Self‐Assembly and Characterization of Homo‐ and Heterodinuclear Complexes of Zinc( II ) and Lanthanide( III ) Ions with a Tridentate Schiff‐Base Ligand

Tridentate Schiff‐base ligand H L (L = C 12 H 9 N 2 O) reacts with lanthanide( III ) nitrates to give complexes of formulae [M 2 L 3 (NO 3 ) 3 ], where M = Y 3+ ( 1 ), La 3+ ( 2 ), Nd 3+ ( 3 ), Sm 3+ ( 4 ), Eu 3+ ( 5 ), Gd 3+ ( 6 ), Tb 3+ ( 7 ), Dy 3+ ( 8 ), Ho 3+ ( 9 ), Lu 3+ ( 10 ), and [MM 1 L 3 (NO 3 ) x ], where M = Eu 3+ , and M 1 = Dy 3+ ( 11 ), Zn 2+ ( 12 ); x = 3 for 11 and 2 for 12 . The structures of the complexes have been assigned on the basis of the spectroscopic data (solution analysis) and microanalyses. In the case of complexes 3 , 5 , 8 and 12 the structures have been confirmed by X‐ray crystallography. The structural analysis of the dinuclear complexes showed the presence of two metal atoms [M(1) and M(2)] and three ligands, L . Each lanthanide atom is coordinated to by 9 donor atoms with typical Ln–N and Ln–O distances. Zinc( II ) is coordinated to by two oxygen atoms and four nitrogen atoms from two ligands. The metal ions are bridged by the phenoxo oxygen atoms of the ligands. We have obtained a heterodinuclear complex by a rapid one‐step reaction. Quantum mechanical calculations indicated that the formation of heterodinuclear complex 12 is slightly favored energetically over the homodinuclear complex 5 . (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)