Communications
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The reversibility of thiophene uptake was investigated
thermogravimetrically and by X-ray diffraction studies. A
sample was saturated with thiophene on a thermobalance
following the procedure described above. When the sample
reached constant weight at ambient temperature, the temper-
ature was raised to 1508C. Thiophene desorbed and the
sample weight returned to its initial value (blue data points in
Figure 2). An X-ray powder pattern of the final sample
indicated complete retention of crystallinity. A single crystal
of [V(O)(bdc)](thiophene) was heated to 2008C for 30 min to
remove the thiophene. The results show that the structure
reverts to space group Pnma, and the complete absence of any
electron density in the channels indicates complete desorp-
tion of thiophene. The lattice parameters are a = 6.813(2), b =
16.248(4), and c = 13.749(3) , which indicate a 1% smaller
cell volume than 2 and suggest that annealing at over 2008C is
necessary to allow the framework to completely relax.
The structural details of the four intercalated compounds
presented herein, and the selective and reversible removal of
sulfur-containing molecules from methane, show the impor-
tance of noncovalent oriented weak interactions in the
packing of organic molecules within channels of a specific
metal–organic framework. Such interactions, although rela-
tively weak, can readily cause remarkable deformation and
symmetry changes in the framework, thus pointing to
effective ways of manipulating known materials or designing
new materials with targeted properties through intercalation
chemistry.
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Experimental Section
[V(O)(bdc)](H2bdc)0.71 (1) was synthesized by hydrothermal reaction
from a mixture of VO2, HCl, H2bdc, and H2O (molar ratio =
1:2:0.5:77). The mixture was heated at 2208C in a sealed teflon
vessel for 3 days. By using vacuum filtration and drying in air, red-
brown prisms of 1 were recovered as a major phase together with
dark-green impurities, which were readily removed by washing with
methanol. For the absorption measurements, red prism crystals of 1
were heated in air to 3508C at a rate of 38CminÀ1 to form
[V(O)(bdc)] (2). Intercalation experiments were carried out by
immersing crystals of 2 in liquid aniline, thiophene, and acetone. For
gas-phase absorption, crystals of 1 were heated on a thermobalance to
3508C in air to remove H2bdc. The sample was maintained at constant
temperature for 30 min and then cooled to 288C. When the weight
was constant at 288C, the air flow was switched to 5% CH4/He. After
the weight became constant, the flow of 5% CH4/He was passed
through a bubbler containing liquid (CH3)2S. After a short time, the
weight of [V(O)(bdc)] increased dramatically.
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J. Pastre, J. Mater. Chem. 2006, 16, 626.
[13] 1: Elemental analysis (%) calcd for [V(O)(bdc)](H2bdc)0.71: V
14.6, C 47.08, H 2.37; found: 14.8; C 47.10, H 2.68; crystal data:
space group P212121, a = 6.8094(3), b = 12.4220(6), c =
17.1733(8) , V= 1452.6(1) 3, Z = 4, T= 223 K, dcalcd
=
1.593 gcmÀ3; single-crystal data were collected on a Siemens
SMART/CCD diffractometer (14526 reflections total, 3498
unique, Rint = 0.0478); the structure was solved and refined
with the SHELXTL software package; final refinements con-
verged at R1 = 0.0394 for all 3498 reflections and 188 parame-
ters.
Received: June 26, 2006
Published online: September 13, 2006
Keywords: host–guest systems · intercalation ·
.
metal–organic frameworks · selective absorption · vanadium
[14] Thermogravimetric analyses of 1 carried out in air at 38CminÀ1
showed two weight-loss events. The first between 320 and 4008C
corresponds to the loss of the guest H2bdc. The second between
440 and 4808C corresponds to the loss of framework bdc. A
sample heated at 3908C for 10 h was confirmed to be identical to
MIL-47 by IR spectroscopy (disappearance of the band at
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ca. 1700 cmÀ1 characteristic of free C O species) and single-
À =
crystal X-ray diffraction ([V(O)(bdc)] (2): space group Pnma,
a = 6.8249(8), b = 16.073(2), c = 13.995(2), T= 293 K, dcalcd
=
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 6499 –6503