CN104418906A - Organic blue light electrophosphorescent metal iridium complex as well as preparation method and application of organic blue light electrophosphorescent metal iridium complex - Google Patents
Organic blue light electrophosphorescent metal iridium complex as well as preparation method and application of organic blue light electrophosphorescent metal iridium complex Download PDFInfo
- Publication number
- CN104418906A CN104418906A CN201310394889.1A CN201310394889A CN104418906A CN 104418906 A CN104418906 A CN 104418906A CN 201310394889 A CN201310394889 A CN 201310394889A CN 104418906 A CN104418906 A CN 104418906A
- Authority
- CN
- China
- Prior art keywords
- blue light
- metal complexes
- compd
- compound
- electroluminescent materials
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 77
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 40
- 239000002184 metal Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000010668 complexation reaction Methods 0.000 title 1
- 239000000463 material Substances 0.000 claims abstract description 50
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims description 91
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 51
- 239000000243 solution Substances 0.000 claims description 37
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 36
- 239000012043 crude product Substances 0.000 claims description 36
- 150000001875 compounds Chemical class 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 27
- 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 26
- 238000001035 drying Methods 0.000 claims description 25
- 239000011259 mixed solution Substances 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 229910052763 palladium Inorganic materials 0.000 claims description 17
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 16
- 238000005401 electroluminescence Methods 0.000 claims description 13
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 239000012046 mixed solvent Substances 0.000 claims description 12
- 239000003960 organic solvent Substances 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
- 239000000706 filtrate Substances 0.000 claims description 11
- 230000004044 response Effects 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 claims description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 9
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 9
- 239000003480 eluent Substances 0.000 claims description 9
- 229960004756 ethanol Drugs 0.000 claims description 9
- 238000000605 extraction Methods 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 9
- 238000001953 recrystallisation Methods 0.000 claims description 9
- 238000010898 silica gel chromatography Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 9
- 238000001291 vacuum drying Methods 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
- 238000000746 purification Methods 0.000 claims description 8
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 229960001701 chloroform Drugs 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 abstract description 7
- 125000003545 alkoxy group Chemical group 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 42
- 229910052757 nitrogen Inorganic materials 0.000 description 42
- 150000002460 imidazoles Chemical class 0.000 description 32
- 238000003756 stirring Methods 0.000 description 28
- 230000015572 biosynthetic process Effects 0.000 description 21
- 229910052799 carbon Inorganic materials 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 21
- 239000000047 product Substances 0.000 description 16
- GNUYWXZHCXBVGI-UHFFFAOYSA-N B(O)O.FC=1C=CC=C(C1)C(F)(F)F Chemical compound B(O)O.FC=1C=CC=C(C1)C(F)(F)F GNUYWXZHCXBVGI-UHFFFAOYSA-N 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 14
- 238000001819 mass spectrum Methods 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 210000002659 acromion Anatomy 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 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
- 238000001816 cooling Methods 0.000 description 7
- 239000000539 dimer Substances 0.000 description 7
- 150000003230 pyrimidines Chemical class 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 235000015320 potassium carbonate Nutrition 0.000 description 6
- 125000000714 pyrimidinyl group Chemical group 0.000 description 5
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- RGPBQGGBWIMGMA-BJMVGYQFSA-N 5-[(e)-[5-(4-bromophenyl)-6-hydroxy-3,6-dihydro-1,3,4-oxadiazin-2-ylidene]methyl]-1h-pyrimidine-2,4-dione Chemical compound OC1O\C(=C\C=2C(NC(=O)NC=2)=O)NN=C1C1=CC=C(Br)C=C1 RGPBQGGBWIMGMA-BJMVGYQFSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000006575 electron-withdrawing group Chemical group 0.000 description 3
- -1 iridium (III) compound Chemical class 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- OBBXILSUQUPBJQ-UHFFFAOYSA-N 2-bromo-4-hexoxypyrimidine Chemical compound BrC1=NC=CC(=N1)OCCCCCC OBBXILSUQUPBJQ-UHFFFAOYSA-N 0.000 description 2
- FUTVFKDRMZATOI-UHFFFAOYSA-N 2-bromo-4-icosylpyrimidine Chemical compound BrC1=NC=CC(=N1)CCCCCCCCCCCCCCCCCCCC FUTVFKDRMZATOI-UHFFFAOYSA-N 0.000 description 2
- 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
- 0 C=*c(ccc(F)c1C(F)(F)F)c1F Chemical compound C=*c(ccc(F)c1C(F)(F)F)c1F 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000009826 distribution Methods 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
- 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
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011368 organic material Substances 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
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 230000003335 steric effect Effects 0.000 description 2
- YMMGRPLNZPTZBS-UHFFFAOYSA-N 2,3-dihydrothieno[2,3-b][1,4]dioxine Chemical compound O1CCOC2=C1C=CS2 YMMGRPLNZPTZBS-UHFFFAOYSA-N 0.000 description 1
- DPZWHUYAABAFKP-UHFFFAOYSA-N 2-bromo-5-methoxypyrimidine Chemical compound COC1=CN=C(Br)N=C1 DPZWHUYAABAFKP-UHFFFAOYSA-N 0.000 description 1
- KYCGEJNZMHUBMX-UHFFFAOYSA-N 2-bromo-5-methylpyrimidine Chemical compound CC1=CN=C(Br)N=C1 KYCGEJNZMHUBMX-UHFFFAOYSA-N 0.000 description 1
- AQXNNEIFLPMDQR-UHFFFAOYSA-N 2-bromo-5-tert-butylpyrimidine Chemical class CC(C)(C)C1=CN=C(Br)N=C1 AQXNNEIFLPMDQR-UHFFFAOYSA-N 0.000 description 1
- YECDDOBNSDZUHY-UHFFFAOYSA-N Bc1ncc(C(C)(C)C)cn1 Chemical compound Bc1ncc(C(C)(C)C)cn1 YECDDOBNSDZUHY-UHFFFAOYSA-N 0.000 description 1
- JEOHFLCFHGXRHD-UHFFFAOYSA-N FC(c(c(F)c(cc1)C2=NC=C=CC=N2)c1F)(F)F Chemical compound FC(c(c(F)c(cc1)C2=NC=C=CC=N2)c1F)(F)F JEOHFLCFHGXRHD-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-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
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 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
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 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
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007738 vacuum evaporation 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 belongs to the field of photoelectric materials and particularly relates to an organic blue light electrophosphorescent metal iridium complex with the structural formula as shown in the specification, wherein r is a hydrogen atom, c1-c20 alkyl or c1-c20 alkoxy. By using the organic blue light electrophosphorescent metal iridium complex, blue light emitting wavelength with relatively high light emitting efficiency can be obtained; and the organic blue light electrophosphorescent metal iridium complex also has relatively high phosphorescent quantum efficiency as well as relatively good dissolving property and processability. The invention also provides a preparation method of the organic blue light electrophosphorescent metal iridium complex and application of the organic blue light electrophosphorescent metal iridium complex to an organic electroluminescent device.
Description
Technical field
The present invention relates to field of photovoltaic materials, be specifically related to a kind of iridium metal complexes of blue light organic phosphorescent electroluminescent materials and its preparation method and application.
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.Due to by the restriction of spin statistics theory, the theoretical internal quantum efficiency limit of fluorescent material is only 25%, how to make full use of all the other phosphorescence of 75% and realizes higher luminous efficiency and become hot research direction in after this this field.The title complex of iridium, ruthenium, platinum etc. 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.
Holmes R J, disclosed two [the 2-(4 ' of the people such as Forrest S R, 6 '-difluorophenyl) pyridine-N, C2 '] (2-pyridinecarboxylic) close iridium (FIrpic, its structural formula is as follows) (App.Phys.Lett., 2003, 82 (15): 2422-2424) be that report is maximum at present, also be the best blue light organic phosphorescent electroluminescent materials of over-all properties, but FIrpic the blue light sent out be sky blue, blue light color purity is not good enough, the CIE of the OLED made of FIrpic is (0.13 ~ 0.17, 0.29 ~ 0.39) change between, the CIE (0.137 of this and standard blue light, 0.084) there is very large gap.
The research of people to organic electromechanical phosphorescent material iridium metal complex is being goed deep into always, but there is bottleneck problem in the efficiency decay etc. of the illuminant colour purity of blue emitting phosphor material, luminous efficiency and device.Therefore, the blue phosphorescent organic electroluminescent material developing high color purity becomes the megatrend expanding blue light material research field.
Summary of the invention
The invention provides a kind of iridium metal complexes of blue light organic phosphorescent electroluminescent materials, this material has good blue light luminous efficiency and good processing characteristics.Present invention also offers the preparation method of this iridium metal complexes of blue light organic phosphorescent electroluminescent materials and its application in organic electroluminescence device.
First aspect, the invention provides a kind of iridium metal complexes of blue light organic phosphorescent electroluminescent materials, has following structural formula:
In formula, R is hydrogen atom, C
1~ C
20alkyl or C
1~ C
20alkoxyl group.
This material is that a class is containing complex of iridium material, a kind of be cyclic metal complexes agent structure with 2-(4 ', 6 '-two fluoro-5 '-cyano-phenyl) pyrimidine, take 2-(pyridine-2 '-Ji) imidazoles as the different distribution type metal iridium complex of assistant ligand.Pyrimidyl 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.By on the straight chain of different lengths or the alkyl of straight chain formula or the difference replacement position of alkoxyl group introducing 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.Meanwhile, the introducing of strong electron-withdrawing group fluorine-based, the trifluoromethyl of group and assistant ligand 2-on phenyl ring (pyridine-2 '-Ji) imidazoles can also improve luminescent properties, is beneficial to evaporation, increases film-forming type and improves the stability of device.
Second aspect, the invention provides a kind of preparation method of iridium metal complexes of blue light organic phosphorescent electroluminescent materials, comprises the steps:
S10, the compd A providing following structural formula to represent and compd B:
In formula, R is hydrogen atom, C
1~ C
20alkyl or C
1~ C
20alkoxyl group;
Under S20, protection of inert gas; described compd A and compd B are dissolved in the first organic solvent containing palladium catalyst and alkali by the mol ratio of 1:1.1 ~ 1:1.5; obtain reaction solution; described reaction solution carried out Suzuki linked reaction after 6 ~ 12 hours at 85 ~ 100 DEG C; separation and purification reaction solution; obtain Compound C, its structural formula is as follows:
In formula, R is hydrogen atom, C
1~ C
20alkyl or C
1~ C
20alkoxyl group;
Under S30, protection of inert gas; it is in the cellosolvo of 3:1 and the mixed solvent of water that described Compound C and three hydrated iridium trichloride are dissolved in volume ratio by the mol ratio of 2.2:1 ~ 3.5:1; be heated to back flow reaction subsequently after 22 ~ 25 hours; be chilled to the throw out in collecting by filtration reaction mixture after room temperature; ethanol, n-hexane successively; obtain Compound D after vacuum-drying, its structural formula is as follows:
In formula, R is hydrogen atom, C
1~ C
20alkyl or C
1~ C
20alkoxyl group;
S40, the compd E providing following structural formula to represent:
Under protection of inert gas; described Compound D and compd E are dissolved in the second organic solvent containing sodium methylate or sodium ethylate by the mol ratio of 1:2.5 ~ 1:4; obtain mixing solutions; described mixing solutions carried out Suzuki linked reaction after 15 ~ 25 hours at 40 ~ 83 DEG C; separation and purification; obtain iridium metal complexes of blue light organic phosphorescent electroluminescent materials, its structural formula is as follows:
In formula, R is hydrogen atom, C
1~ C
20alkyl or C
1~ C
20alkoxyl group.
The reaction formula of step S20 is:
In formula, R is hydrogen atom, C
1~ C
20alkyl or C
1~ C
20alkoxyl group.
Preferably, in step S20, palladium catalyst is that dichloro two (triphenylphosphine) changes palladium (Pd (PPh
3)
2cl
2) or four (triphenylphosphines) close palladium (Pd (PPh
3)
4).
Preferably, alkali is wet chemical or aqueous sodium carbonate.
Preferably, the first organic solvent is DMF (DMF) or toluene.
Preferably, the volume ratio of the first organic solvent and wet chemical is 2:1 ~ 2.5:1.
Preferably, the volume ratio of the first organic solvent and aqueous sodium carbonate is 2:1 ~ 2.5:1.
Preferably, the concentration of compd A in reaction solution is 0.1 ~ 0.2mol/L, and the mole dosage of palladium catalyst is 0.03 ~ 0.05 times of compd A, and the mole dosage of alkali is 1 ~ 3 times of compd A.
Preferably, purification procedures in step S20 comprises: after question response liquid is cooled to room temperature, adopt dichloromethane extraction, then neutrality is washed with water to, again after anhydrous magnesium sulfate drying, filter and obtain filtrate, gained filtrate obtains crude product after removing desolventizing under reduced pressure, to be ethyl acetate and the normal hexane mixed solution of 1:4 ~ 2:1 again by volume ratio be crude product that eluent carries out silica gel column chromatography is separated, and obtains Compound C.
The reaction formula of step S30 is:
In formula, R is hydrogen atom, C
1~ C
20alkyl or C
1~ C
20alkoxyl group.
Preferably, the concentration of Compound C in reaction mixed solvent is 0.06 ~ 0.12mol/L.
The reaction formula of step S40 is:
In formula, R is hydrogen atom, C
1~ C
20alkyl or C
1~ C
20alkoxyl group.
Preferably, the second organic solvent is 1,2-ethylene dichloride, methylene dichloride or trichloromethane.
Preferably, the concentration of Compound D in mixing solutions is 0.01 ~ 0.02mol/L, and the mole dosage of sodium methylate or sodium ethylate is 10 ~ 15 times of Compound D.
Preferably, purification procedures in step S40 comprises: question response removes solvent under reduced pressure after stopping being chilled to room temperature, and crude product with methanol washs, crude product, through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, obtains iridium metal complexes of blue light organic phosphorescent electroluminescent materials after drying.
The preparation method of a kind of iridium metal complexes of blue light organic phosphorescent electroluminescent materials provided by the invention is simple, handled easily.
The third aspect, present invention also offers a kind of organic electroluminescence device, comprises luminescent layer, and doped with the iridium metal complexes of blue light organic phosphorescent electroluminescent materials that such as first aspect present invention provides in described luminescent layer, its structural formula is as follows:
In formula, R is hydrogen atom, C
1~ C
20alkyl or C
1~ C
20alkoxyl group.
Organic electroluminescence device provided by the invention has good blue light emitting performance and stability.
A kind of iridium metal complexes of blue light organic phosphorescent electroluminescent materials provided by the invention and its preparation method and application, its beneficial effect had is:
(1) iridium metal complexes of blue light organic phosphorescent electroluminescent materials provided by the invention comprises cyclic metal complexes agent structure 2-(4 ', 6 '-two fluoro-5 '-cyano-phenyl) pyrimidine and assistant ligand 2-(pyridine-2 '-Ji) imidazoles.Pyrimidyl 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.By on the straight chain of different lengths or the alkyl of straight chain formula or the difference replacement position of alkoxyl group introducing pyrimidine ring, produce certain space steric effect, reduce the interaction force between material molecule, reduce the self-quenching phenomenon of triplet exciton, obtain the blue light emitting wavelength that luminous efficiency is higher;
(2) iridium metal complexes of blue light organic phosphorescent electroluminescent materials provided by the invention, due to the introducing of different lengths alkyl or oxyalkyl chain on pyrimidine ring, improve material solubility property in organic solvent, different distribution type title complex can reduce evaporation temperature, the film forming properties of material can be increased, thus improve Drawing abillity and improve the stability of device;
(3) iridium metal complexes of blue light organic phosphorescent electroluminescent materials synthetic reaction condition provided by the invention is gentle, and technique is simple, is easy to preparation;
(4) organic electroluminescence device provided by the invention has good blue light luminous efficiency and higher stability.
Accompanying drawing explanation
Fig. 1 is the utilizing emitted light spectrogram of the iridium metal complexes of blue light organic phosphorescent electroluminescent materials that the embodiment of the present invention 1 provides;
Fig. 2 is the structural representation of the organic electroluminescence device that the embodiment of the present invention 8 provides.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1
Present embodiments provide a kind of two (2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl) pyrimidine-N, C
2') (2-(pyridine-2 '-Ji) imidazoles) close complex of iridium, its chemical structural formula is as shown in P1:
The preparation process of above-mentioned P1 is as follows:
S10, the compd A 1(2-bromo pyrimi piperidine providing following structural formula to represent) and compd B (the fluoro-3-trifluoromethylbenzene boronic acid of 2,4-bis-):
S20, Compound C 1(2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl) pyrimidine) synthesis
Under nitrogen protection; by 1.59g (10mmol) 2-bromo pyrimi piperidine, 2.71g (12mmol) 2; the fluoro-3-trifluoromethylbenzene boronic acid of 4-bis-and 0.58g (0.5mmol) four (triphenyl phosphorus) close palladium and are dissolved in 40mL toluene, stir 10min.The aqueous solution of 20mL containing 2.76g (20mmol) salt of wormwood is dripped subsequently in reaction system.Heating, stirring reaction 6h under 100 DEG C of state of temperatures.After question response liquid cooling to room temperature, with dichloromethane extraction, separatory, then neutrality is washed to, filter with after anhydrous magnesium sulfate drying again, filtrate obtains crude product through removing desolventizing under reduced pressure, and to be the ethyl acetate of 1:4 again by volume ratio with the mixed solution of normal hexane be crude product that eluent carries out silica gel column chromatography is separated, and obtains 1.04g Compound C 1 after drying, yield is 40.0%, and reaction formula is as follows:
The Structural Identification result of Compound C 1 is as follows:
Mass spectrum (MS m/z): 260.0 (M
+)
Ultimate analysis: C11H5F5N2
Theoretical value: C, 50.78; H, 1.94; F, 36.51; N, 10.77;
Measured value: C, 50.73; H, 1.97; F, 36.56; N, 10.74.
The product C 1 that the above-mentioned reaction of above data acknowledgement obtains is 2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl) pyrimidine;
S30, Compound D 1(part be 2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl) pyrimidine containing iridium dichloro dimer) synthesis
Under nitrogen protection; by 0.71g (2mmol) three hydrated iridium trichloride and 1.82g (7mmol) 2-(2 '; 4 '-two fluoro-3 '-trifluoromethyl) to be dissolved in 60mL volume ratio be in the cellosolvo/water mixed liquid of 3:1 to pyrimidine, is heated to stirring reaction 24h under reflux state.Be chilled to the throw out in collecting by filtration reaction mixture after room temperature, ethanol, n-hexane successively, after vacuum-drying the Compound D 1 of 0.92g, yield is 61.7%, and reaction formula is as follows:
S40, P1(two (2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl) pyrimidine-N, C
2') (2-(pyridine-2 '-Ji) imidazoles) close complex of iridium) synthesis
The compd E that theres is provided following structural formula to represent (2-(pyridine-2 '-Ji) imidazoles, english abbreviation is pymH):
Under nitrogen protection; be 2-(2 ' by 0.75g (0.5mmol) part; 4 '-two fluoro-3 '-trifluoromethyl) pyrimidine containing iridium dichloro dimer; 0.22g (1.5mmol) 2-(pyridine-2 '-Ji) imidazoles (pymH) and 0.32g (6mmol) sodium methylate are dissolved in 40mL1, in 2-ethylene dichloride.Stirring reaction mixed solution is heated to 83 DEG C of reaction 16h.Naturally after being chilled to room temperature, remove solvent under reduced pressure, crude product with methanol washing is to remove unreacted pymH.Crude product is through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, and obtain the P1 of 0.36g purifying after drying, yield is 42.1%, and reaction formula is as follows:
The Structural Identification result of compound P1 is as follows:
Mass spectrum (MS m/z): 855.1 (M
+)
Ultimate analysis: C30H14F10IrN7
Theoretical value: C, 42.16; H, 1.65; F, 22.23; Ir, 22.49; N, 11.47;
Measured value: C, 42.12; H, 1.68; F, 22.27; Ir, 22.44; N, 11.49.
The product P 1 that the above-mentioned reaction of above data acknowledgement obtains is two (2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl) pyrimidine-N, C
2') (2-(pyridine-2 '-Ji) imidazoles) close complex of iridium.
As shown in Figure 1, transverse axis is wavelength (Wavelength, unit nm), and the longitudinal axis is normalized photoluminescence intensity, at 298K temperature, and P1 (~ 10
-5m) at CH
2cl
2in solution, the maximum emission peak of emmission spectrum is at 467nm place, has an acromion at 492nm place simultaneously, and the P1 that this display the present embodiment provides can be used as the preparation field that electroluminescent material is widely used in organic electroluminescence device.
In addition, product P 1 (~ 10
-5m) CH
2cl
2solution at 298K temperature, with the Ir (ppy) under the same terms
3cH
2cl
2solution is standard (Φ
pL=0.40) Φ of P1, is recorded
pL=0.13, the iridium electroluminescent organic material that contains of visible the present embodiment has higher luminous quantum efficiency.
Embodiment 2
Present embodiments provide a kind of two (2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl)-5-methylpyrimidine-N, C
2') (2-(pyridine-2 '-Ji) imidazoles) close complex of iridium, its chemical structural formula is as shown in P2:
The preparation process of above-mentioned P2 is as follows:
S10, the compd A 2(2-bromo-5-methylpyrimidine providing following structural formula to represent) and compd B (the fluoro-3-trifluoromethylbenzene boronic acid of 2,4-bis-):
S20, Compound C 2(2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl)-5-methylpyrimidine) synthesis
Under nitrogen protection; by bromo-for 1.73g (10mmol) 2-5-methylpyrimidine, 2.48g (11mmol) 2; the fluoro-3-trifluoromethylbenzene boronic acid of 4-bis-and 0.28g (0.4mmol) dichloro two (triphenyl phosphorus) close palladium and are dissolved in 50mL DMF, stir 10min.The aqueous solution of 25mL containing 3.18g (30mmol) sodium carbonate is dripped subsequently in reaction system.Be heated to stirring reaction 8h under 90 DEG C of state of temperatures.After question response liquid cooling to room temperature, with dichloromethane extraction, separatory, then neutrality is washed to, filter with after anhydrous magnesium sulfate drying again, filtrate obtains crude product through removing desolventizing under reduced pressure, and to be the ethyl acetate of 1:3 again by volume ratio with the mixed solution of normal hexane be crude product that eluent carries out silica gel column chromatography is separated, and obtains 1.04g Compound C 2 after drying, yield is 37.9%, and reaction formula is as follows:
The Structural Identification result of Compound C 2 is as follows:
Mass spectrum (MS m/z): 274.0 (M
+)
Ultimate analysis: C12H7F5N2
Theoretical value: C, 52.57; H, 2.57; F, 34.64; N, 10.22;
Measured value: C, 52.52; H, 2.64; F, 34.57; N, 10.27.
The product C 2 that the above-mentioned reaction of above data acknowledgement obtains is 2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl)-5-methylpyrimidines.
S30, Compound D 2(part be 2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl)-5-methylpyrimidine containing iridium dichloro dimer) synthesis
Under nitrogen protection; by 0.71g (2mmol) three hydrated iridium trichloride; 1.64g (6mmol) 2-(2 '; 4 '-two fluoro-3 '-trifluoromethyl) to be dissolved in 50mL volume ratio be in the cellosolvo/water mixed liquid of 3:1 to-4-methylpyrimidine, is heated to stirring reaction 22h under reflux state.Be chilled to the throw out in collecting by filtration reaction mixture after room temperature, ethanol, n-hexane successively, after vacuum-drying the Compound D 2 of 0.90g, yield is 58.1%, and reaction formula is as follows:
S40, P2(two (2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl)-5-methylpyrimidine-N, C
2') (2-(pyridine-2 '-Ji) imidazoles) close complex of iridium) synthesis
Compd E is as described in Example 1 provided;
Under nitrogen protection; be 2-(4 ' by 0.77g (0.5mmol) part; 6 '-two fluoro-5 '-trifluoromethyl)-5-methylpyrimidine containing iridium dichloro dimer, 0.18g (1.25mmol) 2-(pyridine-2 '-Ji) imidazoles (pymH) and 0.34g (5mmol) sodium ethylate are dissolved in 30mL trichloromethane.Stirring reaction mixed solution is heated to 62 DEG C of reaction 20h.Naturally after being chilled to room temperature, remove solvent under reduced pressure, crude product with methanol washing is to remove unreacted pymH.Crude product is through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, and obtain the P2 of 0.28g purifying after drying, yield is 31.7%, and reaction formula is as follows:
The Structural Identification result of compound P2 is as follows:
Mass spectrum (MS m/z): 883.1 (M
+)
Ultimate analysis: C32H18F10IrN7
Theoretical value: C, 43.54; H, 2.06; F, 21.52; Ir, 21.78; N, 11.11;
Measured value: C, 43.51; H, 2.11; F, 21.47; Ir, 21.84; N, 11.07.
The product P 2 that the above-mentioned reaction of above data acknowledgement obtains is two (2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl)-5-methylpyrimidine-N, C
2') (2-(pyridine-2 '-Ji) imidazoles) close complex of iridium.
At 298K temperature, P2 (~ 10
-5m) CH
2cl
2in solution, the maximum emission peak of emmission spectrum is at 464nm place, has an acromion at 489nm place simultaneously; In addition, 10
-5the CH of M product P 2
2cl
2solution at 298K temperature, with the Ir (ppy) under the same terms
3cH
2cl
2solution is standard (Φ
pL=0.40) Φ of P2, is recorded
pL=0.07.
Embodiment 3
Present embodiments provide a kind of two (2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl)-5-t-butyl pyrimidines-N, C
2') (2-(pyridine-2 '-Ji) imidazoles) close complex of iridium, its chemical structural formula is as shown in P3:
The preparation process of above-mentioned P3 is as follows:
S10, the compound A-13 (2-bromo-5-t-butyl pyrimidines) providing following structural formula to represent and compd B (the fluoro-3-trifluoromethylbenzene boronic acid of 2,4-bis-):
S20, Compound C 3(2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl)-5-t-butyl pyrimidines) synthesis
Under nitrogen protection; by bromo-for 2.15g (10mmol) 2-5-t-butyl pyrimidines, 3.39g (15mmol) 2; the fluoro-3-trifluoromethylbenzene boronic acid of 4-bis-and 0.21g (0.3mmol) dichloro two (triphenyl phosphorus) close palladium and are dissolved in 35mL DMF, stir 10min.The aqueous solution of 15mL containing 1.38g (10mmol) salt of wormwood is dripped subsequently in reaction system.Be heated to stirring reaction 10h under 85 DEG C of states.After question response liquid cooling to room temperature, with dichloromethane extraction, separatory, then neutrality is washed to, filter with after anhydrous magnesium sulfate drying again, filtrate obtains crude product through removing desolventizing under reduced pressure, and to be the ethyl acetate of 1:1 again by volume ratio with the mixed solution of normal hexane be crude product that eluent carries out silica gel column chromatography is separated, and obtains 0.95g Compound C 3 after drying, yield 30.0%, reaction formula is as follows:
The Structural Identification result of Compound C 3 is as follows:
Mass spectrum (MS m/z): 316.1 (M
+)
Ultimate analysis: C15H13F5N2
Theoretical value: C, 56.96; H, 4.14; F, 30.04; N, 8.86;
Measured value: C, 56.90; H, 4.22; F, 30.01; N, 8.87.
The C3 that the above-mentioned reaction of above data acknowledgement obtains is 2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl)-5-t-butyl pyrimidines;
The synthesis of S30, compound d3 (part be 2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl)-5-t-butyl pyrimidines containing iridium dichloro dimer)
Under nitrogen protection; by 0.35g (1mmol) three hydrated iridium trichloride and 0.70g (2.2mmol) 2-(2 '; 4 '-two fluoro-3 '-trifluoromethyl)-5-t-butyl pyrimidines is dissolved in 20mL2-ethoxy ethanol/water (3/1) mixed solution, 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 the compound d3 of 0.41g, yield is 47.8%, and reaction formula is as follows:
S40, P3(two (2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl)-5-t-butyl pyrimidines-N, C
2') (2-(pyridine-2 '-Ji) imidazoles) close complex of iridium) synthesis
Compd E as described in Example 1 is provided;
Under nitrogen protection; be 2-(2 ' by 0.69g (0.4mmol) part; 4 '-two fluoro-3 '-trifluoromethyl)-5-t-butyl pyrimidines containing iridium dichloro dimer; 0.23g (1.6mmol) 2-(pyridine-2 '-Ji) imidazoles (pymH) and 0.41g (6mmol) sodium ethylate are dissolved in 40mL1, in 2-ethylene dichloride.Stirring reaction mixed solution is heated to 83 DEG C of reaction 15h.Naturally after being chilled to room temperature, remove solvent under reduced pressure, crude product with methanol washing is to remove unreacted pymH.Crude product is through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, and obtain the P3 of 0.15g purifying after drying, yield is 19.4%, and reaction formula is as follows:
The Structural Identification result of compound P3 is as follows:
Structural Identification:
Mass spectrum (MS m/z): 967.2 (M
+)
Ultimate analysis: C38H30F10IrN7
Theoretical value: C, 47.20; H, 3.13; F, 19.65; Ir, 19.88; N, 10.14;
Measured value: C, 47.23; H, 3.08; F, 19.69; Ir, 19.83; N, 10.17.
The product P 3 that the above-mentioned reaction of above data acknowledgement obtains is two (2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl)-5-t-butyl pyrimidines-N, C
2') (2-(pyridine-2 '-Ji) imidazoles) close complex of iridium.
At 298K temperature, P3 (~ 10
-5m) CH
2cl
2in solution, the maximum emission peak of emmission spectrum is at 470nm place, has an acromion at 494nm place simultaneously; In addition, 10
-5the CH of M product P 3
2cl
2solution at 298K temperature, with the Ir (ppy) under the same terms
3cH
2cl
2solution is standard (Φ
pL=0.40) Φ of P3, is recorded
pL=0.12.
Embodiment 4
Present embodiments provide a kind of two (2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl)-4-eicosyl pyrimidine-N, C
2') (2-(pyridine-2 '-Ji) imidazoles) close complex of iridium, its chemical structural formula is as shown in P4:
The preparation process of above-mentioned P4 is as follows:
S10, the compd A 4(2-bromo-4-eicosyl pyrimidine providing following structural formula to represent) and compd B (the fluoro-3-trifluoromethylbenzene boronic acid of 2,4-bis-):
S20, Compound C 4(2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl)-4-eicosyl pyrimidine) synthesis
Under nitrogen protection; by 2.20g (5mmol) 2-bromo-4-eicosyl pyrimidine, 1.36g (6mmol) 2; the fluoro-3-trifluoromethylbenzene boronic acid of 4-bis-and 0.23g (0.2mmol) four (triphenyl phosphorus) close palladium and are dissolved in 35mL toluene, stir 10min.The aqueous solution of 15mL containing 1.38g (10mmol) salt of wormwood is dripped subsequently in reaction system.Be heated to stirring reaction 12h under 85 DEG C of state of temperatures.After question response liquid cooling to room temperature, with dichloromethane extraction, separatory, then neutrality is washed to, filter with after anhydrous magnesium sulfate drying again, filtrate obtains crude product through removing desolventizing under reduced pressure, and to be the ethyl acetate of 2:1 again by volume ratio with the mixed solution of normal hexane be crude product that eluent carries out silica gel column chromatography is separated, and obtains 0.49g Compound C 4 after drying, yield 18.1%, reaction formula is as follows:
The Structural Identification result of Compound C 4 is as follows:
Mass spectrum (MS m/z): 540.4 (M
+)
Ultimate analysis: C31H45F5N2
Theoretical value: C, 68.86; H, 8.39; F, 17.57; N, 5.18;
Measured value: C, 68.82; H, 8.44; F, 17.53; N, 5.21.
The C4 that the above-mentioned reaction of above data acknowledgement obtains is 2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl)-4-eicosyl pyrimidine;
S30, Compound D 4(part be 2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl)-4-eicosyl pyrimidine containing iridium dichloro dimer) synthesis
Under nitrogen protection; by 0.18g (0.5mmol) three hydrated iridium trichloride; 0.81g (1.5mmol) 2-(2 '; 4 '-two fluoro-3 '-trifluoromethyl)-4-eicosyl pyrimidine is dissolved in 25mL2-ethoxy ethanol/water (3/1) mixed solution, stirring reaction 25h at reflux.Be chilled to the throw out in collecting by filtration reaction mixture after room temperature, ethanol, n-hexane successively, after vacuum-drying the Compound D 4 of 0.13g, yield is 19.9%, and reaction formula is as follows:
S40, P4(two (2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl)-4-eicosyl pyrimidine-N, C
2') (2-(pyridine-2 '-Ji) imidazoles) close complex of iridium) synthesis
Compd E as described in Example 1 is provided;
Under nitrogen protection; be 2-(2 ' by 0.78g (0.3mmol) part; 4 '-two fluoro-3 '-trifluoromethyl)-4-eicosyl pyrimidine containing iridium dichloro dimer, 0.15g (1mmol) 2-(pyridine-2 '-Ji) imidazoles (pymH) and 0.20g (3.6mmol) sodium methylate are dissolved in 20mL trichloromethane.Stirring reaction mixed solution is heated to 62 DEG C of reaction 20h.Naturally after being chilled to room temperature, remove solvent under reduced pressure, crude product with methanol washing is to remove unreacted pymH.Crude product is through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, and obtain the P4 of 0.04g purifying after drying, yield is 4.7%, and reaction formula is as follows:
The Structural Identification result of compound P4 is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1415.7 (M
+)
Ultimate analysis: C70H94F10IrN7
Theoretical value: C, 59.39; H, 6.69; F, 13.42; Ir, 13.58; N, 6.93;
Measured value: C, 59.34; H, 6.77; F, 13.36; Ir, 13.62; N, 6.91.
The product P 4 that the above-mentioned reaction of above data acknowledgement obtains is two (2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl)-4-eicosyl pyrimidine-N, C
2') (2-(pyridine-2 '-Ji) imidazoles) close complex of iridium.
At 298K temperature, P4 (~ 10
-5m) CH
2cl
2in solution, the maximum emission peak of emmission spectrum is at 492nm place, has an acromion at 517nm place simultaneously; In addition, 10
-5the CH of M product P 4
2cl
2solution at 298K temperature, with the Ir (ppy) under the same terms
3cH
2cl
2solution is standard (Φ
pL=0.40) Φ of P4, is recorded
pL=0.004.
Embodiment 5
Present embodiments provide a kind of two (2-(4 ', 6 '-two fluoro-3 '-trifluoromethyl)-5-methoxy pyrimidine-N, C
2') (2-(pyridine-2 '-Ji) imidazoles) close complex of iridium, its chemical structural formula is as shown in P5:
The preparation process of above-mentioned P5 is as follows:
S10, the compound A-45 (2-bromo-5-methoxy pyrimidine) providing following structural formula to represent and compd B (the fluoro-3-trifluoromethylbenzene boronic acid of 2,4-bis-):
S20, Compound C 5(2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl)-5-methoxy pyrimidine) synthesis
Under nitrogen protection; by bromo-for 1.89g (10mmol) 2-5-methoxy pyrimidine, 2.71g (12mmol) 2; the fluoro-3-trifluoromethylbenzene boronic acid of 4-bis-and 0.58g (0.5mmol) four (triphenyl phosphorus) close palladium and are dissolved in 40mL toluene, continue to stir 10min.The aqueous solution of 20mL containing 2.76g (20mmol) salt of wormwood is dripped subsequently in reaction system.Be heated to stirring reaction 6h under 100 DEG C of state of temperatures.After question response liquid cooling to room temperature, with dichloromethane extraction, separatory, then neutrality is washed to, filter with after anhydrous magnesium sulfate drying again, filtrate obtains crude product through removing desolventizing under reduced pressure, and to be the ethyl acetate of 1:3 again by volume ratio with the mixed solution of normal hexane be crude product that eluent carries out silica gel column chromatography is separated, and obtains 1.04g Compound C 5 after drying, yield 35.8%, reaction formula is as follows:
The Structural Identification result of Compound C 5 is as follows:
Mass spectrum (MS m/z): 290.0 (M
+)
Ultimate analysis: C12H7F5N2O
Theoretical value: C, 49.67; H, 2.43; F, 32.73; N, 9.65; O, 5.51;
Measured value: C, 49.63; H, 2.49; F, 32.66; N, 9.74; O, 5.48.
The C5 that the above-mentioned reaction of above data acknowledgement obtains is 2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl)-5-methoxy pyrimidine;
S30, Compound D 5(part be 2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl)-5-methoxy pyrimidine containing iridium dichloro dimer) synthesis
Under nitrogen protection; by 0.71g (2mmol) three hydrated iridium trichloride; 1.74g (6mmol) 2-(2 '; 4 '-two fluoro-3 '-trifluoromethyl) to be dissolved in 50mL volume ratio be in the cellosolvo/water mixed liquid of 3:1 to-5-methoxy pyrimidine, is heated to stirring reaction 24h under reflux state.Be chilled to the throw out in collecting by filtration reaction mixture after room temperature, ethanol, n-hexane successively, after vacuum-drying the Compound D 5 of 0.89g, yield is 55.2%, and reaction formula is as follows:
S40, P5(two (2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl)-5-methoxy pyrimidine-N, C
2') (2-(pyridine-2 '-Ji) imidazoles) close complex of iridium) synthesis
Compd E as described in Example 1 is provided;
Under nitrogen protection; be 2-(2 ' by 0.81g (0.5mmol) part; 4 '-two fluoro-3 '-trifluoromethyl)-5-methoxy pyrimidine containing iridium dichloro dimer, 0.18g (1.25mmol) 2-(pyridine-2 '-Ji) imidazoles (pymH) and 0.27g (5mmol) sodium methylate are dissolved in 25mL methylene dichloride.Stirring reaction mixed solution is heated to 40 DEG C of reaction 25h.Naturally after being chilled to room temperature, remove solvent under reduced pressure, crude product with methanol washing is to remove unreacted pymH.Crude product is through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, and obtain the P5 of 0.27g purifying after drying, yield is 29.5%, and reaction formula is as follows:
The Structural Identification result of compound P5 is as follows:
Structural Identification:
Mass spectrum (MS m/z): 915.1 (M
+)
Ultimate analysis: C32H18F10IrN7O2
Theoretical value: C, 42.02; H, 1.98; F, 20.77; Ir, 21.01; N, 10.72; O, 3.50;
Measured value: C, 42.07; H, 1.92; F, 20.79; Ir, 21.04; N, 10.71; O, 3.47.
The product P 5 that the above-mentioned reaction of above data acknowledgement obtains is two (2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl)-5-methoxy pyrimidine-N, C
2') (2-(pyridine-2 '-Ji) imidazoles) close complex of iridium.
At 298K temperature, P5 (~ 10
-5m) CH
2cl
2in solution, the maximum emission peak of emmission spectrum is at 463nm place, has an acromion at 489nm place simultaneously; In addition, 10
-5the CH of M product P 5
2cl
2solution at 298K temperature, with the Ir (ppy) under the same terms
3cH
2cl
2solution is standard (Φ
pL=0.40) Φ of P5, is recorded
pL=0.05.
Embodiment 6
Present embodiments provide a kind of two (2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl)-4-hexyloxy pyrimidine-N, C
2') (2-(pyridine-2 '-Ji) imidazoles) close complex of iridium, its chemical structural formula is as shown in P6:
The preparation process of above-mentioned P6 is as follows:
S10, the compd A 6(2-bromo-4-hexyloxy pyrimidine providing following structural formula to represent) and compd B (the fluoro-3-trifluoromethylbenzene boronic acid of 2,4-bis-):
S20, Compound C 6(2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl)-4-hexyloxy pyrimidine) synthesis
Under nitrogen protection; by 2.59g (10mmol) 2-bromo-4-hexyloxy pyrimidine, 3.39g (15mmol) 2; the fluoro-3-trifluoromethylbenzene boronic acid of 4-bis-and 0.21g (0.3mmol) dichloro two (triphenyl phosphorus) close palladium and are dissolved in 40mL DMF, stir 10min.The aqueous solution of 20mL containing 1.38g (10mmol) salt of wormwood is dripped subsequently in reaction system.Be heated to stirring reaction 10h under 85 DEG C of states.After question response liquid cooling to room temperature, with dichloromethane extraction, separatory, then neutrality is washed to, filter with after anhydrous magnesium sulfate drying again, filtrate obtains crude product through removing desolventizing under reduced pressure, and to be the ethyl acetate of 1:4 again by volume ratio with the mixed solution of normal hexane be crude product that eluent carries out silica gel column chromatography is separated, and obtains 0.73g Compound C 6 after drying, yield 20.2%, reaction formula is as follows:
The Structural Identification result of Compound C 6 is as follows:
Mass spectrum (MS m/z): 360.1 (M
+)
Ultimate analysis: C17H17F5N2O
Theoretical value: C, 56.67; H, 4.76; F, 26.36; N, 7.77; O, 4.44;
Measured value: C, 56.62; H, 4.82; F, 26.33; N, 7.81; O, 4.42.
The C6 that the above-mentioned reaction of above data acknowledgement obtains is 2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl)-4-hexyloxy pyrimidine;
S30, Compound D 6(part be 2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl)-4-hexyloxy pyrimidine containing iridium dichloro dimer) synthesis
Under nitrogen protection; by 0.35g (1mmol) three hydrated iridium trichloride and 0.79g (2.2mmol) 2-(2 '; 4 '-two fluoro-3 '-trifluoromethyl)-4-hexyloxy pyrimidine is dissolved in 20mL2-ethoxy ethanol/water (3/1) mixed solution, 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 the Compound D 6 of 0.38g, yield is 40.2%, and reaction formula is as follows:
S40, P6(two (2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl)-4-hexyloxy pyrimidine-N, C
2') (2-(pyridine-2 '-Ji) imidazoles) close complex of iridium) synthesis
Compd E as described in Example 1 is provided;
Under nitrogen protection; be 2-(2 ' by 0.76g (0.4mmol) part; 4 '-two fluoro-3 '-trifluoromethyl)-4-hexyloxy pyrimidine containing iridium dichloro dimer; 0.22g (1.5mmol) 2-(pyridine-2 '-Ji) imidazoles (pymH) and 0.27g (4mmol) sodium ethylate are dissolved in 30mL1, in 2-ethylene dichloride.Stirring reaction mixed solution is heated to 40 DEG C of reaction 25h.Naturally after being chilled to room temperature, remove solvent under reduced pressure, crude product with methanol washing is to remove unreacted pymH.Crude product is through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, and obtain the P6 of 0.13g purifying after drying, yield is 15.4%, and reaction formula is as follows:
The Structural Identification result of compound P6 is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1055.3 (M
+)
Ultimate analysis: C42H38F10IrN7O2
Theoretical value: C, 47.82; H, 3.63; F, 18.01; Ir, 18.22; N, 9.29; O, 3.03;
Measured value: C, 47.86; H, 3.55; F, 18.07; Ir, 18.18; N, 9.33; O, 3.01.
The product P 6 that the above-mentioned reaction of above data acknowledgement obtains is two (2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl)-4-hexyloxy pyrimidine-N, C
2') (2-(pyridine-2 '-Ji) imidazoles) close complex of iridium.
At 298K temperature, P6 (~ 10
-5m) CH
2cl
2in solution, the maximum emission peak of emmission spectrum is at 478nm place, has an acromion at 505nm place simultaneously; In addition, 10
-5the CH of M product P 6
2cl
2solution at 298K temperature, with the Ir (ppy) under the same terms
3cH
2cl
2solution is standard (Φ
pL=0.40) Φ of P6, is recorded
pL=0.01.
Embodiment 7
Present embodiments provide a kind of two (2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl)-5-eicosane oxygen yl pyrimidines-N, C
2') (2-(pyridine-2 '-Ji) imidazoles) close complex of iridium, its chemical structural formula is as shown in P7:
The preparation process of above-mentioned P7 is as follows:
S10, the compd A 7(2-bromo-5-eicosane oxygen yl pyrimidines providing following structural formula to represent) and compd B (the fluoro-3-trifluoromethylbenzene boronic acid of 2,4-bis-):
S20, Compound C 7(2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl)-5-eicosane oxygen yl pyrimidines) synthesis
Under nitrogen protection; by 2.28g (5mmol) 2-bromo-5-eicosane oxygen yl pyrimidines, 1.36g (6mmol) 2; the fluoro-3-trifluoromethylbenzene boronic acid of 4-bis-and 0.23g (0.2mmol) four (triphenyl phosphorus) close palladium and are dissolved in 35mL toluene, stir 10min.The aqueous solution of 15mL containing 1.38g (10mmol) salt of wormwood is dripped subsequently in reaction system.Be heated to stirring reaction 12h under 85 DEG C of state of temperatures.After question response liquid cooling to room temperature, with dichloromethane extraction, separatory, then neutrality is washed to, filter with after anhydrous magnesium sulfate drying again, filtrate obtains crude product through removing desolventizing under reduced pressure, and to be the ethyl acetate of 1:1 again by volume ratio with the mixed solution of normal hexane be crude product that eluent carries out silica gel column chromatography is separated, and obtains 0.47g Compound C 7 after drying, yield 16.9%, reaction formula is as follows:
The Structural Identification result of Compound C 7 is as follows:
Mass spectrum (MS m/z): 556.4 (M
+)
Ultimate analysis: C31H45F5N2O
Theoretical value: C, 66.88; H, 8.15; F, 17.06; N, 5.03; O, 2.87;
Measured value: C, 66.82; H, 8.23; F, 17.03; N, 5.07; O, 2.85.
The C7 that the above-mentioned reaction of above data acknowledgement obtains is 2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl)-5-eicosane oxygen yl pyrimidines;
S30, Compound D 7(part be 2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl)-5-eicosane oxygen yl pyrimidines containing iridium dichloro dimer) synthesis
Under nitrogen protection; by 0.18g (0.5mmol) three hydrated iridium trichloride; 0.84g (1.5mmol) 2-(2 '; 4 '-two fluoro-3 '-trifluoromethyl)-5-eicosane oxygen yl pyrimidines is dissolved in 25mL2-ethoxy ethanol/water (3/1) mixed solution, stirring reaction 25h at reflux.Be chilled to the throw out in collecting by filtration reaction mixture after room temperature, ethanol, n-hexane successively, after vacuum-drying the Compound D 7 of 0.12g, yield is 17.9%, and reaction formula is as follows:
S40, P7(two (2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl)-5-eicosane oxygen yl pyrimidines-N, C
2') (2-(pyridine-2 '-Ji) imidazoles) close complex of iridium) synthesis
Compd E as described in Example 1 is provided;
Under nitrogen protection; be 2-(2 ' by 0.81g (0.3mmol) part; 4 '-two fluoro-3 '-trifluoromethyl)-5-eicosane oxygen yl pyrimidines containing iridium dichloro dimer; 0.15g (1mmol) 2-(pyridine-2 '-Ji) imidazoles (pymH) and 0.19g (3.6mmol) sodium methylate are dissolved in 30mL1, in 2-ethylene dichloride.Stirring reaction mixed solution is heated to 83 DEG C of reaction 16h.Naturally after being chilled to room temperature, remove solvent under reduced pressure, crude product with methanol washing is to remove unreacted pymH.Crude product is through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, and obtain the P7 of 0.03g purifying after drying, yield is 3.4%, and reaction formula is as follows:
The Structural Identification result of compound P7 is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1447.7 (M
+)
Ultimate analysis: C70H94F10IrN7O2
Theoretical value: C, 58.07; H, 6.54; F, 13.12; Ir, 13.28; N, 6.77; O, 2.21;
Measured value: C, 58.01; H, 6.63; F, 13.07; Ir, 13.34; N, 6.72; O, 2.23.
The product P 7 that the above-mentioned reaction of above data acknowledgement obtains is two (2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl)-5-eicosane oxygen yl pyrimidines-N, C
2') (2-(pyridine-2 '-Ji) imidazoles) close complex of iridium.
At 298K temperature, P7 (~ 10
-5m) CH
2cl
2in solution, the maximum emission peak of emmission spectrum is at 499nm place, has an acromion at 524nm place simultaneously; In addition, 10
-5the CH of M product P 7
2cl
2solution at 298K temperature, with the Ir (ppy) under the same terms
3cH
2cl
2solution is standard (Φ
pL=0.40) Φ of P7, is recorded
pL=0.002.
Embodiment 8
The doping object that the title complex P1 that the present embodiment provides with the embodiment of the present invention 1 is luminescent layer, prepare organic electroluminescence device, as shown in Figure 2, the structure of this organic electroluminescence device comprises the transparent anode 301, hole injection layer 302, luminescent layer 303, electron transfer layer 304, electron injection buffer layer 305, the negative electrode 306 that stack gradually.
The preparation technology of this organic electroluminescence device comprises:
A glass-based plate deposits a layer thickness is 100nm, square resistance is 10 ~ 20 Ω/mouth tin indium oxide (ITO) as transparent anode 301, then on anode 301, spin coating a layer thickness is the PEDOT:PSS (poly-3 of 40nm, 4-ethylenedioxy thiophene/poly styrene sulfonate) hole-injecting material as hole injection layer 302, in nitrogen atmosphere, toast 10min at 120 DEG C of temperature; Chlorobenzene solution spin coating a layer thickness is two (2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl) pyrimidine-N, the C that prepare doped with 12wt% embodiment 1 of 50nm
2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close the PVK (Polyvinyl carbazole) of iridium as luminescent layer 303; Then on this luminescent layer 303 spin coating a layer thickness be TmPyPB (1,3,5-tri-(the m-pyridin-3-yl phenyl) benzene) material of 20nm as electron transfer layer 304,80 DEG C of anneal 60min; Last 5 × 10
-8in Torr vacuum evaporation a layer thickness be the LiF of 1nm as electron injection buffer layer 305, adopt vacuum plating techniques of deposition thickness to be the metal A l of 120nm on the buffer layer, as the negative electrode 306 of device.The concrete structure of this organic electroluminescence device can be expressed as ITO (100nm)/PEDOT:PSS (40nm)/PVK:12wt%Ir title complex (50nm)/TmPyPB (20nm)/LiF (1nm)/Al (120nm); Wherein, P1 is the title complex that the embodiment of the present invention 1 obtains, 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 470nm place, an acromion is had at 495nm place, the maximum external quantum efficiency of device is 5.7%, and maximum lumen efficiency is 4.8lm/W.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (10)
1. an iridium metal complexes of blue light organic phosphorescent electroluminescent materials, is characterized in that, has following structural formula:
In formula, 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:
S10, the compd A providing following structural formula to represent and compd B:
In formula, R is hydrogen atom, C
1~ C
20alkyl or C
1~ C
20alkoxyl group;
Under S20, protection of inert gas; described compd A and compd B are dissolved in the first organic solvent containing palladium catalyst and alkali by the mol ratio of 1:1.1 ~ 1:1.5; obtain reaction solution; described reaction solution carried out Suzuki linked reaction after 6 ~ 12 hours at 85 ~ 100 DEG C; separation and purification reaction solution; obtain Compound C, its structural formula is as follows:
In formula, R is hydrogen atom, C
1~ C
20alkyl or C
1~ C
20alkoxyl group;
Under S30, protection of inert gas; it is in the cellosolvo of 3:1 and the mixed solvent of water that described Compound C and three hydrated iridium trichloride are dissolved in volume ratio by the mol ratio of 2.2:1 ~ 3.5:1; be heated to back flow reaction subsequently after 22 ~ 25 hours; be chilled to the throw out in collecting by filtration reaction mixture after room temperature; ethanol, n-hexane successively; obtain Compound D after vacuum-drying, its structural formula is as follows:
In formula, R is hydrogen atom, C
1~ C
20alkyl or C
1~ C
20alkoxyl group;
S40, the compd E providing following structural formula to represent:
Under protection of inert gas; described Compound D and compd E are dissolved in the second organic solvent containing sodium methylate or sodium ethylate by the mol ratio of 1:2.5 ~ 1:4; obtain mixing solutions; described mixing solutions carried out Suzuki linked reaction after 15 ~ 25 hours at 40 ~ 83 DEG C; separation and purification; obtain iridium metal complexes of blue light organic phosphorescent electroluminescent materials, its structural formula is as follows:
In formula, 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 as claimed in claim 2, it is characterized in that, in described S20, the concentration of described compd A in reaction solution is 0.1 ~ 0.2mol/L; Described first organic solvent is DMF or toluene.
4. the preparation method of iridium metal complexes of blue light organic phosphorescent electroluminescent materials as claimed in claim 2, it is characterized in that, in described S20, described palladium catalyst is that dichloro two (triphenylphosphine) changes palladium or four (triphenylphosphines) close palladium, and the mole dosage of described palladium catalyst is 0.03 ~ 0.05 times of compd A; Described alkali is wet chemical or aqueous sodium carbonate, and the mole dosage of described alkali is 1 ~ 3 times of compd A.
5. the preparation method of iridium metal complexes of blue light organic phosphorescent electroluminescent materials as claimed in claim 2, it is characterized in that, in described S20, described purification procedures comprises: after question response liquid is cooled to room temperature, adopt dichloromethane extraction, then neutrality is washed with water to, again after anhydrous magnesium sulfate drying, filtration obtains filtrate, gained filtrate obtains crude product after removing desolventizing under reduced pressure, to be ethyl acetate and the normal hexane mixed solution of 1:4 ~ 2:1 again by volume ratio be crude product that eluent carries out silica gel column chromatography is separated, and obtains described Compound C.
6. the preparation method of iridium metal complexes of blue light organic phosphorescent electroluminescent materials as claimed in claim 2, it is characterized in that, in described S30, the concentration of Compound C in reaction solution is 0.06 ~ 0.12mol/L.
7. the preparation method of iridium metal complexes of blue light organic phosphorescent electroluminescent materials as claimed in claim 2, it is characterized in that, in described S40, described second organic solvent is 1,2-ethylene dichloride, methylene dichloride or trichloromethane.
8. the preparation method of iridium metal complexes of blue light organic phosphorescent electroluminescent materials as claimed in claim 2, it is characterized in that, in described S40, the concentration of described Compound D in mixing solutions is 0.01 ~ 0.02mol/L, and the mole dosage of described sodium methylate or sodium ethylate is 10 ~ 15 times of described Compound D.
9. the preparation method of iridium metal complexes of blue light organic phosphorescent electroluminescent materials as claimed in claim 2, it is characterized in that, in described S40, described purification procedures comprises: after question response stops being chilled to room temperature, remove solvent under reduced pressure, crude product with methanol washs, and crude product, through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, obtains described iridium metal complexes of blue light organic phosphorescent electroluminescent materials after drying.
10. an organic electroluminescence device, comprises luminescent layer, it is characterized in that, doped with iridium metal complexes of blue light organic phosphorescent electroluminescent materials as claimed in claim 1 in described luminescent layer, its structural formula is as follows:
In formula, R is hydrogen atom, C
1~ C
20alkyl or C
1~ C
20alkoxyl group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310394889.1A CN104418906A (en) | 2013-09-03 | 2013-09-03 | Organic blue light electrophosphorescent metal iridium complex as well as preparation method and application of organic blue light electrophosphorescent metal iridium complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310394889.1A CN104418906A (en) | 2013-09-03 | 2013-09-03 | Organic blue light electrophosphorescent metal iridium complex as well as preparation method and application of organic blue light electrophosphorescent metal iridium complex |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104418906A true CN104418906A (en) | 2015-03-18 |
Family
ID=52969097
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310394889.1A Pending CN104418906A (en) | 2013-09-03 | 2013-09-03 | Organic blue light electrophosphorescent metal iridium complex as well as preparation method and application of organic blue light electrophosphorescent metal iridium complex |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104418906A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106892944A (en) * | 2015-12-17 | 2017-06-27 | 上海和辉光电有限公司 | A kind of pyridine joins the complex of iridium of pyrimidine |
-
2013
- 2013-09-03 CN CN201310394889.1A patent/CN104418906A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106892944A (en) * | 2015-12-17 | 2017-06-27 | 上海和辉光电有限公司 | A kind of pyridine joins the complex of iridium of pyrimidine |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104418906A (en) | Organic blue light electrophosphorescent metal iridium complex as well as preparation method and application of organic blue light electrophosphorescent metal iridium complex | |
| CN104419410A (en) | Organic blue light electrophosphorescent metal iridium complex as well as preparation method and application of organic blue light electrophosphorescent metal iridium complex | |
| CN104178118A (en) | Blue ray organic electroluminescent material and preparation method and application thereof | |
| CN104560023A (en) | Organic electroluminescent material, preparation method of organic electroluminescent material and organic electroluminescent device | |
| CN104177409A (en) | Organic electroluminescence material and preparation method and application | |
| CN104418907A (en) | Organic blue light electroluminescent material as well as preparation method and application of organic blue light electroluminescent material | |
| CN104418914A (en) | Organic blue light electrophosphorescent metal iridium complex as well as preparation method and application of organic blue light electrophosphorescent metal iridium complex | |
| CN104419411A (en) | Organic blue light electrophosphorescent metal iridium complex as well as preparation method and application of organic blue light electrophosphorescent metal iridium complex | |
| CN104418911A (en) | Organic blue light electrophosphorescent metal iridium complex, preparation method thereof and organic electroluminescent device | |
| CN104178116A (en) | Blue ray organic electroluminescent material and preparation method and application thereof | |
| CN104177423A (en) | Organic electroluminescent material, and preparation method and application thereof | |
| CN104560022A (en) | Organic electroluminescent material, preparation method of organic electroluminescent material and organic electroluminescent device | |
| CN104177424A (en) | Blue light organic electroluminescent material, and preparation method and application thereof | |
| CN104327123A (en) | Blue phosphorescent iridium metal complex and preparation method thereof and organic electroluminescent device | |
| CN104418908A (en) | Organic blue light electroluminescent material as well as preparation method and application of organic blue light electroluminescent material | |
| CN104419412A (en) | Organic blue light electroluminescent material as well as preparation method and application of organic blue light electroluminescent material | |
| CN104178111A (en) | Blue light organic electroluminescent material, and preparation method and application thereof | |
| CN104293342A (en) | Blue-light organic electrophosphorescent material, preparation method and application thereof | |
| CN104560020A (en) | Organic electroluminescent material, preparation method of organic electroluminescent material and organic electroluminescent device | |
| CN104560024A (en) | Organic electroluminescent material, preparation method of organic electroluminescent material and organic electroluminescent device | |
| CN104178103A (en) | Organic electroluminescence material and preparation method and application | |
| CN104419406A (en) | Organic blue light electroluminescent material as well as preparation method and application of organic blue light electroluminescent material | |
| CN104419413A (en) | Organic blue light electrophosphorescent material, preparation method thereof and organic electroluminescent device | |
| CN104418909A (en) | Organic blue light electrophosphorescent material, preparation method thereof and organic electroluminescent device | |
| CN104327829A (en) | Blue ray organic electroluminescent material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150318 |
|
| WD01 | Invention patent application deemed withdrawn after publication |