Kinetically locked, trinuclear RuIImetallo-macrocycles—synthesis, electrochemical, and optical properties

Autor:	Timothy L. Easun, Naz Shan, Steven J. Vickers, Harry Adams, James D. Ingram, Michael D. Ward, Jim A. Thomas
Rok vydání:	2006
Předmět:	Inorganic Chemistry Valence (chemistry) Chemistry Intermetallic Moiety Comproportionation Photochemistry Electrochemistry Redox
Zdroj:	Dalton Trans.. :2900-2906
ISSN:	1477-9234 1477-9226
DOI:	10.1039/b516080b
Popis:	Using a [Ru(II)([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 [Ru(II)2Ru(III)] state is valence localised, the [Ru(II)Ru(III)2] state is electronically delocalised. Mechanisms by which this switching effect could occur, which involve the unusual connectivities in these mixed valence species, are presented.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::3cf97da765340d496a5c7d8c8a18cb5d https://doi.org/10.1039/b516080b Zobrazit plný text záznamu