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

doi:10.6023/cjoc202601005

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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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Abstract

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

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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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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

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

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