1,4-Naphthalenediyl-Bridged Molecular Gyrotops: Rotation of the Rotor and Fluorescence in Solution

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• 作者：Yohei Nishiyama ; Yusuke Inagaki ; Kentaro Yamaguchi ; Wataru Setaka
• 刊名：Journal of Organic Chemistry
• 出版年：2015
• 出版时间：October 16, 2015
• 年：2015
• 卷：80
• 期：20
• 页码：9959-9966
• 全文大小：547K
• ISSN：1520-6904

文摘

Macrocage molecules with a bridged 蟺-electron system have been reported as molecular gyrotops in which the 蟺-electron system can rotate within the cage. We recently reported the dynamics of the rotor in solution using 1,4-naphthalenediyl-bridged molecular gyrotops, which consist of cages formed of three C₁₄, C₁₆, or C₁₈ chains. In this work, we synthesized novel gyrotops with C₁₅ and C₁₇ chains and systematically investigated the activation energies for the rotation of the rotor in solution. The activation energies for rotation in solution were found to decrease with increasing size of the cage. Therefore, a rotational barrier can be designed by adjusting the length of the side chains in these molecular gyrotops. Additionally, these gyrotops were fluorescent in solution; the quantum yields and lifetimes of the fluorescence were investigated. However, these properties were not influenced by the chain length owing to a large difference in time scale between fluorescence (10^鈥?鈥?0^鈥? s) and the rotational dynamics inside the cage (10掳鈥?0^鈥? s).