The Synthesis and Application of 1,4-Dithiins, Thianthrenes, and Other Sulfur-Rich Scaffolds
Name
etkind-sietkind-phd-chemistry-2022-thesis.pdf
Description
Thesis PDF
Size
24.59 MB
Format
Adobe PDF
Checksum (MD5)
fee965f575e6d25bec39900ce1281afd
Author(s)
Etkind, Samuel I.
Advisor(s)
Swager, Timothy M.
Date Issued
May 2022
Publisher
Massachusetts Institute of Technology
Abstract
This thesis describes the synthesis and applications of various sulfur rich compounds, focusing on 1,4-dithiins, thianthrenes, and new sulfur-rich macrocycles.
In Chapter 1, we offer a review of the properties, general synthesis, and materials application of 1,4-dithiins and thianthrenes. Additionally, the installation of sulfur atoms in macrocyclic compounds and the benefits thereof is detailed.
In Chapter 2, we design a macrocyclic anion receptor containing electroactive 1,4-dithiin units. The binding affinities for various anions is assessed, as well as the response of the receptor when oxidized in the presence of anionic guests.
In Chapter 3, we disclose the utility of thianthrene-based compounds as electrolytes for symmetric batteries. A range of compounds with bipolar redox-activity are designed and synthesized, and the solvent, supporting salt, and cycling conditions are optimized to fabricate a battery with long cycle life. Implications of this work in the development of storage systems for renewable energy is discussed, as well as further prospects for the field.
In Chapter 4, we develop a sulfurous analog to pillar[n]arene macrocycles in which the bridging methylene groups have been exchanged for sulfurs. The gram-scale production and derivation of the scaffold is explored.
In Chapter 5, we discuss our approach towards porous organic cages. Rational design of a macrocycle as well as attempts for its production and isolation are disclosed. Though we were unable to produce our desired scaffold, we have synthesized useful intermediates that enable access to sulfurous cyclotriveratrylene analogues.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
Terms of Use
In Copyright - Educational Use Permitted
Copyright MIT
Persistent DSpace Link
