Rigidification of a macrocyclic tris-catecholate scaffold leads to electronic localisation of its mixed valent redox product

Greatorex, S., Vincent, K. B., Baldansuren, A., McInnes, E. J.L., Patmore, N. J., Sproules, S. and Halcrow, M. A. (2019) Rigidification of a macrocyclic tris-catecholate scaffold leads to electronic localisation of its mixed valent redox product. Chemical Communications, 55, pp. 2281-2284. (doi:10.1039/C8CC10122A) (PMID:30720027)

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Abstract

The catecholate groups in [{Pt(L)}3(μ3-tctq)] (H6tctq = 2,3,6,7,10,11-hexahydroxy-4b,8b,12b,12d-tetramethyltribenzotriquinacene; L = a diphosphine chelate) undergo sequential oxidation to their semiquinonate forms by voltammetry, with ΔE1/2 = 160–170 mV. The monoradical [{Pt(dppb)}3(μ3-tctq˙)]+ is valence-localised, with no evidence for intervalence charge transfer in its near-IR spectrum. This contrasts with previously reported [{Pt(dppb)}3(μ3-ctc˙)]+ (H6ctc = cyclotricatechylene), based on the same macrocyclic tris-dioxolene scaffold, which exhibits partly delocalised (class II) mixed valency.

Item Type:Articles
Additional Information:This work was funded by the EPSRC (EP/M506552/1) and a Leverhulme Trust Research Project Grant (RPG-2014-303, to NJP and KBV).
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Sproules, Dr Stephen
Authors: Greatorex, S., Vincent, K. B., Baldansuren, A., McInnes, E. J.L., Patmore, N. J., Sproules, S., and Halcrow, M. A.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Chemical Communications
Publisher:Royal Society of Chemistry
ISSN:1359-7345
ISSN (Online):1364-548X
Published Online:31 January 2019
Copyright Holders:Copyright © 2019 The Royal Society of Chemistry
First Published:First published in Chemical Communications 55 2281-2284
Publisher Policy:Reproduced in accordance with the copyright policy of the publisher

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