Switching of reverse charge transfers for a rational design of an OFF-ON phosphorescent chemodosimeter of cyanide anions

Inorg Chem. 2013 May 6;52(9):4890-7. doi: 10.1021/ic302478e. Epub 2013 Apr 8.

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.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Anions / analysis
  • Cyanides / analysis*
  • Luminescent Agents / chemistry*
  • Luminescent Measurements
  • Organoplatinum Compounds / chemistry*
  • Spectrophotometry, Ultraviolet

Substances

  • Anions
  • Cyanides
  • Luminescent Agents
  • Organoplatinum Compounds