Solid–solid and solid–liquid conversion of sodium and silver nano coordination polymers

Article abstract of DOI:10.1016/j.poly.2019.03.032

Solid-state conversion of a three-dimensional sodium coordination polymer [Na(μ₆-HTar)]_n (1), (H₂Tar = (+)‐tartaric acid), synthesized by a sonochemical procedure, to a two-dimensional silver coordination polymer [Ag(μ₃-HTar)(H₂O)]_n (2) has been observed upon mechanochemical cation exchange reaction of 1 with AgNO₃. The conversion of 2 to 1 via solid-state reaction has also been investigated. These samples were characterized by IR spectroscopy, X‐ray powder diffraction (XRD), thermo gravimetric and differential thermal analyses (TG-DTA), Energy-dispersive X-ray spectroscopy (EDAX) and Scanning Electron Microscopy (SEM). It was observed that the conversion of compound 1 to compound 2 is irreversible. In addition it was confirmed that [Ag(μ₃-HTar)(H₂O)]_n (2) converted to [Ag₂(HTar)]_n (3) during solid–liquid reaction in water.

Full text of DOI:10.1016/j.poly.2019.03.032

Accepted Manuscript
Solid-solid and Solid-liquid Conversion of Sodium and Silver Nano Coordina-
tion Polymers
Maryam Hasheminezhad, Kamran Akhbari, Anukorn Phuruangrat
PII:
S0277-5387(19)30205-0
https://doi.org/10.1016/j.poly.2019.03.032
POLY 13833
DOI:
Reference:
Polyhedron
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Accepted Date:
5 January 2019
11 March 2019
19 March 2019
Please cite this article as: M. Hasheminezhad, K. Akhbari, A. Phuruangrat, Solid-solid and Solid-liquid Conversion
of Sodium and Silver Nano Coordination Polymers, Polyhedron (2019), doi: https://doi.org/10.1016/j.poly.
2019.03.032
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Solid-solid and Solid-liquid Conversion of Sodium and Silver Nano
Coordination Polymers
Maryam Hasheminezhad1, Kamran Akhbari1,* and Anukorn Phuruangrat2
1School of Chemistry, College of Science, University of Tehran, Tehran, Iran.
Tel.: +98 21 61113734; fax: +98 21 66495291.
E-mail address: akhbari.k@khayam.ut.ac.ir (K. Akhbari)
2Department of Materials Science and Technology, Faculty of Science, Prince of Songkla
University, Hat Yai, Songkhla, Thailand.
Abstract
Solid-state conversion of a three-dimensional sodium coordination polymer [Na(μ6-HTar)]n (1),
(H2Tar = (+)‐tartaric acid), synthesized by a sonochemical procedure, to a two-dimensional
silver coordination polymer [Ag(μ3-HTar)(H2O)]n (2) has been observed upon mechanochemical
cation exchange reaction of 1 with AgNO3. The conversion of 2 to 1 via solid-state reaction has
also been investigated. These samples were characterized by IR spectroscopy, X‐ray powder
diffraction (XRD), thermo gravimetric and differential thermal analyses (TG-DTA), Energy-
dispersive X-ray spectroscopy (EDAX) and Scanning Electron Microscopy (SEM). It was
observed that the conversion of compound 1 to compound 2 is irreversible. In addition it was
confirmed that [Ag(μ3-HTar)(H2O)]n (2) converted to [Ag2(HTar)]n (3) during solid-liquid
reaction in water.
Keywords: Coordination polymer; Mechanochemistry; Solid-solid; Solid-liquid; Sodium; Silver.
1. Introduction
Coordination polymers (CPs) are the class of materials, comprise from metal clusters as
connectors and organic ligands as linkers [1]. The unsaturated metal site as a Lewis acid and
linkers with functional groups as a Lewis base [2]. The most important key of building these
1

compounds are coordination bonds. Coordination bonds are not as strong as covalent bonds and
not weak as hydrogen bonds [3]. Coordination polymers have different classifies. Metal organic
framework is one of the new classes of CPs with special property like micro porosity, high
internal surface areas and low densities. Over the past two decades, crystal engineering based on
MOFs has attracted [4, 5]. The presence of coordinately unsaturated metal centers can increase
the performance of CPs in the applications like molecular recognition, molecular adsorption,
nonlinear optics, drug delivery, gas storage, purification, molecular sensing, as antibacterial
agents, preparation of nanomaterials and recently useful heat transformation including cooling
application [6-14]. Usually the magnetic nanostructures used for drug delivery systems [15]. We
should control structures to design new compounds [16]. The structure and properties of
coordination polymers depend on the coordination habits and geometries of both metal ions and
connecting ligands [9]. The interest in coordination polymers demands the development of rapid
and high-yielding methods for their synthesis and discovery [17]. The properties of CPs mainly
depend on the structure and other factors such as which metal centers that be used, ligands, some
interactions, guest species and coordination bonds [18]. Although some methods such as
solvothermal conditions are more considered for synthesis of coordination polymers [19],
sonochemical, mechanochemil and microwave reactions and are environment friendly and
efficient [20]. The efficient process is one of the reasons for using ultrasound in nanomaterials,
because of high-energy [21,22]. Ultrasonic irradiation are different from other energy sources
such as heat, light etc [22]. Sonic radiation can break chemical bonds [21]. This event occurs in
sonochemistry which includes creation, growth and collapse of a bubble that is formed in the
liquid [21,23]. The most important reasons for using sonochemistry are improved efficiency and
changed the reaction pathway [24]. The ultrasonic wave radiations are effective on the
morphology and size of the samples [25]. In nano-sized structures, the surface area is more
increased [26]. Mechanochemical reactions are conducted by grinding solid reactants together
without solvent or using a fewer amounts of solvent [27]. Mechanochemistry, a burgeoning field
in CPs, has been utilized to synthesize various CPs from the reactants without solvents or using
liquid or ionic liquid assisted by grinding [28]. The coordination chemistry of group 1 and 2
metal compounds with organic ligand is being more fascinating in recent decades, because most
of them are non-toxic, cheap and soluble. Thus they are used in dye and pharmaceuticals
industry [29]. Therefore, the comprehension of fundamental properties such as electronegativity,
2

size and charge is important because they might influence on solid-state structure [29]. Ion
exchange is being interested in coordination polymers, this can happen in solid-state reaction,
even though there is often, no evidence for occurrence of mechanism [30]. Prevalent ion-
exchange resins with cationic groups and exchangeable counter ions are still the standard ion-
exchange materials [9]. So in this work, a sodium coordination polymer [Na(μ6-HTar)]n (1),
(H2Tar = (+)‐tartaric acid) [31], was synthesized by a sonochemical procedure and its cation
exchange with silver ion was investigated. In addition to solid-solid conversion, a Solid-liquid
reaction was observed in this work. Solid-liquid conversions are very attractive and did not
observe in other works as well as solid-solid conversions [32].
2. Experimental
2.1. Materials and physical techniques
All reagents and solvents for the synthesis and analysis were commercially available and were
used as received. The molecular structure plots were prepared using Mercury [33]. PARSONIC
15S ultrasonic bath (with the frequency 28 KHz) was used for the ultrasonic irradiation. Melting
points were measured on an Electrothermal 9100 apparatus and are uncorrected. IR spectra were
recorded using an Equinox 55 FT-IR spectrometer (Bruker, Bremen, Germany) in ATR form, in
the range of 400-4000 cm‾1 with 4.0 cm‾1 resolution and the 16 scan's numbers. The thermal
behavior was measured with a PL-STA 1500 apparatus between 20 and 800 °C, with a heating
1
rate of 5 °C.min¯ , under a nitrogen atmosphere. X-ray powder diffraction (XRD) measurements
were performed using an X’pert diffractometer manufactured by Philips with monochromatized
CuKα radiation (λ = 1.54056 Å) with step-size of 0.01671 (degree). The X-ray source was
operated under voltage and current of 40 kV and 30 mA, respectively. Bragg-Brentano was used
as source–detector geometry with scintillation detector. Additional attachments or peripheral
equipment such as anti-scatter slit (1°), divergence slit (1°), monochromator and soller slit (0.04
rad) were also used in this diffractometer. The samples were prepared as fine powders on silicon
based material. The EDX model of the MW 2300 Cam Scan was used to determine the
composition of the elemental percentages of synthesized structures. Simulated XRD powder
patterns based on single crystal data were prepared using the Mercury software [33]. The
3

samples were characterized by a scanning electron microscope (Philips XL 30) with gold
coating.
2.2. Synthesis of [Na(μ6-HTar)]n (1) by sonochemical process
To synthesis the sample of 1, 8 mmol of (+)‐tartaric acid (H2Tar) and 8 mmol of NaOH in H2O
(25 mL) was heated and stirred for one hour. Then the transparent solution was transferred to
ultrasonic bath for one hour. The obtained white precipitate was filtered, subsequently washed
with small amount of distilled water (8 mL, because of its solubility in water) and then dried at
room temperature, d.p. = 185 °C, yield: 1.10 g, 79.89%.
2.3. Mechanochemical reaction of 1 with AgNO3 in order to prepare [Ag(μ3-HTar)(H2O)]n
(2)
This reaction was performed between 4 mmol of [Na(μ6-HTar)]n (1) with 5 mmol of AgNO3.
These two reactants were mixed in mortar and ground up for one hour through liquid-assisted
grinding (LAG) method by adding a few droplets of water. Then the mixture was four times
washed with distilled water until the resulting NaNO3 and unreacted AgNO3 removed from it and
the pure white compound of 2 was separated. Compound 2 is not soluble in water. d.p. = 189 °C,
yield: 0.86 g, 78.18%.
2.4. Checking the irreversibility of this solid-state structural transformation
This reaction was performed between 0.6 mmol of [Ag(μ3-HTar)(H2O)]n (2) with 0.7 mmol of
NaNO3. These two reactants were mixed in mortar and ground up for one hour through liquid-
assisted grinding (LAG) method by adding a few droplets of water. The resulting product was
not soluble in water and washed with distilled water for four times. d.p. = 194 °C.
4

3. Results and discussion
The reaction between (+)‐ tartaric acid (H2Tar) and NaOH in water under ultrasonic irradiation
results in the formation of a white powder (1), which was dried at room temperature. Figures 1a
and 1b show the IR spectra of H2Tar and the obtained precipitate, respectively. The IR spectrum
of H2Tar shows very strong adsorption bonds in the frequency of 1090 and 1730 cm−1 attributed
to C−O and C=O bonds in –COOH group, respectively (Figure 1a). The broad absorption bond
between 2250–3300 cm−1 in its IR spectrum (Figure 1a) attributed to existence of various
hydrogen bondings in H2Tar. The weak absorption bands in the frequency of 3340 and 3410
cm−1 attributed to C−H and O−H bonds, respectively (Figure 1a). The obtained white powder
(1), after the reaction of H2Tar with NaOH, shows similar spectrum (Figure 1b) to H2Tar (Figure
1a). In addition to absorption bond in the frequency of 1710 cm−1, another absorption bond in the
frequency of 1650 cm−1 appeared in its IR spectrum (Figure 1b), which shows that probably the
two –COOH groups did not deprotonated completely. The absorption bond in the frequency of
3165 cm−1 attributed to –OH groups which their bond strengths were weakened probably due to
coordination to sodium ions (Figure 1b). A comparison between the IR spectrum of compound 1
after the solid-state mechanochemical reaction with excess AgNO3 (Figure 1c) and that of 1
synthesized by the sonochemical process (Figure 1b) proved that an ion exchange process of the
Na(I) ion by the Ag(I) ion was occurred. Appearance of two absorption bonds in the frequencies
of 1580 and 1700 cm−1, shows that probably the two –COOH groups did not deprotonated
completely in the obtained product (2). The IR spectrum of 2 after removal of produced NaNO3
and unreacted AgNO3 from the product mixture (Figure 1d), showed disappearance of absorption
bond in the frequency of 1700 cm−1 and appearance of two strong absorption bonds in the
frequencies of 1390 and 1595 cm−1, shows that probably the two –COOH groups deprotonated
completely and compound 2 converted to 3 during washing process. The IR spectra of 3 after the
liquid-assisted mechanochemical reaction with NaNO3 (Figure 1e) and its washing process
(Figure 1f) are exactly the same as that observed in Figure 1d, thus during metal ion exchange
process and the mixture washing, compound 3 did not converted back to 1 or 2 and this
conversion is irreversible. The characteristic bands of the two carboxylate groups appeared
around 1532 vs for υas(C-O), 1325 vs for υsym(C-O) and 1621 vs for υas(C-O), 1385 vs for υsym(C-O) for
compound 3.
5

Figure 2a shows the simulated XRD pattern from single crystal X-ray data of [Na(μ6-HTar)]n
[31]. Figure 2b shows the XRD pattern of the typical sample of 1 synthesized by the
sonochemical process. Acceptable matches were observed between the simulated from single-
crystal X-ray data pattern (Figure 2a) and that from the experimental powder X-ray diffraction
pattern of 1 (Figure 2b). Thus [Na(μ6-HTar)]n (1) was synthesized successfully from
sonochemical reaction between H2Tar and NaOH. A comparison between the XRD patterns
simulated from single crystal X-ray data of [Ag(μ3-HTar)(H2O)]n (2) (Figure 2c) and compound
1 after liquid assisted solid-state mechanochemical reaction with excess AgNO3 (Figure 2d)
approved that ion exchange process of Na(I) with Ag(I) was occurred. The XRD pattern of 2
after removal of produced NaNO3 and unreacted AgNO3 from the product mixture (Figure 2e),
showed appearance of new peaks (assigned with *) in addition to those attributed to compound 2
(Figure 2c,d). As it was proposed by IR analyses, in this new compound the two –COOH groups
were deprotonated completely and [Ag2(Tar)] (3) was formed probably. The XRD patterns after
liquid assisted grinding of the mixture (2,3) with NaNO3 and few droplets of water (Figure 2f,g)
showed that the reverse reaction is impossible and compound 3 did not converted back to 1 or 2
and this conversion is irreversible.
Figure 3a shows the primary structural building unit of [Na(μ6-HTar)]n (1). Determination the
structure of the compound 1 by X–ray crystallography showed that compound 1 is a three-
dimensional coordination polymer (Figure 4top). H2Tar was partially deprotonated and HTar¯
bridges between six Na ions (Figure 3a). Each –COO¯ and –COOH groups bridges between two
Na ions and each –OH groups coordinates to one Na ion (Figure 3a). Compound 1 has one type
of Na ion with disordered octahedral NaO6 coordination sphere (Figure 3a). Hydrogen bonding
interactions also exist in three-dimensional structure of 1 between –OH and –COO¯ groups and –
COOH and COO¯ groups [31]. Figure 3b shows the primary structural building unit of [Ag(μ3-
HTar)(H2O)]n (2). Determination the structure of the compound 2 by X–ray crystallography
showed that compound 2 is a two-dimensional coordination polymer (Figures 4down and 5).
H2Tar was partially deprotonated and HTar¯ bridges between three Ag ions (Figure 3b). Each –
OH and –COOH groups coordinates to one Ag ion and the neighboring –OH and –COO¯ groups
chelate to the third Ag ion (Figure 3b). Compound 2 has one type of Ag ion with disordered
trigonal bipyramid AgO5 coordination sphere (Figure 3c). In addition to four oxygen atoms of
HTar¯, one H2O molecule coordinated to Ag atom too (Figure 3c). Hydrogen bonding
6

interactions also exist in two-dimensional structure of 2 between –OH and –OH2 groups and
COOH and COO¯ groups [31]. Our attempt for preparation single crystals of compound 3 was
not successful.
SEM image of compound [Na(μ6-HTar)]n (1), synthesized under ultrasonic irradiation (Figure
6a), showed the formation of compound 1 microstructure. After solid-state mechanochemical
reaction of 1 with excess AgNO3, microcubes of [Ag(μ3-HTar)(H2O)]n (2) with nano layered
structure were formed (Figure 6b). SEM image of 2 after removal of produced NaNO3 and
unreacted AgNO3 from the product mixture (Figure 6c), in addition to microcubes of 2, showed
the formation of nanoflowered liked structure of [Ag2(Tar)]n (3) which was approved by XRD
analyses (Figure 2e). After the liquid-assisted mechanochemical reaction of compounds 2,3
mixture with NaNO3 microcube of 3 was formed (Figure 6d). microcube of 3 changed to
nanoflowered liked structure of 3 again, after washing process (Figure 6e). Thus during the
washing process, the morphology of 3 can be changed with partial desolvation-precipitation
mechanism.
TG-DTA data (Figure 7a) indicated that compound [Na(μ6-HTar)]n (1) which was synthesized
under ultrasonic irradiation is stable up to 220 °C. The observed mass loss of 10.6% between 43-
72 °C is attributed to some adsorbed species, like solvents, via hydrogen bonding interaction on
microstructure surface of 1. Thermal behavior of compound 1 after the solid-state
mechanochemical reaction with excess AgNO3 (Figure 7b) is different from that of 1 (Figure 7a),
which proves the formation of another new compound (2) from this conversion. Thermal
behavior of compound 2 after washing (Figure 7c) shows that [Ag(μ3-HTar)(H2O)]n (2) is stable
up to 75.0 ⁰C and endothermic removal of coordinated water molecule occurs up to 93 ⁰C. The
obtained water free compound is stable up to 145 ⁰C. The final residue which was maintained at
600 ⁰C, is about 54.6% which is higher than 47.6% which observed at 600 ⁰C for compound 1.
The thermal behavior of compound 2 after its mechanochemical reaction with excess NaNO3 was
also examined (Figure 7d). It showed different thermal behavior to Figures 7c and 7a. No
endothermic removal of coordinated water molecules was observed between 70-100 ⁰C. After
washing process of the mixture (Figure 7e), similar thermal behavior to that observed in Figure
7d was observed. Again no endothermic removal of coordinated water molecules was observed
between 70-100 ⁰C, suggested that the new obtained compound has no coordinated water
molecule. The final residue which was maintained at 600 ⁰C, is about 62.1% which is higher
7

than 54.6% which observed at 600 ⁰C for compound 2. Thus in addition to the IR spectroscopy
and XRD analyses, this result also approves that this solid-state conversion is irreversible and a
new compound with free coordinated water molecule and chemical formula of [Ag2(Tar)]n (3)
was formed via solid-liquid process.
EDAX (Energy Dispersive Analysis X-ray) was performed in support of IR, XRD and TG-DTA
observation and to further confirm of the composition of sample A and compound 3 (Tables 1
and 2). EDAX profiles are confirmed the presence of the elements in these compounds (Figure
8a,b). Previous analyses suggested the existence of [Ag(μ3-HTar)(H2O)]n (2) and [Ag2(Tar)]n (3)
in sample A and pure phase of 3 in final process. The weight percent ratio of Ag = 77.13% in B
sample in comparison with Ag = 56.70% in A sample approved the formation of [Ag2(Tar)]n (3)
from [Ag(μ3-HTar)(H2O)]n (2) during washing process of 2 with water (solid-liquid reaction) and
during mechanochemical treatment with NaNO3. Existence of Na = 2.63% and 1.23% in A and B
samples may be due to doping small amount of Na in crystalline structures of compounds 2 and
3.
A comparison between the other published results from our laboratory [17,33,34] and this work
(Table 3) shows that if the silver coordination polymer comprised from the ligands with -SO3H
groups, the solid-solid reaction is reversible and if the silver coordination polymer comprised
from the ligands with -COOH groups also the groups, the solid-solid reaction is irreversible. The
following equation shows that how compound 2 converts to 3 during solid-liquid reaction:
in solution
2 [Ag(μ3-HTar)(H2O)]n (2)
[Ag2(Tar)]n (3) + H2Tar + 2 H2O
→
4. Conclusion
Solid-solid conversion of a three-dimensional sodium coordination polymer [Na(μ6-HTar)]n (1),
synthesized by a sonochemical procedure, to a two-dimensional silver coordination polymer
[Ag(μ3-HTar)(H2O)]n (2) has been observed upon mechanochemical cation exchange reaction of
1 with AgNO3. The disordered octahedral NaO6 coordination sphere in 1 changed to disordered
trigonal bipyramid AgO5 coordination sphere in 2. Two types of hydrogen bonding interactions
exist in 1 and 2. In addition to hydrogen bonding interaction between –COOH and COO¯ groups
which observed in both of them, the hydrogen bonding interaction between –OH and –COO¯
groups in 1 changed to between –OH and –OH2 groups in 2. The conversion of 2 to 1 via solid-
8

state reaction has also been investigated. It was observed that the conversion of compound 1 to
compound 2 is irreversible. In addition it was confirmed that [Ag(μ3-HTar)(H2O)]n (2) converted
to [Ag2(HTar)]n (3) during solid-liquid reaction in water. SEM images also showed that during
the washing process, the morphology of 3 can be changed with partial desolvation-precipitation
mechanism.
Acknowledgements
The authors would like to acknowledge the financial support of University of Tehran for this
research under grant number.
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corrugated tape silver coordination polymer nanoparticles, Inorg. Chem. Commun. 82 (2017) 6-
10.
12

Table 1. The elemental percentages of A sample obtained from EDAX analyses.
Element
Line
Type
K series
Apparent
Concentration
7.66
k Ratio
Wt%
Wt%
Sigma
0.16
Atomic %
C
O
0.07659
0.04648
0.00895
0.35986
14.23
26.44
2.63
34.07
47.52
3.29
K series
K series
L series
13.81
2.12
0.23
0.07
0.25
Na
Ag
35.99
56.70
100.00
15.12
100.00
Total:
Table 2. The elemental percentages of B sample obtained from EDAX analyses.
Element
Line
Type
K series
Apparent
Concentration
3.18
k Ratio
Wt%
Wt%
Sigma
0.11
Atomic %
C
O
0.03179
0.02047
0.00355
0.45476
6.36
15.28
1.23
23.50
42.39
2.38
K series
K series
L series
6.08
0.84
0.20
0.05
0.22
Na
Ag
45.48
77.13
100.00
31.73
100.00
Total:
Table 3. A comparison between the other published results for solid-solid conversion of sodium
to silver coordination polymers and this work.
Ligand
1,5-H2nds
Hdcpa
Sodium coordination
polymer
[Na2(1,5-nds)(H2O)2]n
Silver coordination
polymer
Reversibility
Ref.
34
[Ag2(1,5-nds)]n
yes
No
No
No
[Na(μ2-Hdcpa)(μ3-dcpa)]n
[Na2(OBA)(H2O)]n
[Na(μ6-HTar)]n
[Ag2(μ2- dcpa)2]n
[Ag2(OBA)]n
35
17
H2OBA
[Ag(μ3-HTar)(H2O)]n
This work
H2Tar
1,5-H2nds: 1,5-naphthalenedisulfonic acid
Hdcpa: 2,4-dichlorophenoxyacetic acid
H2OBA: 4,4'-oxybis(benzoic acid)
H2Tar: (+)‐tartaric acid
13

f
e
d
c
b
a
4000 3500 3000 2500 2000 1500 1000 500
Figure 1. IR spectra of a) H2Tar, b) compound [Na(μ6-HTar)]n (1) synthesized under ultrasonic
irradiation, c) compound 1 after mechanochemical reaction with excess AgNO3, d) the
precipitate (A) obtained from washing the previous mixture, e) sample A after mechanochemical
reaction with NaNO3 and f) the precipitate (B) obtained from washing the previous mixture
(compound [Ag2(HTar)]n (3)).
14

Figure 2. XRD patterns; a) simulated pattern based on single crystal data of compound [Na(μ6-
HTar)]n (1), b) compound 1 synthesized under ultrasonic irradiations, c) simulated pattern based
on single crystal data of [Ag(μ3-HTar)(H2O)]n (2), d) compound 1 after mechanochemical
reaction with excess AgNO3, e) the precipitate (A) obtained from washing the previous mixture,
f) sample A after mechanochemical reaction with NaNO3 and g) the precipitate (B) obtained
from washing the previous mixture (compound [Ag2(HTar)]n (3)).
15

a)
b)
c)
Figure 3. Primary structural building unit in a) [Na(μ6-HTar)]n (1) and b,c) [Ag(μ3-HTar)(H2O)]n
(2), (Na = violet, Ag = pink, O = red, C = gray and H = white).
16

Figure 4. A schematic diagram illustrating the solid-state structural transformation of 3D NaI
coordination polymer of [Na(μ6-HTar)]n (1) to 2D AgI coordination polymer of [Ag(μ3-
HTar)(H2O)]n (2) upon mechanochemical reaction of 1 with AgNO3, (along the crystallographic
a axis, Na = violet, Ag = pink, O = red, C = gray and H = white).
17

Figure 5. A fragment of [Ag(μ3-HTar)(H2O)]n (2) two-dimensional layer along the
crystallographic b axis (Ag = pink, O = red, C = gray and H = white).
18

a)
b)
19

c)
d)
20

e)
Figure 6. SEM images of a) compound [Na(μ6-HTar)]n (1) synthesized under ultrasonic
irradiation, b) compound 1 after mechanochemical reaction with excess AgNO3, c) the
precipitate (A) obtained from washing the previous mixture, d) sample A after mechanochemical
reaction with NaNO3 and e) the precipitate (B) obtained from washing the previous mixture
(compound [Ag2(HTar)]n (3)).
21

a)
120
100
80
60
40
20
0
10
TG
0
-10
-20
-30
-40
0
200
400
600
800
b)
120
100
80
60
40
20
0
5
TG
0
-5
-10
-15
-20
-25
0
200
400
600
800
c)
120
100
80
60
40
20
0
4
0
TG
-4
-8
-12
-16
0
200
400
600
800
22

d)
120
100
80
60
40
20
0
10
TG
0
-10
-20
-30
-40
0
200
400
600
800
e)
120
100
80
60
40
20
0
4
TG
0
-4
-8
-12
0
200
400
600
800
Figure 7. Thermal behavior of a) compound [Na(μ6-HTar)]n (1) synthesized under ultrasonic
irradiation, b) compound 1 after mechanochemical reaction with excess AgNO3, c) the
precipitate (A) obtained from washing the previous mixture, d) sample A after mechanochemical
reaction with NaNO3 and e) the precipitate (B) obtained from washing the previous mixture
(compound [Ag2(HTar)]n (3)).
23

a)
b)
Figure 8. EDAX spectra of a) A and b) B precipitates (compound [Ag2(HTar)]n (3)).
A table of contents
24

Solid-solid and Solid-liquid Irreversible solid-solid conversion
Conversion of Sodium and of 3D Na coordination polymer
Silver Nano Coordination to 2D Ag coordination polymer
Polymers
nanostructures has been observed
upon mechanochemical reaction.
In addition it was confirmed that
Ag compound converted to
another Ag coordination polymer
during solid-liquid reaction in
water.
Maryam Hasheminezhad,
Kamran Akhbari,
Anukorn Phuruangrat
25

26