Measurement and analysis of the temperature and pressure dependence of the 7F0→5D0 excitation spectra of Eu(III) complexes with 4-phenylethynyl-2,6-pyridine-dicarboxylic acid

Maupin, Christine L.; Logue, Marshall W.; Leifer, Leslie; Riehl, James P.

doi:10.1016/s0925-8388(99)00738-0

Cited by 9 publications

(12 citation statements)

References 8 publications

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“…Useful information concerning structural differences between the two isomers in equilibrium can also be obtained from examination of the pressure dependence of the excitation spectra. [14][15][16][17] The pressure dependence of the equilibrium constant is related to the difference in molar volume, ∆V, by the following relationship:…”

Section: Resultsmentioning

confidence: 99%

Temperature and Pressure Dependence of Excitation Spectra as a Probe of the Solution Structure and Equilibrium Thermodynamics of a Eu(III) Complex Containing a Modified dota Ligand

et al. 2002

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The temperature and pressure dependence of the 7F0 → 5D0 and 7F1 → 5D0 excitation spectra for aqueous solutions of Eu(III) with racemic-tetra(α-carboxyethyl)DOTA have been measured. Individual excitation and emission peaks have been assigned to square antiprism (SAP) and twisted square antiprism (TSAP) isomers of the complex, and the variation of relative peak areas as a function of temperature and pressure have been used to estimate the enthalpy and volume change associated with the isomer equilibrium. The effects of temperature on the initial state populations have been treated explicitly, although for the data presented, these effects are within the uncertainty of the measurement. The results show that the SAP isomer of Eu(ceDOTA) is the more compact, more ordered, and lower enthalpy structure, consistent with previous NMR experiments on the differences in the observed rate of water exchange for the isomeric species.

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Section: Resultsmentioning

confidence: 99%

Temperature and Pressure Dependence of Excitation Spectra as a Probe of the Solution Structure and Equilibrium Thermodynamics of a Eu(III) Complex Containing a Modified dota Ligand

et al. 2002

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“…The studies include Eu(III) with carbonate (15-35 uC, solvent extraction), 13 Nd(III) with sulfate (30-250 uC, spectrophotometry), 14 Lanthanides (III) with fluoride (5-45 uC, ion exchange), 15 Nd(III)/Sm(III)/Ho(III) with chloride (100-250 uC, spectrophotometry), 16 Pr(III) with acetate (20-95 uC, absorption spectroscopy), 17 Nd(III) with acetate (25-225 uC, potentiometry), 18 (20-70 uC, photoacoustic spectroscopy), 19 (25-70 uC, potentiometry and calorimetry), 20,21 Eu(III) with acetate (25-170 uC, potentiometry), 22 (8-59 uC, fluorescence spectroscopy), 23 Lanthanides (III) with oxydiacetate (5-50 uC, potentiometry and calorimetry), 24 Sm(III) with oxydiacetate (25-70 uC, potentiometry and calorimetry), 25 and Eu(III) with 4-phenylethynyl-2,6-pyridinedicarboxylic acid (25-87.5 uC, fluorescence spectroscopy). 26…”

Section: Trivalent Lanthanides As Chemical Analogsmentioning

confidence: 99%

Thermodynamics of actinide complexation in solution at elevated temperatures: application of variable-temperature titration calorimetry

Rao

2007

Chem. Soc. Rev.

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Studies of actinide complexation in solution at elevated temperatures provide insight into the effect of solvation and the energetics of complexation, and help to predict the chemical behavior of actinides in nuclear waste processing and disposal where temperatures are high. This tutorial review summarizes the data on the complexation of actinides at elevated temperatures and describes the methodology for thermodynamic measurements, with the emphasis on variable-temperature titration calorimetry, a highly valuable technique to determine the enthalpy and, under appropriate conditions, the equilibrium constants of complexation as well.

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“…19 In the present study, lanthanide(III) coordination compounds from the inexpensive, readily available ligand 2,6-dipicolinic acid (2,6-H 2 dpa) have been developed. 2,6-H 2 dpa is known to be able to act as a tridentate ligand (in the solid phase 25,32-43 and in solution [43][44][45][46][47][48][49] ); therefore, if a 1 : 3 metal-to-ligand ratio is applied, the saturation of the Ln(III) coordination sphere can be reached.…”

Section: Introductionmentioning

confidence: 99%

“…Ordinarily, the synthesis of (2,6-H 2 dpa)-based complexes is time-consuming, involving multiple acid-base reactions. [44][45][46][47][48][49] However, it has been found that upon refluxing a 1 : 3 mixture of LnCl 3 (Ln = Eu or Tb) and 2,6-H 2 dpa for only one hour in dimethylformamide (DMF), a microcrystalline, air-stable precipitate is produced, which can be isolated in >80% yield by a simple filtration (see experimental section for details).…”

Section: Introductionmentioning

confidence: 99%

Efficient, stable, tunable, and easy to synthesize, handle and recycle luminescent materials: [H2NMe2]3[Ln(iii)(2,6-dipicolinolate)3] (Ln = Eu, Tb, or its solid solutions)

et al. 2010

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Three compounds with the general formulae [H(2)N(Me)(2)](3)[Ln(2,6-dpa)(3)] were prepared from cheap and readily available reactants. Microcrystalline compounds could be isolated in high yields (>80%) by a simple filtration, after only one hour reaction time in refluxing DMF. The Eu and Tb compounds have been structurally characterized by single crystal X-ray diffraction. The compounds have unusual high-absorption coefficients (>95%) and quantum efficiencies (approximately 70%). Furthermore, they are thermally stable up to 250 degrees C and appear to be UV and water tolerant. The emission colour of the final compound can be easily fine-tuned, by varying the Eu:Tb ratio during the preparation.

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Measurement and analysis of the temperature and pressure dependence of the 7F0→5D0 excitation spectra of Eu(III) complexes with 4-phenylethynyl-2,6-pyridine-dicarboxylic acid

Cited by 9 publications

References 8 publications

Temperature and Pressure Dependence of Excitation Spectra as a Probe of the Solution Structure and Equilibrium Thermodynamics of a Eu(III) Complex Containing a Modified dota Ligand

Temperature and Pressure Dependence of Excitation Spectra as a Probe of the Solution Structure and Equilibrium Thermodynamics of a Eu(III) Complex Containing a Modified dota Ligand

Thermodynamics of actinide complexation in solution at elevated temperatures: application of variable-temperature titration calorimetry

Efficient, stable, tunable, and easy to synthesize, handle and recycle luminescent materials: [H2NMe2]3[Ln(iii)(2,6-dipicolinolate)3] (Ln = Eu, Tb, or its solid solutions)

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