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An Insight into the Complexation of Trivalent Americium Vis‐à‐Vis Lanthanides with Bis(1,2,4‐triazinyl)bipyridine Derivatives
Author(s) -
Bhattacharyya Arunasis,
Mohapatra Manoj,
Mohapatra Prasanta K.,
Gadly Trilochan,
Ghosh Sunil K.,
Manna Debashree,
Ghanty Tapan K.,
Rawat Neetika,
Tomar Bhupendra S.
Publication year - 2017
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201600829
Subject(s) - chemistry , lanthanide , titration , bipyridine , acetonitrile , stability constants of complexes , electrospray ionization , stoichiometry , ligand (biochemistry) , americium , inorganic chemistry , actinide , covalent bond , crystallography , organic chemistry , ion , aqueous solution , crystal structure , biochemistry , receptor
Complexation of Am 3+ and Ln 3+ (La 3+ , Eu 3+ , and Er 3+ ) with two bis(1,2,4‐triazinyl)bipyridine (C 2 BTBP, C 5 BTBP) derivatives has been studied in acetonitrile medium with use of various experimental techniques such as electrospray ionization mass spectrometry (ESI‐MS), time‐resolved fluorescence spectroscopy (TRFS), UV/Vis spectrophotometry, and solution calorimetry. Metal–ligand stoichiometries and conditional stability constants of these complexes were determined. To the best of our knowledge, this is the first report on the complexation of Am 3+ with any of the BTBP derivatives with use of UV/Vis spectrophotometric titration to determine the conditional stability constants. Density functional theory (DFT) calculations are carried out on the An 3+ (U 3+ and Am 3+ ) and Ln 3+ (La 3+ , Nd 3+ , Eu 3+ , Er 3+ , and Lu 3+ ) complexes of BTBP in order to understand the difference between the bonding in actinide and lanthanide complexes. The results indicate a stronger covalent interaction in the An–N bonds as compared to the Ln–N bonds, which leads to an actinide selectivity of this class of ligands.