Flexible Zn-MOF Exhibiting Selective CO2 Adsorption and Efficient Lewis Acidic Catalytic Activity

Article abstract of DOI:10.1021/acs.cgd.8b01462

A two-dimensional, tetragonal porous metal organic framework {[Zn₂(TBIB)₂(HTCPB)₂]·9DMF·19H₂O}_n (1) has been synthesized under hydrothermal conditions by employing 1,3,5-tri(1H-benzo[d]imidazol-1-yl)b

Full text of DOI:10.1021/acs.cgd.8b01462

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Article
Flexible Zn-MOF Exhibiting Selective CO2 Adsorption
and Efficient Lewis Acidic Catalytic Activity
Rashmi A. Agarwal, Anoop K. Gupta, and Dinesh De
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b01462 • Publication Date (Web): 12 Feb 2019
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Flexible Zn-MOF Exhibiting Selective CO2 Adsorption and Efficient Lewis
Acidic Catalytic Activity
Rashmi A. Agarwal,a* Anoop K. Gupta,b Dinesh Deb
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aDepartment of Civil Engineering, Indian Institute of Technology Kanpur, Kanpur 208016,
India
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bDepartment of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208016, India
ABSTRACT: A two dimensional, tetragonal porous metal organic framework
{[Zn2(TBIB)2(HTCPB)2]∙9DMF∙19H2O}n (1) has been synthesized under hydrothermal
conditions by employing 1,3,5-tri(1H-benzo[d]imidazol-1-yl)benzene (TBIB) and 1,3,5-
Tris(4′-carboxyphenyl-)benzene (H3TCPB). But non-covalent supramolecular interactions
between the layers make this framework three dimensional, generating porosity in one
dimension. Flexibility arises due to the presence of two types of large linkers wherein some
functional groups of the ligands are not coordinated with the metal ion. Desolvated polymer
shows moderate CO2 uptake (65 cm3 g1 at 195 K and 1 bar) at low temperature and pressure.
Compound 1 acts as a highly efficient heterogeneous catalyst towards the formation of cyclic
carbonate through cycloaddition of CO2 as well as towards the synthesis of quinoline
derivatives by the Friedländer reaction. Presence of the free -COOH, -C=O groups and
uncoordinated -N atoms on the wall of the pores make this framework an excellent candidate
for the catalytic reactions without activation of the compound.
INTRODUCTION
The field of porous coordination polymers (PCPs) or metal organic frameworks have
attracted a tremendous attention due to their large surface area, tuneable pore sizes and
versatile architectures, lead to a variety of applications such as gas adsorption, separation and
heterogeneous catalysis.1-10 PCPs are often much more dynamic and flexible (3rd generation
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compounds) which is due to the supramolecular non-bonding interactions present within the
framework. Utilization of two large linkers causes flexibility in the framework due to
adjustment of the linkers according to the coordination modes of the metal ion. In the
presence or absence of guest molecules adjustments take place within the framework
according to the availability of the space due to the presence of different types of non-
bonding interactions shown by shrinking or elongation of the framework.11 These structures
can be transformed depending upon the external stimuli and thus having unique properties.
Specifically ligand molecules undergo rotation due to the presence of large space.12
Exertion of abundantly available CO2 towards the synthesis of fine chemicals is a recently
very sustainable approach.13,14 Global warming due to the high release of CO2 from
anthropogenic activities have attracted huge global drive towards the carbon dioxide capture
and sequestration.15
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Most of the previous studies have shown that formation of cyclic carbonate and other
catalytic reactions occur due to presence of open metal sites.16 MOF functionalized with
nitrogen bases and other polar functional groups (–NH2, OH, −NO2, −COOH, −SO3H, etc.)
enhances the selectivity towards CO2.17
In the MOFs, vacant metal sites are generated by removing the metal bound solvent
molecules. This process needs too much time, because first solvent exchange experiment is
performed to replace the lattice as well as metal bound solvent molecules by low boiling
solvent then finally, solvent exchanged sample is applied towards heating under high
vacuum. During these processes, different MOFs can lose their crystallinity as well as, the
chances for collapsing the frameworks are increases.18 But recent studies have shown that
host guest interactions are very important for high gas uptake as well for excellent catalytic
activity.19
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Herein the synthesized MOF have a number of free functional groups (-COOH, C=O and -N)
which efficiently catalyse the reaction without activating the compound. Effective means for
addressing environmental issues, the development of sustainable chemical sciences involves
new technologies and efficient processes. Weaker non-covalent interactions such as hydrogen
bonds, van der Waals forces and π-π contacts may also strongly influence the formation of
coordination polymers.20
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EXPERIMENTAL SECTION
Materials and Physical Measurements. All the chemicals were reagent grade from Aldrich
and used without further purification. Solvents were purchased from S. D. Fine Chemicals,
India. Characteristic spectroscopic techniques and X-ray structural studies have been
provided in the Supporting Information.
Synthesis of 1,3,5-tri(1H-benzo[d]imidazol-1-yl)benzene (TBIB). TBIB was synthesized
according to the previous study.21
Synthesis of 1,3,5-Tris(4′-carboxyphenyl-)benzene (H3BTB). H3BTB was prepared
according to the published procedure.22
Synthesis of {[Zn2(TBIB)2(HBTB)2]∙9DMF∙19H2O}n. A mixture of Zn(NO3)2.6H2O (60
mg, 0.188 mmol), TBIB (20 mg, 0.047 mmol), H3BTB (20.6 mg, 0.047 mmol) and
DMF:H2O (3 ml, 3:1 v/v) was placed in a Teflon-lined stainless steel autoclave. The
autoclave was heated up to 80 °C under autogenous pressure for 48 h and then allowed to
cool to room temperature at a rate of 10 °C/h. Colourless crystals of the complex were
obtained by filtration and washed with DMF followed by acetone. Yield = 80%. Anal. Calcd.
for C135H170N21O40Zn2 = C, 56.71; H, 5.95; N, 10.29%. Found: C, 56.45; H, 5.7; N, 10.40%.
FT-IR (KBr pellets, cm-1): 3362 (broad), 1711 (m), 1672 (s), 1607 (s), 1551 (s), 1501(s),
1382 (s), 1231 (s), 773 (s) (Figure S1).
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General Procedure for the Cycloaddition of CO2 to Epoxides. As-synthesized compound
(heterogeneous catalyst) was used directly without activation. Reactions were carried out in a
Schlenk tube with stirring at room temperature depending on the substrate, and CO2
(99.999%) bubbling. Epoxide (20 mmol), catalyst 1 (10 wt%), and co-catalyst TBAB (1
mmol) were added. Upon completion the reaction, the reaction mixture and catalyst were
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1
separated by filtration to obtain a crude compound. This crude mixture was given for H
NMR (in CDCl3) to calculate the yield.
General Procedure for the Friedlander reaction
The reaction mixture containing 2-aminoaryl ketones (0.5 mmol), ethyl acetoacetate (1
mmol), and catalyst 1 (5 wt%) was placed in a RB at 85 ºC for 24 h with continuous stirring.
As confirmed by the TLC, after completion of the reaction the reaction mixture is filtered to
get the crude product. This crude product was purified by column chromatography by
utilizing ethyl acetate/hexane (1/10 : v/v) as eluent to get the pure product.
RESULTS AND DISCUSSION
A flexible, layered PCP has been synthesized by the hydrothermal reaction of
Zn(NO3)2.6H2O with TBIB and H3TCPB in DMF and water at 80 °C for 48 h. 3D structure
was generated via non-covalent supramolecular interactions between the layers creating
porous structure showing 1D channels. Single crystal X-ray study reveals that 1 crystallizes
in the monoclinic space group P21/c and asymmetric unit consisting of two Zn(II) ions, two
TBIB, two HTPCB2 ligands along with 9 DMF and 19 H2O solvent molecules in the lattice.
Zn1 has tetrahedral geometry MN2O2 with coordination from two N atoms of benzimidazole
of two different TBIB and two O atoms of two carboxylates of two HTCPB2 ligands (Figure
1a). Metal ions in a 1D chain are connected by TBIB ligand and layered structure is created
by metal ion coordination with HTPCB2 (Figure 1b). One benzimidazole -N atom of each
TBIB ligand and two C=O group along with one -COOH of each HTPCB2 are free. Layers
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are stacked in ABAB... fashion (Figure 1c) and are connected via non-covalent hydrogen and
pi-pi bonding interactions as shown in Figure 1d leading to a three dimensional porous
structure with 1D channels (including Vander Wal radii 13.5  8.3 Å2) along the
crystallographic a axis. Solvent accessible void volume was calculated to be 38% after
squeezing solvent molecules. Topological analysis was carried out by using TOPOS software
showing that Zn(II) metal ion has 4 connected node with point symbol {44.62} and
topological type sql/Shubnikov tetragonal plane net (topos&RCSR.ttd) (Figure S2).
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(a)
(c)
(b)
(d)
Figure 1. (a) Coordination environment around Zn(II) metal center, (b) layered structure of
the polymer, (c) 3D structure and 1D pore formation through supramolecular interactions
between layers, (d) interactions between TBIB of two different layers.
Thermal stability of the compound 1 has been checked by thermogravimetric analysis. TGA
curve (Figure S3) shows weight loss of ~36.3% (calculated ~35%) corresponding to loss of
all solvent molecules (water and DMF) from the cavities of the polymer between the
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temperatures 80290 C. Compound is stable up to 350 C after that decomposition takes
place.
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VTPXRD measurements (Figure S4) show that compound breathe at room temperature
because in the PXRD of as-synthesized compound, diffraction peaks are slightly shifted
towards higher 2 value when compared with the simulated pattern. It shows that framework
is slightly shrinked as temperature is increased.
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Gas adsorption studies
Before gas adsorption measurements as-synthesized compound was first activated by
immersing it in the DCM solvent to replace all the solvent molecules with the low boiling
solvent molecules. After that it was heated up to 70 C at high vacuum to make it free from
all DCM molecules to generate 1a (de-solvated).
To check the porosity of de-solvated compound 1a gas adsorption studies have been done at
low pressure (1 bar) and low temperature for H2 and N2 (77 K) and for CO2 (195 K).
Compound exhibits selectivity towards CO2 gas showing type 1 adsorption isotherm
revealing its microporous nature with saturation adsorption up to 65 cm3g1 with slight
hysteresis at low temperature and pressure as shown in Figure 2. The Brunauer-Emmett-
Teller (BET) surface area, calculated from CO2 sorption at 195 K is 138 m2 g−1. As PXRD
measurements (Figure S4) reveal that 1 is a highly flexible coordination polymer because
even at room temperature, its peaks get shifted slightly towards higher 2 angle but at
increasing temperatures peaks shifting is more towards higher 2 angle. It leads to the higher
shrinkage in the polymer with respect to the increase in temperature. That is why at room
temperature CO2 adsorption is only 11.4 cm3g1 due to contraction in the framework (Figure
S6). Pore size distribution analysis shows (Figure S5) that pores have an average diameter of
1.8 nm with pore volume approximately ~0.10 cm3g1 due to shrinkage. H2 gas is not
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adsorbed due to its non-polar nature while framework has polarity due to the presence of free
functional groups in both the linkers. N2 sorption does not takes place at the surface of the
flexible polymer due to the presence of 1D pores and large kinetic diameter of N2. While CO2
is a polar molecule and it needs polar environment to get inside the structure due to having
higher quadrupole moment. Presence of free -COOH, C=O groups and uncoordinated
benzimidazole N atoms provide polarity to the wall of the pore, facilitating CO2 gas
adsorption. But in this MOF there are free carboxylic acid groups which are present at the
pore surface and CO2 groups are also acidic in nature so gas adsorption is decreased due to
repulsive nature of the same charges.
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Previous literature studies show that mesoporous silica materials have larger sorption
properties for CO2 over a wide range of pressures at different temperatures reported by Sayari
et al.23 But modified mesoporous silica structures with triamine and polyethylenimine (PEI)
functionalization with different pore lengths show fast CO2 adsorption properties.24,25 CO2
adsorption in Na-A zeolite at 273333 K temperature and desorption at higher temperature
(573673 K) has been reported by Zukal et. al. where small portion of CO2 retain in the form
of surface carbonates.26 Zeolitic structures cannot be functionalized/tuned according to the
requirement. High CO2 uptake (5.28 mmol/g) have been observed in Mg-MOF-74 (CPO-27-
Mg) at 40 C and at low pressure under dry conditions due to the strong interaction of open
metal sites (OMSs) with CO2 molecules. But presence of moisture affects the gas uptake
because then water molecules are coordinated with the OMSs.27-29 Cu-BTC also have
unsaturated Cu metal sites which helps in CO2 adsorption accurately calculated by employing
a combined DFT-ab initio computational scheme.30 Synthesis of functionalized MOFs by
introducing a high density of free amine groups in Mg-MOF-74 showed exceptionally high
uptake of CO2 due to strong affinity towards CO2 even in the presence of high humidity.31
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Monodentate hydroxide also have strong reversible interaction with CO2 via the formation
and decomposition of bicarbonate.32 But in present case due to flexible nature of the
framework even at room temperature, CO2 adsorption decreases at higher temperature
because of contraction in the framework. Recently selective uptake of CO2 has been done by
a number of different groups wherein MOF featuring free N and carboxylate O atoms.33-35
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Figure 2. Gas adsorption isotherm of 1: CO2 at 195 K temperature, H2 and N2 at 77 K
temperature and 1 atm pressure.
This polymer shows different catalytic reactions without activating the framework due to the
presence of free acidic groups (-COOH) inside the cavities which initiate the catalysis. On the
other hand free C=O and N atoms of the benzimidazole groups are also present in the
structure leading to the enhancement of the rate of the reaction. A great effect of the
flexibility or breathing effect of the 1 even at room temperature which arises due to the
presence of two large linkers having a number of free groups (non-coordinated) which can be
adjusted according to the coordination mode of the metal ion. There are a number of metal
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organic frameworks which undergo these type of reactions having Lewis acidic sites along
with the basic sites in the framework performing synergistic catalysis.36-53 Unsaturated metal
sites can be generated after removal of coordinated solvent molecules during activation at
high temperature. It takes a long time to prepare catalysts for the reaction. Recent MOFs
containing open metal sites along with MNPs (metal nanoparticles) embedded in the cavities
of the polymer have been synthesized for catalytic reactions.54-61 In this case first MOF will
be synthesized after that NPs encapsulation occurs. It is not only a costly process but also a
time consuming process because activation is required after each cycle of the catalysis. In the
case of zeolites, size of the product molecule is limited by the size of the pore apertures as
well as these zeolitic structures are deactivated by the small amount of coke which can block
the access of the reactants towards the active sites.62, 63
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While molecular sieves are not only very expensive but also should not be exposed to water
due to giving off heat. Its dust can also irritate sensitive tissues as well as after following a
shutdown, temperatures in a molecular sieve bed can stay hot for weeks so bed should be
cooled properly to switch it for adsorption.
Cycloaddition of CO2 to Epoxides
The structural observation of 1, shows several important features like the presence of free
protonated carboxylic acid groups, carbonyl groups and the presence of Lewis basic sites
originating from the rich N-containing TBIB ligand. Because of the permanent porosity of the
framework with open channels it captures CO2 selectively which enable substrate diffusion.
Due to these prominent features in 1, heterogeneous catalytic activity has been evaluated
through the cycloaddition of CO2 to various epoxides to yield value added product, cyclic
organic carbonates. Cyclic carbonates have gained much attention due to their broad
spectrum of applications such as polar aprotic solvents, electrolytes for lithium-ion batteries,
pharmaceutical/fine chemical intermediates, and in many biomedical applications.21,22 Cyclic
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carbonates are also used as constituents of oils and paints and as monomers for the synthesis
of polycarbonates23 and polyurethanes22 since they can undergo ring-opening polymerization.
The cycloaddition of styrene oxide with CO2 into phenyl ethylene carbonate was selected as a
model reaction to explore the catalytic behaviour of the MOF. The cycloaddition reaction has
been carried out at room temperature, 1 atm pressure of CO2 under solvent-free conditions
using catalyst (1, 30 mg) with tetra-n-tertbutylammonium bromide (TBAB, 60 mg) as co-
catalyst for 24 h. The results are summarized in Table 1. The cycloaddition reaction could not
occur remarkably in the absence of either of the MOF catalyst or co-catalyst (entry 5 and 6).
If H3TCPB is taken as a homogeneous catalyst along with TBAB as a co-catalyst then 20%
yield of the cyclic carbonate is obtained. It was found that the styrene oxide could be
converted into the corresponding cyclic carbonate with excellent yield (>99 %) when both
catalyst and TBAB were used combinedly (entry 1).
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The activity of the catalyst was then evaluated in more depth. Such, high catalytic activity
was also observed for the cycloaddition of CO2 with various epoxide substrates to produce
corresponding cyclic organic carbonates under the same reaction conditions (Table 1).
Specifically, epichlorohydrin and 1,2-butylene oxide reacts efficiently with the yields of
>99% (Table 1, entry 2) and >99% (Table 1, entry 3), respectively. Phenyl glycidyl ether was
little bit less reactive due to the steric effect of the substrates, while a yield of 82% was still
achieved (Table 1, entry 4).
To judge the heterogeneous nature of the MOF catalyst, filtration test have been performed
with the model reaction using optimized reaction conditions to ensure that the catalytic
activities do not originate from leaching of any metal ions from the MOF structure. After 24
h, the MOF catalyst was removed by filtration and the reaction was allowed to continue. As
expected, there was no significant increase in the formation of styrene carbonate detected
after the MOF catalyst was removed. Indeed, this result primarily provides strong support for
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the fact that the catalytic reaction was heterogeneous in nature. Recycling studies were then
undertaken using the optimized conditions where the reaction mixture was filtered to collect
the catalyst and washed several times with chloroform and then by acetone. After drying at
room temperature the catalyst was regenerated and further used it for subsequent runs and
checked its recyclability. In the model reaction, MOF catalyst was reused up to five
successive times with the yield of styrene carbonate slightly decreasing in the first run to 82%
after that yield is constant till fifth run (Figure S7). PXRD analysis was performed on the
recycled MOF catalyst, in which structural preservation was proven (Figures S8).
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Table 1. Coupling of various epoxides with CO2 at room temperature and at atmospheric
pressure using 1a
O
1
, TBAB
RT
O
O
CO2
O
R
R
Entry
Epoxide
Catalyst
1
Co-catalyst Time (h) Cyclic Carbonate Yield (%)b
O
1
TBAB
24
>99
O
O
O
O
2
3
4
1
1
1
TBAB
TBAB
TBAB
24
24
24
>99
>99
82
O
O
Cl
O
Cl
O
O
O
O
O
O
O
O
O
O
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O
O
5
6
1
None
24
24
7
O
O
O
O
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None
TBAB
12
O
O
O
7
H3TCPB
TBAB
24
20
O
O
O
aReactions were carried out in a 10 mL two-necked round bottom flask at room temperature and CO2
bubbling. Epoxide (20 mmol, 1 equiv), 1 (0.0025 equiv), TBAB (0.05 equiv). No solvent was added.
bYields were calculated using 1H NMR analysis by integration of epoxide versus cyclic carbonate peaks
(see the Supporting Information Figures S9-S12).
As heterogeneous catalyst 1 has free COOH, C=O groups (one COOH group and two C=O
groups free for one H3TCPB linker) along with non-coordinated benzimidazole N atoms
which are decorated at the surface of the pores so there is no need to activate this catalyst due
to the presence of protonated carboxylic acid groups. Recently cyclic carbonate formation in
MOF was demonstrated by Li et al and Wang et al due to the presence of Lewis acidic metal
sites and uncoordinated carboxylate O atoms.34, 35 Previous literature propose the mechanism
that free carboxylic acid groups help in catalyzing the reaction efficiently.64,65 But framework
was activated at higher temperature to remove lattice solvent molecules as well as
coordinated solvent molecules. But in this case as-synthesized compound was used directly.
COOH group of the catalyst initiates formation of non-covalent interaction with the epoxide
substrate followed by ring opening through simultaneous nucleophilic attack of bromide ion
from co-catalyst TBAB. After that CO2 reacts with the O atom of the epoxide in a
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electrophilic manner forming a carbonate intermediate. Finally cyclic carbonate is formed
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Scheme 1. Proposed mechanism for the synthesis of cyclic carbonate by the catalyst 1
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Friedländer reaction : synthesis of quinoline derivatives. As mentioned earlier that high
thermal stability, large pore volume as well as free carboxylic acid (-COOH) groups along
with the free C=O and -N, groups in the frameworks makes it a good Lewis acid
heterogeneous catalyst. To check its Lewis acid nature, Lewis acid catalysed reaction has
been performed. Here, synthesis of quinoline derivatives via the Friedländer reaction, has
been demonstrated by employing catalyst 1 (Scheme 2). Quinoline is an important and
ubiquitous backbone in innumerable biological and pharmaceutical molecules.66 Quinoline
derivatives exhibit antibacterial, antimalarial, anti inflammatory, anti-asthmatic, anti-
hypertensive and tyrosine kinase PDGF-RTK inhibiting properties.67, 68 Moreover, quinolines
act as synthons for the synthesis of nanostructures and polymeric materials that convoy the
optoelectronic or NLO properties with excellent mechanical strengths.69, 70 Since, quinolines
are important in industry, pharmacology and synthetic points of view, numerous versatile
synthetic procedures have been reported for their synthesis.71-74 Among those, the Friedländer
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hetero-annulation is one of the most simple and a direct route for the quinoline synthesis. In
Friedländer hetero-annulation reaction, different poly substituted quinoline derivatives have
been synthesized through reaction between an aromatic 2-aminoaldehyde or ketone and an
active methylene containing carbonyl compounds.75, 76 However, there has been tremendous
development towards the synthesis of quinoline derivatives using acid catalyst, by avoiding
the use of the traditionally basic conditions.77-79 Apart from conventional protic acids, many
other catalysts have also been used for the Friedländer synthesis.80, 81 MOFs having open
metal sites which act as Lewis-acids, have already shown catalytic activity for the Friedländer
reaction.82 Perez-Mayoral et al. investigated CuBTC catalyzed Friedländer condensation by a
combination of different experimental techniques as well as by DFT based modelling and
found that CuBTC showed improved catalytic activity when compared with other MOFs e.g.
in BEA and (Al)SBA-15 containing high concentraion of Lewis acid sites.83, 84
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As already mentioned that the activation process to generate active sites or vacant metal sites
is a prolonged process and the chances for the degradation of frameworks are increases.
In the present study, a carboxylate based Zn-MOF (1) has been designed that have free
carboxylic acid groups at the pore surface of the framework. Catalytic behaviour of 1 showed
its huge potential as a promising acidic heterogeneous catalyst for the synthesis of quinoline
derivatives (Scheme 3).
Scheme 2. Synthesis of quinoline derivatives via the Friedländer reaction between
aromatic 2-aminoketone and active methylene compounds
R2
R2
N
O
O
O
Catalyst (5 wt %)
85 oC, 24 h
R1
R1
O
Y
+
Y
X
NH2
X
Active methylene
compound
Aromatic 2-
aminoketone
Quinoline
derivatives
At first, the model reaction between 2-aminobenzophenone (0.5 mmol) and ethyl acetoacetate
(1 mmol) have been done in the presence of 1 (5 wt%) at 85 ºC for 24 h which gave the
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desired compound in 97% isolated yield (Table 1, Entry 1). A possible mechanism for the
synthesis of quinolines using this catalyst is shown in Scheme 3, where the free carboxylic
acid group catalyses the reaction in the same way as shown by the vacant metal sites in
CuBTC MOF due to the hard Lewis acid character.83 It is shown in the Table 1 that the
various aromatic 2-aminoketone (0.5 mmol) have been used with ethyl acetoacetate (1 mmol)
in presence of catalyst 1 (5 wt%) under solvent-free conditions at 85 ºC for 24 h, to give the
respective quinoline derivatives in moderate to excellent yields. The 98% and 94% yields was
observed with 4-chloro and 4-nitro substituted 2-aminobenzophenone respectively (Table 1,
entries 2 and 3). Also, the catalytic activity of 1 was tested with 2-aminoacetophenone and
ethyl acetoacetate (1 mmol) that afforded product with 95% Yield (Table 1, entry 4). The
heterogeneous catalytic activity of 1 showed superiority over both the homogeneous zinc salt
i.e. zinc acetate as well as the H3TCPB which gave the desired product in low yields that is
26% and 21%, respectively (Table 1, entry 5 and 6). Also, the non-catalyst experiment was
performed, in which 2-aminobenzophenone and ethyl acetoacetate was reacted in absence of
any catalyst that showed very low yield (9%) (Table 2, entry 7), confirming the catalytic
activity of 1.
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Table 2. Friedländer reaction between different aromatic 2-aminoketone and different
active methylene compounds[A]
Entry
Catalyst
Aromatic 2-
aminoketone
Active methylene
compound
Yield
(%)[B]
R1
R2
O
O
O
O
O
O
O
O
O
O
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5
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H
Ph
Ph
Ph
Me
Ph
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95
26
O
O
O
O
O
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Cl
1
NO2
H
1
Zn(OAc)2·(H2O)2
H
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O
O
O
O
6
H3TCPB
H
H
Ph
Ph
21
9
O
O
7
No Catalyst
7
[A]
8
9
2-aminoaryl ketones (0.5 mmol), ethyl acetoacetate (1 mmol), and catalyst 1 (5 wt %),
sealed tube 85 ºC for 24 h. [B] Yield of the isolated product after flash chromatography.
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As described above, the heterogeneous nature of 1 was confirmed by the hot filtration
experiment, as well as the framework is reusable and the framework integrity was maintained
during the recyclability experiments.
These data show that 1 is a proficient Lewis-acid catalyst in Friedländer reactions with varied
1
13
substrates. In each case, the characterization of desired product was achieved by the H, C
NMR spectroscopy (Figures S13–S20).
Scheme 3. Proposed Mechanism for the synthesis of quinoline derivatives through
Friedländer reaction
CONCLUSIONS
Hydrothermally synthesized flexible Zn-based 2D porous coordination polymer shows
selective CO2 gas adsorption. It breathes at room temperature due to the presence of two large
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size linkers, but at higher temperature flexibility is increased. It acts as an excellent
heterogeneous catalyst towards the chemical fixation of CO2 to cyclic carbonates as well as
towards the synthesis of quinoline derivatives through Friedländer reaction. Catalytic activity
is due to the presence of free protonated COOH groups in the polymer which are decorated at
the surface of the pores. There are free C=O groups along with non-coordinated
benzimidazole N atoms which assist the reactivity of the catalyst.
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ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the ACS Publications website at
DOI ;
with Physical measurements, X-ray structural studies, IR, TGA, PXRD and NMR spectra.
X-ray crystallographic data of 1 (CCDC number -1819056).
AUTHOR INFORMATION
Corresponding Author
E-mail: rashmi.a.agarwal@gmail.com
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
The authors would like to thank IIT Kanpur for extending facilities to undertake this study.
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For Table of Contents Use Only
Flexible Zn-MOF Exhibiting Selective CO2 Adsorption and Efficient Lewis
Acidic Catalytic Activity
Rashmi A. Agarwal,a* Anoop K. Gupta,b Dinesh Deb
O
O
O
O
R
R
R2
O
X
R2
O
O
R1
R1
O
Y
+
X
Y
NH2
N
Zn(II) based flexible porous coordination polymer shows excellent heterogeneous catalytic
activity due to the presence of Lewis acidic groups in the large linkers. Transformation of
CO2 in to cyclic carbonates as well as synthesis of quinoline derivatives through Friedländer
reaction could be done successfully by using this polymer.
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