Abstract
In biology, key molecules for life processes rely on cooperation between metal containing porphyrins to function effectively. In technology, (catalysis and sensing) cooperative interactions between the support and metal porphyrins play a key role in their efficiency. In this study, we present a molecular level study of cooperative surface reaction between O2 ligand and Co(II) porphyrin adsorbates as a function of their spatial proximity at the solution/solid interface. Interactions of note include through-support, through-intramolecular-pi structure, and intermolecular communication. Central metal ion reactivity as a function of surface coverage is measured at varying temperatures and ligand concentrations. Reaction rates and thermodynamic parameters are extracted from measurements made on single molecules. DFT calculations are used to provide electronic insights into the observed results.
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