Oligonuclear complexes as tectons in crystal engineering: structural diversity and magnetic properties

This article focuses on the employment of bi- and trinuclear complexes as building blocks in designing novel heterometallic systems. A large variety of polynuclear complexes, ranging from high-nuclearity clusters to high-dimensionality coordination polymers, can be constructed by taking advantage of the high flexibility of the multimetallic nodes. The following oligonuclear complexes are currently used as tectons in our laboratory: (a) bis(alkoxo)-bridged copper(ii) species; (b) homobinuclear species with metal ions held together by end-off, or macrocyclic compartmental ligands; (c) heterometallic complexes with dissymmetric compartmental ligands. The 3d-4f nodes are particularly interesting since the metal ions interact selectively with various spacers. The intra-node exchange interactions, as well as those between the resulting spins, generate interesting magnetic properties.