CN108164462A - 一类用作发光材料的含氮杂环化合物及应用 - Google Patents

一类用作发光材料的含氮杂环化合物及应用 Download PDF

Info

Publication number
CN108164462A
CN108164462A CN201810125434.2A CN201810125434A CN108164462A CN 108164462 A CN108164462 A CN 108164462A CN 201810125434 A CN201810125434 A CN 201810125434A CN 108164462 A CN108164462 A CN 108164462A
Authority
CN
China
Prior art keywords
layer
nitrogen
luminescent material
naphthalene
wavelength
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.)
Pending
Application number
CN201810125434.2A
Other languages
English (en)
Inventor
吴建德
丰佩川
胡灵峰
张国选
杨阳
王磊
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.)
YANTAI XIANHUA CHEM-TECH Co Ltd
Original Assignee
YANTAI XIANHUA CHEM-TECH 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 YANTAI XIANHUA CHEM-TECH Co Ltd filed Critical YANTAI XIANHUA CHEM-TECH Co Ltd
Priority to CN201810125434.2A priority Critical patent/CN108164462A/zh
Publication of CN108164462A publication Critical patent/CN108164462A/zh
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
    • C07D221/06—Ring systems of three rings
    • C07D221/08—Aza-anthracenes
    • 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
    • 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
    • C07D405/04—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 directly linked by a ring-member-to-ring-member bond
    • 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
    • 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
    • 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
    • C07D409/10—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 carbon chain containing aromatic rings
    • 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
    • H10K85/626—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
    • 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
    • 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
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • 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
    • C09K2211/1018—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
    • C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
    • 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
    • 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
    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

本发明属于有机光电材料技术领域，尤其涉及一类用作发光材料的含氮杂环化合物及应用。本发明制得的含氮杂环作为主体发光材料不仅发光效率高，而且发射光的波长可在范围内调节，其最大发光波长可为410‑530nm。此类材料具有相近的骨架结构，HOMO‑LUMO能皆高,能将能量传递給客体发光体材料，从而实现发射光波长从蓝色光到绿色光范围的调节，特别适用在显示器装置中，可以提高发光效率，降低驱动电压。此外，主体发光材料的制备方法基本相同，操作简单。

Description

一类用作发光材料的含氮杂环化合物及应用
技术领域
本发明属于有机光电材料技术领域，尤其涉及一类用作发光材料的含氮杂环化合物及应用。
背景技术
有机发光二极管(英文名Organic Light Emitting Diode，简称OLED)是一种由有机材料薄膜组成的固态器件，施加电压后能够发光。相比于传统的发光二极管(LED)和液晶显示(LCD)，OLED具有自发光、清晰亮丽、轻薄、响应速度快、视角宽、低功耗、适用温度范围大、制造工艺简单等特点。OLED可做成像壁纸般随处折、卷、贴、挂的梦幻显示器，有望将取代液晶显示，被誉为“终极显示技术”。此外，OLED作为平面光源，无论是在结构上还是在光源质量、产品特色等方面都具有传统LED照明无法企及的优势。
发明内容
本发明针对上述现有技术存在的不足，提供一类用作发光材料的含氮杂环化合物及应用。
本发明解决上述技术问题的技术方案如下：一类用作发光材料的含氮杂环化合物，其结构式如下：
其中，R1、R3、R4、R6、R7、R8、R9各自独立地为氢、烷基、硅烷基、卤素、CN、SCN、NO2、CF3或芳香基团；X为C、N或B；
R5、R10各自独立地为氢、氘、烷基、环烷基、羟基、氨基、巯基、烯基、炔基、芳基、杂芳基、烷氧基、芳氧基、胺基、硅烷基、卤素、CN、SCN、NO2、CF3、＝、
优选地，上述含氮杂环化合物，其结构式分别为：
本发明的第二个目的在于提供上述含氮杂环化合物作为电致发光材料，在有机电致发光器件中的应用。
本发明的有益效果是：本发明制得的含氮杂环作为主体发光材料不仅发光效率高，而且发射光的波长可在范围内调节，其最大发光波长可为410-530nm。此类材料具有相近的骨架结构，HOMO-LUMO能皆高,能将能量传递給客体发光体材料，从而实现发射光波长从蓝色光到绿色光范围的调节，特别适用在显示器装置中，可以提高发光效率，降低驱动电压。此外，主体发光材料的制备方法基本相同，操作简单。
附图说明
图1为有机电致发光器件的结构示意图；
图2为应用例1的发光光谱分析图；
图3为应用例2的发光光谱分析图；
图4为应用例3的发光光谱分析图；
图5为应用例4的发光光谱分析图；
图6为应用例5的发光光谱分析图；
图7为应用例6的发光光谱分析图；
图中，1、玻璃衬底；2、阳极层；3、空穴注入层；4、空穴传输层；5、发光层；6、电子传输层；7、电子注入层；8、阴极层。
具体实施方式
以下对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。
本发明实施例中使用的各原料结构式如下：
实施例1
化合物(1)的合成，反应方程式如下：(1)合成中间体A1
(2)合成中间体A2
(3)合成中间体A3
(4)制备化合物(1)
具体制备方法如下：
(1)将3,9-二甲基苯并[G]喹啉(MW:207.2)20.72g(0.1mol)、N-溴代琥珀酰亚胺(MW:177.98)18.7g(0.105mol)、DMF(N,N-二甲基甲酰胺)(MW:73.09)360mL、过氧化二苯甲酰(MW:242.23)0.84g(0.0035mol)置于500mL反应瓶中,***冷凝管和温度计，搅拌反应,升温到100℃,反应12h,反应结束后降温,加入140ml乙醇,再过滤、水洗、烘干,得到10-溴-3,9,-二甲基苯并[G]喹啉(A1)(MW:285.02)26.22g，收率92％；
(2)取1-萘硼酸(MW:172)17.2g(0.1mol)、步骤(1)的10-溴-3,9,-二甲基苯并[G]喹啉(A1)(MW:285.02)26.22g(0.092mol)、Pd(PPh3)4(四(三苯基膦)钯)(MW:1155.58)1.06g、碳酸钠(MW:106)11.67g、甲苯250mL、乙醇60mL和水60mL置于500mL反应瓶中,***冷凝管、温度计，搅拌反应,升溫到65℃,反应18h,反应结束后降温,加入130mL乙醇,再过滤、水洗、烘干,得到3,9,-二甲基-10-(萘-1-基)苯并[G]喹啉(MW:333.43)27.6g，收率90％；
(3)将步骤(2)的3,9,-二甲基-10-(萘-1-基)苯并[G]喹啉(MW:333.43)27.34g(0.082mol)、N-溴代琥珀酰亚胺(MW:177.98)15.43g(0.086mol)、DMF(N,N-二甲基甲酰胺)(MW:73.09)300mL、过氧化二苯甲酰(MW:242.23)0.7g(0.0029mol)置于500mL反应瓶中,***冷凝管、温度计，搅拌反应,升温到100℃,反应12h,反应结束后降温,加入150mL乙醇,再过滤、水洗、烘干,得到5-溴-3,9,-二甲基-10-(萘-1-基)苯并[G]喹啉(MW:412.33)32.16g(0.078mol)，收率95％；
(4)将步骤(3)的5-溴-3,9,-二甲基-10-(萘-1-基)苯并[G]喹啉(MW:412.33)32.16g(0.078mol)、(4-(1-萘)苯基)硼酸(MW:248.1)21.3g(0.086mol)、Pd(PPh3)4(四(三苯基膦)钯)(MW:1155.58)0.9g、碳酸钠(MW:106)9.92g、甲苯250mL、乙醇50mL、水50mL置于500mL反应瓶中,***冷凝管、温度计，搅拌反应,升温到65℃,反应18h,待反应结束后降温,加入150mL乙醇,再过滤、水洗、烘干,得到3,9,-二甲基-10-(萘-1-基)5-(4(萘-1-基)苯)苯并[G]喹啉(MW:535.69)36.76g(0.06864mol)，即为化合物(1)，收率88％。
实施例2
化合物(8)的合成，反应方程式如下：
具体制备方法如下：
步骤(1)(2)(3)与实施例1的制备方法相同，区别在于步骤(4)：
将步骤(3)的5-溴-3,9,-二甲基-10-(萘-1-基)苯并[G]喹啉(MW:412.33)32.16g(0.078mol)、4-(萘-2-基)苯基)硼酸(MW:248.1)21.3g(0.086mol)、Pd(PPh3)4(四(三苯基膦)钯)(MW:1155.58)0.9g、碳酸钠(MW:106)9.92g、甲苯250mL、乙醇50mL、水50mL置于500mL反应瓶中,***冷凝管、温度计，搅拌反应,升温到65℃,反应18h,待反应结束后降温,加入150mL乙醇,再过滤、水洗、烘干,得到3,9,-二甲基-10-(萘-1-基)5-(4(萘-2-基)苯)苯并[G]喹啉(MW:535.69)36.76g(0.06864mol)，即为化合物(8)，收率88％。
实施例3
化合物(57)的合成，反应方程式如下：
具体制备方法如下：
步骤(1)(2)(3)与实施例1的制备方法相同，区别在于步骤(4)：
将步骤(3)的5-溴-3,9,-二甲基-10-(萘-1-基)苯并[G]喹啉(MW:412.33)32.16g(0.078mol)、萘并(2,3-b)苯并呋喃-2-基硼酸(MW:262.08)22.53g(0.086mol)、Pd(PPh3)4(四(三苯基膦)钯)(MW:1155.58)0.9g、碳酸钠(MW:106)9.92g、甲苯250mL、乙醇50mL、水50mL置于500mL反应瓶中,***冷凝管、温度计，搅拌反应,升温到65℃,反应18h,待反应结束后降温,加入150mL乙醇,再过滤、水洗、烘干,得到3,9-二甲基-10-(萘-1基)-5-(萘并〔2,3-b〕苯并呋喃-2-基)苯并[G]喹啉(MW:549.21)36.84g(0.067mol)，即为化合物(57)，收率86％。
实施例4
化合物(1a)的合成，反应方程式如下：(1)合成中间体A1a
(2)合成中间体A2a
(3)合成中间体A3a
(4)制备化合物(1a)
具体制备方法如下：
(1)将苯并[G]喹啉(MW:179)17.9g(0.1mol)、N-溴代琥珀酰亚胺(MW:177.98)18.7g(0.105mol)、DMF(N,N-二甲基甲酰胺)(MW:73.09)360mL、过氧化二苯甲酰(MW:242.23)0.84g(0.0035mol)置于500mL反应瓶中,***冷凝管和温度计搅拌反应,升温到100℃,反应12hrs,待反应結束后降温,加入140mL乙醇,再过滤、水洗、烘干,得到10-溴苯并[G]喹啉(A1a)(MW:256.98)23.64g，收率92％；
(2)取1-萘硼酸(MW:172)17.2g(0.1mol)、步骤(1)的10-溴苯并[G]喹啉(A1a)(MW:256.98)23.6g(0.092mol)、Pd(PPh3)4(四(三苯基膦)钯)(MW:1155.58)1.06g、碳酸钠(MW:106)11.67g、甲苯250mL、乙醇60mL和水60mL置于500mL反应瓶中,***冷凝管、温度计，搅拌反应,升溫到65℃,反应18h,反应结束后降温,加入130mL乙醇,再过滤、水洗、烘干,得到10-(萘-1-基)苯并[G]喹啉(MW:304.39)25.14g，收率90％；
(3)将步骤(2)的10-(萘-1-基)苯并[G]喹啉(MW:304.39)25.14g(0.082mol)、N-溴代琥珀酰亚胺(MW:177.98)15.43g(0.086mol)、DMF(N,N-二甲基甲酰胺)(MW:73.09)300mL、过氧化二苯甲酰(MW:242.23)0.7g(0.0029mol)置于500mL反应瓶中,***冷凝管、温度计，搅拌反应,升温到100℃,反应12h,反应结束后降温,加入150mL乙醇,再过滤、水洗、烘干,得到5-溴-10-(萘-1-基)苯并[G]喹啉(MW:383.29)29.89g(0.078mol)，收率95％；
(4)将步骤(3)的5-溴-10-(萘-1-基)苯并[G]喹啉(MW:383.29)29.89g(0.078mol)、(4-(1-萘)苯基)硼酸(MW:248.1)21.3g(0.086mol)、Pd(PPh3)4(四(三苯基膦)钯)(MW:1155.58)0.9g、碳酸钠(MW:106)9.92g、甲苯250mL、乙醇50mL、水50mL置于500mL反应瓶中,***冷凝管、温度计，搅拌反应,升温到65℃,反应18h,待反应结束后降温,加入150mL乙醇,再过滤、水洗、烘干,得到10-(萘-1-基)5-(4(萘-1-基)苯)苯并[G]喹啉(MW:507.6)34.84g(0.06864mol)，即为化合物(1a)，收率88％。
实施例5
化合物(8a)的合成，反应方程式如下：
具体制备方法如下：
步骤(1)(2)(3)与实施例1的制备方法相同，区别在于步骤(4)：
将步骤(3)的5-溴-10-(萘-1-基)苯并[G]喹啉(MW:383.29)29.89g(0.078mol)、4-(萘-2-基)苯基)硼酸(MW:248.1)21.3g(0.086mol)、Pd(PPh3)4(四(三苯基膦)钯)(MW:1155.58)0.9g、碳酸钠(MW:106)9.92g、甲苯250mL、乙醇50mL、水50mL置于500mL反应瓶中,***冷凝管、温度计，搅拌反应,升温到65℃,反应18h,待反应结束后降温,加入150mL乙醇,再过滤、水洗、烘干,得到10-(萘-1-基)5-(4(萘-2-基)苯)苯并[G]喹啉(MW:507.2)34.81g(0.06864mol)，收率88％。
实施例6
化合物(57a)的合成，反应方程式如下：
具体制备方法如下：
步骤(1)(2)(3)与实施例1的制备方法相同，区别在于步骤(4)：
将步骤(3)的5-溴-10-(萘-1-基)苯并[G]喹啉(MW:383.29)29.89g(0.078mol)、萘并(2,3-b)苯并呋喃-2-基硼酸(MW:262.08)22.53g(0.086mol)、Pd(PPh3)4(四(三苯基膦)钯)(MW:1155.58)0.9g、碳酸钠(MW:106)9.92g、甲苯250mL、乙醇50mL、水50mL置于500mL反应瓶中,***冷凝管、温度计，搅拌反应,升温到65℃,反应18h,待反应结束后降温,加入150mL乙醇,再过滤、水洗、烘干,得到10-(萘-1基)-5-(萘并〔2,3-b〕苯并呋喃-2-基)苯并[G]喹啉(MW:549.21)36.84g(0.067mol)，即为化合物(57a)，收率86％。
如图1、图2所示，有机电致发光器件(OLED)的结构包括依次层叠结合的玻璃衬底1、阳极层2、空穴注入层3、空穴传输层4、发光层5、电子传输层6、电子注入层7和阴极层8。将本发明制得的发光材料应用在OLED的发光层中，表1为应用例1-3的OLED各层成分组成，表2为应用例4-6的OLED各层成分组成。
表1
表2
对照例
在玻璃底衬1上沉积一层厚度为100nm的氧化铟锡(ITO)作为透明阳极层2；在透明阳极层2上真空蒸镀厚度为10nm的NPB(N,N’-二(1-萘基)-N,N’-二苯基-1,1’-联苯-4-4’-二胺)空穴传输材料作为空穴注入层3，其中掺杂质量比3％的F4-TCNQ(2,3,5,6-四氟-7,7',8,8'-四氰二甲基对苯醌)；空穴注入层3上为一层厚度为100nm的spiro-TAD(2,2',7,7'-四(二苯基氨基)-9,9'-螺双芴)作为空穴传输层4；在空穴传输层4上真空蒸镀一层厚度为20nm蓝色荧光主体CBP(4,4'-双(9H-咔唑-9-基)联苯)作为发光层5，其中掺杂有3wt％蓝色荧光掺杂物TMTP(1,3,6,8-四间甲苯芘)；再在发光层5上依次真空蒸镀一层厚度为30nm的TPQ(2,3,5,8-四苯基喹喔啉)作为电子传输层6、厚度为1nm的LiF作为电子注入层7，最后在电子注入层7上采用真空蒸镀膜沉积技术沉积厚度为100nm的金属铝(Al)作为器件的阴极层8。
经性能测试获知，该器件的电致发光光谱的最大发光波长位于490nm，颜色为蓝色，最大外量子效率为5％。
应用例1
在玻璃底衬1上沉积一层厚度为100nm的氧化铟锡(ITO)作为透明阳极层2；在透明阳极层2上真空蒸镀厚度为10nm的NPB(N,N’-二(1-萘基)-N,N’-二苯基-1,1’-联苯-4-4’-二胺)空穴传输材料作为空穴注入层3，其中掺杂质量比3％的F4-TCNQ(2,3,5,6-四氟-7,7',8,8'-四氰二甲基对苯醌)；空穴注入层3上为一层厚度为100nm的spiro-TAD(2,2',7,7'-四(二苯基氨基)-9,9'-螺双芴)作为空穴传输层4；在空穴传输层4上真空蒸镀一层厚度为20nm蓝色荧光主体—化合物(1)作为发光层5，其中掺杂有3wt％蓝色荧光掺杂物TMTP(1,3,6,8-四间甲苯芘)；再在发光层5上依次真空蒸镀一层厚度为30nm的TPQ(2,3,5,8-四苯基喹喔啉)作为电子传输层6、厚度为1nm的LiF作为电子注入层7，最后在电子注入层7上采用真空蒸镀膜沉积技术沉积厚度为100nm的金属铝(Al)作为器件的阴极层8。
经性能测试获知，该器件的电致发光光谱的最大发光波长位于490nm，颜色为蓝色，最大外量子效率为7％。
应用例2
与应用例1相同，与应用例1不同之处在于：发光层5为厚度20nm蓝色荧光主体—化合物(8)作为发光层5，其中掺杂有3wt％蓝色荧光掺杂物(1,3,6,8-四间甲苯芘)。
经性能测试获知，该器件的电致发光光谱的最大发光波长位于490nm，颜色为藍色，最大外量子效率为8％。
应用例3
与应用例1相同，与应用例1不同之处在于：发光层5为厚度20nm蓝色荧光主体—化合物(57)作为发光层5，其中掺杂有3wt％蓝色荧光掺杂物(1,3,6,8-四间甲苯芘)。
经性能测试获知，该器件的电致发光光谱的最大发光波长位于490nm，颜色为蓝色，最大外量子效率为7％。
应用例4
与应用例1相同，与应用例1不同之处在于：发光层5为厚度20nm蓝色荧光主体—化合物(1a)作为发光层5，其中掺杂有3wt％蓝色荧光掺杂物(1,3,6,8-四间甲苯芘)。
经性能测试获知，该器件的电致发光光谱的最大发光波长位于490nm，颜色为蓝色，最大外量子效率为7％。
应用例5
与应用例1相同，与应用例1不同之处在于：发光层5为厚度20nm蓝色荧光主体—化合物(8a)作为发光层5，其中掺杂有3wt％蓝色荧光掺杂物(1,3,6,8-四间甲苯芘)。
经性能测试获知，该器件的电致发光光谱的最大发光波长位于490nm，颜色为蓝色，最大外量子效率为8％。
应用例6
与应用例1相同，与应用例1不同之处在于：发光层5为厚度20nm蓝色荧光主体—化合物(57a)作为发光层5，其中掺杂有3wt％蓝色荧光掺杂物(1,3,6,8-四间甲苯芘)。
经性能测试获知，该器件的电致发光光谱的最大发光波长位于490nm，颜色为蓝色，最大外量子效率为7％。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (3)

1.一类用作发光材料的含氮杂环化合物，其特征在于，其结构式如下：
其中，R1、R3、R4、R6、R7、R8、R9各自独立地为氢、烷基、硅烷基、卤素、CN、SCN、NO2、CF3或芳香基团；X为C、N或B；
R5、R10各自独立地为氢、氘、烷基、环烷基、羟基、氨基、巯基、烯基、炔基、芳基、杂芳基、烷氧基、芳氧基、胺基、硅烷基、卤素、CN、SCN、NO2、CF3、＝、
2.根据权利要求1所述的含氮杂环化合物，其特征在于，其结构式为：
3.一种权利要求1-2任一项所述含氮杂环化合物作为电致发光材料，在有机电致发光器件中的应用。
CN201810125434.2A 2018-02-08 2018-02-08 一类用作发光材料的含氮杂环化合物及应用 Pending CN108164462A (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810125434.2A CN108164462A (zh) 2018-02-08 2018-02-08 一类用作发光材料的含氮杂环化合物及应用

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810125434.2A CN108164462A (zh) 2018-02-08 2018-02-08 一类用作发光材料的含氮杂环化合物及应用

Publications (1)

Publication Number Publication Date
CN108164462A true CN108164462A (zh) 2018-06-15

Family

ID=62513274

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810125434.2A Pending CN108164462A (zh) 2018-02-08 2018-02-08 一类用作发光材料的含氮杂环化合物及应用

Country Status (1)

Country Link
CN (1) CN108164462A (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4015515A4 (en) * 2019-08-16 2023-08-02 LT Materials Co., Ltd. HETEROCYCLIC COMPOUND AND ORGANIC LIGHT EMITTING DEVICE THEREOF
CN116924986A (zh) * 2023-09-18 2023-10-24 山东千铄新材料有限公司 一种含氮杂环的功能层材料、制备方法及应用

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101560186A (zh) * 2008-03-28 2009-10-21 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
CN101684095A (zh) * 2008-06-24 2010-03-31 葛来西雅帝史派有限公司 新型有机电致发光化合物及使用其的有机电致发光设备
KR20100108120A (ko) * 2009-03-27 2010-10-06 덕산하이메탈(주) 벤조 이소퀴놀린 화합물 및 이를 이용한 유기전기소자, 그 단말
CN102165030A (zh) * 2007-07-13 2011-08-24 葛来西雅帝史派有限公司 有机发光材料和使用该材料的有机发光器件
CN102448945A (zh) * 2009-05-29 2012-05-09 出光兴产株式会社 蒽衍生物及使用该蒽衍生物的有机电致发光元件
CN104640848A (zh) * 2013-03-15 2015-05-20 出光兴产株式会社 蒽衍生物及使用其的有机电致发光元件
CN105085488A (zh) * 2015-06-02 2015-11-25 吉林奥来德光电材料股份有限公司 异喹啉类化合物及其制备方法、有机电致发光器件
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
US20160149139A1 (en) * 2014-11-25 2016-05-26 Universal Display Corporation Organic electroluminescent materials and devices
US9583715B2 (en) * 2013-08-09 2017-02-28 Samsung Display Co., Ltd. Anthracene-based compounds and organic light-emitting device including the same
KR20170134264A (ko) * 2016-05-27 2017-12-06 주식회사 엘지화학 유기발광소자

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102165030A (zh) * 2007-07-13 2011-08-24 葛来西雅帝史派有限公司 有机发光材料和使用该材料的有机发光器件
CN101560186A (zh) * 2008-03-28 2009-10-21 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
CN101684095A (zh) * 2008-06-24 2010-03-31 葛来西雅帝史派有限公司 新型有机电致发光化合物及使用其的有机电致发光设备
KR20100108120A (ko) * 2009-03-27 2010-10-06 덕산하이메탈(주) 벤조 이소퀴놀린 화합물 및 이를 이용한 유기전기소자, 그 단말
CN102448945A (zh) * 2009-05-29 2012-05-09 出光兴产株式会社 蒽衍生物及使用该蒽衍生物的有机电致发光元件
CN104640848A (zh) * 2013-03-15 2015-05-20 出光兴产株式会社 蒽衍生物及使用其的有机电致发光元件
US9583715B2 (en) * 2013-08-09 2017-02-28 Samsung Display Co., Ltd. Anthracene-based compounds and organic light-emitting device including the same
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
US20160149139A1 (en) * 2014-11-25 2016-05-26 Universal Display Corporation Organic electroluminescent materials and devices
CN105085488A (zh) * 2015-06-02 2015-11-25 吉林奥来德光电材料股份有限公司 异喹啉类化合物及其制备方法、有机电致发光器件
KR20170134264A (ko) * 2016-05-27 2017-12-06 주식회사 엘지화학 유기발광소자

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4015515A4 (en) * 2019-08-16 2023-08-02 LT Materials Co., Ltd. HETEROCYCLIC COMPOUND AND ORGANIC LIGHT EMITTING DEVICE THEREOF
CN116924986A (zh) * 2023-09-18 2023-10-24 山东千铄新材料有限公司 一种含氮杂环的功能层材料、制备方法及应用
CN116924986B (zh) * 2023-09-18 2024-04-09 山东千铄新材料有限公司 一种含氮杂环的功能层材料、制备方法及应用

Similar Documents

Publication Publication Date Title
Kaur et al. Luminescent metal-organic frameworks and their composites: Potential future materials for organic light emitting displays
Li et al. Dual-emissive 2-(2′-hydroxyphenyl) oxazoles for high performance organic electroluminescent devices: discovery of a new equilibrium of excited state intramolecular proton transfer with a reverse intersystem crossing process
Thejokalyani et al. Novel approaches for energy efficient solid state lighting by RGB organic light emitting diodes–A review
CN103951621B (zh) 一种蓝色有机发光二极管材料
CN102952120B (zh) 用于有机电致发光装置的化合物及使用该化合物的有机电致发光装置
CN108586507A (zh) 一种长寿命含硼有机电致发光化合物及其应用
Yang et al. High-efficiency and high-quality white organic light-emitting diode employing fluorescent emitters
CN105602553B (zh) 基于4‑氟苯乙腈的热活化型延迟荧光材料及其制备和应用
Lai et al. Carbazole–pyrene derivatives for undoped organic light-emitting devices
Tagare et al. Efficient non-doped bluish-green organic light emitting devices based on N1 functionalized star-shaped phenanthroimidazole fluorophores
Si et al. Functional versatile bipolar 3, 3′-dimethyl-9, 9′-bianthracene derivatives as an efficient host and deep-blue emitter
CN107425137B (zh) 一种高显色指数的白光oled器件
Li et al. Solution-processable, high luminance deep-blue organic light emitting devices based on novel naphthalene bridged bis-triphenylamine derivatives
Xu et al. Solution-processed multiple exciplexes via spirofluorene and S-triazine moieties for red thermally activated delayed fluorescence emissive layer OLEDs
CN108164462A (zh) 一类用作发光材料的含氮杂环化合物及应用
CN104447505A (zh) 一种稳定的有机发光二极管
TWI278503B (en) Pyrimidine containing di-fluorene oligomer for OLED
CN107973770A (zh) 一种氰基取代的螺环类延迟荧光材料的制备方法
CN103956436B (zh) 一种有机半导体空穴传输材料
CN105968100B (zh) 一种咪唑类衍生物化合物及其制备方法和发光器件
Oh et al. Triplet bipolar host materials for solution processed organic light-emitting devices
Abedi et al. Study of various evaporation rates of the mixture of Alq3: DCM in a single furnace crucible
CN108264487A (zh) 一种新颖的咪唑类化合物及其应用
CN110183302A (zh) 一种稠合三联苯化合物及其制备方法和用途
TWI289594B (en) Luminescent material of organic light-emitting diode (OLED)

Legal Events

Date Code Title Description
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20180615

RJ01 Rejection of invention patent application after publication