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Investigations on Na+ ion conducting polyvinylidenefluoride-co-hexafluoropropylene/poly ethylmethacrylate blend polymer electrolytes

Sodium ion conducting composite polymer electrolytes (CPE) have been prepared by solution casting technique in the skeleton of polyvinylidenefluoride-co-hexafluoropropylene/poly ethylmethacrylate blend. The binary mixture of diethyl carbonate and ethylene carbonate were used as plasticizer, and nanosized Sb2O3 as filler. The sodium trifluoromethanesulfonate (NaCF3SO3) was used as an ionic conducting source. The a.c. impedance study shows that 10 wt% Sb2O3 containing CPE exhibits the maximum conductivity 0.569 mS cm-1 at ambient temperature. Molecular interactions of the constituents were analyzed by Fourier transform infra red spectroscopy. X-ray diffractogram reveals the amorphous nature of the CPE. A surface morphological feature was studied through scanning electron microscope. The activation energy and coherence length calculated were in support of the ionic transport.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

The important role of Sodium trifluoromethanesulfonate

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Achieving superb sodium storage performance on carbon anodes through an ether-derived solid electrolyte interphase

High specific surface area carbon (HSSAC) is a class of promising high-capacity anode materials for sodium-ion batteries (SIBs). A critical bottleneck of the HSSAC anode, however, is the ultra-low initial coulombic efficiency (ICE) in commonly used ester-based electrolytes. This phenomenon further prohibits improving the specific capacity, long-term stability and rate capability of HSSAC anodes. This work reports the largely enhanced anode performance of several different HSSAC anodes in ether-based electrolytes. Very importantly, with the reduced graphene oxide (rGO) anode as one example, the ICE can be as high as 74.6% accompanied by a large reversible specific capacity of 509 mA h g-1 after 100 cycles at a current density of 0.1 A g-1. 75.2% of the capacity was retained after 1000 cycles at 1 A g-1. Even at a high current density of 5 A g-1, the specific capacity of the rGO anode can be obtained at 196 mA h g-1. This extraordinary performance is ascribed to the stable, thin, compact, uniform and ion conducting solid electrolyte interphase (SEI) formed in an ether-based electrolyte. Fortunately, this SEI-modifying strategy is generic and is independent of the specific microstructures of HSSAC anodes, indicating a promising avenue for manipulating the SEI on HSSAC anodes through utilizing ether solvents to enable achievement of high ICE for large-capacity HSSAC anodes for practical applications.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

More research is needed about 2926-30-9

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Alkyne activation by half-sandwich ruthenium(II) complexes bearing the water-soluble phosphane 1,3,5-triaza-7-phosphaadamantane (PTA)

Complex [RuCl{kappa3(N,N,N)-Tp}(PPh3)(PTA)] (kappa3(N,N,N)-Tp = hydridotris(pyrazolyl)borate) containing the water-soluble phosphane 1,3,5-triaza-7-phosphatricyclo[3.3.1.13,7]decane (PTA) reacts with terminal alkynes producing to the corresponding neutral alkynyl complexes [Ru(C{triple bond, long}CR){kappa3(N,N,N)-Tp}(PPh3)(PTA)] (R = Ph (1a), nBu (1b), 1-cyclopentenyl (1c), p-methoxyphenyl (1d), 6-methoxynaft-2-yl (1e)). When halide is extracted from complex [RuCl{kappa3(N,N,N)-Tp}(PPh3)(PTA)] followed by treatment with propargyl alcohols, the corresponding allenylidene complexes [Ru{kappa3(N,N,N)-Tp}(PPh3)(PTA)(C{double bond, long}C{double bond, long}CPh2)][X] (X = PF6 (2a), CF3SO3 (2b)) and [Ru{kappa3(N,N,N)-Tp}(PPh3)(PTA)(C{double bond, long}C{double bond, long}CC12H8)][PF6] (3) result. Electrophilic attack on the complexes thus obtained leads chemoselectively to the alkynyl complexes [Ru(C{triple bond, long}CR){kappa3(N,N,N)-Tp}(PPh3)(1-CH3-PTA)][CF3SO3] (R = Ph (4a), nBu (4b), and 1-cyclopentenyl (4c)) and to the dicationic allenylidene complexes [Ru{kappa3(N,N,N)-Tp}(PPh3)(1-H-PTA)(C{double bond, long}C{double bond, long}CC12H8)][PF6]2 (5) and [Ru{kappa3(N,N,N)-Tp}(PPh3)(1-CH3-PTA)(C{double bond, long}C{double bond, long}CPh2)][CF3SO3]2 (6).

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

The important role of Sodium trifluoromethanesulfonate

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High efficient Light-Emitting Electrochemical Cells based on ionic liquids 1,2,3-triazolium

The Light-Emitting Electrochemical Cell (LEEC) is one of the simplest kind of electroluminescent solid-state devices. Generally, they are fabricated with only one emitting material layer (EML), so-called active emission layer, that consist of an emitter material mixed with an ionic electrolyte. Apart from the electrolyte, their structure is similar to that of a single layer organic light-emitting diode (OLED). Not only LEECs assemble most of OLEDs applications and their technological advantages, but they also bring additional ones such as (i) low dependence of the electrodes work function, (ii) low dependence to the EML thickness, (iii) low operation voltage and high brightness and finally (iv) LEECs can be printed or sprayed in large areas. To investigate the performance of ionic liquid (IL) based devices we synthesized four organic salts that were compared with devices using four inorganic salts commonly used as electrolyte for LEECs. All devices were fabricated with a commercial poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) as emitter polymer. As a result, we showed that the best device performance was achieved with the Ionic Liquid 1-dodecyl-4-(hydroxymethyl)-3-methyl-1H-1,2,3-triazol-3-ium iodide (dohmtI) presenting a current efficiency of 3.6 cd/A, an external quantum efficiency (EQE) of 1.4% as well as a luminance of 3.2 × 104 cd/m2. Despite the use of MEH-PPV, a polymer not so efficient when compared to the state-of-art of the novel polymers employed nowadays, our realization showed these new ILs have been able to provide the specific requirements of the LEEC devices.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Mesomorphic [2]rotaxanes: Sheltering ionic cores with interlocking components

Two types of liquid crystalline [2]rotaxanes based on a conventional tetracatenar motif (a rod-shaped molecule with two side chains at each end) have been prepared. Dicationic compounds with ester stoppers and tetracationic materials with pyridinium stoppers are compared to each other and their dumbbell shaped analogs. Since the ionic core contributes about 70% to the overall length and molecular weight of the molecules, sheltering the ionic cores with an interlocked neutral macrocycle has considerable effect on the mesomorphism and thermal stability of the materials. The influence of the sheltering macrocycle, the numbers of charges on the core and the size and nature of the side chains (aliphatic vs siloxane) were probed. [2]Rotaxanes with linear side chains and minimum ratios of chain-to-core volumes of about 0.35 and 0.30 for tetra- and dicationic compounds, respectively, display smectic liquid crystal phases. Larger ratios increase the temperature range of the smectic A phases beyond the decomposition temperatures; a disadvantage for processing because no stable isotropic liquid phase is available. The change from tetra- to dicationic [2]rotaxanes increased not only the fluidity of their smectic A phases but also their thermal and chemical stability. Branched side chains (2-hexyldecyl) disfavor the formation of lamellar mesophases and, instead, induce higher ordered soft crystal phases. No liquid crystal phases but soft crystal phases are observed for the analogous di- and tetracationic compounds without an ion sheltering interlocked macrocycle (dumbbells).

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

Simple exploration of Sodium trifluoromethanesulfonate

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Cyano-bridged Fe(II)-Cu(II) bimetallic assemblies: Honeycomb-like and pentanuclear structures

A 2D honeycomb-like compound [Fe(CN)6{Cu(apn)}3] n(ClO4)2n(H2O)4n (1) (apn=N-(3-aminopropyl)-1,3-propanediamine) and a pentanuclear compound [Fe(CN)6{Cu(dmen)2}4](ClO4) 4 (2) (dmen=N,N-dimethylethylenediamine) have been prepared and characterized. In the synthesis, the use of ferricyanide or ferrocyanide yielded identical products due to reduction of Fe(III) ion to Fe(II) in water. For 1, all cyanide groups of ferrocyanide are bonded to six Cu(II) ions of which two symmetry-related Cu atoms are linked to nitrogen atoms of cyanide ligands bound to the neighboring Fe(II) center, resulting in the honeycomb structure. The variations of the geometries around Cu(II) centers are between ideal trigonal bipyramidal and square pyramidal structures, which may arise from the relative structural arrangements of flexible apn ligands. For 2, all the Cu(II) ions can be seen as square pyramidal geometries composed of basal least-squares planes from four dmen nitrogen atoms and apical nitrogen atoms from cyanide bridge. The Cu-NC angle around Cu centers in 2 is 127.9(7), much acuter than that of 1, which is presumably associated with steric interactions between the bulky methyl groups of the dmen ligands on the neighboring Cu ions. Both compounds exhibit very weak antiferromagnetic interactions in the low temperature range.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Deep Eutectic Solvents as Suitable Electrolytes for Electrochromic Devices

The development of chloride free Deep Eutectic Solvents (DES) based on lithium acetate, triflate, bistriflimide, and sodium triflate combined with glycerol, ethylene glycol, and polyethylene glycol (PEG400) as suitable electrolytes was successfully applied in electrochromic devices (ECD). Reversible ECD incorporating selected DES as electrolyte and bipyridinium as electrochromic probes displayed a comparable performance to conventional systems, with slower transition times (2.5 times), improving the coloration contrast and efficiency (147.1 cm2. C-1 at 520 nm) and was stable for at least 1250 redox cycles.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

Discovery of 2926-30-9

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Generation and reactions of heteroaromatic arynes using hypervalent iodine compounds

The heterocyclic aryne precursors, (phenyl)[1-phenyl-6-(trimethylsilyl)benzotriazol-5-yl]iodonium triflate and [3-ethoxycarbonyl-6-(trimethylsilyl)indazol-5-yl](phenyl)iodonium triflate, were prepared from the cycloadducts of 4,5-bis(trimethylsilyl)benzyne generated from (phenyl)[2,4,5-tris(trimethylsilyl)phenyl]iodonium triflate. These precursors provide the corresponding arynes, 1-phenyl-5,6-didehydrobenzotriazole and 3-ethoxycarbonyl-5,6-didehydroindazole, to give the corresponding polycyclic heteroaromatic compounds in good to high yields.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

Brief introduction of Sodium trifluoromethanesulfonate

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Synthesis and characterization of some cationic eta3-propargylpalladium complexes

Some cationic eta3-propargylpalladium complexes were prepared upon treatment of the corresponding eta1-propargyl- or eta1- allenylbis(triphenylphosphine)palladium(II) chloride with Ag[BF4] or Na[BPh4]. The effectiveness of the latter reagent suggests that a eta1- propargyl- or eta1-allenyl(chloro)palladium complex equilibrates with a cationic eta3-propargylpalladium complex with the liberation of a Cl- ligand. A qualitative comparison of trends in a series of analogous equilibrium systems suggests that the eta3-coordination mode is favored to a greater extent when (i) propargyl ligands have an alkyl substituent at the propargylic position, (ii) phosphine ligands are bidentate, such as dppe, (iii) polar solvents are used, and (iv) the liberating ligand is a Cl- one. A possible implication of eta3-coordination of propargyl ligands in a catalytic cycle of Pd-catalyzed transformations of propargylic or allenylic substrates is presented.

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Reference£º
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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PROCESS FOR REDUCTION OF CARBON DIOXIDE WITH ORGANOMETALLIC COMPLEX

Carbon dioxide and water are mixed with an organometallic complex represented by general formula (1) below where R1, R2, R3, R4, R5, and R6 independently represent a hydrogen atom or a lower alkyl group, M represents an element that can be coordinated to the benzene ring, X1 and X2 represent nitrogen-containing ligands, X3 represents a hydrogen atom, a carboxylic acid residue, or H2O, X1 and X2 may be bonded to each other, Y represents an anion species, K represents a valency of a cation species, L represents a valency of an anion species, K and L independently represent 1 or 2, and K, m, L, and n are related to one another by K x m = L x n. This makes it possible to directly reduce carbon dioxide in water.

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Reference£º
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI