Theory-Directed Ligand-Shell Engineering of Ultrasmall Gold Clusters: Remarkable Effects of Ligand Arrangement on...

Ligand-shell engineering of ultrasmall metal clusters is a burgeoning research field aiming to develop cluster-specific properties. However, predicting these properties prior to synthesis is challenging due to their high sensitivity to geometric and/or electronic variations in ultrasmall metal cores, hindering further exploration. In this study, we present a theory-directed ligand-shell design and significant red-shift in absorption of a prolate-shaped [Au₈(diphosphine)₄Cl₂]²⁺ cluster by synthesizing and characterizing enantiopure octagold clusters bearing chiral BINAP-type ligands [BINAP = 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl]. Crystallographic analysis reveals the predesigned ligand arrangement and twisted gold-core framework. The enantiomeric clusters show significant changes in both absorption and photoluminescence compared with a previous Au₈ analogue and exhibit chiroptical signals. Furthermore, theoretical calculations visually unveil the atomic level origins of their optical and chiroptical absorption characteristics. This work not only highlights the effectiveness of ligand-shell engineering in creating unique photophysical properties but also offers a viable, theory-guided strategy for designing and functionalizing ligated metal clusters.