Issue 34, 2024

Cu site differentiation in tetracopper(i) sulfide clusters enables biomimetic N2O reduction

Abstract

Copper clusters feature prominently in both metalloenzymes and synthetic nanoclusters that mediate catalytic redox transformations of gaseous small molecules. Such reactions are critical to biological energy conversion and are expected to be crucial parts of renewable energy economies. However, the precise roles of individual metal atoms within clusters are difficult to elucidate, particularly for cluster systems that are dynamic under operating conditions. Here, we present a metal site-specific analysis of synthetic Cu44-S) clusters that mimic the CuZ active site of the nitrous oxide reductase enzyme. Leveraging the ability to obtain structural snapshots of both inactive and active forms of the synthetic model system, we analyzed both states using resonant X-ray diffraction anomalous fine structure (DAFS), a technique that enables X-ray absorption profiles of individual metal sites within a cluster to be extracted independently. Using DAFS, we found that a change in cluster geometry between the inactive and active states is correlated to Cu site differentiation that is presumably required for efficient activation of N2O gas. More precisely, we hypothesize that the Cuδ+⋯Cuδ pairs produced upon site differentiation are poised for N2O activation, as supported by computational modeling. These results provide an unprecedented level of detail on the roles of individual metal sites within the synthetic cluster system and how those roles interplay with cluster geometry to impact the reactivity function. We expect this fundamental knowledge to inform understanding of metal clusters in settings ranging from (bio)molecular to nanocluster to extended solid systems involved in energy conversion.

Graphical abstract: Cu site differentiation in tetracopper(i) sulfide clusters enables biomimetic N2O reduction

Supplementary files

Article information

Article type
Edge Article
Submitted
29 Jan 2024
Accepted
31 Jul 2024
First published
31 Jul 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2024,15, 13668-13675

Cu site differentiation in tetracopper(I) sulfide clusters enables biomimetic N2O reduction

P. Alayoglu, S. C. Rathnayaka, T. Chang, S. G. Wang, Y. Chen and N. P. Mankad, Chem. Sci., 2024, 15, 13668 DOI: 10.1039/D4SC00701H

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