH
2cl
2solution is standard (Φ
pL=0.40) Φ of end product, is recorded
pL=0.11.
Embodiment 4: title complex two (2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-4-eicosyl pyrimidine-N, C
2') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close the synthesis of iridium
(1) synthesis of 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-4-eicosyl pyrimidine
Under nitrogen protection; 2.20g (5mmol) 2-bromo-4-eicosyl pyrimidine (A4), 1.36g (6mmol) compd B and 0.23g (0.2mmol) four (triphenyl phosphorus) are closed palladium to be dissolved in 35mL toluene, stirs 10min.The aqueous solution forming reactions liquid of 15mL containing 1.38g (10mmol) salt of wormwood is dripped subsequently in reaction system.Stirring reaction 12h 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 4:1 is separated for elutriant carries out silica gel column chromatography with the mixed solution that normal hexane is formed with volume ratio, after drying solid 0.54g, yield is 20.0%.
Structural Identification:
Mass spectrum (MS m/z): 540.4 (M
+);
Ultimate analysis: C
31h
45f
5n
2;
Theoretical value: C, 68.86; H, 8.39; F, 17.57; N, 5.18;
Measured value: C, 68.83; H, 8.45; F, 17.51; N, 5.21.
(2) part be 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-4-eicosyl pyrimidine containing the dimeric synthesis of iridium dichloro
Under nitrogen protection; by 0.18g (0.5mmol) three hydrated iridium trichloride; 0.81g (1.5mmol) 2-(3 '; 5 '-two fluoro-4 '-trifluoromethyl) to be dissolved in 25mL volume ratio be in the mixed solvent that formed of 3:12-ethoxy ethanol and water to-4-eicosyl pyrimidine, stirring reaction 25h at reflux.After being chilled to room temperature, rotating and steam except partial solvent, add appropriate distilled water, filter.Solid uses distilled water, methanol wash successively, and obtain solids 0.10g after drying, yield is 15.3%.
(3) title complex two (2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-4-eicosyl pyrimidine-N, C
2') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close the synthesis of iridium
Under nitrogen protection; be 2-(3 ' by 0.52g (0.2mmol) part; 5 '-two fluoro-4 '-trifluoromethyl)-4-eicosyl pyrimidine be dissolved in 15mL1 containing iridium dichloro dimer and 0.13g (0.6mmol) Compound C; in 2-ethylene dichloride; drip 10mL subsequently containing 1 of 0.11g (2mmol) 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 0.04g pure products through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 7.0%.
Structural Identification:
Mass spectrum (MS m/z): 1484.7 (M
+);
Ultimate analysis: C
70h
92f
13irN
8;
Theoretical value: C, 56.63; H, 6.25; F, 16.63; Ir, 12.95; N, 7.55;
Measured value: C, 56.57; H, 6.34; F, 16.55; Ir, 12.93; N, 7.61.
End product is CH at 298K temperature
2cl
2solution (~ 10
-5the maximum emission peak of the emmission spectrum M), at 493nm place, has an acromion at 516nm place, with the Ir of same concentrations (ppy) simultaneously
3cH
2cl
2solution is standard (Φ
pL=0.40) Φ of end product, is recorded
pL=0.008.
Embodiment 5: title complex two (2-(the fluoro-3'-trifluoromethyl of 4', 6'-bis-)-5-methoxy pyrimidine-N, C
2') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close the synthesis of iridium
(1) synthesis of 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-methoxy pyrimidine
Under nitrogen protection; bromo-for 1.89g (10mmol) 2-5-methoxy pyrimidine (A5), 2.71g (12mmol) compd B and 0.58g (0.5mmol) four (triphenyl phosphorus) are closed palladium to be dissolved in 40mL toluene, continues to stir 10min.The aqueous solution of 20mL containing 2.76g (20mmol) salt of wormwood is dripped subsequently in reaction system.Be heated to stirring reaction 6h under 100 DEG C of state of temperatures.After question response liquid cooling to room temperature, dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying.Filter, filtrate decompression steams solvent and obtains crude product.Be that the ethyl acetate of 2:1 is separated for elutriant carries out silica gel column chromatography with the mixed solution that normal hexane is formed with volume ratio, after drying solid 1.10g, yield is 37.9%.
Structural Identification:
Mass spectrum (MS m/z): 290.0 (M
+);
Ultimate analysis: C
12h
7f
5n
2o;
Theoretical value: C, 49.67; H, 2.43; F, 32.73; N, 9.65; O, 5.51;
Measured value: C, 49.61; H, 2.52; F, 32.65; N, 9.73; O, 5.49.
(2) part be 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-methoxy pyrimidine containing the dimeric synthesis of iridium dichloro
Under nitrogen protection; by 0.71g (2mmol) three hydrated iridium trichloride; 1.74g (6mmol) 2-(3 '; 5 '-two fluoro-4 '-trifluoromethyl)-5-methoxy pyrimidine is dissolved in cellosolvo that 50mL 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 0.64g after drying, yield is 39.7%.Dipolymer, without the need to further purification, can directly drop in next step reaction.
(3) title complex two (2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-methoxy pyrimidine-N, C
2') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close the synthesis of iridium
Under nitrogen protection; 0.81g (0.5mmol) part is 2-(3 '; 5 '-two fluoro-4 '-trifluoromethyl)-5-methoxy pyrimidine be dissolved in 15mL1 containing iridium dichloro dimer and 0.27g (1.25mmol) Compound C; in 2-ethylene dichloride; drip 10mL subsequently containing 1 of 0.27g (5mmol) sodium methylate; 2-dichloroethane solution forms mixing solutions, and stirring heating mixing solutions is warming up to 62 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 0.25g pure products through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 25.4%.
Structural Identification:
Mass spectrum (MS m/z): 984.1 (M
+);
Ultimate analysis: C
32h
16f
13irN
8o
2;
Theoretical value: C, 39.07; H, 1.64; F, 25.11; Ir, 19.54; N, 11.39; O, 3.25;
Measured value: C, 39.03; H, 1.71; F, 25.05; Ir, 19.59; N, 11.35; O, 3.27.
End product is CH at 298K temperature
2cl
2solution (~ 10
-5the maximum emission peak of the emmission spectrum M), at 465nm place, has an acromion at 489nm place, with the Ir of same concentrations (ppy) simultaneously
3cH
2cl
2solution is standard (Φ
pL=0.40) Φ of end product, is recorded
pL=0.06.
Embodiment 6: title complex two (2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-4-hexyloxy pyrimidine-N, C
2') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close the synthesis of iridium
(1) synthesis of 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-4-hexyloxy pyrimidine
Under nitrogen protection; 2.59g (10mmol) 2-bromo-4-hexyloxy pyrimidine (A6), 3.39g (15mmol) compd B and 0.21g (0.3mmol) dichloro two (triphenyl phosphorus) are closed palladium to be dissolved in 40mL DMF, stirs 10min.The aqueous solution forming reactions liquid of 20mL containing 1.38g (10mmol) salt of wormwood is dripped subsequently in reaction system.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 4:1 is separated for elutriant carries out silica gel column chromatography with the mixed solution that normal hexane is formed with volume ratio, after drying solid 0.79g, yield is 21.9%.
Structural Identification:
Mass spectrum (MS m/z): 360.1 (M
+);
Ultimate analysis: C
17h
17f
5n
2o;
Theoretical value: C, 56.67; H, 4.76; F, 26.36; N, 7.77; O, 4.44;
Measured value: C, 56.63; H, 4.83; F, 26.31; N, 7.84; O, 4.39.
(2) part be 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-4-hexyloxy pyrimidine containing the dimeric synthesis of iridium dichloro
Under nitrogen protection; by 0.35g (1mmol) three hydrated iridium trichloride and 0.79g (2.2mmol) 2-(3 '; 5 '-two fluoro-4 '-trifluoromethyl)-4-hexyloxy pyrimidine is dissolved in cellosolvo that 20mL 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 0.31g after drying, yield is 32.8%.
(3) title complex two (2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-4-hexyloxy pyrimidine-N, C
2') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close the synthesis of iridium
Under nitrogen protection; be 2-(3 ' by 0.95g (0.5mmol) part; 5 '-two fluoro-4 '-trifluoromethyl)-4-hexyloxy pyrimidine be dissolved in 20mL methylene dichloride containing iridium dichloro dimer and 0.21g (1mmol) Compound C; drip the dichloromethane solution formation mixing solutions of 15mL containing 0.27g (4mmol) sodium ethylate subsequently, stirring heating mixing solutions 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 0.11g pure products through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 9.8%.
Structural Identification:
Mass spectrum (MS m/z): 1124.2 (M
+)
Ultimate analysis: C42H36F13IrN8O2
Theoretical value: C, 44.88; H, 3.23; F, 21.97; Ir, 17.10; N, 9.97; O, 2.85;
Measured value: C, 44.84; H, 3.28; F, 21.93; Ir, 17.16; N, 9.91; O, 2.88.
End product is CH at 298K temperature
2cl
2solution (~ 10
-5the maximum emission peak of the emmission spectrum M), at 479nm place, has an acromion at 503nm place, with the Ir of same concentrations (ppy) simultaneously
3cH
2cl
2solution is standard (Φ
pL=0.40) Φ of end product, is recorded
pL=0.02.
Embodiment 7: title complex two (2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-eicosane oxygen yl pyrimidines-N, C
2') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close the synthesis of iridium
(1) synthesis of 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-eicosane oxygen yl pyrimidines
Under nitrogen protection; 2.28g (5mmol) 2-bromo-5-eicosane oxygen yl pyrimidines (A7), 1.36g (6mmol) compd B and 0.23g (0.2mmol) four (triphenyl phosphorus) are closed palladium to be dissolved in 35mL toluene, stirs 10min.The aqueous solution forming reactions liquid of 15mL containing 1.38g (10mmol) salt of wormwood is dripped subsequently in reaction system.Stirring reaction 12h 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 ethyl acetate and the normal hexane of 5:1 is separated for mixed solution that elutriant is formed carries out silica gel column chromatography with volume ratio, after drying solid 0.50g, yield is 18.0%.
Structural Identification:
Mass spectrum (MS m/z): 556.4 (M
+);
Ultimate analysis: C
31h
45f
5n
2o;
Theoretical value: C, 66.88; H, 8.15; F, 17.06; N, 5.03; O, 2.87;
Measured value: C, 66.83; H, 8.24; F, 17.04; N, 5.06; O, 2.83.
(2) part be 2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-eicosane oxygen yl pyrimidines containing the dimeric synthesis of iridium dichloro
Under nitrogen protection; by 0.18g (0.5mmol) three hydrated iridium trichloride; 0.84g (1.5mmol) 2-(3 '; 5 '-two fluoro-4 '-trifluoromethyl)-5-eicosane oxygen yl pyrimidines is dissolved in cellosolvo that 25mL volume ratio is 3:1 and the mixed solvent that water is formed, stirring reaction 25h at reflux.After being chilled to room temperature, rotating and steam except partial solvent, add appropriate distilled water, filter.Solid uses distilled water, methanol wash successively, and obtain solids 0.10g after drying, yield is 14.9%.
(3) title complex two (2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl)-5-eicosane oxygen yl pyrimidines-N, C
2') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) close the synthesis of iridium
Under nitrogen protection; be 2-(3 ' by 0.54g (0.2mmol) part; 5 '-two fluoro-4 '-trifluoromethyl)-5-eicosane oxygen yl pyrimidines be dissolved in 20mL trichloromethane containing iridium dichloro dimer and 0.13g (0.6mmol) Compound C; drip the chloroform soln formation mixing solutions of 10mL containing 0.16g (2.4mmol) sodium ethylate 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 0.02g pure products through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 3.3%.
Structural Identification:
Mass spectrum (MS m/z): 1516.7 (M
+);
Ultimate analysis: C
70h
92f
13irN
8o
2;
Theoretical value: C, 55.43; H, 6.11; F, 16.28; Ir, 12.67; N, 7.39; O, 2.11;
Measured value: C, 55.36; H, 6.19; F, 16.30; Ir, 12.62; N, 7.38; O, 2.15.
End product is CH at 298K temperature
2cl
2solution (~ 10
-5the maximum emission peak of the emmission spectrum M), at 499nm place, has an acromion at 523nm place, with the Ir of same concentrations (ppy) simultaneously
3cH
2cl
2solution is standard (Φ
pL=0.40) Φ of end product, is recorded
pL=0.003.
Application Example
The present embodiment is organic electroluminescence device, and it is with the title complex that embodiment 1 is obtained two (2-(3 ', 5 '-two fluoro-4 '-trifluoromethyl) pyrimidine-N, C
2') (3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) 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:
On the glass-based plate of pre-washing and UV-ozone process, a layer thickness is 100nm, square resistance is 10 Ω/ tin indium oxide (ITO) is deposited as transparent anode 301 at one, then on anode 301, spin coating a layer thickness is the PEDOT:PSS (poly-3 of 40nm, 4-ethylenedioxy thiophene/poly styrene sulfonate) hole-injecting material as hole injection layer 302, in nitrogen atmosphere, toast 10min at 120 DEG C of temperature; On hole injection layer spin coating a layer thickness be 50nm be that the PVK (Polyvinyl carbazole) of 12%M1 is as luminescent layer 303 doped with massfraction; Then on this luminescent layer 303 spin coating a layer thickness be TmPyPB (1,3,5-tri-(the m-pyridin-3-yl phenyl) benzene) material of 20nm as electron transfer layer 304, then at 80 DEG C of anneal 60min; Last on electron transfer layer 304 evaporation a layer thickness be the LiF of 1nm as electron injection buffer layer 305, electron buffer layer 305 adopts vacuum plating techniques of deposition thickness be the metal A l of 120nm, as the negative electrode 306 of device.Therefore, the structure of this organic electroluminescence device 300 is: ITO/PEDOT:PSS/PVK:M1/TmPyPB/LiF/Al; Wherein, PVK:M1 represents that M1 is doped in PVK, 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, record the maximum emission wavelength of organic electroluminescence device at 474nm place, an acromion is had at 501nm place, the maximum external quantum efficiency of device is 3.6%, and maximum lumen efficiency is 2.3lm/W.
Should be understood that, the above-mentioned statement for present pre-ferred embodiments is comparatively detailed, and therefore can not think the restriction to scope of patent protection of the present invention, scope of patent protection of the present invention should be as the criterion with claims.
Claims (10)
1. 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 2.2:1 ~ 3:1 is dissolved in the mixed solvent that cellosolvo and water formed with mol ratio by described cyclic metal complexes and three hydrated iridium trichloride, heating mixed solvent is to reflux state stirring reaction 22 ~ 25h; Be cooled to room temperature, separating-purifying, obtaining structural formula is
chlorine bridge dipolymer; 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, heat described 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 in step (1), alkali is sodium carbonate or salt of wormwood, and the mol ratio of described 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, catalyzer described in step (1) is that four (triphenylphosphines) close palladium or dichloro two (triphenyl phosphorus) closes palladium, and the mol ratio of described catalyzer and compd A is 0.03:1 ~ 0.05:1.
5. the preparation method of iridium metal complexes of blue light organic phosphorescent electroluminescent materials according to claim 2, is characterized in that, described in step (1), the volumetric molar concentration of compd A in reaction solution is 0.1 ~ 0.2mol/L.
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 chlorine bridge dipolymer described in step (3) in mixing solutions is 0.0067 ~ 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, described in step (1), the separating-purifying of 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, described in step (2), the separating-purifying of chlorine bridge dipolymer comprises:
After question response stops being chilled to room temperature, filter and obtain solid, solid uses ethanol, n-hexane successively, obtains described chlorine bridge dipolymer after vacuum-drying, or
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, described in step (3), the separating-purifying of 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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| CN114602558B (en) * | 2022-03-24 | 2023-10-31 | 联碳新材料技术(杭州)有限公司 | Metallic iridium photocatalyst and preparation method and application thereof |
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