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Study of Aqueous Am(III)-Aliphatic Dicarboxylate Complexes: Coordination Mode-Dependent Optical Property and Stability Changes

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Title
Study of Aqueous Am(III)-Aliphatic Dicarboxylate Complexes: Coordination Mode-Dependent Optical Property and Stability Changes
Author(s)
Hee-Kyung Kim; Keunhong Jeong; Hye-Ryun Cho; Kyungwon Kwak; Euo Chang Jung; Wansik Cha
Subject
LANTHANIDE(III) COMPLEXES, ; CARBOXYLIC-ACIDS, ; ACETATE, ; OXALATE, ; AMERICIUM(III), ; URANIUM(VI), ; MALONATE, ; AM(III), ; CM(III), ; LUMINESCENCE
Publication Date
2020-10
Journal
INORGANIC CHEMISTRY, v.59, no.19, pp.13912 - 13922
Publisher
AMER CHEMICAL SOC
Abstract
© 2020 American Chemical Society. The thermodynamics of Am(III) complex formation in natural groundwater systems is one of the major topics of research in the field of high-level radioactive waste management. In this study, we investigate the absorption and luminescence properties of aqueous Am(III) complexes with a series of aliphatic dicarboxylates in order to learn the thermodynamic complexation behaviors in relation to binding geometries. The formation of Am(III) complexes with these carboxylate ligands induced distinct red shifts in the absorption spectra, which enabled chemical speciation. The formation constants determined by deconvolution of the absorption spectra showed a linear decrease for the three ligands (oxalate (Ox), malonate (Mal), and succinate (Suc)) and a mild decrease for the remaining ligands (glutarate (Glu) and adipate (Adi)). Time-resolved laser fluorescence spectroscopy (TRLFS) was used to obtain information about the aqua ligand, which indirectly indicated the bidentate bindings of these dicarboxylate ligands. A complementary attenuated total reflectance Fourier transform infrared (ATR-FTIR) study on Eu(III), which is a nonradioactive analogue of Am(III) ion, showed that the coordination modes differ depending on the alkyl chain length. Ox and Mal bind to Am(III) via side-on bidentate bindings with two carboxylate groups, resulting in the formation of stable 5- and 6-membered ring structures, respectively. On the other hand, Suc, Glu, and Adi form end-on bidentate bindings with a single carboxylate group, resulting in a 4-membered ring structure. Density functional theory calculations provided details about the bonding properties and supported the experimentally proposed coordination geometries. This study demonstrates that coordination mode-dependent changes in optical properties occur along with thermodynamic stability changes in Am(III)-dicarboxylate complexes
URI
https://pr.ibs.re.kr/handle/8788114/8467
DOI
10.1021/acs.inorgchem.0c01538
ISSN
0020-1669
Appears in Collections:
Center for Molecular Spectroscopy and Dynamics(분자 분광학 및 동력학 연구단) > 1. Journal Papers (저널논문)
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