New Bifunctional Metal-Organic Frameworks and Their Utilization in One-Pot Tandem Catalytic Reactions

Article abstract of DOI:10.1021/acs.cgd.8b01327

Two new metal-organic framework (MOF) compounds were synthesized by a room temperature slow diffusion reaction. The compounds, [Cd₃(C₈H₃SO₇)₂(C₁₀H₈N₄)₃(C₃H₇NO)₂](C₃H₇NO)₂·(CH₃OH)₄, I, and [Cd₃(C₈H₃SO₇)₂(C₁₂H₁₀N₄)₃(C₃H₇NO)₂](C₁₂H₁₀N₄)·(C₃H₇NO)₂, II, have comparable structures formed by Cd-sulfoisopthalate layers cross-linked by bipyridyl linkers forming three-dimensional structures. The compounds have both Lewis acidic (Cd metal centers) as well as basic (azine, free pyridine, and uncoordinated sulfo oxygens) sites, and they exhibited good catalytic activity for one-pot tandem deacetalization-Knoevenagel condensation reactions. The compounds exhibit catalytic activity both in the presence of a solvent as well as in solvent-free conditions. Compound I also exhibits good proton conductivity at room temperature.

Full text of DOI:10.1021/acs.cgd.8b01327

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Article
New Bi-Functional MOFs and Their Utilization
in One Pot Tandem Catalytic Reactions
Subhradeep Mistry, Anupam Sarkar, and Srinivasan Natarajan
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b01327 • Publication Date (Web): 18 Dec 2018
Downloaded from http://pubs.acs.org on December 19, 2018
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New Bi-Functional MOFs and Their Utilization in One Pot Tandem
Catalytic Reactions
Subhradeep Mistry, Anupam Sarkar, and Srinivasan Natarajan*
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Framework Solids Laboratory, Solid State and Structural Chemistry Unit, Indian Institute of
Science, Bangalore 560012 (India)
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For Correspondence: E-mail: snatarajan@iisc.ac.in
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Abstract:
Two new metal-organic framework (MOF) compounds were synthesized by room
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temperature
slow
diffusion
reaction.
The
compounds,
and
[
[
Cd (C H SO ) (C H N ) (C H NO) ](C H NO) .(CH OH) ,
I,
have
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Cd (C H SO ) (C H N ) (C H NO) ](C H N ).(C H NO) ,
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comparable
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structures formed by Cd- sulfoisopthalate layers cross-linked by bi-pyridyl linkers forming
three-dimensional structures. The compounds have both Lewis acidic (Cd metal centers) as
well as basic (azine, free pyridine and uncoordinated sulfo oxygens) sites, they exhibited
good catalytic activity for the one pot tandem deacetalization−Knoevenagel condensation
reactions. The compounds exhibit catalytic activity both in the presence of a solvent as well
as in solvent-free conditions. Compound I also exhibits good proton conductivity at room
temperature.
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Introduction:
Metal organic frameworks (MOF) or coordination polymers (CP) have occupied a
central stage during the last two decades.1-4 The aesthetic structures, large functional pores,
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which are often flexible and tuneable in nature,5-8 makes this class of compounds attractive
and find applications in storage,9-12 separation,13-16 catalysis,17-22 drug delivery,23-25
sensing26,27 etc.
MOFs with their extra-large pore openings and channels could be candidates for
exploring heterogeneous catalytic studies and can provide good activity as well as
selectivity.28 Thus, there is considerable interest to investigate MOFs as a heterogeneous
catalyst in many catalytic reactions. One of the important developments over the years in
organic reactions/transformations is to generate processes that are environmentally benign
and with good atom economy. One of such process is one-pot tandem reactions. In tandem
or cascade reaction, two or more reactions proceed successively within the same reaction pot,
which reduces energy consumption, waste of chemicals and the reaction time.29
One-pot reaction types include, but not limited to, cascade (domino) process,30,31
32
tandem catalysis (catalysis performed sequentially), multi-functional catalysts having more
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than one active site, and reactions involving two distinct catalysts. The one-pot catalytic
reactions present certain difficulties (i) controlling and optimizing selectivity and (ii)
competing interactions (usually detrimental) between multiple catalytic sites and catalysts,
which presents opportunities to explore newer catalysts.35 The attractive side of these one-
pot reactions, on the other hand, is the possibility of isolating energetically unfavourable
products. We have been interested in these one-pot tandem reactions as the MOFs provide
suitable platform to investigate multifunctional catalysts that would help in different types of
transformations under similar reaction conditions.
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In the present study, we have employed two organic ligands, sodium salt of 5-
sulfoisopthalic acid (Na-C H SO - NaSIPA) and two pyridine based organic linkers 4,4’-
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azopyridine (C H N - ABPY) and 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene (C H N -
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BPDB) along with the cadmium salts to prepare two new three-dimensional (3D) MOFs
[
Cd (C H SO ) (C H N ) (C H NO) ](C H NO) .(CH OH)
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The hexa-coordinated Cd metal centers have been known to act as Lewis acidic
centers and exploited for several applications that include heterogeneous catalysis.36,37 In
addition, the presence of the sulfo group (uncoordinated sulfo oxygens with lone pairs) as
well as azine and uncoordinated pyridine sites can potentially act as Lewis base centers.38-41
The possibility of combining the Lewis acidic and basic properties in a single MOFs provides
an attractive option for exploring catalytic reactions. One reaction that would combine the
Lewis acidity and basicity would be the deacetalization-Knoevenagel (DK) reaction. There
have been studies in the literature exploring such tandem catalytic reaction.42-45 In the
present study, the isolated compounds possess some of the desirable properties to carry out
the tandem catalysis that would involve both the Lewis acidic as well as basic reaction
centers. We have explored such a reaction as part of the present investigations and found that
the present compounds to be active as good heterogeneous catalysts. In addition, we have
also discussed the proton conductivity behaviour of compound I. In this paper, we present
the synthesis, structure, tandem catalytic behaviour and proton conductivity studies on the
two compounds, I and II.
Experimental section:
Synthesis of compound I and II:
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All the chemicals were obtained from commercially available sources. The ligand
BPDB was synthesized following the established procedure.46 All the syntheses of the MOFs
were carried out at room temperature employing slow diffusion of the reactants separated by
immiscible layers. Typically, 0.04 mmol of NaSIPA salt (10.7 mg) and 0.04 mmol of
bipyridine linkers [ABPY for I (7.4 mg) and BPDB for II (8.4 mg)] were dissolved in 2 ml of
methanol, were transferred to a 5 ml culture tube (capped) and carefully layered over a 2 ml
of dimethylformamide (DMF) solution containing 0.04 mmol of Cd(NO ) ,4H O (12.3 mg).
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After 2-3 days reddish orange (I) and yellow (II) coloured crystals starts to form on the wall
of the tubes. The reaction was allowed to continue for one week and then the crystals were
separated from the mother liquor and washed with 1:1 mixture of DMF and methanol
solution under vacuum filtration and dried at ambient conditions. Yields: 89 % (I) and 82 %
(II); based on the metal salts (Table S1).
Initial characterization:
All the compounds were characterized by elemental analysis (C, H, N, S; Thermo
Finnigan EA Flash 1112), powder X-ray diffraction (PXRD; PANalytical, Empyrean), IR
Perking-Elmer Spectrum 1000), thermogravimetric analysis (TGA; Mettler-Toledo) and
(
UV/Vis absorption studies (Perking-Elmer, Lambda-35). Elemental analysis results are
presented in the Table S2. The PXRDs of the samples were recorded at room temperature
(
CuK ) and the observed PXRD patterns were consistent with the simulated PXRD patterns
α
generated from the structures determined by the single-crystal XRD studies (ESI Figure S1).
Room temperature IR spectroscopic studies were carried out in the mid-IR region
using KBr pellets, which exhibit characteristic bands (ESI Figure S2). A sharp band at ~
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735 cm-1 could be assigned to the presence of –COO group of SIPA ligand in the
-1
-1
compounds, I and II. The bands at 1230 cm (I) and 1160 cm (II), could be due to the
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asymmetric and symmetric stretching band of S=O group of the ligand. The strong sharp
band at ~ 1040 cm could be due to the S-O stretching. The strong band near ~ 1610 cm-1
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in II could be assigned to the presence of azine group (-C=N-) of the BPDB ligand.48,49
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sharp band at ~1646 cm (I) and 1640 cm (II)for C=O stretch of DMF. And a band at
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UV-vis spectra of compound I and II were recorded at room temperature exhibit
broad absorption bands in the visible region (ESI Figure S3). For I, two maximas centered at
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~
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330 nm was noted. The absorption bands arise due to the intra-ligand charge transfer (n →
π* or π → π*). The observed UV-vis spectra for I and II are similar to those observed
before.51
The solid-state photoluminescence (PL) studies of compounds I and II were carried
out at room temperature on the powdered sample (ESI Figure S4). The compounds I and II
were excited using a wavelength of 350 nm and 380 nm, respectively. An emission band at ~
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95 nm with two shoulders at ca. 490 nm and 530 nm was observed for compound I (ESI
Figure S4a). For II, a maxima at ~ 450 nm with two shoulders at ~ 485 nm and 525 nm was
observed (ESI Figure S4b). The observed emissions are due to the intra-ligand emissions.
Similar observations have been made before.51,52
Single-crystal structure determination:
Suitable single crystals of compound I and II were selected and mounted with a fibre
loop. The single-crystal data were collected at 100(2) K on an Oxford Xcalibur (Nova)
diffractometer equipped with an EOS CCD detector. The X-ray was generated by operating
at 50 kV and 0.8 mA by using MoKα (λ = 0.71073 a) radiation. The refinement of the cell
and the data reduction was carried out using CrysAlis RED.53 The structures were solved
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using direct method and refinement was accomplished by employing SHELX-2014 present in
WINGx suit of programmes (version 1.63.04a).54 The hydrogens could be assigned from the
difference Fourier map and for the final refinement the hydrogens were fixed at the
geometrically ideal position and refined using the riding mode. The full-matrix least-squares
refinement against |F | was executed on the WinGx package of programs.55 The final
refinements were carried out including atomic positions of all the atoms, anisotropic thermal
parameters for all the non-hydrogen atoms, and isotropic thermal parameters for all the
hydrogen atoms. All the details of structural parameters and refinement details are listed in
Table 1. Important bond lengths and bond angles are presented in the Table S3 and S4. The
supplementary crystallographic data for this paper can be found in CCDC 1838396-1838397.
The Cambridge Crystallographic Data Centre (CCDC) provides free access to the single
crystal data.
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Catalytic Studies:
To perform the tandem catalytic reactions, an optimization of the catalytic conditions
have been investigated. Thus the deacetalization and Knoevenagel condensation reactions
were carried out independently with the MOFs as catalyst in different solvents such as EtOH,
MeOH, toluene, MeCN, DMA, and DMF. The investigations reveal that catalytic
performance was optimal when DMF was employed as the solvent. Thus we have chosen
DMF as the solvent for the tandem one pot DK reactions. The next step is to perform the
catalytic reactions at different temperatures. We observed that the deacetalization was slow
at lower tempeartures. Our studies indicate that optimum products were observed when the
reactions were carried out at 353 K.
To optimize the amount of the catalysts that may be required, we have taken the
catalyst (compound I) in three different amounts [5 mg (0.28 mol %), 10 mg (0.56 mol %)
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and 25 mg (1.4 mol %)] to carry out the tandem DK reactions. The yields were better when
the catalytic studies were carried out using 10 mg of the sample. Higher quantity of the
catalyst did not result in improved yields for the product.
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The independent deacetalization and Knoevenagel condensation reactions were
carried out by taking 1 mmol of the reactants and 10 mg of catalysts in 2 ml of DMF. For the
tandem one-pot DK reaction also we have taken similar quantities of the reactant;
benzaldehyde dimethyl acetal(BA) (1 mmol) and malononitrile(MN) (1 mmol) along with the
catalyst (10 mg; 0.56 mol %) in 2 ml of DMF as the solvent in a round bottom (RB) flask
under nitrogen atmosphere. The catalysts were activated at 373 K overnight before
employing for the catalytic studies. The mixture was first stirred for 3 min. at room
temperature and the catalytic reaction was carried out at 353 K. The progress of the reaction
was monitored by the thin-layer chromatography (TLC) at regular interval of time. After 5
hours of reaction, the mixture was filtered and washed with 1 ml of DMF along with CH Cl .
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purified using silica gel column chromatography (hexane/ethyl acetate) and characterized by
1H-NMR spectroscopy.
Results and discussion
Structure of [Cd (C H SO ) (C H N ) (C H NO) ](C H NO) .(CH OH) (I):
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Compound I crystallizes in triclinic (P-1) space group and has 53 non-hydrogen
atoms present in the asymmetric unit (ESI Figure S5). The asymmetric unit contains one and
a half Cd2+ ions, one SIPA ligand, one and a half ABPY ligands, one coordinated DMF
molecule and one lattice DMF molecule along with two methanol molecules. One of the Cd
atoms, Cd(2), occupies a special position (1a) with a site multiplicity of 0.5. Both the Cd
atoms have a distorted octahedral geometry formed by four oxygen and two nitrogen atoms.
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Cd(1) is bonded with four oxygen atoms of SIPA carboxylates and two ABPY ligands
whereas Cd(2) is bonded with two sulfo groups of SIPA ligand, two ABPY ligands and two
DMF molecules. The Cd-O/N bond lengths are in the range 2.275(1) - 2.385(3) Å (Table
S3).
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The carboxylate groups of the SIPA ligand have different bonding with the cadmium
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centers. Thus, one carboxylate forms a μ -η :η -chelating coordination and the other forms a
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μ -η :η -bridging coordination modes to form a [Cd (CO ) ] unit (Figure 1a). This
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connectivity gives rise to a one-dimensional (1D) double chain along the ‘a’ axis (Figure
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b). The 1D double chains are bonded with Cd(2) atom via a μ -η :η monodentate
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coordination mode through the sulfonate group forming a two-dimensional (2D) layer
Figure 1c-1d). The 2D layers are connected to each other through the ABPY ligands giving
(
rise to the three-dimensional structure (3D) (Figure 1e). This connectivity results in a 1D
pore with a diameter of ~ 5.0 Å X ~ 8.0 Å (atom-atom contact distance not including the Van
der Waals radii) along the ‘a’ axis (ESI Figure S6). The extra-framework DMF and
methanol molecules are located inside the 1D channels in the structure (ESI Figure S7). The
solvent molecules are stabilized by a number of non-covalent interactions with the pore
surface. The prominent C-H···O interactions and their distances are shown in the Figure
(ESI Figure S8).
Structure of [Cd (C H SO ) (C H N ) (C H NO) ](C H N ).(C H NO) (II)
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3
7
2
The structure of II is similar to that of I. Compound II has 60 non-hydrogen atoms,
2
+
which contains one and a half Cd ions, one SIPA ligand, one and a half coordinated BPDB
ligands and half non-coordinated BPDB ligand, one bonded DMF molecule along with half
non-bonded DMF molecule (ESI Figure S9). One of the cadmium atoms, Cd(2), occupies a
special position (1a) with site multiplicity of 0.5. Both Cd(1) and Cd(2) have octahedral
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geometry with Cd(1) connected with four carboxylate oxygens and two nitrogens of BPDB
ligands, and Cd(2) is bonded with two sulfo oxygens of SIPA, two DMF oxygens, and two
nitrogens of BPDB ligand. The Cd-O/N bond length are in the range 2.271(6) - 2.400(4) Å
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(Table S3).
The structure of II has connectivities that are similar to that observed in I. Thus, a
one-dimensional double chain formed by the connectivities between the Cd2+ centers and
sulphonare oxygens are further bonded through the sulfonate oxygen involving Cd(2) forms a
two-dimensional layer. The 2D layers are further connected by the BPDB linkers to form the
3
D structure (Figure 2). This connectivity gives rise to a one-dimensional channel (~ 7.0 Å
X ~ 9.0 Å) along the ‘a’ axis (ESI Figure S10). In structure II, we observed that one
unbounded BPDB molecule along with DMF molecules reside inside the channels (ESI
Figure S11), which nearly fills channel.
Thermal stability and Gas adsorption studies:
Thermogravimetric analysis (TGA) (Mettler-Toledo) of the compounds were carried
°
°
°
out in the temperature range of 30 - 850 C (heating rate = 5 C/min) in oxygen atmosphere
(flow rate = 50 mL/min) (ESI Figure S12). Both the compounds exhibited similar
°
behaviour. For compound I, a continuous weight loss up to the temperature of 175 C,
°
°
followed by a sharp weight loss in the temperature range of 315 - 500 C was noted. The
total observed weight loss was 79.2%, which would correspond to the loss of all the organic
moieties (81.1 %) present in the compound. A similar behaviour was also noted for
compound II with the total observed weight loss was 80.9 % (calculated for the loss of
organic moieties 82.8 %). The final calcined product in both the cases was found to be CdO
(ICSD - 24802) (ESI Figure S13).
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The thermal stability of the compounds was also examined by employing variable
temperature in-situ (up to 483 K) powder X-ray diffraction studies (HTPXRD) (ESI Figure
S14) (Rigaku, SmartLab rotating anode diffractometer (CuK radiation) employing alumina
α
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(
Al O ) sample holder. The in-situ PXRD studies suggest that both I and II, appear to be
2 3
°
stable up to 483 K. The broad peak observed near 2θ = 6 was from the sample holder. The
HTPXRD studies also confirm that the gradual weight loss observed in the TGA is mainly
due to the loss of the solvent molecules from the framework and the collapse of the
°
framework starts only after ~ 300 C. It may be noted that the overall crystallinity of the
compounds was slightly reduced at higher temperatures (ESI Figure S14). The calcined
sample (483 K) was examined employing proton NMR as well as elemental analysis to verify
the removal of the solvent molecules (DMF) from the framework (ESI Figure S15 and Table
S2). The studies indicate that at 483 K the most of the DMF molecules have been removed.
Catalysis:
The present compounds appear to possess more than one functional groups. Thus, we
have explored both the compounds, I and II, as a heterogeneous catalyst in one pot tandem
deacetalization−Knoevenagel condensation reaction. The deacetalization reaction, generally,
is acid-catalysed and produces aldehydes or ketones. The base-catalyzed Knoevenagel
condensation reaction can form nitriles. The catalytic conditions were optimized by carrying
out the reaction by changing the temperature, solvent and catalyst amount (Table S5). As
mentioned in the experimental section, the optimal conditions are: T = 353 K, solvent = DMF
and catalyst = 0.56 mol % (10 mg for I and 11 mg for II). In the present study,
deacetalization reaction produces benzaldehyde (BD) from benzaldehyde dimethyl acetal
(
BA) as a reactant, which is acid-catalysed. The base-catalysed Knoevenagel condensation
reaction produces benzylidene malononitrile (BM) in the presence of the reactants BD and
malononitrile (MN).
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Initially, we have carried out the two reactions separately to monitor which one is the
rate determining step. The first step, deacetalization reaction, was found to be slow with
conversion of ~15 % after 5 hours of reaction at 353 K. The formation of aldehyde did not
improve much even when the reaction was carried out for 12 hours. The Knoevenagel
reaction, on the other hand, was found to be fast under the same reaction conditions.
Typically the reaction was observed to be complete within ~ 3.5 hours for I and ~ 3 hours for
II. The superior conversion in the Knoevenagel reaction inspired us to carry out a tandem
deacetalization-Knoevenagel (DK) reaction by keeping the amounts of the reactants and the
other experimental conditions constant (Scheme 1).
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The tandem reaction was found to be successful with yields of ~ 84% (I) and ~ 95%
(II) after 5 hours of reaction at 353 K. The higher yields of the product in the tandem
reaction are the result of the aldehyde formed by the Lewis acid catalysed reaction being
consumed immediately by the Lewis base catalysis. As observed in the separate experiments,
the Lewis base catalysed reaction was much faster, which helped convert the acetal
immediately to the nitrile. This would facilitate the first reaction to proceed in the forward
direction in a facile manner due to the Le Chatelier's principle. The recyclability of the
catalysts in this tandem reaction was tested up to three cycles, which does not indicate any
major drop in the catalytic activity (ESI Figure S16). The PXRD pattern of the catalysts also
did not reveal any appreciable changes in the crystallinity after the third cycle of the catalytic
studies (ESI Figure S17). The success of the tandem catalysis prompted us to investigate the
DK catalytic reactions employing other substituted BA and the results are listed in Table 2
(
ESI Figure S18). From the studies it appears that the yields of the para-substituted methoxy
-OCH ) and bromo (-Br) groups are comparable to the non-substituted BA under the same
(
3
reaction conditions. On the other hand, the reaction does not proceed well when
phenylacetaldehyde dimethyl acetal was employed. Similar behaviour has been noted
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earlier.56 It is likely that the substitution at the α position does not provide the needed
delocalization energy. We have also attempted to carry out the tandem reactions in a solvent-
free condition at 353 K. Solvent-free reactions provide an opportunity to achieve a greener
and more sustainable route of chemical transformations.57-60 Our studies indicate that the
reactions do proceed to near completion albeit taking longer time (~ 15 hours ). The catalysts
also retain their crystallinity under the solvent-free catalytic reactions as well (ESI Figure
S19). An IR spectroscopic investigations on the catalysts after both the solvent free as well
as with DMF as the solvent catalytic reactions did not reveal any observable changes (ESI
Figure S20). The elemental analysis after the catalytic studies also did not reveal any
changes (Table S2).
1
1
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The catalytic studies indicate that II is more active compared to I. Structurally,
compound I has more open pores compared to II. It is likely that the presence of free BPDB
in II enhances the overall basicity in II and favours the aldehyde to nitrile reaction. In order
to get a better insight into this reaction, we sought to carry out time dependent catalytic
studies. For this reaction, we collected small quantities of the reaction mixture at regular
intervals and analysed employing NMR spectroscopy.
In a typical solvent-free tandem reaction, 25 mmol of BA and MN along with 250 mg
of I and 275 mg of II were reacted at 353 K. Dimethyl terephthalate (0.077mmol) was used
as an internal standard for the NMR study. A small aliquot (0.064 ml) was removed from the
reaction mixture using a syringe starting from t=0 (beginning of the reaction) followed by
every three hours. The mixture was transferred to the NMR tube along with the internal
standard and CDCl as the NMR solvent (ESI Figure S21-22). The distributions of the
3
products from the experiments are shown in Figure 3. The distribution of the reactants and
the products employing I and II appears to be showing similar trends. Initially the
conversion is slow and it becomes maximum in between 9-12 hours for I and it is in between
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-9 hours for II and then the saturation occurs. In addition, the product formation appears to
be faster when II was employed as the catalyst. It was found that after 15 hours the amount
of reactants was negligible in the case of II. A similar observation was also noted employing
DMF as the solvent. It is clear that the catalytic activity of II is superior to that of I. We
have also carried out a hot filtration test to prove the heterogeneity of the reaction.
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The deacetalization-Knoevenagel catalytic reactions have been carried out by
employing MOFs (Table 3). As can be seen, the present compounds are active and exhibit
catalytic activity that is comparable to those reported earlier.42-45, 66-69 It may be noted that in
the present study no post synthetic modifications or nanoparticle incorporation have been
carried out and the compounds were used as synthesized. In addition, the Cd-MOFs exhibit
catalytic activity with minimal quantity of solvent, which would be desirable for the
environmental reasons and a green process.
Proton conductivity:
The TGA investigations along with in-situ PXRD and IR studies suggest that the
solvent molecules may be removed without collapse of the framework. We wanted to
explore the water absorption capability of the preheated samples of the compounds I and II
(BELSORB aqua). The water sorption isotherm studies indicate a gradual water uptake,
which reaches a value of 157 mL/g at p/p0 = 0.9 and 104 mL/g at p/p0 = 0.9 for compounds I
and II, respectively (ESI Figure S23). The adsorbed water would correspond to 12.5 mol of
H O / mol of I and 9.1 mol of H O / mol of II. Compound I exhibits higher water uptake
2
2
compared to II due to the presence of more open channels. The adsorption isotherm for both
the compounds exhibits a hysteresis, which does not close at lower partial pressures. This
suggests that the pores could be hydrophilic in nature and can absorb water irreversibly. The
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PXRD pattern of the water absorbed sample does not show any observable changes, which
suggests that the compounds retain their structures (ESI Figure S24).
The water adsorption studies indicated that the compound I uptakes considerable
amount of water. Structurally I contains pores that are decorated by sulfonate moieties,
which opens up the possibility of accommodating the lattice water molecules either as
clusters or chains along the 1D channel. There have been reports of proton mobility in
compounds having sulfonate functionality along with the solvent molecules. This prompted
us to investigate the possible proton conductivity in I. A pellet of compound I was prepared
and kept at 98% humidity chamber at room temperature for 24 hours. The measurement was
1
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carried out in the frequency range of 0.1−10 Hz with the signal amplitude of 0.12 V (Alpha,
-4 −1
−1
Novocontrol). A proton conductivity value of 0.86 X 10 Ω cm was observed from the
Nyquist plots for compound I at 30 °C (Figure 4). The proton conductivity behaviour of I
found to be temperature dependent as the value was found to increase with the increase of
temperature (Figure 4). The observed proton conductivity value at RT was found to be
comparable with those reported elsewhere. The activation energy was calculated from the
Arrhenius plot, which gave a value of 0.3 eV suggesting a possible Grotthus mechanism in
this compound (ESI Figure S25).61-65
Conclusion:
Two new 3D MOFs [Cd (C H SO ) (C H N ) (C H NO) ](C H NO) .(CH OH) (I)
3
8
3
7 2
10
8
4 3
3
7
2
3
7
2
3
4
and [Cd (C H SO ) (C H N ) (C H NO) ](C H N ).(C H NO) (II) have been prepared
3
8
3
7 2
12 10 4 3
3
7
2
12 10
4
3
7
2
and their structures determined. The compounds have three-dimensional structures with I
having a one-dimensional open channels. The compounds exhibit both Lewis acidic (from
Cd center) as well as Lewis basic (from the sulfo oxygens and azine/free pyridyl group)
functionality. The dual functionality was exploited for one-pot tandem deacetalization-
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Knoevenagel reaction both under the solvent as well as solvent-free conditions. Our studies
reveal that compound II is more active for the tandem catalysis compared to compound I,
possibly due to the presence of azine functionality and uncoordinated BPDB linkers. Proton
conductivity studies on I indicate moderate proton conductivity behaviour at room
temperature.
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Acknowledgement:
SN thanks Science and Engineering Research Board (SERB), Government of India,
for the award of a J C Bose National Fellowship. SN also thanks the Council of Scientific
and Industrial Research (CSIR), Government of India for the award of a research grant. The
authors thank Prof. R. Ranjan and Mr. A. Dey (Materials Engineering, IISc) and Prof. A.J.
Bhattacharyya for their help with the in-situ HTPXRD and proton conductivity studies.
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Separation Medium. J. Am. Chem. Soc. 2016, 138, 2292-2301.
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(
21) Platero-Prats, A. E.; Li, Z.; Gallington, L. C.; Peters, A. W.; Hupp, J. T.; Farha, O.
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8
9
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3
4
5
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7
8
9
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1
2
3
4
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6
7
8
9
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2
2
2
2
2
2
2
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Table 1: Crystal data and structure refinement parameters for all the compounds.
Structural parameter
Empirical formula
I
II
C H N O S Cd C H N O S Cd
6
2
58 16 22
2
3
76 74 20 18
2
3
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Crystal system
Space group
a (Å)
triclinic
triclinic
P-1 (no.2)
10.1392(5)
13.6080(6)
13.6470(6)
73.330(10)
82.470(10)
81.922(10)
1777.71(14)
1
P-1 (no.2)
10.2282(14)
13.5641(19)
15.9140(2)
108.464(3)
98.421(4)
97.469(4)
2034.70(5)
1
b (Å)
c (Å)
α (°)
β (°)
γ (°)
V (Å3)
Z
T/K
100(2)
100(2)
-3
ρ (calc/gcm )
1.663
1.597
-1
μ (mm )
 (Mo Kα/Å)
θ range ( °)
Rint
1.034
0.909
0.71073
0.71073
3.095 to 25.998
0.0509
3.042 to 26.000
0.0333
R indexes [ I > 2 (I)] R
.1306
= 0.0483; wR
= R
0.1714
= 0.0617; wR
=
1
2
1
2
0
R indexes (all data)
R = 0.0498; wR = R = 0.0665; wR =
1
2
1
2
0
.1317
0.1746
2
2
2
2
1/2
2
2
2
R =∑ | Fo | - | Fc ||/∑ | Fo |; wR = {∑ [w (Fo - Fc )]/ ∑ [w (Fo ) ]} . w = 1/[ρ (Fo) + (aP) + bP].
P = [max (Fo, O) + 2(Fc) ]/3 where a = 0.0699 and b = 11.4708 for I and a = 0.0959 and b = 12.9591
for II.
1
2
-2
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Table 2: One-pot tandem catalysis yield with the heterogeneous catalysts compound I and
II.
Substrate
Product
% of Yield
II
I
8
8
7
4
1
6
95
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
92
85
Trace
Trace
Reaction conditions: Benzaldehyde dimethyl acetal (1 mmol), malononitrile (1 mmol), DMF
2 ml) and catalyst (0.56 mol%; 10 mg of compound I/11 mg of compound II). The yields
(
were determined by employing silica gel column chromatography after 5 hours of reaction.
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2
2
2
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3
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4
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4
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Table 3. Table summarizing the various MOF catalysts employed in the tandem
deacetalization-Knoevenagel condensation reaction
Name of Catalyst
Catalyst
amount
Solvent
Temp. Reaction
Yield
Ref.
(°C)
Time
(
%)
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
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2
3
4
5
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7
8
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1
2
3
4
5
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9
0
Cu-PCN-126
0.5
DMSO
50
12 hours
99
42
mol%
Cr-MIL-101-AB-x
Yb-BDC-NH2
4 mol%
2 mol%
100 mg 1,4-dioxane
50 mg
0.5
DMF
DMSO
90
50
90
90
50
2 hours
24 hours
3 hours
5 hours
48 hours
>91
97
94
99
99
43
44
45
66
67
MIL-101(Al)-NH2
Fe O @Cu-HKUST-1
1,4-dioxane
DMSO
3
4
Cu-HNUST-8
mol%
0.5
mol%
Cu-HNUST-6
DMSO
50
70
90
90
48 hours
12 hours
5 hours
99
89
84
95
68
69
PBSA/Cr-MIL-101 +
PMAP/Cr-MIL-101
Compound I
5 mol% DMSO/H O
2
0.56
mol%
0.56
DMF
DMF
This
work
This
work
Compound II
5 hours
mol%
.
PCN-126 = C H Cu N O ,
HNUST-8 = [Cu (PDBAD)] xGuest,
HNUST-6 =
Cr-MIL-101 =
2
3
11
2
.
3
11
2
n
4-
[
Cu (MOPBD )(H O) ] xGuest,
HNUST-1
=
Cu (BTC)
2
2
2
3
2,
[
Cr (O)X(bdc) (H O) ], MIL-101(Al)-NH = Al O(DMF)[(COO)C H NH (COO)] ·nH O.
3
3
2
2
2
3
6
3
2
3
2
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Page 29 of 34
Crystal Growth & Design
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(a)
(b)
(c)
(d)
(e)
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Figure 1: (a) View of [Cd (CO ) ] unit in I (μ -η :η and μ -η :η bridgings can be observed)
2
2 4
1
2
(
b) View of 1D double chain formed by SIPA and Cd metal; (c) View of 2D layer of Cd and
SIPA ligand in abc plane; (d) View of 2D layer from axis a; (e) View of 3D structure of I
lattice solvents and hydrogens are omitted for clarity). (Cd atoms are shown in green
coloured polyhedral)
(
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