Field-induced switching of chirality in undulated ferroelectric and antiferroelectric smCP phases formed by bent-core mesogens

Article abstract of DOI:10.1002/anie.200461490

Switching signs: The polar structure of a tilted smectic C phase formed by a homologous series of bent-core mesogens changes from antiferroelectric to ferroelectric with increasing chain length. The polar switching of the banana-shaped molecules occurs by

Full text of DOI:10.1002/anie.200461490

Communications
Chirality Switching
Field-Induced Switching of Chirality in Undulated
Ferroelectric and Antiferroelectric SmCP Phases
Formed by Bent-Core Mesogens**
Ramaiahgari Amaranatha Reddy, Martin W. Schrꢀder,
Michael Bodyagin, Horst Kresse, Siegmar Diele,
Gerhard Pelzl,* and Wolfgang Weissflog
Chirality is a fundamental property of matter. In most cases
chirality is an inherent molecular property, but it can also
occur in solid crystals even though the constituent moieties
are nonchiral, for example, as a consequence of a spontaneous
discrimination during the crystallization process. Chirality in
liquid systems formed by nonchiral molecules seems to be
impossible because of the mobility of the particles. However,
there are new kinds of mesophases formed by nonchiral bent-
core molecules which are also able to exhibit phase chirality.
The molecules can be packed in a polar fashion because of
their bent shape and give rise to a long-range correlation of
the lateral dipoles and therefore to a macroscopic polar-
ization in the smectic (SmC) layers.[1] In the most widely
studied SmCP phase (P = polar), the polar packed molecules
are tilted with respect to the normal of the layer. As first
shown by Link et al.[2] four structures can be distinguished
depending on the stacking of the molecules in adjacent
smectic layers (Figure 1). The molecules can have either a
synclinic or an anticlinic interlayer correlation which is
indicated in the phase symbol SmCP by the subscripts S and
A after C. The polar order is specified by the suubscripts A
and F, where A corresponds to an antiferroelectric structure
and F designates a ferroelectric structure (the possible phase
symbols are thus SmCAPA, SmCSPA, SmCAPF, and SmCSPF).[2]
The polar packing as well as the tilt of the molecules in the
SmCP phases are two steps of symmetry breaking which
create a layer chirality without any molecular chirality. As
seen in Figure 1, two equivalent layer structures with anti-
parallel polar axes exist for a given tilt direction which are
mirror images of each other. The opposite handedness is
depicted by filled (black) or open (white) molecule symbols.
All layers of a macroscopic domain in the SmCAPA and
SmCSPF structures have the same layer chirality (homochiral
Figure 1. Possible orientations of the tilt and polar axes of bent-core
molecules in adjacent layers that lead to chiral or racemic ferroelectric
and antiferroelectric SmCP phases. Filled and open molecule symbols
designate layers of opposite chirality.
state) whereas the chirality alternates from layer to layer in
the SmCSPA and SmCAPF structures (racemic state).
To avoid bulk polarization an antiferroelectric ground
state exists in most cases where the polarization alternates in
adjacent layers.[3] The antiferroelectric states can be switched
to the corresponding ferroelectric states (Figure 1). This field-
induced reorientation takes place through rotation of the
director around the normal to the layer on the tilt cone such as
occurs in ferro- and antiferroelectric phases of calamitic
compounds. The chirality of the layers is preserved during this
switching process and is also the case for a switch between two
ferroelectric states. Recently, it was found that the polar
switching in “banana phases” can also take place by another
mechanism, which is based on the collective rotation of the
molecules around their long axes (Figure 2a). In polar
Figure 2. Mechanisms of polar switching a) by collective rotation of
the molecules around their long axes and b) by rotation of the director
around the tilt cone. Filled and open molecule symbols designate
layers of opposite chirality.
[*] Dr. R. Amaranatha Reddy, M. W. Schrꢀder, M. Bodyagin,
Prof. Dr. H. Kresse, Dr. S. Diele, Prof. Dr. G. Pelzl,
Prof. Dr. W. Weissflog
smectic A (SmAP) phases[4,5] and in B1rev phases formed by
SmAP-like layer fragments[6] this mechanism is the only
possibility for polar switching. There are a few examples that
this switching mechanism can also occur in tilted SmCPA
phases[7–9] as well as in B1rev phases with SmCP-like layer
fragments,[6] mostly under special experimental conditions.
Nakata et al.[8] and Bedel et al.[9] were able to detect this
switching mechanism above a critical electric field. Schrꢀder
et al.[7] observed this kind of polar switching only on very slow
increase or decrease of the electric field. It should be
emphasized that the field-induced switching in tilted
Institut fꢁr Physikalische Chemie
Martin-Luther-Universitꢂt Halle-Wittenberg
Mꢁhlpforte 1, 06108 Halle/Saale (Germany)
Fax: (+49)345-552-7157
E-mail: pelzl@chemie.uni-halle.de
[**] This work was supported by the Deutsche Forschungsgemeinschaft
(Graduiertenkolleg 894 “Selbstorganisation durch koordinative und
nichtkovalente Wechselwirkungen” and the Fonds der Chemischen
Industrie.
Supporting information for this article is available on the WWW
under http://www.angewandte.org or from the author.
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DOI: 10.1002/anie.200461490
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Table 1: Transition temperatures and corresponding enthalpies of compounds 5–10, 12, and 16.[a]
“banana phases” by rotation around the
long axes is accompanied by an inversion of
the layer chirality.
Herein we focus mainly on the switching
of chirality by external electric fields. We
investigated eight homologues of a new
series of bent-core mesogens in which the
outer linking groups are reversed compared
to isomeric compounds reported in the
literature.[10] We found that all the homo-
logues form a polar tilted smectic C (SmCP)
phase with undulated smectic layers. From
electrooptical experiments it follows that
the short-chain members possess an anti-
ferroelectric ground state while the long-
chain members are ferroelectric. It is the
first example where the switching process is
changed from an antiferroelectric to a
ferroelectric one with increasing chain
Compound
n
Transition (T [8C]) [dH [kJ molꢀ1]]
Transition (T [8C]) [dH [kJ molꢀ1]]
˜
˜
5
6
7
8
5
6
7
8
Cr!SmCPA (168.5) [92.2]
SmCPA!I (163.5) [18.8]
˜
˜
Cr!SmCPA (166.5) [70.9]
SmCPA!I (168.0) [20.6]
˜
˜
Cr!SmCPA (161.5) [79.3]
SmCPA!I (165.0) [11.6]
˜
˜
Cr!SmCPA (160.0) [68.7]
SmCPA!I (168.0) [21.5]
˜
˜
9
9
Cr!SmCPA (157.5) [83.9]
SmCPA!I (165.5) [20.7]
˜
˜
10
12
16
10
12
16
Cr!SmCPF (154.5) [86.7]
SmCPF!I (164.0) [21.7]
˜
˜
Cr!SmCPF (152.0) [79.7]
SmCPF!I (162.0) [23.6]
˜
˜
Cr!SmCPF (151.0) [110.4]
SmCPF!I (160.5) [24.3]
˜
[a] Abbreviations: Cr=crystalline solid, SmCPA =antiferroelectrically switchable undulated tilted
smectic phase, SmCPF =ferroelectrically switchable undulated tilted smectic phase, I=isotropic liquid.
˜
length. Furthermore, for the first time, we found a clear
dependence of the switching mechanism on the experimental
conditions, that is, on the frequency and the temperature. At
higher frequencies or lower temperatures, the polar switching
of the ferroelectric phase takes place in the usual way, that is,
by the rotation of the director around the tilt cone. This
switching process retains the chirality of the layer and
reverses only the polarity of the layer (see Figure 2b). The
other type of polar switching takes place through collective
rotation of the molecules around their long axes at sufficiently
low frequencies or high temperatures. This process, which was
first observed for the ferroelectric tilted “banana phases”,
reverses the polarity of the layer and is now accompanied by
an inversion of the macroscopic chirality (see Figure 2a).
Interestingly, both switching mechanisms compete at inter-
mediate frequencies. By using polarizing microscopy an
irreversible field-induced inversion of chirality could be
clearly visualized in a texture which exhibits circular domains
of opposite handedness. It should be noted that rotation
around the long axes is probably the only mechanism of polar
switching in the antiferroelectric phase of the short-chain
homologues.
All members 5–10, 12, and 16 of the series have been
prepared by esterification of resorcinol with the correspond-
ing 4-(4-n-alkyloxyphenoxycarbonyl)benzoic acids in the
presence of N,Nꢁ-dicyclohexylcarbodiimide (DCC) and 4-
(N,N-dimethylamino)pyridine (DMAP) as the catalyst in
dichloromethane (for the reaction pathway and analytical
data for compound 12, see the Supporting Information). The
transition temperatures together with the enthalpy values are
recorded in Table 1. Compounds 5–9 show similar optical
textures, thus indicating they have the same phase. Cooling
the isotropic liquid of any of these compounds results in the
mesophase growing with ribbonlike textures together with the
helical filaments (Figure 3a). However, the textural features
observed for the higher homologues, namely, compounds 10–
16, are completely different to that of the first group, thus
indicating a different mesophase. The mesophases of these
longer chain compounds only show a spherulytic texture as
shown in Figure 3b.
˜
Figure 3. Optical photomicrographs of a) the SmCPA phase of com-
˜
pound 8 at 1678C and b) the SmCPF phase of compound 12 at 1618C.
The compounds under discussion are interesting from a
structural point of view. X-ray powder diffraction patterns
recorded with a Guinier film camera show strong layer
reflections indicating that the basic structure is smectic. In
addition, satellites of weak intensity could be clearly seen
behind the layer reflections which suggests the presence of an
undulated layer structure. The XRD powder pattern obtained
for the mesophase of compound 6 is shown as an example in
the Supporting Information. Satellites of weak intensity are
obtained for the complete homologous series (see the
Supporting Information). The undulation period increases
from 100 to 150 ꢂ with increasing chain length. The X-ray
diffraction pattern of a partially aligned sample of the
mesophase (see the Supporting Information) allows a tilt
angle of about 208 to be estimated for compound 12
˜
(designated as SmCP, where the symbol ~ indicates the
periodic in-plane density wave according to the recommen-
dation in ref. [11]). This value is relatively small compared
with the tilt angle of smectic phases of other bent-core
compounds. Awide-angle diffuse maximum obtained at 4.7 ꢂ
indicates the absence of any long-range positional order. As
shown by Coleman et al.,[12] the modulated layer structure
formed by bent-core molecules is generated by splayed
polarization with domains of alternate tilt and polarization
periodically arranged. This is another way to avoid bulk
polarization.
In addition to the structural features, the electrooptical
behavior is also particularly interesting. On applying a
triangular-wave electric field[13] to the mesophase of com-
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pound 7, two polarization current peaks per half period were
remains unchanged on terminating the field, thus indicating
bistable switching. Circular domains with extinction crosses
could be obtained on increasing the voltage above a threshold
value (E > Eth). These domains show bistable (ferroelectric)
switching and the extinction crosses remain unchanged after
removing the applied field. These bistable states are stable for
several hours (Figures 4 and 5a), thus confirming the ferro-
electric ground state of this mesophase. We strongly believe
that the appearance of switching chiral domains at higher
electric fields (triangular wave) is the consequence of the
suppression of the undulated structure of the ground state, as
observed for several other compounds.[12] The field-induced
SmCsPF phase is stable on sudden removal of the field.
However, the switching circular domains disappear slowly
when the applied field is slowly reduced, which indicates a
transition back to the undulated ground state. The switching
recorded which indicates an antiferroelectric ground state
(see the Supporting Information). The calculated polarization
value is about 520 nCcmꢀ2. However, the field-induced
circular domains in which the extinction crosses are aligned
along the directions of the crossed polarizers do not change
on reversal of the field. At first sight, these observations could
indicate a racemic ground state for the mesophase. However,
no relaxation of the extinction crosses could be seen on
terminating the applied field, apart from a small change in the
birefringence. If the effect arose from a racemic nature of the
domains, the texture should have shown a striped pattern
parallel to the smectic layers as a result of an alternating
chirality.[2] Instead we only observe a smooth fan-shaped
texture (see the Supporting Information). Therefore, these
observations suggest that the chirality of the layer switches by
collective rotation of molecules around their long axes on
reversing the applied field. A similar switching behavior could
be observed for the homologues (5, 6, 8, and 9) exhibiting
antiferroelectric switching. On the basis of these experimental
observations, mesophases of these compounds have been
˜
mechanism of the ferroelectric SmCP phase clearly depends
on the frequency and on the temperature, which contrasts the
˜
behavior of the antiferroelectric SmCP phase of the short-
chain members.
˜
designated as the SmCPA phase.
The mesophase of compounds with longer aliphatic chains
(10, 12, and 16) shows a different and interesting electro-
optical switching behavior. A ferroelectric switching current
response could be observed in the mesophase of compound 12
(see the Supporting Information); this result was also
confirmed by applying a modified triangular wave (the
plateau is introduced at zero voltage), which shows only a
single polarization peak per half period. Therefore, we
˜
designated this phase as SmCPF. A texture with spherulytic
patterns appeared on cooling the mesophase of compound 12
under a polarizing microscope, and application of an electric
field afforded a texture with bright and dark domains which
depends on the polarity of the applied field. The texture
Figure 4. Bistable (ferroelectric) switching states obtained for the
mesophase of compound 12 (ꢁ40 Vmmꢀ1, 30 Hz at 1498C), which are
stable for several hours.
˜
Figure 5. Frequency-dependent switching mechanism under a triangular-wave field for the SmCPF phase of compound 12 at 1488C and
ꢁ40 Vmmꢀ1. Red and blue molecule symbols designate layers of opposite chirality.
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No change in the position of the extinction crosses and no
change of the birefringence could be seen by reversing the
polarity of the applied field at lower frequencies (< 0.2 Hz),
although the optical effect and a current response could be
clearly detected. These findings indicate that a reversal of the
polarization takes place through the collective rotation
around the long molecular axes. This kind of switching not
only reverses the polarity but also the chirality of the layer.
This result means that the chirality of the whole domain is
inverted in the case of ferroelectric phases (Figure 5b).
At higher frequencies (ꢂ 20 Hz) a fast bistable switching
is observed where the extinction crosses rotate clockwise or
anticlockwise depending on the handedness of the circular
domains (Figure 5c). This observation indicates that reversal
of the polarization occurs by rotation of the director around
the tilt cone. In this case, the chirality of the layer is retained
and only the direction of polarization is reversed, as in SmC*
phases.
Interestingly, at intermediate frequencies (> 0.5 Hz) a
switching process could be clearly seen which takes place in
the frequency of the applied a.c. field (Figure 5d), and
simultaneously a very slow rotation of the extinction crosses
(clockwise or anticlockwise) could be observed. These two
results indicate a combination of both switching mechanisms.
No optical switching could be seen in the temperature
interval 58C below the clearing temperature irrespective of
the frequency, which suggests switching by a rotation around
the molecular long axes. Bistable switching domains slowly
appeared on further cooling the sample, which indicates
switching around the tilt cone. The temperature dependence
could be explained if we assume that the viscosity ca (related
to the rotation around the long axes) is lower than the
viscosity cf (related to the rotation around a tilt cone) for a
given field E and a given polarization P at higher temper-
ature, whereas at lower temperatures the situation is opposite.
We also observed the inversion of the macroscopic
chirality under the influence of an a.c. field over time. As
seen from Figure 6, the texture consists of circular domains of
opposite handedness; there are domains which have both an
outer and inner part (indicated by arrows) with opposite
handedness. If a sufficiently high voltage (a.c. field) is applied
for some time (see snapshots after 30, 60, and 95 seconds) it
can be seen that the inner domain with opposite chirality
grows at the cost of the outer one. After about 60 s, the
nucleation of a new domain begins in the center of the
growing inner domain, again with opposite handedness. In
this way, the field-induced change of chirality can be directly
visualized. In this context it should be noted that an
irreversible changeover of a homochiral into a racemic
[14]
structure was reported in a SmCPA phase
of a triangular electric field.
by application
In conclusion, we have presented a new homologous
series of bent-core mesogens where all members form a polar
tilted smectic C phase with an undulated layer structure. We
have found for the first time that the polar structure is
changed from antiferroelectric to ferroelectric with increasing
˜
Figure 6. Visualization of the inversion of macroscopic chirality with time under a triangular-wave field in the SmCPF phase of compound 12;
ꢁ40 Vmmꢀ1, 30 Hz at 1488C. Filled and open molecule symbols designate layers of opposite chirality.
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chain length. This observation can be explained in terms of
interlayer interactions: they could be stronger for short-chain
members which would clearly favor the formation of an
antiferroelectric polar structure. Another remarkable feature
is the occurrence of two different mechanisms of polar
switching. In the case of ferroelectric phase, the switching
mechanism clearly depends on the experimental conditions.
At low temperatures and high frequencies the polar switching
is based on the rotation of the director around the tilt cone. At
a high temperature and a low frequency the polar switching
takes place through rotation of the long molecular axes.
Furthermore, we were able to change the chirality of circular
domains irreversibly by application of an a.c. field.
Received: July 30, 2004
Published online: December 21, 2004
Keywords: chirality · electrooptical switching · ferroelectric
.
structures · mesophases · phase transitions
[1] T. Niori, T. Sekine, J. Watanabe, T. Furukawa, H. Takezoe, J.
Mater. Chem. 1996, 6, 1231.
[2] D. R. Link, G. Natale, R. Shao, J. E. Maclennan, N. A. Clark, E.
Kꢀrblova, D. M. Walba, Science 1997, 278, 1924.
[3] G. Pelzl, S. Diele, W. Weissflog, Adv. Mater. 1999, 11, 707.
[4] A. Eremin, S. Diele, G. Pelzl, H. Nadasi, W. Weissflog, J.
Salfetnikova, H. Kresse, Phys. Rev. E 2001, 64, 051707.
[5] R. Amaranatha Reddy, B. K. Sadashiva, J. Mater. Chem. 2004,
14, 1936.
[6] J. Szydlowska, J. Mieczkowski, J. Matraszek, D. W. Bruce, E.
Gorecka, D. Pociecha, D. Guillon, Phys. Rev. E 2003, 67, 031702.
[7] M. W. Schrꢀder, S. Diele, G. Pelzl, W. Weissflog, ChemPhys-
Chem 2004, 5, 99.
[8] M. Nakata, R.-F. Shao, W. Weissflog, H. Takezoe, N. A. Clark,
Poster at the Ferroelectric Liquid Crystal Conference, Dublin,
2003.
[9] J. P. Bedel, J. C. Rouillon, J. P. Marcerou, H. T. Nguyen, M. F.
Achard, Phys. Rev. E 2004, 69, 061702.
[10] D. Shen, A. Pegenau, S. Diele, I. Wirth, C. Tschierske, J. Am.
Chem. Soc. 2000, 122, 1593; R. Amaranatha Reddy, B. K.
Sadashiva, Liq. Cryst. 2003, 31, 1031.
[11] M. Baron, Pure Appl. Chem. 2001, 73, 845.
[12] D. A. Coleman, J. Fernsler, N. Chattham, M. Nakata, Y.
Takanishi, E. Korblova, D. R. Link, R.-F. Shao, W. G. Jang,
J. E. Maclennan, O. Mondainn-Monval, C. Boyer, W. Weissflog,
G. Pelzl, L.-C. Chien, J. Zasadzinski, J. Watanabe, D. M. Walba,
H. Takezoe, N. A. Clark, Science 2003, 301, 1204.
[13] K. Miyasato, S. Abe, H. Takezoe, A. Fukuda, E. Kuze, Jpn. J.
Appl. Phys. 1983, 22, L661.
[14] G. Heppke, A. Jꢃkli, S. Rauch, H. Sawade, Phys. Rev. E 1999, 60,
5575.
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