Entropically driven binding in a self-assembling molecular capsule
Entropically driven binding in a self-assembling molecular capsule
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DOI：
10.1038/382239a0
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发表时间：
1996-07-18
期刊：
影响因子：
64.8
通讯作者：
Rebek, J
中科院分区：
文献类型：
--
作者：
Kang, JM;Rebek, J
将分子包封在较大的分子笼或超分子笼中（参见参考文献1）会带来许多有趣的现象，其中包括活性中间体的稳定化（2）、立体异构的新形式（3）以及笼本身的模板化（4，5）。在这里，我们描述了一个自组装氢键分子胶囊，封装客体分子在一个可逆的，显然是熵驱动的过程中，引起不寻常的温度依赖性的形成过程。形成的正熵乍看起来是出乎意料的，这似乎是因为在“裸”笼中包含了不止一个溶剂分子，使得它们被一个大分子（这里是金刚烷或二茂铁）取代，这在熵上是有利的。
THE encapsulation of molecules within larger molecular or supramolecular cages (see ref. 1 for examples) brings about many interesting phenomena, among them the stabilization of reactive intermediates(2), new forms of stereoisomerism(3), and templating of the cage itself 4,5. Here we describe a self-assembling hydrogen-bonded molecular capsule that encapsulates guest molecules in a reversible, apparently entropy-driven process, giving rise to unusual temperature dependence of the formation process. The positive entropy of formation-at first sight unexpected-seems to be the result of the fact that more than one solvent molecule is included in the 'bare' cage, making their replacement by a single large molecule (here adamantane or ferrocene) entropically favourable.