title: Switching of reverse charge transfers for a rational design of an OFF-ON phosphorescent chemodosimeter of cyanide anions.
abstract: A rational approach to luminescence turn-on sensing of cyanide by a dicyanovinyl-substituted acetylide Pt(II) complex, which primarily relies on the nucleophilic addition reaction of cyanide anions to the α-position of the dicyanovinyl group, is described. The strategy used for the design of this cyanide-selective sensor takes advantage of a switch of charge transfer from ML'CT to MLCT/L'LCT in this acetylide Pt(II) sensor. As a result, this chromophore that exhibits almost no basal luminescence displays observable changes in its UV-visible spectrum and acquires strong phosphorescence upon addition of cyanide anions. DFT computations reveal that the frontier molecular orbitals of the anionic system obtained after addition of CN(-) are drastically different from those of the neutral initial species. TD-DFT computations permitted a full assignment of the observed absorption bands and explained well the emissive properties of the species under consideration.
authors.affiliation: Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes 1, 35042 Rennes Cedex, France. jean-luc.fillaut@univ-rennes1.fr
authors.forename: Jean-Luc
authors.initials: JL
authors.lastname: Fillaut
authors.forename: Huriye
authors.initials: H
authors.lastname: Akdas-Kilig
authors.forename: Edouard
authors.initials: E
authors.lastname: Dean
authors.forename: Camille
authors.initials: C
authors.lastname: Latouche
authors.forename: Abdou
authors.initials: A
authors.lastname: Boucekkine
mesh_terms: D000838:Anions / Q000032:analysis; D003486:Cyanides / Q000032:analysis*; D049408:Luminescent Agents / Q000737:chemistry*; D008163:Luminescent Measurements; D009944:Organoplatinum Compounds / Q000737:chemistry*; D013056:Spectrophotometry, Ultraviolet
chemical_list: D000838:Anions; D003486:Cyanides; D049408:Luminescent Agents; D009944:Organoplatinum Compounds