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Photochromism of spiropyrans and spirooxazines in the solid state:
low temperature enhances photocolorationw
Jun Harada,* Yuta Kawazoe and Keiichiro Ogawa*
Received (in Cambridge, UK) 3rd December 2009, Accepted 16th January 2010
First published as an Advance Article on the web 2nd February 2010
DOI: 10.1039/b925514a
Published on 02 February 2010. Downloaded by Brown University on 31/10/2014 03:37:17.
In this study we have revealed that spiropyrans and spiro-
oxazines, which have long been believed to be non-photochromic
in the solid state, are generally photochromic in the solid state at
least at low temperatures and that their photoreactivity increases
greatly as the temperature is lowered.
Photochromic compounds usually show photochromism in
various environments, e.g., in solution, in polymer matrices,
and in the solid state. Although numerous compounds have
been shown to possess photochromic properties, the variety of
compounds that show photochromism in the solid state is
rather limited. In this study we have revealed that spiropyrans
(SP) and spirooxazines (SO), which have long been believed
to be non-photochromic in the solid state, are generally
photochromic even in the solid state, and that their photo-
reactivity increases greatly as the temperature is lowered.
Both SP and SO belong to the most extensively studied
families of photochromic compounds.1 The photochromism of
these compounds is based on the interconversion between the
closed spiro form and open planar merocyanine forms.2 Upon
UV irradiation of the stable spiro form, cleavage of the
Cspiro–O bond takes place through a pericyclic reaction, which
is followed by unfolding of the molecule to a colored planar
merocyanine form [eqn (1)]. The merocyanine form reverts
back to the spiro form by spontaneous fading in the dark or by
irradiation with visible light.
ð1Þ
The photochromic reactions of SP and SO have been
generally believed not to occur in the solid state, while vast
numbers of derivatives have been reported to show photo-
chromism in fluid solution, or in rigid media such as glass
Department of Basic Science, Graduate School of Arts and Sciences,
The University of Tokyo, Komaba, Meguro-ku, Tokyo, Japan.
E-mail: harada@ramie.c.u-tokyo.ac.jp, ogawa@ramie.c.u-tokyo.ac.jp;
Fax: +81 3 5454 6576; Tel: +81 3 5454 6576
w Electronic supplementary information (ESI) available: Experimental
details; crystal data and structure refinements for 1 and 2; ORTEP
diagrams for 1 and 2 (PDF); X-ray crystallographic data (CIF).
CCDC 756906, 756907, 756908 and 756909. For ESI and crystallo-
graphic data in CIF or other electronic format see DOI: 10.1039/
b925514a
This journal is 
c The Royal Society of Chemistry 2010
solutions and polymer films. The photo-inertness in the solid
state has usually been explained in terms of the lack of free
volume in crystals required for the transformation from the
spiro to merocyanine form. Although some SP and SO have
sporadically been reported to show photochromism in
the solid state, their photochromic properties have been
considered to be rather exceptional or due to special molecular
design.3,4 The solid-state photocoloration of some SP and SO
were reported to be induced by intense femtosecond laser pulse
excitation, while steady UV light irradiation did not bring
about the coloration.5 In this study we have investigated the
solid-state photochromism of several SP and SO, mainly by
variable-temperature diffuse reflectance spectroscopy.
1,3,3-Trimethylspiro[indoline-2,3 0 -[3H]-naphtho[2,1-b]pyran]
(1) is the first reported photochromic SP, which was clearly
described not to be photochromic in the solid state.6 As was
expected, a pale pink crystal of 1 did not change its color on
UV irradiation (365 nm, Hg lamp) at room temperature
(Fig. 1a, b). The irradiation at 90 K, however, rapidly changed
the crystal to reddish purple (Fig. 1c).7 The color did not fade
in the dark at 90 K and returned to the original pale pink
after warming to room temperature. The results clearly show
that the crystal of 1, which is not photochromic at room
temperature, undergoes a reversible photocoloration at low
temperature.
1,3,3-Trimethylspiro[indoline-2,3 0 -[3H]-naphth[2,1-b][1,4]-
oxazine] (2) is also the first reported photochromic SO
compound.8 Colorless crystals of 2 showed photochromic
properties similar to those of 1. Compound 2 was reported
to show photochromism even in the solid state when it was
irradiated with intense UV light.4 The slightly photochromic
nature of 2 in the solid state was confirmed by UV irradiation
(365 nm) at room temperature. An almost colorless crystal
turned faint blue after irradiation (Fig. 1e).9 Development of
blue color was much more evident when the crystal was
irradiated at 90 K (Fig. 1f). The dark blue color did not fade
at 90 K and the original colorlessness was resumed after the
Fig. 1 Photographs of the crystals of 1 and 2. (a) 1 and (d) 2 at room
temperature before irradiation; (b) 1 and (e) 2 after UV irradiation at
room temperature; (c) 1 and (f) 2 after UV irradiation at 90 K.
Chem. Commun., 2010, 46, 2593–2595 | 2593
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Fig. 2 Diffuse reflectance spectra of 1 before and after irradiation at

298 and 78 K. The sample was irradiated at each temperature under
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Fig. 3 Diffuse reflectance spectra of 2 before and after irradiation at

the same conditions. 300 and 80 K. The sample was irradiated at each temperature under
the same conditions.

crystal was warmed to room temperature. The results also

show that the photochromism of the crystal of 2 was greatly
enhanced at low temperature.
The temperature dependence of photocoloration in the solid
state was examined by diffuse reflectance spectroscopy of
microcrystalline powders. Fig. 2 shows diffuse reflectance
spectra of the microcrystalline powder of 1 at 298 and 78 K.
Before irradiation the reflectance at both temperatures shows
a slight reduction between 400 and 600 nm in addition to a
sharp fall off in the UV region. The spectra indicate that in
Fig. 4 Variable temperature diffuse reflectance spectra of 1 before,
addition to the strong absorption in the UV region the powder
just after irradiation, and 2.5 min after that. The sample was irradiated
weakly absorbs visible light. The absorption band in the visible
at each temperature under the same conditions. The spectra before
region is assignable to a small amount of merocyanine forms. irradiation at 190 and 160 K are omitted for clarity because they are
This indicated that the merocyanine forms exist in the crystal almost identical to that at 200 K in this wavelength region.
before irradiation, and are responsible for the pale pink color
of the crystals.10
The photochromic reaction was observed only at low Similar results were obtained for irradiation (365 nm,
temperature. Irradiation with 365 nm light at room tempera- 13 mW cm2, 1 min) of 2 (Fig. 5).11 Decreasing the tempera-
ture did not cause any spectral changes, which indicates that ture increased the amount of merocyanine forms and
photocoloration did not occur at the temperature. Irradiation suppressed the thermal back reaction. These results indicate
at 78 K, however, greatly changed the spectrum and the color that the enhancement of the photocoloration of 1 and 2 in the
of the powder. The color change from faint pink to purple was solid state is attributable to the suppression of the color
reflected in the spectrum, which shows a significant decrease in fading, which is a thermal process with some activation
the reflectance between 380 and 620 nm. The spectral changes energy.
correspond to the formation of merocyanine forms in the solid Solid-state photochromism was observed for many other SP
state. When the sample was left at 78 K in the dark, the (3)–(6) and SO (7)–(9). As for the crystals of 1 and 2, UV light
spectrum did not change for at least an hour. irradiation of the crystals of these compounds resulted in no or
Essentially the same results were obtained on 365 nm-light only marginal photocoloration at room temperature. As the
irradiation of compound 2, the photochromic spectral changes temperature was decreased, all the compounds became
of which were almost negligible at room temperature but photochromic. Although not all the crystals exhibited strong
significant at 80 K (Fig. 3). These results show that the
photochromic reactions in the solid state of 1 and 2 proceed
significantly at liquid nitrogen temperature and the photo-
induced merocyanine forms are stable at the temperature.
Spectral studies at intermediate temperatures revealed
that decreasing the temperature gradually enhanced the
photocoloration of 1 and suppressed the fading of the color
(Fig. 4). At each temperature the extent of the photocoloration
and the thermal back reaction were examined by successively
measuring two diffuse reflectance spectra, i.e., just after the
irradiation (365 nm, 13 mW cm2, 3 min) and 2.5 min after the
previous measurement.11 Fig. 4 shows that UV irradiation Fig. 5 Variable temperature diffuse reflectance spectra of 2 before,
produced a larger amount of the merocyanine forms as the just after irradiation, and 2.5 min after that. The sample was irradiated
temperature decreased. Fig. 4 also indicates that the thermal at each temperature under the same conditions. The spectra before
back reaction was suppressed when the temperature was irradiation at 240 and 160 K are omitted for clarity because they are
lowered and became negligible at 160 K. almost identical to that at 260 K in this wavelength region.

2594 | Chem. Commun., 2010, 46, 2593–2595 This journal is 

c The Royal Society of Chemistry 2010

coloration, perceived color and/or reflectance spectra
confirmed that the photochromic reactions were enhanced at
low temperature.
Published on 02 February 2010. Downloaded by Brown University on 31/10/2014 03:37:17.
The reason for the photo-inertness of SP and SO in the solid
state at room temperature can be explained in terms of fast
thermal back reactions during the photo-irradiation. Whether
the photocoloration occurs or not under certain conditions
depends on the rates of photocoloration and thermal back
reaction during the photo-irradiation. Non-photochromic
properties of SP and SO in the solid state have been mentioned
in many papers and considered to be due to the restriction
of the forward photoreaction. The results shown in this
communication, however, indicate that the high rate of
thermal back reactions is a more plausible reason, because
the lowering of temperature, which should not relieve the
restriction of the forward photoreaction, slows down the
thermal fading and enhances the photocoloration. This is,
actually, the same reason for the fact that many SP and SO in
solution do not show durable photocoloration at room
temperature and the steady state spectral measurement of
the photoproducts often requires low temperatures.
Although it is not clear at present whether the reactions take
place at crystal sites under lattice control or only occur at
crystal defects, this study shows that crystals of SP and SO,
which have generally been believed not to be photochromic,
are actually photochromic, at least at low temperatures, and
that photochromism of SP and SO in the solid state is not
an exceptional but a quite ordinary phenomenon. Further
investigation including determination of the structures of
the colored species using X-ray crystallography is now in
progress.
This journal is 
c The Royal Society of Chemistry 2010
View Article Online
This work was supported by a Grand-in-Aid for Scientific
Research in Priority Areas ‘‘New Frontiers in Photochromism
(No. 471)’’ from the Ministry of Education, Culture, Sports,
Science and Technology (MEXT) Japan.
Notes and references
1 For reviews, see: Photochromism. Techniques of Chemistry,
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R. J. Guglielmetti, Plenum Press, New York, 1999, Topics in Applied
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2 Four configurations are possible for planar merocyanine forms
according to the configurations of the central CQC and XQC bonds.
The structure drawn in eqn (1) is supposed to be the most stable isomer.
3 S. Bénard and P. Yu, Adv. Mater., 2000, 12, 48–50; S. Bénard and
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6 E. Fischer and Y. Hirshberg, J. Chem. Soc., 1952, 4522–4524.
7 Single crystal X-ray diffraction analysis of 1 and 2 did not show
any phase transition in the temperature range between room
temperature and 90 K, see ESIw.
8 R. E. Fox, Research Reports and Test Items Pertaining to Eye
Protection of Air Crew Personnel, Final Report on Contract
AF41(657)-215, AD 440226, April 1961.
9 The compound 2 dissolved in the epoxy glue that attaches the
crystal to the glass capillary turned deeper blue.
10 The populations of the merocyanine forms should be very low
because they were not detected by X-ray diffraction analysis.
11 The scan speed of the spectral measurement was 1000 nm min1
and each scan (800–250 nm) took about one minute. After the
photoreaction and subsequent spectral measurements at each
temperature, the photoproduct was completely eradicated by
warming the sample up to 340 K.
Chem. Commun., 2010, 46, 2593–2595 | 2595