The Synthesis and Application of 1,4-Dithiins, Thianthrenes, and Other Sulfur-Rich Scaffolds

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.

Name thesis:degree_name

Doctoral

Department dc:contributor.department

Massachusetts Institute of Technology. Department of Chemistry

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2022

Author dc:creator

• Etkind, Samuel I.

Advisor dc:contributor.advisor

• Swager, Timothy M.

Statement dc:rights

• In Copyright - Educational Use Permitted
• Copyright MIT

Licence dc:rights.uri

• http://rightsstatements.org/page/InC-EDU/1.0/

Handle dc:identifier.uri

https://hdl.handle.net/1721.1/145129

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/145129