Design and synthesis of nanoporous perylene bis-imide linked metalloporphyrin frameworks and their catalytic activity

Article abstract of DOI:10.1007/s12039-015-0994-8

Two nanoporous perylene bis-imide linked metalloporphyrin framework catalysts have been synthesized via condensation of 5,10,15,20-tetrakis-(4 ′ -aminophenyl) iron(III) porphyrin chloride or 5,10, 15,20-tetrakis-(4 ′ -aminophenyl) manganese(III) porphyrin chloride with perylene-3,4,9,10-tetracarboxylic dianhydride. Both the materials were crystalline in nature and were characterized by electron microscopy techniques, solid-state ¹H- ¹³C CP/MS NMR, powder X-ray diffraction (PXRD), and magnetic susceptibility measurements. The nitrogen gas physisorption study has indicated that both materials are porous in nature and have BET surface area with 653 m²/g and 974 m²/g with uniform pore size of 2.8 nm. These materials were found to act as very good heterogeneous catalysts for selective oxidation of alkanes and alkenes with tert-butyl hydroperoxide and were not degraded even after multiple uses up to 10 cycles.

Full text of DOI:10.1007/s12039-015-0994-8

c
J. Chem. Sci. ꢀ Indian Academy of Sciences.
DOI 10.1007/s12039-015-0994-8
Design and synthesis of nanoporous perylene bis-imide linked
metalloporphyrin frameworks and their catalytic activity
MANOJ KUMAR SINGH and DEBKUMAR BANDYOPADHYAY∗
Department of Chemistry, Indian Institute of Technology Delhi, HauzKhas, New Delhi 110 016, India
e-mail: dkbp@chemistry.iitd.ac.in
MS received 25 August 2015; revised 29 September 2015; accepted 19 October 2015
Abstract. Two nanoporous perylene bis-imide linked metalloporphyrin framework catalysts have been
synthesized via condensation of 5,10,15,20-tetrakis-(4ꢁ-aminophenyl) iron(III) porphyrin chloride or 5,10,
15,20-tetrakis-(4ꢁ-aminophenyl) manganese(III) porphyrin chloride with perylene-3,4,9,10-tetracarboxylic
dianhydride. Both the materials were crystalline in nature and were characterized by electron microscopy
1
techniques, solid-state H-13C CP/MS NMR, powder X-ray diffraction (PXRD), and magnetic susceptibility
measurements. The nitrogen gas physisorption study has indicated that both materials are porous in nature and
have BET surface area with 653 m2/g and 974 m2/g with uniform pore size of 2.8 nm. These materials were
found to act as very good heterogeneous catalysts for selective oxidation of alkanes and alkenes with tert-butyl
hydroperoxide and were not degraded even after multiple uses up to 10 cycles.
Keywords. Covalent-organic frameworks (COFs); metalloporphyrins; heterogeneous catalysis; oxidation.
1. Introduction
Thus, at present the focus has been on covalently
linked metalloporphyrin frameworks materials.15–17
These covalently linked metalloporphyrin materials are
amorphous in nature, their catalytic ability and stability
have been improved a lot. In these studies, it has been
observed that when these covalent organic frameworks
(COFs) materials are prepared through reversible organ-
ic reaction pathways the materials become crystalline
in nature. It is believed that reversibility in covalent
bond formation during synthesis is required for mak-
ing crystalline COFs. This probably suggests why the
materials prepared by the irreversible organic reac-
tions (Suzuki coupling) were always amorphous in
nature.18,19 Thus, by taking help of such reversible
organic reactions, such as, boronic acid trimerization,
Schiff base reaction, hydrazine and squaraine linkage
and nitrile trimerization several crystalline COFs are
reported.20–24 The COF materials are in general porous
and are found to be very useful in gas storage/separa-
tion,25–27 CO2 capture,28–30 sensors,31,32 and cataly-
sis.33–35 The amorphous materials of large pore sizes are
indeed found to be more efficient catalysts.36,37 In our
endeavour also we have noted that the materials pre-
pared by irreversible route (Suzuki coupling) became
amorphous, though their catalytic oxidizing ability was
good.38 Herein we report our successful result of mak-
ing two crystalline materials where an imide bond is
formed between the metalloporphyrin moiety and pery-
lene bis anhydride and the material is nanoporous with
Iron(III) and manganese(III) porphyrin catalysed oxi-
dation of alkanes and alkenes remained an interesting
area of research for several decades till date.1–5 In the
early stages, it has been noted that tetrakis-phenyl por-
phyrin iron(III) and manganese(III) complexes were
good to mimic the reactions of Cytochrome P450
enzymes but in both cases the catalysts were damaged
by the now known μ-oxo-bridged product formation.6
In order to resolve the issue, electronegatively substi-
tuted porphyrins were prepared and their iron(III) and
manganese(III) complexes were found to be relatively
more efficient but the problem of the catalyst degrada-
tion was not really resolved.7 In the course of our own
studies also, the degradation of such electronegatively
substituted iron(III) porphyrin catalysts were noted in
similar studies.8–10 There was good success on catalyst
stabilization in attaching the functionalized porphyrins
over silica or polymeric catalysts but the surface area
of the active catalyst was difficult to measure accu-
rately.11,12 In recent studies, the focus has been to make
inorganic coordination polymers (CP) or metal-organic
frameworks (MOFs) with these metalloporphyrins.13,14
In CP materials the activity of the catalysts were im-
proved but the solvolytic decay of the materials to the
monomers caused finally the destruction of the catalyst.
∗For correspondence

Manoj Kumar Singh and Debkumar Bandyopadhyay
larger pore size. The solid state properties and the cat- methanol (50 mL). The solid residue was filtered by
alytic oxidation of these two materials with t-BuOOH G-4 and was washed with THF (5 mL), methanol (15
are also discussed.
mL) and acetone (10 mL). Finally the solid was washed
by soxlet extractor using THF, methanol and acetone
(100 mL each), respectively for 24 h, and then dried in
vacuum to give polymeric material (∼150 mg) as a pur-
ple crystalline solid (in 62% isolated yield). Elemental
analysis (%) Calcd. For {C92H40ClMnN10O8}n (Theo-
retical formula for an infinite 2D polymer) C 73.44, H
2.68, N 9.31, Found by combustion: C 71.43, H 2.82,
N 9.24. Mn Content by ICP-AAS: 4.07 wt%; Found by
EDX analysis (wt%): Mn 3.93. FT IR (ν, cm−1): 3119,
1770, 1699, 1660, 1589, 1502, 1404, 1351, 1300, 1234,
1124, 1020 (δMn–N), 860, 803 and 732. UV-Vis (λ,
nm): 376, 477, 535 and 580.
2. Experimental
2.1 Catalyst Preparation
Details of synthesis and characterization of free base
porphyrin and metallated porphyrin are given in the
Supporting Information. The two nanoporous pery-
lene bis-imide linked metalloporphyrin frameworks
were synthesized by the following methods:
2.1a Synthesis of perylenebis-imide linked iron(III)
porphyrin chloride: Perylene bis-imide linked iron(III)
porphyrin chloride (1) was synthesized by refluxing
5,10,15,20-tetrakis-(4ꢁ-aminophenyl) iron(III) porphy-
rin chloride (120 mg, 0.155 mmol) and perylene-3,4,9,
10-tetracarboxylic dianhydride (122 mg, 0.320 mmol)
in m-cresol (25 mL) under argon. Isoquinolene (2 mL)
was then added to the refluxing mixture after 15 min.
The refluxing was continued for 24 h, and then the
reaction mixture was brought to room temperature and
was poured into methanol (50 mL). The solid residue
was filtered by G-4 and was washed with THF (5
mL), methanol (15 mL) and acetone (10 mL). Finally
the solid was washed by soxlet extractor using THF,
methanol and acetone (100 mL each) respectively for
24 h, and then dried in vacuum to give polymeric
material (∼130 mg) as a reddish crystalline solid (in
54% isolated yield). Elemental analysis (%) Calcd. For
{C92H40ClFeN10O8}n (Theoretical formula for an infi-
nite 2D polymer) C 73.44, H 2.68, N 9.31, Found by
combustion: C 70.47, H 2.81, N 9.06. Fe Content by
ICP-AAS: 3.53 wt%; Found by EDX analysis (wt%):
Fe 3.66. FT IR (ν; cm−1): 3118, 1769, 1698, 1588,
1504, 1401, 1350, 1299, 1237, 1124, 1020 (δFe–N),
858, 803and 736. UV-Vis (λ, nm): 375, 451, 533 and
578.
2.2 Catalyst characterization
1
The H NMR spectra were recorded on a Bruker
spectrospin DPX-300 NMR spectrometer at 300.13
and 75.47 MHz, respectively, using CDCl3 as a sol-
vent at room temperature. Mass spectra (HRMS) were
recorded in the electro-spray ionization (ESI) mode
(10 eV, 180◦C source temperature and sodium formate
as calibrant) on a Bruker micrOTOF-QII, taking the
samples in acetonitrile/methanol. Solid-state H–13C
1
CP/MAS NMR measurements were performed on
a Bruker model 500 MHz NMR spectrometer at a
MAS rate of 15 kHz and a CP contact time of 5 ms.
Magnetic susceptibility measurements were carried
out with Quantum Design model MPMS XL7 SQUID
magnetometer. UV-Vis absorption spectra were mea-
sured in CH2Cl2 in a quartz cell of 1-cm path length
on an Agilent Technologies 8453 model spectrometer
and the diffuse reflectance spectra (Kubleka-Munk
spectrum) were recorded on a Perkin Elmer UV-Vis
Lambda Bio 20 model spectrometer. Infrared spectra
were recorded on an Agilent Technologies Cary 660
model Fourier transform infrared spectrophotometer.
Elemental analysis of C, H, and N were carried out on
a Perkin Elmer instrument series II CHNS/O Analyser
2400 model. Fe and Mn contents were measured by
2.1b Synthesis of perylenebis-imide linked man- ICP-AAS method on a Perkin Elmer instruments Ana-
ganese(III)porphyrin chloride: Perylene bis-imide lyst 100 model plasma spectrometer. Scanning electron
linked manganese(III) porphyrin chloride (2) was sim- microscopy and energy dispersive X-ray spectroscopy
ilarly synthesized by refluxing 5,10,15,20-tetrakis-(4ꢁ- were performed on a ZEISS EVO Series model EVO50
aminophenyl) manganese(III) porphyrin chloride (120 microscope operating at an accelerating voltage of 5.0
mg, 0.155 mmol) and perylene-3,4,9,10-tetracarboxylic kV. Powder X-ray data were collected on a Bruker
dianhydride (122 mg, 0.320 mmol) in m-cresol (25 D8 Advance diffractometer using Ni-filtered CuKα
mL) under argon. Isoquinolene (2 mL) was then added radiation. Data were collected with a step size of
to the refluxing mixture after 15 min. The refluxing 0.02◦ and a count time of 2 s per step over the range
was continued for 24 h, and then the reaction mixture 5◦ < 2θ < 70◦. Nitrogen sorption isotherms were mea-
was brought to room temperature and was poured into sured with Quantachrome NovaWin-Data Acquisition

Nanoporous metalloporphyrin frameworks
analyzer and reduction for NOVA instruments, materials were however characterized by various spec-
Quantachrome Instruments version 10.01 at 77 K. troscopic techniques such as elemental analysis, elec-
Before measurement, the samples were degassed in tron microscopy and Powder X-ray diffraction (PXRD)
vacuum at 200◦C for more than 12 h. The Brunauer- measurements.
Emmett-Teller (BET) method was utilized to calculate
Infrared (IR) spectroscopy provided evidence for the
the specific surface areas and the nonlocal density presence of imide linkage in 1, showing the character-
function theory was applied for the estimation of pore istic vibration bands at 1695 cm−1 and 1353 cm−1 for
size, pore volume and pore distribution.
imide carbonyl and C–N units, respectively (figure S1,
table S2 in Supplementary Information). After conden-
sation reaction, compound 1 did not exhibit the signal
of the anhydride carbonyl group. This observation indi-
cated that the anhydride units have been transformed
to imide. The Fe–N stretching frequency of metallopor-
phyrin was observed at 1020 cm−1. Elemental analysis
showed the content of C, H, and N to be 70.47, 2.81 and
9.06%, respectively (theoretical formula for an infinite
2D polymer {C92H40ClFeN10O8}n C 73.44%, H 2.68%,
N 9.31%). The amount of iron (3.53 wt%) and man-
ganese (4.07 wt%) in 1 and 2 were estimated by ICP-
AAS (Inductively coupled plasma atomic absorption
spectroscopy). Similar type of IR pattern was observed
for 2 (figure S1, table S3), showing that these two
materials are isomorphous in nature.
Perylene is a well-known electron acceptor moi-
ety which in combination with the metalloporphyrin
in COFs may affect the π–π∗ transitions of both
molecules. Therefore, their π electronic properties
are interesting to be elucidated. We conducted solid-
state electronic absorption spectroscopy to evaluate the
absorption bands of 1 and 2 (figures 1a and b).
2.3 Catalytic Experiments
The catalytic oxidations of various olefins were carried
out in 4-mL pyrex glass reactors equipped with
mechanical stirrer. In a typical experiment, 1 or 2 (5
mg), dichloromethane (2 mL), alkanes/alkenes (400
mM) and TBHP (10 mM) were charged in the reactor
and the resulting mixture was stirred under an atmo-
sphere of argon at 298 K. The solution was periodi-
cally analysed by GC-MS (Perkin Elmer Auto System
XL gas chromatography equipped with a Flame Ioniza-
tion Detector (FID). All the products were identified by
the comparison of GC retention times of the standard
samples. Selectivity and conversion were calculated
with respect to oxidant. For the recycling experiments,
after the first reaction was over (6-8 h) another batch of
TBHP (∼3 μL) was added to the same pot and the reac-
tion was continued for another 8 h and then monitored
by GC. The process was repeated similarly for 10 cycles
and the products were analysed each time as stated for
the first cycle.
Compound 1 displayed absorption band at 451 nm
attributed to the soret bands of iron(III) porphyrin unit.
The band at 533 nm appeared due to the imide bond
formation with the perylene moiety. There is a 24 nm
red shift of the soret band of 1 with respect to the cor-
responding (NH2)4TPPFeCl monomer (427 nm). The
compound 2 also exhibited the characteristic imidic
3. Results and Discussion
Considering the known structural features of the por-
phyrin and perylene, the most probable structure of
the proposed materials is shown in scheme 1. These
Scheme 1. The general strategy for the synthesis of imide-linked metalloporphyrin COFs

Manoj Kumar Singh and Debkumar Bandyopadhyay
Figure 1. Absorption spectra computed from the diffuse reflectance spectra (a) for compound 1 and (b) for compound 2.
(a)
(b)
Figure 2. SEM images at magnification (a) 10000X (scale 1 μm) and (b) 6000X (scale 2 μm).
1
Figure 3. Solid-state H-13C CP/MS NMR spectrum of perylene bis-imide
linked iron(III) porphyrin COF, recorded at a MAS rate of 15 kHz and a CP
contact time of 5 ms. Signals marked with * are side bands.
unit at 535 nm. These results indicated the presence of
The compounds 1 and 2 are stable and insoluble
extended π conjugation over the 2D sheet of the COFs. in common organic solvents. Magnetic susceptibility
Scanning electron microscopy (SEM, figure 2a and measurements at room temperature indicated that both
b) revealed that 1 has rough surface with length of sev- the materials are at high spin state due to the d5 and d4
eral tens of micrometres and width of ∼100 nm. The electronic configuration of Fe(III) and Mn(III) (figures S4
presence of iron and manganese in 1 and 2 were con- and S5 in SI), respectively. Owing to the high-spin
firmed by elemental analysis EDX (Energy dispersive paramagnetic effect, the solid-state 1H-13C CP/MS
X-ray, figures S2 and S3 in SI).
NMR spectrum of COFs gave only a weak and broad

Nanoporous metalloporphyrin frameworks
Figure 4. Nitrogen sorption isotherm (absorption (Red), desorption (Blue)) of (a)
Perylene bis-imide linked iron(III) porphyrin and (b) Perylene bis-imide linked
manganese(III) porphyrin, measured at 77 K.
signal. The compound 1 displayed two broad peaks at which indicated that the crystalline skeleton of these
136 and 128 ppm assignable to the perylene linkages two materials are similar. It also probably indicates that
and signals at 118 and 159 ppm owing to the porphyrin the facets of both the materials are similarly oriented
macrocycles (figure 3).
and thus these materials may be classified under 2D
In order to understand the nature of the materials COFs materials.
(crystalline or amorphous), XRD measurements were
In order to understand the 1D channel accessibil-
conducted (figures S6 and S7 in SI). The compound 1 ity and porosity of the COF materials, nitrogen sorp-
and 2 exhibited distinct diffraction peaks at 8.56, 12.28, tion isotherm measurements were conducted for these
24.76 and 28.18 degrees. Interestingly, the peak posi- two materials. Both displayed typical type-IV sorption
tions of both the materials were at the same position, isotherm curve (figure 4) which is the characteristic
of mesoporous materials. The calculated BET surface
areas were 653 and 974 m2/g; the Langmuir surface
areas were 1042 and 1489 m2/g for 1 and 2, respec-
tively. The total pore volumes were estimated to be
1.1 and 1.2 cm3 g−1 for 1 and 2, respectively. The
pore size distributions were evaluated by using the non-
local density functional theory (NL-DFT) method (fig-
ure S8). The polymer has one main peak centred at 2.8-
3.2 nm, which is close to the theoretical value (2.8 nm).
Scheme 2. Reaction scheme for oxidation of norbornene to
exo-2,3-epoxy norbornane.
Table 1. Oxidation of norboronene with t-BuOOH in CH2Cl2 at 25 2◦C.a
Exo-2,3-epoxynorbornane yield %b
Sl. No.
Time (h)
Oxidant
(NH2)4TPPFeCl
(NH2)4TPPMnCl
Catalyst 1
Catalyst 2
1
2
3
4
5
6
7
8
9
0.25
1
2
3
4
5
6
7
8
2
4
6
6
6
6
6
6
6
8
15
18
20
22
25
28
30
31
7
16
20
23
27
30
33
35
35
15
30
34
42
54
65
72
84
>99
17
35
49
61
76
88
>99
>99
>99
[a] norbornene (400 mmol), TBHP (10 mmol), catalyst (3.16 μmol), dichloromethane (2.0 mL) and dodecane (5 mL) sealed
as internal standard in a Teflon-lined screw capped vial and stirred at room temperature for 8 h. [b] Conversion [%] was
determined by GC. The yields are w.r.t. oxidant.

Manoj Kumar Singh and Debkumar Bandyopadhyay
These results indicated that these COFs materials may
be good hosts for suitable gaseous guest molecules or
other substrates of appropriate size.
Now on the basis of these results, we believe that
both these materials to be very good catalysts to mimic
the oxidation reaction of cytochrome P450. As a test
case we have chosen norbornene as the substrate and
t-BuOOH as the oxidant and the results are given below.
In a typical reaction norbornene was found to be selec-
tively oxidized to exo-norbornane oxide (scheme 2).
Norbornene was oxidized to exo-2,3-epoxynorbornane
in 6% yield in 8 h by t-BuOOH alone. The yield was
improved to 31% when monomeric catalyst (NH2)4
TPPFeCl was present in the medium. However, the yield
of epoxide was substantially increased to >99% under
identical reaction conditions when catalyst 1 or 2 was
used (table 1).
Figure 5. Plot of yield % of exo-2,3-epoxy nornoronane
vs time (h) for Catalyst 1, Catalyst 2, (NH4)2TPPFe(III)Cl,
(NH4)2TPPMn(III)Cl and only oxidant t-BuOOH in
dichloromethane.
The plot of the product yield vs. time for non-
catalytic (only oxidant), with monomeric catalyst, with
catalyst 1 and catalyst 2 are given in figure 5. The plot
Table 2. Perylene bis-imide linked Fe(III) porphyrin COF catalysed epoxidation/oxidation of alkenes/alkanes.a
Sl. No.
Substrate
Product
Conversionb (%)
Selectivityc (%)
1
2
3
4
5
6
7
Norbornene
Cyclooctene
Cyclohexene
Styrene
Cyclohexane
Cyclooctane
1-Hexene
Norbornane epoxide
Octane epoxide
Cyclohexen-1-one
99
99
99
99
99
70
65
60
75
35
Styrene epoxide
99[d]
28[e]
58[f]
92[g]
Cyclohexane-1-one
Cyclooctane-1-one
Hexene epoxide
[a] alkenes/alkane (400 mmol), TBHP (10 mmol), catalyst (3.16 μmol), dichloromethane (2.0 mL) and dodecane (5 mL)
sealed as internal standard in a Teflon-lined screw capped vial and stirred at room temperature for 8 h. [b] Conversion [%] and
[c] selectivity [%] were determined by GC. The yields are w.r.t. oxidants. [d] The by-products were benzaldehyde and ben-
zenacetaldehyde. [e] Cyclohexane-1-one (17%) and cyclohexane-1-ol (11%). [f] Cyclooctane-1-one (44%) and cyclooctane-
1-ol (14%). [g] Hexane epoxide (32%), 1-hexene-3-one (27%), 2-hexenal (20%) and by-products were 1-hexene-3-ol (8%)
and 2-hexene-1-ol (5%). The yields are w.r.t. oxidant.
Table 3. Perylene bis-imide linked Mn(III) porphyrin COF catalysed epoxidation/oxidation of alkenes/alkanes.a
Sl. No.
Substrate
Product
Conversionb (%)
Selectivityc (%)
1
2
3
4
5
6
7
Norbornene
Cyclooctene
Cyclohexene
Styrene
Cyclohexane
Cyclooctane
1-Hexene
Norbornane epoxide
Octane epoxide
Cyclohexen-1-one
99
99
99
99
99
72
67
55
52
39
Styrene epoxide
99[d]
32[e]
65[f]
99[g]
Cyclohexane-1-one
Cyclooctane-1-one
Hexene epoxide
[a] Alkenes/alkanes (400 mmol), TBHP (10 mmol), catalyst (3.70 μmol), dichloromethane (2.0 mL) and dodecane (5 mL)
sealed as internal standard in a Teflon-lined screw capped vial and stirred at room temperature for 6 h. [b] Conversion
[%] and [c] selectivity [%] were determined by GC. [d] The by-products were benzaldehyde and benzenacetaldehyde. [e]
Cyclohexane-1-one (18%) and cyclohexane-1-ol (14%). [f] Cyclooctane-1-one (34%) and cyclooctane-1-ol (31%). [g] Hex-
ane epoxide (39%), 1-hexene-3-one (29%), 2-hexenal (20%) and by-products were 1-hexene-3-ol (8%) and 2-hexene-1-ol
(3%). The yields are w.r.t. oxidant.

Nanoporous metalloporphyrin frameworks
clearly indicates that the new catalyst is a reasonably
efficient one.
It has been noted that catalyst 2 completes the conver-
sion in 6 h whereas the corresponding catalyst 1 needs
The oxidizing ability of this new catalyst for other 8 h. The greater surface area of the manganese catalyst
substrates are shown in table 2. We see that cataly- (974 m2/g) compared to iron catalyst (653 m2/g) could
sis with catalyst 2 are similar with the same substrates be the reason for this.
(table 3).
Now, we have also investigated the recyclability of
the catalyst. Thus, after the completion of the first cycle,
4. Conclusions
the new batch (aliquot) of oxidant was added to the
In summary, we have developed the synthesis of two
same pot and the product yield was measured. This
nanoporous perylene based crystalline materials with
process was continued for 10 sets. In all cases, we
improved catalytic activity with respect to CMPs, which
observed that the results of the first cycle was repro-
supports the current thoughts on new COFs. The cat-
duced, confirming that there was almost no catalyst
alyst materials have very selective oxidizing power
damage in these 10 cycles. We have not measured any
for alkanes/alkenes and very good recyclability. Pery-
further cycles, believing that the catalyst is still sur-
lene moiety is a very good electron acceptor, so such
viving as it was in the first cycle. As indicated in
materials may have good application in optoelectronic
table S4, the catalyst1 was not destroyed in ten cycles,
devices. With this advancement, we believe that this
work will initiate the exploration of various catalytic
we have measured. The monomeric catalyst, on the
other hand, was degraded substantially after the first
systems based on COFs via the structural engineering
cycle by the formation of known catalytically inac-
for further improvement of both pores and skeletons.
tive μ-oxo-metalloporphyrin dimmers.39 The catalyst
1 can be easily separated from the reaction mixture via
Supplementary Information
centrifugation and can be re-used repeatedly.
The comparison of the results of the activity of the
monomeric iron and manganese porphyrins versus their
perylene linked new catalysts are interesting. The cata-
lyst 1 showed the catalytic activity with >99% conver-
sion of norbornene to exo-norbornane epoxide, while
the monomeric iron(III) porphyrin has lower catalytic
activity with conversion up to only 31% (table 1). Sim-
ilarly, monomeric manganese(III) porphyrin has lower
catalytic activity with 35% conversion while catalyst 2
gave 99% conversion (table 1). We believe that the oxi-
dation is proceeding through any of the probable reac-
tive intermediates shown eq. 1 and 2.9 The network
structure of 1 and 2 prevents them to form μ-oxo-dimer
(eq. 3). This indeed is the reason for the stability and
greater efficiency of catalysts 1 and 2.
Synthetic methods and characterization of monomeric
free base porphyrins and metalloporphyrins, measure-
ments of FT-IR, EDX, magnetic susceptibility PXRD,
pore size and distribution by NL-DFT, Recyclability
table for the polymeric materials are available at www.
ias.ac.in/chemsci.
Acknowledgements
We thank the Department of Science and Technology
(DST, India) (Project no. SR/S1/IC-48/2010) for fund-
ing and UGC for the fellowship to MKS. We also thank
Prof. R. Chatterjee of the Dept. of Physics, IIT Delhi
for SQUID measurements.
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