Date of Graduation
12-2021
Document Type
Dissertation
Degree Name
Doctor of Philosophy in Chemistry (PhD)
Degree Level
Graduate
Department
Chemistry & Biochemistry
Advisor
Hudson Beyzavi
Committee Member
David Paul
Second Committee Member
Neil Allison
Third Committee Member
Chenguang Fan
Fourth Committee Member
Lauren Greenlee
Keywords
Crystalline polymer, Nanomaterials, Organic chemistry
Abstract
Chapter 1: COFs (covalent organic frameworks) are a new type of microporous crystalline polymer connected by organic units via strong covalent bonds. Due to their well-defined crystalline structures and excellent chemical and thermal stabilities, COF materials are considered promising candidates in applications such as gas adsorption, catalysis, and energy storage.Chapter 2: A new covalent organic framework (COF) based on imine bonds was assembled from 2-(4-formylphenyl)-5-formylpyridine and 1,3,6,8-tetrakis(4-aminophenyl)pyrene, which showed an interesting dual-pore structure with high crystallinity. Postmetallation of the COF with Pt occurred selectively at the N donor (imine and pyridyl) in the larger pores. The metalated COF served as an excellent recyclable heterogeneous photocatalyst for decarboxylative difluoroalkylation and oxidative cyclization reactions. Chapter 3: We describe the design and synthesis of highly stable and irreversible amine-linked COFs. The proposed amine linkage is prepared via irreversible nucleophilic aromatic substitution reactions (SNAr) of 5,10,15,20-tetrakis(perfluorophenyl)porphyrin (TPPF20) L1 with ethane-1,2-diamine L2,1,4-phenylenedimethanamine L3, or cta(3-aminopropyl) silsesquioxanehydrochloride (OAS-POSS) L4 to form COF-21, XYCOF, and SiCOF, respectively. Post-metalation of COF-21 with iron led to FeClCOF-21, in which its model K1 displayed excellent catalytic performance towards a tandem catalytic synthesis of 2-phenyl-1H-benzo[d]imidazole.
Citation
Almansaf, Z. A. (2021). Design, Synthesis, and Catalytic Application of Crystalline Porous Nanomaterials. Graduate Theses and Dissertations Retrieved from https://scholarworks.uark.edu/etd/4317