Light-Triggered Crystallization of a Molecular Host−Guest Complex

The control of structural changes in supramolecular assemblies is a key point in the development of molecular machines. The reversible photoisomerization of organic compounds such as azobenzene using light as an external input is especially suited because no waste products are generated. Based on our previous studies on the quantitative encapsulation of suitably sized bis-sulfonate guests by a self-assembled, metal−organic cage consisting of four rigid, bent bis-monodentate pyridyl ligands and two Pd(II) ions, we show here how the light-switchable guest cis-4,4′-azobenzene bis-sulfonate can be expelled from its 1:1 host−guest complex triggered by its photoisomerization to the trans-isomer. Using a highly soluble, PEGylated cage derivative, the full reversibility of this light-driven encapsulation/release process is demonstrated. In contrast, a sample of the less soluble, unsubstituted cages including 1 equiv of the cis-guest was shown to result in immediate crystallization upon photoisomerization of the guest. X-ray structure analysis confirmed the guest molecules having left the cavity of the host and on the contrary joining the cages into a polymeric material by binding to their Pd(II) centers from outside.