Investigations of the Non-Covalent CH-Π Interactions Using Molecular Torsional Balances

<p>Several bicycle N-arylimide based molecular balances were designed to study aliphatic CH-pi interactions and aromatic CH-pi interactions (edge-to-face arene-arene interactions). In each case, the geometries of the interactions were characterized in the solid-state via X-ray analysis, and the strengths of interactions were characterized in solution by their folded/unfolded ratios, as measured by integration of their 1H NMR spectra. </p> <p> The balances are very sensitive to variations in the strengths of weak non-covalent interactions. Several different aspects of the CH-pi interactions were studied, such as sterics, conformational entropy, cooperativity, deuterium isotope effect, substitution effects, and solvent effects. It showed that due to the weak nature of CH-pi interactions, many forces can contribute on determining their interacting energies with similar magnitudes. Approaches using "double-mutant cycles" to isolate the interactions of interest from secondary effects were presented. The balances can also be used to the study of other non-covalent interaction, and the investigations were included in the last chapter.</p>

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Open Access Dissertation

Discipline thesis:degree_discipline

Chemistry and Biochemistry

Year

2013

Author dc:creator

• Zhao, Chen

Contributors dc:contributor

• Ken D Shimizu
• Qian Wang

• Chemistry
• Physical Sciences and Mathematics

Statement dc:rights

• © 2013, Chen Zhao

Repository record dc:identifier

https://scholarcommons.sc.edu/etd/2401

OAI identifier oai:identifier

oai:scholarcommons.sc.edu:etd-3402