Five porous zinc(II) coordination polymers functionalized with amide groups: Cooperative and size-selective catalysis

Article abstract of DOI:10.1039/c5ta06248a

Five functionalized porous coordination polymers 1-5 with highly ordered amide groups in the channels show notable interaction with guest molecules. The amide groups functioned as trigger sites and catalytically driven forces to activate substrate proximi

Full text of DOI:10.1039/c5ta06248a

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Five porous zinc(II) coordination polymers functionalized with amide
groups: cooperative and size-selective catalysis
a,b*
b
b*
c
b
a
Lufang Ma , Xiaoning Wang , Dongsheng Deng , Feng Luo and Baoming Ji , Jian Zhang
a
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of
Matter, the Chinese Academy of Sciences, Fuzhou, Fujian 350002, P. R. China.
b
College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022,
P. R. China
c
College of Biology, Chemistry and Material Science, East China Institute of Technology, Fuzhou,
Jiangxi, P. R. China.
(
* Corresponding author Tel.: +86 379 65523821; fax: +86 379 65523821.
Eꢀmail address: mazhuxp@126.com and dengdongsheng168@sina.com)
Abstract: Five functionalized porous coordination polymers 1–5 with highly ordered amide
groups in the channels show notable interaction with the guest molecules. The amide groups
functioned as trigger sites and catalytic driven forces to activate the substrate proximity with the
pore. Catalytic studies on catalyst with different porous radii and substrates with different
molecular size revealed that these porous materials are heterogeneous, efficient and reusable
catalysts for the sizeꢀselective Knoevenagel condensation reaction. The solids were stable after the
reactions and were easily recycled and reused under the reaction conditions. Most importantly,
compound 3 with two different functionalities decorated the porous wall displays an elegant
example of cooperative catalysis.
Keywords: porous coordination polymers; heterogeneous catalysis; Knoevenagel reaction;

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1
. Introduction
Nowadays, porous coordination polymers (PCPs) have gained tremendous attention, mainly
1
2
3
because of their potential applications in gas storage, separation, heterogeneous catalysis, and so
4
on. Many PCPs have unique characteristic features such as wellꢀdefined cavity sizes and shapes,
open Lewis acid sites, and active functional organic sites. Thus they can potentially serve as high
efficient catalysts to promote organic transformations with sizeꢀ, regioꢀ, and stereoꢀselectivities, in
5
–10
a manner similar to inorganic zeolites.
As heterogeneous and recyclable catalysts, many
11
functional PCPs have been explored to promote cyanosilylation of aldehyde, alkylation of
1
2
13
14
aromatics, ringꢀopening reaction of epoxide, Knoevenagel condensation, transesterification of
15
esters, and so on. Although impressive progress has been achieved in the fields of catalysis, to
improve the functions of the pores in PCPs for better catalytic performance and selectivity still
remains a major challenge.
To create functional PCPs, some practical strategies, such as direct synthesis and
postꢀsynthetic modification, were used to produce guest accessible sites inside the wellꢀdefined
16–18
spaces, and to introduce functional organic sites to decorate channel surfaces.
Here,
incorporating active ligands including additional functional moieties as guestꢀaccessible sites
within pores of PCPs is a powerful approach to achieve functional flasks to facilitate their
1
7b
applications. An outstanding feature of these PCPs is their chemical functionality that could be
achieved by the uncoordinated active organic groups. To date, there are only few examples of
amideꢀ, pyridylꢀ, hydroxylꢀ, or aminoꢀcontaining MetalꢀOrganic Frameworks (MOFs) obtained by
19
direct synthesis, among more 10000 MOFs reported.
For functional application, amideꢀfunctionalized ligands are good candidates, because amide
group has two types of hydrogen bonding sites: the ꢀNH moiety acts as an electron acceptor and the
carbonyl group acts as an electron donor. Thus, this amide group can be use as baseꢀtype catalytic
20
17b
driving force to prompt several important reactions. For example, Kitagawa et al. have first

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reported that a sizeꢀselective Knoevenagel condensation reaction catalyzed by compound
[Cd(4ꢀbtapa) (NO ]·6H O·2DMF} (4ꢀbtapa 1,3,5ꢀbenzene tricarboxylic acid
{
2
3
)
2
2
n
=
tris[Nꢀ(4ꢀpyridyl)amide]). Next, Su et al. have demonstrated that two amideꢀfunctionalized lead
PCPs display sizeꢀ and shapeꢀselective catalytic activity towards the Knoevenagel condensation
10b
reaction. On the other hand, incorporation of –NH functionality on the pore surface can also
2
9
b,14c,21
yield active catalysts for the Knoevenagel condensation.
It is noted that the weak basicity of
amide groups implied only very low activities. Thus, a smart strategy is to combine two different
basic groups, such as amide and amine groups, exposing in the pores of PCPs so as to exhibit
higher catalytic capacity. However, to the best of our knowledge, PCPs with two different active
organic functionalities are rare.
To our delight, our research group has recently provided five structural isomorphic PCPs that
2
2
possess two different active organic functionalities within the cavities. Moreover, our research
4
4
results reveal that Zn(L)(aip)·(H O) (L = N ,N ’ꢀdi(pyridinꢀ4ꢀyl)biphenylꢀ4,4’ꢀdicarboxamide,
2
2 2
H aip = 5ꢀaminoisophthalic acid) shows the biggest CO adsorption ability among the five
isomorphic PCPs due to the combined effect from both amide group and amine group. The
interesting result promotes us to study other promising applications. As is well known, cooperative
catalysis on a pore of PCP requires the control of the relative spatial arrangement and the relative
molar ratio of two functionalities at the channel surface. Moreover, the distance and spatial
organization of the two active functionalities have to be carefully adjusted in such a way that they
can act synergistically as cooperative catalysts. Indeed, the previous literatures have reported that
some catalysts bearing two different active functionalities are able to individually activate each of
2
3
the two reaction partners in a cooperative manner. Based on the aboveꢀmentioned facts, in order
to find the best candidate for catalyzing the Knoevenagel condensation reaction, it is necessary to
screen the catalytic capacities of the five PCPs. Herein, we report catalytic performance of the five
PCPs toward the Knoevenagel condensation reaction. The catalytic result reveals that, among the
five catalysts, Zn(L)(aip) shows the highest catalytic active due to the cooperation catalysis from

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both amide group and amine group. Furthermore, all the five PCPs display the shapeꢀ and
sizeꢀselective catalytic activity in the Knoevenagel condensation reaction.
2
. Experimental Section
2
.1. General procedures
All reagents and starting material were commercially available and used as received unless
special notice. Powder Xꢀray diffraction (PXRD) data were recorded on a Bruker D8ꢀADVANCE
Xꢀray diffractometer with Cu–Kα (λ = 1.5418 Å). The products were identified by NMR analysis
1
in comparison with authentic samples. HNMR spectra were recorded on a Varian UNITY/NOVA
3 6
400 NMR spectrameter using CDCl or DMSOꢀd as the solvent at room temperature. Chemical
shifts are given in δ relative to TMS. The coupling constants J are given Hz.
2
.2. Typical procedure for the Knoevenagel condensation reaction
A 10 mL roundꢀbottomed flask was charged with aldehyde compound (0.2 mmol),
malononitrile (0.6 mmol) and catalyst (0.004 mmol). The reaction mixture was stirred for the
required time under solventꢀfree condition. The reaction was monitored by the thin layer
chromatography. After the reaction finished, 10 mL of ethanol was added to the reaction mixture.
The mixture was stirred for another 5 min. Then the catalyst was filtered off, and the filtrate was
concentrated under reduced pressure. The crude product was purified by recrystallization from
aqueous ethanol to afford pure compounds. All isolated pure products were fully characterized by
NMR analysis. The recovered catalyst was washed with ethyl acetate, dried, and reused without
further purification or regeneration. Moreover, the recovered catalysts were characterized by the
Xꢀray powder diffraction and showed identical results to those of the fresh samples.
2
.4. Experimental procedure for reusability tests

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The reusability of compound 3 was tested for the Knoevenagel condensation reaction. When
the reaction finished, the mixture was centrifuged, the filtrate was decanted, and the catalyst was
dried under vaccum at room temperature for 8 h, and then reused directly without further
purification for the second run with fresh aldehyde and malononitrile. It was used for four
consecutive runs with minor loss in activity.
3. Results and Discussion
2
2
According to our previous method, we synthesized five structural isomorphic PCPs.，namely,
.
.
.
Zn(L)(ip) (DMF)(H O)
(1a), Zn(L)(hip) (DMF)(H O) (2a), Zn(L)(aip) (H O) (3a),
2
1.5
2
2
.
.
Zn(L)(nip) (DMF)0.5(H
2
O)0.5 (4a), Zn(L)(HBTC)(H
2
O)
2
(5a) (H
2
2
ip = isophthalic acid, H hip =
5
ꢀhydroxyisophthalic acid, H aip = 5ꢀaminoisophthalic acid, H nip = 5ꢀnitroisophthalic acid, and
2 2
3
H BTC = 1,3,5ꢀbenzenetricarboxylic acid). The structural analysis reveals that the 1ꢀD hexagonal
channels of the five PCPs not only possess abundant amide groups but also is decorated by
different functional groups of –H, –OH, –NH , –NO , and –COOH, respectively. TGA data
indicated that PCPs 1a, 2a, 4a, and 5a are lease completely water and DMF molecules exceed
00 °C except PCPs 3a in the temperature range of 30–150°C, to form a guestꢀfree phase Zn(L)(ip)
1), Zn(L)(hip) (2), Zn(L)(aip) (3), Zn(L)(nip) (4), and Zn(L)(HBTC) (5), respectively. The
2
2
2
(
powder Xꢀray diffraction (PXRD) patterns of the guestꢀfree phase 1–5 are almost identical with that
of the asꢀsynthesized 1a–5a, respectively, indicating that the basic 3D framework is retained and
thus the 1D hexagonal channels are accessible to guest molecules.
The previous studies demonstrated that PCPs with amide groups could function as the catalytic
interaction sites on the channel wall. We also expected the amide groups in the channels of the
resulting five PCPs can provide guest interaction sites as base sites (Figure 1). The selective
accommodation and activation of reactants by the five PCPs were confirmed by selective
adsorption experiments toward three active methylene compounds. Three methylene compounds
2
chosen for the reaction were malononitrile (molecular size, 6.9 ×4.5 Å ), ethyl cyanoacetate (10.3

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2
2
×
4.5 Å ), and cyanoꢀacetic acid tertꢀbutyl ester (10.3 ×5.8 Å ). Asꢀsynthesized five PCPs were
immersed in the benzene containing corresponding reagent and stirred, respectively. The powders
1
were filtered and dried in air. The resulting powers were characterized by H NMR and IR
analyses. The corresponding data of compound 3 will be representatively discussed in detail, as
1
shown in Figures 2 and 3. The H NMR spectra showed that compound 3 adsorbs 3.8, 1.6, and 0.5
molecular stoichiometric amounts of malononitrile, ethyl cyanoacetate, and cyanoꢀacetic acid
tertꢀbutyl ester per 3, respectively (Figure 2). The result indicates the smallest malononitrile
molecule was most easily introduced in the channels of 3, and the inclusion amount of
malononitrile for 3 was 2ꢀ8 times larger than those of the other reagents. The IR analysis also
reveals that only malononitrile interacted with 3 (Figure 3). Some conclusions can be deduced
from these results: 1) if an active methylene compound interacts with part of the αꢀH atom, the IR
s
as
band attributed to the C≡N stretching vibration shifts to a lower wavenumber and ʋ CN˗ʋ CN
24
s
as
CN
ꢀ1
splitting appears; 2) the ʋ CN˗ʋ
splitting at 2183 and 2202 cm was observed for
malononitrile in 3, whereas the other reagents showed only the original peak; 3) the IR spectrum
of 3 containing malononitrile shows two types of guests: one interacting with the host 3 and the
other not interacting. Based on the above two analyses, the channels of 3 can selectively adsorb
1
4a
and activate the smallest malononitrile molecule, similar to the previous report.
PCPs with base properties are important heterogeneous catalysts for baseꢀcatalyzed reaction
due to their unique reactivity and selectivity under mild reaction conditions. One of the most
important baseꢀcatalyzed reaction is the Knoevenagel condensation reaction. In this reaction, the
C–C bondꢀforming is promoted by the activation of the carbonyl carbon and the addition of the
active methylene compounds to give rise to α,βꢀunsaturated compounds, a kind of precursors of
fine chemicals and biological compounds.
In a typical reaction, a mixture of benzaldehyde (0.1 mmol) and malononitrile (0.3 mmol)
was added into a 50 mL flask containing the catalyst (0.003 mmol, 3 mol %). The resulting
mixture was stirred at room temperature. The progress of the reaction was monitored by checking

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TLC from the reaction mixture at regular time intervals.
First of all, the reactivity of the five PCPs (1–5) as catalysts was studied. The results reveal
that catalyst 3 yields the product almost quantitatively after 3 h, while the yields for catalysts 1, 2,
4
and 5 were lower than 80, 70, 72 and 60%, respectively (Figure 4). It is noted that all the five
PCPs display good catalytic efficiency towards to the Knoevenagel reaction because the amide
groups are introduces as trigger sites to achieve efficient guest interactions, a powerful catalytic
driving force, and good signal responding communications. The active differences found between
3
and other four polymers (1, 2, 4, and 5) cannot be attributed to the differences in diffusion rate,
because all structural frameworks contained similar pore openings, but must be due to difference
in the basicity strength of the active groups. Possibly the amide and amine groups of 3 in a
cooperative manner show a higher basicity than those groups at the windows of the other four
2
PCPs, because except for amide groups, the pendent NH groups of 3 present at the pore surface
1
6b,
can also promote the Knoevenagel reaction, which has been identified by the previous reports.
21a
Indeed, the distance and organization of the amide and amine functionalities in 3 can be
precisely adjusted in such a way that they can act synergistically as cooperative catalysts.
Accordingly, 3 shows a remarkably superior activity (1.2 times higher than that of 1). However,
the lower activity of 5 might be ascribed to the decrease of base by the acid pendent COOH
groups. Notably, the activity observed for 3 catalyzed the Knoevenagel reaction of benzaldehyde
with malononitrile is superior to those found for [Cd(4ꢀbtapa) (NO ) ] (4 mol% loading, 98%
2
3 2
17b
17d
yield and 12 h), the porous BFꢀCOFꢀ1 (5 mol% loading, 96% yield and 10 h), and the
1
7e
multiꢀfunctional PCNꢀ12 (5 mol% loading, 99% yield and 12 h).

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Figure 1. Perspective views of channels within multifunctional PCPs 1–5 showing the
constructional fragments.
αꢀH
H
H
O
O
NC
αꢀH
H
H
O
NC
O
αꢀH
H
H
NC
CN
1
Figure 2. HꢀNMR (DMSOꢀd
b) ethyl cyanoacetate, and (c) cyanoꢀaceticacidtertꢀbutyl ester. The peaks marked with an asterisk
indicate the L and nip ligands.
6
) spectra of 3 that adsorbed each guest molecule: (a) malononitrile,
(

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Figure 3. IR spectra in the region of C≡N stretching vibration bands of (a) 3 containing
malononitrile, (b) 3 containing ethyl cyanoacetate, and (c) 3 containing cyanoꢀacetic acid
tertꢀbutyl ester. The bands marked with an asterisk indicate the C≡N stretching vibration bands
due to each substrate that is not activated.
Figure 4. Kinetic profiles for Knoevenagel condensation reaction of for PCPs 1–5.
To investigate the advantageous role of the neat conditions, we carried out the above reaction
2 2
in different solvents, such as water, CH Cl , MeCN, and benzene under identical conditions to
obtain the corresponding α,βꢀunsaturated compounds in 40%, 60%, 85%, and 30% yields,
respectively. It is remarkable that the reaction carried out under neat conditions by using catalyst 3

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affords the corresponding α,βꢀunsaturated compounds in excellent yield (99%), which is
significantly higher than that in organic solvents.
Considering the possibility of those compounds containing amide or amine groups to catalyze
the Knoevenagel condensation reaction, we performed control tests with 5ꢀaminoisophthalic acid
4
4
or N ,N ’ꢀdi(pyridinꢀ4ꢀyl)biphenylꢀ4,4’ꢀdicarboxamide as catalysts instead of 3. As in the case of
, the reaction of benzaldehyde with malononitrile in the presence of 5ꢀaminoisophthalic acid gave
the same products with little lower yields under similar reaction conditions (e.g., 92% for H aip vs
3
2
4
4
9
9% for 3). However, the N ,N ’ꢀdi(pyridinꢀ4ꢀyl)biphenylꢀ4,4’ꢀdicarboxamide ligand is very less
efficient to prompt the catalytic transformation, affording the corresponding α,βꢀunsaturated
compounds with 32% yields. When the 5ꢀaminoisophthalic acid was used as catalyst, all the
Knoevenagel condensation reaction did not exhibit any selectivity toward the reaction substrates.
And, the process involving 3 was heterogeneous, catalytic reaction in the presence of H
2
aip was
partially homogeneous, but without achieving complete dissolution of H aip. Therefore, compared
2
2
to H aip, higher activity of 3 may be caused by better accessibility of the catalyst’s active sites.
Taken together, these results indicate that the catalytic activity of 3 is superior to its corresponding
components.
Next, the remarkably simple and convenient reaction conditions, easy work up, and high
yield for the transformation prompted us to extend the scope of 3 as heterogeneous catalyst for the
Knoevenagel condensation reaction of a wide variety of aromatic aldehydes. It gave the
corresponding α,βꢀunsaturated compounds in goodꢀtoꢀexcellent yields (Table 1). On the one hand,
it seems that the nature of the substituent on the aromatic ring had dramatic effect on the reaction
yield; the lowest yield was obtained for an electron donor group like pꢀmethoxybenzaldehyde. On
the other hand, in order to test the size selectivity of 3, a systematic approach must be performed
by varying the size and shape of aldehyde. In the case of 4ꢀphenylbenzaldehyde, a slightly
2
elongated, linear molecule (4.3 × 10.4 Å ), afforded a 90% yield. As for 1ꢀnaphthaldehyde with

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a
entry
substrate
molecular size
.2 Å
time
yield
6
2
molecular dimensions of 6.8 × 6.2 Å , the yield was reduced to 70%. These results suggest that the
Knoevenagel condensation reactions catalyzed by 3 are closely dependent on its pore sizes (7.0 ×
8
.7 Å). Under similar experimental conditions, we have attempted ketones instead of
benzaldehyde derivatives to carry out Knoevenagel condensation reactions. Unfortunately,
ketones seem to not react with malononitrile.
Table 1. Knoevenagel condensation reactions catalyzed by 3
CN
CHO
CN
CN
3 mol%
R
R
CN
solventꢀfree

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CHO
1
3
99
7
.0 Å
CHO
2
3
4
99
99
99
O
2
N
2
6
.7 Å
CHO
CHO
3
2
Cl
7
.5 Å
NC
6
.3 Å
5
6
O N
2
CHO
3
5
99
98
CHO
Cl
6.2 Å
8
.1 Å
CHO
CHO
7
8
4
4
98
99
O
8.0 Å
6
.8 Å
CHO
9
4
4
70
90
1
0.4 Å
CHO
1
0
a
Yield of pure isolated product
To further probe whether the Knoevenagel reaction occurred inside the pores or on the surface
of the solid catalyst, active methylene substrates of increasing dimensions were tested for the
2
catalyst 3. In the case of ethylcyanoacetate, a slightly elongated molecule (4.5 × 10.3 Å ), the

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conversions of these Knoevenagel condensations with benzaldehyde decreased obviously to 70%
2
under the same conditions. As for even larger tertꢀbutyl cyanoacetate (5.8 × 10.3 Å ), the
condensation reactions with benzaldehyde did not proceed (Table 2). Since the pore sizes of 3 are
7
.0 × 8.7 Å which exhibits the confined sizes and cavity, the large substrates might be excluded in
the catalysis due to difficulty in diffusion into the channels of 3. The guestꢀselective reaction
clearly demonstrates that the reaction occurs in the channels and not on the surface of 3.
Finally, the heterogeneity, recyclability and stability of 3 in the Knoevenagel reaction of
benzaldehyde and malononitrile were examined. After the reaction mixture was stirred for 2 h,
removal of the catalysts via filtration resulted in the complete shut down of the reaction, which
verifies the heterogeneous catalysis of 3. In order to examine the recyclability and stability of 3 in
this Knoevenagel reaction, they were recycled in four consecutive experiments. As mentioned
before, a corresponding product yield of 99% is achieved in the first run. In the second, third, and
fourth run the product yields, determined after the same reaction conditions, decrease to 98%,
95% and 93%, respectively. Meanwhile, elemental analyses along with powder Xꢀray analysis
were applied to characterize catalyst 3 before and after catalytic application. Elemental analysis of
the recyclic catalyst 3 showed good agreement between the calculated and experimentally
determined compositions, as summarized in Table 3. The PXRD patterns of catalysts 3 measured
after the reactions show the same profiles as the asꢀsynthesized samples, indicating the unchanged
coordination frameworks although the crystallinity in the fourth run seems to be weakened due to
decreasing dramatically intension of the diffraction peaks, as depicted in Figure 5.

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Figure 5. XRD patterns of 3: (a) the simulated XRD pattern, (b) the first run, (c) after the second run, (d)
after the third run, and (e) after the fourth run.
Table 2. Knoevenagel Condensation Reaction of Benzlaldehydewith Substrates
CHO
CN
3 mol%
CN
R
solventꢀfree
R
a
entry
1
substrate
molecular size
6.9 Å
catalyst yield (%)
NC
CN
3
100
O
2
3
NC
NC
10.3 Å
3
70
O
O
O
3
0
1
0.3
a
Yield of pure isolated product

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Table 3. Elemental analysis of 3
C
H
N
Calculated
Found
60.15 3.63 10.96
60.38 3.65 11.03
60.43 3.67 11.05
First recycling
Second recycling 60.56 3.69 11.09
Third recycling 60.62 3.72 11.12
Fourth recycling 60.78 3.74 11.16
Conclusions
In conclusion, we have developed five desolvated PCPs, which are mild and efficient
heterogeneous catalysts for the Knoevenagel condensation reaction. The amide groups in the five
PCPs work as trigger sites and catalytically driven forces to achieve efficient guest interactions,
enforcing the reaction components proximity within the pore, resulting in excellent sizeꢀselective
towards the substrate. Most importantly, the results clearly demonstrated that compound 3 is the
efficient base catalyst for the Knoevenagel condensation reaction among the five PCPs under
solventꢀfree conditions, because the distance and spatial organization of the amide and amine
groups in 3 can site in such a way that they can act synergistically as cooperative catalysts.
Therefore, the present study is significant, because it displays an elegant example of two different
functionalities decorated the porous wall with cooperative catalysis.
ACKNOWLEDGMENT
We gratefully acknowledges the financial support from the Natural Science Foundation of
China (Grant No. 21371089 and 21272109) and technology innovation team support programs of
Henan Province University (No. 14IRTSTHN008).
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Five desolvated PCPs exhibit efficient base catalysts for the Knoevenagel condensation
reaction and show size selectivity under solvent-free conditions.