Unique inclusion behaviour of 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetraaminothiacalix[4]-arene towards small organic molecules
Unique inclusion behaviour of 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetraaminothiacalix[4]-arene towards small organic molecules
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DOI：
10.1080/10610278.2013.806808
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发表时间：
2013-10
影响因子：
3.3
通讯作者：
Naoya Morohashi;H. Katagiri;Takanori Shimazaki;Y. Kitamoto;Shinya Tanaka;C. Kabuto;Nobuhiko Iki;T. Hattori;S. Miyano
中科院分区：
文献类型：
--
作者：
Naoya Morohashi;H. Katagiri;Takanori Shimazaki;Y. Kitamoto;Shinya Tanaka;C. Kabuto;Nobuhiko Iki;T. Hattori;S. Miyano
四氨基硫杂杯芳烃3含有四个氨基，而不是对叔丁基硫杂杯[4]芳烃2的羟基，在纯净的溶剂或客体溶液中结晶后，对有机小分子表现出不同于化合物2的包合性质。X-射线晶体分析表明，化合物3的锥形空腔中含有硝基甲烷和乙腈，与化合物2的包裹体晶体中常见的一样，而二氯甲烷占据化合物3的两个远端苯环之间的空间，采用1，3-交替构象。形成二聚体的醋酸填充了一个被四个主体分子包围的小孔，这些分子呈锥形结构。此外，具有1，3-交替构象的化合物3的无客体晶体吸收乙腈，得到与结晶得到的晶体结构相同的包合物晶体。因此，化合物3可以根据客体化合物的结构灵活地改变其构象。
Tetraaminothiacalixarene 3, bearing four amino groups instead of the hydroxy groups of p-tert-butylthiacalix[4]arene 2, exhibits inclusion properties different from those of compound 2 towards small organic molecules upon crystallisation from neat solvents or guest solutions. X-ray crystallographic analyses reveal that nitromethane and acetonitrile are included into the cone-shaped cavity of compound 3, as is often seen in inclusion crystals of compound 2, whereas dichloromethane occupies a space between two distal benzene rings of compound 3, adopting a 1,3-alternate conformation. Acetic acid, which forms a dimer, fills a pore surrounded by four host molecules with a pinched cone conformation. Furthermore, guest-free crystals of compound 3 with a 1,3-alternate conformation absorb acetonitrile to give inclusion crystals with the same crystal structure as that obtained by the crystallisation. Thus, compound 3 flexibly changes its conformation according to the structures of guest compounds.