Models to study photoinduced multiple proton coupled electron transfer processes

Abstract

In water-oxidizing photosynthetic organisms, excitation of the reaction-center chlorophylls (P680) triggers a cascade of electron and proton transfer reactions that establish charge separation across the membrane and proton-motive force. An early oxidation step in this process involves proton-coupled electron transfer (PCET) via a tyrosine-histidine redox relay (Yz-H190). Herein, we report the synthesis and structural characterization of two isomeric dyads designed to model this PCET process. Both are based on the same high potential fluorinated porphyrin (model for P680), linked to isomeric pyridylbenzimidazole-phenols (models for Yz-H190). The two isomeric dyads have different hydrogen bond frameworks, which is expected to change the PCET photooxidation mechanism. In these dyads, 1H NMR evidence indicates that in one dyad the hydrogen bond network would support a Grotthuss-type proton transfer process, whereas in the other the hydrogen bond network is interrupted. Photoinduced one-electron, two-proton transfer is expected to occur in the fully hydrogen-bonded dyad upon oxidation of the phenol by the excited state of the porphyrin. In contrast for the isomer with the interrupted hydrogen bond network, an ultrafast photoinduced one-electron one-proton transfer process is anticipated, followed by a much slower proton transfer to the terminal proton acceptor. Understanding the nature of photoinduced PCET mechanisms in these biomimetic models will provide insights into the design of future generations of artificial constructs involved in energy conversion schemes.