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Updated: Jan 29, 2026

Author Spotlight: Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers
Published on: May 12, 2023
Rigidification of a macrocyclic tris-catecholate scaffold leads to electronic localisation of its mixed valent redox
Sam Greatorex1, Kevin B Vincent, Amgalanbaatar Baldansuren
1School of Chemistry, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, UK. m.a.halcrow@leeds.ac.uk.
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.
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