CN115010619A - 一种有机发光材料及其应用 - Google Patents

一种有机发光材料及其应用 Download PDF

Info

Publication number
CN115010619A
CN115010619A CN202210624884.2A CN202210624884A CN115010619A CN 115010619 A CN115010619 A CN 115010619A CN 202210624884 A CN202210624884 A CN 202210624884A CN 115010619 A CN115010619 A CN 115010619A
Authority
CN
China
Prior art keywords
organic light
emitting material
luminescent material
organic
organic luminescent
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
CN202210624884.2A
Other languages
English (en)
Inventor
赖文勇
闫宇
李祥春
王倩
李玉生
黄维
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.)
Nanjing University of Posts and Telecommunications
Original Assignee
Nanjing University of Posts and Telecommunications
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 Nanjing University of Posts and Telecommunications filed Critical Nanjing University of Posts and Telecommunications
Priority to CN202210624884.2A priority Critical patent/CN115010619A/zh
Publication of CN115010619A publication Critical patent/CN115010619A/zh
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C233/65—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C233/66—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by halogen atoms or by nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C233/67—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
    • C07C233/75—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by 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
    • C07C255/60—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 at least one of the singly-bound nitrogen atoms being acylated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/15—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C311/21—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the sulfonamide groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
    • C07D219/02—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems with only hydrogen, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
    • C07D219/04—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems 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
    • C07D219/06—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
    • C07D265/34—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings
    • C07D265/38—[b, e]-condensed with two six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
    • C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
    • C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
    • C07D279/18—[b, e]-condensed with two six-membered rings
    • C07D279/22—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom
    • C07D279/30—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom with acyl radicals attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
    • C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
    • C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
    • C07D279/18—[b, e]-condensed with two six-membered rings
    • C07D279/32—[b, e]-condensed with two six-membered rings with hetero atoms directly attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
    • C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
    • C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
    • C07D279/18—[b, e]-condensed with two six-membered rings
    • C07D279/34—[b, e]-condensed with two six-membered rings with hetero atoms directly attached to the ring sulfur atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/46—Phosphinous acids [R2POH], [R2P(= O)H]: Thiophosphinous acids including[R2PSH]; [R2P(=S)H]; Aminophosphines [R2PNH2]; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/5036—Phosphines containing the structure -C(=X)-P or NC-P
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
    • C07F9/5337—Phosphine oxides or thioxides containing the structure -C(=X)-P(=X) or NC-P(=X) (X = O, S, Se)
    • 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
    • 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
    • C09K2211/1025—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
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
    • 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
    • C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

本发明公开了一种有机发光材料及其应用，所述有机发光材料的结构通式如式I所示，
Figure 923489DEST_PATH_IMAGE001
式I，其中，A选自碳基、砜基中的一种；Ar选自取代或未取代的C6~C40的芳胺基、取代或未取代的C6~C40的芳膦基中的一种；D选自碳原子或氮原子中的一种；E选自氢原子或‑A‑Ar中的一种；本发明同时公开了该有机发光材料的制备方法，所得的材料纯化工艺简单，反应过程容易控制，成本低廉；本发明公开该有机发光材料具有动态发射的特点，可广泛应用于信息加密技术、多彩图案化产品、可视化检测技术、生物成像技术、有机电致发光器件等领域。

Description

一种有机发光材料及其应用
技术领域
本发明属于光电材料技术领域，具体涉及一种有机发光材料及其应用。
背景技术
具有动态响应的有机发光材料在外部刺激后，其发射颜色、强度等发生变化。这样的动态响应的特性使其在信息加密、多彩图案化、可视化检测、生物成像、有机电致发光等领域存在着丰富的应用价值。然而，大多具有动态响应的有机发光材料涉及对如光致变色化合物的改性，例如激发态质子转移类化合物、偶氮化合物、芳基乙烯类衍生物、螺吡喃类化合物等，难以避免复杂的制备方法及高昂的制备成本(e.g.Nat.Nanotechnol.2019,14,347；Adv.Funct.Mater.2019,30,1907507)。另一方面，具有动态响应的有机动态发光通过主-客体能量传递途径(e.g.Angew.Chem.Int.Ed.2020,59,16054.)实现，但存在调控复杂、需要精确的能级匹配以及相分离等缺陷。
近年来，有机发光材料的研究取得了跨越式发展，涵盖了荧光、磷光、热致延迟荧光等多种发光机制，并广泛应用于有机发光二极管(OLED)、有机发光晶体管(OLET)等领域。但根据卡莎规则，发射的波长由最低激发态决定，表现为单一固定的发射。因此，开发具有动态响应的有机发光材料是一项兼具挑战性与吸引性的工作。
发明内容
解决的技术问题：针对现有技术存在的不足，本发明提供一种有机发光材料及其应用，能有效解决上述制备成本高、调控复杂、需要精确的能级匹配以及相分离等技术问题。
技术方案：第一方面，本发明提供了一种有机发光材料，所述有机发光材料的结构通式如下式I所示：
Figure BDA0003676659910000011
其中，A选自羰基、砜基中的任意一种；Ar选自取代或未取代的C6～C40的芳胺基、取代或未取代的C6～C40的芳膦基中的一种；D选自C或N中的任意一种；E选自H或-A-Ar中的任意一种。
优选的，所述Ar选自以下化学结构中的一种：
Figure BDA0003676659910000021
其中，
Figure BDA0003676659910000022
表示基团的连接位点；
R1～R6各自独立地选自氢原子、卤素、氰基、C1～C30的直链或支链烷基、C1～C30的烷氧基或C6～C30的芳香基中的一种；
R选自C1～C30的直链或支链烷基、C1～C30的直链或支链烷氧基，或C6～C30的芳香基中的一种；
a、b、e、f、h各自独立地选自0～5的整数，c、d各自独立地选自0～4的整数，g、i、j各自独立地选自0～7的整数；
X选自氮原子、磷原子、磷氧双键中的一种；
Y选自氧原子、硫原子、羰基、亚砜基、砜基中的一种；
Z选自碳原子、硅原子中的一种。
优选的，所述Ar选自以下化学结构中的一种：
Figure BDA0003676659910000023
Figure BDA0003676659910000031
优选的，所述发光材料为如下所示化学结构中的任意一种：
Figure BDA0003676659910000032
Figure BDA0003676659910000041
Figure BDA0003676659910000051
Figure BDA0003676659910000061
第二方面，本发明提供了一种第一方面所述的有机发光材料的制备方法，包括以下步骤：
(1)在氮气保护及干燥无水的条件下，在反应瓶中加入任意一种Ar基团对应的原料与碱及甲苯溶剂，在80～120℃下搅拌20～30分钟；
所述的碱为氢化钠、叔丁醇钠、碳酸钠、碳酸氢钠、三乙胺中的一种；Ar基团对应的原料与碱的摩尔比为1:1～1:4，每毫摩尔的Ar基团对应的原料加入甲苯2～8mL；
(2)向步骤(1)的反应物中，加入间苯二甲酰氯、1,3,5-均三苯甲酰氯、2,6-吡啶二甲酰氯或苯-1,3-二磺酰氯中的一种，继续反应8～12小时，反应结束后冷却至室温，调节pH值至中性；
所述间苯二甲酰氯、1,3,5-均三苯甲酰氯、2,6-吡啶二甲酰氯或苯-1,3-二磺酰氯与Ar基团对应的原料的摩尔比分别为1:1～1:2、1:1.5～1:3、1:1～1:2、1:1～1:2；
(3)用二氯甲烷与饱和食盐水萃取，用无水硫酸钠干燥，去除有机相溶剂，随后，以石油醚和二氯甲烷作为洗脱剂进行柱层析纯化，重结晶，得到相应化合物；
所述石油醚与二氯甲烷洗脱剂的体积比为1:1～1:4，柱层析所用硅胶目数为100～200目或200～300目。
第三方面，本发明提供了一种第一方面所述的有机发光材料的单晶培育方法，具体为：
采用良溶剂-不良溶剂挥发的方法，选择的良溶剂为甲苯、二氯甲烷、氯仿、四氢呋喃或乙酸乙酯中的一种，选择的不良溶剂为甲醇、乙醇、正己烷或石油醚中的一种，所述的良溶剂-不良溶剂的体积比为1:0.5～1:2。
第四方面，本发明提供了一种有机发光材料的应用，包括以下方面：
所述有机发光材料应用于信息加密技术、多彩图案化产品、可视化检测技术时，将该有机动态发光材料均匀分散在聚乙烯醇或芦荟胶等功能助剂介质中，以丝网印刷方式在滤纸或其他纸张上制备出相应的信息、图案等。
有益效果：本发明有机发光材料具有动态响应的发射特点：在溶液态下，随浓度增加，产生激基缔合物发射；在晶态粉末及单晶态下具有激发依赖和力致生色的性质，其中晶态粉末态，在可见光范围，具有随激发波长增加，主要发射峰蓝移的性质；单晶态具有“荧光-延迟荧光-室温磷光”多重发射的性质，且在不同的激发波长下，各个位置的发射峰强度的相对比例发生变化。这样的动态发光性质可用于信息加密技术、多彩图案化产品、可视化检测技术、生物成像技术和有机电致发光器件等领域。
附图说明
图1为实施例1有机发光材料DDOP(1,3-phenylenebis((9,9-dimethylacridin-10(9H)-yl)methanone))的1H NMR谱图；
图2为实施例1不同含量的有机发光材料DDOP在四氢呋喃溶液中的发射光谱图；
图3为实施例2有机发光材料DDOP的晶态粉末在不同波长处的发射光谱图；
图4为实施例2有机发光材料DDOP的晶态粉末研磨前后发射光谱图；
图5为实施例3有机发光材料DDOP用二氯甲烷/甲醇溶剂生长出的单晶在不同波长处的发射光谱图；
图6为实施例3有机发光材料DDOP用二氯甲烷/甲醇溶剂生长出的单晶在不同波长处的激发态寿命衰减图。
具体实施方式
本发明一种有机发光材料，其结构通式如式I所示，
Figure BDA0003676659910000081
在苯环的间位或吡啶环的2,6位引入2-3个酰化或磺酰化的Ar基生色团，
其中，A选自羰基、砜基中的任意一种；Ar为具有非平面扭曲结构的给电子基团，选自芳胺基、取代或未取代的C6～C40的芳膦基中的任意一种，具体可选择但不限于二苯胺/二苯膦及其衍生物、吩噻嗪/吩噁嗪/吖啶/吖啶酮及其衍生物；D选自碳原子或氮原子中的任意一种；E选自氢原子或-A-Ar中的任意一种。以下通过若干具体实施例对本发明做进一步说明，但实施例不限制本发明的涵盖范围。
实施例提供的一种有机发光材料是如下所示的化学结构中的任意一种：
Figure BDA0003676659910000082
Figure BDA0003676659910000091
Figure BDA0003676659910000101
Figure BDA0003676659910000111
实施例1
有机发光材料DDOP(1,3-phenylenebis((9,9-dimethylacridin-10(9H)-yl)methanone))的合成反应式，及其溶液态光物理性能：
Figure BDA0003676659910000121
在反应瓶中加入9,10-二氢-9,9-二甲基吖啶(1.05g，5mmol)与碳酸钠(1.38g，10mmol)，抽换氮气，注入20mL重蒸及鼓泡后的甲苯溶剂，在90℃下搅拌20分钟。随后向上述反应物中，加入间苯二甲酰氯(1.02g，5mmol)，继续反应8小时。反应结束后冷却至室温，调节pH值至中性，用二氯甲烷与饱和食盐水萃取，用无水硫酸钠干燥，去除有机相溶剂。然后，以体积比为1:2的石油醚和二氯甲烷作为洗脱剂进行柱层析纯化，硅胶目数为100～200目。接着用二氯甲烷和甲醇进行重结晶，得到黄色的目标产物(1.20g,产率45％)。如图1所示，经鉴证，1H NMR(400MHz,CDCl3)δ7.68(d,1H),7.47-7.52(d,4H),7.38-7.43(d,4H),7.30(d,1H),7.27(d,1H),7.18-7.25(m,3H),7.06-7.17(m,5H)；13C NMR(100MHz,CDCl3)δ166.45,138.71,136.21,130.13,129.81,127.08,126.03,125.80,125.62,123.56,38.16,26.67；MALDI-TOF-MS(m/z):calcd.For C38H32N2O2,Molecular Weight:548.69。在溶液态下，随浓度增加，产生激基缔合物发射，可由图2有机发光材料DDOP的在四氢呋喃溶液中的发射光谱图证实。
实施例2
有机发光材料DDOP晶态粉末用于信息加密及多彩显示图案的制备及其晶态粉末的光物理性能：
将200mg DDOP粉末均匀分散在300mg市售芦荟胶中，搅动至混合均匀成胶状。通过丝网印刷技术在市售滤纸上印刷有机动态发光材料DDOP，其中丝网印刷模板预先设定信息及图案。由手提紫外灯照射，在254nm紫外灯照射下，可以识别出正常光下无法识别的黄绿色信息；而在254nm紫外灯照射下，可以识别出正常光下无法识别的黄蓝色信息。在320～360nm的紫外激发源照射下，印刷的图案呈现不同颜色的显示。其不同颜色的显示，说明晶态粉末具有激发依赖和力致生色的性质，均可由图3-图4在不同激发波长下和不同聚集状态下的发射光谱证实。
实施例3
有机发光材料DDOP的单晶培育及其单晶的光物理性能：
将50mg DDOP产物溶解在12mL二氯甲烷良溶剂中，再加入6mL甲醇不良溶剂，使混合溶液缓慢蒸发。最后，在溶液中形成黄色透明的块状晶体。单晶为单斜晶系，空间群为C2/c，晶胞参数为
Figure BDA0003676659910000131
Figure BDA0003676659910000132
α＝90°,β＝120.370(3)°,γ＝90°；Z＝8。其单晶的光物理性能不同于晶态粉末，具有“荧光-延迟荧光-室温磷光”多重发射的性质，可由图5-图6有机发光材料DDOP用二氯甲烷/甲醇溶剂生长出的单晶的发射光谱图和激发态寿命衰减图证实。
实施例4
有机发光材料TDOP(benzene-1,3,5-triyltris((9,9-dimethylacridin-10(9H)-yl)methanone))的合成反应式：
Figure BDA0003676659910000133
本实施例与实施例1制备方法基本相同，不同之处在于反应温度为100℃，反应时间为10h，碱选用叔丁醇钠，选择9,10-二氢-9,9-二甲基吖啶作为原料，且原料与1,3,5-均三苯甲酰氯的摩尔比为3:1。MALDI-TOF-MS(m/z):calcd.For C54H45N3O3,MolecularWeight:783.97。
实施例5
有机发光材料DDOPy(benzene-1,3,5-triyltris((9,9-dimethylacridin-10(9H)-yl)methanone))的合成反应式：
Figure BDA0003676659910000134
本实施例与实施例1制备方法基本相同，不同之处在于反应温度为120℃，反应时间为12h，碱选用氢化钠，选择9,10-二氢-9,9-二甲基吖啶作为原料，且原料与2,6-吡啶二甲酰氯的摩尔比为1:1。MALDI-TOF-MS(m/z):calcd.For C37H31N3O2,Molecular Weight:549.67。
实施例6
有机发光材料DDSOP(1,3-bis((9,9-dimethylacridin-10(9H)-yl)sulfonyl)benzene)的合成反应式：
Figure BDA0003676659910000141
本实施例与实施例1制备方法基本相同，不同之处在于反应温度为100℃，反应时间为12h，碱选用碳酸氢钠，选择9,10-二氢-9,9-二甲基吖啶作为原料，且原料与苯-1,3-二磺酰氯的摩尔比为1:1。MALDI-TOF-MS(m/z):calcd.For C36H32N2O4S2,Molecular Weight:620.78。
实施例7
有机发光材料DPOP(1,3-phenylenebis((10H-phenothiazin-10-yl)methanone))的合成反应式：
Figure BDA0003676659910000142
本实施例与实施例1制备方法基本相同，不同之处在于反应温度为80℃，反应时间为10h，碱选用三乙胺，选择吩噻嗪作为原料，且原料与间苯二甲酰氯的摩尔比为2:1。MALDI-TOF-MS(m/z):calcd.For C32H20N2O2S2,Molecular Weight:528.64。
实施例8
有机动态发光材
DPOPO(1,3-phenylenebis((5,5-dioxido-10H-phenothiazin-10-yl)methanone))的合成反应式：
Figure BDA0003676659910000151
本实施例与实施例1制备方法基本相同，不同之处在于反应温度为110℃，反应时间为10h，碱选用三乙胺，选择10H-phenothiazine 5,5-dioxide作为原料，且原料与间苯二甲酰氯的摩尔比为2:1。MALDI-TOF-MS(m/z),Molecular Weight:592.64。
实施例9
有机发光材料DDOSOP(1,3-bis((9,9-dimethylacridin-10(9H)-yl)sulfonyl)benzene)的合成反应式：
Figure BDA0003676659910000152
本实施例与实施例1制备方法基本相同，不同之处在于反应温度为95℃，反应时间为11h，碱选用碳酸钠，选择吖啶-9-(10H)-酮作为原料，且原料与苯-1,3-二磺酰氯的摩尔比为2:1。MALDI-TOF-MS(m/z),Molecular Weight:592.64。
实施例10
有机动态发光材料DDPOP(1,3-phenylenebis((9,9-diphenylacridin-10(9H)-yl)methanone))的合成反应式：
Figure BDA0003676659910000153
本实施例与实施例1制备方法基本相同，不同之处在于反应温度为105℃，反应时间为12h，碱选用氢化钠，选择9,9-二苯基-9,10-二氢吖啶作为原料，且原料与间苯二甲酰氯的摩尔比为2:1。MALDI-TOF-MS(m/z),Molecular Weight:796.97。
实施例11
有机发光材料1,3-phenylenebis((diphenylphosphaneyl)methanone)的合成反应式：
Figure BDA0003676659910000161
本实施例与实施例1制备方法基本相同，不同之处在于反应温度为115℃，反应时间为11h，碱选用氢化钠，选择二苯膦作为原料，且原料与间苯二甲酰氯的摩尔比为2:1。MALDI-TOF-MS(m/z),Molecular Weight:502.49。
实施例12
有机发光材料benzene-1,3,5-triyltris((diphenylphosphoryl)methanone)的合成反应式：
Figure BDA0003676659910000162
本实施例与实施例1制备方法基本相同，不同之处在于反应温度为110℃，反应时间为12h，碱选用氢化钠，选择二苯基氧化膦作为原料，且原料与1,3,5-均三苯二甲酰氯的摩尔比为3:1。MALDI-TOF-MS(m/z),Molecular Weight:762.67。

Claims (5)

1.一种有机发光材料，其特征在于，所述有机发光材料的结构通式如下式I所示：
Figure FDA0003676659900000011
其中，A选自羰基、砜基中的任意一种；Ar选自取代或未取代的C6～C40的芳胺基、取代或未取代的C6～C40的芳膦基中的一种；D选自碳原子或氮原子中的任意一种；E选自氢原子或-A-Ar中的任意一种。
2.根据权利要求1所述的一种有机发光材料，其特征在于，所述Ar选自以下化学结构中的一种：
Figure FDA0003676659900000012
其中，
Figure FDA0003676659900000013
表示基团的连接位点；
R1～R6各自独立地选自氢原子、卤素、氰基、C1～C30的直链或支链烷基、C1～C30的烷氧基或C6～C30的芳香基中的一种；
R选自C1～C30的直链或支链烷基、C1～C30的直链或支链烷氧基，或C6～C30的芳香基中的一种；
a、b、e、f、h各自独立地选自0～5的整数，c、d各自独立地选自0～4的整数，g、i、j各自独立地选自0～7的整数；
X选自氮原子、磷原子、磷氧双键中的一种；
Y选自氧原子、硫原子、羰基、亚砜基、砜基中的一种；
Z选自碳原子、硅原子中的一种。
3.根据权利要求1或2所述的一种有机发光材料，其特征在于，所述Ar选自以下化学结构中的一种：
Figure FDA0003676659900000021
4.根据权利要求1所述的一种有机发光材料，其特征在于，所述发光材料为如下所示化学结构中的任意一种：
Figure FDA0003676659900000022
Figure FDA0003676659900000031
Figure FDA0003676659900000041
Figure FDA0003676659900000051
5.一种如权利要求1-4任一项所述的有机发光材料在信息加密技术、多彩图案化产品、可视化检测技术、生物成像技术及有机电致发光器件中的应用。
CN202210624884.2A 2022-06-02 2022-06-02 一种有机发光材料及其应用 Pending CN115010619A (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210624884.2A CN115010619A (zh) 2022-06-02 2022-06-02 一种有机发光材料及其应用

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210624884.2A CN115010619A (zh) 2022-06-02 2022-06-02 一种有机发光材料及其应用

Publications (1)

Publication Number Publication Date
CN115010619A true CN115010619A (zh) 2022-09-06

Family

ID=83073914

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210624884.2A Pending CN115010619A (zh) 2022-06-02 2022-06-02 一种有机发光材料及其应用

Country Status (1)

Country Link
CN (1) CN115010619A (zh)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62174188A (ja) * 1986-01-29 1987-07-30 Ricoh Co Ltd 多色感熱記録材料
JPH0912548A (ja) * 1995-06-26 1997-01-14 Sumitomo Electric Ind Ltd アモルファス分子材料
US20070259134A1 (en) * 2006-05-02 2007-11-08 Fujifilm Corporation Cellulose Compound Film, Optical Compensation Sheet, Polarizing Plate, and Liquid Crystal Display Device
CN102329271A (zh) * 2010-07-12 2012-01-25 佛山阿格蕾雅光电材料有限公司 高效合成1，3，5-三（n-苯基苯并咪唑基）苯的方法
CN104380842A (zh) * 2012-05-31 2015-02-25 保土谷化学工业株式会社 有机电致发光器件
CN110746327A (zh) * 2018-07-24 2020-02-04 天津大学 一种偶氮苯—石墨烯复合材料及其在变色加密保密中的应用

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62174188A (ja) * 1986-01-29 1987-07-30 Ricoh Co Ltd 多色感熱記録材料
JPH0912548A (ja) * 1995-06-26 1997-01-14 Sumitomo Electric Ind Ltd アモルファス分子材料
US20070259134A1 (en) * 2006-05-02 2007-11-08 Fujifilm Corporation Cellulose Compound Film, Optical Compensation Sheet, Polarizing Plate, and Liquid Crystal Display Device
CN102329271A (zh) * 2010-07-12 2012-01-25 佛山阿格蕾雅光电材料有限公司 高效合成1，3，5-三（n-苯基苯并咪唑基）苯的方法
CN104380842A (zh) * 2012-05-31 2015-02-25 保土谷化学工业株式会社 有机电致发光器件
CN110746327A (zh) * 2018-07-24 2020-02-04 天津大学 一种偶氮苯—石墨烯复合材料及其在变色加密保密中的应用

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Registry[Online]", COLUMBUS, OHIO, US, pages 299417 - 61 *
KUNIO IKEMURA, ET AL.: "UV-VIS spectra and photoinitiation behaviors of acylphosphine oxide and bisacylphosphine oxide derivatives in unfilled, light-cured dental resins", 《DENTAL MATERIALS JOURNAL》, vol. 27, no. 6, pages 765, XP055467937, DOI: 10.4012/dmj.27.765 *
RONGRONG YU, ET AL.: "Differentially Substituted Phosphines via Decarbonylation of Acylphosphines", 《ORG. LETT.》, vol. 19, pages 1808 - 1811 *

Similar Documents

Publication Publication Date Title
KR100946409B1 (ko) 신규한 유기 발광 화합물 및 이를 발광재료로서 채용하고있는 유기 전계 발광 소자
Chen et al. Dimethylamine substituted bisbenzocoumarins: solvatochromic, mechanochromic and acidochromic properties
CN110128453B (zh) 基于三苯胺和稀土配合物的白色有机电致发光材料制备方法及应用
TWI553003B (zh) 2,6 -雙[3’-(n-咔唑基)苯基] 吡啶類化合物的合成方法
CN113980054B (zh) 一种含膦氧化合物及其制备和应用
CN113402561B (zh) 一种基于螺芴结构的高色纯度铂(ii)配合物发光材料及其应用
CN108558953A (zh) 一种含金属的有机络合物及其有机发光器件
CN115010619A (zh) 一种有机发光材料及其应用
KR100389517B1 (ko) 신규한 적색 형광물질, 이의 제조방법 및 이를 포함하는유기전기발광소자
CN112175607B (zh) 有机室温磷光材料及其制备方法和应用
CN113214155B (zh) 一种长寿命的纯有机室温磷光材料及其制备方法与应用
KR100717696B1 (ko) 유기 전계발광 소자
WO2018120969A1 (zh) 含有香豆素类绿光染料的光转换膜
CN111995637B (zh) 一种有机化合物及其有机电致发光器件
CN105085579B (zh) N‑己基咔唑取代苯基苯并噻唑铱(iii)配合物及其制备
CN113583056A (zh) 基于螺芴-螺芴结构的6/5/6四齿环金属铂或钯配合物的发光材料及其应用
CN107400085A (zh) 一种芳香族胺类稠环化合物及其有机发光器件
CN109824557B (zh) 一种同质多晶的四苯乙烯荧光染料及其制备
CN108558766B (zh) 化合物、其制备方法、化合物晶体和有机电致发光器件
CN113308129B (zh) 同质多晶的对称二四苯乙烯荧光化合物制备方法及其晶体
CN108640950A (zh) 一种铱金属有机配合物及其有机发光器件
CN113735815B (zh) 基于蒽衍生物的激基缔合物发光材料及其制备方法和应用
CN112940035B (zh) 一种有机超长室温磷光材料及其制备方法和应用
CN115583941B (zh) 一类含三氮唑的蒽基蓝光有机半导体材料及其制备方法与应用
CN113501833B (zh) 一种能够发射白光的化合物及其制备方法

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