Sonochemical synthesis of a nano-structured zinc(II) amidic pillar metal-organic framework

Article abstract of DOI:10.1016/j.ultsonch.2015.05.034

A facile and environmentally friendly nano-scale synthesis of a Zn(II) metal-organic framework (MOF), {[Zn₄(BDC)₄(bpta)₄]·5DMF·3H₂O}_n (1) (bpta = N,N′-bis(4-pyridinyl)-1,4-benzenedicarboxamide, BDC =

Full text of DOI:10.1016/j.ultsonch.2015.05.034

Accepted Manuscript
Sonochemical synthesis of a nano-structured zinc(II) amidic pillar metal-or-
ganic framework
Mina Bigdeli, Ali Morsali
PII:
S1350-4177(15)00163-7
DOI:
http://dx.doi.org/10.1016/j.ultsonch.2015.05.034
ULTSON 2893
Reference:
Ultrasonics Sonochemistry
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25 May 2015
Please cite this article as: M. Bigdeli, A. Morsali, Sonochemical synthesis of a nano-structured zinc(II) amidic pillar
metal-organic framework, Ultrasonics Sonochemistry (2015), doi: http://dx.doi.org/10.1016/j.ultsonch.2015.05.034
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Sonochemical synthesis of a nano-structured zinc(II)
amidic pillar metal-organic framework
Mina Bigdeli, Ali Morsali*
Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, P.O. Box 14115-
4838, Tehran, Islamic Republic of Iran
Tel: +98-21-82883449, Fax: +98-21-8009730
Abstract
A facile and environmentally friendly nano-scale synthesis of a Zn(II) metal-organic
framework (MOF), {[Zn4(BDC)4(bpta)4]·5DMF·3H2O}n (1) (bpta = N,N′-bis(4-pyridinyl)-
1,4-benzenedicarboxamide, BDC = 1,4-dicarboxylate, DMF = N,N-dimethylformamide),
with nanorods morphology under ultrasonic irradiation at ambient temperature and
atmospheric pressure has been explored. This MOF has been characterized by scanning
electron microscopy (SEM), powder X-ray diffraction (PXRD) and IR spectroscopy. Some
parameters such as concentration of initial reagents, power ultrasound irradiation and time
effects on size and morphology of nano-structured compound 1 have been studied.
Keywords: metal-organic framework, sonochemical, amidic pillar, nano-structure;
1. Introduction
Metal-organic frameworks (MOFs) are porous organic-inorganic hybrid materials, that are
constructed by joining metal-containing units with organic linkers, using strong bonds to
create open crystalline frameworks with permanent porosity [1, 2]. Because of their porosity
and tunable chemical functionality, they have been used in diverse areas such as gas storage
[3, 4], adsorption [5], separation [6], catalysis [7], magnetism [8, 9] and drug delivery [10].
The key to the design of intriguing MOFs [11] lays in the intelligent ligand design, the proper
choice of metal center and counter ions. Hydrogen bonding, on the other hand, plays a crucial
role in the crystal engineering of organic solids [12]. Combination of both metal–ligand
coordination (MLC) and hydrogen bonding in designing MOFs should be considered an
1

attractive design strategy because of the possibility of structural variations and guest
entrapment induced by specific hydrogen bonding interactions. The amide group is a
fascinating functional group because it possesses two types of hydrogen-bonding sites: the -
NH moiety acts as an electron acceptor and the –C=O group acts as an electron donor. These
multifunctional moieties of amide groups tend to form hydrogen bonds among themselves
and interact negligibly with guest molecules after construction of MOFs [13]. These
structural frameworks have been utilized in applications such as chemical sieving, sensing,
and catalysis, and much progress has been made in all of these areas [14]. By decreasing the
size of metal-organic frameworks in nano-size, surface area would be increased. Hence
making MOFs in nano-scale is certainly a major step forward toward the technological
applications of these new materials [15, 16].
There are several different synthetic approaches for the preparation of metal–organic
frameworks such as slow diffusion, hydrothermal, and solvothermal synthesis methods [17-
19]. In many cases, these methods are needed long reaction times, high temperatures and
pressures. Also, because of the big potential of MOFs for industrial applications, it is
important to develop novel and techno-economically approaches, such as mechanochemical
[20-23], microwave (MW) [24-27], electrochemical synthesis [28, 29] and sonochemical
approach. In recent years many kinds of nano-sized materials have been prepared by
sonochemical method [30-34]. With using ultrasonic irradiation, various chemical reactions,
even some reactions that were previously difficult to realize by other traditional methods, can
also proceed at room temperature easily [35-37]. Sonochemical methods can lead to
homogeneous nucleation and a substantial reduction in crystallization time compared with
conventional oven heating when nanomaterials are prepared [38]. Many researchers have
investigated the effect of ultrasound on chemical reactions, and most theories imply that the
chemical or physical effects of ultrasound originate from acoustic cavitation within
collapsing bubbles, which generates extremely localized hot spots having temperatures of
roughly 5000 K, pressures of about 500 atm, and a lifetime of a few microseconds. Between
the microbubble and the bulk solution, the interfacial region around the bubble has very large
gradients of temperature, pressure, and the rapid motion of molecules leading to the
production of excited states, bond breakage, the formation of free radicals, mechanical
2

shocks, and high shear gradients [39]. The use of high-intensity ultrasound to enhance the
reactivity of metals as a stoichiometric reagent has become a synthetic technique for many
heterogeneous organic and organometallic reactions [40-46]. Ultrasonic irradiation is
considered a green energy source because of shorter reaction times and higher yields in
comparison with thermal energy sources [47] and this method is more convenient, cost
effective and environmentally friendly approach to nano-scale coordination supramolecular
compounds and easily controlled [39, 48, 49]. As a part of our ongoing efforts in the design
and synthesis of facile and environmentally friendly nano-scale materials, we wish to report
herein
on
the
synthesis
of
(1),
a
nano-structure
porous
MOF,
{[Zn4(BDC)4(bpta)4]·5DMF·3H2O}n
(bpta= N,N′-bis(4-pyridinyl)-1,4-
benzenedicarboxamide, BDC=1,4-dicarboxylate) [50], which is synthesized by the reaction
of zinc(II) acetate dehydrate, N,N′-bis(4-pyridinyl)-1,4-benzenedicarboxamide and 1,4-
dicarboxylate under ultrasonic irradiation at ambient temperature and atmospheric presure.
MOF 1 was synthesized in three different concentrations of initial reagents (0.006, 0.01 and
0.04 M) and two different reaction times of 15 and 30 min. MOF 1 was also synthesized
using the ultrasonic method at two different ultrasound powers (12 and 24 W). This metal-
organic framework has potential uses in the context of molecular recognition, catalysis, size-
selective guest transportation, optical materials, molecular magnetism, semiconductors, and
conductors [51].
Because of the unique properties of nano-particles, they have been used in electrical, optical,
magnetic and chemical features which are entirely different from their bulk counterparts [40,
52-55], in particular nanoscale metal–organic frameworks (NMOFs), have potential in
templating, biosensing, magnetic resonance imaging and drug delivery [56, 57].
2. Experimental
2.1. Materials and physical techniques
Except bpta ligand that was synthesized, all reagents and solvents for the synthesis and
analysis were commercially available and were used as received. Powder X-ray diffraction
(PXRD) of compound 1 was carried out on a diffractometer of Philips Company with X’pert
monochromatized Cu kα radiation. Simulated XRD powder patterns were calculated using
3

Mercury based on the single crystal data [50]. FT-IR spectra were recorded on a Nicolet
Fourier Transform IR, Nicolet 100 spectrometer in the range 500–4000 cm-1 using the KBr
disk technique. Ultrasonic generator was carried out on a TECNO-GAZ, S.p.A., Tecna 6,
input: 50–60 Hz/305 W.
2.2. Synthesis of bpta ligand
The N,N′-bis(4-pyridinyl)-1,4-benzenedicarboxamide ligand of bpta is synthesized according to
literature method [58].(Fig.1)
200 mL of CH2Cl2 and 3 mL of NEt3 were successively added to a 500 mL flask containing
terephthaloyl chloride (0.5 g, 2.46 mmol) and 4-aminopyridine (0.48 g, 5.20 mmol). The
resulting mixture was stirred at room temperature for 24 h. The resulting white precipitate
was collected, washed with water (50 mL) and CH2Cl2 (50 mL), and dried. IR (cm-1) selected
bond: 594(m), 835(m), 1118(m), 1296(s), 1416(m), 1505(vs), 1594(vs), 1663(s), 3533(s).
2.3. Synthesis of {[Zn4(BDC)4(bpta)4].5DMF.3H2O}n (1) as single crystal
According to reported method [50], colorless block crystals of compound 1 were obtained
from a mixture of ZnCl2 (20.5 mg, 0.15 mmol), H2BDC (24.9 mg, 0.15 mmol), bpta (47.8
mg, 0.15 mmol), DMF (7 mL) and H2O (0.5 mL) in Teflon-lined stainless steel autoclave
under autogenous pressure and heated at 120 °C for 72 h and then slowly cooled to 30 °C.
o
m.p. > 300 C. IR (cm-1) selected bond: 532(s), 601(m), 748(m), 831(s), 1103(s), 1296(m),
1384(s), 1508(vs), 1595(vs), 1671(s), 3077(m), 3263(m).
2.3. Synthesis of {[Zn4(BDC)4(bpta)4].5DMF.3H2O}n (1) nano-structure by a sonochemical
process
To prepare {[Zn4(BDC)4(bpta)4].5DMF.3H2O}n (1) nanopowder, Zn(OAC)2.2H2O (0.01 M),
BDC and bpta with molar ratio 1:1:1 were added to the one-necked flask that contain 25 ml
DMF as solvent and treated by ultrasound irradiation in ultrasonic bath. The obtained
precipitates were filtered off, washed with DMF several times and then dried in air, m.p. >
o
300 C. IR bands are: 534(s), 602(m), 748(m), 833(s), 1104(s), 1297(m), 1385(s), 1508(vs),
1596(vs), 1671(s), 3079(m), 3267(m).
4

To investigate the role of initial reagent concentrations on size and morphology of nano -
structured compound 1, the above processes were done with different concentrations (0.04,
0.01 and 0.006 mol L-1). For monitoring the role of power ultrasound irradiations on size and
morphology of compound 1 the process with the initial reagents concentration 0.01 M has
been done in three different ultrasound power (12 and 24 W). Sonochemical syntheses of 1
for the reaction times of 15 and 30 min were carried out under ultrasonic irradiation too.
3. Results and discussion
The hydrothermal reaction of zinc(II) chloride with 1,4-dicarboxylate (BDC) and N,N′-bis(4-
pyridinyl)-1,4-benzenedicarboxamide (bpta) as amidic pillar in 1:1:1 mole ratio at 120 °C for
72 h yields colorless crystals of compound 1, which is suitable for X-ray crystallography,
while nano-structures of compound 1 were obtained in DMF by ultrasonic irradiation at room
temperature. Scheme 1 gives an overview of the methods used for the synthesis of
{[Zn4(BDC)4(bpta)4].5DMF.3H2O}n (1) using the two different routes.
The IR spectrum of the nano-structures produced by the sonochemical method and of the
bulk material produced by the solvothermal method were compared with each other in Fig. 2.
The structure of compound 1 was characterized by single-crystal X-ray diffraction techniques
[50]. The molecular structure of the fundamental building unit for 1 is shown in Fig. 3. The
asymmetric unit consists of four Zn(II) atoms, four BDC2− ligands, four bpta linkers, five
DMF, and three water guest molecules. The framework is constructed from a six-connected
dinuclear {Zn2N4O6} node, which is octahedrally bound to four BDC ligands and two
double-bpta-deckered pillars. Each BDC2− ligand acts as a µ3-bridge to link three Zn(II)
atoms, in which one carboxylate group exhibits a µ2-η1:η1-bridging coordination mode, while
the other adopts a monodentate structure (Fig. 3).
Fig. 4 shows the simulated XRD pattern from single crystal X-ray data of compound 1 in
comparison with the XRD pattern of the as synthesized nano-structure of compound 1 by the
sonochemical process. Acceptable matches were observed between the simulated and
experimental XRD patterns. This indicates that the compound obtained by the sonochemical
5

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.
The morphology and size of compound 1 prepared by the sonochemical method was
characterized by scanning electron microscopy (SEM). Fig. 5 shows the SEM of the
compound 1 prepared by ultrasonic generator 12W in concentration of initial reagents [Zn2+]
= [BDC] = [bpta] = 0.04 mol L-1. Also different concentrations of zinc(II), 1,4-
benzenedicarboxylate and N,N′-bis(4-pyridinyl)-1,4-benzenedicarboxamide solution (0.01
and 0.006 mol L-1) were tested (Figs. 6 and 7). In order to investigate the role of
concentration of initial reagents on the nature of products, reactions were performed with
three different concentrations of initial reagents. Comparison between the samples with
different concentrations shows that high concentrations of initial reagents decreased particles
size. Thus, particles sizes produced using lower concentrations of initial reagents (0.006 mol
L-1, Fig. 7) are bigger than particles size produced using higher concentrations (0.04 and 0.01
mol L-1, Figs. 5 and 6, respectively). More interestingly that, as shown in Fig. 7, decreasing
of concentration of initial reagents ultimate to prepared rod-like nano-structure compound 1
(Fig. 7). The morphologies and size of nano-structure of the as-prepared samples for different
reaction times were characterized by SEM. Fig. 8 shows the SEM image of compound 1 with
reaction time of 30 min ( Zn(II) = BDC = bpta = 0.006 mol L-1, 12 W ). The results show that
the size of the nanoparticles increased with increasing reaction times. Thus, smaller particles
(for 15 min, see Fig. 7) were achieved by sonocrystallization at shorter times when compared
with 30 min (Fig. 8). To investigate the role of power ultrasound irradiation on the nature of
products, reactions were performed under diverse power ultrasound irradiation too (Zn(II) =
BDC = bpta = 0.006 mol L-1, 12 and 24W). Comparison between the samples with different
powers ultrasound irradiation shows that increasing of power from 12 to 24W leads to
decreasing of sizes of the nanoparticles (Fig. 9). Table 1 gives an overview of the
comparison of the concentration of initial reagents, times effect and different powers of
ultrasonic irradiation on the morphologies and sizes of nano-structure of the compound 1.
Thermogravimetric analysis of 1 showed that guest molecules are eliminated from the
network (calcd 16.1%; found 16.5%, which correspond to loss of 20 DMF molecules and 12
6

H2O molecules per unit cell) when the temperature is increased from room temperature to
about 270 °C [50].
4. Conclusions
Nanoparticles
and
nanorods
of
porous
,(bpta
metal-organic
framework,
{[Zn4(BDC)4(bpta)4].5DMF.3H2O}n
(1)
= N,N′-bis(4-pyridinyl)-1,4-
benzenedicarboxamide, BDC = 1,4-dicarboxylate, DMF = N,N-dimethylformamide) have
been synthesized under ultrasound irradiation. Structural information of the nanoparticles was
compared with the structural information of crystals of compound 1. Morphology and sizes of
the nano-structures were investigated in different concentrations of initial reagents, different
powers of ultrasonic irradiation and various reaction times. Results show an increase in the
particles size as the concentrations of initial reagents is decreased. It is an interesting point
that low concentration of initial reagents leaded to rod-like nano-structures morphology. Also
the shorter reaction times and using of different powers of ultrasonic irradiation lead to
decreasing the size of nano-structures.
Acknowledgement
Support of this investigation by Tarbiat Modares University is gratefully acknowledged.
7

Scheme 1. Materials produced and synthetic methods.
Fig. 1. bpta ligand
8

Fig. 2. IR spectrum of (a) nanostructures of compound 1 produced by sonochemical method and (b) bulk
materials of 1.
9

Fig. 3. Molecular-packing diagram of {[Zn4(BDC)4(bpta)4].5DMF.3H2O}n (1) viewed along the b-axis,
Zn(yellow), O(red), N(blue), C(purple and green), H(grey).
10

Fig. 4. XRD patterns of simulated patteern based on single crystal data of compound 1 (blue), as synthesized and
nanostructures of 1 prepared by sonoc
h
h
emical process (red)
11

Fig. 5. SEM photographs of compound 1 nanoparticles prepared by ultrasonic generator 12W in concentration
of initial reagents [Zn2+] = [bpta] = 0.04 mol L-1.
12

Fig. 6. SEM photographs of compound 1 nanoparticles prepared by ultrasonic generator 12W in concentration
of initial reagents [Zn2+] = [bpta] = 0.01 mol L-1.
13

Fig. 7. SEM photographs of compound 1 nanoparticles prepared by ultrasonic generator 12W in concentration
of initial reagents [Zn2+] = [bpta] = 0.006 mol L-1.
14

Fig. 8. The SEM image of compound 1 with reaction time of 30 min (Zn(II) = bpta = 0.006 mol L-1, 12 w).
15

Fig. 9. SEM photographs of compound 1 nanoparticles prepared by ultrasonic generator 24W in concentration
of initial reagents [Zn2+] = [bpta] = 0.006 mol L-1.
16

Concentration
(M)
Time
(min)
15
Power
(W)
12
Size
(nm)
74
Morphology
0.04
spherical
nanorod
nanorod
nanorod
nanorod
0.01
15
12
85
0.006
15
12
109
135
89
0.006
30
12
0.006
15
24
Table 1. Comparison of the concentration of initial reagents, times effect and different powers of ultrasonic
irradiation on the morphologies and sizes of nano-structure of the compound 1.
17

Reference
[1] H. Furukawa, K.E. Cordova, M. O’Keeffe, O.M. Yaghi, The chemistry and applications of metal-organic
frameworks, Science, 341 (2013) 1230444.
[2] H.-L. Jiang, T.A. Makal, H.-C. Zhou, Interpenetration control in metal–organic frameworks for functional
applications, Coord. Chem. Rev, 257 (2013) 2232-2249.
[3] M. Dinca, A. Dailly, Y. Liu, C.M. Brown, D.A. Neumann, J.R. Long, Hydrogen storage in a microporous
metal-organic framework with exposed Mn2+ coordination sites, J. Am. Chem. Soc, 128 (2006) 16876-16883.
[4] X. Zhao, B. Xiao, A.J. Fletcher, K.M. Thomas, D. Bradshaw, M.J. Rosseinsky, Hysteretic adsorption and
desorption of hydrogen by nanoporous metal-organic frameworks, Science, 306 (2004) 1012-1015.
[5] K. Biradha, M. Fujita, A Springlike 3D‐Coordination Network That Shrinks or Swells in a Crystal‐to‐Crystal
Manner upon Guest Removal or Readsorption, Angew. Chem, 114 (2002) 3542-3545.
[6] L. Pan, D.H. Olson, L.R. Ciemnolonski, R. Heddy, J. Li, Separation of hydrocarbons with a microporous
metal–organic framework, Angew. Chem, 118 (2006) 632-635.
[7] K.H. Park, K. Jang, S.U. Son, D.A. Sweigart, Self-supported organometallic rhodium quinonoid
nanocatalysts for stereoselective polymerization of phenylacetylene, J. Am. Chem. Soc, 128 (2006) 8740-8741.
[8] M.A. Abu-Youssef, A. Escuer, D. Gatteschi, M.A. Goher, F.A. Mautner, R. Vicente, Synthesis, structural
characterization, magnetic behavior, and single crystal EPR spectra of three new one-dimensional manganese
azido systems with FM, alternating FM-AF, and AF coupling, Inorg. Chem, 38 (1999) 5716-5723.
[9] A. Caneschi, D. Gatteschi, N. Lalioti, C. Sangregorio, R. Sessoli, G. Venturi, A. Vindigni, A. Rettori, M.G.
Pini, M.A. Novak, Cobalt (II)‐Nitronyl Nitroxide Chains as Molecular Magnetic Nanowires, Angew. Chem. Int.
Ed, 40 (2001) 1760-1763.
[10] J. An, S.J. Geib, N.L. Rosi, Cation-triggered drug release from a porous zinc− adeninate metal− organic
framework, J. Am. Chem. Soc, 131 (2009) 8376-8377.
[11] N. Adarsh, D.K. Kumar, P. Dastidar, Metal–organic frameworks derived from bis-pyridyl-bis-amide
ligands: Effect of positional isomerism of the ligands, hydrogen bonding backbone, counter anions on the
supramolecular structures and selective crystallization of the sulfate anion, CrystEngComm, 11 (2009) 796-802.
[12] G.R. Desiraju, Supramolecular synthons in crystal engineering—a new organic synthesis, Angew. Chem.
Int. Ed, 34 (1995) 2311-2327.
[13] S. Hasegawa, S. Horike, R. Matsuda, S. Furukawa, K. Mochizuki, Y. Kinoshita, S. Kitagawa, Three-
dimensional porous coordination polymer functionalized with amide groups based on tridentate ligand: selective
sorption and catalysis, J. Am. Chem. Soc, 129 (2007) 2607-2614.
[14] B.C. Tzeng, T.H. Chiu, B.S. Chen, G.H. Lee, Novel Single‐Crystal‐to‐Single‐Crystal Anion Exchange and
Self‐Assembly of Luminescent d10 Metal (CdII, ZnII, and CuI) Complexes Containing C3‐Symmetrical Ligands,
Chem. Eur. J, 14 (2008) 5237-5245.
[15] T. Uemura, S. Kitagawa, Nanocrystals of coordination polymers, Chem. Lett, 34 (2005) 132-137.
[16] V. Safarifard, A. Morsali, Sonochemical syntheses of nano lead (II) iodide triazole carboxylate
coordination polymer: Precursor for facile fabrication of lead (II) oxide/iodide nano-structures, Inorg. Chim.
Acta, 398 (2013) 151-157.
[17] W. Pisula, A. Menon, M. Stepputat, I. Lieberwirth, U. Kolb, A. Tracz, H. Sirringhaus, T. Pakula, K.
Müllen, A zone‐casting technique for device fabrication of field‐effect transistors based on discotic
hexa‐peri‐hexabenzocoronene, Adv. Mater, 17 (2005) 684-689.
[18] S.S.-Y. Chui, S.M.-F. Lo, J.P. Charmant, A.G. Orpen, I.D. Williams, A chemically functionalizable
nanoporous material [Cu3(TMA)2(H2O)3]n, Science, 283 (1999) 1148-1150.
18

[19] O. Yaghi, H. Li, T. Groy, Construction of porous solids from hydrogen-bonded metal complexes of 1, 3, 5-
benzenetricarboxylic acid, J. Am. Chem. Soc, 118 (1996) 9096-9101.
[20] S.L. James, C.J. Adams, C. Bolm, D. Braga, P. Collier, T. Friščić, F. Grepioni, K.D. Harris, G. Hyett, W.
Jones, Mechanochemistry: opportunities for new and cleaner synthesis, Chem. Soc. Rev, 41 (2012) 413-447.
[21] H. Sakamoto, R. Matsuda, S. Kitagawa, Systematic mechanochemical preparation of a series of
coordination pillared layer frameworks, Dalton trans, 41 (2012) 3956-3961.
[22] T. Friščić, D.G. Reid, I. Halasz, R.S. Stein, R.E. Dinnebier, M.J. Duer, Ion‐and Liquid‐Assisted Grinding:
Improved Mechanochemical Synthesis of Metal–Organic Frameworks Reveals Salt Inclusion and Anion
Templating, Angew. Chem, 122 (2010) 724-727.
[23] T. Friščić, L. Fábián, Mechanochemical conversion of a metal oxide into coordination polymers and porous
frameworks using liquid-assisted grinding (LAG), CrystEngComm, 11 (2009) 743-745.
[24] L. Hashemi, A. Morsali, Microwave assisted synthesis of a new lead (ii) porous three-dimensional
coordination polymer: study of nanostructured size effect on high iodide adsorption affinity, CrystEngComm, 14
(2012) 779-781.
[25] J. Klinowski, F.A.A. Paz, P. Silva, J. Rocha, Microwave-assisted synthesis of metal–organic frameworks,
Dalton Trans, 40 (2011) 321-330.
[26] Z. Ni, R.I. Masel, Rapid production of metal-organic frameworks via microwave-assisted solvothermal
synthesis, J. Am. Chem. Soc, 128 (2006) 12394-12395.
[27] S.H. Jhung, J.H. Lee, P.M. Forster, G. Férey, A.K. Cheetham, J.S. Chang, Microwave Synthesis of Hybrid
Inorganic–Organic Porous Materials: Phase‐Selective and Rapid Crystallization, Chem. Eur. J, 12 (2006) 7899-
7905.
[28] A. Martinez Joaristi, J. Juan-Alcañiz, P. Serra-Crespo, F. Kapteijn, J. Gascon, Electrochemical synthesis of
some archetypical Zn2+, Cu2+, and Al3+ metal organic frameworks, Cryst. Growth Des, 12 (2012) 3489-3498.
[29] U. Mueller, M. Schubert, F. Teich, H. Puetter, K. Schierle-Arndt, J. Pastre, Metal–organic frameworks—
prospective industrial applications, J. Mater. Chem, 16 (2006) 626-636.
[30] N. Soltanzadeh, A. Morsali, Sonochemical synthesis of a new nano-structures bismuth (III) supramolecular
compound: new precursor for the preparation of bismuth (III) oxide nano-rods and bismuth (III) iodide nano-
wires, Ultrason. Sonochem, 17 (2010) 139-144.
[31] M.Y. Masoomi, G. Mahmoudi, A. Morsali, Sonochemical syntheses and characterization of new nanorod
crystals of mercury (II) metal–organic polymer generated from polyimine ligands, J. Coord. Chem, 63 (2010)
1186-1193.
[32] M.A. Alavi, A. Morsali, Syntheses and characterization of Sr(OH)2 and SrCO3 nanostructures by ultrasonic
method, Ultrason. Sonochem, 17 (2010) 132-138.
[33] L. Hashemi, A. Morsali, Sonichemical Synthesis of a New Ethylene Diamine Lead (II) Coordination
Polymer as Precursor for Preparation of PbO Nano-Structure, Journal of Inorganic and Organometallic
Polymers and Materials, 22 (2012) 272-277.
[34] L. Hashemi, A. Morsali, Sonichemical Synthesis of a New Ethylene Diamine Lead (II) Coordination
Polymer as Precursor for Preparation of PbO Nano-Structure, Journal of Inorg. Organomet. Polym, 22 (2012)
272-277.
[35] Y. Kojima, S. Koda, H. Nomura, Effects of sample volume and frequency on ultrasonic power in solutions
on sonication, Jpn. J. Appl. Phys, 37 (1998) 2992.
[36] S. Koda, T. Kimura, T. Kondo, H. Mitome, A standard method to calibrate sonochemical efficiency of an
individual reaction system, Ultrason. Sonochem, 10 (2003) 149-156.
[37] G. Cravotto, L. Boffa, S. Mantegna, P. Perego, M. Avogadro, P. Cintas, Improved extraction of vegetable
oils under high-intensity ultrasound and/or microwaves, Ultrason. Sonochem, 15 (2008) 898-902.
[38] W.-J. Son, J. Kim, J. Kim, W.-S. Ahn, Sonochemical synthesis of MOF-5, Chem. Comm, (2008) 6336-
6338.
[39] L.-G. Qiu, Z.-Q. Li, Y. Wu, W. Wang, T. Xu, X. Jiang, Facile synthesis of nanocrystals of a microporous
metal–organic framework by an ultrasonic method and selective sensing of organoamines, Chem. Comm,
(2008) 3642-3644.
[40] A. Aslani, A. Morsali, M. Zeller, Nano-structures of two new lead (II) coordination polymers: New
precursors for preparation of PbS nano-structures, Solid State Sci, 10 (2008) 1591-1597.
[41] M.A. Alavi, A. Morsali, Syntheses and characterization of Mg(OH)2 and MgO nanostructures by ultrasonic
method, Ultrason. Sonochem, 17 (2010) 441-446.
19

[42] A. Askarinejad, A. Morsali, Synthesis of cadmium (II) hydroxide, cadmium (II) carbonate and cadmium
(II) oxide nanoparticles; investigation of intermediate products, Chem. Eng. J, 150 (2009) 569-571.
[43] V. Safarifard, A. Morsali, S.W. Joo, Sonochemical synthesis and characterization of nano-sized lead (II)
3D coordination polymer: Precursor for the synthesis of lead (II) oxybromide nanoparticles, Ultrason.
Sonochem, 20 (2013) 1254-1260.
[44] V. Safarifard, A. Morsali, Sonochemical syntheses of a nano-sized copper (II) supramolecule as a precursor
for the synthesis of copper (II) oxide nanoparticles, Ultrason. Sonochem, 19 (2012) 823-829.
[45] A.R. Abbasi, K. Akhbari, A. Morsali, Dense coating of surface mounted CuBTC Metal–Organic
Framework nanostructures on silk fibers, prepared by layer-by-layer method under ultrasound irradiation with
antibacterial activity, Ultrason. Sonochem, 19 (2012) 846-852.
[46] Z.-Q. Li, L.-G. Qiu, T. Xu, Y. Wu, W. Wang, Z.-Y. Wu, X. Jiang, Ultrasonic synthesis of the microporous
metal–organic framework Cu3(BTC)2 at ambient temperature and pressure: an efficient and environmentally
friendly method, Mater. Lett, 63 (2009) 78-80.
[47] A. Alizadeh, H. Sedighian, R. Ghanbaripour, An Approach to the Synthesis of
7‐Amino‐6‐imino‐9‐phenyl‐6H‐benzo [c] chromene‐8‐carbonitrile Derivatives via a Three‐Component Reaction
under Ultrasonic Irradiation, Helv. Chim. Acta, 97 (2014) 447-452.
[48] A.R. Armstrong, P.G. Bruce, Synthesis of layered LiMnO2 as an electrode for rechargeable lithium
batteries, Nature, 381 (1996) 499-500.
[49] V. Safarifard, A. Morsali, Sonochemical syntheses of a new fibrous-like nano-scale manganese (II)
coordination supramolecular compound; precursor for the fabrication of octahedral-like Mn3O4 nano-structure,
Ultrason. Sonochem, 21 (2014) 253-261.
[50] C.-H. Lee, H.-Y. Huang, Y.-H. Liu, T.-T. Luo, G.-H. Lee, S.-M. Peng, J.-C. Jiang, I. Chao, K.-L. Lu,
Cooperative Effect of Unsheltered Amide Groups on CO2 Adsorption Inside Open-Ended Channels of a Zinc
(II)–Organic Framework, Inorg. Chem, 52 (2013) 3962-3968.
[51] Z. Qin, M.C. Jennings, R.J. Puddephatt, Self-assembly in palladium (II) and platinum (II) chemistry: The
biomimetic approach, Inorg. Chem, 42 (2003) 1956-1965.
[52] M. Martos, J. Morales, L. Sanchez, R. Ayouchi, D. Leinen, F. Martin, J.R. Barrado, Electrochemical
properties of lead oxide films obtained by spray pyrolysis as negative electrodes for lithium secondary batteries,
Electrochim. Acta, 46 (2001) 2939-2948.
[53] A.V. Murugan, R. Sonawane, B. Kale, S. Apte, A.V. Kulkarni, Microwave–solvothermal synthesis of
nanocrystalline cadmium sulfide, Mater. Chem. Phys, 71 (2001) 98-102.
[54] S.-H. Yu, J. Yang, Z.-H. Han, Y. Zhou, R.-Y. Yang, Y.-T. Qian, Y.-H. Zhang, Controllable synthesis of
nanocrystalline CdS with different morphologies and particle sizes by a novel solvothermal process, J. Mater.
Chem, 9 (1999) 1283-1287.
[55] H. Shi, L. Qi, J. Ma, H. Cheng, Polymer-directed synthesis of penniform BaWO4 nanostructures in reverse
micelles, J. Am. Chem. Soc, 125 (2003) 3450-3451.
[56] W. Lin, W.J. Rieter, K.M. Taylor, Modular synthesis of functional nanoscale coordination polymers,
Angew. Chem. Int. Ed, 48 (2009) 650-658.
[57] R.K. Bhakta, J.L. Herberg, B. Jacobs, A. Highley, R. Behrens Jr, N.W. Ockwig, J.A. Greathouse, M.D.
Allendorf, Metal− Organic Frameworks As Templates for Nanoscale NaAlH4, J. Am. Chem. Soc, 131 (2009)
13198-13199.
[58] S.-S. Sun, A.J. Lees, P.Y. Zavalij, Highly sensitive luminescent metal-complex receptors for anions
through charge-assisted amide hydrogen bonding, Inorg. Chem, 42 (2003) 3445-3453.
20

• Nanorods of a Zinc(II) metal-organic framework were synthesized
• The morphology of the nanorods depend on the concentration of initial
reagents
• Low concentrations of initial reagents leaded to rod-like morphology
• The time effect on size of nano-structured MOF have been studied
• The shorter reaction times lead to decreasing the size of nano-structures
21