CuAAC-based assembly and characterization of a ruthenium–copper dyad containing a diimine–dioxime ligand framework

Nicolas Queyriaux (1) , Eugen S. Andreiadis (1) , Stéphane Torelli (1) , Jacques Pécaut (2, 3) , Brad S. Veldkamp (4, 5) , Eric A. Margulies (4, 5) , Michael R. Wasielewski (4, 5) , Murielle Chavarot-Kerlidou (1) , Vincent Artero (1)

1 LCBM - UMR 5249 - Laboratoire de Chimie et Biologie des Métaux
2 CIBEST - Chimie Interface Biologie pour l’Environnement, la Santé et la Toxicologie
3 INAC - Institut Nanosciences et Cryogénie
4 Department of Chemistry [Evanston]
5 ANSER - Argonne-Northwestern Solar Energy Research Center

The design of molecular dyads combining a light-harvesting unit with an electroactive centre is highly demanded in the field of artificial photosynthesis. The versatile Copper-catalyzed Azide–Alkyne Cycloaddition (CuAAC) procedure was employed to assemble a ruthenium tris-diimine unit to an unprecedented azide-substituted copper diimine–dioxime moiety. The resulting RuIICuII dyad 4 was characterized by electrochemistry, 1H NMR, EPR, UV-visible absorption, steady-state fluorescence and transient absorption spectroscopies. Photoinduced electron transfer from the ruthenium to the copper centre upon light-activation in the presence of a sacrificial electron donor was established thanks to EPR-monitored photolysis experiments, opening interesting perspectives for photocatalytic applications.

Mots clés: Copper; ruthenium; CuAAC coupling; light-activated dyad; EPR; photolysis

Domaines: Chimie de coordination; Catalyse

Nicolas Queyriaux, Eugen S. Andreiadis, Stéphane Torelli, Jacques Pécaut, Brad S. Veldkamp, et al.. CuAAC-based assembly and characterization of a ruthenium–copper dyad containing a diimine–dioxime ligand framework. Faraday Discussions, 2017, 198, pp.251-261. ⟨10.1039/C6FD00204H⟩. ⟨hal-01534973⟩