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.

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