Heterogenization of manganese porphyrin via hydrogen bond in zeolite imidazolate framework-8 matrix, a host-guest interaction, as catalytic system for olefin epoxidation

Article abstract of DOI:10.1142/S1088424618500931

A heterogenized meso-tetrakis(2,3-dihydroxyphenyl)porphyrinatomanganese(III) acetate at zeolite imidazolate framework-8 (T(2,3-OHP)PorMn@ZIF-8) is investigated for the catalytic olefin epoxidation reactions at room temperature. Heterogenization is accompl

Full text of DOI:10.1142/S1088424618500931

Journal of Porphyrins and Phthalocyanines
J. Porphyrins Phthalocyanines 2018; 22: 1–9
DOI: 10.1142/S1088424618500931
Published at http://www.worldscinet.com/jpp/
Heterogenization of manganese porphyrin via hydrogen
bond in zeolite imidazolate framework-8 matrix, a host–guest
interaction, as catalytic system for olefin epoxidation
Mojtaba Bagherzadeh* and Elnaz Mesbahi
Chemistry Department, Sharif University of Technology, P.O. Box 11155-3615, Tehran, Iran
Received 17 April 2018
Accepted 2 July 2018
ABSTRACT: A heterogenized meso-tetrakis(2,3-dihydroxyphenyl)porphyrinatomanganese(III) acet-
ate at zeolite imidazolate framework-8 (T(2,3-OHP)PorMn@ZIF-8) is investigated for the catalytic
olefin epoxidation reactions at room temperature. Heterogenization is accomplished through a non-
classical hydrogen bond proposed between T(2,3-OHP)PorMn bearing O–H groups and C–H of the
2-methylimidazolate linkers in the ZIF-8 structure. The aforementioned compound is characterized
by X-ray powder diffraction (XRD), atomic absorption spectroscopy (AAS), nitrogen adsorption−
desorption, FT-IR spectroscopy, field emission scanning electron microscopy (FE-SEM), transmission
electron microscopy (TEM) and Raman spectroscopy. The catalytic system with rather high potential
of reusability is proposed as a fairly efficient epoxidation catalyst compared to reports in homogeneous
media.
KEYWORDS: manganese porphyrin, Zeolite Imidazolate Framework-8, non-classical hydrogen
bonding, catalytic epoxidation.
capable of forming such non-classical weak hydrogen
INTRODUCTION
bonds [20, 21]. There are some reports in literature
Mimicking catalytic function of biological systems
documenting existence of the aforementioned category
including cytochrome-P450, hemoglobin, peroxidase
of hydrogen bonds in metalloporphyrin catalytic
and other oxidative enzymes has always been one of the
homogeneous systems [22]. Unusual co-catalytic
most interesting targets for scientific researchers [1–7].
activity of 2,6-dimethylpyridine in the presence of meso-
Metalloporphyrins have been extensively considered as
tetrakis(pentafluorophenyl) porphyrinatomanganese(III)
proper models of enzymes in olefin epoxidations [8–14].
acetate (MnTPFPP(OAc)) is proported to arise from
To the best of our knowledge the catalytic activity and
stability of metalloporphyrins are influenced by various
hydrogen bonding between the ortho-C–F moieties of
Mn(Por) and the ortho methyls on pyridine [23, 24]. The
electronic and steric properties [15, 16]. Recently more
importance of hydrogen bond presence is also evidenced
attention has been paid to the importance of some
based on the higher activity of manganese porphyrins with
interactions such as hydrogen bonds as a dominant factor
hydroxy or methoxy groups at the 2 and 3 positions of
playing a role in the active site of natural enzymes [17]. A
category of carbon–oxygen hydrogen bonding (CH…O)
the phenyls on the meso-substituted porphyrins [25, 26].
Moreover, it has been revealed that meso-tetrakis(2,3-
differing from the previously well-known classic type
dihydroxyphenyl)porphyrinatomanganese(III) acetate
[19] has been documented in biological structures during
performs as a preferable epoxidation catalyst in the
the last four decades [18]. Aliphatic carbon atoms are
presence of 2-methylimidazole in homogeneous media,
although it still suffers from lack of recyclability [27].
To overcome this problem, heterogenization of such
systems through encapsulation in the cages of the
*Correspondence to Mojtaba Bagherzadeh, email bagherzadeh@
sharif.edu.
Copyright © 2018 World Scientific Publishing Company

2
M BAGHERZADEH & E MESBAHI
porous materials such as metal organic frameworks
(MOFs) with their favorable properties would help
[28–32]. Zeolite imidazolate framework-8 (ZIF-8) is a
MOF composed of tetrahedrally-coordinated Zn ions
connected by 2-methylimidazolate linkers with external
surfaces having hydrophilic properties [33–36]. Its
six-membered ring pore windows are narrow enough
to prevent the exit of the stuck metalloporphyrins. It
is worth mentioning that the existence of a functional
group with the ability to produce hydrogen bonds on the
porphyrin compound is essential for the encapsulation
process [37].
In this work, Mn(por) bearing OH substituents in
the ortho and meta positions of the phenyl groups
is heterogenized in a zeolite imidazolate framework
(ZIF-8) matrix via host–guest interaction (Fig. 1). The OH
groups are capable of producing non-classical hydrogen
bond with the aliphatic C–H on the 2-methylimidazolate
parts of the matrix in the periphery of the porphyrin.
Olefin epoxidation in the presence of the heterogenized
metalloporphyrin and tetra-n-butylammonium hydrogen
monopersulfate as oxidant has been examined. It seems
that combination of T (2,3-OHP)PorMnOAc with ZIF-8
(T(2,3-OHP)PorMn@ZIF-8) brings about a desirable
oxidation catalyst for cyclooctene and cyclohexene,
overcoming the reusability problem.
RESULTS AND DISCUSSION
Characterization of T (2,3-OHP)PorMn@ZIF-8
In order to characterize the catalyst structure, the
XRD patterns of MnPor@ZIF-8 and ZIF-8 are measured
(Fig. 2 and S1). The XRD patterns of both compounds
show highly crystalline structures consistent with
previous literature reports (Fig. 2) [36, 38]. The similar
pattern of characteristic peaks for MnPor@ZIF-8 with
a negligible decrease in the intensities indicates that
the crystalline structure of ZIF-8 is likely to be retained
without significant changes; however, it is influenced by
the host–guest interaction.
The formation of such structures was confirmed by
the FT-IR technique as well (Fig. 3 and S2) [39]. The
characteristic band of ZIF-8 structure relating to Zn–N
stretching at 421 cm-1 is clearly observed [38, 40]. A very
slight shift in the band location around 2931 cm-1 which
is ascribed to the aliphatic C–H stretch of 2-methylimid-
azole [41–43] could be occured as a result of a weak
hydrogen bond between C–H of 2-methylimidazole and
the porphyrin bearing OH groups.
The amount of T(2,3-OHP)PorMn loaded as
determined by atomic absorption spectroscopy was
3.1 mg/g.It is noteworthy that the loading process of
Fig. 1. Schematic structure of (a) T(2,3-OHP)PorMn@ZIF-8 and the moieties prone to hydrogen bonding formation (b) probable
hydrogen bond orientation between hydroxy groups of phenyl rings in the effective isomer of T(2,3-OHP)PorMnOAc and
2-methylimidazolate linkers in ZIF-8
Copyright © 2018 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2018; 22: 2–9

HETEROGENIZATION OF MANGANESE PORPHYRIN VIA HYDROGEN BOND
3
T(2,3-OHP)PorMn@ZIF-8 compared to that of ZIF-8
may suggest that the host–guest interactions occur
mostly on the outer surface of ZIF-8 [45]. In addition,
the swing of the imidazolate moieties in ZIF-8 would
likely be involved in order to have an appropriate
orientation and so the facility of participating in
interaction with hydroxyl groups prone to hydrogen
bonding [46].
In order to gain more insight into the presence
of such interactions, Raman spectra of ZIF-8 and
T(2,3-OHP)PorMn@ZIF-8 were compared (Fig. 5). The
peak appearing around 1460 cm-1 is related to the C–H
bonding of the methyl group in the 2-methylimidasolate
linkers of ZIF-8 [46]. Whenever any kind of hydrogen
bonding takes place, it could affect the appearance
of the peak mentioned above and thus shift it slightly.
Hence, considering the clear broadening and the slight
shift, such an interaction may occur between the OH
group moieties on the periphery of the porphyrin and
the 2-methylimidasolate in the ZIF-8 structure (Fig. 1).
Note that the presence of this unusual kind of hydrogen
bonding has already been documented in homogeneous
Fig. 2. PXRD pattern of ZIF-8 (blue) and T (2,3-OHP)PorMn@
ZIF-8 (red)
media [25, 27].
The morphology of T(2,3-OHP)PorMn@ZIF-8 has
beeninvestigatedthroughfield-emissionscanningelectron
microscopy (FE-SEM) and high resolution transmission
electron microscopy (HR-TEM) (Fig. 6). It seems that the
sample particles are highly eager to aggregate, as shown
in the figure. The particular honeycomb of the ZIF-8
structure is also observed [36, 38].
T(2,3-OHP)PorMn at ZIF-8 was accompanied by a
change in color from cream to gray (Fig. 2). The surface
area and pore volume of T(2,3-OHP)PorMn@ZIF-8
has been surveyed through the nitrogen adsorption–
desorption method (Fig. S3). As shown in Fig. 4, a type I
isotherm is obviously obtained through this investigation
with concern to the ones reported by IUPAC [44]. The
surface area of BET (Brunauer–Emmett–Teller) and
pore volume of T(2,3-OHP)PorMn@ZIF-8 gained
Catalytic epoxidation reaction
Epoxidation of various olefins was investigated in
the presence of the heterogenized manganese porphyrin
(T(2,3-OHP)PorMn@ZIF-8) in a mixture of CH2Cl2 and
methanol (in a ratio of 5:1). Tetra-n-butylammonium
2
-1
3
-1
.
.
104.19 m g and 0.1187 cm g respectively (Table 1).
A slight increase in the surface area and pore volume of
Fig. 3. FT-IR spectra of 2-methylimidazole (blue), ZIF-8 (purple) and T (2,3-OHP)PorMn@ZIF-8 (red)
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M BAGHERZADEH & E MESBAHI
Fig. 4. Representative N2 adsorption and desorption isotherms
of (a) ZIF-8 and (b) T(2,3-OHP)PorMn@ZIF-8
Fig. 5. Raman spectrum of ZIF-8 (red) and T (2,3-OHP)
PorMn@ZIF-8 (blue)
Table 1. Textural properties, aS,BET (BET surface area) and
Vp (pore volume)
-1
-1
Sample
as,BET (m2 g ) Vp (cm3 g )
. .
greater conversion percentage is achieved (entries 3–6).
Moreover, the greater amount of conversion obtained
for 4-methoxystyrene in comparison to the analogue
species might take place as a result of a more readily
entrance or access to the active sites of the catalyst in
the hydrophilic moieties. It seems that the active sites
of the catalyst are inaccessible in the case of the bulky
substrates such as 1-octene, cis-stilbene and trans-
stilbene considering the low conversion and selectivity
(entries 7–9).
In order to survey the reusability of our catalyst, it
was separated, washed thoroughly with ethanol and dried
after centrifuging the reaction mixture at the end of the
reaction time. The catalyst was utilized for the next run
after preparation as mentioned above. It was revealed
that T(2,3-OHP)PorMn@ZIF-8 could be used in six
subsequent runs without a considerable decrease in its
performance (Fig. 9). The XRD pattern of T (2,3-OHP)
PorMn@ZIF-8 after usage in 7 runs seems to be altered
compared to those represented in Fig. 2 and indicates a
change in the catalyst structure (Fig. 10).
ZIF-8
97.325
104.19
0.049182
0.1187
T(2,3-OHP)PorMn@ZIF-8
hydrogen monopersulfate (n-Bu4NHSO5) was used as
an oxidant in all the reactions. The ratio of the reactants,
catalyst and oxidant concentrations and the reaction
time were optimized (Figs 7 and 8). The reactions
were all carried out at room temperature and the results
obtained through injection into GC after stirring for
18 h. The conversion percentage for various alkenes
and selectivity to their corresponding epoxides are
presented in Table 2. According to the results shown in
Table 2, the greatest amount of conversion is obtained
for cyclooctene and cyclohexene. The lower selectivity
in the case of cyclohexene compared to cyclooctene
is due to the formation of other oxidation products
rather than epoxide (entries 1 and 2). Among styrene
derivatives, the more electron rich the double bond is, the
Fig. 6. (a) FESEM of T(2,3-OHP)PorMn@ZIF-8 with the scale bar of 500 nm; (b) HRTEM of T(2,3-OHP)PorMn@ZIF-8
Copyright © 2018 World Scientific Publishing Company
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HETEROGENIZATION OF MANGANESE PORPHYRIN VIA HYDROGEN BOND
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Table 2. Conversion percentage and selectivity to corresponding epoxide of various alkenes in
epoxidation reaction
Entry
1
Substrate
Product
Conversion %
87
Selectivity to epoxide %
98
O
2
97
52
O
O
!
!
3
4
5
6
7
70
55
24
28
11
50
36
O
O
29
O
89
>99
O
8
7
43 (21)
O
9
31
77 (19)
Substrate (0.2 mmol), n-Bu4NHSO5 (0.4 mmol), catalyst (3 × 10-4 mmol), CH2Cl2/methanol (5:1),
room temperature, 18 h, internal standard method was used.
Comparison of analogue homogenous
and heterogeneous media
the presence of T(4-OHP)PorMn@ZIF-8, which is in
agreement with its higher BET surface area (Table S1).
To compare the performance of T(2,3-OHP)
PorMn@ZIF-8 with various analogues reported in
literature, the results and conditions of cyclooctene
epoxidation in the presence of diverse homogenous
and heterogeneous catalytic media is presented in
Table 3 [25, 27, 37]. In homogeneous media, the
cooperating interplay of hydrogen bonding gives
rise to higher conversions in the case of T(2,3-OHP)
PorMn/2-methylimidazole and T(2,3-OHP)PorMn/
acetate compared to the cases showing a lack of such
interaction (entry 2,4 and 3,5).
EXPERIMENTAL
Materials
T(2,3-OHP)PorMnOAc and T(4-OHP)PorMnOAc
were synthesized based on the porphyrin demethylation
method of James [47] starting from 5,10,15,20-tetrakis-
(2,3-dimethoxyphenyl)porphyrinatomanganese(III)ace-
tate (T(2,3-OMeP)PorMnOAc) and 5,10,15,20-tetrakis(4-
methoxyphenyl)porphyrinatomanganese(III) acetate
(T(4-OMeP)PorMnOAc). The corresponding free-base
porphyrins were prepared by the Lindsey method [48] and
metallated by Mn(OAc)2 ·4H2O according to the Adler
method [49]. In the end, purification of aforementioned
porphyrins with some modification in James’ method
brought about demethylation and conversion into
porphyrins bearing hydroxyl groups. The green mixture
containing BBr3 in CH2Cl2 was exposed to heat up to
50°C so that the extra acid not utilized in the reaction and
the solvent were evaporated [25].
Note that the idea of heterogenization of
T(2,3-OHP)PorMn by the usage of such interactions with
…
2-methylimidazolate linkers of ZIF-8 (Por–O HMe–Im,
Fig. 1) improved reusability in addition to the increase
in conversions. To our surprise, T(4-OHP)PorMn@
ZIF-8 showed an impressive increase in conversions
compared to the T(4-OHP)PorMn/acetate suffering
from lack of such hydrogen bonding in homogeneous
media [25]. Thus, T(2,3-OHP)PorMn@ZIF-8 could
be considered as a reusable catalyst with the ability
to convert cyclooctene to the epoxide (entries 6, 5).
The kinetic profile of T(4-OHP)PorMn@ZIF-8 and
T(2,3-OHP)PorMn@ZIF-8 in the cyclooctene epoxi-
dation is represented in Fig. 11. An enhancement in the
reaction rate is revealed for cyclooctene epoxidation in
T(2,3-OHP)PorMn@ZIF-8 and T(4-OHP)PorMn@
ZIF-8 were prepared through the template-directed
strategy method. 2-Methylimidazolate (0.33 mmol) and
Zn (NO3)2 (0.28 mmol) were mixed with manganese
porphyrin (0.02 mmol) in DMF (10 ml) and transferred
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M BAGHERZADEH & E MESBAHI
Fig. 8. Conversion percentage of cyclooctene vs. reaction
time in the presence of T(2,3-OHP)PorMn@ZIF-8 at room
temperature, in the mixture of CH2Cl2/methanol (5:1)
Instrumentation
Diverse instruments were employed to characterize the
prepared catalyst. X-ray diffraction (XRD) patterns were
obtained by XPERT-PRO diffractometer system (MPD
PANalytical Company) using a Cu Ka radiation source
(the scan range (2q) was from 2° to 80°). Nitrogen
adsorption−desorption measurements were performed
on a Tri Star II surface area and porosity analyzer
(Micromeritics). FT-IR spectra were gained through an
ABB Bomem MB-100 FT-IR spectrophotometer utilizing
KBr disks at room temperature. Raman spectra were
recorded on a Rigaku micro Raman spectrometer with
a HeNe red laser (1064 nm) and 490 mW laser power
(exposure time: 3000 ms). The amount of manganese
was determined by a Shimadzu (AA680) atomic
absorption/flame emission spectrometer utilizing air and
acetylene. Field emission scanning electron micrography
(FE-SEM) was obtained using a TESCAN MIRA II field-
emission scanning electron microscope. Transmission
electron microscopy (TEM) was performed on a JEM-
2100F (JEOL) microscope operating at 200 kV. Gas
chromatographic (GC) analyses were carried out on
an Agilent Technologies 6890 N, 19019 J-413 HP-5,
capillary 60 m × 250 µm × 1 µm.
Fig. 7. Optimization of T(2,3-OHP)PorMn@ZIF-8 (green)
and n-Bu4NHSO5 (purple) in cyclooctene epoxidation at room
temperature, in the mixture of CH2Cl2/methanol (5:1)
into Teflon-lined Parr pressure vessels. The Teflon liners
were placed in autoclaves, and heated to 408 K for
36 h [37].
n-Bu4NHSO5, which is the corresponding soluble salt
of oxone (the commercial triple potassium salt insoluble
in organic solvents), was prepared by a previous method
[50].
All other chemical substances were purchased from
the Merck, Fluka and Alfa Aesar companies.
Fig. 9. Profile of cyclooctene conversion % obtained in each run
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HETEROGENIZATION OF MANGANESE PORPHYRIN VIA HYDROGEN BOND
7
Epoxidation reactions
Epoxidation of olefins was investigated in the
presence of n-Bu4NHSO5 and MnPor@ZIF-8. The
reactions were all carried out in the optimized medium
(CH2Cl2 and methanol, 5:1) at room temperature. The
following molar ratios were used: substrate (0.2 mmol),
n-octane (0.12 mmol) as the internal standard, catalyst
(3 × 10-4 mmol) and n-Bu4NHSO5 (0.4 mmol). The
reactions proceeded in a closed system with stirring
for 18 h. The reaction solution (0.2 µL) was injected
into the GC system after separation of the catalyst by
centrifugation. For reusability studies, the catalyst was
washed thoroughly with ethanol and then prepared for
Fig. 10. PXRD pattern of T(2,3-OHP)PorMn@ZIF-8 after
usage in 7 runs
usage in the next run.
Table 3. Epoxidation of cyclooctene in distinct catalytic systems
Entry
1
Catalyst
Conditions
Heterogeneous
Conversion %
87
T(2,3-OHP)PorMn@ZIF-8
CH2Cl2/methanol
n-Bu4NHSO5
room temperaturea, 18 h
2
3
4
5
6
7
8
9
T(2,3-OHP)PorMnOAc
T(2,3-OHP)PorMnOAc
T(2,3-OHP)PorMnOAc
T(4-OHP)PorMnOAc
T(4-OHP)PorMn@ZIF-8
Mn-TAPP@ZIF-8
ZIF-8
Homogeneous CH2Cl2/methanol
2-methylimidazole
n-Bu4NHSO5
67
26
75
38
89
62
39
10
room temperature, 10 h (24 h) [27]
Homogeneous CH2Cl2/methanol
imidazole
n-Bu4NHSO5
room temperature, 10 h [27]
Homogeneous CH2Cl2/methanol
Tetra-n-butylammonium acetate
n-Bu4NHSO5
room temperature, 10 h [25]
Homogeneous CH2CL2/methanol
Tetra-n-butylammonium acetate
n-Bu4NHSO5
room temperature, 10 h [25]
Heterogeneous
CH2Cl2/methanol
n-Bu4NHSO5
room temperature, 18 h
Heterogeneous
Acetonitrile
TBHP
80ºC, 24 h [37]
Heterogeneous
CH2Cl2/methanol
n-Bu4NHSO5
room temperature, 18 h
no catalyst
CH2Cl2/methanol
n-Bu4NHSO5
room temperature, 18 h
No significant difference was observed in results in the presence of imidazole.
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M BAGHERZADEH & E MESBAHI
Fig. 11. Kinetic profile of T (2,3-OHP)PorMn@ZIF-8 (red) and T (4-OHP)PorMn@ZIF-8 (gray) in cyclooctene epoxidation
reaction
6. Bertini I, Gray HB, Lippard SJ and Valentine JS.
CONCLUSIONS
Bioinorganic Chemistry, University Science Books:
T(2,3-OHP)PorMn@ZIF-8 and T(4-OHP)PorMn@
Mill Valley, CA, 1994.
ZIF-8 were synthesized via the hydrogen bond direct
approach. The cooperating interplay of a kind of non-
classical weak hydrogen bonding has allowed our
catalytic system to possess the advantage of heterogeneous
catalysts adjoined to analogue homogeneous ones.
This is supported by fairly good reusability and also
enhanced catalytic efficiency of the catalyst presented.
T(2,3-OHP)PorMn@ZIF-8 was consecutively reused five
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Sharif University of Technology is appreciated.
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Figures S1–S3 and Table S1 are given in the
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