A pseudo-cubic metal-organic cage with conformationally switchable faces for dynamically adaptive guest encapsulation.

The creation of hosts capable of accommodating different guest molecules may enable these hosts to play useful roles in chemical purifications, among other applications. Metal-organic cages are excellent hosts for various guests, but they generally incorporate rigid structural units that hinder dynamic adaptation to specific guests. Here we report a conformationally adaptable pseudo-cubic cage that can dynamically increase its cavity volume to fit guests with differing sizes.

A CuL Cage Dynamically Reconfigures to Form Suit[4]anes and Selectively Bind Fluorinated Steroids.

Simple organic ligands can self-assemble with metal ions to generate metal-organic cages, whose cavities bind guests selectively. This binding may enable new methods of chemical separation or sensing, among other useful functions. Here we report the preparation of a CuL pseudo-octahedral metal-organic cage, the ligands of which self-assemble from simple organic building blocks.

A Double-Walled Tetrahedron with Ag Vertices Binds Different Guests in Distinct Sites.

A double-walled tetrahedral metal-organic cage assembled in solution from silver(I), 2-formyl-1,8-naphthyridine, halide, and a threefold-symmetric triamine. The Ag X clusters at its vertices each bring together six naphthyridine-imine moieties, leading to a structure in which eight tritopic ligands bridge four clusters in an (Ag X) L arrangement. Four ligands form an inner set of tetrahedron walls that are surrounded by the outer four.

Enantioselective fullerene functionalization through stereochemical information transfer from a self-assembled cage.

The regioselective functionalization of C remains challenging, while the enantioselective functionalization of C is difficult to explore due to the need for complex chiral tethers or arduous chromatography. Metal-organic cages have served as masks to effect the regioselective functionalization of C. However, it is difficult to control the stereochemistry of the resulting fullerene adducts through this method.

Controlling catalyst activity, chemoselectivity and stereoselectivity with the mechanical bond.

Mechanically interlocked molecules, such as rotaxanes and catenanes, are receiving increased attention as scaffolds for the development of new catalysts, driven by both their increasing accessibility and high-profile examples of the mechanical bond delivering desirable behaviours and properties. In this Review, we survey recent advances in the catalytic applications of mechanically interlocked molecules organized by the effect of the mechanical bond on key catalytic properties, namely, activity, chemoselectivity and stereoselectivity, and focus on how the mechanically bonded structure leads to the observed behaviour. Our aim is to inspire future investigations of mechanically interlocked catalysts, including those outside of the supramolecular community.

A Hydrogen-Bonded Ravel Assembled by Anion Coordination.

Anion-coordination-driven assembly (ACDA) is showing increasing power in the construction of anionic supramolecular architectures. Herein, by expanding the anion centers from oxoanion (phosphate or sulfate) to organic tris-carboxylates, an Archimedean solid (truncated tetrahedron) and a highly entangled, double-walled tetrahedron featuring a ravel topology have been assembled with tris-bis(urea) ligands. The results demonstrate the promising ability of tris-carboxylates as new anion coordination centers in constructing novel topologies with increasing complexity and diversity compared to phosphate or sulfate ions on account of the modifiable size and easy functionalization character of these organic anions.

A chiral interlocking auxiliary strategy for the synthesis of mechanically planar chiral rotaxanes.

Rotaxanes can display molecular chirality solely due to the mechanical bond between the axle and encircling macrocycle without the presence of covalent stereogenic units. However, the synthesis of such molecules remains challenging. We have discovered a combination of reaction partners that function as a chiral interlocking auxiliary to both orientate a macrocycle and, effectively, load it onto a new axle.

Synthesis of a Mechanically Planar Chiral Rotaxane Ligand for Enantioselective Catalysis.

Rotaxanes are interlocked molecules in which a molecular ring is trapped on a dumbbell-shaped axle because of its inability to escape over the bulky end groups, resulting in a so-called mechanical bond. Interlocked molecules have mainly been studied as components of molecular machines, but the crowded, flexible environment created by threading one molecule through another has also been explored in catalysis and sensing. However, so far, the applications of one of the most intriguing properties of interlocked molecules, their ability to display stereogenic units that do not rely on the stereochemistry of their covalent subunits, termed "mechanical chirality," have yet to be properly explored, and prototypical demonstration of the applications of mechanically chiral rotaxanes remain scarce.

Simplicity in the Design, Operation, and Applications of Mechanically Interlocked Molecular Machines.

Mechanically interlocked molecules are perhaps best known as components of molecular machines, a view further reinforced by the Nobel Prize in 2016 to Stoddart and Sauvage. Despite amazing progress since these pioneers of the field reported the first examples of molecular shuttles, genuine applications of interlocked molecular machines remain elusive, and many barriers remain to be overcome before such molecular devices make the transition from impressive prototypes on the laboratory bench to useful products. Here, we discuss simplicity as a design principle that could be applied in the development of the next generation of molecular machines with a view to moving toward real-world applications of these intriguing systems in the longer term.