Hybrid Cu-Containing Compounds Based on Lacunary Strandberg Anions: Synthesis under Mild Conditions, Crystal...

A one-pot reaction of a copper source (metallic powder Cu⁰ or Cu²⁺ salts) and bpy (bpy = 2,2'-bipyridine) in the presence of (NH₄)₂HPO₄ and (NH₄)₆Mo₇O₂₄·4H₂O yields heterometallic hybrid compounds of the general type {[Cu(bpy)(H₂O)][P₂MoO]}. The structures exhibit a number of phosphomolybdate POMs including not only a common Strandberg anion [P₂Mo₅O₂₃]^6- but also its unprecedented bi- and trilacunary derivatives [P₂Mo₃O₁₈]^8- and [P₂Mo₂O₁₅]^8-. The structural determinants including the metal source (copper powder vs copper salts), counterion of the salts, and stoichiometry of the reagents were examined. An ex situ EPR study revealed the formation of different Cu^II complexes in the reaction mixture depending on the copper precursor. The obtained compounds have been found to possess selectivity toward the sorption of methylene blue in a mixture of organic dyes. DC magnetic measurements of 1-3 indicate rather strong antiferromagnetic metal-metal exchange interactions. Compound 1 exhibits field-induced slow magnetic relaxation in AC magnetic measurements, which is a rarely observed phenomenon among Cu(II) complexes.