Fate of Oxidation States at Actinide Centers in Redox-Active Ligand Systems Governed by Energy Levels of 5 f Orbitals.

We report the formation of a NpIV complex from the complexation of NpVI O2 2+ with the redox-active ligand tBu-pdiop2- =2,6-bis[N-(3,5-di-tert-butyl-2-hydroxyphenyl)iminomethyl]pyridine. To the best of our knowledge, this is the first example of the direct complexation-induced chemical reduction of NpVI O2 2+ to NpIV . In contrast, the complexation of UVI O2 2+ with tBu-pdiop2- did not induce the reduction of UVI O2 2+ , not even after the two-electron electrochemical reduction of [UVI O2 (tBu-pdiop)]. This contrast between the Np and U systems may be ascribed to the decrease of the energy of the 5 f orbitals in Np compared to those in U. The present findings indicate that the redox chemistry between UVI O2 2+ and NpVI O2 2+ should be clearly differentiated in redox-active ligand systems.

Crystal Structures of Ce(IV) Nitrates with Bis(2-pyrrolidone) Linker Molecules Deposited from Aqueous Solutions with Different HNO3 Concentrations.

We investigated the molecular and crystal structures of Ce(IV) compounds deposited under different [HNO3] with bis(2-pyrrolidone) linker molecules having a trans-1,4-cyclohexyl bridging moiety (L). As a result, we found that, after loading L, Ce(IV) in HNO3(aq) exclusively provides one of different crystalline phases, (HL)2[Ce(NO3)6] or [Ce2(µ-O)-(NO3)6(L)2]n 2D MOF, depending on [HNO3]. The former has been obtained at [HNO3] = 4.70-9.00 M and is isomorphous with the analogous (HL)2[An(NO3)6] we reported previously. In contrast, the deposition of the latter phase at the lower [HNO3] conditions (1.00-4.30 M) demonstrates that hydrolysis and oxolation of Ce4+ proceed even below pH 0 to provide a [Ce-O-Ce]6+ unit included in this compound. These different Ce(IV) phases are exchangeable with each other under soaking in HNO3(aq), implying that chemical equilibria of dissolution/deposition of these crystalline phases and hydrolysis and oxolation of Ce4+ and its complexation with NO3- occur in parallel. Indeed, such coordination chemistry of Ce(IV) in HNO3(aq) was well corroborated by 17O NMR, Raman, and IR spectroscopy.

Solid-State Schikorr Reaction from Ferrous Chloride to Magnetite with Hydrogen Evolution as the Kinetic Bottleneck.

The selective formation of meta-stable Fe3O4 from ferrous sources by suppressing its oxidative conversion to the most stable hematite (α-Fe2O3) is challenging under oxidative conditions for solid-state synthesis. In this work, we investigated the conversion of iron(II) chloride (FeCl2) to magnetite (Fe3O4) under inert atmosphere in the presence of steam, and the obtained oxides were analyzed by atomic-resolution TEM, 57Fe Mössbauer spectroscopy, and the Verwey transition temperature (Tv). The reaction proceeded in two steps, with H2O as the oxide source in the initial step and as an oxidant in the second step. The initial hydrolysis occurred at temperatures higher than 120 °C to release gaseous HCl, via substituting lattice chloride Cl- with oxide O2-, to give iron oxide intermediates. In the first step, the construction of the intermediate oxides was not topotactic. The second step as a kinetic bottleneck occurred at temperatures higher than 350 °C to generate gaseous H2 through the oxidation of FeII by H+. A substantially large kinetic isotope effect (KIE) was observed for the second step at 500 °C, and this indicates the rate-determining step is the hydrogen evolution. Quantitative analysis of evolved H2 revealed that full conversion of ferrous chloride to magnetite at 500 °C was followed by additional oxidation of the outer sphere of magnetite to give a Fe2O3 phase, as supported by X-ray photoelectron spectroscopy (XPS), and the outer phase confined the conductive magnetite phase within the insulating layers, enabling kinetic control of magnetite synthesis. As such, the reaction stopped at meta-stable magnetite with an excellent saturation magnetization (σs) of 86 emu g-1 and Tv > 120 K without affording the thermodynamically stable α-Fe2O3 as the major final product. The study also discusses the influence of parameters such as reaction temperature, initial grain size of FeCl2, the extent of hydration, and partial pressure of H2O.

Fully Chelating N3O2-Pentadentate Planar Ligands Designed for the Strongest and Selective Capture of Uranium from Seawater.

Based on the unique fivefold equatorial coordination of UO22+, water-compatible pentadentate planar ligands, H2saldian and its derivatives, were designed for the strong and selective capture of UO22+ in seawater. In the simulated seawater condition (0.5 M NaCl + 2.3 mM HCO3-/CO32-, pH 8), saldian2- shows the strongest complexation with UO22+ to form UO2(saldian) (log ß11 = 28.05 ± 0.07), which is more than 10 order of magnitude greater than amidoxime-based or -inspired ligand systems most commonly employed for U capture from seawater. Good selectivity for UO22+ from other metal ions coexisting in seawater was also demonstrated.

Hydrophobic core formation and secondary structure elements in uranyl(VI)-binding peptides.

Cyclic peptides as well as a modified EF-hand motif of calmodulin have been newly designed to achieve high affinity towards uranyl(VI). Cyclic peptides may be engineered to bind uranyl(VI) to its backbone under acidic conditions, which may enhance its selectivity. For the modified EF-hand motif of calmodulin, strong electrostatic interactions between uranyl(VI) and negatively charged side chains play an important role in achieving high affinity; however, it is also essential to have a secondary structure element and formation of hydrophobic cores in the metal-bound state of the peptide.

Effects of Substituents on the Molecular Structure and Redox Behavior of Uranyl(V/VI) Complexes with N3O2-Donating Schiff Base Ligands.

Uranyl(VI) complexes with pentadentate N3O2-donating Schiff base ligands having various substituents at the ortho (R1) and/or para (R2) positions on phenolate moieties, R1,R2-Mesaldien2-, were synthesized and thoroughly characterized by 1H nuclear magnetic resonance, infrared, elemental analysis, and single-crystal X-ray diffraction. Molecular structures of UO2(R1,R2-Mesaldien) are more or less affected by the electron-donating or -withdrawing nature of the substituents. The redox behavior of all UO2(R1,R2-Mesaldien) complexes was investigated to understand how substituents introduced onto the ligand affect the redox behavior of these uranyl(VI) complexes. As a result, the redox potentials of UO2(R1,R2-Mesaldien) in dimethyl sulfoxide increased from -1.590 to -1.213 V with an increase in the electron-withdrawing nature of the substituents at the R1 and R2 positions. The spectroelectrochemical measurements and theoretical calculation [density functional theory (DFT) and time-dependent DFT calculations] revealed that the center U6+ of each UO2(R1,R2-Mesaldien) complex undergoes one-electron reduction to afford the corresponding uranyl(V) complex, [UO2(R1,R2-Mesaldien)]-, regardless of the difference in the substituents. Consequently, the redox active center of uranyl(VI) complexes seems not to be governed by the redox potentials but to be determined by whether the LUMO is centered on a U 5f orbital or on one π* orbital of a surrounding ligand.

Crystal Structure of Regularly Th -Symmetric [U(NO3 )6 ]2- Salts with Hydrogen Bond Polymers of Diamide Building Blocks.

Hexanitratouranate(IV), [U(NO3 )6 ]2- , has been crystallized with anhydrous H+ -involving hydrogen bond polymers connected by selected diamide building blocks. Thanks to the significant moderation of electrostatic interactions between the anions and cations, the molecular structure of [U(NO3 )6 ]2- in these compounds is regularly Th -symmetric. The f-f transitions stemming from 5f2 configuration of U4+ are strictly forbidden by the Laporte selection rule in such a centrosymmetric system, so that the obtained compounds are nearly colourless in contrast to other UIV species usually coloured in green.

Molecular and Crystal Structures of Uranyl Nitrate Coordination Polymers with Double-Headed 2-Pyrrolidone Derivatives.

Double-headed 2-pyrrolidone derivatives (DHNRPs) were designed and synthesized as bridging ligands for the efficient and selective separation of UO22+ from a HNO3 solution by precipitation. The building blocks, UO2(NO3)2 and DHNRPs, were successfully connected to form an infinite 1D coordination polymer. The solubility of [UO2(NO3)2(DHNRP)]n is no longer correlated to the hydrophobicity of the ligand but is exclusively governed by the ligand symmetry and packing efficiency. The newly designed DHNRP family can be used to establish a new spent nuclear fuel reprocessing scheme.

Experimental and theoretical approaches to redox innocence of ligands in uranyl complexes: what is formal oxidation state of uranium in reductant of uranyl(VI)?

Redox behavior of [UO2(gha)DMSO](-)/UO2(gha)DMSO couple (gha = glyoxal bis(2-hydroxanil)ate, DMSO = dimethyl sulfoxide) in DMSO solution was investigated by cyclic voltammetry and UV-vis-NIR spectroelectrochemical technique, as well as density functional theory (DFT) calculations. [UO2(gha)DMSO](-) was found to be formed via one-electron reduction of UO2(gha)DMSO without any successive reactions. The observed absorption spectrum of [UO2(gha)DMSO](-), however, has clearly different characteristics from those of uranyl(V) complexes reported so far. Detailed analysis of molecular orbitals and spin density of the redox couple showed that the gha(2-) ligand in UO2(gha)DMSO is reduced to gha(•3-) to give [UO2(gha)DMSO](-) and the formal oxidation state of U remains unchanged from +6. In contrast, the additional DFT calculations confirmed that the redox reaction certainly occurs at the U center in other uranyl(V/VI) redox couples we found previously. The noninnocence of the Schiff base ligand in the [UO2(gha)DMSO](-)/UO2(gha)DMSO redox couple is due to the lower energy level of LUMO in this ligand relative to those of U 5f orbitals. This is the first example of the noninnocent ligand system in the coordination chemistry of uranyl(VI).

Controlling mixed-valence states of pyridyldiimino-bis(o-phenolato) ligand radical in uranyl(VI) complexes.

Combination of a uranyl(VI) ion (UVIO22+) with a redox-active ligand results in characteristic electronic structures that cannot be achieved by either component alone. In this study, three UVIO22+ complexes that bear symmetric or asymmetric 2,6-diiminopyridine-based ligands were synthesized and found to exhibit a first redox couple between -1.17 V and -1.31 V (vs. Fc0/+) to afford singly reduced complexes. The unique electronic transitions of the singly reduced UVIO22+ complexes observed in the NIR region allowed us to combine spectroelectrochemistry and time-dependent density functional theory (TD-DFT) calculations to determine the redox-active site in these UVIO22+ complexes, i.e., to clarify the distribution of the additional unpaired electron. By exploiting the push-pull effect of electron-donating and -withdrawing substituents, the ligand-based π-radical of the singly reduced UVIO22+ complexes, which tends to delocalize over the ligand, can be localized to specific sites.

Towards tailoring hydrophobic interaction with uranyl(VI) oxygen for C-H activation.

Bovine serum albumin (BSA) has a uranyl(VI) binding hotspot where uranium is tightly bound by three carboxylates. Uranyl oxygen is "soaked" into the hydrophobic core of BSA. Isopropyl hydrogen of Val is trapped near UO22+ and upon photoexcitation, C-H bond cleavage is initiated. A unique hydrophobic contact with "yl"-oxygen, as observed here, can be used to induce C-H activation.

Actinide chemistry in ionic liquids.

This Forum Article provides an overview of the reported studies on the actinide chemistry in ionic liquids (ILs) with a particular focus on several fundamental chemical aspects: (i) complex formation, (ii) electrochemistry, and (iii) extraction behavior. The majority of investigations have been dedicated to uranium, especially for the 6+ oxidation state (UO2(2+)), because the chemistry of uranium in ordinary solvents has been well investigated and uranium is the most abundant element in the actual nuclear fuel cycles. Other actinides such as thorium, neptunium, plutonium, americium, and curiumm, although less studied, are also of importance in fully understanding the nuclear fuel engineering process and the safe geological disposal of radioactive wastes.

How does chemistry contribute to circular economy in nuclear energy systems to make them more sustainable and ecological?

While one should be aware that its zero CO2 emission is actually achievable only when electric power is generated, nuclear power is one of the most viable and proven "carbon-free" energy sources to provide baseload electricity to the current energy-demanding society. Even after the power generation, the major part of spent nuclear fuels still consists of recyclable nuclear fuel materials such as U and Pu, promising circular economy of nuclear energy systems in principle. However, actual situations are not very simple due to the following issues: (1) resource security of nuclear fuel materials, (2) issues of depleted uranium, and (3) treatment and disposal of high-level radioactive wastes. In this Perspective, I discussed how chemistry can contribute to resolving these problems and what task academic research in fundamental chemistry should take on there.

Simplest homoleptic metal-centered tetrahedrons, [M(OH2)4]2+, in 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid (M = Co, Ni, Cu).

Dissolution of a tetrafluoroborate or perchlorate salt of [M(OH(2))(6)](2+) (M = Co, Ni, Cu) in 1-ethyl-3-methylimidazolium tetraluforoborate ionic liquid ([emim]BF(4)) results in significant solvatochromism and increasing intensity of color. These observations arise from partial dehydration from the octahedral [M(OH(2))(6)](2+) and formation of the tetrahedral [M(OH(2))(4)](2+). This reaction was monitored by the intense absorption band due to the d-d transition in the UV-vis absorption spectrum. The EXAFS investigation clarified the coordination structures around M(2+) {[Co(OH(2))(4)](2+), R(Co-O) = 2.17 Å, N = 4.2; [Cu(OH(2))(4)](2+), R(Cu-O) = 2.09 Å, N = 3.8}. (1)H and (19)F NMR study suggested that both [emim](+) and BF(4)(-) are randomly arranged in the second-coordination sphere of [M(OH(2))(4)](2+).

Formation of soluble hexanuclear neptunium(IV) nanoclusters in aqueous solution: growth termination of actinide(IV) hydrous oxides by carboxylates.

Complexation of Np(IV) with several carboxylates (RCOO(-); R = H, CH(3), or CHR'NH(2); R' = H, CH(3), or CH(2)SH) in moderately acidic aqueous solutions was studied by using UV-vis-NIR and X-ray absorption spectroscopy. As the pH increased, all investigated carboxylates initiated formation of water-soluble hexanuclear complexes, Np(6)(µ-RCOO)(12)(µ(3)-O)(4)(µ(3)-OH)(4), in which the neighboring Np atoms are connected by RCOO(-)syn-syn bridges and the triangular faces of the Np(6) octahedron are capped with µ(3)-O(2-)/µ(3)-OH(-). The structure information of Np(6)(µ-RCOO)(12)(µ(3)-O)(4)(µ(3)-OH)(4) in aqueous solution was extracted from the extended X-ray absorption fine structure data: Np-O(2-) = 2.22-2.23 Å (coordination number N = 1.9-2.2), Np-O(RCOO(-)) and Np-OH(-) = 2.42-2.43 Å (N = 5.6-6.7 in total), Np···C(RCOO(-)) = 3.43 Å (N = 3.3-3.9), Np···Np(neighbor) = 3.80-3.82 Å (N = 3.6-4.0), and Np···Np(terminal) = 5.39-5.41 Å (N = 1.0-1.2). For the simpler carboxylates, the gross stability constants of Np(6)(µ-RCOO)(12)(µ(3)-O)(4)(µ(3)-OH)(4) and related monomers, Np(RCOO)(OH)(2)(+), were determined from the UV-vis-NIR titration data: when R = H, log ß(6,12,-12) = 42.7 ± 1.2 and log ß(1,1,-2) = 2.51 ± 0.05 at I = 0.62 M and 295 K; when R = CH(3), log ß(6,12,-12) = 52.0 ± 0.7 and log ß(1,1,-2) = 3.86 ± 0.03 at I = 0.66 M and 295 K.

Effects of coordinating heteroatoms on molecular structure, thermodynamic stability and redox behavior of uranyl(vi) complexes with pentadentate Schiff-base ligands.

Uranyl(vi) complexes with pentadentate N3O2-, N2O3- and N2O2S1-donating Schiff base ligands, tBu,MeO-saldien-X2- (X = NH, O and S), were synthesized and thoroughly characterized by 1H NMR, IR, elemental analysis, and single crystal X-ray diffraction. The crystal structures of UO2(tBu,MeO-saldien-X) showed that the U-X bond strength follows U-O ≈ U-NH > U-S. Conditional stability constants (ß X) of UO2(tBu,MeO-saldien-X) in ethanol were investigated to understand the effect of X on thermodynamic stability. The log ß X decrease in the order of UO2(tBu,MeO-saldien-NH) (log ß NH = 10) > UO2(tBu,MeO-saldien-O) (log ß O = 7.24) > UO2(tBu,MeO-saldien-S) (log ß S = 5.2). This trend cannot be explained only by Pearson's Hard and Soft Acids and Bases (HSAB) principle, but rather follows the order of basicity of X. Theoretical calculations of UO2(tBu,MeO-saldien-X) suggested that the ionic character of U-X bonds decreases in the order of U-NH > U-O > U-S, while the covalency increases in the order U-O < U-NH < U-S. Redox potentials of all UO2(tBu,MeO-saldien-X) in DMSO were similar to each other regardless of the difference in X. Spectroelectrochemical measurements and DFT calculations revealed that the center U6+ of each UO2(tBu,MeO-saldien-X) undergoes one-electron reduction to afford the corresponding uranyl(v) complex. Consequently, the difference in X of UO2(tBu,MeO-saldien-X) affects the coordination of tBu,MeO-saldien-X2- with UO2 2+. However, the HSAB principle is not always prominent, but the Lewis basicity and balance between ionic and covalent characters of the U-X interactions are more relevant to determine the bond strengths.

Synthesis and characterization of a uranyl(VI) complex with 2,6-pyridine-bis(methylaminophenolato) and its ligand-centred aerobic oxidation mechanism to a diimino derivative.

A uranyl(VI) complex with 2,6-bis(3,5-di-tert-butyl-o-phenolateaminomethyl)pyridine (UO2(tBu-pdaop), 1) was synthesized and thoroughly characterized by 1H NMR, IR, elemental analysis, and single-crystal XRD. Right after the dissolution of complex 1 in pyridine or DMSO, the solution was pale red, whereas it gradually turned to dark purple under an ambient atmosphere. 1H NMR spectra at the initial and final states suggested that both of the two aminomethyl groups in 1 were converted to azomethine ones through aerobic oxidation. Indeed, a uranyl(VI) complex with 2,6-bis(3,5-di-tert-butyl-o-phenolateiminomethyl)pyridine (UO2(tBu-pdiop), 2) was obtained from the concentrated solution once the reaction was completed, and was characterized by IR, and single-crystal XRD. Kinetic analyses as well as mechanistic studies based on quantum chemical calculations suggested that hydrogen atom transfer from one of the amino groups in complex 1 to nearby O2 initiates the stepwise oxidation processes to finally afford 2. The present findings demonstrate the novel reactivity of a uranyl(VI) complex, and provide new insights to construct thermally-driven molecular conversion systems by a UO22+ complex catalyst.

Non-aqueous bonding of leuprorelin to ochratoxin A for peptide-based solid-phase extraction.

The anticancer therapeutic leuprorelin was found to have excellent affinity to the carcinogen ochratoxin A (OTA), with an equilibrium constant of 2.2 × 108 M-1 at 273 K (dissociation constant Kd = 4.5 nM) when functionalized into a mesoporous polymer. Binding between the surface-bound leuprorelin and mycotoxin was corroborated with DFT calculations, and it was extended to the extraction of OTA from the heavily fatty matrices of coffee, achieving 95% recovery with improved cyclability as compared with immunoaffinity. This work presents the potential of peptide-mycotoxin interactions for durable non-aqueous extraction.

Spectroelectrochemical identification of a pentavalent uranyl tetrachloro complex in room-temperature ionic liquid.

Reduction of U(VI)O(2)Cl(4)(2-) in a mixture of 1-ethyl-3-methylimidazolium tetrafluoroborate and its chloride at E°' = -0.996 V vs Fc/Fc(+) and 298 K affords U(V)O(2)Cl(4)(3-), which is kinetically stable and exhibits typical character of U(V) in the UV-vis-NIR absorption spectrum.

Complexation-Distribution Separated Solvent Extraction Process Designed for Rapid and Efficient Recovery of Inert Platinum Group Metals.

Previously, we have demonstrated that thermal-assisted techniques can accelerate the extraction of inert platinum group metals (PGMs), while they still have several concerns about difficulty of temperature control in actual extraction contactors and safety risks arising from heating organic solvents. In this study, we report a complexation-distribution separated extraction process for the accelerated extraction of inert PGMs. This extraction method includes two steps: (1) complexation of PGMs with extractants in aqueous solution and (2) distribution of the formed complex from the aqueous phase to organic one. We separately investigated the complexation and distribution processes for typical inert PGMs such as Ru(III) and Rh(III) in the presence of water-soluble N,N,N',N'-tetra-alkylpyridinediamide ligands (PDA) and bis(trifluoromethylsulfonyl)amide (Tf2N-) counteranions. As a result, the water-soluble complexes of Ru(III) and Rh(III) with PDA can be formed in 0.5 M HNO3(aq) within 3 h under heating at 356 K. The formed complexes were extracted to the 1-octanol layer containing Tf2N- within 5 min at room temperature, where this hydrophobic anion plays an important role to promote extraction of PGMs as an anionic phase-transfer catalyst (PTC). Consequently, we successfully established and demonstrated the complexation-distribution separated extraction process for the accelerated extraction of inert PGMs using a water-soluble ligand and anionic PTC.