In situ synthesis of metallophthalocyanines into pores of MIL-101: A novel and green strategy for preparation of host–guest catalysts

Article abstract of DOI:10.1002/aoc.3715

A novel strategy is developed to encapsulate metallophthalocyanines (MPcs, M?=?Cu, Ni and Co) into MIL-101 to give MPcs@MIL-101 via in situ synthesis of MPcs from component fragments in 1-butyl-3-methylimidazolium bromide as an ionic liquid. This strategy overcomes some drawbacks of existing methods for encapsulation of MPcs into metal–organic frameworks. The chemical and structural properties of MPcs@MIL-101 were determined using scanning electron microscopy, powder X-ray diffraction, and Fourier transformation infrared and flame atomic absorption spectroscopies. The results showed that CuPc@MIL-101, which was used as a ‘ship-in-a-bottle’ catalyst, demonstrates excellent catalytic performance in the oxidative amidation of aldehydes with amine salts. It is confirmed that CuPc@MIL-101 can be reused up to five times without significant loss of its activity.

Full text of DOI:10.1002/aoc.3715

Received: 4 October 2016
DOI 10.1002/aoc.3715
Revised: 23 November 2016
Accepted: 25 November 2016
F U L L PA P E R
In situ synthesis of metallophthalocyanines into pores of MIL‐101:
A novel and green strategy for preparation of host–guest catalysts
Mahmoud Borjian Boroujeni | Alireza Hashemzadeh | Ahmad Shaabani | Mostafa M. Amini
Faculty of Chemistry, Shahid Beheshti University,
A novel strategy is developed to encapsulate metallophthalocyanines (MPcs,
M = Cu, Ni and Co) into MIL‐101 to give MPcs@MIL‐101 via in situ synthesis
of MPcs from component fragments in 1‐butyl‐3‐methylimidazolium bromide as
an ionic liquid. This strategy overcomes some drawbacks of existing methods for
encapsulation of MPcs into metal–organic frameworks. The chemical and structural
properties of MPcs@MIL‐101 were determined using scanning electron micros-
copy, powder X‐ray diffraction, and Fourier transformation infrared and flame
atomic absorption spectroscopies. The results showed that CuPc@MIL‐101, which
was used as a ‘ship‐in‐a‐bottle’ catalyst, demonstrates excellent catalytic perfor-
mance in the oxidative amidation of aldehydes with amine salts. It is confirmed that
CuPc@MIL‐101 can be reused up to five times without significant loss of its
activity.
GC, PO Box 19396‐4716, Tehran, Iran
Correspondence
Ahmad Shaabani and Mostafa M. Amini, Faculty
of Chemistry, Shahid Beheshti University, GC,
PO Box 19396‐4716, Tehran, Iran.
Email: a‐shaabani@sbu.ac.ir; m‐pouramini@sbu.
ac.ir
Funding information
Catalyst Center of Excellence (CCE) of Shahid
Beheshti University
KEYWORDS
encapsulation, host–guest catalysts, metallophthalocyanines, MIL‐101, oxidative
amidation
[
10]
1
| INTRODUCTION
polyoxometalate,
organometallic complexes and organo-
metallic compounds into MIL‐101 provides efficient hetero-
geneous catalysts for a wide range of organic transformations.
Metallophthalocyanines (MPcs) are an important class of
compounds that have attracted considerable attention due to
their excellent properties and have many applications in
dye‐synthesized solar cells, photodynamic therapy, pigments,
Over the past decade, metal–organic frameworks (MOFs), as
a new class of porous material, have been used in diverse
fields, including separation, sensing, gas storage and cataly-
[1]
sis. Unique features of MOFs such as structure design abil-
ity, high specific surface area and ordered porous structure
mean that they are excellent supports for immobilization of
[
11]
dyes and biomimetic catalysis. Several methods have been
[
2]
metal nanoparticles or catalytically active complexes. This
class of materials also can make a significant difference from
catalyst recycling, selectivity and conversion value point of
developed for the immobilization of MPcs on organic and
[
12]
inorganic supports, including impregnation,
covalent
[
13]
[14]
grafting
and encapsulation.
Because of the low
[
3]
view. Microporous and mesoporous MOFs in comparison
to zeolites give better molecular accessibility when it comes
to larger substrates and products through bigger windows
and pores. Among the MOFs, MIL‐101 shows good
solubility of MPcs in common solvents, the use of the
impregnation method is limited to using substituted and
soluble MPcs such as RuPcF , (FePctBu4) N and iron
1
6
2
[
15]
tetrasulfophthalocyanine.
Recently, Ma and co‐workers
[
4]
resistance to common solvents, water and temperature.
developed a new strategy to encapsulate a metal‐functionalized
guest molecule such as CoPc into a bio‐MOF‐1 via metal‐
Due to the high stability of MIL‐101 towards the leaching
of Cr(ΙΙΙ) to solution, non‐carcinogenic and non‐mutagenic
Cr(ΙΙΙ) compounds, it is an attractive compound as a support
[
16]
cation‐directed de novo assembly.
Although this method
is efficient for encapsulating guest molecules into MOFs,
application of this strategy is limited because of the use
of an anionic MOF, multiple steps and long reaction time
[5]
in heterogeneous catalysis. Immobilization of Cu nanopar-
[
6]
[7]
[8]
[9]
ticles,
Pd,
PdAg alloy,
Au–Pd nanoparticles,
Appl Organometal Chem. 2017;e3715.
wileyonlinelibrary.com/journal/aoc
Copyright © 2017 John Wiley & Sons, Ltd.
1 of 7
https://doi.org/10.1002/aoc.3715

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BOROUJENI ET AL.
for preparation of MPcs into MOF, and tedious work‐up.
Therefore, development of a simple, fast and green strategy
to encapsulate MPcs into MOFs is in high demand.
NMR spectra were recorded with a Bruker DRX‐300 Avance
spectrometer using CDCl and DMSO‐d as solvents and
tetramethylsilane as internal standard. The melting points of
the products were measured using an Electrothermal 9100
apparatus. The concentration of copper was estimated using
3
6
The amide functional group is one of the most important
in the structures of natural products, pharmaceuticals and
polymers, and the development of benign and efficient
methods for the formation of amide bonds has attracted
a
Shimadzu AA‐680 flame atomic absorption
spectrophotometer.
[
17]
considerable attention from both industry and academia.
The most frequently used methods for amide formations
involve the reaction of activated carboxylic acid derivatives
2.2 | General procedure for synthesis of MIL‐101
[
18]
and amines.
These methodologies have some drawbacks,
MIL‐101 was prepared by hydrothermal reaction according
such as use of expensive and hazardous reagents, poor
[30]
to a previous report.
Briefly, Cr(NO ) ⋅9H O (2.00 g,
3
3
2
atom‐efficiency and generation of a significant amount of
5
.00 mmol), terephthalic acid (0.82 g, 5.00 mmol) and deion-
[
18]
waste.
To overcome these drawbacks, several innovative
ized water (24 ml) were loaded in a hydrothermal chamber
and heated at 220 °C for 18 h. The resulting pale green solid
was collected and washed several times with deionized water,
dimethylformamide (DMF) and hot ethanol and then soaked
in 95% ethanol for 24 h. Finally, the powder was dried
overnight at 150 °C.
strategies such as catalytic acylation of amines with carbox-
[
19]
ylic acid,
azides
hydrative coupling reaction of alkynes with
[
20]
[21]
and direct oxidative amidation of aldehydes
dehydrogenative amidation of alcohols with amines
or
[22]
have
emerged. Among them, oxidative amidation of aldehydes
with amines offers green and significant protocols for
construction of amides due to the stability and availability
[23]
of the starting materials. A number of protocols have been
developed for this transformation, which use heterogeneous
2
.3 | General procedure for preparation of
2+
Cu @MIL‐101
[
24]
[25]
[26]
or homogeneous catalysts based on Rh,
Ru,
Ag,
2+
[27]
[28]
Cu @MIL‐101 was prepared via double solvents method
[31]
Au
and Cu.
Therefore, development of new methods
according to pervious reports.
Typically, activated
for the facile construction of amides is highly desirable. To
the best of our knowledge, there is no report on the use of
MPcs@MIL‐101 as a heterogeneous catalyst for oxidative
amidation.
MIL‐101 (0.200 g) was suspended in 50 ml of dry n‐hexane
as a hydrophobic solvent in a round‐bottomed flask and the
mixture was sonicated for 30 min until the sample was
dispersed in the n‐hexane. To this mixture 0.123 ml of a
In continuation of our ongoing research on sustainable
benign pathways for organic transformations and
1
M solution of dehydrated Cu(ΙΙ) chloride as hydrophilic
[
29]
solvent was added dropwise under continuous vigorous
stirring. The resulting mixture was stirred for 3 h and then
the green powder was filtered and dried under vacuum at
nanocatalysis,
we introduce a novel strategy for in situ
synthesis of MPcs into MIL‐101 and investigate the catalytic
activity as heterogeneous catalysts for oxidative amidation of
aldehydes with amines. Notable features of our work include
2+
1
50 °C. The Cu(ΙΙ) content of Cu @MIL‐101 was deter-
mined using flame atomic absorption spectroscopy, it being
found to be 3.0 wt%.
(i) simple, fast and green approach to encapsulate MPcs into
a three‐dimensional MOF, (ii) using commercially available
raw materials for preparation of MPcs@MIL‐101, (iii) easy
work‐up of products and (iv) utilizing ionic liquids for the
synthesis of catalyst and elimination of the use of organic
solvents.
2
.4 | General procedure for synthesis of
CuPc@MIL‐101
2+
Cu @MIL‐101 (0.200 g) was suspended in 2 ml of
ethanol and phthalonitrile (0.064 g, 0.500 mmol) was added
to this suspension and stirring was continued for 1 h. Then
the solvent was evaporated under vacuum. The residue and
2
2
| EXPERIMENTAL
1‐butyl‐3‐methylimidazolium bromide ([Bmim]Br; 0.438 g,
.1 | Materials and methods
2
.00 mmol) were heated at 180 °C for 1 h to afford
Fourier transform infrared (FT‐IR) spectra were recorded
with a Bomem MB‐Series FT‐IR spectrometer. Powder X‐
ray diffraction (XRD) patterns were recorded using a STOE
diffractometer with Cu Kα radiation (λ = 1.5418 Å).
Scanning electron microscopy (SEM) and energy‐dispersive
X‐ray spectroscopy (EDS) analyses were performed using a
CuPc@MIL‐101 as indicated by the change of colour of
the mixture to deep blue. Upon completion and cooling
the mixture to room temperature, the mixture was washed
with distilled water three times and ethanol. Finally the
solid was dried under vacuum at 150 °C. The amount of
MPc in the cages of MIL‐101 was analysed using induc-
tively coupled plasma atomic emission spectroscopy, and
a value of 18 wt% loading was obtained.
Philips XL‐30 instrument. All samples for morphological
1
studies were sputtered with gold before observation.
H

BOROUJENI ET AL.
3 of 7
2.5 | General procedure for oxidative amidation of
benzaldehyde with amine salts
A mixture of CuPc@MIL‐101 (30.0 mg), benzaldehyde
(1.00 mmol), amine hydrochloride salt (1.20 mmol), CaCO3
(110 mg, 1.10 mmol) and tert‐butyl hydroperoxide (TBHP;
70% in water, 0.16 ml, 1.10 mmol) in acetonitrile (2 ml)
was added in a 25 ml round‐bottom flask and the reaction
mixture was stirred at room temperature for 4 h. Upon
completion the reaction (TLC monitoring), the catalyst was
filtered and the volatiles were removed under reduced
pressure. The crude product was purified by column chroma-
tography on silica gel (petroleum ether–ethyl acetate) to
afford amide product.
FIGURE 1 XRD patterns of (A) MIL‐101 and (B) CuPc@MIL‐101
Figure 4, the SEM images confirm that the structure of
MIL‐101 is stable in the catalyst preparation process. Also,
EDS analysis indicates the presence of copper in
CuPc@MIL‐101 (Figure 5).
3
| RESULTS AND DISCUSSION
Our novel strategy for the preparation of CuPc@MIL‐101
includes two steps (Scheme 1): (i) immobilizing Cu(ΙΙ) ions
inside the pores of MIL‐101 prepared using the double
solvent method
bling of fragments under the direction of copper ions into
According to BET data, specific surface area and total
2
−1
pore volume of MIL‐101 are estimated to be 1835 m g
[
32]
3
−1
and (ii) preparation of MPcs by assem-
and 0.87 cm g . These values for CuPc@MIL‐101 are
2 3
−1
−1
1516 m g and 0.78 cm g . The reduction of specific sur-
face area and total pore volume indicates that CuPc mole-
cules are certainly encapsulated within the pores of MIL‐101.
The applicability of the in situ synthesis for the prepara-
tion of other MPcs into the pores of MIL‐101 was investi-
gated, and CoP@MIL‐101 and NiPc@MIL‐101 were
successfully synthesized in the presence ionic liquid by
heating at 180 °C. Powder XRD, FT‐IR and UV–visible
spectroscopic, SEM and EDS studies confirm their formation
(supporting information, Figures S2–S11).
the MIL‐101 pores in the presence of ionic liquid.
Figure 1 shows the XRD patterns of MIL‐101 and
CuPc@MIL‐101. The XRD pattern of MIL‐101 does not
change after the synthesis of the CuPc into the pores of
MIL‐101, which implies the structure of MIL‐101 remains
intact after reaction. Since CuPc is dispersed into the cavities
of MIL‐101, the characteristic reflections of CuPc are not
observed in the XRD pattern of CuPc@MIL‐101.
To confirm the assembly of phthalonitrile into Pc, FT‐IR
spectroscopy was used. Notably, the CN stretching vibration
band at 2230 cm is absent in the phthalonitrile‐loaded
Cu @MIL‐101 spectrum and the characteristic vibrations of
CuPc at 721, 748, 1087, 1114, 1161 and 1712 cm−1 for
CuPc@MIL‐101 appear (Figure 2). These observations
imply the successful formation of CuPc into MIL‐101.
UV–visible absorption spectroscopy is an important
technique for characterizing the optical properties of MPcs
and identification of their chemical structures. Successful
formation of the CuPc into the cavities of MIL‐101 was
confirmed using UV–visible spectroscopy. The UV–visible
spectrum of CuPc@MIL‐101 reveals two bands at 710 and
To elaborate the advantages of the in situ synthesis
strategy compared to existing methods, the preparation of
CuPc@MIL‐101 using the impregnation approach was
attempted. Immersing MIL‐101 into a mixture of CuPc and
tetrahydrofuran ultrasonically dispersed at room temperature
for 20 h provided CuPc@MIL‐101, but due to the low solu-
−
1
2
+
[
33]
bility of CuPc,
this method failed and only a negligible
amount of phthalocyanine was loaded on MIL‐101 without
good dispersity. Therefore, this observation highlights the
7
95 nm (Figure 3), which are characteristic bands of phthalo-
[
5]
cyanines. In addition, CuPc@MIL‐101 powder is blue, as
compared to the green colour of MIL‐101, indicating the
association of CuPc molecules into the pores of MIL‐101.
SEM analysis was carried out to study the structure and
morphology of MIL‐101 and CuPc@MIL‐101. As shown in
2
+
FIGURE 2 FT‐IR spectra of (A) phthalonitrile‐loaded Cu @MIL‐101,
(B) CuPc and (C) CuPc@MIL‐101
SCHEME 1 Procedure for in situ synthesis of CuPc@MIL‐101

4
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BOROUJENI ET AL.
FIGURE
3
UV–visible spectra of the MIL‐101 (green) and
CuPc@MIL‐101 (blue)
FIGURE 5 EDS analysis of CuPc@MIL‐101
novelty of the in situ synthesis of CuPc into MIL‐101. It is
interesting to note that one of the most important advantages
of this method is the controlled loading of phthalocyanine
into the pores of MIL‐101.
To evaluate the catalytic properties of CuPc@MIL‐101,
at the outset, a model reaction of benzaldehyde and
benzylamine hydrochloride to form N‐benzylbenzamide was
selected. This reaction in the presence of CoPc@MIL‐101,
NiPc@MIL‐101 and CuPc@MIL‐101 affords certain yields
of product (Table 1, entries 1–3). Among these catalysts,
CuPc@MIL‐101 is found to be the best catalyst to give
N‐benzylbenzamide in 55% yield (Table 1, entry 3). When
the reaction is carried out in the presence of pristine
MIL‐101, the product is obtained in 35% yield within 6 h
at 60 °C (Table 1, entry 4). As the amount of
CuPc@MIL‐101 is increased, the reaction goes to comple-
tion at room temperature (Table1, entries 5–8). Reaction in
2+
the presence of Cu @MIL‐101 as a heterogeneous catalyst
produces the desired product in good yield after 5 h
(
Table1, entry 10). It is important to note that the catalytic
2+
activity of Cu @MIL‐101 decreases in the next runs in
the reaction conditions experiment due to leaching of cop-
per ions into the solution. Therefore, CuPc@MIL‐101 is a
2+
better catalyst than Cu @MIL‐101 with either a higher
catalytic activity in shorter reaction times or more stability
towards the leaching Cu(ΙΙ) ions. Control experiments in
the presence of the CuPc and a mixture of the CuPc and
MIL‐101 give the product in 10 and 40% yields under the
same reaction conditions (Table1, entries 11 and 12),
whose catalytic activity is also lower than that of
CuPc@MIL‐101. The effect of various solvents was exam-
ined (Table1, entries 13–17), and it is found that acetoni-
trile is the preferred solvent. In order to determine the
best oxidant, various oxidants, including air, oxygen, urea
hydrogen peroxide (UHP) and TBHP, were tested (Table1,
entries 18–20). TBHP is the best oxidant for this reaction.
The effect of base in the reaction was also investigated
(
Table1, entries 21–23). CaCO is the base that gives the
3
best results. Control experiments (Table 1, entries 24–26)
reveal that catalyst, base and oxidant are all necessary for
this reaction. The optimized conditions for the oxidative
amidation are 0.030 g of catalyst and 1.1 mmol of CaCO3
in acetonitrile using TBHP as an oxidant at room tempera-
ture for 4 h.
With the optimized reaction conditions established, a
wide range of benzaldehydes was used for this reaction.
Fairly good to excellent yields of amides were obtained in
most cases (Table 2).
FIGURE 4 SEM images of (A) MIL‐101 and (B) CuPc@MIL‐101

BOROUJENI ET AL.
5 of 7
a
TABLE 1 Screening of reaction conditions
b
Entry
Catalyst (amount, g)
Solvent
Base
Oxidant
Time (h)
Yield (%)
1
2
3
4
5
6
7
8
9
NiPc@MIL‐101 (0.01)
CoPc@ML‐101 (0.01)
CuPc@MIL‐101 (0.01)
MIL‐101 (0.03)
CH
CH
CH
CH
CH
CH
CH
CH
CH
CH
CH
CH
3
3
3
3
3
3
3
3
3
3
3
3
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
CaCO
CaCO
CaCO
CaCO
CaCO
CaCO
CaCO
CaCO
CaCO
CaCO
CaCO
CaCO
CaCO
CaCO
CaCO
CaCO
CaCO
CaCO
CaCO
CaCO
3
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
4
4
40
45
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
4
55
c
6
35
CuPc@MIL‐101 (0.015)
CuPc@MIL‐101 (0.020)
CuPc@MIL‐101 (0.025)
CuPc@MIL‐101 (0.030)
CuPc@MIL‐101 (0.035)
4
63
72
84
92
92
80
40
10
52
45
46
35
48
27
18
24
32
23
16
11
0
4
4
4
4
2
+
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
Cu @MIL‐101
5
CuPc‐MIL‐101 (0.03)
CuPc (0.008)
5
5
CuPc@MIL‐101 (0.030)
CuPc@MIL‐101 (0.030)
CuPc@MIL‐101 (0.030)
CuPc@MIL‐101 (0.030)
CuPc@MIL‐101 (0.030)
CuPc@MIL‐101 (0.030)
CuPc@MIL‐101 (0.030)
CuPc@MIL‐101 (0.030)
CuPc@MIL‐101 (0.030)
CuPc@MIL‐101 (0.030)
CuPc@MIL‐101 (0.030)
CuPc@MIL‐101 (0.030)
CuPc@MIL‐101 (0.030)
—
DMF
7
DMSO
EtOH
7
7
H
2
O
7
Toluene
7
CH
CH
CH
CH
CH
CH
CH
CH
CH
3
3
3
3
3
3
3
3
3
CN
CN
CN
CN
CN
CN
CN
CN
CN
O
2
12
15
15
8
Air
UHP
TBHP
TBHP
TBHP
TBHP
—
Na
2
CO
3
K
2
CO
3
8
NaOH
8
—
15
15
15
CaCO
CaCO
3
3
TBHP
8
a
Reaction conditions: benzaldehyde (1.00 mmol, 0.068 g), amine hydrochloride salt (1.20 mmol),oxidant, solvent, base, catalyst.
b
Isolated yield.
c
Reaction temperature was 60 °C.
a
TABLE 2 CuPc@MIL‐101‐catalyzed oxidative amidation from aldehydes and amine hydrochloride salts
Entry
R
1
R
2
Product
Time (h)
Yield (%)b
Melting point (°C)
[
[
[
[
[
[
[
[
34]
35]
36]
34]
34]
35]
37]
38]
1
2
3
4
5
6
7
8
H
H
3a
3b
3c
4
5
5
4
4
6
4
5
92
80
85
83
88
84
90
85
102–104
128–131
137–139
161–163
166–168
134–137
138–140
140–142
OMe
Me
Cl
H
H
H
H
H
3d
3e
Br
NO
H
2
3f
Me
Me
3 g
3 h
Me
a
3
Reaction conditions: CuPc@MIL‐101 (30.0 mg), aldehyde (1.00 mmol), amine hydrochloride salt (1.20 mmol), CaCO (110 mg, 1.10 mmol) and TBHP (70% in water,
0
.16 ml, 1.10 mmol), acetonitrile (2 ml), room temperature.
b
Isolated yield.

6
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BOROUJENI ET AL.
complexes and metallorganic compounds on supports for
heterogeneous catalysis investigations.
ACKNOWLEDGEMENTS
SCHEME 2 Plausible reaction mechanism
We gratefully acknowledge financial support from the
Catalyst Center of Excellence (CCE) of Shahid Beheshti
University and the Iran National Elites Foundation (INEF).
REFERENCES
[
[
1] H.‐C. Zhou, J. R. Long, O. M. Yaghi, Chem. Rev. 2012, 112, 673.
2] L. W. Zhang, S. H. Wu, Y. Liu, F. F. Wang, X. Han, H. Y. Shang, Appl.
Organometal. Chem. 2016, 30, 684.
[
3] a) P.‐Z. Li, X.‐J. Wang, J. Liu, J. S. Lim, R. Zou, Y. Zhao, J. Am. Chem. Soc.
2016, 138, 2142; b) J. Liu, X. B. Zhang, J. Yang, L. Wang, Appl.
Organometal. Chem. 2014, 28, 198.
[
4] F. Zhang, Y. Jin, J. Shi, Y. Zhong, W. Zhu, M. S. El‐Shall, Chem. Eng. J.
2015, 269, 236.
[
[
5] F. Wu, L.‐G. Qiu, F. Ke, X. Jiang, Inorg. Chem. Commun. 2013, 32, 5.
6] F. Zhang, Y. Jin, Y. Fu, Y. Zhong, W. Zhu, A. A. Ibrahim, M. S. El‐Shall,
J. Mater. Chem. A 2015, 3, 17008.
FIGURE 6 Recycling of CuPc@MIL‐101 for oxidative amidation of
benzaldehyde with benzylamine salt
[
[
7] J. Hermannsdoerfer, R. Kempe, Chem. – Eur. J. 2011, 17, 8071.
8] Y.‐Z. Chen, Y.‐X. Zhou, H. Wang, J. Lu, T. Uchida, Q. Xu, S.‐H. Yu, H.‐L.
Jiang, ACS Catal. 2015, 5, 2062.
[39]
Based on previous reports,
a plausible mechanism is
[
9] X. Gu, Z.‐H. Lu, H.‐L. Jiang, T. Akita, Q. Xu, J. Am. Chem. Soc. 2011, 133,
proposed, as shown in Scheme 2. Because of the potential
for oxidation of free amines in the presence of TBHP, using
amine salts is necessary. Slow formation of amines using
11822.
[
10] J. Han, D. Wang, Y. Du, S. Xi, Z. Chen, S. Yin, T. Zhou, R. Xu, Appl. Catal.
A 2016, 521, 83.
amine salts and CaCO as the base minimizes amine oxida-
[11] A. B. Sorokin, Chem. Rev. 2013, 113, 8152.
3
tion under the reaction conditions. The reaction of amine
and benzaldehyde produces a hemiaminal intermediate which
is oxidized to amide in the presence of CuPc@MIL‐101.
The stability of CuPc@MIL‐101 towards the leaching
Cu(ΙΙ) ion was also examined. After removal of
CuPc@MIL‐101 by filtration, no detectable CuPc or Cu(ΙΙ)
ions in the reaction solution was observed. The recyclability
of CuPc@MIL‐101 was surveyed for oxidative amidation
under the optimized conditions. After completion of the reac-
tion, CuPc@MIL‐101 was filtered, was washed and dried at
[
12] A. Rezaeifard, M. Jafarpour, A. Naeimi, R. Haddad, Green Chem. 2012, 14,
3386.
[13] P. Chauhan, N. Yan, RSC Adv. 2015, 5, 37517.
[14] Y. Tanamura, T. Uchida, N. Teramae, M. Kikuchi, K. Kusaba, Y. Onodera,
Nano Lett. 2001, 1, 387.
[
15] E. Kockrick, T. Lescouet, E. V. Kudrik, A. B. Sorokin, D. Farrusseng, Chem.
Commun. 2011, 47, 1562.
[
16] B. Li, Y. Zhang, D. Ma, T. Ma, Z. Shi, S. Ma, J. Am. Chem. Soc. 2014, 136,
1202.
[17] V. R. Pattabiraman, J. W. Bode, Nature 2011, 480, 471.
[18] C. L. Allen, J. M. J. Williams, Chem. Soc. Rev. 2011, 40, 3405.
[19] R. M. Lanigan, P. Starkov, T. D. Sheppard, J. Org. Chem. 2013, 78, 4512.
[20] S. H. Cho, E. J. Yoo, I. Bae, S. Chang, J. Am. Chem. Soc. 2005, 127, 16046.
[21] J. Gao, G.‐W. Wang, J. Org. Chem. 2008, 73, 2955.
[
[
150 °C and was used in the next run. It was found that
CuPc@MIL‐101 could be reused for five cycles without a
significant decrease in its catalytic activity (Figure 6).
22] X. Xie, H. V. Huynh, ACS Catal. 2015, 5, 4143.
23] S. C. Ghosh, J. S. Y. Ngiam, A. M. Seayad, D. T. Tuan, C. L. L. Chai, A.
4
| CONCLUSIONS
Chen, J. Org. Chem. 2012, 77, 8007.
[
24] Z. Wu, K. L. Hull, Chem. Sci. 2016, 7, 969.
In summary, we developed a novel strategy for encapsulation
of MPc into the cavities of MIL‐101. This method demon-
strates unique advantages such as using ionic liquid, simple
synthetic method, utilizing commercially available raw mate-
rials, elimination of the use of organic solvents and short reac-
tion time compared to approaches for preparation of MPcs on
supports. CuPc@MIL‐101 was efficiently employed as a new
heterogeneous catalyst for oxidative amidation. The reaction
was carried out at room temperature with good to excellent
yields. Ongoing work in our laboratory includes using this
novel strategy for simple preparation of organometallic
[
25] a) B. Kang, Z. Fu, S. H. Hong, J. Am. Chem. Soc. 2013, 135, 11704; b) A. J.
A. Watson, A. C. Maxwell, J. M. J. Williams, Org. Lett. 2009, 11, 2667.
[26] C. Chen, S. H. Hong, Org. Biomol. Chem. 2011, 9, 20.
[27] J.‐F. Soulé, H. Miyamura, S. Kobayashi, J. Am. Chem. Soc. 2011, 133,
18550.
[
28] T. Hamada, X. Ye, S. S. Stahl, J. Am. Chem. Soc. 2008, 130, 833.
[29] a) A. Shaabani, M. Borjian Boroujeni, M. S. Laeini, Appl. Organometal.
Chem. 2016, 30, 154; b) A. Shaabani, M. Borjian Boroujeni, M. S. Laeini,
RSC Adv. 2016, 6, 27706; c) M. Mahyari, M. S. Laeini, A. Shaabani, Chem.
Commun. 2014, 50, 7855.
[
30] L. Bromberg, Y. Diao, H. Wu, S. A. Speakman, T. A. Hatton, Chem. Mater.
2012, 24, 1664.

BOROUJENI ET AL.
7 of 7
[
31] a) Q. Yang, Y.‐Z. Chen, Z. U. Wang, Q. Xu, H.‐L. Jiang, Chem. Commun.
015, 51, 10419; b) Y. Liu, S.‐Y. Jia, S.‐H. Wu, P.‐L. Li, C.‐J. Liu, Y.‐M.
[39] a) W.‐J. Yoo, C.‐J. Li, J. Am. Chem. Soc. 2006, 128, 13064; b) S. C. Ghosh,
J. S. Y. Ngiam, C. L. L. Chai, A. M. Seayad, T. T. Dang, A. Chen, Adv.
Synth. Catal. 2012, 354, 1407.
2
Xu, F.‐X. Qin, Catal. Commun. 2015, 70, 44.
[
32] a) M. Yadav, Q. Xu, Chem. Commun. 2013, 49, 3327; b) A. Aijaz, A.
Karkamkar, Y. J. Choi, N. Tsumori, E. Rönnebro, T. Autrey, H. Shioyama,
Q. Xu, J. Am. Chem. Soc. 2012, 134, 13926; c) Q.‐L. Zhu, J. Li, Q. Xu,
J. Am. Chem. Soc. 2013, 135, 10210.
SUPPORTING INFORMATION
Additional Supporting Information may be found online in
the supporting information tab for this article.
[33] F. Ghani, J. Kristen, H. Riegler, J. Chem. Eng. Data 2012, 57, 439.
[34] R. A. Green, D. Pletcher, S. G. Leach, R. C. D. Brown, Org. Lett. 2016, 18,
1
198.
How to cite this article: Boroujeni MB,
Hashemzadeh A, Shaabani A, Amini MM. In situ
synthesis of metallophthalocyanines into pores of
MIL‐101: A novel and green strategy for preparation
of host–guest catalysts. Appl Organometal Chem
[
35] T. K. Achar, P. Mal, J. Org. Chem. 2015, 80, 666.
[
36] H. Morimoto, R. Fujiwara, Y. Shimizu, K. Morisaki, T. Ohshima, Org. Lett.
2
014, 16, 2018.
[
37] F. Li, J. Ma, L. Lu, X. Bao, W. Tang, Catal. Sci. Technol. 2015, 5, 1953.
38] S. Khamarui, R. Maiti, D. K. Maiti, Chem. Commun. 2015, 51, 384.
2
017;e3715. https://doi.org/10.1002/aoc.3715
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