Abstract

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, new forms of stereoisomerism, and templating of the cage itself. 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.

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