Graduation Year

2023

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

Shengqian Ma, Ph.D.

Committee Member

H. Lee Woodcock, Ph.D.

Committee Member

Vinay K. Gupta, Ph.D.

Keywords

Metalloporphyrin, MOF, Encapsulation, Spectroscopy, MMPF, Sensing, Catalysis

Abstract

Porphyrins are a group of heterocyclic macrocycles that play crucial roles in various biological processes such as electron transfer, catalysis, and sensing. Hemoglobin, which carries oxygen in the blood of mammals, and chlorophyll, which drives photosynthesis in plants and algae, are both porphyrins. The ability of porphyrins to bind metal ions and their unique electronic and photophysical properties make them an excellent platform for designing functional materials for various applications, often drawing inspiration from their function in nature. Metal-organic frameworks (MOFs) are a class of porous materials that have been extensively studied in recent years due to their high surface area, tunable pore size, and potential for various applications such as gas storage, separations, and catalysis. The incorporation of porphyrins into MOFs has attracted considerable attention due to their versatile functionality and the synergy between MOF material characteristics and porphyrin applications. In this dissertation, we focus on the use of porphyrin-based MOFs and porphyrins encapsulated into MOFs for sensing and catalysis applications. Herein, we synthesize novel porphyrins and incorporate MOFs, either as part of a new framework or encapsulated inside the framework of a known MOF. These porphyrin MOFs have been used as efficient catalysts for cycloaddition reactions, epoxidation and alcoholysis reactions, degradation of mustard simulant, and nitroaromatics fluorescence quenching detection, which has potential applications in the detection of explosives. Additionally, we have investigated the impact of using synthetically modified porphyrins to assemble MOFs on the photophysics of the porphyrin. The electronic properties of porphyrins make them highly sensitive to changes in the local environment, but also excellent sensors. By studying the photophysics of porphyrin MOFs, we gain insights into their sensing mechanisms and lay groundwork for the reticular design of porphyrinic MOF sensors. Further, the photophysics of fixed-distance Forster resonance energy transfer and photoinduced electron transfer between co-encapsulated metalloporphyrin and ruthenium polyimine complex were investigated for energy conversion and storage applications. This dissertation presents a comprehensive study of the use of porphyrin-based MOFs for sensing and catalysis applications. Our findings demonstrate the potential of porphyrin MOFs for a wide range of applications, including environmental remediation and detection of hazardous compounds. These studies provide insights into the photophysics of porphyrin MOFs, which can guide the design of new porphyrin-based materials for sensing and optoelectronic applications.

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