Analysis of the fluorescence spectra of europium(III)-bis-phenanthroline-tris-carboxylate complexes

Sinha, Shyama P.; Butter, E.

doi:10.1080/00268976900100331

Cited by 41 publications

(8 citation statements)

References 25 publications

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“…When the Eu 3+ ion is inserted into a chemical environment, the (2 J + 1)‐degenerate J ‐levels are split by ligand‐field effects into so‐called Stark sublevels, the number of which depends on the site symmetry of the metal ion. Here again, the Eu 3+ ion is used as a local crystal‐field probe to characterize the structure and site symmetry, as done by different groups including ours …”

Section: Resultsmentioning

confidence: 99%

Probing Site Symmetry Around Eu³⁺ in Nanocrystalline ThO₂ Using Time Resolved Emission Spectroscopy

et al. 2014

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ThO 2 :Eu 3+ nanoparticles were synthesized at 300°C by combustion route using urea as a fuel and characterized by thermogravimetric/differential thermal analysis, X-ray diffraction, transmission electron microscopy, and photoluminescence techniques. To investigate the effect of annealing temperature, as synthesized powder were heated further at 500°C, 700°C, and 900°C. It was observed that extent of asymmetry around Eu 3+ at 700°C/900°C is very high as compared to as-prepared or 500°C annealed sample. Based on the time resolved emission spectroscopic investigations, it was inferred that two different types of Eu 3+ ions were present in the ThO 2 nanoparticles. In ThO 2 structure, Eu 3+ ions occupy two sites; cubic (O h ) and noncubic (

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Section: Resultsmentioning

confidence: 99%

Probing Site Symmetry Around Eu³⁺ in Nanocrystalline ThO₂ Using Time Resolved Emission Spectroscopy

et al. 2014

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“…6) indicate that the ligand to metal charge transfer band at 247 nm is much stronger as compared to the f → f transition bands. 34,35 The doublet at ∼593 nm due to the 5 D 0 → 7 F 0 transition and singlet at ∼616 nm due to the 5 D 0 → 7 F 0 transition is the signature of D 3 symmetric 1 : 3 complexes. Such a strong ligand sensitization was not observed in molecular diluents (vide supra).…”

Section: Luminescence Studymentioning

confidence: 99%

“…This is indicative of D n , D nd or D nh site symmetry around the Eu 3+ ion. 34,35 The doublet at ∼593 nm due to the 5 D 0 → 7 F 0 transition and singlet at ∼616 nm due to the 5 D 0 → 7 F 0 transition is the signature of D 3 symmetric 1 : 3 complexes. 36,37 The anion present in bulk (NTf 2 − ) in the RTIL medium is a weak anion and, therefore, cannot compete with the R-BTP ligands.…”

Section: Luminescence Studymentioning

confidence: 99%

A remarkable enhancement in Am³⁺/Eu³⁺selectivity by an ionic liquid based solvent containing bis-1,2,4-triazinyl pyridine derivatives: DFT validation of experimental results

et al. 2015

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Mutual separation of trivalent actinide (An(3+)) and lanthanide (Ln(3+)) using several soft (N) donor ligands (bis(5,6-dialkyl-1,2,4-triazinyl)pyridine (R-BTP)) is attempted for the first time in room temperature ionic liquid (RTIL) medium. The results indicate a spectacular enhancement in the selectivity as compared to that in molecular diluents with a separation factor (S.F.) of >3000 for Am(3+) over Eu(3+) using the methyl derivative (Me-BTP) in RTIL medium using [C(n)mim]·[NTf2] as the diluents (where n = 2, 3, 4, 6 or 8). Such a high S.F. value has never been reported before with any of the R-BTP derivatives in molecular diluents. An opposite trend in the distribution ratio values of both Am(3+) and Eu(3+) with the increasing size of the alkyl (R) group is observed in RTIL medium when compared with that in molecular diluents. The differences in the extraction behaviour of R-BTPs in RTILs vis-à-vis molecular diluents are explained on the basis of the difference in the nature of complexes extracted in these two distinctly different media as supported by the time resolved fluorescence (TRFS) study. An unusually high extractability and selectivity for Am(3+) over Eu(3+) with Me-BTP was attributed to the formation of a 1 : 4 complex for Am(3+), which was never reported earlier with any of the R-BTP derivatives in molecular diluents. DFT studies indicated higher metal 'd' and 'f' orbital participation (covalence) in the bonding with R-BTP in the case of Am(3+) complexes as compared to that in the case of Eu(3+) complexes, which resulted in the selectivity of these classes of ligands. The observed results may have a great significance in the radioactive waste management involving the partitioning and transmutation strategy.

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“…While ignoring the unresolved controversy regarding the origin of hypersensitivity in the absorption and emission spectra of lanthanide compounds [8][9][10][11], researchers have utilized the phenomena to obtain detailed information regarding the coordination [12][13][14]. Extensive thermodynamic data and stability constants [14] and in some cases the Ln3+ site symmetry [12,13] have been obtained from the oscillator strength, shifts and shape of the hypersensitive peaks. In Fig.…”

Section: Resultsmentioning

confidence: 99%

The thermal characteristics of potassium oxalato lanthanates: K3LnOx3 · n H2O (Ln=La−Tb) and K8Ln2Ox7 · 14 H2O (Ln=Tb−Yb, Y)

Kahwa

Selbin

1983

Journal of Thermal Analysis

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The title compounds were studied by TG, DTA, DSC, IR and absorption spectroscopy. The complexes go through dehydration (70-200~ an irreversible exothermic process (in air or N 2 atmosphere, 250--300~ and decomposition to a mixture of oxides and carbonates (385--700~The exothermic process occurs without weight loss and corresponding heats of reaction fall in the range 0-26 k J/tool. The absorption spectrum of the Nd complex in the range 5000-6000 A was employed to monitor perturbations in the coordination sphere of Nd 3+ arising from the exothermic process. Involvement of the Nd3+ cation is implied and the heats of reaction show a close relationship to the radii of Ln 3+. The interpretation of these data was made with the aid of valuable structural information obtained previously.Recently we reported a successful synthesis of potassium oxalato lanthanates: K3LnOx 3 9 n H20 (n=6 for Ln= La, n=5.5 for Ln=Ce, Pr and n=3 for Ln = Nd, Sm, Eu, Gd, Tb) and K8Ln2Ox 7 ~ 14 H20 for Ln = Tb, Dy, Ho, Er, Yb and Y [1]. In that report the detailed crystal structures of the complexes of Nd, Gd, Er and Y were described and cell parameters of the complexes of Sm, Eu, Tb, Dy, Yb were given. The complexes of Nd, Sm, Eu, Gd are triclinic with space group P 1 and those of Dy, Ho, Er, Yb and Y are monoclinic with space group C2/c. Tb forms a monoclinic complex K8Tb2Ox 7 9 14 H20 and a triclinic complex K3TbOx 3 ~ 3 H20. The complexes of La, Ce and Pr have a different crystal structure which is currently being investigated.In a further investigation of these complexes we have studied their thermal characteristics by differential thermal analysis (DTA), differential scanning calorimetry (DSC), thermogravimetry (TG) and absorption spectroscopy. The complexes show dehydration and finally decomposition into a mixture of oxides and carbonates in the range 50-200 and 385-700 ~ (Ce complex decomposes at 320-330 ~ respectively. In addition to these endothermic stages an irreversible exothermic peak is observed without weight loss at 250-300 ~ and DSC studies indicate energies involved to be in the range 0-26 kJ/mol of Ln 3+ .~On study leave from the

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Analysis of the fluorescence spectra of europium(III)-bis-phenanthroline-tris-carboxylate complexes

Cited by 41 publications

References 25 publications

Probing Site Symmetry Around Eu³⁺ in Nanocrystalline ThO₂ Using Time Resolved Emission Spectroscopy

Probing Site Symmetry Around Eu³⁺ in Nanocrystalline ThO₂ Using Time Resolved Emission Spectroscopy

A remarkable enhancement in Am³⁺/Eu³⁺selectivity by an ionic liquid based solvent containing bis-1,2,4-triazinyl pyridine derivatives: DFT validation of experimental results

The thermal characteristics of potassium oxalato lanthanates: K3LnOx3 · n H2O (Ln=La−Tb) and K8Ln2Ox7 · 14 H2O (Ln=Tb−Yb, Y)

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Analysis of the fluorescence spectra of europium(III)-bis-phenanthroline-tris-carboxylate complexes

Cited by 41 publications

References 25 publications

Probing Site Symmetry Around Eu3+ in Nanocrystalline ThO2 Using Time Resolved Emission Spectroscopy

Probing Site Symmetry Around Eu3+ in Nanocrystalline ThO2 Using Time Resolved Emission Spectroscopy

A remarkable enhancement in Am3+/Eu3+selectivity by an ionic liquid based solvent containing bis-1,2,4-triazinyl pyridine derivatives: DFT validation of experimental results

The thermal characteristics of potassium oxalato lanthanates: K3LnOx3 · n H2O (Ln=La−Tb) and K8Ln2Ox7 · 14 H2O (Ln=Tb−Yb, Y)

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Probing Site Symmetry Around Eu³⁺ in Nanocrystalline ThO₂ Using Time Resolved Emission Spectroscopy

Probing Site Symmetry Around Eu³⁺ in Nanocrystalline ThO₂ Using Time Resolved Emission Spectroscopy

A remarkable enhancement in Am³⁺/Eu³⁺selectivity by an ionic liquid based solvent containing bis-1,2,4-triazinyl pyridine derivatives: DFT validation of experimental results