Electrochromism viologens

Examples of electrochromic polymers bearing perfluoro chains (poly(54)) [147], dendrons (poly(170)), or viologen groups, e.g., (poly(171)) [150] have been reported. In this later case, introduction of a second electrochromic viologen pendant group increases the contrast between the oxidized and the neutral states. 

Metal Oxide Electrochromism Viologen Electrochromism Prussian Blue Electrochromism Conducting Polymer Electrochromism... 

The divalent cation methyl viologen is highly colored in reduced form and is used as an electrochromic in solution cells (Eig. 11). 

The added electron is delocalized on the monovalent radical ion to which it is reduced (3). There is no general agreement on the molecular representation of the reduced stmcture. Various other viologen compounds have been mentioned (9,12). Even a polymeric electrochromic device (15) has been made, though the penalty for polymerization is a loss in device speed. Methylviologen dichloride [1910-42-5] was dissolved in hydrated... 

Organic Molecules It can be seen from our earlier discussion that the presence of a transition metal ion is not always required for an electrochromic effect. Indeed, many organic molecules can yield colored products as a result of reversible reduction or oxidation. 4,4 -Bipyridinium salts are the best known example of such compounds. These compounds can be prepared, stored, and purchased in colorless dicationic form (bipm +). One electron reduction of the dication leads to the intensely colored radical cation (bipm+ ). Such radical cations exist in equilibrium with their dimers (bipm ). In the case of methyl viologen, the radical cation is blue and the dimer is red. By varying the substient group in the molecule, different colors can be obtained. 

Metallopolymer films have also been prepared by oxidative polymerization of complexes of the type [M(phen)2(4,4 -bipy)2]2+ (M = Fe, Ru, or Os phen= 1,10-phenanthroline, 4,4 -bipy = 4,4 -bipyridine).23 Such films are both oxidatively and reductively electrochromic reversible film-based reduction at potentials below —IV lead to dark purple films,23 the color and potential region being consistent with the viologen dication/radical cation electrochromic response. A purple state at high negative potentials has also been observed for polymeric films prepared from [Ru(L13)3]2+.24 Electropolymerized films prepared from the complexes [Ru(L16)-(bipy)2][PF6]22 and [Ru(L17)3][PF6]226,27 exhibit reversible orange/transparent electrochromic behavior associated with the Run/Ruin interconversion. 

The author was brought up in Hastings, on England s south coast, where he attended a local comprehensive school. Despite this education, he achieved entrance to the University of Exeter to read Chemistry. Having obtained a B.Sc. degree and then a doctorate (in 1989) on the electrochemistry of the viologens, he was awarded a fellowship at the University of Aberdeen to study the electrochromism of thin films of tungsten trioxide. 

He enjoys writing, and is also the author of the books Electrochromism Fundamentals and Applications and The Viologens, both of these published by John Wiley Sons. 

For instance, inclusion of l,T-dimethyl-4,4 -dipyridyl cation-radical (the cation-radical of methyl viologen) into a cavity of sulfocalixarenes prevents the disadvantageous n dimerization. This is important for more effective use of viologens as components of electrochromic displays and electric condnctors (Gno et al. 2007, references therein). 

This type of electrochrome, in its pale or colourless state, is soluble in the electrolyte. However, on electron transfer, the coloured form of the electrochrome that is produced is insoluble and is deposited onto the surface of an electrode. Viologens with hydrophobic chains, such as heptyl (1.90 R = form deeply coloured radical... 

Figure 6.38 Electron flow diagram of the switching processes that take place for an electrochromic window based on viologen/Ti02 and phenothiazine/Sn02-Sb modified electrodes. Reprinted with permission from D. Cummins, G. Boschloo, M. Ryan, D. Corr, S. N. Rao and D. Fitzmaurice, /. Phys. Chem., B, 104, 11449 (2000). Copyright (2000) American Chemical Society...

Electrochromic materials are of three basic types [i]. In a given -> electrolyte solution, type I materials are soluble in both the reduced and oxidized (redox) states, an example being l,l -di-methyl-4,4 -bipyridylium ( methyl viologen ), which, on reduction, switches from the colorless di-cation to the blue radical cation. Type II materials are soluble in one redox state, but form a solid film on the surface of an electrode following electron transfer. An example here is l,l -di-heptyl-4,4 -bipyridylium ( heptyl viologen ). In type III materials, such as -> tungsten oxide, - Prussian blue, and electroactive conjugated polymers, both... 

The properties of benzothiazolinone azine redox systems have been studied with a view to their practical applications Shelepin and co-workers studied a mixed system involving 3-ethylbenzothiazolin-2-one azine and methyl viologen as an electrochromic system activated by optically transparent electrodes Sharp has described perchlorate-sensitive electrodes also involving 3-ethylbenzothiazolin-2-one azine solid-state electrical properties of salts of the 3-methylbenzothiazolin-2-one azine radical-cation have been reported. ... 

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