The electronic and solvatochromic properties of [Co(L)(bipyridine)2]+ (L =o-catecholato, o-benzenedithiolato) species: A combined experimental and computational study

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Abstract

Complexes of Co(iii) containing mixed chelating diimine and o-quinone ligand sets are of fundamental interest on account of their fascinating magnetic and electronic properties. Whilst complexes of this type containing one diimine and two o-quinone ligands have been studied extensively, those with the reverse stoichiometry (two diimines and one o-quinone) are much rarer. Herein, we describe a ready route to the synthesis of the complex [CoIII(o-catecholate) (2,2′-bipyridine)2]+ (1), and also report the synthesis of [CoIII(o-catecholate)(5,5′-dimethyl-2,2′-bipyridine)2]+ (2) and [CoIII(o-benezenedithiolate)(5,5′-dimethyl-2,2′-bipyridine)2]+ (3) for the first time. Spectroscopic studies show that complex 2 displays intriguing solvatochromic behaviour as a function of solvent hydrogen bond donation ability, a property of this type of complex which has hitherto not been reported. Time-dependent density function theory (TD-DFT) shows that this effect arises as a result of hydrogen bonding between the solvent and the oxygen atoms of the catecholate ligand. In contrast, the sulfur atoms in the benzenedithiolate analogue 3 are much weaker acceptors of hydrogen bonds from the solvent, meaning that complex 3 is only very weakly solvatochromic. Finally, we show that complex 2 has some potential as a molecular probe that can report on the composition of mixed solvent systems as a function of its absorbance spectrum.

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Cioncoloni, G., Senn, H. M., Sproules, S., Wilson, C., & Symes, M. D. (2016). The electronic and solvatochromic properties of [Co(L)(bipyridine)2]+ (L =o-catecholato, o-benzenedithiolato) species: A combined experimental and computational study. Dalton Transactions, 45(39), 15575–15585. https://doi.org/10.1039/c6dt02807a

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