Investigation of Perylene Diimide Functional Supramolecular Polymers

Abstract

In this project, 4-bromobenzamide di-substituted perylene diimide (PDI-BA-1) was synthesized and investigated by solvent-, concentration- and temperature-dependent studies. Controllable self-assembly behaviour and morphologies were observed by ultraviolet-visible-near infrared absorbance spectrometry (UV-Vis) and transmission electron microscopy (TEM), providing a ground for further investigation of formation of supramolecular polymers. Solubilities of PDI-BA-1 in fourteen solvents were evaluated by Hansen solubility parameters (HSP). A relationship between solvent HSP and self-assembly behaviour of PDI-BA-1 was proposed. By tuning the hydrogen-bonding component and dipolar cohesive component of HSP (δH, δP), controllable self-assembly behaviour was observed in the ethyl acetate/n-hexane dual-solvent system. A set of computational methods were studied for monomeric PDI-BA-1 geometry optimization and excitation behaviour. Two critical conformers of PDI-BA-1 (reactive-open and trapped-closed) regarding controllable inter-/intra-molecular hydrogen bonds were found and optimized. To further explore functional supramolecular perylene diimide derivatives, a preliminary synthesis and modelling work of tetra(aniline)-substituted perylene diimide (TANI-PDI) was started, which lays the groundwork for further studies in the future.

Date of Award	21 Jan 2021
Original language	English
Awarding Institution	University of Bristol
Supervisor	Charl F J Faul (Supervisor)