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



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 non-innocent Co6Se8 support. Chemical oxidation studies enable the isolation of two types of oxidized Fe/Co6Se8 clusters, in which the counterion is either directly coordinated to the Fe, or completely dissociated. Experimental characterization by single crystal X-ray diffraction, 57Fe Mössbauer spectroscopy, and 31P 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, and that anion coordination perturbs the density of unpaired electrons on Co6Se8.


Supplementary material

Supporting Information
General experimental considerations, synthetic protocols, and experimental characterization including crystallographic data, NMR studies, and computational investigations.