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.

Tetradentate Ligand's Chameleon-Like Behavior Offers Recognition of Specific Lanthanides.

The surging demand for high-purity individual lanthanides necessitates the development of novel and exceptionally selective separation strategies. At the heart of these separation systems is an organic compound that, based on its structural features, selectively recognizes the lighter or heavier lanthanides in the trivalent lanthanide (Ln) series. This work emphasizes the significant implications resulting from modifying the donor group configuration within an N,O-based tetradentate ligand and the changes in the solvation environment of Ln ions in the process of separating Lns, with the unique ability to achieve peak selectivity in the light, medium, and heavy Ln regions. The structural rigidity of the bis-lactam-1,10-phenanthroline ligand enforces size-based selectivity, displaying an exceptional affinity for Lns having larger ionic radii such as La. Modifying the ligand by eliminating one preorganization element (phenanthroline → bipyridine) results in the fast formation of complexes with light Lns, but, in the span of hours, the peak selectivity shifts toward middle Ln (Sm), resulting in time-resolved separation. As expected, at low nitric acid concentrations, the neutral tetradentate ligand complexes with Ln3+ ions. However, the change in extraction mechanism is observed at high nitric acid concentrations, leading to the formation and preferential extraction of anionic heavy Ln species, [Ln(NO3)x+3]x-, that self-assemble with two ligands that have undergone protonation, forming intricate supramolecular architectures. The tetradentate ligand that is structurally balanced with restrictive and unrestrictive motifs demonstrates unique, controllable selectivity for light, middle, and heavy Lns, underscoring the pivotal role of solvation and ion interactions within the first and second coordination spheres.

Transient Covalency in Molten Uranium(III) Chloride.

Uranium is arguably the most essential element in the actinide series, serving as a crucial component of nuclear fuels. While U is recognized for engaging the 5f orbitals in chemical bonds under normal conditions, little is known about its coordination chemistry and the nature of bonding interactions at extreme conditions of high temperature. Here we report experimental and computational evidence for the shrinkage of the average U-ligand distance in UCl3 upon the solid-to-molten phase transition, leading to the formation of a significant fraction of short, transient U-Cl bonds with the enhanced involvement of U 5f valence orbitals. These findings reveal that extreme temperatures create an unusual heterogeneous bonding environment around U(III) with distinct inner- and outer-coordination subshells.

Ionic Pairs-Engineered Fluorinated Covalent Organic Frameworks Toward Direct Air Capture of CO2.

The covalent organic frameworks (COFs) possessing high crystallinity and capability to capture low-concentration CO2 (400 ppm) from air are still underdeveloped. The challenge lies in simultaneously incorporating high-density active sites for CO2 insertion and maintaining the ordered structure. Herein, a structure engineering approach is developed to afford an ionic pair-functionalized crystalline and stable fluorinated COF (F-COF) skeleton. The ordered structure of the F-COF is well maintained after the integration of abundant basic fluorinated alcoholate anions, as revealed by synchrotron X-ray scattering experiments. The breakthrough test demonstrates its attractive performance in capturing (400 ppm) CO2 from gas mixtures via O─C bond formation, as indicated by the in situ spectroscopy and operando nuclear magnetic resonance spectroscopy using 13C-labeled CO2 sources. Both theoretical and experimental thermodynamic studies reveal the reaction enthalpy of ≈-40 kJ mol-1 between CO2 and the COF scaffolds. This implies weaker interaction strength compared with state-of-the-art amine-derived sorbents, thus allowing complete CO2 release with less energy input. The structure evolution study from synchrotron X-ray scattering and small-angle neutron scattering confirms the well-maintained crystalline patterns after CO2 insertion. The as-developed proof-of-concept approach provides guidance on anchoring binding sites for direct air capture (DAC) of CO2 in crystalline scaffolds.

Development of 225Ac-doped biocompatible nanoparticles for targeted alpha therapy.

Targeted alpha therapy (TAT) relies on chemical affinity or active targeting using radioimmunoconjugates as strategies to deliver α-emitting radionuclides to cancerous tissue. These strategies can be affected by transmetalation of the parent radionuclide by competing ions in vivo and the bond-breaking recoil energy of decay daughters. The retention of α-emitting radionuclides and the dose delivered to cancer cells are influenced by these processes. Encapsulating α-emitting radionuclides within nanoparticles can help overcome many of these challenges. Poly(lactic-co-glycolic acid) (PLGA) nanoparticles are a biodegradable and biocompatible delivery platform that has been used for drug delivery. In this study, PLGA nanoparticles are utilized for encapsulation and retention of actinium-225 ([225Ac]Ac3+). Encapsulation of [225Ac]Ac3+ within PLGA nanoparticles (Zave = 155.3 nm) was achieved by adapting a double-emulsion solvent evaporation method. The encapsulation efficiency was affected by both the solvent conditions and the chelation of [225Ac]Ac3+. Chelation of [225Ac]Ac3+ to a lipophilic 2,9-bis-lactam-1,10-phenanthroline ligand ([225Ac]AcBLPhen) significantly decreased its release (< 2%) and that of its decay daughters (< 50%) from PLGA nanoparticles. PLGA nanoparticles encapsulating [225Ac]AcBLPhen significantly increased the delivery of [225Ac]Ac3+ to murine (E0771) and human (MCF-7 and MDA-MB-231) breast cancer cells with a concomitant increase in cell death over free [225Ac]Ac3+ in solution. These results demonstrate that PLGA nanoparticles have potential as radionuclide delivery platforms for TAT to advance precision radiotherapy for cancer. In addition, this technology offers an alternative use for ligands with poor aqueous solubility, low stability, or low affinity, allowing them to be repurposed for TAT by encapsulation within PLGA nanoparticles.

Harnessing the Hybridization of a Metal-Organic Framework and Superbase-Derived Ionic Liquid for High-Performance Direct Air Capture of CO2.

Direct air capture (DAC) of CO2 has emerged as the most promising "negative carbon emission" technologies. Despite being state-of-the-art, sorbents deploying alkali hydroxides/amine solutions or amine-modified materials still suffer from unsolved high energy consumption and stability issues. In this work, composite sorbents are crafted by hybridizing a robust metal-organic framework (Ni-MOF) with superbase-derived ionic liquid (SIL), possessing well maintained crystallinity and chemical structures. The low-pressure (0.4 mbar) volumetric CO2 capture assessment and a fixed-bed breakthrough examination with 400 ppm CO2 gas flow reveal high-performance DAC of CO2 (CO2 uptake capacity of up to 0.58 mmol g-1 at 298 K) and exceptional cycling stability. Operando spectroscopy analysis reveals the rapid (400 ppm) CO2 capture kinetics and energy-efficient/fast CO2 releasing behaviors. The theoretical calculation and small-angle X-ray scattering demonstrate that the confinement effect of the MOF cavity enhances the interaction strength of reactive sites in SIL with CO2 , indicating great efficacy of the hybridization. The achievements in this study showcase the exceptional capabilities of SIL-derived sorbents in carbon capture from ambient air in terms of rapid carbon capture kinetics, facile CO2 releasing, and good cycling performance.

Reining in Radium for Nuclear Medicine: Extra-Large Chelator Development for an Extra-Large Ion.

Targeted α therapy (TAT) of soft-tissue cancers using the α particle-emitting radionuclide 223Ra holds great potential because of its favorable nuclear properties, adequate availability, and established clinical use for treating metastatic prostate cancer of the bone. Despite these advantages, the use of 223Ra has been largely overshadowed by other α emitters due to its challenging chelation chemistry. A key criterion that needs to be met for a radionuclide to be used in TAT is its stable attachment to a targeting vector via a bifunctional chelator. The low charge density of Ra2+ arising from its large ionic radius weakens its electrostatic binding interactions with chelators, leading to insufficient complex stability in vivo. In this study, we synthesized and evaluated macropa-XL as a novel chelator for 223Ra. It bears a large 21-crown-7 macrocyclic core and two picolinate pendent groups, which we hypothesized would effectively saturate the large coordination sphere of the Ra2+ ion. The structural chemistry of macropa-XL was first established with the nonradioactive Ba2+ ion using X-ray diffraction and X-ray absorption spectroscopy, which revealed the formation of an 11-coordinate complex in a rare anti pendent-arm configuration. Subsequently, the stability constant of the [Ra(macropa-XL)] complex was determined via competitive cation exchange with 223Ra and 224Ra radiotracers and compared with that of macropa, the current state-of-the-art chelator for Ra2+. A moderate log KML value of 8.12 was measured for [Ra(macropa-XL)], which is approximately 1.5 log K units lower than the stability constant of [Ra(macropa)]. This relative decrease in Ra2+ complex stability for macropa-XL versus macropa was further probed using density functional theory calculations. Additionally, macropa-XL was radiolabeled with 223Ra, and the kinetic stability of the resulting complex was evaluated in human serum. Although macropa-XL could effectively bind 223Ra under mild conditions, the complex appeared to be unstable to transchelation. Collectively, this study sheds additional light on the chelation chemistry of the exotic Ra2+ ion and contributes to the small, but growing, number of chelator development efforts for 223Ra-based TAT.

Construction of Boron- and Nitrogen-Enriched Nanoporous π-Conjugated Networks Towards Enhanced Hydrogen Activation.

Boron-enriched scaffolds have demonstrated unique features and promising performance in the field of catalysis towards the activation of small gas molecules. However, there is still a lack of facile approaches capable of achieving high B doping and abundant porous channels in the targeted catalysts. Herein, construction of boron- and nitrogen-enriched nanoporous π-conjugated networks (BN-NCNs) was achieved via a facile ionothermal polymerization procedure with hexaazatriphenylenehexacarbonitrile [HAT(CN)6 ] sodium borohydride as the starting materials. The as-produced BN-NCN scaffolds were featured by high heteroatoms doping (B up to 23 wt. % and N: up to 17 wt. %) and permanent porosity (surface area up to 759 m2 g-1 mainly contributed by micropores). With the unsaturated bonded B species acting as the active Lewis acid sites and defected N species acting as the active Lewis base sites, those BN-NCNs delivered attractive catalytic performance towards H2 activation/dissociation in both gaseous and liquid phase, acting as efficient metal-free heterogeneous frustrated Lewis pairs (FLPs) catalysts in hydrogenation procedures.

Mixed-Valence CuI /CuIII Metal-Organic Frameworks with Non-innocent Ligand for Multielectron Transfer.

We report two novel three-dimensional copper-benzoquinoid metal-organic frameworks (MOFs), [Cu4 L3 ]n and [Cu4 L3 ⋅ Cu(iq)3 ]n (LH4 =1,4-dicyano-2,3,5,6-tetrahydroxybenzene, iq=isoquinoline). Spectroscopic techniques and computational studies reveal the unprecedented mixed valency in MOFs, formal Cu(I)/Cu(III). This is the first time that formally Cu(III) species are witnessed in metal-organic extended solids. The coordination between the mixed-valence metal and redox-non-innocent ligand L, which promotes through-bond charge transfer between Cu metal sites, allows better metal-ligand orbital overlap of the d-π conjugation, leading to strong long-range delocalization and semiconducting behavior. Our findings highlight the significance of the unique mixed valency between formal Cu(I) and highly-covalent Cu(III), non-innocent ligand, and pore environments of these bench stable Cu(III)-containing frameworks on multielectron transfer and electrochemical properties.

Defect-Regulated Frustrated-Lewis-Pair Behavior of Boron Nitride in Ambient Pressure Hydrogen Activation.

The construction of heterogeneous frustrated Lewis pairs (FLPs) with performance comparable to or surpassing the homogeneous counterparts in H2 activation is a long-standing challenge. Herein, sterically hindered Lewis acid ("B" center) and Lewis base ("N" center) sites were anchored within the rigid lattice of highly crystalline hexagonal boron nitride (h-BN) scaffolds. The active sites were created via precision defect regulation during the molten-salt-involved (NaNH2 and NaBH4) h-BN construction procedure. The as-afforded h-BN scaffolds achieved highly efficient H2/D2 activation and dissociation under ambient pressure via FLP-like behavior, and attractive catalytic efficiency in hydrogenation reactions surpassing the current heterogeneous analogues.

Complete Description of the LaCl3-NaCl Melt Structure and the Concept of a Spacer Salt That Causes Structural Heterogeneity.

Lanthanides are important fission products in molten salt reactors, and understanding their structure and that of their mixtures is relevant to many scientific and technological problems including the recovery and separation of rare earth elements using molten salt electrolysis. The literature on molten salts and specifically on LaCl3 and LaCl3-NaCl mixtures is often fragmented, with different experiments and simulations coinciding in their explanation for certain structural results but contradicting or questioning for others. Given the very practical importance that actinide and lanthanide salts have for energy applications, it is imperative to arrive at a clear unified picture of their local and intermediate-range structure in the neat molten state and when mixed with other salts. This article aims to unequivocally answer a set of specific questions: is it correct to think of long-lived octahedral coordination structures for La3+? What is the nature as a function of temperature of networks and intermediate-range order particularly upon dilution of the trivalent ion salt? Is the so-called scattering first sharp diffraction peak (FSDP) for neat LaCl3 truly indicative of intermediate-range order? If so, why is there a new lower-q peak when mixed with NaCl? Are X-ray scattering and Raman spectroscopy results fully consistent and easily described by simulation results? We will show that answers to these questions require that we abandon the idea of a most prominent coordination state for M3+ ions and instead think of multiple competing coordination states in exchange due to significant thermal energy in the molten state.

Two Ligands of Interest in Recovering Uranium from the Oceans: The Correct Formation Constants of the Uranyl(VI) Cation with 2,2'-Bipyridyl-6,6'-dicarboxylic Acid and 1,10-Phenanthroline-2,9-dicarboxylic Acid.

The ligands BDA (2,2'-bipyridyl-6,6'-dicarboxylic acid) and PDA (1,10-phenanthroline-2,9-dicarboxylic acid) are of interest as functional group types for ion-exchange materials for extracting uranium from the oceans, reported in a previous paper for PDA Lashley, M. A. ( Inorg. Chem. 2016 55 10818 10829). Yang, Y. ( Inorg. Chem. 2019, 58, 6064 6074) have published what they claim to be a more accurate result for the formation of the UO22+/PDA complex of log K1 = 22.84 compared with our reported value of log K1 = 16.5, as well as log K1 = 21.52 for the BDA complex. The determination of log K1 for the PDA and BDA complexes with the UO22+ cation was carried out by Yang et al. using a competition reaction between DTPA (diethylenetriamine pentaacetic acid) and BDA or PDA, monitoring the absorbance due to the BDA and PDA ligands. This competition method using absorbance versus pH titrations was developed for determining the formation constants of the complexes of several polypyridyl ligands plus PDA complexes of metal ions, which were too stable for log K determination by competition with protons. A key feature of such titrations is that in the competition reaction, the displacement of the pyridyl donor ligand (e.g., PDA) by the competing ligand (e.g., DTPA), the absorbance spectrum of the displaced pyridyl donor ligand should be observed. Competing ligands used to date have been EDTA (ethylenediamine tetraacetic acid), DTPA, or the hydroxide ion. In the study of Yang et al., no such displaced PDA or BDA was apparent in the absorbance spectra in their titrations so that their reported log K1 values have no validity. Their log K1 values are so much higher than log K1 for the uranyl DTPA complex (∼13.6) that DTPA could not possibly displace BDA or PDA from the uranyl cation, and a competition reaction could not possibly occur. We report the correct value of log K1 = 15.4 (ionic strength = zero) for the uranyl BDA complex, to illustrate the correct determination of such a constant by a competition reaction between BDA and hydroxide, showing how the characteristic absorbance spectrum for a BDA complex, here the UO22+ complex, disappears, and the distinctive absorbance spectrum of the free nonprotonated BDA ligand appears as the pH is increased, and BDA is displaced by the hydroxide ion.

Improving the theoretical description of Ln(III)/An(III) separation with phosphinic acid ligands: a benchmarking study of structure and selectivity.

The efficient separation of trivalent lanthanides from minor actinides with soft-donor ligands, while showing experimental promise, has theorists continuing to search for suitable approaches for describing and interpreting selectivity. To remedy this, we employ several computational methods in describing the structure of model M(H2PX2)3 complexes, with M = Eu and Am, and X = O, S, Se, and Te, and predicting the selectivity of model phosphinic acid ligands in Eu(III)/Am(III) separation. After first establishing a set of MP2 and CCSD(T)-DKH3 results as benchmarks, we evaluate several density functionals and descriptions of valence shells for their accuracy with respect to metal-ligand bonding and selectivity. We find that commonly employed functionals with a 0-27% range of exact exchange used with small-core effective core potentials or with an explicit treatment of the relativistic effects (DKH2) incorrectly predict a decrease in the metal-ligand bond distance in going from Eu(III) to Am(III) and completely fail to track a selectivity trend, even giving a wrong sign for some or all ligands. Surprisingly, when these functionals are used in conjunction with an f-in-core description of metal ions, the correct trend in selectivity is recovered, though Am-X distances are overestimated in relation to Eu-X. Functionals with high components of exact exchange (50%) and double-hybrid functionals are reasonably aligned with benchmark results, pointing to the problems of DFT with small exact exchange fractions to handle f-electrons. Natural bond orbital analyses reveal that these poorly performing functionals disproportionately overpopulate outer f orbitals in the model complexes. We anticipate that recommendations resulting from this work will lead to more accurate theoretical descriptions of lanthanide/actinide selectivity with soft-donor chalcogen-based ligands in the future.

Exploring Soft Donor Character of the N-2-Pyrazinylmethyl Group by Coordinating Trivalent Actinides and Lanthanides Using Aminopolycarboxylates.

The trivalent f-element coordination chemistry of a novel aminopolycarboxylate complexant was investigated. The novel reagent is an octadentate complexant that resembles diethylenetriamine-N,N,N',N″,N″-pentaacetic acid (DTPA), but a single N-acetate pendant arm was substituted with a N-2-pyrazinylmethyl functional group. Thermodynamic studies of ligand protonation and trivalent lanthanide, americium and curium, complexation by N-2-pyrazinylmethyldiethylenetriamine-N,N',N″,N″-tetraacetic acid (DTTA-PzM) emphasize the strong electron withdrawing influence of the N-2-pyrazinylmethyl group. Specifically, DTTA-PzM is more acidic compared to a N-2-pyridinylmethyl-substituted structural equivalent, DTTA-PyM, with a substantial lowering of pK7, corresponding to the protonation of a second aliphatic amine site. The participation of the pyrizyl nitrogen in the metal ion coordination sphere is evident from the fluorescence lifetime decay measurements of metal hydration and the interpretation of the stability constants for ML- and MHL(aq) complexes. The overall conditional stability constants for the trivalent f-element complexation by DTTA-PzM complexes decrease, relative to DTTA-PyM, as expected based on the lower basicity of pyrazine in water relative to pyridine. Replacement of the N-2-pyridinylmethyl group with N-2-pyrazinylmethyl, while enhancing the total acidity of DTTA-PzM, also reduces its softness, as manifested by a small lowering of ß101Am/Nd and liquid-liquid separation of trivalent lanthanides from trivalent americium. Despite this, the 4f/5f separation is doubled when DTTA-PzM replaces DTPA as an aqueous complexant in solvent extraction.

Structure and dynamics of the molten alkali-chloride salts from an X-ray, simulation, and rate theory perspective.

Molten salts are of great interest as alternative solvents, electrolytes, and heat transfer fluids in many emerging technologies. The macroscopic properties of molten salts are ultimately controlled by their structure and ion dynamics at the microscopic level and it is therefore vital to develop an understanding of these at the atomistic scale. Herein, we present high-energy X-ray scattering experiments combined with classical and ab initio molecular dynamics simulations to elucidate structural and dynamical correlations across the family of alkali-chlorides. Computed structure functions and transport properties are in reasonably good agreement with experiments providing confidence in our analysis of microscopic properties based on simulations. For these systems, we also survey different rate theory models of anion exchange dynamics in order to gain a more sophisticated understanding of the short-time correlations that are likely to influence transport properties such as conductivity. The anion exchange process occurs on the picoseconds time scale at 1100 K and the rate increases in the order KCl < NaCl < LiCl, which is in stark contrast to the ion pair dissociation trend in aqueous solutions. Consistent with the trend we observe for conductivity, the cationic size/mass, as well as other factors specific to each type of rate theory, appear to play important roles in the anion exchange rate trend.

Dynamic Effects of Laser Action on Quasi-Two-Dimensional Dusty Plasma Systems of Charged Particles.

We present the results of an experimental study of the behavior of a colloidal plasma system formed by copper-coated and uncoated polymer particles under the action of laser irradiation. A comparative study of particle velocity distribution profiles depending on the power of the pushing laser was conducted. In the case of uncoated melamine-formaldehyde (MF) particles, we observed the well-known action of light pressure, causing shear stress in the colloidal plasma structure and leading to the occurrence of a laminar flow within the affected area. For the copper-coated MF particles, we revealed some additional patterns of behavior for the dust particles, i.e., kinetic temperature growth due to laser radiation absorption by the copper coating, as well as the appearance of chaotic particle motion. We believe that this happens due to the existence of defects in the coating, causing asymmetric heating of the particles, which in turn leads to chaotic deviations of the photophoretic force pushing the particles in different directions.

Efficient Separation of Light Lanthanides(III) by Using Bis-Lactam Phenanthroline Ligands.

Due to the ever-increasing demand for high-purity individual rare-earth elements, novel and highly selective separation processes are increasingly sought after. Herein, we report a separation protocol that employs shape-persistent 2,9-bis-lactam-1,10-phenanthroline (BLPhen) ligands exhibiting unparalleled selectivity for light trivalent lanthanides. The highly preorganised binding pockets of the ligands allowed for the separation of lanthanides with high fidelity, even in the presence of competing transition metals, in a biphasic separation system. Notably, the selectivity trends of the BLPhen ligands towards metal ions across the lanthanide series can be chemically modulated by altering the molecular rigidity of the extractant.

Influence of a Heterocyclic Nitrogen-Donor Group on the Coordination of Trivalent Actinides and Lanthanides by Aminopolycarboxylate Complexants.

The novel metal chelator N-2-(pyridylmethyl)diethylenetriamine-N,N',N″,N″-tetraacetic acid (DTTA-PyM) was designed to replace a single oxygen-donor acetate group of the well-known aminopolycarboxylate complexant diethylenetriamine-N,N,N',N″,N″-pentaacetic acid (DTPA) with a nitrogen-donor 2-pyridylmethyl. Potentiometric, spectroscopic, computational, and radioisotope distribution methods show distinct differences for the 4f and 5f coordination environments and enhanced actinide binding due to the nitrogen-bearing heterocyclic moiety. The Am3+, Cm3+, and Ln3+ complexation studies for DTTA-PyM reveal an enhanced preference, relative to DTPA, for trivalent actinide binding. Fluorescence studies indicate no changes to the octadentate coordination of trivalent curium, while evidence of heptadentate complexation of trivalent europium is found in mixtures containing EuHL(aq) complexes at the same aqueous acidity. The denticity change observed for Eu3+ suggests that complex protonation occurs on the pyridyl nitrogen. Formation of the CmHL(aq) complex is likely due to the protonation of an available carboxylate group because the carbonyl oxygen can maintain octadentate coordination through a rotation. The observed suppressed protonation of the pyridyl nitrogen in the curium complexes may be attributed to stronger trivalent actinide binding by DTTA-PyM. Density functional theory calculations indicate that added stabilization of the actinide complexes with DTTA-PyM may originate from π-back-bonding interactions between singly occupied 5f orbitals of Am3+ and the pyridyl nitrogen. The differences between the stabilities of trivalent actinide chelates (Am3+, Cm3+) and trivalent lanthanide chelates (La3+-Lu3+) are observed in liquid-liquid extraction systems, yielding unprecedented 4f/5f differentiation when using DTTA-PyM as an aqueous holdback reagent. In addition, the enhanced nitrogen-donor softness of the new DTTA-PyM chelator was perturbed by adding a fluorine onto the pyridine group. The comparative characterization of N-(3-fluoro-2-pyridylmethyl)diethylenetriamine-N,N',N″,N″-tetraacetic acid (DTTA-3-F-PyM) showed subdued 4f/5f differentiation due to the presence of this electron-withdrawing group.

Trefoil-Shaped Outer-Sphere Ion Clusters Mediate Lanthanide(III) Ion Transport with Diglycolamide Ligands.

Outer-sphere ion clusters are inferred in many important natural and technological processes, but their mechanisms of assembly and solution structures are difficult to define. Here, we characterize trefoil-shaped outer-sphere lanthanide chloride and nitrate ion clusters in hydrocarbon solutions formed during liquid-liquid extraction with diglycolamide ligands. These are assembled through steric and electrostatic forces, where the anions reside in equidistant "clefts" between coordinating diglycolamide ligands in positions that satisfy both repulsive and attractive ion-ion interactions. Our study shows how sterically directed electrostatic interactions may assemble stable outer-sphere ion clusters in organic solutions, elucidating new strategies for controlling ion cluster assembly and extraction.

"Straining" to Separate the Rare Earths: How the Lanthanide Contraction Impacts Chelation by Diglycolamide Ligands.

The subtle energetic differences underpinning adjacent lanthanide discrimination are explored with diglycolamide ligands. Our approach converges liquid-liquid extraction experiments with solution-phase X-ray absorption spectroscopy (XAS) and density functional theory (DFT) simulations, spanning the lanthanide series. The homoleptic [(DGA)3Ln]3+ complex was confirmed in the organic extractive solution by XAS, and this was modeled using DFT. An interplay between steric strain and coordination energies apparently gives rise to a nonlinear trend in discriminatory lanthanide ion complexation across the series. Our results highlight the importance of optimizing chelate molecular geometry to account for both coordination interactions and strain energies when designing new ligands for efficient adjacent lanthanide separation for rare-earth refining.