Structure and Dynamics of NaCl/KCl/CaCl2-EuCln (n = 2, 3) Molten Salts.

Modern molten salt reactor design and the techniques of electrorefining spent nuclear fuels require a better understanding of the chemical and physical behavior of lanthanide/actinide ions with different oxidation states dissolved in various solvent salts. The molecular structures and dynamics that are driven by the short-range interactions between solute cations and anions and long-range solute and solvent cations are still unclear. In order to study the structural change of solute cations caused by different solvent salts, we performed first-principles molecular dynamics simulations in molten salts and extended X-ray absorption fine structure (EXAFS) measurements for the cooled molten salt samples to identify the local coordination environment of Eu2+ and Eu3+ ions in CaCl2, NaCl, and KCl. The simulations reveal that with the increasing polarizing the outer sphere cations from K+ to Na+ to Ca2+, the coordination number (CN) of Cl- in the first solvation shell increases from 5.6 (Eu2+) and 5.9 (Eu3+) in KCl to 6.9 (Eu2+) and 7.0 (Eu3+) in CaCl2. This coordination change is validated by the EXAFS measurements, in which the CN of Cl- around Eu increases from 5 in KCl to 7 in CaCl2. Our simulation shows that the fewer Cl- ions coordinated to Eu leads to a more rigid first coordination shell with longer lifetime. Furthermore, the diffusivities of Eu2+/Eu3+ are related to the rigidity of their first coordination shell of Cl-: the more rigid the first coordination shell is, the slower the solute cations diffuse.

Oxidizing Americium(III) with Sodium Bismuthate in Acidic Aqueous Solutions.

Historic perspectives describing f-elements as being redox "inactive" are fading. Researchers continue to discover new oxidation states that are not as inaccessible as once assumed for actinides and lanthanides. Inspired by those contributions, we studied americium(III) oxidation in aqueous media under air using NaBiO3(s). We identified selective oxidation of Am3+(aq) to AmO22+(aq) or AmO21+(aq) could be achieved by changing the aqueous matrix identity. AmO22+(aq) formed in H3PO4(aq) (1 M) and AmO21+(aq) formed in dilute HCl(aq) (0.1 M). These americyl products were stable for weeks in solution. Also included is a method to recover 243Am from the americium and bismuth mixtures generated during these studies.

Advancing the Am Extractant Design through the Interplay among Planarity, Preorganization, and Substitution Effects.

Advancing the field of chemical separations is important for nearly every area of science and technology. Some of the most challenging separations are associated with the americium ion Am(III) for its extraction in the nuclear fuel cycle, 241Am production for industrial usage, and environmental cleanup efforts. Herein, we study a series of extractants, using first-principle calculations, to identify the electronic properties that preferentially influence Am(III) binding in separations. As the most used extractant family and because it affords a high degree of functionalization, the polypyridyl family of extractants is chosen to study the effects of the planarity of the structure, preorganization of coordinating atoms, and substitution of various functional groups. The actinyl ions are used as a structurally simplified surrogate model to quickly screen the most promising candidates that can separate these metal ions. The down-selected extractants are then tested for the Am(III)/Eu(III) system. Our results show that π interactions, especially those between the central terpyridine ring and Am(III), play a crucial role in separation. Adding an electron-donating group onto the terpyridine backbone increases the binding energies to Am(III) and stabilizes Am-terpyridine coordination. Increasing the planarity of the extractant increases the binding strength as well, although this effect is found to be rather weak. Preorganizing the coordinating atoms of an extractant to their binding configuration as in the bound metal complex speeds up the binding process and significantly improves the kinetics of the separation process. This conclusion is validated by the synthesized 1,2-dihydrodipyrido[4,3-b;5,6-b]acridine (13) extractant, a preorganized derivative of the terpyridine extractant, which we experimentally showed was four times more effective than terpyridine at separating Am3+ from Eu3+ (SFAm/Eu ∼ 23 ± 1).

Characterizing Polyoxovanadate-Alkoxide Clusters Using Vanadium K-Edge X-Ray Absorption Spectroscopy.

A number of technologies would benefit from developing inorganic compounds and materials with specific electronic and magnetic exchange properties. Unfortunately, designing compounds with these properties is difficult because metal⋅⋅⋅metal coupling schemes are hard to predict and control. Fully characterizing communication between metals in existing compounds that exhibit interesting properties could provide valuable insight and advance those predictive capabilities. One such class of molecules are the series of Lindqvist iron-functionalized and hexavanadium polyoxovanadate-alkoxide clusters, which we characterized here using V K-edge X-ray absorption spectroscopy. Substantial changes in the pre-edge peak intensities were observed that tracked with the V 3d-electron count. The data also suggested substantial delocalization between the vanadium cations. Meanwhile, the FeIII cations were electronically isolated from the polyoxovanadate core.

Gamma and Decay Energy Spectroscopy Measurements of Trinitite.

We report gamma ray spectroscopy measurements of trinitite samples and analogous samples obtained from detonation sites in Nevada and Semipalatinsk, as well as in situ measurements of topsoil at the Trinity site. We also report the first isotopic composition measurements of trinitite using the novel forensics technique of decay energy spectroscopy (DES) as a complement to traditional forensics techniques. Our gamma spectroscopy and DES measurements are compared to other published results.

Resonant inelastic X-ray scattering using a miniature dispersive Rowland refocusing spectrometer.

X-ray absorption spectroscopy (XAS) beamlines worldwide are steadily increasing their emphasis on full photon-in/photon-out spectroscopies, such as resonant inelastic X-ray scattering (RIXS), resonant X-ray emission spectroscopy (RXES) and high energy resolution fluorescence detection XAS (HERFD-XAS). In such cases, each beamline must match the choice of emission spectrometer to the scientific mission of its users. Previous work has recently reported a miniature tender X-ray spectrometer using a dispersive Rowland refocusing (DRR) geometry that functions with high energy resolution even with a large X-ray spot size on the sample [Holden et al. (2017). Rev. Sci. Instrum. 88, 073904]. This instrument has been used in the laboratory in multiple studies of non-resonant X-ray emission spectroscopy using a conventional X-ray tube, though only for preliminary measurements at a low-intensity microfocus synchrotron beamline. This paper reports an extensive study of the performance of a miniature DRR spectrometer at an unfocused wiggler beamline, where the incident monochromatic flux allows for resonant studies which are impossible in the laboratory. The results support the broader use of the present design and also suggest that the DRR method with an unfocused beam could have important applications for materials with low radiation damage thresholds and that would not survive analysis on focused beamlines.

Preparation of an Actinium-228 Generator.

Advances in targeted α-therapies have increased the interest in actinium (Ac), whose chemistry is poorly defined due to scarcity and radiological hazards. Challenges associated with characterizing Ac3+ chemistry are magnified by its 5f06d0 electronic configuration, which precludes the use of many spectroscopic methods amenable to small amounts of material and low concentrations (like EPR, UV-vis, fluorescence). In terms of nuclear spectroscopy, many actinium isotopes (225Ac and 227Ac) are equally "unfriendly" because the actinium α-, ß-, and γ-emissions are difficult to resolve from the actinium daughters. To address these issues, we developed a method for isolating an actinium isotope (228Ac) whose nuclear properties are well-suited for γ-spectroscopy. This four-step procedure isolates 228Ra from naturally occurring 232Th. The relatively long-lived 228Ra (t1/2 = 5.75(3) years) radioisotope subsequently decays to 228Ac. Because the 228Ac decay rate [t1/2 = 6.15(2) h] is fast, 228Ac rapidly regenerates after being harvested from the 228Ra parent. The resulting 228Ac generator provides frequent and long-term access (of many years) to the spectroscopically "friendly" 228Ac radionuclide. We have demonstrated that the 228Ac product can be routinely "milked" from this generator on a daily basis, in chemically pure form, with high specific activity and in excellent yield (∼95%). Hence, in the same way that developing synthesis routes to new starting materials has advanced coordination chemistry for many metals by broadening access, this 228Ac generator has the potential to broaden actinium access for the inorganic community, facilitating the characterization of actinium chemical behavior.

A Solid-State Support for Separating Astatine-211 from Bismuth.

Increasing access to the short-lived α-emitting radionuclide astatine-211 (211At) has the potential to advance targeted α-therapeutic treatment of disease and to solve challenges facing the medical community. For example, there are numerous technical needs associated with advancing the use of 211At in targeted α-therapy, e.g., improving 211At chelates, developing more effective 211At targeting, and characterizing in vivo 211At behavior. There is an insufficient understanding of astatine chemistry to support these efforts. The chemistry of astatine is one of the least developed of all elements on the periodic table, owing to its limited supply and short half-life. Increasing access to 211At could help address these issues and advance understanding of 211At chemistry in general. We contribute here an extraction chromatographic processing method that simplifies 211At production in terms of purification. It utilizes the commercially available Pre-Filter resin to rapidly (<1.5 h) isolate 211At from irradiated bismuth targets (Bi decontamination factors ≥876 000), in reasonable yield (68-55%) and in a form that is compatible for subsequent in vivo study. We are excited about the potential of this procedure to address 211At supply and processing/purification problems.

Advancing Chelation Chemistry for Actinium and Other +3 f-Elements, Am, Cm, and La.

A major chemical challenge facing implementation of 225Ac in targeted alpha therapy-an emerging technology that has potential for treatment of disease-is identifying an 225Ac chelator that is compatible with in vivo applications. It is unclear how to tailor a chelator for Ac binding because Ac coordination chemistry is poorly defined. Most Ac chemistry is inferred from radiochemical experiments carried out on microscopic scales. Of the few Ac compounds that have been characterized spectroscopically, success has only been reported for simple inorganic ligands. Toward advancing understanding in Ac chelation chemistry, we have developed a method for characterizing Ac complexes that contain highly complex chelating agents using small quantities (µg) of 227Ac. We successfully characterized the chelation of Ac3+ by DOTP8- using EXAFS, NMR, and DFT techniques. To develop confidence and credibility in the Ac results, comparisons with +3 cations (Am, Cm, and La) that could be handled on the mg scale were carried out. We discovered that all M3+ cations (M = Ac, Am, Cm, La) were completely encapsulated within the binding pocket of the DOTP8- macrocycle. The computational results highlighted the stability of the M(DOTP)5- complexes.

Energy-Degeneracy-Driven Covalency in Actinide Bonding.

Evaluating the nature of chemical bonding for actinide elements represents one of the most important and long-standing problems in actinide science. We directly address this challenge and contribute a Cl K-edge X-ray absorption spectroscopy and relativistic density functional theory study that quantitatively evaluates An-Cl covalency in AnCl62- (AnIV = Th, U, Np, Pu). The results showed significant mixing between Cl 3p- and AnIV 5f- and 6d-orbitals (t1u*/t2u* and t2 g*/eg *), with the 6d-orbitals showing more pronounced covalent bonding than the 5f-orbitals. Moving from Th to U, Np, and Pu markedly changed the amount of M-Cl orbital mixing, such that AnIV 6d - and Cl 3p-mixing decreased and metal 5f - and Cl 3p-orbital mixing increased across this series.

Advancing Understanding of the +4 Metal Extractant Thenoyltrifluoroacetonate (TTA-); Synthesis and Structure of MIVTTA4 (MIV = Zr, Hf, Ce, Th, U, Np, Pu) and MIII(TTA)4- (MIII = Ce, Nd, Sm, Yb).

Thenoyltrifluoroacetone (HTTA)-based extractions represent popular methods for separating microscopic amounts of transuranic actinides (i.e., Np and Pu) from macroscopic actinide matrixes (e.g. bulk uranium). It is well-established that this procedure enables +4 actinides to be selectively removed from +3, + 5, and +6 f-elements. However, even highly skilled and well-trained researchers find this process complicated and (at times) unpredictable. It is difficult to improve the HTTA extraction-or find alternatives-because little is understood about why this separation works. Even the identities of the extracted species are unknown. In addressing this knowledge gap, we report here advances in fundamental understanding of the HTTA-based extraction. This effort included comparatively evaluating HTTA complexation with +4 and +3 metals (MIV = Zr, Hf, Ce, Th, U, Np, and Pu vs MIII = Ce, Nd, Sm, and Yb). We observed +4 metals formed neutral complexes of the general formula MIV(TTA)4. Meanwhile, +3 metals formed anionic MIII(TTA)4- species. Characterization of these M(TTA)4x- ( x = 0, 1) compounds by UV-vis-NIR, IR, 1H and 19F NMR, single-crystal X-ray diffraction, and X-ray absorption spectroscopy (both near-edge and extended fine structure) was critical for determining that NpIV(TTA)4 and PuIV(TTA)4 were the primary species extracted by HTTA. Furthermore, this information lays the foundation to begin developing and understanding of why the HTTA extraction works so well. The data suggest that the solubility differences between MIV(TTA)4 and MIII(TTA)4- are likely a major contributor to the selectivity of HTTA extractions for +4 cations over +3 metals. Moreover, these results will enable future studies focused on explaining HTTA extractions preference for +4 cations, which increases from Np IV to PuIV, HfIV, and ZrIV.

A Pseudotetrahedral Uranium(V) Complex.

A series of uranium amides were synthesized from N, N, N-cyclohexyl(trimethylsilyl)lithium amide [Li][N(TMS)Cy] and uranium tetrachloride to give U(NCySiMe3) x(Cl)4- x, where x = 2, 3, or 4. The diamide was isolated as a bimetallic, bridging lithium chloride adduct ((UCl2(NCyTMS)2)2-LiCl(THF)2), and the tris(amide) was isolated as the lithium chloride adduct of the monometallic species (UCl(NCyTMS)3-LiCl(THF)2). The tetraamide complex was isolated as the four-coordinate pseudotetrahedron. Cyclic voltammetry revealed an easily accessible reversible oxidation wave, and upon chemical oxidation, the UV amido cation was isolated in near-quantitative yields. The synthesis of this family of compounds allows a direct comparison of the electronic structure and properties of isostructural UIV and UV tetraamide complexes. Spectroscopic investigations consisting of UV-vis, NIR, MCD, EPR, and U L3-edge XANES, along with density functional and wave function calculations, of the four-coordinate UIV and UV complexes have been used to understand the electronic structure of these pseudotetrahedral complexes.

Covalency in Americium(III) Hexachloride.

Developing a better understanding of covalency (or orbital mixing) is of fundamental importance. Covalency occupies a central role in directing chemical and physical properties for almost any given compound or material. Hence, the concept of covalency has potential to generate broad and substantial scientific advances, ranging from biological applications to condensed matter physics. Given the importance of orbital mixing combined with the difficultly in measuring covalency, estimating or inferring covalency often leads to fiery debate. Consider the 60-year controversy sparked by Seaborg and co-workers ( Diamond, R. M.; Street, K., Jr.; Seaborg, G. T. J. Am. Chem. Soc. 1954 , 76 , 1461 ) when it was proposed that covalency from 5f-orbitals contributed to the unique behavior of americium in chloride matrixes. Herein, we describe the use of ligand K-edge X-ray absorption spectroscopy (XAS) and electronic structure calculations to quantify the extent of covalent bonding in-arguably-one of the most difficult systems to study, the Am-Cl interaction within AmCl63-. We observed both 5f- and 6d-orbital mixing with the Cl-3p orbitals; however, contributions from the 6d-orbitals were more substantial. Comparisons with the isoelectronic EuCl63- indicated that the amount of Cl 3p-mixing with EuIII 5d-orbitals was similar to that observed with the AmIII 6d-orbitals. Meanwhile, the results confirmed Seaborg's 1954 hypothesis that AmIII 5f-orbital covalency was more substantial than 4f-orbital mixing for EuIII.

Buoyancy driven mixing of miscible fluids by volumetric energy deposition of microwaves.

An experiment that seeks to investigate buoyancy driven mixing of miscible fluids by microwave volumetric energy deposition is presented. The experiment involves the use of a light, non-polar fluid that initially rests on top of a heavier fluid which is more polar. Microwaves preferentially heat the polar fluid, and its density decreases due to thermal expansion. As the microwave heating continues, the density of the lower fluid eventually becomes less than that of the upper, and buoyancy driven Rayleigh-Taylor mixing ensues. The choice of fluids is crucial to the success of the experiment, and a description is given of numerous fluid combinations considered and characterized. After careful consideration, the miscible pair of toluene/tetrahydrofuran (THF) was determined as having the best potential for successful volumetric energy deposition buoyancy driven mixing. Various single fluid calibration experiments were performed to facilitate the development of a heating theory. Thereafter, results from two-fluid mixing experiments are presented that demonstrate the capability of this novel Rayleigh-Taylor driven experiment. Particular interest is paid to the onset of buoyancy driven mixing and unusual aspects of the experiment in the context of typical Rayleigh-Taylor driven mixing.

A combined inorganic-organic titanium-44/scandium-44g radiochemical generator.

Scandium-44g (t1/2 = 4.0 h) is an emerging radioisotope for positron emission tomography. It can be produced with a radiochemical generator using its long-lived parent, titanium-44 (t1/2 = 59.1 years). This work presents a new inorganic substrate for 44Ti/44gSc radiochemical generator design based on porous TiO2 microbeads (80 µm and 110 µm particle size, 60 Å pores). Comprehensive evaluation of conditions optimal for generator construction (44Ti loading) and use (44gSc elution) is provided in three steps. For stable 44Ti loading onto titania, heat-treatment at 180 °C for 90 min is shown to be effective while 0.3 M HCl(aq) is identified as the medium of choice for 44gSc elution. Two titania-based 3.6 MBq generators prepared under optimized conditions are characterized with respect to 44gSc recovery and 44Ti breakthrough. Each of these generators employed a different guard substrate to minimize 44Ti breakthrough, TiO2 microbeads and ZR resin. Both are shown to provide comparable 44gSc recoveries close to 50% but differ in 44Ti breakthrough, which is significantly lower with the organic ZR resin guard substrate at 0.0002%. This concept represents a new inorganic-organic approach to 44Ti/44gSc generator design. Benefits of both substrates are exploited: TiO2 has potential for durability necessary for utilizing the long half-life of the 44Ti parent while ZR resin guard segments minimize 44Ti breakthrough.

Production of zirconium-88 via proton irradiation of metallic yttrium and preparation of target for neutron transmission measurements at DICER.

A process for the production of tens to hundreds of GBq amounts of zirconium-88 (88Zr) using proton beams on yttrium was developed. For this purpose, yttrium metal targets (≈20 g) were irradiated in a ~16 to 34 MeV proton beam at a beam current of 100-200 µA at the Los Alamos Isotope Production Facility (IPF). The 88Zr radionuclide was produced and separated from the yttrium targets using hydroxamate resin with an elution yield of 94(5)% (1σ). Liquid DCl solution in D2O was selected as a suitable 88Zr sample matrix due to the high neutron transmission of deuterium compared to hydrogen and an even distribution of 88Zr in the sample matrix. The separated 88Zr was dissolved in DCl and 8 µL of the obtained solution was transferred to a tungsten sample can with a 1.2 mm diameter hole using a syringe and automated filling station inside a hot cell. Neutron transmission of the obtained 88Zr sample was measured at the Device for Indirect Capture Experiments on Radionuclides (DICER).

Evaluation of 134Ce as a PET imaging surrogate for antibody drug conjugates incorporating 225Ac.

INTRODUCTION: The in vivo generator 134Ce/134La has the potential to serve as a PET imaging surrogate for both alpha-emitting 225Ac and 227Th radionuclides due to the unique CeIII/CeIV redox couple and the relatively long half-life of 134Ce. The purpose of this study was to demonstrate the compatibility of 134Ce with DOTA-based antibody drug conjugates, which would act as therapeutic agents when incorporating 225Ac. METHODS: The in vivo biodistributions of [134Ce]Ce-DOTA and [134Ce]Ce-citrate were assayed by microPET imaging over 25 h in Swiss Webster mice to determine the in vivo stability of the [134Ce]Ce-DOTA complex. L3-edge X-ray absorption spectroscopy measurements were used to confirm the Ce oxidation state and the formation of a fully coordinated Ce-DOTA complex. The in vivo biodistribution of [134Ce]Ce-DOTA-Trastuzumab was assayed over 147 h by microPET imaging in SK-OV-3 tumor-bearing NOD SCID mice to evaluate tumor uptake and in vivo stability. Mice were euthanized at 214 h after administration of the radiolabeled antibody conjugate, and imaged 1 h later. An ex vivo biodistribution experiment was then performed in order to corroborate the PET images. RESULTS: [134Ce]Ce-DOTA displayed rapid renal elimination and high in vivo stability over 25 h, with negligible bone and liver uptake, in comparison to [134Ce]Ce-citrate. L3-edge X-ray absorption spectroscopy experiments confirmed the 3+ oxidation state within the stable Ce-DOTA complex. MicroPET images of [134Ce]Ce-DOTA-Trastuzumab displayed elevated tumor uptake over 214 h, with minimal bone and liver uptake analogous to previously reported [225Ac]Ac-DOTA-Trastuzumab biodistribution results, and the ex vivo biodistribution of [134Ce]Ce-DOTA-Trastuzumab corroborated the final PET images. CONCLUSION: These results demonstrate that 134Ce allows for long-term tumor targeting with DOTA-based antibody drug conjugates and may therefore be used to trace antibody drug conjugates incorporating 225Ac.

Photochemical separation of plutonium from uranium.

Plutonium-based technologies would benefit if chemical hazards for purifying plutonium were reduced. One critical processing step where improvements could be impactful is the adjustment of plutonium oxidation-states during separations. This transformation often requires addition of redox agents. Unfortunately, many of the redox agents used previously cannot be used today because their properties are deemed incompatible with modern day processing facilities and waste stream safety requirements. We demonstrated herein that photochemistry can be used as an alternative to those chemical agents. We observed that (1) Pu4+ → Pu3+ and UO22+ → U4+ photoreduction proceeded in HCl(aq) and HNO3(aq) and (2) photogenerated Pu3+(aq) and U4+(aq) could be separated using anion exchange chromatography (high yield, >90%; good separation factor, 322).

Synthesis, solid-state, solution, and theoretical characterization of an "in-cage" scandium-NOTA complex.

Developing chelators that strongly and selectively bind rare-earth elements (Sc, Y, La, and lanthanides) represents a longstanding fundamental challenge in inorganic chemistry. Solving these challenges is becoming more important because of increasing use of rare-earth elements in numerous technologies, ranging from paramagnets to luminescent materials. Within this context, we interrogated the complexation chemistry of the scandium(III) (Sc3+) trication with the hexadentate 1,4,7-triazacyclononane-1,4,7-triacetic acid (H3NOTA) chelator. This H3NOTA chelator is often regarded as an underperformer for complexing Sc3+. A common assumption is that metalation does not fully encapsulate Sc3+ within the NOTA3- macrocycle, leaving Sc3+ on the periphery of the chelate and susceptible to demetalation. Herein, we developed a synthetic approach that contradicted those assumptions. We confirmed that our procedure forced Sc3+ into the NOTA3- binding pocket by using single crystal X-ray diffraction to determine the Na[Sc(NOTA)(OOCCH3)] structure. Density functional theory (DFT) and 45Sc nuclear magnetic resonance (NMR) spectroscopy showed Sc3+ encapsulation was retained when the crystals were dissolved. Solution-phase and DFT studies revealed that [Sc(NOTA)(OOCCH3)]1- could accommodate an additional H2O capping ligand. Thermodynamic properties associated with the Sc-OOCCH3 and Sc-H2O capping ligand interactions demonstrated that these capping ligands occupied critical roles in stabilizing the [Sc(NOTA)] chelation complex.

Using molten salts to probe outer-coordination sphere effects on lanthanide(III)/(II) electron-transfer reactions.

Controlling structure and reactivity by manipulating the outer-coordination sphere around a given reagent represents a longstanding challenge in chemistry. Despite advances toward solving this problem, it remains difficult to experimentally interrogate and characterize outer-coordination sphere impact. This work describes an alternative approach that quantifies outer-coordination sphere effects. It shows how molten salt metal chlorides (MCln; M = K, Na, n = 1; M = Ca, n = 2) provided excellent platforms for experimentally characterizing the influence of the outer-coordination sphere cations (Mn+) on redox reactions accessible to lanthanide ions; Ln3+ + e1- → Ln2+ (Ln = Eu, Yb, Sm; e1- = electron). As a representative example, X-ray absorption spectroscopy and cyclic voltammetry results showed that Eu2+ instantaneously formed when Eu3+ dissolved in molten chloride salts that had strongly polarizing cations (like Ca2+ from CaCl2) via the Eu3+ + Cl1- → Eu2+ + ½Cl2 reaction. Conversely, molten salts with less polarizing outer-sphere M1+ cations (e.g., K1+ in KCl) stabilized Ln3+. For instance, the Eu3+/Eu2+ reduction potential was >0.5 V more positive in CaCl2 than in KCl. In accordance with first-principle molecular dynamics (FPMD) simulations, we postulated that hard Mn+ cations (high polarization power) inductively removed electron density from Lnn+ across Ln-Cl⋯Mn+ networks and stabilized electron-rich and low oxidation state Ln2+ ions. Conversely, less polarizing Mn+ cations (like K1+) left electron density on Lnn+ and stabilized electron-deficient and high-oxidation state Ln3+ ions.