Two ruthenium complexes capable of storing multiple electrons on a single ligand – photophysical, photochemical and electrochemical properties of [Ru(phen)2(TAPHAT)]2+ and [Ru(phen)2(TAPHAT)Ru(phen)2]4+

Troian-Gautier, Ludovic;Marcélis, L.;De Winter, J.;Gerbaux, P.;Moucheron, C.
(2017) Dalton Transactions — Vol. 46, n° 44, p. 15287-15300 (2017)

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Abstract
The photophysical, photochemical and electrochemical properties of two newly synthesized ruthenium complexes, [Ru(phen)2(TAPHAT)]2+ and [Ru(phen)2(TAPHAT)Ru(phen)2]4+, are reported. We have developed a novel synthetic methodology that involves the metal-free oxidative coupling of diamino compounds to form a desired “pyrazine-type” core. This methodology is employed both on the free diamino ligand as well as on the different ruthenium complexes, therefore illustrating the applicability of this reaction. The TAPHAT ligand, which possesses 7 aromatic rings and 10 nitrogen atoms for 20 carbon atoms, gives rise to ruthenium complexes that can undergo up to three consecutive reductions centered on said ligand, a critical parameter for electron storage applications. A temperature-dependent study has confirmed the presence of a 4th MLCT state. Excited-state quenching in the presence of guanine or hydroquinone allows to foresee biomedical applications.
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Troian-Gautier, L., Marcélis, L., De Winter, J., Gerbaux, P., & Moucheron, C. (2017). Two ruthenium complexes capable of storing multiple electrons on a single ligand – photophysical, photochemical and electrochemical properties of [Ru(phen)2(TAPHAT)]2+ and [Ru(phen)2(TAPHAT)Ru(phen)2]4+. Dalton Transactions, 46(44), 15287-15300. https://doi.org/10.1039/c7dt03232c (Original work published 2017)