Preparation and characterization of uranyl complexes with phosphonate ligands

Hnatejko, Zbigniew; Lis, Stefan; Stryla, Zdzislaw

doi:10.1007/s10973-009-0195-0

Cited by 13 publications

(6 citation statements)

References 38 publications

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“…The PLQY of Na@U 6 P 6 was 33%, which is higher than that of UO 2 (NO 3 ) 2 ·6H 2 O (27%). The luminescence of the uranyl ion is related to the type of complex that it is a part of, the presence of water molecules around the U 6+ atom, counterbalance ions, and the solvent type because all of these affect the vibration of the OUO double bonds . The greater the vibration of the OUO bonds, the greater the energy loss during the transition process, which negatively impacts the luminescence.…”

Section: Results and Discussionmentioning

confidence: 99%

Sandwich-Type Uranyl Phosphate–Polyoxometalate Cluster Exhibiting Strong Luminescence

et al. 2021

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A pure inorganic uranyl phosphate–polyoxometalate of Na17{Na@[(SbW9O33)2(UO2)6(PO3OH)6]}·xH2O (abbreviated as Na@U 6 P 6 , with x ≈ 46) featuring a sandwich-type structure was prepared using Keggin-type trilacunary [α-B-SbW9O33]9– units as building blocks, which were formed in situ by SbCl3 and Na2WO4·2H2O. Crystal structural analysis showed that six UO2 2+ cations and six PO3OH2– anions generated a wheel-like cluster unit with a Na+ center ([Na@(UO2)6(PO3OH)6]+) that is stabilized by two [α-B-SbW9O33]9– units. Na@U 6 P 6 displayed a solid-state photoluminescence quantum yield of 33% at 300 K. The temperature-dependent fluorescence emission spectra showed that Na@U 6 P 6 has temperature-sensitive fluorescence in which its emission intensity decreased by 77% as the temperature increased from 200 to 300 K. These results suggest that such uranyl phosphate–polyoxometalate clusters could serve as potential temperature-sensitive molecular materials.

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Section: Results and Discussionmentioning

confidence: 99%

Sandwich-Type Uranyl Phosphate–Polyoxometalate Cluster Exhibiting Strong Luminescence

et al. 2021

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“…On the other hand metal‐centered excitation at 415 nm results exclusively in uranyl‐centered emission and no radiative energy transfer to the ligand is observed. Independent of the excitation wavelength (415 nm or others), the uranium‐centered emissions show very low quantum yields (<1 %) suggesting higher vibrational relaxation in case of phosphonate ester coordination , …”

Section: Resultsmentioning

confidence: 99%

Coordination Polymers based on the Neutral Ditopic Ligand (C₆H₄PO(OCH₃)₂)₂ Involving some f‐Block Elements

Krekić

Käkel

Klintuch

et al. 2018

Zeitschrift anorg allge chemie

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An improved synthesis using microwave heating affords (C6H4PO(OCH3)2)2 in excellent isolated yield (95 %). The ligand properties of this bisphosphonateester were explored towards hard metal centers M 2+ (M = Ca, UO2) and M 3+ (M = La, Ce, Sm, Eu) resulting in coordination polymers, for which the reduction of ionic size of the central metal atom resulted in lower‐dimensional structural motifs as opposed to higher dimensional networks obtained for the larger ions. All coordination polymers were characterized by single‐crystal X‐ray diffraction, IR spectroscopy, and combustion analysis. The ligand was furthermore characterized with multinuclear NMR spectroscopy.

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“…16 Whilst the luminescence of uranyl salts in aqueous media has been explored in detail, similar studies of uranyl complexes bearing organic-based ligands in protic solvents remain relatively uncommon. 17 The principal reason for this, is that the majority of organic complexes are not emissive at room temperature in fluid solution. 18,19 The p-p* and n-p* absorption transitions of common organic ligands (historically, b-diketonates and Schiff bases) overlap significantly with the uranyl emission spectrum; the uranyl emission is quenched by thermally-activated back energy transfer to low-lying excited states of the ligand.…”

Section: Introductionmentioning

confidence: 99%

Probing the local coordination environment and nuclearity of uranyl(vi) complexes in non-aqueous media by emission spectroscopy

et al. 2011

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We describe the synthesis, solid state and solution properties of two families of uranyl(VI) complexes that are ligated by neutral monodentate and anionic bidentate P=O, P=NH and As=O ligands bearing pendent phenyl chromophores. The uranyl(VI) ions in these complexes possess long-lived photoluminescent LMCT (3)Π(u) excited states, which can be exploited as a sensitive probe of electronic structure, bonding and aggregation behaviour in non-aqueous media. For a family of well defined complexes of given symmetry in trans-[UO(2)Cl(2)(L(2))] (L = Ph(3)PO (1), Ph(3)AsO (2) and Ph(3)PNH (3)), the emission spectral profiles in CH(2)Cl(2) are indicative of the strength of the donor atoms bound in the equatorial plane and the uranyl bond strength; the uranyl LMCT emission maxima are shifted to lower energy as the donor strength of L increases. The luminescence lifetimes in fluid solution mirror these observations (0.87-3.46 μs) and are particularly sensitive to vibrational and bimolecular deactivation. In a family of structurally well defined complexes of the related anion, tetraphenylimidodiphosphinate (TPIP), monometallic complexes, [UO(2)(TPIP)(thf)] (4), [UO(2)(TPIP)(Cy(3)PO)] 5), a bimetallic complex [UO(2)(TPIP)(2)](2) (6) and a previously known trimetallic complex, [UO(2)(TPIP)(2)](3) (7) can be isolated by variation of the synthetic procedure. Complex 7 differs from 6 as the central uranyl ion in 7 is orthogonally connected to the two peripheral ones via uranyl → uranium dative bonds. Each of these oligomers exhibits a characteristic optical fingerprint, where the emission maxima, the spectral shape and temporal decay profiles are unique for each structural form. Notably, excited state intermetallic quenching in the trimetallic complex 7 considerably reduces the luminescence lifetime with respect to the monometallic counterpart 5 (from 2.00 μs to 1.04 μs). This study demonstrates that time resolved and multi-parametric luminescence can be of value in ascertaining solution and structural forms of discrete uranyl(VI) complexes in non-aqueous solution.

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Preparation and characterization of uranyl complexes with phosphonate ligands

Cited by 13 publications

References 38 publications

Sandwich-Type Uranyl Phosphate–Polyoxometalate Cluster Exhibiting Strong Luminescence

Sandwich-Type Uranyl Phosphate–Polyoxometalate Cluster Exhibiting Strong Luminescence

Coordination Polymers based on the Neutral Ditopic Ligand (C₆H₄PO(OCH₃)₂)₂ Involving some f‐Block Elements

Probing the local coordination environment and nuclearity of uranyl(vi) complexes in non-aqueous media by emission spectroscopy

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Preparation and characterization of uranyl complexes with phosphonate ligands

Cited by 13 publications

References 38 publications

Sandwich-Type Uranyl Phosphate–Polyoxometalate Cluster Exhibiting Strong Luminescence

Sandwich-Type Uranyl Phosphate–Polyoxometalate Cluster Exhibiting Strong Luminescence

Coordination Polymers based on the Neutral Ditopic Ligand (C6H4PO(OCH3)2)2 Involving some f‐Block Elements

Probing the local coordination environment and nuclearity of uranyl(vi) complexes in non-aqueous media by emission spectroscopy

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Coordination Polymers based on the Neutral Ditopic Ligand (C₆H₄PO(OCH₃)₂)₂ Involving some f‐Block Elements