Synthesis of [1]Rotaxane via Covalent Bond Formation and Its Unique Fluorescent Response by Energy Transfer in the Presence of Lithium Ion

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• 作者：Kazuhisa Hiratani ; Maiko Kaneyama ; Yoshinobu Nagawa ; Emiko Koyama ; and Masatoshi Kanesato
• 刊名：Journal of the American Chemical Society
• 出版年：2004
• 出版时间：October 27, 2004
• 年：2004
• 卷：126
• 期：42
• 页码：13568 - 13569
• 全文大小：70K
• 年卷期：v.126,no.42(October 27, 2004)
• ISSN：1520-5126

文摘

Although there have been a lot of reports on the synthesis and properties of [n]rotaxanes (mainly n = 2), only a few reports on the synthesis of [1]rotaxane has been published by Vögtle's group and others (see ref 5). Generally speaking, [1]rotaxane might be expected to exhibit properties different from other rotaxanes, because the rotor and the axle in the [1]rotaxane is bound covalently and closely. We report on a novel method to make [1]rotaxanes via covalent bond formation from a macrocyclic compound. That is, we first prepared a bicyclic compound from macrocycle and then proceeded to [1]rotaxane by aminolysis. This is the first synthetic example of preparation of [1]rotaxane via covalent bond formation, not utilizing weak interactions such as hydrogen bonding, charge transfer, via metal complexation, etc. This method might provide a powerful and new tool for construction of [1]rotaxane as a new supramolecular system. In addition, we investigated energy transfer from rotor to axle using [1]rotaxane that we prepared. Energy transfer occurred perfectly from the naphthalene ring of the rotor to the anthracene ring of the axle. We found also that only lithium ion among alkali ions can drastically enhance the fluorescence intensity. This finding could be applicable to ion-sensing systems, switching devices, and so on.