Switching of Reverse Charge Transfers for a Rational Design of an OFF-ON Phosphorescent Chemodosimeter of Cyanide Anions


Fillaut J., Akdas-Kilig H. , Dean E., Latouche C., Boucekkine A.

INORGANIC CHEMISTRY, vol.52, no.9, pp.4890-4897, 2013 (Journal Indexed in SCI) identifier identifier identifier

  • Publication Type: Article / Article
  • Volume: 52 Issue: 9
  • Publication Date: 2013
  • Doi Number: 10.1021/ic302478e
  • Title of Journal : INORGANIC CHEMISTRY
  • Page Numbers: pp.4890-4897

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 alpha-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 acetylicle 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.