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Funder: Deutsche Forschungsgemeinschaft, A tetrahedral FeII4L4 cage assembled from the coordination of triangular chiral, face-capping ligands to iron(II). This cage exists as two diastereomers in solution, which differ in the stereochemistry of their metal vertices, but share the same point chirality of the ligand. The equilibrium between these cage diastereomers was subtly perturbed by guest binding. This perturbation from equilibrium correlated with the size and shape fit of the guest within the host; insight as to the interplay between stereochemistry and fit was provided by atomistic well-tempered metadynamics simulations. The understanding thus gained as to the stereochemical impact on guest binding enabled the design of a straightforward process for the resolution of the enantiomers of a racemic guest.

An enantiopure ligand with four bidentate metal-binding sites and four (S)-carbon stereocenters self-assembles with octahedral ZnII or CoII to produce O-symmetric M8L6 coordination cages. The Λ- or Δ-handedness of the metal centers forming the corners of these cages is determined by the solvent environment: the same (S)-ligand produces one diastereomer, (S)24-Λ8-M8L6, in acetonitrile but another with opposite metal-center handedness, (S)24-Δ8-M8L6, in nitromethane. Van 't Hoff analysis revealed the Δ stereochemical configuration to be entropically favored but enthalpically disfavored, consistent with a loosening of the coordination sphere and an increase in conformational freedom following Λ-to-Δ transition. The binding of 4,4'-dipyridyl naphthalenediimide and tetrapyridyl Zn-porphyrin guests did not interfere with the solvent-driven stereoselectivity of self-assembly, suggesting applications where either a Λ- or Δ-handed framework may enable chiral separations or catalysis.

The allosteric regulation of biomolecules, such as enzymes, enables them to adapt and alter their conformation to fit specific substrates, expressing different functionalities in response to stimuli. Different stimuli can also trigger synthetic coordination cages to change their shape, size, and nuclearity by reconfiguring the dynamic metal-ligand bonds that hold them together. Here we demonstrate an abiological system consisting of different organic subcomponents and ZnII metal ions, which can respond to simple stimuli in complex ways. A ZnII20L12 dodecahedron transforms to give a larger ZnII30L12 icosidodecahedron through subcomponent exchange, as an aldehyde that forms bidentate ligands is displaced in favor of one that forms tridentate ligands together with a penta-amine subcomponent. In the presence of a chiral template guest, the same system that produced the icosidodecahedron instead gives a ZnII15L6 truncated rhombohedral architecture through enantioselective self-assembly. Under specific crystallization conditions, a guest induces a further reconfiguration of either the ZnII30L12 or ZnII15L6 cages to yield an unprecedented ZnII20L8 pseudo-truncated octahedral structure. The transformation network of these cages shows how large synthetic hosts can undergo structural adaptation through the application of chemical stimuli, opening pathways to broader applications.