Angewandte

Reviews Chemie

International Edition: DOI: 10.1002/anie.201711163

Liquid Crystals German Edition: DOI: 10.1002/ange.201711163

Functional Liquid Crystals towards the Next Generation

of Materials
Takashi Kato,* Junya Uchida, Takahiro Ichikawa, and Takeshi Sakamoto

Keywords:
liquid crystals · materials science ·
nanomaterials · self-assembly ·
supramolecular chemistry

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Since the discovery of the liquid-crystalline state in 1888, liquid crystal From the Contents
science has made great advances through fusion with various tech-
1. Introduction 3
nologies and disciplines. Recently, new molecular design strategies and
new self-assembled structures have been developed as a result of the 2. New Design of Molecules and
progress made in synthetic procedures and characterization tech- Molecular Assemblies for Liquid
niques. Since these liquid crystals exhibit new functions and properties Crystals 4
derived from their nanostructures and alignment, a variety of new
3. New Nanostructured
functions for liquid crystals, such as transport for energy applications, Functional Materials Based on
separation for environmental applications, chromism, sensing, elec- Dynamic Ordering 6
trooptical effects, actuation, and templating have been proposed. This
Review presents recent advances of liquid crystals that should 4. Nanostructured Liquid Crystals
for Energy
contribute to the next generation of materials.
Applications 7

5. Separation 10

1. Introduction 6. New Functionalization of

Liquid crystals are basically molecular materials that
combine molecular order and mobility.[1–7] They can be
recognized as a class of functional materials that have great
potential to be used in fields of information, energy, environ-
ment, separation, and healthcare. Since the discovery of liquid
crystals in 1888 by Reinitzer,[8] liquid crystals have been
studied for about 130 years in multiple disciplines, such as
chemistry, physics, biophysics, and engineering, leading to
progress in basic science and technologies.
Nanosegregated liquid-crystalline (LC) phases, such as
micellar cubic, columnar, smectic, and bicontinuous cubic
phases, have been used for the construction of functional
materials.[5–7, 9–11] A variety of new molecular designs for
nanosegregated assemblies have emerged. These molecules
have block structures consisting of more than two immiscible
parts. The conventional rod-like moiety is not always needed
for the induction of thermotropic LC phases because phase
segregation and intermolecular interactions, such as hydrogen
bonding[4, 12] and ionic interactions,[4, 13] lead to the induction
and stabilization of LC structures. These thermotropic LC
nanostructures, such as columnar, smectic, and cubic phases,
are similar to lyotropic LC nanostructures formed by
amphiphilic molecules with water.[14] The recent progress in
the studies of nanostructured liquid crystals is greatly
dependent on the development of advanced techniques for
the characterization of molecular order,[15, 16] allowing rela-
tionships between functions and structures to be more widely
understood. It has been possible to incorporate p-conjugated
mesogens, such as hexabenzocolonenes,[17, 18] oligothio-
phenes,[19–21] as well as triphenylenes[22] into the mesogens.
Such p-conjugated mesogens have widened the applicability
of the liquid crystals. It should be noted that progress in
synthetic organic chemistry,[23] including the discovery and
advances of coupling reactions, have largely contributed to
the design of LC aromatic molecules.
In contrast to nanostructured liquid crystals, nematic
liquid crystals which form the simplest LC structures have
been applied to flat-panel displays as a result of their three
important characteristics, fluidity (low viscosity), responsive-
Nematic Liquid Crystals 12
7. Summary and Outlook 14
ness to electric fields, and easy formation of mono-domains.[2]
This successful application of nematic liquid crystals results
from the cooperation and accumulation of studies by many
scientists and engineers in a variety of fields related to liquid
crystals. Furthermore, high mechanical strength fibers and
plastics[24] and optical compensation films[25] have also been
developed by fixing the molecular oriented structures formed
by nematic or nematic columnar liquid crystals. In addition to
these conventional liquid crystals, new designs for functional
nematic liquid crystals have emerged recently.[26]
In this Review, we describe topics on recent progress in
LC materials in view of the design of molecular structures and
the relationships between molecular self-assembled struc-
tures and functions. In particular, we focus on the design of
new self-assembled structures for LC materials for potential
applications as unique nanostructured materials.
[*] Prof. Dr. T. Kato, Dr. J. Uchida, Dr. T. Sakamoto
Department of Chemistry and Biotechnology, School of Engineering
The University of Tokyo
Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan)
E-mail: kato@chiral.t.u-tokyo.ac.jp
Prof. Dr. T. Ichikawa
Department of Biotechnology, Tokyo University of Agriculture and
Technology
Nakacho, Koganei, Tokyo 184-8588 (Japan)
and
PRESTO (Japan) Science and Technology Agency (JST)
4-1-8 Honcho, Kawaguchi 332-0012 (Japan)
The ORCID identification number(s) for the author(s) of this article
can be found under:
https://doi.org/10.1002/anie.201711163.
This article is part of the Special Issue to commemorate the 350th
anniversary of Merck KGaA, Darmstadt, Germany. More articles can
be found at www.angewandte.org.

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2. New Design of Molecules and Molecular Assem-
blies for Liquid Crystals
Recently nonconventional chemical structures for liquid
crystals have been developed based on rod-like and disc-like
mesogens.[4, 5, 9, 27–29] Rod-shaped mesogens have been the most
fundamental structures since the discovery of liquid crys-
tals.[30] If one longer alkyl chain is attached on each side of
simple rod-shaped aromatic mesogens, nanosegregated
phases, such as smectic phases are formed.[30] In the case of
polycatenar structures, columnar and cubic phases are also
induced.[27] For example, oligothiophene-based polycatenar
liquid crystal 1 exhibiting smectic, columnar, and micellar
cubic phases was designed to prepare photo- and electro-
functional LC materials (Figure 1 a).[20] Polycatenar structures
are currently important to obtain functional LC assemblies.[31]
For further ordered materials design, more non-meso-
genic functional objects with complicated structures are
required to be introduced into LC order. However, simple
mixing of the objects with liquid crystals leads to macrophase
separation owing to low solubility, hence the introduction of
the objects into the order states fails. Forklike structures,
which have several mesogenic moieties at one phenyl ring
through flexible spacers, have been employed as mesogenic
components to strongly induce LC properties for functional
non-mesogenic molecules.[28, 32, 33] These forklike units need
only one single point to attach, which makes molecular design
and synthesis easier. A variety of functional LC materials
incorporating fullerenes,[33] p-conjugated molecules,[34] cluster
compounds,[35, 36] and supramolecular moieties,[37–41] such as
catenanes[38] and rotaxanes,[39, 40] are constructed by connect-
ing functional objects to forklike mesogens. Spherical metal
complexes bearing 72 rod-like moieties at the periphery are
formed by self-assembly of 24 forklike ligands 2 and 12 palla-
Takashi Kato received his Ph.D. degree at
the University of Tokyo in 1988. After his
post-doctoral research at Cornell University
with Professor Jean M. J. Frchet on supra-
molecular liquid crystals and polymers
(1988–1989), and he joined the University
of Tokyo. Since 2012 he is Research Super-
visor of PRESTO research “Molecular Tech-
nology” of the Japan Science and Technology
Agency. His research focuses on the design,
synthesis and functionalization of self-assem-
bled functional materials.
Junya Uchida received his Ph.D. from the
University of Tokyo in 2018 working on the
topic of self-assembly of supramolecular
liquid crystals under the supervision of Pro-
fessor Takashi Kato.
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dium ions (Figure 1 b).[37] Discrete Cs2Mo6Br14 metal clusters
can also be incorporated into LC phases by electrostatic and
host–guest interactions between Cs+ cations and mesogenic
diazacrown derivatives 3 (Figure 1 b).[36]
Star-shaped three-arm mesogens having C3-symmetry
behave differently from conventional rod- and disk-shaped
mesogens because they have void space between the arms.[29]
Compound 4 is a star-shaped mesogen consisting of rigid-rod
parts. A helical stacking model for 4 is shown in Figure 1 c.
One advantage of the void space is the ability to incorporate
functional guest molecules through covalent or non-covalent
bonding.[42, 43] The LC phases of star-shaped mesogens can be
tuned by attaching guest molecules to the groove.[42] Photo-
luminescent star-shaped materials have also been pre-
pared.[44–46] Bent-core liquid crystals have emerged as a new
type of LC molecules over the past two decades because they
can produce a variety of LC phases with unique structures and
properties.[47] One of the specific features of the bent-core
liquid crystals is ferroelectric behavior.[48] Some bent-core
liquid crystals show spontaneous polarization and polar
switching in the LC phases. Another interesting behavior of
bent-core liquid crystals is spontaneous achiral symmetry
breaking.[5] It should be noted that achiral bent-core mole-
cules can form chiral domains with opposite handedness. A
new chiral structure, which is classified as a helical nanofila-
ment phase, is formed by self-assembly of bent-core liquid
crystals.[49]
Rod-like mesogens having several immiscible flexible
components, such as alkyl, oxyethylene,[50] siloxane,[51] and
perfluoro[52] moieties have been used for the induction of new
assembled structures with functions. A representative mole-
cule is shown in Figure 1 d.[53] They have an aromatic biphenyl
part with diol groups on both sides and a long alkyl- and
alkylfluoro-block chain at the center which leads to the
Takahiro Ichikawa received his Ph.D. from
the University of Tokyo in 2013. From
2010–2015 he was an Assistant Professor at
TUAT. During this time, he obtained a posi-
tion as a JST PRESTO project researcher. In
June 2015, he established his laboratory at
TUAT and started his current research focus-
ing on the functionalization of gyroid-struc-
tured materials.
Takeshi Sakamoto obtained his Ph.D. at the
University of Tokyo in 2009 in the field of
inorganic/organic hybrids. After working as
a postdoctoral researcher at the University of
Tokyo from 2009 until 2011, he became an
assistant professor, working in the field of
inorganic/organic hybrids, biomineralization
and liquid-crystalline polymers.
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Figure 1. a) Molecular structure of oligothiophene-based polycatenar liquid crystals 1. Reprinted from Ref. [20] with permission from Wiley.
b) Molecular structure of forklike ligands 2 and 3. 24 molecules of ligand 2 and 12 palladium ions co-organize into a spherical metal complex.
Cs2Mo6Br14 and mesogenic ligands 3 assemble to form LC clusters. Reprinted from Ref. [36] and Ref. [37] with permission from American
Chemical Society and Wiley, respectively. c) Molecular structure and stacking model of star-shaped three-arm mesogens 4. Reprinted from
Ref. [29] with permission from Wiley. d) Rod-like compounds 5 with perfluoro flexible chains forming bicontinuous cubic assemblies. Reprinted
from Ref. [53] with permission from Wiley.

formation of complex LC nanostructures.[53] Depending on bicontinuous cubic phases. For example, compound 5 exhibits
the volume balance between the immiscible parts, these a bicontinuous cubic phase from 130 to 146 8C. The electron
molecules form various nanosegregated structures including density map in these LC phases is shown in Figure 1 d.

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Without rigid-rod- or disc-shape moieties, nanostructured
liquid crystals can be formed. Dendrimers and dendrons are
branched molecules whose molecular structures are charac-
terized by the generations of branching.[54] Self-assembly of
dendrons and dendrimers into ordered states has been
intensively studied.[55–58] For example, Percec and co-workers
prepared liquid crystals exhibiting micellar cubic and colum-
nar phases by tuning the molecular structures based on
Frchet-type dendron molecules.[59] These dendrons have
been used for a variety of LC functional nanostructured
materials.[4, 6]
By employing ionic structures in liquid crystal design,
a variety of molecular assembled structures can be
obtained.[4, 7, 9, 13, 15] These ionic liquid crystals have been
designed and functionalized,[4, 9, 13, 60–66] which have been sum-
marized in several Reviews.[4, 9, 60–63] Herein a few representa-
tive nanostructured ionic functional materials are described.
For example, a systematic study on wedge-shaped imidazo-
lium and ammonium salts by Kato and co-workers has shown
information on relationship between molecular structures and
their self-assembled structures.[15, 67–69] For example, com-
pound 6 a exhibits a bicontinuous cubic phase from 42 to
82 8C (Figure 2 a). The electron density map in the bicontin-
uous cubic phases was resolved by synchrotron X-ray
diffraction (XRD) measurements.[15] The Fourier transforma-
tion of the XRD pattern for 6 a provides a well-defined 3D
electron density map image 1(6 a) (Figure 2 b), which clearly
shows the formation of 3D interwoven ionic nanochannels
with high electron density. In the same manner, 1(6 b) was
Figure 2. a) Wedge-shaped ammonium salts 6 forming bicontinuous
cubic phases. b) The electron density map (1[6 a]) in the assembled
states. c) A differential electron density map between 1[6 a] and 1[6 b].
Reprinted from Ref. [15] with permission from the American Chemical
Society. d) Dendron-type compound 7 forming micellar cubic phases.
e) The electron density map (1[7]) in the assembled states. f) A
differential electron density map between 1[7 a] and 1[7 a0.87 b0.2].
Reprinted from Ref. [70] with permission from the American Chemical
Society.
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also reconstructed. Based on an assumption that the differ-
ence between 1(6 a) and 1(6 b) should result from the electron
density of the counter anions, it was expected that the
subtraction of 1(6 a) from 1(6 b) would give important
information on the presence of counter anions in the
assembled states. The differential electron density map
between the two was created as shown in Figure 2 c. The
difference in electron density can be seen in the central parts
of the 3D ionic nanochannel domains, which indicates that the
counter anions are in the nanochannels.
As shown above, XRD measurement is a powerful tool to
analyze nanostructures. By using XRD analysis, the formation
of a variety of new LC phases has been confirmed. It should
be noted that the XRD pattern obtained for LC materials are
different from those for crystalline materials because LC
molecules have dynamic properties in the assembled state and
the position of the component molecules is not precisely fixed
in the LC state. To resolve the complicated assembled
molecular structures, the construction of electron density
maps from XRD patterns is a useful approach.[59] To achieve
this, the correct determination of the phase of individual
XRD reflections is significant. Based on this technique,
Percec and Ungar et al. constructed the electron density maps
of compound 7 a in the micellar cubic phase with Pm3n
symmetry (Figure 2 d,e).[70] To obtain further insight into the
assembled structures, they developed a new technique that
takes the differences between two electron density maps
obtained for analogous compounds. For example, they
prepared the 4:1 molar mixture of compounds 7 a and 7 b
which have micellar cubic phases. By subtracting the electron
density map of 7 a from that of 7 a/7 b mixture, the electron
density difference has been visualized (Figure 2 f). The differ-
ence in the electron density maps clearly indicates that the
electron-density-rich region is located in the center of micelle
domains.
3. New Nanostructured Functional Materials Based
on Dynamic Ordering
Liquid crystal materials exhibit a variety of phase
transition properties: Cryst-LC, LC-LC, and LC-Iso transi-
tions (Cryst: Crystal, Iso: Isotropic). These order–order and
order–disorder transitions are important for the functional-
ization of liquid crystals.[4, 6, 71] For thermotropic liquid crystals,
transitions are mainly triggered by increasing or decreasing
the temperature. In addition to such thermal stimuli,
photo[72–76] and mechanical stimulation,[6, 77–86] and electric
fields[87–96] have been found to induce phase transitions.
Photo-stimuli have been used to manipulate the molec-
ular order of liquid crystals.[73] Photochromic molecules, such
as azobenzene, have been incorporated into liquid crystals to
induce order–disorder transitions by trans--cis isomerization.
The orientation of azobenzene-doped liquid crystals can be
modulated by UV light, leading to the induction of an LC-
isotropic phase transition.[74] Other photochromic molecules
including diarylethene, fulgide, and overcrowded alkenes
have also been used to induce dynamic changes in molecular
orientation upon UV irradiation.[74] Order-decreasing phase
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transitions are normally induced for these photochromic
molecules, but order-increasing transitions, such as nematic to
smectic transitions, can be realized for LC mixtures contain-
ing naphthopyran derivatives.[75] In addition to the phase
transitions, LC molecular orientation has been directed by the
isomerization of photochromic compounds. Macroscopic
photocontrol of ion-conductive pathways is achieved by
combining an imidazolium moiety with a forklike mesogen
bearing three azobenzene moieties.[76]
Mechano-stimuli can be used to obtain macroscopically
aligned liquid crystals. This method has been used to form
oriented columnar LC phases, which results in the enhance-
ment of transport properties of charge and ions, and polarized
photoemission.[4, 9, 20, 67, 68] Mechano-stimuli can also trigger
phase transitions of LC material.[77–86] Recently, mechano-
induced LC phase transitions have been shown to be useful
for the development of new chromic materials (Figure 3 a).[77]
Kato and Sagara reported mechanochromic nanostructured
liquid crystals that change luminescent colors by a shear-
induced micellar cubic-columnar phase transition.[78, 79] Koz-
hevnikov and Bruce demonstrated luminescent color change
of platinum-based metallomesogens in response to mechan-
ical disturbance.[80] These concepts were extended to the
preparation of more complex mechano-responsive materials.
For example, tricolored luminescence from a single chromo-
phore was achieved for an equimolar mixture of dumbbell-
shaped compound 8 containing 9,10-bis(phenylethynyl)an-
thracene and dendron 9 (Figure 3 b).[81] A tricolored lumines-
cent image is obtained by combination of thermal and
mechanical stimuli. The three luminescent colors observed
for the mixture can be explained by the change of assembled
structures of the luminescent core moiety. Reversible ambi-
ent-temperature luminescent color changes were also found
for oligothiophene-based mechanochromic liquid crystals 10
(Figure 3 c).[82] The emission colors and stimuli-responsive
properties can be tuned by changing the number of thiophene
rings. Yagai and co-workers designed mechano-responsive
amphiphilic molecule 11 with the oligo(p-phenylenevinylene)
luminophore (Figure 3 d).[83] Application of mechanical stim-
uli converts the assembled structures of this amphiphilic
dipolar molecule from metastable aggregates into more stable
structures, which induces luminescent color changes. They
also demonstrated that molecule 11 can be applied for
invisible inkjet imaging. New metallomesogens composed of
copper iodide clusters and phosphine ligands bearing three
cyanobiphenyl mesogens show mechanochromic lumines-
cence as a result of the modulation of intramolecular
interactions.[84] Mechanochromic properties were also
induced for LC polymers.[85, 86] An LC block copolymer
composed of polythiophene and polyphenylisocyanide deriv-
atives exhibits vapor-induced liquid crystallinity and self-
recover mechanochromism under ambient conditions.[86]
Electric-field stimuli have been a major driving force to
align liquid crystals. Flat-panel display devices have been
realized by preparing low viscous and polar nematic mole-
cules.[2] For the alignment of nanostructured liquid crystals,
ferroelectric liquid crystals exhibiting chiral smectic C phases
were intensively studied.[87] Columnar liquid crystals can also
be oriented under electric fields.[88, 89] The alignment of one-
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dimensional columnar LC assemblies is desirable to explore
transporting materials.[90] Propylenecarbonate-based colum-
nar liquid crystals complexed with lithium salts can be
homeotropically aligned by the application of electric
fields.[90] The monodomain columnar assemblies form con-
ductive paths along the columnar axes, which facilitates
lithium-ion conduction. Ferroelectric switching of columnar
liquid crystals has also been studied. One of the earliest
examples is polar switching based on urea-based columnar
liquid crystals.[91] The linear hydrogen bonds of the urea
moieties in the columns play a key role in electro-responsive
switching.Bent-shaped polycatenar molecules also show
polarization under the electric field in the LC columnar
phase.[92] Recently, a fan-shaped molecule bearing polar
phthalonitrile and amide groups has been described to exhibit
ferroelectric properties in the columnar phase, in which the
macroscopic polarization is maintained after the applied
electric field is turned off.[93] These ferroelectric columnar
liquid crystals are promising candidates for the creation of
high-density memory devices.
In contrast to the electric-field-induced switching of
liquid-crystal orientation, examples of electric-field-induced
LC phase transitions are limited. Kutsumizu and co-workers
prepared 4’-docosyloxy-3’-nitrobiphenyl-4-carboxylic acid
which undergoes phase transitions from smectic C to Im3m-
type cubic phases under applied electric fields.[94] The rate of
the electric-field-induced phase transition depends on the
temperature of the sample and the frequency of the applied
electric field. The application of electric fields to the materials
was found to promote nucleation of the cubic phase, which
leads to the electric-field-induced phase transition.[95] Bene-
duci and co-workers reported electrofluorochromic liquid
crystals in connection with an electric-field-induced phase
transition from isotropic to smectic phases.[96] The emission
color and intensity are reversibly modulated in response to
the electric field. New applications are expected for these
electric-field-responsive materials.
4. Nanostructured Liquid Crystals for Energy
Applications
The development of advanced energy generators and
storage devices including fuel cells, solar cells, and batteries is
required for the realization of the sustainable society. These
devices are generally composed of electrodes and electrolytes.
Recently, it has been demonstrated that nanostructured LC
materials are capable of being used as new electrolyte
materials.[9, 71, 97–101] The basic concept is that segregated
structures at the nanometer scale consisting of ionophilic
and ionophobic parts yield two different functions, such as ion
transport nanochannels and insulating moieties. The insulat-
ing parts are expected to act as mechanically and thermally
stable moieties. Further advantages of using liquid crystals is
that anisotropic macroscopic alignment of the materials can
enhance the conductivities. Phase transitions of liquid crystals
can also be incorporated into functional design, which induces
switching of functions.
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Figure 3. a) Concept for the design of new chromic materials. b) Molecular structures of dendron-type molecule 8, having an anthracene core, and
compound 9. An explanation for the relationship between the change of its molecular assembled structures and luminescent colors. Reprinted
from Ref. [81] with permission from Wiley. c) Molecular structure of oligothiophene-based mechanochromic liquid crystals 10. Reprinted from
Ref. [82] with permission from the Royal Society of Chemistry. d) Mechano-responsive amphiphilic molecule 11 with the oligo(p-phenylenevinylene)
luminophore. Reprinted from Ref. [83] with permission from Springer Nature.

A variety of ion conductive LC materials have been
designed to allow the control of the nanostructure pat-
terns.[97–109] For example, ion-conductive columnar liquid
crystals forming 1D ionic nanochannels[102] and bicontinuous
cubic liquid crystals forming 3D ionic nanochannels[103–105] as
well as smectic LC materials,[106–109] have been developed and
studied. By employing specific ion-active groups, LC materi-
als transporting Li+ and I have been designed, which can be
used as electrolytes for lithium batteries[110] and dye-sensitized
solar cells (DSSCs),[111–113] respectively. LC materials con-

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ducting other ions including H+[114–116] have also been
examined for the development of fuel cells and the other
devices.
For the preparation of superior proton conductive mate-
rials, the key is to align the sulfonic acid group regularly on
the macroscopic scale to create a continuous hydrogen-
bonding network of water molecules through which the
proton can be transported at high speed by the Grotthuss
mechanism.[117] Self-organization of liquid crystals is expected
to be a powerful strategy for aligning the sulfonic acid
group.[118–121] Zwitterions are a class of ionic compounds
showing specific ion-conduction properties when mixed with
some acids.[114] Several ionic liquid crystals based on zwitter-
ions have been designed and employed for proton-conductive
materials.[115, 116, 122–127] For example, compound 12 exhibits
a bicontinuous cubic phase in the co-existence of sulfonyli-
mide derivatives 13 (Figure 4 a).[127] In the bicontinuous cubic
assembly, a 3D continuous gyroid minimal surface is formed
on which the sulfonic acid groups are arranged regularly. The
fixing of the 3D molecular assembled structures has been
achieved by modifying the ionic moiety to show glassification
instead of crystallization.[127] The obtained glassy bicontinu-

Figure 4. a) Pyridinium-based amphiphilic zwitterions 12 forming bicontinuous cubic phases in the presence of sulfonyl imide-type acids 13.
Reprinted from Ref. [127] with permission from Wiley. b) Propylenecarbonate-based liquid crystal 14 forming smectic phases with two dimensional
ion conductive layers. The mixtures of 14 and LiTf2N function as electrolytes for lithium-ion batteries. Reprinted from Ref. [110] with permission
from Wiley. c) Molecular structures of rod-shaped compound 15 having a propylenecarbonate moiety and rod-shaped compound 17 having an
imidazolium moiety. The mixtures of 15 and 16 or 17 can be used for electrolytes for dye-sensitized solar cells. Reprinted from Ref. [112] and
Ref. [113] with permission from the American Chemical Society. d) Wedge-shaped benzenammonium salts 18 exhibiting switching of ion
conductivity. The electron density maps are also shown. Reprinted from Ref. [130] with permission from the American Chemical Society.

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ous cubic liquid crystal can incorporate water molecules while
maintaining the 3D nanostructure and the water incorpora-
tion leads to a significant increase of ionic conductivity from
on the order of 10 8 to 10 5 S cm 1.
Lithium-ion batteries containing LC electrolytes have also
been reported.[110] For example, Kato et al. have designed the
rod-like LC molecule 14 which has a cyclic carbonate moiety
(Figure 4 b). The mixture of 14 and lithium bis(trifluorome-
thylsulfonyl)imide (LiTf2N) functions as an electrolyte having
electrochemical and thermal stability, and efficient ionic
conductivity. Using the LC electrolyte, lithium-ion batteries
which can undergo reversible charge–discharge have been
prepared. Gin and co-workers have designed a polymerizable
wedge-shaped ionic compound which has lyotropic LC
behavior in the presence of propylene carbonate.[128] By
performing in situ polymerization of the compound in the
bicontinuous cubic LC state, a nanostructured polymer film
with 3D ionic nanochannels has been prepared. This polymer
film functions as a polymer electrolyte playing the roles of
both electrolyte and separator.
Electrolytes of DSSCs normally has organic solvents, such
as acetonitrile, which is volatile and unstable over 50 8C. To
overcome this weakness, the use of ionic liquids has attracted
increasing attention owing to their non-volatile nature.[129]
Following the success in the development of DSSCs based on
ionic liquids, LC electrolytes transporting I have been
designed and prepared.[111–113] The mixture of compound 15
and ionic liquid 16 in DSSCs shows a power conversion
efficiency (PCE) of 6 % at room temperature. The PCE
values for DSSCs with electrolytes, such as acetonitrile and
ionic liquids, generally exhibit temperature dependence and
decrease as temperature increases. The operating-temper-
ature limits have been increased by designing compound 17
(Figure 4 c). The use of the 17-based electrolyte enables the
generation of electric power even at 120 8C with a PCE of
about 3 %.
Dynamic change of molecular-assembled structures of LC
materials can be used for designing soft materials that switch
their functions drastically.[4, 6] This design has been used for
ion-conductive liquid crystals.[130, 131] For example, Kato and
co-workers designed wedge-shaped ammonium salts 18
exhibiting rectangular columnar and hexagonal columnar
phases (Figure 4 d).[130] The electron-density maps in these
columnar phases are given in Figure 4 d. It shows that the
center of the columns has a higher electron density and the
columnar periphery has a lower electron density. This
compound shows an abrupt increase in the ionic conductivity
upon the phase transition from the rectangular columnar to
hexagonal columnar phases. For example, it shows ionic
conductivity in the order of 10 8 S cm 1 in the rectangular
columnar phases while showing ionic conductivity on the
order of 10 4 S cm 1 in the hexagonal columnar phases. To
clarify the origin of the dramatic change in ionic conductivity,
GIWAXS was performed. It revealed that the difference in
the degree of positional freedom of the anions results in the
difference in the ionic conductivity.
Not limited to ion-conductive materials, liquid crystals
have been used for various transport materials. For example,
thermally conductive insulating materials with LC nano-
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structures have been developed.[132, 133] Kim and co-workers
prepared discotic nematic LC films by in situ photo-polymer-
ization of homeotropically aligned LC monomers, which show
highly anisotropic thermally conductive behavior.[134] These
materials are important for controlling heat dissipation
properties in modern electronic devices. The introduction of
long alkyl chains into p-conjugated cores, such as disc-like
triphenylene and rod-like oligothiophene, provides columnar
and smectic LC electron transport materials.[20–22] The rela-
tionships between the molecular design and electron-trans-
porting functions has been summarized in some Reviews.[21, 22]
5. Separation
The supply of clean water is an important global issue.
Separation using polymer membranes to desalinate seawater
and to clean brackish water is a promising approach to resolve
this issue. Polymer membranes, such as reverse osmosis (RO)
and nanofiltration (NF) membranes, are now widely used for
water purification.[135–139] Commercial RO and NF mem-
branes contain cross-linked aromatic polyamides or cellulose
acetates as separation functional layers.[140, 141] Sub-nanopores
in these polymers serve as pathways for water, but their pore
size is non-uniform. Uniform size of pores may significantly
improve the separation properties of these membranes.
Porous materials with well-ordered sub-nanopores with uni-
form diameter have attracted attention as filtration mem-
branes.[135–138] LC polymers,[136, 142–146] carbon-based materials,
such as graphene oxide[147] and carbon nanotubes,[148] and
channel peptides[149] are potential representative materials of
such porous materials. Nanostructured films based on poly-
merized thermotropic or lyotropic liquid crystals have been
shown to provide sub-nanopores with uniform diameter.
There have been some reports on the use of these nano-
structured polymers for separation membranes.[135, 136] The
advantages of LC nanostructures as nano-porous materials
are as follows: 1) possibility of formation of defect-free films
because the initial melt LC states are transformed into solid
membranes by in situ polymerization; 2) designable channels
to give desired and uniform structures; 3) a high number
density of channels. For example, the pore sizes and proper-
ties of the pore walls can be tuned by post-modification
procedures, such as removal of non-polymerized components
or ionization of the functional groups.
Gin and co-workers applied lyotropic liquid crystals as
separation membranes. They demonstrated that water-treat-
ment membranes based on lyotropic LC states showed
rejection selectivity depending on the size of the nano-
channels and the solutes.[142–144] These membranes were
obtained by in situ polymerization of bicontinuous cubic
structures of ionic gemini surfactants[142, 143] as well as hex-
agonal columnar structures of a benzoate derivative.[144] For
example, a crosslinkable gemini imidazolium system with
pores of 0.75 nm in diameter demonstrated a high salt
rejection ability which was comparable with that of RO
membranes.[142] This high rejection rate of the membrane can
be due to the thick (ca. 2 mm) separating layer of the
membrane, which reduced the water permeability of the
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membrane. Control of the thickness of the LC separating
layer is important to enable higher flux and high rejection
rates.
Nanostructured membranes showing unique salt rejection
properties were obtained from thermotropic ionic liquid
crystal 19 forming bicontinuous cubic structures.[145, 146] The
membrane consists of three layers (Figure 5 a). The separating
Figure 5. a) Composite membrane for water treatment based-on poly-
merized triethylammonium liquid crystal 19. Reprinted from Ref. [145]
with permission from Wiley. b) Nano-porous membrane with defect (
left) and ordered pores (right). Reprinted from Ref. [146] with permis-
sion from Wiley.
layer is obtained by polymerization of the quaternary
ammonium compound generating the bicontinuous cubic
phase on the substrate. The bicontinuous cubic membrane
had NaCl rejection properties and water permeability,[145]
which are comparable to commercial nanofiltration mem-
branes. In addition, the salt rejection selectivity of the
ammonium bicontinuous cubic membrane is unique: rejec-
tion rates of Br and NO3 through the bicontinuous cubic
membrane (ca. 80 %) were higher than that of SO42 (ca.
30 %), which has larger hydrated radius. The unique selectiv-
ity of the bicontinuous cubic membrane can be attributed to
the ionic nature of the nanopores. These results suggest that
further selective filtration may be achieved by chemical
design of the surface of nanopores.
A potential application of the LC membranes in health-
care was shown by Kato, Katayama, and co-workers who
demonstrated a high rejection of viruses by the mem-
branes.[146] Viruses in water are usually removed and inacti-
vated using sterilization technologies, such as UV irradiation,
heating, solvent detergents, chlorination, or acid treat-
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ment.[150] Filtration is one of the most efficient non-chemical
treatment techniques and it purifies water by acting as a real
barrier against micro-organisms. The bicontinuous cubic
membranes developed by Kato et al. show significant rejec-
tion of viruses, Qb bacteriophage (ca. 20 nm diameter), with
an efficiency of higher than 99.9999 % (Figure 5 b).[146] The
bicontinuous cubic LC membranes have a regular channel
size, which contributes to the selective filtration, and they
have fewer defects because of the fixing of the self-assembled
LC material. These factors lead to the high rejection rate of
the membrane.
An ideal arrangement of channels in the separating layer
would be vertically aligned pores spanning the layer, but the
spontaneously formed interconnecting networks of bicontin-
uous cubic structures could also provide a good pathway. The
short pathways offered by straight channels allows increased
material transport. Film formation from homeotropically
aligned thermotropic columnar liquid crystals was achieved
by using special substrates on a amine-modified glass
substrate.[102] For lyotropic columnar liquid crystals, alignment
control of compound 20 using PDMS substrates or magnetic
fields was reported by Osuji and co-workers (Fig-
ure 6 a).[151–153] For the thinner films (< 5 mm), effects of the
interface on the alignment of columnar structures are enough
to form homeotropic aligned structures. For the thicker films
(> 5 mm), interaction between the aromatic rings and mag-
netic field control the orientation of columns.
Polymer materials with LC nanopores can be also used as
adsorbents at the molecular level as well as in filtration
membranes. In addition, the size of pores in LC polymer films
can be tuned by post-modification procedures. Polymerizable
host molecules and non-polymerizable content were com-
bined using non-covalent bonding[153–156] and dynamic cova-
lent bonding.[157] Formation of the LC state and subsequent
in situ polymerization for example by photopolymeriza-
tion[153–155] or acyclic diene metathesis (ADMET) polymeri-
zation[156, 157] gives polymer films with nanochannels filled with
non-polymerized small compounds. The LC nanopores were
obtained by removal of the non-polymerized small molecules
in the nanochannels (Figure 6 b). The LC nanopores selec-
tively adsorb molecules and ions which are of a suitable size
and charge. The adsorption properties of the pores can be
tuned by modifying the wall surfaces of the pores by chemical
reaction with chemically active groups.[157]
The preparation of nanoporous films with 2D smectic
structures and their molecular sieving properties were
reported by Broer and co-workers (Figure 6 c).[158–160] The
networks are composed of a polyacrylate containing a benzoic
acid in the side-chain. The benzoic acid forms dimerized
supramolecular structures through hydrogen bonding. This
“locked” polymer network can be opened by soaking the film
in an alkaline solution. The carboxylate groups formed 2D
channel structures and the integrity of the film is maintained
by a small amount of the covalent cross-linkers. The periodic
lateral 2D anionic pores selectively capture cations and
cationic dyes. In addition, the stored cationic dyes can be
released by soaking the dye-filled films in acidic aqueous
solution.[159, 160]
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Figure 6. Preparation of nanostructured polymer films: a) vertically aligned columnar channels; b) uniformed 1D nanoporous structures; c) 2D
nanoporous structures.
The use of nanostructured membranes is a significant
method to obtain well-organized nanopores. The introduction
of greater selectivity for ions and chemical species is possible
for these nanostructured membranes. Alignment control of
nanopores and size tuning of 1–3 nm scale are current
challenging issues.
6. New Functionalization of Nematic Liquid
Crystals
A nematic phase is the simplest LC phase and it has long
history of study and application.[1, 2, 26] However, new nematic
structures and materials and their functionalization, and
alignment methods for nematic phases have also received
much attentions. These new aspects of nematic liquid crystals
may open a new field of materials science.[74, 161–166]
Liquid crystal dimers, in which two mesogenic moieties
are connected by an aliphatic flexible spacer, were initially
synthesized as a model of main-chain LC polymers.[167] A
variety of mesogens and spacers was introduced into these
liquid crystal dimers.[168] Recently, a new twist-bend nematic
order was demonstrated for liquid crystal dimer 21 with an
odd number of methylene groups in the spacer (Fig-
ure 7 a).[161] In the twist-bend nematic phase, a helical arrange-
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ment with a director shaped as an oblique helicoid is formed
by self-assembly of achiral molecules. The oblique helicoidal
structures were employed to produce electrically tunable
materials, where a low driving electric field was sufficient
owing to the small bending constant of these materials.[169]
Orientational switching of nematic liquid crystals under
an electric field has been utilized for the manufacture of flat
panel displays.[2] Generally, the electrooptical response of LC
phases has been one of the most useful properties for
applications. Blue phases, which have double chiral nematic
structures, were reported to exhibit fast responses, optically
isotropic nature, and no requirement for rubbing process for
applications of displays.[162, 170, 171] Blue-phase materials are
also studied for use in optical lasers.[172] For these applications,
the narrow temperature range of blue phases was a serious
problem. To improve the stability of blue phases, Kikuchi and
co-workers added acrylate monomers to the blue-phase liquid
crystals and polymerized them. This approach leads to
stabilization of the blue phases over a wide temperature
range of more than 60 K including room temperature.[171] New
LC host nematic molecules were developed. For example,
compound 22 is T-shaped and forms stabilized blue phases
when this molecule is mixed with chiral molecule 23 (Fig-
ure 7 b).[170] Considerable efforts have also been made to the
structure elucidation of blue phases, these efforts have been
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Figure 7. New design of nematic materials. a) Liquid-crystal dimer 21
exhibiting a twist-bend nematic phase. b) T-shaped molecule 22 and
chiral compound 23 for the formation of blue phases. c) Polymerizable
lysine-based gelator 24 forming LC gels. d) Mesogenic surfactant 25
having bio-recognition moieties for sensing applications.
aided by recent advances in characterization techniques, such
as confocal laser scanning microscopy,[173] transmission elec-
tron microscopy,[174] and small-angle X-ray scattering meas-
urements.[175]
Liquid crystals mixed with self-assembled fibers or
covalently bonded polymer networks have been classified as
liquid-crystal gels, which are capable of exhibiting electro-
optical, photoresponsive, and electric properties as well as
memory effects.[163] Since the solvents are anisotropic for
these materials, cooperation of liquid crystals and self-
assembled fibers leads to the enhancement of properties
and the induction of new properties. The electrooptical and
magnetic properties of the anisotropic gels based on nematic
and cholesteric liquid crystals have been examined.[176–180]
Mixtures of polymerizable lysine-based gelator 24 and
a nematic liquid crystal, 4-cyano-4’-pentylbiphenyl (5CB),
are applied for the formation of fibrous polymerized networks
(Figure 7 c).[178, 179] These polymerized LC gels show improved
light-scattering properties compared with non-polymerized
LC gels. Aligned self-assembled fibers of organic radical
gelators exhibiting magnetic properties were also devel-
oped.[180]
Photo-responsive properties have been exploited for
nematic liquid crystals for the past three decades.[72, 181, 182]
For example, polarized light was used as an external stimuli
for the alignment of nematic liquid crystals.[74, 181–183] Solid
surfaces containing photo-reactive moieties, such as azoben-
zenes, have been used to manipulate LC orientation.[2, 181]
These photoreactive functional groups interact with LC
molecules on the surface and their photoreactions can
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switch the nematic LC orientation (Figure 8 a).[181, 182] The
azobenzene systems, known as “command surfaces”, are
angled selectively by azobenzene excitation with linearly
polarized light lead to in-plane alignment control of LC
Figure 8. Orientational control of liquid crystals using photo-reactive
matrices. a) “Command surface” system. b) “Command skin layer”
system. Reprinted from Ref. [183] with permission from Springer
Nature.
molecules. Photo-alignment of LC molecules without photo-
reactive solid substrate was achieved by Seki and co-work-
ers.[183] In their system, the ordering of LC molecules was
induced by a skin layer at the free surface (Figure 8 b), which
was prepared using a non-photoresponsive LC polymer film
and an azobenzene containing LC block copolymer. The
photoreactive skin layer was formed by spontaneous surface
segregation of the azobenzene polymer or ink jet printing
techniques. This “command skin layer” method will enable
various applications of photo-alignment LC materials.
Recently, Shishido reported hybrid alignment of dye-doped
liquid crystals for use in photonic applications.[184] The optical
response in the hybrid alignment cell was induced at low light
intensity compared to simple homeotropic alignment cell.
The dynamic behavior of nematic liquid crystals at an
interface can be used in sensors.[164, 185] Sensing systems using
amphiphilic surfactants and nematic liquid crystals have been
developed by Abbott and co-workers.[164, 186–191] These sensors
are classified as thin-film type (Figure 9)[186–189] or droplet
type.[190, 191] For the thin-film type, the LC layer was embedded
in a gold grid on a glass substrate soaked in a water solution
and surfactants self-assembled at the interfaces between the
LC phase and aqueous phase align the bulk LC molecules
homeotropically.[186–189] For the droplet type, liquid crystals
were encapsulated in polymeric surfactant microcap-
sules.[190, 191] The droplet sensors show high biocompatibility.
Mammalian cells can be decorated with the encapsulated LC
droplets by anchoring the droplets on the cell membranes.
The droplet can report on the presence of toxic agents in
surrounding media in real-time. In both systems, interfacial
events, such as binding of phospholipase from the aqueous
solution due to the specific interaction, induce re-ordering of
the LC molecules, which are optically observed as a change of
the LC textures. Designed surfactant 25 has a bio-recognition
moiety (Figure 7 d)[189] and was used to obtain an interface
which can enter into specific interactions with biological
molecules. These systems can be powerful tools for healthcare
use. For example, Abbott and co-workers achieved early stage
detection of b-amyloid formation (amyloid fibril which is
related to various significant neurodegenerative diseases,
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Figure 9. Molecular sensing system using nematic liquid crystals.
Optical images for a) homeotropic alignment induced by the amphi-
philic surfactant and b) homogeneous alignment induced by adsorp-
tion of biomolecules. Scale bar: 300 mm. c) Illustration of the orienta-
tion changes of the liquid crystals. Reprinted from Ref. [187] with
permission from the American Chemical Society.
such as Alzheimers)[188] and quantifying of exposure to
bacterial endotoxin (a major cause of disease and contami-
nation) at pg mL 1 concentrations.[190]
Dynamic and ordered states of nematic liquid crystals can
be applied for the preparation of LC actuators,[165] as well as
optical materials. Polymer films with well-organized molec-
ular order were obtained by Broer and co-workers based on
photopolymerization of LC monomers containing an infrared
(IR)-absorbing dye on patterned alignment layers.[192] These
LC polymer networks undergo macroscopic deformation into
cone or saddle shapes upon heating by IR irradiation. White
and co-workers precisely controlled orientation of liquid
crystals within local volume elements, leading to program-
mable shape changes of the LC actuators in response to
temperature changes.[193] Azobenzene-based LC molecules
show fast photoresponsive properties because the azobenzene
mesogen works as a photochromic moiety and efficiently
converts light energy into modulation of LC order.[72, 73] Based
on this concept, a variety of photo-controlled LC actuators
bearing azobenzene moieties have been prepared. Ikeda and
co-workers initially described directed bending of LC poly-
mer films possessing azobenzene moieties by irradiation with
polarized light.[72] The simple bending motion has been
extended to more complex motions, such as twisting, rotation,
and wave motion, by elaborating the design and alignment of
LC molecules.[73, 194] Chiral nematic structures have also been
applied for LC actuators. Deformation of chiral nematic LC
gels induced by an electric field was examined by Urayama
and co-workers.[195] Modulation of the optical properties
accompanied by the electric-field-induced deformation was
observed as a consequence of the variation of the helical
pitch. Actuation of chiral nematic liquid crystals is also
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utilized for modulating the height of fingerprint patterns on
the surface.[196] Manipulation of surface friction by UV
irradiation was demonstrated.[196] This mechanical motion in
response to external stimuli will be useful for application in
fields such as robotics and functional surfaces.
In addition to molecules with anisotropic shapes, aniso-
tropic colloidal particles also form ordered nematic struc-
tures. Suspensions of anisotropic colloidal particles, such as
rod-like nanocrystals of cellulose and nano-sheets of clays
form ordered nematic phases depending on their concentra-
tions.[166, 197] Recently, biodegradable and bio-friendly colloi-
dal LC hybrids have emerged.[198] These hybrids consisting of
rod-shaped CaCO3 nano-crystals were prepared using amor-
phous precursors stabilized with an acidic polymer additive.
Mechanical shearing can align the orientation of the colloidal
CaCO3 liquid crystals.
Colloidal liquid crystals of crystalline polysaccharides can
be used as templates to develop hybrid materials with helical
structures showing mechanical toughness, that are environ-
mental benign, and have optical functions.[199–201] CaCO3/
polymer composites with helically ordered structures were
prepared using colloidal chiral nematic liquid crystals of chitin
nano-whiskers (Figure 10).[199, 200] Acidification of the chitin
templates increase affinity between the organic templates and
the inorganic components. In nature, the cholesteric struc-
tures of chitin fibril, acidic proteins, and CaCO3 are shown in
the exoskeletons of crustaceans and these helical hybrid
structures are responsible for the mechanical toughness of the
composites.[202]
Figure 10. Preparation of organic–inorganic hybrid materials from
colloidal LC suspension of chitin whiskers. Reprinted from Ref. [199]
with permission from Wiley.
7. Summary and Outlook
New molecular structures and materials have been
generated from liquid crystal science. The formation of new
assembled structures and phases, including chiral phases, have
been reported.[5, 49, 203, 204] New usage of noncovalent interac-
tions for the supramolecular self-assembly of liquid crystals
has been shown.[5, 9] LC materials that can be categorized
between thermotropic and lyotropic liquid crystals have been
used as functional materials.[113, 205, 206] For example, mixtures
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of ionic liquids and wedge-shaped molecules having diol
moieties form stable columnar phases.[206, 207] These materials
show ion conductivities higher than the corresponding
imidazolium-based covalently bonded molecules. In this
case, the imidazolium-based ionic liquids can be regarded as
one component of functional binary mixtures for thermo-
tropic liquid crystals or as just isotropic solvents for lyotropic
liquid crystals. Moreover, carbon-based liquid crystals,[208, 209]
liquid crystals with colloidal particles[210] and fibrous aggre-
gates[163] are attracting attention. Liquid crystal materials that
do not conform to the conventional classification will be
developed, and enhanced or new functions will be achieved
for these anisotropic materials.
For applications of liquid crystals, we have shown some
new approaches to photo-, mechano-, electric-field-respon-
sive materials, ion-, electron-, thermo-conductors, separation
membranes, sensors, actuators, templates, and self-assembled
molecular machines. New bio-related applications[211] are
being proposed, for example, in tissue engineering.[212–215]
To achieve high functionality, the control of liquid crystal
structures, including domain formation and orientation con-
trol, and control of interactions to construct heterogeneous
and hierarchical structures, has to be given more attention.
The interactions with other fields of chemistry, physics,
biology, materials science, and engineering are important
for the further development and new industrialization of
liquid crystals.
Acknowledgements
We acknowledge partial financial support of KAKENHI
22107003 (Grant-in-Aid for Scientific Research on Innovative
Areas of Fusion Materials, no.2206) from the Ministry of
Education, Culture, Sports, Science and Technology (MEXT).
This work was partially supported by JST, CREST,
JPMJCR1422 and JPMJCR15Q3. J.U. is grateful for financial
support from the JSPS Research Fellowship for Young
Scientists and Program for Leading Graduate Schools
(MERIT). T.I. is grateful for financial support from the
Precursory Research for Embryonic Science and Technology
(PRESTO) from the Japan Science and Technology Agency
(JST) (no. JPMJPR1413). We thank Prof. Hirotsugu Kikuchi
and Prof. Yasushi Okumura at Kyushu University and
Masanari Nakayama at the University of Tokyo for helpful
discussions.
Conflict of interest
The authors declare no conflict of interest.
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Manuscript received: October 31, 2017
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Angew. Chem. Int. Ed. 2018, 57, 2 – 19
 Angewandte
Reviews Chemie

Reviews
Liquid Crystals New molecules and self-assembled
structures have been developed recently
T. Kato,* J. Uchida, T. Ichikawa, for liquid crystals. As a result a variety of
T. Sakamoto &&&&—&&&& new functions for liquid crystals, such as
transport for energy applications, sepa-
Functional Liquid Crystals towards the ration, chromism, sensing, electrooptical
Next Generation of Materials effects, actuation, and template have also
been described.

Angew. Chem. Int. Ed. 2018, 57, 2 – 19  2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.angewandte.org &&&&
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These are not the final page numbers!