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

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journal contribution
posted on 2021-02-23, 15:06 authored by Christophe Kahlfuss, Shagor Chowdhury, Adérito Fins Carreira, Raymond Grüber, Elise Dumont, Denis Frath, Floris Chevallier, Eric-Saint-Aman, Christophe Bucher
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.