Angewandte
Chemie
supports the proposed mechanism (see the Supporting
Information).
This organic supramolecular material can be regarded as a
new type of macroporous material. We confirmed the
existence of the macropores by using a mercury intrusion
porosimeter (Figure 5a). The result shows the development
Experimental Section
The detailed synthesis of 1 is provided in the Supporting Information.
To generate parallelogrammatic pipes, 20% w/v solution of 1 in
ethanol was prepared at 968C and allowed to drop onto a silicon
wafer that had been freshly washed with piranha solution. The drop
was allowed to evaporate at RT. The process of the structure
evolution was imaged by a Nikon ME600L microscope equipped with
a Photron Focuscope all-in-focus system. FE-SEM studies were
performed on Philips XL30S FE-SEM for Au-sputtered samples.
Powder XRD patterns were obtained on Rigaku D/MAX Ultima
diffractometer with scan speed of 28minꢀ1, sampling width of 0.018,
and CuKa (l = 0.154 nm) as a light source. Mercury porosimetry
isotherms were obtained with an AutoPore III (Micromeritics). The
samples were evacuated under vacuum (below 3 10ꢀ2 Torr) at room
temperature prior to intrusion of mercury. The Kelvin equation was
used to determine the pore-size distribution of the samples. The
contact angle between sample and mercury was chosen as 1408.
Received: March 5, 2006
Revised: July 2, 2006
Published online: August 29, 2006
Keywords: crystal growth · polymorphism · self-assembly ·
.
X-ray diffraction
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¯
[5] Crystal data for 1L: C20H30F3NO2, triclinic, space group P1, scan
range 3.4 < 2q < 56.38, T= 293(2) K, a = 4.9837(13), b =
8.952(2), c = 23.931(6) , a = 93.495(5), b = 90.810(5), g =
93.460(5)8,
Figure 5. a) Typical pore-size distribution of the pipes. The sample was
prepared from a 40% w/v solution in ethanol. Porosity: 73%. Max-
V= 1063.5(5) 3,
Z = 2, 1calcd = 1.166 gcmꢀ3
,
imum mean pore diameter: 41.1 mm. b) Plotof content(% w/v) of
1
m(MoKa) = 0.092 mmꢀ1, 12062 unique reflections, of which 4746
were taken as observed [I > 2s(I)], R j F2 j = 0.2093, wR = 0.1397.
CCDC-600374 contains the supplementary crystallographic data
for this paper. These data can be obtained free of charge from
cam.ac.uk/data_request/cif.
in ethanol versus maximum mean pore diameter and bulk density of
the pipes. Filled dots: bulk density. Empty squares: maximum pore
diameter. Dashed line: least-squares fit of maximum pore diameter
plot( R=99.2%).
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of pipes with the average pore diameter of tens of micro-
meters, which corresponds to those observed by SEM. The
average pore diameter of the pipes was gradually reduced
with increases of the concentration of 1 (Figure 5b), which
indicates that it is possible to tune the pore size.
In summary, we developed a novel self-templating tech-
nique between polymorphs and demonstrated the formation
of organic macroporous parallelogrammatic pipes through
drying-mediated assembly. We expect that this strategy to
generate organic materials with lower symmetries in a
macroscopic dimension will open a route to develop hollow
macroscopic structures with unusual shapes.
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ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim