Liquid Crystalline Bolaamphiphiles
A R T I C L E S
phiphilic self-organization with the organizing forces provided
by rigid (in most cases rodlike) segments is another route to novel
mesophase morphologies. One of the first important steps in
this direction was done with polycatenar molecules (rodlike
molecules with more than one chain at each terminus), where
the parallel organization of extended linear rigid cores is in
competition with the space filling of the alkyl chains attached
to the ends.16 Rod-coil molecules17 and molecules incorporating
bulky oligosiloxane18 or perfluoroalkyl segments19-21 also
follow this design strategy. Polyphilic molecules, supermol-
ecules, and dendrimers incorporating rodlike segments were
found to organize into ABC-triple layer and “onion-like”
superstructures.18,19,22 In these polyphilic molecules the organiz-
ing forces provided by the rigid segments are in line with the
Figure 1. General phase sequence of conventional amphiphiles with respect
to the increasing volume fraction of one of the incompatible parts.
two different molecular parts usually change their organization
depending on the volume fractions of the two incompatible parts.
Thereby, starting from layer structures (smectic phases) for
nearly equal volume fractions, the mesophase morphology
changes at first to columnar phases and then to mesophases
composed of spheroidic aggregates with increasing volume frac-
tion of one of the parts (see Figure 1).7-11 Additionally, bicontin-
uous cubic phases (CubV) and perforated layer structures were
observed as intermediate phases at the transition from lamellar
to columnar organization.7,9,10 However, the number of possible
structures which can be realized with these binary amphiphiles
is limited mainly to these rather simple morphologies.
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Mesophase morphologies with higher levels of complexity
can be achieved with polyphilic (macro)molecules, combining
more than two incompatible units, as successfully demonstrated
for ABC-triblock copolymers.7,12-15 The combination of am-
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Liq. Cryst. 1991, 10, 389-396. (b) Doi, T.; Sakurai, Y.; Tamatani, A.;
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(14) Selected examples of complex morphologies in linear ABC triblock
copolymers: (a) Mogi, Y.; Nomura, M.; Kotsuji, H.; Ohnishi, K.;
Matsushita Y.; Noda, I. Macromolecules 1994, 27, 6755-6760. (b)
Matsushita, Y.; Tamura M.; Noda, I. Macromolecules 1994, 27, 3680-
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Macromol. Chem. Phys. 1997, 198, 1051-1083. (e) Breiner, U.; Krappe
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(15) Examples of complex morphologies in ABC heteroarm star terpolymers:
(a) Sioula, S.; Hadjichristidis N.; Thomas, E. L. Macromolecules 1998,
31, 8429-8432. (b) Hu¨cksta¨dt, H.; Go¨pfert A.; Abetz, V. Macromol. Chem.
Phys. 2000, 201, 296-307. (c) Yamauchi, K.; Takahashi, K.; Hasegawa,
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(20) Disklike mesogens with perfluorinated chains: (a) Dahn, U.; Erdelen, C.;
Ringsdorf, H.; Festag, R.; Wendorff, J. H.; Heiney, P. A.; Maliszewskyj,
N. C. Liq. Cryst. 1995, 19, 759-764. (b) Terasawa, N.; Monobe, H.;
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(21) Examples of taper-shaped and dendritic LC with perfluorinated chains: (a)
Johanssson, G. J.; Percec, V.; Ungar, G.; Zhau, J. P. Macromolecules 1996,
29, 646-660. (b) Percec, V.; Johansson, G.; Ungar, G.; J. Zhou, J. Am.
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(d) Pegenau, A.; Cheng, X. H.; Tschierske, C.; Go¨ring, P.; Diele, S. Angew.
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H. Nature 2002, 419, 384-387. (f) Cheng, X.; Das, M. K.; Diele, S.;
Tschierske, C. Langmuir 2002, 18, 6521-6529. (g) Percec, V.; Glodde,
M.; Johannsson, G.; Balagurusamy, V. S. K.; Heiney, P. A. Angew. Chem.
Int. Ed. 2003, 42, 4338-4342.
(22) (a) Gehringer, L.; Bourgogne, C.; Guillon, D.; Donnio, B. J. Am. Chem.
Soc. 2004, 126, 3856-3867. (b) Marcos, M.; Omenat, A.; Serrano, J. L.
C. R. Chim. 2003, 6, 947-957.
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