Mirzaei, Saber
(2023)
Template-Assisted Synthesis of Supramolecular Nanotubes, Anion Receptors, and Molecular Gloves.
Doctoral Dissertation, University of Pittsburgh.
(Unpublished)
This is the latest version of this item.
Abstract
Supramolecular chemistry has been an exciting branch of organic chemistry during the past decades. Among macrocyclic molecules, macrocyclic arenes are the most well-known and explored type of compounds. In the present thesis, I explored the chemistry of a well-known macrocyclic arene, resorcin[4]arene, as the template to synthesize contorted and strained aromatic compounds, and anion receptors. Chapter 1 provides a general introduction on supramolecular chemistry and has been divided into three sections: 1) macrocyclic molecules, 2) C–H hydrogen bonding architectures, and 3) contorted conjugated macrocycles.
In Chapter 2, I introduce our approach employing derivatized resorcin[4]arenes as templates towards the synthesis of highly strained aromatic molecules. The top rim of these molecules consists of eight para connected phenylenes and resembles the structure of [8]cyclo-para-phenylene. Chapter 3 demonstrates how the same basic template (resorcin[4]arene) can be used towards zigzag tubularenes by incorporating subtle changes in the synthetic approach. The end result is best described as radially-oriented cyclo-meta-phenylenes. The experimental and computational techniques are discussed for these novel species.
Anion recognition molecules are described in Chapter 4. Here, I demonstrate how derivatized resorcin[4]arenes form the basis to create hosts with an unprecedented ability to bind anions via C–H hydrogen bonding. The overall structure is tuned by a late-stage functionalization of the resorcin[4]arene template with a wide range of aromatic building blocks. Our novel approach demonstrates that by rigidifying and installing electron-withdrawing groups (mainly fluorine atoms), we can produce a new family of anion hosts with highly electropositive hydrogen atoms residing within the cavity of these hosts which are used to sequester non-spherical anions.
Finally, Chapter 5 presents a novel application of resorcin[4]arenes in the gram-scale synthesis of an octa-bromo cavitand, which is used in a two-step synthetic approach towards a rigid basket-like molecule that we colloquially refer to as “nanoglove”, since it is able to host or “catch” fullerenes with high affinity. In contrast to the conjugated systems reported in Chapters 2 and 3, the top rim of this molecule is made of twelve conjugated phenylenes producing an aperture suitable for fullerene binding.
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Details
| Item Type: |
University of Pittsburgh ETD
|
| Status: |
Unpublished |
| Creators/Authors: |
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| ETD Committee: |
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| Date: |
26 January 2023 |
| Date Type: |
Publication |
| Defense Date: |
6 December 2022 |
| Approval Date: |
26 January 2023 |
| Submission Date: |
15 November 2022 |
| Access Restriction: |
1 year -- Restrict access to University of Pittsburgh for a period of 1 year. |
| Number of Pages: |
208 |
| Institution: |
University of Pittsburgh |
| Schools and Programs: |
Dietrich School of Arts and Sciences > Chemistry |
| Degree: |
PhD - Doctor of Philosophy |
| Thesis Type: |
Doctoral Dissertation |
| Refereed: |
Yes |
| Uncontrolled Keywords: |
Supramolecular chemistry
Host-Guest
Noncovalent Interactions |
| Date Deposited: |
26 Jan 2023 13:49 |
| Last Modified: |
26 Jan 2024 06:15 |
| URI: |
http://d-scholarship.pitt.edu/id/eprint/44001 |
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Template-Assisted Synthesis of Supramolecular Nanotubes, Anion Receptors, and Molecular Gloves. (deposited 26 Jan 2023 13:49)
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