A two-ligand system composed of the predesigned multivalent and complementary terpyridine-based ligands was exploited to construct heteroleptic metallo-supramolecules and to investigate the self-assembly mechanism. Molecular stellation of the trimeric hexagon [Cd6 L 2 3] gave rise to the exclusive self-assembly of the star hexagon [Cd18 L 1 6 L 3 3] through complementary ligand pairing between the ditopic and octatopic tectons. To understand how the intermolecular heteroleptic complexation influenced the self-assembly pathway, the star hexagon was truncated into two triangular fragments: [Cd12 L 1 3 L 4 3] and [Cd12 L 1 3 L 5 3]. In the self-assembly of [Cd12 L 1 3 L 4 3], the conformational movements of hexatopic ligand L 4 could be regulated by L 1 to promote the subsequent coordination event, which was the key step to the successful multicomponent self-assembly. In contrast, the formation of [Cd12 L 1 3 L 5 3] was hampered by the geometrically mismatched intermediates.

Upon treatment with Zn ions, a series of BINOL-bridged bis(phenanthroline) ligands was self-assembled into [ML] metallocages, which were carefully characterized by NMR spectroscopy and ESI-MS spectrometry. Among them, a racemic mixture of the BINOL-bridged bis(phenanthrolines) underwent chiral self-sorting to afford two homochiral metallocages. The narcissistic self-sorting process of the metallocages was observed in the complexation reaction of the constitutionally isomeric bis(phenanthrolines) with varying connection positions. Moreover, the endo hydroxyl-functionalized metallocage [Zn{( S)-L2}] exhibited catalytic activity and substrate selectivity for the Knoevenagel condensation reactions of aromatic tricarbaldehydes with malononitrile.