Dynamic Molecular Metamorphism Involving Palladium-Assisted Dimerization of π-Cation Radicals |
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Authors: | Dr Christophe Kahlfuss Dr Raymond Grüber Prof Elise Dumont Prof Guy Royal Floris Chevallier Dr Saioa Cobo Prof Eric Saint-Aman Dr Christophe Bucher |
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Institution: | 1. Laboratoire de Chimie UMR 5182, CNRS–Univ. Lyon, ENS de Lyon, Université Claude Bernard Lyon 1, 69342 Lyon, France;2. Département de Chimie Moléculaire (UMR 5250), Univ. Grenoble Alpes, CNRS, DCM, 38000 Grenoble, France |
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Abstract: | A dynamic supramolecular approach is developed to promote the π-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 π-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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Keywords: | dyes/pigments metamorphism palladium pi-dimers redox chemistry self-assembly |
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