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Cite this: Dalton Trans., 2011, 40, 321

www.rsc.org/dalton PERSPECTIVE
Microwave-Assisted Synthesis of Metal–Organic Frameworks
Jacek Klinowski,*a,b Filipe A. Almeida Paz,*b Patrı́cia Silvab and João Rocha*b
Received 22nd June 2010, Accepted 9th September 2010
DOI: 10.1039/c0dt00708k
Published on 21 October 2010 on http://pubs.rsc.org | doi:10.1039/C0DT00708K

Microwave heating, used in organic chemistry for several decades, has only recently been applied to the
preparation of multi-dimensional coordination polymers, more commonly known as metal–organic
frameworks (MOFs). Microwave heating allows short reaction times, fast kinetics of crystal nucleation
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and growth, and high yields of desirable products which can be isolated with few or no secondary
products. The most significant developments in the use of microwave heating for the preparation of
MOFs are briefly reviewed from this perspective, emphasizing systematic studies of well-characterised
materials, which lead to their isolation in large quantities over economically-viable periods of time.
Emphasis is given to the growth of nano-sized crystallites which may find direct applications in
functional devices.

1. Introduction and Robson4 expanded the concept to coordinative bonds when

they described the design of diamond-type frameworks based on
The branch of supramolecular chemistry known as “crystal covalent bonds, now known as MOFs, coordination polymers
engineering” focuses on the construction of large molecular or coordination frameworks.1a,5 Covalent bonding affects the
networks with predictable topologies and properties controlled properties of the products,1a,1g,6 and particular attention has been
by the chemical nature of the individual components.1 The work given to the design of highly porous structures suitable for host–
of Desiraju2 and Etter3 on organic crystals assembled via hydrogen guest exchange and gas storage, and possessing catalytic, electrical,
bonds is considered the beginning of crystal engineering. Hoskins magnetic or photoluminescent properties.
Organic ligands and metal ions are considered the “primary
a
Department of Chemistry, University of Cambridge, Lensfield Road, building units”, and larger aggregates formed by multidentate
Cambridge, UK, CB2 1EW. E-mail: jk18@cam.ac.uk
b linkers “secondary building units” (SBUs).1f ,g,6c,7 Both terms
Department of Chemistry and CICECO, University of Aveiro, Campus
Universitário de Santiago, 3810-193, Aveiro, Portugal. E-mail: filipe. have been imported from zeolite chemistry. Unfortunately, unlike
paz@ua.pt, patricia@ua.pt, rocha@ua.pt with zeolites,8 the number of possible combinations of metal

Jacek Klinowski has the degrees Filipe Almeida Paz, born in 1978,
of Ph.D. from the Jagiellonian obtained a first degree in ana-
University, Kraków, Poland lytical chemistry at the Univer-
(where he studied chemistry sity of Aveiro, Portugal, in 2000,
and mathematics) and from and in 2004 a Ph.D. in Natural
the University of London, UK, Sciences from the University of
and MA and Sc.D. from the Cambridge, UK, under the super-
University of Cambridge, UK, vision of Jacek Klinowski. He has
where he is now Professor been an Auxiliary Researcher at
of Chemical Physics at the the Centre for Research in Ce-
Department of Chemistry ramics and Composite Materials
and a Professorial Fellow of (CICECO) at Aveiro since 2004.
Peterhouse. His interests include His research interests are the de-
Jacek Klinowski the solid-state NMR of a great Filipe A. Almeida Paz sign of functional metalorganic
variety of materials (micro- and mesoporous molecular sieves, frameworks, the development of novel synthetic methods for their
glasses, proton sponges, minerals, ceramics, fullerenes etc.); carbon preparation and the use of X-ray diffraction techniques for the
and silica nanotubes, graphite oxide; and periodic minimal surfaces structure solution of microporous materials.
which appear in many inorganic, organic and biological structures.
He has collaborated with João Rocha and Filipe Almeida Paz for
many years.

This journal is © The Royal Society of Chemistry 2011 Dalton Trans., 2011, 40, 321–330 | 321
 View Article Online

cations and organic linkers is enormous, and we are still un- 2.2 Microwave-Assisted Synthesis
able to predict which structure will result from any particular
combination. Microwave heating was discovered accidentally in 1946 by P.L.
Synthetic methods used for the preparation of MOFs developed Spencer at the Raytheon Corporation when a chocolate bar melted
in three stages. At first, they relied on slow evaporation of the in his pocket while he was working on radar applications of
solvents or their diffusion over time to create large single crystals microwaves, electromagnetic waves with wavelengths in the 1 m to
in very small quantities over periods from weeks to months. Later, 1 mm range (300 MHz to 300 GHz). The frequency of radiation
solvothermal approaches, borrowed from conventional zeolite used in domestic microwave ovens is 2.45 GHz (12.24 cm), with
synthesis, started to be implemented, allowing reaction times to maximum power of ca. 800 W.
be reduced to a few days. Although microcrystalline powders Microwaves are normally generated by a magnetron, consisting
are usually obtained under these conditions, the method can of an oscillator converting high-voltage direct current into high-
be finely tuned so as to lead to the isolation of single crystals. frequency radiation. In a typical laboratory instrument waveguides
transfer the generated energy from the magnetron to the sample
Published on 21 October 2010 on http://pubs.rsc.org | doi:10.1039/C0DT00708K

The present task facing crystal engineers is to reduce reaction

times further, increase yields and produce functional materials in chamber (Fig. 1 – top). Many molecules, notably water, possess
large amounts. Current research is mainly driven by the desire dielectric moments and rotate to align themselves with the
to develop industrial applications of MOFs as functional devices. alternating electric field of the microwaves. The heat generated
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Microwave synthetic approaches may soon replace conventional

solvothermal synthesis based on convection of heat, and reports
of MOFs prepared under these conditions can already be found
in the literature. This review gives a brief overview of the research
so far, describing the advantages and limitations of microwave
heating. We note that Noro and Nakamura9 have already included
a small section on this synthetic approach in their general
review.

2. Background
2.1 Conventional Solvothermal Synthesis

Synthesis of MOFs proceeds via the self-assembly of primary

building units through a self-recognition process. The vast ma-
jority of reported structures have been prepared by solvothermal
synthesis which usually requires long reaction times (days to
weeks), bulky equipment and heavy energy consumption. To
overcome these limitations, new approaches have been developed, Fig. 1 (top) Schematic representation of the basic components of a
such as electrochemical essays7b,10 and solvothermal synthesis with monomode microwave oven designed for scientific research. (bottom)
immiscible solvents.7b,11 An even more promising route involves Comparison of heating profiles inside the reaction vessels for standard
microwave-assisted synthesis.12 conductive and microwave heating.

Patrı́cia Silva, born in 1984, com- João Rocha, born in 1962, com-
pleted a first degree in chemistry pleted undergraduate studies in
in 2006 and an M.A. in analytical physics and chemistry at the Uni-
chemistry and quality control in versity of Aveiro, Portugal, where
2007 at the University of Aveiro, he is now Professor of Chem-
Portugal. In 2008 she enrolled istry. He is a member of the
in the doctoral programme in Lisbon Academy of Sciences.
chemistry under the supervision João Rocha obtained a Ph.D.
of Filipe Almeida Paz at the in 1990 under the supervision of
Centre for Research in Ceramics Jacek Klinowski at the University
and Composite Materials (CI- of Cambridge, UK, where he then
CECO). Her current research is remained for a year as a post-
focused on the design, synthesis doctoral fellow. Since 2002 he has
Patrı́cia Silva and development of photolumi- João Rocha been the director of the Centre
nescent metal–organic frameworks. for Research in Ceramics and Composite Materials (CICECO)
at Aveiro, Portugal. His research interests include microporous
transition metal and lanthanide silicates, organic frameworks,
photoluminescent materials and solid-state NMR.

322 | Dalton Trans., 2011, 40, 321–330 This journal is © The Royal Society of Chemistry 2011
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by the molecular movement is dispersed as the molecules collide ∑ [Mg(Thz)(H2 O)4 ] (one-dimensional chain), [Ca2 (Thz)2 (H2 O)8 ]
with other molecules. The sample chamber is a Faraday cage (one-dimensional chain), [Sr(Thz)(H2 O)3 ] (one-dimensional
which prevents the microwaves escaping into the environment. chain) and [Ba2 (Thz)2 (H2 O)7 ] (lamellar structure).22
The main advantage of microwave heating is its energy efficiency Studies of known materials such as MOF-5,17j IR-
because power is only applied within the reactive mixture. Energy is MOF1, IRMOF2 and IRMOF3,17d or [Cu3 (BTC)2 (H2 O)3 ] and
generated directly throughout the bulk of the material instead of by [Cu2 (OH)(BTC)(H2 O)]·2nH2 O17o are most useful for the specific
conduction from the external surface (Fig. 1 – bottom). Microwave examination of crystallinity, morphology, particle size and the
heating is almost instantaneous, takes place without heating the design of new applications. As the preparation of these materials
air or the container, and allows the use of temperatures above the is already known, modifications can be introduced which may
boiling point of a solvent within pressurized vessels.13 The heating open new possibilities for functionalization.
is specific, with different materials responding differently to
microwave energy. For example, pharmaceuticals can be sterilised
Published on 21 October 2010 on http://pubs.rsc.org | doi:10.1039/C0DT00708K

without damaging the packaging. 3.1 Influence of Reaction Conditions

Research in this field is mainly performed using microwave ovens
specifically designed for chemical synthesis, which allow control Reaction conditions in microwave heating vary considerably with
of the various parameters (e.g., irradiation power, time of the respect to (i) the MOF system under study, (ii) the apparatus
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reaction, temperature inside the vessels, among other parameters employed and (iii) the preferences of the particular research
– see Section 3.1), but good quality domestic microwave ovens group. Some specific parameters of the synthetic procedure,
can also be used. Although the literature contains many reports such as temperature, irradiation power, time of the reaction and
on materials synthesised using modified domestic instruments, the composition of the reactive mixtures can be varied; others are
reproducibility varies with the brand of the instrument and the size specific to the system under investigation. Typically, synthesis
and geometry of the microwave cage. proceeds above 100 ◦ C and its duration is systematically varied in
Microwave heating may have a beneficial effect on the properties order to establish the best conditions for the isolation of the desired
and performance of materials. For example, sintering zirconia in product. Such is also common practice with the conventional
a microwave furnace produces uniform grain size. It can also give hydrothermal approach. However, since the reactions are fast and
better control of the mechanical and optical properties of the the number of variable parameters is large, probing just one system
products than conventional heating. On the other hand, working could be very time consuming. For example, Sonnauer and Stock23
with microwaves raises some concerns with respect to safety developed a high-throughput methodology which allowed speedy
and reproducibility. Although reactions are very fast and usually investigation of a large part of the parameter space for the isolation
proceed at low temperatures, the morphology and phase purity of of [Ln(O3 P–C2 H4 –SO3 )] (where Ln3+ = Ho3+ to Lu3+ , Y3+ ). They
the products can be adversely affected if the reaction conditions are also concluded that stirring the reaction mixture reduced yields
not strictly controlled (see below), thus affecting the mechanical but these can be improved by increasing synthesis duration.
strength, conductivity and chemical reactivity of the products.14 The most important instrumental parameter in microwave
While the development of microwave synthesis has been mainly heating is the power of irradiation and the question of how it
driven by the pharmaceutical industry, the technique has been is created, delivered and controlled throughout the reaction. This
successfully used in organic synthesis15 and in the preparation depends mainly on the device employed. Schlesinger et al.24 have
of nanoporous inorganic materials.16 Although its use in the recently identified differences in experimental set-up as the main
preparation of MOFs is still in its infancy, several interesting reason for the different conclusions reached by them and Seo
reports are available.17 Microwave heating allows a considerable et al.17o in the preparation of HKUST. A selection of the conditions
reduction of the reaction time,16e enables phase selectivity18 and for some of the best documented reactions is given in Table 1. In
the control of crystal morphology.19 In the following sections we general, reactions occur between a few seconds and some minutes,
describe some remarkable examples of the preparation of new and with times rarely exceeding 1 h.
known hybrid porous solids. Choi et al. investigated the crystallinity and morphology of
MOF-5 by varying the power level, irradiation time, temperature,
3. Microwave-Assisted Synthesis of MOFs solvent concentration and substrate composition.17j Conventional
heating (105 ◦ C, 24 h) was used for comparison. The temperature
Many known and novel MOFs structures produced using mi- of microwave heating was varied between 95 and 135 ◦ C, the
crowave irradiation can be found in the literature. Different reaction time between 10 and 60 min and the irradiation power was
research groups adopt different strategies and the choice of a 600, 800 and 1000 W. Remarkable insights into the preparation of
chemical system to study is somewhat haphazard. Some remark- this porous structure were obtained:
able recent reports devoted to the synthesis and structural features i) microwave irradiation leads to crystals after only 15 mins of
of MOFs clearly demonstrate the scientific curiosity aroused by reaction while 12 h are necessary with the conventional method
the method itself: (30 mins and 24 h, respectively, for high quality crystals);
∑ [Ag(dpa)], [Co(O3 PH)(4,4¢-bpy)(H2 O)], [Zn(O3 PH)(4,4¢- ii) crystals are smaller than those obtained using conventional
bpy)0.5 ] and [Mn[O2 PH(C6 H5 )]2 (4,4¢-bpy)].20 heating (20–25 mm vs. 500 mm) – see Fig. 2a and 2b.
∑ Tl(l) cyanoximates [Tl(2Cl-PhCO)] and [Tl(4Br-PhCO)].21 iii) the surface area and CO2 sorption capacity are not affected
∑ Two new isostructural MOFs, (EMIm)2 [M3 (BTC)2 (OAc)2 ] when compared with the conventional approach;
(where M2+ = Ni2+ or Co2+ ) prepared using the ionic liquid EMIm vi) crystal degradation and surface defects occur when irradia-
(melting point 83 ◦ C) as solvent and template.17c tion lasts over 30 mins (Fig. 2c).

This journal is © The Royal Society of Chemistry 2011 Dalton Trans., 2011, 40, 321–330 | 323
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Table 1 Reaction conditions for selected microwave-assisted syntheses of MOFs

MOFs Reaction conditions Reference

IRMOF1, IRMOF2, IRMOF3 25 s Ni and Masel17d

(EMIm)2 [Ni3 (TMA)2 (OAc)2 ] (EMIm)2 [Co3 (TMA)2 (OAc)2 ] 200 ◦ C, 50 min Lin et al.17c
[Ni20 (C5 H6 O4 )20 (H2 O)8 ]·40H2 O 150–220 ◦ C within 1 min Jhung et al.17q
[Ni22 (C5 H6 O4 )20 (OH)4 (H2 O)10 ]·38H2 O
Cr-MIL-101 210 ◦ C, 1–40 min Jhung et al.17h
[Cu2 (pyz)2 (SO4 )(H2 O)2 ]n 180 ◦ C, 20 min, 6 h Amo-Ochoa et al.17f
[Cu2 (oba)2 (DMF)2 ]·5.25(DMF) single-step: 160 ◦ C, 1–150 min; Wang et al.17l
multi-step: 80–160 ◦ C, 2 h
[Mn3 (BTC)2 (H2 O)]6 120 ◦ C, 10 min Taylor et al.32
[Cd(HIDC)(bbi)0.5 ] 2.0 Mpa, 20 min Liu et al.17k
MOF-5 95–135 ◦ C, 10–60 min Choi et al.17j
[Cu3 (BTC)2 (H2 O)3 ] [Cu2 (OH)(BTC)(H2 O)]·2nH2 O 140 ◦ C, 60 min; Seo et al.17o
Published on 21 October 2010 on http://pubs.rsc.org | doi:10.1039/C0DT00708K

[Cu(H2 BTC)2 (H2 O)2 ]·3H2 O 170 ◦ C, 10 min

[Zn2 (NDC)2 (DPNI)] 120 ◦ C, 1 h Bae et al.30
[Co3 (NDC)3 (DMF)4 ] and [Mn3 (NDC)3 (DMF)4 ] 110 ◦ C, 30 min Liu et al.31
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Fig. 3 Comparison of the sorption isotherms of benzene of MIL-101

prepared using microwave heating, active carbon, zeolite HZSM-5 and
mesoporous SBA-15. Images reproduced from Jhung et al.17h

IRMOF1, IRMOF2 and IRMOF3 have been prepared by Ni

and Masel17d using microwave irradiation (150 W) in under a few
seconds. The crystal size could be fine-tuned to the submicrometre
scale by careful manipulation of the reactive mixtures, more dilute
mixtures being preferable.
Seo et al. compared microwave irradiation (300 W, 60
Fig. 2 SEM images of MOF-5 prepared under (a) conventional solvother- mins, 140 ◦ C) and conventional heating for the synthe-
mal synthesis and (b) microwave heating. (c) MOF-5 crystal degradation sis of HKUST-1, [Cu3 (BTC)2 (H2 O)3 ], one of the best well-
with exposure to microwave irradiation. Images reproduced from Choi documented MOFs.17o Apart from HKUST-1 and the known
et al.17j [Cu2 (OH)(BTC)(H2 O)]·2nH2 O, a new phase was isolated:
[Cu(H2 BTC)2 (H2 O)2 ]·3H2 O. Several important conclusions were
v) variation of the composition of the reaction mixture (e.g., drawn:
Zn2+ content) can modify the size and quality of the crystals. i) a lower reaction temperature (120 ◦ C) for the microwave
The properties of MOF-5 were also investigated by Lu irradiation is insufficient to obtain the desired material;
et al.25 who compared the adsorption ability of crystals prepared ii) at 150 ◦ C HKUST-1 is isolated in addition to an
under reflux and under microwave irradiation. Once again, the unknown intermediate phase which can be converted into
conclusion was that the latter approach produces better developed [Cu2 (OH)(BTC)(H2 O)]·2nH2 O at higher temperatures;
crystals with a higher capacity to absorb CO2 . iii) small particles with high surface area can be isolated;
Jhung et al.17h prepared nanoporous Cr-MIL-101 as nano-sized vi) variation of the reaction mixtures has a profound
crystals and found that reaction time was of crucial importance: effect on the product: reduced water content leads to
crystal size and distribution increases with increasing irradiation [Cu2 (OH)(BTC)(H2 O)]·2nH2 O; increased initial concentration of
time, ultimately allowing the isolation of particles with a high the reactants promotes large crystals; there is a non-linear increase
surface area. The microwave-prepared nano-crystals adsorbed in surface area and pore volume with concentration due to the
benzene significantly more rapidly than some commercial alterna- presence of impurities;
tives (Fig. 3). We note the excellent recent review on the structure v) increased irradiation time leads to high yields and larger
and properties of MIL-101.26 crystals, unlike in the conventional heating approach.

324 | Dalton Trans., 2011, 40, 321–330 This journal is © The Royal Society of Chemistry 2011
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Schlesinger et al.24 have recently compared a series of different single-step reaction (160 ◦ C for 1–150 mins) and (iii) multi-step
approaches to the preparation of HKUST-1, reaching identical preparation (heating ramps between 80 and 160 ◦ C and an overall
general conclusions. They also studied the variation of the yield reaction time of 2 h). As MCF-23 contains 3D nanochannels,
with respect to the irradiation time, showing that 30 mins are the synthetic route is important when potential applications are
required to get quantitative amounts whatever solvent is employed considered. While the conventional method is inefficient because
(Fig. 4). In a complementary study, Khan et al.27 demonstrated it leads to impurities, the microwave route produces highly
that the efficiency of microwave heating relies basically on the crystalline phase-pure materials. With single-step synthesis, large
very fast rate of nucleation while the activation energy remains single crystals are rarely obtained and increased reaction time does
unaltered. Reaction kinetics are improved due to a similar effect not improve yields (Fig. 5a–e). However, the multi-step synthetic
found in inorganic framework materials: a pre-exponential factor route addresses both questions, leading to large crystals and yields
in the Arrhenius equation arises from the increased number of of ca. 80% (Fig. 5f).
local reactive sites.
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Fig. 4 Yield of the microwave preparation of HKUST-1 as a function of

the irradiation time. Images reproduced from Schlesinger et al.24

Phase-selectivity of the microwave heating was described

by Jhung et al.17q for the preparation of the nickel(II) Fig. 5 SEM pictures of MCF-23 obtained from microwave synthesis with
glutarates [Ni20 (C5 H6 O4 )20 (H2 O)8 ]·40H2 O (MIL-77, cubic) and a single-step (a to e) or multi-step reaction (f). Images reproduced from
Wang et al.17l
[Ni22 (C5 H6 O4 )20 (OH)4 (H2 O)10 ]·38H2 O (tetragonal). For a low tem-
perature and pH the cubic phase is isolated and, as the reaction
∑ Amo-Ochoa et al.17f isolated large single-crystals of
progresses, the product is tetragonal (high temperature and
[Cu2 (pyz)2 (SO4 )(H2 O)2 ] at 180 ◦ C for 0.3–6 h, obtaining the prod-
pH). Interestingly, the tetragonal phase could only be isolated
uct in a higher yield than that of conventional approaches (37.7%
with microwave heating. More recently, Delgado and Zamora28
vs. 12.0%). However, a secondary material, [Cu(pyz)(SO4 )(H2 O)],
reported a one-dimensional polymer which can only be isolated
was also obtained.
using microwave irradiation.
∑ [Cd(HIDC)(bbi)0.5 ] prepared by Liu et al.17k could be isolated
Close control of the pH of the reactive mixtures may also have
directly as large single crystals at a pressure of 2.0 MPa for 20
a profound effect while using microwaves, as found by Liu et al.17n
mins.
Several materials were prepared in just under 20 mins by control-
∑ The first microporous lanthanide-containing MOF isolated
ling the pH of the reaction mixtures: [Mg2 (BTEC)(H2 O)4 ]·2H2 O
directly by microwave synthesis was recently described by Silva
(framework-type structure, pH 4.6), [Mg2 (BTEC)(H2 O)6 ] (lamel-
et al.:29 [Ce2 (pydc)2 (Hpydc)(H2 O)2 ]Cl·(9+y)H2 O (Fig. 6).
lar, pH 4.2) and [Mg2 (BTEC)(H2 O)8 ] (one-dimensional chain, pH
4.8).
3.3 Preparation of Functional MOFs for Applications
3.2 Preparation of Large Crystals The main purpose of a fast, inexpensive and easily controllable
approach is to prepare large quantities of MOFs for functional
Microcrystalline powders or nano-sized crystals are most often
devices. Most attention has been given to porous MOFs for use
isolated under microwave heating due to the fast kinetics of
in gas sorption, storage and separation, and to thin films as
crystal nucleation and growth. Thus, one challenge with mi-
contrasting agents for magnetic resonance imaging, in catalysis
crowave heating is controlling crystallite size. Large crystals are
or conductive materials.
usually more difficult to obtain than in typical solvothermal
approaches. Because structural elucidation is crucial to MOF Gas Separation. [Zn2 (NDC)2 (DPNI)] was used for the sepa-
research, microwave heating may be considered unsuitable for the ration of CO2 from CH4 .30 The material can be prepared under
investigation of new phases. Nevertheless, careful design of the microwave irradiation in high yields at 120 ◦ C in under 1 h, as
synthetic conditions may overcome this limitation: opposed to 48 h in the conventional approach. Crystals from
∑ The Mg2+ system studied by Liu et al.17n (see above) produced microwave irradiation are considerably smaller than those from
crystals as large as 50 mm through strict control of the reaction conventional heating. Remarkably, Bae et al. found that the
conditions. surface area, micropore volume and adsorption capacity are all
∑ [Cu2 (oba)2 (DMF)2 ]·5.25(DMF) (MCF-23) studied by Wang considerably smaller for the microwave sample. Nevertheless, the
et al.17l was prepared in DMF using (i) conventional solvothermal material has a much larger selectivity (ca. 30 times) for CO2 than
synthesis (160 ◦ C for 72 h); (ii) microwave synthesis with a for CH4 when low pressures are employed; for higher pressures

This journal is © The Royal Society of Chemistry 2011 Dalton Trans., 2011, 40, 321–330 | 325
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Published on 21 October 2010 on http://pubs.rsc.org | doi:10.1039/C0DT00708K

Fig. 6 (a) Crystal packing of [Ce2 (pydc)2 (Hpydc)(H2 O)2 ]Cl (9+y)H2 O viewed in perspective along the c-axis, emphasising the large one-dimensional
channels housing water molecules of crystallization and charge-balancing chloride anions. (b) SEM picture of one large crystal as directly obtained from
the microwave synthesis. Images reproduced from Silva et al.29
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the selectivities are similar for the materials prepared using both sions at room temperature. Morphological modification was
approaches. performed using a surfactant under microwave irradiation (120 ◦ C
Mg2+ cations, rarely used in MOF synthesis, enable the for 10 mins, 800 W), leading to block-like crystals. Surface
preparation of [Mg2 (BTEC)(H2 O)4 ]·2H2 O, a functional material functionalization produced a target-specific magnetic resonance
reported by Liu et al. and mentioned above.17n The evacua- imaging material which can be delivered to cancer cells. Another
tion of this framework at 150 ◦ C leads to a functional ma- application concerns nanocrystalline MIL-101 with Fe3+ prepared
terial, [Mg15 (BTEC)6 (HBTEC)2 (H2 O)12 ]·4H2 O, which selectively by Taylor-Pashow et al.33 under microwave irradiation, in which
absorbs H2 but not N2 . The opposite behaviour was found the bridging terephthalic acid was partially substituted with 2-
by Liu et al.31 for [M3 (NDC)3 (DMF)4 ] (M2+ = Co2+ or Mn2+ ): aminoterephthalic acid. This approach introduced anchoring sites
reversible structural change occurred upon desolvating, producing inside the channels which allowed the attachment of biologically-
microporous frameworks which can store H2 in an equal manner, relevant moieties. For example, an optical contrast agent (e.g.,
but the Co2+ -containing material is much more selective for N2 BODIPY dye) and an ethoxysuccinatocisplatin anticancer pro-
(Fig. 7). drug were successfully incorporated (Fig. 8). MIL-101 could also
be impregnated with Pd, Cu or Pd–Cu nanoparticles, typically
Theurapeutic Agents or Catalysts. The Mn2+ -based nano- 2–3 nm in size as described by El-Shall et al.34 In this application
MOF with trimesic acid prepared by Taylor et al.32 was obtained as microwaves were used to reduce the metal precursors, with the
spiral [Mn3 (BTC)2 (H2 O)6 ] nanorods in reverse-phase microemul- final materials exhibiting high oxidation ability for CO.

Fig. 7 (top) Crystal packing of [Co3 (NDC)3 (DMF)4 ] drawn from the CIF data deposited with the Cambridge Structural Database (refcode XIHSEN01).
(bottom left) Nitrogen and (bottom right) hydrogen gas sorption isotherms at 77 K for [M3 (NDC)3 (DMF)4 ] (M2+ = Co2+ (1) or Mn2+ (2); H2 NDC =
2,6-naphthalenedicarboxylic acid; DMF = N,N¢-dimethylformamide). Isotherms reproduced from Liu et al.31

326 | Dalton Trans., 2011, 40, 321–330 This journal is © The Royal Society of Chemistry 2011
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Fig. 8 Schematic representation of the chemical modification of the inner channels of nano-sized particles of MIL-101 by using an optical contrast agent
(BODIPY) and an ethoxysuccinatocisplatin anticancer pro-drug. Grafted crystals exhibited poor stability to the PBS buffer solution and were coated
with a silica layer to reduce the release of the active agents. Images reproduced from Taylor-Pashow et al.33

Thin Films. Because crystal growth is fast under microwave designed by preparing a MOF-5/silicate-1 film deposited on an
irradiation, preparation of thin films offers a promising application Au-coated substrate (Fig. 9d and 9e). The same group prepared
for most materials. In addition, the surfaces of the support do MOF-5 membranes on porous a-alumina substrates, starting from
not need to be chemically modified or have atomically smooth a microwave-induced thermal deposition of seeds which were
surfaces and electrostatical compatibility. With this in mind, Yoo solvothermally treated to grow larger crystals (Fig. 10).17p
and Jeong used microwave irradiation to grow porous and strongly
adherent MOF-5 thin films on several substrates (Fig. 9).17m Three
aluminium oxide substrates were used (Fig. 9a–c): uncoated,
amorphous carbon-coated and graphite-coated. Microwaves em-
ployed had an irradiation power of 500 W and reaction times
of 5–30 s. It was also shown that multilayer films could be

Fig. 10 SEM images of (top and cross-sections) (a) an orientated MOF-5

seed layer and (b) an orientated MOF-5 membrane. Images reproduced
from Yoo et al.17p

Electrical Conductors. [Cu9 (2-dpds)8 (SH)8 ](BF4 ) prepared by

Delgado et al.35 just under 2 h (600 W) is a one-dimensional
Fig. 9 SEM images of MOF-5 grown (30 s irradiation time) on (a) polymer formed by the assembly of metallic Cu9 empty cages.
bare anodized aluminium oxide (AAO) substrate; (b) amorphous carbon The solid product exhibits remarkable electrical conductivity, an
coated AAO and (c) graphite coated AAO. (d) Patterned growth of uncommon feature among MOFs.
MOF-5 crystals on amorphous carbon coated AAO using a TEM grid. (e)
Multilayer MOF-5/silicalite-1 on gold-coated AAO. Images reproduced Heterogeneous Catalysis. [Co4 O(bdpb)3 ] (Fig. 11 - left) was
from Yoo and Jeong.17m prepared by Tonigold et al.36 by the solvothermal method (DMF,

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Fig. 11 (left) Representation of crystal packing in [Co4 O(bdpb)3 ] emphasizing the large channels of the structure. (right) Variation of the initial rate of
production of tert-butyl-2-cyclohexenyl-1-peroxide as a function of the catalyst loading. The plot emphasises the higher activity of the microwave-prepared
material in all studied ranges. Images reproduced from Tonigold et al.36
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120 ◦ C) and with microwave heating. The latter allowed a numbers and predictable topologies, structural features more
straightforward isolation of the bulk material in a few minutes, compatible with the fast kinetics of crystal growth. On the other
with smaller crystallite size and with uniform distribution. The hand, lanthanides promote more flexible frameworks which are
structure is similar to Zn-MOF-5, but contains redox-active sites more difficult to isolate.
capable of oxidizing cyclohexene into tert-butyl-2-cyclohexenyl-1- We note another synthetic approach which uses low reaction
peroxide in the presence of tert-butyl hydroperoxide, which activity temperatures and can compete with microwaves: sonication. The
is significantly increased due to the smaller crystal size of the most striking example is that of Jung et al.38 who used three syn-
microwave prepared material (Fig. 11 – right). thetic approaches for the preparation of MOF-177: a conventional
solvothermal synthesis, microwave irradiation and sonication of
the reactive mixture. Sonication led to the best results: after only
4. Conclusions and Perspectives 30 min the material was isolated with high yield and crystallinity,
and exhibited the best CO2 adsorption capability. Surprisingly,
The constantly expanding research on the design and preparation the material resulting from microwave heating exhibited poor
of MOFs can greatly benefit from the use of synthetic approaches crystallinity and texture. The use of ultrasound was also found
based on microwave heating. The results described in this short to be effective in the preparation of HKUST-1.39
perspective highlight several advantages of this technique: fast All things considered, one should bear in mind that MOFs are
reaction rates accompanied by short reaction periods; high always constructed by self-assembly. It is thus only necessary for
yields with remarkable phase purity and, in several cases, phase the chemist to intervene at the recognition step by selecting the
selectivity; the real possibility of controlling crystal size, going best reactive conditions to promote the chemical encounter of the
from microcrystals to nano-sized particles; the possibility of using reactants. At present, microwave heating seems the most promising
compact synthetic devices with low energy consumption while way to achieve short reaction times and small crystallite sizes,
producing small amounts of chemical waste. It is not surprising both crucial for applications in devices. We invite every synthetic
that this approach has led to industrial patents. One example chemist (not just those working on the preparation of MOFs) to
comes from the work of Chang et al. in Korea who patented explore microwave heating in the hope of discovering new reactions
the synthesis of a porous zinc-based carboxylate coordination and new products.
polymer37 in a wide range of conditions: frequency in the range
of 0.3–300 GHz and temperature of 20–120 ◦ C. This MOF
was demonstrated to have great potential in catalysis, as an ion 6. List of ligand abbreviations
exchanger, as nanoreactor, sensor, in optoelectronics and as a
medical material. 2-dpds 2,2¢-Dipyridyldisulfide
Microwave heating also poses some limitations, starting with 4,4¢-bipy 4,4¢-Bipyridine
the instrumental apparatus itself. The possibility of varying the bbi 1,1¢-(1,4-Butanediyl)bis(imidazole)
reaction conditions by controlling the irradiation power, time of DMF N,N¢-dimethylformamide
reaction and the temperature is also its limitation because different dpa 2,2¢-dipyridylamine
instruments are unable to deliver the same conditions, ultimately DPNI N,N¢-di-(4-pyridyl)-1,4,5,8-naphthalene
hindering reproducibility. tetracarboxydiimide
The majority of reports on the microwave synthesis of MOFs is EMIm 1-Ethyl-3-methyl imidazolium bromide
based solely on the use of transition metal centres. Only a handful H(2Cl-PhCO) 2-chlorophenyl(oximino)acetonitrile
of structures contain other types of metallic nodes and only two H(4Cl-PhCO) 4-chlorophenyl(oximino)acetonitrile
reports, by Sonnauer and Stock23 and by our group29 concern H2 bdpb 1,4-bis[(3,5-dimethyl)-pyrazol-4-yl]benzene
lanthanides. From the self-assembly perspective, transition metal H2 NDC 2,6-naphthalenedicarboxylic acid
centres promote more rigid geometries, with low coordination H2 pydc 2,5-Pyridinedicarboxylic acid

328 | Dalton Trans., 2011, 40, 321–330 This journal is © The Royal Society of Chemistry 2011
 View Article Online

H2 Thz 2,5-Thiazolo[5,4-d]thiazoledicarboxylic acid 10 U. Mueller, M. Schubert, F. Teich, H. Puetter, K. Schierle-Arndt and

H3 BTC Trimesic acid J. Pastre, J. Mater. Chem., 2006, 16, 626–636.
11 P. M. Forster, P. M. Thomas and A. K. Cheetham, Chem. Mater., 2002,
H3 IDC 4,5-Imidazoledicarboxylic acid 14, 17–20.
H4 BTEC 1,2,4,5-Benzenetetracarboxilic acid 12 D. E. Clark and W. H. Sutton, Annu. Rev. Mater. Sci., 1996, 26, 299–
pyz Pyrazine 331.
13 B. L. Foster and M. E. Cournoyer, Chem. Health Saf., 2005, 12,
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