Copper(I) iodide supported on modified cellulose-based nano-magnetite composite as a biodegradable catalyst for the synthesis of 1,2,3-triazoles

Article abstract of DOI:10.1002/aoc.3660

Nano-Fe₃O₄@Cellulose-NH₂-CuI as a novel magnetically separable composite was prepared and fully characterized using various techniques including Fourier transform infrared, X-ray photoelectron and energy-dispersive X-ray spectroscopies, X-ray diffraction, field-emission scanning and transmission electron microscopies, thermogravimetric analysis and vibrating sample magnetometry. To obtain an appropriate structure and also to describe to some extent the different kinds of metal–ligand interactions present in the nano-Fe₃O₄@Cellulose-NH₂-CuI composite, covalent and electrostatic interactions, density functional theory model chemistry and quantum theory of atoms in molecules method were employed, respectively. This cellulose-based heterogeneous catalyst can effectively promote the one-pot three-component reaction of a variety of terminal alkynes bearing substituted phenyls or propargylic alcohol together with substituted benzyl halides and sodium azide, so-called click reaction, in water to afford the corresponding 1,4-disubstituted 1,2,3-triazoles with improved yields and regioselectivity. The magnetic catalyst was conventionally recovered using an external magnet and reused in at least four successive runs under the optimal reaction conditions, without appreciable loss of its activity.

Full text of DOI:10.1002/aoc.3660

Received: 25 July 2016
DOI 10.1002/aoc.3660
Revised: 6 September 2016
Accepted: 20 September 2016
F U L L PA P E R
Copper(I) iodide supported on modified cellulose‐based
nano‐magnetite composite as a biodegradable catalyst for the
synthesis of 1,2,3‐triazoles
Samaneh Sabaqian1 | Firouzeh Nemati1 | Majid M. Heravi2 | Hossein Taherpour Nahzomi3
1 Department of Chemistry, Semnan University,
Nano‐Fe3O4@Cellulose‐NH2‐CuI as a novel magnetically separable composite was
Semnan 35131‐19111, Iran
2 Department of Chemistry, School of Science,
prepared and fully characterized using various techniques including Fourier
transform infrared, X‐ray photoelectron and energy‐dispersive X‐ray spectroscopies,
X‐ray diffraction, field‐emission scanning and transmission electron microscopies,
thermogravimetric analysis and vibrating sample magnetometry. To obtain an
appropriate structure and also to describe to some extent the different kinds of
metal–ligand interactions present in the nano‐Fe3O4@Cellulose‐NH2‐CuI compos-
ite, covalent and electrostatic interactions, density functional theory model chemis-
try and quantum theory of atoms in molecules method were employed,
respectively. This cellulose‐based heterogeneous catalyst can effectively promote
the one‐pot three‐component reaction of a variety of terminal alkynes bearing
substituted phenyls or propargylic alcohol together with substituted benzyl halides
and sodium azide, so‐called click reaction, in water to afford the corresponding
1,4‐disubstituted 1,2,3‐triazoles with improved yields and regioselectivity. The mag-
netic catalyst was conventionally recovered using an external magnet and reused in
at least four successive runs under the optimal reaction conditions, without apprecia-
ble loss of its activity.
Alzahra University, Vanak, Tehran, Iran
3 Department of Chemistry, Payame Noor
University, Tehran, Iran
Correspondence
Firouzeh Nemati, Department of Chemistry,
Semnan University, Semnan 35131‐19111, Iran.
Email: fnemati_1350@yahoo.com;
fnemati@semnan.ac.ir
KEYWORDS
1,4‐disubstituted 1,2,3‐triazoles, biodegradable support, magnetic composite, metal–
ligand interactions, quantum chemistry
1
|
INTRODUCTION
successfully achieved and reported.[7] The more nucleophilic
amino group enhances the surface‐modified cellulose perfor-
Cellulose is the most abundant, inexpensive, renewable
organic raw material on the earth. It is produced by nature
at a rate of 1011–1012 tons per year.[1–3] It is a carbohydrate
polymer made up of repeating β‐D‐glucopyranose units and
consists of three hydroxyl groups per anhydroglucose unit.
In this way the cellulose molecule gains a high degree of
functionality.[4] The greater the OH functionality, the more
the inter‐ or intramolecular hydrogen bonding, which is less
attractive as a solid support.[5] So, to get a higher degree of
applicability and efficiency the surface needs to be modi-
fied.[6] For this purpose, the introduction of amino groups
onto the surface of cellulose via reaction with
mance especially as an electron donor ligand and a stronger
metal–ligand interaction would be observed.[8] All these fea-
tures make it a good biocompatible support.[3]
Catalysts play a key role in green chemistry by providing a
clean and sustainable route for the organic synthesis of fine
chemicals and intermediates.[9] Nowadays, heterogeneous
catalysis is attracting much attention. Conducting a reaction
under heterogeneous catalysis shows several advantages such
as ease of handling, toleration of a wide range of temperatures
and pressures, and easy and inexpensive removal from reac-
tion mixtures by filtration and centrifugation.[10] Recently,
biopolymers such as cellulose,[11] chitosan[12] or wool[13] have
been used in heterogeneous catalyst systems. Nevertheless,
(3‐aminopropyl)triethoxysilane
(APTES)
has
been
Appl Organometal Chem 2016; 1–12
wileyonlinelibrary.com/journal/aoc
Copyright © 2016 John Wiley & Sons, Ltd.
1

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SABAQIAN ET AL.
their use as supports is restricted in industry due to their stable
dispersion which hinders facile separation for recycling. For
this reason, they have been coated with magnetic nanoparticles
which leads to the formation of inorganic–organic hybrid
nanocomposites.[14] Magnetically recoverable catalysts often
exhibit excellent selectivity, giving high yields, and have sev-
eral additional advantages. They can be easily separated with
purity, thus showing good reusability.[15] Among them, mag-
netic iron oxide nanoparticles containing magnetite (Fe3O4)
have been widely studied. They are highly efficient recover-
able catalysts, and are useful in targeted drug delivery, clinical
diagnosis, etc.[16] In addition, they are nontoxic, mostly com-
mercially available or easily accessible, amenable to
functionalization and easy to handle.[17]
three‐component reactions of alkyl halides, sodium azide
and terminal alkynes.
Enhanced environmental consciousness has promoted the
efficiency of chemical reactions under benign conditions
with recycling and reuse of catalysts, a trait that has become
an adjunct of much chemical research today.[35] In this
regard, cellulose base materials could be attractive as
potential supports in heterogeneous catalysis due to low cost,
biodegradability, stability against various chemical environ-
ments and low toxicity.
In continuation of our studies of the design of nano‐
magnetic heterogeneous catalysts[36] and their applications
in several organic transformations[37] and our efforts to
develop regioselective synthesis of 1,4‐disubstituated 1,2,3‐
triazoles via click reaction,[38] in the present paper, we
describe the preparation and characterization of a novel
nano‐magnetic cellulose‐based CuI composite as a recover-
able heterogeneous catalyst. The catalytic application of this
magnetic composite was examined in the reaction of
phenylacetylene, benzyl bromide and sodium azide in water
as a model reaction, which proceeded smoothly to afford the
corresponding 1,4‐substituted 1,2,3‐triazole as sole product,
regioselectively.
Multicomponent coupling reactions are recognized as
very powerful tools for the synthesis of various organic
compounds from simple starting materials via a one‐pot pro-
cess. Especially, multicomponent reactions that provide
polyfunctionalized heterocyclic compounds in a single oper-
ation are of great importance in synthetic organic and medic-
inal chemistry.[18] Click chemistry is an important approach
to the synthesis of drug‐like molecules that can accelerate
the drug delivery process by utilizing a few practical and reli-
able reactions, and has attracted much attention from biolog-
ical and chemical points of view.[19] ‘Click chemistry’ is a
term that was introduced by Sharpless and co‐workers in
2001 to describe reactions that exhibit high yields, high
regio‐ and stereo‐specificity and create only by‐products that
simply could be removed.[20] During the last few decades,
these types of reactions have attracted much attention in dif-
ferent fields of organic chemistry, material science and drug
discovery.[21] Huisgen 1,3‐dipolar cycloaddition is the reac-
tion of terminal alkynes, alkyl halides and sodium azide, pro-
viding 1,2,3‐triazoles. Triazoles are an important class of
heterocycles with a wide range of applications in various
research fields. Examples are anti‐HIV activity,[22] antibacte-
rial activity,[23] anti‐allergic activity,[24] agrochemicals, dyes,
corrosion inhibitors, photostabilizers and photographic mate-
rials.[25] Triazoles are usually produced through copper‐
catalysed azide–alkyne cycloaddition,[26] which is one of
the most reliable click reactions,[27] and has provided a prac-
tical and efficient route to prepare 1,4‐disubstituted 1,2,3‐
triazoles, from a wide range of substrates with excellent
selectivity.[28] Unfortunately, the copper compounds usually
lead to considerable amount of salt‐containing effluent beside
the desired products. They are not easy to handle, are difficult
to separate and have limited reuse potential often due to con-
tamination with final products or formation of metal com-
plexes. So, immobilization of catalysts on suitable insoluble
supports is one of the most reliable methods for improving
the efficiency and recovery of catalysts and strongly recom-
mended from the viewpoint of green chemistry.[29] Zeo-
lites,[30] montmorillonite,[31] polystyrene,[32] chitosan[33]
and modified KIT‐5[34] are some of the notable supports that
bring about the heterogeneous catalysis of regioselective,
2
| EXPERIMENTAL
2.1 | Materials and instrumentation
Chemical reagents of high purity were purchased from Merck
and Aldrich and were used without further purification. Melt-
ing points were determined in open capillaries using an Elec-
trothermal 9100 without further corrections. Fourier
transform infrared (FT‐IR) spectra were obtained with potas-
sium bromide pellets in the range 400–4000 cm−1 using a
Shimadzu 8400 s spectrometer. X‐ray diffraction (XRD) was
conducted with a Philips instrument using Cu Kα radiation
with a wavelength of 1.54 Å. Field‐emission scanning elec-
tron microscopy (SEM) in conjunction with energy‐dispersive
X‐ray (EDX) analysis was performed using a Tescanvega II
XMU digital scanning microscope. Samples were coated with
gold at 10 mA for 2 min prior to analysis. The magnetic prop-
erties were characterized using vibrating sample magnetome-
try (VSM; Lakeshore7407) at room temperature.
Transmission electron microscopy (TEM) was performed
using a CM30 300 kV digital transmission microscope. X‐
ray photoelectron spectroscopy (XPS) was conducted using
a Gammadata‐scienta ESCA200 hemispherical analyser
equipped with an Al Kα (1486.6 eV) X‐ray source.
2.2 | Preparation of catalyst
2.2.1
| Preparation of cellulose‐NH2
Reactive amino groups were introduced onto the surface of
cellulose materials by reaction of cellulose with APTES. In
brief, dried cellulose microcrystals (0.2 g) were mixed with

SABAQIAN ET AL.
3
APTES (2.86 mmol) and anhydrous dimethylformamide
(DMF; 20 ml). The reaction lasted for 2 h at room tempera-
ture. The activated cellulose substrates were separated by
centrifugation, rinsed with anhydrous DMF three times and
dried.[7]
2.2.2
| Preparation of nano‐Fe3O4@Cellulose‐NH2‐CuI
Magnetic nanoparticles were obtained by alkaline hydrolysis
of iron(II) chloride and iron(III) chloride (molar ratio of 1:2)
in aqueous solution according to the co‐precipitation method
described in our earlier report.[37] The magnetic composite
was prepared by adding an aqueous solution of cellulose‐
NH2 (2 wt%) to an aqueous mixture of the magnetic nanopar-
ticles (10 mg ml−1) and CuI (500 mg). The resulting mixture,
CuI, cellulose‐NH2 and magnetic nanoparticles (nanoparti-
cles‐to‐cellulose ratio of 1:1 v/v), was heated at 80 °C and
magnetically stirred for 5 h under nitrogen atmosphere. The
mixture was filtered magnetically and the obtained solid,
nano‐Fe3O4@Cellulose‐NH2‐CuI, was washed with water
and dried under vacuum at 60 °C.
SCHEME 1 Preparation of nano‐Fe3O4@Cellulose‐NH2‐CuI catalyst
mixture of the magnetic nanoparticles (10 mg ml−1) and CuI
(200 mg) (Scheme 1). The structural and chemical nature of
the catalyst was characterized using the corresponding data
provided by FT‐IR spectroscopy, XRD, SEM, TEM, VSM,
XPS and thermogravimetric analysis (TGA).
2.3 | Synthesis of 1‐Benzyl‐4‐phenyl‐1H‐1,2,3‐triazole:
general procedure
Nano‐Fe3O4@Cellulose‐NH2‐CuI (0.01 g) was added to a
solution of phenylacetylene (0.102 g, 1 mmol), benzyl chlo-
ride (0.126 g, 1 mmol) and NaN3 (0.071 g, 1.1 mmol) in
water (3 ml). The reaction mixture was magnetically stirred
under reflux for the required time. The progress of the reac-
tion was monitored by TLC (n‐hexane–ethyl acetate, 7:3).
Upon completion of the reaction, the solution was decanted.
The leftover residue was diluted with hot ethanol and the cat-
alyst was separated from this mixture using an external mag-
net, washed with acetone (2 × 10 ml), dried in an oven and
stored for use in subsequent runs under the same conditions.
After separation of catalyst, the solution was evaporated to
dryness, and crude product was obtained. The residue was
purified by recrystallization from EtOH–H2O (3:1 v/v) to
afford 1‐benzyl‐4‐phenyl‐1H‐1,2,3‐triazole (0.22 g, 95%).
Some products had to be purified by chromatography on sil-
ica gel, using a short column.
3.2 | Catalyst characterization
3.2.1
| FT‐IR spectra
The FT‐IR spectra of nano‐Fe3O4, cellulose, cellulose‐NH2
and nano‐Fe3O4@Cellulose‐NH2‐CuI were recorded and are
depicted in Figure 1. As can be seen in the spectrum of
nano‐Fe3O4 (Figure 1a), the strong band at 595 cm−1 corre-
sponds to Fe─O vibration, and the bands at 3420 and
3
| RESULTS AND DISCUSSION
3.1 | Catalyst preparation
Scheme 1 shows the synthesis of the nano‐Fe3O4@Cellulose‐
NH2‐CuI magnetic composite. The nano‐magnetic composite
was prepared from commercially available, inexpensive
materials. In the first step, cellulose was successfully func-
tionalized using APTES in DMF at room temperature. The
magnetic Fe3O4 nanoparticles were prepared by co‐precipita-
tion of iron(II) and iron(III) ions in alkali medium. Then,
nano‐Fe3O4@Cellulose‐NH2‐CuI was prepared by adding
an aqueous solution of cellulose‐NH2 (2 wt%) to an aqueous
FIGURE 1 FT‐IR spectra of (a) nano‐Fe3O4, (b) cellulose, (c) Cellulose‐
NH2 and (d) nano‐Fe3O4@Cellulose‐NH2‐CuI

4
SABAQIAN ET AL.
1630 cm−1 are assigned to the stretching and bending vibra-
tions of hydroxyl groups on the surface of Fe3O4 nanoparti-
cles.[39] Typical wavenumbers for hydroxyl groups for
cellulose, such as ─CH─OH and ─CH2─OH stretching, are
in the range 3300–3400 cm−1. The methylene group stretching
bands, from the incorporated molecule, are located at 2900 cm
−1 and the band in the range 2800–3000 cm−1 is attributed to
─C─H groups. The bending vibrations of OH on the cellulose
surface are located at 1639 cm−1, the primary and secondary
hydroxyl bending bands appear in the range 1200–1500 cm−1
and C─O stretching vibration is observed at 1100 cm−1
(Figure 1b).[39,40] After functionalization of cellulose, the
N─H bending vibration at around 690 cm−1, NH2 symmetric
bending vibration at 1536 cm−1 and stretching vibration of
C─N at 1220 cm−1 confirm the presence of APTES moieties
on the cellulose surface[4] (Figure 1c). A decrease in intensity
of broad band due to hydroxyl groups (Figure 1d) indicates
the interaction of modified cellulose with nano‐Fe3O4 and
CuI, which was further verified from other techniques.
diameter of Fe3O4 crystallite was determined using Scherrer's
equation to be 8.91 nm. The characteristic peaks at 2θ of
25.5°, 29.5°, 42.2°, 50.0°, 61.2°, 67.45° and 77.20° can be
attributed to cubic CuI (JCPDS card no. 01–076‐0207),
which strongly evidences the immobilization of CuI on the
nano‐magnetic composite (Figure 2d). However, the amount
of CuI particles is very low relative to carriers so that the dif-
fraction peaks are very weak.
3.2.3
| SEM, EDX and TEM
The morphology and chemical purity of nano‐
Fe3O4@Cellulose‐NH2‐CuI were investigated using SEM
(Figure 3a) and EDX analysis (Figure 4a). Appearance of
Au element in EDX analysis shows the material being coated
by a layer of Au for by EDX and SEM characterization.
Figure 3(a) shows the SEM image of nano‐
3.2.2
| XRD analysis
Figure 2 shows XRD patterns of as‐synthesized nano‐Fe3O4,
cellulose, cellulose‐NH2 and nano‐Fe3O4@Cellulose‐NH2‐
CuI. The typical diffraction peaks located approximately at
30.1°, 35.5°, 43.2°, 53.4°, 57.1° and 62.7° can be well
assigned to the diffraction of Fe3O4 nanoparticles with cubic
phase from the (111), (220), (311), (400), (422), (511) and
(440) planes, respectively[41] (Figure 2a).
It is clear that the cellulose and modified cellulose have
typical diffraction angles at around 14.87°, 16.25° and
22.64° (Figure 2b and c).[2] In the XRD pattern of nano‐
Fe3O4@Cellulose‐NH2‐CuI (Figure 2d), the characteristic
peaks of cellulose and Fe3O4 are observed, indicating that
the Fe3O4 nanoparticles are embedded in the modified cellu-
lose and the Fe3O4 structure had not changed. The mean
FIGURE 2 XRD patterns of as‐synthesized (a) nano‐Fe3O4, (b) cellulose,
(c) Cellulose‐NH2 and (d) nano‐Fe3O4@Cellulose‐NH2‐CuI
FIGURE 3 SEM images of surface of (a) nano‐Fe3O4@Cellulose‐NH2‐CuI
and (b) nano‐Fe3O4@Cellulose‐NH2

SABAQIAN ET AL.
5
FIGURE 5 TEM image of nano‐Fe3O4@Cellulose‐NH2‐CuI
3.2.4
| Magnetization study
The magnetic behaviour of the as‐synthesized nano‐Fe3O4,
nano‐Fe3O4@Cellulose‐NH2 and nano‐Fe3O4@Cellulose‐
NH2‐CuI was investigated using VSM. The magnetization
curves were recorded at room temperature and are shown in
Figure 6. The saturation magnetization of the uncoated nano-
particles is 61.6 emu g−1, which is typical for maghemite
nanoparticles. The nano‐Fe3O4@Cellulose‐NH2 and nano‐
Fe3O4@Cellulose‐NH2‐CuI samples have saturation magne-
tizations of 22.13 and 21.11 emu g−1, respectively. Due to
the nonmagnetic properties of amino‐modified cellulose and
CuI on the particle surface, the mean saturation magnetiza-
tion decreases after the coating process. The difference
FIGURE 4 EDX spectra of surface of (a) nano‐Fe3O4@Cellulose‐NH2‐CuI
and (b) nano‐Fe3O4@Cellulose‐NH2
Fe3O4@Cellulose‐NH2‐CuI with the optimized amount of
CuI required for catalytic activity. The morphology of the
composite displays a homogeneous structure. As shown in
Figure 4(a), the EDX spectrum of nano‐Fe3O4@Cellulose‐
NH2‐CuI indicates that there are C, O, N, Fe, Cu and I
elements in the catalyst that confirms the presence of CuI
along with iron in the structure of nano‐Fe3O4@Cellulose‐
NH2‐CuI. The amount of CuI loading in nano‐
Fe3O4@Cellulose‐NH2 is estimated to be 2.25% from EDX
analysis (Figure 4a). Also, for comparison, SEM image and
EDX spectrum of nano‐Fe3O4@Cellulose‐NH2 are shown in
Figures 3(b) and 4(b). A comparison of Figure 3(a) and (b)
with Figure 4(a) and (b) indicates that CuI is loaded on
nano‐Fe3O4@Cellulose‐NH2. This also guarantees the immo-
bilization of CuI species on nano‐Fe3O4@Cellulose‐NH2.
A TEM image of the prepared nano‐Fe3O4@Cellulose‐
NH2‐CuI is shown in Figure 5. The TEM image shows the exis-
tence of three regions with different size and electron density
which confirms the formation of the composite: two electron‐
dense regions of different sizes which correspond to Fe3O4
nanoparticles and CuI microparticles and a less dense and more
translucent region which corresponds to cellulose matrix.
Figure 5 confirms the stable and homogeneous dispersion of
Fe3O4 nanoparticles on the surface of modified cellulose.
FIGURE 6 Magnetic hysteresis curves for as‐synthesized (a) nano‐Fe3O4,
(b) nano‐Fe3O4@Cellulose‐NH2 and (c) nano‐Fe3O4@Cellulose‐NH2‐CuI

6
SABAQIAN ET AL.
between magnetic saturation of nano‐Fe3O4@Cellulose‐NH2
and nano‐Fe3O4@Cellulose‐NH2‐CuI is negligible. Clearly,
with such high saturated magnetization, the nano‐
Fe3O4@Cellulose‐NH2‐CuI could be easily and quickly
separated from a reaction mixture by applying an external
magnet field.
3.2.5
| XPS analysis
The XPS elemental survey scan of the surface of the nano‐
Fe3O4@Cellulose‐NH2‐CuI composite is shown in Figure 7.
Peaks corresponding to carbon, oxygen, iron, iodine and
copper are clearly observed.
The corresponding high‐resolution XPS spectra of C
1 s, O 1 s and Fe 2p regions are shown in Figure 8. The
XPS spectra show two major peaks with binding energies
of ca 293.82 and 539 eV, corresponding to C 1 s (Figure 8a)
and O 1 s (Figure 8b), respectively, and characteristic of the
presence of the cellulose phase.[42] The peaks appearing in
Figure 8c are located at 709.23 and 723.88 eV, which are
ascribed to Fe 2p3/2 and Fe 2p1/2 of Fe in Fe3O4.[43] Because
of the low loading of CuI in the nano‐Fe3O4@Cellulose‐
NH2‐CuI composite, very faint signals appear at 942.3 and
962.5 eV. They are assigned to Cu+ state, which is in accor-
dance with the data reported in the literature.[37]
3.2.6
| Thermogravimetric analysis
In order to obtain information on the thermal stability, TGA
experiments were carried out by heating nano‐Fe3O4, cellu-
lose, cellulose‐NH2 and nano‐Fe3O4@Cellulose‐NH2‐CuI
up to 600 °C in air. These experiments confirm the
functionalization of cellulose and the presence of Fe3O4 and
CuI in the composite (Figure 9).
Figure 9(a) shows the TGA curve for bare Fe3O4 nano-
particles. The curve reveals little change in terms of mass
loss. Loss of strongly adsorbed water and dehydration of sur-
face hydroxyl groups occur at approximately 250 °C. Pure
cellulose shows a 5–10% weight loss between 35 and
FIGURE 8 High‐resolution XPS spectra of nano‐Fe3O4@Cellulose‐NH2‐
CuI composite: (a) C 1 s; (b) O 1 s; (c) Fe 2p
150 °C, due to the evaporation of adsorbed moisture. Another
sharp mass loss appears at 275 °C, which could be attributed
to the degradation of cellulose chains.[1] For cellulose‐NH2
the decomposition process can be divided into two stages
within the range from 35 to 500 °C. Between 35 and
150 °C, the initial weight loss of the samples is below 5–
10%, presumably due to the evaporation of adsorbed water.
At higher temperatures (150–500 °C), a different pattern of
loss of weight from cellulose can be seen, indicating the deg-
radation of organic material, that is, aminocellulose.[2] The
weight loss of nano‐Fe3O4@Cellulose‐NH2‐CuI is about
60% at 270–320 °C, corresponding to the thermal
FIGURE 7 XPS pattern of as‐synthesized nano‐Fe3O4@Cellulose‐NH2‐
CuI composite

SABAQIAN ET AL.
7
3.3.2
| Computational assessment
On the basis of our obtained DFT and QTAIM computational
results, we can present a quantitative description for metal–
ligand interactions of the nano‐Fe3O4@Cellulose‐NH2‐CuI
complex 2.
In this case, structures 1 and 2 are considered as simple
models for cellulose‐NH2 ligand and nano‐Fe3O4@Cellulose‐
NH2‐CuI complex, respectively (Scheme 2). Also, a tetrahe-
drally coordinated high‐spin Fe(III) moiety has been consid-
ered as a model for nano‐Fe3O4 with inverse spinel crystal
lattice structure. The choice of the position of the tethered Si
side chain on the ring is arbitrary, as upon surveying the
pertinent literature it appeared that, because of the complex
structure of the FT‐IR spectrum, no attempt to precisely assign
the newly formed Si─O bonds was made in any of the previous
researches. Additionally, our calculation on another complex
structure involving the exchanged positions of CuI and Fe moi-
eties resulted in a complex which is 38.6 kcal mol−1 higher in
energy than 2, and as a consequence, further calculations were
performed on 2 as found to be the more stable structure.
In Figure 10, we present the optimized geometries of
ligand 1 and complex 2 calculated using the M06 method
with the atomic numbering. In Figure 10, we also present
M06 calculated C─N bond length (and also bond order in
parentheses) in each of 1 and 2. Comparative survey of the
optimized structures of 1 and 2 demonstrates a geometrical
deformation in 1 through complexation. In the following,
the structural stability of 2 is analysed based on the various
electronic indicators.
FIGURE 9 TGA curves for the synthesized (a) nano‐Fe3O4, (b) cellulose,
(c) Cellulose‐NH2 and (d) nano‐Fe3O4@Cellulose‐NH2‐CuI
decomposition of cellulose chains over Fe3O4 NPs and CuI.
The remaining weight loss for nano‐Fe3O4@Cellulose‐NH2‐
CuI at temperature higher than 300 °C is related to the
Fe3O4 and CuI that are loaded in the composite.
3.3 | Computation
3.3.1
| Computational details
Recently, we have assessed computationally metal–ligand
interactions in modified poly(styrene‐co‐maleic anhydride)
palladium nanocatalyst,[44] copper(I) aminated KIT‐5[38]
and APTES‐KIT‐5 mesoporous silica‐supported copper(II)
acetate complex[45] via quantum chemistry approaches.
Armed with these experiences, we present a quantitative
description for metal–ligand interactions in the nano‐
Fe3O4@Cellulose‐NH2‐CuI complex by performing density
functional theory (DFT)[46] and quantum theory of atoms in
molecules (QTAIM) computations.[47,48] In this respect, we
have designed an effective model for cellulose‐NH2 (ligand 1)
and nano‐Fe3O4@Cellulose‐NH2‐CuI (complex 2) consider-
ing that this model is a credible comprise between accuracy
and time‐saving efficiency of computational procedure. We
first determined the optimized structure of compounds 1
and 2 using the M06 method in combination with the basis
sets 6‐31G for C, H, O and N atoms and 6‐31G(d) for Si
atom, and in the cases of Cu, Fe and I atoms, the effective
core potential, LANL2DZ, were used together with the
accompanying basis set to describe the valence electron den-
sity.[49] It should be mentioned that M06 functional has been
introduced recently as a hybrid meta‐GGA (generalized gra-
dient approximation) exchange‐correlation functional that
was parameterized including both transition metals and
non‐metals and was recommended for application in organo-
metallic and thermochemistry, kinetic studies and
noncovalent interactions.[50] The stationary points were
determined as minima through verifying the presence of all
real frequencies. All DFT computations were performed
using the Gaussian 09 suite of programs.[51]
The bond orders of some key bonds in 1 with their corre-
sponding bonds in complex 2 are listed in Table 1 to charac-
terize the variation of bond orders via complexation. The data
in Table 1 demonstrate that the bond order of C1─N1,
C2─N2, C4─O2 and C3─O1 bonds decreases in 2 compared
to 1, through complexation.
In the next step, we focused on topological analysis of
electron density via the QTAIM method[48,49] to interpret
SCHEME 2 Simple model for cellulose‐NH2 ligand

8
SABAQIAN ET AL.
TABLE 1 Calculated values of some selected bond orders in ligand 1 and
complex 2 obtained at M06/6‐31G level of theory (numbering of atoms is in
accordance with Figure 10)
Bonded atoms
Ligand 1
Complex 2
N1─C1
N1─H1
N1─H2
O2─H5
O2─C4
O1─C3
N2─C2
N2─H3
N2─H4
N1─Cu
O1─Cu
O2─Cu
Cu─I
0.913
0.796
0.863
0.721
0.875
0.786
0.957
0.858
0.859
—
0.820
0.803
0.815
0.717
0.833
0.741
0.796
0.809
0.809
0.380
0.205
0.199
0.946
0.281
0.076
—
—
—
N2─Fe
H5─I
—
—
FIGURE 10 Atomic numbering and optimized structures obtained at M06/
6‐31G level of theory for 1 and 2. Also shown are the C─N bond lengths
(and bond orders) calculated at M06/6‐31G level of theory
the nature of metal–ligand interactions in complex 2. In this
respect, we analysed M06/6‐31G calculated wave function
of electron density using the Multiwfn program package.[52]
QTAIM molecular graphs of ligand 1 and complex 2 includ-
ing all bond and ring critical points and their associated bond
paths are displayed in Figure 11.
Table 2 gives the QTAIM calculated values of electron
density, ρb, its Laplacian, ∇2ρb, electronic kinetic energy
density, Gb, electronic potential energy density, Vb, total
electronic energy density, Hb, and |Vb|/Gb ratio at some
selected bond critical points (BCPs) for ligand 1 and com-
plex 2. It is important to mention that the electron density
at BCPs usually corresponds to the strength of the bond
between two atoms. Values of ρb < 0.1 au are indicative
of an electrostatic interaction; it is usually correlated with
a relatively small and positive value of ∇2ρb.[49–52] By con-
trast, for a covalent interaction, usually ρb > 0.1 au and
∇2ρb is usually negative with the same order as ρb.[48–52]
Moreover, a good authentic indicator for classifying inter-
atomic interactions is the total electronic energy density
that is defined as Hb = Gb + Vb at BCPs. For electrostatic
interactions, Hb has a positive value and for covalent inter-
actions it is negative.
FIGURE 11 Complete molecular graphs of 1 and 2 obtained using QTAIM
analysis of M06/6‐31G electron density functions. BCPs: brown circles; ring
critical points: yellow circles; bond paths: green lines
On the basis of the results collected in Table 2, the fol-
lowing can be stated: (i) through complexation, calculated
values of ρb decrease at N1─C1, N2─C2, O2─C4 and
O1─C3 BCPs, which confirms the donation of shared elec-
trons to the metal centres; (ii) the large values of electron
density together with the negative values of ∇2ρb and Hb
at N1─C1, N2─C2, O2─C4, O1─C3 and N─Hs BCPs
indicate the covalent character of these chemical bonds in
1 and 2; and (iii) the small values of electron density with
the positive values of ∇2ρb and Hb at N1─Cu, O1─Cu,
O2─Cu and N2─Fe BCPs demonstrate that the

SABAQIAN ET AL.
9
TABLE 2 Mathematical properties of some selected BCPs in ligand 1 and complex 2. The properties have been obtained via QTAIM analysis of the M06/6‐
31G calculated wave function of electron density (numbering of atoms is in accordance with Figure 10)
Bonded atoms of BCPs
ρb
∇2ρb
Gb
Vb
Hb
|Vb|/Gb
Ligand 1
N1─C1
N2─C2
O1─C3
O2─H5
O2─C4
Complex 2
N1─C1
N2─C2
O1─C3
O2─H5
O2─C4
N1─Cu
O1─Cu
O2─Cu
Cu─I
0.2545
0.2515
0.2178
0.3226
0.2312
−0.5803
−0.5618
−0.2637
−0.1523
−0.3688
0.1189
0.1167
0.1698
0.0631
0.1544
−0.3829
−0.3738
−0.4055
−0.5070
−0.4010
−0.2640
−0.2571
−0.2357
−0.4439
−0.2466
3.2204
3.2031
2.3883
8.0386
2.5972
0.2301
0.2288
0.2104
0.3203
0.2232
0.0745
0.0386
0.0307
0.0519
0.0678
−0.4438
−0.4393
−0.2165
−0.1513
−0.3214
0.4756
0.1073
0.1127
0.1709
0.6190
0.1546
0.1194
0.0526
0.0313
0.417
−0.3255
−0.3353
−0.3959
−0.5020
−0.3895
−0.1198
−0.0468
−0.0315
−0.0492
−0.0953
−0.2182
0.2226
3.0336
2.9752
2.3166
0.8110
2.5194
1.0034
0.8902
1.0004
1.1795
1.0341
−0.2250
−0.4401
−0.2349
−0.0005
0.0058
0.2334
0.1240
−0.0003
−0.0075
−0.0031
0.1368
N2─Fe
0.3559
0.0921
metal–ligand interactions do not have covalent character.
For N1─Cu, O1─Cu and O2─Cu BCPs, calculated values
of 1 < |Vb|/Gb < 2 confirm the presence of partially cova-
lent–electrostatic interactions.
Therefore, the weight ratio of Cellulose‐NH2:nano‐Fe3O4:
CuI of 2:1:1 was selected. The copper loading in nano‐
Fe3O4@Cellulose‐NH2‐CuI was determined using atomic
absorption spectroscopy. For this purpose, the magnetic com-
posite was dissolved in aqua regia (3:1 HCl–HNO3) solution,
filtered and analysed. Cu loading in nano‐Fe3O4@Cellulose‐
NH2‐CuI was found to be 2 wt%. Comparison of EDX
(Figure 3) and atomic absorption analysis of nano‐
Fe3O4@Cellulose‐NH2‐CuI confirms the loading of copper
to the modified support, which is a good evidence for the for-
mation of metal complex with anchored ligand.
3.4 | Application of Nano‐Fe3O4@Cellulose‐NH2‐CuI
magnetic catalyst
After the successful preparation and characterization of the
nano‐Fe3O4@Cellulose‐NH2‐CuI magnetic catalyst, its cata-
lytic activity with different weight ratios of CuI was exam-
ined using
a
model reaction of benzyl bromide,
The reaction of benzyl bromide, sodium azide and
phenylacetylene was selected as a model reaction in various
solvents, temperatures and loadings of magnetic catalyst.
The results for the optimization of the reaction conditions
are summarized in Table 4. The reaction proceeds in
refluxing water, giving the highest yield of product for which
an inert atmosphere is not required (Table 4, entry 4). We
carried out the model reaction in the presence of nano‐
Fe3O4@Cellulose‐NH2 as a catalyst under reflux in water
and a poor yield of product is obtained even after 2 h (Table 4,
entries 9 and 10). As expected, the reaction does not proceed
in the absence of the catalyst, even after prolonged
reaction time (Table 4, entry 8). This indicates that
phenylacetylene and sodium azide (Huisgen cycloaddition
reaction), to obtain 1‐benzyl‐4‐phenyl‐1H‐1,2,3‐triazole (4a)
(Scheme 3), as sole product, using 0.01 g of magnetic com-
posite under reflux in water. The products are obtained in
high yield and excellent regioselectivity. The result shows
that this click reaction proceeds with regioselectivity, among
other merits, resulting from the use of this novel catalyst sys-
tem for the aforementioned model reaction. In order to estab-
lish the strategy, various terminal alkynes, substituted benzyl
bromides and sodium azide were reacted in the presence of
catalytic amounts of nano‐Fe3O4@Cellulose‐NH2‐CuI to
afford the corresponding 1,4‐disubstituted 1,2,3‐triazoles,
regioselectively and in good yields.
As evident from Table 3, the catalytic performance of mag-
netic composite with a weight ratio of 2:1:1 of Cellulose‐NH2:
nano‐Fe3O4:CuI gives the best result (Table 3, entry 5). It is
observed that increasing the CuI loading in the magnetic
composite does not result in any improvement in the yields.
TABLE 3 Optimization of CuI for magnetic catalyst in model reaction
Entry
Cellulose‐NH2 (g)
Nano‐Fe3O4:CuI (g)
Yield (%)
1
2
3
4
5
6
1
1
1
1
1
1
0.5:0.1
0.5:0.2
0.5:0.3
0.5:0.4
0.5:0.5
0.05:0.6
37
50
70
85
95
95
SCHEME 3 Click reaction catalysed by nano‐Fe3O4@Cellulose‐NH2‐CuI

10
SABAQIAN ET AL.
TABLE 4 Optimization of three‐component synthesis of 1‐benzyl‐4‐phenyl‐1H‐1,2,3‐triazole (4a)a
Entry
Catalyst (g)
Conditions
H2O/r.t.
Time (h:min)
Yield (%)b
1
Nano‐Fe3O4@Cellulose‐NH2‐CuI (0.01)
Nano‐Fe3O4@Cellulose‐NH2‐CuI (0.01)
Nano‐Fe3O4@Cellulose‐NH2‐CuI (0.01)
Nano‐Fe3O4@Cellulose‐NH2‐CuI (0.01)
Nano‐Fe3O4@Cellulose‐NH2‐CuI (0.01)
Nano‐Fe3O4@Cellulose‐NH2‐CuI (0.015)
Nano‐Fe3O4@Cellulose‐NH2‐CuI (0.005)
—
2:00
0:20
0:20
0:20
0:20
0:20
0:20
12:00
2:00
2:00
2:00
2:00
2:00
0:20
2:00
2:00
Trace
35
2
H2O/50 °C
3
H2O/75 °C
82
4
H2O/reflux
95
5
H2O/110 °C
95
6
H2O/reflux
95
7
H2O/reflux
53
8
H2O/reflux
—
9
Nano‐Fe3O4@Cellulose‐NH2 (0.01)
Nano‐Fe3O4@Cellulose‐NH2 (0.02)
Nano‐Fe3O4@Cellulose‐NH2‐CuI (0.01)
Nano‐Fe3O4@Cellulose‐NH2‐CuI (0.01)
Nano‐Fe3O4@Cellulose‐NH2‐CuI (0.01)
Nano‐Fe3O4@Cellulose‐NH2‐CuI (0.01)
Nano‐Fe3O4@Cellulose‐NH2‐CuI (0.01)
Nano‐Fe3O4@Cellulose‐NH2‐CuI (0.01)
H2O/reflux
Trace
Trace
62
10
11
12
13c
14c
15c
16c
H2O/reflux
Solvent free/100 °C
DMF/100 °C
Toluene/100 °C
Ethanol/reflux
H2O–DMSO (2:1)/reflux
CH3CN/reflux
45
56
85
50
70
aReaction conditions: benzyl bromide (1 mmol), sodium azide (1.1 mmol), phenylacetylene (1 mmol) and catalyst (0.010 g) in water under reflux.
bIsolated yield.
cSolvent (2 ml).
nano‐Fe3O4@Cellulose‐NH2‐CuI as a catalyst plays a crucial
role in the synthesis of 4a. A higher reaction temperature or
catalyst amount does not make an obvious difference in the
yield of product (Table 4, entries 5, 6). But, a lower amount
of catalyst decreases the yield of the reaction (Table 4, entry
7). Accordingly, the best results are obtained when the reac-
tion is performed under reflux in water in the presence of
0.01 g of nano‐Fe3O4@Cellulose‐NH2‐CuI.
Thus, with the optimized reaction conditions in hand, the
substrate scope of reaction was extended to various structur-
ally diverse terminal alkynes and benzyl halides (Table 5).
In general, various substituted phenylacetylenes and benzyl
halides bearing electron‐donating substituents as well as elec-
tron‐withdrawing groups provide an array of 1,4‐disubsti-
tuted 1,2,3‐ triazoles smoothly and cleanly, in good to
excellent yields (75–95%) within relatively short times
TABLE 5 Three‐component click reaction of benzyl halides, terminal alkynes and sodium azide using nano‐Fe3O4@Cellulose‐NH2‐CuI magnetic catalysta
Halide
precursor
Time
(min)
Yield
(%)b
Entry
Alkyne
Product
1
20
25
30
20
95
88
85
88
2
3
4
5
6
25
30
90
89
7
8
25
25
90
83
(Continues)

SABAQIAN ET AL.
TABLE 5 (Continued)
Entry
11
Halide
precursor
Time
(min)
Yield
Alkyne
Product
(%)b
9
20
25
87
87
10
11
12
13
30
25
85
86
66
180
aReaction conditions: alkyl halide (1 mmol), sodium azide (1.1 mmol), acetylene (1 mmol) and nano‐Fe3O4@Cellulose‐NH2‐CuI (0.010 g), H2O (2 ml), reflux.
bIsolated yield.
(15–80 min). As shown in Table 5, the aliphatic terminal
alkynes bearing hydroxyl as functional group gave the
desired triazoles in high yields.
led to desired products without significant changes in terms
of the reaction time and yield. The yields for the four runs
were found to be 95, 92, 90 and 89%, respectively
(Figure 12). In addition only negligible difference between
the copper content of fresh and the reused catalyst was
observed as determined using atomic absorption spectros-
copy, indicating the low amount of CuI catalyst leaching
into the reaction mixture.
3.5 | Recycling and leaching of catalyst
One of the main advantages of magnetic catalysts is their
ease of separation as well as their reusability in further
runs.[53] In this regard, the recyclability of the nano‐
Fe3O4@Cellulose‐NH2‐CuI magnetic catalyst was practi-
cally examined in a one‐pot synthesis of 4a under opti-
mized conditions. A model reaction was conducted four
times with recycled catalyst under similar conditions and
no appreciable loss of weight was observed in the obtained
desired compound. After each cycle, the catalyst was
removed using a magnet, washed with water and ethyl ace-
tate, dried in an oven at 70 °C and reused in another run of
the model reaction without any further modification. This
process was carried out over four runs and all reactions
4
| CONCLUSIONS
In this study we have used magnetic modified cellulose as an
inexpensive and biodegradable support for stabilization of
CuI. The novel composite demonstrated efficient catalytic
activity in terms of yield and reaction time in outstanding
synthesis of 1,4‐disubstituted 1,2,3‐triazoles. Short reaction
time, high yield, recyclability and reusability of the catalyst
are the main notable advantages of this methodology which
make the protocol economic.
ACKNOWLEDGMENTS
FN is gratefully acknowledge the financial support from
Semnan University Research Council. MMH is thankful to
Iran National Science Foundation (INSF) for its financial
support and Alzahra University research council for the
encouragements.
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FIGURE 12 Recycling results for nano‐Fe3O4@Cellulose‐NH2‐CuI
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12
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How to cite this article: Sabaqian, S., Nemati, F.,
Heravi, M. M., and Nahzomi, H. T. (2016), Copper
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