Two M L 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 and Ag ) are depicted. Remarkably, based on a combination of specific structural and electronic features, the polycationic self-assembled Ag 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.

An electron-rich M2L4 cage is depicted, in which the four peripheral redox-active ligands (L) are 9-(1,3-dithiol-2-ylidene)fluorene units.