Solvent-mediated chirality inversion in orthogonal hierarchical assembly of achiral carbene-anchored gold cluster

Precisely constructing homochiral helical nanostructures from achiral molecules by non-covalent interactions remains challenging owing to the untraceable handedness control at different hierarchical levels. Here, we present an aurophilicity-assisted orthogonal assembly strategy, enabling not only the homochiral assembly of an achiral carbene-anchored trinuclear gold cluster with chiral amines but also the inversion of circularly polarized luminescence (CPL). This gold cluster could spontaneously form random right- or left-handed helices, while introduction of chiral amines effectively drives the formation of hierarchically homochiral twists with |glum| of 10⁻², directed by inherent aurophilicity of gold cluster and orthogonal intermolecular C-H⋅⋅⋅O/N interactions. Furthermore, by fine-tuning the assembly conditions from DMF to DMF/H₂O solvent, the morphology of assemblies can be specifically controlled, resulting in inversion of CPL signals. This study highlights the potential of aurophilicity-driven orthogonal assembly strategy in effectively controlling hierarchical chirality and paves the way for advancing chiral metallo-superstructures.