A Model Elastomer with Modular Metal-Ligand Crosslinking

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Craig, Stephen L

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Johnson, Patricia Nicole

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2022-09-21T13:54:26Z

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2022-09-22T08:17:13Z

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2022

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Chemistry

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Metallosupramolecular polymers are increasingly of interest for functional and degradable polymeric materials. In these materials, the metal-ligand bonds often bear an external mechanical load, but little is yet understood about the nature of mechanically-triggered reactions of metal-ligand bonds and how that reactivity influences the mechanical limits of the material. This dissertation presents a poly(cyclooctene) polymer bearing 2,6-bis(1′-methyl-benzimidazolyl)pyridine (Mebip) ligands on sidechains, which provides easy incorporation into polymer backbones and sidechains, binding to a large variety of metal species, and facile synthesis with sites for future study substituent effects. This platform is employed in proof-of-concept studies comparing the crosslinking behavior of iron(II) trifluoromethanesulfonate and copper(II) trifluoromethanesulfonate. It was found through small molecule spectroscopic studies that both metal species bind in the desired 2:1 MeBip:metal stoichiometry for crosslinking. When these small molecule complexes are polymerized as crosslinkers in gel and solid networks, though the extent of crosslinking is found to be similar, the copper(II)-crosslinked networks exhibited a faster relaxation than the iron(II)-crosslinked networks. Further, under high strains, the copper(II)-crosslinked networks exhibited significantly higher extensibility. This work lays the foundation for further investigations of the effect of metal-ligand bonding on force-coupled properties of materials.

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https://hdl.handle.net/10161/25749

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Polymer chemistry

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Materials Science

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Chemistry

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chelator

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coordination polymer

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crosslinking

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Mechanochemistry

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Organometallic

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Supramolecular

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A Model Elastomer with Modular Metal-Ligand Crosslinking

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Dissertation

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-0.06575342465753424

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