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Notable differences between oxidized diruthenium complexes bridged by four isomeric diethynyl benzodithiophene ligands

Ou, Y. P., Zhang, J., Zhang, F., Kuang, D., Hartl, F., Rao, L. and Liu, S. H. (2016) Notable differences between oxidized diruthenium complexes bridged by four isomeric diethynyl benzodithiophene ligands. Dalton Transactions, 45 (15). pp. 6503-6516. ISSN 1364-5447

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To link to this item DOI: 10.1039/c6dt00109b


Four new diruthenium complexes [{(η5-C5Me5)Ru(dppe)}2(μ-CuC–L–CuC)] featuring different bridging isomeric diethynyl benzodithiophenes viz. L = benzo[1,2-b;4,5-b’]dithiophene (complex 1), benzo[2,1-b;4,5b’]dithiophene (complex 2), benzo[1,2-b;3,4-b’]dithiophene (complex 3) and benzo[1,2-b;4,3-b’]-dithiophene (complex 4), were synthesized and characterized by molecular spectroscopic and crystallographicmethods. The subtle changes in the molecular structure introduced by the diethynyl benzodithiophene isomers have a notable impact on the stability of the oxidized complexes and their absorption characteristics in the visible-NIR and IR spectral domains. Electronic properties of stable oxidized complexes[1]n+ and [4]n+ (n = 1, 2) were investigated by cyclic voltammetry, UV-vis-NIR and IR spectroelectrochemistry as well as DFT and TDDFT calculations. The results document the largely bridgelocalized character of the oxidation of parents 1 and 4. Cations [2]+ and [3]+ are too unstable at ambient temperature to afford their unambiguous characterization. UV-vis-NIR absorption spectral data combined with TDDFT calculations (BLYP35) reveal that the broad electronic absorption of [1]+ and [4]+ in the NIR region has a mixed intraligand π–π* and MLCT character, with similar contribution from their spin-delocalized trans and cis conformers. A spin-localized (mixed-valence) rotamer was only observed for [1]+ at ambient temperature as a minor component on the time scale of IR spectroscopy.

Item Type:Article
Divisions:Interdisciplinary centres and themes > Chemical Analysis Facility (CAF)
Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
ID Code:58583
Publisher:Royal Society of Chemistry

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