Term | Value | Language |
---|---|---|
dc.contributor.advisor | Jasti, Ramesh | |
dc.contributor.author | Gillett, Leyla | |
dc.date.accessioned | 2024-08-30T19:16:40Z | |
dc.date.available | 2024-08-30T19:16:40Z | |
dc.date.issued | 2024 | |
dc.identifier.uri | https://scholarsbank.uoregon.edu/xmlui/handle/1794/29929 | |
dc.description | 50 pages | |
dc.description.abstract | Many common, commercially available fluorophores exist that have a variety of applications, such as in biological imaging. However, these molecules often have significant limitations, namely photobleaching. As such, continued development of new fluorophores and fluorescent scaffolds is expected to facilitate tasks in areas such as biological analysis, where visualization of systems with consistently good quality and high resolution is vital. Cycloparaphenylenes (CPPs) are of interest in fluorescence research, as these cyclic macromolecules (also referred to as “nanohoops”) are promising candidates for fluorescent scaffolds, because not only do they generally overcome these limitations, but they also have tunable fluorescence based on their size and functionality. While synthetic routes for achieving [n]cycloparaphenylenes ([n]CPPs, where “n” refers to the number of ring units within the larger nanohoop) have been well-established, further exploration of certain types of these fluorescent molecules continue to show interesting results, including as alternative fluorophores for live cell imaging. This research examines the [9+1] internal alkyne-containing CPP (which contains 9 phenyl units, plus an integrated carbon-carbon triple-bond unit, hence the “9+1”), where the distortion of the alkyne unit promotes increased reactivity that will allow for the synthesis of a range of undiscovered CPP derivatives. This project highlights new routes for synthetic exploration with these uniquely fluorescent nanohoops, motivated by utilizing angular-strained motifs and classic Diels-Alder reactions. As molecular properties generally change with different functionalities, the reactivity and photophysical properties of the class CPP derivatives explored here are unprecedented. After completing the synthesis of the [9+1]CPP following an established synthetic route, Diels-Alder reactivity was explored with tetraphenyl cyclopentadienone (TPCPD) in order to 3 introduce new functionality at the site of the alkyne. TPCPD was selected as it is an important building block for many organic and organometallic compounds, and there are literature precedents describing the potential of the central ring to react as a diene with dienophiles in a Diels-Alder reaction, similar to the alkyne in the [9+1]CPP. This successful late-stage functionalization of a fluorophore in relatively high yield (69%) shows promising results as a new way to achieve desired modifications of fully-synthesized CPPs, opening new avenues for research into molecules capable of “clicking” to the alkyne-containing CPP that provide useful functions. | en_US |
dc.language.iso | en_US | |
dc.publisher | University of Oregon | |
dc.rights | CC BY-NC-ND 4.0 | |
dc.subject | Cycloparaphenylene | en_US |
dc.subject | Nanohoop | en_US |
dc.subject | Organic chemistry | en_US |
dc.subject | Click chemistry | en_US |
dc.subject | Fluorescence | en_US |
dc.title | Exploring Diels-Alder Reactivity of Alkyne-Containing Cycloparaphenylenes | |
dc.type | Thesis/Dissertation | |
dc.identifier.orcid | 0009-0006-0488-6189 |