Hypersensitivity in the electronic transitions of lanthanide and actinide complexes

Henrie, D.E.; Fellows, R.L.; Choppin, Gregory R.

doi:10.1016/s0010-8545(00)82044-5

Cited by 345 publications

(153 citation statements)

References 69 publications

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“…Hypersensitive transitions are one of the most intriguing phenomena in lanthanide Much attention has been paid in the literature to the explanation of the phenomenon of hypersensitivity, but there is still no commonly accepted theory [83,94,127,735]. It is safe to conclude that different factors contribute to the intensity of hypersensitive transitions, and that it is not possible to correlate hypersensitivity with just one experimental parameter, such as the symmetry of the Eu 3+ site or the polarizability of the ligands.…”

Section: Hypersensitivitymentioning

confidence: 99%

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Interpretation of europium(III) spectra

Binnemans

2015

Coordination Chemistry Reviews

2,452

108

1,912

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Section: Hypersensitivitymentioning

confidence: 99%

“…A covalency model of hypersensitivity was developed by Henrie, Fellows and Choppin [83]. Judd has tried in collaboration with Carnall to find general relationships between the  2 parameter and the polarizability  of the ligands [661,745].…”

Section: Hypersensitivitymentioning

confidence: 99%

Interpretation of europium(III) spectra

Binnemans

2015

Coordination Chemistry Reviews

2,452

108

1,912

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“…The emission spectra allow identification of the ions coordination environment in this site, using the splitting pattern and the relative intensity of the ( 5 D 0 → 7 F 1 )-and ( 5 D 0 → 7 F 2 )-transitions, the so-called hypersensitive effect. 29 We can improve the level of detail of the structural characterization by making use of the polarization dependence of the selection rules for transitions of the Eu 3+ fluorescence emission. 30 In single crystals, where orientations are not averaged isotropically, emission spectra may show different splitting patterns depending on the polarization direction of the exciting laser and the symmetry of the local coordination environment of Eu 3+ .…”

Section: Introductionmentioning

confidence: 99%

Characterization of powellite-based solid solutions by site-selective time resolved laser fluorescence spectroscopy

et al. 2013

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We present a comprehensive study of the solid solution system Ca 2 (MoO 4 ) 2 -NaGd(MoO 4 ) 2 on the molecular scale, by means of site-selective time resolved laser fluorescence spectroscopy (TRLFS). Eu 3+ is used as a trace fluorescent probe, homogeneously substituting for Gd 3+ in the solid solution crystal structure. Site-selective TRLFS of a series of polycrystalline samples covering the whole composition range of the solid solution series from 10% substitution of Ca 2+ to the NaGd end-member reveals it to be homogeneous throughout the whole range. The trivalent ions are incorporated into the powellite structure in only one coordination environment, which exhibits a very strong ligand-metal interaction. Polarizationdependent measurements of a single crystal of NaGd(Eu)(MoO 4 ) 2 identify the coordination geometry to be of C 2v point symmetry. The S 4 symmetry of the Ca site within the powellite lattice can be transformed into C 2v assuming minor motion in the first coordination sphere.

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“…The highest permissible molar excesses of other ions (i.e., causing a ±5% relative error in the third-derivative absorption signals) were as follows: Mg (20). Larger amounts decreased the absorption signals.…”

Section: Effect Of Diverse Ionsmentioning

confidence: 95%

“…A narrow absorption band at 483 nm corresponding to the 3 H4 → 3 P0 transition 20 of Pr 3+ , allows its determination by means of the derivative spectra. The other lanthanide complexes in this wavelength range show only pure complex background absorption, except that the 4f electron transitions of the holmium complex at 450 nm was lightly enhanced.…”

Section: Absorption Spectramentioning

confidence: 99%

Absorption Spectra of the 4f Electron Transitions of the Praseodymium Complex with 1-Cyclopropyl-6-fluoro-1,4-dihydro-7-(4-ethyl-1-piperazinyl)-4-oxo-3-quinoline Carboxylic Acid Hydrochloride and Its Analytical Application

Wang

Jiang

et al. 2001

ANAL. SCI.

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A number of metallochromic reagents have been described for the spectrophotometric determination of praseodymium. [1][2][3][4][5] None of them are specific for praseodymium in the presence of other rare earths because of a considerable overlap between their broad absorption spectra. However, there has long been interest in the determination of individual elements based on the absorption bands of their 4f electron transitions. [6][7][8][9][10][11] In recent papers, the third/second derivative spectrophotometric determination of complexes formed by some rare earths with 8-hydroxylquinoline and its derivative, 12-15 β-diketones 16,17 and inorganic salts 18,19 were investigated, which can be utilized for the determination of neodymium, holmium and erbium. However, applications to praseodymium are rare.1-Cyclopropyl-6-fluoro-1,4-dihydro-7-(4-ethyl-1-piperazinyl)-4-oxo-3-quinoline carboxylic acid hydrochloride (NNFX) is the third representative of antibacterial medicine, namely the quinolone group, used extensively in clinical treatment with higher potential and a broad antibacterial spectrum as well as fewer side effect. However, its utilization as a reagent for the determination of rare earth elements has not been reported. In the present work, the absorption spectra of the praseodymium complex with NNFX was investigated by applying both normal and derivative spectrophotometric methods. On this basis, a method was developed for the direct determination of praseodymium in rare earth mixtures. The analytical results obtained are satisfactory. Experimental ApparatusA Shimadzu UV-3000 double-beam spectrophotometer (Kyoto, Japan) with 4.0-cm cells was used. The pH-values of the solutions were measured with a pHs-2 meter (Analytical Apparatus Plant, Shanghai, China). Reagents and chemicalsStock lanthanide solutions (0.01 M) were prepared by dissolving an appropriate amount of pure oxides (Johnson Matthey, Royston, Hertfordshire, UK) in hydrochloric acid (1+1), and working solutions were prepared by dilution with water. A solution of 1-cyclopropyl-6-fluoro-1,4-dihydro-7-(4-ethyl-1-piperazinyl)-4-oxo-3-quinoline carboxylic acid hydrochloride (NNFX, 0.05 M) was prepared by dissolving 1.797 g of NNFX (Zibo Pharmacy Plant, People's Republic of China) in 100 ml of distilled water in a calibrated flask. A buffer solution of pH 6.0 was prepared by dissolving 200 g of hexamethylene tetramine in 500 ml of distilled water, the pH being adjusted with hydrochloric acid (1+1) and diluting to 1000 ml with distilled water.Analytical-reagent grade chemicals were used whenever possible. ProcedureA known volume of a lanthanide solution (containing Pr up to 50 µg) was transferred into a 10 ml calibrated flask; 3.0 ml of 0.05 M NNFX and 4.0 ml of pH 6.0 buffer solutions were added. The mixture was diluted to the mark with distilled water, and after 30 min the third-derivative spectra were recorded against a reagent blank using 4.0-cm cells with a ∆λ of 2.8 nm, a band pass of 1.0 nm and a scan rate = 50 nm min -1 as instrumental parameters. Th...

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Hypersensitivity in the electronic transitions of lanthanide and actinide complexes

Cited by 345 publications

References 69 publications

Interpretation of europium(III) spectra

Interpretation of europium(III) spectra

Characterization of powellite-based solid solutions by site-selective time resolved laser fluorescence spectroscopy

Absorption Spectra of the 4f Electron Transitions of the Praseodymium Complex with 1-Cyclopropyl-6-fluoro-1,4-dihydro-7-(4-ethyl-1-piperazinyl)-4-oxo-3-quinoline Carboxylic Acid Hydrochloride and Its Analytical Application

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