Chloride and pseudohalide hydride-carbonyl ruthenium(II) complexes with 4-pyrrolidinopyridine as co-ligand

Chloride and pseudohalide (N₃ ^?, NCS^?) hydride-carbonyl ruthenium(II) complexes with 4-pyrrolidinopyridine as co-ligand were synthesized and characterized by IR, ¹H, and ³¹P NMR, electronic absorption and emission spectroscopy and X-ray crystallography. The electronic structures of the complexes were calculated by density functional theory (DFT) on their crystal structures. The spin-allowed singlet–singlet electronic transitions of the complexes were calculated by time-dependent DFT, and the UV–Vis spectra have been discussed on these basis. The emission properties of the complexes were also studied.     

Complexation between uranyl(VI) and CMPO in a hydroxyl-functionalized ionic liquid: An extraction,spectrophotography, and calorimetry study

The extraction complexes of uranyl(VI) in HNO₃ to a hydroxyl-functionalized ionic liquid (IL) phase, HOEtmimNTf₂ bearing CMPO, were investigated. Three possibly successive extraction complexes, UO₂L²⁺ (L = CMPO), UO₂L₂²⁺ and UO₂L₃²⁺, were detected based on variable U/L ratios. Uranyl(VI) prefers to be extracted as complex UO₂L₃²⁺, combining with the ions from HOEtmimNTf₂ to construct a solid material through self-assembly. The thermodynamics of complexes, UO₂L_j²⁺ (j = 1-3), were studied by spectrophotometry and microcalorimetry. All the formation reactions are principally driven by entropy, although a small part of the driving force of complexes UO₂L₂²⁺ and UO₂L₃²⁺ comes from enthalpy. Based on the thermodynamic properties for complex UO₂L₃²⁺, we provide a possible coordination mode in HOEtmimNTf₂: the first CMPO molecule coordinates with UO₂²⁺ in a bidentate fashion while the others do in a monodentate fashion. The results offer a thermodynamic insight into the formation behaviors of the uranyl(VI)/CMPO complexes involving the special IL HOEtmimNTf₂, which is of significance to advance the novel IL extraction strategy.     

New Ionic Liquid Based on the CMPO Pattern for the Sequential Extraction of U(VI), Am(III) and Eu(III)

Extraction of U(VI), Eu(III) and Am(III) has been performed from acidic aqueous solutions (HNO₃, HClO₄) into the ionic liquid [C₄mim][Tf₂N] in which a new extracting task-specific ionic liquid, based on the CMPO unit {namely 1-[3-[2-(octylphenylphosphoryl)acetamido]propyl]-3-methyl-1H-imidazol-3-ium bis(trifluoromethane)sulfonamide, hereafter noted OctPh-CMPO-IL}, was dissolved at low concentration (0.01 mol·L^?1). EXAFS and UV–Vis spectroscopy measurements were performed to characterize the extracted species. The extraction of U(VI) is more efficient than the extraction of trivalent Am and Eu using this TSIL, for both acids and their concentration range. We obtained evidence that the metal ions are extracted as a solvate (UO₂(OctPh-CMPO-IL)₃) by a cation exchange mechanism. Nitrate or perchlorate ions do not play a direct role in the extraction by being part of the extracted complexes, but the replacement of nitric acid for perchloric acid entails a drop in the selectivity between U and Eu. However, our TSIL allows a sequential separation of U(VI) and Eu/Am(III) using the same HNO₃ concentration and same nature of the organic phase, just by changing the ligand concentration.     

Reaction of ZnCl2 and HgCl2 metal salts with a bidentate Schiff base ligand in methanol solution, X-ray crystal structure, and theoretical studies

From the reaction of ZnCl₂ and HgCl₂ metal salts with (E)-4-chloro-N-(pyridine-2-ylmethylene)benzeneamine (L) in methanol solution, two binuclear Schiff base complexes were prepared. Both complexes were characterized by elemental analysis, UV–Vis, and IR spectrophotometry. X-ray crystal structure analysis showed that metal ion in the resulting centrosymmetric dinuclear ML₂Cl₄ complexes is in a distorted trigonal bipyramidal and a distorted square pyramidal coordination environment in the case of Zn(II) and Hg(II) metal ions, respectively. Three types of reaction between MCl₂ salts and ligand L producing three different types of products—ML₂ ²⁺, MLCl₂, and M₂L₂Cl₄—were simulated in both the gas phase and solution. The gas phase calculations at DFT (B3LYP) level of theory using SDD, CEP-121G, and LanL2DZ basis sets showed that the binuclear M₂L₂Cl₄ complexes are more stable than corresponding mononuclear MLCl₂ complexes. Furthermore, both the gas phase and solution studies showed that the formation of M₂L₂Cl₄ complexes from the metal cations, chloride anion, and ligand molecule is energetically more favored than that of MLCl₂ and ML₂ ²⁺ complexes.     

Synthesis,characterization of Uranyl(VI), Th(IV), Zr(IV) mixed-ligand complexes with S-methyl-2-(4-methoxybenzylidine)dithiocarbazate and N-donor co-ligand,and their evaluation as antimicrobial agent

Schiff base, S-methyl-2-(4-methoxybenzylidine) dithiocarbazate as a primary ligand (HL₁), quinoline (L₂) as a co-ligand, and hydrated metal salts have been reacted in ethanol in 1:2:1 M ratio to produce mixed-ligand complexes of the type, [M(L₁)(L₂)].NO₃ [M = Uranyl(VI), Th(VI), Zr(IV)], The isolated products have been structurally investigated by elemental analyses, ¹H NMR, IR and UV–Vis studies. The electronic studies shows octahedral geometry for all the studied complexes, whereas the molar conductance data suggest an ionic nature. Density functional computation (DFT) studies are also carried out in order to determine the bonding inside the structure of the complexes. The studied mixed-ligand complexes showed moderate antibacterial activity when evaluated against four pathogenic bacteria: Shigella dysenteriae, Bacillus subtilis, Agrobacterium tumefaciens, and Escherichia coli. In addition, molecular docking analysis for all the complexes, using the CLC Drug Discovery Workbench software, showed that they virtually docked on S. dysenteriae, B. subtilis, A. tumefaciens, and E. coli.     

Dioxouranium Complexes with Acetylpyridine Benzoylhydrazones and Related Ligands

Acetylpyridine benzoylhydrazone and related ligands react with common dioxouranium(VI) compounds such as uranyl nitrate or [NBu₄]₂[UO₂Cl₄] to form air‐stable complexes. Reactions with 2, 6‐diacetylpyridinebis(benzoylhydrazone) (H₂L^1a) or 2, 6‐diacetylpyridinebis(salicylhydrazone) (H₂L^1b) give yellow products of the composition [UO₂(L¹)]. The neutral compounds contain doubly deprotonated ligands and possess a distorted pentagonal‐bipyramidal structure. The hydroxo groups of the salicylhydrazonato ligand do not contribute to the complexation of the metal. The equatorial coordination spheres of the complexes can be extended by the addition of a monodentate ligand such as pyridine or DMSO. The uranium atoms in the resulting deep‐red complexes have hexagonal‐bipyramidal coordination environments with the oxo ligands in axial positions. The sterical strains inside the hexagonal plane can be reduced when two tridentate benzoylhydrazonato ligands are used instead of the pentadentate 2, 6‐diacetylpyridine derivatives. Acetylpyridine benzoylhydrazone (HL²) and bis(2‐pyridyl)ketone benzoylhydrazone (HL³) deprotonate and form neutral, red [UO₂(L)₂] complexes. The equatorial coordination spheres of these complexes are puckered hexagons. X‐ray diffraction studies on [UO₂(L^1a)(pyridine)], [UO₂(L^1b)(DMSO)], [UO₂(L²)₂] and [UO₂(L³)₂] show relatively short U—O bonds to the benzoylic oxygen atoms between 2.328(6) and 2.389(8) Å. This suggests a preference of these donor sites of the ligands over their imino and amine functionalities (U—N bond lengths: 2.588(7)—2.701(6) Å ).     

Infrared Spectroscopy of Dioxouranium(V) Complexes with Solvent Molecules: Effect of Reduction

UO₂⁺–solvent complexes having the general formula [UO₂(ROH)]⁺ (R=H, CH₃, C₂H₅, and n‐C₃H₇) are formed using electrospray ionization and stored in a Fourier transform ion cyclotron resonance mass spectrometer, where they are isolated by mass‐to‐charge ratio, and then photofragmented using a free‐electron laser scanning through the 10 μm region of the infrared spectrum. Asymmetric O=U=O stretching frequencies (ν₃) are measured over a very small range [from ～953 cm^?1 for H₂O to ～944 cm^?1 for n‐propanol (n‐PrOH)] for all four complexes, indicating that the nature of the alkyl group does not greatly affect the metal centre. The ν₃ values generally decrease with increasing nucleophilicity of the solvent, except for the methanol (MeOH)‐containing complex, which has a measured ν₃ value equal to that of the n‐PrOH‐containing complex. The ν₃ frequency values for these U(V) complexes are about 20 cm^?1 lower than those measured for isoelectronic U(VI) ion‐pair species containing analogous alkoxides. ν₃ values for the U(V) complexes are comparable to those for the anionic [UO₂(NO₃)₃]^? complex, and 40–70 cm^?1 lower than previously reported values for ligated uranyl(VI) dication complexes. The lower frequency is attributed to weakening of the O?U?O bonds by repulsion related to reduction of the U metal centre, which increases electron density in the antibonding π* orbitals of the uranyl moiety. Computational modelling of the ν₃ frequencies using the B3LYP and PBE functionals is in good agreement with the IRMPD measurements, in that the calculated values fall in a very small range and are within a few cm^?1 of measurements. The values generated using the LDA functional are slightly higher and substantially overestimate the trends. Subtleties in the trend in ν₃ frequencies for the H₂O–MeOH–EtOH–n‐PrOH series are not reproduced by the calculations, specifically for the MeOH complex, which has a lower than expected value.     

A combined spectroscopic and light scattering study of hydrolysis of uranium(VI) leading to colloid formation in aqueous solutions

This study mainly focuses hydrolysis reactions of uranium(VI) under an ambient atmosphere leading to colloid formation in near neutral solution using light scattering, UV–Vis and FTIR-ATR studies. UV–Vis and IR spectrum was recorded for uranyl solution at different pH range. U(VI) hydrolyzed colloids were detected and it was confirmed by the appearance of a band at 941 cm^?1 in the IR spectra. Light scattering measurements were performed on colloidal U(VI) solutions formed at pH range of 7–8. The average particle diameter was determined as 32–36 nm using dynamic light scattering. Well defined colloidal species are formed with no considerable change in particle size with increasing U(VI) concentration. The weight average molecular weight of colloidal species was predicted as 763 Da by Debye plot. The second virial coefficient (A₂) was found to be ?0.1139 ml g^?1 Da. The present study confirms that behaviour of U(VI) contradicts conventional Zr(IV), Th(IV) and Pu(IV) solution chemistry. U(VI) polymerization is less extensive and in neutral solutions it forms only oligomers with 2–3 uranyl units.     

Ligational behavior of thiosemicarbazone,semicarbazone and thiocarbohydrazone ligands towards VO(IV), Ce(III), Th(IV) and UO2(VI) ions: Synthesis,structural characterization and biological studies

Mono- and binuclear VO(IV), Ce(III), Th(IV) and UO₂(VI) complexes of thiosemicarbazone, semicarbazone and thiocarbohydrazone ligands derived from 4,6-diacetylresorcinol were synthesized. The structures of these complexes were elucidated by elemental analyses, IR, UV–vis, ESR, ¹H NMR and mass spectra as well as conductivity and magnetic susceptibility measurements and thermal analyses. The thiosemicarbazone (H₄L¹) and the semicarbazone (H₄L²) ligands behave as dibasic pentadentate ligands in case of VO(IV) and UO₂(VI) complexes, tribasic pentadentate in case of Ce(III) complexes and monobasic pentadentate in case of Th(IV) complexes. However, the thiocarbohydrazone ligand (H₃L³) acts as a monobasic tridentate ligand in all complexes except the VO(IV) complex in which it acts as a dibasic tridentate ligand. The antibacterial and antifungal activities were also tested against Rhizobium bacteria and Fusarium-Oxysporium fungus. The metal complexes of H₄L¹ ligand showed a higher antibacterial effect than the free ligand while the other ligands (H₄L² and H₃L³) showed a higher effect than their metal complexes. The antifungal effect of all metal complexes is lower than the free ligands.     

六聚吡咯大环与铀/超铀酰基离子相互作用:成键、热力学和光谱性质

采用全电子相对论密度泛函理论探索多种六聚吡咯大环锕酰基配合物(nAn;n=1~3;An=U,Np and Pu)的电子结构本质、成键规律和化学反应特性。结构优化发现大环配体空穴大小与锕酰离子尺寸相当时,配合物锕酰基采用性对规则的六角双锥结构,而当空穴尺寸相对大时,配合物则采取扭曲结构以降低体系能量。当配体相同时,随着铀、镎、钚变化,An=O伸缩振动频率逐渐变小,这与优化的键长和键级变化规律相一致。QTAIM(quantum theory of atoms in molecule)拓扑分析显示An-N为弱共价单键特征,具有较大离子性成分。依据不同铀源,得到与大环配体的反应自由能均小于146 kJ·mol~(-1),与实验合成配合物的反应能计算数值相当。对含铀配合物电子吸收光谱计算显示,低能(近红外和可见光区)的吸收带具有全部或较大的配体→金属电荷转移性质贡献。     

Encapsulating nanosilica into polyacrylic acid and chitosan interpenetrating network hydrogel for preconcentration of uranium from aqueous solutions

Polyacrylic acid, Chitosan and nanosilica particles composite (PCNS) was prepared for enrichment of U (VI) from aqueous solutions. Adsorption tests controlled by different parameters including contact time, pH, initial concentration of UO₂²⁺ and coexistence ions were examined. FTIR, SEM and EDX studies proved the formation of composite and confirmed efficient adsorption of UO₂²⁺ by PCNS. The experimental datas fit the Langmuir and pseudo-second-order models, the R_L (0.115–0.645) indicates the adsorption of UO₂²⁺ onto PCNS are favorable. The value of q_m (451.118 mg g^?1) and adsorption–desorption experiments showed PCNS hydrogel can be reckoned as a high efficienct and sustainable material for removal of U (VI).     

Synthesis and Characterization of Novel Gold(III) Complexes of Asymmetrically Aryl‐Substituted 1,2‐Dithiolene Ligands Featuring Potential‐Controlled Spectroscopic Properties

The tetrabutylammonium (TBA⁺) salts of square‐planar monoanionic gold complexes of the unsymmetrically substituted Ar,H‐edt^2? 1,2‐dithiolene ligands (Ar,H‐edt^2?=arylethylene‐1,2‐dithiolato; Ar=phenyl ( 1 ^?), 2‐naphthyl ( 2 ^?), and 1‐pyrenyl ( 3 ^?)) were synthesized and characterized by spectroscopic and electrochemical methods and the corresponding neutral species ( 1 , 2 , and 3 , respectively) were obtained in CH₂Cl₂ solution at room temperature by diiodine oxidation. The single‐crystal X‐ray diffraction structural data collected for (TBA⁺)( 2 ^?), supported by DFT theoretical calculations, are consistent with the ene‐1,2‐dithiolate form of the ligand and the Au^III oxidation state. All complexes feature intense near‐IR absorptions (at about 1.5 μm) in their neutral states and Vis‐emitting properties in the 400–550 nm range, the energy of which is controlled by the charge of the complex in the case of the 3 ^?/ 3 couple. The spectroscopic and electrochemical features of 1 ^x? and 2 ^x? (x=0, 1), both in their cis and trans conformations, were investigated by means of DFT and time‐dependent (TD) DFT calculations.     

A DFT study of uranyl hydroxyl complexes: structure and stability of trimers and tetramers

A DFT study of U(VI) hydroxy complexes was performed with special attention paid to the [(UO₂)₃(OH)₅(H₂O)_4–7]⁺ and [(UO₂)₄(OH)₇(H₂O)_5–8]⁺ species. It was established that the ionicity of the U=O bond increased when moving from [(UO₂)(H₂O)₅]²⁺, [(UO₂)₂(OH)(H₂O)₈]³⁺, [(UO₂)₂(OH)₂(H₂O)₆]²⁺, [(UO₂)₃(OH)₅(H₂O)_4–6]⁺ to [(UO₂)₄(OH)₇(H₂O)_5–8]⁺ species. In both [(UO₂)₃(OH)₅(H₂O)_4–6]⁺ and [(UO₂)₄(OH)₇(H₂O)_5–8]⁺ complexes, the U=O bond was observed to have a range of different lengths which depended on the composition of the first coordination sphere of UO₂ ²⁺. The cyclic structures of trimeric complexes were somewhat more stable than their linear structures, which was probably due to the steric effect.

     

Preparation,structural characterization and biological studies of some new levofloxacin metal complexes

A new series of metal complexes of Ti(IV), V(IV), Y(III), Zr(IV), Ce(IV) and U(VI) with levofloxacin (Levo) were synthesized and characterized by elemental analysis, molar conductivity, magnetic moment measurements, UV–Vis, FT-IR and ¹H NMR, XRD as well as TG-DTG techniques. The data indicated that levofloxacin reacts as a bidentate ligand chelate to the metal ion through the pyridone oxygen and one carboxylato oxygen. The thermal dehydration and decomposition of the complexes were studied kinetically using Coats–Redfern and Horowitz–Metzger methods, and the thermodynamic data reflected the thermal stability for all complexes. The calculated bond length and the bond stretching force constant, F(U=O), values for UO₂ bond are 1.86 Å and 690.67 N m^?1. The biological activities of the levofloxacin, meta-salts and their metal complexes were assayed against different bacterial and fungal species as well as their effect on degradation of calf thymus DNA.     

Thermodynamic and Structural Trends in Hexavalent Actinyl Cations: Complexation of Dipicolinic Acid with NpO22+ and PuO22+ in Comparison with UO22+

The complexation of NpO₂²⁺ and PuO₂²⁺ with dipicolinic acid (DPA) has been investigated in 0.1 M NaClO₄ by spectrophotometry, microcalorimetry, and single crystal diffractometry. Formation of 1:1 and 1:2 (metal/ligand molar ratio) complexes of DPA with NpO₂²⁺ and PuO₂²⁺ were identified and the thermodynamic parameters were determined and compared with those of UO₂²⁺. All three hexavalent actinyl cations form strong 1:1 DPA complexes with slightly decreasing but comparable stability constants from UO₂²⁺ to PuO₂²⁺, whereas the stability constants of the 1:2 complexes (log β₂) decrease substantially along the series (16.3 for UO₂L₂^2?, 15.17 for NpO₂L₂^2?, and 14.17 for PuO₂L₂^2? at 25 °C). The enthalpies of complexation for the 1:2 complexes become less exothermic from UO₂L₂^2? (?28.9 kJ mol^?1), through NpO₂L₂^2? (?27.2 kJ mol^?1), and to PuO₂L₂^2? (?22.7 kJ mol^?1). The trends in the thermodynamic parameters are discussed in terms of the effective charge of the cations and the steric constraints in the structures of the complexes. In addition, the features of the absorption spectra, including the wavelength and intensity of the absorption bands, are related to the perturbation of the ligand field and the symmetry of the actinyl complexes.     

Spectroscopic investigation of uranium sorption on soil surface using X-ray photoelectron spectroscopy

A study was carried out to understand the sorption of uranium (U) onto soil surface and identify the species of U on soil surface using X-Ray Photoelectron Spectroscopy (XPS). For the study soil was amended with uranyl nitrate and surface speciation study was carried out by investigating the energy region for U in spectrum. Analysis of spectrum revealed that U is present in U(VI) state. Deconvolution of XPS spectrum of U(VI) sorbed on soil surface revealed that U(VI) species such as, UO₂ ²⁺ and (UO₂)_x(OH) _y ^(2x?y)+ form complex with silanol, aluminol and goethite sites. The possible surface complexation is: ≡Al(OH)₂UO₂ ²⁺, ≡SiO₂UO₂, ≡SiO₂(UO₂)₃(OH)₅ and ≡Fe(OH)₂UO₂.     

Synthesis, characterisation and chemical reactivity of some new dioxouranium(VI) complexes of 2-aminobenzoylhydrazone of butane-2,3-dione

A new series of dioxouranium(VI) complexes of a potential ONNO tetradentate donor 2-aminobenzoylhydrazone of butane-2,3-dione (L₁H₂) have been synthesized. At pH 2·5–4·0, the donor (L₁H₂) reacts in the keto form and complexes of the type [UO₂(L₁H₂)(X)₂] (X⁻=Cl⁻, Br⁻, NO ₃ ⁻ , NCS⁻, ClO ₄ ⁻ , CH₃COO⁻, 1/2SO ₄ ²⁻ ) are obtained. At higher pH (6·5–7), the complex of the enol form having the formula [UO₂(L₁)(H₂O)] has been isolated. On reaction with a monodentate lewis base (B), both types of complexes yield adducts of the type [UO₂(L₁)(B)]. All these complexes have been characterised adequately by elemental analyses and other standard physicochemical techniques. Location of the bonding sites of the donor molecule around the uranyl ion, status of the uranium-oxygen bond and the probable structure of the complexes have also been discussed.     

Predicting the redox properties of uranyl complexes using electronic structure calculations

A plethora of chemical reactions is redox driven processes. The conversion of toxic and highly soluble U(VI) complexes to nontoxic and insoluble U(IV) form are carried out through proton coupled electron transfer by iron containing cytochromes and mineral surfaces such as machinawite. This redox process takes place through the formation of U(V) species which is unstable and immediately undergo the disproportionation reaction. Thus, theoretical methods are extremely useful to understand the reduction process of U(VI) to U(V) species. We here have carried out the structures and reduction properties of several U(VI) to U(V) complexes using a variety of electronic structure methods. Due to the lack of experimental ionization energies for uranyl (UO₂(V)‐UO₂(VI)) couple, we have benchmarked the current and popularly used density functionals and cost effective ab initio methods against the experimental electron detachment energies of [UO₂F₄]^1‐/2‐ and [UO₂Cl₄]^1‐/2‐. We find that electron detachment energy of U(VI) predicted by RI‐MP2 level on the BP86 geometries correlate nicely with the experimental and CCSD(T) data. Based on our benchmark studies, we have predicted the structures and electron detachment energies of U(V) to U(VI) species for a series of uranium complexes at the RI‐MP2//BP86 level which are experimentally inaccessible till date. We find that the redox active molecular orbital is ligand centered for the oxidation of U(VI) species, where it is metal centered (primarily f‐orbital) for the oxidation of U(V) species. Finally, we have also calculated the detachment energies of a known uranyl [UO₂]¹⁺ complex whose X‐ray crystal structures of both oxidation states are available. The large bulky nature of the ligand stabilizing the uncommon U(V) species which cannot be routinely studied by present day CCSD(T) methods as the system size are more than 20–30 atoms. The success of our efficient computational strategy can be experimentally verified in the near future for the complex as the structures are stable in gas phase which can undergo oxidation.     

Tuning the Electronic Properties in Ruthenium–Quinone Complexes through Metal Coordination and Substitution at the Bridge

A rare example of a mononuclear complex [(bpy)₂Ru(L¹_?H)](ClO₄), 1 (ClO₄) and dinuclear complexes [(bpy)₂Ru(μ‐L¹_?2H)Ru(bpy)₂](ClO₄)₂, 2 (ClO₄)₂, [(bpy)₂Ru(μ‐L²_?2H)Ru(bpy)₂](ClO₄)₂, 3 (ClO₄)₂, and [(bpy)₂Ru(μ‐L³_?2H)Ru(bpy)₂](ClO₄)₂, 4 (ClO₄)₂ (bpy=2,2′‐bipyridine, L¹=2,5‐di‐(isopropyl‐amino)‐1,4‐benzoquinone, L²=2,5‐di‐(benzyl‐amino)‐1,4‐benzoquinone, and L³=2,5‐di‐[2,4,6‐(trimethyl)‐anilino]‐1,4‐benzoquinone) with the symmetrically substituted p‐quinone ligands, L, are reported. Bond‐length analysis within the potentially bridging ligands in both the mono‐ and dinuclear complexes shows a localization of bonds, and binding to the metal centers through a phenolate‐type “O^?” and an immine/imminium‐type neutral “N” donor. For the mononuclear complex 1 (ClO₄), this facilitates strong intermolecular hydrogen bonding and leads to the imminium‐type character of the noncoordinated nitrogen atom. The dinuclear complexes display two oxidation and several reduction steps in acetonitrile solutions. In contrast, the mononuclear complex 1 ⁺ exhibits just one oxidation and several reduction steps. The redox processes of 1 ¹⁺ are strongly dependent on the solvent. The one‐electron oxidized forms 2 ³⁺, 3 ³⁺, and 4 ³⁺ of the dinuclear complexes exhibit strong absorptions in the NIR region. Weak NIR absorption bands are observed for the one‐electron reduced forms of all complexes. A combination of structural data, electrochemistry, UV/Vis/NIR/EPR spectroelectrochemistry, and DFT calculations is used to elucidate the electronic structures of the complexes. Our DFT results indicate that the electronic natures of the various redox states of the complexes in vacuum differ greatly from those in a solvent continuum. We show here the tuning possibilities that arise upon substituting [O] for the isoelectronic [NR] groups in such quinone ligands.     

Abiotic reduction of uranium by mackinawite (FeS) biogenerated under sulfate-reducing condition

Sulfate-reducing bacteria and their by-products, such as iron sulfides, are widely distributed in groundwater and sediments, and can affect subsurface aqueous chemistry. Here we show the catalytic reduction of hexavalent uranium by FeS particles, which were largely generated by the activities of Desulfovibrio desulfuricans and D. vulgaris in anaerobic condition. Characterization of FeS particles by X-ray diffraction and high-resolution transmission electron microscopy revealed the presence of mackinawite having thin and flexible platy sheets with 0.5-nm lamellar spacing. This biogenic phase mediated abiotic reduction of U(VI) to U(IV) which was confirmed by UV–Vis absorption spectroscopy. The U conversion occurred through surface catalysis that involved adsorption of aqueous U(VI)–carbonate complexes (predominantly UO₂(CO₃) ₃ ^4? ) onto the mackinawite, but the transformed uranium was then released and remained in suspended form in the solution phase. This surface catalysis and subsequent U(IV) remobilization has not been reported as a pathway to occur under sulfate-reducing conditions. Our results suggest that the iron sulfide solid, which is characteristic of conductive property, is very sensitive and variable depending on the electron supplying and transferring environment, negatively affecting the surface uranium to be strongly stabilized and fixed on the FeS surface.