Browse
Submit Data
Databases
API
Help

Dataset Information

10 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Triple-Vertex Linkage of (BO₄ )-Tetrahedra in a Borosulfate: Synthesis, Crystal Structure, and Quantum-Chemical Investigation of Sr[B₃ O(SO₄ )₄ (SO₄ H)].

ABSTRACT: Borosulfates are classified as silicate analogue materials. The number of crystallographically characterized compounds is still limited, whereas the structural diversity is already impressive. The anionic substructures of borosulfates exhibit vertex-connected (BO₄ )- and (SO₄ )-tetrahedra, whereas bridging between two (SO₄ )- or even between two (BO₄ )-tetrahedra is scarce. The herein presented compound Sr[B₃ O(SO₄ )₄ (SO₄ H)] is the first borosulfate with a triple-vertex linkage of three (BO₄ ) tetrahedra via one common oxygen atom. DFT calculations complement the experimental studies. Bader charges (calculated for all atoms) as well as charge-density calculations give hint to the electron distribution within the anionic substructure and density-of-states calculations support the interpretation of the bonding situation.

SUBMITTER: Pasqualini LC

PROVIDER: S-EPMC8456809 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Borate Hydrides as a New Material Class: Structure, Computational Studies, and Spectroscopic Investigations on Sr5 (BO3 )3 H and Sr5 (11 BO3 )3 D.

Project description:The unprecedented borate hydride Sr5 (BO3 )3 H and deuteride Sr5 (11 BO3 )3 D crystallizing in an apatite-related structure are reported. Despite the presence of hydride anions, the compound decomposes only slowly in air. Doped with Eu2+ , it shows broad-band orange-red emission under violet excitation owing to the 4f6 5d-4f7 transition of Eu2+ . The observed 1 H NMR chemical shift is in good agreement with previously reported 1 H chemical shifts of ionic metal hydrides as well as with quantum chemical calculations and very different from 1 H chemical shifts usually found for hydroxide ions in similar materials. FTIR and Raman spectroscopy of different samples containing 1 H, 2 H, nat B, and 11 B combined with calculations unambiguously prove the absence of hydroxide ions and the sole incorporation of hydride ions into the borate. The orange-red emission obtained by doping with Eu2+ shows that the new compound class might be a promising host material for optical applications.

| S-EPMC7540042 | biostudies-literature

Investigation of Molecular Iridium Fluorides IrFn (n=1-6): A Combined Matrix-Isolation and Quantum-Chemical Study.

Project description:The photo-initiated defluorination of iridium hexafluoride (IrF6 ) was investigated in neon and argon matrices at 6 K, and their photoproducts are characterized by IR and UV-vis spectroscopies as well as quantum-chemical calculations. The primary photoproducts obtained after irradiation with λ=365 nm are iridium pentafluoride (IrF5 ) and iridium trifluoride (IrF3 ), while longer irradiation of the same matrix with λ=278 nm produced iridium tetrafluoride (IrF4 ) and iridium difluoride (IrF2 ) by Ir-F bond cleavage or F2 elimination. In addition, IrF5 can be reversed to IrF6 by adding a F atom when exposed to blue-light (λ=470 nm) irradiation. Laser irradiation (λ=266 nm) of IrF4 also generated IrF6 , IrF5 , IrF3 and IrF2 . Alternatively, molecular binary iridium fluorides IrFn (n=1-6) were produced by co-deposition of laser-ablated iridium atoms with elemental fluorine in excess neon and argon matrices under cryogenic conditions. Computational studies up to scalar relativistic CCSD(T)/triple-ζ level and two-component quasirelativistic DFT computations including spin-orbit coupling effects supported the formation of these products and provided detailed insights into their molecular structures by their characteristic Ir-F stretching bands. Compared to the Jahn-Teller effect, the influence of spin-orbit coupling dominates in IrF5 , leading to a triplet ground state with C4v symmetry, which was spectroscopically detected in solid argon and neon matrices.

| S-EPMC9310635 | biostudies-literature

Quantum vertex model for reversible classical computing.

Project description:Mappings of classical computation onto statistical mechanics models have led to remarkable successes in addressing some complex computational problems. However, such mappings display thermodynamic phase transitions that may prevent reaching solution even for easy problems known to be solvable in polynomial time. Here we map universal reversible classical computations onto a planar vertex model that exhibits no bulk classical thermodynamic phase transition, independent of the computational circuit. Within our approach the solution of the computation is encoded in the ground state of the vertex model and its complexity is reflected in the dynamics of the relaxation of the system to its ground state. We use thermal annealing with and without 'learning' to explore typical computational problems. We also construct a mapping of the vertex model into the Chimera architecture of the D-Wave machine, initiating an approach to reversible classical computation based on state-of-the-art implementations of quantum annealing.

| S-EPMC5437300 | biostudies-literature

Where Is the Fluoro Wall?: A Quantum Chemical Investigation.

Project description:Despite their isoelectronic properties, fluoro and oxo ligands exhibit completely different chemical behavior. Formally speaking, the first is known to exclusively form single bonds, while the latter is generally observed to form double (or even triple) bonds. The biggest difference, however, lies in what is known among inorganic chemists as the Oxo Wall: the fact that six-coordinate tetragonal transition metal oxo complexes are not observed beyond group 7 elements. While the Oxo Wall was explained a few decades ago, some questions regarding the nature of the Oxo Wall remain unanswered. For example, why do group 8 oxo complexes with high oxidation states not violate the Oxo Wall? Moreover, why are transition metal fluoro complexes observed through the whole transition metal series? In order to understand how the small difference between these two isoelectronic ligands can give rise to such different chemical behaviors, we conducted an extensive computational analysis of the geometric and electronic properties of model fluoro and oxo complexes with metals around the Oxo Wall. Among many insights into the details of the Oxo Wall, we mostly learned that the oxygen 2p orbitals are prone to meaningfully interact with transition metal d orbitals, because they match not only spatially but also energetically, while for fluorine the p orbital energies are lower to an extent that interaction with transition metal d orbitals is much reduced. This in turn implies that in those instances where the metal d orbitals principally accessible for interaction are occupied, the oxygen 2p orbitals are too exposed to be stable.

| S-EPMC6978815 | biostudies-literature

Catalytic peroxidation of acrylic acid from aqueous solution incorporated with highly active La0.5Sr0.5BO3 (B=Cu, Fe and Ni) perovskite-like catalysts.

Project description:In the current study, catalytic behaviour of La0.5Sr0.5BO3 (B=Cu, Fe and Ni) perovskite-like catalysts synthesized by sol-gel method were examined in catalytic peroxidation of acrylic acid as a model organic compound and further characterized by X-ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) with energy dispersive X-ray (EDX), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The effect of various parameters such as catalyst dose, H2O2/acrylic acid molar ratio, temperature, pH and initial acrylic acid concentration on acrylic acid and COD removal was studied. The maximum acrylic acid and COD removal of 86.79% and 71.57% were observed at optimum operating conditions (e.g., La0.5Sr0.5CuO3 catalyst dose = 600 mg/L, stoichiometric molar ratio of H2O2/acrylic acid = 1.5, pH = 3, temperature 65 °C and reaction time = 3 h). The ROS scavenging studies were performed to identify in-situ generated reactive oxidant species, e.g., hydroxyl radicals (•OH), superoxide radicals (O2 •־) and singlet oxygen (1O2) and treated with their respective quencher during catalytic peroxidation of acrylic acid. Acrylic acid removal kinetics was performed by first order and Langmuir-Hinshelwood kinetic models. The plausible degradation mechanism was proposed based on intermediates identified by GC-MS analysis during catalytic peroxidation of acrylic acid.

| S-EPMC7721942 | biostudies-literature

Tautomerism of Warfarin: Combined Chemoinformatics, Quantum Chemical, and NMR Investigation.

Project description:Warfarin, an important anticoagulant drug, can exist in solution in 40 distinct tautomeric forms through both prototropic tautomerism and ring-chain tautomerism. We have investigated all warfarin tautomers with computational and NMR approaches. Relative energies calculated at the B3LYP/6-311G++(d,p) level of theory indicate that the 4-hydroxycoumarin cyclic hemiketal tautomer is the most stable tautomer in aqueous solution, followed by the 4-hydroxycoumarin open-chain tautomer. This is in agreement with our NMR experiments where the spectral assignments indicate that warfarin exists mainly as a mixture of cyclic hemiketal diastereomers, with an open-chain tautomer as a minor component. We present a diagram of the interconversion of warfarin created taking into account the calculated equilibrium constants (pK(T)) for all tautomeric reactions. These findings help with gaining further understanding of proton transfer and ring closure tautomerization processes. We also discuss the results in the context of chemoinformatics rules for handling tautomerism.

| S-EPMC7724503 | biostudies-literature

Quantum chemical investigation of the antiradical property of avenanthramides, oat phenolics.

Project description:Avenanthramides (AVs) are polyphenolic components found in oats. The present work is devoted to the exploration of structure-based radical scavenging activity of nine AVs; 2p, 2f, 2c, 1p, 1c, 1f, 1s, 2s, and 3f, using M06-2X functional level of density functional theory with basis set 6-31+G(d, p) both in gas and ethanol medium. The act of compounds towards the electron transfer mechanism was analyzed with the help of a Donor-acceptor map (DAM) and classified as antioxidants and anti-reductants. The main mechanism of radical action, HAT, SET-PT, and SPLET were examined and found to be the preference of HAT and SPLET respectively in the gas phase and ethanol medium. The computed quantum mechanical atom in molecule (QTAIM) parameters; the intramolecular H-bonding, Noncovalent interactions, aromaticity also acted as pillars to supports the activity of compounds. The activity was found to be increasing with the stabilizing group ortho to the reactive phenolic OH group.

| S-EPMC7859309 | biostudies-literature

NMR hyperfine shifts in blue copper proteins: a quantum chemical investigation.

Project description:We present the results of the first quantum chemical investigations of 1H NMR hyperfine shifts in the blue copper proteins (BCPs): amicyanin, azurin, pseudoazurin, plastocyanin, stellacyanin, and rusticyanin. We find that very large structural models that incorporate extensive hydrogen bond networks, as well as geometry optimization, are required to reproduce the experimental NMR hyperfine shift results, the best theory vs experiment predictions having R2 = 0.94, a slope = 1.01, and a SD = 40.5 ppm (or approximately 4.7% of the overall approximately 860 ppm shift range). We also find interesting correlations between the hyperfine shifts and the bond and ring critical point properties computed using atoms-in-molecules theory, in addition to finding that hyperfine shifts can be well-predicted by using an empirical model, based on the geometry-optimized structures, which in the future should be of use in structure refinement.

| S-EPMC2761745 | biostudies-literature

Crystal structure of Ba2Co(BO3)2.

Project description:Single crystals of dibarium cobalt(II) bis-(orthoborate), Ba2Co(BO3)2, have been obtained from the melt. The crystal structure is composed of two isolated (BO3)3- triangles linked to Co2+ cations. The resulting [CoO5] square pyramids and the borate anions make up branched rows extending parallel to [010]. The barium cations occupy two sites in the voids of this arrangement and exhibit coordination numbers of nine each. A comparison with the structures of other A 2 M(BO3)2 compounds reveals a unique five-coordination of the small metal M in the title compound instead of four- or six-coordination for the other A 2 M(BO3)2 compounds with M = Cu, Zn, Mg, Ca, or Cd.

| S-EPMC6399684 | biostudies-literature

Crystal structure of Li3Ga(BO3)2.

Project description:The crystal structure of trilithium gallium bis-(orthoborate), Li3Ga(BO3)2, is isotypic with Li3Al(BO3)2 in a triclinic cell in space-group type P-1. The three Li and the unique Ga atom are coordinated by four O atoms each in tetra-hedra, and the two B atoms are coordinated by three O atoms in orthoborate triangles. Chains with composition [Ga2(BO3)4]6- extend along the a axis. The Li atoms inter-leave these chains in tetra-hedral inter-stices. A comparison is made between the structure model of the title compound and that of a previously reported model for a compound with the same composition [Abdullaev & Mamedov (1972 ▸). Zh. Strukt. Khim. 13, 943-946.].

| S-EPMC5347076 | biostudies-literature