Metallosupramolecular Architectures of Pseudoterpyridine-Type Ligands and Zn^II Metal Ions

Abstract

This paper reports the solid state structures of two new metallosupramolecular complexes resulting from pseudoterpyridine bis-hydrazone-type 3 and bis-acylhydrazone-type 4 ligands and ZnII metal ions. The complex 32ZnII are quantitatively trapped by crystallization via constitutionally driven selection from binary solutions of 1:1 and 2:1 3:ZnII (mol:mol). The constitutional internal overlap between the phenyl moieties and the central pyridine moiety clearly plays an important role for internal holding and stabilizing the duplex formation by π−π stacking. The crystal 4ZnII*4 heterostructure and its packing reported in this paper present uncommon features with many other similar architectures reported by now. This structure shows a relatively new structural concept: the 4ZnII complex in which the ZnII ions are coordinated by one ligand rolling the axial position of the metal ion, further interacting by H-bonding with the free ligand 4 in the crystal, allowing one to obtain 2D-layered architectures.