Redox‐Driven Transformation of a Discrete Molecular Cage into an Infinite 3D Coordination Polymer

Two M12L6 redox‐active self‐assembled cages constructed from an electron‐rich ligand based on the extended tetrathiafulvalene framework (exTTF) and metal complexes with a linear geometry (PdII and AgI) are depicted. Remarkably, based on a combination of specific structural and electronic features, the polycationic self‐assembled AgI coordination cage undergoes a supramolecular transformation upon oxidation into a three‐dimensional coordination polymer, that is characterized by X‐ray crystallography. This redox‐controlled change of the molecular organization results from the drastic conformational modifications accompanying oxidation of the exTTF moiety. Assembly required: A redox‐driven supramolecular transformation of a silver‐based electro‐active M12L6 self‐assembled cage into a cationic three‐dimensional coordination polymer is achieved. This redox‐controlled change of the molecular organization beneficiates from the conformational modification accompanying oxidation of the extended‐tetrathiafulvalene framework (exTTF).