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

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.