Porous metalloporphyrinic frameworks constructed from metal 5,10,15,20-tetrakis(3,5-biscarboxylphenyl)porphyrin for highly efficient and selective catalytic oxidation of alkylbenzenes

Article abstract of DOI:10.1021/ja303728c

We incorporate metal 5,10,15,20-tetrakis(3,5-biscarboxylphenyl)porphyrin (M-H₈OCPP), for the first time, into porous metal-organic frameworks. The self-assembled porous metalloporphyrinic frameworks [Mn₅Cl ₂(MnCl-OCPP)(DMF)₄(H₂O)₄] ?2DMF?8CH₃COOH?14H₂O (ZJU-18; ZJU = Zhejiang University), [Mn₅Cl₂(Ni-OCPP)(H ₂O)₈]?7DMF?6CH₃COOH?11H ₂O (ZJU-19), and [Cd₅Cl₂(MnCl-OCPP)(H ₂O)₆]?13DMF?2CH₃COOH?9H ₂O (ZJU-20) are isostructural as revealed by their single X-ray crystal structures. The metalloporphyrin octacarboxylates (M-OCPP) (M = Mn ^IIICl for ZJU-18 and ZJU-20, M = Ni^II for ZJU-19) are bridged by binuclear and trinuclear metal carboxylate secondary building units to form a 3-periodic, binodal, edge-transitive net with Reticular Chemistry Structure Resource symbol tbo with pore windows of about 11.5 A and pore cages about 21.3 A in diameter. The porous nature of these metalloporphyrinic frameworks is further established by sorption studies in which different substrates such as ethanol, acetonitrile, acetone, cyclohexane, benzene, toluene, ethylbenzene, and acetophenone can readily have access to the pores. Their catalytic activities for the oxidation of alkylbenzenes were examined at 65 °C using tert-butyl hydroperoxide as the oxidant. The results indicate that ZJU-18 is much superior to ZJU-19, ZJU-20, and homogeneous molecular MnCl-Me₈OCPP, exhibiting highly efficient and selective oxidation of ethylbenzene to acetophenone in quantitative >99% yield and a turnover number of 8076 after 48 h.

Full text of DOI:10.1021/ja303728c

Article
pubs.acs.org/JACS
Porous Metalloporphyrinic Frameworks Constructed from Metal
,10,15,20-Tetrakis(3,5-biscarboxylphenyl)porphyrin for Highly
Efficient and Selective Catalytic Oxidation of Alkylbenzenes
5
Xiu-Li Yang, Ming-Hua Xie, Chao Zou, Yabing He, Banglin Chen,* Michael O’Keeffe,∥
†
†
†
§
,‡,§
,
†
and Chuan-De Wu*
†
‡
Department of Chemistry and State Key Laboratory of Silicon Materials, Cyrus Tang Center for Sensor Materials and Applications,
Department of Materials Science & Engineering, Zhejiang University, Hangzhou 310027, People’s Republic of China
§
Department of Chemistry, University of Texas at San Antonio, One UTSA Circle, San Antonio, Texas 78249-0698, United States
∥Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85287, United States
*
S Supporting Information
ABSTRACT: We incorporate metal 5,10,15,20-tetrakis(3,5-
biscarboxylphenyl)porphyrin (M-H OCPP), for the first time,
8
into porous metal−organic frameworks. The self-assembled
porous metalloporphyrinic frameworks [Mn Cl (MnCl-OCPP)-
5
2
(
DMF) (H O) ]·2DMF·8CH COOH·14H O (ZJU-18; ZJU =
4 2 4 3 2
Zhejiang University), [Mn Cl (Ni-OCPP)(H O) ]·7DMF-
5
2
2
8
·
6CH COOH·11H O (ZJU-19), and [Cd Cl (MnCl-OCPP)-
3 2 5 2
(
H O) ]·13DMF·2CH COOH·9H O (ZJU-20) are isostructural
2 6 3 2
as revealed by their single X-ray crystal structures. The
III
metalloporphyrin octacarboxylates (M-OCPP) (M = Mn Cl
for ZJU-18 and ZJU-20, M = Ni for ZJU-19) are bridged by binuclear and trinuclear metal carboxylate secondary building units
II
to form a 3-periodic, binodal, edge-transitive net with Reticular Chemistry Structure Resource symbol tbo with pore windows of
about 11.5 Å and pore cages about 21.3 Å in diameter. The porous nature of these metalloporphyrinic frameworks is further
established by sorption studies in which different substrates such as ethanol, acetonitrile, acetone, cyclohexane, benzene, toluene,
ethylbenzene, and acetophenone can readily have access to the pores. Their catalytic activities for the oxidation of alkylbenzenes
were examined at 65 °C using tert-butyl hydroperoxide as the oxidant. The results indicate that ZJU-18 is much superior to ZJU-
1
9, ZJU-20, and homogeneous molecular MnCl-Me OCPP, exhibiting highly efficient and selective oxidation of ethylbenzene to
8
acetophenone in quantitative >99% yield and a turnover number of 8076 after 48 h.
INTRODUCTION
molecular recognitions and thus to realize their applications in
■
gas separation, sensing, heterogeneous catalysis, bioimaging,
and even drug delivery, as well established in the traditional
Porphyrin and metalloporphyrin molecules have unique
chemical, physical, and electronic structures and properties
and play a number of important roles in molecular binding,
reaction catalysis, energy and electron transfer, and light
17−22
porous MOF materials.
Although this metalloporphyrinic
framework approach is very promising to target functional
materials, the progress on such a research endeavor has been
very slow. The first several MPFs by making use of (5,10,15,20-
1
,2
harvesting. Accordingly, they have been widely explored as
the building blocks for the construction of diverse functional
materials, ranging from photonic devices to conductive
polymers, chemical sensors, receptors for selective catalysis,
material for magnetic ordering, and light-harvesting materi-
2
+
tetra-4-pyridyl-21H,23H-porphinato)metal (metal = Pd and
2
+
Cu ) building blocks were synthesized and structurally
23
characterized back in the early 1990s. Significant progress
was only made when Suslick established the permanent
porosity of the PIZA-1 constructed from cobalt(III) tetrakis-
3
−9
als.
To incorporate these porphyrin and metalloporphyrin
building blocks into the emerging metal−organic framework
MOF) materials (we specifically term this subclass of MOFs
metalloporphyrinic frameworks (MPFs)), the three-dimen-
sional periodical arrangements of these moieties within the
frameworks have enabled them to collaboratively interact with
(
p-carboxyphenyl)porphyrin by sorption studies in 2002 and
later realized the catalytic properties of the PIZA-3 built from
(
24
manganese(III) tetrakis(p-carboxyphenyl)porphyrin in 2005.
Over the past two decades, the explored metalloporphyrin
building blocks have been mainly focused on commercially
available porphyrin linkers, including the two mentioned above,
10−16
each other and thus to enhance their functionalities.
Functionalities can be further explored beyond the traditional
applications once the pore structures have been introduced into
such framework materials to direct their specific and selective
Received: April 18, 2012
©
XXXX American Chemical Society
A
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bis(4-pyridyl)porphyrin, and bis(p-carboxyphenyl)-
2
5−30
porphyrin.
As demonstrated in the development of porous metal−
organic frameworks, the exploitation of new organic linkers has
played a crucial role in targeting some prototypic porous MOFs
exhibiting superior properties. For example, the introduction of
1
,3,5-tris(4-carboxyphenyl)benzene (H BTB) in 2001 led to
3
the discovery of the extraordinarily highly porous MOF-177 in
31
2
004 and MOF-200 in 2010. Given the fact that the m-
benzenedicarboxylate moieties are very powerful organic
32
groups to stabilize the frameworks, we expect that the
metal 5,10,15,20-tetrakis(3,5-biscarboxylphenyl)porphyrin (M-
H OCPP; Scheme 1) having four m-benzenedicarboxylate
8
Scheme 1. Metal 5,10,15,20-Tetrakis(3,5-
biscarboxylphenyl)porphyrin Metalloligands
moieties will be an excellent metalloligand to construct porous
33
MPF materials for practical applications. Herein we, for the
first time, explore this new type of metalloporphyrin linker and
report the syntheses, structures, sorption properties, and
catalytic alkylbenzene oxidation of three isostructural MPFs
[
M n C l ( M n C l - O C P P ) ( D M F ) ( H O ) ] ·2 DMF-
5 2 4 2 4
·8CH COOH·14H O (ZJU-18; ZJU = Zhejiang University),
3 2
[
(
Mn Cl (Ni-OCPP)(H O) ]·7DMF·6CH COOH·11H O
5 2 2 8 3 2
ZJU-19), and [Cd Cl (MnCl-OCPP)(H O) ]·13DMF-
5
2
2
6
·2CH COOH·9H O (ZJU-20). ZJU-18 exhibits highly efficient
3 2
III
and selective catalytic oxidation of alkylbenzenes at 65 °C using
tert-butyl hydroperoxide (TBHP) as the oxidant.
Figure 1. (a) Mn Cl-H OCPP metalloligand centered by a MnN Cl
8 4
square pyramid and (b) same unit connected to binuclear
Mn (COO) and trinuclear Mn (COO) (μ-H O) SBUs in the crystal
2
4
3
4
2
2
RESULTS AND DISCUSSION
structure of ZJU-18. Mn-centered polyhedra are shown in different
shades of blue.
■
The three MPFs were synthesized by heating a mixture of M-
III
II
H OCPP (M = Mn Cl or Ni ) and manganese(II) chloride or
8
cadmium chloride in a mixed solvent of DMF and acetic acid at
II
80 °C for one week. The composition of the as-synthesized
Mn (COO) Cl paddlewheel with the four carboxylate C
2
4
2
MPFs was figured out on the basis of the elemental analysis,
thermogravimetric analysis (TGA), and single-crystal structure.
Single-crystal X-ray diffraction analysis revealed that the three
compounds are isomorphous and crystallize in the ortho-
atoms forming the points of extension. A fourth node of the
underlying net is the 3-coordinated branch point of the organic
component (Figure 2d). These are linked together in the
crystal as shown in Figure 2e to form a 3-periodic net.
Remarkably the three metal-containing SBU nodes are all the
same topologically, and the underlying net is the binodal, edge-
transitive net with Reticular Chemistry Structure Resource
34
rhombic Fmmm space group. The representative crystal
structure of ZJU-18 was discussed in detail. The structure is
III
made up of an octatopic Mn Cl-OCPP metalloligand joined to
36
two metal-containing secondary building units (SBUs),
(RCSR) symbol tbo. This net was first found in an MOF
37a
binuclear Mn (COO) and trinuclear Mn (COO) (μ-H O)
structure in HKUST-1; more recently isoreticular materials
2
4
3
4
2
2
(
Figure 1). We analyze the topology of the structure in the
of exceptional porosity and specific surface area have been
reported. This net in its most symmetrical realization has
large cavities of about 21.3 Å (the yellow ball in Figure 2e), and
the corresponding pore window in the structure of ZJU-18 is
35
37
manner suggested by O’Keeffe and Yaghi. There are three
metal SBUs as shown in Figure 2. The first is a Mn N Cl
square pyramid with the four N atoms acting as points of
extension. The second SBU has the composition
Mn (COO) (μ-H O) (H O) with again four carboxylate C
III
4
approximately 11.5 Å in diameter. Apparently, the porphyrin
III
Mn N Cl sites are readily accessible to the substrates.
3
4
2
2
2
6
4
atoms as points of extension. The third one is a
PLATON calculations indicate that ZJU-18 consists of 59.8%
B
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vacuum for 6 h, powder X-ray diffraction (PXRD) analysis of
the sample showed that the sharp diffraction pattern almost
disappears. This result suggests that ZJU-18 loses its long-range
order upon the removal of included solvent molecules.
However, the sharp diffraction peaks can be restored by
immersing the evacuated samples in DMF for 24 h. (For
comparison, the evacuated sample was also exposed to the
vapor of DMF at 80 °C for 24 h. The PXRD of the resulting
regenerated ZJU-18 by DMF vapor sorption is basically
identical to that of the regenerated ZJU-18 by immersion in
DMF. See Figure S7 in the Supporting Information.) Hence,
the solvent-free activated sample was immersed in various
solvents for 6 h at room temperature to study the guest
inclusion properties of ZJU-18 in which triphenylmethane was
used as an internal standard. GC−MS analysis on the
supernatants indicates that the activated ZJU-18 can readily
take up a large amount of different solvent molecules such as
ethanol, acetonitrile, acetone, cyclohexane, benzene, toluene,
39
ethylbenzene, and acetophenone, as shown in Figure 3.
Figure 3. Illustration of the sorption ability of ZJU-18 per formula unit
as probed by GC−MS.
We examine these three MPFs for their catalytic oxidation of
alkylbenzenes. The ethylbenzene oxidation by MPFs was
performed in a mixed solvent of acetonitrile, acetic acid, and
water at 65 °C for 18 h using TBHP as the oxidant. GC−MS
analysis after the reaction showed that ZJU-18 efficiently
catalyzes this chemical transformation in which ethylbenzene
was converted to the only product acetophenone quantitatively
II
in >99% yield (Table 1, entry 1), while ZJU-19 having Ni -
OCPP porphyrin centers displayed basically negligible catalytic
activity in which only 9% acetophenone was formed (entry 2).
The significant difference between ZJU-18 and ZJU-19 for their
catalytic transformation of ethylbenzene to acetophenone
III
clearly indicates the crucial roles of the Mn Cl-OCPP sites
within ZJU-18 as the efficient catalytic sites. We speculate that
III
Figure 2. Mn-containing SBUs (a) Mn N Cl, (b) trinuclear
II
4
the manganese sites on the SBU nodes Mn (COO) Cl and
3
4
2
Mn (COO) (μ-H O) (H O) , and (c) binuclear paddlewheel
Mn (COO) Cl and (d) their linkage to the 3-coordinated node to
form (e) the net from four nodes in the actual crystal structure of ZJU-
8. Yellow and blue balls are centered in the large and small cavities in
II
3
4
2
2
2
6
Mn (COO) (μ-H O) (H O) within ZJU-18 might also be
II
3
4
2
2
2
6
2
4
2
III
partially responsible and work collaboratively with Mn Cl-
OCPP sites to enforce such efficient catalytic activity, given the
fact that ZJU-20’s catalytic activity is much lower than that of
1
the structure.
ZJU-19 (entry 3, conversion of 69%; in the structure of ZJU-20,
I I
t h e S B U s a r e C d
( C O O ) ( H O )
a n d
2
4
2
2
II
void space which can encapsulate many of the solvent
Cd (COO) Cl (H O) ). We also studied the catalytic activity
3 4 2 2 4
3
8
molecules.
of MnCl , Mn-Me OCPP, or Ni-Me OCPP (entries 4−6) for
III
2
8
8
The access of different substrate molecules into the pores of
the activated ZJU-18 was further examined by sorption studies.
After the as-synthesized ZJU-18 was heated at 90 °C under
comparison, again to confirm that Mn Cl-OCPP sites within
ZJU-18 play the most important roles for highly efficient and
selective oxidation of ethylbenzene. ZJU-18 can also catalyti-
C
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a
Table 1. Selective Oxidation of Alkylbenzenes Catalyzed by MPFs for the Formation of Phenyl Ketones
a
Alkylbenzene (0.1 mmol), TBHP (0.15 mmol), catalyst (0.005 mmol), acetonitrile (1.0 mL), acetic acid (0.2 mL), and water (0.2 mL) were stirred
b
c
at 65 °C for 18 h. Conversion (%) and selectivity (%) were determined by GC−MS on an SE-54 column. Fifteenth cycle, and the byproduct is 1-
phenylethanol. Third cycle.
d
cally oxidize various alkylbenzenes (Table 1, entries 7−11)
under the above-mentioned reaction conditions. The con-
version of substrate decreases gradually when the size of the
substrate increases. The much lower catalytic conversion for the
larger substrates (entries 10 and 11) might be attributed to
their difficult access to the interior pores of ZJU-18, so the
catalytic reaction mainly occurs on ZJU-18 exterior surfaces. In
fact, ZJU-18 exhibits even lower catalytic activity than the
(Table 1, entries 12 and 13 versus 10 and 11) because of the
difficult access of these larger substrates into the interior pores
of ZJU-18. It needs to be mentioned again that ZJU-18 displays
much higher catalytic activity than the molecular MnCl-
Me OCPP catalyst for the catalytic oxidation of smaller
8
substrate ethylbenzene (entry 4 versus 1). These results clearly
indicate that catalytic properties of ZJU-18 for the oxidation of
alkylbenzenes are substrate size-selective, as well established in
molecular MnCl-Me OCPP catalyst for the catalytic oxidation
8
40
of larger substrates diphenylmethane and 4-ethylbiphenyl
other types of solid porous catalysts, though steric constraint
D
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and the electronic effect of the different reactant substrates
might also have some effects.
during the catalytic process (see Figure S11 in the Supporting
Information), leading to its high catalytic activities even after 15
cycles. This is significantly different from the homogeneous
counterpart. The recovered homogeneous catalyst MnCl-
We intentionally interrupted the catalytic reaction after 5 h
and collected the catalyst ZJU-18 solid to study the chemical
species adsorbed inside the pores. GC−MS analysis of the
desorbed species from this reacted ZJU-18 suggests that it
incorporates about seven ethylbenzene and two acetophenone
molecules per ZJU-18. This study clearly demonstrates that the
catalytic oxidation of ethylbenzene into acetophenone does
occur inside the pores of ZJU-18. However, when the same
procedure was applied for the oxidation of larger substrate 4-
ethylbiphenyl, only trace substrate and product molecules were
detected by GC−MS. These results further confirm the
substrate size-selective property of ZJU-18 for the oxidation
of alkylbenzenes. The easy access of small substrate ethyl-
benzene into the pore space of ZJU-18 has maximized the
catalytic activity and efficiency of the immobilized catalytic
Me OCPP basically lost its catalytic activity after three cycles
8
(Table 1, entry 15). It is speculated that the mechanism of the
catalytic reaction inside the pores of ZJU-18 is similar to those
of reactions catalyzed by homogeneous metalloporphyrin
catalysts: the formation of reactive oxometalloporphyrin
intermediates and hydrogen abstraction from a benzylic carbon
42
atom (see Scheme S1 in the Supporting Information).
However, the homogeneous metalloporphyrin catalysts have
very high suicidal inactivation because of the formation of
43
catalytically inactive μ-oxometalloporphyrin dimers. The
incorporation of these catalytically active metalloporphyrin
species into the porous metalloporphyrinic framework solid
catalysts has not only heterogenized the catalysts, but also
significantly enhanced and sustained their catalytic activities by
blocking the formation of the catalytically inactive dimetallo-
porphyrinic species.
III
Mn sites inside the pores, while the large substrate 4-
ethylbiphenyl is very difficult to diffuse into the pores of ZJU-
18, so the catalytic oxidation of 4-ethylbiphenyl mainly takes
place on the surface of ZJU-18, leading to the much lower
catalytic activity.
CONCLUSION
■
As shown in Figure 3, the pores within ZJU-18 are large
enough to take up both ethylbenzene and acetophenone
molecules. After the activated ZJU-18 was immersed into the
mixture of ethylbenzene and acetophenone (v/v = 1/1) with a
triphenylmethane internal standard for 6 h at room temper-
ature, GS−MS analysis showed that ZJU-18 preferably takes up
ethylbenzene (23 molecules) over acetophenone (5 molecules)
per formula unit of ZJU-18. Such preferred sorption of
substrate reactant over the product will significantly facilitate
the recognition of the substrate and the release of the product,
which is certainly also responsible for the remarkable catalytic
activity of ZJU-18 for the oxidation of ethylbenzene.
To make use of the new metalloporphyrin ligands metal
,10,15,20-tetrakis(3,5-biscarboxylphenyl)porphyrin (M-
H OCPP) (M = Mn Cl and Ni ), we, for the first time,
have successfully constructed three porous metalloporphyrinic
frameworks whose structures are 3-periodic, binodal, edge-
transitive nets with RCSR symbol tbo, having intercrossed pore
windows of about 11.5 Å and pore cages about 21.3 Å in
5
III
II
8
III
diameter. Because of the immobilization of Mn -porphyrin
catalytic sites onto the pore surfaces of the resulting porous
metalloporphyrinic frameworks, the developed catalyst ZJU-18
exhibits highly efficient and selective oxidation of alkylbenzene
in which 99% yield has been realized for the transformation of
After a mixture of ZJU-18 and TBHP in a mixed solvent of
acetonitrile, acetic acid, and water was heated at 65 °C for 18 h
under stirring, ethylbenzene and additional TBHP were
subsequently added into the filtered hot filtrate, which was
further heated at 65 °C for another 18 h. GC analysis only
detects a trace of product, which is identical to that of the
background reaction. This result demonstrates the heteroge-
neous catalytic nature of ZJU-18. ZJU-18 is easily recovered by
centrifugation to remove the supernatant, washed with
acetonitrile several times, and subsequently used in the
successive runs for 15 cycles (Table 1, entry 14; Figures S8
and S9, Supporting Information). The remarkable stability of
ZJU-18 further encouraged us to study the kinetic behavior by
using a large amount of substrate. As shown in Figure S10 in
ethylbenzene to acetophenone. ZJU-18 is very superior to the
III
molecular Mn Cl-Me OCPP counterpart in terms of their
8
catalytic activities, indicating that such a porous metal-
loporphyrinic framework approach has not only heterogenized
the homogeneous catalysts, but also significantly sustained and
enhanced their catalytic activities by blocking the formation of
the catalytically inactive dimetalloporphyrinic species and by
making use of their substrate-selective properties. The new
metalloporphyrin ligands M-H OCPP have multicarboxylates
8
to stabilize the porous frameworks; it is expected that this work
will facilitate much more extensive research on these metal-
loporphyrin ligands for their construction of functional porous
metalloporphyrinic frameworks; thus, more functional MPF
materials for gas separation, sensing, light harvesting, and
heterogeneous catalysis will be emerging in the near future.
the Supporting Information, the turnover number (TON)
reaches 8076 with a turnover frequency (TOF) of 168 h−1 after
4
1
8 h without loss of catalytic activity in the following runs. ZJU-
8 is significantly superior to other reported heterogeneous
EXPERIMENTAL SECTION
■
catalysts such as polyoxometalates, metal oxides, immobilized
metalloporphyrins, mesoporous materials, and others for the
Materials and Methods. All of the chemicals were obtained from
commercial sources and were used without further purification, except
5,10,15,20-tetrakis(3,5-biscarboxylphenyl)porphyrin was prepared ac-
41
oxidation of ethylbenzene. These known catalysts suffer from
a lower oxidation selectivity, which leads to a certain amount of
side products 1-phenylethanol and benzaldehyde; while the
highest TON is up to 90. The high selectivity of ZJU-18 for the
oxidation of ethylbenzene to exclusively produce acetophenone
at high yield and extremely high TON of the ZJU-18 catalyst is
really remarkable.
4
4
cording to the literature. IR spectra were collected from KBr pellets
on an FTS-40 spectrophotometer. Thermogravimetric analyses (TGA)
were carried out under a N atmosphere on a NETZSCH STA 409
2
−1
PC/PG instrument at a heating rate of 10 °C min . Elemental
analyses were performed on a ThermoFinnigan Flash EA 1112
element analyzer. GC−MS spectra were recorded on a SHIMADZU
GCMS-QP2010. PXRD data were recorded on a RIGAKU D/MAX
1
The PXRD patterns of the recovered solid ZJU-18 showed
2550/PC for Cu Kα radiation (λ = 1.5406 Å). H NMR spectra were
that the structural integrity of the catalyst was maintained
recorded on a 500 MHz spectrometer in CDCl solution, and the
3
E
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chemical shifts were reported relative to the internal standard TMS (0
ppm).
Typical Procedure for Oxidation of Alkylbenzenes. Ethyl-
benzene (0.1 mmol), TBHP (0.15 mmol), catalyst (0.005 mmol),
acetonitrile (1.0 mL), acetic acid (0.2 mL), and water (0.2 mL) were
stirred at 65 °C for 18 h. The identity of the product was determined
by analyzing aliquots of the bulk solution using GC−MS and
compared with the authentic samples analyzed under the same
conditions, while the conversion and selectivity were obtained by GC
analysis with an FID using a capillary SE-54 column. The used ZJU-18
was recovered by centrifugation to remove the supernatant, washed
with acetonitrile several times, and subsequently used in the successive
runs.
Typical Procedure To Study the Chemical Species Adsorbed
inside the Pores of ZJU-18 during Oxidation of Alkylbenzenes.
Ethylbenzene (0.2 mmol), TBHP (0.3 mmol), catalyst (0.01 mmol),
acetonitrile (2.0 mL), acetic acid (0.4 mL), and water (0.4 mL) were
stirred at 65 °C for 5 h. After the reaction mixture was cooled to room
temperature, the solid was recovered by filtration and thoroughly
washed with acetonitrile three times. The solid was digested by using
dilute aqueous ammonia solution, which was extracted with ethyl
ether. The aliquot of the bulk solution was subjected to GC−MS
analysis and compared with the authentic samples analyzed under the
same conditions.
Synthesis of ZJU-18. MnCl-H OCPP (5.3 mg, 0.005 mmol) and
8
MnCl ·4H O (9.9 mg, 0.05 mmol) were dissolved in a mixture of
2
2
DMF (2.0 mL) and HOAc (0.2 mL). The mixture was sealed in a
screw cap vial and heated at 80 °C for one week. Brown crystals of
ZJU-18 were filtered, washed with DMF, EtOH, and Et O, and dried
2
at room temperature. Yield: 85%. Anal. Calcd for
C H Cl Mn N O : C, 39.19; H, 4.97; N, 5.31. Found: C, 39.36;
8
6
130
3
6
10 56
−1
H, 4.76; N, 5.32. IR (KBr pellet, ν/cm ): 1656(s), 1613(s), 1560(s),
1
1
7
4
498(w), 1437(s), 1367(s), 1334(w), 1242(m), 1207(w), 1144(w),
111(m), 1058(w), 1013(m), 943(w), 915(w), 819(w), 780(s),
37(w), 712(s), 688(w), 669(w), 617(w), 570(w), 536(w), 457(w),
38(w), 414(w).
Synthesis of ZJU-19. Ni-H OCPP (5.1 mg, 0.005 mmol) and
8
MnCl ·4H O (9.9 mg, 0.05 mmol) were dissolved in a mixture of
2
2
DMF (2.0 mL) and HOAc (0.2 mL). The mixture was sealed in a
screw cap vial and heated at 80 °C for one week. Brown crystals of
ZJU-19 were filtered, washed with DMF, EtOH, and Et O, and dried
2
at room temperature. Yield: 80%. Anal. Calcd for
C H Cl Mn N NiO : C, 39.64; H, 5.13; N, 5.98. Found: C,
8
5
131
2
5
11
54
−1
4
1
1
6
0.79; H, 5.09; N, 5.94. IR (KBr pellet, ν/cm ): 1611(s), 1561(s),
437(s), 1370(s), 1249(m), 1147(w), 1110(w), 1081(w),1055(w),
013(m), 934(m), 802(w), 781(s), 736(w), 712(s), 688(w), 669(w),
53(w), 611(w), 537(w), 438(w), 415(w).
Study of the TONs for Oxidation of Ethylbenzene Catalyzed
by ZJU-18. Ethylbenzene (20 mmol), TBHP (30 mmol), ZJU-18
(
(
0.002 mmol), acetonitrile (8 mL), acetic acid (1.6 mL), and water
1.6 mL) were stirred at 65 °C for 48 h. The solid catalyst was
Synthesis of ZJU-20. The preparation procedures are similar to
centrifugated and washed with acetonitrile three times. The aliquots
were regularly taken out for GC analysis to determine the conversion
of ethylbenzene, the yield of acetophenone, TONs (TON is defined as
the mole ratio of the substrate converted to the catalyst), and TOFs
(TOF is defined as the moles of substrate converted per mole of
catalyst per hour).
those of ZJU-18, except CdCl ·2.5H O was used instead of
2
2
MnCl ·4H O. Brown crystals of ZJU-19 were filtered, washed with
2
2
DMF, EtOH, and Et O, and dried at room temperature. Yield: 73%.
2
Anal. Calcd for C H Cd Cl MnN O : C 37.77; H, 4.97; N, 7.88.
9
5
149
5
3
17 48
−1
Found: C, 38.02; H, 5.09; N, 7.85. IR (KBr pellet, ν/cm ): 1654(s),
1
1
8
611(s), 1561(s), 1501(w), 1436(s), 1367(s), 1301(w), 1251(w),
207(w), 1145(w), 1105(m), 1055(w), 1014(m), 944(w), 918(w),
04(w), 779(s), 736(w), 715(s), 669(m), 611(w), 410(w).
Typical Procedure for the Reuse of MnCl-Me OCPP in the
8
Catalytic Oxidation of Ethylbenzene. MnCl-Me OCPP (0.005
8
mmol), ethylbenzene (0.1 mmol), TBHP (0.15 mmol), acetonitrile
Single-Crystal X-ray Data Collection and Structure Deter-
(
1.0 mL), acetic acid (0.2 mL), and water (0.2 mL) were stirred at 65
C for 18 h, and the liquid was subsequently evaporated under
mination. The determination of the unit cells and data collection for
the crystals of ZJUs-18, -19, and -20 were performed on an Oxford
Xcalibur Gemini Ultra diffractometer with an Atlas detector. The data
were collected using graphite-monochromatic enhanced ultra Cu
radiation (λ = 1.54178 Å) at 293 K. The data sets were corrected by
empirical absorption correction using spherical harmonics, imple-
°
vacuum. The resulting solid was washed with ethyl ether three times.
The combined Et O solution was subjected to GC−MS analysis, while
2
the recovered MnCl-Me OCPP solid was subsequently used in the
8
successive runs.
45
mented in the SCALE3 ABSPACK scaling algorithm. The structures
ASSOCIATED CONTENT
of all compounds were solved by direct methods and refined by full-
■
4
6
matrix least-squares methods with the SHELX-97 program package.
*
S
Supporting Information
The solvent molecules in these compounds are highly disordered; the
Crystallographic, IR, TGA, and PXRD data, catalytic study data
including turnover figures, MS and NMR spectra of the
products, and CIF data. This material is available free of charge
via the Internet at http://pubs.acs.org.
SQUEEZE subroutine of the PLATON software suit was used to
4
7
remove the scattering from the highly disordered guest molecules.
The resulting new files were used to further refine the structures. The
H atoms on C atoms were generated geometrically.
Deconstruction of the Structure. We analyze the topology of
3
5
the structure in the manner suggested by O’Keeffe and Yaghi. The
metal-containing SBUs and their points of extension are identified.
Nodes of the underlying net are then placed at the center of the SBUs.
The valence (coordination number or “connectivity”) of these nodes is
the same as the number of points of extension. Further nodes are
placed at branch points (if any) of the organic component.
AUTHOR INFORMATION
■
Corresponding Author
banglin.chen@utsa.edu; cdwu@zju.edu.cn
Notes
The authors declare no competing financial interest.
Typical Procedure for Substrate Adsorption Experiments. A
sample of ZJU-18 (0.03 mmol) was treated under vacuum at 90 °C for
ACKNOWLEDGMENTS
■
6
h. The evaluated sample was subsequently immersed in ethylbenzene
(
0.25 mL) with triphenylmethane as an internal standard at room
This work was financially supported by the National Natural
Science Foundation of China (Grant 21073158), Zhejiang
Provincial Natural Science Foundation of China (Grant
Z4100038), and Fundamental Research Funds for the Central
Universities (Grant 2010QNA3013) and partially supported by
the Welch Foundation (Grant AX-1730 to B.C.).
temperature. The mixture was determined by analyzing an aliquot of
the bulk solution using GC−MS with a flame ionization detector
(
FID) using a capillary SE-54 column and compared with the
authentic sample analyzed under the same conditions. We have further
performed additional experiments to confirm that the ethylbenzene
was adsorbed in the void space. After the solid was thoroughly washed
with ethyl ether to remove surface-adsorbed molecules, the solid was
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56
3
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8
24
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36
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5
4
24
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G
dx.doi.org/10.1021/ja303728c | J. Am. Chem. Soc. XXXX, XXX, XXX−XXX

Journal of the American Chemical Society
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