An Insight into the Complexation of Trivalent Americium Vis‐à‐Vis Lanthanides with Bis(1, 2, 4‐triazinyl)bipyridine Derivatives. Issue 4 (23rd December 2016)

• Record Type: Journal Article
• Authors: Bhattacharyya, Arunasis; Mohapatra, Manoj; Mohapatra, Prasanta K.; Gadly, Trilochan; Ghosh, Sunil K.; Manna, Debashree; Ghanty, Tapan K.; Rawat, Neetika; Tomar, Bhupendra S.
• Is Part Of: European journal of inorganic chemistry. Issue 4(2017)
• Page Start: 820
• Page End: 828
• Publication Date: 2016-12-23
• Subjects: Americium -- Lanthanides -- Actinides -- N ligands -- Complexation -- Density functional calculations; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201600829
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : Complexation of Am 3+ and Ln 3+ (La 3+, Eu 3+, and Er 3+ ) with two bis(1, 2, 4‐triazinyl)bipyridine (C2 BTBP, C5 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. Abstract : The experimentally observed higher complexation ability of two bis(1, 2, 4‐triazinyl)bipyridine (BTBP) derivatives for Am 3+ over Ln 3+ is explained on the basis of higher metal–ligand orbital overlap and higher bond order in the Am 3+ complex.