期刊
INORGANIC CHEMISTRY
卷 50, 期 7, 页码 3087-3096出版社
AMER CHEMICAL SOC
DOI: 10.1021/ic200025s
关键词
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资金
- Fuel Cycle Research and Development Program of Office of Nuclear Energy (NE FCRD)
- Office of Science, Office of Basic Energy Sciences, the U.S. Department of Energy (DOE) at Lawrence Berkeley National Laboratory [DE-AC02-05CH11231]
- DOE [DE-AC07-05ID14517]
Stability constants of two DTPA (diethylenetriaminepentaacetic acid) complexes with lanthanides (ML2- and MHL-, where M stands for Nd and Eu and L stands for diethylenetriaminepentaacetate) at 10, 25, 40, 55, and 70 degrees C were determined by potentiometry, absorption spectrophotometry, and luminescence spectroscopy. The enthalpies of complexation at 25 degrees C were determined by microcalorimetry. Thermodynamic data show that the complexation of Nd3+ and Eu3+ with DTPA is weakened at higher temperatures, a 10-fold decrease in the stability constants of ML2- and MHL- as the temperature is increased from 10 to 70 degrees C. The effect of temperature is consistent with the exothermic enthalpy of complexation directly measured by microcalorimetry. Results by luminescence spectroscopy and density functional theory (DFT) calculations suggest that DTPA is octa-dentate in both the EuL2- and EuHL- complexes and, for the first time, the coordination mode in the EuHL- complex was clarified by integration of the experimental data and DFT calculations. In the EuHL- complex, the Eu is coordinated by an octa-dentate H(DTPA) ligand and a water molecule, and the protonation occurs on the oxygen of a carboxylate group.
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