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Regioselectivity of concerted proton-electron transfer at the surface of a polyoxovanadate cluster.

ABSTRACT: Proton-coupled electron transfer (PCET) is an important process in the activation and reactivity of metal oxide surfaces. In this work, we study the electronic structure of a reduced polyoxovanadate-alkoxide cluster bearing a single bridging oxide moiety. The structural and electronic implications of the incorporation of bridging oxide sites are revealed, most notably resulting in the quenching of cluster-wide electron delocalization in the most reduced state of the molecule. We correlate this attribute to a change in regioselectivity of PCET to the cluster surface (e.g. reactivity at terminal vs. bridging oxide groups). Reactivity localized at the bridging oxide site enables reversible storage of a single H-atom equivalent, changing the stoichiometry of PCET from a 2e^-/2H⁺ process. Kinetic investigations indicate that the change in site of reactivity translates to an accelerated rate of e^-/H⁺ transfer to the cluster surface. Our work summarizes the role which electronic occupancy and ligand density play in the uptake of e^-/H⁺ pairs at metal oxide surfaces, providing design criteria for functional materials for energy storage and conversion processes.

SUBMITTER: Schreiber E

PROVIDER: S-EPMC9906639 | biostudies-literature | 2023 Feb

REPOSITORIES: biostudies-literature

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Regioselectivity of concerted proton-electron transfer at the surface of a polyoxovanadate cluster.

Schreiber Eric E Brennessel William W WW Matson Ellen M EM

Chemical science 20221220 6

Proton-coupled electron transfer (PCET) is an important process in the activation and reactivity of metal oxide surfaces. In this work, we study the electronic structure of a reduced polyoxovanadate-alkoxide cluster bearing a single bridging oxide moiety. The structural and electronic implications of the incorporation of bridging oxide sites are revealed, most notably resulting in the quenching of cluster-wide electron delocalization in the most reduced state of the molecule. We correlate this a ...[more]

PMID: 36794190

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Project description:The coupling between electrons and protons and the long-range transport of protons play important roles throughout biology. Biomimetic systems derived from benzimidazole-phenol (BIP) constructs have been designed to undergo proton-coupled electron transfer (PCET) upon electrochemical or photochemical oxidation. Moreover, these systems can transport protons along hydrogen-bonded networks or proton wires through multiproton PCET. Herein, the nonequilibrium dynamics of both single and double proton transfer in BIP molecules initiated by oxidation are investigated with first-principles molecular dynamics simulations. Although these processes are concerted in that no thermodynamically stable intermediate is observed, the simulations predict that they are predominantly asynchronous on the ultrafast time scale. For both systems, the first proton transfer typically occurs ∼100 fs after electron transfer. For the double proton transfer system, typically the second proton transfer occurs hundreds of femtoseconds after the initial proton transfer. A machine learning algorithm was used to identify the key molecular vibrational modes essential for proton transfer: a slow, in-plane bending mode that dominates the overall inner-sphere reorganization, the proton donor-acceptor motion that leads to vibrational coherence, and the faster donor-hydrogen stretching mode. The asynchronous double proton transfer mechanism can be understood in terms of a significant mode corresponding to the two anticorrelated proton donor-acceptor motions, typically decreasing only one donor-acceptor distance at a time. Although these PCET processes appear concerted on the time scale of typical electrochemical experiments, attaching these BIP constructs to photosensitizers may enable the detection of the asynchronicity of the electron and multiple proton transfers with ultrafast two-dimensional spectroscopy. Understanding the fundamental PCET mechanisms at this level will guide the design of PCET systems for catalysis and energy conversion processes.

Dataset Information

Regioselectivity of concerted proton-electron transfer at the surface of a polyoxovanadate cluster.

Publications

Regioselectivity of concerted proton-electron transfer at the surface of a polyoxovanadate cluster.

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