Large Breathing Effects in Three-Dimensional Porous Hybrid Matter

This article was published as part of the
2009 Metalorganic frameworks issue

Reviewing the latest developments across the interdisciplinary area of
metalorganic frameworks from an academic and industrial perspective
Guest Editors Jeffrey Long and Omar Yaghi
Please take a look at the issue 5 table of contents to access
the other reviews.
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View Article Online / Journal Homepage / Table of Contents for this issue
Large breathing eects in three-dimensional porous hybrid matter:
facts, analyses, rules and consequencesw
Ge rard Fe rey*
ab
and Christian Serre
b
Received 2nd October 2008
First published as an Advance Article on the web 26th February 2009
DOI: 10.1039/b804302g
This critical review focusses on a strange behaviour of crystallized solid matter: its reversible
swelling with large magnitude. This will be of interest for experts in porous solids but also for
solid state chemists and physicists. Some examples, classied according to the dimensionality of
the inorganic subnetwork, present the general requirements and the structural rules which govern
the existence of this phenomenon. Its consequences concern specic applications related to
sensors, energy savings, sustainable development and health (100 references).
1. Introduction
Breathing is associated with life, at the macroscopic level and
at the molecular scale as well. Biological matter is known for a
long time to imply molecular movements with large magnitude
during biochemical reactions, and can be mimicked by clever
organic chemists.
1,2
On the contrary, inorganic matter is often
associated with rigid bodies and a quasi-immobility except
during phase transitions in the solid state.
However, some recent papers run counter to these pre-
conceived ideas and describe solids which, under an external
stimulus (temperature, pressure, chemical inclusion. . .),
exhibit a very important exibility, while retaining the same
or similar topologies. The atomic displacements reach some-
times several A
. This paper will analyze some of these solids

and try to explain the dierent origins of such exibility. We
shall call this phenomenon breathing
36
which, according to
other authors, is also labelled as dynamic frameworks,
7
springlike,
8
sponge like
9,10
or accordion
11
eects.
Breathing is associated with reversible movements between
two states corresponding to expansion and contraction,
respectively. It is obvious for humans who inhale oxygen
and breathe out carbon dioxide. However, as seen below,
two situations are possible: many times, expansion is
associated with an input and contraction with an output but
the inverse phenomenon can occur: expansion 3output and
contraction 3input. Whatever the sense of the breathing, the
external stimulus generates the movement.
An important point of the breathing is also its magnitude.
Generally, in solid state matter, the movements are very small
(o0.8 A
) and often occur during displacive (without bond

breaking) phase transitions. A good example is provided by
the distortions of the perovskites
12
or the FeF
3
structure
(Fig. 1) with the ReO
3
type structure.
13
The rhombohedral
room temperature variety (contracted form) corresponds to
the tilting of octahedra represented in Fig. 1(a). It transforms
reversibly by heating at 400 1C into the ideal cubic ReO
3
type,
a
Institut universitaire de France, France.
E-mail: ferey@chimie.uvsq.fr. E-mail: gferey@wanadoo.fr
b
Institut Lavoisier, (CNRS 8180), University of Versailles, 45,
Avenue des Etats-Unis, F-78035 Versailles Cedex, France
w Part of the metalorganic frameworks themed issue.
Ge rard Fe rey
Gerard Ferey received his PhD
from Paris VI University in
1977. He was Professor of
Inorganic Chemistry rst
in Le Mans University
(19811996) and then in
Versailles University where
he created the Institut
Lavoisier (1996. . .). He is
now Professor at Institut
universitaire de France and
member of the French Acad-
emy des Sciences. He has re-
ceived many international
Awards. After working on the
magnetism of transition metal
inorganic uorides, his current interests concern the structural
chemistry of inorganic and hybrid porous solids, their mechan-
isms of formation and their applications in gas storage, energy,
drug delivery and nanosciences.
Christian Serre
Christian Serre, 38 years old,
is an engineer from the Ecole
Superieure de Physique et de
Chimie Industrielles de Paris.
He obtained a PhD in
Inorganic Chemistry in 1999.
After a post-doctoral fellow-
ship in the USA, he moved to
a permanent CNRS research
position in 2001 in the group of
Prof. Ferey in Versailles. He
is currently working on the
synthesis, structure determina-
tion and applications of porous
hybrid solids. He received the
CNRS bronze medal in 2006
and a European research council young researchers grant
in 2008.
1380 | Chem. Soc. Rev., 2009, 38, 13801399 This journal is c The Royal Society of Chemistry 2009
CRITICAL REVIEW www.rsc.org/csr | Chemical Society Reviews
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showing no tilting, after a cooperative movement of all the
uoride ions of 0.56 A
(Fig. 1(b)).
This phenomenon, despite being general in inorganic solid
state chemistry and in zeolites,
14
implies however too small
atomic displacements for being further considered in this
paper, devoted exclusively to large breathing eects in three-
dimensional organicinorganic hybrid solids containing only
strong bonds. For this reason, the purely organic or bio-
organic compounds, which exhibit similar displacements
15,16
and are governed by hydrogen bond interactions between
molecular species, will not be considered here. In a similar
way, two-dimensional hybrids are also excluded. Only the
layers are hybrid. Guests are incorporated between the sheets,
leading to a rich guest exchange chemistry, but the guest
extraction can render (reversibly or not
9
) the solid amorphous,
due a disordered arrangement of the layers to a (turbostratic
disorder).
Large breathing eects represent a new aspect of non-
organic matter. From the description of some exible solids
and of some counter examples, this paper will analyze the
structural reasons of breathing and try to generate some
building rules for obtaining such swelling phases. In a nal
part, the consequences of this breathing eect will be examined
in several domains such as energy, energy savings, sensors,
molecular recognition, and gas storage for sustainable devel-
opment and health.
2. General requirements for breathing in
crystalline hybrid solids
The need of a chemical or physical stimulus for generating
reversible movements was already noticed. From the
structural point of view, the exibility inherent to breathing
implies also a contrast in the strength, the directivity and the
nature of the dierent bonds existing in the solid. Such eects
are particularly evident in hybrid solids. In their skeleton,
these compounds generally associate ionic or ionocovalent
bonds in the inorganic part, and covalent and sometimes
pp ones in the organic moieties. Hydrogen or van der Waals
interactions
18,19
occur between the framework and the
occluded species.
The spatial occupancy of the dierent parts of the hybrid
solid plays a role. Indeed, the inorganic part is often associated
with a rigid behaviour, whereas the organic moieties corres-
pond to exibility. The amount of each component in the
nal solid will inuence the degree of breathing of the solid.
Therefore, one must consider not only the whole dimension-
ality of the hybrid solid, but also the dimensionality of each
subnetwork. In a rst step, if one excepts the case of molecular
solids, two groups of three situations occur with non-
interpenetrated solids.
for three-dimensional frameworks, the inorganic subnet-
work can be either two-, one ot zero-dimensional and linked
by organic moieties in one, two or three directions.
the same situation occurs for the inorganic contribution in
two-dimensional solids, but this time, the organic linkage
occurs only within the layers, the space between the latter
being occupied by the occluded species (solvents,
templates. . .). Hydrogen and pp bonds are involved, and
have been discussed in papers of Kitagawa.
17
Fig. 1 Perspective view of (a) rhombohedral and (b) cubic FeF
3
which correspond to the contracted and expanded forms of this solid
(see text).
Fig. 2 The six classes of Kitagawa. In all the classes, G is the symbol for Guest. In the 1D class, the voids between the chains are occupied by small
molecules and can exhibit ion exchange. In the rst case of 2D class, the manner of stacking of the layers (superimposed or shifted) is strongly
dependent on the nature of the guest and the weak interactions they have with the layers. In the second case, the interdigitated layers are
superimposed and form 1D channels. Closed without guests, they open with some of them, resulting in an elongation of the stacking parameter. In
the 3D cases, three situations occur. When pillared layers are concerned, the reversible phenomenon of interlayer elongation and shortening is
realized by non-rigid pillars. The expanding and shrinking frameworks act as sponges. Keeping the same topology, the drastic volume change is
induced by strong hostguest interactions. Depending on the structure, the volume increase is associated with either the evacuation or the inclusion
of the guests. Finally, in the case of interpenetrated grids, they are densely packed in the absence of guests and the introduction of molecules
generates a sliding of one network.
This journal is c The Royal Society of Chemistry 2009 Chem. Soc. Rev., 2009, 38, 13801399 | 1381
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A special situation concerns the interpenetrated or inter-
woven networks
17,18,20,21
which must take also into account
the interactions between the two (or more) framework contri-
butions. All these cases led Kitagawa
17
to propose six classes for
the breathing of dynamic coordination polymers (Fig. 2)
A third requirement obviously concerns the need of a free
space in the structure (which is often realized for hybrid
porous solids) in order to accommodate the modications of
the steric hindrance of the exible part during the movements.
Finally, and related to the contrast between the nature of
the bonds (ionic, covalent. . .), non-rigid areas (hereafter
denoted as weak points) must exist in the solid to allow the
breathing modes. Even if it is not obvious, their existence is
necessary but not sucient for generating breathing, as seen
later. The topology of some elements of the structure also
plays a crucial role. All these requirements will be illustrated in
the following examples.
3. Structural analysis of some illustrative examples
of three-dimensional networks
3.1 Two-dimensional inorganic subnetworks. The case of
pillared c-zirconium phosphates
The interesting two forms, a and g, of hydrated zirconium
phosphates (often labelled a- and b-ZrP) have been the subject
of many studies and applications since their discovery thirty
years ago (see for instance the references contained in refs. 11
and 2225) They are lamellar solids with guest water molecules
within the layers, and correspond to type a-1 in the Kitagawas
classication.
17
The layers are built from the dense corner-
sharing connection of zirconium octahedra and phosphorus
tetrahedra. For our purpose, g-ZrP or Zr
2
(HPO
4
)
4
4H
2
O
(Fig. 3(a) and (b)) is of particular interest. Indeed, Alberti
11
and Cleareld
25
proved that the phosphate groups of the
layers could be substituted, totally or partially, by mono- or
diphosphonate groups (linking two layers) with variable
length of aliphatic chains. Alberti
11
alone looked at
the thermal behaviour of these phases which were, to
our knowledge, the rst to exhibit such a drastic breathing
(B8 A
in the best case).

The study of the system Zr/phosphorous acid/
alkanediphosphonic acids/acetone/water at 350 K lead
to a series of phases of general formula ZrPO
4
[O
2
P(OH)
2
]
1x
-
[O
2
P(OH)(CH
2
)
n
(HO)PO
2
]
x/2
mH
2
O with 4 r n r 16
corresponding to the number of carbons in the alkyl chain;
x was allowed to vary from 0 to 1, x = 0 corresponding to
g-ZrP, x = 1 to the fully pillared Zr diphosphonate, and
intermediate values between 0 and 1 to an increasing degree of
pillaring between the layers of g-ZrP. Two examples of
complete pillaring are shown in Fig. 3(c) (for n = 4) and
Fig. 3 (a) Polyhedral projection of the structure of g-ZrP along [010] and (b) along [001]; (c) and (d) [010] projections of the completely pillared Zr
1,4- and 1,10-alkane diphosphonates, (e) a schematic view of the fully hydrated phosphate/diphosphonate and (f) of the corresponding dehydrated
sample showing the contraction of the carbon chain. Zr octahedra are in pale blue, phosphate groups in yellow, water molecules in dark blue,
OH groups in red and white and the carbons in black.
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Fig. 3(d) (for n = 10) and the distance between the layers
increases linearly following the law d
001
= 0.93 + 0.127n sin a
(a being the angle 52.71 in this familybetween the alkyl
chain and the plane of the layer). In the case of full pillaring,
three features are noteworthy: (i) the conguration of the
chains corresponds to the most stable arrangement (maximum
elongation), (ii) the distance between the chains is xed by the
distance separating the phosphorus atoms within the same side
of the layer (ca. 5.4 A
) and therefore (iii) the steric hindrance

of the chains authorizes neither degrees of freedom for the
conformation of the chains nor the insertion of additional
water molecules, since m, which represents the number of H
2
O
molecules per Zr remains 1. As a consequence, the fully
pillared series do not exhibit any exibility.
Breathing occurs (Fig. 3(e) and (f)) for low values of x. They
correspond to situations where two dierent alkanediphos-
phonic chains are separated, in a direction parallel to the
layer, by [O
2
P(OH)
2
] groups. For a given n, either when the
solids are wet or exposed to an atmosphere with 100% of
relative humidity (r.h.) (which represents the stimulus at
300 K)), the distance is, whatever x, the same as for the
completely pillared material. In this case, additional water
molecules take the place of the missing chains, which explains
why m is important for low x (for n = 10, m = 3.0 for x = 0.1
instead of m = 1 for x = 1). Their role implies, at this stage,
only space lling up to an amount which preserves the
maximum stability of the carbon chain.
However, a thorough study of the term n = 10 proves that,
varying the r.h. conditions and/or temperature, ecient
breathing occurs mainly for low values of x (Fig. 4(a) and
(b)). Compared to the fully hydrated sample for r.h. = 100%,
the decrease of r.h. to 75% leads, for instance for x = 0.1, to a
small (2.6 ) 2.4) but signicant decrease of m and, correla-
tively, an important decrease of the d
001
distance (19.2 A
)
14.1 A
). For the same x, the completely dehydrated sample

(which can be considered as either the 0% r.h. or the result of
the stimulus of temperature), corresponds to the following
changes: 2.6 ) 1.0 for m and 19.2 A
) 11.2 A
(decrease
of 8 A
!) for d
001
. Rehydration of the dehydrated solid
regenerates the initial fully hydrated sample with all its
specications. Fig. 4(a) and (b) show the evolution of the
dierent characteristics of breathing as a function of the
pillaring percentage x in this series.
This example provides a rst analysis of the reasons for such
a large breathing, whereas the structural topology remains the
same. Not only the stimulus is necessary but also its intensity
(in this case, water vapor pressure). Keeping the dense and
rigid arrangement of the layers, breathing (here uniaxial)
indeed occurs only for low values of the pillaring percentage x.
It is noteworthy that a threshold around 66% maximum seems
to be necessary for such an eect. Below, this corresponds
to the creation of enough space for the mobility of species and,
therefore, a exibility up to a certain amount, depending on
the intensity of the stimulus.
Two features are responsible of these movements: (i) as soon
as the carbon chains have sucient space between them, they
can develop their extraordinary plasticity due to the covalent
bonding and the free rotation around the axis of the bonds.
The torsion of these chains by increasing the cis-positions can
lead to variations in length of more than 50% even if,
thermodynamically, they are unstable as such. In the case of
the Albertis phosphonates, and even if no structural determi-
nation was given in their paper, the evolution of the d
001
distance between the fully hydrated and the dehydrated phase
can be explained by an helicoidal arrangement of the chain. It
is indeed easy to calculate
26
that, for n = 10, such a helix coils
around a cylinder with a radius of 1.08 A
, the pitch of the helix

being 0.668 A
. The length between the two terminal carbons of

the chains is then 6.012 A
(instead of 11.2 A
for the elongated

chain) and explains the 19.2 A
) 11.2 A
decrease for d
001
.
The weak point is then the carbon chain which acts as a
spring, which is compressed in the anhydrous form and
elongated for the fully hydrated one. This spring eect (ii) is
allowed because the water molecules are only loosely bound to
the skeleton and can move easily in the structure and give
enough space to the chain for its contraction.
3.2 One-dimensional inorganic subnetworks
3.2.1 The case of trivalent metal terephthalates (MIL-47
and -53)
36
. This situation was recently discovered in the
laboratory
3,4
during the search of functionalized hybrid
nanoporous solids with large pores.
27,28
It concerns metal
1,4-benzenedicarboxylates (BDC) [M(X)[BDC]xG (M is
V
IV
, with X = O for MIL-47, and trivalent Al, Cr, Fe, Ga
and X = OH, F for MIL53). The templates (G) are
terephthalic acid H
2
BDC, water or solvents such as DMF.
Fig. 4 (a) For n = 10, evolution of the number m of occluded water
molecules per Zr atom and of the decrease of the d
001
parameter
between the layers vs. the pillaring percentage x for dierent values of
r.h. (b) Evolution of the d
001
parameter vs. x and dierent situations of
conditioning of the samples (n = 10).
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At variance to the others, MIL-47 does not breathe. Indeed,
there are no OH groups in the skeleton in MIL-47, and it will
be shown below that these hydroxyl groups play a major role
in MIL-53 for the creation of symmetrical hydrogen bonds
with the oxygens of the occluded water.
At variance to MIL-47, MIL-53 breathes. According to the
dierent treatments, three variants of MIL-53 (hereafter
labelled -as, -ht and -lt) appear. They have in common a
three-dimensional network composed of corner-shared trans
chains of metallic octahedra (the OH groups being the shared
species) linked in the two other directions by terephthalate
ions. This determines large unidimensional lozenge-based
tunnels (Fig. 5(a)). In terms of nets, the topology of MIL-53
corresponds to a 4
4
lattice.
In the as-synthesized form MIL-53-as (V = 1440 A
3
) the
tunnels are occupied by structurally disordered molecules of
neutral terephthalic acid (Fig. 5(b)). They leave the structure
by heating at 573 K, and create the structure MIL-53-ht, with
empty tunnels (V = 1486 A
3
). By cooling in air, the structure
reabsorbs water. This leads to the third form MIL-53-lt
(V = 1012 A
3
). This transition is fully reversible when water
is involved, but the structure shows a very high selectivity
toward other adsorbable species. Indeed, whereas MIL-53-ht
is strictly inactive for the readsorption of acetone and ethanol
even after 4 days, it immediately adsorbs DMF in a reversible
way. Moreover, in MIL-53-lt, water is easily exchanged by
DMF, showing the great anity of DMF for this type of
structure. The resulting product has cell parameters inter-
mediate between MIL-53-as and MIL-53-lt, proving the
adaptability of the breathing network to the shape of the
chemical stimulus. Note that the introduction of large
amounts of some gases leads to the largest cell (see section 4.2).
The structures of the three forms, solved from X-ray powder
diraction, allow to quantify the large breathing eects during
the transformations, characterized, at constant topology, by
movements of large amplitude each time, created when either
adsorbed species or temperature act as stimuli.
For MIL-53(Cr) [X: O,F], the disappearance of the template
H
2
BDC during the transition MIL-53-as ) MIL-53-ht
corresponds to an increase by 3.16% of the volume of the
cell (Fig. 5(c)) with signicant variations of two of the cell
parameters (17.34 A
) 16.73 A
and 12.18 A
) 13.04 A
). The
third, which corresponds to the direction of the metallic
octahedral chains, remains invariant (B6.8 A
). The breathing
out paradoxically relates to an expansion of the cell instead of
the expected contraction. During the transition MIL-53-ht )
MIL-53-lt, the adsorption of water (the inhaling step) corres-
ponds (Fig. 5(d)) to a drastic decrease of the cell volume
(32%) associated this time with very large variations of the
two parameters involved above (16.7 A
) 19.7 A
(Dd: 3 A
)
and 13.0 A
) 7.85A
(Dd: 5.15 A
)).
The reasons for such changes are not the same as for the
diphosphonates. Indeed, now, if the rigidity of the inorganic
moieties remains almost the same, the sp
2
hybridization in the
phenyl rings renders the carbon skeleton rigid. The area of
exibility of the structure, the weak point, is restricted to the
connection between the inorganic chain and the carboxylic
function of the terephthalate (Fig. 5(e) and (f)). The two
oxygens of the latter are covalently bound to carbon but are
linked to chromium via a ionocovalent bond. This means
a possible rotation around the OO axis (which acts as a
kneecap) of the two planes OCrCrO and OCO
(Fig. 5(f)). The corresponding dihedral angle a between these
two planes (177.51 for -as, 1801 for -ht and 1391 for -lt)
characterizes mechanically the extent of breathing better than
the angles between two chains, depicted in Fig. 5(b)(d). It is
of note that the most expanded structure corresponds to a
dihedral angle of 1801.
This potential exibility is activated by the presence of
inserted species in the tunnels and the creation of weak bonds
between the guest and the skeleton. Here, the oxygens of the
chromium octahedra are involved. The onset of these addi-
tional bonds decreases the distance between the chains along
the short diagonal of the lozenge. They are separated by 13 A
in the expanded empty MIL-53-ht (Fig. 5(c)). The distance is

lowered by 0.9 A
in MIL-53-as when the template H

2
BDC is
present and the shrinkage reaches 5.2 A
in MIL-53-lt when
xed water molecules are involved and create a lock-in
between the chains, assimilating inhalation with contraction.
The strong rotation around the O O axis of the carboxylate
functions simultaneously induces some small changes for the
tilting angle M(OH)M in the chains, as proved by NMR
and IR measurements. Therefore, the rigidity of the inorganic
moiety is less strict for a 1D subnetwork than it was for a 2D
Fig. 5 (a) Perspective view of MIL-53-ht; (b)(d) projection along the
direction of the tunnels of (b) MIL-53-as (with some atoms of the
disordered terephthalic acid in blue), (c) MIL-53-ht, and (d) MIL-53-lt
with variable parameters; (e), (f) perspective views of the connection
between the chromium chains and the terephthalate ions. Chromium
octahedra are in green, water molecules in dark blue, OH groups in
pale blue, oxygens in red and carbons in black.
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one. This allows more degrees of freedom for this type of
breathing which is, at variance to the rst example, essentially
two-dimensional.
Moreover, in situ solid-state
13
C,
1
H and
27
Al NMR
experiments of the Al-homologue
5
during rehydration have
shown that the water molecules show three types of hydrogen
bonds (Fig. 6). The rst corresponds to a guestguest inter-
action of the water molecules along the axis of the tunnels. The
two others relate to hostguest interactions between (i) the
oxygen of the guest with the OH group of the host alterna-
tively with one chain and the other and (ii), between one
hydrogen of the water molecule and one oxygen of the
carboxylate linked to Al. The latter is clearly evidenced
by
13
C NMR experiments. The COO contribution of the
dehydrated sample progressively disappears during hydration
and is replaced by the COOH
2
O signal, which exists alone for
the fully hydrated sample.
27
Al NMR also conrms the
structural results and the small distortions and tiltings of the
Al(OH)
2
O
4
octahedra occuring during hydration.
The above interactions seemed to be sucient for explaining
the breathing phenomenon but, very recently, the study of the
Fe(III) analog, with the same topology, provided surprising
results.
29
Indeed, whereas its hydrated form is identical to the
other ones, the full dehydration of MIL-53(Fe) increases
the shrinkage of the structure in two subtle steps, instead of
the expansion of the others. This means that, beside the above
interactions, hosthost interactions must also be considered.
The comparison of the various distances observed in all the
hydrated forms does not allow to nd a geometrical criterion
able to explain the above dierence.
Anyhow, two possible reasons could be assumed for the
moment: (i) the inuence of the nature of the metal and
(ii) strong pp interactions. In most cases, the cation is a 3d
transition metal and magnetic dipolar interactions between the
chains may be taken into account. These interactions are
proportional to the number of unpaired d electrons. While
they can be considered as very weak with chromium(III) (d
3
)
and vanadium (d
2
), they become signicant with iron (d
5
) and
may participate in the stability of the structure. In the case of
MIL-53(Fe), this could explain that they are strong enough for
keeping the structure closed in the absence of water within the
tunnels. However, even if it is possible, the argument is
unlikely due to the long distance between the closest Fe(III)
along the short diagonal of the tunnel (7.64 A
(hydrated) and
6.87 A
(anhydrous)).
The distances between the phenyl rings of the terephthalates
can be used to estimate the strength of pp interactions.
Usually, they are considered as strong when the smallest
distances between the rings lie in the range 2.93.5 A
. Here,
they are in the range 3.7 (Fe)4,1 A
(Al, Cr) for the whole

family of MIL-53 hydrated solids. The signicantly smaller
distance in hydrated MIL-53(Fe) (Dd E0.4 A
) could explain
why the anhydrous MIL-53(Fe) remains closed. In such a case,
this would imply that it corresponds to the strongest hosthost
interaction in this topology. The evolution of the short ring
ring distances in MIL-53(Fe) [3.73 A
(hydrated form) and

3.41 A
when anhydrous], indicates an enhancement of the pp

interaction when the steric inuence of the occluded water
disappears. It is probably sucient for keeping the structure
closed. On the contrary, the larger distances observed for
the Al and Cr solids (44.1 A
), allow the opening of the

structure upon dehydration. The pp interactions obviously
play a role and a threshold seems to exist in the series of
values, below which opening is forbidden. This is conrmed
by MIL-69,
30
an aluminium naphthalene-dicarboxylate
Al
III
(OH)[O
2
CC
10
H
6
CO
2
], with the same topology, with
naphthalene rings replacing phenyl ones. It also remains
closed after dehydration (shorter ringring distances 3.78 A
).
3.2.2 The structural counter example of vanadium
terephthalate MIL-68. and the inuence of the topology. Besides
MIL-53, another three-dimensional vanadium(III) phase
(MIL-68
6
) appears in the same system, when using a non-
aqueous solvent. It has the same chemical formula as MIL-53:
M
III
(OH)[BTC]xG but its density is ca. 75% of that of
MIL-53. It represents a lacunar variant (25% vacancies)
of MIL-53 (Fig. 7). In terms of nets, MIL-68 is 6.3.6.3. instead
of 4
4
for MIL-53. According to OKeee and Hyde,
31
no direct
transition can occur between these two nets. However, both
structures are formed with the same octahedral chains and
linked in the same way by the same ligands. Only the topology
is dierent: MIL-68 contains hexagonal and triangular tunnels
parallel to the metallic chains, with angles being strictly 120 and
601, respectively, instead of lozenge sections in MIL-53.
The thermodiractometry of MIL-68 shows that the cell
remains unchanged, whatever the temperature, up to 350 1C,
which is the temperature of collapse of the structure. This
time, the absence of breathing has only one reason: the
existence of triangular cycles, already known to be strictly
rigid. They forbid any exibility at the weak points of the
previous type of structure and MIL-68 does not breathe. This
example illustrates the role of the whole topology on the
possibility of breathing.
As a rst conclusion of this part, breathing eects result
from the combination of several factors: (i) the existence of
only even cycles in the structure and of weak points, which
allow the structure to distort under the action of a guest
stimulus, and (ii) the occurrence of strong guestguest and
hostguest interactions, stronger than hosthost ones. The
Fig. 6 (a) Pespective view of the disposition of the water molecules
within the tunnel of MIL-53-lt with the hydrogen bonds.
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latter, if the strongest, prevent the opening of the structure.
This point will be later developed in section 3.4.
3.3 Zero-dimensional inorganic subnetworks. Examples and
counter examples
For such a type of dimensionality, it is now common to speak
about porous coordination polymers (PCP), a continuously
expanding domain. In such solids, the inorganic part has
nite dimensions and corresponds either to single metallic
polyhedra or to oligomeric clusters. The dynamic eects have
already been documented by the groups of Kitagawa
and Rosseinsky from the experimental point of view, with
numerous examples,
7,3236
and the reader is recommended to
return to the reviews and the references they contain.
Without going into detail, one can distinguish two types of
exibility resulting from (i) displacive phase transitions in
which the skeleton remains the same, while distorted or
(ii) reconstructive transitions with reversible cleavage/
formation of a metalcarboxylate bond and a scissoring
motion induced by the size of the guest.
36
The rst case is illustrated by the jungle gym solid
[Zn
2
(1,4-BDC)
2
(DABCO)]G.
3741
It is based on Zn
2
dimers
which, by linkage with four 1,4-BDC molecules, provide 2D
square grids. The pillaring of the latter by the nitrogens of
DABCO ensures the 3D structure (Fig. 8).
For example, during the adsorption of propane 2-ol
(IPA),
41
a monoclinic distortion of the primitive tetragonal
unit cell rst occurs after the introduction of up to three IPA
molecules per cell. The volume decreases by 21% with a
signicant (0.3 and 0.9 A
) unexpected decrease of the length

of the edges, since it corresponds to the length of both rigid
linkers. The distortion corresponds to a shift of the square
grids from one to the other by 161. By increasing the amount
of IPA up to 4.5 IPA regenerates the dimensions of the
original cell. This structural behaviour is obviously similar to
that observed with MIL-53(Cr) (section 4.2). The sequence
dimerDABCOdimer corresponds to a rigid moiety, as also
for the chains in MIL-53. The O O axis of the BDC plays the
same role of kneecap in both cases. Unfortunately, the high
disorder of isopropanol molecules prevents an accurate struc-
tural determination and therefore, any discussion about the
nature of interactions, at least for three IPA in the cell. The
same behaviour also occurs in a solid recently discovered by
Long et al.
42
with a cobalt (1,4-benzenedipyrazolate).
Displacive transitions are also observed in interpenetrating
and interdigitated 3D frameworks. This time, it is only the
slipping motion of the rigid interpenetrated layers which
occurs under the action of the stimulus. This behaviour is
one of the aspects of the gate eect.
43
The original phase can
Fig. 7 Perspective view of MIL-68, with hexagonal and triangular
tunnels.
Fig. 8 Structure of the jungle gym [Zn
2
(1,4-BDC)
2
(DABCO)]xIPA, and a scheme of its intermediary distortion.
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be non-porous although, under a stimulus, it opens.
For instance, the (ZnI
2
)
3
(tpt)
2
framework
44
undergoes
considerable motion of the two interpenetrating (10,3b)
networks during nitrobenzene guest removal and reintroduc-
tion. In the same way, Kitagawa described
45
a copper(II)
coordination polymer [Cu(dhbc)
2
(4-4
0
-bipy]H
2
O which is
non-porous up to 50 bar but opens above, when the pressure
of nitrogen increases.
The reconstructive phase transitions are by far more
rare. Up to now, only [Cu
2
(pzdc)
2
(dpyg)]8H
2
O
46
and
[Ni
2
(4,4
0
bipy)
3
(NO
3
)
4
]
35,47,48
exhibit this behaviour. The rst
solid is a 3D pillared structure. It undergoes a transformation
during the adsorption process, attributed to cleavage/
formation of the Cucarboxylate bond. During adsorption
of methanol and water, it shrinks with a 27,9% contraction
and then expands, but not with methane.
These few examples (and many others) exhibit signicant
changes for the cell volume which reached, until recently,
ca. 40%. They also identify the eect of the stimulus on the
structural changes in the skeleton but, for several reasons (high
disorder of the guests, partial structure determination. . .) in
most of the cases, attention was not paid enough to the
localization of the guests in order to determine what part of
the skeleton is aected by hostguest interactions, and to
evaluate the nature and the intensity of the latter, either
structurally or using computer simulations.
49,50
Moreover,
in situ X-ray powder diraction studies in real time are not
enough developed in order to understand the dynamics of the
evolution during adsorption. This will be discussed later
(section 4.2) in detail from recent examples.
This was recently performed in our group on a new series of
isoreticular solids (families MIL-88
51,52
and -89
53,54
) which
represents the largest expansions ever evidenced: the ratio
between the volumes of the open and closed forms can
reach more than 300%. These solids are iron(III) or
chromium(III) carboxylates with a general formula
[M
III
3
O(X)
3
[
OOC(CH)
n
COO
]
3
]xG (X = CH
3
OH, H
2
O, F).
The organic moieties, always rigid, can be either an alkyl chain
with double bonds (fumarate [
OOC(CH)
2
COO
] (MIL-
88A) and muconate [
OOC(CH)
4
COO
]) (MIL-89) or ben-
zyl moieties (1,4-benzene dicarboxylate (1,4-BDC) [MIL-88B],
naphthalene dicarboxylate (NDC) [MIL-88C], or diphenyl
dicarboxylate (DPDC) [MIL-88D]. They all have an hexago-
nal symmetry (P
6
2
c).
The inorganic cluster is a trimer of M
III
3
O octahedra
sharing a m
3
-oxygen (Fig. 9). Each of the six carboxylate
functions links two octahedra of the trimer, with three above
the trimer and three below. The second COO function of the
dicarboxylate is grafted on another trimer of the structure,
leading to a three-dimensional network.
In the as-synthesized products, the corresponding arrange-
ment gives rise to two types of cavities: large tunnels and large
cages having a triangular bipyramid (TBP) shape, within
which solvent molecules are located (Fig. 9). The vertices of
the bipyramid are occupied by the trimers. The distance
between two trimers of the TBP corresponds to the a
hex
cell
parameter, whereas the distance between the apical trimers of
the TBP refers to the c
hex
parameter. The linking dicarboxylates
are on the oblique edges of the bipyramid; there is no link in
the equatorial plane of the TBP. This absence of a rigid
linker in this case is an essential point for breathing because
the distance between the three equatorial trimers can vary
without constraints under the inuence of a stimulus (in this
case, the hydrogen and van der Waals bonds created by the
occluded species). As in MIL-53, the kneecap role of the
O O axis of the COO group is preserved. For a given length
of the linker, its exibility allows the bipyramid to breathe
because it has two degrees of freedom: (i) the absence of
linkage between equatorial trimers (which avoids any
constraint in the equatorial plane of the bipyramid), and
(ii) the possibility of rotation of the COO group around its
O O axis (Fig. 10).
When the solvent molecules leave the structure, the original
space group is preserved (P
6
2
c), but one observes a drastic
increase of the length between the two non-equatorial trimers
(c
hex
cell parameter), correlated with a decrease of the distance
between the equatorial ones (a
hex
cell parameter). On the other
hand, when the solvent is incorporated in the structure, the
bipyramid attens and its volume increases (Fig. 9). In the
MIL-88D structure using diphenyl dicarboxylate as a linker,
the passage from the empty to the lled form corresponds to
an increase of a
hex
from 10.1 (as) to 20.04 A
(Dd = 10 A
)
whereas c
hex
decreases from 27.8 to 22.9 A
(Dd = 4.9 A
).
Correlatively, the cell volume increases from 2362 to 7968 A
3
Fig. 9 Views of the cages (top) and of the (001) projections (down) of
the dierent forms: dry, as (as synthesized) and open of MIL-88D. The
inorganic trimers are clearly shown on the projection.
Fig. 10 Local movements of the inorganic trimer and of the linker
during the swelling.
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which means a nal volume more than three times the initial
one and reversible atomic displacements of ca. 10A
. . .
The most surprising feature concerns the fact that this
breathing occurs without any apparent bond breaking. It is
dicult to imagine that such variations could occur without a
phase transition. However, if the latter occurred, both phases
would coexist, at least during a few minutes, in the X-ray
powder pattern. This is denitively not the case. During the
dehydrationrehydration process of MIL-88D a continuous
evolution of the pattern, with drastic changes in the position of
the Bragg peaks is observed.
The evolution of the volume can be calculated analytically.
Indeed, a exible bipyramid is a polyhedron in which the
length a of the oblique edges is xed, whereas the length xa
((a
hex
) of the edges of the equatorial plane can vary. In these
conditions, it is easy to show that c
hex
can be expressed as h =
[aO( 3 x
2
)]/O3 and the volume as V = (1/6)x
2
a
3
O(3 x
2
) ,
maximum for x = O2. The value x = O3, for which V = 0,
corresponds to the complete attening of the bipyramid
(Fig. 11). The value of the experimental cell parameters for
MIL-88A-D shows that their open form always corresponds
to a complete lling.
Another interesting point must be mentioned. The pore
opening is strongly dependent of the nature of the solvent,
indicating some selectivity in adsorption. The soaking with
various polar and non-polar liquids shows three degrees of
pore opening: (i) small polar molecules (water and methanol)
and polar solvents induce a small swelling magnitude (68% in
volume); (ii) more hydrophobic but still polar liquids (butanol,
DMF, dimethyl carbonate) generate larger pore openings
(1560%) whereas (iii) pyridine and diethylformamide
completely open the structure. The reason of such dierences
in the magnitude of opening can be found in the characteristics
of the tunnels of the structure and in the nature of the guest
and its associated interactions. Indeed, along the tunnels,
hydrophilic inorganic parts of constant thickness (2.9 A
) and
aperture of 3.7 A
alternate with hydrophobic organic parts

(free aperture 3.2 A
), the thickness of these depending on the

length of the linker. Therefore, the small polar liquids will
interact with the inorganic trimer, non-polar liquids interact
only with the linker via van der Waals, pp or CHp
interactions but the presence of water on the trimer does not
favour their adsorption.
52
Finally, these experiments shed
some light on the kinetics of adsorption, an aspect rarely
taken into account in the literature. It seems that the kinetics
of breathing is distinctive for each MIL-88. For example,
MIL-88A and MIL-88B breathe in a few seconds in the
presence of ethanol, but it takes several days to MIL-88B to
open its pores completely when water and nitrobenzene are
used. In the same way, MIL-88C opens rapidly with pyridine
(o1 min) but slowly with DEF (hours).
The above examples could indicate that breathing is a
general phenomenon, but, on the whole, it is rather scarce
and many MOFs do not swell. This is the case for the well
known zinc (1,4-benzenedicarboxylate) MOF-5
55
and the
series of IRMOF-n
56
which correspond to the replacement
of 1,4-BDC by longer organic ligands. They do not breathe,
despite the existence of large windows (8 A
for MOF-5) which

allow an easy access to dierent molecules and the possibility
of breathing. However, a structure determination at 350 1C
shows
21
that, even without guests, the structure remains
unaltered and therefore insensible to the temperature stimulus.
Why MOF-5 does not breathe? Why the jungle-gym do? The
origin of such an inertness must be found not only from the
topology, as before, but from the structure of the zinc cluster
itself. Indeed, if the symmetry of the cell was taken alone into
account, the presence of the guest species could at least lead to
a rhombohedral cell distortion (elongation or compression
along one diagonal of the cube), which corresponds in both
cases to a decrease of its volume (the volume of a rhombo-
hedron V = a
3
(1 3cos
2
a + 2cos
3
a)
1/2
is maximum for
a = 901) in agreement with the disappearance of the guests.
The terephthalate ions could accommodate such a distortion
owing to the kneecap role of the OCO moieties, which
would allow to privilege one of the four threefold axes of the
original cubic cell if the cluster had a dierent symmetry.
However, considering the tetrahedron of tetrahedra forming
the cluster (Fig. 12) a cooperative movement of the ligands is
impossible during a rhombohedral elongation (for example).
If the ligands of the upper part of Fig. 12 satisfy this
movement because the O O axes of the carboxylates are
perpendicular to the elongation axis, those of the lower part
are almost parallel to this axis, which renders impossible a
rotation of the ligands in the same way owing to the rigid sp
2
conguration of the COO group. MOF-5 illustrates the case
when the conguration of the cluster prohibits breathing
because the positions of some of the ligands do not allow a
cooperative and symmetrical rotation of the linkers. This is
probably due to the octahedral disposition of the carbons of
the carboxylates around Zn
4
, which creates odd cycles between
these carbons, a condition which does not favour breathing, as
seen for MIL-68. Therefore, a new condition for swelling
Fig. 11 The geometry of the bipyramid (left) and the analytical
evolution of the volume vs. x.
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arises from this example: not all inorganic bricks (SBU) can
allow dynamic eects, which are possible only if the carboxylates
have mirror positions around the organic brick.
In conclusion, one can ask a question: why does the jungle
gym [Zn
2
(1,4-BDC)
2
(DABCO)], described above, swell
despite the fact that it is cubic like MOF-5, has the same
topology as MOF-5, and has six ligands in octahedral disposi-
tion around the cluster? The brick is not the same, however:
instead of a tetrahedron of tetrahedra, it is a dimer, but also
there are two types of ligands: four 1,4-BDC and two DABCO
in trans position. The latter are intrinsically monodentate, with
strong and rigid metalnitrogen bonds which do not allow
rotations around N. Therefore, the distortion can only occur
in the square grids formed by four carboxylates which can
present cooperative and symmetrical rotation.
A question arises from all these observations: can empirical
rules be extracted for predicting possible breathings of the
skeleton of hybrid porous solids?
3.4 Some empirical structural rules for possible breathing
(a) The rst rule concerns the inorganic brick (SBU). Inde-
pendently of the nature of the ligand, it seems clear that the
only bricks which permit swelling are those which possess a
mirror plane with the carboxylates in symmetrical position
towards it. This is the case of the dimer of the jungle gym
[Zn
2
(1,4-BDC)
2
(DABCO)] and of the trimer of MIL-88
(Fig. 13(a) and (b)). Otherwise, the situation of MOF-5 occurs
(Fig. 13(c)). This will be an a priori indication for colleagues
discovering new clusters before trying any experiment related
to dynamic eects. This also incites chemists to search for new
inorganic bricks, the currently existing ones being rather
rare.
57
(b) It seems that the ratio C/M (C: number of carbons of the
carboxylate surrounding the cluster; M: number of metallic
atoms within the cluster) is a good indicator of the possibility
of the brick to potentially allow swelling. From the few results
in the literature, it seems that C/M must be Z2 for such an
eect. This is the case for [Zn
2
(1,4-BDC)
2
(DABCO)] and of
MIL-88 (4/2 and 6/3, respectively), but not for MOF-5 and
IRMOF-n (6/4) but this rule needs to be validated in many
other examples.
(c) Breathing eects can only occur with ditopic carboxylates.
Between two clusters, the kneecaps provided by the
O O axes of the dierent carboxylates ought to be parallel
for possible phase rotations. This condition obviously prohi-
bits the use of tri- or tetratopic ligands for expecting swelling.
This is typically the case of MOF-77,
58
MIL-103
59
which
contains tritopic 1,3,5-benzene trisbenzoate and MIL-102
60
formed with the naphthalene 1,4,5,8-tetracarboxylate.
(d) The existence of odd cycles in the structure, both at the
level of the cluster and/or at the level of the topology of the
skeleton, is unfavourable for dynamic eects, owing to their
rigidity (MIL-68, MOF-5 for instance). A particularly illus-
trative example is provided by MIL-101
61
which, despite
favorable conditions (trimeric brick, ditopic ligand) does not
breathe only because most of the windows of the cages are
pentagonal. But, at variance to the other rules, it cannot be
predicted because the topology is known a posteriori.
(e) Breathing occurs only if all the conditions above are
satised simultaneously.
(f) As it will be shown below, as soon as the above
geometrical conditions are fullled, adsorptiondesorption
phenomena can exhibit hysteretic eects (gate eect, multi-
ple-step adsorption. . .) depending on the nature of the guest
and on the relative energies of hostguest and guestguest
interactions.
Fig. 12 Explanation of the absence of breathing in MOF-5. The stars
indicate the impossibility of rotation of the linker in the direction of
the elongation axis.
Fig. 13
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4. Consequences of breathing for academic
knowledge and possible applications
4.1 Sensors and adsorbateadsorbant interactions
The extreme sensitivity of breathing solids toward the action
of a stimulus suggests using them as sensors for evaluating
hostguest interactions for a better understanding of their role
in the dynamics of the framework.
This was realized very recently in our group using the
MIL-53 type.
62
Starting from the hydrated form of
MIL-53(Fe) immersed in water, and placed in the beam of
the synchrotron radiation source, the solvent molecules were
introduced dropwise (an impregnation of MIL-53 in another
solvent leads to an immediate and full exchange with water,
preventing a kinetic study) and the X-ray powder patterns
were collected after each droplet addition in order to follow
structurally the evolution of the cell volume during the
exchange.
Looking rst at the volumes of the fully exchanged samples,
whatever the evolution of the space groups (C2/c -Pnam -
Imcm, when the volume increases), it appears that:
(i) The structural changes occur even for the very smallest
added amounts of guests.
(ii) the topology of the structure of MIL-53 remains
invariant and can be described in all the cases from a reduced
unit cell with a lozenge-based prism. The ratio d/D of the two
diagonals d (smallest distances between chains) and D
therefore characterizes the extent of breathing. Small ratios
relate to the shrunk form of MIL-53 and large ones to the
expanded variety; d is the signature of the strength of the
hostguest interactions and the strong shrinkage of hydrated
MIL-53 shows the strength of the hydrogen bonds which link
the inserted water molecules to both the OH groups and the
oxygens of the carboxylates of the inorganic octahedral
chains.
5
All the experimental data related to the dierent guest
molecules t nicely with the theoretical evolution of the cell
volume vs. d/D (Fig. 14). This proves that all the molecules
involved in this study have each a selective response in terms of
swelling, and the evolution of the cell volumes provides a
quantitative classication of the strength of the hostguest
interactions: the smaller the expansion, the stronger the
interaction.
(iii) The size of the molecules does not play any steric role
during the swelling. Only hostguest (through the OH groups
of the chains and/or the phenyl rings) and guestguest inter-
actions are involved in the process.
(iv) Except for the transient phase with methanol and light
alcohols, only the Bragg reections of the starting and nal
phases are observed without any evolution of their position, at
least on the time-scale of the experiment, implying a dramatic
stepwise expansion of the material, even in the presence of
minute amounts of guests which however open up the struc-
ture (Fig. 15). This is what we called the forceps eect during
the adsorption, indicating that there is no solid solution during
the exchange which corresponds to a biphasic system.
(v) The time-resolved study of the exchange with pyridine,
lutidine and m-xylene also shows that the kinetics of adsorp-
tion is strongly dependent on the nature of the guest. This is
fast for pyridine (o10 mn) while full exchange occurs in one
hour for lutidine and in 90 mn for m-xylene.
Fig. 14 Comparison of the theoretical evolution of the volume vs.
d/D (black squares) with the fully exchanged experimental ones
(red, green and blue lled circles) associated with the changes of
symmetry and space groups during swelling. These discontinuities
illustrate the inuence of hostguest interactions on the phenomenon.
The orange stars correspond to the increase of the swelling of the
transient watermethanol phase at t = 0, 25 and 40 mn.
62
Fig. 15 Evolution of the powder patterns of MIL-53(Fe)H
2
O during
the dropwise addition of lutidine. The Miller indices on the left refer to
the original MIL-53(Fe)H
2
O, and those on the right to MIL-53(Fe)
lutidine. It is clearly seen that the positions of the peaks do not change
during the exchange and that, in this biphasic system, the lutidine
phase appears quasi-immediately after the introduction of the rst
drops, even if the contribution is not very visible on the graph during
the rst minutes (see text).
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(vi) For alcohols (methanol and ethanol), the same forceps
eect occurs when introducing minute amounts of guests,
before the appearance of intermediary phases during the
exchange. The parameters of these transient phases follow
the normal evolution of volumes. This implies that the
methanolhost interactions are rather strong although weaker
than the waterhost ones. Moreover, and, at variance to the
observation with pyridine and lutidine, once the transient
phase formed, further addition of methanol provides a slight
increase of the cell volume (and therefore a decrease of
hostalcohol interactions). Within a certain range of composi-
tions (corresponding to a solid solution behaviour) which
stabilise the intermediate phase, the wateralcohol mixture
within the tunnels plays a specic structural role. In terms of
guestguest interactions, strong hydrogen bonding may be
evoked for explaining this behaviour.
A few structures of the MIL-53(Fe) type with dierent
guests have been solved recently.
6368
They shed more light
on the dierent interactions which are responsible of the
swelling of the tunnels. Three types of interactions are
currently evidenced: (i) guestguest ones (hereafter denoted
GG), (ii) hostguest ones through pp and CHp interactions
between the guests and the terephthalate of the skeleton
(HG-p), and (iii) for N containing guests, interactions
between them and the OH of the structure (HG
N
).
Depending on their relative importance, three situations
occur (Fig. 16), illustrated by the cases of the room- and
high-temperature forms of MIL-53(Fe)quinone
68
and of
MIL-53(Fe), 0.85pyridine:
63
(a) In the room-temperature form of MIL-53(Fe)quinone
(V = 1454 A
3
), whatever the tunnel, all the guest molecules
have the same disposition, parallel to one half of the
terephthalates (BDC) of the skeleton, and creating CHp
bonds with the other half. Between two rows of the same
tunnel, the O O axes of the quinone are orthogonal. This
indicates three types of interactions: (i) strong pp ones
between the centers of the phenyl rings of the BDC and of
quinone (d: 4.06 A
), (ii) medium CHp ones between the H of

quinone and the BDC and (iii) weaker guestguest interactions
(4.99 A
). However, despite this ranking, all the interactions are

relatively weak since the volume is very high as seen in the
curve of Fig. 15.
(b) In the high-temperature form of MIL-53(Fe)quinone,
the interactions are a little weaker than above (V = 1494 A
3
).
The main dierence with (a) concerns the disposition of the
guests between two adjacent tunnels. Whereas the disposition
of quinones within one tunnel remains roughly the same apart
of a small deviation, it becomes orthogonal from one tunnel to
the other instead of parallel in case (a) but the characteristic
distances are very close. This corresponds to a thermally
induced transition, showing also that this hostguest inter-
action drastically depends on weak variations of the tempera-
ture. The same situation is encountered with molecules such
as m-xylene
66
in MIL-53(Fe), and aniline and thiophene in
MIL-47(V).
64,65
(c) When N donors exist in the inserted molecule, the
situation is completely dierent. This is the case for pyridine
(py), DMF
63
and lutidine in MIL-53(Fe).
68
This time, the
molecules are stacked head to tail with a small shift along the
axis of the tunnel. The predominant interaction exists between
the N atom and the OH groups linking two octahedra of the
skeleton chains (d = 2.68 A
for py). Two facts prove that this

interaction is rather strong: (i) the lower volume (V = 1393 A
3
),
(ii) the comparison with what is observed in solid pyridine
(4.7 A
). This enhancement of the strength relates to conne-

ment eects. Otherwise, the GG interaction between two
consecutive py is rather strong since the distance between
two rings is 3.47 A
. The other interactions are weaker.

Some remarks can be made around these situations, parti-
cularly when N donors are involved. Is has been noted that
MIL-53(Fe), as well as MIL-63(Ga)
67
accepts a maximum of
0.85 py per Fe, with no means of introducing more. This
implies some disorder within the tunnels. This is suppressed
with Al, with the 1 : 1 stoichiometry being reached. This time,
the organization of pyridine molecules corresponds to the
situation described in (a).
67
Two conclusions emerge from this
fact: (i) within a structure type, the nature of the metal plays a
Fig. 16 The three dierent dispositions of the guests within the
tunnels of MIL-53(Fe): (a) quinone at 300 K; (b) quinone at 333 K;
pyridine at 300 K.
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role on the relative strength of all the interactions and (ii) small
variations in the amount of the guest in the pore induce drastic
modications of the relative strengths of all the interactions
which occur within the tunnels. However, by exposure to air,
the stoichiometric Al terephthalate loses 0.15 py to give the
classical MIL-53(Al)0.85py with the same characteristics as
the Fe and Ga solids.
A second remark concerns the comparison of the
behaviours of pyridine and lutidine (or dimethylpyridine) in
MIL-53(Fe). The cell volume with lutidine (V = 1575 A
3
) is
considerably larger than for pyridine (V = 1393 A
3
)
suggesting weaker interactions. A preliminary structural
study
68
indicates that while the relative disposition of the
guests remains the same in both solids, the characteristic
distances change. If the lutidinelutidine interactions, even if
slightly longer (3.66 A
), remain almost the same, this is not the

case for the NOH interactions which increase signicantly
because the nitrogen atom is masked by the two methyl groups
surrounding it, weakening the interaction for steric reasons.
The increase of the volume decreases correlatively the
connement eects of the tunnel and the positions of lutidine
are not as constrained as those of pyridine. It explains why the
local environments of lutidine in its solid state or included in
the tunnels are very close. In pyridine, the two states are
dierent.
The third remark concerns the existence of another type
of interaction encountered once: acido-basic one. This was
demonstrated in the solid [Cu
2
(pzdc)
2
(pyz)] (pzdc = pyrazine-
2,3-dicarboxylate, pyz = pyrazine) with permanent 1D
channels with cross-section 4 6 A
.
70
After adsorption of
C
2
H
2
, these molecules reside in the channels in such a way that
the acidic hydrogens of acetylene interact with the terminal
oxygens of the skeleton and electron density calculations
69
proved that there is an overlap between the electronic clouds
of the two atoms, indicative of a weak acidobasic reaction.
The nal remark is more general and concerns a beginning
of justications of the conditions of synthesis in chemistry.
Indeed, looking at the recipes leading to hybrid solids (and not
only in this domain), it can be seen that the solvent is just
mentioned by the authors, with of course, no reason for its
choice. It is the art of the chemist is replied to those who ask
for the question. . . Art can become science too! And probably,
this study of the breathing eect can provide some elements of
an answer. Indeed, it proves indirectly that, even during the
reaction, and depending on the nature of the solvents and of
the species (inorganic bricks (also called Secondary Building
Units (SBU)) and linkers as well) in the solution, the dierent
interactions involved in the process can change as a function
of their strength and orientate the crystallization of one phase
or another.
To conclude this section, the reversible sponge-like
properties of MIL-53(Fe) applies to a variety of simple organic
molecules (including both protic and non-protic species and
polar and non-polar molecules). Its extreme sensitivity and
selectivity toward organic molecules have provided interesting
information about the hostguest and guestguest interactions
which govern the adsorption and separation phenomena, as
well as their dierent strengths. This could nd applications in
the eld of sensors for their detection in small amounts.
4.2 Adsorption and diusion
These phenomena are obviously the rst application of
breathing solids since the adsorption of gases or liquids is
one of the possible stimuli for the swelling eect. We shall
restrict our discussions to physisorption, whereas breathing
eects involving chemisorption can arise, particularly with
molecular solids.
71
This review does not aim at presenting a
large amount of data relative to adsorption; such data are
found in the reviews of the Kitagawa and Rosseinsky groups.
On the contrary, this review extracts from some selected
examples, the specicity of adsorption by breathing matter
in its dierent macroscopic behaviours, in relation with the
structures when data are available. As yet this is not general
and most authors simply mention the adsorption curves
without following at least in situ the evolution of the
X-ray diraction pattern to evaluate the cell parameters. Full
structural determinations of the lled samples are currently
extremely rare.
The isotherms of adsorptiondesorption will rst depend
simultaneously on the nature of the adsorbate and of the
surface of the adsorbant, on the strength of hostguest
interaction, but also on the state of the starting material,
either lled by guests/closed by previous activation, or opened
by the same treatment.
If the starting structure is closed or lled by initial guests, it
is extremely dicult to force entry into the structure. In
doing so, high pressures are necessary for opening.
[Cu(4,4
0
-bipy)(dhbc)
2
]2H
2
O
72
represents a textbook example
for illustrating the gate eect in this case (Fig. 17(a)). No
Fig. 17 (a) Adsorption isotherms of N
2
, O
2
, CH
4
and CO
2
in
[Cu(4,4
0
-bipy)(dhbc)
2
]2H
2
O
72
showing the gate eect as a function
of the nature of the gas. (b) Adsorption isotherm of N
2
in [Co(BDP)
2DEFH
2
O] with the strange ve steps.
74
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adsorption is observed at low pressures except for CO
2
and the
pressure threshold for adsorption strongly depends on the
nature of the gas. The pressure of opening is an indirect
signature of the energy of adsorbate/adsorbant interaction
(or the exothermic enthalpy of adsorption, unfortunately
scarcely measured). The larger the enthalpy, the lower the
threshold. This behaviour was also observed during the
adsorption of methanol by [Cu
2
(pzdc)
2
(dpyg)]8H
2
O.
73
This
eect opens large possibilities in separation processes. This will
be developed in section 4.3.
Until very recently, it was thought that this behaviour
corresponded to a one-step transition, but a recent paper by
Long
74
with the study of the adsorption of N
2
by cobalt
(1,4-benzenepyrazolate (BDP)) [Co(BDP)2DEFH
2
O] shows
that the problem is more complex. This structure is topo-
logically equivalent to the jungle gym [Zn
2
(1,4-BDC)
2
(DABCO)],
with dimeric corner-sharing Co tetrahedra replacing the Zn
dimers. The activation of the tetragonal solid distorts the
structure in a way not solved for the moment, but probably
of the same type as MIL-53. During the rst stages of the N
2
adsorption at low pressure and 77 K, the isotherm exhibits
an unprecedended ve steps (Fig. 17(b)), the last one corres-
ponding to the characteristics of the original unit cell.
Increasing slightly the temperature of adsorption (87 K)
makes the steps less and less visible. The reason of this strange
behaviour is currently unknown but in situ measurements of
the evolution of the diraction patterns vs. pressure is
currently under way. Anyhow, this example is interesting
because it may be supposed that the successive plateaus
correspond to the xation of N
2
on dierent sites of the
distorted structure. The resolution of the dierent structures
during adsorption will be of paramount importance for the
understanding of this phenomenon. Note that the isotherm of
adsorption of H
2
exhibits only a single step.
At variance to the above cases, the structure of
MIL-53(Cr,Al) opens under activation. For a better under-
standing of the adsorption of gases, a detailed study, both
experimental and theoretical, was undertaken when H
2
, CO
2
and CH
4
and homologous alkanes are concerned, both on
MIL-53(Cr,Al) solids and their counter example MIL-47 (V),
which remains opened and does not breathe. The main struc-
tural dierence between the two types results from the presence
or not of m
2
-OH groups linking the octahedra of the chains.
Experimentally, two situations occur. In the rst, the
adsorption curves exhibit a classical type I behaviour; no
unusual behavior is observed in the curve of amount adsorbed
vs. pressure (Fig. 18). This situation is encountered for all the
solids with hydrogen and methane and only with MIL-47
adsorbing CO
2
. The second, encountered only a few
times,
47,7577
belongs to a new case of adsorption in the eld
of hybrid porous solids. It is a two-step behaviour. After a fast
adsorption at very low pressure, the curve reaches a plateau
in a certain range of pressure before increasing once more.
Even at 70 kbar, saturation is not reached. This phenomenon
occurs only with MIL-53(Cr,Al) during CO
2
adsorption
(Fig. 19). As mentioned in ref. 77 this two-step behaviour is
still dicult to understand.
For this reason, we undertook a series of experiments
combining for each gas in situ powder diraction in real time
at various pressures, with microcalorimetry and molecular
simulations in order to provide complementary elements of
explanations for such an unusual feature. Powder diraction
was performed at the ESRF Grenoble using a new set-up
placed in the beam. The gas is introduced at increasing
pressures in the tube containing the activated solid and the
powder patterns are collected for each pressure. This gives
the evolution of the cell parameters for each pressure with the
possibility, if the product is suciently well crystallized, to solve
the complete structure in order to provide structural informa-
tion about the location of the guests. Quasi-elastic neutron
scattering (QENS) permits access to the dynamics of diusion.
Microcalorimetry provides experimentally the thermodynamic
elements, in particular the adsorption enthalpy, which indicates
the strength of the guesthost interactions. Finally, molecular
simulations (DFT, Monte Carlo, molecular dynamics) combine
experiment and theory for the t of the isotherms and give an
image of the movements of the guests within the tunnels and
their jumps from one adsorption site to another.
Our recent series of papers
7987
shed some light on the
explanation of adsorption phenomena.
Concerning hydrogen,
78,79
the enthalpies of adsorption are
very weak (37 kJ mol
1
) and the solids do not breathe. QENS
shows
7987
however that MIL-47(V) and MIL-53(Cr) have
some points of dierence in their behaviours in terms of
self-diusivity. In both cases, diusivity coecients D indicate
an orientationally averaged motion, but MIL-47(V) exhibits a
higher diusivity than MIL-53(Cr) , which is consistent with a
lower activation energy (experimentally 0.6 kJ mol
1
for
MIL-47; 1.6 kJ mol
1
for MIL-53; calculated 0.6 and
1.3 kJ mol
1
, respectively). In particular, the self-diusivity
coecient of MIL-47(V) (2 10
6
m
2
s
1
at 300 K) is much
higher than those observed in liquid hydrogen (10
8
m
2
s
1
)
and in zeolites (10
8
10
10
m
2
s
1
). In these conditions, it is
illusory to try to localize H
2
molecules in the tunnels.
However, in order to more deeply understand the diusion
mechanism of H
2
in the tunnels, molecular dynamics simula-
tions were performed. They show that the diusion of H
2
in
MIL-53(Cr) is mainly governed by the interaction between H
2
and the m
2
-OH groups of the chains, leading to a 1D diusion
Fig. 18 Adsorption isotherms of H
2
78
in MOF-5, MIL-53(Al) and
HKUST-1 (a copper 1,3,5-benzene tricarboxylate).
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along the tunnel via a jump sequence involving these OH
groups. In contrast, in MIL-47(V), the simulation shows a
three-dimensional diusion process with random motions
within the pore of the material.
More attention has been paid to CH
4
and CO
2
. In terms of
breathing, CH
4
, like H
2
does not lead to swelling as proved by
its Type I isotherms.
75
In MIL-47(V), ve molecules of
methane per tunnel are present at 30 bar. The experimental
adsorption enthalpies increase from 15 to 19.5 kJ mol
1
between 0 and 20 bar, and suggest that methane probes
MIL-47(V) as a homogeneous energetic surface with no pre-
ferential adsorption sites within the pore. QENS experiments
indicate strong similarities with those obtained for H
2
:
unidirectional diusion, high self-diusivity coecient
[4.2 10
7
m
2
s
1
at 300 K], but lower than for hydrogen.
The comparison of the probability density in both solids
MIL-47(V) and MIL-53(Cr) is fruitful (Fig. 20). Except for
adsorption enthalpies which remain constant (17 kJ mol
1
),
it once more evidences the inuence of the presence of m
2
-OH
groups on the unidimensional process. It shows that the lower-
energy regions are centered around the m
2
-OH as well as at the
middle of the tunnel. In MIL-47(V), this latter region is much
more favourable for the methane molecules. In MIL-53(Cr),
one can imagine a sequence of jumps between two consecutive
OH groups. According to QENS data, it is possible to estimate
average jump lengths of 5.6 A
(MIL-53) and 8.1 A
(MIL-47)
(with a large distribution) with characteristic intervals of
7.3 and 6.0 ps, respectively.
With CO
2
, the situation is completely dierent. It breathes
with the m
2
-OHcontaining MIL-53(Al) and (Cr) but not with
MIL-47(V) which does not possess OH groups. Our in situ
structural study of MIL-53(Cr) during adsorption and
desorption of CO
2
81
proves rst that, when activated the
structure is open with a cell volume of 1486 A
3
. Second,
during the rst steps of adsorption (Fig. 19), a large amount
of CO
2
is adsorbed (two molecules per unit cell) and leads to a
plateau in the adsorption isotherm) between 1 and 4 bar.
In situ diraction shows that, at that moment, the structure is
contracted by ca. 32% (V = 1072 A
3
instead of 1013 when
water is adsorbed). A further adsorption of CO
2
at higher
pressures reopens the framework while accepting additional
CO
2
molecules into a newly formed tunnel (ca. 9 molecules per
unit cell). From the structure determination at 2 bar, (Fig. 21),
it appears that the CO
2
molecules interact with the two
opposite chains corresponding to the small diagonal of the
rhomblike section of the tunnel. The linear molecules are lined
up along the axis of the latter, with an intermolecular distance
of 3.4 A
, in the same order of magnitude as distances existing

in solid CO
2
(3.243.57 A
) and indicates strong guestguest

interactions within the tunnel. Regarding the interactions
between CO
2
molecules and the framework, the interatomic
distances suggest two scenarios: (i) interaction between the
carbon atom of CO
2
with the oxygen atom of the OH group of
the chain (d
CO
= 2.8 A
) and (ii) as the CO

2
molecule
has a strong quadrupolar moment (1.4 10
35
C m), a
quadrupolardipolar interaction between CO
2
and OH
(the distance between the two oxygens is 3.06 A
).
To improve the knowledge of these interactions, in situ IR
spectroscopic experiments were performed in the same
conditions as for the diraction studies. They provide
an elegant signature of the dynamics of swelling during
Fig. 19 Adsorption isotherms of methane and carbon dioxide
75
in MIL-53(Al) (left) and the corresponding enthalpies of adsorption.
Fig. 20 2D free-energy maps of methane in MIL-53(Cr) (left) and
MIL-47(V) (right) at 250 K obtained through the xz plane of a given
tunnel for a loading of ve CH
4
molecules per unit cell. White
corresponds to regions of lower free energy, and black to regions of
higher free energy. The dashed lines are guides to the eye.
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adsorptiondesorption.
82,83
The increasing amount of
adsorbed CO
2
is estimated from the evolution of the integrated
intensity of the n2 bands between 645 and 665 cm
1
. The shift
from1022 to 1017 cm
1
of the n18a ring mode of the terephthalate
entities corresponds to the passage from the open to
the closed forms of the skeleton. At lower wavenumbers
(550600 cm
1
), the evolution of the spectra characterizes
the distortions of the framework under the action of the
CO
2
molecules. The split of the n2 band into two components
at 653 and 662 cm
1
also reveals that the main interaction
involves the formation of electron donoracceptor complexes
between the C atom of the CO
2
molecule and the electron
donor center of the framework. Clearly, CO
2
acts as an
electron acceptor while the OH group plays the role of donor.
Incidently, this is the rst time that such an interaction
between CO
2
and OH is characterized in a solid.
Computer simulation experiments provide more details
about the phenomenon. For MIL-53(Al),
84,85
the calculated
enthalpy of adsorption is 37 kJ mol
1
(exptl. 35 kJ mol
1
)
and the distances between the oxygens of CO
2
molecules and
the hydrogens of the OH groups are calculated as 1.94 and
2.02 A
. In conformity with the structural data at 2 bar

(2 molecules/u.c.), a double interaction between the oxygen
atoms of the adsorbate and the two hydrogen atoms on the
hydroxyl groups on opposite pore walls is the preferential
adsorption arrangement and is responsible of the shrinkage of
the tunnel. At increasing pressures, the favourable geometry is
broken, due to the interaction between the additional CO
2
molecules. The resulting arrangement corresponds to a less
energetic single interaction between the adsorbate and the OH
group, and therefore, the structure reopens. The same study
with MIL-53(Cr)
86
conrms the results obtained with MIL-
53(Al), with an enthalpy of adsorption is 35 kJ mol
1
. It
provides also an important new information which could not
be obtained experimentally due to the extremely fast CO
2
uptake: the situation when only one CO
2
molecule is in the
tunnel instead of two at the plateau (Fig. 22). For one
molecule, calculations prove that the structure remains open
and that the contraction occurs only above two CO
2
molecules
per unit cell (in agreement with the experimental results). The
structure begins to re-expand between 5 and 6 guests cell
1
.
This result is very important for the explanation of the
phenomenon. It shows that, even for molecules having a high
enthalpy of adsorption, breathing occurs only for a minimum
number of guests in the cell, a minimum which corresponds to
the establishment (for reasons of proximity) of strong
guestguest interactions within the tunnel These CO
2
CO
2
interactions act as a backbone for the adsorbed species and
allow the double interaction between the oxygen atoms of the
adsorbate and two hydrogen atoms on the hydroxyl groups on
opposite chains. This symmetry and a threshold intensity
of the interactions is essential for the occurrence of the
contraction. This last remark regarding intensity is crucial
and explains why MIL-53 does not breathe with methane. Its
enthalpy of adsorption is too low and, mainly due to the
spherical and apolar characters of methane, rules out the
development of strong guestguest interactions which could
lead to a contraction. In a recent paper,
87
we prove that with
superior linear alkanes, both the larger enthalpies (which
increase roughly by 10 kJ per additional carbon in the chain)
and their stronger interactions make that the corresponding
solids breathe once more.
In other words, explaining the swelling phenomenon is
indeed dicult because many parameters occur in order to
allow the dynamic movements. However the general picture is
becoming more clear now. Beside this important improve-
ment, other aspects are of course of potential interest in
relation with the breathing phenomenon. They concern
dedicated properties and applications which are detailed
below. They have not received the same level of attention as
above but future studies should be forthcoming.
4.3 Adsorption and separation
Separation is based on the selective times of adsorption of
dierent molecules on a surface or by the dierent boiling
Fig. 21 The CO
2
molecules in the shrunk tunnel. The OH groups of
the skeleton appear as large grey spheres in the chains.
Fig. 22 Top: Calculation of the evolution with time of the cell volume
of MIL-53(Cr) for dierent values of the number of CO
2
molecules
within one unit cell; Bottom: the evolution of the cell volume vs. the
number of CO
2
molecules within the cell. Lines are simply a guide for
the eye.
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temperatures of the constituents of a mixture. It is a strategic
problem for industry which, most of the time, requires the use
of energy to perform these separations, and an evaluation of
the induced costs. Hybrid solids can provide in some cases a
solution at room temperature in order to circumvent the
problem. We shall present two examples in this area, using
the same family of solids, one breathing (MIL-53(Cr)), the
other non-breathing (MIL-47).
It has been seen above that depending on their nature and
that of the skeleton, molecules are oriented in a specic
manner within the pores, which governs their time of residence
on the surface. It is therefore assumed that isomers, despite
similar orientations, will present dierent energies of surface
adsorption in relation with the positions of the substituents in
the molecule.
With this in mind, the De Vos group
66
has recently proved
that the non-breathing MIL-47, which remains open whatever
the guest (see above) is a very good material for the separation
of the isomers of xylene. Their separation, in a mixture with
ethylbenzene is quantitative and eective in less than 20 min at
room temperature.
The second example uses MIL-53(Cr). It was previously
seen that, when it is activated (open), the CO
2
adsorption
corresponds to a two-step behaviour whereas that of methane
shows a type I isotherm. When adsorption measurements are
performed on the hydrated form of this solid, the situation
becomes completely dierent (Fig. 23). The adsorption of
methane becomes close to zero while, for CO
2
, the curve is
characteristic of a gate eect, and therefore of a one-step
behaviour.
88
All the examples above (threshold of the gate eect depend-
ing on the nature of the gas for the same structure type, two-
step behaviour depending on the activation of the solid,
dierent temperatures of adsorption. . .) make breathing solids
excellent candidates for separation at room temperature,
playing on the dierent parameters cited above. They are
highly selective towards mixtures of guests and could represent
a cheap alternative for current processes.
4.4 Conducting materials
This title seems surprising as hybrid solids are well known for
being insulators. This relates to a general feature of hybrid
solids. Except in a few cases with copper-based solids, the
metals of the skeleton are in a single valence state. The idea
was therefore to introduce mixed-valency for metals using a
post-treatment procedure. This was performed electro-
chemically by introduction of lithium in MIL-53(Fe).
89
It
must be remembered that this solid, in its dehydrated form,
is shrunk (V = 900 A
3
) at variance to its Cr rand Al
analogues. The process was followed by in situ methods
(diraction, Mo ssbauer spectroscopy) in real time. These
prove that (i) both Fe
2+
and Fe
3+
coexist in the nal solid
with a maximum ratio Fe
2+
: Fe
3+
of 3 : 2; (ii) the trans-
formed solid becomes a conductor and exhibits both electronic
and ionic conductivity; (iii) the structure swells during the
charging process with a complete opening of the structure
(V = 1562 A
3
) and the process is reversible during discharge.
The breathing occurs not only from the introduction of
lithium but also from the simultaneous insertion of the
electrolyte. The extent of the swelling depends on the nature
of the latter. This presence of electrolyte ensures better
contacts in the half-cell during the conductivity measurements
and opens possibilities of using breathing solids as new
electrode materials for fuel cells.
Incidently, and beside its aspect, it must be noted that, after
this work, the introduction of lithium in MOFs has become
topical for hydrogen storage purposes. From ideas of
Goddard
90
and Blomquist,
91
some attempts were successfully
realized
92,93
for introducing Li chemically in the structures of
MOFs. This indeed improves the performances of H
2
storage
of these MOFs.
4.5 Drug storage and delivery
The synthesis of new bioactive compounds of very high
molecular weight with therapeutic activity and/or with a low
aqueous solubility becomes more and more complex and the
processes of their commercialization very slow. This requires
the use of carrier systems to improve the activity of known
molecules. These systems usually allow a better control of the
drug plasmatic eects, increasing the eciency and decreasing
the toxicity, as well as an increase in the drug stability by
protection of the biodegradation. Until recently, polymeric
and mixed systems have been proposed for a better controlled
release of drugs.
94,95
In particular, mesoporous inorganic
solids such as the ordered mesoporous silicas (pure or func-
tionalized by a post-synthesis modication) are now used.
96
However, this process leads to a decrease of the drug storage
capacity.
97,98
Recently, our group proposed an alternative route
(the hybrid route), using for the rst time porous MOFs as
new controlled delivery systems
99
because of their high pore
volume, regular porosity and the presence of tunable organic
groups within the framework which allow an easy modulation
of the size of the pores. The rst example concerned the
adsorption of the model molecule ibuprofen in the rigid MOFs
MIL-100 and MIL-101 with mesopores. They exhibit a very
high drug storage capacity, up to an unprecedented 1.4 gram
Fig. 23 Comparison of the performances of anhydrous and hydrated
forms of MIL-53(Cr) in terms of CO
2
and CH
4
adsorptions, indicating
a high selectivity for the latter.
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of drug per gram of porous solid, and a complete drug
controlled release under physiological conditions from
3 to 6 days (Fig. 24).
For studying the eect of this breathing phenomenon on the
drug adsorption and delivery properties of pharmacological
molecules, Ibuprofen (hereafter denoted Ibu) was once more
chosen as a test molecule for looking at two points (i) the
inuence of breathing on drug adsorption and (ii) the
characterizations and the induced eects of the hostdrug
interactions (including kinetics of delivery in a simulated
physiological environment). Two exible materials were used:
(i) MIL-53(Cr) solid as a model material despite the well-
known toxicity of chromium compounds and which, when
activated, presents its open form; (ii) the much less-toxic iron
analogue MIL-53(Fe) (rat oral dose: DL
50
(Fe) = 30 g kg
1
,
DL
50
(terephthalic acid 46.4 g kg
1
) which is closed after
activation.
Both solids adsorb ca. 20 wt% of ibuprofen
100
(Fig. 24). The
lled samples are non-porous. The nal cell volume after
treatment is roughly the same for the two compounds
(V E 1400 A
3
), corresponding to a slight contraction (6%)
for the opened MIL-53(Cr) and an important expansion
(55%) for the Fe analogue. Using IR spectroscopy, the shift
of the n(CQO) band of the carboxylic group of Ibu (1695 -
1725 cm
1
) correlated to that of the vibrational n(OH) band
of the inorganic chains (3656 - 3639 cm
1
) indicates the
formation of a strong hydrogen bond between these two
groups. The dierent
1
H and
13
C solid-state NMR character-
izations conrm this fact and also provide information about
the dynamics of ibuprofen within the tunnel.
13
C NMR
indicates a slight conformational distribution of the drug in
the pores, which concerns essentially the aromatic part of Ibu.
However, it shows also that the mean conformation is close to
that of the pure form of ibuprofen. All these features were
conrmed by DFT calculations which also suggest (Fig. 25),
beside the main interaction, the possibility of van der Waals
and/or CHp interactions between the hydroxyls of the skele-
ton and the methyl groups of Ibu. This provides an estimate of
the drugmatrix interaction energy of 57 kJ mol
1
, larger
than that observed for CO
2
in MIL-53(Cr) (35 kJ mol
1
).
The most striking feature of the phenomenon concerns the
kinetics of delivery. In the rst place, the delivery is complete.
The kinetic study was performed using a simulated body uid
(SBF) with similar inorganic composition as human plasma, at
37 1C under continuous stirring. Surprisingly, a very slow
delivery, complete only after 3 weeks, is observed with clearly
two steps in the process. Despite the slight changes of slope,
the results were treated as a rst approximation, as having a
zero-order kinetics. A model was proposed to explain this fact.
These facts suggest a specic behaviour of exible frame-
works on the adsorption of species (gases, vapours, drugs...),
compared to rigid ones. They are adaptative and take, within
the same topology, a conguration where the interactions
between guest molecules and the framework are optimised
while taking also into account the steric hindrance of the guest
molecules and their number. If the latter increases due to a
additional stimulus (increase of pressure for instance), the
structure will open more. This adaptability might explain the
long time of delivery. Indeed, due to its exibility, MIL-53 can
be considered as an intrinsically tailor-made container which
ts with the geometrical and energetical characteristics of the
guest and therefore enhances the connement eects. If the
Fig. 24 Ibuprofen delivery performances of exible MIL-53(Cr) and -(Fe) (left) and of rigid MIL-100 and MIL-101 (right).
Fig. 25 (a) Localization of ibuprofen in the pores of MIL-53(Fe);
comparison of the conformations of ibuprofen conned in the tunnels
(b) and in its pure solid form (c).
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latter are optimized, they will not favour rapid evacuation of
the guests and therefore explain the long times for release.
Finally, we could expect very long therapies using exible
MOFs for drug delivery. Also, the possibility of having drug
carriers with zero-order kinetics represents an important
progress since a unique administration could be provided.
This would lead to a stable blood concentration, a mini-
misation of the toxicity eects as well as a decrease in patient
discomfort. Moreover, the slow release will protect the
drug from degradation processes by increasing its plasmatic
half-life, its bioavailability and therefore its eciency.
5. Conclusion
At the outset, breathing eects were considered as laboratory
curiosities. Their careful academic study has allowed to
understand not only the structural requirements for such a
phenomenon, but also its dierent manifestations and their
reasons. They result from the juxtaposition of structural
characteristics of the skeleton (mainly the existence of weak
points in the structure which allow exibility), of the nature of
the internal surface, on the complex and competitive nature of
the dierent interactions (guestguest and hostguest). Beside
these academic features, some potential applications of this
eect have appeared, due to the large amounts of species that
the expansion of the cells allow to store compared to rigid
frameworks. These applications relate to energy and sustain-
able development (adsorption, separation, storage. . .), and to
health (drug delivery). Their development is ongoing.
Acknowledgements
The authors are grateful to their colleagues in Versailles and
also to the groups of M. Daturi (Caen), H. Jobic (Lyon),
P. L. Llewellyn (Marseille) and G. Maurin (Montpellier) for
their outstanding contributions to the knowledge of the
breathing eect.
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Large Breathing Effects in Three-Dimensional Porous Hybrid Matter

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Large Breathing Effects in Three-Dimensional Porous Hybrid Matter

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This article was published as part of the

2009 Metalorganic frameworks issue

. This paper will analyze some of these solids

) and often occur during displacive (without bond

in the best case).

) and therefore (iii) the steric hindrance

). For the same x, the completely dehydrated sample

, the pitch of the helix

. The length between the two terminal carbons of

for the elongated

in the expanded empty MIL-53-ht (Fig. 5(c)). The distance is

in MIL-53-as when the template H

(Al, Cr) for the whole

(hydrated form) and

when anhydrous], indicates an enhancement of the pp

), allow the opening of the

) unexpected decrease of the length

alternate with hydrophobic organic parts

), the thickness of these depending on the

for MOF-5) which

), (ii) medium CHp ones between the H of

). However, despite this ranking, all the interactions are

for py). Two facts prove that this

). This enhancement of the strength relates to conne-

. The other interactions are weaker.

), remain almost the same, this is not the

(MIL-53) and 8.1 A

, in the same order of magnitude as distances existing

) and indicates strong guestguest

) and (ii) as the CO

. In conformity with the structural data at 2 bar

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