A Polyoxovanadate-Resorcin[4]arene-Based Porous Metal-Organic Framework as an Efficient Multifunctional Catalyst for the Cycloaddition of CO2 with Epoxides and the Selective Oxidation of Sulfides

Article abstract of DOI:10.1021/acs.inorgchem.7b01685

In this work, we report a new polyoxovanadate-resorcin[4]arene-based metal-organic framework (PMOF), [Co₂L_0.5V₄O₁₂]·3DMF·5H₂O (1), assembled with a newly functionalized wheel-like resorcin[4]arene ligand (L). 1 features an elegant porous motif and represents a rare example of PMOFs composed of both a resorcin[4]arene ligand and polyoxovanadate. Remarkably, 1 shows open V sites in the channel, which makes 1 an efficient heterogeneous Lewis acid catalyst for the cycloaddition of carbon dioxide to epoxides with high conversion and selectivity. Strikingly, 1 also exhibits high catalytic activity for the heterogeneous oxidative desulfurization of sulfides. Particularly, the heterogeneous catalyst 1 can be easily separated and reused with good catalytic activity.

Full text of DOI:10.1021/acs.inorgchem.7b01685

Article
pubs.acs.org/IC
A Polyoxovanadate−Resorcin[4]arene-Based Porous Metal−Organic
Framework as an Efficient Multifunctional Catalyst for the
Cycloaddition of CO2 with Epoxides and the Selective Oxidation of
Sulfides
Bing-Bing Lu, Jin Yang,* Ying-Ying Liu, and Jian-Fang Ma*
Key Lab of Polyoxometalate Science, Department of Chemistry, Northeast Normal University, Changchun 130024, China
S
* Supporting Information
ABSTRACT: In this work, we report a new polyoxovanadate−
resorcin[4]arene-based metal−organic framework (PMOF),
[Co2L0.5V4O12]·3DMF·5H2O (1), assembled with a newly function-
alized wheel-like resorcin[4]arene ligand (L). 1 features an elegant
porous motif and represents a rare example of PMOFs composed of
both a resorcin[4]arene ligand and polyoxovanadate. Remarkably, 1
shows open V sites in the channel, which makes 1 an efficient
heterogeneous Lewis acid catalyst for the cycloaddition of carbon
dioxide to epoxides with high conversion and selectivity. Strikingly,
1 also exhibits high catalytic activity for the heterogeneous oxidative
desulfurization of sulfides. Particularly, the heterogeneous catalyst 1
can be easily separated and reused with good catalytic activity.
structures adjusted by different functionalized moieties.44−47
INTRODUCTION
■
However, studies on the coordination chemistry of the
Carbon dioxide (CO2), as the main greenhouse gas, is
functionalized resorcin[4]arenes as versatile linkers to construct
suspected of causing global warming as well as subsequent
MOFs are limited.48−51 Particularly, decorating POM into
climate changes in the past few decades.1−4 As a result,
resorcin[4]arene-based MOFs remains almost unknown.52−55
considerable attention has been devoted to the development of
Over the past several years, we have performed an
CO2 sequestration technologies, which would positively reduce
investigation on resorcin[4]arene-based metal−organic motifs
the greenhouse emissions and satisfy human demand for raw
featuring elegant structures and properties.56−58 In this work,
chemical materials.5−9 Thus far, quite a lot of effort has been
we designed a newly functionalized wheel-like resorcin[4]arene
made to convert CO2 into highly valuable chemical
ligand (L) with eight powerful chelating 2-(2-pyridyl)imidazole
products.10−12 In this domain, the coupling reaction of CO2
substituents (Scheme 1). By utilizing the new resorcin[4]arene-
with epoxides is regarded as one of the most popular routes for
functionalized L ligand, a new PMOF, [Co2L0.5V4O12]·3DMF·
CO2 conversion because of the high atom efficiency and
5H2O (1), which features a porous architecture with 1D open
important application of cyclic carbonates.13−17 In terms of the
channels, has been synthesized under solvothermal conditions.
cycloaddition of CO2 with epoxides, various homogeneous
To our knowledge, 1 represents an exceedingly rare PMOF
composed of both resorcin[4]arene ligand and polyoxovana-
catalysts have been employed for the catalytic generation of
cyclic carbonates.18−21 Nevertheless, homogeneous catalytic
date (POV). Most strikingly, the open V sites in the pores
systems suffer from the inherent limitations of the separation of
make 1 an efficient Lewis acid catalyst for the cycloaddition of
the product and catalyst recycling.22,23 To overcome these
CO2 with epoxides into cyclic carbonates. Remarkably, 1 also
exhibits high catalytic activity for the heterogeneous oxidative
desulfurization of different sulfides.
limitations, heterogeneous catalysts including zeolites, metal
oxides, and functional polymers have been well developed.24−28
Very recently, the emerging metal−organic frameworks
(MOFs) or polyoxometalate (POM)-based MOFs (PMOFs),
RESULTS AND DISCUSSION
■
as promising heterogeneous candidate catalysts, have attracted
increasing interest.29−34
Crystal Structure of 1. Crystals of 1 were synthesized by
using Co(NO3)2·6H2O, NH4VO3, and L under solvothermal
conditions. Single-crystal X-ray diffraction analysis reveals that
In general, organic linkers have an important role in the
design and synthesis of PMOF catalysts because of their
tunable structural features.35−41 In this context, calixarene, as a
well-known macrocyclic compound, has been actively studied
in supramolecular chemistry.42,43 In this regard, resorcin[4]-
arenes are particularly attractive because of their variable
1 crystallizes in the triclinic system with space group P1. During
̅
Received: July 2, 2017
© XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.7b01685
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
Scheme 1. Synthetic Route for the L Ligand Used in This Work
Figure 1. (a) Coordination environments of the CoII and VV cations in 1. (b) View of the [V4O12]4− cycle. (c) Coordination mode of the L ligand.
(d) Inorganic−organic hybrid layer structure of 1. (e) View of the porous packing structure of 1. H atoms are omitted for clarity. Symmetry codes:
#1, −x + 1, −y + 1, −z; #2, −x + 4, −y + 2, −z + 1; #3, −x + 3, −y + 1, −z + 1.
B
DOI: 10.1021/acs.inorgchem.7b01685
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
the refinement, the SQUEEZE routine in PLATON was
employed because of the highly disordered solvents.59 In
each unit cell, there exist three free N,N′-dimethylformamide
(DMF) and five lattice water molecules, established by
thermogravimentric analysis (TGA), elemental analysis, and
electron diffraction density (Figure S1). As shown in Figure 1a,
the asymmetric unit of 1 consists of two unique CoII cations
(Co1 and Co2), a half of a L ligand, and two halves of a
[V4O12]4− unit. Each CoII cation was surrounded by two O
atoms from one [V4O12]4− unit and four N atoms from two 2-
(2-pyridyl)imidazole groups of the same L ligand in an
octahedral geometry. V1 and V2 and their symmetry-related
species share corner O atoms to yield a [V4O12]4− cycle, as
illustrated in Figure 1b. In the [V4O12]4− cycle, each V center
exhibits a VO4 tetrahedral coordination sphere. As depicted in
Figure 1c, every L ligand bridges four CoII cations via its eight
chelating 2-(2-pyridyl)imidazole moieties to produce a [Co4L]
secondary building unit (SBU). Further, adjacent [Co4L] SBUs
are linked by [V4O12]4− cycles to result in a charming
inorganic−organic hybrid layer with an open channel along
the a axis (ca. 9.6 Å × 15.2 Å; Figure 1d). Neighboring hybrid
layers are stacked on each other to yield a highly porous
supramolecular architecture (Figure 1e). The solvent-accessible
volume is about 45.5% of the unit cell volume (5686.0 Å3),
calculated by the PLATON program.59
trace of the catalytic product was achieved without n-Bu4NBr or
catalyst 1 at 80 °C and CO2 pressure of 1 atm (Figure S10a,b).
Noticeably, when 1 and n-Bu4NBr were employed as
cocatalysts, conversion of 2-(butoxymethyl)oxirane was drasti-
cally enhanced (Figure S10e, entry 5). With increasing
temperatures from 25 to 80 °C, conversion of 2-
(butoxymethyl)oxirane increases from 25% to the final >99%
after 6 h of catalytic reaction (Figure S10c−e, entries 3−5). On
the basis of the above catalytic conditions, the following
catalytic experiments were performed with 1 and n-Bu4NBr as
cocatalysts at 80 °C and 1 atm.
To further explore the catalytic generality of catalyst 1, the
substrates were extended to other epoxides under the
optimized catalytic conditions. As shown in Table 2, the
corresponding conversion of epichlorohydrin can reach 92%
after 6 h of the catalytic reaction (entry 1). The substrates 2-
(butoxymethyl)oxirane, 1,4-butanediol diglycidyl ether, benzyl
glycidyl ether, and glycidyl phenyl ether can be fully converted
to the corresponding cyclic carbonates within 6 h (Figures S5,
S6, S8, and S9, entries 4, 5, 7, and 8). The much higher catalytic
conversions of the substrates mainly account for the electron-
withdrawing groups in their structures.60 In contrast, only 72%
of the overall 1,2-epoxyethylbenzene was converted to the
catalytic product at the same time (Figure S7). When the
reaction time was further prolonged to 12 h, almost all of the
substrates were fully converted to the corresponding cyclic
carbonates (Figure S11), except the electron-donor 1,2-
epoxyethylbenzene (Figure S11e, entry 6).
Cycloaddition of CO2 with Epoxides. Given the high
porosity, together with the exposed V sites, the catalytic
performance of the Lewis acid catalyst 1 was evaluated for the
cycloaddtion of CO2 with epoxides at 1 and 20 atm,
respectively. As shown in Scheme 2, 2-(butoxymethyl)oxirane
To further investigate the reaction kinetics, the substrates
with electron-withdrawing groups, namely, 1,4-butanediol
diglycidyl ether, glycidyl phenyl ether, 2-(butoxymethyl)-
oxirane, and benzyl glycidyl ether, were selected to couple
with CO2 at 1 atm. As shown in Figure 2, the conversions are
more than 80% for 1,4-butanediol diglycidyl ether, glycidyl
phenyl ether, and 2-(butoxymethyl)oxirane within 2 h, and the
conversion of benzyl glycidyl ether is only up to 70% at the
same time. Finally, these substrates are almost fully converted
to the catalytic product within 6 h.
Scheme 2. Schematic Representation of CO2 Cycloaddition
to Epoxides
Moreover, catalyst 1 can be easily separated from the
reaction mixture through centrifugation and filtration. The
separated samples were washed with dichloromethane, dried in
air, and then reused for at least five cycles with catalytic activity
without obvious change (Figures 3 and S12). The result
demonstrates that catalyst 1 shows good stability and
recyclability.61−63
We also conduct the high-pressured cycloaddtion of CO2 to
epoxides with 1 as the catalyst in a microreactor at 80 °C and a
CO2 pressure of 20 atm. In the presence of n-Bu4NBr (1
mmol) and catalyst 1 (0.01 mmol based on V), most of the
substrates could be converted to the cyclic carbonates at a high
conversion rate of more than 90% after 4 h of catalytic reaction
(Table 3 and Figure S14). In particular, conversion of
epichlorohydrin and glycidyl phenyl ether can reach 98%
with a high turnover number (TON) of 1960 within 4 h
(entries 1 and 8). Notably, 1,2-epoxyethylbenzene only can be
converted to the cyclic carbonates in a relatively low conversion
rate of 80% because of its electron-donor effect (entry 6).64,65
The results indicate that the catalytic activity and selectivity of
catalyst 1 toward the substrates at 20 atm are similar to those
demonstrated at 1 atm.
was first chosen as a model substrate for the CO2 cycloaddtion
to investigate the optimum reaction conditions. During the
cycloaddtion of CO2 with epoxides, the catalytic products were
certified by 1H NMR data (Figures S2−S9), and the conversion
of the cyclic carbonate was calculated by gas chromatography
(GC; Figures S10 and S11). As illustrated in Table 1, only a
Table 1. Cycloaddition of CO2 with 2-
(Butoxymethyl)oxirane at Different Conditions
a
catalyst 1
(mmol)
n-Bu4NBr
(mmol)
time
(h)
temperature
conversion
b
entry
(°C)
(%)
1
2
3
4
5
0.01
0
0
6
6
6
6
6
80
80
25
50
80
trace
47
0.25
0.25
0.25
0.25
0.01
0.01
0.01
25
76
>99
a
The catalytic reaction dynamic was further explored in the
presence of the substrate 1,2-epoxyethylbenzene with 1 (0.01
mmol based on V) and n-Bu4NBr (1 mmol) as cocatalysts at 80
Reaction conditions: 1 (0.01 mmol based on V), epoxide (5 mmol),
b
and n-Bu4NBr (0.25 mmol); CO2 (1 atm). Isolated yields were
calculated by GC.
C
DOI: 10.1021/acs.inorgchem.7b01685
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
a
Table 2. Syntheses of Cyclic Carbonates from CO2 and Epoxides Catalyzed by 1
a
b
Reaction conditions: 1 (0.01 mmol based on V), epoxide (5 mmol), and n-Bu4NBr (0.25 mmol); CO2 (1 atm), 80 °C, 12 h. Isolated yields were
calculated by GC.
Figure 3. Recycling catalytic experiments with 1 and n-Bu4NBr as
cocatalysts at a CO2 pressure of 1 atm.
Figure 2. Conversion curves of the differently substituted epoxides
coupled with CO2 along with increasing reaction time.
°C and a CO2 pressure of 20 atm. As shown in Figure 4,
conversion of 1,2-epoxyethylbenzene increases with increasing
reaction time. Finally, a total conversion of 99% is achieved
after 8 h and the TON is close to 2000 (Figures S15 and S14f),
which are much higher than those at 1 atm, demonstrating that
the high pressure supports the cycloaddition of CO2 with
epoxides to produce cyclic carbonates.66 This TON for the
CO2 cycloaddition with epoxides is close to the recent values
found in the nanotube-based MOF catalyst67 but is much
higher than most of the related heterogeneous MOF
catalysts.68−70 Notably, conversion of 2-(butoxymethyl)oxirane
still remains more than 95% after five runs (Figures 5 and S16).
A possible synergistic catalytic mechanism for the cyclo-
addition of CO2 to epoxide was proposed, as shown in Scheme
3. In the initial step, the O atom of the epoxide interacts with
the Lewis acid V sites of 1.71,72 The epoxide ring was activated
and then opened by nucleophilic attack of the Br− anion,
forming the metal-coordinated bromoalkoxide I.73 After that,
CO2 coupled with the O atom of the intermediate I to yield the
metal carbonate II. Then the O atom of II attacks its C atom to
release Br−, producing the final cyclic carbonate.74 It could be
deduced that the synergistic effects of the V sites and n-Bu4NBr
as cocatalysts play a crucial role in promoting the catalytic
performance effectively.
D
DOI: 10.1021/acs.inorgchem.7b01685
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
a
Table 3. Syntheses of Cyclic Carbonates from CO2 and Epoxides Catalyzed by 1
a
b
Reaction conditions: epoxide (20 mmol), 1 (0.01 mmol based on V), and n-Bu4NBr (1 mmol); CO2 (20 atm), 80 °C, 4 h. Isolated yields were
calculated by GC.
Figure 4. Conversion curve of 1,2-epoxyethylbenzene coupled with
Figure 5. Recycling catalytic experiments with 1 and n-Bu4NBr as
CO2 at different reaction times.
cocatalysts at a CO2 pressure of 20 atm.
Catalytic Oxidative Desulfurization. POMs as environ-
mentally friendly redox catalysts have received considerably
attention in recent years.75−80 Here, the catalytic sulfoxidation
reactions were investigated by using 1 as the heterogeneous
catalyst.81 A preliminary investigation on oxidation of the
model methyl phenyl sulfide (MBT) was carried out to achieve
optimum reaction conditions using 1 as the catalyst (0.002
mmol) and 70% tert-butyl hydroperoxide (TBHP) as the
oxidant (1 mmol) in CH2Cl2 at 50 °C (Scheme 4). The
corresponding oxidized sulfoxide and sulfone products were
confirmed by Fourier transform infrared (FT-IR) spectrosco-
py82 (Figure S17), and the conversions were detected by high-
performance liquid chromatography (HPLC) analysis (Figure
S18). As illustrated in Table 4, when the reaction was carried
out without oxidant, no catalytic products were achieved
(Figure S18e, entry 1). Notably, the conversion of MBT is very
low when TBHP was replaced by H2O2 as the oxidant (Figure
S18f, entry 2).83 Thus, we can deduce that the oxidant TBHP
has an important role in the catalytic reaction.84 Once the
reaction was conducted without catalyst 1, conversion only
reaches 35% within 4 h (Figure S18g, entry 3). Using 1 as the
catalyst and TBHP as the oxidant, conversion of MBT gradually
increased from 38% to 99% along with prolonging the reaction
time from 1 to 4 h (Figure S18a−d, entries 4−7). Thus, the
following catalytic reactions were conducted in the presence of
both catalyst 1 and TBHP at 50 °C for 4 h.
E
DOI: 10.1021/acs.inorgchem.7b01685
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
have tried to further prolong the reaction time, conversion of
4,6-DMDBT cannot be promoted effectively.
Scheme 3. Proposed Catalytic Mechanism for the
Cycloaddition of CO2 to Epoxide Using 1 and n-Bu4NBr as
Cocatalysts
Exploratory experiments on the reusability of 1 were
performed using model sulfoxidation of MBT. Conversion of
MBT was calculated by GC (Figures S21 and S22). After
catalysis, the samples of catalyst 1 were separated from the
reaction mixture through centrifugation and filtration. Then the
separated catalyst 1 was reused for at least five cycles with good
catalytic activity, as shown in Figure 7.
The POM-based MOFs have been widely used for catalytic
oxidative desulfurization.88−93 It is proposed that a perox-
yvanadic acid complex was generated in the presence of the
oxidant TBHP. Then the sulfur-containing aromatic substrate
engages in a nucleophilic attack on the peroxo moiety and
achieves one O atom from the active species of the
peroxyvanadic acid complex. As a result, the sulfur-containing
substrate was oxidized to sulfoxide and sulfone.94,95
CONCLUSION
■
In summary, we have synthesized a newly functionalized wheel-
like resorcin[4]arene ligand, and subsequently it has been
utilized for the construction of a 2D POV−resorcin[4]arene-
based porous PMOF (1). The resulting 1 represents an
exceedingly rare example of PMOFs composed of both
resorcin[4]arene and POVs. The constructed PMOF 1 exhibits
exposed V sites in the channel and then was exploited as a
heterogeneous catalyst for the CO2−epoxide coupling reaction
and oxidative desulfurization of sulfides with high conversion
and selectivity. Significantly, the heterogeneous catalyst 1 can
be easily separated and reused with no obvious decrease in the
catalytic activity.
Scheme 4. Schematic Representation of Sulfoxidation
Reaction with Catalyst 1 and TBHP
Table 4. Results of Sulfoxidation Reactions Catalyzed by 1 at
a
Different Conditions
b
entry
catalyst
oxidant
time (h)
conversion (%)
EXPERIMENTAL SECTION
1
2
3
4
5
6
7
1
none
4
4
4
1
2
3
4
trace
trace
35
■
1
H2O2
Materials and Methods. All chemicals were commercially
available and were employed without further purification. FT-IR
spectra were conducted on a Mattson Alpha Centauri spectrometer.
Elemental analyses were recorded on a PerkinElmer 240 CHN
elemental analyzer. TGA measurement was carried out on a
PerkinElmer model TG-7 analyzer. PXRD patterns were measured
on a Rigaku Dmax 2000 X-ray diffractometer with graphite-
monochromatized Cu Kα radiation (λ = 0.154 nm). 1H NMR spectra
were determined on a Varian 500 MHz. The catalytic products for the
cycloaddtion of CO2 were determined by GC equipment with a
capillary (30 m long × 0.25 mm i.d., WondaCAP 17) and a flame
ionization detector (GC-2014C, Shimadzu, Japan). Sulfoxidation
products were detected by HPLC with a UV−vis detector at λ =
254 nm using an Inertsil (5 μm, 4.6 × 150 mm) ODS C18 column
(Agilent-1220). A mass spectrometry (MS) spectrum for L was
recorded on a Bruker AutoflexIII Smartbeam matrix-assisted laser
desorption/ionization time-of-flight (MALDI-TOF) mass spectrom-
eter. High-resolution MS spectra for the catalytic products were
recorded on a Bruker MicroTOF spectrometer.
X-ray Crystallography. Crystallographic data of 1 were collected
on an Oxford Diffraction Gemini R CCD diffractometer with graphite-
monochromated Mo Kα radiation (λ = 0.71073 Å) at room
temperature. The structure was solved by direct methods and refined
on F2 by full-matrix least squares using the SHELXS-2014 crystallo-
graphic software package.96−98 During the refinement, the SQUEEZE
function in PLATON was applied because of the highly disordered
solvents in the channel.59 All non-H atoms were refined with
anisotropic temperature parameters except disordered solvent
molecules. The H atoms attached to C atoms were generated
geometrically. Crystallographic data are listed in Table S1.
none
TBHP
TBHP
TBHP
TBHP
TBHP
1
1
1
1
38
72
91
99
a
Reaction conditions: substrate (0.4 mmol), 1 (0.002 mmol), TBHP
(1 mmol), and CH2Cl2 (5 mL). Isolated conversions were calculated
by HPLC.
b
To evaluate the catalytic generality of catalyst 1, a series of
substrates were selected under the optimized reaction
conditions. As shown in Table 5, when diphenyl sulfide was
utilized as the substrate, the catalytic oxidation conversion of
diphenyl sulfide reaches more than 99% within 4 h (Figure
S19a, entry 2). However, for sulfur-containing aromatic
substrates such as dibenzothiophene (Figure S19b, entry 3),
4,6-dimethyldibenzothiophene (4,6-DMDBT; Figure S19c,
entry 4), and benzothiophene (Figure S19d, entry 5), 93%,
88%, and 75% conversions were achieved after 12 h of catalytic
reactions, respectively. The results indicate that the catalytic
oxidation of the thiophene substrates is more difficult than that
of the sulfur ethers during sulfoxidation reactions.85−87
Further, the catalytic reaction dynamics of 4,6-DMDBT were
explored at the same conditions. Conversion of 4,6-DMDBT
was detected every 2 h (Figures 6 and S20). In the initial
reaction, conversions of 4,6-DMDBT was drastically enhanced,
reached 76% within 8 h, and then slowly increased from 76% to
88% in the next 4 h. The results demonstrate that the reaction
is nearly accomplished at the beginning of 8 h. Although we
Synthesis of L. A mixture of sodium methoxide (19.5 g, 0.36 mol),
resorcinol (20.0 g, 0.18 mol), methanol (200 mL), and 1-bromo-3-
chloropropane (171.9 g, 1.09 mol) was stirred at 80 °C for 12 h. The
F
DOI: 10.1021/acs.inorgchem.7b01685
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
a
Table 5. Results of Sulfoxidation Reactions Catalyzed by 1 Using TBHP as the Oxidant
a
b
Reaction conditions: substrate (0.4 mmol), 1 (0.002 mmol), TBHP (1 mmol), and CH2Cl2 (5 mL). Isolated conversions were calculated by
HPLC.
mixture was then filtered, and the liquor was collected. The solvent
and excess 1-bromo-3-chloropropane were removed under reduced
pressure to give a yellow oil residue. The product was further washed
using NaOH (1 mol L−1) and water. The precursor I was achieved in a
64% yield after drying with anhydrous sodium sulfate and evaporation
of the solvent (Scheme 1).
Further, BF3·OEt2 (5.68 g, 0.04 mmol) was added dropwise to a
mixture of the precursor I (2.76 g, 0.02 mmol), benzaldehyde (5.26 g,
0.02 mol), and anhydrous dichloromethane (200 mL) under an ice
bath and then stirred for 48 h at room temperature. The reaction
mixture was washed three times with water, and then the organic layer
was dried with anhydrous sodium sulfate. The raw product was
achieved after the solvent was evaporated. The precursor II was
obtained in 53% yield after acetone was added to the raw product
(Scheme 1).
A mixture of the precursor II (22.48 g, 0.016 mol), 2-(2-
pyridyl)imidazole (27.84 g, 0.192 mol), 60% NaH (6.4 g, 0.16 mol),
Figure 6. Dynamic conversion curve of 4,6-DMDBT catalyzed by 1.
and DMF (100 mL) was stirred for 48 h at 120 °C. After the reaction
finished, the solvent was evaporated, and washed with 0.1 M NaOH
and water. The milk-white L was achieved in 85% yield. IR data (KBr,
cm−1): 3434 (w), 2928 (w), 2872 (w), 1609 (w), 1587 (s), 1489 (s),
1463 (s), 1408 (m), 1298 (s), 1192 (s), 1157 (w), 1094 (s), 1034 (m),
1
792 (m), 744 (m), 706 (s), 623 (w), 593 (w). H NMR (DMSO): δ
8.45−8.50 (m, 8H, Ar−H), 7.99−8.08 (m, 8H, Ar−H), 7.78−7.83 (m,
8H, Ar−H), 7.20−7.32 (m, 8H, Ar−H), 6.91−6.98 (m, 16H, N−CH),
6.79−6.81 (S, 4H Ar−H), 6.70−6.78 (m, 8H, Ar−H), 6.63−6.69 (m,
8H, Ar−H), 6.20−6.47 (m, 8H, Ar−H), 5.77−5.78 (m, 4H, CH),
4.25−4.49 (m, 8H, OCH2), 4.08−4.18 (m, 8H, OCH2), 3.33−3.97
(m, 16H, CH2N), 1.80−2.08 (m, 16H, CH2). MALDI-TOF-MS.
Calcd for C140H128O8N24 ([M − e]−): m/z 2274.0. Found: m/z 2274.0
(Figure S23).
Synthesis of [Co2L0.5V4O12]·3DMF·5H2O (1). A mixture of
NH4VO3 (0.02 g, 17 mmol), Co(NO3)2·6H2O (0.023 g, 0.8 mmol),
L (0.023 g, 0.1 mmol), DMF (4 mL), H2O (4 mL), and 1 M HCl (2
drops) was sealed in a 15 mL Teflon reactor and heated at 130 °C for
3 days. The red crystals were achieved in 41% yield. Anal. Calcd for
C79H95N15O24Co2V4 (Mr = 1960.32): C, 48.36; H, 4.85; N, 10.71.
Figure 7. Recycling experiments of sulfoxidation reactions of MBT
using 1 as the catalyst and TBHP as the oxidant.
Found: C, 47.28; H, 4.78; N, 11.45. IR data (KBr, cm−1): 3365 (m),
3113 (m), 2929 (m), 2876 (m), 1655 (m), 1604 (s), 1474 (s), 1408
(m), 1379 (w), 1074 (w), 1053 (w), 1040 (w), 789 (s), 417 (w).
G
DOI: 10.1021/acs.inorgchem.7b01685
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
Cycloaddtion of CO2 to Epoxides at 1 atm. The cycloaddtion
of CO2 with epoxides was performed in a 10 mL round-bottomed flask
at 1 atm. Typically, epoxide (5 mmol), n-Bu4NBr (80 mg, 0.25 mmol),
and catalyst 1 (4.9 mg, 0.0025 mmol) were added to the round-
bottomed flask at a CO2 pressure of 1 atm and then stirred for 12 h at
80 °C. The catalytic products were certified by 1H NMR data, and the
yields were calculated by GC.
(5) Lee, J. H.; Lee, H. J.; Lim, S. Y.; Kim, B. G.; Choi, J. W.
Combined CO2-philicity and ordered mesoporosity for highly selective
CO2 capture at high temperatures. J. Am. Chem. Soc. 2015, 137, 7210−
7216.
(6) Lin, S.; Diercks, C. S.; Zhang, Y. B.; Kornienko, N.; Nichols, E.
M.; Zhao, Y. B.; Paris, A. R.; Kim, D.; Yang, P. D.; Yaghi, O. M.;
Chang, C. J. Covalent organic frameworks comprising cobalt
porphyrins for catalytic CO2 reduction in water. Science 2015, 349,
1208−1213.
(7) Voicu, D.; Abolhasani, M.; Choueiri, R.; Lestari, G.; Seiler, C.;
Menard, G.; Greener, J.; Guenther, A.; Stephan, D. W.; Kumacheva, E.
Microfluidic studies of CO2 sequestration by frustrated Lewis pairs. J.
Am. Chem. Soc. 2014, 136, 3875−3880.
Cycloaddtion of CO2 to Epoxides at 20 atm. Catalyst 1 (4.9
mg, 0.0025 mmol), n-Bu4NBr (322 mg, 1 mmol), and epoxide (20
mmol) were placed in a 25 mL stainless steel high-pressure reactor at a
1
CO2 pressure of 20 atm and stirred for 4 h at 80 °C. H NMR data
were used to certify the catalytic products. The yields of the products
were calculated by GC.
Catalytic Oxidative Desulfurization. In a typical procedure,
catalyst 1 (7.8 mg, 0.004 mmol), TBHP (90 mg, 1 mmol), and MBT
(50 mg, 0.4 mmol) were added to CH2Cl2 (5 mL) in a round-
bottomed flask and heated at 50 °C for 4−12 h with stirring. The
products were identified by FT-IR spectroscopy, and the yields were
detected by HPLC and GC. All analyses were conducted with the
mobile phase of CH3CN and H2O (9:1) at an operating flow rate of 1
mL min−1.
(8) Dey, S.; Bhunia, A.; Breitzke, H.; Groszewicz, P. B.; Buntkowsky,
G.; Janiak, C. Two linkers are better than one: enhancing CO2 capture
and separation with porous covalent triazine-based frameworks from
mixed nitrile linkers. J. Mater. Chem. A 2017, 5, 3609−3620.
(9) Schlager, S.; Fuchsbauer, A.; Haberbauer, M.; Neugebauer, H.;
Sariciftci, N. S. Carbon dioxide conversion to synthetic fuels using
biocatalytic electrodes. J. Mater. Chem. A 2017, 5, 2429−2443.
(10) Kauffman, D. R.; Thakkar, J.; Siva, R.; Matranga, C.; Ohodnicki,
P. R.; Zeng, C. J.; Jin, R. C. Efficient electrochemical CO2 conversion
powered by renewable energy. ACS Appl. Mater. Interfaces 2015, 7,
15626−15632.
ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.7b01685.
(11) Yang, X.; Fugate, E. A.; Mueanngern, Y.; Baker, L. R.
Photoelectrochemical CO2 reduction to acetate on iron−copper
oxide catalysts. ACS Catal. 2017, 7, 177−180.
(12) Aresta, M.; Dibenedetto, A.; Angelini, A. Catalysis for the
valorization of exhaust carbon: from CO2 to chemicals, materials, and
fuels. Technological use of CO2. Chem. Rev. 2014, 114, 1709−1742.
(13) Jiang, W.; Yang, J.; Liu, Y. Y.; Song, S. Y.; Ma, J. F. A porphyrin-
based porous rtl metal−organic framework as an efficient catalyst for
the cycloaddition of CO2 to epoxides. Chem. - Eur. J. 2016, 22, 16991−
16997.
TGA curve, GC, FT-IR, MALDI-TOF-MS, HPLC, and
1H NMR spectra, PXRD patterns, and tables (PDF)
Accession Codes
CCDC 1556497 contains 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.
(14) Li, P. Z.; Wang, X. J.; Liu, J.; Lim, J. S.; Zou, R. Q.; Zhao, Y. L. A
triazole-containing metal−organic framework as a highly effective and
substrate size-dependent catalyst for CO2 conversion. J. Am. Chem. Soc.
2016, 138, 2142−2145.
́
(15) Alkordi, M. H.; Weselinski, Ł. J.; D’Elia, V.; Barman, S.; Cadiau,
AUTHOR INFORMATION
Corresponding Authors
*E-mail: yangj808@nenu.edu.cn (J.Y.).
*E-mail: majf247@nenu.edu.cn (J.-F.M.). Fax: +86-431-
85098620.
A.; Hedhili, M. N.; Cairns, A. J.; AbdulHalim, R. G.; Basset, J.-M.;
Eddaoudi, M. CO2 conversion: the potential of porous-organic
polymers (POPs) for catalytic CO2−epoxide insertion. J. Mater.
Chem. A 2016, 4, 7453−7460.
■
(16) Du, Y.; Yang, H. S.; Wan, S.; Jin, Y. H.; Zhang, W. A titanium-
based porous coordination polymer as a catalyst for chemical fixation
of CO2. J. Mater. Chem. A 2017, 5, 9163−9168.
(17) Reiter, M.; Vagin, S.; Kronast, A.; Jandl, C.; Rieger, B. A. Lewis
acid β-diiminato-zinc-complex as all-rounder for co- and terpolymer-
isation of various epoxides with carbon dioxide. Chem. Sci. 2017, 8,
1876−1882.
ORCID
Jian-Fang Ma: 0000-0002-4059-8348
Notes
The authors declare no competing financial interest.
(18) Ding, L.-G.; Yao, B.-J.; Jiang, W.-L.; Li, J.-T.; Fu, Q.-J.; Li, Y.-A.;
Liu, Z.-H.; Ma, J.-P.; Dong, Y.-B. Bifunctional imidazolium-based ionic
liquid decorated UiO-67 type MOF for selective CO2 adsorption and
catalytic property for CO2 cycloaddition with epoxides. Inorg. Chem.
2017, 56, 2337−2344.
(19) Al-Qaisi, F.; Streng, E.; Tsarev, A.; Nieger, M.; Repo, T.
Titanium alkoxide complexes as catalysts for the synthesis of cyclic
carbonates from carbon dioxide and epoxides. Eur. J. Inorg. Chem.
2015, 2015, 5363−5367.
ACKNOWLEDGMENTS
This work was supported by the National Natural Science
Foundation of China (Grants 21471029 and 21371030).
■
REFERENCES
■
(1) Sumida, K.; Rogow, D. L.; Mason, J. A.; McDonald, T. M.; Bloch,
E. D.; Herm, Z. R.; Bae, T. H.; Long, J. R. Carbon dioxide capture in
metal−organic frameworks. Chem. Rev. 2012, 112, 724−781.
(2) Nakajima, T.; Tamaki, Y.; Ueno, K.; Kato, E.; Nishikawa, T.;
Ohkubo, K.; Yamazaki, Y.; Morimoto, T.; Ishitani, O. Photocatalytic
reduction of low concentration of CO2. J. Am. Chem. Soc. 2016, 138,
13818−13821.
(3) Kirchner, B.; Intemann, B. Molecular transport: catch the carbon
dioxide. Nat. Chem. 2016, 8, 401−402.
(4) Pounds, J. A.; et al. Widespread amphibian extinctions from
epidemic disease driven by global warming. Nature 2006, 439, 161−
167.
(20) Zhao, Y. C.; Yao, C. Q.; Chen, G. W.; Yuan, Q. Highly efficient
synthesis of cyclic carbonate with CO2 catalyzed by ionic liquid in a
microreactor. Green Chem. 2013, 15, 446−452.
(21) Decortes, A.; Castilla, A. M.; Kleij, A. W. Salen-complex-
mediated formation of cyclic carbonates by cycloaddition of CO2 to
epoxides. Angew. Chem., Int. Ed. 2010, 49, 9822−9837.
(22) Yamaguchi, R.; Ikeda, C.; Takahashi, Y.; Fujita, K. I.
Homogeneous catalytic system for reversible dehydrogenation−
hydrogenation reactions of nitrogen heterocycles with reversible
H
DOI: 10.1021/acs.inorgchem.7b01685
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
interconversion of catalytic species. J. Am. Chem. Soc. 2009, 131,
8410−8412.
(23) Vidossich, P.; Lledos, A.; Ujaque, G. First-principles molecular
́
(39) Schoedel, A.; Li, M.; Li, D.; O’Keeffe, M.; Yaghi, O. M.
Structures of metal−organic frameworks with rod secondary building
units. Chem. Rev. 2016, 116, 12466−12535.
(40) Xiang, S. C.; Wu, X. T.; Zhang, J. J.; Fu, R. B.; Hu, S. M.; Zhang,
X. D. A 3D canted antiferromagnetic porous metal−organic
framework with anatase topology through assembly of an analogue
of polyoxometalate. J. Am. Chem. Soc. 2005, 127, 16352−16353.
dynamics studies of organometallic complexes and homogeneous
catalytic processes. Acc. Chem. Res. 2016, 49, 1271−1278.
(24) Meng, X.-L.; Nie, Y.; Sun, J.; Cheng, W.-G.; Wang, J.-Q.; He,
H.-Y.; Zhang, S.-J. Functionalized Dicyandiamide−formaldehyde
polymers as efficient heterogeneous catalysts for conversion of CO2
into organic carbonates. Green Chem. 2014, 16, 2771−2778.
(25) Miralda, C. M.; Macias, E. E.; Zhu, M. Q.; Ratnasamy, P.;
Carreon, M. A. Zeolitic imidazole framework-8 catalysts in the
Conversion of CO2 to chloropropene carbonate. ACS Catal. 2012, 2,
180−183.
(26) Yamaguchi, K.; Ebitani, K.; Yoshida, T.; Yoshida, H.; Kaneda, K.
Mg−Al mixed oxides as highly active acid−base catalysts for
cycloaddition of carbon dioxide to epoxides. J. Am. Chem. Soc. 1999,
121, 4526−4527.
́
́
(41) Santiago-Portillo, A.; Blandez, J. F.; Navalon, S.; Alvaro, M.;
García, H. Influence of the organic linker substituent on the catalytic
activity of MIL-101(Cr) for the oxidative coupling of benzylamines to
imines. Catal. Sci. Technol. 2017, 7, 1351−1362.
(42) Wang, Y.-X.; Zhang, Y.-M.; Liu, Y. Photolysis of an amphiphilic
assembly by calixarene-induced aggregation. J. Am. Chem. Soc. 2015,
137, 4543−4549.
(43) Zhou, J.; Chen, M.; Diao, G. W. Assembling gold and platinum
nanoparticles on resorcinarene modified graphene and their electro-
chemical applications. J. Mater. Chem. A 2013, 1, 2278−2285.
(44) Lv, L.-L.; Yang, J.; Zhang, H.-M.; Liu, Y.-Y.; Ma, J.-F. Metal-ion
exchange, small-molecule sensing, selective dye adsorption, and
reversible iodine uptake of three coordination polymers constructed
by a new resorcin[4]arene-based tetracarboxylate. Inorg. Chem. 2015,
54, 1744−1755.
(27) Kuruppathparambil, R. R.; Babu, R.; Jeong, H. M.; Hwang, G.
Y.; Jeong, G. S.; Kim, M. I.; Kim, D.-W.; Park, D.-W. A solid solution
zeolitic imidazolate framework as a room temperature efficient catalyst
for the chemical fixation of CO2. Green Chem. 2016, 18, 6349−6356.
́
(28) Buaki-Sogo, M.; Vivian, A.; Bivona, L. A.; García, H.;
́
(45) Semeril, D.; Matt, D. Synthesis and catalytic relevance of P(III)
Gruttadauria, M.; Aprile, C. Imidazolium functionalized carbon
nanotubes for the synthesis of cyclic carbonates: reducing the gap
between homogeneous and heterogeneous catalysis. Catal. Sci. Technol.
2016, 6, 8418−8427.
and P(V)-functionalised calixarenes and resorcinarenes. Coord. Chem.
Rev. 2014, 279, 58−95.
(46) Park, Y. S.; Park, J.; Paek, K. Versatile self-assembled molecular
capsule formation of a resorcin[4]arene-based benzamidoiminocavi-
tand. Chem. Commun. 2013, 49, 6316−6318.
(29) Jiang, W.; Yang, J.; Liu, Y.-Y.; Song, S.-Y.; Ma, J.-F. A stable
porphyrin-based porous mog metal−organic framework as an efficient
solvent-free catalyst for C−C bond formation. Inorg. Chem. 2017, 56,
3036−3043.
(30) Jiang, W.; Yang, J.; Liu, Y.-Y.; Ma, J.-F. Porphyrin-based mixed-
valent Ag(I)/Ag(II) and Cu(I)/Cu(II) networks as efficient
heterogeneous catalysts for the azide−alkyne “click” reaction and
promising oxidation of ethylbenzene. Chem. Commun. 2016, 52,
1373−1376.
(31) Hao, X.-L.; Ma, Y.-Y.; Zang, H.-Y.; Wang, Y.-H.; Li, Y.-G.;
Wang, E.-B. A polyoxometalate-encapsulating cationic metal−organic
framework as a heterogeneous catalyst for desulfurization. Chem. - Eur.
J. 2015, 21, 3778−3784.
(32) Bromberg, L.; Diao, Y.; Wu, H. M.; Speakman, S. A.; Hatton, T.
A. Chromium(III) terephthalate metal organic framework (MIL-101):
HF-free synthesis, structure, polyoxometalate composites, and catalytic
properties. Chem. Mater. 2012, 24, 1664−1675.
(33) Han, Q. X.; He, C.; Zhao, M.; Qi, B.; Niu, J. Y.; Duan, C. Y.
Engineering chiral polyoxometalate hybrid metal−organic frameworks
for asymmetric dihydroxylation of olefins. J. Am. Chem. Soc. 2013, 135,
10186−10189.
(34) Liang, J.; Chen, R.-P.; Wang, X.-Y.; Liu, T.-T.; Wang, X.-S.;
Huang, Y.-B.; Cao, R. Postsynthetic ionization of an imidazole-
containing metal−organic framework for the cycloaddition of carbon
dioxide and epoxides. Chem. Sci. 2017, 8, 1570−1575.
(35) Wu, H.; Yang, J.; Su, Z.-M.; Batten, S. R.; Ma, J.-F. An
exceptional 54-fold interpenetrated coordination polymer with 103-srs
network topology. J. Am. Chem. Soc. 2011, 133, 11406−11409.
(36) Liu, B.; Yu, Z.-T.; Yang, J.; Hua, W.; Liu, Y.-Y.; Ma, J.-F. First
three-dimensional inorganic−organic hybrid material constructed from
an “inverted keggin” polyoxometalate and a copper(I)-organic
complex. Inorg. Chem. 2011, 50, 8967−8972.
(37) Liu, B.; Yang, J.; Yang, G.-C.; Ma, J.-F. Four new three-
dimensional polyoxometalate-based metal−organic frameworks con-
structed from [Mo6O18(O3AsPh)2]4− polyoxoanions and copper(I)-
organic fragments: syntheses, structures, electrochemistry, and photo-
catalysis properties. Inorg. Chem. 2013, 52, 84−94.
(47) Soomro, Z. H.; Cecioni, S.; Blanchard, H.; Praly, J.-P.; Imberty,
A.; Vidal, S.; Matthews, S. E. CuAAC synthesis of resorcin[4]arene-
based glycoclusters as multivalent ligands of lectins. Org. Biomol. Chem.
2011, 9, 6587−6597.
(48) Wiegmann, S.; Mattay, J. Inherently chiral resorcin[4]arenes: a
new concept for improving the functionality. Org. Lett. 2011, 13,
3226−3228.
(49) Yasmin, L.; Coyle, T.; Stubbs, K. A.; Raston, C. L. Stereospecific
synthesis of resorcin[4]arenes and pyrogallol[4]arenes in dynamic thin
films. Chem. Commun. 2013, 49, 10932−10934.
(50) Pochorovski, I.; Ebert, M.-O.; Gisselbrecht, J.-P.; Boudon, C.;
Schweizer, W. B.; Diederich, F. Redox-switchable resorcin[4]arene
cavitands: molecular grippers. J. Am. Chem. Soc. 2012, 134, 14702−
14705.
́
(51) Boinski, T.; Cieszkowski, A.; Rosa, B.; Lesniewska, B.; Szumna,
A. Calixarenes with naphthalene units: calix[4]naphthalenes and
hybrid[4]arenes. New J. Chem. 2016, 40, 8892−8896.
(52) Juan-Alcaniz, J.; Ramos-Fernandez, E. V.; Lafont, U.; Gascon, J.;
̃
Kapteijn, F. Building MOF bottles around phosphotungstic acid ships:
one-pot synthesis of bi-functional polyoxometalate-MIL-101 catalysts.
J. Catal. 2010, 269, 229−241.
(53) Du, D. Y.; Qin, J. S.; Li, S. L.; Su, Z. M.; Lan, Y. Q. Recent
advances in porous polyoxometalatebased metal−organic framework
materials. Chem. Soc. Rev. 2014, 43, 4615−4632.
(54) Zhang, Z.-M.; Zhang, T.; Wang, C.; Lin, Z. K.; Long, L.-S.; Lin,
W. B. Photosensitizing metal−organic framework enabling visible-light
driven proton reduction by a wells−dawson-type polyoxometalate. J.
Am. Chem. Soc. 2015, 137, 3197−3200.
(55) Comito, R. J.; Fritzsching, K. J.; Sundell, B. J.; Schmidt-Rohr, K.;
̆
Dinca, M. Single-site heterogeneous catalysts for olefin polymerization
enabled by cation exchange in a metal-organic framework. J. Am. Chem.
Soc. 2016, 138, 10232−10237.
(56) Pei, W.-Y.; Xu, G. H.; Yang, J.; Wu, H.; Chen, B. L.; Zhou, W.;
Ma, J.-F. Versatile assembly of metal-coordinated calix[4]resorcinarene
cavitands and cages through ancillary linker tuning. J. Am. Chem. Soc.
2017, 139, 7648−7656.
(57) Zhang, S.-T.; Yang, J.; Wu, H.; Liu, Y.-Y.; Ma, J.-F. Systematic
investigation of high-sensitivity luminescent sensing for polyoxometa-
lates and iron(III) by MOFs assembled with a new resorcin[4]arene-
functionalized tetracarboxylate. Chem. - Eur. J. 2015, 21, 15806−
15819.
(38) Kan, W.-Q.; Yang, J.; Liu, Y.-Y.; Ma, J.-F. Series of inorganic−
organic hybrid materials constructed from octamolybdates and metal−
organic frameworks: syntheses, structures, and physical properties.
Inorg. Chem. 2012, 51, 11266−11278.
I
DOI: 10.1021/acs.inorgchem.7b01685
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
(58) Zhao, S.-S.; Yang, J.; Liu, Y.-Y.; Ma, J.-F. Fluorescent aromatic
tag-functionalized MOFs for highly selective sensing of metal ions and
small organic molecules. Inorg. Chem. 2016, 55, 2261−2273.
(59) Spek, A. L. PLATON SQUEEZE: a tool for the calculation of
the disordered solvent contribution to the calculated structure factors.
Acta Crystallogr., Sect. C: Struct. Chem. 2015, 71, 9−18.
(60) Dong, J.; Cui, P.; Shi, P.-F.; Cheng, P.; Zhao, B. Ultrastrong
alkali-resisting lanthanide-zeolites assembled by [Ln60] nanocages. J.
Am. Chem. Soc. 2015, 137, 15988−15991.
(61) Kornienko, N.; Zhao, Y. B.; Kley, C. S.; Zhu, C. H.; Kim, D.;
Lin, S.; Chang, C. J.; Yaghi, O. M.; Yang, P. D. Metal−organic
frameworks for electrocatalytic reduction of carbon dioxide. J. Am.
Chem. Soc. 2015, 137, 14129−14135.
(62) Beyzavi, M. H.; Klet, R. C.; Tussupbayev, S.; Borycz, J.;
Vermeulen, N. A.; Cramer, C. J.; Stoddart, J. F.; Hupp, J. T.; Farha, O.
K. A hafnium-based metal−organic framework as an efficient and
multifunctional catalyst forfacile CO2 fixation and regioselective and
enantioretentive epoxide activation. J. Am. Chem. Soc. 2014, 136,
15861−15864.
(75) Monakhov, K. Y.; Bensch, W.; Kogerler, P. Semimetal-
functionalised polyoxovanadates. Chem. Soc. Rev. 2015, 44, 8443−
8483.
̈
(76) Wang, S.-S.; Yang, G.-Y. Recent advances in polyoxometalate-
catalyzed reactions. Chem. Rev. 2015, 115, 4893−4962.
(77) Dolbecq, A.; Dumas, E.; Mayer, C. R.; Mialane, P. Hybrid
organic-inorganic polyoxometalate compounds: from structural
diversity to applications. Chem. Rev. 2010, 110, 6009−6048.
(78) Santoni, M.-P.; La Ganga, G.; Mollica Nardo, V.; 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.
(79) Wang, Y. F.; Weinstock, I. A. Polyoxometalate-decorated
nanoparticles. Chem. Soc. Rev. 2012, 41, 7479−7496.
(80) Walsh, J. J.; Bond, A. M.; Forster, R. J.; Keyes, T. E. Hybrid
polyoxometalate materials for photo(electro-) chemical applications.
Coord. Chem. Rev. 2016, 306, 217−234.
(81) Meninno, S.; Parrella, A.; Brancatelli, G.; Geremia, S.; Gaeta, C.;
Talotta, C.; Neri, P.; Lattanzi, A. Polyoxomolybdate-calix[4]arene
hybrid: a catalyst for sulfoxidation reactions with hydrogen peroxide.
Org. Lett. 2015, 17, 5100−5103.
(82) Liu, D.; Lu, Y.; Tan, H.-Q.; Chen, W.-L.; Zhang, Z.-M.; Li, Y.-
G.; Wang, E.-B. Polyoxometalate-based purely inorganic porous
frameworks with selective adsorption and oxidative catalysis
functionalities. Chem. Commun. 2013, 49, 3673−3675.
(83) Pordea, A.; Creus, M.; Panek, J.; Duboc, C.; Mathis, D.; Novic,
M.; Ward, T. R. Artificial metalloenzyme for enantioselective
sulfoxidation based on vanadyl-loaded streptavidin. J. Am. Chem. Soc.
2008, 130, 8085−8088.
(84) Zhang, B. Y.; Jiang, Z. X.; Li, J.; Zhang, Y. N.; 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.
(85) Patwardhan, P. R.; Timko, M. T.; Class, C. A.; Bonomi, R. E.;
Kida, Y.; Hernandez, H. H.; Tester, J. W.; Green, W. H. Supercritical
water desulfurization of organic sulfides is consistent with free-radical
kinetics. Energy Fuels 2013, 27, 6108−6117.
(86) Yin, J. M.; Wang, J. P.; Li, Z.; Li, D.; Yang, G.; Cui, Y. N.; Wang,
A. L.; Li, C. P. Deep desulfurization of fuels based on an oxidation/
extraction process with acidic deep eutectic solvents. Green Chem.
2015, 17, 4552−4559.
(87) Jalilian, F.; Yadollahi, B.; Farsani, M. R.; Tangestaninejad, S.;
Rudbari, H. A.; Habibi, R. New perspective to keplerate
polyoxomolybdates: green oxidation of sulfides with hydrogen
peroxide in water. Catal. Commun. 2015, 66, 107−110.
(88) Li, J.-K.; Huang, X.-Q.; Yang, S.; Ma, H.-W.; Chi, Y.-N.; Hu, C.-
W. Four alkoxohexavanadate-based Pd-polyoxovanadates as robust
heterogeneous catalysts for oxidation of benzyl-alkanes. Inorg. Chem.
2015, 54, 1454−1461.
(89) Li, J.-K.; Dong, J.; Wei, C.-P.; Yang, S.; Chi, Y.-N.; Xu, Y.-Q.;
Hu, C.-W. Controllable synthesis of lindqvist alkoxopolyoxovanadate
clusters as heterogeneous catalysts for sulfoxidation of sulfides. Inorg.
Chem. 2017, 56, 5748−5756.
(90) Chen, Y.; Song, H.-Y.; Lu, Y.-Z.; Meng, H.; Li, C.-X.; Lei, Z.-G.;
Chen, B.-H. Unified catalytic oxidation−adsorption desulfurization
process using cumene hydroperoxide as oxidant and vanadate based
polyionic liquid as catalyst and Sorbent. Ind. Eng. Chem. Res. 2016, 55,
10394−10403.
(63) Tang, Y.-J.; Gao, M.-R.; Liu, C.-H.; Li, S.-L.; Jiang, H.-L.; Lan,
Y.-Q.; Han, M.; Yu, S.-H. Porous molybdenum-based hybrid catalysts
for highly efficient hydrogen evolution. Angew. Chem., Int. Ed. 2015,
54, 12928−12932.
(64) Castro-Osma, J. A.; Lamb, K. J.; North, M. Cr(salophen)
complex catalyzed cyclic carbonate synthesis at ambient temperature
and pressure. ACS Catal. 2016, 6, 5012−5025.
(65) Yang, S. L.; Peng, L.; Huang, P. P.; Wang, X. S.; Sun, Y. B.; Cao,
C. Y.; Song, W. G. Nitrogen, phosphorus, and sulfur Co-doped hollow
carbon shell as superior metal-free catalyst for selective oxidation of
aromatic alkanes. Angew. Chem., Int. Ed. 2016, 55, 4016−4020.
(66) Xie, S.; Lopez, S. A.; Ramstrom, O.; Yan, M. D.; Houk, K. N.
̈
1,3-dipolar cycloaddition reactivities of perfluorinated aryl azides with
enamines and strained dipolarophiles. J. Am. Chem. Soc. 2015, 137,
2958−2966.
(67) Zhou, Z.; He, C.; Xiu, J. H.; Yang, L.; Duan, C. Y. Metal−
organic polymers containing discrete single-walled nanotube as a
heterogeneous catalyst for the cycloaddition of carbon dioxide to
epoxides. J. Am. Chem. Soc. 2015, 137, 15066−15069.
(68) Ugale, B.; Dhankhar, S. S.; Nagaraja, C. M. Interpenetrated
metal-organic frameworks of cobalt(II): structural diversity, selective
capture, and conversion of CO2. Cryst. Growth Des. 2017, 17, 3295−
3305.
(69) Babu, R.; Roshan, R.; Gim, Y.; Jang, Y. H.; Kurisingal, J. F.; Kim,
D. W.; Park, D.-W. Inverse relationship of dimensionality and catalytic
activity in CO2 transformation: a systematic investigation by
comparing multidimensional metal−organic frameworks. J. Mater.
Chem. A 2017, 5, 15961−15969.
(70) Ai, J.; Min, X.; Gao, C.-Y.; Tian, H.-R.; Dang, S.; Sun, Z.-M. A
copper-phosphonate network as a highperformance heterogeneous
catalyst for the CO2 cycloaddition reactions and alcoholysis of
epoxides. Dalton Trans. 2017, 46, 6756−6761.
(71) Wang, J.-C.; Ding, F.-W.; Ma, J.-P.; Liu, Q.-K.; Cheng, J.-Y.;
Dong, Y.-B. Co(II)-MOF: a highly efficient organic oxidation catalyst
with open metal sites. Inorg. Chem. 2015, 54, 10865−10872.
(72) Zhao, Z. W.; Qin, J.; Zhang, C.; Wang, Y. R.; Yuan, D.; Yao, Y.
M. Recyclable single-component rare-earth metal catalysts for
cycloaddition of CO2 and epoxides at atmospheric pressure. Inorg.
Chem. 2017, 56, 4568−4575.
(73) D’Elia, V.; Dong, H. L.; Rossini, A. J.; Widdifield, C. M.;
Vummaleti, S. V. C.; Minenkov, Y.; Poater, A.; Abou-Hamad, E.;
Pelletier, J. D. A.; Cavallo, L. G.; Emsley, L.; Basset, J.-M. Cooperative
effect of monopodal silica-supported niobium complex pairs enhancing
catalytic cyclic carbonate production. J. Am. Chem. Soc. 2015, 137,
7728−7739.
(74) Zhao, Z. W.; Qin, J.; Zhang, C.; Wang, Y. R.; Yuan, D.; Yao, Y.
M. Recyclable single-component rare-earth metal catalysts for
cycloaddition of CO2 and epoxides at atmospheric pressure. Inorg.
Chem. 2017, 56, 4568−4575.
(91) Mizuno, N.; Kamata, K. Catalytic oxidation of hydrocarbons
with hydrogen peroxide by vanadium-based polyoxometalates. Coord.
Chem. Rev. 2011, 255, 2358−2370.
(92) Larrea, E. S.; Mesa, J. L.; Pizarro, J. L.; Iglesias, M.; Rojo, T.;
Arriortua, M. I. M(C6H16N3)2(VO3)4 as heterogeneous catalysts.
Study of three new hybrid vanadates of cobalt(II), nickel(II) and
copper(II) with 1-(2-aminoethyl)piperazonium. Dalton Trans. 2011,
40, 12690−12698.
(93) Li, J. K.; Huang, X. Q.; Yang, S.; Xu, Y. Q.; Hu, C. W.
Controllable synthesis, characterization, and catalytic properties of
three inorganic-organic hybrid copper vanadates in the highly selective
J
DOI: 10.1021/acs.inorgchem.7b01685
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
oxidation of sulfides and alcohols. Cryst. Growth Des. 2015, 15, 1907−
1914.
(94) Schneider, C. J.; Penner-Hahn, J. E.; Pecoraro, V. L. Elucidating
the protonation site of vanadium peroxide complexes and the
implications for biomimetic catalysis. J. Am. Chem. Soc. 2008, 130,
2712−2713.
(95) Xu, D.; Zhu, W. S.; Li, H. M.; Zhang, J. T.; Zou, F.; Shi, H.; Yan,
Y. S. Oxidative desulfurization of fuels catalyzed by V2O5 in ionic
liquids at room temperature. Energy Fuels 2009, 23, 5929−5933.
(96) Sheldrick, G. M. SHELXS-2014, Program for the crystal structure
solution; University of Gottingen: Gottingen, Germany, 2014.
̈
̈
(97) Sheldrick, G. M. SHELXL-2014, Program for the crystal structure
refinement; University of Gottingen: Gottingen, Germany, 2014.
̈
̈
(98) Farrugia, L. J. WINGX: A Windows Program for Crystal Structure
Analysis; University of Glasgow: Glasgow, U.K., 1988.
K
DOI: 10.1021/acs.inorgchem.7b01685
Inorg. Chem. XXXX, XXX, XXX−XXX