Design and Synthesis of Supramolecular Polymer Network Equipped with Pd-porphyrin: An Efficient and Recoverable Heterogeneous Catalyst for C–C Coupling Reactions

Article abstract of DOI:10.1007/s10562-020-03344-3

Abstract: The present study aimed to explain a modern and attractive protocol for synthesizing hypercross-linked conjugated supramolecular polymer network contains palladium(II) porphyrin based on calix[4]resorcinarene as an efficient heterogeneous cataly

Full text of DOI:10.1007/s10562-020-03344-3

Catalysis Letters
https://doi.org/10.1007/s10562-020-03344-3
Design and Synthesis of Supramolecular Polymer Network Equipped
with Pd‑porphyrin: An Eꢀcient and Recoverable Heterogeneous
Catalyst for C–C Coupling Reactions
Sheida Hamid · Arash Mouradzadegun1
1
Received: 16 June 2020 / Accepted: 26 July 2020
©
Springer Science+Business Media, LLC, part of Springer Nature 2020
Abstract
The present study aimed to explain a modern and attractive protocol for synthesizing hypercross-linked conjugated supra-
molecular polymer network contains palladium(II) porphyrin based on calix[4]resorcinarene as an eꢀcient heterogeneous
catalyst. Thus, characterizations were conducted by using spectroscopic methods including powder X-ray diꢁraction, energy
dispersive spectroscopy, scanning electron microscopy, FT-IR, and UV–Vis spectroscopy. In addition, catalytic activity of
Pd-porphyrin@polymer was evaluated for C–C coupling reactions. The catalyst demonstrated an excellent activity, which
is highly potential for forming new bond under mild conditions.
Graphic Abstract
The synthesis of a novel, green and recoverable heterogeneous catalyst by grafting Pd-porphyrin on the surface of polymeric
calix[4]resorcinarene for the synthesis of C–C coupling reactions.
O
O
O
O
X
OH
B
Pd-porphyrin
OH
R
R
O
O
O
O
X= I, Br, Cl
Keywords Supramolecular polymer network · Pd-porphyrin · Suzuki reaction
1
Introduction
Electronic supplementary material The online version of this
article (https://doi.org/10.1007/s10562-020-03344-3) contains
supplementary material, which is available to authorized users.
Recently, supramolecular polymers, as a combination of
the advantages of supramolecular chemistry and polymeric
materials, have attracted a lot of attention [1]. Supramolecu-
lar polymers display broad application foregrounds such as
stimuli-responsiveness, self-healing, recycling, and degra-
dability due to their robust and adjustable nature [2, 3]. In
*
Arash Mouradzadegun
arash_m@scu.ac.ir
1
Department of Chemistry, Faculty of Science, Shahid
Chamran University of Ahvaz, Ahvaz, Iran
Vol.:(0
1
123456789)
3

S. Hamid, A. Mouradzadegun
addition, network polymerization of the monomer produces
supramolecular polymer networks which can prepare the
materials with macroscopic robustness [4]. Porphyrins and
metalloporphyrins are widely found in nature and play a
signiꢂcant role in the basic mechanisms of vital organisms
2 Experimental Procedure
2.1 General
All the commercial chemicals which were available pur-
chased from Aldrich and Merck companies and utilized
without more puriꢂcation. The products were determined
by their physical constant compared with valid samples.
Then, the reactions were monitored and the purity the
products was determined by using TLC on silica gel Pol-
yGram SILG/UV 254 plates. In addition, the IR spectra
were recorded on a Perkin Elmer Spectrum Version 10.4.4.
FT-IR spectrophotometer was done by implementing KBr
pellets for the related samples and catalyst with the range
[
5–9]. These systems have been evaluated due to the cata-
lytic use of organic synthesis, electrical light applications,
and therapeutic properties. Although they are considered
as homogeneous catalysts and their role can be highlighted
by selectivity [10, 11], the major problem is related to
their recovery. In this regard, immobilized porphyrin was
suggested to solve this problem. Liu et al. reported metal-
loporphyrin supported on SBA-15 as an eꢀcient catalyst
for solvent-free Heck reaction [12]. In another study, metal-
loporphyrin on Dowex 50WX8 and Amberlite IR-120 were
reported as recyclable catalysts in the reactions related to
C–C coupling [13, 14]. However, the above-mentioned pro-
tocols had some drawbacks such as high temperature, low
active sites on supporting catalyst, and very long reaction
times. Nowadays, supramolecular polymers are considered
as the applicable support materials for synthesizing hetero-
geneous catalysts [15, 16]. Thus, expanding the functionali-
zation of this polymer is considered as an important issue for
many scholars related to heterogeneous catalysis. Based on
the results of the former studies on c-methylcalix[4]resor-
cinarene which can be performed by suggesting some diꢁer-
ent moieties at the upper and lower rim [17], the synergetic
impact of functional groups and three-dimensional cavity
of scaꢁolding leads to the creation of novel and attractive
properties. In this regard, synthesis of functionalized supra-
molecular structures through the functional groups which
are anchored covalently onto c-methylcalix[4]resorcinarene
and its polymers have attracted a lot of attention [18–33]. On
the other hand, synthesis of biaryl structural unit can be con-
sidered as one of the most fascinating reactions since there
are a major number of developed materials encompassing
natural, as well as some other synthetic products encompass-
ing biaryl structural units which involved some attractive
biological and pharmaceutical features. The cross-coupling
reactions which are catalyzed by palladium have changed
the chemical industry which is responsible for synthesiz-
ing a vast number of supramolecular and natural products,
medicine, and agrochemicals [34]. This article explains the
synthesis of new functionalized polymeric calix[4]resorcin-
arene contains covalently anchored metalloporphyrin and its
eꢀciency is evaluated as a heterogeneous catalyst in C–C
coupling reactions using the one-pot reaction.
−
1
of 4000–400 cm . Further, a LEO 1455VP scanning elec-
tron microscope which operated at 1–30 kV was used for
conducting the SEM analyses. Thermal stability of the
functionalized catalyst was investigated by NETZSCH STA
409 PC/PG under a nitrogen atmosphere (rate of N2 z 1 L
h_1). Melting points were measured on a Thermo Scien-
tiꢂc IA9200 and were uncorrected. In the next procedure,
ultraviolet–visible (UV–vis) spectra were measured from a
Shimadzu UV-2600 UV–vis spectrophotometer. Further,
1
13
H and C NMR spectra were determined in CDCl on a
3
Bruker Advanced DPX 400 MHz spectrometer through uti-
lizing TMS as internal standard. Finally, the heterogene-
ous catalysts were determined by X-ray powder diꢁraction
(
XRD) through utilizing a STOE diꢁractometer with Cu-Ka
radiation (l=0.15418 nm) at 40 kV and 40 mA.
2.2 Synthetic Procedures
2
.2.1 Preparing Meso‑tetrakis[4‑(methoxycarbonyl)
phenyl]porphyrin(1)
Meso-tetrakis[4-(methoxycarbonyl)phenyl]porphyrin
was made through modifying A. D. Adler-f. R. Longo
method [35]. First, 2.33 mmol of freshly distilled pyrrole
and 2.33 mmol of p-methoxycarbonylbenzaldehyde were
added in 200 ml acetic acid in a typical reaction. Then, the
mixture was reꢃuxed for 4 h and cooled based on the room
temperature. The mixture was added to 100 ml methanol
in an ice bath after cooling. The purple crystals were ꢂl-
trated and washed through using methanol and hot distilled
water. In addition, column chromatography (Silica gel, ethyl
acetate/n-hexane=20:1 as an eluent) was used for purify-
ing crude product, which resulted in creating a desired
purple solid of meso-tetrakis[4-(methoxycarbonyl)phenyl]
porphyrin(H TMCPP) (39%).
2
1
3

Design and Synthesis of Supramolecular Polymer Network Equipped with Pd‑porphyrin: An Eꢀcient…
2
.2.2 Synthesis of Pd‑porphyrin(2)
δ=1.29–1.30 (d, 12H, CH ),4.43–4.49 (q, 4H, H-5), 6.15 (s,
3
13
4
H, H-1), 6.76 (s, 4H, H-4), 8.56 (s, 8H, OH) ppm; CNMR
PdCl (0.135 g) was added into a solution of meso-tetrakis[4-
(100 MHz, DMSO-d ): δ = 22.0 (CH ), 29.0 (C-5), 102.5
2
6
3
(
methoxycarbonyl)phenyl]porphyrin (H TMCPP) (0.3 g,) in
(C-3), 123.5 (C-1), 125.7 (C-2), 152.3 (C-4) ppm.
2
1
00 ml of DMF and reꢃuxed for 12 h. Then, Pd-TMCPP was
puriꢂed by recrystallizing frequently and precipitating from
2.2.4 Synthesizing the 3D‑Network Polymer Based
on Calix[4]resorcinarene(4)
DMF–H O solutions [36].
2
2
.2.3 Synthesizing Calix[4]resorcinarene(3)
The polymer was combined by adding 42 mmol of formal-
dehyde to 14 mmol of the produced calix[4]resorcinarene
which were mixed in 40 ml NaOH solution (10%) by con-
sidering the room temperature. The produced mixture was
heated to 90 °C and kept at 90 °C for 20 h. Then, the sur-
plus alkali was washed by using the gel produced from cold
water. In the next procedure, the gel was kept at 100 °C for
Calix[4]resorcinarene was made based on the already men-
tioned procedure [37]. This structure was conꢂrmed by the
1
H NMR (Fig. 1).
Yield 60%; white powder, m.p.: > 360 °C; IR (KBr):
−1 1
ν=3000–3500 (OH) cm ; H NMR (400 MHz, DMSO-d ):
6
Fig. 1 FT-IR spectra of a synthesized porphyrin. b Pd-porphyrin@polymer. c Polymer. d Pd-porphyrin complex and UV–Vis spectrums of Por-
phyrin (e) and Pd-porphyrin@polymer (f)
1
3

S. Hamid, A. Mouradzadegun
one hour, which changed into the acidic form through treat-
ing with the 0.1 M HCl solution. The produced solid was
dried at 100 °C for 10 h [38]. In Table 1, elemental analy-
sis was investigated for this polymer. The results shown no
nitrogen observed.
preparing the highly ordered Pd-porphyrin onto modiꢂed
network polymer. In addition, FTIR were recorded to deter-
mine the catalyst and confirm the covalent interactions
between porphyrin and polymer and palladium(II) complex
in Pd-porphyrin@polymer (Fig. 1a–d). As shown in Fig. 1a,
b, diꢁerent IR spectra were observed for porphyrin and Pd-
porphyrin complex. The results indicated the stretching and
bending frequencies of the N–H bond related to free base
2.2.5 Synthesis of Pd‑porphyrin@polymer(5)
−
1
According to the method reported by Fareghi-Alamdari [39],
ꢂrst, 5 g of polymer and 0.5 g Pd-porphyrin(2) were added in
porphyrin placed at~3310 and 960 cm . However, the pal-
ladium ion was entered into the porphyrin ring, the N–H
bond vibration frequency of porphyrin ligand was vanished,
and the functional groups of Pd–N bond were established
2
0 ml DMF after heating at 130 °C for 36 h. Then, the reac-
tion mixture was cooled and ꢂltered. In the next procedure,
it was exhaustively washed by using DMF and deionized
water. Finally, the prepared catalyst was dried and stored
under vacuum (Scheme 1).
−
1
at ~ 1000 cm , which resulted in forming Pd-porphyrin
complex [40]. Additionally, the bands as 1722 and
−1
1604 cm were determined for carbonyl related to ester and
C=N, respectively. In addition, based on a broad band at
−
1
2
.3 General Method for the Synthesis of Suzuki C–C
3200–3600 cm , all of the phenolic hydroxyl groups of
polymer 4 were not performed completely due to steric hin-
drance, compared to the IR spectrum of polymer 4 in the
ESI†). Therefore, the quantitative FTIR data demonstrated
grafting the Pd-porphyrin onto the polymer surface the suc-
cessfully. Along with FT-IR spectrum, other techniques were
implemented for conꢂrming the catalyst better (UV–VIS,
SEM, XRD, EDS and TGA). UV–Vis spectroscopy was
used to evaluate the Pd-porphyrin@polymer. As represented
in Fig. 1e, f, the absorptions peaks at 425, 525, 560, 600, and
Coupling
In an ordinary experiment, bromobenzene (0.5 mmol),
phenylboronic acid (0.75 mmol), catalyst (20 mg), K CO
2
3
(
1.5 mmol) and H O:DMF (1:1, 3 ml) were added to a
2
1
0 ml balloon and heated at 80 °C. Then, they were reacted
for the necessary time. The solid was extracted with ethyl
acetate, along with concentrating the liquid. In addition,
the product was created through preparing TLC. Further,
Pd-porphyrin@polymer was separated by centrifugation in
order to recover the catalyst, and accordingly washed with
ethanol, along with water. Additionally, it was dried under
the decreased pressure. Finally, the catalyst was utilized by
fresh charge of solvent and reactant for a subsequent reaction
under the same conditions.
658 nm are relayed on H TMCPP, while the sample gives
2
new absorption peaks at 422, 535, and 580 nm after metala-
tion with the palladium cation (solvent: CHCl ). Morphol-
3
ogy and size of the catalyst were observed by using scanning
electron microscopy (SEM). As displayed in Fig. 2a, the
Pd-porphyrin is placed on the polymer. The energy disper-
sive spectroscopy (EDS) was analyzed to specify the Pd-
porphyrin@polymer, which conꢂrms the presence of nitro-
gen and palladium in the aforesaid catalyst (Fig. 2b). The
wide-angle X-ray diꢁraction was performed to follow the
crystalline structure and size of the supported Pd. As shown
in Fig. 2c, four prominent peaks at 2q values of about 40°,
3
Results and Discussion
As it was already mentioned, one of the most important chal-
lenges in modern chemistry is related to the search for more
eꢀcient catalytic systems which may integrate the advan-
tages of both homogeneous and heterogeneous catalysis.
Thus, Pd-porphyrin was immobilized onto a 3D-network
polymer based on calix[4]resorcinarene. First, the porphyrin
ligand was synthesized based on the results of the previous
studies [35]. Then, the porphyrin ligand was metalated uti-
o
46 68°, and 81° related to the features of crystalline Pd.
(111), (200), (220), and (311) veriꢂed a decrease in Pd ions
[41]. The thermal stability of Pd(II)-porphyrin-based poly-
mer network was examined by thermogravimetric analysis
(TGA). The initial slight weight loss occurs before 150 °C,
which can be attributed to the evaporation of hydrated water
or residual solvent. The second and third one are occurred
at 150–400 °C and they related to the decomposition of met-
alloporphyrin. Thus, TGA analysis demonstrates the high
thermal stability of catalyst. The later loss weight is attrib-
uted to decomposition of polymer network at ~ 450 °C
lizing PdCl and attached onto modiꢂed network polymer
2
through creating the covalent bonding between the carbox-
ylic acid group of Pd-porphyrin and the hydroxyl group
related to network polymer. Scheme 1 displays the route for
(
Fig. 3). Pd-porphyrin@polymer was utilized as an excellent
Table 1 Elemental analysis data
Entry
C (wt%) H (wt%)
4.97
catalyst for C–C coupling reactions after the catalyst was
conꢂrmed by implementing spectroscopic techniques (FT-
IR, UV–Vis, SEM, EDS, XRD, TGA). In addition, the
for polymer4
Polymer 45.74
1
3

Design and Synthesis of Supramolecular Polymer Network Equipped with Pd‑porphyrin: An Eꢀcient…
MeO
2
C
2
CO Me
2
CO Me
N
H
H
N
acetic acid
reflux, 4h
4
4
N
N
H
N
CHO
1
MeO
2
C
CO
2
Me
MeO
2
C
2
CO Me
MeO C
2
CO Me
2
N
N
Pd
N
H
PdCl
DMF, reflux
2
N
N
N
N
H
N
2
MeO
2
C
CO Me
MeO C
2
CO Me
2
2
HO
OH
H C
2
HO
OH
HO
OH
OH
HO
OH
HO
HO
OH
O
HCl
CH
CH
3
3
H
H
3
3
C
O
C H
CH
CH
3
H
H
3
3
C
H
2
4
NaOH
4
H
C
C
H
C
3
H
C
C
3
HO
OH
HO
OH
HO
OH
H
2
C
n
3
4
2
CO Me
2
MeO C
O
O
N
II
Pd
O
O
Polymer 4
N
N
DMF, 36h
O
N
O
O
O
CO
2
Me
2
MeO C
(
5)
2
CO Me
2
MeO C
N
II
Pd
N
N
=
N
2
CO Me
2
MeO C
Scheme 1 Schematic preparation of catalyst
1
3

S. Hamid, A. Mouradzadegun
Fig. 2 SEM images of catalyst (a), EDS spectrum of catalyst (b) and XRD pattern of catalyst (c)
1
3

Design and Synthesis of Supramolecular Polymer Network Equipped with Pd‑porphyrin: An Eꢀcient…
Fig. 3 TGA curves of Pd-por-
phyrin@polymer
reaction of bromobenzene and phenylboronic acid was
selected as a pattern system to obtain optimum conditions
for the purpose of evaluating the catalytic activity of Pd-
porphyrin onto a 3D-network polymer based on calix[4]
resorcinarene as heterogeneous catalyst for synthesizing
C–C coupling. The solid was extracted with ethyl acetate,
and the liquid was concentrated after running the reaction
(Table 2). The progress of the reaction was followed by
TLC. It is worth noting that the reaction stopped in the
absence of the catalyst. Further, the impacts of diꢁerent
parameters such as solvent, base, and time were evaluated to
obtain the highest conversion. Additionally, some experi-
ments were performed to discern the eꢁect of solvent and
base in this reaction. Based on the results in Table 2,
Table 2 Optimization of the reaction conditions
Br
OH
B
OH
Catalyst(20mg)
H O : DMF(1:1), K CO , 80 C
o
2
2
3
Entry
Base
Solvent
Catalyst (mg)
T (°C)
Yield (%)
1
2
3
4
5
6
7
8
K CO
H O
EtOH
DMF
20
20
20
20
20
20
20
20
80
80
100
80
80
80
80
70
75
78
85
95
75
77
2
3
3
3
3
3
3
2
K CO
2
K CO
2
K CO
H O:EtOH (2:1)
2
2
K CO
H O:DMF (2:1)
2
2
K CO
H O:DMF (1:1)
2
2
NaOH
H O:DMF (1:1)
80
80
2
Na CO
H O:DMF (1:1)
2
3
2
Reaction conditions: phenylboronic acid (0.75 mmol), bromobenzene (0.5 mmol), catalyst (20 mg), base (1.5 mmol), solvent (3 ml), 80 °C
1
3

S. Hamid, A. Mouradzadegun
H O:DMF as solvent and K CO as base had the highest
Pd-porphyrin@Polymer is considered as a very beneꢂcial
pattern system for catalyzing the reactions for C–C coupling.
However, the catalyst was removed by centrifugation after
5-min reaction and the reaction proceeded for 1 h without
forming the product in order to evaluate the leaching of Pd-
porphyrin from Pd-porphyrin@polymer in Suzuki coupling
of phenylboronic acid and bromobenzene. By considering
the above results, excellent heterogeneity is observed by Pd-
porphyrin@polymer. The recovery potency from the reac-
tion medium and activity is considered as one of the most
main speciꢂcations of the heterogeneous catalyst. Further,
the reusability of the Pd-porphyrin@polymer catalyst was
examined by recovering consecutively, along with reusing
the catalyst up to six times. As displayed in Fig. 4, the reac-
tion was repeatedly conducted under one constant set of
operating conditions. Thus, the recyclability of catalyst
results in creating an economical and potential process for
commercial applications. Also, after recycling reactions, the
structural and nature of the reused catalyst was investigated
by UV–Vis spectroscopy, FT-IR analysis (Fig. 5). As shown
in Fig. 5, no diꢁerence was observed with the former one.
Reaction conditions: phenylboronic acid (0.75 mmol), bro-
mobenzene (0.5 mmol), catalyst (20 mg), base (1.5 mmol),
solvent (3 ml), 80 °C
2
2
3
conversion. Finally, the amount of Pd-porphyrin@polymer
as heterogeneous catalyst was evaluated to synthesize C–C
coupling. As displayed in Table 3, the best result was
achieved when the reaction was performed in the presence
of 20 mg of Pd-porphyrin@polymer. By considering the
conditions of the optimized reaction, the substrate scope of
the Suzuki coupling reaction was speciꢂed by implementing
phenylboronic acid with various aromatic halides in the
presence of 20 mg of Pd-porphyrin@polymer as the pre-
ferred quantity of catalyst. Based on the results in Table 4,
the catalytic activity of Pd-porphyrin@polymer relied on the
halide in the order ArCl<ArBr<ArI (entries 1–3, 4, 5 and
6
, 7). Further, diꢁerent aryl halides with electron-withdraw-
ing and electron-donating groups resulted in producing
excellent yields at normal time of the reaction (Table 4).
Based on the literatures and experimental results [39], the
mechanism of generation of free Pd(0) and continued it’s
application in catalytic cycle was represented in Scheme 2.
Way A or way B could be happened. After releasing of free
Pd(0), the ꢂrst step is oxidative addition of Pd(0) to the aro-
matic halides to form the organopalladium specie (I). The
reaction with KOH that it generated from aqueous K CO ,
2
3
gives intermediate (II) which via transmetalation with the
boronate complex (III) forms the organopalladium specie
The catalytic eꢀciency of the Pd-porphyrin@Polymer as
heterogeneous catalyst was compared with that of a number
of previously reported catalysts in Suzuki reaction (Table 5).
It is clearly displayed that the presented methodology in
this paper is superior to the most of the previously reported
methods in terms of catalyst amount, reaction time or prod-
uct yield.
(
IV). The reductive elimination of the biaryl product (ꢂnal
product) restores original free Pd(0) which completed cata-
lytic cycle and to beginning next catalytic cycle or go back
to the hole of porphyrin. Detecting a catalyst which remains
consistent even under the harsh conditions is essential. The
Pd-porphyrin@Polymer is considered as a thermal and
chemical stable complex, complete coordinative saturation
of the central atom, as well as a precedence for the Pd(II)
oxidation state. Pd-porphyrin leads to the very limited
release of Pd when heated under coupling reaction
conditions since it involves a very rigid structure and
extraordinarily high complex stability. Additionally,
4 Conclusion
The present study introduce a novel and simple method
for synthesizing Pd-macrocyclic complex supported on
the surface of network polymer. First, meso-tetrakis[4-
(
methoxycarbonyl)phenyl]porphyrin was produced based on
Table 3 Optimization of the amount of the Pd-porphyrin@polymer
Adler’s method. Then, meso-tetrakis[4-(methoxycarbonyl)
phenyl]porphyrin immobilized on 3D- network polymer
based on calix[4]resorcinarene and the product was char-
acterized successfully by FT-IR, SEM, XRD and EDS. In
addition, the catalytic activity of functionalized polymer was
evaluated in the reaction related to carbon–carbon coupling.
Finally, clean reaction proꢂles, short reaction times, easy
procedure, high activity, good recyclability, and no leach-
ing were considered as some of the advantages of using this
heterogeneous catalyst.
Entry
Catalyst (mg)
Time (min)
Yield%
1
2
3
4
5
–
5
10
20
30
80
60
15
15
15
–
70
85
95
95
Reaction conditions: phenylboronic acid (0.75 mmol), bromobenzene
0.5 mmol), base (1.5 mmol), solvent (3 ml), 80 °C
(
1
3

Design and Synthesis of Supramolecular Polymer Network Equipped with Pd‑porphyrin: An Eꢀcient…
Table 4 Synthesis of cross-
coupling reactions catalyzed
by polymer supported
Pd-porphyrin
Entry
1
Aryl halide
Product
Time(min)
10
Yield%
93
M.P
I
66-68
Br
Cl
I
2
3
4
15
95
88
95
66-68
66-68
47-49
140
10
Me
Me
Br
Me
5
6
15
10
93
89
47-49
86-88
Me
I
OMe
OMe
Br
OMe
7
15
15
90
88
86-88
OMe
Br
OH
8
155-158
OH
Br
CHO
9
105
110
86
90
55-57
CHO
Br
NO
2
1
0
103-106
NO
2
1
3

S. Hamid, A. Mouradzadegun
Table 4 (continued)
Reaction conditions: phenylboronic acid (0.75 mmol), bromobenzene (0.5 mmol), catalyst (20 mg), base
(
1.5 mmol), solvent (3 ml), 80 °C
Scheme 2 The plausible
mechanism for Suzuki reaction
in the presence of Pd-porphy-
rin@Polymer
O
O
O
O
N
N
Pd
N
N
O
O
O
O
Pd-porphyrin@polymer
A
X
X
X
Pd
reduction
dissociation
Solv
free PdII
free Pd0
dissociation
reduction
B
Ar
x
Ar
Ph
free Pd0
L
L
PdII Ph
Ar
PdII
X
Catalytic of
Pd-porphyrin@polymer
Ar
L
(
I)
L
(IV)
KOH + KHCO3
KX
H O + K CO
2 2 3
-
+
L
B(OH) K
4
Ar
PdII OH
L
PhB(OH) + KOH
PhB(OH) -
2
4
(
II)
(
III)
1
3

Design and Synthesis of Supramolecular Polymer Network Equipped with Pd‑porphyrin: An Eꢀcient…
Fig. 4 Recyclability of catalyst
Fig. 5 FT-IR spectra of a fresh catalyst; b recycled catalyst and UV–Vis spectrums of Fresh catalyst (c)
1
3

S. Hamid, A. Mouradzadegun
Table 5 Comparison of catalytic activity of Pd-porphyrin@polymer with other heterogeneous catalysts for the C–C coupling
Entry
Catalyst
Reaction conditions
Yield (%)
References
1
1
3
4
5
6
d/KAPs (DCM‐TPP) (20 mg)
K PO ·3H O, H O, 100 °C
98
89
92
99
97
96
[42]
[43]
[39]
[44]
[45]
This work
3
4
2
2
GO-NHC-Pd(II) (0.25 mol% Pd)
Pd(II)-TMCPP-GO (0.7 mol% Pd)
Pd-Schiꢁ base@MWCNT (0.1 mol% Pd)
Pd/Fe O /r-GO (0.36 mol%)
K CO , EtOH:H O, reꢃux, 18 h
2
3
2
K CO , DMF:H O, 70 °C, 40 min
2
3
2
K CO , DMF:H O, 60 °C, 3 h
2
3
2
K CO , H O, 80 °C, 25 min
3
4
2
3
2
Pd-porphyrin@polymer (15 mg)
K CO , H O:DMF, 80 °C, 10 min
2
3
2
Funding Funding was provided by Shahid Chamran University of
23. Ruderisch A, Iwanek W, Pfeiꢁer J, Fischer G, Albert K, Schurig
V (2005) J Chromatogr 1095:40–49
Ahvaz (Grant No. SCU.SC98.357).
2
2
2
4. Jain A, Gupta V, Singh L, Srivastava P, Raisoni J (2005) Talanta
6
5:716–721
5. Barrett ES, Dale TJ, Rebek J (2007) J Am Chem Soc
29:3818–3819
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