RESUMEN
A metal-induced self-assembly strategy is used to promote the π-dimerization of viologen-based radicals at room temperature and in standard concentration ranges. Discrete box-shaped 2:2 (M:L) macrocycles or coordination polymers are formed in solution by self-assembly of a viologen-based ditopic ligand with cis-[Pd(en)(NO3)2], trans-[Pd(CH3CN)2(Cl)2], or [Pd(CH3CN)4(BF4)2]. Changing the redox state of the bipyridium units involved in the tectons, from their dicationic state to their radical cation state, results in a reversible "inflation/deflation" of the discrete 2:2 (M:L) macrocyclic assemblies associated to a large modification in the size of their inner cavity. Viologen-centered electron transfer is also used to trigger a dissociation of the coordination polymers formed with tetrakis(acetonitrile)Pd(II), the driving force of the disassembling process being the formation of discrete box-shaped 2:2 (M:L) assemblies stabilized by π-dimerization of both viologen cation radicals.