Zhang Qingqing, Jin Yunhe, Ma Lin, Zhang Yongqiang, Meng Changgong, Duan Chunying
State Key Laboratory of Fine Chemicals, Zhang Dayu School of Chemistry, Dalian University of Technology, Dalian, 116024, China.
Angew Chem Int Ed Engl. 2022 Sep 12;61(37):e202204918. doi: 10.1002/anie.202204918. Epub 2022 Jul 8.
2,4,6-Triphenylpyrylium (TPT ) functions as a classic organic photocatalyst and exhibits a noteworthy absorption in the visible range, strongly oxidizing excited states, and a somewhat unstable structure. Inspired by the nuclear chromophore and dual catalysis strategy, herein, we report a universal photoredox platform constructed by TPT -mimic bridging ligands and reductive metal ions on the basis of metal-organic supramolecular systems for various organic couplings and molecular oxygen activation under visible-light irradiation. Significant photoinduced electron transfer and ligand-to-metal charge-transfer events are both integrated and regulated by the spatial and kinetic confinement effects of the structurally confined microenvironments, effectively improving the efficiency of electron transfer and radical-radical coupling processes in photocatalysis. This package deal provides a promising way for the design of novel photocatalysts and the development of versatile and sustainable synthetic chemistry.
2,4,6-三苯基吡喃鎓（TPT）作为一种经典的有机光催化剂，在可见光范围内表现出显著的吸收，具有强氧化性的激发态，且结构 somewhat 不稳定。受核发色团和双催化策略的启发，在此，我们报道了一种基于金属有机超分子体系，由TPT模拟桥连配体和还原金属离子构建的通用光氧化还原平台，用于可见光照射下的各种有机偶联和分子氧活化。显著的光致电子转移和配体到金属的电荷转移事件通过结构受限微环境的空间和动力学限制效应进行整合和调控，有效提高了光催化中电子转移和自由基-自由基偶联过程的效率。这一整套方案为新型光催化剂的设计以及通用且可持续的合成化学的发展提供了一条有前景的途径。 （注：原文中“somewhat”不太明确准确意思，这里暂且保留英文，翻译为“ somewhat” ）
