CN104418907A - Organic blue light electroluminescent material as well as preparation method and application of organic blue light electroluminescent material - Google Patents
Organic blue light electroluminescent material as well as preparation method and application of organic blue light electroluminescent material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 69
- 238000006243 chemical reaction Methods 0.000 claims description 65
- 150000001875 compounds Chemical class 0.000 claims description 43
- 238000001035 drying Methods 0.000 claims description 40
- 239000012043 crude product Substances 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 36
- 241001025261 Neoraja caerulea Species 0.000 claims description 32
- 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 31
- 238000003756 stirring Methods 0.000 claims description 28
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 20
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 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 18
- 238000000605 extraction Methods 0.000 claims description 18
- 238000010898 silica gel chromatography Methods 0.000 claims description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 238000005401 electroluminescence Methods 0.000 claims description 13
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 13
- 235000015320 potassium carbonate Nutrition 0.000 claims description 13
- 238000000746 purification Methods 0.000 claims description 13
- 239000011541 reaction mixture Substances 0.000 claims description 13
- 230000004044 response Effects 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- 238000010992 reflux 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
- 239000003480 eluent Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 9
- 239000012074 organic phase Substances 0.000 claims description 9
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 9
- 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
- 238000000926 separation method Methods 0.000 claims description 6
- 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 6
- 125000003963 dichloro group Chemical group Cl* 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
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 36
- 229910052741 iridium Inorganic materials 0.000 description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 28
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 28
- 230000015572 biosynthetic process Effects 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 21
- 239000000047 product Substances 0.000 description 17
- 238000004458 analytical method Methods 0.000 description 14
- 238000001819 mass spectrum Methods 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 210000002659 acromion Anatomy 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 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 7
- 0 CCC1=C(c(c(N)c2N)c(C)cc2N)*(C2/C=C(\C(C(CC3N)=C)C(N)=C3[N+])/*=C/CCC2)=CCCC1 Chemical compound CCC1=C(c(c(N)c2N)c(C)cc2N)*(C2/C=C(\C(C(CC3N)=C)C(N)=C3[N+])/*=C/CCC2)=CCCC1 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
- 238000001816 cooling Methods 0.000 description 7
- 239000000539 dimer Substances 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 125000000714 pyrimidinyl group Chemical group 0.000 description 6
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 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 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 150000003230 pyrimidines Chemical class 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 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 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 description 3
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 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
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 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
- 238000010438 heat treatment Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 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
- 239000011368 organic material Substances 0.000 description 2
- 125000005429 oxyalkyl group Chemical group 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006862 quantum yield reaction Methods 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
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 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
- FUTVFKDRMZATOI-UHFFFAOYSA-N 2-bromo-4-icosylpyrimidine Chemical compound BrC1=NC=CC(=N1)CCCCCCCCCCCCCCCCCCCC FUTVFKDRMZATOI-UHFFFAOYSA-N 0.000 description 1
- DPZWHUYAABAFKP-UHFFFAOYSA-N 2-bromo-5-methoxypyrimidine Chemical compound COC1=CN=C(Br)N=C1 DPZWHUYAABAFKP-UHFFFAOYSA-N 0.000 description 1
- KYCGEJNZMHUBMX-UHFFFAOYSA-N 2-bromo-5-methylpyrimidine Chemical compound CC1=CN=C(Br)N=C1 KYCGEJNZMHUBMX-UHFFFAOYSA-N 0.000 description 1
- AQXNNEIFLPMDQR-UHFFFAOYSA-N 2-bromo-5-tert-butylpyrimidine Chemical class CC(C)(C)C1=CN=C(Br)N=C1 AQXNNEIFLPMDQR-UHFFFAOYSA-N 0.000 description 1
- 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
- XECUMCLPUKPRLJ-UHFFFAOYSA-N [O].C1=CN=CN=C1 Chemical compound [O].C1=CN=CN=C1 XECUMCLPUKPRLJ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012298 atmosphere Substances 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
- 230000005684 electric field Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- -1 iridium (III) compound Chemical class 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000003913 materials processing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 235000012736 patent blue V Nutrition 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 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
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
Abstract
The invention belongs to the field of photoelectric materials and particularly relates to an organic blue light electroluminescent material with the structural formula as shown in the figure p, wherein r is a hydrogen atom, c1-c20 alkyl or c1-c20 alkoxy. The organic blue light electroluminescent material has relatively high lumo energy level and relatively low homo energy level so as to be beneficial to blue shift of light emitting wavelength of the organic blue light electroluminescent material; and the organic blue light electroluminescent material 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 electroluminescent material and application of the organic blue light electroluminescent material to an organic electroluminescent device.
Description
Technical field
The present invention relates to field of photovoltaic materials, be specifically related to a kind of blue-ray organic electroluminescent material 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 [2-(the 4' of the people such as Forrest S R, 6'-difluorophenyl) pyridine-N, C2'] (2-pyridinecarboxylic) close iridium (FIrpic) (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.
In order to make device obtain full-color display, generally must obtain the ruddiness of excellent performance, green glow and blue light material simultaneously.But the development of blue phosphor materials lags behind ruddiness and green glow relatively.So the blue-ray organic electroluminescent material developing high color purity and high-luminous-efficiency is still a large focus of OLED research field.
Summary of the invention
For solving the problem, the invention provides a kind of blue-ray organic electroluminescent material, this material has good blue light luminous efficiency and good processing characteristics.Present invention also offers the preparation method of this blue-ray organic electroluminescent material and its application in organic electroluminescence device.
First aspect, the invention provides a kind of blue-ray organic electroluminescent material, structural formula is as shown in P:
In formula, R is hydrogen atom, C
1~ C
20alkyl or C
1~ C
20alkoxyl group, in described structural formula P, the structural formula of cyclic metal complexes is:
, in formula, n=1 ~ 20.
This blue-ray organic electroluminescent material is that a class contains complex of iridium material, comprises cyclic metal complexes agent structure 2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl) pyrimidine and assistant ligand 2-pyridinecarboxylic, from luminous efficiency: described cyclic metal complexes agent structure, pyrimidyl is the N heterocycle of high lumo energy, electrophilic trifluoromethyl on phenyl ring and two fluorine-based HOMO energy levels that can reduce material of electrophilic, be conducive to effective blue shift of material emission wavelength, secondly, on pyrimidine ring, the electro mass-energy of giving of alkyl or alkoxyl group improves the blue light emitting performance of material further, on the other hand, the introducing of this alkyl or alkoxyl group can produce certain space steric effect, thus the self-quenching phenomenon of direct effect between minimizing atoms metal and triplet exciton, improve the phosphorescence quantum yield of material, and then raising luminous efficiency, in addition, high field intensity assistant ligand 2-pyridinecarboxylic can make the more acceptant electronics of material, thus improve the luminous efficiency of material further, angle from materials processing: pyrimidine ring, the alkyl of different lengths or oxyalkyl chain can increase material solvability in organic solvent, different distribution type title complex can reduce evaporation temperature, increase film-forming properties, thus improve Drawing abillity and improve the stability of device.
Second aspect, the invention provides a kind of preparation method of blue-ray organic electroluminescent material, 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 as shown at c:
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 reflux state stirring reaction subsequently after 22 ~ 25 hours; be cooled to room temperature; separation and purification; obtain Compound D, its structural formula as shown atd:
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 carbonate or salt of wormwood by the mol ratio of 1:2.5 ~ 1:4; obtain mixing solutions; described mixing solutions carried out Suzuki linked reaction after 20 ~ 25 hours at 100 ~ 135 DEG C; separation and purification; obtain blue-ray organic electroluminescent material, its structural formula is as shown in P:
In formula, R is hydrogen atom, C
1~ C
20alkyl or C
1~ C
20alkoxyl group.
Preferably, in described step S20, the concentration of described compd A in reaction solution is 0.1 ~ 0.2mol/L; Described first organic solvent is DMF (DMF) or toluene.
Preferably, in described step S20, the volume ratio of described first organic solvent and wet chemical is about 2:1.
Preferably, in described step S20, the volume ratio of described first organic solvent and aqueous sodium carbonate is about 2:1.
Preferably, in described step 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 3% ~ 5% 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.
Preferably, in described step S20, described purification procedures comprises: after question response liquid is cooled to room temperature, adopt dichloromethane extraction, be then washed with water to neutrality, then after anhydrous magnesium sulfate drying, filtration obtains filtrate, gained filtrate obtains crude product after removing desolventizing under reduced pressure, and 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.
Preferably, in described step S30, the concentration of described Compound C in reaction solution is 0.06 ~ 0.12mol/L.
Preferably, in described step S30, described purification procedures comprises: after question response stopping is chilled to room temperature, rotates and steam except partial solvent, add appropriate distilled water, filter and obtain solid, solid uses distilled water, methanol wash successively, obtains described Compound D after drying.
Preferably, in described step S30, described purification procedures comprises: filter reaction mixture and obtain solid, solid uses ethanol, n-hexane successively, obtains described Compound D after vacuum-drying.
Preferably, in described step S40, described second organic solvent is 2-methyl cellosolve or cellosolvo.
Preferably, in described step S40, the concentration of described Compound D in mixing solutions is 0.01 ~ 0.0167mol/L, and the mole dosage of described sodium carbonate or salt of wormwood is 8 ~ 12 times of described Compound D.
Preferably, in described step S40, described purification procedures comprises: after question response stops being chilled to room temperature, reaction mixture dichloromethane extraction, then merges organic phase and uses anhydrous magnesium sulfate drying, more after filtration, remove solvent under reduced pressure and obtain crude product, adopt methylene dichloride to be that elutriant carries out silica gel column chromatography separating-purifying to gained crude product subsequently, then steaming desolventize, and obtains described blue-ray organic electroluminescent material after drying.
The preparation method of a kind of blue-ray organic electroluminescent material provided by the invention is simple, handled easily.
In subsequent embodiment, for convenience of statement, compd A, C, D, P use compd A 1, A2, A3, A4...... respectively; C1, C2, C3, C4......D1, D2, D3, D4......; P1, P2, P3, P4...... represent, concrete name is as the criterion with each embodiment.
The third aspect, present invention also offers a kind of organic electroluminescence device, comprises luminescent layer, and doped with blue-ray organic electroluminescent material as described in relation to the first aspect in described luminescent layer, its structural formula is as shown in P:
In formula, R is hydrogen atom, C
1~ C
20alkyl or C
1~ C
20alkoxyl group.
Organic electroluminescence device provided by the invention contains the blue-ray organic electroluminescent material of structural formula as shown in P, and this material has higher lumo energy and lower HOMO energy level, and device can be made to have good blue light emitting performance; In addition, this material filming performance is good, easily processes.
A kind of blue-ray organic electroluminescent material provided by the invention and its preparation method and application, its beneficial effect had is:
(1) blue-ray organic electroluminescent material provided by the invention comprises cyclic metal complexes agent structure 2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl) pyrimidine and assistant ligand 2-pyridinecarboxylic, in described cyclic metal complexes agent structure, pyrimidyl is the N heterocycle of high lumo energy, electrophilic trifluoromethyl on phenyl ring and two electrophilics fluorine-based, be conducive to reducing the HOMO energy level of material, thus make the effective blue shift of the emission wavelength of material, secondly, on pyrimidine ring, the electro mass-energy of giving of alkyl or alkoxyl group improves the blue light emitting performance of material further, on the other hand, the introducing of this alkyl or alkoxyl group can produce certain space steric effect, thus the self-quenching phenomenon of direct effect between minimizing atoms metal and triplet exciton, improve the phosphorescence quantum yield of material, and then raising luminous efficiency, in addition, high field intensity assistant ligand 2-pyridinecarboxylic can make the more acceptant electronics of material, thus improve the luminous efficiency of material further,
(2) blue-ray organic electroluminescent material provided by the invention, due to the introducing of different lengths alkyl chain 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) blue-ray organic electroluminescent material 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 preparation flow schematic diagram of the blue-ray organic electroluminescent material that the embodiment of the present invention 1 provides;
Fig. 2 is the utilizing emitted light spectrogram of the blue-ray organic electroluminescent material that the embodiment of the present invention 1 provides;
Fig. 3 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
The preparation flow schematic diagram of the blue-ray organic electroluminescent material shown in composition graphs 1, present embodiments provides a kind of two (2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl) pyrimidine-N, C
2') (2-pyridinecarboxylic) close complex of iridium, its chemical structure is as shown in P1:
The preparation process of above-mentioned P1 is as follows:
S10, Compound C 1(2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl) pyrimidine) synthesis
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-):
Under nitrogen protection, by compd A 1 (1.59g, 10mmol), compd B (2.71g, 12mmol) and Pd (PPh
3)
4(0.58mg, 0.5mmol) is dissolved in the toluene of 40mL, stirs 10 minutes, then adds the aqueous solution of 20mL containing salt of wormwood (2.76g, 20mmol), stirring reaction 6 hours at 100 DEG C; 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: C
11h
5f
5n
2
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 above-mentioned product C 1 be obtained by reacting of above data acknowledgement is 2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl) pyrimidine;
S20, Compound D 1(part be 2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl) pyrimidine containing iridium dichloro dimer) synthesis
Under nitrogen protection, by Compound C 1 (1.82g, it is, in the cellosolvo of 3:1 and the mixed solvent of water, be heated to reflux state stirring reaction 24 hours that 7mmol) He three hydrated iridium trichloride (0.71g, 2mmol) are dissolved in 60mL volume ratio; After being chilled to room temperature, filter reaction mixture and obtain solid, solid uses ethanol, n-hexane successively, and obtain the Compound D 1 of 0.92g after vacuum-drying, yield is 61.7%, and reaction formula is as follows:
S30, P1(two (2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl) pyrimidine-N, C
2') (2-pyridinecarboxylic) close complex of iridium) and synthesis
The compd E (2-pyridine carboxylic acid) providing following structural formula to represent:
Under nitrogen protection, by Compound D 1 (0.75g, 0.5mmol), sodium carbonate (0.53g, 5mmol) and compd E (0.18g, 1.5mmol) be dissolved in the cellosolvo of 30mL, be heated with stirring to 135 DEG C of reflux states and react 24 hours; Naturally, after being chilled to room temperature, the methylene dichloride continuous extraction of reaction mixture 50mL 3 times, then merges organic phase and uses anhydrous magnesium sulfate drying, more after filtration, removing solvent under reduced pressure and obtain crude product; Be that elutriant carries out silica gel column chromatography separating-purifying to crude product with methylene dichloride, steam subsequently and desolventize, obtain the P1 of 0.54g purifying after drying, yield is 64.8%, and reaction formula is as follows:
The Structural Identification result of compound P1 is as follows:
Mass spectrum (MS m/z): 833.0 (M+)
Ultimate analysis: C
28h
12f
10irN
5o
2
Theoretical value: C, 40.39; H, 1.45; F, 22.82; Ir, 23.09; N, 8.41; O, 3.84
Measured value: C, 40.33; H, 1.53; F, 22.77; Ir, 23.11; N, 8.45; O, 3.81
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-pyridinecarboxylic) close complex of iridium.
As shown in Figure 2, transverse axis is wavelength (Wavelength, unit nm), and the longitudinal axis is standardized photoluminescence intensity (Normalized PL intensity), at 298K temperature, and P1 (~ 10
-5m) at CH
2cl
2in solution, the maximum emission peak of emmission spectrum is at 468nm place, has an acromion at 491nm place simultaneously, and the P1 that this display the present embodiment provides can be used as the preparation field that blue light electroluminescent material is applied 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=0.25, 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-pyridinecarboxylic) close complex of iridium, its chemical structure is as shown in P2:
The preparation process of above-mentioned P2 is as follows:
S10, Compound C 2(2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl)-5-methylpyrimidine) synthesis
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-):
Under nitrogen protection, by compd A 2 (1.73g, 10mmol), compd B (2.48g, 11mmol) and Pd (PPh
3)
2cl
2(0.28mg, 0.4mmol) is dissolved in the DMF of 50mL, stirs 10 minutes, then adds the aqueous solution of 25mL containing sodium carbonate (3.18g, 30mmol), stirs 8 hours at 90 DEG C; 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 sherwood oil of 1:3 again by volume ratio with the mixed solution of methylene dichloride 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: C
12h
7f
5n
2
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)-4-methylpyrimidines.
S20, Compound D 2(part be 2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl)-4-methylpyrimidine containing iridium dichloro dimer) synthesis
Compound C 2 (1.62g, 6mmol) and three hydrated iridium trichloride (0.71g, 2mmol) being dissolved in 50mL volume ratio is, in the cellosolvo of 3:1 and the mixed solvent of water, be heated to reflux state stirring reaction 22 hours; After being chilled to room temperature, filter reaction mixture and obtain solid, solid uses ethanol, n-hexane successively, and obtain the Compound D 2 of 0.90g after vacuum-drying, yield is 58.1%, and reaction formula is as follows:
S30, P2(two (2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl)-4-methylpyrimidine-N, C
2') (2-pyridinecarboxylic) close complex of iridium) and synthesis
Compd E is as described in Example 1 provided;
Under nitrogen protection, by Compound D 2 (0.77g, 0.5mmol), sodium ethylate (0.55g, 4mmol) with compd E (0.25g, 2mmol) be dissolved in the 2-methyl cellosolve of 35mL, stirring heating, back flow reaction 25 hours at 125 DEG C; Naturally, after being chilled to room temperature, the methylene dichloride continuous extraction of reaction mixture 50mL 3 times, then merges organic phase and uses anhydrous magnesium sulfate drying, more after filtration, removing solvent under reduced pressure and obtain crude product; Be that elutriant carries out silica gel column chromatography separating-purifying to crude product with methylene dichloride, steam subsequently and desolventize, obtain the P2 of 0.52g purifying after drying, yield is 60.4%, and reaction formula is as follows:
The Structural Identification result of compound P2 is as follows:
Mass spectrum (MS m/z): 861.1 (M+)
Ultimate analysis: C
30h
16f
10irN
5o
2
Theoretical value: C, 41.86; H, 1.87; F, 22.07; Ir, 22.33; N, 8.14; O, 3.72
Measured value: C, 41.81; H, 1.94; F, 22.04; Ir, 22.37; N, 8.10; O, 3.74
The product P 2 that the above-mentioned reaction of above data acknowledgement obtains is two (2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl)-4-methylpyrimidine-N, C
2') (2-pyridinecarboxylic) close complex of iridium.
At 298K temperature, P2 (~ 10
-5m) CH
2cl
2in solution, the maximum emission peak of emmission spectrum is at 465nm place, has an acromion at 488nm 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=0.204.
Embodiment 3
Present embodiments provide a kind of two (2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl)-5-t-butyl pyrimidines-N, C
2') (2-pyridinecarboxylic) close complex of iridium, its chemical structure is as shown in P3:
The preparation process of above-mentioned P3 is as follows:
S10, Compound C 3(2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl)-5-t-butyl pyrimidines) synthesis
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-):
Under nitrogen protection, by compound A-13 (2.15g, 10mmol), compd B (3.39g, 15mmol) and Pd (PPh
3)
2cl
2(0.21mg, 0.3mmol) is dissolved in the DMF of 35mL, stirs 10 minutes, then adds the aqueous solution of 15mL containing salt of wormwood (1.38g, 10mmol), stirs 10 hours at 85 DEG C; 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: C
15h
13f
5n
2
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 S20, compound d3 (part be 2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl)-5-t-butyl pyrimidines containing iridium dichloro dimer)
Compound C 3 (0.70g, 2.2mmol) and three hydrated iridium trichloride (0.35g, 1mmol) being dissolved in 20mL volume ratio is, in the cellosolvo of 3:1 and the mixed solvent of water, be heated to reflux state stirring reaction 24 hours; After being chilled to room temperature, filter reaction mixture and obtain solid, solid uses ethanol, n-hexane successively, and obtain the compound d3 of 0.41g after vacuum-drying, yield is 47.8%, and reaction formula is as follows:
S30, P3(two (2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl)-5-t-butyl pyrimidines-N, C
2') (2-pyridinecarboxylic) close complex of iridium) and synthesis
Compd E as described in Example 1 is provided;
Under nitrogen protection, by compound d3 (0.86g, 0.5mmol), sodium carbonate (0.64g, 6mmol) and compd E (0.15g, 1.25mmol) be dissolved in the cellosolvo of 40mL, be heated with stirring to 135 DEG C of back flow reaction 20 hours; Naturally, after being chilled to room temperature, after being naturally chilled to room temperature, the methylene dichloride continuous extraction of reaction mixture 50mL 3 times, then merges organic phase and uses anhydrous magnesium sulfate drying, more after filtration, removing solvent under reduced pressure and obtain crude product; Be that elutriant carries out silica gel column chromatography separating-purifying to crude product with methylene dichloride, steam subsequently and desolventize, obtain the P3 of 0.38g purifying after drying, yield is 40.2%, and reaction formula is as follows:
The Structural Identification result of compound P3 is as follows:
Structural Identification:
Mass spectrum (MS m/z): 945.2 (M+)
Ultimate analysis: C
36h
28f
10irN
5o
2
Theoretical value: C, 45.76; H, 2.99; F, 20.11; Ir, 20.34; N, 7.41; O, 3.39
Measured value: C, 45.73; H, 2.96; F, 20.18; Ir, 20.31; N, 7.47; O, the product P 3 that the above-mentioned reaction of more than 3.35 data acknowledgement obtains is two (2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl)-5-t-butyl pyrimidines-N, C
2') (2-pyridinecarboxylic) 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 493nm 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 P2, is recorded
pL=0.264.
Embodiment 4
Present embodiments provide a kind of two (2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl)-4-eicosyl pyrimidine-N, C
2') (2-pyridinecarboxylic) close complex of iridium, its chemical structure is as shown in P4:
The preparation process of above-mentioned P4 is as follows:
S10, Compound C 4(2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl)-4-eicosyl pyrimidine) synthesis
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-):
Under nitrogen protection, by compd A 4 (2.20g, 5mmol), compd B (1.36g, 6mmol) and Pd (PPh
3)
4(0.23mg, 0.2mmol) is dissolved in the toluene of 35mL, stirs 10 minutes, then adds the aqueous solution of 15mL containing salt of wormwood (1.38g, 10mmol), stirs 12 hours at 85 DEG C; 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: C
31h
45f
5n
2
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;
S20, Compound D 4(part be 2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl)-4-eicosyl pyrimidine containing iridium dichloro dimer) synthesis
Compound C 4 (0.81g, 1.5mmol) and three hydrated iridium trichloride (0.18g, 0.5mmol) being dissolved in 25mL volume ratio is, in the cellosolvo of 3:1 and the mixed solvent of water, be heated to reflux state stirring reaction 25 hours; After being chilled to room temperature, rotating and steam except partial solvent, then add appropriate distilled water, filter and obtain solid, solid uses distilled water, methanol wash successively, and obtain the Compound D 4 of 0.13g after drying, yield is 19.9%, and reaction formula is as follows:
S30, P4(two (2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl)-4-eicosyl pyrimidine-N, C
2') (2-pyridinecarboxylic) close complex of iridium) and synthesis
Compd E as described in Example 1 is provided;
Under nitrogen protection, by Compound D 4 (0.52g, 0.2mmol), salt of wormwood (0.28g, 2mmol) and compd E (0.10g, 0.8mmol) be dissolved in the cellosolvo of 20mL, be heated with stirring to 100 DEG C of back flow reaction 24 hours; Naturally, after being chilled to room temperature, after being naturally chilled to room temperature, the methylene dichloride continuous extraction of reaction mixture 20mL 3 times, then merges organic phase and uses anhydrous magnesium sulfate drying, more after filtration, removing solvent under reduced pressure and obtain crude product; Be that elutriant carries out silica gel column chromatography separating-purifying to crude product with methylene dichloride, steam subsequently and desolventize, obtain the P4 of 0.10g purifying after drying, yield is 17.9%, and reaction formula is as follows:
The Structural Identification result of compound P4 is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1393.7 (M+)
Ultimate analysis: C
68h
92f
10irN
5o
2
Theoretical value: C, 58.60; H, 6.65; F, 13.63; Ir, 13.79; N, 5.03; O, 2.30
Measured value: C, 58.64; H, 6.57; F, 13.68; Ir, 13.74; N, 5.09; O, 2.28
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-pyridinecarboxylic) close complex of iridium.
At 298K temperature, P4 (~ 10
-5m) CH
2cl
2in solution, the maximum emission peak of emmission spectrum is at 489nm place, has an acromion at 512nm 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=0.07.
Embodiment 5
Present embodiments provide a kind of two (2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl)-5-methoxy pyrimidine-N, C
2') (2-pyridinecarboxylic) close complex of iridium, its chemical structure is as shown in P5:
The preparation process of above-mentioned P5 is as follows:
S10, Compound C 4(2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl)-5-methoxy pyrimidine) synthesis
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-):
Under nitrogen protection, by compound A-45 (1.89g, 10mmol), compd B (2.71g, 12mmol) and Pd (PPh
3)
4(0.58mg, 0.5mmol) is dissolved in the DMF of 40mL, stirs 10 minutes, then adds the aqueous solution of 20mL containing salt of wormwood (2.76g, 20mmol), stirs 6 hours at 100 DEG C; 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: 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, 49.63; 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;
S20, Compound D 5(part be 2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl)-5-methoxy pyrimidine containing iridium dichloro dimer) synthesis
Compound C 5 (1.74g, 6mmol) and three hydrated iridium trichloride (0.71g, 2mmol) being dissolved in 50mL volume ratio is, in the cellosolvo of 3:1 and the mixed solvent of water, be heated to reflux state stirring reaction 24 hours; After being chilled to room temperature, rotating and steam except partial solvent, then add appropriate distilled water, filter and obtain solid, solid uses distilled water, methanol wash successively, and obtain the Compound D 5 of 0.89g after drying, yield is 55.2%, and reaction formula is as follows:
S30, P5(two (2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl)-5-methoxy pyrimidine-N, C
2') (2-pyridinecarboxylic) close complex of iridium) and synthesis
Compd E as described in Example 1 is provided;
Under nitrogen protection, by Compound D 5 (0.81g, 0.5mmol), salt of wormwood (0.55g, 4mmol) and compd E (0.25g, 2mmol) be dissolved in the 2-methyl cellosolve of 35mL, be heated with stirring to 125 DEG C of back flow reaction 25 hours; Naturally, after being chilled to room temperature, after being naturally chilled to room temperature, the methylene dichloride continuous extraction of reaction mixture 50mL 3 times, then merges organic phase and uses anhydrous magnesium sulfate drying, more after filtration, removing solvent under reduced pressure and obtain crude product; Be that elutriant carries out silica gel column chromatography separating-purifying to crude product with methylene dichloride, steam subsequently and desolventize, obtain the P5 of 0.45g purifying after drying, yield is 50.4%, and reaction formula is as follows:
The Structural Identification result of compound P5 is as follows:
Structural Identification:
Mass spectrum (MS m/z): 893.1 (M+)
Ultimate analysis: C
30h
16f
10irN
5o
4
Theoretical value: C, 40.36; H, 1.81; F, 21.28; Ir, 21.53; N, 7.85; O, 7.17
Measured value: C, 40.32; H, 1.87; F, 21.23; Ir, 21.57; N, 7.80; O, 7.21
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-pyridinecarboxylic) close complex of iridium.
At 298K temperature, P5 (~ 10
-5m) CH
2cl
2in solution, the maximum emission peak of emmission spectrum is at 464nm place, has an acromion at 487nm 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=0.197.
Embodiment 6
Present embodiments provide a kind of two (2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl)-4-hexyloxy pyrimidine-N, C
2') (2-pyridinecarboxylic) close complex of iridium, its chemical structure is as shown in P6:
The preparation process of above-mentioned P6 is as follows:
S10, Compound C 6(2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl)-4-hexyloxy pyrimidine) synthesis
The bromo-4-of the compd A 6(2-own oxygen pyrimidine providing following structural formula to represent) and compd B (the fluoro-3-trifluoromethylbenzene boronic acid of 2,4-bis-):
Under nitrogen protection, by compd A 6 (2.59g, 10mmol), compd B (3.39g, 15mmol) and Pd (PPh
3)
2cl
2(0.21mg, 0.3mmol) is dissolved in the DMF of 40mL, then adds the aqueous solution of 20mL containing salt of wormwood (1.38g, 10mmol), stirs 10 hours at 85 DEG C; 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 sherwood oil of 1:4 again by volume ratio with the mixed solution of methylene dichloride be crude product that eluent carries out silica gel column chromatography is separated, and obtains 0.73g Compound C 6 after drying, yield is 20.2%, and 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: 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, 56.62; H, 4.82; F, 26.33; N, 7.81; O, 4.42
The product C 6 that the above-mentioned reaction of above data acknowledgement obtains is 2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl)-4-hexyloxy pyrimidines.
S20, Compound D 6(part be 2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl)-4-hexyloxy pyrimidine containing iridium dichloro dimer) synthesis
Compound C 6 (0.79g, 2.2mmol) and three hydrated iridium trichloride (0.35g, 1mmol) being dissolved in 20mL volume ratio is, in the cellosolvo of 3:1 and the mixed solvent of water, be heated to reflux state stirring reaction 24 hours; After being chilled to room temperature, rotating and steam except partial solvent, then add appropriate distilled water, filter and obtain solid, solid uses distilled water, methanol wash successively, and obtain the Compound D 6 of 0.38g after drying, yield is 40.2%, and reaction formula is as follows:
S30, P6(two (2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl)-4-hexyloxy pyrimidine-N, C
2') (2-pyridinecarboxylic) close complex of iridium) and synthesis
Compd E is as described in Example 1 provided;
Under nitrogen protection, by Compound D 6 (0.95g, 0.5mmol), sodium carbonate (0.64g, 6mmol) with compd E (0.15g, 1.25mmol) be dissolved in the cellosolvo of 40mL, stirring heating, back flow reaction 20 hours at 135 DEG C; Naturally, after being chilled to room temperature, the methylene dichloride continuous extraction of reaction mixture 50mL 3 times, then merges organic phase and uses anhydrous magnesium sulfate drying, more after filtration, removing solvent under reduced pressure and obtain crude product; Be that elutriant carries out silica gel column chromatography separating-purifying to crude product with methylene dichloride, steam subsequently and desolventize, obtain the P6 of 0.37g purifying after drying, yield is 35.8%, and reaction formula is as follows:
The Structural Identification result of compound P6 is as follows:
Mass spectrum (MS m/z): 1033.2 (M+)
Ultimate analysis: C
40h
36f
10irN
5o
4
Theoretical value: C, 46.51; H, 3.51; F, 18.39; Ir, 18.61; N, 6.78; O, 6.20
Measured value: C, 46.55; H, 3.44; F, 18.37; Ir, 18.67; N, 6.73; O, 6.24
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-pyridinecarboxylic) close complex of iridium.
At 298K temperature, P2 (~ 10
-5m) CH
2cl
2in solution, the maximum emission peak of emmission spectrum is at 477nm place, has an acromion at 501nm 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=0.10.
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-pyridinecarboxylic) close complex of iridium, its chemical structure is as shown in P7:
The preparation process of above-mentioned P7 is as follows:
S10, Compound C 7(2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl)-5-eicosane oxygen yl pyrimidines) synthesis
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-):
Under nitrogen protection, by compd A 7 (2.28g, 5mmol), compd B (1.36g, 6mmol) and Pd (PPh
3)
2cl
2(0.23mg, 0.2mmol) is dissolved in the DMF of 35mL, then adds the aqueous solution of 15mL containing salt of wormwood (1.38g, 10mmol), stirs 12 hours at 85 DEG C; 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: 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, 66.82; 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;
S20, Compound D 7(part be 2-(2 ', 4 '-two fluoro-3 '-trifluoromethyl)-5-eicosane oxygen yl pyrimidines containing iridium dichloro dimer) synthesis
Compound C 7 (0.84g, 1.5mmol) and three hydrated iridium trichloride (0.18g, 0.5mmol) being dissolved in 25mL volume ratio is, in the cellosolvo of 3:1 and the mixed solvent of water, be heated to reflux state stirring reaction 25 hours; After being chilled to room temperature, rotating and steam except partial solvent, then add appropriate distilled water, filter and obtain solid, solid uses distilled water, methanol wash successively, and obtain the Compound D 7 of 0.12g after drying, yield is 17.9%, and reaction formula is as follows:
S30, P3(two (2-(4 ', 6 '-two fluoro-5 '-trifluoromethyl)-5-eicosane oxygen yl pyrimidines-N, C
2') (2-pyridinecarboxylic) close complex of iridium) and synthesis
Compd E as described in Example 1 is provided;
Under nitrogen protection, by Compound D 7 (0.54g, 0.2mmol), salt of wormwood (0.28g, 2mmol) and compd E (0.19g, 0.9mmol) be dissolved in the cellosolvo of 20mL, be heated with stirring to 100 DEG C of back flow reaction 24 hours; Naturally, after being chilled to room temperature, after being naturally chilled to room temperature, the methylene dichloride continuous extraction of reaction mixture 20mL 3 times, then merges organic phase and uses anhydrous magnesium sulfate drying, more after filtration, removing solvent under reduced pressure and obtain crude product; Be that elutriant carries out silica gel column chromatography separating-purifying to crude product with methylene dichloride, steam subsequently and desolventize, obtain the P7 of 0.09g purifying after drying, yield is 15.8%, and reaction formula is as follows:
The Structural Identification result of compound P7 is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1425.7 (M+)
Ultimate analysis: C
68h
92f
10irN
5o
4
Theoretical value: C, 57.29; H, 6.50; F, 13.33; Ir, 13.48; N, 4.91; O, 4.49
Measured value: C, 57.25; H, 6.57; F, 13.27; Ir, 13.52; N, 4.88; O, 4.51
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-pyridinecarboxylic) close complex of iridium.
At 298K temperature, P7 (~ 10
-5m) CH
2cl
2in solution, the maximum emission peak of emmission spectrum is at 494nm place, has an acromion at 517nm 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=0.026.
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 3, 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:
On the glass-based plate of pre-washing and UV-ozone process, a layer thickness is 100nm, square resistance is 20 ~ 25 Ω/mouth 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, and toasts 10min at 120 DEG C of temperature in nitrogen atmosphere; And then spin coating a layer thickness is the two (2-(4' prepared doped with 12wt% embodiment 1 of 50nm on hole injection layer 302, the fluoro-5'-trifluoromethyl of 6'-bis-) pyrimidine-N, C2') (2-pyridinecarboxylic) close the PVK (Polyvinyl carbazole) of iridium (P1) as luminescent layer 303; Then on this luminescent layer 303 spin coating a layer thickness be 1,3,5-tri-(m-pyridin-3-yl phenyl) benzene (TmPyPB) material of 20nm as electron transfer layer 304,80 DEG C of anneal 60min; Last 5 × 10
-8in Torr vacuum, evaporation a layer thickness is that the LiF of 1nm is as electron injection buffer layer 305, and adopting vacuum plating techniques of deposition thickness to be the metal A l of 120nm on the buffer layer, the concrete structure as this organic electroluminescence device of negative electrode 306 of device can be expressed as ITO (100nm)/PEDOT:PSS (40nm)/PVK:12wt%P1 (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 472nm place, and have an acromion at 498nm place, the maximum external quantum efficiency of device is 10.0%, and maximum lumen efficiency is 8.6lm/W.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a blue-ray organic electroluminescent material, is characterized in that, structural formula is as shown in P:
In formula, R is hydrogen atom, C
1~ C
20alkyl or C
1~ C
20alkoxyl group.
2. a preparation method for blue-ray organic electroluminescent material, 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 as shown at c:
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 reflux state stirring reaction subsequently after 22 ~ 25 hours; be cooled to room temperature; separation and purification; obtain Compound D, its structural formula as shown atd:
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 carbonate or salt of wormwood by the mol ratio of 1:2.5 ~ 1:4; obtain mixing solutions; described mixing solutions carried out Suzuki linked reaction after 20 ~ 25 hours at 100 ~ 135 DEG C; separation and purification; obtain blue-ray organic electroluminescent material, its structural formula is as shown in P:
In formula, R is hydrogen atom, C
1~ C
20alkyl or C
1~ C
20alkoxyl group.
3. the preparation method of blue-ray organic electroluminescent material as claimed in claim 2, it is characterized in that, in described step 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 blue-ray organic electroluminescent material as claimed in claim 2, it is characterized in that, in described step 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 3% ~ 5% 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 blue-ray organic electroluminescent material as claimed in claim 2, it is characterized in that, in described step 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 blue-ray organic electroluminescent material as claimed in claim 2, it is characterized in that, in described step S30, described purification procedures comprises: after question response stops being chilled to room temperature, rotate and steam except partial solvent, add appropriate distilled water, filter and obtain solid, solid uses distilled water, methanol wash successively, obtains described Compound D after drying.
7. the preparation method of blue-ray organic electroluminescent material as claimed in claim 2, it is characterized in that, in described step S40, described second organic solvent is 2-methyl cellosolve or cellosolvo.
8. the preparation method of blue-ray organic electroluminescent material as claimed in claim 2, it is characterized in that, in described step S40, the concentration of described Compound D in mixing solutions is 0.01 ~ 0.0167mol/L, and the mole dosage of described sodium carbonate or salt of wormwood is 8 ~ 12 times of described Compound D.
9. the preparation method of blue-ray organic electroluminescent material as claimed in claim 2, it is characterized in that, in described step S40, described purification procedures comprises: after question response stops being chilled to room temperature, reaction mixture dichloromethane extraction, then merge organic phase and use anhydrous magnesium sulfate drying, again after filtration, remove solvent under reduced pressure and obtain crude product, methylene dichloride is adopted to be that elutriant carries out silica gel column chromatography separating-purifying to gained crude product subsequently, steam again and desolventize, after drying, obtain described blue-ray organic electroluminescent material.
10. an organic electroluminescence device, comprises luminescent layer, it is characterized in that, doped with the such as blue-ray organic electroluminescent material shown in structural formula P in described luminescent layer:
In formula, R is hydrogen atom, C
1~ C
20alkyl or C
1~ C
20alkoxyl group.
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