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Inorganic Chemistry

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https://www.readbyqxmd.com/read/28098445/circular-and-chainlike-copper-ii-lanthanide-iii-complexes-generated-by-assembly-reactions-of-racemic-and-chiral-copper-ii-cross-linking-ligand-complexes-with-ln-iii-no3-3%C3%A2-6h2o-ln-iii-gd-iii-tb-iii-dy-iii
#1
Takahiro Ueno, Takeshi Fujinami, Naohide Matsumoto, Masaki Furusawa, Ryo Irie, Nazzareno Re, Takuya Kanetomo, Takayuki Ishida, Yukinari Sunatsuki
The 1:1 assembly reaction of the racemic form of the cross-linking ligand complex Na[Cu(II)L(dpen(1R2R/1S2S))] with Ln(III)(NO3)3·6H2O gave the centrosymmetric circular (Cu(II)Ln(III))2 complex [Cu(II)L(dpen(1R2R/1S2S))Ln(III)(NO3)2]2 (1Ln: Ln = Gd, Tb, Dy), while the reaction of the enantiopure form Na[Cu(II)L(dpen(1R2R))] with Ln(III)(NO3)3·6H2O gave the chiral chainlike (Cu(II)Ln(III))1∞ complex [Cu(II)L(dpen(1R2R))Ln(III)(NO3)2(CH3CN)]1∞·CH3CN (2Ln: Ln = Gd, Tb, Dy), where {Cu(II)L(dpen(1R2R))}(-) is (N-((1R,2R)-2-(((E)-3-ethoxy-2-oxybenzylidene)amino)-1,2-diphenylethyl)-2-oxybenzamide)copper(II) and {Cu(II)L(dpen(1R2R/1S2S))}(-) is the racemic mixture of {Cu(II)L(dpen(1R2R))}(-) and {Cu(II)L(dpen(1S2S))}(-)...
January 18, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28094961/enhancing-the-sensing-properties-of-tio2-nanosheets-with-exposed-001-facets-by-a-hydrogenation-and-sensing-mechanism
#2
Ye Wang, Junfang Liu, Miao Wang, Cuijin Pei, Bin Liu, Yukun Yuan, Shengzhong Liu, Heqing Yang
Hydrogenation is successfully employed to improve sensing performances of the gas sensors based on TiO2 nanosheets with exposed {001} facets for the first time. The hydrogenated TiO2 nanosheets show a significantly higher response toward ethanol, acetone, triethylamine, or formaldehyde than the samples without hydrogenation, and the response further increases with an increase of the hydrogenation temperature. The excellent sensing performances are ascribed to an increase of the density of unsaturated Ti5c atoms on the {001} surface resulting from the hydrogenation process...
January 17, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28094935/sulfonic-group-functionalized-mixed-ligand-coordination-polymers-synthesis-characterization-water-sorption-and-proton-conduction-studies
#3
Dilip Kumar Maity, Kenichi Otake, Saheli Ghosh, Hiroshi Kitagawa, Debajyoti Ghoshal
Five sulfonic acid group functionalized mixed ligand coordination polymers (CPs), namely, {[Zn(bpeH)(5-sip)(H2O)]·(H2O)}n (1), {[Cu(pyz)(5-Hsip)(H2O)2]·(H2O)2}n (2), {[Cu(bpee)0.5(5-sip)(H2O)2]·(H2O)4(bpeeH2)0.5}n (3), {[Cu(bpy)(5-Hsip)(H2O)]·(H2O)2}n (4), and {[Cu(bpy)2(5-H2sip)2]·(H2O)6}n (5) [where sip(3-) = 5-sulfoisophthalate; bpe = 4,4'-bispyridylethane; pyz = pyrazine; bpee = 4,4'-bispyridylethylene; bpy = 4,4'-bipyridine], have been synthesized with varying different N,N'-donor linkers using slow diffusion techniques at room temperature...
January 17, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28094934/donor-acceptor-stabilized-tetra-silanimine
#4
Yu-Liang Shan, Bi-Xiang Leong, Yongxin Li, Rakesh Ganguly, Cheuk-Wai So
The synthesis of an oligo(silanimine) is described. The reaction of the amidinato silylene [LSiN(SiMe3)2] (1, L = PhC(NtBu)2) with SiI4 in toluene afforded a mixture of the silanimine [LSi(I)NSiI3] (2), SiMe3I, and Si2I6. The mechanistic studies showed that 1 reacts with SiI4 to form the silyl ionic intermediate "{LSi(I)N(SiMe3)2}(+){SiI3}(-)", which then eliminates SiMe3I and "SiI2" to form the silanimine intermediate "LSi(I)NSiMe3". It further undergoes a substitution with another molecule of SiI4 to form a mixture of 2 and SiMe3I...
January 17, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28094933/accurate-gas-phase-formation-enthalpies-of-alloys-and-refractories-decomposition-products
#5
Yury Minenkov, Valery V Sliznev, Luigi Cavallo
Accurate gas phase formation enthalpies, ΔHf, of metal oxides and halides are critical for the prediction of the stability of high temperature materials used in the aerospace and nuclear industries. Unfortunately, the experimental ΔHf values of these compounds in the most used databases, such as the NIST-JANAF database, are often reported with large inaccuracy, while some other ΔHf values clearly differ from the value predicted by CCSD(T) methods. To address this point, in this work we systematically predicted the ΔHf values of a series of these compounds having a group 4, 6, or 14 metal...
January 17, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28094932/series-d-f-heteronuclear-metal-organic-frameworks-color-tunability-and-luminescent-probe-with-switchable-properties
#6
Xun Feng, Yuquan Feng, Nan Guo, Yiling Sun, Tian Zhang, Lufang Ma, Liya Wang
A series of five unique d-f heteronuclear luminescent metal-organic frameworks (MOFs) in an entangled polyrotaxane array and the light-harvesting block homonuclear zinc compound have been isolated successfully and characterized. The series of isostructural polymers feature 3,4-connected (4.8(2))(4.8(3).9(2))(6.8.9)2(6.9(2))(8(3)) topology and high stability, exhibiting diverse void spaces. By taking advantage of the isostructural MOFs 2 and 3, the intensities of red and green emissions can be modulated by adjusting the ratios of Eu(III) and Tb(III) ions correspondingly, and white-light emission can be generated by a combination of different doped Tb(III) and Eu(III) concentrations...
January 17, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28094930/fe-and-ln-dotam-f12-are-effective-paramagnetic-fluorine-contrast-agents-for-mri-in-water-and-blood
#7
Kriti Srivastava, Evan A Weitz, Katie L Peterson, Małgorzata Marjańska, Valérie C Pierre
A series of fluorinated macrocyclic complexes, M-DOTAm-F12, where M is La(III), Eu(III), Gd(III), Tb(III), Dy(III), Ho(III), Er(III), Tm(III), Yb(III), and Fe(II), was synthesized, and their potential as fluorine magnetic resonance imaging (MRI) contrast agents was evaluated. The high water solubility of these complexes and the presence of a single fluorine NMR signal, two necessary parameters for in vivo MRI, are substantial advantages over currently used organic polyfluorocarbons and other reported paramagnetic (19)F probes...
January 17, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28094522/modulating-the-primary-and-secondary-coordination-spheres-within-a-series-of-co-ii-oh-complexes
#8
Jason R Jones, Joseph W Ziller, A S Borovik
The interplay between the primary and secondary coordination spheres is crucial to determining the properties of transition metal complexes. To examine these effects, a series of trigonal bipyramidal Co-OH complexes have been prepared with tripodal ligands that control both coordination spheres. The ligands contain a combination of either urea or sulfonamide groups that control the primary coordination sphere through anionic donors in the trigonal plane and the secondary coordination sphere through intramolecular hydrogen bonds...
January 17, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28094521/titanium-iii-member-of-the-family-of-trigonal-building-blocks-with-scorpionate-and-cyanide-ligands
#9
Andrew Brown, Mohamed Saber, Willem Van den Heuvel, Kelsey Schulte, Alessandro Soncini, Kim R Dunbar
The titanium(III) cyanide compound [Et4N][Tp*Ti(CN)3] ([Et4N] = tetraethylamonium; Tp* = 3,5-dimethyltrispyrazolylhydroborate) is reported, which exhibits a trigonally distorted geometry. Magnetic data and ab initio calculations verified that the molecule is an S = (1)/2 paramagnet and that it exhibits significant temperature-independent paramagnetism.
January 17, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28094520/synthesis-crystal-structure-magnetic-properties-and-stability-of-the-manganese-rich-mn3alc-%C3%AE%C2%BA-phase
#10
Hannes Dierkes, Jan van Leusen, Dimitri Bogdanovski, Richard Dronskowski
κ-carbides of varying composition, seemingly responsible for age hardening in high-Al steel alloys, have been detected to precipitate both at grain boundaries and in the bulk grain of steels. Herein we report the bulk-phase synthesis of "Mn3AlC" by arc plasma sintering and rapid solidification. Single crystals have been found suitable for X-ray diffraction using Mo radiation and yield a lattice parameter of a = 3.875(2) Å. We find a mixed occupation of the 1a position by Al and Mn, which, together with the C position being fully occupied, leads to the actual composition Mn3...
January 17, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28094512/a-combined-spectroscopic-molecular-dynamic-study-for-investigating-a-methyl-carboxylated-pei-as-a-potential-uranium-decorporation-agent
#11
Florian Lahrouch, Anne Christine Chamayou, Gaëlle Creff, Magali Duvail, Christoph Hennig, Marisol Janeth Lozano Rodriguez, Christophe Den Auwer, Christophe Di Giorgio
Natural uranium has a very limited radioactive dose impact, but its chemical toxicity due to chronic exposure is still a matter of debate. Once inside the human body, the soluble uranium, under its uranyl form (U(VI)), is quickly removed from the blood system, partially excreted from the body, and partially retained in targeted organs, that is, the kidneys and bone matrix essentially. It is then crucial to remove or prevent the incorporation of uranium in these organs to limit the long-term chronic exposure...
January 17, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28085271/first-order-phase-transition-in-bani2ge2-and-the-influence-of-the-valence-electron-count-on-distortion-of-the-thcr2si2-structure-type
#12
Viktor Hlukhyy, Dmytro Trots, Thomas F Fässler
Structural instability has a strong influence on the understanding of superconductivity in iron-containing 122 phases. Similar to the 122 iron-based high-temperature superconductors, the intermetallic compound BaNi2Ge2 undergoes an orthorhombic-to-tetragonal structural phase transition. The compound was prepared by arc-melting mixtures of the elements under an argon atmosphere. Single crystals were obtained by a special heat treatment in a welded tantalum ampule. The crystal structure of the compound was investigated by powder and single-crystal X-ray diffraction...
January 13, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28085264/urea-metal-organic-frameworks-for-nitro-substituted-compounds-sensing
#13
Alireza Azhdari Tehrani, Leili Esrafili, Sedigheh Abedi, Ali Morsali, Lucia Carlucci, Davide M Proserpio, Jun Wang, Peter C Junk, Tianfu Liu
Urea groups are known to form strong hydrogen bonds with molecules containing atom(s) that can act as hydrogen bond acceptor(s). Thus, urea is a particularly interesting building block for designing receptors for neutral or charged guests. In the quest for new sensors with enhanced performance for the detection of nitro-substituted compounds, two pillared metal-organic frameworks containing urea functional groups were synthesized and structurally characterized. The sensing properties of these frameworks toward nitro-analytes were investigated and compared to each other...
January 13, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28085259/unique-approach-to-copper-i-silylene-chalcogenone-complexes
#14
Nasrina Parvin, Shiv Pal, Shabana Khan, Shubhajit Das, Swapan K Pati, Herbert W Roesky
Silylene-S-thione [PhC(NtBu)2Si(═S)N(SiMe3)2] (2) and silylene-Se-selone [PhC(NtBu)2Si(═Se)N(SiMe3)2] (3) compounds were prepared from the silylene [PhC(NtBu)2SiN(SiMe3)2] (1) with 1 equiv of 1/8 S8 and 1 equiv of Se powder, respectively, in high yields. Furthermore, compounds 2 and 3 reacted with CuCl and CuBr and yielded [{PhC(NtBu)2}Si(═S→CuX)N(SiMe3)2] (X = Cl (4), Br (5)) and [{PhC(NtBu)2}Si(═Se→CuX)N(SiMe3)2] (X = Cl (6), Br (7)), respectively. Complexes 4-7 can also be obtained from the direct reaction of sulfur and selenium with the corresponding silylene copper complexes [{PhC(NtBu)2}Si{N(SiMe3)2}]2Cu2X2 (X = Cl (8), Br (9))...
January 13, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28085257/formation-mechanisms-in-%C3%AE-ca3-po4-2-zno-composites-structural-repercussions-of-composition-and-heat-treatments
#15
Ponnusamy Nandha Kumar, José Maria da Fonte Ferreira, Sanjeevi Kannan
Composites with varied proportions of β-Ca3(PO4)2 and ZnO were obtained through an in situ aqueous precipitation method under slightly basic (pH ≈ 8) conditions. The formation of β-Ca3(PO4)2 phase starts at an early heat-treatment stage (∼800 °C) and incorporates Zn(2+) ions at both Ca(2+)(4) and Ca(2+)(5) sites of the lattice up to its occupancy saturation limit. The incorporation of Zn(2+) in the β-Ca3(PO4)2 lattice enhances its thermal stability delaying the allotropic β-Ca3(PO4)2→α-Ca3(PO4)2 phase transformation...
January 13, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28084072/reactions-of-lithiated-diphosphanes-r2p-p-sime3-li-r-tbu-and-ipr-with-me-nacnacticl2%C3%A2-thf-and-me-nacnacticl3-formation-and-structure-of-titanium-iii-and-titanium-iv-%C3%AE-diketiminato-complexes-bearing-the-side-on-phosphanylphosphido-and-phosphanylphosphinidene
#16
Ł Ponikiewski, A Ziółkowska, J Pikies
β-Diketiminate complexes of Ti(III)-containing phosphanylphosphido ligands [(Me)NacnacTi(Cl){η(2)-P(SiMe3)-PR2}] ((Me)Nacnac(-) = [Ar]NC(Me)CHC(Me)N[Ar]; Ar = 2,6-iPr2C6H3) were prepared by reactions of [(Me)NacnacTiCl2·THF] with lithium derivatives of diphosphanes R2P-P(SiMe3)Li (R = tBu, iPr) in toluene solutions. Surprisingly, reactions of [(Me)NacnacTiCl2·THF] with R2P-P(SiMe3)Li in THF solutions led to Ti(IV) complexes containing phosphanylphosphinidene ligands [(Me)NacnacTi(Cl)(η(2)-P-PtBu2)] via an autoredox path involving a migration of a nitrene NAr from the Nacnac skeleton to the Ti centers...
January 13, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28080044/structural-dependence-of-the-ising-type-magnetic-anisotropy-and-of-the-relaxation-time-in-mononuclear-trigonal-bipyramidal-co-ii-single-molecule-magnets
#17
Feng Shao, Benjamin Cahier, Eric Rivière, Régis Guillot, Nathalie Guihéry, Victoria E Campbell, Talal Mallah
This paper describes the correlation between Ising-type magnetic anisotropy and structure in trigonal bipyramidal Co(II) complexes. Three sulfur-containing trigonal bipyramidal Co(II) complexes were synthesized and characterized. It was shown that we can engineer the magnitude of the Ising anisotropy using ligand field theory arguments in conjunction with structural parameters. To prepare this series of compounds, we used, on the one hand, a tetradentate ligand containing three sulfur atoms and one amine (NS3(tBu)) and on the other hand three different axial ligands, namely, Cl(-), Br(-), and NCS(-)...
January 12, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28079376/synthesis-structures-and-co-release-capacity-of-a-family-of-water-soluble-photocorms-assessment-of-the-biocompatibility-and-their-phototoxicity-toward-human-breast-cancer-cells
#18
Indranil Chakraborty, Samantha J Carrington, Graham Roseman, Pradip K Mascharak
Two manganese(I) carbonyl complexes derived from 2-(pyridyl)benzothiazole (pbt) and 1,10-phenanthroline (phen) release carbon monoxide (CO) under low-power broad-band visible-light illumination. CO photorelease from [Mn(CO)3(pbt)(PTA)]CF3SO3 (1, where PTA = 1,3,5-triaza-7-phosphaadamantane) is accompanied by an emergence of a strong fluorescence around 400 nm from almost nonfluorescent preirradiated 1. However, [Mn(CO)3(phen)(PTA)]CF3SO3 (2) showed no such phenomenon upon prolonged illumination under similar experimental conditions...
January 12, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28079372/effect-of-water-coordination-on-luminescent-properties-of-pyrazine-bridged-dinuclear-cu-i-complexes
#19
Atsushi Kobayashi, Ryuya Arata, Tomohiro Ogawa, Masaki Yoshida, Masako Kato
Two luminescent pyrazine-bridged dinuclear Cu(I) complexes, namely, [{Cu(PPh3)2(H2O)}(μ-MeOpyz){Cu(PPh3)2(CH3CN)}](BF4)2 and [{Cu(PPh3)2(H2O)}(μ-MeOpyz){Cu(PPh3)2(H2O)}](BF4)2 (H2O-Cu2-AN and H2O-Cu2-H2O; PPh3 = triphenylphosphine, MeOpyz = 2-methoxypyrazine), were successfully synthesized and characterized by single-crystal X-ray diffraction and luminescence measurements. X-ray analysis revealed that the water molecules are coordinated to both Cu(I) ions to form almost the same P2N1O1 coordination structure in H2O-Cu2-H2O, whereas one of the two Cu ions in H2O-Cu2-AN was coordinated by acetonitrile instead of water to form a different P2N2 coordination environment...
January 12, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28079368/ligand-design-for-isomer-selective-oxorhenium-v-complex-synthesis
#20
Jinyong Liu, Xiaoge Su, Mengwei Han, Dimao Wu, Danielle L Gray, John R Shapley, Charles J Werth, Timothy J Strathmann
Recently, N,N-trans Re(O)(LN-O)2X (LN-O = monoanionic N-O chelates; X = Cl or Br prior to being replaced by solvents or alkoxides) complexes have been found to be superior to the corresponding N,N-cis isomers in the catalytic reduction of perchlorate via oxygen atom transfer. However, reported methods for Re(O)(LN-O)2X synthesis often yield only the N,N-cis complex or a mixture of trans and cis isomers. This study reports a geometry-inspired ligand design rationale that selectively yields N,N-trans Re(O)(LN-O)2Cl complexes...
January 12, 2017: Inorganic Chemistry
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