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Inorganic Chemistry

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https://www.readbyqxmd.com/read/30232885/europium-based-metal-organic-framework-as-a-dual-luminescence-sensor-for-the-selective-detection-of-the-phosphate-anion-and-fe-3-ion-in-aqueous-media
#1
Purna Chandra Rao, Sukhendu Mandal
A new three-dimensional europium-based metal-organic framework has been synthesized with the newly designed ligand L (6-[1-(4-carboxyphenyl)-1 H-1,2,3-triazol-4-yl]nicotinic acid). This compound acts as a dual sensor for the phosphate anion and Fe3+ ion in aqueous media. The mechanistic aspect of this selectivity and sensitivity was explored through several spectroscopic methods and then correlated with the corresponding structure.
September 20, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/30230331/ligand-isomerism-in-coordination-cages
#2
Hareesha Dasary, Rajamony Jagan, Dillip Kumar Chand
Complexation reactions of palladium(II) nitrate with a set of 3-pyridyl appended nonchelating bidentate ligands possessing regioisomeric phenylene-diurea functionalities as spacers were carried out. The ligands utilized in this study are 1,1'-(1,2-phenylene)bis(3-(pyridin-3-yl)urea), L1; 1,1'-(1,3-phenylene)bis(3-(pyridin-3-yl)urea), L2; and 1,1'-(1,4-phenylene)bis(3-(pyridin-3-yl)urea), L3. The complexation reactions of the ligands (L1, L2, and L3) with palladium(II) produced single discrete isomeric cages (1, 2, and 3) of Pd2 L4 formulation in each case and thereby illustrated ligand-isomerism in coordination cages...
September 19, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/30230330/high-volumetric-hydrogen-adsorption-in-a-porous-anthracene-decorated-metal-organic-framework
#3
Yong Yan, Ivan da Silva, Alexander J Blake, Anne Dailly, Pascal Manuel, Sihai Yang, Martin Schröder
We report an unprecedented ligand-based binding domain for D2 within a porous metal-organic framework (MOF) material as confirmed by neutron powder diffraction studies of D2 -loaded MFM-132a. A tight pocket of 6 Å diameter is formed by the close packing of three anthracene panels, and it is here rather than the open metal sites where D2 binds preferentially. As a result, MFM-132a shows exceptional volumetric hydrogen adsorption (52 g L-1 at 60 bar and 77 K) and the highest density of adsorbed H2 within its pores among all the porous materials reported to date under the same conditions...
September 19, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/30230324/hemiporphyrazine-involved-sandwich-dysprosium-double-decker-single-ion-magnets
#4
Wenbo Liu, Suyuan Zeng, Xin Chen, Houhe Pan, Dongdong Qi, Kang Wang, Jianmin Dou, Jianzhuang Jiang
Both heteroleptic (phthalocyaninato)(hemiporphyrazinato) and homoleptic bis(hemiporphyrazinato) dysprosium double-decker complexes, Dy[H(Hp)2 ] (1) and Dy[H(Pc)(Hp)] (2) (H2 Pc = metal-free phthalocyanine; H2 Hp = metal-free hemiporphyrazine), were designed, synthesized, and structurally characterized. The dysprosium center in both double-deckers are octa-coordinated with a nearly ideal square-antiprismatic coordination geometry, which provides an increased molecular anisotropy for the dysprosium ion and ensures the strengthened magnetic properties of both single-ion magnets (SIMs) in terms of coordination geometry...
September 19, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/30230323/influence-of-structural-cation-and-anion-order-in-the-superconducting-properties-of-ozone-oxidized-mo-0-3-cu-0-7-sr-2-recu-2-o-y-re-yb-tm-gd-nd-and-pr
#5
Xabier Martínez de Irujo-Labalde, Esteban Urones-Garrote, Susana García-Martín, Miguel Ángel Alario-Franco
The influence of rare earth (RE) elements on superconducting properties of the transition element (TE)-substituted TE x Cu1- x Sr2 RECu2 O y cuprates has not been sufficiently emphasized so far. In the case of molibdo-cuprates with the general formula Mo0.3 Cu0.3 Sr2 RECu2 O y , all the RE element containing compounds except La, Ce, and Lu can be prepared at room pressure. The influence of the crystal structure on the superconducting properties after ozone oxidation of the present system is reported selecting three groups of RE elements attending to their different atom sizes: small (Yb and Tm), medium (Gd), and big (Nd and Pr)...
September 19, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/30226767/effect-of-monoelectronic-oxidation-of-an-unsymmetrical-phenoxido-hydroxido-bridged-dicopper-ii-complex
#6
Aurore Thibon-Pourret, Federica Gennarini, Rolf David, James A Isaac, Isidoro Lopez, Gisèle Gellon, Florian Molton, Laurianne Wojcik, Christian Philouze, David Flot, Yves Le Mest, Marius Réglier, Nicolas Le Poul, Hélène Jamet, Catherine Belle
A (μ-hydroxido, μ-phenoxido)CuII CuII complex 1 has been synthesized using an unsymmetrical ligand bearing an N, N-bis(2-pyridyl)methylamine (BPA) moiety coordinating one copper and a dianionic bis-amide moiety coordinating the other copper(II) ion. Electrochemical mono-oxidation of the complex in DMF occurs reversibly at 213 K at E1/2 = 0.12 V vs Fc+ /Fc through a metal-centered process. The resulting species (complex 1+ ) is only stable at low temperature and has been spectroscopically characterized by UV-vis-NIR cryo-spectroelectrochemical and EPR methods...
September 18, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/30226764/counteranion-modulated-crystal-growth-and-function-of-one-dimensional-homochiral-coordination-polymers-morphology-structures-and-magnetic-properties
#7
Yan Xu, You-Sheng Yu, Xin-Da Huang, Song-Song Bao, Hong-Ming Ding, Yu-Qiang Ma, Li-Min Zheng
Four pairs of enantiomeric dysprosium(III) phosphonates, namely, R- or S-[Dy3 (pempH2 )2 (pempH)7 ]2 (NO3 )4 ·12H2 O ( R-1 or S-1), R- or S-[Dy3 (pempH)7 (pempH2 )2 ]Cl2 ·2H2 O ( R-2 or S-2), R- or S-[Dy3 (pempH)7 (pempH2 )2 ]Br2 ·2H2 O ( R-3 or S-3), and R- or S-[Dy11 (pempH2 )6 (pempH)27 ](CF3 SO3 )6 ·22H2 O ( R-4 or S-4) are reported, where R- or S-pempH2 represent R- or S-(1-phenylethyl)amino] methylphosphonic acid. All show homochiral chain structures, charge-balanced by counteranions. A comparison of the crystal morphologies of the R-isomers reveals that the overall shapes are quite similar for the four compounds, but the aspect ratio changes remarkably following the sequence: R-1 < R-2 < R-3 < R-4...
September 18, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/30226763/dysprosium-compounds-with-hula-hoop-like-geometries-the-influence-of-magnetic-anisotropy-and-magnetic-interactions-on-magnetic-relaxation
#8
Mei Guo, Yi-Quan Zhang, Zhenhua Zhu, Jinkui Tang
Single-ion anisotropy is one of the crucial properties for mononuclear and even polynuclear single-molecule magnets (SMMs), which can be enhanced by the judicious choice of the coordination geometry around the metal centers. Meanwhile, magnetic interactions also play a significant role in high-performance polynuclear SMMs, especially the dinuclear SMMs. For exploring the influence of those two factors on the magnetic properties, we report a novel series of lanthanide complexes, [Dy(L)3 (HL)(THF)2 ] (1), [Dy2 (Py3 CO)2 (CF3 SO3 )4 (H2 O)2 ]·CH3 CN (2), and [Dy2 (Py3 CO)2 (PhCOO)4 (MeOH)2 ]·MeOH (3), with hula-hoop-like geometries around the DyIII ions...
September 18, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/30226759/a-heptanuclear-copper-iodide-nanocluster
#9
Hani El Moll, Marie Cordier, Grégory Nocton, Florian Massuyeau, Camille Latouche, Charlotte Martineau-Corcos, Sandrine Perruchas
Nanoscale molecular clusters are attractive for the design of materials exhibiting original functions and properties. In particular, copper iodide clusters of high nuclearity are well-known for their stimuli-responsive luminescence properties. The synthesis and characterization of an unprecedented copper(I) iodide molecular cluster based on an original heptanuclear inorganic core are reported. This nanometer-size cluster is formulated as [Cu7 I7 (P(C6 H4 CF3 )3 )6 (CH3 CN)] and its novel structure has been characterized by X-ray diffraction and multinuclear solid-state 63 Cu, 31 P, 13 C, 19 F, and 1 H NMR spectroscopy...
September 18, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/30226758/clarifying-the-copper-coordination-environment-in-a-de-novo-designed-red-copper-protein
#10
Karl J Koebke, Leela Ruckthong, Jennifer L Meagher, Emilie Mathieu, Jill Harland, Aniruddha Deb, Nicolai Lehnert, Clotilde Policar, Cédric Tard, James E Penner-Hahn, Jeanne A Stuckey, Vincent L Pecoraro
Cupredoxins are copper-dependent electron-transfer proteins that can be categorized as blue, purple, green, and red depending on the spectroscopic properties of the Cu(II) bound forms. Interestingly, despite significantly different first coordination spheres and nuclearity, all cupredoxins share a common Greek Key β-sheet fold. We have previously reported the design of a red copper protein within a completely distinct three-helical bundle protein, α3 DChC2. (1) While this design demonstrated that a β-barrel fold was not requisite to recapitulate the properties of a native cupredoxin center, the parent peptide α3 D was not sufficiently stable to allow further study through additional mutations...
September 18, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/30226372/two-keggin-based-isostructural-pomof-hybrids-synthesis-crystal-structure-and-catalytic-properties
#11
Soumyabrata Roy, Vamseedhara Vemuri, Sthitadhi Maiti, Kaja Sai Manoj, Udumula Subbarao, Sebastian C Peter
In this work we synthesized two novel isostructural twin hybrids Comp1: [H(C10 H10 N2 )Cu2 ][PMo12 O40 ] & Comp2: [H(C10 H10 N2 )Cu2 ][PW12 O40 ], based on the Keggin ions (PMo12 O40 -3 & PW12 O40 -3 ), Cu(I) cation, and 4,4'-bipyridine, by in situ hydrothermal reduction of Cu, facilitated through extensive standardizations of synthetic pH conditions. Both compounds crystallized in monoclinic P21 / c space group with similar lattice parameters and crystal structures. The structural similarity prompted us to explore comparative catalytic properties of the hybrids, to understand the relative role of the POM species in the activity...
September 18, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/30226057/direct-evidence-enhanced-c-2-h-6-and-c-2-h-4-adsorption-and-separation-performances-by-introducing-open-nitrogen-donor-sites-in-a-mof
#12
Xiu-Yuan Li, Zhen-Jing Li, Yong-Zhi Li, Lei Hou, Zhonghua Zhu, Yao-Yu Wang
To comparably analyze the influence of a porous environment on the gas adsorption in MOFs, based on an imidazole-decorated MOF, {[Zn(imtp)]·DMA·1.5H2 O} n (1-im, H2 imtp = 2-(imidazol-1-yl) terephthalic acid), an analogue MOF, {[Zn(tztp)]·DMA} n (1-tz, H2 tztp = 2-(1 H-1,2,4-triazol-1-yl) terephthalic acid) has been synthesized by replacing imidazole with triazole motifs. The two MOFs are isostructural frameworks containing 1D channels; however, they possess different porous wall environments. The open nitrogen-decorated channels in 1-tz lead to significantly enhanced C2 H6 (76...
September 18, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/30222334/remarkable-changes-of-the-acidity-of-bound-nitroxyl-hno-in-the-ru-me-3-9-anen-3-l-2-no-n-family-n-1-3-systematic-structural-and-chemical-exploration-and-bioinorganic-chemistry-implications
#13
Natalia Levin, Nicolás Osa Codesido, Juan Pablo Marcolongo, Pablo Alborés, Thomas Weyhermüller, José A Olabe, Leonardo D Slep
This work demonstrates that the acidity of nitroxyl (HNO) coordinated to a metal core is significantly influenced by its coordination environment. The possibility that NO- complexes may be the predominant species in physiological environments has implications in bioinorganic chemistry and biochemistry. This (apparently simple) result pushed us to delve into the basic aspects of HNO coordination chemistry. A series of three closely related {RuNO}6,7 complexes have been prepared and structurally characterized, namely [Ru(Me3 [9]aneN3 )(L2 )(NO)]3+/2+ , with L2 = 2,2'-bipyridine, 4,4'-dimethoxy-2,2'-bipyridine, and 2,2'-bipyrimidine...
September 17, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/30222331/dicopper-i-complexes-incorporating-acetylide-functionalized-pyridinyl-based-ligands-synthesis-structural-and-photovoltaic-studies
#14
Maharaja Jayapal, Ashanul Haque, Idris J Al-Busaidi, Nawal Al-Rasbi, Mohammed K Al-Suti, Muhammad S Khan, Rayya Al-Balushi, Shahidul M Islam, Chenghao Xin, Wenjun Wu, Wai-Yeung Wong, Frank Marken, Paul R Raithby
Heteroaryl incorporated acetylide-functionalized pyridinyl ligands (L1-L6) with the general formula Py-C≡C-Ar (Py = pyridine and Ar = thiophene-2-yl, 2,2' -bithiophene]-5-yl, 2,2' :5',2″ -terthiophene]-5-yl, thieno[2,3- b]thiophen-2-yl, quinoline-5-yl, benzo[c][1,2,5]thiadiazole-5-yl) have been synthesized by Pd(0)/Cu(I)-catalyzed cross-coupling reaction of 4-ethynylpyridine and the respective heteroaryl halide. Ligands L1-L6 were isolated in respectable yields and characterized by microanalysis, IR spectroscopy, 1 H NMR spectroscopy, and ESI-MS mass spectrometry...
September 17, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/30222330/endor-characterization-of-n-2-fe-ii-%C3%AE-h-2-fe-i-n-2-a-spectroscopic-model-for-n-2-binding-by-the-di-%C3%AE-hydrido-nitrogenase-janus-intermediate
#15
Hao Yang, Jonathan Rittle, Amy R Marts, Jonas C Peters, Brian M Hoffman
The biomimetic diiron complex 4-(N2 )2 , featuring two terminally bound Fe-N2 centers bridged by two hydrides, serves as a model for two possible states along the pathway by which the enzyme nitrogenase reduces N2 . One is the Janus intermediate E4 (4H), which has accumulated 4[e-/H+], stored as two [Fe-H-Fe] bridging hydrides, and is activated to bind and reduce N2 through reductive elimination (RE) of the hydride ligands as H2 . The second is a possible RE intermediate. 1 H and 14 N 35 GHz ENDOR measurements confirm that the formally Fe(II)/Fe(I) 4-(N2 )2 complex exhibits a fully delocalized, Robin-Day type-III mixed valency...
September 17, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/30222328/uranyl-complexes-with-aroylbis-n-n-dialkylthioureas
#16
Christelle Njiki Noufele, Chien Thang Pham, Adelheid Hagenbach, Ulrich Abram
The reaction of isophthaloylbis( N, N-diethylthiourea), H2 L1 , with UO2 (CH3 COO)2 ·2H2 O and NEt3 as a supporting base gives a tetranuclear, anionic complex of the composition [{UO2 (L1 )}4 (OAc)2 ]2- , in which the uranyl ions are S, O-chelate bonded. Each two of them are additionally linked by an acetato ligand. Similar reactions of various uranyl starting materials (uranyl acetate, uranyl nitrate, (NBu4 )2 [UO2 Cl4 ]) with corresponding pyridine-centered ligands (pyridine-2,6-dicarbonylbis( N, N-dialkylthioureas), H2 L2 ) yield mononuclear, neutral compounds, in which the thiourea derivatives are coordinated as S, N, N, N, S-five-dentate chelators...
September 17, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/30222324/facial-and-meridional-isomers-of-tris-bidentate-ir-iii-complexes-unravelling-their-different-excited-state-reactivity
#17
Sylvio Arroliga-Rocha, Daniel Escudero
The use of tris(bidentate) Ir(III) complexes as light active components in phosphorescent organic light-emitting diodes (PhOLEDs) is currently the state-of-the-art technology to attain long-lasting and highly performing devices. Still, further improvements of their operational lifetimes are required for their practical use in lighting and displays. Facial/meridional stereoisomerism of the tris(bidentate) Ir(III) architectures strongly influences their emissive properties and thereto their PhOLEDs performances and operational device stabilities...
September 17, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/30221939/impact-of-carbonate-ions-on-the-synthesis-of-thsio-4-under-hydrothermal-conditions
#18
Paul Estevenon, Eleonore Welcomme, Stephanie Szenknect, Adel Mesbah, Philippe Moisy, Christophe Poinssot, Nicolas Dacheux
Multiparametric study of the hydrothermal synthesis of thorite, ThSiO4 , was performed with the aim to determine the most efficient conditions to form single phase thorite samples. Among the experimental parameters investigated, temperature of the hydrothermal process, concentration of carbonate ions, thorium and silicon reactants, and pH of the reactive media significantly affect the composition of the final system obtained. Single phase samples of ThSiO4 were prepared in weakly basic reactive media and at temperatures over 150 °C, for thorium and silicate concentrations higher than 8 × 10-3 mol L-1 and carbonate concentrations of at least 8 × 10-2 mol L-1 ...
September 17, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/30221516/cause-for-the-orbital-ordering-of-cs-2-agf-4-and-its-effect-on-thermoelectric-properties
#19
Changhoon Lee, Ji-Hoon Shim, Myung-Hwan Whangbo
The cause for the orbital-ordered structure of orthorhombic Cs2 AgF4 and its effect on thermoelectric properties were probed by density functional theory calculations. The orbital-ordered structure of orthorhombic Cs2 AgF4 has been regarded as caused by a cooperative Jahn-Teller (JT) distortion of the AgF6 octahedra of tetragonal Cs2 AgF4 . However, each AgF6 octahedron of tetragonal Cs2 AgF4 is axially compressed and hence has no JT instability. The orbital-ordering transition of Cs2 AgF4 is best described as a metal-to-insulator transition driven by a bandgap opening at the Fermi level...
September 17, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/30221514/aqueous-synthesis-of-copper-ii-imidazolate-nanoparticles
#20
María F Navarro Poupard, Ester Polo, Pablo Taboada, Ana Arenas-Vivo, Patricia Horcajada, Beatriz Pelaz, Pablo Del Pino
A green, simple, and efficient room-temperature aqueous synthetic route for the fabrication of novel porous coordination polymer nanoparticles (NPs) composed of Cu2+ and imidazolate was developed. Colloidal stability, morphology changes, and structural and chemical integrity of the developed NPs, in several solvents having different polarity, were investigated. Basic physicochemical properties of selected NPs (i.e., NP1, NP2, and NP3), such as size, optical and magnetic activity, porosity, thermal stability, structure, aging, and catalytic activity, were determined...
September 17, 2018: Inorganic Chemistry
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