Photoswitchable Catalytic Divergent Synthesis by a Viologen‐Functionalized Lanthanide‐Organic Tetrahedral Cage

Abstract Photoswitchable catalysis presents a significant challenge, particularly in the modulation of reaction pathways. In this study, we describe a redox‐active lanthanide‐organic tetrahedral cage 1 , self‐assembled from a viologen‐functionalised ditopic tridentate ligand and Eu(III) ions. Complexation‐induced charge redistribution and spatial rearrangement of ligands in the assembly endow 1 with distinct photochromic properties and redox activities compared to free ligand L . 1 can serve as a photoswitchable catalyst for divergent chemical transformations of various tetraarylborates, giving biaryls and phenols via photo‐oxidative coupling reaction under 365 nm light irradiation, or producing mono‐arene products through catalytic de‐composition process in the absence of light. This work represents the first example of photoswitchable divergent synthesis by a single self‐assembled coordination cage, paving the way for the design and construction of novel supramolecular edifices with switchable functions.