Syntheses, structural properties, and charge-transfer complexes of pyrenophanes.
Syntheses, structural properties, and charge-transfer complexes of pyrenophanes.
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DOI：
10.1039/b509719c
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发表时间：
2005-09
影响因子：
3.2
通讯作者：
A. Tsuge;Megumi Otsuka;Tetsuji Moriguch;K. Sakata
中科院分区：
文献类型：
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作者：
A. Tsuge;Megumi Otsuka;Tetsuji Moriguch;K. Sakata
合成了在苯环内、外位带有不同官能团的二硫杂[3.3]（4，9）苯并吡喃类化合物。取代基位于相对苯环内侧的芘番具有芘和苯组分以平行方式存在的构象（平行构象）。相反，芘和苯组分的垂直取向的构象特征已被确认为在相对苯环的外部位置具有取代基的芘番（垂直构象）。观察到对侧苯环上的内氨基与芘环之间的NH-pi相互作用。形成的pyrenophanes和四氰基乙烯（TCNE）的电荷转移复合物进行。研究发现，两个芳香组分的取向、NH-pi相互作用以及对侧苯环上取代基的电子性质对该芘吩体系中电荷转移复合物的性质有重要影响。
Dithia[3.3](4,9)benzenopyrenophanes carrying various functional groups at the inner position or the outer position of the benzene ring have been prepared. The pyrenophanes with the substituent at the inner position of the opposite benzene ring exhibit the conformation in which the pyrene and the benzene components exist in the parallel manner (parallel conformation). On the contrary the conformation characterized by the perpendicular orientation of the pyrene and the benzene components has been confirmed for the pyrenophanes having the substituent at the outer position of the opposite benzene ring (perpendicular conformation). The NH-pi interaction between the inner amino group on the opposite benzene ring and the pyrene ring was observed. Formation of charge-transfer complexes of the pyrenophanes and tetracyanoethylene (TCNE) was performed. It has been found out that the orientation of two aromatic components and the NH-pi interaction as well as the electronic nature of the substituent on the opposite benzene ring significantly affect characteristics of the charge-transfer complexes in this pyrenophane system.