Self-Assembled Hosts for Applications in Guest Binding and Catalysis

Abstract

Living organisms can perform complex chemical reactions precisely in the confined pockets of enzymes. In this regard, numerous aesthetic 2D and 3D discrete architectures have been constructed using metal-ligand coordination and hydrogen bonding over the past two decades.[1a] Simultaneously, “dynamic covalent chemistry” (DCC) has been advantageous in making purely covalent organic cages and macrocycles from simple and readily available building organic molecules.[1b] In the thesis work, chapter 1 briefly discusses the self-assembly process for constructing 2D and 3D supramolecular architectures. Chapter 2 demonstrates the syntheses of metal-ligand coordination-driven self-assembled octa-nuclear PtII/PdII barrels and their application in unusual structural isomerization of a photochromic guest inside the barrel’s molecular space.[2] Chapter 3 introduces the design of analogous organic barrel structures using the DCC approach, including using such barrels as templates for the nucleation of tiny AgNPs for potential application in photocatalysis.[3] Chapter 4 describes the fabrication of an organic cage with a truncated tetrahedral topology and its application in nucleating PdNPs for selective homocoupling reactions.[4] Chapter 5 presents the post-synthetic modification of dynamic imine-bonded cage/macrocycle to obtain chemically and thermally robust amide-bonded analogs. Furthermore, the confined pocket of the amide cage showed high selectivity for fluoride anion.[5]