Complexation of trivalent americium and lanthanides with terdentate 'N' donor ligands: the role of rigidity in the ligand structure

摘要

A systematic study on the Ln~(3+) complexation behaviour with two terdentate 'N' donor ligands of varying structural rigidity, viz. 5,6-dimethyl-(1,2,4)-triazinylbipyridine (Me_2TBipy) and 5,6-dimethyl-(1,2,4)-triazinylphenanthroline (Me_2TPhen), is performed in the present work by UV-Vis spectrophotometry, time resolved fluorescence spectroscopy (TRFS) and electrospray ionization mass spectrometric (ESI-MS) studies. These studies indicate the formation of a 1 : 1 complex of La~(3+), 1 : 2 complexes of Eu~(3+) and Er~(3+) with both the ligands. Density functional theoretical (DFT) study is carried out to determine the solution phase structure of the Eu~(3+) complex considering the species (from UV-Vis spectrophotometry) and C_(2v) site symmetry around the Eu~(3+) ion (from TRFS study). Me_2TPhen is found to be a stronger complexing ligand as compared to Me_2TBipy irrespective of the Ln~(3+) ions. The solid state crystal structure of the La~(3+) complex of Me_2TPhen is determined using the single crystal X-ray diffraction (SCXRD) technique. The complexation of the trivalent Am3+ ion is also studied with both these ligands using UV-Vis spectrophotometric titrations which show the formation of 1 : 2 complexes with higher complexation constant values as compared to all the Ln~(3+) ions studied, indicating the selectivity of these ligands for the trivalent actinides over the lanthanides.