Chemical Transformations in Confined Space of Coordination Architectures

Abstract

The scholastic significance of supramolecular chemistry continues to grow with the recent development of catalytic transformations in confined space of supramolecular architectures. It has come a long way from a natural cavity containing molecules to modern smart materials capable of manipulating reaction pathways. The rise of self-assembled coordination complexes provided a diverse array of host structures. Starting from purely organic compounds to metalloligand surrogates, supramolecular host cavities were tuned according to the requirement of the reactions. The understanding of their participation in a reaction led to better usage of those assemblies for specific reaction sequences. Commencing from cyclodextrin, a wide range of organic molecules was used for cage-catalyzed organic transformations. However, difficulties in synthesis and a tedious purification procedure led chemists to choose a different pathway of metal-ligand coordination-driven self-assembly. The latter stood out as a potential replacement of the organic cages, overcoming the previous drawbacks. In the glut of different transition-metal assemblies used for catalytic transformations, many of them showed chemo- and stereoselective products. However, the small cavity size in some of them led to premature failure of the reaction. In that context, "molecular barrels" showed good efficacy for the catalytic reaction sequence. The large cavity size and bigger orifice for intake of the substrate and easy release of the product made them a better choice for catalysis. Additionally these are mostly used in aqueous media, which reinforces the idea of green and environmentally nonhazardous chemistry. In this Viewpoint, we discuss the use of metal-ligand coordination-driven self-assembled molecular containers used for catalysis with special emphasis on molecular barrels. This paper built on existing literature provides a thorough development of the fertile ground of the coordination architecture for catalysis and its future direction of propagation.