A R T I C L E S
Devic et al.
depending on both the nature of guests and the temperature,
evolve from a narrow pore (np) to a large pore (lp) form (see
Figure 1) with a variation of their cell volume (up to 40%)
without any bond breaking.
3
5,36,39,40
47
The explored guests up to now are water,
carbon
41,42
43-45
46
dioxide,
liquids.
linear alkanes,
Ibuprofen, xylenes, or other
Moreover, the nature of the form strongly depends
on the nature of the M metal, with a very different flexible
compared with its Cr,
While the Al, Cr dried solids possess
a large pore structure at room temperature that might shrink or
48-50
III
3
7,46
character for the MIL-53(Fe) solid
Al, or Ga analogues.
3
9,51
41,43,44
not upon adsorption,
the iron solid exhibits a close narrow
pore dried form that turns into larger pore forms through two
39,45,48
structural transitions upon adsorption of guest molecules.
MIL-53(Ga) exhibits an intermediate behavior with a narrow
pore dried form at room temperature that further reopens at
5
1
higher temperature. It was shown that the narrow pore and
the large pore forms are rather close in energy and that the
host-guest interactions should overcome an energy barrier (∼20
-
1
40,43
kJ mol for MIL-53(Cr)
other.
) to switch from one form to the
Figure 1. View of the structure of MIL-53(M). Left: chains of corner
42
4 2
sharing MO (OH) octahedra. Right: the 3-dimensional framework shown
along the pores axis, in both its large pore (top) and narrow pore (bottom)
form.
First attempts of functionalization have concerned a basic
group (introduction of one -NH per linker for MIL-53(Al,
acidic groups (introduction of one -OH or two
2
3
2,52,53
Fe),
2
CO H per linker in MIL-53(Al) and (Fe) respectively),
35-38
shaped one-dimensional channels (Figure 1).
This structure
54
55
-
currently represents the archetype of flexible solids which,
and apolar groups (introduction of one phenyl or four -CH
3
56
57
groups per linker in MIL-53(Al) and (Cr) respectively). Polar
(
(
(
(
(
(
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128 J. AM. CHEM. SOC. 9 VOL. 132, NO. 3, 2010