Molecular Photoelectrocatalysis for Radical Reactions

作者：Peng Xiong, Hai‐Chao Xu · 发表于：Accounts of Chemical Research · 年份：2025 · DOI：10.1021/acs.accounts.4c00739 · 被引用次数：110 · 研究领域：Radical Photochemical Reactions、Sulfur-Based Synthesis Techniques、CO2 Reduction Techniques and Catalysts

Conspectus Molecular photoelectrocatalysis, which combines the merits of photocatalysis and organic electrosynthesis, including their green attributes and capacity to offer novel reactivity and selectivity, represents an emerging field in organic chemistry that addresses the growing demands for environmental sustainability and synthetic efficiency. This synergistic approach permits access to a wider range of redox potentials, facilitates redox transformations under gentler electrode potentials, and decreases the use of external harsh redox reagents. Despite these potential advantages, this area did not receive significant attention until 2019, when we and others reported the first examples of modern molecular photoelectrocatalysis. These studies showcased the immense synthetic potential of this hybrid strategy, which not only inherits the strengths of its parent fields but also unlocks unprecedented reactivity and selectivity, enabling challenging transformations under mild conditions while minimizing the reliance on external stoichiometric harsh oxidants or reductants. In this Account, we present our efforts to develop photoelectrocatalytic strategies that leverage homogeneous catalysts to facilitate diverse radical reactions. By integrating electrocatalysis with key photoinduced processes such as single electron transfer (SET), ligand-to-metal charge transfer (LMCT), and hydrogen atom transfer (HAT), we have established photoelectrocatalytic methods to transform substrates ...