Ion‐Size‐Dependent Formation of Mixed Titanium/Lanthanide Oxo Clusters

Artner, Christine; Kronister, Stefan; Czakler, Matthias; Schubert, Ulrich

doi:10.1002/ejic.201402670

Cited by 25 publications

(19 citation statements)

References 14 publications

(23 reference statements)

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“…In the case of sepiolite samples saturated with lanthanide ions La, Eu, and Lu, a significantly smaller surface reduction was observed than in the case of the sepiolite U-1mM-ODTMA or sepiolite samples 1mM-, 5mM-ODTMA. This can be explained by the smaller sizes of Ln 3+ (about 1 Å) or Ln-O (less than 2.64 Å) [26] compared to uranium ions that can reach 6 Å, depending on the type of coordination sphere. Large and smaller pores are occupied by…”

Section: Surface Propetries Of the Sepiolitementioning

confidence: 99%

“…The most intensive vibrations at 800-440, 1220-980 cm −1 , 1470-60 cm −1 , 1670-50 cm −1 , 2930-2850 cm −1 , and 3600-3400 cm −1 are shown by the sepiolite and ODTMA-sepiolite FTIR-spectra ( Figure 3). The band at 441-440 cm −1 originates from the octahedral-tetrahedral bonds (Si-O-Mg bonds) and the bands at 650-648 cm −1 correspond to vibrations of the Mg-OH bond [26,27]. The bands at 690 cm −1 are assigned to the Si-O bonds deformation and bending modes [28].…”

Section: Fourier-transform Infrared Spectroscopy and Fluorescence Spementioning

confidence: 99%

“…The band at 441-440 cm −1 originates from the octahedral-tetrahedral bonds (Si-O-Mg bonds) and the bands at 650-648 cm −1 correspond to vibrations of the Mg-OH bond [26,27]. The bands at 690 cm −1 are assigned to the Si-O bonds deformation and bending modes [28].…”

Section: Fourier-transform Infrared Spectroscopy and Fluorescence Spementioning

confidence: 99%

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Adsorption Properties of Sepiolite in Relation to Uranium and Lanthanide Ions

Gładysz–Płaska

2019

Minerals

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The batch technique was used to study the adsorption of La(III), Eu(III), Lu(III), and U(VI) ions on sepiolite and ODTMA–sepiolite under ambient conditions. The effects of pH, time, and initial concentration were investigated. The highest U(VI) adsorption was found on ODTMA-sepiolite in the pH range of 6–8, while in the case of lanthanide ions, adsorption on sepiolite was 80% in the pH range of 4–8 and 98% for pH values above 8. The adsorption capacity of ODTMAsepiolite was found to be 285.6 mg/g for uranium, and raw sepiolite: 142.8 mg/g for U(VI), 91.6 mg/g for La(III), 91.4 mg/g for Eu (III), and 104.9 mol/g for Lu(III). ODTMA–sepiolite turned out to be a weak sorbent for lanthanide ions. Two short- and long-lived fluorescence species were observed in the TRLFS spectra of U(VI) adsorbed on sepiolite at pH 6.5. The average lifetimes of short- (τ1) and long-lived (τ2) fluorescence are τ1 = 2420 ± 430 ns and τ2 = 37950 ± 5710 ns for U-sepiolite; τ1 = 3523 ± 160 ns and τ2 = 45400 ± 1830 ns for U-ODTMA–sepiolite.

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Section: Surface Propetries Of the Sepiolitementioning

confidence: 99%

Section: Fourier-transform Infrared Spectroscopy and Fluorescence Spementioning

confidence: 99%

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Adsorption Properties of Sepiolite in Relation to Uranium and Lanthanide Ions

Gładysz–Płaska

2019

Minerals

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“…30 This limitation can be overcome with the assistance of highly absorbing 'antenna' ligands located in close proximity to the Ln 3+ ions via the classic S 0 → S 1 → T 1 → Ln 3+ energy transfer route. 31 In the literature, the majority of the previous reports on Ln-POT cages, however, have primarily focused on their syntheses and structural characterization, [15][16][17][18][19][20][21][22][23][24][25] leaving the photoluminescence properties less explored. In 2015, Wang et al studied the photoluminescence behaviour of anthracenecarboxylate-modified Ln-POT cages (with Ln 2 Ti 10 cores, Ln = Eu and Nd) and investigated the energy transfer process between the ligands and the Ln 3+ centres.…”

Section: +mentioning

confidence: 99%

Energy transfer and photoluminescence properties of lanthanide-containing polyoxotitanate cages coordinated by salicylate ligands

Subramanian

Matthews

et al. 2018

Dalton Trans.

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Polyoxotitanate (POT) cages have attracted considerable attention recently; much of this from the fact that they can be considered to be structural models for the technologically important semiconductor TiO2. Among the reported POT cages, lanthanide-containing (Ln-POT) cages are of particular interest owing to the fascinating luminescence properties of Ln3+ ions and the versatile coordination environments that they can adopt. In the present study, we report the energy transfer mechanism and photoluminescence properties of a series of isostructural Ln-POT cages coordinated by salicylate ligands, of general formula [LnTi6O3(OiPr)9(salicylate)6] (Ln-1, Ln = La to Er excluding Pm). Both visible (for Pr-1, Sm-1, Eu-1, Ho-1 and Er-1) and near-infrared (for Nd-1 and Er-1) Ln3+-centred photoluminescence can be sensitised in solution, and most importantly, their excitation bands all extend well into the visible region up to 475 nm. With the assistance of steady-state and time-resolved photoluminescence spectroscopy, an energy-transfer mechanism involving the salicylate-to-Ti4+ charge-transfer state is proposed to account for the largely red-shifted excitation wavelengths of these Ln-1 cages. The photoluminescence quantum yield of Nd-1 upon excitation via the charge-transfer state reaches 0.30 ± 0.01% in solution, making it among the highest reported values for Nd3+-complexes in the literature.

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“…The structures of most titanium-containing heterobimetallic clusters are based on a few common motifs, despite variation of coordination number, ionic size, and charge of the second metal. Some clusters with Pb, Sr [ 1 ], La, and Ce [ 2 ] are structurally derived from cyclic Ti 8 O 8 (OOCR) 16 . Another series is based on partial replacements of the Ti atoms in Ti 6 O 4 (OR) 8 (OOCR’) 8 by Fe, Zn, Cd, Ca, or Sr, with concomitant rearrangement of the ligand shell [ 3 ].…”

Section: Introductionmentioning

confidence: 99%