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Kinetically locked, trinuclear Ru-II metallo-macrocycles - synthesis, electrochemical, and optical properties

Shan, N., Ingram, J. D., Easun, Timothy ORCID: https://orcid.org/0000-0002-0713-2642, Vickers, S. J., Adams, H., Ward, M. D. and Thomas, J. A. 2006. Kinetically locked, trinuclear Ru-II metallo-macrocycles - synthesis, electrochemical, and optical properties. Dalton Transactions (23) , pp. 2900-2906. 10.1039/B516080B

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Abstract

Using a [RuII([9]aneS3)] templating moiety, kinetically-locked, metallomacrocycles incorporating adenine based ligands have been synthesised through self-assembly. The kinetically robust nature of these structures is confirmed by electrochemical studies: each can be reversibly oxidised in a four-member redox series, containing two formally mixed valence states. Unusually, the electrochemically derived comproportionation constants for these mixed valence states are very different, suggesting that intermetallic coupling differs between the two states. Spectroelectochemistry studies confirm that while the [RuII2RuIII] state is valence localised, the [RuIIRuIII2] state is electronically delocalised. Mechanisms by which this switching effect could occur, which involve the unusual connectivities in these mixed valence species, are presented.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Subjects: Q Science > QD Chemistry
Publisher: Royal Society of Chemistry
Last Modified: 28 Oct 2022 08:30
URI: https://orca.cardiff.ac.uk/id/eprint/71030

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