四氰基取代蒽并苊烯二酰亚胺的四芳基功能化及其可调的光电性质

doi:10.6023/cjoc202601005

研究论文

四氰基取代蒽并苊烯二酰亚胺的四芳基功能化及其可调的光电性质

马志鹏^a, 刘文涛^a, 孙承华^b, 孙继斌^b,*, 陈华杰^a,*

^a湘潭大学化学学院环境友好化学与应用教育部重点实验室湖南湘潭 411105;
^b中国科学院理化技术研究所光化学转换与功能材料重点实验室北京 100190

收稿日期:2026-02-27 修回日期:2026-03-21
基金资助:
国家自然科学基金(No. 22275157)资助项目.

Tetra-aryl Functionalization of Tetracyanodiacenaphthoanthracene Diimides and their Tunable Optoelectronic Properties

Ma Zhipeng^a, Liu Wentao^a, Sun Chenghua^b, Sun Jibin^b,*, Chen Huajie^a,*

^aKey Laboratory of Environmentally Friendly Chemistry and Application of Ministry of Education, College of Chemistry, Xiangtan University, Xiangtan, Hunan 411105;
^bKey Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing, 100190

Received:2026-02-27 Revised:2026-03-21
Contact: *E-mail: chenhjoe@xtu.edu.cn; sunjibin@mail.ipc.ac.cn
Supported by:
National Natural Science Foundation of China (No. 22275157).

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摘要/Abstract

本研究开发了二溴代苊醌酰亚胺中间体, 随后将其与2,2',2'',2'''-(苯-1,2,4,5-四酰基)四乙腈进行一步四重Knoevenagel缩合反应, 成功开发另一个重要的中间体, 即为四溴功能四氰基取代蒽并苊烯二酰亚胺(TCDADI-4Br). 通过Suzuki偶联反应, 成功将TCDADI-4Br转化成一系列含四芳基取代TCDADI衍生物, 包括TCDADI-4Ph, TCDADI-4OMe, TCDADI-4CF₃, TCDADI-4CN和TCDADI-4NMe₂. 结合理论计算和实验表征, 对比研究了不同芳基取代对所得材料骨架结构、吸收光谱、荧光性质、电化学能级以及非线性光学性质的影响. 研究发现: 1) 给电特性的甲氧基和二甲氨基的引入显著增强了TCDADI-4OMe和TCDADI-4NMe₂的分子内电荷转移作用, 从而导致其吸收光谱范围较TCDADI明显拓宽; 2) 强缺电特性的氰基和三氟甲基的引入显著提升了TCDADI-4CN和TCDADI-4CF₃的荧光量子产率, 其值分别达98.1%和98.7%. Z-值扫描实验测试表明: TCDADI-4OMe和TCDADI-4NMe₂呈现典型的反饱和吸收行为, 然而其他材料均呈现出明显的饱和吸收特性. 当入射激光能量为5 μJ时, TCDADI-4OMe和TCDADI-4NMe₂的非线性消光系数值分别达到232和109 cm GW^-1. 以上结果表明, TCDADI的四芳基功能化是调控其结构和光电性质的有效方法. 该类化合物在荧光染料、生物传感器以及有机非线性光学等领域具有潜在的应用前景.

关键词: 多环芳烃二酰亚胺, 苊酰亚胺, Knoevenagel缩合, 光电性质, 非线性光学性质

In this study, we report the synthesis of a dibrominated acenaphthenequinone imide intermediate, which is subsequently used to conduct the one-step fourfold Knoevenagel condensation with 2,2',2'',2'''-(benzene-1,2,4,5- tetrayl)tetraacetonitrile to give another important intermediate, namely, tetra-brominated tetracyanodiacenaphthoanthracene diimides (TCDADI-4Br). By applying Suzuki coupling reactions, TCDADI-4Br is successfully converted into a novel series of tetra-aryl substituted TCDADI derivatives, including TCDADI-4Ph, TCDADI-4OMe, TCDADI-4CF₃, TCDADI-4CN, and TCDADI-4NMe₂. The effect of different aryl substituents on the materials' backbone structures, absorption spectra, fluorescence properties, electrochemical energy levels as well as nonlinear optical properties has been studied comparatively by combining theoretical calculations and experimental characterizations. It is found that: 1) incorporating the electron-donating methoxy and dimethylamino groups into TCDADI-4OMe andTCDADI-4NMe₂ endows them with extended absorption bands compared to TCDADI, resulting from the improved intramolelcular charge-transfer interactions; 2) both TCDADI-4CN and TCDADI-4CF₃featuring electron-poor cyano and ‌trifluoromethyl group are proven to show extremely high fluorescence quantum yields of up to 98.1% and 98.7%, respectively. The Z-scan experiments indicate the typical reverse saturable absorption behaviors for both TCDADI-4OMe and TCDADI-4NMe₂, while the saturable absorption characteristics are clearly detectable for the other materials of this series. Upon treatment with the incident laser energy of 5 μJ, TCDADI-4OMe and TCDADI-4NMe₂ achieve the nonlinear absorption coefficients of 232 and 109 cm GW^-1, respectively. This study indicates that tetra-aryl functionalization of tetracyanodiacenaphthoanthracene diimides is an effective approach to regulate their molecular structures and optoelectronic properties. The tetra-aryl substituted TCDADI derivatives reported here hold promising application potentials in various fields like ‌fluorescent dyes, biosensors and organic nonlinear optics.

Key words: Polycyclic aromatic diimides, Acenaphthenequinone imide, Knoevenagel condensation, Optoelectronic property, Nonlinear optical property

引用此文

马志鹏, 刘文涛, 孙承华, 孙继斌, 陈华杰. 四氰基取代蒽并苊烯二酰亚胺的四芳基功能化及其可调的光电性质[J]. 有机化学, doi: 10.6023/cjoc202601005.

Ma Zhipeng, Liu Wentao, Sun Chenghua, Sun Jibin, Chen Huajie. Tetra-aryl Functionalization of Tetracyanodiacenaphthoanthracene Diimides and their Tunable Optoelectronic Properties[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202601005.

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