Insights into the Free-Energy Dependence of Intramolecular Dissociative Electron Transfer

To study the relationship between rate and driving force of intramolecular dissociative electron transfers, a series of donor-spacer-acceptor (D-Sp-A) systems has been devised and synthesized. cis-1,4-Cyclohexanedyil and a perester functional group were kept constant as the spacer and acceptor, respectively. By changing the aryl substituents of the phthalimide moiety, which served as the donor, the driving force could be varied by 0.74 eV. X-ray diffraction crystallography and ab initio conformational calculations pointed to D-Sp-A molecules having the cis-(cyclohexane) eqiuatorial(phthalimido)axial(perester) conformation and the same D/A orientation.