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Cite this: Dalton Trans., 2011, 40, 9977
www.rsc.org/dalton PAPER
Intercalation synthesis of functional hybrid materials based on layered simple
hydroxide hosts and ionic liquid guests a pathway towards multifunctional
ionogels without a silica matrix?
Emilie Delahaye,
a
Zailai Xie,
b
Andreas Schaefer,
b
Laurent Douce,
c
Guillaume Rogez,
c
Pierre Rabu,
c
Christina G unter,
d
Jochen S. Gutmann
a,e
and Andreas Taubert*
b, f
Received 4th May 2011, Accepted 27th June 2011
DOI: 10.1039/c1dt10841g
Functional hybrid materials on the basis of inorganic hosts and ionic liquids (ILs) as guests hold
promise for a virtually unlimited number of applications. In particular, the interaction and the
combination of properties of a dened inorganic matrix and a specic IL could lead to synergistic
effects in property selection and tuning. Such hybrid materials, generally termed ionogels, are thus an
emerging topic in hybrid materials research. The current article addresses some of the recent
developments and focuses on the question why silica is currently the dominating matrix used for
(inorganic) ionogel fabrication. In comparison to silica, matrix materials such as layered simple
hydroxides, layered double hydroxides, clay-type substances, magnetic or catalytically active solids, and
many other compounds could be much more interesting because they themselves may carry useful
functionalities, which could also be exploited for multifunctional hybrid materials synthesis. The
current article combines experimental results with some arguments as to how new, advanced functional
hybrid materials can be generated and which obstacles will need to be overcome to successfully achieve
the synthesis of a desired target material.
Introduction
Ionic liquids (ILs) have attracted tremendous interest in the recent
past. The advantages of ILs have been put forward and discussed
extensively,
15
sufce to mention here that there is virtually no
area of chemical research, development, and engineering that
has not at least seen some attempts of making use of ILs. A
eld, which has recently picked up momentum is the general
area of (inorganic) materials chemistry in and with ILs. Initially,
many publications have focused on the synthesis, stabilization, and
application (in particular in catalysis) of inorganic nanoparticles
in and fromILs.
613
Several studies have shown that it is possible to
stabilize inorganic nanoparticles in ILs.
6,1425
Their properties such
as size and size distribution (and hence their optical and catalytic
properties) can be adjusted by a number of parameters such as the
chemistry of the IL, the inorganic, the precursor for the inorganic,
a
Max Planck Institute for Polymer Research, D-15528, Mainz, Germany
b
Institute of Chemistry, University of Potsdam, Karl-Liebknecht-Str. 24/25,
Building 26, D-14476, Golm, Potsdam, Germany. E-mail: ataubert@
uni-potsdam.de; Tel: +49 (0) 331 977 5773
c
Institut de Physique et Chimie des Mat eriaux de Strasbourg, UMR7504
CNRS-Universit e de Strasbourg, France
d
Institute of Earth and Environmental Sciences, University of Potsdam, D-
14476, Golm, Germany
e
Physical Chemistry, University of Duisburg-Essen, D-45117, Essen,
Germany
f
Max Planck Institute of Colloids and Interfaces, D-14476, Potsdam,
Germany
and the reaction process.
23,2633
In particular, the interaction of
the IL with the growing inorganic surfaces appears to be a key
point in the growth process; it is however so far only poorly
understood.
23,32
Initially, relatively simple synthetic processes such as the
chemical reduction of metal salts in ILs have been studied and a
wide variety of (mostly metal oxide and hydroxide) nanoparticles
has been reported.
1213
Later porous materials such as metal
organic frameworks (MOFs),
89,3435
mesoporous silica,
3640
and
nanostructured rutile
38,41
have also been synthesized from ILs.
Recently, nanoparticle synthesis protocols with a more elegant
experimental design have been reported. For example, Janiak
and coworkers and Santini and colleagues have published the
synthesis of inorganic nanoparticles, predominantly metals, using
zero-valent metal precursors such as metal carbonyls as starting
materials.
24,4248
The nanoparticles formby thermal decomposition
of the metal carbonyls to the respective metal particles. The
interesting aspect of this approach is that the reactions need
not predominantly be diffusion limited, as is the case with
conventional chemical reduction processes. This may not always
be an important point as far as work in a research laboratory is
concerned. It is, however, important in the context of conducting
reactions in large volumes, where the IL viscosity, which can be
orders of magnitudes larger than that of conventional (molecular)
solvents,
12,4
makes the processing difcult. As a result, the
approach by Janiak, Santini, and others is one option towards
alleviating issues with the synthesis of nanoparticles in ILs.
This journal is

The Royal Society of Chemistry 2011 Dalton Trans., 2011, 40, 99779988 | 9977
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Besides nanoparticle synthesis in ILs, the fabrication of
nanoparticle dispersions is an area that has, so far, largely been
ignored. The authors are only aware of a few publications dealing
with the synthesis, structure, and properties of dispersions of
inorganic particles in ILs. Nakashima and Kawai showed that
CdTe nanocrystals with a positively charged surface are efciently
extracted into the hydrophobic IL 1-butyl-3-methylimidazolium
bis(triuoromethylsulfonyl)imide [Bmim][NTf
2
].
49
Guerrero-
Sanchez et al. and Altin et al. have studied the rheological
behavior of magnetic nanoparticle dispersions in ILs.
5051
Lunstroot et al. have reported the dispersion of luminescent
nanoparticles in ILs
52
and Khare et al. have synthesized
dispersions of magnetic Fe
3
C nanoparticles in ILs.
53
As some
of these dispersions exhibit rather interesting properties, further
research and development into this area can be envisioned.
54
Arguably, however, within the eld of materials chemistry in
and with ILs, ionogels have attracted the most rapidly growing
attention. Ionogels are hybrid materials based on a (continuous)
matrix and an IL.
55
The most popular inorganic matrix at the
moment is silica.
56
Obviously this stems from the fact that
silica chemistry is well established and countless strategies for
the synthesis, structuring, functionalization, and application of
silica have been published.
57
Vioux and colleagues have recently
reviewed the state of the art in silica ionogel research,
56,58
but a few
key studies need to be discussed here as well.
Silica ionogels are interesting because they are easily syn-
thesized, transparent, and exhibit properties such as high
ionic conductivity,
55,59
luminescence (if doped with a lumines-
cent species),
52,6061
or lithium ion transport (if containing a
Li source).
6263
Ionogels are often thermally stable (until ca.
250

C)
55,59,6466
or exhibit an interesting change of the ILproperties
upon connement.
6568
The interaction strength between the IL
and the silica inuences the dynamics (ionic mobility) of the
whole system and can be affected by sample preparation (in
situ
23,32,55,5960,67,6970
or post-synthesis functionalization
6566
) but also
by the structure and chemical composition of the IL. N eouze
et al. found a liquid-like behavior of [Bmim][NTf
2
] conned
in silica.
59,70
Liu et al. have shown that the surface of SiO
x
nanoparticles leads to a melting point depression of imidazolium
ILs.
71
Sha et al. have used computer simulations to study the
interaction of ILs with inorganic surfaces; they suggest that
negative surface charges lead to a bilayer formation in 1-ethyl-3-
methylimidazolium hexauorophosphate [Emim][PF
6
].
72
N eouze
and colleagues have demonstrated that organically crosslinked
silica nanoparticle networks exhibit a short range order within
the organic bridges and that these hybrid materials are capable
of anion exchange.
7375
Finally, G obel et al. have shown that
the pore wall of silica ionogels can readily be functionalized
with organic pendant groups.
65
These groups strongly affect the
behavior of the ILs in the ionogels. For example, additional
phase transitions appear in the DSC. These changes depend
on both the pore wall chemistry and the IL composition. The
above studies therefore suggest that the surface/IL interaction is
a key parameter for property tuning of the IL (and therefore the
ionogel). As a result, pore wall modication of silica constitutes
an attractive, yet largely unexplored, approach for property tuning
of ionogels for a large variety of applications (of course, pore
wall modication as such has been explored in silica materials
synthesis).
7682
Despite the many advantages of silica, it is evident to the
inorganic and hybrid materials chemist that there must be more
thanone matrix material, silica, whichis suitable for the generation
of useful ionogels. There are, however, surprisingly few examples,
where inorganic matrices other than silica have been used for
ionogel formation (there are of course polymeric or organic
gelators,
56,61,8390
but this is not the topic of this article).
Afewstudies report on the behavior of ILs in carbon nanotubes
and graphite. Chen et al. demonstrated that connement of 1-
butyl-3-methylimidazolium hexauorophosphate [Bmim][PF
6
] in
a carbon nanotube raises the IL melting point by 200

C.
91
Graphite also strongly affects the phase behavior of ILs.
9294
In
both cases, pp interactions between the matrix and the IL cations
have beenheldresponsible for the changes inILproperties. Indeed,
Dou et al. have recently shown that ILs forman ordered layer close
to a graphite surface, which strongly attaches to the graphite and
leads to a pronounced diffusion of the IL components parallel to
the graphite surface.
95
Exploiting this interaction, ILs have been
used for the exfoliation of graphite into graphene-like sheets.
9697
Besides silica and carbon, there are only very few examples of
inorganic ionogel matrix materials.
40,4951
Using a somewhat exotic
matrix, mesoporous silver, N eouze and coworkers have postulated
that silver-conned ILs exhibit a two-phase regime, where the IL
close to the pore wall is solid, and the IL in the center of the pore
is liquid-like.
98
The porosity of the silver matrix is rather low and
the IL fraction correspondingly small. The investigation of such
an ionogel is therefore quite a challenge. Vioux and coworkers
have reported on an SnO
2
-based ionogel, although the focus of
this study was on the synthesis of porous SnO
2
(rather than the
structure and properties of the initial ionogel) using different ILs
as templates, which were subsequently removed.
68
Finally, there are two reports on the synthesis, structure, and
properties of IL-intercalated organic/inorganic hybrid materials.
Wu et al. have synthesized zinc hydroxyuoride nanobers from
Zn
5
(OH)
8
(NO
3
)
2
using a microwave approach in the IL 1,2,3-
trimethylimidazolium tetrauoroborate [Tmim][BF
4
].
99
These au-
thors claim that their reaction product forms and organizes due to
hydrogen bonding and pp stacking of the imidazoliumlayers and
the BF
4
-
anions. Unfortunately, no evidence of either interaction
was presented in the publication. It is thus not clear at the moment
if the structure proposed by the authors is the one actually present
inthe material. The hydrogenbonding inparticular must be viewed
with care, because the authors used a tri-substituted imidazolium
cation where the most acidic proton in the imidazolium moiety
(the 2-H) is replaced by a much less efcient hydrogen donor, a
methyl group.
Oaki et al. report on a fundamentally different approach
towards anIL/inorganic hybridmaterial.
100
Unlike the approaches
described above, it is not based on the intercalation of the complete
IL. Rather, the authors intercalated the respective imidazole into
the interlayers of the host material, a-Co(OH)
2
, and subsequently
transformed it to the desired imidazolium cation by reaction
with the corresponding alkyl bromide. The authors claim to have
generated a novel hybrid material based on a layered inorganic
matrix and an intercalated IL. However, the X-ray data of the
two materials before and after quaternization of the imidazole
are essentially identical. Moreover, there is no additional analysis
except energy dispersive X-ray (EDX) spectra. The spectra do
provide evidence for the presence of Br (although not for the
9978 | Dalton Trans., 2011, 40, 99779988 This journal is

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presence of the bromide anion), but the authors do not discuss
elemental analysis or IR spectroscopy data; the entire structure
assignment therefore remains somewhat inconclusive.
Overall, the few data available on non-siliceous and non-
carbonaceous IL/inorganic hybrid materials
68,98100
indicate that
further investigation into this topic is a worthy endeavor. In
particular, the combination of a functional matrix (instead of
silica, which typically just sits there and holds the ionogel together)
could add a tremendous potential to the respective ionogels.
Why is it, then, that so little work has been done in that area?
Presumably there is more than one answer to this question. We
will in the remainder of the article discuss reasons and combine
experimental and theoretical arguments to evaluate promising
pathways towards multifunctional IL hybrid materials based on
(crystalline) inorganic matrix materials.
Some of the authors of this article have a history of magnetic
hybrid materials research
101103
and it is thus straightforward to use
magnetic materials such as layered hydroxides or hydroxyacetates
as test cases towards new ionogels with non-siliceous and non-
carbonaceous matrices. This is particularly true because the
insertion of a wide variety of organic molecules into the inter-
layers of, for example, Zn
5
(OH)
8
(OAc)
2
, affects the structure and
properties of the resulting new hybrid materials.
101106
More work
has been done on zinc or nickel/zinc hydroxynitrates, carbonates,
or chlorides.
107114
With ILs instead of conventional organic
guest molecules, such experiments would enable an identication,
quantication, and rationalization of the effects of chemical and
physical properties of a specic IL on the structure and properties
of the resulting hybrid material and therefore the construction
of entirely new hybrid materials. We have therefore investigated
protocols for incorporation of a series of ILs into several layered
magnetic host materials. In a rst attempt to answer the above
question why there are so few reports on inorganic non-silica-
based ionogels we will in the following address some of the
issues by combining experimental work with comparison of the
little published data available and identify the major reasons
obstructing a more efcient synthesis and application of ionogels
based on matrices other than silica and carbon.
It must at this point clearly be stated that there is a signicant
difference between the classical ionogels in silica and the ma-
terials discussed here. The inorganic matrix of the former (silica)
is typically amorphous and mesoporous, while the host materials
discussed here are crystalline and highly ordered. Because of the
signicant differences in the order and the chemical composition
of the two types of matrix materials, it is at the moment (also due to
the lack of information on the latter) not clear how closely related
the resulting IL/inorganic hybrids and silica ionogels are. We will
therefore at the moment assume that both are ionogels although
there will certainly be differences that will need to be worked out
in detail in the future.
Experimental
Chemicals
Cu(OAc)
2
H
2
O, Zn(OAc)
2
2H
2
O, and Co(OAc)
2
4H
2
O were pur-
chased from ABCR. Sodium dodecylsulfonate (NaDS
0
) was
purchased from VWR. The IL 1-ethyl-3-methylimidazolium
hexauorophosphate [Emim][PF
6
] was purchased from IoLiTec.
All products were used as received. 3-(1-Methylimidazolium-3-
yl)propane-1-sulfonate PmimSO
3
115116
and the ILs 1-methyl-3-
(3-carboxypropyl-)-imidazolium tetrauoroborate [PmimCO
2
H]-
[BF
4
],
117
1-methyl-3-(3-sulfopropyl-)-imidazoliumparatoluenesul-
fonate [PmimSO
3
H][PTS]
115116
and 1-methyl-3-(3-cyanopropyl-)-
imidazolium chloride [PmimCN][Cl]
118
were synthesized using
modied published protocols. Scheme 1 shows the compounds
used in this work.
Scheme 1 Compounds used in this work: 1-ethyl-3-methylimidazolium
hexauorophosphate [Emim][PF
6
], 1-methyl-3-(3-carboxypropyl-)-
imidazolium tetrauoroborate [PmimCO
2
H][BF
4
], 1-methyl-3-(3-
sulfopropyl-)-imidazolium paratoluenesulfonate [PmimSO
3
H][PTS], and
1-methyl-3-(3-cyanopropyl-)-imidazolium chloride [PmimCN][Cl], and
the betaine 3-(1-methylimidazolium-3-yl)propane-sulfonate PmimSO
3
.
Preparation of 3-(1-methylimidazolium-3-yl)propane-sulfonate
PmimSO
3
.
115116
A solution of 1-methylimidazole (1.642 g, 20 mmol) in acetone
(20 mL) was prepared in a three necked round bottom ask. Then
a solution of 1,3-propanesultone (2.443 g, 20 mmol) in acetone
(20 mL) was added slowly to this solution. The mixture was
stirred at room temperature under N
2
for 4 days and a white
precipitate progressively formed. The mixture was ltered and
the white powder was washed with acetone, followed by drying
under vacuum. Yield=85%. Elemental analysis: C
7
H
12
N
2
SO
3
(M=
204.25 g/mol): found (calc., %): C 41.17 (41.16); H 5.91 (5.92); N
13.68 (13.72); S 15.75 (15.70).
1
H-NMR (D
2
O): 8.65 (s, 1), 7.45
(d, 2), 7.35 (d, 1), 4.70 (d, 1), 3.80 (s, 3), 2.8 (d, 2), 2.25 (t, 2). IR
(transmittance, KBr pellet, cm
-1
): 3453 w, 3133 s, 3075 s, 3035 s,
2951 m, 2928 w, 2871 w, 2840 w, 1800 w, 1766 sh, 1688 w, 1572 m,
1561 m, 1388 w, 1344 m, 1266 m, 1238 s, 1211 s, 1144 s, 1116 s,
1077 m, 1033 s, 877 m, 805 s, 755 m, 733 s, 655 s, 627 s, 594 s, 527
s, 444 m.
Preparation of 1-methyl-3-(3-sulfopropyl-)-imidazolium
paratoluenesulfonate [PmimSO
3
H][PTS].
115116
PmimSO
3
(2.041 g, 10 mmol) was added to solid para-
toluenesulfonic acid(1.901 g, 10 mmol) andthe mixture was stirred
at 110

C overnight. A viscous transparent liquid was obtained.
After a few weeks, this viscous liquid turned into a white solid.
This phenomenon has already been described for ILs bearing -
SO
3
-
groups.
119
Yield = 80%. Elemental analysis: C
14
H
20
N
2
S
2
O
6
(M = 376.45 g/mol): found (calc., %): C 44.41 (44.67); H 5.37
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(5.35); N 7.13 (7.44); S 16.93 (17.04).
1
H-NMR (D
2
O): 8.60 (s, 1),
7.55 (d, 2), 7.35 (s, 1), 7.30 (s, 1), 7.20 (d, 2), 4.15 (d, 2), 3.70 (s,
3), 2.70 (d, 2), 2.25 (s, 3), 2.15 (t, 2).
13
C-NMR (D
2
O + 5 drops
of DMSO-d
6
): 144, 140, 136, 130, 126, 124, 122, 48, 37, 27, 21.
IR (transmittance, KBr pellet, cm
-1
): 3383 m, 3161 s, 3111 s, 2966
w, 2922 w, 1702 m, 1600 w, 1573 m, 1498 w, 1453 w, 1231 s, 1164
s, 1120 s, 1035 s, 1006 s, 911 w, 817 m, 746 m, 680 s, 622 w, 567
m, 522 w. IR (reectance, cm
-1
): 3458 w, 3153 m, 3111 m, 2959 w,
2923 w, 2861 w, 1694 m, 16040 w, 1569 m, 1494 w, 1453 m, 1231 s,
1168 s, 1122 s, 1031 s, 1004 s, 904 w, 818 m, 742 m, 677 m, 620 w.
Synthesis of 1-methyl-3-(3-cyanopropyl-)-imidazolium chloride
[PmimCN][Cl]*1.5 H
2
O.
118
1-Methylimidazole (4.105 g, 50 mmol) and 4-chlorobutyronitrile
(6.215 g, 60 mmol) were mixed in a round bottom ask and the
mixture was stirred at 80

C for 24 h. After cooling, the resulting

oily and slightly yellow liquid was washed with diethyl ether (3 *
15 mL) and dried under vacuum. Yield = 94%. Elemental analysis:
C
8
H
14.6
N
3
O
1.3
Cl (M = 206.68 g/mol): Found (calc., %): C 46.03
(45.96); H 7.01 (7.04); N 19.92 (20.10); Cl 16.99 (16.96).
1
H-NMR
(D
2
O): 8.60 (s, 1), 7.55 (d, 1), 7.35 (d, 1), 4.25 (t, 2), 3.75 (s, 3), 2.65
(t, 2), 2.20 (q, 2).
13
C-NMR (D
2
O): 123.98, 122.27, 120.19, 48.08,
35.88, 25.16, 13.84. IR (reectance, cm
-1
): 3375 m, 3074 m, 2246
m, 1637 m, 1574 s, 1453 m, 1426 m, 1339 w, 1166 s, 1022 w, 847
m, 759 m, 648 m, 621 s, 556 m.
Preparation of 1-methyl-3-(3-carboxypropyl-)-imidazolium
tetrauoroborate [PmimCO
2
H][BF
4
]*0.5 H
2
O.
120
Under an inert nitrogen atmosphere, equimolar quantities of 1-
methylimidazole and 3-chloropropionic acid were dissolved in
methanol at roomtemperature. The mixtures were heated to 75

C
with stirring and allowed to react for 20 h. The resulting reaction
mixture was treated with NaBF
4
(1.2 equiv) and stirred for 18 h
at room temperature. After removing the precipitated NaCl the
ltrate was concentrated by rotary evaporation. The yellow and
viscous product was washed with diethyl ether and dried under
vacuum to afford the neat IL. Yield = 68%. Elemental analysis:
C
8
H
14
N
2
O
2.5
BF
4
(M = 265,1 g/mol): found (calc., %): C 36.03
(36.26); H 5.56 (5.32); N 10.84 (10.57).
1
H-NMR (D
2
O): 8.60 (s,
1), 7.45 (s, 1), 7.40 (s, 1), 4.20 (m, 2), 3.80 (s, 3), 2.40 (m, 2), 2.10
(m, 2). IR (reectance, cm
-1
): 3330 w, 3152 w, 3111 w, 2966 w,
1722 m, 1566 m, 1430 w, 1166 m, 1028 s, 861 m, 750 m, 625 m,
513 m.
Intercalation
The layered simple hydroxides (LSH) Cu
2
(OH)
3
(OAc),
121
Co
2
(OH)
3
(OAc),
122
Zn
5
(OH)
8
(OAc)
2
,
104,107108,123
and
Co
2
(OH)
3
(DS
0
)
123124
(where DS
0
is dodecylsulfonate) were
prepared as previously described. In a typical procedure, the
LSH was reacted with an excess of IL (around 4 equivalents of
IL per equivalent of LSH) suspended in aqueous NaOH (pH
was adjusted to 89.5 with 1 M NaOH). Upon completion of
the reaction, the powder was ltered and washed with water and
ethanol. All reactions were done under argon with the reaction
time and temperature being variable parameters (see Table 1
below). In the case of [Emim][PF
6
], a few drops of ethanol were
added to the aqueous medium to ascertain complete dissolution
of the IL; no base was used in this case and the pH of the nal
solution was around 7.7.
Elemental analysis
C, H, N, S, and metals analysis were carried out at the Analytische
Laboratorien GmbH Lindlar.
Table 1 Reaction parameters and products
Starting materials
Entry IL Hydroxide pH Temperature Time Final product
1 [Emim][PF
6
] Zn
5
(OH)
8
(OAc)
2
8 RT 4h Zn(OH)
2
+ LSH Zn
2 Zn
5
(OH)
8
(OAc)
2
8 40

C 4h Zn(OH)
2
+ LSH Zn
3 Zn
5
(OH)
8
(OAc)
2
8 90

C 4h ZnO
4 Co
2
(OH)
3
(DS
0
) 8 RT 4h no reaction
5 Co
2
(OH)
3
(DS
0
) 8 40

C 4h no reaction
6 [PmimCO
2
H][BF
4
] Co
2
(OH)
3
(DS
0
) 7.7 RT 6h no reaction
7 Co
2
(OH)
3
(DS
0
) 7.7 40

C 6h no reaction
8 Co
2
(OH)
3
(DS
0
) 8.7 40

C 6h no reaction
9 Co
2
(OH)
3
(DS
0
) 7.7 80

C 6h no reaction
10 Cu
2
(OH)
3
(OAc) 8.7 90

C 2h CuO
11 Zn
5
(OH)
8
(OAc)
2
7.7 90

C 2h ZnO
12 [PmimSO
3
H][PTs] Co
2
(OH)
3
(DS
0
) 8.8 50

C 6h no reaction
13 Co
2
(OH)
3
(DS
0
) 8.8 50

C 24h no reaction
14 Zn
5
(OH)
8
(OAc)
2
9.3 50

C 4h Zn/PTS + LSH Zn
15 Zn
5
(OH)
8
(OAc)
2
9.3 50

C 17h Zn/PTS + LSH Zn

16 Zn
5
(OH)
8
(OAc)
2
9.3 50

C 48h Zn/PTS
17 Co
2
(OH)
3
(OAc) 9.3 50

C 4h Co/PTS
18 Cu
2
(OH)
3
(OAc) 9.3 50

C 4h Cu/PTS
19 PmimSO
3
Zn
5
(OH)
8
(OAc)
2
9.5 50

C 24h Zn(OH)
2
19 Cu
2
(OH)
3
(OAc) 9.5 50

C 24h CuO
21 [PmimCN][Cl] Cu
2
(OH)
3
(OAc) 6.6 50

C 24h Cu
2
(OH)
3
(Cl)
22 Cu
2
(OH)
3
(OAc) 9.5 50

C 24h Cu
2
(OH)
3
(Cl)
23 Zn
5
(OH)
8
(OAc)
2
6.6 50

C 4h Zn
5
(OH)
8
(Cl)
2
24 Zn
5
(OH)
8
(OAc)
2
9.5 50

C 24h Zn
5
(OH)
8
(Cl)
2
9980 | Dalton Trans., 2011, 40, 99779988 This journal is

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X-ray diffraction
Powder XRDpatterns were collected on a Siemens/Bruker D5005
diffractometer (Cu K
a1
= 1.540598 A

) between 2 and 70 degrees

2q.
Spectroscopy
Infrared spectra were recorded on KBr pellets on a Nicolet
FT-IR Nexus 470 or in ATR mode on a Nicolet FT-IR 730.
UV/Vis/NIR spectra were recorded on a Perkin-Elmer Lambda
950 spectrometer (reection mode using a 150 mm integrating
sphere with a mean resolution of 2 nm and a sampling rate of
300 nmmin
-1
). Liquid NMRwas measured using a Bruker Avance
250 spectrometer. The spectra were calibrated with respect to the
H
2
O peak (4.70 ppm) from the D
2
O solvent.
Scanning Electron Microscopy
SEM images were obtained with a JEOL 6700F with a eld
emission gun, operating at 3 and 15 kV in the SEI mode. Prior
to SEM, powder samples were deposited on a double-faced sticky
tape and coated with an evaporated carbon layer.
Thermogravimetric analysis
TGA was done on a Mettler Toledo TGA/SDTA 851 in air from
20 to 900

C with a heating rate of 10

C min
-1
.
Differential scanning calorimetry
DSC experiments were done on a Mettler Toledo DSC 822.
Samples of about 5 mg were placed in aluminumpans with pierced
lids. DSC traces were recorded from -40 to 200

C with a heating
rate of 10 Kmin
-1
. To reduce water traces, the samples were heated
to 200

C before the rst cooling cycle. Heating and cooling cycles

were repeated twice for reproducibility. Isothermal times were
5 min.
Results
We have used a series of ILs and layered simple hydroxides (LSHs)
toexplore the parameter space for the synthesis of well-denedand
single phase IL/LSH hybrid materials. For clarity, the results are
discussed in order of the ILs used in the study. With the exception
of [Emim][PF
6
], materials were synthesized by dispersing the LSH
in a basic aqueous solution containing the IL (see Experimental
for details).
1. Intercalation of 1-ethyl-3-methylimidazolium
hexauorophosphate [Emim][PF
6
]
1.1 Intercalation into Zn
5
(OH)
8
(OAc)
2
. Fig. 1 shows X-ray
diffraction (XRD) patterns of products obtained after 4 h of
reaction between Zn
5
(OH)
8
(OAc)
2
and [Emim][PF
6
] at different
temperatures. Samples obtained at room temperature (RT) and
at 40

C exhibit a progressive disappearance of the lamellar
starting compound Zn
5
(OH)
8
(OAc)
2
. Accordingly, a new phase is
observed, Zn(OH)
2
(wuelngite, JCPDS 38-385). Upon treatment
at 90

C, the starting lamellar phase Zn
5
(OH)
8
(OAc)
2
completely
transforms into ZnO (wurtzite, JCPDS 36-1451).
Fig. 1 Powder XRD patterns of the starting compound Zn
5
(OH)
8
(OAc)
2
(black) and of the compounds obtained after 4 h of reaction between
Zn
5
(OH)
8
(OAc)
2
and [Emim][PF
6
] at RT (red), at 40

C (blue), and at
90

C (green).
Fig. 2 shows the corresponding scanning electron microscopy
(SEM) data. Samples treated at 40

C contain rather large crystals
with well-developed faces and edges. This is consistent with
(1) the observation of sharp reections in the XRD patterns
and (2) with earlier reports on the morphology of wuelngite
Zn(OH)
2
.
123
Samples treated at 90

C contain particles with a
poorly dened hexagonal prismatic morphology. Most particles
exhibit the central grain boundary known from other reports
on ZnO precipitated from aqueous solution.
125128
SEM further
suggests that the particles are not single crystals, but mesocrystals,
similar to other examples known from the literature.
129133
Fig. 2 SEM images of the compounds obtained after for 4 h of reaction
between Zn
5
(OH)
8
(OAc)
2
and [Emim][PF
6
] at 40

C (left) and at 90

C
(right). Scale bars are 1 mm.
Fig. 3 shows the corresponding IR spectra. IR spectroscopy
clearly shows the disappearance of the vibration bands at
1540 cm
-1
and 1388 cm
-1
corresponding to the antisymmetric
and symmetric stretch vibration of the carboxylate groups of
the starting LSH Zn
5
(OH)
8
(OAc)
2
. Moreover, IR spectra of the
products obtained at RT and 40

C show new bands at 1090,
1032, 718, and 484 cm
-1
. None of these bands is present in the
original LSH. They can be attributed to asymmetric stretching
vibrations of ZnOZn and bridge-oxygen in the orthorhombic
structure (1090 and 1032 cm
-1
), to n
OH
groups (718 cm
-1
) and to
the lattice vibrations of ZnO metaloxygen bonds (484 cm
-1
).
134
The compound obtained at 90

C exhibits a new band at 545 cm
-1
which can be assigned to ZnO vibrations.
134
However, none
of the compounds exhibits bands of the IL, in particular the
hexauorophosphate anion around 830 cm
-1
, which is clearly
visible in the original IL. In summary, therefore, XRD, SEM,
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Fig. 3 Infrared spectra of the starting compound Zn
5
(OH)
8
(OAc)
2
(black) and of the compounds obtained after 4 h of reaction between
Zn
5
(OH)
8
(OAc)
2
and [Emim][PF
6
] at RT (red), at 40

C (blue), at 90

C
(green) and neat IL [Emim][PF
6
] (grey).
and IR spectroscopy show that [Emim][PF
6
] does not intercalate
into the LSHZn
5
(OH)
8
(OAc)
2
. Simple adaptation of intercalation
protocols from layered hybrid materials is therefore not possible
for IL/LSH hybrid materials.
1.2 Intercalation into Co
2
(OH)
3
(DS
0
) [that is, Co
2
(OH)
3
(OAc)
pre-intercalated with dodecylsulfonate DS
0
]
Fig. 4 shows the IR spectra and XRD patterns of the start-
ing material and the products obtained after 4 h of reaction
between [Emim][PF
6
] and pre-intercalated Co
2
(OH)
3
(DS
0
). The
difference to the above example is that here, the inorganic matrix,
Co
2
(OH)
3
(OAc), has been treated with sodium dodecylsulfonate
prior to ILintercalation. The goal of this approach was to generate
a more hydrophobic interlayer environment, which, possibly,
would be more suitable for IL intercalation. Unlike the example
discussed above, there is no phase transition of the inorganic.
The only modication observed in XRD is a decreasing reection
intensity, in particular of the (001) reection. The exact reason
for this reduction is hard to identify: either, a partial removal of
the dodecylsulfonate from the LSH hosts leads to a lower electron
density near the basal planes of the inorganic layer, which in turn
leads toa lower signal intensity. Alternatively, the reducedintensity
is due to a reduced order in the layers, although, possibly, in this
Fig. 4 XRD patterns (left) and IR spectra (right) of the starting
compound Co
2
(OH)
3
(DS
0
) (black) and the compounds obtained after 4 h
of reaction between Co
2
(OH)
3
(DS
0
) and [Emim][PF
6
] at RT (red) and at
40

C (blue). The infrared spectrum of the neat IL [Emim][PF

6
] is shown
in the right part in grey. A modication of the pH from 7.7 to 8.7 does not
change the nal product (data not shown).
case a line broadening should also be observed. There is, however,
no indication of IL incorporation into the inorganic.
IR spectroscopy supports XRD in that also here essentially the
signals of the starting compound Co
2
(OH)
3
(DS
0
) are observed.
Moreover, no band originating from the IL (in particular the
PF
6
band around 830 cm
-1
) is present in the IR spectra of the
compounds obtained after reaction with [Emim][PF
6
].
2. Intercalation of 1-carboxypropyl-3-methylimidazolium
tetrauoroborate [PmimCO
2
H][BF
4
]
It has been demonstrated above that the LSH Zn
5
(OH)
8
(OAc)
2
is not stable under the experimental conditions studied so
far (Fig. 1). Co
2
(OH)
3
(DS
0
) is stable (Fig. 4), but does not
show intercalation with [Emim][PF
6
]. One of the reasons for
the failed intercalation could be an unfavorable interaction of
the IL cation with the LSH hosts. We have thus exchanged
[Emim][PF
6
] for 1-carboxypropyl-3-methylimidazolium tetrauo-
roborate [PmimCO
2
H][BF
4
] which bears an additional carboxylic
acid functionality in the side chain. The carboxylate group
strongly interacts with LSHs,
101,103105,107108,110,122135136
and a better
incorporation into the LSH can therefore be envisioned.
Fig. 5 shows the results of the intercalation experiments with
[PmimCO
2
H][BF
4
] and Co
2
(OH)
3
(DS
0
). Somewhat surprisingly,
the XRD patterns are strikingly similar to those of the products
of the reaction between [Emim][PF
6
] and Co
2
(OH)
3
(DS
0
), Fig. 4.
Again, XRD suggests a degradation of Co
2
(OH)
3
(DS
0
) by DS
0
release, but no IL incorporation. Comparison experiments at
80

C only yield a small amount of product, which could not
be analyzed further. However, the brown color of the resulting
solid suggests the formation of oxides. IR spectroscopy conrms
the XRD data. The IR spectra of the two compounds obtained
after the reaction are essentially identical to the spectra of the
starting compound. No vibration band originating from BF
4
-
or
-CO
2
-
groups is present in the IR spectra of the products.
So far, we did not observe any IL incorporation into the LSH
host materials. One possible explanation can be found in the
rather poor stability of the PF
6
-
and the BF
4
-
anions against
hydrolysis. To determine the stability of the IL [PmimCO
2
H][BF
4
]
we have performed an acidbase titration, Fig. 6. Clearly, the curve
displays two steps. The rst step corresponds to the deprotonation
of the CO
2
H group and the second step corresponds to the
hydrolysis of the BF
4
groups. Titration therefore clearly shows
that [PmimCO
2
H][BF
4
] is not stable in a neutral or basic aqueous
medium (which is used for our synthesis). This conrms previous
work on the stability of the PF
6
-
and BF
4
-
anions.
137
3. Intercalation of 1-propylsulfonate-3-methylimidazolium
para-toluene sulfonate [PmimSO
3
H][PTS]
Intercalation into Cu
2
(OH)
3
(OAc), Zn
5
(OH)
8
(OAc)
2
, and
Co
2
(OH)
3
(OAc). Besides carboxylates, sulfonates efciently at-
tach to the inorganic layers in LSHs. We have therefore, in a next
attempt towards stable IL/LSH hybrid materials, replaced the
carboxylate group for a sulfonate group and the labile anions PF
6
-
and BF
4
-
for the stable anion para-toluene sulfonate (tosylate).
Fig. 7 shows the IR spectra and XRD patterns of the prod-
ucts obtained after 4 h of reaction at 50

C between the IL
[PmimSO
3
H][PTS] and different LSHs. All XRD patterns show
9982 | Dalton Trans., 2011, 40, 99779988 This journal is

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Fig. 5 XRD patterns (left) and IR spectra (right) of the starting compound Co
2
(OH)
3
(DS
0
) (black) and the products obtained after 4 h of reaction
between Co
2
(OH)
3
(DS
0
) and [PmimCO
2
H][BF
4
] at RT (red) and at 40

C (blue). The IR spectrum of the neat IL [PmimCO
2
H][BF
4
] is shown in the right
part in grey.
Fig. 6 Titration curve of the IL [PmimCO
2
H][BF
4
].
a new lamellar phase with an interlamellar distance of 13.5, 16.9,
and 17.6 A

for the LSH based on Cu, Zn and Co, respectively. In

the case of the ZnLSH the reaction is not complete and it was
necessary to increase the reaction time to 48 h to obtain a single
phase with an interlamellar distance of 16.9 A

(data not shown).

IR spectra conrm XRD suggesting that here, for the rst time,
new hybrid materials have formed. The IR spectra can, however,
not be assigned to the target hybrid materials. Rather, the signals
suggest that not the IL is incorporated but something else, leading
to a well-ordered material.
Fig. 8 shows IRandNMRspectra of a sample obtainedfromthe
reaction of Zn
5
(OH)
8
(OAc)
2
and [PmimSO
3
H][PTS]. This sample
was dissolved in aqueous HCl to isolate the organic component in
the hybrid.
1
H-NMR spectra can only be assigned to the para-
toluenesulfonate (PTS
-
) counter ion of the original IL. NMR
therefore shows that not the IL, but only the PTS
-
anion is inserted
in the LSH. Moreover, although NMR cannot readily be used
for the Cu and Co LSHs since these metals are paramagnetic,
the similarity of all IR spectra of the reaction products with the
different LSHs and [PmimSO
3
H][PTS] suggests that in all cases
(Co, Cu, Zn) only the PTS
-
anion is inserted into the LSH. This
is further conrmed by elemental analysis (data not shown).
Intercalation into the pre-intercalated LSH Co
2
(OH)
3
(DS
0
) with
[PmimSO
3
H][PTS]. As demonstrated above for [Emim][PF
6
],
(see Fig. 4), the pre-intercalation of an LSHwith dodecylsulfonate
does not improve the intercalation with the IL[PmimSO
3
H][PTS].
Again, the XRD patterns and the IR spectra of the compounds
obtained after 6 or 24 h of reaction at 50

Cresemble the respective

data of the starting compound (except for the intensity of the XRD
peaks, data not shown).
4. Intercalation of the betaine
1-propylsulfonate-3-methylimidazolium [PmimSO
3
]
It has just been mentioned that IL intercalation into
Co
2
(OH)
3
(DS
0
) has so far not been successful. In contrast
(although not the entire ILbut only the anion PTS
-
has been incor-
porated), intercalation into Cu
2
(OH)
3
(OAc) and Zn
5
(OH)
8
(OAc)
2
is at least a partial success. We have therefore rationalized that
removal of the PTS
-
anion could result in the incorporation of the
Fig. 7 XRD patterns (left) and IR spectra (right) of the starting compounds Cu
2
(OH)
3
(OAc) (black), Zn
5
(OH)
8
(OAc)
2
(brown), Co
2
(OH)
3
(OAc) (grey),
and of the compounds obtained after 4 h of reaction at 50

C between [PmimSO
3
H][PTS] and Cu
2
(OH)
3
(OAc) (red), and Zn
5
(OH)
8
(OAc)
2
(blue), and
Co
2
(OH)
3
(OAc) (green). The IR spectrum of the neat IL [PmimSO
3
H][PTS] is shown on the right (grey).
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Fig. 8 NMR (left) and IR (right) spectra of the compound obtained from the reaction of Zn
5
(OH)
8
(OAc)
2
and [PmimSO
3
H][PTS] (48 h at 50

C). The
NMR spectrum was obtained after dissolution of the sample in aqueous HCl. The IR spectrum of the hybrid material is shown in blue.
[PmimSO
3
] betaine unit because the competing insertion of the
PTS
-
anion is eliminated.
Fig. 9 shows the IR and XRD data of a sample obtained by
reaction of Zn
5
(OH)
8
(OAc)
2
with [PmimSO
3
] after 24 h at 50

C.
Unfortunately, as already observed for the case of [Emim][PF
6
],
the XRD pattern of the product can be assigned to Zn(OH)
2
(wuelngite, JCPDS 38-385) and not to an IL/LSH hybrid
material.
XRD is conrmed by IR spectroscopy. The bands corre-
sponding to the antisymmetric and symmetric vibration of the
carboxylate -CO
2
-
(1540 and 1388 cm
-1
, respectively) in the
starting material disappear. New bands at 1090 and 1032 (asym-
metric stretching vibration of ZnOZn and bridge-oxygen in the
orthorhombic structure, respectively), 718 (d
OH
), and 508 and
484 cm
-1
(lattice vibrations of ZnO) appear.
134
But once again,
there is nosignal of anILcomponent, inthis case PmimSO
3
, visible
in the reaction product. Both XRD and IR therefore suggest no
IL incorporation. In the case of Cu
2
(OH)
3
(OAc) a brown powder
indicative of CuO was obtained. This is conrmed by infrared
spectroscopy (data not shown) but the very low yield prevented
diffraction analysis.
5. Intercalation of 1-cyanopropyl-3-methylimidazolium chloride
[PmimCN][Cl]
Fig. 10 shows the results of the reaction of Zn
5
(OH)
8
(OAc)
2
and
Cu
2
(OH)
3
(OAc) with [PmimCN][Cl] after 24 h at 50

C. In both
cases, a newlamellar product with an interlamellar distance of 5.71
(Cu) and 7.61 A

(Zn) is obtained, suggesting that, possibly, here

indeed the IL is incorporated into the LSH matrix. Unfortunately,
however, these interlamellar distances correspond to the well-
known lamellar compounds Cu
2
(OH)
3
(Cl) and Zn
5
(OH)
8
(Cl)
2
.
XRD therefore demonstrates that not the IL but, once again, only
the anion (in this case chloride) is incorporated into the LSHhost.
IR spectroscopy conrms this nding, as mainly MO vibration
bands, but no IL signals are observed. Further modications of
the conditions, such as altering the pH from 6.6 to 9.5 during the
reaction do not further change this nding.
Discussion
For clarity, Table 1 summarizes the results of the experiments
presented above. The main outcomes are (1) that the synthesis of
IL/inorganic hybrid materials is much more difcult with LSHs
than with silica or carbon host materials, (2) that almost every
combination of IL and LSH host yields a different product, and
(3) that the anion of the IL appears to intercalate much more
readily into the LSH than the entire IL, even in cases where the
imidazoliummoiety bears a coordinating function, i.e. carboxylate
or sulfonate. There are however also ner details which will be
discussed below.
Overall, the current experiments and the two studies on related
approaches
99100
suggest that the synthesis of IL/inorganic hybrid
Fig. 9 Powder XRD patterns (left) and IR spectra (right) of the starting compound Zn
5
(OH)
8
(OAc)
2
(black) and of the compound obtained after 24 h
of reaction between Zn
5
(OH)
8
(OAc)
2
and PmimSO
3
at 50

C (red). The IR spectrum of PmimSO
3
is shown in the right part in grey.
9984 | Dalton Trans., 2011, 40, 99779988 This journal is

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Fig. 10 Powder XRD patterns (left) and IR spectra (right) of the starting compounds Cu
2
(OH)
3
(OAc) (black), Zn
5
(OH)
8
(OAc)
2
(brown), and of the
compounds obtained after 24 h of reaction at 50

C between [PmimCN][Cl] and Cu
2
(OH)
3
(OAc) (red), and Zn
5
(OH)
8
(OAc)
2
(blue). The IR spectrum of
the IL [PmimCN][Cl] is shown on the right (grey).
materials is much more difcult once the inorganic host is a
crystalline, well-ordered substance. In contrast to amorphous
silica
55,5960,6567,6970
or different carbon
72,9195
hosts, where a fairly
large number of ILs has readily been incorporated, the insertion
into LSHs and related compounds appears to be much more
dependent on the chemical nature of the host (LSH) and guest
(IL) and the specics of their interaction. Indeed, ILs show a
large number of different interactions
138
and it is thus necessary
to evaluate these different interactions for their importance in the
current problem.
Among others, ILs exhibit ionic, hydrogen bonding, hydropho-
bic, and pp interactions both between IL components and the
surroundings such as the inorganic host material. In the case
of silica surfaces SiO
x
, some authors report a melting point
depression,
71
which is different than what has been reported for
ILs immobilized in carbon nanotubes.
91
Sha et al. suggest that
negative surface charges leadtoa bilayer formationin[Emim][PF
6
]
although they did not specify the chemical nature of the surface.
72
One may thus argue (although this question has not been answered
conclusively as of now) that in some cases also positive surface
charges may lead to specic interactions between the IL anion
and matrix. Indeed, G obel et al. have shown that the modication
of pore walls in mesoporous silica with neutral and positively
charged pendant groups strongly affects the phase behavior of the
conned IL.
65
This is one of the rst experimental datasets of a
surface charge effect onthe behavior of a connedIL. However, the
pendant groups used in this study are aromatic and pp stacking
could therefore also be of importance. Indeed, pp stacking
between the imidazolium ions and the p-system of graphite or
carbonnanotubes has beensuggestedas a key interactionaffecting
the behavior of ILs.
71,8387
Further experiments are therefore needed
to separate the contributions of the charge from the pp stacking
contributions to the IL behavior in connements.
The cases of silver
98
and SnO
2
68
hosts remain currently open,
because of the lack of data. Obviously, for example hydrogen
bonding is a possible key interaction in the case of SnO
2
, but
this remains to be proven in the future. Overall these data
nevertheless suggest that in carbon host materials pp interactions
are important, while in all other inorganic matrices presumably
ionic interactions and hydrogen bonding dominate.
Let us now turn to the problem at hand, the incorporation of
ILs in a chemically and crystallographically well-dened inorganic
matrix such as LSHs. Essentially, our results suggest that in the
worst case, the matrix is not stable and transformation into an
undesired inorganic such as wuelngite or zincite occurs (Fig. 1
3). The other key outcome is that there is no incorporation
of a molecular entity containing a cation. Neither simple IL
cations such as [Emim] (Fig. 1) nor more complex molecules
like [PmimCO
2
H] (Fig. 5) or the less highly charged [PmimCN]
(Fig. 10) are found anywhere in the reaction products. Pre-
intercalation with dodecylsulfonate (Fig. 4) does not alter this
behavior.
In contrast, anions like tosylate (Fig. 7 and 8) or chloride
(Fig. 10) readily exchange with the acetate of the LSH. This
suggests that there is a general problem with the concomitant
incorporation of the cationic counterpart of the IL. Indeed, LSHs
are anion exchange materials. As a result, an incorporation of ILs
will strongly depend on the balance between electrostatic repulsion
by the layers where the anion exchange occurs and the bonding
between the two components of the ILs (the inorganic layers in
LSHare neutral since the anionic interlayer species coordinate the
metal ions; a transition state with locally positively charged layers
can therefore be envisaged during the anion exchange reaction.
This would, however, not aid a cation exchange).
Indeed, recent work by Oaki et al. suggests that another
approach could be more successful.
100
Instead of intercalating the
IL, these authors have incorporated a carboxylated imidazole into
layered a-Co(OH)
2
. Only after incorporation, the imidazole was
reacted with an alkyl bromide. The rationale behind this approach
is that cations are hard to incorporate into many inorganic
matrices (which is also conrmed by the experiments reported
here). As pointed out in the introduction, however, there are issues
with the reported characterization of the resulting material. XRD
patterns of the products before and after imidazole quaternization
are virtually identical and except EDX data, no further analysis is
reported. The structure assignment therefore remains somewhat
ambiguous and it is thus at the moment not possible to conclude
on the potential of the intercalation-quaternization approach
introduced by Oaki et al.
Finally, Wu et al. reported on zinc hydroxyuoride nanobers
synthesized with ILs.
99
The authors draw a rather specic image
of how and where the IL anion (BF
4
-
) and the IL cation
(1,2,3-trimethylimidazolium) are located in their material. It must
however be concluded that the analysis (as it is reported in the
publication) does not entirely support this claim. For example,
there is no discussion of the d-spacings vs. the sizes of the IL
This journal is

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anions and cations or with respect to a non-substituted (that is,
without organic component) zinc hydroxyuoride control sample.
In spite of these shortcomings the work by Wu et al. is interesting
because it is the rst report of a non-siliceous hybrid material
where a 1,2,3-trisubstituted imidazolium IL has been used. As the
2-Hsite in imidazoliumcations is quite acidic, this work may serve
as a prototype for materials where this 2-H acidity is a problem.
This possibly also includes some of the materials that have been
studied by us in the current manuscript.
Having said all the above, it is important to note that there is
a type of crystalline inorganic matrix, which has been used quite
successfully for the fabrication of inorganic/IL hybrid materials:
clays. Initially, a few studies have focused on the fabrication of
these materials, mostly based on kaolinite or montmorillonite.
While an early study focused on the sorption properties of several
inorganic surfaces,
139
subsequent publications focused on the op-
timization of the intercalation procedure and a detailed structural
characterization.
140142
Among others these studies clearly show
that successful IL intercalation often, but not exclusively, needs a
suitable pre-intercalation, for example with DMSO
140
or urea.
141
This suggests that intercalation may also be possible with the
materials used in the current study or those used by Oaki et al.
100
and Wu et al.,
99
but that a suitable pre-intercalation process is yet
to be developed. Furthermore, application oriented-approaches
have then explored the potential of clay/IL hybrid materials for
catalysis,
143146
sensing,
147149
electrochemistry,
150
and mechanical
reinforcement.
151
It must be noted at this point that not in all
cases the interaction of the IL with the clay has been studied in
detail; it is therefore not possible to draw a nal conclusion as to
why, for example, in some cases pre-intercalation is necessary for
successful fabrication of a homogeneous and well-dened hybrid
material and not in others.
Nevertheless, based on the currently available data it is possible
to formulate some rst, basic rules or hypotheses for the synthesis
of IL/inorganic hybrid materials which will need to be further
evaluated in the future. (1) The ILs (including the cations, see
the discussion on the 2-H acidity problem in imidazolium above)
must be stable in the medium chosen for the reaction. This seems
trivial, but as shown in this study, even a slow degradation
of IL components (for example [BF
4
] or [PF
6
])
99
releases ions
or molecules that can dramatically change the outcome of the
reaction, Fig. 13. (2) Pre-intercalation does, at least until now,
not seem a useful strategy for successful intercalation in the case
of metal hydroxides, although it has been successfully used in
clays.
140141
Even relatively hydrophobic ILs such as [Emim][PF
6
]
are not incorporated into the hydrophobic pre-intercalated in-
terlayer spaces of the metal hydroxides, Fig. 4. This suggests
that, possibly, hydrophobic interactions are less important for IL
incorporation than some others. (3) Electrostatic interactions are
a key parameter to investigate further, even though they may be
rather short ranged, because of the high ion concentration.
100
This is clearly supported by some work on clays, which have
charged inorganic layers.
142,144146,148,151
The current study, where
the inorganic layers are electrically neutral, shows a clear selection
between anion and cation incorporation, e.g. Fig. 7 and 8. Only
anions such as the [PTS] ion are incorporated into the interlayer,
but neither simple cations like [Emim] nor betaine-like molecules
such as [PmimSO
3
] or functionalized cations such as [PmimCO
2
H]
are found in the products. (4) Possibly, competing intercalation of
two chemically similar IL components (for example [PmimSO
3
H]
and [PTS]
-
, Scheme 1) is another factor to consider. If the
[PTS]
-
anion is incorporated much faster, the [PmimSO
3
H] cation
may not stand a chance for incorporation because the nal
interaction with the inorganic matrix is roughly the same (both via
a sulfonate group) and there is thus no net energy gain for a [PTS]
[PmimSO
3
H] exchange. This may be different if the IL anion is
much bulkier than the betaine. (5) Finally, if the IL contains ions,
in particular anions, that efciently coordinate to the inorganic
layer they must be selected such that they do not alter the structure
into an undesired compound. For example, ILs with a chloride or
bromide anion may generally not be suitable, because they will
lead to, for example, Cu
2
(OH)
3
(Cl) and Zn
5
(OH)
8
(Cl)
2
, which are
not the desired products, but are hard to transform any further.
The current study therefore shows that, although there are
two reports
99100
on the successful formation of IL/inorganic
hybrid materials, there is so far no generic approach towards this
interesting class of hybrid materials (with the exception of some
clays). There is thus a need to further investigate the interaction of
ILs with different inorganic hosts and to continue the development
of synthesis protocols. One possibility may indeed be the approach
put forward by Oaki et al.
100
of rst intercalating a precursor into
the matrix followed by formation of the cation. Other alternatives
include (1) the use of other matrix materials, for example layered
double hydroxides, oxalates, perovskites, or mesoporous metal
oxides,
152153
(2) other synthetic processes such as ionothermal
synthesis
89
or (3) exfoliation and casting of the hybrid materials
from an inorganic/IL mixed solution. So far there are no reports
on any of these approaches, although two versatile exfoliation
protocols for inorganic solids have recently been reported.
154155
Overall, the combination of many interesting matrix materials
withthe well knownproperties of ILs couldleadtomultifunctional
hybrid materials with combined, possibly synergistic properties
such as a (switchable) coupling between the magnetic layers of
a matrix material mediated by the IL in the interlayer spacings.
These properties will obviously depend on the exact composition
of both the host (the inorganic) and the guest (the IL) and will
need to be evaluated in much greater detail in the future.
Conclusion
IL/inorganic hybrid materials, predominantly in the formof silica
ionogels, have attracted increasing attention from the materials
community. Related, but chemically and structurally very different
materials based on layered, crystalline inorganic matrix materials
such as layered simple hydroxides (LSHs) hold promise for the
construction of highly advanced IL/inorganic hybrid materials.
As discussed in this article, however, the synthesis of these
materials is signicantly more complicated than the synthesis
of silica ionogels. Up to now there are interesting concepts
but no generic approaches towards such materials available
in the literature. The fabrication, and consequently also the
characterization and application therefore remain a challenge for
the materials chemistry community.
Acknowledgements
E.D. acknowledges an MPG-CNRS postdoctoral fellowship. We
thank Dr E.I. Unuabonah for useful discussion. Financial support
9986 | Dalton Trans., 2011, 40, 99779988 This journal is

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by the University of Potsdam, the Fonds der Chemischen
Industrie, the MPI of Colloids and Interfaces (Colloid Chemistry
Department), and the MPI for Polymer Research is gratefully
acknowledged.
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