Adjacent backbone interactions control self-sorting of chiral heteroleptic Pd3A2B4 isosceles triangles and Pd4A4C4 pseudo-tetrahedra

Taking inspiration from biological structures, self-assembled nano-objects promise application potential, e.g., in selective catalysis, smart materials, and drug delivery. While integrating multiple different building blocks greatly enhances their versatility, it is a challenge to design low-symmetry multicomponent structures without generating statistical mixtures. Based on adjacent backbone interactions (ABIs), we introduce here a series of integratively self-sorted PdnL2n (n = 3, 4) assemblies, each comprising two distinct, easily accessible ligands. In these Pd3A2B4 isosceles triangles and Pd4A4C4 pseudo-tetrahedra, one ligand is always chiral. Noteworthy, the triangular structures contrast previously described heteroleptic Pd3L6 assemblies in that the two differentiable ligands are not contained in equal stoichiometries. The chiral assemblies bind and strongly discriminate chiral guests. They can coexist orthogonally, leading to cage populations under heteromeric narcissistic self-sorting. We further present a computational toy model toward structure prediction of such assemblies, opening avenues for the rational design of discrete metallosupramolecular three-dimensional architectures.