Cis-trans isomerisation of azobenzenes studied by NMR spectroscopy with in situ laser irradiation and DFT calculations

NMR spectroscopy with in situ laser irradiation has been used to investigate the photo- and thermal isomerisation of eight azobenzene derivatives; diphenyldiazene (azobenzene), p-phenylazoaniline (p-aminoazobenzene), 4-(dimethylamino)azobenzene (Methyl Yellow), 4-dimethylamino-2-methylazobenzene (o-Methyl-Methyl Yellow), p-nitroazobenzene, 4-nitro-4’-dimethylaminoazobeneze (Dimethyl-nitroazobenzene), 4-(4-nitrophenylazo)aniline (Disperse Orange 3) and N-ethyl-N-(2-hydroxyethyl)-4-(4-nitrophenylazo) (Disperse Red 1). The rate constants and activation parameters of the thermal cis-to-trans isomerisation have been measured experimentally and correlated to the mechanism of isomerisation in two solvents. The experimental data show that the values of the activation energy (related to the enthalpy of activation) and the entropy of activation (related to the Arrhenius pre-exponential factor) vary significantly from molecule to molecule and thus both of these parameters influence the inter-molecule variation of the rate constant. Similarly, both of these parameters influence the solvent-dependence of the rate constant. Complementary computational studies have been carried out in the gas phase and in solution using density functional theory (DFT) to predict the structures of the cis and trans isomers and the transition state, and to explore the reaction coordinate. The theoretically predicted activation parameters are compared with those determined experimentally, and the utility of DFT calculations in predicting the effects of molecular structure and solvation on the kinetics of cis-to-trans isomerisation assessed. The DFT-predicted values of the activation energy and Gibbs free energy of activation in DMSO are in good agreement with the experimental values, while the values in benzene tend to be in less good agreement. The DFT calculations are unsuccessful at predicting the entropy of activation, where in all cases there is a large discrepancy between the theoretical and experimental values. The DFT- calculated energy differences between the activation energies of the two inversion pathways for the asymmetric azobenzenes suggests the favourable phenyl ring for inversion. The formation of a linear transition state from a dihedral rotation potential energy curve is explained in terms of the lower activation barrier of the more favourable inversion route (α-inversion) than that of the dihedral rotation pathway, and suggests the inversion through the α-phenyl ring to be the favoured pathway for substituted azobenzene. DFT calculations are able to obtain a transition state corresponding to pure rotation pathway for two azobenzene derivatives. The higher activation barrier for the formation of the transition state corresponding to this pathway compared to that of the formation of the α-transition state confirmed the previous conclusion. DFT predictions of the effect of protonation on the thermal rates of isomerisation of azobenzenes substituted with electron-donating group were in good agreement with the experimental results; both conclude faster isomerisation and lower activation barriers on protonation. However, DFT calculations could not confirm the postulation of rotational transition state for the isomerisation of the protonated molecule, as a result of weakening of the N=N bond by protonation