Diastereoselective Formation of Homochiral Helicates through Subcomponent Self‐Assembly

Homochiral helicates were prepared through subcomponent self‐assembly with a C 2 ‐symmetric chiral building block based on a 6,6′‐substituted 1,1′‐bi‐2‐naphthol (BINOL) scaffold. The resulting complexes were analysed through a broad variety of NMR spectroscopy experiments, high‐resolution mass spectrometry, CD and UV/Vis spectroscopy, and single‐crystal X‐ray diffraction. As proven by these experiments, the self‐assembly occurs through a completely diastereoselective and narcissistic self‐sorting manner to form homochiral Fe 2 L 3 helicates. The stereochemistry of the metal centres is directed by the axial chirality of the BINOL‐based backbone; the ( M )‐configured ligand forms the (Δ,Δ) complex, and the ( P )‐configured ligand forms the (Λ,Λ) complex.