Synergistic Effect of Serendipity and Rational Design in Supramolecular Chemistry

Abstract

Many of the higher nuclearity Werner-type clusters are fortuitous discoveries. This clearly suggests that the principles which control cluster formation are still poorly understood from the point of view of rational design. However, the predictable nature of coordination chemistry has been used successfully for the specific generation of the metalla-topomers of the well-known organic-based coronates and cryprates. Furthermore, it has been shown that the metal coordination geometry and the orientation of the interacting sites in a given ligand provide the instruction, or blueprint, for the rational design of high symmetry coordination clusters. Based on these principles, and the interplay with serendipity, directed syntheses for polynuclear metalla-coronates, sandwich complexes, manifold metalla-cryptates, and metalla-cylinders have been developed. Only recently, the combination of detailed symmetry considerations with the basic protocols of coordination chemistry have made the design of rational strategies for the construction of a variety of nanoscale systems with procured shape and size feasible. Highlights among these species are cube-like clusters and multicompartmental cylindrical nanostructures.