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Electrochemical Properties (electrochemical + property)
Selected AbstractsCORRELATION BETWEEN SPECTRAL, SEM/EDX AND ELECTROCHEMICAL PROPERTIES OF MAYA BLUE: A CHEMOMETRIC STUDY*ARCHAEOMETRY, Issue 6 2009A. DOMÉNECH Visible spectra, composition from SEM/EDX and solid-state electrochemical data are correlated for a set of 12 Maya Blue samples from different archaeological sites of Campeche and Yucatán (Mexico). In addition to indigo and dehydroindigo, indirubin and other possibly indigo-type compounds can be detected in Maya Blue samples. Application of hierarchical cluster analysis techniques allows similarity relationships to be established between samples from different sites, confirming prior results which suggest that the preparation of Maya Blue pigment evolved with time during the Maya culture following a ramified scheme. [source] Electrochemical Properties of Ordered Mesoporous Carbon Film Adsorbed onto a Self-Assembled Alkanethiol Monolayer on Gold ElectrodeELECTROANALYSIS, Issue 2 2009Dan Zheng Abstract A stable ordered mesoporous carbon (OMC) film electrode was successfully constructed by adsorbing OMC onto a self-assembled monolayer (SAM) of C18H37SH chemisorbed on the Au electrode. Transmission electron microscopy (TEM), atomic force microscopy (AFM), and electrochemical methods were used to characterize the properties of the OMC film electrode. The adsorbed OMC can restore the heterogeneous electron transfer almost totally blocked by the alkanethiol monolayer. Nyquist plots show a sharply decrease of the charge transfer resistance (Rct) of the Fe(CN) couple at the OMC film electrode. Furthermore, the OMC film electrode is found to possess a significantly reduced interfacial capacitance and largely enhanced current response of hydrogen peroxide. This novel approach to the fabrication of stable OMC film electrode with excellent electrochemical properties is believed to be very attractive for electrochemical studies and electroanalytical applications. [source] Electroconductive Hydrogels: Electrical and Electrochemical Properties of Polypyrrole-Poly(HEMA) CompositesELECTROANALYSIS, Issue 7 2005Sean Brahim Abstract Composites of inherently conductive polypyrrole (PPy) within highly hydrophilic poly(2-hydroxyethyl methacrylate)-based hydrogels (p(HEMA)) have been fabricated and their electrochemical properties investigated. The electrochemical characteristics observed by cyclic voltammetry suggest less facile reduction of PPy within the composite hydrogel compared to electropolymerized PPy, as shown by the shift in the reduction peak potential from ,472,mV for electropolymerized polypyrrole to ,636,mV for the electroconductive composite gel. The network impedance magnitude for the electroconductive hydrogel remains quite low, ca. 100,,, even upon approach to DC, over all frequencies and at all offset potentials suggesting retained electronic (bipolaronic) conductivity within the composite. In contrast, sustained application of +0.7 V (vs. Ag/AgCl, 3,M Cl,) for typically 100,min. (conditioning) to reduce the background amperometric current to <1.0,,A, resulted in complete loss of electroactivity. Nyquist plots suggest that sustained application of such a modest potential to the composite hydrogel results in impedance characteristics that resembles p(HEMA) without evidence of the conducting polymer component. PPy composite gels supported a larger ferrocene monocarboxylate diffusivity (Dappt=7.97×10,5,cm2,s,1) compared to electropolymerized PPy (Dappt=5.56×10,5,cm2,s,1), however a marked reduction in diffusivity (Dappt=1.01×10,5,cm2,s,1) was observed with the conditioned hydrogel composite. Cyclic voltammograms in buffer containing H2O2 showed an absence of redox peaks for electrodes coated with PPy-containing membranes, suggesting possible chemical oxidation of polypyrrole by the oxidant [source] Magnetic and Electrochemical Properties of a Heterobridged ,-Phenoxido,,1,1 -Azide Dinickel(II) Compound: A Unique Example Demonstrating the Bridge Distance Dependency of Exchange IntegralEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 33 2009Rajesh Koner Abstract The synthesis, structure, magnetic and electrochemical properties of the heterobridged ,-phenoxido,,1,1 -azide dinickel(II) compound [NiII2(HL1)3(,1,1 -N3)]·3H2O (1) derived from the tetradentate Schiff base ligand N -(2-hydroxyethyl)-3-methoxysalicylaldimine (H2L1) are described. The title compound crystallizes in the triclinic system (space group P). Electrochemical analyses reveal that compound 1 exhibits two-step quasireversible couples in the reduction window with E1/2 values of ,1412 and ,1762 mV. The variable-temperature (2,300 K) magnetic susceptibilities at 1 T of the title compound were measured. The interaction between the metal centres is weak ferromagnetic (J = 5.0 cm,1, g = 2.23, D1 = 29.2 cm,1 and D2 = 10.7 cm,1). Comparison of the exchange integral of 1 with that of the only reported ,-phenoxido,,1,1 -azide dinickel(II) compound results in the emergence of a unique example of the dependence of strength of magnetic exchange interaction on the metal,ligand bridge distance. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Variable Coordination Modes of Benzaldehyde Thiosemicarbazones , Synthesis, Structure, and Electrochemical Properties of Some Ruthenium ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 29 2008Swati Dutta Abstract Reaction of benzaldehyde thiosemicarbazones [H2LR, where H2 stands for the two protons, the hydrazinic proton, and the phenyl proton at the ortho position, with respect to the imine function and R (R = OCH3, CH3, H, Cl, and NO2) for the para substituent] with [Ru(PPh3)2(CO)2Cl2], carried out in refluxing ethanol, afforded monomeric complexes of type [Ru(PPh3)2(CO)(HLR)(H)]. The crystal structure of the [Ru(PPh3)2(CO)(HLNO2)(H)] complex was determined. The thiosemicarbazone ligand is coordinated to the ruthenium center as a bidentate N,S-donor ligand forming a four-membered chelate ring. When the reaction of the thiosemicarbazones with [Ru(PPh3)2(CO)2Cl2] was carried out in refluxing toluene, a family of dimeric complexes of type [Ru2(PPh3)2(CO)2(LR)2] were obtained. The crystal structure of [Ru2(PPh3)2(CO)2(LCl)2] was determined. Each thiosemicarbazone ligand is coordinated to one ruthenium atom, by dissociation of the two protons, as a dianionic tridentate C,N,S-donor ligand, and at the same time the sulfur atom is also bonded to the second ruthenium center. 1H NMR spectra of the complexes of both types are in excellent agreement with their compositions. All the dimeric and monomeric complexes are diamagnetic (low-spin d6, S = 0) and show intense absorptions in the visible and ultraviolet regions. Cyclic voltammetry of the [Ru(PPh3)2(CO)(HLR)(H)] and [Ru2(PPh3)2(CO)2(LR)2] complexes show the ruthenium(II),ruthenium(III) oxidation within 0.48,0.73 V vs. SCE followed by a ruthenium(III),ruthenium(IV) oxidation within 1.09,1.47 V vs. SCE. Potentials of both the oxidations are found to correlate linearly with the electron-withdrawing character of the substituent R. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Synthesis, Characterization, and Electrochemical Properties of Novel Transition Metal,Fullerene Complexes Containing Di- and Tetraphosphane LigandsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 2 2006Li-Cheng Song Abstract This paper reports the synthesis, characterization, and some properties of transition metal,fullerene complexes containing trans -1,1,-bis(diphenylphosphanyl)ethylene (dppet, trans -Ph2PCH=CHPPh2) and N,N,N,,N,-tetra(diphenylphosphanylmethyl)ethylene diamine (dppeda, [(Ph2PCH2)2NCH2]2), including [(,2 -C60M)(dppet)2] (M = Pt 1, Pd 2), [(,2 -C60M)(dppet)]2 (M = Pt 3, Pd 4), [(,2 -C60Pd)(,2 -C60Pt)(dppet)2](5), [(,2 -C60Pd)(,2 -C70Pd)(dppet)2] (6), [(,2 -C70Pd)(dppet)]2 (7), [(,2 -C60M)(dppeda)] (M = Pt 8, Pd 9), and [(,2 -C60M)2(dppeda)] (M = Pt 10, Pd 11). Interestingly, while complexes 1, 2, 8, and 9 are the first examples of metallacyclopropafullerene diphosphane ligands containing fullerene cores, complexes 3,7, 10, and 11 are the first group 10 metal-containing, dumbbell-shaped bisfullerenes. All the complexes 1,11 were characterized by elemental analysis, spectroscopy, and, particularly for 4 and 5, by X-ray crystallography and cyclic voltammetry. Pathways for the formation of 1,11 are suggested. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Synthesis, Characterization, and Electrochemical Properties of Dinuclear Complexes Assembled from Asymmetric CoIII Bis(dioximates) and Boronic AcidsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 19 2005Renata Dreos Abstract Bis(methylphenylglyoximate)cobalt(III) complexes exist both as cis and trans isomers due to the asymmetry of the equatorial ligand, and, when the axial ligands are different, the trans isomer is chiral. The reaction of racemic trans -[CH3Co(mpgH)2py] (1) with either 3- or 4-pyridylboronic acid affords dimeric units arranged on a crystallographic symmetry center such that the pyridyl nitrogen of one moiety coordinates to the Co atom of the symmetry-related unit. In principle, three structurally different dimeric species (two homodimers and one heterodimer) can be obtained. Time-resolved 1H NMR spectra of a 1:1 mixture of racemic 1 and either 3- or 4-pyridylboronic acid in CDCl3/CD3OD show that the reaction does not converge toward a unique species in solution. Nevertheless, X-ray structures show that the heterochiral dimers are the only products that crystallize from the reaction mixture. The nature of the dioximate side groups does not affect the geometry of the dimeric arrangements assembled by 4-pyridylboronic acid ("molecular box"). On the contrary, the geometry of the species assembled by 3-pyridylboronic acid varies from the "molecular parallelogram" obtained from the bis(dimethylglyoximates) to the highly squeezed "molecular box" obtained from bis(methylphenylglyoximates). Cyclic voltammetry studies show that the metal centers in the dimeric species do not interact with each other and undergo a simultaneous redox process. However, depending on the geometry of the systems, the redox process involves a single four-electron reduction for 3 and 5 or two consecutive two-electron reduction steps for 4 and 6. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Synthesis and Electrochemical Properties of Tetrasubstituted TetraphenylethenesEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 15 2006Alina Schreivogel Abstract Tetrakis(4-acetoxyphenyl and 4-benzoyloxyphenyl)ethenes 1f and 1g were obtained by acylation of tetrakis(4-hydroxyphenyl)ethene 1b. Ullmann etherification of 4,4,-dihydroxybenzophenone 2b and subsequent McMurry coupling yielded tetrakis(phenoxyphenyl)ethene 1i. The tetrakis(acetamidophenyl)ethene 1h was prepared in three steps from tetraphenylethene 1c by nitration, Raney-Ni reduction and subsequent acetylation. Alternatively, trifluoroacetamide 1j, 2-methylhexanamide 1k and 2,4-dimethylbenzamide 1l, with less tendency to form 2D hydrogen bonding networks and thus increased solubility as compared to 1h, were prepared by acylation of 4,4,-diaminobenzophenone 2a and subsequent McMurry coupling. Compounds 1f,l were investigated by cyclic voltammetry. While the phenyl ether derivative 1i displays single-electron processes during oxidation, a two-electron process was discovered for trifluoroacetamide 1j as was also supposed for the esters 1f and 1g. In addition, comproportionation constants were shown to be dependent on the solvent. In situ IR spectroelectrochemistry provided evidence for quinoidal type substructures in the dioxidized forms of tetraphenylethenes 1. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Preparation, Structure, and Electrochemical Properties of Reduced Graphene Sheet FilmsADVANCED FUNCTIONAL MATERIALS, Issue 17 2009Longhua Tang Abstract This paper describes the preparation, characterization, and electrochemical properties of reduced graphene sheet films (rGSFs), investigating especially their electrochemical behavior for several redox systems and electrocatalytic properties towards oxygen and some small molecules. The reduced graphene sheets (rGSs) are produced in high yield by a soft chemistry route involving graphite oxidation, ultrasonic exfoliation, and chemical reduction. Transmission electron microscopy (TEM), X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy clearly demonstrate that graphene was successfully synthesized and modified at the surface of a glassy carbon electrode. Several redox species, such as Ru(NH3)63+/2+, Fe(CN)63,/4,, Fe3+/2+ and dopamine, are used to probe the electrochemical properties of these graphene films by using the cyclic voltammetry method. The rGSFs demonstrate fast electron-transfer (ET) kinetics and possess excellent electrocatalytic activity toward oxygen reduction and certain biomolecules. In our opinion, this microstructural and electrochemical information can serve as an important benchmark for graphene-based electrode performances. [source] Fabrication and Electrochemical Properties of Epitaxial Samarium-Doped Ceria Films on SrTiO3 -Buffered MgO SubstratesADVANCED FUNCTIONAL MATERIALS, Issue 11 2009Simone Sanna Abstract Thin films of samarium-oxide-doped (20,mol%) ceria (SDC) are grown by pulsed-laser deposition (PLD) on (001) MgO single-crystal substrates. SrTiO3 (STO) prepared by PLD is used as a buffer layer on the MgO substrates to enable epitaxial growth of the fluorite-structured SDC film; the STO layer provides a proper crystalline match between SDC and MgO, resulting in highly crystalline, epitaxial SDC films grown in the (001) orientation. Film conductivity is evaluated by electrochemical impedance spectroscopy measurements, which are performed at various temperatures (400,775,°C) in a wide range of oxygen partial pressure (pO2) values (10,25,1,atm) in order to separate ionic and electronic conductivity contributions. At 700,°C, SDC/STO films on (100) MgO exhibit a dominant ionic conductivity of about 7,×,10,2,S cm,1, down to pO2 values of about 10,15,atm. The absence of grain boundaries make the SDC/STO/MgO heterostructures stable to oxidation-reduction cycles at high temperatures, in contrast to that observed for the more disordered SDC/STO films, which degraded after hydrogen exposure. [source] Physical and Electrochemical Properties of PVdF-HFP/SiO2 -Based Polymer Electrolytes Prepared Using Dimethyl Acetamide Solvent and Water Non-SolventMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 8 2007Kwang Man Kim Abstract Poly[(vinylidene fluoride)- co -hexafluoropropylene]/SiO2 polymer electrolytes were prepared by a phase inversion technique using DMAc solvent and water non-solvent. Cast film electrolytes filled with the same amount of SiO2 using DMAc were also made to compare physical and electrochemical properties. DMAc had a higher solubility to PVdF-based polymers than NMP, and DMAc produced highly porous structures with bigger cavities and influenced the reduction of crystallinity. Due to the highly porous nature of phase inversion membranes, the uptake of electrolyte solution reached more than 400% and room-temperature ionic conductivity was more than 10,3 S,·,cm,1. All of the liquid absorbed, however, did not necessarily contribute to increases in ionic conductivity. This was due to the different conduction modes of lithium cations in a complicated porous structure. Comprehensively optimizing all the properties measured, the phase inversion membrane electrolytes with 10,30 wt.-% SiO2 were the best candidates for use as the polymer electrolyte of lithium rechargeable batteries. [source] Multilayer Thin Films by Layer-by-Layer Assembly of Hole- and Electron-Transport Polyelectrolytes: Optical and Electrochemical PropertiesMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 20 2006Kyungsun Choi Abstract Summary: In this paper, we present the synthesis of a series of p-type and n-type semiconducting polyelectrolytes with triarylamine, oxadiazole, thiadiazole and triazine moieties. The synthesized polymeric hole and electron transport materials were examined optically and electrochemically using UV/Vis spectroscopy, PL spectroscopy and CV. Based on the optical and electrochemical data, each of the energy levels were calculated and all values suggested that they were promising hole- (p-type) or electron-transport (n-type) materials for devices. Moreover, the synthesized ionic polymers were suitable for LBL thin film deposition from dilute polymer solutions and the multilayers were fully characterized by UV/Vis, PL spectroscopy and CV. [source] New , -Conjugated Polymers Containing 1,3,5-Triazine Units in the Main Chain: Synthesis and Optical and Electrochemical Properties of the Polymers,MACROMOLECULAR RAPID COMMUNICATIONS, Issue 12 2005Shijie Ren Abstract Summary: Three new soluble , -conjugated polymers containing 1,3,5-triazine units in the main chain, Pa,Pc, were synthesized. The polymers showed optical properties in solution that were mainly dependant on the properties of the substituting R groups, on the triazine ring. Hence, Pa and Pb (R,=,H and OCH3, respectively) showed blue photoluminescent (PL) emission with high quantum yields (QY) even in polar solvents, whereas Pc (R,=,N,N -dimethylamino) gave green-blue PL emission with very low QY. The PL spectra of the polymers in solution were concentration and polarity dependent, which suggested the formation of an exciplex. The three new soluble , -conjugated polymers containing 1,3,5-triazine units in the main chain synthesized here. [source] ChemInform Abstract: Synthesis and Electrochemical Properties of Substituted para-Benzoquinone Derivatives.CHEMINFORM, Issue 33 2010Faiz Ahmed Khan Abstract Oxidation of phenols with PbO2 in combination with HClO4 affords the target compounds whose electrochemical properties are studied in detail. [source] ChemInform Abstract: Crystal Structure and Electrochemical Properties of A2MPO4F Fluorophosphates (A: Na, Li; M: Fe, Mn, Co, Ni).CHEMINFORM, Issue 31 2010Brian L. Ellis Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] ChemInform Abstract: Biomimetic Synthesis of Metal Ion-Doped Hierarchical Crystals Using a Gel Matrix: Formation of Cobalt-Doped LiMn2O4 with Improved Electrochemical Properties Through a Cobalt-Doped MnCO3 Precursor.CHEMINFORM, Issue 25 2010Takao Kokubu Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] ChemInform Abstract: Yb@C2n (n = 40, 41, 42): New Fullerene Allotropes with Unexplored Electrochemical Properties.CHEMINFORM, Issue 25 2010Xing Lu Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] ChemInform Abstract: Synthesis, Photophysical and Electrochemical Properties of a D-,-A Ensemble Derived from Porphyrazine and Tetrathiafulvalene.CHEMINFORM, Issue 46 2009Ruibin Hou Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] ChemInform Abstract: Bis-Carbene Adducts of Non-IPR La2@C72: Localization of High Reactivity Around Fused Pentagons and Electrochemical Properties.CHEMINFORM, Issue 2 2009Takeshi Akasaka Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] ChemInform Abstract: Cobalt(II)/Nickel(II)-Centered Keggin-Type Heteropolymolybdates: Syntheses, Crystal Structures, Magnetic and Electrochemical Properties.CHEMINFORM, Issue 28 2008Guang-Gang Gao Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Characterization and Electrochemical Properties of Molecular Icosanuclear and Bidimensional Hexanuclear Cu(II) Azido Polyoxometalates.CHEMINFORM, Issue 36 2007Celine Pichon Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] Synthesis, Characterization, and Electrochemical Properties of Ag2V4O11 and AgVO3 1-D Nano/Microstructures.CHEMINFORM, Issue 18 2007Shaoyan Zhang Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] Antifluorite-Type Lithium Chromium Oxide Nitrides: Synthesis, Structure, Order, and Electrochemical Properties.CHEMINFORM, Issue 1 2005Jordi Cabana Abstract For Abstract see ChemInform Abstract in Full Text. [source] Synthesis of Redox-Active Biscalix[4]quinones and Their Electrochemical Properties.CHEMINFORM, Issue 12 2003Kriengkamol Tantrakarn No abstract is available for this article. [source] Dendritic Cavitands: Preparation and Electrochemical Properties.CHEMINFORM, Issue 48 2002Rosa Toba No abstract is available for this article. [source] Synthesis, Structures, and Optical and Electrochemical Properties of BenzoporphycenesCHEMISTRY - A EUROPEAN JOURNAL, Issue 39 2009Daiki Kuzuhara Abstract The first facile syntheses of free-base di- and tetrabenzoporphycenes and their metal complexes are reported, based on retro-Diels,Alder reactions of the corresponding bicyclo[2.2.2]octadiene-fused porphycenes, prepared by McMurray coupling of ,,,,-diformyldipyrrole. The photophysical and electrochemical properties are analyzed based on UV/Vis absorption, magnetic circular dichroism (MCD), and fluorescence emission, lifetime and quantum yield measurements, cyclic and differential pulse voltammetry (CV and DPV) and time-dependent DFT calculations based on B3LYP geometry optimizations. Benzoporphycenes are found to be prime candidates for future use in photodynamic therapy. [source] Electrochemical Properties and Computations of Stable Radicals of the Heavy Group,14 Elements (Si, Ge, and Sn)CHEMISTRY - A EUROPEAN JOURNAL, Issue 34 2009James Abstract A series of stable radicals centered on persilyl-substituted heavy Group,14 elements, (tBu2MeSi)3E. (E=Si, Ge, Sn), was studied by cyclic voltammetry in different solvents to determine their first oxidation and reduction potentials and to compare their ease of oxidation and reduction with known experimental and computed ionization energies (Ei) and electron affinities (Eea), respectively. It has been observed that all of the first oxidation and reduction potentials for the three radicals studied are irreversible in o -dichlorobenzene (o -DCB), whereas the reduction waves are quasi-reversible in THF. A good correlation has been found between measured oxidation potentials and ionization energy values, but no correlation between reduction potentials and electron affinity values was found, probably due to kinetic and surface effects. [source] (Pentamethylcyclopentadienyl)ruthenium ,-Complexes of Metalloporphyrins: Platforms with Novel Photo- and Electrochemical PropertiesCHEMISTRY - A EUROPEAN JOURNAL, Issue 33 2008Luciano Cuesta Dr. Unusually accepting: A series of metalloporphyrin,ruthenocene complexes, synthesized by direct coordination of a [Ru(Cp*)]+ fragment to the ,-electron "face" of several metallooctaethylporphyrins (see graphic), undergo efficient photoinduced electron transfer from the ruthenocene unit (acting as the electron donor) to the singlet excited state of the metalloporphyrin unit (acting as the electron acceptor) to give a charge-separated state. [source] Fe2 and Fe4 Clusters Encapsulated in Vacant Polyoxotungstates: Hydrothermal Synthesis, Magnetic and Electrochemical Properties, and DFT CalculationsCHEMISTRY - A EUROPEAN JOURNAL, Issue 10 2008Céline Pichon Abstract While the reaction of [PW11O39]7, with first row transition-metal ions Mn+ under usual bench conditions only leads to monosubstituted {PW11O39M(H2O)} anions, we have shown that the use of this precursor under hydrothermal conditions allows the isolation of a family of novel polynuclear discrete magnetic polyoxometalates (POMs). The hybrid asymmetric [FeII(bpy)3][PW11O39Fe2III(OH)(bpy)2],12,H2O (bpy=bipyridine) complex (1) contains the dinuclear {Fe(,-O(W))(,-OH)Fe} core in which one iron atom is coordinated to a monovacant POM, while the other is coordinated to two bipyridine ligands. Magnetic measurements indicate that the FeIII centers in complex 1 are weakly antiferromagnetically coupled (J=,11.2,cm,1, H=,JS1S2) compared to other {Fe(,-O)(,-OH)Fe} systems. This is due to the long distances between the iron center embedded in the POM and the oxygen atom of the POM bridging the two magnetic centers, but also, as shown by DFT calculations, to the important mixing of bridging oxygen orbitals with orbitals of the POM tungsten atoms. The complexes [Hdmbpy]2[FeII(dmbpy)3]2[(PW11O39)2Fe4IIIO2(dmbpy)4],14,H2O (2) (dmbpy=5,5,-dimethyl-2,2,-bipyridine) and H2[FeII(dmbpy)3]2[(PW11O39)2Fe4IIIO2(dmbpy)4],10,H2O (3) represent the first butterfly-like POM complexes. In these species, a tetranuclear FeIII complex is sandwiched between two lacunary polyoxotungstates that are pentacoordinated to two FeIII cations, the remaining paramagnetic centers each being coordinated to two dmbpy ligands. The best fit of the ,MT=f(T) curve leads to Jwb=,59.6,cm,1 and Jbb=,10.2,cm,1 (H=,Jwb(S1S2+S1S2*+S1*S2+S1*S2*),Jbb(S2S2*)). While the Jbb value is within the range of related exchange parameters previously reported for non-POM butterfly systems, the Jwb constant is significantly lower. As for complex 1, this can be justified considering FewO distances. Finally, in the absence of a coordinating ligand, the dimeric complex [N(CH3)4]10[(PW11O39FeIII)2O],12,H2O (4) has been isolated. In this complex, the two single oxo-bridged FeIII centers are very strongly antiferromagnetically coupled (J=,211.7,cm,1, H=,JS1S2). The electrochemical behavior of compound 1 both in dimethyl sulfoxide (DMSO) and in the solid state is also presented, while the electrochemical properties of complex 2, which is insoluble in common solvents, have been studied in the solid state. [source] Biomimetic Synthesis of Metal Ion-Doped Hierarchical Crystals Using a Gel Matrix: Formation of Cobalt-Doped LiMn2O4 with Improved Electrochemical Properties through a Cobalt-Doped MnCO3 PrecursorCHEMISTRY - AN ASIAN JOURNAL, Issue 4 2010Takao Kokubu Abstract We have synthesized spinel type cobalt-doped LiMn2O4 (LiMn2,yCoyO4, 0,y,0.367), a cathode material for a lithium-ion battery, with hierarchical sponge structures via the cobalt-doped MnCO3 (Mn1- xCoxCO3, 0,x,0.204) formed in an agar gel matrix. Biomimetic crystal growth in the gel matrix facilitates the generation of both an homogeneous solid solution and the hierarchical structures under ambient condition. The controlled composition and the hierarchical structure of the cobalt-doped MnCO3 precursor played an important role in the formation of the cobalt-doped LiMn2O4. The charge,discharge reversible stability of the resultant LiMn1.947Co0.053O4 was improved to ca. 12,% loss of the discharge capacity after 100,cycles, while pure LiMn2O4 showed 24,% loss of the discharge capacity after 100,cycles. The parallel control of the hierarchical structure and the composition in the precursor material through a biomimetic approach, promises the development of functional materials under mild conditions. [source] | |||||||||||||||||||||||||||||||||||||