Fast cis-trans isomerization of an azobenzene derivative in liquids and liquid crystals under a low electric field

Article abstract of DOI:10.1002/anie.200705699

A dramatically increased rate of cis-trans isomerization of an azobenzene derivative dissolved in liquids (e.g. benzonitrile) and liquid crystals relative to the corresponding thermally activated process can be achieved by applying a low static electric field (see picture) without adding any supporting electrolyte. This electric-field-induced isomerization can affect the electrooptical behavior of azobenzene-doped liquid crystals. (Chemical Equation Presented)

Full text of DOI:10.1002/anie.200705699

Communications
DOI: 10.1002/anie.200705699
Electroisomerization
Fast Cis–Trans Isomerization of an Azobenzene Derivative in Liquids
and Liquid Crystals under a Low Electric Field**
Xia Tong, Maxime Pelletier, Andrzej Lasia, and Yue Zhao*
Reversible trans–cis photoisomerization of azobenzene and
its derivatives has been extensively studied and exploited as a
photoswitch in numerous molecular systems and functional
materials.[1] Thermally activated cis–trans isomerization is
also well understood, the rate of which depends on the
substituents on the azobenzene and the environment sur-
roundingthe chromophore. [1,2] Little attention has been paid
to the effect of an electric field on the isomerization of
azobenzene. Fujishima et al. first reported an electrochemical
process inducingthe conversion of cis-azobenzene to trans-
azobenzene.[3] With amphiphilic azobenzene derivatives
forming a Langmuir–Blodgett (LB) monolayer film on an
electrode, cis-azobenzene formed on UV irradiation can be
reduced to hydrazobenzene (two-electron reduction in aque-
ous solution), which is then reoxidized to trans-azobenzene.
This coupled photochemical and electrochemical isomeriza-
tion was suggested for high-density information storage.[3]
Later, the same group found that cis-azobenzene in such an
LB monolayer could return to the trans isomer by an
for cis–trans isomerization was also in the range of 103 Vmmꢀ1.
The effect of high electric fields on the isomerization of other
chromophores was also reported.[7] Here we report the
astonishingfindingthat with an azobenzene derivative
dissolved in liquids or liquid crystals, a low static electric
field applied on the mixture between two conductive electro-
des can induce fast cis–trans isomerization. In benzonitrile, for
instance, the rate constant of cis–trans isomerization under an
external field strength of 1 Vmmꢀ1 could be six orders of
magnitude faster than thermal isomerization in the absence of
the field. We show that this drastic electric-field-induced
effect could have important implications for doped liquid
crystals usingazobenzene as a photoswitch to control the
electrooptical properties.
The cis–trans isomerization of the used azobenzene
derivative, 4-hexyloxy-4’-(4-hexyloxybenzoate)azobenzene
(HHBAzo),[8] proceeded very slow in solution at ca. 228C in
the dark. Figure 1a shows the UV/Vis spectra of a solution of
[4]
electrostatic process involvingno redox reaction. Since the
azobenzene derivative was deposited on the workingelec-
trode dipped in an electrolyte solution, cis–trans isomeriza-
tion was attributed to the interaction of azobenzene with the
high electric field on the order of 103 Vmmꢀ1 present in the
electrical double layer. However, the underlyingmechanism
remains unknown, since even with a high field of 103 Vmmꢀ1,
direct interaction with azobenzene, the trans and cis isomers
of which have different dipole moments (Dm ꢁ 3 D for
unsubstituted azobenzene) cannot be responsible for a drastic
loweringof the cis–trans isomerization barrier.[4] More
recently, reversible cis–trans isomerization of individual
azobenzene molecules on a metal surface was achieved by
scanningtunnelingmicroscopy (STM), first with tunneling
electrons[5] and then by means of the electric field at the STM
junction.[6] In the latter case, the measured threshold voltage
HHBAzo in benzonitrile (ca. 3 wt%), which was filled into a
parallely rubbed indium-tin-oxide (ITO)-coated liquid-crystal
(LC) cell with a 5-mm gap (E.H.C. Japan). As the cell is
transparent to l > 330 nm, the absorption peak of the trans-
azobenzene at about 360 nm (p–p* transition) can clearly be
seen. After UV irradiation of the solution (ca. 365 nm,
15 mWcmꢀ2, 10 s), disappearance of this peak indicates
efficient trans–cis photoisomerization. The weak absorption
peak of the cis-azobenzene around 450 nm (n–p* transition)
is difficult to see due to the undulatingbaseline caused by the
interference of the glass cell. The spectrum recorded one hour
after UV irradiation is almost unchanged owing to the very
slow thermal conversion of the cis-azobenzene back to the
trans form. By contrast, when a rectangular electric pulse of
5 V (1 Vmmꢀ1) and 300 ms duration is applied across the
solution, recovery of the absorption peak of trans-azobenzene
indicates fast cis–trans isomerization under the low static
electric field. The fact that the recovered absorbance is even
slightly higher than the initial absorbance suggests the
existence of a small amount of cis-azobenzene prior to the
UV irradiation. Figure 1b shows the time-resolved increase of
the absorbance at 356 nm under a rectangular electric pulse of
variable amplitude (0.4–1 Vmmꢀ1) with a fixed duration of
500 ms. The cis–trans isomerization starts at a threshold field
of about 0.5 Vmmꢀ1, becomes faster with increasingfield
strength and can reach completion within 500 ms under 0.8
[*] X. Tong, M. Pelletier, Prof. Dr. A. Lasia, Prof. Dr. Y. Zhao
DØpartement de chimie
UniversitØ de Sherbrooke
Sherbrooke, QuØbec, J1K2R1 (Canada)
Fax: (+1)819-821-8017
E-mail: yue.zhao@usherbrooke.ca
Homepage: http://pages.usherbrooke.ca/yzhao/
[**] Financial support from the Natural Sciences and Engineering
Research Council of Canada and le Fonds quØbØcois de la recherche
sur la nature et les technologies of QuØbec via The Centre for Self-
Assembled Chemical Structures (CSACS) is acknowledged. We are
grateful to Profs. Patrick Ayotte and Jean Lessard for helpful
discussions.
Supporting information for this article is available on the WWW
under http://www.angewandte.org or from the author.
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Figure 2. Azobenzene derivative in the nematic liquid crystal 5CB.
Figure 1. Azobenzene derivative in benzonitrile. a) UV/Vis spectra
showing that fast cis–trans isomerization occurred under a low static
electric field (electric pulse: 1 Vmmꢀ1, 300 ms); c initial solution,
b immediately after irradiation, a 1 h after UV irradiation, g
after electric pulses following UV irradiation. b) Kinetics of cis–trans
isomerization under a 500-ms rectangular electric pulse of various low
amplitudes.
a) UV/Vis spectra showing the electric-field-induced cis–trans isomer-
ization (electric field: 18 Vmmꢀ1, 20 s); c initial mixture, b
immediately after irradiation, a 10 min at 388C after UV irradiation,
g after electric field following UV irradiation. b) Change in absorb-
ance of the trans-azobenzene before, under, and after application of
the electric field (electric field: 18 Vmmꢀ1, 20 s).
and 1 Vmmꢀ1. At E < 0.8 Vmmꢀ1, cis–trans isomerization
stops when the voltage is turned off. The electrically induced
isomerization appears to be a first-order reaction; fittingthe
curve at 1 Vmmꢀ1 yielded a rate constant of about 11.4 sꢀ1,
which is six orders of magnitude faster than thermal cis–trans
isomerization in the absence of the field, which has a rate
constant of about 1.15 ” 10ꢀ5 sꢀ1. We emphasize that the
results in Figure 1b were obtained by using the same solution.
That is, after each application of the electric pulse, the
solution was re-irradiated with UV light to convert the trans-
azobenzene back to the cis-azobenzene before an electric
pulse of a different strength was applied again. The coupled
photo- and voltage-induced isomerization processes are
reversible. However, isomerization from trans- to cis-azoben-
zene under an applied electric field was not observed.
Benzonitrile is a polar solvent havinga high dielectric
constant (e = 26 at 208C). Even though the benzonitrile used
was anhydrous and of high purity (> 99%), some ions may be
present. The question can be raised whether the fast cis–trans
isomerization may be caused by heatingof the solution due to
a current flowingthrough the cell. To answer this question,
and to verify the generality of the phenomenon as well, we
investigated HHBAzo (ca. 4%) dissolved in a nematic liquid
crystal (LC), namely, 4’-pentyl-4-cyanobiphenyl (5CB, e =
14). The results in Figure 2 basically show the same phenom-
enon for HHBAzo in the LC solvent, although it takes a
higher field (18 Vmmꢀ1) and longer time (20 s) than in
benzonitrile. On UV irradiation trans–cis photoisomerization
takes place, while after 20 s under the electric field, the cis-
azobenzene is converted into the trans form (Figure 2a). For
the sake of argument, the mixture was purposely heated to
388C for 10 min, but the recorded spectrum showed very
limited thermal cis–trans isomerization of HHBAzo in 5CB
(as little as for thermal relaxation 1 h at room temperature
after UV irradiation; spectrum not shown). From the result in
Figure 2b, we can deduce that under the applied electric field
the mixture could not have a temperature above the nematic–
isotropic transition temperature Tni of 5CB (ca. 358C).
Figure 2b shows the time-resolved change in absorbance at
356 nm of trans-azobenzene in 5CB under the voltage. The
apparently peculiar behavior is due to the concomitant
change in electric field-induced liquid-crystal orientation.
When the voltage is on, the quick drop and oscillating
variation in absorbance is caused by the dynamic change in
liquid crystal reorientation that alters the transmittance of the
mixture, that is, the baseline of the whole spectrum. At longer
times (> 8 s), the steady increase in absorbance is due to
conversion of the cis-azobenzene back to the trans-azoben-
[8]
zene. However, trans-azobenzene, beingliquid-crystalline,
is aligned with the surrounding 5CB molecules perpendicular
to the substrate surface, so that they cannot absorb the beam
of the spectrophotometer. At the end of the electric pulse
(field-off), trans-azobenzene relaxed with 5CB molecules to
lie in the plane, and hence their absorption at 356 nm jumped
to the initial level before the UV-induced trans–cis photo-
isomerization. This result indicates that 5CB remains in the
nematic phase under the electric field, which is also confirmed
by polarizingoptical microscopy. Therefore, no heatingof the
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mixture to T> Tni occurred, because otherwise 5CB would
beingoxidized and brought back to the neutral trans form.[10]
In the ITO-coated LC cell, the azobenzene solution of small
volume (due to the small gap of the cell) is in contact with
large surfaces of the electrodes, and hence the above reactions
could quickly propagate through the bulk solution by
diffusion. We also carried out control tests, and the results
support the electrochemical origin of the observed phenom-
enon (see the SupportingInformation). We note that
although the ITO in the LC cell is coated with a very thin
polyimide layer, passage of electric current is allowed.[11]
Although the most probable mechanism is based on the
known electrochemical reduction of azobenzene, the
reported fast cis–trans isomerization of azobenzenes in liquids
and liquid crystals without any added supportingelectrolytes
under a low external electric field was unknown until now.
The findingis important because it shows that an electric field
can affect the cis–trans isomerization of azobenzene deriva-
tives much more easily than previously thought, and this must
be taken into account in switchingor device applications in
which an electric field is involved. In particular, the reversible
photoisomerization of azobenzene derivatives has been much
used as a photoswitch to alter the optical and electrooptical
behavior of LCs;[1] obviously, the conversion of cis-azoben-
zene to the trans isomer under an applied electric field may
have important consequences for the performance. We
designed an experiment to investigate the possible impact of
this phenomenon on the properties of azobenzene-doped
LCs. Figure 3a shows the changes in transmittance of nematic
BL006 containing15% of HHBAzo in response to combined
UV exposure and an electric field. In this case, the mixture
was filled into a perpendicularly rubbed, ITO-coated LC cell
with 5-mm gap, in which LC molecules are aligned to adopt a
twist orientation. Between two crossed polarizers, the mixture
initially is homogeneous and highly transparent. On UV
exposure (20 mWcmꢀ2), the transmittance drops as a result of
the phase separation induced by trans–cis photoisomerization
(a phase rich in cis-azobenzene is immiscible with BL006).[8]
When the UV light is turned off, the two-phase morphology of
the mixture and the reduced transmittance remain quite
stable in the dark for several hours due to the very slow
thermal cis–trans relaxation. In this experiment, however,
about 15 s after turningoff the UV light, the mixture was
subjected to six rectangular electric pulses of 40 V (8 Vmmꢀ1)
and 2-s duration, separated by 20 s of zero voltage. The
resultingvariation of transmittance reveals the effect of the
electric-field-induced cis–trans isomerization. With each
pulse, when the electric field is on, the transmittance of the
mixture drops to the dark state due to the homeotropic
orientation of LC molecules (BL006 and HHBAzo) in the two
phases, whereas when the field is off the transmittance
increases due to orientational relaxation of LC molecules.
Interestingly, after the six electric pulses, the transmittance
does not recover to the level correspondingto the two-phase
morphology formed after UV irradiation inducing trans-cis
photoisomerization; instead it reaches the initial transmit-
tance of the homogeneous mixture before UV irradiation,
which indicates complete conversion of the cis-azobenzene
back to the trans isomer, which is miscible with BL006. The
morphological changes giving rise to the observed changes in
have become an isotropic liquid. This experiment rules out
the possibility that the phenomenon comes from thermal
relaxation of cis-azobenzene due to severe heatingof the
solution under the electric field.
The fast cis–trans isomerization under a low electric field
takes place in polar solvents such as benzonitrile and DMSO
(e = 48), as well as in liquid crystals like 5CB and BL006 (a
nematic eutectic mixture with a high Tni of 1068C). However,
in nonpolar solvents of decreasingpolarity such as dichloro-
ethane (e = 9.1) and THF (e = 2.4), cis–trans isomerization
becomes increasingly difficult. Moreover, the phenomenon is
not unique to HHBAzo; it was also observed for a benzoni-
trile solution of a polymer which contains a different
azobenzene derivative, namely, poly{6-[4-(4-cyanophenyla-
zo)phenoxy]hexyl methacrylate (M ꢁ 20000; see the Support-
ingInformation).
How can these findings be expained? The electric field
applied across the cell containingthe azobenzene solution is
the external field; the local (i.e., Lorentz field)[9] is actually
much higher according to
Elocal = (e + 2)/3Eexternal. For
HHBAzo dissolved in benzonitrile (Figure 1), the applied
1 Vmmꢀ1 corresponds to a local field of 9.3 Vmmꢀ1, while in
5CB under the applied 18 Vmmꢀ1 (Figure 2), the local field is
96 Vmmꢀ1. However, these local field strengths are still much
smaller than the high electric field at the STM junction[6] and
within the electric double layer in an electrolyte solution,[4]
both of which are in the range of 103 Vmmꢀ1. It is thus unlikely
that the phenomenon reported here originates from the same
mechanism. On the other hand, when an electric field is
applied to the azobenzene solution in the ITO-coated cell, it is
possible that some existingions move to the electrodes and
develop a higher electric field at the electrode/solution
interface, but a high electric field like that associated with
the electrical double layer in the electrolyte solution[4] is
unlikely. While no experimental evidence indicates that the
fast cis–trans isomerization is caused by direct interaction of
the cis-azobenzene with the electric field, a number of
experiments support the most probable mechanism respon-
sible for the phenomenon, as described by the following
reactions [Eqs. (1)–(3)].[10]
ꢀÁ
Rcis þ eꢀ ! R
ð1Þ
ð2Þ
ð3Þ
cis
ꢀÁ
ꢀÁ
R
! R
cis
trans
ꢀÁ
R
þ Rcis ! Rtrans þ RcꢀisÁ
trans
Indeed, it is known that cis-azobenzene in aprotic solvents
can be reduced to the radical anion by a one-electron process
in an electrochemical cell (in the presence of a supporting
electrolyte).[10] In our study, applyingan external electric field
is equivalent to application of a potential difference between
two conductive electrodes. Such a potential difference may
cause electrolysis, that is, reduction of cis-azobenzene at the
cathode and some oxidation reaction on the anode, even in
the absence of a supportingelectrolyte. The radical anion of
cis-azobenzene can isomerize to the trans radical anion, which
in turn can reduce other cis-azobenzene in the solution while
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ITO-coated cell containingthe azobenzene solution was placed in the
compartment of a spectrophotometer (Varian 50), and a UV/Vis spot-
curingsystem (Novacure) was used to deliver the UV lihgt for
inducingthe trans–cis photoisomerization in the solution through a
flexible light guide fixed in the proximity of the cell. The whole setup
was kept in the dark (covered with aluminum foil) duringthe
experiment. A high-voltage waveform generator (WFG500, FLC
Electronics) was used to apply electric pulses of various amplitudes
and widths across the cell. By usingthe kinetics software, time-
resolved changes in absorbance could be measured with the cell under
an electric field followingUV irradiation. A picture of the exper-
imental setup, with the different components identified, is given in the
SupportingInformation.
For the measurements of coupled photooptical and electrooptical
behavior, the mixture of HHBAzo with BL006, filled into a cell, was
placed between two crossed polarizers, and the transmittance of a
probe light (633 nm from a 4-mW He–Ne laser) passing through the
cell was measured with a high-speed photodetector (Displaytech)
connected to a digital oscilloscope (Tektronix, TDS 420A). Any
changes in transmittance of the mixture in response to either UV
exposure (photooptical behavior) or an electric pulse (electrooptical
behavior) could be monitored to yield information on the photo-
induced trans–cis photoisomerization or the electric-field-induced
cis–trans isomerization of HHBAzo. For photoisomerization, UV
light was applied to the cell at an angle of about 308 with respect to the
cell normal, and by placinga nontransparent plate with a small hole
(ca. 2 mm in diameter) in front of the photodetector, the irradiation
beam caused no interference in the measured transmittance. The
mixture in the cell was equilibrated at 1408C for 10 min before being
cooled to room temperature for the measurement.
Figure 3. Azobenzene derivative in nematic liquid crystal BL006.
a) Changes in transmittance (633-nm probe light) in response to UV
irradiation (20 mWcmꢀ1) and electric pulses (8 Vmmꢀ1, 2-s duration).
b) Polarizing optical micrographs showing the morphological changes
of the mixture, which correspond to the changes in transmittance
(image area: 50”50 mm2): 1) before UV irradiation, 2) after UV irradi-
ation, 3) after switching on the E field, 4) after six electric pulses.
Received: December 12, 2007
Revised: February 15, 2008
Published online: March 31, 2008
Keywords: azo compounds · electrooptical properties ·
.
isomerization · liquid crystals · photochemistry
optical transmittance were confirmed by optical microscopy
observations under crossed polarizers (Figure 3b).
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In conclusion, we have found that a low static electric field
can dramatically increase the rate of cis–trans isomerization
of an azobenzene derivative dissolved in polar liquids and
liquid crystals without any added electrolytes. The electro-
chemical reduction of the cis-azobenzene appears to be the
origin of the phenomenon. We demonstrated that when
azobenzene derivatives are used as photoswitches to change
the optical and electrooptical behaviors of liquid crystals, the
cis isomer may be unstable under an applied voltage due to
electric-field-induced cis–trans isomerization, which impacts
the electrooptical behavior. However, since an electric field
can be used to switch the isomeric form of azobenzene
derivatives much more easily than previously believed, this
findingalso opens new opportunities for molecular switches
usingthe combined actions of light and electric fields.
[2] C. Barrett, A. Natansohn, P. Rochon, Macromolecules 1994, 27,
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[3] Z.-F. Liu, K. Hashimoto, A. Fujishima, Nature 1990, 347, 658 –
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3813.
Experimental Section
While HHBAzo was directly dissolved in a given organic solvent (e.g.,
benzonitrile), to prepare the mixtures with 5CB or BL006, HHBAzo
and the liquid crystal were first dissolved in THF, and then THF was
removed under reduced pressure. To monitor the electric-field-
induced cis–trans isomerization by UV/Vis spectroscopy, the sealed
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