A porphyrin-based microporous network polymer that acts as an efficient catalyst for cyclooctene and cyclohexane oxidation under mild conditions

Article abstract of DOI:10.1016/j.catcom.2017.05.024

The highly efficient dibenzodioxin-forming reaction between the (pentafluorophenyl)porphyrin manganese(III) (MnP) and hexahydroxytriptycene (HHT) provide a new microporous network polymer (P1), which demonstrated a large surface area (1080 m² g

Full text of DOI:10.1016/j.catcom.2017.05.024

Accepted Manuscript
A porphyrin-based microporous network polymer that acts as an
efficient catalyst for cyclooctene and cyclohexane oxidation under
mild conditions
Ariana R. Antonangelo, C. Grazia Bezzu, Sabeeha S. Mughal,
Talita Malewschik, Neil B. McKeown, Shirley Nakagaki
PII:
DOI:
Reference:
S1566-7367(17)30218-2
doi: 10.1016/j.catcom.2017.05.024
CATCOM 5059
To appear in:
Catalysis Communications
Received date:
Revised date:
Accepted date:
1 February 2017
19 May 2017
22 May 2017
Please cite this article as: Ariana R. Antonangelo, C. Grazia Bezzu, Sabeeha S. Mughal,
Talita Malewschik, Neil B. McKeown, Shirley Nakagaki , A porphyrin-based microporous
network polymer that acts as an efficient catalyst for cyclooctene and cyclohexane
oxidation under mild conditions. The address for the corresponding author was captured
as affiliation for all authors. Please check if appropriate. Catcom(2017), doi: 10.1016/
j.catcom.2017.05.024
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ACCEPTED MANUSCRIPT
A porphyrin-based microporous network polymer that acts as an efficient catalyst for
cyclooctene and cyclohexane oxidation under mild conditions
Ariana R. Antonangeloa, C. Grazia Bezzub, Sabeeha S. Mughalc, Talita Malewschika, Neil B.
McKeownb and Shirley Nakagakia*
aDepartamento de Química, Universidade Federal do Paraná (UFPR), Curitiba, Brazil, 81531-
990.
bEastChem School of Chemistry, The University of Edinburgh, Edinburgh, Scotland, UK, EH9
3FJ.
cSchool of Chemistry, Cardiff University, Cardiff, Wales, UK, CF10 3AT.
*Corresponding author: e-mail address: shirleyn@ufpr.br

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KEYWORDS:Porphyrins; Polymers of Intrinsic Microporosity (PIMs); Porous; Heterogeneous
catalysis; Oxidation.
ABSTRACT: The
highly
efficient
dibenzodioxin-forming reaction between the
(pentafluorophenyl)porphyrin manganese(III) (MnP) and hexahydroxytriptycene (HHT) provide a
new microporous network polymer (P1), which demonstrated a large surface area (1080 m2 g-1)
and proved to be an efficient solid for heterogeneous catalysis for cyclooctene and cyclohexane
oxidation under mild conditions and with high capacity of recovery and reuse in many catalytic
cycles.

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1. Introduction
Oxidation reactions of organic compounds, especially alkenes and alkanes, play an
important role in the chemical industry, both in organic synthesis and in the production of bulk
and fine chemicals. The development of efficient and selective methods that employ mild
conditions and avoid toxic metal reagents is the major challenge in this area [1]. In this regard,
significant progress has been achieved within the area of homogeneous molecular catalysis,
especially using porphyrins. Synthetic metalloporphyrins, particularly those containing iron and
manganese cations, have been widely studied as catalysts in many oxidation processes and as
models for cytochrome P450 enzymes [2-6].
The synthetic development of novel catalysts is based upon a growing understanding of
the mechanism of action and has led to improve catalytic results in homogeneous catalysis
using porphyrins [,4-6]. Despite the efforts in the synthesis of more robust porphyrins, the
catalytic process employing such compounds in homogeneous medium still have some
drawbacks, such as difficulty or impossibility of the catalyst recovery, formation of µ-oxo
dimmers or oxidative degradation of the porphyrin ring (even in a small extent) and
contamination of the products formed at the end of the reaction [2-6]. In this regard, the search
for more stable, efficient and selective catalysts, combined with the desire for recovery and
reuse has also led to a growing interest in using porphyrin-based materials for heterogeneous
catalysis [7-14].Hence, metalloporphyrins have been immobilized on many different supports [7-
9], and also incorporated within porous materials, such as Metal Organic Frameworks (MOFs)
[9,10] and porous network polymers [11-14]. These materials function as solid catalyst for
heterogeneous process since the presence of porous enhances access of the substrate to the
active metal catalytic centers of the solid catalyst. Moreover, the high density of active sites in
these materials enhances catalytic performance. Although a number of research groups have
explored the use of metalloporphyrins as building blocks for the design of porous polymers,
catalytic studies using these materials are still rare [9-14].
Polymers of Intrinsic Microporosity (PIMs) are highly rigid amorphous materials, easily
prepared using dibenzodioxin forming reactions, for which microporosity is generated from their
rigid and contorted structures [15]. Insoluble networks PIMs with high surface area (up to 1000
m2g-1) and potential use in heterogeneous catalysis have been prepared previously using planar
functional units such as phthalocyanines and porphyrins [12,13,16]. These materials are
assembled via covalent bond formation rather than by formation of usually weaker coordination

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or hydrogen bonds and display high chemical and thermal stability which encourage the
synthesis of new network PIMs and their assessment for heterogeneous oxidation catalysis.
For the present study, the dibenzodioxin-forming reaction [16] between
(pentafluorophenyl)porphyrin
manganese(III)
(MnP)
and
9,10-diethyl-2,3,6,7,12,13-
hexahydroxytriptycene (HHT) was used to prepare a new network PIM porphyrin-based (P1)
(Scheme 1). The new polymer exhibits remarkable activity and stability on catalytic oxidation of
cyclooctene and cyclohexane under heterogeneous conditions with high capacity of recovery.
Scheme 1. Schematic representation of P1 preparation.
2. Experimental
2.1 General information
The free-base porphyrin (H2P) [17], the metalloporphyrin (MnP) [18], the compounds 9,10-
diethyl-2,3,6,7,12,13-hexahydroxytriptycene
(HHT) [19] and the 2,3-dihydroxy-9,10-
dimethyltriptycene (DHT) [20] were synthesized as reported previously (see Supporting
Information SI). Iodosylbezene (PhIO) was prepared according to a literature procedure [21],
assayed by iodometric titrations and stored in a freezer.
2.2 Synthesis and characterization of the network PIM porphyrin P1
The polymer P1 was prepared by reacting the metalloporphyrin MnP (monomer A1) and
9,10-diethyl-2,3,6,7,12,13-hexahydroxytriptycene HHT (monomer B1) (Scheme 1) according to

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the reported procedure [16]. The metalloporphyrin MnP (0.17 g, 0.156 mmol), 9,10-diethyl-
2,3,6,7,12,13-hexahydroxytriptycene HHT (0.1 g, 0.208 mmol) and anhydrous K2CO3 (0.32 g,
2.34 mmol) were stirred in anhydrous NMP (5 mL) at 170 °C under nitrogen atmosphere. After
about 24 h the system was allowed to reach room temperature, methanol (30 mL) was added
and the mixture was stirred for 30 min, from which a black solid (P1) was filtered off. The solid
was purified by Soxhlet extraction and reflux in various solvents (in the order THF, CHCl3,
CHCl2, acetone and methanol). The solid was dried in vacuum oven for 6 h at 110 °C (yield
90%). Elemental analysis (%) for C78H32O10F12N4Mn: calcd C 63.82, H 2.20, N 3.82; found: C
55.40, H 1.80, N 4.20 ICP OES (Mn, %) calcd.: 3.74, found: 3.24. BET surface area =1080 m2
g-1. IR (cm-1):1651, 1455, 1419, 1334, 1300, 1254, 1157, 1064, 1006, 947, 797, 759, 705. UV-
VIS λmax(mineral oil, nm): 475, 376.TGA (nitrogen):~ 3.5% loss of mass < 200 °C. Initial weight
loss due to thermal degradation commences at ~400 ºC (Figure S17, SI). Note that the mass
loss < 200 °C is ascribed to the removal of adsorbed gas (O2, N2, CO2) and solvent or water
molecules, which we account for the lower than expected carbon content from elemental
analysis. Moreover, thermal degradation results in a loss of mass of only ~50% of original
weight up to 1000 °C, indicating that carbonization is occurring, which is consistent with the low
values for carbon obtained during elemental analysis.
2.3 Catalytic reactions
The efficiency of the network PIM porphyrin (P1) as catalyst for oxidation reactions was
tested using (Z)-cyclooctene (previously purified on neutral alumina column) and cyclohexane
as substrates using iodosylbenzene as oxygen donor. The reactions were performed in a 1.5
mL glass flask equipped with a magnetic stirrer, in a dark chamber. The solvent mixture
(acetonitrile/dichloromethane,ACN:DCM 1:1, v/v) and the substrates were purged with argon for
15 min. The catalyst P1 (0.001 g, 0.00059 mmol) and the oxidant iodosylbenzene (0.0013 g,
0.0059 mmol) (P1/PhIO at a molar ratio of 1:10) were added in the reaction flask and they were
also purged with argon for 15 min. Then, the mixture of solvents (ACN:DCM, 1:1) was added to
the reactions flasks, followed by addition of the substrates (P1/PhIO/substrate molar ratio of
1:10:1000). The molar ratio was based on the amount of metal of the polymer P1 measures by
ICP (heterogeneous catalysis) or based on the molecular mass of the metalloporphyrin MnP
(homogeneous catalysis). The oxidation reactions were performed under magnetic stirring, for 1
hour, at room temperature, in the absence of light. At the end of the reaction, the excess of
iodosylbenzene was eliminated by adding a solution of sodium sulfite in acetonitrile. The
catalyst P1 remained insoluble during the reaction, so the process was heterogeneous in all

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cases. At the end of the heterogeneous reaction, the reaction mixture was separated from the
insoluble catalysts by centrifugation and the supernatant was transferred to a volumetric flask (2
mL). The solid catalyst was washed three times with the mixture of solvents (ACN:DCM) to
extract any reaction products that might have adsorbed onto the solids catalysts. The washing
solutions were added to the previously separated reaction supernatant in a volumetric flask (2
mL). In case of the homogeneous catalysis (MnP), the reaction mixture was transferred directly
to a volumetric flask (2 mL) by the end of the reaction.
To study the recyclability of P1, the solid catalyst was recovered after each use by
centrifugation, washed with different solvents (water, acetonitrile, dichloromethane and
methanol) and dried at 100 °C on a vacuum oven for about 12h. The dried solid was then
reused in a new catalytic reaction in the same conditions as the ones described above.
The products were analyzed by gas chromatography using bromobenzene as internal
standard. Product yields were based on the quantity of PhIO added to each reaction.
3. Results and discussion
3.1 Synthesis and characterization of the network PIM porphyrin P1
Significant nitrogen (N2) adsorption at 77 K for P1 at low values of relative pressure (P/P0)
and the isotherm shape (Type I) [22] are both consistent with a predominantly microporous
structure (Fig. 1a). The isotherm permitted an apparent BET surface area of 1080 m2/g to be
calculated. The hysteresis observed for P1 extends down to low relative pressures and this
characteristic may be attributed to swelling of the polymer rather than to the presence of
mesopores [12,15,23].
The UV-VIS spectrum in mineral oil (Fig. 1b) of the metalloporphyrin MnP showed the
Soret band at 475 nm and the charge transfer band at 365 nm, both consistent with Mn(III)
porphyrins [24]. The same bands were observed in the spectrum of the polymer P1 which
suggest the presence of the Mn(III)porphyrin in its structure.
(a)
(b)

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380
360
340
320
300
280
260
240
220
200
180
475
365
Ads
Des
MnP
P1
475
0.0
0.2
0.4
0.6
0.8
1.0
300 350 400 450 500 550 600 650 700
0
Wavelength (nm)
p/p
Figure 1. (a) Nitrogen adsorption/desorption isotherm for P1 (BET surface area = 1080 m2 g-1),
(b) UV-VIS spectra of the MnP (monomer A1) and network PIM porphyrin P1 (both samples in
mineral oil).
Thermogravimetric analysis (TGA) (SI, Fig. S17) indicated that the polymer P1 has
excellent thermal stability with decomposition starting as high as 350 °C, which can be important
for some catalytic processes.
The synthesis of the polymer P1 involves an aromatic nucleophilic substitution (SNAr)
mechanism. As reported previously, the fluorine atoms in the para position of the porphyrin core
are readily substituted by nucleophiles [25,26]. This is followed by a second rapid intramolecular
substitution on the neighboring fluorine atoms when catechols are used as nucleophiles [16].
Therefore, in order to confirm the reaction between the monomers MnP and HHT (Scheme 1), a
model SNAr reaction using the free-base tetrakis(pentafluorophenyl)porphyrin (H2P) and four
molar equivalents of the 2,3-dihydroxy-9,10-dimethyltriptycene (DHT) was performed (Scheme
2), according to the reported procedure [16]. The novel triptycene-substituted porphyrin
1
(H2Porph1) was characterized by MALDI-MS and H and 19F NMR spectroscopy, all of which
confirmed its structure (see S I).

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Scheme 2. Schematic representation of the H2Porph1 preparation.
3.2 Catalytic reactions
(Z)-cyclooctene is a useful diagnostic substrate as it is easily oxidized in the presence of
metalloporphyrins as catalysts and (Z)-cycloocteneoxide is usually the sole product [27,28]. For
comparison, the performance of MnP as catalyst was also determined (Table 1)) as it had
shown previously high catalytic activity in homogeneous oxidation reactions [27]. This enhanced
performance of the porphyrin MnP can be attributed mainly to its greater stability under
oxidation conditions, resulting from the electron withdrawing nature of the pentafluorophenyl
substituents.
The polymer P1 showed excellent activity for the oxidation of (Z)-cyclooctene (80% yield)
(Table 1), similar to the activity of the MnP in homogeneous medium (86% yield) suggesting
that the catalytic centers of MnP in the P1 structure are readily accessible to both cyclooctene
and PhIO reactants. The control reaction using PhIO in the absence of any catalyst showed low
epoxide yield (7%), proving that catalytic activity is due to the presence of MnP or P1.
Table 1 Oxidation of (Z)-Cyclooctene using PhIO as
oxidant and the porphyrin PIM network P1 as solid
catalyst for heterogeneous process or the precursor
MnP as homogeneous one.

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Catalyst
(Z)-Cyclooctenea
Epoxide (%)b
86.1 ± 0.4
MnPc
P1
80.0 ± 3.0
PhIOd
7.20 ± 0.2
aReactions conditions: reaction time= 1 h, solvent
mixture of acetonitrile/dichlorometane (ACN:DCM,
1:1 v/v), room temperature (25 °C), Catalyst
b
(P1)/PhIO/substrate molar ratio= 1:10:1000. The
product yields were calculated based on the amount
of
iodosylbenzene
used
in
the
the
reactions.cHomogeneous
catalysis
with
metalloporphyrin MnP (monomer A1). dControl
reaction using only substrate + PhIO.
Cyclohexane is less reactive than cyclooctene and its oxidation can produce a mixture of
cyclohexanone (K) and cyclohexanol (A) (so-called K–A oil), which is of considerable
importance in the industrial production of nylon [1].
The catalytic oxidation using metalloporphyrins usually affords both cyclohexanone (K)
and cyclohexanol (A) (as major products [27,28]. Both MnP and P1 showed selectivity for the
alcohol in the cyclohexane oxidation (Table 2), which is also in agreement with homogeneous
catalysis using other metalloporphyrins [27-30]. The polymer P1 showed catalytic activity similar
to that achieved with the MnP in homogeneous medium (~50% yield) and a higher alcohol
selectivity (98% for P1 and 83% for MnP) as shown in Table 2. Although much effort has been
made in the development of catalysts for oxidation of cyclohexane [27,29-31], few catalysts with
efficient catalytic activity under mild conditions have been reported in heterogeneous catalysis
[9-11,28,32]. Furthermore, in some cases the catalyst showed selectivity for ketone rather than
alcohol [7,10,33]. Nevertheless, few studies have shown recyclability tests using cyclohexane
as substrate [10].
Table 2 Oxidation of cyclohexane using PhIO as oxidant and the
porphyrin PIM network P1 as heterogeneous catalyst or the
precursor porphyrin MnP as homogeneous catalysts.

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Catalyst
Cyclohexanea
Ketoneb (%)
Alcoholb (%)
Alcohol
Selectivity (%)
MnPc
P1
54.0 ± 3.0
53.1 ± 1.3
10.7 ± 0.5
1.0 ± 0.4
83.6
98.2
-
PhIOd
Not detected
Not detected
aSolvent mixture of acetonitrile/dichlorometane (ACN:DCM, 1:1 v/v),
room temperature (25 °C), Catalyst (P1)/PhIO/substrate molar ratio
= 1:10:1000.bThe products yields were calculated based on the
c
amount of iodosylbenzene used in the reactions. Homogeneous
d
catalysis with the metalloporphyrin MnP (monomer A1). Control
reaction using only substrate and PhIO.
The catalytic activity and the alcohol selectivity of P1 for cyclohexane oxidation is
impressive in comparison to some previously catalytic results using other materials in
heterogeneous medium [8,27,29-31]. In general, for cyclohexane oxidation, metalloporphyrins
show lower catalytic activity in heterogeneous medium than in solution (homogeneous catalysis)
[27-30]. These impressive results suggest the stability of the active sites within the P1 structure
and also the easy accessibility of the catalytic centers to the cyclohexane substrate in the
polymer structure.
In general, microporous materials usually show better catalytic activity for substrates of
smaller size [33-35].The excellent catalytic activity of polymer P1 after only one hour of reaction
and under mild conditions for both substrates investigated, suggests that they can readily
access the catalytic sites inside the porous structure of the material. Further investigations using
substrates of different steric bulk are being planned.
As mentioned before, one of the main advantages of heterogeneous catalysis in relation
to homogeneous one is the recyclability of the catalyst. Therefore, the polymer P1 was easily
recovered from the reaction medium and reused without loss of the catalytic activity during at

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least four catalytic cycles (Fig 2). Moreover, the catalyst P1 maintained the high alcohol
selectivity in all cycles studied.
We ascribe this remarkable retention of catalytic activity to the highly robust nature of the
polymer and its rigidity, which maintains site-isolation of the metal centres and stops self-
oxidation of the porphyrin ligands.
In addition, heterogeneous catalysis using P1 provides greater purity of the products
compared to homogeneous using MnP since they are separated by simple centrifugation and
washing of the solid catalyst.
Alcohol
53,1
Ketone
Alcohol Selectivity
100
90
80
70
60
50
40
30
20
10
0
55
53
52,1
2
2
2
1
1º Cycle
2º Cycle
3º Cycle
4º Cycle
Figure 2. Study of the recyclability of the catalyst solid P1 for cyclohexane oxidation reaction
under the same conditions mentioned in the Table 2.
4. Conclusions
To conclude, a microporous network polymer P1 was easily prepared by an efficient
dibenzodioxin-forming reaction from a simple manganese(III)porphyrin precursor (MnP) which
has recognized catalytic activity in homogenous oxidation catalysis. The polymer P1 proved to
be a highly active catalyst for (Z)-cyclooctene and cyclohexane oxidation, showing catalytic
activity comparable to the MnP precursor in solution (homogeneous catalysis). In addition, the
P1 polymer showed excellent catalytic activity in the oxidation of cyclohexane with high alcohol

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selectivity under mild conditions and was also easily recovered by centrifugation and reused
without loss of catalytic activity, maintaining a high alcohol selectivity in all cycles studied.
We expected that this work will contribute scientifically to research on porous porphyrinic
materials for heterogeneous catalysis under mild conditions, mainly for the oxidation of inert
substrates like cyclohexane, and thus leads to the development of some industrially useful
materials in the future.
Acknowledgment
The authors are gratefulto CAPES (Coordenação de Aperfeiçoamento de Pessoal de
Nível Superior), CNPq (Conselho Nacional de Desenvolvimento Científico e Tecnológico)-
Science without Borders, Fundação Araucaria, Universidade Federal do Paraná and The
University of Edinburgh, for financial support.
Appendix A. Supporting Information.
Supporting data to this article can be found online at
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Highlights
 Efficient dibenzodioxin-forming reaction with Mnporphyrin and hexahydroxytriptycene.
 A new microporous network polymer which large surface area (1080 m2 g-1).
 An efficient solid for heterogeneous catalysis of oxidation reactions.
 Solid catalyst with high capacity of recovery and reuse in many catalytic cycles.