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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Voltammetry
Scaffolds
Charge transfer
Oxidation
Oxidation-Reduction

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Greatorex, Sam ; Vincent, Kevin ; Baldansuren, Amgalanbaatar ; McInnes, Eric ; Patmore, Nathan ; Sproules, Stephen ; Halcrow, Malcolm. / Rigidification of a macrocyclic tris-catecholate scaffold leads to electronic localisation of its mixed valent redox product. In: Chemical Communications. 2019 ; Vol. 55, No. 16. pp. 2281-2284.
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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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Rigidification of a macrocyclic tris-catecholate scaffold leads to electronic localisation of its mixed valent redox product. / Greatorex, Sam; Vincent, Kevin; Baldansuren, Amgalanbaatar; McInnes, Eric; Patmore, Nathan; Sproules, Stephen; Halcrow, Malcolm.

In: Chemical Communications, Vol. 55, No. 16, 25.02.2019, p. 2281-2284.

Research output: Contribution to journalArticle

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T1 - Rigidification of a macrocyclic tris-catecholate scaffold leads to electronic localisation of its mixed valent redox product

AU - Greatorex, Sam

AU - Vincent, Kevin

AU - Baldansuren, Amgalanbaatar

AU - McInnes, Eric

AU - Patmore, Nathan

AU - Sproules, Stephen

AU - Halcrow, Malcolm

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AB - 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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