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Cite This: ACS Omega 2019, 4, 13845−13852 http://pubs.acs.org/journal/acsodf

Sonochemically Synthesized Spin-Canted CuFe2O4 Nanoparticles for

Heterogeneous Green Catalytic Click Chemistry
Bibhas Mondal,†,‡ Mousumi Kundu,† Siba Prasad Mandal,† Rajat Saha,*,† Ujjal Kanti Roy,*,†
Anirban Roychowdhury,§,∥ and Dipankar Das∥
†
Department of Chemistry, Kazi Nazrul University, Asansol 713340, India
‡
Department of Chemistry, NIT-Durgapur, Durgapur 713209, India
§
Department of Physics, Krishnath College, Berhampore 742101, West Bengal, India
∥
UGC-DAE Consortium for Scientific Research, Kolkata Centre, III/LB-8, Bidhannagar, Kolkata 700098, India
*
S Supporting Information

ABSTRACT: Heterogeneous green catalysis by using magnetically separable nanometal−oxide catalysts has become a subject
of prime focus recently. PXRD (powder X-ray diffraction), FESEM (field emission scanning electron microscopy), and HRTEM
(high-resolution tunneling electron microscopy) with IR and Raman spectroscopy are applied to analyze the structural and
microstructural properties of nanosized (∼15.3 nm) CuFe2O4 synthesized by both sonochemical and mechanochemical
processes. The sonochemical process provides a better uniformity of sizes of the nanoparticles (NPs). Rietveld refinement with
the PXRD pattern reveals the inverse spinel-like architecture of CuFe2O4 NPs. The Raman spectra also indicate the phase purity
of the synthesized material. The static magnetic measurements are performed at different magnetic fields and temperature
ranges from 300 to 5 K, which confirms the existence of the ferrimagnetic phase mixed with some finer superparamagnetic
(SPM) nanophases within the sample. Unsaturated magnetization is observed even at an applied 5 T magnetic field for the
presence of spin-canting nature in the partially inverted copper ferrite phases at the surfaces of the nanoparticles. Now, these
coupled magnetic CuFe2O4 NPs are used as a heterogeneous catalyst for three-component Huisgen 1,3-dipolar cycloaddition
click reaction in aqueous media. By this catalyst system, we were able to couple alkyl halide, epoxide, or boronic acid with
alkynes efficiently to furnish 1,4-disubstituted 1,2,3-triazoles in excellent yields within very short reaction time. The test for
heterogeneity, reusability, and reproducibility of the catalyst has also been performed successfully without prominent decrease
in yield up to the fifth cycle.

1. INTRODUCTION chemistry, while usage of magnetically separable spinel ferrites

Heterogeneous green catalytic click chemistry is very
important from several perspectives: (a) green chemistry: the
reaction proceeds without using any solvent only in the
presence of the catalyst, (b) easy separation: the catalyst can be
separated from the mixture by simple filtration, (c) click
chemistry: click chemistry provides the maximum conversion.1
Catalytic click chemistry is a unique approach for the
conversion of reactant molecules to a particular desired
product in a single step or consecutive steps. Several types of
heterogeneous catalysts such as MOFs,2 metal nanoparticles
(NPs),3 and metal−oxide NPs4 are used for such click
for such application is relatively scarce.5 On the other hand,
copper-catalyzed azide−alkyne cycloaddition (CuAAC) is an
important “click chemistry” reaction which has been
extensively applied in chemical biology, medicinal chemistry,
and materials science. The CuAAC reaction of terminal
alkynes provides a mild and efficient synthesis of 1,4-
disubstituted 1,2,3-triazoles. However, such reaction in the
Received: May 21, 2019
Accepted: August 2, 2019
Published: August 16, 2019

© 2019 American Chemical Society 13845 DOI: 10.1021/acsomega.9b01477

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case of internal alkynes to afford trisubstituted triazoles, is still azide and subsequently their coupling with terminal and
very challenging. internal alkynes in the presence of CuFe2O4 NPs. Leaching is a
In recent times, the nanosized spinel ferrites have been used major limitation in the use of heterogeneous catalysts, and it
as a potent applicant in the field of materials science not only can completely cripple application. However, we observed
due to their widespread technological applications but also to negligible amount of leaching in our synthesized catalyst. The
understand the fundamentals of nanomagnetism.6 Interest- click reaction of internal alkynes with azides, producing
ingly, the physical properties of such nanometric substances trisubstituted triazoles, is extremely challenging.13 However
differ enormously from their bulk properties. Thus, under- in our hand, from the point of reactivity, there is no difference
standing and discovering a technique for controlling super- between terminal and internal alkynes. This result is very
paramagnetism, collective magnetic excitation, spin canting promising because there are only few reports to couple internal
effect, and spin-glass (SG)-type nature of ferrite nanomaterials alkynes with azides.14
require considerable thought to expand their broad scale
application in electronic and magnetic devices (microwave, 2. RESULTS AND DISCUSSIONS
radiofrequency, optoelectronic devices, etc.), ferrofluid tech- 2.1. Structural and Microstructural Analyses. Phase
nology, magnetic resonance imaging, and hyperthermia for purity of the bulk material has been analyzed by the PXRD
cancer treatment.7 According to the phase diagram proposed pattern (Figure 1) of the synthesized material at the solid state,
by Villain, Poole, and Farach, with the introduction of
nonmagnetic ions in place of magnetic ions at tetrahedral
(A) and octahedral [B] sites, different magnetic orders evolve
in the spinel ferrite systems, and this is mainly due to the
modifications in the inter-sublattice A−O−B (JAB) and intra-
sublattice A−O−A (JAA) and B−O−B (JBB) exchange
interactions.8
Among various spinel ferrites, nanosized copper ferrite
(CuFe2O4) has drawn significant attention because it is easy to
synthesize, gives high yield at low cost, and is mechanically
hard and chemically stable.9 Furthermore, it is an attractive
magnetic material extensively used in a variety of applications,
such as catalysis, sensor technology, high-density data storage,
magnetic resonance imaging, and magnetically guided drug
delivery.10 Magnetic and electrical properties of copper ferrite
nanostructures are sharply guided by the cation distribution in
their specified magnetic sites.11 Copper ferrite occurs naturally
in two crystallographic spinel structures: the high-temperature
cubic phase (c-CuFe2O4) and the low-temperature tetragonal Figure 1. XRD pattern of CuFe2O4 NPs.
phase (t-CuFe2O4). It is ferrimagnetic (Néel temperature
approximately 780 K) at room temperature (RT). The and also a detailed structural analysis has been carried out by
magnetization of sublattice-A is antiparallel to sublattice-B, using Rietveld analysis. Initially, the PXRD pattern of our
and both sublattices (A and B) are ferromagnetically coupled. sample was indexed by statistical analysis using DICVOL0615
The overall μeff of copper ferrite arises as a result of and TREOR90 of the Fullprof.2k package.16 The correspond-
uncompensated magnetic moments of eight Cu2+ ions in ing Miller indices and peak positions are perfectly matched
sublattice-B. The relatively small energy difference of Cu2+ ions with the standard PXRD pattern of spinel ferrites.17 Structural
in A and B sites helps to originate five types of cation and microstructural properties, phase purity along with the
redistributions, and this is strongly dependent on annealing crystal structure, bond lengths, and bond angles were
temperature as well as the cooling rate.12 Thus on an A site, a investigated by the Rietveld refinement of the PXRD pattern
single Cu2+ ion per unit cell doubles the magnetic moment. for our sample using the GSAS program18 with the EXPGUI
Under this background, we have synthesized monodispersed, interface.19 The results are shown in Figure 2. The refinement
uniform-sized CuFe2O4 NPs by the sonochemical process and parameters, metal−oxide bond lengths, and bond angles are
characterized them by powder X-ray diffraction (PXRD), high-
resolution transmission electron microscopy (HRTEM),
dynamic light scattering, selected area electron diffraction
(SAED), and energy-dispersive X-ray spectroscopy techniques
to investigate its various physical properties. Rietveld analysis
reveals that CuFe2O4-NPs are crystallized in the cubic Fd3̅m
space group, and the corresponding JCPDS file number is 77-
0010. The NPs were also characterized by IR and Raman
spectral analyses. The magnetic study indicates that CuFe2O4-
NPs show strong ferromagnetic interaction with spin-canting
behavior. These CuFe2O 4 NPs are employed for the
heterogeneous catalytic conversion of Huisgen 1,3-dipolar
cycloaddition click reaction in water. Through this article, we
want to report in situ generation of alkyl or aromatic azides
from corresponding halide/boronic acid/epoxide and sodium Figure 2. Structural diagram of CuFe2O4 NP.

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listed in Table S1 (Supporting Information), and the fractional the analysis of Raman active modes. Figure 4 shows the Raman
coordinate as well as occupancy of different ions obtained from spectra of CF NPs at RT indicating 10 prominent peaks at 154,
the refinement by the GSAS program are provided in Table S2
(Supporting Information). According to the literature, the
Cu2+ ions have B-sites affinity rather than A-sites.20 We have
fitted the PXRD pattern of the sample with three different
concentrations of Cu2+ ions occupying [A] and [B] sites
mentioned in Lakhani et al.21 It has been found that “Chi-
square” (χ2) values obtained for this
(Cu0.20Fe0.80)A[Cu0.80Fe1.20]BO4 cation distribution suggest
good refinement of the PXRD pattern of the sample.
The average crystallite size of the sample is calculated from
the broadening of well-defined peaks of the sample in the
(XRD) pattern by using the Debye−Scherrer equation
⟨D⟩ = 0.9λ /(β1/2 cos θ )
Figure 4. Raman spectrum of CF NPs.
where ⟨D⟩ is the average crystallite size, “λ” is the wavelength
of the incident X-ray radiation, and “θ” is the Bragg angle.
Here, “β1/2” is the full-width at half-maximum of the XRD 219, 282, 338, 399, 471, 555, 604, 645, and 686 cm−1. All these
peak. The average estimated crystallite size of the sample is ∼9 peaks are assigned to the cubic inverse-spinel CuFe2O4. The
nm which indicates the nanocrystalline nature of the sample bands around 215, 278, 481, 586, and 656 cm−1 are assigned to
and in the range of superparamagnetic limit. The lattice F2g (1), E g, F2g (2), F2g (3), and A1g, respectively,
parameter of the sample is calculated by taking consideration corresponding to the cubic ferrite structure. The appearance
of all peaks in the XRD pattern and is given by ∼8.2 nm. of additional Raman peaks may be due to the breakdown of the
2.2. FESEM and HRTEM Study. To have a deep insight momentum conservation rule because the excitation wave-
into the morphology of the nanocrystalline CuFe2O4, HRTEM length (632 nm) is much larger compared to particle diameter
images were taken and shown in Figure 3. During the HRTEM (∼9 nm).
Therefore, the number of Raman phonon modes found is
incompatible with cubic symmetry. From the observed Raman
spectra of CF, the nonappearance of the Raman mode
corresponding to α-Fe2O3 and Fe clusters implies that no
unnecessary impure phase is present in the sample. In the IR
spectra of CuFe2O4, there are two strong absorption bands at
about 490 cm−1 which correspond to M−O stretching
vibration and O−M−O bending vibration of CuFe2O4,
respectively.
Figure 3. (a) HRTEM image, (b) SAED pattern, and (c) fringe 2.4. Magnetic Study. To know about the magnetic
pattern of CF NPs. property of our sample, SQUID analysis under field-cooled
(FC) and zero field-cooled (ZFC) conditions was recorded in
observation of the SAED patterns, some representative the quantum design superconducting quantum interference
micrographs and typical lattice fringe patterns recorded are device (SQUID) at a constant dc magnetic field starting from
shown in Figure 3. The representative pattern of the 300 K down to 5 K. The M versus T curve is displayed in
micrograph having distribution of particle size of the CF Figure 5. The corresponding ZFC−FC magnetization curves in
sample is shown in Figure 3a. From this study, it is observed the temperature range of 5−300 K were recorded during
that the NPs are monodispersed of more or less spherical
shape with uniform size. The average crystallite size obtained
from the TEM micrograph is ∼9 nm. The SAED pattern of CF
is shown in Figure 3b. The lattice planes corresponding to CF
were detected in the SAED pattern, and these planes are also
assigned in Figure 3b. The clear rings with different diameters
(i.e., different lattice planes of CF) in Figure 3b point out the
polycrystalline nature of the CF sample. A clear lattice fringe
pattern of CF is shown in Figure 3c which indicates the well-
crystalline nature of the sample. In Figure 3c, the separations
between the consecutive parallel fringes are assigned and
marked according to the calculation, and the calculated values
are 2.53 and 2.10 Å and these correspond to the (311) and
(400) lattice planes of CF. The HRTEM study also ruled out
the existence of the unnecessary impurity phase in our CF
material (Figure 3b,c) which is consistent with XRD analysis.
2.3. IR and Raman Spectroscopy. We gathered
information on formation of the desired phase, existence of Figure 5. Temperature-dependent magnetization ZFC−FC curves for
any impurity, structural defects, crystallinity, and so forth from CF NPs.

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heating after cooling in the presence of an applied magnetic
field of 250 Oe. In addition, another comparatively higher field
of 250 Oe was applied to obtain a considerable difference
between the ZFC and FC magnetizations because this
difference was used for the evaluation of the average particle
size as well as the spin-glass-like phases present in the sample.
The ZFC−FC curves of CF are bifurcated below RT and
branched out prominently with decreasing temperature.
However, with decreasing temperature below 150 K, the
magnetic moment related to the ZFC curve decreases while
FC curve increases, and this forms a clear hump in ZFC−FC
curves. Below the freezing temperature, the system proceeds
into a glassy state and a strong irreversibility between the ZFC
and FC curve is shown in the M versus T curve, a typical
superparamagnetism (SPM) relaxation phenomenon of a SG-
or cluster-like system.22 Because our synthesized NPs have size
below 10 nm, it conversely indicates that the hump observed in
the ZFC and FC curves is indicating the presence of the SPM
blocked state of the NPs. This temperature corresponding to
this hump is called blocking temperature. For monodispersed
NPs, the maximum point in the ZFC curve and the bifurcation
point of FC and ZFC curves are very closely spaced. In
monodispersed NPs, usually the blocking condition is defined
by single temperature, but two temperatures (TB and TP) are
required to explain the blocking condition phenomenon for
distributed particles, where TB is considered as the highest
temperature at which the ZFC and FC magnetizations are
bifurcated corresponding to the larger group of NPs present.
Tp is the temperature corresponding to the peak obtained in
thermal variation of the ZFC magnetization. In fact, the ZFC
magnetization decreases below TP for the existence of tiny
particles along with lower TP than TB for such systems. In this
analysis, we have found TB is ∼300 K and that TP is near about
150 K (Figure 5). Possibly, this is due to the size distribution
of CF NPs.
The magnetic hysteresis behavior of the sample was
recorded in temperatures 300, 150, and 5 K as shown in
Figure 6. This figure exhibits a clear “S”-like symmetry. The
opening of the MH loop at lower temperatures results in the
ferromagnetic character. Apparently, the magnetic system
exhibits the coexistence of ferromagnetism and SG. The
magnetization becomes a nonlinear function of applied
magnetic field and shows ferromagnetic hysteresis nature in
the lower magnetic field range. The magnetization value of CF
Figure 6. Magnetic hysteresis loops of CF-NPs at 300, 150, and 5 K
temperatures.
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increases as the applied magnetic field increases. The
maximum magnetization that is saturation magnetization
(MS) of CF (at 5 T) is quite high as compared to other
copper ferrite NPs.23 As the temperature decreases, the
saturation magnetization increases, and the rise in magnet-
ization may be attributed to a variety of factors, namely,
freezing of uncompensated surface spins, enhancing ferrimag-
netic fraction by lowering the temperature, decreasing
nanocrystalline anisotropy, and so forth. The saturation
magnetizations of CF at 300, 150, and 5 K are found to be
6.6, 7.7, and 9.3 emu g−1, respectively. The high value of
saturation magnetization authenticates that our sample can be
emerged as a proper material for applications in soft magnetic
devices. Here, very low coercivity at RT confirms soft magnetic
nature of our sample. Also, with decreasing temperature, the
coercive field increases accordingly and is found to be ∼2800
Oe at 5 K temperature. At relatively low temperature, this huge
enhancement of coercivity is mainly due to the blocking of
single-domain NPs present in the soft magnetic system.
2.5. Heterogeneous Catalytic Click Chemistry. Huis-
gen 1,3-dipolar cyclo-addition reaction between terminal
alkynes with organic azides to afford 1,4-regioisomers of
1,2,3-triazoles is an example of copper(I)-catalyzed click
reaction and is known as CuAAC. The coupling product 1,4-
diaryl-1,2,3-triazoles have been recognized for its anticancer
activity.24 For the click reaction of alkynes and azides, a
number of homogeneous copper catalysts have been employed
though these were not applicable in practical cases. In spite of
important productivity, improved yield, high selectivity, and
simplicity of optimization of the reported homogeneous
catalysts, they have problems of product separation and
purification from the catalyst, which creates environmental
barriers to expand their scope, thus limiting their wide range of
use in a number of applications. Trace amounts of catalyst
removal from the end products is very important as metal
contamination can create toxicity, especially in the pharma-
ceutical industry. Even by means of careful utilization of several
methods such as chromatographic or distillation techniques,
the extraction or elimination of trace amounts of the catalyst
remains a challenge. Again, the utilization of heterogeneous
and recyclable catalysts and eco-benign solvents for the
coupling of three or more components in a single step is
highly important and exciting in green chemistry. The starting
reagents need not be completely soluble for the successful
reaction. The end product can be filtered from the solution
easily in many cases, as only the purification step is required.
The use of water as an economical and safer solvent has a lot of
advantages over expensive, combustible, and toxic organic
solvents, diminishing atmospheric pollution and ease of
separation of final products because most of the organic
compounds are insoluble in water. Under such conditions, the
heterogenization of click catalysis is an attractive alternative
because of the benefits of easy removal, recovery, and
reusability.
Metal NPs have received much attention as dynamic
catalysts for various organic conversions and, in particular,
because of enormous availability of copper(II) NPs, they have
gained very good impact in catalysis and biology. In recent
times, magnetically separable metal NPs have been industrial-
ized to show potential for immobilization with the applications
in catalytic transformations as readily available, very strong,
and high-surface area heterogeneous catalysts due to their ease
of separation after catalytic conversions to overcome time-
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consuming and difficult separation steps. Additionally, these higher temperature (Table 1, entry 1). When CuFe2O4 is
catalysts can be used to give the desired products in aqueous replaced by Fe2O3 in similar reaction conditions, trace amounts
conditions in very short reaction times with high yields. of yield of the product could be obtained (Table 1, entry 2).
Copper(I)-catalyzed azide−alkyne cycloaddition (CuAAC) Organic solvents such as dichloromethane, tetrahydrofuran,
is describe here with in situ generation of alkyl or aromatic diethyl ether, ethanol and so forth proved to be less effective or
azides from corresponding halide/boronic acid/epoxide and ineffective. When the temperature of the reaction is increased
sodium azide and subsequently their coupling with terminal to 80 °C, yield of the reaction is increased to 90% with reduced
and internal alkynes in the presence of CuFe2O4 NPs. The time (Table 1, entry 4). This reaction condition is found to be
click reaction of internal alkynes with azides, to afford optimized. In the optimized reaction condition, we are pleased
trisubstituted triazoles, is very challenging.13 However, in our to choose phenylboronic acid, tolyl boronic acid, styrene oxide,
hand, from the point of reactivity, there is no difference allyl bromide and 4-bromo benzyl bromide, and so forth as
between terminal and internal alkynes. They are showing very coupling partners (Table 2). Phenylacetylene can be replaced
similar reactivity with respect to yield and time. by 4-tert-butyl phenylacetylene, diphenylacetylene, o-nitro-
To evaluate the scope of synthetic applicability and phenyl propargyl ether, propargyl alcohol, amylacetylene, or
standardization, we selected benzyl bromide, sodium azide, 1 heptynyltrimethylsilyl acetylene.
and phenylacetylene as coupling partners for azide−alkyne 2.6. Recycling the Catalyst and Leaching. Recycling of
cycloaddition (AAC) reactions. To optimize this facile AAC the catalyst can be easily achieved for this AAC reaction. The
process, we struggled a lot and took several attempts. A typical magnetically separated and recovered catalyst was washed with
optimization for coupling of phenylacetylene with benzyl azide water and dichloromethane sequentially, dried, and used for
is described here. To optimize the catalyst, we used the next cycle. No significant loss of activity was found up to
commercial Fe2 O3 and sonochemically prepared nano the fifth cycle (Table 3).
CuFe2O4. We found that efficient coupling can take place A model reaction of phenylacetylene, benzyl bromide, and
only by CuFe2O4 (Table 1). Yield of the coupling product was NaN3 was designed to investigate catalyst leaching during the
reaction time. The reaction was carried out in optimized
Table 1. Results for Different Conditions on the AACa conditions. After half of the reaction time (90 min), the
catalyst was separated magnetically. The rest of the reaction
mixture (in the absence of the catalyst) was allowed to stir for
another 90 min. As seen, no triazole was produced after
catalyst removal. These results indicate that the catalyst is
perfectly heterogeneous and catalyst leaching is negligible
under these reaction conditions. In another experiment, the
entry catalyst solvent temp (°C) time (h) yield (%)
water extract of the reaction mixture after removal of the
1 H2O RT to 90 12 catalyst and organic layer was used for abovementioned model
2 Fe2O3 H2O RT to 90 12 reaction. However, trace amounts of the desired triazole
3 CuFe2O4 H2O RT 10 80 product were obtained. These experiments prove that there is
4 CuFe2O4 H2O 90 3 90 negligible amount of leaching of our catalyst.
5 CuFe2O4 C2H5OH 70 10 30
6 CuFe2O4 CH3CN 90 10 15
7 CuFe2O4 toluene 110 10 10
3. CONCLUSIONS
8 CuFe2O4 acetone 70 10 trace In this endeavor, we have presented the synthesis and
9 CuFe2O4 CH3OH 70 10 40 characterization of bifunctional spin-canted CuFe2O4 NPs for
10 CuFe2O4 DCM 50 12 trace use in magnetically separable heterogeneous catalytic green
11 CuFe2O4 THF 80 12 trace click chemistry. Phase pure, highly uniformed CuFe2O4 NPs
12 CuFe2O4 Dioxane 90 12 trace have been synthesized by the sonochemical method and
13 CuFe2O4 Et2O 70 12 trace identified by PXRD and Raman studies. The crystal structure
a
Conditions: halide (A) 4 mmol, NaN3 4 mmol, solvent 4 mL, and inverse nature of this spinel have been determined by the
catalyst (commercial Fe2O3/sonochemically prepared nano CuFe2O4) Rietveld refinement method. Field emission scanning electron
0.4 mmol, acetylene (B) 4 mmol. microscopy (FESEM) and HRTEM agree with the particle size
of ∼15.3 nm evaluated from the Debye−Scherrer formula. The
CuFe2O4 NPs show spin-canted behavior with the presence of
found to be maximum in aqueous solvent rather than miscible both superparamagnetic and ferrimagentic phases, and it shows
organic solvent. Our initial success began with the reaction of magnetic unsaturation even at 5 T. Because of its strong
benzyl bromide (4 mmol) and phenylacetelene (4 mmol) as magnetization, we have successfully applied the material for
reactants and CuFe2O4 as the catalyst (0.4 mmol, 10 mol %). magnetically separable heterogeneous catalysis for the three-
In the first step, benzyl bromide (4 mmol), sodium azide (4 component click chemistry in aqueous medium. A simple and
mmol), and CuFe2O4 (0.4 mmol) were mixed in water at RT efficient three-component green procedure has been developed
and stirred for 4 h. After consumption of benzyl bromide, by using the magnetically separable heterogeneous CuFe2O4
phenylacetylene (4 mmol) was added to the reaction mixture catalyst to synthesize 1,4 disubstituted 1,2,3-triazoles in
and stirred until it is completely consumed [thin layer excellent yield.
chromatography (TLC) monitoring, hexane/ethyl acetate =
9:1]. The overall yield of the reaction is found to be 80%
(Table 1, entry 3). A control reaction conducted in the same 4. EXPERIMENTAL DETAILS
reaction condition but in the absence of the catalyst gave no 4.1. Materials and Methods. Copper(II) chloride,
yield of the product despite prolonged reaction time and dehydrate, ferric(III) chloride, and hexahydrate were pur-
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Table 2. Substrate Scope of Catalyzed AACa
a
Conditions: boronic acid/epoxide/halide 4 mmol, NaN3 4 mmol,
solvent 4 mL H2O, CuFe2O4 0.4 mmol, acetylene 4 mmol, 80 °C.
chased from Merck Chemical Company. All other chemicals
used were of AR grade. Raman spectra in the wavenumber
range of 100−800 cm−1 of the spinel ferrite were recorded at
RT using a T64000 Raman spectrophotometer (J.Y. HORIBA)
fitted with an argon ion laser using 514.5 nm as the exciting
13850
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Table 3. Recycling of the Reagentsa
sl. no. cycle no. yield (%)
1 1st 90
2 2nd 88
3 3rd 86
4 4th 85
5 5th 84
a
Conditions: halide (A) 4 mmol, NaN3 4 mmol,H2O 4 mL, CuFe2O4
0.4 mmol, acetylene (B) 4 mmol.
radiation in the Raman spectrometer that interfaced with the
computer in the photon counting mode. The nanocrystalline
CuFe2O4 sample was characterized by the PXRD technique,
using a Bruker D8 ADVANCE diffractometer, with Cu Kα
radiation (λ = 1.5406 Å) in the range of 2θ = 10°−80° in steps
of 0.02°. To have an idea of microstructural information, the
samples were characterized by HRTEM (JEOL, JEM-2011,
operating at 200 kV, Japan with resolution = 1.9 Å). Static
magnetic measurements, namely, magnetic hysteresis loops
and temperature-dependent magnetization curves under ZFC
and FC conditions were carried out by a SQUID magneto-
meter (Quantum Design, MPMS XL-7) in the temperature
range of 5−300 K. Reactions were performed in oven-dried
glassware. 1H and 13C{1H} NMR spectra were recorded in
Bruker AVANCE III 400 and 300 MHz NMR spectrometers.
Chemical shifts (δ) are expressed in ppm using the residual
proton resonance of the solvent as an internal standard
(CHCl3: δ = 7.26 ppm for 1H spectra, 77.36 ppm for 13C{1H}
spectra, CHDCl2/CH2Cl2, 5.32 ppm; all coupling constants (J)
are expressed in hertz and only given for 1H−1H couplings.
The following abbreviations were used to indicate multiplicity:
s (singlet), d (doublet), t (triplet), dd (doublet of doublets), dt
(doublet of triplets), m (multiplet), bs (broad singlet), and bm
(broad multiplet).
4.2. Synthesis of CuFe2O4 NPs. Two separately prepared
100 mL solutions of CuCl2·2H2O and FeCl3 were mixed
together by intense ultrasonication for 30 min at RT. Now, 6 N
NaOH solution was added dropwise to the homogeneous
mixture to maintain pH ≈ 9 for precipitation. After 2 h,
complete coprecipitation was obtained, and then, the
coprecipitated particles were rigorously stirred for another 2
h. Finally, the coprecipitated particles were filtered by the
vacuum filtration method, and the residue was washed several
times by deionized triple distilled water and propanol to
neutralize the pH and remove extra ions. The filtered
coprecipitated particles were dried at 80 °C for 24 h in a
hot chamber and then it was annealed at 600 °C for 6 h in
vacuum to obtain the desired pure crystalline phase.
4.3. General Procedure for Catalytic 1,3-Dipolar
Cycloaddition. The catalytic reactions were carried out in a
glass batch reactor according to the following procedure. To a
stirred solution of the desired halide/epoxide/boronic acid (4
mmol) in 4 mL water, 4 mmol sodium azide and 0.4 mmol
CuFe2O4 were added, and the reaction mixture was stirred at
80 °C for 1 h and monitored continuously by TLC (hexane/
ethyl acetate = 9:1). The reactions were performed in open air.
After consumption of the starting material, acetylene (4 mmol)
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was added dropwise and stirred for 1−3 h. After completion of
the reaction mixture, the catalyst was separated and recovered
by a strong magnet, and the remaining mixture was diluted
with water and extracted with ethyl acetate thrice. The
combined organic layer was dried over anhydrous Na2SO4,
filtered, and concentrated to afford the crude material. The
crude material was then purified by column chromatography
(silica 100−200 mesh, ethyl acetate−hexane 5−10%) to afford
the desired triazole product (yield = 55−95%). The magneti-
cally separated and recovered catalyst was washed with water
and dichloromethane sequentially, dried, and used for the next
cycle.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsome-
ga.9b01477.
Analytical data and NMR spectra (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: uroccu@gmail.com. Phone: 9732657939 (U.K.R.).
ORCID
Ujjal Kanti Roy: 0000-0001-7567-8762
Author Contributions
The manuscript was written through contributions of all the
authors. All the authors have given approval to the final version
of the manuscript.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
U.K.R. acknowledges financial support of this work by SERB-
New Delhi, SR/FT/CS-137/2011 dated 12.07.2012, and
Science and Technology and Biotechnology-WB, 50(Sanc.)/
ST/P/S&T/15G-10/2018 dated 30.01.2019 to UKR is
gratefully acknowledged. U.K.R. acknowledges help from Dr.
Joyanta Choudhury (IISER Bhopal) and Dr. Sanjay Pratihar
(Tezpur University, now at CSIR Bhabnagar) for providing
instrumental facilities.
■ ABBREVIATIONS
CCR2, CC chemokine receptor 2; CCL2, CC chemokine
ligand 2; CCR5, CC chemokine receptor 5; TLC, thin layer
chromatography
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13852 DOI: 10.1021/acsomega.9b01477

ACS Omega 2019, 4, 13845−13852