New heterotrinuclear complexes with the general formula [Cu2Ln(H2L)(HL)(NO3)2]·MeOH (Ln = Ho (1), Er (2), H4L = N,N'-bis(2,3-dihydroxybenzylidene)-1,3-diaminopropane) were synthesized using compartmental Schiff base ligand in conjugation with auxiliary ligands. The compounds were characterized by elemental analysis, ATR-FTIR spectroscopy, X-ray diffraction, TG, DSC, TG-FTIR and XRD analysis. The N2O4 salen-type ligand coordinates 3d and 4f metal centers via azomethine nitrogen and phenoxo oxygen atoms, respectively, to form heteropolynuclear complexes having CuO2Ln cores. In the crystals 1 and 2, two terminal Cu(II) ions are penta-coordinated with a distorted square-pyramidal geometry and a LnIII ion with trigonal dodecahedral geometry is coordinated by eight oxygen atoms from [CuII(H2L)(NO3)]- and [CuII(HL)(NO3)]2- units. Compounds 1 and 2 are stable at room temperature. During heating, they decompose in a similar way. In the first decomposition step, they lose solvent molecules. The exothermic decomposition of ligands is connected with emission large amounts of gaseous products e.g., water, nitric oxides, carbon dioxide, carbon monoxide. The final solid products of decomposition 1 and 2 in air are mixtures of CuO and Ho2O3/Er2O3. The measurements of magnetic susceptibilities and field dependent magnetization indicate the ferromagnetic interaction between CuII and HoIII ions 1.
Keywords: ATR-FTIR spectroscopy; TG-FTIR; compartmental Schiff base; heteronuclear CuIILnIIICuII complex; thermal analysis TG/DSC.