Crystal structures of new uranyl glutarate coordination polymers (NH4)2[(UO2)2(glt)3]·nH2O (n= 3 or 6) and R[UO2(glt)(Hglt)]·H2O (R = Na, K, Rb or Cs)

Новиков, С. А.; Сережкина, Л. Б.; Григорьев, М. С.; Manakov, N. V.; Сережкин, В. Н.

doi:10.1016/j.poly.2016.06.052

Cited by 10 publications

(5 citation statements)

References 49 publications

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“…The last compound in the present series, [(UO 2 ) 2 K 2 (C7) 3 (H 2 O)]·0.5H 2 O ( 9 ), contains a counterion quite different from those in complexes 1 – 8 , since it is a single alkali metal cation. Although uranyl ion complexes with C n 2– dicarboxylate ligands incorporating alkali or alkaline-earth metal cations have been reported for n = 4 (succinate) and n = 5 (glutarate), − for example (with formation of hydrogen bonded interpenetrated frameworks in one case), no example has been reported with larger n values. The asymmetric unit in 9 , which crystallizes in the Sohncke group P 2 1 2 1 2 1 , contains two uranyl cations, both chelated by three carboxylate groups [U–O(oxido) 1.763(8)–1.774(9) Å, U–O(carboxylate) 2.443(7)–2.508(7) Å], and two potassium cations in different environments (Figure ).…”

Section: Resultsmentioning

confidence: 99%

“…The network is binodal (dicarboxylate ligand and uranyl cations), the nickel(II) cations being simple links, and it has the point symbol {4 2 .6 3 .8}{4 2 .6} and the V2O5 topological type. Due to the tilting of the ribbons within the layers, the carboxylic groups are directed toward the interlayer space; however, those pertaining to different layers do not face exactly each other so as to form double hydrogen bonds as in 3, but each of them is bound instead to a lattice water molecule which is itself linked to one carboxylate oxygen atom and to a carboxylic group of the adjacent layer (Figure 9), thus forming a water-mediated 3D Although uranyl ion complexes with Cn 2dicarboxylate ligands incorporating alkali or alkaline-earth metal cations have been reported for n = 4 (succinate), 48 and n = 5 (glutarate), [49][50][51][52] for example (with formation of hydrogen bonded interpenetrated frameworks in one case 50 crystallizes in the same space group as 9, and with quite similar unit cell parameters. 12 These networks are very convoluted, being built of central chains running parallel to one another and surrounded on either side by two sets of chains running in the transverse direction ( Figure 11).…”

Section: Methodsmentioning

confidence: 99%

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Structure-Directing Effects of Counterions in Uranyl Ion Complexes with Long-Chain Aliphatic α,ω-Dicarboxylates: 1D to Polycatenated 3D Species

2018

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Nine uranyl ion complexes were synthesized under (solvo-)hydrothermal conditions using α,ωdicarboxylic acids HOOC-(CH2)n-2-COOH (H2Cn, n = 6-9) and diverse counterions. Complexes [PPh4][UO2(C6)(NO3)] (1) and [PPh4][UO2(C8)(NO3)] (2) contain zigzag one-dimensional (1D) chains, further polymerization being prevented by the terminal nitrate ligands. [PPh3Me][UO2(C7)(HC7)] (3) crystallizes as a 1D polymer with a curved section, hydrogen bonding of the uncomplexed carboxylic groups giving rise to formation of threefold interpenetrated two-dimensional (2D) networks. [PPh4][H2NMe2][(UO2)2(C7)3] (4) and [PPh3Me]2[(UO2)2(C8)3] (5) contain 1D chains, either ladderlike or containing doubly bridged dimers, while [PPh3Me]2[(UO2)2(C9)3]⋅2H2O (6) displays interdigitated, strongly corrugated honeycomb 2D nets. Ladderlike 1D polymers in [Cu(R,S-Me6cyclam)][(UO2)2(C7)2(C2O4)]⋅4H2O (7) are associated into columns by the hydrogen bonded counterions, whereas the [Ni(cyclam)] 2+ moieties are part of the 2D polymeric arrangement in [(UO2)2(C7)2(HC7)2Ni(cyclam)]⋅2H2O (8) due to axial coordination of the nickel(II) centre, hydrogen bonding mediated by water molecules generating a three-dimensional (3D) net. [(UO2)2K2(C7)3(H2O)]⋅0.5H2O (9) contains convoluted uranyl dicarboxylate 2D subunits which generate a 3D framework through 2D  3D parallel polycatenation similar to that previously found in [NH4]2[(UO2)2(C7)3]⋅2H2O; further linking of these subunits is provided by bonding of the potassium cations to carboxylate and uranyl oxido groups. The solid state emission spectra of complexes 1-6 and 9 display maxima positions typical of hexacoordinated uranyl carboxylate complexes, but uranyl luminescence is quenched in 7. A solid-state photoluminescence quantum yield of 11.5% has been measured for complex 1, while those for compounds 3-6 and 9 are in the range of 2.0-3.5%.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Structure-Directing Effects of Counterions in Uranyl Ion Complexes with Long-Chain Aliphatic α,ω-Dicarboxylates: 1D to Polycatenated 3D Species

2018

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“…Two of them form 2D-layered structures that are further extended into 3D-networks through hydrogen bonds between layers, water molecules and ammonium ions. Some of the other structures reported in that work extend as 1D chains; however, alkaline metal counterions between chains increase their dimensionality through edge and corner sharing between coordination polyhedra of various alkaline metal counterions with the UO 8 -polyhedra …”

Section: Results and Discussionmentioning

confidence: 90%

“…Some of the other structures reported in that work extend as 1D chains; however, alkaline metal counterions between chains increase their dimensionality through edge and corner sharing between coordination polyhedra of various alkaline metal counterions with the UO 8 -polyhedra. 98 U 6 (NO 3 ) 4 (Glut) 4 (O) 4 (OH) 4 (H 2 O) 6 •12H 2 O (5). When the reaction between [UO 2 (NO 3 ) 2 ]•6H 2 O, Na 2 TP, and Na 2 Glut involved a short reaction time, compound 1 was obtained.…”

Section: Crystal Growth and Designmentioning

confidence: 99%

Network Dimensionality of Selected Uranyl(VI) Coordination Polymers and Octopus-like Uranium(IV) Clusters

Zehnder

Boncella

Cross

et al. 2017

Crystal Growth & Design

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Using slow diffusion methods at room temperature, five uranium coordination polymers were obtained, which either employ glutarate (Glut), terephthalate (TP), or 2-aminoterephthalate (TPNH 2 ) as bridging systems. Four of these networks are based on the uranyl(VI)-unit, UO 2 2+ , and one formed through the integration of tetravalent uranium as the coordinating metal center. 1) arranges as intermeshed one-dimensional (1D) infinite linear chains, locked into a three-dimensional (3D) network through hydrogen bonds with a uninodal 4-coordinated uom topology. 2) assembles as intermeshed two-dimensional (2D) layers, also stabilized as a 3D network through hydrogen bonding with a 2-nodal 4coordinated pts network topology. Na 2 [[UO 2 ] 2 (TP) 3 ]•9H 2 O (3) forms parallel layers that are stacked in an AB pattern. Layers possess the uninodal 3-coordinate honeycomb (hcb 4) assembles as a 3D-coordination network with a uninodal 3-c srs (SrSi 2 ) topology. The fifth compound contains uranium(IV) and the glutarate entity; U 6 (NO 3 ) 4 (Glut) 4 (O) 4 (OH) 4 (H 2 O) 6 •12H 2 O (5). The long-range structure of 5 adopts a 3D open framework, as it includes the flexible glutarate linker, in which U 6 O 8 secondary building units assemble as U 6 O 38 superclusters. These clusters are interlinked by the glutarate spacers resulting in a body centered cubic (bcu) topology.

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“…Both U-glutarate phases were isolated at a 1:2 M:L ratio; the resulting differences in nuclearity and chloride binding may point to the role that solution conditions play in directing speciation. Protonation of the glutarate (p K a1 = 4.34, p K a2 = 5.22) at a low pH is fairly common in solid-state U(VI) chemistry , and limits the number of coordinating carboxylate sites on the ligand, subsequently restricting the resulting dimensionality as well. It may be expected that an increase in the pH would not only deprotonate the ligand but also likely increase the propensity for hydrolysis and condensation reactions to occur.…”

Section: Resultsmentioning

confidence: 99%

Synthesis, Characterization, and Solid-State Structural Chemistry of Uranium(IV) Aliphatic Dicarboxylates

Murray

Wacker

Bertke

et al. 2021

Crystal Growth & Design

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Examinations of uranium(IV) complexation by aliphatic dicarboxylates, ranging from the three-carbon malonate to the six-carbon adipate, yielded six novel phases. Single crystals of the compounds were prepared through either evaporation or solvent layering, and the structures were determined via single-crystal X-ray diffraction. The compounds were further characterized via IR and Raman spectroscopies. For the phases synthesized via solvent layering, correlations between the solution- and solid-state speciation were probed using UV–visible absorption spectroscopy. In the presence of malonate (MA), [U(MA)2(H2O)3] n (U-1a) was isolated. As the crystals were not suitable for structure determination, reactions of MA with thorium were pursued. These efforts yielded polymorphs, Th-1a and Th-1b; in both An-1a (An = Th, U) and Th-1b, the An(IV) metal centers are bridged via the MA ligands into 2D sheets. Upon increasing the length of the aliphatic backbone, monodentate and bridging bidentate binding modes are observed. Two distinct ligand-bridged extended networks that vary in metal ion nuclearity were observed for succinate (SA): [UCl2(SA)(H2O)2] n (U-2) and [U6O4(OH)4(SA)4(H2O)10]·4Cl·mH2O (U-3). Whereas U-2 consists of mononuclear U(IV) atoms that are bridged through the organic carboxylate into a 3D network, U-3 is built from hexanuclear U(IV)-hydroxo-oxo clusters that are further bridged into a 3D network. From glutarate (GA) ligand systems, two phases were isolated including [UCl2(HGA)2(H2O)2] n (U-4) that consists of ligand-bridged one-dimensional chains and [U2Cl6(HGA)2(H2O)2] n (U-5), which is built from chloride-bridged {U2Cl2} dimers that are further linked via GA into two-dimensional sheets. Finally, in the presence of adipate (AA), [U6O4(OH)4(AA)4(H2O)8]·4Cl·7(H2O) (U-6) is observed; the structure consists of hexameric [U6O4(OH)4]12+ clusters that are propagated into one-dimensional chains via the AA and uranium-bound water molecules that directly link adjacent clusters. Taken together, this work provides a systematic examination of the influence of the identity of the dicarboxylate backbones on actinide structural chemistry and highlights the role that the organic ligand plays in stabilizing unique tetravalent actinide structural units.

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Crystal structures of new uranyl glutarate coordination polymers (NH4)2[(UO2)2(glt)3]·nH2O (n= 3 or 6) and R[UO2(glt)(Hglt)]·H2O (R = Na, K, Rb or Cs)

Cited by 10 publications

References 49 publications

Structure-Directing Effects of Counterions in Uranyl Ion Complexes with Long-Chain Aliphatic α,ω-Dicarboxylates: 1D to Polycatenated 3D Species

Structure-Directing Effects of Counterions in Uranyl Ion Complexes with Long-Chain Aliphatic α,ω-Dicarboxylates: 1D to Polycatenated 3D Species

Network Dimensionality of Selected Uranyl(VI) Coordination Polymers and Octopus-like Uranium(IV) Clusters

Synthesis, Characterization, and Solid-State Structural Chemistry of Uranium(IV) Aliphatic Dicarboxylates

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