Date of Graduation


Document Type


Degree Name

Doctor of Philosophy in Chemistry (PhD)

Degree Level



Chemistry & Biochemistry


Matt McIntosh

Committee Member

Robert Coridan

Second Committee Member

Jackson Lay, Jr.

Third Committee Member

Nan Zheng

Fourth Committee Member

Peter Pulay


CO2 Fixation, Metal Organic Frameworks, Tandem Catalysis, Thin Films


Metal-organic frameworks (MOFs) are crystalline, porous materials comprised of symmetric organic linkers coordinated to positively charged metal atoms or metal oxide nodes. This dissertation uses strategies in crystal engineering to advance the study of functional MOFs with emphasis on thin film deposition. The first chapter of this dissertation will introduce the field of reticular chemistry to the reader and describe synthetic efforts to develop useful building blocks for MOF materials: namely porphyrin macrocycles and carboxylate capped zirconium-oxo and hafnium-oxo clusters. The building blocks for MOFs developed in the first chapter will be employed in the second and third chapters through incorporation into MOF thin films through molecular deposition and bulk deposition respectively. New methods for the molecular deposition of Hf-based MOF films are described which will expand the available MOF types which are known to be deposited in a molecular layer-by-layer fashion. A key methodology is the use of Hf-oxo clusters capped by carboxylate ligands to be used as a potential Hf source for molecular layer-by-layer Hf-MOF deposition. Using an automated epitaxial workstation, films of UiO-66 (Hf) are fabricated for the first time and porphyrinic Hf-based MOFs are developed for catalytic applications. Following these efforts, experiments regarding the bulk-deposition of UiO-66 and UiO-66 (Hf) films are laid out. The UiO-66 (Hf) bulk deposited films are shown to be a promising catalyst for CO2 fixation to epoxides for cyclic carbonate synthesis.