{"id":{"repo_id":"cambridge","oai_identifier":"oai:www.repository.cam.ac.uk:1810/292825"},"canonical_url":"https://search.dev.ndltd.org/etd/cambridge/oai:www.repository.cam.ac.uk:1810/292825","repository":{"repo_id":"cambridge","name":"Cambridge University","base_url":"https://api.repository.cam.ac.uk/server/oai/request"},"display":{"title":"Design, Synthesis and Characterisation of π-Extended Viologen-Based Molecular and Supramolecular Complexes with Cucurbit[n]urils","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 modulated. % Here, the effect of the aromatic extension ([X]) on EV[X]MVs before and upon complexation with CB[7] and CB[8] is investigated using nuclear magnetic resonance (NMR), steady-state UV-Vis and photoluminescence (PL) spectroscopies as well as isothermal titration calorimetry (ITC) and cyclic voltammetry (CV). % Interestingly, dimerisation of selected extended methyl viologens with CB[8] and the charge accumulative properties of the resultant complexes were observed. In Chapter 3, synthesis and characterisation of a family of extended viologens with aromatic substituents (EV[X]R, further denoted as extended aryl viologens), their interactions with CB[7] and CB[8] macrocycles as well as physiochemical properties of the resultant host-guest systems are studied. % The design and synthesis of these new class of $\\pi$-conjugated viologen derivatives are elaborated involving different aromatic bridging units, as well as rigid aromatic peripheral functionalisation with electron donating and electron withdrawing groups on the pyridinium rings. % Upon mixing with CB[8], the extended aryl viologen derivatives functionalised with electron donating groups self-assemble into 2:2 complexes. % Moreover, the extended work on EV[X]R molecules functionalised with different aromatic substituents, which are simultaneously encapsulated within CB[8] to form heteroquarternery complexes is discussed. % The nature and dynamics of the resulting ${\\mathrm{CB[8]_2}}\\cdot{(\\mathrm{EV[X]R})_2}$ homo- and hetero-complexes are studied both in the ground as well as exited states upon interaction with light utilising NMR, steady-state and time-resolved spectroscopies as well as ITC experiments. Finally, in Chapter 4 the synthetic approach towards asymmetric aryl viologen (AV) and extended aryl viologen (EV[X]RR', where [X]= naphthalene) is presented. % Firstly, synthetic pathways based on the Zinke reaction for asymmetric aryl substitution of AV and EV are discussed. % Secondly, the supramolecular binding of the obtained asymmetric EV[Np]RR' with CB[8] is investigated along with the effect of supramolecular dimer formation on the optical properties. % Finally, the application of asymmetric aryl viologens in the formation of a bio-inspired nanofibers is presented.","abstract_html":"Viologens, 4,4'-bipyridinium dications (V2+), 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, V2+, to radical monocations, V+.. % Moreover, the dynamic interactions of V2+ 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 V2+ based inclusion complexes make these systems highly attractive for supramolecular chemistry and dynamic nanosystems, i.e. molecular machines. % This doctoral thesis focuses on design, synthesis and characterisation of π-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 (MV2+) 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 MV2+ can be modulated. % Here, the effect of the aromatic extension ([X]) on EV[X]MVs before and upon complexation with CB[7] and CB[8] is investigated using nuclear magnetic resonance (NMR), steady-state UV-Vis and photoluminescence (PL) spectroscopies as well as isothermal titration calorimetry (ITC) and cyclic voltammetry (CV). % Interestingly, dimerisation of selected extended methyl viologens with CB[8] and the charge accumulative properties of the resultant complexes were observed. In Chapter 3, synthesis and characterisation of a family of extended viologens with aromatic substituents (EV[X]R, further denoted as extended aryl viologens), their interactions with CB[7] and CB[8] macrocycles as well as physiochemical properties of the resultant host-guest systems are studied. % The design and synthesis of these new class of π-conjugated viologen derivatives are elaborated involving different aromatic bridging units, as well as rigid aromatic peripheral functionalisation with electron donating and electron withdrawing groups on the pyridinium rings. % Upon mixing with CB[8], the extended aryl viologen derivatives functionalised with electron donating groups self-assemble into 2:2 complexes. % Moreover, the extended work on EV[X]R molecules functionalised with different aromatic substituents, which are simultaneously encapsulated within CB[8] to form heteroquarternery complexes is discussed. % The nature and dynamics of the resulting {CB[8]2}\\cdot{(EV[X]R)2} homo- and hetero-complexes are studied both in the ground as well as exited states upon interaction with light utilising NMR, steady-state and time-resolved spectroscopies as well as ITC experiments. Finally, in Chapter 4 the synthetic approach towards asymmetric aryl viologen (AV) and extended aryl viologen (EV[X]RR', where [X]= naphthalene) is presented. % Firstly, synthetic pathways based on the Zinke reaction for asymmetric aryl substitution of AV and EV are discussed. % Secondly, the supramolecular binding of the obtained asymmetric EV[Np]RR' with CB[8] is investigated along with the effect of supramolecular dimer formation on the optical properties. % Finally, the application of asymmetric aryl viologens in the formation of a bio-inspired nanofibers is presented.","abstract_has_math":true,"creators":["Olesinska, Magdalena"],"institution":"University of Cambridge","degree_name":"Doctor of Philosophy (PhD)","degree_level":"Doctoral","degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":["Scherman, Oren Alexander"],"committee_chairs":[],"committee_members":[],"year":2019,"date_issued":"2019-07-19","date_published":"2019-07-19","updated_at":"2026-07-24T01:33:23Z","subjects":["Cucrbit[n]uril","Extended viologen","Extended aryl viologen","Asymmetric viologen","Viologen dimerisation","Excimers"],"languages":["en"],"rights":[],"rights_urls":["https://www.repository.cam.ac.uk/bitstreams/2c96ff6d-2990-4c36-bd38-46ed115ee61e/download","https://www.rioxx.net/licenses/all-rights-reserved/"],"identifier_entries":[]},"links":{"outbound_url":"https://doi.org/10.17863/CAM.39981","outbound_label":"DOI","outbound_source":"dc:identifier.doi"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Scherman, Oren Alexander"]},{"key":"dc:contributor.sponsor","label":"Sponsor","values":["The Marie Curie FP7 SASSYPOL ITN (607602) programme"]},{"key":"dc:creator","label":"Author","values":["Olesinska, 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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 modulated. % Here, the effect of the aromatic extension ([X]) on EV[X]MVs before and upon complexation with CB[7] and CB[8] is investigated using nuclear magnetic resonance (NMR), steady-state UV-Vis and photoluminescence (PL) spectroscopies as well as isothermal titration calorimetry (ITC) and cyclic voltammetry (CV). % Interestingly, dimerisation of selected extended methyl viologens with CB[8] and the charge accumulative properties of the resultant complexes were observed. In Chapter 3, synthesis and characterisation of a family of extended viologens with aromatic substituents (EV[X]R, further denoted as extended aryl viologens), their interactions with CB[7] and CB[8] macrocycles as well as physiochemical properties of the resultant host-guest systems are studied. % The design and synthesis of these new class of $\\pi$-conjugated viologen derivatives are elaborated involving different aromatic bridging units, as well as rigid aromatic peripheral functionalisation with electron donating and electron withdrawing groups on the pyridinium rings. % Upon mixing with CB[8], the extended aryl viologen derivatives functionalised with electron donating groups self-assemble into 2:2 complexes. % Moreover, the extended work on EV[X]R molecules functionalised with different aromatic substituents, which are simultaneously encapsulated within CB[8] to form heteroquarternery complexes is discussed. % The nature and dynamics of the resulting ${\\mathrm{CB[8]_2}}\\cdot{(\\mathrm{EV[X]R})_2}$ homo- and hetero-complexes are studied both in the ground as well as exited states upon interaction with light utilising NMR, steady-state and time-resolved spectroscopies as well as ITC experiments. Finally, in Chapter 4 the synthetic approach towards asymmetric aryl viologen (AV) and extended aryl viologen (EV[X]RR', where [X]= naphthalene) is presented. % Firstly, synthetic pathways based on the Zinke reaction for asymmetric aryl substitution of AV and EV are discussed. % Secondly, the supramolecular binding of the obtained asymmetric EV[Np]RR' with CB[8] is investigated along with the effect of supramolecular dimer formation on the optical properties. % Finally, the application of asymmetric aryl viologens in the formation of a bio-inspired nanofibers is presented."]},{"key":"dc:format.checksum.md5","label":"Dc Format Checksum Md5","values":["d19d4d1f7ca416cfe3a137d1f24c3ba1","87eda9de84448d1f82354d60eee3eb5f"]},{"key":"dc:title","label":"Title","values":["Design, Synthesis and Characterisation of π-Extended Viologen-Based Molecular and Supramolecular Complexes with Cucurbit[n]urils"]}]}],"canonical_facts":{"dc:contributor.advisor":["Scherman, Oren Alexander"],"dc:contributor.sponsor":["The Marie Curie FP7 SASSYPOL ITN (607602) programme"],"dc:creator":["Olesinska, Magdalena"],"dc:date.issued":["2019-07-19"],"dc:description.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 modulated. % Here, the effect of the aromatic extension ([X]) on EV[X]MVs before and upon complexation with CB[7] and CB[8] is investigated using nuclear magnetic resonance (NMR), steady-state UV-Vis and photoluminescence (PL) spectroscopies as well as isothermal titration calorimetry (ITC) and cyclic voltammetry (CV). % Interestingly, dimerisation of selected extended methyl viologens with CB[8] and the charge accumulative properties of the resultant complexes were observed. In Chapter 3, synthesis and characterisation of a family of extended viologens with aromatic substituents (EV[X]R, further denoted as extended aryl viologens), their interactions with CB[7] and CB[8] macrocycles as well as physiochemical properties of the resultant host-guest systems are studied. % The design and synthesis of these new class of $\\pi$-conjugated viologen derivatives are elaborated involving different aromatic bridging units, as well as rigid aromatic peripheral functionalisation with electron donating and electron withdrawing groups on the pyridinium rings. % Upon mixing with CB[8], the extended aryl viologen derivatives functionalised with electron donating groups self-assemble into 2:2 complexes. % Moreover, the extended work on EV[X]R molecules functionalised with different aromatic substituents, which are simultaneously encapsulated within CB[8] to form heteroquarternery complexes is discussed. % The nature and dynamics of the resulting ${\\mathrm{CB[8]_2}}\\cdot{(\\mathrm{EV[X]R})_2}$ homo- and hetero-complexes are studied both in the ground as well as exited states upon interaction with light utilising NMR, steady-state and time-resolved spectroscopies as well as ITC experiments. Finally, in Chapter 4 the synthetic approach towards asymmetric aryl viologen (AV) and extended aryl viologen (EV[X]RR', where [X]= naphthalene) is presented. % Firstly, synthetic pathways based on the Zinke reaction for asymmetric aryl substitution of AV and EV are discussed. % Secondly, the supramolecular binding of the obtained asymmetric EV[Np]RR' with CB[8] is investigated along with the effect of supramolecular dimer formation on the optical properties. % Finally, the application of asymmetric aryl viologens in the formation of a bio-inspired nanofibers is presented."],"dc:format.checksum.md5":["d19d4d1f7ca416cfe3a137d1f24c3ba1","87eda9de84448d1f82354d60eee3eb5f"],"dc:identifier.doi":["10.17863/CAM.39981"],"dc:identifier.uri":["https://www.repository.cam.ac.uk/bitstreams/03e8be11-3968-463b-9dcf-d49e802c46d5/download"],"dc:language":["en"],"dc:publisher.institution":["University of Cambridge"],"dc:relation.isreferencedby.uri":["https://www.repository.cam.ac.uk/handle/1810/292825"],"dc:rights":["https://www.repository.cam.ac.uk/bitstreams/2c96ff6d-2990-4c36-bd38-46ed115ee61e/download","https://www.rioxx.net/licenses/all-rights-reserved/"],"dc:subject":["Cucrbit[n]uril","Extended viologen","Extended aryl viologen","Asymmetric viologen","Viologen dimerisation","Excimers"],"dc:title":["Design, Synthesis and Characterisation of π-Extended Viologen-Based Molecular and Supramolecular Complexes with Cucurbit[n]urils"],"dc:type":["Thesis"],"dc:type.qualificationlevel":["Doctoral"],"dc:type.qualificationname":["Doctor of Philosophy (PhD)"]},"updated_at":"2026-07-24T01:33:23Z"}