A critical account on π–π stacking in metal complexes with aromatic nitrogen-containing ligands †

Abstract

A geometrical analysis has been performed on π–π stacking in metal complexes with aromatic nitrogen-containing ligands based on a Cambridge Structural Database search and on X-ray data of examples in the recent literature. It is evident that a face-to-face π–π alignment where most of the ring-plane area overlaps is a rare phenomenon. The usual π interaction is an offset or slipped stacking, i.e. the rings are parallel displaced. The ring normal and the vector between the ring centroids form an angle of about 20° up to centroid–centroid distances of 3.8 Å. Such a parallel-displaced structure also has a contribution from π–σ attraction, the more so with increasing offset. Only a limited number of structures with a near to perfect facial alignment exists. The term π–π stacking is occasionally used even when there is no substantial overlap of the π-ring planes. There is a number of metal–ligand complexes where only the edges of the rings interact in what would be better described a C–H⋯π attraction.

Cite this paper

Related papers

1. The Chemistry and Applications of Metal-Organic Frameworks2013
2. Functional Porous Coordination Polymers2004
3. A new family of mesoporous molecular sieves prepared with liquid crystal templates1992
4. Selective gas adsorption and separation in metal–organic frameworks2009
5. Porous, Crystalline, Covalent Organic Frameworks2005