Chiral perylene diimide containing macrocycles and rotaxanes

Abstract

This thesis describes an investigation into a class of chiral organic dyes, perylene diimides (PDIs). Specifically, configurationally stable PDI dyes are targeted through the design, synthesis and analysis of PDI-based macrocycles and rotaxanes. Chapter One introduces PDIs and outlines how the synthetic diversity of PDI derivatives impacts their photophysical, redox, supramolecular and chiral properties, with a particular focus on the integration of PDIs into macrocycles and rotaxanes. Chapter Two describes the design and synthesis of a series of novel chirally-locked PDI-based macrocycles, including an investigation into kinetic templation in the macrocyclisation reaction. The successful synthesis of PDI-based macrocycles with πelectron donors in the macrocycle linkers evidences the importance of π-π donor-acceptor interactions. Chapter Three explores kinetic templation in PDI-based macrocycles containing a second chiral aromatic component. Here, the diastereoselective synthesis of a PDI-based macrocycle is realised, in which templating non-covalent interactions between the aromatic units that direct the outcome of the dynamic kinetic resolution are discussed. Chapter Four describes the progress towards a configurationally stable chiral PDI through mechanical bonding by the synthesis of a novel [3]rotaxane containing a PDI-based axle and two macrocycle components. When positioned in close proximity to the chiral PDI, the macrocycles are shown to slow down PDI atropisomer interconversion. The pH-induced molecular shuttling of these macrocycles is also presented. Chapter Five describes the experimental procedures used throughout this work and details the characterisation of novel compounds. Chapter Six provides a summary of the major conclusions from the research described in this thesis