Calorimetric and spectroscopic studies of Eu(III) complexation with tetramethylmalonamide and tetramethylsuccinamide in acetonitrile and dimethylsulfoxide

The complexation of Eu(III) with two N,N,N',N'-alkyl-substituted diamide ligands, tetramethylmalonamide (TMMA) and tetramethylsuccinamide (TMSA), was studied in organic solvents using titration calorimetry, FT IR and luminescence spectroscopy. The formation constants and enthalpy changes of the complexation were determined in pure acetonitrile and in acetonitrile containing small amounts of dimethyl sulfoxide (DMSO). It was observed that TMMA forms stronger complexes with Eu(III) than TMSA in the latter systems, which is attributed to the structural difference between TMMA and TMSA and an entropy effect. The effect of Eu(III) solvation by DMSO on the formation of the Eu(III)-diamide complexes is also discussed.