Graduation Year

2026

Document Type

Dissertation

Degree

Ph.D.

Degree Name

Doctor of Philosophy (Ph.D.)

Degree Granting Department

Chemistry

Major Professor

Randy W. Larsen, Ph.D.

Committee Member

Theresa Evans-Nguyen, Ph.D.

Committee Member

Ioannis Spanopulos, Ph.D.

Committee Member

Erin Kimmerle, Ph.D.

Keywords

MOF, Optical Sensing, Photophysics, Porphyrin

Abstract

Metal–organic frameworks (MOFs) are highly tunable nanoporous materials with broad applications in gas separation, drug delivery, light harvesting, and chemical sensing. The incorporation of photoactive components into MOFs enables the development of optical sensors capable of detecting a wide range of analytes. Porphyrins and metalloporphyrins are particularly attractive for such applications due to their high molar absorptivity, strong emission quantum yields, and versatile interactions with chemical species.

In this work, two porphyrinic MOFs, PCN-222 and MOF1(Cd), are investigated. Both frameworks utilize tetrakis(4-carboxyphenyl)porphyrin (TCPP) as the organic linker, imparting optical functionality to the materials. Integration of TCPP into the framework induces structural distortions in the porphyrin macrocycle, which significantly influence the photophysical properties. These changes, in combination with exciton coupling effects, contribute to altered absorption and emission behavior within the frameworks.

The sensing capabilities of these MOFs are explored for both environmental and biomedical applications. Nitroaromatic compounds, commonly used in industrial explosives, are persistent environmental pollutants with significant health risks, including skin, eye, and respiratory irritation. The ability of MOFs to detect trace levels of nitroaromatics offers a promising, environmentally friendly alternative to traditional detection methods.

In addition to environmental sensing, these materials are evaluated for their potential in biological detection. Nucleobases, the fundamental components of DNA, are critical targets for genetic analysis and forensic identification. Current DNA sequencing techniques, such as polymerase chain reaction (PCR), require amplification steps that are costly and laboratory-intensive. Porphyrinic MOFs present a potential platform for more economical and sustainable detection of nucleobases, with implications for genetic disease diagnostics and forensic profiling.This dissertation examines the relationship between structural distortion, exciton interactions, and photophysical behavior in porphyrinic MOFs, and evaluates their effectiveness as optical sensors for both environmental and biomedical applications.

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