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Dynamic Covalent Self-Assembly of 2- and 3-Tiered Stacks

Ren, Fengfeng
http://orcid.org/0000-0003-2447-2398
http://rave.ohiolink.edu/etdc/view?acc_num=miami1515171393581691

Abstract Details

2018, Doctor of Philosophy, Miami University, Chemistry and Biochemistry.
Dynamic covalent chemistry is a powerful synthetic tool for the construction of complex molecules. Imine formation is a well-characterized dynamic covalent reaction that has been extensively applied to the synthesis of various two-dimensional and three-dimensional covalent organic materials. In chapter two, simple discotic cores functionalized with rigid reactive arms have been assembled into two- and three-tiered covalent stacks through imine formation. The targets are obtained in good yields, but competing formation of misassembled byproducts highlights some of the challenges inherent to the thermodynamically controlled assembly of rigid, compact, three-dimensional architectures. The structures comprise a central stack of arenes surrounded by a triple helix of interconnected arms. The racemization rate is strongly dependent on the number of tiers, suggesting that cooperative conformational coupling rigidifies these multi-tiered structures. In chapter three, some alternate strategies were examined to address some problems encountered during the assembly of the 3-tiered stacks in Chapter 2: there was competing formation of misassembled byproducts and a halting of assembly at the 2-tiered stack. In an effort to overcome these challenges, different monomers were synthesized and studied. Two monomers were successfully prepared; however, no desired 2- and 3-tiered stacks were obtained. In chapter four, benzene cores functionalized with flexible amino and aldehyde-arms were assembled into 2- and 3-tiered covalent stacks through imine formation. The benzene core and the reactive arms were connected with ethylene groups. This introduced more flexibility to the monomers compared to our previously used monomers, which were connected through acetylene moieties. The new stacks were obtained in good yield despite the increased flexibility of the systems. Further, the previous problems in assembling rigid three-tiered stacks, which showed competing byproduct formation, were solved. Structural flexibility affords a faster conformational racemization rate.
C. Scott Hartley (Advisor)
Richard Taylor (Committee Chair)
Dominik Konkolewicz (Committee Member)
David Tierney (Committee Member)
Saul Justin (Committee Member)
94 p.
Chemistry
dynamic covalent chemistry, self-assembly, imine metathesis, covalent stacks, thermodynamic control

Recommended Citations

Citations

  • Ren, F. (2018). Dynamic Covalent Self-Assembly of 2- and 3-Tiered Stacks [Doctoral dissertation, Miami University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=miami1515171393581691

    APA Style (7th edition)

  • Ren, Fengfeng. Dynamic Covalent Self-Assembly of 2- and 3-Tiered Stacks. 2018. Miami University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=miami1515171393581691.

    MLA Style (8th edition)

  • Ren, Fengfeng. "Dynamic Covalent Self-Assembly of 2- and 3-Tiered Stacks." Doctoral dissertation, Miami University, 2018. http://rave.ohiolink.edu/etdc/view?acc_num=miami1515171393581691

    Chicago Manual of Style (17th edition)

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This open access ETD is published by Miami University and OhioLINK.