The structure and spectroscopic characterization of complexes with tetraethyl methylenediphosphonate in solution and in solid state

Piskuła, Zbigniew; Manszewski, Tomasz; Kubicki, Maciej; Lis, Stefan

doi:10.1016/j.molstruc.2011.12.054

Cited by 7 publications

(3 citation statements)

References 21 publications

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“…It is known that the characteristic vibronic fine structure represents the certain symmetry (and geometry) of the first coordination sphere of the uranyl complexes, , which enables structure elucidation by UV–vis spectra. The spectra in Figure show typical band splitting in the 380–450 nm region, and this character is much different from the spectra of pentagonal coordinated species (e.g., [UO 2 (H 2 O) 5 ] 2+ ) and the hexagonal coordinated 1:1 complex of TAMBP with uranyl nitrate . By means of spectral characters of this complex, it can be inferred that the real L/U ratio must be 2.0 (a tetragonal coordination to the uranyl with the four O-donors from the two bidentate ligands).…”

Section: Resultsmentioning

confidence: 84%

“…On the other hand, studies using multidentate extractants such as octyl(phenyl)- N , N -diisobutylcarbamoylmethyl phosphine oxide (CMPO) and diglycolamides have shown improved efficiencies in ILs versus molecular organic solvents. The tetraalkyl methylenebisphosphonates (TAMBPs) are also a class of bidentate extractants for lanthanides and actinides, and their 1:1 adducts with uranyl nitrate have been well studied . The extraction of uranium to ILs by using TAMBPs, as well as the complexation of TAMBPs with uranyl in ILs, have not been reported yet.…”

Section: Introductionmentioning

confidence: 99%

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A 2:1 Dicationic Complex of Tetraethyl Methylenebisphosphonate with Uranyl Ion in Acetonitrile and Ionic Liquids

2012

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A new 2:1 dicationic complex formed by TEMBP with uranyl ion in acetonitrile and two hydrophobic ILs, [BMIm][NTf(2)] and [N(4111)][NTf(2)], has been identified with combination of optical spectroscopic and mass spectrometric studies. With excess of TEMBP ligand (L/U > 2.0), the uranyl is completely coordinated by two ligands to form a dicationic complex [UO(2)(TEMBP)(2)](2+). The UV-vis spectra of [UO(2)(TEMBP)(2)](2+) in acetonitrile and in the two ILs are similar. The vibronic fine structures in UV-vis spectrum of [UO(2)(TEMBP)(2)](2+) show characters of tetragonal coordination in the uranyl equatorial plane. The symmetry of proposed structure of [UO(2)(TEMBP)(2)](2+) is D(2h), and its UV-vis spectrum is tentatively interpreted based on the structural similarity to the well studied [UO(2)Cl(4)](2-) complex. The luminescence emission spectrum of [UO(2)(TEMBP)(2)](2+) shows typical vibronic bands, having a mirror relationship with the 455-500 nm region of the corresponding absorption spectrum. The stoichiometry of [UO(2)(TEMBP)(2)](2+) is confirmed by electrospray ionization-ion trap mass spectrometry (ESI-ITMS) studies with acetonitrile as solvent. The "naked" dication (m/z 423) is characterized by the remarkable eight peaks with interval of 14 m/z units in its tandem mass spectra, representing the fragmentation of ligands by losing C(2)H(4) units from their ethoxy groups. However, the dication tends to exist as a weak adduct with either an additional ligand or an anion in the ESI mass spectrum. The adducts {[UO(2)(TEMBP)(2)](2+) + TEMBP} (m/z 567) and {[UO(2)(TEMBP)(2)](2+) + [ClO(4)](-)} (m/z 945) are favorable in pure acetonitrile, while only one adduct {[UO(2)(TEMBP)(2)](2+) + [NTf(2)](-)} (m/z 1126) is predominant in [BMIm][NTf(2)] (diluted with acetonitrile). The results of ESI-ITMS study are consistent with those of optical spectroscopic studies.

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Section: Resultsmentioning

confidence: 84%

Section: Introductionmentioning

confidence: 99%

A 2:1 Dicationic Complex of Tetraethyl Methylenebisphosphonate with Uranyl Ion in Acetonitrile and Ionic Liquids

2012

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“…These compounds crystallize in both chiral and achiral space groups, influenced by the organic templates. The architectures of uranyl phosphonates are typically adapted by the degree of deprotonation of the phosphonate ligand caused by the amino templates such as aliphatic amines ,,− and aromatic amines. − …”

Section: Introductionmentioning

confidence: 99%

Porous Uranium Diphosphonate Frameworks with Trinuclear Units Templated by Organic Ammonium Hydrolyzed from Amine Solvents

et al. 2017

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By varying solvent systems, the solvothermal treatment of uranyl nitrate and methylenediphosphonic acid (HPCP) afforded three new porous uranyl-organic frameworks (UOFs). All were structurally characterized by single-crystal X-ray diffraction and formulated as (EtNH)[(UO)(PCP)](HO) (1), (MeNH)(HO)[(UO)(PCP)(HO)] (2), and [Na(HO)](HO)[(UO)(PCP)(HO)](HO) (3). These compounds crystallize with three-dimensional anionic frameworks containing U(VI) and distinct cationic species due to in situ solvent hydrolysis. The solvent systems diethylformamide (DEF), N-methyl-2-pyrrolindone (NMP), and the additive sodium vanadate (NaVO) significantly impact the resultant structures, affording diethyl ammonium, methyl ammonium, and sodium cations captured in channels of the anionic frameworks of 1-3. In 1, a trinuclear UO unit formed by three uranyl polyhedra that share edges is connected into a three-dimensional framework. Compound 2 has a three-dimensional framework formed from a uranyl-methylenediphosphonate layer that is pillared by UO pentagonal bipyramids. With the inclusion of sodium cations, 3 is a porous framework containing UO pentagonal bipyramids within a layer, with sodium cations and UO square bipyramids linking the adjacent layers. Compounds 1-3 feature the uranyl/ligand ratio of 3:2, but present diverse structural building units ranging from edge-shared trinuclear to heteronuclear assemblies. The compounds have been characterized by infrared (IR), Raman, and UV-vis spectroscopies, X-ray diffraction, and thermogravimetric analysis.

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Hybrid Materials of the f-Elements Part II

Surbella

Cahill

2015

Handbook on the Physics and Chemistry of Rare Earths

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The structure and spectroscopic characterization of complexes with tetraethyl methylenediphosphonate in solution and in solid state

Cited by 7 publications

References 21 publications

A 2:1 Dicationic Complex of Tetraethyl Methylenebisphosphonate with Uranyl Ion in Acetonitrile and Ionic Liquids

A 2:1 Dicationic Complex of Tetraethyl Methylenebisphosphonate with Uranyl Ion in Acetonitrile and Ionic Liquids

Porous Uranium Diphosphonate Frameworks with Trinuclear Units Templated by Organic Ammonium Hydrolyzed from Amine Solvents

Hybrid Materials of the f-Elements Part II

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