A temperature-resolved assembly of a series of the largest scandium-containing polyoxotungstates

Article abstract of DOI:10.1039/c7dt00892a

We report a temperature-resolved assembly of a series of novel nanoscale hexameric Sc-containing polyoxometalates of {Sb₆Sc₁₁W₆₀}, {Sb₈Sc₇W₆₀}, and {Sb₈Sc₆W₆₀}. These compounds include the largest Sc-containing polyoxotungstates and contain the largest number of Sc³⁺ ions of any polyoxotungstates reported to date.

Full text of DOI:10.1039/c7dt00892a

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Joseph T. Hupp, Omar K. Farha et al.
Efficient extraction of sulfate from water using
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DOI: 10.1039/C7DT00892A
Journal Name
COMMUNICATION
Temperature-Resolved Assembly of a Series of the Largest
Scandium-Containing Polyoxotungstates
Received 00th January 20xx,
Accepted 00th January 20xx
Zhen-Wen Cai, Tao Yang, Yan-Jie Qi, Xin-Xiong Li, and Shou-Tian Zheng*,a,b
a
a
a
a,b
DOI: 10.1039/x0xx00000x
www.rsc.org/
We report the temperature-resolved assembly of a sereis of novel separation, ferroelectric relaxors, and ceramics.8 The
3+
nanoscale hexmeric Sc-containing polyoxometalates of integration of Sc ions with POMs could afford new types of
Sb Sc 60}, and {Sb Sc 60}. These compounds Sc-based materials with novel structures and interesting
exhibit the largest Sc-containing polyoxotungstates and contain properties. There is thus a strong impetus for us to explore the
{
6
Sc11W
60}, {Sb
8
7
W
8
6
W
3+
the largest number of Sc ions of any polyoxotungstates reported Sc-containing POM chemistry.
to date.
Herein, we report the first series of hexameric Sc-containing
POTs, namely 11-Sc-containing Na (-
4 5 6 2
K H18[Sc11W O20(OH)
Due to diverse structures, compositions, and properties, there
has long been an interest in introducing transition metals (TMs)
into polyoxometalates (POMs) to construct TM-containing
POM materials,1 especially for the multi-TM-containing POMs.
H
H
2
O)16(SbW
23[Sc Sb
9
O
33
)
6
]
·
18H
O) (SbW
Sb
]). These novel POTs not only are the largest Sc-
2
O (Na
4
K
33
5
H
18
[
1
]), 7-Sc-containing Na
16H O (Na ]), and 6-
O) (SbW 48H
6 2
K -
7
2
W
6
O
20(H
2
8
9
O
)
6
]
·
2
6
K
2
H
23
[
33
2
)
Sc-containing Na
Na
5
K
10
H
17[Sc
6
2
W
6
O
19(H
2
6
9
O
6
]
·
2
O
-6
(
5
K
10
H
17
[
3
Up to now, most 3d TMs including Ti , Mn2+/3+, Fe2+/3+, Co ,
4+
2+
containing POTs, but also contain the largest number of Sc
centers of any POTs to date. Interestingly, the giant polyanions
1, 2, and 3 were obtained from the same reaction at different
temperatures of 100 C, room temperature (RT, about 30 C),
and 180 C, respectively. Moreover, a rare structural
transformation from chair-like configuration to boat-like
configuration between nanosized POM hexamers can be found.
2+
2+
2+
Ni , Cu , and Zn have been successfully incorporated into
POMs to form a vast library of TM-containing POMs with
remarkable structural diversity (e.g., from monomeric, dimeric
to multimeric structures).2 What’s more, a diversity of
intriguing multi-TM-containing POMs with dozens of 3d TM
o
o
o
centers have been obtained. Some typical examples include
multimeric {Mn40
tetrameric {[Co (OH)
en) (BTC)1.5(PW
P
3
32
W
224
O
(PW
888},3a
cage-lile {Mo72Fe30},
]},3c octameric {[Ni
3b
4
PO
4
]
4
O
9 34
)
4
6
(Tris)-
which
3d,e
(
3
9
O
34)]
8
}
8 7 22 8
and {Cu25.5O (Nb O ) },
contain the largest number of Mn, Fe, Co, Ni and Cu centers in
molecular POMs, respectively.
In comparison, the introduction of 3d Sc3+ into POMs remains
largely unexplored probably owing to the relative difficulty in
crystallization of Sc-based complexes. To date, the known Sc-
containing POMs are very rare. In polyoxotungstate (POT)
chemistry, only a dimeric Sc-containing POT constructed from
2
two mono-metal-containing {Sc(H O)(α-SiW11O39)} clusters has
7
been reported to our knowledge. It has been shown that Sc-
based composite materials, such as Sc-organic frameworks and
Sc-containing alloys, have attractive potential applications in
the areas of heterogeneous catalysis, gas adsorption,
a.State Key Laboratory of Photocatalysis on Energy and Environment, College of
Chemistry, Fuzhou University, Fuzhou, Fujian 350108, China.
b.
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the
Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China.
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See Figure 1. a)-c) Structures of {Sc
5
(SbW
9 3 6
) }, {ScW }, and polyanion
DOI: 10.1039/x0xx00000x
1, respectively. Tungstate octahedra: red/yellow.
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Journal Name
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DOI: 10.1039/C7DT00892A
Figure 2. a)-c) Structures of {Sc11
6 2 7 2 6
W (OH) O20}, {Sc Sb W O16},
6 2 6
and {Sc Sb W O15}, respectively.
All polyoxoanions
1-3 crystallized in the triclinic space group
P-1 and as mixed sodium-potassium salts, whose phase
purities have been confirmed by PXRD measurements except
that
To begin with, polyoxoanion
POT with 60 W, 11 Sc, and 6 Sb centers, which was obtained
1
is some impure (Figures S1-3).
1
is the largest Sc-containing
III
8
from the hydrothermal reaction of Na
9 9
[B-α-Sb W O33],
ScCl ·6H O, and KCl in NaAc/HAc buffer solution (pH=4.8) at
3
2
o
1
00 C. Polyanion
1
5
has a centrosymmetric structure built from
III
two identical {Sc
fragment (Figure 1). The {Sc
three trilacunary {SbW
(Sb W
9
)
3
} trimers joined by a {ScW
(SbW
33} clusters interlinked by three Sc
6
}
5
9
)
3
} trimer is composed of
3+
9
O
cations into a triangular ring (Figure 1a), which encapsulates
an additional binuclear {Sc (OH)} unit onto the vacancies of Figure 3. a)-d) Structures of 1, 2, 3, {Sc
one of its three {SbW
33} clusters. Additionally, as shown in core, respectively. Tungstate octahedra: red/yellow.
Figure 1b, the {ScW } linker consists of two V-shaped trinuclear
10 units with three corner-sharing WO octahedra, which
are C -symmetry-related by a central [Sc(H
1 Sc3+ cations in polyanion
are all 6-coordinate octahedral
configurations but can be divided into three groups in accord polyanion
increased to 180
33} clusters within the two can be obtained. Crystallographic analyses reveal polyanions
} trimers, each of which coordinates with four
-O and
atoms from two {SbW
33} clusters, one µ-O atom from the containing POT, respectively. As shown in Figure 3, structure
central {ScW
} unit, and one terminal water ligand. The two can be derived from by replacing the two binuclear {Sc (OH)}
Sc (OH)} dimers occupying at the vacant sites of two {SbW
33} units with two Sb atoms. And thus, similar to , compound
can be described as a centrosymmetric structure built from
2
3 2 9 3 6 7
Sb (SbW ) }, and {W O }
9
O
6
W
3
O
6
Fascinatingly, the reaction of
Sc-containing POTs at different reaction temperatures. If
reaction temperature is decreased to 30 C, a new hexameric
can be isolated. While if reaction temperature is
1 can yield different hexameric
3+
i
2
O)
2
]
cation. The
o
1
1
2
3+
o
C, the third kind of hexameric polyanion
3
2
with their positions in
linkers between adjacent {SbW
Sc (SbW
1. The first group includes the 6 Sc
9
O
{
5
9
)
3
µ
3 represent the first 7-Sc-containing POT and the first 6-Sc-
9
O
2
1
2
6
{
2
9
O
1
2
3
+
clusters form the second group, in which each Sc cation
bonds to one µ-OH group, one µ-O atom from a {SbW
two identical trimers of {Sc Sb (SbW } (Figure 3d) joined by a
cluster, two µ-O atoms from the central {ScW
} unit, and two {ScW } fragment. Alternatively, structure can also be viewed
as a chair-like hexamer formed by six trilacunary {SbW O }
O
33
}
3
2
9 3
)
9
6
2
6
3+
terminal water ligands. The third group is the Sc cation
located at the inversion center of
, whose octahedral clusters joined by
configuration is completed by four µ-O atoms from four WO
{Sc Sb 16} (Figure 2b).
octahedra and two terminal water ligands. All the Sc-O and Sc-
Similar to , polyanion
O bond lengths are in the ranges of 1.904(1)-2.259(1) Å and trimers, however, their structures are remarkably different. As
9
33
1
a 15-nuclearity trimetal-oxide core
7
2 6
W O
6
2
3
consists of two {Sc
Sb
3 2
(SbW
9 3
) }
H
2
2
.011(1)-2.403(1) Å, respectively.
Notably, without regard to the {SbW
shown in Figure 3c, the two trimeric {Sc
, the in are fused together in a face-to-face manner via a unique
belt-like hexanuclear W-O core {W O } to form the hexameric
3 2 9 3
Sb (SbW ) } subunits
9
O
33} clusters in
1
3
remainder 17 metals including 11 Sc3+ and six W cations can
6+
6
7
be interconnected by 22 µ-O bridges to give rise to a unique polyanion
3
with a boat-like conformation, which is different
and with a chair-lie conformation. Further,
spatially separated or isolated each other (Figure 2a). And thus, the belt-like hexanuclear {W } core is formed by six corner-
the nanosized polyanion
with dimensions of 3.0 × 1.9 × 1.4 sharing WO octahedra (Figure 3e), differing from the figure-8-
shaped heptanuclear heterometal-oxide core {ScW O } found
1
7-nuclearity bimetal-oxide core {Sc11
W
6
(OH)
2
O
20} instead of from polyanions
1
2
6 7
O
1
6
3
nm (atom-to-atom distance) also can be described as a
hexamer with chair-like conformation constructed from six in
6 8
1
and
2
(Figure 1b). Additionally, the 6-Sc-containing
also can be viewed as a hexameric POM formed by
six trilacunary {SbW 33} clusters linked together by a 14-
trilacunary {SbW
core {Sc11 (OH)
9
O
33} clusters hold together by a heterometal polyanion 3
W
6
2
O20}.
9
O
2
| J. Name., 2012, 00, 1-3
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Journal Name
nuclearity trimetal-oxide core {Sc
COMMUNICATION
6
Sb
2
W
2
6
O
15} instead of Table 1. Results for oxygenation of various thioethVeierws Awrtiictlhe O3n0li%ne
DOI: 10.1039/C7DT00892A
{
Sc11
W
6
(OH)
It is worth mentioning that a common feature of polyanions
-3 is that all of them contain two trimeric fragments of
2
O
20} in
1
and {Sc
7
Sb
2
W
6
O
16} in
(Figure 2c).
H
2
O
Entry
2
catalyzed by
3
in MeCN.
Substrate
Time
Temp Conva
Selectivity
(%)b
(h)
(℃)
(%)
1
{
Sc
3
(SbW
9
3
)
3
+
} made up of three {SbW
9
O
33} clusters bridged by
9 3
(SbW ) }
1c
SCH
3
3
80
100
99
99
three Sc cations (Figure S4), indicating the {Sc
fragment should be an essential building unit and exist in the
reaction solution over the whole reaction temperature range
from RT to 180 C. Fascinatingly, the {Sc
3
2
3
4
5
6
3
3
3
3
3
80
80
80
80
80
100
100
99
O
S
o
3
(SbW
9
)
3
} fragments
can sanwich various multi-nuclearity Sc/W-O cores (such as
Sc } in , {ScSb } in , and {W } in ) at different
temperatures. Additionally, another common feature in is
that part of {SbW 33} clusters within the {Sc (SbW } trimer
has disordered W 13 groups (Figure S5). It has been known
that the starting ordered {B-α-SbW 33} cluster is composed of
three corner-sharing W 13 groups. While, some W 13 groups
within are found to be disordered, each of which is
SCH
3
100
92
{
5
W
6
1
2
W
6
2
6
3
1-3
O
2
N
SCH
3
9
O
3
9 3
)
3
O
9
O
Br
SCH
3
3
99
95
3
O
3
O
1-3
H
3
CO
SCH
99
97
disordered into two groups (Figure S6).
Temperature-resolved assembly of more than two kinds of
o
crystalline POMs in the temperature range from RT to 200 C is
7
8
3
3
80
80
97
93
77
58
S
S
not common. The syntheses of 1-3 represent a rare temperature-
resolved assembly of three types of nanosized POMs in the
temperature range of RT to 180 C. Bond-valence sum
o
calculations show the oxidation states of all the W, Sc, and Sb
9
atoms in
1
-
3
are +6, +3, and +3, respectively. To balance the
9
3
3
80
Trace
100
S
charges, eighteen, twenty-three, and seventeen protons
should be added into , and , respectively. These protons
1
0
80
b
100
S
1
,
2
3
a
The conversion is based on substrate consumed. Selectivity (%) = sulfone
mol)/(sulfoxide (mol) +sulfone (mol) ). Reaction conditions: substrate, 0.5
mmol; H O , 1.1 mmol; solid 3, 0.25×10 mmol; MeCN, 10 ml.
2 2
can not be located and are assumed to be delocalized on the
overall structures, which are common in POMs.10
c
(
-2
Further, the catalytic activity of compound
by a series of H -based catalytic oxidation reactions of MSB
derivatives under the optimum reaction conditions. In the
absence of , both conversion of substrates and selectivity of
products RR’SO
When catalyst
3 was evaluated
2 2
O
3
Scheme 1. Catalytic Oxidation of Thioethers.
2
/RR’SO of all reactions are low (Table S5).
was added into the reactions, conversion and
3
Organosulfur compounds such as sulfoxides and sulfones
selectivity of all reactions were greatly improved. Nevertheless,
compound exhibited different catalytic activity for different
MSB derivatives. As shown in Table 1, compared with MSB, the
introduction of electron-donating groups (e.g., CH and CH
in entries 2 and 3) on the aromatic ring of MSB has no effect
on the conversion of substrates and the selectivity of products.
While, the introduction of electron-withdrawing groups
remain a topical interest owing to its widely potential
utilities.11 The reported literatures show thioethers can be oxidized
3
by H
1
2
O
2
to produce sulfoxides RR’SO and sulfones RR’SO
), however, the conversion of substrates and selectivity of
products RR’SO and RR’SO are low. The conversion and selectivity
of the above reactions can be increased by using some metals or
2
(Scheme
12
3
3
O
2
13
metal complexes such as Sc, Ti, and POMs as catalysts, which
triggers us to check if Sc-containing POMs can display excellent
catalytic performances in the oxidation reactions of thioethers.
(entries 4-6) leads to a slightly decrease of the conversion and
selectivity. Additionally, through the reactions of entries 7-9, it
can be found that steric hindrance has a significant effect on
the catalytic oxidations of sulfides. With the increase of steric
hindrance from entries 7 to 9, the conversion and selectivity
Compound
3 was taken as a representative example for the
investigation of the catalytic oxidation of thioethers. Firstly, an
initial oxidation reaction of 0.5 mmol methylsulfanyl-benzene
decreased rapidly. Except for aryl sulfides, sample
3 also
(
MSB) and 0.5 mmol 30% H
confirm that is an effective catalyst for oxygenation of
thioethers by H . And then, a series of experiments were
2 2
O in 10 ml MeCN was run to
exhibits excellent catalytic activity for the oxidation of alkyl
sulfides in high conversion and selectivity (such as the case of
entry 10). Compound 3, as a kind of POM, has a strong redox
nature, which is responsible for the catalytic activity of the
thioether-POM system. A possible mechanism involves the
3
2 2
O
conducted to obtain the optimum reaction conditions. The
results showed that 0.5 mmol MSB could be completely
converted into sulfone
(
RR’SO
2
) in a 99% yield by refluxing the
and 2.5
peroxo functions of POM
2 2
3 by H O , followed by an oxygen
substrate in 10 ml MeCN with 1.1 mmol 30% H
2 2
O
o
transfer to thioethers to yield the sulfoxide (SO) and sulfone
µmol 3 at 80 C for 3 h (Tables S1-4).
15
2
(SO ) products.
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5
a) S. Reinoso, M. Giménez-Marqués, J. R. GalánV-MiewaAsrctiaclreóOsn,liPne.
DOI: 10.1039/C7DT00892A
49, 8384; b) C. Ritchie, E. G. Moore, M. Speldrich, P. Kögerler,
To confirm the recyclability of the catalyst
worked as an example. Additional substrate and H O
2 2
3
, the entry 6
were
added into the reaction mixture when the previous run was
completed. The results showed has very good recyclability
without an obvious loss of catalytic activity for at least five-run
duplicate operations (Table S6), indicating is a potential
heterogeneous catalyst for the oxidation of thioethers.
Moreover, both PXRD patterns and IR spectra confirmed that
could maintain its structural integrity after catalytic reaction
Figure S6,7). Finally, reactions of entries 1 and 6 based on
using and as catalysts were performed as examples to
Vitoria, J. M. Gutiérrez-Zorrilla, Angew. Chem. Int. Ed. 2010,
C. Boskovic, Angew. Chem. Int. Ed, 2010, 49, 7702; b) M.
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3
3
3
(
1
2
show they also have good catalytic performance for catalytic
oxidation of thioethers (Table S7,8).
6
a) Z. G. Jiang, K. Shi, Y. M. Lin, Q. M. Wang, Chem. Commun,
In summary, it is rare to obtain a series of Sc-containing
POM hexamers that can be synthesized sequentially as a
function of temperature by using the same reaction. These
compounds are by far the largest Sc-containing POTs.
Interestingly, a structure transformation between nanoclusters
from chair-like conformation to boat-like conformation can be
2
014, 50, 2353; b) R. Al-Oweini, A. Sartorel, B. S. Bassil, M.
Natali, S. Berardi, F. Scandola, U. Kortz, M. Bonchio, Angew.
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,
7
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observed, which is reminiscent of the chair
of cyclohexane. The successful syntheses of
the posibility of the inroduction of multi-Sc cations (
/
boat-isomerization
demonstrate
3) into
1-3
7
8
9
D. Zhang, S. Zhang, P. Ma, J. Wang, J. Niu, Inorg. Chem.
Commun, 2012, 20, 191.
≥
polyoxotungstates, which unveils the potential for further
development of Sc-containing POM chmeistry.
The work was funded by the National Natural Science
Foundation of China (No. 21371033 and 21401195) and
Projects from State Key Laboratory of Structural Chemistry of
China (Grants 20150001 and 20160020).
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Dalton Transactions
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DOI: 10.1039/C7DT00892A
Graphical contents
Temperature-Resolved Assembly of a Series of the Largest
Scandium-Substituted Polyoxometalates
Zhen-Wen Cai, Tao Yang, Yan-Jie Qi, Xin-Xiong Li, and Shou-Tian Zheng*
The first series of hexameric scandium-substituted polyoxometalates have been isolated from
the same reaction by a temperature-resolved crystallization process, which represent the largest
scandium-containing polyoxometalates with the largest number of scandium cations.