To reduce high-level radiotoxic waste generated by nuclear power plants, highly selective separation agents for minor actinides are mandatory. The mixed N,O-donor ligand N,N,N',N'-tetrakis[(6-carboxypyridin-2-yl)methyl] ethylenediamine (H(4)TPAEN; 1) has shown good performance as a masking agent in Am3+/Eu3+ separation studies. Adjustments on the pyridyl backbone to raise the hydrophilicity led to a decrease in selectivity and a decrease in M3+-N-am interactions. An enhanced basicity of the pyridyl N-donors was given as a cause. In this work, we examine whether a decrease in O-donor basicity can promote the M3+-N-am interactions. Therefore, we replace the deprotonated "charged" carboxylic acid groups of TPAEN(4-) by neutral amide groups and introduce N,N,N',N'-tetrakis[(6-N '',N ''-diethylcarbamoylpyridin-2-yl)methyl]ethylenediamine (TPAMEN; 2) as a new ligand. TPAMEN was crystallized with Eu(OTf),, and Eu(NO3)(3)center dot 6H(2)O to form positively charged 1:1 [Eu(TPAMEN)](3+) complexes in the solid state. Alterations in the M-O/N bond distances are compared to [Eu(TPAEN)](-) and investigated by DFT calculations to expose the differences in charge/energy density distributions at europium(III) and the donor functionalities of the TPAEN(4-) and TPAMEN. On the basis of estimations of the bond orders, atomic charges spin populations, and density of states in the Eu and potential Am and Cm complexes, the specific contributions of the donor-metal interaction are analyzed. The prediction of complex formation energy differences for the [M(TPAEN)](-) and [M(TPAMEN)](3+) (M3+ = Eu3+, Am3+) complexes provide an outlook on the potential performance of TPAMEN in Am3+/Eu3+ separation.