期刊
INORGANIC CHEMISTRY
卷 60, 期 14, 页码 10656-10673出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.1c01319
关键词
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资金
- German Federal Ministry of Education and Research (BMBF) [02NUK039B, 033R127D]
- French government through the Program Investissement d'avenir (LABEX) [CaPPA/ANR-11-LABX0005-01, I-SITE ULNE/ANR-16-IDEX-0004 ULNE]
- Ministry of Higher Education and Research
- Hauts de France Council
- European Regional Development Fund (ERDF) through the Contrat de Projets Etat-REgion (CPER-CLIMIBIO)
- French research network GDR [2035 SolvATE]
In this study, the coordination chemistry of Cm(III) with aqueous phosphates was investigated using laser-induced luminescence spectroscopy and ab initio simulations. The formation of Cm(H2PO4)(2)(+) was confirmed for the first time, along with deriving complexation constants and thermodynamic parameters. The results showed a temperature-dependent coordination change for the Cm(III)-phosphate complexes, with different coordination numbers observed at different temperatures.
The coordination chemistry of Cm(III) with aqueous phosphates was investigated by means of laser-induced luminescence spectroscopy and ab initio simulations. For the first time, in addition to the presence of Cm(H2PO4)(2+), the formation of Cm(H2PO4)(2)(+) was unambiguously established from the luminescence spectroscopic data collected at various H+ concentrations (-log(10) [H+] = 2.52, 3.44, and 3.65), ionic strengths (0.5-3.0 mol.L-1 NaClO4), and temperatures (25-90 degrees C). Complexation constants for both species were derived and extrapolated to standard conditions using the specific ion interaction theory. The molal enthalpy Delta H-R(m)0 and molal entropy Delta S-R(m)0 of both complexation reactions were derived using the integrated van't Hoff equation and indicated an endothermic and entropy-driven complexation. For the Cm(H2PO4)(2)(+) complex, a more satisfactory description could be obtained when including the molal heat capacity term. While monodentate binding of the H2PO4- ligand(s) to the central curium ion was found to be the most stable configuration for both complexes in our ab initio simulations and luminescence lifetime analyses, a different temperature-dependent coordination to hydration water molecules could be deduced from the electronic structure of the Cm(III)-phosphate complexes. More precisely, where the Cm(H2PO4)(2+) complex could be shown to retain an overall coordination number of 9 over the entire investigated temperature range, a coordination change from 9 to 8 was established for the Cm(H2PO4)(2)(+) species with increasing temperature.
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