Cis-Trans isomerisation of azobenzenes studied by laser-coupled NMR spectroscopy and DFT calculations

Nuha A. Wazzan, Patricia R. Richardson, Anita C. Jones

Research output: Contribution to journalArticlepeer-review

Abstract

In a combined experimental and computational study of a group of para-substituted azobenzenes, the effects of substituents and solvent on the kinetics of thermal cis-to-trans isomerisation have been examined and the success of DFT calculations in predicting kinetic parameters assessed. Mono-substituted species are predicted to isomerise by inversion in both non-polar and polar solvent, whereas for push-pull azobenzenes the mechanism is predicted to change from inversion to rotation on going from non-polar to polar solvent. Computed free energies of activation qualitatively reproduce experimental trends but do not quantitatively predict the kinetics of cis-trans isomerisation. The polarisable continuum model of solvation fails to predict the experimentally observed influence of solvent on the entropy of activation.

Original languageEnglish
Pages (from-to)968-974
Number of pages7
JournalPhotochemical & Photobiological Sciences
Volume9
Issue number7
Early online date24 May 2010
DOIs
Publication statusPublished - 1 Jul 2010

Keywords

  • QUANTUM-CHEMICAL CALCULATIONS
  • PUSH-PULL AZOBENZENES
  • SUBSTITUTED AZOBENZENES
  • THERMAL-ISOMERIZATION
  • INVERSION MECHANISM
  • AZO DYES
  • SOLVENT
  • PHOTOISOMERIZATION
  • DERIVATIVES
  • TEMPERATURE

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