Superatomic molecules with internal electric fields for light harvesting

Traditional p-n junctions used for photovoltaics require an interface where a light induced electron-hole pair is separated by an electric field. Developing alternative strategies for forming strong internal electric fields for electron-hole pair separation offers the possibility for better performance. We demonstrate that fusing two superatomic clusters with donor/acceptor ligands on opposite sides of the cluster leads to such a strong internal electric field. In two fused metal-chalcogenide Re₆S₈Cl₂(L)₄ clusters with donor PMe₃ ligands and acceptor CO ligands on the opposite sides of the fused clusters, the electronic levels undergo shifts analogous to band bending in traditional p-n junctions. The fused cluster has a large dipole moment, and an optical spectrum that strongly absorbs excitation above the HOMO-LUMO gap of the fused clusters, but is optically very weak for the lowest energy excitation that can lead to electron-hole pair recombination. This is because the electron is localized on the CO portion of the fused cluster, while the electron-hole pair is localized on the PMe₃ side of the cluster. It is shown that the electronic states localized on each side of the cluster can be aligned/misaligned by applying a voltage in different directions, offering diode like characteristics.