Trivalent actinide and lanthanide complexation of 5,6-dialkyl-2,6-bis(1,2, 4-triazin-3-yl)pyridine (RBTP; R = H, Me, Et) derivatives: A combined experimental and first-principles study
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Output type: Journal article
Author list: Bhattacharyya A., Kim E., Weck P., Forster P., Czerwinski K.
Publisher: American Chemical Society
Publication year: 2013
Journal: Inorganic Chemistry (0020-1669)
Volume number: 52
Issue number: 2
Start page: 761
End page: 776
Number of pages: 16
ISSN: 0020-1669
eISSN: 1520-510X
URL: http://api.elsevier.com/content/abstract/scopus_id:84872593109
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Abstract
Complexations of lanthanide ions with 5,6-dialkyl-2,6-bis(1,2,4-triazin-3- yl)pyridine [RBTP; R = H (HBTP), methyl (MeBTP), ethyl (EtBTP)] derivatives have been studied in the acetonitrile medium by electrospray ionization mass spectrometry, time-resolved laser-induced fluorescence spectroscopy, and UV-vis spectrophotometric titration. These studies were carried out in the absence and presence of a nitrate ion in order to understand the effect of the nitrate ion on their complexation behavior, particularly in the poor solvating acetonitrile medium where strong nitrate complexation of hard lanthanide ions is expected. Consistent results from all three techniques undoubtedly show the formation of lower stoichiometric complexes in the presence of excess nitrate ion. This kind of nitrate ion effect on the speciation of Ln complexes of RBTP ligands has not so far been reported in the literature. Different Am and Ln complexes were observed with RBTP ligands in the presence of 0.01 M tetramethylammonium nitrate, and their stability constant values are determined using UV-vis spectrophotometric titrations. The formation of higher stoichiometric complexes and higher stability constants for Am compared to Ln ions indicates the selectivity of these classes of ligands. A single-crystal X-ray diffraction (XRD) study of europium(III) complexes shows the formation of a dimeric complex with HBTP and a monomeric complex with EtBTP, whereas MeBTP forms both the dimeric and monomeric complexes. Density functional theory calculations confirm the findings from single-crystal XRD and also predict the structures of Eu and Am complexes observed experimentally. © 2012 American Chemical Society.
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