Electron-Triggered Metamorphism in Palladium-Driven Self-Assembled Architectures

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 solution by a ditopic ligand with cis-[Pd(en)(NO3)2], trans-[Pd(CH3CN)2(Cl)2], [Pd(CH3CN)4(BF4)2]. Changing redox state bipyridium units involved tectons, from their dicationic radical cation state, results reversible inflation/deflation discrete macrocyclic assemblies associated large modification size inner cavity. Viologen-centered electron transfer also trigger dissociation tetrakis(acetonitrile)Pd(II), driving force disassembling process being formation stabilized both viologen radicals.