4f/5d Hybridization Induced Single-Electron Delocalization in an Azide-Bridged Dicerium Complex.

Dilanthanide complexes with one-electron delocalization are important targets for understanding the specific 4f/5d-bonding feature in lanthanide chemistry. Here, we report an isolable azide-bridged dicerium complex 3 [{(TrapenTMS)Ce}2(µ-N3)]• [Trapen = tris (2-aminobenzyl)amine; TMS = SiMe3], which is synthesized by the reaction of tripodal ligand-supported (TrapenTMS)CeIVCl complex 2 with NaN3. The structure and bonding nature of 3 are fully characterized by X-ray crystal diffraction analysis, electron paramagnetic resonance (EPR), magnetic measurement, cyclic voltammetry, X-ray absorption spectroscopy, and quantum-theoretical studies. Complex 3 presents a trans-bent central Ce-N3-Ce unit with a single electron of two mixed-valent Ce atoms. The unique low-temperature (2 K) anisotropic EPR signals [g = 1.135, 2.003, and 3.034] of 3 indicate that its spin density is distributed on the central Ce-N3-Ce unit with marked electron delocalization. Quantum chemical analyses show strong 4f/5d orbital mixing in the singly occupied molecular orbital of 3, which allows for the unpaired electron to extend throughout the cerium-azide-cerium unit via a multicentered one-electron (Ce-N3-Ce) interaction. This work extends the family of mixed-valent dilanthanide complexes and provides a paradigm for understanding the bonding motif of ligand-bridged dilanthanide complexes.

Thermally Induced Orderly Alignment of Porphyrin Photoactive Motifs in Metal-Organic Frameworks for Boosting Photocatalytic CO2 Reduction.

Efficient transfer of charge carriers through a fast transport pathway is crucial to excellent photocatalytic reduction performance in solar-driven CO2 reduction, but it is still challenging to effectively modulate the electronic transport pathway between photoactive motifs by feasible chemical means. In this work, we propose a thermally induced strategy to precisely modulate the fast electron transport pathway formed between the photoactive motifs of a porphyrin metal-organic framework using thorium ion with large ionic radius and high coordination number as the coordination-labile metal node. As a result, the stacking pattern of porphyrin molecules in the framework before and after the crystal transformations has changed dramatically, which leads to significant differences in the separation efficiency of photogenerated carriers in MOFs. The rate of photocatalytic reduction of CO2 to CO by IHEP-22(Co) reaches 350.9 µmol·h-1·g-1, which is 3.60 times that of IHEP-21(Co) and 1.46 times that of IHEP-23(Co). Photoelectrochemical characterizations and theoretical calculations suggest that the electron transport channels formed between porphyrin molecules inhibit the recombination of photogenerated carriers, resulting in high performance for photocatalytic CO2 reduction. The interaction mechanism of CO2 with IHEP-22(Co) was clarified by using in-situ electron paramagnetic resonance, in-situ diffuse reflectance infrared Fourier transform spectroscopy, in-situ extended X-ray absorption fine structure spectroscopy, and theoretical calculations. These results provide a new method to regulate the efficient separation and migration of charge carriers in CO2 reduction photocatalysts and will be helpful to guide the design and synthesis of photocatalysts with superior performance for the production of solar fuels.

Sequential Water Sorption/Desorption of a Nonporous Adaptive Organic Ligand Bridged Coordination Polymer for Atmospheric Moisture Harvesting.

Moisture harvesters with favourable attributes such as easy synthetic availability and good processability as alternatives for atmospheric moisture harvesting (AWH) are desirable. This study reports a novel nonporous anionic coordination polymer (CP) of uranyl squarate with methyl viologen (MV2+ ) as charge balancing ions (named U-Squ-CP) which displays intriguing sequential water sorption/desorption behavior as the relative humidity (RH) changes gradually. The evaluation of AWH performance of U-Squ-CP shows that it can absorb water vapor under air atmosphere at a low RH of 20 % typical of the levels found in most dry regions of the world, and have good cycling durability, thus demonstrating the capability as a potential moisture harvester for AWH. To the authors' knowledge, this is the first report on non-porous organic ligand bridged CP materials for AWH. Moreover, a stepwise water-filling mechanism for the water sorption/desorption process is deciphered by comprehensive characterizations combining single-crystal diffraction, which provides a reasonable explanation for the special moisture harvesting behaviour of this non-porous crystalline material.

Theoretical Insights into the Substitution Effect of Phenanthroline Derivatives on Am(III)/Eu(III) Separation.

Separation of trivalent actinides (An(III)) and lanthanides (Ln(III)) poses a huge challenge in the reprocessing of spent nuclear fuel due to their similar chemical properties. N,N'-Diethyl-N,N'-ditolyl-2,9-diamide-1,10-phenanthroline (Et-Tol-DAPhen) is a potential ligand for the extraction of An(III) from Ln(III), while there are still few reports on the effect of its substituent including electron-withdrawing and electron-donating groups on An(III)/Ln(III) separation. Herein, the interaction of Et-Tol-DAPhen ligands modified by the electron-withdrawing groups (CF3, Br) and electron-donating groups (OH) with Am(III)/Eu(III) ions was investigated using scalar relativistic density functional theory (DFT). The analyses of bond order, quantum theory of atoms in molecules (QTAIM), and molecular orbital (MO) indicate that the substitution groups have a slight effect on the electronic structures of the [M(L-X)(NO3)3] (X = CF3, Br, OH) complexes. However, the thermodynamic results suggest that a ligand with the electron-donating group (L-OH) improves the extraction ability of metal ions, and the ligand modified by the electron-withdrawing group (L-Br) has the best Am(III)/Eu(III) selectivity. This work could render new insights into understanding the effect of electron-withdrawing and electron-donating groups in tuning the selectivity of Et-Tol-DAPhen derivatives and pave the way for designing new ligands modified by substituted groups with better extraction ability and An(III)/Ln(III) selectivity.

Theoretical Insights into the Selectivity of Hydrophilic Sulfonated and Phosphorylated Ligands to Am(III) and Eu(III) Ions.

The separation of lanthanides and actinides has attracted great attention in spent nuclear fuel reprocessing up to date. In addition, liquid-liquid extraction is a feasible and useful way to separate An(III) from Ln(III) based on their relative solubilities in two different immiscible liquids. The hydrophilic bipyridine- and phenanthroline-based nitrogen-chelating ligands show excellent performance in separation of Am(III) and Eu(III) as reported previously. To profoundly explore the separation mechanism, herein, we first of all designed four hydrophilic sulfonated and phosphorylated ligands L1, L2, L3, and L4 based on the bipyridine and phenanthroline backbones. In addition, we studied the structures of these ligands and their neutral complexes [ML(NO3)3] (M = Am, Eu) as well as the thermodynamic properties of complexing reactions through the scalar relativistic density functional theory. According to the changes of the Gibbs free energy for the back-extraction reactions, the phenanthroline-based ligands L2 and L4 have stronger complexing capacity for both Am(III) and Eu(III) ions while the phosphorylated ligand L3 with the bipyridine framework has the highest Am(III)/Eu(III) selectivity. In addition, the charge decomposition analysis revealed a higher degree of charge transfer from the ligand to Am(III), suggesting stronger donor-acceptor interactions in the Am(III) complexes. This study can provide theoretical insights into the separation of actinide(III)/lanthanide(III) using hydrophilic sulfonated and phosphorylated N-donor ligands.

Theoretical Insights on the Complexation of Americium(III) and Europium(III) with Diglycolamide- and Dimethylacetamide-Functionalized Calix[4]arenes.

Separation of minor actinides from lanthanides is one of the biggest challenges in spent fuel reprocessing due to the similar physicochemical properties of trivalent lanthanides (Ln(III)) and actinides (An(III)). Therefore, developing ligands with excellent extraction and separation performance is essential at present. As an excellent pre-organization platform, calixarene has received more attention on Ln(III)/An(III) separation. In this work, we systematically explored the complexation behaviors of the diglycolamide (DGA)/dimethylacetamide (DMA)-functionalized calix[4]arene extractants for Eu(III) and Am(III) using relativistic density functional theory (DFT). These calix[4]arene-derived ligands were obtained by functionalization with two or four binding units at the narrow edge of the calix[4]arene platform. All bonding nature analyses suggested that the Eu-L complexes possess stronger interaction compared to Am-L analogues, resulting in the higher extraction capacity of the these calix[4]arene ligands toward Eu(III). Thermodynamic analysis demonstrates that these pre-organized ligands on the calix[4]arene platform with four binding units yield better extraction abilities than the single ligands. Although DMA-functionalized ligands show stronger complexation stability for metal ions, in acidic solutions, the calix[4]arene ligands with DGA binding units have better extraction performance for Eu(III) and Am(III) due to the basicity of the DMA ligand. This work enabled us to gain a deeper understanding of the bonding properties between supramolecular ligands and lanthanides/actinides and afford useful insights into designing efficient supramolecular ligands for separating Ln(III)/An(III).

Th6-Based Multicomponent Heterometallic Metal-Organic Frameworks Featuring 6,12-Connected Topology for Iodine Adsorption.

Its high coordination number and tendency to cluster make Th4+ suitable for constructing metal-organic frameworks (MOFs) with novel topologies. In this work, two novel thorium-based heterometallic MOF isomers (IHEP-17 and IHEP-18) were assembled from a Th6 cluster, a multifunctional organic ligand [4-(1H-pyrazol-4-yl)benzoic acid (HPyba)], and Cu2+/Ni2+ cations via the one-pot solvothermal synthesis strategy. The framework features a 6,12-connected new topology net and contains two kinds of supramolecular cage structures, Th36M4 and Th24M2, suitable for guest exchange. Both MOF materials can efficiently adsorb I2. X-ray photoelectron spectroscopy, Raman spectroscopy, and single-crystal X-ray diffraction indicate that the adsorbed iodine is uniformly distributed within the Th36M4 cage but not the Th24M2 cage in the form of I3-.

Unveiling the Reduction Mechanism of Pu(IV) by Acetaldoxime.

The separation of plutonium (Pu) from spent nuclear fuel was achieved by effectively adjusting the oxidation state of Pu from +IV to +III in the plutonium uranium reduction extraction (PUREX) process. Acetaldoxime (CH3CHNOH) as a free salt reductant can rapidly reduce Pu(IV), but the reduction mechanism remains indistinct. Herein, we explore the reduction mechanism of two Pu(IV) ions by one CH3CHNOH molecule, where the second Pu(IV) reduction is the rate-determining step with the energy barrier of 19.24 kcal mol-1, which is in line with the experimental activation energy (20.95 ± 2.34 kcal mol-1). Additionally, the results of structure and spin density analyses demonstrate that the first and second Pu(IV) reduction is attributed to hydrogen atom transfer and hydroxyl ligand transfer, respectively. Analysis of localized molecular orbitals unveils that the reduction process is accompanied by the breaking of the Pu-OOH bond and the formation of the OOH-H and C-OOH bonds. The reaction energies confirm that the reduction of Pu(IV) by acetaldoxime is both thermodynamically and kinetically accessible. In this work, we elucidate the reduction mechanism of Pu(IV) with CH3CHNOH, which provides a theoretical understanding of the rapid reduction of Pu(IV).

Insights into the Reduction Mechanisms of Np(VI) to Np(V) by Carbohydrazide.

An efficient approach to Np separation in the Plutonium Uranium Reduction EXtraction (PUREX) process is to adjust Np(VI) to Np(V) by free-salt reductants, such as hydrazine and its derivatives. Recently, carbohydrazide (CO(N2H3)2), a derivative of hydrazine and urea, has received much attention, which can reduce Np(VI) to Np(V) in the extraction reprocessing of spent nuclear fuel. Herein, according to the experimental observations, we examine the reduction mechanism of four Np(VI) by one carbohydrazide molecule using multiple theoretical calculations. The fourth Np(VI) reduction with a 22.26 kcal mol-1 energy barrier is the rate-determining step, which is in accordance with the experimental observations (20.54 ± 1.20 kcal mol-1). The results of spin density reflect that the reduction of the first and third Np(VI) ion is an outer-sphere electron transfer, while that of the second and fourth Np(VI) ion is the hydrogen transfer. Localized molecular orbitals (LMOs) uncover that the breaking of the N-H bond and formation of the Oyl-H bond are accompanied by the reaction from initial complexes (ICs) to intermediates (INTs). This work offers basic perspectives for the reduction mechanism of Np(VI) to Np(V) by CO(N2H3)2, which is also expected to design excellent free-salt Np(VI) reductants for the separation of Np in the advanced PUREX process.

Theoretical Probing of Size-Selective Crown Ether Macrocycle Ligands for Transplutonium Element Separation.

Effective separation and recovery of chemically similar transplutonium elements from adjacent actinides is extremely challenging in spent fuel reprocessing. Deep comprehension of the complexation of transplutonium elements and ligands is significant for the design and development of ligands for the in-group separation of transplutonium elements. Because of experimental difficulties of transplutonium elements, theoretical calculation has become an effective means of exploring transplutonium complexes. In this work, we systematically investigated the coordination mechanism between transplutonium elements (An = Am, Cm, Bk, Cf) and two crown ether macrocyclic ligands [N,N'- bis[(6-carboxy-2-pyridyl)methyl]-1,10-diaza-18-crown-6 (H2bp18c6) and N,N'-bis[(6-methylphosphinic-2-pyridyl)methyl]-1,10-diaza-18-crown-6 (H2bpp18c6)] through quasi-relativistic density functional theory. The extraction complexes of [Anbp18c6]+ and [Anbpp18c6]+ possess similar geometrical structures with actinide atoms located in the cavity of the ligands. Bonding nature analysis indicates that the coordination ability of the coordinating atoms in pendent arms is stronger than that in the crown ether macrocycle because of the limitation of the macrocycle. Most of the coordination atoms of the H2bp18c6 ligand have a stronger ability to coordinate with metal ions than those of the H2bpp18c6 ligand. In addition, the bonding strength between the metal ions and ligands gradually weakens from Am to Cf, which is mainly attributed to the size selectivity of the ligands. Thermodynamic analysis shows that the H2bp18c6 ligand has a stronger extraction capacity than the H2bpp18c6 ligand, while the H2bpp18c6 ligand is superior in terms of the in-group separation ability. The extraction capacity of the two ligands for metal ions gradually decreases across the actinide series, indicating that these crown ether macrocycle ligands have size selectivity for these actinide cations as a result of steric constraint of the crown ether ring. We hope that these results offer theoretical clues for the development of macrocycle ligands for in-group transplutonium separation.

Theoretical Insights into Phenanthroline-Based Ligands toward the Separation of Am(III)/Eu(III).

The bistriazinyl-phenanthroline representative ligand, BTPhen, shows excellent extraction and separation ability for trivalent actinides and lanthanides. Herein, we first designed three phenanthroline-based nitrogen-donor ligands (L1, L2, and L3), and then studied the structural and bonding properties as well as thermodynamic properties of the probable complexes, ML(NO3)3 (M = Am or Eu and L = L1, L2, or L3), using scalar relativistic density functional theory. Our charge decomposition analysis revealed an obviously higher charge transfer from the ligand to Am(III) compared with the Eu(III) case for the studied complexes. Spin density analysis further showed a more significant degree of Am-to-ligand spin delocalization and the corresponding spin polarization on the ligands. According to the thermodynamic analysis, ligand L3 has the strongest complexation capacity for both Am(III) and Eu(III) ions, while ligand L1 has the highest Am(III)/Eu(III) selectivity in binary octanol/water solutions. We expected that this work can provide valuable theoretical support for the design of effective ligands for actinide(III)/lanthanide(III) separation in high level liquid waste.

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

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 La, bipyridine Lb, and phenanthroline Lc) 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 Lb and Lc with metal ions is almost the same, which is stronger than that of La. However, La 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 MLa(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).

Encapsulation of Polymetallic Oxygen Clusters in a Mesoporous/Microporous Thorium-Based Porphyrin Metal-Organic Framework for Enhanced Photocatalytic CO2 Reduction.

Solar-initiated CO2 reduction is significant for green energy development. Herein, we have prepared a new mesoporous/microporous porphyrin metal-organic framework (MOF), IHEP-20, loaded with polymetallic oxygen clusters (POMs) to form a composite material POMs@IHEP-20 for visible-light-driven photocatalytic CO2 reduction. The as-made composite material exhibits good stability in water from pH 0 to 11. After POMs were introduced to IHEP-20, they showed superior activity toward photocatalytic CO2 reduction with a CO production rate of 970 µmol·g-1·h-1, which is 3.27 times higher than that of pristine IHEP-20. This study opens a new door for the design and synthesis of high-performance catalysts for the photocatalytic reduction of CO2.

Coordination-Adaptive Polydentate Pseudorotaxane Ligand for Capturing Multiple Uranyl Species.

The propensity of uranyl for hydrolysis in aqueous environments prevents precise control of uranyl species in the scenarios of on-demand separation and tailored synthesis. Herein, using cucurbit[7]uril (CB[7]) as the macrocyclic molecule and 4,4'-bipyridine-N,N'-dioxide (DPO) as the string molecule, we propose a new kind of multidentate pseudorotaxane ligand, DPO@CB[7] for capturing uranyl species at different pH's. With the aprotic nature of DPO for metal coordination, the coordination ability of the DPO@CB[7] ligand is less affected by pH and can work in a wide range of pH's. Furthermore, by adaptive uranyl coordination, this aprotic pseudorotaxane ligand achieves effective recognition for different uranyl species ranging from monomeric to tetrameric originating from hydrolysis at varying pH's, and four novel uranyl-rotaxane compounds (URC1-4) are successfully obtained. Single-crystal X-ray diffraction analysis reveals that the DPO@CB[7] ligand coordinates with uranyl centers from monomeric to tetrameric in four different modes, as a result of structural flexibility of the DPO@CB[7] pseudorotaxane ligand. A detailed discussion for conformation flexibility of the DPO@CB[7] ligand has been conducted on the position changes of the DPO ligand trapped in the CB[7], which thus reveals good adaptivity of DPO@CB[7] that is noncovalently bonded as a supramolecular motif. In addition, characterization of the physicochemical properties of URC1 and URC2 with high phase purity, including powder X-ray diffraction (PXRD), infrared spectroscopy (IR), thermogravimetric analysis (TGA), and luminescence properties, are also provided. This work provides a good case of an adaptive pseudorotaxane ligand for the recognition and capture of different uranyl species and will bring valuable hints to the design of multifunctional supramolecular ligands for actinide separation in the future.

Mixed-Ligand Uranyl Squarate Coordination Polymers: Structure Regulation and Redox Activity.

The electron-rich squarate ion (C4O42-, SA2-) possesses electronic delocalization over the entire molecule and good redox activity, and the functionalization of metal-organic complexes with the SA2- group is desirable. In this work, a mixed-ligand method is used to construct novel uranyl squarate coordination polymers utilizing 4,4'-bipyridine (bpy), 4,4'-bipyridine-N,N'-dioxide (bpydo), 1,10-phenanthroline (phen), 4,4'-vinylenedipyridine (vidpy), and in situ formed oxalate (OA2-) as ancillary ligands. Seven mixed-ligand uranyl compounds, [(UO2)(OH)(SA)](Hbpy) (1), [(UO2)(H2O)(SA)2](H2bpy) (2), (UO2)(H2O)(SA)(bpydo)·2H2O (3), (UO2)(H2O)(SA)(phen)·H2O (4), (UO2)(OH)(SA)0.5(phen)·H2O (5), [(UO2)(SA)(OA)0.5](Hphen) (6), and [(UO2)(SA)(OA)0.5](Hvidpy) (7), with varying crystal structures were synthesized under hydrothermal conditions. Compound 1, together with bpy molecules filling in the interlayer space as template agents, has a two-dimensional (2D) network structure, while 2 gives a one-dimensional (1D) chain based on mononuclear uranium units. Compound 3 shows a neutral 2D network through the combined linkage of SA2- and bpydo. Both 4 and 5 have a similar chain-like structure due to the capping effect of phen motifs, while phen molecules in 6 act as templating agents after protonation. Similar to 6, compound 7 has a "sandwich-like" structure in which the Hvidpy motifs locate in the voids of layers of 2D uranyl-squarate networks. The redox properties of typical mixed-ligand uranyl-squarate compounds, 1, 4, and 5 with high phase purity, are characterized using cyclic voltammetry. All three of these uranyl coordination compounds show anode peaks (Ea) at 0.777, 0.804, and 0.760 V, respectively, which correspond to the oxidation process of SA2- → SA. Meanwhile, cathodic peaks (Ec) at -0.328, -0.315, and -0.323 V corresponding to the reduction process of U(VI) → U(V) are also observed. The results reveal that all three of these uranyl coordination compounds show good redox activity and, most importantly, the interplay between two different redox-active motifs of SA2- organic linker and uranyl node. This work enriches the library of redox-active uranyl compounds and provides a feasible mixed-ligand method for regulating the synthesis of functional actinide compounds.

Synthesis of Trapen Ligand-Based U(IV) and Th(IV) 2-Phosphaethynolate Complexes and Comparison of Covalency with Corresponding Ti(IV) Analogues.

The involvement of the 2-phosphaethynolate anion species with ambident nucleophilic properties serves as an essential protocol for synthesizing oxygen-bound or phosphorus-bound complexes. This work mainly describes the synthesis and characterization of U, Th, and Ti phosphaethynolate complexes featuring a preferential O-coordination fashion. Among these complexes, the first examples of a Ti(IV)-OCP complex 3A, Th(IV)-OCP complex 3B, and U(IV)-OCP complex 3C were assembled by a salt metathesis reaction between M(TrapenTMS)(Cl) (M = Ti, Th, U) and NaOCP(dioxane)2.5 and were all crystallographically characterized. The structural similarity of this series of phosphaethynolate complexes allows us to compare the bonding properties of d- and f-block elements in the corresponding compounds. The well-established density functional theory (DFT) computational method was employed to explore the electronic structures and covalency in M-O bonding, and the results showed a consistent pattern. The calculation result showed that 2-phosphaethynolate complexes exhibited the covalency trend of U-O > Th-O > Ti-O due to the involvement of 5f orbitals.

Actinide-doped boron clusters: from borophenes to borospherenes.

Similar to graphene and fullerene, metal-doping has been considered to be an effective approach to the construction of highly stable boron clusters. In this work, a series of actinide metal-doped boron clusters AnB36 (An = Pa, Np, Pu, Am, Cm, Bk, and Cf) have been explored using extensive first-principles calculations. We found that the quasi-planar structure of B36 transforms to an endohedral borospherene An@B36 after actinide metal doping. Actinoborospherenes exhibit C2h symmetry with Pa, Np, and Pu dopants and for Am, Cm, Bk and Cf dopants with larger atomic radii, the symmetry of An@B36 is reduced to Ci. Bonding property analyses such as bond order, molecular orbital (MO) and quantum theory of atoms in molecules (QTAIM) analysis show that the covalency of the An-B bonds in C2h An@B36 (An = Pa, Np, and Pu) is higher than that in Ci An@B36 (An = Am, Cm, Bk, and Cf). These endohedral borospherenes are robust according to thermodynamic and dynamic analyses. As expected, the Ci An@B36 clusters are less stable compared to C2h An@B36, which is consistent with the stronger covalent bonds of the latter. These results indicate that the existence of the actinide-boron bonding is essential for the high stability of the An@B36 clusters, confirming that the fullerene-like boron cages can be stabilized by actinide encapsulation. This work is expected to provide potential routes for the construction of robust borospherenes.

Reduction of Np(VI) with hydrazinopropionitrile via water-mediated proton transfer.

Effectively adjusting and controlling the valence state of neptunium (Np) is essential in its separation during spent fuel reprocessing. Hydrazine and its derivatives as free-salts can selectively reduce Np(VI) to Np(V). Reduction mechanisms of Np(VI) with hydrazine and four derivatives have been explored using multiple theoretical methods in our previous works. Herein, we examine the reduction mechanism of Np(VI) with hydrazinopropionitrile (NCCH2N2H3) which exhibits faster kinetics than most other hydrazine derivatives probably due to its σ-π hyperconjugation effect. Free radical ion pathways I, II and III involving the three types of hydrazine H atoms were found that correspond to the experimentally established mechanism of reduction of two Np(VI) via initial oxidation to [NCCH2N2H3]+˙, followed by conversion to NCCH2N2H (+2H3O+) and ultimately to CH3CN + N2. Potential energy profiles suggest that the second redox stage is rate-determining for all three pathways. Pathway I with water-mediated proton transfer is energetically preferred for hydrazinopropionitrile. Analyses using the approaches of localized molecular orbitals (LMOs), quantum theory of atoms in molecules (QTAIM), and intrinsic reaction coordinate (IRC) elucidate the bonding evolution for the structures on the reaction pathways. The results of the spin density reveal that the reduction of the first Np(VI) ion is the outer-sphere electron transfer, while that of the second Np(VI) ion is the hydrogen transfer. This work offers new insights into the nature of reduction of Np(VI) by hydrazinopropionitrile via water-mediated proton transfer, and provides a basis for designing free-salt reductants for Np separations.

Theoretical Insights on Improving Amidoxime Selectivity for Potential Uranium Extraction from Seawater.

Extraction of uranium from seawater is one of the important ways to solve the shortage of terrestrial uranium resources. Thereinto, the competition between uranyl and vanadium cations is a significant challenge in the commonly used amidoxime-based adsorbents for extracting uranium from seawater. An in-depth understanding of the extraction behaviors of modified amidoxime groups with uranyl and vanadium ions is one of the effective means to design and develop efficient adsorbents for selective uranium sequestration. In this work, we have designed and systematically investigated the alkyl and amino functionalized amidoxime, (Z)-2-amino-N'-hydroxy-N,N-dimethylbenzimidamide (L1), and its phenyl and methoxy derivatives ((Z)-3-amino-N'-hydroxy-N,N-dimethyl-2-naphthimidamide (L2) and (Z)-2-amino-N'-hydroxy-4-methoxy-N,N-dimethylbenzimidamide (L3)) by quantum chemistry calculations. In the uranyl complexes, the amidoxime groups prefer to act as η2-coordinated ligands as the amidoximes increase, and there exist substantial hydrogen bond interactions, which are different from the vanadium complexes. Various bonding analyses show that the L1 ligand possesses a stronger binding affinity to UO22+, and the -C6H5 and -CH3O substituent groups seem to have no effect on the improvement of extraction ability. Thermodynamic analysis confirms that the L1 ligand has a stronger extraction capability to uranyl ion compared to L2 and L3. According to the calculations of the vanadium (V) (VO2+ and VO3+) complexes with the L1 ligand, L1 is more likely to react with [H2VO4]- and [HVO4]2- to form VO2+ complexes. Expectantly, thermodynamic analysis displays a higher extraction capacity for uranyl ions than vanadium ions. Therefore, these alkyl and amino functionalized amidoxime ligands demonstrate high selectivity for uranyl over vanadium ions, which is mainly due to the coordination mode changes of these ligands toward vanadium in conjunction with the considerable hydrogen bonds in the uranyl complexes. These results are expected to afford useful clues for the design of efficient adsorbents for uranium extraction from seawater.

Construction of the Largest Metal-Centered Double-Ring Tubular Boron Clusters Based on Actinide Metal Doping.

Metal doping has been considered to be an effective approach to stabilize various boron clusters. In this work, we constructed a series of largest metal-centered double-ring tubular boron clusters An@B24 (An = Th, Pa, Pu, and Am). Extensive global minimum structural searches combined with density functional theory predicted that the global minima of An@B24 (An = Th, Pu, and Am) are double-ring tubular structures. Formation energy analysis indicates that these boron clusters are highly stable, especially for Th@B24 and Pa@B24. Detailed bonding analysis shows that the significant stability of An@B24 is determined by the covalent character of the An-B bonding, which stems from the interactions of An 5f and 6d orbitals and B 2p orbitals. These results show that actinide metal doping is a feasible route to construct stable large metal-centered double-ring tubular boron clusters, offering the possibility to design boron nanomaterials with special physiochemical properties.