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Inorganic Chemistry

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https://www.readbyqxmd.com/read/28234010/structural-perceptions-and-mechanical-evaluation-of-%C3%AE-ca3-po4-2-c-ceo2-composites-with-preferential-occupancy-of-ce-3-and-ce-4
#1
Ponnusamy Nandha Kumar, Sandeep Kumar Mishra, Sanjeevi Kannan
The role of cerium in the formation of stable β-Ca3(PO4)2/c-CeO2 composites and their structural analysis with varied compositional ratios were investigated. The composite formation was attempted through an in situ precipitation technique, and the gradual structural changes during heat treatments to yield the pure form of β-Ca3(PO4)2/c-CeO2 composites was presented. The cerium was found in Ce(3+) and Ce(4+) oxidation states in composites. Ce(3+) prefers to occupy the Ca(2+)(1), Ca(2+)(2), and Ca(2+)(3) sites of β-Ca3(PO4)2, whereas, beyond the saturation occupancy limit, excess cerium prefers to crystallize in the form of thermodynamically stable cubic ceria (c-CeO2)...
February 24, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28233995/hydrothermal-synthesis-structure-and-superconductivity-of-simple-cubic-perovskite-ba0-62k0-38-bi0-92mg0-08-o3-with-tc-%C3%A2-30-k
#2
Mirza H K Rubel, Takahiro Takei, Nobuhiro Kumada, M Mozahar Ali, Akira Miura, Kiyoharu Tadanaga, Kengo Oka, Masaki Azuma, Eisuke Magome, Chikako Moriyoshi, Yoshihiro Kuroiwa
We have synthesized a new superconducting perovskite bismuth oxide by a facile hydrothermal route at 220 °C. The choice of starting materials, their mixing ratios, and the hydrothermal reaction temperature was crucial for obtaining products with superior superconducting properties. The structure of the powder sample was investigated using laboratory X-ray diffraction, high-resolution synchrotron X-ray diffraction (SXRD) data, and electron diffraction (ED) patterns [transmission electron microscopy (TEM) analysis]...
February 24, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28230991/electron-accumulation-on-naphthalene-diimide-photosensitized-by-ru-2-2-bipyridine-3-2
#3
Michael Skaisgirski, Xingwei Guo, Oliver S Wenger
In a molecular triad comprised of a central naphthalene diimide (NDI) unit flanked by two [Ru(bpy)3](2+) (bpy = 2,2'-bipyridine) sensitizers, NDI(2-) is formed after irradiation with visible light in deaerated CH3CN in the presence of excess triethylamine. The mechanism for this electron accumulation involves a combination of photoinduced and thermal elementary steps. In a structurally related molecular pentad with two peripheral triarylamine (TAA) electron donors attached covalently to a central [Ru(bpy)3](2+)-NDI-[Ru(bpy)3](2+) core but no sacrificial reagents present, photoexcitation only leads to NDI(-) (and TAA(+)), whereas NDI(2-) is unattainable due to rapid electron transfer events counteracting charge accumulation...
February 23, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28230368/structural-electronic-and-optical-properties-of-k2sn3o7-with-an-offset-hollandite-structure
#4
Rebecca D McAuliffe, Christopher A Miller, Xiao Zhang, Benjamin S Hulbert, Ashfia Huq, Clarina Dela Cruz, André Schleife, Daniel P Shoemaker
We present the compound K2Sn3O7, a Sn(4+)-containing oxide with a unique structure type among oxides. The compound is orthorhombic and reminiscent of an offset hollandite, where open channels hold a row of four K(+) per channel per cell. UV-visible spectroscopy indicates a wide band gap semiconductor, which is confirmed by first-principles electronic-structure calculations of band structures, densities of states, and optical properties. The continued discovery of new structure types in ternary tin oxides should remain a priority for the identification of prospective ion conductors and transparent conducting compounds...
February 23, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28225611/magneto-structural-correlations-in-pseudotetrahedral-forms-of-the-co-sph-4-2-complex-probed-by-magnetometry-mcd-spectroscopy-advanced-epr-techniques-and-ab-initio-electronic-structure-calculations
#5
Elizaveta A Suturina, Joscha Nehrkorn, Joseph M Zadrozny, Junjie Liu, Mihail Atanasov, Thomas Weyhermüller, Dimitrios Maganas, Stephen Hill, Alexander Schnegg, Eckhard Bill, Jeffrey R Long, Frank Neese
The magnetic properties of pseudotetrahedral Co(II) complexes spawned intense interest after (PPh4)2[Co(SPh)4] was shown to be the first mononuclear transition-metal complex displaying slow relaxation of the magnetization in the absence of a direct current magnetic field. However, there are differing reports on its fundamental magnetic spin Hamiltonian (SH) parameters, which arise from inherent experimental challenges in detecting large zero-field splittings. There are also remarkable changes in the SH parameters of [Co(SPh)4](2-) upon structural variations, depending on the counterion and crystallization conditions...
February 22, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28225607/reactivity-study-of-unsymmetrical-%C3%AE-diketiminato-copper-i-complexes-effect-of-the-chelating-ring
#6
Wan-Jung Chuang, Sung-Po Hsu, Kuldeep Chand, Fu-Lun Yu, Cheng-Long Tsai, Yu-Hsuan Tseng, Yuh-Hsiu Lu, Jen-Yu Kuo, James R Carey, Hsuan-Ying Chen, Hsing-Yin Chen, Michael Y Chiang, Sodio C N Hsu
β-Diketiminato copper(I) complexes play important roles in bioinspired catalytic chemistry and in applications to the materials industry. However, it has been observed that these complexes are very susceptible to disproportionation. Coordinating solvents or Lewis bases are typically used to prevent disproportionation and to block the coordination sites of the copper(I) center from further decomposition. Here, we incorporate this coordination protection directly into the molecule in order to increase the stability and reactivity of these complexes and to discover new copper(I) binding motifs...
February 22, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28225602/exploring-the-detection-of-metal-ions-by-tailoring-the-coordination-mode-of-v-shaped-thienylpyridyl-ligand-in-three-mofs
#7
Li-Juan Han, Wei Yan, Shu-Guang Chen, Zhen-Zhen Shi, He-Gen Zheng
By employing a rational design approach, we synthesized three luminescent metal-organic frameworks (MOFs) 1-3 affording different coordination modes of V-shaped thienylpyridyl ligand. Their application in detecting metal ions was explored, and the mechanism was inferred. And the result exhibits that MOF 3 is a dual-responsive luminescent probe for Fe(3+) and Al(3+) ions.
February 22, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28225599/cubic-sr2scgao5-perovskite-structural-stability-oxygen-defect-structure-and-ion-conductivity-explored-on-single-crystals
#8
Serena Corallini, Monica Ceretti, Alain Cousson, Clemens Ritter, Marco Longhin, Philippe Papet, Werner Paulus
Oxygen-deficient Sr2ScGaO5 single crystals with a cubic perovskite structure were grown by the floating-zone technique. The transparent crystals of this pure 3D oxygen electrolyte are metastable at ambient temperature, showing one-sixth of all oxygen positions vacant. While neutron single-crystal diffraction, followed by maximum entropy analysis, revealed a strong anharmonic displacements for the oxygen atoms, a predominant formation of ScO6 octahedra and GaO4 tetrahedra is indicated by Raman spectroscopic studies, resulting in a complex oxygen defect structure with short-range order...
February 22, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28225268/structure-and-characterization-of-a-zero-dimensional-alkali-tin-dihalides-compound-cs3sn3f2cl7-with-the-sn2f2cl4-2-clusters
#9
Pifu Gong, Siyang Luo, Ke Xiao, Qian Huang, Yi Yang, Hongwei Huang, Yicheng Wu, Chuangtian Chen, Zheshuai Lin
A new perovskite stoichiometric alkali tin dihalides compound, Cs3Sn3F2Cl7, is synthesized by a hydrothermal method. This compound belongs to the monoclinic space group of P21/c with cell parameters of a = 9.5645(4) Å, b = 14.2057(7) Å, c = 13.5828(6) Å, and β = 93.2450(10)°. Unlike the common perovskites in which octahedra are interconnected to be a three-dimensional network, Cs3Sn3F2Cl7 possesses a zero-dimensional structure consisting of Cs(+) cations, isolated [SnCl3](-) trigonal pyramids, and dimer structural units [Sn2F2Cl4](2-); the latter microscopic unit is found for the first time...
February 22, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28225252/luminescent-re-i-carbonyl-complexes-as-trackable-photocorms-for-co-delivery-to-cellular-targets
#10
Indranil Chakraborty, Jorge Jimenez, W M C Sameera, Masako Kato, Pradip K Mascharak
A family of Re(I) carbonyl complexes of general formula [ReX(CO)3(phen)](0/1+) (where X = Cl(-), CF3SO3(-), MeCN, PPh3, and methylimidazole) derived from 1,10-phenanthroline (phen) exhibits variable emission characteristics depending on the presence of the sixth ancillary ligand/group (X). All complexes but with X = MeCN exhibit moderate CO release upon irradiation with low-power UV light and are indefinitely stable in anaerobic/aerobic environment in solution as well as in solid state when kept under dark condition...
February 22, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28221786/chemical-trends-in-solid-alkali-pertechnetates
#11
Jamie Weaver, Chuck Z Soderquist, Nancy M Washton, Andrew S Lipton, Paul L Gassman, Wayne W Lukens, Albert A Kruger, Nathalie A Wall, John S McCloy
Insight into the solid-state chemistry of pure technetium-99 ((99)Tc) oxides is required in the development of a robust immobilization and disposal system for nuclear waste stemming from the radiopharmaceutical industry, from the production of nuclear weapons, and from spent nuclear fuel. However, because of its radiotoxicity and the subsequent requirement of special facilities and handling procedures for research, only a few studies have been completed, many of which are over 20 years old. In this study, we report the synthesis of pure alkali pertechnetates (sodium, potassium, rubidium, and cesium) and analysis of these compounds by Raman spectroscopy, X-ray absorption spectroscopy (XANES and EXAFS), solid-state nuclear magnetic resonance (static and magic angle spinning), and neutron diffraction...
February 21, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28221785/homogeneous-synthesis-and-electroluminescence-device-of-highly-luminescent-cspbbr3-perovskite-nanocrystals
#12
Song Wei, Yanchun Yang, Xiaojiao Kang, Lan Wang, Lijian Huang, Daocheng Pan
Highly luminescent CsPbBr3 perovskite nanocrystals (PNCs) are homogeneously synthesized by mixing toluene solutions of PbBr2 and cesium oleate at room temperature in open air. We found that PbBr2 can be easily dissolved in nonpolar toluene in the presence of tetraoctylammonium bromide, which allows us to homogeneously prepare CsPbBr3 perovskite quantum dots and prevents the use of harmful polar organic solvents, such as N,N-dimethylformamide, dimethyl sulfoxide, and N-methyl-2-pyrrolidone. Additionally, this method can be extended to synthesize highly luminescent CH3NH3PbBr3 perovskite quantum dots...
February 21, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28221777/rhenium-complexes-based-on-2-pyridyl-1-2-3-triazole-ligands-a-new-class-of-co2-reduction-catalysts
#13
H Y Vincent Ching, Xia Wang, Menglan He, Noemi Perujo Holland, Régis Guillot, Cyrine Slim, Sophie Griveau, Hélène C Bertrand, Clotilde Policar, Fethi Bedioui, Marc Fontecave
A series of [Re(N^N)(CO)3(X)] (N^N = diimine and X = halide) complexes based on 4-(2-pyridyl)-1,2,3-triazole (pyta) and 1-(2-pyridyl)-1,2,3-triazole (tapy) diimine ligands have been prepared and electrochemically characterized. The first ligand-based reduction process is shown to be highly sensitive to the nature of the isomer as well as to the substituents on the pyridyl ring, with the peak potential changing by up to 700 mV. The abilities of this class of complexes to catalyze the electroreduction and photoreduction of CO2 were assessed for the first time...
February 21, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28221770/the-triple-salt-sr14-ta4n13-tan4-o-a-nitridotantalate-oxide-with-19-fold-rock-salt-superstructure
#14
Matthias Wörsching, Martin Daiger, Constantin Hoch
A new structure motif in nitridometalate chemistry is the tetracatena-nitridotantalate anion [Ta4N13](19-). It occurs in the crystal structure of the triple salt Sr14[Ta4N13][TaN4]O (monoclinic, space group P21/c with a = 15.062(2) Å, b = 7.2484(6) Å, c = 24.266(3) Å, and β = 97.280(10)(o)) together with ortho-tantalate and isolated oxide anions. Synthesis followed a new approach with employment of Sr surplus and reductive conditions aimed at the preparation of subvalent compounds. The new structure type was established on the basis of single-crystal X-ray diffraction data and also Rietveld refinement...
February 21, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28221038/molecular-and-electronic-structures-of-m2o7-m-mn-tc-re
#15
Keith V Lawler, Bradley C Childs, Daniel S Mast, Kenneth R Czerwinski, Alfred P Sattelberger, Frederic Poineau, Paul M Forster
The molecular and electronic structures of the group 7 heptoxides were investigated by computational methods as both isolated molecules and in the solid-state. The metal-oxygen-metal bending angle of the single molecule increased with increasing atomic number, with Re2O7 preferring a linear structure. Natural bond orbital and localized orbital bonding analyses indicate that there is a three-center covalent bond between the metal atoms and the bridging oxygen, and the increasing ionic character of the bonds favors larger bond angles...
February 21, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28218861/18-electron-resonance-structures-in-the-bcc-transition-metals-and-their-cscl-type-derivatives
#16
Anastasiya I Vinokur, Daniel C Fredrickson
Bonding in elemental metals and simple alloys has long been thought of as involving intense delocalization, with little connection to the localized bonds of covalent systems. In this Article, we show that the bonding in body-centered cubic (bcc) structures of the group 6 transition metals can in fact be represented, via the concepts of the 18-n rule and isolobal bonding, in terms of two balanced resonance structures. We begin with a reversed approximation Molecular Orbital (raMO) analysis of elemental Mo in its bcc structure...
February 20, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28218839/phosphenium-hydride-reduction-of-cod-mx2-m-pd-pt-x-cl-br-snapshots-on-the-way-to-phosphenium-metal-0-halides-and-synthesis-of-metal-nanoparticles
#17
Jan Nickolaus, Dominik A Imbrich, Simon H Schlindwein, Adrian H Geyer, Martin Nieger, Dietrich Gudat
The outcome of the reduction of [(cod)PtX2] (X = Cl, Br; cod = 1,5-cyclooctadiene) with N-heterocyclic phosphenium hydrides (R)NHP-H depends strongly on the steric demand of the N-aryl group R and the nature of X. Reaction of [(cod)PtCl2] with (Dipp)NHP-H featuring bulky N-Dipp groups produced an unprecedented monomeric phosphenium metal(0) halide [((Dipp)NHP)((Dipp)NHP-H)PtCl] stabilized by a single phosphine ligand. The phosphenium unit exhibits a pyramidal coordination geometry at the phosphorus atom and may according to DFT calculations be classified as a Z-type ligand...
February 20, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28218836/magnetic-and-hfepr-studies-of-exchange-coupling-in-a-series-of-%C3%AE-cl-dicobalt-complexes
#18
Jia-Jia Liu, Shang-Da Jiang, Petr Neugebauer, Joris van Slageren, Yanhua Lan, Wolfgang Wernsdorfer, Bing-Wu Wang, Song Gao
We report three dinuclear cobalt(II) complexes, [Co(L)Cl2]2 (L = bpy, mbpy, and dmpbt), that are bridged solely by chloride ions. High-field electron paramagnetic resonance and magnetometric measurements were applied to investigate the magnetic intramolecular Co-Co interactions. Simulation results based on the multispin model reveal that the complexes are weakly ferromagnetically coupled and that the isotropic exchange coupling constants differ slightly for the three complexes. Moreover, the competing effects of zero-field splitting and magnetic coupling on the temperature-dependent magnetic susceptibility were analyzed...
February 20, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28218541/electronic-structures-of-reduced-and-superreduced-ir2-1-8-diisocyanomenthane-4-n-complexes
#19
Stanislav Záliš, Bryan M Hunter, Harry B Gray, Antonín Vlček
Molecular and electronic structures of Ir2(1,8-diisocyanomenthane)4(n+) (Ir(dimen)(n+)) complexes have been investigated by DFT for n = 2, 1, 0 (abbreviated 2+, 1+, 0). Calculations reproduced the experimental structure of 2+, ν(C≡N) IR, and visible absorption spectra of all three oxidation states, as well as the EPR spectrum of 1+. We have shown that the two reduction steps correspond to successive filling of the Ir-Ir pσ orbital. Complexes 2+ and 1+ have very similar structures with 1+ having a shorter Ir-Ir distance...
February 20, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28218540/perovskite-like-organic-inorganic-hybrid-lead-iodide-with-a-large-organic-cation-incorporated-within-the-layers
#20
Chen-Jie Que, Chong-Jiao Mo, Zhao-Qi Li, Guang-Lin Zhang, Qin-Yu Zhu, Jie Dai
A great effort has been made to investigate 2D perovskites to improve the stability and controllability in the fabrication of photoelectronic devices. As far as we know, only small organic cations such as methylammonium can incorporate into the multilayered perovskite structure except the cations sandwiched between the inorganic layers. We report here a new layered lead iodide, (H2Aepz)3Pb4I14 (1), where larger organic cations, bis-protonated 2-(2-aminoethyl)pyrazole (Aepz), not only were sandwiched between the inorganic layers but also were incorporated within the perovskite-like PbI layered structure...
February 20, 2017: Inorganic Chemistry
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