Complexation of Trivalent Lanthanides with Hexaalkyl Nitrilotriacetamides into Methylimidazolium-Based Ionic Liquids: Spectroscopic, Electrochemical, Calorimetric, and Theoretical Insights

Exothermic, spontaneous inner-sphere complexation of trivalent lanthanides with N,N,N′,N′,N″,N″-hexaalkyl-substituted nitrilotriacetamides (HRNTAs) into 1-hexyl-3-methylimidazolium-bis(trifluoromethylsulfonyl)imide (C6mim NTf2) is reported with a predominant presence of ML and ML2 complexes having complexation constants, β1Eu 3.10 ± 0.02 ,β1Nd 2.67 ± 0.03 and β2Eu 5.22 ± 0.04, β2Nd 4.95 ± 0.02, respectively, for the n-butyl-substituted HRNTA (HBNTA); while those for the n-hexyl derivative (HHNTA) are β1Eu 4.27 ± 0.03, β1Nd 3.71 ± 0.03 and β2Eu 7.70 ± 0.03, β2Nd 7.18 ± 0.04, respectively. HHNTA shows better complexing ability; whereas the stronger complexation of the Nd3+ over Eu3+ is attributed to the lanthanide contraction. Furthermore, the nature of the ionic liquid also influences the extent of complexation with the trend: C4mim NTf2 > C6mim NTf2 > C8mim NTf2, which follows the order of their dielectric constants. Judd–Ofelt parameters were calculated from photoluminescence data to get an idea about the symmetry of the Eu3+ complexes. Electrochemical investigations give diffusion coefficient values of 1.17 × 10–7 and 8.26 × 10–8 cm2/s for the Eu3+ complexes of HBNTA and HHNTA, respectively. Changes in the spectral characteristics and peak positions are evidenced in the FTIR spectra on the complexation of Eu3+ with the HRNTA ligands in C6mim NTf2. Structure optimization for the complexes was performed by DFT computations.