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

Sam Greatorex, Kevin Vincent, Amgalanbaatar Baldansuren, Eric McInnes, Nathan Patmore, Stephen Sproules, Malcolm Halcrow

Research output: Contribution to journalArticle

Abstract

The catecholate groups in [{Pt(L)}33-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)}33-tctq˙)]+ is valence-localised, with no evidence for intervalence charge transfer in its near-IR spectrum. This contrasts with previously reported [{Pt(dppb)}33-ctc˙)]+ (H6ctc = cyclotricatechylene), based on the same macrocyclic tris-dioxolene scaffold, which exhibits partly delocalised (class II) mixed valency.
Original languageEnglish
Pages (from-to)2281-2284
Number of pages4
JournalChemical Communications
Volume55
Issue number16
DOIs
Publication statusPublished - 25 Feb 2019

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