Considerable efforts have been made to increase the topological complexity of mechanically interlocked molecules over the years. Three‐dimensional catenated structures composed of two or several (usually symmetrical) cages are one representative example. However, owing to the lack of an efficient universal synthetic strategy, interlocked structures made up of dissymmetric cages are relatively rare. Since the space volume of the inner cavity of an interlocked structure is smaller than that outside it, we developed a novel synthetic approach with the voluminous reductant NaBH(OAc)3 that discriminates this space difference, and therefore selectively reduces the outer surface of a catenated dimer composed of two symmetric cages, thus yielding the corresponding catenane with dissymmetric cages. Insight into the template effect that facilitates the catenation of cages was provided by computational and experimental techniques.

Considerable efforts have been made to increase the topological complexity of mechanically interlocked molecules over the years. Three‐dimensional catenated structures composed of two or several (usually symmetrical) cages are one representative example. However, owing to the lack of an efficient universal synthetic strategy, interlocked structures made up of dissymmetric cages are relatively rare. Since the space volume of the inner cavity of an interlocked structure is smaller than that outside it, we developed a novel synthetic approach with the voluminous reductant NaBH(OAc)3 that discriminates this space difference, and therefore selectively reduces the outer surface of a catenated dimer composed of two symmetric cages, thus yielding the corresponding catenane with dissymmetric cages. Insight into the template effect that facilitates the catenation of cages was provided by computational and experimental techniques.

Spontaneous deracemization has been used to separate homochiral domains from the racemic system. However, homochirality can only be referred to when the scales of these domains and systems are specified. To clarify this, we report self‐assembly of racemates of dissymmetric cages DC‐1 with a cone‐shape propeller geometry, forming a centrosymmetric columnar crystalline phase (racemic at crystallographic level). Owing to their anisotropic geometry, the two enantiomers are packed in a frustrated fashion in this crystalline phase; single‐handed double helices are observed (single‐handedness at supramolecular level). The frustrated packing (layer continuity break‐up) in turn facilitates screw dislocation during the crystal growth, forming left‐ or right‐handed spiral platelets (symmetry‐breaking at morphological level), although each platelet is composed of DC‐1 racemates. The symmetry correlation between DC‐1 molecules, the crystalline phase and spiral platelets, all exhibit C3 symmetry.

Six trigonal prismatic metallocages (TPMs) composed of 24 components, namely {(Cu3L3)(Cu2X2)3(Cu3L3)}·xG (HL = 4-(quinoline-8-thio)-3,5-dimethyl-1H-pyrazole, G = benzene (B), methylbenzene (MB), 1,3,5-triphenylbenzene (TPB), x = 3 for B, MB and 1...

Spontaneous deracemization has been used to separate homochiral domains from the racemic system. However, homochirality can only be referred to when the scales of these domains and systems are specified. To clarify this, we report self‐assembly of racemates of dissymmetric cages DC‐1 with a cone‐shape propeller geometry, forming a centrosymmetric columnar crystalline phase (racemic at crystallographic level). Owing to their anisotropic geometry, the two enantiomers are packed in a frustrated fashion in this crystalline phase; single‐handed double helices are observed (single‐handedness at supramolecular level). The frustrated packing (layer continuity break‐up) in turn facilitates screw dislocation during the crystal growth, forming left‐ or right‐handed spiral platelets (symmetry‐breaking at morphological level), although each platelet is composed of DC‐1 racemates. The symmetry correlation between DC‐1 molecules, the crystalline phase and spiral platelets, all exhibit C3 symmetry.