Journal article
Tuning valence tautomerism in a family of dinuclear cobalt complexes incorporating a conjugated bridging bis(dioxolene) ligand with weak communication
TE Fischer, JT Janetzki, FZ M. Zahir, RW Gable, AA Starikova, C Boskovic
Dalton Transactions | ROYAL SOC CHEMISTRY | Published : 2024
DOI: 10.1039/d3dt04162j
Abstract
Valence tautomerism (VT) involves the stimulated reversible intramolecular electron transfer between a redox-active metal and ligand. Dinuclear cobalt complexes bridged by bis(dioxolene) ligands can undergo thermally-induced VT with access to {CoIII-cat-cat-CoIII}, {CoIII-cat-SQ-CoII} and {CoII-SQ-SQ-CoII} states (cat2− = catecholate, SQ˙− = semiquinonate, CoIII refers to low spin CoIII, CoII refers to high spin CoII). The resulting potential for two-step VT interconversions offers increased functionality over mononuclear examples. In this study, the bis(dioxolene) ligand 3,3′,4,4′-tetrahydroxy-5,5′-dimethoxy-benzaldazine (thMH4) was paired with Mentpa (tpa = tris(2-pyridylmethyl)amine, n = ..
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Grants
Awarded by Australian Government
Funding Acknowledgements
We would like to thank the Australian Research Council for financial support (DP220100398) and an equipment grant (LE210100009). T. E. F. thanks the University of Melbourne for a Dr Jim Desmarchelier Scholarship. J. T. J. acknowledges support from the Australian Government for a Research Training Stipend. A. A. S. thanks the Ministry of Science and Higher Education of the Russian Federation (State assignment in the field of scientific activity, project no. FENW-2023-0017). This work was performed, in part, at the Trace Analysis for Chemical, Earth and Environmental Sciences (TrACEES) Platform at the University of Melbourne. This research was undertaken, in part, using the MX1 and MX2 beamlines at the Australian Synchrotron, part of ANSTO, Victoria, Australia and made use of the Australian Cancer Research Foundation (ACRF) detector (for MX2). We are grateful to Dr Gemma Gransbury for her invaluable feedback and discussions, and for providing Fig. S1 dagger/Fig. 6.