Dynamic Molecular Metamorphism involving Palladium-Assisted Dimerization of π-Cation Radicals
Résumé
A dynamic supramolecular approach is developed to promote the π-dimerization of viologen radicals at room temperature and in standard concentration ranges. It involves cis-or trans-protected palladium centers serving as inorganic hinges linking two functionalized viologens endowed with metal-ion coordinating properties. On the ground of detailed spectroscopic, electrochemical and computational data, we show that the one electron electrochemical reduction of the viologen units in different dynamic metal:ligand mixtures leads to the formation of the same intramolecular -dimer, regardless of the initial environment around the metallic precursor and of the relative ratio between metal and ligand initially introduced in solution. The large scale electron-triggered reorganization of the building blocks introduced in solution thus involves drastic changes in the stoichiometry and stereochemistry of the palladium/viologen complexes proceeding in some cases through a palladium centered trans →cis isomerization of the coordinated ligands
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