Octahedral Cavities Research Articles

Establishing the Link across the Synthesis Reaction Kinetics, Structural Changes, and Photocatalytic Efficiency of an Enhanced Chitosan–Clay (1:3) Nanocomposite

This research investigates the influence of synthesis kinetics on the structural and photocatalytic properties of chitosan–clay nanocomposites (Cs/MMT) and chitosan–hectorite nanocomposites (Cs/HET), employing an optimized initial stoichiometry of 1:3. Utilizing a variety of analytical techniques, including X-ray diffraction (XRD), transmission electron microscopy (TEM), and Fourier-transform infrared spectroscopy (FTIR), the study explores the structural evolution of the nanocomposites and their photocatalytic performance using semiconductor catalysts TiO2 and ZnO. The findings emphasize the significant impact of reaction kinetics, particularly after 3 h of reaction time, on the structural features of the nanocomposites. Notably, Cs/MMT demonstrates greater crystalline stability compared to Cs/HET due to variations in octahedral cavity occupancy in the initial clays. FTIR and TEM analyses depict the progressive evolution of the nanocomposites during the reaction, shedding light on how reaction kinetics drive the formation of specific bonds within the nanocomposites. In terms of photocatalytic activity, this study provides insights into the complex dynamics of photocatalytic degradation, with a specific focus on the performance of TiO2 and ZnO under diverse experimental conditions. The superior efficacy of TiO2 as a catalyst, particularly when integrated with Cs/MMT nanocomposites, is unequivocally demonstrated, with degradation rates exceeding 80%. This preference stems from TiO2 consistently exhibiting higher degradation rates compared to ZnO, attributed to structural disparities between montmorillonite and hectorite, influencing catalyst–support interactions. The findings underscore the critical importance of selecting suitable catalyst and support matrix combinations for optimizing performance in specific applications.

Polysubstitution Induced Centrosymmetric-to-Noncentrosymmetric Structural Transformation and Nonlinear-Optical Behavior: The Case of Na0.45Ag0.55Ga3Se5.

Obtaining compounds with large nonlinear-optical (NLO) coefficients and wide band gaps is challenging due to their competitive requirements for chemical bonds. Herein, the first member with mixed cations on the A site in the A-M3-Q5 or A-Ag-M6-Q10 (A = alkali metal; M = Ga, In; Q = S, Se, Te) family, viz. Na0.45Ag0.55Ga3Se5 (NAGSe), was obtained by a solid-state reaction. Its structure features [GaSe4] tetrahedra built three-dimensional {[Ga3Se5]-}∞ network, with Na and Na/Ag cations located at the octahedral cavities. Noncentrosymmetric (R32) NAGSe can also be transformed from centrosymmetric RbGa3S5 (P21/c) via multiple-site cosubstitution. NAGSe exhibits the highest NLO response (1.9 × AGS) in the A-Ag-M-Q family. Crystal structure analysis and theoretical calculations suggest that the NLO response is mainly contributed by the regularly arranged [GaSe4] units. This work enriches the exploration of the undeveloped A-M3-Q5 or A-Ag-M6-Q10 family as potential infrared NLO materials.

Ba3SnGa10-xInxO20 (0 ≤ x ≤ 2): site-selective doping, band structure engineering and photocatalytic overall water splitting.

Developing new photocatalysts and deciphering the structure-property relationship are always the central topics in photocatalysis. In this study, a new photocatalyst Ba3SnGa10O20 containing two d10 metal cations was prepared by a high temperature solid state reaction, and its crystal structure was investigated by Rietveld refinements of monochromatic X-ray powder diffraction data for the first time. There are 2 Ba, 4 metal cations and 6 O independent atoms in a unit cell. Sn4+ and Ga3+ co-occupy the octahedral cavities named M1 and M2 sites, and the other two metal sites are fully occupied by Ga3+. Rational In3+-to-Ga3+ substitution was performed to reduce the potential of the conduction band minimum and enhance the light absorption ability, which was indeed confirmed using UV-vis diffuse reflectance spectra and Mott-Schottky plots for Ba3SnGa10-xInxO20 (0 ≤ x ≤ 2). Interestingly, In3+ exhibits site selective doping at M1 and M2 sites exclusively. With the light absorption ability enhanced, the photocatalytic overall water splitting activity was also improved, i.e. the photocatalytic H2 generation rate was 1.7(1) μmol h-1 for Ba3SnGa10O20, and the optimal catalyst Ba3SnGa8.5In1.5O20 loaded with 1.0 wt% Pd exhibited the H2 generation rate of 27.5(4) μmol h-1 and the apparent quantum yield at 254 nm was estimated to be 2.28% in pure water.

Phase Chemistry for Hydration Sensitive (De)intercalation of Lithium Aluminum Layered Double Hydroxide Chlorides.

Lithium aluminum layered double hydroxide chlorides (LADH-Cl) have been widely used for lithium extraction from brine. Elevation of the performances of LADH-Cl sorbents urgently requires knowledge of the composition-structure-property relationship of LADH-Cl in lithium extraction applications, but these are still unclear. Herein, combining the phase equilibrium experiments, advanced solid characterization methods, and theoretical calculations, we constructed a cyclic work diagram of LADH-Cl for lithium capture from aqueous solution, where the reversible (de)hydration and (de)intercalation induced phase evolution of LADH-Cl dominates the apparent lithium "adsorption-desorption" behavior. It is found that the real active ingredient in LADH-Cl type lithium sorbents is a dihydrated LADH-Cl with an Al:Li molar ratio varying from 2 to 3. This reversible process indicates an ultimate reversible lithium (de)intercalation capacity of ∼10 mg of Li per g of LADH-Cl. Excessive lithium deintercalation results in the phase structure collapse of dihydrated LADH-Cl to form gibbsite. When interacting with a concentrated LiCl aqueous solution, gibbsite is easily converted into lithium saturated intercalated LADH-Cl phases. By further hydration with a diluted LiCl aqueous solution, this phase again converts to the active dihydrated LADH-Cl. In the whole cyclic progress, lithium ions thermodynamically favor staying in the Al-OH octahedral cavities, but the (de)intercalation of lithium has kinetic factors deriving from the variation of the Al-OH hydroxyl orientation. The present results provide fundamental knowledge for the rational design and application of LADH-Cl type lithium sorbents.

The Crystal Structure of Manganotychite, Na6Mn2(CO3)4(SO4), and Structural Relations in the Northupite Group

The crystal structure of manganotychite has been refined using the holotype specimen from the Alluaiv Mountain, Lovozero massif, Kola peninsula, Russia. The mineral is cubic, Fd3¯, a = 14.0015(3) Å, V = 2744.88(18) Å3, Z = 8, R1 = 0.020 for 388 independently observed reflections. Manganotychite is isotypic to tychite and ferrotychite. Its crystal structure is based upon a three-dimensional infinite framework formed by condensation of MnO6 octahedra and CO3 groups by sharing common O atoms. The sulfate groups and Na+ cations reside in the cavities of the octahedral-triangular metal-carbonate framework. In terms of symmetry and basic construction of the octahedral-triangular framework, the crystal structure of manganotychite is identical to that of northupite, Na3Mg(CO3)2Cl. The transition northupite → tychite can be described as a result of the multiatomic 2Cl− → (SO4)2− substitution, where both chlorine and sulfate ions are the extra-framework constituents. However, the positions occupied by sulfate groups and chlorine ions correspond to different octahedral cavities within the skeletons of Na atoms. The crystal structure of northupite can be considered as an interpenetration of two frameworks: anionic [Mg(CO3)2]2− octahedral-triangular framework and cationic [ClNa3]2− framework with the antipyrochlore topology. Both manganotychite and northupite structure types can be described as a modification of the crystal structure of diamond (or the dia net) via the following steps: (i) replacement of a vertex of the dia net by an M4 tetrahedron (no symmetry reduction); (ii) attachment of (CO3) triangles to the triangular faces of the M4 tetrahedra (accompanied by the Fd3¯m → Fd3¯ symmetry reduction); (iii) filling voids of the resulting framework by Na+ cations (no symmetry reduction); and (iv) filling voids of the Na skeleton by either sulfate groups (in tychite-type structures) or chlorine atoms (in northupite). As a result, the information-based structural complexity of manganotychite and northupite exceeds that of the dia net.

Porous Organic Cage as a Sulfur Host for Upgrading Capacity and Longevity of Li–S Batteries

Suffering from the severe shuttle effect, constructing high-performance lithium–sulfur (Li–S) batteries with high capacity and prolonged cycling life remains a great challenge. Developing porous host materials for sulfur loading remains a tendency. Porous organic cages (POCs), as a kind of porous material, exhibit potential in energy storage and conversion because of their inherent cavities and plentiful active sites. Herein, two POC materials of CPOC-301 and HPOC-401 with large octahedral cavities and abundant N and O heteroatoms were explored as host materials for loading a high sulfur content of 84 wt % in Li–S batteries. The resulting CPOC-301-S and HPOC-401-S cathodes exhibit improved electrochemical performances with high specific capacity (1302 and 1109 mA h g–1 at 0.05 C, respectively) and excellent cycling reversibility and stability (a low average capacity fading rate of 0.015% for 2500 cycles at 5 C for CPOC-301-S). Moreover, the interconversion of keto-enamine in CPOC-301 could accelerate the redox kinetics. This work provides the blueprint for POC families applied as promising host materials for advanced Li–S batteries.

Highly Connected Three-Dimensional Covalent Organic Framework with Flu Topology for High-Performance Li-S Batteries.

Lithium-sulfur batteries (LSBs) have been considered as a promising candidate for next-generation energy storage devices, which however still suffer from the shuttle effect of the intermediate lithium polysulfides (LiPSs). Covalent-organic frameworks (COFs) have exhibited great potential as sulfur hosts for LSBs to solve such a problem. Herein, a pentiptycene-based D2h symmetrical octatopic polyaldehyde, 6,13-dimethoxy-2,3,9,10,18,19,24,25-octa(4'-formylphenyl)pentiptycene (DMOPTP), was prepared and utilized as a building block toward preparing COFs. Condensation of DMOPTP with 4-connected tetrakis(4-aminophenyl)methane affords an expanded [8 + 4] connected network 3D-flu-COF, with a flu topology. The non-interpenetrated nature of the flu topology endows 3D-flu-COF with a high Brunauer-Emmett-Teller surface area of 2860 m2 g-1, large octahedral cavities, and cross-linked tunnels in the framework, enabling a high loading capacity of sulfur (∼70 wt %), strong LiPS adsorption capability, and facile ion diffusion. Remarkably, when used as a sulfur host for LSBs, 3D-flu-COF delivers a high capacity of 1249 mA h g-1 at 0.2 C (1.0 C = 1675 mA g-1), outstanding rate capability (764 mA h g-1 at 5.0 C), and excellent stability, representing one of the best results among the thus far reported COF-based sulfur host materials for LSBs and being competitive with the state-of-the-art inorganic host materials.

Prominent Free Charges Tunneling Through Organic Interlayer of 2D Perovskites.

The diversity of organic cations greatly enriches the species of 2D perovskites; traditional 2D Ruddlesden-Popper (RP) and Dion-Jacobson (DJ) perovskites are synthesized by two different organic amines. Here, according to the difference in pKa values between conjugated acids of monoprotonated and biprotonated 4-(2-Aminoethyl)pyridine (4AEPy) ions, the 2D perovskites of RP (4AEPy)2 PbI4 and DJ (4AEPy)PbI4 from same organic amine is reported, which can realize reversible transformation under the treatment of HI and NH3 , respectively. The interaction of N-H···N hydrogen bond between adjacent organic molecules in (4AEPy)2 PbI4 leads to the bending conformation of ethylamine groups, which results in a 2.4 Å reduction in layer spacing compared to typical phenylethylamine lead iodine ((PEA)2 PbI4 ) 2D perovskite. Besides, the ethylamine groups of organic layers in (4AEPy)PbI4 are deeply inserted into octahedral cavities and directly participate in the construction of the conduction band minimum, which leads to a small exciton binding energy of 27.3 meVtogeneratefreecharges. The stronger coupling between the organic and inorganic layers and the minor exciton binding energy can promote the DJ phase to possess a more stable structure and better optoelectronic properties. Thusthe (4AEPy)PbI4 device displays better light response and X-ray detection capability with a high sensitivity of 5627 µC Gyair -1 cm-2 and the lowest detectable dose rate of 20 nGyair s-1 .

Lateral Fractal Formation by Crystallographic Silicon Micromachining

A novel wafer-scale silicon fractal fabrication method is presented here for forming pyramids only in the lateral direction using the crystal orientation of silicon. Fractals are fabricated in silicon by masking only the corners (corner lithography) of a cavity in silicon with silicon nitride, where the shape is determined by the crystal {111} planes of the silicon. The octahedral cavity shaped by the {111} planes was previously only used for forming octahedral fractals in all directions, but by using a planar silicon dioxide hard-mask on a silicon (100) wafer, the silicon octahedral cavity is “cut in half”. This creates a pyramid with sharper edges and vertices at its base than those determined by just the {111} planes. This allows selective corner lithography patterning at the vertices of the base while leaving the apex unpatterned, leading to lateral growing of pyramidal fractals. This selective patterning is shown mathematically and then demonstrated by creating a fractal of four generations, with the initial pyramid being 8 µm and the two final generations being of submicron size.

Partial substitution induced structural transformation and enhanced nonlinear optical properties of Na2GaxIn6-xSe10 (x = 3, 3.76)

Chalcogenides are the most promising candidates for nonlinear optical (NLO) applications in the middle infrared region due to their high nonlinear coefficients and wide IR transmission ranges. In particular, polar tetrahedral units are one type of typical functional motifs contribute large NLO coefficients. Based on this background, two quaternary selenides Na2Ga3In3Se10 (1) and Na2Ga3.76In2.24Se10 (2) were derived using NaIn3Se5 as parent. By partial congener substitution of In with Ga, the structure transforms from P32 for NaIn3Se5 to R32 for 1 and 2. Their 3D structures are constructed by InSe4 and GaSe4 tetrahedra, and Na+ ions occupy the octahedral cavities. Both of them exhibit wonderful hybrid NLO properties, witnessed by their large phase-matchable second harmonic generation responses of 1.5 (1) and 1.1 (2) × AgGaS2 (AGS), and enhanced laser-induced damage thresholds of 2.0 (1) and 2.8 (2) × AGS. The results of first-principle calculations show that their band gaps are mainly determined by the valence orbitals of Ga and Se, with a minor contribution from In. The simple design strategy adopted in this work can stimulate more research on various known materials, which will provide useful inspiration for further exploration of high-performance NLO materials. Besides, the successful discovery of 1 and 2 will stimulate more interest in the undeveloped A-MШ3-Q5 or A2-MШ6-Q10 (A = alkali metal; MШ = Ga, In; Q = S, Se, Te) family and their derivatives in the NLO field.

Effect of reactant ratio and nanofillers type on the microstructural properties, porosity fluctuations and heavy metal removal ability of chitosan-clay hybrid materials

The structure, porosity, and functionality of synthesized chitosan-clay nanocomposites (NCs) are examined throughout this work in relation to the initial stoichiometry and octahedral cavity occupation of the clay fraction. Dioctahedral and trioctahedral smectite are selected as starting materials. X-Ray Diffraction analysis (XRD) confirms the accomplishment of the NCs synthesis process. The stoichiometry fluctuation implies a crystallite exfoliation process provided that the clay fraction contribution must not reach twice the organic ones. From 1:3 stoichiometry ratio, The intercalation process is enhanced by the interlamellar space (IS) closures, and crystallite size increases with crystallinity degree. According to transmission electron microscopy-energy dispersive X-ray (TEM-EDX) investigations, the exfoliation of "clay-particles" wrapping the organic fraction and the intercalation process occurred as the clay fraction abundance increased. Despite the low proportion approved from the synthesis beginning process, Fourier transform infrared spectroscopy (FTIR) reveals the polymer fraction characteristics absorption bands. The Brunauer, Emmett and Teller (BET) analysis of specific surface area and Barrett-Joyner-Halenda (BJH) Analysis of pore size distribution (PSD) supports the findings from TEM/EDX. For slightly saturated soil solution with Pb2+ or Cd2+ cation, Atomic absorption spectroscopy (AAS) evaluate the NCs adsorption capacity. The outcomes are extremely positive for dioctahedral smectite.

Photoluminescence of Bi3+ in LiCaY5(BO3)6 and color-tunable emission through energy transfer to Eu3+/Tb3+

Bi3+ has an outer shell lone pair electrons and the energy of 6p orbitals are also sensible to the coordination environment, therefore its typical wide band excitation and emission spectra are highly dependent on the host structure. The recently reported LiCaY5(BO3)6 has multiple sites suitable for cationic doping. In this work, Bi3+ singly doped phosphors and Bi3+/Eu3+ and Bi3+/Tb3+ co-doped phosphors were prepared by high temperature solid state reactions. Careful Rietveld refinements on powder X-ray diffraction suggest the site-preferential doping of Bi3+ into M3 site, which has an octahedral cavity. By 1 atom% doping, Bi3+ exhibits a broad emission band centered at 364 nm with an internal quantum efficiency of 39.8%. The energy transfer to Eu3+/Tb3+ are firmly proved by both the emission intensity change and the decay curves, which is likely through the dipole-dipole interactions. Color-tunable emissions from blue to red, or from blue to green have been realized and the combination with 275 nm LED chip gives the bright blue, red and green emission for LiCa(Y0.99Bi0.01)5(BO3)6, LiCa(Y0.69Bi0.01Eu0.3)5(BO3)6, and LiCa(Y0.69Bi0.01Tb0.3)5(BO3)6, respectively.

Chemically Stable Low-Dimensional Electrides in Transition Metal-Rich Monochalcogenides: Theoretical and Experimental Explorations

Electrides, which are ionic crystals composed of excess anionic electrons, are of great interest as an exotic material for fundamental research and practical applications in broad fields of science and technology. However, an inherent chemical instability under ambient conditions at room temperature has been a fatal drawback to be addressed. Here, we report that transition metal-rich monochalcogenides are an emerging class of low-dimensional electrides with excellent chemical and thermal stability in air and water at room temperature through a comprehensive exploration of theoretical prediction and experimental verification. We predict new two-dimensional (2D) electrides crystallized in hexagonal P3̅m1 and P63/mmc structures with strong localization of anionic electrons in a dumbbell shape at the tetrahedral cavity of the interlayer space, which are distinct from the anionic electrons localized at the octahedral cavity in the hexagonal R3̅m structure of the previous 2D [Ca2N]+·e- and [Y2C]2+·2e- electrides. We successfully synthesized the room-temperature stable [Ti2O]2+·2e-, [Ti2S]2+·2e-, [Zr2S]2+·2e-, and primary solid solution [Hf2SxSe1-x]2+·2e- electrides, showing no structural degradation in air and water. Among them, we found that the synthesized [Ti2S]2+·2e- and [Zr2S]2+·2e- electrides are crystallized in orthorhombic symmetry (Pnnm), showing the feature of a one-dimensional (1D) electride with an anionic electron chain, which has never been reported yet. In addition to the successful finding of new 1D and 2D electrides, we discuss the self-passivation effect-driven chemical stability and the role of anionic electrons in determining the physical properties of the newly discovered electrides.

Capture of Gaseous Iodine in Isoreticular Zirconium-Based UiO-n Metal-Organic Frameworks: Influence of Amino Functionalization, DFT Calculations, Raman and EPR Spectroscopic Investigation.

A series of Zr-based UiO-n MOF materials (n=66, 67, 68) have been studied for iodine capture. Gaseous iodine adsorption was collected kinetically from a home-made set-up allowing the continuous measurement of iodine content trapped within UiO-n compounds, with organic functionalities (-H, -CH3 , -Cl, -Br, -(OH)2 , -NO2 , -NH2 , (-NH2 )2 , -CH2 NH2 ) by in-situ UV-Vis spectroscopy. This study emphasizes the role of the amino groups attached to the aromatic rings of the ligands connecting the {Zr6 O4 (OH)4 } brick. In particular, the preferential interaction of iodine with lone-pair groups, such as amino functions, has been experimentally observed and is also based on DFT calculations. Indeed, higher iodine contents were systematically measured for amino-functionalized UiO-66 or UiO-67, compared to the pristine material (up to 1211 mg/g for UiO-67-(NH2 )2 ). However, DFT calculations revealed the highest computed interaction energies for alkylamine groups (-CH2 NH2 ) in UiO-67 (-128.5 kJ/mol for the octahedral cavity), and pointed out the influence of this specific functionality compared with that of an aromatic amine. The encapsulation of iodine within the pore system of UiO-n materials and their amino-derivatives has been analyzed by UV-Vis and Raman spectroscopy. We showed that a systematic conversion of molecular iodine (I2 ) species into anionic I- ones, stabilized as I- ⋅⋅⋅I2 or I3 - complexes within the MOF cavities, occurs when I2 @UiO-n samples are left in ambient light.

Epoxidation catalysts prepared by encapsulation of molybdenum hexacarbonyl in UiO-66(Zr/Hf)-type metal-organic frameworks

The confinement and catalytic behavior of Mo(CO)6 species inside UiO-66 (zirconium and hafnium) metal-organic frameworks (MOFs) have been investigated by means of multitechnique characterization and catalytic olefin epoxidation. Mo(CO)6 was encapsulated in nanocrystalline MOFs by solvothermal and vapor phase impregnation methods (STI and VPI, respectively), resulting in Mo loadings of 2.0–8.8 wt% (STI) or 15 wt% (VPI). Powder X-ray diffraction, SEM-EDS, N2 adsorption, FT-IR and 13C{1H} CP MAS NMR collectively confirmed immobilization within the pore spaces of the hosts, which maintained their bulk crystallinity and crystal morphologies. CO resonances in the 13C{1H} CP MAS NMR spectra were assigned to hexacarbonyl guest molecules located in the larger pore spaces, such as the octahedral cavities (for STI and VPI samples), and in more restricted environments such as the tetrahedral cavities (for the VPI sample). FT-IR spectra displayed the characteristic pattern of νCO stretching modes for an octahedral symmetry molecule slightly perturbed by interaction of one of the carbonyl groups with the MOF support. The spectra evidenced the formation of a weak hydrogen bonding interaction of the type μ3-OH···OCMo(CO)5 involving the μ3-OH groups that are exclusively present in the tetrahedral cavities of the UiO-66 structure. The Mo(CO)6 loaded MOFs are active and reusable pre-catalysts for cis-cyclooctene epoxidation, exhibiting excellent epoxide selectivity (up to quantitative epoxide yield within 1 h reaction) and tert-butyl hydroperoxide efficiency. Catalyst recycling and retention of structural integrity were demonstrated for UiO-66(Hf) loaded with 8.8 wt% Mo by the STI method. The UiO-66(Hf) host may be a better catalyst support than its Zr counterpart due its smaller crystallite size (≈100 nm) and higher defectivity. The substrate scope was broadened for Mo(8.8-STI)/Hf-MOF which promoted the epoxidation of biobased olefins (methyl oleate and dl-limonene) and oxidative dehydrogenation of cyclooctanol to cyclooctanone.

PHASE FORMATION BASED ON TlInP2Se6 COMPOUND

Special attention of scientists in the field of inorganic synthesis is paid to the M2P2X6 type chalcogenide compounds (X - S, Se), which have a number of promising properties (ferroelectric, piezoelectric, electro-optical, thermoelectric) for functional materials. According to the directions of "chemical design", the improvement of the properties of M2P2X6 compounds is possible by heterovalent substitution in the composition of two M2+ metal ions, which form a cationic sublattice of crystal structure by two different ions M1+ and M23+. Also, the formation of limited solid solutions based on complex compounds M1M2P2X6 contributes to obtaining of materials with the same structure and different chemical composition, which allows enables purposefully change their properties.
 The TlInP2Se6 quaternary compound with melts congruently at 875 K is formed in the Tl2Se–In2Se3–“P2Se4” ternary system. Physical-chemical analysis of the interaction on the In2Se3–TlInP2Se6, TlInP2Se6–Tl4P2Se6, TlInSe2–TlInP2Se6, TlInP2Se6–In4(P2Se6)3 sections showed the formation of limiting solid solutions (up to 7 mol.%) based on the TlInP2Se6 compound.
 To study the formation mechanisms of solid solutions, alloys of solid solutions (TlInP2Se6)0.95(Tl4P2Se6)0.05, (TlInP2Se6)0.95(In4(P2Se6)3)0.05, (TlInP2Se6)0.95(Tl2Se)0.05, (TlInP2Se6)0.95(TlInSe2)0.05, (TlInP2Se6)0.95(In2Se3)0.05 were synthesized and investigated by X-ray phase and X-ray diffraction analyzes (DRON 4-13 diffractometer, Guinier Huber G670 X-ray chamber, WinCSD program). Crystal structure of TlInP2Se6 compound (SG P-1 (2), a=6.4488(7), b=7.5420(9), c=12.166(2) Å, a=100.72(0), b=93.63(0), g=113.32(0), V=527.7 Å3) is form anionic sublattice by layers of atom groups [P2Se6]4– in the two fused tetrahedrons shape. Cation atoms occupy positions between layers of atoms of anionic groups. In3+ cations are located at the boundary between tetrahedral and octahedral cavities (in the same plane with the centers of the anionic groups [P2Se6]4–), Tl+ cations are slightly shifted toward the octahedral cavities. The volume of the unit cell (V) is a slight decrease during the transition from the basic matrix structure of TlInP2Se6 to solid solutions (from 527.7 Å3 to 523.9 Å3), which indicates the formation of defects in the basic structure. The study of the formation mechanisms of solid solutions based on TlInP2Se6 quaternary compound from the standpoint of crystal chemical formulas showed the formation of solid solutions by the mechanism of substitution (cationic sublattice) and subtraction (anionic sublattice), which leads to the formation of defects in the crystal structure, and respectively should lead to changes in optical properties.
 Experimental studies of the diffusion reflection spectra R=f(λ) showed that the compound TlInP2Se6 and solid solutions belong to indirect semiconductors. During the transition from pure compound to solid solutions the phonons energy conductivity Ephonon decreases (0.082-0.068 eV), the band gap value Eg increases (2.13-2.15 eV).

Preparation and superconducting behavior of triammonium fulleride

The synthesis of triammonium fulleride (NH4)3C60 by ion exchange of either K3C60 or Rb3C60 with NH4Cl in absolute toluene is reported. According to the Rietveld refinement of a synchrotron radiation-based X-ray diffraction pattern, (NH4)3C60 belongs to the same structure type as both K3C60 and Rb3C60 featuring an fcc lattice with intercalated cations occupying tetrahedral and octahedral cavities of the close-packing formed by fullerene С60 spheres. The ion exchange is incomplete and the final formulation of the product is [(NH4)2.88K0.12]C60. In contrast to earlier suggestions and tabulated ionic radii values, the (NH4)3C60 crystal structure is characterized by a lattice parameter slightly smaller than that of K3C60. A similar reaction between K4C60 and NH4Cl proceeds differently involving the redox step and affords [(NH4)0.48K2.52]C60 again emphasizing the fact that ammonium and potassium in the fulleride phase tend to form substitutional solid solutions. According to low-frequency inductive method, all (NH4)3C60-related phases studied are superconducting with similar temperatures of the superconducting transition around Tc = 16.4 K.

Mixed-cation driven magnetic interaction of interstitial electrons for ferrimagnetic two-dimensional electride

Magnetism of pure electrons is fundamental for understanding diverse magnetic phenomena in condensed matters but has not been fully investigated in experiments due to the lack of a tractable model system. Such an exotic material necessitates an exclusive magnetic interaction of electrons being devoid of orbital and lattice degrees of freedom. Here, we report the two-dimensional mixed-cation [YGdC]2+∙2e− electride, showing ferrimagnetic nature from the direct exchange interaction of magnetic interstitial electrons in interlayer space. We identify that magnetic interstitial electrons are periodically localized in octahedral and tetrahedral cavities between 2D cationic Y2−xGdx arrays. The mixed configuration of non-magnetic and magnetic cations in cavities induces divergent spin states and interactions of magnetic interstitial electrons, in which their direct exchange interaction overwhelms the interactions with magnetic cations, triggering the ferrimagnetic spin-alignment. This discovery facilitates further exploration of magnetic electrides and nurtures the study of two-dimensional magnetism of layered crystals and electron phases.

A Series of Pentanary Salt-Inclusion Chalcogenoborates Containing a B12Q12 (Q = S, Se) Cluster Exhibiting a Kleinman-Forbidden Frequency-Doubling Effect.

A series of pentanary chalcogenoborates (A3X)[InB12(InQ4)3] (A = K, Rb, Cs; X = Cl, Br, I; Q = S, Se) were obtained by high-temperature solid-state reactions. These salt-inclusion chalcogenides crystallize in the hexagonal space group P6322, a type of Kleinman-forbidden noncentrosymmetric structure. Their structures feature a [InB12(InQ4)3] open framework built by InQ6 octahedra and InQ4 tetrahedra consolidated B12 cluster, which accomodates octahedral cavities for XA6 units. They are second-harmonic generation active, and their optical properties were studied experimentally and theoretically. This work can evoke more interest in chalcogenoborate-based second-order nonlinear optical materials.

Low-temperature photoluminescence of C60 single crystals intercaled with nitrogen molecules in the wide range of temperatures

The optical properties of C60 single crystals, intercalated with nitrogen molecules, were studied by the spectral-luminescence method at a temperature T = 30 K and excitation by the He–Ne laser (Eexc = 1.96 eV). Intercalation was carried out at a pressure of 30 atm in a temperature range of 200–550 °C. It was found that at sorption temperatures up to 400 °C, the bands of the low-temperature luminescence spectrum of the C60–N2 solutions are broadened without significant energy shift. As a rule, this situation is typical for the case of an increased contribution of the luminescence of “deep X-traps.” The concentration of such exciton emission centers is determined by the degree of occupation of the octahedral cavities of the fullerite fcc lattice by intercalated molecules. This indicates the formation of an equilibrium C60–N2 interstitial solution as a result of physisorption. At sorption temperatures above 400 °C, a significant shift of the luminescence spectrum towards low energies with a considerable inhomogeneous broadening of spectral bands was found for the first time. The shift and significant nonuniform broadening of the luminescence bands are explained by the emergence of a chemical interaction (chemisorption) of nitrogen with fullerene molecules, with the formation of a new nitrogen-containing substance in this case.