Constructing hierarchical superstructures to achieve comparable complexity and functions to proteins with four-level hierarchy is challenging, which relies on the elaboration of novel building blocks with complex structures. We present a series of catenated cages with unique structural complexity and tailorability. The rational design was realized as such: A catenane of two symmetric cages (CSC), CSC-1, with all rigid imine panels was converted to a catenane of two dissymmetric cages (CDC), CDC-1, with two exterior flexible amine panels, and CDC-5 was tailored from CDC-1 by introducing an additional methyl group on each blade to increase lateral hindrance. CDC-1s with the most irregular and flexible configuration formed supramolecular dimers, which self-organized into 3D continuous wavelike plank with a three-level hierarchy, previously undiscovered by conventional building blocks. A drastically different 3D triclinic crystalline phase with a four-level hierarchy and trigonal phase with a three-level hierarchy were constructed of distorted CSC-1s and the most symmetric CDC-5s, respectively. The wavelike plank exhibited the lowest order, and the triclinic phase had a lower order than the trigonal phase which had the highest order. It correlates with the configuration of the primary structures, namely, the most disordered shape of CDC-1, the low-order configuration of CSC-1, and the most ordered geometry of CDC-5. The catenated cages with subtle structural differences therefore provide a promising platform for the search of emerging hierarchical superstructures that might be applied to proton conductivity, ferroelectricity, and catalysis.

The spontaneous resolution of racemates, from natural compounds to artificial structures, has long been pursued to shed light on the origin of homochirality in life. Even though diverse synthetic systems have been elegantly devised to elaborate the underlying principles of spontaneous symmetry breaking, their complexity is still unparalleled to the natural masterpieces including DNA helix and proteins, which convey remarkable coalescence at both molecular and supramolecular levels. Here, we report on the spontaneous resolution of a pair of homochiral entities from a racemic mixture of a triply interlocked cage-catenane comprising 720 possible stereoisomers. This cage-catenane comprises six methyldithiane ring-containing linkers (denoted rac-2). As each methyldithiane ring has two chiral centers, it exhibits four possible diastereomers. These otherwise equimolar diastereomers are preferentially differentiated with the equatorial conformers over their axial analogues, leading to the dominant formation of ( S , R )-2 and ( R , S )-2, i.e., diastereomeric enrichment at the molecular level. This diastereomeric enrichment is unbiasedly transferred from precursor rac-2 to cage-catenane rac-4, from which a pair of homochirals ( S , R ) 6 -4 and ( R , S ) 6 -4 is narcissistically self-sorted upon crystallization. This powerful symmetry breaking is attributed to a supramolecular synergy of directional π–π stacking with the multivalency of erstwhile weak S···S contacts (with an unusual distance of 3.09 Å) that are cooperatively arranged in a helical fashion. This work highlights the attainability of complex homochiral entities by resorting to coalesced covalent and noncovalent contributions and therefore provides additional clues to the symmetry breaking of sophisticated yet well-defined architectures.