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Fine tuning of the metalorganic framework Cu3(BTC)2 HKUST-1 crystal

size in the 100 nm to 5 micron range
Lik H. Wee,a Martin R. Lohe,b Nikki Janssens,a Stefan Kaskelb and Johan A. Martens*a
Received 24th November 2011, Accepted 24th April 2012
DOI: 10.1039/c2jm31536j
Cu3(BTC)2 (BTC 1,3,5-benzene tricarboxylate) was synthesized from cooled reagents in ethanol
water solvent mixtures and in ethanol solvent at room temperature involving quenching at 196  C and
freeze drying in order to limit crystal growth. These approaches are handy to synthesize this MOF with
narrow particle size distribution in the range of 100 nm to 5 microns and to achieve excellent
crystallinity and unprecedented porosity. The nano-version of Cu3(BTC)2 outperforms micron size
crystals in catalyzing methanolysis of styrene oxide.

Introduction
Metalorganic frameworks (MOFs) are an emerging class of
hybrid crystalline materials constructed from organic ligands
bridging inorganic moieties.13 They exhibit permanent porosity,4
tunable pore size512 and high surface area.13 Potential applications
spread over a wide area including gas storage, adsorption,1421
separation,2225 and catalysis.2629 Recently, the preparation of
nanosized MOFs has been proven to be significant in expanding
the spectrum of applications from liquid phase catalysis30,31 and
adsorption32 to multimodal bioimaging and drug release3336
among others.37 However, to date, only a limited number of reports
on nanosized MOFs have been published mainly due to the lack of
preparation techniques. Currently available methods for the
preparation of nanosized MOFs are solvent precipitation,3841
microwave heating,42 microemulsion,43,44 mechanochemistry,45 and
solvothermal synthesis.46 In most cases, additional chemical additives such as surfactants31,47 or capping agents48 are required.
Cu3(BTC)2, also denoted as HKUST-1, is a well known MOF
material constructed from dimer Cu paddle wheels linked by 1,3,5benzenetricarboxylates and was first reported by Chui et al.49 The
preparation technique involving conventional solvothermal heating at 180  C resulted in crystalline Cu3(BTC)2, but using that
procedure also the formation of impurities such as Cu2O was
noted. Bein and coworkers reported the high throughput synthesis
of phase pure Cu3(BTC)2 at lower temperature (75120  C).50
However, longer synthesis times ($1 day to weeks) were required.
Recently, we reported the synthesis of nanosized Cu3(BTC)2
encapsulating a Keggin-type phosphotungstic acid from

a
Centre for Surface Chemistry and Catalysis, Catholic University of
Leuven, Kasteelpark Arenberg 23, B3001 Leuven, Belgium. E-mail:
Johan.Martens@biw.kuleuven.be; Fax: +32 16 321998; Tel: +32 16
321637
b
Department of Inorganic Chemistry I, Dresden University of Technology,
Bergstrasse 66, 01069 Dresden, Germany
These authors contributed equally to this study.

13742 | J. Mater. Chem., 2012, 22, 1374213746

a waterethanol mixture at room temperature. Crystal growth

could be limited by quenching the synthesis mixture at 196  C.30
The product powder was recovered via freeze drying. The Keggin
ion, in this case, serves as a molecular template in prompting direct
formation of Cu3(BTC)2 bearing Keggin ions in its cavities.51 Our
attempt to prepare phase pure Cu3(BTC)2 from waterethanol
media of different ratios in the absence of Keggin ions at room
temperature was not successful. Instead an unknown phase was
obtained.51
Herein, we report two simple and efficient methods for the
preparation of nanosized versions of the popular Cu3(BTC)2 MOF.
The approach involves crystallization from ethanolic solutions
without using chemical additives or heating. According to the first
method, the nanosized Cu3(BTC)2 was formed via freeze drying of
a solution of the reagents. In a typical synthesis, nanosized
Cu3(BTC)2 was prepared by dissolving Cu(NO3)2$3H2O and
H3BTC in absolute ethanol followed by immediate freezing in
liquid nitrogen (196  C). Subsequently the solvent was removed
via lyophilization treatment. The second approach involved cooling
of ethanolic copper and H3BTC solutions prior to their mixing.
The ethanolic synthesis solutions were cooled to below 60  C and
mixed afterwards. At temperatures below 50  C no precipitation
occurs when mixing the educts due to kinetic inhibition of deprotonating the acid molecules. Upon letting the reaction mixture
slowly warm up to room temperature precipitation occurred,
leading to nanosized crystalline Cu3(BTC)2. The nanocrystalline
structure of Cu3(BTC)2 formed after mixing of the Cu and BTC
sources was confirmed by X-ray diffraction (XRD) and scanning
electron microscopy (SEM). The pre-cooling method was found to
be generic and applicable to other types of MOF too.

Experimental
MOF synthesis
In a typical synthesis involving freeze drying, nanosized Cu3(BTC)2
was prepared by dissolving 1.2 g of Cu(NO3)2$3H2O (99104%,
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Sigma-Aldrich) and 0.6 g of BTC (98%, Acros) in 20 mL of

absolute ethanol (BDH) followed by immediate freezing in liquid
nitrogen (196  C). The solvent was removed via lyophilization
treatment. The solid was washed with a water : ethanol mixture
1 : 1 (v/v) via a series of centrifugations and redispersion. The
second approach involved a cooling step prior to mixing the
ethanolic copper and trimesic acid solutions. Therefore 1.724 g of
Cu(NO3)2$3H2O and 0.5 g of BTC were dissolved in 10 mL of
ethanol each and cooled to below 60  C. A precipitate was
obtained upon letting the reaction mixture warm to room
temperature. The solid was recovered via a series of centrifugations
and redispersion in ethanol and dried in an oven at 60  C. For the
preparation of Cu3(BTC)2 at room temperature, 1.2 g of
Cu(NO3)2$3H2O was mixed with 0.6 g of BTC and dissolved in
20 mL of ethanol. The synthesis mixture was stirred for 24 h. The
precipitate was washed with a water : ethanol mixture 1 : 1 (v/v).
Micron-sized Cu3(BTC)2 was prepared according to the method
reported by Biemmi et al.50 0.349 g of Cu(NO3)2$3H2O was dissolved in 10 mL of distilled water. Another solution containing
0.1785 g of BTC dissolved in 10 mL of absolute ethanol was
prepared. Both solutions were mixed under vigorous stirring for
1 min and thermally treated in a PTFE-lined stainless steel autoclave at 180  C for 16 h. The precipitate was washed with
a water : ethanol mixture 1 : 1 (v/v), and dried in an oven at 60  C.
Amino zinc carboxylate IsoRecticular MOF-3 (amino IRMOF-3)
was prepared based on the method reported by Savonnet et al.52
2.4 g of Zn(NO3)3$3H2O and 0.66 g of 2-amino terephthalic acid
were dissolved in 80 mL of dimethylformamide (DMF) and the
solution was cooled to 40  C. 4.4 mL of triethylamine was then
added slowly to the cooled synthesis mixture and stirred for 1 h.
The temperature was slowly raised to 4  C after 1 h. The solid was
washed with DMF through repeated centrifugation and redispersion. The final product was dried in an oven at 60  C. Similar
procedures were applied for the synthesis of IRMOF-3 at room
temperature for 1 h.

analysis (GC, Chrompack 8760 WCOT fused silica capillary

column, 30 m long). The yields of the product were determined
by using nonane as the external standard considering the
response factors unity. Leaching test and evidence of heterogeneity in the catalysis of styrene oxide ring opening by methanol
were determined by removing the solid catalysts via centrifugation after 10 minutes of the reaction time and the clear reaction
mixture was continued under similar reaction conditions for
a further 140 minutes.

Results and discussion

Conventional solvothermal synthesis of Cu3(BTC)2 leads to
crystal sizes of tens of microns (Fig. 1a). According to SEM
investigations (Fig. 1b), aggregated crystals with irregular
morphology and sizes of about 200300 nm diameter were
observed in the present synthesis in ethanol at room temperature.
These crystals were slightly smaller than those reported by
Zhuang et al.38 who showed the preparation of 2 mm sized
Cu3(BTC)2 crystals using the ethanol precipitation approach. By
freezing the reaction mixture in liquid nitrogen immediately after
mixing and freeze drying, 100 nm sized crystals were obtained
(Fig. 1c). Freeze drying is a well known method for its application in drying and preserving biological specimens and has also
been developed for the preparation of porous micro- and
nanostructured materials with systematic control of pore
morphology and pore volume.53 In this study, the freeze drying
approach was found to be very efficient for controlling the crystal
growth. In a freeze drying experiment, the solvent molecules
undergo sublimation under vacuum from direct solid to gas
conversion without intervention of a liquid phase, thus inhibiting
further crystal growth.

Characterization
The as-synthesized Cu3(BTC)2 nanomaterials were characterized
by a scanning electron microscope (SEM, Philips XL-30 FEG
equipped with a tungsten filament), a powder X-ray diffractometer
(PXRD, STOE StadiP diffractometer in high-throughput transmission mode employing Cu Ka1 radiation), a thermogravimetric
instrument (TGA, Q 500), and a N2 adsorption instrument
(Micromeritics Tristar 3000), and by a FTIR spectroscope (Bruker,
IFS 66v/s).
Catalytic reaction
Catalytic reactions for ring opening of styrene oxide (97+%,
Acros) with methanol (HPLC grade, BDH) were performed in
close vials inserted into a copper block. In a typical reaction,
1.25 mmol of styrene oxide was added to 7.5 mL of methanol. 50
mg of solid catalysts were used. The reaction temperature was set
at 40  C and the content was magnetically stirred at 1000 rpm.
Aliquots of the reaction mixture were periodically withdrawn
with a microsyringe at the intervals of 10, 30, 60, 90, 120 and 150
minutes throughout the reaction. Clear aliquots were obtained
via centrifugation and filtration prior to gas chromatography
This journal is The Royal Society of Chemistry 2012

Fig. 1 SEM images of Cu2(BTC)3 materials prepared from: (a)

conventional hydrothermal treatment, scale bar: 10 mm; (b) room
temperature, scale bar: 1 mm; (c) freeze drying approaches, scale bar: 1 mm
and (d) pre-cooling method, scale bar: 500 nm.

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However, in the case of Cu3(BTC)2 nanocrystals prepared

according to the pre-cooling method this inhibition of crystal
growth is less distinct. Due to crystallization and Oswald
ripening processes in the solution the particle size distribution is
broader compared to the freeze drying method. Nevertheless the
primary particle size ranges between 50 and 500 nm and even the
smallest particles were highly crystalline as shown in Fig. 1d.
Another interesting observation for this preparation procedure is
that both precipitation temperature and particle size could be
tuned over a broad range. By adding water to the educt solutions
the precipitation temperature could be raised and thus significantly larger particles were prepared. This effect is highlighted in
Fig. 2 for different ethanol to water ratios.
The crystallinity and cubic HKUST-1 structure of Cu3(BTC)2
nanocrystals were confirmed by comparing the XRD patterns
with the hydrothermally synthesized Cu3(BTC)2 reference
material (Fig. 3a). No Cu2O was observed as evidenced by XRD,
indicating high phase purity for freeze dried and pre-cooling
samples (Fig. 3c and d, respectively). The permanent porosity of
the nanosized Cu3(BTC)2 samples was verified by N2 physisorption analysis (Fig. 4a). N2 adsorptiondesorption showed
type I behavior which is attributed to a microporosity with given
BrunauerEmmetTeller (BET) and Langmuir surface areas of
999 and 1378 m2 g1 for freeze dried samples and unprecedented
1805 and 2052 m2 g1 for pre-cooling samples, respectively. A
small hysteresis loop was noted in the range of 0.51.0 relative
pressure, possibly due to the intercrystalline packing of the
nanocrystals. The difference of specific surface area between
freeze dried and pre-cooling samples likely is due to a different
degree of crystal imperfections.54 In the freeze drying procedure
the crystallization time is very short (about 1 min), while in the

Fig. 2 SEM images of Cu3(BTC)2 materials prepared via the pre-cooling

method with different ethanol to water ratios ranging from pure ethanol
(a) to 75% ethanol (f) in 5% steps (scale bar ac: 1 mm; df: 5 mm).

13744 | J. Mater. Chem., 2012, 22, 1374213746

Fig. 3 XRD patterns of Cu2(BTC)3 materials prepared from: (a)

conventional hydrothermal treatment, (b) room temperature, (c) freeze
drying and (d) pre-cooling approaches. The reflection ascribed to Cu2O is
marked by a vertical line at 36.4 (2 theta).

pre-cooling method the warming of the synthesis mixture to

room temperature takes a much longer time. The TGA result
confirmed the thermal stability of the nanosized Cu3(BTC)2
which was comparable to the reported bulk Cu3(BTC)2.49 Three
steps of weight loss were noted (Fig. 4b). The first two steps of

Fig. 4 (a) N2 adsorptiondesorption isotherms of the nanosized

Cu3(BTC)2 MOF prepared from pre-cooling (top) and freeze drying
(bottom) approaches and (b) TGA profile of a typical nanosized
Cu3(BTC)2 MOF.

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weight loss from 40130  C and 130240  C temperature ranges

are attributed to the physically and chemically adsorbed water in
the HKUST-1 framework, respectively. The structure decomposes in the temperature range 240450  C.
In order to verify whether the new concept could be applied for
the synthesis of other types of nanosized MOFs, the pre-cooling
approach was attempted for the synthesis of amino MOF-3.
Amino IRMOF-3 was prepared from zinc nitrate hexahydrate,
2-amino terephthalic acid and triethylamine. Spontaneous
precipitation was observed upon addition of the triethylamine to
the synthesis solution containing zinc nitrate hexahydrate and
2-amino terephthalic acid cooled at 40  C. According to SEM,
nanocrystallites of amino IRMOF-3 MOF were obtained with
a particle size of ca. 150 nm as shown in Fig. 5b compared to
large agglomerates and micron-sized cubic shaped crystals
obtained from room temperature synthesis52 (Fig. 5a) and solvothermal synthesis approaches,55,56 respectively. The results
proved that the pre-cooling method was also useful for nanosizing amino IRMOF-3. The crystallinity of the as-synthesized
amino IRMOF-3 was confirmed by XRD (Fig. 5c). The presence
of the free amino groups in the framework structure was
confirmed by means of FTIR spectroscopy (Fig. 5d). Observed
bands at 3360 and 3472 cm1 are assigned to the symmetric and
asymmetric stretching of primary amines, respectively.52,55,56
The catalytic performance of nanosized Cu3(BTC)2 was evaluated for styrene oxide methanolysis under mild reaction
conditions in comparison to micron sized Cu3(BTC)2. The
organic synthesis product of 2-methoxy-2 phenylethanol is
a valuable organic solvent and an intermediate for the pharmaceutical and chemical industries.57 The epoxide ring opening
reactions, which are catalyzed by strong acid or base catalysts,
require a long reaction time and high reaction temperature, often
leading to low product selectivity. Ring opening of styrene oxide
with methanol catalyzed by nanosized Cu3(BTC)2 showed better
catalytic activity and selectivity with achieved 90% conversion

Fig. 6 (a) Methanolysis of styrene oxide catalyzed by Cu3(BTC)2 of

different crystal sizes and (b) heterogeneity test of 100 nm sized
Cu3(BTC)2 by removing the solid catalyst after 10 min and continued up
to 150 min showing no further conversion of substrate. Reaction conditions: 1.25 mmol of styrene oxide, 7.5 mL of methanol, 50 mg of catalyst,
40  C, 1000 rpm, 2.5 h.

and 100% selectivity after 2.5 h at 40  C (Fig. 6a). It should be

noted that hydrothermally synthesized Cu3(BTC)2 and the
control experiment gave less than 2% conversion under similar
conditions (Fig. 6a). The kinetic studies of activity over reaction
time showed that the nanosized Cu3(BTC)2 was more active than
the room temperature synthesized Cu3(BTC)2. The observed
enhanced catalytic activity for the nanosized catalyst could
probably originate from shorter diffusional pathways which
efficiently reduce diffusional limitations, typical for liquid phase
catalysis. The stability and heterogeneity of the catalyst were
evaluated by removing the solid via centrifugation after 10 min of
reaction time and the conversion of styrene oxide in the clear
supernatant was monitored for a further 140 min. No further
conversion of the substrate was noted (Fig. 6b), indicating that
the ring opening reaction of styrene oxide with methanol catalyzed by the nanosized Cu3(BTC)2 is truly heterogeneous.

Conclusions

Fig. 5 SEM images of amino IRMOF-3 nanocrystals prepared by: (a)

room temperature synthesis (scale bar 2 mm) and (b) pre-cooling
approach (scale bar 2 mm). (c) XRD patterns of amino IRMOF-3
prepared using pre-cooling (top) and room temperature synthesis
(bottom). (d) IR spectrum of nanosized IRMOF-3 material prepared
using the pre-cooling method.

This journal is The Royal Society of Chemistry 2012

In conclusion, two convenient synthesis procedures involving

either reactant mixing and freeze drying, or mixing of cooled
reagents, were found efficient for tuning of the Cu3(BTC)2 MOF
crystal size in the sub-micrometer range. Pure phase Cu3(BTC)2
with specific particle sizes ranging from 100 nm up to 5 mm could
be synthesized. These new methods avoid the need of crystal
growth preventing additives. The pre-cooling drying synthesis
concept could also be used to synthesize nanosized amino
IRMOF-3. Our work opens up alternative routes for MOF
synthesis at low temperature. Easy and convenient preparation
techniques enable future scale up processes depending on the
availability of large scale freeze drying equipment.
J. Mater. Chem., 2012, 22, 1374213746 | 13745

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Acknowledgements
The authors gratefully acknowledge financial support from the
EU FP7 NANOMOF project. J.A.M. thanks the Flemish
Government (long-term Methusalem Funding) and the Belgium
Government (IAP-PAI networking).

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Notes and references

1 G. F
erey, Chem. Soc. Rev., 2008, 37, 191.
2 O. M. Yaghi, M. OKeeffe, N. W. Ockwig, H. K. Chae, M. Eddaoudi
and J. Kim, Nature, 2003, 423, 705.
3 M. J. Rosseinsky, Microporous Mesoporous Mater., 2004, 73, 15.
4 H. Hayashi, A. P. C^
ot
e, H. Furukawa, M. OKeeffe and O. M. Yaghi,
Nat. Mater., 2007, 6, 501.
5 G. F
erey, C. Mellot-Draznieks, C. Serre, F. Millange, J. Dutour,
S. Surbl
e and I. Margiolaki, Science, 2005, 309, 2040.
6 M. Eddaoudi, J. Kim, N. Rosi, D. Vodak, J. Wachter, M. OKeeffe
and O. M. Yaghi, Science, 2002, 295, 469.
7 Y. K. Park, S. B. Choi, H. Kim, K. Kim, B.-H. Won, K. Choi,
J.-S. Choi, W.-S. Ahn, N. Won, S. Kim, D. H. Jung, S.-H. Choi,
G.-H. Kim, S.-S. Cha, Y. H. Jhon, J. K. Yang and J. Kim, Angew.
Chem., Int. Ed., 2007, 46, 8230.
8 N. Klein, I. Senkovska, K. Gedrich, U. Stoeck, A. Henschel,
U. Mueller and S. Kaskel, Angew. Chem., Int. Ed., 2009, 48, 9954.
9 B. Wang, A. P. C^
ot
e, H. Furukawa, M. OKeeffe and O. M. Yaghi,
Nature, 2008, 453, 207.
10 X.-S. Wang, S. Ma, D. Sun, S. Parkin and H.-C. Zhou, J. Am. Chem.
Soc., 2006, 128, 16474.
11 P. Horcajada, S. Surbl
e, C. Serre, D.-Y. Hong, Y.-K. Seo,
J.-S. Chang, J.-M. Greneche, I. Margiolaki and G. F
erey, Chem.
Commun., 2007, 2820.
12 Y. Zhao, J. Zhang, B. Han, J. Song, J. Li and Q. Wang, Angew.
Chem., Int. Ed., 2011, 50, 636.
13 H. Furukawa, N. Ko, Y. B. Go, N. Aratani, S. B. Choi, E. Choi,
Yazaydin, R. Q. Snurr, M. OKeeffe, J. Kim and
A. O.
O. M. Yaghi, Science, 2010, 329, 424.
14 Y. Li and R. T. Yang, Langmuir, 2007, 23, 12937.
15 P. L. Llewellyn, S. Bourrelly, C. Serre, A. Vimont, M. Daturi,
L. Hamon, G. D. Weireld, J.-S. Chang, D.-Y. Hong, Y. J. Hwang,
S. H. Jhung and G. F
erey, Langmuir, 2008, 24, 7245.
16 S. N. Klyamkin, E. A. Berdonosova, E. K. Kogan, K. A. Kovalenko,
D. N. Dybtsev and V. P. Fedin, Chem.Asian J., 2011, 6, 1854.
17 S. Ma and H.-C. Zhou, Chem. Commun., 2010, 46, 44.
18 N. L. Rosi, J. Eckert, M. Eddaoudi, D. T. Vodak, J. Kim,
M. OKeeffe and O. M. Yaghi, Science, 2003, 300, 1127.
19 S. S. Kaye, A. Dailly, O. M. Yaghi and J. R. Long, J. Am. Chem. Soc.,
2007, 129, 14176.
20 Y. Liu, J. F. Eubank, A. J. Cairns, J. Eckert, V. Ch. Kravtsov,
R. Luebke and M. Eddaoudi, Angew. Chem., Int. Ed., 2007, 46, 3278.
21 J. L. C. Rowsell and O. M. Yaghi, Angew. Chem., Int. Ed., 2005, 44,
4670.
22 D. Britt, H. Furukawa, B. Wang, T. G. Clover and O. M. Yaghi,
Proc. Natl. Acad. Sci. U. S. A., 2009, 106, 20637.
23 L. Alaerts, M. Maes, L. Giebeler, P. A. Jacobs, J. A. Martens,
J. F. M. Denayer, C. E. A. Kirschhock and D. E. De Vos, J. Am.
Chem. Soc., 2008, 130, 14170.
24 M. Maes, F. Vermoortele, L. Alaerts, J. F. M. Denayer and D. E. De
Vos, J. Phys. Chem. C, 2011, 115, 1051.
25 M. Maes, F. Vermoortele, L. Alaerts, S. Couck, C. E. A. Kirschhock,
J. F. M. Denayer and D. E. De Vos, J. Am. Chem. Soc., 2010, 132,
15277.

13746 | J. Mater. Chem., 2012, 22, 1374213746

26 D. Farrusseng, S. Aguado and C. Pinel, Angew. Chem., Int. Ed., 2009,

48, 7502.
27 A. Corma, H. Garc
a and F. X. Llabr
es i Xamena, Chem. Rev., 2010,
110, 4606.
28 J. Lee, O. K. Farha, J. Roberts, K. A. Scheidt, S. T. Nguyen and
J. T. Hupp, Chem. Soc. Rev., 2009, 38, 1450.
29 L. Ma, C. Abney and W. Lin, Chem. Soc. Rev., 2009, 38, 1248.
30 L. H. Wee, S. R. Bajpe, N. Janssens, I. Hermans, K. Houthoofd,
C. E. A. Kirschhock and J. A. Martens, Chem. Commun., 2010, 46,
8186.
31 D. Jiang, T. Mallat, F. Krumeich and A. Baiker, Catal. Commun.,
2011, 12, 602.
32 D. Tanaka, A. Henke, K. Albrecht, M. Moeller, K. Nakagawa,
S. Kitagawa and J. Groll, Nat. Chem., 2010, 2, 410.
33 W. Lin, W. J. Rieter and K. M. L. Taylor, Angew. Chem., Int. Ed.,
2009, 48, 650.
34 K. M. L. Taylor-Pashow, J. D. Rocca, Z. Xie, S. Tran and W. Lin, J.
Am. Chem. Soc., 2009, 131, 14261.
35 P. Horcajada, T. Chalati, C. Serre, B. Gillet, C. Sebrie, T. Baati,
J. F. Eubank, D. Heurtaux, P. Clayette, C. Kreuz, J.-S. Chang,
Y. K. Hwang, V. Marsaud, P.-N. Bories, L. Cynober, S. Gil,
G. F
erey, P. Couvreur and R. Gref, Nat. Mater., 2010, 9, 172.
36 M. R. Lohe, K. Gedrich, T. Freudenberg, E. Kockrick, T. Dellmann
and S. Kaskel, Chem. Commun., 2011, 47, 3075.
37 A. Carn
e, C. Carbonell, I. Imaz and D. Maspoch, Chem. Soc. Rev.,
2011, 40, 291.
38 J.-L. Zhuang, D. Ceglarek, S. Pethuraj and A. Terfort, Adv. Funct.
Mater., 2011, 21, 1442.
39 G. Yuan, C. Zhu, Y. Liu and Y. Cui, Chem. Commun., 2011, 47, 3180.
40 S. K. Nune, P. K. Thallapally, A. Dohnalkova, C. Wang, J. Liuc and
G. J. Exarhosc, Chem. Commun., 2010, 46, 4878.
41 J. Cravillon, S. M
unzer, S.-J. Lohmeier, A. Feldhoff, K. Huber and
M. Wiebcke, Chem. Mater., 2009, 21, 1410.
42 S. Diring, S. Furukawa, Y. Takashima, T. Tsuruoka and
S. Kitagawa, Chem. Mater., 2010, 22, 4531.
43 K. M. L. Taylor, W. J. Rieter and W. Lin, J. Am. Chem. Soc., 2008,
130, 14358.
44 K. E. deKrafft, Z. Xie, G. Cao, S. Tran, L. Ma, O. Z. Zhou and
W. Lin, Angew. Chem., Int. Ed., 2009, 48, 9901.
45 M. Klimakow, P. Klobes, A. F. Th
unemann, K. Rademann and
F. Emmerling, Chem. Mater., 2010, 22, 5216.
46 D. Zacher, J. Liu, K. Huber and R. A. Fischer, Chem. Commun.,
2009, 1031.
47 M. Ma, D. Zacher, X. Zhang, R. A. Fischer and N. Metzler-Nolte,
Cryst. Growth Des., 2011, 11, 185.
48 W. J. Rieter, K. M. L. Taylor, H. Y. An, W. Lin and W. Lin, J. Am.
Chem. Soc., 2006, 128, 9024.
49 S. S.-Y. Chui, S. M.-F. Lo, J. P. H. A. Charmant, G. A. Orpen and
I. D. Williams, Science, 1999, 283, 1148.
50 E. Biemmi, S. Christian, N. Stock and T. Bein, Microporous
Mesoporous Mater., 2009, 117, 111.
51 R. S. Bajpe, C. E. A. Kirschhock, A. Aerts, E. Breynaert, G. Absillis,
T. N. Parac-Vogt, L. Giebeler and J. A. Martens, Chem.Eur. J.,
2010, 16, 3926.
52 M. Savonnet, S. Aguado, U. Ravon, D. Bazer-Bachi, V. Lecocq,
N. Bats, C. Pinel and D. Farrusseng, Green Chem., 2009, 11, 1729.
53 L. Qian and H. J. Zhang, J. Chem. Technol. Biotechnol., 2011, 86, 172.
54 P. Chowdhury, C. Bikkina, D. Meister, F. Dreisbach and S. Gumma,
Microporous Mesoporous Mater., 2009, 117, 406.
55 H. Yim, E. Kang and J. Kim, Bull. Korean Chem. Soc., 2010, 31, 1041.
56 J. Gascon, U. Aktay, M. O. Hernandez-Alonso, G. P. M. van Klink
and F. Kapteijn, J. Catal., 2009, 261, 75.
57 M. Tokunaga, J. F. Larrow, F. Kakiuchi and E. N. Jacobsen, Science,
1997, 277, 936.

This journal is The Royal Society of Chemistry 2012