The Design and Synthesis of Monomers for use in Two-Dimensional Polymerizations
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Authors
Patterson, Dustin D.
Issue Date
2017
Type
Dissertation
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Keywords
acene , monomer , polymer , two-dimensional
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Abstract
The focus of this dissertation is the design and synthesis of monomers for use in the synthesis of two dimensional polymers (2DPs). 2DPs can be described as laterally connected repeat units which cover a plane with no gaps or overlaps. Monomers used for the synthesis of 2DPs must be designed with at least three reactive functional groups; this permits polymerization into a 2D sheet of repeat units. A total of seven different monomer designs were synthetically sought out. Three of the seven monomers, 1-H, 1-MeO, and 1-F are previously reported and their synthesis was improved upon. Synthesis of three novel monomers, 1-FOH, 1-FPOH, and 1-PZn was attempted with the completion of two of the three targets 1-FOH, 1-PZn and a known derivative, 1-P. The above monomers were designed with anthraceno functionalities intended to undergo [4+4] cycloadditions during solid state and air-water interface polymerizations. The monomers intended for polymerization at the air-water interface (1-FOH, 1-FPOH and 1-PZn) were designed with synthetic handles for attachment of a hydrophilic substituent. A pyridine-DEG ligand was synthesized to ligate 1-PZn at the air-water interface. Growth of single crystals of 1-P and 1-H:C70 co-crystals were grown and irradiated at 365 nm, 400 nm, and 465 nm at 100 K-250 K. However, no polymerization occurred because a proper packing motif allowing a topochemical 2D polymerization was not achieved.Monomer, 1-pyz, was synthesized using a novel route which takes advantage of Suzuki coupling chemistry. 1-pyz possesses three pyrazole functionalities intended to undergo coordination with a metal center during polymerization. Monomer 1-pyz relies on reversible coordinative bonding in solution to form a metal coordinated lamellar crystal that can be exfoliated into single 2DP sheets. The highly insoluble monomer was reacted with various Ag, Au, and Mn salts under high temperature and superheated high pressure conditions towards polymerization. A single crystal containing metal coordinated layers of 1-pyz has yet to be realized.
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