Theoretical unraveling the complexation and separation of uranyl–ligand complexes towards chiral R/S‐profenofos

Liu, Linfeng; Lu, Yao; Liao, Lifu; Xiao, Xilin; Nie, Changming

doi:10.1002/aoc.6686

Cited by 7 publications

(7 citation statements)

References 89 publications

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“…Figure 5 shows the MOs diagrams 6,11,12 of the six complexes with significant U–X interactions and the contribution (%) of atoms (U, X) to their orbitals 68 . The two diagrams in Figure 5a,b are the MO diagrams of the primary coordination site O 5 of the guest and the receptor (orbital number 79), which has the largest coverage of the isosurfaces compared to the other four MO diagrams, and it is thus clear that the U and O 5 atoms contribute the most to this orbital.…”

Section: Resultsmentioning

confidence: 99%

“…In addition, the larger ΔE L-H of the molecule itself represents the more difficult it can be excited and the greater stability of the molecular T A B L E 4 Orbital energies of the receptor, guests, and six guest-receptor complexes at the B3LYP/def2-SVP/RECP level (unit: eV). Figure 5 shows the MOs diagrams 6,11,12 of the six complexes with significant U-X interactions and the contribution (%) of atoms (U, X) to their orbitals. 68 The two diagrams in Figure 5a,b are the MO diagrams of the primary coordination site O 5 of the guest and the receptor (orbital number 79), which has the largest coverage of the isosurfaces compared to the other four MO diagrams, and it is thus clear that the U and O 5 atoms contribute the most to this orbital.…”

Section: Mos and Ets-nocv Analysismentioning

confidence: 99%

“…16 Liu et al designed two receptors, Uranyl-TMMT and Uranyl-TMMO, to study the separation and coordination capacity for profenofos and presented good separation results. 11 Inspired by the TMMT/TMMO ligands and considering the non-polluting incineration of the ligand molecules containing only C, H, O, and N atoms, 34,35 we designed the 2-(9-[1H-pyrazole-1-carbonyl]-1,10-phenanthroline-2-yl)-1H-inden-1-one (HPIDO) ligand with o-phenanthroline as the basic skeleton and bound it to the uranyl ion to form a chiral-at-uranium complex of Uranyl-HPIDO receptor and further unraveled the binding and enantioseparation ability of Uranyl-HPIDO to R/S-MLXs. The chemical structures of the ligand (HPIDO), receptor (Uranyl-HPIDO), and chiral guests (R/S-MLXs) are shown in Figure 1.…”

Section: Introductionmentioning

confidence: 99%

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Unraveling complexation and enantioseparation of a new chiral‐at‐uranium complex to chiral pesticides R/S‐malaoxons

Guo,

Ouyang,

Wang

et al. 2024

Applied Organom Chemis

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Unraveling uranium complexes has become a popular study topic in recent years to address the problem of spent fuel treatment. An important and promising investigation is the enantiomer separation of chiral organophosphorus pesticides (OPs) via uranyl‐containing receptors. Among them, malaoxon (MLX), as a chiral OP with high toxicity and good selectivity, is controversial because of the different toxicity differences caused by the R and S configurations to target and non‐target organisms. Therefore, it is crucial to explore effective methods for separating its enantiomers. In this work, a novel 2‐(9‐[1H‐pyrazole‐1‐carbonyl]‐1,10‐phenanthrolin‐2‐yl)‐1H‐inden‐1‐one (HPIDO) ligand, which combines with uranyl to form the chiral‐at‐uranium complex (Uranyl‐HPIDO receptor), was designed for the enantioseparation of R/S‐malaoxons (R/S‐MLXs). Based on density functional theory (DFT), we explored the potential coordination modes between the Uranyl‐HPIDO receptor and R/S‐MLXs at various sites. The analyses of bonding properties, orbital interactions, and weak interactions of intramolecular groups of the complexes, along with the study of thermodynamic properties, revealed that the Uranyl‐HPIDO receptor preferred to bind to the phosphoryl oxygen (O5) of R/S‐MLXs to form stable complexes. Good enantioseparations of the two enantiomers were achieved in various solvents (water, n‐Butanol, n‐Octanol, dichloromethane, propanoic acid, toluene, and cyclohexane); the separation factors (SFR/S) ranged 21–853, and the enantioselectivity coefficients (ESCR/S) were more than 95%. The findings could theoretically offer useful information and guidance for the separation of R/S‐MLXs, in addition to providing fresh concepts for the creation of novel uranyl receptors.

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Section: Resultsmentioning

confidence: 99%

Section: Mos and Ets-nocv Analysismentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Unraveling complexation and enantioseparation of a new chiral‐at‐uranium complex to chiral pesticides R/S‐malaoxons

Guo,

Ouyang,

Wang

et al. 2024

Applied Organom Chemis

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“…This seems to imply that metal-ligand interactions are in the category of ionic bonds and so have negligible pre-relaxation effects. In this study, the Am-ligand, Cm-ligand and Eu-ligand bonds in the studied complexes also have low ρ(r c ) and small delocalization indexes δ (0.14-0.27 a.u., see Table 6) and small H(r c ) and are ionic interactions, similar to the above case of U-ligand bonds and transition metal-ligand bonds, so the prerelaxation effects should be negligible, thus the QTAIM metrics ρ(r c ), δ and H(r c ) may be used to evaluate the strength of the M-ligand bonds [48].…”

Section: Density-based Analyses On Bonding Naturementioning

confidence: 96%

Theoretical insight on Cm(III) and Eu(III) competing with Am(III) for binding to N‐donor extractants with different dentate numbers

Wu,

Zhang,

2023

Int J of Quantum Chemistry

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The separation of actinides (An) from lanthanides (Ln) is crucial for nuclear resource recovery and reducing long‐term radiotoxicity. While numerous N‐donor ligands have been examined for the extraction separation of An and Ln, few studies have investigated the effect of the number of ligand dentate on bonding and extraction separation. To address this issue, we designed six pyridine‐based ligands with different numbers of coordination dentate. We employed density functional methods to investigate their bonding properties with Am(III), Cm(III), and Eu(III), as well as the thermodynamic differences in extracting and separating these metal ions. The NBO and QTAIM analyses indicate that the metal–ligand bonds are predominantly ionic. However, the Am‐N bond exhibits higher covalency compared to the Cm‐N and Eu‐N bonds, and it is also stronger than the latter two. This difference in bonding can be attributed to the greater involvement of the 5f orbitals of Am in coordination with the ligands, in contrast to the involvement of the Cm 5f and Eu 4f orbitals. Thermodynamic analysis reveals that the coordination ability of the ligands with metals does increase with the number of coordination teeth. However, the extraction separation effect of the ligand for Am/Cm and Am/Eu does not show a strong correlation with the number of coordination dentate. We hope that this study can offer valuable theoretical support for the design of ligands aimed at the separation of actinide(III) and lanthanide(III) ions.

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“…[17] Because of the frequent occurrence of mixed chelation in biological fluids, mixed ligand complexes play a significant role in biological and catalytic chemistry. [18][19][20] Mixed ligand complexes synthesis and characterization are becoming more and more important. This inspires the creation of mixed ligand complexes with a range of characteristics.…”

Section: Introductionmentioning

confidence: 99%

New Benzimidazole‐Based Fe (III) and Cr (III) Complexes: Characterization, Bioactivity Screening, and Theoretical Implementations Using DFT and Molecular Docking Analysis

Elkanzi

Ali

Albqmi

et al. 2022

Applied Organom Chemis

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Two new Fe (III) and Cr (III) complexes had been synthesized and structurally characterized. The new complexes were based on 2‐methyl‐benzimidazole (MB) and salicylic acid (H2L). Elemental analyses, Fourier transform infrared spectroscopy, UV‐–Vis, mass spectra, conductivity, magnetic, and thermal measurements were used to formulate the compounds structures. The results revealed octahedral geometry for both of Fe (III) and Cr (III) complexes. Structure elucidation of these complexes was also supported by density functional theory (DFT) along with optimized geometrical parameters. Natural bond orbital analysis and molecular electrostatic potential were also investigated. Electronic absorption spectra were theoretically performed using the time‐dependent TD‐DFT/B3LYP in gas phase and acetonitrtile as a solvent. Furthermore, the bio‐mimicking activity as antimicrobial and anti‐inflammatory activity of the understudy compounds was in vitro screened. The results showed that the Fe (III) and Cr (III) complexes exhibited higher pathogenic action than the free ligands. Molecular docking investigation against 3T88 (E. Coli) and 5IKT (Cyclooxygenase‐2) was carried out to provide deep insights into their role in inhibiting the growth of pathogenic microbes.

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Theoretical unraveling the complexation and separation of uranyl–ligand complexes towards chiral R/S‐profenofos

Cited by 7 publications

References 89 publications

Unraveling complexation and enantioseparation of a new chiral‐at‐uranium complex to chiral pesticides R/S‐malaoxons

Unraveling complexation and enantioseparation of a new chiral‐at‐uranium complex to chiral pesticides R/S‐malaoxons

Theoretical insight on Cm(III) and Eu(III) competing with Am(III) for binding to N‐donor extractants with different dentate numbers

New Benzimidazole‐Based Fe (III) and Cr (III) Complexes: Characterization, Bioactivity Screening, and Theoretical Implementations Using DFT and Molecular Docking Analysis

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