Synthesis and characterization of a novel Gd(III)–Cu(II) dinuclear adduct

Two novel Gd(III)–Cu(II) dinuclear complexes have been prepared by the acid–base reaction between Gd(hfa)3 and Cu(2,2-oxomac) (1, Cu(2,2-oxomac)Gd(hfa)3) and between Gd(hfa)3 and Cu(3,2-oxomac) (2, Cu(3,2-oxomac)Gd(hfa)3). These complexes have been characterized by elemental analysis and infrared spectroscopy. The structure of 1 has been determined by X-ray diffraction. The copper atom is square pyramidal, bound to the four planar nitrogen atoms of the macrocycle and weakly bound to the oxygen atom of a dimethylformamide (dmf) molecule. The gadolinium atom is at the center of a tricapped trigonal prism. The nine-coordinate gadolinium atom is bound to six oxygen atoms of three hfa ligands, the two oxamide oxygen atoms of the copper macrocycle, and one oxygen atom of a second coordinated dmf molecule. Unsymmetric binding of the copper macrocycle to gadolinium leads to a distortion in the bridging atoms not observed in reactions of the copper macrocycles with transition metal hfa’s.