A distorted cubic tetranuclear copper(II) phosphonate cage with a double-four-ring-type core

摘要

The reaction of Cu-2(O2CMe)(4)-2H(2)O with tert-butylphosphonic acid and 3,5-di-tert-butylpyrazole in the presence of triethylamine leads to a high-yield synthesis of the tetranuclear compound [Cu-2(3,5-t-Bu(2)PzH)(2)(t-BuPO3)(2)](2) (1). The latter has a distorted cubic cage structure and its core resembles the D4R (double-four-ring) motif found in zeolites. The phosphonate, [t-BuPO3](2-), functions as a dianionic tridentate ligand, while the pyrazole ligands are neutral and are monodentate. The coordination geometry at each copper atom is distorted square planar with a 3O,1N coordination environment. Magnetic measurements on 1 reveal that the chi T product continuously decreases to reach a value very close to zero at 1.8 K, indicating dominant antiferromagnetic interactions between Cu(II) ions that leads to an S = 0 ground state. The tetranuclear cage 1 functions as a very effective artificial nuclease in the presence of an external oxidant, magnesium monoperoxyphthalate.