Heterogeneous single-cluster catalysts (SCCs) comprising atomically precise and isolated metal clusters stabilized on appropriately chosen supports offer exciting prospects for enabling novel chemical reactions owing to their broad structural diversity with unparalled opportunities for engineering their properties. Although the pioneering work revealed intriguing performance trends of size-selected metal clusters deposited on supports, synthetic and analytical challenges hindered a thorough understanding of surface chemistry under realistic conditions. This Review underscores the importance of considering the cluster environment in SCCs, encompassing the development of robust metal-support interactions, precise control over the ligand sphere, the influence of reaction media and dynamic behaviour, to uncover new reactivities. Through examples, we illustrate the criticality of tailoring the entire catalytic ensemble in SCCs to achieve stable and selective performance with practically relevant metal coverages. This expansion in application scope transcends from model reactions to complex and technically relevant reactions. Furthermore, we provide a perspective on the opportunities and future directions for SCC design within this rapidly evolving field.
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