Synthesis and ultrafast spectroscopy of porphyrin molecular wires
<p>Porphyrins, found in nature in cyclic light harvesting arrays, are a fascinating class of compounds. Their synthesis and assembly into advanced light harvesting architectures have challenged chemists for decades, and their resulting photophysical properties such as energy transfer and charg...
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| Format: | Thesis |
| Language: | English |
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2019
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| _version_ | 1797111209375301632 |
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| author | Kendrick, W |
| author2 | Anderson, H |
| author_facet | Anderson, H Kendrick, W |
| author_sort | Kendrick, W |
| collection | OXFORD |
| description | <p>Porphyrins, found in nature in cyclic light harvesting arrays, are a fascinating class of compounds. Their synthesis and assembly into advanced light harvesting architectures have challenged chemists for decades, and their resulting photophysical properties such as energy transfer and charge localisation continue to teach us about fundamental physical effects. This thesis explores both of these aspects, starting first with the synthesis of a porphyrin nanoball before exploring the ultrafast spectroscopy of porphyrin molecular wires. </p>
<p>Chapter 1 introduces the chemistry of porphyrins. The syntheses of porphyrin monomers are discussed, highlighting the key route to functionalised porphyrins. A range of cyclic porphyrin arrays are presented, and the syntheses compared and contrasted. Finally, 3D porphyrin nanostructures are discussed, comparing and contrasting their formation via self-assembly and template-directed syntheses. </p>
<p>Chapter 2 presents a novel 3D pyridyl template for the formation of a 10-porphyrin nanoball. Several ball precursors are identified and synthesised, before ball formation proved unsuccessful. The factors affecting the unsuccessful ball formation are discussed in detail with the help of <sup>1</sup>H NMR and UV-vis-NIR titrations. The lessons learnt are applied to the design of a new template, for which a synthesis is suggested.</p>
<p>In Chapter 3 π-conjugated compounds are summarised. Two ultrafast spectroscopy techniques are introduced, 2D-infrared and time-resolved infrared, and their spectra derived from model examples to aid the reader in interpretation. The literature regarding ultrafast spectroscopy applied to π-conjugated polymers is summarised, before an area of underexplored research is identified.</p>
<p>Chapter 4 presents an in-depth ultrafast spectroscopic study of the radical cations of porphyrin oligomeric molecular wires. Using spectroelectrochemistry to generate the radical cations, 2D-IR and TRIR were undertaken to elucidate the mechanism of infrared band activation. The data show that the intensification of infrared bands upon oxidation is a result of strong coupling between vibrational motion and charge.</p> |
| first_indexed | 2024-03-07T08:07:03Z |
| format | Thesis |
| id | oxford-uuid:b8416a9b-b9a3-456d-a621-79917ffb1c1c |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T08:07:03Z |
| publishDate | 2019 |
| record_format | dspace |
| spelling | oxford-uuid:b8416a9b-b9a3-456d-a621-79917ffb1c1c2023-11-01T15:29:09ZSynthesis and ultrafast spectroscopy of porphyrin molecular wiresThesishttp://purl.org/coar/resource_type/c_db06uuid:b8416a9b-b9a3-456d-a621-79917ffb1c1cChemistry, OrganicPhysical ChemistrySupramolecular ChemistryMaterials ChemistryEnglishORA Deposit2019Kendrick, WAnderson, H<p>Porphyrins, found in nature in cyclic light harvesting arrays, are a fascinating class of compounds. Their synthesis and assembly into advanced light harvesting architectures have challenged chemists for decades, and their resulting photophysical properties such as energy transfer and charge localisation continue to teach us about fundamental physical effects. This thesis explores both of these aspects, starting first with the synthesis of a porphyrin nanoball before exploring the ultrafast spectroscopy of porphyrin molecular wires. </p> <p>Chapter 1 introduces the chemistry of porphyrins. The syntheses of porphyrin monomers are discussed, highlighting the key route to functionalised porphyrins. A range of cyclic porphyrin arrays are presented, and the syntheses compared and contrasted. Finally, 3D porphyrin nanostructures are discussed, comparing and contrasting their formation via self-assembly and template-directed syntheses. </p> <p>Chapter 2 presents a novel 3D pyridyl template for the formation of a 10-porphyrin nanoball. Several ball precursors are identified and synthesised, before ball formation proved unsuccessful. The factors affecting the unsuccessful ball formation are discussed in detail with the help of <sup>1</sup>H NMR and UV-vis-NIR titrations. The lessons learnt are applied to the design of a new template, for which a synthesis is suggested.</p> <p>In Chapter 3 π-conjugated compounds are summarised. Two ultrafast spectroscopy techniques are introduced, 2D-infrared and time-resolved infrared, and their spectra derived from model examples to aid the reader in interpretation. The literature regarding ultrafast spectroscopy applied to π-conjugated polymers is summarised, before an area of underexplored research is identified.</p> <p>Chapter 4 presents an in-depth ultrafast spectroscopic study of the radical cations of porphyrin oligomeric molecular wires. Using spectroelectrochemistry to generate the radical cations, 2D-IR and TRIR were undertaken to elucidate the mechanism of infrared band activation. The data show that the intensification of infrared bands upon oxidation is a result of strong coupling between vibrational motion and charge.</p> |
| spellingShingle | Chemistry, Organic Physical Chemistry Supramolecular Chemistry Materials Chemistry Kendrick, W Synthesis and ultrafast spectroscopy of porphyrin molecular wires |
| title | Synthesis and ultrafast spectroscopy of porphyrin molecular wires |
| title_full | Synthesis and ultrafast spectroscopy of porphyrin molecular wires |
| title_fullStr | Synthesis and ultrafast spectroscopy of porphyrin molecular wires |
| title_full_unstemmed | Synthesis and ultrafast spectroscopy of porphyrin molecular wires |
| title_short | Synthesis and ultrafast spectroscopy of porphyrin molecular wires |
| title_sort | synthesis and ultrafast spectroscopy of porphyrin molecular wires |
| topic | Chemistry, Organic Physical Chemistry Supramolecular Chemistry Materials Chemistry |
| work_keys_str_mv | AT kendrickw synthesisandultrafastspectroscopyofporphyrinmolecularwires |