Designed assembly of heterometallic cluster organic frameworks based on anderson-type polyoxometalate clusters

Article abstract of DOI:10.1002/anie.201602087

A new approach to prepare heterometallic cluster organic frameworks has been developed. The method was employed to link Anderson-type polyoxometalate (POM) clusters and transition-metal clusters by using a designed rigid tris(alkoxo) ligand containing a pyridyl group to form a three-fold interpenetrated anionic diamondoid structure and a 2D anionic layer, respectively. This technique facilitates the integration of the unique inherent properties of Anderson-type POM clusters and cuprous iodide clusters into one cluster organic framework. All linked up: Two unprecedented heterometallic cluster organic frameworks were constructed through directly linking Anderson-type polyoxometalate (POM) clusters with different cuprous iodide clusters by using a rigid bifunctional tris(alkoxo) ligand under solvothermal conditions.

Full text of DOI:10.1002/anie.201602087

Angewandte
Communications
Chemie
International Edition: DOI: 10.1002/anie.201602087
German Edition: DOI: 10.1002/ange.201602087
Cluster Organic Frameworks
Designed Assembly of Heterometallic Cluster Organic Frameworks
Based on Anderson-Type Polyoxometalate Clusters
Xin-Xiong Li, Yang-Xin Wang, Rui-Hu Wang,* Cai-Yan Cui, Chong-Bin Tian, and
Guo-Yu Yang*
Abstract: A new approach to prepare heterometallic cluster
organic frameworks has been developed. The method was
employed to link Anderson-type polyoxometalate (POM)
clusters and transition-metal clusters by using a designed
rigid tris(alkoxo) ligand containing a pyridyl group to form
a three-fold interpenetrated anionic diamondoid structure and
a 2D anionic layer, respectively. This technique facilitates the
integration of the unique inherent properties of Anderson-type
POM clusters and cuprous iodide clusters into one cluster
organic framework.
oxygen-rich compositions and preferentially bond to metal
cations rather than carboxylate anions or N-donor ligands,
whereas TM clusters are only stable in the presence of
carboxylate anions or N-donor ligands. Therefore, the search
for suitable organic ligands to bridge the gap between POM
clusters and TM clusters is an attractive but highly challenging
task since heterometallic cluster organic frameworks should
combine the physiochemical properties of the two different
SBUs and provide the chance to produce multifunctional
materials.
In this Communication, we chose 2-(hydroxymethyl)-2-
[
1]
C
luster organic frameworks, composed of cluster secon-
(pyridin-4-yl)-1,3-propanediol (H L) as the bridging ligand
3
dary build units (SBUs) and organic linkers, have attracted
extensive interest because of their fascinating structures and
based on the following considerations: 1) it is a rigid bifunc-
tional ligand containing three hydroxy groups and a 4-pyridyl
group on opposite sides, enabling the L ligand to act as
a linear bridge; 2) The hydroxy groups can be easily
incorporated into POM clusters (so far, tris(alkoxo) ligand
[2–4]
potential applications.
area has focused on the assembly of transition-metal (TM)
cluster organic frameworks, leading to the development of
some intriguing framework structures. However, the design
and synthesis of cluster organic frameworks from polyoxo-
metalate (POM) clusters is still in its infancy. POMs are
anionic metal oxide clusters with not only versatile applica-
tions but also different shapes, sizes, and compositions,
providing a variety of SBUs for assembling novel cluster
So far, the majority of work in this
[5]
[7]
[8]
[9]
grafted Anderson,
Lindqvist,
Dawson,
and other
[10]
POMs
have been documented); 3) The 4-pyridyl group
[
11]
may capture and stabilize TM clusters formed in situ. As
a result, extended cluster organic frameworks containing
POM and TM clusters might be obtained (Scheme 1).
Herein, we report the designed syntheses and structures of
two unprecedented heterometallic cluster organic frame-
works (TBA) [Cu I ][MnMo O L ] ·2DMA (2) and (TBA) -
[6]
[
1]
organic frameworks. For instance, we have reported a series
of cluster organic frameworks based on {Ni PW } SBUs and
multi-carboxylate linkers,
6
9
6
4
4
6
18
2
2
6
[1a]
+
and Dolbecq et al. have used
[Cu I ][MnMo O (L) ] ·4DEF (3; TBA = n-Bu N , DEF =
2
2
6
18
2
2
4
[1b,c]
{
Zn PMo O } SBUs to make porous frameworks.
More
N,N-diethylformamide,
DMA = N,N-dimethylacetamide).
4
12 40
recently, Su and co-workers reported two frameworks
obtained by linking {Zn PMo O } SBUs with multicarbox-
4
12 40
[1d]
ylate ligands.
In contrast to the above-mentioned cluster organic frame-
works which only contain either POM or TM cluster SBUs,
the assembly of heterometallic cluster organic frameworks
containing both POM and TM cluster SBUs has been largely
unexplored, mainly because POM clusters and TM clusters
are two different SBUs with different inherent characteristics.
POM clusters usually have large negative charges and
[
*] Dr. X.-X. Li, Y.-X. Wang, Prof. Dr. R.-H. Wang, C.-Y. Cui, Dr. C.-B. Tian
State Key Laboratory of Structural Chemistry
Fujian Institute of Research on the Structure of Matter
Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China)
E-mail: ruihu@fjirsm.ac.cn
Prof. Dr. G.-Y. Yang
MOE Key Laboratory of Cluster Science, School of Chemistry
Beijing Institute of Technology, Beijing 100081 (China)
E-mail: ygy@bit.edu.cn
ygy@fjirsm.ac.cn
Supporting information for this article can be found under:
http://dx.doi.org/10.1002/anie.201602087.
Scheme 1. Synthetic route to cluster organic frameworks 1–3.
6
462
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3
À
These cluster organic frameworks are based on the combina-
tion of Anderson-type POM and cuprous iodide cluster SBUs
and were prepared through a two-step strategy (Scheme 1).
To date, though a few cluster organic frameworks containing
dral Cu4I4 clusters linked by the linear [MnMo O L ]
6 18 2
cluster bridges. The asymmetric unit consists of one
[MnMo O L ] anion, two TBA cations, two TBA moieties,
and one Cu I moiety (Figure S3). As a basic tetrahedral
3À
6
18
2
4
4
[1e–i,12]
different SBUs have been reported,
the direct connec-
building unit, each Cu I cluster in 2 is composed of four
4 4
+
À
tion of POM clusters and TM clusters through organic linkers
into higher dimensional architectures has been rarely
reported. To our knowledge, 2 and 3 represent the first
examples of heterometallic cluster organic frameworks based
on Anderson-type POMs and cuprous halide clusters.
The synthetic strategy for the preparation of 2 and 3 is
shown in Scheme 1. First, we grafted L onto both sides of the
Anderson POM and obtained a new L-functionalized POM,
tetrahedrally coordinated Cu ions bonded by four m -I
3
anions (Figure 1b). The Cu···Cu distances vary from 2.553
to 2.647 Š. Each Cu I cluster is stabilized by four pyridyl
nitrogen atoms from different [MnMo O L ] ions (Fig-
4
4
3
À
6
18
2
ure 1c), and the CuÀN bond lengths are 2.019(8) and
1.996(9) Š, which are in agreement with those in the reported
[5f]
Cu I -based
cluster
organic
framework.
The
4
4
3
À
[MnMo O L ] ion serves as a linear bridge to link two
6
18
2
(
TBA) [MnMo O L ]·2CH CN (1), which was prepared in
adjacent Cu4I4 clusters, and the distance between Cu4I4
clusters is about 1.86 nm. As expected, such connections
between Cu4I4 and [MnMo O L ] clusters lead to the
6 18 2
3
6
18
2
3
good
(
yield
by
heating
(TBA) [a-Mo O ],
Mn-
4
8
26
3
À
CH COO) ·2H O, and H L in dry acetonitrile. The structural
3
3
2
3
analysis revealed that 1 contains three TBA cations, one L-
formation of an open 3D anionic cluster organic framework
with diamondoid topology (Figure 1e). The sizes of the
channels based on opposite polyhedra are about 2.78 ”
2.92 nm, and the diameter of each diamondoid cavity is
about 2.88 nm (Figure 1d,e; Figure S4). Such an extremely
large cavity induces three-fold interpenetration of three
symmetry-related cluster organic frameworks in 2 (Figure 1 f;
Figures S5,S6). Despite the three-fold interpenetration, the
whole structure still shows large 1D irregular channels with
3
À
grafted Anderson-type cluster [MnMo O L ] (Figure 1a),
6
18
2
3
À
and two lattice acetonitrile molecules. The [MnMo O L ]
6
18
2
can be described as a well-known B-type Anderson cluster
3
À
[
MnMo O ] capped by two deprotonated L ligands on both
6 24
sides. The length of the Anderson-type cluster is about
.47 nm (Figure 1a). Second, when 1 is used as a starting
material to react with CuI, the free 4-pyridyl groups on both
1
3À
sides of cluster [MnMo O L ] successfully capture and
6
18
2
2
stabilize cuprous iodide clusters formed in situ. As a result,
yellow block crystals of 2 (see Figure S1 in the Supporting
Information) and lamellar crystals of 3 (Figure S2) were
obtained under different conditions.
the sizes of 1.01 ” 1.01 nm along the c axis (Figure 1g), where
the bulky TBA cations and disordered solvent molecules are
located for balancing the charge and stabilizing the cluster
organic framework (Figure S7). PLATON calculations shows
that the total empty volume of the anionic cluster organic
Single-crystal X-ray diffraction analysis revealed that 2
crystallizes in the tetragonal space group P4 2 2, and features
3
framework is 14047.4 Š , corresponding to 69.4% of the total
3
1
3
a 4-connected porous anionic framework containing tetrahe-
crystal volume (20253.2 Š ). This value is higher than that in
3
À
Figure 1. a) Structure of the cluster [MnMo O L ] in 1; b) Ball and stick representation of the Cu I cluster in 2; c) View of the coordination
6
18
2
4 4
3
À
environment of the Cu I cluster in 2; d) View of the diamondoid cavity consisting of twelve Cu I clusters and twelve [MnMo O L ] clusters in
; e) View of the 3D anionic cluster organic framework based on Cu I clusters and [MnMo O L ] clusters; f) View of the 3-fold interpenetrated
4 4 6 18 2
4
4
4
4
6
18 2
3
À
2
cluster organic framework in 2; g) View of the 3D cluster organic framework of 2 along the c axis. Color codes in a), c), d), e), and g):
MoO =red; MnO =yellow.
6
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2
some of the most open zeolites, such as faujasite, in which the
free space is 45–50% of the crystal volume.
with decreased sizes of 2.30 ” 2.45 nm along the a axis
(Figure 2c), in which the charge-compensated TBA cations
and guest solvent molecules are located (Figure S10). After
the removal of TBA cations and solvent molecules, the total
potential accessible volume of 3 is 71.4%, based on PLATON
calculations, which is slightly higher than that in 2.
[
13]
Variation of the reaction conditions led to the formation
of another interesting cluster organic framework 3, which is
3À
based on rhombohedral Cu I and [MnMo O L ] clusters.
2
2
6
18
2
The asymmetric unit of 3 contains one Cu I moiety and two
2
2
3À
[14]
independent [MnMo O L ] moieties, one TBA cation, and
Bond valence sum (BVS) calculations based on bond
6
18
2
one TBA moiety (Figure S8). As another conventional
cuprous iodide cluster, the Cu I cluster can be viewed as
lengths revealed that the oxidation states of Mo and Mn ions
in 1–3 are + 6 and + 3, respectively (Table S2). The average
BVS values for Cu ions in 2 and 3 are 1.155 and 1.042,
respectively, suggesting Cu ions are in the + 1 oxidation state.
These results are consistent with the charge-balanced require-
ment of the anions and the frameworks. 2 and 3 are stable in
air and the good agreement between powder X-ray diffrac-
tion (PXRD) patterns for the as-synthesized samples and the
simulated ones based on single-crystal data indicate the phase
purities of 2 and 3 (Figure S11,S12). Thermogravimetric
analyses (TGA) of 2 and 3 (Figure S13) show weight losses of
3.88% and 8.43% in 30–2408C and 30–1908C, respectively,
corresponding to the removal of free DMA (calculated as
3.52% for 2) and DEF molecules (calculated as 8.92% for 3),
respectively. As shown in Figure S11, in situ variable-temper-
ature PXRD patterns indicate that the anionic framework of
2 remains intact up to 2508C, whereas the thermal stability of
3 is lower than that of 2. 3 is only stable at temperatures lower
than 2208C, as evidenced by the variable-temperature PXRD
patterns (Figure S12), which further confirms that the frame-
work with the diamondoid topology is more stable than the
2
2
+
À
two tetrahedrally coordinated Cu ions linked by two m -I
2
anions. The Cu···Cu distance in the Cu I cluster is 2.582 Š,
2
2
which is comparable with that in 2.
As shown in Figure 2a, each Cu I cluster in 3 is ligated by
2
2
3À
four pyridyl groups from four [MnMo O L ] bridges with
6
18
2
CuÀN bond lengths of 2.042(5) and 2.050(5) Š. Four symme-
try-related nitrogen atoms bound to the Cu I unit are
2
2
coplanar, with a N-Cu-N bond angle of 111.5(1)8, leading to
the formation of an unprecedented 2D cluster organic
framework (Figure 2b). In each layer, the coordination
3
À
connectivity between Cu2I2 clusters and [MnMo O L ]
6
18
2
anions generates giant parallelogram-shaped rings with sizes
2
of 2.46 ” 3.05 nm (measured between opposite atoms). Each
3
À
ring is circumscribed by four Cu I and four [MnMo O L ]
2
2
6
18
2
clusters. The 2D layers are stacked in parallel along the a axis,
and each layer is slightly shifted with respect to the next one
(
4
Figure S9). The distance between the adjacent layers is about
.877 Š. Such stacking of the layers gives rise to 1D channels
2
D structure. In the IR spectra of 1–3 (Figure S14), the
characteristic vibrational bands of Anderson-type anions for
the terminal Mo=O units and the bridging Mo-O-Mo groups
À1
À1 [7g]
are located at 840–980 cm and 620–730 cm , respectively.
À1
The bands at 1366–1460 and 3025-2815 cm are ascribed to
[15]
the stretching vibrations of TBA cations. These results are
consistent with their single-crystal structural analyses.
The variable-temperature photoluminescent properties of
the as-synthesized framework 2 were studied in the temper-
ature range of 77–350 K (Figure 3). Upon excitation at l =
3
27 nm at 77 K, 2 exhibits a remarkable emission band with
a maximum around l = 656 nm. The emission may be
attributed to a “cluster-centered” triplet excited state that
involves both Cu and I tetrahedral units and has mixed
4
4
iodide-to-metal charge transfer and “metal-cluster-centered”
1
0
9
1
[16]
(d
Cu!d s Cu) character. As the temperature increases,
the emission intensities sharply decrease without an obvious
shift of the emission maximum, and the emission is nearly
quenched at room temperature. Such emission variation may
be attributed to the quenching effects caused by the solvent
molecules or other components gradually become stronger as
the temperature increases. The UV/Vis diffuse reflectance
spectra (Figure S15) of the polycrystalline samples showed
that the band gaps of 2 and 3 can be calculated as 2.20 and
[
17]
1
.96 eV, respectively. Pure inorganic POMs are usually
[18]
insulators,
however, the interactions between organic
ligands and the POM clusters can affect energy levels near
the Fermi level to make such hybrid POMs as potential
Figure 2. a) View of the coordination environment of the Cu I cluster
2
2
[19]
3À
semiconductors.
The magnetic susceptibility of 2 was
in 3; b) View of the 2D layer based on Cu I and [MnMo O L ]
2
2
6
18 2
measured under an applied magnetic field of 1 kOe in the
temperature range from 300 to 2 K (Figure S16). At 300 K,
clusters in 3; c) View of the 3D stacking style of 2D layers, showing 1D
channels along the a axis.
6
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directly linking Anderson-type POM clusters with different
cuprous iodide clusters. The deliberate choice of the rigid
bifunctional tris(alkoxo) ligand containing a pyridyl group is
crucial for designing and developing these frameworks. 2
exhibits a combination of the photoluminescence and mag-
netic properties as well as the catalytic activity derived from
the integration of both cuprous iodide clusters and POM
clusters within one cluster organic framework. The interesting
properties of these novel cluster organic frameworks testify
that the linkage of different types of clusters with distinct
properties is an effective method in the exploration of
multifunctional materials. This work not only provides
a new perspective towards the development of heterometallic
cluster organic frameworks, but also confirms the potential
for developing new classes of multifunctional materials by
Figure 3. Variable-temperature photoluminescence spectra of 2 in the
[5a]
using various TM clusters, such as Zn O(CO ) , Cu (OH) -
4
2
6
2
2
solid state. For the excitation (ex) spectrum, l =327 nm; for the
ex
[
5b]
[5c]
[5d]
(
(
CO ) ,
Zr O (OH) (CO ) ,
Cr O (CO ) ,
In O-
3
emission (em) spectra, lem =656 nm.
2
4
6
4
4
2
12
[5h]
3
4
2
6
[5e]
[5g]
[5i]
CO ) , WS Cu , Cu OCl , and Re (m - Se) , together
2
3
4
4
4
6
6
3
8
with POM clusters with different shapes as SBUs.
3
À1
the c T value is 2.91 cm mol K, which is very close to the
m
3
À1
III
value of 3.00 cm mol K for an isolated Mn ion with g = 2.0.
Upon cooling, the c T value remains constant to about 35 K; Acknowledgements
m
subsequently, it decreases abruptly to a minimum value of
3
À1
2
.20 cm mol K at 2 K. Such magnetic behavior is typical for
This work was supported by the 973 Program (no.
2011CBA00502), the NSFC (nos. 21273239, 21401195, and
21571016) and the NSF for Young Scholars of Fujian Province
(no. 2015J05041).
III
[20]
a high-spin Mn compound. The decrease of the c T value
at low temperature should be attributed to the zero-field
splitting of Mn ions rather than antiferromagnetic intermo-
m
III
lecular interactions. The absence of antiferromagnetic inter-
molecular interactions was confirmed by the very small and
negative Weiss constant q = À0.47 K, obtained based on 1/cm
versus T plots in the temperature range of 2–300 K according
to the Curie–Weiss law (Figure S16).
Keywords: cluster organic frameworks · copper ·
heterometallic structures · luminescence · polyoxometalates
How to cite: Angew. Chem. Int. Ed. 2016, 55, 6462–6466
Angew. Chem. 2016, 128, 6572–6576
The catalytic performance of 2 was initially investigated
I
by its application in a Cu -catalyzed three-component azide–
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sodium azide, and phenylacetylene in the presence of 2
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2
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Received: February 29, 2016
Published online: April 9, 2016
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