ABSTRACT

The robust interdisciplinary aspects of supramolecular catalysis are described in this chapter. Modifications of the nature of substrate binding and activation, redox properties through weak interactions and confinement are fundamentals of supramolecular catalyzed reactions. The changes in environment through complementary interactions provide superior reactivity and control in supramolecular catalysis over catalytic reactions lacking supramolecular features. Stimuli-guided reactivity in supramolecular catalysis for changes in the redox and photochemical properties of a component makes a large difference in selectivity and enables supramolecular catalysts to sort reactants from a mixture to carry out transformation of a specific substrate. Assemblies in the solid state are useful in carrying out photochemical cycloaddition reactions and mechanochemical reactions of solids by using a suitable host or cocrystals. The acid–base properties of a host are influenced by the substituent and affect supramolecular catalytic activities. Selective ion binding influences catalytic efficiency and product specificity. The size of the cavity, weak interactions and hydrophobicity associated with hosts such as cyclodextrin, cucurbiturils and metal cages have provided a new impetus in the growth of supramolecular catalysis. Understanding the mechanism of catalytic intermediates in enzyme catalysis has helped in developing various enzyme mimics. In this chapter, emphasis is put on divulging the principles of developing catalysts by taking select examples from the literature. Metal organic frameworks in supramolecular catalysis are introduced and the modifications of MOF through ligands and the variation of linkers for designing artificial metalloenzymes based on metal organic frameworks are discussed. Specific examples of enhancing reactivity, selectivity in catalytic reactions and use of green catalysts are the other issues discussed in this chapter.