CN111978289A - 一种化合物及其应用、包含其的有机电致发光器件 - Google Patents
一种化合物及其应用、包含其的有机电致发光器件 Download PDFInfo
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- CN111978289A CN111978289A CN201910437045.8A CN201910437045A CN111978289A CN 111978289 A CN111978289 A CN 111978289A CN 201910437045 A CN201910437045 A CN 201910437045A CN 111978289 A CN111978289 A CN 111978289A
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- -1 nitro, hydroxyl Chemical group 0.000 claims description 6
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 claims description 6
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- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 claims description 4
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- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 claims description 3
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- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims description 2
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- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
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- JWJQEUDGBZMPAX-UHFFFAOYSA-N (9-phenylcarbazol-3-yl)boronic acid Chemical group C12=CC=CC=C2C2=CC(B(O)O)=CC=C2N1C1=CC=CC=C1 JWJQEUDGBZMPAX-UHFFFAOYSA-N 0.000 description 1
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- JNGKNTZYAKKNLQ-UHFFFAOYSA-N 2-chloro-4,6-diphenyl-1h-triazine Chemical compound N=1N(Cl)NC(C=2C=CC=CC=2)=CC=1C1=CC=CC=C1 JNGKNTZYAKKNLQ-UHFFFAOYSA-N 0.000 description 1
- VDIHPLIBGUXRLI-UHFFFAOYSA-N 2-chloro-4-phenyl-6-(4-phenylphenyl)pyrimidine Chemical compound N=1C(Cl)=NC(C=2C=CC=CC=2)=CC=1C(C=C1)=CC=C1C1=CC=CC=C1 VDIHPLIBGUXRLI-UHFFFAOYSA-N 0.000 description 1
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- 101000766357 Ruditapes philippinarum Big defensin Proteins 0.000 description 1
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- ALTSSZFRWDVXPB-UHFFFAOYSA-N [9-(3-phenylphenyl)carbazol-3-yl]boronic acid Chemical group C12=CC=CC=C2C2=CC(B(O)O)=CC=C2N1C(C=1)=CC=CC=1C1=CC=CC=C1 ALTSSZFRWDVXPB-UHFFFAOYSA-N 0.000 description 1
- JHYLKGDXMUDNEO-UHFFFAOYSA-N [Mg].[In] Chemical compound [Mg].[In] JHYLKGDXMUDNEO-UHFFFAOYSA-N 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- LPTWEDZIPSKWDG-UHFFFAOYSA-N benzenesulfonic acid;dodecane Chemical compound OS(=O)(=O)C1=CC=CC=C1.CCCCCCCCCCCC LPTWEDZIPSKWDG-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical group OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- GSRACRUJMDHCAF-UHFFFAOYSA-N boric acid;9h-carbazole Chemical compound OB(O)O.C1=CC=C2C3=CC=CC=C3NC2=C1 GSRACRUJMDHCAF-UHFFFAOYSA-N 0.000 description 1
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Inorganic materials [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 1
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- 125000002091 cationic group Chemical group 0.000 description 1
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- 150000004696 coordination complex Chemical class 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
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- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
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- 239000010408 film Substances 0.000 description 1
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- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
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- 229910052744 lithium Inorganic materials 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Inorganic materials [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07D401/02—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 two hetero rings
- C07D401/04—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 two hetero rings directly linked by a ring-member-to-ring-member bond
-
- 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
- C07D401/02—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 two hetero rings
- C07D401/10—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 two hetero rings linked by a carbon chain containing aromatic rings
-
- 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
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/06—Peri-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
-
- 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
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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Abstract
Description
技术领域
本发明涉及一种新型有机化合物,尤其涉及一种用于有机电致发光器件的化合物及在有机电致发光器件中的应用。
背景技术
近年来,基于有机材料的光电子器件已经变得越来越受欢迎。有机材料固有的柔性令其十分适合用于在柔性基板上制造,可根据需求设计、生产出美观而炫酷的光电子产品,获得相对于无机材料无以比拟的优势。此类有机光电子器件的示例包括有机发光二极管(OLED),有机场效应管,有机光伏打电池,有机传感器等。其中OLED发展尤其迅速,已经在信息显示领域取得商业上的成功。OLED可以提供高饱和度的红、绿、蓝三颜色,用其制成的全色显示装置无需额外的背光源,具有色彩炫丽,轻薄柔软等优点。
OLED器件核心为含有多种有机功能材料的薄膜结构。常见的功能化有机材料有:空穴注入材料、空穴传输材料、空穴阻挡材料、电子注入材料、电子传输材料,电子阻挡材料以及发光主体材料和发光客体(染料)等。通电时,电子和空穴被分别注入、传输到发光区域并在此复合,从而产生激子并发光。
人们已经已经开发出多种有机材料,结合各种奇特的器件结构,可以提升载流子迁移率、调控载流子平衡、突破电致发光效率、延缓器件衰减。出于量子力学的原因,常见的荧光发光体主要利用电子和空血结合时产生的单线态激子发光,现在仍然广泛地应用于各种OLED产品中。有些金属络合物如铱络合物,可以同时利用三线态激子和单线态激子进行发光,被称为磷光发光体,其能量转换效率可以比传统的荧光发光体提升高达四倍。热激发延迟荧光(TADF)技术通过促进三线态激子朝单线态激子的转变,在不采用金属配合物的情况下,仍然可以有效地利用三线态激子而实现较高的发光效率。热激发敏化荧光(TASF)技术则采用具TADF性质的材料,通过能量转移的方式来敏化发光体,同样可以实现较高的发光效率。
随着OLED产品逐步进入市场,人们对这类产品的性能有越来越高的要求。当前使用的OLED材料和器件结构无法完全解决OLED产品效率、寿命、成本等各方面的问题。本发明的研究人员通过认真思考和不断实验,发现了一种巧妙的分子设计/器件设计方案,并在下文中详细地进行说明。令人惊讶地,本发明所揭示的化合物非常适合应用于OLED并提升器件的性能。
现有技术KR1020120095832A中报道的化合物公开了在母核结构上的取代基团有非常多的选择,但是其针对母核上R取代基并没有具体的设计和合成方案。
发明内容
为了克服以上现有技术中传统主体材料的缺点,本发明提供一类有机化合物并将其应用于有机电致发光器件中。本发明化合物将供电子与吸电子基团引入母核中,使材料具备双极性特性,实现了载流子的平衡传输,由此得到了具备低电压、高效率的优势的新型化合物。
本发明公开了下式(Ⅰ)的通式化合物:
X1-X10分别独立地选自CR1、N或CR2,且其中至少一个为CR2;
优选的,X2、X3、X4、X7、X8和X9中至少一个选自CR2;进一步优选的,X3、X4、X7和X8中至少一个选自CR2;更一步优选的,X4或X7选自CR2;
R1独立地选自氢、C1~C12烷基、C3~C12环烷基、C1~C12烷氧基、卤素、氰基、硝基、羟基、硅烷基、氨基中的一种;
R2独立地选自取代或未取代的C6~C30芳基氨基、取代或未取代的C3~C30杂芳基氨基、取代或未取代的C6~C30芳基、取代或未取代的C3~C30杂芳基中的一种;
优选的,R2独立地选自取代或未取代的C6~C30芳基氨基、取代或未取代的C3~C30杂芳基氨基、取代或未取代的C3~C30杂芳基中的一种;
进一步优选的,R2独立地选自取代或未取代的下述基团:咔唑基团、二苯并呋喃、二苯并噻吩中的一种;
进一步优选的,R2独立地选自取代或未取代的下述结构式B1至B10:
进一步优选的,R2独立地选自的下述结构式A1至A15:
“*”代表与母核的连接位点。
式(Ⅰ)中:
L选自单键、取代或未取代的C6-C30的亚芳基、取代或未取代的C3~C30亚杂芳基中的一种;
优选的,L选自单键或取代或未取代的下述基团:C6-C18的亚芳基、C3-C18的亚杂芳基;
进一步优选的,L选自单键或取代或未取代的下述基团:亚苯基,亚联苯基、亚萘基、亚菲基中的一种。
Ar1为取代或未取代的C3~C30缺电子基团;
优选的,Ar1为取代或未取代C3~C30且至少含有两个N的缺电子基团;
进一步优选的,Ar1为取代或未取代的下述基团:喹唑啉、喹喔啉;
优选的,Ar1选自取代或未取代的下述结构式D1或D2:
“*”代表与L的连接位点。
进一步优选的,Ar1为取代或未取代的下述基团:三嗪、嘧啶;
优选的,Ar1选自取代或未取代的下述结构式D3或D4:
“*”代表与L的连接位点。
当上述基团存在取代基时,所述取代基团分别独立选自C1~C12烷基、C3~C12环烷基、C1~C12烷氧基、卤素、氰基、硝基、羟基、硅烷基、氨基、C6-C30的单环芳烃或稠环芳烃基团中的一种。
进一步地,本发明的通式化合物中,可以优选出下述具体结构化合物,这些化合物仅为代表性的。
作为本发明的另一方面,本发明上述通式化合物在有机电致发光器件中作为磷光主体材料使用。本发明的化合物优选用于红光的磷光发光主体材料。
作为本发明的又一个方面,本发明还提供了一种有机电致发光器件,包括第一电极、第二电极和插入在所述第一电极和第二电极之间的至少包含一层发光层的有机层,其特征在于,所述有机层中含有如上所述通式(Ⅰ)表示的化合物。
上述本发明化合物用作有机电致发光器件中的磷光主体材料性能优异的具体原因尚不明确,推测可能是以下的原因:
本发明的通式化合物采用新的空穴型取代基团与电子型取代基团组合设计方式,确保材料分子具有双极性特性,从而能够达到实现载流子传输平衡的目的。本发明母核结构设计中已限定至少要包括一个取代基团R2作为供电子基团,此设计可以调节材料分子的HOMO能级变浅,从而使得空穴更易传输,同时本发明母核结构中引入Ar1作为吸电子基团,从而使得本发明化合物分子的LUMO能级可以与有机电致发光器件中与其相邻的电子传输层材料的能级相匹配,从而也确保了电子传输的顺畅,这样本发明化合物在实用中可以促进实现器件中电子传输与空穴传输的平衡。因而,采用本发明化合物作为磷光主体材料所制备的有机电致发光器件具备低电压、高效率以及长寿命的有益效果。
具体实施方式
为了使本领域技术人员更好地理解本发明,下面结合具体实施方式对本发明作进一步详细说明。
本发明中未提到的合成方法的化合物的都是通过商业途径获得的原料产品。本发明中所用溶剂和试剂,例如二氯甲烷、石油醚、乙醇、四氢呋喃、N,N-二甲基乙酰胺、喹唑啉、三嗪、喹喔啉等等化学试剂,均可以从国内化工产品市场购买,例如购买自国药集团试剂公司、TCI公司、上海毕得医药公司、百灵威试剂公司等。另外,本领域技术人员也可以通过公知方法合成。
下面对本发明化合物的合成方法进行简要的说明。
代表性合成路径:
其中X代表卤素,*代表硼酸或者卤素,R2和Ar1如通式定义范围,更具体地,以下给出本发明的代表性化合物的合成方法。
合成实施例1:
化合物P1的合成
将S1(100mmol)、N-苯基咔唑-3-硼酸(100mmol)、碳酸钾150mmol,二氧六环300ml,水50ml于反应瓶中,加热至回流反应5h,TLC监控反应完成,加水淬灭后二氯甲烷萃取,有机相浓缩后柱层析纯化得产品P1-A。
将P1-A(50mmol)、2-氯-4-苯基喹唑啉(55mmol)、碳酸铯(100mmol)、DMF500ml回流反应6h,TLC监控反应完全后将反应也倒入水中,过滤滤饼乙醇洗涤后,甲苯重结晶纯化得P1。
1H NMR(500MHz,Chloroform)δ8.55(dd,J=14.2,3.7Hz,1H),8.38–8.29(m,2H),8.24(d,J=2.9Hz,1H),8.13(dd,J=15.0,3.1Hz,1H),8.07–7.97(m,2H),7.87–7.74(m,4H),7.70–7.43(m,15H),7.22–7.05(m,4H).
合成实施例2:
化合物P6的合成
同合成实施例1,不同在于将N-苯基咔唑-3-硼酸替换成等当量的N-(3-联苯基)咔唑-3-硼酸,得化合物P6。
1H NMR(500MHz,Chloroform)δ8.52(ddd,J=29.9,14.6,3.3Hz,2H),8.21(t,J=2.9Hz,1H),8.18–8.07(m,2H),8.07–7.87(m,4H),7.85–7.32(m,21H),7.22–7.02(m,3H),6.60(d,J=15.0Hz,1H).
合成实施例3:
化合物P21的合成
将S2(100mmol)、2-氯-4-苯基喹唑啉(110mmol)、碳酸铯(1500mmol)、DMF500ml回流反应6h,TLC监控反应完全后将反应也倒入水中,过滤滤饼乙醇洗涤后,甲苯重结晶纯化得P21-A。
将P21-A(50mmol)、4-联苯胺(55mmol)、叔丁醇钠(80mmol)、三(二亚苄基丙酮)二钯0.5g、2-二环己基膦-2′,6′-二甲氧基-联苯0.5g加入300ml甲苯的反应瓶中,加热至回流反应5h,TLC监控反应完全,降温后反应液过硅胶后浓缩得,棕色油状物。柱层析纯化得淡黄色固体P21。
1H NMR(500MHz,Chloroform)δ8.17–8.08(m,2H),8.02(ddd,J=15.0,5.7,2.8Hz,2H),7.86–7.71(m,6H),7.70–7.33(m,15H),7.29–7.19(m,2H),7.10(dddd,J=19.1,16.3,6.0,3.3Hz,4H),7.04–6.94(m,1H).
合成实施例4:
化合物P24的合成
同合成实施例1,不同在于将2-氯-4-苯基喹唑啉替换成等当量的2-氯-3-(3-联苯基)喹喔啉,得到化合物P24。
1H NMR(500MHz,Chloroform)δ8.60–8.42(m,4H),8.33(dd,J=15.0,2.9Hz,1H),8.17(d,J=2.9Hz,1H),8.03(dd,J=15.0,2.6Hz,1H),7.89–7.32(m,23H),7.13(pd,J=15.0,3.6Hz,2H),7.01–6.89(m,1H),6.58(dd,J=15.0,3.1Hz,1H).
合成实施例5:
化合物P39的合成
同合成实施例3,不同在于将2-氯-4-苯基喹唑啉替换成等当量的2-氯-3-(3-联苯基)喹喔啉,得到化合物P39。
1H NMR(500MHz,Chloroform)δ8.56–8.40(m,2H),8.33(dd,J=15.0,2.9Hz,1H),8.03(dd,J=15.0,2.6Hz,1H),7.85–7.32(m,25H),7.30–7.18(m,2H),7.12–7.05(m,2H),7.05–6.94(m,2H),6.42(dd,J=14.9,3.0Hz,1H).
合成实施例6:
化合物P42的合成
同合成实施例1,不同在于将2-氯-4-苯基喹唑啉替换成等当量的2-氯-4,6-二苯基三嗪,得到化合物P42。
1H NMR(500MHz,Chloroform)δ8.55(dd,J=14.2,3.7Hz,1H),8.43–8.24(m,5H),8.07–7.91(m,3H),7.82(dt,J=17.0,8.5Hz,1H),7.78–7.70(m,2H),7.69–7.33(m,17H),7.30–7.21(m,2H),7.21–7.03(m,3H),6.46(dd,J=15.0,3.1Hz,1H).
合成实施例7:
化合物P54的合成
将S3(100mmol)、N-(苯基-3-基)咔唑硼酸(100mmol)、碳酸钾150mmol,二氧六环300ml,水50ml于反应瓶中,加热至回流反应5h,TLC监控反应完成,加水淬灭后二氯甲烷萃取,有机相浓缩后柱层析纯化得产品P54-A。
将P54-A(50mmol)、2-氯-4-苯基6-(联苯-4-基)嘧啶(55mmol)、碳酸铯(100mmol)、DMF500ml回流反应6h,TLC监控反应完全后将反应也倒入水中,过滤滤饼乙醇洗涤后,甲苯重结晶纯化得P54。
1H NMR(500MHz,Chloroform)δ8.52(ddd,J=29.9,14.6,3.3Hz,2H),8.37–8.26(m,2H),8.24–8.14(m,2H),8.11(d,J=14.8Hz,1H),8.02(dt,J=9.9,4.9Hz,1H),7.99–7.89(m,3H),7.89–7.80(m,3H),7.79–7.34(m,16H),7.28–7.05(m,5H),6.70(d,J=15.0Hz,1H).
器件实施例
实施方式
OLED包括位于第一电极和第二电极,以及位于电极之间的有机材料层。该有机材料又可以分为多个区域。比如,该有机材料层可以包括空穴传输区、发光层、电子传输区。
在具体实施例中,在第一电极下方或者第二电极上方可以使用基板。基板均为具有机械强度、热稳定性、防水性、透明度优异的玻璃或聚合物材料。此外,作为显示器用的基板上也可以带有薄膜晶体管(TFT)。
第一电极可以通过在基板上溅射或者沉积用作第一电极的材料的方式来形成。当第一电极作为阳极时,可以采用铟锡氧(ITO)、铟锌氧(IZO)、二氧化锡(SnO2)、氧化锌(ZnO)等氧化物透明导电材料和它们的任意组合。第一电极作为阴极时,可以采用镁(Mg)、银(Ag)、铝(Al)、铝-锂(Al-Li)、钙(Ca)、镁-铟(Mg-In)、镁-银(Mg-Ag)等金属或合金以及它们之间的任意组合。
有机材料层可以通过真空热蒸镀、旋转涂敷、打印等方法形成于电极之上。用作有机材料层的化合物可以为有机小分子、有机大分子和聚合物,以及它们的组合。
空穴传输区位于阳极和发光层之间。空穴传输区可以为单层结构的空穴传输层(HTL),包括只含有一种化合物的单层空穴传输层和含有多种化合物的单层空穴传输层。空穴传输区也可以为包括空穴注入层(HIL)、空穴传输层(HTL)、电子阻挡层(EBL)中的至少一层的多层结构。
空穴传输区的材料可以选自、但不限于酞菁衍生物如CuPc、导电聚合物或含导电掺杂剂的聚合物如聚苯撑乙烯、聚苯胺/十二烷基苯磺酸(Pani/DBSA)、聚(3,4-乙撑二氧噻吩)/聚(4-苯乙烯磺酸盐)(PEDOT/PSS)、聚苯胺/樟脑磺酸(Pani/CSA)、聚苯胺/聚(4-苯乙烯磺酸盐)(Pani/PSS)、芳香胺衍生物如下面HT-1至HT-34所示的化合物;或者其任意组合。
空穴注入层位于阳极和空穴传输层之间。空穴注入层可以是单一化合物材料,也可以是多种化合物的组合。例如,空穴注入层可以采用上述HT-1至HT-34的一种或多种化合物,或者采用下述HI1-HI3中的一种或多种化合物;也可以采用HT-1至HT-34的一种或多种化合物掺杂下述HI1-HI3中的一种或多种化合物。
发光层包括可以发射不同波长光谱的的发光染料(即掺杂剂,dopant),还可以同时包括主体材料(Host)。发光层可以是发射红、绿、蓝等单一颜色的单色发光层。多种不同颜色的单色发光层可以按照像素图形进行平面排列,也可以堆叠在一起而形成彩色发光层。当不同颜色的发光层堆叠在一起时,它们可以彼此隔开,也可以彼此相连。发光层也可以是能同时发射红、绿、蓝等不同颜色的单一彩色发光层。
根据不同的技术,发光层材料可以采用荧光电致发光材料、磷光电致发光材料、热活化延迟荧光发光材料等不同的材料。在一个OLED器件中,可以采用单一的发光技术,也可以采用多种不同的发光技术的组合。这些按技术分类的不同发光材料可以发射同种颜色的光,也可以发射不同种颜色的光。
在本发明的一方面,发光层采用磷光电致发光的技术。其发光层主体材料选自、但不限于GPH-1至GPH-80中的一种或多种的组合。
在本发明的一方面,发光层采用磷光电致发光的技术。其发光层磷光掺杂剂可以选自、但不限于以下所罗列的RPD-1至RPD-28的一种或多种的组合。
OLED有机材料层还可以包括发光层与阴极之间的电子传输区。电子传输区可以为单层结构的电子传输层(ETL),包括只含有一种化合物的单层电子传输层和含有多种化合物的单层电子传输层。电子传输区也可以为包括电子注入层(EIL)、电子传输层(ETL)、空穴阻挡层(HBL)中的至少一层的多层结构。
本发明的一方面,电子传输层材料可以选自、但不限于以下所罗列的ET-1至ET-57的一种或多种的组合。
器件中还可以包括位于电子传输层与阴极之间的电子注入层,电子注入层材料包括但不限于以下罗列的一种或多种的组合。
LiQ,LiF,NaCl,CsF,Li2O,Cs2CO3,BaO,Na,Li,Ca。
下面通过将本发明的化合物具体应用到有机电致发光器件中测试实际使用性能来展示和验证本发明的技术效果和优点。
为了方便比较本发明的发光材料的器件应用性能,使用下述所示的化合物C1和C2作为对比材料:
器件实施例1的制备步骤如下:
将涂布了ITO透明导电层的玻璃板在商用清洗剂中超声处理,在去离子水中冲洗,在丙酮:乙醇混合溶剂中超声除油,在洁净环境下烘烤至完全除去水份,用紫外光和臭氧清洗,并用低能阳离子束轰击表面;
把上述带有阳极的玻璃基片置于真空腔内,抽真空至<1×10-5Pa,在上述阳极层膜上按先后顺序真空热蒸镀10nm的HT-4:HIL-3(97/3,w/w)混合物作为空穴注入层,60nm的化合物HT-4作为空穴传输层,40nm的化合物P1:RPD-8(100:3,w/w)二元混合物作为发光层;25nm的化合物ET-46:ET-57(50/50,w/w)混合物作为电子传输层,1nm的LiF作为电子注入层,150nm的金属铝作为阴极。所有有机层和LiF的蒸镀总速率控制在0.1nm/秒,金属电极的蒸镀速率控制在1nm/秒。
器件实施例2~实施例11采用和器件实施例1同样的方法制作,只是把发光层中采用的主体材料P1分别替换成P6、P21、P24、P39、P42、P54、P92、P93、P100和P101;
器件对比实施例1和对比实施例2采用和器件实施例1同样的方法制作,只是发光层中采用的主体材料P1分别替换成C1和C2。
对由上述过程制备的有机电致发光器件进行如下性能测定:
在同样亮度下,使用数字源表及亮度计测定实施例以及对比例制备得到的有机电致发光器件的驱动电压和电流效率以及器件的寿命。具体而言,以每秒0.1V的速率提升电压,测定当有机电致发光器件的亮度达到5000cd/m2时的电压即驱动电压,同时测出此时的电流密度;亮度与电流密度的比值即为电流效率;LT95的寿命测试如下:使用亮度计在10000cd/m2亮度下,保持恒定的电流,测量有机电致发光器件的亮度降为9500cd/m2的时间,单位为小时。所制备的有机电致发光器件性能见下表1:
表1:
就实施例1-11与对比例1和2而言,在有机电致发光器件结构中其他材料相同的情况下,本发明涉及的化合物相比于对比例1中的主体材料C1及对比例2中的主体此类C2,器件的电压均有降低,效率和寿命均有较大幅度提升。
原因推测可能是:现有技术中的化合物C2的分子结构中母核的空穴型很弱,导致HOMO能级加深,不利于空穴的传输,不能有效形成大量的激子,势必导致采用该化合物制备的器件中的载流子传输难以平衡,从而影响器件的综合性能,而本发明中新的化合物制备到器件发光层中后,提高器件的电子传输与空穴传输的平衡能力;
对比化合物C1虽然含有强供电性的芳胺结构,但是其连接在吸电基团上,造成HOMO与LUMO分布重叠在一起,造成与功能层的能级不匹配,导致其光电性能不如本发明化合物,再者其吸电基团被部分芳胺类结构取代,在激子存在的电化学结构中本身存在不稳定性,导致寿命也偏短。
以上结果表明,本发明的新型有机材料用于有机电致发光器件,可以有效的延长器件寿命,降低器件电压和提升器件的效率,由上可见,本发明所公开的此类新型化合物是性能良好的主体材料。
尽管结合实施例对本发明进行了说明,但本发明并不局限于上述实施例,应当理解,在本发明构思的引导下,本领域技术人员可进行各种修改和改进,所附权利要求概括了本发明的范围。
Claims (11)
1.一种通式化合物,如下式(Ⅰ)所示:
其中:X1~X10分别独立地选自CR1、N或CR2,且其中至少一个为CR2;
R1独立地选自氢、C1~C12烷基、C3~C12环烷基、C1~C12烷氧基、卤素、氰基、硝基、羟基、硅烷基、氨基中的一种;
R2独立地选自取代或未取代的C6~C30芳基氨基、取代或未取代的C3~C30杂芳基氨基、取代或未取代的C6~C30芳基、取代或未取代的C3~C30杂芳基中的一种;
L选自单键、取代或未取代的C6~C30的亚芳基、取代或未取代的C3~C30亚杂芳基中的一种;
Ar1为取代或未取代的C3~C30含N的缺电子基团;
当上述基团存在取代基时,所述取代基团分别独立选自C1~C12烷基、C3~C12环烷基、C1~C12烷氧基、卤素、氰基、硝基、羟基、硅烷基、氨基、C6~C30的单环芳烃或稠环芳烃基团中的一种。
2.根据权利要求1所述的通式化合物,其中:
X2、X3、X4、X7、X8和X9中至少一个选自CR2;
优选的,X3、X4、X7和X8中至少一个选自CR2;
进一步优选的,X4或X7选自CR2。
3.根据权利要求1或2中任一所述的通式化合物,其中:
R2独立地选自取代或未取代的C6~C30芳基氨基、取代或未取代的C3~C30杂芳基氨基、取代或未取代的C3~C30杂芳基中的一种;
优选的,R2独立地选自取代或未取代的下述基团:咔唑基团、二苯并呋喃、二苯并噻吩中的一种。
5.根据权利要求1-4中任一所述的通式化合物,其中:
L选自单键或取代或未取代的下述基团:C6-C18的亚芳基、C3-C18的亚杂芳基;
优选的,L选自单键或取代或未取代的下述基团:亚苯基、亚联苯基、亚萘基、亚菲基中的一种。
6.根据权利要求1-5中任一所述的通式化合物,其中:
Ar1为取代或未取代的C3~C30且至少含有两个N的缺电子基团。
10.权利要求1所述的通式化合物的应用,所述应用为在有机电致发光器件中作为发光层材料。
11.一种有机电致发光器件,该器件包括第一电极、第二电极和插入所述第一电极和第二电极之间的一层或多层有机层,其特征在于,所述有机层中包括至少一种由权利要求1中通式(1)所述的化合物。
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