Probing Edge/Support Electronic Cooperativity in Single Edge Fe/Co₆Se₈ Clusters

Thisstudy provides insights into the electronic structure of anatomically precise Fe/Co6Se8 cluster and theextent of redox cooperativity between the Fe active site and the noninnocentCo(6)Se(8) support. Chemical oxidation studies enablethe isolation of two types of oxidized Fe/Co6Se8 clusters, in which the nature of the counterion (I- or OTf-) significantly impacts the structuralinteractions between Fe and the Co6Se8 unit.Experimental characterization by single crystal X-ray diffraction, Fe-57 Mo''ssbauer spectroscopy, and P-31{H-1} NMR spectroscopy is complemented by computational analysis.In aggregate, the study reveals that upon oxidation, the charge isshared between the Fe edge site and the Co6Se8 core. This study investigates theedge/core localization of thecharge upon removing an electron from an Fe/Co6Se8 single edge cluster. The counterion identity reveals the tippingpoint between strong edge/support binding when the anion is triflate,and Fe-Se bond cleavage when the anion is iodide.