Self-Assembly of Giant Spherical Liquid-Crystalline Complexes and Formation of Nanostructured Dynamic Gels that Exhibit Self-Healing Properties

Article abstract of DOI:10.1002/anie.201707740

Supramolecular self-assembly of 24 forklike mesogenic ligands and 12 transition metal ions led to the formation of giant spherical coordination complexes that exhibit liquid-crystalline (LC) phases. Self-healing LC supramolecular gels were also obtained t

Full text of DOI:10.1002/anie.201707740

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Accepted Article
Title: Self-Assembly of Giant Spherical Liquid-Crystalline Complexes
and Formation of Nanostructured Dynamic Gels Exhibiting Self-
Healing Properties
Authors: Junya Uchida, Masafumi Yoshio, Sota Sato, Hiroyuki
Yokoyama, Makoto Fujita, and Takashi Kato
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201707740
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Self-Assembly of Giant Spherical Liquid-Crystalline Complexes
and Formation of Nanostructured Dynamic Gels Exhibiting Self-
Healing Properties
[
a]
[a]
[b,c]
[b]
[b]
Junya Uchida, Masafumi Yoshio,* Sota Sato,* Hiroyuki Yokoyama, Makoto Fujita,* and
Takashi Kato*[a]
Abstract: Supramolecular self-assembly of 24 forklike mesogenic
ligands and 12 transition metal ions leads to formation of giant
spherical coordination complexes that exhibit liquid-crystalline (LC)
phases. Self-healing LC supramolecular gels have also been
obtained by introduction of these LC nanostructured supramolecular
giant spherical complexes into dynamic covalent networks formed by
cross-linkers and bifunctional polymers. The giant spherical
structures of the Pd(II) complexes with 72 rodlike moieties on the
periphery have been characterized by NMR, diffusion-ordered NMR
spectroscopy, and mass spectrometry. These complexes are stable
and exhibit lyotropic LC behavior, while the mesogenic ligands show
thermotropic LC properties. The self-assembled LC structures of the
spherical complexes can be tuned by the length of the rodlike
moieties.
Introduction of dynamic and ordered states of liquid crystals[1]
into nonmesogenic spherical clusters has attracted much
attention[2–4] because it enables combination of the unique
properties of the isotropic spheres with the anisotropic features
of liquid crystals. Liquid-crystalline (LC) fullerenes,[2]
silsesquioxanes, and metal clusters[4] have been fabricated by
attaching mesogenic moieties to each core structure. Here, our
intention is to develop new self-assembled materials composed
of giant metal–organic spherical complexes that exhibit LC
ordered structures and self-healing properties by multivalent
modification of the spheres (Figure 1). These self-organized
spheres,[5] which are stabilized by the cooperation of multiple
interactions,[6] contain well-defined nanospaces. The hollow
spheres can be potentially used to control encapsulation and
release of guests,[7a] and for catalysis,[7b,c] drug delivery,[7d] ion
transport,[7e] and separation.[7f] We expect that introduction of
[3]
[
a]
J. Uchida, Dr. M. Yoshio, and Prof. Dr. T. Kato
Department of Chemistry and Biotechnology, School of Engineering,
The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-8656,
Japan
E-mail: kato@chiral.t.u-tokyo.ac.jp
Current address for M. Y.: Semiconductor Nano-interfaces Group,
Research Center for Functional Materials, National Institute for
Materials Science, Namiki, Tsukuba, Ibaraki 305-0044, Japan
E-mail: YOSHIO.Masafumi@nims.go.jp
[
b]
c]
Prof. Dr. S. Sato, H. Yokoyama, and Prof. Dr. M. Fujita
Department of Applied Chemistry, School of Engineering, The
University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
E-mail: mfujita@appchem.t.u-tokyo.ac.jp
[
Prof. Dr. S. Sato
WPI-AIMR, Department of Chemistry and JST ERATO, Tohoku
University, Katahira, Aoba-ku, Sendai 980-8577, Japan
Current address for S. S.: Department of Chemistry, School of
Science and JST ERATO, The University of Tokyo, Hongo, Bunkyo-
ku, Tokyo 113-0033, Japan
Figure 1. (a) Material design of LC giant spherical complex 1a assembled
from 12 Pd(II) ions and 24 mesogenic ligands of 2a. Ligand 2b also gives the
corresponding M12L24 sphere. (b) LC self-assembly of the spherical complex
E-mail: satosota@chem.s.u-tokyo.ac.jp
and its gelation through formation of a dynamic covalent polymer network.
Supporting information for this article is given via a link at the end of
the document.
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these self-organized spheres into LC order has great potential
Herein, we report giant spherical LC complexes based on
metal–organic spherical frameworks (M12L ) with a core
24
for production of anisotropically functional materials.[1g,h]
A
number of nonmesogenic functionalized spheres have been
obtained by supramolecular assembly of metal ions (M) and 1,3-
bis(4-pyridyl)benzene-based ligands (L) with the desired
moieties.[8] Thus, we envision that by incorporating mesogens
into the convex position of bis(pyridine) ligands, the periphery of
the sphere could be coated with 72 rodlike moieties and the
diameter of 3.5 nm (Figure 1a) obtained by supramolecular self-
assembly of 24 mesogenic ligands and 12 Pd(II) ions.
Nanostructured self-healing LC gels constructed by formation of
dynamic covalent bonds (Figure 1b) are also described.
Molecular design of ligands 2a and 2b is based on
attachment of mesogenic forklike dendrons through a flexible
triethylene glycol spacer at the convex position of 1,3-bis(4-
pyridyl)benzene. The mesogenic core of the dendron of 2a is a
fluoro-substituted cyclohexylbiphenyl moiety, while that of 2b is
a cyclohexylphenyl group. Both mesogens tend to show smectic
LC phases over wide temperature ranges.[
resulting M12L24 spheres could be organized into LC assembled
structures (Figure 1a). Discrete supramolecular mesomorphic
complexes were formed by directed self-assembly between
multivalent ligands and metal ions.[9] However, synthesis of LC
ordered hollow spherical molecules with rigid cores with a
diameter of a few nanometers is challenging because of
limitations in conventional synthetic chemistry. If the bottom-up
process of coordination chemistry is used to construct spherical
complexes, giant monodisperse functional LC spheres with an
inner cavity can be formed. Furthermore, use of dynamic
12]
M
12
L
24 coordination sphere 1a was obtained when ligand 2a
was treated with Pd(NO in CDCl /dimethyl sulfoxide-d
(DMSO-d
) (3:1) at 50 °C for 3 h, which was confirmed by 1H
3
)
2
3
6
6
NMR spectroscopy (Figure 2a). The significantly broadened
signals and downfield shift of the pyridine α and β protons are
indicative of formation of a very large coordination complex
(Figure 2a). Diffusion-ordered NMR spectroscopy (DOSY)
shows generation of a single species of complex 1a with a
covalent networks is
structurally dynamic and free-standing materials.
a promising approach to develop
[10]
Given the
mild reaction conditions for formation of dynamic bonds,[10] we
also aimed to incorporate LC self-organized complexes into
dynamic network structures. Combining LC molecules and
network structures leads to formation of LC gel networks, which
diffusion coefficient of 6.7 × 10−11 m s (Figure 2b). From this
diffusion coefficient, the diameter of the rigid core of 1a was
calculated to be 6.8 nm, which is larger than that of the core
framework (3.5 nm in diameter). The diameter of 1a with
peripheral mesogenic moieties was estimated to be 12 nm by
molecular modeling. This difference in the size indicates that the
flexible ethylene oxide chains are not fully extended in solution.
These NMR observations are consistent with formation of
spherical complex 1a. Similarly, the NMR results for complex 1b,
which is formed from ligand 2b, are in agreement with formation
of a spherical framework. The spherical complexes are stable for
one week in both the solid and solution states under ambient
conditions. They are also thermally stable up to about 150 °C.
Cold-spray ionization mass spectrometry (CSI-MS) was
performed to determine the molecular weights of coordination
2
−1
are emerging as new materials for
applications.[11]
a wide range of
−
n+
complexes 1a and 1b. For 1b, a series of [1b–(BF
3) peaks was observed after anion exchange from nitrate
NO
−) to tetrafluoroborate (BF −) ions. These results clearly
show that the composition of complex 1b is M12 24 with a
4
)
n
]
(n = 10–
1
(
3
4
L
molecular weight of 42772 Da. The peaks from spherical
complex 1a could not be obtained, probably because of the very
large molecular weight of 50246 Da and strong aggregation of
1a.
Ligands 2a and 2b both show smectic A LC phases over
wide temperature ranges including room temperature. The
clearing temperature of ligand 2a is much higher than that of 2b
(
2
by 46 °C), suggesting that strong intermolecular interactions of
a stabilize the LC phase. In contrast, the low glass transition
temperatures of ligands 2a and 2b are attributed to the flexible
ethylene oxide chains connected by mesogenic moieties.
Figure 2. (a) 1H NMR (500 MHz, CDCl
/DMSO-d
6
= 3:1, 300 K) spectra of
/DMSO-
3
−
salt). (b) 1H DOSY (600 MHz, CDCl
ligand 2a and complex 1a (NO
3
3
6
d = 3:1, 300 K) spectrum of complex 1a.
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Figure 4. (a) Polarizing optical micrograph of the lyotropic LC phase of
−
complex 1b in DMF (NO
3
salt). (b) SAXD pattern of the lyotropic liquid crystal
of complex 1b in DMF at 28 °C.
and 39 Å at 28 °C, which are assigned to the (001) and (002)
diffraction peaks of the smectic phase (Figure 4b). It is
interesting that the layer spacing of 1b in DMF (77 Å) is greater
than that of 1a in chloroform (64 Å), even though 1b has a
smaller molecular size. This can be explained by formation of a
nanosegregated assembly of 1b in DMF.[14]
Figure 3. (a) Schematic illustration of the LC behavior of ligand 2b and
spherical complex 1b. (b) Comparison of the size of the M12L24 spherical
complex with the sizes of fullerene C60, octasilsesquioxane, and the Mo
cluster.
6
We have designed new LC hybrid dynamic covalent network
materials incorporating spherical complexes using lyotropic
liquid crystals of spherical complexes as LC media (Figure 1b,
bottom). Dynamic covalent bonds are used to construct adaptive
materials that show responses to environmental stimuli and self-
healing.[10]
In contrast to the thermotropic LC properties of ligands 2a
and 2b, lyotropic LC behavior is induced for both giant spherical
complexes 1a and 1b (Figure 3), whose affinity with solvents is
dependent on the mesogenic structure. Dissolution of 20 mM 1a
in chloroform leads to formation of a viscous and turbid solution.
Birefringence and fluidity of the solution of spherical complex 1a
are observed with a polarizing microscope, suggesting formation
of lyotropic LC phases (see Supporting Information). For 1b, the
typical texture of smectic phases is observed in
dimethylformamide (DMF) at 23 mM 1b (Figure 4a).
Here, our new approach is to combine spherical LC M12
L
24
1b with the dynamic covalent network formed by the reaction
between aldehyde and hydrazide moieties, which provides free-
standing supramolecular LC materials exhibiting self-healing
properties. We prepared dynamic cross-linker 1c with 24
Small-angle X-ray diffraction (SAXD) measurements were
performed to elucidate the assembled structures of complexes
aldehyde groups on the surface of the sphere by supramolecular
assembly of ligand 2c and Pd2+ ions (Figure 5a). We expected
1
a and 1b. Spherical complex 1a in chloroform (20 mM 1a)
shows peaks at 64 Å and 32 Å at 28 °C, corresponding to the
001) and (002) diffractions. The interlayer distance of 64 Å is
that dynamic covalent supramolecular LC gels would form
through hybridization of 1b, 1c, and poly(ethylene glycol) (PEG)
bishydrazide 3 (Figure 5b). We mixed spherical complexes 1b,
(
about half the molecular length of 1a, which suggests formation
of an interdigitated structure in the LC state. Similar
interdigitated structures have been observed for dumbbell-
1
c, and PEG bishydrazide 3 in a mixed solvent of DMF and
DMSO. The composite exhibits a smectic phase with similar
[
13]
shaped molecules,
including our LC luminescent materials
with forklike mesogens.[12e] In contrast, the SAXD pattern of 23
mM 1b in DMF shows two peaks at 77 Å
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Acknowledgements
This work was partly supported by Grants-in-Aid for Scientific
Research (no. 22107003 for T.K. and no. 23107509 for S.S.) on
Innovative Areas for “Fusion Materials“ (area no. 2206) and
“
Stimuli-responsive Chemical Species“ (no. 15H00921 for M.Y.)
from the Ministry of Education, Culture, Sports, Science, and
Technology (MEXT). T.K. appreciates partial support by CREST,
JST (no. JPMJCR1422). J.U. is grateful for financial support
from the Japan Society for the Promotion of Science (JSPS)
Research Fellowship for Young Scientists and the JSPS
Program for Leading Graduate Schools (MERIT).
Conflict of Interest
The authors declare no conflict of interest.
Keywords: cage compounds • liquid crystals • palladium • self-
assembly • supramolecular chemistry
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6
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Angewandte Chemie International Edition
10.1002/anie.201707740
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J. Uchida, M. Yoshio,* S. Sato,* H.
Yokoyama, M. Fujita,* T. Kato*
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Self-Assembly of Giant Spherical
Liquid-Crystalline Complexes and
Formation of Nanostructured
Dynamic Gels Exhibiting Self-Healing
Properties
Giant well-defined spherical complexes decorated with 72 rodlike mesogens on the
surface of the spheres have been developed by metal complexation of 24
mesogenic ligands with 12 Pd(II) ions. The spheres self-assemble to form liquid-
crystalline smectic phases in concentrated organic solution. Nanostructured self-
healing materials are formed when the liquid-crystalline spherical complex is
introduced into a dynamic covalent network.
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