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

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.

• Publication year

  2019

• Venue

  Chemical Communications

• Publication date

  2019-02-19

• Fields of study

  Medicine, Chemistry

• Identifiers
  DOI 10.1039/c8cc10122aPMID 30720027
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar, PubMed

• No claims are published for this paper.

• No concepts are published for this paper.

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