Update 1 of: Electrochemical Approach to the Mechanistic Study of Proton-Coupled Electron Transfer

Costentin, Cyrille; Robert, Marc; Savéant, Jean‐Michel

doi:10.1021/cr100038y

Cited by 169 publications

(161 citation statements)

References 345 publications

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“…At first sight, the answer is expected to be positive by reference to CPET reactions with no heavy-atom bond breaking where small but significant (of the order of 2) H/D kinetic isotope effects are commonly observed (8)(9)(10)28). There is, however, an important difference between these reactions and the present ones, namely the large irreversibility caused by the breaking of the heavy-atom bond, as pictured in Fig.…”

Section: Resultsmentioning

confidence: 81%

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Concerted heavy-atom bond cleavage and proton and electron transfers illustrated by proton-assisted reductive cleavage of an O–O bond

Costentin

Hajj

Robert

et al. 2011

Proc. Natl. Acad. Sci. U.S.A.

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Electron transfer may be concerted with proton transfer. It may also be concerted with the cleavage of a bond between heavy atoms. All three events may also be concerted. A model is presented to analyze the kinetics of these all-concerted reactions for homogeneous or electrochemical reduction or oxidation processes. It allows the estimation of the kinetic advantage that derives from the increase of the bond-breaking driving force resulting from the concerted proton transfer. Application of the model to the electrochemical reductive cleavage of the O–O bond of an organic peroxide in the presence of a proximal acid group illustrates the applicability of the model and provides an example demonstrating that electron transfer, heavy-atom bond breaking, and proton transfer may be all concerted. Such analyses are expected to be useful for the invention, analysis, and optimization of reactions involved in contemporary energy challenges as well as for the comprehension of major biochemical processes, a number of which involve electron and proton transfer together with cleavage of bonds between heavy atoms.

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Section: Resultsmentioning

confidence: 81%

“…In this framework, uncovering the mechanisms and modeling the kinetic characteristics of these reactions has attracted and continues to attract a great deal of attention concerning both heavy-atoms bonds (2-4) and proton transfers (5)(6)(7)(8)(9)(10)(11). As pictured in Fig.…”

mentioning

confidence: 99%

Concerted heavy-atom bond cleavage and proton and electron transfers illustrated by proton-assisted reductive cleavage of an O–O bond

Costentin

Hajj

Robert

et al. 2011

Proc. Natl. Acad. Sci. U.S.A.

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“…The entire electrochromic process presumably involves a triple-electron-coupled proton transfer, which is summarized in a potential-proton diagram 45 (Figure 7). This diagram, which is commonly referred to as a Pourbaix diagram, expresses the relationship of protonated species and various redox.…”

Section: Design and Synthesis Of The Switchable Moleculementioning

confidence: 99%

A single-molecule multicolor electrochromic device generated through medium engineering

et al. 2015

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Multicolor organic electrochromic materials are important for the generation of full-color devices. However, achieving multiple colors using a single-molecule material has proved challenging. In this study, a multicolor electrochromic prototype device is generated by integrating medium engineering/in situ 'electro base'/laminated electrode technologies with the simple flying fish-shaped methyl ketone TM1. This multicolor electrochromic (green, blue and magenta) device is durable and has a high coloration efficiency (350 cm 2 C 21 ), a fast switching time (50 ms) and superior reversibility. This study is a successful attempt to integrate solvatochromism and basochromism in an electronic display. This integration not only introduces a new avenue for color tuning, in addition to the structural design of the colorant, but will also inspire further developments in the tuning of many other properties by this medium engineering approach, such as conductance and the redox property, and thereby accelerate versatile applications in data recording, ultrathin flexible displays, and optical communication and sensing. Keywords: electrochromic materials; laminated electrodes; microenvironment; multicolor devices; solvatochromic materials INTRODUCTION Owing to the increasing demand for low-power, ultrathin, flexible electronic displays, organic electrochromic materials 1-3 have become a research focus because of their distinct merits: low weight, high contrast, wide viewing angle, flexibility and the potential for low power consumption. Because the realization of a multicolor switch is preferred in the majority of their applications in displays, 4-10 various electrochromic materials including polymers, 11,12 small organic molecules 13,14 and metal-organic complexes, 15 and technologies aimed at multicolor switches have been intensively explored. Transition metals based on metal-organic complex multicolor electrochromic materials exhibit attractive properties, such as high stability and chemiluminescence. 16 However, the expense and scarcity of the precious metals, such as ruthenium, 15,16 osmium 17 and iridium, 18 limit their practical applications. Polymeric multicolor electrochromic materials with different electrochromic activation units [19][20][21] possess the advantages of easy processing, diverse resources and facile color tunability. However, some intrinsic problems, such as the lack of colorless states, poor transparency, poor color purity and complicated synthesis procedures, hinder their applications. Compared with electrochromic polymers, small organic color switches possess the advantages of low cost, good color purity, distinct transition from colorless to colored states and fine tunability of their photoelectronic properties via easy structure modifications. The lack of multicolor abilities is their intrinsic

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“…The associated E ri and k ri values are functions of pK ai 's and solution pH, of which equations can be found elsewhere. 8,21 The reduction potential and rate constant for the overall redox reaction are designated as E app and k app , and E app is the average of E r1 and E r2 .…”

mentioning

confidence: 99%

“…electrons and protons are transferred individually in kinetically distinct steps. However, there are increasing reports of concerted transfer of electron and proton, 8,35,36 and k app has been modified to take the concerted pathway into account.…”

mentioning

confidence: 99%

The Electrochemical Reaction Mechanism and Applications of Quinones

Kim¹,

Chung²

2014

Bulletin of the Korean Chemical Society

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This tutorial review provides a general account of the electrochemical behavior of quinones and their various applications. Quinone electrochemistry has been investigated for a long time due to its complexity. A simple point of view is developed that considers the relative stability of the reduced quinone species and the values of the first and second reduction potentials. The 9-membered square scheme in buffered aqueous solutions is explained and semiquinone radical stability is discussed in this context. Quinone redox reaction has also been employed in various studies. Diverse examples are presented under three broad categories defined by the roles of quinone: molecular tool for physical chemistry, versatile electron mediator, and charge storage for energy conversion devices.

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Update 1 of: Electrochemical Approach to the Mechanistic Study of Proton-Coupled Electron Transfer

Cited by 169 publications

References 345 publications

Concerted heavy-atom bond cleavage and proton and electron transfers illustrated by proton-assisted reductive cleavage of an O–O bond

Concerted heavy-atom bond cleavage and proton and electron transfers illustrated by proton-assisted reductive cleavage of an O–O bond

A single-molecule multicolor electrochromic device generated through medium engineering

The Electrochemical Reaction Mechanism and Applications of Quinones

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