CN108484592A - 基于大位阻空间电荷转移的tadf材料及其合成方法与应用 - Google Patents
基于大位阻空间电荷转移的tadf材料及其合成方法与应用 Download PDFInfo
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- CN108484592A CN108484592A CN201810341440.1A CN201810341440A CN108484592A CN 108484592 A CN108484592 A CN 108484592A CN 201810341440 A CN201810341440 A CN 201810341440A CN 108484592 A CN108484592 A CN 108484592A
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- aromatic
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- 239000000463 material Substances 0.000 title claims abstract description 44
- 238000012546 transfer Methods 0.000 title claims abstract description 20
- 238000010189 synthetic method Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- -1 bromo aromatic hydrocarbon Chemical class 0.000 claims abstract description 16
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004327 boric acid Substances 0.000 claims abstract description 10
- 239000012467 final product Substances 0.000 claims abstract description 9
- 238000005401 electroluminescence Methods 0.000 claims abstract description 8
- 238000006467 substitution reaction Methods 0.000 claims abstract description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000001246 bromo group Chemical group Br* 0.000 claims abstract description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 12
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 8
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 6
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- ZSZKAQCISWFDCQ-UHFFFAOYSA-N 2-fluorobenzenesulfonyl chloride Chemical class FC1=CC=CC=C1S(Cl)(=O)=O ZSZKAQCISWFDCQ-UHFFFAOYSA-N 0.000 claims description 4
- RCVAFPIOURWVLC-UHFFFAOYSA-N bromobenzene;sulfuryl dichloride Chemical class ClS(Cl)(=O)=O.BrC1=CC=CC=C1 RCVAFPIOURWVLC-UHFFFAOYSA-N 0.000 claims description 4
- NZCKTGCKFJDGFD-UHFFFAOYSA-N 2-bromobenzoyl chloride Chemical class ClC(=O)C1=CC=CC=C1Br NZCKTGCKFJDGFD-UHFFFAOYSA-N 0.000 claims description 3
- RAAGZOYMEQDCTD-UHFFFAOYSA-N 2-fluorobenzoyl chloride Chemical class FC1=CC=CC=C1C(Cl)=O RAAGZOYMEQDCTD-UHFFFAOYSA-N 0.000 claims description 3
- ZZPNDIHOQDQVNU-UHFFFAOYSA-N 2-hydroxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound CC1(C)OB(O)OC1(C)C ZZPNDIHOQDQVNU-UHFFFAOYSA-N 0.000 claims description 3
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000000468 ketone group Chemical group 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims 1
- 239000003205 fragrance Substances 0.000 claims 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 12
- 238000003786 synthesis reaction Methods 0.000 abstract description 12
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 48
- 238000003756 stirring Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 235000010338 boric acid Nutrition 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 238000010898 silica gel chromatography Methods 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- SPWVRYZQLGQKGK-UHFFFAOYSA-N dichloromethane;hexane Chemical compound ClCCl.CCCCCC SPWVRYZQLGQKGK-UHFFFAOYSA-N 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 0 Cc1ccccc1P1(c2ccccc2-c2c1cccc2)=* Chemical compound Cc1ccccc1P1(c2ccccc2-c2c1cccc2)=* 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VHUXLBLPAMBOJS-UHFFFAOYSA-N Cc(cc1)cc2c1[s]c1ccccc21 Chemical compound Cc(cc1)cc2c1[s]c1ccccc21 VHUXLBLPAMBOJS-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000002027 dichloromethane extract Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Substances C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000003809 water extraction Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CYPVTICNYNXTQP-UHFFFAOYSA-N 10-[4-[4-(9,9-dimethylacridin-10-yl)phenyl]sulfonylphenyl]-9,9-dimethylacridine Chemical compound C12=CC=CC=C2C(C)(C)C2=CC=CC=C2N1C1=CC=C(S(=O)(=O)C=2C=CC(=CC=2)N2C3=CC=CC=C3C(C)(C)C3=CC=CC=C32)C=C1 CYPVTICNYNXTQP-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- GIAJEDAGCHTSBO-UHFFFAOYSA-N C1=CC=CC=2C3=CC=CC=C3NC12.BrC1=CC=CC=C1 Chemical compound C1=CC=CC=2C3=CC=CC=C3NC12.BrC1=CC=CC=C1 GIAJEDAGCHTSBO-UHFFFAOYSA-N 0.000 description 1
- BNHXZDRWXJEWEG-UHFFFAOYSA-N CC1(C)c(cccc2)c2N(C)c2c1cccc2 Chemical compound CC1(C)c(cccc2)c2N(C)c2c1cccc2 BNHXZDRWXJEWEG-UHFFFAOYSA-N 0.000 description 1
- VTKMFJSESAHMLR-UHFFFAOYSA-N Cc(cc1)cc2c1[o]c1ccccc21 Chemical compound Cc(cc1)cc2c1[o]c1ccccc21 VTKMFJSESAHMLR-UHFFFAOYSA-N 0.000 description 1
- DHRJNYVWARQVMI-UHFFFAOYSA-N Cc(cc1)ccc1P(c1ccccc11)=C2C1=CC=C[CH]2 Chemical compound Cc(cc1)ccc1P(c1ccccc11)=C2C1=CC=C[CH]2 DHRJNYVWARQVMI-UHFFFAOYSA-N 0.000 description 1
- GOKQFMBZDMECDK-UHFFFAOYSA-N Cc(cc1)ccc1P1(c(cccc2)c2-c2c1cccc2)=O Chemical compound Cc(cc1)ccc1P1(c(cccc2)c2-c2c1cccc2)=O GOKQFMBZDMECDK-UHFFFAOYSA-N 0.000 description 1
- FYZUJSOIGUIRTE-UHFFFAOYSA-N Cc1c(C)c([N](c2c(C)cccc2)(O)O)ccc1 Chemical compound Cc1c(C)c([N](c2c(C)cccc2)(O)O)ccc1 FYZUJSOIGUIRTE-UHFFFAOYSA-N 0.000 description 1
- LEIKPMFRIYWHKW-UHFFFAOYSA-N Cc1c2Sc(cccc3)c3Sc2ccc1 Chemical compound Cc1c2Sc(cccc3)c3Sc2ccc1 LEIKPMFRIYWHKW-UHFFFAOYSA-N 0.000 description 1
- NICUQYHIOMMFGV-UHFFFAOYSA-N Cc1c2[s]c3ccccc3c2ccc1 Chemical compound Cc1c2[s]c3ccccc3c2ccc1 NICUQYHIOMMFGV-UHFFFAOYSA-N 0.000 description 1
- FOLYJXDWKIYWND-UHFFFAOYSA-N Cc1cc(N2c3ccccc3Sc3c2cccc3)ccc1 Chemical compound Cc1cc(N2c3ccccc3Sc3c2cccc3)ccc1 FOLYJXDWKIYWND-UHFFFAOYSA-N 0.000 description 1
- GCXJMHPAYQCQIL-UHFFFAOYSA-N Cc1cc(P(c2ccccc22)=C3C2=CC=C[CH]3)ccc1 Chemical compound Cc1cc(P(c2ccccc22)=C3C2=CC=C[CH]3)ccc1 GCXJMHPAYQCQIL-UHFFFAOYSA-N 0.000 description 1
- JMKRZNCIDROVCI-UHFFFAOYSA-N Cc1cc(P2(c3ccccc3-c3c2cccc3)=[U])ccc1 Chemical compound Cc1cc(P2(c3ccccc3-c3c2cccc3)=[U])ccc1 JMKRZNCIDROVCI-UHFFFAOYSA-N 0.000 description 1
- XLTFRTTTZWMJJQ-UHFFFAOYSA-N Cc1cccc2c1[o]c1ccccc21 Chemical compound Cc1cccc2c1[o]c1ccccc21 XLTFRTTTZWMJJQ-UHFFFAOYSA-N 0.000 description 1
- XTXVVLPQOYBPGL-UHFFFAOYSA-N Cc1ccccc1P(c1ccccc11)=C2C1=CC=C[CH]2 Chemical compound Cc1ccccc1P(c1ccccc11)=C2C1=CC=C[CH]2 XTXVVLPQOYBPGL-UHFFFAOYSA-N 0.000 description 1
- QQEHXJUOFPMHFN-UHFFFAOYSA-N O=C=S(c(cc1)ccc1F)(c(cccc1)c1F)=O Chemical compound O=C=S(c(cc1)ccc1F)(c(cccc1)c1F)=O QQEHXJUOFPMHFN-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000002061 vacuum sublimation Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
- C07D417/02—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 two hetero rings
- C07D417/12—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 two hetero rings linked by a chain containing hetero atoms as chain links
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
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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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- 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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- 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
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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
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- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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Abstract
本发明公开了一种基于大位阻空间电荷转移的TADF材料及其合成方法与应用,其可通过先得到2位取代的氟代或溴代的中间体,再将和相对应的硼酸通过Sizuki反应或者与相对应的芳香胺通过取代反应得到最终产物;或者先得到对应的硼酸酯中间体,再和相对应的溴代芳香烃通过Sizuki反应得到最终产物。本发明合成工艺简单,纯化容易,所合成的TADF发光材料具有高的发光效率,发光颜色可调的特性,同时可作为发光层用于制备高效率、低成本以及稳定性好的有机电致发光器件。
Description
技术领域
本发明涉及新材料领域,特别是一种基于大位阻空间电荷转移的热激活延迟荧光材料,以及合成方法及其作为发光层材料在有机电致发光器件中的应用。
技术背景
有机发光二极管(Organic Light-Emitting Devices,OLEDs)从首次报道至今到现在已经有二十多年,在材料开发与器件制备工艺方面都得到了快速的发展。OLED应用于手机、数码相机、电脑等的显示屏幕,尤其在电视显示技术领域,大尺寸、透明性、可弯曲的OLED屏幕是目前发展的方向。但是,目前有机发光二极管还存在发光效率低、使用寿命短、稳定性差以及制作成本高等一系列不足,还不能实现大规模商业化应用。
现阶段,已经实现商业化的有机电致发光材料主要是磷光材料,磷光材料由于可以同时利用单线态激子和三线态激子,因此其理论内量子效率可以达到100%。但磷光材料主要使用价格昂贵的贵金属(铱、铂)配合物,因此磷光电致发光器件的制备成本较高。此外,磷光电致发光材料还存在蓝光材料发光性能不稳定,其电致发光器件的最长使用寿命只有1000小时左右,远不能满足商业化应用;由于磷光电致发光材料的激子浓度很高而且寿命较长,因此存在比较严重的效率滚降。故发展低成本、高效率、稳定性好的有机电致发光材料是实现OLED大规模商业化应用的必要条件之一。
2008年,日本九州大学Adachi教授课题组率先提出了内量子效率高达100%的热活化延迟荧光(TADF)的机理(Endo,A.;Ogasawara,M.;Takahashi,A.;Yokoyama,D.;Kato,Y.;Adachi,C.,Adv.Mater.,2009,21(47),4802-6.),并合成了一系列性能优异的TADF材料,比较典型的是外量子效率高达19.5%的蓝光TADF材料DMAC-DPS(Zhang,Q.;Li,B.;Huang,S.;Nomura,H.;Tanaka,H.;Adachi,C.,Nat.Photonics,2014,8(4),326-332.)。说明TADF材料有望替代磷光材料,可以有效地解决磷光材料高成本和蓝光材料不稳定的问题。2015年,Cheng等[出了一种设计高效率TADF材料的新策略(Rajamalli,P.;Senthilkumar,N.;Gandeepan,P.;Huang,P.Y.;Huang,M.J.;Ren-Wu,C.Z.;Yang,C.Y.;Chiu,M.J.;Chu,L.K.;Lin,H.W.;Cheng,C.H.,J.Am.Chem.Soc.,2016,138(2),628-34.),通过邻位取代使分子的电子受体部分和电子给体部分在空间上相互靠近,形成强的分子内作用力,可以有效地抑制非辐射跃迁途径,并且可以有效减少单线态和三线态间的能级差ΔEST,为三线态激子的反系间窜越提供了条件,使得该化合物内量子效率达100%。2017年,Swager等报道了具有类似结构的高效热激活延迟荧光材料(Tsujimoto,H.;Ha,D.G.;Markopoulos,G.;Chae,H.S.;Baldo,M.A.;Swager,T.M.,J.Am.Chem.Soc.,2017,139(13),4894-4900.),通过一个基团作为支架,在合适的位点引入合适的电子受体基团和电子给体基团,形成了一类U型分子。通过单晶结构可以发现,此类U型分子的电子受体部分和电子给体部分均存在π-π作用力(d为)。作者还发现这种分子内π-π作用力不仅可以有效地抑制非辐射跃迁的过程,还可形成分子内空间电荷转移,最终得到高效率的TADF材料。同年,Lu等]也报道了类似的U型分子的蓝光TADF材料,溶液加工制备的非掺杂蓝光电致发光器件的最大外量子效率为19.1%(Chen,X.L.;Jia,J.H.;Yu,R.;Liao,J.Z.;Yang,M.X.;Lu,C.Z.,Angew.Chem.Int.Ed.,2017,56(47),15006-15009.)
由此可见,通过在支架基团的合适位点引入电子给体和电子受体基团可以实现大位阻特性和分子内空间电荷转移特性,从而获得高发光效率的TADF材料。
发明内容
本发明的目的是提供一种基于大位阻空间电荷转移的TADF材料,其具有高荧光量子效率且低成本等优点。
本发明的另一个目的是提供上述基于大位阻空间电荷转移的TADF材料的合成方法,该方法合成简单、提纯容易而且产率很高,并且可以通过改变支架基团、电子给体基团和电子受体基团来调节材料的发光颜色。
本发明还有一个目的是将上述大位阻空间电荷转移的TADF材料应用在有机电致发光器件上。
为实现上述目的,本发明提供一种基于大位阻空间电荷转移的TADF材料,其结构如通式所示:
其中,X为酮基或者砜基;R为芳香环或芳香杂环取代基,或者是H原子、卤素原子、甲氧基、二甲基胺、硝基、氰基或羧基;Ar为芳香环或芳香杂环取代基。
上述基于大位阻的空间电荷转移TADF材料的合成方法,其特征包括以下步骤:
方法一:
(1)将2-溴苯磺酰氯、2-氟苯磺酰氯、2-溴苯甲酰氯或2-氟苯甲酰氯与氟苯或溴苯通过傅-克反应得到2位取代的氟代或溴代的中间体;
(2)再将步骤(1)得到的中间体和相对应的硼酸通过Sizuki反应或者与相对应的芳香胺通过取代反应得到最终产物。
方法二:
(1)将溴代芳香化合物与联硼酸频那醇酯通过Suziki反应得到对应的硼酸酯中间体;
(2)再将步骤(1)得到的中间体和相对应的溴代芳香烃通过Sizuki反应得到最终产物。
其中,硼酸是包含有Ar基团的硼酸;芳香胺是包含有Ar基团的芳香胺或是包含有R基团的芳香胺;溴代芳香化合物是包含有Ar基团的溴代芳香化合物。
上述大位阻空间电荷转移的TADF材料应用于制备有机电致发光器件。
本发明是基于大位阻的空间电荷转移TADF发光材料,其合成工艺简单,纯化容易,所合成的TADF发光材料具有高的发光效率,发光颜色可调的特性,同时作为发光层制备高效率、低成本以及稳定性好的有机电致发光器件。
附图说明
图1是本发明实施例1-3产物薄膜(厚度为100nm)的稳态光谱图。
具体实施方式
本发明是一种基于大位阻空间电荷转移的TADF材料,其结构如通式所示:
其中,X为酮基或者砜基;R为芳香环或芳香杂环取代基,或者是H原子、卤素原子、甲氧基、二甲基胺、硝基、氰基或羧基;Ar为芳香环或芳香杂环取代基。
优选的,当Ar、R为芳香环或芳香杂环取代基时,可相同或不同,选自:
其中,R1和R2相同或不同,选自H原子、卤素原子、甲基、叔丁基、甲氧基、二甲基胺或三氟甲基。
上述基于大位阻的空间电荷转移TADF材料的合成方法,其特征包括以下步骤:
方法一:
(1)将2-溴苯磺酰氯、2-氟苯磺酰氯、2-溴苯甲酰氯或2-氟苯甲酰氯与氟苯或溴苯通过傅-克反应得到2位取代的氟代或溴代的中间体;
(2)再将步骤(1)得到的中间体和相对应的硼酸通过Sizuki反应或者与相对应的芳香胺通过取代反应得到最终产物。
方法二:
(1)将溴代芳香化合物与联硼酸频那醇酯通过Suziki反应得到对应的硼酸酯中间体;
(2)再将步骤(1)得到的中间体和相对应的溴代芳香烃通过Sizuki反应得到最终产物。
其中,硼酸是包含有Ar基团的硼酸;芳香胺是包含有Ar基团的芳香胺或是包含有R基团的芳香胺;溴代芳香化合物也是包含有Ar基团。
上述大位阻空间电荷转移的TADF材料应用于制备有机电致发光器件。
以下通过具体的实施例子对本发明作进一步的阐述,但本发明并不限于此特定例子。
实施例1
(1)中间体【2-溴-4’-氟二苯砜】的合成
2-溴苯磺酰氯10mmol和氟苯25mmol到三口瓶中,在氮气气氛保护下搅拌溶解,加入三氯化铁13mmol,在40℃温度下搅拌反应70min。加入2M盐酸50mL终止反应。用适量二氯甲烷萃取三次,得到的有机相再加入纯水萃取三次。有机相加入无水硫酸钠干燥,过滤,减压旋蒸得2-溴-4’-氟二苯砜。产率90%。
(2)中间体【2-溴-4’-吩噻嗪二苯砜】的合成
在氮气气氛保护下,吩噻嗪10mmol加入三口瓶中,加入N,N-二甲基甲酰胺20mL搅拌使之溶解。加入叔丁醇钾10mmol,搅拌10min后,加入2-溴-4’-氟二苯砜10mmol。升温至100℃继续搅拌反应5h。反应液倒入100mL水中进行沉淀,抽滤,水洗。粗产物用硅胶柱层析提纯,淋洗液为1:1的二氯甲烷-正己烷混合溶剂。得淡黄色的结晶产物,产率80%。
(3)最终产物【2-苯咔唑-4’-吩噻嗪二苯砜】的合成
在氮气气氛保护下,2-溴-4’-吩噻嗪二苯砜10mmol和4-咔唑苯硼酸12mmol加入三口瓶中,加入甲苯50mL搅拌使之溶解。加入碳酸钾水溶液14mmol/2ml H2O和0.5ml相转移剂,搅拌5min后,加入0.05g四三苯基膦钯作为催化剂。搅拌回流36h后将反应液冷却,抽滤,滤液用旋转蒸发仪蒸干。用硅胶柱层析的方法进行提纯,淋洗液为体积比2:1的二氯甲烷和正己烷的混合溶液。得淡黄色结晶产物,产率66%。
实施例2
(1)中间体【2-氟-4’-氟二苯砜】的合成
2-氟苯磺酰氯10mmol和氟苯25mmol到三口瓶中,在氮气气氛保护下搅拌溶解,加入三氯化铁13mmol,在40℃温度下搅拌反应70min。加入2M盐酸50mL终止反应。用适量二氯甲烷萃取三次,得到的有机相再加入纯水萃取三次。有机相加入无水硫酸钠干燥,过滤,减压旋蒸得2-氟-4’-氟二苯砜。产率90%。
(2)中间体【2-氟-4’-吩噻嗪二苯砜】的合成
在氮气气氛保护下,吩噻嗪10mmol加入三口瓶中,加入N,N-二甲基甲酰胺20mL搅拌使之溶解。加入叔丁醇钾10mmol,搅拌10min后,加入2-氟-4’-氟二苯砜10mmol。升温至100℃继续搅拌反应5h。反应液倒入100mL水中进行沉淀,抽滤,水洗。粗产物用硅胶柱层析提纯,淋洗液为1:1的二氯甲烷-正己烷混合溶剂。得淡黄色的结晶产物,产率80%。
(3)最终产物【2-咔唑-4’-吩噻嗪二苯砜】的合成
在氮气气氛保护下,咔唑10mmol加入三口瓶中,加入N,N-二甲基甲酰胺20mL搅拌使之溶解。加入叔丁醇钾10mmol,搅拌10min后,加入2-氟-4’-吩噻嗪二苯砜10mmol。升温至100℃继续搅拌反应5h。反应液倒入100mL水中进行沉淀,抽滤,水洗。粗产物用硅胶柱层析提纯,淋洗液为2:1的二氯甲烷-正己烷混合溶剂。得淡黄色的结晶产物,产率80%。
实施例3
(1)中间体【2-咔唑苯硼酸酯】的合成
在氮气气氛保护下,2-溴苯咔唑10mmol和双(频那醇合)二硼10mmol加入三口瓶中,加入二氧六环50mL搅拌使之溶解,通氮气30min。加入醋酸钾10mmol,升温至100℃继续搅拌反应12h。粗产物用硅胶柱层析提纯,淋洗液为2:1的二氯甲烷-正己烷混合溶剂。得白色的结晶产物,产率80%。
(2)最终产物【4-(2-苯咔唑)二苯酮】的合成
在氮气气氛保护下,4-溴二苯酮10mmol和2-咔唑苯硼酸酯12mmol加入三口瓶中,加入甲苯50mL搅拌使之溶解。加入碳酸钾水溶液14mmol/2ml H2O和0.5ml相转移剂,搅拌5min后,加入0.05g四三苯基膦钯作为催化剂。搅拌回流36h后将反应液冷却,抽滤,滤液用旋转蒸发仪蒸干。用硅胶柱层析的方法进行提纯,淋洗液为体积比2:1的二氯甲烷和正己烷的混合溶液。得白色结晶产物,产率66%。
将实施例1-3的产物通过真空升华的方式得到厚度为100nm的无定形的薄膜,测定其稳态光谱图,如图1所示,曲线1、2、3分别对应实施例1、2、3。从图1可以看出,通过改变化合物的给受体基团可以调节化合物薄膜的发光颜色从天蓝光到绿光再到黄光,说明该类TADF材料发光颜色可调。
Claims (5)
1.一种基于大位阻空间电荷转移的TADF材料,其结构如通式所示:
其中,X为酮基或者砜基;R为芳香环或芳香杂环取代基,或者是H原子、卤素原子、甲氧基、二甲基胺、硝基、氰基或羧基;Ar为芳香环或芳香杂环取代基。
2.根据权利要求1所述的基于大位阻空间电荷转移的TADF材料,其特征在于:当Ar、R为芳香环或芳香杂环取代基时,相同或不同,选自:
其中,R1和R2相同或不同,选自H原子、卤素原子、甲基、叔丁基、甲氧基、二甲基胺或三氟甲基。
3.权利要求1或2所述基于大位阻的空间电荷转移TADF材料的合成方法,其特征在于包括以下方法:
方法一:
(1)将2-溴苯磺酰氯、2-氟苯磺酰氯、2-溴苯甲酰氯或2-氟苯甲酰氯与氟苯或溴苯通过傅-克反应得到2位取代的氟代或溴代的中间体;
(2)再将步骤(1)得到的中间体和相对应的硼酸通过Sizuki反应或者与相对应的芳香胺通过取代反应得到最终产物。
方法二:
(1)将溴代芳香化合物与联硼酸频那醇酯通过Suziki反应得到对应的硼酸酯中间体;
(2)再将步骤(1)得到的中间体和相对应的溴代芳香烃通过Sizuki反应得到最终产物。
4.根据权利要求3所述的基于大位阻的空间电荷转移TADF材料的合成方法,其特征在于:所述的硼酸是包含由Ar基团的硼酸;芳香胺是包含有Ar基团的芳香胺或是包含有R基团的芳香胺;溴代芳香化合物是包含Ar基团的溴代芳香化合物。
5.权利要求1或2所述大位阻空间电荷转移的TADF材料应用于制备有机电致发光器件。
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WO2020211122A1 (zh) * | 2019-04-16 | 2020-10-22 | 武汉华星光电半导体显示技术有限公司 | 双极性热活化延迟荧光材料及其制备方法与有机电致发光二极管器件 |
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