TY - JOUR
T1 - Thermodynamic, spectroscopic, and computational studies of lanthanide complexation with diethylenetriaminepentaacetic acid
T2 - Temperature effect and coordination modes
AU - Tian, Guoxin
AU - Martin, Leigh R.
AU - Zhang, Zhiyong
AU - Rao, Linfeng
PY - 2011/4/4
Y1 - 2011/4/4
N2 - 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 °C were determined by potentiometry, absorption spectrophotometry, and luminescence spectroscopy. The enthalpies of complexation at 25 °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 ML 2- and MHL- as the temperature is increased from 10 to 70 °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.
AB - 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 °C were determined by potentiometry, absorption spectrophotometry, and luminescence spectroscopy. The enthalpies of complexation at 25 °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 ML 2- and MHL- as the temperature is increased from 10 to 70 °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.
UR - http://www.scopus.com/inward/record.url?scp=79953176365&partnerID=8YFLogxK
U2 - 10.1021/ic200025s
DO - 10.1021/ic200025s
M3 - Article
C2 - 21375350
AN - SCOPUS:79953176365
SN - 0020-1669
VL - 50
SP - 3087
EP - 3096
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 7
ER -