Compartmentalization of Incompatible Polymers within Metal–Organic Frameworks towards Homogenization of Heterogeneous Hybrid Catalysts for Tandem Reactions

Article abstract of DOI:10.1002/chem.201801416

New catalytic systems that contain incompatible catalytic sites were constructed by the in situ polymerization of acidic and basic polymers into metal–organic frameworks, which resulted in highly porous, recyclable, and durable catalytic composites with excellent compartmentalization, so that opposing agents were spatially isolated. These synthesized hybrid catalysts exhibited excellent catalytic activity for one-pot “wolf and lamb” reactions (deacetalization/Knoevenagel or Henry), which was attributed to their unique characteristic of having a locally homogeneous, but globally heterogeneous, structure.

Full text of DOI:10.1002/chem.201801416

A Journal of
Accepted Article
Title: Compartmentalization of Incompatible Polymers within Metal-
Organic Framework towards Homogenization of Heterogeneous
Hybrid Catalysts for Tandem Reactions
Authors: Jin-Hao Zhao, Yong Yang, Jin-Xin Che, Jun Zuo, Xiao-Hua Li,
Yong-Zhou Hu, Xiao-Wu Dong, Liang Gao, and Xin-Yuan Liu
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To be cited as: Chem. Eur. J. 10.1002/chem.201801416
Link to VoR: http://dx.doi.org/10.1002/chem.201801416
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Compartmentalization of Incompatible Polymers within Metal-
Organic Framework towards Homogenization of Heterogeneous
Hybrid Catalysts for Tandem Reactions
Jin-Hao Zhao,[b] Yong Yang,[ab] Jin-Xin Che,[a] Jun Zuo,[b] Xiao-Hua Li,[c] Yong-Zhou Hu,[a] Xiao-Wu
Dong,*[a] Liang Gao,*[d] Xin-Yuan Liu,*[c]
Abstract: New catalytic systems bearing incompatible catalytic sites
can be designed via In situ polymerization of acidic and basic
polymers into MOFs, resulting in highly porous, recyclable, and
durable catalytic composites with excellent compartmentalization to
spatially isolate opposing agents. These synthesized hybrid catalysts
exhibit excellent catalytic activity for one-pot “wolf and lamb”
reactions (deacetalization-Knoevenagel/Henry), which would be
attributed to their unique characteristic of locally homogeneous but
globally heterogeneous structure.
strategies involving solid supports can be classified into two
types: 1) anchorage/encapsulation of catalytic groups with
opposite properties onto insoluble solids to form
heterogeneous catalyst; with this technique, the active sites,
which can react with each other in solution, can be
physically separated;[4,5] 2) fabrication of soluble core-
confined star/bottlebrush polymers, where the incompatible
reactive agents are located in the core and sterically
isolated from each other by fully extended long hydrophobic
brush.[6,7] The first strategy renders relatively easy
separation from the products and solution; however, the
heterogeneous catalysts typically bear the drawbacks of
insufficient contact with the organic reactants. The second
strategy affords homogeneous multifunctional catalysts,
which have demonstrated high activity, but whose
recyclability is still a challenge. Therefore, a mechanistically
distinct strategy needs to be developed for the rational
design of multifunctional catalysts for cascade reactions.
Introduction
Enzymatic catalysis is one of the most advanced synthetic
processes.[1] In addition to adaptive properties, enzymatic
catalysis combines multiple incompatible catalytic sites that
can effectively catalyze tandem reactions. The cascade
process demonstrates superior performance to that of two-
step conventional reaction.[2] Work on developing catalysts
that can act like enzymes has attracted intense attention;
however, progress has been slowed because, in
conventional catalytic systems, these incompatible catalysts
can be quenched or deactivated during the reaction. The
trade-off between isolation of active site and preservation of
activity is still a challenging issue.[3]
The concept of “wolf and lamb” reactions emerges as a
powerful tool to probe site-isolation effects. To catalyze
“wolf and lamb” reaction, the incompatible active sites are
separately embedded in different heterogeneous solid
supports. Various solid supports have been employed, such
as resin,[4] sol−gel colloids,[5] Pickering emulsions,[6] or
polymeric micelles.[7] In general, the precedent catalytic
Figure 1. Compartmentalization of incompatible polymers within MOF via
in situ polymerization of hostile vinyl substrates for Tandem Reaction.
[a]
Y. Yang, J.-X. Che, Prof. Dr. Y.-Z. Hu, Dr. X.-W.Dong
College of Pharmaceutical Sciences
Zhejiang University, Hangzhou, 310058 (P. R. China)
E-mail: dongxw@zju.edu.cn
Metal-organic frameworks (MOFs) have become particularly
attractive for a wide range of applications, such as gas
storage,[8a,b] separation,[8c] drug delivery,[8d] and catalysis.[8e-g]
Recently, Kitagawa, Uemura, and co-workers reported a series
of MOF/polymer composites,[9] providing a powerful tool for the
integration of functional polymers and MOF.[10] This new class of
porous composites has the linear polymer threading throughout
the nano-space of MOFs. In principle, although there may exist
strong interaction between pore wall of MOF and polymers (e.g.,
hydrophobic interaction, electrostatic interaction), the solvent
can significantly reduce net segment-segment forces (e.g.,
electrostatic, van der Waals force). Therefore, when in contact
with appropriate solvents, the polymer in the polymer/MOF
composite can detach from the wall of MOFs, but reside in the
channel of MOFs due to the confinement effect, while the
skeleton of MOFs remains unchanged. In this sense, the
[b]
[c]
Dr. J.-H.Zhao, Y. Yang, J. Zuo
Institute of Pesticide and Environmental Toxicology
Zhejiang University, Hangzhou, 310029, China
Dr. X.-H. Li, Prof. Dr. X.-Y. Liu
Department of Chemistry,
South University of Science and Technology of China, Shenzhen,
518055, China
E-mail: liuxy3@sustc.edu.cn
Dr. Liang Gao
School of Chemical Engineering and Light Industry
Guangdong University of Technology, Guangzhou, 510006, China
E-mail: gaoliang@gdut.edu.cn
[d]
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
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composite has the characteristics of a locally homogeneous but
globally heterogeneous structure. These features make
polymer/MOF an ideal support to demonstrate the concept of
“wolf and lamb” reactions.
In juxtaposition to the abovementioned strategies, the use of
polymer/MOF can combine heterogenous and homogenous
properties in one single catalytic system, exploiting their
respective advantages while effectively avoiding their
To confirm the polymeric and chemical structure of the
polymer inside the MOF, the linear polymers (PBSA and PMAP)
within cavities of PBSA/MIL-101 and PMAP/MIL-101 are
released and collected by digesting MIL-101 with strong alkaline.
As shown in Figure 3a, proton chemical shifts match with those
of bulk PBSA and PMAP prepared using solution approach (for
the preparative protocol, see supporting information). The broad
peaks around 7.5 ppm belong to the aromatic H of BSA, while
the ones in the spectrum of PMAP/MIL-101 ~2.96, 4.40, 6.50,
6.80, and 8.10 ppm are associated to the N-methyl of pyridine,
benzyl hydrogen protons, and aromatic H of polymeric styrene
and pyridine, respectively. Furthermore, the released PBSA and
PMAP polymers were characterized via gel permeation
chromatography (GPC) to have a number-average molecular
weight of ~Mn=3600 and 7000, respectively (Figure S1,
supporting information). This is equivalent to ca. 27 and 34
repeat units of PBSA and PMAP, the length of which is enough
to intertwine within the cavities of Cr-MIL-101. The existence of
acidic and basic active sites is also confirmed via using solid-
state Fourier transform infrared spectroscopy (FTIR). In FTIR
spectra of polymer/MOF composites, characteristic bonds (e.g.,
S-O and C=N) of the included polymers are observed (Figure S2,
supporting information). These NMR and FTIR results
demonstrate the successful anchorage of BSA and MAP during
the in-situ polymerization, respectively. Then, the loading
amounts of polymers are quantified, showing that there are 1.01
mmol and 0.34 mmol of acidic and basic groups per gram of
PBSA/MIL-101 and PMAP/MIL-101, respectively (Eqs. 1-2).
Examination of the gas adsorption behavior indicates that all of
the functionalized MOFs are porous (Figure 2b, Table 1). Their
surface areas are still very large to ensure good contact with
reactants. Furthermore, scanning electron microscopy (SEM)
and transmission electron microscopy (TEM) experiments
revealed that most of the vinyl monomers were polymerized
inside the microspore of MIL-101 without bulk polymer formation
on the external surface (Figures S3 and S4, supporting
information). Thermogravimetric analysis (TGA, Figure S5,
supporting information) confirms the thermal stability of
PBSA/MIL-101 and PMAP/MIL-101. The thermal decomposition
temperature of the loaded polymer can be higher (e.g., PBSA is
~400 ℃ ) than that of MIL-101 (~350 ℃ ). Powder X-ray
diffraction (PXRD, Figure 3c) confirms retention of the parent
framework structure of octahedron-like morphology and the
crystallinity of the resultant MOF-polymer composites.
shortcomings. Herein, we develop
a novel “site-isolation”
methodology via convenient in situ polymerization of hostile vinyl
substrates within MOFs to compartmentalize incompatible
polymers (Figure 1). The excellent catalytic performance of the
so-prepared MOF/polymer composites was demonstrated in a
sequential two-step reaction.
Results and Discussion
To validate the feasibility of the above proposed “site-isolation”
strategy, we selected the Cr-MIL-101 as a host material due to
its interconnected cage-type pore, sufficiently large pore size to
allow monomer penetration (Figure 2) and reasonable stability
against common solvents.[11,12] Benzene sulfonic acid (BSA) and
methylaminopyridine (MAP) are chosen as agents to offer
incompatible active sites. The preparation of the acidic
PBSA/MIL-101 and basic PMAP/MIL-101 is accomplished in two
steps via in situ polymerization strategy: (1) a solution of BSA- or
MAP-containing vinyl derivative S1 (for the preparative protocol,
see supporting information) and 2,2-azobisisobutyronitrile
(AIBN) in DMF/H2O is impregnated into the porous cavities of
Cr-MIL-101; (2) in situ radical polymerization of the preloaded
vinyl compounds is initiated by heating. Upon sufficient contact,
the monomer-containing solution can be expected to penetrate
into Cr-MIL-101; when polymerization occurs, the monomer
units in different cages can polymerize together through
neighboring cavities, so that the formed polymer can be
physically interlocked inside MOFs. In situ polymerization is
conducted to encapsulate BSA- or MAP-containing vinyl
monomers onto polystyrene, leading to the formation of the
desired MOF/acidic/basic polymer (Figure 1). The resulting
polymeric chains can be isolated by ordered pores of the MOF.
Table 1. Textural structure and amount of active site of MOFs and its
composites.
Pore
size[a]
(nm)
Pore
volume[b]
(mL/g)
Amount of
active site[c]
(mmol/g)
BET surface
area (m3/g)
Sample
MIL-101
3024
564
2.5
2.3
2.3
1.43
0.27
0.52
0
PMAP/MIL-101
PBSA/MIL-101
0.34
1.01
1107
[a] Pore size distribution is calculated based on BJH model and
desorption branch; b Total pore volume; cActive site is defined as either
acidic or basic groups on the polymer and the amount is determined
based on the loadings of polymer in the composites (see below).
Figure 2. The topological characteristic of (a) Cr-MIL-101, (b) the proposed
model for encapsulated linear polymer PBSA and PMAP (six repetitive
Besides, due to the nature of linear, relatively short, and
isolated polymeric chains within MOF, the dissolution/swelling
process would be facile due to the minimized polymer-polymer
units)
.
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10.1002/chem.201801416
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interaction. The dissolution process of the chiral polymeric
chains is significantly easier than routine BSA-containing cross-
linked PPBSA and MAP-containing cross-linked PPMAP resin
(Figure S6, supporting information).
can relate the catalytic performance to their structure features:
the high porosity of PBSA/MIL-101 and PMAP/MIL-101 would
provide sufficiently guest-accessible room for catalysis. In
addition, the unique structures of the MOF/chiral polymer
composites featuring with heterogeneous matrix and local
homogeneous active domain would contribute to the efficient
catalytic site-exposure of PBSA/MIL-101 and PMAP/MIL-101.
The recyclability of the bifunctional catalyst PBSA~PMAP/MIL-
101 is also excellent. The yield of the 4th run is about 83% of the
value of the 1st run. After recycling, the crystallinity of the
catalyst has been maintained as verified by PXRD (Figure S7,
supporting information).
Table 2. One pot sequential deacetalization-Knoevenagel reaction.[a]
Conv. of
1a (%)[b]
Yield of
2a (%)[c]
Yield of
4a (%)[c]
Entry
Catalyst
1
2
3
4
5
MIL-101/PBSA~PMAP
TPSA + DMAP
100
Trace
40
Trace
Trace
33
89
Trace
Trace
Trace
9
PPBSA+PPMAP
PBSA~PMAP/MIL-101 +MAP
PBSA~PMAP/MIL-101+ TPSA
Trace
100
Trace
91
Figure
2
(a) 1H-NMR spectra of encapsulated polymers of the digested
[a] Reaction conditions: 1a (0.25 mmol), 3a (0.3 mmol), DMSO/H2O
(40/1, v/v), 70 oC, 12h. [b] Conversion of was determined from 1H NMR
of the crude reaction mixtures. [c] The yield was determined by isolated
yield.
PBSA/MIL-101, PMAP/MIL-101 and the bulk PP1 (MeOH-d4) prepared in a
solution approach; (b) N2 isotherms for Cr-MIL-101, PBSA/MIL-101 and
PMAP/MIL-101; (c) PXRD measurements of Cr-MIL-101, PBSA/MIL-101 and
PMAP/MIL-101.
Table 3. PBSA~PMAP/MIL-101 catalyzed one pot deacetalization-
These functionalized acidic/basic polymers/MOF composites
are used to catalyze one-pot tandem reactions (Table 2),
involving two steps: a) deacetalization reaction by acid catalysis;
b) Knoevenagel reaction by basic catalysis. It is notable that the
linear PBSA and PMAP released from the alkaline digestion of
MIL-101 framework are completely soluble in the reaction
solvent (DMSO/H2O: 40/1, v/v) with solubility more than 20
mg/mL (Figure S6, supporting information). This further supports
the coexistence of global heterogeneous and local homogenous
domains in our designed catalytic system. We examined the
reaction of p-fluoro-benzaldehyde glycol acetal and ethyl
cyanoacetate in the presence of various heterogeneous and
homogeneous catalysts as a model reaction. A mixture of a
catalytic amount (5 mol%) of PBSA/MIL-101 and PMAP/MIL-101
(PBSA~PMAP/MIL-101) efficiently catalyzes this reaction to give
4a in a quantitative yield after 12 h (Table 2, entry 1), whereas a
mixture of p-toluene sulfonic acid (PTSA) and 4-
dimethylaminopyridine (MAP) as a homogeneous catalyst (5
mol%) shows no activity (Table 2, entry 2), maybe due to the
fast acid-base neutralization. In contrast, the use of a mixture of
routine cross-linked polystyrene resins PPBSA and PPMAP can
only lead to the deacetalization product 2a in 33% yield; the
desired product has, thus, not been formed, revealing that the
exposure of incompatibly catalytic sites on the surface of solid
materials can also remarkably interfere with each other when
mixing them up. Moreover, the addition of excessive amounts of
Knoevenagel reaction.[a]
Entry
1
3
Yield of 4[%]
1
2
3
4
5
6
1b: R1=H
1c: R1=OCH3
1d: R1=F
3a: R2=COOEt
3a: R2=COOEt
3c: R2=COOMe
3d: R2=COOi-Pr
3d:R2=COOi-Bu
3d:R2=COOt-Bu
4b: 93
4c: 90
4e: 86
4f: 88
4g: 78
4h: 75
1d: R1=F
1d: R1=F
1d: R1=F
7
3a: R2=COOEt
4i: trace
[a] Reaction conditions: compound
1 (0.25 mmol), 3 (0.3 mmol),
PBSA~PMAP/MIL-101 (5 mmol%, 0.0125 mmol), DMSO/H2O (40/1, v/v),
70 oC, 12h.
To demonstrate the universality of these catalysts, we further
extended the scope of this protocol to other aldehyde glycol
acetals with cyanoacetate derivatives. As shown in Table 3, the
electron-donating (OMe), electron-withdrawing groups (F), and
neutral (R=H) on para position of the benzene ring of aldehyde
glycol acetal are all well tolerated to produce the expected
products in good yields (Table 3, entry 1-3). Besides, the size of
ester group (iPr, i-Bu, and t-Bu) of cyanoacetate showed slightly
influence on the reaction outcome (Table 3, entries 4-6),
affording the desired products in moderate to good yields. Next,
we turned our attention toward the bulk aldehyde glycol acetal
1e as a substrate for this reaction, which is even larger than the
free acid (TPSA,
5
eq.) or base (MAP
5
eq.) to
PBSA~PMAP/MIL-101 can entirely stop the catalytic activity
(Table 2, entries 5 and 6), demonstrating that the opening
channel filled with catalytic sites can be readily reached for
reaction substrate/opposite agents. This contrasting experiment
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were purchased and used without further purification from commercial
suppliers (Sigma-Aldrich, Alfa Aesar, TCI, and others).
window size of Cr-MIL-101. Accordingly, the expected products
4i were only obtained in trace (Table 3, entry 7), revealing that
the catalytic reactions occur mostly in the cavities of the catalyst
rather than on the external surface, and thus exhibiting reagent
size selectivity for such heterogeneous catalyst.
The synthesis of the PBSA/MIL-101 composites. A solution of sodium
4-styrenesulfonate (300 mg, 1.46 mmol) and 2,2-azobisisobutyronitrile
(AIBN, 45 mg, 0.27 mmol, as radical initiator) in 1.5 mL DMF/H2O (5:1,
v/v) was impregnated into Cr-MIL-101 (0.7 g). The mixture was ground in
a mortar and then allowed to stand at 4 °C for 12 hours to reach
distribution equilibrium of the monomers through the cavities of MIL-101.
The polymerization was conducted under a nitrogen atmosphere at 80 °C
for 5 days. The so-obtained powder was soaked in DMF for 3 days and
intensively washed with DMF to completely remove all unreacted
monomer and loosely attached polymers. The residue DMF was then
removed by soaking and washing with acetone. Finally, the obtained
composite was acidified by soaking in 12N HCl for 12 hours, filtered and
further dried at 80 °C for overnight.
Furthermore, PBSA~PMAP/MIL-101 has also been evaluated in
a tandem reaction involving the hydrolysis of an acetal and a
subsequent Henry reaction (Scheme 1). Remarkably, the
bifunctional catalytic composites can convert benzaldehyde
glycol acetal 5 into desired product 7 with a good yield of 94%
without any aldehyde intermediate.
The synthesis of the PMAP/MIL-101 composites. A solution of
compound S1 (300 mg, 1.34 mmol, see supporting information) and 2,2-
azobisisobutyronitrile (AIBN, 45 mg0.27 mmol), as a radical initiator, in
toluene (1.5 mL) was impregnated into Cr-MIL-101 (0.7 g). The mixture
was ground finely in a mortar and then allowed to stand at 4 °C for 12
hours to reach distribution equilibrium of the monomers through the
cavities of MIL-101. The polymerization was conducted under a nitrogen
atmosphere at 80 °C for 5 days. The obtained powder was firstly soaked
in DMF for 3 days and then washed with acetone to remove the residue
DMF. Finally, the powder was repeatedly washed with 1N HCl to
completely remove all unreacted monomer and loosely attached
polymers between MIL-101 particles. After soaked in 5 % NaHCO3 for 12
hours, the desired polymer composite PMAP/MIL-101 was obtained and
further dried at 80 °C for overnight.
Scheme 1. PBSA~PMAP/MIL-101 catalyzed one pot deacetalization-henry
reaction.
Conclusions
We have demonstrated the “Wolf and Lamb” concept with
bifunctionlized linear polymer/MOF composites. The acidic and
basic polymers are separately accommodated into MOF via the
steps of loading corresponding monomers and then
polymerization. These two types of polymers/MOF catalysts
bearing isolated active sites work together to catalyze one-pot
tandem reactions. The tightly intertwined state of linear polymers
and MOF architecture ensures this heterogeneous material to
The extraction of the linear polymer PBSA (or PMAP) from the
PBSA/MIL-101 (or PMAP/MIL-101) composites for NMR and GPC
analyses. PBSA/MIL-101 (200 mg) was first fully digested by 10 wt.%
NaOH at 120 °C for 10 min. The pH of the obtained solution was
adjusted by 6 N HCl to slightly lower than 7. The NaPBSA together with
terephthalic acid was precipitated out by adding an excessive amount of
acetone. The precipitation was collected by filtration and washed with
diethyl ether to remove the terephthalic acid; however, pure NaPBSA
polymer cannot be obtained even though intensive washings was
conducted. Then, the precipitation was dried and soaked in 2 mL H2O.
The insoluble solid was removed by filtration, and the filtrate was
evaporated in vacuum. The resulting white solid was further dried by oil
pump at 120 oC for 4 hours to afford encapsulated PBSA.1H-NMR (500
MHz, D2O): 7.83 (d, J = 7.8 Hz, 2H), 6.78 (s, 2H), 2.68~1.04 (m, 3H). b)
PMAP/MIL-101 (200 mg) was first fully digested by 10 wt.% NaOH at
120 °C for 10 min. The precipitation was collected by filtration and fully
dried. Then, the precipitation was soaked in 10 mL CH2Cl2. The insoluble
solid was removed by filtration, and the filtrate was evaporated in vacuum.
The resulting solid was further dried by oil pump at 120 °C for 4 hours to
afford encapsulated PMAP. 1H-NMR (500 MHz, CDCl3): 8.11 (s, 2H),
7.16~6.10 (m, 6H), 4.59~4.10 (m, 2H), 3.04 (m, 3H), 2.07~0.64 (m, 4H).
have
good
recyclability
and
provide
excellent
compartmentalization to spatially isolate incompatible or
opposing reagents. More importantly, by contrast to the previous
strategies to realize site-isolated catalysts, the polymer/MOF
composite can provide unique local homogeneous and global
heterogeneous micro-domain.
Experimental Section
Chemicals and instrument information. NMR spectra were recorded
on a Brüker DPX-400/500 spectrometer at 400/500 MHz for 1H-NMR and
100/125 MHz for 13C-NMR. Data for 1H-NMR are recorded as follows:
chemical shift (ppm), multiplicity (s, singlet; d, doublet; t, triplet; q,
quarter; m, multiplet), coupling constant (Hz), integration. Data for 13C-
NMR are reported in terms of chemical shift (δ, ppm). Mass spectra were
determined on an Esquire-LC-00075 mass spectrometer. All infrared
experiments were performed on a Brüker Alpha FT-IR spectrometer
using ~1.0 mg of the solid sample at a 4 cm-1 resolution. Powder X-ray
diffraction (PXRD) data were collected at ambient temperature on a
Bruker D8 Advance diffractometer at 40 kV, 40 mA for Cu Kα (λ= 1.5418
Å), with a scan speed of 1 sec/step, a step size of 0.02° and a 2θ range
of 5-40°. The Brunauer−Emmer−Teller (BET) surface areas were
measured via Micromeritics ASAP 2020 analyzer at 77 K.
Thermogravimetric Analysis (TGA) data were collected at Perkin Elmer
TGA 7 running from 50 °C to 500 °C with a scan rate of 10 °C/min.
Analyses of the morphology and chemical composition of the samples
were conducted via a Hitachi S-4800 field-emission scanning electron
microscope (FE-SEM). The computational modeling for the topological
characteristic of the host, monomers, and linear polymers were archived
by Discovery Studio 2.5 (Accelrys Software Inc., San Diego, CA). Gel
permeation chromatography (GPC) analysis was performed on Waters
1525 with refractive index (RI) detector. Starting materials and solvents
Qualification for the PBSA loading amount with a unit of mmol/g in
the PBSA/MIL-101 composite. CHNS element analysis gives the value
of S weight ratio in PBSA/MIL-101. S can only derive from the PBSA
within MOF. The molecular formula of PBSA are well defined (WPBSA, -
(C8H8O3S)n-); therefore, if we know the S weight content (Ws, %), the
PBSA loading amount with a unit of mmol/g (C) in PBSA/MIL-101
composite can be calculated based on the following Eq. 1:
푊
32 ∗ 100
푠
∗ 푊푃퐵푆퐴 ∗ 1000
퐶 =
퐸푞. 1
푊푃퐵푆퐴
Qualification for the PMAP loading amount with a unit of mmol/g in
the PMAP/MIL-101 composite. PMAP/MIL-101 (2 g) was first fully
digested by 10 wt.% NaOH at 120 °C for 10 min. The precipitation was
collected by filtration and fully dried. Then, the precipitation was extracted
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10.1002/chem.201801416
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by CH2Cl2 (50 mL x 3). The organic layer was combined and evaporated
in vacuum. The 1H-NMR analysis was performed using dibromomethane
(CH2Br2) as the internal standard (174 mg, 1 mmol). The molecular
formula of PBSA are well defined (WPBSA, -(C15H16N2)n-), Indeed, NMR
analysis gives the value of PMAP/CH2Br2 molar ratio, which can be
calculated by the ratio of integral area between δPMAP (IAPMAP, ~4.9 ppm)
and δCH2Br2(IACH2Br2, ~5.5 ppm). Therefore, the PMAP loading amount
with a unit of mmol/g (C) in can be calculated based on Eq. 2:
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퐼퐴푃푀퐴푃 /퐼퐴퐶퐻2퐵푟2 ∗ 1 ∗ 푊푃푀퐴푃
퐶 =
퐸푞. 2
푊푃푀퐴푃 ∗ 2
Typical reaction procedure for the deacetalization-Knoevenagel
reaction in one pot. A suspension of PBSA/MIL-101 (12.3 mg, 0.0125
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Acknowledgements
The authors gratefully acknowledge Prof. Chi-Ming Che at The Hong Kong
University for their knowledge sharing and suggestions on Homogenization of
Heterogeneous composites as catalytic system. Financial support from the
National Natural Science Foundation of China (Nos. 21572096, 51603046),
the National Key Basic Research Program of China (973 Program
2013CB834802), Shenzhen overseas high level talents innovation plan of
technical innovation project (KQCX20150331101823702), Shenzhen special
funds for the development of biomedicine, Internet, new energy, and new
material industries (JCYJ20150430160022517) and South University of
Science and Technology of China (FRG-SUSTC1501A-16) is greatly
appreciated.
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Keywords: Metal-organic Framework • Hybrid Catalysts •
Tandem Reaction • in situ polymerization • Incompatible
Polymers
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This article is protected by copyright. All rights reserved.

10.1002/chem.201801416
Chemistry - A European Journal
FULL PAPER
FULL PAPER
New catalytic system
J.-H. Zhao, Y. Yang, J.-X. Che, J. Zuo,
X.-H. Li, Y.-Z. Hu, X.-W. Dong,* L. Gao,*
X.-Y. Liu*
compartmentalizing incompatible
catalytic sites is realized, exhibiting
excellent catalytic activity for one-pot
“wolf and lamb” reactions.
Page No. – Page No.
Compartmentalization of
Incompatible Polymers within Metal-
Organic Framework towards
Homogenization of Heterogeneous
Hybrid Catalysts for Tandem
Reactions
This article is protected by copyright. All rights reserved.