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Crystal Engineering of Giant Molecules Based on Perylene Diimide Conjugated Polyhedral Oligomeric Silsesquioxane Nano-Atom

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2016, Doctor of Philosophy, University of Akron, Polymer Science.
Molecular architectures and topologies are found contributing to the formation of supramolecular structures of giant molecules. Dr. Cheng’s research group developed a diverse of giant molecules via precisely controlled chemistry synthetic routes. These giant molecules can be categorized into several different families, namely giant surfactants, giant shape amphiphiles and giant polyhedron. By analyzing the hierarchical structures of these carefully designed and precisely synthesized giant molecules, the structural factors which affect, or even dominates, in some cases, the formation of supramolecular structures are revealed in these intensive researches. The results will further contribute to the understanding of dependence of supramolecular structures on molecular designs as well as molecular topology, and providing a practical solution to the scaling up of microscopic molecular functionalities to macroscopic material properties. Molecular Nano Particles (MNPs), including fullerene (C60), POSS, Polyoxometalate (POM) and proteins etc., is defined and applied as a specific type of building blocks in the design and synthesis of giant molecules. The persistence in shape and symmetry is considered as one of the major properties of MNPs. This persistence will support the construction of giant molecules for further supramolecular structures’ study by introducing specific shapes, or precisely located side groups which will facilitate self-assembling behaviors with pre-programmed secondary interactions. Dictating material physical properties by its chemical composition is an attractive yet currently failed approach in the study of materials. However, the pursuit of determining material properties by microscopic molecular level properties is never seized, and found its solution when the idea of crystal engineering is raised: should each atom in the material is located exactly where it is designed to be and is properly bonded, the property of the material is hence determined. In such “bottom-up” approach, the precise fabrication of 2 nm ~ 100 nm nanostructures, is of great research interest. In this thesis, crystal engineering of giant molecules based on PDI conjugated POSS Nano-Atom (PDI-BPOSS) nano-atoms via self-assembly is performed and studied. Herein, three different giant molecules were synthesized: shape amphiphile, m-phenyl-(PDI-BPOSS)2 (S1) and tetrahedron, R-(PDI-BPOSS)4 (S2) and S-(PDI-BPOSS)4 (S3). Single crystals were grown for S1 and S2, X-ray diffraction (XRD), Scanning Electron Microscopy (SEM) and transmission electron microscopy (TEM) were performed, and crystal structures of these samples were determined, while hexagonal superlattice without crystal order can be observed for S3 to exhibit crystal-like morphology.
Stephen Z. D. Cheng (Advisor)
Yu Zhu (Committee Chair)
Toshikazu Miyoshi (Committee Member)
Tianbo Liu (Committee Member)
Thein Kyu (Committee Member)
154 p.

Recommended Citations

Citations

  • Ren, H. (2016). Crystal Engineering of Giant Molecules Based on Perylene Diimide Conjugated Polyhedral Oligomeric Silsesquioxane Nano-Atom [Doctoral dissertation, University of Akron]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=akron1461014185

    APA Style (7th edition)

  • Ren, He. Crystal Engineering of Giant Molecules Based on Perylene Diimide Conjugated Polyhedral Oligomeric Silsesquioxane Nano-Atom. 2016. University of Akron, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=akron1461014185.

    MLA Style (8th edition)

  • Ren, He. "Crystal Engineering of Giant Molecules Based on Perylene Diimide Conjugated Polyhedral Oligomeric Silsesquioxane Nano-Atom." Doctoral dissertation, University of Akron, 2016. http://rave.ohiolink.edu/etdc/view?acc_num=akron1461014185

    Chicago Manual of Style (17th edition)