CN112409314A - 一种有机电致发光化合物及其制备方法和应用 - Google Patents
一种有机电致发光化合物及其制备方法和应用 Download PDFInfo
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- CN112409314A CN112409314A CN202011156601.3A CN202011156601A CN112409314A CN 112409314 A CN112409314 A CN 112409314A CN 202011156601 A CN202011156601 A CN 202011156601A CN 112409314 A CN112409314 A CN 112409314A
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 57
- 238000003756 stirring Methods 0.000 claims description 49
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 44
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
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- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 18
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 claims description 18
- 125000001072 heteroaryl group Chemical group 0.000 claims description 17
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- 125000000753 cycloalkyl group Chemical group 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 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 claims description 9
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- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 9
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 9
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 8
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 125000006584 (C3-C10) heterocycloalkyl group Chemical group 0.000 claims description 6
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- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 2
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
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- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 5
- 238000004949 mass spectrometry Methods 0.000 description 5
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- 150000003839 salts Chemical class 0.000 description 5
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- 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 2
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- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 2
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- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 description 1
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 1
- KDOQMLIRFUVJNT-UHFFFAOYSA-N 4-n-naphthalen-2-yl-1-n,1-n-bis[4-(n-naphthalen-2-ylanilino)phenyl]-4-n-phenylbenzene-1,4-diamine Chemical compound C1=CC=CC=C1N(C=1C=C2C=CC=CC2=CC=1)C1=CC=C(N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C3C=CC=CC3=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C3C=CC=CC3=CC=2)C=C1 KDOQMLIRFUVJNT-UHFFFAOYSA-N 0.000 description 1
- 125000005865 C2-C10alkynyl group Chemical group 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
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- 230000005283 ground state Effects 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GIFAOSNIDJTPNL-UHFFFAOYSA-N n-phenyl-n-(2-phenylphenyl)naphthalen-1-amine Chemical group C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=CC=C1C1=CC=CC=C1 GIFAOSNIDJTPNL-UHFFFAOYSA-N 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
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- 108091008695 photoreceptors Proteins 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
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- 239000002356 single layer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/96—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings spiro-condensed with carbocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
- C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/10—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
- C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
- C07D407/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 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
- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
- C07D407/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing three or more hetero rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
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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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
- C07F7/0816—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring comprising Si as a ring atom
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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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]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting 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
- H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
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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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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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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Abstract
本发明公开了一种有机电致发光化合物,所述有机电致发光化合物的结构通式如化学式1所示:
Description
技术领域
本发明涉及有机光电材料技术领域,更具体的说是涉及一种有机电致发 光化合物及其制备方法和应用。
背景技术
有机电致发光是近20年来研究得最多的一种显示技术,被业界公认为可 能替代液晶的、未来最有希望的平板显示技术之一。与液晶相比,有机电致 发光器件具有超薄、自发光、视角宽、响应快、发光效率高、温度适应性好、 生产工艺简单、驱动电压低、能耗低、成本低等特点,其发光层由几十纳米 的有机分子薄膜构成,显示器件的厚度也只有几毫米。
有机电致发光元件是利用了如下原理的自发光元件:通过施加电场,利 用由阳极注入的空穴与由阴极注入的电子的复合能使磷光性物质发光。它具 有如下结构:阳极、阴极以及介于两者之间的有机材料层。为了提高有机电 致发光元件的效率和稳定性,有机材料层通常包括具有不同材料的多层,例 如空穴注入层(HIL)、空穴传输层(HTL)、发光层、电子传输层(ETL) 和电子注入层(EIL)。在这种有机发光元件中,当在阳极和阴极之间施加电压时,来自阳极的空穴和来自阴极的电子注入有机材料层,产生的激子在迁 移至基态时产生具有特定波长的光。其中空穴传输层可改变空穴到发光层的 空穴传输效率、发光效率、寿命等。因此,目前使用铜酞菁(CuPc)、4,4′-双[N-(1- 萘基)-N-苯基氨基]联苯(NPB)、N,N′-二苯基-N,N′-双(3-甲基苯基)-(1,1′-联 苯)-4,4′-二胺(TPD)等作为空穴传输材料。
目前,有机电致发光材料的研究已经在学术界和工业界广泛开展,大量 性能优良的有机电致发光材料陆续被开发出来。总体来看,未来有机电致发 光器件的方向是发展高效率、长寿命、低成本的白光器件和全彩色显示器件, 但是,该技术的产业化进程仍面临许多关键问题。
因此,如何研制一种使器件发光性能稳定、发光效率高的化合物,是本 领域技术人员亟需解决的问题。
发明内容
有鉴于此,本发明提供了一种高电子传输性能电子传输材料,提高电子 迁移率,促进载流子注入平衡,进而使器件发光性能稳定、发光效率高的有 机电致发光化合物。
为了实现上述目的,本发明采用如下技术方案:一种有机电致发光化合 物,所述有机电致发光化合物的结构通式如化学式1所示:
其中,m、n、p均为0或1,且不能同时为0;
X为连接键;或X选自-O-、-S-、-SO2-、-C(R3)(R4)-、-N(R5)-、-Si(R6)(R7)-、 -Sn(R8)(R9)-和-Ge(R10)(R11)中的一种;
L1-L3各自独立地表示连接键;或L1-L3各自独立地表示取代或未取代的 C6-C30亚芳基、取代或未取代的3-10元亚杂芳基;
R1和R2各自独立地表示氢、氘、卤素、氰基、羧基、硝基、羟基、氨基、 硅基、硼烷基、取代或未取代的C1-C30烷基、取代或未取代的C2-C30烯基、 取代或未取代的C2-C30炔基、取代或未取代的C3-C30环烷基、取代或未取 代3-30元杂环烷基、取代或未取代的C6-C30芳基、取代或未取代的3-20元 杂芳基、取代或未取代的3-25元杂芳基胺基、取代或未取代的C6-C60芳基 胺基、取代或未取代的C1-C30烷氧基、取代或未取代的C6-C60芳氧基;
或,所述R1和R2彼此连接形成环;
R3-R11各自独立地表示取代或未取代的C1-C30烷基、取代或未取代的 C3-C10环烷基、取代或未取代的3-10元杂环烷基、取代或未取代C6-C30芳 基、取代或未取代的3-30元杂芳基、取代或未取代的3-30元杂芳基胺基、取 代或未取代的C6-C60芳基胺基;
Ar1-Ar6各自独立地表示取代或未取代的C3-C30环烷基、取代或未取代 的3-20元杂环烷基、取代或未取代的C6-C30芳基或经取代或未经取代的3-10 元杂芳基、取代或未经取代的3-15元杂芳基胺基、取代或未经取代的C6-C60 芳基胺基。
优选地,所述R1和R2彼此连接形成环时,表示为环A;
所述化学式1还可以表示为:
其中,q为0或1,且m、n、p、q不能同时为0;
L4为连接键;或L4选自取代或未取代的C6-C30亚芳基、取代或未取代的 3-10元亚杂芳基;
Ar7和Ar8各自独立地表示取代或未取代的C3-C30环烷基、取代或未代 的3-20元杂环烷基、取代或未取代的C6-C30芳基或取代或未取代的3-10元 杂芳基、取代或未取代的3-15元杂芳基胺基、取代或未取代的C6-C60芳基 胺基。
环A表示取代或未取代C3-C10环烷基、取代或未取代的3-10元杂环烷 基、取代或未取代的C6-C15芳基、取代或未取代的3-15元杂芳基。
优选地,所述R3-R11各自独立地表示取代或未取代的C1-C10烷基、取代 或未取代的C3-C7环烷基、取代或未取代的3-10元杂环烷基、取代或未取代 的C6-C15芳基、取代或未取代的3-15元杂芳基、取代或未取代的3-10元杂 芳基胺基、取代或未取代的C6-C30芳基胺基。
优选地,所述Ar1-Ar8各自独立地表示取代或未取代的C6-C30芳基、取 代或未取代的3-15元杂芳基、取代或未取代的3-15元杂芳基胺基、取代或未 取代的C6-C60芳基胺基。
优选地,所述环烷基、杂环烷基、杂芳基及杂芳基胺基中的杂原子均选 自氧、氮、硫中的一种。
上述术语中,“取代”意指与化合物的碳原子键合的氢原子变成另外的取代 基,并且取代的位置没有限制,只要该位置为氢原子被取代的位置(即,取代 基可以取代的位置)即可,并且当两个或更多个取代基取代时,两个或更多个 取代基可以彼此相同或不同。
即上述的“取代或未经取代”中的“取代”,可优选的取代基为氘、氰基、卤 素、硝基、羟基、磷酸基、硼烷基、硅基、C1-C8烷基、C2-C15烯基、C2-C10 炔基、C6-C20芳基、C3-C10杂芳基、C1-C10烷氧基、C6-C20芳基氨基中的 一种或多种。
在上述技术方案中,所述有机电致发光化合物选自化学式1优选地结构 的化合物如下HT-(1-88):
本发明中还提供了一种有机电致发光化合物的制备方法,包括以下步骤:
(1)在氮气保护下,在原料B中加入四氢呋喃,并降温至(-70)-(-78)℃, 然后滴加正丁基锂,搅拌混合,得到混合液A;将原料A滴加到混合液A中, 搅拌反应,制备得到中间体1;
(2)在中间体1中加入冰醋酸加热,并滴加浓硫酸,搅拌均匀,冷却, 然后加入碳酸氢钠溶液终止反应,制备得到固体中间体2。
(3)在氮气保护下,将中间体2和原料C溶于甲苯、乙醇和水的混合溶 液中,然后加入四三苯基膦钯和碳酸钾,搅拌均匀,升温并回流,制备得到 中间体3;
(4)在氮气保护下,将中间体3和原料D溶于甲苯溶液中,加入三(二 亚苄基丙酮)二钯、三叔丁基膦及叔丁醇钠,搅拌均匀,升温并回流,制备 得到化学式1或化学式1-1;
化学式1的合成路线为:
化学式1-1的合成路线为:
其中,所述Hal1和Hal2为除氯以外的卤素。
当L1、L2、L3和L4表示连接键时,化学式1及化学式1-1可由中间体 2和原料D进行合成。
优选地,所述原料B的摩尔、所述正丁基锂及所述原料A的摩尔比为
(30-50):(36-60):(30-50),所述原料A与所述四氢呋喃的摩尔体积 比为(30-50)mmol:(80-160)mL;
所述搅拌混合的温度为(-70)℃-(-78)℃,时间为1.5-2.5h。
优选地,步骤(2)中,所述中间体1、所述冰醋酸及所述碳酸氢钠溶液 的摩尔体积比为(24-44)mmol:(125-200)mL:(24-44)mL;所述搅拌 温度为110℃-130℃,时间为5min。
优选地,步骤(3)中,所述中间体2、所述原料C、所述四三苯基膦钯 及所述碳酸钾的摩尔比为:(18-33):(0.18-0.34):(36-65);所述中间 体2的及所述混合溶液的摩尔体积比为(18-34)mmol:(110-200)mL;所 述甲苯、乙醇及水的体积比为(2.5-3.5):(0.5-1.5):(0.5-1.5);所述升温 至80℃-100℃,回流时间为4.5-5.5h;
步骤(4)中,所述中间体3、所述原料D、所述三(二亚苄基丙酮)二 钯、所述三叔丁基膦及所述叔丁醇钠的摩尔比为(14-27):(14-27): (0.14-0.28):(0.7-1.4):(28-56);所述中间体3与所述甲苯溶液的摩 尔体积比为(14-27)mmol:(110-270)mL;所述升温至80℃-100℃,回流 时间为4.5-5.5h。
本发明中还提供了一种有机电致发光化合物在有机电致发光器件中的应 用。
本发明中还提供了一种有机电致发光器件,包括第一电极、第二电极以 及有机层;所述第一电极及第二电极之间至少设置一层有机层;
有机发光器件的有机材料层为单层结构;或,形成为两个或更多个有机 材料层的多层结构;
有机发光器件可以具有包括空穴注入层、空穴传输层、空穴注入和传输 层、电子阻挡层、发光层、电子传输层、电子注入层、空穴阻挡层、电子注 入和传输层作为有机材料层的结构。
然而,有机发光器件的结构不限于此,并且可以包括更少数量的有机材 料层或更多数量的有机材料层。
本发明提供的有机电致发光器件可应用在有机发光器件(OLED)、有机太 阳电池(OSC)、电子纸(e-paper)、有机感光体(OPC)或有机薄膜晶体管(OTFT) 上。
经由上述的技术方案可知,与现有技术相比,本发明公开提供了一种有 机电致发光化合物及其制备方法和应用,本发明中的有机电致发光化合物通 过杂环配体配位,调节取代基的位置或取代基的活性;并且,配合物上的胺 单元具有较低的离子化电位,较好的给电子性,较高的空穴迁移率。同时降 低分子的对称性,增加分子的构象异构体;同时,在结构式中的R1、R2位置 上连有取代基或互相连接行成取代或未取代的单环或多环结构,使化合物具 有刚性平面结构,增加了分子量,则分子间不易结晶、不易聚集,使材料具 有较高的光热稳定性;得到的空穴传输材料在用于有机电致发光器件后,使 得器件的发光效率得到提高,寿命得到延迟,驱动电压得到降低。
具体实施方式
下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完 整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部 的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性 劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1:制备化合物HT-9
1.在氮气保护下,将原料B-9(50.00mmol)加入到三口瓶中,加入160.00 mL无水四氢呋喃,随后将反应体系降温至-78℃,滴加n-BuLi(60.00mmol), 在-78℃下搅拌2h,得到混合液。将原料A-9(50.00mmol)溶于150.00mL 四氢呋喃溶液中,然后滴加至上述混合液中,滴加完毕后升温至室温,并搅 拌10h。然后,加入饱和氯化铵溶液猝灭反应,用乙酸乙酯萃取反应液3次, 合并有机相,并相继用水、饱和食盐水洗涤,之后用20g无水硫酸镁干燥。然后将干燥得到的固体加入乙醇溶液中,并升温至80℃,搅拌5小时,随后 趁热将溶液抽滤,得到固体,然后用石油醚淋洗,烘干(80℃,3.5h),制备 得到中间体1(18.99g,产率:87.31%);
2.将中间体1(43.67mmol)加入三口瓶中,加入200.00mL冰醋酸,加 热至120℃,滴加4.40mL浓硫酸,搅拌5min。冷却至室温,加入44.00mL 碳酸氢钠溶液终止反应,分液,水相用二氯甲烷萃取三次,收集有机相,加 入30g无水硫酸镁干燥,通过旋转蒸发仪除去溶剂,将固体有机物加入乙醇 溶液中,升温至80℃,并搅拌5小时,待溶液冷却至室温后,将溶液抽滤得 到固体,随后用石油醚淋洗,烘干(80℃,3.5h),制备得到中间体2(14.69g, 产率:80.67%);
3.在氮气保护下,将中间体2(33.58mmol)和原料C-9(33.58mmol) 溶于200.00mL甲苯、乙醇和水(V甲苯:V乙醇:V水=3:1:1)的混合溶液中, 加入四三苯基膦钯(0.34mmol)和碳酸钾(67.16mmol),搅拌均匀,升温 至90℃,并回流5小时,待溶液冷却至室温后,保留有机相,然后用乙酸乙 酯萃取水相;合并有机相后,使用30g无水硫酸镁进行干燥,并且使用旋转 式蒸发器去除溶剂,得到固体有机物。使用二氯甲烷将固体有机物完全溶解, 然后缓慢滴加到石油醚溶液中,搅拌均匀,有沉淀析出,抽滤得固体,依次 用无水乙醇、石油醚淋洗,烘干(80℃,3.5h),制备得到中间体3(15.58g, 产率:86.59%);
4.在氮气保护下,将中间体3(27.91mmol)和原料D-9(27.91mmol) 溶于270.00mL甲苯溶液中,加入三(二亚苄基丙酮)二钯(0.28mmol), 三叔丁基膦(1.40mmol)及叔丁醇钠(55.82mmol),搅拌均匀,升温至90℃, 并回流反应5h;反应结束后,稍降温度至75℃,使用硅藻土进行过滤,除去 盐以及催化剂,滤液冷却至室温后,水洗三遍,保留有机相,接着用乙酸乙 酯萃取水相;合并有机相后,使用40g无水硫酸镁进行干燥,并且使用旋转 式蒸发器去除溶剂;利用二氯甲烷和石油醚(V二氯甲烷:V石油醚=10:4)的 混合溶液,通过柱色谱法纯化剩余物质获得化合物HT-9。(21.66g,产率: 83.44%,Mw:930.15)。
对所得化合物HT-9进行检测分析,结果如下:
HPLC纯度:>99%。
质谱测试:理论值为930.16;测试值为930.15。
元素分析:
计算值为:C,91.68;H,5.09;N,1.51;O,1.72。
测试值为:C,91.67;H,5.10;N,1.52;O,1.71。
实施例2:制备化合物HT-25
1.在氮气保护下,将原料B-25(30.00mmol)加入到三口瓶中,加入90.00 mL无水四氢呋喃,随后将反应体系降温至-78℃,滴加n-BuLi(36.00mL), 在-78℃下搅拌2h,得到混合液。将原料A-25(30.00mL)溶于70.00mL四 氢呋喃溶液中,然后滴加至上述混合液中,滴加完毕后升温至室温,并搅拌 10h。然后,加入饱和氯化铵溶液猝灭反应,用乙酸乙酯萃取反应液3次,合 并有机相,并相继用水、饱和食盐水洗涤,之后用20g无水硫酸镁干燥。然 后将干燥得到的固体加入乙醇溶液中,并升温至80℃,搅拌5小时,随后趁 热将溶液抽滤,得到固体,然后用石油醚淋洗,烘干(80℃,3.5h),制备得 到中间体1;(11.40g,产率:87.38%);
2.将中间体1(25.29mmol)加入三口瓶中,加入125.00mL冰醋酸,加 热至120℃,滴加2.50mL浓硫酸,搅拌5min。冷却至室温,加入25.00mL 碳酸氢钠溶液终止反应,分液,水相用二氯甲烷萃取三次,收集有机相,加 入30g无水硫酸镁干燥,通过旋转蒸发仪除去溶剂,将固体有机物加入乙醇 溶液中,升温至80℃,并搅拌5小时,待溶液冷却至室温后,将溶液抽滤得 到固体,随后用石油醚淋洗,烘干(80℃,3.5h),制备得到中间体2(8.50g, 产率:80.62%);
3.在氮气保护下,将中间体2(19.19mmol)和原料C-25(19.19mmol) 溶于140.00mL甲苯、乙醇和水(V甲苯:V乙醇:V水=3:1:1)的混合溶液中, 加入四三苯基膦钯(0.19mmol)和碳酸钾(38.38mmol),搅拌均匀,升温 至90℃,并回流5小时,待溶液冷却至室温后,保留有机相,然后用乙酸乙 酯萃取水相;合并有机相后,使用30g无水硫酸镁进行干燥,并且使用旋转 式蒸发器去除溶剂,得到固体有机物。使用二氯甲烷将固体有机物完全溶解, 然后缓慢滴加到石油醚溶液中,搅拌均匀,有沉淀析出,抽滤得固体,依次 用无水乙醇、石油醚淋洗,烘干(80℃,3.5h),制备得到中间体3(10.20g, 产率:86.54%);
4. 在氮气保护下,将中间体3(16.27mmol)和原料D-25(16.27mmol)溶于 170.00mL甲苯溶液中,加入三(二亚苄基丙酮)二钯(0.16mmol),三叔 丁基膦(0.81mmol)及叔丁醇钠(32.54mmol),搅拌均匀,升温至90℃, 并回流反应5h;反应结束后,稍降温度至75℃,使用硅藻土进行过滤,除去 盐以及催化剂,滤液冷却至室温后,水洗三遍,保留有机相,接着用乙酸乙 酯萃取水相;合并有机相后,使用40g无水硫酸镁进行干燥,并且使用旋转 式蒸发器去除溶剂;利用二氯甲烷和石油醚(V二氯甲烷:V石油醚=10:4)的 混合溶液,通过柱色谱法纯化剩余物质获得化合物HT-25(13.39g,产率: 83.51%,Mw:985.21)
对所得化合物HT-25进行检测分析,结果如下:
HPLC纯度:>99%。
质谱测试:理论值为985.20;测试值为985.21。
元素分析:
计算值为:C,89.00;H,4.91;N,2.84;O,3.25。
测试值为:C,89.01;H,4.92;N,2.83;O,3.24。
实施例3:制备化合物HT-42
1.在氮气保护下,将原料B-42(30.00mmol)加入到三口瓶中,加入100.00 mL无水四氢呋喃,随后将反应体系降温至-78℃,滴加n-BuLi(36.00mmol), 在-78℃下搅拌2h,得到混合液。将原料A-42(30.00mmol)溶于100.00mmol 四氢呋喃溶液中,然后滴加至混合液中,滴加完毕后升温至室温,并搅拌10h。 然后,加入饱和氯化铵溶液猝灭反应,用乙酸乙酯萃取反应液3次,合并有 机相,并相继用水、饱和食盐水洗涤,之后用20g无水硫酸镁干燥。然后将 干燥得到的固体加入乙醇溶液中,并升温至80℃,搅拌5小时,随后趁热将 溶液抽滤,得到固体,然后用石油醚淋洗,烘干(80℃,3.5h),制备得到中 间体1;(14.12g,产率:87.35%);
2.将中间体1(25.97mmol)加入三口瓶中,加入130.00mL冰醋酸,加 热至120℃,滴加2.60mL浓硫酸,搅拌5min。冷却至室温,加入26.00mL 碳酸氢钠溶液终止反应,分液,水相用二氯甲烷萃取三次,收集有机相,加 入30g无水硫酸镁干燥,通过旋转蒸发仪除去溶剂,将固体有机物加入乙醇 溶液中,升温至80℃,并搅拌5小时,待溶液冷却至室温后,将溶液抽滤得 到固体,随后用石油醚淋洗,烘干(80℃,3.5h),制备得到中间体2;(10.87g, 产率:80.65%);
3.在氮气保护下,将中间体2(19.27mmol)和原料D-42(19.27mmol) 溶于180.00mL甲苯溶液中,加入三(二亚苄基丙酮)二钯(0.19mmol), 三叔丁基膦(0.96mmol)及叔丁醇钠(38.54mmol),搅拌均匀,升温至90℃, 并回流反应5h;反应结束后,稍降温度至75℃,使用硅藻土进行过滤,除去 盐以及催化剂,滤液冷却至室温后,水洗三遍,保留有机相,接着用乙酸乙 酯萃取水相;合并有机相后,使用30g无水硫酸镁进行干燥,并且使用旋转 式蒸发器去除溶剂;利用二氯甲烷和石油醚(V二氯甲烷:V石油醚=10:4)的 混合溶液,通过柱色谱法纯化剩余物质获得化合物HT-42(14.09g,产率: 83.48%,Mw:876.12)。
对所得化合物HT-42进行检测分析,结果如下:
HPLC纯度:>99%。
质谱测试:理论值为876.11;测试值为876.12。
元素分析:
计算值为:C,87.94;H,4.96;N,1.60;O,1.83;S,3.67。
测试值为:C,87.95;H,4.95;N,1.61;O,1.84;S,3.65。
实施例4:制备化合物HT-49
1.在氮气保护下,将原料B-49(30.00mmol)加入到三口瓶中, 加入80.00mL无水四氢呋喃,随后将反应体系降温至-78℃,滴加n-BuLi(36.00 mmol),在-78℃下搅拌2h,得到混合液。将原料A-49(30.00mmol)溶于 80.00mL四氢呋喃溶液中,然后滴加至混合液中,滴加完毕后升温至室温, 并搅拌10h。然后,加入饱和氯化铵溶液猝灭反应,用乙酸乙酯萃取反应液3 次,合并有机相,并相继用水、饱和食盐水洗涤,之后用20g无水硫酸镁干 燥。然后将干燥得到的固体加入乙醇溶液中,并升温至80℃,搅拌5小时, 随后趁热将溶液抽滤,得到固体,然后用石油醚淋洗,烘干(80℃,3.5h), 制备得到中间体1;(11.83g,产率:87.40%);
2.将中间体1(24.39mmol)加入三口瓶中,加入125.00mL冰醋酸,加 热至120℃,滴加2.40mL浓硫酸,搅拌5min。冷却至室温,加入24.00mL 碳酸氢钠溶液终止反应,分液,水相用二氯甲烷萃取三次,收集有机相,加 入30g无水硫酸镁干燥,通过旋转蒸发仪除去溶剂,将固体有机物加入乙醇 溶液中,升温至80℃,并搅拌5小时,待溶液冷却至室温后,将溶液抽滤得 到固体,随后用石油醚淋洗,烘干(80℃,3.5h),制备得到中间体2(8.51g, 产率:80.61%);
3.在氮气保护下,将中间体2(18.48mmol)和原料C-49(18.48mmol)溶 于110.00mL甲苯、乙醇和水(V甲苯:V乙醇:V水=3:1:1)的混合溶液中, 加入四三苯基膦钯(0.18mmol)和碳酸钾(36.96mmol),搅拌均匀,升温 至90℃,并回流5小时,待溶液冷却至室温后,保留有机相,然后用乙酸乙 酯萃取水相;合并有机相后,使用30g无水硫酸镁进行干燥,并且使用旋转 式蒸发器去除溶剂,得到固体有机物。使用二氯甲烷将固体有机物完全溶解, 然后缓慢滴加到石油醚溶液中,搅拌均匀,有沉淀析出,抽滤得固体,依次 用无水乙醇、石油醚淋洗,烘干(80℃,3.5h),制备得到中间体3(8.92g, 产率:86.57%);
4.在氮气保护下,将中间体3(14.35mmol)和原料D-49(14.35mmol) 溶于110.00mmol甲苯溶液中,加入三(二亚苄基丙酮)二钯(0.14mmol), 三叔丁基膦(0.72mmol)及叔丁醇钠(28.70mmol),搅拌均匀,升温至90℃, 并回流反应5h;反应结束后,稍降温度至75℃,使用硅藻土进行过滤,除去 盐以及催化剂,滤液冷却至室温后,水洗三遍,保留有机相,接着用乙酸乙 酯萃取水相;合并有机相后,使用无水硫酸镁进行干燥,并且使用旋转式蒸 发器去除溶剂;利用二氯甲烷和石油醚(V二氯甲烷:V石油醚=10:4)的混合 溶液,通过柱色谱法纯化剩余物质获得化合物HT-49(8.93g,产率:83.47%, Mw:745.97)。
对所得化合物HT-49进行检测分析,结果如下:
HPLC纯度:>99%。
质谱测试:理论值为745.98;测试值为745.97。
元素分析:
计算值为:C,88.56;H,5.27;N,1.88;S,4.30。
测试值为:C,88.57;H,5.26;N,1.87;S,4.31。
实施例5:制备化合物HT-77
1.在氮气保护下,将原料B-72(30.00mmol)加入到三口瓶中, 加入80.00mL无水四氢呋喃,随后将反应体系降温至-78℃,滴加n-BuLi(36.00 mmol),在-78℃下搅拌2h,得到混合液。将原料A-72(36.00mmol)溶于 110.00mL四氢呋喃溶液中,然后滴加至混合液中,滴加完毕后升温至室温, 并搅拌10h。然后,加入饱和氯化铵溶液猝灭反应,用乙酸乙酯萃取反应液3 次,合并有机相,并相继用水、饱和食盐水洗涤,之后用20g无水硫酸镁干 燥。然后将干燥得到的固体加入乙醇溶液中,并升温至80℃,搅拌5小时, 随后趁热将溶液抽滤,得到固体,然后用石油醚淋洗,烘干(80℃,3.5h), 制备得到中间体1;(14.54g,产率:87.33%);
2.将中间体1(25.22mmol)加入三口瓶中,加入140.00mL冰醋酸,加 热至120℃,滴加2.50mL浓硫酸,搅拌5min。冷却至室温,加入25.00mL 碳酸氢钠溶液终止反应,分液,水相用二氯甲烷萃取三次,收集有机相,加 入30g无水硫酸镁干燥,通过旋转蒸发仪除去溶剂,将固体有机物加入乙醇 溶液中,升温至80℃,并搅拌5小时,待溶液冷却至室温后,将溶液抽滤得 到固体,随后用石油醚淋洗,烘干(80℃,3.5h),制备得到中间体2(10.89g, 产率:80.64%);
3.在氮气保护下,将中间体4(18.69mmol)和原料D2-72(18.69mmol) 溶于170.00mL甲苯溶液中,接着氮气置换空气3次,加入三(二亚苄基丙酮) 二钯(0.18mmol),三叔丁基膦(0.93mmol)及叔丁醇钠(37.38mmol), 搅拌均匀,升温至90℃,并回流反应5h;反应结束后,稍降温度至75℃,使 用硅藻土进行过滤,除去盐以及催化剂,滤液冷却至室温后,水洗三遍,保 留有机相,接着用乙酸乙酯萃取水相;合并有机相后,使用30g无水硫酸镁进行干燥,并且使用旋转式蒸发器去除溶剂;利用二氯甲烷和石油醚(V二 氯甲烷:V石油醚=10:4)的混合溶液,通过柱色谱法纯化剩余物质获得化合物 HT-77(13.89g,产率:83.50%,Mw:890.17)。
对所得化合物HT-77进行检测分析,结果如下:
HPLC纯度:>99%。
质谱测试:理论值为890.18;测试值为890.17。
元素分析:
计算值为:C,86.35;H,4.87;N,1.57;S,7.20。
测试值为:C,86.36;H,4.88;N,1.56;S,7.19。
其他化合物的合成方法与上述实施例相同,在此不一一赘述,其他合成 实施例质谱和分子式如下表1所示:
表1
采用TMA4000对上述实施例合成的化合物测试其玻璃化转变温度(tg), 如表2所示:
表2:
化合物 | 玻璃化转变温度(tg) | 化合物 | 玻璃化转变温度(tg) |
9 | 177.3 | 56 | 181.1 |
15 | 180.1 | 62 | 179.5 |
20 | 178.3 | 68 | 180.6 |
25 | 179.7 | 71 | 181.7 |
29 | 177.6 | 77 | 182.3 |
36 | 178.4 | 85 | 178.9 |
42 | 181.5 | 88 | 178.6 |
49 | 179.2 |
从表2中可以看出,本公开的空穴传输材具有较高的热稳定性。
采用上述实施例提供的空穴传输材料制备得到的有机电致发光器件,其 中,该有机电致发光器件包括阳极、空穴注入层、空穴传输层、发光层、电 子传输层、电子注入层、阴极。
当有机物层包括空穴传输层时,所述空穴传输层包括上述实施例提供的 空穴传输材料。
器件实施例1:
所制备OLED器件的结构为:ITO阳极/HIL/HTL/EML/ETL/EIL/阴极/光取 出层
a、ITO阳极:将涂层厚度为的ITO(氧化铟锡)-Ag-ITO(氧化铟锡) 玻璃基板在蒸馏水中清洗2次,超声波洗涤30min,再用蒸馏水反复清洗2次, 超声波洗涤10min,洗涤结束后,用甲醇、丙酮、异丙醇依次超声波洗涤(每 次洗涤5min),干燥,然后转移至等离子体清洗机内洗涤5min,再送至蒸镀 机中,以该基板为阳极,在其上依次蒸镀其它功能层。
b、HIL(空穴注入层):蒸镀2-TNATA(即N1-(2-萘基)-N4,N4-二(4-(2- 萘基(苯基)氨基)苯基)-N1-苯基苯-1,4-二胺)10nm,形成空穴注入层。
c、HTL(空穴传输层):蒸镀上述实施例1制备的化合物HT-915nm,形 成空穴传输层。
d、EML(发光层):主体材料EMH-1和掺杂材料EMD-1,以重量比97∶3 混合蒸镀40nm,形成发光层。其中主体材料EMH-1和掺杂材料EMD-1的结构 式如下;
f、ETL(电子传输层):蒸镀ET-1和Liq 40nm,形成电子传输层。其中 ET-1和Liq的重量比为60:40,其中ET-1的结构式如下
g、EIL(电子注入层):蒸镀Yb 1.0nm,形成电子注入层。
h、阴极:蒸镀镁和银18nm,其重量比为1:9,得到OLED器件。
i、光取出层:在阴极上真空蒸镀厚度为70nm的IDX001,作为光取出层。
参照上述器件实施例1提供的方法,分别选用化合物HT-15、HT-20、 HT-25、HT-29、HT-36、HT-42、HT-49、HT-56、HT-62、HT-68、HT-71、 HT-77、HT-85、HT-88替代化合物HT-9,进行空穴传输层的蒸镀,并制备得 到相应的有机电致发光器件,分别记为器件实施例2-15。
器件对比例1:
该对比例提供了一种有机电致发光器件,该有机电致发光器件的制备方法 与器件实施例1的唯一区别在于,该有机电致发光器件是采用现有的对比化 合物A替代上述器件实施例1中的空穴传输材料(化合物HT-9)进行蒸镀, 制备得到相应的有机电致发光器件,记为器件对比例1。其中,对比化合物A 的化学结构式为:
器件对比例2:
参照上述器件对比例1提供的方法,选用化合物TCTA替代化合物A, 进行空穴传输层的蒸镀,并制备得到相应的有机电致发光器件,记为器件对 比例2。其中,TCTA的化学结构式为:
在6000(nits)亮度下对上述器件实施例1~15以及器件对比例1~2得到 的有机电致发光器件的驱动电压、发光效率以及寿命进行表征,测试结果如 下表3:
从上表3可知:由本发明提供的有机电致发光化合物作为空穴传输层 制备的有机电致发光器件相对于两种对比化合物作为空穴传输层制备的有机 电致发光器件,具有更低的启动电压,且发光效率和寿命得到了显著的提高。
对所公开的实施例的上述说明,使本领域专业技术人员能够实现或使用 本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易 见的,本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下, 在其它实施例中实现。因此,本发明将不会被限制于本文所示的这些实施例, 而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。
Claims (10)
1.一种有机电致发光化合物,其特征在于,所述有机电致发光化合物的结构通式如化学式1所示:
其中,m、n、p均为0或1,且不能同时为0;
X为连接键;或X选自-O-、-S-、-SO2-、-C(R3)(R4)-、-N(R5)-、-Si(R6)(R7)-、-Sn(R8)(R9)-和-Ge(R10)(R11)中的一种;
L1-L3各自独立地表示连接键;或L1-L3各自独立地表示取代或未取代的C6-C30亚芳基、取代或未取代的3-10元亚杂芳基;
R1和R2各自独立地表示氢、氘、卤素、氰基、羧基、硝基、羟基、氨基、硅基、硼烷基、取代或未取代的C1-C30烷基、取代或未取代的C2-C30烯基、取代或未取代的C2-C30炔基、取代或未取代的C3-C30环烷基、取代或未取代的3-30元杂环烷基、取代或未取代的C6-C30芳基、取代或未取代的3-20元杂芳基、取代或未取代的3-25元杂芳基胺基、取代或未取代的C6-C60芳基胺基、取代或未取代的C1-C30烷氧基、取代或未取代的C6-C60芳氧基;
或,所述R1和R2彼此连接形成环;
R3-R11各自独立地表示取代或未取代的C1-C30烷基、取代或未取代的C3-C10环烷基、取代或未取代的3-10元杂环烷基、取代或未取代C6-C30芳基、取代或未取代的3-30元杂芳基、取代或未取代的3-30元杂芳基胺基、取代或未取代的C6-C60芳基胺基;
Ar1-Ar6各自独立地表示取代或未取代的C3-C30环烷基、取代或未取代的3-20元杂环烷基、取代或未取代的C6-C30芳基、取代或未取代的3-10元杂芳基、取代或未取代的3-15元杂芳基胺基、取代或未取代的C6-C60芳基胺基。
2.根据权利要求1所述的一种有机电致发光化合物,其特征在于,所述R1和R2彼此连接形成环时,表示为环A;
所述化学式1为:
其中,q为0或1,且m、n、p、q不能同时为0;
L4为连接键;或L4选自取代或未取代的C6-C30亚芳基、取代或未取代的3-10元亚杂芳基;
Ar7和Ar8各自独立地表示取代或未取代的C3-C30环烷基、取代或未代的3-20元杂环烷基、取代或未取代的C6-C30芳基或、取代或未取代的3-10元杂芳基、取代或未取代的3-15元杂芳基胺基、取代或未取代的C6-C60芳基胺基。
环A表示取代或未取代C3-C10环烷基、取代或未取代的3-10元杂环烷基、取代或未取代的C6-C15芳基、取代或未取代的3-15元杂芳基。
3.根据权利要求2所述的一种有机电致发光化合物,其特征在于,所述R3-R11各自独立地表示取代或未取代的C1-C10烷基、取代或未取代的C3-C7环烷基、取代或未取代的3-10元杂环烷基、取代或未取代的C6-C15芳基、取代或未取代的3-15元杂芳基、取代或未取代的3-10元杂芳基胺基、取代或未取代的C6-C30芳基胺基。
4.根据权利要求3所述的一种有机电致发光化合物,其特征在于,所述Ar1-Ar8各自独立地表示取代或未取代的C6-C30芳基、取代或未取代的3-15元杂芳基、取代或未取代的3-15元杂芳基胺基、取代或未取代的C6-C60芳基胺基。
5.根据权利要求4所述的一种有机电致发光化合物,其特征在于,所述环烷基、杂环烷基、杂芳基及杂芳基胺基中的杂原子均选自氧、氮、硫中的一种。
6.一种如权利要求1-5所述的有机电致发光化合物的制备方法,其特征在于,包括以下步骤:
(1)在氮气保护下,在原料B中加入四氢呋喃,并降温至(-70)-(-78)℃,然后滴加正丁基锂,搅拌混合,得到混合液A;将原料A滴加到混合液A中,搅拌反应,制备得到中间体1;
(2)在中间体1中加入冰醋酸加热,并滴加浓硫酸,搅拌均匀,冷却,然后加入碳酸氢钠溶液终止反应,制备得到固体中间体2。
(3)在氮气保护下,将中间体2和原料C溶于甲苯、乙醇和水的混合溶液中,然后加入四三苯基膦钯和碳酸钾,搅拌均匀,升温并回流,制备得到中间体3;
(4)在氮气保护下,将中间体3和原料D溶于甲苯溶液中,加入三(二亚苄基丙酮)二钯、三叔丁基膦及叔丁醇钠,搅拌均匀,升温并回流,制备得到化学式1或化学式1-1;
化学式1的合成路线为:
化学式1-1的合成路线为:
其中,所述Hal1和Hal2为除氯以外的卤素。
7.根据权利要求6所述的有机电致发光化合物的制备方法,其特征在于,所述原料B、所述正丁基锂及所述原料A的摩尔比为(30-50):(36-60):(30-50),所述原料A与所述四氢呋喃的摩尔体积比为(30-50)mmol:(80-160)mL;
所述搅拌混合的温度为(-70)℃-(-78)℃,时间为1.5-2.5h。
8.根据权利要求6所述的有机电致发光化合物的制备方法,其特征在于,步骤(2)中,所述中间体1的摩尔、所述冰醋酸的体积及所述碳酸氢钠溶液的体积比为(24-44)mmol:(125-200)mL:(24-44)mL;所述搅拌温度为110℃-130℃,时间为5min。
9.根据权利要求6所述的有机电致发光化合物的制备方法,其特征在于,步骤(3)中,所述中间体2、所述原料C、所述四三苯基膦钯及所述碳酸钾的摩尔比为:(18-33):(0.18-0.34):(36-65);所述中间体2及所述混合溶液的摩尔体积比为(18-34)mmol:(110-200)mL;所述甲苯、乙醇及水的体积比为(2.5-3.5):(0.5-1.5):(0.5-1.5);所述升温至80℃-100℃,回流时间为4.5-5.5h;
步骤(4)中,所述中间体3、所述原料D、所述三(二亚苄基丙酮)二钯、所述三叔丁基膦及所述叔丁醇钠的摩尔比为(14-27):(14-27):(0.14-0.28):(0.7-1.4):(28-56);所述中间体3与所述甲苯溶液的摩尔体积比为(14-27)mmol:(110-270)mL;所述升温至80℃-100℃,回流时间为4.5-5.5h。
10.一种如权利要求1-5任一项所述的有机电致发光化合物或权利要求6-9任一项所述方法制备的有机电致发光化合物在有机电致发光器件中的应用。
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