The Properties, Synthesis, and Materials Applications of 1,4-Dithiins and Thianthrenes

Abstract

Abstract1,4-Dithiin and its dibenzo-analogue, thianthrene, represent a class of non-aromatic, sulfur-rich heterocycles. Their unique properties, stemming from both their non-planar structures and reversible one- and two-electron oxidations, serve as primary motivators for their use in the development of new materials. The applications of 1,4-dithiins and thianthrenes are rich and diverse, having been used for energy storage and harvesting, and the synthesis of phosphorescent compounds and porous polymers, among other uses. This review offers first an overview of the properties of 1,4-dithiin and thianthrene. Next, we describe enabling synthetic methodology to access 1,4-dithiins and thianthrenes with various substitution patterns. Lastly, the utility of 1,4-dithiin and thianthrene in the construction and design of new materials is detailed using select literature examples.1 Introduction2 Properties of 1,4-Dithiins and Thianthrenes3 Synthesis of 1,4-Dithiins and Thianthrenes3.1 Synthesis of 1,4-Dithiins3.2 Synthesis of Thianthrenes4 Application of 1,4-Dithiins and Thianthrenes in Materials4.1 Thianthrene-Containing Polymers4.2 Thianthrene in Redox-Active Materials4.3 Thianthrenes and 1,4-Dithiins in Supramolecular Chemistry and Self-Assembly4.4 Thianthrenes in Phosphorescent Materials4.5 Thianthrenes with Other Interesting Photophysical Properties4.6 Thianthrenes in the Synthesis of Non-natural Products5 Conclusion