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Inorganic Chemistry

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https://www.readbyqxmd.com/read/28921973/evans-showell-type-polyoxometalates-constructing-high-dimensional-inorganic-organic-hybrid-compounds-with-copper-organic-coordination-complexes-synthesis-and-oxidation-catalysis
#1
Haiyan An, Yujiao Hou, Lin Wang, Yumeng Zhang, Wei Yang, ShenZhen Chang
Four new hybrid architectures containing a [Co2Mo10H4O38](6-) polyoxoanion, (en)[Cu3(ptz)4(H2O)4][Co2Mo10H4O38]·24H2O (1), (Hbim)2[{Cu(bim)2(H2O)2}2{Co2Mo10H4O38}]·5H2O (2), H2[Cu(dpdo)3(H2O)4][{Cu2(dpdo)3(H2O)4(CH3CN)}2{Co2Mo10H4O38}2]·9H2O (3), and (H2bpp)4[{Cu(H2O)2}{NaCo2Mo10H4O38}2]·10H2O (4), where ptz = 5-(4-pyridyl)-1H-tetrazole, en = ethylenediamine, bim = benzimidazole, dpdo = 4,4'-bipyridine-N,N'-dioxide, and bpp = 1,3-bis(4-pyridyl)propane, have been prepared and characterized through elemental analysis, thermogravimetric analysis, IR spectroscopy, and powder and single-crystal X-ray diffraction...
September 18, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28921970/tris-heteroleptic-iridium-complexes-based-on-cyclometalated-ligands-with-different-cores
#2
Yanouk Cudré, Felipe Franco de Carvalho, Gregory R Burgess, Louise Male, Simon J A Pope, Ivano Tavernelli, Etienne Baranoff
A series of tris-heteroleptic iridium complexes of the form [Ir(C^N(1))(C^N(2))(acac)] combining 2-phenylpyridine (ppy), 2-(2,4-difluorophenyl)pyridine (dFppy), 1-phenylpyrazole (ppz), and 1-(2,4-difluorophenyl)pyrazole (dFppz) as the C^N ligands have been synthesized and fully characterized by NMR, X-ray crystallography, UV-vis absorption and emission spectroscopy, and electrochemical methods. It is shown that "static properties" (e.g., absorption and emission spectra and redox potentials) are primarily dictated by the overall architecture of the complex, while "dynamic properties" (e...
September 18, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28921964/versatile-synthetic-route-for-%C3%AE-functionalized-chlorins-and-porphyrins-by-varying-the-size-of-michael-donors-syntheses-photophysical-and-electrochemical-redox-properties
#3
Nivedita Chaudhri, Nitika Grover, Muniappan Sankar
One-pot facile synthesis and characterization of novel β-substituted meso-tetraphenylporphyrins and/or chlorins were described. The high regioselective reactivity of active methylene compounds in Michael addition reaction was reported to access β-substituted trans-chlorins. Size-dependent approach was applied for the fine-tuning of product formation from porphyrins to chlorins. Notably, we were able to isolate mono/trisubstituted porphyrin and/or di/tetra-substituted chlorin from one-pot synthesis for the first time in porphyrin chemistry...
September 18, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28921960/boron-difluoride-adducts-of-a-flexidentate-pyridine-substituted-formazanate-ligand-property-modulation-via-protonation-and-coordination-chemistry
#4
Stephanie M Barbon, Jasmine V Buddingh, Ryan R Maar, Joe B Gilroy
The synthesis and characterization of a flexidentate pyridine-substituted formazanate ligand and its boron difluoride adducts, formed via two different coordination modes of the title ligand, are described. The first adduct adopted a structure that was typical of other boron difluoride adducts of triarylformazanate ligands and contained a free pyridine subsituent, while the second was formed via the chelation of nitrogen atoms from the formazanate backbone and the pyridine substituent. Stepwise protonation of the pydridine-functionalized adduct, which is essentially nonemissive, resulted in a significant increase in the fluorescence quantum yield up to a maximum of 18%, prompting the study of this adduct as a pH sensor...
September 18, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28920698/correlating-bridging-ligand-with-properties-of-ligand-templated-mn-ii-3x3-3-clusters-x-br-cl-h-meo
#5
Kevin J Anderton, David M Ermert, Pedro A Quintero, Mackenzie W Turvey, Majed S Fataftah, Khalil A Abboud, Mark W Meisel, Erik Čižmár, Leslie J Murray
Polynuclear manganese compounds have garnered interest as mimics and models of the water oxidizing complex (WOC) in photosystem II and as single molecule magnets. Molecular systems in which composition can be correlated to physical phenomena, such as magnetic exchange interactions, remain few primarily because of synthetic limitations. Here, we report the synthesis of a family of trimanganese(II) complexes of the type Mn3X3L (X = Cl(-), H(-), and MeO(-)) where L(3-) is a tris(β-diketiminate) cyclophane. The tri(chloride) complex (2) is structurally similar to the reported tri(bromide) complex (1) with the Mn3X3 core having a ladder-like arrangement of alternating M-X rungs, whereas the tri(μ-hydride) (3) and tri(μ-methoxide) (4) complexes contain planar hexagonal cores...
September 18, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28920686/high-pressure-synthesis-of-the-cobalt-pyrochlore-oxide-pb2co2o7-with-large-cation-mixed-occupancy
#6
Junye Yang, Jianhong Dai, Zhehong Liu, Runze Yu, Hajime Hojo, Zhiwei Hu, Tunwen Pi, Yunliang Soo, Changqing Jin, Masaki Azuma, Youwen Long
The novel A2B2O7-type compound Pb2Co2O7 was synthesized at 8 GPa and 1673 K. Synchrotron X-ray diffraction shows a cubic pyrochlore structure with space group Fd3̅m. Rietveld structural analysis reveals a large cation mixed occupancy at both A and B sites by about 40%, the greatest value found in the pyrochlore family. In combination with the X-ray absorption spectroscopy results, the specific chemical composition and charge states are determined to be (Co0.6Pb0.4)(3+)2(Pb0.6Co0.4)(4+)2O7, in which both the A-site Co(3+) and the B-site Co(4+) are low-spin...
September 18, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28920685/evaluation-of-the-intramolecular-charge-transfer-properties-in-solvatochromic-and-electrochromic-zinc-octa-carbazolyl-phthalocyanines
#7
Shereen A Majeed, Basma Ghazal, Dustin E Nevonen, Philip C Goff, David A Blank, Victor N Nemykin, Saad Makhseed
2,3,9,10,16,17,23·24-Octakis-(9H-carbazol-9-yl) phthalocyaninato zinc(II) (3) and 2,3,9,10,16,17,23·24-octakis-(3,6-di-tert-butyl-9H-carbazole) phthalocyaninato zinc(II) (4) complexes were prepared and characterized by NMR and UV-vis spectroscopies, magnetic circular dichroism (MCD), matrix-assisted laser desorption ionization mass spectrometry, and X-ray crystallography. UV-vis and MCD data are indicative of the interligand charge-transfer nature of the broad band observed in 450-500 nm range for 3 and 4...
September 18, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28920680/a-restricted-open-configuration-interaction-with-singles-method-to-calculate-valence-to-core-resonant-x-ray-emission-spectra-a-case-study
#8
Dimitrios Maganas, Serena DeBeer, Frank Neese
In this work, a new protocol for the calculation of valence-to-core resonant X-ray emission (VtC RXES) spectra is introduced. The approach is based on the previously developed restricted open configuration interaction with singles (ROCIS) method and its parametrized version, based on a ground-state Kohn-Sham determinant (DFT/ROCIS) method. The ROCIS approach has the following features: (1) In the first step approximation, many-particle eigenstates are calculated in which the total spin is retained as a good quantum number...
September 18, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28920677/group-10-metal-benzene-1-2-dithiolate-derivatives-in-the-synthesis-of-coordination-polymers-containing-potassium-countercations
#9
Oscar Castillo, Esther Delgado, Carlos J Gómez-García, Diego Hernández, Elisa Hernández, Avelino Martín, José I Martínez, Félix Zamora
The use of theoretical calculations has allowed us to predict the coordination behavior of dithiolene [M(SC6H4S)2](2-) (M = Ni, Pd, Pt) entities, giving rise to the first organometallic polymers {[K2(μ-H2O)2][Ni(SC6H4S)2]}n and {[K2(μ-H2O)2(thf)]2[K2(μ-H2O)2(thf)2][Pd3(SC6H4S)6]}n by one-pot reactions of the corresponding d(10) metal salts, 1,2-benzenedithiolene, and KOH. The polymers are based on σ,π interactions between potassium atoms and [M(SC6H4S)2](2-) (M = Ni, Pd) entities. In contrast, only σ interactions are observed when the analogous platinum derivative is used instead, yielding the coordination polymer {[K2(μ-thf)2][Pt(SC6H4S)2]}n...
September 18, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28915029/rapid-one-pot-solvothermal-batch-synthesis-of-porous-nanocrystal-assemblies-composed-of-multiple-transition-metal-elements
#10
Masataka Ohtani, Tomoyuki Muraoka, Yuki Okimoto, Kazuya Kobiro
The ability of a rapid-heating solvothermal process to synthesize porous nanocrystal assemblies composed of the multiple transition metals was demonstrated. The rapid heating facilitated the quick formation of nascent nanocrystals to generate homogeneous mixed transition-metal oxides. Systematic studies of the synthesis of mixed-metal oxides under various experimental conditions indicated that the present simple method is suitable to develop a wide variety of binary and ternary transition-metal systems such as Co/Mn, Ni/Mn, and Co/Mn/Fe mixed-metal oxides...
September 15, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28915026/supercubes-supersquares-and-superrods-of-face-centered-cubes-fcc-atomic-and-electronic-requirements-of-mm-sr-l-pr-3-8-q-nanoclusters-m-coinage-metals-and-their-implications-with-respect-to-nucleation-and-growth-of-fcc-metals
#11
Boon K Teo, Huayan Yang, Juanzhu Yan, Nanfeng Zheng
Understanding the nucleation and growth pathways of nanocrystallites allows precise control of the size and shape of functional crystalline nanomaterials of importance in nanoscience and nanotechnology. This paper provides a detailed analysis of the stereochemical and electronic requirements of three series of nanoclusters based on face-centered cubes (fcc) as the basic building blocks, namely, 1-, 2-, and 3-D assemblages of fcc to form superrods (n), supersquares (n(2)), and supercubes (n(3)). The generating functions for calculating the numbers (and arrangements) of surface and interior metal atoms, as well as the number and dispositions of the ligands, for these particular sequences of fcc metal clusters of the general formula [Mm(SR)l(PR'3)8](q) (where M = coinage metals; SR = thiolates (or group XI ligands), and PR'3 = phosphines) are presented...
September 15, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28915024/synthesis-and-crystal-structure-of-suboxide-solid-solutions-ti12-%C3%AE-gaxbi3-xo10
#12
Shinsaku Amano, Hisanori Yamane
Single crystals of suboxide solid solutions Ti12-δGaxBi3-xO10 (x = 1.42-1.74; δ = 0.77-0.62) were prepared at 900 °C with a Bi flux. Crystal structure analysis by X-ray diffraction (XRD) revealed that the solid solutions are isostructural with Ti12-δSn3O10 (cubic, space group Fm3̅m). The cell parameter a decreases from 13.5616(3) to 13.5402(5) Å with increasing Ga content, x, while the total valence electron number of Ti12-δGaxBi3-xO10 is maintained at 117.1 by decreasing Ti defects, δ. Stella octangula is formed by sharing of the edges of four supertetrahedra composed of O-centered Ti tetrahedra and trigonal bipyramids (oxide part)...
September 15, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28915022/cobalt-ii-ions-connecting-co-ii-4-helicates-into-a-2-d-coordination-polymer-showing-slow-relaxation-of-the-magnetization
#13
Paula Cucos, Lorenzo Sorace, Catalin Maxim, Sergiu Shova, Delia Patroi, Andrea Caneschi, Marius Andruh
The reactions of cobalt(II) perchlorate with a diazine tetratopic helicand, H4L, in the presence of sodium carbonate afford two coordination polymers constructed from tetranuclear anionic helicates as building blocks: ∞(3)[Co4L3Na4(H2O)4]·4H2O (1) and ∞(2)[Co5L3Na2(H2O)9]·2.7H2O·DMF (2). The tetranuclear triple-stranded helicates, {Co(II)4L3}(4-), are connected in 1 by sodium(I) ions and in 2 by sodium(I) and cobalt(II) ions (H4L results from the condensation reaction between 3-formylsalicylic acid and hydrazine)...
September 15, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28915020/rotating-magnetocaloric-effect-in-an-anisotropic-two-dimensional-cu-ii-w-v-cn-8-3-molecular-magnet-with-topological-phase-transition-experiment-and-theory
#14
Piotr Konieczny, Robert Pełka, Dominik Czernia, Robert Podgajny
Conventional (MCE) and rotating (RMCE) magnetocaloric effects have been explored in the two-dimensional (2D) coordination polymer {(tetren)H5)0.8Cu(II)4[W(V)(CN)8]4·7.2H2O}n (WCu-t; tetren = tetraethylenepentamine). The unusual magnetostructural properties were exploited, including the bilayered Prussian Blue like coordination skeleton and the XY easy-plane magnetic anisotropy based on the in-plane correlation between W(V) and Cu(II) spins of (1)/2, underlying the Berezinskii-Kosterlitz-Thouless (BKT) topological phase transition to the long-range-ordered state at TC = 33 K...
September 15, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28915017/cationic-and-anionic-disorder-in-cztsse-kesterite-compounds-a-chemical-crystallography-study
#15
Pierre Bais, Maria Teresa Caldes, Michaël Paris, Catherine Guillot-Deudon, Pierre Fertey, Bernadette Domengès, Alain Lafond
The cationic and anionic disorder in the Cu2ZnSnSe4-Cu2ZnSnS4 (CZTSe-CZTS) system has been investigated through a chemical crystallography approach including X-ray diffraction (in conventional and resonant setup), (119)Sn and (77)Se NMR spectroscopy, and high-resolution transmission electron microscopy (HRTEM) techniques. Single-crystal XRD analysis demonstrates that the studied compounds behave as a solid solution with the kesterite crystal structure in the whole S/(S + Se) composition range. As previously reported for pure sulfide and pure selenide compounds, the (119)Sn NMR spectroscopy study gives clear evidence that the level of Cu/Zn disorder in mixed S/Se compounds depends on the thermal history of the samples (slow cooled or quenched)...
September 15, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28915015/small-scale-metal-based-syntheses-of-lanthanide-iodide-amide-and-cyclopentadienyl-complexes-as-analogues-for-transuranic-reactions
#16
Cory J Windorff, Megan T Dumas, Joseph W Ziller, Andrew J Gaunt, Stosh A Kozimor, William J Evans
Small-scale reactions of the Pu analogues La, Ce, and Nd have been explored in order to optimize reaction conditions for milligram scale reactions of radioactive plutonium starting from the metal. Oxidation of these lanthanide metals with iodine in ether and pyridine has been studied, and LnI3(Et2O)x (1-Ln; x = 0.75-1.9) and LnI3(py)4 (2-Ln; py = pyridine, NC5H5) have been synthesized on scales ranging from 15 mg to 2 g. The THF adducts LnI3(THF)4 (3-Ln) were synthesized by dissolving 1-Ln in THF. The viability of these small-scale samples as starting materials for amide and cyclopentadienyl f-element complexes was tested by reacting KN(SiMe3)2, KCp' (Cp' = C5H4SiMe3), KCp'' (Cp'' = C5H3(SiMe3)2-1,3), and KC5Me4H with 1-Ln generated in situ...
September 15, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28915014/a-bispidol-chelator-with-a-phosphonate-pendant-arm-synthesis-cu-ii-complexation-and-64-cu-labeling
#17
Raphaël Gillet, Amandine Roux, Jérémy Brandel, Sandrine Huclier-Markai, Franck Camerel, Olivier Jeannin, Aline M Nonat, Loïc J Charbonnière
Here we present the synthesis and characterization of a new bispidine (3,7-diazabicyclo[3.3.1]nonane) ligand with N-methanephosphonate substituents (L2). Its physicochemical properties in water, as well as those of the corresponding Cu(II) and Zn(II) complexes, have been evaluated by using UV-visible absorption spectroscopy, potentiometry, (1)H and (31)P NMR, and cyclic voltammetry. Radiolabeling experiments with (64)Cu(II) have been carried out, showing excellent radiolabeling properties. Quantitative complexation was achieved within 60 min under stoichiometric conditions, at room temperature and in the nanomolar concentration range...
September 15, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28915013/a-polyoxovanadate-resorcin-4-arene-based-porous-metal-organic-framework-as-an-efficient-multifunctional-catalyst-for-the-cycloaddition-of-co2-with-epoxides-and-the-selective-oxidation-of-sulfides
#18
Bing-Bing Lu, Jin Yang, Ying-Ying Liu, Jian-Fang Ma
In this work, we report a new polyoxovanadate-resorcin[4]arene-based metal-organic framework (PMOF), [Co2L0.5V4O12]·3DMF·5H2O (1), assembled with a newly functionalized wheel-like resorcin[4]arene ligand (L). 1 features an elegant porous motif and represents a rare example of PMOFs composed of both a resorcin[4]arene ligand and polyoxovanadate. Remarkably, 1 shows open V sites in the channel, which makes 1 an efficient heterogeneous Lewis acid catalyst for the cycloaddition of carbon dioxide to epoxides with high conversion and selectivity...
September 15, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28914533/m%C3%A3-ssbauer-spectroscopic-characterization-of-iron-iii-polysaccharide-coordination-complexes-photochemistry-biological-and-photoresponsive-materials-implications
#19
Hendrik Auerbach, Giuseppe E Giammanco, Volker Schünemann, Alexis D Ostrowski, Carl J Carrano
While polycarboxylates and hydroxyl-acid complexes have long been known to be photoactive, simple carboxylate complexes which lack a significant LMCT band are not typically strongly photoactive. Hence, it was somewhat surprising that a series of reports demonstrated that materials synthesized from iron(III) and polysaccharides such as alginate (poly[guluronan-co-mannuronan]) or pectate (poly[galacturonan]) formed photoresponsive materials that convert from hydrogels to sols under the influence of visible light...
September 15, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28902998/activation-of-c-h-bonds-of-alkyl-and-arylnitriles-by-the-tacl5-pph3-lewis-pair
#20
Md Mamdudur Rahman, Mark D Smith, José A Amaya, Thomas M Makris, Dmitry V Peryshkov
A new pathway of activation of C-H bonds of alkyl- and arylnitriles by a cooperative action of TaCl5 and PPh3 under mild conditions is reported. Coordination of nitriles to the highly Lewis acidic Ta(V) center resulted in an activation of their aliphatic and aromatic C-H bonds, allowing nucleophilic attack and deprotonation by the relatively weak base PPh3. The propensity of Ta(V) to form multiple bonds to nitrogen-containing ligands is an important driving force of the reaction as it led to a sequence of bond rearrangements and the emergence of, in the case of benzonitrile, a zwitterionic enediimido complex of Ta(V) through C═C double bond formation between two activated nitrile fragments...
September 13, 2017: Inorganic Chemistry
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