Stable Mixed‐Valent Radicals from Platinum(II) Complexes of a Bis(dioxolene) Ligand |
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| Authors: | Dr. Jonathan J. Loughrey Dr. Stephen Sproules Prof. Eric J. L. McInnes Prof. Michaele J. Hardie Prof. Malcolm A. Halcrow |
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| Affiliation: | 1. School of Chemistry, University of Leeds, Woodhouse Lane, Leeds, LS2 9JT (UK), Fax: (+44)?113‐343‐6565;2. Current address: Department of Chemistry and Biochemistry, University of Arizona, P.O. Box 210041, 1306 East University Blvd., Tucson, AZ 85721‐0041 (USA);3. School of Chemistry and Photon Science Institute, University of Manchester, Oxford Road, Manchester, M13 9PL (UK);4. Current address: School of Chemistry, University of Glasgow, Joseph Black Building. University Avenue, Glasgow, G12 8QQ (UK) |
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| Abstract: | Three diplatinum(II) complexes [{PtL}2(μ‐thea)] (H4thea=2,3,6,7‐tetrahydroxy‐9,10‐dimethyl‐9,10‐dihydro‐9,10‐ethanoanthracene) have been prepared, with diphosphine or bipyridyl “L” co‐ligands. One‐electron oxidation of these complexes gave radical cations containing a mixed‐valent [thea ]3? ligand with discrete catecholate and semiquinonate centers separated by quaternary methylene spacers. The electronic character of these radicals is near the Robin–Day class II/III border determined by UV/Vis/NIR and EPR spectroscopies. Crystal‐structure determinations and a DFT calculation imply that oxidation of the thea4? ligand may lead to an increased through‐space interaction between the dioxolene π systems. |
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| Keywords: | charge transfer dioxolenes mixed‐valent compounds platinum radical ions |
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