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1,4-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 Introduction 2 Properties of 1,4-Dithiins and Thianthrenes 3 Synthesis of 1,4-Dithiins and Thianthrenes 3.1 Synthesis of 1,4-Dithiins 3.2 Synthesis of Thianthrenes 4 Application of 1,4-Dithiins and Thianthrenes in Materials 4.1 Thianthrene-Containing Polymers 4.2 Thianthrene in Redox-Active Materials 4.3 Thianthrenes and 1,4-Dithiins in Supramolecular Chemistry and Self-Assembly 4.4 Thianthrenes in Phosphorescent Materials 4.5 Thianthrenes with Other Interesting Photophysical Properties 4.6 Thianthrenes in the Synthesis of Non-natural Products 5 Conclusion [ABSTRACT FROM AUTHOR]

The design and synthesis of new macrocycles with well-defined cavities represent a promising avenue for the development of new supramolecular hosts. Moreover, the ability to diversify a macrocycle through chemical manipulations enables the fine-tuning and tailoring of properties. In this report, the synthesis and functionalization of thiapillar[6]arene, a pillar[6]arene analogue in which the bridging methylene groups are replaced by sulfurs, are described. First, we demonstrate the scalable synthesis of the parent thiapillar[6]arene. Next, the diversification of thiapillar[6]arene is demonstrated via functionalization of the phenols and oxidation of the sulfur atoms. The solid-state structures of two thiapillar[6]arene derivatives are reported, and the effect of sulfur oxidation state on the macrocyclic conformation is discussed. All sulfone derivatives described were found to demonstrate high luminescence quantum yields (ΦF = 0.43–0.66) in CH2 Cl2 with emission maxima between λ = 404 and 462 nm. Lastly, assessment of the electrochemical properties of the sulfone derivatives by square-wave voltammetry revealed electron-accepting ability owing to the oxidation of the sulfur atoms, with four reduction events observed for the analogues surveyed. Overall, this work implicates thiapillar[6]arene as a modular scaffold amenable for further applications in host–guest chemistry and sensing. [ABSTRACT FROM AUTHOR]