CN113201021B - 基于1,8-取代咔唑的高辐射速率铂配合物及应用 - Google Patents
基于1,8-取代咔唑的高辐射速率铂配合物及应用 Download PDFInfo
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- CN113201021B CN113201021B CN202110436077.3A CN202110436077A CN113201021B CN 113201021 B CN113201021 B CN 113201021B CN 202110436077 A CN202110436077 A CN 202110436077A CN 113201021 B CN113201021 B CN 113201021B
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- carbazole
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- -1 8-substituted carbazole Chemical class 0.000 title claims abstract description 47
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 66
- 230000005855 radiation Effects 0.000 claims abstract description 14
- 239000012044 organic layer Substances 0.000 claims description 16
- 125000000623 heterocyclic group Chemical group 0.000 claims description 15
- 125000001072 heteroaryl group Chemical group 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 125000004104 aryloxy group Chemical group 0.000 claims description 11
- 125000003342 alkenyl group Chemical group 0.000 claims description 10
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 7
- 125000003282 alkyl amino group Chemical group 0.000 claims description 7
- 229910052805 deuterium Inorganic materials 0.000 claims description 7
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 7
- 125000004986 diarylamino group Chemical group 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 230000003111 delayed effect Effects 0.000 claims description 4
- 150000002431 hydrogen Chemical group 0.000 claims 3
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims 1
- 239000003446 ligand Substances 0.000 abstract description 29
- 230000005281 excited state Effects 0.000 abstract description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 11
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 abstract description 10
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 abstract description 9
- 125000001424 substituent group Chemical group 0.000 abstract description 7
- 238000012546 transfer Methods 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 98
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 75
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 57
- 229910052757 nitrogen Inorganic materials 0.000 description 49
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 42
- 239000010410 layer Substances 0.000 description 41
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- 238000005481 NMR spectroscopy Methods 0.000 description 29
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
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- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 16
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- 239000002184 metal Substances 0.000 description 15
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- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 14
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
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- 238000001228 spectrum Methods 0.000 description 10
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000003480 eluent Substances 0.000 description 9
- 239000012074 organic phase Substances 0.000 description 9
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 8
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 8
- 229910000160 potassium phosphate Inorganic materials 0.000 description 8
- 235000011009 potassium phosphates Nutrition 0.000 description 8
- 238000004821 distillation Methods 0.000 description 7
- 238000000295 emission spectrum Methods 0.000 description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 125000004466 alkoxycarbonylamino group Chemical group 0.000 description 6
- 125000005133 alkynyloxy group Chemical group 0.000 description 6
- 125000005162 aryl oxy carbonyl amino group Chemical group 0.000 description 6
- 125000001841 imino group Chemical group [H]N=* 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 238000010926 purge Methods 0.000 description 6
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 6
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- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 6
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- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 6
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 5
- 238000003775 Density Functional Theory Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 150000001408 amides Chemical class 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000005525 hole transport Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 150000001716 carbazoles Chemical group 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 2
- 238000004057 DFT-B3LYP calculation Methods 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- VVAOPCKKNIUEEU-PHFPKPIQSA-L dichloro(cycloocta-1,5-diene)platinum(ii) Chemical compound Cl[Pt]Cl.C\1C\C=C/CC\C=C/1 VVAOPCKKNIUEEU-PHFPKPIQSA-L 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 1
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 1
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 1
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- FBTOLQFRGURPJH-UHFFFAOYSA-N 1-phenyl-9h-carbazole Chemical compound C1=CC=CC=C1C1=CC=CC2=C1NC1=CC=CC=C12 FBTOLQFRGURPJH-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical class [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
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- 239000000969 carrier Substances 0.000 description 1
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- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125773 compound 10 Drugs 0.000 description 1
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- NPOMSUOUAZCMBL-UHFFFAOYSA-N dichloromethane;ethoxyethane Chemical compound ClCCl.CCOCC NPOMSUOUAZCMBL-UHFFFAOYSA-N 0.000 description 1
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- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-M picolinate Chemical compound [O-]C(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-M 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- 238000004904 shortening Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
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- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
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- 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
- C07F15/0086—Platinum compounds
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- H—ELECTRICITY
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- 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
- H10K85/346—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising platinum
-
- 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
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- 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
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
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- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
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- H10K50/18—Carrier blocking layers
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
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Abstract
本发明提供了一种基于1,8‑取代咔唑的高辐射速率铂配合物及应用。本发明的发光材料通过在咔唑的1,8‑位引入取代基,可高效调控材料分子激发态性质,增加金属到配体电荷转移态(MLCT)成分,提高分子的系间窜越速率;同时咔唑的1,8‑位引入取代基可增加其和吡啶环之间的二面角增加,可提高分子刚性,有效减少由于分子中咔唑环振动和转动所消耗的能量,减少非辐射衰减。上述因素可共同提高材料分子的辐射速率,缩短激发态寿命。
Description
技术领域
本发明属于发光材料领域,尤其涉及一种基于1,8-取代咔唑的高辐射速率铂配合物及应用。
背景技术
自美国柯达公司的邓青云博士(C.W.Tang)和VanSlyke于1987年成功制备出第一个高效有机电致发光器件(OLED)以来,历经三十多年的研究,OLED已经发展成为新一代的全彩显示和固态照明技术。OLED是自发光体系,具有制作成本和能耗低、发光效率高、视角广、响应快、等优点,在全彩显示和照明领域具有广阔的应用前景。
发光材料是OLED器件的核心材料,但是稳定高效能够满足商业化应用的发光材料依然及其稀少,尤其是量子效率高的磷光和延迟荧光材料。因此,新型高性能发光材料的设计发展依然是促进OLED领域发展的重要方向。此外,OLED器件的稳定性依然是制约其发展的瓶颈问题,而发光材料的辐射速率(kr obs)是影响OLED器件的稳定性的重要因素。提高发光材料分子的辐射速率可以使分子高效辐射发光;同时缩短分子处于激发态的时间,减小分子激发态寿命τobs,减少或避免发生三线态-三线态激子湮灭而产生高能量的单线态激子;此外,减少激发态分子非辐射弛豫产生的热能,提高材料分子和OLED器件的稳定性。因此,设计发展具有高辐射速率kr obs和短激发态寿命τobs的发光材料对于提高材料分子和OLED器件的稳定性具有重要意义。
发明内容
本发明的目的在于针对现有技术的不足,提供一种基于1,8-取代咔唑的高辐射速率铂配合物及应用。本发明发光材料基于苯基咔唑分子母核且含有1,8-取代咔唑的四齿环金属铂(II)配合物,具有高辐射速率kr obs和短激发态寿命τobs。
本发明的目的是通过以下技术方案来实现的:一种基于1,8-取代咔唑的高辐射速率铂配合物发光材料,是含有1,8-双取代咔唑的四齿环金属铂(II)配合物,化学式如通式(1)所示:
其中,L为五元或六元杂芳环。
Ra和Rb均不为氢原子且各自独立地代表烷基、烷氧基、环烷基、杂环基、烯基、取代或未取代的芳基、取代或未取代的芳氧基、取代或未取代的杂芳基、卤素、羟基、巯基、硝基、氰基、氨基、羧基、磺基、肼基、脲基、炔氧基、酯基、酰胺基、磺酰基、亚磺酰基、磺酰基胺基、磷酰基胺基、烷氧基羰基胺基、芳氧基羰基胺基、甲硅烷基、烷基胺基、双烷基胺基、单芳基胺基、双芳基胺基、亚脲基、亚胺基或其组合。
R1、R2、R3、R4、R5和R6各自独立地代表氢、氘、烷基、烷氧基、环烷基、杂环基、烯基、取代或未取代的芳基、取代或未取代的芳氧基、取代或未取代的杂芳基、卤素、羟基、巯基、硝基、氰基、氨基、羧基、磺基、肼基、脲基、炔氧基、酯基、酰胺基、磺酰基、亚磺酰基、磺酰基胺基、磷酰基胺基、烷氧基羰基胺基、芳氧基羰基胺基、甲硅烷基、烷基胺基、双烷基胺基、单芳基胺基、双芳基胺基、亚脲基、亚胺基或其组合。
R1、R2、R3、R4、R5和R6中的两个或者多个可以相连形成稠环,所述稠环还可以与其它环稠合。
Ru、Rv、Rw、Rx和Ry各自独立地表示单取代、双取代、三取代、四取代或者无取代,且Ru、Rv、Rw、Rx和Ry各自独立地为氢、氘、烷基、烷氧基、环烷基、杂环基、烯基、取代或未取代的芳基、取代或未取代的芳氧基、取代或未取代的杂芳基、卤素、羟基、巯基、硝基、氰基、氨基、羧基、磺基、肼基、脲基、炔氧基、酯基、酰胺基、磺酰基、亚磺酰基、磺酰基胺基、磷酰基胺基、烷氧基羰基胺基、芳氧基羰基胺基、甲硅烷基、烷基胺基、双烷基胺基、单芳基胺基、双芳基胺基、亚脲基、亚胺基或其组合;且两个或者多个邻近的Ru、Rv、Rw、Rx和Ry各自独立或者选择性连接形成稠环。
进一步地,具有如下化学结构中的一种:
其中,R均不为除甲基以外的烷基、烷氧基、环烷基、杂环基、烯基、取代或未取代的芳基、取代或未取代的芳氧基、取代或未取代的杂芳基,或其氘代取代基。
一种上述基于1,8-取代咔唑的高辐射速率铂配合物发光材料在有机发光元件中的应用。
进一步地,所述有机发光元件为有机发光二极管、发光二极管或发光电化学电池。
一种上述基于1,8-取代咔唑的高辐射速率铂配合物发光材料的应用,作为有机发光器件中的磷光发光材料或延迟荧光材料。
一种发光器件,包括第一电极、第二电极和有机层;有机层设置于第一电极和第二电极之间,且至少有一个有机层;所述有机层包括上述发光材料。
本发明的有益效果是:
(1)通过在配体中咔唑的1,8-位引入取代基,可增加取代咔唑环和吡啶环之间的二面角,减小二者之间的共轭,调控材料分子激发态性质,增加金属到配体电荷转移态(MLCT)大大增加成分,提高分子的系间窜越速率,进而提高辐射速率kr obs和缩短激发态寿命τobs;同时提高材料分子的磷光量子效率;
(2)取代咔唑环和吡啶环之间的二面角增加,可提高分子刚性,有效减少由于分子中咔唑环振动和转动所消耗的能量,减少非辐射衰减,提高磷光量子效率。
附图说明
图1为通过密度泛函理论(DFT)计算得到的PtPN1-Cz和PtDMCz的优化分子结构和对应的咔唑/吡啶和1,8-二甲基/吡啶之间的二面角示意图;
图2为PtON1-Cz在各种环境下的发射光谱图比较示意图;其中,2-MeTHF为2-甲基四氢呋喃,DCM为二氯甲烷,RT代表室温;
图3为PtDMCz在各种环境下的发射光谱图比较示意图;其中,2-MeTHF为2-甲基四氢呋喃,DCM为二氯甲烷,PMMA为聚甲基丙烯酸甲酯,RT代表室温;
图4为PtDMCz在室温下二氯甲烷溶液中的发光强度衰减曲线示意图;其中,DCM为二氯甲烷,RT代表室温;
图5为PtDMCz、PtDMCz-ppz、PtDMCz-2-ptz、PtDMCz-1-ptz、PtDMCz-piz、PtDMCz-ppy、PtDMCz-NHC和PtDMCz-Ph-NHC在室温下二氯甲烷溶液中的发射光谱图;
图6为PtDMCz和PdDMCz的光稳定性测试比较;
图7为有机发光元件的结构示意图;其中,从下到上依次表示衬底、阳极、空穴注入层、空穴传输层、发光层、电子传输层和阴极。
具体实施方式
以下对本发明的内容进行详细说明。以下所记载的构成要件的说明有时是基于本发明的代表性实施方式或具体例而成,但本发明并不限定于此种实施方式或具体例。
本发明一种基于1,8-取代咔唑的高辐射速率铂配合物发光材料,是含有1,8-双取代咔唑的四齿环金属铂(II)配合物,化学式如通式(1)所示:
其中,L为五元或六元杂芳环。
Ra和Rb均不为氢原子且各自独立地代表烷基、烷氧基、环烷基、杂环基、烯基、取代或未取代的芳基、取代或未取代的芳氧基、取代或未取代的杂芳基、卤素、羟基、巯基、硝基、氰基、氨基、羧基、磺基、肼基、脲基、炔氧基、酯基、酰胺基、磺酰基、亚磺酰基、磺酰基胺基、磷酰基胺基、烷氧基羰基胺基、芳氧基羰基胺基、甲硅烷基、烷基胺基、双烷基胺基、单芳基胺基、双芳基胺基、亚脲基、亚胺基或其组合。
R1、R2、R3、R4、R5和R6各自独立地代表氢、氘、烷基、烷氧基、环烷基、杂环基、烯基、取代或未取代的芳基、取代或未取代的芳氧基、取代或未取代的杂芳基、卤素、羟基、巯基、硝基、氰基、氨基、羧基、磺基、肼基、脲基、炔氧基、酯基、酰胺基、磺酰基、亚磺酰基、磺酰基胺基、磷酰基胺基、烷氧基羰基胺基、芳氧基羰基胺基、甲硅烷基、烷基胺基、双烷基胺基、单芳基胺基、双芳基胺基、亚脲基、亚胺基或其组合,R1、R2、R3、R4、R5和R6中的两个或者多个可以相连形成稠环,所述稠环还可以与其它环稠合。
Ru、Rv、Rw、Rx和Ry各自独立地表示单取代、双取代、三取代、四取代或者无取代,且Ru、Rv、Rw、Rx和Ry各自独立地为氢、氘、烷基、烷氧基、环烷基、杂环基、烯基、取代或未取代的芳基、取代或未取代的芳氧基、取代或未取代的杂芳基、卤素、羟基、巯基、硝基、氰基、氨基、羧基、磺基、肼基、脲基、炔氧基、酯基、酰胺基、磺酰基、亚磺酰基、磺酰基胺基、磷酰基胺基、烷氧基羰基胺基、芳氧基羰基胺基、甲硅烷基、烷基胺基、双烷基胺基、单芳基胺基、双芳基胺基、亚脲基、亚胺基或其组合;且两个或者多个邻近的Ru、Rv、Rw、Rx和Ry各自独立或者选择性连接形成稠环。
本发明具体可为如下化学结构中的一种,但是不限于此:
其中,R均不为除甲基以外的烷基、烷氧基、环烷基、杂环基、烯基、取代或未取代的芳基、取代或未取代的芳氧基、取代或未取代的杂芳基,或其氘代取代基。
本发明上述基于1,8-取代咔唑的高辐射速率铂配合物发光材料可作为有机发光元件中的中的磷光发光材料或延迟荧光材料。所述有机发光元件为有机发光二极管、发光二极管或发光电化学电池。
本发明还提供一种发光器件,包括第一电极、第二电极和有机层;本发明的发光材料用作其中的有机层,设置于第一电极和第二电极之间,且至少设有一个有机层。
下面举例说明下述通式(1)代表的本发明的磷光发光材料的具体实例,然而,不解释为限制本发明。
除非另有说明,以下试验中所涉及到的所有商业试剂购买后直接使用,没有进一步纯化。核磁共振氢谱和碳谱均在氘代氯仿(CDCl3)或氘代二甲基亚砜(DMSO-d6)溶液中测得,氢谱使用400或500兆赫兹的核磁共振谱仪,碳谱使用100或126兆赫兹的核磁共振谱仪,化学位移以四甲基硅烷(TMS)或残留溶剂为基准。如果用CDCl3作溶剂,则氢谱和碳谱分别以TMS(δ=0.00ppm)和CDCl3(δ=77.00ppm)作为内标。如果用DMSO-d6作溶剂,则氢谱和碳谱分别以TMS(δ=0.00ppm)和DMSO-d6(δ=39.52ppm)作为内标。以下缩写(或组合)用于解释氢谱峰:s=单峰,d=双重峰,t=三重峰,q=四重峰,p=五重峰,m=多重峰,br=宽峰。高分辨质谱在Applied Biosystems公司的ESI-QTOF质谱仪上测得,样品电离模式为电喷雾电离。
实施例1:四齿环金属铂(II)配合物磷光发光材料PtDMCz合成路线如下:
中间体3的合成:向带有磁力搅转子和冷凝管的干燥三口烧瓶中依次加入化合物1(1.00g,5.31mmol,1.0当量),化合物2(2.07g,6.38mmol,1.2当量),碘化亚铜(51mg,0.27mmol,5mol%),2-甲酸吡啶(65mg,0.53mmol,10mol%),磷酸钾(2.26g,10.62mmol,2.0当量),然后抽换氮气三次,在氮气保护下加入二甲基亚砜(20mL)。该混合物在90℃油浴中搅拌反应2天,薄层色谱监测至原料反应完毕,冷却至室温。加入少量的盐水,并用乙酸乙酯萃取。有机层用水洗涤两次,水层用乙酸乙酯萃取两次。合并有机相,无水硫酸钠干燥,过滤。减压蒸馏除去溶剂,所得粗品用硅胶层析柱分离提纯,洗脱剂:石油醚/乙酸乙酯=10:1-3:1-2:1,得到中间体3,粘稠液体1.80g,收率88%。1H NMR(DMSO-d6,400MHz):δ2.15(s,3H),2.30(s,3H),6.06(s,1H),7.07(dd,J=8.0,2.4Hz,1H),7.13-7.16(m,3H),7.30-7.32(m,1H),7.36-7.40(m,2H),7.52(t,J=8.0,1H),7.57(dd,J=7.6,1.2Hz,1H),7.59-7.64(m,1H),7.75(td,J=7.6,1.2Hz,1H),7.97(dd,J=8.0,1.2Hz,1H)。
中间体4的合成:向带有磁力搅转子和冷凝管的干燥三口烧瓶中依次加入化合物3(1.71g,4.41mmol,1.0当量),三苯基膦(3.47g,13.23mmol,3.0当量),然后抽换氮气三次,在氮气保护下加入邻二氯苯(25mL)。该混合物在180℃油浴中搅拌反应24小时,薄层色谱监测至原料反应完毕,冷却至室温。减压蒸馏除去溶剂,所得粗品用硅胶层析柱分离提纯,洗脱剂:石油醚/二氯甲烷=10:1-5:1,得到中间体4,白色固体1.43g,收率92%。1H NMR(500MHz,CDCl3):δ2.26(s,3H),2.27(s,3H),5.96(s,1H),6.81(d,J=2.0Hz,1H),6.92(dd,J=8.5,2.0Hz,1H),6.97-7.00(m,1H),7.07(t,J=2.0Hz,1H),7.14-7.16(m,1H),7.21-7.25(m,1H),7.31-7.37(m,3H),7.96(d,J=8.5Hz,1H),8.01(d,J=7.5Hz,1H),8.53(s,1H)。
配体1的合成:向带有磁力搅转子和冷凝管的干燥三口烧瓶中依次加入化合物4(1.00g,2.83mmol,1.0当量),化合物5(955mg,3.11mmol,1.1当量),三(二亚苄基丙酮)二钯(104mg,0.11mmol,4mol%),配体JohnPhos(68mg,0.23mmol,8mol%),叔丁醇钠(544mg,5.66mmol,2.0当量),然后抽换氮气三次,在氮气保护下加入甲苯(30mL)和二氧六环(30mL)。该混合物在100℃油浴中搅拌反应2天,薄层色谱监测至原料反应完毕,冷却至室温。过滤,并用乙酸乙酯淋洗,滤液用水洗涤两次,水层用乙酸乙酯萃取两次。合并有机相,无水硫酸钠干燥。减压蒸馏除去溶剂,所得粗品用硅胶层析柱分离提纯,洗脱剂:石油醚/二氯甲烷=10:1-1:1,得到配体1,泡沫状固体1.50g,收率85%。HRMS(ESI):C42H34N5O[M+H]+的计算值为624.2758,实测值为624.2761。1H NMR(500MHz,CDCl3):δ2.05(s,6H),2.23(s,3H),2.24(s,3H),5.93(s,1H),6.99-7.01(m,1H),7.06(dd,J=8.5,2.0Hz,1H),7.10-7.15(m,4H),7.19(t,J=7.5Hz,2H),7.29-7.35(m,2H),7.38(td,J=7.5,1.5Hz,1H),7.43(dd,J=5.0,1.5Hz,1H),7.67(d,J=2.5Hz,1H),7.75(d,J=8.0Hz,1H),7.81(d,J=2.0Hz,1H),7.98(d,J=7.5Hz,2H),8.04(d,J=8.5Hz,2H),8.78(d,J=5.0Hz,1H)。13C NMR(125MHz,CDCl3):δ12.40,13.39,19.65,102.73,107.16,110.77,113.65,114.58,116.80,118.17,118.95,119.93,120.75,120.77,120.99,121.11,121.14,121.63,123.95,124.31,124.61,125.91,129.34,129.87,139.21,139.61,140.38,140.41,141.16,148.99,149.74,152.28,153.08,155.66,158.2。
PtDMCz的合成:向带有磁力搅转子和冷凝管的干燥三口烧瓶中依次加入配体1(624mg,1.00mmol,1.0当量),亚氯铂酸钾(457mg,1.10mmol,1.1当量),四丁基溴化铵(32mg,0.10mmol,10mol%),然后抽换氮气三次,在氮气保护下加入醋酸(60mL),氮气鼓泡25分钟。该混合物在室温下搅拌8小时,再在110℃的油浴锅中搅拌反应2天,冷却至室温。然后减压蒸馏除去溶剂,所得粗品用硅胶层析柱分离提纯,洗脱剂:石油醚/二氯甲烷=10:1-5:1,得到Pt1,黄色固体595mg,收率73%。HRMS(ESI):C42H32N5O195Pt[M+H]+的计算值为817.2249,实测值为817.2236。1H NMR(500MHz,DMSO-d6):δ2.06(s,6H),2.47(s,3H),2.75(s,3H),6.45(s,1H),6.99(dd,J=8.0,1.0Hz,1H),7.15-7.26(m,6H),7.30-7.36(m,3H),7.53(dd,J=8.5,2.0Hz,1H),7.87(d,J=8.0Hz,1H),7.90-7.93(m,1H),8.09-8.14(m,3H),8.43(d,J=2.0Hz,1H),9.40(d,J=6.5Hz,1H)。13C NMR(125MHz,CDCl3):δ14.44,15.84,19.90,99.56,106.99,110.05,110.32,113.28,113.40,114.32,115.51,116.40,117.59,118.33,120.11,120.53,120.94,120.96,123.37,124.26,124.67,124.84,129.48,137.94,139.85,141.39,142.01,147.76,148.98,149.24,152.63,152.68,152.90,153.91。
实施例2:四齿环金属铂(II)配合物磷光发光材料PtDMCz-2-ptz合成路线如下:
配体DMCz-2-ptz的合成:向带有磁力搅转子和冷凝管的干燥三口烧瓶中依次加入化合物6(454mg,1.00mmol,1.0当量),化合物5(246mg,1.10mmol,1.1当量),碘化亚铜(19mg,0.10mmol,10mol%),2-吡啶甲酸(25mg,0.20mmol,20mol%),磷酸钾(425mg,2.00mmol,2.0当量),然后抽换氮气三次,在氮气保护下加入二甲基亚砜(20mL)。该混合物在100℃油浴中搅拌反应2天,薄层色谱监测至原料反应完毕,冷却至室温。加入乙酸乙酯,水洗涤两次,水层用乙酸乙酯萃取两次,合并有机相,无水硫酸钠干燥。减压蒸馏除去溶剂,所得粗品用硅胶层析柱分离提纯,洗脱剂:石油醚/二氯甲烷=10:1-3:1,得到配体DMCz-2-ptz,泡沫状固体518mg,收率87%。1H NMR(500MHz,CDCl3):δ2.01(s,6H),7.02(ddd,J=8.0,3.0,1.0Hz,1H),7.07(d,J=7.5Hz,2H),7.10(dd,J=8.5,2.0Hz,1H),7.18(t,J=7.5Hz,2H),7.32-7.38(m,2H),7.39-7.43(m,2H),7.63(d,J=2.5Hz,1H),7.66(s,2H),7.71(ddd,J=7.5,2.5,1.0Hz,1H),7.78(t,J=2.0Hz,1H),7.82-7.84(m,2H),7.96(d,J=7.5Hz,2H),8.06-8.08(m,2H),8.78(d,J=5.5Hz,1H)。13C NMR(125MHz,CDCl3):δ19.61,102.27,109.23,111.04,113.47,113.67,114.74,115.21,117.41,118.17,119.93,120.73,121.08,121.33,121.70,123.97,124.59,125.98,129.32,130.35,135.46,139.74,140.36,140.90,149.76,149.93,152.12,152.34,153.15,155.71,158.51,164.75。
PtDMCz-2-ptz的合成:向带有磁力搅转子和冷凝管的干燥三口烧瓶中依次加入配体DMCz-2-ptz(200mg,0.34mmol,1.0当量),亚氯铂酸钾(153mg,0.37mmol,1.1当量),四丁基溴化铵(10mg,0.03mmol,10mol%),然后抽换氮气三次,在氮气保护下加入醋酸(20mL),氮气鼓泡25分钟。该混合物在110℃的油浴锅中搅拌反应2天,冷却至室温。然后减压蒸馏除去溶剂,所得粗品用硅胶层析柱分离提纯,洗脱剂:石油醚/二氯甲烷=10:1-3:1,得到PtDMCz-2-ptz,黄色固体102mg,收率39%。1H NMR(500MHz,DMSO-d6):δ2.15(s,6H),7.16-7.23(m,5H),7.30-7.37(m,4H),7.57(dd,J=8.0,1.5Hz,1H),7.60(dd,J=6.0,2.0Hz,1H),7.90-7.91(m,1H),7.97(d,J=8.5Hz,1H),8.11(dd,J=8.5,1.0Hz,2H),8.15-8.17(m,1H),8.50(d,J=0.5Hz,1H),8.54(d,J=2.0Hz,1H),8.79(d,J=0.5Hz,1H),9.44(d,J=6.0Hz,1H)。
实施例3:四齿环金属铂(II)配合物磷光发光材料PtDMCz-1-ptz合成路线如下:
配体DMCz-1-ptz的合成:向带有磁力搅转子和冷凝管的干燥三口烧瓶中依次加入化合物6(454mg,1.00mmol,1.0当量),化合物7(246mg,1.10mmol,1.1当量),碘化亚铜(19mg,0.10mmol,10mol%),2-吡啶甲酸(25mg,0.20mmol,20mol%),磷酸钾(425mg,2.00mmol,2.0当量),然后抽换氮气三次,在氮气保护下加入二甲基亚砜(20mL)。该混合物在100℃油浴中搅拌反应2天,薄层色谱监测至原料反应完毕,冷却至室温。加入乙酸乙酯,水洗涤两次,水层用乙酸乙酯萃取两次,合并有机相,无水硫酸钠干燥。减压蒸馏除去溶剂,所得粗品用硅胶层析柱分离提纯,洗脱剂:石油醚/二氯甲烷=10:1-3:1,得到配体DMCz-1-ptz,泡沫状固体509mg,收率85%。1H NMR(500MHz,CDCl3):δ2.03(s,6H),7.08-7.10(m,4H),7.19(t,J=2.5Hz,2H),7.34(t,J=2.5Hz,1H),7.39-7.45(m,5H),7.64(d,J=2.0Hz,1H),7.76(d,J=1.0Hz,1H),7.80-7.84(m,3H),7.98(d,J=7.5Hz,2H),8.08(t,J=7.5Hz,2H),8.79(d,J=5.0Hz,1H)。13C NMR(125MHz,CDCl3):δ19.67,102.73,110.60,111.03,113.76,114.82,118.23,118.26,120.04,120.83,120.99,121.12,121.22,121.43,121.59,121.82,124.04,124.27,124.64,126.17,129.39,130.83,134.36,138.11,139.72,140.32,140.41,149.81,152.31,153.17,155.21,159.04。
PtDMCz-1-ptz的合成:向带有磁力搅转子和冷凝管的干燥三口烧瓶中依次加入配体DMCz-1-ptz(100mg,0.17mmol,1.0当量),亚氯铂酸钾(77mg,0.18mmol,1.1当量),四丁基溴化铵(6mg,0.02mmol,10mol%),然后抽换氮气三次,在氮气保护下加入醋酸(10mL),氮气鼓泡25分钟。该混合物在110℃的油浴锅中搅拌反应2天,冷却至室温。然后减压蒸馏除去溶剂,所得粗品用硅胶层析柱分离提纯,洗脱剂:石油醚/二氯甲烷=10:1-3:1,得到PtDMCz-1-ptz,黄色固体41mg,收率31%。1H NMR(500MHz,DMSO-d6):δ2.15(s,6H),7.04-7.08(m,5H),7.29-7.34(m,3H),7.39(t,J=8.0Hz,1H),7.76(d,J=7.5Hz,1H),7.80-7.82(m,1H),7.91(dd,J=6.0,2.0Hz,1H),7.99(d,J=8.5Hz,1H),8.11(dd,J=7.0,1.0Hz,2H),8.15-8.18(m,1H),8.43(dd,J=2.0,1.0Hz,1H),8.46(d,J=0.5Hz,1H),9.44(d,J=1.5Hz,1H),10.36(d,J=6.0Hz,1H)。
实施例4:四齿环金属铂(II)配合物磷光发光材料PtDMCz-piz合成路线如下:
配体DMCz-piz的合成:向带有磁力搅转子和冷凝管的干燥三口烧瓶中依次加入化合物6(363mg,0.80mmol,1.0当量),化合物8(228mg,0.96mmol,1.1当量),碘化亚铜(15mg,0.08mmol,10mol%),2-吡啶甲酸(20mg,0.16mmol,20mol%),磷酸钾(340mg,1.60mmol,2.0当量),然后抽换氮气三次,在氮气保护下加入二甲基亚砜(16mL)。该混合物在100℃油浴中搅拌反应2天,薄层色谱监测至原料反应完毕,冷却至室温。加入乙酸乙酯,水洗涤两次,水层用乙酸乙酯萃取两次,合并有机相,无水硫酸钠干燥。减压蒸馏除去溶剂,所得粗品用硅胶层析柱分离提纯,洗脱剂:石油醚/二氯甲烷=10:1-3:1,得到配体DMCz-piz,泡沫状固体268mg,收率81%。1H NMR(500MHz,CDCl3):δ1.97(s,6H),3.58(s,3H),6.87(s,1H),7.00(dd,J=8.5,2.0Hz,1H),7.04(d,J=7.0Hz,2H),7.06-7.08(m,1H),7.10-7.13(m,3H),7.22(s,1H),7.24-7.27(m,1H),7.32(dd,J=8.5,1.5Hz,1H),7.35(d,J=5.0Hz,2H),7.37(dd,J=5.0,1.5Hz,1H),7.57(d,J=2.0Hz,1H),7.71(d,J=8.5Hz,1H),7.75(d,J=1.5Hz,1H),7.91(d,J=7.5Hz,2H),7.99(dd,J=7.5,1.5Hz,2H),8.72(d,J=5.0Hz,1H)。13C NMR(125MHz,CDCl3):δ19.64,34.40,102.37,110.88,113.53,118.14,118.50,118.72,119.89,120.65,120.74,120.98,121.13,121.18,121.65,122.46,123.36,123.94,124.35,124.58,125.89,128.18,129.36,129.87,131.97,139.63,140.36,140.37,149.75,152.31,153.07,156.02,157.77。
PtDMCz-piz的合成:向带有磁力搅转子和冷凝管的干燥三口烧瓶中依次加入配体DMCz-piz(94mg,0.15mmol,1.0当量),亚氯铂酸钾(70mg,0.17mmol,1.1当量),四丁基溴化铵(6mg,0.02mmol,10mol%),然后抽换氮气三次,在氮气保护下加入醋酸(10mL),氮气鼓泡25分钟。该混合物在110℃的油浴锅中搅拌反应2天,冷却至室温。然后减压蒸馏除去溶剂,所得粗品用硅胶层析柱分离提纯,洗脱剂:石油醚/二氯甲烷=10:1-3:1,得到PtDMCz-piz,黄色固体69mg,收率56%。1H NMR(500MHz,DMSO-d6):δ2.14(s,6H),4.13(s,3H),7.08(dd,J=8.0Hz,1H),7.17-7.23(m,4H),7.24(d,J=8.5Hz,1H),7.27(t,J=7.5Hz,1H),7.32-7.34(m,2H),7.59(d,J=1.0Hz,1H),7.61(dd,J=6.5,2.0Hz,1H),7.63-7.65(m,2H),7.86(d,J=8.0Hz,1H),8.09-8.12(m,4H),8.46(d,J=2.0Hz,1H),9.42(d,J=6.0Hz,1H)。
实施例5:四齿环金属铂(II)配合物磷光发光材料PtDMCz-ppy合成路线如下:
配体DMCz-ppy的合成:向带有磁力搅转子和冷凝管的干燥三口烧瓶中依次加入化合物6(454mg,1.00mmol,1.0当量),化合物9(258mg,1.10mmol,1.1当量),碘化亚铜(19mg,0.10mmol,10mol%),2-吡啶甲酸(25mg,0.20mmol,20mol%),磷酸钾(425mg,2.00mmol,2.0当量),然后抽换氮气三次,在氮气保护下加入二甲基亚砜(20mL)。该混合物在100℃油浴中搅拌反应2天,薄层色谱监测至原料反应完毕,冷却至室温。加入乙酸乙酯,水洗涤两次,水层用乙酸乙酯萃取两次,合并有机相,无水硫酸钠干燥。减压蒸馏除去溶剂,所得粗品用硅胶层析柱分离提纯,洗脱剂:石油醚/二氯甲烷=10:1-3:1,得到配体DMCz-ppy,泡沫状固体490mg,收率81%。1H NMR(500MHz,CDCl3):δ1.91(s,6H),6.99(d,J=7.0Hz,2H),7.03(d,J=2.5Hz,1H),7.05(d,J=1.5Hz,1H),7.07-7.14(m,3H),7.24-7.27(m,1H),7.28(dd,J=5.0,1.5Hz,1H),7.30-7.34(m,2H),7.46(d,J=7.5Hz,1H),7.52(d,J=2.0Hz,1H),7.57(t,J=6.5Hz,2H),7.65(t,J=2.0Hz,1H),7.75-7.78(m,2H),7.87(d,J=7.5Hz,2H),7.98(d,J=8.0Hz,2H),8.48(d,J=4.0Hz,1H),8.68(d,J=5.0Hz,1H)。
PtDMCz-ppy的合成:向带有磁力搅转子和冷凝管的干燥三口烧瓶中依次加入配体DMCz-ppy(100mg,0.16mmol,1.0当量),亚氯铂酸钾(75mg,0.18mmol,1.1当量),四丁基溴化铵(6mg,0.02mmol,10mol%),然后抽换氮气三次,在氮气保护下加入醋酸(10mL),氮气鼓泡25分钟。该混合物在110℃的油浴锅中搅拌反应2天,冷却至室温。然后减压蒸馏除去溶剂,所得粗品用硅胶层析柱分离提纯,洗脱剂:石油醚/二氯甲烷=10:1-3:1,得到PtDMCz-ppy,黄色固体54mg,收率41%。1H NMR(500MHz,CDCl3):δ2.10(s,6H),7.08(d,J=7.0Hz,2H),7.15(d,J=7.5Hz,2H),7.18(d,J=2.0Hz,1H),7.20-7.26(m,4H),7.32-7.36(m,2H),7.55(dd,J=5.0,3.0Hz,1H),7.68(d,J=8.0Hz,1H),7.73(d,J=8.0Hz,1H),7.87-7.90(m,1H),7.93(d,J=7.5Hz,4H),8.36(d,J=1.5Hz,1H),8.64(d,J=5.5Hz,1H),9.11(d,J=6.0Hz,1H)。
实施例6:四齿环金属铂(II)配合物磷光发光材料PtDMCz-NHC合成路线如下:
中间体11的合成:向带有磁力搅转子和冷凝管的干燥三口烧瓶中依次加入化合物6(676mg,1.49mmol,1.0当量),化合物10(500mg,1.79mmol,1.2当量),碘化亚铜(29mg,0.15mmol,10mol%),2-吡啶甲酸(37mg,0.30mmol,20mol%),磷酸钾(633mg,2.98mmol,2.0当量),然后抽换氮气三次,在氮气保护下加入二甲基亚砜(20mL)。该混合物在100℃油浴中搅拌反应2天,薄层色谱监测至原料反应完毕,冷却至室温。加入乙酸乙酯,水洗涤两次,水层用乙酸乙酯萃取两次,合并有机相,无水硫酸钠干燥。减压蒸馏除去溶剂,所得粗品用硅胶层析柱分离提纯,洗脱剂:石油醚/二氯甲烷=10:1-3:1,得到中间体11,泡沫状固体801mg,收率82%。1H NMR(500MHz,CDCl3):δ1.28(s,9H),2.05(s,6H),6.39(t,J=7.5Hz,1H),6.87(s,1H),7.07(d,J=2.0Hz,1H),7.09(d,J=1.5Hz,1H),7.10-7.12(m,2H),7.14(s,1H),7.20(t,J=7.5Hz,2H),7.23-7.27(m,1H),7.32-7.35(m,1H),7.40(dd,J=8.5,2.0Hz,1H),7.42-7.44(m,2H),7.69(d,J=2.0Hz,1H),7.79(d,J=8.5Hz,1H),7.83(d,J=2.0Hz,1H),7.99(d,J=2.5Hz,2H),8.08(t,J=6.5Hz,2H),8.78(d,J=5.0Hz,1H)。
配体DMCz-NHC的合成:向带有磁力搅转子干燥封管中加入中间体11(800mg,1.23mmol,1.0当量),然后抽换氮气三次,在氮气保护下加入甲苯(40mL)和碘甲烷(210mg,1.48mmol,1.2当量)。该混合物在100℃的油浴锅中搅拌反应2天,冷却至室温,过滤,滤液用石油醚淋洗,干燥,所得灰色固体加入到甲醇/水(40mL/4mL)中,搅拌溶解后加入六氟磷酸铵(302mg,1.85mmol,1.5当量),室温搅拌反应3天。加入水,减压蒸去大部分甲醇,过滤,先水洗后石油醚洗,干燥,得到配体DMCz-NHC,灰色固体810mg,收率81%。1H NMR(500MHz,DMSO-d6):δ1.23(s,9H),2.15(s,6H),3.32(s,3H),6.93(t,J=2.5Hz,1H),7.01(dd,J=8.0,0.5Hz,1H),7.18-7.27(m,6H),7.33-7.37(m,2H),7.54(dd,J=7.5,0.5Hz,1H),7.60(dd,J=6.0,2.0Hz,1H),7.88-7.91(m,2H),8.09-8.11(m,2H),8.13-8.14(m,1H),8.31(d,J=2.0Hz,1H),8.50(d,J=2.0Hz,1H),8.93(d,J=2.5Hz,1H),9.42(d,J=6.5Hz,1H),11.94(s,1H)。
PtDMCz-NHC的合成:向带有磁力搅转子的封管中依次加入配体DMCz-NHC(200mg,0.25mmol,1.0当量),(1,5-环辛二烯)二氯化铂(97mg,0.26mmol,1.05当量)和醋酸钠(61mg,0.74mmol,3.0当量),然后抽换氮气三次,在氮气保护下加入二乙二醇二甲醚(20mL),鼓氮气30分钟。该混合物避光条件下在120℃的油浴锅中搅拌反应3天,冷却至室温,加入蒸馏水淬灭反应,减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯,淋洗剂:石油醚/二氯甲烷=10:1-3:1,得到PtDMCz-NHC,黄色固体71mg,收率34%。1H NMR(500MHz,DMSO-d6):δ1.43(s,9H),2.15(s,6H),4.11(s,3H),6.99(d,J=2.5Hz,1H),7.25-7.30(m,4H),7.37-7.40(m,3H),7.42(d,J=2.0Hz,1H),7.54(d,J=2.5Hz,1H),7.58(dd,J=6.0,1.5Hz,1H),7.93-7.96(m,2H),8.15-8.18(m,3H),8.30(d,J=2.0Hz,1H),8.43(d,J=2.5Hz,1H),9.75(d,J=6.0Hz,1H)。
实施例7:四齿环金属铂(II)配合物磷光发光材料PtDMCz-Ph-NHC合成路线如下:
中间体13的合成:向带有磁力搅转子和冷凝管的干燥三口烧瓶中依次加入化合物6(1.80g,3.97mmol,1.0当量),化合物12(1.44g,4.37mmol,1.1当量),碘化亚铜(76mg,0.40mmol,10mol%),2-吡啶甲酸(97mg,0.79mmol,20mol%),磷酸钾(1.69g,7.94mmol,2.0当量),然后抽换氮气三次,在氮气保护下加入二甲基亚砜(60mL)。该混合物在100℃油浴中搅拌反应2天,薄层色谱监测至原料反应完毕,冷却至室温。加入乙酸乙酯,水洗涤两次,水层用乙酸乙酯萃取两次,合并有机相,无水硫酸钠干燥。减压蒸馏除去溶剂,所得粗品用硅胶层析柱分离提纯,洗脱剂:石油醚/二氯甲烷=10:1-3:1,得到中间体13,泡沫状固体2.25g,收率81%。1H NMR(500MHz,CDCl3):δ1.32(s,9H),2.06(s,6H),7.00(s,1H),7.09-7.12(m,3H),7.17-7.21(m,4H),7.26-7.36(m,6H),7.40(td,J=8.5,1.5Hz,1H),7.43(dd,J=5.0,1.5Hz,1H),7.75-7.77(m,2H),7.85(d,J=1.0Hz,1H),7.98(d,J=7.5Hz,2H),8.07(d,J=7.0Hz,1H),8.09(d,J=8.5Hz,1H),8.79(d,J=5.0Hz,1H)。
配体DMCz-Ph-NHC的合成:向带有磁力搅转子干燥封管中加入中间体13(400mg,0.57mmol,1.0当量),然后抽换氮气三次,在氮气保护下加入甲苯(40mL)和碘甲烷(97mg,0.68mmol,1.2当量)。该混合物在100℃的油浴锅中搅拌反应2天,冷却至室温,过滤,滤液用石油醚淋洗,干燥,所得灰色固体加入到甲醇/水(40mL/4mL)中,搅拌溶解后加入六氟磷酸铵(140mg,0.86mmol,1.5当量),室温搅拌反应3天。加入水,减压蒸去大部分甲醇,过滤,先水洗后石油醚洗,干燥,得到配体DMCz-Ph-NHC,灰色固体364mg,收率74%。1H NMR(500MHz,CDCl3):δ1.36(s,9H),2.07(s,6H),4.20(s,3H),7.03(t,J=2.5Hz,1H),7.11-7.14(m,3H),7.19(t,J=2.5Hz,2H),7.30-7.33(m,1H),7.37-7.40(m,2H),7.45-7.47(m,2H),7.54-7.58(m,1H),7.63-7.66(m,2H),7.70-7.75(m,3H),7.83(d,J=1.5Hz,1H),7.97(d,J=7.5Hz,2H),8.05(d,J=7.5Hz,1H),8.11(d,J=8.5Hz,1H),8.81(d,J=5.0Hz,1H),9.34(s,1H)。13CNMR(125MHz,CDCl3):δ19.71,30.95,33.77,35.49,102.95,110.73,110.84,113.22,113.30,113.75,116.76,117.77,118.26,120.15,120.90,120.99,121.13,121.35,121.64,121.82,124.17,124.23,124.66,126.19,127.70,127.88,129.42,131.17,132.03,133.33,139.60,140.43,140.45,140.86,149.98,152.22,153.21,154.70,157.05,159.15。
PtDMCz-Ph-NHC的合成:向带有磁力搅转子的封管中依次加入配体DMCz-Ph-NHC(100mg,0.12mmol,1.0当量),(1,5-环辛二烯)二氯化铂(49mg,0.13mmol,1.05当量)和醋酸钠(48mg,0.35mmol,3.0当量),然后抽换氮气三次,在氮气保护下加入二乙二醇二甲醚(10mL),鼓氮气30分钟。该混合物避光条件下在120℃的油浴锅中搅拌反应3天,冷却至室温,加入蒸馏水淬灭反应,减压蒸馏除去溶剂。所得粗品用硅胶层析柱分离提纯,淋洗剂:石油醚/二氯甲烷=10:1-3:1,得到PtDMCz-Ph-NHC,黄色固体82mg,收率77%。1H NMR(500MHz,DMSO-d6):δ1.47(s,9H),2.11(s,6H),4.14(s,3H),7.03(d,J=1.5Hz,1H),7.18-7.22(m,4H),7.32-7.35(m,3H),7.51-7.52(m,1H),7.54(t,J=7.5Hz,2H),7.64(d,J=1.5Hz,1H),7.82(d,J=8.0Hz,1H),7.92(d,J=8.0Hz,2H),8.10-8.14(m,3H),8.30(d,J=8.0Hz,1H),8.48(d,J=2.0Hz,1H),9.77(d,J=6.0Hz,1H)。
实施例8:四齿环金属铂(II)配合物磷光发光材料PtDMCz-ppz合成路线如下:
配体DMCz-ppz的合成:向带有磁力搅转子和冷凝管的干燥三口烧瓶中依次加入化合物6(454mg,1.00mmol,1.0当量),化合物14(245mg,1.10mmol,1.1当量),碘化亚铜(19mg,0.10mmol,10mol%),2-吡啶甲酸(25mg,0.20mmol,20mol%),磷酸钾(425mg,2.00mmol,2.0当量),然后抽换氮气三次,在氮气保护下加入二甲基亚砜(20mL)。该混合物在100℃油浴中搅拌反应2天,薄层色谱监测至原料反应完毕,冷却至室温。加入乙酸乙酯,水洗涤两次,水层用乙酸乙酯萃取两次,合并有机相,无水硫酸钠干燥。减压蒸馏除去溶剂,所得粗品用硅胶层析柱分离提纯,洗脱剂:石油醚/二氯甲烷=10:1-3:1,得到配体DMCz-ppz,泡沫状固体506mg,收率85%。1H NMR(500MHz,CDCl3):δ2.02(s,6H),6.37(dd,J=2.5,2.0Hz,1H),6.93-6.95(m,1H),7.07-7.09(m,3H),7.18(d,J=7.5Hz,2H),7.30-7.35(m,4H),7.38-7.40(m,1H),7.41-7.43(m,2H),7.62(t,J=1.5Hz,1H),7.78-7.82(m,3H),7.97(d,J=8.0Hz,2H),8.06(d,J=8.0Hz,2H),8.78(dd,J=5.5,0.5Hz,1H)。13C NMR(125MHz,CDCl3):δ19.65,102.38,107.65,109.49,110.99,113.51,113.65,116.22,118.20,119.95,120.76,120.82,121.06,121.14,121.29,121.72,123.98,124.36,124.65,125.98,126.66,129.36,130.43,139.71,140.33,140.42,141.09,141.40,149.77,152.35,153.15,155.81,158.68。
PtDMCz-ppz的合成:向带有磁力搅转子和冷凝管的干燥三口烧瓶中依次加入配体DMCz-ppz(100mg,0.17mmol,1.0当量),亚氯铂酸钾(77mg,0.18mmol,1.1当量),四丁基溴化铵(6mg,0.02mmol,10mol%),然后抽换氮气三次,在氮气保护下加入醋酸(15mL),氮气鼓泡25分钟。该混合物在110℃的油浴锅中搅拌反应2天,冷却至室温。然后减压蒸馏除去溶剂,所得粗品用硅胶层析柱分离提纯,洗脱剂:石油醚/二氯甲烷=10:1-3:1,得到PtDMCz-ppz,黄色固体65mg,收率49%。1H NMR(500MHz,DMSO-d6):δ2.10(s,6H),6.63(t,J=2.5Hz,1H),7.05-7.11(m,4H),7.15-7.18(m,4H),7.22-7.26(m,2H),7.33(d,J=8.5Hz,1H),7.66(d,J=8.5Hz,1H),7.73(d,J=8.5Hz,1H),7.81(d,J=2.0Hz,1H),7.90-7.94(m,3H),8.05(d,J=2.5Hz,1H),8.36(d,J=2.0Hz,1H),9.33(d,J=6.5Hz,1H)。
电化学、光物理测试和理论计算说明:
吸收光谱在Agilent 8453紫外-可见光光谱仪上测量,使用Horiba Jobin YvonFluoroLog-3光谱仪上进行稳态发射实验和寿命测量。低温(77K)发射光谱和寿命在用液氮冷却的2-甲基四氢呋喃溶液中测量。Pd(II)配合物使用Gaussian 09软件包进行理论计算,利用密度泛函理论(DFT)优化了基态(S0)分子的几何结构,使用B3LYP泛函进行DFT计算,其中C、H、O和N原子使用6-31G(d)基组,Pd原子使用LANL2DZ基组。光稳定性测试条件为5%的发光材料:聚苯乙烯薄膜在375nm紫外光激发下(光强:500W/m2)的发光强度衰减。
实验数据及分析:
为了证明咔唑1,8-位引入取代基的必要性,我们将Pt-DMCz与文献中已报道的Pt1(J.Pgys.Chem.Lett,2018,9,2285)、PtON1(Inorg.Chem.,2017,56,8244)、PtON1-Ph(Inorg.Chem.,2017,56,8244)和PtON1-Cz(Inorg.Chem.,2017,56,8244)做了进一步比较,其结构式如下所示,其光物理性质数据如下表1所示。
表1:四齿环金属铂(II)配合物发光材料光物理性质数据列表
注:a为了便于比较,取基于优化后的S0态在B3LYP/6-31G(d)/LANL2DZ水平下的理论计算值。λ为发射波长;τobs为材料激发态寿命;ΦPL为磷光量子效率;kr obs为辐射速率;其中kr obs=ΦPL/τobs。
由附图1可知,通过理论计算优化结构后的PtON1-Cz和PtDMCz中(取代)咔唑/吡啶之间的二面角分别为51°和88°,表明在PtDMCz中咔唑的1,8-位引入甲基可以大大增加取代咔唑/吡啶之间的二面角。
由附图2和附图3中PtON1-Cz和PtDMCz的低温发射光谱可知,PtON1-Cz为具有精细振动结构的谱图,为典型的电荷转移态(CT)发光;而PtDMCz则为光滑且缺少振动峰的光谱,表明其发光中的金属到配体电荷转移态(MLCT)大大增加,进而使其激发态寿命缩短,由表一盒附图4中的实验数据可知,PtDMCz在室温下二氯甲烷溶液中的激发态寿命缩短至1.1微秒(μs);同时由于取代咔唑环和吡啶环之间的二面角增加,可提高分子刚性,有效减少由于分子中咔唑环振动和转动所消耗的能量,减少非辐射衰减,提高磷光量子效率至88%。以上两个方面的因素使PtDMCz的辐射跃迁速率(kr obs=ΦPL/τobs)大大提高。由表一中实验数据可知PtDMCz的辐射跃迁速率kr obs是其同系物发光材料的Pt1、PtON1、PtON1-Ph和PtON1-Cz的2.72-4.91倍。
从图5中PtDMCz、PtDMCz-ppz、PtDMCz-2-ptz、PtDMCz-1-ptz、PtDMCz-piz、PtDMCz-ppy、PtDMCz-NHC和PtDMCz-Ph-NHC在室温下二氯甲烷溶液中的发射光谱图比较可知,通过对杂环结构的调控可以对其光物理性质,如发射光谱图的半峰宽和发射波长进行有效调控。其中PtDMCz-1-ptz在此条件下的绝对量子效率可高达98%。
从图6中PtDMCz和PdDMCz的光稳定性测试比较中可看出,PtDMCz比其对应的钯(II)配合物PdDMCz具有明显的稳定性提升。
以上实验数据和理论计算结果充分表明,本发明中发展的基于基于1,8-取代咔唑的四齿环金属铂(II)配合物发光材料具有激发态寿命短、辐射跃迁速率大、磷光量子效率高的特点,使其在OLED领域有着巨大的应用前景。
在有机发光元件中,从正负两电极向发光材料中注入载子,产生激发态的发光材料并使其发光。通过通式(1)代表的本发明的络合物可作为磷光发光材料应用于有机光致发光元件或有机电致发光元件等优异的有机发光元件。有机光致发光元件具有在衬底上至少形成了发光层的结构。另外,有机电致发光元件具有至少形成了阳极、阴极、及阳极和阴极之间的有机层的结构。有机层至少包含发光层,可以仅由发光层构成,也可以除发光层以外具有1层以上的有机层。作为这种其它有机层,可以列举空穴传输层、空穴注入层、电子阻挡层、空穴阻挡层、电子注入层、电子传输层、激子阻挡层等。空穴传输层也可以是具有空穴注入功能的空穴注入传输层,电子传输层也可以是具有电子注入功能的电子注入传输层。具体的有机发光元件的结构示意如图7所示。在图7中,从下到上共7层,依次表示衬底、阳极、空穴注入层、空穴传输层、发光层、电子传输层和阴极,其中发光层为客体材料掺杂入主体材料的混合层。
本发明的磷光发光材料作为客体材料掺杂入主体材料制成发光层可应用于OLED器件,结构表示为:
ITO/HATCN(10nm)/TAPC(65nm)/mCBP:实施例中所表示的化合物(4-20wt.%,20nm)/PPT(2nm)/Li2CO3:Bepp2(5%,30nm)/Li2CO3(1nm)/Al(100nm)
其中,ITO为透明阳极;HATCN是空穴注入层,TAPC是空穴传输层,mCBP是主体材料,所表示的化合物(4-20wt.%是掺杂浓度,20nm是发光层的厚度)是客体材料,PPT是空穴阻隔层,Li2CO3:Bepp2为电子传输层,Li2CO3为电子注入层,Al为阴极。括号中单位为纳米(nm)的数字为薄膜的厚度。
在上述器件结构未经优化的情况下,以PtDMCz作为掺杂发光材料的OLED器件外量子效率(EQE)可达20%以上,且具有较小的效率滚降,明显优于相同器件结构中对比掺杂发光材料PtON1-Cz的器件性能。相信通过器件结构的优化和主体材料的改进,其器件性能会进一步提高。
需要说明的是,所述结构为本发明发光材料的一个应用的举例,不构成本发明所示发光材料的具体OLED器件结构的限定,磷光发光材料也不限于实施例中所表示的化合物。
器件中应用材料的分子式如下:
本领域的普通技术人员可以理解,上述各实施方式是实现本发明的具体实施例,而在实际应用中,可以在形式上和细节上对其作各种改变,而不偏离本发明的精神和范围。例如,在不背离本发明的精神的情况下,这里描述的许多取代基结构可以用其它结构代替。
Claims (8)
1.一种基于1,8-取代咔唑的高辐射速率铂配合物发光材料,其特征在于,其化学式如通式(1)所示:
其中,L为五元杂芳环;
Ra和Rb均不为氢原子且各自独立地为烷基、烷氧基、环烷基;
R1、R2、R3、R4、R5和R6各自独立地为氢、氘、烷基、烷氧基、环烷基、杂环基、烯基、未取代的芳基、未取代的芳氧基;
Ru为单取代、双取代、三取代,且Ru为氢、氘、烷基、烷氧基、环烷基;
Rv、Rw、Rx和Ry各自独立地为单取代、双取代、三取代、四取代或者无取代,且Rv、Rw、Rx和Ry各自独立地为氢、氘、烷基、烷氧基、环烷基、杂环基、烯基、未取代的芳基、未取代的芳氧基、卤素、羟基、巯基、硝基、氰基、氨基、羧基、酯基、甲硅烷基、烷基胺基、双烷基胺基、单芳基胺基、双芳基胺基或其组合。
2.根据权利要求1所述基于1,8-取代咔唑的高辐射速率铂配合物发光材料,其特征在于,杂环基为未取代的杂芳基。
4.一种权利要求1-3任一项所述基于1,8-取代咔唑的高辐射速率铂配合物发光材料在有机发光元件中的应用。
5.如权利要求4所述应用,其特征在于,所述有机发光元件为发光二极管或发光电化学电池。
6.如权利要求5所述应用,其特征在于,所述发光二极管为有机发光二极管。
7.一种如权利要求1-3任一项所述基于1,8-取代咔唑的高辐射速率铂配合物发光材料的应用,其特征在于,作为有机发光器件中的磷光发光材料或延迟荧光材料。
8.一种发光器件,其特征在于,包括第一电极、第二电极和有机层;有机层设置于第一电极和第二电极之间,且至少有一个有机层;所述有机层包括权利要求1-3任一项所述发光材料。
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