FULL PAPER

DOI: 10.1002/chem.201301538

Triblock Polyphiles through Click Chemistry: Self-Assembled Thermotropic

Cubic Phases Formed by Micellar and Monolayer Vesicular Aggregates

Xiaoping Tan,[a] Leiyang Kong,[a] Heng Dai,[a] Xiaohong Cheng,*[a] Feng Liu,*[b] and
Carsten Tschierske*[c]

Abstract: Three series of triblock poly-
philes consisting of a rigid 4-phenyl-
1,2,3-triazole or 1,4-diphenyl-1,2,3-tria-
zole core with three lipophilic and flex-
ible alkoxyl chains at one end and
a polar glycerol group at the opposite
end were synthesized by copper-cata-
lyzed azide–alkyne click reactions.
Their mesophase behavior was studied
by polarizing optical microscopy, differ-
ential scanning calorimetry, and XRD.
Depending on alkyl chain length and
core length, a transition from hexago-
nal columnar to Pm3n-type cubic
phases was observed. In the cubic
phases, the molecules are organized as
spherical objects. Remarkably, com-
pounds with a longer core unit have
a higher tendency to form these cubic
phases, and their stability is strongly
enhanced over those of the compounds
with a shorter core, despite longer
cores having a smaller cone angle and
Keywords: click chemistry · liquid
crystals · phase transitions · self-as-
sembly · triblock polyphiles
therefore being expected to disfavor
the formation of spherical objects.
There is a large difference in the
number of molecules involved in the
spherical aggregates formed by com-
pounds with long and short cores.
Whereas the aggregates in the cubic
phases of the compounds with short
rod units are small and could be re-
garded as micellar, the long-core com-
pounds form much larger aggregates
which are regarded as a kind of mono-
layer vesicular aggregate.

Introduction configurations in rugged energy landscapes.[4] In recent

The understanding of the spatial ordering of molecules into
well-defined three-dimensional structures is of relevance for
nanotechnological studies.[1] Liquid-crystalline (LC) phases,
which combine periodic order with molecular mobility, are
ideal self-assembling systems for which the fundamental re-
lations between molecular structure and supramolecular or-
ganization can be studied in a systematic way,[2, 3] as the mo-
lecular motions provide a random force on the systems de-
grees of freedom and enable them to find minimum-energy
[a] X. Tan, L. Kong, H. Dai, Prof. Dr. X. Cheng
Key Laboratory of Medicinal Chemistry for Natural Resources
Yunnan University
Kunming, Yunnan, 650091 (P. R. China)
Fax: (+ 86) 871-65032905
E-mail: xhcheng@ynu.edu.cn
[b] Prof. Dr. F. Liu
State Key Laboratory for Mechanical Behavior of Materials
Xi’an Jiaotong University
Xi’an, 710049 (P. R. China)
Fax: (+ 86) 29-82663453
E-mail: feng.liu@mail.xjtu.edu.cn
[c] Prof. Dr. C. Tschierske
Institute of Chemistry
Martin-Luther University Halle-Wittenberg
Kurt-Mothes Strasse 2, 06120 Halle/Saale (Germany)
Fax: (+ 49) 345-55-27346
E-mail: carsten.tschierske@chemie.uni-halle.de
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.201301538.
years, cubic LC phases have received considerable attention,
because of their often quite complex three-dimensional
structures.[5–8] There are two distinct types of cubic phases.
The bicontinuous cubic phases (CubV) appearing as inter-
mediate phases at the transition from lamellar to columnar
organization, which form different types of continuous inter-
woven 3D networks of channels. The other type, the so-
called discontinuous or micellar cubic phases (CubI), are
based on the self-assembly of spherical supramolecular ag-
gregates. The occurrence of these cubic phases depends
strongly on the curvature of the interfaces between microse-
gregated regions formed by the self-assembly of incompati-
ble molecular parts in different subspaces.[9] Though micellar
cubic phases are well known modes of self-assembly in lyo-
tropic systems,[10] in solvent-free thermotropic LCs, these su-
perstructures have more recently been discovered for gluca-
mide-based amphiphiles.[11] Since then, micellar cubic phases
have been found in numerous different classes of com-
pounds, most often for cone-shaped dendritic and amphi-
philic molecules,[2, 12–22] whereas for rodlike[23] and disklike
molecules[24–26] formation of micellar cubic phases has rarely
been observed. We recently reported thermotropic cubic LC
phases for the rodlike imidazolium salts Am/n with 3,4,5-tri-
alkoxybenzyl ether units and related 3,4,5-trialkoxyben-
zoates Bm/n (Scheme 1).[20] In the aggregates of these cubic
phases, the short alkyl chains at the imidazolium end form
the interior of the aggregates, which is separated by aromat-
ic shells from the continuum formed by the three chains at
the nonionic end. This leads to a kind of monolayer vesicu-

Chem. Eur. J. 2013, 19, 16303 – 16313  2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 16303
Scheme 1. Self-assembly of polycatenar imidazolium salts Am/n and
Bm/n into monolayer vesicular columnar and vesicular cubic phases. Re-
produced from reference [20a].
lar structure of the aggregates forming these cubic phases
(Scheme 1).[20]
Vesicular LC phases are a subject of current interest, and
besides the monolayer vesicular cubic phases mentioned
above, bilayer vesicular cubic phases have been reported by
Percec et al. for dendritic molecules incorporating rodlike
units and a limited number of alkyl chains at the periph-
ery.[27] Herein, we report another kind of spheroidic cubic
phases formed by a new type of nondendritic polyphiles
I3/n–III3/n, composed of a bent, rigid aromatic core with
three lipophilic alkyl chains at one end and a polar glycerol
group at the other (Scheme 2). In addition, representative
examples of compounds with a reduced number of alkyl
chains (I1/12 and II2/16 in Scheme 2) were synthesized and
investigated; however, the focus is on the three chain com-
pounds showing cubic phases.
For the synthesis of these polyphilic compounds, an ap-
proach involving copper-catalyzed azide–alkyne cycloaddi-
tion (CuAAC)[28] was used, which has widely been applied
in the fields of synthetic chemistry, biomedicine, and materi-
als science.[29] Such reactions usually proceed regioselective-
ly, give high yields in reasonable reaction times, and tolerate
a large range of functional groups. The resulting compounds
contain the 1,2,3-triazole heterocycle, which provides advan-
tageous properties, such as high chemical stability (in gener-
Abstract in Chinese:
16304 www.chemeurj.org  2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Scheme 2. Compounds under investigation.
al, inert to severe hydrolytic, oxidizing, and reducing condi-
tions even at high temperature), a large dipole moment (m =
5.2–5.6 D),[30] and electron-donor properties, lowering the
bandgap of aromatic p systems to which they are attached.
This makes them also good candidates for semiconducting
organic materials.[31] Hence, CuAAC click chemistry can not
only be used to interconnect smaller units to give larger en-
tities, but the resulting triazole ring can also act as a p-con-
jugated core structure providing desirable materials proper-
ties. A few reports on application of the CuAAC reaction
for the synthesis of rodlike,[32] disklike, star-shaped,[33] and
bent-core[34] liquid crystals have appeared quite recently.
Materials with nematic, SmA, SmC, columnar phases, and,
in one case, a bicontinuous cubic phase[33d] have been ob-
tained by this approach. Herein, we report the first use of
this synthetic method for the synthesis of polyphilic com-
pounds forming micellar and vesicular cubic phases. Three
series of compounds I–III (Scheme 2) were synthesized. All
compounds incorporate a rigid and significantly bent 1,4-dis-
ubstituted 1,2,3-triazole unit providing a bending angle of
about 1088.[32d] Series Im/n has a 4-phenyl-1,2,3-triazole core
which is connected with a substituted benzyl ether unit (m =
1: 4-alkoxybenzyl; m = 2: 3,4-dialkoxybenzyl; m = 3: 3,4,5-
trialkoxybenzyl). Series II3/n and III3/n have longer 1,4-di-
phenyl-1,2,3-triazole cores, connected with a 3,4,5-trialkoxy-
benzyl ether unit (series II3/n, X = CH2O) or a 3,4,5-trialkox-
ybenzoate unit (series III3/n, X = COO); in all cases the su-
perscript m gives the number of alkyl chains, and the
number n after the slash identifies the chain length.
Depending on the number and length of alkyl chains, hex-
agonal columnar and cubic phases with Pm3n lattice are
formed. Remarkably, the cubic phases are more dominant
for compounds II3/14 and III3/n with a longer aromatic core
than in the series I3/n, which has a shorter core. The number
of molecules organized in the spherical supramolecular ag-
gregates is much larger and more than doubled for com-
Chem. Eur. J. 2013, 19, 16303 – 16313
Triblock Polyphiles through Click Chemistry
pounds II3/14 and III3/n compared to compounds I3/n. The
aggregates in the cubic phases of compounds II3/14 and
III3/n, which contain about 120–137 molecules, have a core/
shell structure in which a polar core is surrounded by a shell
of the aromatic units, and these core/shell aggregates are or-
ganized in the continuum of the terminal alkyl chains. These
cubic phases can be considered as a kind of monolayer ve-
sicular LC phase in which the interior is filled with a differ-
ent material than the continuum outside.
Results
Synthesis: All of the target compounds were synthesized by
CuAAC between the appropriate substituted benzyl azides
9m/n or one of the larger aromatic azides (10/n or 11/n) and
the alkynyl benzene 6 carrying the acetonide-protected glyc-
erol group (Scheme 3). The 4-alkoxy-, 3,4-dialkoxy-, and
3,4,5-trialkoxybenzyl azides 9m/n were obtained by nucleo-
philic substitution of the appropriately substituted benzyl
chlorides 7m/n with sodium azide. 4-Azidophenol (1) was
synthesized from 4-aminophenol by formation of the diazo-
nium salt and subsequent substitution with sodium azide.
For the synthesis of compounds IIm/n and IIIm/n, 1 was
etherified with the corresponding 3,4,5-trialkoxybenzyl
FULL PAPER
chlorides 73/n to give the 3,4,5-trialkoxybenzyl 4-azidophenyl
ethers 10/n and acylated with the appropriate 3,4,5-trialkox-
ybenzoic acids 8/n to give the 4-azidophenyl 3,4,5-trialkoxy-
benzoates 11/n. The acetylenic building block 6, carrying the
protected glycerol unit, was synthesized from 4-iodophenol,
which was firstly etherified with allyl bromide, followed by
dihydroxylation of the double bonds with OsO4/N-methyl-
morpholine N-oxide (NMMNO).[35] Protection of the diol
groups of the obtained 1-glyceryl 4-iodophenyl ether (3)
with 2,2-dimethoxypropane produced the acetonide-protect-
ed glycerol ether 4, which was then coupled with 2-methyl-
but-3-yn-2-ol in a Sonogashira coupling reaction to intro-
duce the ethynyl group, giving compound 5. The ethynyl
group of 5 was deprotected with KOH to produce building
block 6, which was used for the CuAAC reactions with the
aryl azides 9m/n, 10/n, and 11/n to yield the acetonide-pro-
tected intermediates 12m/n, 13 a/n, and 13 b/n, respectively.
In the final step, the acetonide groups were cleaved (HCl in
CH3OH) and the obtained target polyphiles Im/n, II3/14, and
III3/n were purified by column chromatography. Detailed
synthetic procedures and analytical data are given in the
Supporting Information.
Investigations: The properties of the synthesized polyphiles
were studied by polarizing optical microscopy (POM, Nikon

Scheme 3. Synthesis of compounds I1/n–I3/n, II3/n, and III3/n: Reagents and conditions: i) a) NaNO2/HCl, H2O, 0 8C; b) NaN3, 0–5 8C, 5 h, 76 %; ii) K2CO3,
CH3CN, allyl bromide, reflux, 6 h, 96 %; iii) OsO4, NMMNO, H2O, acetone, 45 8C, 10 h, 80 %; iv) 2,2-dimethoxypropane, pyridinium p-toluenesulfonate,
25 8C, 12 h, 86 %; v) 2-methylbut-3-yne-2-ol, [PdACHTUNGRE(PPh3)4], CuI, THF, Et3N, 25 8C, 15 h, 93 %; vi) KOH, toluene, reflux, 5 h, 83 %; vii) KI, NaN3, DMF,
25 8C, 6 h, 93–99 %; viii) K2CO3, DMF, reflux, 10 h, 60 %; ix) dicyclohexylcarbodiimide, 4-dimethylaminopyridine, CH2Cl2, 0–5 8C, 18 h, 76–84 %; x) CuI,
NEt3, toluene, 25 8C, 12 h, 51–67 %; xi) tert-Butyl alcohol, H2O, THF, CuSO4·5 H2O, sodium ascorbate, 25 8C, 20 h, 75–82 %; xii) 10 % HCl, methanol,
reflux, 2 h, 80–95 %.

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 X. Cheng, F. Liu, C. Tschierske et al.

Optiphot 2 in conjunction with Table 1. Phase transitions of compounds I–III (see Scheme 2).[a]
a Mettler FP 82 HT heating Comp T [8C] [DH [kJ mol1]] Tcr [8C]
stage), differential scanning cal- 1
I /12 Cr 79 [31.3] Iso –[d]
orimetry (DSC, Netzsch I2/16 Cr 127 [77.3] Colhex 147 [1.0] Iso 104
DSC200F3), and X-ray diffrac- I3/6 Cr 92 [24.3] (Colhex 81 [0.8]) Iso –[d]
I3/8 Cr 97 [15.0] Colhex 103 [1.0] Iso 33
tion (XRD) of powder samples.
I3/10 Cr 85 [42.4] Colhex 111 [1.0] Iso 37
For selected compounds, a syn- I3/12 Cr 86 [42.1] Colhex 103 [0.2] CubI/Pm 3n 113 [0.2] Iso 51
chrotron X-ray source was used I3/14 Cr 63 [32.3] Colh 80 [0.7] CubI/Pm 3n 124 [< 0.1] Iso[b] 39
for the investigation of the I3/16 Cr 61 [41.4] Colhex 69 [2.0] CubI/Pm 3n 134 [0.3] Iso 55
powder samples (beamline II3/14 Cr 67 [23.2] CubSph/Pm 3n 181 [0.2] Iso 53
III3/10 Cr 141 [39.2] Colh 177 [0.6] Iso –[d]
BL16B1 at Shanghai Synchro- III3/12 Cr1 114 [14.6] Cr2 123 [10.3] (Colh 91 [0.3])[c] CubSph/Pm
3n 176 [0.2] Iso 55
tron Radiation Facility, SSRF) III3/14 Cr 128 [45.2] CubSph/Pm 3n 184 [0.3] Iso 94
at a wavelength of 1.2 . The III3/16 Cr 117 [20.9] CubSph/Pm 3n 168 [0.1] Iso 72
transition temperatures of the [a] Transition temperatures were determined by DSC (10 K min1) and confirmed by POM; peak temperatures
synthesized polyphiles are col- from the first heating scan are given; values in brackets are transitions on cooling; abbreviations: Cr = crystal-
lected in Table 1. line solid, Iso = isotropic liquid; Colh/Colhex = hexagonal columnar phases (Colhex = hexagonal lattice confirmed
by XRD, Colh = hexagonal symmetry deduced from optical properties and textures); CubI/Pm 3n = micellar
cubic mesophase with space group Pm 3n; CubSph/Pm 3n = spheroidic cubic mesophase with space group Pm3n
Series I: hexagonal columnar (compared to CubI phases the aggregates are significantly larger; the aggregates have a core/shell structure,
phases: Compounds in series I and the material in the core is different from the material forming the continuum); Tcr = crystallization temper-
have a relatively short rigid ature (10 K min1). [b] Transition temperature determined by POM. [c] Colh–Cub transition was taken from
core and a methylene linking the cooling scan. [d] No crystallization observed down to 25 8C.

group connecting the alkoxy-

substituted end group with the
triazole unit (Scheme 1). Whereas the single chain com- Table 2. Comparison of XRD data, lattice parameters, and other data[a]
pound I1/12 does not show any LC phase, a hexagonal col- for compounds Im/n, II3/14, and III3/n (see Scheme 2) and related imida-
zolium salts A4/14 and B2/12 for comparison (see compounds Am/n and
umnar phase was observed for the two-chain compound
Bm/n shown in Scheme 1; here m, n indicate the chain lengths).[20]
I2/16, with lattice parameter ahex = 4.84 nm (at T = 130 8C,
Comp. Phase, Plane/space group L [nm] a [nm] (T [8C]) n a [8]
Table 2; Table S1 and Figure S4a in the Supporting Informa-
tion). I2/16 Colhex/p6mm 4.1 4.84 (130) 6.7 53.7
I3/6 Colhex/p6mm 2.8 4.16 (80) 6.8 52.9
Columnar phases were found for all compounds I3/n with I3/8 Colhex/p6mm 3.1 4.31 (100) 6.3 57.1
three alkoxyl chains. The textures of the columnar meso- I3/10 Colhex/p6mm 3.3 4.54 (80) 6.1 59.0
phases, as observed by POM, are characterized by typical I3/12 Colhex/p6mm 3.6 4.68(90) 5.7 63.1
spherulitic domains, as shown in Figure 1 for compound I3/12 CubI/Pm 3n 8.99ACHTUNGRE(110) 61.0 5.9
I3/16 Colhex/p6mm 4.1 5.32 (60) 6.3 57.1
I3/12 as an example (for additional examples, see also Fig-
I3/16 CubI/Pm 3n 9.55 (110) 60.0 6.0
ure S2a–f in the Supporting Information). These columnar II3/14 CubSph/Pm 3n 4.2 12.19 (150) 127.2 2.8
phases are optically uniaxial, as indicated by the completely III3/12 CubSph/Pm 3n 4.0 12.10 (150) 137.3 2.6
dark appearance of regions with homeotropic alignment of III3/14 CubSph/Pm 3n 4.2 12.18 (150) 126.8 2.8
III3/16 CubSph/Pm 3n 4.5 12.33 (130) 120.2 3.0
A4/14 Colhex/p6mm 4.0 4.9 (120) 5.5 65.5
B2/14 CubVes/Pm3n 3.7 10.4 (150) 85 4.24
[a] L = maximum molecular length in the most extended conformation
with all-trans conformation of the alkyl chains and measured between the
end of the 4-alkyl chain and the primary OH group of the glycerol unit;
a = lattice parameter; n = number of molecules in the cross section of
a column in the Colhex phases (with assumed height of 0.45 nm) or
number of molecules in each aggregate of the cubic/Pm 3n lattice (ncell/8);
a = projection of the cone angle, calculated according to a = 360/n;[38] ab-
breviations: CubVes/Pm3n = vesicular cubic phase with space group Pm3n;
for other abbreviations, see Table 1.

the columns (columns perpendicular to the glass substrates,

Figure 1. Typical texture (crossed polarizers, directions of the polarizers
are vertical and horizontal) of the Colhex phase of compound I3/12 at
102 8C. For a figure showing the same region with l-retarder plate, see
Figure S1 in the Supporting Information.
see Figure S2b in the Supporting Information) and they are
optically negative, as indicated by investigation with a l-re-
tarder plate (Figure S1b in the Supporting Information).
This means that in the columns the preferred direction of
the intramolecular p-conjugation pathway (i.e., the long axis
of the aromatic cores) is on average perpendicular to the
column long axis.

16306 www.chemeurj.org  2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eur. J. 2013, 19, 16303 – 16313
Triblock Polyphiles through Click Chemistry
Figure 2. a) DSC heating and cooling curves of I3/16 (10 K min1); the
inset shows an enlargement of the DSC peaks corresponding to the
CubI–Iso and Iso–CubI transitions. b, c) SAXS diffractograms of the
Colhex phase at 60 8C (b) and the CubI/Pm
3n phase at 110 8C (c).
High-resolution small-angle powder diffraction experi-
ments were carried out for most of the compounds and are
described here for compound I3/16 as an example (see Fig-
ure 2 b and c, Table 2, and Tables S2 and S3 in the Support-
ing Information). In the temperature range of the columnar
phase there are three small angle reflections with a ratio of
1
reciprocal spacings of 1:3 = :2, which can be indexed to the
2
10, 11, and 20 reflections of a hexagonal lattice (Figure 2 b)
with ahex = 5.32 nm (at T = 60 8C). For the hexagonal phase
of compounds I3/n, the lattice parameter increases from
4.16 nm for n = 6 to 5.32 nm for n = 16 (Table 2 and Ta-
Chem. Eur. J. 2013, 19, 16303 – 16313  2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
FULL PAPER
bles S1 and S2 in the Supporting Information). The number
of molecules n organized in a stratum of the columns with
a height of h = 0.45 nm was estimated by using Equation (1)
and assuming a density of 1 = 1 g cm3 (NA = Avogadro con-
stant, M = molecular mass) to be about n = 6 for compound
I3/16. Similar values of n = 6–7 were found for the other in-
vestigated Colhex phases occurring in series I (see Table 2
and Table S8 in the Supporting Information).
2 pffiffiffi
n ¼ ða 2Þ 3hðNA =MÞ1 ð1Þ
The columns show rosettelike packing (Figure 3 a) or
packing in bilayer ribbons (Figure 3 b) with time- and space-
averaged random orientation of the ribbons. It must also be
Figure 3. Models showing the organization of compounds I3/n in the hex-
agonal columnar LC phases. Schematic sketches of a rosette (a) and
a ribbon (b) formed by six molecules in the cross section. c) Hexagonal
lattice formed by the resulting columns.
considered that the strong bend of the rigid units, due to the
presence of the triazole ring, could possibly favor a more
disordered packing of these units. The diameter of the glyc-
erol column core was determined with molecular models to
be about 1.5 nm, which corresponds to the diameter of the
red/yellow high-electron density regions in the electron-den-
sity map of the Colhex phase of I3/16 (Figure 4 a). The length
of the molecular core, including the aromatics and the glyc-
erol units, is 1.7–1.9 nm for compounds I3/n, which is in
good agreement with the diameter of the regions of medium
electron density, shown in green, which have a diameter of
about 3.4 nm. These diameters also agree with the sizes of
the polar (yellow) and aromatic (blue) circles in the molecu-
lar dynamics (MD) annealed model in Figure 4 b. The alkyl
chains are completely disordered and interdigitated in the
continuum of low electron density around these columns.
Series I3/n: transition from columnar to micellar cubic
phases: The short homologues I3/n with n = 6–10 form exclu-
sively the columnar phase in the whole mesomorphic tem-
perature range (Table 1 and Figure S4 in the Supporting In-
formation), whereas additional optically isotropic phases
www.chemeurj.org 16307

with cubic lattice were found for higher homologues I3/n
with n = 12–16 (Figure 2). In all cases the cubic phase is the
high-temperature phase above the columnar phase
(Table 1). Hence, on chain elongation or increasing the tem-
perature a transition from a columnar to a cubic phase takes
place. As the curvature of the aromatic/aliphatic interface is
also expected to increase with increasing temperature or
alkyl chain length in the above-mentioned order, the cubic
phases of these compounds are expected to be micellar
cubic phases (CubI).[11, 12]
In the cubic phase of compound I3/16 the positions of the
sharp powderlike reflections in the small-angle region can
be indexed to be a cubic phase with space group Pm3n and
lattice parameter acub = 9.55 nm (see Figure 2 c, Table 2, and
Table S3 in the Supporting Information). The Pm3n lattice
is the most commonly observed lattice for micellar cubic
phases occurring in systems formed by spheroidic aggregates
with soft corona.[14, 36] In this type of cubic phases the mole-
cules are organized in closed spheroidic aggregates, and
there are eight of these aggregates in each unit cell (see Fig-
ure 4 d). On the basis of the size of the unit cell and the mo-
lecular volume (determined by using crystal-volume incre-
ments[37]), it was calculated that for compound I3/16 each of
the eight micelles is on average formed by approximately 60
molecules. A comparable value was obtained for the CubI/
Pm 3n phase of the shorter homologue I3/12 (Table 2).
Compounds II3/14 and III3/n: cubic phases composed of
large spherical objects: Compound II3/14 has an elongated
1,4-diphenyl-1,2,3-triazole core and a flexible benzyl ether
linkage connecting this core with the taper-shaped unit. This
compound forms exclusively a cubic mesophase with signifi-
cantly enhanced stability compared to compound I3/14 with
a shorter 4-phenyl-1,2,3-triazole core. Although the clearing
temperature is strongly increased to 181 8C by core elonga-
tion, the melting point of compound II3/14 is only slightly
enhanced (Tm = 67 8C, see Table 1). This leads to the broad-
est cubic phase range (114 K) among the compounds report-
ed herein. It is surprising that a molecule with such an ex-
tended core, and hence small cone angle (a = 2.88),[38] can
still form a cubic phase, and that the cubic phase formed by
this compound (TCub–Iso = 181 8C) is even more stable than
that of I3/14 (TCub–Iso = 124 8C) with a much shorter core unit
and hence much larger cone angle (a  68 for the CubI
phases of compounds I3/n). It is especially notable that core
elongation leads to complete suppression of the columnar
phase of I3/14; no transition to a columnar phase was ob-
served for compound II3/14 on cooling to 53 8C, at which
crystallization occurs (see Figure S3a in the Supporting In-
formation). XRD investigations confirm a Pm3n-type cubic
phase with a calculated lattice parameter of acub = 12.19 nm,
and each spherical object is formed by approximately 127
molecules (Table 2, Table S4 and Figure S5a in the Support-
ing Information). This number is more than twice that ob-
served for the micellar aggregates of the cubic phase of I3/16
(60 molecules).
16308 www.chemeurj.org  2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
X. Cheng, F. Liu, C. Tschierske et al.
Compounds in series III3/n have the same fundamental
structure as II3/14, but the benzyl ether group (X = CH2O) is
replaced by the more polar and also more rigid carboxyl
group (X = COO). All compounds III3/n also have signifi-
cantly enhanced mesophase stability compared to com-
pounds I3/n with a shorter core unit. The effect of the link-
ing group X on mesophase stability appears to be only mar-
ginal, though the melting temperatures are significantly en-
hanced for the ester compounds (cf. II3/14 and III3/14 in
Table 1). Compound III3/10 with the shortest chains (Fig-
ure S2g in the Supporting Information) shows a hexagonal
columnar phase; compound III3/12 has a columnar/cubic di-
morphism with a monotropic columnar phase occurring
below 92 8C (see Figure S3b in the Supporting Information),
and the higher homologues with n = 14 and 16 show only
cubic phases in the whole observable temperature region
(see Table 1). Also for these cubic phases a Pm3n lattice
was confirmed by XRD (see Table 2, Figure 4 c and Ta-
bles S5–S7 and Figure S5b,c in the Supporting Information).
Using the diffraction intensities from the powder SAXS pat-
tern (Figure 4 c and Table S7 in the Supporting Information),
we reconstructed the 3D electron-density map for the cubic
phase of compound III3/16 (Figure 4 d). The isoelectron sur-
face is set at the level at which, according to the volume
fraction versus electron-density histogram (see Figure S6 in
the Supporting Information), the volume fraction enclosed
within the high-density spheres is 0.07, that is, the calculated
volume fraction of the polar end of compound III3/16. This
means that the predominantly polar ends are located within
the spherical objects (high electron density, red/yellow in
Figure 4 d), while the continuum outside the spheres is
mainly aliphatic (low electron density, blue). The calculated
lattice parameter increases from acub = 12.1 nm for III3/12 to
acub = 12.3 nm for III3/16, and the number of molecules per
aggregate is also unusually large and decreases slightly with
growing alkyl chain length from n = 137 for III3/12 to n =
120 for III3/16 (see Table 2). This chain-length effect on ag-
gregate size is in line with the slight increase of the cone
angle on chain elongation; larger cone angles lead to a small-
er number of molecules organized in the aggregates. The
cubic phases of compounds II and III, formed by larger
spherical aggregates, are assigned as CubSph and will be dis-
cussed in more detail in the following section.
Discussion
Comparison of compounds II3/14 and III3/n with other elon-
gated rigid molecules forming cubic LC phases: It was
shown herein that polyphilic polycatenar molecules
I3/n–III3/n with relatively long and bent rigid core units can
form broad regions of cubic phases composed of spherical
objects. Especially for II3/14 and the compounds of series
III3/n, this was unexpected, as the large distance between
the alkyl substituted end and the polar glycerol group gives
rise to a rather small projection cone angle (a = 2.6–3.08, see
Table 2). This small cone angle and the presence of a rela-
Chem. Eur. J. 2013, 19, 16303 – 16313
Triblock Polyphiles through Click Chemistry
Figure 4. a) Reconstructed electron-density map of the Colhex phase of
I3/16 and b) snapshot of the structure of (a) after MD annealing simula-
tions (polar ends are colored red and bent aromatic cores green). The
yellow and blue circles represent the boundaries between high–medium
and medium–low electron density regions, respectively. c) SAXS diffrac-
togram of the CubSph/Pm 3n phase of compound III3/16. d) Reconstructed
electron-density map of the CubSph/Pm 3n phase (see Table S7 in the Sup-
porting Information). The isoelectron surface level is set so as to divide
the space in the ratio 0.07 (high-density polar fraction within the spheres)
to 0.93 (aromatic and aliphatic fractions outside the spheres).
Chem. Eur. J. 2013, 19, 16303 – 16313  2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
FULL PAPER
Figure 5. Collection of LC molecules combining an extended aromatic
core unit with a 3,4,5-trialkoxy-substituted end (CubV = bicontinuous
cubic phase; Lam = lamellar soft crystalline phase).[21, 39–41, 43, 44]
tively long core unit are usually expected to favor the for-
mation of lamellar, modulated smectic phases (ribbon
phases) or bicontinuous cubic phases with reduced interfa-
cial curvature, as known from the investigation of rodlike
polycatenar mesogens having three alkyl chains at one end
and only one or no alkyl chain at the other.[39] Figure 5
shows a selection of such structurally related compounds in-
corporating an extended aromatic core, three alkyl chains at
one end, and different types of substituents with different
polarity at the opposite end.[21, 39–41, 43, 44] In polycatenar com-
pounds like C with alkyl chains at both ends, three at one
and only one at the other, the antiparallel packing of the
molecules is preferred for steric reasons, and the presence of
identical chains at both ends additionally favors antiparallel
organization. In this way the interfacial curvature is mini-
mized and layers can still be formed, but there is an excess
interfacial area for the mixed alkyl chains over the aromat-
ics, which leads to layer curvature with formation of bicon-
tinuous cubic phases or ribbonlike aggregates.[39] If the
single chain at one end is partly or completely removed and
replaced by a single OH group (e.g., compounds D and E),
the bicontinuous cubic phases are retained.[40, 41] However, if
this chain is replaced by a much stronger polar group, as in
the phosphonic acid G[43] and the sulfonium salt H,[44] then
segregation of these strongly polar groups from the rodlike
aromatic units and the aliphatic chains inhibits the antiparal-
lel intercalation of these cores and leads to a preferred par-
www.chemeurj.org 16309
 X. Cheng, F. Liu, C. Tschierske et al.

allel side-by-side packing of the molecules with the polar

groups at the apex assembled exclusively in the centers of
the resulting aggregates. This gives rise to stronger interfa-
cial curvature between aliphatic chains and core region, and
leads to the formation of hexagonal columnar phases. Only
for compound F[21] with a hydrogen-bonding imidazole
group at the apex and for the long-chain compounds I3/n,
II3/n, and III3/n (with n = 12–16) reported herein, having
glycerol groups at the apex, were spheroidic cubic phases
observed. It appears that hydrogen-bonding groups at the
apex, providing medium polarity, are favorable for forma-
tion of this type of cubic phase.

Micellar versus vesicular cubic phases: Hexagonal columnar

and Pm 3n cubic phases were also reported for the imidazoli-
um salts Am/n and Bm/n (see Scheme 1 and compounds
A4/14 and B2/14 in Table 2).[20] These molecules have alkyl
chains at both ends, one at the imidazolium unit (m) and
three at the end (n), similar to the tetracatenar compound
C, but the core unit is amphiphilic. In this case, the polar–
apolar segregation along the core can favor parallel side-by-
side packing of the cores and segregation of short and long
alkyl chains. In this way the bulky ends are forced to organ-
ize side by side, and this leads to strong interfacial curva-
ture, giving rise to the formation of hexagonal columnar and
Pm 3n cubic phases, very similar to those formed by other
taper-shaped and conical molecules[9, 11, 12] or dendrimers with
a polar apex.[2] However, for compounds Am/n and Bm/n, in
the resulting structures, some alkyl chains are enclosed in Figure 6. Development of columnar and cubic mesophase structures of
the interior of the aggregates, and these chains are separated compounds I3/n–III3/n (with n = 12–16) depending on the length of the ar-
by the aromatic shells from the continuum formed by the omatic core.

majority of chains (Scheme 1). As the interior inside the ag-

gregates is identical with the material surrounding the ag-
gregates, these aggregates have some similarity to monolay-
er vesicles formed by bolaamphiphiles in aqueous systems[45]
and therefore are assigned here as vesicular cubic phases
(CubVes). In the spherical aggregates of compounds II3/n and
III3/n, the polar glycerol groups replace the short alkyl
chains inside the vesicular aggregates of compounds Am/n
and Bm/n (Scheme 1), and hence stabilize the aggregates by
segregation of these polar groups from the apolar alkyl
chains, that is, the chain amphiphilicity (RH versus glycerol)
replaces the core amphiphilicity. In the resulting aggregates,
the material in the interior is different from the material in
the outside continuum (Figure 6).
There is a considerable difference in the size of the spher-
ical aggregates in the cubic phases of compounds I3/n (  60
molecules per aggregate) compared to about 120–137 mole-
cules per aggregate for compounds II3/14 and III3/n (see
Table 2). Considering the number of molecules per sphere
in the cubic phases of compounds II3/14 and III3/n, the
volume of the glycerol groups amounts to around 14 nm3, as
calculated with crystal-volume increments.[37] This value cor-
responds to a diameter of the spherical aggregate cores of
between 2.9 and 3.0 nm for the investigated compounds. In
the electron-density map shown in Figure 4 d, this value cor-
responds approximately to the diameter of the yellow
spheres covering the region of high electron density (red/
yellow). For complete filling of the centers with the glycerol
groups, molecular fluctuations are required, which may be
supported by the presence of the polar triazole ring in the
core unit. The triazole units of some of the molecules can
temporarily be incorporated into the hydrogen-bonding net-
works of the glycerol groups. These fluctuations could con-
tribute to the softness of these spheres, and this is favorable
for organization in a Pm3n lattice instead of any other cubic
lattice type.[14, 36] In these cubic phases the aromatic cores
form a distinct shell separating the polar cores from the lip-
ophilic outside continuum, which makes these aggregates
different from the usual micellar structures which are small-
er and do not have a core/shell structure.
Whereas the LC phases reported here can be considered
as vesicular monolayer structures, Percec et al. reported ve-
sicular LC phases formed by the spatial organization of
curved bilayers. These bilayer vesicular phases can form
even larger spherical aggregates incorporating from several
hundreds up to a thousand molecules.[27b] This type of vesic-
ular phase was already proposed by Luzzati, Skoulios, and
Mustacchi in 1958 for lyotropic hexagonal columnar phases
with unusually large lattice parameters, formed by aqueous
soaps and assigned as complex hexagonal phases.[46] More

16310 www.chemeurj.org  2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eur. J. 2013, 19, 16303 – 16313
Triblock Polyphiles through Click Chemistry
recently, columnar and cubic vesicular LC phases were also
reported by Watanabe et al. for some bent-core mole-
cules.[47] Overall, it appears that there is a whole series of
mesophases with a vesicle-like structure for which a variety
of distinct phase structures could be expected and which are
obviously found in quite different classes of compounds. In
addition, there is a relatively broad diversity of different
possible phase structures; besides monolayer and bilayer
structures, there is the possibility that aggregate cores and
continuum are identical or different and the difference
could be based on a polar/apolar incompatibility[48] or any
other mode of incompatibility, such as RF/RH.[49, 50]
Hence, the cubic phases composed of spherical objects
can be classified into micellar cubic phases assigned as CubI,
vesicular cubic phases assigned as CubVes, and an intermedi-
ate type assigned as CubSph. CubVes phases are core/shell
structures having the same material in the interior of the
spheres as in the continuum, whereas cubic phases formed
by core/shell spheres and having different material in con-
tinuum and interior are assigned here as CubSph phases.
Effects of core structure on aggregate size and micelle-vesi-
cle transitions: The question arises why a distinct jump in
the size of spherical aggregates in the cubic phases was ob-
served on core elongation from compounds I3/n to II3/14
and III3/n (with n = 12–16). It is known that the molecular
shape, especially the cone angle a, of amphiphiles[10, 11, 12] and
dendrimers[38] determines the interfacial curvature and
hence the sphere size, whereby a decreasing cone angle
leads to decreasing curvature and increasing size. However,
with increasing sphere size a packing problem arises in the
center, as the space there cannot be filled completely. Usual-
ly this is avoided by a transition to other aggregate types
with reduced interfacial curvature, leading to the phase se-
quence CubI–Colhex–CubV–Sm on decreasing the cone angle.
This is the usually observed behavior in lyotropic systems[10]
and for the thermotropic phase sequences of solvent-free
binary amphiphiles.[11, 12] Remarkably, on reducing the cone
angle from compounds I3/n to compounds II3/14 and III3/n
(n = 12–16), this transition does not take place and a spheri-
cal shape of the aggregates is retained; only the size of the
spheres is increased. It appears that the formation of large
spherical aggregates is favored by the extended aromatic
cores, which are a third incompatible unit and hence lead to
polyphilic (triphilic) molecules.[3, 9] The three covalently con-
nected units not only have distinct cohesive energy densities,
but also provide distinct conformations, shapes, and mobili-
ty. A possible explanation for the preferred formation of
larger vesiclelike spheres could be that the vesicular struc-
tures allow increased chain disorder compared to alternative
modes of self-assembly, such as columns and lamellae. This
provides an entropic advantage, as enhanced conformational
chain disorder increases the entropy stored in the chain re-
gions.[42] The entropy reservoir provided by the disordered
chains (at both ends) becomes more important if rigid units
are involved in the molecular structure which have less de-
grees of conformational freedom and therefore can store
Chem. Eur. J. 2013, 19, 16303 – 16313  2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
FULL PAPER
less entropy. Hence, larger rodlike cores require more chain
flexibility and therefore increase the tendency to form vesic-
ular aggregates. As this entropy term is in competition with
the energy term requiring minimization of the interfacial
areas, the importance of the entropic term grows as the
energy term becomes smaller, that is, as the chemical incom-
patibility, and hence the strength of segregation, is reduced.
Therefore, a relatively weak amphiphilicity appears to be fa-
vorable for formation of vesicular aggregates.[27] For the
compounds reported herein, the possibility of hydrogen
bonding with the triazole unit may reduce the incompatibili-
ty between aromatic core and polar glycerol groups to some
extent. In this way the triazole units also allow molecular
fluctuations required to completely fill the polar interior of
the large spheroidic aggregates. Alternatively, in other cases,
as for dendritic and rod-coil compounds a certain number of
molecules can adopt a reversed orientation to optimize
space filling.[27, 51] In the case of dendritic compounds an in-
creasing number of reversed molecules can lead to bilayer-
like structures, which further reduce the interfacial curva-
ture and ultimately give rise to giant bilayer-type vesicular
aggregates.[27]
Besides the problem of filling the centers, larger aggre-
gates must also deviate from an ideal spherical shape and
adapt to the actual shape of the interface; for spherical ag-
gregates, this is the minimum-energy Weaire–Phelan froth,
leading to the Pm3n lattice.[36] Hence, there are complex
regulatory networks which determine the resulting energy
and entropy landscapes and the precise mode of soft self-as-
sembly.
Conclusion
The combination of amphiphilicity with distinct molecular
shapes and topologies leads to new modes of LC self assem-
bly which are more complex than the simple and well-estab-
lished sequence SmA–CubV–Col–CubI.[9] Previous examples
were provided by T-shaped and X-shaped molecules with
laterally attached alkyl chains forming honeycomb LC
phases.[3] This work has shown that for end-branched mole-
cules with a linear or slightly bent shape, a transition from
micellar to a kind of vesicular self-assembly in CubSph
phases takes place on core elongation from compounds I3/n
to II3/14 and III3/n (n = 12–16, see Figure 6). There are rela-
tions with other vesicular modes of self-assembly, reported
for dendritic molecules (bilayer type)[27] and polycatenar
imidazolium salts (monolayer type).[20] Though a number of
questions still remains open, this work contributes to the un-
derstanding of the nontrivial relation between self-assembly
and molecular structure in the fluid LC phases of different
types of polyphilic molecules, focusing on the transition be-
tween micellar and distinct types of vesicular structures of
spheroidic self-assembled units.
www.chemeurj.org 16311

Experimental Section
For synthesis, analytical data, and additional X-ray data, see the Support-
ing Information.
Acknowledgements
This work was supported by the National Natural Science Foundation of
China (No. 21274119, 21074105 and 20973133), the Yunnan Science
Foundation (2013A007 and 2010CD018) and the DFG (FG 1145). We
thank Prof. Yumei Zhang at the College of Materials Science and Engi-
neering, Donghua University, China, for allowing use of their Material
Studio (Accelrys Inc.). For help with the synchrotron experiments, we
also thank Dr. Xiuhong Li and Dr. Feng Tian (beamline BL16B1) at
Shanghai Synchrotron Radiation Facility (SSRF), China.
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Received: April 22, 2013
Revised: August 4, 2013
Published online: October 14, 2013
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