Synthesis, X-ray structures, and spectroscopic and electrochemical properties of (mu-oxo)bis(mu-carboxylato)diruthenium complexes having six imidazole bases as terminal ligands

Complexes [Ru2O(O2CR)(2)(1-MeIm)(6)](ClO4)(2) (la-c), [Ru2O(O2CR)(2)(ImH)(6)](ClO4)(2) (2a,b), and [Ru2O(O2CR)(2)(4-MeImH)(6)](ClO4)(2) (3a,b) with a (mu-oxo)bis(mu-carboxylato)diruthenium(III) core have been prepared by reacting Ru2Cl(O2CR)(4) with the corresponding imidazole base, viz. 1-methylimidazole (1-MeIm), imidazole (ImH), and 4-methylimidazole (4-MeImH) in methanol, followed by treatment with NaClO4 in water (R: Me, a; C6H4-p-OMe, b; C6H4-p-Me, c). Diruthenium(III,IV) complexes [Ru2O(O2CR)(2)(1-MeIm)(6)](ClO4)(3) (R: Me, 4a; C6H4-p-OMe, 4b; C6H4-p-Me, 4c) have been prepared by one-electron oxidation of 1 in MeCN with K2S2O8 in water. Complexes la, 2a . 3H(2)O, and 4a . 1.5H(2)O have been structurally characterized. Crystal data for the complexes are as follows: la, orthorhombic, P2(1)2(1)2(1), a = 7.659(3) Angstrom, b = 22.366(3) Angstrom, c = 23.688(2) Angstrom, V = 4058(2) Angstrom(3), Z = 4, R = 0.0475, and R-w = 0.0467 for 2669 reflections with F-o > 2 sigma(F-o); 2a . 3H(2)O, triclinic, , a = 13.735(3) Angstrom, b = 14.428(4) Angstrom, c = 20.515(8) Angstrom, alpha = 87.13(3)degrees, beta = 87.61(3)degrees, gamma = 63.92(2)degrees, V = 3646(2) Angstrom(3), Z = 4, R = 0.0485 and R-w = 0.0583 for 10 594 reflections with F-o > 6 sigma(F-o); 4a . 1.5H(2)O triclinic, , a = 11.969(3) Angstrom, b = 12.090(6) Angstrom, c = 17.421(3) Angstrom, alpha = 108.93(2)degrees, beta = 84.42(2)degrees, gamma = 105.97(2)degrees, V = 2292(1) Angstrom(3), Z = 2, R = 0.0567, and R-w = 0.0705 for 6775 reflections with F-o > 6 sigma(F-o). The complexes have a diruthenium unit held by an oxo and two carboxylate ligands, and the imidazole ligands occupy the terminal sites of the core. The Ru-Ru distance and the Ru-O-oxo-Ru angle in la and 2a . 3H(2)O are 3.266(1), 3.272(1) Angstrom and 122.4(4), 120.5(2)degrees, while in 4a . 1.5H(2)O these values are 3.327(1) Angstrom and 133.6(2)degrees. The diruthenium(III) complexes 1-3 are blue in color and they exhibit an intense visible band in the range 560-575 nm. The absorption is charge transfer in nature involving the Ru(III)-d pi and O-oxo-p pi orbitals. The diruthenium(III,IV) complexes are red in color and show an intense band near 500 nm. The diruthenium(III) core readily gets oxidized with K2S2O8 forming quantitatively the diruthenium(III,IV) complex. The visible spectral record of the conversion shows an isosbestic point at 545 nm for 1 and at 535 nm for 2 and 3. Protonation of the oxide bridge by HClO4 in methanol yields the [Ru-2(mu-OH)(mu-O2CR)(2)](3+) core. The hydroxo species shows a visible band al 550 nm. The pK(a) value for la is 2.45. The protonated species are unstable. The 1-MeIm species converts to the diruthenium(III,IV) core, while the imidazole complex converts to [Ru(ImH)(6)](3+) and some uncharacterized products. Complex [Ru(ImH)(6)](ClO4)(3) has been structurally characterized. The diruthenium(III) complexes are essentially diamagnetic and show characteristic H-1 NMR spectra indicating the presence of the dimeric structure in solution. The diruthenium(III,IV) complexes are paramagnetic and display rhombic EPR spectral features. Complexes 1-3 are redox active. Complex 1 shows the one-electron reversible Ru-2(III)/(RuRuIV)-Ru-III, one-electron quasireversible (RuRuIV)-Ru-III/Ru-2(IV), and two-electron quasireversible Ru-2(III)/Ru-2(II) couples near 0.4, 1.5, and -1.0 V vs SCE In MeCN-0.1 M TBAP, respectively, in the cyclic and differential pulse voltammetric studies. Complexes 2 and 3 exhibit only reversible Ru-2(III)/(RuRuIV)-Ru-III and the quasireversible (RuRuIV)-Ru-III/Ru-2(IV) couples near 0.4 and 1.6 V vs SCE, respectively, The observation of a quasireversible one-step two-electron transfer reduction process in 1 is significant considering its relevance to the rapid and reversible Fe-2(III)/Fe-2(II) redox process known for the tribridged diiron core in the oxy and deoxy forms of hemerythrin.

Ferrocene in conjugation with a Fischer carbene: Synthesis, NLO, and electrochemical behavior of a novel organometallic push-pull system

Using an iterative sequence of Wittig olefination, reduction, oxidation, and condensation of an active methylene group to carbonyl, it was possible to prepare a series of organometallic push-pull molecules [(CO)(5)M=C(OCH3)(-CH=CH-)(n)(C5H4)Fe(C5H5), M = W, Cr, n = 1-4] in which ferrocene is the donor element and a Fisher carbene moeity is the acceptor group. The molecular first hyperpolarizability beta was determined by hyper-Rayleigh scattering experiments. The beta values ranged from 110 x 10(-30) to 2420 x 10(-30) esu in acetonitrile, and they are among the highest reported for organometallic molecules so far. Electrochemical measurements are consistent with the push-pull nature of these compounds.

Liquefaction And Pore Water Pressure Generation In Sand - A Cyclic Strain Approach

This paper presents the results of laboratory investigation carried out on Ahmedabad sand on the liquefaction and pore water pressure generation during strain controled cyclic loading. Laboratory experiments were carried out on representative natural sand samples (base sand) collected from earthquake-affected area of Ahmedabad City of Gujarat State in India. A series of strain controled cyclic triaxial tests were carried out on isotropically compressed samples to study the influence of different parameters such as shear strain amplitude, initial effective confining pressure, relative density and percentage of non-plastic fines on the behavior of liquefaction and pore water pressure generation. It has been observed from the laboratory investigation that the potential for liquefaction of the sandy soils depends on the shear strain amplitude, initial relative density, initial effective confining pressure and non-plastic fines. In addition, an empirical relationship between pore pressure ratio and cycle ratio independent of the number of cycles of loading, relative density, confining pressure, amplitude of shear strain and non-plastic fines has been proposed.

Hydrogel-polymer electrolytes for electrochemical capacitors: an overview

Electrochemical capacitors are electrochemical devices with fast and highly reversible charge-storage and discharge capabilities. The devices are attractive for energy storage particularly in applications involving high-power requirements. Electrochemical capacitors employ two electrodes and an aqueous or a non-aqueous electrolyte, either in liquid or solid form; the latter provides the advantages of compactness, reliability, freedom from leakage of any liquid component and a large operating potential-window. One of the classes of solid electrolytes used in capacitors is polymer-based and they generally consist of dry solid-polymer electrolytes or gel-polymer electrolyte or composite-polymer electrolytes. Dry solid-polymer electrolytes suffer from poor ionic-conductivity values, between 10(-8) and 10(-7) S cm(-1) under ambient conditions, but are safer than gel-polymer electrolytes that exhibit high conductivity of ca. 10(-3) S cm(-1) under ambient conditions. The aforesaid polymer-based electrolytes have the advantages of a wide potential window of ca. 4 V and hence can provide high energy-density. Gel-polymer electrolytes are generally prepared using organic solvents that are environmentally malignant. Hence, replacement of organic solvents with water in gel-polymer electrolytes is desirable which also minimizes the device cost substantially. The water containing gel-polymer electrolytes, called hydrogel-polymer electrolytes, are, however, limited by a low operating potential-window of only about 1.23 V. This article reviews salient features of electrochemical capacitors employing hydrogel-polymer electrolytes.

Study of texture evolution in metastable beta-Ti alloy as a function of strain path and its effect on alpha transformation texture

Texture evolution in a low cost beta titanium alloy was studied for different modes of rolling and heat treatments. The alloy was cold rolled by unidirectional and multi-step cross rolling. The cold rolled material was either aged directly or recrystallized and then aged. The evolution of texture in alpha and beta phases were studied. The rolling texture of beta phase that is characterized by the gamma fiber is stronger for MSCR than UDR; while the trend is reversed on recrystallization. The mode of rolling affects alpha transformation texture on aging with smaller alpha lath size and stronger alpha texture in UDR than in MSCR. The defect structure in beta phase influences the evolution of a texture on aging. A stronger defect structure in beta phase leads to variant selection with the rolled samples showing fewer variants than the recrystallized samples.

Dynamic strain ageing in Ni-base superalloy 720Li

An experimental investigation into the dynamic strain ageing (DSA) of a wrought Ni-base superalloy 720Li was conducted. Characteristics of jerky, flow have been studied at intermediate temperatures of 350, 400 and 450 degrees C at strain-rates between 10(-3) and 10(-5) s(-1). Serrations of Type C are predominant within the temperature/strain-rate range explored. The major characteristics of the serrations-i.e. (a) critical plastic strain for onset of serrations, epsilon(c); (b) average stress decrement, Delta sigma(avg); and (c) strain increment between serrations. Delta epsilon(BS)-have been examined at selected temperatures and strain-rates. Negative strain-rate sensitivity was observed in the DSA regime. However. temperature did not influence tensile properties such as yield strength, ultimate strength. elongation, reduction in area, and work hardening rate or fracture features in DSA regime. Analysis of the results Suggests that locking of the mobile dislocations by substitutional alloying elements is responsible for the DSA in alloy 720Li.

Quasi-static and dynamic strain sensing using carbon nanotube/epoxy nanocomposite thin films

Thin films are developed by dispersing carbon black nanoparticles and carbon nanotubes (CNTs) in an epoxy polymer. The films show a large variation in electrical resistance when subjected to quasi-static and dynamic mechanical loading. This phenomenon is attributed to the change in the band-gap of the CNTs due to the applied strain, and also to the change in the volume fraction of the constituent phases in the percolation network. Under quasi-static loading, the films show a nonlinear response. This nonlinearity in the response of the films is primarily attributed to the pre-yield softening of the epoxy polymer. The electrical resistance of the films is found to be strongly dependent on the magnitude and frequency of the applied dynamic strain, induced by a piezoelectric substrate. Interestingly, the resistance variation is found to be a linear function of frequency and dynamic strain. Samples with a small concentration of just 0.57% of CNT show a sensitivity as high as 2.5% MPa-1 for static mechanical loading. A mathematical model based on Bruggeman's effective medium theory is developed to better understand the experimental results. Dynamic mechanical loading experiments reveal a sensitivity as high as 0.007% Hz(-1) at a constant small-amplitude vibration and up to 0.13%/mu-strain at 0-500 Hz vibration. Potential applications of such thin films include highly sensitive strain sensors, accelerometers, artificial neural networks, artificial skin and polymer electronics.

Pt metal-CeO2 interaction: Direct observation of redox coupling between Pt-0/Pt2+/Pt4+ and Ce4+/Ce3+ states in Ce0.98Pt0.02O2-delta catalyst by a combined electrochemical and x-ray photoelectron spectroscopy study

Pt ions-CeO2 interaction in Ce1-xPtxO2-delta (x=0.02) has been studied for the first time by electrochemical method combined with x-ray diffraction and x-ray photoelectron spectroscopy. Working electrodes made of CeO2 and Ce0.98Pt0.02O2-delta mixed with 30% carbon are treated electrochemically between 0.0-1.2 V in potentiostatic (chronoamperometry) and potentiodynamic (cyclic voltametry) mode with reference to saturated calomel electrode. Reversible oxidation of Pt-0 to Pt2+ and Pt4+ state due to the applied positive potential is coupled to simultaneous reversible reduction of Ce4+ to Ce3+ state. CeO2 reduces to CeO2-y (y=0.35) after applying 1.2 V, which is not reversible; Ce0.98Pt0.02O2-delta reaches a steady state with Pt2+:Pt4+ in the ratio of 0.60:0.40 and Ce4+:Ce3+ in the ratio of 0.55:0.45 giving a composition Ce0.98Pt0.02O1.74 at 1.2 V, which is reversible. Composition of Pt ion substituted compound is reversible between Ce0.98Pt0.02O1.95 to Ce0.98Pt0.02O1.74 within the potential range of 0.0-1.2 V. Thus, Ce0.98Pt0.02O2-delta forms a stable electrode for oxidation of H2O to O-2 unlike CeO2. A linear relation between oxidation of Pt2+ to Pt4+ with simultaneous reduction in Ce4+ to Ce3+ is observed demonstrating Pt-CeO2 metal support interaction is due to reversible Pt-0/Pt2+/Pt4+ interaction with Ce4+/Ce3+ redox couple.

Synergy between tribo-oxidation and strain rate response on governing the dry sliding wear behavior of titanium.

The present work provides an insight into the dry sliding wear behavior of titanium based on synergy between tribo-oxidation and strain rate response. Pin-on-disc tribometer was used to characterize the friction and wear behavior of titanium pin in sliding contact with polycrystalline alumina disk under ambient and vacuum condition. The sliding speed was varied from 0.01 to 1.4 ms(-1), normal load was varied from 15.3 to 76 N and with a sliding distance of 1500 m. It was seen that dry sliding wear behavior of titanium was governed by combination of tribo-oxidation and strain rate response in near surface region of titanium. Strain rate response of titanium was recorded by conducting uni-axial compression tests at constant true strain rate of 100 s(-1) in the temperature range from 298 to 873 K. Coefficient of friction and wear rate were reduced with increased sliding speed from 0.01 to 1.0 ms(-1). This is attributed to the formation of in situ self lubricating oxide film (TiO) and reduction in the intensity of adiabatic shear band cracking in the near surface region. This trend was confirmed by performing series of dry sliding tests under vacuum condition of 2 x 10(-4) Torr. Characterization tools such as optical microscopy, scanning electron microscopy, and X-ray diffractometer provided evidence of such processes. These experimental findings can be applied to enhance the dry sliding wear behavior of titanium with proper choice of operating conditions such as sliding speed, normal load, and environment.

Electrochemical phase formation (ECPF): Nucleation growth vis-a-vis adsorption models

The nucleataon growth model of electrochemical phase formation is analysed for the hnear potential sweep input Apart from deducing diagnostic criteria and method~ of estimating model parameters, the predictions of the nucleation growth model are compared and contrasted with those of a sample adsorption model A dastlnCtlOn is made possible between adsorption and phase transition, which seems useful for understanding the nature of ECPF phenomena, especially underpotentlal deposition (UPD).

Flow of metal into the flash gap in the last stages of a plane-strain closed-die forging operation

In closed-die forging the flash geometry should be such as to ensure that the cavity is completely filled just as the two dies come into contact at the parting plane. If metal is caused to extrude through the flash gap as the dies approach the point of contact — a practice generally resorted to as a means of ensuring complete filling — dies are unnecessarily stressed in a high-stress regime (as the flash is quite thin and possibly cooled by then), which reduces the die life and unnecessarily increases the energy requirement of the operation. It is therefore necessary to carefully determine the dimensions of the flash land and flash thickness — the two parameters, apart from friction at the land, which control the lateral flow. The dimensions should be such that the flow into the longitudinal cavity is controlled throughout the operation, ensuring complete filling just as the dies touch at the parting plane. The design of the flash must be related to the shape and size of the forging cavity as the control of flow has to be exercised throughout the operation: it is possible to do this if the mechanics of how the lateral extrusion into the flash takes place is understood for specific cavity shapes and sizes. The work reported here is part of an ongoing programme investigating flow in closed-die forging. A simple closed shape (no longitudinal flow) which may correspond to the last stages of a real forging operation is analysed using the stress equilibrium approach. Metal from the cavity (flange) flows into the flash by shearing in the cavity in one of the three modes considered here: for a given cavity the mode with the least energy requirement is assumed to be the most realistic. On this basis a map has been developed which, given the depth and width of the cavity as well as the flash thickness, will tell the designer of the most likely mode (of the three modes considered) in which metal in the cavity will shear and then flow into the flash gap. The results of limited set of experiments, reported herein, validate this method of selecting the optimum model of flow into the flash gap.

Two-dimensional phase transitions at electrochemical interfaces

A two-state Ising model has been applied to the two-dimensional condensation of tymine at the mercury-water interface. The model predicts a quadratic dependence of the transition potential on temperature and on the logarithm of the adsorbate concentration. Both predictions have been confirmed experimentally.

Electrochemical Reduction of Oriented Graphene Oxide Films: An in Situ Raman Spectroelectrochemical Study

Graphene oxide (GO) is assembled on a gold substrate by a layer-by-layer technique using a self-assembled cystamine monolayer. The negatively charged GO platelets are attached to the positively charged cystamine monolayer through electrostatic interactions. Subsequently, it is shown that the GO can be reduced electrochemically using applied DC bias by scanning the potential from 0 to -1 V vs a saturated calomel electrode in an aqueous electrolyte. The GO and reduced graphene oxide (RGO) are characterized by Raman spectroscopy and atomic force microscopy (AFM). A clear shift of the G band from 1610 cm-1 of GO to 1585 cm-1 of RGO is observed. The electrochemical reduction is followed in situ by micro Raman spectroscopy by carrying out Raman spectroscopic studies during the application of DC bias. The GO and RGO films have been characterized by conductive AFM that shows an increase in the current flow by at least 3 orders of magnitude after reduction. The electrochemical method of reducing GO may open up another way of controlling the reduction of GO and the extent of reduction to obtain highly conducting graphene on electrode materials.

Deformation mechanisms during large strain deformation of nanocrystalline nickel

In this letter, a conclusive evidence of the operation of planar slip along with grain boundary mediated mechanisms has been reported during large strain deformation of nanocrystalline nickel. Dislocation annihilation mechanism such as mechanical recovery has been found to play an important role during the course of deformation. The evidences rely on x-ray based techniques, such as dislocation density determination and crystallographic texture measurement as well as microstructural observation by electron microscopy. The characteristic texture evolution in this case is an indication of normal slip mediated plasticity in nanocrystalline nickel.