Modular enhancement of circularly polarized luminescence in Pd₂A₂B₂ heteroleptic cages

Metal-mediated assembly allows us to combine an achiral emissive ligand A with different chiral ligands (such as B) in a non-statistical fashion, obtaining Pd₂A₂B₂ heteroleptic cages showing circularly polarized luminescence (CPL). By using the 'shape complementary assembly' (SCA) strategy, the cages are exclusively obtained as cis-Pd₂A₂B₂ stereoisomers, as confirmed by NMR, MS and DFT analyses. Their unique chiroptical properties derive from the synergy of all the building blocks. Ligand B imparts the chiral information of its aliphatic backbone, comprising two stereogenic sp³ carbon centres, to the overall structure, causing CD and CPL signal induction for the chromophore on ligand A. The heteroleptic cage shows CPL with a |g_lum| value of 2.5 × 10^-3, which is 3-times higher than that for a progenitor based on aromatic helical building block H, thus opening a rational route towards optimizing the CPL properties of self-assembled nanostructures in a modular way.