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Copper(I) iodide-based organic–inorganic hybrid compounds as phosphor materials

  • Xiuze Hei , Yang Fang , Simon J. Teat , Colin Farrington , Megan Bonite and Jing Li EMAIL logo
Published/Copyright: October 5, 2021
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Zeitschrift für Naturforschung B
From the journal Zeitschrift für Naturforschung B Volume 76 Issue 10-12

Abstract

Two photoluminescent copper(I) iodide inorganic-organic hybrid materials have been synthesized and structurally characterized as 1D-Cu2I2(bpoe)2 (1) and 1D-Cu2I2(bbtpe-m)2 (2) (bpoe = 1,2-bis(pyridin-3-yloxy)ethane, bbtpe-m = 1,1′-(3-methylpentane-1,5-diyl)bis(1H-benzo[1,2,3]triazole). Both are chain-like structures composed of Cu2I2 rhomboid dimers connected by bidentate ligands. Their emission colors range from cyan to yellow with relatively high internal quantum yields in the solid state. The tunable band gap and emission color is achieved by varying the LUMO energies of the ligands. The structures are robust and remain stable up to T = 260 °C, and coupled with their efficient and adjustable luminescence, facile synthesis, and non-toxic nature, these compounds demonstrate potential as rare earth element (REE)-free phosphors.

1 Introduction

Currently, the market of the white-light-emitting diodes (WLEDs) used for general lighting applications is still dominated by the phosphor-converted WLEDs (pc-WLEDs), which heavily rely on the rare earth element (REE)-containing phosphors [1], [2], [3]. However, due to the severe pollution caused by the mining and extraction processes of REEs, as well as increasing demand for many high-tech applications, these commercial phosphors are subject to potential supply, cost, and environmental risks [4], [5], [6]. Therefore, the search for alternative REE-free phosphor materials has been pushed to high importance. Several types of materials have been reported as alternatives for this use and demonstrate intriguing promise, such as colloidal quantum dots and perovskites. Among them, copper(I) halide-based inorganic-organic hybrid semiconductors have risen to prominence [7], [8], [9], [10], [11].

The main advantages of copper halide (CuX)-based crystalline hybrid materials lie in their non-toxic nature, facile and easily scalable synthesis, intensive photoluminescence, optical tunability, and structural diversity [7, 12, 13]. This class of compounds is generally formulated as Cu a X b L c , their inorganic motifs range from zero-dimensional (0D) molecular clusters to three-dimensional (3D) frameworks and lead to 0D–3D hybrid structures via coordinative bonds with organic ligands [8, 13]. Among them, 1D chain-like hybrid structures containing discrete Cu2I2 rhomboid dimers are of great interest due to their tunable band gaps and optical properties, as well as their simple synthesis [14], [15], [16], [17]. Previous research has revealed that such band gap tunability originates from the interplay between both the inorganic and organic motifs [18], [19], [20], [21]. While the valence band maximum (VBM) originates mainly from Cu 3d and I 5p atomic orbitals, the conductive band minimum (CBM) is largely made of the lowest unoccupied molecular orbitals (LUMO) of the organic ligands [21]. Thus, the band gap of the as-synthesized hybrid materials can be systematically modulated by altering the LUMO of the ligands. In these structures, the photoluminescence (PL) mechanism involves mainly metal-to-ligand charge transfer (MLCT) and halide-to-ligand charge transfer (XLCT), or (M + X)LCT, which has also been observed in many other CuX-based hybrid materials [19, 21], [22], [23], [24].

Herein, we report two new chain-like hybrid materials based on Cu2I2 rhomboid dimers, namely 1D-Cu2I2(bpoe)2 (1) and 1D-Cu2I2(bbtpe-m)2 (2) (bpoe = 1,2-bis(pyridin-3-yloxy)ethane, bbtpe-m = 1,1′-(3-methylpentane-1,5-diyl)bis(1H-benzo[1,2,3]triazole). These hybrid structures demonstrate intense photoluminescence in the cyan to yellow region under 360 nm irradiation, with internal quantum yields (IQYs) reaching 45%. All compounds remain stable up to T = 200 °C.

2 Experimental section

2.1 Materials

CuI (98%, Alfa Aesar); 1H-benzo [1,2,3]-triazole (99%, Alfa Aesar); potassium iodide (99%, Alfa Aesar); acetonitrile (99.5%, VWR); methanol (99%, Alfa Aesar); dimethyl sulfoxide (99%, Alfa Aesar); 3-hydroxypyridine (98%, TCI); 1,2-dibromoethane (98%, Alfa Aesar); sodium hydroxide (98%, TCI); 1,5-dibromo-3-methylpentane (98%, Alfa Aesar) and sodium salicylate (99%, Merck).

2.2 Preparation of 1,2-bis(pyridin-3-yloxy)ethane (bpoe)

3-Hydroxypyridine (1.9 g, 20 mmol) and sodium hydroxide (1.2 g, 30 mmol) were added to 20 mL DMSO and the mixture was stirred for 10 min before the addition of 1,2-dibromoethane (1.7 g, 9 mmol). The reaction mixture was stirred at 80 °C overnight. After cooling to room temperature, it was poured into DI water and extracted with ethyl acetate three times. The organic phase was combined and dried with sodium sulfate before evaporation of all volatiles under reduced pressure. The remaining brown solid was recrystallized from acetone/hexane to give white crystals as the final product. Yield: 79%.

2.3 Preparation of 1,1′-(3-methylpentane-1,5-diyl)bis(1H-benzo[1,2,3]triazole) (bbtpe-m)

1H-benzo[1,2,3]-triazole (2.4 g, 20 mmol), sodium hydroxide (1.2 g, 30 mmol), and 1,5-dibromo-3-methylpentane (2.2 g, 9 mmol) were added to 20 mL DMSO. The reaction mixture was stirred at 80 °C overnight. After cooling to room temperature, it was poured into DI water and extracted with ethyl acetate three times. The organic phase was combined and all volatiles evaporated under reduced pressure. The residue was purified by column chromatography on silica gel using hexanes-ethyl acetate (4:1), giving an oil-like liquid as the final product. Yield: 51%.

2.4 Synthesis of 1D-Cu2I2(bpoe)2 (1)

CuI (38 mg, 0.2 mmol) was dissolved in KI saturated aqueous solution (2 mL) in a reaction vial. Acetonitrile (2 mL) was added as another layer followed by the slow addition of the ligand bpoe (43 mg, 0.2 mmol) in methanol solution (2 mL). The reaction mixture was kept undisturbed at 60 °C for three days. Yellow single crystals, along with a crystalline powder, of compound 1 were collected after filtration. Yield: 47%.

2.5 Synthesis of 1D-Cu2I2(bbtpe-m)2 (2)

Compound 2 was synthesized from reactions similar to those used in producing 1 except that bbtpe-m was used as the ligand. Pale yellow block-like crystals of compound 2 were collected after filtration. Yield: 63%.

2.6 Single-crystal X-ray diffraction (SCXRD)

Single-crystal data of 1 and 2 were collected using a D8 goniostat equipped with a Bruker PHOTON100 CMOS detector at the Advanced Light Source (ALS), Lawrence Berkeley National Laboratory, using synchrotron radiation. The structures were solved by Direct Methods and refined by full-matrix least-squares on F 2 using the Bruker Shelxtl package [25]. Table 1 summarizes the crystal structure data.

Table 1:

Crystal structure data for 1 and 2.

1D-Cu2I2(bpoe)2 (1) 1D-Cu2I2(bbtpe-m)2 (2)
Empirical formula C26H27Cu2I2N5O4 C18H20CuIN6
M r 854.40 510.84
Crystal system; space group Triclinic; P 1 ‾ Triclinic; P 1 ‾
a, Å 8.4168(3) 10.0710(4)
b, Å 12.6023(4) 10.2510(4)
c, Å 14.1462(5) 10.2974(4)
α, deg 79.930(2) 82.409(1)
β, deg 84.018(2) 63.528(1)
γ, deg 81.486(2) 82.412(1)
V, Å3 1456.37(9) 940.07(6)
Z 2 2
D calcd, g cm−3 1.948 1.805
μ(MoKα), cm−1 4.540 2.993
F(000), e 828 504
hkl range ±14, ±21, ±23 ±15, ±15, ±15
θ range, deg 2.209–40.270 2.273–34.135
Refl. measured 26,943 36,783
Refl. unique 13,808 7172
R int 0.0322 0.0472
Param. refined 353 283
R(F)/wR(F 2)a (I > 2 σ(I)) 0.0393/0.0763 0.0237/0.0562
R(F)/wR(F 2)a (all data) 0.0723/0.0877 0.0260/0.0575
GoF (F 2)b 1.023 1.082
Δρ fin (max/min), e Å−3 2.17/−1.87 0.80/−1.22

  1. a R(F) = ||F o| – |F c||/Σ|F o|, wR(F 2) = [Σw(F o 2 – F c 2)2/Σw(F o 2)2]1/2, w = [σ 2(F o 2) + (AP)2 + BP]−1, where P = (Max(F o 2, 0) + 2F c 2)/3; bGoF = [Σw(F o 2 – F c 2)2/(n obs – n param)]1/2.

CCDC 2105005 and 2105006 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

2.7 Powder X-ray diffraction (PXRD) analysis

Powder X-ray diffraction (PXRD) analysis was carried out on a Rigaku Ultima-IV unit using CuKα radiation (λ = 1.5406 Å). The operation power was 40 kV/44 mA. Data was collected in a 2θ range of 3°–40° with a scan speed of 2° min−1.

2.8 Thermogravimetric analysis (TGA)

Thermogravimetric analyses (TGA) of the samples were performed using the TA Instrument Q5000IR with nitrogen flow and sample purge rates at 10 and 12 mL min−1, respectively. Samples were heated from room temperature to 450 °C at a rate of 10 K min−1 under a nitrogen flow.

2.9 Photoluminescence measurements

Photoluminescence measurements were carried out on a Horiba Duetta fluorescence spectrophotometer at room temperature. Excitation spectra were measured and monitored at the maximum of the emission spectra.

2.10 Optical absorption experiments

Diffuse reflectance data was recorded on a Shimadzu UV-3600 UV/Vis-NIR spectrometer at room temperature. The reflectance was converted to a Kubelka–Munk function, α/S = (1 − R)2/2R (α is the absorption coefficient, R is the reflectance and S is the scattering coefficient. S was treated as a constant since the average particle size of the samples is significantly larger than 5 µm.

2.11 Internal quantum yield (IQY) measurements

IQYs were recorded using a C9920-02 absolute quantum yield measurement system (Hamamatsu Photonics) with a 150 W Xenon monochromatic light source and a 3.3-inch integrating sphere. Sodium salicylate was used as the standard with a reported IQY of 60%.

2.12 DFT calculations

The density-of-states (DOS) of selected compounds were calculated using the Cambridge Serial Total Energy Package (CASTEP) in the Materials studio package [26] using the crystal structures obtained from single-crystal X-ray analysis. Generalized gradient approximations (GGA) with Perdew–Burke–Ernzerhof (PBE) exchange correlation functional (xc) were used for all calculations. The plane-wave kinetic energy cutoff was set as 351 eV, ultrasoft pseudopotentials were used for all chemical elements and the total energy tolerance was set to be 1 × 10−5 eV atom−1.

3 Results and discussion

The layered diffusion method has been demonstrated as an efficient method for obtaining high-quality crystals of CuI-based hybrid structures [8, 20]. Direct mixing of CuI with the ligands at room temperature generally afford powdery compounds immediately, due to the fast nucleation rate. To obtain highly crystalline compounds, a buffer layer, namely acetonitrile was placed between the solutions containing CuI (in KI aqueous solution) and the ligands (in methanol solution), respectively. Single crystals of both new hybrid compounds were obtained via this method. The single-crystal X-ray analyses revealed that these compounds share a formula of Cu2I2(L)2 and both crystalize in space group P 1 ‾ . Detailed crystallographic data are summarized in Table 1. Their structures feature Cu2I2 rhomboid dimers connected by the bidentate ligands as shown in Figure 1. All Cu atoms are tetrahedrally coordinated to two iodine atoms and two N atoms from two ligands, and all halogen atoms are bridging to two copper atoms. The Cu–N coordinative bond lengths are in the range of 2.0–2.1 Å, comparable to those of similar structures [23, 27], [28], [29].

Figure 1: (a) Schematic drawing illustrating the connectivity in crystals of compounds 1 and 2 with the Cu2I2 inorganic module and the two ligands. Structural plots and the copper coordination environments of (b) compound 1, 1D-Cu2I2(bpoe)2 and (c) compound 2, 1D-Cu2I2(bbtpe-m)2. Color scheme: cyan: Cu; purple: I; gray: C; blue: N. All H atoms and disorders are omitted for clarity.
Figure 1:

(a) Schematic drawing illustrating the connectivity in crystals of compounds 1 and 2 with the Cu2I2 inorganic module and the two ligands. Structural plots and the copper coordination environments of (b) compound 1, 1D-Cu2I2(bpoe)2 and (c) compound 2, 1D-Cu2I2(bbtpe-m)2. Color scheme: cyan: Cu; purple: I; gray: C; blue: N. All H atoms and disorders are omitted for clarity.

The photophysical properties of the compounds were investigated using UV/Vis optical absorption spectroscopy and photoluminescence (PL) emission spectroscopy at ambient conditions. Both compounds emit in the visible-light region, as shown in Figure 2a. Their emission colors range from cyan with Commission International del’Eclairage (CIE) color coordinates (x, y) of (0.27, 0.46) to yellow with CIE color coordinates of (0.43, 0.50) (Figure 2b). The emission profile of both compounds demonstrates single band features, with an average of full-width at half-maximum (FWHM) of ∼100 nm, which has been observed for many CuX-based hybrid materials [28, 30], [31], [32]. The internal quantum yields (IQYs) of both compounds were measured at room temperature using 360 nm as excitation wavelength. The IQYs of compounds 1 and 2 are 45 and 25%, respectively (Table 2).

Figure 2: (a) Normalized excitation and emission spectra of title compounds. (b) Luminescence chromaticity of compounds 1 and 2. (c) Optical absorption spectra of compounds 1 and 2.
Figure 2:

(a) Normalized excitation and emission spectra of title compounds. (b) Luminescence chromaticity of compounds 1 and 2. (c) Optical absorption spectra of compounds 1 and 2.

Table 2:

Summary of important physical properties of compounds 1 and 2.

Compound Band Gap (eV) Emission (nm) CIE IQY (%) T d (°C)a
1D-Cu2I2(bpoe)2 (1) 2.5 560 (0.43, 0.50) 45 200
1D-Cu2I2(bbtpe-m)2 (2) 2.7 510 (0.27, 0.46) 25 260

  1. a T d: decomposition temperature.

The optical absorption spectra of both compounds were collected at room temperature and converted to the Kubelka–Munk function as shown in Figure 2c. Estimated from their absorption edges, the band gap of the compounds 1 and 2 are determined as 2.5 and 2.7 eV, respectively. These numbers are well in trend with their emission energies.

To gain insight into the origin of the emission, density functional theory (DFT) calculations were conducted to calculate the density of states (DOS) of both compounds using the Cambridge Serial Total Energy Package (CASTEP) in Material Studio [26]. As shown in Figure 3, the projected DOS (PDOS) of both compounds share the same features. The VBM is made up primarily of the inorganic components, namely Cu 3d and I 5p atomic orbitals; while the CBM dominantly comes from the organic ligands. Suggested by the calculations, the emission mechanism of both compounds can be attributed to a combination of MLCT and XLCT, or (M + X)LCT. Similar results have been observed for many other reported CuX-based hybrid materials [4, 11, 14, 33]. The calculated band gaps of compounds 1 and 2 have relatively smaller values, as the local density approximation (LDA) or generalized gradient approximation (GGA) functionals alone underestimate the band gaps [34].

Figure 3: Total density of states (DOS) and projected density of states (PDOS) for compounds 1 and 2. Line color scheme: dashed black: total; cyan: Cu(3d); purple: I(5p); black: C(2p); blue: N(2p); red: O(2p).
Figure 3:

Total density of states (DOS) and projected density of states (PDOS) for compounds 1 and 2. Line color scheme: dashed black: total; cyan: Cu(3d); purple: I(5p); black: C(2p); blue: N(2p); red: O(2p).

Thermogravimetric analysis (TGA) was performed on both compounds to evaluate their thermal stability. It has been proven that with increased dimensionality, the thermal and photo-stability of neutral CuI(L) hybrid structures generally get enhanced [8, 27]. As shown in Figure 4a, the decomposition temperatures of compounds 1 and 2 are 200 and 260 °C, respectively. These decomposition temperatures are notably higher than those of 0D molecular clusters made of the same Cu2I2 rhomboids, which usually decompose below T = 100 °C [14, 35]. It is worth noting that the strength of the Cu–N coordination bond also plays a role [12, 24, 36]. The N atoms in benzotriazole generally have higher electron-donating ability than the N atoms in pyridine [23], thus leading to the formation of stronger Cu–N bonds than with the latter, which also agrees with the relatively shorter Cu–N bonds in compound 2 (∼2.04 Å), compared to those in compound 1 (∼2.07 Å). Compound 2 was selected to evaluate the air/water stability of these hybrids. After heating to T = 120 °C for four days without any protection, its PXRD pattern remains highly crystalline and has no sign of decomposition or impurity phase formation. Similarly, no change was observed after being placed in boiling water for four days.

Figure 4: (a) Thermogravimetric (TG) plots of compounds 1 and 2, along with a 0D-Cu2I2(3-pc)4 structure which is made of the same Cu2I2 rhomboid dimer core. (b) PXRD patterns of compound 2 taken under different conditions.
Figure 4:

(a) Thermogravimetric (TG) plots of compounds 1 and 2, along with a 0D-Cu2I2(3-pc)4 structure which is made of the same Cu2I2 rhomboid dimer core. (b) PXRD patterns of compound 2 taken under different conditions.

4 Conclusions

In summary, two chain-like crystalline organic-inorganic hybrid materials made of Cu2I2 rhomboid dimers and bidentate ligands have been synthesized and structurally characterized. These compounds demonstrate efficient photoluminescence ranging from cyan to yellow color with IQYs reaching 45% when excited by UV (λ = 360 nm) light. Both compounds exhibit excellent resistance to heat and moisture with decomposition temperatures exceeding 200 °C, significantly higher than many previously reported 0D clusters made of the same rhomboid dimer of Cu2I2 inorganic module. The robustness, efficient photoluminescence, and facile synthesis of these compounds, coupled with their earth-abundant and non-toxic components, make them promising candidates for REE-free phosphors for general lighting applications.

Corresponding author: Jing Li, Department of Chemistry and Chemical Biology, Rutgers University, Piscataway, NJ 08854, USA, E-mail:

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

Funding source: U.S. Department of Energy

Award Identifier / Grant number: DE-SC0019902

Funding source: Office of Science

Award Identifier / Grant number: DE-AC02-05CH11231

  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 used the Advanced Light Source, which is a DOE Office of Science User Facility under contract No. DE-AC02-05CH11231. The authors acknowledge the partial support from the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences (Grant No. DE-SC0019902) for the synthesis and part of characterization work.

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

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Received: 2021-08-29
Accepted: 2021-09-25
Published Online: 2021-10-05
Published in Print: 2021-11-25

© 2021 Walter de Gruyter GmbH, Berlin/Boston

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
https://doi.org/10.1515/znb-2021-0126

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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