北京理工大学Jie Zhang团队报道了通过激发态过程对电荷转移的光调制——指导供体-受体结合动力学。相关研究成果发表在2024年9月5日出版的《德国应用化学》。

调节供体和受体分子之间的电荷转移（CT）相互作用可能会导致物理化学性质的独特动态变化，这在超分子化学和材料科学中具有重要意义。

该文中，研究人员首次展示了固态中供体-受体（D-A）CT相互作用的可逆光调制。具有π共轭D-A结构的吡啶基发色团不仅可以作为良好的电子受体进行光诱导电子转移（ET）或参与分子间CT相互作用，还可以根据激发波长表现出独特的双发射。D-A对中的可旋转C-C单键增强了分子结构的可调性。

通过光诱导ET和激发态构象变化的协同作用，分子间CT相互作用可以通过交替的光照射来开启和关闭，从而可逆地调节供体和受体分子之间的亲和力，同时伴随着视觉颜色切换和荧光开关作为反馈信号。

附：英文原文

Title: Photomodulation of Charge Transfer through Excited-State Processes: Directing Donor-Acceptor Binding Dynamics

Author: Jia-Qi Pan, Hao-Ran Wei, Yun-Rui Chen, Meng-Ze Jia, Bin Tan, Jie Zhang

Issue&Volume: 2024-09-05

Abstract: Modulating charge transfer (CT) interactions between donor and acceptor molecules may give rise to unique dynamic changes in physicochemical properties, exhibiting great importance in supramolecular chemistry and materials science. In this work, we demonstrate the first instance of reversible photomodulation of donor-acceptor (D-A) CT interaction in the solid state.Pyridinium-based chromophore featuring π-conjugated D-A structures can not only function as a good electron acceptor to undergo photoinduced electron transfer (ET) or engage in intermolecular CT interaction, but also exhibit unique dual emission depending on the excitation wavelengths. The rotatable C-C single bonds within D-A pairs enhance the tunability of molecular structure. Through the synergy of a photoinduced ET and an excited-state conformational change, the intermolecular CT interaction can be switched on and off by alternate light irradiation to enables reversibly modulation of the affinity between donor and acceptor molecules, accompanied by visual color switching and fluorescence on-off as feedback signals.

DOI: 10.1002/anie.202412790

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202412790