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Frank–Kasper, quasicrystalline and related phases in liquid crystals

Goran Ungar* and Xiangbing Zeng
Received 17th February 2005, Accepted 5th April 2005
First published as an Advance Article on the web 20th April 2005
DOI: 10.1039/b502443a

The review covers 3-dimensional and some 2-dimensional self-assembly patterns of

supramolecular liquid crystals possessing either quasi-periodic or closely related truly periodic
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order. Compounds showing such structures are amphiphilic, and most often wedge-shaped, with
dendrons being the most common examples. The topology is described in terms of 3D and 2D
tiling of a variety of polyhedra or polygons, respectively. Analogy is made with structures of
Published on 20 April 2005 on http://pubs.rsc.org | doi:10.1039/B502443A

metallic alloys and soap froth. The recently discovered dodecagonal liquid quasicrystal is
compared with the different tetrahedrally close packed Frank–Kasper phases in thermotropic and
lyotropic liquid crystals. Parallels are also drawn with honeycomb columnar phases with related
plane tilings, including that of distorted pentagons. The potential for the creation of nearly
isotropic photonic bandgap materials is mentioned.

Ordered organic mesostructures are generated by molecular
self-assembly of dendrimers, block polymers and liquid
crystals (LCs). They have potential applications as materials
for molecular electronics (ion channels and molecular wires),
photonics, controlled drug release, nanoporous catalysts, and
lyotropic systems.1 In recent years there has been a prolifera-
tion of new phases in thermotropic (solvent-free) liquid
crystals with complex 2D and 3D geometries. Novel types of
order in soft matter have been discovered, including quasiper-
iodic packing of supramolecular spheres and periodic packing
of pentagonal cylinders. The richness in ordering patterns
arises from the different types of frustration in such systems.
As will become clear, there are strong parallels between
packing modes in liquid crystal phases and other apparently
unrelated systems on a range of scales from atomic to
macroscopic.
We begin with a brief historical introduction to packing of
particles and cells, the two being topological duals.2 We
then describe 3D periodic structures formed by packing of
*g.ungar@shef.ac.uk
supramolecular spheres, which is followed by a review of
quasiperiodic liquid crystal structures, i.e. those possessing
crystallographically ‘‘forbidden’’ symmetry. The review con-
cludes with an overview of some columnar liquid crystals
which have 2D ordering patterns closely related to those in the
3D patterns described in the preceding sections.
Some historical notes on packing of cells and spheres
It is generally accepted that the packing mode of neatly
stacked cannon balls, i.e. the face-centred cubic (FCC) or
hexagonal close packing (HCP), is the closest possible periodic
packing of hard spheres. Although it was Kepler who
proposed this conjecture, a rigorous mathematical proof was
much harder to achieve. A century ago Hilbert included a
variant of this question in his list of 23 most worthwhile
unsolved mathematical problems, and it was eventually solved
by Hales in 1997.3 A similar problem exists in two dimensions.
In the 4th century A.D. Pappus of Alexandria noted that a
‘‘divine sense of symmetry’’ guides bees to create highly regular
hexagonal honeycombs. Proving that this is the way of
creating a 2D array of identical cells using a minimum of

Goran Ungar obtained his Xiangbing Zeng graduated in

B.Sc. and master degrees in
Physical Chemistry from the
University of Zagreb, and his
Ph.D. from the University of
Bristol. After spending several
years at the Rud̄er Bošković
Institute in Zagreb and at the
University of Bristol, he moved
to the University of Sheffield
where he is now Professor in
the Department of Engineering
Materials. His research inter-
ests are crystalline polymers,
Goran Ungar liquid crystals and supramole-
cular assemblies.
1992 from the University of
Science and Technology of
China and received his M. S.
degree in condensed matter
physics at the Institute of
Physics, Chinese Academy of
Sciences. He received his Ph.D.
degree at the University of
Sheffield, where he is now a
Lecturer. His main research
interests are polymer and liquid
crystal structure, scattering
methods and polymer physics.
Xiangbing Zeng

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wax (the ‘‘honeycomb conjecture’’) has been another long-
standing challenge,4 resolved only in 2001 again by Hales.5
If the above conjectures presented such mathematical
difficulties, efficient 3D packing of soft or semi-soft spheres
presents an even greater challenge. Packing of compressed lead
shot or water-swollen peas has often been quoted as an
example. The ultimate soft spheres, the soap bubbles, and their
packing as froth of minimum wall area, were studied in the
19th century, particularly by Plateau6 and by Kelvin.7 Kelvin’s
interest in froth arose primarily from his belief that a
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constrained gasless foam has zero modulus, and was thus a
good mechanical model for ether, which was supposed to carry
light waves with no longitudinal component. Whether a 3D
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foam has zero modulus is debatable, but the statement is true
for the 2D analogue, the hexagonal honeycomb, which can be
deformed while preserving the orientation of the walls. An
interesting link can be made here with hexatic smectic liquid
crystals,8 which possess bond orientational but no positional
long range order in the layer plane.
In the first half of 20th century packing patterns were
studied intensely by biologists,9 who wanted to know, among
other things, if the tissue is shaped by packing considerations
(like lead shot) or by surface tension (like soap froth).10
Around the 1950s metallurgists and crystallographers took the
lead, with studies of atomic liquids11 and solids.12 Since atoms
are soft spheres, a lot of similarity in packing consideration
exists between metal atoms, soap froth and biological tissue.13
Structures of clathrates and gas inclusion crystal hydrates14
also have much in common. Liquid crystals fit well in this
wider context and give the subject a new dimension.
Frank–Kasper phases in liquid crystals
Thermotropic liquid crystal phases have traditionally been
observed in molecules with rod-like or disk-like shape.15
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Tapered wedge-shaped molecules were included at a later
stage.16 Prominent amongst those are dendron compounds of
different generations, including the first.17,18 Suitable mole-
cules would have an aromatic17 or other19 dendritic core,
terminated by alkyl, fluoroalkyl,20,21 or oxyethylene22 tails.
Compounds I–III represent some examples.17,23 Such mole-
cules self-assemble into supramolecular objects. Weakly
bonding substituents at the apex of the molecule, such as
hydrogen-bonding or ionic groups, stabilise the self-assembly,
but are not essential. If the dendron has a linear taper, i.e. its
cross-section area A increases linearly with the distance r from
the apex, or A(r) 3 r, then that compound will form a
columnar phase.24 As illustrated schematically at the top of
Fig. 1, the ‘‘pizza slices’’ will stack up in columns whose axes
form a long range ordered 2D lattice, usually hexagonal.16,20
If, however, the wedge is quadratic, i.e. A(r) 3 r2, then the
dendrons have a conical shape and will assemble in spheres, or
‘‘micelles’’ (Fig. 1 bottom). In turn such spheres pack on
different 3D lattices. In practice a quadratic wedge would
represent e.g. a dendron with a higher branching functionality
(three branches per monomer as against two branches) or an
increased number of terminal chains. Two systematic studies
of phase behaviour of benzylether-based dendron libraries
have been carried out, up to the 5th generation, including
tailored compounds with branch functionality varying from
one generation to another.25,26
Three such micellar phases with 3D long range order have
been found in the last decade: a body-centred cubic phase
with Im3̄m symmetry,27 another cubic phase with Pm3̄n
symmetry,28–30 and a tetragonal phase, with a large unit cell
and P42/mnm symmetry.24 All three phases have since been
found in many dendritic17,18,24–26 and other amphiphilic
compounds,21,23 with the Pm3̄n phase particularly recurrent.
It was shown that the molecular taper can be adjusted not
only by chemical design of the compound, but also by mixing
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Fig. 1 Liquid crystal self-assembly of wedge-shaped molecules such
as dendrons. a–c: flat ‘‘pizza slices’’ form columnar phases with 2D
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long-range order; d–f: cone-shaped molecules form supramolecular
spheres which pack on different 3D lattices (after ref. 17).
Fig. 2 Binary phase diagram of a mixture of a cubic-forming
amphiphilic quadratic wedge compound (right) and a negatively
linearly tapered compound (left) (after ref. 31).
two tapered mesogens with different gradients. Fig. 2 is
a binary phase diagram of a mixture of a cubic-forming
quadratic wedge compound (right) and a negatively linearly
tapered compound (left). The typical ‘‘lyotropic sequence’’ of
phases is observed, covering smectic, columnar and micellar
phases, with a bicontinuous cubic phase in the region denoted
A, intermediate between smectic and columnar.31 In Fig. 2 the
average taper of the mixture spans the range from A(r) 3 2r
(inverse columnar, far left), via A(r) 5 const. (smectic) and
A(r) 3 r (columnar) to A(r) 3 r2 (cubic, far right). Transitions
between these phases can also be induced by changing
temperature.25 Diagrams like that in Fig. 2 are familiar in
lyotropic systems of surfactants or lipids, where water content
is the usual variable. The ‘‘micellar’’ phases are at the extremes
of the lyotropic series, i.e. at very high or very low water
content (‘‘direct’’ and ‘‘inverse’’ phases, respectively).32 A
phase sequence similar to the lyotropic series applies also to
block copolymers, where the primary variable is the volume
ratio of the two blocks.33
The body-centred cubic (BCC) Im3̄m phase in supramole-
cular dendrimers (Fig. 3)27 has previously been found in block
copolymers,34 and recently also in a lyotropic micellar
system.35 There exists another lyotropic32 and another
thermotropic36 phase with Im3̄m symmetry, but both of these
occur in the range between lamellar (smectic) and hexagonal
(columnar) phases and have a double network and a recently
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Fig. 3 (a) Reconstructed electron density map of the BCC phase by
self-assembly of monodendrons. The isoelectron surfaces enclose the
high density regions, i.e. the aromatic dendritic cores. The low-density
continuum (green) represents the terminal alkyl chains. (b) Structural
model (cf. ref. 27).
established triple network, respectively. The 3D electron
density map of a unit cell of the dendrimer BCC phase,
obtained by reconstruction from small-angle X-ray intensities,
is shown in Fig. 3a. The high density regions, enclosed within
the spherical isoelectron surface, contain the aromatic cores,
while the continuum of low and constant density contains the
molten alkyl chains (see also the schematic in Fig. 3b).
As mentioned, the most widely occurring micellar thermo-
tropic phase is the Pm3̄n cubic. The structure was determined
on the 2nd, 3rd and 4th generation n-dodecyl-terminated
benzyl ether dendrons,28 and is shown schematically in
Fig. 4a.29 A unit cell contains eight ‘‘micelles’’, or supramo-
lecular dendrimers, each containing on average 12, 6 or 2
dendron molecules, respectively, for the three compounds. The
unit cell length is typically of the order of 10 nm, although
recently a dendron was successfully synthesised giving a cell
parameter of 22 nm.37 The structure of the phase in Fig. 4a was
confirmed by the isomorphous replacement method, whereby
(a) the outer parts of the alkyl chains were selectively
perfluorinated, and (b) Rb ions were introduced as carboxylate
salts.38 As expected, the electron-rich fluorine and Rb showed
up at the periphery and the centre of the micelles, respectively.
A Pm3̄n phase with an analogous structure also exists as a
direct (oil in water) micellar lyotropic phase in lipids.39 No
equivalent is known in block copolymers.
The third micellar phase in thermotropic liquid crystals has
a large tetragonal unit cell with P42/mnm symmetry.24 The cell
contains 30 nearly spherical micelles (Fig. 4b). The P42/mnm
phase has been observed in a number of dendrons, and it
invariably occurs at higher temperatures than the Pm3̄n
phase, but below the temperature of the Im3̄m BCC phase.
Fig. 4 Schematic drawings of the unit cells of the Pm3̄n cubic
and P42/mnm tetragonal micellar phases. There are 2 and 5 types
of crystallographically non-equivalent spheres in the Pm3̄n and the
P42/mnm unit cells respectively, as indicated by different symbols
(after ref. 24).
Soft Matter, 2005, 1, 95–106 | 97

The volume of a tetragonal unit cell is 3.6 times that of the
Pm3̄n cell.
While not made up of spherical aggregates, the body-centred
tetragonal thermotropic phase of calamitic (‘‘rod–coil’’)
mesogens should be mentioned here for completeness.40 The
rod–coil molecules also display a variety of interesting phases,
not covered here.41
It is interesting that all three micellar phases, i.e. the Im3̄m
BCC, the Pm3̄n and the P42/mnm, are well known structures in
metals and alloys. For example, BCC is the structure of a-iron;
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the Pm3̄n structure is found in a series of binary transition
metal alloys such as Cr3Si or Nb3Sn, and is known as A15; the
tetragonal P42/mnm structure is known as s-phase occurring
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in a number of alloys, such as Fe46Cr54.42 No pure metal shows
the A15 structure, although at one time it was thought to be
the structure of b-W, whereas the s-phase is virtually
isomorphous with one pure metal phase, b-U. The remaining
micellar phases in lyotropic liquid crystals, i.e. the Fd3̄m
cubic,39 and the two close-packed structures, face-centred
cubic (FCC, spacegroup Fm3̄m)35 and hexagonal close packing
(HCP, P63/mmc),43 are also well known in metals. While the
latter two are widespread in pure metals, the Fd3̄m structure is
that of the MgCu2 Laves phase, also known as C15.
The Pm3̄n, P42/mnm and Fd3̄m are all members of the class
of tetrahedrally close packed (TCP) structures, or Frank–
Kasper phases.12 There are 24 confirmed FK phases in
transition metal alloys.44 These structures contain only
tetrahedral interstices. For a system of a few equal-sized
spheres, tetrahedral packing is the densest possible (Fig. 5a).
However, packing based exclusively on regular tetrahedra
cannot fill the space. As mentioned in the introduction, if the
objective is to pack hard spheres on a regular lattice with a
minimal unoccupied volume, the solutions are the two ‘‘close
packings’’, FCC and HCP. However, both of these contain
octahedral as well as tetrahedral interstices (Fig. 5b). The
centre of an octahedron is significantly further from the
surrounding spheres than is the centre of a tetrahedron. Each
atom in FCC or HCP has co-ordination 12, and the co-
ordination polyhedron has 6 square and 8 triangular faces and
24 edges.45 If one tries to devise a purely tetrahedral structure,
one soon realizes that a non-integer number, 5.1, of tetrahedra
can be placed around a common edge (Fig. 5c). Thus in order
to fit five and close the gap, the tetrahedra must be somewhat
stretched. By adding two further layers of tetrahedra on top, as
in Fig. 5d, a regular icosahedron is created. The central atom
Fig. 5 Different packing modes of spheres: (a) tetrahedral packing; (b) hexagonal close packing (HCP), showing an octahedral vacancy
(tetrahedral vacancies are indicated by small circles); (c) there are 5.1 tetrahedra around a common edge; (d) icosahedron built of nearly regular
tetrahedra; (e) CN14 polyhedron consisting of more distorted tetrahedra.
98 | Soft Matter, 2005, 1, 95–106
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has again co-ordination number 12 (CN12), but the poly-
hedron has only triangular faces and 30 edges. This means
that the atoms on the co-ordination shell are more closely
packed than in FCC or HCP, having 30 rather than 24 mutual
close contacts. Because the tetrahedra are distorted, the
distance from the central atom to the shell atoms is 10%
shorter than that between the shell atoms.
Icosahedral packing is particularly suitable for soft equal-
size spheres, where the 10% contraction could be tolerated.
However, although this packing is best for 13 spheres,
icosahedra cannot fill the entire space. An icosahedron, point
symmetry 5̄3̄(2/m) can be thought of as a pentagonal antiprism
with the centres of the pentagons pulled out to form vertices 11
and 12. Thus if one imagines placing the icosahedra side-by-
side, the space filling problem can be related to the inability of
regular pentagons to tile a plane. Nevertheless, it turns out44
that all but two TCP structures in alloys are layered structures,
with alternating densely populated and sparsely populated
planes of atoms. Alternative horizontal planes in Fig. 4 are the
dense planes for Pm3̄n and P42/mnm unit cells. Although all
Frank–Kasper phases feature distorted icosahedra promi-
nently, they all contain other polyhedra too. Kasper46 deduced
that at least some of the following polyhedra are also required:
CN14, CN15 and CN16. Fig. 5e shows how the CN14 poly-
hedron is created by squeezing in two additional tetrahedra
into the icosahedron, creating what can now be regarded as a
hexagonal antiprism with bulging base-centred hexagons.
It is common in crystallography to replace co-ordination
polyhedra with their topological duals, the tessellating
Voronoi or Wigner–Seitz polyhedra.47 Thus, e.g. the Voronoi
cell of a co-ordination icosahedron is a pentagonal dodecahe-
dron. The Voronoi polyhedra corresponding to CN14, CN15
and CN16 contain respectively 2, 3 and 4 hexagonal sides,
additional to the twelve pentagons. A unit cell of the Pm3̄n
phase contains two Voronoi 12-hedra and six 14-hedra.48 In
Fig. 6a a unit cell of the P42/mnm phase in an alkoxy-
terminated benzyl ether dendron is represented by both
isoelectron surfaces enclosing the high-density aromatic
dendritic cores (yellow spheres), and the Voronoi polyhedra
surrounding them. Of the 30 polyhedra in the unit cell, ten are
12-hedra, sixteen are 14-hedra and four are 15-hedra (see
Fig. 6b–d). All these polyhedra are distorted to a degree, and
two different types of distortion are present in both 12- and 14-
hedra, giving a total of five different co-ordination environ-
ments of the 30 micelles.
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Fig. 6 (a) Isoelectron surface (yellow) enclosing high density regions
of micelles in the reconstructed electron density map of the P42/mnm
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dendron structure. Voronoi polyhedra (blue) surrounding the
micelles are also shown; these are either 12-hedra (b), 14-hedra (c) or
15-hedra (d).
The fact that in the same dendrimer structure micelles of
a pure compound can have five different environments,
and hence shapes, suggests that the free energy is minimised
globally at some expense to that of the individual micelle.
The supramolecular dendrimer spheres are believed to have
sufficient compliance to adapt. An even larger difference in
micellar sizes is found in the lyotropic Fd3̄m phase,49 a TCP
structure made up of CN12 and CN16 inverse micelles
(Fig. 7).50 It is unlikely that this phase will be found in pure
thermotropic LCs, although it might possibly occur in
mixtures where larger molecules would inhabit the larger
CN16 micelles. Notably the equivalent metallurgical Laves
phase C15 occurs only in alloys with a large atom size
difference.
The Frank–Kasper layers of atoms are made up of triangles,
squares and hexagons. Triangles are those on surfaces of CN
polyhedra. Fig. 8 shows both the sparse layers (large circles)
and the dense layers, displaced by ¡z/4 (small black and white
circles, respectively) for the Pm3̄n and P42/mnm phases. The
distorted hexagonal antiprism (CN14 polyhedron) is promi-
nent in both structures, centred on each atom of the sparse
layer. Pentagonal faces are tilted to the primary layers and do
not form continuous planes. This is how the awkward problem
of pentagonal tiling is resolved in periodic 3D structures.
What makes dendrimers and metals adopt equivalent
complex packing patterns is the similarity in the soft inter-
action potential between the spheres, albeit on different length
scales. The ‘‘softness’’ of atomic d-orbitals plays a significant
role in determining TCP structures in transition metals.51
Supramolecular dendrimers have been approximated by hard
Fig. 7 (a) Packing of inverse micelles in the Fd3̄m cubic phase in
lyotropic lipid–water systems; Voronoi polyhedra with protruding
spheres (schematic) for micelles with coordination number (b) 16 and
(c) 12 (after ref. 50).
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Fig. 8 Packing of spheres in (a) Pm3̄n and (b) P42/mnm phases
viewed along the z axis. Both the sparse layers (large circles) and the
dense layers, displaced by ¡z/4 (small black and white circles,
respectively) are shown.
spherical cores and soft aliphatic coronas with a tendency for
surface minimisation.52 The optimum solution of the packing
problem for such a system coincides with the solution of the
Kelvin problem of the minimum energy dry foam (minimum
surface area per bubble).53 Kelvin’s original solution was the
Im3̄m BCC structure,7 but in 1994 Weaire and Phelan54
proposed the cubic Pm3̄n structure as having a 0.4% smaller
total surface area. Since froth is not a dynamic system, it was
difficult to prove that the new solution was indeed ultimately
the best. The appearance of Pm3̄n as the equilibrium structure
in many supramolecular dendrimers and other LCs was taken
as experimental vindication of the Weaire–Phelan solution.52
While at higher temperatures increased conformational
disorder leads to lateral expansion of the dendrimer’s aliphatic
corona, at low temperatures the driving force is its area
minimisation. When the alkyl chains are offered too much
lateral area by the spherical surface, and too little by the
cylindrical surface, the system looks for a packing equivalent
to the solution of the Kelvin problem. In most supramolecular
dendrimers, where there is a LC phase below the temperature
range of the Pm3̄n, that phase is hexagonal columnar.25,26,55
This suggests that, of the structures described so far, only a
2D honeycomb foam is a better solution than that of Weaire
and Phelan.52
In order to explain why spherical supramolecular dendri-
mers pack on lattices other than Pm3̄n, the average radial
distribution functions of volume dV/dr have been calculated
for different 3D structures.24 These functions give the ideal
dendron shapes that would fill the unit cell of a given phase
perfectly uniformly. Imagine spheres of radius r growing
simultaneously from the centre of each Voronoi polyhedron
(cf. Fig. 6 and Fig. 7b,c). Let vi(r) be that part of the volume of
the Voronoi cell i which is within the sphere. At the beginning
which is within small r the spheres grow freely and dV/dr 3 r2.
As a sphere i hits the walls of its Voronoi polyhedron, the
growth rate of its volume vi slows and begins to decrease. Fig. 9
P
shows the averaged functions dV/dr, where V~ð1=N Þ N i~1 vi is
the mean v and N is the number of polyhedra in the unit cell. As
the furthermost vacancies are filled dV/dr reverts to zero. It is
worth noting that a similar calculation was carried out to compare
simple cubic, BCC and FCC micellar packings in diblock
copolymers.56
A way to relate the dV/dr functions to the molecular shape is
to imagine the conical molecule (inset a) rolled out flat in the
direction perpendicular to the cone axis, into a parabolic (r2)
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Fig. 10 Packing frustration in the inverse hexagonal phase (from

Fig. 9 Radial distribution of volume functions dV/dr for different ref. 50 by permission of American Chemical Society).
micellar phases: FCC, BCC, P42/mnm and Pm3̄n. For explanation of
insets see text (after ref. 24).
adjusted than that of e.g. the dendrimer core is probably the
reason for the Fd3̄m structure being observed in inverse
fan as schematically drawn in inset b in Fig. 9 (compare also lyotropic but not in thermotropic LCs.
with the chemical structures of dendron I). The ideal envelope In the above the term ‘‘direct lyotropic phase’’ was restricted
of the molecular fan for each phase is represented by the to systems with non-polar chains terminated by small polar
corresponding dV/dr, with r 5 0 at the acute apex of the groups, e.g. to ionic surfactants or lipids. In case of non-ionic
molecule. The rectangle in inset b indicates the limited region surfactants, such as C12H25(OCH2CH2)12OH (C12EO12), a
of dV/dr shown in the diagram. water-containing ‘‘direct’’ lyotropic phase could still experi-
The dV/dr distribution for BCC differs from those for Pm3̄n ence space-filling restrictions described for thermotropics.
and P42/mnm in that it has a slightly higher peak and shorter The C12EO12–water phase diagram in Fig. 1135 shows the
tail. This explains why BCC is always seen at a higher following sequence of ‘‘direct’’ phases with increasing
temperature than the other two phases:25 it is precisely this water content just above 0 uC: solid A hexagonal (HI) A
change in molecular envelope that is expected from a lateral Pm3̄n A BCC (Im3̄m) A FCC (Fm3̄m). This sequence
thermal expansion and longitudinal contraction of alkyl agrees well with the sequence of dV/dr curves in Fig. 9,
chains. The dV/dr curves for Pm3̄n and P42/mnm phases are assuming that an effective increasing molecular taper is
very similar, and indeed the two phases have often been found produced by an increasing degree of swelling of the oxyethyl-
to appear interchangeably, although the low-temperature ene chain by water. It could be argued that ‘‘solvating’’ water
stable phase was always Pm3̄n. A comparison of the more causes lateral expansion of the EO part, while the remaining
sensitive derivative curves dV/dr could distinguish between ‘‘free’’ water, if available, fills the interstices, including the
Pm3̄n and P42/mnm and indeed supported the observed octahedral ones in FCC.
temperature sequence.24
Fig. 9 also suggests the reason for FCC structure never
having been observed in dendrimers or other thermotropics
LCs (the same applies to HCP). A high peak and a long tail of
the relevant dV/dr are incompatible with the shape of the
existing dendrons. It was proposed24 that a possible FCC
candidate should have a short branch on one of the first
carbons of the alkyl tail, and should include a small fraction
of extra long chains. The long chains are required to fill the
‘‘tail’’ of the dV/dr curve, i.e. reach the centres of octahedral
vacancies.
It is indicative that the only inverse micellar lyotropic phase,
Fd3̄m, is a TCP structure, whereas FCC and HCP occur as
direct phases. In direct micelles water is available to fill the
octahedral vacancies. In contrast, the situation with inverse
micelles is similar to that in thermotropics. Fig. 10 illustrates
the packing frustration in the inverse hexagonal phase, which
is also applicable in principle to inverse micellar structures.50
The intermicellar distance is adjusted as a compromise
between the enforced compression and extension of alkyl
chains at different positions on the soft micellar corona. The Fig. 11 Binary phase diagram for the system C12EO12–water (from
fact that the shape of the central water bubble is more easily ref. 35 by permission of American Chemical Society).

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Liquid quasicrystal
It has been a long-standing belief that crystals must be
periodic, consequently rotational symmetries other than 2-, 3-,
4-, and 6-fold were considered ‘‘forbidden’’ in crystallography.
However, this was challenged by the discovery of a phase in
Al–Mn alloys, the diffraction pattern of which showed
icosahedral symmetry.57 The discrete sharp diffraction peaks,
which indicated beyond doubt the existence of long range
order, were in apparent contradiction with the 5-fold
symmetry displayed by the diffraction pattern. Subsequently
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a series of metal alloys were discovered with ‘‘forbidden’’ 5-,
8-, 10-, or 12-fold rotational symmetries,58 and the term
‘‘quasicrystal’’ was coined59 for this unconventional structure
Published on 20 April 2005 on http://pubs.rsc.org | doi:10.1039/B502443A
of matter. These developments led to a re-examination of the
assumption that long-range translational symmetry is equiva-
lent to periodicity, and to the extension of the definition of
crystal to include quasicrystals.60,61 The famous Penrose tiling
shows how a ‘‘forbidden’’ 5-fold symmetry can be achieved in
a pattern with both long range translational and orientational
orders, but without periodicity (Fig. 12a).62 Penrose tiling can
also be constructed in 3 dimensions, having icosahedral
symmetry (Fig. 12b).62 The Fourier transform of the Penrose
tiling pattern has pentagonal symmetry and consists of sharp
Bragg spots (Fig. 12c).62
With hindsight, given the analogy between micellar LC
phases and metallic structures, it could be said that the recent
discovery of a micellar liquid crystal phase with dodecagonal
quasicrystalline symmetry63 should not have been entirely
unexpected. Before discussing this phase, however, we give a
brief survey of earlier associations made between quasicrystals
and liquid crystals.
The possibility of a liquid crystal possessing quasicrystalline
symmetry was suggested back in 1986 for the blue phase III in
chiral liquid crystals.64 It was proposed that this optically
isotropic phase had a broken icosahedral symmetry created by
the quasiperiodic arrangement of disclination lines within the
structure. However, no Bragg diffraction corresponding to
such an ordered structure was observed. It is now generally
Fig. 12 Penrose tiling (a) in two dimensions, showing pentagonal symmetry, and (b) in three dimensions with icosahedral symmetry. (c) Fourier
transform of (b) along the five-fold symmetry axis. (b) is an exploded view of tessellating polyhedra, which can all be broken down into two types of
elementary rhombohedra (after ref. 62).
This journal is ß The Royal Society of Chemistry 2005
View Article Online
agreed that the phase is disordered instead, and its transition
to the standard high-temperature isotropic phase is analogous
to that of the liquid–gas transition.65
Special behaviour of thin films of a TGB liquid crystal has
also been considered in terms of quasicrystalline ‘‘forbidden’’
rotational symmetry.66,67 In 1988, Renn and Lubensky
predicted the existence of the twist grain boundary (TGB)
phase occurring between the cholesteric and smectic phases in
chiral systems by making the analogy with the Abrikosov
phase in type II superconductors.68 Almost at the same time,
but independently, the phase was found experimentally.69,70
The TGB phase is a result of competing tendencies for smectic
layering and helical twist due to strong chirality. The structure
consists of slabs of constant thickness lb (Fig. 1371), usually
on a scale of y100 nm, stacked in a helical fashion along
an axis parallel to (TGBA), or at an angle to (TGBC), the
smectic layers.
In the TGB phases, the molecular director n (the average
direction of molecular long axes) is rotated between adjacent
slabs by an angle a (it should be noted that TGBC structures
are more complex than implied in Fig. 12. In various TGBC
structures reported, neither the smectic normal nor the
molecular director are necessarily perpendicular to the TGB
helical axis. The molecular director n can rotate in a helical
fashion within a smectic slab, and an undulated, 3D
modulated phase has also been reported. A detailed review
of the TGBC phase is given in ref. 72). Under normal
circumstances a/2p is an irrational number. However, rational
values of a/2p 5 p/q, where p and q are mutually prime
integers, have been observed in thin films of TGBC66,67 and
TGBA73 liquid crystals confined between glass plates with
rubbed surfaces. There is thus a q-fold screw axis, and non-
crystallographic values q ? 2, 3, 4 or 6 were observed. Lock-in
transitions between different q-values occurred with changing
temperature. However, the occurrence of a spontaneous
commensurate lock-in over large distances (the helical period
is normally .1 mm) was considered unlikely. It is still an open
question whether the commensurability is intrinsic to the TGB
phase or whether it is an artefact due to small sample thickness
Soft Matter, 2005, 1, 95–106 | 101
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Fig. 13 Schematic drawing of the twist grain boundary (TGBA) phase. Slabs of periodically spaced smectic planes are separated by grain
boundaries consisting of parallel screw dislocations. The layer normals of adjacent smectic slabs are rotated by a (after ref. 71).
Published on 20 April 2005 on http://pubs.rsc.org | doi:10.1039/B502443A

Fig. 14 Experimental and simulated X-ray diffraction patterns of the dodecagonal liquid quasicrystal (LQC). Single-crystal pattern (a) along and
(b) perpendicular to the 12-fold axis. The reciprocal lattice plane in (b) cuts through the uppermost and the lowermost of the 12 strong diffraction
spots in (a). The reflections are indexed on a 5-dimensional reciprocal lattice, with the unit vectors qi indicated. The intensities of outer diffraction
peaks in (a) and (b) are scaled up by 100. Simulated diffraction patterns are superimposed, with the reflections represented by circles whose area is
proportional to log(amplitude) (from ref. 63 by permission of Macmillan Press).

and the imposed layer alignment at the rubbed surfaces.74,75 If
it could be shown that the lock-in is intrinsic, the structure
could be considered as quasicrystalline.
In a number of supramolecular dendrimers of the benzyl
ether type a phase of unknown structure was observed above
the temperature region of the columnar phase. Its powder
diffraction pattern could not be indexed, and it was only when
a compound was obtained in which the phase formed directly
from isotropic melt (compound I) that monodomains could be
grown. The quasicrystalline nature of the phase was revealed
by the distinctive 12-fold symmetry of the single-crystal small
angle X-ray diffraction pattern (Fig. 14a). The structure of
this liquid quasicrystal (LQC) is periodic in the direction of the
12-fold axis, but quasiperiodic in the plane perpendicular to it.
The structure of the LQC is believed to be analogous to that
of dodecagonal quasicrystals found in metal alloys. Four such
alloys are known at present. In LQC the supramolecular
‘‘micelles’’ stand in place of the metal atoms. The characteristic
length of the quasicrystal is thus increased by nearly two
orders of magnitude, from a few angstroms to nearly 10 nm. In
liquid crystals as well as metal alloys, the dodecagonal phase is
found in the vicinity of the Pm3̄n and P42/mnm phases in the
phase diagram, and it is thus expected that their structures are
closely related. In fact, as shown in Fig. 15, a model of the
dodecagonal quasicrystal can be constructed by dodecagonal
quasiperiodic tiling76,77 of the basic structural elements found
in the Pm3̄n and P42/mnm structures78 (cf. Fig. 8). The
simulated X-ray diffraction patterns (Fig. 14) of the model give
a reasonable fit to experimental ones in both the position and
relative intensity of the diffraction spots. However, discre-
pancies in intensities remain, suggesting that the model needs
further improvement.
Note that the most frequently occurring vertex in the tiling
in Fig. 15 joins, in circular sequence, two triangles, a square, a
triangle and a square (denoted 32.4.3.4, Fig. 15c). This vertex
presents 83.7% of all vertices in the model by Stampfli76 and
84.7% of those obtained by simulation in which the condition
was enforced that square tiles should be next to triangular

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Published on 20 April 2005 on http://pubs.rsc.org | doi:10.1039/B502443A
Fig. 15 (a) Proposed model of sphere packing in the dodecagonal
LQC. Like the related TCP structures Pm3̄n and P42/mnm, it can be
generated by 2D tiling, this time quasiperiodic, of only squares and
equilateral triangles, which are ‘decorated’ with spheres at different
elevations (b). (c) The frequently occurring vertex 32.4.3.4. The length
of the tile edge, as well as the periodicity along the 12-fold axis, is
8.14 nm at room temperature (after ref. 63).
ones.79 The 32.4.3.4 vertex represents 100% of vertices in
the P42/mnm phase (Fig. 8b). It should be noted that in a
number of dendrimers, including compound I, the LQC phase
transforms on heating directly to the P42/mnm phase.
It is instructive to consider periodic structures which
approximate the quasiperiodic dodecagonal LQC, the so-
called approximants. Four such approximants are shown in
Fig. 16 with increasing unit cells, starting with the Pm3̄n
structure.63 The simulated diffraction pattern approaches
more closely that of the quasicrystal as the unit cell of the
approximant increases. However, for the satellite reflections to
become indistinguishable from the main peaks, it is estimated
that the size of the unit cell would have to be unrealistically
large, with a base of at least 100 6 100 nm2.
Fig. 16 Structure models viewed along the c-axis (top) and the corresponding simulated diffraction patterns (bottom) of a series of approximants
of the dodecagonal quasicrystal. The cell parameters are a 5 b 5 8.14 nm (Pm3̄n), 15.73 nm (P42/mnm), 30.38 nm (approx. 3) and 58.69 nm
(approx. 4). c 5 8.14 nm in all cases. The number of micelles in the unit cell is 8, 30, 112 and 418, respectively (after ref. 63).
This journal is ß The Royal Society of Chemistry 2005
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According to the model in Fig. 15, the alternation of densely
and sparsely populated layers is carried through from Frank–
Kasper structures to that of the dodecagonal LQC, and the
latter appears to belongs to the family of tetrahedrally close
packed structures even if it is not periodic. Each micelle on a
sparse layer is at the centre of a hexagonal antiprism, as in
Fig. 5e. The ABCB stacking of layers of spheres can indeed be
seen in the preliminary atomic force micrographs (ref. 63,
supplementary information). Determination of the atomic
positions in a quasicrystal by microscopy is extremely difficult
for metal alloys due to limited resolution: current experimental
methods can not reliably resolve structures at the atomic scale.
Since the size of the spheres in LQC is of the order of 4 nm, it
is anticipated that a detailed AFM study will be able to
determine the positions of micelles in the dodecagonal LQC
unambiguously.
Regarding its relation with other mesophases, it is interest-
ing to note that the micellar LQC has so far always been
observed at temperatures above the columnar phase but below
any other micellar phase. While it cannot be ascertained that
LQC was always the stable phase, by all accounts it is
thermodynamically stable in some cases, such as in compound
I, where annealing for up to a week close to the isotropisation
temperature caused no phase change. The possibility is thus
raised of dodecagonal quasicrystals replacing the Pm3̄n struc-
ture54 as the best solution of the Kelvin problem of minimum
energy foam.
Columnar LC analogues: pentagonal, square and
triangular honeycombs
A whole new class of thermotropic columnar liquid crystal
phases has been introduced in recent years, where the columns
are cells with walls containing aromatic rod-like mesogens.
The largest groups of mesogens forming such phases are
the T-shaped bolaamphiphiles80 and facial amphiphiles.81
Soft Matter, 2005, 1, 95–106 | 103

Bolaamphiphiles have an aromatic rod-like core terminated by
two polar chains, and a laterally attached nonpolar chain; in
facial amphiphiles the positions of the polar and nonpolar
chains are reversed as in compounds IV and V.
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Published on 20 April 2005 on http://pubs.rsc.org | doi:10.1039/B502443A
In most cases the rod-like cores lie perpendicular to the
column axis. The side-groups form the ‘‘soft’’ centres, while
the aromatic rods form ‘‘hard’’ walls of the columns which
have a polygonal cross-section. Depending on the relative
volume of the side group, the polygon has a smaller or a larger
number of sides. Each side is one or sometimes two rods long,
with an additional allowance for the end-groups. Polygons
from triangle to hexagon have been reported as column cross-
sections.80 An illustrative example is provided by a recent
study on facial amphiphiles IV and V. These triblock
amphiphiles both form a phase with a square 2D unit cell of
p4gm symmetry. Electron density maps in Fig. 17a and c show
that both phases consist of a mixture of pentagonal, square
and triangular columns. However, the difference between them
Fig. 17 Reconstructed electron density maps (a–c) and corresponding
models of molecular organization (d–f) of honeycomb columnar
phases consisting of pentagonal (a,d), square (b,e) and mixed square
and triangular (c,f) columns formed by compound IV (a,d) and V
(c,d,e,f) (after ref. 81).
104 | Soft Matter, 2005, 1, 95–106
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Fig. 18 The dual tilings of the topological class (32.4.3.4). (a) and
dashed lines: tiling by identical pentagons; (b) and solid lines: tiling by
squares and triangles (from ref. 81 by permission of American
Association for the Advancement of Science).
is that in compound IV the polar chains (purple colour) are
contained in pentagonal columns, whereas in compound V,
being shorter, they are contained in the triangular and square
columns. The yellow–red areas are columns containing low
electron density alkyl groups—Fig. 17d and f. At a somewhat
higher temperature compound V displays another square
columnar phase, plane group p4mm, in which the polar groups
are contained in square columns (Fig. 17b,e). The reason for
this transition from square–triangle to pure square column
arrangement on heating is the preferential thermal expansion
of the oligo(ethylene oxide) (EO) groups.
The two types of EO columns in Fig. 17d and f are
schematically shown in Fig. 18 superimposed on a grid formed
exclusively by 32.4.3.4 vertices (see preceding section). Note
that the grid is identical to the tiling of the sparse layers in the
3D P42/mnm phase in spherical dendrimers or metal alloys
(Fig. 8b). Similarly, the tiling pattern in the square columnar
p4mm phase (Fig. 17b,e) is the same as that of the sparse layers
in the Pm3̄n cubic phase (Fig. 8a). The pentagonal tiling
(Fig. 18a, compound IV) is the topological dual of the square-
triangle tiling in compound V (Fig. 18b). Thus, while regular
pentagons cannot tile a plane, distorted pentagons can, and
liquid crystals provide sufficient flexibility to tolerate the
necessary distortion. Consideration of possible 2D tiling
patterns82 suggests a considerable number of viable but yet
unobserved columnar phases.81
The overall structure of the LC phases in Fig. 17 is still
periodic, but their discovery raises the intriguing possibility
that a quasiperiodic columnar phase might be discovered in the
future. It is also interesting to note a recent simulation work
where a model 2D liquid crystal system showed dodecagonal
symmetry by self-assembly.83
Conclusions
The remarkable similarity of structures of liquid crystals, metal
alloys and foams underlines the universality of packing
principles across length scales. It is worth noting that, due
to their high symmetry, quasicrystals are superior to crystals
in providing a full, nearly isotropic, photonic bandgap
(PBG).84 In recent years complete PBG has been demonstrated
in artificial 2D quasicrystals with 8-, 10- and 12-fold rotational
symmetries,85–87 with potential applications in quantum
electronic devices, distributed feed-back mirrors, microwave
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antennae substrates etc. The possibility of scaling up the
characteristic length from #5 nm in the current LQC to that
of light wavelengths, as has been achieved in block copoly-
mers,88 raises the prospect of producing self-assembled
photonic quasicrystals. The discovery of supramolecular
quasicrystals also points to the possibility of finding self-
assembled quasicrystals in other liquid crystalline or colloidal
systems, including those of different dimensionalities and
symmetries.
Downloaded by UNIVERSITY OF ALABAMA AT BIRMINGHAM on 17 January 2013
Goran Ungar* and Xiangbing Zeng
Department of Engineering Materials, Sheffield University, Sheffield,
UK S1 3JD. E-mail: g.ungar@shef.ac.uk
Published on 20 April 2005 on http://pubs.rsc.org | doi:10.1039/B502443A
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