Anion modules: Building blocks of supramolecular assemblies by combination with π-conjugated anion receptors

Article abstract of DOI:10.1021/ja203880d

Dipyrrolyldiketone boron complexes, as π-conjugated acyclic anion receptors, act as building subunits of various assemblies through noncovalent interactions in the form of receptor-anion complexes. Instead of, or in addition to, the modification of receptor structures, the introduction of anion modules as building blocks for the assemblies was found to be useful in forming various soft materials. Gallic carboxylate derivatives 3-n (n = 16, 18, 20), as tetrabutylammonium (TBA) salts, form receptor-anion-module complexes that can be used to fabricate supramolecular assemblies. Combinations of aliphatic anion modules 3-n and receptors 1a,b along with a TBA cation afforded products with mesophases, which were indicated by differential scanning calorimetry and polarized optical microscopy. X-ray diffraction measurements of the solid states and mesophases of 1a?3-n?TBA and 1b?3-n?TBA revealed highly ordered structures including lamellar structures, which could be modulated by the lengths of the alkyl chains of the modules. Functional materials exhibiting electrical conductivity were fabricated by using combinations of anionic building blocks that form assemblies by themselves and π-conjugated acyclic receptors.

Full text of DOI:10.1021/ja203880d

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pubs.acs.org/JACS
Anion Modules: Building Blocks of Supramolecular Assemblies by
Combination with π-Conjugated Anion Receptors
Hiromitsu Maeda,*,† Kazumasa Naritani,† Yoshihito Honsho,‡ and Shu Seki‡,§
†College of Pharmaceutical Sciences, Institute of Science and Engineering, Ritsumeikan University, Kusatsu 525-8577, Japan
‡Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita 565-0871, Japan
§PRESTO, Japan Science and Technology Agency (JST), Kawaguchi 332-0012, Japan
S Supporting Information
b
ABSTRACT: Dipyrrolyldiketone boron complexes, as
π-conjugated acyclic anion receptors, act as building sub-
units of various assemblies through noncovalent interac-
tions in the form of receptorÀanion complexes. Instead of,
or in addition to, the modification of receptor structures, the
introduction of anion modules as building blocks for the
Figure 1. (a) π-Conjugated acyclic anion receptors 1a,b and their
anion-binding mode and (b) gallic acid derivatives 2-n and 3-n (n = 1, 16,
18, 20).
assemblies was found to be useful in forming various soft
materials. Gallic carboxylate derivatives 3-n (n = 16, 18, 20),
as tetrabutylammonium (TBA) salts, form receptorÀanion-
module complexes that can be used to fabricate supramo-
lecular assemblies. Combinations of aliphatic anion modules
3-n and receptors 1a,b along with a TBA cation afforded
products with mesophases, which were indicated by differ-
ential scanning calorimetry and polarized optical micro-
scopy. X-ray diffraction measurements of the solid states and
mesophases of 1a 3-n TBA and 1b 3-n TBA revealed
highly ordered structures including lamellar structures,
which could be modulated by the lengths of the alkyl chains
of the modules. Functional materials exhibiting electrical
conductivity were fabricated by using combinations of
anionic building blocks that form assemblies by themselves
and π-conjugated acyclic receptors.
functionalized module anions such as gallic carboxylate derivatives
(3-n, n = 1, 16, 18, 20; Figure 1b) by the replacement of spherical
halide anions would result in the fabrication of utility organized
structures. This would be possible by complexing with π-con-
jugated receptors as planar platforms, on the basis of van der Waals
interactions between the alkyl chains. In this Communication,
the formation and properties of supramolecular assemblies based
on anion modules by combinations of the modules with acyclic
anion receptors are reported. The assemblies are a new type of soft
materials formed by electrostatic interactions between charged
components and are different from related materials that have
thus far been reported as liquid crystals on the basis of ionic
mesogens.5À7
3
3
3
3
Gallic acid derivatives 2-n (n = 1, 16, 18, 20) are commercially
available for 2-1 and were synthesized for 2-n (n = 16, 18, 20)
according to the procedures described in the literature.8 The
corresponding carboxylates 3-n (n = 16, 18, 20) were obtained by
treating the carboxylic acids of 2-n with excess tetrabutylammo-
nium (TBA) hydroxide in CH2Cl2, followed by recrystallization
from tetradecane for 3-n (n = 16, 18, 20). On the other hand, 3-1
was obtained by mixing 2-1 with 1 equiv of tetrapropylammo-
nium (TPA) hydroxide. Subsequently, 3-n as TPA or TBA salts
were subjected to equivalent amounts of 1a and 1b to form
complexes. Receptors 1a and 1b did not yield soft materials but
formed 3D organized crystal structures in the presence of
tetraalkylammonium salts of ClÀ and BrÀ.4a,b,e The formation
and purification of complexes between 1a,b and 3-n (n = 1, 16,
18, 20) are performed by recrystallization from CH2Cl2/Et2O
(n = 1 as a TPA salt) and 1,4-dioxane (n = 16, 18, 20 as TBA
salts). The identification of 3-n (n = 1, 16, 18, 20) as TPA or TBA
salts and their complexes with 1a,b was performed by 1H NMR
and elemental analyses. A carboxylate-binding mode is indicated
nteractions between two complementary components are
efficient strategies to form various supramolecular organized
I
structures.1 Among various interactions, anion binding is an
effective process for achieving the formation of such assemblies
owing to its electrostatic hydrogen bonding, which can tightly
connect multiple building units using a small number of non-
covalent bonds.2 Appropriate negatively charged species and
open-chain receptors could provide various complexes, which
may be suitable for assembled structures when assisted by sup-
plementary interactions. As π-conjugated planar acyclic anion
receptors, dipyrrolyldiketone boron complexes (e.g., 1a,b), which
bind anions by the inversion (flipping) of two pyrrole rings
(Figure 1a),3,4 behave as essential building blocks of supramole-
cular assemblies such as supramolecular gels4b,d and thermotropic
liquid crystals4d based on the core π-planes in the presence of
aliphaticside chains. Inparticular, combinationsof the halide anion
complexes of receptors bearing long alkyl chains and appropriate
cations afford charge-by-charge assemblies consisting of alternately
stacking planar charged species.4f Instead of the modification of
receptor structures or in addition to that, the introduction of
Received: April 27, 2011
Published: May 17, 2011
r
2011 American Chemical Society
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Figure 2. Single-crystal X-ray structure of 1a 3-1 as a TPA salt: (a) top
3
view and (b) side packing view. One chiral conformation is represented.
TPA cations are omitted in the top view. Atom color code: brown, pink,
yellow, green, blue, and red indicate carbon, hydrogen, boron, fluorine,
nitrogen, and oxygen, respectively.
by various spectra9 along with theoretical studies10 and the single-
crystal X-ray analysis of 1a 3-1 as a TPA salt (Figure 2a).11
3
In the solid state, two carboxylate oxygens of 3-1 form
hydrogen bonding with two pyrrole NH and bridging CH with
N(ÀH) O and C(ÀH) O distances of 2.707/2.697 and
3 3 3
3 3 3
3.179 Å, respectively. A less symmetrical interaction results in a
dihedral angle of 47.19° between the receptor and the aryl moiety
of 3-1 to afford chiral conformation in 1a 3-1. The benzoate is
3
associated with 1a in an unsymmetrical fashion, as observed from
the angle of the bridging-CÀcarboxylate-CÀipso-C given by
142.65°, which is a substantial aberration from the 180° value in
the case of a symmetrical binding arrangement. The same chiral
conformations of the receptorÀbenzoate complexes are aligned
and form layers, two of which are located in the alternate stacking
with the layers of TPA (Figure 2b). Further, solid-state absorp-
tion of 1a 3-16 TBA at, for example, 450 nm (λmax) is red-
Figure 3. POM images of (a) 1a 3-16 TBA at 90 °C, (b) 1a 3-
3
3
3
18 TBA at 95 °C, (c) 1a 3-20 TBA at 92 and 80 °C (inset), (d) 1b 3-
3
3
3
3
16 TBA at 80.5 °C, (e) 1b 3-18 TBA at 83 °C, and (f) 1b 3-20 TBA
3
3
3
3
3
at 86 °C. All the measurements were conducted during cooling
processes. Like 1a 3-20 TBA, multiple mesophases were often ob-
3
3
served by POM.
3
3
shifted to that in solution (430 nm), owing to interactions
between the receptorÀanion-module complex units in the
solid state.
Organized structures of the complexes of 1a,b and the
aliphatic anion modules 3-n (n = 16, 18, 20) as TBA salts were
examined. Differential scanning calorimetry (DSC) of the com-
plexes 1a 3-n TBA and 1b 3-n TBA (n = 16, 18, 20) exhibited
3
3
3
3
the existence of mesophases with transition temperatures (°C) of
42/56/103 (1a 3-16 TBA), 67/73/101 (1a 3-18 TBA), 67/
81/96 (1a 3-20 TBA), 40/61/81 (1b 3-16 TBA), 53/64/86
3
3
3
3
3
3
3
3
(1b 3-18 TBA), and 61/82/89 (1b 3-20 TBA) during the
3
3
3
3
second heating (5 °C/min).12 The tendencies pertaining to
melting and clearing seem to be dependent on the alkyl chain
lengths of anion modules and the presence or absence of
R-phenyl moieties in the receptors. Further, polarized optical
microscopy (POM) images of 1a 3-n TBA and 1b 3-n TBA
Figure 4. XRD pattern (left) and an assembled model (right) of 1b
3
3-16 TBA as the solid state at rt prepared after melting. The assembled
3
structure indicated by XRD seems more disordered than the proposed
model. The value of 2.58 nm was estimated by theoretical study.
3
3
3
3
(n = 16, 18, 20) in the mesophases exhibit a birefringence
attributable to liquid crystal properties with, for example, focal
conic and mosaic textures (Figure 3). In these mesophases, the
emergence of POM textures is significantly dependent on the
conditions of formation processes such as heating and cool-
ing paces.
in 1b 3-n TBA are consistent with the approximately summed
3
3
lengths of the two receptorÀanion-module complexes, as supported
by molecular modeling. Further, there are no clear diffractions
assignable to the repeated distances of the receptorÀanion-
module complexes, suggesting that more disordered structures
are constructed around the anionic components (receptorÀ
anion-module complexes) and cations (TBA), which can form
charge-by-charge assemblies. Under the consideration of the
solid-state assembled mode of 1a 3-1 TPA, the anion modules
3-n may be located with distorted angles to the receptor plane
and can predominantly control the assembled modes through
van der Waals interactions of aliphatic chains (Figure 4, right panel).
This is one of the characteristic points of assemblies comprising
Structures in the solid states and mesophases of 1a 3-n and
3
1b 3-n (n = 16, 18, 20) as TBA salts were examined by
3
synchrotron X-ray diffraction (XRD) analysis at variable tempera-
tures (BL40B2 at SPring-8); the structures exhibited fairly com-
plicated diffraction patterns in many cases. However, the solid
states at rt after melting once to isotropic liquids (Iso) had clear
and simple XRD patterns, exhibiting the formation of lamellar
structures with c = 4.34, 4.56, and 4.76 nm for 1b 3-n TBA
3
3
3
3
(n = 16, 18, 20), respectively (Figure4, left panel).13 These c values
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Journal of the American Chemical Society
COMMUNICATION
anion modules. Similarly, the solid state of 1a 3-20 TBA forms
’ ASSOCIATED CONTENT
3
3
a lamellar structure with c = 4.64 nm, in comparison with the
broad peaks of 1a 3-16 TBA and 1a 3-18 TBA. On the other
S
Supporting Information. Synthetic procedures and analy-
b
3
3
3
3
tical data, anion-binding properties, a CIF file for the X-ray
structural analysis of 1a 3-1 TPA, and complete ref 10b. This
material is available free of charge via the Internet at http://pubs.
acs.org.
hand, mesophases of 1a 3-n TBA and 1b 3-n TBA (n = 16,
3
3
3
3
18, 20) exhibited complicated and relatively sharp XRD pat-
terns, which were presumably derived from soft crystals as
significantly ordered states of liquid crystals.6b,14 Although the
exact packing structures cannot be determined at present,
mesophases are basically constructed by lamellar and related
structures in highly ordered modes as can be speculated from
the patterns obtained from the solid states. Among various
3
3
’ AUTHOR INFORMATION
Corresponding Author
maedahir@ph.ritsumei.ac.jp
conditions and combinations of receptors and modules, 1a 3-
3
16 TBA at 93 °C and 1a 3-18 TBA at 90 °C during the
3
3
3
second heating exhibit lamellar structures with c = 5.53 and
5.89 nm, respectively. Further, diffractions possibly assignable
to repeated distances of charge-by-charge assemblies (ca. 7À8
Å) were also observed, for example, at 7.61 and 7.49 Å at 53 and
’ ACKNOWLEDGMENT
This work was supported by PRESTO/JST (2007À2011),
Grants-in-Aid for Young Scientists (B) (No. 21750155) and (A)
(No. 23685032) from the MEXT and Ritsumeikan R-GIRO
project (2008À2013). The authors thank Prof. Atsuhiro Osuka,
Dr. Naoki Aatani, and Mr. Eiji Tsurumaki, Kyoto University, and
Dr. Yohei Haketa, Ritsumeikan University, for single-crystal
X-ray analysis; Prof. Hiroshi Shinokubo and Dr. Satoru Hiroto
(Nagoya University) for ESI-MS measurements; Prof. Sono
Sasaki (Kyoto Institute of Technology at present) and Dr.
Noboru Ohta, JASRII/SPring-8, for synchrotron XRD analyses;
and Prof. Tomonori Hanasaki and Prof. Hitoshi Tamiaki,
Ritsumeikan University, for various measurements.
93 °C, respectively, for 1a 3-16 TBA and at 7.68 and 7.62 Å at
3
3
70 and 90 °C, respectively, for 1a 3-18 TBA during the second
3
3
heating. This suggests that the interaction between the anionic
planes of the receptorÀanion-module complex and the TBA
cations is weak but contributes to the construction of assembled
structures.
Ordered assembled structures, as observed in the recep-
torÀanion-module complexes, are suitable for use as charge-
conductive materials. Therefore, we conducted flash-photolysis
time-resolved microwave conductivity (FP-TRMC) measurements,15
which allow the estimation of the behavior of mobile charge
carriers. ReceptorÀanion-module complexes 1a 3-16 TBA and
’ REFERENCES
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3
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3
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3
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3
3
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3
3
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