Efficiency of intramolecular electron transfer from the second excited state of the donor in molecular triads D–A1–A2

It is found that intramolecular and intermolecular electron transfer from the second singlet excited state of the donor in all molecular dyads studied up to now is accompanied by ultrafast recombination into the first excited state, resulting in a low quantum yield of the thermalized state with separated charges. The ultrafast photoinduced intramolecular charge transfer in donor‒acceptor 1‒acceptor 2 molecular triads is studied to ascertain the possibilities of increasing the quantum yield of ionic state. It is demonstrated that nonthermal (hot) electron transfer from the primary acceptor to the secondary acceptor can, in parallel with relaxation of a polar solvent, efficiently suppress the ultrafast recombination of charges into the first excited state of the donor and increase the yield of the ionic state. It is established that the angle between the directions of reaction coordinates corresponding to the electron transfer from the donor to the primary acceptor and from the primary acceptor to the secondary acceptor play the most important role in describing these processes. It is concluded that the value of this angle is governed by the ratio between the reorganization energies of the three possible electron transfers in the triad and can vary within wide limits. The parametric regions with maximum quantum yield of the thermalized ionic state are revealed. The strong effect the geometry of a studied triad has on charge separation efficiency is observed.