Thiophene insertion for continuous modulation of the photoelectronic properties of triphenylamine-based metal–organic frameworks for photocatalytic sulfonylation–cyclisation of activated alkenes
作者:Tiexin Zhang、Yusheng Shi、Sen Zhang、Chen Jia、Cheng He、Chunying Duan
DOI:10.1039/c8nj04151b
日期:——
ligand engineering strategy of inserting different numbers of thiophenes into the scaffold of triphenylamine (TPA)-based ligands was developed to improve the visible light absorption, enhance the oxidation potentials of the ground states, and decrease the reduction potentials of the excited states, providing a powerful tool for continuous modulation of the photoelectronic properties of metal–organic
诸如光催化磺酰化的药学上有意义的转化要求对光催化剂的光电子性质的精确控制。开发了一种配体工程设计策略,该策略可将不同数量的噻吩插入基于三苯胺(TPA)的配体支架中,以改善可见光吸收,增强基态的氧化电势并降低激发态的还原电势,从而提供一个强大的工具,用于连续调节基于金属有机骨架(MOF)的多相光催化剂的光电特性。发现插入两个噻吩的配体具有良好的光电性能,并赋予了相应的MOF Zn–BCTA具有良好的可见光捕集能力和适度的激发态还原电势,具有最小的超电势,可避免光诱导产生磺酰基自由基,同时避免了磺酰基部分的竞争性过度还原。TPA基配体的C 3对称性的破坏伪造了MOF Zn 4 O节点的扭曲配位几何,以提供潜在的活性位点,以促进α,β-不饱和羰基底物的固定和活化,以及双重互穿框架进一步增强了封装基板与光氧化还原活性中心之间的空间接近性。Zn – BCTA的微调光电特性的协同作用 孔内的空间限制效