Packing requirements and short-range interactions as structure-directing forces in the intercluster compounds based on silver clusters

Although being composed of high valent ions, the crystal structures of four new supramolecular intercluster compounds, presented in this article, display a major contribution of short-range intermolecular interactions, i.e., aromatic π–π interactions. These structure-directing forces has lead to the formation of an distorted NaCl-type packing in [Ag5(2,2′-bipyridine)4(CCtBu)2][PW12O40] and [Ag5(2,2′-bipyridine)4(CCtBu)2][PMo12O40], and a CsCl-type packing in [Ag8(2,2′-bipyridine)6(CCtBu)4(C3H7NO)2][SiW12O40] and [Ag8(2,2′-bipyridine)6(CCtBu)4(C3H7NO)2][SiMo12O40].

The crystal structures of supramolecular intercluster compounds, consisting of charged nanometer sized building blocks, display a major contribution of the short-range interactions between the cationic building blocks. These short-range interactions support the rock salt, or CsCl-type, respectively, packing of the building blocks on one hand, but on the other causes a distortion of the ideal coordination polyhedra.Figure optionsDownload as PowerPoint slide