PAPER

www.rsc.org/materials | Journal of Materials Chemistry

Flying-seed-like liquid crystals

Kazuchika Ohta,* Tomoyuki Shibuya and Masahiro Ando
Received 25th May 2006, Accepted 1st August 2006
First published as an Advance Article on the web 15th August 2006
DOI: 10.1039/b607466a
In 1911, Vorlarnder reported liquid-crystalline properties of unique flying-seed-like alkali metal
carboxylates. They are neither rod-like nor disk-like. Moreover, they have neither a rigid
core nor flexible long chains. The molecular shapes are totally different from about 93 000 general
liquid crystalline compounds. These flying-seed-like liquid crystals have been forgotten for about
100 years. We revealed and established for the first time from precise microscopic observations
and temperature-dependent X-ray diffraction studies that sodium diphenylacetate exhibits a
hexagonal columnar mesophase, and that potassium diethylacetate and potassium
dimethylacetate exhibit a smectic A mesophase. These old and new flying-seed-like liquid
crystals will become a novel field of science.

1. Introduction
In the East, there is a proverb called Weng Gu Zhi Xin{
(On Ko Chi Shin{). This implies that to investigate old
things is to find new things. In 1888, the first liquid crystals
were discovered by Reinitzer.1 Since then people believed for
many years that liquid crystalline compounds were rod-like
molecules. In 1977, Chandrasekhar et al. discovered that
disk-like molecules also show liquid crystalline properties.2
Accordingly, in recent years people believe that liquid crystalline molecules are rod-like as chopsticks or disk-like as dishes
(Fig. 1). Actually, there are few exceptions. To date, about
93 000 liquid crystalline compounds have bee reported.
Generally, each of the liquid crystalline molecules consists of
a strip-like or disk-like core in the centre as the rigid part
and two or more than six molten long alkyl chains in the
surroundings as the soft part.
Recently we noticed that about 100 years ago, in 1911,
Vorlander reported some liquid crystalline compounds3 which
are totally out of the general category mentioned above. As
illustrated in Fig. 1, this liquid crystalline compound has
neither a rigid core nor a flexible long alkyl chain. Moreover,
the molecular shape is neither rod-like nor disk-like but
flying-seed-like. The photograph shows maple seeds which
are abundantly seen in Shinshu University Ueda Campus from
autumn to winter. They blow off from the branches and fly by
rotating. Various kinds of flying seeds are seen world-wide and
are very familiar to many people. We wondered whether such
unique-shaped molecules really exhibit liquid crystalline
properties, and what type of mesophases they show.
In the past 100 years, these flying-seed-like liquid crystals
have seldom or never been investigated. As far as we know,
there have been only three papers which were reported by
Demus et al.4 and Sanesi et al.5,6 about 30 years ago. Table 1
Smart Materials Science and Technology, Interdisciplinary Graduate
School of Science and Technology, Shinshu University, Ueda, 386-8567,
Japan. E-mail: ko52517@giptc.shinshu-u.ac.jp;
Fax: +81-(0)268-21-5492; Tel: +81-(0)268-21-5492
{ In Chinese pronunciation.
{ In Japanese pronunciation.

This journal is The Royal Society of Chemistry 2006

lists 24 alkali metal carboxylates prepared in this study.

The molecular shapes are rod-like for A1, B1, C1 and D0-M,
whereas all the others are flying-seed-like. The salts denoted

Fig. 1 Conventional molecular type of liquid crystals, R and D, and a

novel type of liquid crystal, F. R: Rod-like (calamitic) liquid crystal, r:
Photo of a chopstick; D: disk-like (discotic) liquid crystal, d: photo of a
dish; F: flying-seed-like liquid crystal, f: photo of maple seeds.

J. Mater. Chem., 2006, 16, 36353639 | 3635

Table 1

List of alkali metal carboxylates synthesized in this work

Compound nameb,c,d

Substituent
Classa

R1

R2

R3

M = Li

M = Na

M=K

Ph
H
H

#1
#1
A1
Ph
Ph
H
A2-Li
A2-Na #1,2 A2-K #1
A2
Ph
Ph
Ph
A3-Li
A3-Na
A3-K
A3
C2H5 H
H
B1-Li #1 B1-Na #1
B1-K #1
B1
C2H5 C2H5 H
B2-Li #4 B2-Na #1,4 B2-K #1,4
B2
C2H5 C2H5 C2H5

B3
CH3
H
H
C1-Li #1 C1-Na #1
C1-K #1
C1
CH3
CH3
H
C2-Li #1 C2-Na #1
C2-K #1,3
C2
CH3
CH3
CH3
C3-Li #4 C3-Na #4
C3-K #4
C3
H
H
H
D0-Li #1 D0-Na #1
D0-K #1
D0
a
Nomenclature: compounds A, B, C and D represent phenyl-groupsubstituted derivatives, ethyl-group-substituted derivatives, methylgroup-substituted derivatives, and non-substituted derivatives,
respectively. The subscripts, 0y3, represent the number of
substituents. b Compounds in italics were reconfirmed in this work
to show mesomorphism. c : the corresponding carboxylic acids
were not commercially available. Phenylacetic acid is prohibited to
buy by the narcotics and psychotropics control law. d References: #1
Vorlander (1911): see ref. 3; #2 Demus et al. (1970): see ref. 4; #3
Ferloni et al. (1978): see ref. 5; #4 Sanesi et al. (1978): see ref. 6.

by #1#4 in Table 1 were investigated previously.36 However,

the mesophase structures were not clarified by the temperature-dependent X-ray diffraction technique. In this study, we

Table 2

have, hence, clarified the precise mesomorphic properties and

mesophase structures of two-winged flying-seed-like alkali
metal carboxylates, A2-M, B2-M and C2-M (M = Li, Na, K),
by using differential scanning calorimetry (DSC), polarizing
optical microscopy (POM), and temperature-dependent X-ray
diffraction. We wish to report here the striking results.

2. Experimental
2-1 Synthesis
As starting materials were employed commercially available
acetic acid, propionic acid, dimethylacetic acid (isobutyric
acid), trimethylacetic acid, butyric acid, diethylacetic acid,
diphenylacetic acid, triphenylacetic acid, lithium hydroxide,
sodium hydroxide, and potassium hydroxide. After mixing the
acid and an equimolecular amount of the alkali hydroxide in
ethanol, the resulting salt was recovered by the evaporation of
the solvent. The procedure for the representative compound,
potassium diethylacetate, was as follows.
Potassium diethylacetate. To a 100 ml flask, diethylacetic
acid (0.90 g, 7.3 mmol) and an equimolecular amount of
potassium hydroxide (0.50 g, 7.3 mmol) were added and 20 ml
of ethanol was poured in. The solution was refluxed for 1 hour
with stirring. The hot solution was filtered to remove the
insoluble materials. The solvent was removed by a rotary
evaporator and then the residue was dried under vacuum
overnight to afford 1.1 g of potassium diethylacetate as white
crystals in 100% yield.

Phase transition sequences of the alkali metal carboxylatesa

Compound

Reference

A2-Li: Ph2CHCOOLi

This work

A2-Na: Ph2CHCOONa

This work

A2-K: Ph2CHCOOK
B2-Li: Et2CHCOOLi

This work
Sanesi et al.

K . 400

B2-Na: Et2CHCOONa

Sanesi et al.

B2-K: Et2CHCOOK

This work

C2-Li: Me2CHCOOLi

This work

C2-Na: Me2CHCOONa

This work

C2-K: Me2CHCOOK

This work

Phase nomenclature: K = crystal, M = mesophase, and I.L. = isotropic liquid, (d) = gradual decomposition.

3636 | J. Mater. Chem., 2006, 16, 36353639

This journal is The Royal Society of Chemistry 2006

2-2 Measurements
The phase transition behaviour of these compounds was
observed by using a polarizing microscope (Olympus BH2),
equipped with a heating plate controlled by a thermoregulator
(Mettler FP82HT hot stage, Mettler FP90 central processor)
and measured by a differential scanning calorimeter
(Shimadzu DSC-50). The X-ray diffraction measurements
were carried out with Cu-Ka radiation by using a Rigaku
RAD X-ray diffractometer equipped with a hand-made
heating plate7 controlled by a thermoregulator.

3. Results and discussion

3-1 The mesomorphism of alkali metal diphenylacetates (A2-M)
Table 2 summarizes the phase transition temperatures of the
alkali metal (Li, Na, and K) diphenylacetates. The lithium
salt (A2-Li) directly melted from the crystal phase (K) to the
isotropic liquid (I.L.) at ca. 310 uC with gradual decomposition
and did not show mesomorphism. On the other hand, the

Fig. 2 Photomicrographs of the mesophases: (a) A2-Na:

Ph2CHCOONa at 250 uC, (b) B2-K: Et2CHCOOK at 200 uC, (c)
C2-K: Me2CHCOOK at 310 uC.

This journal is The Royal Society of Chemistry 2006

potassium salt (A2-K) did not melt till 400 uC. We could not
find the mesophase of A2-K to be established, although
Vorlarnder reported the mesomorphism. The sodium salt
(A2-Na) only showed a mesophase M1 from 251 uC to the
clearing point of ca. 300 uC on the heating run (10 uC min21),
and on the cooling run (210 uC min21) the M1 mesophase
resolidified at 213 uC. Fig. 2(a) shows the dendric texture of
this M1 mesophase resulting from cooling from the I.L. to
250 uC. The dendric texture has C6 symmetry characteristic of
a hexagonal columnar mesophase.
The X-ray diffraction pattern of the M1 phase in the A2-Na
was successfully obtained at a very high temperature of 280 uC.
Fig. 3(a) shows the X-ray diffraction pattern of the M1 phase
and Table 3 lists the X-ray data. The pattern gave four sharp
reflections. All their observed spacings are in good accordance

Fig. 3 X-Ray diffraction patterns of (a) A2-Na: Ph2CHCOONa

at 280 uC, (b) B2-K: Et2CHCOOK at 200 uC and (c) C2-K:
Me2CHCOOK at 310 uC.

J. Mater. Chem., 2006, 16, 36353639 | 3637

Table 3

X-Ray diffraction data of the mesophases

Compound

Peak no.

dobs./s

dcalcd./s

A2-Na at 280 uC, M1 = Colh,

a = 15.1 s

1
2
3
4
5
6
1
2
3
4
5
6
1
2
3
4

ca. 23
13.06
7.60
4.99
ca. 4.5
3.02
ca. 25
13.14
6.58
4.38
3.29
2.63
ca. 23
12.27
6.14
3.07

13.06
7.54
4.94

3.00

13.14
6.57
4.38
3.29
2.63

12.27
6.13
3.07

B2-K at 200 uC, M2 = SA,

a = 13.1 s

C2-K at 310 uC, M3 = SA,

a = 12.3 s

(hkl)
a

(100)
(110)
(210)
a

(320)
a

(001)
(002)
(003)
(004)
(005)
a

(001)
(002)
(004)

Broad halo.

with a two-dimensional hexagonal reciprocal lattice having a

. Thus, this mesophase could be
lattice constant a = 15.1 A
identified as a hexagonal columnar (Colh) mesophase. This
identification is compatible with the middle phase (= lyotropic
hexagonal columnar phase) designated from microscopic
observations by Demus et al. in 1970.4 Hereupon, it should
be emphasized that this diffraction pattern gave two additional
and ca. 23 A
. The conventional broad
broad halos at ca. 4.5 A
halo of rod-like and disk-like liquid crystals can be observed at
, which generally corresponds to the molten long alkyl
ca. 4.5 A
chains. Since the present compound has no long alkyl chains,
may represent the average distances of
the halo at ca. 4.5 A
thermally turbulent rotating aromatic moieties. Moreover, it is
could be observed
very interesting that the halo at ca. 2225 A
for all the flying-seed-like liquid crystals (see Peak 1 in
Fig. 3). Nevertheless, it is not clear at the present stage to what
the halos correspond. It is an interesting open question for
further studies.
The molecular dimension of the sodium salt (A2-Na) is
estimated from the CPK model. This molecule is
610 A
, the obtained diameter of
evidently much smaller than 15.1 A
the column in the Colh mesophase. Thereby it can be thought
that the column consists of aggregates as illustrated in Fig. 4(a).
Although the columnar structure of this phase is almost the
same as that of the conventional discotic hexagonal columnar
mesophase Colh, the disk-like units cannot be seen in the
columns. Each of the columns may have a metal wire in the
centre, which is formed by one-dimensional aggregates of
sodium metal. In the surrounding aromatic tube, the diphenyl
groups may freely rotate to form the soft part.
This sodium diphenylacetate (A2-Na) may be the first
thermotropic columnar liquid crystal before the discovery of
discotic columnar liquid crystals by Chandrasekhar in 1977.2

B2-K exhibited a typical fan-shaped texture. From this texture

we tentatively assigned this mesophase M2 as a smectic A (SA)
phase. Fig. 3(b) shows an X-ray diffraction pattern of B2-K at
200 uC. As can be seen from Table 3, this mesophase gave
five (00l) reflections. This implies that this mesophase has
thickness. Therefore, the
a layer structure having 13.1 A
present mesophase M2 could be assigned as an SA phase from
this X-ray study and the focal-conic texture mentioned above.
Fig. 4(b) illustrates a phase structure model of this mesophase.
Each of the layers may have a two-dimensional metal sheet
sandwiched above and below by two aliphatic sheets. In
the aliphatic sheets, the diethyl groups may freely rotate to
form the soft part.
3-3 The mesomorphism of alkali metal dimethylacetates (C2-M)
Table 2 also summarizes the phase transition temperatures of
alkali metal dimethylacetates C2-M(M = Li, Na, and K). The
lithium salt (C2-Li) showed not mesomorphism but double
melting behaviour. The sodium salt (C2-Na) exhibited single
melting behaviour. On the other hand, the potassium salt
(C2-K) has a mesophase, M3. The C2-K salts melted from the
K2 phase into the M3 mesophase at 282 uC and cleared into the
I.L. at 355 uC with considerably rapid decomposition. Fig. 2(c)
showed that the M3 phase at 310 uC gave many terraces8 with
viscosity. Since it looked likely to be optically isotropic, we
thought that it might be a cubic phase. However, the terraces
may correspond to a layered structure, which is not compatible
with the isotropic nature.
Therefore, X-ray diffraction studies were carried out for this
M3 phase (Fig. 3(c)). The diffraction data at 310 uC are
summarized in Table 3. It gave three sharp reflections. As can
be seen from Table 3, all the observed spacing values are in
very good accordance with a layered structure having a lattice
. Therefore, this M3 mosophase could be
constant, a = 12.3 A
assigned as an SA mesophase strongly exhibiting spontaneous
homeotropic alignment. The molecular dimension of the
estimated from the
potassium dimethylacetate is about 67 A
CPK model. The molecular dimension is much smaller
. Hence, the SA phase of
than the lattice constant, a = 12.3 A
C2-K has a phase structure as illustrated in Fig. 4(b), the same
as B2-K.

3-2 The mesomorphism of alkali metal diethylacetates (B2-M)

As can be seen from Table 2, B2-K only shows a mesophase
(M2) among the B2-M (M = Li, Na, K) salts. We could not
find any mesomorphic properties for B2-Li and B2-Na,
similarly to the report of Sanesi et al.6 As shown in Fig. 2(b),
3638 | J. Mater. Chem., 2006, 16, 36353639

Fig. 4 Proposed mesophase structure models of (a)

(Ph2CHCOONa),
(b)
B2-K
(Et2CHCOOK)
and
(Me2CHCOOK).

A2-Na
C2-K

This journal is The Royal Society of Chemistry 2006

4. Conclusions
Thus, we have established for the first time from temperaturedependent X-ray diffraction studies that sodium diphenylacetate (A2-Na) exhibits a hexagonal columnar mesophase (Colh),
and that both potassium diethylacetate (B2-K) and potassium
dimethylacetate (C2-K) exhibit a smectic A mesophase. These
salts are flying-seed-like and completely different from
general molecular shapes of all the conventional liquid
crystalline materials, because their molecular shapes are
neither rod-like nor disk-like, and because they have neither
flexible long chains nor a rigid flat core. We believe that these
old and new flying-seed-like mesogens will become a novel
field of science.

Acknowledgements
This work was partially supported by a Grant-in-Aid for the
21st Century COE Program and Priority Area Research

This journal is The Royal Society of Chemistry 2006

(18039013) by the Japanese Ministry of Education, Culture,

Sports, Science and Technology.

References
1 H. Keller, Mol. Cryst. Liq. Cryst., 1973, 21, 148; V. Vill, Condens.
Matter News, 1992, 1, 2528.
2 S. Chandrasekhar, B. K. Sadashiva and K. A. Suresh, Pramana,
1977, 9, 471480.
3 D. Vorlander, Ber. Dtsch. Chem. Ges., 1911, 43, 31203125.
4 D. Demus, H. Sackmann and K. Seibert, Wiss. Z. Univ. Halle,
Math.-Naturwiss. Reihe, 1970, 19, 4762.
5 P. Ferloni, M. Sanesi, P. L. Tonelli and P. Franzosini, Z.
Naturforsch., A, 1978, 33, 240242.
6 M. Sanesi, P. Ferloni, G. Spinolo and P. L. Tonelli, Z. Naturforsch.,
A, 1978, 33, 386388.
7 H. Ema, Master Thesis, Shinshu University, Ueda, 1988, ch. 7;
H. Hasebe, Master Thesis, Shinshu University, Ueda, 1991,
ch. 5.
8 See Plate 90 in the following book: D. Demus and L. Richter,
Textures of Liquid Crystals, Second Edition, VEB, Leipzig,
Germany, 1978.

J. Mater. Chem., 2006, 16, 36353639 | 3639