Donor-acceptor tubular nanoaggregates of cyclic oligothiophenes. A theoretical study

The geometries of neutral, monooxidized, and monoreduced donor-acceptor tubular aggregates of cyclo[8]thiophene, cyclo[8](3,4-dicyanothiophene), and the corresponding donor-acceptor tubular nanoaggregates containing up to 4 repeating units were fully optimized at MPWB1K/3-21G* level of theory. The binding energies between macrocycles in neutral donor-acceptor tubular aggregates (77-84 kcal/mol) were found to be much higher compared to donor (43-45 kcal/mol) or acceptor (27-28 kcal/mol) aggregates. The oxidation or the reduction of the donor-acceptor tubular aggregates lead to a decrement in the binding energy. However, the reduction increases the binding in acceptor aggregates and decreases in donor ones, whereas the oxidation causes the opposite effect. In spite of a decrease in the binding energy in donor-acceptor aggregates in oxidized or reduced states, they remain the most thermodynamically stable formations. Donor-acceptor aggregates possess the lowest band gap among all studied systems (1.31 eV for the tetramer) and the photoexcitation of donor-acceptor aggregates results in almost complete electron transfer from donor to acceptor fragment, thus showing a very strong charge separation in the excited-state, which is highly desirable in materials with potential application in photovoltaic devices. Polaron cations are localized at donor fragments, whereas polaron anions are located at acceptor units.