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)

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