Dynamic Molecular Metamorphism Involving Palladium-Assisted Dimerization of π-Cation Radicals
Abstract A dynamic supramolecular approach is developed to promote the Ï-dimerization of viologen radicals at room temperature and in standard concentration ranges. The approach involves cis- or trans-protected palladium centers serving as inorganic hinges linking two functionalized viologens endowed with metal-ion coordinating properties. Based on 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 Ï-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 transâcis isomerization of the coordinated ligands.
Références
- Titre
- Dynamic Molecular Metamorphism Involving Palladium-Assisted Dimerization of π-Cation Radicals
- Type de publication
- Article de revue
- Année de publication
- 2019
- Auteurs
- Kahlfuss, Christophe, Grüber Raymond, Dumont Elise, Royal Guy, Chevallier Floris, Cobo Saioa, Saint-Aman Eric, and Bucher Christophe
- Revue
- Chemistry A European Journal
- Volume
- 25
- Pagination
- 1573-1580
Soumis le 3 septembre 2019