Correlation of electrochemical and theoretical parameters in perylenediimide-[60]fullerene dyads

The electronic structures of complex molecular systems containing fullerene C60 covalently linked to perylenediimide (PDI) have been studied using ab initio Density Functional Theory (DFT) and Hartree-Fock (HF) methods. Semi-empirical PM3 calculations have been used to obtain the optimized geometries, giving an excellent correlation between the torsion angles of the PDI core tetrasubstituted on the bay region and the crystallographic values issued from literature. A satisfactory agreement was found using the DFT/B3LYP method (basis 6-31G(2d,p)), between the theoretically calculated LUMO energies and the cathodic peak potentials measured by cyclic voltammetry of perylenediimide-C60 dyads.