A Uranyl Metal Organic Framework Arising from the Coordination of a Partially Hydrolyzed Tetrauranyl Node with the Tautomerically Diverse 1,4-(Diamidoximyl)benzene Ligand

Mishra, Manish Kumar; Patil, Yogesh P.; Kelley, Steven P.; Rogers, Robin D.

doi:10.1021/acs.cgd.9b00544

Cited by 9 publications

(6 citation statements)

References 27 publications

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“…The group led by Rogers [83] investigated the reactions of the uranyl cation and 1,4-(diamidoximyl)benzene (H 4 L2 in Figure 7) in order to understand electronic and cooperativity effects on the coordination chemistry of the amidoxime group. There are two amidoxime groups in the molecule separated by an aromatic spacer, which would be tautomerized to their zwitterionic forms.…”

Section: An Uranyl Mof Containing a Partially Hydrolyzed Tetranuclear...mentioning

confidence: 99%

Synthetic and Structural Chemistry of Uranyl-Amidoxime Complexes: Technological Implications

et al. 2023

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Resource shortage is a major problem in our world. Nuclear energy is a green energy and because of this and its high energy density, it has been attracting more and more attention during the last few decades. Uranium is a valuable nuclear fuel used in the majority of nuclear power plants. More than one thousand times more uranium exists in the oceans, at very low concentrations, than is present in terrestrial ores. As the demand for nuclear power generation increases year-on-year, access to this reserve is of paramount importance for energy security. Water-insoluble polymeric materials functionalized with the amidoxime group are a technically feasible platform for extracting uranium, in the form of {UO2}2+, from seawater, which also contains various concentrations of other competing metal ions, including vanadium (V). An in-depth understanding of the coordination modes and binding strength of the amidoxime group with uranyl and other competing ions is a key parameter for improving extraction efficiency and selectivity. Very limited information on the complexation of {UO2}2+ with amidoximes was available before 2012. However, significant advances have been made during the last decade. This report reviews the solid-state coordination chemistry of the amidoxime group (alone or within ligands with other potential donor sites) with the uranyl ion, while sporadic attention on solution and theoretical studies is also given. Comparative studies with vanadium complexation are also briefly described. Eight different coordination modes of the neutral and singly deprotonated amidoxime groups have been identified in the structures of the uranyl complexes. Particular emphasis is given to describing the reactivity of the open-chain glutardiamidoxime, closed-ring glutarimidedioxime and closed-ring glutarimidoxioxime moieties, which are present as side chains on the sorbents, towards the uranyl moiety. The technological implications of some of the observed coordination modes are outlined. It is believed that X-ray crystallography of small uranyl-amidoxime molecules may help to build an understanding of the interactions of seawater uranyl with amidoxime-functionalized polymers and improve their recovery capacity and selectivity, leading to more efficient extractants. The challenges for scientists working on the structural elucidation of uranyl coordination complexes are also outlined. The review contains six sections and 95 references.

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Section: An Uranyl Mof Containing a Partially Hydrolyzed Tetranuclear...mentioning

confidence: 99%

Synthetic and Structural Chemistry of Uranyl-Amidoxime Complexes: Technological Implications

et al. 2023

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“…The realization of this strategy requires, among others, molecular inorganic chemistry (coordination chemistry) approaches. Thus, few uranyl complexes with amidoxime-based ligands have been isolated and structurally characterized [13,[16][17][18][19][20][21][22][23][24][25][26][27].…”

Section: Introductionmentioning

confidence: 99%

Understanding the Selective Extraction of the Uranyl Ion from Seawater with Amidoxime-Functionalized Materials: Uranyl Complexes of Pyrimidine-2-amidoxime

Tsantis,

Lada,

Skiadas

et al. 2024

Inorganics

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The study of small synthetic models for the highly selective removal of uranyl ions from seawater with amidoxime-containing materials is a valuable means to enhance their recovery capacity, leading to better extractants. An important issue in such efforts is to design bifunctional ligands and study their reactions with trans-{UO2}2+ in order to model the reactivity of polymeric sorbents possessing both amidoximate and another adjacent donor site on the side chains of the polymers. In this work, we present our results concerning the reactions of uranyl and pyrimidine-2-amidoxime, a ligand possessing two pyridyl nitrogens near the amidoxime group. The 1:2:2 {UO2}2+/pmadH2/external base (NaOMe, Et3N) reaction system in MeOH/MeCN provided access to complex [UO2(pmadH)2(MeOH)2] (1) in moderate yields. The structure of the complex was determined by single-crystal X-ray crystallography. The UVI atom is in a distorted hexagonal bipyramidal environment, with the two oxo groups occupying the trans positions, as expected. The equatorial plane consists of two terminal MeOH molecules at opposite positions and two N,O pairs of two deprotonated η2 oximate groups from two 1.11000 (Harris notation) pmadH− ligands; the two pyridyl nitrogen atoms and the –NH2 group remain uncoordinated. One pyridyl nitrogen of each ligand is the acceptor of one strong intramolecular H bond, with the donor being the coordinated MeOH oxygen atom. Non-classical Caromatic-H⋯X (X=O, N) intermolecular H bonds and π–π stacking interactions stabilize the crystal structure. The complex was characterized by IR and Raman spectroscopies, and the data were interpreted in terms of the known structure of 1. The solid-state structure of the complex is not retained in DMSO, as proven via 1H NMR and UV/Vis spectroscopic techniques as well as molar conductivity data, with the complex releasing neutral pmadH2 molecules. The to-date known coordination chemistry of pmadH2 is critically discussed. An attempt is also made to discuss the technological implications of this work.

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“…Thuery et al studied tubular uranyl phenyldiacetate, used separable and reversible ligands to obtain chiral uranyl ion coordination frames [10]. Mishra et al investigated the preparation of uranyl metal organic skeletons based on 1,4‐(diaminooximino)benzene [11]. Zhao et al synthesized a three‐dimensional porous uranyl phosphonate MOF by a hydrothermal method for uranyl spill prevention and recovery [12].…”

Section: Introductionmentioning

confidence: 99%

Probing into complexation and separation of chiral‐at‐uranium complex to chiral sulphur enantiomers R/S‐ethiproles

Xiao

et al. 2023

Applied Organom Chemis

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Chiral pesticides R/S-ethiproles(R/S-EPLs) have different biotoxicity. Due to the difficulty in the separation of chiral sulphur enantiomers, it is of great significance to study the selective recognition and separation of chiral sulphur enantiomers R/S-ethiproles. Based on DFT method, we theoretically designed a novel asymmetrical ligand of 4-amino-6-(9-[5-hydroxy-1H-indol-6-yl]-4,7-dimethoxy-1,10-phenanthrolin-2-yl)-1H-indol-5-ol (AHPIL). Then we further constructed the chiral-at-uranium complex, namely, Uranyl-AHPIL, to recognize and separate the enantiomers R/S-EPLs. Various analyses, including electrostatic potential (ESP), molecular geometric structures, Mayer bond order (MBO), electron density difference diagram (EDDM), independent gradient model based on Hirschfield partition (IGMH), quantum theory of atoms in molecules (QTAIM), molecular orbitals, the extended transition state-natural orbitals for chemical valence (ETS-NOCV), hard-soft acid-base (HSAB), relaxed force constants (RFCs) and binding free energy, furthermore unravelled the selective complexation and chiral separation ability of Uranyl-AHPIL receptor to R/S-EPLs guests. The results all indicated that the novel ligand could coordinate with uranyl to form a stable chiral-at-uranium complex, which more inclined selectively to bind with R/S-EPLs through thiyl oxygen O 22 , and its complexation ability to S-EPL was much greater than to R-EPL. In solvents water, acetone, dichloromethane, benzene, cyclohexane and in gas phase, the separation factors of Uranyl-AHPIL towards R/S-EPL were in range of 189-633, and the enantioselectivity coefficients were all above 99%. These results provide a theoretical guidance for the complexation and separation of chiral pesticides and at the same time offer a new reference for the design of actinide complexes.

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A Uranyl Metal Organic Framework Arising from the Coordination of a Partially Hydrolyzed Tetrauranyl Node with the Tautomerically Diverse 1,4-(Diamidoximyl)benzene Ligand

Cited by 9 publications

References 27 publications

Synthetic and Structural Chemistry of Uranyl-Amidoxime Complexes: Technological Implications

Synthetic and Structural Chemistry of Uranyl-Amidoxime Complexes: Technological Implications

Understanding the Selective Extraction of the Uranyl Ion from Seawater with Amidoxime-Functionalized Materials: Uranyl Complexes of Pyrimidine-2-amidoxime

Probing into complexation and separation of chiral‐at‐uranium complex to chiral sulphur enantiomers R/S‐ethiproles

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