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Challenges in chemical synthesis at the border of solution-based and solid-state chemistry—Synthesis and structure of [CH3CH2Ge9{Si(SiMe3)3}]2−

Nasim Kakesh

Soheil Sayyahi

Rashid Badri

lable at ScienceDirect
C. R. Chimie 21 (2018) 1023e1028Contents lists avaiComptes Rendus Chimie
www.sciencedirect.comFull paper/MemoireMagnetic nanoparticle coated with ionic organic networks: A
robust catalyst for Knoevenagel condensation
Nasim Kakesh a, b, Soheil Sayyahi c, *, Rashid Badri a
a Department of Chemistry, Ahvaz Branch, Islamic Azad University, Ahvaz, Iran
b Department of Chemistry, Khuzestan Science and Research Branch, Islamic Azad University, Ahvaz, Iran
c Department of Chemistry, Mahshahr Branch, Islamic Azad University, Mahshahr, Irana r t i c l e i n f o
Article history:
Received 4 May 2018
Accepted 13 September 2018
Available online 17 October 2018
Keywords:
Poly(ionic liquid)
Magnetic nanoparticles
Carbonecarbon bond
Knoevenagel condensation* Corresponding author.
E-mail address: sayyahi.soheil@gmail.com (S. Sa
https://doi.org/10.1016/j.crci.2018.09.009
1631-0748/© 2018 Académie des sciences. Publishea b s t r a c t
Novel poly(ionic liquid) coated magnetic nanoparticles (Fe3O4ePIL) were synthesized for
the first time and fully characterized by transmission electron microscopy, field-emission
scanning electron microscopy, energy-dispersive X-ray, thermogravimetricedifferential
thermal gravimetric (DTG), Fourier transform infrared, and vibrating sample magnetom-
etry (VSM) techniques. Then, the catalytic efficiency of Fe3O4ePIL was investigated in
Knoevenagel condensations of various aldehydes with malononitrile using ultrasonic
irradiation in aqueous medium. Fortunately, the catalyst showed pretty high activity and
reusability with no difference in reaction time.
© 2018 Académie des sciences. Published by Elsevier Masson SAS. All rights reserved.1. Introduction
To date, the attention from the research community for
developing nanocatalysis based on Earth-abundant transi-
tion metals including Mn, Fe, Co, Ni, and Cu and early
transition metals Ti, V, Cr, Zr, Nb, and W is explosively
growing [1]. Among them, Fe-based nanocatalysts are
generally robust, inexpensive, easy to prepare, nontoxic,
magnetically recoverable, and reusable and therefore have
attracted considerable interest and are used in awide range
of reactions such as MiyauraeSuzuki, Heck, Sonogashira,
Knoevenagel, Hiyama, alkyneeazide cycloaddition, hydro-
genation, reduction, oxidation, arylation, alkylation, epox-
idation of alkenes, multicomponent reactions, Fenton-like
reaction, and so forth [2,3].
Poly(ionic liquid)s (PILs) [4,5], or polymerized ionic
liquids, are a class of polyelectrolytes that comprise a
polymeric backbone and an ionic liquid species in mono-
mer repeating units. The architecture of PILs can be easily
redesigned by both the polymer backbone and outer ion.yyahi).
d by Elsevier Masson SAS. AThe chemical and mechanical properties of PILs can be
tuned not only by postpolymerization but also by in situ ion
exchange. Today, they are used in various applications
across a countless of fields, such as stimuli-responsive
materials, catalysis, precursor for carbon materials,
porous polymers, antimicrobial materials, separation and
absorption materials, and energy harvesting/generation as
well as several special interest applications [6e8]. In this
regard, merging physical and chemical properties of PILs
with magnetic nanoparticles (MNPs) has been efficiently
exploited in catalytic reactions [9e11].
The Knoevenagel condensation is the reaction between
an aldehyde or ketone and any compound having an active
methylene group [12]. Because of the mild reaction condi-
tions and its broad applicability, the Knoevenagel reaction is
awidely usedmethod for carbonecarbon bond formation in
organic synthesis with numerous applications in the syn-
thesis of fine chemicals, hetero-DielseAlder reactions, and
in the synthesis of carbocyclic as well as heterocyclic com-
pounds of biological significance [13,14]. Recently, a wide
range of studies using MNP-supported catalyst like
Fe3O4emethylene diphenyl diisocyanate-guanidine [15],
Fe3O4@SiO2-3N (where 3N ¼ N1-(3-trimethoxysilylpropyl)ll rights reserved.
N. Kakesh et al. / C. R. Chimie 21 (2018) 1023e10281024diethylenetriamine) [16], Fe3O4eBetti base [17],
Fe3O4ecysteamine hydrochloride [18], Fe3O4@SiO2@TiO2
[19], nano-NiFe2O4 [20], CoFe2O4 [21], and Fe3O4@propyl-
amine modified with imidazolium ionic moiety [22] have
been reported for Knoevenagel condensation. In continua-
tion of these studies, this present study reports on the
synthesis and characterization of a novel MNP coated with
ionic organic networks (Fe3O4ePILs) and its catalytic appli-
cation in the Knoevenagel condensation of aldehydes with
malononitrile.
2. Experimental section
2.1. Materials and instruments
All chemicals used in this work were commercially
available and used without further purification. Reactions
were monitored by thin-layer chromatography (TLC) per-
formed on 0.25 mm Merck TLC silica gel 60 F254 plates,
using UV light as a visualizing agent. The synthesized
Fe3O4ePIL composite was characterized through various
techniques. The Fourier transform infrared (FT-IR) spectra
(nmax) were recorded using a BOMEMMB-Series 1998 FT-IR
spectrometer and samples analyzed as a KBr disk and at a
scanning range of 4000e400 cm1. Scanning electron mi-
croscopy (SEM) analyses were carried out using Tescan
Mira 3 LMU instrument coupled with energy-dispersive X-
ray (EDX) spectroscopy at a potential of 15 kV with 1 nm
resolution for microanalysis and mapping of the Fe3O4ePIL
nanoparticles. The transmission electronmicroscopy (TEM)
image was recorded using a Zeiss-EM10C at 80 kV. The
magnetic properties were investigated using a vibrating
sample magnetometer (Meghnatis Daghigh Kavir Co,
Kashan, Iran) at room temperature. The thermal stability of
the Fe3O4ePIL composite was assessed using a PerkinElmer
Pyris diamond thermogravimetric analysisedifferential
thermal analysis (TGAeDTA) by heating the sample from
room temperature to 600 C at a heating rate of 10 Cmin1
under nitrogen.
2.2. Preparation of Fe3O4ePIL composite
By using the procedure analogous to that described by
Zhang et al. [23], the as prepared Fe3O4 MNPs (1 g) wereScheme 1. Synthesis of Fedispersed in DMSO (18 mL) by ultrasonic irradiation. Then,
1,3,5-tris(bromomethyl)benzene (2mmol, 0.357 g) and 1,4-
bis(imidazol-1-yl)-butane (3 mmol, 0.285 g) were added,
and the resulting mixture was heated under nitrogen
bubbling and reflux conditions to 80 C for 72 h. The MNPs
were collected by an external magnet, washedwith ethanol
(2  10 mL), and mixed with NaOAC (15 mL, 1 M) at room
temperature for 24 h. Finally, the composite was separated,
washed with deionized water, and dried in an oven at 50 C
for 24 h.
2.3. General procedure for the Knoevenagel condensation
using the Fe3O4ePIL nanocatalyst
In a vial equipped with a magnetic stirrer, aldehyde
(1 mmol), malononitrile (1 mmol), Fe3O4ePIL nonmagnetic
catalyst (0.05 g), and water (3 mL) were placed and soni-
cated for desired times. The progress of the reaction was
monitored via TLC. Upon completion of the reaction, the
catalyst was removed from the mixture with the aid of an
external magnet and the filtrate was transferred to a sep-
aratory funnel. Then, dichloromethane (10 mL) was added
and the obtained organic phase was separated and dried
with calcium chloride and removed in vacuo. Finally, the
residue was isolated by column chromatography on silica.
All products were known and confirmed by comparing
their physical and spectral datawith the authentic samples.
2.4. Reusability test of the Fe3O4ePIL nanocatalyst in the
Knoevenagel condensation
For this purpose and according to the general procedure,
the conversion of 4-nitrobenzaldehyde was selected as the
model and was performed under the same conditions for
seven consecutive times. After completion of the reaction
on each run, the catalyst was carefully separated and
washed with ethyl acetate (10 mL) and reused for the next
run. From the results, the reaction time increased with a
gentle slope from 10 to 12 min.
3. Results and discussion
In this work, the protocol regarded to synthesize the
catalyst is based on our previous experiments [24e27].3O4ePIL composite.
N. Kakesh et al. / C. R. Chimie 21 (2018) 1023e1028 1025First, the Fe3O4 nanoparticles were prepared by coprecipi-
tation method. Then, SN2 between 1,3,5-tris (bromo-
methyl)benzene and 1,4-bis (imidazol-1-yl)-butane was
used for the formation of ionic organic network coating
Fe3O4 cores, which act as a hard template generating
Fe3O4ePIL composite, followed by anion exchange with
sodium acetate to increase the basicity of the MNPs
(Scheme 1). We assumed that coating of the ionic organic
network onto Fe3O4 nanoparticles surface is achieved by
electrostatic attractions between positive charge of imida-
zolium rings and bromide or acetate anions with oxygen
and iron atoms in the magnetite crystals, respectively. Also,Fig. 1. TEM images of synthesized Fe3O4ePIL particles
Fig. 2. FESEM image and SEM-energy dispersive X-Ray spectroscopy (EDS) elethis modification not only prevents Fe3O4 particles from
agglomeration similar to the classic, Derjaugin-Landau-
Verwey-Overbeeketype coulombic repulsion model
[28,29], but also increases organophilicity of magnetic
particles.
Then, different physicochemical characterization tech-
niques were used to probe the structure of the
organiceinorganic composite.
To study the size and morphology of the nanoparticles,
Fe3O4ePILs were subjected to TEM and field-emission
scanning electron microscopy (FESEM). The TEM images
showed that Fe3O4ePIL particles have a nearly sphericalat the scale of 150 nm (left) and 40 nm (right).
mental mapping images of C, N, O, Fe, and Br in Fe3O4ePIL composite.
N. Kakesh et al. / C. R. Chimie 21 (2018) 1023e10281026shape with the size range almost less than 20 nm (Fig. 1). In
addition, dark Fe3O4 cores coated with the brighter PIL
layers can be visualized.
Fig. 2 presents the FESEM image of the synthesized
Fe3O4ePIL nanoparticles. As seen from the figure, the sur-
face is rough with wrinkles. The elemental mapping indi-
cated the good distribution of carbon (blue), nitrogen
(mustard), oxygen (green), iron (red), and bromine (cyan)
over the surface of Fe3O4ePIL composite.Fig. 3. EDX of Fe3O4eP
Fig. 4. TGeDTG analysis forThe EDS spectrum shows signals corresponding to C, N,
and Br in addition to Fe and O, which further prove the
presence of PIL on the surface of Fe3O4 particles (Fig. 3).
To investigate the thermal stability and determine
operating temperature range of PIL@Fe3O4, TGAwas carried
out (Fig. 4). The combined TGAeDTG curves show weight
loss from room temperature to 100 C, which is due to the
removal of physically adsorbed water and ethanol. Also,
weight loss from 200 to 350 C corresponding to theIL nanoparticles.
Fe3O4ePIL composite.
N. Kakesh et al. / C. R. Chimie 21 (2018) 1023e1028 1027decomposition of the PIL coated on Fe3O4 particles was
observed.
The FT-IR spectrum of the Fe3O4ePIL nanoparticles
showed various peaks corresponding to Fe3O4 and PIL
components (Fig. 5). The band at ~613 cm1 belonged to Fe-
O stretching vibration in the tetrahedral sites, which is
originally at ~585 cm1 in bare Fe3O4 and shifted after
coating of PIL on the MNP surface. Also, the peaks at ~3100
and ~2800e2950 cm1 and weak bands at ~1460 and
~1563 cm1 were associated with aromatic C-H, alkyl C-H,
C]C (the benzene ring), C]C and C]N (the imidazole
ring) stretching vibration, respectively [30]. In addition, the
band at ~1635 cm1 and a broad one at ~3383 cm1 can be
attributed to OeH stretching vibration of the deformation
vibrations of water molecules trapped in the Fe3O4 colloidal
particles and physisorbed water, respectively [31,32].
Room temperature magnetic properties of Fe3O4ePIL
nanoparticles and bare MNPs were investigated (Fig. 6).Fig. 5. FT-IR spectra of PIL (bottom), Fe3
Fig. 6. Hysteresis loops of MNPs (The superparamagnetic characteristics of the two samples
were proved because the M (H) hysteresis loops for the two
samples were completely reversible. Also, Fe3O4ePIL and
uncoated Fe3O4 nanoparticles presented saturation
magnetization values of about 50 and 90 emu g1, respec-
tively. This decrease is attributed to the coating of
nonmagnetic PIL over MNPs.
It has been observed that ultrasound as an alternative to
conventional energy sources reduces the reaction temper-
ature and higher reaction rates can be achieved under
ambient conditions [33]. Also, water is the safest of all
solvents and is favorable from green chemistry viewpoint.
Thus, a strong collaboration between ultrasonic irradiation
and aqueous medium holds the key to the development of
an environmentally sustainable protocol [34].
Accordingly, we investigate the reaction of 4-nitro-
benzaldehyde with malononitrile under ultrasonic condi-
tion inwater. To our delight, products were obtained in 94%O4 (middle), and Fe3O4ePIL (top).
left) and Fe3O4ePIL (right).
Table 1
Knoevenagel reaction of aromatic aldehydes catalyzed by Fe3O4ePIL in
water under ultrasound condition.
Entry Aldehyde Yield (%)a
1 Benzaldehyde 92
2 4-Nitrobenzaldehyde 94, Trace,b 30,c 65,d 45e
3 4-Bromobenzaldehyde 92
4 4-Hydroxybenzaldehyde 82
5 4-Cyanobenzaldehyde 92
6 4-Fluorobenzaldehyde 91
7 4-Chlorobenzaldehyde 94
8 2-Furaldehyde 91
9 4-Methoxybenzaldehyde 83
10 2,4-Dichlorobenzaldehyde 86
11 4-Methylbenzaldehyde 80
12 2-Chlorobenzaldehyde 85
13 2,4-Dimethoxybenzaldehyde 77f
14 3-Nitrobenzaldehyde 94
15 4-(Dimethylamino)benzaldehyde 72
a Yields refer to chromatographically pure material.
b Without catalyst.
c 0.02 g of the catalyst.
d Five minutes.
e Under reflux condition.
f Fifteen minutes.
Fig. 7. Separation of the MNPs from reaction media with an external
magnet.
N. Kakesh et al. / C. R. Chimie 21 (2018) 1023e10281028yield when 0.05 g of Fe3O4ePIL catalyst was used (more
details on optimization of the reaction conditions are pro-
vided in Table 1, entry 2). With the knowledge of optimized
reaction conditions, a series of substituted aldehydes with
electron-donating and electron-withdrawing groups were
investigated in the Knoevenagel condensation and fortu-
nately provided excellent yields (Table 1, entries 1e15).
Recovery and reusability of the catalyst without losing
its activity is an important feature of the use of MNPs as a
catalyst support in organic synthesis [35e37]. This feature
was successfully investigated (Fig. 7 and Section 2).4. Conclusions
To the best of our knowledge, this is the first synthetic
report of the poly ionic network coated on MNPs. This new
nanocomposite presented high catalytic activity and
robustness for the Knoevenagel condensation reaction in
addition to easy magnetic separation and filtration, and
recyclability. The catalyst could be recycled seven times
without significant loss of activity.
Acknowledgments
We are sincerely grateful to the Ahvaz Branch, Islamic
Azad University, for the financial support of this project.
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Magnetic nanoparticle coated with ionic organic networks: A robust catalyst for Knoevenagel condensation

Ivana Šagud

Irena Škorić

Marija Šindler-Kulyk

Excited state transformations of heterostilbenes: Pathways to polycyclic skeleta

Not a member yet

Theoretical study of Sn adsorbed on the MgO(100) surface with defects

Reprogramming the chemical reactivity of iron in cancer stem cells

Recent trends in perfluorinated sulfoximines

Editorial Board - French

Design and development of several polymeric metal–organic frameworks, spectral characterization, and their antimicrobial activity

One-pot four-component domino strategy for the synthesis of novel spirooxindole–pyrrolidine/pyrrolizidine-linked 1,2,3-triazole conjugates <i>via</i> stereo- and regioselective [3+2] cycloaddition reactions: <i>In vitro</i> antibacterial and antifungal studies

Sommaire / Contents

Challenges in chemical synthesis at the border of solution-based and solid-state chemistry—Synthesis and structure of [CH<sub>3</sub>CH<sub>2</sub>Ge<sub>9</sub>{Si(SiMe<sub>3</sub>)<sub>3</sub>}]<sup>2−</sup>

Magnetic nanoparticle coated with ionic organic networks: A robust catalyst for Knoevenagel condensation

Excited state transformations of heterostilbenes: Pathways to polycyclic skeleta

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