Compounds In Solid State Research Articles

Colorimetric oxygen sensor based on nano-sized black TiO2 catalysts: DFT modeling and experiments

There are the imperious demands for novel oxygen (O2) sensors in cutting-edge biochemical technologies and industrial hygiene. Here, we develop a colorimetric O2 sensor based on a spherical nano-sized reduced TiO2 (TiO2 –x) catalyst, which resolves the critical bottlenecks of conventional systems. The sensing mechanism of our O2 sensors relies on two characteristics which are proven by simulations based on density functional theory (DFT) calculations. First, nano-TiO2–x, in the partially reduced form, shows a rapid, reversible O2 uptake at room temperature. Second, the partially reduced form of nano-TiO2–x, called black TiO2, shows a change in the lightness of color. Owing to these characteristics, the developed sensor it is well-suited for use at ambient temperature/pressure in the absence of a reference gas, in contrast with the conventional system. Also, it allows long-term operations and it can withstand degradation because the former comprises solid-state inorganic compounds.

Ammoniates of Zintl Phases: Similarities and Differences of Binary Phases A4E4 and Their Corresponding Solvates

The combination of electropositive alkali metals A (A = Na-Cs) and group 14 elements E (E = Si-Pb) in a stoichiometric ratio of 1:1 in solid state reactions results in the formation of polyanionic salts, which belong to a class of intermetallics for which the term Zintl compounds is used. Crystal structure analysis of these intermetallic phases proved the presence of tetrahedral tetrelide tetraanions [E4]4− precast in solid state, and coulombic interactions account for the formation of a dense, three-dimensional cation-anion network. In addition, it has been shown that [E4]4− polyanions are also present in solutions of liquid ammonia prepared via different synthetic routes. From these solutions crystallize ammoniates of the alkali metal tetrahedranides, which contain ammonia molecules of crystallization, and which can be characterized by X-ray crystallography despite their low thermal stability. The question to be answered is about the structural relations between the analogous compounds in solid state vs. solvate structures, which all include the tetrahedral [E4]4− anions. We here investigate the similarities and differences regarding the coordination spheres of these anions and the resulting cation-anion network. The reported solvates Na4Sn4·13NH3, Rb4Sn4·2NH3, Cs4Sn4·2NH3, Rb4Pb4·2NH3 as well as the up to now unpublished crystal structures of the new compounds Cs4Si4·7NH3, Cs4Ge4·9NH3, [Li(NH3)4]4Sn4·4NH3, Na4Sn4·11.5NH3 and Cs4Pb4·5NH3 are considered for comparisons. Additionally, the influence of the presence of another anion on the overall crystal structure is discussed by using the example of a hydroxide co-crystal which was observed in the new compound K4.5Sn4(OH)0.5∙1.75 NH3.

Performance of the strongly constrained and appropriately normed density functional for solid-state materials

Constructed to satisfy all known exact constraints and appropriate norms for a semilocal density functional, the strongly constrained and appropriately normed (SCAN) meta-generalized gradient approximation functional has shown early promise for accurately describing the electronic structure of molecules and solids. One open question is how well SCAN predicts the formation energy, a key quantity for describing the thermodynamic stability of solid-state compounds. To answer this question, we perform an extensive benchmark of SCAN by computing the formation energies for a diverse group of nearly one thousand crystalline compounds for which experimental values are known. Due to an enhanced exchange interaction in the covalent bonding regime, SCAN substantially decreases the formation energy errors for strongly-bound compounds, by approximately 50% to 110 meV/atom, as compared to the generalized gradient approximation of Perdew, Burke, and Ernzerhof (PBE). However, for intermetallic compounds, SCAN performs moderately worse than PBE with an increase in formation energy error of approximately 20%, stemming from SCAN's distinct behavior in the weak bonding regime. The formation energy errors can be further reduced via elemental chemical potential fitting. We find that SCAN leads to significantly more accurate predicted crystal volumes, moderately enhanced magnetism, and mildly improved band gaps as compared to PBE. Overall, SCAN represents a significant improvement in accurately describing the thermodynamics of strongly-bound compounds.

Cerium Tetrakis(tropolonate) and Cerium Tetrakis(acetylacetonate) Are Not Diamagnetic but Temperature-Independent Paramagnets.

A new synthesis of cerium tetrakis(tropolonate), Ce(trop)4, where trop is deprotonated 2-hydroxy-2,4,6-cycloheptatrienone) or Ce(O2C7H5)4, is developed that results in dark-purple crystals whose X-ray crystal structure shows that the geometry of the eight-coordinate compound closely resembles a D2 d dodecahedron, based on shape parameters. The magnetic susceptibility as a function of the temperature (4-300 K) shows that it is a temperature-independent paramagnet, χ = 1.2(3) × 10-4 emu/mol, and the LIII-edge X-ray absorption near-edge structure spectrum shows that the molecule is multiconfigurational, comprised of a f1:f0 configuration mixture in a 50:50 ratio. Ce(acac)4 and Ce(tmtaa)2 (where acac is acetylacetonate and tmtaaH2 is tetramethyldibenzotetraaza[14]annulene) have similar physical properties, as does the solid-state compound CeO2. The concept is advanced that trop-, acac-, tmtaa2-, cot2-, and O2- are redox-active ligands that function as electron donors, rendering the classification of these compounds according to their oxidation numbers misleading because their magnetic susceptibilities, χ, are positive and their effective magnetic moments, μeff, lie in the range of 0.1-0.7 μB at 300 K.

High-Pressure Synthesis: A New Frontier in the Search for Next-Generation Intermetallic Compounds.

The application of high pressure adds an additional dimension to chemical phase space, opening up an unexplored expanse bearing tremendous potential for discovery. Our continuing mission is to explore this new frontier, to seek out new intermetallic compounds and new solid-state bonding. Simple binary elemental systems, in particular those composed of pairs of elements that do not form compounds under ambient pressures, can yield novel crystalline phases under compression. Thus, high-pressure synthesis can provide access to solid-state compounds that cannot be formed with traditional thermodynamic methods. An emerging approach for the rapid exploration of composition-pressure-temperature phase space is the use of hand-held high-pressure devices known as diamond anvil cells (DACs). These devices were originally developed by geologists as a way to study minerals under conditions relevant to the earth's interior, but they possess a host of capabilities that make them ideal for high-pressure solid-state synthesis. Of particular importance, they offer the capability for in situ spectroscopic and diffraction measurements, thereby enabling continuous reaction monitoring-a powerful capability for solid-state synthesis. In this Account, we provide an overview of this approach in the context of research we have performed in the pursuit of new intermetallic compounds. We start with a discussion of pressure as a fundamental experimental variable that enables the formation of intermetallic compounds that cannot be isolated under ambient conditions. We then introduce the DAC apparatus and explain how it can be repurposed for use as a synthetic vessel with which to explore this phase space, going to extremes of pressure where no chemist has gone before. The remainder of the Account is devoted to discussions of recent experiments we have performed with this approach that have led to the discovery of novel intermetallic compounds in the Fe-Bi, Cu-Bi, and Ni-Bi systems, with a focus on the cutting-edge methods that made these experiments possible. We review the use of in situ laser heating at high pressure, which led to the discovery of FeBi2, the first binary intermetallic compound in the Fe-Bi system. Our work in the Cu-Bi system is described in the context of in situ experiments carried out in the DAC to map its high-pressure phase space, which revealed two intermetallic phases (Cu11Bi7 and CuBi). Finally, we review the discovery of β-NiBi, a novel high-pressure phase in the Ni-Bi system. We hope that this Account will inspire the next generation of solid-state chemists to boldly explore high-pressure phase space.

Intermetallic Ni2Ta Electrocatalyst for the Oxygen Evolution Reaction in Highly Acidic Electrolytes.

The identification of materials capable of catalyzing the oxygen evolution reaction (OER) in highly acidic electrolytes is a critical bottleneck in the development of many water-splitting technologies. Bulk-scale solid-state compounds can be readily produced using high-temperature reactions and therefore used to expand the scope of earth-abundant OER catalysts capable of operating under strongly acidic conditions. Here, we show that high temperature arc melting and powder metallurgy reactions can be used to synthesize electrodes consisting of intermetallic Ni2Ta that can catalyze the OER in 0.50 M H2SO4. Arc melted Ni2Ta electrodes evolve oxygen at a current density of 10 mA/cm2 for >66 h with corrosion rates 2 orders of magnitude lower than that of pure Ni. The overpotential required for pellets of polycrystalline Ni2Ta to produce a current density of 10 mA/cm2 is 570 mV. This strategy can be generalized to include other first-row transition metals, including intermetallic Fe2Ta and Co2Ta systems.

2:2 Complexes from Diphenylpyridiniums and Cucurbit[8]uril: Encapsulation‐Promoted Dimerization of Electrostatically Repulsing Pyridiniums

Rigid linear compounds G1 and G2, which contained two 4-phenylpyridinium (PhPy+ ) units, have been prepared to investigate their binding with cucurbit[8]uril (CB[8]). X-ray crystallographic structures revealed that in the solid state both compounds were included by CB[8], through antiparallel stacking, to form 2:2 quaternary complexes (G1)2 @(CB[8])2 and (G2)2 @(CB[8])2 . For the former complex, CB[8] entrapped G1 by holding two heterodimers of its Py+ and benzyl units, which were at opposite ends of the backbone. In contrast, for the first time, the second complex disclosed parallel stacking of two cationic Py+ units of G2 in the cavity of CB[8] in the solid state, despite the generation of important electrostatic repulsion. Isothermal titrations in water afforded high apparent association constants of 4.36×106 and 6.43×106 m-1 for 1:1 complexes G1@CB[8] and G2@CB[8], respectively, and 1 H NMR spectroscopy experiments in D2 O confirmed a similar stacking pattern to that observed in the solid state. A previous study and crystal structures of the 2:1 complexes formed between three new controls, G3-5, and CB[8] did not display such unusual stacking of the cationic Py+ unit; this may be attributed to the multivalency of the two CB[8] encapsulation interactions.

Fabrication and study the effect of the laser on the properties of the compound Tl2-xHgxBa2-ySryCa2Cu3O10+δ superconductor

This study included the fabrication of compound (Tl2-xHgxBa2-ySryCa2Cu3O10+δ) in a manner solid state and under hydrostatic pressure ( 8 ton/cm2) and temperature annealing(850°C), and determine the effect of the laser on the structural and electrical properties elements in the compound, and various concentrations of x where (x= 0.1,0.2,0.3 ). Observed by testing the XRD The best ratio of compensation for x is 0.2 as the value of a = b = 5.3899 (A °), c = 36.21 (A °) show that the installation of four-wheel-based type and that the best temperature shift is TC= 142 K .When you shine a CO2 laser on the models in order to recognize the effect of the laser on these models showed the study of X-ray diffraction of these samples when preparing models with different concentrations of the values ​​of x, the best ratio of compensation is 0.2 which showed an increase in the values ​​of the dimensions of the unit cell a=b = 5.3929 (A °), c = 36.238 (A°). And the best transition temperature after shedding laser is TC=144 K.

Room Temperature Hard Radiation Detectors Based on Solid State Compound Semiconductors: An Overview

Si and Ge single crystals are the most common semiconductor radiation detectors. However, they need to work at cryogenic temperatures to decrease their noise levels. In contrast, compound semiconductors can be operated at room temperature due to their ability to grow compound materials with tunable densities, band gaps and atomic numbers. Highly efficient room temperature hard radiation detectors can be utilized in biomedical diagnostics, nuclear safety and homeland security applications. In this review, we discuss room temperature compound semiconductors. Since the field of radiation detection is broad and a discussion of all compound materials for radiation sensing is impossible, we discuss the most important materials for the detection of hard radiation with a focus on binary heavy metal semiconductors and ternary and quaternary chalcogenide compounds.

Frontispiece: Usefulness of the σ‐Aromaticity and σ‐Antiaromaticity Concepts for Clusters and Solid‐State Compounds

The usefulness of the concepts of σ-aromaticity and σ-antiaromaticity in the chemistry of small clusters to bulky solid-state compounds is discussed in this Review. For example, the counter-intuitive geometry of the global minimum structure of the Li2Mg2 cluster can be explained by using the σ-aromaticity based on the particular delocalized bonding pattern and energy considerations. For more details of different examples, see the Review by A. I. Boldyrev and co-workers on page 292 ff.

Photoluminescence and energy transfer behavior of narrow band red light emitting Li3Ba2Tb3(MoO4)8:Eu3.

This work concerns the polycrystalline red emitting solid state compound Li3Ba2(Tb1-xEux)3(MoO4)8, from which a series of powder samples was prepared by a conventional solid-state reaction. The phase formation of the samples was investigated by X-ray diffraction which revealed the formation of a solid solution without a miscibility gap. Photoluminescence (PL) spectra and decay curves were recorded as a function of Tb3+ and Eu3+ concentration and temperature. It turned out that the external quantum efficiency of Eu3+ photoluminescence is between 30 and 80%, while the highest quantum yield is achieved for about 60% Tb3+. An increase of emission intensity can be realized by co-doping of Eu3+ and Tb3+. Moreover, the emission has a luminous efficacy of 275 lm Wopt-1 which is a distinct advantage over the widely applied Mn4+ activated fluorides. The time dependent photoluminescence as a function of Tb3+ concentration demonstrates the presence of an efficient energy transfer from Tb3+ to Eu3+. Temperature dependent PL measurements revealed that Li3Ba2(Tb1-xEux)3(MoO4)8 loses just 20% of PL efficiency up to 400 K. Therefore, the investigated phosphors are attractive for application in pcLEDs. It is finally demonstrated that the application of a Eu3+/Tb3+ co-doped ceramic disc is useful for the colour conversion of a blue emitting LED with a higher conversion rate compared to Li3Ba2(La1-xEux)3(MoO4)8.

Chemical Pressure Maps of Molecules and Materials: Merging the Visual and Physical in Bonding Analysis.

The characterization of bonding interactions in molecules and materials is one of the major applications of quantum mechanical calculations. Numerous schemes have been devised to identify and visualize chemical bonds, including the electron localization function, quantum theory of atoms in molecules, and natural bond orbital analysis, whereas the energetics of bond formation are generally analyzed in qualitative terms through various forms of energy partitioning schemes. In this Article, we illustrate how the chemical pressure (CP) approach recently developed for analyzing atomic size effects in solid state compounds provides a basis for merging these two approaches, in which bonds are revealed through the forces of attraction and repulsion acting between the atoms. Using a series of model systems that include simple molecules (H2, CO2, and S8), extended structures (graphene and diamond), and systems exhibiting intermolecular interactions (ice and graphite), as well as simple representatives of metallic and ionic bonding (Na and NaH, respectively), we show how CP maps can differentiate a range of bonding phenomena. The approach also allows for the partitioning of the potential and kinetic contributions to the interatomic interactions, yielding schemes that capture the physical model for the chemical bond offered by Ruedenberg and co-workers.

Titanium-Based Hydrides as Heterogeneous Catalysts for Ammonia Synthesis.

The problem of activating N2 and its subsequent hydrogenation to form NH3 has been approached from many directions. One of these approaches involves the use of transition metal hydride complexes. Recently, transition metal hydride complexes of Ti and Ta have been shown to activate N2, but without catalytic formation of NH3. Here, we show that at elevated temperatures (400 °C, 5 MPa), solid-state hydride-containing Ti compounds (TiH2 and BaTiO2.5H0.5) form a nitride-hydride surface similar to those observed with titanium clusters, but continuously (∼7 days) form NH3 under H2/N2 flow conditions to achieve a catalytic cycle, with activity (up to 2.8 mmol·g·-1·h-1) almost comparable to conventional supported Ru catalysts such as Cs-Ru/MgO or Ru/BaTiO3 that we have tested. As with the homogeneous analogues, the initial presence of hydride within the catalyst is critical. A rare hydrogen-based Mars van Krevelen mechanism may be at play here. Conventional scaling rules of pure metals predict essentially no activity for Ti, making this a previously overlooked element, but our results show that by introducing hydride, the repertoire of heterogeneous catalysts can be expanded to include formerly unexamined compositions without resorting to precious metals.

Usefulness of the σ-Aromaticity and σ-Antiaromaticity Concepts for Clusters and Solid-State Compounds.

In this Review we present examples of clusters, molecules, and solid-state compounds, for which the use of σ-aromaticity and σ-antiaromaticity concepts is essential for understanding of chemical bonding. We show that the bonding patterns in these σ-aromatic and σ-antiaromatic compounds are similar to those of the corresponding π-aromatic and π-antiaromatic chemical systems, respectively. Undoubtedly, σ-aromaticity helps us understand why the high symmetry isomers are the most stable among myriads of other potential structures. We also show that besides systems exhibiting either σ- or π-aromatic features, there are species, which can possess multiple aromaticity/antiaromaticity, or conflicting aromaticity patterns. We believe that the σ-aromaticity and σ-antiaromaticity concepts will be helpful in rationalizing chemical bonding, structure, stability, and molecular properties of chemical species in both organic and inorganic chemistry. We hope that they will also be useful for other areas of science such as material science, catalysis, nanotechnology, and biochemistry.

Rational design of slightly twisted coumarin molecules with remarkable solution and solid dual efficient luminescence

Endowing slightly twisted molecules highly emissive in both solution and solid state is of great importance for understanding the principle of maximizing the luminescent efficiency of luminophores. To this end, a series of slightly twisted coumarin luminophores CMs with different alkoxyl substituents at the 7-positions were synthesized. The effect of the substitutes on the diversity photophysical properties of the four compounds in solution, THF/H2O mixtures and solid state were investigated. Comparing to the referenced compound CM (3-p-tolyl-2H-chromen-2-one) that without a substitute, the introduced electron-rich alkoxyl substitutes not only enhanced the intramolecular charge transfer (ICT) effect, but also significantly modified their molecular packing patterns in the crystals. The combined effect of increasing the radiative and suppressing the nonradiactive pathways boosted the luminescence efficiency of CM1-CM3 in solution and the solid state simultaneously. Eventually, compound CM2 with an ethoxyl substitute exhibited the strongest blue emission with fluorescence quantum yields as high as 73.2% and 96.7% in solution and the solid state, respectively. This work presents an efficient strategy towards dual strong fluorescent luminophores in both solution and the solid state.

Encapsulation of Isolated Luminophores within Supramolecular Cages.

The sequestration of luminophores within supramolecular polyhedral compartments of a crystalline zeolite-like hydrogen-bonded framework illustrates a unique approach to limiting the self-quenching ordinarily exhibited at the high concentrations achievable in this framework. A range of differently sized luminescent guests, namely coumarin 1, coumarin 4, fluorescein, [Ru(bpy)3 ]Cl2 , and rhodamine B, can be encapsulated in amounts of up to one molecule per cage, equivalent to a concentration of 0.175 m, which is significantly higher than the concentration at which aggregation-induced quenching occurs in other media. The luminescence spectra of the encapsulated guests are consistent with the presence of isolated monomers and the absence of self-quenching. The emission color of the single crystals can be tuned readily from blue to red through the choice of guest molecules. These observations promise an approach to organic solid-state lasing compounds if crystals of sufficient size and quality can be prepared.

New aspects of relationship between the enthalpies of fusion of aromatic compounds at the melting temperatures and the enthalpies of solution in benzene at 298.15 K. Part I

In the present work the relationship between the enthalpies of fusion at the melting temperatures and the enthalpies of solution in benzene at 298.15K of aromatic compounds is discussed in details. The difference between the fusion enthalpy at the melting temperature and the solution enthalpy at 298.15K is determined by the temperature dependence of the fusion enthalpy, the solution enthalpy of the compound in the hypothetical liquid state at 298.15K and the enthalpies of solid–solid phase transitions occurring between 298.15K and the melting temperature. The latter contribution into the difference can be measured directly. The first two contributions were analyzed in a series of 17 aromatic compounds which do not exhibit solid-solid phase transitions between 298.15K and the melting temperature. We calculated the fusion enthalpies at 298.15K of these compounds in two different ways. On the one hand, they were derived from the fusion enthalpies at the melting temperature according to Kirchhoff’s law using experimental data on solid and liquid heat capacities. It was assumed that the linear temperature dependence of melt heat capacity can be extrapolated down to 298.15K. On the other hand, the fusion enthalpies at 298.15K were calculated from the solution enthalpies in benzene at 298.15K of the compounds in solid and hypothetical liquid states. Good agreement between the fusion enthalpies at 298.15K calculated in different ways was demonstrated.The solution enthalpies of eight solid and six liquid aromatic compounds in benzene at 298.15K and the fusion enthalpies of two aromatic compounds were measured.

Novel antihelmintic activity of tinidazole coordination compounds. Relevance of the metal ion and structural properties

The in vitro and in vivo antihelmintic activity of cobalt(II), copper(II) and zinc(II) coordination compounds of tinidazole (tnz) were investigated in cultivated spotted rose snapper, infested with dactylogyrid monogeneans. The tinidazole coordination compounds [Co(tnz)2Cl2], [Co(tnz)2Br2], [Cu(tnz)2Cl2], [Cu(tnz)2Br2], [Zn(tnz)2Cl2] and [Zn(tnz)2Br2] were synthesized and spectroscopically characterized. Their molecular structures were determined by their single crystal X-ray diffraction. The metal ions presented distorted tetrahedral geometries, with an intramolecular bifurcated lone pair SO⋯π, from the sulfone group with the imidazolic ring, which contributed to the stability of the compounds in solid state and in solution. Adults of dactylogyrids were exposed in vitro to tinidazole and its coordination compounds. The effective median concentrations of copper(II) coordination compounds were lower than those of cobalt(II) and zinc(II), tnz showed no activity. In vivo oral intubation tests were carried out with [Cu(tnz)2Br2], [Zn(tnz)2Br2] and tnz on snappers infected with dactylogyrids, where the copper(II) compound showed better activity. The absorption and distribution assessment for the [Cu(tnz)2Br2], showed that copper concentrations in liver were significantly higher than in blood and gills, indicating bioaccumulation in this organ. In vivo baths of [Cu(tnz)2Br2] at 25mg/L showed an effective (95% at 8h) antihelmintic effect, while [Zn(tnz)2Br2] had low antihelmintic efficacy. This study indicates that [Cu(tnz)2Br2] has an effective antihelmintic activity towards dactylogyrids monogeneans affecting cultivated spotted red snapper.

Linking Solution Structures and Energetics: Thorium Nitrate Complexes.

Seeking predictive insights into how metal-ion speciation impacts solution chemistry as well as the composition and structure of solid-precipitates, thorium correlations, with both solvent and other solute ions, were quantitatively probed in a series of acidic, nitrate/perchlorate solutions held at constant ionic strength. Difference pair-distribution functions (dPDF), obtained from high-energy X-ray scattering (HEXS) data, provide unprecedented structural information on the number of Th ligating ions in solution and how they change with increasing nitrate concentration. A fit of the end member solution, Th (4 m perchloric acid and no nitrate), reveals a homoleptic Th aqua ion with 10 waters in its first coordination shell. Analyses of the acidic solutions containing nitrate reveal exclusively bidentate NO3- complexation with Th, consistent with published solid-state MIV nitrate structures, where MIV = Ce, Th, U, Np, Pu. Metrical fits of Th coordination as a function of nitrate concentration are used to calculate Th-NO3 stability constants, information important to a molecular-scale description of reaction energetics. The coordination environments of Th in solution were compared with single-crystal structures obtained from their precipitates, Th(NO3)4(H2O)4 and Th(NO3)4(H2O)3·(H2O)2. Relative stabilities of the solid-state compounds, assessed based on the results of molecular quantum chemical calculations, reveal the importance of including an accurate description of complexed waters when predicting relative energetics of dissolved ions in aqueous solution.

Single-crystal-to-single-crystal intercalation of a low-bandgap superatomic crystal.

The controlled introduction of impurities into the crystal lattice of solid-state compounds is a cornerstone of materials science. Intercalation, the insertion of guest atoms, ions or molecules between the atomic layers of a host structure, can produce novel electronic, magnetic and optical properties in many materials. Here we describe an intercalation compound in which the host [Co6Te8(PnPr3)6][C60]3, formed from the binary assembly of atomically precise molecular clusters, is a superatomic analogue of traditional layered atomic compounds. We find that tetracyanoethylene (TCNE) can be inserted into the superstructure through a single-crystal-to-single-crystal transformation. Using electronic absorption spectroscopy, electrical transport measurements and electronic structure calculations, we demonstrate that the intercalation is driven by the exchange of charge between the host [Co6Te8(PnPr3)6][C60]3 and the intercalant TCNE. These results show that intercalation is a powerful approach to manipulate the material properties of superatomic crystals.