Design, Synthesis, and Self-Assembly of Nano-Sized Shape Amphiphiles Based on Polyhedral Oligomeric Silsesquioxane and Perylene Bisimides

Design, Synthesis, and Self-Assembly of Nano-Sized Shape Amphiphiles Based on Polyhedral Oligomeric Silsesquioxane and Perylene Bisimides

Bibliographic Details
Main Author: Huang, Jiahao
Language:English
Published: University of Akron / OhioLINK 2020
Subjects:
Polymers
Materials Science
Chemistry
Polymer Chemistry
Online Access:http://rave.ohiolink.edu/etdc/view?acc_num=akron1603670714151325
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spelling ndltd-OhioLink-oai-etd.ohiolink.edu-akron16036707141513252021-08-03T07:16:22Z Design, Synthesis, and Self-Assembly of Nano-Sized Shape Amphiphiles Based on Polyhedral Oligomeric Silsesquioxane and Perylene Bisimides Huang, Jiahao Polymers Materials Science Chemistry Polymer Chemistry In modern materials science and associated technology, self-assembly of molecules have been extensively utilized to fabricated desired or designed microscopic structures, which is usually referred as “bottom-up” approach. The underlying principle is that the macroscopic properties and functions of materials do not solely depend on the chemical structures and composition of constituting molecules, but also their molecular packing across multiple length scales. Compared to the tremendous efforts on the precise controls of primary chemical structures and compositions of molecules and their further correlation to the hierarchal ordered structures and macroscopic functions of materials, the explicit shape, symmetry, and size effects (geometrical effects) of molecules on their self-assembled supramolecular structures and materials properties are far from being fully appreciated and investigated. “Shape amphiphiles”, constructed by conjugating molecular building blocks with distinct shapes and competing interactions, emerge as a very promising molecular system. In this dissertation, based on conjugates of cubic functionalized polyhedral oligomeric silsesquioxanes (POSS) and discotic perylene bisimides (PBIs) and other related arylene bisimides (RBIs), the molecular design and synthesis of a class of giant shape amphiphiles with precisely defined chemical structures are presented. The dedicate balance between entropic and enthalpic interactions is critical for the supramolecular assembly of shape amphiphiles, which is highly sensitive to the subtle change of molecular size and shape of constructing molecular building blocks. Specifically, the conjugation and spatial arrangement of these two different shaped molecular building blocks were adopted in two different symmetries, facilitating the detailed investigation on the specific size, shape, and symmetry effects on their self-assembled supramolecular structures. First, a series of POSS-based giant shape amphiphiles were synthesized and investigated, which are constructed by symmetrically attaching six isobutyl-functionalized POSS (BPOSS) or octyl-functionalized POSS (OPOSS) cages to the planar aromatic cores of RBIs at their both imide positions with tunable linkage lengths and chemical structures. Consequently, by systematically tuning the size and shape of molecular building blocks and the linkage, a series of spherical packing phases were observed in these giant shape amphiphiles including body-centered cubic (BCC), Frank-Kasper (FK) A15, FK σ phase, and a rarely observed FK Z phase in soft matter. Second, adopted in a totally different tetrahedral symmetry, two giant shape amphiphiles constructed by attaching four bulky BPOSS cages to a rigid PBI-based tetrahedral scaffold were synthesized and investigated. Surprisingly, different from the spherical packing phases observed in first class of POSS-based giant shape amphiphiles, hexagonal columnar supramolecular structures were clearly identified in the second class of POSS-based giant shape amphiphiles. Therefore, it is concluded that our POSS-based giant shape amphiphiles provide a feasible platform to further explore how molecular parameters beyond primary chemical structures and compositions affect their self-assembled supramolecular structures, especially in the aspect of fine tuning on their molecular size, shape, and symmetry. 2020 English text University of Akron / OhioLINK http://rave.ohiolink.edu/etdc/view?acc_num=akron1603670714151325 http://rave.ohiolink.edu/etdc/view?acc_num=akron1603670714151325 restricted--full text unavailable until 2025-12-31 This thesis or dissertation is protected by copyright: all rights reserved. It may not be copied or redistributed beyond the terms of applicable copyright laws.
collection NDLTD
language English
sources NDLTD
topic Polymers
Materials Science
Chemistry
Polymer Chemistry
spellingShingle Polymers
Materials Science
Chemistry
Polymer Chemistry
Huang, Jiahao
Design, Synthesis, and Self-Assembly of Nano-Sized Shape Amphiphiles Based on Polyhedral Oligomeric Silsesquioxane and Perylene Bisimides
author Huang, Jiahao
author_facet Huang, Jiahao
author_sort Huang, Jiahao
title Design, Synthesis, and Self-Assembly of Nano-Sized Shape Amphiphiles Based on Polyhedral Oligomeric Silsesquioxane and Perylene Bisimides
title_short Design, Synthesis, and Self-Assembly of Nano-Sized Shape Amphiphiles Based on Polyhedral Oligomeric Silsesquioxane and Perylene Bisimides
title_full Design, Synthesis, and Self-Assembly of Nano-Sized Shape Amphiphiles Based on Polyhedral Oligomeric Silsesquioxane and Perylene Bisimides
title_fullStr Design, Synthesis, and Self-Assembly of Nano-Sized Shape Amphiphiles Based on Polyhedral Oligomeric Silsesquioxane and Perylene Bisimides
title_full_unstemmed Design, Synthesis, and Self-Assembly of Nano-Sized Shape Amphiphiles Based on Polyhedral Oligomeric Silsesquioxane and Perylene Bisimides
title_sort design, synthesis, and self-assembly of nano-sized shape amphiphiles based on polyhedral oligomeric silsesquioxane and perylene bisimides
publisher University of Akron / OhioLINK
publishDate 2020
url http://rave.ohiolink.edu/etdc/view?acc_num=akron1603670714151325
work_keys_str_mv AT huangjiahao designsynthesisandselfassemblyofnanosizedshapeamphiphilesbasedonpolyhedraloligomericsilsesquioxaneandperylenebisimides
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