High Uptake of ReO4? and CO2 Conversion by a Radiation-Resistant Thorium–Nickle [Th48Ni6] Nanocage-Based Metal–Organic Framework

Article abstract of DOI:10.1002/anie.201901786

Assembled from [Th₄₈Ni₆] nanocages, the first transition-metal (TM)-thorium metal–organic framework (MOF, 1) has been synthesized and structurally characterized. 1 exhibits high solvent and acid/base stability, and resistance to 400 kGy β irradiation. Notably, 1 captures ReO₄^? (an analogue of radioactive ⁹⁹TcO₄^?, a key species in nuclear wastes) with a maximum capacity of 807 mg g^?1, falling among the largest values known to date. Furthermore, 1 can enrich methylene blue (MB) and can also serve as an effective and recyclable catalyst for CO₂ fixation with epoxides; there is no significant loss of catalytic activity after 10 cycles. Theoretical studies with nucleus-independent chemical shifts and natural bond orbital analysis reveal that the [Th₆O₈] clusters in 1 have a unique stable electronic structure with (d–p)π aromaticity, partially rationalising 1′s stability.

Full text of DOI:10.1002/anie.201901786

A Journal of the Gesellschaft Deutscher Chemiker
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International Edition Chemie
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Accepted Article
Title: High Uptake of ReO4− by a Radiation Resistant [Th48Ni6]
Nanocage-Based Metal−Organic Framework
Authors: Bin Zhao, Hang Xu, Chun-Shuai Cao, Han-She Hu, Shi-Bin
Wang, Jin-Cheng Liu, Peng Cheng, Nikolas Kaltsoyannis, and
Jun Li
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201901786
Angew. Chem. 10.1002/ange.201901786
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Angewandte Chemie International Edition
10.1002/anie.201901786
COMMUNICATION
High Uptake of ReO
−
4
by a Radiation Resistant [Th48Ni ] Nanocage-Based
6
Metal−Organic Framework
[a]
[a]
[b,c]
[b]
[b]
[a]
Hang Xu, Chun-Shuai Cao, Han-Shi Hu,* Shi-Bin Wang, Jin-Cheng Liu, Peng Cheng,
[
c]
[b]
[a]
Nikolas Kaltsoyannis,* Jun Li, Bin Zhao*
Abstract: Assembled from [Th48Ni
6
]
nanocages, the first
crust (similar to lead);[7,8] 2) Th has a relatively low toxicity, no
higher than Al3+ or Cr ;
3+ [9,10]
3) it is usually found in the +IV
transition-metal (TM)-Th metal-organic framework (MOF, 1) has
been synthesized and structurally characterized. 1 exhibits high
4
+
oxidation state, and similarly highly charged metal ions (e.g. Zr ,
4
+
[11-13]
solvent and acid/base stability, and resistance to 400 kGy β
Hf ) have been shown to yield robust MOF frameworks;
and
−
4+
irradiation. Notably, 1 captures ReO
4
(an analog of radioactive
4) flexible coordination of Th
can yield unprecedented
99
−
TcO
4
, a key species in nuclear wastes) with a maximum capacity
frameworks and topologies that cannot be accessed by transition
or lanthanide metals.
of 807 mg/g, falling among the largest values known to date.
Furthermore, 1 can enrich methylene blue (MB) and can also serve
Since O’Hare et al. reported the first Th-MOF in 2003,[14] other
as an effective and recyclable catalyst for CO
2
fixation with epoxides;
6
Th-MOFs, especially the stable Th -cluster with carboxylate
there is no significant loss of catalytic activity after 10 cycles.
Theoretical studies with nucleus-independent chemical shifts and
ligands, have also been synthesized in which gas absorption and
ion exchange were investigated.[15-19] However, heterometallic
MOFs containing Th and d-block TM ions have not been reported
hitherto. In this contribution, we report the synthesis of the first
6 8
natural bond orbital analysis reveal that the [Th O ] clusters in 1 have
a unique stable electronic structure with (d-p) aromaticity, partialy
rationalising 1’s stability.
TM-Th MOF, which exhibits radiation resistance, high stability,
−
and a capacity of ReO
4
uptake (as an analog of radioactive
−
TcO
TcO
4
). This work sheds light on further advanced materials for
Radioactive by-products of the fission process used to
generate nuclear power are of potential concern regarding their
impact on the environment and human beings, and thus much
effort has been devoted to nuclear waste disposal.[1] A key issue
−
4
capture.
is the enrichment and separation of radioactive 99TcO −
, because
4
it is highly water-soluble, mobile, and stable, potentially posing a
threat to the environment. Furthermore, hundreds of metric
−
have accumulated during fission of 235U or 239Pu
tonnes of TcO
4
−
over the past 70 years, increasing the urgency for TcO
uptake.[2,3]
4
To remove TcO −
, traditional anion exchange resins are
4
widely used.[4] However they lack strong radiation resistance and
chemical stability under extreme conditions.[5] Therefore,
designing and synthesizing novel, stable and porous materials,
possessing both strong radiation resistance and high uptake of
−
TcO
4
from contaminated water systems or during fuel
reprocessing, is of critical and urgent importance.[6]
Seeking porous compounds with strong radiation resistance,
we focused on the construction of porous metal-organic
frameworks (MOFs) built from thorium. We did so because 1) Th
is only modestly radioactive and relatively abundant in the earth’s
[a]
[b]
[c]
Dr. H. Xu, Dr. C.-S. Cao, Prof. Dr. P. Cheng, Prof. Dr. B. Zhao
Department of Chemistry
Key Laboratory of Advanced Energy Material Chemistry
Nankai University
Tianjin, 300071, China
E-mail: zhaobin@nankai.edu.cn
Prof. Dr. H.-S. Hu, Dr. W.-S. Bin, Mr. J. C. Liu, Prof. Dr. J. Li
Department of Chemistry and Key Laboratory of Organic
Optoelectronics & Molecular Engineering of Ministry of Education
Tsinghua University
Beijing 100084, China
-cluster and Ni2+ unit. (b) The structure of [Th48Ni
6 6
Figure 1. (a) The Th ]
nanocage. (c) The 3D network with cubic cavities.
E-mail: hshu@mail.tsinghua.edu.cn
Prof. Dr. H.-S. Hu, Prof. Dr. N. Kaltsoyannis
School of Chemistry
The University of Manchester
Oxford Road, Manchester, M13 9PL, UK
E-mail: nikolas.kaltsoyannis@manchester.ac.uk
3 4
Solvothermal reaction of isonicotinic acid (HIN), Th(NO )
and Ni(OAc)
yielded
2
in N,N-diethylformamide for one day at 120 o
C
1
jade-green
(μ -OH) (IN)12)(H
crystals
(OH)
of
2
n
·5 DMF·2 H O} ).
(
{[Ni
3
Th
6
(μ
3
-O)
4
3
4
2
O)12
]
·
6
Supporting information for this article is given via a link at the end of
the document.
Crystallographic analysis of 1 showed that it crystallizes in the
cubic system with space group Pm-3m (Table S1). The 3D
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Angewandte Chemie International Edition
10.1002/anie.201901786
COMMUNICATION
framework 1 is assembled from cubic [Th48Ni
diameters of 11.08 Å (Figure 1b), in which each Th
6
] cages with inner
-cluster
4.19 eV for Th
electronic stability of the cluster core.
6
(μ
3
-O)
4
(μ
3
-OH)
4
(COOH)12, indicating the high
6
occupies one vertex and each face of the cube contains a
To analyze the electronic structure of the cluster, we adopt
discrete Ni2+ ion (Figure 1b). Additionally, compound 1 belongs to
an O
valence MO-level pattern between Th
h 6 3 8
-symmetry [Th (μ -O)
]8+ model cluster as there is similar
-
a cationic framework, and free OH anions exists in the structure
6
(μ
3 4 3 4
-O) (μ -OH) (COOR)12
4
-
for balancing the charge (see detailed analysis in the SI). From
and Th (μ -O) (COOR)12 (R = H to mimic the bulky phenyl
6 3 8
the topological point of view, each Th
Th-O bond length of 2.38 Å, coordinates to twelve IN ligands,
forming a 12-connected node. Each Ni2+ links four Th
and can be considered as a 4-connected unit. The resulting
network can be described as a (4, 12)-connected framework with
the ftw-type topology, similar to the structure of Cu
3
Au alloy.[20]
6
-cluster, with an average
group), as listed in Figure S5. The general MO level pattern is
shown in the left side of Figure 3, where the froniter valence-MO
group orbitals are seperated with gaps of 10.87 eV and 1.81 eV
from the lower and higher groups. This valence group, as shown
in the middle of Figure 3, is composed of 102 valence MOs,
including mainly three parts: the lowest one is mostly 2p-band
-
6
-clusters,
The stability of compound 1 was investigated by various ways
with 24 MOs of O
MOs of Th fragment, and the third part is mainly 6d- and
7s-band with 36 MOs of Th fragment. The 2p-band is the valent,
occupied MOs that is seprated by 3.66 eV from the unoccupied
5f-band. This large metal-ligand energy gap also helps to confirm
]8+ cluster. Besides, due to
6 3 8
the stability of this [Th (μ -O)
8
fragment, the second part is 5f-band with 42
as below. First, its resistance to radiation was explored. Under a
6
5
5
5
total of 2×10 , 4×10 Gy β irradiation and 10 Gy γ irradiation with
6
4
a dose rate of 2×10 Gy/hour, 3D frameworks of 1 remain intact,
as is evidenced by PXRD of samples before and after irradiation
Figure S3a). It should be noted that humans cannot survive for
(
more than two days under 50 Gy total irradiation, and the
radiation dosage from the Hiroshima atomic bomb was about 10
Gy/hour.[23] Compound 1 clearly possesses radiation resistance.
Investigation of iodine adsorption on both un- and irradiated
samples showed that the adsorbing capacity is not significantly
affected by 200 kGy β irradiation (Figure S4), further supporting
the radiation resistance of 1. As far as we know, only a few stable
MOFs with radioresistance ability was explored under less than
metal-ligand (d-p) interaction there is significant mixing of 5f-
and 6d-orbitals in the 2p-band, as listed in Table S3 where the
symmetries, energies, MO compositions and 3D isosurfaces of
these frontier MOs are collected. HOMO-9 to HOMO contain 48
electrons and feature the principal 24 2p-band orbitals.
Especially notworthy is the eight electrons from four MOs
(HOMO-8 & HOMO-5 in Table S3), which provides the net
bonding interactions due to the significnat mixing of Th 5f- and
6d-orbitals with O-2p orbitals. These are multi-centre bonds
5
[1c,21,22,27]
2
×10 Gy
β
irradiation (Table S9),
whereas the
5
6 3 8
delocalized within [Th (μ -O)
]8+ core (Table S3), making this
investigations on stability of MOFs under 4×10 Gy β irradiation
have not been reported so far.
highly symmetric cage potentially aromatic. To further investigate
this aromatic stability, nucleus-independent chemical shift (NICS)
indices were calculated. Three types of sites were chosen: the
centres of the cage, the rhombus face composed of Th-O-Th-O,
and at 1 Å above the plane of the rhombus face. All the NICS
values at these points are negative (Table 1), indicating that the
We next explored the solvent stability of 1 by soaking it in
different solvents for 20 h; the PXRD patterns show that 1
possesses very good solvent stability (Figure S3b). Finally, the
acid/base stability of 1 was also investigated. 1 was immersed in
a series of solutions from pH 1 to 14, and the corresponding
PXRD patterns show that 1 remains intact from pH 1-13 (Figure
S3c). In summary, compound 1 displays radiation resistance and
excellent stability to solvent and pH, making it promising for
nuclear waste applications.
8+
[Th
6
(μ
3
-O)
8
]
cluster posseses aromatic character. In
comparision, the prototypical aromatic molecule benzene has a
NICS(0) value of -8.0 ppm and a NICS(1) of -10.2 ppm.[24]
We performed density functional theory (DFT) studies on
4
-
several
Th (μ -O)
the number of hydroxyl replacing oxygen (n = 0, 4 and 8) for the
model clusters, including [Th
6 3 8
(μ -O) (IN)12] ,
(IN)12]4+ according to
6
3
4
(μ
3
-OH) (IN)12 and [Th (μ -OH)
4
6
3
8
8+
6 8
core cluster of [Th O ] . As shown in Figure 2, the optimized
Th-O (Th-OH) bond lengths are, respectively, shorter and longer
than the measured one for n = 0 and 8. For n = 4, however, the
average Th-O bond length of 2.395 Å matches well the
experimentally determined Th-O bond lengths of 2.38 Å (Table
S2). As these three model clusters were studied via constrained
geometry optimizations, we additionally performed full geometry
optimizations of simplified model clusters Th
6
(μ
3
-O)
8
(COOH)124-,
Figure 2. DFT constrained optimization of three model clusters. (a)
[Th (μ -O) (IN)12] . (b) Th (μ -O) (μ -OH) (IN)12. (c) [Th (μ -OH) (IN)12]] .
6 3 8 6 3 4 3 4 6 3 8
Yellow, red, blue, grey and white spheres represent Th, O, N, C and H atoms,
respectively.
(COOH)124 by
+
4-
4+
Th (μ -O) (μ -OH) (COOH)12 and Th (μ -OH)
6
3
4
3
4
6
3
8
replacing the IN ligand with a formate anion (HCOO-). It is found
that these fully optimized RTh-O and RTh-OH bond lengths are
4
-
8+
almost the same as those from the [Th
Th (μ -O) (μ -OH) (IN)12 and [Th (μ -OH)
(IN)12]4+ clusters,
respectively, as shown in Table S2. All these results help to
confirm the formula of Th (μ -O) (μ -OH) (IN)12. Furthermore, as
shown in Figure S5, there is large HOMO-LUMO energy gap of
6
(μ
3
-O)
8
(IN)12] ,
We have also analysed the bonding in [Th O ] using the
6
8
6
3
4
3
4
6
3
8
natural bond orbital (NBO) and electron localisation function
(ELF) approaches. The NBO results show that the four Th- -oxo
3
6
3
4
3
4
linkages are highly oxygen-localised, with composition of 5.7%
d f + 94.3% O
Th (sp0.40 3.50 1.19) (sp2.10). Clearly, there is
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Angewandte Chemie International Edition
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COMMUNICATION
non-negligible Th particiation, despite the ionic feature. The ionic
nature of the Th-O bond is also revealed through ELF analysis.
of MOF attributes to both the electrostatic and covalent
interactions between Th , Ni cations and IN anions.
4
+
2+
-
8
+
The calculated 3D ELF contour of [Th
6
O
8
]
cluster with five
Table 2. Summary of the ReO −
adsorbing capacity of MOFs.
4
different values of the isosurface is shown in Figure S6. The
delocalized electron-pair density - evidence for Th-O connection
MOFs
Adsorbing Capacity (mg/g)
References
-
is shown only at small isosurface values (0.1 and 0.2), while for
Th-MOF
807
786
602
553
217
this work
larger values (0.3, 0.4 and 0.5), only localized closed-shell
distributions are present. The ELF diagrams provide evidence
that there is non-negligible, albeit weak, covalent and strong ionic
interaction in the Th-O bonds, similar to the conclusion from the
NBO analysis.
Ag(4,4′-bipyridine)NO
SLUG-21
3
25
26
27
21
SCU-100
SCU-101
6 8
Table 1. NICS values (ppm) of [Th O
]8+ cluster core.
NU-1000
210
159
28
29
Type
NICS
-2.17
-5.13
-1.51
UiO-66-NH
2
NICS(0), cubic center
The combination of radiation resistance and the large
[Th48Ni ] cage in a stable cationic framework, led us to wonder if
NICS(0), rhombus face center
NICS(1), 1 Å above rhombus face
6
1 can capture and enrich ReO
analog of 99TcO
radioactive TcO
anhydrous CH Cl for seven days, with fresh anhydrous CH Cl
2
4
−. The latter is a non-radioactive
−
As the Ni-IN metal-ligand bonding can be a potential weak
point in the stability of this MOF, the bonding interaction between
a Ni2+ center and four IN ligands has been calculated, and the
4
and is often used as a simulation of the
. 30 mg samples of 1 were immersed in
−
4
2
2
2
-
being added every day during the process. The treated samples
were outgassed under dynamic vacuum at 80 oC for 10 h to
results are shown in Figure S7. Both IN and HIN ligands are
investigated for charge balance consideration. The interaction
energies are ca. -1189 and -719 kcal/mol, respectively. The
former is larger due to stronger electrostatic interaction between
cation and anion. This large bonding interaction energy partially
aids the stability of this MOF structure.
remove the solvent. Then, the ReO -
adsorption of compound 1
was performed at room temperature. The activated samples
were immersed in 0.05 mM ReO -
solution for 10 h, and the
corresponding samples were centrifuged and washed by water to
4
4
remove the attached ReO -
was performed to determine the adsorption mass of ReO
. Inductively Coupled Plasma (ICP)
4
-
4
; this
can reach 807 mg/g, which are falling among the highest values
known for MOF (Table 2 and S4).[21,25-29] Subsequently, in order
-
-
-
4
to explore the selectivity of 1 for capturing ReO , 5 mM Cl , OAc
2
-
-
and SO
4
were simultaneously mixed with 0.05 mM ReO
4
solution. ICP showed that under these conditions 1 can still
enrich ReO -
to about 410 mg/g, indicating excellent selectivity
4
for capturing ReO -
. Besides, the exchange capacity of ReO
−
4
4
5
was also explored after 1 treated with 4×10 Gy β irradiation and
5
1
0 Gy γ irradiation, respectively. ICP results suggested that the
−
capacity of capturing ReO
4
exhibited a negligible influence by a
dose of 4×105 Gy β or 105 Gy γ irradiation (Table S4). These
results reveal that framework 1 is potentially an attractive
candidate for dealing with 99TcO -
The mechanism for capturing ReO -
in nuclear waste disposal.
was further explored.
4
4
6 3 8
(μ -O)
]8+. Left, the general MO energy
Figure 3. The energy levels of [Th
levels; middle, the frontier MO energy levels including O 2p-, Th 5f- and
Initially, this was done via X-ray single-crystal analysis, including
-
much effort to produce single crystals of 1 with ReO
define the position of ReO -
diffraction data of the crystals after exchanging ReO -
poor to determine the molecular structure. Nevertheless, based
4
in order to
6d-,7s-bands; right, the enlarged O 2p-based levels.
4
in the pores, but the corresponding
are too
Meanwhile, periodic DFT calculations were performed for the
4
MOF structure of ({[Ni
3
Th
6
3
(μ -O)
4
(μ
3
-OH)
4
(IN)12]}(OH)
6
)
n
)
to
-
4+
investigate the interaction between IN ligand and Th in the core
cluster, as well as between IN ligand and Ni2+ in terms of solid
MOF geometry. The partial density of states (DOS) of Th and O
from IN- (Figure S8) reveal that at valence states Th ions
distribute above fermi level, and only little overlap with O,
indicative of that the interactions between Th4+ and IN mainly
originate from electrostatic interaction. On the other hand, the
partial DOS overlap between Ni and N shows more covalent
contribution between Ni and N than that of Th and O (Figure S9).
These two different interaction types are also further confirmed
by charge density difference analysis (Figure S10). The stability
on the structure characteristics of [Th48Ni
ICP results, we propose that the mechanism is that ReO
6
] nanocage and the
-
-
4
anions
can be captured within the cavities of the nanocages by anion
exchange and adsorption. We base this on the following
-
considerations: 1) Samples after exchanging ReO
4
were
-
centrifuged and carefully washed with water many times to
remove attached ReO -
4
on the surface; therefore precipitation
outside of the MOF can be excluded; 2) single-crystal structural
] cage contains six free OH-
analyses revealed that each [Th48Ni
6
and can exchange six ReO -
4
as the balanced anion; 3) ICP
] cage captures 10.91 ReO -
shows that each [Th48Ni
6
4
. This
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Angewandte Chemie International Edition
10.1002/anie.201901786
COMMUNICATION
-
and 4.91 ReO -
+
5
89
includes 6 exchanged ReO
4
4
and K ; the amount
+
+
of K is very close to 5.01 K determined by ICP analysis (Table
-
S4); 4) ReO
4
is potentially well stabilized in the cage because
-
the OH anions in the Th
6
-cluster, and Ni-coordinated H
2
O, can
[
a] Reaction conditions: epoxides (240.3 mg, 2.0 mmol), solvent-free, catalyst 1
40 mg， based on metal center, about 2.5 mol %), TBAB (16.2 mg, 0.05
mmol), CO
(0.1 MPa), 12 h. [b] Total yield determined by 1H NMR using
1,3,5-trimethoxybenzene as an internal standard.
-
generate hydrogen bonding network with ReO
4
. Additionally, the
(
-
+
3
total volume of 10.91 ReO
4
and 4.91 K is about 1.98 nm (the
2
-
and K+ is 0.143 nm and 0.085 nm ,
3
3
volume of ReO
4
respectively), and the available volume of each [Th48Ni
about 2.05 nm (after considering the van der Waals radii of each
atom in one cage), indicating that these ions can be
6
] cage is
1
can be straightforwardly isolated from the reaction mixtures
3
through centrifugation, allowing us to evaluate its recycle
performance. This was explored as follows: the used compound
was separated from the reaction mixture, and the cycloaddition
reaction with styrene oxide was repeated using the recovered 1
as catalyst. Pleasingly, the corresponding cyclic carbonate is still
produced in excellent yield (99%, Figure S13), suggesting that 1
can serve as a recoverable catalyst for CO
epoxides. To further probe this, the process was repeated up to
0 times, with no obvious loss in catalytic activity (Figure S13).
The PXRD of used catalyst 1 was measured (Figure S14),
revealing that the framework of 1 is still intact and keeps its
crystalline state throughout the cycling. The ICP of the filtered
liquor was also tested; no Ni2+ ion was detected, indicating only
trace amounts of leakage from the robust framework. We
therefore conclude that compound 1 is a highly recoverable
catalyst for these cycloaddition reactions.
accommodated in one cage. Finally, PXRD of samples treated
1
-
with ReO
4
was performed to explore the stability. As shown in
Figure S3d, PXRD well matches the simulated one, indicating
that the framework keeps intact during the adsorption process.
To confirm the existence of large pores in framework 1, the
adsorption of methylene blue (MB) by 1 was explored. As shown
in Figure S11, the dark blue MB solution gradually becomes
colourless over 5 h, and 1 changes from light green to bottle
green, with the maximum MB adsorbing capacity reaching 266
2
conversion with
1
mg/g. Investigation of CO
2
adsorption was also carried out, and
the adsorption CO by activited compound 1 was studied at 198
2
K, and the result is shown in Figure S12a; 1 can capture CO
2
3
with an adsorbing capacity of 42.44 cm /g.
The Th
for catalytic reactions. Therefore, porous framework 1 might be
expected to be promising for the capture and reaction of CO
6
-cluster should provide Lewis acidic and defect sites
In principle, both the Th
6
-cluster and Ni2+ in 1 can act as
catalytic sites in this cycloaddition reaction. To probe this, the
isostructural compound 2 was prepared through an approach
similar to 1 except that Co(OAc)
2
with epoxides. To explore this hypothesis, a series of reactions
were performed with styrene oxide as a model substrate to
determine optimal reaction conditions (Table S5). These
conditions were then used in a further set of reactions with
several typical epoxides; all of the corresponding cyclic
carbonates were obtained in excellent yield (89-99%, Table 3)
2 2
•4H O was used instead of
Ni(OAc) •4H O. The reactions were performed using the same
2
2
conditions as detailed in Tables S5 and 3, and the corresponding
results are recorded in Tables S6 and S7. Generally, Ni2+ is a
stronger Lewis acid than Co2+ and, as Lewis acidity directly
relates to the yield of CO
catalyst should show better catalytic performance than
Co-based one, as has been shown previously. However, 1 and
display similar catalytic results, indicating that the different
transition metals in the framework do not significantly affect the
catalytic efficiency. This suggests that the Th cluster plays the
decisive role in the catalytic reaction, especially as Zr4 and Hf
show excellent catalytic performance in CO conversion with
indicating that compound
1 possesses significant catalytic
2
cycloaddition reactions, a Ni-based
capacity for cycloaddition reactions with CO
epoxides.
2
and various
a
[
30]
2
Table 3. Synthesis of various cyclic carbonates from CO
catalyst 1.
2
and epoxides with
[
a]
6
+
4+
2
epoxide under mild conditions,[31] whereas such yields always
require more rigorous reaction conditions (e.g. higher
temperature and pressure) when Ni/Co-based MOFs are used as
catalyst.
Entry[a]
1
Epoxides
Products
Yield (%)[b]
>99
Taking into account our data and previous reports,[32]
possible mechanism for this cycloaddition reaction is proposed
Figure S15). First, 1 can capture CO and enrich the substrate in
nanocages of [Th48Ni ]. Second, the coupling reaction occurs
between the Th -cluster in 1 and the oxygen atom of the epoxide,
a
(
2
6
2
3
4
>99
93
6
and the epoxy ring in the epoxide is activated. Third, the
-
nucleophilic Br anion attacks the carbon atom in the epoxy ring,
resulting in ring opening. Finally, CO
anion in the opened epoxy ring, and the Th
2
reacts with the oxygen
-cluster stabilizes the
6
resulting alkyl carbonate salt, which is further converted into the
corresponding cyclic carbonate through intramolecular ring
closure. Hence, the cyclic carbonate is obtained in high yield with
95
1
as the catalyst.
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Angewandte Chemie International Edition
10.1002/anie.201901786
COMMUNICATION
In conclusion, a unique framework 1, constructed of [Th48Ni
6
]
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4
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[
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This work was supported by NSFC (21625103, 21571107,
21421001, 21590792, 91426302, and 21433005), the National
Programs of the Nano-Ket Project (2017YFA0206700), and 111
Project (B12015). HSH is grateful to the University of Manchester
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Angewandte Chemie International Edition
10.1002/anie.201901786
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
The stable [Th48Ni
nanocage-based
metal−organic framework
6
]
Hang Xu,[a] Chun-Shuai Cao,[a]
*[b,c]
Han-Shi Hu,
Shi-Bin
Wang,[ Jin-Cheng Liu, Peng
b]
[b]
Cheng,[ Nikolas
a]
exhibits radiation resistance,
Kaltsoyannis, Jun Li,[b] Bin
*[c]
−
effectively enriches ReO
and catalytically converts
CO into epoxides.
4
Zhao*
[a]
2
Page No. – Page No.
−
High Uptake of ReO
4
by a
Radiation Resistant [Th48Ni
6
]
Nanocage-Based
Metal−Organic Framework
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