Grids with Unusual, High Nuclearity – A Structural Approach

Polynuclear supramolecular homoleptic grid‐like architectures containing s2 (s = 3, 4, 5) metal ions arranged like the elements of a square matrix and located in the coordination spheres generated at the intersection points (“nodes”) of the 2s bridging s‐topic ligands (the “bars” of the grid), are quite rare, but they are fascinating by their formation by self‐assembly, their structures and properties. Moreover, heteroleptic hexanuclear complete [2 × 3] grids, as well as other kinds of grids containing more than four metal centres were reported. The access to such grids necessitates the design of appropriate polytopic ligands. However, in several cases, incomplete grids were obtained instead of the expected complete grids. The structural diversity of the grids with unusual, high nuclearity reported until now is herein reviewed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)