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

Research output: Contribution to journalArticle

  • External authors:
  • Sam Greatorex
  • Kevin B. Vincent
  • Amgalanbaatar Baldansuren
  • Nathan J. Patmore
  • Stephen Sproules
  • Malcolm A. Halcrow

Abstract

The catecholate groups in [{Pt(L)} 33 -tctq)] (H 6 tctq = 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 ΔE 1/2 = 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)] + (H 6 ctc = cyclotricatechylene), based on the same macrocyclic tris-dioxolene scaffold, which exhibits partly delocalised (class II) mixed valency.

Bibliographical metadata

Original languageEnglish
Pages (from-to)2281-2284
Number of pages4
JournalChemical Communications
Volume55
Issue number16
Early online date31 Jan 2019
DOIs
Publication statusPublished - 2019