Synthesis, Structural Characterization, and Magnetic Studies of Polynuclear Iron Complexes with a New Disubstituted Pyridine Ligand

A series of novel polyiron species have been prepared from the reaction of iron chloride with the 2,5-disubstituted pyridines H2Ln (H2L1 = N,N‘-bis(n-butylcarbamoyl)pyridine-2,6-dicarboxamide; H2L2 = N,N‘-bis(n-ethylcarbamoyl)pyridine-2,6-dicarboxamide). By small modifications of the experimental conditions under which the reactions are carried out, it has been possible to prepare the quadruply stranded diiron(II) complex [Fe2(μ-H2L1)4(μ-Cl)2][FeCl4]2 (1), the metallamacrocycle [Fe2(μ-H2L1)2(THF)4Cl2][FeCl4]2 (2), the hexairon(III) compound [Fe6(L1)2(μ-OMe)6(μ4-O)2Cl4] (3), and the mixed-valence trinuclear iron complexes [Fe3(Ln)3(μ3-O)] (n = 1, 4; n = 2, 5). The X-ray crystal structures of 3 and 5 and magnetic studies for all the compounds are herein presented. Interestingly, the structural analysis of 5 at room temperature indicates that one of the iron centers is FeIII while the other two have an average valence state between FeII and FeIII. The five complexes herein presented demonstrate the great versatility that the new ligand has as a building block for the formation of supramolecular coordination assemblies.