An Inherently Chiral Au₂₄ Framework with Double‐Helical Hexagold Strands

Abstract

Abstract 2,3‐bis(diphenylphosphino)butane enantiomers (chiraphos, L) used as chiral auxiliaries results in the preferential formation of an unprecedented Au 24 framework with inherent chirality. The crystal structure of [Au 24 L 6 Cl 4 ] 2+ ( 1 ) has a square antiprism‐like octagold core twinned by two helicene‐like hexagold motifs, where the inherent chirality is associated with the helical arrangement. The clusters carrying ( R , R )‐ and ( S , S )‐ diphosphines had right‐ and left‐handed strands, respectively. Circular dichroism spectra showed peaks in the visible to near‐IR region, some of which did not coincide with absorption bands, suggesting the enantiomeric Au 24 frameworks possess unique chiroptical properties. The Au 24 frameworks were thermally robust, which could be attributed to the superatomic concept (18 e − system) and the steric constraint effects of the bridging ligand units.