Intramolecular Hydrogen Bonding Effect on the Electron-Transfer Thermodynamics of a Series of o-Nitrobenzyl Alcohol Derivatives.

From thermoelectrochemical experiments and electronic structure calculations of a series of nitrobenzyl alcohol derivatives, the effect of intramolecular hydrogen bonding (IHB) on the electron transfer thermodynamics is discussed on a molecular basis. A linear correlation between formal reduction potential (E1/2) values and temperature was obtained for the temperature range from 300 to 350 K. Estimated electron transfer entropy values (ΔS)─determined from this dependence─and the enthalpy (ΔΔH) changes relative to o-nitrobenzyl alcohol confirmed that the effect of the formation of IHB proved to be decisive in the charge-transfer thermodynamics. The possibility of intermolecular hydrogen bonding is further discussed upon comparing thermodynamic data among three different solvents.

Insights into dissociative electron transfer in esterified shikonin semiquinones by in situ ESR/UV-Vis spectroelectrochemistry.

In this work, electrogenerated anion and dianion species from shikonin and its ester derivative isovalerylshikonin were characterized by means of ESR/UV-Vis spectroelectrochemistry. Analysis of the spectra supported the proposal that stepwise dissociative electron transfer (DET) takes place during the second reduction process of the esterified compound. Quantum chemical calculations were performed for validating the occurrence of this mechanistic pathway and for obtaining thermodynamic information on the electron transfer process; ΔG(cleavage)(0) was estimated to be -0.45 eV, considering that the two possible products of the overall reaction scheme are both a quinone and carboxylate anions.