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Aerobic homocoupling of arylboronic acids

Cite this: Green Chem., 2014, 16,
catalysed by copper terephthalate metal–organic
2865 frameworks†
Pillaiyar Puthiaraj,a Palaniswamy Suresha,b and Kasi Pitchumani*a,b
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Copper terephthalate MOF is utilised as an environmentally benign, efficient and reusable heterogeneous
catalyst to effect the aerobic homocoupling of arylboronic acids yielding the corresponding symmetrical
biphenyls under mild reaction conditions. This method tolerates various substituents present in arylboro-
nic acids such as halogens, cyano and nitro groups. The catalytic performance has been compared with
that of other copper based MOFs namely MOF-101, [Cu(pdc)2]NH2Me2, [Cu2(ndc)2ted]n and [Cu(H2L)]n as
well as with other copper salt catalysts. Sheldon test confirmed the heterogeneity of the catalyst, which
Received 12th January 2014, can be reused under optimized conditions with only a minor loss in its activity. A mechanism for the
Accepted 24th February 2014
homocoupling reaction is also proposed. The simplicity of catalyst preparation, its stability, substrate
DOI: 10.1039/c4gc00056k selectivity, easy recovery and regeneration designate possible utilization of this catalytic system in a multi-
www.rsc.org/greenchem tude of catalytic reactions and industrial processes.

Introduction zeolites, these MOFs have the potential for a more flexible
rational design through control of the architecture,
functionalization of the pores and substantially higher metal
Metal–organic frameworks (MOFs) have emerged as a hot
loading, which offers the opportunity to significantly reduce
topic in heterogeneous catalysis.1 They are composed of metal
the overall amount of catalyst, provided that the internal metal
ions as nodes and organic ligands as linkers, creating infinite
centres are accessible to the substrates.7
polymeric frameworks with regular void spaces that can
Aryl C–C (sp2–sp2) bond formation is an important and
accommodate small gas and solvent molecules in their pores.2
challenging process in both synthetic and industrial points of
Over the past decade, chemists have focused only on design
view. Symmetrical and unsymmetrical biaryls are important
and synthesis of new MOFs and studying their role in gas
structural motifs exhibiting a wide variety of physical and
storage, separations and sensors.3 MOFs have recently
chemical properties8 with versatile applications in drugs, agro-
emerged as a particular class of functional materials owing to
chemicals, dyes, semi-conductor and optically active ligands.9
their high inner surface area, tenability of pore size, chemical
These couplings have been achieved by palladium catalysed
tenability and topologies.4 MOFs contain a large percentage of
processes such as Suzuki reaction, modified Ullmann reaction
transition metals that can act as catalytic sites5 provided that
and Hiyama–Kumada reaction.10 Particularly, palladium cata-
they have free coordination positions not compromised in the
lysed homocoupling of boronic acids has been extensively
construction of MOFs. These materials are expected to have
reported.11 However there are limitations in these palladium
many similarities from the structural point of view with zeo-
catalysed methods: (1) palladium is expensive and additional
lites and related microporous solids. Consequently MOFs are
ligands are needed to stabilize the palladium species,11c,i,j (2)
attractive catalysts for organic transformations, though,
stoichiometric amount of oxidants are needed to restore the
however, only a relatively limited number of studies have
catalytically active palladium(II) species,11g,h (3) require a base
focussed on the investigation of the catalytic activity of these
to improve the yields,11c,i, j and (4) need of high temperature.11h
MOFs.1a,c,6 Another advantage is, compared to conventionally
Consequently many research groups have reported the homo-
used microporous and mesoporous inorganic materials like
coupling of boronic acids also by other metals.12 The synthetic
use of boronic acids are more common as they are more stable
and less toxic than other organometallic reagents.13 Generally
a
School of Chemistry, Madurai Kamaraj University, Madurai 625 021, India homocoupling of arylboronic acids is also very slow.14 In con-
b
Centre for Green Chemistry Processes, School of Chemistry, Madurai Kamaraj
cordance with the principles of green chemistry,15 air is an
University, Madurai 625021, India. E-mail: [email protected]
† Electronic supplementary information (ESI) available. See DOI: ideal oxidant because of its abundance, low cost, safety, lack of
10.1039/c4gc00056k toxic by-products and it is cheap for industrial applications.16

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Recently, Singh et al. reported the clay encapsulated Cu(OH)x Initially phenylboronic acid was selected as a model sub-
catalysed homocoupling of arylboronic acids,17a Xiao et al. strate in the presence of different catalysts under various con-
reported the Mg–Al oxides stabilised gold nanoparticles cata- ditions with the aim of optimizing the yield and the results are
lysed homocoupling reaction17b and Sakurai et al. reported the summarized in Table 1. All reactions were conducted at room
gold nanoparticles catalysed homocoupling of arylboronic temperature (RT) in air. No product was detected either in the
acids under acidic conditions.17c Fe3O4 nanoparticle-supported absence of catalyst or in an inert atmosphere (Table 1, entries
Cu(II)-β-cyclodextrin complex is also employed as a reusable 1 and 32). When the reaction was conducted using Cu(BDC)
catalyst for homocoupling of arylboronic acids.18 However, pre- MOF in DMSO, a 75% yield of homocoupling product
vious investigations of copper-mediated coupling reactions for (Table 1, entry 2) was observed. When the reaction was con-
the synthesis of biaryls required a stoichiometric amount of ducted using other copper sources like Cu(OAc)2, CuSO4·5H2O
catalyst and ligand, and a higher reaction time.12 Although and CuCl2 respectively (Table 1, entries 3–5) a lower yield of
homogeneous catalysts have been extensively investigated for homocoupling products was observed (42, 18 and 31%). When
coupling reactions, the challenges are very significant as the the amount of Cu(OAc)2, CuSO4·5H2O and CuCl2 catalysts was
catalysts are expensive, metal contamination in the reaction reduced to 50 mol%, the homocoupled product was also
mixture, cannot be reused and the products are difficult to sep- reduced to 34, 12, 22%. When Cu(NO3)2·3H2O was used as
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arate from the reaction mixture, chances of undesired product catalyst, no product was observed but in the presence of ter-
formation due to the requirement of ligands and additional ephthalic acid as an additive, a very low yield was noticed
reagents.19 In order to overcome these problems, MOFs (Table 1, entries 6 and 7). This observation of a significantly
provide unique advantages as these heterogeneous materials decreased yield with other Cu(II) sources, eliminates the possi-
are easily prepared and are cheap. Recently, Yaghi et al. bility of a Cu(0)/Cu(II) cycle in the present study as the major
reported the Cu3(BTC)2 catalysed homocoupling of arylboronic reaction pathway. These results indicate that the catalytic
acids with external cyclohexylamine base20 and observed the centres might be ligated by the terephthalic acid, which
arylated Chan–Lam cross coupling by-products. Corma et al. cannot be easily approached by the substrates. When the reac-
reported the Cu(BDC) MOF as catalyst for three-component tion was conducted using Cu(BDC) MOF in DMF, an excellent
couplings of amines, aldehydes and alkynes.21 Recently Phan yield of homocoupling product (Table 1, entry 8) was obtained.
et al. reported the use of Cu(BDC) MOF as catalyst for the One of the main reasons for the high catalytic activity of
modified Friedlander reaction.22 To the best of our knowledge, copper terephthalate MOF is that it is a porous material and
there are no reports describing the copper terephthalate MOF has a high surface area,23 which is favourable for the accessi-
catalysed homocoupling of arylboronic acids. bility of reactants to the active metal sites of MOF. To gain an
In this study, we have demonstrated copper terephthalate insight into the role of the substituents, the presence of
Cu(BDC) MOF as an efficient heterogeneous reusable catalyst heteroatoms and the size of the linkers, the following four
towards the aerobic homocoupling of arylboronic acids additional MOFs namely MOF-101, [Cu( pdc)2]NH2Me2,
without losing the crystallinity and structure of the Cu(BDC) [Cu2(ndc)2ted]n and [Cu(H2L)]n, were synthesised (see ESI† for
MOF (Scheme 1). The Cu(BDC) catalysed protocol offers their structure and characterization) and their catalytic activity
several advantages, compared to the conventional approach in in the homocoupling reaction was studied (Table 1, entries
the formation of biphenyl derivatives and the observed results 9–12). With an ortho-substituent namely bromine as in
are discussed below. MOF-101, a small decrease in yield was noticed (71%), which
may be attributed to steric effects. When a heteroatom is
present in the linker as in [Cu( pdc)2]NH2Me2 MOF, the
decrease in the yield of homocoupled product was significant,
Results and discussion probably due to the presence of an alternative binding site.
Herein, we report the heterogeneous copper terephthalate With more bulkier and flexible linkers as in [Cu2(ndc)2ted]n
MOF catalysed homocoupling of arylboronic acids in air at and [Cu(H2L)]n, and the presence of more heteroatoms as in
room temperature. To the best of our knowledge, the MOF [Cu2(ndc)2ted]n and [Cu(H2L)]n, the homocoupling reaction
catalysed aerobic homocoupling of arylboronic acids has not did not proceed at all, indicating clearly that steric effects and
been reported so far. In addition, Cu(BDC) MOF is shown as the presence of heteroatoms play a very significant role in the
an efficient and environmentally-friendly heterogeneous, reu- above reaction. It is also likely that in these cases, the linkers
sable catalyst. The various factors determining the reactivity of themselves bind strongly to the central copper metal atom
boronic acids under different experimental conditions are dis- thereby affecting the overall reaction. When the reaction was
cussed below. also conducted with MOF-101, [Cu( pdc)2]NH2Me2, [Cu2(ndc)2-
ted]n and [Cu(H2L)]n, MOFs containing an identical amount of
copper species as Cu(BDC), the homocoupled product was
obtained in only 76 and 62%, and there was no reaction with
the other two MOFs (Table 1, entries 13–16). Interestingly,
Cu(BDC) MOF showed no catalytic activity in non-polar sol-
Scheme 1 Homocoupling of arylboronic acids. vents, namely toluene, xylene, DCM, DCE, dioxane, THF and

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Table 1 Optimization of reaction conditionsa

Yieldb [%]

Entry Catalyst Additives Solvent Time Biphenyl Phenol

1 — DMSO 18 — —
2 Cu(BDC) DMSO 18 75 —
3c Cu(OAc)2 DMSO 18 42 (34)i —
4c CuSO4·5H2O DMSO 18 18 (12)i Traces
5c CuCl2 DMSO 18 31 (22)i —
6c Cu(NO3)2·3H2O DMSO 18 — —
7c Cu(NO3)2·3H2O Terephthalic acid DMSO 18 10 —
8 Cu(BDC) DMF 18 97 —
—
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9 MOF-101 DMF 18 71
10 [Cu(pdc)2]NH2Me2 DMF 18 60 —
11 [Cu2(ndc)2ted]n DMF 18 — —
12 [Cu(H2L)]n DMF 18 — —
13d MOF-101 DMF 18 76 —
14e [Cu(pdc)2]NH2Me2 DMF 18 62 —
15 f [Cu2(ndc)2ted]n DMF 18 — —
16g [Cu(H2L)]n DMF 18 — —
17 Cu(BDC) DMF 16, 14, 12, 10 97, 82, 68, 48 —
18 Cu(BDC) Toluene 18 — —
19 Cu(BDC) Xylene 18 — —
20 Cu(BDC) DCM 18 — —
21 Cu(BDC) DCE 18 — —
22 Cu(BDC) Dioxane 18 — —
23 Cu(BDC) THF 18 — —
24 Cu(BDC) CHCl3 18 — —
25 Cu(BDC) H2O 18 8 74
26 Cu(BDC) Methanol 18 26 29
27 Cu(BDC) Ethanol 18 42 38
28 Cu(BDC) Na2CO3 DMF 18 49 —
29 Cu(BDC) K2CO3 DMF 18 37 —
30 Cu(BDC) Cs2CO3 DMF 18 22 —
31 Cu(BDC) NEt3 DMF 18 62 —
32h Cu(BDC) DMF 18 — —
33 Cu(BDC) DMF–H2O 18 68 12
a
Reaction conditions: phenylboronic acid (2 mmol), catalyst (100 mg), solvent (2 mL), RT. b Isolated yield. c 100 mol% of catalyst. d 155 mg of
catalyst. e 130 mg of catalyst. f 105 mg of catalyst. g 120 mg of catalyst. h Nitrogen atmosphere. i 50 mol% of catalyst; H2L = (Z)-4-((2-
hydroxynaphthalen-1-yl) methyleneamino)benzene-1,3-dioic acid; ndc = 1,4-naphthalenedicarboxylic acid; ted = triethylenediamine; BDC = 1,4-
benzenedicarboxylic acid.

CHCl3 for the homocoupling reaction of arylboronic acid The biaryl yield was also found to increase rapidly with an
(Table 1, entries 18–24). As the aryl substrates are more soluble increase in the amount of catalyst. As the amount of catalyst
in nonpolar solvents, their binding to Cu(BDC) MOF is very was increased to 100 mg, biphenyl was obtained in highest
slow, resulting in the absence of homocoupling. When the yield and the further addition of catalyst had no obvious
reaction was conducted in protic polar solvents like water, effects on the yield of biphenyl (Fig. 1). Thus the optimized
methanol and ethanol, the biphenyl product was obtained in conditions for the homocoupling of arylboronic acid are use of
only 8, 26 and 42% yields respectively, along with consider- Cu(BDC) MOF as a catalyst in DMF under air for 16 h at room
able amounts of phenol (Table 1, entries 25–27). When protic temperature.
solvents were used, the conversion of the C–B bond into a C–O This Cu(BDC) MOF promoted aerobic homocoupling reac-
bond via a peroxyboronate intermediate was promoted result- tion was also successfully extended to various substituted aryl-
ing in a considerable amount of phenol formation.17c Gener- boronic acids. As depicted in Table 2, this reaction worked very
ally, as the base can improve the reaction yield for some well for a wide range of substrates with both electron-donating
catalytic systems,24 we have used different bases for this reac- and electron-withdrawing substituents. It can be concluded
tion and only 20–60% yields were observed (Table 1, entries that the nature of the substituent, either electron-donating or
28–31). When carried out in DMF–water (1 : 1) mixture, 68% withdrawing, did not show any significant change in the
yield of the biphenyl and 12% of phenol were observed overall yield. Both para- and meta-substituted arylboronic acids
(Table 1, entry 33). gave homocoupling products in excellent yields (Table 2,

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1-boronic acid, 2,6-difluorophenylboronic acid and 2,4,6-tri-

methylphenylboronic acid did not give the corresponding
homocoupling products (Table 2, entries 22–24) as the steri-
cally hindered boronic acids did not bind with MOF metal
centers. The biphenyl and their derivatives were characterised
by m.p. and NMR techniques.
To verify whether catalysis by Cu(BDC) MOF is truly hetero-
geneous or due to some leached copper species present in the
filtrate, the Sheldon test was performed. The reaction was
carried out under the optimized conditions and the copper ter-
ephthalate MOF catalyst was filtered from the reaction mixture
at 48% of biphenyl formation (Table 3). After removal of MOF
catalyst, the filtrate was further stirred for an additional 6 h
Fig. 1 Dependence of yield on the amount of catalyst for homo- and no further biphenyl product was observed. The absence of
coupling of phenylboronic acid. metal leaching was also confirmed from atomic absorption
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spectroscopy analyses of the filtrate from the reaction mixture

and also of the filtrate from a stirred solution of Cu(BDC) in
Table 2 Cu(BDC) MOF catalysed homocoupling of various arylboronic
acidsa DMF under identical reaction conditions. Thus the atomic
absorption spectroscopic data clearly demonstrate that
Cu(BDC) MOF is truly heterogeneous in nature.
Reusability of the Cu(BDC) MOF was also studied. After
completion of the reaction, the catalyst was recovered by fil-
Boronic Yieldb tration and washed with ethyl acetate, heated with 2 mL of
Entry acid (R) Products (%) fresh DMF at 100 °C for 2 h, activated under vacuum at room
temperature for 4 h, which was subsequently reused and the
1 4-CH3–C6H4– 4,4′-Dimethylbiphenyl 95
2 4-OCH3–C6H4– 4,4′-Dimethoxybiphenyl 96
results are presented in Fig. 2. It is clear that the decrease in
3 4-F–C6H4– 4,4′-Difluorobiphenyl 94
4 4-Br–C6H4– 4,4′-Dibromobiphenyl 93
5 4-Cl–C6H4– 4,4′-Dichlorobiphenyl 87
6 4-CN–C6H4– 4,4′-Dicyanobiphenyl 89
7 4-OCF3–C6H4– 4,4-Di(trifluoromethoxy)- 95 Table 3 Sheldon testa
biphenyl
8 4-CF3–C6H4–C2H2– 1,1′-(1E,3E)-1,3-Butadiene- 92 Yield (%)
1,4-diylbis[4-(trifluoromethyl)-
benzene Catalyst 10 h (10 + 6) h Reused catalyst
9 4-C2H5–C6H4– 4,4′-Diethylbiphenyl 88
10 3-Cl–C6H4– 3,3′-Dichlorobiphenyl 90 Cu(BDC) 48 48 97
11 3-NO2–C6H4– 3,3′-Dinitrobiphenyl 98
12 3-OCH3–C6H4– 3,3′-Dimethoxybiphenyl 89 a
Reaction conditions: phenylboronic acid (2 mmol), Cu(BDC)
13 3-CH3–C6H4– 3,3′-Dimethylbiphenyl 96 (100 mg), DMF (2 mL), RT.
14 3,4-(CH3)2–C6H3– 3,3′,4,4′-Tetramethylbiphenyl 93
15 3,4-F2–C6H3– 3,3′,4,4′-Tetrafluorobiphenyl 98
16 3-Cl-4-F–C6H3– 3,3′-Dichloro-4,4′- 97
difluorobiphenyl
17 2-Br–C6H4– 2,2′-Dibromobiphenyl 49
18 2-CH3–C6H4– 2,2′-Dimethylbiphenyl 52
19 2-OCH3-5-F–C6H3– 2,2′-Dimethoxy-5,5′- 35
fluorobiphenyl
20 4-Pyridinyl- 4,4′-Bipyridyl 62
21 3-F-4-pyridinyl– 3,3′-Difluoro-4,4′-bipyridyl 55
22 1-Naphthyl- — —
23 2,5-F2-4-OCH3– — —
C6H2–
24 2,4,6-(CH3)3–C6H2– — —
a
Reaction conditions: arylboronic acid (2 mmol), Cu(BDC) MOF
(100 mg), DMF (2 mL), RT, 16 h. b Isolated yield.

entries 1–16). But in the case of ortho-substituted arylboronic

acids only lower yields (Table 2, entries 17–19) are observed.
The hetero arylboronic acids also gave only moderate yields
(Table 2, entries 20 and 21), as the heteroatom is likely to bind
with the metal centre. Bulkier substrates such as naphthalene- Fig. 2 Reusability of Cu(BDC) catalyst experiments.

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transmetallation of Cu(II) with two molecules of arylboronic

acid affords a Ar–Cu(II)–Ar, which undergoes air oxidation to
yield a Cu(III) intermediate, reductive elimination of which
releases the homocoupled product Ar–Ar. An alternative
pathway involving a Cu(0)/Cu(II) cycle is ruled out on the basis
of the control experiments discussed earlier.
With a rigid framework as in the present MOF, a bimetallic
mechanism is also likely to yield the homocoupled product.
In the IR spectrum of the copper containing MOF,
recorded with the reaction intermediate, the DMF carbonyl
stretching frequency 1663 cm−1 had disappeared and the
B–OH band shift from 3480 to 3442 cm−1 peak was observed
(Fig. 4). In the original catalyst, there is no peak around
3442 cm−1 (Fig. 5b).
Data on reaction conditions, activity and efficiency of the
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various other catalysts employed earlier for the homocoupling

of arylboronic acids are given in Table 4. Comparison of the
results indicates that our catalytic system (entry 27) exhibits
Fig. 3 Powder XRD patterns of fresh and reused catalyst. better catalytic activity compared to conventional catalysts
such as Cu, Pd, Fe and Au. These systems require additional
base (entries 1, 3, 10, 11–17, 20 and 24–26), external additives
the activity of the catalyst resulted in a minor loss of product (entries 3, 5, 9, 11, 12, 15 and 25), additional oxidants (entries
yield even after five times of its reuse. 3, 5, 9, 11, 12, 15, 25 and 26) and higher reaction time (entries
Comparison of the powder XRD patterns of the fresh, three 2, 5, 6, 11, 20, 22, 24, 26 and 25).
and five times reused MOF were also recorded (Fig. 3) which
clearly show that the reused catalyst exhibits a similar powder
XRD pattern. The specific surface area and average pore
volume for the fresh and reused Cu(BDC) MOF were measured
using BET surface area analysis. The BET isotherms show a Experimental section
small decrease in the surface area (590 m2 g−1 and 564 m2 g−1
for fresh Cu(BDC) and fifth time used Cu(BDC) respectively). General methods
The pore volume of the fresh and reused MOF is 0.268 cm3 g−1 All reactions were carried out under aerobic conditions. All
and 0.264 cm3 g−1 from the BET analysis. These BET surface chemicals were used without further purification as commer-
area analyses and powder XRD pattern results clearly demon- cially available unless otherwise noted. NMR spectra were
strate that no appreciable change in the structural integrity is recorded at 500, 400 and 300 MHz (mentioned in respective
observed during/after the reuse. NMR data itself) on a Bruker spectrometer. All 1H NMR and
13
To demonstrate the potential utility of this method for pre- C NMR spectra were measured in CDCl3 with TMS as the
parative purposes, the reaction was also carried out in the opti- internal standard. The powder XRD pattern of the catalyst
mized reaction conditions on a 1.2 gram scale, giving 94% sample was measured with a SHIMADZU XD-D1 and X’Pert
yields which are comparable to those obtained for a small- PANalytical Diffractometer instrument using a Cu Kα radiation
scale reaction (reaction condition: phenylboronic acid, 10 mL at room temperature. Brunauer Emmett Teller (BET) surface
DMF, RT, 16 h). area analysis was carried out using the Quantachrome-Auto-
By analogy with these reports and previous report,12a–d,18,20,34 sorb at 77 K. Elemental analysis with atomic absorption spec-
a plausible reaction pathway is proposed as shown in trophotometry (AAS) was performed on Varian AA 240. IR
Scheme 2. The copper terephthalate MOF shows a larger spectral analyses were performed using a JASCO FT/IR-410
surface area and the presence of the copper atom and its instrument by the KBr pellet technique in the range of
exposed apical coordination sites might also lead to catalytic 4000–500 cm−1. Thermogravimetric analysis (TGA) was per-
applications.23 Terephthalate ligands are coordinated in a formed with a TGA/Shimadzu Thermal Analyser under a nitro-
bidentate bridging fashion to Cu(II) dimer, separated vertically gen atmosphere in the temperature range 50–570 °C in a flow
by 2.63 Å. Each Cu(II) is also coordinated to a molecule of DMF of nitrogen at a heating rate of 10 °C min−1. Electrospray
to give the Cu(II) atom a square-planar geometry. The catalyti- ionization mass spectrometry (ESI-MS) analyses were recorded
cally active copper present in the channel walls of MOF can in LCQ Fleet, Thermo Fisher Instruments Limited, US. ESI-MS
promote the homocoupling reaction of various arylboronic was performed in negative ion mode. The collision voltage and
acids. During the homocoupling reaction, in the first step the ionization voltage were −70 V and −4.5 kV, respectively, using
solvent molecule may be replaced by the arylboronic acid. The nitrogen as atomization and desolvation gas. The desolvation
proposed mechanism involves a Cu(I)/Cu(III) cycle. Double temperature was set at 300 °C.

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Scheme 2 Plausible mechanism for the homocoupling of arylboronic acid.

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MCM-41 where broader peaks were normally observed on their

diffractograms.25 Elemental analysis by atomic absorption
spectroscopy (AAS) indicated a copper loading of 3.87 mmol
g−1. The FT-IR spectra of the Cu(BDC) MOF exhibited the pres-
ence of a strong peak at 1603 cm−1, which was lower than the
value for CvO stretching vibration observed in free carboxylic
acids (1760–1690 cm−1) (Fig. 5a and b). This strong peak was
due to the stretching vibration of carboxylate anions present in
the material. After removal of DMF, the 1603 cm−1 peak was
shifted to 1576 cm−1 and the DMF carbonyl frequency peak
(1665 cm−1) disappeared (Fig. 5c). Thermogravimetric analysis
(TGA) was carried out to examine the stability of the frame-
work. For the as-synthesised samples, the TGA of Cu(BDC)
showed a loss of ligated form of DMF molecules in the temp-
erature range 160–260 °C. After 260 °C, the phase remains
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completely changed, which was stable upto over 370 °C

(Fig. 6). The overall powder XRD patterns, IR spectrum and the
Fig. 4 FT-IR spectra of phenylboronic acid (a) and reaction intermedi-
ate (b).
thermal stability of the copper terephthalate MOF were in
good agreement with the literature.23
The Cu(BDC) MOF was dissolved in HNO3, diluted and ana-
lysed with AAS and the results show that the copper concen-
tration in Cu(BDC) MOF was found to be 3.87 mmol g−1. To
see if there was any metal leaching, the following control
experiment was performed. Cu(BDC) MOF (0.100 g) was added
to a mixture of phenylboronic acid (2 mmol), in DMF (2 mL)
and stirred at RT for 16 h. After completion of reaction, the
reaction mixture was filtered. The filtrate and reused Cu(BDC)
MOF (dissolved in HNO3) were analysed by AAS. The copper
concentration in the filtrate was found to be BDL (below
detectable limit). In the reused Cu(BDC) MOF (dissolved in
HNO3), the copper concentration was found to be 3.86 mmol
g−1. This result shows that no leaching of copper has taken
place from the solid to the liquid phase. This proves that the
catalyst is heterogeneous in nature.

Fig. 5 FT-IR spectra of 1,4-benzenedicarboxylic acid (a), Cu(BDC) (b)

and Cu(BDC) after removal of DMF (c). Synthesis of MOF-101
2-Bromoterephthalic acid was prepared according to the pub-
Synthesis of copper terephthalate MOF [Cu(BDC)] lished procedure.38 The prepared 2-bromoterephthalic acid
Cu(BDC) MOF was prepared according to the procedure was characterized by ESI-MS spectrum (ESI-MS: m/z calcd for
reported by Tannenbaum et al.23 Equimolar quantities of C8H5BrO4: 243.94; found, 243.00 (M − H)). MOF-101 was pre-
copper nitrate trihydrate (15 mmol) and terephthalic acid pared according to the published procedure.39 An equimolar
(15 mmol) in 300 mL DMF were used. This solution was amount of 2-bromoterephthalic acid and Cu(NO3)2·2.5H2O in
placed in a closed flask in an oven at 110 °C for 36 h. It was DMF in a capped vial at room temperature gave blue crystals of
observed the blue crystals precipitated in a yield of 75% which the MOF-101. The prepared MOF-101 was characterized by
is comparable to that of the reported procedure.23 FT-IR and powder XRD techniques (see ESI†). The FT-IR
spectra of the MOF-101 exhibited the presence of a strong
peak at 1623 cm−1, which was lower than the value for the
Characterization of copper terephthalate MOF [Cu(BDC)] CvO stretching vibration observed in free carboxylic acids
The Cu(BDC) MOF was characterized using a variety of 1704 cm−1. This strong peak was due to the stretching
different techniques. A very sharp peak below 15° (with 2θ of vibration of carboxylate anions present in the material. The
10.27) was observed on the powder X-ray diffractogram of the DMF solvent carbonyl stretching frequency band appears to be
Cu(BDC) MOF, indicating that a highly crystalline material 1666 cm−1 for a molecule that is coordinated to the copper
(Fig. 3). Furthermore, the powder XRD patterns of the metal centre. These powder XRD pattern and FT-IR spectra
Cu(BDC) MOF exhibited a better crystallinity as compared to were in good agreement with that reported.39 Elemental analy-
that of silica-based materials such as SBA-15, SBA-16 and sis by AAS indicated a copper loading of 2.48 mmol g−1.

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Table 4 Comparison with reported catalytic systems for homocoupling of arylboronic acidsa

Temp. Time Yield

Entry Catalyst Additive Base Solvent Oxidant (°C) (h) (%) References

1 Au/CeO2 — K2CO3 Toluene — 60 15 100 12h

2 Pd/C — — H2O–2-propanol Air 75 1 94 26
(9 : 1)
3 Pd(OAc)2 NaClO4 i
Pr2NEt ACN–H2O (7/1) TEMPO Electro — 88 11e
oxidation
4 Fe3O4–Cu2-β-CD — — DMF Air 70 24 90 18
5 PdCl2 PS-NMe2 — Water CO2, O2 100 6 90 27
6 Pd(OAc)2 : 2PPh3 — — DMF Air 90 2 83 28
7 Cu2-β-CD — — DMF Air RT-90 14 83 12c
8 CuSO4/MS — — DMF Air 50 1 80 12b
9 Cu(OAc) 1,10-Phenanthroline — 2-Propanol Air RT 4 83 12a
10 Cyclopalladated — K3PO4·7H2O n-Propanol–H2O Air RT 12 99 11i
ferrocenylimine (1/2)
11 PdNPs/Te-DPs Tris-HCl buffer, — H2O Air 100 24 90 11f
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pH 8.9
12 Pd(OAc)2 [Bmim]PF6 K2CO3 H2O — 60 3 92 29
13 Pd(OAc)2 — K2CO3 Acetone–H2O Air RT 15 91 30
14 Pd(OAc)2 — K2CO3 ACN–H2O TEMPO Electro — 86 11g
oxidation
15 PdCl2 p-Toluenesulfonyl Na2CO3 H2O N2 RT 12 95 31
chloride
16 AuCl — K2CO3 EtOH Air 50 24 76 32
17 AuNPs : L — K2CO3 H2O Air RT 24 86 33
18 CuCl — — MeOH Air RT 4 93 12d
19 Au/chitosan — — H2O Air 30 7 96 17c
20 Au-PEG — NaOH EtOH–H2O — 80 25 60 35
21 Cu(OAc)2 — — DMF O2 RT 24 78 34
22 Au/MAO — — MeOH O2 100 12 90 17b
23 Au-CNPs — — Toluene–H2O Air 70 7 86 36
24 Au-(MCM-41) — K2CO3 Xylene — 130 24 99 12g
25 Pd(OAc)2 p-Benzoquinone Na2SO4 DMF — 80 2.1 99 11h
26 — I2 K2CO3 PEG-400 Air 140 48 97 37
27 Cu(BDC) — — DMF Air RT 16 97 Present work
a
ACN = acetonitrile, TEMPO = 2,2,6,6-tetramethylpiperidinyloxy, CD = cyclodextrin, PPh3 = triphenylphosphine, PS = polystyrene, MS = molecular
sieves, Te = Thermosynechococcus elongatus, DPs = DPs protein, [Bmim]PF6 = butylmethylimidazolium hexafluorophosphate, L = m-ferrocenyl
benzoic acid, PEG = polyethylene glycol, MAO = Mg–Al mixed oxides, CNPs = carbon nanoparticles.

Synthesis of copper pyridine-2,5-dicarboxylate MOF

([Cu( pdc)2]NH2NMe2)
[Cu( pdc)2]NH2NMe2 was prepared according to the previously
reported procedure40 and the prepared MOF was characterized
by FT-IR and powder XRD techniques (see ESI†). The FT-IR
spectra of the [Cu( pdc)2]NH2NMe2 exhibited the presence of a
strong peak at 1652 cm−1, which was lower than the value for
CvO stretching vibration observed in free carboxylic acids
1732 cm−1. This strong peak was due to the stretching
vibration of carboxylate anions present in the material. The
carboxylate ion is coordinated to the copper metal centre.
These characterization results were in good agreement with
reported crystal powder XRD simulated patterns.40 Elemental
analysis by AAS indicated a copper loading of 2.92 mmol g−1.

Synthesis of [Cu2(ndc)2ted]n MOF

[Cu2(1,4-naphthalenedicarboxylate)2ted]n was prepared accord-
ing to the reported procedure.41 The prepared MOF was
characterized by FT-IR and powder XRD techniques (see ESI†).
Fig. 6 TGA of Copper terephthalate MOF. The prepared [Cu2(ndc)2ted]n was characterized by FT-IR and

2872 | Green Chem., 2014, 16, 2865–2875 This journal is © The Royal Society of Chemistry 2014
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powder XRD techniques (see ESI†). The FT-IR spectra of the advantages: low cost, higher stability, substrate selectivity,
[Cu2(ndc)2ted]n exhibited the presence of a strong peak at easily separated and recyclability. The leaching test and re-
1615 cm−1, which was lower than the value for CvO stretching cycling experiment clearly demonstrate that the copper MOF is
vibration observed in free carboxylic acids 1702 cm−1. The car- truly heterogeneous in nature.
boxylate ion is coordinated to the central copper metal. This
strong peak was due to the stretching vibration of carboxylate
anions present in the material. These results were in good
agreement with those reported.41 Elemental analysis by AAS Acknowledgements
indicated a copper loading of 3.68 mmol g−1.
PP gratefully acknowledges financial support from University
Synthesis of [Cu(H2L)]n Grants Commission (UGC), New Delhi, for UGC-BSR-SRF.
KP thanks DST, New Delhi for financial support.
(Z)-4-((2-Hydroxynaphthalen-1-yl)methyleneamino)benzene-1,3-
dioic acid (H2L) was prepared according to the reported pro-
cedure.42 The prepared H2L was characterized by ESI-MS spec-
trum (ESI-MS: m/z calcd for C19H13NO5: 335.08; found, 334.11 References
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(M − H)). [Cu(H2L)]n was prepared according to the reported

procedure.42 The prepared MOF was characterized by FT-IR 1 (a) A. Corma, H. Garcia and F. X. L. Xamena, Chem. Rev.,
and powder XRD techniques (see ESI†). The FT-IR spectra of 2010, 110, 4606; (b) D. Farrusseng, S. Aguado and C. Pinel,
the [Cu(H2L)]n exhibited the presence of a strong peak at Angew. Chem., Int. Ed., 2009, 48, 7502; (c) J. Y. Lee,
1598 cm−1, which was lower than the value for the CvO O. K. Farha, J. Roberts, K. A. Scheidt, S. T. Nguyen and
stretching vibration observed in free carboxylic acids J. T. Hupp, Chem. Soc. Rev., 2009, 38, 1450; (d) Z. Wang,
1717 cm−1. This strong peak was due to the stretching G. Chen and K. Ding, Chem. Rev., 2009, 109, 322.
vibration of carboxylate anions present in the material. The 2 E. Jeong, W. R. Lee, D. W. Ryu, Y. Kim, W. J. Phang,
carboxylate ion is coordinated to the copper metal centre. E. K. Koh and C. S. Hong, Chem. Commun., 2013, 49, 2329.
These characterization results were in good agreement 3 (a) K. Sumida, D. L. Rogow, J. A. Mason, T. M. McDonald,
with the reported crystal powder XRD simulated patterns.42 E. D. Bloch, Z. R. Herm, T. H. Bae and J. R. Long, Chem.
Elemental analysis by AAS indicated a copper loading of Rev., 2012, 112, 724; (b) M. P. Suh, H. J. Park, T. K. Prasad
3.26 mmol g−1. and D. W. Lim, Chem. Rev., 2012, 112, 782; (c) J. R. Li,
J. Sculley and H. C. Zhou, Chem. Rev., 2012, 112, 869;
General experimental procedure for the Cu(BDC) MOF (d) X. Zhu, H. Zheng, X. Wei, Z. Lin, L. Guo, B. Qiu and
catalysed homocoupling reaction of arylboronic acid G. Chen, Chem. Commun., 2013, 49, 1276.
A solution of Cu(BDC) MOF (100 mg) and arylboronic acids 4 N. Stock and S. Biswas, Chem. Rev., 2012, 112, 933.
(2 mmol) was taken in 2 mL of DMF under an air atmosphere. 5 (a) L. Alaerts, E. Seguin, H. Poelman, F.-T. Starzyk,
After stirring at room temperature for 16 h, the mixture was P. A. Jacobs and D. E. DeVos, Chem. – Eur. J., 2006, 12,
diluted with ethyl acetate (5 mL) and then the catalyst removed 7353; (b) P. Horcajada, S. Surble, C. Serre, D. Y. Hong,
by filtration, followed by solvent evaporation under reduced Y. K. Seo, J. S. Chang, J. M. Greneche, I. Margiolaki and
pressure, the resulting crude product was finally purified by G. Ferey, Chem. Commun., 2007, 2820.
column chromatography on silica gel (60–120 mesh) with 6 M. Yoon, R. Srirambalaji and K. Kim, Chem. Rev., 2012,
petroleum ether and ethyl acetate as eluting solvent to give the 112, 1196.
desired product upto 97% yield. The recovered catalyst was 7 M. J. Beier, W. Kleist, M. T. Wharmby, R. Kissner,
thoroughly washed with ethyl acetate and heated with 2 mL of B. Kimmerle, P. A. Wright, J.-D. Grunwaldt and A. Baiker,
fresh DMF at 100 °C for 2 h, activated under vacuum at room Chem. – Eur. J., 2012, 18, 887.
temperature for 4 h, which was subsequently reused. 8 (a) Y. Liao, W. Hung, T. Hou, C. Lin and K. Wong, Chem.
Mater., 2007, 19, 6350; (b) J. Hassan, M. Sevignon, C. Gozzi,
E. Schulz and M. Lemaire, Chem. Rev., 2002, 102,
Conclusions 1359.
9 (a) J.-P. Corbet and G. Mignani, Chem. Rev., 2006, 106,
In conclusion, we have demonstrated the utility of a simple 2651; (b) B. Yuan, Y. Pan, Y. Li, B. Yin and H. Jiang, Angew.
and highly efficient heterogeneous catalyst for promoting the Chem., Int. Ed., 2010, 49, 4054; (c) F. Monnier and
aerobic homocoupling of arylboronic acid involving Cu(BDC) M. Taillefer, Angew. Chem., Int. Ed., 2009, 48, 6954;
MOF as the catalyst at room temperature without any additives (d) B. Karimi and P. F. Akhavan, Chem. Commun., 2009,
and bases. The reaction employs environmentally benign air 3750; (e) B. Karimi, D. Elhamifar, J. H. Clark and
as oxidant under mild reaction conditions. The catalyst is A. J. Hunt, Chem. – Eur. J., 2010, 16, 8047; (f ) D. Lee,
stable, shows no metal leaching and the reused catalyst exhibi- J. H. Kim, B. H. Jun, H. Kang, J. Parkand and Y. S. Lee, Org.
ted only a minor loss of catalytic activity. In comparison to Lett., 2008, 10, 1609; (g) S. Martin and L. Buhwald, Acc.
other catalysts, framework-immobilization confers multiple Chem. Res., 2008, 41, 1461.

This journal is © The Royal Society of Chemistry 2014 Green Chem., 2014, 16, 2865–2875 | 2873
 View Article Online

Paper Green Chemistry

10 (a) A. Fihri, M. Bouhrara, B. Nekoueishahraki, J.-M. Basset Appl. Catal., A, 2014, 470, 232; (b) L. Wang, W. Zhang,
and V. Polshettiwar, Chem. Soc. Rev., 2011, 40, 5181; D. S. Su, X. Meng and F.-S. Xiao, Chem. Commun., 2012, 48,
(b) A. Molnarc, Chem. Rev., 2011, 111, 2251; 5476; (c) R. N. Dhital, A. Murugadoss and H. Sakurai,
(c) L.-C. Campeau and K. Fagnou, Chem. Soc. Rev., 2007, 36, Chem. – Asian J., 2012, 7, 55.
1058. 18 B. Kaboudin, R. Mostafalu and T. Yokomatsu, Green Chem.,
11 (a) M. Shimizua, I. Nagao, Y. Tomioka, T. Kadowaki and 2013, 15, 2266.
T. Hiyama, Tetrahedron, 2011, 67, 8014; (b) S.-Y. Xu, 19 (a) A. W. Thomas and S. V. Ley, Angew. Chem., Int. Ed.,
Y.-B. Ruan, X.-X. Luo, Y.-F. Gao, J.-S. Zhao, J.-S. Shen and 2003, 42, 5641; (b) J.-B. Lan, G.-L. Zhang, X.-Q. Yu,
Y.-B. Jiang, Chem. Commun., 2010, 46, 5864; (c) Z. Jin, J.-S. You, L. Chen, M. Yan and R.-G. Xie, Synlett, 2004,
S.-X. Guo, X.-P. Gu, L.-L. Qiu, H.-B. Song and J.-X. Fang, 1095; (c) M. L. Kantam, G. T. Venkanna, C. Sridhar,
Adv. Synth. Catal., 2009, 351, 1575; (d) S. R. Cicco, B. Sreedhar and B. M. Choudary, J. Org. Chem., 2006, 71,
G. M. Farinola, C. Martinelli, F. Naso and M. Tiecco, 9522; (d) J. X. Qiao and P. Y. S. Lam, Synthesis, 2011, 829.
Eur. J. Org. Chem., 2010, 2275; (e) K. Mitsudo, T. Shiraga 20 O. M. Yaghi, A. U. Czaja, B. Wang and Z. Lu, US Patents,
and H. Tanaka, Tetrahedron Lett., 2008, 49, 6593; 2012/0130113, 2012.
(f) A. Prastaro, P. Ceci, E. Chiancone, A. Boffi, G. Fabrizi 21 I. Luz, F. X. L. I. Xamena and A. Corma, J. Catal., 2012, 285,
Published on 24 February 2014. Downloaded on 07/05/2014 16:25:58.

and S. Cacchi, Tetrahedron Lett., 2010, 51, 2550; 285.

(g) K. Mitsudo, T. Shiraga, D. Kagen, D. Shi, J. Y. Becker 22 N. T. S. Phan, T. T. Nguyen, K. D. Nguyen and A. X. T. Vo,
and H. Tanaka, Tetrahedron, 2009, 65, 8384; (h) C. Amatore, Appl. Catal., A, 2013, 464–465, 128.
C. Cammoun and A. Jutand, Eur. J. Org. Chem., 2008, 4567; 23 C. G. Carson, K. Hardcastle, J. Schwartz, X. Liu,
(i) B. Mu, T. Li, Z. Fu and Y. Wu, Catal. Commun., 2009, 10, C. Hoffmann, R. A. Gerhardt and R. Tannenbaum,
1497; ( j) A. Ciric and F. Mathey, Organometallics, 2010, 29, Eur. J. Inorg. Chem., 2009, 2338.
4785. 24 (a) R. N. Dhital, C. Kamonsatikul, E. Somsook,
12 For examples of other transition-metal mediators, see: Cu: K. Bobuatong, M. Ehara, S. Karanjit and H. Sakurai, J. Am.
(a) N. Kirai and Y. Yamamoto, Eur. J. Org. Chem., 2009, Chem. Soc., 2012, 134, 20250; (b) Y. Dingyi and Z. Yugen,
1864; (b) B. Kaboudin, T. Haruki and T. Yokomatsu, Syn- Green Chem., 2011, 13, 1275; (c) E. Bernoud, C. Alayrac,
thesis, 2011, 1, 91; (c) B. Kaboudin, Y. Abedi and O. Delacroix and A.-C. Gaumont, Chem. Commun., 2011, 47,
T. Yokomatsu, Eur. J. Org. Chem., 2011, 6656; (d) G. Cheng 3239; (d) Y.-X. Liao, C.-H. Xing, M. Israel and Q.-S. Hu, Org.
and M. Luo, Eur. J. Org. Chem., 2011, 2519; Mn: Lett., 2011, 13, 2058; (e) K. D. Hesp, R. J. Lundgren and
(e) A. S. Demir, O. Reis and M. Emrullahoglu, J. Org. Chem., M. Stradiotto, J. Am. Chem. Soc., 2011, 133, 5194.
2003, 68, 578; Au: (f ) H. Tsunoyama, H. Sakurai, N. I. kuni, 25 D. Zhao, Q. Huo, J. Feng, B. F. Chmelka and G. D. Stucky,
Y. Negishi and T. Tsukuda, Langmuir, 2004, 20, 11293; J. Am. Chem. Soc., 1998, 120, 6024.
(g) C. G. Arellano, A. Corma, M. Iglesias and F. Sanchez, 26 J.-S. Chen, K. K. Jespersen and J. G. Khinast, J. Mol. Catal.
Chem. Commun., 2005, 1990; (h) S. Carrettin, J. Guzman A: Chem., 2008, 285, 14.
and A. Corma, Angew. Chem., Int. Ed., 2005, 44, 2242; 27 L. Zhou, Q. X. Xu and H. F. Jiang, Chin. Chem. Lett., 2007,
(i) A. Primo and F. Quignard, Chem. Commun., 2010, 46, 18, 1043.
5593; ( j) A. Kar, N. Mangu, H. M. Kaiser, M. Bellerab and 28 M. S. Wong and X. L. Zhang, Tetrahedron Lett., 2001, 42, 4087.
M. K. Tse, Chem. Commun., 2008, 386; Rh: (k) T. Volgler 29 K. Cheng, B. Xin and Y. Zhang, J. Mol. Catal. A: Chem.,
and A. Studer, Adv. Synth. Catal., 2008, 350, 1963; 2007, 273, 240.
(l) K. R. Reddy, K. Rajgopal and M. L. Kantam, Catal. Lett., 30 Z. Xu, J. Mao and Y. Zhang, Catal. Commun., 2008, 9, 97.
2007, 114, 36. 31 G. W. Kabalka and L. Wang, Tetrahedron Lett., 2002, 43, 3067.
13 (a) Z.-L. Shen, S.-Y. Wang, Y.-K. Chok, Y.-H. Xu and 32 T. Matsuda, T. Asai, S. Shiose and K. Kato, Tetrahedron
T.-P. Loh, Chem. Rev., 2013, 113, 271; (b) H. F. Sore, W. R. J. Lett., 2011, 52, 4779.
D. Galloway and D. R. Spring, Chem. Soc. Rev., 2012, 41, 33 L. Chaicharoenwimolkul, A. Munmai, S. Chairam,
1845; (c) C. E. I. Knappke and A. J. V. Wangelin, Chem. Soc. U. Tewasekson, S. Sapudom, Y. Lakliang and E. Somsook,
Rev., 2011, 40, 4948. Tetrahedron Lett., 2008, 49, 7299.
14 (a) E. M. Campi, W. R. Jacksonand and S. M. Marcuccio, 34 A. S. Demir, O. Reis and M. Emrullahoglu, J. Org. Chem.,
J. Chem. Soc., Chem. Commun., 1994, 2395; (b) T. Gillmann 2003, 68, 10130.
and T. Weeber, Synlett, 1994, 649; (c) Z. Z. Songand and 35 K. Rahme, M. T. Nolan, T. Doody, G. P. McGlacken,
H. N. C. Wong, J. Org. Chem., 1994, 59, 33. M. A. Morris, C. O’Driscoll and J. D. Holmes, RSC Adv.,
15 P. T. Anastas and J. C. Warner, Green Chemistry Theory and 2013, 3, 21016.
Practice, Oxford University Press, New York, 1998. 36 M. P. Sk, C. K. Jana and A. Chattopadhyay, Chem. Commun.,
16 (a) A. E. Wendlandt, A. M. Suess and S. S. Stahl, Angew. 2013, 49, 8235.
Chem., Int. Ed., 2011, 50, 11062; (b) Z. Shi, Y. Cui and 37 J. Mao, Q. Hua, G. Xie, Z. Yao and D. Shi, Eur. J. Org.
N. Jiao, Org. Lett., 2010, 12, 2908. Chem., 2009, 2262.
17 (a) B. A. Dara, S. Singh, N. Pandey, A. P. Singh, P. Sharma, 38 X.-T. Zhang, L.-M. Fan, X. Zhao, D. Sun, D.-C. Li and
A. Lazar, M. Sharma, R. A. Vishwakarma and B. Singh, J.-M. Dou, CrystEngComm, 2012, 14, 2053.

2874 | Green Chem., 2014, 16, 2865–2875 This journal is © The Royal Society of Chemistry 2014
 View Article Online

Green Chemistry Paper

39 M. Eddaoudi, J. Kim, M. O. Keeffe and O. M. Yaghi, J. Am. 41 T. Uemura, Y. Ono, K. Kitagawa and S. Kitagawa, Macro-
Chem. Soc., 2002, 124, 376. molecules, 2008, 41, 87.
40 J.-L. Lu, D.-S. Zhang, L. Li and B.-P. Liu, Acta Crystallogr., 42 Y. H. Fan, Y. F. Wang, C. F. Bi, Q. Wang, X. Zhang and
Sect. E: Struct. Rep. Online, 2006, E62, m3321–m3322. X. Y. Liu, Russ. J. Coord. Chem., 2010, 36, 509.
Published on 24 February 2014. Downloaded on 07/05/2014 16:25:58.

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