Mono-, di-, and trinuclear phosphonate oxygen-bridged copper(II) complexes: syntheses, structures, and properties

Reactions of copper salts, zoledronic acid, and 2,2′-bipyridine/1,10-phenanthroline in aqueous ethanolic solutions afforded four phosphonate oxygen-bridged copper complexes, Cu(bipy)(H4zdn)(HSO4) (1), [Cu2(bipy)2(H2zdn)(H2O)(Cl)]·4H2O (2), [Cu2(phen)2(H2zdn)(H2O)(Cl)]·2.5H2O (3), and [Cu3(bipy)3(H4zdn)(H2zdn)(SO4)]·5H2O (4) (H5zdn = zoledronic acid, bipy = 2,2′-bipyridine, phen = 1,10-phenanthroline). The copper centers of 14 have square pyramidal coordination geometries. The Cu(II) ions are coordinated to bipy/phen, zoledronate, and HSO4/Cl forming mononuclear units for 1, dinuclear for 2 and 3, and trinuclear for 4. These building units are further extended into 3-D supramolecular networks via multiple hydrogen bond interactions. Temperature-dependent magnetic properties of 2 and 4 suggest weak antiferromagnetic coupling (J = −4.53(8) cm−1 for 2, J = −1.69(4) cm−1 for 4). The antitumor activity of 2 was evaluated against the human lung cancer cell line and indicates effective time- and dose-dependent cytotoxic effects.