In situ preparation and characterization of novel CuI-functionalized poly[(methyl methacrylate)-co-maleimide] as an efficient heterogeneous catalyst in the regioselective synthesis of 1,2,3-triazoles via click reaction: Experimental and computational chemistry

Article abstract of DOI:10.1002/aoc.4967

A CuI-functionalized poly[(methyl methacrylate)-co-maleimide] (CuI@[PMMA-co-MI]) nanocatalyst was prepared from in situ polymerization and functionalization of poly[(methyl methacrylate)-co-(maleic anhydride)] and well characterized using various techniques. From a computational viewpoint, we assessed two complexation models between copper nanoparticles and [PMMA-co-MI]. In this line, the metal–ligand interaction strength was also studied via density functional theory calculations and frontier molecular orbital analysis. Moreover, for presenting a quantitative description of the electronic features of immobilization of copper nanoparticles on polymeric support, the topological analysis of electron density and its Laplacian was performed through quantum theory of atoms in molecules. Finally, the catalytic activity of CuI@[PMMA-co-MI] as a heterogeneous nanocatalyst was successfully examined in the highly regioselective synthesis of 1,4-disubstituted 1,2,3-triazoles via click reaction.

Full text of DOI:10.1002/aoc.4967

Received: 15 January 2019
DOI: 10.1002/aoc.4967
Revised: 16 March 2019
Accepted: 1 April 2019
F U L L P A P E R
In situ preparation and characterization of novel CuI‐
functionalized poly[(methyl methacrylate)‐co‐maleimide]
as an efficient heterogeneous catalyst in the regioselective
synthesis of 1,2,3‐triazoles via click reaction: Experimental
and computational chemistry
Nargess Pourmohammad1 | Majid M. Heravi1
| Shervin Ahmadi2 | Tayebe Hosseinnejad1
1 Department of Chemistry, School of
A
CuI‐functionalized
poly[(methyl
methacrylate)‐co‐maleimide]
Science, Alzahra University, PO Box
1993891176, Vanak, Tehran, Iran
(CuI@[PMMA‐co‐MI]) nanocatalyst was prepared from in situ polymerization
and functionalization of poly[(methyl methacrylate)‐co‐(maleic anhydride)]
and well characterized using various techniques. From a computational view-
point, we assessed two complexation models between copper nanoparticles
and [PMMA‐co‐MI]. In this line, the metal–ligand interaction strength was
also studied via density functional theory calculations and frontier molecular
orbital analysis. Moreover, for presenting a quantitative description of the elec-
tronic features of immobilization of copper nanoparticles on polymeric sup-
port, the topological analysis of electron density and its Laplacian was
performed through quantum theory of atoms in molecules. Finally, the cata-
lytic activity of CuI@[PMMA‐co‐MI] as a heterogeneous nanocatalyst was suc-
cessfully examined in the highly regioselective synthesis of 1,4‐disubstituted
1,2,3‐triazoles via click reaction.
2 Department of Polymer Processing, Iran
Polymer and Petrochemical Institute,
Tehran, Iran
Correspondence
Majid, M. Heravi, Department of
Chemistry, School of Science, Alzahra
University, PO Box 1993891176, Vanak,
Tehran, Iran.
Email: mmh1331@yahoo.com
Shervin Ahmadi, Department of Polymer
Processing, Iran Polymer and
Petrochemical Institute, Tehran, Iran.
Email: sh.ahmadi@ippi.ac.ir
Funding information
Iran National Scientific foundation
(INSF); Alzahra University
KEYWORDS
click reaction, CuI@[PMMA‐co‐MI] nanocatalyst, density functional theory, organometallic catalyst,
polymer‐supported catalyst
1 | INTRODUCTION
In heterogeneous catalysis, the facile separation, recov-
ery and reusability of the catalysts are of great signifi-
Heterogeneous catalysis is of paramount importance in
many areas of the chemical industries as well as in acade-
mia. The separation of reaction products from catalysts is
a foremost problem existing in many homogeneously
catalysed organic transformations. Nowadays, the inher-
ent advantages of heterogeneous catalysis over homoge-
neous catalysis are well known and well established,[1,2]
thus attracting much attention from synthetic organic
chemists.
cance. Therefore, the immobilization of various metals
onto different supports, such as aluminium oxyhydroxide
fibres,[3] zeolites,[4] amine‐functionalized silica[5] and
amine‐functionalized polymers, is a common strategy
for the preparation of various effective heterogeneous
catalysts.[6]
Nano‐size distribution and functionalization of metals
allows better dispersion of particles, higher stability and
good recycling properties, promoting such systems to act
Appl Organometal Chem. 2019;e4967.
wileyonlinelibrary.com/journal/aoc
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https://doi.org/10.1002/aoc.4967

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POURMOHAMMAD ET AL.
as effective catalysts. Moreover, these supported catalysts
can be used under aqueous conditions in the same way as
their homogeneous counterparts to give desired products
in good to excellent yields and in short reaction
times.[3,7,8]
Applications of various forms of polymer‐supported
CuI as reusable and recoverable heterogeneous catalysts
for the reigoselective synthesis of 1,4‐disubstituted 1,2,3‐
triazoles from the reaction between alkynes and azides
have been reported in the last decade.[24,25] Interest in
metal nanoparticle‐based catalysis is strongly increasing
as a stable and competitive alternative to conventional
catalysis.[26–28]
Such nanoparticles possess large surface areas, and are
the best choice as support surface due to their maximized
surface area.[29,30] They are thus effective in various
organic heterogeneously catalysed reactions.[31]
The Huisegn 1,3‐dipolar azide/alkyne cycloaddition
reaction represents a valuable process with wide scope
and molecular diversity which was first implemented
and reported by German chemist Rolf Huisgen in 1961.
As a matter of fact, Huisegn 1,3‐dipolar cycloaddition is
refers to an uncatalysed reaction between an azide and
a terminal or internal alkyne, leading to 1,2,3‐triazoles.[32]
This reaction particularly attracted the attention of the
US chemist Barry K. Sharpless (2001 Nobel Laureate)
who referred to Cu(I)‐catalysed 1,3‐dipolar cycloaddition
as ‘the cream of the crop’ of ‘click chemistry’.[33] The
Cu(I)‐catalysed 1,3‐dipolar cycloaddition reaction of
organic azides and terminal alkynes gives 1,4‐
disubstituted 1,2,3‐triazoles regioselectively under mild
reaction conditions.[34,35]
The click reaction was initially introduced in 2001 by
Sharpless and co‐workers, then used for the Cu(I)‐
catalysed regioselective synthesis of 1,4‐disubstitued
1,2,3‐triazoles.[34] Click chemistry has been used in a vari-
ety of scientific areas[36] such as drug discovery,
bioconjugation and polymer and supermolecular chemis-
try.[37,38] In addition, the importance of the 1,2,3‐triazole
family with a wide range of applications and biological
activities is considerable.[39,40] In the last decade, click
reactions and regioselective synthesis of 1,2,3‐triazoles
using various modified heterogeneous and homogeneous
catalysts have attracted much attention.[41]
The reaction of di(2‐pyridyl)methylamine with SMA
for the synthesis of
a recoverable and effective
immobilized catalyst for cross‐coupling reactions was
reported by Na’jera and co‐workers in 2005.[9] Since then,
the use of various polymers as supports has received
growing attention, and thus a plethora of different hetero-
geneous catalysts have been developed by immobilization
of metals on polymeric supports.[10]
In comparison with previously reported methods,
SMA, which is prepared by reaction between polar co‐
monomer (maleic anhydride) and nonpolar monomer
(styrene), in the presence of peroxide during in situ reac-
tive mixing, has been used as a polymer support in pro-
ducing heterogeneous catalysts.[11,12] In SMA, maleic
anhydride promotes the polarity of polymer chains which
has a great effect on dispersion and distribution of
nanocatalysts in polar reaction media. Increasing the
polarity of the composition will improve dispersion and
distribution of catalyst leading to an increase in the sur-
face area between catalyst and media which shows a
great effect on the activity of the catalyst.
Poly[(methyl methacrylate)‐co‐(maleic anhydride)], or
[PMMA‐co‐MAH], is an amorphous engineering thermo-
plastic with excellent mechanical and optical properties
that has great potential for use in electronics, coatings,
adhesives, energy storage, shielding of electromagnetic
waves, sensors and antistatic materials.[13]
In recent years, in situ polymerization has attracted
special attention because of improved product morphol-
ogy and interface between matrix and nanoparticles as
well as providing appropriate distribution of nanoparti-
cles in a polymer matrix which results in a better reaction
mixing process.[14,15]
Nanoparticle agglomerations reduce the particle con-
tact area thus decreasing the formation of a network
structure.[16] To improve the stability of nanoparticle dis-
persions in organic media or polymer matrices, it is nec-
essary to improve the compatibility between matrix and
nanoparticles through reaction between nanoparticles
and polymer chains.
[PMMA‐co‐MAH] is a copolymer including active
anhydride groups that can be modified with various
nucleophilic reagents. This structure can provide an
attractive and useful polymer support for the design of
various interesting materials[17–22] and more importantly
can be used for the immobilization of a variety of metals
for the preparation of a wide range of easily separable and
reusable effective heterogeneous catalysts.[23]
Due to our interest in the synthesis, characterization
and computational investigations of heterogeneous catal-
ysis,[42–45] in the work reported here we initially prepared
[PMMA‐co‐MAH] via in situ bulk polymerization and
functionalization, using 4‐aminopyridine, to afford
poly[(methyl methacrylate)‐co‐maleimide], or [PMMA‐
co‐MI]. Then, copper nanoparticles were fully character-
ized. Copper iodide was immobilized on the polymer sur-
face of [PMMA‐co‐MI] to afford CuI@[PMMA‐co‐MI] as
a polymer‐supported Cu(I) nanoparticle catalyst. We also
focused on a quantitative description of the structural and
electronic features of interactions between copper nano-
particles and [PMMA‐co‐MI] via density functional the-
ory (DFT),[46] frontier molecular orbital (FMO)

POURMOHAMMAD ET AL.
3 of 17
theory[47] and quantum theory of atoms in molecules
(QTAIM)[48] approaches. Then the catalytic activity of
the well‐characterized Cu@[PMMA‐co‐MI] was success-
fully examined in one the classic organic transformations,
click reaction. This novel Cu(I) heterogeneous
nanocatalyst showed all the merits expected for an effec-
tive heterogeneous catalyst such as ease of separation and
recovery as well as effective reusability for several cycles
with no appreciable loss of activity.
In continuation of our studies on the catalysed regiose-
lective synthesis of 1,2,3‐triazoles via click reaction,[49,50]
here we report the in situ preparation of CuI@[PMMA‐
co‐MI] nanocomposite which was successfully employed
as an effective catalyst in the reaction of terminal alkynes,
α‐haloketones or alkyl halides and sodium azide in aque-
ous media at room temperature to afford 1,4‐disubstitued
1,2,3‐triazoles regioselectively, in short reaction times and
in high yields (Scheme 1).
liquid chromatography method in which the components
of a mixture are separated on the basis of size.
Fourier transform infrared (FT‐IR) spectra (obtained
with a Bruker Equinox 55) were used to characterize
the structure of the prepared samples. The thermal
behaviour of [PMMA‐co‐MAH] samples was assessed
using thermogravimetric analysis (TGA) with a Metler
NETZSCH instrument. Morphology of the samples was
investigated using scanning electron microscopy (SEM;
Vega IIXMU, Tescan, Czech Republic) and transmission
electron microscopy (TEM; Philips EM 208s) at an accel-
erating voltage of 100 kV.
Characterization
of
CuI@[PMMA‐co‐MI]
was
achieved using Brunauer–Emmett–Teller (BET) analysis
with a BELSORP Mini II apparatus, inductively coupled
plasma atomic emission spectroscopy (ICP‐AES), SEM
and energy‐dispersive X‐ray spectroscopy (EDX).
Progress of click reactions was monitored by Thin‐
Layer‐Chromatography (TLC) using aluminium‐backed
plates of silica gel 60 F254 and visualized by ultraviolet
light. All click reaction products were known and identi-
fied by comparison of their melting points measured with
Electrothermal 9100 and their FT‐IR with those of
authentic compounds, already reported in literature. For
2 | EXPERIMENTAL
2.1 | Materials and instrumentation
1
The catalyst was synthesized using the following
chemicals: methyl methacrylate, benzoyl peroxide, maleic
anhydride, triethylamine, 4‐aminopyridine, acetic anhy-
dride, sodium acetate, CuI, acetone, methanol,
dimethylformamide (DMF), etc. They were purchased
from Aldrich or Merck in high‐grade quality and used
without further purification.
more accurate identification, HNMR spectra of couple
of samples were also recorded with of a Bruker DRX‐
400 spectrometer at 400 and 100 MHz, respectively.
2.2 | Preparation of catalyst
To perform click reactions, α‐haloketones, alkyl
halides, sodium azide and terminal alkynes were used.
All chemicals were obtained from Sigma‐Aldrich and
were of analytical grade.
To characterize [PMMA‐co‐MAH], weight‐average
molecular weight (Mw) and polydispersity index (PDI) of
copolymer samples were measured using gel permeation
chromatography (GPC; model 1100, Agilent Co.). GPC,
also referred to as size exclusion chromatography, is a
2.2.1 | Preparation of polymer support:
synthesis of [PMMA‐co‐MAH]
The preparation of [PMMA‐co‐MAH] was conducted by
in situ bulk polymerization, according to the formulations
listed in Table 1. Initially, monomer (methyl methacry-
late) and co‐monomer (maleic anhydride) were reacted
in the presence of benzoyl peroxide as an initiator in ace-
tone as solvent under nitrogen atmosphere at 70°C for
SCHEME 1 Cu(I)‐catalysed reaction of
sodium azide, acetylenes and halides

4 of 17
POURMOHAMMAD ET AL.
TABLE 1 Molecular weight and molecular weight distribution values of [PMMA‐co‐MAH] samples obtained by GPC
Formulation according to part per hundred (phr) method
Mw
(g mol−1
Mn
(g mol−1
Sample
Monomer
Co‐monomer
Initiator
)
)
PDI
P1
P2
P3
P4
P5
90
90
90
90
90
10
10
10
10
10
0.1
0.3
0.5
1
2.72 × 104
2.73 × 104
2.74 × 104
2.77 × 104
2.79 × 104
1.36 × 104
1.39 × 104
1.64 × 104
1.38 × 104
1.43 × 104
2
1.96
1.67
2
1.5
1.95
1.5 h. Then, the reaction mixture was cooled to room
temperature, and the precipitate was filtered and washed
with hot acetone. The solid precipitate was dried over-
night in a vacuum oven at 60°C to afford the required
compound.
temperature and added gradually to a beaker containing
MeOH (50 ml) to give a white precipitate which was fil-
tered off to dryness and washed with MeOH to afford
the required compound.
2.2.3 | Immobilization of CuI nanoparti-
cles on [PMMA‐co‐MI]: synthesis of
CuI@[PMMA‐co‐MI]
2.2.2 | In situ functionalization of polymer
support: synthesis of [PMMA‐co‐MI]
In
a
100 ml three‐neck round‐bottom flask, 4‐
CuI (0.247 mg, 0.001 mmol) was dissolved in acetonitrile
(5 ml) under ultrasonic treatment to give a dark yellow
solution (the molar ratio of Cu to amine was 1.0:2.4).
DMF (20 ml) was then added at room temperature to
yield CuI nanoparticles.[24] Next, dry [PMMA‐co‐MI]
(1.000 g) was added to the mixture and refluxed for 5 h
under nitrogen atmosphere. After filtration, the obtained
solid CuI@[PMMA‐co‐MI] was washed with acetonitrile
and dried under vacuum at 60°C.
aminopyridine (1.54 g, 16 mmol) was treated with
[PMMA‐co‐MAH] (1.00 g) in dry DMF (15 ml) under
nitrogen atmosphere at 35°C for 3.5 h. Then, acetic anhy-
dride (0.6 ml, 6 mmol), sodium acetate (0.33 g, 4 mmol)
and triethylamine (0.3 ml, 2 mmol) were added into the
flask using a syringe (Scheme 2). The temperature was
raised to 75°C and stirring was continued for 3.5 h.[11]
Afterwards, the reaction mixture was cooled to room
Based on previous studies, by comparison of the size of
the immobilized copper particles in methods, test results
showed that the organometallic catalyst prepared in
DMF exhibited better immobilization and smaller size
of CuI nanoparticles.[11]
2.3 | Synthesis of 1‐benzyl‐4‐phenyl‐1H‐
1,2,3‐triazoles: general procedure
α‐Haloketone or alkyl halide (1 mmol), an appropriate
terminal alkyne (2a, 2b; 1 mmol) and sodium azide
(1.3 mmol) were reacted in the presence of
CuI@[PMMA‐co‐MI] (0.02 g) in water (10 ml). The prog-
ress of the reaction was monitored by TLC (ethyl
acetate–n‐hexane; 2:8). After completion of the reaction,
the heterogeneous catalyst was separated by simple filtra-
tion and washed with ethanol. Then, the recovered cata-
lyst was rinsed with acetone and dried under vacuum at
70°C for 5 h for further use. Afterwards, the filtrate was
evaporated and the solid residue was recrystallized from
EtOH–H2O (3:1 v/v) to afford the corresponding 1,2,3‐
triazoles (4a–k) with high purity (Scheme 1).
SCHEME 2 Procedure for synthesis of CuI@[PMMA‐co‐MI]

POURMOHAMMAD ET AL.
5 of 17
For further characterization of the [PMMA‐co‐MAH]
structure, the molecular weights of the samples were
determined using GPC. The results are presented in
Table 2 that show the rate of reaction conversion accord-
ing to weight loss by monomer extraction. Results
showed that by increasing the amount of peroxide in for-
mulations, the rate of reaction increases, but the cage
effect appears for high quantity of peroxide, increasing
the residual content.
The high concentration and good reactivity of the
cyclic anhydride groups of [PMMA‐co‐MAH] make this
polymer an ideal support for the synthesis of organic
compounds, as a coordinating agent. In our study, we
selected inexpensive commercially available 4‐
aminopyridine for the modification and in situ
functionalization of [PMMA‐co‐MAH] to obtain
[PMMA‐co‐MI] under the aforementioned conditions
(Scheme 2). To confirm the chemical structural of the
product, FT‐IR spectra were considered (Figure 2).
3 | RESULTS AND DISCUSSION
3.1 | Preparation and characterization of
catalyst
The practical procedure for the preparation of the
CuI@[PMMA‐co‐MI] catalyst includes three steps, which
are shown in Scheme 2. Initially, [PMMA‐co‐MAH] was
prepared via in situ bulk polymerization of methyl meta
acrylate in the presence of maleic anhydride as a co‐
monomer and benzoyl peroxide as initiator. To character-
ize the product in this step, FT‐IR and GPC techniques
were used. Comparing the obtained spectra, it was
observed that all the spectra show similar patterns and
accurate absorption, which confirmed the correct given
structure of the composition (Figure 1).
The weight‐average molecular weight (Mw) and
number‐average molecular weight (Mn) of the samples
were found to be close together. The PDI (Mw/Mn) was
calculated by increasing the amount of the initiator. Mw
and Mn of samples P1, P2, P3, P4 and P5 as a comparison
are presented in Table 1. These data can be verified by
concluding that the molecular weight of polymers pro-
duced by free radical polymerization is inversely propor-
tional to initiator concentration.[51]
TABLE 2 Conversion rate during reaction
Conversion (%)
Time
(min)
1
2
3
4
5
0
0
0
0
0
0
By increasing the amount of initiator, more free radi-
cals are generated.[52] Thus, Mw was increased,[53–55] rela-
tive to Mw of samples with same composition of the
initiator. It was observed that molecular weights of sam-
ples P1, P2, P3, P4 and P5 were increased. Among the five
samples, P5 containing maleic anhydride co‐monomer
with the least amount of initiator has the highest Mw
and sharpest PDI. Among all samples, P3 showed more
similarity in chains.
10
10.0
20.0
60.0
98.0
98.5
98.5
99.0
10
15
30
65
80
83
89
89
89
30
69
87
90
92
92
92
30
24
45
60
67
88
90
99
90
120
150
>150
99
91
99.5
99.5
92
92.0
FIGURE 1 FT‐IR spectra of [PMMA‐
co‐MAH] samples P1, P2, P3, P4 and P5

6 of 17
POURMOHAMMAD ET AL.
FIGURE 2 FT‐IR spectra of 4‐
aminopyridine (a), [PMMA] (b), [PMMA‐
co‐MAH] (c), [PMMA‐co‐MI] (d) and
CuI@[PMMA‐co‐MI] (e)
To evaluate the effectiveness of the [PMMA‐co‐MI] sup-
port, CuI nanoparticles were immobilized on the surface of
this polymer. CuI nanoparticles were prepared in situ and
then exposed to [PMMA‐co‐MI] in DMF under reflux and
nitrogen atmosphere conditions (the molar ratio of Cu to
amine was 1.0:2.4). To remove the residual CuI from the
product, we washed the final product with acetonitrile
which dissolves the excess CuI. This procedure suppressed
agglomeration of the nanoparticles and afforded the
polymer‐supported CuI nanoparticle catalyst (Scheme 2).
For full characterization, the FT‐IR spectra were com-
pared to those obtained from previous steps (Figure 2).
FIGURE 3 TGA curves of samples P1 to P5

POURMOHAMMAD ET AL.
7 of 17
FIGURE 4 1H NMR spectra of [PMMA‐
co‐MAH] and CuI@[PMMA‐co‐MI]
1
The results of TGA (Figure 3), H NMR (Figure 4), SEM,
interaction of copper ion with nitrogen atom of pyridine
(Figure 2).
EDX and ICP‐AES clearly showed that the CuI nanopar-
ticles were homogeneously immobilized on the [PMMA‐
co‐MI] surface.
Next, samples P1, P2, P3, P4 and P5 of [PMMA‐co‐MI]
were analysed, using TGA. The thermograms of the vari-
ous samples are depicted in Figure 3. It can be concluded
that the effect of changing the amount of peroxide in for-
mulations is insignificant since all samples showed simi-
lar thermal behaviour, undergoing reduction at 350°C,
one major at 450°C and two also at 600 and 618°C which
can be attributed to the decomposition of polymer. More-
over, the TGA results for Cu@[PMMA‐co‐MI] showed
that all of the samples which contain Cu in their struc-
tures have similar thermal behaviour with the residue
depending on the amount of Cu content (Table 3).
Moreover, the 1H NMR spectrum of [PMMA‐co‐MAH]
(Figure 4) in comparison with that of Cu@[PMMA‐co‐
MI] (Figure 4) showed a similar pattern.[24] The expected
proton signals of [PMMA‐co‐MAH] )a) and Cu@[PMMA‐
co‐MI] (b) were observed as follows: (a) 0.78 (t, 3H), 1.15
(d, 3H), 1.41 (s, 3H), 1.78 (q, 2H), 2.46 (m, 1H), 3.40 (d,
1H), 4.25 (s, 3H); (b) 0.90 (t, 3H), 1.31 (d, 3H), 1.51 (s,
The presence of MAH in the [PMMA‐co‐MAH] chain
was confirmed by FT‐IR analysis (Figure 2). The modifi-
cation of the MAH moiety in [PMMA‐co‐MAH] with 4‐
aminopyridine to afford [PMMA‐co‐MI] was confirmed
by FT‐IR spectroscopy (Figure 2). Figure 2 shows the
spectra of 4‐aminopyridine, [PMMA], [PMMA‐co‐MAH]
before imidization, the prepared [PMMA‐co‐MI] and the
desired catalyst. In the spectrum of PMMA, the carbonyl
stretching band of the ester can be observed at 1731 cm−1
.
The peaks at 1272–1147 cm−1 are attributed to C─CO,
O─C─C and C─C─C stretching vibrations, while the
peak at 2956 cm−1 can be assigned to (─O─CH3)
stretching and other sp3 carbons.
The peaks at 1780 cm−1(weak stretching vibration)
and 1853 cm−1 (strong stretching vibration) can be
assigned to the anhydride group of [PMMA‐co‐MAH].
After the reaction of [PMMA‐co‐MAH] with 4‐
aminopyridine, a new imide band at 1700–1785 cm−1
was observed in the FT‐IR spectrum of [PMMA‐co‐MI]
(Figure 2) confirming the full imidization of [PMMA‐
co‐MAH] characteristic for amino group of 4‐
aminopyridine without any residual [PMMA‐co‐MAH].
Moreover, the band at 3300–3500 cm−1 which is related
to 4‐aminopyridine is absent in the FT‐IR spectrum of
[PMMA‐co‐MI]. The FT‐IR spectrum of the final desired
CuI@[PMMA‐co‐MI] composite shows a slight change
in stretching vibration frequency of C═N and C─N
of pyridine ring which can be attributed to the
TABLE 3 TGA results of samples P1 to P5
T1p
(°C)
T1end
(°C)
T2p
(°C)
T2end
(°C)
Residual ash
at 800°C (%)
Sample
Cu@P1
Cu@P2
Cu@P3
Cu@P4
Cu@P5
352
352
352
352
352
449
449
449
449
449
600
600
600
600
600
618
618
618
618
618
4.75
5.42
6.93
3.89
1.28

8 of 17
POURMOHAMMAD ET AL.
3H), 1.80 (q, 2H), 2.31 (m, 1H), 2.74 (d, 1H), 3.44 (s, 3H)
as well as two doublets at 8.12–8.42 ppm which are
assigned to C─H protons of the pyridine group with no
N─H peaks observed. These spectroscopic results con-
firmed the in situ functionalization of all amino groups
that were converted into the corresponding amides in
the polymer side chains.
observed, confirming the conjugation of this functional-
ity. This clearly shows that the CuI nanoparticles were
immobilized homogeneously on the [PMMA‐co‐MI] sur-
face. EDX results showed the increasing amount and uni-
form distribution of Cu.
The SEM images were recorded in two steps. In the
first step, the samples were taken out of the reaction ves-
sel, washed with acetonitrile to remove the residual CuI
and dried in a vacuum oven at 50 C, and images of poly-
mer after washing residual CuI were obtained. Then
SEM
micrographs
of
surfaces
of
washed
CuI@[PMMA‐co‐MI] are shown in Figure 5. The uniform
distribution of Cu on polymer chains can vividly be
FIGURE 5 SEM micrographs (a) and EDX analysis (b, c) of CuI@[PMMA‐co‐MI] samples P1 to P5

POURMOHAMMAD ET AL.
9 of 17
images of samples were used along with EDX to deter-
mine the incorporation of Cu nanoparticles, and image
maps were obtained for displaying the distribution of
nanoparticles. In this way the presence of copper nano-
particles, their distribution and non‐agglomeration can
be confirmed.
Additionally, the EDX traces of CuI@[PMMA‐co‐MI]
are illustrated in Figure 5. The EDX spectrum of the cat-
alyst confirms the attachment of copper onto the surface
of the polymer matrix. The presence of I and Cu can be
indicative of incorporation of CuI in the structure of the
Cu nanoparticles and observation of C, N and O atoms
can be representative of general uniform distribution of
Cu in the [PMMA‐co‐MI] structure, proven by combina-
tion of SEM and EDX results.
To prove the nano‐sized distribution of the Cu nano-
particles, a sample containing the highest amount of cop-
per was formed into a thin sheet with a thickness of
1 mm by hot pressing at 220°C at a pressure of 25 MPa.
Then the sheet was broken after liquid nitrogen treat-
ment and the surface of the fracture was analysed by
SEM. The result showed that the copper particle size
was less than 60 nm, thus confirming the nanoscale dis-
tribution of Cu (Figure 6).
TEM images proved the existence of Cu in the matrix
with nanoscale dimensions and the formation of Cu
nanoparticles. Results revealed that the average size of
copper species is around 8 nm (Figure 7).
FIGURE 7 TEM image of CuI@[PMMA‐co‐MI]
samples for analysis were prepared as follows. The metal
complex of CuI@[PMMA‐co‐MI] was digested in a con-
centrated acidic solution of HNO3 and HCl (1:1). Then
the filtrate was subjected to ICP‐AES. The content of
CuI was measured to be about 6.93% (w/w) for the
selected sample. Comparison with other polymer molecu-
lar weights, the results showed that by increasing the
molecular weight of polymer chain after P3, the incorpo-
ration of copper ions on the polymer surface is decreased
significantly. The direct dependency of Cu content scaled
as 1/PDI (Figure 8).
To determine the copper content in CuI@[PMMA‐co‐
MI], CuI was measured using ICP‐AES analysis. Initially,
3.2 | Computational details
We comparatively assessed the coordination behaviour of
the immobilized copper nanoparticles on the [PMMA‐co‐
MI] support, using DFT calculations[46] and the
QTAIM[48,56] approach. In this line, in order to interpret
FIGURE 8 ICP‐AES analysis of CuI@[PMMA‐co‐MI] samples P1
FIGURE 6 SEM image of CuI@[PMMA‐co‐MI] fracture surface
to P5

10 of 17
POURMOHAMMAD ET AL.
computationally the effect of uniformity in distribution of
methyl methacrylate chains, two effective structural
models were designed for copper complexes denoted as
CuI/PMMA‐MI1 and CuI/PMMA‐MI2 complexes. In the
next step, we determined the optimized structure of
CuI/PMMA‐MI1 and CuI/PMMA‐MI2 via DFT calcula-
tions at the M08HX/6‐31G* level of theory. It is notewor-
thy that the M08HX functional is intended for main
group and transition metal thermochemistry, kinetics
and non‐covalent interactions including two functionals
with a high percentage of Hartree–Fock exchange
contribution.[57] All DFT computations were performed
using the GAMESS suite of programs.[58] Figure 9 shows
the optimized structures of CuI/PMMA‐MI1 and
CuI/PMMA‐MI2 complexes, calculated at the M08HX/6‐
31G* level of theory.
The bond order analysis of metal–ligand interaction
site demonstrated that Cu–N interaction in CuI/PMMA‐
MI2 complex is stronger than in CuI/PMMA‐MI1 com-
plex (0.350 and 0.318 for Cu–N bond order in
CuI/PMMA‐MI2 and CuI/PMMA‐MI1 complexes, respec-
tively). Furthermore, N–C bond order calculated values
FIGURE 9 Optimized structures obtained at M08HX/6‐31G* level of theory for CuI/PMMA‐MI1 and CuI/PMMA‐MI2 complexes
FIGURE 10 Complete molecular graphs of PMMA‐MI ligand and CuI/PMMA‐MI1 and CuI/PMMA‐MI2 complexes obtained by QTAIM
analysis of M08HX/6‐31G* electron density functions. Bond critical points: green circles; ring critical points: red circles; bond paths: grey lines

POURMOHAMMAD ET AL.
11 of 17
in pyridine ring decreased from 1.393 and 1.395 in
PMMA‐MI2 ligand to 1.271 and 1.280 in CuI/PMMA‐
MI2 complex. This property can be essentially due to
the donation of shared electrons from this bond to copper
atom via the coordination that is in agreement with our
FT‐IR spectroscopic data.
To bring forward a more accurate explanation for the
electronic features of interaction between copper nano-
particles and the [PMMA‐co‐MI] support surface, we
studied the QTAIM analysis of M08HX/6‐31G*‐calculated
wave function of electron density obtained for the opti-
mized geometry of CuI/PMMA‐MI1 and CuI/PMMA‐
MI2 complexes. The complete QTAIM molecular graphs
of CuI/PMMA‐MI1 and CuI/PMMA‐MI2 complexes and
PMMA‐MI ligand (including all bond critical points
(BCPs), ring critical points and bond paths) are presented
in Figure 10. Moreover, Table 4 presents M08HX/6‐31G*‐
calculated values of electron density (ρb), its Laplacian
(∇2ρb), electronic kinetic energy density (Gb), electronic
potential energy density (Vb), total electronic energy den-
sity (Hb) and |Vb|/Gb ratio of some selected BCPs for
CuI/PMMA‐MI1 and CuI/PMMA‐MI2 complexes and
PMMA‐MI ligand. It should be mentioned that topologi-
cal analysis of wave functions of electron density was per-
formed using the AIM2000 program package.[59]
TABLE 4 Mathematical properties of BCPs associated with some
selected bonds in PMMA‐MI ligand and CuI/PMMA‐MI1 and CuI/
PMMA‐MI2 complex models. The properties were obtained via
QTAIM analysis of M08HX/6‐31G*‐calculated wave functions of
electron density
ρb
∇2ρb
Gb
Vb
Hb
∣Vb ∣ /Gb
CuI/PMMA‐MI1
Cu–N 0.085
0.330 0.118 −0.154 −0.036 1.305
N–C1
N–C2
0.332 −0.705 0.369 −0.915 −0.546 2.479
0.332 −0.715 0.366 −0.911 −0.545 2.489
CuI/PMMA‐MI1
Cu–N 0.115
0.510 0.179 −0.231 −0.052 1.290
N–C1
N–C2
0.330 −0.705 0.364 −0.904 −0.540 2.483
0.330 −0.714 0.362 −0.903 −0.541 2.494
The comparative investigation of QTAIM‐calculated
results revealed the following features. (I) At Cu–N BCPs
in CuI/PMMA‐MI1 and CuI/PMMA‐MI2 complexes, the
small calculated values of electron density with the posi-
tive values of ∇2ρb and small negative values of Hb and also
PMMA‐MI ligand
N–C1
N–C2
0.340 −0.846 0.351 −0.914 −0.563 2.603
0.341 −0.849 0.351 −0.915 −0.564 2.606
FIGURE 11 FMOs of CuI/PMMA‐MI1 and CuI/PMMA‐MI2 complexes obtained at M08HX/6‐31G* level of theory

12 of 17
POURMOHAMMAD ET AL.
1 < |Vb|/Gb < 2 can be attributed to the semi‐covalent–
electrostatic aspect of interactions. (II) The calculated
values of ρb at C–N BCPs in pyridine ring are reduced
through the donation of shared electrons at C–N bonds to
the copper centre in the complexation process. This behav-
iour confirms the observed decrease in the stretching fre-
quency of bands in the FT‐IR spectrum. (III) Comparison
of the calculated electron density values of Cu–N BCPs in
CuI/PMMA‐MI1 and CuI/PMMA‐MI2 complexes demon-
strates that metal–ligand interactions in CuI/PMMA‐MI2
complex are stronger than in CuI/PMMA‐MI1.
we selected one of the classic Cu‐catalysed multicompo-
nent reactions, the so‐called click reaction. This reaction
is a Cu(I)‐catalysed Huisegn 1,3‐dipolar cycloaddition,
leading to the regioselective construction of 1,2,3‐triazoles
which are interesting biologically active compounds. As a
model reaction, we performed a three‐component reaction
involving phenylacetylene, benzyl bromide and sodium
azide in the presence of our freshly made supported Cu
nanoparticles in various solvents and at a range of temper-
atures from ambient to solvent boiling points. We also con-
ducted the reaction under solvent‐free conditions and
compared the results in terms of the yields of the corre-
sponding product (Table 5). Next, other reaction variables,
such as catalyst loading amount and temperature, were
examined (Table 5). The optimal reaction conditions in
terms of higher yields and shorter reaction times as well
as considering the principles of green chemistry were
found to be as follows: benzyl bromide, phenylacetylene
(1 mmol) and sodium azide (1.3 mmol) being reacted in
the presence of CuI@[PMMA‐co‐MI] (0.02 g) in water
(10 ml) at room temperature (Table 6).[60,61]
The results indicated that CuI@[PMMA‐co‐MI] could
effectively catalyse the regioselective synthesis of 1,4‐
disubstitued 1,2,3‐trizole derivatives via click reaction. It
is worth mentioning that the results showed alkyl and
aryl halides react better than haloketones in terms of
yields and reaction times. The efficiency of
CuI@[PMMA‐co‐MI] in click reaction was also compared
with that of previously reported catalysts under various
reaction conditions (Table 7).[11,28,61–76] By comparison,
it can be concluded that CuI@[PMMA‐co‐MI] as a novel
nanocatalyst has several merits such as higher or
In the final step, we focused on the FMO analysis[47] of
CuI/PMMA‐MI1 and CuI/PMMA‐MI2 complexes at the
M08‐HX/6‐31G* level of theory (Figure 11). HOMO–
LUMO gap energy values were obtained at around 0.2
eV for CuI/PMMA‐MI1 and CuI/PMMA‐MI2 complexes,
which indicated the effective Cu–N coordination through
interactions between filled non‐bonding orbitals (HOMO)
on pyridine nitrogen and an empty dσ orbital (LUMO) on
copper atoms.
Based on our obtained computational results, we can
claim that copper nanoparticles were immobilized more
effectively to pyridine nitrogen of CuI/PMMA‐MI2 com-
plex in comparison with CuI/PMMA‐MI1 complex and
subsequently the decrease in polydispersity of PMMA
chains has a positive effect on the interaction strength.
3.3 | Catalytic activity
Finally, the catalytic activity of CuI@[PMMA‐co‐MI] in
organic transformations was examined. For this purpose,
TABLE 5 Optimization of conditions in click reaction of phenylacetylene, benzyl bromide and sodium azidea in presence of CuI@[PMMA‐
co‐MI]
Entry
CuI@[PMMA‐co‐MI] (g)
Cu (mol%)
Condition (solvent/temperature (°C))
Time (min)
Yield (%)b
1
0.02
0.02
0.04
0.04
0.01
None
0.02
0.02
0.02
0.02
0.02
0.36
0.36
0.72
0.72
0.18
—
H2O/r.t.
10
10
10
10
10
50
10
15
20
30
55
98
94
97
94
75
30
75
80
70
60
45
2
H2O/100
3
H2O/r.t.
4
H2O/100
5
H2O/r.t.
6
H2O/r.t.
7
0.36
0.36
0.36
0.36
0.36
Solvent free/r.t.
H2O/EtOH(1:1)/r.t.
EtOH/r.t.
8
9
10
11
CHCl3/r.t.
Toluene/r.t.
aReactions were run in 5 ml solvent with phenylacetylene (1.0 equiv.), benzyl bromide (1.0 equiv.) and sodium azide (1.3 equiv.).
bYield refers to isolated and pure product.

POURMOHAMMAD ET AL.
13 of 17
TABLE 6 Three‐component reaction of alkyne, alkyl halide and sodium azide, catalysed by CuI@[PMMA‐co‐MI]
α‐Haloketone
Entry or alkyl halide Alkyne
Product
Time (min) Yield (%) M.p., obs. (°C) M.p., lit. (°C)
1
10
98
127–129
127–128[60]
2
10
94
126–127
127–128[61]
3
4
5
6
7
12
15
15
22
22
90
91
88
92
90
78–79
77–79[61]
76–78
77–79[61]
168–170
115–116
104–105
169–171[60]
115–118[61]
102–104[61]
8
25
25
40
95
94
89
158
157–159[61]
111–113[61]
156–158[61]
9
110–111
157–159
10
11
45
93
181
180–183[61]
comparable yield of the desired product in shorter reac-
tion time. It should be mentioned that there are some
reports in which higher yields of products were achieved
using a low amount of catalyst loading. However,
CuI@[PMMA‐co‐MI] promotes the click reaction effi-
ciently (not the best) at room temperature in water, as
well as showing good recyclability, and thus can be con-
sidered as a good candidate for use in an eco‐friendly pro-
tocol in the field of organic synthesis.
To investigate the effect of the chain polymer tailoring
on the efficiency of the catalyst, the sample with the low-
est Cu content (P5) also was used in the click reaction.

14 of 17
POURMOHAMMAD ET AL.
TABLE 7 Comparison of catalytic activity of CuI@[PMMA‐co‐MI] with that other recently reported catalysts in click reaction
Catalyst
amount
Reaction
conditionsa
Time
(h:min)
Entry
Catalyst
Yield (%)b
Ref.
1
CuI@[PMMA‐co‐MI]
SMI–CuI NPs
0.36 mol%
0.03 g
H2O/r.t.
98
88
84
95
99
93
99
91
98
93
94
96
95
99
98
94
95
96
0:10
0:20
0:20
3
This work
[11]
2
H2O/reflux
[28]
[61]
[62]
[63]
[64]
[65]
[66]
[67]
[68]
[69]
[70]
[71]
[72]
[73]
[74]
[75]
3
CuI/AK NPs
0.03 g
H2O/reflux
4
MNP@PILCu
0.7 mol%
5 mg
H2O/Na ascorbate/50°C
H2O/r.t.
5
MNPs@BiimCu(I)
Cu NPs
0:30
8
6
4.3 mol%
0.6 mol%
2 mg
CH3CN/r.t.
7
PS‐C22‐CuI
H2O/r.t.
15
8
Au‐TiO2
H2O/r.t.
0:30
3
9
Cu NPs/C
0.5 mol%
20 mg
H2O/70°C
10
11
12
13
14
15
16
17
18
Fe3O4@TiO2/Cu2O
Cell‐CuI
H2O/reflux
0:15
6
3.5 mol%
0.3 mol%
10 mg
H2O/70°C
MNP@PDMA‐Cu
Nano‐Fe3O4@Cellulose‐NH2‐CuI
MNP@SPAAm/Cu
Cu1‐MMT
H2O/Na ascorbate/50°C
H2O/reflux
2
0:20
1
0.5 mol%
5 mg
H2O/Na ascorbate/50°C
H2O/r.t.
2
γ‐Fe2O3@TiO2‐EG‐CuII
4 mol%
1 mol%
0.05 mol%
H2O/70°C
0:0.5
12
POSS–SAL–Cu
H2O/70°C
Corn‐cob cellulose‐supported
Na ascorbate/70°C
2:30
poly(hydroxamic) Cu complex
[75]
[75]
[75]
[76]
19
20
21
22
Corn‐cob cellulose‐supported
poly(hydroxamic) Cu complex
0.005 mol%
Na ascorbate/90°C
Na ascorbate/70°C
Na ascorbate/70°C
H2O/r.t.
94
91
93
98
2:30
6
Corn‐cob cellulose‐supported
poly(hydroxamic) Cu complex
0.005 mol%
Corn‐cob cellulose‐supported
poly(hydroxamic) Cu complex
0.1 mg = 50 mol ppm
0.48 mol%
20
CuI@HNTs‐2 N‐Sal
0:12
aReaction conditions: phenylactylene, benzyl bromide and sodium azide reacted under different conditions.
bIsolated yield.
The reaction proceeded more sluggishly (35 min) and
gave lower yield (55%) at 45°C, which indicates that
changes in the molecular characteristics of the polymer
support can influence copper loading and totally change
the expected results.
co‐MI] were studied. The catalyst was separated, recov-
ered and reused several times in the selected model
reaction. The results (Figure 12) indicated that recycling
can be successfully done for up to six reactions
runs with slight loss of catalytic activity (2–3%). This
observation indicated the good recyclability of
CuI@[PMMA‐co‐MI].
The other important feature for a true heterogeneous
catalyst is leaching, because a supported catalyst should
not leach into the reaction mixture. Thus, leaching of
CuI species was examined using ICP‐AES analysis. Based
on the obtained results, not only was insignificant
leaching of CuI (0.03 wt%) confirmed, but also the good
efficiency of [PMMA‐co‐MI] for immobilization of CuI
nanoparticles and preventing them from leaching was
proved.
3.4 | Catalyst recycling
The importance of recyclability of a heterogeneous
catalyst is one of the essential features that we expect
from an efficient catalyst. Effective reusability of a
catalyst makes the whole process economically promis-
ing, and thus the process can be a good candidate for
being examined at pilot‐plant level. To examine this
benefit, the recovery and reusability of CuI@[PMMA‐

POURMOHAMMAD ET AL.
15 of 17
recyclability of the catalyst was found to be satisfactory,
and low leaching of CuI species was observed. Further-
more, the reused catalyst preserved its structure and mor-
phology which are good reasons for its satisfactory
recyclability.
ACKNOWLEDGEMENTS
The authors are grateful to Alzahra University for partial
financial assistance. MMH acknowledges the individual
granted research chair given by Iran National Scientific
foundation (INSF).
ORCID
Majid M. Heravi https://orcid.org/0000-0003-2978-1157
FIGURE 12 Recyclability of CuI@[PMMA‐co‐MI] catalyst in
click reaction
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the regioselective synthesis of 1,2,3‐triazoles via
click reaction: Experimental and computational
chemistry. Appl Organometal Chem. 2019;e4967.
https://doi.org/10.1002/aoc.4967
How to cite this article: Pourmohammad N,
Heravi MM, Ahmadi S, Hosseinnejad T. In situ
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