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

Benjamin S Mitchell; Andrei Chirila; Kevin J Anderton; Werner Kaminsky; Alexandra Velian

doi:10.1021/acs.inorgchem.3c01661

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

Inorg Chem. 2023 Jul 3;62(26):10497-10503. doi: 10.1021/acs.inorgchem.3c01661. Epub 2023 Jun 15.

Authors

Benjamin S Mitchell¹, Andrei Chirila¹, Kevin J Anderton², Werner Kaminsky¹, Alexandra Velian¹

Affiliations

¹ Department of Chemistry, University of Washington, Seattle, Washington 98195, United States.
² Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States.

PMID: 37318196
DOI: 10.1021/acs.inorgchem.3c01661

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.