Combination of covalent and hydrogen bonding in the formation of 3D uranyl-carboxylate networks

Dalai, Sudipta; Bera, Madhusudan; Rana, Abhinandan; Chowdhuri, Durga Sankar; Zangrando, Ennio

doi:10.1016/j.ica.2010.06.043

Cited by 28 publications

(24 citation statements)

References 55 publications

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“…The five oxygen atoms located on the equatorial plane are O1, O4, and O2A provided by three pmb ligands, as well as O9 and O10B from the oxalate ligand (symmetric codes for 1: A: -x+2, -y+1, -z+1; B: -x+1, -y+2, -z+1). The origin of the unexpected oxalate ligand could be the acetate ion from the uranyl acetate used as the starting material, since such in situ formation of oxalate from the carboxylate groups have been reported previously [53].…”

Section: Resultsmentioning

confidence: 66%

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Structural and spectroscopic characterization of two new layered uranyl(VI) p-xylenediphosphonate compounds synthesized via ionothermal method

Zheng

Gao

Chen

et al. 2015

Inorganica Chimica Acta

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∆ These authors contributed equally to this work ABSTRACT.2 Two new uranyl phosphonates were synthesized by using p-xylenediphosphonic acid (pmbH 4 ) to react with uranyl salts in Emim or BMMim ([EMim][PF 6 ]=1-ethyl-3-methylimidazolium hexafluorophosphate;[BMMim]Cl=1-butyl-2,3-dimethylimidazolium chloride) at elevated temperature, namely [EMim][UO 2 (pmbH 2 ) 0.5 (pmbH 2 ) 0.5 (ox) 0.5 ] (1) and[BMMim] 2 [(UO 2 ) 2 (pmbH 2 )(pmb)] (2). Both compounds adopt two dimensional structures, consisting of an anionic layer of uranyl phosphonate, with cations filled in the interlayer spaces.The spectroscopic properties of the compounds were studied extensively using UV-Vis absorption, temperature dependent fluorescence, Raman and IR spectroscopies. The UV-Vis absorption spectrum contains typical peaks of uranyl complexes at around 320 nm and 420 nm, which are originated from the charge transfer transitions from O 2p orbitals to the U 5f/6d orbitals. Both compounds adopt five strong emission peaks, whose intensities increase with the decrease of temperature, as observed in the temperature dependent fluorescence spectra. In Raman and IR spectra, the peaks corresponding to the stretch of C-H/O-H, P-O/P=O, and O•U•O bonds could all be located and assigned.

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Section: Resultsmentioning

confidence: 66%

“…The oxalate ligand formed in situ by using acetate anion during the reaction [53]. The pmb ligands, with coordination modes A and B (Scheme 2), act as the bridging units.…”

Section: Resultsmentioning

confidence: 99%

Structural and spectroscopic characterization of two new layered uranyl(VI) p-xylenediphosphonate compounds synthesized via ionothermal method

Zheng

Gao

Chen

et al. 2015

Inorganica Chimica Acta

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“…The previously reported complex [UO 2 (L)(OH)] ( 1 ) was obtained from a 1:2:2 mixture of uranyl nitrate hexahydrate, LH, and NaOH (sufficient to convert LH to L – ) in water, which was heated at 160 °C, then cooled, and filtered 12. Here, it may be that the conditions of high temperature and pressure were simply advantageous for forming a homogeneous solution of the initial reactants.…”

Section: Resultsmentioning

confidence: 99%

“…Indeed, it is this form of the ligand that is found in the lanthanide(III)–copper(II) heterometallic complexes described by Gunning and Cahill, which crystallize as 3D frameworks with the expected ligand connectivity 11. Significantly, in the only previously known homometallic uranyl complex with this ligand, [UO 2 (L)(OH)] ( 1 ), which crystallizes as a 1D polymer,12 the anion functions exclusively as a carboxylate O donor. In an investigation of the suitability of HL for building uranyl–d‐block‐cation heterometallic systems, we have obtained a uranyl–copper(II) complex that crystallizes as a 3D framework.…”

Section: Introductionmentioning

confidence: 94%

Uranyl Ion Complexes with trans‐3‐(3‐Pyridyl)acrylic Acid Including a Uranyl–Copper(II) Heterometallic Framework

Thuéry

Harrowfield

2014

Eur J Inorg Chem

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As a heterofunctional pro‐ligand with both hard and soft coordination sites, trans‐3‐(3‐pyridyl)acrylic acid (LH) is of potential interest for the design of heterometallic complexes of f‐ and d‐block cations, as previously shown in the case of lanthanides. The reaction of LH with uranyl nitrate in water/acetonitrile at 180 °C yields the complex [(UO2)3(L)(HL)(O)(OH)3]·2.5H2O·CH3CN (2), which is different from the previously reported complex [UO2(L)(OH)] (1). Complex 2 crystallizes as a ribbon‐like 1D coordination polymer with a skeleton bridged by oxido and hydroxido ligands, in which the uranyl cation is bound to the bridging bidentate carboxylato groups, and the pyridyl groups (one of them protonated) are directed sideways. In the presence of copper nitrate, the reaction affords the heterometallic complex [(UO2)2Cu(L)3(O)(H2O)](NO3) (3), in which the harder uranium atom is bound to two μ3‐oxido anions and to chelating and bridging carboxylato groups to generate a tetranuclear secondary building unit, whereas the softer copper cations are bound to three pyridyl groups and only one carboxylato donor. The copper atoms are further involved in cation–cation interactions with uranyl oxido groups, and the Cu–O(oxido) bond lengths of 2.162(13) and 2.248(16) Å are among the shortest measured to date. 3 crystallizes as a 3D assembly, which displays narrow channels, and it illustrates the ability of copper cations, in combination with a ditopic ligand, to assemble discrete uranyl‐containing units into a framework structure. The emission spectra of complexes 1 and 2 in the solid state display the usual vibronic progression of the uranyl ion in the range 450–650 nm, and the width of the bands indicates that they may be the superposition of slightly different series, due to the inequivalent uranyl centres in the lattices.

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“…[3] Uranium offers interesting architectures due to its higher coordination number in comparison to main group/transition elements and the structural diversity depends upon the reaction condition as well as the choice of organic ligands. [4,5] It is perceptible; however, that the tricky application of hydrogen bonding and other non-covalent interactions during the synthesis of such materials are becoming an area of interest and the possibility of generating unpredicted dimensionality is opening up in connection to novel topologies. [6] It is well known that uranium(VI) tends to form linear cation with two oxygen atoms UO 2 2+ which can be further surrounded by a number of anions commonly laying in one plain, which is perpendicular to O-U-O structure.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Characterization, and Crystal Structure of New Complex, Based on Proton Transfer to Uranium(VI) Complex

Saravani

Mozafaripoor

2015

Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-

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Combination of covalent and hydrogen bonding in the formation of 3D uranyl-carboxylate networks

Cited by 28 publications

References 55 publications

Structural and spectroscopic characterization of two new layered uranyl(VI) p-xylenediphosphonate compounds synthesized via ionothermal method

Structural and spectroscopic characterization of two new layered uranyl(VI) p-xylenediphosphonate compounds synthesized via ionothermal method

Uranyl Ion Complexes with trans‐3‐(3‐Pyridyl)acrylic Acid Including a Uranyl–Copper(II) Heterometallic Framework

Synthesis, Characterization, and Crystal Structure of New Complex, Based on Proton Transfer to Uranium(VI) Complex

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