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Design, Synthesis, and Geometry Directed Self-Assembly of Oligo-Fluorene Based Giant Molecules

Yan, Xiaoyun
http://rave.ohiolink.edu/etdc/view?acc_num=akron160375167282586

Abstract Details

2020, Doctor of Philosophy, University of Akron, Polymer Science.
Shapes of nano-objects matter significantly during their self-aggregation process. Other than the chemical compositions, people start to recognize such geometric effects of the basic building in all aspect blocks fundamentally drive the system into diverse mesostructures. Huge amount of research effects have been paid in the investigation of geometric effects in physiochemical systems. Depending on their length-scales, the effects lying under the geometry of nano-building blocks are demonstrated in directional interactions, shape-persistent molecules/molecular fragments, and larger nanoparticles/colloids. They are in all dimensions and at all scales, which largely ravel the problem and necessitate a prototype system to be scientifically designed and systematically studied. The molecular LEGO approach, therefore, becomes crucial. This approach was conceptualized by the modular synthesis and precise architecture while constructing the shape determined nano building blocks. By finely altering the functional groups at the atomic level, the yielded molecules would form a systematic library and therefore greatly facilitate the following study towards their self-assembly behaviors. In this dissertation, we would follow this approach to demonstrate the essential features of geometric effects in self-assembly. To grab the pivotal principle of them, we choose a simple shape-persistent fragment—“rod-like” motif and studied its interplay with other geometric units. In the following sections, the detailed experimental methods, conditions, and characterization data are presented. Three general molecular arrangements are adopted: rod-coil, rod-sphere-coil and rod-sphere. Within them, some subtypes of molecular geometries (e.g. I-shaped, T-shaped geometries based on the attachment modes) are also investigated. Based on the morphologies obtained, a strong correlation between the self-assembly behavior and molecular architectures are constructed. For the rod-coil molecules, a propensity to form a layered structure was observed. The introduced rod-like unit largely expend the region of the lamellar phase. For rod-sphere-coil arrangement, since the introduced hydrophilic spherical motifs are bulky, a framework like structure was observed. In this structure, multiple molecules come together to form the molecular bundles which then ligate with each other forming the hexagonally arranged cell. A similar phenomenon was observed in the formation of the novel bicontinuous phase. Based on the highly complex texture captured under TEM, we speculate a novel network like structure was involved. Similarly, when a longer coil part was introduced, a highly asymmetric lamellar structure was formed. To our knowledge, this is the system that achieves the largest asymmetric ratios among all systems. This interesting phase behavior was rationalized by the transition from a double-layered hydrophilic domain to a single-layered hydrophilic domain which entropically stabilizes the structure. In the last, we investigate the self-assembly of rod-sphere conjugates in solution. Novel morphologies, including bilayer vesicles, interdigitated nanosheets, and hexagonally structured colloids were obtained. We attribute the abundant yielded phases by modulating geometric parameters to variant mismatching interfacial areas. From a thermodynamic perspective, the delicate balance between bending energy and interfacial energy determines the final structure. The experimental studies were carried out in either bulk or solution suggesting the principles would be widely applied. Also, these studies indicate that “bottom-up” self-assemble based on well-defined giant molecules approach can be rather powerful to fabricate usually complicated hierarchical structures and open up a wide field of supramolecular self-assembly with unexpected structure and properties.
Stephen Cheng (Advisor)
Tianbo Liu (Committee Member)
Toshikazu Miyoshi (Committee Member)
Yu Zhu (Committee Member)
Chrys Wesdemiotis (Committee Member)
293 p.
Polymers

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Citations

  • Yan, X. (2020). Design, Synthesis, and Geometry Directed Self-Assembly of Oligo-Fluorene Based Giant Molecules [Doctoral dissertation, University of Akron]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=akron160375167282586

    APA Style (7th edition)

  • Yan, Xiaoyun. Design, Synthesis, and Geometry Directed Self-Assembly of Oligo-Fluorene Based Giant Molecules. 2020. University of Akron, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=akron160375167282586.

    MLA Style (8th edition)

  • Yan, Xiaoyun. "Design, Synthesis, and Geometry Directed Self-Assembly of Oligo-Fluorene Based Giant Molecules." Doctoral dissertation, University of Akron, 2020. http://rave.ohiolink.edu/etdc/view?acc_num=akron160375167282586

    Chicago Manual of Style (17th edition)

akron160375167282586
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This open access ETD is published by University of Akron and OhioLINK.