Dual-ligand luminescent metal-organic frameworks towards environmental remediation efforts

Rapid industrialization during the 20th century has left an indelible mark on the global landscape. Often, industrial processes cannot be regulated to match the pace at which nations are developing—infrastructures become more complex without proper management. Contamination of local environments from these operations has plagued ecosystems and can lead to detrimental effects on a larger scale. In recent decades, the development of “green” industrial agendas has diminished pollution and enriched efforts for environmentally sustainable technologies, however this progression does not remediate the contamination that already exists. Functional materials that can detect ultralow concentrations of pollutants are essential before they accumulate and cause extensive damage. Furthermore, dual-performance compounds that sense and extract contaminants would streamline environmental purification efforts and simplify remediation procedures. Luminescent metal-organic frameworks (LMOFs) are a rapidly growing category of functional, crystalline materials useful for a broad range of applications. LMOFs are comprised of single metal ions or clusters linked together through organic ligands. Extended, multidimensional frameworks are formed that boast tunable surfaces and optical properties. The ability to alter porosity and chemical functionalities within the material enhance the effectiveness to interact with specifically targeted analytes. Organic ligands within LMOFs, through the scope of this work, contain aromatic groups that undergo optical emission under specific irradiation. Linker molecules with varying functional moieties are also incorporated into LMOFs. When assembled together, the materials that are produced exhibit altered optical emission profiles through strong guest-host interactions as well as the interplay between the optically-active and functionalized organic ligands. Additionally, enhanced uptake of guest molecules into the LMOF channels highlight the dual-performance of these materials. Overall, this dissertation focuses on the design, synthesis, characterization and application of LMOFs for the luminescence-based sensing and extraction of various inorganic/organic species, important for both contamination remediation and energy-related applications.Ph.D.Includes bibliographical referencesby Nathan D. Rud