Highly Stable Copper(I)–Thiacalix[4]arene-Based Frameworks for Highly Efficient Catalysis of Click Reactions in Water

Article abstract of DOI:10.1002/chem.201903966

Environmentally friendly metal–organic frameworks (MOFs) have gained considerable attention for their potential use as heterogeneous catalysts. Herein, two Cu^I-based MOFs, namely, [Cu₄Cl₄L]?CH₃OH?1.5 H₂

Full text of DOI:10.1002/chem.201903966

DOI: 10.1002/chem.201903966
Full Paper
&
Metal–Organic Frameworks
Highly Stable Copper(I)–Thiacalix[4]arene-Based Frameworks for
Highly Efficient Catalysis of Click Reactions in Water
Xue-Xia Wang,[a] Jin Yang,[a] Xianxiu Xu,[b] and Jian-Fang Ma*[a]
Abstract: Environmentally friendly metal–organic frame-
works (MOFs) have gained considerable attention for their
potential use as heterogeneous catalysts. Herein, two CuI-
based MOFs, namely, [Cu4Cl4L]·CH3OH·1.5H2O (1-Cl) and
[Cu4Br4L]·DMF·0.5H2O (1-Br), were assembled with new func-
tionalized thiacalix[4]arenes (L) and halogen anions XÀ (X=
Cl and Br) under solvothermal conditions. Remarkably, cata-
lysts 1-Cl and 1-Br exhibit great stability in aqueous solu-
tions over a wide pH range. Significantly, MOFs 1-Cl and 1-
Br, as recycled heterogeneous catalysts, are capable of
highly efficient catalysis for click reactions in water. The MOF
structures, especially the exposed active CuI sites and 1D
channels, play a key role in the improved catalytic activities.
In particular, their catalytic activities in water are greatly su-
perior to those in organic solvents or even in mixed sol-
vents. This work proposes an attractive route for the design
and self-assembly of environmentally friendly MOFs with
high catalytic activity and reusability in water.
Introduction
functional polymers, surface modification, and supramolecular
chemistry.[17–19] To date, various homogeneous CuI catalysts
have been studied for CuAAC reactions.[20,21] Homogeneous
copper(I) catalysts are effective, but they are difficult to sepa-
rate from the reaction system, which restricts their wide use.[22]
To overcome this limitation, recycled heterogeneous catalysts
have been developed accordingly.[23–26]
Currently, the catalytic syntheses of chemicals and pharma-
ceuticals through green and sustainable technologies have re-
ceived considerable attention.[1,2] To date, continuous efforts
have been made to develop sustainable and effective strat-
egies for organic catalytic reactions.[3–6] In this regard, the use
of organic solvents for chemical conversions is one of the most
important issues in green chemistry, owing to their harmful in-
fluence on the environment and human health.[7–9] Therefore,
the use of less toxic solvents and the development of recycled
heterogeneous catalysts are key strategies for green chemis-
try.[10,11] The replacement of harmful solvents by environmen-
tally friendly water, ionic liquids, or supercritical carbon dioxide
has become one of the most desirable routes for sustainable
chemistry.[12] Water is the most green solvent, in view of envi-
ronmental protection.[13]
Metal–organic frameworks (MOFs), as one type of promising
heterogeneous catalyst, have been widely used in various cata-
lytic reactions.[27–31] In this regard, heterogeneous CuI-based
MOF catalysts for click reactions exhibit some advantages,
such as improved stability, easy separation, and high reusabili-
ty.[32–34] Nevertheless, the reported works directly using CuI
MOFs as heterogeneous catalysts for click’ reactions are usually
conducted in organic or mixed solvents (such as ethanol and
water).[35–37] By contrast, water, as a cheap, nontoxic, safe, and
green solvent, has received far less attention in CuAAC reac-
tions with CuI MOFs as heterogeneous catalysts.[38,39]
Click chemistry, as an important catalytic reaction type, has
been extensively employed in different domains of organic
synthesis, medicinal chemistry, and molecular biology.[14–16] For
example, CuI-catalyzed azide–alkyne cycloaddition (CuAAC) has
received significant attention in many research fields, such as
Generally, organic ligands play an important role in the ra-
tional construction of MOF catalysts featuring tunable struc-
tures.[40,41] Calix[4]arenes, as one type of excellent candidate
ligand, have attracted considerable attention from researchers
due to the ease of modifying their upper and lower
edges.[42–48] Particularly, calix[4]arenes substituted by coordina-
tion hybrid atoms, such as N and S, can improve the stability
of the resulting CuI MOFs as recycled catalysts.[49–53]
[a] Dr. X.-X. Wang, Prof. J. Yang, Prof. J.-F. Ma
Key Lab of Polyoxometalate Science, Department of Chemistry
Northeast Normal University, Changchun 130024 (P.R. China)
E-mail: majf247@nenu.edu.cn
Based on above consideration, we prepared a flexible thiaca-
lix[4]arene with potential S and N coordination sites (L;
Scheme 1).[54] Through the self-assembly of L and CuCl2·2H2O
(X=Cl and Br), two isostructural CuI MOFs, namely,
[Cu4Cl4L]·CH3OH·1.5H2O (1-Cl) and [Cu4Br4L]·DMF·0.5H2O (1-Br),
are afforded. In 1-Cl and 1-Br, the S and N atoms of the thiaca-
lix[4]arenes and XÀ anions bridge the CuI atoms to give a lay-
ered structure. Remarkably, the CuI MOFs are exceedingly
[b] Dr. X. Xu
College of Chemistry, Chemical Engineering and Materials Science
Key Laboratory of Molecular and Nano Probes, Ministry of Education
Shandong Normal University, Jinan 250014 (P.R. China)
Supporting information and the ORCID identification number(s) for the
author(s) of this article can be found under:
https://doi.org/10.1002/chem.201903966. It contains crystallographic data
in CIF format, H NMR spectra, GC spectra, tables, thermogravimetric
curves, and powder XRD patterns.
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Scheme 1. Synthetic procedure for L.
stable in aqueous solutions over a wide range of pH values.
Significantly, MOFs 1-Cl and 1-Br, as recycled heterogeneous
catalysts, exhibit excellent catalytic capability for click reactions
in water; thus representing a new series of green and efficient
catalysts.
Results and Discussion
Crystal structures of 1-Cl and 1-Br
Crystallographic analysis revealed that 1-Cl and 1-Br were iso-
morphic (Figure S1 in the Supporting Information) and crystal-
lized in the same tetragonal space group, I4(1)/a. Accordingly,
only the crystal structure of 1-Cl is discussed herein. The asym-
metric unit of 1-Cl contains one ClÀ anion, a quarter of L, and
one CuI cation. Each CuI cation shows a tetrahedral coordina-
tion geometry, coordinated by one nitrogen atom from one L
ligand, a sulfur atom from one L ligand, and two ClÀ anions
(Figure 1a). Each pyridyl nitrogen atom is involved in coordi-
nating with one CuI cation with a CuÀN bond length of
2.029 ꢁ. Two ClÀ anions, as bridging nodes, link two adjacent
CuI cations into a [Cu2Cl2] unit (Figure 1a). Meanwhile, adjacent
[Cu2Cl2] units are bridged by L ligands through nitrogen and
sulfur atoms to yield a layered structure with a CuÀS bond
length of 2.3354 ꢁ (Figure 1b). Furthermore, neighboring
layers are held together through a 3.566 ꢁ CÀH···Cl hydrogen
bond (Table S2 in the Supporting Information) to afford a 3D
supramolecular architecture with channel dimensions of about
6.6ꢂ10 ꢁ2 along the crystallographic c axis, in which the meth-
anol and water molecules may be filled (Figure 1c and d). The
total potential solvent-accessible void volume was calculated
by using PLATON to be about 16.5% (911.9 ꢁ3/5532.1 ꢁ3) after
the removal of solvent molecules.[55]‘
Figure 1. a) Coordination environment of CuI in 1-Cl (symmetry code: #1 1Àx,
Ày, 1Àz).[68] b) Layered structure of 1-Cl. c) The 3D hydrogen-bonding supra-
molecular architecture of 1-Cl. d) Packing structure of 1-Cl.
Catalytic studies
ures S2 and S3 in the Supporting Information) are well re-
tained; thus demonstrating their high structural stability.
Based on the stability of 1-Cl and 1-Br, their catalytic proper-
ties for the azide–alkyne cycloaddition (AAC) reactions were
studied. To optimize the reaction conditions, catalytic experi-
ments were conducted with phenylacetylene and benzyl azide
Samples of 1-Cl and 1-Br were immersed in organic solvents
(methanol, ethanol, acetone, DMF, and dimethylacetamide) or
aqueous solutions of different pH ranges for 24 h. As shown in
Figures 2 and 3, the powder X-ray diffraction (PXRD) patterns
indicate that the framework structures of 1-Cl and 1-Br (Fig-
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Table 1. AAC reactions of benzyl azide and phenylacetylene.[a]
Entry
Cat.
Amount [mg]
T [8C]
Solvent
Yield [%][b]
1
2
3
4
5
6
7
8
1-Cl
1-Cl
1-Cl
1-Cl
1-Cl
1-Cl
1-Cl
1-Cl
1-Cl
1-Cl
1-Cl
1-Cl
1-Cl
CuCl
1-Br
0
5
60
60
60
60
30
40
50
60
60
60
60
60
60
60
60
H2O
H2O
H2O
H2O
H2O
H2O
H2O
MeCN
CH2Cl2
EtOH
MeOH
acetone
H2O
14
90
99
99
44
49
90
47
45
92
99
46
99
46
90
10
15
10
10
10
10
10
10
10
10
10
3.2
12
9
10
11
12
13
14
15
H2O
H2O
Figure 2. PXRD patterns of 1-Cl after immersion in aqueous solutions of dif-
ferent pH values.
[a] Reaction conditions: amyl acetate (120 mg, 0.92 mmol), phenylacetyl-
ene (204 mg, 2 mmol), and benzyl azide (133 mg, 1 mmol). [b] The yield
was calculated with amyl acetate as an internal standard.
catalytic yield was up to 99% in water under the same condi-
tions (Table 1, entries 8–13, and Figure S4c and i–m in the Sup-
porting Information). Therefore, water was chosen as a catalyt-
ic reaction medium for the AAC reactions. In addition, if the
amount of catalysts 1-Cl and 1-Br was up to 0.008 mmol, the
conversions reached 99 and 90%, respectively (Table 1, en-
tries 13 and 15, and Figure S4c and s in the Supporting Infor-
mation). Eventually, the catalytic AAC reaction was performed
by using 1-Cl (10 mg) in water at 608C.
Under the optimized conditions, we conducted a kinetic
study with phenylacetylene and benzyl azide as substrates.
The product yield reached 97% after 6 h, and then rose slowly
from 97 to 99% in the following 2 h (Figure 4 and Figure S4n–
q in the Supporting Information). To further study the applica-
Figure 3. PXRD patterns of 1-Cl after immersion in different organic sol-
vents.
as model substrates and 1-Cl as a catalyst at varying tempera-
tures and in different solvents. Initially, the yields of the catalyt-
ic products varied from 40 to 99% (Table 1, entries 5–7 and 13,
and Figure S4e–h in the Supporting Information), with reaction
temperatures changing from 30 to 608C, water as the solvent,
and 1-Cl as a catalyst (10 mg, 0.008 mmol) after 8 h. After the
amounts of 1-Cl were increased from 5 to 15 mg, the corre-
sponding product yields increased from 90 to 99% at 608C in
water (Table 1, entries 2–4, and Figure S4b–d in the Supporting
Information). Notably, in the absence of catalyst 1-Cl, the yield
was only up to 14% after 8 h (Table 1, entry 1, and Figure S4a)
under the same conditions. If CuCl was used as a catalyst, the
yield reached 46% (Table 1, entry 14, and Figure S4r in the
Supporting Information). To explore the solvent effect, catalysis
was carried out in various solvents, including acetonitrile, di-
chloromethane, methanol, acetone, and ethanol. Compared
with that in acetonitrile, acetone, and dichloromethane, the
Figure 4. Catalytic kinetic behavior for the reaction between benzyl azide
and phenylacetylene with catalyst 1-Cl (black) and that in the filtrate after
removal of 1-Cl 2 h after catalysis (red).
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bility of the catalyst, a variety of alkynes and azides with sub-
stituted terminal groups were applied as substrates for the
AAC reactions. The catalytic AAC reactions gave very high con-
versions for all selected substrates (Table 2); thus indicating
cycle, catalyst 1-Cl was recovered by filtration, washed with
methanol, and used in the next cycle of the reaction under the
same conditions. The yield of each run was almost the same
(Figure 5 and Figure S6 in the Supporting Information). Nota-
bly, the PXRD patterns demonstrate that the structural integrity
of 1-Cl remained after each cycle (Figure S7 in the Supporting
Information). The formation of the desired 1,2,3-triazole com-
Table 2. Catalytic reactions of various benzyl azide and phenylacetylene
substrates with catalyst 1-Cl.[a]
1
pounds was confirmed by means of H NMR spectroscopy (Fig-
Entry Azide
Alkyne
Product
Yield
[%][b]
ures S8–S17 in the Supporting Information).
1
2
99
99
3
4
99
99
5
99
99
92
89
97
99
6
7
Figure 5. Conversions obtained in recycling experiments for the AAC reac-
tion with 1-Cl as a catalyst.
8
Notably, catalyst 1-Cl features efficient catalytic performan-
ces for the AAC reactions under relatively mild reaction condi-
tions. For example, the product yield is up to 99% for the AAC
reaction of benzyl azide and phenylacetylene with catalyst
1-Cl at 608C for 8 h. Nevertheless, for related catalysts
9
10
[a] Reaction conditions: azide (1 mmol), 1-Cl (10 mg, 0.008 mmol), alkyne
(2 mmol), and amyl acetate (120 mg, 0.92 mmol), water, 608C, 8 h. [b] The
yield of product isolated was calculated through GC analysis.
[Cu4(SiW12O40)(L1)]·6H2O·2DMF
(L1=resorcin[4]arene-based
ligand)[36] and [Cu4(SiW12O40)(L2)2(DMF)2]·2EtOH·DMF (L2=thia-
calix[4]arene-based ligand),[35b] the same AAC reaction was ac-
complished (99%) if the reaction temperature was elevated to
808C and the reaction time was prolonged to 12 h. In addition,
catalyst 1-Cl features a remarkable recyclability for the AAC re-
action. For instance, a product yield of 97% was still retained
in the fifth run, whereas the corresponding yield for the cata-
lyst {[Cu6(bpz)6(CH3CN)3(CN)3Br]·2OH·14CH3CN}n (bpz=3,3’,5,5’-
tetramethyl-4,4’-bipyrazole) was only up to 68%.[35a] The good
catalytic recyclability of 1-Cl may account for its framework sta-
bility.
that catalyst 1-Cl is effective for substrates with electron- with-
drawing or -donating groups on the phenyl rings (Figure S5a–j
in the Supporting Information). For example, if phenylacety-
lene reacts with benzyl azide derivatives, the yield can reach
99%. If the catalytic reactions of benzyl azide with various phe-
nylacetylene derivatives were performed, slightly lower conver-
sions of about 92 and 89% (Table 2, entries 7 and 8) were
achieved for Cl- and Br-substituted phenylacetylenes, respec-
tively; this may arise due to the steric hindrance effect of the
substituted groups.[36,56]
Moreover, a possible catalytic reaction mechanism was as-
sumed (Scheme 2). CuI-based catalyst 1-Cl possesses a high ac-
tivity for the AAC reaction because of its active CuI sites.[57] The
reaction process mainly involves the generation of CuI–acetyl-
ide product (B) through the interaction of the alkyne with
CuI.[58] Then the product (B; Scheme 2) attacks the azides to
produce intermediate C.[59] Afterward, the N3 atom in C inter-
acts with the C4 atom of the alkyne, forming the CuI–metalla-
cycle (D).[53,60a] In the metallacycle, ring contraction results in
intermediate species E.[56] Finally, catalyst 1-Cl is recovered
with the formation of the target product 1,4-disubstituted
1,2,3-triazole.
The heterogeneous nature of the reaction for phenylacetyl-
ene with benzyl azide was studied in the filtrate (Figure S4t–v
in the Supporting Information). After 2 h of the AAC reaction,
catalyst 1-Cl was filtered. Notably, no clear reaction occurred in
the filtrate under the same conditions (Figure 4). Further, in-
ductively coupled plasma analysis indicates that no catalyst
leaching is observed during the catalytic reaction; thus certify-
ing the heterogeneous nature of the AAC reaction. To probe
the reusability of 1-Cl, the recycled catalytic reactions were ex-
amined by using alkynes and azides as substrates. In each
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Figure 6. Catalytic kinetic curve of 2-(phenoxymethyl)oxirane, sodium azide,
and phenylacetylene with 1-Cl as a catalyst (black) and the filtrate upon re-
moving 1-Cl after 2 h of catalysis (red).
Scheme 2. Proposed mechanism for the AAC reaction with 1-Cl as a catalyst.
Based on the catalytic activity of 1-Cl and 1-Br for the AAC
reactions, three-component epoxy ring-opening reactions of
epoxy derivatives, sodium azide, and phenylacetylene were
also studied. The catalytic experiments were conducted under
the optimized conditions, with 2-(phenoxymethyl)oxirane,
sodium azide, and phenylacetylene as substrates and 1-Cl
(10 mg) as a catalyst in water at 608C for 8 h (Table 3 and Fig-
ure S18a–m, r, and s in the Supporting Information). Notably,
in the absence of 1-Cl, only 13% yield was obtained under the
same reaction conditions (Table 3, entry 1, and Figure S18a in
the Supporting Information). If CuCl was used as a catalyst, the
yield was only up to 34% (Table 3, entry 14, and Figure S18r in
the Supporting Information).
the beginning, to 95% over the next 4 h, and finally up to
99% (Figure S18n–q in the Supporting Information).
To further study the wide application of catalyst 1-Cl, a
series of epoxy and phenylacetylene derivatives were utilized
as substrates for the epoxy ring-opening reactions. As listed in
Table 4, for epoxides with aliphatic or aromatic substituents,
the corresponding cyclic carbonates revealed excellent yields
(Figure S19a–k in the Supporting Information). Phenylacetyl-
ene substrates with electron-withdrawing or -donating groups
gave high conversions. However, a slightly lower conversion of
about 91% was achieved if OCH3-substituted phenylacetylene
was used as a substrate; this may arise from the steric hin-
drance effect of the substituted groups.[56,60b]
The kinetic reaction was explored at different time intervals
under the optimized conditions, with 2-(phenoxymethyl)oxi-
rane, sodium azide, and phenylacetylene as substrates. As
shown in Figure 6, the yields increased rapidly from 65% at
As shown in Figure 6, filtration experiments for 2-(phenoxy-
methyl)oxirane, sodium azide, and phenylacetylene demon-
strate the heterogeneity of the catalytic reaction with 1-Cl as
Table 3. The epoxy ring-opening reaction of 2-(phenoxymethyl)oxirane, sodium azide, and phenylacetylene under various reaction conditions.[a]
Entry
Cat.
Amount [mg]
T [8C]
Solvent
Yield [%][b]
1
2
3
4
5
6
7
8
1-Cl
1-Cl
1-Cl
1-Cl
1-Cl
1-Cl
1-Cl
1-Cl
1-Cl
1-Cl
1-Cl
1-Cl
1-Cl
CuCl
1-Br
0
5
60
60
60
60
30
40
50
60
60
60
60
60
60
60
60
H2O
H2O
H2O
H2O
H2O
H2O
H2O
MeCN
CH2Cl2
EtOH
MeOH
acetone
H2O
13
90
99
99
32
50
90
32
21
65
90
24
99
34
90
10
15
10
10
10
10
10
10
10
10
10
3.2
12
9
10
11
12
13
14
15
H2O
H2O
[a] Reaction conditions: epoxide (1.5 mmol), NaN3 (97.5 mg, 1.5 mmol), and phenylacetylene (1 mmol), water (4 mL), 608C, 8 h. [b] The yield was deter-
mined by means of GC with ethylbenzene as an internal standard.
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Table 4. Catalytic reactions of epoxide derivatives, sodium azide, and phenylacetylenes with substituted groups catalyzed by 1-Cl.[a]
Entry
Azide
Alkyne
Product
Yield [%][b]
1
99
2
3
4
99
95
99
5
6
97
97
7
8
9
99
99
96
10
11
99
91
[a] Reaction conditions: alkyne (1 mmol), 1-Cl (10 mg, 0.008 mmol), epoxide (1.5 mmol), and NaN3 (97.5 mg, 1.5 mmol), water (4 mL), 608C, 8 h. [b] Ethyl-
benzene was used as an internal standard to calculate the yield.
catalyst (Figure S18t–v in the Supporting Information). To
probe the reusability of catalyst 1-Cl, recycled catalyst experi-
ments were examined with NaN3, epoxypropyl phenyl ether,
and phenylacetylene as substrates. In each cycle, catalyst 1-Cl
was recovered by filtration, washed, dried under vacuum, and
then used for the next run under the same conditions
(Figure 7). It is noteworthy that the product yield in the fifth
run was almost the same as that in the first run (Figure S20a–e
in the Supporting Information). Notably, the PXRD patterns
demonstrate the framework integrity of catalyst 1-Cl after each
cycle of catalysis, as shown in Figure S21 in the Supporting In-
formation. The expected product, b-hydroxy-1,2,3-triazole was
also confirmed by means of 1H NMR spectroscopy (Figures
S22–S32 in the Supporting Information).
(4-pyridyl)salicylidene]-1,2-diphenylethylenediame),[61] the cor-
responding yield only reached 77% with identical substrates in
water at 608C for 24 h. The result indicates that 1-Cl is an effi-
cient catalyst for the epoxy ring-opening reaction.
Remarkably, catalyst 1-Cl exhibits high catalytic activity for
epoxy ring-opening reactions relative to that of the known re-
lated MOF.[61] For example, a product yield of 95% was achiev-
ed for catalyst 1-Cl with 2-butyloxirane, sodium azide, and
phenylacetylene as substrates at 608C for 8 h. For the catalyst
[(Cu4I4)2(L3)4]·20DMF·3CH3CN (L3=(R,R)-N,N’-bis[3-tert-butyl-5-
Figure 7. Recycling experiments for the three-component epoxy ring-open-
ing reaction catalyzed by 1-Cl.
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As shown in Scheme 3, a possible mechanism for the three-
component epoxy ring-opening reaction is proposed. Catalyst
1-Cl presents high activity for the epoxy ring-opening reaction
due to its catalytically active CuI species.[62] It is well established
that the phenylacetylene first coordinates with CuI to generate
Conclusion
Two layered CuI MOFs were successfully assembled by using a
thiacalix[4]arene-based ligand with S and N coordination sites.
MOFs 1-Cl and 1-Br are exceedingly stable in aqueous solu-
tions over a wide range of pH values. Most strikingly, they fea-
ture highly effective catalytic activities for click reactions as re-
cycled heterogeneous catalysts. The exposed active CuI sites
and 1D channels in these MOF structures play an important
role in improved catalytic activities. In particular, the catalytic
activities of 1-Cl and 1-Br in water are superior to those in or-
ganic solvents or even in mixed solvents. The results demon-
strate that 1-Cl and 1-Br are suitable for potential applications
as environmentally friendly catalysts. This work provides a new
route for the development of environmentally friendly MOF
catalysts for use in water.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (grant no. 21471029). Theory calculations
were supported by Dr. Shi-Zheng Wen at Huaiyin Normal Uni-
versity and Prof. Hong-Liang Xu at Northeast Normal Universi-
ty.
Scheme 3. Possible mechanism for the epoxy ring-opening reaction with 1-
Cl.
the CuI–acetylide product (B).[63] The a-carbon of the epoxide
À
is attacked by the N3 anion to produce the azide. Afterward,
Conflict of interest
the intermediate (F) interacts with the product (B) to yield an-
other intermediate (G).[64] Intermediate E was achieved through
CÀN bond formation between the end nitrogen of the coordi-
nated azide and the b-carbon of CuI–acetylide.[50,65] Intermedi-
ate H results from the ring contraction of intermediate E. Even-
tually, the CuI catalyst was recovered after protonolysis with
formation of the final product, b-hydroxy-1,2,3-triazole.
The authors declare no conflict of interest.
Keywords: click chemistry · green chemistry · heterogeneous
catalysis · metal–organic frameworks · thiacalixarenes
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MOF 1-Cl is an effective catalyst for click reactions toward
the substrates used.[36] The open MOF structure plays a key
role in the improved catalytic efficiency. To understand the cat-
alytic reaction environment, DFT simulations were carried out
for the diffusion and interaction of phenylacetylene with the
CuI site in the channels of 1-Cl (Figures S33–S35 in the Sup-
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ÝÝ These are not the final page numbers!

Full Paper
FULL PAPER
Going green: Copper(I)–thiacalix[4]ar-
ene-based frameworks are investigated
as stable, recyclable heterogeneous cat-
alysts for the click reaction in water. The
metal–organic framework structures, es-
pecially exposed active CuI sites and 1D
channels, play a key role in the im-
&
Metal–Organic Frameworks
X.-X. Wang, J. Yang, X. Xu, J.-F. Ma*
&& – &&
Highly Stable Copper(I)–
Thiacalix[4]arene-Based Frameworks
for Highly Efficient Catalysis of Click
Reactions in Water
proved catalytic activities (see scheme).
Chem. Eur. J. 2019, 25, 1 – 9
www.chemeurj.org
9
ꢀ 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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These are not the final page numbers! ÞÞ