Rational design of a flu -type heterometallic cluster-based Zr-MOF

Article abstract of DOI:10.1039/c6cc08191f

Following the HSAB principle, the cooperative assembly of tetrahedral [Cu₄I₄(Ina)₄]^4- metalloligands and 8-connecting [Zr₆(μ₃-OH)₈(OH)₈]⁸⁺ building units leads to the first heterometallic cluster-based Zr-MOF (1). The results provide a successful strategy for rational design of heterometallic cluster-based Zr-MOFs.

Full text of DOI:10.1039/c6cc08191f

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DOI: 10.1039/C6CC08191F
A table of contents entry
First heterometallic cluster-based Zr-MOF with flu-type topology was rationally designed by the
4
-
8+
4 4 4 6 3 8 8
cooperative assembly of [Cu I (Ina) ] and [Zr (μ -OH) (OH) )] clusters.

Please d Co h ne omt Ca do j mu s mt margins
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DOI: 10.1039/C6CC08191F
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Rational Design of Flu-Type Heterometallic Cluster-Based Zr-MOF
a
a,b
a,b
,a
Yan-Xi Tan, Xue Yang, Bei-Bei Li, and Daqiang Yuan*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
Abstract Following the HSAB principle, the cooperative assembly date there are only a handful of Zr-MOFs that are composed of
4
-
8
of tetrahedral [Cu I (Ina) ] metalloligands and 8-connecting tetrahedral ligands, in which just the two of them are fluorite
4
+
4
4
8
8a, 8e
[
Zr (μ -OH) (OH) )]
building units leads to the first
(
flu) topology (PCN-521 and MOF-841).
The flu topology is
6
3
8
8
heterometallic cluster-based Zr-MOF (1). The results provide a especially intriguing for the construction of highly porous
successful strategy on rational design of heterometallic cluster- materials, because the structure can be conceived as large
9
based Zr-MOF.
unoccupied dodecahedral cavities with Ca and F as vertexes.
Additionally, these frameworks with flu topology cannot
undergo a translation in any direction without overlapping
with themselves, leaving large dodecahedral cavities without
self-interpenetration. To our knowledge, no experimental
effort has focused on determining the heterometallic Zr-MOFs
based on tetrahedral Cu I cluster, which inspires us to explore
Zr(IV)-based metal-organic frameworks (Zr-MOFs) have been
explored not only because of their designable structures, high
1
2
3
surface areas, exceptional chemical stability, but also
because of the potential catalytic activity as heterogeneous
4
catalysts. Up to now, all of the reported Zr-MOFs are made up
4
4
of monotonous zirconium clusters linked by multi-carboxylate
the heterometallic cluster-based Zr-MOFs with flu topology. By
employing symmetry-guided design, we propose to use the Zr-
MOFs with flu topology as blueprint to construct
heterometallic cluster-based Zr-MOFs (Scheme 1).
5
ligands. The cluster-based metalloligands remain rarely
6
known in formation of heterometallic cluster-based Zr-MOFs,
because Zr(IV) as very hard acid has much stronger affinity to
O atoms from carboxylic groups than those of other metallic
ions. To address this problem, Hard-Soft-Acid-Base (HSAB)
theory is a useful strategy toward heterometallic cluster-based
Zr-MOFs to use organic ligands with different functional
groups and different donor atoms, like O and N atoms. During
the reaction process, the carboxylic acid can selectively
coordinate to the in-situ formed Zr(IV) clusters and the N
atoms can coordinate with other “soft” metal ions such as Cu(I)
at the same time, thus inducing the formation of
heterometallic Zr-MOFs. It is reported that the cooperative
4
-
assembly of tetrahedral [Cu I L ] metalloligands and metal- Scheme 1. Left and middle: A representation of the fluorite structure containing
4
4 4
carboxylate clusters leads to some heterometallic 3d-3d unoccupied dodecahedral cavities (yellow). Ca Green and F black. Right: The
7
4-
predictable fluorite structure results from rationally designed heterometallic
cluster-based Zr-MOFs with two different clusters as augmented nodes. C black,
O red, N sky blue and Zr green.
MOFs. Thus, the tetrahedral [Cu I L ] metalloligand can
4
4 4
reproduce the framework of the Zr-MOFs constructed by
tetrahedral carboxylic ligands to form heterometallic cluster-
based Zr-MOFs with two different inorganic building blocks. To
Here, we report the first heterometallic cluster-based Zr-
MOF, namely [Zr (μ -OH) (OH) )][Cu I (Ina) ] ·xguest (
1
; Ina =
6
3
8
8
4 4
4 2
a.
isonicotinate). The three-dimensional (3D) flu-type framework
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the
Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, Fujian, China.
E-mail: ydq@fjirsm.ac.cn
8+
of
1 consists of 8-connecting [Zr (μ -OH) (OH) )] building
6 3 8 8
4
-
units linked by tetrahedral [Cu I (Ina) ] metalloligands, and
4
4
4
b.
University of the Chinese Academy of Sciences, Beijing, 100049, China.
rich Zr-OH groups as Brønsted acid face the pores of
Electronic Supplementary Information (ESI) available: Experimental details, single-
crystal structure determination, materials characterization (TGA, PXRD, NMR), dodecahedral cages. The Brønsted acid catalytic activity of
1
GCMC simulation and typical experimental procedure for catalysis. CCDC 1507758.
was evaluated by using the styrene oxide ring-opening
See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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reaction. The result shows that catalyst
activity and size selectivity during the test reaction of styrene tetrahedral [Cu I (Ina) ] metalloligands ligands, while each
oxide ring-opening reaction.
Journal Name
8+
1
has perfect catalytic structure, each [Zr (μ -OH) (OH) ] SBU is surrounded by eight
6 3 8 8
View Article Online
4
-
DOI: 10.1039/C6CC08191F
4
4
4
4
-
8+
[Cu I (Ina) ] links four [Zr (μ -OH) (OH) ] SBUs.
4 4 4 6 3 8 8
Moreover, in the whole framework, there is an open
dodecahedral cage with a diameter of about 17.5 × 17.5 × 34.7
3
Å , which is formed by eight [Cu I ] tetrahedrons and six
[
4
4
8+
Zr (μ -OH) (OH) ] SBUs as vertexes and twenty-four Ina
6 3 8 8
ligands as edges (Fig. 1b). The face-centered cubic packing of
these dodecahedral cages via sharing all of the rhombic facets
further extend the structure into a 3D open framework (Fig. 1d
and 1e). From the topological point of view, the [Zr (μ -
6
3
8+
4-
OH) (OH) ]
SBUs
and
tetrahedral
[Cu I (Ina) ]
4 4 4
8
8
metalloligands can be regarded as 8- and 4-connecting nodes,
4
-
respectively.
Hence,
the
tetrahedral
[Cu I (Ina) ]
4 4 4
8+
metalloligands link to the [Zr (μ -OH) (OH) ] SBUs in a 2:1
6
3
8
8
ratio to form a 4,8-connected net with the flu topology (Fig. 1f),
which has been known in two reported rigid Zr-MOFs (PCN-
5
21 and MOF-841) based on the similar inorganic [Zr (μ -
6 3
8+
8a, 8d
OH) (OH) ] units connected by organic ligands.
It should
is the first MOF combined zirconium cluster
and other metal cluster specie into its framework.
8
8
be noted that
1
4-
4 4 4
Fig. 1 a) The distorted conformation of the [Cu I (Ina) ] metalloligand and its
topological representation. (green and pink color highlight the benzoate rings
lying in the mirror planes.) C black, O red, N sky blue, Cu blue, I crimson, Zr green.
b) The 8-connected Zr
6
cluster and its topological representation. c) A
dodecahedral cage with rhombic open faces, d) Natural tiling showing the
packing of the dodecahedral cages (green tiles). e) View of the 3D porous
framework of
presented as golden balls. f) The augmented flu topology of
and cyan polyhedra represent 4- and 8-connected nodes, respectively.
1
along the a- or b-axis. The free spaces in the framework are
1
, where the blue
Bright-yellow octahedral single crystals of
1, formulated as
[
Zr (μ -OH) (OH) )][Cu I (Ina) ] , were obtained by
a
6
3
8
8
4 4
4 2
Fig. 2 The GCMC N
distribution as seen by GCMC simulation for
2
isotherms of 1 at 77.35 K. Insert: The simulated pore size
solvothermal reaction of zirconium n-propoxide, CuI,
1.
isonicotinic acid (HIna) and benzoic acid in a mixed solution of
o
N,N-dimethylformamide (DMF) / ethanol (EtOH) at 100 C for
Within these large dodecahedral cages, the framework of
1
1
2 h. Single-crystal X-ray diffraction reveals that compound
1
possesses considerable void space, and the solvent accessible
volume is estimated by PLATON to be about 69.7% of the total
crystal volume. The dodecahedral cages are interconnected,
thereby forming 3D open channels with an aperture diameter
crystallizes in the tetragonal space group I4/mmm and consists
8
+
of the 8-connected [Zr (μ -OH) (OH) ] clusters linked by
6
3
8
8
4
-
tetrahedral [Cu I (Ina) ] metalloligands (Fig. 1a). In each
Zr (μ -OH) (OH) ] cluster, all of the triangular faces are
6 3 8 8
4
4
8
4
+
[
of 1.4 nm. On the basis of the crystal structure of
1, high
capped by μ -OH groups and eight edges are bridged by
3
porosity and open channel, which are needed to efficiently
transport substrate and product molecule to facilitate catalysis,
4-
carboxylates from tetrahedral [Cu I (Ina) ] metalloligands,
4
4
4
while the remaining positions are occupied by terminal -OH
are all obtained. However, N adsorption measurements are
8+
2
groups. The [Zr (μ -OH) (OH) ] cluster in
1
has the same D4h
6
3
8
8
unsuccessful to give the expected experimental Brunauer-
Emmett-Teller (BET) specific surface area by adopting various
symmetry as reported ones in PCN-222, PCN-521 and PCN-
2
c, 8a
5
[
23.
Correspondingly, the symmetry of the tetrahedral
activated methods such as traditional solvent exchange,
4
-
Cu I (Ina) ] metalloligands is reduced from T to D because
10
4
4
4
d
2d
freeze-drying and even supercritical CO exchange (Fig. S3). It
o
o
2
the angles of two adjacent Ina ligands about 92 and 122 ,
which deviate ideal 109.47 in tetrahedron (Fig. 1a). This
might be attributed to framework distortion upon solvent
removal, which is a common phenomenon observed for high
o
symmetry reduction makes the tetrahedral metalloligands
11
porous MOFs. Despite of that, powder X-ray diffraction
8+
symmetrically compatible with the Zr (μ -OH) (OH) ] clusters.
6
3
8
8
patterns of fresh wet samples for
1, as shown in Fig. S2,
In addition, four peripheral benzoates of the tetrahedral
indicate that the frameworks are stable in some alcohols. It is
very important for epoxide ring-opening reactions, which are
4
-
[
Cu I (Ina) ] metalloligands lie in two mirror planes. In the
4 4 4
2
| J. Name., 2012, 00, 1-3
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usually performed in alcohols solution. In order to better times in this reaction without obvious reducedVieawcAtritvicilteyO.nlTinoe
understand the pore structures, the atomistic Grand Canonical prove the heterogeneous mechanism of DthOeI: r10e.a10ct3i9o/nC,6CleCa0c8h1i9n1gF
Monte Carlo (GCMC) simulations were performed to estimate test of
the adsorption isotherms of N at 77.35 K for using RASPA2 h and continuing reaction for another 23 h. No further
which implements the latest state-of-the-art conversion was noted, proving heterogeneity of the catalyst.
1 was carried out by removing the solid catalyst after 1
1
2
1
2
code,
algorithms for molecular dynamics. As show in the Fig. 2, the
GCMC N sorption of clearly shows type-I isotherms. The
calculated pore volume and the simulated BET surface areas
Table 1. Highly efficient and selective styrene oxide ring-opening reactions catalyzed by
catalyst 1.
1
2
3
2
for
The inserted plot in Fig. 2 shows the simulated pore size
distribution (PSD) by GCMC simulation for without
coordinated solvents. The PSD of shows a peak at 13.6 Å,
1
are estimated as 0.67 cm /g and 1824 m /g, respectively.
Entry
Alcohols
Time (h)
Conversion (%)
trace
Selectivity (%)
[
a]
[f]
1
3
4
5
6
7
8
9
24
0.5
1
2
4
\
26.52
49.61
79.13
94.70
98.81
99.06
100.00
99.5
95.12
95.15
95.02
95.02
95.31
95.19
95.21
95.16
95.01
95.18
93.85
94.04
93.80
90.32
90.76
90.67
1
1
corresponding to the uniform dodecahedral cages in structure.
8
12
[
b]
24
[
c]
d]
e]
1
1
1
1
1
1
16
17
18
0
1
2
3
4
5
24
[
24
24
98.8
[
49.62
92.89
98.03
100.00
82.85
86.23
95.29
Scheme 2. Styrene oxide ring-opening reaction with mono alcohols, catalyzed by
catalyst 1.
8
12
24
8
12
24
As shown in Fig. 1c, Zr-OH groups face the dodecahedral
cages in the MOF, which makes the catalytically active sites
easily accessible. As the terminal hydroxides of defective Zr6
nodes in
1
can function as Brønsted acid catalytic sites, we
[f]
1
9
24
< 1
\
sought to test them as catalysts for the ring-opening of styrene
oxide with a series of monohydric alcohols. In accordance with
the two possible sites of nucleophilic attack of monohydric test after reaction for 1 h. Not calculated.
alcohols on styrene oxide, two products are possible: the
a
b
c
d
e
No catalyst 1. The first run. The second run. The third run. The filtration
f
With these results in hand, we set out to change the
substrates diverse in sizes to explore the relationship between
catalytic activities and pore properties for catalyst . Thus,
ring-opening reactions of styrene oxide with other monohydric
alcohols were performed to evaluate the catalytic activities of
primary alcohol (A, β-alkoxy alcohols) and the secondary
alcohol (B). β-alkoxy alcohols as a kind of important synthetic
intermediates can be used to synthesize alkoxy ketones or
alkoxy acids, as well as some other special drug intermediate
1
13
compounds. As shown in Scheme 2, the reaction of styrene
o
1
, in which three kinds of monohydric alcohols with different
oxide and ethanol was carried out at 55 C with 1 mol% MOF
sizes, shapes and nucleophilicity (Scheme 2 and Table 1) were
employed. Still under the same conditions described above,
the ring-opening reactions of styrene oxide with diverse
monohydric alcohols were carried. It can be note that catalytic
catalyst, with detailed procedures in the Electronic
supplementary information (ESI). It is noted that no significant
reactivity can be observed for this reaction in the absence of a
catalyst because of the poor nucleophilicity of alcohols. The
result affirmed that the β-alkoxy alcohol, β-ethoxy-2-
phenylethanol, is the principal product confirmed by gas
activities of
1 are dependent on the structural features of
monohydric alcohols. As shown in Table 1, desired products
are obtained but with different yields and regioselectivities.
For two structural isomers n-propyl alcohol and isopropyl
alcohol, although isopropyl group has stronger electron-
donating ability than propyl group, isopropyl alcohol with large
steric effect induces lower conversion and regioselectivity than
n-propyl alcohol. For isopropyl alcohol, the catalytic activity is
1
chromatography and H NMR spectroscopy (Fig. S4-S7). After 8
hours, the reaction leaded to a 99.18% conversion of styrene
oxide and a 95.31% selectivity of β-ethoxy-2-phenylethanol.
After 24 hours, the final conversion of styrene oxide and
selectivity of β-ethoxy-2-phenylethanol can be reached 100%
and 95.21%, respectively. Judging from the powder X-ray
diffraction (PXRD) patterns of the catalyst after ring-opening
1
4
slightly lower than that of Zr-MOF-808 and Hf-MOF-808, but
much better than a series of UiO-type MOFs, such as Zr-UiO-66,
Hf-UiO-66, Zr-UiO-67, Hf-UiO-67, Zr-PCN-57, Hf-PCN-57, Zr-NU-
reaction, the framework of
1 is intact after usage as a catalyst
(Fig. S2). Compared to the PXRD pattern of the as-synthesized
1
4
1
000 and Hf-NU-1000. Furthermore, no product can be
sample, a slim redistribution of the peak intensities, but no
change of the peak positions is observed. A recycling test with
obtained even after 24 h when the reaction was run with
phenethyl alcohol as the nucleophile. This is consistent with
our hypothesis that the narrow window size of the
dodecahedral cages will hamper the diffusion of larger
substrates and transfer of productions during catalytic reaction.
three consecutive runs was performed to check if catalyst
1
can be reused. For all three reactions, the conversion and
regioselectivity after 24 hours are always in excess of 98% and
9
5%. The results indicate that catalyst 1 can be reused several
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Journal Name
2
2
016,
6, 235; (b) H. Fei and S. M. Cohen, J. Am. Chem. Soc.,
View Article Online
A tentative mechanism is proposed for the ring-opening
reaction into β-alkoxy alcohols catalyzed by 1. First, the less-
hindered O of epoxide is attacked by a proton from –OH to
015, 137, 2191; (c) W. Y. Gao, H. Wu, K. Leng, Y. Sun and S.
DOI: 10.1039/C6CC08191F
Ma, Angew. Chem. Int. Ed., 2016, 55, 5472; (d) Z. Li, N. M.
Schweitzer, A. B. League, V. Bernales, A. W. Peters, A. B.
Getsoian, T. C. Wang, J. T. Miller, A. Vjunov, J. L. Fulton, J. A.
Lercher, C. J. Cramer, L. Gagliardi, J. T. Hupp and O. K. Farha,
J. Am. Chem. Soc., 2016, 138, 1977; (e) K. Manna, P. Ji, F. X.
Greene and W. Lin, J. Am. Chem. Soc., 2016, 138, 7488; (f) M.
Rimoldi, A. Nakamura, N. A. Vermeulen, J. J. Henkelis, A.
Blackburn, J. T. Hupp, J. F. Stoddart and O. K. Farha, Chem.
δ+
activate the epoxy ring, leaving a positively charged O .
δ+
Secondly, the electrons in β C−O bonds transfer to the O ,
breaking the bond and effectively transferring the positive
charge to the carbon. Thirdly, an oxygen atom from a nearby
R-OH molecule attacks the electrophilic carbon from a
direction opposite. The finally step is a rapid proton transfer to
give the desired β-alkoxy alcohols and the catalytic species.
In summary, through the cooperative assembly of
Sci., 2016, 7, 4980; (g) X. Yu and S. M. Cohen, J. Am. Chem.
Soc., 2016, 138, 12320.
5
6
. (a) D. Alezi, I. Spanopoulos, C. Tsangarakis, A. Shkurenko, K.
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B. Li, B. Gui, G. Hu, D. Yuan and C. Wang, Inorg. Chem., 2015,
4
-
tetrahedral [Cu I (Ina) ] metalloligands and Zr clusters, the
4
4
4
6
first heterometallic cluster-based Zr-MOF
1
has been
successfully synthesized and structurally characterized as a
high porous flu-type network composed of the face-centered
54, 5139.
cubic packing of dodecahedral cages. Compound
1 with rich
. (a) W.-X. Zhang, P.-Q. Liao, R.-B. Lin, Y.-S. Wei, M.-H. Zeng
and X.-M. Chen, Coord. Chem. Rev., 2015, 293-294, 263; (b) L.
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metal-bound Brønsted acid (M-OH) has notable catalytic
activity on epoxide ring-opening reaction. The results reveal
that catalytic activities of
1 are mainly dependent on the size
and steric hindrance of alkyl substituent in primary alcohols. 7. (a) Y.-X. Tan, Y.-P. He and J. Zhang, Chem. Mater., 2012, 24
,
4
711; (b) J. Qian, F. Jiang, K. Su, J. Pan, Z. Xue, L. Liang, P. P.
This work not only illustrates a successful case of designing
heterometallic cluster-based Zr-MOFs with a desired topology,
but also demonstrates that heterometallic cluster-based Zr-
MOFs are potential catalysts for future applications.
Bag and M. Hong, Chem. Commun., 2014, 50, 15224; (c) X. X.
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This work was financially supported by the National Nature 8. (a) M. Zhang, Y. P. Chen, M. Bosch, T. Gentle, 3rd, K. Wang, D.
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Science Foundation of China (21371169 and 21603229), the
Strategic Priority Research Program of the Chinese Academy of
Sciences (XDB20000000), and the Nature Science Foundation
of Fujian Province (2016J01080).
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3
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