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

Two M₁₂ L₆ 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 (Pd^II and Ag^I ) are depicted. Remarkably, based on a combination of specific structural and electronic features, the polycationic self-assembled Ag^I 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.