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

Author:
Greatorex, Sam, Vincent, Kevin B., Baldansuren, Amgalanbaatar, McInnes, Eric J. L., Patmore, Nathan J., Sproules, Stephen, Halcrow, Malcolm A.
Source:
Chemical communications 2019 v.55 no.16 pp. 2281-2284
ISSN:
1364-548X
Subject:
chemical compounds, electron transfer, oxidation
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.
Agid:
6312531