The reaction of Cu2(O2CMe)(4).2H2O 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 [Cu2(3,5-t-Bu2PzH)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 chiT 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.

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http://dx.doi.org/10.1021/ic701948gDOI Listing

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