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Issue 16, 2019
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Do An(III) and Ln(III) ions form heteroleptic complexes with diglycolamide and hydrophilic BT(B)P ligands in solvent extraction systems? A spectroscopic and DFT study

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Abstract

Time-Resolved Laser Fluorescence Spectroscopy (TRLFS) was used to study the complexation of Cm(III) and Eu(III) in solvent extraction systems consisting of an organic phase containing TODGA (tetra-n-octyl diglycolamide) as an extracting agent and an aqueous phase containing hydrophilic complexing agents, tetrasodium salts of 2,6-bis(5,6-di(3-sulphophenyl)-1,2,4-triazin-3-yl)pyridine, SO3-Ph-BTP4−, or 6,6′-bis(5,6-di(3-sulphophenyl)-1,2,4-triazin-3-yl)-2,2′-bipyridine, SO3-Ph-BTBP4−. Only one complex, homoleptic [Cm(TODGA)3](NO3)3, was found in the organic phase. No heteroleptic complexes of Cm(III) with TODGA and SO3-Ph-BTP4− have been detected. In contrast, in dilute aqueous HClO4 solutions containing TEDGA (a hydrophilic homologue of TODGA) and SO3-Ph-BTP4− ligands, seven different Cm(III) species were identified by their distinct emission spectra. Apart from the emission bands corresponding to the hydrated Cm3+ cation and to the complexes [Cm(SO3-Ph-BTP)] and [Cm(TEDGA)n]3+ (n = 1–3), two further emission bands were ascribed to heteroleptic complexes [Cm(TEDGA)(SO3-Ph-BTP)] and [Cm(TEDGA)2(SO3-Ph-BTP)]. In a similar aqueous solution containing TEDGA and SO3-Ph-BTBP4−, only one heteroleptic complex was identified, [Cm(TEDGA)(SO3-Ph-BTBP)]. In addition, quantum chemical optimisation of the structures of the postulated heteroleptic complexes was performed.

Graphical abstract: Do An(iii) and Ln(iii) ions form heteroleptic complexes with diglycolamide and hydrophilic BT(B)P ligands in solvent extraction systems? A spectroscopic and DFT study

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Publication details

The article was received on 06 Feb 2019, accepted on 20 Mar 2019 and first published on 21 Mar 2019


Article type: Paper
DOI: 10.1039/C9NJ00651F
New J. Chem., 2019,43, 6314-6322
  • Open access: Creative Commons BY-NC license
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    Do An(III) and Ln(III) ions form heteroleptic complexes with diglycolamide and hydrophilic BT(B)P ligands in solvent extraction systems? A spectroscopic and DFT study

    I. Herdzik-Koniecko, C. Wagner, M. Trumm, U. Müllich, B. Schimmelpfennig, J. Narbutt, A. Geist and P. J. Panak, New J. Chem., 2019, 43, 6314
    DOI: 10.1039/C9NJ00651F

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