Ultrasonics Sonochemistry 23 (2015) 208–211
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Ultrasonics Sonochemistry
journal homepage: www.elsevier.com/locate/ultson
Ultrasonic irradiation assisted syntheses of one-dimensional
di(azido)-dipyridylamine Cu(II) coordination polymer nanoparticles
Ahmad Morsali a, Hassan Hosseini Monfared a, Ali Morsali b,⇑, Christoph Janiak c
a
Department of Chemistry, Zanjan University, P.O. Box 45195-313, Zanjan, Islamic Republic of Iran
Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, P.O. Box 14115-175, Tehran, Islamic Republic of Iran
c
Institut für Anorganische Chemie und Strukturchemie Universität Düsseldorf Universitätsstr. 1, D-40225 Düsseldorf, Germany
b
a r t i c l e
i n f o
Article history:
Received 26 April 2014
Received in revised form 8 June 2014
Accepted 8 June 2014
Available online 16 June 2014
Keywords:
Coordination polymer
Sonochemistry
Nano-structure
2,20 -Dipyridylamine
a b s t r a c t
The Cu(II) coordination polymer, [Cu(dpa)(N3)2]n (1), has been synthesized by the reaction of 2,20 -dipyridylamine (dpa) and a mixture of Cu(ClO4)26H2O and sodium azide under ultrasonic irradiation. The
products were characterized by infrared (FT-IR) spectroscopy, X-ray powder diffraction, and scanning
electron microscopy (SEM). The CuO nano particles were prepared from calcination of compound 1 at
873 K. The CuO nanoparticles were characterized by X-ray powder diffraction (XRD), scanning electron
microscopy (SEM). This study demonstrates that sonochemistry is a suitable method for the preparation
of coordination polymer nano-structures and that the calcination temperature can be an effective parameter to control the size of CuO nano-structures prepared by direct calcination of a coordination polymer.
Ó 2014 Elsevier B.V. All rights reserved.
1. Introduction
The design and construction of coordination polymers is of current interest in the field of supramolecular chemistry and crystal
engineering owing to their potential applications as well as their
structural variations that are currently of interest in the field of
materials [1–3]. Coordination polymers with different metal ions
and ligands incorporated, solvent and counter ions can be designed
and have led to a wide range of potential applications in molecular
adsorption, catalysis, magnetism, luminescence, nonlinear optics,
and molecular sensing that are not found in mononuclear compounds [4–10]. Copper(II) coordination polymers are of considerable interest because of their structural and photoluminescent
biological function, catalytic, luminescence and magnetic properties [11]. Hence design and construction of coordination polymers
in size and morphologies of nanostructured materials can be interest in the field of materials of basic sciences as well as applied technology [12–17]. CuO is important as a semiconductor showing
narrow band gaps and has also been appealing to heterogeneous
catalysis [18–21]. CuO is an oxidation reduction catalyst which is
applied in organic chemistry catalysis, high-critical-temperature
(high-Tc) superconductors [22], gas sensors [23], and steam
reforming [24]. Recently organic compounds like tetrahydrobenzofurans and benzoheterocyclic compounds were
⇑ Corresponding author. Fax: +98 2182884416.
E-mail address: [email protected] (A. Morsali).
http://dx.doi.org/10.1016/j.ultsonch.2014.06.005
1350-4177/Ó 2014 Elsevier B.V. All rights reserved.
synthesized using a CuO nano catalyst [25,26]. These organic compounds are important and of interest in the field of pharmaceutical
applications [27–30]. Several methods are available to prepare CuO
nanoparticles. These methods include the metal organic chemical
vapor deposition (MOCVD) [31], a wet-chemistry route [32], sonochemical preparation [33], and solid-state reaction in the presence
of a surfactant [34]. However the use of supramolecular complexes
as precursors for the preparation of inorganic nano materials has
not yet been investigated thoroughly. This article focuses on the
preparation and description of the Cu(II) compound,
[Cu(dpa)(N3)2]n (1) and its conversion into nanostructured CuO
by calcination at 873 K under air atmosphere.
2. Experimental
2.1. Materials and physical techniques
All reagents and solvents for the synthesis and analysis were
commercially available and used as received. Elemental analyses
(C, H, and N) were performed on a Perkin–Elmer 2400 CHN Elemental Analyzer. X-ray powder diffraction (XRD) measurements
were performed using an X’pert diffractometer of Philips Company
with monochromatized CuKa radiation (k = 1.54056 Å). The samples were characterized with a scanning electron microscope
(SEM) (Philips XL 30) with gold coating. IR spectra were recorded
on a SHIMADZU-IR460 spectrometer in a KBr matrix. Particles
size distribution histogram has been drawn using a manual
A. Morsali et al. / Ultrasonics Sonochemistry 23 (2015) 208–211
microstructure distance measurement program. Ultrasonic generation was carried out on a TECNO-GAZ, S.p.A., Tecna 6, input: 50–
60 Hz/305 W.
2.2. Preparation of [Cu(dpa)(N3)2]n (1)
Compound 1 was prepared according to the literature [35], from
the ligand dpa (0.0855 g, 0.5 mmol), and a mixture of Cu(ClO4)2
6H2O (0.0186 g, 0.5 mmol) and sodium azide (0.0065 g, 1.0 mmol).
The resulting light blue powder was filtered off, washed with
methanol and dried at 60 °C Yield 65%. M.p. 217–219 °C. The formation of compound 1 was confirmed by X-ray powder diffraction,
infra-red spectroscopy and elemental analysis. Anal Calc. for CuC10
H9N9: C, 37.68; H, 2.85; N, 39.54. Found: C, 37.65;H, 2.89; N, 39.49.
IR bands (cm1): 3342 w, 2082 vs, 2036 vs,1635 m, 1590 m,
1527 m, 1481 s, 1434 w, 1415 w, 1234 m, 1166 m,1016 m, 910w,
761 m.
209
(EO) N3 ion in N:N mode with another N3 as terminal ligand. The
Cu–N distances are 2.030 and 2.371 Å, and the Cu–N3–Cu angle
is 124.11°. The intra-chain Cu. . .Cu distance is 3.890 Å, which is
rather large compared to other Cu(II) compounds with azido
anions bridging in an end-on mode between two equatorial positions [35]. The end-on azido bridges and the terminal azides are
almost linear with bond angles of \N4-N5-N6 = 178.6° and \N7N8-N9) = 178.3°. The bond lengths of N4-N5, N5-N6, N7-N8, and
N8-N9 (1.203, 1.147, 1.182, and 1.157 Å, respectively) are approximately equal to each other, and the longer bonds involving the
nitrogen atom are linked to the Cu(II) ions. This is consistent with
2.3. Preparation of [Cu(dpa)(N3)2]n (1) as nano-structures
In order to synthesize compound 1 in nanostructured form
Cu(ClO4)26H2O (0.0148 g, 0.4 mmol) in 10 mL ethanol was added
to 0.069 g (0.4 mmol) (dpa) and sodium azide (0. 065 g, 1.0 mmol)
under ultrasound irradiation for 1 h at 25 °C. These pellet-like
nano-particles were separated from the solution by centrifugation,
washed with ethanol and dried at 60 °C. Yield 75%. M.p. 217–
219 °C. Anal Calc. for CuC10H9N9: C, 37.68; H, 2.85; N, 39.54. Found:
C, 37.66; H, 2.85; N, 39.46. IR bands (cm1): 3342 w, 2082 vs,
2036 vs,1635 m, 1590 m, 1527 m, 1481 s, 1434 w, 1415 w,
1234 m, 1166 m,1016 m, 910w, 761 m. The formation of nanoparticles with the composition of 1 was confirmed by infrared spectroscopy, elemental analysis and powder XRD analyses. The SEM
photograph shows pellet-like morphology for these particles
(Fig. 4b).
2.4. Preparation of CuO nanoparticles
The precursor 1 (0.0318 g, 0.1 mmol) obtained under the upper
mentioned conditions was calcinated at 873 K in a furnace and static atmosphere of air for 4 h. At the end of the reaction, a black precipitate was formed. The dark solid was washed with ethanol and
dried under nitrogen. The CuO nanoparticles were characterized by
powder X-ray diffraction (XRD) and scanning electron microscopy
(SEM).
Fig. 2. IR spectra of (a) nano-particles of compound 1 produced by sonochemical
method, (b) bulk material of compound 1.
3. Results and discussion
A one-dimensional coordination polymer, [Cu(dpa)(N3)2]n (1),
dpa = 2,20 -dipyridylamine has been synthesized by sonochemical
conventional solution chemistry under ambient conditions and
under sonochemical conditions. The crystal structure of compound
1 (Fig. 1) shows that the Cu(II) ions are bridged by a single end-on
Fig. 1. The uniform EO-N3 bridged chain of 1 with the atom-labeling.
Fig. 3. XRD patterns: (a) simulated pattern based on single crystal data of
compound 1, (b) measured pattern of nano compound 1 prepared by sonochemical
process.
210
A. Morsali et al. / Ultrasonics Sonochemistry 23 (2015) 208–211
Fig. 6. XRD pattern of CuO nanostructure prepared by calcination of compound 1 at
873 K.
Fig. 4. SEM photographs of (a) synthesized compound 1 without using ultrasound
irradiation, (b) compound 1 nano-structure prepared using ultrasound method.
the structural results obtained with other end-on azido bridged
complexes [36].
The IR spectrum of the complex displays characteristic bands of
bridging azide. In the region expected for the mas-(N3) absorption,
compound 1 exhibits two well-separated neighboring sharp and
strong bands in the 2100–2030 cm1 range, attributable to the
presence of two kinds of azide in compound 1. The IR spectrum
of nano-structured compound 1 produced by the sonochemical
method is very similar to that of the conventionally prepared compound 1 (Fig. 2). The IR spectra of the nano-structures and of the
single crystalline material show the same characteristic absorption
bands for the dpa and N
3 anion.
Fig. 3 shows the simulated XRD pattern from single crystal
X-ray data (see below) of compound 1 (Fig. 3a) and the comparison
Fig. 7. SEM photographs from CuO nanoparticles prepared by calcination of
compound 1 at 873 K.
with the XRD pattern of the typical sample of compound 1 prepared by the sonochemical process (Fig. 3b). Acceptable matches,
with slight differences in 2h, were observed between the simulated
and experimental powder X-ray diffraction patterns. This indicates
that the compound obtained by the sonochemical process as nanoparticles is identical to the investigated single crystal.
The morphology and size of compound 1 prepared by the sonochemical method was investigated by Scanning Electron Microscopy (SEM). Fig. 4a shows SEM images of the precipitate of
Fig. 5. Particle size histograms of compound 1 nanoparticles prepared by ultrasound method.
A. Morsali et al. / Ultrasonics Sonochemistry 23 (2015) 208–211
211
Fig. 8. Particle size histogram of CUO nanoparticles prepared by calcination of compound 1 at 873 K.
compound 1 prepared without sonochemical method which exhibits non-spherical particles that are not well separated and larger
particles up to several micrometers in size.
The image in Fig. 4b shows the SEM image of nanoparticles prepared by ultrasound irradiation As can be seen, nanometer scale
particles are obtained, albeit with large size distribution. Still, the
size of particles produced with ultrasound is smaller than the ones
prepared without sonication. The distribution histogram of the
nanoparticles has been extracted using a manual microstructure
measurement program and yields particles with sizes of about
25–75 nm (Fig. 5).
Fig. 6 shows the XRD pattern of the residue obtained from calcination of compound 1 prepared by ultrasound irradiation. The
pattern matches with the standard pattern of monoclinic CuO with
the lattice parameters (a = 4.6883(4), b = 3.4229(2), c = 5.1319(3),
space group C2/c and Z = 4, (JCPDS card number 48-1548). An
SEM image of the residue which is obtained from the calcination
of nano-sized compound 1 prepared by the sonochemical process
at 873 K shows the formation of agglomerated CuO nanoparticles
(Fig. 7). Fig. 8 shows the size distribution of CuO nanoparticles with
sizes of about 50–90 nm.
4. Conclusion
Nanoparticles of a Cu(II)-azido coordination polymer with
dipyridylamine ligand, [Cu(dpa)(N3)2]n (1) have been synthesized
via ultrasound irradiation and characterized by IR, powder XRD
and scanning electron microscopy (SEM). The nanoparticles of
compound 1 were used for preparation of CuO nanoparticles by
direct calcination. CuO nanoparticles were characterized by powder X-ray diffraction and scanning electron microscopy. In all cases
the products have suitable separation and distribution size.
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
[28]
Acknowledgement
This work was supported by the Zanjan and Tarbiat Modares
Universities.
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