CN104447878A - Liquid crystal modified carbazole derivative organic electrophosphorescent materials as well as preparation method and application thereof - Google Patents
Liquid crystal modified carbazole derivative organic electrophosphorescent materials as well as preparation method and application thereof Download PDFInfo
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- CN104447878A CN104447878A CN201410763268.0A CN201410763268A CN104447878A CN 104447878 A CN104447878 A CN 104447878A CN 201410763268 A CN201410763268 A CN 201410763268A CN 104447878 A CN104447878 A CN 104447878A
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- 239000000463 material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 239000004973 liquid crystal related substance Substances 0.000 title abstract description 7
- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 title abstract 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 91
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical class [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052697 platinum Chemical class 0.000 claims abstract description 6
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 4
- 239000002585 base Substances 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 46
- 125000003545 alkoxy group Chemical group 0.000 claims description 39
- 125000000217 alkyl group Chemical group 0.000 claims description 37
- 125000004432 carbon atom Chemical group C* 0.000 claims description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 238000006467 substitution reaction Methods 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- 125000001153 fluoro group Chemical group F* 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 11
- 238000005401 electroluminescence Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- -1 2-pyrimidyl Chemical group 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 230000005540 biological transmission Effects 0.000 claims description 8
- UZVGSSNIUNSOFA-UHFFFAOYSA-N dibenzofuran-1-carboxylic acid Chemical compound O1C2=CC=CC=C2C2=C1C=CC=C2C(=O)O UZVGSSNIUNSOFA-UHFFFAOYSA-N 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 8
- 239000007924 injection Substances 0.000 claims description 8
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 7
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 claims description 7
- IYZMXHQDXZKNCY-UHFFFAOYSA-N 1-n,1-n-diphenyl-4-n,4-n-bis[4-(n-phenylanilino)phenyl]benzene-1,4-diamine Chemical group C1=CC=CC=C1N(C=1C=CC(=CC=1)N(C=1C=CC(=CC=1)N(C=1C=CC=CC=1)C=1C=CC=CC=1)C=1C=CC(=CC=1)N(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 IYZMXHQDXZKNCY-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical group [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- SIOXPEMLGUPBBT-UHFFFAOYSA-N Picolinic acid Natural products OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 235000011187 glycerol Nutrition 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 claims description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 229920001940 conductive polymer Polymers 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910010272 inorganic material Inorganic materials 0.000 claims description 3
- 239000011147 inorganic material Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- MNCMBBIFTVWHIP-UHFFFAOYSA-N 1-anthracen-9-yl-2,2,2-trifluoroethanone Chemical group C1=CC=C2C(C(=O)C(F)(F)F)=C(C=CC=C3)C3=CC2=C1 MNCMBBIFTVWHIP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 2
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 claims description 2
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 125000002339 acetoacetyl group Chemical group O=C([*])C([H])([H])C(=O)C([H])([H])[H] 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 125000004351 phenylcyclohexyl group Chemical group C1(=CC=CC=C1)C1(CCCCC1)* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- KZVLNAGYSAKYMG-UHFFFAOYSA-N pyridine-2-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=N1 KZVLNAGYSAKYMG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 150000002503 iridium Chemical class 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 239000007787 solid Substances 0.000 description 18
- 238000001704 evaporation Methods 0.000 description 17
- 230000008020 evaporation Effects 0.000 description 17
- 238000003756 stirring Methods 0.000 description 17
- 238000010992 reflux Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000009413 insulation Methods 0.000 description 8
- IUYHWZFSGMZEOG-UHFFFAOYSA-M magnesium;propane;chloride Chemical compound [Mg+2].[Cl-].C[CH-]C IUYHWZFSGMZEOG-UHFFFAOYSA-M 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- 230000007704 transition Effects 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 230000000630 rising effect Effects 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 229960001866 silicon dioxide Drugs 0.000 description 6
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 5
- 239000005695 Ammonium acetate Substances 0.000 description 5
- 229940043376 ammonium acetate Drugs 0.000 description 5
- 235000019257 ammonium acetate Nutrition 0.000 description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 0 C[C@]1[C@@](C)(C(C(C2)C3C(*)C(*)C4C)C5C2*CCC5)C1(C)[C@@]3C4P Chemical compound C[C@]1[C@@](C)(C(C(C2)C3C(*)C(*)C4C)C5C2*CCC5)C1(C)[C@@]3C4P 0.000 description 4
- 150000001716 carbazoles Chemical class 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 150000003057 platinum Chemical class 0.000 description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- YHYKLKNNBYLTQY-UHFFFAOYSA-N 1,1-diphenylhydrazine Chemical compound C=1C=CC=CC=1N(N)C1=CC=CC=C1 YHYKLKNNBYLTQY-UHFFFAOYSA-N 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000014443 Pyrus communis Nutrition 0.000 description 1
- 229940008309 acetone / ethanol Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004802 cyanophenyl group Chemical group 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- KYKLWYKWCAYAJY-UHFFFAOYSA-N oxotin;zinc Chemical compound [Zn].[Sn]=O KYKLWYKWCAYAJY-UHFFFAOYSA-N 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000011787 zinc oxide Substances 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
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/18—Benzimidazoles; Hydrogenated benzimidazoles with aryl radicals directly attached in position 2
-
- 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
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
-
- 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)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses liquid crystal modified carbazole derivative organic electrophosphorescent materials as well as a preparation method and application thereof. A structural general formula of the materials is shown in a formula I in the specification. The invention provides a series of iridium or platinum complex electrophosphorescent materials with chiral groups because efficient electrophosphorescent materials with good film-forming properties and shorter phosphorescence lifetime are needed and in order that the luminescent efficiency and the properties of luminescent devices are improved at the same time. The compounds have the characteristics of excellent film-forming properties, high luminescent efficiency, and the like, are accessible in raw materials, are simple and convenient to prepare, have high total yields, have the effect of greatly reducing the costs of phosphorescent materials and have important application values.
Description
Technical field
The invention belongs to field of liquid crystals, relate to carbazoles derivative organic electromechanical phosphorescent material of a kind of liquid crystal modification and preparation method thereof and application.
Background technology
For organic electroluminescent (being called for short OLED) and relevant research, first find the electro optical phenomenon of organic compound single-crystal anthracene as far back as people such as pope in 1963.A kind of amorphous membranous type device has been made by the method for evaporation organic molecule by the Kodak of the U.S. in 1987, has been dropped within 20V by driving voltage.This kind of device owing to having ultra-thin, all solidstate, luminous, brightness is high, visual angle is wide, fast response time, driving voltage are low, power consumption is little, bright in luster, contrast gradient is high, technological process is simple, good temp characteristic, can realize the advantages such as soft display, flat-panel monitor and area source can be widely used in, therefore obtain and study widely, develop and use.
Through the development of twenties years, organic EL Material is red, blue, the green emitting of round Realization, and Application Areas also extend to the field such as polymer and metal complex from small molecules.Recent years, organic electroluminescent technique of display obtained huge progress, and achieved Red, Blue, Green luminescence.But the material that there will be a known practical value and potentiality is at present also very limited, particularly the organic materials of overall target excellence is badly in need of Study and Development, although wherein green phosphorescent material can meet commercialization substantially, but still is short of to some extent in stability and efficiency.Therefore, stable, high-level efficiency green light material molecular designing with become important research contents.
Summary of the invention
The object of this invention is to provide carbazoles derivative organic electromechanical phosphorescent material of a kind of liquid crystal modification and preparation method thereof and application.
The carbazoles derivative organic electromechanical phosphorescent material that liquid crystal provided by the invention is modified, its general structure such as formula shown in I,
In described formula I, R
1, R
2, R
3and R
4all be selected from H ,-F ,-Cl ,-Br ,-CN ,-CF
3,-OCF
3, any one in the aliphatic group of C1-C50 that replaces of the total number of carbon atoms alkyl that is 1-15, the total number of carbon atoms alkoxyl group that is 1-15, the total number of carbon atoms be the normal olefine base of 2-15, the total number of carbon atoms of fluoro is the alkyl of 1-15, the total number of carbon atoms of fluoro is the alkoxyl group of 1-15, the total number of carbon atoms of fluoro is 2-15 normal olefine base, trans-cycloh, phenylcyclohexyl, the aliphatic group of C1-C50 and cyclohexyl;
R
5be selected from the alkyl that the total number of carbon atoms is 1-15, the total number of carbon atoms is the alkoxyl group of 1-15, the total number of carbon atoms is the normal olefine base of 2-15, the total number of carbon atoms of fluoro is the alkyl of 1-15, the total number of carbon atoms of fluoro is the alkoxyl group of 1-15, the total number of carbon atoms of fluoro is the normal olefine base of 2-15, N-phenyl-carbazole-2-base, N-phenyl-carbazole-3-base, 9-anthryl, 1-naphthyl, 2-naphthyl, phenyl, 4-xenyl, 3-xenyl, 4-triphenylamine base, 2-pyrimidyl, 3-carbazyl, 3-pyridyl, 1, 3, 4-oxadiazole-2-base, dibenzo [b, d] furans-2-base, dibenzo [b, d] furans-4-base, dibenzo [b, d] thiophene-2-base and dibenzo [b, d] any one in thiophene-4-base,
X is 1,2 or 3;
Y is 0,1,2 or 3; And x is when being 3, y is 0;
M be selected from metal iridium and platinum any one; And M is when being platinum, x is not 3;
It is any one in the acetoacetyl of 5-25 that L is selected from acetylacetone based, 2-pyridine carboxylic acid base, 2-pyridine-sulfonic acid base, 2-phenylpyridyl and the total number of carbon atoms with side chain.
In described formula I, R
3for propylcyclohexyl phenyl or the own phenyl of propyl group dicyclo.
Shown in described formula I, compound is specially any one in compound shown in following RIr-AC-I, RPt-AC-I, RIr-AP-I, RPt-AP-I and RIr-AC-II:
In described RIr-AC-I, RPt-AC-I, RIr-AP-I, RPt-AP-I and RIr-AC-II, R
1to R
5definition identical with the definition in previously described formula I;
R in described formula I
1to R
5definition in, described the total number of carbon atoms is the alkyl that the alkyl of 1-15 is specifically selected from C2-C15, the alkyl of C3-C15, the alkyl of C4-C15, the alkyl of C5-C15, the alkyl of C6-C15, the alkyl of C1-C7, the alkyl of C2-C7, the alkyl of C3-C7, the alkyl of C4-C7, the alkyl of C5-C7, the alkyl of C6-C7, the alkyl of C1-C6, the alkyl of C2-C6, the alkyl of C3-C6, the alkyl of C4-C6, the alkyl of C5-C6, the alkyl of C1-C5, the alkyl of C2-C5, the alkyl of C3-C5, the alkyl of C4-C5, the alkyl of C1-C4, the alkyl of C2-C4, the alkyl of C3-C4, the alkyl of C1-C3, the alkyl of C1-C10, the alkyl of C2-C10, the alkyl of C3-C10, the alkyl of C1-C10, at least one in the alkyl of C1-C2 and the alkyl of C2-C3,
Described the total number of carbon atoms is the alkoxyl group that the alkoxyl group of 1-15 is specifically selected from C2-C15, the alkoxyl group of C3-C15, the alkoxyl group of C4-C15, the alkoxyl group of C5-C15, the alkoxyl group of C6-C15, the alkoxyl group of C1-C7, the alkoxyl group of C2-C7, the alkoxyl group of C3-C7, the alkoxyl group of C4-C7, the alkoxyl group of C5-C7, the alkoxyl group of C6-C7, the alkoxyl group of C1-C6, the alkoxyl group of C2-C6, the alkoxyl group of C3-C6, the alkoxyl group of C4-C6, the alkoxyl group of C5-C6, the alkoxyl group of C1-C5, the alkoxyl group of C2-C5, the alkoxyl group of C3-C5, the alkoxyl group of C4-C5, the alkoxyl group of C1-C4, the alkoxyl group of C2-C4, the alkoxyl group of C3-C4, the alkoxyl group of C1-C3, the alkoxyl group of C1-C10, the alkoxyl group of C2-C10, the alkoxyl group of C3-C10, the alkoxyl group of C1-C10, at least one in the alkoxyl group of C1-C2 and the alkoxyl group of C2-C3,
Described the total number of carbon atoms is the normal olefine base that the normal olefine base of 2-15 is specifically selected from C3-C15, the normal olefine base of C4-C15, the normal olefine base of C5-C15, the normal olefine base of C6-C15, the normal olefine base of C1-C6, the normal olefine base of C2-C6, the normal olefine base of C3-C6, the normal olefine base of C4-C6, the normal olefine base of C5-C6, the normal olefine base of C2-C5, the normal olefine base of C3-C5, the normal olefine base of C4-C5, the normal olefine base of C2-C4, the normal olefine base of C3-C4, the normal olefine base of C2-C10, the normal olefine base of C3-C10, at least one in the normal olefine base of C2-C8 and the normal olefine base of C2-C3,
Wherein, shown in described RIr-AC-I, compound is specially any one in compound shown in following RIr-AC-I-001 to RIr-AC-I-096:
Shown in described RPt-AC-I, compound is specially any one in compound shown in following RPt-AC-I-001 to RPt-AC-I-096:
Shown in described RIr-AP-I, compound is specially any one in compound shown in following RIr-AP-I-001 to RIr-AP-I-096:
Shown in described RPt-AP-I, compound is specially any one in compound shown in following RPt-AP-I-001 to RPt-AP-I-096:
Shown in described RIr-AC-II, compound is specially any one in compound shown in following RIr-AC-II-001 to RIr-AC-II-096:
The method of compound shown in preparation formula I provided by the invention is any one in following method one to method three;
Wherein, method one comprises the steps:
Will
in solvent, mix backflow with methyl ethyl diketone and alkali and carry out substitution reaction, react the complete x that obtains for compound shown in RIr-AC-I or RPt-AC-I of 1 or 2;
Described method two comprises the steps:
Will
with
in solvent, mix backflow with alkali and carry out substitution reaction, react the complete x that obtains for compound shown in RIr-AP-I or RPt-AP-I of 1 or 2;
Described method three comprises the steps:
Will
with
in solvent mixing carry out substitution reaction, react complete obtain x for 3 time RIr-AC-II shown in compound;
In described method one to three, R
1-R
5, M definition identical with the definition in previously described formula I.
The reaction scheme of above-mentioned three methods is as follows:
In the method one of aforesaid method,
the mole dosage that feeds intake of methyl ethyl diketone and alkali, than being 1:2-4:2-10, is specially 1:2:10; In described substitution reaction step, the time is 10-24 hour;
In described method two,
compare for 1:2-4:2-10 with the mole dosage that feeds intake of alkali, be specially 1:2:10; In described substitution reaction step, the time is 4-10 hour, is specially 8 hours;
In described method three,
with
mass ratio be 1:3-4, be specially 1.08:3.97;
In described substitution reaction step, temperature is 170-190 DEG C, is specially 180 DEG C; Time is 7-9 hour, is specially 8 hours.
In described method one and method two, described alkali is all selected from least one in anhydrous sodium carbonate and Anhydrous potassium carbonate;
In described method one to three, described reaction is carried out all in an inert atmosphere; Described inert atmosphere is specially nitrogen atmosphere;
Described solvent is all selected from least one in ethylene glycol ethyl ether, tetrahydrofuran (THF), normal hexane, toluene, ethanol, water, glycerine, Isosorbide-5-Nitrae-dioxane, acetonitrile and chloroform.
In aforesaid method, as initial reactant,
with
can be prepared as follows and obtain:
1) by 1-R
1-2-R
2-3-R
3-4-R
4after benzene and isopropylmagnesium chloride react 2h in 0 DEG C in THF solution, then add DMF in 0 DEG C of reaction 2h, then acidifying 0.5h under hydrochloric acid, obtains
2) by step 1) product that obtains
with
ammonium acetate is stirring and refluxing reaction 48h in solvent, reacts complete and obtains
3) by step 2) product that obtains
iridium salt or platinum salt reflux and carry out substitution reaction 10-24 hour in solvent, react complete and obtain
In each reaction materil structure general formula of aforesaid method, R
1-R
5, M and x definition respectively with R in previously described formula I
1-R
5, M with x definition identical.
The step 1 of aforesaid method) in, 1-R
1-2-R
2-3-R
3-4-R
4the molar ratio of benzene and isopropylmagnesium chloride is 1:1 ~ 3, specifically can be 1:1,1:1.2,1:1.5,1:2,1:2.5,1:3, preferred 1:1.1 ~ 1.5; Described 1-R
1-2-R
2-3-R
3-4-R
4the molar ratio of benzene and DMF is 1:1 ~ 3, specifically can be 1:1,1:1.2,1:1.5,1:2,1:2.5,1:3, preferred 1:1.5 ~ 2;
Step 2) in, described alkali is all selected from least one in anhydrous sodium carbonate and Anhydrous potassium carbonate;
with
ammonium acetate molar ratio is 1:0.5-1:2-20, is specially 1:0.9:20
Step 3) in, iridium salt is IrCl
3, IrCl
33H
2o or IrCl
4;
Platinum salt is K
2ptCl
4, PtCl
2or KPtCl
4;
Described
compare for 1:0.3-0.6 with the mole dosage that feeds intake of iridium salt or platinum salt, be specially 1:0.5;
Described step 1) to 3) in reaction carry out all in an inert atmosphere; Described inert atmosphere is specially nitrogen atmosphere;
Described step 1) to 3) in, solvent is all selected from least one in ethylene glycol ethyl ether, tetrahydrofuran (THF), methyltetrahydrofuran, methyl tertiary butyl ether, normal hexane, toluene, ethanol, water, glycerine, Isosorbide-5-Nitrae-dioxane, acetonitrile and chloroform.
Luminescent material containing compound shown in the formula I that the invention described above provides and this compounds, preparing the application in luminescent material, also belong to protection scope of the present invention.Wherein, described luminescent material is organic electroluminescent phosphorescence luminescent material.
In addition, compound shown in the formula I that the invention described above provides as luminescent layer the application prepared in organic electroluminescence device and containing compound shown in formula I as the organic electroluminescence device of luminescent layer, also belong to protection scope of the present invention.Wherein, described organic electroluminescence device is organic electro-phosphorescent luminescent device.
Concrete, described organic electroluminescence device is made up of transparent substrate, anode layer, hole injection layer, hole transmission layer, organic luminous layer, electron transfer layer and cathode layer from the bottom to top successively;
Wherein, the material forming described transparent substrate is glass or flexible substrate;
The material forming described anode layer is inorganic materials or organic conductive polymer; Wherein, described inorganic materials is specially tin indium oxide, zinc oxide, zinc tin oxide, gold and silver or copper; Described organic conductive polymer is selected from least one in Polythiophene, polyvinylbenzenesulfonic acid sodium and polyaniline;
The material forming described hole injection layer is TDATA;
The structural formula of described TDATA is as follows:
The material forming described hole transmission layer is NPB;
The structural formula of described NPB is as follows:
The material forming described organic luminous layer is made up of compound shown in aforementioned formula I provided by the invention and material of main part;
Wherein, described material of main part be mCP, CBP, NATZ or
Wherein, the structural formula of mCP, CBP and NATZ is as follows:
The quality of compound shown in formula I is the 1-10% of material of main part quality, is specially 5%;
The material forming described electron transfer layer is Alq3, Gaq3, BPhen or TPBi;
Wherein, the structural formula of Alq3, Gaq3, BPhen and TPBi is as follows successively:
The material forming described cathode layer is selected from any one or any alloys of two kinds of compositions in following element or the fluorochemical of following element: lithium, magnesium, silver, calcium, strontium, aluminium, indium, copper, Jin Heyin.
Wherein, the thickness of described hole injection layer is 30-50nm, is specially 40nm;
The thickness of described hole transmission layer is 5-15nm, is specially 10nm;
The thickness of described organic luminous layer is 10-100nm, is specially 50nm;
The thickness of described electron transfer layer is 10-30nm, is specially 20nm;
The thickness of described cathode layer is 90-110nm, is specially 100nm.
The present invention is based on the film forming properties that electromechanical phosphorescent material has needed and the high efficiency phosphorescent material with shorter phosphorescent lifetime, improve luminous efficiency simultaneously, improve the performance of luminescent device, provide a series of iridium or the platinum complex electroluminescent phosphorescence luminescent material with chiral radicals.This compounds has film-forming properties and becomes excellent, luminous efficiency high, and raw material is easy to get, and prepare easy, overall yield is high, the cost of the phosphor material greatly reduced, and has important using value.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described starting material all can obtain from open commercial sources if no special instructions.
In following embodiment, THF represents tetrahydrofuran (THF), and n-BuLi represents n-Butyl Lithium, and DCM represents methylene dichloride, and KOtBu represents potassium tert.-butoxide.
Following embodiment the testing tool of performance test is carried out to OLED material and device and method as follows:
Emission wavelength and tristimulus coordinates: use spectrum scanner PhotoResearch PR-655 test;
Current density and a bright voltage: use digital sourcemeter Keithley 2420 to test;
Power efficiency: use NEWPORT 1931-C test.
In following embodiment 1, shown in G-2 used, initial reactant is prepared as follows and obtains:
The first step: the preparation of compound G-0
24.6g 4-(4-iodophenyl)-4 '-propyl group bis cyclohexane is dissolved in 350ml THF, and cryosel bath temperature is down to 0 DEG C, slowly drips 33ml isopropylmagnesium chloride under nitrogen protection; dropwise rear insulation reaction 2h, start to drip 9ml DMF, after insulation reaction 1h; stirring reaction rises to normal temperature naturally, adds the hydrochloric acid soln of 90ml 4mol/L, acidifying 0.5h; PH is 1; ethyl acetate separatory, washing organic phase, revolves steamed post; finally obtain 15.4g white solid G-0, yield 82.3%.
Second step: the preparation of compound G-1'
Adjacent for upper step product G-03.432g and 1.84g aminodiphenylamine, 15.4g ammonium acetate are added in 250ml eggplant-shape bottle, add 160ml ethanol, stirring and refluxing reaction 48h, be cooled to normal temperature, suction filtration, wash 4-5 time, obtain faint yellow solid, stir recrystallization with after 10 times of sherwood oils and ethyl acetate heating for dissolving, obtain 1.3g product G-1, yield 27.3%.
3rd step: the preparation of compound G-2
The IrCl of compound G-1 and the 0.46g of 1.23g
33H
2in the ethylene glycol ethyl ether that O is dispersed in 15ml and 5ml water, under nitrogen protection, temperature rising reflux carries out substitution reaction 24 hours, cool to room temperature, and filter, filter cake washes with water, vacuum-drying, obtains the compound G-2 of 2.43g, yellow solid.
In following embodiment 4, shown in G-2-1 used, initial reactant is prepared as follows and obtains:
The first step: the preparation of compound G-0
24.6g 4-(4-iodophenyl)-4 '-propyl group bis cyclohexane is dissolved in 350ml THF, and cryosel bath temperature is down to 0 DEG C, slowly drips 33ml isopropylmagnesium chloride under nitrogen protection; dropwise rear insulation reaction 2h, start to drip 9ml DMF, after insulation reaction 1h; stirring reaction rises to normal temperature naturally, adds the hydrochloric acid soln of 90ml 4mol/L, acidifying 0.5h; PH is 1; ethyl acetate separatory, washing organic phase, revolves steamed post; finally obtain 15.4g white solid G-0, yield 82.3%.
Second step: the preparation of compound G-1-1
By upper step product G-03.432g and 1.44g O-Phenylene Diamine, 17.0g ammonium acetate is added in 250ml eggplant-shape bottle, add 160ml ethanol, stirring and refluxing reaction 48h, be cooled to normal temperature, suction filtration, wash 4-5 time, obtain faint yellow solid, recrystallization is stirred with after 10 times of sherwood oils and ethyl acetate heating for dissolving, obtain 2.15g product, 100ml pear shape bottle is added with 50mlDMF, be cooled to 0 DEG C, add 0.105gNaH in batches, after insulation reaction 2h, add 1g methyl iodide, normal-temperature reaction 2h after insulation reaction 2h, after adding 20ml water stirring 0.5h, separatory, wash with ethanol after organic phase underpressure distillation, obtain 1.6g product, yield 34.8%.
3rd step: the preparation of compound G-2-1
The IrCl of compound G-1-1 and the 0.52g of 1.25g
33H
2in the ethylene glycol ethyl ether that O is dispersed in 15ml and 5ml water, under nitrogen protection, temperature rising reflux carries out substitution reaction 24 hours, cool to room temperature, and filter, filter cake washes with water, vacuum-drying, obtains the compound G-2-1 of 2.53g, yellow solid.
In following embodiment 7, the preparation method of initial reactant G-4' used is as follows:
The first step: prepared by the fluoro-5-of compound 3-itrile group-2-(4 '-propyl group dicyclohexyl-4-base) phenyl aldehyde
The fluoro-6-of 2-(the 4 '-propyl group dicyclohexyl-4-base) cyanophenyl of 3.27g, 1.24g KOtBu and
7.5ml is dissolved in the anhydrous tetrahydro furan of 60ml; under nitrogen protection; with liquid nitrogen cooling to-80 DEG C, slowly drip the n-Butyl Lithium of the 2.5M of 4.8mol, insulation reaction 1h; slow dropping DMF; naturally rise to normal temperature after dropwising rear insulation 1h, add 20ml concentrated hydrochloric acid, after reaction 0.5h, PH detection aqueous phase PH=1. is extracted with ethyl acetate; 5.5g white solid is spin-dried for obtain, yield 75% after washing twice.
Second step: the preparation of compound G-1'
Adjacent for upper step product G-03.905g and 1.84g aminodiphenylamine, 15.4g ammonium acetate are added in 250ml eggplant-shape bottle, add 160ml ethanol, stirring and refluxing reaction 48h, be cooled to normal temperature, suction filtration, wash 4-5 time, obtain pale solid, stir recrystallization with after 10 times of sherwood oils and ethyl acetate heating for dissolving, obtain 2.13g product G-1', yield 41.0%.
3rd step: the preparation of compound G-4'
Get the compound G-1 ' of 2.076g and the K of 906.4mg
2ptCl
4in the ethylene glycol ethyl ether being dispersed in 48ml and 16ml water, under nitrogen protection, be warming up to 80 DEG C of stirrings and carry out substitution reaction 24 hours, cool to room temperature, filter, filter cake washes with water, vacuum-drying, obtains the compound G-4 ' of 1.3g, brown solid.
The preparation (method one) of embodiment 1, compound R Ir-AC-I-001
The methyl ethyl diketone of compound G-2 and 192mg (2mmol) of 1.406g (1mmol) and the anhydrous sodium carbonate of 1.038g (10mmol) are dispersed in the acetonitrile of 80ml and the chloroform of 80ml, under nitrogen protection, temperature rising reflux carries out substitution reaction 24 hours, cool to room temperature, reaction solution is poured into water, extract with DCM, organic phase is dry, filter, filtrate reduced in volume is done, residue by silicagel column separation and purification, obtains the compound R Ir-AC-I-001 of 650mg, yellow solid;
Experimental data:
(1)1HNMR(δ、C2D6SO)：0.8～1.0(23H,m)；1.0～1.3(10H,m)；1.3～1.7(15H,d)；1.7～2.0(7H,m)；3.2～3.5(6H,m)；5.2～5.5(1H,m)；6.0～6.2(2H,q)；6.2～6.5(4H,t)；7.0～7.2(2H,t)；7.2～7.8(15H,m)。Confirm that the material be obtained by reacting is compound R Ir-AC-I-001 really;
(2) second-order transition temperature (DSC): 270.44 DEG C;
(3) UV maximum absorption wavelength (DCM): 252nm, 303nm, 316nm;
(4) phosphorescent emissions wavelength (DCM): 520nm.
As from the foregoing, this product structure is correct, is target compound.
The preparation (method three) of embodiment 2, compound R Ir-AC-II-001
By the glycerine dispersed with stirring of compound 80ml shown in compound and 4.76g G-1 shown in 1.4g G-2, under nitrogen protection; be warming up to 180 DEG C; stirring and refluxing carries out substitution reaction 8 hours; cool to room temperature; reaction solution is poured in the 1M dilute hydrochloric acid of 200ml; suction filtration, filter cake wash with water, will obtain the separation and purification of solid silicagel column, obtain the RIr-AC-I-001 of 0.84g, white solid.
Experimental data:
(1)1HNMR(δ、C2D6SO)：0.8～1.0(35H,m)；1.0～1.3(15H,m)；1.3～1.7(21H,d)；1.7～2.0(11H,m)；6.0～6.2(5H,q)；6.2～6.5(7H,t)；7.0～7.2(3H,t)；7.2～7.8(20H,m)。Confirm that the material be obtained by reacting is compound R Ir-AC-II-001 really;
(2) second-order transition temperature (DSC): 264.3 DEG C;
(3) UV maximum absorption wavelength (DCM): 256nm, 314nm, 332nm;
(4) phosphorescent emissions wavelength (DCM): 532nm.
As from the foregoing, this product structure is correct, is target compound.
The preparation (method two) of embodiment 3, compound R Ir-AP-I-001
Isosorbide-5-Nitrae-the dioxane of the 2-pyridine carboxylic acid of 2.8g compound G-2 and 707mg, the Anhydrous potassium carbonate of 324mg and 50ml, temperature rising reflux stirs and carries out substitution reaction 8 hours, concentrating under reduced pressure is done, residue over silica gel column separating purification, obtains the compound R Ir-AP-I-001 of 1.4g, yellow solid.
Experimental data:
(1)1HNMR(δ、C2D6SO)：0.8～1.0(23H,m)；1.0～1.3(10H,m)；1.3～1.7(15H,d)；1.7～2.0(7H,m)；3.2～3.5(6H,m)；5.2～5.5(2H,m)；6.0～6.2(3H,q)；6.2～6.5(5H,t)；6.6～6.8(2H,m)7.0～7.2(3H,t)；7.2～7.8(17H,m)。Confirm that the material be obtained by reacting is compound R Ir-AP-I-001 really;
(2) second-order transition temperature (DSC): 268.6 DEG C;
(3) UV maximum absorption wavelength (DCM): 258nm, 307nm, 324nm;
(4) phosphorescent emissions wavelength (DCM): 512nm.
As from the foregoing, this product structure is correct, is target compound.
The preparation (method one) of embodiment 4, compound R Ir-AC-I-049
The methyl ethyl diketone of compound G-2-1 and 192mg (2mmol) of 1.284g (1mmol) and the anhydrous sodium carbonate of 1.038g (10mmol) are dispersed in the acetonitrile of 80ml and the chloroform of 80ml; under nitrogen protection; temperature rising reflux carries out substitution reaction 24 hours; cool to room temperature; reaction solution is poured into water; extract with DCM; organic phase is dry; filter; filtrate reduced in volume is done; residue by silicagel column separation and purification, obtains the compound R Ir-AC-I-049 of 500mg, yellow solid.
Experimental data:
(1)1HNMR(δ、C2D6SO)：0.8～1.0(23H,m)；1.0～1.3(7H,m)；1.3～1.7(12H,d)；1.7～2.0(5H,m)；3.0～3.5(12H,m)；5.2～5.5(1H,m)；6.0～6.2(2H,q)；6.2～6.5(4H,t)；6.7～7.2(5H,t)；7.2～7.8(9H,m)。Confirm that the material be obtained by reacting is compound R Ir-AC-I-049 really;
(2) second-order transition temperature (DSC): 294.2 DEG C;
(3) UV maximum absorption wavelength (DCM): 250nm, 300nm, 3165nm;
(4) phosphorescent emissions wavelength (DCM): 510nm.
The preparation (method three) of embodiment 5, compound R Ir-AC-II-049
By the glycerine dispersed with stirring of compound 80ml shown in compound and 4.76g G-1-1 shown in 1.284g G-2-1, under nitrogen protection; be warming up to 180 DEG C; stirring and refluxing carries out substitution reaction 8 hours; cool to room temperature; reaction solution is poured in the 1M dilute hydrochloric acid of 200ml; suction filtration, filter cake wash with water, will obtain the separation and purification of solid silicagel column, obtain the RIr-AC-I-049 of 0.74g, white solid.
Experimental data:
(1)1HNMR(δ、C2D6SO)：0.8～1.0(35H,m)；1.0～1.3(13H,m)；1.3～1.7(21H,d)；1.7～2.0(11H,m)；6.0～6.2(3H,q)；6.2～6.5(7H,t)；7.0～7.2(1H,t)；7.2～7.8(20H,m)。Confirm that the material be obtained by reacting is compound R Ir-AC-II-049 really;
(2) second-order transition temperature (DSC): 275.2 DEG C;
(3) UV maximum absorption wavelength (DCM): 266nm, 304nm, 335nm;
(4) phosphorescent emissions wavelength (DCM): 536nm.
The preparation (method two) of embodiment 6, compound R Ir-AP-I-049
The 2-pyridine carboxylic acid of 2.568g compound G-2-1 and 707mg, the Anhydrous potassium carbonate of 324mg and 1 of 50ml, 4-dioxane, temperature rising reflux stirs and carries out substitution reaction 8 hours, concentrating under reduced pressure is done, residue over silica gel column separating purification, obtain the compound R Ir-AP-I-049 of 1.4g, yellow solid.
Experimental data:
(1)1HNMR(δ、C2D6SO)：0.8～1.0(20H,m)；1.0～1.3(8H,m)；1.3～1.7(13H,d)；1.7～2.0(7H,m)；3.2～3.5(10H,m)；5.2～5.5(2H,m)；6.0～6.2(3H,q)；6.2～6.5(3H,t)；6.6～6.8(2H,m)7.0～7.2(3H,t)；7.2～7.8(7H,m)。Confirm that the material be obtained by reacting is compound R Ir-AP-I-049 really;
(2) second-order transition temperature (DSC): 285.6 DEG C;
(3) UV maximum absorption wavelength (DCM): 268nm, 317nm, 330nm;
(4) phosphorescent emissions wavelength (DCM): 526nm.
The preparation (method one) of embodiment 7, compound R Pt-AC-I-006
The anhydrous sodium carbonate of the methyl ethyl diketone and 334mg of getting compound G-4 ' 1.4g and 158mg is dispersed in the ethylene glycol ethyl ether of 20ml, under nitrogen protection, is warming up to 100 DEG C of stirring and refluxing and carries out substitution reaction 24 hours; cool to room temperature; filter, filter cake washes with water, then dissolves with DCM; filter; filtrate is dry, filters, and filtrate reduced in volume is done; obtain the compound R Pt-AC-I-006 of 320mg, dark yellow solid.
Experimental data:
(1)1HNMR(δ、C2D6SO)：0.8～1.0(12H,m)；1.0～1.3(6H,m)；1.3～1.7(8H,d)；1.7～2.0(4H,m)；3.2～3.5(3H,m)；5.2～5.5(1H,m)；6.0～6.2(2H,q)；6.2～6.5(2H,t)；7.0～7.2(2H,t)；7.2～7.8(7H,m)。Confirm that the material be obtained by reacting is compound R Pt-AC-I-001 really;
(2) second-order transition temperature (DSC): 243.5 DEG C;
(3) UV maximum absorption wavelength (DCM): 262nm, 313nm, 328nm;
(4) phosphorescent emissions wavelength (DCM): 530nm.
As from the foregoing, this product structure is correct, is target compound.
Embodiment 8, fabricate devices OLED-1, OLED-2, OLED-3
1) the glass substrate supersound process 30 minutes in clean-out system will ITO conductive layer being coated with, rinse in deionized water, in acetone/ethanol mixed solvent ultrasonic 30 minutes, be baked to complete drying under a clean environment, 10 minutes are irradiated with ultraviolet rays cleaning machine, and with low energy positively charged ion bundle bombarded surface.
2) the above-mentioned ito glass substrate handled well is placed in vacuum chamber, is evacuated to 1 × 10
-5~ 9 × 10
-3pa, above-mentioned anode tunic continues difference evaporation compound TDATA as hole injection layer, evaporation rate is 0.1nm/s, and evaporation thickness is 40nm;
Wherein, the structural formula of TDATA is as follows:
3) on above-mentioned hole injection layer, continuing evaporation NPB is hole transmission layer, and evaporation rate is 0.1nm/s, and evaporation thickness is 10nm;
Wherein, the structural formula of NPB is as follows:
4) on hole transmission layer, continue evaporation one deck embodiment 1 prepare compound R Ir-AC-I-001 and CBP shown in gained formula I as the organic luminous layer of device, the evaporation rate of compound R Ir-AC-I-001 and CBP is than being 1:100, the consumption of compound R Ir-AC-I-001 is 5% of CBP quality, evaporation rate is 0.1nm/s, and the thickness of evaporation gained organic luminous layer is 50nm;
5) on organic luminous layer, continue the electron transfer layer of evaporation one deck Alq3 material as device, evaporation rate is 0.1nm/s, and evaporation thickness is 20nm;
Wherein, the structural formula of Alq3 is as follows:
6) on electron transfer layer successively evaporation magnesium/ag alloy layer as the cathode layer of device, wherein the evaporation rate of magnesium/ag alloy layer is 2.0 ~ 3.0nm/s, evaporation thickness is 100nm, and the mass ratio of magnesium and silver is 10:1, obtains device OLED-1 provided by the invention.
According to upper identical step, only by step 4) RIr-AC-I-001 used replaces with RIr-AC-I-006, obtains OLED-2 provided by the invention;
According to upper identical step, only by step 4) RIr-AC-I-001 used replaces with RIr-AC-I-011, obtains OLED-3 provided by the invention.
The performance test results of obtained device OLED-1 to OLED-3 is as shown in table 1.
The performance test results of table 1, OLED-1 to OLED-3
Embodiment 9, fabricate devices OLED-4 ~ OLED-8
According to the step identical with embodiment 5, only by step 4) RIr-AC-I-001 used replaces with RIr-AC-II-001, obtains OLED-4 provided by the invention;
According to the step identical with embodiment 5, only by step 4) RIr-AC-I-001 used replaces with RIr-AC-II-006, obtains OLED-5 provided by the invention.
According to the step identical with embodiment 5, only by step 4) RIr-AC-I-001 used replaces with RIr-AC-II-008, obtains OLED-6 provided by the invention;
According to the step identical with embodiment 5, only by step 4) RIr-AC-I-001 used replaces with RIr-AC-II-011, obtains OLED-7 provided by the invention.
According to the step identical with embodiment 5, only by step 4) RIr-AC-I-001 used replaces with RIr-AC-II-019, obtains OLED-8 provided by the invention;
The performance test results of obtained device OLED-4 to OLED-8 is as shown in table 2.
The performance test results of table 2, OLED-4 to OLED-8
Embodiment 10, fabricate devices OLED-9 ~ OLED-11
According to the step identical with embodiment 5, only by step 4) RIr-AC-I-001 used replaces with RIr-AP-I-001, obtains OLED-9 provided by the invention;
According to the step identical with embodiment 5, only by step 4) RIr-AC-I-001 used replaces with RIr-AP-I-007, obtains OLED-10 provided by the invention.
According to the step identical with embodiment 5, only by step 4) RIr-AC-I-001 used replaces with RIr-AP-I-019, obtains OLED-11 provided by the invention;
The performance test results of obtained device OLED-9 to OLED-11 is as shown in table 3.
The performance test results of table 3, OLED-9 to OLED-11
As from the foregoing, utilize the organic electroluminescent of compound gained shown in formula I provided by the invention OLED, there is excellent luminous efficiency and device performance, there is important using value.
Claims (10)
1. compound shown in formula I,
In described formula I, R
1, R
2, R
3and R
4all be selected from H ,-F ,-Cl ,-Br ,-CN ,-CF
3,-OCF
3, any one in the aliphatic group of C1-C50 that replaces of the total number of carbon atoms alkyl that is 1-15, the total number of carbon atoms alkoxyl group that is 1-15, the total number of carbon atoms be the normal olefine base of 2-15, the total number of carbon atoms of fluoro is the alkyl of 1-15, the total number of carbon atoms of fluoro is the alkoxyl group of 1-15, the total number of carbon atoms of fluoro is 2-15 normal olefine base, trans-cycloh, phenylcyclohexyl, the aliphatic group of C1-C50 and cyclohexyl;
R
5be selected from the alkyl that the total number of carbon atoms is 1-15, the total number of carbon atoms is the alkoxyl group of 1-15, the total number of carbon atoms is the normal olefine base of 2-15, the total number of carbon atoms of fluoro is the alkyl of 1-15, the total number of carbon atoms of fluoro is the alkoxyl group of 1-15, the total number of carbon atoms of fluoro is the normal olefine base of 2-15, N-phenyl-carbazole-2-base, N-phenyl-carbazole-3-base, 9-anthryl, 1-naphthyl, 2-naphthyl, phenyl, 4-xenyl, 3-xenyl, 4-triphenylamine base, 2-pyrimidyl, 3-carbazyl, 3-pyridyl, 1, 3, 4-oxadiazole-2-base, dibenzo [b, d] furans-2-base, dibenzo [b, d] furans-4-base, dibenzo [b, d] thiophene-2-base and dibenzo [b, d] any one in thiophene-4-base,
X is 1,2 or 3;
Y is 0,1,2 or 3; And x is when being 3, y is 0;
M be selected from metal iridium and platinum any one; And M is when being platinum, x is not 3;
It is any one in the acetoacetyl of 5-25 that L is selected from acetylacetone based, 2-pyridine carboxylic acid base, 2-pyridine-sulfonic acid base, 2-phenylpyridyl and the total number of carbon atoms with side chain.
2. compound according to claim 1, is characterized in that: in described formula I, R
3for propylcyclohexyl phenyl or the own phenyl of propyl group dicyclo.
3. compound according to claim 1 and 2, is characterized in that: compound shown in described formula I is any one in compound shown in following RIr-AC-I, RPt-AC-I, RIr-AP-I, RPt-AP-I and RIr-AC-II:
In described RIr-AC-I, RPt-AC-I, RIr-AP-I, RPt-AP-I and RIr-AC-II, R
1to R
5definition identical with claim 1.
4. preparing a method for compound shown in formula I described in claim 3, is any one in following method one to method three;
Wherein, method one comprises the steps:
Will
in solvent, mix backflow with methyl ethyl diketone and alkali and carry out substitution reaction, react the complete x that obtains for compound shown in RIr-AC-I or RPt-AC-I of 1 or 2;
Described method two comprises the steps:
Will
in solvent, mix backflow with alkali and carry out substitution reaction, react the complete x that obtains for compound shown in RIr-AP-I or RPt-AP-I of 1 or 2;
Described method three comprises the steps:
Will
in solvent mixing carry out substitution reaction, react complete obtain x for 3 time RIr-AC-II shown in compound;
In described method one to three, R
1-R
5, M definition identical with the definition in claim 1.
5. method according to claim 4, is characterized in that: in described method one,
the mole dosage ratio that feeds intake of methyl ethyl diketone and alkali is 1:2-4:2-10; In described substitution reaction step, the time is 10-24 hour;
In described method two,
compare for 1:2-4:2-10 with the mole dosage that feeds intake of alkali; In described substitution reaction step, the time is 4-10 hour;
In described method three,
mass ratio be 1:3-4;
In described substitution reaction step, temperature is 170-190 DEG C; Time is 7-9 hour.
In described method one and method two, described alkali is all selected from least one in anhydrous sodium carbonate and Anhydrous potassium carbonate;
In described method one to three, described reaction is carried out all in an inert atmosphere;
Described solvent is all selected from least one in ethylene glycol ethyl ether, tetrahydrofuran (THF), normal hexane, toluene, ethanol, water, glycerine, Isosorbide-5-Nitrae-dioxane, acetonitrile and chloroform.
6. the luminescent material containing compound shown in the arbitrary described formula I of claim 1-3;
Shown in the arbitrary described formula I of claim 1-3, compound is preparing the application in luminescent material.
7. luminescent material according to claim 6 or application, is characterized in that: described luminescent material is organic electroluminescent phosphorescence luminescent material.
8. shown in the arbitrary described formula I of claim 1-3, compound is preparing the application in organic electroluminescence device as luminescent layer;
Containing the organic electroluminescence device of compound shown in the arbitrary described formula I of claim 1-3 as luminescent layer.
9. application according to claim 8 or organic electroluminescence device, is characterized in that: described organic electroluminescence device is organic electro-phosphorescent luminescent device;
Described organic electroluminescence device is specially the device of following structure:
Described organic electroluminescence device is made up of transparent substrate, anode layer, hole injection layer, hole transmission layer, organic luminous layer, electron transfer layer and cathode layer from the bottom to top successively;
Wherein, the material forming described transparent substrate is glass or flexible substrate;
The material forming described anode layer is inorganic materials or organic conductive polymer;
The material forming described hole injection layer is TDATA;
The structural formula of described TDATA is as follows:
The material forming described hole transmission layer is NPB;
The structural formula of described NPB is as follows:
The material forming described organic luminous layer is made up of compound shown in the arbitrary described formula I of claim 1-3 and material of main part;
Wherein, described material of main part be mCP, CBP, NATZ or
Wherein, the structural formula of mCP, CBP and NATZ is as follows:
The quality of compound shown in described formula I is the 1-10% of material of main part quality;
The material forming described electron transfer layer is Alq3, Gaq3, BPhen or TPBi;
Wherein, the structural formula of Alq3, Gaq3, BPhen and TPBi is as follows successively:
The material forming described cathode layer is selected from any one or any alloys of two kinds of compositions in following element or the fluorochemical of following element: lithium, magnesium, silver, calcium, strontium, aluminium, indium, copper, Jin Heyin.
10. application according to claim 9 or organic electroluminescence device, is characterized in that: the thickness of described hole injection layer is 30nm-50nm;
The thickness of described hole transmission layer is 5nm-15nm;
The thickness of described organic luminous layer is 10nm-100nm;
The thickness of described electron transfer layer is 10nm-30nm;
The thickness of described cathode layer is 90nm-110nm.
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