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Sonochemical synthesis of nano lead(II) metal-organic coordination polymer; New precursor for the preparation of nano-materials
Accepted Manuscript Sonochemical synthesis of nano lead(II) metal-organic coordination polymer; new precursor for the preparation of nano-materials Babak Mirtamizdoust PII: DOI: Reference:
S1350-4177(16)30340-6 http://dx.doi.org/10.1016/j.ultsonch.2016.10.001 ULTSON 3385
To appear in:
Ultrasonics Sonochemistry
Received Date: Revised Date: Accepted Date:
22 August 2016 1 October 2016 2 October 2016
Please cite this article as: B. Mirtamizdoust, Sonochemical synthesis of nano lead(II) metal-organic coordination polymer; new precursor for the preparation of nano-materials, Ultrasonics Sonochemistry (2016), doi: http:// dx.doi.org/10.1016/j.ultsonch.2016.10.001
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Sonochemical synthesis of nano lead(II) metal-organic coordination polymer; new precursor for the preparation of nano-materials by Babak Mirtamizdousta*) a)
Department of Chemistry, Faculty of Science, University of Qom, PO Box 37185-359,
Qom, Iran.
*
(Tel: +98 25 32103097 E-Mail: [email protected] )
1
Abstract: Nano-sheets of a novel Pb(II)-based 3D metal-organic coordination polymer [Pb2(nih)2(NO3)4(CH3OH)]n (1) were synthesized by a branched-tube method and sonochemical reaction. The synthesis was done using various times, concentrations of initial reagents, and irradiation power. The compound was characterized by scanning electron microscopy (SEM), elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA), differential thermal analysis (DTA), X-ray powder diffraction (XRD), and single-crystal Xray analysis. The X-ray analysis of the structures revealed the composition and stereochemistry
of
the basic
building block,
which
had
with a
formula
of
{Pb2(nih)2(NO3)4(CH3OH)}. These blocks are connected by covalent bonds originating from the nih and nitrate ligands and form infinite 3D metal-organic polymeric chains. The effect of triethylamine on the speed of nucleation was also investigated. Lead oxide nanoparticles were obtained by thermolysis of 1 at 180 °C using oleic acid as a surfactant. The average diameter of the nanoparticles was estimated by XRD to be 36 nm. The morphology and size of the PbO nanoparticles were also studied using SEM.
Key words: Ultrasonic irradiation, branched tube method, Pb(II), Nano coordination polymer, Nano-sheet, PbO nanoparticles.
2
1. Introduction Polymers are high-molecular-weight molecules composed of repeating monomer units connected by covalent bonds. Metal-organic coordination polymers are infinite systems that have organic ligands and metal ions as main basic units that are linked via coordination bonds and other weak chemical interactions [1]. These compounds are called metal organic coordination systems or metal organic networks in the case of ordered structures [2]. The components in coordination polymers mainly exist in a solid state. In solution, small units create building blocks through coordination interactions and weak forces, such as hydrogen bonding, π-π stacking, and van der Waals interactions. Based on these interactions, coordination polymers then grow through self-assembly processes (Fig. S1) [3]. Metal-organic coordination polymers and porous metal-organic systems with regularpore structure have attracted considerable attention in recent years for applications in gas storage, heterogeneous catalysis, selective guest adsorption, and sensing technologies [5–8]. Compared with traditional porous carbons and inorganic zeolites, these porous materials are built from metal ions (or metallic clusters) and organic ligands. They have great potential due to their ease of processability, flexibility, structural diversity, and geometrical control. There are four main synthetic methods for obtaining metal-organic coordination polymers [3,4]. It is essential to improve the quality of single crystals so that they are suitable for X-ray measurements. Several processes with the same starting reagents sometimes lead to different isomeric or polymorphic products (For reviewing the methods please see the supporting information file). Generally, such materials are synthesized by slow diffusion techniques, hydrothermal methods, and solvothermal synthesis methods [9–11]. Very recently, a microwave-assisted hydrothermal method was applied to prepare metal-organic coordination compounds [12-14]. In the past two decades, sonochemical methods have been widely used in nanomaterial synthesis [15-22]. The effects of ultrasound are usually divided into chemical and mechanical effects. High temperatures are responsible for the chemical effects, such as radical formation and sonoluminescence, whereas the strong shear gradients induce mechanical effects. Local hot spots can have temperatures of roughly 5000 °C and pressures of about 500 atm, but they last for only a few microseconds. These extreme conditions can drive chemical reactions as well as promote the formation of nano-sized structures. This mostly results from the instantaneous formation of many crystallization nuclei [23,24]. This 3
concept has been widely used to fabricate nano-sized structures from a variety of compounds. Recently, the application of ultrasound in synthetic organic chemistry has gathered attention because ultrasonic waves in liquids are known to cause chemical reactions in homogeneous and heterogeneous systems [25]. To date, the application of ultrasonic methods for the construction of nano metalorganic coordination compounds has been relatively unexplored. Our focus is the design and synthesis of metal-organic coordination compounds, and we have recently reported on nano lead (II) and other metal-organic coordination compounds [26–32]. As a continuation of a previous study, a novel lead(II) 3D metal-organic coordination polymer was synthesized based on a flexible hydrazonate ligand nicotinohydrazide (nih) (Scheme 1) and nitrate as an N-donor inorganic ligand. The synthesis was done using branched-tube and sonochemical methods, and we investigated the effect of the ultrasonic irradiation time, power, and concentration of initial reagents on the shape and size of particles. PbO nanoparticles were also obtained via thermolysis of the compound at 180 °C. 2. Experimental Commercially available reagents and solvents were used without further purification. An Elementar Vario CHN–O Rapid Analyzer was used for C, H, and N elemental analyses of the samples. IR spectra were obtained on a Bruker Vector 22 FT-IR spectrometer using KBr disks in the range of 4000–400 cm-1. The thermal behavior was measured with a SETARAM LABSYS thermal analyzer under air at 30–700˚C with a heating rate of 3˚C/min. Ultrasound was generated in an ultrasonic bath (SONICA-2200 EP) at a frequency of 40 KHz. X-ray powder diffraction (XRD) measurements were performed using an X’pert diffractometer (Panalytical) using monochromatized Cu kα radiation. Simulated XRD powder patterns were prepared based on single-crystal data using Mercury 2.4 [33]. The crystallite sizes of selected samples were estimated using the Scherrer formula. After gold coating, the morphology of samples was investigated using a scanning electron microscope (Philips XL 30). Diffraction data for a single crystal of 1 were collected on an Xcalibur™2 diffractometer (Oxford Diffraction Ltd.) equipped with a Sapphire2 CCD detector using Mo Kα radiation (monochromator Enhance, Oxford Diffraction Ltd.) and ωscan rotation techniques at 130 K. Data collection, cell parameter refinements, and data reduction were performed with the CrysAlis software package (Oxford Diffraction Ltd.) [34]. 4
Multi-scan absorption correction in CrysAlis was applied to the data for 1. The structure was solved by direct methods using SHELXS and refined anisotropically on all F2 data using a full-matrix weighted least-squares procedure (SHELX-2014) [35] with weight w = 1/[σ2(Fo)2 + (0.035P)2], where P = (Fo2 + 2Fc2)/3. All H-atoms were found from Fourier maps and refined using a riding model with C−H distances of 0.95 Å, N−H distances of 0.88 Å, and Uiso(H) values of 1.2Ueq(C,N). Molecular graphics were made using Mercury 2.4 [33] and DIAMOND [36]. Crystal data and structure refinement for 1 are given in Table 1, while selected bond lengths and angles are summarized in Table 2. Single crystals of [Pb2(nih)2(NO3)4(CH3OH)]n (1) were isolated by placing nih (1 mmol) and lead(II) nitrate (1 mmol) in the main arm of a branched tube. Methanol was carefully added to fill both arms. The tube was sealed, the main arm was immersed in an oil bath at 60 °C, and the other arm was kept at ambient temperature. After 6 days, crystals deposited in the cooler arm were isolated, filtered out, washed with acetone and ether, and air dried. Product: decomposition point = 177 °C, yield: 70%. Elemental analysis calculated (%) for C13H18N10O15Pb2: C: 16.12, H: 1.87, N: 14.46; found: C: 16.50, H: 2.00, N: 14.50. IR (cm-1) selected bonds: 695m, 727m, 814m, 1320(vs, nitrate), 1562m, 1606s, 1652(m, C=O), 3517m-br, 3269m-br. Ultrasonic synthesis of the compound was carried out in an ultrasonic bath at ambient temperature and atmospheric pressure for 30, 60, and 90 minutes (Table 3). The obtained precipitates were filtered out, washed with water and MeOH, and dried in air. Product: decomposition point = 175 °C, yield: 65%. Elemental analysis calculated (%) for C13H18N10O15Pb2: C: 16.12, H: 1.87, N: 14.46; found: C: 16.50, H: 2.00, N: 14.50. IR (cm-1) selected bonds: 693m, 728m, 815m, 1320(vs, nitrate), 1562m, 1606s, 1652(m, C=O), 3518mbr, 3270m-br. To study the effect of the initial reagent concentrations on the size and morphology of nano-structured 1, the above processes were performed with [nih] concentrations ([Pb(NO3)2]) of [0.05], [0.025], and [0.0125] M. The effect of triethylamine (TEA) was investigated by adding 3 mL of TEA (in 20 ml DMF) to adjust the pH to 7. Two different ultrasound powers (12 and 36 W) were applied to achieve the best morphology (Table 3).
3. Results and discussion 5
The reaction between the nih ligand and a solution of lead(II) nitrate led to the formation of 1. Its nanostructure was obtained by ultrasonic irradiation in a methanolic solution, and single-crystalline material was obtained by applying a heat gradient applied to a solution of the reagents (the branched tube method). The elemental analysis and IR spectra of the nano-structure and the single-crystalline material are indistinguishable (see Fig. 1 and table 3). The IR spectra of the nano structures and the single crystalline materials show characteristic absorption bands of the nih ligand. The relatively weak band around 3010 cm-1 is attributed to the stretching vibrations of the aromatic C–H groups. The absorption band in the range of 1400–1600 cm-1 corresponds to aromatic ring vibrations of the nih ligand. The absorption bands with strong intensities at 1652 cm-1 correspond to the C=O stretching vibrations of the carbonyl group of the nih ligands. The band at 1320 cm-1 corresponds to the nitrate group. The simulated powder XRD patterns derived from the single-crystal structures were compared with the experimental patterns from the sonochemically synthesized powder. The results confirm that the nanostructure of 1 was structurally identical to that obtained via the branched-tube method, as shown in Fig. 2 (this was also evidenced by elemental analysis). The X-ray structure of 1 revealed a composition and stereochemistry with a fundamental building block of {Pb2(nih)2(NO3)4(CH3OH)}. These blocks are connected by covalent bonds originating from the nih and nitrate ligands into infinite 3D metal-organic polymeric chains. Fig. 3 shows the molecular structure of 1 and the atom numbering scheme. Each Pb(II) atom is coordinated by one oxygen atom of the nih ligand with Pb–O distances of 2.448 (4) Ǻ for Pb1 and 2.505 (4) Ǻ for Pb2; two nitrogen atoms of two nih ligands with Pb–N distances of 2.613 (5) and 2.728 (5) Ǻ for Pb1 and 2.658 (5) and 2.731 (5) Ǻ for Pb2; four oxygen atoms of three nitrate ligands for Pb2 with Pb2–O distances of 2.684 (5), 2.800 (4), 2.804 (5), and 2.594 (5) Å; four oxygen atoms of three nitrate ligands with Pb1–O distances 2.645 (6), 2.631 (4), 2.711 (5), and 2.585 (5) Ǻ for Pb1, as well as one oxygen atom of methanol for Pb2 with a Pb2–O distance of 2.713 (4) Ǻ in an 8-atom fashion for Pb1 and Pb2 with a PbN2O6 donor set. Thus, the coordination number of the Pb(II) atoms is eight. However, in Pb2, two of the Pb–O distances (Pb2–O2 = 2.804 (5) and Pb2–O1 =2.800 (4) Ǻ) are slightly longer than the others, as shown in Table 2. This is attributed to the effect of the 6s2 lone electron pair localized within the valence shell of the lead (II) atom. If the stereochemically active lone pair [37] were not present, more symmetry would be expected. We found some differences in 6
the Pb-ligand bond distances from the regular bond lengths, which could have resulted from the lead (II) 6s2 lone pair of active electrons [37]. There are C–H···O interactions and N–H···O interactions among the weak noncovalent contacts between adjacent fragments (Figure 4). The distances of these interactions (Table 4) suggest relatively strong interactions within these contacts [38]. Consequently, the labile interactions also allow for self-assembly of a 3D network (Fig. 4). Thus, covalent interactions, the lone pair activity, and H-bonding interactions may control the coordination sphere of lead(II) ions in this complex. The morphology and size of compound 1 from the sonochemical method was investigated using scanning electron microscopy (SEM) while controlling the nucleation and changing the sonication time, sonication power, concentration of the starting materials. Almost in all cases Nano-cross sheets was the dominant morphology. For compound 1, the sonication time as a parameter was changed at a constant concentration of [0.025] M of starting materials. Nano-cross sheets of compound 1 were obtained for all three sonication times (30, 60, and 90 min). For this metal-organic coordination polymer, the thickness of sheets grew from 37 to 43 nm upon increasing the sonication time (Fig. 5). Therefore, with a sonication time of 30 min, the concentration of initial reagents was changed to half and twice the first concentration ([0.0125] and [0.05] M). In this case, thinner sheets of 30 to 60 nm were collected at lower concentrations (Figs. 6 E and F). Thinner sheets (~60 nm) were also acquired when using TEA in the reaction for 30 min with a concentration of [0.025] M (Fig. 6G). This means that fast nucleation has the same effect as the reduction of concentrations in this case. Finally, in order to find the effect of ultrasonic power on the morphology and size, the experimental conditions of the best sample (sample E) were used with ultrasonic power of 36 W. In this case, uniformly sheet-like morphology with thickness of 65–80 nm was obtained (Fig. 6H). Nano lead oxide was generated by thermolysis of 1 at 180 °C with oleic acid as a surfactant. The powder XRD patterns (Fig. 7) match the standard pattern of orthorhombic PbO with a = 5.8931 Å and z= 4 (JCPDS card file No. 77-1971), which confirms the formation of PbO powder. Significant broadening of the peaks of the nanostructure indicates that the particles have nanometer dimensions. The average size of the particles was estimated by the Scherrer formula as 36 nm. The morphology and size of the prepared PbO samples were further investigated using SEM. The bulk powder of 1 produces regularly shaped Pb(II) oxide nanoparticles with diameter of about 36 nm (Fig. 8). 7
Thermal analysis plays an important role in studying the structure and properties of metal complexes. TGA and DTA were performed on 1 at 30 to 700 oC in air. The TG curves showed neither weight loss nor structural changes up to about 165 °C, demonstrating that the framework of [Pb2(nih)2(NO3)4(CH3OH)]n was retained at these high temperatures. Thermal decomposition occurs in a four-step process from 250 to 600
o
C, with complete
decomposition of the complex occurring with loss of all ligands, methanol, and nitrate (65%). An endothermic effect occurs at 175 °C, and four exothermic effects occur at 329, 350, 390, and 460 °C in DTA. Solid residue is formed at the end of the decomposition, which is suggested to contain lead oxide (Fig. 9).
4. Conclusion A branched-tube method was used to synthesize a novel 3D Pb(II) metal-organic coordination polymer containing an nih ligand and N-donor inorganic nitrate ligands. A simple sonochemical method was presented for the preparation of nanosheets of this coordination polymer and PbO nanoparticles. Various parameters such as the time and concentration of initial reagents were investigated. The crystal structure of the compound was determined and indicated that the composition and stereochemistry had a fundamental building block with a formula of {Pb2(nih)2(NO3)4(CH3OH)}, which formed a threedimensional polymer in solid state. The results of the sonochemical method show that a lower concentration of reagents leads to a decrease in particle size. TEA influences the speed of the nucleation during the synthesis and decreases the particle size, while increasing the power of ultrasonic irradiation led to uniform sheet-like morphology with thickness ranging from 30 to 60 nm. Finally, PbO nanoparticles were obtained by thermolysis of 1 at 180 °C in air atmosphere.
5. Supplementary material Crystallographic data for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as a supplementary publication with CCDC- 1495590 for [Pb2(nih)2(NO3)4(CH3OH)]n (1). Copies of the data can be obtained upon
8
request from CCDC, 12 Union Road, Cambridge CB2 1EZ, UK [Fax: +44-1223-336033; Email: [email protected]].
Acknowledgements Support of this investigation by University of Qom is gratefully acknowledged.
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Table 1. Crystal data and structure refinement for 1.
Chemical formula
C13H18N9O12Pb2·NO3
Mr
968.75
Crystal system, space group
Monoclinic, P21/c
Temperature (K)
130
a, b, c (Å)
7.4359 (1), 22.4522 (3), 14.4797 (3)
β (°)
93.374 (2) 3
V (Å )
2413.23 (7)
Z
4
Radiation type
Mo Kα
-1
µ (mm )
14.03
Crystal size (mm)
0.26 × 0.19 × 0.16
Tmin, Tmax
0.351, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections
17589, 5475, 4549
Rint
0.042 -1
0.650
(sin θ/λ)max (Å ) 2
2
2
R[F > 2σ(F )], wR(F ), S
0.034, 0.074, 1.06
No. of reflections
5475
No. of parameters
364
No. of restraints
13
H-atom treatment
H atoms treated by a mixture of independent and constrained refinement
∆〉max, ∆〉min (e Å-3)
1.56, -1.71
13
Table 2. Selected interatomic parameters [Å, °] for 1.
O5—Pb2
2.684 (5)
O13—Pb2
2.713 (4)
O4—Pb1
2.645 (6)
i
Pb1—O14
2.448 (4)
O12—Pb2
2.594 (5)
Pb1—O8
2.631 (4)
N7—Pb2
2.658 (5)
Pb1—O7
i
N10—Pb1
i
2.711 (5)
2.613 (5)
i
Pb1—N10
2.613 (5)
O14—Pb1
2.448 (4)
Pb2—O15
2.505 (4)
Pb2—N8
2.731 (5)
Pb1—O1
2.585 (5)
i
N5—Pb1
2.728 (5)
Pb2—O1
2.800(4)
Pb2—O2
2.804(5)
O4—Pb1—O7
151.63 (17)
O5—Pb2—O13
110.37 (17)
i
81.41 (19)
O5—Pb2—N8
70.82 (18)
i
76.95 (14)
O12—Pb2—O5
142.18 (16)
73.48 (15)
O12—Pb2—N7
82.68 (17)
O14 —Pb1—N10
63.16 (14)
O12—Pb2—O13
100.53 (15)
O8—Pb1—O4
138.1 (2)
O12—Pb2—N8
88.34 (16)
O8—Pb1—O7
O14 —Pb1—O4 O14 —Pb1—O8 i
O14 —Pb1—O7 i
i
47.77 (12)
N7—Pb2—O5
91.19 (18)
i
88.59 (18)
N7—Pb2—O13
64.54 (14)
i
112.03 (14)
N7—Pb2—N8
136.63 (15)
i
N10 —Pb1—O7
68.54 (14)
O13—Pb2—N8
158.44 (14)
O15—Pb2—O13
126.57 (13)
O15—Pb2—O5
73.48 (16)
O15—Pb2—N8
74.87 (14)
O15—Pb2—O12
70.69 (15)
O15—Pb2—N7
62.10 (14)
N10 —Pb1—O4 N10 —Pb1—O8
Symmetry transformation used to generate equivalent atoms: (i) -x+2, -y+1, -z+1.
14
Table 3. Experimental details for synthesis of nano [Pb2(nih)2(NO3)4(CH3OH)]n (1).
Samples name
Concentration [nih]/[Pb(NO3)2] (M)
Time
Power
Elemental analysis,
Yield
(min)
(W)
found (%)*
(%)
Morphology
A
[0.025]/[0.025]/[0.025]
30
12
C: 16.45, H: 1.95, N: 14.50
67
Nano-cross sheets
B
[0.025]/[0.025]/[0.025]
60
12
C: 16.40, H: 1.90, N: 14.45
66
Nano-cross sheets
C
[0.025]/[0.025]/[0.025]
90
12
C: 16.45, H: 2.00, N: 14.50
73
Nano-cross sheets
D
[0.05]/[0.05]/[0.05]
30
12
C: 16.40, H: 1.90, N: 14.50
70
Nano-cross sheets
E
[0.0125]/[0.0125]/[0.0125]
30
12
C: 16.40, H: 1.90, N: 14.50
68
Nano-cross sheets
F
[0.025]/[0.025]/[0.025],
30
12
C: 16.40, H: 2.00, N: 14.45
60
Nano-cross sheets
30
36
C: 16.45, H: 2.00, N: 14.50
71
Nano-cross sheets
TEA = 3 ml, pH = 7
G
[0.0125]/[0.0125]/[0.0125]
* calculated (%) for C13H18N10O15Pb2: C: 16.12, H: 1.87, N: 14.46
15
Table 4. Selected non-covalent contacts in the crystal structure of 1 [Å and °].
D-H...A
d(D-H)
d(H...A)
d(D...A)
<(DHA)
N(6)-H(6)...O(4) N(7)-H(7)...O(2) N(9)-H(9)...O(8) C(2)-H(2)...O(12) C(9)-H(9)...O(5) C(3)-H(3)...O(8) C(2)-H(2)...O(13)
0.88 0.88 0.88 0.95 0.95 0.95 0.95
2.102 2.125 2.061 2.733 2.690 2.571 2.599
2.937(4) 2.881(4) 2.897(5) 3.198(6) 3.499(5) 3.299(6) 3.221(5)
150.1 154.4 158.4 110.2 139.7 133.8 132.0
16
Scheme 1. A schematic representation of the nih molecule showing the possible coordination.
17
Figure. 1. IR spectra of crystal and nanostructure of [Pb2(nih)2(NO3)4(CH3OH)]n (1) produced by branched-tube method and sonochemical method.
18
Figure 2. PXRD patterns of [Pb2(nih)2(NO3)4(CH3OH)]n (1) prepared by (a) branched-tube method and (b) sonochemical reaction.
19
Figure 3. Asymmetric unification of [Pb2(nih)2(NO3)4(CH3OH)]n (1)
20
Figure 4. a) A part of the crystal structure of 1; b) crystal structure showing the weak interactions; c) self-assembly of 3D structure
21
Figure 5. SEM images of nanosheets of 1 synthesized by sonochemical reaction with reagent concentration of [0.025] M and sonication times of (a) 30 min, (b) 60 min, and (c) 90 min. 22
Figure 6. SEM images of 1 synthesized by sonochemical reaction: (a) sample E, (b) sample D, (c) sample F, and (d) sample G. 23
Figure 7. XRD pattern of nano lead oxide after calcination of 1 at 180 °C
24
Figure 8. SEM photograph of nano lead oxide (produced by the thermolysis of nanostructures of 1 at 180 °C) and particle size histogram.
25
Figure 9. TG and DTA curves of complex 1.
26
• •
• • •
A new Pb(II)-based 3D metal-organic coordination polymer was synthesized. Branched-tube method and sonochemical reaction used to synthesis of compounds Ultrasound synthesis of nano-sheets coordination polymer have been reported. The crystal structure of the compound is reported. The morphology of lead oxide were further observed using SEM.
27
S1350-4177(16)30340-6 http://dx.doi.org/10.1016/j.ultsonch.2016.10.001 ULTSON 3385
To appear in:
Ultrasonics Sonochemistry
Received Date: Revised Date: Accepted Date:
22 August 2016 1 October 2016 2 October 2016
Please cite this article as: B. Mirtamizdoust, Sonochemical synthesis of nano lead(II) metal-organic coordination polymer; new precursor for the preparation of nano-materials, Ultrasonics Sonochemistry (2016), doi: http:// dx.doi.org/10.1016/j.ultsonch.2016.10.001
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Sonochemical synthesis of nano lead(II) metal-organic coordination polymer; new precursor for the preparation of nano-materials by Babak Mirtamizdousta*) a)
Department of Chemistry, Faculty of Science, University of Qom, PO Box 37185-359,
Qom, Iran.
*
(Tel: +98 25 32103097 E-Mail: [email protected] )
1
Abstract: Nano-sheets of a novel Pb(II)-based 3D metal-organic coordination polymer [Pb2(nih)2(NO3)4(CH3OH)]n (1) were synthesized by a branched-tube method and sonochemical reaction. The synthesis was done using various times, concentrations of initial reagents, and irradiation power. The compound was characterized by scanning electron microscopy (SEM), elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA), differential thermal analysis (DTA), X-ray powder diffraction (XRD), and single-crystal Xray analysis. The X-ray analysis of the structures revealed the composition and stereochemistry
of
the basic
building block,
which
had
with a
formula
of
{Pb2(nih)2(NO3)4(CH3OH)}. These blocks are connected by covalent bonds originating from the nih and nitrate ligands and form infinite 3D metal-organic polymeric chains. The effect of triethylamine on the speed of nucleation was also investigated. Lead oxide nanoparticles were obtained by thermolysis of 1 at 180 °C using oleic acid as a surfactant. The average diameter of the nanoparticles was estimated by XRD to be 36 nm. The morphology and size of the PbO nanoparticles were also studied using SEM.
Key words: Ultrasonic irradiation, branched tube method, Pb(II), Nano coordination polymer, Nano-sheet, PbO nanoparticles.
2
1. Introduction Polymers are high-molecular-weight molecules composed of repeating monomer units connected by covalent bonds. Metal-organic coordination polymers are infinite systems that have organic ligands and metal ions as main basic units that are linked via coordination bonds and other weak chemical interactions [1]. These compounds are called metal organic coordination systems or metal organic networks in the case of ordered structures [2]. The components in coordination polymers mainly exist in a solid state. In solution, small units create building blocks through coordination interactions and weak forces, such as hydrogen bonding, π-π stacking, and van der Waals interactions. Based on these interactions, coordination polymers then grow through self-assembly processes (Fig. S1) [3]. Metal-organic coordination polymers and porous metal-organic systems with regularpore structure have attracted considerable attention in recent years for applications in gas storage, heterogeneous catalysis, selective guest adsorption, and sensing technologies [5–8]. Compared with traditional porous carbons and inorganic zeolites, these porous materials are built from metal ions (or metallic clusters) and organic ligands. They have great potential due to their ease of processability, flexibility, structural diversity, and geometrical control. There are four main synthetic methods for obtaining metal-organic coordination polymers [3,4]. It is essential to improve the quality of single crystals so that they are suitable for X-ray measurements. Several processes with the same starting reagents sometimes lead to different isomeric or polymorphic products (For reviewing the methods please see the supporting information file). Generally, such materials are synthesized by slow diffusion techniques, hydrothermal methods, and solvothermal synthesis methods [9–11]. Very recently, a microwave-assisted hydrothermal method was applied to prepare metal-organic coordination compounds [12-14]. In the past two decades, sonochemical methods have been widely used in nanomaterial synthesis [15-22]. The effects of ultrasound are usually divided into chemical and mechanical effects. High temperatures are responsible for the chemical effects, such as radical formation and sonoluminescence, whereas the strong shear gradients induce mechanical effects. Local hot spots can have temperatures of roughly 5000 °C and pressures of about 500 atm, but they last for only a few microseconds. These extreme conditions can drive chemical reactions as well as promote the formation of nano-sized structures. This mostly results from the instantaneous formation of many crystallization nuclei [23,24]. This 3
concept has been widely used to fabricate nano-sized structures from a variety of compounds. Recently, the application of ultrasound in synthetic organic chemistry has gathered attention because ultrasonic waves in liquids are known to cause chemical reactions in homogeneous and heterogeneous systems [25]. To date, the application of ultrasonic methods for the construction of nano metalorganic coordination compounds has been relatively unexplored. Our focus is the design and synthesis of metal-organic coordination compounds, and we have recently reported on nano lead (II) and other metal-organic coordination compounds [26–32]. As a continuation of a previous study, a novel lead(II) 3D metal-organic coordination polymer was synthesized based on a flexible hydrazonate ligand nicotinohydrazide (nih) (Scheme 1) and nitrate as an N-donor inorganic ligand. The synthesis was done using branched-tube and sonochemical methods, and we investigated the effect of the ultrasonic irradiation time, power, and concentration of initial reagents on the shape and size of particles. PbO nanoparticles were also obtained via thermolysis of the compound at 180 °C. 2. Experimental Commercially available reagents and solvents were used without further purification. An Elementar Vario CHN–O Rapid Analyzer was used for C, H, and N elemental analyses of the samples. IR spectra were obtained on a Bruker Vector 22 FT-IR spectrometer using KBr disks in the range of 4000–400 cm-1. The thermal behavior was measured with a SETARAM LABSYS thermal analyzer under air at 30–700˚C with a heating rate of 3˚C/min. Ultrasound was generated in an ultrasonic bath (SONICA-2200 EP) at a frequency of 40 KHz. X-ray powder diffraction (XRD) measurements were performed using an X’pert diffractometer (Panalytical) using monochromatized Cu kα radiation. Simulated XRD powder patterns were prepared based on single-crystal data using Mercury 2.4 [33]. The crystallite sizes of selected samples were estimated using the Scherrer formula. After gold coating, the morphology of samples was investigated using a scanning electron microscope (Philips XL 30). Diffraction data for a single crystal of 1 were collected on an Xcalibur™2 diffractometer (Oxford Diffraction Ltd.) equipped with a Sapphire2 CCD detector using Mo Kα radiation (monochromator Enhance, Oxford Diffraction Ltd.) and ωscan rotation techniques at 130 K. Data collection, cell parameter refinements, and data reduction were performed with the CrysAlis software package (Oxford Diffraction Ltd.) [34]. 4
Multi-scan absorption correction in CrysAlis was applied to the data for 1. The structure was solved by direct methods using SHELXS and refined anisotropically on all F2 data using a full-matrix weighted least-squares procedure (SHELX-2014) [35] with weight w = 1/[σ2(Fo)2 + (0.035P)2], where P = (Fo2 + 2Fc2)/3. All H-atoms were found from Fourier maps and refined using a riding model with C−H distances of 0.95 Å, N−H distances of 0.88 Å, and Uiso(H) values of 1.2Ueq(C,N). Molecular graphics were made using Mercury 2.4 [33] and DIAMOND [36]. Crystal data and structure refinement for 1 are given in Table 1, while selected bond lengths and angles are summarized in Table 2. Single crystals of [Pb2(nih)2(NO3)4(CH3OH)]n (1) were isolated by placing nih (1 mmol) and lead(II) nitrate (1 mmol) in the main arm of a branched tube. Methanol was carefully added to fill both arms. The tube was sealed, the main arm was immersed in an oil bath at 60 °C, and the other arm was kept at ambient temperature. After 6 days, crystals deposited in the cooler arm were isolated, filtered out, washed with acetone and ether, and air dried. Product: decomposition point = 177 °C, yield: 70%. Elemental analysis calculated (%) for C13H18N10O15Pb2: C: 16.12, H: 1.87, N: 14.46; found: C: 16.50, H: 2.00, N: 14.50. IR (cm-1) selected bonds: 695m, 727m, 814m, 1320(vs, nitrate), 1562m, 1606s, 1652(m, C=O), 3517m-br, 3269m-br. Ultrasonic synthesis of the compound was carried out in an ultrasonic bath at ambient temperature and atmospheric pressure for 30, 60, and 90 minutes (Table 3). The obtained precipitates were filtered out, washed with water and MeOH, and dried in air. Product: decomposition point = 175 °C, yield: 65%. Elemental analysis calculated (%) for C13H18N10O15Pb2: C: 16.12, H: 1.87, N: 14.46; found: C: 16.50, H: 2.00, N: 14.50. IR (cm-1) selected bonds: 693m, 728m, 815m, 1320(vs, nitrate), 1562m, 1606s, 1652(m, C=O), 3518mbr, 3270m-br. To study the effect of the initial reagent concentrations on the size and morphology of nano-structured 1, the above processes were performed with [nih] concentrations ([Pb(NO3)2]) of [0.05], [0.025], and [0.0125] M. The effect of triethylamine (TEA) was investigated by adding 3 mL of TEA (in 20 ml DMF) to adjust the pH to 7. Two different ultrasound powers (12 and 36 W) were applied to achieve the best morphology (Table 3).
3. Results and discussion 5
The reaction between the nih ligand and a solution of lead(II) nitrate led to the formation of 1. Its nanostructure was obtained by ultrasonic irradiation in a methanolic solution, and single-crystalline material was obtained by applying a heat gradient applied to a solution of the reagents (the branched tube method). The elemental analysis and IR spectra of the nano-structure and the single-crystalline material are indistinguishable (see Fig. 1 and table 3). The IR spectra of the nano structures and the single crystalline materials show characteristic absorption bands of the nih ligand. The relatively weak band around 3010 cm-1 is attributed to the stretching vibrations of the aromatic C–H groups. The absorption band in the range of 1400–1600 cm-1 corresponds to aromatic ring vibrations of the nih ligand. The absorption bands with strong intensities at 1652 cm-1 correspond to the C=O stretching vibrations of the carbonyl group of the nih ligands. The band at 1320 cm-1 corresponds to the nitrate group. The simulated powder XRD patterns derived from the single-crystal structures were compared with the experimental patterns from the sonochemically synthesized powder. The results confirm that the nanostructure of 1 was structurally identical to that obtained via the branched-tube method, as shown in Fig. 2 (this was also evidenced by elemental analysis). The X-ray structure of 1 revealed a composition and stereochemistry with a fundamental building block of {Pb2(nih)2(NO3)4(CH3OH)}. These blocks are connected by covalent bonds originating from the nih and nitrate ligands into infinite 3D metal-organic polymeric chains. Fig. 3 shows the molecular structure of 1 and the atom numbering scheme. Each Pb(II) atom is coordinated by one oxygen atom of the nih ligand with Pb–O distances of 2.448 (4) Ǻ for Pb1 and 2.505 (4) Ǻ for Pb2; two nitrogen atoms of two nih ligands with Pb–N distances of 2.613 (5) and 2.728 (5) Ǻ for Pb1 and 2.658 (5) and 2.731 (5) Ǻ for Pb2; four oxygen atoms of three nitrate ligands for Pb2 with Pb2–O distances of 2.684 (5), 2.800 (4), 2.804 (5), and 2.594 (5) Å; four oxygen atoms of three nitrate ligands with Pb1–O distances 2.645 (6), 2.631 (4), 2.711 (5), and 2.585 (5) Ǻ for Pb1, as well as one oxygen atom of methanol for Pb2 with a Pb2–O distance of 2.713 (4) Ǻ in an 8-atom fashion for Pb1 and Pb2 with a PbN2O6 donor set. Thus, the coordination number of the Pb(II) atoms is eight. However, in Pb2, two of the Pb–O distances (Pb2–O2 = 2.804 (5) and Pb2–O1 =2.800 (4) Ǻ) are slightly longer than the others, as shown in Table 2. This is attributed to the effect of the 6s2 lone electron pair localized within the valence shell of the lead (II) atom. If the stereochemically active lone pair [37] were not present, more symmetry would be expected. We found some differences in 6
the Pb-ligand bond distances from the regular bond lengths, which could have resulted from the lead (II) 6s2 lone pair of active electrons [37]. There are C–H···O interactions and N–H···O interactions among the weak noncovalent contacts between adjacent fragments (Figure 4). The distances of these interactions (Table 4) suggest relatively strong interactions within these contacts [38]. Consequently, the labile interactions also allow for self-assembly of a 3D network (Fig. 4). Thus, covalent interactions, the lone pair activity, and H-bonding interactions may control the coordination sphere of lead(II) ions in this complex. The morphology and size of compound 1 from the sonochemical method was investigated using scanning electron microscopy (SEM) while controlling the nucleation and changing the sonication time, sonication power, concentration of the starting materials. Almost in all cases Nano-cross sheets was the dominant morphology. For compound 1, the sonication time as a parameter was changed at a constant concentration of [0.025] M of starting materials. Nano-cross sheets of compound 1 were obtained for all three sonication times (30, 60, and 90 min). For this metal-organic coordination polymer, the thickness of sheets grew from 37 to 43 nm upon increasing the sonication time (Fig. 5). Therefore, with a sonication time of 30 min, the concentration of initial reagents was changed to half and twice the first concentration ([0.0125] and [0.05] M). In this case, thinner sheets of 30 to 60 nm were collected at lower concentrations (Figs. 6 E and F). Thinner sheets (~60 nm) were also acquired when using TEA in the reaction for 30 min with a concentration of [0.025] M (Fig. 6G). This means that fast nucleation has the same effect as the reduction of concentrations in this case. Finally, in order to find the effect of ultrasonic power on the morphology and size, the experimental conditions of the best sample (sample E) were used with ultrasonic power of 36 W. In this case, uniformly sheet-like morphology with thickness of 65–80 nm was obtained (Fig. 6H). Nano lead oxide was generated by thermolysis of 1 at 180 °C with oleic acid as a surfactant. The powder XRD patterns (Fig. 7) match the standard pattern of orthorhombic PbO with a = 5.8931 Å and z= 4 (JCPDS card file No. 77-1971), which confirms the formation of PbO powder. Significant broadening of the peaks of the nanostructure indicates that the particles have nanometer dimensions. The average size of the particles was estimated by the Scherrer formula as 36 nm. The morphology and size of the prepared PbO samples were further investigated using SEM. The bulk powder of 1 produces regularly shaped Pb(II) oxide nanoparticles with diameter of about 36 nm (Fig. 8). 7
Thermal analysis plays an important role in studying the structure and properties of metal complexes. TGA and DTA were performed on 1 at 30 to 700 oC in air. The TG curves showed neither weight loss nor structural changes up to about 165 °C, demonstrating that the framework of [Pb2(nih)2(NO3)4(CH3OH)]n was retained at these high temperatures. Thermal decomposition occurs in a four-step process from 250 to 600
o
C, with complete
decomposition of the complex occurring with loss of all ligands, methanol, and nitrate (65%). An endothermic effect occurs at 175 °C, and four exothermic effects occur at 329, 350, 390, and 460 °C in DTA. Solid residue is formed at the end of the decomposition, which is suggested to contain lead oxide (Fig. 9).
4. Conclusion A branched-tube method was used to synthesize a novel 3D Pb(II) metal-organic coordination polymer containing an nih ligand and N-donor inorganic nitrate ligands. A simple sonochemical method was presented for the preparation of nanosheets of this coordination polymer and PbO nanoparticles. Various parameters such as the time and concentration of initial reagents were investigated. The crystal structure of the compound was determined and indicated that the composition and stereochemistry had a fundamental building block with a formula of {Pb2(nih)2(NO3)4(CH3OH)}, which formed a threedimensional polymer in solid state. The results of the sonochemical method show that a lower concentration of reagents leads to a decrease in particle size. TEA influences the speed of the nucleation during the synthesis and decreases the particle size, while increasing the power of ultrasonic irradiation led to uniform sheet-like morphology with thickness ranging from 30 to 60 nm. Finally, PbO nanoparticles were obtained by thermolysis of 1 at 180 °C in air atmosphere.
5. Supplementary material Crystallographic data for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as a supplementary publication with CCDC- 1495590 for [Pb2(nih)2(NO3)4(CH3OH)]n (1). Copies of the data can be obtained upon
8
request from CCDC, 12 Union Road, Cambridge CB2 1EZ, UK [Fax: +44-1223-336033; Email: [email protected]].
Acknowledgements Support of this investigation by University of Qom is gratefully acknowledged.
9
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[19] K. Akhbari, M. Hemmati, A. Morsali, J. Inorg. Organomet. Polym., 21 (2011) 352-359. [20] K. Akhbari, A. Morsali, J. Organomet. Chem., 692 (2007) 5141-5146. [21] K. Akhbari, A. Morsali, Polyhedron, 30 (2011) 1456-1462. [22] K. Akhbari, A. Morsali, Inorg. Chem. Commun. 10 (2007) 1189-1193. [23] H. F. Mark, Encyclopedia of Polymer Science and Technology; WileyInterscience: New York, 2005, ' 2005 John Wiley & Sons, Inc. [24] H. Sadeghzadeh, A. Morsali, Ultrason. Sonochem.18 (2011) 80-84 and references therein. [25] A. Aslani, A. Morsali, M. Zeller, Solid State Sciences 10 (2008) 1591-1597. [26] A. Valipour, B. Mirtamizdoust, M. Ghaedi, F. Taghizadeh, P. Talemi, J. Inorg. Organomet. Polym., 26(2016) 197-207. [27] Y. Hanifehpour, B. Mirtamizdoust, A. Morsali, S.W. Joo, Ultrason. Sonochem., 23 (2015) 275-281. [28] Y. Hanifehpour, B. Mirtamizdoust, A. Morsali, S.W. Joo, Ultrason. Sonochem., 31 (2016) 201-205. [29] Y. Hanifehpour, B. Mirtamizdoust, B. Khomami, S.W. Joo, Z. Anorg. Allg. Chem. 641 (2015) 2466–2472. [30] B. Mirtamizdoust. Z. Trávníček, Y. Hanifehpour, P. Talemi, H. Hammud, S.W. Joo, Ultrason. Sonochem., 34 (2015) 255-261. [31] B. Mirtamizdoust, D. Bieńko, Y. Hanifehpour, E.R.T. Tiekink, V.T. Yilmaz, P. Talemi. S.W. Joo, J. Inorg. Organomet. Polym., 26(2016) 819-828. [32] B. Mirtamizdoust, M. Ghaedi, Y. Hanifehpour, G.T. Mague, S.W. Joo, Mater. Chem. Phys., 182 (2016) 101-109. [33] Mercury 2.4, Copyright Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, CB2 1EZ, UK, 2001–2010. [34] Oxford Diffraction. CrysAlis RED and CrysAlis CCD software (Ver.1.171.32.5), Oxford Diffraction Ltd.: Abingdon, Oxfordshire, UK, 2003. [35] Sheldrick, G.M. Acta Cryst. A64 (2008) 112–122. 11
[36] Brandenburg, K. And Putz, H., DIAMOND, Crystal and Molecular Structure Visualization, Release 3.2g, Crystal Impact GbR: Bonn, Germany, 2011. [37] L. Shimonni-Livny, J. P. Glusker, C. W.Bock, Inorg. Chem. 37 (1998) 18531867. [38] T. Dorn, C. Janiak, K. Abu-Shandi, CrystEngComm.7 (2005) 633-641.
12
Table 1. Crystal data and structure refinement for 1.
Chemical formula
C13H18N9O12Pb2·NO3
Mr
968.75
Crystal system, space group
Monoclinic, P21/c
Temperature (K)
130
a, b, c (Å)
7.4359 (1), 22.4522 (3), 14.4797 (3)
β (°)
93.374 (2) 3
V (Å )
2413.23 (7)
Z
4
Radiation type
Mo Kα
-1
µ (mm )
14.03
Crystal size (mm)
0.26 × 0.19 × 0.16
Tmin, Tmax
0.351, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections
17589, 5475, 4549
Rint
0.042 -1
0.650
(sin θ/λ)max (Å ) 2
2
2
R[F > 2σ(F )], wR(F ), S
0.034, 0.074, 1.06
No. of reflections
5475
No. of parameters
364
No. of restraints
13
H-atom treatment
H atoms treated by a mixture of independent and constrained refinement
∆〉max, ∆〉min (e Å-3)
1.56, -1.71
13
Table 2. Selected interatomic parameters [Å, °] for 1.
O5—Pb2
2.684 (5)
O13—Pb2
2.713 (4)
O4—Pb1
2.645 (6)
i
Pb1—O14
2.448 (4)
O12—Pb2
2.594 (5)
Pb1—O8
2.631 (4)
N7—Pb2
2.658 (5)
Pb1—O7
i
N10—Pb1
i
2.711 (5)
2.613 (5)
i
Pb1—N10
2.613 (5)
O14—Pb1
2.448 (4)
Pb2—O15
2.505 (4)
Pb2—N8
2.731 (5)
Pb1—O1
2.585 (5)
i
N5—Pb1
2.728 (5)
Pb2—O1
2.800(4)
Pb2—O2
2.804(5)
O4—Pb1—O7
151.63 (17)
O5—Pb2—O13
110.37 (17)
i
81.41 (19)
O5—Pb2—N8
70.82 (18)
i
76.95 (14)
O12—Pb2—O5
142.18 (16)
73.48 (15)
O12—Pb2—N7
82.68 (17)
O14 —Pb1—N10
63.16 (14)
O12—Pb2—O13
100.53 (15)
O8—Pb1—O4
138.1 (2)
O12—Pb2—N8
88.34 (16)
O8—Pb1—O7
O14 —Pb1—O4 O14 —Pb1—O8 i
O14 —Pb1—O7 i
i
47.77 (12)
N7—Pb2—O5
91.19 (18)
i
88.59 (18)
N7—Pb2—O13
64.54 (14)
i
112.03 (14)
N7—Pb2—N8
136.63 (15)
i
N10 —Pb1—O7
68.54 (14)
O13—Pb2—N8
158.44 (14)
O15—Pb2—O13
126.57 (13)
O15—Pb2—O5
73.48 (16)
O15—Pb2—N8
74.87 (14)
O15—Pb2—O12
70.69 (15)
O15—Pb2—N7
62.10 (14)
N10 —Pb1—O4 N10 —Pb1—O8
Symmetry transformation used to generate equivalent atoms: (i) -x+2, -y+1, -z+1.
14
Table 3. Experimental details for synthesis of nano [Pb2(nih)2(NO3)4(CH3OH)]n (1).
Samples name
Concentration [nih]/[Pb(NO3)2] (M)
Time
Power
Elemental analysis,
Yield
(min)
(W)
found (%)*
(%)
Morphology
A
[0.025]/[0.025]/[0.025]
30
12
C: 16.45, H: 1.95, N: 14.50
67
Nano-cross sheets
B
[0.025]/[0.025]/[0.025]
60
12
C: 16.40, H: 1.90, N: 14.45
66
Nano-cross sheets
C
[0.025]/[0.025]/[0.025]
90
12
C: 16.45, H: 2.00, N: 14.50
73
Nano-cross sheets
D
[0.05]/[0.05]/[0.05]
30
12
C: 16.40, H: 1.90, N: 14.50
70
Nano-cross sheets
E
[0.0125]/[0.0125]/[0.0125]
30
12
C: 16.40, H: 1.90, N: 14.50
68
Nano-cross sheets
F
[0.025]/[0.025]/[0.025],
30
12
C: 16.40, H: 2.00, N: 14.45
60
Nano-cross sheets
30
36
C: 16.45, H: 2.00, N: 14.50
71
Nano-cross sheets
TEA = 3 ml, pH = 7
G
[0.0125]/[0.0125]/[0.0125]
* calculated (%) for C13H18N10O15Pb2: C: 16.12, H: 1.87, N: 14.46
15
Table 4. Selected non-covalent contacts in the crystal structure of 1 [Å and °].
D-H...A
d(D-H)
d(H...A)
d(D...A)
<(DHA)
N(6)-H(6)...O(4) N(7)-H(7)...O(2) N(9)-H(9)...O(8) C(2)-H(2)...O(12) C(9)-H(9)...O(5) C(3)-H(3)...O(8) C(2)-H(2)...O(13)
0.88 0.88 0.88 0.95 0.95 0.95 0.95
2.102 2.125 2.061 2.733 2.690 2.571 2.599
2.937(4) 2.881(4) 2.897(5) 3.198(6) 3.499(5) 3.299(6) 3.221(5)
150.1 154.4 158.4 110.2 139.7 133.8 132.0
16
Scheme 1. A schematic representation of the nih molecule showing the possible coordination.
17
Figure. 1. IR spectra of crystal and nanostructure of [Pb2(nih)2(NO3)4(CH3OH)]n (1) produced by branched-tube method and sonochemical method.
18
Figure 2. PXRD patterns of [Pb2(nih)2(NO3)4(CH3OH)]n (1) prepared by (a) branched-tube method and (b) sonochemical reaction.
19
Figure 3. Asymmetric unification of [Pb2(nih)2(NO3)4(CH3OH)]n (1)
20
Figure 4. a) A part of the crystal structure of 1; b) crystal structure showing the weak interactions; c) self-assembly of 3D structure
21
Figure 5. SEM images of nanosheets of 1 synthesized by sonochemical reaction with reagent concentration of [0.025] M and sonication times of (a) 30 min, (b) 60 min, and (c) 90 min. 22
Figure 6. SEM images of 1 synthesized by sonochemical reaction: (a) sample E, (b) sample D, (c) sample F, and (d) sample G. 23
Figure 7. XRD pattern of nano lead oxide after calcination of 1 at 180 °C
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Figure 8. SEM photograph of nano lead oxide (produced by the thermolysis of nanostructures of 1 at 180 °C) and particle size histogram.
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Figure 9. TG and DTA curves of complex 1.
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A new Pb(II)-based 3D metal-organic coordination polymer was synthesized. Branched-tube method and sonochemical reaction used to synthesis of compounds Ultrasound synthesis of nano-sheets coordination polymer have been reported. The crystal structure of the compound is reported. The morphology of lead oxide were further observed using SEM.
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