The near infra red (NIR) chiroptical properties of nickel dithiolene complexes †

Yann Le Gal (1) , Antoine Vacher (1) , Vincent Dorcet (1) , Marc Fourmigué (1) , Jeanne Crassous (1) , Dominique Lorcy (1)

1 ISCR - Institut des Sciences Chimiques de Rennes

Enantiomerically pure dianionic, monoanionic and neutral dithiolene complexes formulated as[Ni((R,R)-CHMePh-thiazdt)2]2,1,0 and [Ni((S,S)-CHMePh-thiazdt)2]2,1,0 (CHMePh-thiazdt: N-(1-phenylethyl)-1,3-thiazoline-2-thione-4,5-dithiolate) have been synthesized from the enantiopure N-(1-phenylethyl)-1,3-thiazoline-2-thione precursors. The electrochemical and spectro-electrochemical investigations carriedout on these complexes show that the CHMePh-thiazdt ligands act as electron rich ligands and that thecomplexes are strong near infrared (NIR) absorbers in the range of 800–1100 nm for the neutral species and1050–1500 nm for the reduced radical anion species. Circular dichroism (CD) thin layer spectroelectrochemicalexperiments carried out on the neutral (R,R) enantiomer, [Ni((R,R)-CHMePh-thiazdt)2],revealed a redox switching of CD-active bands, not only in the UV-vis but also in the NIR region.

Domains: Chemical Sciences; Organic chemistry

Yann Le Gal, Antoine Vacher, Vincent Dorcet, Marc Fourmigué, Jeanne Crassous, et al.. The near infra red (NIR) chiroptical properties of nickel dithiolene complexes †. New Journal of Chemistry, 2015, 39 (1), pp.122-129. ⟨10.1039/c4nj01244e⟩. ⟨hal-01160235⟩