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.

Automated summary

This study provides insights into the electronic structure of the Fe/Co6Se8 cluster and the redox cooperativity between the Fe active site and the Co6Se8 support. Different types of oxidized Fe/Co6Se8 clusters are isolated depending on the counterion used, and experimental characterization and computational analysis are used to investigate the charge distribution. The findings show that the charge is shared between the Fe edge site and the Co6Se8 core upon oxidation.