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Inorganic Chemistry

Ethan P McMoran, Douglas R Powell, Felio Perez, Gerard T Rowe, Lei Yang
A series of copper complexes supported by a simple dipyridylamide ligand (H2pcp) were isolated and characterized. Treatment of H2pcp with NaH and copper(I) salts led to the formation of [Cu2(2pcp)2] (1a) and {Na[(Cu2(2pcp)2)2]PF6}n (1b). The X-ray crystal structures of both complexes feature Cu(I)Cu(I) cores with close Cu···Cu interactions. Electrochemical studies of 1a showed a reversible one-electron oxidation wave in CH2Cl2. On the basis of the work on 1a, we began studying the mixed-valence copper species supported by this ligand...
October 26, 2016: Inorganic Chemistry
C Gunnar Werncke, Mohammed-Amine Bouammali, Julie Baumard, Nicolas Suaud, Cyril Martins, Nathalie Guihéry, Laure Vendier, Jianxia Zheng, Jean-Baptiste Sortais, Christophe Darcel, Sylviane Sabo-Etienne, Jean-Pascal Sutter, Sébastien Bontemps, Céline Pichon
A family of four-coordinate Fe(II) complexes formed with N,N'-chelating amido-pyridine ligands was synthesized, and their magnetic properties were investigated. These distorted tetrahedral complexes exhibit significant magnetic anisotropy with zero-field splitting parameter D ranging between -17 and -12 cm(-1). Ab initio calculations enabled identification of the structural factors that control the nature of the magnetic anisotropy and the rationalization of the variation of D in these complexes. It is shown that a reduced N-Fe-N angle involving the chelating nitrogen atoms of the ligands is at the origin of the negative D value and that the torsion between the two N-Fe-N planes imposed by steric hindrances further increases the |D| value...
October 26, 2016: Inorganic Chemistry
Léa Gustin, Yoshiteru Hosaka, Cédric Tassel, Tomoko Aharen, Yuichi Shimakawa, Hiroshi Kageyama, John B Wiley
Synthesis, characterization, and thermal modification of the new layered perovskite FeLa2Ti3O10 have been studied. FeLa2Ti3O10 was prepared by ion exchange of the triple-layered Ruddlesden-Popper phase Li2La2Ti3O10 with FeCl2 at 350 °C under static vacuum. Rietveld refinement on synchrotron X-ray diffraction data indicates that the new phase is isostructural with CoLa2Ti3O10, where Fe(II) cations occupy slightly compressed/flattened interlayer tetrahedral sites. Magnetic measurements on FeLa2Ti3O10 display Curie-Weiss behavior at high temperatures and a spin-glass transition at lower temperatures (<30 K)...
October 26, 2016: Inorganic Chemistry
Shoutao Zhang, Li Zhu, Hanyu Liu, Guochun Yang
Inspired by the diverse properties of hydrogen sulfide, iron sulfide, and iron hydrides, we combine first-principles calculations with structure prediction to find stable structures of Fe-S-H ternary compounds with various FexSyHz (x = 1-2; y = 1-2; z = 1-6) compositions under high pressure with the aim of finding novel functional materials. It is found that Fe2SH3 composition stabilizes into an orthorhombic structure with Cmc21 symmetry, whose remarkable feature is that it contains dumbbell-type Fe with an Fe-Fe distance of 2...
October 26, 2016: Inorganic Chemistry
Zhaoqi Guo, Yunlong Wu, Chongqing Deng, Guoping Yang, Jiangong Zhang, Zhihua Sun, Haixia Ma, Chao Gao, Zhongwei An
Two new energetic coordination polymers (CPs) [Pb(BT)(H2O)3]n (1) and [Pb3(DOBT)3(H2O)2]n·(4H2O)n (2) with 1D and 3D structures were synthesized by employing two rational designed ligands, 1H,1'H-5,5'-bitetrazole (H2BT) and 1H,1'H-[5,5'-bitetrazole]-1,1'-diol ligands (DHBT), respectively. Thermal analyses and sensitivity tests show that the 3D architecture reinforces the network of 2 which has higher thermal stability and lower sensitivity than that of 1. Through oxygen-bomb combustion calorimetry the molar enthalpy of formation of 2 is derived to be much higher than that of 1 as well as the reported CPs...
October 26, 2016: Inorganic Chemistry
Zhen Chen, Yuexiao Pan, Luqing Xi, Ran Pang, Shaoming Huang, Guokui Liu
In most Eu(3+) activated phosphors, only red luminescence from the (5)D0 is obtainable, and efficiency is limited by concentration quenching. Herein we report a new phosphor of Ca4LaO(BO3)3:Eu(3+) (CLBO:Eu) with advanced photoluminescence properties. The yellow luminescence emitted from the (5)D1,2 states is not thermally quenched at room temperature. The relative intensities of the yellow and red emission bands depend strongly on the Eu(3+) doping concentration. More importantly, concentration quenching of Eu(3+) photoluminescence is absent in this phosphor, and the stoichiometric compound of Ca4EuO(BO3)3 emits stronger luminescence than the Eu(3+) doped compounds of CLBO:Eu; it is three times stronger than that of a commercial red phosphor of Y2O3:Eu(3+)...
October 26, 2016: Inorganic Chemistry
Otmar M Ten Kate, Rong-Jun Xie, Chun-Yun Wang, Shiro Funahashi, Naoto Hirosaki
Novel Sr2-yEuyB2-2xSi2+3xAl2-xN8+x phosphors were investigated as a function of the boron and aluminum over silicon ratio and as a function of the Eu(2+) concentration. Samples were prepared via solid-state reaction synthesis by carefully controlling the synthesis conditions and composition. At high boron and aluminum content, that is, x = 0, a Eu(2+) 5d-4f emission is observed of which the maximum shifts from 595 nm for low Eu concentrations (y = 0.005) toward 623 nm for high Eu concentrations (y = 0.5). The samples can be excited by UV or blue light up to ∼475 nm...
October 25, 2016: Inorganic Chemistry
Samuel L Esarey, Joel C Holland, Bart M Bartlett
We analyze the stability of the non-heme water oxidation catalyst (WOC), Fe(bpmcn)Cl2 toward oxygen and illumination under nonaqueous and acidic conditions. Fe(bpmcn)Cl2 has been previously used as a C-H activation catalyst, a homogeneous WOC, and as a cocatalyst anchored to WO3 for photoelectrochemical water oxidation. This paper reports that the ligand dissociates at pH 1 with a rate constant k = 19.8(2) × 10(-3) min(-1), resulting in loss of catalytic activity. The combination of UV-vis experiments, (1)H NMR spectroscopy, and cyclic voltammetry confirm free bpmcn and Fe(2+) present in solution under acidic conditions...
October 25, 2016: Inorganic Chemistry
Jipeng Fu, Su Zhang, Ran Pang, Yonglei Jia, Wenzhi Sun, Haifeng Li, Lihong Jiang, Chengyu Li
Infrared (IR) light-emitting materials have wide applications. However, variety and economical accesses to obtain IR materials and devices are still limited, because the IR-emitting materials are always suffering from two obstacles, namely, lower absorption and lower emission efficiency. In this work, using a modified high-temperature solid-state reaction an efficient short-wavelength IR luminescent material is successfully synthesized. On the basis of the excellent luminescent properties, a convenient IR light-emitting diode (LED) device is fabricated by combining the novel IR material with a commercial UV LED chip...
October 25, 2016: Inorganic Chemistry
Ismail Fidan, Emel Önal, Yusuf Yerli, Dominique Luneau, Vefa Ahsen, Catherine Hirel
The synthesis of a homogeneous neutral hexaradical architecture consisting of six imino nitroxide radical moieties covalently bonded on a cyclotriphosphazene scaffold was reported. The synthesis of hexaradical imino nitroxide compounds follows the Ullman procedure involving the condensation of 2,3-bis(hydroxylamino)-2,3-dimethylbutane with hexa-(4-formylphenoxy)cyclotriphosphazene (3) followed by oxidation of the condensation product hexa-[4-(1-hydroxy-4,4,5,5-tetramethyl-2-imidazoline-2-yl)phenoxy]cyclotriphosphazene (2) by NaIO4...
October 25, 2016: Inorganic Chemistry
Jianyan Ding, Quansheng Wu, Yanyan Li, Qiang Long, Yichao Wang, Xinlong Ma, Yuhua Wang
Defect luminescence has been considered to be one of the most efficient ways to resolve the problem of the recent limited supply and increased demand for rare-earth elements. So, in this work, a novel self-activated long-persistent green-yellow and yellow emitting phosphors of α-Ca3B2N4 and β-Ca3B2N4 has been successfully synthesized by sample-pressuring sintering. The α-Ca3B2N4 and β-Ca3B2N4 all have a broad excitation band peaked at 300 and 350 nm and emit yellow-green light peaked at 550 nm and yellow light peaked at 575 nm respectively with the long afterglow properties...
October 25, 2016: Inorganic Chemistry
Ben Zercher, Todd A Hopkins
Materials that emit circularly polarized light have application in several important industries. Because they show large optical activity and emit sharp visible light transitions, europium complexes are often exploited in applications that require circularly polarized luminescence (CPL). Chiral and coordinating ionic liquids based on prolinate, valinate, and aspartate anions are used to induce CPL from a simple achiral europium triflate salt. The sign of the induced CPL is dependent on the handedness (l vs d) of the amino acid anion...
October 24, 2016: Inorganic Chemistry
Lina G AbdulHalim, Zahra Hooshmand, Manas R Parida, Shawkat M Aly, Duy Le, Xin Zhang, Talat S Rahman, Matthew Pelton, Yaroslav Losovyj, Peter A Dowben, Osman M Bakr, Omar F Mohammed, Khabiboulakh Katsiev
Noble metal nanoclusters (NCs) play a pivotal role in bridging the gap between molecules and quantum dots. Fundamental understanding of the evolution of the structural, optical, and electronic properties of these materials in various environments is of paramount importance for many applications. Using state-of-the-art spectroscopy, we provide the first decisive experimental evidence that the structural, electronic, and optical properties of Ag44(MNBA)30 NCs can now be tailored by controlling the chemical environment...
October 24, 2016: Inorganic Chemistry
Akio Hayashi, Hiromi Ota, Xavier López, Norihito Hiyoshi, Nao Tsunoji, Tsuneji Sano, Masahiro Sadakane
Dipotassium cation (K(+))-encapsulated Preyssler-type phosphotungstate, [P5W30O110K2](13-), was prepared by heating monobismuth (Bi(3+))-encapsulated Preyssler-type phosphotungstate, [P5W30O110Bi(H2O)](12-), in acetate buffer in the presence of an excess amount of potassium cations. Characterization of the isolated potassium salt, K13[P5W30O110K2] (1a), and its acid form, H13[P5W30O110K2] (1b), by single crystal X-ray structure analysis, (31)P and (183)W nuclear magnetic resonance (NMR), Fourier transform infrared (FT-IR) spectroscopy, cyclic voltammetry (CV), high-resolution electrospray ionization mass spectroscopy (HR-ESI-MS), and elemental analysis revealed that two potassium cations are encapsulated in the Preyssler-type phosphotungstate molecule with formal D5h symmetry, which is the first example of a Preyssler-type compound with two encapsulated cations...
October 24, 2016: Inorganic Chemistry
Yuji Mikata, Risa Ohnishi, Risa Nishijima, Hideo Konno
The tetrakisquinoline ligand HT(6-MeO8Q)HPN (N,N,N',N'-tetrakis(6-methoxy-8-quinolylmethyl)-2-hydroxy-1,3-propanediamine) exhibited Zn(2+)-induced fluorescence enhancement with high specificity and sensitivity (IZn/I0 = 57 and ICd/IZn = 6% in the presence of 2 equiv of Zn(2+); LOD (limit of detection) = 15 nM). This ligand also exhibited fluorescence enhancement specific to inorganic phosphate (PO4(3-)) in DMF-HEPES buffer (50 mM HEPES, 100 mM KCl, pH = 7.5) (1:1) in the presence of 2 equiv of Zn(2+). The structure of the unprecedented tetranuclear zinc complex with a μ4-PO4 bridge was elucidated by X-ray crystallography as the key species responsible for fluorescence enhancement...
October 24, 2016: Inorganic Chemistry
Cleve Dionel Mboyi, Carine Maaliki, Amelle Mankou Makaya, Yves Canac, Carine Duhayon, Remi Chauvin
With the view to enhancing the unique coordinating ability of the known phenyl-tetrakis(diisopropylamino)dicyclopropeniophosphine (Ph-DCP), replacement of the phenyl substituent by a tert-butyl substituent was envisaged. Both α-dicationic R-DCP phosphines, with R = Ph and (t)Bu, were prepared in 54%-55% yield by substitution of RPCl2 with two equivalents of bis(diisopropylamino)-dicyclopropenylidene (BAC) and metathesis with NaBF4. This method is implicitly consistent with the representation of R-DCPs as BAC-phosphenium adducts...
October 21, 2016: Inorganic Chemistry
Bo Zhang, Jun Li, Cheng-Feng Du, Mei-Ling Feng, Xiao-Ying Huang
An open-framework chalcogenidostannate, namely, [CH3NH3]2Ag4Sn(IV)2Sn(II)S8 (1), has been solvothermally synthesized and structurally characterized, which represents the first organically templated three-dimensional (3D) Ag-Sn-S compound containing the mixed valence of Sn(IV)/Sn(II) and displays visible-light-driven photocatalytic activity for degradation of crystal violet (CV).
October 21, 2016: Inorganic Chemistry
Wenjing Liu, Rami Al-Oweini, Karen Meadows, Bassem S Bassil, Zhengguo Lin, Jonathan H Christian, Naresh S Dalal, A Martin Bossoh, Israël M Mbomekallé, Pedro de Oliveira, Jamshed Iqbal, Ulrich Kortz
The dichromium(III)-containing heteropoly-16-tungstates [Cr(III)2(B-β-Si(IV)W8O31)2](14-) (1) and [Cr(III)2(B-β-Ge(IV)W8O31)2](14-) (2) were prepared via a one-pot reaction of the composing elements in aqueous, basic medium. Polyanions 1 and 2 represent the first examples of Cr(III)-containing heteropolytungstates comprising the octatungstate unit {XW8O31} (X = Si, Ge). Magnetic studies demonstrated that, in the solid state, the two polyanions exhibit a weak antiferromagnetic interaction between the two Cr(III)centers with J = -3...
October 21, 2016: Inorganic Chemistry
Guoping Li, Pengfei Hao, Junju Shen, Tanlai Yu, Huihui Li, Yunlong Fu
Matched with 3,5-bis(pyridine-2-yl)-1,2,4-triazole (2-bpt), a new electron donor-acceptor-based chlorobismuthate(III) hybrid, [2-bpt]2[Bi2Cl10(H2O)]·5H2O was prepared solvothermally and characterized. The title compound (hydrated form) and its dehydrated form exhibit photo- and thermo-induced intermolecular electron transfer (ET), which correspond to dual ET photo/thermochromism for hydrated form, charge transfer thermochromism during dehydration, and simultaneously photoluminescent responses, respectively...
October 21, 2016: Inorganic Chemistry
Sk Imran Ali, Reinhard K Kremer, Mats Johnsson
The new quaternary layered oxide CoMo2Sb2O10 was synthesized by hydrothermal synthesis techniques, and its structure was determined from single-crystal X-ray diffraction data. CoMo2Sb2O10 crystallizes in the monoclinic space group C2/c with one Sb(3+), Mo(6+), and Co(2+) atom site per unit cell, respectively. The crystal structure contains building units consisting of [Co2O8]n, [Mo2O8]n, and [SbO2]n chains. These are connected through corner sharing to form charge-neutral [CoMo2Sb2O10]n layers. Thermal decomposition of CoMo2Sb2O10 starts at 550 °C...
October 21, 2016: Inorganic Chemistry
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