Figure 1.

a, b) Synthesis of ligands L¹ and L² from 2,15‐dibromo[6]helicene 3 followed by separation into the P (red) and M (green) enantiomers. The addition of stoichiometric amounts of Pd^II leads to the quantitative formation of different coordination cages, depending on the enantiomeric composition and length of the ligand. Racemic L¹ exclusively gives C1 ^meso, whereas racemic L² leads to a statistical mixture of all possible stereoisomers (PPPM/MMMP/PPMM/PMPM/PPPP/MMMM, shown in gray). The enantiopure ligands give the chiral coordination cages C1 ^P/M and C2 ^P/M and the interpenetrated dimer DC2 ^P/M.