Probing Edge/Support Electronic Cooperativity in Single Edge Fe/CoSe Clusters.

This study provides insights into the electronic structure of an atomically precise Fe/CoSe cluster and the extent of redox cooperativity between the Fe active site and the noninnocent CoSe support. Chemical oxidation studies enable the isolation of two types of oxidized Fe/CoSe clusters, in which the nature of the counterion (I or OTf) significantly impacts the structural interactions between Fe and the CoSe unit. Experimental characterization by single crystal X-ray diffraction, Fe Mössbauer spectroscopy, and P{H} 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 CoSe core.