Erratum: Redox-induced reversible metal assembly through translocation and reversible ligand coupling in tetranuclear metal sandwich frameworks
Tetsuro MurahashiKatsunori ShiratoAzusa FukushimaKohei TakaseTomoyoshi SuenobuShunichi FukuzumiSensuke OgoshiHideo Kurosawa
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In this article, novel experiments on the topic of redox reactions are presented. These reactions take place in small sodium alginate beads, containing some of the reactants. By immersing the beads in various solutions, the pH-dependence of the redox potentials of some redox systems and different redox states can be visualized by eye.
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This chapter contains sections titled: Solvent Effects on Various Types of Redox Reactions Fundamentals of Redox Reactions Solvent Effects on Redox Potentials and Redox Reaction Mechanisms Dynamical Solvent Effects on the Kinetics of Redox Reactions Redox Properties of Solvents and Potential Windows Redox Titrations in Non-Aqueous Solutions Titrations with Oxidizing Agents Titrations with Reducing Agents
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Electrochemical signals may be affected by the presence of iron oxide magnetic particles (MPs) on an electrode owing to their distinct magnetic and redox properties. Recognizing their significance in electrochemical detection, we investigated the changes in electrochemical signals in the presence of MPs and their underlying causes. In the presence of MPs, the cyclic voltammograms of (quasi)reversible redox species (e.g., Fe(CN)64– and Ru(NH3)63+) exhibit different current-enhancing behaviors, depending on their formal potentials. Several redox species, such as Fe(CN)63– and Os(2,2′-bipyridyl)2Cl2, display non-zero initial currents at non-oxidizing or -reducing applied potentials in the presence of MPs. These findings are primarily attributed to the rapid redox reaction between the redox species and MP rather than the enhancement of mass transfer via magnetoconvection. The reaction between a redox species and an MP leads to a positive or negative shift in the equilibrium potential of the MP, which depends on the formal potential of the redox species. This enables MPs to act as adaptable, reversible redox reservoirs, facilitating current enhancement via redox cycling involving the MPs at specific potentials or during anodic and cathodic scanning. We applied signal enhancement via redox cycling to electrochemical Cu2+ detection. Cu2+ is rapidly reduced to Cu+ by the MPs during incubation, and Cu+ is then measured by using redox cycling. The calculated detection limit is approximately 15 nM, which is ∼100-fold lower than that observed without using MPs.
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Phthalonitrile
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Half-reaction
Electron exchange
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The significance of Schiff base (SB) to form metal complexes is its capability to stabilize metal ions in various oxidation states. Mononuclear metal complex of a SB ligand can be synthesized by taking one mole of metal salt with that of 1 mol of ligand to form mononuclear metal complex of a single ligand. Dinuclear metal complex of a SB ligand can be synthesized by considering metal to ligand in the ratio 2:1 to form dinuclear metal complex of a single ligand. Titanium complexes can form octahedral and dodecahedral complexes with SB ligands depending on the presence of donor atoms in the ligand. Copper metal can form tetrahedral, square planar, and octahedral metal complexes depending upon the presence of donor atoms present in the ligand, number of donor atoms, and the ratio of ligand used to synthesize metal complexes.
Non-innocent ligand
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Redox titration
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A procedure for the estimation of the redox potentials of chemically (or electrochemically) irreversible couples based on optical measurements and on the Marcus and Hush equations has been proposed and tested through the determination of redox potentials of different Co(NH3)5L3+/2+ redox couples. The results are in agreement with the expectations based on the reactivity of these complexes.
Reactivity
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Phthalonitrile
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The fluorescence emission switching behavior based on the redox reaction of quinone-Eu complexes was investigated. The addition of caused positive shifts in the potential and induced a fully irreversible two-electron redox reaction around 0.2 V, which is similar to that of the proton. In the presence of the redox reaction of quinones takes place accompanied by ion transfer, and the redox activation efficiency of is 100 times greater than that of the proton. The emission is investigated by complexation with the hydroquinone. Here, we show that we first found this fluorescence switching based on the redox reaction of the benzoquinone-hydroquinone exchange. © 2004 The Electrochemical Society. All rights reserved.
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