A new synthetic route towards heterotrimetallic complexes. Synthesis, crystal structure and magnetic properties of a [CuIIMnIICrIII] trinuclear complex

The heterotrimetallic complex, [{LCuMn(H2O)}{Cr(phen)(C2O4)2}](ClO4) · H2O (1), has been obtained by assembling heterobinuclear cations, [LCuMn]2+, with [Cr(phen)(C2O4)2]− ions (H2L is the compartmental Schiff-base resulting from the stepwise condensation of 2,6-diformyl-p-cresol with ethylenediamine and diethylenetriamine). The copper(II) and manganese(II) ions are hosted into the compartments of the macrocyclic ligand. [Cr(phen)(C2O4)2]− acts as a ligand, being coordinated through one oxalato oxygen atom to the apical position of the square pyramidal copper(II) ion. The cryomagnetic investigation of 1 reveals an antiferromagnetic interaction between CuII and MnII within the compartmental ligand (J = −39 cm−1). The interaction between CuII and CrIII across the oxalato bridge is negligible. The crystal structure of [LCuPb](ClO4)2 · H2O, a useful precursor in obtaining 3d–3d′ complexes, is also reported.

Graphical abstractA heterotrimetallic complex, [{LCuMn(H2O)}{Cr(phen)(C2O4)2}](ClO4) · H2O, has been obtained by assembling heterobinuclear cations, [LCuMn]2+, with [Cr(phen)(C2O4)2]− ions (H2L is the compartmental Schiff-base resulted from the stepwise condensation of 2,6-diformyl-p-cresol with ethylenediamine and diethylenetriamine).Figure optionsDownload full-size imageDownload as PowerPoint slide