Effect of group electronegativity on electron transfer in bis(hydrazine) radical cations

J Phys Chem A. 2011 Apr 14;115(14):3116-21. doi: 10.1021/jp110724f. Epub 2011 Mar 17.

Abstract

The radical cation of 4,10-ditert-butyl-5,9-diisopropyl-4,5,9,10-tetraazatetracyclo[6.2.2.2]-tetradecane (sBI4T(+)), as well as its substituted bis(hydrazine) radical cations, is chosen for the investigation of the electronegativity dependence of its intramolecular electron transfer. To do so, two parameters, reorganization energy and electronic coupling, are calculated with several ab initio approaches. It is found that the electronic couplings decrease with the increase of the group electronegativity while the reorganization energies do not show an explicit dependency. Furthermore, Marcus formula is employed to reveal those effect on the electron transfer rates. The predicted rates of electron transfer generally decrease with increasing group electronegativity, although not monotonically.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Cations / chemistry
  • Electrons*
  • Free Radicals / chemistry
  • Hydrazines / chemistry*
  • Molecular Structure
  • Quantum Theory

Substances

  • Cations
  • Free Radicals
  • Hydrazines