Temperature-dependent luminescence spectroscopic investigations of uranyl(<scp>vi</scp>) complexation with the halides F<sup>−</sup>and Cl<sup>−</sup>

Demnitz, Maximilian; Hilpmann, Stephan; Lösch, Henry; Bok, Frank; Steudtner, Robin; Patzschke, Michael; Stumpf, Thorsten; Huittinen, Nina

doi:10.1039/d0dt00646g

Cited by 24 publications

(22 citation statements)

References 47 publications

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“…PLQYs vary widely within the series, many being lower than 1% and some having values of 5–20% (which are however moderate compared with some literature values − ). In these cases in which the PLQYs are sufficiently large, the emission spectra are intense and well resolved, and they show the usual fine structure associated with the vibronic progression corresponding to the S 11 → S 00 and S 10 → S 0ν (ν = 0–4) electronic transitions. , The spectra of compounds 5 , 10 , 11 , 14 , and 15 , which have PLQYs of 5, 17, 10, 7, and 20%, respectively, are shown in Figure , together with that of uranyl nitrate hexahydrate given as a reference. While complexes 10 and 15 , with the highest PLQY values, both involve aliphatic dicarboxylate ligands, there is no obvious overall correlation of PLQY with the aliphatic or aromatic nature of the carboxylates.…”

Section: Resultsmentioning

confidence: 80%

“…In these cases in which the PLQYs are sufficiently large, the emission spectra are intense and well resolved, and they show the usual fine structure associated with the vibronic progression corresponding to the S 11 → S 00 and S 10 → S 0ν (ν = 0−4) electronic transitions. 74,75 The spectra of compounds nature of the carboxylates. These five complexes illustrate very neatly the redshift associated with the transition from uranyl with six (5 and 11) to five equatorial donors (10, 14, and 15).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Zwitterionic and Anionic Polycarboxylates as Coligands in Uranyl Ion Complexes, and Their Influence on Periodicity and Topology

et al. 2022

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The three zwitterionic di- and tricarboxylate ligands 1,1′-[(2,3,5,6-tetramethylbenzene-1,4-diyl)bis(methylene)]bis(pyridin-1-ium-4-carboxylate) (pL1), 1,1′-[(2,3,5,6-tetramethylbenzene-1,4-diyl)bis(methylene)]bis(pyridin-1-ium-3-carboxylate) (mL1), and 1,1′,1″-[(2,4,6-trimethylbenzene-1,3,5-triyl)tris(methylene)]tris(pyridin-1-ium-4-carboxylate) (L2) have been used as ligands to synthesize a series of 15 uranyl ion complexes involving various anionic coligands, in most cases polycarboxylates. [(UO2)2(pL1)2(cbtc)(H2O)2]·10H2O (1, cbtc4– = cis,trans,cis-1,2,3,4-cyclobutanetetracarboxylate) is a discrete, dinuclear ring-shaped complex with a central cbtc4– pillar. While [UO2(pL1)(NO3)2] (2), [UO2(pL1)(OAc)2] (3), and [UO2(pL1)(HCOO)2] (4) are simple chains, [(UO2)2(mL1)(1,3-pda)2] (5, 1,3-pda2– = 1,3-phenylenediacetate) is a daisy chain and [UO2(pL1)(pdda)]3·10H2O (6, pdda2– = 1,2-phenylenedioxydiacetate) is a double-stranded, ribbon-like chain. Both [UO2(pL1)(pht)]·5H2O (7, pht2– = phthalate) and [(UO2)3(mL1)(pht)2(OH)2] (8) crystallize as diperiodic networks with the sql topology, the latter involving hydroxo-bridged trinuclear nodes. [(UO2)2(pL1)(c/t-1,3-chdc)2] (9, c/t-1,3-chdc2– = cis/trans-1,3-cyclohexanedicarboxylate) and [UO2(pL1)(t-1,4-chdc)]·1.5H2O (10, t-1,4-chdc2– = trans-1,4-cyclohexanedicarboxylate) are also diperiodic, with the V2O5 and sql topologies, respectively. Both [(UO2)2(mL1)(c/t-1,4-chdc)2] (11) and [(UO2)2(pL1)(1,2-pda)2] (12, 1,2-pda2– = 1,2-phenylenediacetate) crystallize as diperiodic networks with hcb topology, and they display threefold parallel interpenetration. [HL2][(UO2)3(L2)(adc)3]Br (13, adc2– = 1,3-adamantanedicarboxylate) contains a very corrugated hcb network with two different kinds of cells, and the uncoordinated HL2+ molecule associates with the coordinated L2 to form a capsule containing the bromide anion. [(UO2)2(pL1)(kpim)2] (14, kpim2– = 4-ketopimelate) is a three-periodic framework with pL1 molecules pillaring fes diperiodic subunits, whereas [(UO2)2(L2)2(t-1,4-chdc)](NO3)1.7Br0.3·6H2O (15), the only cationic complex in the series, is a triperiodic framework with dmc topology and t-1,4-chdc2– anions pillaring fes diperiodic subunits. Solid-state emission spectra and photoluminescence quantum yields are reported for all complexes.

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Section: Resultsmentioning

confidence: 80%

Section: ■ Results and Discussionmentioning

confidence: 99%

Zwitterionic and Anionic Polycarboxylates as Coligands in Uranyl Ion Complexes, and Their Influence on Periodicity and Topology

et al. 2022

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“…For the bromide samples however, as the 1:0- and 1:1-complexes are spectrally very similar in luminescence, it can be assumed that their transient spectra are also very similar and are difficult to be separated spectrally due to the broad character of transient absorptions. Additionally, their temporal behavior is coupled via the complexation equilibrium, which makes them both appear as one component in a PARAFAC deconvolution and leading to a reduced number of components observable in the bromide samples.…”

Section: Resultsmentioning

confidence: 99%

Quenching Mechanism of Uranyl(VI) by Chloride and Bromide in Aqueous and Non-Aqueous Solutions

et al. 2021

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A major hindrance in utilizing uranyl(VI) luminescence as a standard analytical tool, for example, in environmental monitoring or nuclear industries, is quenching by other ions such as halide ions, which are present in many relevant matrices of uranyl(VI) speciation. Here, we demonstrate through a combination of time-resolved laser-induced fluorescence spectroscopy, transient absorption spectroscopy, and quantum chemistry that coordinating solvent molecules play a crucial role in U(VI) halide luminescence quenching. We show that our previously suggested quenching mechanism based on an internal redox reaction of the 1:2-uranyl–halide-complex holds also true for bromide-induced quenching of uranyl(VI). By adopting specific organic solvents, we were able to suppress the separation of the oxidized halide ligand X2 · – and the formed uranyl(V) into fully solvated ions, thereby “reigniting” U(VI) luminescence. Time-dependent density functional theory calculations show that quenching occurs through the outer-sphere complex of U(VI) and halide in water, while the ligand-to-metal charge transfer is strongly reduced in acetonitrile.

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“…Bathochromic shift has been observed because of the displacement of the naphthalic hydrogens during the chelation process. It is known that deprotonation of phenols is accompanied by a bathochromic shift of the absorption band [ 44 , 45 ].…”

Section: Resultsmentioning

confidence: 99%

Spectroscopic Determination of Fluoride Using Eriochrome Black T (EBT) as a Spectrophotometric Reagent from Groundwater

G/Mariam

Diro

Asere

et al. 2021

International Journal of Analytical Chemistry

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Fluoride health problem is a great concern worldwide, most often as a result of groundwater intake. Thus, determination of fluoride is vital to take appropriate measures upon fluoride contamination of water. Potentiometric method of analysis is reliable for the determination of fluoride in various samples. In addition, spectroscopic methods are found important to quantify fluoride levels from water; however, several factors hinder its easier determination. Among the bottlenecks, the use of toxic chemicals and tedious steps in preparing chemicals (e.g., SPADNS method) are to mention a few. In this study, a spectrophotometric method was developed for the determination of fluoride from groundwater using Eriochrome Black T (EBT) as a spectroscopic reagent. Experimental parameters that influence the determination of fluoride including ligand type, kinetics, pH, and ligand-to-metal ratio were assayed. Evaluation of fluoride levels showed that Beer–Lambert’s law is obeyed in the range of 0.3–5.0 mg/L at 544 nm. The calibration curve, resulting in good linearity (R2 = 0.9997), was considered during quantitative analysis of the samples and in the spiking analysis. The limits of detection (LOD) and quantification (LOQ) of the method were found to be 0.19 and 0.64 mg/L, respectively. The precision studied in terms of intraday and interday at three concentration levels showed less than 5.4% RSD. Applicability of the method was investigated by analyzing groundwater samples spiked with fluoride standards, and satisfactory recoveries in the range of 98.18–111.4 were demonstrated. The developed spectrophotometric method has been successfully applied for fluoride determinations in groundwater samples. Thus, it could be used as an attractive alternative for the determination of fluoride from groundwater.

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Temperature-dependent luminescence spectroscopic investigations of uranyl(vi) complexation with the halides F⁻and Cl⁻

Abstract: Uranyl(vi) complexation with fluoride and chloride was investigated with luminescence spectroscopy, and the strong quenching by chloride was overcome by freezing.

Cited by 24 publications

References 47 publications

Zwitterionic and Anionic Polycarboxylates as Coligands in Uranyl Ion Complexes, and Their Influence on Periodicity and Topology

Zwitterionic and Anionic Polycarboxylates as Coligands in Uranyl Ion Complexes, and Their Influence on Periodicity and Topology

Quenching Mechanism of Uranyl(VI) by Chloride and Bromide in Aqueous and Non-Aqueous Solutions

Spectroscopic Determination of Fluoride Using Eriochrome Black T (EBT) as a Spectrophotometric Reagent from Groundwater

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Temperature-dependent luminescence spectroscopic investigations of uranyl(vi) complexation with the halides F−and Cl−

Abstract: Uranyl(vi) complexation with fluoride and chloride was investigated with luminescence spectroscopy, and the strong quenching by chloride was overcome by freezing.

Cited by 24 publications

References 47 publications

Zwitterionic and Anionic Polycarboxylates as Coligands in Uranyl Ion Complexes, and Their Influence on Periodicity and Topology

Zwitterionic and Anionic Polycarboxylates as Coligands in Uranyl Ion Complexes, and Their Influence on Periodicity and Topology

Quenching Mechanism of Uranyl(VI) by Chloride and Bromide in Aqueous and Non-Aqueous Solutions

Spectroscopic Determination of Fluoride Using Eriochrome Black T (EBT) as a Spectrophotometric Reagent from Groundwater

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Temperature-dependent luminescence spectroscopic investigations of uranyl(vi) complexation with the halides F⁻and Cl⁻