A Nanosized Propeller-like Polyoxometalate-linked Copper(I)-Resorcin[4]arene for Efficient Catalysis

Article abstract of DOI:10.1021/acs.inorgchem.0c02404

The design and assembly of polyoxometalate-resorcin[4]arene-based metal-organic molecular materials are particularly attractive for their elegant structures and potential functions. By applying a newly designed resorcin[4]arene ligand (TPC4R-II), a copper(I)-coordinated polyoxometalate-based metal-organic molecular material, namely, [CuI6(Br)3(TPC4R-II)3(PMo12O40)]·8H2O (1), was rationally assembled. Three copper(I)-coordinated resorcin[4]arenes are held together by a central [PMo12O40]3- to yield a supramolecular propeller. 1 features efficient catalytic performances for oxidation desulfurization (ODS) and azide-alkyne cycloaddition (AAC) reactions. This work affords a feasible method for the nanosized polyoxometalate-based metal-resorcin[4]arene assemblies by well combinating two types of large composites as well as low coordination metal cations.

Full text of DOI:10.1021/acs.inorgchem.0c02404

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A Nanosized Propeller-like Polyoxometalate-linked Copper(I)-
Resorcin[4]arene for Efficient Catalysis
Yan-Ling Xiong,† Ming-Yue Yu,† Ting-Ting Guo, Jin Yang,* and Jian-Fang Ma*
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ABSTRACT: The design and assembly of polyoxometalate-resorcin[4]-
arene-based metal−organic molecular materials are particularly attractive for
their elegant structures and potential functions. By applying a newly
designed resorcin[4]arene ligand (TPC4R-II), a copper(I)-coordinated
polyoxometalate-based metal−organic molecular material, namely,
[CuI6(Br)3(TPC4R-II)3(PMo12O40)]·8H2O (1), was rationally assembled.
Three copper(I)-coordinated resorcin[4]arenes are held together by a
central [PMo12O40]3− to yield a supramolecular propeller. 1 features
efficient catalytic performances for oxidation desulfurization (ODS) and
azide−alkyne cycloaddition (AAC) reactions. This work affords a feasible
method for the nanosized polyoxometalate-based metal-resorcin[4]arene
assemblies by well combinating two types of large composites as well as low
coordination metal cations.
of Keggin-type [PMo12O40]3−, TPC4R-II, and CuBr2 affords a
new metal−organic molecular material, namely,
[CuI6(Br)3(TPC4R-II)3(PMo12O40)]·8H2O (1). Remarkably,
the central [PMo12O40]3− anion bridges three copper(I)-
coordinated resorcin[4]arenes to produce a unique supra-
molecular propeller. 1 as a heterogeneous catalyst features
highly effecient catalytic activities for oxidation desulfurization
(ODS) and azide−alkyne cycloaddition (AAC) reactions.
INTRODUCTION
■
Polyoxometalates (POMs), a unique family of polynuclear
metal−oxygen clusters,1,2 exhibit compositional varieties and
extensive applications in magnetism, material science, electro-
chemistry, and catalysis.3−10 In this regard, POMs-based
metal−organic supramolecular assemblies have attracted
great attention for their fascinating structural diversities and
potential functions.11 It is well-known that suitable organic
ligands act as a significant role in the construction of POMs-
based metal−organic supramoleculers.12−14 In this facet,
functionalized calix[4]arenes with potential coordination
features are excellent candidates for building the POMs-
based metal−organic supramolecular materials.15
As an important subfamily of calix[4]arenes, resorcin[4]-
arenes with bowl-shaped cavities can be modified by
substituents, making them versatile organic ligands.16−21
Over the past several years, we have engaged in the elaborate
design and synthesis of the functionalized resorcin[4]-
arenes.22−31 By applying the resorcin[4]arenes as organic
linkers, some coordination materials with elegant structures
and functions were successfully obtained.22−31 However, it still
remains exceedingly difficult to assemble POMs-resorcin[4]-
arene-based metal−organic supramolecular materials because
of the well matching combination of two types of large
composites.15,25,26 To our knowledge, there is no report of a
discrete propeller-like supramolecular assembly based on
POMs-linked metal-resorcin[4]arenes.25,26
RESULTS AND DISCUSSION
■
Crystal Structure of [CuI6(Br)3(TPC4R-II)3(PMo12O40)]·
8H2O (1). Brown crystals of 1 were prepared by solvothermal
reaction of H3PMo12O40·xH2O, TPC4R-II, and CuBr2.
Crystallographic determination shows that 1 crystallizes in
monoclinic space group C2/c with a = 38.7877(18) Å, b =
22.1834(7) Å, c = 23.4775(14) Å, and β = 104.463(5)° (Table
S1). The asymmetric unit of 1 consists of three Cu(I) cations,
one-and-a-half Br− anions, one-and-a-half TPC4R-II ligands,
and a half [PMo12O40]3− anion (Figure 1a). The Cu(I) cations
show three different coordination environments, i.e., Cu1 or
Cu3 is four-coordinated by two nitrogen atoms of one TPC4R-
II, one Br− anion, and one terminal oxygen of one
[PMo12O40]3− in a tetrahedral [CuN2OBr] coordination
Received: August 11, 2020
Here, a new resorcin[4]arene with four 2-mercaptopiper-
idine substituents (TPC4R-II) was successfully designed
(Scheme 1), which exhibits semiflexibility around the −S−
groups when coordinated with metal cations.15,25 Self-assembly
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Scheme 1. Synthetic Procedure for [CuI6(Br)3(TPC4R-II)3(PMo12O40)]·8H2O (1)
Figure 1. (a) View of the copper(I)-coordinated metal−organic supramolecular propeller constructed from one POM and three
resorcinol[4]arenes. (b) View of the C−H···O hydrogen-bonded supramolecular layer constructed from supramolecular propellers.
Scheme 2. Schematic Drawing of Oxidation Desulfurization
for MBT
Table 1. ODS Reactions with Catalyst 1 under Different
Conditions
a
b
entry catalyst oxidant time (h) temperature (°C) conversion (%)
1
2
3
4
5
6
7
1
1
none
1
1
1
1
none
H2O2
3
3
3
3
1
2
3
40
40
40
25
40
40
40
6
54
20
41
47
71
99
TBHP
TBHP
TBHP
TBHP
TBHP
geometry, while Cu2 is two-coordinated with one Br− anion
and one N atom from one TPC4R-II ligand in a linear
[CuNBr] coordination mode. Cu1 and Cu2 are held together
by one Br− anion to produce a Cu(I) dimer with Cu−Br bond
distances of 2.218 and 2.128 Å, respectively (Table S2). Three
TPC4R-II ligands reveal two different coordination modes, i.e.,
one TPC4R-II ligand bridges two Cu(I) cations through four
pyrimidine groups, while each of the two remaining TPC4R-II
a
b
Sulfide (0.4 mmol) and CH2Cl2 (5 mL). Yield based on HPLC
with biphenyl as the internal standard.
B
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a
Table 2. Selective ODS of Various Sulfides with 1 as the Catalyst and TBHP as the Oxidant in CH2Cl2
a
b
Reaction conditions: TBHP (135 mg, 1.5 mmol), substrate (0.4 mmol), CH2Cl2 (5 mL), and 1 (30 mg, 0.0051 mmol). The biphenyl was
selected as an internal standard, and the conversion was recorded by GC or HPLC.
ligands coordinates with two Cu(I) cations via three
pyrimidine moieties. It is interesting to note that three
Cu(I)-coordinated TPC4R-II ligands are linked by one
[PMo12O40]3− anion to produce a remarkable propeller-like
supramolecular motif with Cu−O bond disances of 2.553 and
2.735 Å, respectively. The overall dimension of the supra-
molecular propeller is ca. 3 × 3 × 3 nm3. Notably, to our
knowledge, 1 represents the first crystallographic example that
three resorcinol[4]arenes are linked together by one POMs via
copper(I) cations.15,25 It is noted that adjacent supramolecular
propellers are further interlinked by weak C−H···O hydrogen
bonds (C21···O33#2 = 3.377(14) Å, C70···O28 = 3.389(15) Å;
∠C21−H21B···O33#2 = 157.9, and ∠C70−H70A···O28 =
155.0#2, −x + 1/2, y − 1/2, −z + 1/2) to give a supramolecular
network (Table S3 and Figure 1b).
C
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shown in Scheme 2. When the ODS reaction was performed
without the oxidant, a trace of product was obtained (entry 1
in Table 1, Figure S2a). The conversion of MBT was greatly
enhanced when the H2O2 was replaced by tert-butly hydro-
peroxide (TBHP) as oxidant (entry 2 in Table 1, Figure S2b),
thus indicating that the oxidant TBHP acts as a key role in the
ODS reaction.35−37 When the catalytic reaction was performed
in the absence of 1, the conversion was only up to 20% within
3 h (entry 3 in Table 1, Figure S2c). Nevertheless, only 41%
conversion of MBT was achieved within 3 h using TBHP as
the oxidant and 1 as the catalyst at 25 °C (entry 4 in Table 1,
Figure S2d). The corresponding conversion of MBT reached
up to 99% within 3 h with the increased reaction temperatures
from 25 to 40 °C (entries 5−7 in Table 1, Figures S2e−S2g).
Thereby, the following catalytic reactions were carried out with
TBHP as the oxidant and 1 as the catalyst at 40 °C for 3 h.
Further, the ODS was investigated with a wide range of
substrates under the same condition. As illustrated in Table 2,
the substrates with electron-withdrawing and -donating groups
were selected in the ODS process. The substrates MBT and
ethylphenyl sulfide with electron-donating moieties could be
completely converted into the catalytic products within 3 h
(entries 1 and 2 in Table 2, Figure S3a). For the allylphenyl
sulfide and 4-methoxythioanisole, the conversions are up to
99% within 2 h (entries 3 and 4 in Table 2, Figures S3b and
S3c), respectively. The conversions also can reach to 99% for
the weak electron-withdrawing substrates such as 4-chlor-
othioanisole and 4-bromothiaonisole within 3 h (entries 5 and
6 in Table 2, Figures S3d and S3e). However, within 5 h the
conversion was up to 99% for 4-nitrothioanisole containing an
electron-withdrawing group (entry 7 in Table 2, Figure S3f).
The catalytic oxidation conversion is ca. 99% within 5 h when
the diphenyl sulfide was used as the substrate (entry 8 in Table
2, Figure S3g). However, for the substrates with rich aromatic
species such as dibenzothiophene (DBT) and 4,6-dimethyldi-
benzothiophene (4,6-DMDBT), only 70% and 74% con-
versions were obtained after 12 h (entries 9 and 10 in Table 2,
Figures S3h and S3i), respectively. Obviously, the catalytic
reactions of sulfur ethers are easier than the species of
thiophenes in the ODS reactions, which may account for the
strong antioxidant characters of DBT and 4,6-DMDBT.38−40
Noticeably, the catalytic ODS activity of 1 is comparable to
those of known POMs-based metal−organic heterogeneous
catalysts. For example, the conversion of MBT catalyzed by 1
is up to 99% at 40 °C within 3 h, while the MBT could be
completely converted to the corresponding products with
Mo8O264−@2 (0.2 equiv) and (Mo6O192−)2@2 (0.1 equiv) (2
= Pd4L2-type nanocapsule) as catalysts at the increased
temperature (60 °C) within the prolonged reaction time (9
h).35 For catalyst [Ag4(PMo12O40)(L)2]·OH (L = thiacalix[4]-
arene-based ligand), the similar catalytic oxidation of MBT was
accomplished at the same temperature within the prolonged
reaction time (4 h).25 In addition, we also compared the
catalytic performance of 1 with the reported Zr6(μ3−
OH)8(OH)8(TBAPy)2 (H4TBAPy = 1,3,6,8-tetrakis(p-benzoic
acid)pyrene). In contrast, about 80% of MBT was converted to
the product with Zr6(μ3−OH)8(OH)8(TBAPy)2 as catalyst
and H2O2 as oxidant at the raised temperature (60 °C) within
the same reaction time (3 h).41 Evidently, 1 shows superior
catalytic performance for the ODS reaction.
Figure 2. Conversion curve of the ODS reaction of 4-nitrothioanisole
with 1 as catalyst.
Figure 3. Recycling experiments for the ODS reactions of MBT in the
presence of 1 and TBHP.
Table 3. AAC Reactions of Phenylacetylene and Benzyl
a
Azide under Different Conditions
b
entry catalyst 1 (mg) temperature (°C)
solvent
conversion (%)
1
2
3
4
10
10
none
10
25
40
60
60
CH3OH
CH3OH
CH3OH
CH3OH
26
49
16
99
a
Amyl acetate (120 mg, 0.92 mmol), phenylacetylene (204 mg, 2
mmol), reaction time (24 h), and benzyl azide (133 mg, 1 mmol).
b
The conversion was determined by GC.
Scheme 3. Schematic Drawing of the Typical AAC Reaction
Catalytic Oxidation Desulfurization (ODS). The crystals
of 1 were stable in air. Before the catalytic reaction, the sample
of 1 was immersed in water for 24 h. The PXRD patterns
correspond to the simulated one (Figure S1). Considering the
stability of POM-based 1, the catalytic ODS reaction was
explored using 1 as catalyst.25,32−34 In an initial investigation
on the ODS, methyl phenyl sulfide (MBT) was used as the
model substrate to obtain the optimum reaction condition, as
Moreover, the ODS dynamics for 4-nitrothioanisole were
studied with 1. The resulting product was measured every 1 h
(Figure S4). The conversions of 4-nitrothioanisole were
D
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a
Table 4. Azide−Alkyne Cycloaddition Reactions with Catalyst 1
a
Reaction conditions: reaction time (24 h), amyl acetate (120 mg, 0.92 mmol), azide derivative (1 mmol), reaction temperature (60 °C), alkyne (2
b
mmol), and 1 (30 mg, 0.0051 mmol). The conversion was calculated by GC.
enhanced drastically (82% within 3 h) and varied from 82% to
99% in the following 2 h (Figure 2), demonstrating that the
catalytic ODS reaction almost finished at the beginning of 3 h.
Additionally, the recycled experiments for the ODS reactions
of MBT were also investigated with 1 as the catalyst (Figure
3). After catalysis, 1 was separated and reused for the next
cycle (Figures S5 and S6). Noticeably, the conversions were
well maintained after five cycles, demonstrating the good
reusability of 1 (Figure S7).
A possible mechanism of the ODS reaction was proposed.42
The Mo atom was attacked by TBHP to produce
peroxomolybdic active species,15 which further oxidized the
E
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reactions of the benzyl azide with various substituted
ethynylbenzenes were also studied. When the benzyl azide
reacts with ethynylbenzenes possessing electron-withdrawing
substituents, including -F, -Cl, -Br, and -CN, the conversions
after 24 h are only up to 92%, 88%, 73%, and 80% (entries 6−9
in Table 4, Figures S17e−S17h), respectively. Nevertheless,
when the substrates with electron-donating substituents were
used in the reaction system, the 4-methylphenylacetylene and
4-methoxyphenylacetylene were completely converted into the
products (entries 10 and 11 in Table 4, Figures S17i and S17j).
The results further demonstrate that the catalytic efficiencies
for alkynes and azides are highly dependent on the electron-
donating or -withdrawing groups of the substrates. Notably, 1
features higher catalytic activities than those of related
copper(I)-resorcin[4]arene-based heterogeneous catalysts.25
Further, the AAC reaction dynamics were also investigated.
The reaction of benzyl azide and phenylacetylene was
measured using catalyst 1 at 60 °C for 24 h. The conversion
was determined every 4 h in the study of the catalytic
processes. As illustrated in Figure 4, the conversion of the
substrate reached 86% after 16 h. After 24 h, the substrate was
completely converted to the catalytic product (Figures S18a−
S18f).
In addition, the catalytic AAC performance of 1 has been
compared with the reported catalysts. In this work, the 99%
conversion was achieved for the reaction between benzyl azide
and phenylacetylene at 60 °C for 24 h (entry 4 in Table 3). In
contrast, only 51.3% of the corresponding substrates was
converted to the product at the increased temperature (100
°C) within the same reaction time when complex [Cu(H2L1)-
(H2O)2]·2H2O (L1 = arylhydrazone-benzenesulfonate-based
ligand) was used as the catalyst.52 The result reveals that 1
shows the efficient catalytic performance for the AAC reaction.
Figure 4. AAC reaction dynamics of phenylacetylene and benzyl azide
with catalyst 1.
sulfurs to form the corresponding sulfoxides.15 Meanwhile, the
[PMo12O40]3− anion was recovered.26
Azide−Alkyne Cycloaddition (AAC) Reaction. The
AAC reaction, as one representative case of “click chemistry”,
has received attractive attention owing to its extensive
utilization in pharmaceutical chemistry and organic syn-
thesis.43−46 Based on the active Cu(I) species, the heteroge-
neous AAC reactions were explored with 1 as the catalyst. The
catalytic experiment was performed via the one-pot reaction of
phenylacetylene and benzyl azide.47,48 Before the catalytic
reaction, the sodium azide reacts with benzyl chloride to
produce benzyl azide in situ. Then, the reaction between the
resulting benzyl azide and phenylacetylene generates catalytic
triazole products (Figures S8−S15).49−51 The conversions
were determined by GC with internal standard amyl acetate. At
the beginning, the optimization of the AAC reaction was
evaluated carefully (Table 3). As shown in Scheme 3, when the
AAC reaction of benzyl azide and phenylacetylene was
conducted with 1 (10 mg, 0.0017 mmol) at 25 °C in
CH3OH for 24 h, only 26% conversion was achieved (entry 1
in Table 3, Figure S16a). With the elevating temperatures from
25 °C through 40 to 60 °C, the final conversion reached up to
99% for 24 h (entries 2 and 4 in Table 3, Figures S16b and
S16c).
Moreover, the AAC reactions catalyzed by 1 were further
studied with different substrates. For instance, various terminal
alkyne derivatives (such as methoxy-, cyano-, halogen, and
methyl moieties) and benzyl azides with substituted moeties
(including cyano-, methoxy-, methyl, and halogen moieties)
were selected as substrates to explore the AAC reactions.
Noticeably, the catalytic reaction is greatly efficient with
quantitative conversions of the substituted 1,2,3-triazole
products, as illustrated in Table 4. First, the AAC reactions
of alkyne and various azides were explored. The results indicate
that the electron-withdrawing or -donating moeties on the
azides have an effective influence on the AAC reaction with 1
as the catalyst. For example, the conversion was up to 99%
when the ethynylbenzene reacts with the electron-withdrawing
4-cyanobenzyl azide or 2-fluorobenzyl azide within 24 h
(entries 4 and 5 in Table 4, Figures S17a and S17b).
Nevertheless, the reactions of the electron-donating 3-
methylbenzyl azide and 4-methylbenzyl azide with ethynyl-
benzene only afford 84% and 86% conversion yields,
respectively, under the same condition (entries 2 and 3 in
Table 4, Figures S17c and S17d). Second, the catalytic
CONCLUSIONS
■
In summary, a new nanosized propeller-like supramolecular
motif was successfully constructed from POMs, resorcin[4]-
arenes, and copper(I) cations. Remarkably, 1 is highly stable
and features active POMs and Cu(I) sites, making it an
efficient heterogeneous catalyst for the catalytic ODS and AAC
reactions. This work affords a general strategy to design and
synthesize the new nanosized metal−organic supramolecular
motifs by combining different functionalized large composites
of POMs and resorcin[4]arenes as well as low coordination
metal cations.
ASSOCIATED CONTENT
■
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* Supporting Information
The Supporting Information is available free of charge at
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Experimental section, GC spectra, HPLC spectra, tables,
1
crystallographic data, and H NMR spectra (PDF)
Accession Codes
CCDC 2020779 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
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AUTHOR INFORMATION
■
Corresponding Authors
Jin Yang − Key Lab for Polyoxometalate Science, Department of
Chemistry, Northeast Normal University, Changchun 130024,
China; Email: yangj808@nenu.edu.cn
Jian-Fang Ma − Key Lab for Polyoxometalate Science,
Department of Chemistry, Northeast Normal University,
Changchun 130024, China; orcid.org/0000-0002-4059-
8348; Email: majf247@nenu.edu.cn; Fax: +86-431-
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Authors
Yan-Ling Xiong − Key Lab for Polyoxometalate Science,
Department of Chemistry, Northeast Normal University,
Changchun 130024, China
Ming-Yue Yu − Key Lab for Polyoxometalate Science,
Department of Chemistry, Northeast Normal University,
Changchun 130024, China
Ting-Ting Guo − Key Lab for Polyoxometalate Science,
Department of Chemistry, Northeast Normal University,
Changchun 130024, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.inorgchem.0c02404
Author Contributions
†These authors contributed equally.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported by the National Natural Science
Foundation of China (21771034 and 21471029).
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