Self-Assembled Polyoxometalate-Based Metal-Organic Polyhedra as an Effective Heterogeneous Catalyst for Oxidation of Sulfide

Article abstract of DOI:10.1021/acs.cgd.0c01375

Two polyoxovanadate-based metal-organic polyhedra with octahedral (oct) and rhombic dodecahedral (rdo) geometries have been constructed from a concave molecular building block and linear and triangular carboxylate ligands. VMOP-7 is constructed from {V5O9Cl} SBU and a linear anthracene-9,10-dicarboxylic acid ligand in which all the anthracene groups are perpendicular to the edge of the octahedron. Such an arrangement mode can effectively reduce the steric hindrance between ligands. VMOP-8 is constructed from {V5O9Cl} SBU and a triangular biphenyl 3,4,5-tricarboxylate ligand, which exhibits an elongated rhombic dodecahedral configuration due to the geometry of the ligand. Furthermore, VMOP-8 can serve as a heterogeneous catalyst and exhibits efficient and common catalytic activity for oxidative desulfurization.

Full text of DOI:10.1021/acs.cgd.0c01375

pubs.acs.org/crystal
Article
Self-Assembled Polyoxometalate-Based Metal-Organic Polyhedra as
an Effective Heterogeneous Catalyst for Oxidation of Sulfide
Hong-Mei Gan, Chao Qin, Liang Zhao,* Chunyi Sun, Xing-Long Wang,* and Zhong-Min Su*
Cite This: Cryst. Growth Des. 2021, 21, 1028−1034
Read Online
sı
*
Metrics & More
Article Recommendations
Supporting Information
ACCESS
ABSTRACT: Two polyoxovanadate-based metal-organic polyhe-
dra with octahedral (oct) and rhombic dodecahedral (rdo)
geometries have been constructed from a concave molecular
building block and linear and triangular carboxylate ligands.
VMOP-7 is constructed from {V5O9Cl} SBU and a linear
anthracene-9,10-dicarboxylic acid ligand in which all the
anthracene groups are perpendicular to the edge of the octahedron.
Such an arrangement mode can effectively reduce the steric
hindrance between ligands. VMOP-8 is constructed from
{V5O9Cl} SBU and a triangular biphenyl 3,4,5-tricarboxylate
ligand, which exhibits an elongated rhombic dodecahedral configuration due to the geometry of the ligand. Furthermore, VMOP-8
can serve as a heterogeneous catalyst and exhibits efficient and common catalytic activity for oxidative desulfurization.
vertices to form MOPs by connecting organic linkers are
composed of {(VO)3(OMe)4} (V3-SBU, 3-v);21 {V4O8Cl}
(V4-SBU, 4-v);22,23 {V5O9Cl} (V5-SBU, 4-v);23−25 {V6O6-
(OMe)9SO4} (V6-SBU, 3-v);26−30 {V7O9(OMe)9SO4} (V7-
SBU, 3-v);31 and {V6O11(SO4)(CO2)5} (VV5-SBU, 5-v)6,32
(SBU with n extension points is referred to as n-valent) (Figure
1). In 2001, Hartl et al. synthesized the first cubic VMOP with
V3-SBU.21 Subsequently, Zaworotko and co-worker reported
several organic-inorganic hybrid nano-balls based on V4- or V5-
SBU, and our group also reported a series of truncated
octahedrons based on V5-SBU.23 Inspiringly, rare icosahedrons
based on VV5-SBU have been successfully designed and
synthesized recently.6,32 Combining with the theory of reticular
chemistry and these elegant architectures, more novel VMOPs
can be predicted and designed. Among these polyoxovanadate-
based SBUs, the angle η of V5-SBU can be observed to change
flexibly in the range of 55−61°. Therefore, V5-SBU still has
greater potential to construct more VMOPs. Over the past
decade, the self-assembly synthesis of VMOPs has made initial
achievements, but all previous efforts have focused on the
characteristics of attractive geometric cavities and unique
stacking networks, where the size-matched cavities or unique
pores can encapsulate fullerene guest molecules or selectively
adsorb cationic dyes. Besides, a tetrahedron has permanent
INTRODUCTION
■
As a new type of inorganic-organic hybrid material, metal-
organic polyhedra (MOPs) have attracted extensive interests
because of their single-molecular properties, which are
different from the classic crystalline MOFs with infinite
structures.1−6 MOPs have been applied in many fields as a
new tpye of supramolecular aggregation, such as chiral
separation,7,8 biomedical,9,10 catalysis,11,12 host−guest chem-
istries,13−17 etc. However, due to the scarcity of suitable
molecular building blocks, the target synthesis of MOPs with
the predictable structure is still a challenge in crystal
engineering.6 Unlike MOFs, the secondary building unit
(SBU) used to construct MOPs required to be expanded in
a controllable direction; that is to say, the SBU must have a
specific curvature.18,19 Encouragingly, O’Keffee and Yaghi
summarized some typical geometries of MOPs from the
topological perspective.1 Such an excellent analysis based on
reticular chemistry provides a theoretical basis for the design
and synthesis of MOPs. This theory involves simplifying the
SBUs into topological polygons and connecting them through
linkers to form a closed polyhedron, also giving two critical
angles to characterize the geometries of the polyhedra. One is
the angle η between the expansion directions in the SBUs, and
the second is the bending angle θ of the ditopic linkers.
However, since there are no advantages in the number of
examples that can be referenced, it is still difficult to find
suitable SBUs that meet the conditions for constructing MOPs.
Polyoxovanadates (POVs), formed by sharing edges or
vertices of the VOx (x = 5 or 6) triangular bipyramid or
octahedron, are a promising kind of metal−oxygen SBU to
construct MOPs due to the diversity of coordination.20 So far,
the reported polyoxovanadate-based SBUs that can be used as
Received: October 5, 2020
Revised: December 10, 2020
Published: January 6, 2021
https://dx.doi.org/10.1021/acs.cgd.0c01375
Cryst. Growth Des. 2021, 21, 1028−1034
© 2021 American Chemical Society
1028

Crystal Growth & Design
pubs.acs.org/crystal
Article
room temperature, green crystals were obtained (washed with
MeOH) with a yield of 58% based on H3BPT. Anal. Calcd: C,
29.56; H, 1.15; N, 3.09. Found: C, 29.97; H, 1.26; N, 3.87. IR (KBr,
cm−1): 3029 (br), 1714 (w), 1657 (w), 1609 (m), 1542 (w), 1484
(s), 1448 (m), 1413 (s), 1288 (w), 1114 (w), 986 (vs), 859 (w), 759
(w), 722 (s), 632 (m).
Single-Crystal X-ray Structure Determination of the
VMOPs. The crystallographic data and structural refinements are
given in Table S1. Intensity data were collected at 298 K on a Bruker
D8 VENTURE with Mo Kα radiation (λ = 0.71073 Å) for the
VMOP-8 crystal sample and Cu Kα radiation (λ = 1.5418 Å) for the
crystallographic VMOP-7. The data were collected using the program
APEX 3 and processed using the program SAINT routine in APEX 3.
The structures were solved by direct methods with OLEX-2 and
refined by full-matrix least-squares techniques with the SHELXL-2014
program. The countercations or disordered solvents cannot be
accurately assigned from the weak reflections. Thus, the SQUEEZE
routine in PLATON was applied in order to model the diffuse
electron density caused by disordered dimethylamine molecules and
solvents. The restrained DFIX, SIMU, and ISOR instructions were
used to make the structures more reasonable.
Catalytic Oxidative Desulfurization. 70% tert-butyl hydro-
peroxide (TBHP) (128.7 mg, 1 mmol) and substrate (0.4 mmol)
were added into a 15 mL round-bottom flask with 5 mL of methanol,
and VMOP-8 (10 mg, 0.002 mmol) was added as the catalyst. The
reaction system was kept at room temperature or 50 °C for 1−12 h
with stirring. The conversion rate of methyl phenyl sulfide (MBT)
was detected by gas chromatography (GC), and the remaining
substrates were detected by high performance liquid chromatography
(HPLC). The corresponding sulfoxide and sulfone products were
identified by Fourier transform infrared (IR) spectra.
Figure 1. Structures of the reported polyoxovanadate-based SBUs
(SBUs with n extension points are referred to as n-valent).
porosity for selective gas adsorption.33 However, the
anticipative typical resistance to oxidation and flexible redox
states probably caused by POVs as the important subcompo-
nents in VMOPs are still undeveloped.
In recent years, acid rain has caused great harm to the
environment and is mainly caused by sulfur oxides (SOx)
produced by the combustion of sulfur-containing fuels.34,35
Therefore, reducing the sulfur content in fuels has become an
urgent issue to be solved.36,37 Oxidative desulfurization (ODS)
has received a great deal of attention as a potential solution,
which can convert oxidized sulfides into easily removable
sulfones and sulfoxides.38−40 As far as we know, the catalytic
oxidation performance has never been studied in the reported
VMOPs, so it makes sense to design and synthesize new
VMOPs as the heterogeneous catalysts for sulfide oxidation.
On the basis of the above, the V5-SBU is used as an extension
point to successfully construct two new VMOPs (NH2Me2)12-
[(V5O9Cl)6(L)n]·[MeOH]m, VOMP-7 (L = H2ADC: anthra-
cene-9,10-dicarboxylic acid, n = 12, m = 11) and VMOP-8 (L
= H3BPT: biphenyl 3,4,5-tricarboxylate, n = 8, m = 7), by
connecting with the linear ligand H2ADC and a 3-connected
ligand H3BPT. Remarkably, VMOP-8 also exhibits excellent
catalytic activity for the oxidative desulfurization.
RESULTS AND DISCUSSION
■
Structures of VMOP-7 and VMOP-8. Single-crystal X-ray
diffraction analysis revealed that VMOP-7 crystallized in
tetragonal space group P42/n, while VMOP-8 crystallized in
the tetragonal system with space group I4/mmm. The phase
purities of VMOP-7 and 8 were confirmed by comparison of
the observed and calculated powder X-ray diffraction (PXRD)
patterns (Figure S1). The molecular size of VMOP-7 is about
25 × 25 × 25 Å3 and 22 × 22 × 31 Å3 for VMOP-8 (Figure
S2). In these two cage structures, the {V5O9Cl} cluster, as the
primary secondary building block, is formed by five vanadium
atoms with two coordination modes by sharing the edges of
the polyhedra centered on the V atom (Figure 2). One
EXPERIMENTAL SECTION
■
Synthesis of VMOP-7. In a solvothermal synthesis, VOSO4·xH2O
(0.03 g, 0.18 mmol), VCl4 (0.02 g, 0.10 mmol), and H2ADC (0.02 g,
0.007 mmol), were dissolved in a 3 mL mixture of DMF (N,N-
dimethylformamide), MeCN (acetonitrile), and MeOH (methanol)
(4:1:1, v/v/v), which was transferred to a Teflon-lined stainless steel
vessel and heated to 130 °C for 48 h. After slowly cooling to room
temperature, the green block crystals were obtained through filtering
and washing with MeOH several times with a yield of 37% based on
H2ADC. Anal. Calcd: C, 39.89; H, 1.66; N, 2.65. Found: C, 39.71; H,
1.78; N, 2.93. IR (KBr, cm−1): 3066 (br), 1701 (s), 1624 (vs), 1596
(m), 1538 (w), 1445 (s), 1329 (s), 1283 (m), 1001 (m), 901 (m),
821 (m), 789 (w), 728 (w), 675 (s), 597 (m), 522 (s).
Figure 2. Structure of {V5O9Cl} (V5-SBU) and the coordination
mode of vanadium atoms. Four {VO5Cl} octahedra share the
quadrangled edge with the {VO5} apex to form the V5-SBU.
vanadium V1 atom is coordinated with five oxygen atoms to
form a tetragonal pyramidal {VO5} cluster in which the V−O
bond distances range from 1.577 to 1.886 Å. The other four
vanadium atoms form six-coordinate octahedral {VO5Cl}
clusters, and their bond distances between vanadium atoms
and oxygen atoms are between 1.573 and 2.027 Å (Table S2).
Synthesis of VMOP-8. The mixture of VOSO4·xH2O (0.03 g,
0.18 mmol), VCl4 (0.02 g, 0.10 mmol), and (H3BPT) (0.02 g, 0.007
mmol) was dissolved in 2 mL of DMF (N,N-dimethylformamide), 0.3
mL of MeOH, and 0.2 mL of MeCN and transferred to a Teflon-lined
stainless steel vessel heated to 130 °C for 48 h. After slowly cooling to
1029
https://dx.doi.org/10.1021/acs.cgd.0c01375
Cryst. Growth Des. 2021, 21, 1028−1034

Crystal Growth & Design
pubs.acs.org/crystal
Article
Overall bond valence sum (BVS) calculations indicate that the
V1 ion in the center apex is +5, while the remaining four V2
ions at the bottom are +4, and this result is consistent with
previous reports (Tables S2 and S3).25 Each {V5O9Cl} cluster
is coordinated with four carboxylate ligands, generating a four-
connected vertex. Six {V5O9Cl} vertexes are further bridged by
eight organic ligands, thereby affording an octahedron
(VMOP-7) and a rhombic dodecahedron (VMOP-8). The
12 negative charges are balanced by dimethylamine cations
(H2NMe2)+ (the byproduct of in situ decomposition of DMF
molecules), which can be confirmed by the swell peaks near
3500 cm−1 in the IR spectra and TGA curves (Figures S3, S4).
For VMOP-7, each cage is composed of 250 atoms, including
6 V5-SBUs and 12 H2ADC ditopic linkers. When the V5-SBUs
are regarded as quadrilateral faces, both of the polyhedra
display similar truncated octahedral geometries (Figure 3).
shown in Figure S5a, therein each molecule is arranged in the
closest stacking mode along crystallographic axes, and the
distance between the two adjacent molecules is 21 Å (Figure
S5b). However, the packing structure of VMOP-7 is different
from that of VMOP-8. Three crystal axes are not perpendicular
to each other, and the distance between two adjacent
molecules is 23 Å (Figure S6).
In order to understand the configuration of the two VMOPs
in-depth, the topological analysis is applied to the analysis of
the two structures. As shown in Figure 5, if each V5-SBU is
Figure 3. Self-assembly of VMOPs from tetragonal V5-SBUs and
linear or triangular ligands. Simplified polyhedral diagrams clearly
show two different windows. Triangular recessed windows for
VMOP-7 (left); rectangular windows for VMOP-8 (right).
However, in order to reduce the steric hindrance during the
self-assembly, the plane of each anthracene points to the center
of the octahedron to form a carambola-like non-convex
truncated octahedron with a triangle recessed window on
each face. Additionally, this arrangement results in only a small
remaining inner cavity, which is found to be 364 Å3 after an
estimate of the VOIDOO program based on the 1.4 Å probe
(Figure 4a). For VMOP-8, if eight H3BPT ligands are
approximated as isosceles triangles, as shown in Figure 3,
eventually an elongated truncated octahedron is generated,
which is an ordinary convex polyhedron, and the internal
cavity volume is calculated to be 1133 Å3 (Figure 4b).
Meanwhile, the rectangular window can be observed with a
size of 3.3 Å × 11.5 Å. The packing structure of VMOP-8 is
Figure 5. Topological analysis based on VMOP-7, 8. (a) 4-connected
{V5O9Cl}, 2-connected ligand H2ADC, and 3-connected ligand
H3BPT. (b) The size of VMOP-7 is 25 Å. (c) VMOP-8, 31.4 Å.
(d) {V5O9Cl} is regarded as 4-valent SBU, η = 60° (in VMOP-7), η =
43.6° (in VMOP-8). The bending angle θ of the ditopic linker
H2ADC is 180°; H3BPT serves as 3-valent SBU with η2 = 43.6°. (e, f)
H2ADC act as ditopic linkers; H3BPT serves as 3-valent SBU. VMOP-
7 can be simplified into an octahedron (otc), while VMOP-8 can be
simplified into a more sophisticated rhombic dodecahedron (rdo).
(g−i) Replacing the original topological vertices by a quadrilateral,
two derived topological polyhedrons otc-a and rdo-a were obtained.
reduced to a 4-valent vertex, the H2ADC ligand acts as a
ditopic linker, while the H3BPT ligand serves as a 3-valent
SBU. VMOP-7 can be simplified into an octahedron (otc),
while a more sophisticated rhombic dodecahedron (rdo) is
achieved with the same simplification for VMOP-8. Both
polyhedra belong to edge-transitive polyhedra, although they
have different configurations. As summarized in the reticular
chemistry of MOPs proposed by O’Keffee and Yaghi, for an
octahedron, it is composed of one kind of SBU as vertex linked
by a ditopic linker, and including two extreme cases, η = 60°, θ
= 180° and η = 90°, θ = 90°, corresponding to the limit
conditions, respectively.1 The geometry of VMOP-7 almost
meets the conditions of the first extreme case (Figure 5d,e).
While, for a rhombic dodecahedron, three extreme cases
include η1 = 48.2°, η2 = 120°; η1 = 70.5°, η2 = 109.5°; and η1 =
Figure 4. VOIDOO-calculated void space as shown (yellow mesh)
within the crystal structure of VMOP-7 (a) and VMOP-8 (b).
1030
https://dx.doi.org/10.1021/acs.cgd.0c01375
Cryst. Growth Des. 2021, 21, 1028−1034

Crystal Growth & Design
pubs.acs.org/crystal
Article
90°, η2 = 60°, representing three different geometries. The
topology of VMOP-8 (η1 = 43.6°, η2 = 120°) conforms to the
first extreme case, and a small deviation in η1 (48.2−43.6 =
4.6°) was observed to coordinate the effect caused by the
shape of H3BPT on topology (Figure 5d,f). In addition, the
angle of V5-SBU in VMOP-8 is also the minimum value found
so far. Further inspired by reticular chemistry, the vertices in
the simplest topology can be as extension points, replacing the
original topological vertices by a polygon with the number of
sides equal to the valence of those vertices; two new derived
networks are obtained and denoted as otc-a and rdo-a,
respectively, as shown in Figure 5g−i.
VMOP-8 as a catalyst. As shown in Table 1, the conversion
rate of diphenyl sulfide can reach more than 99% within 4 h
Table 1. Results of Sulfoxidation Reactions Catalyzed by
a
VMOP-8 at Different Conditions
Catalyst Properties. Researchers have paid attention to
the catalytic oxidation of sulfides because sulfone and sulfoxide
often play an essential role in the synthesis of many industrial
products. POMs are given priority as well-known and
environmentally friendly redox catalysts.41−44 VMOP-8 was
chosen as a catalyst to study its catalytic performance for
sulfoxidation reaction. First, a preliminary study of VMOP-8
for the oxidation of methyl phenyl sulfide (MBT) was carried
out. In methanol solvent, VMOP-8 (0.002 mmol) is used as
the catalyst, tert-butyl hydroperoxide (TBHP 1 mmol) as the
oxidant for the reaction (Scheme 1), and the conversion rate is
Scheme 1. Schematic Representation of Sulfoxidation
Reaction with MBT as an Example under VMOP-8 and
TBHP
a
Reaction conditions: substrate (0.4 mmol), VMOP-8 (0.002 mmol),
b
TBHP (1 mmol), and MeOH (5 mL). Isolated conversions were
calculated by GC or HPLC.
monitored by gas chromatography (GC). At room temper-
ature, the conversion of MBT quickly reached 90% within 10
min (Figure S7). After 1 h of reaction, the conversion rate is
close to 100% (Figure 6a). As a control experiment, the
conversion rate of MBT is only 22% in the blank control test
after 1 h without catalysts (Figure S8). Thus, we can conclude
that VMOP-8 can efficiently catalyze the sulfur oxidation
reaction.
(Figure S9). In addition, two kinds of substrates with different
electron effect substituents were also used, under the same
reaction conditions for 1 h. The conversion rate of 4-nitro-
methyl phenyl sulfide with an electron-withdrawing group was
81.33%, while 4-methoxy-methyl phenyl sulfide with an
electron-donating group was almost completely converted
(Figures S10 and S11). From the experimental results, we can
draw a conclusion that the electron-withdrawing group in the
substrate is not conducive to the catalytic oxidation process of
A series of substrates were then selected for sulfur oxidation
under the same conditions to evaluate the generality of
Figure 6. (a) Conversion curve of methyl phenyl sulfide with different reaction times. (b) Dynamic conversion curve of diphenyl sulfide catalyzed
by VMOP-8 (blue) and filter out the catalyst during the reaction (orange). Reaction conditions: substrate (0.4 mmol), VMOP-8 (0.002 mmol),
TBHP (1 mmol), and MeOH (5 mL), 25 °C.
1031
https://dx.doi.org/10.1021/acs.cgd.0c01375
Cryst. Growth Des. 2021, 21, 1028−1034

Crystal Growth & Design
pubs.acs.org/crystal
Article
thioether, whereas, for sulfur-containing aromatic substrates,
such as dibenzothiophene, 4,6-dimethyl dibenzothiophene, and
benzothiophene, the conversion rates, respectively, reach to
69.1%, 54.4%, and 30.3% after 12 h (Figures S12−S14). These
results show that the sulfur oxidation of thiophene substrates is
more difficult than that of thioether, and the catalytic effect of
the catalyst on the oxidation process of such substrates is not
ideal at room temperature. Therefore, in order to improve the
conversion rate, the reaction temperature was increased to 50
°C. The conversion rate of the two dibenzothiophene
substrates reached 97.2% and 83.7% after 6 h, and the
corresponding sulfoxide and sulfone products were identified
by IR spectra (Figure S15). Besides, benzothiophene can also
be effectively oxidized, and its conversion rate can reach 96.7%
after 12 h. Next, diphenyl sulfide was also selected to study the
dynamics of catalytic oxidation at 1 h intervals. As shown in
Figure 6b, the catalyst was hot filtered in a set of parallel
reactions and the solution continued to react, but the
conversion rate hardly improved. This further indicates that
VMOP-8 plays a vital role in the oxidation of thioethers as a
heterogeneous catalyst.
CONCLUSION
■
In summary, two new VMOPs based on the {V5O9Cl} SBU
and organic ligands with different configurations were
successfully synthesized under solvothermal conditions.
Through topology analysis, the geometry of VMOP-7 is an
octahedron (otc) and the configuration of VMOP-8 is a
rhombic dodecahedron (rdo). The angle η = 43.6° of V5-SBU
in VMOP-8 is also the smallest in the reported VMOPs. In
addition, the catalytic oxidation performance of VMOP-8 was
explored for oxidative desulfurization. According to the results,
VMOP-8 can effectively catalyze the conversion of sulfur-
containing substrates to sulfone and sulfoxide. This research
provides a new perspective for developing more excellent
properties of VMOPs. Besides, the selectivity of the catalyst
will be improved in the follow-up work and the environ-
mentally friendly catalyst will be tried to explore better
conditions.
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.cgd.0c01375.
■
sı
The results of sulfur oxidation experiments show that
VMOP-8 is a good and general heterogeneous oxidation
catalyst. The possible catalytic mechanism of VMOP-8 can be
inferred from the work of the typical polyoxovanadates
windmill-shaped V8 cluster applied to oxidative desulfurization
(Scheme 2).19 First, in the presence of the oxidant TBHP, the
The figures of the powder X-ray diffractions, IR spectra,
TGA curves, and additional structural figures. All GC
and HPLC spectra used to calculate the conversion rate
of the oxidation of sulfide reactions (PDF)
Accession Codes
Scheme 2. Proposed Catalytic Mechanism for the Oxidation
CCDC 2024517 and 2024518 contain the supplementary
crystallographic data for this paper. These data can be obtained
free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by
emailing data_request@ccdc.cam.ac.uk, or by contacting The
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
of Sulfides with VMOP-8
AUTHOR INFORMATION
Corresponding Authors
■
Liang Zhao − Institute of Functional Material Chemistry,
Local United Engineering Lab for Power Batteries, Northeast
Normal University, Changchun 130024, Jilin, People’s
Republic of China; Email: zhaol352@nenu.edu.cn
Xing-Long Wang − Institute of Functional Material
Chemistry, Local United Engineering Lab for Power Batteries,
Northeast Normal University, Changchun 130024, Jilin,
People’s Republic of China; orcid.org/0000-0002-5758-
6351; Email: wangxl824@nenu.edu.cn
Zhong-Min Su − Institute of Functional Material Chemistry,
Local United Engineering Lab for Power Batteries, Northeast
Normal University, Changchun 130024, Jilin, People’s
Republic of China; orcid.org/0000-0002-3342-1966;
Email: zmsu@nenu.edu.cn
exposed POV-based V5 clusters are converted into metal
peroxide intermediates. Next, the sulfur-containing aromatic
substrate is oxidized by the peroxovanadate intermediate and
gets oxygen atoms to form sulfoxide; the regeneration of the
catalysts also accompanies this process. Finally, sulfoxide can
be further nucleophilically attacked by metal peroxide
intermediates and oxidized to sulfone. Most likely, the catalytic
oxidation process is too fast and results in poor product
selectivity. Therefore, follow-up work will focus on improving
the selectivity of sulfoxide or sulfone as single products and
exploring better reaction conditions for replacing TBHP with
environmentally friendly oxidants.
Authors
Hong-Mei Gan − Institute of Functional Material Chemistry,
Local United Engineering Lab for Power Batteries, Northeast
Normal University, Changchun 130024, Jilin, People’s
Republic of China
Chao Qin − Institute of Functional Material Chemistry, Local
United Engineering Lab for Power Batteries, Northeast
Normal University, Changchun 130024, Jilin, People’s
Republic of China; orcid.org/0000-0001-7139-1094
Chunyi Sun − Institute of Functional Material Chemistry,
Local United Engineering Lab for Power Batteries, Northeast
1032
https://dx.doi.org/10.1021/acs.cgd.0c01375
Cryst. Growth Des. 2021, 21, 1028−1034

Crystal Growth & Design
pubs.acs.org/crystal
Article
(15) Inokuma, Y.; Arai, T.; Fujita, M. Networked molecular cages as
crystalline sponges for fullerenes and other guests. Nat. Chem. 2010,
2, 780−783.
Normal University, Changchun 130024, Jilin, People’s
Republic of China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.cgd.0c01375
(16) Rizzuto, F. J.; Nitschke, J. R. Stereochemical plasticity
II
modulates cooperative binding in a Co12 L6 cuboctahedron. Nat.
Chem. 2017, 9, 903−908.
Author Contributions
(17) Luo, D.; Zhou, X. P.; Li, D. Beyond molecules: mesoporous
supramolecular frameworks selfassembled from coordination cages
and inorganic anions. Angew. Chem., Int. Ed. 2015, 54, 6190−6195.
(18) Gosselin, E. J.; Rowland, C. A.; Bloch, E. D. Permanently
microporous metal-organic polyhedra. Chem. Rev. 2020, 120, 8987−
9014.
The manuscript was written through contributions of all
authors. All authors have given approval to the final version of
the manuscript.
Notes
The authors declare no competing financial interest.
(19) Tranchemontagne, D. J.; Mendoza-Cortes, J. L.; O’Keeffe, M.;
Yaghi, O. M. Secondary building units, nets and bonding in the
chemistry of metal-organic frameworks. Chem. Soc. Rev. 2009, 38,
1257−1283.
(20) Breen, J. M.; Schmitt, W. Hybrid organic-inorganic
polyoxometalates: functionalization ofviv vv nanosized clusters to
produce molecular capsules. Angew. Chem., Int. Ed. 2008, 47, 6904−
6908.
ACKNOWLEDGMENTS
■
This work was financially supported by the NSFC of China
(nos. 21771035, 21671034).
REFERENCES
■
(21) Spandl, J.; Brudgam, I.; Hartl, H. Solvothermal synthesis of a
̈
(1) Tranchemontagne, D. J.; Ni, Z.; O’Keeffe, M.; Yaghi, O. M.
Retikulre Chemie metall-organischer Polyeder. Angew. Chem. 2008,
120, 5214−5225.
24-nuclear, cube-shaped squarato-oxovanadium (IV) framework:
[N(nBu)4]8[V24O24(C4 O4 (OCH3)12)32 ]. Angew. Chem., Int. Ed.
2001, 40, 4018−4020.
(2) Perry, J. J.; Perman, J. A.; Zaworotko, M. J. Design and synthesis
of metal-organic frameworks using metal-organic polyhedra as
supermolecular building blocks. Chem. Soc. Rev. 2009, 38, 1400−
1417.
(3) Li, J. R.; Zhou, H. C. Bridging-ligand-substitution strategy for the
preparation of metal-organic polyhedra. Nat. Chem. 2010, 2, 893−
898.
(4) Fujita, D.; Ueda, Y.; Sato, S.; Mizuno, N.; Kumasaka, T.; Fujita,
M. Self-assembly of tetravalent Goldberg polyhedra from 144 small
components. Nature 2016, 540, 563−566.
(5) Eddaoudi, M.; Kim, J.; Wachter, J. B.; Chae, H. K.; O’Keeffe, M.;
Yaghi, O. M. Porous metal-organic polyhedra: 25 Å cuboctahedron
constructed from 12 Cu2(CO2)4 paddle-wheel building blocks. J.
Am. Chem. Soc. 2001, 123, 4368−4369.
(6) Xu, N.; Gan, H. M.; Qin, C.; Wang, X. L.; Su, Z. M. Evolution
from octahedral to icosahedral metal-organic polyhedra assembled by
two types of polyoxovanadate clusters. Angew. Chem., Int. Ed. 2019,
58, 4649−4653.
(7) Luo, D.; Wang, X. Z.; Yang, C.; Zhou, X. P.; Li, D. Self-Assembly
of Chiral Metal-Organic Tetartoid. J. Am. Chem. Soc. 2018, 140, 118−
121.
(8) Wu, K.; Li, K.; Hou, Y. J.; Pan, M.; Zhang, L. Y.; Chen, L.; Su, C.
Y. Homochiral D4-symmetric metal-organic cages from stereogenic
Ru(II) metalloligands for effective enantioseparation of atropisomeric
molecules. Nat. Commun. 2016, 7, 10487.
(9) Sepehrpour, H.; Fu, W.; Sun, Y.; Stang, P. J. Biomedically
relevant self-assembled metallacycles and metallacages. J. Am. Chem.
Soc. 2019, 141, 14005−14020.
(10) Zheng, Y.; Gan, H. M.; Zhao, Y.; Li, W.; Wu, Y.; Yan, X.; Wang,
Y.; Li, J.; Li, J.; Wang, X. L. Self-assembly and antitumor activity of a
polyoxovanadatebased coordination nanocage. Chem. - Eur. J. 2019,
25, 15326−1533.
(11) Hang, X.; Yang, W.; Wang, S.; Han, H.; Liao, W.; Jia, J.
Calixarene-Based {Co26} burr puzzle: an efficient oxygen reduction
catalyst. ACS Appl. Nano. Mater. 2019, 2, 4232−4237.
(12) Brown, C. J.; Toste, F. D.; Bergman, R. G.; Raymond, K. N.
Supramolecular catalysis in metal-ligand cluster hosts. Chem. Rev.
2015, 115, 3012−3035.
(13) Li, K.; Zhang, L. Y.; Yan, C.; Wei, S. C.; Pan, M.; Zhang, L.; Su,
C. Y. Stepwise assembly of Pd6(RuL3)8 nanoscale rhombododecahe-
dral metal-organic cages via metalloligand strategy for guest trapping
and protection. J. Am. Chem. Soc. 2014, 136, 4456−4459.
(14) Liu, Y.; Hu, C.; Comotti, A.; Ward, M. D. Supramolecular
archimedean cages assembled with 72 hydrogen bonds. Science 2011,
333, 436−440.
(22) Zhang, Z.; Wojtas, L.; Zaworotko, M. J. Organic-inorganic
hybrid polyhedra that can serve as supermolecular building blocks.
Chem. Sci. 2014, 5, 927−931.
(23) Zhang, Y. T.; Wang, X. L.; Li, S. B.; Song, B. Q.; Shao, K. Z.;
Su, Z. M. Ligand-Directed Assembly of Polyoxovanadate-Based
Metal- Organic Polyhedra. Inorg. Chem. 2016, 55, 8770−8775.
(24) Zhang, Y.-T.; Wang, X.-L.; Zhou, E.-L.; Wu, X.-S.; Song, B.-Q.;
Shao, K.-Z.; Su, Z.-M. Polyoxovanadate-based organic-inorganic
hybrids: from {V5O9Cl} clusters to nanosized octahedral cages.
Dalton Trans. 2016, 45, 3698−3701.
(25) Zhang, Y.-T.; Wang, X.-L.; Zhou, E.-L.; Wu, X.-S.; Song, B.-Q.;
Shao, K.-Z.; Su, Z.-M. Polyoxovanadate-based organic-inorganic
hybrids: from {V5O9Cl} clusters to nanosized octahedral cages.
Dalton Trans. 2016, 45, 3698−3701.
(26) Zhang, Y. T.; Wang, X. L.; Li, S. B.; Gong, Y. R.; Song, B. Q.;
Shao, K. Z.; Su, Z. M. Anderson-like alkoxo-polyoxovanadate clusters
serving as unprecedented second building units to construct metal-
organic polyhedra. Chem. Commun. 2016, 52, 9632−9635.
(27) Gong, Y. R.; Chen, W. C.; Zhao, L.; Shao, K. Z.; Wang, X. L.;
Su, Z. M. Functionalized polyoxometalate-based metal- organic
cuboctahedra for selective adsorption toward cationic dyes in aqueous
solution. Dalton Trans. 2018, 47, 12979−12983.
(28) Gong, Y. R.; Zhang, Y. T.; Qin, C.; Sun, C. Y.; Wang, X. L.; Su,
Z. M. Bottom-up construction and reversible structural trans-
formation of supramolecular isomers based on large truncated
tetrahedra. Angew. Chem., Int. Ed. 2019, 58, 780−784.
(29) Gong, Y. R.; Tao, Y. L.; Xu, N.; Sun, C. Y.; Wang, X. L.; Su, Z.
M. Two polyoxovanadate-based metal-organic polyhedra with
undiscovered ‘near-miss Johnson solid’’ geometry. Chem. Commun.
2019, 55, 10701−10704.
(30) Gong, Y. R.; Qin, C.; Zhang, Y. T.; Sun, C. Y.; Pan, Q. H.;
Wang, X. L.; Su, Z. M. Face-directed assembly of molecular cubes: in
situ substitution of a predetermined concave cluster. Angew. Chem.,
Int. Ed. 2020, 59, 22034.
(31) Zhang, Y. T.; Li, S. B.; Wang, X. L.; Gong, Y. R.; Shao, K. Z.;
Su, Z. M. Synthesis, structures, and magnetic properties of metal-
organic polyhedra based on unprecedented {V7} isopolyoxometalate
clusters. Dalton Trans. 2016, 45, 14898−14901.
(32) Zhang, Y. T.; Gan, H. M.; Qin, C.; Wang, X. L.; Su, Z. M.;
Zaworotko, M. J. Self-assembly of Goldberg polyhedra from a concave
[WV5O11(RCO2)5(SO4)]3‑ building block with 5-fold symmetry. J.
Am. Chem. Soc. 2018, 140, 17365−17368.
(33) Augustyniak, A. W.; Fandzloch, M.; Domingo, M.; Lakomska,
I.; Navarro, J. A. A vanadium(IV) pyrazolate metal-organic
1033
https://dx.doi.org/10.1021/acs.cgd.0c01375
Cryst. Growth Des. 2021, 21, 1028−1034

Crystal Growth & Design
pubs.acs.org/crystal
Article
polyhedron with permanent porosity and adsorption selectivity. Chem.
Commun. 2015, 51, 14724−14727.
(34) Astle, M. A.; Rance, G. A.; Loughlin, H. J.; Peters, T. D.;
Khlobystov, A. N. Molybdenum Dioxide in Carbon Nanoreactors as a
Catalytic Nanosponge for the Efficient Desulfurization of Liquid
Fuels. Adv. Funct. Mater. 2019, 29, 1808092.
(35) Zhang, Y.; Li, G.; Kong, L.; Lu, H. Deep oxidative
desulfurization catalyzed by Ti-based metal-organic frameworks.
Fuel 2018, 219, 103−110.
(36) Cape, J. N.; Fowler, D.; Davison, A. Ecological effects of sulfur
dioxide, fluorides, and minor air pollutants: recent trends and research
needs. Environ. Int. 2003, 29, 201−211.
(37) Komintarachat, C.; Trakarnpruk, W. Oxidative Desulfurization
Using Polyoxometalates. Ind. Eng. Chem. Res. 2006, 45, 1853−1856.
(38) Yin, P.; Wang, J.; Xiao, Z.; Wu, P.; Wei, Y.; Liu, T.
Polyoxometalate-organic hybrid molecules as amphiphilic emulsion
catalysts for deep desulfurization. Chem. - Eur. J. 2012, 18, 9174−
9178.
(39) Zhang, B.; Jiang, Z.; Li, J.; Zhang, Y.; Lin, F.; Liu, Y.; Li, C.
Catalytic oxidation of thiophene and its derivatives via dual activation
for ultra-deep desulfurization of fuels. J. Catal. 2012, 287, 5−12.
(40) Zhang, J.; Wang, A.; Li, X.; Ma, X. Oxidative desulfurization of
dibenzothiophene and diesel over [Bmim]3PMo12O40. J. Catal. 2011,
279, 269−275.
(41) Monakhov, K. Y.; Bensch, W.; Kogerler, P. Semimetal-
functionalised polyoxovanadates. Chem. Soc. Rev. 2015, 44, 8443−
8483.
(42) Santoni, M. P.; La Ganga, G.; Nardo, V. M.; Natali, M.;
Puntoriero, F.; Scandola, F.; Campagna, S. The use of a vanadium
species as a catalyst in photoinduced water oxidation. J. Am. Chem.
Soc. 2014, 136, 8189−8192.
(43) Zhao, X.; Duan, Y.; Yang, F.; Wei, W.; Xu, Y.; Hu, C. Efficient
mechanochemical synthesis of polyoxometalate⊂ZIF complexes as
reusable catalysts for highly selective oxidation. Inorg. Chem. 2017, 56,
14506−14512.
(44) Cao, J. P.; Xue, Y. S.; Li, N. F.; Gong, J. J.; Kang, R. K.; Xu, Y.
Lewis acid dominant windmill-shaped V8 clusters: a bifunctional
heterogeneous catalyst for CO2 cycloaddition and oxidation of
sulfides. J. Am. Chem. Soc. 2019, 141, 19487−19497.
1034
https://dx.doi.org/10.1021/acs.cgd.0c01375
Cryst. Growth Des. 2021, 21, 1028−1034