Highly efficient iridium(III) complexes with diphenylquinoline ligands for organic light-emitting diodes: Synthesis and effect of fluorinated substitutes on electrochemistry, photophysics and electroluminescence

A series of novel cyclometalated iridium(III) complexes bearing 2,4-diphenylquinoline ligands with fluorinated substituent were prepared and characterized by elemental analysis, NMR and mass spectroscopy. The cyclic voltammetry, absorption, emission and electroluminescent properties of these complexes were systematically investigated. Electrochemical studies showed that the oxidation of the fluorinated complexes occurred at more positive potentials (in the range 0.57-0.69 V) than the unfluorinated complex 1 (0.42 V). In view of the energy level, the lowering of the LUMO by fluorination is significantly less than that of the HOMO. The weak and low energies absorption bands in the range of 300-600 nm are well resolved, likely associated with MLCT and (3)pi-pi* transitions. These complexes show strong orange red emission both in the solution and solid state. The emission maxima of the fluorinated complexes showed blue shift by 9, 24 and 15 nm for 2, 3 and 4, respectively, with respect to the unfluorinated analogous 1. Multilayered organic light-emitting diodes (OLEDs) were fabricated by using the complexes as dopant materials. Significantly higher performance and lower turn-on voltage were achieved using the fluorinated complexes as the emitter than that using the unfluorinated counterpart 1 under the same doping level.

Electrochemistry of hydroquinone derivatives at metal and iodine-modified metal electrodes

The difference in the electrochemical behavior of hydroquinone and pyrocatechol. at platinum and gold surfaces was analyzed using voltammetry and attenuated total reflection Fourier transform infrared spectroscopy. The results show that the hydroquinone derivatives are adsorbed on a gold surface with vertical orientation, which makes the electron transfer between the bulk species and the electrode surface easier than that in the case of flat adsorption of hydroquinone derivatives that occurs at a platinum electrode. The formation of the vertical conformation and the rapid process of electron transfer were also confirmed by quantum chemistry calculations. In addition, the pre-adsorbed iodine on the electrodes played a key role on the adsorbed configuration and. electron transfer of redox species.

Electrochemical study of PW12O403- in poly(ethylene glycol) electrolyte

The electrochemical properties Of PW12O403- (abbreviated as PW12) anion in poly(ethylene glycol) (PEG) have been studied by cyclic voltammetry, complex impedance and FT-IR spectroscopy. The PW12 anion in PEG-LiClO4 electrolyte shows reasonable facile electrochemistry, and the diffusion coefficients Of PW12 were measured with microelectrode. It is shown that ionic conductivity of polymer electrolytes based on low molecular weight PEG can be improved by the addition of PW12. The increase of conductivity is coupled with decrease of transient cross-links density of polymer chains which is evidenced by the downshift of C-O-C stretching mode. The phenomena are explained in view of ion-ion and ion-polymer interactions.

Defect formation induced by PAMAM dendrimers on Pt-supported bilayer lipid membranes investigated by electrochemistry

The interaction of polyamidoamine (PAMAM) dendrimers (generations 1-7) with supported bilayer lipid membranes was studied by cyclic votammetry and ac impedance. It is shown that the dendrimers (generations 4-6) can induce defects in the Pt-electrode-supported bilayer lipid membrane. The ability of dendrimers to induce defects was dependent on their shapes and surface charge. The results are consistent with a change in the morphology of the dendrimers from an open, branched structure for generations 1-4 to a closed, increasingly compact surface for generations 5-7.

Electrochemical and Raman studies of the biointeraction between Escherichia coli and mannose in polydiacetylene derivative supported on the self-assembled monolayers of octadecanethiol on a gold electrode

Here, we describe a new method to study the biointeraction between Escherichia coli and mannose by using supramolecular assemblies composed of polydiacetylene supported on the self-assembled monolayer of octadecanethiol on a gold electrode. These prepared bilayer materials simply are an excellent protosystem to study a range of important sensor-related issues. The experimental results from UV-vis spectroscopy, resonance Raman spectroscopy, and electrochemistry confirm that the specific interactions between E. coli and mannose can cause conformational changes of the polydiacetylene backbone rather than simple nonspecific adsorption. Moreover, the direct electrochemical detection by polydiacetylene supramolecular assemblies not only opens a new path for the use of these membranes in the area of biosensor development but also offers new possibilities for diagnostic applications and screening for binding ligands.

In situ analysis of electropolymerization of aniline by combined electrochemistry and surface plasmon resonance

The combination of electrochemistry with surface plasmon resonance (SPR) has been used to characterize the growth of polyaniline (PAn) on a gold electrode surface during potential cycling. Potential-modulated SPR characteristics of the PAn film were also revealed. The potential switch between the oxidized and reduced states of PAn can lead to a large change of SPR response due to the variation in the imaginary part of the dielectric constant of PAn film resulting from the transition of the film in conductivity. The redox transition of the PAn film during potential cycling is very profitable to the SPR measurements. Two modes of SPR measurement, SPR angular scan (R-theta) and the time evolution of the reflectivity change at a fixed angle (R-t), were displayed to study the growth process of the PAn film. The angle shift of the resonance minimum recorded at each cathodic limit of cyclic potential scanning allows for the unambiguous measurement of the film growth. During cyclic potential scanning, the R-t curve was repeatedly modulated with the direction of the potential ramp as a result of the redox switch of the PAn film, and the amplitude of potential-modulated reflectivity change was well correlated with the cyclic number. The time differential of the R-t curve permits continuous monitoring of the film growth process. These results illustrate that the combined technique is suitable for studying the electropolymerization process of a conducting polymer.

Grafting of diaminoalkane on glassy carbon surface and its functionalization

Diaminoalkanes (NH2(CH2)(n)NH2, n = 7,10,12) were grafted onto a glassy carbon electrode (GCE) surface by amino cation radical formed during electrooxidation of amino group. The presence of diamine grafted layer at the GCE is demonstrated by X-ray photoelectron spectroscopy. The effect of the grafted layer at the GCE surface on the redox responses of Ru(NH3)(6)(3+) and Fe(CN)(6)(3-) redox probes has been investigated. Electrochemical impedance experiments indicate that the kinetics of electron transfer are slowed down when the scan rate taken to modify the GCE is low, and that diaminoalkane with longer alkyl-chain used has higher blocking characteristics. The amine-functionalized GCE is versatile not only to further covalently immobilize ferrocene acetic acid via carbodiimide coupling, but also as a charge-rich substrate to successfully adsorb heteropolyanion P2W18 in acidic solution by electrostatic interaction. (C) 2000 Elsevier Science S.A. All rights reserved.

Preparation, structures, and electrochemistry of a new polyoxometalate-based organic/inorganic film on carbon surfaces

The preparation, structure, and electrochemical and electrocatalytical properties of a new polyoxometalate-based organic/inorganic film, composed of cetyl pyridinum 11-molybdovanadoarsenate (CPMVA) molecules, have been studied. Cyclic potential scanning in acetone solution led to a stable CPMVA film formed on a highly oriented pyrolytic graphite (HOPG) surface. X-ray photoelectron spectroscopy, scanning tunneling microscopy, and cyclic voltammetry were used for characterizing the structure and properties of the CPMVA film. These studies indicated that self-aggregated clusters were formed on a freshly cleaved HOPG surface, while a self-organized monolayer was formed on the precathodized HOPG electrode. The CPMVA film exhibited reversible redox kinetics both in acidic aqueous and in acetone solution, which showed that it could be used as a catalyst even in organic phase. The CPMVA film remained stable even at pH > 7.0, and the pH dependence of the film was much smaller than that of its inorganic film (H4AsMo11VO40) in aqueous solution. The CPMVA film showed strong electrocatalysis on the reduction of bromate, and the catalytic currents were proportional to the square of the concentration of bromate. The new kind of polyoxometalate with good stability may have extensive promise in catalysis.

Self-assembled monolayer of polyoxometalate on gold surfaces: Quartz crystal microbalance, electrochemistry, and in-situ scanning tunneling microscopy study

A new kind of inorganic self-assembled monolayer (SAM) was prepared by spontaneous adsorption of polyoxometalate anion, AsMo11VO404-, onto a gold surface from acidic aqueous solution. The adsorption process, structure, and electrochemical properties of the AsMo11VO404- SAM were investigated by quartz crystal microbalance (QCM), electrochemistry, and scanning tunneling microscopy (STM). The QCM data suggested that the self-assembling process could be described in terms of the Langmuir adsorption model, providing the value of the free energy of adsorption at -20 KJ mol(-1). The maximum surface coverage of the AsMo11VO404- SAM on gold surface was determined from the QCM data to be 1.7 x 10(-10) mol cm(-2), corresponding to a close-packed monolayer of AsMo11VO404- anion. The analysis of the voltammograms of the AsMo11VO404- SAM on gold electrode showed three pairs of reversible peaks with an equal surface coverage of 1.78 x 10(-10) mol cm(-2) for each of the peaks, and the value was agreed well with the QCM data. In-situ STM image demonstrated that the AsMo11VO404- SAM was very uniform and no aggregates or multilayer could be observed. Furthermore, the high-resolution STM images revealed that the AsMo11VO404- SAM on Au(lll) surface was composed of square unit cells with a lattice space of 10-11 Angstrom at +0.7 V (vs Ag\AgCl). The value was quite close to the diameter of AsMo11VO404- anion obtained from X-ray crystallographic study. The surface coverage of the AsMo11VO404- SAM on gold electrode estimated from the STM image was around 1.8 x 10(-10) mol cm(-2), which was consistent with the QCM and electrochemical results.

Paint-freeze method to form self-assembled alkanethiol/phospholipid bilayers on gold

A paint-freeze method for preparing self-assembled alkanethiol/phospholipid bilayers on a gold surface has been described (by cyclic voltammetry, a.c impedance, polarized FTIR-ATR) to be well-ordered and packed, stable, solvent-free bilayers. The lipid order parameter was 0.67, calculated from the dichroic ratio, consistent with a well-ordered lipid film in which the methylene groups have segmental flexibility and are disordered to a degree which is typical for a lipid bilayer in the liquid-crystalline phase. Such a supported membrane provides a useful way for studies in biophysics, physiology and electrochemistry.

Electrochemistry of vanadium hexacyanoferrate film

Two stable redox couples, accompanying clear color switches between yellow green and blue, can be observed when the VHCF-coated film platinum electrodes are cyclic potential scanned in 3.6 M H2SO4 and 0.2 M K2SO4 electrolyte solution. Electrochemical results and in situ Fourier transfer infrared (FT-IR) spectroscopy demonstrate that the redox reaction of the electroactive iron sites is related to the first redox couple (E-1/2 = 0.81 V) while the second redox couple (E-1/2 = 1.01 V) is due to the redox reactions of the electroactive vanadyl ions. Under the proper conditions, such as in high acidic solutions or thin films (deposition time is less than 2 min) and so on, the third redox couple (E-1/2 = 0.89-0.94 V) can be observed on the cyclic voltammograms, which originates from the redox reactions of the interstitial vanadyl ions. This electrochemical reaction mechanism is investigated by in situ probe beam deflection technique, exchange of K+ ions accompanies with redox reaction of the iron sites, but for redox reaction of the vanadyl ions, both H+ ions, K+ ions and water molecules are involved.

Structure and impedance of ZrO2 doped with SC2O3 and CeO2

Scandia and ceria doped zirconia samples, with 10 mol% SC2O3 and different content of CeO2, were synthesized and characterized. The XRD results depict that the sintered samples have a cubic phase structure. However, Raman spectra show that besides the main cubic phase, a secondary phase is also present in the sintered samples. The addition of CeO2 can raise the content of the cubic phase, but the minor metastable tetragonal phase (t'-phase) exists even at the CeO2 content as high as 10 mol%. The near-UV Raman spectra indicate that the deformed tetragonal structure predominates at the grain boundary. The addition of CeO2 can reduce the impurity at grain boundary, and no impurity can be found by near-UV Raman spectroscopy at the grain boundary of the samples with high CeO2 content. The impedance measurements show that with the increase of CeO2 content, the impedance of grain boundary decreases and the bulk impedance increases. The low impedance of grain boundary can be attributed to the formation of a clean grain boundary upon CeO2 doping, and the increase of the bulk impedance is due to the blocking effect of the large Ce(IV) ions. (c) 2005 Elsevier B.V All rights reserved.

A study of the oxygen electrochemistry of ruthenium and iridium

This thesis is concerned with an investigation of the anodic behaviour of ruthenium and iridium in aqueous solution and particularly of oxygen evolution on these metals. The latter process is of major interest in the large-scale production of hydrogen gas by the electrolysis of water. The presence of low levels of ruthenium trichloride ca. 10-4 mol dm-3 in acid solution give a considerable increase in the rate of oxygen evolution from platinum and gold, but not graphite, anodes. The mechanism of this catalytic effect was investigated using potential step and a.c. impedance technique. Earlier suggestions that the effect is due to catalysis by metal ions in solution were proved to be incorrect and it was shown that ruthenium species were incorporated into the surface oxide film. Changes in the oxidation state of these ruthenium species is probably responsible for the lowering of the oxygen overvoltage. Both the theoretical and practical aspects of the reaction were complicated by the fact that at constant potential the rates of both the catalysed and the uncatalysed oxygen evolution processes exhibit an appreciable, continuous decrease with either time or degree of oxidation of the substrate. The anodic behaviour of iridium in the oxide layer region has been investigated using conventional electrochemical techniques such as cyclic voltammetry. Applying a triangular voltage sweep at 10 Hz, 0.01 to 1.50V increases the amount of electric charge which the surface can store in the oxide region. This activation effect and the mechanism of charge storage is discussed in terms of both an expanded lattice theory for oxide growth on noble metals and a more recent theory of irreversible oxide formation with subsequent stoichiometry changes. The lack of hysteresis between the anodic and cathodic peaks at ca. 0.9 V suggests that the process involved here is proton migration in a relatively thick surface layer, i.e. that the reaction involved is some type of oxide-hydroxide transition. Lack of chloride ion inhibition in the anodic region also supports the irreversible oxide formation theory; however, to account for the hydrogen region of the potential sweep a compromise theory involving partial reduction of the outer regions of iridium oxide film is proposed. The loss of charge storage capacity when the activated iridium surface is anodized for a short time above ca. 1.60 V is attributed to loss by corrosion of the outer active layer from the metal surface. The behaviour of iridium at higher anodic potentials in acid solution was investigated. Current-time curves at constant potential and Tafel plots suggested that a change in the mechanism of the oxygen evolution reaction occurs at ca. 1.8 V. Above this potential, corrosion of the metal occurred, giving rise to an absorbance in the visible spectrum of the electrolyte (λ max = 455 nm). It is suggested that the species involved was Ir(O2)2+. A similar investigation in the case of alkaline electrolyte gave no evidence for a change in mechanism at 1.8 V and corrosion of the iridium was not observed. Oxygen evolution overpotentials were much lower for iridium than for platinum in both acidic and alkaline solutions.

Electrochemistry of Hg(II) Salts in Room-Temperature Ionic Liquids

The electrochemistry of HgCl(2) and [Hg(NTf(2))(2)] ([NTf(2)](-) = bis-{(trifluoromethyl)sulfonyl}imide) has been studied in room temperature ionic liquids. It has been found that the cyclic voltammetry of Hg(II) is strongly dependent on a number of factors (e.g., concentration, anions present in the mixture, and nature of the working electrode) and differs from that found in other media. Depending on conditions, the cyclic voltammetry of Hg(II) can give rise to one, two, or four reduction peaks, whereas the reverse oxidative scans show two to four peaks. Diffuse reflectance UV-vis spectroscopy and X-ray powder diffraction have been used to aid the assignment of the voltammetric waves.

Combined studies of DFT atomistic modelling and in situ FTIR spectroscopy on surface oxidants and CO oxidation at Ru electrodes

We report the combined studies of density functional theory (DFT) calculations and electrochemical in situ FTIR spectroscopy on surface oxidants and mechanisms of CO oxidation at the Ru(0001) electrodes. It is shown that CO can co-adsorb with both O and OH species at lower potential region where a low coverage of the (2 x 2)-O/OH adlayer formed; the oxidation of CO adsorbates takes place at higher potentials where a high coverage of the (1 x 1)-O/OH adlayer formed. Surface O species are not the active oxidants under all coverages studied, due to the high reaction barriers between CO and O (>1 eV). However, surface OH species with higher coverage are identified as the active oxidants, and CO oxidation takes place via a two-steps' mechanism of CO + 3OH -> COOH + 2OH -> CO2 + H2O + OH, in which three nearby OH species are involved in the CO2 formation: CO reacts with OH, forming COOH; COOH then transfers the H to a nearby OH to form H2O and CO2, at the same time, another H in the H2O transfers to a nearby OH to form a weak adsorbed H2O and a new OH. The reaction barrier of these processes is reduced significantly to around 0.50 eV. These new results not only provide an insight into surface active oxidants on Ru, which is directly relevant to fuel cell catalysis, but also reveals the extra complexity of catalytic reactions taking place at solid/liquid electrochemical interface in comparison to the relatively simpler ones at solid/gas phase.