- High current density electrodeposition of silver from silver-containing liquid metal salts with pyridine-N-oxide ligands
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New cationic silver-containing ionic liquids were synthesized and used as non-aqueous electrolytes for the electrodeposition of silver layers. In the liquid state of these ionic liquids, a silver (i) cation is coordinated by pyridine-N-oxide (py-O) ligands in a 1:3 metal-to-ligand ratio, although in some cases a different stoichiometry of the silver center crystallized out. As anions, bis(trifluoromethanesulfonyl)imide (Tf2N), trifluoromethanesulfonate (OTf), methanesulfonate (OMs) and nitrate were used, yielding compounds with the formulae [Ag(py-O)3][Tf2N], [Ag(py-O)3][OTf], [Ag(py-O)3][OMs] and [Ag(py-O) 3][NO3], respectively. The compounds were characterized by CHN analysis, FTIR, NMR, DSC, TGA and the electrodeposition of silver was investigated by cyclic voltammetry, linear potential scans, scanning electron microscopy (SEM) and energy-dispersive X-ray spectrometry (EDX). With the exception of [Ag(py-O)3][Tf2N], which melts at 108 °C, all the silver(i) compounds have a melting point below 80 °C and were tested as electrolytes for silver electrodeposition. Interestingly, very high current densities were observed at a potential of -0.5 V vs. Ag/Ag+ for the compounds with fluorine-free anions, i.e. [Ag(py-O)3][NO 3] (current density of -10 A dm-2) and [Ag(py-O) 3][OMs] (-6.5 A dm-2). The maximum current density of the compound with the fluorinated anion trifluoromethanesulfonate, [Ag(py-O) 3][OTf], was much lower: -2.5 A dm-2 at -0.5 V vs. Ag/Ag+. Addition of an excess of ligand to [Ag(py-O) 3][OTf] resulted in the formation of the room-temperature ionic liquid [Ag(py-O)6][OTf]. A current density of -5 A dm-2 was observed at -0.5 V vs. Ag/Ag+ for this low viscous silver salt. The crystal structures of several silver complexes could be determined by X-ray diffraction, and it was found that several of them had a stoichiometry different from the 1:3 metal-to-ligand ratio used in their synthesis. This indicates that the compounds form crystals with a composition different from that of the molten state. The electrochemical properties were measured in the liquid state, where the metal-to-ligand ratio was 1:3. Single crystal X-ray diffraction measurements showed that silver(i) is six coordinate in [Ag(py-O) 3][Tf2N] and [Ag(py-O)3][OTf], while it is five coordinate in the other complexes. In [Ag3(py-O)8][OTf] 3, there are two different coordination environments for silver ions: six coordinate central silver ions and five coordinate for the outer silver ions. In some of the silver(i) complexes, silver-silver interactions were observed in the solid state. The Royal Society of Chemistry.
- Sniekers, Jeroen,Brooks, Neil R.,Schaltin, Stijn,Van Meervelt, Luc,Fransaer, Jan,Binnemans, Koen
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- Syntheses, X-ray structures and CVD studies of trimethylphosphite stabilized silver(I) methanesulfonates
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The preparation of {[(MeO)3P]n·AgO 3SCH3} (n = 1, 2a; n = 2, 2b) is described. The molecular structure of 2a was determined by using X-ray single crystal analysis. Complex 2a contains an Ag4 rectangular make-up, the centroid of which constitutes an inversion center. Complex 2b was used as precursor in the deposition of silver films using metal organic chemical vapor deposition (MOCVD) technique for the first time. The silver films obtained were characterized using scanning electron microscopy (SEM) and energy-dispersion X-ray (EDX) analysis.
- Tao, Xian,Shen, Ke-Cheng,Shen, Ying-Zhong
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- Self-Assembly and Disassembly of Vesicles as Controlled by Anion-π Interactions
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Anion-π interactions have been widely studied as new noncovalent driving forces in supramolecular chemistry. However, self-assembly induced by anion-π interactions is still largely unexplored. Herein we report the formation of supramolecular amphiphiles through anion-π interactions, and the subsequent formation of self-assembled vesicles in water. With the π receptor 1 as the host and anionic amphiphiles, such as sodium dodecylsulfate (SDS), sodium laurate (SLA), and sodium methyl dodecylphosphonate (SDP), as guests, the sequential formation of host-guest supramolecular amphiphiles and self-assembled vesicles was demonstrated by SEM, TEM, DLS, and XRD techniques. The intrinsic anion-π interactions between 1 and the anionic amphiphiles were confirmed by crystal diffraction, HRMS analysis, and DFT calculations. Furthermore, the controlled disassembly of the vesicles was promoted by competing anions, such as NO3-, Cl-, and Br-, or by changing the pH value of the medium. May the best guest win: Supramolecular amphiphiles formed by anion-π interactions between an anionic amphiphile (anionic part in red in the picture) and a macrocyclic π system (light blue) underwent self-assembly into vesicles in water. The controlled disassembly of the vesicles was promoted by competing anions or a decrease in the pH value (see picture).
- He, Qing,Ao, Yu-Fei,Huang, Zhi-Tang,Wang, De-Xian
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- MANUFACTURING METHOD OF FLUORINATED HYDROCARBON
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PROBLEM TO BE SOLVED: To provide a method for industrially advantageously manufacturing fluorinated hydrocarbon (3). SOLUTION: There is provided a method for manufacturing fluorinated hydrocarbon represented by the formula (3), including contacting a secondary or tertiary ether compound represented by the formula (1) and acid fluoride represented by the formula (2) in the presence of a silver salt in a hydrocarbon solvent. R1 and R2 are each independently a C1 to 3 alkyl group, R1 and R2 may bind to form a ring structure, R3 is H, a methyl group or an ethyl group, R4 and R5 are each independently a methyl group or an ethyl group. SELECTED DRAWING: None COPYRIGHT: (C)2018,JPOandINPIT
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Paragraph 0061
(2018/05/08)
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- TRIFUNCTIONAL ADDITIVES FOR ELECTROLYTE COMPOSITION FOR LITHIUM BATTERIES
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An electrolyte composition containing (i) at least one aprotic organic solvent; (ii) at least one conducting salt; (iii) at least one compound of formula (I); and (iv) optionally one or more additives.
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Page/Page column 26-27
(2018/08/20)
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- Nonaqueous preparation of stable silver nanoparticles dispersions from organic sulfonic acids
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The conditions for stable silver nanoparticles dispersions synthesis from organic sulfonic acids in an anhydrous medium of ethylene glycol and its methyl ester were studied. Ascorbic acid and potassium citrate were used as reducing agents.
- Glushko, Valentina,Blokhina, Lidiya,Sadovskaya, Natalya,Kozhukhov, Vadim
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p. 789 - 797
(2016/07/06)
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- Synthesis and characterization of organophosphine/phosphite stabilized silver(I) methanesulfonates: Crystal structures of [Ph3PAgO3SCH3] and [(Ph3P)2AgO3SCH3]
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Six organophosphine/phosphite stabilized silver(I) methanesulfonates of type [LnAgO3SCH3] (L = Ph3P, n = 1, 2a; n = 2, 2b; n = 3, 2c; L = (EtO)3P; n = 1, 2d; n = 2, 2e; n = 3, 2f) were synthesized by the reaction of silver methanesulfonates with triphenylphosphine or triethylphosphite in dichloromethane under nitrogen atmosphere. These complexes were obtained in high yields and characterized by elemental analysis, 1H-, 13C{H} NMR, IR spectroscopy and thermogravimetric analysis (TGA), respectively. X-ray single crystal analysis reveals that complex 2a is a tetramer [Ph3PAgO3SCH3]4 and complex 2b is a monomer. The thermal stability of 2a has been studied by applying thermogravimetric analysis. It starts to decompose between 50 and 440 °C in a three-step process. The final residue (Ag) is about 20.50%.
- Zhang, Yi-Ying,Wang, Yan,Tao, Xian,Wang, Ning,Shen, Ying-Zhong
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p. 2501 - 2505
(2009/02/07)
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- Heterotopic Assemblage of Two Different Disk-Shaped Ligands through Trinuclear Silver(I) Complexation: Ligand Exchange-Driven Molecular Motion
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The sandwich-shaped heterotopic trinuclear Ag+ complex Ag 31·2 was exclusively formed from two different tris(thiazolyl) and hexa(thiazolyl) disk-shaped ligands, 1 and 2, with the aid of three Ag + ions. The variable-temperature 1H NMR study on its complexation behavior revealed that metal-ligand exchanges between the two neighboring thiazolyl nitrogen donors of 2 take place at the three Ag + centers in concert. ΔH? and ΔS? for the exchange process were calculated to be 50.5 kJ mol-1 and -26.7 J mol-1 K-1, respectively, and its energy barrier at 298 K was estimated to be 58.5 kJ mol-1. Each concerted metal-ligand exchange leads to an intramolecular 60°-rotational motion ((P) ? (M) conversion) between the two disk-shaped ligands.
- Hiraoka, Shuichi,Shiro, Motoo,Shionoya, Mitsuhiko
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p. 1214 - 1218
(2007/10/03)
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