Abstract

Mechanically interlocked molecules (MIMs) possess unique architectures and non-traditional degrees of freedom that arise from well-defined topologies that are achieved through precise mechanical bonding. Incorporation of MIMs into materials can thus provide an avenue to discover new and emergent macroscale properties. Here, the synthesis of a phenanthroline-based [2]catenane crosslinker and its incorporation into polyacrylate organogels is described. Specifically, Cu(I) metalation and de-metalation was used as a post-gelation strategy to tune the mechanical properties of a gel by controlling the conformational motions of integrated MIMs. The organogels were prepared via thermally initiated free radical polymerization, and Cu(I) metal was added in MeOH to the pre-treated, swollen gels. De-metalation of the gels was achieved by adding lithium cyanide and washing the gels. Changes in Young’s and shear moduli, as well as tensile strength, were quantified through oscillatory shear rheology and tensile testing. The reported approach provides a general method for post-gelation tuning of mechanical properties using metals and well-defined catenane topologies as part of a gel network architecture.

Committee Chair

Jonathan C Barnes

Committee Members

Kevin Moeller

Comments

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Degree

Doctor of Philosophy (PhD)

Author's Department

Chemistry

Author's School

Graduate School of Arts and Sciences

Document Type

Dissertation

Date of Award

Winter 12-15-2022

Language

English (en)

Author's ORCID

http://orcid.org/0000-0003-1498-7734

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