CN108033887B - 有机发光化合物及制备方法和应用 - Google Patents

有机发光化合物及制备方法和应用 Download PDF

Info

Publication number
CN108033887B
CN108033887B CN201711444693.3A CN201711444693A CN108033887B CN 108033887 B CN108033887 B CN 108033887B CN 201711444693 A CN201711444693 A CN 201711444693A CN 108033887 B CN108033887 B CN 108033887B
Authority
CN
China
Prior art keywords
stirring
methanol
reaction
compound
substituted
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201711444693.3A
Other languages
English (en)
Other versions
CN108033887A (zh
Inventor
王永光
于哲
孙毅
高伟
李国强
李建行
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jilin Optical and Electronic Materials Co Ltd
Original Assignee
Jilin Optical and Electronic Materials Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jilin Optical and Electronic Materials Co Ltd filed Critical Jilin Optical and Electronic Materials Co Ltd
Priority to CN201711444693.3A priority Critical patent/CN108033887B/zh
Publication of CN108033887A publication Critical patent/CN108033887A/zh
Application granted granted Critical
Publication of CN108033887B publication Critical patent/CN108033887B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
    • C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
    • C07C217/92—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the nitrogen atom of at least one of the amino groups being further bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/58—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton
    • 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
    • C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/38—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
    • 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
    • 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
    • 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
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
    • 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
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
    • 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
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • 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
    • 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
    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • 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
    • H10K85/649—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
    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1022—Heterocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
    • 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
    • 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
    • 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
    • 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
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom

Abstract

本发明的目的是：提供一种能够使器件的发光效率及寿命提高、具有适当的色坐标的新型结构的有机发光化合物及制备方法和应用。本发明提供的有机发光化合物具有高的电子传达效率，从而能够在制造器件时防止结晶，并能够很容易地形成层，由此改善了器件的电流特性。本发明提供的有机发光化合物作为发光层掺杂材料制备得到的有机电致发光器件的发光效率及寿命均有显著提高。本发明提供的有机发光化合物的制备方法，原料易得，工艺简单，适合于工业化生产。

Description

有机发光化合物及制备方法和应用
技术领域
本发明涉及发光材料领域，具体涉及一种有机发光化合物及制备方法和应用。
背景技术
有机电致发光器件(organic electroluminescence device:OLED)是在有机发光材料中加以电压，使电能转化为光能的一种器件，通常结构是以阳极(anode)，阴极(cathode)和两极之间的有机物层组成。有机物层可以由空穴注入层，空穴传输层，电子阻断层，发光层(包括主体材料及掺杂材料)，电子缓冲层，空穴阻断层，电子传输层，电子注入层等形成。此种有机电致发光器件加以电压后，从阳极注入空穴，从阴极注入电子至发光层，通过空穴与电子复合形成高能量的激子，释放出能量，将能量传递给有机发光物质的分子，使其从基态跃迁到激发态，受激分子再从激发态回到基态，辐射跃迁而产生发光现象。
其中发光层材料是决定器件发光效率、寿命和性能的最重要的因素。发光层材料包括主体材料及掺杂材料，但有机发光主体材料一般载流子的迁移率都普遍较低，因此采用掺杂技术可以大大地提高有机主体材料的迁移率，降低 OLED的驱动电压。所以能否研制出新型结构的掺杂材料，能够使器件的发光效率及寿命提高显得至关重要。
发明内容
本发明的目的是：提供一种能够使器件的发光效率及寿命提高、具有适当的色坐标的新型结构的有机发光化合物及制备方法和应用。
为了实现上述目的，本发明的技术方案具体如下：
一种有机发光化合物，其结构式如下：
Figure BDA0001527305790000021
式中，Ar1和Ar2各自独立地选自取代或未取代的苯基、取代或未取代的稠环芳基、或取代或未取代的芳族杂环基。
在上述技术方案中，Ar1和Ar2各自独立地选自碳原子数为6-18的取代或未取代的苯基、碳原子数为10-25的取代或未取代的稠环芳基、或碳原子数为12-18的取代或未取代的芳族杂环基。
在上述技术方案中，Ar1和Ar2各自独立地选自碳原子数为8-16的取代或未取代的苯基、碳原子数为12-24的取代或未取代的稠环芳基、或碳原子数为12-15的取代或未取代的芳族杂环基。
在上述技术方案中，Ar1和Ar2各自独立地选自碳原子数为10-15的取代或未取代的苯基、碳原子数为14-18的取代或未取代的稠环芳基、或碳原子数为15-18 的取代或未取代的芳族杂环基。
在上述技术方案中，Ar1和Ar2各自独立地选自碳原子数为11-14的取代或未取代的苯基、碳原子数为15-16的取代或未取代的稠环芳基、或碳原子数为12的取代或未取代的芳族杂环基。
在上述技术方案中，Ar1和Ar2各自独立地选自碳原子数为12-13的取代或未取代的苯基、碳原子数为10的取代或未取代的稠环芳基、或碳原子数为15的取代或未取代的芳族杂环基。
在上述技术方案中，Ar1和Ar2各自独立地选自碳原子数为7-9的取代或未取代的苯基、碳原子数为12的取代或未取代的稠环芳基、或碳原子数为18的取代或未取代的芳族杂环基。
在上述技术方案中，所述有机发光化合物为下述结构中的任意一个：
Figure BDA0001527305790000031
Figure BDA0001527305790000041
Figure BDA0001527305790000051
Figure BDA0001527305790000061
一种有机发光化合物的制备方法，包括以下步骤：
在氮气条件下，将化合物1-1，化合物1-2，碳酸钾，1,4-二恶烷，加入甲苯，在70℃搅拌，相同温度下，加入四三苯基膦钯和蒸馏水，回流搅拌过夜，反应结束后，冷却到室温，加入甲醇，将反应液浓缩后，固体用蒸馏水和甲醇洗涤，用甲苯回流搅拌，在50℃条件下干燥，得到中间体1；
在氮气条件下，将中间体1加入到四氢呋喃中搅拌直至固体完全溶解，0℃冷却后，滴加甲基氯化镁，搅拌反应过夜，滴加氯化铵溶液，分离有机层后，加入乙酸乙酯和蒸馏水萃取，将滤液减压浓缩后，浓缩液柱层析，得到中间体2；
将中间体2加入二氯甲烷中，完全溶解后，加入甲磺酸，反应结束后，将反应液减压浓缩，用甲醇重结晶，搅拌，用甲醇洗涤，加入丙酮，在70℃回流搅拌过夜，冷却至室温后，过滤，用丙酮洗涤，得到中间体3；
在三口瓶中加入中间体3，NBS和氯仿，常温下搅拌24小时，反应完成后，减压蒸馏，将析出的固体产物过滤，用甲醇洗涤，得到中间体4；
氮气条件下，向圆底烧瓶中加入中间体4，含Ar1和Ar2基团的胺化物及叔丁醇钠，再加入甲苯溶解后，继续加入三(二亚苄基丙酮)钯和正丁基膦，在110℃条件下，回流搅拌反应12小时，反应结束后，用水/甲醇洗涤、过滤，然后加入氯苯、活性炭和无水硫酸镁，溶解后过滤氯苯，甲醇重结晶，得到式1所示的化合物；
合成路线如下：
Figure BDA0001527305790000071
式中，Ar1和Ar2各自独立地选自取代或未取代的苯基、取代或未取代的稠环芳基、或取代或未取代的芳族杂环基。
上述式1所示的有机发光化合物用作有机电致发光器件发光层的掺杂材料。
本发明的有益效果是：
本发明提供的有机发光化合物具有高的电子传达效率，从而能够在制造器件时防止结晶，并能够很容易地形成层，由此改善了器件的电流特性。本发明提供的有机发光化合物作为发光层掺杂材料制备得到的有机电致发光器件的发光效率及寿命均有显著提高。
本发明提供的有机发光化合物的制备方法，原料易得，工艺简单，适合于工业化生产。
具体实施方式
本发明提供一种有机发光化合物，其结构式如下：
Figure BDA0001527305790000072
Figure BDA0001527305790000081
式中，Ar1和Ar2各自独立地选自取代或未取代的苯基、取代或未取代的稠环芳基、或取代或未取代的芳族杂环基。
优选的是，Ar1和Ar2各自独立地选自碳原子数为6-18的取代或未取代的苯基、碳原子数为10-25的取代或未取代的稠环芳基、或碳原子数为12-18的取代或未取代的芳族杂环基。
优选的是，Ar1和Ar2各自独立地选自碳原子数为8-16的取代或未取代的苯基、碳原子数为12-24的取代或未取代的稠环芳基、或碳原子数为12-15的取代或未取代的芳族杂环基。
优选的是，Ar1和Ar2各自独立地选自碳原子数为10-15的取代或未取代的苯基、碳原子数为14-18的取代或未取代的稠环芳基、或碳原子数为15-18的取代或未取代的芳族杂环基。
优选的是，Ar1和Ar2各自独立地选自碳原子数为11-14的取代或未取代的苯基、碳原子数为15-16的取代或未取代的稠环芳基、或碳原子数为12的取代或未取代的芳族杂环基。
优选的是，Ar1和Ar2各自独立地选自碳原子数为12-13的取代或未取代的苯基、碳原子数为10的取代或未取代的稠环芳基、或碳原子数为15的取代或未取代的芳族杂环基。
优选的是，Ar1和Ar2各自独立地选自碳原子数为7-9的取代或未取代的苯基、碳原子数为12的取代或未取代的稠环芳基、或碳原子数为18的取代或未取代的芳族杂环基。
最优选的是，所述有机发光化合物为下述结构中的任意一个：
Figure BDA0001527305790000091
Figure BDA0001527305790000101
Figure BDA0001527305790000111
本发明还提供一种有机发光化合物的制备方法，包括以下步骤：
在氮气条件下，将化合物1-1，化合物1-2，碳酸钾，1,4-二恶烷，加入甲苯，在70℃搅拌，相同温度下，加入四三苯基膦钯和蒸馏水，回流搅拌过夜，反应结束后，冷却到室温，加入甲醇，将反应液浓缩后，固体用蒸馏水和甲醇洗涤，用甲苯回流搅拌，在50℃条件下干燥，得到中间体1；
在氮气条件下，将中间体1加入到四氢呋喃中搅拌直至固体完全溶解，0℃冷却后，滴加甲基氯化镁，搅拌反应过夜，滴加氯化铵溶液，分离有机层后，加入乙酸乙酯和蒸馏水萃取，将滤液减压浓缩后，浓缩液柱层析，得到中间体2；
将中间体2加入二氯甲烷中，完全溶解后，加入甲磺酸，反应结束后，将反应液减压浓缩，用甲醇重结晶，搅拌，用甲醇洗涤，加入丙酮，在70℃回流搅拌过夜，冷却至室温后，过滤，用丙酮洗涤，得到中间体3；
在三口瓶中加入中间体3，NBS和氯仿，常温下搅拌24小时，反应完成后，减压蒸馏，将析出的固体产物过滤，用甲醇洗涤，得到中间体4；
氮气条件下，向圆底烧瓶中加入中间体4，含Ar1和Ar2基团的胺化物及叔丁醇钠，再加入甲苯溶解后，继续加入三(二亚苄基丙酮)钯和正丁基膦，在110℃条件下，回流搅拌反应12小时，反应结束后，用水/甲醇洗涤、过滤，然后加入氯苯、活性炭和无水硫酸镁，溶解后过滤氯苯，甲醇重结晶，得到式1所示的化合物；
合成路线如下：
Figure BDA0001527305790000121
式中，Ar1和Ar2各自独立地选自取代或未取代的苯基、取代或未取代的稠环芳基、或取代或未取代的芳族杂环基。
上述式1所示的有机发光化合物用作有机电致发光器件发光层的掺杂材料。
中间体的合成
Figure BDA0001527305790000131
在氮气条件下，将中间体1-1(43.4g,105.52mmol)，2-乙酰基苯基硼酸 (34.6g,211.04mmol)，碳酸钾(18.23g,131.9mmol)，400mL 1,4-二恶烷，加入甲苯 300mL，在70℃搅拌，相同温度下，加入四三苯基膦钯(2.54g,2.19mmol)和40mL 蒸馏水，回流搅拌过夜，反应结束后，冷却到室温，加入100mL甲醇，将反应液浓缩后，固体用蒸馏水和甲醇洗涤，用300mL甲苯回流搅拌，在50℃条件下干燥，得到38.8g中间体1-2(收率75％)，质谱：测量值为490，理论值为490.19 。
在氮气条件下，将中间体1-2(16.6g,33.77mmol)，放入400mL四氢呋喃中搅拌直至固体完全溶解，0℃冷却后，慢慢滴加101.3mL(303.98mmol)甲基氯化镁，搅拌反应过夜，慢慢滴加1.5L氯化铵溶液，分离有机层后，加入乙酸乙酯和蒸馏水萃取，将滤液减压浓缩后，浓缩液柱层析，得到9.7g白色中间体1-3 (收率55％)，质谱：测量值为522，理论值为522.26。
将中间体1-3(9.1g,17.41mmol)，300mL二氯甲烷，完全溶解后，加入5.65mL(87.09mmol)甲磺酸(MSA)，反应结束后，将反应液减压浓缩，用200mL甲醇重结晶，搅拌一段时间后，用甲醇洗涤，加入400mL丙酮，在70℃回流搅拌过夜，冷却至室温后，过滤，用200mL丙酮洗涤，得到5.9g中间体1-4(收率70％)，质谱：测量值为486，理论值为486.23。
在三口瓶中加入中间体1-4(20.9g,42.86mmol)，NBS(8.35g,47.1mmol)， 360mL氯仿(三氯甲烷)，常温下搅拌24小时，反应完成后，减压蒸馏，将析出的固体产物过滤，用甲醇洗涤，得到19.4g中间体1-5(收率80％)，质谱：测量值为564，理论值为564.15。
[合成例1]化合物1的合成
Figure BDA0001527305790000141
氮气条件下，向500mL的圆底烧瓶中加入中间体1-5(11.2g,19.8mmol)，二苯胺(7.37g,43.56mmol)及叔丁醇钠(3.2g,33.7mmol)，再加入甲苯160mL 溶解后，继续加入三(二亚苄基丙酮)钯(0.454g,0.5mmol)和正丁基膦(0.6g,1.49 mmol)，在110℃条件下，回流搅拌反应12小时，反应结束后，用水/甲醇洗涤、过滤，然后加入氯苯、活性炭和无水硫酸镁，溶解后过滤氯苯，用甲醇重结晶，得到7g化合物1(收率75％)，质谱：测量值为653，理论值为653.31 。
[合成例2]化合物12的合成
Figure BDA0001527305790000142
使用中间体1-5(11.8g,19.75mmol)，中间体12-1(6.4g,19.8mmol)，三(二亚苄基丙酮)钯(0.75g,0.79mmol)，叔丁醇钠(2.85g,29.63mmol)，三叔丁基膦 (0.77mL,1.58mmol)，按照化合物1相同的制备方法制备得到12.9g化合物12(收率81％)，质谱：测量值为805，理论值为805.37 。
[合成例3]化合物16的合成
Figure BDA0001527305790000151
使用中间体1-5(23.6g,9.5mmol)，中间体16-1(16.3g,40mmol)，三(二亚苄基丙酮)钯(0.75g,0.79mmol)，叔丁醇钠(5.7g,59.3mmol)，三叔丁基膦 (1.54mL,3.16mmol)，按照和化合物1相同的制备方法制备化合物16(28.5g， 81％)，质谱：测量值为891，理论值为891.39。
[合成例4]化合物18的合成
Figure BDA0001527305790000152
使用中间体1-5(11.8g,19.75mmol)，中间体18-1(6.4g,19.8mmol)，三(二亚苄基丙酮)钯(0.75g,0.79mmol)，叔丁醇钠(2.85g,29.63mmol)，三叔丁基膦 (0.77mL,1.58mmol)，按照和化合物1相同的制备方法制备14g化合物18(收率 88％)，质谱：测量值为805，理论值为805.37。
[合成例5]化合物25的合成
Figure BDA0001527305790000153
使用中间体1-5(14.2g,23.7mmol)，中间体25-1(10.5g,24mmol)，三(二亚苄基丙酮)钯(0.75g,0.79mmol)，叔丁醇钠(3.4g,35.6mmol)，三叔丁基膦 (1.54mL,3.16mmol)，按照和化合物1相同的制备方法制备17.3g化合物25(收率 79％)，质谱：测量值为921，理论值为921.43。
按照上述合成例的合成方法合成其它化合物。
有机电致发光器件的制备与性能评价
有机电致发光器件的制备
1、蓝色有机电致发光器件
比较例1
用化学式a表示的化合物a作为蓝色荧光主体材料，化学式b表示的化合物 b作为掺杂材料，N1-(萘-2-yl)-N4,N4-二(4-(萘-2-yl(苯基)氨基)苯基)-N1-苯基苯- 1,4-二胺("2-TNATA")作为空穴注入物质，制备具有以下结构的有机电致发光器件：ITO/2-TNATA(80nm)/α-NPD(30nm)/化合物a+化合物b(30nm)/Alq3(30nm)/Li F(0.5nm)/Al(60nm)。
阳极使用在康宁公司(Corning)的15Ω/cm2
Figure BDA0001527305790000162
ITO玻璃基板。玻璃基板切断50mmx 50mmx 0.7mm大小，丙酮、异丙基醇、水中各自15分钟超声波洗涤以后，30分钟UV臭氧清洗后使用。以上基板上面蒸镀80nm 2-TANATA空穴注入层、蒸镀空穴传输层30nmα-NPD、蒸镀30nm化合物a+化合物b(5％掺杂)形成发光层。蒸镀30nmAlq3形成电子传输层。以上电子传输层上面蒸镀LiF 0.5nm(电子注入)和Al 60nm(阴极)按顺序蒸镀制备出比较样品1。
Figure BDA0001527305790000161
Figure BDA0001527305790000171
比较例2
将比较例1中的化合物b替换为化学式c表示的化合物c外，其他同比较例 1，得到比较样品2。
<化学式c>
Figure BDA0001527305790000172
比较例3
将比较例1中的化合物b替换为化学式d表示的化合物d外，其他同比较例1，得到比较样品3。
<化学式d>
Figure BDA0001527305790000173
比较例4
将比较例1中的化合物b替换为化学式f表示的化合物f外，其他同比较例 1，得到比较样品4。
<化学式f>
Figure BDA0001527305790000181
实施例1-54
将比较例1中的化合物b分别替换为合成例合成的化合物1-54外，其他同比较例1，得到实施例样品1-54。
评价例1：比较样品1、2、3、4，及实施例样品1-54的发光性能评价
比较示例1-4及实施例样品1-54使用Keithley sourcemeter“2400”,KONIKAMINOLTA“CS-2000”仪器评价发光亮度、发光效率、发光峰。评价结果表示在表 1。上述示例发光峰蓝光448～463nm范围。
表1
Figure BDA0001527305790000182
Figure BDA0001527305790000191
Figure BDA0001527305790000201
由表1能看出实施例1-54跟比较示例1-4比较具有更向上的发光特性。
评价例2：比较样品1、2、3、4，及实施例样品1-54的寿命特性评价
比较样品1-4及实施例样品1-54利用ENC technology公司的LTS-1004AC 寿命测试装置3000nit为基准测试达到97％时间结果表示下表2。
Figure BDA0001527305790000202
Figure BDA0001527305790000211
由表2能看出，实施例1-54跟比较例1-4相比具有更好的寿命特性。
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。

Claims (3)

1.一种有机发光化合物，其特征在于，其为下述结构中的任意一个：
Figure FDA0002616601550000011
Figure FDA0002616601550000021
Figure FDA0002616601550000031
Figure FDA0002616601550000041
2.权利要求1所述的有机发光化合物的制备方法，其特征在于，包括以下步骤：
在氮气条件下，将化合物1-1，化合物1-2，碳酸钾，1,4-二恶烷，加入甲苯，在70℃搅拌，相同温度下，加入四三苯基膦钯和蒸馏水，回流搅拌过夜，反应结束后，冷却到室温，加入甲醇，将反应液浓缩后，固体用蒸馏水和甲醇洗涤，用甲苯回流搅拌，在50℃条件下干燥，得到中间体1；
在氮气条件下，将中间体1加入到四氢呋喃中搅拌直至固体完全溶解，0℃冷却后，滴加甲基氯化镁，搅拌反应过夜，滴加氯化铵溶液，分离有机层后，加入乙酸乙酯和蒸馏水萃取，将滤液减压浓缩后，浓缩液柱层析，得到中间体2；
将中间体2加入二氯甲烷中，完全溶解后，加入甲磺酸，反应结束后，将反应液减压浓缩，用甲醇重结晶，搅拌，用甲醇洗涤，加入丙酮，在70℃回流搅拌过夜，冷却至室温后，过滤，用丙酮洗涤，得到中间体3；
在三口瓶中加入中间体3，NBS和氯仿，常温下搅拌24小时，反应完成后，减压蒸馏，将析出的固体产物过滤，用甲醇洗涤，得到中间体4；
氮气条件下，向圆底烧瓶中加入中间体4，含Ar1和Ar2基团的胺化物及叔丁醇钠，再加入甲苯溶解后，继续加入三(二亚苄基丙酮)钯和正丁基膦，在110℃条件下，回流搅拌反应12小时，反应结束后，用水和甲醇洗涤、过滤，然后加入氯苯、活性炭和无水硫酸镁，溶解后过滤氯苯，甲醇重结晶，得到式1所示的化合物；
合成路线如下：
Figure FDA0002616601550000051
式中，Ar1和Ar2对应权利要求1中各结构化合物上的取代基团。
3.权利要求1所述的有机发光化合物用作有机电致发光器件发光层的掺杂材料的应用。
CN201711444693.3A 2017-12-27 2017-12-27 有机发光化合物及制备方法和应用 Active CN108033887B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711444693.3A CN108033887B (zh) 2017-12-27 2017-12-27 有机发光化合物及制备方法和应用

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711444693.3A CN108033887B (zh) 2017-12-27 2017-12-27 有机发光化合物及制备方法和应用

Publications (2)

Publication Number Publication Date
CN108033887A CN108033887A (zh) 2018-05-15
CN108033887B true CN108033887B (zh) 2020-11-17

Family

ID=62098027

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711444693.3A Active CN108033887B (zh) 2017-12-27 2017-12-27 有机发光化合物及制备方法和应用

Country Status (1)

Country Link
CN (1) CN108033887B (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112079731B (zh) * 2020-09-18 2023-04-28 吉林奥来德光电材料股份有限公司 一种发光辅助材料及其制备方法和应用
CN112457201A (zh) * 2020-11-13 2021-03-09 阜阳欣奕华材料科技有限公司 化合物与有机电致发光器件、显示装置

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007072952A1 (en) * 2005-12-20 2007-06-28 Canon Kabushiki Kaisha 4-aminofluorene compound and organic light emitting device
WO2014106522A1 (de) * 2013-01-03 2014-07-10 Merck Patent Gmbh Materialien für elektronische vorrichtungen

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007072952A1 (en) * 2005-12-20 2007-06-28 Canon Kabushiki Kaisha 4-aminofluorene compound and organic light emitting device
WO2014106522A1 (de) * 2013-01-03 2014-07-10 Merck Patent Gmbh Materialien für elektronische vorrichtungen

Also Published As

Publication number Publication date
CN108033887A (zh) 2018-05-15

Similar Documents

Publication Publication Date Title
JP6182145B2 (ja) 発光素子用のスピロビフルオレン化合物
WO2013157367A1 (ja) 新規なトリフェニレン誘導体及び該誘導体が使用されている有機エレクトロルミネッセンス素子
JP7119204B2 (ja) 有機発光化合物及びこれを用いた有機電界発光素子
TW201714869A (zh) 有機電激發光裝置及其材料
JP2014131983A (ja) アミン誘導体、有機発光材料及びそれを用いた有機エレクトロルミネッセンス素子
KR20150043669A (ko) 유기전기 소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치
KR20140095923A (ko) 유기전기 소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치
CN110078755B (zh) 化合物、显示面板以及显示装置
CN114040916A (zh) 新型硼化合物及包括该新型硼化物的有机发光元件
EP3683852B1 (en) Organic electroluminescent element
CN111116628A (zh) 一种有机化合物和使用该化合物的有机电致发光器件
KR20140098502A (ko) 유기전기 소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치
CN113528123B (zh) 主体材料和包含其的有机电致发光器件
CN108033887B (zh) 有机发光化合物及制备方法和应用
KR101321988B1 (ko) 방향족 유도체 및 이를 포함하는 유기전기발광소자
CN109897029B (zh) 三联吡啶类衍生物及其制备方法、应用和器件
KR101311840B1 (ko) 신규한 3차 아릴 아민 및 이를 포함한 유기전계 발광소자
KR20140070360A (ko) 유기 전계 발광 소자용 정공 수송 재료 및 그것을 사용한 유기 전계 발광 소자
KR20110106192A (ko) 축합 아릴아민계 화합물 및 이를 포함하는 유기전계발광소자
CN108178729B (zh) 一种有机发光化合物及其制备方法和应用
CN113307770A (zh) 一种发光辅助材料及其制备方法和应用
CN110078727B (zh) 一种有机电致发光化合物及其制法和有机电致发光器件
KR20150010579A (ko) 유기 일렉트로루미네센스 소자용 재료 및 이를 사용한 유기 일렉트로루미네센스 소자
CN108084038B (zh) 一种有机发光化合物及其制备方法和电致发光器件
KR20150114658A (ko) 유기발광 화합물 및 이를 포함하는 유기전계발광소자

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant