A C3-symmetric macrocycle-based, hydrogen-bonded, multiporous hexagonal network as a motif of porous molecular crystals

Article abstract of DOI:10.1002/anie.201411438

A C₃-symmetric π-conjugated macrocycle combined with an appropriate hydrogen bonding module (phenylene triangle) allowed the construction of crystalline supramolecular frameworks with a cavity volume of up to 58%. The frameworks were obtained t

Full text of DOI:10.1002/anie.201411438

Angewandte
Chemie
DOI: 10.1002/anie.201411438
Supramolecular Chemistry
C -Symmetric Macrocycle-Based, Hydrogen-Bonded, Multiporous
3
Hexagonal Network as Motif of Porous Molecular Crystals**
Ichiro Hisaki,* Shoichi Nakagawa, Norimitsu Tohnai, and Mikiji Miyata*
Abstract: A C -symmetric p-conjugated macrocycle combined
3
with an appropriate hydrogen bonding module (phenylene
triangle) allowed the construction of crystalline supramolec-
ular frameworks with a cavity volume of up to 58%. The
frameworks were obtained through non-interpenetrated stack-
ing of a hexagonal sheet possessing three kinds of pores with
different sizes and shapes. The activated porous material
3
À1
absorbed CO up to 96 cm g at 195 K under 1 atm.
2
T
wo-dimensional (2D) hexagonal networks (HexNets) have
attracted much attention not only because of their topology-
[
1]
generated physical properties, but also their porous archi-
tectures. Namely, the construction of a 2D HexNet with large
voids and subsequent accumulation of the network without
interpenetration can yield materials applicable for storage of
[
2]
certain chemical species or for a platform to build supra-
[
3]
molecular architectures. Particularly, a HexNet connected
by hydrogen bonds (H-HexNet) can provide a reversible
dynamic behavior when chemical events occur. To date, 3D
assemblies based on porous H-HexNets have been con-
structed from molecules such as 1,3,5-substituted benzene
[
3,4]
[5]
derivatives,
aliphatic tricarboxylic acids, hexasubstituted
[
6]
[7]
benzene derivatives,
phosphazene derivatives,
and
[
8]
others. However, it still remains challenging to construct
a 3D assembly of H-HexNet with voids that are well-
controlled in size, shape, and multiplicity, although such
Figure 1. Porous HexNets composed of a) C - and C -symmetric radial
[9]
3
6
porous 2D networks were recently achieved on a surface.
molecules (conventional systems), and of b) a C -symmetric macro-
3
The difficulty in 3D systems is caused mainly by the following
three factors: 1) Crystallization of a building block with
hydrogen bonding groups needs highly polar solvents, which,
however, frequently results in failure of 2D networking by
trapping of the hydrogen bonding groups by the solvent
cyclic molecule with alternate short and long sides (this work), which
provides three types of voids I, II, and III. c) Chemical structure of
macrocyclic 1 that can form a triangular supramolecular motif named
“phenylene triangle (PhT)” (d).
[10]
molecules. 2) Even when a porous 2D network structure is
formed, voids disappear by interpenetration of the net-
[
4a]
work. 3) Conventional systems such as 1,3,5- and hexasub-
[
3,4]
stituted benzene derivatives
usually result in a network
[
+]
with uniform-shaped voids (Figure 1a).
[
*] Dr. I. Hisaki, S. Nakagawa, Dr. N. Tohnai, Prof. M. Miyata
Department of Material and Life Science
Graduate School of Engineering, Osaka University
In this regard, we planned to construct a novel 3D
assembly of H-HexNet possessing multiple pores with differ-
ent shape and size, based on a new strategy as follows
(Figure 1b): 1) As a building block core, we used dodeca-
dehydrotribenzo[18]annulene (DBA 1) (Figure 1c), a C3-
symmetric planar macrocycle because a) its planarity and
2-1 Yamadaoka, Suita, Osaka 565-0871 (Japan)
E-mail: hisaki@mls.eng.osaka-u.ac.jp
miyata@mls.eng.osaka-u.ac.jp
[11]
+
[
] Present address: The Institute of Scientific and Industrial Research
Osaka University
-1 Mihogaoka, Ibaraki, Osaka 567-0047 (Japan)
**] This work was supported by Grant-in-Aid for Young Scientists (A)
24685026) from MEXT. Crystallographic data was partly collected
[12]
rigidity are advantageous in forming coplanar assemblies,
8
b) it can provide a multiporous system due to two different
lengths of the sides as well as an inherent shape-persistent
void in the molecule. 2) To arrange a DBA core into a porous
H-HexNet, three 4,4’-carboxy-o-terphenyl groups were intro-
duced in the core. This is based on the hypothesis that the
group can form triangular porous motifs through hydrogen-
bonded dimerization of carboxy groups (Figure 1d). We
[
(
using a synchrotron radiation at the BL38B1 in the SPring-8 with
approval of JASRI (proposal Nos. 2013B1245, 2014A1252, and
2014B1168).
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/anie.201411438.
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[
13]
named the triangular motif as “phenylene triangle (PhT)”.
motifs to give a ladder-type porous network structure (Fig-
ure 2d). These results indicate that, although the 4,4’-
carboxy-o-terphenyl unit does not always form the PhT
motif, geometrically or electrostatically well-preorganized
derivatives can form the PhT motif. Another trivial interest is
that the PhT includes conformational frustration originating
from sterical requirements (see Figure S6).
The group is also expected to increase solubility into a solvent
and to prevent interpenetrated crystal packing, due to
nonplanarity and sterical hindrance of the phenylene moi-
eties.
Herein, we describe that 1 gave low-density H-HexNets
possessing three kinds of voids with different sizes and shapes
and that non-interpenetrated lamination of the H-HexNets
can provide a new class of porous materials. The stacking
manner of the sheets can be varied statistically and dynam-
ically by changing template molecules adsorbed in the voids.
Subsequently, 1 was crystallized under various conditions
(Scheme 1) to construct a 3D assembly of H-HexNet, yielding
Furthermore, the activated porous material can absorb CO
gas up to 96 cm g at 195 K at 1 atm.
2
3
À1
Preliminary, to confirm whether PhT is a robust supra-
molecular motif in a solid state, reference compounds 2a, 2b,
and 3 (Figure 2a) were crystallized from a solution of DMF,
Scheme 1. Crystallization conditions of 1.
three types of crystals (1-1D, 1-2D1, and 1-2D2). Crystalliza-
[
14]
tion from a DMF solution yielded 1-1D (Figure S7),
in
which DMF molecules are bonded through hydrogen bonds
with four carboxy groups of 1 to prevent the H-HexNet
structure. On the other hand, crystallization of 1 in the
presence of aromatic additives gave low-density H-HexNets.
DBA 1 dissolved in a mixture of DMF and methyl benzoate
[
14]
(
MeBz) at 508C yielded 1-2D1(MeBz) crystals (Figures 3a
Figure 2. Formation of the phenylene triangles (PhTs) in the crystalline
state. a) Chemical structures of reference compounds. b) PhT structure
composed of 2b. c) Intermolecular CH/Br interactions. d) PhT struc-
ture composed of 3. Molecules of 135TCB or 124TCB included in the
voids are omitted for clarity.
Figure 3. PhT motifs composed of 1 with 75% displacement ellipsoid
plots. a) PhT of 1-2D1(MeBz), in which one carboxy dimer includes
conformational frustration. b) PhT of 1-2D2(DMF,124TCB), in which
a DMF molecule is inserted in the carboxy dimer.
1
,2,4-trichlorobenzene (124TCB), and 1,3,5-trichlorobenzene
and 4a–d). The 1-2D1(MeBz) crystal involves the PhT motif
(Figure 3a), in which one pair of the hydrogen-bonded
carboxy phenyl groups shows conformational frustration.
Molecules of 1 were linked by the PhT to give a H-HexNet
(Figure 4a). The H-HexNet contains three types of voids I, II,
and III. The smallest triangular one, I with 3.5 ꢀ on a side and
a diameter of 3.2 ꢀ, includes no guest. The PhTꢁs void II
[
14]
(
135TCB) at 508C. X-ray crystallographic analysis of the
obtained single crystals revealed that, although 2a formed an
infinite zigzag strand (Figure S1), 2b achieved the PhT
through hydrogen-bonded dimerization of the carboxy
groups (Figure 2b). The PhT possesses a triangular void
with 12.5 ꢀ on a side and a diameter of 9.7 ꢀ. The PhT
interacts with the neighboring PhTunits through threefold CÀ accommodates one or two molecule(s) of MeBz. The largest
H···Br interactions (H···Br distances: 2.79–2.96 ꢀ, C-H-Br
angles: 144–1678) (Figure 2c) to form a hexagonally packed
coplanar structure (Figure S4). Similarly, 3 formed PhT
nonregular hexagonal void III with alternate sides of 4.8 ꢀ
and 13.4 ꢀ and a diameter of ca. 20.5 ꢀ accommodates more
than two molecules of MeBz. Overall, 36 molecules of MeBz
2
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Figure 4. Crystal structures of 1-2D1(MeBz) (a–d) and 1-2D2(DMF,124TCB) (e–h). a,e) Multiporous HexNets with three types of voids I, II, and
III. b,f) Packing diagrams of three layers colored light green, light blue, and red stacking without interpenetration. c,g) Stacking manners of the
adjacent two rhombic motifs. d,h) Schematic representations for stacking diagrams of six layers (colored of the layers, 1st: red, 2nd: orange, 3rd:
light green, 4th: green, 5th: light blue, 6th: blue). Arabic numbers point to the DBA core in the each layer. Hydrogen-bonding of DMF molecules
with the framework is colored green in (e–g). Guest molecules included in the voids are omitted for clarity.
are accommodated in the unit cell with a host/guest ratio of
:6 (Figures S8, S16, and S20). The H-HexNet was stacked
ure 4c, a rhombic frame of the 1-2D1(MeBz) crystal stacks
1
with another rhombic frame lying on the neighboring sheet in
[16]
without interpenetration to give a 3D framework (Figure 4b).
The cavity volume of the framework was calculated to 58%
an inverted way so that these frames contact each other.
1-2D2(DMF,124TCB), on the other hand, has two stacking
ways of the rhombic frame: one is similar with that of
1-2D1(MeBz) (Figure 4g, top), whereas the second has
a smaller overlap compared with the former (Figure 4g,
bottom). The latter stacking way is caused by steric repulsion
between the DMF molecules and/or by packing of guests in
the voids. Schematic stacking diagrams (Figure 4d and h)
show that 1-2D1(MeBz) has a wider bottle neck of the
inclusion space than 1-2D2(DMF,124TCB).
To remove the accommodated molecules and activate
the H-HexNet assembly, the crystalline bulk of 1-2D2-
(DMF,124TCB) was soaked with benzene followed by the
application of vacuum, resulting in desolvated crystalline
material (i.e., 1-2D-apo). A powder X-ray diffraction
(PXRD) pattern of the material shows slightly broad but
unambiguous peaks (Figure 5a). A peak at 3.748 (d spacing:
23.6 ꢀ) attributed to the 001 face of 1-2D2(DMF,124TCB)
disappeared and one at 4.128 (d spacing: 21.4 ꢀ) newly
appeared, combined with those at 4.968 and 6.588 upon
guest desorption. Assuming that the porous H-HexNet could
remain, the above-mentioned changes in the PXRD pattern
indicate that the layer was slipped by ca. 3 ꢀ along a certain
[
15]
by PLATON software. The form 1-2D1 was also obtained
when N,N-dimethylaniline (DMA) was applied instead of
MeBz (Figure S9).
Similarly, crystallization of 1 from a DMF and 124TCB
solution at 508C yielded the 1-2D2(DMF,124TCB) crystal
[
14]
(
Figures 3b and 4 e–h).
Although 1-2D2(DMF,124TCB)
has a PhT similar to that of 1-2D1(MeBz), a DMF molecule is
inserted to the frustrated dimer moiety to release the
distortion (Figure 3b). The resulting H-HexNet involves
three types of void spaces similar to that of 1-2D1(MeBz)
(
Figure 4e). The PhTꢁs void involves one 124TCB molecule
and the hexagonal void was estimated to accommodate seven
24TCB molecules (Figures S10, S17, and S21). The sheet was
stacked without interpenetration (Figure 4 f). The cavity
1
[15]
volume of the framework was calculated at 49%.
form 1-2D2 was also obtained when N-methylpyrrolidone
NMP) or N,N-dimethylacetamide (DMAA) was applied
instead of DMF for crystallization (Figures S11 and S12).
Interestingly, although 1-2D1(MeBz) and
D2(DMF,124TCB) exhibits quite similar H-HexNets, the
The
(
1-
2
networks accumulate in a different way. As shown in Fig-
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struct 3D porous molecular architecture. The activated
porous material showed CO2 gas adsorption. The results
promise that the present system could open a door to develop
a new class of highly porous functional materials. Further-
more, the stacking manner of the H-HexNet can be changed
statistically and dynamically depending on the guest mole-
cules. Turning of the stacking manner, for example, to the on-
[21]
top arrangement surely provides three kinds of channels,
which is under investigation in our laboratory.
Received: November 26, 2014
Published online: && &&, &&&&
Keywords: annulenes · hydrogen bonds · phenylene triangle ·
.
porous materials · supramolecular chemistry
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[
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14] The detailed crystal data are shown in Table S1 in the Supporting
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(
DMA)), 1035282 (1-2D2(DMF,124TCB)), 1035281
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Communications
Supramolecular Chemistry
Construction of porous crystalline two-
dimensional frameworks is achieved
through non-interpenetrated stacking of
a multiporous hexagonal network pos-
sessing three kinds of voids with different
sizes and shapes. A cavity volume of up
to 58% is obtained.
I. Hisaki,* S. Nakagawa, N. Tohnai,
M. Miyata*
&&& — &&&
C3-Symmetric Macrocycle-Based,
Hydrogen-Bonded, Multiporous
Hexagonal Network as Motif of Porous
Molecular Crystals
6
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Angew. Chem. Int. Ed. 2015, 54, 1 – 6
These are not the final page numbers!