Ueda Masafumi, Isozaki Moe, Mazaki Yasuhiro
Department of Chemistry, Graduate School of Science, Kitasato University, Sagamihara 252-0373, Kanagawa, Japan.
Molecules. 2023 Jul 17;28(14):5462. doi: 10.3390/molecules28145462.
Sulfur-containing macrocycles have attracted substantial interest because they exhibit unique characteristics due to their polygonal ring-shaped skeleton. In this study, a thianthrene-based cyclic tetramer with the sulfur linker, thiacalix[4]-2,8-thianthrene (TC[4]TT), was successfully prepared from a cyclo--phenylenesulfide derivative using acid-induced intramolecular condensation. Single crystal X-ray diffraction revealed that TC[4]TT adopts an alternative octagonal form recessed to the inner side. Its internal cavity included small solvents, such as chloroform and carbon disulfide. Due to its polygonal geometry, TC[4]TT laminated in a honeycomb-like pattern with a porous channel. Furthermore, TC[4]TT showed fluorescence and phosphorescence emission in a CHCl solution at ambient and liquid nitrogen temperatures. Both emission bands were slightly redshifted compared with those of the reference compounds (di(thanthren-2-yl)sulfane (TTS) and thianthrene (TT)). This work describes a sulfur-containing thiacalixheterocycle-based macrocyclic system with intriguing supramolecular chemistry based on molecular tiling and photophysical properties in solution.
含硫大环化合物因其多边形环状骨架展现出独特特性而备受关注。在本研究中，通过酸诱导分子内缩合反应，成功从环亚苯基硫醚衍生物制备出了带有硫连接基的噻蒽基环状四聚体，即硫代杯[4]-2,8-噻蒽（TC[4]TT）。单晶X射线衍射表明，TC[4]TT呈现出向内凹陷的交替八边形结构。其内腔包含氯仿和二硫化碳等小分子溶剂。由于其多边形几何结构，TC[4]TT以蜂窝状图案堆积，形成了多孔通道。此外，在常温及液氮温度下，TC[4]TT在CHCl溶液中表现出荧光和磷光发射。与参考化合物（二（噻蒽-2-基）硫醚（TTS）和噻蒽（TT））相比，这两种发射带均有轻微红移。这项工作描述了一种基于硫代杯杂环的含硫大环体系，该体系具有基于分子平铺的有趣超分子化学以及溶液中的光物理性质。
