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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 [Pnnn]+, namely [Pnnnn]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 ̈inorganic hybrid perovskites̈, 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.

The binary GdNi adopting the orthorhombic CrB-type (oS8, Cmcm) dissolves up to 21 at% Co (GdCo0.42Ni0.58), but when the Co content reaches 23.7 at% the crystal structure of the GdCoxNi1−x phase changes from the orthorhombic CrB-type to the tetragonal MoB-type (tI16, I41/amd). The latter remains stable between 23.7 and 36.0 at% Co (0.47 ≤ xCo ≤ 0.72), and there is a two-phase region compositional gap of ≈ 2.5 at% Co between the two structures. One of the two 8e sites available in the MoB-type structure is filled by Gd atoms, while Co and Ni atoms are randomly occupying the other 8e site. The lattice parameter a increases from 3.9485(1) Å to 3.9591(1) Å, while c decreases from 21.3286(1) Å to 21.2404(1) Å as xCo increases, both following a quadratic trend. As a result, the unit cell volume increases from 332.53(2) Å3 to 332.93(2) Å3 for, respectively, the Co-poor (GdCo0.47Ni0.53) and the Co-rich (GdCo0.72Ni0.28) sides of the solid solution, also following a quadratic trend with a negative deviation of the Zen's law. The title compound becomes ferromagnetic with TC increasing linearly from 150 K for GdCo0.50Ni0.50 to 171 K for GdCo0.70Ni0.30; linear interpolation leads to TC = 127 K and 174 K for the two ends of the solid solution with xCo = 0.47 and 0.72, respectively. The magnetic susceptibility follows the Curie-Weiss law, indicating a trivalent state of Gd ions, with an effective magnetic moment slightly increasing with the Co content. The magnetocaloric effect, calculated in terms of the isothermal magnetic entropy change, decreases slightly as xCo increases, remaining large in the range 127–174 K.

In search of ionic liquids (ILs) with multiple types of soft donor atoms capable of preferentially complexing a range of soft metal ions over harder ions, we investigated structural clues to the role of hydrogen bonding in IL behavior through a series of salts with anions containing both N- and S-donor atoms based on azole thiolates. Reaction of equimolar amounts of triethylamine (Et3N) or diisobutylamine (DBA) with 1-phenyl-1H-tetrazole-5-thiol (PhTzSH), 1-methyl-1H-tetrazole-5-thiol (MeTzSH), or 5-methyl-1,3,4-dithiazole-2-thiol (MeDiTSH) yielded [Et3NH][MeTzS] (1), a yellow liquid, and the low melting yellow solids [DBAH][MeTzS] (2), [Et3NH][PhTzS] (3), [DBAH][PhTzS] (4), [Et3NH][MeDiTS] (5), and [DBAH][MeDiTS] (6). Thermal analysis revealed that all of them qualify as ILs with melting points below 100 °C. Single crystal X-ray structure analysis of 2-6 revealed the presence of an extensive H-bonding network that includes the rare N-H⋯S hydrogen bonds in 3, 4, and 6. These weaker interactions appear to significantly influence thermal behavior, where strong bonding leads to higher melting temperatures and lower decomposition points.

In the search for new multifunctional materials, particularly for application in solid-state lighting, a set of terbium salicylato (Sal) complexes of general composition [Cat][Tb(Sal)4] with the commonly ionic liquid-forming (IL) cations [Cat] = (2-hydroxyethyl)trimethylammonium (choline) (Chol+), diallyldimethylammonium (DADMA+), 1-ethyl-3-methylimidazolium (C2C1Im+), 1-butyl-3-methylimidazolium (C4C1Im+), 1-ethyl-3-vinylimidazolium (C2Vim+), and tetrabutylphosphonium (P4444+) were synthesized. All Tb compounds exhibit strong green photoluminescence of high color purity by energy transfer from the ligand in comparison with what the analogous La compounds show, and quantum yields can reach up to 63% upon ligand excitation. When excited with an HF generator, the compounds show strong green electroluminescence with the same features of mission. The findings promise a high potential of application as emitter materials in solid-state lighting. As an additional feature, the Tb compounds show a strong response to applied external fields, rendering them multifunctional materials., Terbium-containing organic-inorganic hybrid materials such as ionic complexes allow for unique property combinations that can open up new applications

Sc38Co144Si97 was prepared from the elements by arc melting under argon and subsequent annealing at 800 ​°C for 350 ​h. Single-crystal X-ray diffraction reveals Sc38Co144Si97 to crystallize in a new hexagonal structure type: Pearson's symbol hP279, space group P63/m, a ​= ​33.624(7), c ​= ​3.639(1) Å. The crystal structure of Sc38Co144Si97 can be considered as a 2D intergrowth of three kinds of fragments of simpler structure types: hexagons and quadrilaterals with the arrangements of the Sc6Co30Si19-type and triangles with the arrangement of the Gd4Co13(Si, P)9-type. Quantum chemical calculations have been performed to analyze the electronic structure and provide deeper insight into the structure-property relationships. The Extended Hückel (EH) calculation indicates that Co in Sc38Co144Si97 adopts close to a d10 configuration owing to the covalent interaction with Si. The Sc–Co and Sc–Si interactions are more ionic, and Co–Co and Co–Si bonds are more covalent interactions.

Open framework materials such as zeolites and metalorganic frameworks are garnering tremendous interest because of their intriguing architecture and attractive functionalities. Thus, new types of open framework materials are highly sought after. Here, we present the discovery of completely new inorganic framework materials, where, in contrast to conventional inorganic open frameworks, the scaffold is not based on tetrahedral EO

Aqueous solutions of a series of short carbon chain tetra(n-alkyl)ammonium hydroxides, [Nnnnn][OH] with n = 2: n-ethyl, 3: n-propyl, 4: n-butyl, have been serendipitously found to be potential candidates for direct air carbon capture (DAC) when being used as reagents in more complicated reactions. Aqueous solutions of [N3333][OH], [N2222][OH], or [N3333][OH] with UO2SO4·3H2O and 1,4-diamidoximylbenzene, and [N4444][OH] with cytosine (HCyt) directly absorb CO2 from the atmosphere upon mild heating in the open atmosphere crystallizing in complexes reaching up to 2 : 1 CO2/[Nnnnn]OH ratio. [N2222][HCO3]·3H2O (1), [N2222]2[H(HCO3)3]·5H2O (2), [N3333][HCO3]·0.5H2O (3), [N3333][H(HCO3)2] (4), [N3333]2[(tpa)(H2CO3)2] (5; tpa = terephthalate), [N4444][H(Cyt)(HCO3)]·H2O (6) and [N4444][H2(Cyt)2(HCO3)]·H2O (7) have been isolated in crystalline form and structurally characterized by single crystal X-ray diffraction. The compounds are characterized by complex polyanionic formations from bicarbonate dimers ([(HCO3)2·(H2O)]24−) or chains ([H(HCO3)2]nn− or [H2(tpa)(HCO3)2]n2n−) to water-bicarbonate associates ([(HCO3)2·6H2O]2− and [(H2CO3·(HCO3)2)2·6H2O·2H2O]2−) and three-component anionic layers ([H(Cyt)(HCO3)·H2O]nn− and [H2(Cyt)2(HCO3)·H2O]nn−) frequently showing proton sharing. While some hydroxides themselves can maintain a high CO2/[Nnnnn][OH] ratio, particularly 2 and 4, the presence of secondary hydrogen bond donors/acceptors may increase the sorption efficiency through decreased solubility and enhanced crystallization.

We report two new rare-earth (R) ternary intermetallic compounds—Ho2Ni0.8T1.2 with T = Si and Ge—that correspond to the R5Ni2T3 phase earlier reported to form in Dy–Ni–T and Ho–Ni–T ternary systems. The compounds crystallize in a filled version of the orthorhombic Zr2Ni1–xP-type structure with x = 0.52; their stoichiometry, determined from both single-crystal and powder X-ray diffraction data, is centered on Ho2Ni0.8T1.2 with a narrow solid solubility range for the silicide, while the germanide appears to be a line phase. In addition to R = Dy and Ho, R2Ni0.8T1.2 compounds also form for R = Y and Tb, representing the first examples of rare-earth-based compounds adopting the Zr2Ni1–xP structural prototype. Bulk magnetization data reveal the main transitions of the ferrimagnetic or ferromagnetic type at TC = 38 K for Ho2Ni0.8Si1.2 and TC = 37 K for Ho2Ni0.8Ge1.2, which are followed by subsequent magnetic reordering at lower temperatures. Neutron diffraction shows complex magnetic structures below TC with both ferromagnetic and antiferromagnetic components and magnetic propagation vector κ1 = [0, 0, 0]. Below TN ≅ 24 K (22 K) for the silicide (germanide), an additional antiferromagnetic coupling following an incommensurate magnetic propagation vector κ2 = [κx, 0, 0] appears to coexist with the first magnetic structure., The crystal structure of Ho2Ni0.8Si1.2 (and Ho2Ni0.8Ge1.2) [Zr2Ni0.48P-type (oP32-Pnma)] viewed along the b axis is given. The Ho, Ni1, Ni2/Si, Si1 and Si2 atoms are represented as red, turquoise, blue, light-gray, and dark-gray spheres, respectively. The distinctive structural fragment is built up of five differently oriented trigonal prisms. The magnetic structure of Ho2Ni0.8Ge1.2 with the antiferromagnetic component in the c direction and the ferromagnetic component along the a axis.

A new family of oxofluorophoshates, AFe(PO 3F) 2(A = K, (NH 4) 2Cl, NH 4, Rb, and Cs), was synthesized via ionothermal methods using PF 6ionic liquids. Single-crystal and powder X-ray diffraction reveal that AFe(PO 3F) 2with A = (NH 4) 2Cl crystallizes in a trigonal structure, while AFe(PO 3F) 2with A = NH 4, Rb, and Cs crystallizes in a triclinic structure. Dimorphic KFe(PO 3F) 2crystallizes in both the trigonal and triclinic forms. The structures of all compounds feature Yavapaiite-like Fe(PO 3F) 2slabs, which are characterized by triangular Fe layers, planar in the case of the trigonal structure and undulated in the case of the triclinic one. Magnetization measurements reveal all compounds to order antiferromagnetically at low temperatures. The trigonal phases AFe(PO 3F) 2(A = K and (NH 4) 2Cl) display complex magnetic H-T phase diagrams. The observation of magnetization plateaus at M sat/3 (M sat= saturation magnetization) indicates the existence of the up-up-down (UUD) and V-phases at applied magnetic fields in the magnetically ordered state. Powder neutron diffraction measurements of KFe(PO 3F) 2confirm the 120° spin structure at zero fields. Along c, the magnetic moments form a commensurate spiral since the spins in each plane are rotated by 90° with respect to the adjacent one. To our knowledge, this is the first time such a non-centrosymmetric version of the 120° spin structure with a 90° rotation between nearest planes has been reported.

Continuing our investigations of ionic liquid (IL) based routes to a library of f-element/soft donor complexes which could be studied crystallographically, we have explored the dissolution of f-ele...

Our attempts to use an ionic liquid strategy to force f-element coordination of soft donor adenine and 4,5-dicyanoimidazole using 1-pot reactions in water using hydrated lanthanide salts failed, instead resulting in the isolation of anhydrous lanthanide nitrate salts. Reactions of previously ground mixtures of 40 % aq. [P 4444][OH] and adenine with Nd(NO 3) 3·6H 2O or Sm(NO 3) 3·6H 2O followed by hand grinding and heating to 90 °C for 10 h led to hot crystallization of anhydrous [P 4444] 2[Nd(NO 3) 5] and [P 4444] 2[Sm(NO 3) 5]. The same reaction with 4,5-dicyanoimidazole and Nd(NO 3) 3·6H 2O but without heating (10 h, room temperature) to prevent ligand decomposition, led to crystallization of anhydrous [P 4444] 3[Nd(NO 3) 6]. [P 4444] 3[Nd(NO 3) 6] could also be isolated by conducting the first reaction without using adenine. The single crystal X-ray diffraction structures of the three new anhydrous salts were examined to provide clues to the observed behavior. The [P 4444] + cations allow charge balance while forming box-type encapsulations around the anionic counterpart which has been previously reported in similar structures. The fact that these anhydrous salts were prepared from water with hydrated starting materials and no precautions taken to keep the crystal growing process anhydrous, suggests synthetic strategies that can potentially be beneficial for more advanced separations procedures.

Four mono-substituted N-butylpyridinium salts, 1-butyl-4-dimethylaminopyridinium chloride [b4dmapy]Cl, 1-butyl-4-methylpyridinium bromide [b4mpy]Br, 1-butyl-4-methylpyridinium hexafluorophosphate [...

The metal–organic material UVO(UVIO2)2(OH)5(Triaz)2 (Triaz = 1,2,4-triazolate) has been isolated from the reaction of UO2(NO3)2·6H2O with 1,2,4-triazole in the ionic liquid 1-ethyl-3-methylimidazol...

CrystEngComm 23(8), 1785 - 1795 (2021). doi:10.1039/D0CE01672A, Ionic liquids (ILs) are receiving growing interest as highly tunable, multifunctional materials. Remarkably for liquids, they tend to display a high level of structural order. This structural order may even lead to the formation of mesophases such as liquid crystals (LCs). Imidazolium compounds are by far the most popular ILs, because they offer a widely versatile platform for property tuning. To investigate what is driving structural order in imidazolium-based ILs a series of asymmetrical 1-dodecyl-2-methyl-3-alkylimidazolium bromides, [C$_{12}$C$_1$C$_n$im][Br] with n = 0���12 have been synthesized, fully characterized and their structures and properties compared with the analogous 1-dodecyl-3-alkylimidazolium as well as the 1,2,3-triazolium bromides. The aim is to examine the influence of the replacement of the most acidic 2-H proton on the imidazolium head group by methylation on the properties and structure of ILs. For all compounds, except for compounds with butyl- and hexyl-chains as well as the protonated species, mesophase formation can be observed. Obviously, the simple presence of long alkyl chains such as dodecyl (a design concept frequently put forward in the literature) is not sufficient to support mesophase formation alone. Rather, for the formation of a liquid crystalline phase, a balance between attractive van der Waals forces, hydrogen bonds, and electrostatic interactions is required. Data from temperature-dependent small-angle X-ray scattering (SAXS) and polarizing optical microscopy (POM) suggest three different cation conformations for the studied [C$_{12}$C$_1$C$_n$im][Br]: cations with 0 ��� n ��� 4 exhibit a near-linear conformation; for 5 ��� n ��� 10 a V-shape is adopted, and for n = 11 or 12 a U-shape is found. We demonstrated that the structural possibility for an interdigitation of the long chains is an influential factor for the formation of a mesophase., Published by RSC, London

A carefully designed red-light-emitting iridium (III) cationic complex yields light-emitting electrochemical cells (LECs) with exceptional efficiency and stability. [Ir­(4Fppy)2(biq)]­[PF6] (4Fppy = 2-(4-fluorophenyl)­pyridinato, biq = 2,2′-biquinoline), whose structure was authenticated by single-crystal X-ray diffraction, emits in the red region of light with photoluminescence (upon 360 nm excitation) and electroluminescence maxima at 629 nm. Astonishingly, it is based on a fluorinated ligand, a design concept more commonly used for green emitter materials. Pairing it with a ligand that has comparatively low-lying frontier orbitals allows for a red shift of the band gap. The uncommon electronic structure of the complex allows overcoming the common problem of strong metal–ligand antibonding interactions in the excited state, rendering it extremely stable under operation. The complex displays a high photoluminescence quantum yield of 27.1% giving rise to an extremely efficient LEC with an initial maximum luminance of 326 cd m–2, current efficiency of 3.26 cd A–1, and power efficiency of 2.27 lm W–1, surpassing the current state of the art. Remarkably, the efficient red LEC has a lifetime of 167 h when driven under a block-wave pulsed current at a frequency of 1000 Hz, an average current density of 100 A m–2, and a duty cycle of 50%. Increasing the duty cycle to 75% led to a decrease in the device average voltage, increasing the power efficiency to an exceptional value of 2.97 lm W–1 without compromising the device stability.

A robust general route to lanthanide dicyanamide (DCA–) complexes has been developed where f-element salts are dissolved in DCA–-based ionic liquids (ILs) directly or formed in situ, forcing coordination of these normally weakly coordinating soft N-donor anions, even in an ambient, non-moisture-excluding environment. A series of lanthanide complexes [C2mim][Ln(DCA)4(H2O)4] (C2mim = 1-ethyl-3-methylimidazolium; Ln = La, Nd, Eu, Tb, Dy, and Yb) and [C2mim]3n[La(OH2)4(μ2-DCA)4]n[La(OH2)2(μ3-DCA)3(μ2-DCA)4]2n(Cl)4n were crystallized under a variety of conditions using this methodology and structurally characterized using single crystal X-ray diffraction. Although not all examples were isostructural, the dominant feature across the series was the presence of [Ln(DCA)4(H2O)4]− anionic nodes with all terminal DCA– ligands accepting hydrogen bonds from the coordinated water molecules forming a 3D metal organic framework. To determine if any structural clues might aid in the further development of the synthetic methodology, the metal-free IL [C1mim][DCA] (C1mim = 1,3-dimethylimidazolium), a room-temperature solid, crystalline analogue of the reaction IL, which is liquid at room temperature, was also prepared and structurally characterized. The ready isolation of these compounds allowed us to begin an investigation of the physical properties such as the luminescence at room and low temperatures for the Eu, Tb, and Dy representatives., Direct dissolution of lanthanide chloride hydrates in the DCA− ionic liquids leads to coordination of DCA− anions to Ln3+ under full displacement of chloride and partial displacement of water ligands leading to the formation of metal organic frameworks under ambient conditions. X-ray analyses reveal a significant influence of the hydrogen bonding and lanthanides’ size on crystallographic disorder in their crystal structures.

Starting generally with a 4:6:3 molar ratio of Pt, Sn, and R (where R = La–Sm), with or without the application of a NaCl flux, seven ternary compounds were obtained as single crystals. The platinides Pt4Sn6R3 (R = La–Nd) crystallize with the Pt4Ge6Pr3 type of structure (oP52, Pnma, a = 27.6–27.8 Å, b = 4.59–4.64 Å, c = 9.33–9.40 Å). With R = Pr, Pt4Sn6Pr3–x (oP52, Pnma, a = 7.2863(3) Å, b = 4.4909(2) Å, c = 35.114(1) Å) is also obtained, which might be considered a high-temperature polymorph with disorder on the Sn- and Pr-sites. For R = Nd and Sm, a structurally related isostructural series with a slightly different composition Pt3Sn5R2–x (oP52, Cmc21, a = 4.50–4.51 Å, b = 26.14–26.30 Å, c ≈ 7.29 Å) has been observed, together with Pt7Sn9Sm5 (oS42, Amm2, a = 4.3289(5) Å, b = 28.798(4) Å, c = 7.2534(9) Å) under the same conditions. The latter exhibits the rare Zr5Pd9P7-type structure, linking polar intermetallics to metal phosphides, in accord with P7Pd9Zr5≡Pt7Sn9Sm5. All structures may be described in terms of either negative Pt/Sn networks encapsulating positive R atoms, or {PtSnx} clusters (x = 5, 6, or rarely 7) sharing vertices and edges with R in the second coordination sphere and with considerable heterometallic Pt–R bonding contributions., A family of ternary intermetallic compounds has been observed for the light lanthanides from Ce to Eu, with Nd being a transition point. All compounds contain ∼30 at. % Pt but show high variability of the Pt@Snx bonding motifs with the lanthanide size, causing minor compositional and soft structural changes along the series.

We investigated whether the relatively Lewis basic imidazole-2-thiones could be used to substitute water ligands bound to f-element cations and generate f-element soft donor complexes. Reactions of 1,3-diethylimidazole-2-thione (C2C2ImT) with Nd(NO3)3·6H2O and UO2Cl2·3H2O led to the isolation of the anhydrous thione complexes Nd(NO3)3(C2C2ImT)3 and UO2Cl2(C2C2ImT)2, characterized by single crystal X-ray diffraction. Differences in the strength of metal-thione interactions have been examined by means of the crystal structure analysis and density functional theory (DFT) calculations. The C2C2ImT ligands were found to be affected by both coordination and noncovalent interactions, making it impossible to deconvolute the effects of one from the other. Calculated partial atomic charges indicated greater ligand-to-metal charge transfer in the [UO2]2+ complex, indicative of a stronger interaction. The reactivity of C2C2ImT demonstrates its usefulness in the preparation of f-element soft donor complexes from readily available hydrates that could be useful intermediates for promoting the coordination and studying the effects of soft donor anions.

By dehydrating actinide salts with an ionic liquid containing a common anion and subsequent reaction with N-heterocyclic ligands, we challenge the concept that actinides prefer O- over N-donors; rather the acidic hydrogen atoms of protic solvents hinder the formation of more elusive f-element N-donor coordination complexes.

The central part of the La-Ni-Si system has been investigated at 800 °C by means of single crystal X-ray diffraction, microscopy and analytical microprobe techniques. The result led to the identification of four new metal-rich silicides: LaNi2Si (R3̄m, a = 4.0263(3) Å, c = 15.066(2) Å, Z = 3), La2Ni3Si2 (P21/c, a = 6.8789(7) Å, b = 6.2167(3) Å, c = 12.214(1) Å, β = 90.92(1), Z = 4), La3Ni3Si2 (Pnma, a = 7.501(2) Å, b = 14.316(4) Å, c = 6.149(2) Å, Z = 4), La6Ni7Si4 (Pbcm, a = 6.066(1) Å, b = 7.488(1) Å, c = 29.682(5) Å, Z = 4). LaNi2Si belongs to the SrCu2Ga structure type, which is not represented among silicides, while La2Ni3Si2 crystallizes in its own structure type. Both compounds feature layered polyanionic motifs consisting of Ni and Si, which are separated by La. Instead, La6Ni7Si4 and La3Ni3Si2 are characterized by polyanionic networks. The former compound belongs to the Pr6Ni7Si4 structure type, with only two other representatives (Ce and Nd); the latter has been observed only with Rh and Ir. The two structures reveal close structural relationships having multiple identical slabs. Tight-binding electronic structure calculations by linear muffin-tin-orbital methods were performed for LaNi2Si, La2Ni3Si2 and La3Ni3Si2 to gain insights into their structure-bonding relationships. Their band structures suggest a metallic character for all compounds. The overall crystal orbital Hamilton populations are dominated by polar Ni-Si bonds, though homoatomic Ni-Ni and La-Ni(Si) bond contributions are not negligible. The variety of bonding patterns may serve as a logical explanation for the number of discovered compounds in this system as well as for the diversity of the observed structures.

Two new quaternary selenides of the α-TlSe structure type have been synthesized and characterized. Single crystal X-ray diffraction analysis has revealed that Tl2Ga2SnSe6 crystallizes with space group I4/mmc, a = 8.095(1), c = 6.402(1) Å, with a refined composition of Tl1− x Ga1− y Sn y Se2 (x = y = 0.345(5)), Z = 4, R1 = 0.028; wR2 = 0.066. The crystal structure of the isostructural compound Tl2Ga2GeSe6 has been determined by means of powder X-ray diffraction: space group I4/mmc, Z = 4, a = 8.0770(4), c = 6.2572(5) Å, refined composition Tl1− x Ga1− y Ge y Se2, x = 0.343(5), y = 0.35(2), (R B(I) = 0.084; R P = 0.041; R Pw = 0.058). According to their optical absorption spectra all compounds are semiconductors with relatively narrow direct band gaps of 2.15(3) and 2.05(5) eV for the Ge and Sn phase, respectively.

The reaction of 1,3-dimethylimidazolium-2-carboxylate with elemental iodine in acetonitrile rapidly affords crystalline iodide salts of the 1,3-dimethyl-2-iodoimidazolium cation ([C1mim-2-I]+), [C1...

Ionic liquids present a versatile, highly tunable class of soft functional materials. Aside from being low melting salts, they can be endowed with additional functionalities. In N-alkylimidazolium ...

Significance With rare exceptions, an antiferromagnetic (AFM) transition in zero magnetic field is thermodynamically of second order where the thermal-average magnetic moments of the magnetic atoms (ordered moments) vary continuously on cooling through the AFM ordering temperature T N with no latent heat at the transition. Such materials include the AFM pnictides CaMn 2 As 2 , SrMn 2 As 2 , CaMn 2 Sb 2 , SrMn 2 Sb 2 , and CaMn 2 Bi 2 . Here we demonstrate that the closely related SrMn 2 P 2 and CaMn 2 P 2 insulators instead exhibit first-order AFM transitions at T N = 53 and 70 K, respectively, where the heat capacity exhibits a latent heat at T N . The mechanism causing these first-order transitions remains to be explained, but its understanding may lead to the development of novel magnetic materials of technological interest.

SrMn(2)P(2) and CaMn(2)P(2) are insulators that adopt the trigonal CaAl(2)Si(2)-type structure containing corrugated Mn honeycomb layers. Magnetic susceptibility χ and heat capacity versus temperature T data reveal a weak first-order antiferromagnetic (AFM) transition at the Néel temperature [Formula: see text] K for SrMn(2)P(2) and a strong first-order AFM transition at [Formula: see text] K for CaMn(2)P(2). Both compounds exhibit isotropic and nearly T-independent [Formula: see text] , suggesting magnetic structures in which nearest-neighbor moments are aligned at [Formula: see text] to each other. The (31)P NMR measurements confirm the strong first-order transition in CaMn(2)P(2) but show critical slowing down above [Formula: see text] for SrMn(2)P(2), thus also evidencing second-order character. The (31)P NMR measurements indicate that the AFM structure of CaMn(2)P(2) is commensurate with the lattice whereas that of SrMn(2)P(2) is incommensurate. These first-order AFM transitions are unique among the class of (Ca, Sr, Ba)Mn(2) (P, As, Sb, Bi)(2) compounds that otherwise exhibit second-order AFM transitions. This result challenges our understanding of the circumstances under which first-order AFM transitions occur.

A set of different open framework iron phosphates have been synthesized ionothermally using a task-specific ionic liquid, 1-butyl-4-methylpyridinium hexafluorophosphate, that acts in the synthesis as the reaction medium and mineralizer: (NH4)2Fe2(HPO4)(PO4)Cl2F (1) and K2Fe2(HPO4)(PO4)Cl2F (2) exhibit similar composition and closely related structural features. Both structures consist of {Fe2(HPO4)(PO4)Cl2F}2- macroanions and charge balancing ammonium or potassium cations. Their open framework structure contains layers and chains of corner-linked {Fe(1)O2Cl4} and {Fe(2)F2O4} octahedra, respectively, interconnected by PO4 tetrahedra forming 10-ring channels. KFe(PO3F)F2 (3) is built up by {Fe[(PO3F)4/3F2/2]}{Fe(PO3F)2/3F2/2F2} layers separated by K+ cations. Chains of alternating {FeF2O4} and {FeO2F4} octahedra, which are linear for 1 but undulated for 2, are linked to each other via corner-sharing {PO3F} tetrahedra with the fluorine pointing into the interlayer space. The compounds were characterized by means of single crystal and powder X-ray diffraction, infrared spectroscopy, and magnetic measurements. 1 reveals a strong ground state spin anisotropy with a spin 5/2 state and a magnetic moment of 5.3 μB/Fe3+. Specific heat and magnetic data unveil three magnetic transitions at 95, 50, and 3.6 K. Compound 2 has a very similar crystal structure as compared to 1 but exhibits a different magnetic behavior: a slightly lower magnetic moment of 4.7 μB/Fe3+ and a magnetic transition to a canted antiferromagnetic state below 90 K. Compound 3 exhibits typical paramagnetic behavior close to room-temperature (5.71 μB/Fe3+). There are no clear indications for a phase transition down to 2 K despite strong antiferromagnetic spin-spin interactions; only a magnetic anomaly appears at 50 K in the zero-field cooled data.

Direct quaternization of 1-methyl-1,2,4-triazole with n-alkyl methanesulfonates (alkyl = butyl, octyl, dodecyl) showed to be an atom-economic, convenient, mild, solvent- and halide-free way to obta...

An ionothermal synthesis study of transition metal phosphates using the ionic liquid 1-butyl-4-methylpyridinium hexafluorophosphate [C4mpy][PF6] yielded four new, different open framework manganese compounds, that is, K2Mn3(HPO4)2(PO3F)F2 (1), (NH4)2Mn3(HPO4)2(PO3F)F2 (2), KMn3(H2PO4)(HPO4)2F2 (3), and (NH4)Mn3(H2PO4)(PO3F)2F2 (4). The obtained products not only feature new framework topologies unprecedented in the family of phosphates but also interesting properties as the transition metal gives rise to both luminescent (rendering them potential nonrare earth containing red emitting phosphors) and unconventional magnetic properties governed by geometric frustrations. Aside from the structural analysis (powder and single-crystal X-ray diffraction, infrared spectroscopy), a variety of characterization methods (photoluminescence spectroscopy and magnetic measurements) were applied to study the material’s properties. Single crystal X-ray studies reveal that 1 (P21/c with a = 5.501(1), b = 14.203(3), c = 16.9...

Materials showing thermoelectric properties known as thermoelectrics can reversibly convert a temperature gradient into electricity. Since the vast majority of energy we use comes from thermal proc...

The kinetic arrest observed in the parent Gd5Ge4 gradually vanishes when a small fraction (x = 0.025, 0.05 and 0.10) of Gd is replaced by Sc in (Gd1−xScx)5Ge4, and the magnetic ground state changes from antiferromagnetic (AFM) to ferromagnetic (FM). A first order phase transition coupled with the FM-AFM transition occurs at TC = 41 K for x = 0.05 and at TC = 53 K for x = 0.10 during heating in applied magnetic field of 1 kOe, and the thermal hysteresis is near 10 K. The first-order magnetic transition is coupled with the structural Sm5Ge4-type to Gd5Si4-type transformation. The magnetization measured as a function of applied magnetic field shows sharp metamagnetic-like behavior. At the same time, the AFM to paramagnetic transition in (Gd1−xScx)5Ge4 with x = 0.10, is uncharacteristically broad indicating development of strong short-range AFM correlations above the Neel temperature. Comparison of the magnetization data of bulk, powdered, and metal-varnish composite samples of (Gd0.95Sc0.05)5Ge4 shows that mechanical grinding and fabrication of a composite have little effect on the temperature of the first-order transformation, but short-range ordering and AFM/FM ratio below TC are surprisingly strongly affected.

Access to lanthanide acetate coordination compounds is challenged by the tendency of lanthanides to coordinate water and the plethora of acetate coordination modes. A straightforward, reproducible synthetic procedure by treating lanthanide chloride hydrates with defined ratios of the ionic liquid (IL) 1‐ethyl‐3‐methylimidazolium acetate ([C2mim][OAc]) has been developed. This reaction pathway leads to two isostructural crystalline anhydrous coordination complexes, the polymeric [C2mim] n [{Ln2(OAc)7} n ] and the dimeric [C2mim]2[Ln2(OAc)8], based on the ion size and the ratio of IL used. A reaction with an IL : Ln‐salt ratio of 5 : 1, where Ln=Nd, Sm, and Gd, led exclusively to the polymer, whilst for the heaviest lanthanides (Dy−Lu) the dimer was observed. Reaction with Eu and Tb resulted in a mixture of both polymeric and dimeric forms. When the amount of IL and/or the size of the cation was increased, the reaction led to only the dimeric compound for all the lanthanide series. Crystallographic analyses of the resulting salts revealed three different types of metal‐acetate coordination modes where η 2 μκ 2 is the most represented in both structure types., A straightforward pathway to synthesize anhydrous lanthanide acetate complexes from lanthanide chloride hydrates and the ionic liquid (IL) 1‐ethyl‐3‐methylimidazolium acetate ([C2mim][OAc]) is described. The combination of the lanthanide size and the amount of IL introduced allows the selective formation of two isostructural crystalline anhydrous compounds the dimeric, [C2mim]2[Ln2(OAc)8], and the polymeric, [C2mim] n [{Ln2(OAc)7} n ].

Many crystalline materials form polymorphs and undergo solid-solid transitions between different forms as a function of temperature or pressure. However, there is still a poor understanding of the mechanism of transformation. Conclusions about the transformation process are typically drawn by comparing the crystal structures before and after the conversion, but gaining detailed mechanistic knowledge is strongly impeded by the generally fast rate of these transitions. When the crystal morphology does not change, it is assumed that crystallinity is maintained throughout the process. Here we report transformation between polymorphs of ZnCl2(1,3-diethylimidazole-2-thione)(2) which are sufficiently slow to allow unambiguous assignment of single crystal to single crystal transformation with shape preservation proceeding through an amorphous intermediate phase. This result fundamentally challenges the commonly accepted views of polymorphic phase transition mechanisms. Funding Agencies|Novo Nordisk FoundationNovo Nordisk FoundationNovocure Limited; Knut and Alice Wallenberg FoundationKnut & Alice Wallenberg Foundation; Royal Academy of Sciences, Sweden; Swedish Research Council (Vetenskapsradet, VR)Swedish Research Council [2018-05973, 2020-05405, 2018-00233, 2020-04600, SNIC 2020-3-29]

The ternary-arsenide compound BaCo

A new molecular thermometric sensor based on the terbium(III) complex [C2mim][Tb(fod)4] (C2mim – 1-methyl-3-ethylimidazolium, fod− - tetrakis-6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate), doped with 0.015% of its europium(III) analogue (1, [C2mim][Tb(fod)4]0.99985:[C2mim][Eu(fod)4]0.00015), was prepared and its thermochromic behaviour evaluated from ambient temperature up to 75 °C, including in the physiological range (35–45 °C). It was found that the intensity ratio of the 5D4→7F5 (TbIII) and 5D0→7F2 (EuIII) transitions is correlated with temperature having three different linear regimes. Visual colorimetry allowed the evaluation of the temperature in different ranges from green at ambient temperature, to yellow and finally red at higher temperatures. The TbIII complex emission intensity is extremely sensitive to small temperature variations, particularly between 25 and 35 °C, were it reaches only 40% of the initial intensity. Confinement of the dopped TbIII tetrakis-complex in the organic polymeric matrix poly(methylmethacrylate) (PMMA) induced higher thermal stability in 1, together with a strong temperature dependence of the most intense emissive transition of the TbIII complexes. The photoluminescence quantum yield of polymer-lanthanide hybrid materials increased significantly compared with that of 1. Under 366 nm irradiation, the hybrid material presents a green colour at 25 °C that evolves to yellow at 30 °C and to a white tone at 35 °C.

A new ionothermal synthesis utilizing 1-alkyl-pyridinium hexafluorophosphates [C

A simple, environmentally benign, and efficient chemical separation of rare earth oxalates (CSEREOX) within two rare earth element (REE) subgroups has been developed. The protocol allows for selective solubilization of water-insoluble oxalates of rare earth elements, and results in efficient REE extraction even at low initial concentrations (

Significance All genetic information on Earth is encrypted in DNA and RNA with the nucleobases and their pairs being the main information units. There are strict established rules how nucleobases can interact between each other in the DNA. These rules can though be affected by external factors such as radiation causing formation of the deprotonated charged species. Although such species are extremely unstable and low in abundance, they may affect local connectivity and introduce wrong units in the DNA chain, so proper characterization of their interactions is of enhanced importance. Here we could obtain anionic nucleobases in stable form in the solid state, opening the possibility to study them crystallographically and develop theoretical models for real biological systems., Utilizing an ionic liquid strategy, we report crystal structures of salts of free anionic nucleobases and base pairs previously studied only computationally and in the gas phase. Reaction of tetrabutylammonium ([N4444]+) or tetrabutylphosphonium ([P4444]+) hydroxide with adenine (HAd) and thymine (HThy) led to hydrated salts of deprotonated adenine, [N4444][Ad]·2H2O, and thymine, [P4444][Thy]·2H2O, as well as the double salt cocrystal, [P4444]2[Ad][Thy]·3H2O·2HThy. The cocrystal includes the anionic [Ad−(HThy)] base pair which is a stable formation in the solid state that has previously not even been suggested. It exhibits Watson–Crick connectivity as found in DNA but which is unusual for the free neutral base pairs. The stability of the observed anionic bases and their supramolecular formations and hydrates has also been examined by electronic structure calculations, contributing to more insight into how base pairs can bind when a proton is removed and highlighting mechanisms of stabilization or chemical transformation in the DNA chains.

Although rare-earth-metal–transition-metal (R/T) phase diagrams have been explored extensively, our recent studies have uncovered new previously nonexistent binary intermetallics. These compounds belong to a narrow region between 70 and 71.4 atom % of the rare-earth metal but represent four different structure types. The binaries Tb7Pd3 and Er17Pd7 are compositionally approaching (less than 1 atom % difference) the previously reported R2.16Pd0.89 (R = Tb and Er), and apparently form by peritectoid transformation, thus, being hard to detect by fast cooling. Tb7Pd3 (1) crystallizes in the Th7Fe3 structure type (hP20, P63mc, a = 9.8846(4) Å, c = 6.2316(3) Å, Z = 2) while Er17Pd7 (2) belongs to the Pr17Co7 type being its second reported representative (cP96, P213, a = 13.365(2) Å, Z = 4). Er17Pd7 (2) is overlapping with the cubic F-centered Er2.11Pd0.89 (3b, Fd3̅m, a = 13.361(1) Å, Z = 32) with practically identical unit cell parameters but a significantly different structure. Electronic structure calculations confirm that heteroatomic R–T bonding strongly dominates in all structures; T–T bonding interactions are individually strong but do not play a significant role in the total bonding., Polyicosahedral {Pd4Er22} and {Pd3Er20} anti-Mackay type clusters with prismatic bridges in the crystal structures of Er17Pd7 and Er2.11Pd0.89.

Single crystals of $\mathrm{Ca}{({\mathrm{Co}}_{1\ensuremath{-}x}{\mathrm{Ir}}_{x})}_{2\ensuremath{-}y}{\mathrm{As}}_{2}$ with $0\ensuremath{\le}x\ensuremath{\le}0.35$ and $0.10\ensuremath{\le}y\ensuremath{\le}0.14$ have been grown using the self-flux technique and characterized by single-crystal x-ray diffraction (XRD), energy-dispersive x-ray spectroscopy, magnetization $M$, and magnetic susceptibility $\ensuremath{\chi}$ measurements versus temperature $T$, magnetic field $H$, and time $t$, and heat-capacity ${C}_{\mathrm{p}}(H,T)$ measurements. The XRD refinements reveal that all the Ir-substituted crystals crystallize in a collapsed-tetragonal structure as does the parent ${\mathrm{CaCo}}_{2\ensuremath{-}y}{\mathrm{As}}_{2}$ compound. A small 3.3% Ir substitution for Co in ${\mathrm{CaCo}}_{1.86}{\mathrm{As}}_{2}$ drastically lowers the A-type antiferromagnetic (AFM) transition temperature ${T}_{\mathrm{N}}$ from 52 to 23 K with a significant enhancement of the Sommerfeld electronic heat-capacity coefficient. The A-type AFM structure consists of $ab$-plane layers of spins ferromagnetically aligned along the $c$ axis with AFM alignment of the spins in adjacent layers along this axis. The positive Weiss temperatures obtained from Curie-Weiss fits to the $\ensuremath{\chi}(Tg{T}_{\mathrm{N}})$ data indicate that the dominant magnetic interactions are ferromagnetic (FM) for all $x$. A magnetic phase boundary is inferred to be present between $x=0.14$ and $x=0.17$ from a discontinuity in the $x$ dependencies of the effective moment and Weiss temperature in the Curie-Weiss fits. FM fluctuations that strongly increase with increasing $x$ are also revealed from the $\ensuremath{\chi}(T)$ data. The magnetic ground state for $x\ensuremath{\ge}0.17$ is a spin glass as indicated by hysteresis in $\ensuremath{\chi}(T)$ between field-cooled and zero-field-cooled measurements and from the relaxation of $M$ in a small field that exhibits a stretched-exponential time dependence. The spin glass has a small FM component to the ordering and is hence inferred to be comprised of small FM clusters. The competing AFM and FM interactions along with crystallographic disorder associated with Ir substitution are inferred to be responsible for the development of a FM cluster-glass phase. A logarithmic $T$ dependence of ${C}_{\mathrm{p}}$ at low $T$ for $x=0.14$ is consistent with the presence of significant FM quantum fluctuations. This composition is near the $T=0$ boundary at $x\ensuremath{\approx}0.16$ between the A-type AFM phase containing ferromagnetically-aligned layers of spins and the FM cluster-glass phase.

We investigated whether the relatively Lewis basic imidazole-2-thiones could be used to substitute water ligands bound to f-element cations and generate f-element soft donor complexes. Reactions of 1,3-diethylimidazole-2-thione (C

Complex metallic alloys belong to the vast family of intermetallic compounds and are hallmarked by extremely large unit cells and, in many cases, extensive crystallographic disorder. Early studies of complex intermetallics were focusing on the elucidation of their crystal structures and classification of the underlying building principles. More recently, ab initio computational analysis and detailed examination of the physical properties have become feasible and opened new perspectives for these materials. The present review paper provides a summary of the literature data on the reported compositions with exceptional structural complexity and their properties, and highlights the factors leading to the emergence of their crystal structures and the methods of characterization and systematization of these compounds.