Date of Award

Spring 2019

Document Type

Open Access Dissertation

Department

Chemistry and Biochemistry

First Advisor

Natalia B. Shustova

Abstract

The current landscape of technological and industrial related fields is looking for novel materials with enhanced performances, which will not only improve various fields in science, but also can ensure increased environmental safety. Recently, metal-organic frameworks (MOFs) have been shown as a promising type of material for a wide range of applications including gas storage and separation, sensing, and heterogeneous catalysis. The main advantages of MOFs rely on their modular structures as well as their porosity. For instance, the modular nature of MOFs provides a control over chromophore arrangement, systematic tuning of ligand design and synthetic conditions allowing one to systematically tune photophysical or electronic properties. Thus, these materials could be utilized as a tool to address the current need in enhancement of material performance.

This work presented within the following nine chapters is focused on the design, synthesis, and characterization of MOFs that target fundamental understanding of photophysical properties, energy transfer processes, and the ability to tune electronic structures of these materials. The first chapter reviews MOF applications in areas for which development is highly dependent on fundamental studies of MOF photophysics. Next four chapters discuss a utilization of MOF as an efficient replica of a protein β- barrel to maintain chromophore emission. The major principles governing chromophore photophysical response inside a confined environment are examined. Chapters six and seven describe the key factors responsible for tunability of MOF electronic structure as a function of second metal or mixed valence sites incorporation. Chapter eight demonstrates the unprecedented role of MOF modularity necessary for engineering of radionuclide containing materials. Finally, chapter nine reveals the possibility of MOF electronic structure modulation as a function of external light stimuli.

Overall, this work shows the possibility of MOF engineering towards various applications ranging from photocatalysts to optoelectronic devices.

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Chemistry Commons

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