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Inorganic Chemistry

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https://www.readbyqxmd.com/read/29792699/water-soluble-ruthenium-ii-carbonyls-with-1-3-5-triaza-7-phosphoadamantane
#1
Federica Battistin, Gabriele Balducci, Barbara Milani, Enzo Alessio
As a continuation of our strategy for preparing new Ru(II) precursors with improved water solubility through the introduction of highly water-soluble 1,3,5-triaza-7-phosphoadamantane (PTA) supporting ligands in the coordination sphere, in this work, we address the largely unexplored preparation of Ru(II)-PTA carbonyls. Two complementary synthetic approaches were used: (1) the treatment of a series of neutral Ru(II)-CO-dmso compounds of general formula RuCl2 (CO) n (dmso)4- n ( n = 1-3, 1-5) with PTA; (2) the reaction of Ru(II)-PTA complexes with CO...
May 24, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29792695/bond-dissociation-energies-of-metallo-supramolecular-building-blocks-insight-from-fragmentation-of-selectively-self-assembled-heterometallic-metallo-supramolecular-aggregates
#2
Yvonne Lorenz, Albert Gutiérrez, Montserrat Ferrer, Marianne Engeser
A series of selectively self-assembled metallo-supramolecular square-like macrocycles with unsymmetric ditopic linkers and two different types of metal corners, i.e., {Pd(η3 -2-Me-C3 H4 )} and {M(dppp)} with dppp = 1,3-bis(diphenylphosphino)propane and M = Pd2+ or Pt2+ , have been studied in the gas phase using collision-induced dissociation. The aggregates show distinct fragmentation patterns determined by ligand length, i.e, aggregate size, and type of metal corner. Information on relative binding strength can be deduced...
May 24, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29792693/a-titanium-oxo-cluster-model-study-of-synergistic-effect-of-co-coordinated-dye-ligands-on-photocurrent-responses
#3
Jin-Le Hou, Peng Huo, Zheng-Zhen Tang, Li-Na Cui, Qin-Yu Zhu, Jie Dai
The use of multiple sensitizers in dye sensitized solar cells has been attractive as a promising way to achieve highly efficient photovoltaic performance. However, except for the complementary absorption, synergistic effects among the dye components have not been well understood. Herein, using ferrocene-1-carboxylate (FcCO2 ) and catechol (Cat) as dye ligands, two titanium oxo clusters (TOCs), [Ti3 O(Oi Pr)6 (Cat)(FcCO2 )2 ] (1) and [Ti7 O4 (Oi Pr)8 (Cat)5 (FcCO2 )2 ] (2), were synthesized and structurally characterized...
May 24, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29792691/the-role-of-small-nanoparticles-on-the-formation-of-hot-spots-under-microwave-assisted-hydrothermal-heating
#4
Gema Cabello, Rogério A Davoglio, Luis G Cuadrado
Herein, we report a detailed study of microwave-matter interaction focused on the role of small nanoparticles and the effects on microwave thermal heating. We have used a model reaction (degradation of methylene blue) to study the influence of temperature, size, and catalytic properties of the nanoparticles in the potential formation of hot spots. Total mineralization was achieved after 3 h microwave heating at 200 °C in the presence of 2 nm TiO2 nanoparticles (92% calculated TOC decay), but the reaction resulted in a mixture of intermediates (52% TOC decay) in the absence of TiO2 ...
May 24, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29792424/comprehensive-investigation-into-luminescent-properties-of-ir-iii-complexes-an-integrated-computational-study-of-radiative-and-nonradiative-decay-processes
#5
Yu Wang, Peng Bao, Jian Wang, Ran Jia, Fu-Quan Bai, Hong-Xing Zhang
A comprehensive and concrete exploration into the deactivation mechanisms of luminescent materials is imperative, with the improvement of simulating and computing technology. In this study, an integrated calculation scheme is employed on five Ir(III) complexes for thorough investigation of their photophysical properties, including radiative ( kr ) and nonradiative ( knr ) decay rates. As a most famous Ir(III) complex with superior quantum efficiency, fac-Ir(ppy)3 herein serves as a reference relative to the other four β-diketonate complexes...
May 24, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29792421/high-temperature-structural-evolution-in-the-ba-3-mo-1-x-w-x-nbo-8-5-system-and-correlation-with-ionic-transport-properties
#6
Andrea Bernasconi, Cristina Tealdi, Lorenzo Malavasi
The evolution of the hybrid structure between 9R hexagonal perovskite and palmierite in the entire Ba3 Mo(1- x) W x NbO8.5 solid solution (where x = 0, 0.25, 0.5, 0.75, and 1) was probed in the 100-900 K range by synchrotron high-resolution powder diffraction. Each sample exhibits a chemical-dependent structural model in the low-temperature regime (from 100 to 500 K) in which 9R and palmierite structures compete each other, the former being progressively favored as tungsten replaces molybdenum. Above 500 K, unit cell parameters and metal site occupancies start to converge toward a similar structural arrangement that is completely reached at 900 K...
May 24, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29792420/enhanced-thermoelectric-properties-of-double-filled-cosb-3-via-high-pressure-regulating
#7
Libin Wang, Le Deng, Jieming Qin, Xiaopeng Jia
It has been discussed for a long time that synthetic pressure can effectively optimize thermoelectric properties. The beneficial effect of synthesis pressures on thermoelectric properties has been discussed for a long time. In this paper, it is theoretically and experimentally demonstrated that appropriate synthesis pressures can increase the figure of merit (ZT) through optimizing thermal transport and electronic transport properties. Indium and barium atoms double-filled CoSb3 samples were prepared use high-pressure and high-temperature technique for half an hour...
May 24, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29792418/self-assembled-pd-ii-6-molecular-spheroids-and-their-proton-conduction-property
#8
Rupak Saha, Aloke Kumar Ghosh, Rudra Narayan Samajdar, Partha Sarathi Mukherjee
A series of molecular spheroids (SP1-SP4) was synthesized using pseudolinear bisimidazole and bisbenzimidazole donors in combination with Pd(NO3 )2 acceptor via coordination-driven self-assembly. They were characterized by NMR and mass spectrometry, and the solid-state structures of SP1 and SP3 were confirmed by X-ray diffraction. Crystal packing revealed the presence of molecular channels with water molecules in the channels as proton source. All the systems showed proton conductivity across a wide range of temperature and relative humidity...
May 24, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29792415/two-photon-active-organotin-iv-complexes-for-antibacterial-function-and-superresolution-bacteria-imaging
#9
Lei Hu, Hui Wang, Tingting Xia, Bin Fang, Yu Shen, Qiong Zhang, Xiaohe Tian, Hongping Zhou, Jieying Wu, Yupeng Tian
Antibacterial agents with two-photon absorption are expected to play a significant role in biomedical science. Herein, two novel organotin complexes, HLSn1 and HLSn2, based on coumarin were designed, synthesized, and systematically investigated. It was found that these complexes possessed suitable two-photon-active cross sections in the near-infrared region. Moreover, complex HLSn1 could efficiently inhibit the growth of Gram-negative Escherichia coli and Gram-positive Bacillus subtilis, especially the latter with a minimum inhibitory concentration (MIC; 90%) of 2 ± 0...
May 24, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29792414/hybrid-assembly-of-different-sized-supertetrahedral-clusters-into-a-unique-non-interpenetrated-mn-in-s-open-framework-with-large-cavity
#10
Hongxiang Wang, Wei Wang, Dandan Hu, Min Luo, Chaozhuang Xue, Dongsheng Li, Tao Wu
Reported here is a unique crystalline semiconductor open-framework material built from the large-sized supertetrahedral T4 and T5 clusters with the Mn-In-S compositions. The hybrid assembly between T4 and T5 clusters by sharing terminal μ2 -S2- is for the first time observed among the cluster-based chalcogenide open frameworks. Such three-dimensional structure displays non-interpenetrated diamond-type topology with extra-large nonframework volume of 82%. Moreover, ion exchange, CO2 adsorption, as well as photoluminescence properties of the title compound are also investigated...
May 24, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29792332/ligation-enhanced-%C3%AF-hole%C3%A2-%C3%A2-%C3%A2-%C3%AF-interactions-involving-isocyanides-effect-of-%C3%AF-hole%C3%A2-%C3%A2-%C3%A2-%C3%AF-noncovalent-bonding-on-conformational-stabilization-of-acyclic-diaminocarbene-ligands
#11
Alexander S Mikherdov, Mikhail A Kinzhalov, Alexander S Novikov, Vadim P Boyarskiy, Irina A Boyarskaya, Margarita S Avdontceva, Vadim Yu Kukushkin
The reaction of cis-[PdCl2 (CNXyl)2 ] (Xyl = 2,6-Me2 C6 H3 ) with the aminoazoles [1 H-imidazol-2-amine (1), 4 H-1,2,4-triazol-3-amine (2), 1 H-tetrazol-5-amine (3), 1 H-benzimidazol-2-amine (4), 1-alkyl-1 H-benzimidazol-2-amines, where alkyl = Me (5), Et (6)] in a 2:1 ratio in the presence of a base in CHCl3 at RT proceeds regioselectively and leads to the binuclear diaminocarbene complexes [(ClPdCNXyl)2 {μ-C(N-azolyl)N(Xyl)C═NXyl}] (7-12; 73-91%). Compounds 7-12 were characterized by C, H, N elemental analyses, high-resolution ESI+ -MS, Fourier transform infrared spectroscopy, 1D (1 H, 13 C) and 2D (1 H,1 H-COSY, 1 H,1 H-NOESY, 1 H,13 C-HSQC, 1 H,13 C-HMBC) NMR spectroscopies, and X-ray diffraction (XRDn)...
May 24, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29792320/modular-cavities-induced-fit-of-polar-and-apolar-guests-into-halogen-based-receptors
#12
Kentaro Aoki, Kazuya Otsubo, Garry S Hanan, Kunihisa Sugimoto, Hiroshi Kitagawa
Neutral triangular macrocyclic compounds, [PdX2 (4,7-phen)]3 ·(DMF)3 ·Et2 O (X = Cl, Br; 4,7-phen = 4,7-phenanthroline; DMF = N, N'-dimethylformamide; Et2 O = diethyl ether), were synthesized, and their molecular structures were characterized. Solution-state 1 H NMR results suggested the formation of metal-ligand bonds, and single-crystal X-ray crystallography revealed clear triangular structures. A detailed examination of the structures indicated the formation of two kinds of cavities in the solid state, where a triangular unit works as a halogen-based receptor for polar and apolar solvents through weak hydrogen-bonding and dipole-dipole interaction...
May 24, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29792317/in-situ-reduction-from-uranyl-ion-into-a-tetravalent-uranium-trimer-and-hexamer-featuring-ion-exchange-properties-and-the-alexandrite-effect
#13
Jian Lin, Zenghui Yue, Mark A Silver, Meiying Qie, Xiaomei Wang, Wei Liu, Xiao Lin, Hong-Liang Bao, Lin-Juan Zhang, Shuao Wang, Jian-Qiang Wang
By utilizing zinc amalgam as an in situ reductant and pH regulator, mild hydrothermal reaction between UO2 (CH3 COO)2 ·2H2 O, H2 SO4 , and Cs2 CO3 or between UO2 (CH3 COO)2 ·2H2 O, C2 H4 (SO3 H)2 , and K2 CO3 yielded a novel cesium UIV sulfate trimer Cs4 [U3 O(SO4 )7 ]·2.2H2 O (1) and a new potassium UIV disulfonic hexamer K[U6 O4 (OH)5 (H2 O)5 ][C2 H4 (SO3 )2 ]6 ·6H2 O (2), respectively. Compound 1 features a lamellar structure with a honeycomb lattice, and it represents an unprecedented trimeric UIV cluster composed of purely inorganic moieties...
May 24, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29791149/a-tricopper-i-complex-competent-for-o-atom-transfer-c-h-bond-activation-and-multiple-o-2-activation-steps
#14
Brian J Cook, Gianna N Di Francesco, Matthew T Kieber-Emmons, Leslie J Murray
Oxygenation of a tricopper(I) cyclophanate (1) affords reactive transients competent for C-H bond activation and O atom transfer to various substrates (including toluene, dihydroanthracene, and ethylmethylsulfide) based on 1 H NMR, gas chromatography/mass spectrometry (MS), and electrospray ionization (ESI)/MS data. Low product yields (<1%) are determined for C-H activation substrates (e.g, toluene, ethylbenzene), which we attribute to competitive ligand oxidation. The combined stopped-flow UV/visible, electron paramagnetic resonance, ESI/MS, 1 H NMR, and density functional theory (DFT) results for reaction of 1 with O2 are consistent with transient peroxo- and di(oxo)-bridged intermediates...
May 23, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29791147/investigations-of-the-magnetic-and-spectroscopic-properties-of-v-iii-and-v-iv-complexes
#15
Casey Van Stappen, Dimitrios Maganas, Serena DeBeer, Eckhard Bill, Frank Neese
Herein, we utilize a variety of physical methods including magnetometry (SQUID), electron paramagnetic resonance (EPR), and magnetic circular dichroism (MCD), in conjunction with high-level ab initio theory to probe both the ground and ligand-field excited electronic states of a series of V(IV) ( S = 1 /2 ) and V(III) ( S = 1) molecular complexes. The ligand fields of the central metal ions are analyzed with the aid of ab initio ligand-field theory (AILFT), which allows for a chemically meaningful interpretation of multireference electronic structure calculations at the level of the complete-active-space self-consistent field with second-order N-electron valence perturbation theory...
May 23, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29791143/water-soluble-silver-i-complexes-featuring-the-hemilabile-3-7-dimethyl-1-3-5-triaza-7-phosphabicyclo-3-3-1-nonane-ligand-synthesis-characterization-and-antimicrobial-activity
#16
Declan Armstrong, Sarah M Kirk, Cormac Murphy, Antonella Guerriero, Maurizio Peruzzini, Luca Gonsalvi, Andrew D Phillips
This paper describes the preparation and comprehensive characterization of a series of water-soluble cationic silver(I)-centered complexes featuring the hemilabile P, N-ligand known as 3,7-dimethyl-1,3,5-triaza-7-phosphabicyclo[3.3.1]nonane (herein abbreviated as PTN(Me)) and differing types of monoanionic counterions including known biologically active sulfadiazine and triclosan. The complexes primarily differed though the number of coordinating PTN(Me) ligands. The bis-substituted Ag(I) complexes revealed P, N bidentate coordination, while the only P-monocoordination of the metal center was observed for the tris-substituted systems...
May 23, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29790349/high-pressure-phase-relations-and-crystal-structures-of-postspinel-phases-in-mgv-2-o-4-fev-2-o-4-and-mncr-2-o-4-crystal-chemistry-of-ab-2-o-4-postspinel-compounds
#17
Takayuki Ishii, Tsubasa Sakai, Hiroshi Kojitani, Daisuke Mori, Yoshiyuki Inaguma, Yoshitaka Matsushita, Kazunari Yamaura, Masaki Akaogi
We have investigated high-pressure, high-temperature phase transitions of spinel (Sp)-type MgV2 O4 , FeV2 O4 , and MnCr2 O4 . At 1200-1800 °C, MgV2 O4 Sp decomposes at 4-7 GPa into a phase assemblage of MgO periclase + corundum (Cor)-type V2 O3 , and they react at 10-15 GPa to form a phase with a calcium titanite (CT)-type structure. FeV2 O4 Sp transforms to CT-type FeV2 O4 at 12 GPa via decomposition phases of FeO wüstite + Cor-type V2 O3 . MnCr2 O4 Sp directly transforms to the calcium ferrite (CF)-structured phase at 10 GPa and 1000-1400 °C...
May 23, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29790340/%C3%AE-diimines-as-versatile-derivatizable-ligands-in-ruthenium-ii-p-cymene-anticancer-complexes
#18
Lorenzo Biancalana, Lucinda K Batchelor, Tiziana Funaioli, Stefano Zacchini, Marco Bortoluzzi, Guido Pampaloni, Paul J Dyson, Fabio Marchetti
α-Diimines are among the most robust and versatile ligands available in synthetic coordination chemistry, possessing finely tunable steric and electronic properties. A series of novel cationic ruthenium(II) p-cymene complexes bearing simple α-diimine ligands, [(η6 - p-cymene)RuCl{κ2 N-(HCNR)2 }]NO3 (R = Cy, [1]NO3 ; R = 4-C6 H10 OH, [2]NO3 ; R = 4-C6 H4 OH, [3]NO3 ), were prepared in near-quantitative yields as their nitrate salts. [2]NO3 displays high water solubility. The potential of the α-diimine ligand in [3]NO3 as a carrier of bioactive molecules was investigated via esterification reactions with the hydroxyl groups...
May 23, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29790338/improvement-of-the-heat-resistance-of-prussian-blue-nanoparticles-in-a-clay-film-composed-of-smectite-clay-and-%C3%AE%C2%B5-caprolactam
#19
Kenta Ono, Takashi Nakamura, Takeo Ebina, Manabu Ishizaki, Masato Kurihara
Prussian blue (PB) is limited in its application by its breakdown at elevated temperatures. To improve the heat resistance of PB, we prepared a composite film comprising PB nanoparticles (NPs), smectite clay, and an organic compound. The composite film had a microstructure in which PB NPs were intercalated between smectite/organic compound layers. The predominant oxidation temperature of the PB NPs in the composite film was around 500 °C in air, higher than the oxidation temperature of bulk PB in air (250 °C)...
May 23, 2018: Inorganic Chemistry
https://www.readbyqxmd.com/read/29787261/selective-conversion-of-planar-trans-chlorins-into-highly-twisted-doubly-fused-porphyrins-or-chlorins-via-oxidative-fusion
#20
Nivedita Chaudhri, Nitika Grover, Muniappan Sankar
β-to- o-phenyl doubly fused porphyrins (DFPs) or chlorins (DFCs) were selectively synthesized by facile oxidative fusion of trans-chlorins using 2,3-dichloro-5,6-dicyano-1,4- benzoquinone (DDQ) in good-to-excellent yields (70-92%) under mild reaction conditions with high atom economy. The selectivity in product formation (difused porphyrin or chlorin) was controlled by the presence or absence of a Ni(II) ion in the macrocyclic core. Notably, nickel(II) trans-chlorins selectively yielded DFPs, whereas free-base trans-chlorins afforded only DFCs...
May 22, 2018: Inorganic Chemistry
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