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Metallo-Responsive Liquid Crystalline Monomers, Polymers and Networks

McKenzie, Blayne M.
http://rave.ohiolink.edu/etdc/view?acc_num=case1295565872

Abstract Details

2011, Doctor of Philosophy, Case Western Reserve University, Macromolecular Science and Engineering.
This dissertation focuses on the preparation and properties of a number of liquid crystalline derivatives of the 2,6-bisbenzimidazolylpyridine (Bip) ligand and incorporation of these mesogens into polymers and networks for metallo-responsive polymer actuators. First, a versatile one-pot synthetic platform for the preparation of a range of functionalized Bip derivatives is presented. This protocol significantly reduces the cost and time of previous synthetic routes, while facilitating scale up to multi-gram quantities in good yields (63-90%). Via this platform, a series of liquid crystalline monomers with chemo-responsive properties has been prepared and studied. Tailoring the size of the aromatic core and the length of two pairs of alkyl substituents allows the preparation of calamitic mesogens with a range of tunable thermal liquid crystalline transitions and phase geometries. Depending on the length of the alkyl substituents, the binding of lanthanide- and/or transition metal salts results in either a transition from a nematic or smectic liquid crystalline state to an isotropic material or the manifestation of a metallomesogen. From these monomers, thiol-ene and metathesis chemistry were utilized to prepare oligomeric, polymeric and network liquid crystalline materials. A liquid crystalline elastomer has been prepared which displays soft shape memory, as flexibility is retained in both the permanent and temporary shapes. By incorporating the metallo-responsive mesogen into the backbone of the network polymer, a material which exhibits thermal shape memory behavior as well as light and metal-ion triggered recovery has been accessed. While the metallo-network itself does not exhibit further shape memory properties, this behavior is recovered upon removal of the metal ions from the Bip binding sites.
Stuart Rowan, PhD (Advisor)
LaShanda Korley, PhD (Committee Member)
John Protasiewicz, PhD (Committee Member)
Lei Zhu, PhD (Committee Member)
250 p.
Chemistry; Organic Chemistry; Polymer Chemistry
liquid crystals; shape memory; stimuli-responsive; actuator; elastomer

Recommended Citations

Citations

  • McKenzie, B. M. (2011). Metallo-Responsive Liquid Crystalline Monomers, Polymers and Networks [Doctoral dissertation, Case Western Reserve University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=case1295565872

    APA Style (7th edition)

  • McKenzie, Blayne. Metallo-Responsive Liquid Crystalline Monomers, Polymers and Networks. 2011. Case Western Reserve University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=case1295565872.

    MLA Style (8th edition)

  • McKenzie, Blayne. "Metallo-Responsive Liquid Crystalline Monomers, Polymers and Networks." Doctoral dissertation, Case Western Reserve University, 2011. http://rave.ohiolink.edu/etdc/view?acc_num=case1295565872

    Chicago Manual of Style (17th edition)

case1295565872
788
© 2011, all rights reserved.
This open access ETD is published by Case Western Reserve University School of Graduate Studies and OhioLINK.
Release 3.2.12