First Example of a Nonanuclear Silver Sulfate Hybrid Cluster: Green Approach for Synthesis of Lewis Acid Catalyst

Article abstract of DOI:10.1021/acs.cgd.8b01258

Finding a high nuclearity hybrid framework with novel structure and properties by an environmentally benign approach is a really challenging task. Herein, a green strategy for synthesis of a new inorganic-organic hybrid framework solid has been described. The framework contains silver sulfate clusters with nine different silver ions with shortest silver-silver connectivity. The present compound is the first example of nonanuclear silver sulfate hybrid framework with a new topology. The hybrid solid compound shows a highly active Lewis acidic nature for the various heterogeneous catalytic reactions such as cyanosilylation, ketalization, and esterification with quantitative transformation and recyclability.

Full text of DOI:10.1021/acs.cgd.8b01258

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Communication
First Example of a Nonanuclear Silver Sulfate Hybrid Cluster:
Green Approach for Synthesis of Lewis Acid Catalyst
Avijit Kumar Paul, Kumari Naveen, Nikhil Kumar, Rajendiran Kanagaraj, V M Vidya, and Tanmay Rom
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b01258 • Publication Date (Web): 24 Oct 2018
Downloaded from http://pubs.acs.org on October 25, 2018
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First Example of a Nonanuclear Silver Sulfate Hybrid Cluster:
Green Approach for Synthesis of Lewis Acid Catalyst
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Avijit Kumar Paul,* Kumari Naveen, Nikhil Kumar, Rajendiran Kanagaraj, V. M. Vidya and
Tanmay Rom
Department of Chemistry, National Institute of Technology Kurukshetra, Kurukshetra-136119, Haryana, India.
Supporting Information Placeholder
synthesis of products in laboratory as well as in industry.
Solvent-free or solvent-assisted mechanochemical reactions
are widely used for the last few years to synthesize the metal-
organic frameworks, coordination polymers or hybrid
frameworks.32-38 In this report, we have applied the high
energy mechanochemical strategy to obtain the completely
pure hybrid catalyst. Solvent drop grinding strategy was
adopted to synthesize new silver sulfate, [Ag8
(SO4)4(C3H6N6)3] (I), framework compound. The present
three-dimensional extended solid has been used for various
heterogeneous catalytic reactions due to its Lewis acidic
nature. Herein, we are communicating the novel synthetic
strategy, crystal structure, characterizations, topology and
various heterogeneous catalytic behaviors.
Single crystal of the present compound was prepared by
using solvothermal conditions in the presence of water and
ethanol at 125 oC in a Teflon-lined autoclave (see ESI).
Although the single crystal of compound I was synthesized
in solvothermal condition, the complete phase pure product
was not obtained under solvothermal conditions. Once the
single crystal was obtained using above condition, the pure
polycrystalline powder compound was synthesized by
mechanochemical synthetic strategy with solvent drop
approach. Exact molar ratio was ground for 2 hours to
homogenize properly. Afterwards few drops of EtOH were
added at the time of grinding for improvement of
homogeneity. The finely ground mixture was kept inside the
oven at 125 oC for 3 days. The pure white powdered
compound was characterized by PXRD which shows the
purity of the compound (See ESI, Fig. S1). Elemental analyses
(using CHN analyser) were carried out for polycrystalline
powdered compound and single crystals obtained from
solvothermal synthesis. The observed results (C: 6.57%; H:
1.15%; N: 15.59%) of powdered sample well matched with
single crystals (C: 6.60%; H: 1.13%; N: 15.55%) and calculated
elemental percentage (C: 6.64%; H: 1.10%; N: 15.50%). Hence,
all further characterizations and catalytic studies were
performed using the powdered compound I synthesized by
mechanochemical strategy.
ABSTRACT: Finding of high nuclearity hybrid framework
with novel structure and properties in an environmentally
benign approach is a really challenging task. Herein, a green
strategy for synthesis of a new inorganic-organic hybrid
framework solid has been described. The framework contains
silver sulfate clusters with nine different silver ions with
shortest silver-silver connectivity. Present compound is the
first example of nonanuclear silver sulfate hybrid framework
with a new topology. Hybrid solid compound shows highly
active Lewis acidic nature for the various heterogeneous
catalytic reactions such as cyanosilylation, ketalization and
esterification with quantitative transformation and
recyclability.
Functional organic-inorganic hybrid frameworks are
intensively studied because of their fundamental scientific
interest and potential applications in adsorption, separation,
catalysis, sensor, ion-exchange and photoluminescence.1-8
The bonding nature of inorganic ion plays vital role for
structural variation whereas the organic moiety produces the
multi-functional properties. Constant efforts on research in
hybrid framework materials have evolved a variety of
inorganic building moieties and organic linkers. From last
few decades, silicate, phosphate, phosphite, sulfate, sulfite,
selenate, selinite, borate, carbonate and thiosulfate ions are
mainly used for the synthesis of new hybrid framework
materials.9-26 Sulfate based hybrid frameworks are not
investigated comp1rehensively as few 3d-transition metals
and lanthanum based sulfate frameworks are reported
earlier.27-31 Our past efforts have resulted few hybrid
cadmium sulfate frameworks with versatile topology and
catalytic activity.31 As the nitrogen containing aromatic
organic ligands are very significant to enhance the
dimensionality and functionality of the hybrid framework
structures, polyazaheterocyles and their derivatives are of
particular interest in our present study. Any functional
hybrid becomes more exciting when it can be synthesized
with greener approach along with their sustainable
applications.
Mechanochemical reaction,
a promising synthetic
The asymmetric unit of I contains 56 non hydrogen
technique, leads to form the product by applying the
mechanical force with addition of negligible amount of
solvent. This strategy is superior from Green Chemistry point
of view which avoids the environment pollution. Hence, this
alternative synthetic approach is readily acceptable for the
atoms, of which four
S
and nine Ag atoms are
crystallographically independent (Fig. 1a). Out of nine silver
atoms, Ag(6) and Ag(9) occupy special position (2i) with a
site multiplicity of 0.5. Ag(1), Ag(3) and Ag(7) have the
similar coordination environment (See ESI, Fig. S5-S6). They
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are coordinated with three oxygen atoms of sulfate units and
assembled with 12-connected [Ag16(SO4)8] units and 8-
connected [Ag4(SO4)2] units. Second complex features 14-
connected [Ag10(SO4)5] clusters with highest connectivity
Ag(I) cluster SBU reported till the date. A series of silver
sulfate coordination polymers have been synthesized in
presence of bipyrazole ligands by Hou et. al.40 Here, the
structural diversity and dimensionality arises mainly due to
the flexible orientation of bipyrazole ligands. Tong and
coworkers have also reported one luminescent octanuclear
silver (I) cluster [Ag8(SO4)2] with two-dimensional layer
structure.41 All the above silver sulfate compounds have weak
argentophilic interactions with Ag-Ag distances above 3.00
Å. Such Ag∙∙∙Ag interactions are more significant for silver
based framework materials.42,43 Beside the silver sulfate
compounds, Jin et. al have also communicated one
one nitrogen atom of the melamine unit forming the
distorted tetrahedral geometry (AgO3N, CN = 4). Ag(2) and
Ag(4) have also shown the similar geometry by coordinating
with three oxygen atoms of sulfate units, one nitrogen atom
of the melamine unit and one silver ion forming the
distorted trigonal bipyramidal geometry (AgO3NAg, CN = 5).
Ag(5) and Ag(8) have the similar coordination environment.
They are coordinated with two oxygen atoms from sulfate
units, one nitrogen atom of the melamine unit and one silver
ion forming the distorted tetrahedral geometry (AgO2NAg,
CN = 4). Ag(6) is coordinated with two oxygen atoms of
sulfate units, one nitrogen atom of the melamine unit and
two silver ions forming the distorted trigonal bipyramidal
geometry (AgO2NAg2, CN = 5). The remaining Ag(9) is
forming the distorted tetrahedral geometry by coordinating
with one oxygen atom of sulfate unit, one nitrogen atom of
the melamine unit and two silver ions (AgONAg2, CN = 4).
Interestingly, nine Ag-ions are showing five characteristic
coordination environments possessing tetrahedral or trigonal
bipyramidal geometry (See ESI, Fig. S5-S6). The Ag-O bond
distances are in the range of 2.246(14) - 2.604(19) Å (av. Ag-O
= 2.424 Å) and Ag-N bond distances are in the range of
2.216(15) - 2.305(15) Å (av. Ag-N = 2.251 Å). There are five
distinguished Ag-Ag bonds present in the structure. Ag-Ag
bonds are in the range of 2.389(7) - 3.315 (2) Å (av. Ag-Ag =
2.953 Å) which is comparable with the earlier literatures.39-45
There are four sulfate units with average S-O bond distances
of 1.443 Å. The sulfate unit possesses an average angle of
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octanuclear
Ag8-cluster
stabilized
with
adamentanedicarboxylic acid.44 The compound exhibits 2D-
layer of Ag-Ag interactions including ten kinds of Ag-Ag
contacts ranging from 2.98 Å to 3.66 Å. Rao et al.
communicated one dimeric silver cluster with cyanuric acid
possessing silver sheets of average Ag-Ag distances around
2.95 Å.45 Above literature survey clearly reveals the distinct
connectivity as well as shortest Ag(I)-Ag(I) bonding
interactions in our present silver sulfate hybrid framework
compounds. The TOPOS analysis was also performed to
understand the simplified structural-connectivity.46-48 Three
different nodes were presented for silver ions, sulfate units
and melamine units as all the units are containing more than
two coordination sites. Overall net is formed by 3-, 4-, 5-
connected 16 nodal points. Point symbol of the net is
{3.62.73.82.92} {3.62.73} {32.4.62.7}2 {4.63.82}2 {6.102} {6.82} {63.73}2
{63.83}{63}5. The detailed analysis showed that the observed
net is unique as it forms completely new topology (See ESI,
109.4ο, which is indicative of
a
regular tetrahedral
arrangement. The crystallographic parameters and selected
bond distances are listed in Table T1-T2 (See ESI).
The present silver sulfate compound has three-
dimensional extended structure. The structure can be
understood in simplified way by taking the silver and sulfate
coordination at first. As the structure has nine different silver
ions and four different sulfate ions, the connectivity of both
the ions make three-dimensional extended structure (See
ESI, Fig. S8). Six silver ions and six sulfate units form a 12-
membered ring in which the melamine unit is connected to
three alternate silver ions (Fig 1b). The presence of melamine
units eradicates the porosity of the open-framework
structure. Such 12-membered rings grow along three
directions to make the three-dimensional extended structure
(Fig. 2). The coordination numbers of silver ions are four and
five which include various Ag-O, Ag-N and most importantly
Ag-Ag bonds. Interestingly minimum Ag-Ag distance is 2.39
Å which is observed for the first time though the metallic Ag-
Ag bond distance is 2.91 Å. As silver exists in +1 oxidation
state, so the present distance is slightly greater than the ionic
distance (2.25 Å) of two silver ions.
The present compound possesses unusual structural
diversity as the metal shows the variable bonding
connectivity from four to five. Compared to the earlier
reported silver sulfate framework compounds, the present
structure shows the novel bonding connectivity with unique
cluster formation. A list of the compounds with silver
clusters and their observed properties have also been given
(see ESI, Table 3). Mak and coworkers have reported two
Fig. S11).
Figure 1. (a) Presence of nine different silver ions, four
sulfate units and three melamine units in asymmetric unit of
I. (b) Connectivity of one melamine unit with three different
porous
silver
clusters
The
[Ag16(SO4)8][Ag4(SO4)2]
and
[Ag10(SO4)5].39
complex containing
[Ag16(SO4)8][Ag4(SO4)2] subunits exhibits two kinds of cages
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silver ions forming 12-membered ring. (c) Unit-cell
representation of the compound I.
many Cd based framework catalysts. The ketalizations of
various ketones also reflect the Lewis acid nature of the
present compound. For ketal formation, we used three
different ketones i.e. acetone, 2-butanone and 3-pentanone.
1
All product yields were determined by H NMR spectra (See
5
ESI). Three different aliphatic ketones have been converted
quantitatively to the respective ketals (Scheme 1). In each
reaction, we used catalyst and ketone ratio 1:800. Such high
efficiency of this catalytic activity was successfully observed
to various keton without depending on substrate structure.
At last, we carried out the esterification between acetic
acid and ethanol with silver sulfate catalyst. Catalyst and
substrate ratio was 1:800 similar to the ketalization.
Esterification reaction gave a yield of 55% after 10 h reaction
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o
at 60 C with continuous stirring. It was not observed any
improvement to the yield even after longer reaction time.
The yield for this reaction was considerably less, but the
reactivity appears to be promising as observed in the ketal
formation reaction. Blank experiments were carried out for
each catalysis reaction under similar conditions without any
catalyst, only negligible product formation confirming the
effective catalytic activity of silver sulfate. The recyclability
nature of the compound was checked for each reaction by
performing three cycles. The similar yields were obtained in
each cycles and the negligible weight loss of the catalyst was
obtained after each cycle. To understand changes in the
chemical environment or structure under catalytic
conditions, we examined the powder x-ray diffraction
patterns of the catalyst after each catalytic reaction. PXRD
pattern of the catalyst remains completely same and the
amount of the recovered catalyst matches well with the
added catalyst (see ESI, Fig. S12). Overall, the high efficiency
and reusability presented here prove that our new silver
sulfate framework is a new example of Lewis acid catalyst for
various heterogeneous catalysis reactions.
Figure 2. Three-dimensional polyhedral view of compound I
along the bc plane.
Considering the lower coordination sites of Ag(I)-ions, we
are keen to check its catalytic activity. A catalyst is designed
in such a way that it provides negligible toxicity, higher
recyclability and shows better cost effective performance in
economic aspects. Recently, metal-organic frameworks and
various metal-clusters are extensively used for heterogeneous
catalysis reactions along with their multifunctional
49-54
applications.
Our earlier efforts on cadmium sulfate
catalysts proved that 4d-transition metal-based frameworks
can be used as Lewis acid catalyst. It has been well
established when a metal center with larger ionic radius is
coordinately unsaturated; it can be served as Lewis acid
catalyst. In the present compound I, the coordination
numbers of silver ions vary from four to five which can
accommodate
additional
coordinating
ligands
for
heterogeneous catalytic activity. The Lewis acid character
was examined through few well-known catalytic reactions i.e.
cyanosilylation, ketalization and esterification. The above
mentioned reactions generally require acid as the catalyst to
increase the nucleophilicity of the carbonyl and imine-
carbon. Instead of mineral acids, the acidity can be achieved
by silver-ions as it works as Lewis acidic center with
heterogeneous catalytic behavior.
Initially, we checked the catalytic activity of compound
I for cyanosilylation reaction as it was studied earlier with
silver and cadmium based few hybrid framework
compounds.30-31,55 The addition of cyanide group occurs
through the carbon-carbon bond formation in carbonyl
carbon or imine compounds. The cyanohydrin products are
intermediates in several organic compounds, e.g.,
aminoalcohal, hydroxyaldehydes, hydroxyacids. Here
a
model imine was taken to perform the catalytic reaction with
the finely powdered polycrystalline compound (Scheme 1).
The product was analyzed and evaluated for the conversion
1
of the reactants (99%) through H NMR spectra (See ESI).
The catalyst to imine mole ratio was 1:100 which is notable
and the present result shows better activity compared to
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Scheme 1: Various heterogeneous catalytic reactions
observed in presence of compound I.
The applicability of hybrid structures composed by d10
shell metal ions in the field of catalysis remains
uninvestigated where the Lewis acidity arises due to the
presence of low-coordinate open sites. The Lewis acidic
nature of metal cations can be explained on the basis of e/r
ratio (where e = charge and r = ionic radius), which is the
basic criteria for the measurement of the electron-
withdrawing ability of the metal cations. Although the
charge of the silver ion is less but more number of
coordinately unsaturated silver ions increase the efficiency in
catalytic reactions. On the basis of present investigations, a
plausible mechanism is displayed in Scheme 2. Here,
electron-rich nucleophilic oxygen atoms present on the
surface of Ag cluster framework initiate the reaction and
transferred electrons to the trimethylsilyl group of TMSCN,
with the formation of weak coordinated Si-O bond. The
pentavalent silicon intermediate has weakened C-Si bond
and increases the nucleophilicity of cyanide group, resulting
attachment to the Lewis acidic Ag sites. The electron rich
In summary, we have reported solvent drop green
synthesis of new silver sulfate hybrid cluster comprising
stability upto 400 C. The crystal structure analysis has been
0
shown the shortest Ag-Ag bond length consisting nine
different silver atoms in asymmetric unit. The compound
forms a new topology with 16-nodal points. The hybrid silver
sulfate framework is applicable as heterogeneous catalyst for
the cyanosilylation, ketalization and esterification reactions.
Present compound is unique with its structural novelty along
with potential applicability. The present study can motivate
for the further research on synthesis of new heterogeneous
solid acid catalyst by economical and environment-friendly
mechanochemistry.
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ASSOCIATED CONTENT
Supporting Information
Tables listing crystallographic data, selected bond lengths,
PXRD patterns, IR spectrum, TGA plot, few structures, SEM
1
image, Gas-adsorption plot, Topological analysis, H-NMR
plot for catalysis reactions. This material is available free of
charge via the Internet at http://pubs.acs.org.
nitrogen atom of imines formed
a weak bond with
neighboring Lewis acidic Ag sites. Then, further nucleophilic
CN group attacked to carbon and formed cyanosilylated
species which comes out as a product in next step. In
ketalization reactions, our cation-rich silver-based hybrid
framework activates the oxygen of the carbonyl group and
permits glycol to replace for the carbonyl group. The carbon
atom of the carbonyl group undergoes nucleophilic attack by
the hydroxyl group of ethyl alcohol resulted in the bond
formation between the carbon atom of the carbonyl group
and the hydroxyl group of ethyl alcohol with the removal of
water. The similar activation will be observed with acetic
acid also. But the electrophilicity of the carbonyl carbon will
be the higher in carbonyl group compared to acid group.
Hence the complete conversation can be observed in ketones
as reported earlier.
Corresponding Author: *Email: apaul@nitkkr.ac.in
ACKNOWLEDGMENT
Authors acknowledge the financial support from the
Department of Science and Technology through INSPIRE
Award (No. IFA14-CH-144) & Science and Engineering
Research Board, India in the form of Start-Up Research Grant
(No. SB/FT/CS-098/2014). The authors thank Prof. S.
Natarajan of Indian Institute of Science, for help with the
Single Crystal data collection and fruitful discussion.
Scheme 2: Plausible mechanism for the Lewis acid catalyzed
cyanosilylation of imines.
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(19) Paul, A. K. Tuning of coordination behavior of thiosulfate
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First Example of a Nonanuclear Silver Sulfate Hybrid Cluster: Green Approach for
Synthesis of Lewis Acid Catalyst
Avijit Kumar Paul,* Kumari Naveen, Nikhil Kumar, Rajendiran Kanagaraj, V. M. Vidya and
Tanmay Rom
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A hybrid silver sulfate framework featuring nine silver atoms in the asymmetric unit with
shortest Ag–Ag bond is synthesized under mechanochemical strategy. The framework has new
topology and found to be very efficient heterogeneous catalyst for cyanosilylation, ketalization
and esterification reactions.
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