Hexameric Lanthanide–Organic Capsules with Tertiary Structure and Emergent Functions

Biological macromolecules always function through a collective behavior of the aggregated constituents, which usually are self-assembled together via noncovalent interactions. Likewise, artificial supramolecular assemblies, whose properties and functions are mainly derived from their primary and secondary structures, may also aggregate into high-order architectures with emergent functions not available on the individual components. Here we report the first example of an insulin-like hexamerization of lanthanide triple helicates toward a 4 nm diameter hexameric capsule via consecutive metal-directed and anion-directed assembly processes. Hierarchical chiral-sorting self-assembly endows hexamers with aggregation-induced stability and emission enhancement. Furthermore, emergent guest-encapsulation function and enantioselectivity toward terpene drugs have been realized in the late-formed central cavity of the hexamers. This study not only provides a feasible strategy for constructing sophisticated and multifunctional lanthanide–organic materials but also sheds some light on the self-assembly processes in nature.