WO2022062597A1 - 一种热激活延迟荧光材料及其应用 - Google Patents
一种热激活延迟荧光材料及其应用 Download PDFInfo
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- WO2022062597A1 WO2022062597A1 PCT/CN2021/106770 CN2021106770W WO2022062597A1 WO 2022062597 A1 WO2022062597 A1 WO 2022062597A1 CN 2021106770 W CN2021106770 W CN 2021106770W WO 2022062597 A1 WO2022062597 A1 WO 2022062597A1
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- Prior art keywords
- thermally activated
- activated delayed
- fluorescent material
- delayed fluorescent
- substituted
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- 239000000463 material Substances 0.000 title claims abstract description 61
- 230000003111 delayed effect Effects 0.000 title claims abstract description 29
- 239000010410 layer Substances 0.000 claims description 54
- 150000001875 compounds Chemical class 0.000 claims description 24
- -1 tert-butylphenyl Chemical group 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- 238000002347 injection Methods 0.000 claims description 11
- 239000007924 injection Substances 0.000 claims description 11
- 230000000903 blocking effect Effects 0.000 claims description 7
- 230000005525 hole transport Effects 0.000 claims description 7
- 239000012044 organic layer Substances 0.000 claims description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- 238000005401 electroluminescence Methods 0.000 claims description 6
- 125000003944 tolyl group Chemical group 0.000 claims description 6
- 125000004802 cyanophenyl group Chemical group 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 3
- 125000001072 heteroaryl group Chemical group 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- 125000003373 pyrazinyl group Chemical group 0.000 claims description 3
- 125000002098 pyridazinyl group Chemical group 0.000 claims description 3
- 125000004076 pyridyl group Chemical group 0.000 claims description 3
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 claims 1
- 230000009477 glass transition Effects 0.000 abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
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- 239000000543 intermediate Substances 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
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- 229910021641 deionized water Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
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- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 3
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 description 2
- LELMSURPXIAXOW-UHFFFAOYSA-N 5,8-dibromo-2,3-diphenylquinoxaline Chemical compound C=1C=CC=CC=1C=1N=C2C(Br)=CC=C(Br)C2=NC=1C1=CC=CC=C1 LELMSURPXIAXOW-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
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- 238000002425 crystallisation Methods 0.000 description 2
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- 238000010586 diagram Methods 0.000 description 2
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
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- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 description 2
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- JSRLURSZEMLAFO-UHFFFAOYSA-N 1,3-dibromobenzene Chemical compound BrC1=CC=CC(Br)=C1 JSRLURSZEMLAFO-UHFFFAOYSA-N 0.000 description 1
- ZHXUWDPHUQHFOV-UHFFFAOYSA-N 2,5-dibromopyridine Chemical compound BrC1=CC=C(Br)N=C1 ZHXUWDPHUQHFOV-UHFFFAOYSA-N 0.000 description 1
- FEYDZHNIIMENOB-UHFFFAOYSA-N 2,6-dibromopyridine Chemical compound BrC1=CC=CC(Br)=N1 FEYDZHNIIMENOB-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- AWFYPPSBLUWMFQ-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,6,7-tetrahydropyrazolo[4,3-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=C2 AWFYPPSBLUWMFQ-UHFFFAOYSA-N 0.000 description 1
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- QBWKPGNFQQJGFY-QLFBSQMISA-N 3-[(1r)-1-[(2r,6s)-2,6-dimethylmorpholin-4-yl]ethyl]-n-[6-methyl-3-(1h-pyrazol-4-yl)imidazo[1,2-a]pyrazin-8-yl]-1,2-thiazol-5-amine Chemical compound N1([C@H](C)C2=NSC(NC=3C4=NC=C(N4C=C(C)N=3)C3=CNN=C3)=C2)C[C@H](C)O[C@H](C)C1 QBWKPGNFQQJGFY-QLFBSQMISA-N 0.000 description 1
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 1
- 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 1
- JSEQNGYLWKBMJI-UHFFFAOYSA-N 9,9-dimethyl-10h-acridine Chemical compound C1=CC=C2C(C)(C)C3=CC=CC=C3NC2=C1 JSEQNGYLWKBMJI-UHFFFAOYSA-N 0.000 description 1
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 1
- NUGPIZCTELGDOS-QHCPKHFHSA-N N-[(1S)-3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-pyridin-3-ylpropyl]cyclopentanecarboxamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CC[C@@H](C=1C=NC=CC=1)NC(=O)C1CCCC1)C NUGPIZCTELGDOS-QHCPKHFHSA-N 0.000 description 1
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGNDCEVUMONOKF-UGPLYTSKSA-N benzyl n-[(2r)-1-[(2s,4r)-2-[[(2s)-6-amino-1-(1,3-benzoxazol-2-yl)-1,1-dihydroxyhexan-2-yl]carbamoyl]-4-[(4-methylphenyl)methoxy]pyrrolidin-1-yl]-1-oxo-4-phenylbutan-2-yl]carbamate Chemical compound C1=CC(C)=CC=C1CO[C@H]1CN(C(=O)[C@@H](CCC=2C=CC=CC=2)NC(=O)OCC=2C=CC=CC=2)[C@H](C(=O)N[C@@H](CCCCN)C(O)(O)C=2OC3=CC=CC=C3N=2)C1 KGNDCEVUMONOKF-UGPLYTSKSA-N 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
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- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
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- 230000005693 optoelectronics Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000003252 quinoxalines Chemical class 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
- C07D241/40—Benzopyrazines
- C07D241/42—Benzopyrazines with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
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- 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
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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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
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
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- 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
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
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- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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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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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
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- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
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- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
Definitions
- OLEDs are devices prepared by depositing a layer of organic material between two metal electrodes by spin coating or vacuum evaporation.
- a classic three-layer organic electroluminescent device includes a hole transport layer, In the light-emitting layer and the electron transport layer, the holes generated by the anode are combined with the electrons generated by the cathode through the electron transport layer to form excitons in the light-emitting layer through the hole transport layer, and then emit light.
- the organic electroluminescent device can be adjusted to emit various required light by changing the material of the light-emitting layer as required.
- the present application provides a thermally activated delayed fluorescent material and an application thereof, the material has good thermal stability, and the organic electroluminescence device prepared from the material has higher efficiency, lower operating voltage and longer duration service life.
- the present application provides a thermally activated delayed fluorescent material, and the material structure is shown in formula I:
- L 2 represents one of C6-C30 substituted or unsubstituted aryl, C3-C30 substituted or unsubstituted heteroaryl;
- Ar 1 to Ar 4 each independently represent a C6-C30 substituted or unsubstituted aryl group.
- the Ar is phenyl
- each of said R 1 and R 2 independently represents one of methyl, phenyl and tolyl.
- the Ar 1 -Ar 4 are each independently represented as one of phenyl, tolyl, tert-butylphenyl, fluorenyl, dibenzofuranyl, dibenzothienyl, and phenylcarbazolyl.
- the thermally activated delayed fluorescent material is any one of the following compounds:
- the present application provides an organic electroluminescent device comprising an anode, a cathode and an organic layer, the organic layer comprising a light emitting layer, and a hole injection layer, a hole transport layer, a hole One or more layers of a hole blocking layer, an electron injection layer, and an electron transport layer, wherein the light-emitting layer contains the thermally activated delayed fluorescent material according to the structural formula I.
- the thermally activated delayed fluorescent material is used as any one of a guest material and a host material in the light-emitting layer.
- the beneficial effects of the present application are as follows: the TADF material of the present application has a novel structure and good optoelectronic properties, and is suitable for use as a light-emitting material for organic electroluminescent devices, and organic electroluminescent devices using the light-emitting material. It has higher device efficiency and service life, and at the same time, the thermally activated delayed fluorescent material described in the present application has very good thermal stability and film-forming properties, and the glass transition temperature is as high as 215° C., so it has good thermal stability.
- FIG. 1 is a schematic structural diagram of an organic electroluminescent device according to the present application.
- L 2 represents one of C6-C30 substituted or unsubstituted aryl, C3-C30 substituted or unsubstituted heteroaryl;
- Ar 1 to Ar 4 each independently represent a C6-C30 substituted or unsubstituted aryl group.
- the Ar is a phenyl group.
- R 1 and R 2 are each independently represented as one of methyl, phenyl and tolyl.
- the L 2 is one of phenyl, pyridyl, pyrimidinyl, naphthyl, biphenyl, pyrazinyl, pyridazinyl, trifluoromethylphenyl, and cyanophenyl.
- Ar 1 -Ar 4 are each independently represented as one of phenyl, tolyl, tert-butylphenyl, fluorenyl, dibenzofuranyl, dibenzothienyl, and phenylcarbazolyl .
- thermally activated delayed fluorescent material is any one of the following compounds:
- the present application also provides an organic electroluminescence device, the organic electroluminescence device comprising an anode, a cathode and an organic layer, the organic layer comprising a light emitting layer, and a hole injection layer, a hole transport layer, a hole blocking layer One or more layers of the layer, the electron injection layer, and the electron transport layer, wherein the light-emitting layer contains the thermally activated delayed fluorescent material as described in structural formula I.
- the thermally activated delayed fluorescent material is used as either a guest material or a host material in the light-emitting layer.
- Test Example 1 Test of the glass transition temperature of the compounds of Examples 1-5
- DSC 2920 Differential scanning calorimeter Pyris Diamond
- Tg glass transition temperature
- a light-emitting layer 160 Evaporating a light-emitting layer 160 with a thickness of 20 nm on the electron blocking layer.
- 85% by weight of CBP is used as the host material, and the compound of the present application is the guest material;
- Table 2 shows the device performance measured at a luminance of 100 cd/m 2 for the devices prepared by using the compounds of Examples 1-5 of the present application as guest light-emitting materials in the light-emitting layer (see Figure 1 for a schematic diagram of the structure).
- the preparation method of the device described in Comparative Example 2 is the same as the preparation method of the device in Examples 6-10, wherein EM1 is used instead of the compound of the present application as the luminescent guest material.
- the organic electroluminescent devices prepared in Examples 6-10 were tested for performance at a brightness of 100 cd/m 2 , and compared with the comparative organic electroluminescent devices prepared in Comparative Example 2. The test results are shown in Table 2.
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Abstract
一种热激活延迟荧光材料及其应用，所述热激活延迟荧光材料具有双喹喔啉结构，结构新颖，具有良好的光电性能，适合作为有机电致发光器件的发光材料，采用所述发光材料制备得到的有机电致发光器件具有更高的器件效率和使用寿命。同时，所述热激活延迟荧光材料具有非常好的热稳性和成膜性，玻璃化转变温度高达215℃。
Description
本申请属于有机电致发光器件技术领域，特别涉及一种热激活延迟荧光材料及其应用。
有机电致发光器件(OLEDs)为在两个金属电极之间通过旋涂或者真空蒸镀沉积一层有机材料制备而成的器件，一个经典的三层有机电致发光器件包含空穴传输层、发光层和电子传输层，由阳极产生的空穴经空穴传输层跟由阴极产生的电子经电子传输层结合在发光层形成激子，而后发光。有机电致发光器件可以根据需要通过改变发光层的材料来调节发射各种需要的光。
有机电致发光器件作为一种新型的显示技术，具有自发光、宽视角、低能耗、效率高、薄、色彩丰富、响应速度快、适用温度范围广、低驱动电压、可制作柔性可弯曲与透明的显示面板以及环境友好等独特优点，可以应用在平板显示器和新一代照明上，也可以作为LCD的背光源。
热激活延迟荧光材料(TADF,thermally activated delayed fluorescence)是一种新型的有机发光材料，其发光原理是三线态T1激子在热激活作用下反向系间窜越生成单线态S1激子，获得100％单线态激子，进而辐射跃迁产生荧光，既避免了使用昂贵的重金属配合物，且器件效率可与磷光器件相媲美。由于无需金属配合物，所以TADF材料具有价格低廉、环境友好等优点，使得在OLED、生物等领域具有广阔应用前景。
从2009年TADF材料发明以来，已经取得了快速发展，但是，现有的TADF材料及其OLED器件还是存在很多不足，特别是材料的稳定性、器件的稳定性和使用寿命。因此，开发高效稳定的TADF材料具有重要意义。根据TADF的特性，匹配的HOMO能级和LUMO能级能够降低分子内电子云的重叠，并且可以通过在推电子基团和吸电子基团中间加入阻隔基团来实现电子云的分离，降低分子的三重态激发态和单重态激发态之间的能级差，提高发光效率和降低电压。
另外，相比较传统的荧光材料，TADF材料的稳定性存在不足，效率滚降比 较厉害，因此，需要开发具有高稳定性和高效率的热激活延迟荧光材料。
发明内容
本申请提供了一种热激活延迟荧光材料及其应用，所述材料具有良好的热稳定性，并以此材料制备的有机电致发光器件具有更高的效率、更低的工作电压和更长的使用寿命。
一方面，本申请提供了一种热激活延迟荧光材料，所述材料结构如式I所示：
其中，L
1和L
3各自独立地表示为空、单键、O、S、Se、NAr、CR
1R
2，Ar表示为C6-C30取代或者未取代的芳基，R
1和R
2各自独立地表示为C1-C12取代或者未取代烷基、C6-C30取代或者未取代的芳基；
L
2表示为C6-C30取代或未取代的芳基、C3-C30取代或未取代的杂芳基之一；并且
Ar
1-Ar
4各自独立地表示为C6-C30取代或者未取代的芳基。
优选地，所述Ar为苯基。
优选地，所述R
1和R
2各自独立地表示为甲基、苯基、甲苯基之一。
优选地，所述L
2为苯基、吡啶基、嘧啶基、萘基、联苯基、吡嗪基、哒嗪基、三氟甲基苯基、氰基苯基之一。
优选地，所述Ar
1-Ar
4各自独立地表示为苯基、甲苯基、叔丁基苯基、芴基、二苯并呋喃基、二苯并噻吩基、苯基咔唑基之一。
优选地，所述热激活延迟荧光材料为如下化合物中的任意一种：
另一方面，本申请提供了一种有机电致发光器件，所述有机致电发光器件包含阳极、阴极和有机层，所述有机层包含发光层，以及空穴注入层、空穴传输层、空穴阻挡层、电子注入层、电子传输层中的一层或一层以上，其中所述发光层含有如结构式I所述的热激活延迟荧光材料。
优选地，所述热激活延迟荧光材料用作发光层中的客体材料、主体材料中的任意一种。
与现有技术相比，本申请的有益效果是：本申请的TADF材料结构新颖，具有良好的光电性能，适合作为有机电致发光器件的发光材料，采用所述发光材料的有机电致发光器件具有更高的器件效率和使用寿命，同时，本申请所述热激活延迟荧光材料具有非常好的热稳性和成膜性，玻璃化转变温度高达 215℃，因此具有良好的热稳定性。
图1为本申请的一种有机电致发光器件结构示意图。
图中：110、玻璃基板，120、阳极，130、空穴注入层，140、空穴传输层，150、发光层，160、空穴阻挡层，170、电子传输层，180、电子注入层，190、阴极。
下面通过具体实施例，并结合附图，对本申请的技术方案作进一步的具体说明。
本申请提供了一种热激活延迟荧光材料，所述材料结构如式I所示：
其中，L
1和L
3各自独立地表示为空、单键、O、S、Se、NAr、CR
1R
2，Ar表示为C6-C30取代或者未取代的芳基，R
1和R
2各自独立地表示为C1-C12取代或者未取代烷基、C6-C30取代或者未取代的芳基；
L
2表示为C6-C30取代或未取代的芳基、C3-C30取代或未取代的杂芳基之一；
Ar
1-Ar
4各自独立地表示为C6-C30取代或者未取代的芳基。
本申请中，所述Ar为苯基。
本申请中，所述R
1和R
2各自独立地表示为甲基、苯基、甲苯基之一。
本申请中，所述L
2为苯基、吡啶基、嘧啶基、萘基、联苯基、吡嗪基、哒嗪基、三氟甲基苯基、氰基苯基之一。
本申请中，所述Ar
1-Ar
4各自独立地表示为苯基、甲苯基、叔丁基苯基、芴 基、二苯并呋喃基、二苯并噻吩基、苯基咔唑基之一。
本申请中，所述热激活延迟荧光材料为如下化合物中的任意1种：
本申请还提供了一种有机电致发光器件，所述有机电致发光器件包含阳极、阴极和有机层，所述有机层包含发光层，以及空穴注入层、空穴传输层、空穴阻挡层、电子注入层、电子传输层中的一层或一层以上，其中发光层含有如结构式I所述的热激活延迟荧光材料。
本申请中，所述热激活延迟荧光材料用作发光层中的客体材料、主体材料中的任意一种。
本申请中，所述有机层中的发光层含有如结构式I所述的热激活延迟荧光材料。
本申请提供了若干个示例性的化合物。在随后的具体实施例中，对部分化合物的合成方法进行示例性的描述，并对相应化合物制备的有机电致发光器件进行示例性描述，但本申请的保护范围绝不仅限于此。
实施例 中间体的制备
1.中间体I的合成
在烧瓶中加入5,8-二溴-2,3-二苯基喹喔啉(10g，22.7mmol)，咔唑(3.4g，20.3mmol)，叔丁醇钠(3.3g，34.3mmol)，Pd
2(dba)
3(0.15g)，三叔丁基膦(0.1g)和100mL无水甲苯，回流反应2小时，加稀盐酸调至弱酸性分液，干燥，浓缩，粗品经甲苯重结晶得到7.2g，产率为60％。
1H NMR(400MHz,CDCl
3)δ:8.11-8.14(m,2H),8.04(d,J＝7.2Hz,1H),7.82(d,J＝7.6Hz,1H),7.61-7.63(m,2H),7.50-7.57(m,4H),7.32-7.38(m,8H),7.20-7.24(m,2H).HRMS(ESI,m/z):[M+H]
+526.10.
2.中间体II的合成
在烧瓶中加入中间体I(7g，13.3mmol)，联硼酸频哪醇酯(4.1g，16.1mmol)，醋酸钾(3.9g，39.7mmol)，Pd(PPh
3)
3Cl
2(0.07g)，70mL无水甲苯，回流反应5小时，冷却，过硅胶，甲苯淋洗，浓缩至约30mL，滴加30mL乙醇析晶，过滤，烘干，得到7.1g类白色产品，产率为93％。
1H NMR(400MHz,CDCl
3)δ:8.10-8.13(m,2H),7.91(d,J＝7.2Hz,1H),7.63-7.65(m,2H),7.52-7.58(m,5H),7.39-7.43(m,2H),7.32-7.38(m,6H),7.22-7.26(m,2H),1.24(s,12H).HRMS(ESI,m/z):[M+H]
+574.25.
3.中间体III的合成
在烧瓶中加入5,8-二溴-2,3-二苯基喹喔啉(10g，22.7mmol)，9,9-二甲基-9,10-二氢吖啶(4.3g，20.5mmol)，叔丁醇钠(3.3g，34.3mmol)，Pd
2(dba)
3(0.15g)，三叔丁基膦(0.1g)和100mL无水甲苯，回流反应2小时，加稀盐 酸调至弱酸性分液，干燥，浓缩，粗品经甲苯重结晶得到8g白色产品，产率为62％。
1H NMR(400MHz,CDCl
3)δ:8.01(d,J＝8.0Hz,1H),7.51-7.61(m,5H),7.31-7.39(m,6H),7.11-7.21(m,6H),7.00-7.02(m,2H),1.53(s,6H).HRMS(ESI,m/z):[M+H]
+561.12.
4.中间体IV的合成
在烧瓶中加入中间体III(7g，12.3mmol)，联硼酸频哪醇酯(3.75g，14.8mmol)，醋酸钾(3.6g，36.7mmol)，Pd(PPh
3)
3Cl
2(0.07g)，70mL无水甲苯，回流反应5小时，冷却，过硅胶，甲苯淋洗，浓缩至约30mL，滴加30mL乙醇析晶，过滤，烘干，得到6.9g类白色产品，产率为91％。
1H NMR(400MHz,CDCl
3)δ:7.85(d,J＝7.6Hz,1H),7.54-7.60(m,4H),7.41(d,J＝7.2Hz,1H),7.34-7.38(m,6H),7.17-7.21(m,4H),7.09-7.13(m,2H),7.00-7.03(m,2H),1.53(s,6H),1.24(s,12H).HRMS(ESI,m/z):[M+H]
+616.33.
实施例1 化合物1的合成
在烧瓶中加入中间体II(2.0g，3.49mmol)，1,4-二溴苯(0.40g，1.70mmol)，碳酸钾(0.70g，5.09mmol)，Pd(PPh
3)
4(0.01g)，再加入甲苯(10mL)，乙醇(5mL)和去离子水(5mL)，氮气保护下回流反应5小时，分液，浓缩，粗品经柱色谱得到1.4g白色产品，产率为86％。
1H NMR(400MHz,CDCl
3)δ:8.11-8.14(m,4H),7.93(d,J＝6.4Hz,2H),7.79(d,J＝6.4Hz,2H),7.53-7.59(m,12H),7.47-7.49(m,4H),7.30-7.37(m,16H),7.19-7.24(m,4H).HRMS(ESI,m/z):[M+H]
+969.35.
实施例2 化合物9的合成
在烧瓶中加入中间体II(2g，3.49mmol)，2,5-二溴吡啶(0.40g，1.69mmol)，碳酸钾(0.70g，5.06mmol)，Pd(PPh
3)
4(0.01g)，再加入甲苯(10mL)，乙醇(5mL)和去离子水(5mL)，氮气保护下回流反应5小时，分液，浓缩，粗品经柱色谱得到1.3g白色产品，产率为80％。
1H NMR(400MHz,CDCl
3)δ:9.43(d,J＝2.0Hz,1H),8.07-8.14(m,6H),7.94(d,J＝6.8Hz,1H),7.80-7.88(m,3H),7.54-7.59(m,8H),7.47-7.49(m,4H),7.30-7.37(m,16H),7.19-7.24(m,4H).HRMS(ESI,m/z):[M+H]
+970.35.
实施例3 化合物8的合成
在烧瓶中加入中间体IV(2g，3.25mmol)，1,4-二溴苯(0.37g，1.57mmol)，碳酸钾(0.65g，4.70mmol)，Pd(PPh
3)
4(0.01g)，再加入甲苯(10mL)，乙醇(5mL)和去离子水(5mL)，氮气保护下回流反应5小时，分液，浓缩，粗品经柱色谱得到1.4g白色产品，产率为85％。
1H NMR(400MHz,CDCl
3)δ:7.89(d,J＝7.2Hz,2H),7.50-7.59(m,14H),7.30-7.37(m,12H),7.20-7.24(m,8H),7.10-7.15(m,4H),6.97-6.99(m,4H),1.56(s,12H).HRMS(ESI,m/z):[M+H]
+1053.44.
实施例4 化合物23的合成
在烧瓶中加入中间体IV(2g，3.25mmol)，1,3-二溴苯(0.37g，1.57mmol)，碳酸钾(0.65g，4.70mmol)，Pd(PPh
3)
4(0.01g)，再加入甲苯(10mL)，乙醇(5mL)和去离子水(5mL)，氮气保护下回流反应5小时，分液，浓缩，粗品经柱色谱得到1.4g白色产品，产率为85％。
1H NMR(400MHz,CDCl
3)δ:8.25(t,J＝1.6Hz,1H),7.89(d,J＝7.2Hz,2H),7.54-7.59(m,9H),7.49(d,J＝7.6Hz,2H), 7.40-7.43(m,2H),7.30-7.36(m,12H),7.20-7.23(m,8H),7.10-7.15(m,4H),6.97-6.99(m,4H),1.56(s,12H).HRMS(ESI,m/z):[M+H]
+1053.47.
实施例5 化合物25的合成
在烧瓶中加入中间体IV(2g，3.25mmol)，2,6-二溴吡啶(0.375g，1.58mmol)，碳酸钾(0.6g，4.78mmol)，Pd(PPh
3)
4(0.01g)，再加入甲苯(10mL)，乙醇(5mL)和去离子水(5mL)，氮气保护下回流反应5小时，分液，浓缩，粗品经柱色谱得到1.4g白色产品，产率为84％。
1H NMR(400MHz,CDCl
3)δ:8.25(t,J＝1.6Hz,1H),7.89(d,J＝7.2Hz,2H),7.54-7.59(m,9H),7.49(d,J＝7.6Hz,2H),7.40-7.43(m,2H),7.30-7.36(m,12H),7.20-7.23(m,8H),7.10-7.15(m,4H),6.97-6.99(m,4H),1.56(s,12H).HRMS(ESI,m/z):[M+H]
+1054.45.
试验例1 实施例1-5的化合物玻璃化转化温度的测试
用差示扫描量热仪Pyris Diamond(DSC 2920)在氮气保护下，以10℃/分钟的加热和冷却速度分别测试实施例1-5制备得到的化合物的玻璃化转变温度(Tg)，并以化合物EM1作为对比例1进行对比。具体如表1所示。
化合物EM1的结构式如下所示：
表1各化合物的玻璃化转变温度
| 化合物 | 玻璃化温度(℃) | |
| 实施例1 | 1 | 198 |
| 实施例2 | 9 | 207 |
| 实施例3 | 8 | 211 |
| 实施例4 | 23 | 225 |
| 实施例5 | 25 | 237 |
| 对比例1 | EM1 | 134 |
从表1可以看出，本申请的化合物的玻璃化温度明显高于对比例1已经公开的化合物EM1，说明本申请采用两个喹喔啉作为吸电子基团可以有效地改善有机电致发光材料的热稳定性。
实施例6-10 有机电致发光器件的制备
本申请中得到的TADF化合物可以作为发光客体材料用在有机电致发光器件上，为进一步说明本申请得到的TADF材料的应用，采用本申请实施例1-5的化合物并通过以下方法制备对应的OLED器件：
a.将带有阳极120的透明导电ITO玻璃基板110(中国南玻集团股份有限公司)依次经：去离子水、乙醇、丙酮和去离子水洗净，再用氧等离子处理30秒；
b.在ITO上蒸镀3nm厚的MnO
3(氧化钼)为空穴注入层130；
c.在空穴注入层上蒸镀50nm厚的TAPC为空穴传输材料140；
d.蒸镀TCTA，形成5nm厚的电子阻挡层150；
e.在电子阻挡层上蒸镀20nm厚的发光层160，发光层160中，以85％重量比的CBP作为主体材料，本申请化合物为客体材料；
f.在发光层上蒸镀40nm厚的BmPYPB作为电子传输层170；
g.蒸镀1nm LiF为电子注入层180和80nm Al作为器件阴极190。
采用本申请实施例1-5的化合物作为发光层客体发光材料所制备的器件(结构示意图见图1)测得的在100cd/m
2的亮度下的器件性能如表2。
对比例2 对比有机电致发光器件的制备
对比例2所述器件的制备方法同实施例6-10器件的制备方法，其中采用EM1代替本申请化合物作为发光客体材料。
试验例2 实施例6-10的有机电致发光器件性能测试
对实施例6-10制备得到的有机电致发光器件在100cd/m
2的亮度下进行性能 测试，并与对比例2制备得到的对比有机电致发光器件进行对比，测试结果见表2。
| 化合物 | 电流效率(cd/A) | 外量子效率 | 发光颜色 | |
| 实施例6 | 1 | 39 | 15.7％ | 红光 |
| 实施例7 | 9 | 41 | 16.4％ | 红光 |
| 实施例8 | 8 | 42 | 16.7％ | 红光 |
| 实施例9 | 23 | 45 | 17.2％ | 红光 |
| 实施例10 | 25 | 47 | 18.3％ | 红光 |
| 对比例2 | EM | 28 | 10.1％ | 红光 |
其中，器件制备过程中中涉及化合物的结构式如下：
从表2中可以看出，本申请制备得到的热激活延迟荧光材料用于有机电致发光器件，可以降低工作电压，提高器件效率，是具有优良性能的TADF材料。
综上所述，本申请的化合物具有高的稳定性，同时制备的有机电致发光器件具有高的效率和光纯度。
以上所述的实施例只是本申请的较佳方案，并非对本申请作任何形式上的限制，在不超出权利要求所记载的技术方案的前提下还有其它的变体及改型。
Claims (8)
- 一种热激活延迟荧光材料，其结构如式I所示：
其中，L 1和L 3各自独立地表示为空、单键、O、S、Se、NAr、CR 1R 2，Ar表示为C6-C30取代或者未取代的芳基，R 1和R 2各自独立地表示为C1-C12取代或者未取代烷基、C6-C30取代或者未取代的芳基；L 2表示为C6-C30取代或未取代的芳基、C3-C30取代或未取代的杂芳基之一；并且Ar 1-Ar 4各自独立地表示为C6-C30取代或者未取代的芳基。 - 根据权利要求1所述一种热激活延迟荧光材料，其中，所述Ar为苯基。
- 根据权利要求1所述一种热激活延迟荧光材料，其中，所述R 1和R 2各自独立地表示为甲基、苯基、甲苯基之一。
- 根据权利要求1所述一种热激活延迟荧光材料，其中，所述L 2为苯基、吡啶基、嘧啶基、萘基、联苯基、吡嗪基、哒嗪基、三氟甲基苯基、氰基苯基之一。
- 根据权利要求1所述一种热激活延迟荧光材料，其中，所述Ar 1-Ar 4各自独立地表示为苯基、甲苯基、叔丁基苯基、芴基、二苯并呋喃基、二苯并噻吩基、苯基咔唑基之一。
- 根据权利要求1所述一种热激活延迟荧光材料，其中，所述热激活延迟荧光材料为如下化合物中的任意一种：
- 一种有机电致发光器件，其包含阳极、阴极和有机层，所述有机层包含发光层，以及空穴注入层、空穴传输层、空穴阻挡层、电子注入层、电子传输层中的一层或一层以上，其中所述发光层含有如权利要求1-6任一项所述的热激活延迟荧光材料。
- 根据权利要求7所述一种有机电致发光器件，其中，所述热激活延迟荧光材料用作发光层中的客体材料、主体材料中的任意一种。
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