Supramolecular macrocycles reversibly assembled by Te…O chalcogen bonding

Organic molecules with heavy main-group elements frequently form supramolecular links to electron-rich centres. One particular case of such interactions is halogen bonding. Most studies of this phenomenon have been concerned with either dimers or infinitely extended structures (polymers and lattices) but well-defined cyclic structures remain elusive. Here we present oligomeric aggregates of heterocycles that are linked by chalcogen-centered interactions and behave as genuine macrocyclic species. The molecules of 3-methyl-5-phenyl-1,2-tellurazole 2-oxide assemble a variety of supramolecular aggregates that includes cyclic tetramers and hexamers, as well as a helical polymer. In all these aggregates, the building blocks are connected by Te(…)O–N bridges. Nuclear magnetic resonance spectroscopic experiments demonstrate that the two types of annular aggregates are persistent in solution. These self-assembled structures form coordination complexes with transition-metal ions, act as fullerene receptors and host small molecules in a crystal

Enantiopure Supramolecular Cages: Synthesis and Chiral Recognition Properties

International audienceEnantiopure compounds are ubiquitous in the chemical sciences and present a particular interest in the field of molecular recognition and host-guest systems. Indeed, chiral molecular receptors are at the basis of numerous biological recognition processes and have important implications in biochemistry or pharmacology. Chemists have been investigating this field for several decades, which has led to the development of the synthesis of chiral hosts, their enantiomeric differentiation, and the studies of their recognition properties towards important and bio-relevant chiral guest substrates. The design of molecular cages is a rather difficult task that is even more demanding when enantiopure molecules are required. In this review we chose to present the main families of synthetic organic supramolecular cages that have been developed, whose structures contain stereogenic centers or present an inherent chirality, giving rise to chiral supramolecular cages. Particular attention is given to obtaining enantiopure compounds. Their recognition properties are also underlined. A last important aspect of the review is to present how chiroptical spectroscopies can be used to characterize the recognition phenomena displayed by supramolecular cages