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Salts of octabismuth(2+) polycations crystallized from Lewis-acidic ionic liquids

  • Maximilian Knies and Michael Ruck EMAIL logo
Published/Copyright: May 31, 2021
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Zeitschrift für Naturforschung B
From the journal Zeitschrift für Naturforschung B Volume 76 Issue 10-12

Abstract

The reaction of Bi and BiCl3 with RbCl or CsCl in the Lewis-acidic ionic liquid (IL) [BMIm]Cl·4AlCl3 at T = 200 °C yielded air-sensitive, shiny black crystals. X-ray diffraction on single crystals revealed the hexagonal structures of two new salts (Bi8)M[AlCl4]3 (M = Rb, Cs), which are isostructural to the high-temperature form of (Bi8)Tl[AlCl4]3. The known (Bi8)2+ polycation is a square antiprism and can be interpreted as an arachno cluster following modified Wade rules. The crystal structure is a complex variant of the hexagonal perovskite structure type ABX 3 with A = (Bi8)2+, B = M + and X = [AlCl4]–. Chiral strands ∞ { M [ AlCl 4 ] 3 } 2 − ∞ 1 (M = Rb, Cs) run along [001]. The (Bi8)2+ polycations are only weakly coordinated inside a cage of 24 chloride ions and show dynamic rotational disorder at room temperature. Upon slow cooling to 170 K, the reorientation of the clusters was frozen, yet no long-range order was established.

Keywords: bismuth polycations; crystal structure; ionic liquids

1 Introduction

Compounds containing homonuclear bismuth polycations are known since Corbett and Hershaft synthesized “bismuth monochloride” Bi6Cl7 in 1962 [1]. Over the course of the following decades, the number of compounds containing these cationic clusters has increased gradually. Isolated bismuth polycations of varying shapes, sizes and charges were observed [2], [3], [4], [5], [6], [7], [8], [9], [10], [11], [12], [13], [14], [15], [16] as well as cluster complexes involving electron-rich transition metals, M, either coordinated by or centering bismuth clusters (M = Au, Cu, Pd, Pt, Ru) [17], [18], [19], [20], [21], [22], [23], [24]. Recently, we reported on the synthesis and crystal structure of (Bi8)Tl[AlCl4]3, which contains isolated Bi8 2+ polycations and shows characteristics that often impede the crystal structure determination of such cluster compounds [16]. The tetrahedral shape and the weakly coordinating nature of [EX 4]– anions (E = Al, Ga, In; X = Cl, Br, I) generates pseudosymmetry and allows for high degrees of rotational freedom of all polyhedral groups in the structure. The symmetry of the bismuth cluster is usually lower than that of its coordination environment, leading to a number of (almost) equivalent orientations for the cluster cation. This results, at best, in a finite number of resolvable disoriented positions [5, 7, 18–20, 22, 24] or, at worst, in the formation of semiplastic crystals with electron densities modeling a hollow sphere at the cluster position [10]. Depending on the rotation barriers and the temperature, the disorder can be dynamic or static. Only in few cases, slow cooling does not only freeze the disordered situation but generates an ordered structure. However, such an ordered low-temperature structure has typically a much lower point and translational symmetry than the disordered average structure, which leads to multiple twinning and antiphase boundaries and, in some cases, a starfield-like diffraction pattern. (Bi8)Tl[AlCl4]3 is a rare case, where a slow cooling process resulted in a largely ordered low-temperature structure that could be solved [16].

In this work, we present two new compounds containing rubidium and cesium cations alongside Bi8 2+ polycations. Both compounds show a structure with (pseudo-)hexagonal symmetry at room temperature, apparently isostructural to the one observed in the high-temperature form of (Bi8)Tl[AlCl4]3.

2 Results and discussion

2.1 Synthesis

The reaction of stoichiometric amounts of Bi, BiCl3 and RbCl or CsCl in the Lewis-acidic ionic liquid (IL) [BMIm]Cl·4AlCl3 (BMIm = 1-n-butyl-3-methylimidazolium) at 200 °C resulted in air-sensitive, shiny black crystals of (Bi8)Rb[AlCl4]3 (1) or (Bi8)Cs[AlCl4]3 (2). Compound 1 crystallizes as elongated hexagonal prisms, a special form of the crystal class 6/m, while 2 forms elongated hexagonal bipyramids, the general form of the crystal class 6/m (Figure 1). Both products were obtained in estimated yields of 50–60%. In both cases (Bi5)[AlCl4]3 and the tetrachloridoaluminate of the respective alkali metal M[AlCl4] (M = Rb, Cs) [25], [26] were observed as side products together with residuals of AlCl3 and traces of a yet unknown phase (Figure S1). To avoid the co-precipitation of (Bi5)[AlCl4]3 is almost impossible, because of dynamic equilibria between the different bismuth polycations in the IL solution. Yet, the side products can easily be distinguished visually: (Bi5)[AlCl4]3 forms red cubes, M[AlCl4] colorless planks, and AlCl3 colorless hexagonal plates. Energy-dispersive X-ray (EDX) spectroscopy confirmed the ratio of bismuth to the alkali metal of 8:1 for 1 and 2.

Figure 1: Scanning electron microscope images of (Bi8)Rb[AlCl4]3 crystals (left) and of (Bi8)Cs[AlCl4]3 crystals (right).
Figure 1:

Scanning electron microscope images of (Bi8)Rb[AlCl4]3 crystals (left) and of (Bi8)Cs[AlCl4]3 crystals (right).

2.2 Crystal structures

X-ray diffraction on a single crystal of octabismuth(2+)-rubidium-tris[tetrachloridoaluminate(III)] at room temperature revealed a hexagonal structure in the space group P63/m (no. 176) with two formula units per unit cell and lattice parameters a = 1320.4(2) and c = 1056.9(1) pm. Atomic parameters and interatomic distances are listed in Tables S1 and S2 of the Supplementary Material available online. The structure of (Bi8)Rb[AlCl4]3 consists of (Bi8)2+ square-antiprisms, Rb+ cations and [AlCl4]– tetrahedra (Figure 2). The rubidium cations and [AlCl4]– anions form ∞ { Rb [ AlCl 4 ] 3 } 2 − ∞ 1 strands along the [001] direction, following the 63 screw axes. The orientation of the tetrahedra renders the strands chiral, but all investigated crystals were merohedral twins. The bismuth polycations are located between the strands on the threefold rotation axes. The basic structural motif is a hexagonal perovskite ABX 3 with A = (Bi8)2+, B = Rb+ and X = [AlCl4]– [27], [28].

Figure 2: Crystal structure of (Bi8)Rb[AlCl4]3 (1) at room temperature along [001]. Ellipsoids comprise 70% of the probability densities of the atoms. For a graphical representation of the crystal structure of (Bi8)Cs[AlCl4]3 see Figure S2 (Supplementary Material).
Figure 2:

Crystal structure of (Bi8)Rb[AlCl4]3 (1) at room temperature along [001]. Ellipsoids comprise 70% of the probability densities of the atoms. For a graphical representation of the crystal structure of (Bi8)Cs[AlCl4]3 see Figure S2 (Supplementary Material).

The structure of compound 1 is isostructural to the disordered room-temperature phase of (Bi8)Tl[AlCl4]3. The M···Cl distances in the distorted [RbCl12]– icosahedron are 344.5(4) and 382.5(5) pm, which match those in Rb[AlCl4] (336.7(2) to 433.5(2) pm) [25], [26], but are longer than for M = Tl, despite the tabulated ionic radii being almost identical for the two cations ([12] r Rb = 172 pm; [12] r Tl = 170 pm) [29]. This is directly reflected in the elongation of the lattice parameter c by about 17 pm in 1. Consequently, the distance between the [AlCl4]– tetrahedra within each strand increases as well, leaving more space for the (Bi8)2+ polycation than in the thallium compound. The Bi···Cl distances in 1 range from 333(1) to 461(1) pm, those in (Bi8)Tl[AlCl4]3 from 327(1) to 451(1) pm [16]. The weakly coordinating environment of the bismuth cluster comprises 24 chloride ions, forming a distorted snub cube, one of the 13 Archimedean solids [30].

For the isostructural cesium compound 2, atomic parameters and interatomic distances are listed in Tables S3 and S4 of the Supplementary Material. Remarkably, the lattice parameters a = 1319.3(1) and c = 1050.6(1) pm at room temperature are slightly smaller than for the rubidium compound 1 (confirmed by powder X-ray diffraction), although the radius of cesium cations was reported to be 16 pm larger ([12] r Cs = 188 pm) [29]. The Cs···Cl distances of 341.0(7) and 384(1) pm span a similar range as in 1. Compared to the distances in Cs[AlCl4] (358.4(4)–436.4(4) pm) [25], the first coordination sphere is significantly closer to the cation. The Bi···Cl distances of 333(1)–454(1) pm are also very similar to those mentioned for 1.

The (Bi8)2+ square-antiprism has been known since 1982, when Krebs et al. managed to determine the crystal structure of (Bi8)[AlCl4]2 [3], [31]. Following modified Wade rules and in accordance with quantum chemical calculations, the polycation can be interpreted as an arachno cluster with 22 skeletal electrons [32], [33], [34]. In 1 and 2, the (Bi8)2+ cation is disordered at room temperature, similar as in (Bi8)[AlC14]2 [3] and (Bi8)3Bi[InI4]9 [10]. Its symmetry does not match the crystallographic threefold axis that runs through its center (site symmetry 6 ‾ ), which results in three superimposed orientations (Figure 3). From other compounds that contain (Bi8)2+, e.g., the fully ordered structure of Bi8[Ta2O2Br7]2 [35], it is known that the antiprism slightly deviates from D 4d symmetry, as the twist angle between its coplanar square faces is not exactly 45° (C 4 symmetry). Thus, also the mirror plane included in the structure model cannot be correct. We applied an approximation with a minimum of atomic positions that represents the three main orientations of the polycation and covers the additional minor deviations in large displacement ellipsoids. This model could be refined without any constraints, but the resulting (too short) interatomic distances cannot be taken as a reference for (Bi8)2+. Twin refinements in the monoclinic subgroup P 1 1 21, which would allow for an ordered arrangement of polyhedra with only C 1 symmetry, did not resolve the disorder. Attempts to induce ordering by cooling to 170 K at a rate of −6 K h−1 resulted in freezing of the various bismuth cluster orientations. However, we observed a dramatic reduction of the Bragg intensities upon cooling, which suggests the formation of very small domains of an ordered structure with lower translational symmetry. This also implies that the disorder is dynamic at room temperature, but probably with a very low frequency of cluster reorientation, which prevents ordering at the applied cooling rate.

Figure 3: a) Superimposed orientations of (Bi8)2+ polycations in (Bi8)Rb[AlCl4]3, b) with identification of the three main orientations by different colors of the bonds. Ellipsoids comprise 70% of the probability densities of the atoms at room temperature.
Figure 3:

a) Superimposed orientations of (Bi8)2+ polycations in (Bi8)Rb[AlCl4]3, b) with identification of the three main orientations by different colors of the bonds. Ellipsoids comprise 70% of the probability densities of the atoms at room temperature.

3 Conclusions

Lewis-acidic ILs containing an excess of AlCl3 again proved to be a versatile reaction medium for the synthesis of bismuth-rich compounds. The two new cluster compounds (Bi8)Rb[AlCl4]3 and (Bi8)Cs[AlCl4]3 contain the known polycation (Bi8)2+ in a weakly coordinating, almost spherical environment that allows reorientation of this arachno cluster at room temperature. The freezing of the disorder upon slow cooling to 170 K indicates comparatively high rotation barriers and thus low frequencies of the reorientation in both compounds.

4 Experimental

4.1 Synthesis and chemical analysis

All compounds were handled in an argon-filled glove box (M. Braun; p(O2)/p 0 < 1 ppm, p(H2O)/p 0 < 1 ppm). The reactions were carried out in silica ampoules with a length of 120 mm and a diameter of 14 mm. The syntheses took place in the IL [BMIm]Cl·4AlCl3, which acted as solvent and reactant.

For the synthesis of (Bi8)Rb[AlCl4]3, an ampoule was loaded with 12.0 mg of RbCl (0.1 mmol, 99%, abcr), 153.6 mg of Bi (0.73 mmol, 99.9%, Alfa Aesar, treated twice with H2 at 220 °C), 21.0 mg of BiCl3 (0.67 mmol, 98%, Alfa Aesar, sublimed three times), 150.0 mg of [BMIm]Cl (0.86 mmol, 98%, Sigma Aldrich, dried under vacuum at 100 °C) and 450.0 mg of AlCl3 (3.38 mmol, sublimed three times). (Bi8)Cs[AlCl4]3 was obtained from a mixture containing 16.8 mg of CsCl (0.1 mmol, 99%, Chemapol), 153.0 mg of Bi (0.73 mmol), 21.0 mg of BiCl3(0.67 mmol), 150.0 mg of [BMIm]Cl (0.86 mmol) and 450.0 mg of AlCl3 (3.38 mmol).

The evacuated and sealed ampoules were heated at 200 °C for 36 h in a tube furnace and then cooled to room temperature at the rate of −6 K h−1. The furnace was tilted before cooling to allow the IL to separate from already precipitated byproducts. The crystals of 1 and 2 were identified visually, according to their color and shape, and separated mechanically from other crystalline species and most of the IL. No further treatment was applied to these crystals, as the small amounts of residual IL on the crystal surface did not impede the following investigations.

EDX spectroscopy was employed to check the chemical composition of the crystals, using a SU8020 (Hitachi) SEM equipped with a Silicon Drift Detector (SDD) X-MaxN (Oxford). Several issues impeded the interpretation of the data. Since the samples could not be polished due to their high sensitivity to moisture, the surface of the crystals was uneven and the crystals themselves tilted against the beam. Furthermore, the compounds partially decompose in the electron beam (acceleration voltage of 25 kV) that is necessary to activate the metal atoms for this measurement. EDX analysis was therefore mainly used as a semi-quantitative analysis to check the ratio between the alkali metal and bismuth. Calculated/measured ratio Bi:Rb:Al:Cl (at.%) in (Bi8)Rb[AlCl4]3: 33.3:4.2:12.5:50/34.5(8):3.8(2):19(1):42(1); Bi:Cs:Al:Cl (at.%) in (Bi8)Cs[AlCl4]3: 33.3:4.2:12.5:50/37(2):4.4(2):20(1):39(3).

4.2 X-ray crystal structure determination

Powder X-ray diffraction was performed at 296(3) K with an X’Pert Pro MPD diffractometer (PANalytical) equipped with a Ge(220) hybrid-monochromator using CuKα 1 radiation (λ = 154.056 pm). Due to their sensitivity to moisture, the samples were contained in a glass capillary (Hilgenberg) with an outer diameter of 0.3 mm.

Single-crystal X-ray diffraction was measured on a four-circle Kappa APEX II CCD diffractometer (Bruker) with a graphite(002) monochromator and a CCD detector at T = 296(1) K. MoKα radiation (λ = 71.073 pm) was used. After integration [36], a numerical absorption correction based on an optimized crystal description was applied [37]. The initial structure solution was performed with Jana2006 [38] and further refinement processed in Shelxl against F o 2 [39], [40], [41].

(Bi8)Rb[AlCl4]3: hexagonal; space group P63/m (no. 176); T = 296(2) K; a = 1320.4(1) pm, c = 1056.9(1) pm, V = 1595.8(3) × 106 pm3; Z = 2; ρ calcd. = 4.71 g cm−3; μ(MoKα) = 46.5 mm−1; 2θ max = 49.9°, −15 ≤ h ≤ 15, −15 ≤ k ≤ 15, −6 ≤ l ≤ 12; 15,132 measured, 992 unique reflections, R int = 0.104, R σ = 0.050; 65 parameters, R 1 [583 F o > 4 σ(F o)] = 0.066, wR 2 (all F o 2) = 0.075, GooF = 2.34, min./max. residual electron density: −1.55/1.88 e × 10−6 pm−3. For atomic parameters see Table S2 of the Supplementary Material.

(Bi8)Cs[AlCl4]3: hexagonal; space group P63/m (no. 176); T = 296(2) K; a = 1319.3(1) pm, c = 1050.6(1) pm, V = 1583.6(3) × 106 pm3; Z = 2; ρ calcd. = 4.85 g cm−3; μ(MoKα) = 46.5 mm−1; 2θ max = 48.8°, −15 ≤ h ≤ 15, −15 ≤ k ≤ 15, −12 ≤ l ≤ 9; 14,584 measured, 927 unique reflections, R int = 0.070, R σ = 0.025; 65 parameters, R 1 [677 F o > 4 σ(F o)] = 0.112, wR 2 (all F o 2) = 0.121, GooF = 6.37, min./max. residual electron density: −3.50/2.67 e × 10−6 pm−3. For atomic parameters see Table S4 of the Supplementary Material.

Further details of the crystal structure determinations are available from the Fachinformationszentrum Karlsruhe, D-76344 Eggenstein-Leopoldshafen (Germany), , on quoting the depository number CSD-2071323 for (Bi8)Rb[AlCl4]3 and CSD-2071319 for (Bi8)Cs[AlCl4]3.

5 Supporting information

A projection of the structure of (Bi8)Cs[AlCl4]3 as well as powder diffractograms and atomic coordinates including displacement parameters for both compounds are given as supplementary material available online (https://doi.org/10.1515/znb-2021-0042).

Dedicated to: Professor Richard Dronskowski of the RWTH Aachen on the occasion of his 60th birthday.

Corresponding author: Michael Ruck, Fakultät Chemie und Lebensmittelchemie, Technische Universität Dresden, 01062 Dresden, Germany; and Max-Planck-Institut für Chemische Physik fester Stoffe, Nöthnitzer Straße 40, 01187 Dresden, Germany, E-mail: . https://tu-dresden.de/mn/chemie/ac/ac2/

Funding source: Deutsche Forschungsgemeinschaft

Acknowledgment

We acknowledge technical support by M. Münch and A. Brünner (TU Dresden).

  1. Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.

  2. Research funding: This research was funded by the Deutsche Forschungsgemeinschaft (DFG) within the Priority Program SPP 1708.

  3. Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

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Supplementary Material

The online version of this article offers supplementary material (https://doi.org/10.1515/znb-2021-0042).

Received: 2021-03-26
Accepted: 2021-05-12
Published Online: 2021-05-31
Published in Print: 2021-11-25

© 2021 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

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  2. In this issue
  3. Laudatio/Preface
  4. Celebrating the 60th birthday of Richard Dronskowski
  5. Review
  6. Orbital-selective electronic excitation in phase-change memory materials: a brief review
  7. Research Articles
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  9. d- and s-orbital populations in the d block: unbound atoms in physical vacuum versus chemical elements in condensed matter. A Dronskowski-population analysis
  10. Single-crystal structures of A 2SiF6 (A = Tl, Rb, Cs), a better structure model for Tl3[SiF6]F, and its novel tetragonal polymorph
  11. Na2La4(NH2)14·NH3, a lanthanum-rich intermediate in the ammonothermal synthesis of LaN and the effect of ammonia loss on the crystal structure
  12. Linarite from Cap Garonne
  13. Salts of octabismuth(2+) polycations crystallized from Lewis-acidic ionic liquids
  14. High-temperature diffraction experiments and phase diagram of ZrO2 and ZrSiO4
  15. Thermal conversion of the hydrous aluminosilicate LiAlSiO3(OH)2 into γ-eucryptite
  16. Crystal structure of mechanochemically prepared Ag2FeGeS4
  17. Effect of nanostructured Al2O3 on poly(ethylene oxide)-based solid polymer electrolytes
  18. Sr7N2Sn3: a layered antiperovskite-type nitride stannide containing zigzag chains of Sn4 polyanions
  19. Exploring the frontier between polar intermetallics and Zintl phases for the examples of the prolific ALnTnTe3-type alkali metal (A) lanthanide (Ln) late transition metal (Tn) tellurides
  20. Zwitterion coordination to configurationally flexible d 10 cations: synthesis and characterization of tetrakis(betaine) complexes of divalent Zn, Cd, and Hg
  21. An approach towards the synthesis of lithium and beryllium diphenylphosphinites
  22. Synthesis, crystal and electronic structure of CaNi2Al8
  23. Crystal and electronic structure of the new ternary phosphide Ho5Pd19P12
  24. Synthesis, structure, and magnetic properties of the quaternary oxysulfides Ln 5V3O7S6 (Ln = La, Ce)
  25. Synthesis, crystal and electronic structure of BaLi2Cd2Ge2
  26. Structural variations of trinitrato(terpyridine)lanthanoid complexes
  27. Preparation of CoGe2-type NiSn2 at 10 GPa
  28. Controlled exposure of CuO thin films through corrosion-protecting, ALD-deposited TiO2 overlayers
  29. Experimental and computational investigations of TiIrB: a new ternary boride with Ti1+x Rh2−x+y Ir3−y B3-type structure
  30. Synthesis and crystal structure of the lanthanum cyanurate complex La[H2N3C3O3]3 · 8.5 H2O
  31. Cd additive effect on self-flux growth of Cs-intercalated NbS2 superconducting single crystals
  32. 14N, 13C, and 119Sn solid-state NMR characterization of tin(II) carbodiimide Sn(NCN)
  33. Superexchange interactions in AgMF4 (M = Co, Ni, Cu) polymorphs
  34. Copper(I) iodide-based organic–inorganic hybrid compounds as phosphor materials
  35. On iodido bismuthates, bismuth complexes and polyiodides with bismuth in the system BiI3/18-crown-6/I2
  36. Synthesis, crystal structure and selected properties of K2[Ni(dien)2]{[Ni(dien)]2Ta6O19}·11 H2O
  37. First low-spin carbodiimide, Fe2(NCN)3, predicted from first-principles investigations
  38. A novel ternary bismuthide, NaMgBi: crystal and electronic structure and electrical properties
  39. Magnetic properties of 1D spin systems with compositional disorder of three-spin structural units
  40. Amine-based synthesis of Fe3C nanomaterials: mechanism and impact of synthetic conditions
  41. Enhanced phosphorescence of Pd(II) and Pt(II) complexes adsorbed onto Laponite for optical sensing of triplet molecular dioxygen in water
  42. Theoretical investigations of hydrogen absorption in the A15 intermetallics Ti3Sb and Ti3Ir
  43. Assembly of cobalt-p-sulfonatothiacalix[4]arene frameworks with phosphate, phosphite and phenylphosphonate ligands
  44. Chiral bis(pyrazolyl)methane copper(I) complexes and their application in nitrene transfer reactions
  45. UoC-6: a first MOF based on a perfluorinated trimesate ligand
  46. PbCN2 – an elucidation of its modifications and morphologies
  47. Flux synthesis, crystal structure and electronic properties of the layered rare earth metal boride silicide Er3Si5–x B. An example of a boron/silicon-ordered structure derived from the AlB2 structure type
https://doi.org/10.1515/znb-2021-0042
Keywords for this article
bismuth polycations; crystal structure; ionic liquids

Articles in the same Issue

  1. Frontmatter
  2. In this issue
  3. Laudatio/Preface
  4. Celebrating the 60th birthday of Richard Dronskowski
  5. Review
  6. Orbital-selective electronic excitation in phase-change memory materials: a brief review
  7. Research Articles
  8. Solving the puzzle of the dielectric nature of tantalum oxynitride perovskites
  9. d- and s-orbital populations in the d block: unbound atoms in physical vacuum versus chemical elements in condensed matter. A Dronskowski-population analysis
  10. Single-crystal structures of A 2SiF6 (A = Tl, Rb, Cs), a better structure model for Tl3[SiF6]F, and its novel tetragonal polymorph
  11. Na2La4(NH2)14·NH3, a lanthanum-rich intermediate in the ammonothermal synthesis of LaN and the effect of ammonia loss on the crystal structure
  12. Linarite from Cap Garonne
  13. Salts of octabismuth(2+) polycations crystallized from Lewis-acidic ionic liquids
  14. High-temperature diffraction experiments and phase diagram of ZrO2 and ZrSiO4
  15. Thermal conversion of the hydrous aluminosilicate LiAlSiO3(OH)2 into γ-eucryptite
  16. Crystal structure of mechanochemically prepared Ag2FeGeS4
  17. Effect of nanostructured Al2O3 on poly(ethylene oxide)-based solid polymer electrolytes
  18. Sr7N2Sn3: a layered antiperovskite-type nitride stannide containing zigzag chains of Sn4 polyanions
  19. Exploring the frontier between polar intermetallics and Zintl phases for the examples of the prolific ALnTnTe3-type alkali metal (A) lanthanide (Ln) late transition metal (Tn) tellurides
  20. Zwitterion coordination to configurationally flexible d 10 cations: synthesis and characterization of tetrakis(betaine) complexes of divalent Zn, Cd, and Hg
  21. An approach towards the synthesis of lithium and beryllium diphenylphosphinites
  22. Synthesis, crystal and electronic structure of CaNi2Al8
  23. Crystal and electronic structure of the new ternary phosphide Ho5Pd19P12
  24. Synthesis, structure, and magnetic properties of the quaternary oxysulfides Ln 5V3O7S6 (Ln = La, Ce)
  25. Synthesis, crystal and electronic structure of BaLi2Cd2Ge2
  26. Structural variations of trinitrato(terpyridine)lanthanoid complexes
  27. Preparation of CoGe2-type NiSn2 at 10 GPa
  28. Controlled exposure of CuO thin films through corrosion-protecting, ALD-deposited TiO2 overlayers
  29. Experimental and computational investigations of TiIrB: a new ternary boride with Ti1+x Rh2−x+y Ir3−y B3-type structure
  30. Synthesis and crystal structure of the lanthanum cyanurate complex La[H2N3C3O3]3 · 8.5 H2O
  31. Cd additive effect on self-flux growth of Cs-intercalated NbS2 superconducting single crystals
  32. 14N, 13C, and 119Sn solid-state NMR characterization of tin(II) carbodiimide Sn(NCN)
  33. Superexchange interactions in AgMF4 (M = Co, Ni, Cu) polymorphs
  34. Copper(I) iodide-based organic–inorganic hybrid compounds as phosphor materials
  35. On iodido bismuthates, bismuth complexes and polyiodides with bismuth in the system BiI3/18-crown-6/I2
  36. Synthesis, crystal structure and selected properties of K2[Ni(dien)2]{[Ni(dien)]2Ta6O19}·11 H2O
  37. First low-spin carbodiimide, Fe2(NCN)3, predicted from first-principles investigations
  38. A novel ternary bismuthide, NaMgBi: crystal and electronic structure and electrical properties
  39. Magnetic properties of 1D spin systems with compositional disorder of three-spin structural units
  40. Amine-based synthesis of Fe3C nanomaterials: mechanism and impact of synthetic conditions
  41. Enhanced phosphorescence of Pd(II) and Pt(II) complexes adsorbed onto Laponite for optical sensing of triplet molecular dioxygen in water
  42. Theoretical investigations of hydrogen absorption in the A15 intermetallics Ti3Sb and Ti3Ir
  43. Assembly of cobalt-p-sulfonatothiacalix[4]arene frameworks with phosphate, phosphite and phenylphosphonate ligands
  44. Chiral bis(pyrazolyl)methane copper(I) complexes and their application in nitrene transfer reactions
  45. UoC-6: a first MOF based on a perfluorinated trimesate ligand
  46. PbCN2 – an elucidation of its modifications and morphologies
  47. Flux synthesis, crystal structure and electronic properties of the layered rare earth metal boride silicide Er3Si5–x B. An example of a boron/silicon-ordered structure derived from the AlB2 structure type
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