Date of Award:

5-2022

Document Type:

Dissertation

Degree Name:

Doctor of Philosophy (PhD)

Department:

Chemistry and Biochemistry

Committee Chair(s)

Alexander I. Boldyrev

Committee

Alexander I. Boldyrev

Committee

Steve Scheiner

Committee

Yi Rao

Committee

David Farrelly

Committee

Xiaojun Qi

Abstract

You may find plenty of definitions of chemistry but all of them, explicitly or not, are centered around chemical bonds. When we say “chemical properties”, “reactivity”, “stability”, “structure” etc., we have in mind chemical bonds and their reorganization which almost completely defines the behavior of the matter. Why some materials are ultrahard and can cut through steel while others are so soft that you can form them with your bare hands? You probably have already guessed that it occurs because their chemical bonding is very different. Although the elemental composition could be the same! In this Dissertation, we report results which might seem eclectic at first but under the hood all of them are closely related. They employ paradigms of chemical bonding to design new species and decode bonds of already known ones to furtherly advance our knowledge. We discuss design and synthesis of NaBH3-, a first exotic cluster with Na- bonded to neutral BH3 fragment; design and experimental confirmation of B2Al3-, a cluster exhibiting triple B-B bond; delocalized bonds (known as aromaticity) and their transformation in Au clusters; expansion of the same concept of delocalized bonding to 2D semiconducting materials; and finally, a special case of mechanical bond, when stability of two interlocked molecular rings provides the state known as kinetic trap.

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