Constructing octa- and hexadecanuclear manganese clusters from tetrahedral Mn(III)(3)Mn(II) cores bridged by quinquedentate Schiff base and versatile azide groups.

Reactions of MnX(2) meltsalt (X = Cl and ClO(4)) and a quinquedentate Schiff base ligand together with its coligand azides in MeOH produced the unprecedented assembly of novel octa- and hexadecanuclear manganese clusters containing two and four alternant tetrahedral Mn(III)(3)Mn(II) cores bridged by Schiff base ligands and versatile azides groups. The magnetic measurements on both compounds indicate dominant antiferromagnetic interactions between the metal centers. This synthetic approach may suggest a promising pathway to the design of novel Schiff base-based polynuclear manganese clusters and novel magnetic materials.