CN111875602B - A kind of cyano group-modified pyridoimidazole derivatives and preparation method and application thereof - Google Patents

A kind of cyano group-modified pyridoimidazole derivatives and preparation method and application thereof Download PDF

Info

Publication number
CN111875602B
CN111875602B CN202010681777.4A CN202010681777A CN111875602B CN 111875602 B CN111875602 B CN 111875602B CN 202010681777 A CN202010681777 A CN 202010681777A CN 111875602 B CN111875602 B CN 111875602B
Authority
CN
China
Prior art keywords
cyano
modified
pyridoimidazole
derivatives
derivative
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
CN202010681777.4A
Other languages
Chinese (zh)
Other versions
CN111875602A (en
Inventor
霍延平
邱志鹏
黄酬
付裕
陈文铖
籍少敏
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.)
Guangdong University of Technology
Original Assignee
Guangdong University of Technology
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 Guangdong University of Technology filed Critical Guangdong University of Technology
Priority to CN202010681777.4A priority Critical patent/CN111875602B/en
Priority to PCT/CN2020/122079 priority patent/WO2022011863A1/en
Publication of CN111875602A publication Critical patent/CN111875602A/en
Application granted granted Critical
Publication of CN111875602B publication Critical patent/CN111875602B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D471/00Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04Ortho-condensed systems
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07BGENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13Crystalline forms, e.g. polymorphs
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10Non-macromolecular compounds
    • C09K2211/1003Carbocyclic compounds
    • C09K2211/1007Non-condensed systems
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10Non-macromolecular compounds
    • C09K2211/1018Heterocyclic compounds
    • C09K2211/1025Heterocyclic compounds characterised by ligands
    • C09K2211/1044Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

The invention discloses a cyano-modified pyridoimidazole derivative, a preparation method and application thereof, wherein the cyano-modified pyridoimidazole derivative has a molecular structure shown as a formula (I):
Figure DDA0002586116600000011
wherein R1 is hydrogen or cyano, R2 is hydrogen or cyano, and R1 and R2 are not simultaneously hydrogen. The invention introduces C \8230, H \8230, pi stacking structure and cyano group into the pyridine imidazole derivatives to obtain higher fluorescence quantum yield, enhanced electron-withdrawing capability of acceptor groups and red shift of spectra, and the derivatives also have better AIE effect, high-efficiency Thermally Activated Delayed Fluorescence (TADF) property, good thermal stability and solubility, can be used as red light emitting materials, light emitting devices or light emitting intelligent materials and the like, and can be applied to the fields of full-color display, solid state lighting and the like.

Description

一种氰基修饰吡啶并咪唑类衍生物及其制备方法和应用A kind of cyano group-modified pyridoimidazole derivatives and preparation method and application thereof

技术领域technical field

本发明涉及有机发光材料技术领域,更具体地,涉及一种氰基修饰吡啶并咪唑类衍生物及其制备方法和应用。The invention relates to the technical field of organic light-emitting materials, and more particularly, to a cyano group-modified pyridoimidazole derivative and a preparation method and application thereof.

背景技术Background technique

有机发光材料用作有机发光二极管(OLED)的技术在平板显示、智能手机以及固体发光等领域有广泛的应用,归功于有机发光材料具有大面积和高质量显示与照明、超高分辨率、超快响应速度和柔性等显著优势。The technology of organic light-emitting materials used as organic light-emitting diodes (OLEDs) has a wide range of applications in flat panel displays, smart phones, and solid-state light emitting. Significant advantages such as fast response speed and flexibility.

但是,目前有机发光材料中的红光发光材料由于其固有的窄带隙会极大增强分子的非辐射跃迁速率,从而导致较大的能量损失,因此存在固态荧光量子产率不高、热稳定性和溶解性不好的问题。However, due to its inherent narrow band gap, the red light emitting materials in the current organic light emitting materials will greatly enhance the non-radiative transition rate of molecules, resulting in large energy loss, so there are low solid-state fluorescence quantum yield, thermal stability. and poor solubility.

如中国专利CN102070632B公开了一种吡啶并咪唑衍生物及其在有机电致发光器件中的应用,所述的吡啶并咪唑衍生物通过引入刚性结构的取代基团使其发光位置红移到可见光区域,提高发光效率,同时破坏分子共平面性,提高化合物的热稳定性,但是该化合物还存在荧光量子产率较低、溶解性不好的问题。For example, Chinese patent CN102070632B discloses a pyridoimidazole derivative and its application in an organic electroluminescent device. The pyridoimidazole derivative red-shifts its light-emitting position to the visible light region by introducing a substituent group with a rigid structure , improve the luminous efficiency, destroy the coplanarity of the molecules, and improve the thermal stability of the compound, but the compound still has the problems of low fluorescence quantum yield and poor solubility.

发明内容SUMMARY OF THE INVENTION

本发明要解决的技术问题是克服现有吡啶并咪唑类衍生物发光材料的荧光量子产率较低、溶解性不好的缺陷和不足,提供一种氰基修饰吡啶并咪唑类衍生物,其荧光量子产率高,能产生聚集诱导发光(AIE)效应,可以发出红光,同时具有较好的热稳定性和溶解性。The technical problem to be solved by the present invention is to overcome the defects and deficiencies of low fluorescence quantum yield and poor solubility of the existing pyridoimidazole derivative light-emitting materials, and provide a cyano group-modified pyridoimidazole derivative, which is It has high fluorescence quantum yield, can produce aggregation-induced emission (AIE) effect, can emit red light, and has good thermal stability and solubility.

本发明的又一目的是提供一种氰基修饰吡啶并咪唑类衍生物的制备方法。Another object of the present invention is to provide a preparation method of cyano group-modified pyridoimidazole derivatives.

本发明的另一目的是提供一种氰基修饰吡啶并咪唑类衍生物的应用。Another object of the present invention is to provide an application of cyano group-modified pyridoimidazole derivatives.

本发明上述目的通过以下技术方案实现:The above-mentioned purpose of the present invention is achieved through the following technical solutions:

一种氰基修饰吡啶并咪唑类衍生物,具有如式(Ⅰ)所示的分子结构:A cyano group-modified pyridoimidazole derivative has the molecular structure shown in formula (I):

Figure BDA0002586116580000021
其中R1为氢或氰基,R2为氢或氰基,R1和R2不同时为氢。
Figure BDA0002586116580000021
wherein R1 is hydrogen or cyano, R2 is hydrogen or cyano, and R1 and R2 are not both hydrogen.

本发明提供的氰基修饰吡啶并咪唑类衍生物,一方面由于其结构中含N芳香蒽基(或称为氢化吩噁嗪基)与羰基之间引入桥联的苯环,形成较大的共轭平面;另一方面,由于存在C…H…π堆积(由氢化吩噁嗪基与吡啶并咪唑上的N原子提供),以上结构均有利于分子发光,获得较高的荧光量子产率。此外,分子中还引入的氰基,使分子给电子能力增强,导致光谱红移,发出红光,单线态和三线态能级差显著减小,使得热激活延迟荧光(TADF)性质更加卓越。由于该氰基修饰吡啶并咪唑类衍生物还含有羰基,可以造成分子振动,能产生聚集诱导发光(AIE)效应,可以有效地抑制激子湮灭,使分子在高浓度聚集态下比低浓度下有更强的荧光发射,从而具有较高的发光强度,具有较好的AIE性能。并且,由于该氰基修饰吡啶并咪唑类衍生物的相对分子量较大,含N杂环结构(吡啶并咪唑基团)和含N芳香蒽基结构存在共轭情况,使得制备的该氰基修饰吡啶并咪唑类衍生物具有热稳定性良好的优点。另外,上述氰基修饰吡啶并咪唑类衍生物结构上的芳环体积较小,溶解性较好。The cyano group-modified pyridoimidazole derivatives provided by the present invention, on the one hand, due to the introduction of a bridged benzene ring between the N-aromatic anthracenyl group (or called hydrogenated phenoxazinyl group) and the carbonyl group in its structure, it forms a larger Conjugated planes; on the other hand, due to the existence of C…H…π stacking (provided by hydrogenated phenoxazine groups and N atoms on pyridoimidazole), the above structures are all conducive to molecular luminescence and obtain higher fluorescence quantum yields . In addition, the cyano group also introduced into the molecule enhances the electron-donating ability of the molecule, resulting in a red shift of the spectrum, red light emission, and a significant reduction in the energy level difference between the singlet state and the triplet state, which makes the thermally activated delayed fluorescence (TADF) properties more excellent. Because the cyano group-modified pyridoimidazole derivatives also contain carbonyl groups, they can cause molecular vibrations, can produce aggregation-induced emission (AIE) effect, can effectively inhibit exciton annihilation, and make molecules in a high-concentration aggregation state than in a low-concentration state. It has stronger fluorescence emission, thus has higher luminescence intensity and better AIE performance. In addition, due to the relatively large relative molecular weight of the cyano-modified pyridoimidazole derivatives, the N-containing heterocyclic structure (pyridimidazole group) and the N-containing aromatic anthracenyl structure are conjugated, so that the prepared cyano group-modified Pyridimidazole derivatives have the advantage of good thermal stability. In addition, the aromatic ring on the structure of the above-mentioned cyano-modified pyridoimidazole derivatives has a smaller volume and better solubility.

优选地,所述R1为氰基时,R2为氢时,氰基修饰吡啶并咪唑类衍生物结晶于正交晶系,空间群为P21/n,晶胞参数为

Figure BDA0002586116580000022
Figure BDA0002586116580000023
β=95.651(2)°;Preferably, when R1 is a cyano group, and when R2 is a hydrogen group, the cyano group-modified pyridoimidazole derivatives are crystallized in an orthorhombic crystal system, the space group is P21/n, and the unit cell parameter is
Figure BDA0002586116580000022
Figure BDA0002586116580000023
β=95.651(2)°;

或者所述R1为氢时,R2为氰基时,氰基修饰吡啶并咪唑类衍生物结晶于正交晶系,空间群为P21/c,

Figure BDA0002586116580000024
β=102.328(2)°。Or when R1 is hydrogen and R2 is cyano, the cyano group-modified pyridoimidazole derivatives are crystallized in an orthorhombic system, and the space group is P21/c,
Figure BDA0002586116580000024
β=102.328(2)°.

本发明保护上述氰基修饰吡啶并咪唑类衍生物的制备方法,将吡啶并咪唑类衍生物与10-氢-吩噁嗪通过Buchwald-Hartwig交叉偶联反应制得式(Ⅰ)化合物;所述吡啶并咪唑类衍生物为4-(2-(4-溴苯)咪唑并[1,a])吡啶-3-基)苄腈、4-(2-(4-溴苯)咪唑并[1,a])吡啶-3-基)吡啶腈、4-(2-(4-溴苯)咪唑并[1,a])吡啶-3-基)苄-吡啶腈中的一种。The present invention protects the preparation method of the above-mentioned cyano group-modified pyridoimidazole derivatives, wherein the compound of formula (I) is prepared by Buchwald-Hartwig cross-coupling reaction between the pyridoimidazole derivatives and 10-hydro-phenoxazine; The pyridoimidazole derivatives are 4-(2-(4-bromophenyl)imidazo[1,a])pyridin-3-yl)benzonitrile, 4-(2-(4-bromophenyl)imidazo[1] ,a]) One of pyridin-3-yl)pyridinenitrile and 4-(2-(4-bromophenyl)imidazo[1,a])pyridin-3-yl)benzyl-pyridinenitrile.

优选地,所述吡啶并咪唑类衍生物与10-氢-吩噁嗪的摩尔比为1∶1~2。Preferably, the molar ratio of the pyridoimidazole derivatives to 10-hydro-phenoxazine is 1:1-2.

更优选地,所述吡啶并咪唑类衍生物与10-氢-吩噁嗪的摩尔比为1∶1~1.2。More preferably, the molar ratio of the pyridoimidazole derivatives to 10-hydro-phenoxazine is 1:1-1.2.

进一步优选地,所述吡啶并咪唑类衍生物与10-氢-吩噁嗪的摩尔比为1∶1.1。Further preferably, the molar ratio of the pyridoimidazole derivatives to 10-hydro-phenoxazine is 1:1.1.

优选地,所述Buchwald-Hartwig交叉偶联反应在120~130℃下,反应12~15h。Preferably, the Buchwald-Hartwig cross-coupling reaction is carried out at 120-130° C. for 12-15 hours.

更优选地,所述Buchwald-Hartwig交叉偶联反应在128~130℃下,反应13~15h。More preferably, the Buchwald-Hartwig cross-coupling reaction is carried out at 128-130° C. for 13-15 hours.

进一步优选地,所述Buchwald-Hartwig交叉偶联反应在130℃下,反应15h。Further preferably, the Buchwald-Hartwig cross-coupling reaction is carried out at 130° C. for 15 hours.

优选地,所述Buchwald-Hartwig交叉偶联反应在pH值为10~14下进行。Preferably, the Buchwald-Hartwig cross-coupling reaction is carried out at a pH of 10-14.

优选地,所述Buchwald-Hartwig交叉偶联反应的催化剂为钯催化剂。Preferably, the catalyst for the Buchwald-Hartwig cross-coupling reaction is a palladium catalyst.

优选地,所述的钯催化剂为醋酸钯。Preferably, the palladium catalyst is palladium acetate.

优选地,所述Buchwald-Hartwig交叉偶联反应在惰性氛围中进行。Preferably, the Buchwald-Hartwig cross-coupling reaction is carried out in an inert atmosphere.

优选地,所述惰性氛围为氮气、氩气、氦气中的一种。Preferably, the inert atmosphere is one of nitrogen, argon and helium.

优选地,所述(4-(2-(4-溴苯)咪唑并[1,a])吡啶-3-基)苄腈由(E)-4-(3-(4-溴苯肼)苄腈和2-氨基吡啶在碘单质存在下进行Michael环合反应得到。Preferably, the (4-(2-(4-bromophenyl)imidazo[1,a])pyridin-3-yl)benzonitrile is derived from (E)-4-(3-(4-bromophenylhydrazine) Benzonitrile and 2-aminopyridine are obtained by Michael cyclization reaction in the presence of iodine element.

优选地,所述(E)-4-(3-(4-溴苯肼))苄腈、2-氨基吡啶与碘单质的摩尔比为1~1.1∶2~2.2∶0.23~0.25。Preferably, the molar ratio of (E)-4-(3-(4-bromophenylhydrazine))benzonitrile, 2-aminopyridine and iodine is 1-1.1:2-2.2:0.23-0.25.

更优选地,所述((E)-4-(3-(4-溴苯肼))苄腈、2-氨基吡啶与碘单质的摩尔比为1∶2∶0.23。More preferably, the molar ratio of ((E)-4-(3-(4-bromophenylhydrazine))benzonitrile, 2-aminopyridine and iodine is 1:2:0.23.

优选地,所述(4-(2-(4-溴苯)咪唑并[1,a])吡啶-3-基)吡啶腈由(E)-4-(3-(4-溴苯肼))苄和2-氨基4-氰基吡啶在碘单质存在下进行Michael环合反应得到。Preferably, the (4-(2-(4-bromophenyl)imidazo[1,a])pyridin-3-yl)pyridinecarbonitrile is derived from (E)-4-(3-(4-bromophenylhydrazine) ) benzyl and 2-amino 4-cyanopyridine are obtained by Michael cyclization reaction in the presence of iodine element.

优选地,所述((E)-4-(3-(4-溴苯肼))苄、2-氨基-4-氰基吡啶与碘单质的摩尔比为1~1.1∶2~2.2∶0.23~0.25。Preferably, the molar ratio of ((E)-4-(3-(4-bromophenylhydrazine))benzyl, 2-amino-4-cyanopyridine and iodine element is 1~1.1:2~2.2:0.23 ~0.25.

更优选地,所述((E)-4-(3-(4-溴苯肼))苄、2-氨基-4-氰基吡啶与碘单质的摩尔比为1∶2∶0.23。More preferably, the molar ratio of ((E)-4-(3-(4-bromophenylhydrazine))benzyl, 2-amino-4-cyanopyridine and iodine is 1:2:0.23.

优选地,所述Michael环合反应的溶剂为二氯乙烷。Preferably, the solvent for the Michael cyclization reaction is dichloroethane.

优选地,所述Michael环合反应是在空气中,115~120℃反应10~13h。Preferably, the Michael cyclization reaction is performed in air at 115-120° C. for 10-13 hours.

更优选地,所述Michael环合反应是在空气中,118~120℃反应10~12h。More preferably, the Michael cyclization reaction is performed in air at 118-120° C. for 10-12 hours.

进一步优选地,所述Michael环合反应是在空气中,120℃反应12h。Further preferably, the Michael cyclization reaction is performed in air at 120° C. for 12 hours.

优选地,所述制备方法还包括冷却、蒸馏、萃取、干燥、浓缩、分离的后处理步骤。Preferably, the preparation method further includes post-processing steps of cooling, distillation, extraction, drying, concentration and separation.

具体地,所述后处理步骤为冷却收集得到黄色浑浊液,将浑浊液减压蒸馏除去甲苯,所剩固体用二氯甲烷萃取三次,合并三次得有机相,用无水硫酸镁干燥,再减压蒸馏有机相得到粗产品,最后用乙酸乙酯与石油醚作为洗脱剂进行硅胶柱层析分离出式(Ⅰ)化合物。Specifically, the post-processing step is cooling and collecting to obtain a yellow turbid liquid, the turbid liquid is distilled under reduced pressure to remove toluene, the remaining solid is extracted three times with dichloromethane, combined three times to obtain an organic phase, dried with anhydrous magnesium sulfate, and then reduced The organic phase is distilled under pressure to obtain a crude product, and finally the compound of formula (I) is isolated by silica gel column chromatography using ethyl acetate and petroleum ether as eluents.

优选地,还包括将氰基修饰吡啶并咪唑类衍生物溶解于有机溶剂中,得饱和溶液,再加入正己烷,于20~30℃中析出氰基修饰吡啶并咪唑类衍生物晶体样品。Preferably, the method also includes dissolving the cyano-modified pyridoimidazole derivative in an organic solvent to obtain a saturated solution, and then adding n-hexane to precipitate a crystal sample of the cyano-modified pyridoimidazole derivative at 20-30°C.

由于氰基修饰吡啶并咪唑类衍生物在正己烷中溶解度较小,缓慢加入正己烷有利于晶体的析出。Since the cyano-modified pyridoimidazole derivatives have low solubility in n-hexane, slow addition of n-hexane is beneficial to the precipitation of crystals.

更优选地,所述结晶的温度为25℃。结晶温度如果过低,不利于有机溶剂与正己烷溶剂的挥发,不利于晶体的析出,而温度过高,有机溶剂挥发过快,容易长出针状的多晶,晶型不好。More preferably, the temperature of the crystallization is 25°C. If the crystallization temperature is too low, it is not conducive to the volatilization of the organic solvent and the n-hexane solvent, and is not conducive to the precipitation of crystals. If the temperature is too high, the organic solvent volatilizes too quickly, and needle-like polycrystals are easy to grow, and the crystal form is not good.

优选地,所述有机溶剂为四氢呋喃、二氯甲烷,甲苯中的一种。Preferably, the organic solvent is one of tetrahydrofuran, dichloromethane and toluene.

优选地,所述有机溶剂与正己烷的体积比为1∶1~2。Preferably, the volume ratio of the organic solvent to n-hexane is 1:1-2.

优选地,加入正己烷的速度为0.5~1.0mL/min。Preferably, the rate of adding n-hexane is 0.5-1.0 mL/min.

优选地,所述析出氰基修饰吡啶并咪唑类衍生物晶体样品后,还包括过滤、洗涤、烘干的后处理步骤。Preferably, after the cyano group-modified pyridoimidazole derivative crystal sample is precipitated, post-processing steps of filtration, washing and drying are further included.

优选地,所述洗涤使用正己烷为洗涤剂。Preferably, the washing uses n-hexane as a detergent.

本发明还保护上述氰基修饰吡啶并咪唑类衍生物在有机发光材料中的应用。The present invention also protects the application of the above-mentioned cyano group-modified pyridoimidazole derivatives in organic light-emitting materials.

具体地,氰基修饰吡啶并咪唑类衍生物在有机红光发光材料中的应用。Specifically, the application of cyano group-modified pyridoimidazole derivatives in organic red light-emitting materials.

本发明所制得的氰基修饰吡啶并咪唑类衍生物在实际应用中,能够组装成单层的发光器件,具有较好的发光性能,并简化工艺,降低成本。In practical application, the cyano group-modified pyridoimidazole derivatives prepared by the invention can be assembled into a single-layer light-emitting device, have good light-emitting performance, simplify the process and reduce the cost.

与现有技术相比,本发明的有益效果是:Compared with the prior art, the beneficial effects of the present invention are:

本发明提供的氰基修饰吡啶并咪唑类衍生物含N芳香蒽基,与羰基之间引入桥联的苯环,形成较大的共轭平面,存在C…H…π堆积,具有较高的荧光量子产率,并且引入氰基,使得受体基团吸电子能力增强,分子内的电荷转移现象更加突出,光谱红移,可发出红光,并且本发明的氰基修饰吡啶并咪唑类衍生物还具有较好的AIE效应、卓越的TADF性质、良好的热稳定性和溶解性,可作为一种性能好、成本较低的新型可溶性发光分子,可用作红光发光材料、发光器件或发光智能材料等,可应用于全彩显示和固态照明等领域。The cyano group-modified pyridoimidazole derivatives provided by the present invention contain N aromatic anthracenyl groups, and a bridged benzene ring is introduced between the cyano group and the carbonyl group to form a larger conjugated plane. Fluorescence quantum yield, and the introduction of a cyano group enhances the electron-withdrawing ability of the acceptor group, the intramolecular charge transfer phenomenon is more prominent, the spectrum is red-shifted, and red light can be emitted, and the cyano group-modified pyridoimidazole derivatives of the present invention It also has good AIE effect, excellent TADF properties, good thermal stability and solubility, and can be used as a new type of soluble light-emitting molecule with good performance and low cost, which can be used as red light-emitting materials, light-emitting devices or Light-emitting smart materials, etc., can be applied to fields such as full-color display and solid-state lighting.

附图说明Description of drawings

图1为实施例1制得的氰基修饰吡啶并咪唑类衍生物Ben-CN的氢谱图。Fig. 1 is the hydrogen spectrum of the cyano group-modified pyridoimidazole derivative Ben-CN prepared in Example 1.

图2为实施例1制得的氰基修饰吡啶并咪唑类衍生物Ben-CN的质谱图。FIG. 2 is the mass spectrum of the cyano group-modified pyridoimidazole derivative Ben-CN prepared in Example 1. FIG.

图3为实施例2制得的氰基修饰吡啶并咪唑类衍生物Bd-CN的氢谱图。FIG. 3 is the hydrogen spectrum of the cyano group-modified pyridoimidazole derivative Bd-CN prepared in Example 2. FIG.

图4为实施例2制得的氰基修饰吡啶并咪唑类衍生物Bd-CN的质谱图。FIG. 4 is the mass spectrum of the cyano group-modified pyridoimidazole derivative Bd-CN prepared in Example 2. FIG.

图5为实施例1制得的氰基修饰吡啶并咪唑类衍生物Ben-CN的紫外可见吸收光谱图。FIG. 5 is the UV-Vis absorption spectrum of the cyano group-modified pyridoimidazole derivative Ben-CN prepared in Example 1. FIG.

图6为实施例2制得的氰基修饰吡啶并咪唑类衍生物Bd-CN的紫外可见吸收光谱图及荧光发射图。FIG. 6 is the ultraviolet-visible absorption spectrum and fluorescence emission of the cyano group-modified pyridoimidazole derivative Bd-CN prepared in Example 2. FIG.

图7为实施例1制得的氰基修饰吡啶并咪唑类衍生物Ben-CN的在不同含水量的溶液中的AIE光谱图。7 is the AIE spectrum of the cyano-modified pyridoimidazole derivative Ben-CN prepared in Example 1 in solutions with different water contents.

图8为实施例2制得的氰基修饰吡啶并咪唑类衍生物Bd-CN的在不同含水量的溶液中的AIE光谱图。8 is the AIE spectrum of the cyano-modified pyridoimidazole derivative Bd-CN prepared in Example 2 in solutions with different water contents.

图9为实施例1制得的氰基修饰吡啶并咪唑类衍生物Ben-CN的溶剂化效应图。FIG. 9 is a diagram showing the solvation effect of the cyano-modified pyridoimidazole derivative Ben-CN prepared in Example 1. FIG.

图10为实施例1制得的氰基修饰吡啶并咪唑类衍生物Ben-CN的循环伏安图。10 is a cyclic voltammogram of the cyano group-modified pyridoimidazole derivative Ben-CN prepared in Example 1.

图11为实施例2制得的氰基修饰吡啶并咪唑类衍生物Bd-CN的循环伏安图。FIG. 11 is the cyclic voltammogram of the cyano group-modified pyridoimidazole derivative Bd-CN prepared in Example 2. FIG.

图12为实施例1制得的氰基修饰吡啶并咪唑类衍生物Ben-CN的单晶结果图。12 is a graph showing the single crystal result of the cyano group-modified pyridoimidazole derivative Ben-CN prepared in Example 1. FIG.

图13为实施例2制得的氰基修饰吡啶并咪唑类衍生物Bd-CN的单晶结果图。13 is a graph showing the single crystal result of the cyano group-modified pyridoimidazole derivative Bd-CN prepared in Example 2.

图14为实施例1制得的氰基修饰吡啶并咪唑类衍生物Ben-CN的单晶与纯膜荧光发射图。FIG. 14 is the single crystal and pure film fluorescence emission diagrams of the cyano group-modified pyridoimidazole derivative Ben-CN prepared in Example 1. FIG.

图15为实施例2制得的氰基修饰吡啶并咪唑类衍生物Bd-CN的单晶与纯膜荧光发射图。15 is the single crystal and pure film fluorescence emission diagrams of the cyano-modified pyridoimidazole derivative Bd-CN prepared in Example 2. FIG.

图16为实施例1及实施例2制得的氰基修饰吡啶并咪唑类衍生物Ben-CN及Bd-CN的热稳定性图。FIG. 16 is a thermal stability diagram of the cyano group-modified pyridoimidazole derivatives Ben-CN and Bd-CN prepared in Example 1 and Example 2. FIG.

图17为实施例1制得的氰基修饰吡啶并咪唑类衍生物Ben-CN的常温荧光及低温磷光的测试光谱。17 is the test spectrum of room temperature fluorescence and low temperature phosphorescence of the cyano-modified pyridoimidazole derivative Ben-CN prepared in Example 1.

图18为实施例2制得的氰基修饰吡啶并咪唑类衍生物Bd-CN的常温荧光及低温磷光的测试光谱。18 is the test spectrum of the room temperature fluorescence and low temperature phosphorescence of the cyano-modified pyridoimidazole derivative Bd-CN prepared in Example 2.

具体实施方式Detailed ways

下面结合具体实施方式对本发明作进一步的说明,但实施例并不对本发明做任何形式的限定。除非另有说明,本发明实施例采用的原料试剂为常规购买的原料试剂。The present invention will be further described below in conjunction with specific embodiments, but the embodiments do not limit the present invention in any form. Unless otherwise specified, the raw material reagents used in the examples of the present invention are conventionally purchased raw material reagents.

实施例1Example 1

一种氰基修饰吡啶并咪唑类衍生物,命名为Ben-CN,具有如下所示的分子结构:A cyano group-modified pyridoimidazole derivative, named Ben-CN, has the following molecular structure:

Figure BDA0002586116580000061
Figure BDA0002586116580000061

上述Ben-CN的制备方法,包括如下步骤:The preparation method of above-mentioned Ben-CN, comprises the steps:

称取(E)-4-(3-(4-溴苯肼))苄腈150mg,2-氨基吡啶80mg碘单质60mg与3mL二氯乙烷于10mL封管内,温度120℃条件下进行Michael环合反应,处理后得到(4-(2-(4-溴苯)咪唑并[1,a])吡啶-3-基)苄腈;DCE为二氯乙烷;Weigh (E)-4-(3-(4-bromophenylhydrazine)) benzonitrile 150mg, 2-aminopyridine 80mg iodine element 60mg and 3mL dichloroethane in a 10mL sealed tube, carry out Michael ring at 120℃ After treatment, (4-(2-(4-bromophenyl)imidazo[1,a])pyridin-3-yl)benzonitrile is obtained; DCE is dichloroethane;

其反应方程式为:Its reaction equation is:

Figure BDA0002586116580000062
Figure BDA0002586116580000062

称取上述制得的(4-(2-(4-溴苯)咪唑并[1,a])吡啶-3-基)苄腈180mg,10-氢-吩噁嗪115mg,叔丁醇钾80mg,三叔丁基膦4mg,醋酸钯5.5mg和5mL的甲苯于封管内,搅拌抽掉装置中空气并充以氮气保护,在130℃氮气保护下加热搅拌回流反应15h,反应完后,将粗产物经过冷却、蒸馏、萃取、干燥、浓缩、分离;冷却收集得到黄色浑浊液,将浑浊液减压蒸馏除去甲苯,所剩固体用二氯甲烷萃取三次,合并三次所得有机相,用无水硫酸镁干燥,再减压蒸馏有机相得到粗产品;最后用乙酸乙酯与石油醚作为洗脱剂进行硅胶柱层析分离;得到的纯产物溶液减压蒸馏并真空干燥后得到90mg黄色固体,即为Ben-CN,纯度99%,产率50%;进一步将产物加入到四氢呋喃与正己烷1:1混合溶液中,在室温下缓慢挥发溶剂后得到晶体;Weigh out 180 mg of (4-(2-(4-bromophenyl)imidazo[1,a])pyridin-3-yl)benzonitrile prepared above, 115 mg of 10-hydro-phenoxazine, and 80 mg of potassium tert-butoxide. , 4 mg of tri-tert-butylphosphine, 5.5 mg of palladium acetate and 5 mL of toluene were placed in a sealed tube, and the air in the device was removed by stirring and filled with nitrogen protection. The product is cooled, distilled, extracted, dried, concentrated and separated; the yellow turbid liquid is obtained by cooling and collection, the turbid liquid is distilled under reduced pressure to remove toluene, the remaining solid is extracted three times with dichloromethane, and the organic phases obtained three times are combined, and anhydrous sulfuric acid is used. After drying over magnesium, the organic phase was distilled under reduced pressure to obtain a crude product; finally, ethyl acetate and petroleum ether were used as eluents for separation by silica gel column chromatography; the obtained pure product solution was distilled under reduced pressure and dried under vacuum to obtain 90 mg of a yellow solid, namely It is Ben-CN, with a purity of 99% and a yield of 50%; the product is further added to a 1:1 mixed solution of tetrahydrofuran and n-hexane, and the solvent is slowly evaporated at room temperature to obtain crystals;

其反应方程式如下:Its reaction equation is as follows:

Figure BDA0002586116580000071
Figure BDA0002586116580000071

实施例2Example 2

一种氰基修饰吡啶并咪唑类衍生物,命名为Bd-CN,具有如下所示的分子结构:A cyano group-modified pyridoimidazole derivative, named Bd-CN, has the following molecular structure:

Figure BDA0002586116580000072
Figure BDA0002586116580000072

上述Bd-CN的制备方法与实施例1相同,区别在于,将(E)-4-(3-(4-溴苯肼))苄腈替换为(E)-4-(3-(4-溴苯肼))腈,2-氨基吡啶替换为2-氨基-4-氰基-吡啶制得(4-(2-(4-溴苯)咪唑并[1,a])吡啶-3-基)吡啶腈;The preparation method of the above-mentioned Bd-CN is the same as that in Example 1, except that (E)-4-(3-(4-bromophenylhydrazine))benzonitrile is replaced by (E)-4-(3-(4- Bromophenylhydrazine)) nitrile, 2-aminopyridine was replaced by 2-amino-4-cyano-pyridine to obtain (4-(2-(4-bromophenyl)imidazo[1,a])pyridin-3-yl ) pyridine nitrile;

其反应方程式如下:Its reaction equation is as follows:

Figure BDA0002586116580000081
Figure BDA0002586116580000081

实施例3Example 3

一种氰基修饰吡啶并咪唑类衍生物,具有如下所示的分子结构:A cyano group-modified pyridoimidazole derivative has the following molecular structure:

Figure BDA0002586116580000082
Figure BDA0002586116580000082

上述氰基修饰吡啶并咪唑类衍生物的制备方法与实施例1相同,区别在于,将(4-(2-(4-溴苯)咪唑并[1,a])吡啶-3-基)苄腈替换为(4-(2-(4-溴苯)咪唑并[1,a])吡啶-3-基)苄-吡啶腈。The preparation method of the above cyano group-modified pyridoimidazole derivatives is the same as that in Example 1, the difference is that (4-(2-(4-bromophenyl)imidazo[1,a])pyridin-3-yl)benzyl The nitrile was replaced with (4-(2-(4-bromophenyl)imidazo[1,a])pyridin-3-yl)benzyl-pyridinecarbonitrile.

其反应方程式如下:Its reaction equation is as follows:

Figure BDA0002586116580000083
Figure BDA0002586116580000083

Figure BDA0002586116580000091
Figure BDA0002586116580000091

对比例1Comparative Example 1

本对比例的氰基修饰吡啶并咪唑类衍生物,具有如下所示的分子结构:The cyano group-modified pyridoimidazole derivatives of this comparative example have the following molecular structures:

Figure BDA0002586116580000092
Figure BDA0002586116580000092

上述氰基修饰吡啶并咪唑类衍生物的制备方法与实施例1相同,区别在于,将(E)-4-(3-(4-溴苯肼))苯酮替换为(E)-4-(3-(4-溴苯肼))苄腈。The preparation method of the above-mentioned cyano group-modified pyridoimidazole derivatives is the same as that in Example 1, except that (E)-4-(3-(4-bromophenylhydrazine))benzophenone is replaced by (E)-4- (3-(4-Bromophenylhydrazine))benzonitrile.

其反应方程式如下:Its reaction equation is as follows:

Figure BDA0002586116580000093
Figure BDA0002586116580000093

结构表征及性能测试Structural Characterization and Performance Testing

1、核磁共振和质谱1. Nuclear Magnetic Resonance and Mass Spectrometry

采用核磁共振扫描了该实施例1制得的Ben-CN的氢信号;将实施例1及2制得的氰基修饰吡啶并咪唑类衍生物溶于乙腈,配成浓度为1mg/mL的溶液,采用液质联用仪LCMS-2020,进行质谱测试。The hydrogen signal of Ben-CN prepared in Example 1 was scanned by nuclear magnetic resonance; the cyano-modified pyridoimidazole derivatives prepared in Examples 1 and 2 were dissolved in acetonitrile to prepare a solution with a concentration of 1 mg/mL , using a liquid mass spectrometer LCMS-2020 for mass spectrometry.

实施例1制得的Ben-CN的核磁图谱(图1)δ(ppm)为1H NMR(400MHz,Chloroform-d)δ8.55–8.46(m,2H),8.07(d,J=7.0Hz,1H),7.84(dd,J=19.1,8.6Hz,3H),7.75(d,J=8.1Hz,2H),7.51–7.45(m,2H),7.39(ddd,J=9.1,6.6,1.1Hz,1H),6.96(td,J=6.9,1.1Hz,1H),6.75–6.64(m,4H),6.61(td,J=7.5,1.9Hz,2H),6.01(dd,J=7.8,1.5Hz,2H).从Ben-CN质谱图(图3)中可以看到,图中相对分子质量为505.17,减去一个H,与所合成的Ben-CN的相对分子质量一致。结合以上核磁和质谱的结果可知,实施例1制得的产物为Ben-CN。The nuclear magnetic spectrum of Ben-CN prepared in Example 1 (Fig. 1) δ(ppm) is 1 H NMR (400MHz, Chloroform-d) δ8.55-8.46(m, 2H), 8.07(d, J=7.0Hz ,1H),7.84(dd,J=19.1,8.6Hz,3H),7.75(d,J=8.1Hz,2H),7.51–7.45(m,2H),7.39(ddd,J=9.1,6.6,1.1 Hz, 1H), 6.96 (td, J=6.9, 1.1Hz, 1H), 6.75–6.64 (m, 4H), 6.61 (td, J=7.5, 1.9Hz, 2H), 6.01 (dd, J=7.8, 1.5Hz, 2H). From the Ben-CN mass spectrum (Figure 3), it can be seen that the relative molecular mass in the figure is 505.17, minus one H, which is consistent with the relative molecular mass of the synthesized Ben-CN. Combining the above NMR and mass spectrometry results, it can be known that the product prepared in Example 1 is Ben-CN.

实施例2制得的Bd-CN的核磁图谱(图2)δ(ppm)为1H NMR(400MHz,Chloroform-d)δ8.40(d,J=8.4Hz,2H),8.19(d,J=7.6Hz,1H),7.74(d,J=8.3Hz,1H),7.61–7.51(m,4H),7.44(t,J=7.9Hz,2H),7.15(t,J=7.8Hz,1H),7.01(dd,J=7.1,1.7Hz,1H),6.73–6.58(m,6H),5.97(dd,J=7.9,1.4Hz,2H).从Bd-CN质谱图(图4)中可以看到,图中相对分子质量为505.17,减去一个H,与所合成的Bd-CN的相对分子质量一致。结合以上核磁和质谱的结果可知,实施例2制得的产物为Bd-CN。The nuclear magnetic spectrum of Bd-CN prepared in Example 2 (Fig. 2) δ (ppm) is 1 H NMR (400MHz, Chloroform-d) δ 8.40 (d, J=8.4 Hz, 2H), 8.19 (d, J =7.6Hz,1H),7.74(d,J=8.3Hz,1H),7.61–7.51(m,4H),7.44(t,J=7.9Hz,2H),7.15(t,J=7.8Hz,1H) ), 7.01 (dd, J=7.1, 1.7Hz, 1H), 6.73–6.58 (m, 6H), 5.97 (dd, J=7.9, 1.4Hz, 2H). From the Bd-CN mass spectrum (Fig. 4) It can be seen that the relative molecular mass in the figure is 505.17, minus one H, which is consistent with the relative molecular mass of the synthesized Bd-CN. Combining the above NMR and mass spectrometry results, it can be known that the product prepared in Example 2 is Bd-CN.

2、紫外可见吸收光谱2. UV-Vis absorption spectrum

采用岛津紫外可见光分光光度计UV-2700,将实施例1和2制得的氰基修饰吡啶并咪唑类衍生物溶于THF中配成1×10-3mol/L的母液,稀释成1×10-5mol/L进行测试。Using a Shimadzu UV-Vis spectrophotometer UV-2700, the cyano-modified pyridoimidazole derivatives prepared in Examples 1 and 2 were dissolved in THF to prepare a 1×10 -3 mol/L mother solution, and diluted to 1 ×10 -5 mol/L for testing.

从图5中看出,Ben-CN的主要吸收峰位置为334nm,发射波长为601nm,为红光发射。It can be seen from Figure 5 that the main absorption peak position of Ben-CN is 334 nm, and the emission wavelength is 601 nm, which is red light emission.

从图6中看出,Bd-CN的主要吸收峰位置为334nm,发射波长为610nm,为红光发射。而对比例1的分子发射波长为574nm,不能产生红光。It can be seen from Fig. 6 that the main absorption peak position of Bd-CN is 334 nm, and the emission wavelength is 610 nm, which is red light emission. In contrast, the molecule of Comparative Example 1 has an emission wavelength of 574 nm and cannot generate red light.

3、AIE性能3. AIE performance

将氰基修饰吡啶并咪唑类衍生物溶于四氢呋喃中配成1×10-3mol/L的母液,维持测试溶液总体积为3mL。保持测试溶液中氰基修饰吡啶并咪唑类衍生物的浓度为1×10- 5mol/L,调节测试溶液中四氢呋喃和水的比例。例如:水含量为90%时,各成分加入量为母液∶水∶四氢呋喃=30uL∶2700uL∶270uL。采用FLS980荧光仪测试氰基修饰吡啶并咪唑类衍生物的AIE光谱图。The cyano-modified pyridoimidazole derivatives were dissolved in tetrahydrofuran to prepare a 1×10 -3 mol/L mother solution, and the total volume of the test solution was maintained at 3 mL. Keep the concentration of cyano-modified pyridoimidazole derivatives in the test solution at 1×10 - 5 mol/L, and adjust the ratio of tetrahydrofuran and water in the test solution. For example: when the water content is 90%, the addition amount of each component is mother liquor: water: tetrahydrofuran=30uL:2700uL:270uL. The AIE spectra of cyano-modified pyridoimidazole derivatives were measured by FLS980 fluorometer.

分别测试了氰基修饰吡啶并咪唑类衍生物Ben-CN在水含量为0%~99%的四氢呋喃-水溶液中的荧光光谱,如图7所示,箭头指示方向为6条荧光图线所对应的溶液的水含量依次增加方向,Ben-CN的发射波长为600nm;当水含量低于95%时,Ben-CN在溶液中的荧光发射波长出现明显的红移;而当水含量超过95%后,光谱蓝移,分子在溶液中析出聚集,对应荧光强度均发生大幅度增强,可知Ben-CN存在明显的AIE现象。The fluorescence spectra of cyano-modified pyridoimidazole derivatives Ben-CN in tetrahydrofuran-water solution with water content of 0% to 99% were tested respectively, as shown in Figure 7, the direction indicated by the arrows corresponds to the 6 fluorescence graph lines The water content of the solution increases in turn, and the emission wavelength of Ben-CN is 600 nm; when the water content is lower than 95%, the fluorescence emission wavelength of Ben-CN in the solution has an obvious red shift; and when the water content exceeds 95% After that, the spectrum blue-shifted, the molecules precipitated and aggregated in the solution, and the corresponding fluorescence intensity was greatly enhanced. It can be seen that Ben-CN has obvious AIE phenomenon.

分别测试了Bd-CN在水含量为0%~99%的四氢呋喃-水溶液中的荧光光谱;如图8所示,箭头指示方向为4条荧光图线所对应的溶液的水含量依次增加方向,Bd-CN的发射波长为610nm;当水含量低于95%时,Bd-CN在溶液中的荧光发射波长出现明显的红移;而当水含量超过95%后,光谱蓝移,分子在溶液中析出聚集,对应荧光强度均发生大幅度增强,可知Bd-CN存在明显的AIE现象。The fluorescence spectra of Bd-CN in tetrahydrofuran-water solution with water content of 0% to 99% were tested respectively; as shown in Figure 8, the direction indicated by the arrows is the direction in which the water content of the solution corresponding to the four fluorescence graph lines increases in turn, The emission wavelength of Bd-CN is 610 nm; when the water content is less than 95%, the fluorescence emission wavelength of Bd-CN in solution has a significant red shift; when the water content exceeds 95%, the spectrum is blue-shifted, and the molecule is in the solution. The precipitation and aggregation in Bd-CN were greatly enhanced, and the corresponding fluorescence intensity was greatly enhanced, indicating that Bd-CN had obvious AIE phenomenon.

4、溶剂化效应4. Solvation effect

采用FLS980荧光仪测试氰基修饰吡啶并咪唑类衍生物在不同溶剂里归一化的光谱图。The normalized spectra of cyano-modified pyridoimidazole derivatives in different solvents were measured by FLS980 fluorometer.

从图9可以看出,氰基修饰吡啶并咪唑类衍生物Ben-CN在不同溶剂(按照溶剂极性由大到小排列:正己烷n-hex、甲苯Tol、二氯甲烷DCM、四氢呋喃THF、乙酸乙酯EtaOH)里,随着溶剂极性的增强,其光谱表现出明显的溶剂化变色效应,这是由于分子内的电荷转移效应(ICT),即电荷转移激发态所引起的。It can be seen from Figure 9 that the cyano group-modified pyridoimidazole derivatives Ben-CN are in different solvents (in descending order of solvent polarity: n-hexane n-hex, toluene Tol, dichloromethane DCM, tetrahydrofuran THF, In ethyl acetate (EtaOH), with the enhancement of solvent polarity, the spectrum shows obvious solvatochromic effect, which is caused by the intramolecular charge transfer effect (ICT), that is, the charge transfer excited state.

5、循环伏安图5. Cyclic voltammogram

采用电化学工作站PGSTAT302测试实施例1和实施例2制备得到的氰基修饰吡啶并咪唑类衍生物Ben-CN和Bd-CN的循环伏安图。The cyclic voltammograms of the cyano group-modified pyridoimidazole derivatives Ben-CN and Bd-CN prepared in Example 1 and Example 2 were tested by electrochemical workstation PGSTAT302.

将氰基修饰吡啶并咪唑类衍生物溶于乙腈中配成1mg/mL的溶液,在电化学工作站下通过循环伏安法测得Ben-CN和Bd-CN的氧化电位为E=0.74eV及E=0.75eV(如图10,图11所示)。与对比例1的E=0.67V相比,Ben-CN和Bd-CN具有氧化电位值更强,更有利于红光的生成。The cyano-modified pyridoimidazole derivatives were dissolved in acetonitrile to make a solution of 1 mg/mL. The oxidation potentials of Ben-CN and Bd-CN were measured by cyclic voltammetry under the electrochemical workstation. E=0.74 eV and E=0.75eV (as shown in Figure 10, Figure 11). Compared with E=0.67V of Comparative Example 1, Ben-CN and Bd-CN have stronger oxidation potential values, which are more conducive to the generation of red light.

6、溶解性6. Solubility

实施例1制得的Ben-CN溶于丙酮、乙酸乙酯、四氢呋喃、二氯甲烷溶剂中,具体以10毫克样品溶于1毫升溶剂中。结果如表1所示,其中“+”表示能够溶于对应的溶剂中,“+”个数越多表示在对应的溶剂中溶解度越大。The Ben-CN prepared in Example 1 was dissolved in acetone, ethyl acetate, tetrahydrofuran, and dichloromethane solvent, specifically, 10 mg of the sample was dissolved in 1 ml of solvent. The results are shown in Table 1, where "+" indicates that it can be dissolved in the corresponding solvent, and the more "+", the greater the solubility in the corresponding solvent.

表1实施例1及实施例2制得的Ben-CN和Bd-CN的溶解性Table 1 Solubility of Ben-CN and Bd-CN prepared in Example 1 and Example 2

Figure BDA0002586116580000111
Figure BDA0002586116580000111

Figure BDA0002586116580000121
Figure BDA0002586116580000121

以上表1结果表明,Ben-CN和Bd-CN的溶解性较好。The results in Table 1 above show that Ben-CN and Bd-CN have better solubility.

7、单晶X-射线衍射7. Single crystal X-ray diffraction

晶体结构采用德国布鲁克X单晶衍射仪测定。测试方法:选择大小适度,晶质良好的单晶体作试样,利用X射线射到一粒单晶体上会发生衍射,由对衍射线的分析可以解析出原子在晶体中的排列规律,收集衍射数据,指标化衍射图,求出晶胞常数,依据全部衍射线的衍射指标,总结出消光规律,推断晶体所属的空间群。将测得的衍射强度作吸收校正,LP校正等各种处理以得出结构振幅|F|。利用派特逊函数法,推测相角和初结构。The crystal structure was determined by Bruker X single crystal diffractometer in Germany. Test method: Select a single crystal with a moderate size and good crystal quality as a sample. When X-rays are irradiated on a single crystal, diffraction will occur. By analyzing the diffraction lines, the arrangement law of atoms in the crystal can be analyzed, and the diffraction data can be collected. Index the diffractogram, obtain the unit cell constant, sum up the extinction law according to the diffraction index of all diffraction lines, and infer the space group to which the crystal belongs. The measured diffraction intensity is subjected to absorption correction, LP correction and other processing to obtain the structural amplitude |F|. Using the Paterson function method, the phase angle and initial structure are inferred.

如图12所示,单晶X-射线衍射数据表明,实施例1的Ben-CN属于正交晶系,空间群为P21/n,

Figure BDA0002586116580000122
β=95.651(2)°,
Figure BDA0002586116580000123
Z=4。从晶体的作用力图可以看到,分子之间存在C…H…O/N及C…H…π堆积,这有利于分子的发光,并且,采用FLS980的积分球测试其绝对量子产率,结果显示Ben-CN获得大于50%的高荧光量子产率。As shown in Figure 12, the single crystal X-ray diffraction data shows that the Ben-CN of Example 1 belongs to the orthorhombic system, and the space group is P21/n,
Figure BDA0002586116580000122
β=95.651(2)°,
Figure BDA0002586116580000123
Z=4. It can be seen from the force diagram of the crystal that there are C…H…O/N and C…H…π stacking between the molecules, which is beneficial to the luminescence of the molecules, and the absolute quantum yield of the molecules was tested by using the integrating sphere of FLS980. The result It is shown that Ben-CN achieves high fluorescence quantum yields greater than 50%.

如图13所示,单晶X-射线衍射数据表明,实施例2的Bd-CN属于正交晶系,空间群为P21/c,

Figure BDA0002586116580000124
β=102.328(2)°,
Figure BDA0002586116580000125
Z=4。从晶体的作用力图可以看到,分子之间存在C…H…O/N及C…H…π堆积,这有利于分子的发光,并且,采用FLS980的积分球测试其绝对量子产率,结果显示Bd-CN获得大于50%的高荧光量子产率。As shown in Figure 13, the single crystal X-ray diffraction data shows that the Bd-CN of Example 2 belongs to the orthorhombic system, and the space group is P2 1 /c,
Figure BDA0002586116580000124
β=102.328(2)°,
Figure BDA0002586116580000125
Z=4. It can be seen from the force diagram of the crystal that there are C…H…O/N and C…H…π stacking between the molecules, which is beneficial to the luminescence of the molecules, and the absolute quantum yield of the molecules was tested by using the integrating sphere of FLS980. The result It is shown that Bd-CN achieves high fluorescence quantum yields greater than 50%.

8、单晶荧光发射测试8. Single crystal fluorescence emission test

荧光光谱:采用爱丁堡FL980瞬态稳态荧光磷光光谱仪进行固体荧光光谱测试;设置激发波长370nm,设置狭缝宽度,使其纵坐标数值接近一百万,然后进行光谱测试获得谱图。Fluorescence spectrum: use Edinburgh FL980 transient steady-state fluorescence phosphorescence spectrometer for solid fluorescence spectrum test; set the excitation wavelength to 370nm, set the slit width so that the ordinate value is close to one million, and then perform the spectrum test to obtain the spectrum.

如图14及图15所示,在370nm的光激发下,实施例1及实施例2制得的Ben-CN和Bd-CN晶体和纯膜(将Ben-CN和Bd-CN分别真空蒸镀在石英片上制得薄膜)在600nm出现最大发射峰。通过比较,可以发现晶体发射波峰较宽,这可能归因于:与无定型的纯膜相比,在晶体结构中,分子之间存在比较明显的C…H…π堆积。纯膜中实施例1及实施例2制得的Ben-CN和Bd-CN都获得了大于600nm的荧光发射,与对比例1的574nm的荧光发射相比,体现出本发明制得的分子在红光发射上的优越性。并且,在纯膜中实施例1及实施例2制得的Ben-CN和Bd-CN都获得了接近40%的荧光量子产率,而对比例1的薄膜的荧光量子产率为30.2%,说明在薄膜状态下Ben-CN和Bd-CN相对于对比例1的分子具有更好的发光性能。As shown in Figure 14 and Figure 15, under the light excitation of 370 nm, the crystals and pure films of Ben-CN and Bd-CN prepared in Example 1 and Example 2 (Ben-CN and Bd-CN were vacuum evaporated respectively Thin films prepared on quartz wafers) exhibit an emission maximum at 600 nm. By comparison, it can be found that the crystal emission peak is wider, which may be attributed to the obvious C…H…π stacking between molecules in the crystal structure compared with the pure amorphous film. In the pure film, Ben-CN and Bd-CN prepared in Example 1 and Example 2 both obtained fluorescence emission greater than 600 nm. Compared with the fluorescence emission of 574 nm in Comparative Example 1, it showed that the molecules prepared by the present invention were in Superiority in red light emission. Moreover, in the pure film, Ben-CN and Bd-CN prepared in Example 1 and Example 2 both obtained fluorescence quantum yield close to 40%, while the fluorescence quantum yield of the thin film of Comparative Example 1 was 30.2%, It shows that Ben-CN and Bd-CN have better luminescence properties than the molecules of Comparative Example 1 in the thin film state.

如图16所示,在氮气氛围下以20℃的温度梯度升温,可知实施例1及实施例2制得的Ben-CN和Bd-CN的热分解温度都超过400℃,与对比例1的热分解温度为369.1℃,证明该实施例1及实施例2更优秀的热稳定性。As shown in Fig. 16, the temperature was increased at a temperature gradient of 20°C under nitrogen atmosphere. It can be seen that the thermal decomposition temperatures of Ben-CN and Bd-CN prepared in Example 1 and Example 2 all exceeded 400°C, which was higher than that of Comparative Example 1. The thermal decomposition temperature was 369.1° C., which proved that Example 1 and Example 2 had better thermal stability.

如图17及图18所示,在氮气氛围下,用FLS980仪器对实施例1及实施例2制得的Ben-CN和Bd-CN进行常温荧光及低温磷光的测试,根据光谱计算出来的最低单线态S1及最低三线态T1能级差分别低至0.03和0.02个电子伏特,与对比例1的0.05eV能级差相比,说明本发明的两种分子均具有更高效的TADF性能。As shown in Figure 17 and Figure 18, under nitrogen atmosphere, the Ben-CN and Bd-CN prepared in Example 1 and Example 2 were tested for room temperature fluorescence and low temperature phosphorescence with FLS980 instrument. The energy level difference of the singlet state S 1 and the lowest triplet state T 1 is as low as 0.03 and 0.02 electron volts, respectively, compared with the 0.05 eV energy level difference of the comparative example 1, indicating that the two molecules of the present invention have more efficient TADF performance.

显然,本发明的上述实施例仅仅是为清楚地说明本发明所作的举例,而并非是对本发明的实施方式的限定。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。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明权利要求的保护范围之内。Obviously, the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. For those of ordinary skill in the art, changes or modifications in other different forms can also be made on the basis of the above description. There is no need and cannot be exhaustive of all implementations here. Any modifications, equivalent replacements and improvements made within the spirit and principle of the present invention shall be included within the protection scope of the claims of the present invention.

Claims (10)

1. A cyano-modified pyridoimidazole derivative is characterized by having a molecular structure shown as a formula (I):
Figure FDA0003775992020000011
wherein R1 is hydrogen and R2 is cyano; or R1 is cyano and R2 is hydrogen.
2. The cyano-modified pyridoimidazole derivative according to claim 1, wherein R is 1 When it is cyano, R 2 When the crystal is hydrogen, the cyano-modified pyridoimidazole derivative is crystallized in an orthorhombic system, the space group is P21/n, and the unit cell parameter is
Figure FDA0003775992020000013
β=95.651(2)°;
Or when R1 is hydrogen and R2 is cyano, the cyano-modified pyridoimidazole derivative is crystallized in an orthorhombic system, the space group is P21/c, and the unit cell parameter is
Figure FDA0003775992020000014
Figure FDA0003775992020000015
β=102.328(2)°。
3. The method for preparing cyano-modified pyridoimidazole derivatives according to claim 1 or 2, characterized in that the compound of formula (i) is prepared by Buchwald-Hartwig cross-coupling reaction of the pyridoimidazole derivatives with 10-hydro-phenoxazine; the structural formula of the pyridoimidazole derivatives is shown in the specification
Figure FDA0003775992020000012
4. The preparation method according to claim 3, characterized in that the molar ratio of the pyridoimidazole derivative to the 10-hydro-phenoxazine is 1: 1-2.
5. The preparation method of claim 3, wherein the Buchwald-Hartwig cross-coupling reaction is carried out at 120-130 ℃ for 12-15 h.
6. The method of claim 3, wherein the Buchwald-Hartwig cross-coupling reaction is carried out at a pH of 10 to 14.
7. The method of claim 3, wherein the catalyst for the Buchwald-Hartwig cross-coupling reaction is a palladium catalyst.
8. The method of claim 3, wherein the Buchwald-Hartwig cross-coupling reaction is performed in an inert atmosphere.
9. The preparation method according to claim 3, characterized by further comprising dissolving the cyano-modified pyridoimidazole derivative in an organic solvent to obtain a saturated solution, adding n-hexane, and precipitating a cyano-modified pyridoimidazole derivative crystal sample at 20-30 ℃.
10. The application of the cyano-modified pyridoimidazole derivatives in organic luminescent materials according to claim 1 or 2.
CN202010681777.4A 2020-07-15 2020-07-15 A kind of cyano group-modified pyridoimidazole derivatives and preparation method and application thereof Active CN111875602B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN202010681777.4A CN111875602B (en) 2020-07-15 2020-07-15 A kind of cyano group-modified pyridoimidazole derivatives and preparation method and application thereof
PCT/CN2020/122079 WO2022011863A1 (en) 2020-07-15 2020-10-20 Cyano-modified pyridino imidazole derivative, preparation method therefor, and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010681777.4A CN111875602B (en) 2020-07-15 2020-07-15 A kind of cyano group-modified pyridoimidazole derivatives and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN111875602A CN111875602A (en) 2020-11-03
CN111875602B true CN111875602B (en) 2022-10-21

Family

ID=73156062

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010681777.4A Active CN111875602B (en) 2020-07-15 2020-07-15 A kind of cyano group-modified pyridoimidazole derivatives and preparation method and application thereof

Country Status (2)

Country Link
CN (1) CN111875602B (en)
WO (1) WO2022011863A1 (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112645949B (en) * 2020-12-25 2022-04-19 广东工业大学 Aromatic amine derivative containing benzophenone group and preparation method and application thereof
CN112979649A (en) * 2021-03-16 2021-06-18 广东工业大学 Pyridoimidazole derivative and preparation method and application thereof
CN113620947B (en) * 2021-09-08 2022-05-31 广东工业大学 An anthracene derivative and its preparation method and application
CN114716416B (en) * 2022-04-11 2023-06-16 湖北大学 3, 4-dihydropyrrole derivative and one-pot synthesis thereof
CN116768940A (en) * 2023-06-14 2023-09-19 大连理工大学 A cyano-bridged trinuclear spin change complex and its preparation method and application
NL2036209B1 (en) * 2023-11-08 2024-06-06 Univ Guangdong Technology Use of cyano-modified pyridino imidazole derivative in preparing organic photoelectric devices

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102070632A (en) * 2009-11-20 2011-05-25 中国科学院理化技术研究所 Pyridoimidazole Derivatives and Their Applications in Organic Electroluminescent Devices
CN109320459A (en) * 2018-10-09 2019-02-12 广东工业大学 A kind of fluorene-containing phenanthroimidazole derivatives, crystal and preparation method and application thereof
CN109705041A (en) * 2019-01-29 2019-05-03 广东工业大学 A triphenylamine substituted-vinyl modified phenanthroimidazole compound, its preparation method and its application as an electroluminescent device
CN110117283A (en) * 2019-03-22 2019-08-13 广东工业大学 A kind of N heterocycle Benzophenone analog derivative and preparation method thereof containing hydrogenation phenthazine group
CN110283169A (en) * 2019-03-22 2019-09-27 广东工业大学 A kind of N heterocycle Benzophenone analog derivative and preparation method thereof containing substituted hydrogenated acridine group

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102070632A (en) * 2009-11-20 2011-05-25 中国科学院理化技术研究所 Pyridoimidazole Derivatives and Their Applications in Organic Electroluminescent Devices
CN109320459A (en) * 2018-10-09 2019-02-12 广东工业大学 A kind of fluorene-containing phenanthroimidazole derivatives, crystal and preparation method and application thereof
CN109705041A (en) * 2019-01-29 2019-05-03 广东工业大学 A triphenylamine substituted-vinyl modified phenanthroimidazole compound, its preparation method and its application as an electroluminescent device
CN110117283A (en) * 2019-03-22 2019-08-13 广东工业大学 A kind of N heterocycle Benzophenone analog derivative and preparation method thereof containing hydrogenation phenthazine group
CN110283169A (en) * 2019-03-22 2019-09-27 广东工业大学 A kind of N heterocycle Benzophenone analog derivative and preparation method thereof containing substituted hydrogenated acridine group

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Stimuli-Responsive Aggregation-Induced Delayed Fluorescence Emitters Featuring the Asymmetric D-A Structure with a Novel Diarylketone Acceptor Toward Efficient OLEDs with Negligible Efficiency Roll-Off;Zhiwen Yang et al.;《ACS Applied Materials & Interfaces》;20200608;第12卷(第26期);29528-29539 *

Also Published As

Publication number Publication date
WO2022011863A1 (en) 2022-01-20
CN111875602A (en) 2020-11-03

Similar Documents

Publication Publication Date Title
CN111875602B (en) A kind of cyano group-modified pyridoimidazole derivatives and preparation method and application thereof
Chen et al. Mechanofluorochromism, polymorphism and thermochromism of novel D–π–A piperidin-1-yl-substitued isoquinoline derivatives
CN110903294B (en) Compound with benzo [1,2-b:5, 4-b' ] dibenzofuran as core and application thereof
CN113929709B (en) Organic compound containing boron and nitrogen and organic electroluminescent device containing same
CN110467606B (en) Heterocyclic compound with xanthone as core, preparation method and application thereof
Wang et al. Highly efficient electroluminescence from evaporation-and solution-processable orange–red thermally activated delayed fluorescence emitters
CN108440424A (en) Acenaphthene and pyrazines derivatives and its application
CN110818675A (en) Organic compound and application thereof
CN110885335A (en) Compound with benzo [1,2-b:4, 5-b' ] dibenzofuran as core and application thereof
CN111205295B (en) Compound with imidazocarbazole as receptor and application thereof
CN113004298B (en) Anthracene ketone five-membered ring organic compound and application thereof
CN110790766A (en) TADF compound, application thereof and electronic device containing TADF compound
CN111253374A (en) Naphtho five-membered ring benzo fused heterocycle organic compound and application thereof
CN113980054B (en) A kind of phosphine oxide compound and its preparation and application
CN112552225A (en) Triarylamine organic compound with carbazole as core and application thereof
CN114644632A (en) Thermal activation delayed fluorescence material based on bispyridophenazine receptor and preparation method and application thereof
CN111362866A (en) Azabenzene modified organic compound and application thereof
CN106831791B (en) A class of ethylated pyrazinoquinoxaline derivatives and its preparation method
CN112479904B (en) Organic compound with indeno-anthracene derivative as core and application thereof
CN112479901B (en) Organic compound with indeno-anthracene derivative as core and application thereof
CN109400519B (en) A tetraphenylethylene-benzophenone-carbazole derivative, crystal and its preparation method and application
CN114075229A (en) A boron-containing organic compound and its application in organic electroluminescent devices
CN111423455A (en) Bithiophene fused heterocycle organic compound and application thereof
CN114478588B (en) Organic compound based on pyrene and indolocarbazole, organic electroluminescent composition and organic electroluminescent device
Kwak et al. Integration of a bulky adamantane unit with 9-phenyl-9 H-3, 9′-bicarbazole: a novel host design for solution-processed narrowband TADF-OLEDs

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