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Issue 32, 2014
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Complexation of trivalent americium and lanthanides with terdentate ‘N’ donor ligands: the role of rigidity in the ligand structure

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Abstract

A systematic study on the Ln3+ complexation behaviour with two terdentate ‘N’ donor ligands of varying structural rigidity, viz. 5,6-dimethyl-(1,2,4)-triazinylbipyridine (Me2TBipy) and 5,6-dimethyl-(1,2,4)-triazinylphenanthroline (Me2TPhen), 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 La3+, 1 : 2 complexes of Eu3+ and Er3+ with both the ligands. Density functional theoretical (DFT) study is carried out to determine the solution phase structure of the Eu3+ complex considering the species (from UV-Vis spectrophotometry) and C2v site symmetry around the Eu3+ ion (from TRFS study). Me2TPhen is found to be a stronger complexing ligand as compared to Me2TBipy irrespective of the Ln3+ ions. The solid state crystal structure of the La3+ complex of Me2TPhen 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 Ln3+ ions studied, indicating the selectivity of these ligands for the trivalent actinides over the lanthanides.

Graphical abstract: Complexation of trivalent americium and lanthanides with terdentate ‘N’ donor ligands: the role of rigidity in the ligand structure

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Publication details

The article was received on 06 May 2014, accepted on 21 Jun 2014 and first published on 24 Jun 2014


Article type: Paper
DOI: 10.1039/C4DT01342E
Citation: Dalton Trans., 2014,43, 12422-12429
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    Complexation of trivalent americium and lanthanides with terdentate ‘N’ donor ligands: the role of rigidity in the ligand structure

    A. Bhattacharyya, T. Gadly, P. Pathak, S. K. Ghosh, M. Mohapatra, T. K. Ghanty and P. K. Mohapatra, Dalton Trans., 2014, 43, 12422
    DOI: 10.1039/C4DT01342E

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