Observation of a promethium complex in solution.

Lanthanide rare-earth metals are ubiquitous in modern technologies1-5, but we know little about chemistry of the 61st element, promethium (Pm)6, a lanthanide that is highly radioactive and inaccessible. Despite its importance7,8, Pm has been conspicuously absent from the experimental studies of lanthanides, impeding our full comprehension of the so-called lanthanide contraction phenomenon: a fundamental aspect of the periodic table that is quoted in general chemistry textbooks. Here we demonstrate a stable chelation of the 147Pm radionuclide (half-life of 2.62 years) in aqueous solution by the newly synthesized organic diglycolamide ligand. The resulting homoleptic PmIII complex is studied using synchrotron X-ray absorption spectroscopy and quantum chemical calculations to establish the coordination structure and a bond distance of promethium. These fundamental insights allow a complete structural investigation of a full set of isostructural lanthanide complexes, ultimately capturing the lanthanide contraction in solution solely on the basis of experimental observations. Our results show accelerated shortening of bonds at the beginning of the lanthanide series, which can be correlated to the separation trends shown by diglycolamides9-11. The characterization of the radioactive PmIII complex in an aqueous environment deepens our understanding of intra-lanthanide behaviour12-15 and the chemistry and separation of the f-block elements16.

Synergistic Assembly of Charged Oligomers and Amino Acids at the Air-Water Interface: An Avenue toward Surface-Directed CO2 Capture.

Interfaces are considered a major bottleneck in the capture of CO2 from air. Efforts to design surfaces to enhance CO2 capture probabilities are challenging due to the remarkably poor understanding of chemistry and self-assembly taking place at these interfaces. Here, we leverage surface-specific vibrational spectroscopy, Langmuir trough techniques, and simulations to mechanistically elucidate how cationic oligomers can drive surface localization of amino acids (AAs) that serve as CO2 capture agents speeding up the apparent rate of absorption. We demonstrate how tuning these interfaces provides a means to facilitate CO2 capture chemistry to occur at the interface, while lowering surface tension and improving transport/reaction probabilities. We show that in the presence of interfacial AA-rich aggregates, one can improve capture probabilities vs that of a bare interface, which holds promise in addressing climate change through the removal of CO2 via tailored interfaces and associated chemistries.

Reaction Layer Formation on MgO in the Presence of Humidity.

Mineralization by MgO is an attractive potential strategy for direct air capture (DAC) of CO2 due to its tendency to form carbonate phases upon exposure to water and CO2. Hydration of MgO during this process is typically assumed to not be rate limiting, even at ambient temperatures. However, surface passivation by hydrated phases likely reduces the CO2 capture capacity. Here, we examine the initial hydration reactions that occur on MgO(100) surfaces to determine whether they could potentially impact CO2 uptake. We first used atomic force microscopy (AFM) to explore changes in reaction layers in water (pH = 6 and 12) and MgO-saturated solution (pH = 11) and found the reaction layers on MgO are heterogeneous and nonuniform. To determine how relative humidity (R.H.) affects reactivity, we reacted samples at room temperature in nominally dry N2 (∼11-12% R.H.) for up to 12 h, in humid (>95% R.H.) N2 for 5, 10, and 15 min, and in air at 33 and 75% R.H. for 8 days. X-ray reflectivity and electron microscopy analysis of the samples reveal that hydrated phases form rapidly upon exposure to humid air, but the growth of the hydrated reaction layer slows after its initial formation. Reaction layer thickness is strongly correlated with R.H., with denser reaction layers forming in 75% R.H. compared with 33% R.H. or nominally dry N2. The reaction layers are likely amorphous or poorly crystalline based on grazing incidence X-ray diffraction measurements. After exposure to 75% R.H. in air for 8 days, the reaction layer increases in density as compared to the sample reacted in humid N2 for 5-15 min. This may represent an initial step toward the crystallization of the reaction layer. Overall, high R.H. favors the formation of a hydrated, disordered layer on MgO. Based on our results, DAC in a location with a higher R.H. will be favorable, but growth may slow significantly from initial rates even on short timescales, presumably due to surface passivation.

Near Quantitative Removal of Selenate and Sulfate Anions from Wastewaters by Cocrystallization with Chelating Hydrogen-Bonding Guanidinium Ligands.

Selenium (Se) has become an environmental contaminant of aquatic ecosystems as a result of human activities, particularly mining, fossil fuel combustion, and agricultural activities. By leveraging the high sulfate concentrations relative to Se oxyanions (i.e., SeO n 2-, n = 3, 4) present in some wastewaters, we have developed an efficient approach to Se-oxyanion removal by cocrystallization with bisiminoguanidinium (BIG) ligands that form crystalline sulfate/selenate solid solutions. The crystallization of the sulfate, selenate and selenite, oxyanions and of sulfate/selenate mixtures with five candidate BIG ligands are reported along with the thermodynamics of crystallization and aqueous solubilities. Oxyanion removal experiments with the top two performing candidate ligands show a near quantitative removal (>99%) of sulfate or selenate from solution. When both sulfate and selenate are present, there is near quantitative removal (>99%) of selenate, down to sub-ppb Se levels, with no discrimination between the two oxyanions during cocrystallization. Reducing the selenate concentrations by 3 orders of magnitude or more relative to sulfate, as found in many wastewaters, led to no measurable loss in Se removal efficiencies. This work offers a simple and effective alternative to selective separation of trace amounts of highly toxic selenate oxyanions from wastewaters, to meet stringent regulatory discharge limits.

A Photoresponsive Receptor with a 105 Magnitude of Reversible Anion-Binding Switching.

Invited for the cover of this issue are Jeffrey Einkauf, Vyacheslav Bryantsev, Bruce Moyer, and Radu Custelcean from Oak Ridge National Laboratory. The image depicts an anion receptor functionalized with a new photoswitchable chromophore, the diiminoguanidinium group, with exceptionally strong sulfate-binding affinity that can be turned off by photoirradiation with UV light. Read the full text of the article at 10.1002/chem.202200719.

A Photoresponsive Receptor with a 105 Magnitude of Reversible Anion-Binding Switching.

In a leap toward anion separation that uses only energy input for binding and release cycles, we report herein a new class of photoswitchable anion receptors featuring a diiminoguanidinium functionality that displays a change of more than five orders of magnitude in switched-off binding strength towards sulfate, a representative oxyanion, upon photoirradiation with UV light. The (E,E)-2-pyridyl-diiminoguanidinium cation, synthesized as the triflate salt, binds sulfate with extraordinary strength in [D6 ]DMSO owing to its bidentate guanidinium hydrogen bonding, which can chelate the O-S-O edge of sulfate. Upon photoisomerization to the Z,Z isomer, the anion-binding site is essentially shut off by intramolecular hydrogen bonds to the 2-pyridyl substituents, as shown by anion-binding titrations, theoretical calculations, and X-ray structural analysis. This approach will allow the development of advanced anion-separation cycles that use only energy input and generate no chemical waste, and thus address challenging chemical separation problems in a more sustainable way.

Spectroscopic characterization of neptunium(VI), plutonium(VI), americium(VI) and neptunium(V) encapsulated in uranyl nitrate hexahydrate.

The coordination of crystalline products resulting from the co-crystallization of Np(vi), Pu(vi), Am(vi), and Np(v) with uranyl nitrate hexahydrate (UNH) has been revealed through solid-state spectroscopic characterization via diffuse reflectance UV-Vis-NIR spectroscopy, SEM-EDS, and extended X-ray absorption fine structure (EXAFS) spectroscopy. Density functional and multireference wavefunction calculations were performed to analyze the An(vi/v)O2(NO3)2·2H2O electronic structures and to help assign the observed transitions in the absorption spectra. EXAFS show a similar coordination between the U(VI) in UNH and Np(vi) and Pu(vi); while Am resulted in a similar coordination to Am(iii), as reduction of Am(vi) occurred prior to EXAFS data being obtained. The co-crystallization of the oxidized transuranic species-penta- and hexavalent-with UNH, represents a significant advance from not only a practical standpoint in providing an elegant solution for used nuclear fuel recycle, but also as an avenue to expand the fundamental understanding of the 5f electronic behavior in the solid-state.

Correction: Solid state characterization of oxidized actinides co-crystallized with uranyl nitrate hexahydrate.

Correction for 'Solid state characterization of oxidized actinides co-crystallized with uranyl nitrate hexahydrate' by Jeffrey D. Einkauf et al., Dalton Trans., 2020, 49, 608-612.

Solid state characterization of oxidized actinides co-crystallized with uranyl nitrate hexahydrate.

Characterization of the penta- and hexavalent dioxo cations of NpO2+, NpO22+, PuO22+, and AmO22+ has been carried out by diffuse reflectance UV-Vis-NIR spectroscopy, with the first observations of NpO2+, NpO22+, and AmO22+ in the solid state. Absorbance measurements confirmed the presence of the higher actinides of Np, Pu, and Am, with shifts in their absorbance bands indicating the formation of the dinitrate species in the crystalline phase. The oxidized actinides were prepared in the solid state by co-crystallization with UO2(NO3)2·6H2O by a simple reduction in temperature. The hexavalent species were all co-crystallized in near proportion to UO22+ and the pentavalent species was co-crystallized in a slightly less efficient manner, roughly 83% of that of UO22+.

Solubility and Complexation of the Bismuthate Ion in Nitric Acid Systems.

The dissolution rate and solubility of NaBiO3 have been investigated in nitric acid systems ranging from 4 to 6 M HNO3 and were found to be 58-76 µg/cm2·d and 490-830 mM, respectively. The presence of 50 mM U(VI) drastically increased the solubility to 540-1200 mM, while rates of dissolution were relatively unchanged. The solubility of NaBiO3 increased with an increase in U(VI) concentrations at 4 M HNO3, with log-log analysis indicating a one-to-one complex between Bi and U and infrared spectroscopic evidence monitoring uranyl stretching, suggesting complex formation. Absorbance spectra were obtained experimentally and computationally with an absorbance band in the range of 450-600 nm that has been attributed to Bi(V). The ingrowth and decay of Bi(V) in solution was also studied as a function of mass of solid NaBiO3 present, acidity, and temperature. The activation energies of dissolution and decomposition were calculated to be 39 ± 4 and 61 ± 6 kJ/mol, respectively. These results indicate that dissolution of NaBiO3 into the respective Na+ and BiO3-occurs prior to undergoing reduction, a process which conventionally has been believed to occur in the reverse order.

Bismuth(iii)-thiophenedicarboxylates as host frameworks for lanthanide ions: synthesis, structural characterization, and photoluminescent behavior.

Three bismuth-2,5-thiophenedicarboxylates (Bi-TDC) and two europium-2,5-thiophenedicarboxylates (Eu-TDC) were synthesized under ambient conditions. The structures were determined through single crystal X-ray diffraction, and three of the phases were further characterized by powder X-ray diffraction, Raman spectroscopy, and thermogravimetric analysis. Reactions of bismuth nitrate, 2,5-thiophenedicarboxylate, and pyridine in an acidic solution of acetic acid and ethanol yield Hpy[Bi(TDC)2(H2O)]·1.5H2O (1), whereas reactions in a water/ethanol mixture produce a minor phase, [Hpy]3[Bi2(TDC)4(HTDC)(H2O)]·xH2O (2) along with a major product, (Hpy)2[Bi(TDC)2(HTDC)]·0.36H2O (3). The structures of 1-3 are all built from anionic Bi-TDC chains that are further bridged through additional TDC linkages into interpenetrated 2D sheets. Addition of an aqueous lanthanide solution to the reaction mixtures that yielded 1 and 2-3 resulted in the formation of doped phases, Hpy[Bi1-xLnx(TDC)2(H2O)]·1.5H2O (Bi1-xLnx-1), where Ln = Nd, Sm, Eu, Tb, Dy, and Yb, and (Hpy)2[Bi0.99Eu0.01 (TDC)2(HTDC)]·0.36H2O (Bi0.99Eu0.01-3). Using europium nitrate rather than the bismuth precursor resulted in the formation of two homometallic europium based phases, [Eu(TDC)(NO3)(H2O)]n (4) and [Eu2(TDC)3(H2O)9]·5H2O (5), which adopt an extended 3D network and an interpenetrated 2D structure, respectively. Photophysical measurements were carried out for 1 and the lanthanide containing phases and quantum yield and lifetime values were determined for the visible light emitters. Herein, the structural chemistry, spectroscopic properties, and luminescence of the bismuth phases, their lanthanide doped analogs, and the europium compounds are presented.

A General Model of Sensitized Luminescence in Lanthanide-Based Coordination Polymers and Metal-Organic Framework Materials.

Luminescent lanthanides containing coordination polymers and metal-organic frameworks hold great potential in many applications due to their distinctive spectroscopic properties. While the ability to design coordination polymers for specific functions is often mentioned as a major benefit bestowed on these compounds, the lack of a meaningful understanding of the luminescence in lanthanide coordination polymers remains a significant challenge toward functional design. Currently, the study of these compounds is based on the antenna effect as derived from molecular systems, where organic antennae are used to facilitate lanthanide-centered luminescence. This molecular-based approach does not take into account the unique features of extended network solids, particularly the formation of band structure. While guidelines for the antenna effect are well established, they require modification before being applied to coordination polymers. A series of nine coordination polymers with varying topologies and organic linkers were studied to investigate the accuracy of the antenna effect in coordination polymer systems. By comparing a molecular-based approach to a band-based one, it was determined that the band structure that occurs in aggregated organic solids needs to be considered when evaluating the luminescence of lanthanide coordination polymers.

Rethinking Sensitized Luminescence in Lanthanide Coordination Polymers and MOFs: Band Sensitization and Water Enhanced Eu Luminescence in [Ln(C15H9O5)3(H2O)3]n (Ln = Eu, Tb).

A coordination polymer [Ln(C15H9O9)3(H2O)3]n (1-Ln = Eu(III), Tb(III)) assembled from benzophenonedicarboxylate was synthesized and characterized. The organic component is shown to sensitize lanthanide-based emission in both compounds, with quantum yields of 36% (Eu) and 6% (Tb). Luminescence of lanthanide coordination polymers is currently described from a molecular approach. This methodology fails to explain the luminescence of this system. It was found that the band structure of the organic component rather than the molecular triplet state was able to explain the observed luminescence. Deuterated (Ln(C15H9O9)3(D2O)3) and dehydrated (Ln(C15H9O9)3) analogues were also studied. When bound H2O was replaced by D2O, lifetime and emission increased as expected. Upon dehydration, lifetimes increased again, but emission of 1-Eu unexpectedly decreased. This reduction is reasoned through an unprecedented enhancement effect of the compound's luminescence by the OH/OD oscillators in the organic-to-Eu(III) energy transfer process.