Probing Edge/Support Electronic Cooperativity in Single Edge Fe/Co6Se8 Clusters
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Updated: Jul 26, 2025

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Published on: September 28, 2016
Benjamin S Mitchell1, Andrei Chirila1, Kevin J Anderton2
1Department of Chemistry, University of Washington, Seattle, Washington 98195, United States.
Abstract:
This study provides insights into the electronic structure of an atomically precise Fe/Co6Se8 cluster and the extent of redox cooperativity between the Fe active site and the noninnocent Co6Se8 support. Chemical oxidation studies enable the isolation of two types of oxidized Fe/Co6Se8 clusters, in which the nature of the counterion (I- or OTf-) significantly impacts the structural interactions between Fe and the Co6Se8 unit. Experimental characterization by single crystal X-ray diffraction, 57Fe Mössbauer spectroscopy, and 31P{1H} NMR spectroscopy is complemented by computational analysis. In aggregate, the study reveals that upon oxidation, the charge is shared between the Fe edge site and the Co6Se8 core.
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