Luminescence study of complexation of europium and dicarboxylic acids

Barthelemy, P.; Choppin, Gregory R.

doi:10.1021/ic00316a023

Cited by 203 publications

(121 citation statements)

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“…The values are in good agreement with those previously observed for Eu(aq) 3+ (108, 113 µs) 13,31 and that estimated for EuNO 3 (aq) 2+ (159 µs). 13 It is evident that the luminescence lifetime becomes longer as C nitrate is increased, suggesting the number of water molecules in the primary coordination sphere of Eu 3+ is reduced due to the complexation with nitrate.…”

Section: Emission Spectra and Lifetime Of The Luminescence Of Eu(iii)supporting

confidence: 92%

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Complexation of Lanthanides with Nitrate at Variable Temperatures: Thermodynamics and Coordination Modes

Rao

Tian

2008

Inorg. Chem.

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Complexation of neodymium(III) with nitrate was studied at variable temperatures (25, 40, 55 and 70ºC) by spectrophotometry and microcalorimetry. The NdNO 3 2+ complex is weak and becomes slightly stronger as the temperature is increased. The enthalpy of complexation at 25ºC was determined by microcalorimetry to be small and positive, (1.5 ± 0.2) kJ·mol -1 , in good agreement with the trend of the stability constant at variable temperatures. Luminescence emission spectra and lifetime of Eu(III) in nitrate solutions suggest that inner-sphere and bidentate complexes form between trivalent lanthanides (Nd 3+ and Eu 3+ ) and nitrate in aqueous solutions. Specific Ion Interaction approach (SIT) was used to obtain the stability constants of NdNO 3 2+ at infinite dilution and variable temperatures.

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Section: Emission Spectra and Lifetime Of The Luminescence Of Eu(iii)supporting

confidence: 92%

“…Using the relationship between the luminescence lifetime and the hydration number (n H2O = 1.05 × τ H2O -1 -0.7, where τ H2O is in milliseconds), 31 the average number of water molecules in the primary coordination sphere of Eu 3+ (n H2O,exp ) was obtained ( Table 2).…”

Section: Emission Spectra and Lifetime Of The Luminescence Of Eu(iii)mentioning

confidence: 99%

Complexation of Lanthanides with Nitrate at Variable Temperatures: Thermodynamics and Coordination Modes

Rao

Tian

2008

Inorg. Chem.

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“…[c] The errors in parentheses correspond to a fitting of the time vs. q dependence; q in any time point was determined by Choppins method [54] with precision of AE 0.5…”

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confidence: 99%

Lanthanide(III) Complexes of 4,10‐Bis(phosphonomethyl)‐1,4,7,10‐tetraazacyclododecane‐1,7‐diacetic acid (trans‐H₆do2a2p) in Solution and in the Solid State: Structural Studies Along the Series

Campello¹,

Lacerda²,

Pereira

et al. 2010

Chemistry A European J

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Complexes of 4,10-bis(phosphonomethyl)-1,4,7,10-tetraazacyclododecane-1,7-diacetic acid (trans-H(6)do2a2p, H(6)L) with transition metal and lanthanide(III) ions were investigated. The stability constant values of the divalent and trivalent metal-ion complexes are between the corresponding values of H(4)dota and H(8)dotp complexes, as a consequence of the ligand basicity. The solid-state structures of the ligand and of nine lanthanide(III) complexes were determined by X-ray diffraction. All the complexes are present as twisted-square-antiprismatic isomers and their structures can be divided into two series. The first one involves nona-coordinated complexes of the large lanthanide(III) ions (Ce, Nd, Sm) with a coordinated water molecule. In the series of Sm, Eu, Tb, Dy, Er, Yb, the complexes are octa-coordinated only by the ligand donor atoms and their coordination cages are more irregular. The formation kinetics and the acid-assisted dissociation of several Ln(III)-H(6)L complexes were investigated at different temperatures and compared with analogous data for complexes of other dota-like ligands. The [Ce(L)(H(2)O)](3-) complex is the most kinetically inert among complexes of the investigated lanthanide(III) ions (Ce, Eu, Gd, Yb). Among mixed phosphonate-acetate dota analogues, kinetic inertness of the cerium(III) complexes is increased with a higher number of phosphonate arms in the ligand, whereas the opposite is true for europium(III) complexes. According to the (1)H NMR spectroscopic pseudo-contact shifts for the Ce-Eu and Tb-Yb series, the solution structures of the complexes reflect the structures of the [Ce(HL)(H(2)O)](2-) and [Yb(HL)](2-) anions, respectively, found in the solid state. However, these solution NMR spectroscopic studies showed that there is no unambiguous relation between (31)P/(1)H lanthanide-induced shift (LIS) values and coordination of water in the complexes; the values rather express a relative position of the central ions between the N(4) and O(4) planes.

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“…The detection of trace water in organic solvents such as DMSO is an interesting project that has been studied extensively. 7,8 We observed that the emissions of Eu 3+ in DMSO are very strong and very sensitive to water. The emission band from the 5 D 0 → 7 F 2 transition has two peaks at 613 and 617 nm, and these two peaks change in opposite ways when water is added to the DMSO.…”

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confidence: 82%

Reply to Comment on “Hypersensitive Luminescence of Eu³⁺ in Dimethyl Sulfoxide As a New Probing for Water Measurement”

Chen

Yao

2012

Anal. Chem.

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Luminescence of rare earth ions in dimethyl sulfoxide (DMSO) has been recently observed and reported by our group.1,2 Potentially, luminescence of rare earth/DMSO compounds has many applications including the probing of trace water in organic solvents like DMSO. The measurement based on the relative intensity changes in two peaks is more reliable and selective than using the intensity change of only one emission peak. Both measurements based on intensity and lifetime changes have advantages and disadvantages. Techniques based on luminescence intensity changes are easy, fast, convenient, and cost-effective. Decay lifetime-based measurement is complimentary to intensity-based detection; however, it will likely never replace intensity-based techniques for practical applications.It has been reported previously that no luminescence could be observed for rare earth ions (RE) dissolved in dimethyl sulfoxide (DMSO).3−6 However, intense luminescence was recently observed and reported by our group by dissolving RE in DMSO at high temperatures.1,2 Luminescent RE/DMSO compounds may find applications in lighting, sensing, labeling, and imaging. The detection of trace water in organic solvents such as DMSO is an interesting project that has been studied extensively. 7,8 We observed that the emissions of Eu 3+ in DMSO are very strong and very sensitive to water. The emission band from the 5 D 0 → 7 F 2 transition has two peaks at 613 and 617 nm, and these two peaks change in opposite ways when water is added to the DMSO. Using the relative changes of the two peaks for measurement, as reported in our paper, is more reliable than using the change of only one peak. However, we did point out that the measurement based on the two intensity changes is only valid in a certain range of water concentration in DMSO; it is not applicable for the entire concentration range. We did explain that the excitation and emission spectra were measured on a commercially available Shimadzu RF-5301PC fluorometer. Standard procedure was followed for the spectral measurement, and spectra measured with a standard fluorometer are not like the spectra measured using homemade systems that need special calibrations. For a Shimadzu RF-5301PC fluorometer, the light source is a 150 W xenon lamp and the wavelength scale is from 220 to 990 nm. In the emission spectral measurement, the bandwidth is set at 1.5 nm and the measurement wavelength accuracy is ±1.5 nm. The data and spectra reported in our paper are valid, reliable, accurate, and repeatable.We prefer to use the emission peak intensity rather the emission area for the measurement because the measurement of the peak intensity is easier and more accurate because the two peaks are overlapped and a deconvolution of them might induce errors due to possible artificial elements. Furthermore, for practical applications, particularly field applications, using the peak intensity is always easier and more convenient.In our preliminary studies, we use the intensity ratios of the two peaks at 613 and 617 nm for water ...

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Luminescence study of complexation of europium and dicarboxylic acids

Cited by 203 publications

References 2 publications

Complexation of Lanthanides with Nitrate at Variable Temperatures: Thermodynamics and Coordination Modes

Complexation of Lanthanides with Nitrate at Variable Temperatures: Thermodynamics and Coordination Modes

Lanthanide(III) Complexes of 4,10‐Bis(phosphonomethyl)‐1,4,7,10‐tetraazacyclododecane‐1,7‐diacetic acid (trans‐H₆do2a2p) in Solution and in the Solid State: Structural Studies Along the Series

Reply to Comment on “Hypersensitive Luminescence of Eu³⁺ in Dimethyl Sulfoxide As a New Probing for Water Measurement”

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Luminescence study of complexation of europium and dicarboxylic acids

Cited by 203 publications

References 2 publications

Complexation of Lanthanides with Nitrate at Variable Temperatures: Thermodynamics and Coordination Modes

Complexation of Lanthanides with Nitrate at Variable Temperatures: Thermodynamics and Coordination Modes

Lanthanide(III) Complexes of 4,10‐Bis(phosphonomethyl)‐1,4,7,10‐tetraazacyclododecane‐1,7‐diacetic acid (trans‐H6do2a2p) in Solution and in the Solid State: Structural Studies Along the Series

Reply to Comment on “Hypersensitive Luminescence of Eu3+ in Dimethyl Sulfoxide As a New Probing for Water Measurement”

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Lanthanide(III) Complexes of 4,10‐Bis(phosphonomethyl)‐1,4,7,10‐tetraazacyclododecane‐1,7‐diacetic acid (trans‐H₆do2a2p) in Solution and in the Solid State: Structural Studies Along the Series

Reply to Comment on “Hypersensitive Luminescence of Eu³⁺ in Dimethyl Sulfoxide As a New Probing for Water Measurement”