Design, Synthesis and Characterisation of π-Extended Viologen-Based Molecular and Supramolecular Complexes with Cucurbit[n]urils
type: CreativeWork
description: Viologens, 4,4'-bipyridinium dications (V$^{2+}$), have attracted much attention as electron mediators in a variety of photochemical, electrochemical and chemical processes ranging from catalysis, electrochromic devices to solar energy conversion and storage systems. % The different applications of viologens are related primarily to their facile one electron reduction of dicationic species, V$^{2+}$, to radical monocations, V$^{+.}$. % Moreover, the dynamic interactions of V$^{2+}$ derivatives with cucurbit[n]uril (CB[n], for n=7 or 8) macrocycles, the dimerisation of V$^{+.}$ radical cations inside the CB[8] molecular cavity as well as redox controlled stoichiometry of V$^{2+}$ based inclusion complexes make these systems highly attractive for supramolecular chemistry and dynamic nanosystems, $\textit{i.e.}$ molecular machines. % This doctoral thesis focuses on design, synthesis and characterisation of $\pi$-extended viologen-based molecular and supramolecular systems. % Integral to the project was to study assembly processes that involve extended viologen derivatives and CB[n] macrocycles as well as characterisation of the physicochemical properties of resulting host-guest systems. % A brief overview of viologen and CB[n] chemistry as well as fundamentals regarding self-assembly processes and how can they influence the optoelectronic properties of materials are discussed in Chapter~1. % % Chapter 2 describes the synthesis and characterisation of extended methyl viologen (EV[X]MV) derivatives with an aromatic extension between the pyridinium rings (X= phenylene, naphthalene, pyrene, chrysene, thiophene and dithiophene), their interactions with CB[7] and CB[8] macrocycles as well as physicochemical properties of the resultant host-guest systems are studied. % Methyl viologen (MV$^{2+}$) is a well-known guest for both CB[7] and CB[8] macrocycles. % On account of the different binding modes with CB[n], the optical as well as redox properties of MV$^{2+}$ can be modula…
abstract: Viologens, 4,4'-bipyridinium dications (V$^{2+}$), have attracted much attention as electron mediators in a variety of photochemical, electrochemical and chemical processes ranging from catalysis, electrochromic devices to solar energy conversion and storage systems. % The different applications of viologens are related primarily to their facile one electron reduction of dicationic species, V$^{2+}$, to radical monocations, V$^{+.}$. % Moreover, the dynamic interactions of V$^{2+}$ derivatives with cucurbit[n]uril (CB[n], for n=7 or 8) macrocycles, the dimerisation of V$^{+.}$ radical cations inside the CB[8] molecular cavity as well as redox controlled stoichiometry of V$^{2+}$ based inclusion complexes make these systems highly attractive for supramolecular chemistry and dynamic nanosystems, $\textit{i.e.}$ molecular machines. % This doctoral thesis focuses on design, synthesis and characterisation of $\pi$-extended viologen-based molecular and supramolecular systems. % Integral to the project was to study assembly processes that involve extended viologen derivatives and CB[n] macrocycles as well as characterisation of the physicochemical properties of resulting host-guest systems. % A brief overview of viologen and CB[n] chemistry as well as fundamentals regarding self-assembly processes and how can they influence the optoelectronic properties of materials are discussed in Chapter~1. % % Chapter 2 describes the synthesis and characterisation of extended methyl viologen (EV[X]MV) derivatives with an aromatic extension between the pyridinium rings (X= phenylene, naphthalene, pyrene, chrysene, thiophene and dithiophene), their interactions with CB[7] and CB[8] macrocycles as well as physicochemical properties of the resultant host-guest systems are studied. % Methyl viologen (MV$^{2+}$) is a well-known guest for both CB[7] and CB[8] macrocycles. % On account of the different binding modes with CB[n], the optical as well as redox properties of MV$^{2+}$ can be modula…
author: Olesinska, Magdalena
language: en
keywords: Cucrbit[n]uril, Extended viologen, Extended aryl viologen, Asymmetric viologen, Viologen dimerisation, Excimers
license: https://www.repository.cam.ac.uk/bitstreams/2c96ff6d-2990-4c36-bd38-46ed115ee61e/download
license: https://www.rioxx.net/licenses/all-rights-reserved/
date published: 2019-07-19
date modified: 2026-07-24T01:33:23Z
provider: Cambridge University
publisher: Networked Digital Library of Theses and Dissertations
type: WebPage
source organization: University of Cambridge

PropertyValue
property ID: DOI
value: 10.17863/CAM.39981