Author ORCID Identifier

https://orcid.org/0000-0001-7709-2650

Date of Award

Summer 7-31-2025

Document Type

Thesis (Ph.D.)

Department or Program

Chemistry

First Advisor

Katherine A. Mirica

Second Advisor

David S. Glueck

Third Advisor

Wenlin Zhang

Abstract

Conductive frameworks are a promising class of materials with electronic, electrochemical, and stimuli-responsive properties that allow scientists to utilize tunable, polymeric structures within valuable applications. This dissertation serves as a fundamental investigation of the structure–property relationships within conductive framework materials and the host-guest chemistry which governs chemiresistive sensing.

Chapter 1 highlights recent investigations into metallophthalocyanine-based metal─organic frameworks (MOFs) ranging from fundamental structure-property relationships to applications of metallophthalocyanine-based MOFs, and it comments on the status of the field while pointing to future opportunities and uses of these functional materials.

Chapter 2 examines the synthesis and characterization of an electronic textile (e-textile), named bismuth 2,3,6,7,10,11-hexahydroxytriphenylene [Bi(HHTP)]. Bi(HHTP) e-textiles demonstrated sensitive chemiresistive detection and gaseous uptake towards hydrogen sulfide gas. This work demonstrates the promise of e-textiles as smart membrane materials.

Chapter 3 investigates three copperphthalocyanine (CuPc)-based MOFs linked with nickel, copper, and zinc (CuPc-O-Ni, CuPc-O-Cu, and CuPc-O-Zn) for the differences in structure-property relationships. This research conveys the impact of molecular structure on the function of the framework material, demonstrating how the differences in material stacking brought about by the linking metal node impact charge transport properties.

Chapter 4 analyzes an array of nine structurally analogous MPc-based framework materials for the chemiresistive sensing of toxic gases such as hydrogen sulfide, nitric oxide, and carbon monoxide. This research demonstrates the structure-property relationships of MPc-based MOFs, as well as the periodic trends in chemical sensing and the host-guest chemistry which governs the mechanism of gas sensing for metallophthalocyanine-based MOFs.

The appendices provide preliminary data that highlight promising future directions: exploring the utility of MPc-based MOFs within a chemiresistive array for the determination of cell health and investigating the development of an e-textile with radiation shielding and sensing capabilities.

In summary, a discussion positions this dissertation within the context of the greater scientific enterprise, highlights fundamental insights into the fields of coordination polymer chemistry and electronic textiles, and details the implications and limitations of the research presented. Investigating fundamental chemistry and the structure-property ii relationships of materials enhances the development and designability of materials for tailored properties and applications.

Available for download on Saturday, August 14, 2027

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