Reversible liquid assisted mechanochemical conversion of sodium coordination polymer nanorods to organosilver coordination polymer nanosheets

Article abstract of DOI:10.1016/j.inoche.2016.10.034

Reversible solid-state structural transformation of sodium(I) coordination polymer nanorods, prepared by sonochemical procedure, to organosilver coordination polymer nanosheets has been observed upon liquid assisted mechanochemical reaction of compound [N

Full text of DOI:10.1016/j.inoche.2016.10.034

Reversible liquid assisted mechanochemical conversion of sodium coordina-
tion polymer nanorods to organosilver coordination polymer nanosheets
Fatemeh Shahangi Shirazi, Kamran Akhbari, Satoshi Kawata, Ken Kanazashi
PII:
DOI:
Reference:
S1387-7003(16)30315-X
doi:10.1016/j.inoche.2016.10.034
INOCHE 6471
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Inorganic Chemistry Communications
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4 September 2016
18 October 2016
19 October 2016
Please cite this article as: Fatemeh Shahangi Shirazi, Kamran Akhbari, Satoshi Kawata,
Ken Kanazashi, Reversible liquid assisted mechanochemical conversion of sodium coor-
dination polymer nanorods to organosilver coordination polymer nanosheets, Inorganic
Chemistry Communications (2016), doi:10.1016/j.inoche.2016.10.034
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ACCEPTED MANUSCRIPT
Reversible Liquid Assisted Mechanochemical Conversion of Sodium
Coordination Polymer Nanorods to Organosilver Coordination Polymer
Nanosheets
a
a,
b
b
Fatemeh Shahangi Shirazi , Kamran Akhbari *, Satoshi Kawata and Ken Kanazashi
a
School of Chemistry, College of Science, University of Tehran, P.O. Box 14155-6455, Tehran,
Islamic Republic of Iran. Tel.: +98 21 61113734; fax: +98 21 66495291.
E-mail address: akhbari.k@khayam.ut.ac.ir (K. Akhbari)
b
Department of Chemistry, Fukuoka University, 8-19-1 Nanakuma, Jonan-ku, Fukuoka, 814-
0
180, Japan.
Abstract
Reversible solid-state structural transformation of sodium(I) coordination polymer nanorods,
prepared by sonochemical procedure, to organosilver coordination polymer nanosheets has been
observed upon liquid assisted mechanochemical reaction of compound [Na (1,5-nds)(H O) ]
2 n
2
2
(
1), [1,5-H nds = 1,5-naphthalenedisulfonic acid] with AgNO . During this conversion, two
2
3
coordinated H O molecules were removed from 1 and substituted with two carbon atoms from
2
2
1
,5-nds ‾ ligand in 2. Thus organosilver coordination polymer of 2 was formed during this
conversion and distorted trigonal-bipyramidal coordination geometery in 1 with NaO5
coordination sphere was converted to distorted tetrahedral geometry in 2 (regarding the C=C
group as one donor) with AgO C coordination sphere.
3
2
Keywords: Solid-state conversion, Organosilver, Nanorods, Nanosheets, Coordination Polymer.
Last two decades, the rational design and synthesis of novel coordination polymers has made
considerable progress [1-6]. The importance of coordination polymers is based not only on their
intriguing structural motifs, but they also exhibit a range of potentially useful applications [7-12].
Solid-state transformations of coordination polymers are interesting since they involve breaking
and forming of coordination bonds in more than one direction. There are several types of
1

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structural transformations that are primarily influenced by the expansion of the metal
coordination numbers, thermal dissociation/association, condensation, rearrangement of bonds or
the removal/exchange of solvents [13-17]. Solid-state reactions by manual or mechanical
grinding with minimal or no solvent for molecular synthesis have triggered lots of attention [18-
2
3]. Mechanochemistry refers to reactions, normally of solids, induced by the input of
mechanical energy, such as by grinding in ball mills. It is becoming more intensely studied partly
because it can promote reactions between solids quickly and quantitatively, with either no added
solvent or only nominal amounts. Historically it has been a sideline approach to chemical
synthesis, and solution-based methods have been adopted by default. However,
mechanochemistry could in future become a more mainstream technique for two reasons. Firstly,
it is increasingly clear that is effective, and even advantageous, in ever-widening types of
synthesis. Secondly, our current dependence on solvents appears increasingly unsustainable since
it is wasteful of fossil-derived materials (e.g. 85% of chemicals used in the pharmaceutical
industry are solvents and even if recycled typical recovery rates are only 50–80%) [24],
environmentally problematic, hazardous and energy-demanding with regard to solvent
production, purification and recycling [25]. Structural transformations of coordination polymers
in the solid-state are involving the formation and breakage of at least a chemical bond [26].
Coordination polymers exhibit a variety of solid-state reactions that involve changes in
coordination spheres by the loss, uptake or exchange of ligands or guest molecules and by
external stimuli [26]. The vacant coordination sites at the metal centres created by the removal of
ligands are often found to be re-established by the free donor sites of the neighbouring ligands or
guest molecules in the solid. In the past, many interesting structural transformations, where
single crystallinity was lost, have been overlooked or left unexplored due to the lack of such
modern techniques [26]. J. J. Vittal et. al. anticipate that with the help of modern structure
determining tools, many systems undergoing single crystalline-to-polycrystalline and crystalline-
to-amorphous-to-crystalline transformations can be routinely studied; and many new discoveries
will be made which will establish new milestones on the path of progress of modern solid-state
science [26]. Thus in this work, during the course of syntheses coordination polymers from 1,5-
naphthalenedisulfonic acid (1,5-H nds) in our laboratory, we decided to synthesis nanostructures
2
2

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of [Na (1,5-nds)(H O) ] (1) [27] by sonochemical procedure [28–31] and then study structural
2
2
2 n
conversion of it to [Ag (1,5-nds)] (2) [32] by cation exchange mechanochemical reaction.
2
n
The reaction between 1,5-Naphthalenedisulfonic acid and NaOH in ultrasonic bath results in
formation of white powder which was dried at room temperature. A comparison between the
XRD patterns simulated from single crystal X-ray data of [Na (1,5-nds)(H O) ] (1) [27] (Figure
2
2
2 n
1
a) and that of the prepared powder (Figure 1b), approved the formation of it with 3D network
2
(
Figure 2). A side view of primary unit of 1 shows that 1,5-nds ‾ acts as a bridging ligand
between six sodium ions (Figure S1a in the SI). Only one type of sodium ion exists in 1 which is
2
coordinated with three oxygen atoms from three different sulfonate groups of 1,5-nds ‾ ligands
and two oxygen atoms from two water molecules (Figure S1a in the SI). The water molecules in
1
bridge between two sodium ions and finally we have three dimensional coordination polymer
in 1 (Figure S1b in the SI). SEM image of the obtained powder approved that compound 1
nanorods were formed under ultrasonic irradiations (Figure 3a). Silver(I), with Van der Waals
radius of 1.72 Å, is similar in structure and chemical properties of their compounds to sodium(I),
with Van der Waals radius of 2.27 Å [33,34]. Thus we decided to study the structural changes of
2
1
during conversion of it to Ag(I) coordination polymer of 1,5-nds ‾, [Ag (1,5-nds)] (2) [31],
2
n
2
which has similar structure to 1. In 2, 1,5-nds ‾ acts as a bridging ligand between eight silver ions
(Figure S2a in the SI). Only one type of silver ion exists in 2 which is coordinated with three
2
oxygen atoms from three different sulfonate groups of 1,5-nds ‾ ligands, similar to 1, and two
carbon atoms from aromatic naphthalene ring (Figure S2 in the SI). Finally we can consider 2 as
three-dimensional coordination polymer (Figure 2). In order to consider the possibility of this
conversion (1 to 2 which has approximately similar coordination sphere around metal ions), we
studied liquid assisted mechanochemical reaction of 1 with excess AgNO . The XRD pattern of
3
compound 1 after solid-state mechanochemical reaction with excess AgNO (Figure 1d)
3
approved that ion exchange process of Na(I) with Ag(I) was occurred. After removal of NaNO3
and unreacted AgNO from the products mixture, the pure phase of 2 was separated (Figure 1f).
3
SEM image of the mixture obtained from mechanochemical reaction of 1 with excess AgNO3
indicates the formation of nanocubes (Figure 3b). After washing the prepared mixture with
water, surprisingly we observed that nanorods of 1 were converted to nanosheets of 2 (Figure
3
c). The XRD pattern of 2 after mechanochemical reaction of it with NaNO (Figure 1h) shows
3
3

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the formation of compound 1 from the reverse reaction. Thus this transformation is reversible
(
Figure 2). Because the prepared mixture was soluble in water, we could not wash AgNO from
3
resulting mixture, to obtain the pure phase of compound 1 from the reverse reaction. Although
the SEM image of the prepared sample from the reverse reaction (Figure 3d) indicates the
formation of compound 1 nanorods which is exactly similar to that obtained in ultrasonic bath
from the reaction between 1,5-H nds ligand and NaNO (Figure 3a). From the SEM images it is
2
3
obvious that compounds 1 and 2 tend to form nanorods and nanosheets, respectively. We could
conclude that reversible conversion of [Na (1,5-nds)(H O) ] (1) nanorods to [Ag (1,5-nds)] (2)
2
2
2 n
2
n
nanosheets is possible during solid-state mechanochemical reaction.
A comparison between the coordination geometry of the Na and Ag atoms in the coordination
polymers of [Na (1,5-nds)(H O) ] (1) and [Ag (1,5-nds)] (2) allows us to explain this reversible
2
2
2 n
2
n
+
+
solid-state transformation. As illustrated in Figure 4, during the exchange of Na ion with Ag ,
two coordinated H O molecules were removed and substituted with two carbon atoms from 1,5-
2
2
nds ‾ ligand. Thus organosilver coordination polymer of 2 was formed during this conversion
and distorted trigonal-bipyramidal coordination geometery in 1 with NaO coordination sphere
5
was converted to distorted tetrahedral geometry in 2 (regarding the C=C group as one donor)
with AgO C coordination sphere. C. Thompson, et. al. used microscopic techniques to reveal
3
2
the mechanism of anion exchange in crystalline coordination polymers [34]. They showed that
the anion exchange, and subsequent structural transformation, proceeds via a solvent mediated
mechanism, rather than a purely solid-state one [35]. It seems that similar mechanism could be
propose for cation exchange in coordination polymers through liquid-assisted grinding (LAG)
method.
TGA data (Figure S3a in the SI) indicates that endothermic removal of H O molecules from
2
[
Na (1,5-nds)(H O) ] (1) nanorods starts at 60 °C and this process is continued up to 236 °C
2 2 2 n
with a mass loss of 7.1% (calcd 9.7%). The remaining compound is stable up to 510 °C. Single
crystals of 1 also show similar thermal behavior (Figure S3b in the SI). The thermal behavior of
compound 1 after solid-state mechanochemical reaction with excess AgNO (Figure S3c in the
3
SI) is different from 1 (Figure S3a,b in the SI) which approved formation of other new
compound (2) from this conversion. Thermolysis of compound 1 is accompanied with an
exothermic peak at 209 °C which do not observed in this mixture (Figure S3c in the SI). The
4

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thermal behavior of compound [Ag (1,5-nds)] (2) after washing the mixture obtained from
2
n
solid-state mechanochemical reaction (Figure S3d in the SI) shows that compound 2 with
nanosheet morphology is stable up to 157 °C. Interestingly, in this case we observed that single
crystal of 2 has more thermal stability than nanosheet of it and thermolysis of its crystal occurs
above 290 °C (Figure S3e in the SI). We also examined thermal behavior of compound 2 after
mechanochemical reaction of it with excess NaNO (Figure S3f in the SI). The result shows the
3
mass loss between 120-150 °C which accompanied with an endothermic peak at 145 °C and may
be attributed to removal of coordinated H O molecules from 1. This observation also indicates
2
that conversion of 1 to 2 is reversible and in this stage we only have mixture of 1 and AgNO3.
In summary, solid-state structural conversion of [Na (1,5-nds)(H O) ] (1) nanorods with
2
2
2 n
I
three-dimensional network to three-dimensional Ag coordination polymer [Ag (1,5-nds)] (2)
2
n
with nanosheet morphology has been observed upon liquid assisted mechanochemical reaction of
compound 1 with AgNO . This conversion is reversible and the nano structure morphologies also
3
converted to each other reversibly. A comparison between the coordination geometry of the Na
and Ag atoms in these two coordination polymers allows us to explain this reversible solid-state
+
+
transformation. During the exchange of Na ion with Ag , two coordinated H O molecules were
2
2
removed and substituted with two carbon atoms from 1,5-nds ‾ ligand. Thus organosilver
coordination polymer of 2 was formed during this conversion and distorted trigonal-bipyramidal
coordination geometery in 1 with NaO coordination sphere was converted to distorted
5
tetrahedral geometry in 2 (regarding the C=C group as one donor) with AgO C coordination
3
2
sphere. Studying these types of solid-state mechanochemical reaction is being investigated in our
laboratory.
Acknowledgements
The authors would like to acknowledge the financial support of University of Tehran for this
research under grant number 01/1/389845.
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Figure 1. XRD patterns; a) simulated pattern based on single crystal data of compound [Na (1,5-
2
nds)(H O) ] (1), b) compound 1 nanorods synthesized under ultrasonic irradiations, c)
2
2 n
compound 1 single crystal, d) compound 1 nanorods after liquid-assisted mechanochemical
reaction with excess AgNO , e) simulated pattern based on single crystal data of [Ag (1,5-nds)]
3
2
n
8

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(2), f) pure phase of compound 2, g) compound 2 single crystal and h) compound 2 nanosheets
after mechanochemical reaction with NaNO3.
I
Figure 2. A schematic diagram illustrating the solid-state structural transformation of 3D Na
I
coordination polymer of 1 to 3D Ag coordination polymer of 2 upon mechanochemical reaction
9

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of 1 with AgNO , (Na = green, Ag = violet, O = red, S = yellow, C = gray and H = white).
3
1
synthesized under ultrasonic irradiations
1
0

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Figure 4. Schematic representation of changes in Na(I) coordination sphere during the solid-
state structural transformation of 1 (left) to 2 (right) during liquid assisted mechanochemical
reaction of 1 with AgNO3.
Graphical absrtact
Reversible
solid-state
structural
transformation of sodium(I) coordination
polymer nanorods, prepared by sonochemical
procedure, to organosilver coordination
polymer nanosheets has been observed upon
liquid assisted mechanochemical reaction.
Research highlights:




Solid-state conversion of Na(I) to organometallic Ag(I) CP was studied.
During this conversion morphology change from nanorods to nanosheets was observed.
This conversion was studied via liquid assisted mechanochemical reaction.
During this conversion, H O molecules were removed and substituted with carbon atoms.
2
1
1