Structural properties of the chelating agent 2,6-bis(1-(3-hydroxypropyl)-1,2,3-triazol-4-yl)pyridine: a combined XRD and DFT structural study

Dugoni, Greta Colombo; Baggioli, Alberto; Famulari, Antonino; Sacchetti, Alessandro; Martí‐Rujas, Javier; Mariani, Mario; Macerata, Elena; Mossini, Eros

doi:10.1039/d0ra04142d

Cited by 2 publications

(2 citation statements)

References 55 publications

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“…16 The remarkable discrimination can originate from multiple effects, including supramolecular recognition from microscopic to macroscopic scales and the kinetic control at the interface. 16,53 Theoretical calculations confirmed that the extraction efficiency and selectivity are significantly affected by the capacity of EBBs solved in the IL phase assembling to [EBB] n clusters. 16 Herein, we believe that the idea of oxidation state control can further enhance the selectivity of the MSSA extraction method in the redox reactions involved in the MSSA process.…”

Section: +mentioning

confidence: 90%

Spontaneous Multi-scale Supramolecular Assembly Driven by Noncovalent Interactions Coupled with the Continuous Marangoni Effect

Shi,

Shen

2024

Langmuir

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Reported herein is the multi-scale supramolecular assembly (MSSA) process along with redox reactions driven by supramolecular interactions coupled with the spontaneous Marangoni effect in ionic liquid (IL)-based extraction systems. The black powder, the single sphere with a black exterior, and the single colorless sphere were formed step by step at the interface when an aqueous solution of KMnO 4 was mixed with the IL phase 1-(2-hydroxyethyl)-3-methylimidazolium bis(trifluoromethylsulfonyl) imide (C 2 OHmimNTf 2 ) bearing octyl(phenyl)-N,Ndiisobutylcarbamoylmethylphosphine oxide (CMPO). The mechanism of the whole process was studied systematically. The phenomena were related closely to the change in the valence state of Mn. The MnO 4 − ion could be reduced quickly to δ-MnO 2 and further to Mn 2+ slowly by the hydroxyl-functionalized IL C 2 OHmimNTf 2 . Based on Mn 2+ , Mn(CMPO) 3 2+ , elementary building blocks (EBBs), and [EBB] n clusters were generated step by step. The [EBB] n clusters with the large enough size that were transferred to the interface, together with the remaining δ-MnO 2 , assembled into the single sphere with a black exterior, driven by supramolecular interactions coupled with the spontaneous Marangoni effect. When the remaining δ-MnO 2 was used up, the mixed single sphere turned completely colorless. It was found that the reaction site of C 2 OHmim + with Mn(VII) and Mn(IV) was distributed mainly at the side chain with a hydroxyl group. The MSSA process presents unique spontaneous phase changes. This work paves the way for the practical application of the MSSA-based separation method developed recently. The process also provides a convenient way to observe in situ and characterize directly the continuous Marangoni effect.

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Section: +mentioning

confidence: 90%

Spontaneous Multi-scale Supramolecular Assembly Driven by Noncovalent Interactions Coupled with the Continuous Marangoni Effect

Shi,

Shen

2024

Langmuir

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“…These recent developments on the back-extraction An(III) applied with hydrophilic N-type donor ligands inspired us to elucidate the electronic structures, bonding nature, and complexing ability of Am(III)/Eu(III) complexes with these ligands. Nowadays, density functional theory (DFT) calculations as a powerful tool have been used to evaluate the solvent extraction of f-block metal ions. − There are several investigations on designing lipophilic ligands for the efficient separation of actinide ions. ,,− However, there is a lack of theoretical studies on the selective separation of An(III)/Ln(III) with hydrophilic ligands. In this work, based on the structures of the experimentally available L a and L c ligands , and theoretically designed 2,9-bis[(1-hydroylpropyl)-1 H -1,2,3-triazol-4-yl]-4,4-bipyridine ( L b , Scheme ), we explored the electronic structures of the three similar ligands with different bridging skeletons and examined their bonding nature and complexing ability with Am(III)/Eu(III) ions using scalar-relativistic DFT.…”

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confidence: 99%

Theoretical Insights into the Selective Separation of Am(III)/Eu(III) Using Hydrophilic Triazolyl-Based Ligands

Wang

et al. 2022

Inorg. Chem.

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Designing ligands with efficient actinide (An(III))/lanthanide (Ln(III)) separation performance is still one of the key issues for the disposal of accumulated radioactive waste and the recovery of minor actinides. Recently, the hydrophilic ligands as promising extractants in the innovative Selective ActiNide Extraction (i-SANEX) process show excellent selectivity for Am(III) over Eu(III), such as hydroxylated-based ligands. In this work, we investigated the selective back-extraction toward Am(III) over Eu(III) with three hydrophilic hydroxylated triazolyl-based ligands (the skeleton of pyridine L a , bipyridine L b , and phenanthroline L c ) using scalar-relativistic density functional theory. The properties of three hydrophilic hydroxylated ligands and the coordination structures, bonding nature, and thermodynamic properties of the Am(III) and Eu(III) complexes with three ligands have been evaluated using multiple theoretical methods. The results of molecular orbitals (MOs), quantum theory of atoms in molecules (QTAIMs), and natural bond orbital (NBO) reveal that Am–N bonds possess more covalent character compared to Eu–N bonds. The thermodynamic results indicate that the complexing ability of L b and L c with metal ions is almost the same, which is stronger than that of L a . However, L a has the best Am(III)/Eu(III) selectivity among three ligands, which is attributed to the largest difference in covalency between Am–Ntrzl and Eu–Ntrzl bonds in ML a (NO3)3. This work provides an in-depth understanding of the preferential selectivity of the hydrophilic hydroxylated ligands with An(III) over Ln(III) and also provides theoretical support for designing potential hydrophilic ligands with excellent separation performance of Am(III)/Eu(III).

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Structural properties of the chelating agent 2,6-bis(1-(3-hydroxypropyl)-1,2,3-triazol-4-yl)pyridine: a combined XRD and DFT structural study

Abstract: Dispersion corrected DFT analysis in combination with single crystal X-ray structural analysis provides insights into the ability of PTD to chelate metal ions of radiotoxic waste from nuclear fuel.

Cited by 2 publications

References 55 publications

Spontaneous Multi-scale Supramolecular Assembly Driven by Noncovalent Interactions Coupled with the Continuous Marangoni Effect

Spontaneous Multi-scale Supramolecular Assembly Driven by Noncovalent Interactions Coupled with the Continuous Marangoni Effect

Theoretical Insights into the Selective Separation of Am(III)/Eu(III) Using Hydrophilic Triazolyl-Based Ligands

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