Journal article
Tuning Valence Tautomerism in Dinuclear Cobalt Complexes by Modulating Communication in the Bridging Ligand
JT Janetzki, GK Gransbury, RW Gable, MJ Giansiracusa, AA Starikova, C Boskovic
European Journal of Inorganic Chemistry | Wiley-VCH Verlag | Published : 2024
Abstract
The capability of bis(dioxolene) ligands to access multiple redox states makes them ideal candidates to tune the electronic properties of metal complexes, for example to achieve valence tautomerism (VT). In this study, a family of dinuclear cobalt complexes have been isolated with the bridging bis(dioxolene) thean− ligand in the cat2−-cat2−, cat2−-SQ⋅− and SQ⋅−-SQ⋅− states (cat2−=catecholate, SQ⋅−=semiquinonate): [{CoIII(tpa)}2(theacat−cat)](PF6)2 (1), [{CoIII(tpa)}2(theacat−SQ)](PF6)3 (2), and [{CoIII(tpa)}2(theaSQ−SQ)](PF6)4 (3) (theaH4=2,3,6,7-tetrahydroxy-9,10-dimethyl-9,10-dihydro-9,10-ethanoanthracene, tpa=tris(2-pyridylmethyl)amine). Multi-technique analysis confirms that 1, 2 and 3 a..
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Awarded by Australian Government
Funding Acknowledgements
C.B. thanks the Australian Research Council for funding (FT190100293). J.T.J. acknowledges support from the Australian Government for a Research Training Stipend. We acknowledge the Australian Research Council for an equipment grant (LE210100009). 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). G.K.G. thanks the European Research Council (CoG-816268), awarded to Prof. David Mills. 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 beamlines at the Australian Synchrotron, part of ANSTO, Australia. This work was performed in part at the EPSRC UK National Electron Paramagnetic Resonance Service. We thank Dr Guy Jameson for preliminary EPR measurements. Open Access publishing facilitated by The University of Melbourne, as part of the Wiley - The University of Melbourne agreement via the Council of Australian University Librarians.