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Inorganic Chemistry

Yang Wang, Xueping Kong, Wei Xu, Fengrui Jiang, Bao Li, Lixin Wu
A series of triol ligand [CH3 C(CH2 OH)3 ] covalently decorated polyoxometalates (POMs), which could be ascribed to the primary complexes with structural formulas {M2 [Mo2 O4 (CH3 C(CH2 O)3 )2 ]3 }2- (M = Cu2+ , Co2+ , Ni2+ , Zn2+ ), have been synthesized in organic solvents. Single-crystal X-ray structural analysis reveals that the synthesized polyanionic clusters are comprised of three {Mo2 } units and two divalent transition-metal ions connecting to each other in an alternating style, where all {Mo2 } blocks were covalently decorated by two triol ligands in the trans conformation...
March 19, 2018: Inorganic Chemistry
Meng-Ting Li, Xi-Ya Yang, Ji-Sen Li, Ning Sheng, Guo-Dong Liu, Jing-Quan Sha, Ya-Qian Lan
For exploring the multifold helical fabrication of polyoxometalate (POM)-based hybrid compounds, four POM-based crystalline compounds with different meso-helices, H3 [Ag27 (trz)16 (H2 O)6 ][SiW12 O40 ]2 ·5H2 O (1), H[Ag27 (trz)16 (H2 O)4 ][PW12 O40 ]2 ·2H2 O (2), [Ag23 (trz)14 (H2 O)2 ][HSiW12 O40 ] (3), and [Ag23 (trz)14 (H2 O)2 ][PW12 O40 ] (4), were successfully isolated by using the delicate 1,2,3-triazole ligand and silver ions in this work. Crystal analysis reveals that compounds 1 and 2 and compounds 3 and 4 are isomorphous and display 2-/4-fold mixed meso-helices and simple 2-fold meso-helices, respectively...
March 19, 2018: Inorganic Chemistry
Weiwei Cao, Xiaoyan Yang, Fengqi Lu, Wenfeng Zhu, Laijun Liu, Xiaojun Kuang, Mathieu Allix
Isovalent substitution of Zr4+ for smaller Ti4+ was performed in the 8-layer twinned hexagonal perovskite (referred to as 8H) tantalate Ba8 Ti3 Ta4 O24 , which stabilizes a 10-layer twinned hexagonal perovskite (referred to as 10H). The formation of the 10H phase occurs at low substitution concentration ( x = 0.1) in Ba8 Zrx Ti3- x Ta4 O24 at 1300 °C and reverts back to the 8H phase upon heating at elevated temperatures. Such a 10H-to-8H phase transformation is suppressed at higher Zr-substitution contents ( x > 0...
March 19, 2018: Inorganic Chemistry
Henry H Wilson, Connor A Koellner, Zain M Hannan, Caroline B Endy, Mark W Bezpalko, Nicholas A Piro, W Scott Kassel, Matthew D Sonntag, Christopher R Graves
The synthesis and full characterization of a series of neutral ligand α-diimine complexes of aluminum are reported. The compounds [Al(LAr )2 Cl2 )][AlCl4 ] [LAr = N, N'-bis(4-R-C6 H4 )-2,3-dimethyl-1,4-diazabutadiene] are structurally analogous, as determined by multinuclear NMR spectroscopy and solid-state X-ray diffraction, across a range of electron-donating [R = Me (2),t Bu (3), OMe (4), and NMe2 (5)] and electron-withdrawing [R = Cl (6), CF3 (7), and NO2 (8)] substituents in the aryl side arm of the ligand...
March 19, 2018: Inorganic Chemistry
Shin-Ichiro Kawano, Takafumi Murai, Takahiro Harada, Kentaro Tanaka
Columnar assemblies of liquid-crystalline (LC) macrocycles hold promise for the construction of nanochannels in fluid materials. Metal-assisted self-assembly is an efficient way to prepare LC macrocycles. A large π-conjugated ligand, 9,10-diphenylanthracene (DPA) bearing two β-diketones, was prepared as a building unit for the macrocycle, and a series of side chains were incorporated into the DPA to yield LC materials. The bis(β-diketone) ligands on DPA allow for the efficient formation of triangular 3:3 metallomacrocycles in the presence of square-planar Cu2+ ions...
March 19, 2018: Inorganic Chemistry
Takahiko Kojima, Fumiya Ogishima, Takahisa Nishibu, Hiroaki Kotani, Tomoya Ishizuka, Toshihiro Okajima, Shunsuke Nozawa, Yoshihito Shiota, Kazunari Yoshizawa, Hiroyoshi Ohtsu, Masaki Kawano, Takuya Shiga, Hiroki Oshio
An iron(III) complex having a dibenzotetraethyltetraamido macrocyclic ligand (DTTM4- ), (NEt4 )2 [FeIII (DTTM)Cl] (1), was synthesized and characterized by crystallographic, spectroscopic, and electrochemical methods. Complex 1 has a square-pyramidal structure in the S =3 /2 spin state. The complex exhibited two reversible redox waves at +0.36 and +0.68 V (vs SCE) in the cyclic voltammogram measured in CH2 Cl2 at room temperature. The stepwise oxidation of 1 using chemical oxidants allowed us to observe clear and distinct spectral changes with distinct isosbestic points for each step, in which oxidation occurred at the phenylenediamido moiety rather than the iron center...
March 16, 2018: Inorganic Chemistry
Joyce Pham, Gordon J Miller
Using density functional theory, the crystal structure variation of AAuAl (A = Ca, Sc, and Ti) from orthorhombic Co2 Si-type to distorted hexagonal Fe2 P-type and then Ni2 In-type structures is shown to correlate with their electronic structures and valence electron counts, sizes of the active metals A, and site preferences for Au and Al atoms, which are arranged to maximize Au-Al nearest neighbor contacts. An evaluation of chemical pressure imposed by the varying A metals using total energy vs volume calculations indicates that larger unit cell volumes favor the orthorhombic structure, whereas smaller volumes favor the hexagonal structures...
March 16, 2018: Inorganic Chemistry
Nimai Pathak, Partha Sarathi Ghosh, Suryansh Saxena, Dhanadeep Dutta, Ashok Kumar Yadav, Dibyendu Bhattacharyya, Shambhu Nath Jha, Ramakant Mahadeo Kadam
Activator-free zinc aluminate (ZA) nanophosphor was synthesized through a sol-gel combustion route, which can be used both as a blue-emitting phosphor material and a white-emitting phosphor material, depending on the annealing temperature during synthesis. The material also has the potential to be used in optical thermometry. These fascinating color-tunable emission characteristics can be linked with the various defect centers present inside the matrix and their changes upon thermal annealing. Various defect centers, such as anionic vacancy, cationic vacancy, antisite defect, etc...
March 16, 2018: Inorganic Chemistry
Fan Sun, Zhongnan Guo, Ning Liu, Dan Wu, Jiawei Lin, Erjian Cheng, Tianping Ying, Shiyan Li, Wenxia Yuan
In this work, we report the discovery of a new Ni-based quasi-one-dimensional selenide: Cs0.9 Ni3.1 Se3 . This compound adopts the TlFe3 Te3 -type structure with space group P63 / m, which consists of infinite [Ni3 Se3 ] chains with face-sharing Ni6 octahedra along the c direction. The lattice parameters are calculated as a = 9.26301(4) Å and c = 4.34272(2) Å, with the Ni-Ni distance in the ab plane as 2.582(3) Å, suggesting the formation of a Ni-Ni metallic bond in this compound. Interestingly, it has been found that Cs0...
March 16, 2018: Inorganic Chemistry
Andreu Presa, Guillem Vázquez, Leoní A Barrios, Olivier Roubeau, Luís Korrodi-Gregório, Ricardo Pérez-Tomás, Patrick Gamez
The development of photoactivatable metal complexes with potential anticancer properties is a topical area of current investigation. Photoactivated chemotherapy using coordination compounds is typically based on photochemical processes occurring at the metal center. In the present study, an innovative approach is applied that takes advantage of the remarkable photochemical properties of diarylethenes. Following a proof-of-concept study with two complexes, namely, C1 and C2, a series of additional platinum(II) complexes from dithienylcyclopentene-based ligands was designed and prepared...
March 15, 2018: Inorganic Chemistry
Somali Mukherjee, Sumi Ganguly, Krishnendu Manna, Sanchaita Mondal, Supratim Mahapatra, Debasis Das
Five new coordination polymers (CPs) namely, [{Zn(μ2 -H2 O)0.5 (5N3 -IPA)(2,2'-bpe)}]∞ (1), [{Zn(μ2 -H2 O)0.5 (5N3 -IPA)(1,10-phen)}]∞ (2), [{Zn(5N3 -IPA)(1,2-bpe)}]∞ (3), [{Zn(5N3 -IPA)(1,2-bpey)}]∞ (4), and [{Zn(H2 O)(5N3 -IPA)(4,4'-tme)}(H2 O)0.5 ]∞ (5) (5N3 -H2 IPA = 5-azidoisophthalic acid, 2,2'-bpe= 2,2'-bipyridine, 1,10-phen = 1,10-phenanthroline, 1,2-bpe = 1,2-bis(4-pyridyl)ethane, 1,2-bpey = 1,2-bis(4-pyridyl)ethylene, 4,4'-tme = 4,4'-trimethylenedipyridine), have been synthesized based on a mixed ligand approach adopting a solvothermal technique...
March 15, 2018: Inorganic Chemistry
Lizhu He, Zhen Song, Xionghui Jia, Zhiguo Xia, Quanlin Liu
T-phase (Ba,Ca)2 SiO4 :Eu2+ , showing excellent luminescent thermal stability, has a positionally disordered structure with the splitting of five atom sites, but until now the reason has remained unclear. Herein, we investigate the coordination environments of each cation site in detail to understand the origins of the atom site splitting. We find that the three cation sites in the split-atom-site model are optimally bonded with ligand O atoms compared to the unsplit-atom-site model. This atom site splitting results in larger room and smaller room for each splitting cation site, which just accommodates larger Ba2+ ions and smaller Ca2+ ions, respectively, leading to more rigid structure...
March 15, 2018: Inorganic Chemistry
Shohei Kumagai, Shinya Takaishi, Mengqi Gao, Hiroaki Iguchi, Brian K Breedlove, Masahiro Yamashita
MX chains have been widely studied as a 1D mixed-valence system. Although there have been a large number of studies on the boundary between class II and III materials of the Robin-Day classification, there are few studies of compounds at the boundary between classes I and II. In this study, we synthesized a series of Pt- and Pd- MX-chain compounds with perrhenate counterions, [M(en)2 ][M(en)2 X2 ](ReO4 )4 (X = Br for M = Pd and X = Cl, Br, and I for M = Pt). All compounds were isostructural, and the metal-metal distances within the chain exceed 6 Å, which is the longest among MX-chain compounds thus far reported...
March 15, 2018: Inorganic Chemistry
Stefano Nuzzo, Brendan Twamley, James A Platts, Robert J Baker
A series of uranyl thiocyanate and selenocyanate of the type [R4 N]3 [UO2 (NCS)5 ] (R4 =n Bu4 , Me3 Bz, Et3 Bz), [Ph4 P][UO2 (NCS)3 (NO3 )] and [R4 N]3 [UO2 (NCSe)5 ] (R4 = Me4 ,n Pr4 , Et3 Bz) have been prepared and structurally characterized. The resulting noncovalent interactions have been examined and compared to other examples in the literature. The nature of these interactions is determined by the cation so that when the alkyl groups are small, chalcogenide···chalcogenide interactions are present, but this "switches off" when R =n Pr and charge assisted U═O···H-C and S(e)···H-C hydrogen bonding remain the dominant interaction...
March 15, 2018: Inorganic Chemistry
Fatimah Alahmari, Bambar Davaasuren, Abdul-Hamid Emwas, Alexander Rothenberger
The new thioaluminogermanate Na(AlS2 )(GeS2 )4 (1) was successfully synthesized by a direct combination reaction. The compound crystallizes in the monoclinic space group P21 / n (no. 14) with unit cell parameters a = 6.803(3) Å, b = 38.207(2) Å, c = 6.947(4) Å, and β = 119.17(3)°. The crystal structure is composed of a [(AlS2 )(GeS2 )4 ]- 3D polyanionic network, in which Al and Ge atoms share the atomic positions and Na cations occupy the channels and voids formed by the connection of (Ge/Al)S4 tetrahedra...
March 14, 2018: Inorganic Chemistry
Miguel A Esteruelas, Ana M López, Enrique Oñate, Ainhoa San-Torcuato, Jui-Yi Tsai, Chuanjun Xia
The preparation and photophysical properties of heteroleptic iridium(III) complexes containing a dianionic C,C,C,C-tetradentate ligand and a cyclometalated phenylpyridine group are described. Complex [Ir(μ-OMe)(COD)]2 (1, COD = 1,5-cyclooctadiene) reacts with 1,1-diphenyl-3,3-butylenediimidazolium iodide ([PhIm(CH2 )4 ImPh]I2 ), in the presence NaOt Bu, to give [Ir(μ-I){κ4 - C, C, C, C-[C6 H4 Im(CH2 )4 ImC6 H4 ]}]2 (2), which leads to {[Ir{κ4 - C, C, C, C-[C6 H4 Im(CH2 )4 ImC6 H4 ]}]2 (μ-OH)(μ-OMe)} (3) by treatment first with silver trifluoromethanesulfonate (AgOTf) in acetone-dichloromethane and subsequently with KOH in methanol...
March 14, 2018: Inorganic Chemistry
Piotr Pander, Rachel Bulmer, Ross Martinscroft, Stuart Thompson, Frank W Lewis, Thomas J Penfold, Fernando B Dias, Valery N Kozhevnikov
This article describes a convenient method for the synthesis of ONNO-type tetradentate 6,6'-bis(2-phenoxy)-2,2'-bipyridine (bipyridine bisphenolate, BpyBph) ligands and their platinum(II) complexes. The methodology includes the synthesis of 1,2,4-triazine precursors followed by their transformation to functionalized pyridines by the Boger reaction. Two complementary routes employing 3,3'- and 5,5'-bis-triazines allow a modification of the central pyridine rings in different positions, which was exemplified by the introduction of cyclopentene rings...
March 14, 2018: Inorganic Chemistry
Carla F Pereira, Flávio Figueira, Ricardo F Mendes, João Rocha, Joseph T Hupp, Omar K Farha, Mário M Q Simões, João P C Tomé, Filipe A Almeida Paz
The use of 5,10,15,20-tetrakis( p-phenylphosphonic acid)porphyrin (H10 TPPA) as a linker in the preparation of porphyrin-based metal-organic frameworks (Por-MOFs) through coordination to lanthanides cations is reported. The resulting unprecedented materials, formulated as [M(H9 TPPA)(H2 O)x ]Cl2 · yH2 O [ x + y = 7; M3+ = La3+ (1), Yb3+ (2), and Y3+ (3)], prepared using hydrothermal synthesis, were extensively characterized in the solid-state, for both their structure and thermal robustness, using a myriad of solid-state advanced techniques...
March 13, 2018: Inorganic Chemistry
Kuppuswamy Arumugam, Malathy Selvachandran, Antony Obanda, Mohamed C Shaw, Perumalreddy Chandrasekaran, Sonya L Caston Good, Joel T Mague, Stephen Sproules, James P Donahue
Compounds of the type [(S2 C2 R2 )M(μ-tpbz)M(S2 C2 R2 )] (R = CN, Me, Ph, p-anisyl; M = Ni, Pd, Pt; tpbz = 1,2,4,5-tetrakis(diphenylphosphino)benzene) have been prepared by transmetalation with [(S2 C2 R2 )SnR'2 ] reagents, by direct displacement of dithiolene ligand from [M(S2 C2 R2 )2 ] with 0.5 equiv of tpbz, or by salt metathesis using Na2 [S2 C2 (CN)2 ] in conjunction with X2 M(μ-tpbz)MX2 (X = halide). X-ray crystallography reveals a range of topologies (undulating, chair, bowed) for the (S2 C2 )M(P2 C6 P2 )M(S2 C2 ) core...
March 13, 2018: Inorganic Chemistry
Yuanyuan Ma, Haiyue Peng, Jianing Liu, Yonghui Wang, Xiuli Hao, Xiaojia Feng, Shifa Ullah Khan, Huaqiao Tan, Yangguang Li
Polyoxometalates (POMs) show considerable catalytic performance toward the selective oxidation of alkenes to aldehydes, which is commercially valuable for the production of pharmaceuticals, dyes, perfumes, and fine chemicals. However, the low specific surface area of POMs as heterogeneous catalysts and poor recyclability as homogeneous catalysts have hindered their wide application. Dispersing POMs into metal-organic frameworks (MOFs) for the construction of POM-based MOFs (POMOFs) suggests a promising strategy to realize the homogeneity of heterogeneous catalysis...
March 13, 2018: Inorganic Chemistry
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