ZnII–Salphen Complexes as Versatile Building Blocks for the Construction of Supramolecular Box Assemblies

Abstract

Zn^II–salphen complexes are readily accessible and interesting supramolecular building blocks with a large structural diversity. Higher‐order supramolecular assemblies, such as molecular boxes based on a bis‐Zn^II–salphen building block and various ditopic bipyridine ligands, have been constructed by means of supramolecular, coordinative Zn^II–N_pyr interactions. The use of bipyridine ligands of differing sizes enables the construction of structures with predefined box diameters. The features of the 2:2 box assemblies were investigated in detail by (variable temperature) NMR spectroscopy, UV‐visible spectroscopy, NMR titrations, and X‐ray crystallographic studies. The spectroscopic studies reveal a high association constant for the Zn^II–salphen–pyridyl motif, which lies in the range 10⁵–10⁶ M⁻¹. The strong interaction between the Zn^II center and pyridine donors was supported by PM3 calculations that showed a relatively high Lewis acid character of the metal center in the salphen complex. Titration curves monitored by UV‐visible show a cooperative effect between the two bipyridine ligands upon complexation to the bis‐Zn^II template, suggesting the formation of 2:2 complexes. The crystal structures of two supramolecular boxes have been determined. In both examples such a 2:2 assembly is present in the solid state, and the box size is different because they consist of different building blocks. Interestingly, the box assemblies line up in the solid state to form porous channels that are potentially useful in a number of applications.