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Exciton Coupling in Redox‐Active Salen based Self‐Assembled Metallacycles

Abstract : The incorporation of a redox-active nickel salen complex into supramolecular structures was explored via coordination-driven self-assembly with homobimetallic ruthenium complexes (bridged by oxalato or 5,8-dihydroxy-1,4-naphthoquinato ligands). The self-assembly resulted in the formation of a discrete rectangle using the oxalato complex and either a rectangle or a catenane employing the larger naphthoquinonato complex. The formation of the interlocked self-assembly was determined to be solvent and concentration dependent. The electronic structure and stability of the oxidized metallacycles was probed using electrochemical experiments, UV-Vis-NIR absorption, EPR spectroscopy and DFT calculations, confirming ligand radical formation. Exciton coupling of the intense near-infrared (NIR) ligand radical intervalence charge transfer (IVCT) bands provided further confirmation of the geometric and electronic structures in solution.
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https://hal-cnrs.archives-ouvertes.fr/hal-03773681
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Submitted on : Friday, September 9, 2022 - 1:57:17 PM
Last modification on : Tuesday, September 27, 2022 - 4:38:02 AM

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Khrystyna Herasymchuk, Magali Allain, Gregory Macneil, Vincent Carré, Frédéric Aubriet, et al.. Exciton Coupling in Redox‐Active Salen based Self‐Assembled Metallacycles. Chemistry - A European Journal, Wiley-VCH Verlag, 2021, 27 (65), pp.16161-16172. ⟨10.1002/chem.202102745⟩. ⟨hal-03773681⟩

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