Ferrocenyl Benzoic Acid Rare Earth Complexes, Synthesis, Structure And Performance Research

A series of m-ferrocenylbenzoate [m-ferrocenylbenzoate= m-OOCH4C6Fc, Fc= (η5-C5H5)Fe(η5-C5H4)] lanthanide coordination polymers, [Ln(μ2-OOCH4C6Fc)(η2-OOCH4C6Fc)μ2-η2-OOCH4C6Fc)(CH3OH)2]n [Ln= La (1), Pr (2), Nd (3), Sm (4), Gd (5), Dy (6), Er (7), Yb (8) and Lu (9)], have been synthesized by reactions of with Ln(NO3)3·6H2O in this paper. Three m-ferrocenylbenzoate copper complexes [Cu(μ2-OOCH4C6Fc)4(CH3OH)2] (10), [Cu(η2-OOCH4C6Fc)2(4,4'-bpy)]n (bpy= bipyridine) (11) and [Cu(η2-OOCH4C6Fc)2(2,2'-bpy)] (12) have been synthesized by reactions of m-NaOOCH4C6Fc with Cu(CH3COO)2·H2O as well as 4,4'-bpy and 2,2'-bpy.X-ray structural analyses reveal that 1,2 and 5 are isostructural with a one-dimensional linear chain structure. Three types of coordination modes for m-ferrocenylbenzoate are observed in the unit structure which consists of the eight-membered metallacycle Ln2(COO)2 and the rhomboid Ln2O2.10 displays a dimer structure. In 11,4,4'-bpy bridges Cu(II) to form a one-dimensional zigzag structure.12 possesses a monomer structure.Electrochemical studies indicate that 1-9 exhibit a reversible redox wave of FeⅡ/FeⅢand the half-wave potentials of 1-9 are slightly more positive than that of m-ferrocenylbenzoic acid. Magnetic investigations show that an antiferromagnetic interaction between Gd(Ⅲ) ions exists in 5. There is an antiferromagnetic coupling between Cu(II) ions in 10.