A set of IL-forming ion combinations has been studied to gain a deeper understanding of how, aside from obvious electrostatic interactions and ion size effects, secondary bonding such as hydrogen as well as halogen bonding and van der Waals interactions along with conformational and structural flexibility influence the crystallization behavior of potentially IL forming salts. The scrutinized ions have been specifically chosen to allow for unraveling preferential interactions of functional groups that may favor or disfavor crystallization with respect to secondary bonding interactions, i.e., primary and quaternary ammonium cations of variable alkyl chain lengths, which were also endowed with hydroxy groups, combined with formate and bis(trifluoromethanesulfonyl)amide anions. The background is to provide a deeper fundamental understanding of how to intentionally pair cations and anions that will not support the formation of a crystalline solid but rather IL formation, an approach described as “anti-crystal engineering”. This concept is based on the idea to avoid combining ions that are strong supramolecular synthons for crystallization. To this avail, the crystallization behavior of salts constituted of combinations of selected ions bearing different structural, supramolecular crystallization motifs has been studied in detail by low-temperature differential scanning calorimetry (DSC). Single crystal X-ray structure analysis has been used to elucidate ion packing and preferential interactions whenever crystalline solid formation is observed. The study reveals that the lowest melting points are supported by cation-anion combinations that have the least hydrogen bonding. However, if there are multiple possibilities of H-bonding for an ion with its counteranion, this bonding frustration leads as well to low melting points-albeit they are still higher compared to ion combinations with no H-bonding capacity. Through a careful balance of primary and secondary, directional and nondirectional interactions, it was possible to rationally identify a record class of ionic liquids, which combine exceptionally high decomposition points (440-450 °C) with an enormously high liquid range around of more than 500 °C and no tendency for solidification down to well below ambient temperature (−90 °C). These ILs are formed by bis(trifluoromethane)sulfonylamides with quaternary ammonium ions that bear an −OH group in the side chain.

Three nonhalogenated ionic liquids (ILs) dissolved in 2-ethylhexyl laurate (2-EHL), a biodegradable oil, are investigated in terms of their bulk and electro-interfacial nanoscale structures using small-angle neutron scattering (SANS) and neutron reflectivity (NR). The ILs share the same trihexyl(tetradecyl)phosphonium ([P_6,6,6,14]⁺) cation paired with different anions, bis(mandelato)borate ([BMB]⁻), bis(oxalato)borate ([BOB]⁻), and bis(salicylato)borate ([BScB]⁻). SANS shows a high aspect ratio tubular self-assembly structure characterized by an IL core of alternating cations and anions with a 2-EHL-rich shell or corona in the bulk, the geometry of which depends upon the anion structure and concentration. NR also reveals a solvent-rich interfacial corona layer. Their electro-responsive behavior, pertaining to the structuring and composition of the interfacial layers, is also influenced by the anion identity. [P_6,6,6,14][BOB] exhibits distinct electroresponsiveness to applied potentials, suggesting an ion exchange behavior from cation-dominated to anion-rich. Conversely, [P_6,6,6,14][BMB] and [P_6,6,6,14][BScB] demonstrate minimal electroresponses across all studied potentials, related to their different dissociative and diffusive behavior. A mixed system is dominated by the least soluble IL but exhibits an increase in disorder. This work reveals the subtlety of anion architecture in tuning bulk and electro-interfacial properties, offering valuable molecular insights for deploying nonhalogenated ILs as additives in biodegradable lubricants and supercapacitors.

Our recent observations of an unexpected Ce(III) hydrolysis product from the reaction of 4-amino-1,2,4-triazole (4-NH₂-1,2,4-Triaz) with CeCl₃·7H₂O, [Ce₆(μ₃-O)₄(μ₃-OH)₂(μ₃-Cl)₂(Cl)₆(μ₂-4-NH₂-1,2,4-Triaz)₁₂]·7H₂O, the first high-nuclearity lanthanide complex where all Ln atoms are connected pairwise through 12 N-donor ligands or 12 neutral bridging ligands of any type, prompted us to explore the utility of this ligand in trapping additional f-element examples. Reactions of LnCl₃·6H₂O (Ln = Nd, Eu, Ho) with a large excess of 4-NH₂-1,2,4-Triaz (20 equiv) and with the addition of small amounts of water to help solubilize the metal salts led to the isolation of the unique hydrolysis products [Nd₆(μ₃-OH)₈Cl₆(μ₂-4-NH₂-1,2,4-Triaz)₁₂][Cl₄]·2H₂O, [Eu₆(μ₆-Cl)_0.23(μ₃-O_0.77)4(μ₃-O)_2.6(μ₃-Cl)_0.4Cl₆(μ₂-4-NH₂-1,2,4-Triaz)₁₂], and [Ho₆(μ₆-Cl)_0.21(μ₃-O_0.79)₄(μ₃-OH)₂Cl₆(μ₂-4-NH₂-1,2,4-Triaz)₁₂][Cl]_3.4. We also report a Ce(III) analogue prepared in glassware contaminated with Pb(OAc)₂, namely, [Ce₆(μ₃-OH)₈(BrPbBr₅)(μ₂-4-NH₂-1,2,4-Triaz)_11.5(OH₂)₆][Pb_0.84Br_4.2][Br]_3.8·2(4-NH₂-1,2,4-Triaz)·3.6H₂O. The Nd(III) complex is the structurally most ordered with a clear [Nd₆(μ₃-OH)₈] cluster core, while the Eu(III) and Ho(III) compounds contain partial occupancy of a μ6 position and thus result in an incomplete Ln₆O₉ cluster core formation. The crystallographic results suggest that the 4-NH₂-1,2,4-Triaz ligand brings Ln(III) ions together, followed by the formation of an Ln₆O₈ or Ln₆O₉ core with whatever remaining anions or ligands can be incorporated. Given the complexity of the hydrolysis products of nuclear waste, we expect to continue to find a myriad of closely related complex structures of these types for the f-elements. 

Two series of isostructural intermetallics have been discovered in our search for new compounds with fused honeycomb motifs, both stable at elevated temperatures (1073 K). They crystallize with orthorhombic unit cells - La4Co4M (M = Sn, Sb, Te, Pb, Bi, SG Pbam, a = 8.247-8.315(2), b = 21.913-22.137(7), c = 4.750-4.664(2) angstrom, V = 850.5-869.5(4) angstrom 3, Z = 4) and La3Ni3M (M = Al, Ga, SG Cmcm, a = 4.1790-4.2395(1), b = 10.4921-10.6426 (6), c = 13.6399-13.7616(8) angstrom, V = 606.72-612.05(7), Z = 3). The crystal structures represent interesting variations of semiregular tilings of corrugated anionic layers and predominantly cationic zigzag motifs. The La4Co4M compounds reveal a complex type of ordering with a high degree of frustration as could be expected for the Kagome ' -related lattices, while magnetic ordering in the La3Ni3M series is less evident. Electronic structure calculations have been performed for multiple compounds within both series revealing metallic character and visible local minima around the Fermi level. The bonding picture is characterized by nearly equal contributions from the anionic and the cationic components.

The La-poor part of the ternary La–Ni–Si system has been explored leading to the discovery and structural characterization of four new polar intermetallic compounds. LaNi₅Si₂ [BaAu₅Ga₂ type, oP64, space group Pnma, a = 7.8223(7) Å, b = 6.3894(6) Å, c = 17.843(2) Å, V = 891.8(2) ų, Z = 8] features a diamond (lonsdaleite)-like homoatomic Ni framework and is the first Ni representative of a larger family of compounds typically formed by aurides. La₂Ni₈Si₃ [Eu₂Ni₈Si₃ type, tP52, P4₂/nmc, a = 10.0278(3) Å, c = 7.5047(4) Å, V = 754.65(6) ų, Z = 4] is characterized by homoatomic Ni₄ tetrahedra and rectangles. LaNi₅Si₃ [SrNi₅P₃ type, oS36, Cmcm, a = 3.722(2) Å, b = 11.759(5) Å, c = 11.622(3) Å, V = 508.7(3) ų, Z = 4] is governed by extensive heteroatomic bonding and characterized by homopolyhedral packing. La₃Ni₄Si₂ [Ce₃Ni₄Si₂ type, mC36, C2/c, a = 15.819(1) Å, b = 6.0068(5) Å, c = 7.4918(6) Å, β = 103.163(5)°, V = 693.17(10) ų, Z = 4] is a new member of homologous series that includes La₃Ni₃Si₂ and La₃Ni_3.5Si₂. We conclude that the similar radii and electronegativities of Ni and Si are the reason for the incredible diversity of compositions and structures in this system.

Magnetic materials with noncollinear spin arrangements are of considerable interest owing to their potential use in emerging computational technologies and memory devices. Competing magnetic interactions, i.e., magnetic frustration, are one of the main origins of noncollinear magnetic structures. While frustrated systems have been mainly studied among magnetic insulators, combining magnetic frustration with electrical conductivity can allow simultaneous charge and spin manipulation, which is crucial for the design of electronic devices. Here, we present a new intermetallic solid solution LaMn_2–xAu_4+x, whose crystal structure accommodates magnetically frustrated Mn square nets. Powder neutron diffraction and first-principles analysis provide evidence that the metallic LaMn_2–xAu_4+x phase can host the frustration-driven hedgehog spin-vortex crystal─a rare noncollinear magnetic state, which was previously exclusively observed for iron pnictides. 

Commercial (protiated) samples of the green and biodegradable bioester 2-ethylhexyl laurate (2-EHL) were mixed with D-2-EHL synthesized by hydrothermal deuteration, with the mixtures demonstrating bulk structuring in small-angle neutron scattering measurements. Analysis in a polymer scattering framework yielded a radius of gyration (R (g)) of 6.5 angstrom and a Kuhn length (alternatively described as the persistence length or average segment length) of 11.2 angstrom. Samples of 2-EHL dispersed in acetonitrile formed self-assembled structures exceeding the molecular dimensions of the 2-EHL, with a mean aggregation number (N-agg) of 3.5 +/- 0.2 molecules across the tested concentrations. We therefore present structural evidence that this ester can function as a nonionic (co)-surfactant. The available surfactant-like conformations appear to enable performance beyond the low calculated hydrophilic-lipophilic balance value of 2.9. Overall, our data offer an explanation for 2-EHL's interfacial adsorption properties via self-assembly, resulting in strong emolliency and lubricity for this sustainable ester-based bio-oil.

Yb3+-doped inorganic materials are constantly in demand due to a strong interest in fundamental and applied research. The simplicity of the 4f1³ electronic structure minimizes de-excitation processes and enables a quasi-three-level laser emission scheme at 1 μm employed for IR laser devices. In this work, we present an unusual simultaneous emission from two of the lowest levels of the 2F5/2 excited state observed at 77 K, measured for the first time and confirmed by the barycenter law for Yb3+-doped tetragonal LuPO4 revealing the lowest crystal field among Yb3+ ion-activated oxide crystals. Three series of tetragonal lutetium orthophosphate powders, containing various concentrations of Yb3+ ions (0.5–5 mol %), were analyzed in nano and micro-crystalline forms. The ionic liquid-assisted (IL) hydrothermal (HT) method was used for the nano-powders' preparation. This route enabled the fabrication of fine nano-powders with particle sizes of 15 nm in an ethylene glycol (GE) reaction medium and 30 nm in a water (W) medium, each exhibiting the desired well-crystallized single-phase phosphate. For comparative studies, the micro-crystalline samples were synthesized via reaction in the solid phase at a relatively high temperature. The Yb3+ ion also served as a structural probe, its spectroscopy i.e., absorption at 4.2 K, selectively excited luminescence at 77 K, and fluorescence decays were used to assign Yb3+ energy levels in only one D2d center precisely. This assignment was based on exceptional features due to the unique emissions observed from the two lowest levels of the 2F5/2 excited state, split only by 27 cm−1, confirmed by calculation of the crystal field parameters from Zeeman spectra.

Emerging organic light-emitting devices, such as light-emitting electrochemical cells (LECs), offer a multitude of advantages but currently suffer from that most efficient phosphorescent emitters are based on expensive and rare metals. Herein, it is demonstrated that a rare metal-free salt, bis(benzyltriphenylphosphonium)tetrabromidomanganate(II) ([Ph₃PBn]₂[MnBr₄]), can function as the phosphorescent emitter in an LEC, and that a careful device design results in the fact that such a rare metal-free phosphorescent LEC delivers broadband white emission with a high color rendering index (CRI) of 89. It is further shown that broadband emission is effectuated by an electric-field-driven structural transformation of the original green-light emitter structure into a red-emitting structure. 

Light-emitting materials based on earth-abundant metals, such as manganese hold great promise as emitters for organic lighting devices. In order to apply such emitter materials and, in particular, to overcome the problem of self-quenching due to cross-relaxation, we investigated a series of tetrabromidomanganate ([MnBr₄]²⁻) salts with bulky tetraalkylphosphonium counter cations [P_nnn]⁺, namely [P_nnnn]₂[MnBr₄] (n = 4 (1), 6 (2) and 8 (3)), which can be obtained by a straightforward reaction of the respective phosphonium bromide and MnBr₂. Variation of the cation size allows control of the properties of the resulting ionic materials. 1 and 3 qualify as ionic liquids (ILs), where 1 features a melting point of 68 °C, and 3 is liquid at room temperature and even at very low temperatures. Furthermore, 1 and 2 show the formation of higher-ordered thermotropic mesophases. For 1 a transition to a thermodynamically metastable smectic liquid crystalline phase can be observed at room temperature upon reheating from the metastable glassy state; 2 appears to form a plastic crystalline phase at ∼63 °C, which persists up to the melting point of 235 °C. The photoemission is greatly affected by phase behaviour and ion dynamics. A photoluminescence quantum yield of 61% could be achieved, by balancing the increase in Mn²⁺-Mn²⁺ separation and reducing self-quenching through increasingly large organic cations which leads to adverse increased vibrational quenching. Compared to analogous ammonium compounds, which have been promoted as @#x0308;inorganic hybrid perovskite, the phosphonium salts show superior performance, with respect to photoluminescent quantum yield and thermal and air/humidity stability. As the presented compounds are not sensitive to the atmosphere, in particular moisture, and show strong visible electroluminescence in the green region of light, they are important emitter materials for use in organic light-emitting devices.