Inner‐Sphere Single Electron Transfer in Polynuclear Gold Photocatalysis

Abstract Photo‐induced electron transfer is a fundamental step in photochemical reactions, where light energy is used to drive chemical transformations. However, conventional outer‐sphere single electron transfer mechanisms encounter multiple limitations, notably requiring redox potential matching between photocatalysts and substrates, thereby impeding the activation of non‐activated carbon‐halogen bonds. In this concept review, we present an elucidation of the photophysical and photochemical properties exhibited by polynuclear gold photocatalysts, with a particular emphasis on their inner‐sphere single electron transfer mechanism. By exploring these intricate aspects, we endeavor to furnish readers with a more profound insight into the remarkable potential of polynuclear gold photocatalysts and the indispensable role played by inner‐sphere electron transfer in the realm of photocatalysis.