CN105481901A - Iridium-containing red metal complex, preparation method thereof, and organic electroluminescent device adopting complex - Google Patents
Iridium-containing red metal complex, preparation method thereof, and organic electroluminescent device adopting complex Download PDFInfo
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- CN105481901A CN105481901A CN201510874661.1A CN201510874661A CN105481901A CN 105481901 A CN105481901 A CN 105481901A CN 201510874661 A CN201510874661 A CN 201510874661A CN 105481901 A CN105481901 A CN 105481901A
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- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 51
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 38
- 238000005401 electroluminescence Methods 0.000 claims abstract description 23
- 125000003118 aryl group Chemical group 0.000 claims abstract description 20
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 17
- 125000003107 substituted aryl group Chemical group 0.000 claims abstract description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 118
- 238000000926 separation method Methods 0.000 claims description 71
- 150000001875 compounds Chemical class 0.000 claims description 70
- 238000000746 purification Methods 0.000 claims description 62
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 59
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 44
- 239000012074 organic phase Substances 0.000 claims description 43
- 239000002904 solvent Substances 0.000 claims description 43
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 229910052751 metal Inorganic materials 0.000 claims description 38
- 239000002184 metal Substances 0.000 claims description 38
- 238000001035 drying Methods 0.000 claims description 35
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 34
- 230000001681 protective effect Effects 0.000 claims description 34
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 33
- JYGXADMDTFJGBT-VWUMJDOOSA-N hydrocortisone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 JYGXADMDTFJGBT-VWUMJDOOSA-N 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 26
- 239000000376 reactant Substances 0.000 claims description 25
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 22
- 238000002347 injection Methods 0.000 claims description 20
- 239000007924 injection Substances 0.000 claims description 20
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- 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
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 17
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 16
- 229960000890 hydrocortisone Drugs 0.000 claims description 16
- 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 16
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 239000003480 eluent Substances 0.000 claims description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 14
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
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- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 11
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 11
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 claims description 11
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 11
- SYSZENVIJHPFNL-UHFFFAOYSA-N (alpha-D-mannosyl)7-beta-D-mannosyl-diacetylchitobiosyl-L-asparagine, isoform B (protein) Chemical compound COC1=CC=C(I)C=C1 SYSZENVIJHPFNL-UHFFFAOYSA-N 0.000 claims description 10
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 10
- JFZJMSDDOOAOIV-UHFFFAOYSA-N 2-chloro-5-(trifluoromethyl)pyridine Chemical compound FC(F)(F)C1=CC=C(Cl)N=C1 JFZJMSDDOOAOIV-UHFFFAOYSA-N 0.000 claims description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052794 bromium Inorganic materials 0.000 claims description 9
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 7
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 6
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 5
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 150000003233 pyrroles Chemical class 0.000 claims description 4
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- 125000002252 acyl group Chemical group 0.000 claims description 3
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- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims description 3
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 claims description 3
- 235000015320 potassium carbonate Nutrition 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
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- 229930192474 thiophene Natural products 0.000 claims description 3
- ZHXUWDPHUQHFOV-UHFFFAOYSA-N 2,5-dibromopyridine Chemical compound BrC1=CC=C(Br)N=C1 ZHXUWDPHUQHFOV-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- 238000003786 synthesis reaction Methods 0.000 abstract description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 239000012044 organic layer Substances 0.000 description 21
- 229910052757 nitrogen Inorganic materials 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 12
- 150000002220 fluorenes Chemical class 0.000 description 10
- 239000007795 chemical reaction product Substances 0.000 description 8
- 238000010898 silica gel chromatography Methods 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 7
- 239000004411 aluminium Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052754 neon Inorganic materials 0.000 description 6
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 6
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- 239000012153 distilled water Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 5
- 230000000903 blocking effect Effects 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- -1 separatory Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
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- 229910045601 alloy Inorganic materials 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
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- 239000011575 calcium Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
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- 238000001228 spectrum Methods 0.000 description 3
- DIVZFUBWFAOMCW-UHFFFAOYSA-N 4-n-(3-methylphenyl)-1-n,1-n-bis[4-(n-(3-methylphenyl)anilino)phenyl]-4-n-phenylbenzene-1,4-diamine Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 DIVZFUBWFAOMCW-UHFFFAOYSA-N 0.000 description 2
- 0 C*(C)c(cc1C(*)(*)c2c3)ccc1-c2ccc3N(c(cc1)ccc1OC)c(cc1)ccc1OC Chemical compound C*(C)c(cc1C(*)(*)c2c3)ccc1-c2ccc3N(c(cc1)ccc1OC)c(cc1)ccc1OC 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
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- 238000007738 vacuum evaporation Methods 0.000 description 2
- DXLHOCYBTWOELM-UHFFFAOYSA-N 9,9-diethylfluorene Chemical class C1=CC=C2C(CC)(CC)C3=CC=CC=C3C2=C1 DXLHOCYBTWOELM-UHFFFAOYSA-N 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
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- 150000003624 transition metals Chemical class 0.000 description 1
- MJRFDVWKTFJAPF-UHFFFAOYSA-K trichloroiridium;hydrate Chemical compound O.Cl[Ir](Cl)Cl MJRFDVWKTFJAPF-UHFFFAOYSA-K 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
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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
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- C—CHEMISTRY; METALLURGY
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Abstract
The present invention relates to a kind of metal complex of feux rouges containing iridium, preparation method and using the organic electroluminescence device of the complex. Wherein this contains iridium feux rouges metal complex, has the following structure:
Wherein R is alkyl, aryl, substituted aryl, heterocyclic aryl or substituted heterocycle aryl. For the metal complex of feux rouges containing iridium of the invention compared with existing phosphor material, light, the thermal stability of material are high, can be with long-term preservation; Luminescence generated by light and electroluminescent efficiency are high; Synthesis technology is simple, low in cost, is the feux rouges phosphor material of function admirable.
Description
Technical field
The invention belongs to electroluminescent organic material technical field, be specifically related to a kind of containing iridium ruddiness metal complexes, preparation method and the organic electroluminescence device adopting this title complex.
Background technology
Organic electroluminescence device (OrganicLight-EmittingDiodes, OLED) owing to having, brightness is high, driving voltage is low, lightweight, can be used for large area flexible indicating meter preparation and fabrication low cost and other advantages, be subject to the extensive concern of academia and industrial community, become the first-selection of following technique of display.
According to the difference of principle of luminosity, electroluminescent organic material can be divided into the large class of fluorescence and phosphorescence two.Because phosphor material can utilize singlet and triplet excitons simultaneously, the internal quantum efficiency of device can be made in theory to reach 100%.Therefore, transition metal complex is widely used in the high efficiency organic electroluminescence device of preparation.Wherein, complex of iridium is particularly important, because it has suitable triplet lifetime and high luminous efficiency, and by can realize the luminescence of different wave length to the adjustment of the first and second parts.
Meanwhile, phosphor material physical doping is prepared organic luminescent device in the polymer also to receive much concern.Because on the one hand, which make use of the machinable advantage of polymers soln, and can pass through spin coating, silk screen printing, the low cost process such as spray ink Printing carry out fabricate devices, avoid the shortcoming that small molecule material needs the contour cost process of vacuum evaporation; On the other hand, make use of again the advantage that phosphor material can realize high-luminous-efficiency, thus the luminous efficiency of device can be improved.
The phosphor material be used in white light OLED s has indigo plant, green, red three primary colors.Wherein, for preparing gratifying white light OLED s, the red dye of solution processable is essential.At present, the red dye of efficient solution processing is very rare, limits the development of ruddiness OLEDs and white light OLED s.
Therefore, developing the ruddiness phosphorescent coloring that can improve organic electroluminescence device luminescent properties is the megatrend expanding now red light material research field.
Summary of the invention
In order to solve the technical problem existed in prior art, the object of the present invention is to provide a kind of containing iridium ruddiness metal complexes, preparation method and the organic electroluminescence device adopting this title complex.
In order to solve the problems of the technologies described above, technical scheme of the present invention is specific as follows:
A kind of containing iridium ruddiness metal complexes, there is following structure:
Wherein R is alkyl, aryl, substituted aryl, heterocyclic aryl or substituted heterocycle aryl.
In technique scheme,
Described aryl is benzene, biphenyl, naphthalene, anthracene, phenanthrene, Bi Huo perylene;
Described heterocyclic aryl is pyrroles, pyridine, furans, thiophene or carbazole;
The substituting group of described substituted aryl or substituted heterocycle aryl is halogen atom, alkyl, alkoxyl group, amino, ester group, boric acid ester group, acyl group, amide group, cyano group, aryloxy, aromatic base or heterocyclic substituent; Substituent replacement number is one or more.
The above-mentioned preparation method containing iridium ruddiness metal complexes, comprises the steps:
(1) in protective gas atmosphere, be dissolved in dimethyl sulfoxide (DMSO) by 2-bromine fluorenes and Tetrabutyl amonium bromide, the mass ratio adding sodium hydroxide and water is the aqueous sodium hydroxide solution of 1:1 ~ 3, adds compd A, react 6 ~ 24 hours, after separation and purification, obtain compd B; Wherein, the structural formula of compd A is: R-Br, and the structural formula of compd B is
r is alkyl, aryl, substituted aryl, heterocyclic aryl or substituted heterocycle aryl;
(2) dissolved in glacial acetic acid by compd B, slowly drip nitrosonitric acid, cooling bath reaction 3 ~ 24 hours, obtain Compound C after separation and purification, the structural formula of Compound C is
(3) under room temperature, Compound C is dissolved in the mixed solvent of tetrahydrofuran (THF) and ethanol, the volume ratio of tetrahydrofuran (THF) and ethanol is 1:1 ~ 4, add Pd/carbon catalyst, be heated to 60 ~ 70 DEG C, drip hydrazine hydrate, reacting by heating 3 ~ 24 hours, obtain Compound D after separation and purification, the structural formula of Compound D is
(4) in protective gas atmosphere; be that Compound D and the 4-iodanisol of 1:2.1 ~ 3.0 is dissolved in p-Xylol by mol ratio; add cuprous iodide/phenanthroline as catalyzer; add potassium hydroxide; be heated to 100 ~ 145 DEG C of reactions 36 ~ 48 hours; obtain compd E after separation and purification, the structural formula of compd E is
(5) in protective gas atmosphere, compd E is dissolved in tetrahydrofuran (THF) (THF), at-78 DEG C, add n-Butyl Lithium, react 40 ~ 60 minutes, add trimethyl borate, react 4 ~ 12 hours under room temperature, add hydrochloric acid afterwards and make solution be acid; Obtain compound F 17-hydroxy-corticosterone after separation and purification, the structural formula of compound F 17-hydroxy-corticosterone is
(6) in protective gas atmosphere; be that 2-chloro-5-trifluoromethylpyridine and the compound F 17-hydroxy-corticosterone of 1:1.1 ~ 2.0 is dissolved in the first solvent by mol ratio; add the aqueous solution of organic palladium catalyzer and carbonate; carry out Suzuki linked reaction 8 ~ 24h; obtain compound G after separation and purification, the structural formula of compound is
(7) in protective gas atmosphere, be that described compound G and three hydrated iridium trichloride of 2 ~ 3:1 are dissolved in the second solvent by mol ratio, react 12 ~ 24 hours at 70 ~ 90 DEG C, obtain compound H after separation and purification, the structural formula of described compound H is
(8) in protective gas atmosphere; be that compound H and the methyl ethyl diketone of 1:3 ~ 5 is dissolved in the 3rd solvent by mol ratio; add sodium carbonate; react 12 ~ 24 hours at being heated to 70 ~ 90 DEG C; obtain ruddiness phosphorescent metal complex after separation and purification, the structural formula of described ruddiness phosphorescent iridium metal complexes is
In described step (1), reactant consumption molfraction meter is: 2-bromine fluorenes is 1 part, and compd A is 2.1 ~ 3 parts, and Tetrabutyl amonium bromide is 0.02 ~ 0.1 part, and aqueous sodium hydroxide solution is 5 ~ 15 parts, and dimethyl sulfoxide (DMSO) is 2 ~ 5 parts;
In described step (2), reactant consumption molfraction meter is: compd B is 1 part, and nitrosonitric acid is 3 ~ 10 parts, and Glacial acetic acid is 2 ~ 50 parts;
In described step (3), reactant consumption molfraction meter is: Compound C is 1 part, and hydrazine hydrate is 1.1 ~ 5 parts, and Pd/carbon catalyst is 0.05 ~ 0.15 part, and the mixed solution of tetrahydrofuran (THF) and ethanol is 2 ~ 50 parts;
In described step (4), reactant consumption molfraction meter is: Compound D is 1 part, and 4-iodanisol is 2.1 ~ 3 parts, cuprous iodide is 0.1 ~ 0.2 part, phenanthroline is 0.2 ~ 0.4 part, and potassium hydroxide is 7 ~ 10 parts, and p-Xylol is 2 ~ 50 parts;
In described step (5), reactant consumption molfraction meter is: compd E is 1 part, and n-Butyl Lithium is 1.1 ~ 1.5 parts, and trimethyl borate is 3 ~ 8 parts, and tetrahydrofuran (THF) is 2 ~ 50 parts.
In technique scheme,
The first solvent in described step (6) is toluene or tetrahydrofuran (THF);
The second solvent in described step (7) is the mixture of cellosolvo and water, and the volume ratio of described cellosolvo and water is 3:1;
The 3rd solvent in described step (8) is cellosolvo.
In technique scheme, described organic palladium catalyzer is tetra-triphenylphosphine palladium; The mol ratio of described organic palladium catalyzer and described compound F 17-hydroxy-corticosterone and 2-chloro-5-trifluoromethylpyridine is 3:100-5:100.
In technique scheme, described carbonate is at least one in salt of wormwood and sodium carbonate.
In technique scheme, the concrete grammar obtaining ruddiness phosphorescent iridium metal complexes in step (8) after separation and purification is:
After reaction terminates, reaction solution is chilled to room temperature, removes at least part of 3rd solvent, with dichloromethane extraction, organic phases washed with water three times, with anhydrous magnesium sulfate drying, filters organic phase, solvent in removing organic phase obtains solid crude product, be eluent with methylene dichloride and sherwood oil, crude product purified by silica gel pillar layer separation is purified, except desolventizing, after drying, the mixed solution re-using methylene dichloride and methyl alcohol carries out recrystallization and obtains the ruddiness phosphorescent iridium metal complexes after purifying.
Adopt the organic electroluminescence device of above-mentioned title complex, comprising:
Substrate;
Be arranged at the anode on described substrate;
Be arranged at the organic layer on described anode, the number of organic layer is more than or equal to two, and the one deck in organic layer is luminescent layer, and electron injection/transport layer is on luminescent layer;
Be arranged at the negative electrode in electron injection/transport layer;
The material of described luminescent layer comprises: light emitting host material and the light emitting guest material be doped in light emitting host material; Described light emitting guest material is above-mentioned containing iridium ruddiness metal complexes.
In technique scheme, the thickness of described electron injection/transport layer is 0.1 ~ 100nm; The thickness of described substrate is 0.3 ~ 0.7mm.
In technique scheme, the thickness of described electron injection/transport layer is 50nm.
The present invention has following beneficial effect:
The iridium ruddiness metal complexes that contains of the present invention is compared with existing phosphor material, and the present invention has following technique effect:
1, the light of material, thermostability are high, can preserve for a long time.
2, photoluminescence and electroluminescent efficiency high.
3, synthesis technique is simple, with low cost, is the ruddiness phosphor material of excellent property.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Fig. 1 is the preparation method's schematic diagram containing iridium ruddiness metal complexes that the present invention relates to;
Fig. 2 is the electroluminescent spectrum that the red phosphorescent two [9,9-diethyl-7-(5-5-flumethiazine base) fluorenes] [N, N-(4-p-methoxy-phenyl) amine-N, C] (methyl ethyl diketone) of embodiment 1 closes complex of iridium;
Fig. 3 is the current density-brightness-voltage characteristic figure of the organic electroluminescence device of embodiment 5;
Fig. 4 is the luminance-current efficiency figure of the organic electroluminescence device of embodiment 5.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in detail.
The present invention characterizes the structure of material by nucleus magnetic resonance, mass spectrum etc., and the method for studied the photophysical property of these title complexs under solution state in great detail by ultraviolet-visible and fluorescence emission spectrum, being processed by solution has carried out device simulation.
Containing a preparation method for iridium ruddiness metal complexes, comprise the following steps:
(1) in protective gas atmosphere; 2-bromine fluorenes and Tetrabutyl amonium bromide are dissolved in dimethyl sulfoxide (DMSO); add the aqueous sodium hydroxide solution (mass ratio of sodium hydroxide and water is 1:1 ~ 3) of newly joining; add compd A; react 6 ~ 24 hours; obtain compd B after separation and purification, the structural formula of compd A is: R-Br, and the structural formula of compd B is
wherein R is alkyl, aryl, substituted aryl, heterocyclic aryl or substituted heterocycle aryl.
Protective gas is argon gas, nitrogen or neon.
In described step (1), reactant consumption molfraction meter is: 2-bromine fluorenes is 1 part, and compd A is 2.1 ~ 3 parts, and Tetrabutyl amonium bromide is 0.02 ~ 0.1 part, and the aqueous sodium hydroxide solution of new preparation is 5 ~ 15 parts, and dimethyl sulfoxide (DMSO) is 2 ~ 5 parts.
Obtain after separation and purification in the step of compd B, the method of separation and purification is specially: after reaction terminates, be extracted with ethyl acetate, organic phase massive laundering three times, with anhydrous magnesium sulfate drying, filter organic phase, solvent in removing organic phase obtains faint yellow solid crude product, is eluent, is purified by crude product purified by silica gel pillar layer separation with sherwood oil, except desolventizing, after drying, obtain the compd B after purifying.
Be appreciated that the method for separation and purification is not limited to aforesaid method, the method for separation and purification can be carried out to above-mentioned reaction product all passable.
(2) under ventilation condition, dissolved in glacial acetic acid by compd B, slowly drip nitrosonitric acid, cooling bath reaction 3 ~ 24 hours, obtain Compound C after separation and purification, the structural formula of Compound C is
Wherein R is alkyl, aryl, substituted aryl, heterocyclic aryl or substituted heterocycle aryl.
In described step (2), reactant consumption molfraction meter is: compd B is 1 part, and nitrosonitric acid is 3 ~ 10 parts, and Glacial acetic acid is 2 ~ 50 parts.
Obtain after separation and purification in the step of Compound C, the method for separation and purification is specially: after reaction terminates, in reaction solution, add sodium carbonate, make reaction solution alkalize, be extracted with ethyl acetate, organic phases washed with water three times, with anhydrous magnesium sulfate drying, filter organic phase, solvent in removing organic phase obtains faint yellow solid crude product, is eluent, is purified by crude product purified by silica gel pillar layer separation with methylene dichloride/sherwood oil, except desolventizing, after drying, obtain the Compound C after purifying.
Be appreciated that the method for separation and purification is not limited to aforesaid method, the method for separation and purification can be carried out to above-mentioned reaction product all passable.
(3) under room temperature, Compound C is dissolved in the mixed solvent of tetrahydrofuran (THF) and ethanol, the volume ratio of tetrahydrofuran (THF) and ethanol is 1:1 ~ 4, add Pd/carbon catalyst, be heated to 60 ~ 70 DEG C, drip hydrazine hydrate, reacting by heating 3 ~ 24 hours, obtain Compound D after separation and purification, the structural formula of Compound D is
Wherein R is alkyl, aryl, substituted aryl, heterocyclic aryl or substituted heterocycle aryl.
In described step (3), reactant consumption molfraction meter is: Compound C is 1 part, and hydrazine hydrate is 1.1 ~ 5 parts, and Pd/carbon catalyst is 0.05 ~ 0.15 part, and the mixed solution of tetrahydrofuran (THF) and ethanol is 2 ~ 50 parts.
Obtain after separation and purification in the step of Compound D, the method of separation and purification is specially: after reaction terminates, be extracted with ethyl acetate, organic phase massive laundering three times, with anhydrous magnesium sulfate drying, filter organic phase, solvent in removing organic phase obtains brown crude product, is eluent, is purified by crude product purified by silica gel pillar layer separation with methylene dichloride/sherwood oil, except desolventizing, after drying, obtain the Compound D after purifying.
Be appreciated that the method for separation and purification is not limited to aforesaid method, the method for separation and purification can be carried out to above-mentioned reaction product all passable.
(4) in protective gas atmosphere; be that Compound D and the 4-iodanisol of 1:2.1 ~ 3.0 is dissolved in p-Xylol by mol ratio; add cuprous iodide/phenanthroline as catalyzer; add potassium hydroxide; be heated to 100 ~ 145 DEG C of reactions 36 ~ 48 hours; obtain compd E after separation and purification, the structural formula of compd E is
Wherein R is alkyl, aryl, substituted aryl, heterocyclic aryl or substituted heterocycle aryl.
Protective gas is argon gas, nitrogen or neon.
In described step (4), reactant consumption molfraction meter is: Compound D is 1 part, and 4-iodanisol is 2.1 ~ 3 parts, cuprous iodide is 0.1 ~ 0.2 part, phenanthroline is 0.2 ~ 0.4 part, and potassium hydroxide is 7 ~ 10 parts, and p-Xylol is 2 ~ 50 parts.
Obtain after separation and purification in the step of compd E, the method for separation and purification is specially: after reaction terminates, be chilled to room temperature, add a small amount of Glacial acetic acid, with toluene extraction, organic phase aqueous sodium carbonate washes three times, wash three times again with water, with anhydrous magnesium sulfate drying, filter organic phase, the solvent in removing organic phase obtains solid crude product, be eluent with methylene dichloride/sherwood oil, crude product purified by silica gel pillar layer separation is purified, except desolventizing, after drying, obtains the compd E after purifying.
Be appreciated that the method for separation and purification is not limited to aforesaid method, the method for separation and purification can be carried out to above-mentioned reaction product all passable.
(5) in protective gas atmosphere, compd E is dissolved in tetrahydrofuran (THF) (THF), at-78 DEG C; add n-Butyl Lithium, react 40 ~ 60 minutes, add trimethyl borate; react 4 ~ 12 hours under room temperature, add hydrochloric acid afterwards and make solution be acid.Obtain compound F 17-hydroxy-corticosterone after separation and purification, the structural formula of compound F 17-hydroxy-corticosterone is
Wherein R is alkyl, aryl, substituted aryl, heterocyclic aryl or substituted heterocycle aryl.
Protective gas is argon gas, nitrogen or neon.
In described step (5), reactant consumption molfraction meter is: compd E is 1 part, and n-Butyl Lithium is 1.1 ~ 1.5 parts, and trimethyl borate is 3 ~ 8 parts, and tetrahydrofuran (THF) is 2 ~ 50 parts.
Obtain after separation and purification in the step of compound F 17-hydroxy-corticosterone, the method of separation and purification is specially: after reaction terminates, by extracted with diethyl ether, organic phases washed with water three times, with anhydrous magnesium sulfate drying, filters organic phase, solvent in removing organic phase obtains solid crude product, by petroleum ether three times, except desolventizing, after drying, obtain the compound F 17-hydroxy-corticosterone after purifying.
Be appreciated that the method for separation and purification is not limited to aforesaid method, the method for separation and purification can be carried out to above-mentioned reaction product all passable.
(6) in protective gas atmosphere; be that 2-chloro-5-trifluoromethylpyridine and the compound F 17-hydroxy-corticosterone of 1:1.1 ~ 2.0 is dissolved in the first solvent by mol ratio; add the aqueous solution of organic palladium catalyzer and carbonate; carry out Suzuki linked reaction 8 ~ 24h; obtain compound G after separation and purification, the structural formula of compound G is
Wherein R is alkyl, aryl, substituted aryl, heterocyclic aryl or substituted heterocycle aryl.
Protective gas is argon gas, nitrogen or neon.
First solvent is toluene or tetrahydrofuran (THF) (THF).The consumption of the first solvent is fully dissolved as suitable to make compound F 17-hydroxy-corticosterone and 2-chloro-5-trifluoromethylpyridine.
Organic palladium catalyzer is tetra-triphenylphosphine palladium (Pd (PPh
3)
4), preferably, the mol ratio of described organic palladium catalyzer and described compound F 17-hydroxy-corticosterone and 2-chloro-5-trifluoromethylpyridine is 3:100-5:100.
The aqueous solution of carbonate is sodium carbonate or salt of wormwood.The mol ratio of carbonate is 3-5 times of 2-chloro-5-trifluoromethylpyridine.
The method that separation and purification obtains compound G is specially: after reaction terminates, be chilled to room temperature, be extracted with ethyl acetate, organic phase washed with water three times, by organic phase anhydrous magnesium sulfate drying, filter organic phase, solvent in removing organic phase obtains solid product, with sherwood oil/methylene dichloride for eluent, uses silica gel column chromatography separating-purifying, except desolventizing, after drying, obtain the compound G after purifying.
Be appreciated that the method for separation and purification is not limited to aforesaid method, the method for separation and purification can be carried out to above-mentioned reaction product all passable.
(7) in protective gas atmosphere, be that described compound G and three hydrated iridium trichloride of 2 ~ 3:1 are dissolved in the second solvent by mol ratio, react 12 ~ 24 hours at 70 ~ 90 DEG C, obtain compound H after separation and purification, the structural formula of described compound H is
Wherein R is alkyl, aryl, substituted aryl, heterocyclic aryl or substituted heterocycle aryl.
Protective gas is argon gas, nitrogen or neon.
Second solvent is the mixture of cellosolvo and water, and the volume ratio of cellosolvo and water is 3:1.The consumption of the second solvent is dissolved as suitable to make compound G and three hydrated iridium trichloride.
After reaction terminates, reaction solution is chilled to room temperature, adds precipitating after water, collects solid, described solid is used distilled water and methanol wash successively after filtration, obtains the compound H after purifying after drying.
Be appreciated that the method for separation and purification is not limited to aforesaid method, the method for separation and purification can be carried out to above-mentioned reaction product all passable.
(8) in protective gas atmosphere; be that compound H and the methyl ethyl diketone of 1:3 ~ 5 is dissolved in the 3rd solvent by mol ratio; add sodium carbonate; react 12 ~ 24 hours at being heated to 70 ~ 90 DEG C; obtain ruddiness phosphorescent metal complex after separation and purification, the structural formula of described ruddiness phosphorescent iridium metal complexes is
Wherein R is alkyl, aryl, substituted aryl, heterocyclic aryl or substituted heterocycle aryl.
Protective gas is argon gas, nitrogen or neon.
3rd solvent is cellosolvo.The consumption of the 3rd solvent is suitable to make compound H and methyl ethyl diketone be dissolved as.
The molar weight of the sodium carbonate added is 5 ~ 10 times of compound H.
The method of separation and purification is: after reaction terminates, reaction solution is chilled to room temperature, and remove portion the 3rd solvent, with dichloromethane extraction, organic phase washed with water three times, by organic phase anhydrous magnesium sulfate drying, filter organic phase, the solvent in removing organic phase obtains red solid, with sherwood oil/methylene dichloride for eluent, use silica gel column chromatography separating-purifying, except desolventizing, the mixed solution re-using methylene dichloride and methyl alcohol after drying carries out recrystallization and obtains the ruddiness phosphorescent iridium metal complexes after purifying.
Be appreciated that the method for separation and purification is not limited to aforesaid method, the method for separation and purification can be carried out to above-mentioned reaction product all passable.
The above-mentioned synthetic route containing iridium ruddiness metal complexes as shown in Figure 1.
Above-mentioned preparation method's reaction conditions containing iridium ruddiness metal complexes is gentle, and lower to equipment requirements, preparation cost is low, is conducive to scale operation.
Adopt this to contain the organic electroluminescence device of iridium ruddiness metal complexes, comprising:
Substrate;
Be arranged at the anode on described substrate;
Be arranged at the organic layer on described anode, the number of organic layer is more than or equal to two, and the one deck in organic layer is luminescent layer, and electron injection/transport layer is on luminescent layer
Be arranged at the negative electrode in electron injection/transport layer.
Described organic electro luminescent layer just comprises compound described above.
The present invention does not have particular requirement to described substrate, and be preferably glass or plastics, the thickness of described substrate is 0.3 ~ 0.7mm.According to the present invention, described anode is the material being easy to hole transport, is preferably conducting metal or conducting metal oxide, is more preferably indium tin oxide.
Described organic layer can be multilayer, has at least one deck to comprise compound described in technique scheme in described luminescent layer.Described can as dyestuff containing iridium ruddiness metal complexes, and carry out doping with material of main part and be configured with organic electroluminescent layer, the present invention is not particularly limited described material of main part, selects according to material well known to those skilled in the art.
After described organic layer is formed, form electron injection/transport layer in its surface.The generation type of the present invention to described electron injection/transport layer is not particularly limited, according to method well known to those skilled in the art.The mode spin-coating film can processed by solution.The material of described electron injection/transport layer is not particularly limited, according to material well known to those skilled in the art.
Described negative electrode preferable alloy, includes but not limited to calcium, magnesium, barium, aluminium and silver, is preferably aluminium.
In order to improve performance and the efficiency of device, the organic layer between described anode and organic electro luminescent layer preferably also comprises hole injection layer, hole transmission layer and electronic barrier layer; Organic layer between described negative electrode and organic electro luminescent layer preferably also comprises hole blocking layer.The present invention does not have particular requirement to the material of described hole injection layer, hole transmission layer, electronic barrier layer and hole blocking layer and thickness, can select according to material well known to those skilled in the art and thickness.
The preparation method of the present invention to described organic electroluminescence device is not particularly limited, and can carry out in accordance with the following methods:
Form anode over the substrate;
Described anode is formed multilayer organic layer, and wherein one deck is luminescent layer, is hole blocking layer above luminescent layer.
Described organic layer forms negative electrode.
In the described organic electroluminescence device of preparation, form anode first over the substrate, the present invention is not particularly limited generation type, according to method well known to those skilled in the art.Invention does not have particular requirement to described substrate, and be preferably glass or plastics, the thickness of described substrate is 0.3 ~ 0.7mm.According to the present invention, described anode is the material being easy to hole transport, is preferably conducting metal or conducting metal oxide, is more preferably indium tin oxide.
After obtaining anode, described anode forms organic layer.Luminescent layer in described organic layer comprises the compound described in such scheme.The generation type of the present invention to the organic layer below described luminescent layer and luminescent layer is not particularly limited, and can be formed by solution spin coating, spray ink Printing, offset printing or stereosopic printing on anode.After described organic luminous layer is formed, hole blocking layer and electron injection/transport layer can be formed by the mode of vacuum evaporation or spin coating from the teeth outwards.The preferred thickness of described electron injection/transport layer is 0.1 ~ 100nm, is more preferably 50 ~ 100nm.
Described organic layer prepares negative electrode after having prepared in its surface, and the anticathode preparation method of the present invention is not particularly limited, and is preferably method well known to those skilled in the art, includes but not limited to deposition.Described negative electrode preferable alloy, includes but not limited to calcium, magnesium, barium, aluminium and silver, is preferably aluminium.
In order to understand the present invention further, be described below in conjunction with embodiment.Protection scope of the present invention is not limited by the following examples.
It is below specific embodiment.
Embodiment 1 ruddiness phosphorescent iridium complex two [9,9-diethyl-7-(5-5-flumethiazine base) fluorenes] [N, N-(4-p-methoxy-phenyl) amine N, C] (methyl ethyl diketone) close complex of iridium (containing iridium ruddiness metal complexes) and preparation method thereof.
The structural formula that ruddiness phosphorescent iridium complex two [9,9-diethyl-7-(5-5-flumethiazine base) fluorenes] [N, N-(4-p-methoxy-phenyl) amine N, C] (methyl ethyl diketone) closes complex of iridium is as follows:
(1) synthesis of bromo-9, the 9-diethyl fluorenes of 2-
Under argon shield; 5.0g2-bromine fluorenes is dissolved in 10mL dimethyl sulfoxide (DMSO) (DMSO); add 0.26g Tetrabutyl amonium bromide (TBABr) again; add the sodium hydroxide solution (mass ratio of sodium hydroxide and water is 1:1) that 10mL newly prepares; after mixing; add 4.8mL monobromethane, react 8 hours at 75 DEG C.After reaction terminates, be chilled to room temperature, be extracted with ethyl acetate, separatory, organic phase massive laundering three times, with anhydrous magnesium sulfate drying, filters organic phase, after being spin-dried for, be that eluent carries out silica gel column chromatography separation with sherwood oil, after drying solid 5.7g, productive rate is 93%.
(2) synthesis of bromo-9, the 9-diethyl fluorenes of 2-nitro-7-
Bromo-for the 2-of 3.5g 9,9-diethyl fluorenes are dissolved in the Glacial acetic acid of 30mL, slowly drip the nitrosonitric acid of 2.8mL, react 4 hours under cooling bath condition.After having reacted, add sodium carbonate and finally make solution alkaline, be extracted with ethyl acetate afterwards, separatory, organic phases washed with water three times, with anhydrous magnesium sulfate drying, filtering organic phase, after being spin-dried for, is that eluent carries out silica gel column chromatography separation with methylene dichloride/sherwood oil, obtain light yellow solid 3.2g after drying, productive rate is 80%.
(3) synthesis of bromo-9, the 9-diethyl fluorenes of 2-amino-7-
Be dissolved in the mixed solution of tetrahydrofuran (THF) and ethanol by bromo-for 3.5g2-nitro-7-9,9-diethyl fluorenes, tetrahydrofuran (THF) is 35mL, ethanol is 20mL, adds 0.35g Pd/carbon catalyst, slowly drips the hydrazine hydrate of 16mL when being heated to 70 DEG C, after dripping off, react 12 hours.After reaction terminates, be chilled to room temperature, by extracted with diethyl ether, separatory, organic phases washed with water three times, organic phase anhydrous magnesium sulfate drying, filters organic phase, after being spin-dried for, carry out silica gel chromatography separation with methylene dichloride/sherwood oil as eluent, obtain reddish-brown oily liquids 2.2g after drying, productive rate is 69%.
(4) bromo-9, the 9-diethyl fluorenes-N of 7-, the synthesis of N-4-methoxy diphenylamine
Under argon shield, by melt and dissolved in 30mL p-Xylol to bromo-for 1.8g2-amino-7-9,9-diethyl fluorenes, 3.3g4-iodanisol, 0.11g cuprous iodide, 0.22g phenanthroline and 2.2g potassium hydroxide, vigorous stirring, 100 DEG C are reacted 36 hours.After reaction terminates, be chilled to room temperature, add 25mL Glacial acetic acid, extract with toluene, separatory, organic phase aqueous sodium carbonate washes three times, then washes three times with water, organic phase anhydrous magnesium sulfate drying, filter organic phase, after being spin-dried for, carry out silica gel chromatography separation with methylene dichloride/sherwood oil as eluent, obtain solid 1.6g after drying, productive rate is 53%.
(5) synthesis of N, N-4-methoxy diphenylamine base-9,9-diethyl fluorenes boric acid
Under argon shield, by bromo-for 2.0g7-9,9-diethyl fluorenes-N; N-4-methoxy diphenylamine is dissolved in the tetrahydrofuran (THF) of 30mL drying, at-78 DEG C, adds the n-Butyl Lithium of 2.4mL; react 1 hour, add the trimethyl borate of 2.1mL afterwards, react 4 hours under room temperature.After reaction terminates, the hydrochloric acid adding 2mol/L makes solution be acid, by extracted with diethyl ether, and separatory, organic phases washed with water three times, organic phase anhydrous magnesium sulfate drying, filters organic phase, after being spin-dried for, by petroleum ether three times, without the need to further purification, can directly be used as next step reaction.Obtain white solid 1.8g after drying, productive rate is 97%.
(6) synthesis of [9,9-diethyl-7-(5-5-flumethiazine base) fluorenes] [N, N-(4-p-methoxy-phenyl)] amine
Under argon shield; by 0.49g2-chloro-5-trifluoromethylpyridine, 2.gN; the solution of potassium carbonate of N-4-methoxy diphenylamine base-9,9-diethyl fluorenes boric acid, 0.1g tetra-triphenylphosphine palladium and 9mL2mol/L joins in 50mL toluene, stirring reaction 24 hours at 110 DEG C.After having reacted, be extracted with ethyl acetate, separatory, be washed to neutrality, anhydrous magnesium sulfate drying.Filtering, after being spin-dried for, is that eluent carries out silica gel column chromatography separation with sherwood oil/methylene dichloride, obtains greenish yellow solid 1.0g, productive rate 63% after drying.
(7) [9,9-diethyl-7-(5-5-flumethiazine base) fluorenes] [N, N-(4-p-methoxy-phenyl)] amine that part is contains the dimeric synthesis of iridium dichloro
Under argon shield; 0.1g tri-chloride hydrate iridium; 0.5g part [9; 9-diethyl-7-(5-5-flumethiazine base) fluorenes] [N; N-(4-p-methoxy-phenyl)] amine is dissolved in the mixed solution (volume ratio of cellosolvo and water is 3:1) of 6mL2-ethoxy ethanol and water, stirring reaction 24 hours at 80 DEG C.After being chilled to room temperature, rotating and boil off partial solvent, add appropriate distilled water, filter.Solid uses distilled water, methanol wash successively, and obtain solid 0.48g after drying, yield is 72%.Dipolymer, without the need to further purification, can directly drop in next step reaction.
(8) two [9,9-diethyl-7-(5-5-flumethiazine base) fluorenes] [N, N-(4-p-methoxy-phenyl) amine N, C] (methyl ethyl diketone) closes the synthesis of complex of iridium
Under argon shield; 0.48g part is [9; 9-diethyl-7-(5-5-flumethiazine base) fluorenes] [N; N-(4-p-methoxy-phenyl)] amine be dissolved in 6mL2-ethoxy ethanol containing iridium dichloro dimer and 0.1g methyl ethyl diketone; add 0.2g sodium carbonate, stirring reaction 18 hours at 80 DEG C.After being chilled to room temperature, remove portion solvent, adds appropriate distilled water, with dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying, solvent in removing organic phase obtains red solid, with sherwood oil/methylene dichloride (volume ratio is for 1:1) for eluent, uses silica gel column chromatography separating-purifying, except desolventizing, after drying, using the mixed solution of methylene dichloride and methyl alcohol to carry out recrystallization and obtain red solid 0.15g, is 60% by productive rate.Through nuclear magnetic resonance spectroscopy,
1hNMR (400MHz, DMSO) δ 8.59 (s, 2H), 8.41 (d, J=8.8Hz, 2H), 8.26 (d, J=8.9Hz, 2H), 7.81 (s, 2H), 6.97 (d, J=8.3Hz, 2H), 6.87 (d, J=9.0Hz, 8H), 6.80 (d, J=9.0Hz, 8H), 6.68 (d, J=1.7Hz, 2H), 6.57 (dd, J=8.3, 1.8Hz, 2H), 6.22 (s, 2H), 5.32 (s, 1H), 3.66 (s, 12H), 1.86 (dd, J=13.5, 7.2Hz, 3H), 1.78 – 1.65 (m, 8H), 1.65 – 1.48 (m, 3H), 0.26 (t, J=7.3Hz, 6H),-0.00 (t, J=7.2Hz, 6H).
13cNMR (101MHz, CDCl
3) δ 185.14,172.42,155.37,152.44,148.50,145.26,143.91,142.55,141.26,140.18,134.05,133.43,125.76,122.79,120.46,120.31,119.60,117.72,116.02,114.44,100.67,77.26,76.92,76.60,55.33,55.04,32.85,32.23,29.59,28.53,8.80,8.50. mass spectrum (MSm/z): 1478.5. electroluminescent spectrum as shown in Figure 1.
Embodiment 2 another containing iridium ruddiness metal complexes and preparation method thereof.
This embodiment is with the difference of embodiment 1:
Structure containing iridium ruddiness metal complexes is
Wherein, R is naphthalene.
In the preparation process containing iridium ruddiness metal complexes, be following steps with the difference of embodiment 1:
(1), in aqueous sodium hydroxide solution, the mass ratio of sodium hydroxide and water is 1:3; After adding compd A, react 6 hours;
(2) dissolved in glacial acetic acid by compd B, slowly drip nitrosonitric acid, cooling bath reacts 3 hours;
(3) volume ratio of tetrahydrofuran (THF) and ethanol is 1:4; Add Pd/carbon catalyst, be heated to 65 DEG C, drip hydrazine hydrate, reacting by heating 3 hours, obtains Compound D after separation and purification;
(4) in protective gas atmosphere, be that Compound D and the 4-iodanisol of 1:3.0 is dissolved in p-Xylol by mol ratio, add cuprous iodide/phenanthroline as catalyzer, add potassium hydroxide, be heated to 120 DEG C of reactions 42 hours, after separation and purification, obtain compd E;
(5) in protective gas atmosphere, compd E is dissolved in tetrahydrofuran THF, at-78 DEG C, adds n-Butyl Lithium, react 40 minutes, add trimethyl borate, react 8 hours under room temperature, add hydrochloric acid afterwards and make solution be acid;
(6) in protective gas atmosphere, be that 2-chloro-5-trifluoromethylpyridine and the compound F 17-hydroxy-corticosterone of 1:1.1 is dissolved in the first solvent by mol ratio, add the aqueous solution of organic palladium catalyzer and carbonate, carry out Suzuki linked reaction 8h, after separation and purification, obtain compound G;
(7) in protective gas atmosphere, be that described compound G and three hydrated iridium trichloride of 2:1 are dissolved in the second solvent by mol ratio, react 16 hours at 70 DEG C;
(8) in protective gas atmosphere, be that compound H and the methyl ethyl diketone of 1:3 is dissolved in the 3rd solvent by mol ratio, add sodium carbonate, react 12 hours at being heated to 70 DEG C.
In described step (1), reactant consumption molfraction meter is: 2-bromine fluorenes is 1 part, and compd A is 2.1 parts, and Tetrabutyl amonium bromide is 0.02 part, and aqueous sodium hydroxide solution is 5 parts, and dimethyl sulfoxide (DMSO) is 2 parts;
In described step (2), reactant consumption molfraction meter is: compd B is 1 part, and nitrosonitric acid is 3 parts, and Glacial acetic acid is 2 parts;
In described step (3), reactant consumption molfraction meter is: Compound C is 1 part, and hydrazine hydrate is 1.1 parts, and Pd/carbon catalyst is 0.05 part, and the mixed solution of tetrahydrofuran (THF) and ethanol is 2 parts;
In described step (4), reactant consumption molfraction meter is: Compound D is 1 part, and 4-iodanisol is 2.1 parts, and cuprous iodide is 0.1 part, and phenanthroline is 0.2 part, and potassium hydroxide is 7 parts, and p-Xylol is 2 parts;
In described step (5), reactant consumption molfraction meter is: compd E is 1 part, and n-Butyl Lithium is 1.1 parts, and trimethyl borate is 3 parts, and tetrahydrofuran (THF) is 2 parts.
The first solvent in described step (6) is tetrahydrofuran (THF).
Another contains iridium ruddiness metal complexes and preparation method thereof to embodiment 3 again.
This embodiment is with the difference of embodiment 1:
Structure containing iridium ruddiness metal complexes is
Wherein, R is pyrroles.
In the preparation process containing iridium ruddiness metal complexes, be following steps with the difference of embodiment 1:
(1), in aqueous sodium hydroxide solution, the mass ratio of sodium hydroxide and water is 1:2; After adding compd A, react 24 hours;
(2) dissolved in glacial acetic acid by compd B, slowly drip nitrosonitric acid, cooling bath reacts 24 hours;
(3) volume ratio of tetrahydrofuran (THF) and ethanol is 1:3; Add Pd/carbon catalyst, be heated to 70 DEG C, drip hydrazine hydrate, reacting by heating 24 hours, obtains Compound D after separation and purification;
(4) in protective gas atmosphere, be that Compound D and the 4-iodanisol of 1:2.1 is dissolved in p-Xylol by mol ratio, add cuprous iodide/phenanthroline as catalyzer, add potassium hydroxide, be heated to 145 DEG C of reactions 36 hours, after separation and purification, obtain compd E;
(5) in protective gas atmosphere, compd E is dissolved in tetrahydrofuran THF, at-78 DEG C, adds n-Butyl Lithium, react 50 minutes, add trimethyl borate, react 12 hours under room temperature, add hydrochloric acid afterwards and make solution be acid;
(6) in protective gas atmosphere, be that 2-chloro-5-trifluoromethylpyridine and the compound F 17-hydroxy-corticosterone of 1:2.0 is dissolved in the first solvent by mol ratio, add the aqueous solution of organic palladium catalyzer and carbonate, carry out Suzuki linked reaction 16h, after separation and purification, obtain compound G;
(7) in protective gas atmosphere, be that described compound G and three hydrated iridium trichloride of 3:1 are dissolved in the second solvent by mol ratio, react 12 hours at 90 DEG C;
(8) in protective gas atmosphere, be that compound H and the methyl ethyl diketone of 1:5 is dissolved in the 3rd solvent by mol ratio, add sodium carbonate, react 24 hours at being heated to 90 DEG C.
In described step (1), reactant consumption molfraction meter is: 2-bromine fluorenes is 1 part, and compd A is 3 parts, and Tetrabutyl amonium bromide is 0.1 part, and aqueous sodium hydroxide solution is 15 parts, and dimethyl sulfoxide (DMSO) is 5 parts;
In described step (2), reactant consumption molfraction meter is: compd B is 1 part, and nitrosonitric acid is 10 parts, and Glacial acetic acid is 50 parts;
In described step (3), reactant consumption molfraction meter is: Compound C is 1 part, and hydrazine hydrate is 5 parts, and Pd/carbon catalyst is 0.15 part, and the mixed solution of tetrahydrofuran (THF) and ethanol is 50 parts;
In described step (4), reactant consumption molfraction meter is: Compound D is 1 part, and 4-iodanisol is 3 parts, and cuprous iodide is 0.2 part, and phenanthroline is 0.4 part, and potassium hydroxide is 10 parts, and p-Xylol is 50 parts;
In described step (5), reactant consumption molfraction meter is: compd E is 1 part, and n-Butyl Lithium is 1.5 parts, and trimethyl borate is 8 parts, and tetrahydrofuran (THF) is 50 parts.
In other embodiment, R can also be alkyl, aryl, substituted aryl, heterocyclic aryl or substituted heterocycle aryl; Preferred described aryl is benzene, biphenyl, naphthalene, anthracene, phenanthrene, Bi Huo perylene; Described heterocyclic aryl is pyrroles, pyridine, furans, thiophene or carbazole; The substituting group of described substituted aryl or substituted heterocycle aryl is halogen atom, alkyl, alkoxyl group, amino, ester group, boric acid ester group, acyl group, amide group, cyano group, aryloxy, aromatic base or heterocyclic substituent; Substituent replacement number is one or more.
Embodiment 4 adopts the organic electroluminescence device containing iridium ruddiness metal complexes of the present invention.
Adopt the organic electroluminescence device containing iridium ruddiness metal complexes of the present invention, comprising: substrate, be arranged at the anode on described substrate, be arranged at the organic layer on described anode, be arranged at the negative electrode in electron injection/transport layer.
Wherein, the number of organic layer is two-layer, and have one deck organic layer to be luminescent layer, electron injection/transport layer is on luminescent layer; The material of described anode is indium tin oxide.The material of described luminescent layer comprises light emitting host material and is doped in the light emitting guest material in light emitting host material, described light emitting guest material be in above-described embodiment containing iridium ruddiness metal complexes.
The thickness of described electron injection/transport layer is 0.1nm.The thickness of described substrate is 0.3mm.
Described negative electrode preferable alloy, includes but not limited to calcium, magnesium, barium, aluminium and silver, is preferably aluminium.
In other embodiments, the number of organic layer can also be 3 layers or more, and wherein one deck organic layer is luminescent layer; The thickness of described electron injection/transport layer also can be 50nm or 100nm.The thickness of described substrate also can be 0.5mm or 0.7mm.
Embodiment 5 adopts the preparation of the organic electroluminescence device containing iridium ruddiness metal complexes of the present invention.
First use tin indium oxide (ITO) clean-out system to clean indium tin oxide-coated glass (ito glass), then clean with distilled water, last UV ozone (UVO) processes 25min; With the speed of 3000 revs/min spin coating Polyglycolic acid fibre-poly-(styrene sulfonate) (PEDOT) a minute on indium tin oxide-coated glass, 120 DEG C are dried 1 hour, obtain the anode of organic electroluminescence device.Described anode is arranged on substrate.
By 10mg4,4'; 4 " complex of iridium prepared by-three (N-3-methylphenyl-N-phenyl is amino) triphenylamine (m-MTDATA) and embodiment 1 and 1mL chlorobenzene mix, be configured to the chlorobenzene solution of 10mg/mL, again with the speed of 1500 revs/min spin coating one minute on described anode, 100 DEG C of thermal treatment 30min, obtain organic electro luminescent layer in an inert atmosphere;
By described organic electro luminescent layer 4 × 10
-4under the vacuum tightness of Pa, electron injection/transport layer 1 that evaporation 50nm is thick, 3,5-tri-[(3-pyridyl)-3-phenyl] benzene (TmPyPB), the Al that LiF and 100nm that evaporation 1nm is thick is afterwards thick, described LiF and Al is compound negative electrode, and finally obtaining structure is ITO/PEDOT:PSS (40nm)/m-MTDATA:xwt.% complex of iridium/TmPyPB (60nm)/LiF (1nm)/Al (100nm) organic electroluminescence device.
As shown in Figures 3 and 4, test above-mentioned organic electroluminescence device current-voltage-brightness characteristic by Keithley source measuring system (Keithley2400Sourcemeter), test its electroluminescent spectrum with SpectraScanPR650spectrophotometer.All measurements are all carried out under atmosphere at room temperature.Recording organic electroluminescence device, to open bright voltage be 2.4V, and maximum lumen efficiency is 24.5%, and maximum power efficiency is 31.2lm/W.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among the protection domain of the invention.
Claims (10)
1., containing an iridium ruddiness metal complexes, it is characterized in that there is following structure:
Wherein R is alkyl, aryl, substituted aryl, heterocyclic aryl or substituted heterocycle aryl.
2. according to claim 1 containing iridium ruddiness metal complexes, it is characterized in that,
Described aryl is benzene, biphenyl, naphthalene, anthracene, phenanthrene, Bi Huo perylene;
Described heterocyclic aryl is pyrroles, pyridine, furans, thiophene or carbazole;
The substituting group of described substituted aryl or substituted heterocycle aryl is halogen atom, alkyl, alkoxyl group, amino, ester group, boric acid ester group, acyl group, amide group, cyano group, aryloxy, aromatic base or heterocyclic substituent; Substituent replacement number is one or more.
3. the preparation method containing iridium ruddiness metal complexes according to claim 1, is characterized in that, comprise the steps:
(1) in protective gas atmosphere, be dissolved in dimethyl sulfoxide (DMSO) by 2-bromine fluorenes and Tetrabutyl amonium bromide, the mass ratio adding sodium hydroxide and water is the aqueous sodium hydroxide solution of 1:1 ~ 3, adds compd A, react 6 ~ 24 hours, after separation and purification, obtain compd B; Wherein, the structural formula of compd A is: R-Br, and the structural formula of compd B is
r is alkyl, aryl, substituted aryl, heterocyclic aryl or substituted heterocycle aryl;
(2) dissolved in glacial acetic acid by compd B, slowly drip nitrosonitric acid, cooling bath reaction 3 ~ 24 hours, obtain Compound C after separation and purification, the structural formula of Compound C is
(3) under room temperature, Compound C is dissolved in the mixed solvent of tetrahydrofuran (THF) and ethanol, the volume ratio of tetrahydrofuran (THF) and ethanol is 1:1 ~ 4, add Pd/carbon catalyst, be heated to 60 ~ 70 DEG C, drip hydrazine hydrate, reacting by heating 3 ~ 24 hours, obtain Compound D after separation and purification, the structural formula of Compound D is
(4) in protective gas atmosphere; be that Compound D and the 4-iodanisol of 1:2.1 ~ 3.0 is dissolved in p-Xylol by mol ratio; add cuprous iodide/phenanthroline as catalyzer; add potassium hydroxide; be heated to 100 ~ 145 DEG C of reactions 36 ~ 48 hours; obtain compd E after separation and purification, the structural formula of compd E is
(5) in protective gas atmosphere, compd E is dissolved in tetrahydrofuran (THF), at-78 DEG C, adds n-Butyl Lithium, react 40 ~ 60 minutes, add trimethyl borate, react 4 ~ 12 hours under room temperature, add hydrochloric acid afterwards and make solution be acid; Obtain compound F 17-hydroxy-corticosterone after separation and purification, the structural formula of compound F 17-hydroxy-corticosterone is
(6) in protective gas atmosphere; be that 2-chloro-5-trifluoromethylpyridine and the compound F 17-hydroxy-corticosterone of 1:1.1 ~ 2.0 is dissolved in the first solvent by mol ratio; add the aqueous solution of organic palladium catalyzer and carbonate; carry out Suzuki linked reaction 8 ~ 24h; obtain compound G after separation and purification, the structural formula of compound is
(7) in protective gas atmosphere, be that described compound G and three hydrated iridium trichloride of 2 ~ 3:1 are dissolved in the second solvent by mol ratio, react 12 ~ 24 hours at 70 ~ 90 DEG C, obtain compound H after separation and purification, the structural formula of described compound H is
(8) in protective gas atmosphere; be that compound H and the methyl ethyl diketone of 1:3 ~ 5 is dissolved in the 3rd solvent by mol ratio; add sodium carbonate; react 12 ~ 24 hours at being heated to 70 ~ 90 DEG C; obtain ruddiness phosphorescent metal complex after separation and purification, the structural formula of described ruddiness phosphorescent iridium metal complexes is
In described step (1), reactant consumption molfraction meter is: 2-bromine fluorenes is 1 part, and compd A is 2.1 ~ 3 parts, and Tetrabutyl amonium bromide is 0.02 ~ 0.1 part, and aqueous sodium hydroxide solution is 5 ~ 15 parts, and dimethyl sulfoxide (DMSO) is 2 ~ 5 parts;
In described step (2), reactant consumption molfraction meter is: compd B is 1 part, and nitrosonitric acid is 3 ~ 10 parts, and Glacial acetic acid is 2 ~ 50 parts;
In described step (3), reactant consumption molfraction meter is: Compound C is 1 part, and hydrazine hydrate is 1.1 ~ 5 parts, and Pd/carbon catalyst is 0.05 ~ 0.15 part, and the mixed solution of tetrahydrofuran (THF) and ethanol is 2 ~ 50 parts;
In described step (4), reactant consumption molfraction meter is: Compound D is 1 part, and 4-iodanisol is 2.1 ~ 3 parts, cuprous iodide is 0.1 ~ 0.2 part, phenanthroline is 0.2 ~ 0.4 part, and potassium hydroxide is 7 ~ 10 parts, and p-Xylol is 2 ~ 50 parts;
In described step (5), reactant consumption molfraction meter is: compd E is 1 part, and n-Butyl Lithium is 1.1 ~ 1.5 parts, and trimethyl borate is 3 ~ 8 parts, and tetrahydrofuran (THF) is 2 ~ 50 parts.
4. preparation method according to claim 3, is characterized in that,
The first solvent in described step (6) is toluene or tetrahydrofuran (THF);
The second solvent in described step (7) is the mixture of cellosolvo and water, and the volume ratio of described cellosolvo and water is 3:1;
The 3rd solvent in described step (8) is cellosolvo.
5. preparation method according to claim 3, is characterized in that, described organic palladium catalyzer is tetra-triphenylphosphine palladium; The mol ratio of described organic palladium catalyzer and 2,5-dibromo pyridine is 3 ~ 5:100.
6. preparation method according to claim 3, is characterized in that, described carbonate is at least one in salt of wormwood and sodium carbonate.
7. preparation method according to claim 3, is characterized in that, the concrete grammar obtaining ruddiness phosphorescent iridium metal complexes in step (8) after separation and purification is:
After reaction terminates, reaction solution is chilled to room temperature, removes at least part of 3rd solvent, with dichloromethane extraction, organic phases washed with water three times, with anhydrous magnesium sulfate drying, filters organic phase, solvent in removing organic phase obtains solid crude product, be eluent with methylene dichloride and sherwood oil, crude product purified by silica gel pillar layer separation is purified, except desolventizing, after drying, the mixed solution re-using methylene dichloride and methyl alcohol carries out recrystallization and obtains the ruddiness phosphorescent iridium metal complexes after purifying.
8. adopt the organic electroluminescence device of title complex according to claim 1, it is characterized in that, comprise and stacking gradually: anode, luminescent layer and negative electrode;
The material of described luminescent layer comprises: light emitting host material and the light emitting guest material be doped in light emitting host material;
Described light emitting guest material is for containing iridium ruddiness metal complexes described in claim 1.
9. organic electroluminescence device according to claim 8, is characterized in that, the thickness of described electron injection/transport layer is 0.1 ~ 100nm; The thickness of described substrate is 0.3 ~ 0.7mm.
10. organic electroluminescence device according to claim 9, is characterized in that, the thickness of described electron injection/transport layer is 50nm.
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| CN109988099A (en) * | 2019-04-24 | 2019-07-09 | 武汉华星光电半导体显示技术有限公司 | Electroluminescent material, the preparation method of electroluminescent material and luminescent device |
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