Porous organic polymer bearing triazine and pyrene moieties as an efficient organocatalyst

Article abstract of DOI:10.1016/j.mcat.2020.111198

Materials with high specific surface area and bearing abundant basic sites at their pore surface are very demanding as heterogeneous catalyst for the eco-friendly base catalyzed reactions. Here we have developed a new secondary amine linked triazine and p

Full text of DOI:10.1016/j.mcat.2020.111198

Molecular Catalysis 497 (2020) 111198
Contents lists available at ScienceDirect
Molecular Catalysis
journal homepage: www.journals.elsevier.com/molecular-catalysis
Porous organic polymer bearing triazine and pyrene moieties as an
efficient organocatalyst
Sabuj Kanti Das, Avik Chowdhury, Debabrata Chakraborty, Utpal Kayal, Asim Bhaumik*
School of Materials Sciences, Indian Association for the Cultivation of Science, 2A & 2B Raja S. C. Mullick Road, Jadavpur, Kolkata, 700032, India
A R T I C L E I N F O
A B S T R A C T
Keywords:
Materials with high specific surface area and bearing abundant basic sites at their pore surface are very
demanding as heterogeneous catalyst for the eco-friendly base catalyzed reactions. Here we have developed a
new secondary amine linked triazine and pyrene containing microporous organic polymer (TrzPyPOP) through a
simple polycondensation reaction between tetramine1,4-bis(4,6-diamino-s-triazin-2-yl)-benzene (SL-1) and
monoaldehyde pyrene-1-carboxaldehyde. This new porous organic polymer TrzPyPOP is very rich in N-content
with high BET surface area (1016 m2 gꢀ 1). High surface area and N-rich surface basic sites have been explored in
its potential as heterogeneous organocatalyst for the synthesis of dihydropyrimidones via Biginelli condensation
involving three-component coupling reaction. Only a very little amount of catalyst was effective for the synthesis
of dihydropyrimidones derivatives (yields = 88–99 %) together with high recycling efficiency under the opti-
mum reaction conditions.
Porous organic polymer
Surface area
Heterogeneous catalysis
Multi component reaction
Biginelli reaction
1. Introduction
Being a one-pot process involving multiple reactants, the products ob-
tained from the MCR are economically favorable too. However, under
Convenient and eco-friendly strategies for the synthesis of dihy-
dropyrimidones (DHPMs) [1] have attracted considerable attention over
the years in medicinal chemistry as these compounds worked efficiently
for the treatment of cardiovascular diseases [2]. DHPMs show close
structural as well as compositional resemblance with nifedipine, often
used to regulate high blood pressure. Further, the activity of the DHPMS
can be tuned by changing the axial aromatic group, which bisect the
boat conformation [3]. Thus, continuous research efforts are directed for
the modification of the reactants and reaction conditions [4] for better
yield of DHPMs together with its high purity in shorter reaction time. In
this context, multicomponent condensation reaction between reactive
small organic molecules in the presence of suitable catalyst can offer
viable route for the synthesis of DHPM derivatives. In synthetic organic
chemistry multicomponent reactions (MCR) [5] are very demanding
especially in the discovery of novel drug molecules. In the year 1891,
Italian chemist Petro Biginelli [6] has introduced a one-pot multicom-
ponent reaction featuring the condensation between ethyl acetoacetate,
benzaldehyde and urea. This reaction has versatile potential for the
synthesis of a series of DHPM derivatives. The reaction can easily be
carried out by heating the reactants in the presence of solvent with
catalytic amount of hydrochloric acid at the refluxing temperature.
this reaction conditions often moderate yields of the products are ob-
tained together with no scope for recyclability.
Subsequently scientific community has paid huge attention to
develop several homogeneous and heterogeneous catalytic systems for
synthesizing analogous heteroatom containing chemicals [7] by
exploring different synthetic routes. Several heterogeneous catalysts can
catalyzes the modified Biginelli reactions with good recyclability, easi-
ness in separation of the catalysts from reaction mixture together with
enhanced purity of the product, leaching of active metal sites are the
major issues in these cases for prolonged operation. In this context
metal-free heterogeneous base catalyst or organocatalysts [8] bearing
reactive organic functional groups at the catalyst surface can be utilized
to carry out this MCR for the synthesis of value added DHPMs. Biginelli
condensation reaction has been conducted over a large variety of ho-
mogeneous and heterogeneous catalysts such as Fe(NO3)3.9H2O [9],
12-molybdophosphoric acid [10], Fe(III)/Si-MCM-41 [11], poly
(2-acrylamido-2-methylpropane
sulphonic
acid)
[12],
polystyrene-supported Al(III) [13], Ce-MCM-41 [14] etc. The magnetic
Fe3O4 nanoparticles supported imidazolium-based ionic liquids [15]
and many more surface functionalization strategies [16–20] have been
undertaken for catalyst modification as well as enhancement of the rate
* Corresponding author.
E-mail address: msab@iacs.res.in (A. Bhaumik).
https://doi.org/10.1016/j.mcat.2020.111198
Received 1 July 2020; Received in revised form 26 August 2020; Accepted 29 August 2020
Available online 21 September 2020
2468-8231/© 2020 Elsevier B.V. All rights reserved.

S.K. Das et al.
Molecular Catalysis 497 (2020) 111198
Scheme 1. Synthesis of TrzPyPOP material through the polycondensation of tetramine and monoaldehyde.
of this reaction. Previously we had reported the Fe3O4 nanoparticles
supported functionalized SBA-15 [21] as magnetically recoverable
nanocatalyst for carrying out the Biginelli condensation reaction. But
optimization of the product yields under mild reaction conditions and
purity concern are still remained as major issues for this reaction.
Moreover, only few basic organocatalysts are reported so far for this
Biginelli condensation reaction.
2. Experimental section
2.1. Chemicals
Terephthalonitrile, dicyandiamide, 1-pyrene-carboxaldehyde and
the aldehydes used as substrates for the catalytic reactions, like 4-meth-
ylbenzaldehyde, 4-bromobenzaldehyde, 4-chlorobenzaldehyde, 4-for-
mylbenzonitrile, 4-nitrobenzaldehyde and furan-2-carbaldehyde, were
purchased from Sigma-Aldrich. Ethyl acetoacetate, ethyl cyanoacetate
were received from Loba Chemie, whereas thiourea and urea were
procured from Merck India. Organic solvents such as 2-metoxyethanol,
dimethylsulphoxide (DMSO), ethanol, tetrahydrofuran (THF) and
acetonitrile were purchased from Spectrochem, India.
Porous organic materials have attracted significant interest in solv-
ing several issues of energy and environment in the recent times. Co-
valent organic frameworks (COFs) [22–24], covalent triazine
frameworks (CTFs) [25], conjugated microporous polymers (CMPs) [26,
27] and related other porous organic polymers (POPs) [28–31] are
intensively studied in several frontline applications like catalysis
[32–34], selective gas adsorption [35], water purification [36], light
harvesting [37] and so on. Among all these porous organic materials,
POPs have more flexibility in the synthesis due to their high specific
surface area, ease of synthesis in bulk quantities, ease of the introduction
of the desired functional group and high chemical stability. As POPs are
insoluble in all common organic solvents, they can be used as a het-
erogeneous catalyst for a series of organic transformation and after re-
action the catalyst can be easily isolated, which offer high recyclability
of catalyst after several reaction cycles. Further, abundance of aminal
linkages in the POP network is helpful for carrying out the base cata-
lyzed reactions [38]. Herein we report the facile metal-free base cata-
lyzed Biginelli reaction over a new triazine and pyrene containing
porous organic polymer TrzPyPOP as a heterogeneous organocatalyst
synthesized through a very convenient polycondendation reaction be-
2.2. Material characterizations
The amine monomer SL-1 had been synthesized by Antonpaar
Monowave 300, microwave synthesis reactor. We have used Perkin-
Elmer Spectrum 100 spectrophotometer for investigating the bonding
connectivity through FTIR spectroscopy. The crystalline or amorphous
nature of the powder POP material was analyzed by using wide angle
PXRD data taken in a Bruker AXS D-8 Advanced SWAX diffractometer,
where Cu-Kα (λ =0.15406 nm) radiation was used as X-ray source. After
synthesizing the TrzPyPOP material it was solvent extracted for 3 days
through a Soxhlet apparatus using equimolar mixture of THF and
methanol to remove the adsorbed guest molecules occupied inside the
pores of the material. The porosity and BET surface area of TrzPyPOP
was investigated by analyzing N2 adsorption/desorption isotherm at
-196 ◦C taken in an Autosorb-iQ of Quantachrome Instruments, USA.
Before the BET analysis the TrzPyPOP material was degassed at 150 ◦C
for 4 h. The pore size distribution profile was obtained from the sorption
isotherm by employing non-local density functional theory (NLDFT).
tween
1,4-bis(4,6-diamino-s-triazin-2-yl)-benzene
and
pyrene-1-carboxaldehyde as shown in Scheme 1.
Fig. 2. 13C CP/MAS NMR spectrum of TrzPyPOP. 13C signals are marked with
the corresponding colors of the carbon atoms drawn in the model framework
of TrzPyPOP.
Fig. 1. FT-IR spectra of pyrene-1-aldehyde (a), SL-1 (b) and TrzPyPOP (c).
2

S.K. Das et al.
Molecular Catalysis 497 (2020) 111198
desired solvent in a two neck round bottomed flask and the reaction
mixture was heated for 30 min at different temperature (40–80 ℃).
Then 1.3 mmol of urea was added into the reaction mixture and it was
refluxed for 2-7 h at elevated temperatures. After the reaction, the
products were collected through filtration and purified to obtain the
respective isolated products. All the reaction products were fully char-
acterized by NMR spectroscopy (ESI, Section S1 and Figure S1-S7). After
completion of the catalysis, the reaction mixture was allowed to cool at
room temperature. Then the catalyst was removed from the reaction
mixture by filtration. This was followed by solvent evaporation under
reduced pressure. Then the product was taken in 50 mL of water in a 100
mL beaker and stirred for 30 min. Then the solid product was collected
by filtration. Solid compound was further washed three times by 15 mL
of hexane (each time). Finally, the pure product was obtained by
recrystallization from ethanol and characterized by 1H NMR.
3. Results and discussion
Fig. 3. N2 adsorption (black field square)/desorption (red half field circle)
isotherm of TrzPyPOP at 77 K. Respective pore size distribution is shown in
the inset.
We have synthesized the triazine based four armed amine function-
alized ligand (SL-1) by microwave assisted thermal condensation (at
195℃) between terepthalonitrile and dicyandiamide under alkaline
medium (Scheme 1). This is followed by the polycondensation reaction
between SL-1 with pyrene-1-carboxaldehyde under refluxing conditions
to yield TrzPyPOP. The as synthesized material has been characterized
by several characterization tools and these are summarized below.
Bruker Advance II spectrometer was used to investigate the 1H and 13
C
NMR using deuterated NMR solvents. The 13C CP MAS NMR of insoluble
polymeric material was taken in 8 kHz magic angle spinning frequency
using a 4 nm MAS probe. The particle size and morphological analysis of
the TrzPyPOP polymer have been carried out by collecting HRTEM
images with JEOL JEM 2010 at an accelerating voltage of 200 kV.
Thermal stability of TrzPyPOP was investigated by thermogravimetric
analysis using TA-SDT Q-600 of TA Instruments, USA. The elemental
composition (i.e. carbon, hydrogen and nitrogen) of the TrzPyPOP ma-
terial has been investigated by Perkin Elmer 2400 Series II CHN
analyzer.
3.1. Spectroscopic analysis
The bonding connectivity in TrzPyPOP has been investigated by
Synthesis of 1, 4-Bis(4, 6-diamino-s-triazin-2-yl) benzene (SL-1)
The targeted tetradented ligand (SL-1) was synthesized following our
previously reported literature [39]. In this typical synthesis, at first 640
mg of terephthalonitrile (5 mmol, 640 mg), dicyandiamide (10 mmol,
841 mg), and KOH (1.75 mmol, 100 mg) were taken into a microwave
G-30 vial followed by addition of 15 ml of 2-methoxyethanol solvent.
Then the reaction vial was placed into the microwave reactor and re-
action was carried out at 195 ◦C for 10 min. After that the reaction
mixture was cooled down and it was placed into hot water. Then the
product was filtered off and washed with plenty of water followed by
methanol and finally with acetone to get pure tetraammine ligand SL-1.
75 % yield of the SL-1 product was obtained. The 13C and 1H NMR
analysis of SL-1 compound are: 13C NMR (100 MHz, DMSO-d6) δ =
170.10, 167.59, 139.57, 127.24 ppm. 1H NMR (400 MHz, DMSO-d6) δ =
8.35 (s, 4H, Ar), 6.81 (br s, 8H, NH2).
2.3. Synthesis of TrzPyPOP
The TrzPyPOP was synthesized by the simple polycondensation be-
tween pyrene-1-aldehyde (3 mmol, 420.48 mg) and SL-1 (3 mmol, 891
mg) in 25 ml of dimethylsulphoxide (anhydrous), the under N2 atmo-
sphere at 180 ℃ (Scheme 1). The reaction has been continued for 48 h
and the material is obtained as buff color precipitate. The mixture was
cooled to room temperature and then it was filtered followed by washing
with water, methanol, THF and finally by acetone. The product was
filtered for another 3 days by a mixture of MeOH and THF (1:1) by using
Soxhlet’s apparatus the crude product is dried under vacuum at 180 ◦C
for 24 h thus finally pyrene containing triazine based guest free porous
organic polymer (TrzPyPOP) obtained with isolated yield of 70 %.
2.4. Catalytic reactions over TrzPyPOP
In a typical catalytic reaction a mixture of aldehyde (1.0 mmol),
ethyl acetoacetate (1.1 mmol) and 10.0 mg of TrzPyPOP was taken in a
Fig. 4. Wide angle PXRD (a) and TGA profile diagram (b) of TrzPyPOP.
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S.K. Das et al.
Molecular Catalysis 497 (2020) 111198
Fig. 5. HR-TEM images of as synthesized TrzPyPOP (a and b) and those after sixth catalytic cycle (c and d).
Table 1
Optimization of the Biginelli reaction conditions catalyzed by TrzPyPOP a: Pure isolated product yield.
Entry
Solvent
Time(h)
Temperature
Yielda (%)
1
2
3
4
5
6
7
THF
24
24
24
1.5
24
24
24
RT
80
80
65
70
50
40
–
CH3CN
DCE
34
20
98
40
30
–
THF
EtOH
THF
DCM
a
Pure isolated product yield.
using Fourier-transform infrared spectroscopy (Fig. 1). The peak at 1547
cmꢀ 1 in SL-1 amine as well as in TrzPyPOP indicates the presence of
triazine moiety in TrzPyPop. Further, peak at 1684 cmꢀ 1 in pyrene-1-
carboxaldehyde is absent in the final TrzPyPOP material, which
linkages [40] as of our predicted framework model shown in Scheme
1. To investigate the bonding and structural integrity of the organo-
catalyst, FT-IR spectrum of TrzPyPOP has been collected after 6th cycles
(ESI, Figure S9), where we could not observed any significant changes in
the spectral pattern. This result suggested high robustness of the porous
network in TrzPyPOP. To confirm the formation of the organic frame-
work of TrzPyPOP and the chemical environment of different carbon
atoms in it, 13C CP MAS NMR spectroscopic analysis has been performed
(Fig. 2). The spectrum consist of four sharp and intense peaks at 166.59,
140.05, 128.58 and 56.07 ppm. The NMR signal at 166.59 ppm confirms
the presence of triazine moiety [39]. 13C signal appeared at 140.05 ppm
–
confirm the absence of C O moiety in material, and thus the poly-
–
condensation reaction proceeds completely. The absence of IR band at
around 1640 cmꢀ 1 also confirms the imine (C N) bond is not formed in
–
–
the TrzPyPOP, whereas the signal at around the (1645–1660) cmꢀ 1
confirms the presence of deformation band of aminal linkage (-NH-).
The absence of imine moiety, presence of -NH- deformation band and
the presence of hump at 3300 cmꢀ 1 confirms the presence of aminal-
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S.K. Das et al.
Molecular Catalysis 497 (2020) 111198
3.2. Nanostructure and porosity analysis
Table 2
Substrate scope for the TrzPyPOP catalyzed MCR in THF.
Entry
Aldehyde
Urea
Ester
Product
Time
Yieldh
The porosity and surface area of the TrzPyPOP is investigated by
measuring volumetric N2 adsorption/desorption and the corresponding
isotherm at liquid N2 temperature is shown in Fig. 3. This isotherm in-
dicates high uptake of N2 at low relative pressure (<0.1 P/P0) con-
firming the presence of microporous nature of the polymeric network
together with a steady increase in N2 uptake at high pressure (>0.9 P/
P0) is due to the interparticle voids formation between the polymeric
nanoparticles [41,42]. Thus, this isotherm suggested the presence of
both type I and type IV BET sorption isotherms according to IUPAC
classification [43]. The BET (Brunauer-Emmett-Teller) surface area
1.
1a
2
3
2.0
98
2.
1b
2
3
1.5
98
calculated from the N2 adsorption/desorption isotherm is 1016 m2 gꢀ 1
,
and the pore size distribution graph (inset of Fig. 3) indicated the
presence of hierarchical porosity with peak pore sizes of 1.6 and 2.6 nm.
The high BET surface area and microporosity along with some meso-
porosity is the organic framework is very demanding as it could over-
come the diffusional limitation that faced by the microporous materials
when used alone in heterogeneous catalysis [44]. To investigate the
structural integrity of organocatalyst TrzPyPOP, surface area and
porosity analysis has been conducted with the reused catalyst after sixth
reaction cycle following above method (ESI, Figure S10). The BET sur-
face area of this used catalyst was 1012 m2 gꢀ 1, which is almost same as
that of the fresh catalyst. Pore size distribution of the reused material
also remained unchanged with reference to fresh TrzPyPOP. This result
suggested high structural integrity of the polymer network.
3.
4.
1c
1d
2
2
3
3
2.0
7.0
99
77
5.
1e
2
3
6.5
88
6.
7.
1f
2
2
3
3
1.5
2.0
98
99
3.3. Powder XRD, thermogravimetric and elemental analysis
For sustainable catalytic operation, thermal and chemical stability of
the catalyst is very essential. The amorphous nature of the polymeric
material TrzPyPOP could be attributed to random co-polymerization
between the monomer units (SL-1 and pyrene-1-aldehyde) and this
has been revealed by a very broad hump obtained between 12◦ to 30◦ in
the wide angle (2θ = 2◦ to 60◦) PXRD pattern (Fig. 4a). [36] Further,
thermal stability of the TrzPyPOP material has been evaluated from the
thermogravimetric analysis (TGA) under N2 atmosphere from 25 to 900
◦C with continuous ramping rate of 10 ◦C (Fig. 4b). The TGA profile
diagram showed a sharp weight loss after 450 ◦C, which concludes the
material decomposed after this temperature. The CHN elemental anal-
ysis data on the other hand suggested the presence of 76.44 % carbon,
19.38 % nitrogen and 4.18 % hydrogen in TrzPyPOP.
1g
1a: R = 4-tolyl, 1b: R = 4-bromophenyl, 1c: R = 4-chlorophenyl, 1d: R = 4-nitro-
phenyl, 1e: R = 4-ciyanophenyl, 1f: R = 2-furyl, 1g: R = pyrene, h: pure isolated
yield. 2: urea, 3: ethyl acetoacetate.
3.4. Morphological analysis
The morphological features of the TrzPyPOP material is obtained
from high resolution transmission electron microscopic (HR-TEM)
analysis. The microscopic images of the as-synthesized material and
recycled catalyst after six reaction cycles are shown in Fig. 5. The HR-
TEM images show sphere like particle morphology with particle size
ranging 15–20 nm. The TEM images of recycled materials clearly sug-
gested that the morphology remains unchanged after catalytic reactions.
Thus, HR-TEM analysis suggested no structural deformation during
liquid-phase catalysis.
Fig. 6. Recycling efficiency of TrzPyPOP for the Biginelli condensation be-
3.5. Basicity measurement
tween 4-methylbenzaldehyde, urea and ethyl acetoacetate.
For performing the heterogeneous base catalyzed Beginelli conden-
sation reaction, measurement of the total basic strength of the catalyst is
very much necessary. Direct acid-base titration method has been
employed to measure the basicity of the TrzPyPOP catalyst. From the
volumetric acid-base titration we have measured the basicity of TrzPy-
POP as 0.5432 mmol gꢀ 1. Detail calculation is represented in ESI, sec-
tion S2.
is responsible for the aromatic carbons attached with the triazine ring
and aliphatic carbon atom adjacent to ‘N’ atom of secondary amine
linkage [39]. Broad peak at 128.58 ppm is an indication the rest of the
carbon atoms come from aromatic pyrene moiety. The aliphatic carbon
atoms between the aminal linkages of TrzPyPOP material give up-field
signal in 56.07 ppm.
5

S.K. Das et al.
Molecular Catalysis 497 (2020) 111198
Fig. 7. Probable mechanistic pathway for the Biginelli condensation catalyzed by N-rich POP TrzPyPOP.
3.6. Heterogeneous organocatalysis over TrzPyPOP
urea) and we got desired product ethyl-6-methyl-2-thioxo-4-(p-tolyl)-
1,2,3,4-tetrahydropyrimidine-5-carboxylate in 73 % yield. This prod-
uct has been identified by 1H NMR spectroscopy. (ESI, Figure S8).
3.6.1. Optimization of catalytic reactions
To optimize the catalytic activity of TrzPyPOP, we have started our
catalytic reaction with 4-methylbenzaldehyde (1a), urea (2) and ethyl
acetoacetate (3) as model reactants to synthesize ethyl 6-methyl-2-oxo-
4-(p-tolyl)-1,2,3,4-tetrahydropyrimidine-5-carboxylate in various sol-
vents and catalyst-solvent combinations. We have also varied the reac-
tion temperature to obtain optimum yield of DHPM. We have observed
that at 65 ◦C the reactants give 98 % yield of the corresponding DHPM in
tetrahydrofuran (THF) medium within 1.5 h. Detailed optimization re-
sults are summarized in Table1.
3.6.2. Recyclability and possible mechanism
Recyclability of the heterogeneous catalyst is a very essential
parameter for its sustainable operation. We have carried out the recy-
cling experiment by using 4-methylbenzaldehyde as the aldehyde pre-
cursor and in Fig. 6 we have plotted the product yields in six consecutive
cycles. As seen from this plot that the product yields have only decreased
from 98 % to 96 %. This result suggested high recycling efficiency of the
TrzPyPOP organocatalyst. A plausible mechanism for this MCR over
TrzPyPOP is shown in Fig. 7, where we have proposed that the acidic
hydrogen from ethyl acetoacetate get deprotonated by our N-rich base
catalyst (TrzPyPOP) under the reaction conditions [45]. This is followed
by the attack of the nucleophile generated to the electrophilic carbonyl
carbon of the aldehyde to yield the intermediate I. These intermediate
moieties I reacts with one equivalent of urea and give Schiff base adduct
II with the release of one equivalent of water. Finally through the
intramolecular cyclization of adduct II produces involving hydride
transfer to form the desired DHPM derivatives [46].
Substrate scope for the synthesis of 3, 4-dihydropyrimidinones over
TrzPyPOP
After optimization of the reaction conditions, a mixture of 1.0 mmol
of aldehyde, 1.1 mmol of ethyl acetoacetate and 10.0 mg of TrzPyPOP
was taken in THF and heated for half an hour, then urea (1.3 mmol) was
added and refluxed for 2 h at 65℃. The reaction mixture was cooled and
poured into ice cold water with stirring, then crude product was filtered
followed by washed with cold water, dried and purified. We have varied
carried out this MCR with different aromatic aldehyde of tolyl, bromo-
phenyl, chlorophenyl, nitrophenyl, ciyanophenyl, furyl and pyrenes.
Results are summarized in Table 2. As seen from this table that apart
from electron withdrawing nitro and cyano groups the DHPM yields
were very high for all the substrates. Turnover numbers have been
calculated for different DHPM derivatives, and the values are ranging
from 143 to 183. Detailed calculation procedure and values are shown in
ESI, Section S3 and Table S1. This result suggested very high catalytic
activity of TrzPyPOP for the synthesis of DHPMs for a wide range of
activated aromatic aldehydes. Further, we have performed the same
catalytic reaction using 4-methyl benzaldehyde and thiourea (instead of
4. Conclusions
Our experimental observations suggested that a novel hierarchically
porous organic polymer TrzPyPOP bearing pyrene and triazine moieties
can be synthesized through a convenient polycondensation reaction
between four armed amine and pyrene aldehyde. TrzPyPOP showed
hierarchical porous polymeric structure with BET surface area 1016 m2
gꢀ 1. By virtue of its high specific surface area, hierarchical porosity in
nanoscale, and mild surface basicity due to presence of aminal linkages,
6

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Molecular Catalysis 497 (2020) 111198
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Declaration of Competing Interest
There are no conflicts to declare.
Acknowledgements
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SKD wishes to thank UGC New Delhi and IACS for his senior research
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