Electrochrome Types

In the case of the coloured electrolyte type, the two complementary electrochromes are dissolved in the electrolyte between the transparent electrodes. One becomes coloured by oxidation and the other by reduction and consequently the electrolyte becomes coloured (see 1.5.2.1). The electrolyte remains coloured only whilst a current is being passed, becoming colourless once the charge is removed. 

The materials that change colour on passing a charge are called electrochromes, and these can be classified into three groups. In the first type the colouring species remain in solution in the second type the reactants are in solution but the coloured product is a solid the third type are those where all the materials are solids, e.g. in films. The first type is used in car, anti-dazzle, rear-view mirrors, the second type in larger mirrors for commercial vehicles and the third type in smart windows (see section 1.5.4.2). 

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The zirconia electrode served as a reference electrode not only for the platinum electrode measuring the oxygen fugacity of the melt, but also for the platinum contact of the ZS crucible during the reaction between ZS and melt and was also short-circuited with the ZS contact in order to change the course of the reaction. The study resulted in an electrochromic-type... 

Metal Oxides Tungsten trioxide, undoubtedly the most widely studied electrochromic material, is used in several types of commercial electrochromic devices. 

Other Inorganic Compounds Prussian Blue represents another type of inorganic mixed valence electrochromic materials. This material is known in three states ... 

It is important, however, to realize that whilst many types of chemical species exhibit electro-chromism, only those with favorable electrochromic performance parameters1 are potentially useful in commercial applications. Thus, most applications require electrochromic materials with a high contrast ratio, coloration efficiency, cycle life, and write-erase efficiency.1 Some performance parameters are application dependent displays need low response times, whereas smart windows can tolerate response times of up to several minutes. 

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. 

In the last few years McCleverty, Ward, and co-workers have reported the NIR electrochromic behavior of a series of mononuclear and dinuclear complexes containing the oxo-Mo(iv) v core unit [Mo(Tp )(0)Cl(OAr)], where Ar denotes a phenyl or naphthyl ring system [Tp = hydro-hydrotris(3,5-dimethylpyrazolyl)borate].184-189 Mononuclear complexes of this type undergo reversible MoIV/Mov and Mov/MoVI redox processes with all three oxidation states accessible at modest potentials. Whilst reduction to the MoIV state results in unremarkable changes in the electronic spectrum, oxidation to MoVI results in the appearance of a low-energy phenolate- (or naphtholate)-to-MoVI LMCT process.184,185... 

In addition, the integration of modem optical technology and electrochemical techniques for sensing applications appears to be a powerful new approach. A new type of optoelectrochemical sensor for chlorine, based on an electrochromic thin-film sensing layer placed on top of a planar waveguide, has demonstrated the applicability of this combined approach. 

Coordination compounds composed of tetrapyrrole macrocyclic ligands encompassing a large metal ion in a sandwich-like fashion have been known since 1936 when Linstead and co-workers (67) reported the first synthesis of Sn(IV) bis(phthalocyanine). Numerous homoleptic and heteroleptic sandwich-type or double-decker metal complexes with phthalocyanines (68-70) and porphyrins (71-75) have been studied and structurally characterized. The electrochromic properties of the lanthanide pc sandwich complexes (76) have been investigated and the stable radical bis(phthalocyaninato)lutetium has been found to be the first example of an intrinsic molecular semiconductor (77). In contrast to the wealth of literature describing porphyrin and pc sandwich complexes, re-... 

Stabilization of the redox cycle is relatively important in construction of potentially useful electrochromic materials, because the molecules needed for application require high redox-stability. Recently, S. Hiinig et al. proposed the concept of violene-cyanine hybrid to produce stabilized organic electrochromic materials (3). The hybrid is constructed by a violene-type redox system containing delocalized closed-shell polymethine dyes as end groups. The hybrid is expected to exhibit the color of a cyanine dye, by an overall two-electron... 

Figure 8.1 Beer s law-type plot of change in optical absorbance against charge density q for the cell WO3 polymer electrolyte Prussian Blue. Reprinted from Inaba, H Iwaka, M., Nakase, K., Yasukawa, H., Seo, I. and Oyama, N., Electrochromic display device of tungsten trioxide and Prussian Blue films using polymer gel electrolyte of methacrylate , Electrochim. Acta, 40, 227-232 (1995), Copyright 1995, with permission from Elsevier Science.

PB and its derivatives are of interest for a variety of reasons, the most important of which is its electrochromism [93]. In addition, it is an electrocatalyst for several different types of substrates, notably hydrogen peroxide, as will be seen below. Synthesis of nanopartides of Prussian Blue is relatively straightforward. It relies on many of the prindples of colloid chemistry, and produces ionically stabilized colloidal solutions (Figure 4.7). As a consequence, the electrochemical behavior of PB N Ps has been examined by several groups. In this section, we discuss the behavior of P B N Ps immobilized at electrodes. 

Dnring the process of colouration in electrochromic cells by passing a charge in one direction, a colour can form in one or both of the electrodes or in the electrolyte adjacent to the electrodes. When the colour is formed by reduction at a negative electrode it is called cathodic coloration and, conversely, at the anode it is anodic coloration. Two different types of cells are shown schematically in Figure 1.31. ... 

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... 

Several other organic systems have been stndied as potential electrochromes because of their redox behaviour. These include carbazoles, methoxybiphenyls, fluorenones, benzoquinones, naphthaquinones and anthraqninones, tetracyanoquinodimethane, tetrathiafnlvalene and pyrazolines. ° Of particnlar interest are the 1,4-phenylenedi-amines, which form highly colonred species on oxidation. These, known as Wurster s salts, exemplified by Wnrster s Bine (1.97), are anodically colouring and this type of material has found nse in composite electrochromic systems for car rearview mirrors (see 1.5.4.1). 

Electrochromic materials of interest can be classified according to three types of color change (1) from a bleached state (transparent) to a colored state, (2) between two colored states, and (3) between several colored states, if more than two redox states are accessible. This behavior is called polyelectrochromic... 

Stability tests performed in sandwich-type cells containing the dyes adsorbed on Sn02/Sb electrodes demonstrated a high stability, with optical density changes lower than 2% after cycling the electrochromic device 20000 times between -0.5 and +0.5 V. 

In the most important series of polymers of this type, the metallotetraphenylporphyrins, a metalloporphyrin ring bears four substituted phenylene groups X, as is shown in 7.19. The metals M in the structure are typically iron, cobalt, or nickel cations, and the substituents on the phenylene groups include -NH2, -NR2, and -OH. These polymers are generally insoluble. Some have been prepared by electro-oxidative polymerizations in the form of electroactive films on electrode surfaces.79 The cobalt-metallated polymer is of particular interest since it is an electrocatalyst for the reduction of dioxygen. Films of poly(trisbipyridine)-metal complexes also have interesting electrochemical properties, in particular electrochromism and electrical conductivity.78 The closely related polymer, poly(2-vinylpyridine), also forms metal complexes, for example with copper(II) chloride.80... 

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