Supramolecular assembly of new heteropolymetalic molecules based on tetraiminodiphenolate macrocycle and hexacyanometallate anions: Magnetostructural and spectroscopic properties

Herein we report on the synthesis, single crystal X-ray structure, spectroscopic and magnetic properties of [{Cu2(tidf)(H2O)}2(μ-CN)2Fe(CN)4]·6H2O (1), [Cu2(tidf)(H2O)2][Ni(CN)4] (2) and [Cu2(tidf)(H2O)2][Fe(CN)5NO]·H2O (3) (tidf = a Robson type macrocyclic ligand obtained on condensation of 2,6-diformyl-4-methylphenol and 1,3-diaminopropane). Complex (1) is pentanuclear; two paramagnetic dicopper(II) units are linked by a hexacyanoferrate(II) ion through two cyano-bridges. All compounds exhibit extensive, three-dimensional, supramolecular structures supported by classic hydrogen bonding between the coordinated aqua ligands, water molecules and cyano groups. Magnetism as a function of the temperature of complexes 1–3 is consistent with a strong antiferromagnetism with exchange parameters 2J estimated −783(29), −913(2), −905(1), respectively.

{Cu2(tidf)(H2O)}2(μ-CN)2Fe(CN)4·6H2O (1), [Cu2(tidf)(H2O)2][Ni(CN)4] (2) and [Cu2(tidf)(H2O)2][Fe(CN)5NO]·H2O (3) (tidf = a Robson type macrocyclic ligand) were prepared and characterized structurally, magnetically and spectroscopically. All compounds exhibit extensive three-dimensional supramolecular structures supported by classic hydrogen bonding between the coordinated aqua ligands, water molecules and cyano groups.Figure optionsDownload as PowerPoint slideHighlights
► Supramolecular structures.
► Electronic structure, magnetic and stereochemical correlations.
► Complex hydrogen-bonding structures.