He Ben, Zhang Sikun, Zhang Yueyan, Li Guoping, Zhang Bingjie, Ma Wenqiang, Rao Bin, Song Ruitong, Zhang Lei, Zhang Yanfeng, He Gang
School of Chemistry, Xi'an Jiaotong University, Xi'an, Shaanxi Province 710049, People's Republic of China.
Key Laboratory of Thermo-Fluid Science and Engineering of Ministry of Education, Frontier Institute of Science and Technology, State Key Laboratory for Strength and Vibration of Mechanical Structures, Xi'an Jiaotong University, Xi'an, Shaanxi Province 710054, People's Republic of China.
J Am Chem Soc. 2022 Mar 16;144(10):4422-4430. doi: 10.1021/jacs.1c11577. Epub 2022 Feb 10.
A series of novel terphenylene viologen derivatives (TPV) with through-space conjugation (TSC) via the combination of terphenylene skeletons with viologen structure is reported. Their optoelectronic properties can be adjusted by -arylation or -alkylation reactions. Compared with other viologen derivatives, TPV not only exhibits strong photoluminescence but also retards the charge recombination process and stabilizes the diradical state without forming a quinoid structure due to the special TSC effect. Based on their special redox characteristics, TPV was applied to the photocatalytic oxidative coupling of benzylamine with 96% yield. In addition, TA-TPV (tethered with -toluic acid)-modified g-CN was used for visible-light-driven hydrogen production for the first time, exceeding 15 times the rate over unmodified g-CN.
报道了一系列通过将对亚苯基骨架与紫精结构相结合而具有空间共轭（TSC）的新型对亚苯基紫精衍生物（TPV）。它们的光电性质可通过芳基化或烷基化反应进行调节。与其他紫精衍生物相比，由于特殊的TSC效应，TPV不仅表现出强烈的光致发光，而且还延缓了电荷复合过程并稳定了双自由基状态，而不会形成醌型结构。基于其特殊的氧化还原特性，TPV被应用于苄胺的光催化氧化偶联反应，产率达96%。此外，TA-TPV（与对甲苯甲酸相连）修饰的g-CN首次用于可见光驱动的产氢反应，产氢速率超过未修饰的g-CN的15倍。
