d- or f-mononuclear and related heterodinuclear complexes with [1+1] asymmetric compartmental macrocycles

d- or f-mononuclear and d,f-heterodinuclear complexes with the [1+1] asymmetric compartmental macrocycles H2LA, H2LB, H2LC or H2LD, 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'-(3,6-dioxaoctane-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)(CH3OH)] (MLn = LaCu, LaZn, TbCu) shows the metal(II) ion residing in the N2O2 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 O2O4 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.