Robust Bifunctional Lanthanide Cluster Based Metal-Organic Frameworks (MOFs) for Tandem Deacetalization-Knoevenagel Reaction

Article abstract of DOI:10.1021/acs.inorgchem.7b03084

A series of 12-connected lanthanide cluster based metal-organic frameworks (MOFs) have been constructed by [Ln₆(μ₃-OH)₈(COO-)₁₂] secondary building units (SBUs) and 2-aminobenzenedicarboxylate (BDC-NH₂) ligands. These obtained materials exhibit high chemical stability and generic thermal stability, especially in acidic and basic conditions. They also present commendable CO₂ adsorption capacity, and Yb-BDC-NH₂ was further confirmed by a breakthrough experiment under both dry and wet conditions. Moreover, these materials possess both Lewis acid and Br?nsted base sites that can catalyze one-pot tandem deacetalization-Knoevenagel condensation reactions.

Full text of DOI:10.1021/acs.inorgchem.7b03084

Article
Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX
pubs.acs.org/IC
Robust Bifunctional Lanthanide Cluster Based Metal−Organic
Frameworks (MOFs) for Tandem Deacetalization−Knoevenagel
Reaction
†
‡
,†
†
†
‡
Yue Zhang, Yuxiang Wang, Lin Liu,* Na Wei, Ming-Liang Gao, Dan Zhao,
and Zheng-Bo Han*
,†
†
College of Chemistry, Liaoning University, Shenyang 110036, People’s Republic of China
‡
Department of Chemical & Biomolecular Engineering, National University of Singapore, 117585, Singapore
S Supporting Information
*
ABSTRACT: A series of 12-connected lanthanide cluster based metal−
organic frameworks (MOFs) have been constructed by [Ln (μ -
6
3
OH) (COO−) ] secondary building units (SBUs) and 2-aminobenzenedi-
8
12
carboxylate (BDC-NH ) ligands. These obtained materials exhibit high
2
chemical stability and generic thermal stability, especially in acidic and basic
conditions. They also present commendable CO adsorption capacity, and
2
Yb-BDC-NH was further confirmed by a breakthrough experiment under
2
both dry and wet conditions. Moreover, these materials possess both Lewis
acid and Brønsted base sites that can catalyze one-pot tandem
deacetalization−Knoevenagel condensation reactions.
23−27
1
. INTRODUCTION
reactions.
For example, the Zhou group reported a Cu
paddlewheel-based MOF, denoted PCN-124, to be an excellent
catalyst for one-pot tandem deacetalization−Knoevenagel
condensations reaction for the synthesis of benzylidene
Recent years, metal−organic frameworks (MOFs) have been
intensely studied as heterogeneous catalysts and applied in the
field of organic chemistry, mainly because they possess
extremely high surface areas, tunable pore size, and
recoverability, as well as a wide range of accessible catalytic
28
malononitrile.
In our previous work, a series of trinuclear, pentanuclear, and
1
−6
hexanuclear Ln cluster based MOFs were designed and
sites. Stability and catalytic activity are important features for
catalysts, which can be found in some MOFs. For instance,
MIL-53(Al), UiO-66, UiO-67, UiO-68, and ZIF-8 are
undecomposed at temperatures lower than 500 °C and are
15,29,30
synthesized.
Among these, trinuclear and pentanuclear
Ln cluster based MOFs gave preeminent catalytic activity
toward the cycloaddition of CO and epoxides, hexanuclear Ln
2
7
−9
cluster based MOFs possessed luminescence, and all showed
good stability. In this work, a series of 12-connected
hexanuclear Ln (Ln = Yb, Dy, Sm) cluster based MOFs
incorporating [Ln (μ -OH) (COO−) ] and an amino-func-
stable in common organic solvents.
In addition, polynuclear
lanthanide (Ln) cluster based MOFs, showing high stability and
10−12
good catalytic activity, have been applied in various fields.
6
3
8
12
Ln clusters assembled with multifunctional organic ligands can
be used in an efficient strategy to design MOFs with special
functions. Currently, a few polynuclear Ln cluster based MOFs
tionalized ligand (2-aminobenzenedicarboxylate, BDC-NH )
2
have been synthesized by solvothermal reactions with the
13−15
formula [(CH ) NH ] [Ln (μ -OH) (BDC-NH ) (H O) ]·
3
2
2 2
6
3
8
2
6
2
6
have been reported with noticeable catalytic activities.
x(solv) (Ln = Yb, Dy, Sm) (Figure 1). These compounds
show high chemical stability and generic thermal stability in
common organic solvents and water with pH values ranging
Tandem reactions are economical, efficient, and environ-
mentally friendly chemical methods and have been attracting
1
6−18
widespread research interest.
Tandem reactions are
from 2 to 12. Due to the existence of −NH groups, they show
sequentially carried out with two or multiple individual
reactions in one pot, which can reduce the use of chemicals,
mitigate the generation of pollutants, and shorten reaction
2
high adsorption capacity for CO . In addition, the CO
2
2
adsorption capacity of Yb-BDC-NH was further studied by
2
1
9
breakthrough experiments under both dry and wet conditions.
More strikingly, the Ln clusters afford Lewis acid sites and
ligands offer Brønsted base sites, making them highly efficient
time. In the organocatalytic field, the development of tandem
reactions has become a new direction to offer opportunities for
improving chemical transformations, such as hydrogenation
reactions, alkene metathesis, and Michael/Morita−Baylis−
2
0−22
Hillman reactions.
Recently, some MOFs have been
Received: December 7, 2017
reported to be high-performance catalysts for tandem
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.7b03084
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
C H Yb N O : C, 25.50; H, 2.72; N, 4.57. Found: C, 25.74; H,
52
66
6
8
38
2
.69; N, 4.61.
.2.2. Synthesis of Dy-BDC-NH , [(CH ) NH ] [Dy (μ -OH) (BDC-
2
2
3 2
2 2
6
3
8
NH ) (H O) ]·x(solv) (2). The synthesis process of 2 was similar to that
2
6
2
6
of 1 except with Dy(NO ) ·6H O instead of ytterbium nitrate. Yield:
3
3
2
6
8% (based on the crystals dried in air). Anal. Calcd for
C H Dy N O : C, 27.00; H, 2.88; N, 4.84. Found: C, 26.97; H,
52
66
6
8
38
2
.90; N, 4.86.
.2.3. Synthesis of Sm-BDC-NH , [(CH ) NH ] [Sm (μ -OH) (BDC-
2
2
3 2
2 2
6
3
8
NH ) (H O) ]·x(solv) (3). The synthesis process of 3 was similar to that
2
6
2
6
of 1 except with Sm(NO ) ·6H O instead of ytterbium nitrate. Yield:
3
3
2
7
2% (based on the crystals dried in air). Anal. Calcd for
C H Sm N O : C, 26.17; H, 2.79; N, 4.70. Found: C, 26.21; H,
52
66
6
8
38
2
.76; N, 4.66.
.3. X-ray Crystallography. Crystallographic data of Yb-BDC-
NH , Dy-BDC-NH , and Sm-BDC-NH were collected at 173 K with
Figure 1. (a) Ball and stick representation of the hexanuclear unit
2
2
[
Ln (μ -OH) (COO) ] (yellow. C; red. O; green. Ln). (b)
6 3 8 12
2
2
Representation of the BDC-NH ligand. (c) Packing of two types of
2
a Bruker D8 Quest diffractometer with Mo Kα radiation (λ = 0.71073
Å) and a graphite monochromator using the ω-scan mode. All
measured intensities were corrected for Lorentz and polarization
effects. Absorption corrections were applied using the programs
SADABS and HABITUS.
methods and refined on F by full-matrix least squares using the
SHELXTL-2014 crystallographic software package. Non-hydrogen
atoms were treated anisotropically. Positions of hydrogen atoms were
generated geometrically. There is a large solvent-accessible pore
volume in the structures of Yb-BDC-NH , Dy-BDC-NH , and Sm-
cages: the tetrahedral cage and the octahedral cage.
bifunctional catalysts for one-pot tandem deacetalization−
Knoevenagel condensation reaction.
3
2,33
2
The structure was solved by direct
3
4
2
. EXPERIMENTAL SECTION
2
.1. Materials and Methods. All chemicals for synthesis were
commercially available reagents of analytical grade and were used
without further purification. C, H, and N microanalyses were carried
out with a PerkinElmer 240 elemental analyzer. FT-IR spectra were
2
2
BDC-NH , which is occupied by highly disordered solvent molecules.
2
No satisfactory disorder model for these solvent molecules could be
achieved, and therefore the SQUEEZE program implemented in
PLATON was used to remove these electron densities of these
disordered species. Crystallographic data for structural analyses are
summarized in Table S1. The CCDC reference numbers are 1569272,
−1
recorded from KBr pellets in the 4000−450 cm range on a Nicolet
5
DX spectrometer. Thermogravimetric analyses (TGA) were taken on
−1
a PerkinElmer Pyrisl instrument (35−800 °C, 5 °C min , flowing N
35
2
gas). Powder X-ray diffraction was recorded with a Bruker D8
ADVANCE automated diffractometer with Cu Kα radiation. Variable-
temperature PXRD studies were conducted by heating the sample at a
1
569273, and 1569274 for Yb-BDC-NH , Dy-BDC-NH , and Sm-
2 2
BDC-NH , respectively.
−1
2
constant rate of 5 °C min from room temperature to 100, 150, 200,
2.4. Catalytic Performance Evaluation. Before the reactions, the
2
50, 300, and 350 °C in air, respectively. The products of catalysis
catalysts were activated at 298 K for 24 h under vacuum to remove the
residual solvent molecules on the surface of MOFs. The catalytic
reactions were carried out in a 10 mL reaction tube using
benzaldehyde dimethyl acetal (2.0 mmol) and malononitrile (2.1
mmol) in DMSO-d (2.0 mL) with magnetic stirring. Catalysts (100
mg) were then added and maintained at 50 °C for 24 h under a N2
atmosphere. When the reaction was completed, the reactor was cooled
to room temperature. The products were monitored by H NMR. The
catalysts were separated by filtration, washed abundantly with
CH OH, placed in a vial, and soaked in CH OH for 4 h and
subsequently dried under vacuum at room temperature and then
1
reactions were monitored by H NMR spectra recorded on a Varian
3
00 MHz NMR spectrometer.
N sorption isotherms were measured at 77 K using a liquid-N
2
2
bath. CO sorption isotherms were measured at 273 K using an ice/
2
6
water bath and at 298 K using a water bath. N and CO adsorption−
2
2
desorption experiments were carried out on an automated gas sorption
analyzer (Quantachrome Instruments ASiQC). The samples of Yb-
BDC-NH , Dy-BDC-NH , and Sm-BDC-NH were activated by
1
2
2
2
washing the as-synthesized crystals with DMF followed by solvent
exchange in CH OH and CH Cl for 3 days, respectively. The solution
3
3
3
2
2
was refreshed several times daily during this period. In a typical
experiment, 80−100 mg of each activated sample was transferred (dry)
to a 6 mm large bulb glass sample cell and was first evacuated at room
temperature using a turbo molecular vacuum pump and then gradually
heated to 150 °C to hold for 24 h and cooled to room temperature.
Breakthrough experiments were carried out using a home-built
setup coupled with a mass spectrometer (Hiden QGA). A dry powder
reused in the recycle reaction.
3
. RESULTS AND DISCUSSION
3.1. Crystal Structure. Compounds Yb-BDC-NH
, Dy-
2
BDC-NH , and Sm-BDC-NH2 are isostructural with the
2
36
previously reported Eu-based MOF (Eu-BDC-NH2), which
is also constructed by hexanuclear Ln clusters and BDC-NH2
linkers with fcu topology. Thus, only the crystal structure of Yb-
BDC-NH2 is simply described here. Single-crystal X-ray
crystallography indicates that Yb-BDC-NH crystallizes in the
cubic space group Fm3
of Yb-BDC-NH (500 mg for 7 cm column) was packed in a stainless
2
steel column with a diameter of 0.635 cm as the adsorbent bed. The
packed column was heated at 120 °C for 12 h under a constant He
3
−1
flow (4 ± 0.5 cm min at 298 K and 2 bar) to activate the MOF.
After that, a mixed gas containing CO /N (15/85) with a flow rate of
2
2
2
3
−1
̅
4
.75 ± 0.75 cm min (298 K, 2 bar) was introduced to the column.
Breakthrough tests of CO and N (15 ± 0.5)/(85 ± 0.5) mixtures
are linked by BDC-NH ligands to form the 3D framework
2
2
2
3
1
under wet conditions (80 ± 5% RH) were also carried out.
.2. Synthesis of Compounds. 2.2.1. Synthesis of Yb-BDC-NH ,
enclosing two types of polyhedral cages: octahedral and
tetrahedral (Figure 1). The empirical chemical formula is
[(CH ) NH ] [Yb (μ -OH) (BDC-NH ) (H O) ]·11DMF,
which was estimated by H NMR measurements for digested
Yb-BDC-NH crystals in DCl/D O/DMSO (Figure S1).
2
2
[
(CH ) NH ] [Yb (μ -OH) (BDC-NH ) (H O) ]·x(solv) (1). A mixture of
3 2 2 2 6 3 8 2 6 2 6
3
2
2
2
6
3
8
2
6
2
6
H BDC-NH (9.0 mg, 0.05 mmol), Yb(NO ) ·6H O (19.3 mg, 0.04
1
2
2
3
3
2
mmol), and 2-fluorobenzoic acid (48.7 mg) were dissolved in 2.9 mL
2
2
of a mixed solvent of DMF (2.2 mL), H O (0.5 mL), and HNO (0.2
2
3
3
.2. Chemical and Thermal Stability. The compounds
mL, 3.57 M in DMF) in a 3.5 mL scintillation vial. The resulting
mixture was kept in an oven at 105 °C for 72 h. After the vial was
cooled to room temperature, the as-synthesized sample was purified
through repeated washing with DMF to yield khaki octahedral crystals.
Yield: 63% (based on the crystals dried in air). Anal. Calcd for
Yb-BDC-NH , Dy-BDC-NH , and Sm-BDC-NH possess high
2
2
2
chemical stability and general thermal stability. The chemical
stability tests were carried out by soaking the samples in various
organic solvents (methanol, ethanol, dichloromethane, 1,4-
B
DOI: 10.1021/acs.inorgchem.7b03084
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Inorganic Chemistry
Article
Figure 2. (a) PXRD patterns of Yb-BDC-NH soaked in various organic solvents for 24 h. (b) Thermal stability tests for Yb-BDC-NH monitored
2
2
by variable-temperature PXRD analysis.
dioxane, cyclohexane, toluene), water, and even acidic and basic
solutions (i.e., HCl (pH 2) and NaOH (pH 12)) for 24 h. The
unaltered PXRD patterns of three compounds indicate no
framework collapse or phase transition during these tests
In order to verify the ligand functionalization effect of the
three compounds, the CO sorption capacities of Yb-BDC-
2
NH , Dy-BDC-NH , and Sm-BDC-NH were evaluated
2
2
2
(Figure 4). When the total pressure of CO gets close to 760
2
3
−1
(Figure 2a and Figures S2 and S4−S6). The thermal stability
Torr, the CO uptakes reach 57.3, 79.1, and 112.3 cm g at
2
was investigated by variable-temperature PXRD and thermog-
ravimetric analysis (TGA). The results confirm that these
compounds are stable up to 300 °C in air (Figure 2b and
Figures S3−S7).
273 K, respectively, which are higher than those of a few
reported MOFs possessing multinuclear metal cluster moieties
3
−1
at the same pressure, such as PCN-56 (ca. 55 cm g ) and Y-
3
−1 41,42
ftw-MOF-2 (ca. 56 cm g ),
but lower than that for fcu-
3
−1 43
3
.3. FT-IR Spectra. The IR spectra (Figure S8) of Yb-BDC-
MOF (ca. 134 cm g ). At 298 K, the CO uptakes of Yb-
2
NH , Dy-BDC-NH , and Sm-BDC-NH exhibit characteristic
2
2
2
BDC-NH , Dy-BDC-NH , and Sm-BDC-NH could reach
2
2
2
−1
3
−1
bands of carboxyl groups at 1664 and 1572 cm for the
antisymmetric stretching vibrations and at 1430 and 1384 cm
for the symmetric stretching vibrations. The separations (Δ)
between νasym(CO ) and ν (CO ) indicate the presence of
3
5.6, 41.2, and 59.0 cm g , respectively. The isosteric heat of
−1
adsorption (Q ) was calculated on the basis of the CO
st
2
37
adsorption isotherms at 273 and 298 K using the Clausius−
44
2
sym
2
Clapeyron equation, revealing that Q values of Yb-BDC-
st
bidentate bridging coordination modes in the three compounds
NH , Dy-BDC-NH , and Sm-BDC-NH at zero surface
2
2
2
−
1
38
(
234 and 188 cm ). In addition, the asymmetric and
−1
coverage are 13.3, 20.3, and 27.4 kJ mol , respectively. The
−1
symmetric −NH absorption bands at 3428 and 3344 cm as
2
amino-functionalized MOFs have a higher CO adsorption
2
−1
well as the N−H bending vibration at 1621 cm and the C−N
energy, which could be mainly attributed to a stronger
interaction between CO2 and the amino groups in the
−1
stretching vibration absorption bands at 1257 cm confirm
39,40
that free −NH groups exist in the three compounds.
45
2
pores. The formation of electron donor−acceptor complexes
3
.4. Gas Sorption. N sorption isotherms (Figure 3) of Yb-
2
between CO and the amino-functionalized MOF structure
2
BDC-NH , Dy-BDC-NH , and Sm-BDC-NH at 77 K display a
46
2
2
2
may have an effect on the CO sorption.
2
3
.5. Breakthrough Experiments. The coadsorption of the
mixed gas N /CO in Yb-BDC-NH was completed by using
2
2
2
dynamic column breakthrough tests under both dry and wet
conditions.
Typically, a longer breakthrough time represents a higher gas
uptake capacity, and a greater difference of breakthrough time
among various gas components indicates better gas separation
performance. Under dry conditions, the CO breakthrough
2
time of Yb-BDC-NH is around 500 s (Figure 5). To estimate
2
the breakthrough time in the presence of water, we introduced
a gas mixture containing 15 ± 1% of dry CO and 85 ± 1% of
2
wet N (80 ± 5% RH) to the MOF-packed column. The
2
breakthrough time of Yb-BDC-NH under wet conditions
2
showed an almost 80% decrease in comparison to that in the
absence of moisture (Figure S9). This can be attributed to the
open metal sites in this MOF that were occupied by water
Figure 3. N adsorption/desorption isotherms of Yb-BDC-NH , Dy-
2
2
BDC-NH , and Sm-BDC-NH at 77 K.
2
2
molecules under humid conditions, leading to reduced CO
2
4
7,48
fully reversible type I shape, confirming their microporosity.
Utilizing the BET (Brunauer−Emmett−Teller) method, the
surface areas of Yb-BDC-NH , Dy-BDC-NH , and Sm-BDC-
sorption site and therefore reduced CO uptake capacity.
2
Therefore, water has some influence on the CO
BDC-NH2.
uptake in Yb-
2
2
2
2
−1
NH were calculated to be 107.7, 148.2, and 171.7 m g ,
3.6. Catalytic Deacetalization−Knoevenagel Reaction.
2
respectively.
Yb-BDC-NH , Dy-BDC-NH , and Sm-BDC-NH contain Ln
2
2
2
C
DOI: 10.1021/acs.inorgchem.7b03084
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Inorganic Chemistry
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Figure 4. (a) Adsorption/desorption isotherms of CO (273 and 298 K) for Yb-BDC-NH . (b) Adsorption/desorption isotherms of CO (273 and
2
2
2
2
98 K) for Dy-BDC-NH . (c) Adsorption/desorption isotherms of CO (273 and 298 K) for Sm-BDC-NH . (d) Isosteric heats of CO adsorption
2
2
2
2
(
Q ) of the three compounds calculated from the adsorption isotherms at 273 and 298 K.
st
Table 1. One-Pot Deacetalization−Knoevenagel
a
Condensation Reactions and Yields
entry
conversn of a (%)
yield of b (%)
yield of c (%)
Yb-BDC-NH2
Dy-BDC-NH2
Sm-BDC-NH2
second recycle
third recycle
fourth recycle
no catalyst
97.0
82.0
76.0
93.0
92.0
90.2
∼0
trace
trace
trace
2.7
97.0
82.0
76.0
90.3
91.6
90.0
trace
0.4
0.2
Figure 5. Breakthrough curves of a CO /N mixture in Yb-BDC-NH
2
2
2
trace
3
−1
with a total CO /N mixture flow rate of 4.75 ± 0.25 cm min (P = 2
2
2
a
Reaction conditions: benzaldehyde dimethyl acetal (2.0 mmol),
malononitrile (2.1 mmol), DMSO-d (2 mL), and catalyst (100 mg);
bar) at 298 K.
6
reaction temperature 50 °C; reaction time 24 h. The conversions were
1
determined by H NMR.
ions which possess Lewis acidic activity to catalyze the
deprotection of benzaldehyde dimethyl acetal to give
benzaldehyde. An amino group as a weak Brønsted base can
catalyze the Knoevenagel condensation reaction between
benzaldehyde and malononitrile (Table 1). The amino groups
undergo nucleophilic attack on the carbonyl carbon, and water
is released in the formation of an imine intermediate. Then,
malononitrile reacts with the intermediate. Finally, products are
activity for tandem deacetalization−Knoevenagel condensation
reactions.
The catalytic reactions were performed with 2 mmol of each
substrate in DMSO-d (2 mL) an the catalyst (100 mg) in a 10
6
1
mL reaction tube at 50 °C under a N atmosphere for 24 h. H
2
NMR spectroscopy was utilized to detect this tandem reaction
process. Experimental results are given in Table 1. After 24 h of
reaction, the yields of product c catalyzed by Yb-BDC-NH2,
Dy-BDC-NH , and Sm-BDC-NH reach about 97.0, 82.0, and
49
formed and the amino groups are regenerated. Thus, the
three compounds are a kind of potential bifunctional acid−base
2
2
catalyst. In order to prove this point, Yb-BDC-NH , Dy-BDC-
76.0%, respectively. In comparison with previous catalysts
(Table S2), the three compounds also exhibit good catalytic
2
NH , and Sm-BDC-NH were utilized to study their catalytic
2
2
D
DOI: 10.1021/acs.inorgchem.7b03084
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Inorganic Chemistry
Article
activity toward the deacetalization−Knoevenagel condensation
ACKNOWLEDGMENTS
■
reaction. Among them, Yb-BDC-NH demonstrates the highest
2
This work was financially supported by the National Natural
Science Foundation of China (Grants 21671090, 21701076,
and 21271096).
catalytic activity due to the smaller ionic radius and stronger
5
0
Lewis acidity (Table 1). Hence, Yb-BDC-NH was chosen to
2
explore the dynamic change of the reaction over time (Figure
S10) and catalyst recovery. Though the activity of catalyst Yb-
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2
■
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loss of catalytic activity during the reuse cycles. Our future work
will deal with systematically synthesizing multifunctional
polynuclear Ln cluster based MOFs and exploring their
properties in one-pot tandem reactions.
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Exceptional Chemical and Thermal Stability of Zeolitic Imidazolate
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Supporting Information
The Supporting Information is available free of charge on the
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chem.7b03084.
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Accession Codes
CCDC 1569272−1569274 contain the supplementary crystal-
lographic data for this paper. These data can be obtained free of
charge via www.ccdc.cam.ac.uk/data_request/cif, or by email-
ing data_request@ccdc.cam.ac.uk, or by contacting The
Cambridge Crystallographic Data Centre, 12 Union Road,
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AUTHOR INFORMATION
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*
*
(14) Guillerm, V.; Weselinski, L.; Belmabkhout, Y.; Cairns, A. J.;
Corresponding Authors
E-mail for L.L.: liulin@lnu.edu.cn.
E-mail for Z.-B.H.: ceshzb@lnu.edu.cn.
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ORCID
Dan Zhao: 0000-0002-4427-2150
Zheng-Bo Han: 0000-0001-8635-9783
heterogeneous catalysts for CO conversion. Appl. Catal., B 2017,
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The authors declare no competing financial interest.
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