Chromic Phenomena

The Technological Applications

of Colour Chemistry

Peter Bamfield
Consultant
ISBN 0-8404-474-4

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Contents iii

CHAPTER 1

Phenomena Involving a
Reversible Colour Change

1.1 Introduction
Any changes in the colour of an object, whether this is from white to black, colour-
less to coloured or from one colour to another, can be easily detected by the human
eye or by using simple spectrophotometric instruments. Such changes in colour
therefore provide very important visual signals that can be used to convey useful
information to an observer, the most obvious being traffic control signals. In
addition, by selective absorption or transmission of light by a material, it is possible
to restrict the light energy impinging upon an observer, as experienced with the
darkened glass in sun spectacles. When a third parameter is introduced, namely an
external stimulus, whether this is chemical or physical, that causes the change
of colour or the restriction of light transmission, especially when this change is
reversible, the potential applications significantly widen. Consequently, research
into chemicals that undergo reversible changes in colour upon the application
of an external stimulus has been extensive, and the products of this work have found
uses in a wide variety of outlets, in both low and high technology areas.
These colour change phenomena are classified and named after the stimulus that
causes the change. Accordingly, photochromism is a change in colour, usually
colourless to coloured, brought about normally by UV light, electrochromism is a
reversible colour change upon oxidation or reduction brought about by an electrical
current or potential, thermochromism is a colour change brought about by heat,
solvatochromism by solvents and ionochromism by ions, etc. A list of these and other
phenomena are given in Table 1.1, together with a selection of the many areas where
they have found application. The most important commercially of these phenomena,
namely photochromism, thermochromism, electrochromism and ionochromism, will
be covered in some detail in the sections below.

1.2 Photochromism
Photochromism is a chemical process in which a compound undergoes a reversible
change between two states having separate absorption spectra, i.e. different colours.
The change in one direction occurs under the influence of electromagnetic radiation,

7
8 Chapter 1
Table 1.1 Colour change phenomena and their applications
Phenomena Stimulus Applications
Photochromism Light Ophthalmic lenses, novelty printing, security
printing, cosmetics, optical data storage, memo-
ries and switches, sensors
Thermochromism Heat (intrinsic Thermochromic pigments, temperature indicators
and indirect) and thermometers, security and novelty printing
Electrochromism Electrical current Windows, mirrors, displays
Solvatochromism Solvent polarity Analysis, sensors, monitoring of polymers and
polymerisation
Ionochromism Ions Colour formers, thermal fax papers, indicators,
metal ion detection
(Halochromism) (pH change) (ditto)
Tribochromism Mechanical friction
Piezochromism Mechanical pressure

usually UV light, and in the other direction by altering or removing the light source
or alternatively by thermal means.
Usually the change in colour in the forward direction is to longer wavelength, i.e.
bathochromic, and reversibility of this change is key to the many uses of photo-
chromism. In many systems, e.g. spiropyrans, spirooxazines and chromenes, the
back reaction is predominantly thermally driven but in others the photochemically
induced state is thermally stable and the back reaction must be driven photo-
chemically (e.g. fulgides and diarylethenes). The assistance of heat in the reversion
of colour can be regarded as an example of thermochromism, but in this text the term
is reserved for those systems where heat is the main cause of the colour change (see
section 1.3).
Photochromism is a vast field and in this section of the book we will cover only the
main classes of photochromic compounds and their synthesis and then go on to
describe the current commercial applications for these materials and also some of a
more speculative nature. For more detailed accounts the reader should consult
the books on photochromics edited by Crano and Guglielmetti 1,2 and Durr and
Bouas-Laurent.3

1.2.1 Main Chemical Classes

The ideal properties required from any class of organic photochromic compounds are

1. Colour development. The material must develop rapidly a strong colour upon
irradiation with UV light
2. Control of return back to colourless state. The fade rate back to the colourless
state must be controllable
3. Wide colour range. The range of colours must be across the visible spectrum
4. Long life. The response must be constant through many colouration cycles
5. Colourless rest state. The colourless rest state must have as little colour as
possible, preferably colourless
Phenomena Involving a Reversible Colour Change 9
There are five main classes of compounds which can approach these ideal require-
ments; spiropyrans, specifically spiroindolinobenzopyrans, spironaphthoxazines,
naphthopyrans, fulgides and diarylethenes.

1.2.2 Spirobenzopyrans
Spirobenzoyrans are a very widely studied chemical class of compounds which
exhibit photochromism. They consist structurally of a pyran ring, usually a 2H-1-
benzopyran, linked via a common spiro group to another heterocyclic ring, e.g. (1.1).
Irradiation of the colourless spirobenzopyran (1.1) with UV light causes heterolytic
cleavage of the carbon–oxygen bond forming the ring-opened coloured species,
often called the ‘merocyanine’ form, which can be either cis-(1.2) or trans-(1.3), or
the ortho-quinoidal form represented by (1.4) in Figure 1.1. In fact the structure of
the ring-opened form is probably best represented by a delocalised system with par-
tial charges on nitrogen and oxygen atoms. For simplicity’s sake we will use the
equivalent of the trans-merocyanines structure (1.3) in this text.

H3C CH3 H3C CH3

N O N+ -O

CH3 CH3

(1.1) (1.2)
Colourless Coloured

H3C H3CCH3
CH3 -O
O

N
CH3

(1.4)

1.2.3 Spironaphthoxazines
Spirooxazines, the nitrogen containing analogues of the spiropyrans, are very resist-
ant to photodegradation This resistance to photodegradation, known in this field as
fatigue resistance, is an essential property for those photochromic materials designed
for applications in solar protection uses, e.g. in sun spectacles. The photochromic
ring opening of a spironaphthoxazine derivative to its coloured form is shown in
Figure 1.3.
H3C CH3
H3C CH3
N

N O
CH3 N N

CH3
O

Colourless Coloured (+ isomers)

Figure 1.3 Spironaphthoxazine photochromic
forms
10 Chapter 1
1.2.4 Benzo and Naphthopyrans (Chromenes)
The photochromic compounds of potential interest, based on the 2H-chromene ring
system, are the 2H-benzopyrans (1.18) or the three isomeric naphthopyrans (1.19–
1.21). However, 2H-naphtho[2,3-b]pyrans (1.21) show little or no useful
photochromic behaviour and can be discounted from any further discussion.
Although R1 and R2 can be part of a carbocyclic spiro ring, they are more commonly
unconnected substituents such as gem dialkyl or aryl groups.

R1
O
R2 R1
(1.18) O
R2
(1.19)

R1
O
R2 R1
O
R2
(1.20) (1.21)

The photochromic mechanism for the chromenes is very similar to that for
spiropyrans given in Figure 1.1. Under the influence of UV the C–O bond in the
pyran ring is broken to give either the zwitterionic form or, more likely, the cis- and
trans-quinoidal forms (Figure 1.6). Studies suggest that formation of the cis-
quinoidal species occurs in picoseconds, followed by generation of the trans-form in
nanoseconds.
The two naphthopyrans of interest (1.19) and (1.20) show quite different pho-
tochromic behaviour. Isomer (1.20; R1, R2 = Ph) produces a more bathochromic
coloured state than (1.19; R1, R2 = Ph), (max = 481 nm versus 432 nm), a large

h

heat
O O

O
O
trans-quinoidal cis-quinoidal
Figure 1.6 Photochromic behavior of chromenes.
increase in coloration, but a very slow fade rate back to the colourless state.9 Because
of the slow kinetics, coupled with a greater ease in synthesis, most of the work,
until the mid-1990s when these problems were overcome, concentrated on the 3H-
Phenomena Involving a Reversible Colour Change 11
naphtho[2,1-b]pyrans (1.19).

Cl Cl
O
OH

(1.30; X = NR 2 or OR)
Figure 1.9 Synthetic route to 6-amino and 6-alkoxy-3,3-diaryl-3H-naphtho[2,1-b]pyrans.
(Reproduced with permission of Kluwer Academic/Plenum Publishers.

1.2.5 Fulgides
Stobbe was the first to observe photochromism in fulgides (1.33) when he synthe-
sised them by the condensation of an arylaldehyde or ketone with a substituted
methylene succinate.15 However, it was not until the 1970s, during the course of the
extensive work carried out by Heller and his collaborators, that their chemistry and
use in photochromism was truly exploited.16,17 Heller’s work showed, amongst many
other things, the importance of R1 in (1.33) being a 5-membered ring heterocycle,
e.g. furan.
Fulgides can exist as E or Z isomers by rotation around the double bonds in (1.33).
This is illustrated for the furano derivative in Figure 1.10. Isomerisation of the yel-
low Z-fulgide (1.34) to the E-fulgide (1.35) and cyclisation of this to the red coloured
photochrome (1.36), designated as C here but often called the P state, occurs on irra
diation with UV light. The coloured species (1.36) is converted back into the E-
fulgide (1.35) by white light but not by heat. Thermally assisted reversion of
coloured to colourless is not observed, because the interactions between the two syn
methyl groups prevent the symmetry allowed, disrotatory mode of opening of the
electrocyclic ring from occurring.18 Since both the forward and back reactions
require light energy it is important that they both show good quantum yields.
-
 12 Chapter 1

CO2CH2CO2CH2CH3

H3C

(1.31)

H3C H3C CH3

OH

R1
O
OMe
O
R2
O

R3

CH3 O

(1.32) (1.33)

CH3
O

H3C

O
O
CH3 (1.35)
O
E-
CH3 H3C
O CH3
conrotatory

H3C

O CH3
O

H3C

O
H3C CH3 O
H3C
O

O
CH3 CH3 O
H3C

(1.36)
(1.34) C
Z-

Figure 1.10 Photochromic process for fulgides.

(Reproduced with permission of University of
Leeds, Department of Colour Chemistry.)
 Phenomena Involving a Reversible Colour Change 13

1.2.6 Diarylethenes
The well-known photoisomerisation of stilbenes has been brought into the useful
photochromic range by replacing the phenyl rings with thiophenes, and the bridging
ethylene group by a maleic anhydride or perfluorocyclopentene group, as shown in
Figure 1.11. The thiophene ring can be annulated with a benzene ring or replaced
with indoles, furans and thiazole rings.
The reversible electrocyclic interconversion between the colourless ring-open
state and the coloured ring closed state on irradiation with light occurs at well-sepa-
rated wavelengths. The thermal conversion is not favoured and the compounds show
very high fatigue resistance.21,22

NH2
NH2

CN
CN

H3C O
H3C CH3 O
O CH3
O
O
O

720 nm
(1.44)

R
R

UV
H3C Visible
R1 R2
S CH3 S R1 S S R2
CH3 CH3
colourless coloured

F
F
F
O
O O F
R= or F
F

Figure 1.11 Photochromic behaviour of dithiophenylethenes.

1.2.7 Applications of Photochromic Materials

A reversible change in colour is not the only alteration in physical property experi-
enced during photochemical transformations of photochromic materials. There are
also changes in refractive index, relative permittivity (dielectric constant), oxida-
tion/reduction potentials and of course geometrical structure. Besides the well estab-
 14 Chapter 1
lished use of photochromic materials in ophthalmics, especially in plastic lenses for
sun glasses, there is therefore a growing list of other potential application areas,
including actinometry and heat measurement, optical memories for data storage
both 3D and near-field, photo-optical switches, filters, displays, self-developing
photography and many others.22 The incorporation of photochromes into polymers,
both in chain and side chain, is also an active area of research.28

1.2.8.1 Applications in Ophthalmics

Spectacle lenses that darken when exposed to strong sunlight and reverse back to
colourless in low light situations, such as indoors, offer the wearer personal comfort
and safety. During most of the last century spectacle lenses were made of glass and
the photochromic systems of choice were inorganic systems, based on silver halide.
The first of these was developed and launched by Corning Inc. in 1966, and over the
years proved to be quite satisfactory in protecting wearers. However, in the last
decade of the 20th century, plastic lenses were introduced and rapidly replaced glass
as the material of choice in the developed world. The established silver halide photo-
chromic systems could not be adapted to work well in plastic and hence there was a
need for alternative materials, and these have turned out to be photochromic dyes.
Pioneers in this application area were PPG industries with their Transitions photo-
chromic plastic lenses.
The demands on the photochromic materials are quite severe, a major issue is the
ability to obtain the ‘correct’ colour, and optical density in the lens. The generally
preferred tints in photochromic eyewear are switchable neutral greys or browns,
because they allow the sky to look blue and do not interfere with red danger signals.
These shades are readily obtainable in glass because the silver halide system absorbs
broadly in the visible and can be manipulated to obtain greys or browns. There is no
single photochromic compound that can do this and colour formulators need to resort
to mixtures of products to produce the desired colours in the lens. Apart from being
able to deliver the desired colour, photochromic materials have to satisfy other crite-
ria, including a matching of the activation and fade rates, showing a balanced
response to UV absorbance, having matching temperature dependency on the change
from coloured to colourless, and also matching fatigue rates and life expectancy in
use.
The three main classes that have been much studied for ophthalmic applications
are spiroindolinonaphthoxazines (see section 1.2.3), diarylnaphthopyrans (see sec-
tion 1.2.4) and fulgides (see section 1.2.5). How these different photochromic classes
match up to the desired criteria for use in lenses is shown in Table 1.9. From this it
can be seen that fulgides exhibit only a fair fatigue resistance and spiroindolinon-
aphthoxazines suffer from a high temperature dependency. Consequently, for this
photochromic outlet, naphthopyrans have become the molecules of choice. Typical
Table 1.9 Photochromic properties of commercially available classes
Performance Temperature
Class (OD, act/fade rate) dependency Fatigue
Spiroindolinonaphthoxazines Good High Good
Naphthopyrans Good Medium Good
Fulgides Good Medium Fair
 Phenomena Involving a Reversible Colour Change 15

compounds used to produce greys and browns are the yellow (1.31) and the blue
(1.32), the properties of which are given in Table 1.10. This pair offer a well matched
build up to saturation optical density but their fade rates, whilst close, are far from
perfectly matched.14 Commercial products have been produced that do achieve the
correct balance, but information on their actual composition is commercially sensi-
tive and hence is not disclosed in detail in the open literature.

Table 1.10 Photochromic properties of naphthopyrans in ophthalmic plastic

H3C
OH CH3

CO2CH2CO2CH2CH3
CH3

OCH3

O O

H3C

CH3
OCH3
(1.31) (1.32)

Compound max/nm Optical density T1/2 (Fade)/s

30 s 120 s At saturation
131 464 0.16 0.29 0.37 60
132 582 0.12 0.25 0.36 80

1.2.8.2 Novelty Printing and Textile Applications

The use of photochromics in novelty printing is a significant commercial outlet.
Because of their ability to show resistance to thermal fade rates fulgides have been
the class most commonly used for this application. Typical uses are on children’s
toys and for logos on T-shirts.
For instance, it is possible to produce mass pigmented polypropylene by dissolv-
ing different photochromic materials into molten polypropylene. By melt spinning, a
thread is produced that is photoactive and is used to embroider designs on apparel
garments etc. Indoors, away from UV light, the design is white on the fabric but
changes its colour on exposure to UV radiation in daylight. A range of colours is
available from yellow through red to purple and green.29

1.2.8.3 Optical Memories and Switches

The establishment of the recording of information by light in digital optical systems
has triggered the search for molecular materials that will allow much higher storage
densities and faster switching rates. Consequently, photoactive materials, which can
interchange between one or more distinct states, are of particular interest. The major
target for work on molecular switches has been their use in reversible data storage.
 16 Chapter 1

The term optical data storage (ODS) refers to those systems that use laser light to
record and reproduce information. A more detailed discussion of ODS systems is
given in Chapter 4 (section 4.3). The main targets for developers of ODS systems in
recent years have been CD-R (recordable) and CD-RW (rewritable) compact disks
and digital versatile disks (DVDs). The most highly developed erasable and
rewritable media are either magneto-optic or phase change materials, both of which
utilise heat-mode effects. The development of phase change systems based on
organic dyes has meant that products based on other organic systems, such as photo-
chromics, are more likely to be accepted by the industry.
Photochromic optical memories, in contrast to heat-mode recording systems, use
photon-mode recording, operating on changes in physical properties such as trans-
mittance, reflectance or fluorescence. Potential advantages of photon-mode over
heat-mode recording include higher resolution and speed of writing, and multiplex
recording capability by use of wavelength, polarisation and phase changes.
For a photochromic material to be of any use in optical memories it must meet the
minimum requirements in the following physical properties:30

• Thermal stability – very low thermal re-conversion

• Fatigue resistance – long-term stability during read and write cycles
• Non-destructive readout capability – the read out process must not induce inter-
conversion of the two forms
• High efficiency of the photoreaction – large quantum yields and molar
coefficients
• High speed of the photoreactions
• Diode laser susceptibility
• Solubility in polymer matrix

Of those properties on the list, the most difficult to attain is a non-destructive readout
procedure. Two approaches have been adopted to overcome this problem.22,27

1. Single-mode system.
Detect the two forms, A (colourless) and B (coloured), using light of a lower
energy than the UV–Visible light used for the interconversion (A into B, B into A).
The readout can be measured as the difference in the reflecting light intensity of
the laser (e.g. diode), or by fluorescence or infrared absorption signals in the two
forms.22,23
2. Dual-mode system
Involves two reversible processes. In the first, irradiation with light in the UV–
Visible range causes the interconversion of A and B. In the second process a
photon, an electron or a proton is used to prevent the interconversion of A and B
by transforming them into stable A’ and B’ products. The two forms in the system
can therefore be locked or unlocked.31

Photochromic systems that have been examined in both of these approaches

include spiropyrans, spirooxazines, diarylethenes, dihydroindolizines and azoben-
zenes.22,27,30–33 A schematic of a disk structure is shown in Figure 1.14. To produce the
Phenomena Involving a Reversible Colour Change 17
resin
reflective layer
photochrome / PMMA
substrate

laser

Figure 1.14 Schematic of an optical memory disk.

recording layer the photochromic material is laid down in an acrylic resin (e.g.
PMMA) onto a reflective layer of gold or aluminium. The recording medium is
addressed by a recording/writing laser, e.g. He-Cd laser at 325 nm, or a frequency
doubled diode laser, and a readout laser such as a AlGaAs 784 nm diode laser, oper-
ating through the glass substrate.
Several approaches can be adopted when trying to achieve very high-density opti-
cal storage. These include the development of short wavelength blue lasers; a halv-
ing of the wavelength of the laser reduces the spot radius by 2 and therefore the
recorded, two-dimensional density by 4 (See Chapter 5, section 5.5). In the field of
optical recording and memories the following methods are being examined.

1. Near-field optics, in which recording density depends only on the size diameter
of the probe tip aperture22
2. 3D-Memory by use of additional axial dimensions to the recording system33
3. Optical holography (see Chapter 5, section 5.4)

Rentzepis, in 1989, was the first to propose the use of photochromic compounds in 3D
optical memories, the principle of which is illustrated in Figure 1.15. The potential for
this 3D memory principle was demonstrated using the spirobenzopyran (1.59).34 It is
a two-photon process in which two laser beams are used to access a point in a 3D
memory block. Writing requires excitation in the UV range and for this purpose a two-
photon absorption, e.g. a 1064 nm and a 532 nm photon (equivalent to 355 nm exci-
tation) or two 532 nm photons (equivalent to 266 nm excitation), is used. Absorption
of two photons by A causes it to isomerise to B, the coloured form. Reading can also
be carried out by a similar two-photon process; for instance two 1064 nm photons to
excite fluorescence in only the written molecules in form B, but the process is destruc-
tive due to partial reversion of B to A. Consequently, alternative read out procedures
must be used, the most promising of which is the detection of refractive index changes
observed when photoisomerisation is induced by long-wavelength light.33

1.2.8.4 Other Optical Applications

A considerable amount of work has been done on incorporating photochromic com-
pounds into organic or inorganic hybrid materials or synthesising preformed poly-
mers to produce photoresponsive materials. 28,35 These materials are being designed
for use in optical applications such as wave-guides, shutters, light modulators etc.,
systems which are considered further in Chapter 5.
18 Chapter 1

laser
beam
splitter

Frequency
doubl er

memory
block

NO2
H3C CH3 H3C CH3
Cl Cl
h

N O NO2 Vis N O
CH3 CH3

A B
(1.59)
Figure 1.15 Principle of 3D optical memory and a model photochrome.
(Reproduced with permission of the American Chemical Society.)

1.2.8.5 Biological Applications

It is possible to attach photochromic molecules onto naturally occurring receptors
and enzymes and by so doing be able to photoregulate their binding and catalytic
activities. These materials have the potential to be used as chemotherapeutic agents
and biosensors, and as bioelectronic materials.36,37 In most of this work to date
spiropyrans have been used as the photochromic element in the system.

1.3 Thermochromism
Day, in his seminal work, defined thermochromism as “an easily noticeable
reversible colour change brought about by the boiling point of each liquid, the boil-
ing point of the solvent in the case of a solution or the melting point for solids”.38
Whilst this definition is academically accurate for many inorganic and organic
materials, the label ‘thermochromic’ has also been applied to important technical
areas that involve other external influences as well as heat in the observed colour
change, e.g. thermochromic pigments.
A technically more appropriate approach is to separate reversible organic ther-
mochromism into ‘intrinsic’ systems, where heat is the sole cause of the colour
change, from ‘indirect’ systems, in which the colour variation involves changes in
Phenomena Involving a Reversible Colour Change 19
39
the environment around the chromophore brought about by heat. Technical appli-
cations where the indirect colour change is desired to be irreversible, e.g. thermal fax
colour formers, will be covered under ionochromism (see section 1.4) as these sys-
tems are probably best considered as being essentially initiated by changes in pH,
similar to indicator dyes.

1.3.1 Inorganic and Organometallic Materials

Inorganic materials, usually involving transition metals, and organometallics exhibit
a thermochromic response over a wide range of temperatures and by a variety of
mechanisms.39,40 Examples include:

• The transition between different phases of different colour, e.g. Cu2HgI4 is red at
20 °C and black at 70 °C38
• A decrease in the band-gap of semi-conductors with rise in temperature, e.g.
white ZnO becomes yellow at high temperatures; In 2O3 is yellow at lower tem-
perature and changes to yellow–brown on heating40
• Variations in the crystal field, e.g. 1:9 Cr2O3–Al2O3 is red at 20 °C and grey at
400 °C,41
• A change in ligand geometry, e.g. (Et2NH2)2CuCl4 is bright green at 20 °C
(square planar) and yellow at 43 °C (tetrahedral)42
• A change in co-ordination number, e.g. Isopropanolic CoCl2 at 25 °C exists in its
pink octahedral geometry around the Co2+ ion and changes to the blue of the
tetrahedral geometry at 75 °C39

1.3.2 Reversible Intrinsically Thermochromic Organic Systems

In these systems heating alone, without the need for any other agent, causes the
change in colour of a chromophore, and on removal of the source of heat the colour
reverses to its thermally more stable state.
Systems and molecules showing intrinsic reversible thermochromism can be clas-
sified as follows:

• Molecular rearrangement of molecules by the breaking of covalent bonds, e.g.

spirooxazines
• Stereoisomerism in molecules; interchange between stereoisomers that have dif-
ferent colours, e.g. bianthrones
• Macromolecular systems, e.g. polythiophenes, polysilanes, polydiacetylene
• Supramolecular systems, e.g. cholesteric liquid crystals (see Chapter 5, section
5.2)

1.3.2.1 Molecular Rearrangements

Spiropyrans, and spirooxazines, better known for their photochromic behaviour (see
sections 1.22 and 1.23), also exhibit thermochromism. The ring opening to produce
the highly coloured merocyanine form is induced by heating either the solid or
20 Chapter 1

a solution. They show a strong solvatochromic effect, polar solvents favouring the
formation of the more polar merocyanine form.43
It is possible to produce sequential colour changes using bis-spiropyrans.44 The
colourless bis-spiropyran (1.60), in Figure 1.16, when heated in n-propanol to 60 °C
changes to a red colour, due to the formation of the mono-merocyanine (1.61), and at
70 °C it becomes blue as the bis-merocyanine (1.62) appears.
Schiff bases, from the condensation of salicylaldehydes with anilines, exhibit
either solid-state photochromic or thermochromic behaviour, caused by hydrogen
transfer between the enol–keto tautomeric forms. Whether the molecule exhibits
photo or thermochromism is strongly dependent on their crystal structures. The
thermochromic effect in Schiff bases is restricted to planar molecules, where the
tautomeric equilibrium is toward the keto form, which absorbs at a longer wave-
length (1.63), the colour change being normally from yellow to orange or red. 44 The
aryl rings can be substituted with a range of both electron-withdrawing and electron-
donating groups. If the phenyl ring on the aniline is changed to a pyridyl ring then the
products exhibit only thermochromic behaviour.

NO2
H3C H3C CH3
O N

N O
H3C CH3 CH3
O2N
(1.60)
Colourless

60oC

H3C CH3
H3C
O2N O N

N O
H3C
CH3 CH3
O2N
(1.61)
red

70oC

H3C H3C CH3

O2N O N

N O NO2
H3C
CH3 CH3

(1.62)
blue

Figure 1.16 Sequential thermal colouration of a bis-spiropyran.

Phenomena Involving a Reversible Colour Change 21

R2
R2
R1 R1
N N
1
H
OH O
2

(1.63)

1.3.3 Applications of Thermochromic Materials

Inorganic systems have found only relatively limited applications being mainly used
in paints and crayons for indicating hot spots on equipment etc.38,47 Of the intrinsi-
cally thermochromic organic materials it is only liquid crystals and conjugated
polymers that have found any serious practical application, for instance the latter
are used in optical temperature indicators and thermal recording. 48 The majority of
current commercial applications use composite materials based on indirect
thermochromism.

1.3.4.1 Composite Thermochromic Pigments

Composite thermochromic pigments consist of three components; a pH sensitive
dye, a proton donor, which acts as the colour developer, and a hydrophobic, non-
volatile co-solvent. To achieve the desired effect the components are mixed in
specific ratios and usually encapsulated to protect the system in subsequent applica-
tions. A review of the patent literature on these compositions has been published.49
The pH sensitive dyes, often called colour formers, that are most commonly used
belong to the spirolactone class, e.g. diaryl phthalides (see section 1.4.1.1) or fluo-
rans (see section 1.4.1.3). Ring opening of the colourless lactone on protonation by
the weak acid developer occurs to give the coloured form. Many compounds have
been claimed for use as the colour developer, but the most important commercially is
Bisphenol A, which develops bright colours and changes of high contrast.39 The most
frequently used co-solvents are low-melting fatty acids, amides and alcohols. In the
production of the pigments, the colour former, developer and co-solvent are melted
together and cooled to give the coloured pigment; encapsulation for commercial use
being achieved by the standard techniques of coacervation or interfacial polymerisa-
tion.49 The resultant pigment formulations offer the following advantageous features.

• Switching of colour over a few degrees change in temperature

• Variable switching temperature by choice of co-solvent
• Wide choice of colours from yellow to red, blue, green and black
22 Chapter 1

The pigment is coloured in the solid form of the material because in this state the
colour former interacts with the developer, possibly via an ion-pair complex. Melting
of the composite interferes with this interaction, leading to a negative thermochromic
effect and a loss of colour. This is shown schematically in Figure 1.19. Possible
mechanisms for the colour change have been examined.39
The normal colour change is from coloured to colourless but, by careful selection of
the pH sensitive dye, it can also be from one colour to another. It is also possible to use
mixtures of thermochromic pigments of different melting points; as one component of
the mixture shade becomes colourless on melting, the colour changes to that of the
remaining, higher melting pigment. Alternatively a secondary chromophore can be
present in the spirolactone molecule as with the azo group in (1.65).

+ R NR2
R NR2 H
O CO2H
+
H
O O CO2H
X X
O
coloured
X colourless X

colourless coloured
H3C CH3

H3C CH3
HO OH

Bisphenol A
HO OH
Bisphenol A

Above m.p.

Below m.p.

coloured solid colourless liquid

colour former and developer encapsulated in co-solvent

Figure 1.19 Schematic of a composite organic thermochromic pigment.

Phenomena Involving a Reversible Colour Change 23
R2N O
R2N O
N
N H+ N
N
O CO2H
NR2
NR2
O

yellow red-brown
(1.65)

Thermochromic pigments are finding an ever increasing number of outlets, espe-

cially in inks, paints, and in apparel.50,51 Paints are available for use on a variety of
substrates, including metals, ABS, polypropylene, polyethylene, PVC and poly-
styrene. Inks have been developed for many types of printing processes, such as
screen, gravure and flexographic, and more recently the arrival of pigment formula-
tions that are compatible with offset vehicles has extended the range of application to
offset lithography. Masterbatch plastic concentrates can be made from ABS, poly-
styrene, polypropylene, PVC, nylon and polyester. For apparel applications, thermo-
chromic materials have been incorporated into embroidery and weaving threads and
onto transfer papers for thermal printing of a variety of fabrics.
Examples of the use of these materials include temperature indicators for
children’s food by colour change plastic mugs, indicator stripes on beer and colas to
indicate correct chilling, and on milk cartons to indicate that they have been refriger-
ated. In the security area they can be used for simple verification of a document’s
authenticity, e.g. by heat from the finger on cold days or by cooling on warm days;
for message hiding, e.g. a message will appear when a copy is made with photo-
copiers, alerting for a check on authenticity. In the novelty area, logos on mugs and
printed textiles, such as T-shirts, and in jewellery are common uses.
There are limitations to the use of this technology, not the least of which is the gen-
erally poor fastness of thermochromic pigments to UV in sunlight, generally restrict-
ing its use on garments and printed articles that are not likely to be left in the daylight
for any length of time. Of course they are intrinsically temperature dependent and
articles containing these materials must be protected from any unwanted heat source.

1.3.4.2 Chromogenic Thermotropic Gels

Thermotropic gels or liquids are materials that reversibly change from a transparent
state to a milky white, reflective state at a certain temperature or over a specific range
of temperature. The materials are gels made up of colourless inorganic salts dis-
solved in a mixture of water and a water miscible polymer, such as poly(vinyl alco-
hol). The change in the transparency of these gels is due to the formation of liquid
crystalline phases and also phase separation. They can be used as both light and heat
filters in the milky state, and a special target is their use in switchable glazing units
for sun protection in buildings.52
It is possible to create gels that are also thermochromic by incorporating pH sen-
sitive dyes into the gels.53,54 The gel is made by up mixing a 4800 MW polyalkoxy
polymer, PO:EO ratio of 87:13, with lithium chloride and an aqueous buffer and a pH
sensitive dye. Using Bromothymol Blue (see section 1.4.2.1) the gel is coloured
24 Chapter 1

green and transparent at –5 °C, when the phenolate ion absorption (max 617 nm)
dominates over the phenol (max 408 nm) absorption band. On raising the temperature
the ratio of the two species changes and, over the range 33–37 °C, the gel becomes
yellow and also opaque, due to phase separation. There is a pH change in the gel
from pH 7.8 at 0.5 °C to pH 6.8 at 32.5 °C. The process can be reversed by cooling.
Using Nitrazine Yellow the colour change is from blue at 25 °C to green above 33 °C,
whilst with Chlorophenol Red the change is from red at 5 °C to yellow at 32 °C. 54
These gels have the potential for use as temperature sensors, in the same way as liq-
uid crystals and thermochromic pigments are used. However, to be used in coloured
glazing much more light stable dyes will be required.

1.4 Ionochromism
Ionochromism is the name applied to the phenomenon of a colour change associated
with the interaction of compounds or materials with an ionic species. For the purpose
of this book, the main ionic species is the solvated hydrogen ion, in which case the
terms halochromic, acidochromic or pH sensitive are often used. However, other
common ions include metal ions, and onium cations such as tertiary ammonium and
phosphonium. The organic structures that undergo the colour change on interaction
with the ions are called ionochromes or ionophores. The colour change can be from
colourless to coloured or coloured to coloured and is usually reversible. A closely
related topic is that of fluoroionophores, covered in section 3.5.6, where ions cause a
change in the fluorescent emission of the molecule.

1.4.1 Ionochromic Compounds

The main classes of commercially important pH sensitive dyes are phthalides, tri-
arylmethanes and fluorans. In fact, several chromophores undergo useful colour
changes on protonation, including simple, neutral azo dyes, styryl dyes and indophe-
nols. With metal ions a whole range of chelating ligands can be employed as colour
indicators and sensors, but of special importance are crown ethers and cryptands for
a range of non-traditional uses.

1.4.1.1 Phthalides
Indicator dyes for pH having the phthalide structure fall into two types, the
phthaleins, shown in the lactone form of general structure (1.66) and the sulfoph-
thaleins (1.67). The synthetic pathways to these products are very similar. The
phthaleins (1.66) are made by reacting phenol with phthalic anhydride in the pres-
ence of Lewis acid catalyst, e.g. ZnCl2, whilst (1.67) are obtained by using 2-sul-
fobenzoic anhydride (Figure 1.20).
The response of phthaleins to changes in pH is best exemplified by the parent
dihydroxy derivative, the well-known indicator, with the trivial name of phenolph-
thalein (1.68). The colourless lactone (1.68) on adding alkali undergoes a successive
conversion into the mono and then the diphenolate ion (1.69), which then rearranges
via ring opening of the lactone to give the planar dianion (1.70), which is red (Figure
Phenomena Involving a Reversible Colour Change 25

OH

R4 R1

R3 R2

O
O

O
O
S
O2
O

ZnCl2

R1 R4 R1 R4
HO R2 R3 HO R2 R3
OH OH

R4 R4
R1 R1
R3 O R3 O
R2 R2
CO SO2

(1.66) (1.67)

Figure 1.20 Synthesis of phthaleins and sulfophthaleins.

1.21). The process is reversible and therefore provides an easily visible method for
measuring pH change in the range of 8.5–9.0. The ionisation reactions of sulfoph-
thaleins follow a similar pathway. Substitution in the phenolic rings of the phthaleins
and sulfophthaleins provides a variety of coloured dianions, which change colour
over different ranges of pH (see section 1.4.2.1).
The most important technologically of the phthalides are those based on the
Crystal Violet Lactone structure (1.71) and its heterocyclic analogues.55 This is
because they are used as colour formers in carbonless copying papers and other
digital printing outlets (see section 1.4.2.2). These processes use the fact that the
lactone ring of the colourless form (1.71) opens in the presence of an electron-
accepting donor to give a coloured cationic dye (1.72), as exemplified for Crystal
Violet Lactone in Figure 1.22.
There are two main synthetic routes to Crystal Violet Lactone (CVL) and its ana-
logues (Figure 1.23). The first involves the condensation of 4,4’-bismethyhydrol
(1.73), also called Michler’s Hydrol, with 3-dimethylaminobenzoic acid in dilute
acid to give the leuco CVL, which is then oxidised to CVL. A wide variety of oxi-
dants can be used but the preferred method uses hydrogen peroxide in basic solution.
The oldest, and most versatile route starts by reacting 4-dimethylaminobenzaldehyde
26 Chapter 1
HO OH
O OH

H
O
O

O H
O
(1.68)
H
H H
H

O O O O

CO2 O

O
Red
(1.70) (1.69)

Figure 1.21 Ionisation pathway of phenolphthalein.

(H3C) 2N N(CH3)2 (H3C) 2N N(CH3) 2

D
O CO2 D

O
(H3C) 2N
N(CH3) 2

Colourless Blue
(1.71) (1.72)

Figure 1.22 Colour formation in Crystal Violet Lactone/developer system.

with 3-dimethylaminobenzoic acid to give the 3-(4-dimethylaminophenyl)-6-

dimethylaminophthalide, which is then oxidised to the intermediate bisdimethy-
laminobenzophenone carboxylic acid (1.74). This intermediate is reacted with N,N-
dimethylaniline in acetic anhydride to give CVL.
Whilst CVL has had great commercial success as a colour former, it has very poor
light fastness and requires shading components to produce the desired shade.
Consequently, many other related phthalides have been examined in seeking to
improve on CVL’s properties. The most important of these are the heterocyclic ring
analogues, especially those with indole and pyridine rings having the generic for-
mula (1.76). The general synthetic route to these derivatives involves condensation
of phthalic anhydride, or a pyridine analogue, with a N-alkyl-2-methylindole to give
the indolylbenzoic acid (1.75), followed by reaction with a substituted N,N-
dimethylaniline in acetic anhydride to produce the substituted phthalide (1.76), as
shown in Figure 1.24. The blue producing indolyl phthalides (1.76; X and Y = CH)
have much improved light fastness over CVL. Of the colour formers carrying pyridyl
rings, the isomeric compounds (176; X = N, Y = CH, R, R1 = Et, R2 = OEt) and (176;
X = CH, Y = N, R, R1 = Et, R2 = OEt) and their mixtures have enjoyed commercial
success because they yield intense blue images with excellent fastness when used in
conjunction with organic developers. They are commonly called Pyridyl Blues in
this application.55
Phenomena Involving a Reversible Colour Change 27

1.4.1.1 Fluorans
Fluoran is the trivial name that is commonly used for the spiro[isobenzofuran-1,9’-
xanthen]-3-one class of compounds (1.78). The colour-forming reaction involves
ring opening of the lactone ring by acid to give the coloured quinone form; colour
reversion can be achieved by adding a base. As colour formers, the big advantage
offered by fluorans is that they can provide a wide variety of colours, including a
single component black, as opposed to the blue and orange mixtures required to give
blacks from phthalides and triarylmethanes.56
Yellow colours are derived from dialkoxy fluorans, e.g. (1.78; X and R1 = OR, R2
= CH3); orange from mono-alkylamine derivatives, e.g. (1.78; X = NHcyclohexyl, R1
= Cl, R2 = H); red from mono-dialkylamines, e.g. (1.78; X = NEt2, R1 = CH3, R2 = H);
blue from bis-diarylamines, e.g. (1.78; X and R1 = NAr2 , R2 = H), green by moving
one of the amino substituents into the 2’-position, e.g. (1.78; X = NEt2, R1 = H, R2 =
NEt2); and finally black by changing the 2’-substituent to an arylamino group, e.g.

X O R1
X O R1

Acid R2
R2
O
CO2H
Base

(1.78)

(1.78; X = NEt2, R1 = H, R2 = NHAr). The blacks that are used as commercial colour
formers, (1.82a and 1.82b), are synthesised by reacting 4-alkoxydiphenylamines
(1.79) with the keto acids (1.80) in sulfuric acid to give the intermediate phthalides
(1.81), which are converted into the fluorans by reaction with sodium hydroxide
(Figure 1.25).56

1.4.2 Applications of Ionochromism

Ionochromism has several very important technological applications. The original
use of pH sensitive dyes was as reversible indicators in analytical chemistry, in
which area complexometric methods have been developed in order to detect and esti-
mate metal ion concentrations. Variations in the colour of certain dyes with changes
in pH can also be used to visualise changes in many physical environments. This is
particularly the case where the acidic, ionic or donor species is generated on expo-
sure to light or heat. Examples include the use of ionochromes as colour formers in
pressure and thermal sensitive copying papers, in facsimile papers, and in digital and
other forms of imaging, where irreversibility is one of the desired properties, e.g.
lithographic plate processing. The use of pH sensitive dyes as one of the components
in reversible, composite thermochromic pigments has already been described
(section 1.3.4.1).
28 Chapter 1
1.4.2.1 Analytical Chemistry
Historically, pH sensitive dyes have been extensively used as indicators in acid–base
titrations and in simple spot test papers, even leading to a common phrase in our
everyday language, when people or topics are described as “having passed the litmus
test”. The use of complexometric titrations for metal ions was a later but widely
applicable development, which is best dealt with in specialised texts. 63 However,
with the advent of instrumental techniques and the development of miniaturised,
hand-held machines, suitable for field work, the use of pH sensitive dyes in analysis
has very much diminished. In spite of this diminution in their traditional uses, these
compounds are finding new uses where the ionic response of dyes is exploited (see
also section 1.3.4.2 ). Consequently, a brief description of their properties, as given
below, is justified.
The ionic pathways for the phthaleins have been shown earlier in Figure 1.21. By
modifying the chemical structure of the phthaleins, and especially the closely related
sulfophthaleins, a whole range of reagents can be made with different colours
changes. It should be noted that the change of colour is not sharp but occurs over a
narrow pH range. The structures of some of the more common reagents and their
properties are given in Table 1.11.
Protonation of azo dyes is also used as a method for producing analytical indica-
tors, the two best known ones being Methyl Orange and Methyl Red, the colour
change being generated by formation of the azonium tautomer (Figure 1.27). It
should be noted that some azo dye based indicators, e.g. Methyl Yellow and Congo
Red, are no longer used as they are potential carcinogens (see Chapter 2, section
2.3.1.1).

Table 1.11 Phthalein and sulfophthalein indicators

R2 R2
3
R3 R
HO OH

R1 R1
O

Name R1 R2 R3 X pH range Colour change

Phenolphthalein H H H CO 8.5–9.0 Colourless–red
Cresolphthalein CH3 H H CO 8.2–9.8 Colourless–red
Thymolphthalein CH(CH3)2 H CH3 CO 9.3–10.5 Colourless–blue
Phenol Red H H H SO2 6.8–8.4 Yellow–red
Cresol Red CH3 H H SO2 7.2–8.8 Yellow–red
Chlorophenol Red Cl H H SO2 4.8–6.4 Yellow–red
Bromophenol Red Br H H SO2 5.2–6.8 Yellow–red
Bromophenol Blue Br Br H SO2 3.0–4.6 Yellow–blue
Bromothymol Blue CH(CH3)2 Br CH3 SO2 6.0–7.6 Yellow–blue
Bromocresol Purple CH3 Br H SO2 5.2–6.8 Yellow–purple
Thymol Blue CH(CH3)2 H CH3 SO2 1.2–2.8 Red–yellow
Xylenol Blue CH3 H CH3 SO2 1.2–2.8 Red–yellow
8.0–9.6 Yellow–blue
Phenomena Involving a Reversible Colour Change 29

Indicator R1 R2 pH range Base max/nm Azonium max/nm

Methyl Orange H SO3H 3.1 (red) 506
4.4 (yellow) 442
Methyl Red CO2H H 4.4 (red) 520
6.2 (yellow) 435

1.4.2.2 Carbonless Copying Paper

This, as its name implies, is a process by which multiple copies of a document can be
produced without using carbon paper. The first system was launched by the National
Cash Register Company of the USA in 1954. Since that time many improvements
have been made to the process but the basic technology is the same as it was when
first developed. At its most basic level the process consists of two sheets of specially
coated paper on which the element of the image are implanted using pressure; hence
the term pressure sensitive papers is often used for these materials. The top sheet is
coated on the reverse side with microcapsules containing a pH sensitive leuco
dye, known as the colour former, e.g. Crystal Violet Lactone (1.71), in a non-volatile
solvent. The microcapsules are produced either by a coacervation process using
gelatine or more commonly nowadays by coating with resins such as urea/formalde-
hyde, polyester or polyurethane.56 The surface of the lower sheet is coated with an
acidic material, which can be selected from acidic clays, zinc salicylate and zinc
modified phenolic resins. On application of pressure to the top sheet, the dye is
released from the microcapsules and reacts with the acidic clay on the lower sheet to
produce the coloured image. The process is illustrated schematically in Figure 1.28.
Commercial use of the system is very large, mainly in the continuous production of
multiple copy business bills and receipts from computer generated customer lists,
where more than two layers of paper is the norm.

1.4.2.3 Direct Thermal Printing

The production of a digitised image on a coated paper by a thermal head is known as
direct thermal printing.64,65 The essential difference between this process and carbon-
less copying paper is that the thermosensitive layer contains both the colour former
and the acidic co-reactant, and hence is a single layer process. Simply heating the
surface of the paper with a thermal head causes the components to react and produce
the coloured image. The preferred colour formers for the desired black images are the
fluorans (1.82a and b). All the co-reactants used commercially are phenols, the most
widely used being Bisphenol A, often incorporating a sensitiser, such as benzyl-2-
naphthyl ether, to reduce the energy input and speed up the printing process. Poor
image stability to light and heat is an inherent problem with the system and to help
30 Chapter 1

Microcapsule
of
Pressure
Colour Former

Top
Sheet

Bottom
Sheet
Acidic
Co-reactant

Coloured
Image

Figure 1.28 Schematic representation of carbonless copying paper process.

counteract these problems hindered phenols are included as stabilisers. To prevent

wear on the thermal heads, which come in direct contact with the paper, a lubricant
such a zinc stearate is added and to retain the smoothness of the surface of the paper
anti-pressure agents such as paraffin waxes are included. Typical binders used to hold
the materials to the surface of the paper are poly(vinyl alcohol) or hydroxyethyl
cellulose. The process is shown schematically in Figure 1.29.
By far the largest use of direct thermal printing is in facsimile machines where
digital images transferred via telephone lines are reproduced. There are two
weaknesses in the use of this method of direct printing; firstly the need for specially
coated papers and secondly the poor light stability of the images on the paper. The
special paper problem is somewhat offset by the fact that no special inks or other
materials are required. The machines are very cheap and highly reliable in use; it is
therefore a cost benefit calculation as to which system is used when disposable infor-
mation is involved. However, when the document is required for archival purposes
then image stability is a serious problem. Plain paper fax machines using ink jet
printers to produce the image overcome both of these problems and their arrival on

Thermal
head

Thermo-
sensitive
layer

Coloured
Binder and
dye
Base Paper additives
image

Colour former Co-reactant

Figure 1.29 Direct thermal printing process.

the market has severely curtailed the growth of direct thermal printing (see Chapter
Phenomena Involving a Reversible Colour Change 31
2, section 2.7). Another very significant competitor is the rapid growth of file trans-
fer of data and images via e-mail.
Increasingly there is a requirement for the printing of digital images in full colour.
Whilst some progress has been claimed for direct thermal printing, e.g. the Thermo
Autochrome from Fuji, the complexity of the multilayer papers means that they are
very unlikely to ever compete effectively with ink jet printers.65

1.5 Electrochromism
When an electroactive species undergoes a change in colour upon electron transfer or
oxidation/reduction the process is known as electrochromism. This process normally
involves the passage of an electric current or potential and is reversible. In the late
1960s, because of their reversible change in colour, it was suggested that elec-
trochromic materials could be used to make coloured displays. However, in spite of
the early enthusiasm, it took until the last decade of the century for genuine com-
mercial applications to appear, and then not in displays but in switchable rear-view
mirrors and the so-called smart windows.69 In this section the mechanism of elec-
trochromism in cells will be discussed only briefly, followed by a more detailed
description of the various classes of electrochromic materials, and finally an account
will be presented of the burgeoning applications for these systems.70

1.5.1 Electrochromic Cells

During 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 col-
oration. Two different types of cells are shown schematically in Figure 1.31.69
The most common is the coloured electrode type, in which the transparent
electrodes are coated with an organic or inorganic polymer which becomes coloured
on passing a charge through the cell (see 1.5.2.3). If both electrodes change colour
they must display complementary electrochromism; the colour change that occurs by
oxidation at the first electrode must be the same as that occurring by reduction at the
second electrode. The degree of colouration can be controlled by the amount of
charge passing through the cell. The cell is bistable; i.e. it remains coloured, even
in the absence of applied voltage, until an equal charge is passed in the opposite
direction through the cell. In other words the coloration of the electrochromic cell is
controllable and switchable on demand.
In the case of the coloured electrolyte type, the two complementary elec-
trochromes are dissolved in the electrolyte between the transparent electrodes. One
becomes coloured by oxidation and the other by reduction and consequently the elec-
trolyte 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.
32 Chapter 1
Coloured electrode
OFF ON ON
+- +- +-

OR
electrolyte

electrodes

Coloured electrolyte
Coloured electrolyte
OFF ON
+ -
OFF +ON-
+ - + -

Figure 1.31 Electrochromic cells.

1.5.2 Electrochrome Types

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 mir-
rors for commercial vehicles and the third type in smart windows (see section
1.5.4.2).

1.5.2.1 Solution Electrochromes

In these systems the soluble electrochrome undergoes an electron transfer interaction
on the surface of the appropriate electrode, involving either anodic oxidation or
cathodic reduction, where it changes colour and then returns back to the solution
phase, i.e. a coloured electrolyte is produced (see Figure 1.31). The most widely
studied solution electrochrome is the dimethyl-4,4-bipyridylium dication, also
known as methyl viologen, (1.90; R = CH3), which undergoes a one-electron reduc-
tion to the bright blue coloured radical cation (1.91; R = CH 3).71 Another aqueous
phase electrochrome is Fe(III) thiocyanate, whilst hexacyanoferrates and quinones
such as TCNQ can be used in acetonitrile solution.70

R N N R R N N R

(1.90) (1.91)
Phenomena Involving a Reversible Colour Change 33

1.5.2.2 Solution–Solid Electrochromes

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 pro-
duced is insoluble and is deposited onto the surface of an electrode. Viologens with
hydrophobic chains, such as heptyl (1.90; R = C7H15), form deeply coloured radical
cation salts (1.91; R = C7H15) in water that appear as a thin film deposited on the elec-
trode. Other examples are N,N-bis(4-cyanophenyl)-4,4-bipyridylium salts (1.90; R
= 4-cyanophenyl) in water and methoxyfluorenone in acetonitrile solution.

1.5.2.3 Solution Electrochromes

In these systems the soluble electrochrome undergoes an electron transfer interaction
on the surface of the appropriate electrode, involving either anodic oxidation or
cathodic reduction, where it changes colour and then returns back to the solution
phase, i.e. a coloured electrolyte is produced (see Figure 1.31). The most widely
studied solution electrochrome is the dimethyl-4,4-bipyridylium dication, also
known as methyl viologen, (1.90; R = CH3), which undergoes a one-electron reduc-
tion to the bright blue coloured radical cation (1.91; R = CH 3).71 Another aqueous
phase electrochrome is Fe(III) thiocyanate, whilst hexacyanoferrates and quinones
such as TCNQ can be used in acetonitrile solution.70

R N N R R N N R

(1.90) (1.91)

1.5.2.4 Solution–Solid Electrochromes

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 pro-
duced is insoluble and is deposited onto the surface of an electrode. Viologens with
hydrophobic chains, such as heptyl (1.90; R = C7H15), form deeply coloured radical
cation salts (1.91; R = C7H15) in water that appear as a thin film deposited on the elec-
trode. Other examples are N,N-bis(4-cyanophenyl)-4,4-bipyridylium salts (1.90; R
= 4-cyanophenyl) in water and methoxyfluorenone in acetonitrile solution.

1.5.2.5 Solid Electrochromes

All inorganic electrochromes exist in the solid state in both the colourless and
coloured states, e.g. Prussian Blue and tungsten trioxide. Conducting polymers such
as polyanilines, polypyrroles and polythiophenes also fall into this class of elec-
trochromes (see 1.5.3.5).

1.5.3 Electrochromic Chemicals

A wide range of both inorganic and organic chemicals exhibit electrochromism and
34 Chapter 1
it is only possible to cover those of the greatest importance in this text. Readers
requiring greater details should refer to specialised texts.70,71

1.5.3.1 Inorganic Oxides

Inorganic oxides exhibiting electrochromism include cobalt oxide, nickel oxide,
molybdenum trioxide, vanadium oxide, tungsten trioxide and their mixtures. The
most important of these are those based on tungsten trioxide.

Figure 1.32 Mechanism of colour formation in tungsten trioxide.

Mechanistically the colour is formed by an optical charge-transfer between metal

centres in the solid-state lattice, e.g. in tungsten trioxide this involves partial reduc-
tion of the pale yellow WVI to the blue WV state. This reduction requires partial inser-
tion of a balancing cation, as shown schematically in Figure 1.32, where M is usually
lithium or hydrogen.
Pure tungsten trioxide, WO3, is very pale yellow and practically colourless in thin
films, whilst the reflected colour of the reduction product, M WVI WV O , is
x (1–x) x 3
proportional to the charge injected. The colour changes from blue (x = 0.2), through
purple (x = 0.6) and red (x = 0.7) to bronze (x = 0.8–1.0). Thin films of WO3 are either
amorphous, formed by thermal evaporation under vacuum, or microcrystalline,
produced by thermal sputtering in an oxygen rich atmosphere. An alternative proce-
dure, well suited to the production of large areas as in windows, is the sol–gel method
using colloidal hydrogen tungstate, followed by thermal curing.72

1.5.3.2 Prussian Blue

Prussian Blue is a long established blue pigment for paints and inks, whose use in
photographic prints is the origin of the term ‘blueprint’. The chemical also exhibits
electrochromic behaviour and its application in this field has been widely studied.72,73
Chemically Prussian Blue is Fe(III) hexacyanoferrate(II), with a distribution of
Fe(III) and Fe(II) oxidation states. Prussian Blue belongs to a general class of
potentially electrochromic hexacyanometallates, M1 x[M2CN 6]z, where M are transi-
tion metal ions in different oxidation states, e.g. ruthenium purple, iron(III) hexa-
cyanoruthenate(II). Thin films of Prussian Blue can be electrochemically deposited
onto electrode surfaces by electroreduction of solutions containing Fe( III) and hexa-
cyanoferrates(II).74 Prussian Blue produces the colourless Prussian White on reduc-
Phenomena Involving a Reversible Colour Change 35
tion and is therefore an anodically colouring electrochrome.

[FeIIIFeII(CN) ]1– + e– → [FeIIFeII(CN) ]2–

6 6
(blue) (colourless)

1.5.4 Applications of Electrochromism

The main application areas for electrochromic systems are in electrically switchable
rear-view car mirrors for anti-dazzle, in glazing units for temperature and light con-
trol and in visual displays. The main advantage offered by electrochromic systems in
the first two of these applications is the fact that the cells can be made very large, i.e.
one cell can comprise a whole glazing unit.

1.5.4.1 Rear-view Mirrors

The desirable properties of an electrochromic system for use in both rear-view mir-
rors or glazing units are:81

• Colours – blue, green, red and grey

• Size – up to 2 m  2 m (flat)
• Glass – curved for car mirrors
• Long Life – 25 years in buildings, 5 years in cars
• Transmission range – 15 to 75%
• Total cycles – 5000+ per year
• Temperature range – –20 to +80 °C operating
–40 to +120 °C survival

Electrically switchable rear-view mirrors for cars and trucks have been in commer-
cial production since the early 1990s, the leading company being the Gentex
Corporation.82 The Gentex mirror consists of an ITO–glass surface, with the conduc-
tive side inwards, and a reflective metallic surface, spaced less than a millimetre
apart. In the gap between these two electrodes is the solution electrolyte that is
coloured at the anode by formation of the stable radical cation, similar to Wurster’s
Blue, whilst a viologen is reduced at the cathode (Figure 1.34), the colours being
complementary, producing a deep green colouration. It is essential that a cur- rent
be applied to the cell whilst it is coloured, to avoid the electrode reaction being
reversed in solution. This is because the two types of coloured molecules can diffuse
through the system and react with each other, restoring the bleached states. The col-
oration may be cleared more rapidly by briefly reversing the polarity.
The Donnelly Corporation have also devised a rear-view mirror using an hybrid
system. A metal oxide electrochromic layer is used in conjunction with a non-elec-
trochromic reversible redox complex in the contacting solution.83
The electrochromic, self-dimming mirror market is expanding rapidly, comprising
around 6 M of the estimated 150 M total for mirrors in cars and trucks in 2000. The
market is set to grow to around 15 M by 2010, with additional growth in self-dim-
mable sunroofs and sun visors.
36 Chapter 1

Figure 1.34 Mechanism of an electrochromic cell for a car mirror.

1.5.4.2 Smart Windows

The control of the solar gain within buildings occurring through the glazing units
(Figure 1.35) is a highly desirable objective and has been the subject of much
research, especially by glass manufacturers such as Pilkington, Saint Gobain and
PPG. It would be most attractive to be able to do this dynamically, i.e. change in
response to environmental conditions, and this has led to the idea of ‘smart windows’.
The most widely studied systems for glazing units are those based on tungsten tri-
oxide. A schematic of a cross section through a typical cell is shown in Figure 1.36.

Clear Window Darkened Window

ROOM ROOM

hv hv

heat heat
heat

Figure 1.35 Heat reduction by darkened glazing.

The glass used in the glazing units is coated with a transparent conducting surface,
e.g. indium tin oxide (ITO) or stannic fluorine oxide (SFO). The electrochromic cell
is composed of an active electrode layer of tungsten trioxide (WO 3) coated onto the
conducting surface of one of the glass sheets, and a counter electrode of the non-
stoichiometric lithium vanadium oxide (Li xV 2O 5) or lithium nickel oxide (Li xNiO 2)
laid down on the conducting surface of the other glass sheet. In between these
two there is a thicker layer of a lithium ion polymer electrolyte. On applying a poten-
tial of around 1.5 V to the cell, lithium ions are discharged and dissolved at the
WO3 surface, the lithium being supplied from the counter electrode of LixV2O5. The
colourless WO3 becomes blue coloured (LixWO3) on lithium ion insertion, the
precise depth of colour depending on the degree of insertion; e.g. insertion of
12 mC cm–2 produces a sky blue colour, which reduces the visible light transmission
by a factor of 4. The colour of the window cell is erased on reversing the applied
charge.69
Phenomena Involving a Reversible Colour Change 37
Transparent
conducting film

Glass Counter
electrode

Polymer
electrolyte

Glass Active
electrode

Transparent
conducting film

Figure 1.36 Cross section through an electrochromic window.

Smart windows are ones which automatically darken when the ambient sunlight
reaches a predetermined level. One of the most promising approaches to achieving
this goal involves a combination of dye sensitised solar cells and electrochromic
cells.84,85 This work is based on the use of the dye-sensitised solar cells devised by
Grätzel et al. in the early 1990s, which will be described in greater detail in Chapter
4, section 4.7.1.2. The design principle behind these smart windows is the use of
electrochromic films that undergo changes in colour in response to changes in the
applied voltage, the power source being supplied by a photovoltaic cell working
independently but in tandem with the electrochromic film. This is known as a photo-
electrochromic cell and is illustrated schematically in Figure 1.37.
The dye sensitised semi-conductor electrode is a transparent conducting sheet of
glass coated (5 µm) with nanocrystalline TiO2 (diameter 20 nm) doped with a ruthe-
nium bipyridyl complex. The dye absorbs light, becomes excited and injects elec-
trons into the TiO2 electrode. The electrons travel into the transparent WO3 film and
then, to balance the charge, lithium ions from the electrolyte solution insert into the
WO3 and in so doing create the coloured species as described above. If the light
source is removed then the cell is bleached back to its original colour. However, if the
38 Chapter 1

DSSC EC

glass glass

Li+

I-

conducting
conducting
electrode
electrode electrolyte
solution

Dye doped WO3

Ti O2

Figure 1.37 Smart window from combined DSSC and EC cells.

cell is disconnected form the circuit before the light is removed it remains coloured,
because the electrons cannot escape from the reduced WO3 film.

1.5.4.3 Displays
The big difference between devising electrochromic systems for displays and glazing
is the need to construct arrays of smaller cells rather than one large one. and hence
the need for multiplexing. Since coloration in EC cells is caused by a chemical
change rather than by a light-emitting effect or interference, the colour remains even
when the current is turned off. This has led to the suggestion that the memory effect
could be used in low power large area information billboards.
In the 1980s IBM had a prototype small area, monochrome EC display that used
viologens as the electrochromes.86 At the time this did seem to offer scope for further
development but most projects in the area have been dogged by long-term stability
problems. Several other companies have used variations on metal plating–deplating
technology to lay down films on both electrodes, for instance ones made of bismuth,
using electrolytes containing bismuth bromide and lithium bromide.87,88
However, the difficulty in getting full colour and uniform large area coloration,
coupled with the cost of manufacture, has meant that liquid crystals have remained
the dominant technology into the early years of the 21st century.
Phenomena Involving a Reversible Colour Change 39
More recently, Grätzel’s work on nanocrystalline TiO2 has been extended into the
displays area.89,90 In this system an electrochromic molecule is linked to the surface
of the colourless TiO2 semiconductor on conducting glass. On applying a negative
potential, electrons are injected into the conduction band of the semi-conductor and
the absorbed molecule is reduced and changes colour. Applying a positive potential
reverses the process. The nanocrystalline TiO2 layer (5 µm) is highly porous and able
to absorb several hundred monolayers of the electrochromic molecules, enabling the
system to produce deep colours. Using phosphonated viologens, colour absorbance
changes of more than 2 have been achieved in 0.1 to 0.5 s. To construct closed cells
for use as display units, a counter electrode of zinc was coated with a white reflector
of microcrystalline TiO2 or ZrO2 . In operation, short-circuiting of the two electrodes
causes electrons to flow from the zinc electrode, it being oxidised to Zn2+, to the vio-
logens on the nanocrystalline electrode. The process is reversed by applying a volt-
age of 1–2 V. The oxidation–reduction process is said to be very fast, but the system
needs rapid ion migration in the electrolyte so that the charge can be compensated,
and polar solvents of low viscosity polar solvents, e.g. acetonitrile (switching time of
100 ms). Stability looks good at 150 000 oxidation–reduction cycles without degra-
dation. The system is shown schematically in Figure 1.38.

Glass White
reflector

Electrolye Zinc
View electrode

Conducting
layer
Nanocrystalline
electrode
layer and viologen
5000 nm

HO
O P
O

HO N N
O P
O
Nanoparticle
Absorbed monol ayer
20 nm HO
O
P 2 nm
O
N

Figure 1.38 Nanocrystalline electrochromic display cell.

40 Chapter 1

1.6 Miscellaneous Chromisms

Many of the other chromisms that have been described are irreversible and much less
important in terms of commercial applications. However, they do display interesting
behaviours, which could well prove to be of value in the future.

1.6.1 Piezo and Tribochromisms

Piezochromism and tribochromism are both colour change phenomena that occur by
mechanical means, the former under applied pressure and the latter by friction or
grinding. They have been observed in a few systems, but have not been exploited in
any commercial way.
Poly(3-alkylthiophenes) exhibit piezochromism, i.e. they change colour as pres-
sure is applied. For instance, a thin film of poly(3-dodecylthiophene), which is non-
planar at high temperatures with an absorption maximum at 520 nm, undergoes a
bathochromic shift as the pressure is increased, reaching an maximum absorption of
520 nm at 8 kbar. The shift in wavelength is thought to be due to an increase in the
length of conjugation in the chain as the packing is improved, compensating for con-
formational changes which also occur on heating.45,95,96
Tribochromism is exhibited when compounds crystallise in a metastable state and
give a more highly coloured state when they are ground (see also triboluminescence
in Chapter 3, section 3.9). In these cases the colour change is irreversible, as exem-
plified by the case of the fulgide (1.100). The folded metastable form (1.100a) is
bright yellow in its crystalline state, but turns to a dark red colour on grinding due to
the formation of the stable twisted form (1.100b).20

N N
C N C N
C C

O O

O O

(1.100a) (1.100b)
yellow red
folded metastable twisted stable
Phenomena Involving a Reversible Colour Change 41

1.6.2 Gasochromism
The term gasochromism has been applied to systems which change colour by redox
reactions involving gases; it is closely related to electrochromic behaviour.
The following system has been applied to switchable windows. Hydrogen, at a
concentration below its flammability level, in admixture with nitrogen, is dissociated
by a catalyst and intercalated into a tungsten layer on the glass. The layer turns deep
blue in colour and bleaching is achieved with oxygen. The energy consumption is
said to be lower than in comparable electrochromic systems, with solar transmission
of 75% reduced to 5% in a few seconds.97

1.6.3 Vapochromism
In vapochromic systems dyes change colour in response to a vapour or an aroma, and
therefore an alternative name is aromachromic. Systems based on this principle can
be considered as belonging to the family of ‘synthetic nose’ devices.
In a recent example metalloporphyrins are used as the sensing dyes for a wide vari-
ety of odorants, including alcohols, amines, arenes, ethers, halocarbons, ketones, phos-
phines, thioethers and thiols.98 An array of four different metalloporphyrins are placed
on a substrate and exposed to the vapours for 30 s. The various vapour molecules coor-
dinate onto the central metal atoms of the porphyrins, causing them to change colour
and producing a unique four-colour array. The resulting colour array is compared with
a library of known chemicals or mixtures and identification is achieved.

1.6.4 Chronochromism
Chronochromic systems are usually made from pH indicator type dyes, which are
placed in environments designed to allow the colour change to take place over pre-
determined period of time.99 One example is their use in toothpaste containing meth-
ylene blue and sodium ascorbate. On brushing the teeth the two chemicals interact
and the dye is reduced to a colourless product. Complete disappearance of the origi-
nal blue colour indicates the correct time for the user to brush their teeth.100 Another
outlet is in semi-permanent inks for the temporary marking of documents, e.g. routes
on maps. This uses the ammonium salt of phenolphthalein; the volatile ammonium
cation evaporates with time leaving the colourless phenolphthalein behind.101

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