Premium
Dynamic Molecular Metamorphism Involving Palladium‐Assisted Dimerization of π‐Cation Radicals
Author(s) -
Kahlfuss Christophe,
Grüber Raymond,
Dumont Elise,
Royal Guy,
Chevallier Floris,
Cobo Saioa,
SaintAman Eric,
Bucher Christophe
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201805017
Subject(s) - viologen , palladium , isomerization , chemistry , dimer , intramolecular force , electrochemistry , supramolecular chemistry , photochemistry , ligand (biochemistry) , metal , radical , stoichiometry , radical ion , inorganic chemistry , ion , catalysis , crystallography , stereochemistry , crystal structure , organic chemistry , electrode , biochemistry , receptor
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.