Ultrasonics Sonochemistry 35 (2017) 502–513

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Ultrasonics Sonochemistry
journal homepage: www.elsevier.com/locate/ultson

Ultrasonic synthesis of two new zinc(II) bipyridine coordination

nano-particles polymers: New precursors for preparation of zinc(II)
oxide nano-particles
Mohammad Jaafar Soltanian Fard a,⇑, Payam Hayati b, Azita Firoozadeh a, Jan Janczak c
a
Department of Chemistry, Faculty of Chemical Science, Firoozabad Branch, Islamic Azad University, P.O. Box 74715-117, Firoozabad, Fars, Iran
b
Department of Chemistry, Dashtestan Branch, Islamic Azad University, Borazjan, Iran
c
Institute of Low Temperature and Structure Research Polish Academy of Sciences, P.O. Box 1410 Okolna 2 Str., 50-950 Wroclaw, Poland

a r t i c l e i n f o a b s t r a c t

Article history: Nanoparticles of two zinc(II) coordination polymers (CPs), [Zn(l-4,40 -bipy)Cl2]n (1) and [Zn(l-4,40 -bipy)
Received 16 October 2016 Br2]n (2) L = bpy = 4,40 -bipyridine ligand, have been synthesized by use of a sonochemical process and
Received in revised form 4 November 2016 characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRPD), Fourier trans-
Accepted 5 November 2016
form infrared spectroscopy (FTIR) spectroscopy and elemental analyses. The single crystal X-ray data
Available online 7 November 2016
of compounds 1 and 2 imply that the Zn+2 ions are four coordinated. Topological analysis shows that
1D coordination networks of 1 and 2 can be classified as underlying nets of topological types 2C1.
Keywords:
Nanoparticles of zinc(II) oxide have been prepared by calcination of two different zinc (II) CPs at
Nanoparticles
Zinc(II) oxides
450 °C that were characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRD)
Coordination polymer and IR spectroscopy.
Ultrasonic Ó 2016 Elsevier B.V. All rights reserved.
Crystal

1. Introduction are controlled through the large number of surface molecules,

Over the last 10 years the field of coordination polymers (CPs)
have seen a significant expansion in research efforts [1]. Briefly,
these materials consist of inorganic metal centers assembled by
means of multifunctional polydentate organic ligands. These
hybrid materials display a range of topologies caused by these pair-
ings, including one-, two-, and three-dimensional networks [2–4].
The considerable interest is driven by the affect basic structural
chemistry as well as by possible applications in a number of fields
such as catalysis, molecular adsorption, luminescence, magnetism,
nonlinear optics, and molecular sensing that are not found in
mononuclear compounds [5–7]. Zinc(II) is really a well-known
metal with a variety of applications in numerous areas. However,
zinc has been used for the fabrication of CPs [8–14]. The d10 config-
uration in the Zn(II) ion is assigned to a flexible coordination envi-
ronment to ensure that different geometries can be generated to
tailor-made materials. The CPs in this metal ion can be synthesized
[9].
Nanometer-sized particles of metal coordination polymers
(MCPs) are fascinating to explore, since their unique properties
⇑ Corresponding author.
E-mail addresses: mohammadjaafar_soltanian@yahoo.com, Mj.soltanian@iauf.
ac.ir (M.J.S. Fard).
which experience an entirely different environment than those in
a bulk crystal. Controlling the growth and development of materi-
als at the submicrometer scale is of central importance in the
emerging field of nanotechnology [15–20]. Although considerable
effort has been dedicated to the controlled synthesis of nanoscale
particles of metals, oxides, sulfides, and ceramic materials, little
attention was focused to up to now on nanoparticles of
supramolecular compounds such as CPs.
Sonochemistry is the research area in which molecules undergo
a reaction as result of the application of powerful ultrasound radi-
ation (20 KHz–10 MHz) [21]. In comparison to traditional tech-
niques, sonochemical method is more efficient and easily
controlled and this has been widely used to fabricate nano-sized
structures of various compounds [22–31]. ZnO is a polar inorganic
crystalline material with many different applications due to its
unique combined interesting properties such as non-toxicity, good
electrical, optical and piezoelectric behavior, stability in the hydro-
gen plasma atmosphere and low price [32–35]. ZnO is a well-
known semiconductor with a wide direct band gap (3.37 eV) and
a large exciton binding energy of 60 meV at room temperature
[36,37] and contains a wide range of applications such as solar
cells, luminescent, electrical and acoustic devices, gas and chemical
sensors, coatings, catalysts, micro lasers, memory arrays and
biomedical applications [38]. Up to now, many methods have been

http://dx.doi.org/10.1016/j.ultsonch.2016.11.009
1350-4177/Ó 2016 Elsevier B.V. All rights reserved.
 M.J.S. Fard et al. / Ultrasonics Sonochemistry 35 (2017) 502–513 503

Table 1 designed to synthesize zinc(II) oxide nano-crystals including vapor

Crystal data and structures refinement for ZnCl2(l-4,4-bpy)]n (1) and [ZnBr2(l-4, phase growth [39], vapor-liquid-solid process [40],soft chemical
40 -bipy)]n (2).
method [41], electrophoretic deposition [42], sol-gel process [43],
Empirical formula C10H8Cl2N2Zn C10H8Br2N2Zn homogeneous precipitation [44–45], etc.
Formula weight 292.45 381.37 In this manuscript, we certainly have designed a simple sono-
Temperature 295(2) K 295(2) K
Wavelength 0.71073 Å 0.71073 Å
chemical process to make nano-CPs of [Zn(l-4,40 -bipy)Cl2]n (1)
Crystal system Orthorhombic Monoclinic and [Zn(l-4,40 -bipy)Br2]n (2), Also these compounds were used
Space group P nma C2/c for preparation of ZnO nanoparticles.
Unit cell dimensions a = 17.407(3) Å, a = 15.996(3) Å,
a = 90.00° a = 90.00°
b = 12.463(2) Å, b = 5.4260(10) Å, 2. Experimental
b = 90.00° b = 113.440(10)°
c = 5.138(1) Å, c = 15.018(2) Å,
c = 90.00° c = 90.00° 2.1. Materials and physical techniques
Volume 1114.7(3) Å3 1195.9(4) Å3
Z 4 4 All reagents and solvents for the synthesis and analysis were
Density (calculated) 1.63631 g/cm3 1.61252 g/cm3 commercially available from Merck Company and used as received.
Absorption coefficient 2.647 Mg/m3 8.703 Mg/m3
F(0 0 0) 584.0 728.0
Methanol was used to prepare solutions. A multi wave ultrasonic
Crystal size 0.29  0.27  0.18 mm3 0.28  0.27  0.22 mm3 generator (Sonicator_3000; Misonix, Inc. Farmingdale, NY, USA),
Theta range for data 2.33–29.4° 3.595–25.582° equipped with a converter/transducer and titanium oscillator
collection (horn), 12.5 mm in diameter, operating at 20 kHz with a maximum
l 2.647 mm1 8.703 mm1
power output of 600 W at room temperature for 1 h, was used for
Index ranges 21 6 h 6 24 21 6 h 6 21
16 6 k 6 12 7 6 k 6 7 the ultrasonic irradiation. IR spectra were recorded using Perkin-
6 6 l 6 6 20 6 l 6 20 Elmer 597 and Nicolet 510P spectrophotometers. Microanalyses
(sin h/k)max 0.691 Å1 0.696 Å1 were carried out using a Heraeus CHN-O- Rapid analyzer. Melting
Theta (max) 29.4° 29.7° points were measured on an Electrothermal 9100 apparatus. X-ray
Radiation type Mo Ka Mo Ka
Refinement method Full-matrix least- Full-matrix least-
powder diffraction (XRD) measurements were performed using an
Goodness-of-fit on F2 squares on F2 squares on F2 X’pert diffractometer of Philips company with monochromated
1.027 1.001 Cuka radiation (k = 1.54056 Å). Simulated XRD powder pattern
Refinement R[F2 > 2r(F2)] = 0.037 R[F2 > 2r(F2)] = 0.048 based on single crystal data were prepared using Mercury software
wR(F2) = 0.080 wR(F2) = 0.105
[46]. The crystallite sizes of selected samples were estimated
S = 1.00 S = 1.00
Rint 0.0245 0.0713 using the Scherrer method. The samples were characterized
Largest diff. peak +0.885, 0.299 eA3 +0.505, 0.477 eA3 with a scanning electron microscope (SEM) (Philips XL 30) with
and hole 1454614 1456476 gold coating.
CCDC No.

2.2. Synthesis of [Zn(l-4,40 -bipy)Cl2] (1) as single crystal

Table 2
Selected bond lengths/A° for compound ZnCl2(l-4,4-bpy)]n. Zinc (II) nitrate (1 mmol, 0.189 g), 4,40 -bipyridine (1 mmol,
Zn—N(1) 2.060(3) C(3)—C(2)II 1.374(4) 0.156 g), and potassium chloride (2 mmol, 0.149 g) were loaded
Zn—N(2)I 2.065(3) C(3)—C(4) 1.491(5) into one arm of a branch tube and both of the arms were filled
Zn—Cl(1) 2.2171(9) C(4)—C(5)II 1.365(4) slowly by methanol. The chemical bearing arm was immersed in
Zn—Cl(1)II 2.2171(9) C(4)—C(5) 1.365(4)
an oil bath kept at 60 °C. Crystals were formed on the inside surface
N(1)—C(1) 1.325(3) C(5)—C(6) 1.375(4)
N(1)—C(1)II 1.325(3) C(5)—H(5) 0.9300 of the arm kept at ambient temperature, After 3 days, colorless
C(1)—C(2) 1.370(4) C(6)—N(2) 1.299(3) crystals were deposited in the cooler arm were filtered off, washed
C(1)—H(1) 0.9300 C(6)—H(6) 0.9300 with water and air dried.
C(2)—C(3) 1.374(4) N(2)—C(6)II 1.299(3)
Compound 1: White crystals, m.p. 292 °C. Analysis: found C:
C(2)—H(2) 0.9300 N(2)—ZnIII 2.065(3)
41.47, H: 2.38, N: 9.15%; calculated for C10H8 Cl2N2Zn; C: 41.07,
Symmetry transformations used to generate equivalent atoms: (i) 0.5 + x, y, H: 2.75, N: 9.57%). IR (cm1) selected bands: m = 809(vs), 1070(s),
0.5z; (ii) x, 0.5y, z; (iii) 0.5 + x, y, 0.5z.
1220(s), 1455(vs), 1493(s), 1589(vs), 3020(s), 3427(m).

CH3OH calcination
nano-structure of compound 1
by the ultrasound

Zn(NO3)2 + 4,4'-bpy + KCl nano structure ZnO

CH3OH
suitable single crystals of compound 1
by the branched
tube method

CH3OH calcination
nano-structure of compound 2
by the ultrasound
Zn(NO3)2 + 4,4'-bpy + KBr nano structure ZnO
CH3OH
suitable single crystals of compound 2
by the branched
tube method

Scheme 1. Materials produced and synthetic methods.

504 M.J.S. Fard et al. / Ultrasonics Sonochemistry 35 (2017) 502–513
2.3. Synthesis of [Zn(l-4,40 -bipy)Br2] (2) as single crystal
Zinc (II) nitrate (1 mmol, 0.189 g), 4,40 -bipyridine (1 mmol,
0.156 g), and potassium bromide (2 mmol, 0.238 g) were loaded
into one arm of a branch tube and both of the arms were filled
slowly by methanol. The chemical bearing arm was immersed in
an oil bath kept at 60 °C. Crystals were formed on the inside surface
of the arm kept at ambient temperature, After 5 days, colorless
crystals were deposited in the cooler arm were filtered off, washed
with water and air dried.
Compound 2: White crystals, m.p. 381 °C. Analysis: found C:
31.77, H: 1.96, N: 7.46%; calculated for C10H8 Br2N2Zn; C: 31.49,
H: 2.11, N: 7.34%. IR (cm1) selected bands: m = 807(vs), 1074(s),
1218(s), 1455(vs), 1493(s), 1590(vs), 3024(s), 3421(m).
2.4. Synthesis of [ZnCl2(l-4,40 -bpy)]n (1) nano-structures under
ultrasonic irradiation
High-density ultrasonic probe immersed directly into the solu-
tion of Zinc (II) nitrate (10 mL, 0.1 M) in methanol, then into this
solution, a proper volume of 4,40 -bipyridine ligand and potassium
chloride in methanol solvent (10 mL, 0.1 M) was added in a drop
wise manner. The solution was irradiated by sonochemical with
the power of 60 W and temperature 50 °C for 1 h. The obtained
precipitates were filtered, subsequently washed with water and
then dried.
2.5. Synthesis of [ZnBr2(l-4,40 -bpy)]n (2) nano-structures under
ultrasonic irradiation
High-density ultrasonic probe immersed directly into the solu-
tion of Zinc (II) nitrate (10 mL, 0.1 M) in methanol, then into this
Fig. 1. The coordination environment of Zn+2 cation environment in compound ZnCl2(l-4,4-bpy)]n (up) and in compound [ZnBr2(l-4,40 -bipy)]n (down).
solution, a proper volume of 4,40 -bipyridine ligand and potassium
bromide in methanol solvent (10 mL, 0.1 M) was added in a drop
wise manner. The solution was irradiated by sonochemical with
the power of 60 W and temperature 50 °C for 1 h. The obtained
precipitates were filtered, subsequently washed with water and
then dried.
Compound 1: m.p. 292 °C. Analysis: found C:41.27, H:2.13,
N:9.05%; IR(cm1) selected bands: m = 809(vs), 1070(s), 1220(s),
1455(vs), 1493(s), 1589(vs), 3020(s), 3427(m).
Compound 2: m.p. 381 °C. Analysis: found C:31.49, H:1.78,
N:7.04%; IR(cm1) selected bands: m = 807(vs), 1074(s), 1218(s),
1455(vs), 1493(s), 1590(vs), 3024(s), 3421(m).
2.6. X-ray single crystal measurements
Colorless single crystals of 1 and 2 were used for data collection
on a four-circle KUMA KM4 diffractometer equipped with a
two-dimensional CCD area detector. The graphite monochroma-
tized MoKa radiation (k = 0.71073 Å) and the x-scan technique
(Dx = 1°) were used for data collection. Data collection and reduc-
tion, along with absorption correction, were performed using the
CrysAlis software package [47]. The structures were solved by
direct methods using SHELXS-97 revealing the positions of almost
all non-hydrogen atoms [48]. The remaining atoms were located
from subsequent difference Fourier syntheses. The structures were
refined using SHELXL-2014 with the anisotropic thermal displace-
ment parameters [49]. The hydrogen atoms of the aromatic ring
were refined with the riding model. Details of the data collection
parameters, crystallographic data and final agreement parameters
are collected in Table 1. Selected geometrical parameters are listed
 M.J.S. Fard et al. / Ultrasonics Sonochemistry 35 (2017) 502–513
in Table 2. Visualization of the structures was made with the Dia-
mond 3.0 program [50].
2.7. Synthesis of ZnO as nanoparticles
For preparation of ZnO nano-particles calcinations of nano pow-
der compounds 1 and 2 were done at 450 °C in static atmosphere
of air for 4 h. IR spectrum and powder XRD diffraction show that
calcination was completed and the entire compounds were
decomposed.
3. Results and discussion
Reaction between the organic nitrogen-donor (4,40 -bipyridine)
ligand (L), potassium bromide, potassium chloride and zinc (II)
nitrate yielded crystalline material formulated as new 1D CP [Zn
(l-4,40 -bipy)Cl2]n (1) and [Zn(l-4,40 -bipy)Br2]n (2). Nanocrystals
of compound 1 and 2 were obtained in aqueous solution by
ultrasonic irradiation. Single crystals of compound 1 and 2, suitable
for X-ray crystallography, were prepared by thermal gradient
method applied to an aqueous solution of the reagents the
‘‘branched tube method. Scheme 1 gives an overview of the meth-
ods used for the synthesis of compounds 1 and 2 using the two dif-
ferent routes [Zn(l-4,40 -bipy)Cl2]n (1) and [Zn(l-4,40 -bipy)Br2]n (2)
synthesized by using the two different routes (branched tube and
Fig. 2. Distance of bounds in 1 (up), eight chains surrounding the central one (middle), dashed lines represent van-der-waales bonded (down).
505
ultrasonic method). Single crystal X-ray diffraction analysis (Tables
1–3) of compounds 1 and 2 was carried out and the coordination
environment of the title complexes are shown in (Fig. 1). Single
X-ray crystal analysis reveals that [Zn(l-4,40 -bipy)Cl2]n (1) and
[Zn(l-4,40 -bipy)Br2]n (2) complexes crystallize in orthorhombic
and monoclinic space group, Pnma and C2/c, respectively [51].
The Zn(II) atoms of compound 1 are coordinated by two Cl
atoms and two N atom composing distorted tetrahedral coordina-
tion Cl2N2 (Fig. 1). The asymmetric unit of compound 1 contains
one Zn2+ cations, which coordinate one 4,40 -bipyridine ligand and
one Cl anion. Each 4,40 -bipyridine ligand in compound 1 is coor-
dinated to two Zn atoms by N atom of pyridine ring, and Zn-N dis-
tance is about 2.06 Å. Additionally, two Cl atoms are coordinated
to each Zn(II) atom with contacts distances Zn–Cl in 2.217 Å
(Table 2 and Fig. 2). Ligand is bridging between two Zn2+ cations,
and two Cl are terminal occupying one vertex of base in distorted
tetrahedral coordination polyhedron of each Zn2+. The coordination
interactions can be separated in two groups:
(i) Strong, more valence, in short range of 0.930–2.217 Å;
(ii) Weak, more electrostatic, in long range of 2.874–3.348 Å.
Both terminal Cl ions additionally interact with neighbor
hydrogen of ligand, but with much longer than distances Cl(1)-H
(4) = 2.971 Å and Cl(1)-H(4) = 2.978 Å.
506 M.J.S. Fard et al. / Ultrasonics Sonochemistry 35 (2017) 502–513
Fig. 3. Distance of bounds in 2 (down), ten chains surrounding the central one (middle), dashed lines represent H-bonds (up).
Strong bonds form mononuclear complexes [Zn(L)(Cl)2], which
expanded by relatively weak interactions in polymeric chain [Zn
(l-4,40 -bipy)Cl2]n along a axis (Fig. 2). Simplification of mononu-
clear complexes [Zn(L)(Cl)2] into nodes of the chain underlying
net and its classification by ToposPro package reveals 2C1 topolog-
ical type, which is abundant for 1D CPs (more than 10,800 exam-
ples in TTO collection of ToposPro (Fig. 8) [52]. Every [Zn(l-4,40 -
bipy)Cl2]n chain is surrounded by eight other same chains forming
van-der-waals bonded hexagonal packing of cylinders (Fig. 2).
In compound 2, also are coordinated by two Br atoms and two N
atom composing distorted tetrahedral coordination Br2N2 (Fig. 1).
The asymmetric unit of compound 1 contains one Zn2+ cations,
which coordinate one 4,40 -bipyridine ligand and one Cl anion.
Each 4,40 -bipyridine ligand in compound 1 is coordinated to two
Zn atoms by N atom of pyridine ring, and Zn-N distance is about
2.06 Å. Additionally, two Br atoms are coordinated to each Zn(II)
atom with contacts distances Zn–Br in 2.352 Å (Table 3 and
Fig. 2). Ligand is bridging between two Zn2+ cations, and two Br
are terminal occupying one vertex of base in distorted tetrahedral
coordination polyhedron of each Zn2+. The coordination interac-
tions can be separated in two groups (see Fig. 3):
(i) Strong, more valence, in short range of 0.930–2.2.065 Å;
(ii) Weak, more electrostatic, in long range of 2.981–3.893 Å.
Both terminal Br ions additionally interact with neighbor
hydrogen of ligand, but with much longer than distances Br(1)-H
(1) = 3.058 Å and Br(1)-H(4) = 3.058 Å.
Strong bonds form mononuclear complexes [Zn(L)(Br)2],
which expanded by relatively weak interactions in polymeric
chain [Zn(l-4,40 -bipy)Cl2]n along b axis (Fig. 2). Simplification
of mononuclear complexes [Zn(L)(Br)2] into nodes of the chain
underlying net and its classification by ToposPro package
reveals 2C1 topological type, which is abundant for 1D CPs
(more than 10800 examples in TTO collection of ToposPro
(Fig. 8) [49]. Every [Zn(l-4,40 -bipy)Cl2]n chain is surrounded
 M.J.S. Fard et al. / Ultrasonics Sonochemistry 35 (2017) 502–513 507

(a)

(b)
Fig. 4. The zig-zag chains of 1-D CPs of [ZnCl2(l-4,40 -bipy)]n running along a-axis (a) and of 1-D CPs of [ZnBr2(l-4,40 -bipy)]n running along [1 0 1] direction (b).

Fig. 5. Crystal packing of compounds 1 (up) and 2 (down).

508 M.J.S. Fard et al. / Ultrasonics Sonochemistry 35 (2017) 502–513

Fig. 6. p–p interaction in compounds 1.

Fig. 7. p–p interaction in compounds 2.

 M.J.S. Fard et al. / Ultrasonics Sonochemistry 35 (2017) 502–513 509

Fig. 8. Topological representation of coordination networks in compounds 1 (up) and 2 (down).

Table 3
Selected bond lengths/A° for compound [ZnBr2(l-4,40 -bipy)]n [51]. by ten other same chains forming van-der-waals bonded hexag-
onal packing of cylinders (Fig. 2).
Zn—N(1)I 2.065(3) C(2)—C(3) 1.338(7)
In summary, [Zn(L)(Br)2] and [Zn(L)(Cl)2] units forming respec-
Zn—N(1) 2.065(3) C(2)—H(2) 0.9300
Zn—BrI 2.3524(7) C(3)—C(4) 1.365(7) tive CPs of zinc (II) consisting of zig-zag 1D chains running along a-
Zn—Br 2.3524(7) C(3)—C(3)II 1.498(8) axis ([1 0 0] direction) and b-axis ([0 1 0] direction) in 1 and 2,
N(1)—C(1) 1.304(6) C(4)—C(5) 1.371(7) respectively (Fig. 4a and b). Within the stacks the 4,40 -bipyridine
N(1)—C(5) 1.315(6) C(4)—H(4) 0.9300 molecules are parallel each other and separated by a distance of
C(1)—C(2) 1.380(7) C(5)—H(5) 0.9300
5.14(4) Å in 1 and 5.43(4) Å in 2 (these values are between the
C(1)—H(1) 0.9300 C(2)—C(3) 1.338(7)
Zn—N(1)II 2.065(3) C(2)—H(2) 0.9300 gravity centers of neighboring pyridine rings within the stacks).
Zn—N(1) 2.065(3) C(3)—C(4) 1.365(7) These distances are too long for the effective p-p interactions
between the aromatic rings within the stacks (Figs. 6 and 7) (see
Symmetry transformations used to generate equivalent atoms: (i) 1x, y, 0.5z; (ii)
1.5x, 1.5y, 1z. Fig. 5).

Fig. 9. The IR spectra of (a) bulk materials as synthesized of compound 1, (b) nano-sized compound 1 prepared by sonochemical method.
510 M.J.S. Fard et al. / Ultrasonics Sonochemistry 35 (2017) 502–513

Fig. 10. The IR spectra of (c) bulk materials as synthesized of compound 2, (d) nano-sized compound 2 prepared by sonochemical method.

Fig. 11. XRD patterns: (a) simulated pattern based on single crystal data of compound 1, (b) nano particles of compound 1, (c) simulated pattern based on single crystal data
of compound 2, (d) nano particles of compound 2.
 M.J.S. Fard et al. / Ultrasonics Sonochemistry 35 (2017) 502–513 511

Fig. 12. (a) SEM photograph and the corresponding particle size distribution histogram of compound 1 nanoparticles, (b) SEM photograph and the corresponding particle size
distribution histogram of compound 2 nanoparticles.

The IR spectra display characteristic absorption bands for the 500 cm1 that can be attributed to the stretching modes of Zn-O
ligand bipyridine in compounds 1 and 2. The relatively weak and the weak bands in the range of 1380–3425 cm1 are probably
absorption bands at around 3020 in compound 1 and 3024 cm–1 attributed to the presence of water in the KBr matrix.
in compound 2 are due to the C–H modes involving the aromatic Fig. 13 shows X-ray powder diffraction pattern of ZnO nanopar-
ring hydrogen atoms. The absorption bands with variable intensity ticles after calcination of compounds 1 and 2. The XRD patterns of
in the frequency range 1400–1590 cm1 correspond to ring vibra- ZnO nanoparticles after calcinations of compounds 1–2 are quite
tions of the pyridine moiety of the ligand 4,40 -bipyridine (Figs. 9 the same and are in agreement with the typical zincite structure
and 10). ZnO diffraction (hexagonal phase, space group P63mc, with lattice
Fig. 11 shows the comparison of XRD patterns, simulated from constants a = 3.220 Å, c = 5.200 Å, Z = 2, ICSDNo.01-073-1526).
single crystal X-ray data against the nano powders of compounds Sharp diffraction peaks indicate good crystallinity of ZnO nano-
1 and 2 prepared by the sonochemical process, respectively. The particles. No characteristic peaks of impurities are detected in
comparison between these XRD patterns indicates acceptable
matches with slight differences in 2h. Estimated from the Sherrer
formula for the calculation of particle sizes from the broadening
of the XRD peaks (D = 0.891k/bcosh, where D is the average grain
size, k is the X-ray wavelength (0.15405 nm), and h and b are the
diffraction angle and full-width at half maximum of an observed
peak, respectively) the average size of the particles were found to
be around 64.3 for compound 1 and 54.7 for compound 2. Fig. 12
show the SEM images and the corresponding particle size distribu-
tion histogram of the compounds 1 and 2. Fig. 11 shows if the pick
is sharper, then crystal lattice will be more regular. Also, for crystal
and nano structures compound 1 and 2 are concluded which have
same phase.
Nano-particles of ZnO have been generated by calcination of
compounds 1 and 2. The final product upon calcination of com-
pounds 1–2 at 400 °C, based on their IR and XRD patterns in two
cases is ZnO. The IR spectrum of ZnO nanoparticles after calcina- Fig. 13. XRD pattern of ZnO nanoparticles prepared by calcinations of nano powder
tions of compounds 1–2 shows absorption bands at about of compounds 1 and 2.
512 M.J.S. Fard et al. / Ultrasonics Sonochemistry 35 (2017) 502–513
Fig. 14. SEM image and the corresponding particle size distribution histogram of ZnO nanoparticles prepared by calcination of (a) nano powder of compound 1 at 450 °C, (b)
nano powder of compound 2 at 450 °C.
XRD pattern. Fig. 14 show the SEM image and the corresponding
particle size distribution histogram of ZnO nano-particles obtained
from calcinations of nano-particles of compounds 1–2 at 450 °C.
4. Conclusion
Two new Zn(II) coordination polymer compounds (CPCs) [Zn(l-
4,40 -bipy)Cl2]n (1) and [Zn(l-4,40 -bipy)Br2]n (2) L = bpy = 4,40 -
bipyridine ligand, have been synthesized utilizing a thermal gradi-
ent approach and also by sonochemical irradiation. Compounds 1
and 2 were structurally characterized by single crystal X-ray
diffraction. The crystal structures of compound 1 and 2 are made
up of two 1D CPs compounds and shows the relevant coordination
number for the Zn(II) ions are found to be four. Nano-particles of
compounds 1 and 2 have been characterized by scanning electron
microscopy (SEM), X-ray powder diffraction (XRD), elemental anal-
yses and IR spectroscopy. Nano-particles of zinc (II) oxide have
been prepared by calcinations of two different zinc (II) CPs. The
nano oxides were characterized by scanning electron microscopy
(SEM) images, X-ray powder diffraction (XRD) and IR spectroscopy.
Acknowledgement
This work was supported by the Islamic Azad University of
Firoozabad.
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