Proton-Coupled Electron Transfer for Photoinduced Generation of Two-Electron Reduced Species of Quinone.

Purpose-built molecules that follow the fundamental process of photosynthesis have significance in developing better insight into the natural photosynthesis process. Quinones have a significant role as electron acceptors in natural photosynthesis, and their reduction is assisted through H-bond donation or protonation. The major challenge in such studies is to couple the multielectron and proton-transfer process and to achieve a reasonably stable charge-separated state for the elucidation of the mechanistic pathway. We have tried to address this issue through the design of a donor-acceptor-donor molecular triad (2RuAQ) derived from two equivalent [Ru(bpy)] derivatives and a bridging anthraquinone moiety (AQ). Photoinduced proton-coupled electron transfer (PCET) for this molecular triad was systematically investigated in the absence and presence of hexafluoroisopropanol and -toluenesulfonic acid (PTSA) using time-resolved absorption spectroscopy in the ultrafast time domain. Results reveal the generation of a relatively long-lived charge-separated state in this multi-electron transfer reaction, and we could confirm the generation of AQ and Ru as the transient intermediates. We could rationalize the mechanistic pathway and the dynamics associated with photoinduced processes and the role of H-bonding in stabilizing charge-separated states. Transient absorption spectroscopic studies reveal that the rates of intramolecular electron transfer and the mechanistic pathways associated with the PCET process are significantly different in different solvent compositions having different polarities. In acetonitrile, a concerted PCET mechanism prevails, whereas the stepwise PCET reaction process is observed in the presence of PTSA. The results of the present study represent a unique model for the mechanistic diversity of PCET reactions.