Thianthrene organic materials : synthesis, properties and applications

Abstract

Thianthrene is a heterocyclic molecule with intriguing electrochemical properties. In this thesis, the synthesis, properties and applications of novel thianthrene-containing organic materials will be discussed. In Chapter 1, key concepts essential for understanding this thesis will be reviewed, including structure, electrochemistry and synthesis of thianthrene, nucleophilic aromatic substitution (S[subscript N]Ar), and redox flow battery. In Chapter 2, we exploit the dynamic, self-correcting nature of the SNAr reaction between ortho-aryldithiols and ortho-aryldifluorides to afford molecules with two, three, and four thianthrene moieties respectively, in excellent yields. The same chemistry is also applied to the synthesis of ladder macrocycles and porous polymer networks. In Chapter 3, we further extend the dynamic SNAr reaction to the synthesis of ladder thianthrene polymers, comparing their electrochemical, photophysical and thermal properties to the properties of their dibenzo-,I 4-dioxin analog. The last two chapters focus on the applications of novel organic materials containing thianthrene and its derivatives. Chapter 4 shows how incorporating thianthrenes into resorcinarene-based cavitand enables electrochemically-induced vase-kite conformation changes. In Chapter 5, we propose a new approach toward designing novel dual anolyte-catholyte molecules by deconstruction of relevant electroactive species. Using thianthrene and anthraquinone as examples, we design and synthesize three new molecular scaffolds exhibiting excellent electrochemical stability over a wide potential range and good solubility for symmetric redox flow battery application.