Other types of intelligent textiles are those which change their colour

reversibly according to external environmental conditions, for this reason they

are also called chameleon fibres. Chromic materials are the general term
referring to materials which radiate the colour, erase the colour or just change
it because its induction caused by the external stimuli, as "chromic" is a suffix
that means colour. So we can classify chromic materials depending on the
stimuli affecting them:

• Photochromic: external stimuli energy is light.

• Thermochromic: external stimuli energy is heat.
• Electrochromic: external stimuli energy is electricity.
• Piezorochromic: external stimuli energy is pressure.
• Solvatechromic: external stimuli energy is liquid.
• Carsolchromic: external stimuli energy is electron beam.

The phenomenon produced in photochromic materials is called

photochromism, where the change in colour is due to incident light. However,
to date, photochromism is most important for optical switching data and
imaging systems, rather than in textile applications. It is possible to classify
photochromic fibres into different groups: those which emit the colour when
activated by the visible light and those fibres which emit the colour when
activated by ultraviolet radiation.

Although in the first group we can find both organic and inorganic materials
the most studied are the former because they are colourful, have high density
and a wide range of application. Organic photochromic materials generally do
not show this phenomenon in crystal form, they show their photochromism
after melting in some solvent. The problem is that material behaviour (such as
colour emitted, reaction speed, resistance, density, etc) is largely effected in a
positive or negative way by the solvent nature. For this reason, in order to
apply these materials to fibres, it is important to consider which solvent needs
to be used.

There are fibres which emit fluorescent colour, for example red, green or blue
under ultraviolet radiation in a dark place, though they maintain their original
colour when exposed to natural light. The inorganic fluorescent paints used
for this purpose are mixed at an approximate rate of 10% in the liquid during
the spinning operation. It is important to note that the colour can be freely
controlled by mixing various inorganic paints together or by adding the paints
to the natural colour of the threads.

Thermochromic materials are those whose colour changes as a result of

reaction to heat, especially through the application of thermochromic dyes
whose colours change at particular temperatures. Two types of
thermochromic systems that have been used successfully in textiles are: the
liquid crystal type and the molecular rearrangement type. In both cases, the
dyes are entrapped in microcapsules, applied to garment fabric like a pigment
in a resin binder. The most important types of liquid crystal for thermochromic
systems are the so-called cholesteric types, where adjacent molecules are
arranged so that they form helices. Thermochromism results from the
selective reflection of light by the liquid crystal. The wavelength of the light
reflected is governed by the refractive index of the liquid crystal and by the
pitch of the helical arrangement of its molecules. Since the length of the pitch
varies with temperature, the wavelength of the reflected light is also altered,
and colour changes result.

An alternative means of inducing thermochromism is by means of a

rearrangement of the molecular structure of a dye, as a result of a change in
temperature. The most common types of dye which exhibit thermochromism
through molecular rearrangement are the spirolactones, although other types
have also been identified. A colourless dye precursor and a colour developer
are both dissolved in an organic solvent. The solution is then
microencapsulated, and is solid at lower temperatures. Upon heating, the
system becomes coloured or loses colour at the melting point of the mixture.
The reverse change occurs at this temperature if the mixture is then cooled.
However, although thermochromism through molecular rearrangement in
dyes has aroused a degree of commercial interest, the overall mechanism
underlying the changes in colour is far from clear-cut and is still very much
open to speculation.

In addition to the changing of colour due to reaction to light or heat there are
other chromic fibres presenting other characteristics. These fibres have raised
the interest of people because of their surprising and interesting nature.
Therefore, there is the problem that this "boom" will soon come to an end
because these fibres are only considered to be a temporary fashion material.
In order to establish these fibres in everyday life it is specially necessary to
improve their endurance to light and to their accuracy.

Some of these fibres are those that present the phenomenon called solvate
chromism, whose colour changes when in contact with a liquid, for example
water. These materials are normally used for "design" swimsuits. Other
materials have applied paints which can store light and these are used in
working clothes for road works/repairs in bad light situations or for marking
arrows on carpets to guide people during a power failure. Apart from this, the
most important application for chromic materials is fashion, to create fantasy
designs changing its colour depending on the volume of incident light.

Chromism
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In chemistry, chromism is a process that induces a change, often reversible, in the

colors of compounds. In most cases, chromism is based on a change in the electron
states of molecules, especially the π- or d-electron state, so this phenomenon is
induced by various external stimuli which can alter the electron density of substances.
It is known that there are many natural compounds that have chromism, and many
artificial compounds with specific chromism have been synthesized to date.

Chromism is classified by what kind of stimuli are used. The major kinds of
chromism are as follows.

• thermochromism is chromism that is induced by heat, that is, a change of

temperature. This is the most common chromism of all.
 • photochromism is induced by light irradiation. This phenomenon is based on
the isomerization between two different molecular structures, light-induced
formation of color centers in crystals, precipitation of metal particles in a
glass, or other mechanisms.
• electrochromism is induced by the gain and loss of electrons. This
phenomenon occurs in compounds with redox active sites, such as metal ions
or organic radicals.
• solvatochromism depends on the polarity of the solvent. Most solvatochromic
compounds are metal complexes.
• cathodochromism is induced by electron beam irradiation.

Chromic phenomena
Chromic phenomena are those phenomena in which color is produced when light
interacts with materials in a variety of ways. These can be categorized under the
following five headings:

• Stimulated (reversible) color change

• The absorption and reflection of light
• The absorption of energy followed by the emission of light
• The absorption of light and energy transfer (or conversion)
• The manipulation of light.

Color changing phenomena

Phenomena which involve the change in color of a chemical compound take their
name from the type of external influence, either chemical or physical, which is
involved. Many of these phenomena are reversible. The following list includes all the
classic chromisms plus others of increasing interest in newer outlets.

• Photochromism - color change caused by light.

• Thermochromism - color change caused by heat.
• Electrochromism - color change caused by an electrical current.
• Gasochromism- color change caused by a gas - hydrogen/oxygen redox.
• Solvatochromism - color change caused by solvent polarity.
• Vapochromism - color change caused by vapour of an organic compound due
to chemical polarity/polarisation.
• Ionochromism - color change caused by ions.
• Halochromism - color change caused by a change in pH.
• Mechanochromism - color change caused by mechanical actions.
• Tribochromism - color change caused by mechanical friction.
• Piezochromism - color change caused by mechanical pressure.
• Cathodochromism - color change caused by electron beam irradiation.
• Radiochromism - color change caused by ionising radiation.
• Magnetochromism - color change caused by magnetic field.
• Biochromism - color change caused by interfacing with biological entity.
• Chronochromism - color change indirectly as a result of the passage of time.
• Aggregachromism - color change on dimerisation/aggregation of
chromophores.
• Crystallochromism - color change due to changes in crystal structure of a
chromophore.
Commercial applications of color change materials are very common and include
photochromics in ophthalmics, fashion/cosmetics and optical memory and optical
switches, thermochromics in paints, plastics and textiles and architecture,
electrochromics in car mirrors and smart windows, and solvatochromics in biological
probes.

Dyes and Pigments

Classical dyes and pigments produce color by the absorption and reflection of light;
these are the materials that make a major impact on the color of our daily lives. In
2000, world production of organic dyes was 800,000 tonnes and of organic pigments,
250,000 tonnes. There is also a very large production of inorganic pigments. Organic
dyes are used mainly to color textile fibers, paper, hair, leather, while pigments are
used largely in inks, paints and plastics.

Dyes are also made using the properties of chromic substances: Photochromic dyes
and Thermochromic dyes

Luminescence
The absorption of energy followed by the emission of light is often described by the
term luminescence. The exact term used is based on the energy source responsible for
the luminescence as in color-change phenomena.

• Electrical - electroluminescence Galvanoluminescence Sonoluminescence.

• Photons (light) - Photoluminescence Fluorescence Phosphorescence
Biofluorescence.
• Chemical - Chemiluminescence Bioluminescence Electrochemiluminescence.
• Thermal - Thermoluminescence Pyroluminescence Candololuminescence.
• Electron Beam - Cathodoluminescence Anodoluminescence
Radioluminescence.
• Mechanical - Triboluminescence Fractoluminescence Mechanoluminescence
Crystalloluminescence Lyoluminescence Elasticoluminescence.

Many of these phenomena are widely used in consumer products and other important
outlets. Cathodoluminescence is used in cathode ray tubes, photoluminescence in
fluorescent lighting and plasma display panels, phosphorescence in safety signs and
low energy lighting, fluorescence in pigments, inks, optical brighteners, safety
clothing, and biological and medicinal analysis and diagnostics, chemoluminescence
and bioluminescence in analysis, diagnostics and sensors, and electroluminescence in
the burgeoning areas of light-emitting diodes (LEDs/OLEDs), displays and panel
lighting. Important new developments are taking place in the areas of quantum dots
and metallic nanoparticles.

Light and energy transfer

Absorption of light and energy transfer (or conversion) involves colored molecules
that can transfer electromagnetic energy, usually from a laser light source, to other
molecules in another form of energy, such as thermal or electrical. These laser
addressable colorants are used in optical data storage, organic photoconductors, in
photomedicine (such as photodynamic therapy of cancer, photodiagnosis and
photoinsecticides). The absorption of natural sunlight solar energy by chromophores
is exploited in solar cells for the production of electrical energy by inorganic
photovoltaics and dye sensitized solar cell (DSSC) and also in the production of
useful chemicals via artificial photosynthesis.

Thermochromism
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A mood ring shown face front. Note the band of color change.

Thermochromism is the ability of substance to change color due to a change in

temperature. A mood ring is an excellent example of this, but it has many other uses
such as baby bottles (changes to a different color when cool enough to drink) and
kettles. Thermochromism is one of several types of chromism.

The two basic approaches are based on liquid crystals and leuco dyes. Liquid crystals
are used in precision applications, as their responses can be engineered to accurate
temperatures, but their color range is limited by their principle of operation. Leuco
dyes allow wider range of colors to be used, but their response temperatures are more
difficult to set with accuracy.

Principles
Thermochromatic liquid crystals

Some liquid crystals are capable of displaying different colors at different

temperatures. This change is dependent on selective reflection of certain wavelengths
by the crystallic structure of the material, as it changes between the low-temperature
crystallic phase, through anisotropic chiral or twisted nematic phase, to the high-
temperature isotropic liquid phase. Only the nematic mesophase has thermochromic
properties; this restricts the effective temperature range of the material.

The twisted nematic phase has the molecules oriented in layers with regularly
changing orientation, which gives them periodic spacing. The light passing through
the crystal undergoes Bragg diffraction on these layers, and the wavelength with the
greatest constructive interference is reflected back, which is perceived as a spectral
color. A change in the crystal temperature can result in a change of spacing between
the layers and therefore in the reflected wavelength. The color of the thermochromic
liquid crystal can therefore continuously range from non-reflective (black) through the
spectral colors to black again, depending on the temperature. Typically, the high
temperature state will reflect blue-violet, while the low-temperature state will reflect
red-orange. Since blue is a shorter wavelength than red, this indicates that the distance
of layer spacing is reduced by heating through the liquid-crystal state.

Some such materials are cholesteryl nonanoate or cyanobiphenyls.

Liquid crystals used in dyes and inks often come microencapsulated, in the form of
suspension.

Liquid crystals are used in applications where the color change has to be accurately
defined. They find applications in thermometers for room, refrigerator, aquarium, and
medical use, and in indicators of level of propane in tanks.

Liquid crystals are difficult to work with and require specialized printing equipment.
The material itself is also typically more expensive than alternative technologies.
High temperatures, ultraviolet radiation, some chemicals and/or solvents have a
negative impact on their lifespan.

Leuco dyes
Main article: Leuco dye

Example of a Hypercolor t-shirt. A hairdryer was used to change the blue to turquoise.

Another example of a Hypercolor t-shirt.

Thermochromic dyes are based on mixtures of leuco dyes with suitable other
chemicals, displaying a color change (usually between the colorless leuco form and
the colored form) in dependence on temperature. The dyes are rarely applied on
materials directly; they are usually in the form of microcapsules with the mixture
sealed inside. An illustrative example is the Hypercolor fashion, where microcapsules
with crystal violet lactone, weak acid, and a dissociable salt dissolved in dodecanol
are applied to the fabric; when the solvent is solid, the dye exists in its lactone leuco
form, while when the solvent melts, the salt dissociates, the pH inside the
microcapsule lowers, the dye becomes protonated, its lactone ring opens, and its
absorption spectrum shifts drastically, therefore it becomes deeply violet. In this case
the apparent thermochromism is in fact halochromism.
The dyes most commonly used are spirolactones, fluorans, spiropyrans, and fulgides.
The weak acids include bisphenol A, parabens, 1,2,3-triazole derivates, and 4-
hydroxycoumarin and act as proton donors, changing the dye molecule between its
leuco form and its protonated colored form; stronger acids would make the change
irreversible.

Leuco dyes have less accurate temperature response than liquid crystals. They are
suitable for general indicators of approximate temperature ("too cool", "too hot",
"about OK"), or for various novelty items. They are usually used in combination with
some other pigment, producing a color change between the color of the base pigment
and the color of the pigment combined with the color of the non-leuco form of the
leuco dye. Organic leuco dyes are available for temperature ranges between about −5
°C and 60 °C, in wide range of colors. The color change usually happens in a 3 °C
interval.

Leuco dyes are used in applications where temperature response accuracy is not
critical: eg. novelties, bath toys, flying discs, and approximate temperature indicators
for microwave-heated foods. Microencapsulation allows their use in wide range of
materials and products. The size of the microcapsules typically ranges between 3–
5 µm (over 10 times larger than regular pigment particles), which requires some
adjustments to printing and manufacturing processes.

An application of leuco dyes is in the Duracell battery state indicators. A layer of a

leuco dye is applied on a resistive strip to indicate its heating, thus gauging the
amount of current the battery is able to supply. The strip is triangular-shaped,
changing its resistance along its length, therefore heating up a proportionally long
segment with the amount of current flowing through it. The length of the segment
above the threshold temperature for the leuco dye then becomes colored.

Exposure to ultraviolet radiation, solvents and high temperatures reduce the lifespan
of leuco dyes. Temperatures above about 200–230 °C typically cause irreversible
damage to leuco dyes; a time-limited exposure of some types to about 250 °C is
allowed during manufacturing.

Materials
Inks

Thermochromic inks or dyes are temperature sensitive compounds, developed in the

1970s, that temporarily change color with exposure to heat. They come in two forms,
liquid crystals and leuco dyes. Liquid crystals are used in mood rings. Leuco dyes are
easier to work with and allow for a greater range of applications. These applications
include: flat thermometers, battery testers, clothing, and the indicator on bottles of
maple syrup that change color when the syrup is warm. The most well-known line of
clothing utilizing thermochromics was Hypercolor. The thermometers are often used
on the exterior of aquariums, or to obtain a body temperature via the forehead. Coors
light uses thermochromic ink on its cans now, changing from white to blue to indicate
the can is cold.

Paints

Thermochromic paint is a relatively recent development in the area of color-changing

pigments. It involves the use of liquid crystals or leuco dye technology. After
absorbing a certain amount of light or heat, the crystallic or molecular structure of the
pigment reversibly changes in such a way that it absorbs and emits light at a different
wavelength than at lower temperatures. Thermochromic paints are seen quite often as
a coating on coffee mugs, whereby once hot coffee is poured into the mugs, the
thermochromic paint absorbs the heat and becomes colored or transparent, therefore
changing the appearance of the mug.

Papers

Thermochromic papers are used for thermal printers. One example is the paper
impregnated with the solid mixture of a fluoran dye with octadecylphosphonic acid.
This mixture is stable in solid phase; however, when the octadecylphosphonic acid is
melted, the dye undergoes chemical reaction in the liquid phase, and assumes the
protonated colored form. This state is then conserved when the matrix solidifies again,
if the cooling process is fast enough. As the leuco form is more stable in lower
temperatures and solid phase, the records on thermochromic papers slowly fade out
over years; this may lead to interesting effects in combination with accounting
records, receipts from a thermal printer, and a tax audit.

Others

Another good example of this is the color indicators on batteries. The indicator turns
green if the battery still possesses a charge. This works by passing the charge of the
battery through a small resistor on the battery, and causes the pigment to absorb heat.
Once the paint has absorbed enough heat from the current of the battery, it changes
from black to green (usually), thus indicating that the battery still has a fair amount of
charge left in it. Another approach is using a resistor in the shape of a thin triangular
layer, under a thermochromic pigment. The variable width of the resistor causes it to
be heated unevenly, with the position of transition threshold temperature varying
depending on the current the battery is providing.

A simple-to-make thermochromic compound is zinc oxide, which is white at room

temperature but when heated changes to yellow due to various types of crystal lattice
defects. On cooling the zinc oxide reverts to white. Also lead(II) oxide has a similar
color change on heating. These solids are technically semiconductors, and the color
change is linked to their electronic properties.

Cuprous mercury iodide (Cu2HgI4) undergoes a phase transition at 55 °C, reversibly

changing from a bright red solid material at low temperature to a dark brown solid at
high temperature. Other such material is mercury(II) iodide, a crystalline material
which at 126 °C undergoes reversible phase transition from red alpha phase to pale
yellow beta phase. Yet another example is nickel sulfate, green at room temperature
but becoming yellow at 155 °C. Ag2HgI4 is yellow at low temperatures and orange
above 47–51 °C.[1]

Vanadium dioxide has been investigated for use as a "spectrally-selective" window

coating to block infrared transmission and reduce the loss of building interior heat
through windows. This material behaves like a semiconductor at lower temperatures,
allowing more transmission, and like a conductor at higher temperatures, providing
much greater reflectivity. [2][3] The phase change between transparent semiconductive
and reflective conductive phase occurs at 68 °C; doping the material with 1.9% of
tungsten lowers the transition temperature to 29 °C.

Other thermochromic solid semiconductor materials investigated for commercial use

are CdxZn1–xSySe1–y (x=0.5...1, y=0.5...1), ZnxCdyHg1–x–yOaSbSecTe1–a–b–c (x=0...0.5,
y=0.5...1, a=0...0.5, b=0.5...1, c=0...0.5), HgxCdyZn1–x–ySbSe1–b (x=0...1, y=0...1,
b=0.5...1).[4]

Some minerals are thermochromic as well; for example some chromium-rich pyropes,
normally reddish-purplish, become green when heated to about 80 °C.[5]

References
1. ^ "Thoughts of Amherst". .amherst.edu.
http://www3.amherst.edu/~thoughts/contents/amberger-thermochromism.html.
Retrieved 2010-07-12.
2. ^ "Sol-Gel Vanadium oxide". Solgel.com.
http://www.solgel.com/articles/August00/thermo/Guzman.htm. Retrieved 2010-07-
12.[dead link]
3. ^ "Intelligent Window Coatings that Allow Light In but Keep Heat Out – News
Item". Azom.com. http://www.azom.com/details.asp?ArticleID=2587. Retrieved
2010-07-12.
4. ^ Optical temperature indicator using thermochromic semiconductors U.S. Patent
5,499,597
5. ^ "Thermochromic Garnets". Minerals.gps.caltech.edu.
http://minerals.gps.caltech.edu/mineralogy/undergrad/garnet_2001/garnet.html.
Retrieved 2010-07-12.
Photochromism
From Wikipedia, the free encyclopedia
Jump to: navigation, search

A photochromic eyeglass lens, after exposure to sunlight with part of the lens covered
by paper.

Photochromism is the reversible transformation of a chemical species between two

forms by the absorption of electromagnetic radiation, where the two forms have
different absorption spectra.[1][2] Trivially, this can be described as a reversible change
of colour upon exposure to light. The phenomenon was discovered in the late 1880s,
including work by Markwald, who studied the reversible change of color of 2,3,4,4-
tetrachloronaphthalen-1(4H)-one in the solid state. He labeled this phenomenon
"phototropy", and this name was used until the 1950s when Yehuda Hirshberg, of the
Weizmann Institute of Science in Israel proposed the term "photochromism".[3]
Photochromism can take place in both organic and inorganic compounds, and also has
its place in biological systems (for example retinal in the vision process).

Overview
Photochromism does not have a rigorous definition, but is usually used to describe
compounds that undergo a reversible photochemical reaction where an absorption
band in the visible part of the electromagnetic spectrum changes dramatically in
strength or wavelength. In many cases, an absorbance band is present in only one
form. The degree of change required for a photochemical reaction to be dubbed
"photochromic" is that which appears dramatic by eye, but in essence there is no
dividing line between photochromic reactions and other photochemistry. Therefore,
while the trans-cis isomerization of azobenzene is considered a photochromic
reaction, the analogous reaction of stilbene is not. Since photochromism is just a
special case of a photochemical reaction, almost any photochemical reaction type may
be used to produce photochromism with appropriate molecular design. Some of the
most common processes involved in photochromism are pericyclic reactions, cis-trans
isomerizations, intramolecular hydrogen transfer, intramolecular group transfers,
dissociation processes and electron transfers (oxidation-reduction).

Another requirement of photochromism is two states of the molecule should be

thermally stable under ambient conditions for a reasonable time. All the same,
nitrospiropyran (which back-isomerizes in the dark over ~10 minutes at room
temperature) is considered photochromic. All photochromic molecules back-
isomerize to their more stable form at some rate, and this back-isomerization is
accelerated by heating. There is therefore a close relationship between photochromic
and thermochromic compounds. The timescale of thermal back-isomerization is
important for applications, and may be molecularly engineered. Photochromic
compounds considered to be "thermally stable" include some diarylethenes, which do
not back isomerize even after heating at 80 C for 3 months.

Since photochromic chromophores are dyes, and operate according to well-known

reactions, their molecular engineering to fine-tune their properties can be achieved
relatively easily using known design models, quantum mechanics calculations, and
experimentation. In particular, the tuning of absorbance bands to particular parts of
the spectrum and the engineering of thermal stability have received much attention.

Sometimes, and particularly in the dye industry, the term "irreversible photochromic"
is used to describe materials that undergo a permanent color change upon exposure to
ultraviolet or visible light radiation. Because by definition photochromics are
reversible, there is technically no such thing as an "irreversible photochromic"—this
is loose usage, and these compounds are better referred to as "photochangable" or
"photoreactive" dyes.

Apart from the qualities already mentioned, several other properties of photochromics
are important for their use. These include

• Quantum yield of the photochemical reaction. This determined the efficiency

of the photochromic change with respect to the amount of light absorbed. The
quantum yield of isomerization can be strongly dependent on conditions (see
below).
• Fatigue resistance. In photochromic materials, fatigue refers to the loss of
reversibility by processes such as photodegradation, photobleaching,
photooxidation, and other side reactions. All photochromics suffer fatigue to
some extent, and its rate is strongly dependent on the activating light and the
conditions of the sample.
• Photostationary state. Photochromic materials have two states, and their
interconversion can be controlled using different wavelengths of light.
Excitation with any given wavelength of light will result in a mixture of the
two states at a particular ratio, called the "photostationary state". In a perfect
system, there would exist wavelengths that can be used to provide 1:0 and 0:1
ratios of the isomers, but in real systems this is not possible, since the active
absorbance bands always overlap to some extent.
• Polarity and solubility. In order to incorporate photochromics in working
systems, they suffer the same issues as other dyes. They are often charged in
one or more state, leading to very high polarity and possible large changes in
polarity. They also often contain large conjugated systems that limit their
solubility.

Photochromic complexes

A photochromic complex is a kind of chemical compound that has photoresponsive

parts on its ligand. These complexes have a specific structure: photoswitchable
organic compounds are attached to metal complexes. For the photocontrollable parts,
thermally and photochemically stable chromophores (azobenzene, diarylethene,
spiropyran, etc.) are usually used. And for the metal complexes, a wide variety of
compounds that have various functions (redox response, luminescence, magnetism,
etc.) are applied.
The photochromic parts and metal parts are so close that they can affect each other's
molecular orbitals. The physical properties of these compounds shown by parts of
them (i.e., chromophores or metals) thus can be controlled by switching their other
sites by external stimuli. For example, photoisomerization behaviors of some
complexes can be switched by oxidation and reduction of their metal parts. Some
other compounds can be changed in their luminescence behavior, magnetic interaction
of metal sites, or stability of metal-to-ligand coordination by photoisomerization of
their photochromic parts.

Classes of photochromic materials

Photochromic molecules can belong to various classes: triarylmethanes, stilbenes,
azastilbenes, nitrones, fulgides, spiropyrans, naphthopyrans, spiro-oxazines, quinones
and others.

[edit] Spiropyrans and spirooxazines

Spiro-mero photochromism.

One of the oldest, and perhaps the most studied, families of photochromes are the
spiropyrans. Very closely related to these are the spirooxazines. For example, the
spiro form of an oxazine is a colorless leuco dye; the conjugated system of the
oxazine and another aromatic part of the molecule is separated by a sp³-hybridized
"spiro" carbon. After irradiation with UV light, the bond between the spiro-carbon
and the oxazine breaks, the ring opens, the spiro carbon achieves sp² hybridization
and becomes planar, the aromatic group rotates, aligns its π-orbitals with the rest of
the molecule, and a conjugated system forms with ability to absorb photons of visible
light, and therefore appear colorful. When the UV source is removed, the molecules
gradually relax to their ground state, the carbon-oxygen bond reforms, the spiro-
carbon becomes sp³ hybridized again, and the molecule returns to its colorless state.

This class of photochromes in particular are thermodynamically unstable in one form

and revert to the stable form in the dark unless cooled to low temperatures. Their
lifetime can also be affected by exposure to UV light. Like most organic dyes they are
susceptible to degradation by oxygen and free radicals. Incorporation of the dyes into
a polymer matrix, adding a stabilizer, or providing a barrier to oxygen and chemicals
by other means prolongs their lifetime.
Diarylethenes

Dithienylethene photochemistry.

The "diarylethenes" were first introduced by Irie and have since gained widespread
interest, largely on account of their high thermodynamic stability. They operate by
means of a 6-pi electrocyclic reaction, the thermal analog of which is impossible due
to steric hindrance. Pure photochromic dyes usually have the appearance of a
crystalline powder, and in order to achieve the color change, they usually have to be
dissolved in a solvent or dispersed in a suitable matrix. However, some diarylethenes
have so little shape change upon isomerization that they can be converted while
remaining in crystalline form.

Azobenzenes

Azobenzene photoisomerization.

The photochromic trans-cis isomerization of azobenzenes has been used extensively

in molecular switches, often taking advantage of its shape change upon isomerization
to produce a supramolecular result. In particular, azobenzenes incorporated into
crown ethers give switchable receptors and azobenzenes in monolayers can provide
light-controlled changes in surface properties.

Photochromic quinones

Some quinones, and phenoxynaphthacene quinone in particular, have photochromicity

resulting from the ability of the phenyl group to migrate from one oxygen atome to
another. Quinones with good thermal stability have been prepared, and they also have
the additional feature of redox activity, leading to the construction of many-state
molecular switches that operate by a mixture of photonic and electronic stimuli.

Inorganic photochromics

Many inorganic substances also exhibit photochromic properties, often with much
better resistance to fatigue than organic photochromics. In particular, silver chloride is
extensively used in the manufacture of photochromic lenses. Other silver and zinc
halides are also photochromic.
Applications
Sunglasses

One of the most famous reversible photochromic applications is color changing lenses
for sunglasses, as found in eye-glasses. The largest limitation in using PC technology
is that the materials cannot be made stable enough to withstand thousands of hours of
outdoor exposure so long-term outdoor applications are not appropriate at this time.

The switching speed of photochromic dyes is highly sensitive to the rigidity of the
environment around the dye. As result, they switch most rapidly in solution and
slowest in the rigid environment like a polymer lens. Recently it has been reported
that attaching flexible polymers with low glass transition temperature (for example
siloxanes or poly(butyl acrylate)) to the dyes allows them to switch much more
rapidly in a rigid lens.[4][5] Some spirooxazines with siloxane polymers attached switch
at near solution-like speeds even though they are in a rigid lens matrix.

Supramolecular chemistry

Photochromic units have been employed extensively in supramolecular chemistry.

Their ability to give a light-controlled reversible shape change means that they can be
used to make or break molecular recognition motifs, or to cause a consequent shape
change in their surroundings. Thus, photochromic units have been demonstrated as
components of molecular switches. The coupling of photochromic units to enzymes or
enzyme cofactors even provides the ability to reversibly turn enzymes "on" and "off",
by altering their shape or orientation in such a way that their functions are either
"working" or "broken".

Data storage

The possibility of using photochromic compounds for data storage was first suggested
in 1956 by Yehuda Hirshberg.[6] Since that time, there have been many investigations
by various academic and commercial groups, particularly in the area of 3D optical
data storage which promises discs that can hold a terabyte of data. Initially, issues
with thermal back-reactions and destructive reading dogged these studies, but more
recently more-stable systems have been developed.[citation needed]

Novelty items

Reversible photochromics are also found in applications such as toys, cosmetics,

clothing and industrial applications. If necessary, they can be made to change between
desired colors by combination with a permanent pigment.