Electronic Theses and Dissertations

Date of Award

1-1-2025

Document Type

Thesis

Degree Name

M.S. in Chemistry

First Advisor

Nathan I. Hammer

Second Advisor

Ryan C. Fortenberry

Third Advisor

Vignesh Sundaresan

School

University of Mississippi

Relational Format

dissertation/thesis

Abstract

Raman spectroscopy and computational chemistry are used to explore the effects of non-covalent interactions with the nitrogen-containing building block 2,6-dimethoxypyridine. Previously, we have shown that hydrogen and halogen bonding with simple nitrogen containing heterocycles leads to partial charge transfer and evolving spectroscopic properties. Adding electron donating and withdrawing groups to azabenzenes should allow us then to tune these interactions. Here, 2,6-dimethoxypyridine (DMOP) with its two methoxy substituents offers an excellent opportunity to study the effect of electron withdrawal on spectroscopic observables. Unlike in previous studies, however, hydrogen bonding led to no discernable experimental spectroscopic changes in mixtures of DMOP and water. Computational results suggest that water preferentially binds to the two oxygen atoms in the methoxy groups, rather than the lone nitrogen atom. This competition for binding, as well as steric effects are likely the origins of the lack of experimental shifts. Halogen bonding interactions between DMOP and heptafluoro-2-iodopropane (HFIP), however, resulted in experimental red shifts (shifts to lower energy) in the C-I stretching mode of HFIP, as predicated by computations.

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