Date of Award

8-2020

Degree Name

Master of Science

Department

Chemistry

First Advisor

Dr. Gellert Mezei

Second Advisor

Dr. Ramakrishna Guda

Third Advisor

Dr. Ekkehard Sinn

Keywords

Supramolecular chemistry, inorganic, nanojars, chalcogens, purification

Access Setting

Masters Thesis-Campus Only

Restricted to Campus until

8-31-2022

Abstract

Supramolecular chemistry is a field in chemistry that focuses on intermolecular bonds in a “host-guest complex” or supramolecular assemblies. Nanojars are supramolecular assemblies of the formula [anion⊂{Cu(μ-OH)(μ-pz)}n] (n = 27‒33) which incarcerate kosmotropic anions, such as carbonate (CO32‒), sulfate (SO42‒) and hydrogen phosphate (HPO42‒). Nanojars consist of three [Cu(μ-OH)(μ-pz)]x (x = 6‒14, except 11) rings that are assembled similarly to Matryoshka dolls, where the top and bottom rings act as guests for the central ring. The larger central ring is bound to the two smaller rings by multiple hydrogen bonds and weak oxygen-copper interactions. The three-ring assembly acts as a neutral host for the incarcerated anion. The host binds the anion by a multitude of hydrogen bonds and is capped by tetrabutylammonium counterions.

This work addresses 1) the synthesis and characterization of chalcogen oxyanion-incarcerating nanojars, 2) the use of less hygroscopic reagents to reduce the formation of carbonate nanojars, 3) a purification method to obtain a single-size nanojar, 4) the binding strength of sulfate in the nanojar, and 5) the stability of the nanojars in the presence of biological compounds.

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