A general synthetic route for the preparation of high-spin molecules: Replacement of bridging hydroxo ligands in molecular clusters by end-on azido ligands

A general method of increasing the ground-state total spin value of a polynuclear 3d-metal complex is illustrated through selected examples from cobalt(II) and nickel(II) cluster chemistry that involves the dianion of the gem-diol form of di-2-pyridyl ketone and carboxylate ions as organic ligands. The approach is based on the replacement of hydroxo bridges, that most often propagate antiferromagnetic exchange interactions, by the end-on azido ligand, which is a ferromagnetic coupler.

Incorporation of end-on N3- ligands, instead of OH− ligands, or replacement of OH− bridges by end-on N3- bridges through rational reactivity chemistry can be considered as a general synthetic route of increasing the ground-state total spin value of a 3d-metal cluster.Figure optionsDownload as PowerPoint slide