Survey of temperature, reaction time and ultrasound irradiation power on sonochemical synthesis of two new nanostructured lead(II) coordination supramolecule compounds

Article abstract of DOI:10.1016/j.ultsonch.2016.09.005

Nanoparticles of two new 0D, lead(II) coordination supramolecular compounds, [Pb(L)₂(I)₂] (1) and [Pb(L)(L^/)(H₂O)]·3H₂O (2), (L = 1,10-phenanthroline monohydrate, L^/ = 2,6-pyridinedicarboxlic acid), have been synthesized by a sonochemical process and characterized by scanning electron microscopy (SEM), field emission scanning electron microscopy (FE-SEM), X-ray powder diffraction (XRPD), FT-IR spectroscopy and elemental analyses. The single crystal X-ray data of compounds show that the Pb ion is six coordinated in both 1 and 2. The thermal stability of compound 1 and 2 has been studied by thermal gravimetric (TG) and differential thermal analyses (DTA). The role of temperature, reaction time and ultrasound irradiation power on the size and morphology of the nano-structured compound obtained from 1 and 2, have been investigated. Results indicate that an increase of temperature and sonication power and a decrease in time reaction led to a decrease of particle size. Topological analysis shows that the compound 1 and 2 are new topology for net: 1,4M5-1 and nch, respectively.

Full text of DOI:10.1016/j.ultsonch.2016.09.005

Accepted Manuscript
Survey of temperature, reaction time and ultrasound irradiation power on so-
nochemical synthesis of two new nanostructured lead (II) coordination supra-
molecule compounds
Payam Hayati, AliReza Rezvani, Ali Morsali, Pascal Retailleau, Roberto
Centore
PII:
S1350-4177(16)30316-9
DOI:
http://dx.doi.org/10.1016/j.ultsonch.2016.09.005
ULTSON 3362
Reference:
Ultrasonics Sonochemistry
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27 July 2016
4 September 2016
5 September 2016
Please cite this article as: P. Hayati, A. Rezvani, A. Morsali, P. Retailleau, R. Centore, Survey of temperature,
reaction time and ultrasound irradiation power on sonochemical synthesis of two new nanostructured lead (II)
coordination supramolecule compounds, Ultrasonics Sonochemistry (2016), doi: http://dx.doi.org/10.1016/
j.ultsonch.2016.09.005
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Survey of temperature, reaction time and ultrasound irradiation power on
sonochemical synthesis of two new nanostructured lead (II) coordination
supramolecule compounds
Payam Hayatia, AliReza Rezvani*a, Ali Morsali*b, Pascal Retailleauc, Roberto
Centored
a Department of Chemistry, Faculty of Science, University of Sistan and Baluchestan, P.O. Box
98135-674, Zahedan, Iran.
b Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, P.O. Box
14115-4838, Tehran, Islamic Republic of Iran.
cCentre de Recherche de Gif, Institut de Chimie des Substances Naturelles, CNRS-UPR2301,
1 Avenue de la Terrasse, Bât 27, 91198 Gif sur Yvette cedex, France.
d Department of Chemical Sciences, University of Naples Federico II, Via Cintia, I-80126,
Naples, Italy.
Abstract
Nanoparticles of two new 0D, lead (II) coordination supramolecular compounds, [Pb(L)2(I)2]
(1) and [Pb(L)(L/)(H2O)].3H2O(2), (L =1,10-phenanthroline monohydrate, L/= 2,6-
pyridinedicarboxlic acid ), have been synthesized by a sonochemical process and characterized
by scanning electron microscopy (SEM), field emission scanning electron microscopy (FE-
SEM), X-ray powder diffraction (XRPD), FT-IR spectroscopy and elemental analyses. The
single crystal X-ray data of compounds show that the Pb ion is six coordinated in both 1 and 2.
The thermal stability of compound 1 and 2 has been studied by thermal gravimetric (TG) and
differential thermal analyses (DTA). The role of temperature, reaction time and ultrasound
1

irradiation power on the size and morphology of the nano-structured compound obtained from 1
and 2, have been investigated. Results indicate that an increase of temperature and sonication
power and a decrease in time reaction led to a decrease of particle size. Topological analysis
shows that the compound 1 and 2 are new topology for net: 1,4M5-1and nch, respectively.
Keywords: Coordination polymer, Sonochemical process, Ultrasound irradiation.
1. Introduction
During the last two decades, the rational design and syntheses of novel coordination
supramolecular compounds that involve self-assembly of organic ligands with appropriate
functional groups and metal ions with specific directionality and functionality have made
considerable progress in the field of supramolecular chemistry and crystal engineering [1-5]. The
considerable interest is driven by the impact on basic structural chemistry as well as by possible
applications in numerous fields such as catalysis, molecular adsorption, luminescence,
magnetism, nonlinear optics, and molecular sensing that are not found in mononuclear
compounds [6-9]. The possible stereo-chemical activity from the lone pair of Pb(II) compounds
have been discussed by Shimoni-Livny et al., based on a thorough overview of crystal data
available in the Cambridge Structural Database (CSD)[10]. They classified lead coordination as
the holodirected referring to complexes where the Pb-ligand bonds are directed throughout the
surface of encompassing sphere, whereas the hemidirected referring to those in which the Pb-
ligand bonds are directed merely to a part of the coordination sphere, leaving a gap in the
distribution of bonds towards the ligand. The lead (II) complexes with N-donor ligands [11-23].
A number of different synthetic approaches have already been developed for the preparation
of coordination compounds [24]. Some of them are slow diffusion from the reactants into a
2

polymeric matrix, diffusion from the gas phase, evaporation of the solvent at ambient or reduced
temperatures, precipitation or recrystallisation from a mixture of solvents, temperature controlled
cooling, hydrothermal synthesis and sonochemical syntheses [25, 26].
Over the past decade, using ultrasound for nanomaterial synthesis has been growing at an
enormous rate [27], and is now positioned as one of the most powerful tools in metal–organic
coordination compounds synthesis [28-31 and 56]. Ultrasound causes high-energy chemistry. It
does so through the process of acoustic cavitation, which includes formation, growth, and
implosive collapse of bubbles in the liquid medium. A bubble can overgrow and subsequently
collapse within very short lifetimes (>1010 K s-1). A large energy concentration is achieved
throughout the collapse, resulting in a local temperature of ~5000 K and a pressure of ~1000 bar
[32]. Consequently, various kinds of chemical reactions can proceed using ultrasonic irradiation
[33-36].
Chemical and physical properties of solid materials strongly depend on the shape and size of
the microscopic particles they are made up from. This is especially valid for materials with
morphological features smaller compared to a micron in at least one dimension, which are
generally called nano-scale materials, or simply just nanomaterials. In these materials the ratio of
(the number of) surface area to volume is vastly increased compared to compounds with larger
grain sizes and quantum mechanical effects including ‘‘quantum size effect’’ begin to play a
substantial role. These effects only play a minor role when transferring from macro to micro
dimensions, yet become of prime importance when reaching the nanometer size range.
Controlling the growth of materials in the submicrometer scale is extremely important. In the
emerging field of nanotechnology, nanometer-sized particles of metal coordination polymers are
fascinating to explore, since their unique properties are controlled by the large numbers of
3

surface molecules, which experience a completely different environment than those inside a bulk
crystal. Although considerable effort has been dedicated towards the controlled synthesis of
nanoscale particles of metals, oxides, sulfides, and ceramic materials, little attention has been
focused up to now on nano-structures of coordination polymers [37-41]
The effects of ultrasound radiation on chemical reactions were reported in recent works [35,
54-55]. In this paper, we have developed a simple sonochemical approach to prepare nano-
structures of [Pb(L)2(I)2] and [Pb(L)(L/)(H2O)].3H2O The ultrasonic power, sonicating time and
temperature of reaction are the parameters which were changed for reaching the optimized
condition. For the characterization of the products, scanning electron microscopy (SEM) and
powder X-ray diffraction (PXRD) were used.
2. Experimental
2.1. Materials and physical techniques
Starting reagents for the synthesis were purchased and used without any purification from
industrial suppliers (Sigma–Aldrich, Merck and others). Elemental analyses (carbon, hydrogen,
and nitrogen) were performed employing a Heraeus Analytical Jena, Multi EA 3100 CHNO
rapid analyzer. Fourier transform infrared spectra were recorded on a FT-IR JASCO 680-PLUS
spectrometer as KBr pellets in the 4000–400 cm−1 spectral range. Thermal
gravimetric (TG) and differential thermal analyses (DTA) of the title compound were performed
on a computer-controlled STA - PT 1500 apparatus. Single phase powder sample of 1 - 1, 2 - 1
and crystal structure compounds 1, 2 were loaded into alumina pans and heated with a ramp rate
of 10 °C/min from room temperature to 600 °C under argon atmosphere. Single crystal X-ray
diffraction experiments were carried out for compounds 1 and 2 with MoKꢀ radiation
(λ=0.71073 Å) at ambient temperature. A microfocused Rigaku mm003 source with integrated
4

confocal caxFlux double bounce optic and HPAD Pilatus 200K detector was used for 1, while
for 2 data were measured on a Bruker-Nonius Kappa CCD diffractometer. The structures were
solved by direct methods and refined by full matrix least squares on F2. All non-hydrogen atoms
were refined anisotropically. Hydrogen atoms were included in structure factor calculations from
their location in difference maps. C-bound H atoms were treated as riding in geometrically
idealized positions, with Uiso (H) = kUeq (C), where k = 1.2 for the Csp2 - bound H atoms. For
the water molecules, the oxygen-hydrogen bond lengths were restrained to 0.82(2) Å (DFIX
instruction) and the hydrogen-hydrogen intramolecular distances were restrained to 1.30(4) Å
(DANG instruction). The Uiso value for hydrogen atoms were set to 1.5 times the value of the
water oxygen atom. Computing details: data collection, cell refinement and data reduction:
CrystalClear-SM expert 2.1b43 [42]; program(s) used to solve structure: SHELXT [43];
program(s) used to refine structure: SHELXL-2014/7 [43]; molecular graphics: PLATON [44];
reduction of data and semiempirical absorption correction: SADABS program[45]; direct
methods (SIR97 program[46]); full-matrix least-squares method on F2: SHELXL-97 program
[47] with the aid of the program WinGX [48]. X-ray powder diffraction (XRD) measurements
were performed using an X’pert diffractometer manufactured by Philips with monochromatized
Cuka radiation and simulated XRD powder patterns based on single crystal data were prepared
using the Mercury software [49]. The samples were characterized with a scanning electron
microscope (SEM) (Philips XL 30 and S-4160) and field emission scanning electron microscope
(FE-SEM) (Perkin Elmer Elan 9000) with gold coating. A multi wave ultrasonic generator
(Sonicator_3000; Misonix, Inc., Farmingdale, NY, USA), equipped with a converter/transducer
and titanium oscillator (horn), 12.5 mm in diameter, operating at 20 kHz with a maximum power
5

output of 600 W, were used for the ultrasonic irradiation. Melting points were measured on an
electrothermal 9100 apparatus and are uncorrected.
2.2. Synthesis of [Pb(L)2(I)2] (1) as single crystal
Lead (II) acetate trihydrate (1 mmol, 0.379 g), 1,10-phenanthroline monohydrate (1 mmol,
0.198 g) and potassium iodide (2 mmol, 0.332 g), were loaded into one arm of a branch tube and
both of the arms were filled slowly by water. The chemical bearing arm was immersed in an oil
bath kept at 60 °C. Yellow crystals formed on the inside surface of the arm kept at ambient
temperature after 15 days. They were filtered off, washed with water and air dried. Yield 0.238 g
(58.04 % based on final product). Product 1 (single crystals): m.p >300 °C. Anal. Calc. for C24
H16 I2 N4 Pb: C: 35.06, H: 1.94, N: 6.81%; Found C: 34.95 H: 1.89 N: 6.79 %.IR (selected bands
for compound 1; in cm-1): 3048.15(w), 1673.63(s), 1584.38(w), 1566.49(w), 1448.95(m),
1392.50(s), 1082.78(w), 1012.59(w), 898.94(w), 825.43(s), 767.07(w), 695.55(s), 658.01(w) cm-
1
.
2.3. Synthesis of [Pb(L)2(I)2] (1) nano-structures by use of ultrasonic irradiation
To prepare the nano-structures of [Pb(L)2(I)2] (1) by sonochemical process, a high-density
ultrasonic probe was directly immersed into the solution of lead (II) acetate trihydrate (20 ml,
0.01 M) in water; then, into this solution, a proper volume of potassium iodide and 1,10-
phenanthroline monohydrate in water solvent (20 ml, 0.01 M) was added in a dropwise manner
and the solution was ultrasonically irradiated. In order to study the effect of time, temperature
and power on size and morphology of nano-structured compound 1, the ultrasonic irradiation
was performed for different times (30 min, 1 h), at different temperature (50 °C, 80 °C) and with
different power (60 W, 80 W). The obtained precipitates were filtered, subsequently washed with
water and then dried. Yield 0.315 g (76.82% based on final product). Product 1 (nano structure):
6

m.p >300 °C. Anal. Calc. for C24 H16 I2 N4 Pb: C: 35.06, H: 1.94, N: 6.81%; Found C: 35.02 H:
1.90 N: 6.81 %. IR (selected bands for compound 1; in cm-1): 3043.26(w), 1620.01(s),
1586.77(w), 1514.72(s), 1426.28(m), 1344.59(s), 1143.87(s), 1098.62(s), 853.64(s), 731.93(s),
722.14(s), 681.79(w), 637.93(w) cm-1.
2.4. Synthesis of [Pb(L)(L/)(H2O)].3H2O (2) as single crystal
Lead(II) acetate trihydrate (1 mmol, 0.379 g), 1,10-phenanthroline monohydrate (1 mmol,
0.198 g) and 2, 6-pyridinedicarboxlic acid (1 mmol, 0.166 g) were loaded into one arm of a
branch tube and both of the arms were filled slowly by water. The chemical bearing arm was
immersed in an oil bath kept at 60 °C. Colorless crystals formed on the inside surface of the arm
kept at ambient temperature after 7 days; they were filtered off, washed with water and air dried.
Yield 0.242 g (38.90 % based on final product). Product 2 (single crystals): m.p >300 °C. Anal.
Calc. for C19 H17N3O8Pb: C: 36.62, H: 2.73, N: 6.74, O: 7.71 %; Found C: 36.59, H: 2.71, N:
6.68, O: 7.71 %. IR (selected bands for compound 2; in cm-1): 3418.16(br), 3059.39(w),
1610.13(w), 1587.5(w), 1423.58(s), 1377.27(s), 1273.13(m), 1182.17(w), 1083.95(w),
1020.17(w), 908.96(s), 846.79(m), 727.73(s), 665.97(w), 550.52(w) cm-1.
2.5. Synthesis of [Pb(L)(L/)(H2O)].3H2O (2) nano-structures by use of ultrasonic
irradiation
To prepare the nano-structures of [Pb(L)(L/)(H2O)].3H2O (2) by an sonochemical process, a
high-density ultrasonic probe immersed directly into the solution of lead (II) acetate trihydrate
(20 ml, 0.05 M) in water, then into this solution, a proper volume of 1,10-phenanthroline
monohydrate and 2, 6-pyridinedicarboxlic acid in water solvent (20 ml, 0.05 M) was added in a
drop wise manner and the solution was ultrasonically irradiated. Also in this case, in order to
7

study the effect of time, temperature and power on size and morphology of the nano-structured
compound, the ultrasonic irradiation was performed for different times (30 min, 1 h), at different
temperature (50 °C, 80 °C) and with different power (60 W, 80 W). The obtained precipitates
were filtered, subsequently washed with water and then dried. Yield 0.358 g (57.55 % based on
final product) Product 2 (nano structure): m.p. >300 °C. Anal. Calc. for C19 H17N3O8Pb: C:
36.62, H: 2.73, N: 6.74, O: 7.71 %; Found C: 36.61, H: 2.71, N: 6.69, O: 7.71 %. IR (selected
bands for compound 2; in cm-1): 3436.27(br), 3099.05(w), 1609.87(w), 1579.32(w), 1566.40(w),
1422.68(s), 1380.20(s), 1271.77(m), 1181.07(w), 1069.53(w), 1018.00(w), 913.74(s), 825.11(m),
729.16(s), 663.82(w), 571.99(w), 511.62(w) cm-1.
3. Results and discussion
Reaction between the organic nitrogen-donor 1,10-phenanthroline monohydrate ligand (L),
potassium iodide, and lead(II) acetate trihydrate yielded crystalline material formulated as new
coordination supramolecular [Pb(L)2(I)2] (1). Utilizing 1,10-phenanthroline monohydrate (L) and
2, 6-pyridinedicarboxlic acid (L/) ligands in lead (II) acetate trihydrate leads to formation of new
molecular coordination compound [Pb(L)(L/)(H2O)].3H2O (2). Nano-structures of compound 1
and 2 were obtained in aqueous solution by ultrasonic irradiation, while single crystals of
compound 1 and 2, suitable for X-ray crystallography, were prepared by a heat gradient applied
to an aqueous solution of the reagents (the ‘‘branched tube 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 Single X-ray crystal analysis reveals that
[Pb(L)2(I)2] (1) [Pb(L)(L/)(H2O)].3H2O(2) complexes crystallize in orthorhombic and triclinic
space group Pbcn and Pꢁ.. Also, shows compounds 1 and 2 are 0-D coordination supramolecular.
8

In compound 1, Pb atoms are coordinated by four N atoms, two I- anions and have distorted
octahedral coordination sphere as I2N4 (Fig.1). In the crystal molecules lie on crystallographic
binary axes, so the asymmetric unit contains half of a molecule. Pb–N and Pb-I distances are
about 2.55-3.30Å (Table-2 and Fig. 2).
In compound 1 strong bond construct the monomer complex [Pb(L)2(I)2], which is expanded
in supramolecular monomer complex [Pb(L)2(I)2] by weak interactions. At least 1 is a
supramolecular compound with molecular structure (Fig. 2 and 5). The simplification and
classification of the monomer molecules by ToposPro in 1 gives the underlying topology 1,4M5-
1, which is abundant for 0D coordination compounds (more than 60000 examples in TTO
collection of ToposPro (Fig.11) [53]. Every [Pb(L)2(I)2] monomer is connected to other
monomers by van-der-Waals bonds Pb-H, I-H, C-H, N-H, C-N, C-C, but the area of these
contacts between central molecule and 18 surrounding molecules is different. Thus, the largest
area of interactions are provided ꢂ-ꢂ stacking of L ligands (Fig. 2, 4, and 5). There are only 6
molecules having ꢂ-ꢂ contacts with the central one, they form molecule packing of primitive
cubic topology pcu which additionally have N-H, C-H, Pb-H, I-H, and H-H interactions (Fig. 7).
Two molecules contacts by four common I-H interactions, and four other molecules connected
only by one I-H contact. Also four molecules touch the central one trough three H-H contacts,
and two molecules have only one H-H contact. Obviously ꢂ-ꢂ interactions play major role in
formation of the molecular packaging pcu by surrounding each molecule in distorted octahedral
geometry of connection (Fig. 5).
In compound 2, Pb atoms are coordinated by three N atoms, three O atoms and have distorted
hexagonal coordination sphere as O3N3 (Fig.1). The asymmetric unit cell of compound 2 consists
of one Pb+2 cation, one 1,10-phenanthroline and 2,6-pyridine dicarboxylic acid ligands, and one
9

water molecule. Each Pb atom is coordinated by two nitrogen of 1,10-phenanthroline, one N and
one O from 2,6-pyridinedicarboxylic acid ligand and one O from water. Bond lengths Pb–N and
Pb-O are about 2.43-3.26Å (Table-3 and Fig.3).
In compound 2, strong bonds construct the monomer complex [Pb(L)(L/)(H2O)].3H2O, which is
expanded in supramolecular monomer complex [Pb(L)(L/)(H2O)].3H2O by weak interactions. At
least 2 is supramolecular compound with molecular structure [Pb(L)(L/)(H2O)].3H2O (Fig.4 and
6). The simplification and classification of the monomer molecules by ToposPro in 2 (without
inter-lattice water) gives the underlying topology nch, which is abundant for 0D coordination
compounds (more than 10000 examples in TTO collection of ToposPro (Fig.11) [53]. There are
only 3 molecules having ꢂ-ꢂ contacts with the central one, Also each monomer having hydrogen
bound contacts with one other molecule and every [Pb(L)(L/)(H2O)].3H2O monomer is
connected to twelve other by van-der-Waals contacts: C1-H1, H1-H2, H13-H15, etc. (Fig.4 and
6). Each such monomer is surrounded by sixteen other same monomer forming hydrogen bonded
and Obviously ꢂ-ꢂ interactions play major role in formation of the molecular packaging 1,3M4-1
by surrounding each molecule in distorted octahedral geometry of connection, which is
geometrically is distorted octahedral (Fig.7). Figure 10 (up and down) shows the short contacts
in compound 1 and 2. Short contacts are between C – C, I – C, H – I, N – N, C – H, and H – O,
O – O atoms, respectively.
The IR spectra display characteristic absorption bands for stretching C-H, C=N of the 1,10-
phenanthroline ligand and absorption bands of H2O and C=O and C-O of the 2,6-
pyridinedicarboxlic acid ligand in compounds 1 and 2. The IR spectrum of compound 1 shows
the characteristic stretching frequency of C-H ring group at about 3048.15 cm-1. The absorption
bands around 1448.95, 1392.50 and 825.43 cm-1 are related to stretching of C=C and C=N and
10

=C-H bending of aromatic rings. For compound 2, bands at around 3418.16 and 3059.39 cm-1 are
due to the H2O. The absorption bands with variable intensity in the frequency range 1610.13 cm-
1
correspond to C=O stretching frequency from the carbonyl of the 2,6-pyridinedicarboxlic acid
ligands. Also, characteristic band of the C-O stretching frequency and =C-H bending frequency
appear at 1273.13 and 846.79 cm-1.The elemental analysis and IR spectra of the nano-structure
produced by the sonochemical method as well as the bulk material produced by the branched
tube method are indistinguishable (Figure 12).
Figure 13b and d show the XRD patterns of compounds 1 and 2 simulated from single crystal
X-ray data. While the experimental XRD patterns of compounds 1 and 2 prepared by the
sonochemical process is shown in Fig. 13a and c, respectively. For both compounds, acceptable
matches, with slight differences in 2θ, were observed between the simulated and experimental
powder X-ray diffraction patterns. This indicates that the compound 1 and 2 obtained by the
sonochemical process as nano-structures is identical to that obtained by single crystal diffraction.
The significant broadening of the peaks indicates that the particles are of nanometer dimensions.
In order to look at the thermal stability of the two compounds, thermal gravimetric (TG) and
differential thermal analyses (DTA) were carried out between 30 and 800 °C under argon flow.
The TG curve of compound 1 indicates that the compound does not melt and is stable up to
168.62 °C and then it begins to decompose (Figure 14). The first removal of the aromatic ring
without nitrogen atom 1,10-phenanthroline ligand in 168.62°C, Then removal of two aromatic
rings with nitrogen atom 1,10-phenanthroline ligand are started in 440 °C. Aromatic ring without
nitrogen atom carry out in the range between 168.62 °C and 440 °C with four exothermic effect
at 189.89, 235.33, 298.60 and 357.09 °C. Also two aromatic rings 1,10-phenanthroline take place
in the range between 440 and 600 °C with one exothermic effect at 734.70 °C Mass loss
11

calculations suggests that the ultimate product is an amorphous solid that appears to be PbI2. The
TG curve of compound 2 indicates that this compound is stable up to 30 °C, at which
temperature it begins to decompose (Figure 14). Removal of the three water molecule, aromatic
rings of 1,10-phenanthroline ligand, pyridine aromatic ring and two carboxylate groups of 2,6-
pyridinedicarboxlic acid ligand carry out in 70.03, 224.48 and 453.25 °C, respectively.
Decomposition of the three water molecular, aromatic rings of 1,10-phenanthroline ligand,
pyridine aromatic ring and two carboxylate groups of 2,6-pyridinedicarboxlic acid ligand takes
place in three steps 100.73 °C and mass loss of 11.49 % with one exothermic between from 30
to 150 °C, 264.76 °C and mass loss of 40.15 % with one exothermic between from 220 to 280 °C
and 489.62 °C and mass loss of 58.13 % with one exothermic between 385 and 540 °C,
respectively. Mass loss calculations show that the final decomposition product is PbO (Figure
14).
The corresponding particle size distribution histogram of compound 1 and 2 nanoparticles is
shown in Figure 15 and 16 respectively. Various conditions for preparation of compound 1 and 2
nano-structures are summarized in Table 4. In this Table, sample 1 - 1 and 2 - 1 was studied
without power ultrasound and the other samples were studied under variable temperature, time
and power ultrasound. In order to research the role of power ultrasound irradiation on the
character of product, reactions were performed under completely different power ultrasound
irradiation. Results show a decrease in the particles size as increasing power ultrasound
irradiation [50-52].
In sample 1 - 1, the reactions were studied without power ultrasound. Results show that size
particles sample of 1 - 1 (Fig. 17a) is larger than 1 - 2 (Fig. 17b), these results are similar with
samples 2 – 1, 2 – 2 (Fig. 18a, b). Table 4, show the average diameter field emission scanning
12

electron microscope (FE-SEM) and scanning electron micrographs (SEM) of the prepared
samples. Results show high power ultrasound irradiation decreased agglomeration, and thus led
to decrease particles size. Comparison between samples 1 - 2 and 1 - 3 shows a decrease in
nanoparticle size. Thus, size particles of sample 1 - 3 are smaller than 1 – 2 (Fig. 17b, c). These
facts are repeated in samples 2 – 2 and 2 – 3 (Fig. 18b, c). Table 4, show the average diameter
field emission scanning electron microscope (FE-SEM) and scanning electron micrographs
(SEM) of the prepared samples. However, a reducing the reaction time led to the decrease of size
particles of sample 1 – 3. Particle sizes and morphology of nanoparticle depend on temperature
[50]. Higher temperature (70 °C) results in an increased solubility, and thus a reduced
supersaturation of growth species in the solution, and thus particles size of sample 1 - 4 is
smaller than particles size of sample 1 – 2( Fig. 17d, b). These facts are repeated in samples 2 – 4
and 2 – 2 (Fig.18d, b). Table 4 shows the average diameter of nanoparticles by field emission
scanning electron microscope (FE-SEM) and scanning electron micrographs (SEM).
4. Conclusion
Two new Pb(II) coordination supramolecular compounds [Pb(L)2(I)2] (1) and
[Pb(L)(L/)(H2O)].3H2O (2), (L = 1,10-phenanthroline, L/= 2,6-pyridinedicarboxlic acid ), have
been synthesized utilizing a thermal gradient approach and also by sonochemical irradiation.
Compounds 1 and 2 were structurally characterized by single crystal X- ray diffraction. The
crystal structure of compound 1 and 2 is made up of two 0D supramolecular compound and
shows that the coordination number of Pb (II) ions in compound 1 and 2 is six. Influences of
temperature, power ultrasound and reaction time on the morphological properties of [Pb(L)2(I)2]
and [Pb(L)(L/)(H2O)].3H2O, were studied. The results showed that higher temperature of
reagents led to decrease in particle size and optimum time for the process was obtained 30 min,
13

increasing in the power of ultrasonic irradiation led to decrease particles size for 1 and 2. Also,
the best conditions for getting a small sized and less agglomerated nanostructure materials for
these two lead (II) coordination supramolecular compounds are temperature, reaction time and
the power of ultrasonic irradiation 70 °C, 60 min and 60 W, respectively.
Supplementary material
Crystallographic data for the structure reported in this paper have been deposited with the
Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-1442311 and
CCDC-1442312. Copies of the data can be obtained upon application to CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK (Fax: +44 1223/336033; e-mail: deposit@ccdc.cam.ac.uk).
Acknowledgement
We are deeply indebted to Professor Lucia Carlucci (Milan, Italy) for improving early version
of the paper. We would like to thank Professor Davide M. Proserpio (Milan, Italy) for teaching
ToposPro lessons. Thanks are also due to Eugeny V. Alexandrov (Samara, Russia) for many
fruitful discussions about coordination compounds topology.
Support of this investigation by University of Sistan and Baluchestan (USB) and Tarbiat
Modares University is gratefully acknowledged.
14

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21

Table 1. Crystal data and structures refinement for [Pb(L)2(I)2] and [Pb(L)(L/)(H2O)].3H2O
Empirical formula
Formula weigh
Temperature
C24 H16 N4 I2 Pb
821.40
293(2)K
C19 H11 N3 O5 Pb, 3(H2O)
622.54
293(2)K
Wavelength
Crystal system
Space group
0.71075 Å
Orthorhombic
Pbcn
0.71075 Å
Triclinic
Pꢁ
a = 7.2605 (5) Å, ꢀ = 90.537 (4) °
b = 9.9690 (7) Å, ꢇ = 99.046 (4) °
Unit cell dimensions
a = 13.5170(8) Å, ꢀ = 90°
b =9.0820 (13) Å, ꢇ = 90°
c =18.492 (3)Å, ꢈ = 90°
2270.1(5) Å3
4
c = 14.1054 (10) Å, ꢈ = 100.597 (4) °
Volume
Z
Density(calculated)
F(0 0 0)
µ
990.28(12) Å3
2
2.403 g/cm3
2.08767 g/cm3
596.0
1504
10.71 mm-1
8.57mm-1
-11 ꢉ h ꢉ 16
-8 ꢉ k ꢉ 10
-9 ꢉ h ꢉ 9
Index ranges
-12 ꢉ k ꢉ 12
-18 ꢉ l ꢉ 18
0.651Å−1
-21 ꢉ l ꢉ 20
(sin ꢊ/ꢋ)max
0.594 Å−1
Theta(max)
24.99°
27.584°
Radiation type
Refinement method
Goodness- of- fit on F2
Refinement
Mo Kꢀ
Mo Kꢀ
Full–matrix least–squares on F2
1.028
Full–matrix least–squares on F2
1.053
R[F2> 2ꢌ(F2)]=0.037
wR(F2)=0.097
S=1.03
R[F2> 2ꢌ(F2)]=0.030
wR(F2)=0.068
S=1.05
Rint
0.738
0.059
Largest diff. peak and hole
CCDC no.
1.933 and -1.471 eA-3
1442311
1.83 and -1.37 eA-3
1442312
Table2.Selected bond lengths/ Å and angle/for compound [Pb(L)2(I)2] (1)
C(1)—N(1)
C(1)—C(2)
C(1)—H(1)
C(2)—C(3)
1.318(11)
1.367(14)
0.9300
1.364(14)
0.9300
C(9)—N(2)
C(12)—N(2)
N(1)—Pb(1)
N(2)—Pb(1)
1.358(11)
1.311(12)
2.560(7)
2.566(7)
i
C(2)—H(2)
2.560(7)
Pb(1)—N(1 )
Pb(1)—N(2i)
Pb(1)—I(1i)
Pb(1)—I(1)
C(3)—C(4)
C(3)—H(3)
C(4)—C(5)
1.390(13)
0.9300
1.402(13)
2.566(7)
3.3059(7)
3.3059(7)
Symmetry transformations used to generate equivalent atoms:
(i) 1-x, y, 0.5-z.
22

Table 3. Selected bond lengths/ Å and angle/for compound [Pb(L)(L/)(H2O)].3H2O
Pb(1)—O(1)
Pb(1)—N(1)
Pb(1)—O(0)AA
Pb(1)—N(2)
Pb(1)—N(3)
Pb(1)—O(3)
O(8)—H(8)A
N(1)—C(3)
2.746(3)
2.608(3)
2.589(3)
2.724(3)
2.458(3)
2.435(3)
0.861(15)
1.370(5)
O(8)—H(8)A
O(8)—H(8)B
O(7)—H(7)A
O(6)—H(6)A
C(15)—C(16)
C(16)—H(16)
C(16)—C(17)
C(17)—C(18)
0.861(15)
0.862(15)
0.836(17)
0.858(17)
1.381(7)
0.9300
1.381(6)
1.526(6)
Table 4.The influence of temperature, reaction time and sonication power on the size of
compound 1 and 2 particles.
Compound 1
samples
1 - 1
T (°C)a
T (min)b
Sonication (input power) (W)
SEMc
50
50
50
60
60
30
0
60
60
150
50
47
1 - 2
1 - 3
1 - 4
Compound 2
samples
2 - 1
70
60
60
38
T (°C)a
T (min)b
Sonication (input power) (W)
SEMc
50
50
50
70
60
60
30
60
0
204
100
56
2 - 2
2 - 3
2 - 4
60
60
60
42
a Reaction temperature
b Reaction time
c Average diameter (nm)
23

Fig. 1. The coordination environment of Pb+2cation (up) in compound [Pb(L)2(I)2] (1) and
(down) in compound [Pb(L)(L/)(H2O)].3H2O (2).
24

Fig. 2. Eighteen molecules surrounding one molecule of 1 (up). Dashed lines represent van-
der-waals bonds. Distance of bounds in 1(down).
25

Fig. 3. Sixteen molecules surrounding one molecule 2(up). Dashed lines represent van-der-
waales bonded, Distance of bounds in 2(down).
26

Fig. 4. Weak and interaction between two monomer, distance of bound and two central metal
1(up) and 2 (down)
27

Fig. 5. ꢂ – ꢂ interaction in compound 1.
Fig. 6. ꢂ – ꢂ interaction in compound 2.
28

Fig. 7. Topological representation of molecular packing in compounds 1 (up) and 2 (down).
29