The intriguing interplay of chirality, degree of chelation (denticity), and hydrogen bonding enables the diastereoselective formation of diverse asymmetrical and lowsymmetric architectures (MOC-13-16) through subcomponent self-assembly (Figure ). Enantiopure components bearing H-bond donors and acceptors (S-A) form M4L4 assemblies (MOC-13), whereas racemic mixtures give rise to M3L3 stacks (MOC-14). Chiral amplification was observed within MOC-14 enantiomers upon utilization of 2:1 ratio of R-and S-subcomponent enantiomers. By altering the solvent (from acetonitrile to methanol) or ligating unit (from bidentate 2-formylpyridine (P 1 ) to tridentate 2-formylphenanthroline (P 2 ), the range of structures that can be derived from these building blocks was expanded. This resulted in the selective formation of novel M3L2 (MOC-15) and M2L2 (MOC-16) assemblies.