V= O Functionalized {Tm2}-Organic Framework Designed by Postsynthesis Modification for Catalytic Chemical Fixation of CO2and Oxidation of Mustard Gas

Article abstract of DOI:10.1021/acs.inorgchem.1c00053

In terms of recently documented references, the introduction of V= O units into porous MOF/COF frameworks can greatly improve their original performance and expand their application prospects due to a change in their electronegativity. In this work, by a cation-exchange strategy, a consummate combination of separate 4f [Tm2(CO2)8] SBUs and 3d [VIVO(H2O)2] units generated the functionalized porous metal-organic framework {(Me2NH2)2[VO(H2O)][Tm2(BDCP)2]·3DMF·3H2O}n (NUC-11), in which [Tm2(CO2)8] SBUs constitute the fundamental 3D host framework of {[Tm2](BDCP)2}n along with [VIVO(H2O)2] units being further docked on the inner wall of channels by covalent bonds. Significantly, NUC-11 represents the first example of V= O modified porous MOFs, in which uncoordinated carboxylic groups (-CO2H) further grasp the functional [VIVO(H2O)2] units on the initial basic skeleton along with the formation of covalent bonds as fixed ropes. Furthermore, activated samples of NUC-11 displayed a good catalytic performance for the chemical synthesis of carbonates from related epoxides and CO2 with high conversion rate. Moreover, by employing NUC-11 as a catalyst, a simulator of mustard gas, 2-chloroethyl ethyl sulfide, could be quickly and efficiently oxidized into low-toxicity products of oxidized sulfoxide (CEESO). Thus, this study offers a brand new view for the design and synthesis of functional-units-modified porous MOFs, which could be potentially applied as an excellent candidate in the growing field of efficient catalysis.

Full text of DOI:10.1021/acs.inorgchem.1c00053

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Article
VO Functionalized {Tm2}−Organic Framework Designed by
Postsynthesis Modification for Catalytic Chemical Fixation of CO2
and Oxidation of Mustard Gas
Hongtai Chen, Liming Fan, Tuoping Hu, and Xiutang Zhang*
Cite This: Inorg. Chem. 2021, 60, 5005−5013
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ABSTRACT: In terms of recently documented references, the introduction
of VO units into porous MOF/COF frameworks can greatly improve
their original performance and expand their application prospects due to a
change in their electronegativity. In this work, by a cation-exchange strategy,
a consummate combination of separate 4f [Tm2(CO2)8] SBUs and 3d
[VIVO(H2O)2] units generated the functionalized porous metal−organic
framework {(Me2NH2)2[VO(H2O)][Tm2(BDCP)2]·3DMF·3H2O}n
(NUC-11), in which [Tm2(CO2)8] SBUs constitute the fundamental 3D
host framework of {[Tm2](BDCP)2}n along with [VIVO(H2O)2] units
being further docked on the inner wall of channels by covalent bonds.
Significantly, NUC-11 represents the first example of VO modified
porous MOFs, in which uncoordinated carboxylic groups (−CO2H) further
grasp the functional [VIVO(H2O)2] units on the initial basic skeleton along
with the formation of covalent bonds as fixed ropes. Furthermore, activated samples of NUC-11 displayed a good catalytic
performance for the chemical synthesis of carbonates from related epoxides and CO2 with high conversion rate. Moreover, by
employing NUC-11 as a catalyst, a simulator of mustard gas, 2-chloroethyl ethyl sulfide, could be quickly and efficiently oxidized into
low-toxicity products of oxidized sulfoxide (CEESO). Thus, this study offers a brand new view for the design and synthesis of
functional-units-modified porous MOFs, which could be potentially applied as an excellent candidate in the growing field of efficient
catalysis.
a huge challenge to successfully assemble the targeted porous
Ln-MOFs, their excellent properties in the aspects of selective
separation and storage, luminescence and recognition, and
catalysis continue to attract remarkable attention from many
scientists. Especially, the fact that the rich coordination
geometry of Ln3+ ions due to the ratio of charge to radius
(Z/R) and abundant hybrid orbitals of fnd2+msp3 (n = 0−3, m =
1−3) gives them a wide coordination number range, which
grants octa- or nonacoordinated Ln3+ ions the ability to
polarize small guest molecules, such as CO2, SO2, and H2S.20,21
Recently, one porous Eu-MOF reported by Zhao and co-
workers exhibited an efficient catalytic performance for the
chemical fixation of CO2,22 which confirmed that Ln-MOFs
are subjects worthy of study due to the fact that the high
coordination characteristics of LnIII ions give them ideal Lewis
acid sites. Therefore, the exploration of syntheses and
INTRODUCTION
■
Over the past decade, much attention has been paid to the self-
assembly of porous metal−organic frameworks (MOFs), which
have the characteristics of large specific surface area and can be
potentially applied as gas separators and collectors, catalysts for
chemical reactions, molecular sensors, etc.1−8 Usually, the
substitution of metal cations or organic ligands leads to a
completely novel topology along with realization of the goal of
functionalization, on which basis huge numbers of MOFs with
unique specific functions have been documented.9−14 More-
over, in recent years, in order to enhance the functional
characteristics, in-depth research has concentrated on increas-
ing the specific surface area and adjustable aperture of targeted
MOFs by the typical strategies of employing functional ligands
or mixed ligands, introducing templates postmodification with
polar functional groups. Thus, a great number of MOFs
combining multistage pore structures and specific functions
have emerged. However, in comparison to d-block metal based
MOFs, the adsorption and catalytic performance exhibited by
porous Ln-MOFs have rarely been reported,15−19 which could
be attributed to the defects of hard-sphere and coordination-
geometry flexibility from Ln3+ ions habitually leading to a low-
dimensional framework or interwoven structure. Although it is
Received: January 7, 2021
Published: March 15, 2021
https://dx.doi.org/10.1021/acs.inorgchem.1c00053
© 2021 American Chemical Society
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obtained by cation exchange over 10 days with a Tm:V mole ratio of
2.02:1.00, as determined by ICP analysis.
optimization for Ln-based host skeletons by increasing highly
active sites to achieve targeted catalysts has become inevitable.
In addition, to exploit types of new catalytic materials that
have excellent characteristics including safety, high efficiency,
convenient recyclability, and reusability is momentous from
the perspective of applications. Under this premise, several
representative categories of multihole functional materials
including COFs (covalent-organic frameworks), POPs (po-
rous-organic polymers), and MOFs have aroused the
enthusiasm of researchers,23−33 which has led to the design
and syntheses of novel catalytic models. Recently, on the basis
of the principle of coordination binding, vanadium oxide units
were successfully docked on the skeleton of COFs by Ma and
co-workers to form the heterogeneous catalysts VO-PyTTA-
2,3-DHTA and VOTAPT-2,3-DHTA, which displayed ex-
cellent catalytic performance for Mannich-type reactions due
to the postfunctionalized VO active sites.18 Furthermore,
porous VO(salen)-derived MOFs documented by Cui and co-
workers allowed alcohol derivatives to be effectively catalyzed
into the corresponding aldehydes with an elevated enantiose-
lectivity and activity.10 Moreover, the results reported by Farha
and co-workers verified that 2-chloroethyl ethyl sulfide
(CEES), a simulator of mustard gas, could be oxidized into
an oxidized sulfoxide (CEESO) by VO2-uploaded nanotubes.11
Therefore, the modification of porous MOF platforms by
implanting VO units could realize the functionalization of
the MOF materials and effectively improve the catalytic effect
for specific chemical reactions. However, such related research
has still scarcely been reported so far.
Inspired by the excellent catalytic performance devoted by
previously documented porous VO-dock MOFs/COFs, we
carried out a cation exchange by soaking {(Me2NH2)-
[Tm3(HPTTBA)2]·3DMF·3H2O}n (1-Tm) units to form the
blue crystalline material {(Me2NH2)2[VO(H2O)]-
[Tm2(BDCP)2]·3DMF·3H2O}n (NUC-11), whose structure
could be verified by single-crystal X-ray diffraction analysis of
the incompletely exchanged {(Me2NH2)1. 5[(VO-
(H2O)2)0.5Tm0.5][Tm2(BDCP)2]·3DMF·3H2O}n (NUC-
11H). In NUC-11, [Tm2(CO2)8] SBUs are connected by
four deprotonated carboxyl groups of H5BDCP to form a
porous 3D host framework of {[Tm2](BDCP)2}n. [VIVO-
(H2O)2] units are further decorated on the inner wall of the
channels by two coordination covalent bonds formed from the
remaining spare deprontoated carboxyl group of H5BDCP,
resulting in the targeted VO-docked MOFs with a void volume
of 47.4%.
Catalytic Cycloadditions of CO2 with Various Epoxides.
Typically, certain amounts of fully activated NUC-11, epoxide, and
tetrabutylammonium bromide (Bu4NBr) were employed and sealed
in a 20 mL stainless-steel reactor equipped with a magnetic stirrer,
and then the reactor was transferred into a constant-temperature
water bath to reach the desired temperature. CO2 was continuously
purged into the reactor to manitain the desired pressure condition.
After the reaction was over, the heterogeneous catalyst NUC-11 could
be easily collected by centrifugation separation and resued by washing
1
with DMF and Cl2CH2 in turn. H NMR spectroscopy and GC/MS
were employed to determine the conversion rate and yield of the
transformed product.
Catalytic Oxidation of 2-Chloroethyl Ethyl Sulfide. In a
typical catalytic reaction, 50 mg of the catalyst (NUC-11) with 0.025
mmol of VO active sites, 2.0 mmol of tert-butyl hydroperoxide, and
1 mmol of 2-chloroethyl ethyl sulfide were dispersed in a dram vial in
the presence of 3 mL of acetonitrile. Then the vial was transferred to a
water bath to reach the desired temperature. After completion of the
reaction, the mixture was washed with DMF and reused for successive
catalysis experiments. The desired product was determined by 1H
NMR spectroscopy and GC-MS analysis.
RESULTS AND DISCUSSION
■
Description of Crystal Structure. As judged by a single-
crystal X-ray diffraction (SCXRD) analysis of NUC-11H and
the metal elemental analysis of ICP, NUC-11 crystallized in
the monoclinic space group C2/c with one crystallographically
independent ion of TmIII, one VIVO(H2O)2, and half of
BDCP5− being included in the asymmetric heterometallic unit.
It is worth mentioning that the single-crystal transformation
took place after cation exchange with cell parameters of a =
18.805 Å, b = 23.195 Å, and c = 21.192 Å being converted into
a = 17.982 Å, b = 23.007 Å, and c = 21.643 Å. At the same
time, H6PTTBA was decarboxylated in situ to form the
pentacarboxyl ligand H5BDCP (Scheme 1). As demonstrated
Scheme 1. Cation Exchange Strategy for NUC-11 by an
Impregnation Method
EXPERIMENTAL SECTION
■
in Figure 1, three {Tm2} SBUs were connected by one
BDCP5− to form the 3D host framework {[Tm2](BDCP)2}n,
which was further decorated by the cation [VO(H2O2)]2+ to
result in one anionic 3d−4f 3D heterometallic [VO-
(H2O)2]2[Tm2]-organic framework with 1D open channels.
Such an anionic framework was further charge-balanced by the
dimethylamine cation generated in situ by the decomposition
of DMF molecules. Furthermore, to observe the IR spectrum
shown in Figure S2, the strong adsorption peak at 981 cm−1
confirmed that terminal VO stretches existed. Meanwhile,
the valence of vanadium was confirmed by an XPS spectrum
(Figure S4); characteristic binding energies at 524 and 517 eV
Preparation of NUC-11. {(Me2NH2)[Tm3(HPTTBA)2]·3DMF·
3H2O}n (1-Tm) was prepared by employing a previously reported
synthetic route.36 A 0.1 g portion of freshly obtained single crystals of
1-Tm was soaked in a solution of 0.1 g of VOSO4, 8 mL of H2O, and
2 mL of DMF for 5 days at 310 K. During the soaking period, the
VOSO4 solution was refreshed every day and the crystal sample was
monitored with ICP. Unfortunately, only the partially prepared
product (NUC-11H) could be characterized by single-crystal X-ray
diffraction, which displayed that mononuclear Tm ions have been
half-exchanged, in accordance with the data of ICP and elemental
analysis. Anal. Calcd for the sample of NUC-11H suitable for single-
crystal X-ray diffraction (C127H100N10O49Tm5V): C, 44.27; H, 2.93;
N, 4.06; Tm, 24.51; V, 1.48. Found: C, 44.12; H, 2.85; N, 3.97; Tm,
24.33; V, 1.55. IR (KBr pellet, cm−1, Figure S2): 3417 (vs), 1613 (s),
1385 (s), 1250 (w), 1124 (s), 981 (s), 755 (w), 691 (w), 605 (w),
517 (w). The completely cation exchanged sample of NUC-11 was
were observed, consistent with V 2p3/2 and V 2p1/2
,
respectively, revealing that the oxidation state of vanadium in
NUC-11 was mainly +4.31−34 The component ratio for V and
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rings situated on the 6-position of pyridine from two
neighboring BDCP ligands. Meanwhile, each vanadium was
further coordinated by one aquous molecule except for one
originally teminal oxygen atom (Figure 1b ,c). Undoubtedly,
the successful docking of [VIVO(H2O)2] units could cause the
steadiness of the host three-dimensional skeleton. Moreover, it
is worth mentioning that the immobilized [VIVO(H2O)2] units
were rightly situated in the regions of inner channel surfaces,
which make NUC-11 a potential heterogeneous catalyst for
some specific organic reactions due to the fact that VO
could be taken as strong Lewis acid and base sites.35−38
Meanwhile, as exhibited in Figure 1d, NUC-11 had regular 1D
channels of ca. 7.68 × 8.69 Å2 along the [1,0,−1] axis. Finally,
a topological analysis indicated that the whole structure of
NUC-11 could be defined as a (4,6)-connected network with
the point symbol {62.53.6}2{44.52.62.72.84.9} by defining
BDCP5− and [Tm2(CO2)8] SUBs as 4- and 6-connected
nodes, respectively (Figure S1b).
Water Stability. Their low stability especially in an
aqueous environment and deliquescence during preservation
have caused MOFs to be scarcely popularized in practical
applications.35 Consequently, to test the water stability of the
cation-exchanged framework of NUC-11, several simulated
aquatic systems at different temperatures were employed for
soaking the NUC-11 crystals. After a certain time, the crystals
were separated by centrifugal filtration and the structures
determined by a PXRD analysis. As shown in Figure S5,
whether in normal temperature water or boiling water, PXRD
patterns corresponded to that the pattern of the as-synthesized
NUC-11, implying the strong water tolerance of NUC-11. The
reason for strong water stability is mainly that the modified
VO ions may influence the pore environment and build a
strong hydrophobic inner surface of NUC-11.36
Figure 1. Coordination mode of Tm(III) and V(IV) ions: (a) the 3D
framework and (b) schematic representation of (c) channels in NUC-
11 decorated with [VIVO(H2O)2] units (green, V; pink, Tm; red, O;
blue, N, gray, C). (d) 3D channels containing the framework of NUC-
11 along the [1,0,−1] axis.
Tm obtained from an ICP determination was also consistent
with the conclusion of SCXRD analysis.
Significantly, NUC-11 represents the first example of a V
O modified porous MOF, in which carboxylic groups
(−CO2H) further grasp [VIVO(H2O)2] units on the initial
basic skeleton along with the formation of covalent bonds as
fixed ropes. So far, only Ma and co-workers have obtained
several 2D VO-COFs synthesized from a postsynthetic
modification with vanadyl acetylacetonate, which exhibited
better catalytic performance due to its intrinsic features,
including porous structures and VO groups.33 Moreover,
from the aspect of structural modification, NUC-11 shows
great structural similarity with VO-COFs: that is, VO groups
exist in the form of a suspension on the inner wall of the
channels. Thus, this work offers a feasible synthesis strategy for
the functionalization of porous MOFs by postsynthesis
modification, which could meet the needs of multidimensional
skeleton links and further grasp targeted functional metal units
at the same time.
As displayed in Figure 1a and Figure S1a, the Tm(III) ion
was first chelated by two deprotonated α-carboxyl groups from
two phenyl rings stationed on both sides of the Npyridine atom.
Then two Tm(III) ions were further bridged by four γ-position
μ2-η1:η1 carboxyl groups subordinated to four phenyl rings,
among which two were located at the 4-position of pyridine
and other two at the 2-position of pyridine. Thus, eight
carboxyl groups from six BDCP5− ligands synergistically
connected two Tm(III) ions to form the basic spindle-shaped
binuclear SBUs of [Tm2(CO2)8].
Gas Adsorption Studies. In view of the total solvent-
accessible volume of 47.4% for NUC-11 derived from
PLATON software, the permanent porosity was checked by
a cryogenic nitrogen sorption experiment on the fully activated
sample (Figure S6), which was obtained by the manipulation
of solvent exchange and evacuation at 150 °C for 6 h. As
shown in Figure S7, the N2 sorption isotherms at 77 K
presented a typical reversible type I sorption behavior. The
increaseing adsorption capacity in the low-pressure region
confirmed that NUC-11 had microporous characteristics.37,38
39
With an increase in pressure, the N2 uptake gradually tended to
be saturated, giving a maximum adsorption quantity of 325
cm3 (STP) g−1 at 1 atm with the Langmuir and BET specific
surface areas being 1547.8 and 1326.4 m2 g−1, respectively.
Prior to carrying out the catalytic cycloaddition of CO2, the
sorption performance for CO2 was determined, as illustrated in
Figure 2. The adsorption quantity (1 bar) of CO2 reached 98.3
and 66.4 cm3 g−1 at 273 and 298 K, respectively, which was
better than documented heterometallic doping MOFs with
approximate porosity.39 which should be ascribed to the
contribution from [VIVO(H2O)2] units. Meanwhile, the CO2
isosteric heat (Qst) was calculated by virial method based on
the CO2 isotherms measured at 273 and 293 K, from which the
resulted Qst value was 26.75 kJ mol−1 at zero loading and 24.92
kJ mol−1 at the maximum measured loading (Figure S8).
Furthermore, with CO2 loading, no obvious change in the Qst
value was observed, indicating that the binding sites were
homogeneous. Moreover, it is worth noting that the extremely
high isosteric heat value was probably caused by the additional
contribution of vanadium ions with significant π back-bonding,
Furthermore, as dispalyed in Figure 1b, each ligand of
BDCP5− with the assistance of four carboxyl groups could
connect three {Tm2} SBUs to generate a 3D grid network
featuring 1D channels with a window size of ca. 7.41 × 8.63 Å
alongthe a axis. There was still one remaining carboxyl group
for each BDCP ligand, which renders further modification
feasible. Interestingly, VO ions were grafted into the
established host framwork of {[Tm2](PTTBA)2}n by coordi-
nating to μ1-η1:η0 carboxyl groups subordinated to two phenyl
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reaction of entry 1 indicates that NUC-11 and Bu4NBr with
thier unique superiorities work on different steps for the
second-order coupling reaction. Furthermore, with an increase
in the reaction temperature from 50 to 70 °C (entries 4−6),
the conversion rate accordingly increased, showing that
temperature is an important factor to influence the catalytic
efficency. However, when the quantity of Bu4NBr as cocatalyst
was doubled, the conversion rate could quickly increase to 99%
at 70 °C within 6 h. Therefore, the optimal conditions were
defined as 50 mg of NUC-11, 5 mol % of Bu4NBr, 70 °C, and
6 h. In addition, when the catalyst dose was doubled, a high
reaction yield could be obtained within 4 h (entry 10). To
better understand the synergistic effect of the various active
species in NUC-11, some blank experiments in the presence of
raw materials including Tm(NO3)3, VOSO4, and H5BDCP
ligand as single catalysts were carried out under the optimal
conditions. As shown in Table S4, the catalytic activities of
these compounds were lower than that NUC-11.
Furthermore, a series of epoxide derivatives with different
substitutes and molecular sizes were used to explore the effect
of substituents on the reaction and the catalytic universality of
NUC-11 under the established optimal reaction conditions, in
which the molecular sizes of these epoxide derivatives were all
smaller than the pore diameter of NUC-11 to avoid a surface
catalysis (Table S3). Just as expected, all of the epoxide
derivatives could be successfully transformed into the
corresponding carbonates with high conversion rate of above
93%, as demonstrated in Table 2; the corresponding 1H NMR
spectra of products are given in Figures S13−S16. With regard
to the difference in catalytic efficienciesa, entries 1−4 exhibit a
higher conversion rate in comparison to entry 5; a similar
Figure 2. CO2 adsorption isotherms at 273 and 298 K.
which gave NUC-11 an excellent potential separation perform-
ance for mixed gases, just as was documented for VMOF-
74.39,40
Catalytic Cycloaddition of CO2 and Epoxides. In view
of these remarkable characteristics of NUC-11, including a
high proportion of void volume, a large specific surface area,
abundant active metal sites (VO and TmIII), and moderate
CO2 adsorption capacity, the catalytic activity of NUC-11 was
explored for the cycloaddition reaction of epoxides with CO2,
widely regarded as a two-step catalytic reaction.40−52 To
explore the influence the of reaction conditions on the
conversion rate of epoxide, propylene oxide was selected as a
model substrate and the desired product of propylene
1
carbonate was determined by H NMR (Figure S12). In a
typical experiment, the amount of propylene oxide was fixed at
20 mmol, exhibiting a low conversion rate of 9% in the
presence of only activated NUC-11 at 50 °C (entry 2, Table
1); meanwhile a similarly low conversion rate of 17% was
observed in the presence of only the cocatalyst Bu4NBr (entry
3). However, by simultaneously employing 50 mg of NUC-11
and 2.5% Bu4NBr, the yield could reach 44%, as shown in
entry 4. On the other hand, the almost stagnant coupling
Table 2. Cycloaddition Reaction of CO2 and Various
Epoxides with NUC-11 as Catalyst
a
Table 1. Cycloaddition Reaction of CO2 with 1,2-
a
Epoxypropane under Various Conditions
b
entry NUC-11 (mg) Bu4NBr (mol %) T (°C) time (h) yield (%)
1
2
3
4
5
6
7
8
9
10
0
50
0
50
50
50
50
50
50
100
0
0
50
50
50
50
60
70
50
60
70
70
6
6
6
6
6
6
6
6
6
4
<1
9
2.5
2.5
2.5
2.5
5
5
5
5
17
44
60
75
58
81
99
99
a
Reaction conditions: substrate (20 mmol), Bu4NBr (5 mol %),
a
Reaction conditions: 1,2-epoxypropane (20 mmol), NUC-11 (50
NUC-11 (50 mg, 0.025 mol %, based on the VO ions), CO2 (1
b
mg, containing 0.025 mmol of VO ions), solvent free, CO2 (1 atm),
atm), 70 °C, 6 h. Determined by GC/MS with n-dodecane as the
b
c
6 h. Checked by 1H NMR and GC-MS spectroscopy with n-
internal standard. TON (turnover number) = (mol of product)/
dodecane as the internal standard.
(mol of catalyst).
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phenomenon has been found in other documented MOF-
based catalysts.48−55 From our speculation, the reasons include
mainly (i) epoxide derivatives with a large molecular size will
affect their accessibility into the nanochannels and (ii) large
substituents on the epoxides with strong steric hindrance will
influence the opportunity to contact with catalytically active
sites. Moreover, in comparison to the previously reported
monometallic Ln-organic framework,49−53 cation-exchanged
NUC-11 exhibited a faster catalytic efficiency. The reason for
this, structurally, is thaat the postmodified [VIVO(H2O)2] units
on the surface of the nanochannels protrude into the position
where the substrates could be easily hit, and hence an
improved catalytic efficiency could be realized.
of a bromoalkoxide that coordinated weakly with the VO
ions. Furthermore, the bromoalkoxide undergoes a nucleo-
philic addition with the CO2 molecules polarized by Lewis
acidic sites to form the alkylcarbonate anion. Ultimately, the
transformation of the alkylcarbonate anion into the five-
membered-ring carbonate is accomplished by a closed-loop
step.52−55
Catalytic Oxidation of 2-Chloroethyl Ethyl Sulfide. In
addition to the chemical fixation of CO2, the catalytic efficiency
of NUC-11 for oxidizing a simulator of mustard gas, 2-
chloroethyl ethyl sulfide (CEES), was checked by employing a
70% aqueous solution of tert-butyl hydroperoxide (TBHP)
with acetonitrile as the solvent during the experiments. The
results summarized in Table 3 show that NUC-11 possesses an
Moreover, recycling experiments using 20 mmol of
propylene oxide as the substrate and 50 mg of NUC-11 as
the catalyst were repeated five times under the optimal
conditions. After each cycle, the NUC-11 sample was
recovered by simple filtration and washing with DMF. As
shown in Figure S10, the transformation yield after 6 h is
almost unchanged within five cycles, which might be
interpreted as the catalytic continuity of NUC-11. An
inductively coupled plasma (ICP) analysis demonstrated that
only trace amounts of Tm(III) (∼0.012%) and V(IV)
(∼0.014%) ions were monitored form the filtrate, which
ruled out the leaching of active species in the process of the
catalytic cycloaddition reaction. Such a result was reinforced by
the PXRD pattern of recovered NUC-11 shown inFigure S9;
the fine parallelism with the result of the original catalyst
confirmed the excellent reusability of NUC-11. Meanwhile, a
10-fold amplification reaction by using 500 mg of the catalyst
was simultaneously carried out under the optimal conditions,
as shown in Figure S11. As a result, NUC-11 still had high
catalytic efficiency after five cycles, indicating that NUC-11
possessed excellent practical application prospects.
Table 3. Oxidation of CEES into CEESO under Different
Conditions
a
catalyst NUC-11
time
(h)
conversion
yield
b
b
entry
(mg)
T (°C)
(%)
(%)
1
2
3
4
5
6
50
50
50
50
50
50
25
25
25
25
30
40
1
2
3
4
3
2
58
73
89
99
99
99
71
74
85
89
94
92
a
Reaction conditions: catalyst (NUC-11) 50 mg (containing 0.025
mmol of vanadium), CEES (1 mmol), TBHP (2.0 mmol), acetonitrile
b
3 mL, 100 rpm. Determined by GC/MS with n-dodecane as the
internal standard.
ideal catalytic performance, which is enhanced with an increase
in the time and temperature. The conversion rate at 25 °C
varied from 58% to 99% with time from 1 to 4 h, whereas the
conversion rate could reach almost 100% within 2 h when the
reaction temperature was set at 40 °C. It is worth mentioning
that the conversion rate is one more important indicator that
reflects the transformation of mustard gas into low-toxicity
products of oxidized sulfoxide (CEESO).56−69 Furthermore,
blank experiments employing 0.025 mmol of the related raw
materials of NUC-11 were conducted at 40 °C over 2 h, as
detailed in Table S5. The dramatically decreased conversion
rate implied that the synergistic effect of various active species
exists in NUC-11.
The proposed mechanism of chemical cycloaddition of alkyl
epoxides with CO2 into carbonates is given in Figure 3. First,
substrate molecules of the epoxide dispersed in the nano-
channels were expeditiously polarized by protruding VO
ions in the pore wall. Subsequently, the bromine ion released
from Bu4NBr makes a nucleophilic attack on the α-carbon
atom of epoxide, leaving an instantaneous anionic intermediate
On the basis of the structural features of NUC-11 and
previous documentation by Ma,18 the mechanism of catalytic
oxidation of 2-chloroethyl ethyl sulfide was speculated and is
displayed in Figure 4. First, the active Lewis acid sites of VO
units offered a charge attraction to the oxygen atom of TBHP
and then formed weak coordination bonds along with the V
O double bond being opened, generating the intermediate of
oxygenated compounds. Second, the instantaneous intermedi-
ate made an nucleophilic attack to the sulfur atom of the
approaching 2-chloroethyl ethyl sulfide concentrated in the 1D
channels of NUC-11, consequently achieving the purpose of
synergetic oxygen transfer along with the catalyst recovery.
Remarkably, it is worth noting that NUC-11 exhibited a
better catalytic efficiency in comparison to the documented
VO-COFs, which may be ascribed to the combination of
separate 4f [Tm2(CO2)8] SBUs and 3d [VIVO(H2O)2] units.
In VO-COFs, only VO units could act as the active centers to
take part in the reaction process, just as was elaborated in the
mechanism detailed above. However, in addition the highly
Figure 3. Representation of the possible mechanism of cycloaddition
of epoxide with CO2.
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Article
quickly and efficiently oxidized into low-toxicity products of
oxidized sulfoxide by tert-butyl hydroperoxide in the presence
of the NUC-11 catalyst. Thus, this study offers a new method
for the design and synthesis of functional-unit-modified porous
MOFs by postsynthesis modification.
ASSOCIATED CONTENT
* Supporting Information
■
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.inorgchem.1c00053.
Crystallographic data and refinement parameters of
NUC-11, selected bond lengths and angles, TGA curves
of as-synthesized (black) and activated (red) samples of
NUC-11, PXRD patterns of NUC-11 after water
treatment, IR spectra, and N2 absorption/desorption
isotherms of NUC-11 at 77 K (PDF)
Accession Codes
CCDC 2015095 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 Cam-
bridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
Figure 4. Proposed catalytic mechanism of NUC-11-catalyzed sulfide
oxidation.
active VO units discussed in detail for the catalytic reaction
mechanism, NUC-11 also contained high-coordination-num-
ber Tm3+ ions, which could tend to coordinate with TBHP due
to the fact that the abundant hybrid orbitals fnd2+msp3 around
Tm3+ ions give it a wide coordination number range.
Furthermore, to some extent, both the chemical fixation of
CO2 and the oxidation reaction had an approximate reaction
mechanism, during which the formation of coordination
intermediates existed.
AUTHOR INFORMATION
Corresponding Author
■
Xiutang Zhang − Department of Chemistry, College of Science,
North University of China, Taiyuan 030051, People’s
Republic of China; orcid.org/0000-0002-5654-7510;
Email: xiutangzhang@163.com
Just as was emphasized for the chemical fixation of CO2, the
recoverability and sustained stability of an emerging catalyst
are requirements that must be met before industrial
consideration of applications, which encouraged us to carry
out cyclic oxidization experiments on the NUC-11 catalyst.
After each test, the sample of NUC-11 was collected by
centrifugal separation and then rinsed three times with
methanol to remove the substrates. Consequently, the
obtained NUC-11 sample was immersed in acetone for 10
min, which was easily evaporated after vacuum drying. As
displayed in Figure S17, the conversion rate in the presence of
the recycled NUC-11 catalyst did not change significantly,
which verified that the VO docked MOFs of NUC-11 could
be viewed as one potential candidate for destroying mustard
gas. Meanwhile, the recycled NUC-11 sample was checked by
PXRD, which exhibited that the characteristic peaks could be
well fitted with those of the original crystalline sample, as
shown in Figure S9. The amounts of leached homogeneous
Tm(III) and V(IV) species were only 0.009% and 0.013%,
respectively, in the filtered liquor as monitored by ICP analysis,
verifying that a realistic heterogeneous catalytic process was
feasible.
Authors
Hongtai Chen − Department of Chemistry, College of Science,
North University of China, Taiyuan 030051, People’s
Republic of China
Liming Fan − Department of Chemistry, College of Science,
North University of China, Taiyuan 030051, People’s
Republic of China; orcid.org/0000-0003-4615-0533
Tuoping Hu − Department of Chemistry, College of Science,
North University of China, Taiyuan 030051, People’s
Republic of China; orcid.org/0000-0001-7437-3246
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.inorgchem.1c00053
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work received financial support from the Natural Science
Foundation of China (21101097, 21801230) and the Opening
Foundation of Key Laboratory of Laser & Infrared System of
Shandong University (2019-LISKFJJ-005).
CONCLUSIONS
■
By cation exchange, VO units were successfully docked on
the channel inner walls in the basic porous framwork of 1-Tm
as precursors to generate the novel functional porous
heterometallic-organic framework {[VO(H2 O)]-
[Tm2(BDCP)2]}n, which displayed excellent catalytic perform-
ance for the chemical synthesis of carbonates from related
epoxides and CO2 with a high conversion rate. In addition, a
simulator of mustard gas, 2-chloroethyl ethyl sulfide, could be
REFERENCES
■
(1) Feng, L.; Wang, K.-Y.; Lv, X.-L.; Yan, T.-H.; Li, J.-R.; Zhou, H.-
C. Modular Total Synthesis in Reticular Chemistry. J. Am. Chem. Soc.
2020, 142, 3069−3076.
(2) Yuan, S.; Huang, L.; Huang, Z.; Sun, D.; Qin, J.-S.; Feng, L.; Li,
J.; Zou, X.; Cagin, T.; Zhou, H.-C. Continuous Variation of Lattice
Dimensions and Pore Sizes in Metal-Organic Frameworks. J. Am.
Chem. Soc. 2020, 142, 4732−4738.
5010
https://dx.doi.org/10.1021/acs.inorgchem.1c00053
Inorg. Chem. 2021, 60, 5005−5013

Inorganic Chemistry
pubs.acs.org/IC
Article
(3) Howlader, P.; Zangrando, E.; Mukherjee, P. S. Self-Assembly of
Enantiopure Pd12 Tetrahedral Homochiral Nanocages with Tetrazole
Linkers and Chiral Recognition. J. Am. Chem. Soc. 2020, 142, 9070−
9078.
(4) Mondal, B.; Mukherjee, P. S. Cage Encapsulated Gold
Nanoparticles as Heterogeneous Photocatalyst for Facile and Selective
Reduction of Nitroarenes to Azo Compounds. J. Am. Chem. Soc. 2018,
140, 12592−12601.
(5) Howlader, P.; Mondal, B.; Purba, P. C.; Zangrando, E.;
Mukherjee, P. S. Self-Assembled Pd(II) Barrels as Containers for
Transient Merocyanine Form and Reverse Thermochromism of
Spiropyran. J. Am. Chem. Soc. 2018, 140, 7952−7960.
frameworks for tunable CO2 photoreduction. ACS Catal. 2019, 9,
1726−1732.
(20) Wei, J.-H.; Yi, J.-W.; Han, M.-L.; Li, B.; Liu, S.; Wu, Y.-P.; Ma,
L.-F.; Li, D.-S. A Water-Stable Terbium(III)-Organic Framework as a
Chemosensor for Inorganic Ions, Nitro-Containing Compounds and
Antibioticsin Aqueous Solutions. Chem. - Asian J. 2019, 14, 3694−
3701.
(21) Tian, J.-W.; Wu, Y.-P.; Li, Y.-S.; Wei, J.-H.; Yi, J.-W.; Li, S.;
Zhao, J.; Li, D.-S. Integration of Semiconductor Oxide and a
Microporous (3,10)-Connected Co6-Based Metal-Organic Frame-
work for Enhanced Oxygen Evolution Reaction. Inorg. Chem. 2019,
58, 5837−5843.
(6) Rosen, A. S.; Mian, M. R.; Islamoglu, T.; Chen, H.; Farha, O. K.;
Notestein, J. M.; Snurr, R. Q. Tuning the Redox Activity of Metal-
Organic Frameworks for Enhanced, Selective O2 Binding: Design
Rules and Ambient Temperature O2 Chemisorption in a Cobalt-
Triazolate Framework. J. Am. Chem. Soc. 2020, 142, 4317−4328.
(7) Islamoglu, T.; Chen, Z.; Wasson, M. C.; Buru, C. T.; Kirlikovali,
K. O.; Afrin, U.; Mian, M. R.; Farha, O. K. Metal-Organic
Frameworks Against Toxic Chemicals. Chem. Rev. 2020, 120 (16),
8130−8160.
(8) Wang, H.; Qian, C.; Liu, J.; Zeng, Y.; Wang, D.; Zhou, W.; Gu,
L.; Wu, H.; Liu, G.; Zhao, Y. Integrating Suitable Linkage of Covalent
Organic Frameworks into Covalently Bridged Inorganic/Organic
Hybrids Toward Efficient Photocatalysis. J. Am. Chem. Soc. 2020, 142,
4862−4871.
(9) Idrees, K. B.; Chen, Z.; Zhang, X.; Mian, M. R.; Drout, R. J.;
Islamoglu, T.; Farha, O. K. Tailoring Pore Aperture and Structural
Defects in Zirconium-Based Metal-Organic Frameworks for Krypton/
Xenon Separation. Chem. Mater. 2020, 32, 3776−3782.
(10) Xi, W.; Liu, Y.; Xia, Q.; Li, Z.; Cui, Y. Direct and Post-Synthesis
Incorporation of Chiral Metallosalen Catalysts into Metal-Organic
Frameworks for Asymmetric Organic Transformations. Chem. - Eur. J.
2015, 21, 12581−12585.
(11) Buru, C. T.; Wasson, M. C.; Farha, O. K. H5PV2Mo10O40
Polyoxometalate Encapsulated in NU-1000 Metal-Organic Frame-
work for Aerobic Oxidation of a Mustard Gas Simulant. ACS Appl.
Nano Mater. 2020, 3, 658−664.
(12) Kirlikovali, K. O.; Chen, Z.; Islamoglu, T.; Hupp, J. T.; Farha,
O. K. Zirconium-Based Metal-Organic Frameworks for the Catalytic
Hydrolysis of Organophosphorus Nerve Agents. ACS Appl. Mater.
Interfaces 2020, 12, 14702−14720.
(13) Liu, J.; Zhao, Y.; Dang, L. L.; Yang, G. P.; Ma, L. F.; Li, D. S.;
Wang, Y. Y. Highly stable 3D porous HMOF with enhanced catalysis
and fine color regulation by the combination of d- and p-ions when
compared with those of its monometallic MOFs. Chem. Commun.
2020, 56 (62), 8758−8761.
(14) Wu, Y. P.; Tian, J. W.; Liu, S.; Li, B.; Zhao, J.; Ma, L. F.; Li, D.
S.; Lan, Y. Q.; Bu, X. Bi-Microporous Metal-organic-frameworks with
Cubane [M4(OH)4] (M = Ni, Co) Clusters and Pore Space Partition
for Electrocatalytic Methanol Oxidation Reaction. Angew. Chem., Int.
Ed. 2019, 58, 12185−12189.
(15) Huang, D.; Wu, X.; Tian, J.; Wang, X.; Zhou, Z.; Li, D.
Assembling of a novel 3D Ag(I)-MOFs with mixed ligands tactics:
Syntheses, crystal structure and catalytic degradation of nitrophenol.
Chin. Chem. Lett. 2018, 29, 845−848.
(22) Wang, X.; Li, B.; Wu, Y.-P.; Tsamis, A.; Yu, H.-G.; Liu, S.;
Zhao, Y.; Li, Y.-S.; Li, D.-S. Investigation on the Component
Evolution of a Tetranuclear Nickel-Cluster-Based Metal-Organic
Framework in an Electrochemical Oxidation Reaction. Inorg. Chem.
2020, 59, 4764−4771.
(23) Yu, C.-X.; Wang, K.-Z.; Li, X.-J.; Liu, D.; Ma, L.-F.; Liu, L.-L.
Highly Efficient and Facile Removal of Pb2+ from Water by Using a
Negatively Charged Azoxy-Functionalized Metal-Organic Framework.
Cryst. Growth Des. 2020, 20 (8), 5251−5260.
(24) Yang, X. G.; Zhai, Z. M.; Ma, L. F.; Yan, D. P. Fast
Crystallization-Deposition of Orderly Molecule Level Heterojunction
Thin Films Showing Tunable Up-Conversion and Ultrahigh Photo-
electric Response. ACS Cent. Sci. 2020, 6, 1169−1178.
(25) Fu, H. R.; Wang, N.; Wu, X. X.; Li, F. F.; Zhao, Y.; Ma, L. F.;
Du, M. Circularly Polarized Room-Temperature Phosphorescence
and Encapsulation Engineering for MOF-Based Fluorescent/Phos-
phorescent WLEDs. Adv. Optical Mater. 2020, 8 (13), 2000330.
(26) Yu, C. X.; Hu, F. L.; Song, J. G.; Zhang, J. L.; Liu, S. S.; Wang,
B. X.; Meng, H.; Liu, L. L.; Ma, L. F. Ultrathin two-dimensional
metal-organic framework nanosheets decorated with tetra-pyridyl calix
[4] arene: Design, synthesis and application in pesticide detection.
Sens. Actuators, B 2020, 310, 127819.
(27) Liu, J.; Yang, G. P.; Jin, J.; Wu, D.; Ma, L. F.; Wang, Y. Y. A first
new porous d-p HMOF material with multiple active sites for
excellent CO2 capture and catalysis. Chem. Commun. 2020, 56 (16),
2395−2398.
(28) Zhao, Y.; Wang, Y. J.; Wang, N.; Zheng, P.; Fu, H. R.; Han, M.
L.; Ma, L. F.; Wang, L. Y. Tetraphenylethylene-Decorated Metal-
Organic Frameworks as Energy-Transfer Platform for the Detection of
Nitro-Antibiotics and White-Light Emission. Inorg. Chem. 2019, 58,
12700−12706.
(29) Wu, Y. P.; Tian, J. W.; Liu, S.; Li, B.; Zhao, J.; Ma, L. F.; Li, D.
S.; Lan, Y. Q.; Bu, X. Bi-Microporous Metal-organic-frameworks with
Cubane [M4(OH)4] (M = Ni, Co) Clusters and Pore Space Partition
for Electrocatalytic Methanol Oxidation Reaction. Angew. Chem., Int.
Ed. 2019, 58, 12185−12189.
(30) Zhao, Y.; Yang, X. G.; Lu, X. M.; Yang, C. D.; Fan, N. N.; Yang,
Z. T.; Wang, L. Y.; Ma, L. F. {Zn6} Cluster based metal-organic
framework with enhanced room-temperature phosphorescence and
optoelectronic performances. Inorg. Chem. 2019, 58, 6215−6221.
(31) Cheng, Y. J.; Wang, R.; Wang, S.; Xi, X. J.; Ma, L. F.; Zang, S.
Q. Encapsulating [Mo3S13]2‑ clusters in cationic covalent organic
frameworks: enhancing stability and recyclability by converting a
homogeneous photocatalyst to a heterogeneous photocatalyst. Chem.
Commun. 2018, 54, 13563−13566.
(16) Qin, Z.; Dong, W.; Zhao, J.; Wu, Y.; Zhang, Q.; Li, D. A water-
stable Tb(III)-based metal-organic gel (MOG) for detection of
antibiotics and explosives. Inorg. Chem. Front. 2018, 5, 120−126.
(17) Wu, Y.; Zhou, W.; Zhao, J.; Dong, W.; Lan, Y.; L, D.; Sun, C.;
Bu, X. Surfactant-assisted phase-selective synthesis of new cobalt
MOFs and their efficient electrocatalytic hydrogen evolution reaction.
Angew. Chem., Int. Ed. 2017, 56, 13001−13005.
(18) Vardhan, H.; Verma, G.; Ramani, S.; Nafady, A.; Al-Enizi, A.
M.; Pan, Y.; Yang, Z.; Yang, H.; Ma, S. Covalent Organic Framework
Decorated with Vanadium as a New Platform for Prins Reaction and
Sulfide Oxidation. ACS Appl. Mater. Interfaces 2019, 11, 3070−3079.
(19) Wang, X.; Liu, J.; Zhang, L.; Dong, L.; Li, S.; Kan, Y.; Li, D.;
Lan, Y. Monometallic catalytic models hosted in stable metal-organic
̌
(32) Liu, F.-L.; Kozlevcar, B.; Strauch, P.; Zhuang, G.-L.; Guo, L.-Y.;
Wang, Z.; Sun, D. Robust Cluster Building Unit: Icosanuclear
Heteropolyoxocopperate Templated by Carbonate. Chem. - Eur. J.
2015, 21 (51), 18847−18854.
(33) Wang, X.-P.; Chen, W.-M.; Qi, H.; Li, X.-Y.; Rajnák, C.; Feng,
̌
Z.-Y.; Kurmoo, M.; Boca, R.; Jia, C.-J.; Tung, C.-H.; Sun, D. Solvent-
Controlled Phase Transition of a CoII-Organic Framework: From
Achiral to Chiral and Two to Three Dimensions. Chem. - Eur. J. 2017,
23 (33), 7990−7996.
(34) Wang, Z.; Li, X. Y.; Liu, L. W.; Yu, S. Q.; Feng, Z. Y.; Tung, C.
H.; Sun, D. Beyond Clusters: Supramolecular Networks Self-
5011
https://dx.doi.org/10.1021/acs.inorgchem.1c00053
Inorg. Chem. 2021, 60, 5005−5013

Inorganic Chemistry
pubs.acs.org/IC
Article
Assembled from Nanosized Silver Clusters and Inorganic Anions.
Chem. - Eur. J. 2016, 22 (20), 6830−6836.
(51) Garai, A.; Biradha, K. Cocrystals and Salts of 4,4′-Dinitro-
2,2′,6,6′-tetracarboxybiphenyl with N-Heterocycles: Solid State
Photodimerization of Criss-Cross Aligned Olefins and Photophysical
Properties. Cryst. Growth Des. 2020, 20, 8059−8070.
(52) Moi, R.; Ghorai, A.; Banerjee, S.; Biradha, K. Amino- and
Sulfonate-Functionalized Metal-Organic Framework for Fabrication
of Proton Exchange Membranes with Improved Proton Conductivity.
Cryst. Growth Des. 2020, 20, 5557−5563.
(53) Garai, M.; Biradha, K. Water-Resistant and Transparent Plastic
Films from Functionalizable Organic Polymers:Coordination Poly-
mers as Templates for Solid-State [2++2]-Photopolymerization.
Chem. - Eur. J. 2017, 23, 273−277.
(54) Konavarapu, S. K.; Ghosh, D.; Dey, A.; Pradhan, D.; Biradha,
K. Isostructural NiII Metal-Organic Frameworks (MOFs) for Efficient
Electrocatalysis of Oxygen Evolution Reaction and for Gas Sorption
Properties. Chem. - Eur. J. 2019, 25, 11141−11146.
(55) Mandal, R.; Garai, A.; Peli, S.; Datta, P. K.; Biradha, K.
Photoinduced Bending of Single Crystals of a Linear Bis-Olefin via
Water-Templated Solid-State [2 + 2] Photopolymerization Reaction.
Chem. - Eur. J. 2020, 26, 396−400.
(56) Maity, K.; Nath, K.; Sinnwell, M. A.; Motkuri, R. K.;
Thallapally, P. K.; Biradha, K. Isoreticular Expansion of Metal-
Organic Frameworks via Pillaring of Metal Templated Tunable
Building Layers: Hydrogen Storage and Selective CO2 Capture. Chem.
- Eur. J. 2019, 25, 14500−14505.
(57) Maity, K.; Karan, C. K.; Biradha, K. Porous Metal-Organic
Polyhedral Framework containing Cuboctahedron Cages as SBUs
with High Affinity for H2 and CO2 Sorption: A Heterogeneous
Catalyst for Chemical Fixation of CO2. Chem. - Eur. J. 2018, 24,
10988−10993.
(58) Howlader, P.; Zangrando, E.; Mukherjee, P. S. Self-Assembly of
Enantiopure Pd12 Tetrahedral Homochiral Nanocages with Tetrazole
Linkers and Chiral Recognition. J. Am. Chem. Soc. 2020, 142, 9070−
9078.
(35) Xu, Z.; Han, L.-L.; Zhuang, G.-L.; Bai, J.; Sun, D. In Situ
Construction of Three Anion-Dependent Cu(I) Coordination
Networks as Promising Heterogeneous Catalysts for Azide-Alkyne
“Click” Reactions. Inorg. Chem. 2015, 54 (10), 4737−4743.
(36) Yan, Z.-H.; Li, X.-Y.; Liu, L.-W.; Yu, S.-Q.; Wang, X.-P.; Sun, D.
Single-Crystal to Single-Crystal Phase Transition and Segmented
Thermochromic Luminescence in a Dynamic 3D Interpenetrated Ag-
I Coordination Network. Inorg. Chem. 2016, 55 (3), 1096−1101.
̌
́
(37) Yuan, Y.; Sheng, K.; Zeng, S.; Han, X.; Sun, L.; Loncaric, I.;
Zhan, W.; Sun, D. Engineering Cu/TiO2@N-Doped C Interfaces
Derived from an Atom-Precise Heterometallic CuII TiIV Cluster for
4
5
Efficient Photocatalytic Hydrogen Evolution. Inorg. Chem. 2020, 59,
5456−5462.
̌
́
(38) Liu, Y.-N.; Hou, J.-L.; Wang, Z.; Gupta, R. K.; Jaglicic, Z.;
̌
Jagodic, M.; Wang, W.-G.; Tung, C.-H.; Sun, D. An Octanuclear
Cobalt Cluster Protected by Macrocyclic Ligand: In Situ Ligand-
Transformation-Assisted Assembly and Single-Molecule Magnet
Behavior. Inorg. Chem. 2020, 59, 5683−5693.
̌
(39) Yu, F.; Ji, B.-Q.; Jagodic, M.; Su, Y.-M.; Zhang, S.-S.; Feng, L.;
̌
́
Kurmoo, M.; Jaglicic, Z.; Sun, D. Copper(II)-Assisted Ligand
Fragmentation Leading to Three Families of Metallamacrocycle.
Inorg. Chem. 2020, 59, 13524−13532.
(40) Liang, X.-Q.; Gupta, R.-K.; Li, Y.-W.; Ma, H.-Y.; Gao, L.-N.;
Tung, C.-H.; Sun, D. Structural Diversity of Copper(I) Cluster-Based
Coordination Polymers with Pyrazine-2-thiol Ligand. Inorg. Chem.
2020, 59, 2680−2688.
(41) Ma, C.; Wang, P.; Liu, Z.; Xin, C.; Wang, S.; Jia, J.; Ma, P.; Niu,
J.; Wang, J. Oxyfunctionalization of Alkanes Based on a Tricobalt(II)-
Substituted Dawson-Type Rhenium Carbonyl Derivative as Catalyst.
Inorg. Chem. 2020, 59, 8690−8698.
(42) Liang, Z.; He, Y.; Qiao, Y.; Ma, P.; Niu, J.; Wang, J. Sandwich-
Type Heteropolyniobate Templated by Mixed Heteroanions. Inorg.
Chem. 2020, 59, 7895−7899.
(43) Xu, Q.; Xu, B.; Kong, H.; He, P.; Wang, J.; Kannan, T.; Ma, P.;
Wang, J.; Niu, J. Synthesis and Characterization of a Crown-Shaped
36-Molybdate Cluster and Application in Catalyzing Knoevenagel
Condensation. Inorg. Chem. 2020, 59, 10665−10672.
(44) Zhang, M.; Liu, B.; Zhang, H.; Zhang, C.; Wang, J.; Niu, J.
Synthesis and Mechanism Studies of a High-Nuclear Mn72W48
Cluster. Inorg. Chem. 2020, 59, 13733−13740.
(45) Li, D.; Ma, X.; Wang, Q.; Ma, P.; Niu, J.; Wang, J. Copper-
Containing Polyoxometalate-Based Metal-Organic Frameworks as
Highly Efficient Heterogeneous Catalysts toward Selective Oxidation
of Alkylbenzenes. Inorg. Chem. 2019, 58, 15832−15840.
(46) Singh, V.; Liu, S.; Ma, P.; Drew, M. G. B.; Wang, J.; Niu, J.
Versatile {Cp2Ti} Grafted Hetero-Polyoxotungstate Clusters: Syn-
thesis, Crystal Structure, and Photocurrent Properties. Inorg. Chem.
2020, 59, 1125−1136.
(47) He, J.; Li, J.; Han, Q.; Si, C.; Niu, G.; Li, M.; Wang, J.; Niu, J.
Photoactive Metal-Organic Framework for the Reduction of Aryl
Halides by the Synergistic Effect of Consecutive Photoinduced
Electron-Transfer and Hydrogen-Atom-Transfer Processes. ACS Appl.
Mater. Interfaces 2020, 12, 2199−2206.
(48) Sun, N.; Wang, C.; Wang, H.; Gao, X.; Jiang, J. Photonic
Switching Porous Organic Polymers toward Reversible Control of
Heterogeneous Photocatalysis. ACS Appl. Mater. Interfaces 2020, 12,
56491.
(49) Han, B.; Wang, H.; Wang, C.; Wu, H.; Zhou, W.; Chen, B.;
Jiang, J. Postsynthetic Metalation of a Robust Hydrogen-Bonded
Organic Framework for Heterogeneous Catalysis. J. Am. Chem. Soc.
2019, 141, 8737−8740.
(50) Liu, W.; Li, X.; Wang, C.; Pan, H.; Liu, W.; Wang, K.; Zeng, Q.;
Wang, R.; Jiang, J. A Scalable General Synthetic Approach toward
Ultrathin Imine-Linked Two-Dimensional Covalent Organic Frame-
work Nanosheets for Photocatalytic CO2 Reduction. J. Am. Chem. Soc.
2019, 141, 17431−17440.
(59) Mondal, B.; Mukherjee, P. S. Cage Encapsulated Gold
Nanoparticles as Heterogeneous Photocatalyst for Facile and Selective
Reduction of Nitroarenes to Azo Compounds. J. Am. Chem. Soc. 2018,
140, 12592−12601.
(60) Howlader, P.; Mondal, B.; Purba, P. C.; Zangrando, E.;
Mukherjee, P. S. Self-Assembled Pd(II) Barrels as Containers for
Transient Merocyanine Form and Reverse Thermochromism of
Spiropyran. J. Am. Chem. Soc. 2018, 140, 7952−7960.
(61) Saha, R.; Devaraj, A.; Bhattacharyya, S.; Das, S.; Zangrando, E.;
Mukherjee, P. S. Unusual Behavior of Donor-Acceptor Stenhouse
Adducts in Confined Space of a Water-Soluble PdII8Molecular
Vessel. J. Am. Chem. Soc. 2019, 141, 8638−8645.
(62) Prakasam, T.; Devaraj, A.; Saha, R.; Lusi, M.; Brandel, J.;
Esteban-Gómez, D.; Platas-Iglesias, C.; Olson, M. A.; Mukherjee, P.
S.; Trabolsi, A. Metal-Organic Self-Assembled Trefoil Knots for C
Br Bond Activation. ACS Catal. 2019, 9, 1907−1914.
(63) Bhattacharyya, S.; Venkateswarulu, M.; Sahoo, J.; Zangrando,
E.; De, M.; Mukherjee, P. S. Self-Assembled PtII Metallosupramo-
8
lecular Tubular Cage as Dual Warhead Antibacterial Agent in Water.
Inorg. Chem. 2020, 59, 12690−12699.
(64) Bhattacharyya, S.; Maity, M.; Chowdhury, A.; Saha, M. L.;
Panja, S. K.; Stang, P. J.; Mukherjee, P. S. Coordination-Assisted
Reversible Photoswitching of Spiropyran-Based Platinum Macro-
cycles. Inorg. Chem. 2020, 59, 2083−2091.
(65) Sinha, I.; Mukherjee, P. S. Chemical Transformations in
Confined Space of Coordination Architectures. Inorg. Chem. 2018, 57,
4205−4221.
(66) Bhat, I. A.; Zangrando, E.; Mukherjee, P. S. Coordination-
Driven Self-Assembly of Discrete Molecular Nanotubular Architec-
tures. Inorg. Chem. 2019, 58, 11172−11179.
(67) Siddiqui, M. M.; Saha, R.; Mukherjee, P. S. Ruthenium(II)
Metalla[2]catenanes and Macrocycles via Donor-Dependent Self-
Assembly. Inorg. Chem. 2019, 58, 4491−4499.
(68) Das, P.; Kumar, A.; Chowdhury, A.; Mukherjee, P. S.
Aggregation-Induced Emission and White Luminescence from a
5012
https://dx.doi.org/10.1021/acs.inorgchem.1c00053
Inorg. Chem. 2021, 60, 5005−5013

Inorganic Chemistry
pubs.acs.org/IC
Article
Combination of π-Conjugated Donor-Acceptor Organic Luminogens.
ACS Omega 2018, 3, 13757−13771.
(69) Bhattacharyya, S.; Chowdhury, A.; Saha, R.; Mukherjee, P. S.
Multifunctional Self-Assembled Macrocycles with Enhanced Emission
and Reversible Photochromic Behavior. Inorg. Chem. 2019, 58, 3968−
3981.
5013
https://dx.doi.org/10.1021/acs.inorgchem.1c00053
Inorg. Chem. 2021, 60, 5005−5013