CN108178729B - 一种有机发光化合物及其制备方法和应用 - Google Patents

一种有机发光化合物及其制备方法和应用 Download PDF

Info

Publication number
CN108178729B
CN108178729B CN201711444628.0A CN201711444628A CN108178729B CN 108178729 B CN108178729 B CN 108178729B CN 201711444628 A CN201711444628 A CN 201711444628A CN 108178729 B CN108178729 B CN 108178729B
Authority
CN
China
Prior art keywords
substituted
carbon atoms
unsubstituted
organic light
stirring
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
CN201711444628.0A
Other languages
English (en)
Other versions
CN108178729A (zh
Inventor
王辉
李国强
李建行
姜晓晨
段伟伟
魏忠义
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 CN201711444628.0A priority Critical patent/CN108178729B/zh
Publication of CN108178729A publication Critical patent/CN108178729A/zh
Application granted granted Critical
Publication of CN108178729B publication Critical patent/CN108178729B/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
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
    • 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
    • H10K85/6574—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
    • C09K2211/1011—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
    • C09K2211/1025—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
    • 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
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-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
    • H10K85/649—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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Electroluminescent Light Sources (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

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其制备方法和应用。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

一种有机发光化合物及其制备方法和应用
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其制备方法和应用。
背景技术
有机电致发光器件(OLED)是近年来国际上平板显示领域的一个研究热点。其具有结构简单，成品率高，成本低，主动发光，响应速度快，分辨率高等优点；并且驱动电压低，全固态等优点，被认为是未来最有可能替代夜景显示器。
有机电致发光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。有机物层可以由发光层、空穴注入层，空穴传输层，电子阻断层，电子缓冲层，空穴阻断层，电子传输层，电子注入层等形成。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其制备方法和应用。
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 BDA0001527305230000021
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 BDA0001527305230000031
Figure BDA0001527305230000041
Figure BDA0001527305230000051
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；
在氮气条件下，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，用甲醇重结晶，得到式1所示的化合物；
合成路线如下：
Figure BDA0001527305230000071
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 BDA0001527305230000072
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 BDA0001527305230000081
Figure BDA0001527305230000091
Figure BDA0001527305230000101
Figure BDA0001527305230000111
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；
在氮气条件下，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，用甲醇重结晶，得到式1所示的化合物；
合成路线如下：
Figure BDA0001527305230000121
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。
本发明还提供一种有机发光化合物的应用，上述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 BDA0001527305230000131
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(16.6g,94.2mmol)，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22.1g中间体1-5(收率80％)，质谱：测量值为642，理论值为642.06。
[合成例1]化合物1的合成
Figure BDA0001527305230000141
氮气条件下，向500mL的圆底烧瓶中加入中间体1-5(12.8g,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,1.49mmol)，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12.2g化合物1(收率75％)，质谱：测量值为820，理论值为820.38。
[合成例2]化合物17的合成
Figure BDA0001527305230000142
使用中间体1-5(25.5g,39.5mmol)，化合物17-1(21.6g,80mmol)，Pd2(dba)3(0.75g,0.79mmol)，NaOt-Bu(5.7g,59.3mmol)，(t-Bu)3P(1.54mL,3.16mmol)，按照化合物1相同的制备方法制备得到28.5g化合物17(收率81％)，质谱：测量值为1022，理论值为1022.43。
[合成例3]化合物21的合成
Figure BDA0001527305230000151
使用中间体1-5(15.3g,23.7mmol)，化合物21-1(13g,48mmol)，Pd2(dba)3(0.75g,0.79mmol)，NaOt-Bu(3.4g,35.6mmol)，(t-Bu)3P(1.54mL,3.16mmol)，按照化合物1相同的制备方法制备得到28.5g化合物21(收率81％)，质谱：测量值为1022，理论值为1022.43。
[合成例4]化合物41的合成
Figure BDA0001527305230000152
使用中间体1-5(19.9g,30.8mmol)，化合物41-1(16.4g,62.4mmol)，Pd2(dba)3(0.75g,0.79mmol)，NaOt-Bu(4.4g,46.3mmol)，(t-Bu)3P(1.54mL,3.16mmol)，按照化合物1相同的制备方法制备得到25.2g化合物41(收率81％)，质谱：测量值为1008，理论值为1008.43。
[合成例5]化合物46的合成
Figure BDA0001527305230000153
使用中间体1-5(19.9g,30.8mmol)，化合物46-1(17.8g,62.4mmol)，Pd2(dba)3(0.75g,0.79mmol)，NaOt-Bu(4.4g,46.3mmol)，(t-Bu)3P(1.54mL,3.16mmol)，按照化合物1相同的制备方法制备得到28.2g化合物46(收率87％)，质谱：测量值为1052，理论值为1052.51。
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)/LiF(0.5nm)/Al(60nm)。
阳极使用在康宁公司(Corning)的15Ω/cm2
Figure BDA0001527305230000161
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LiF0.5nm(电子注入)和Al 60nm(阴极)按顺序蒸镀制备出比较样品1。
Figure BDA0001527305230000162
Figure BDA0001527305230000171
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 BDA0001527305230000172
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 BDA0001527305230000173
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 BDA0001527305230000181
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 BDA0001527305230000182
Figure BDA0001527305230000191
Figure BDA0001527305230000201
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。
表2
Figure BDA0001527305230000202
Figure BDA0001527305230000211
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 (9)

1.一种有机发光化合物，其特征在于，其结构式如下：
Figure FDA0002481517520000011
式中，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。
2.根据权利要求1所述的有机发光化合物，其特征在于，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。
3.根据权利要求1所述的有机发光化合物，其特征在于，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。
4.根据权利要求1所述的有机发光化合物，其特征在于，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。
5.根据权利要求1所述的有机发光化合物，其特征在于，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。
6.根据权利要求1所述的有机发光化合物，其特征在于，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。
7.根据权利要求1所述的有机发光化合物，其特征在于，所述有机发光化合物为下述结构中的任意一个：
Figure FDA0002481517520000021
Figure FDA0002481517520000031
Figure FDA0002481517520000041
8.一种权利要求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；
在氮气条件下，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(t-Bu)3P，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，得到式1所示的化合物；
合成路线如下：
Figure FDA0002481517520000061
式中，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。
9.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。
CN201711444628.0A 2017-12-27 2017-12-27 一种有机发光化合物及其制备方法和应用 Active CN108178729B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711444628.0A CN108178729B (zh) 2017-12-27 2017-12-27 一种有机发光化合物及其制备方法和应用

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711444628.0A CN108178729B (zh) 2017-12-27 2017-12-27 一种有机发光化合物及其制备方法和应用

Publications (2)

Publication Number Publication Date
CN108178729A CN108178729A (zh) 2018-06-19
CN108178729B true CN108178729B (zh) 2020-08-25

Family

ID=62547677

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711444628.0A Active CN108178729B (zh) 2017-12-27 2017-12-27 一种有机发光化合物及其制备方法和应用

Country Status (1)

Country Link
CN (1) CN108178729B (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20200098753A (ko) * 2019-02-11 2020-08-21 삼성디스플레이 주식회사 유기 전계 발광 소자 및 유기 전계 발광 소자용 모노아민 화합물
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

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008130840A (ja) * 2006-11-21 2008-06-05 Tosoh Corp 有機電界発光素子
JP2008201769A (ja) * 2007-01-26 2008-09-04 Tosoh Corp ベンゾフルオレン化合物及びその用途
CN101575259A (zh) * 2007-12-04 2009-11-11 葛来西雅帝史派有限公司 新颖的有机电致发光化合物和使用该化合物的有机电致发光器件
KR20090117326A (ko) * 2008-05-09 2009-11-12 주식회사 하나화인켐 유기 발광 소자 및 이에 사용되는 유기 발광 화합물
CN102227486A (zh) * 2008-11-26 2011-10-26 葛来西雅帝史派有限公司 使用电致发光化合物的有机电致发光器件
KR20120112257A (ko) * 2011-04-01 2012-10-11 에스에프씨 주식회사 신규한 화합물 및 이를 포함하는 유기전계발광소자
WO2013081410A1 (ko) * 2011-11-30 2013-06-06 주식회사 두산 안트라센 유도체 및 이를 이용한 유기 전계 발광 소자
CN105514288A (zh) * 2014-10-13 2016-04-20 环球展览公司 新颖化合物和在装置中的用途
CN106467469A (zh) * 2016-06-13 2017-03-01 江苏三月光电科技有限公司 一种有机电致发光化合物及其应用
CN106866542A (zh) * 2017-01-17 2017-06-20 华南理工大学 一种以萘二并茚芴单元为核的双极性小分子发光材料及其制备方法与应用

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10381569B2 (en) * 2014-11-25 2019-08-13 Universal Display Corporation Organic electroluminescent materials and devices

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008130840A (ja) * 2006-11-21 2008-06-05 Tosoh Corp 有機電界発光素子
JP2008201769A (ja) * 2007-01-26 2008-09-04 Tosoh Corp ベンゾフルオレン化合物及びその用途
CN101575259A (zh) * 2007-12-04 2009-11-11 葛来西雅帝史派有限公司 新颖的有机电致发光化合物和使用该化合物的有机电致发光器件
KR20090117326A (ko) * 2008-05-09 2009-11-12 주식회사 하나화인켐 유기 발광 소자 및 이에 사용되는 유기 발광 화합물
CN102227486A (zh) * 2008-11-26 2011-10-26 葛来西雅帝史派有限公司 使用电致发光化合物的有机电致发光器件
KR20120112257A (ko) * 2011-04-01 2012-10-11 에스에프씨 주식회사 신규한 화합물 및 이를 포함하는 유기전계발광소자
WO2013081410A1 (ko) * 2011-11-30 2013-06-06 주식회사 두산 안트라센 유도체 및 이를 이용한 유기 전계 발광 소자
CN105514288A (zh) * 2014-10-13 2016-04-20 环球展览公司 新颖化合物和在装置中的用途
CN106467469A (zh) * 2016-06-13 2017-03-01 江苏三月光电科技有限公司 一种有机电致发光化合物及其应用
CN106866542A (zh) * 2017-01-17 2017-06-20 华南理工大学 一种以萘二并茚芴单元为核的双极性小分子发光材料及其制备方法与应用

Also Published As

Publication number Publication date
CN108178729A (zh) 2018-06-19

Similar Documents

Publication Publication Date Title
TW201714869A (zh) 有機電激發光裝置及其材料
JP2016153394A (ja) 有機エレクトロルミネセンス素子用インデノトリフェニレン系アミン誘導体
US9000171B2 (en) Organic electroluminescence material including a substituted acridine compound and organic electroluminescence device including the same
CN111170974B (zh) 一种主体化合物和使用该化合物的电致发光器件
CN107573306B (zh) 一种有机电致发光化合物
US9196841B2 (en) Arylamine compound and electroluminescence device using the same
CN108178729B (zh) 一种有机发光化合物及其制备方法和应用
US9676767B2 (en) Indoloacridine-containing derivative, preparation process and use thereof, and organic luminescent device
CN113528123B (zh) 主体材料和包含其的有机电致发光器件
KR20140070360A (ko) 유기 전계 발광 소자용 정공 수송 재료 및 그것을 사용한 유기 전계 발광 소자
CN108033887B (zh) 有机发光化合物及制备方法和应用
KR20140138031A (ko) 아릴 아민 유도체 및 그것을 정공 수송 재료로 사용한 유기 전계 발광 소자
KR20110106192A (ko) 축합 아릴아민계 화합물 및 이를 포함하는 유기전계발광소자
KR20150010579A (ko) 유기 일렉트로루미네센스 소자용 재료 및 이를 사용한 유기 일렉트로루미네센스 소자
CN112961134A (zh) 一种有机发光辅助层材料及其制备方法和应用、有机电致发光器件
CN111423386A (zh) 一种新型有机材料及其应用
CN108084038B (zh) 一种有机发光化合物及其制备方法和电致发光器件
KR102209258B1 (ko) 유기 전계 발광 소자용 정공 수송 재료 및 이를 사용한 유기 전계 발광 소자
CN107827879B (zh) 一种可用于柔性显示的材料及其制备方法和有机电致发光器件
CN114874192A (zh) 一种有机电致发光材料及其在有机电致发光器件中的应用
KR20150114658A (ko) 유기발광 화합물 및 이를 포함하는 유기전계발광소자
JP5163853B2 (ja) 有機化合物およびその用途
CN113248519A (zh) 一种有机化合物及使用该化合物的有机发光器件
US20150021574A1 (en) Material for an organic electroluminescence device and organic electroluminescence device using the same
CN111303012A (zh) 一种茚并荧蒽化合物及应用

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