Abstract
d‐ or f‐mononuclear and d,f‐heterodinuclear complexes with the [1+1] asymmetric compartmental macrocycles H~2~L~A~, H~2~L~B~, H~2~L~C~ or H~2~L~D~, derived from the condensation of 1,2‐diaminoethane or 1,3‐diaminopropane with 3,3′‐(3‐oxapentane‐1,5‐diyldioxy)bis(2‐hydroxybenzaldehyde) or 3,3′‐(3,6dioxaoctane‐1,8‐diyldioxy)bis(2‐hydroxybenzaldehyde), have been synthesized and characterized, including by single‐crystal X‐ray structural determinations. The influence of coordinating size and the number of donor atoms of the two adjacent chambers on the preparation of stable d,f‐heterodinuclear complexes has also been tested. The X‐ray structure of the isostructural complexes [MLn(L)(Cl)~3~(CH~3~OH)] (MLn = LaCu, LaZn, TbCu) shows the metal(II) ion residing in the N~2~O~2~ site in a square‐pyramidal coordination, the fifth apical position being filled by a chloride ion, while each lanthanide(III) ion is located in the O~2~O~4~ site and reaches nona‐coordination by linking six oxygen atoms of the macrocyclic ligand, two chloride ions and the oxygen atom of a methanol molecule. Magnetic susceptibility data, complemented by EPR spectroscopy, of the heterodinuclear complexes, studied over the range 2−300 K, show a ferromagnetic coupling for the CuGd complex, whereas, when comparing CeCu and TbCu derivatives with the corresponding Zn derivatives, no appreciable interaction could be detected for the former and a ferromagnetic interaction seems to dominate in the latter. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)