Results
Title

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

Authors

Herasymchuk, Khrystyna; Allain, Magali; MacNeil, Gregory A.; Carré, Vincent; Aubriet, Frédéric; Leznoff, Daniel B.; Sallé, Marc; Goeb, Sébastien; Storr, Tim

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.

Subjects

METALLACYCLES; RUTHENIUM compounds; ELECTRON paramagnetic resonance spectroscopy; ELECTRONIC structure; ELECTROCHEMICAL experiments; EXCITON theory

Publication

Chemistry - A European Journal, 2021, Vol 27, Issue 65, p16161

ISSN

0947-6539

Publication type

Academic Journal

DOI

10.1002/chem.202102745