A Versatile Metalloporphyrinic Framework Platform for Highly Efficient Bioinspired, Photo- and Asymmetric Catalysis

Article abstract of DOI:10.1002/anie.201810294

Even though numerous bioinspired catalysts have been developed, there remain huge gaps between the artificial and natural catalysts, because it is very difficult to imitate simultaneously the complicated constituents, structures, and synergistic effect of enzymes. We report herein a versatile metalloporphyrinic framework platform, which exhibits high efficiency in bioinspired catalysis, photocatalysis, and asymmetric catalysis. The catalytic properties are highly dependent on the tunable constituents and their cooperation, and are significantly superior to the corresponding molecular catalyst systems which lack the synergistic effects. Since there are numerous functional moieties that can readily be incorporated into the metalloporphyrinic framework platform, a myriad of applications can be simply realized by embedding different functional moieties.

Full text of DOI:10.1002/anie.201810294

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Accepted Article
Title: A Versatile Metalloporphyrinic Framework Platform for Highly
Efficient Bioinspired, Photo and Asymmetric Catalysis
Authors: Chuan-De Wu, Wei-Long He, and Min Zhao
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201810294
Angew. Chem. 10.1002/ange.201810294
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10.1002/anie.201810294
Angewandte Chemie International Edition
COMMUNICATION
A Versatile Metalloporphyrinic Framework Platform for Highly
Efficient Bioinspired, Photo and Asymmetric Catalysis
Wei-Long He,[a] Min Zhao,[a] and Chuan-De Wu*[a]
Dedicated to Professor Jin-Shun Huang on the occasion of his 80th birthday
Abstract: Even though numerous bioinspired catalysts have been
developed, there remain huge gaps between the artificial and natural
catalysts, because it is very difficult to imitate simultaneously the
complicated constituents, structures and synergistic effect of
enzymes. We report herein a versatile metalloporphyrinic framework
platform, which exhibits high efficiency in bioinspired catalysis,
photocatalysis and asymmetric catalysis. The catalytic properties are
highly depending on the tunable constituents and their cooperation
work, which are significantly superior to the corresponding molecular
catalyst systems due to lack of synergistic work. Since there have
been numerous functional moieties that are readily being
incorporated into the platform, a myriad of applications can be
therefore simply realized by imbedding different functional moieties.
properties. In the structures of CZJ-18(M), not only the porphyrin
metal centers are systematically tunable, but also the in situ
imbedded acetate moieties in the frameworks are exchangeable
with different functional moieties for highly efficient bioinspired
catalysis, photocatalysis and asymmetric catalysis.
Brownish crystals of metalloporpyrinic frameworks CZJ-
18(M) were synthesized by heating a mixture of M-H8L and
Y(NO3)3·6H2O in a mixed solvent of DMF and acetic acid at 80
°C for one week. These isostructural metalloporpyrinic
frameworks are built from trigonal [Y3(H2O)4(benzoate)8(acetate)]
(abbreviated as {Y3}) secondary building units (SBUs) and
octatopic M-L linkers. In the crystal structures, each
deprotonated M-L linker connects with eight trigonal {Y3} SBUs,
and each {Y3} SBU connects with eight M-L linkers to form 3D
non-interpenetrated networks with pore dimensions of about 1.8
nm (Figure 1a).
Enzymes are a family of intriguing biocatalysts, which are very
powerful in numerous catalytic reactions.1 To imitate the catalytic
properties of enzymes, numerous bioinspired catalysts, similar
to the structures of redox-active centers of enzymes, have been
therefore created.2 However, because the constituents and
structures of biocatalysts are very complicated, and biocatalysis
is the synergistic work of multiple factors, the catalytic properties
of bioinspired catalysts remain much inferior to those of the
native enzymes.3,4 The challenge to realize highly efficient
bioinspired catalysis is how to imitate the catalytic mechanisms
of enzymes for synergistic catalysis by exactly tuning the
constituents, structures and locations of active sites in catalysts.
Metal-organic frameworks (MOFs) are an emerging class of
porous materials constructed from multidentate organic ligands
and metal ions/clusters, featuring high porosity, high surface
areas, and tunable pore sizes and shapes.5-12 The tunable pore
nature and constituents of MOFs endow systematically introduce
different redox-active and auxiliary centers to improve the
catalytic properties.13-23 MOFs represent a very promising class
of porous materials for bioinspired catalysis.3,4 However, the
catalytic properties of bioinspired MOFs remain much inferior to
those of the native enzymes, due to lack of systematically
Figure 1. (A) The crystal structure of CZJ-18(Cu), consisting of accessible
porphyrin
CuII
sites
(pink
balls).
(B)
The
structure
of
[Y3(H2O)4(benzoate)8(acetate)] in CZJ-18(Cu), highlighting the replaceable
acetate moiety. (C) The simulated structure of [Y3(H2O)4(benzoate)8(SB)] in
CZJ-18(Cu)-SB. (D) The simulated structure of [Y3(H2O)4(benzoate)8(Pro)] in
CZJ-18(Cu)-Pro. Color scheme: Cu, pink balls; Y, green polyhedra and cyan
balls; O, red; N, blue; C, deep gray and purple; S, yellow.
tunable MOF platform.21-23 We report herein
metalloporphyrinic framework platform, [Y3(H2O)4(M-
L)(CH3COO)]·solvent (CZJ-18(M); M = 2HI, MnIIICl and CuII;
H10L 5,10,15,20-tetrakis-3,5-bis((4-hydroxycarbonyl)-
a
porous
=
phenyl)phenylporphine; Scheme S1), which is systematically
modifiable with different functional moieties to tune the catalytic
According to the coordination environments of YIII ions,
there are two kinds of YIII ions in [Y3(H2O)4(benzoate)8(acetate)]
(Figure 1b). The acetate moiety acts as an η4-ligand to bridge
firmly three YIII ions, playing very important roles to stabilize and
neutralize the framework structures of CZJ-18(M), which is very
difficult to be exchanged by post-modification. It is interesting
that acetate is systematically replaceable with different
functional moieties consisting of carboxylate groups to tune the
catalytic properties by in situ assembly strategy. When 4-
sulfobenzoate (SB) and L-proline (Pro) were used instead of
[a]
W.-L. He, M. Zhao and Prof. Dr. C.-D. Wu
State Key Laboratory of Silicon Materials
Department of Chemistry
Zhejiang University
Hangzhou, 310027, P. R. China
E-mail: cdwu@zju.edu.cn
Supporting information for this article is given via a link at the end of
the document.
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10.1002/anie.201810294
Angewandte Chemie International Edition
COMMUNICATION
acetic acid during synthesis of CZJ-18(M), these moieties were
readily incorporated into the platform to form CZJ-18(Cu)-SB
and CZJ-18(Cu)-Pro, respectively (Figure 1c and 1d). The
strong attachment of different functional moieties to {Y3} clusters
in CZJ-18(M) would ensure their stability during catalysis.
sensitive to the coordination environment (Figure S39).25 It is
interesting that the binding energies of suspended CuII ions in
CZJ-18(Zn)-Cu are similar to those of porphyrin CuII in CZJ-
18(Cu)-SB. These results indicate that the suspended Cu2+ and
porphyrin CuII have similar electronic coordination environments.
As expected, the differences of the binding energies for
porphyrin and suspended CuII in CZJ-18(Cu)-Cu are negligible
with the Cu 2p3/2 signal centered at 934.5 eV. The EPR signals
of CZJ-18(Zn)-Cu are also different from those of Cu(ClO4)2.
Similar to the XPS results, CZJ-18(Cu)-Cu, consisting of both
porphyrin and suspended CuII, exhibits merged EPR signals
(Figure S40). Compared with our previous results, the above
results indicate that CuII ions should be suspended in the anionic
pores with highly vacant coordination sphere by weakly attached
to the pore surfaces, which are freely mobile in the negative-
charged pore microenvironment for highly efficient catalysis.24 N2
adsorption experiments resulted in a BET surface area of 342.6
m2 g-1 with the average pore width of 1.8 nm, which proved that
suspending redox-active metal ions in the anionic pores does
not significantly affect the porosity for highly efficient catalysis.
Considering that copper ions are the active sites of many
redox enzymes, CZJ-18(Cu)-Cu was used as a bioinspired
catalyst for aerobic oxidation of alcohols.26,27 CZJ-18(Cu)-Cu is
highly active in aerobic oxidation of alcohols in acetonitrile at 65
C under 1 atm O2 atmosphere (Figure 2 and Table S3). CZJ-
18(Cu)-Cu efficiently prompted aerobic oxidation of benzyl
alcohol with high yield of benzaldehyde (>99%). It is significantly
superior to CZJ-18(Cu)-SB and CZJ-18(Cu), and molecular Cu-
Me8OCPP, which are almost inactive in the aerobic oxidation
reaction. CZJ-18(Cu)-Cu is also much superior to a mixture of
Cu-Me8OCPP and copper perchlorate under the identical
conditions (8.5%). These results demonstrate that suspending
redox-active CuII ions in the anionic pores of CZJ-18(Cu)-Cu
would significantly improve the catalytic activity by eliminating
ligation of counter ions to the active sites, and letting catalytic
reaction occur between CuII ions and framework anions to
polarize and activate further the reactant molecules.
CZJ-18(Cu), CZJ-18(Cu)-SB and CZJ-18(Cu)-Pro take up
948, 503 and 434 cm3 g-1 N2 at 77 K and 1 bar, resulting
microporous BET surface areas of 701.1, 386.1 and 490.5 m2/g,
respectively. The average pore widths are of about 1.8 nm,
which are consistent well with the single crystal structures. Such
high surface areas provide enough void space to accommodate
and exchange further with different guest molecules. We
selected CZJ-18(Cu) as a representative example to study the
accessibility of the inside pores to different solvent molecules.
GC results showed that CZJ-18(Cu) can readily take up large
amounts of different solvent molecules, including acetonitrile,
ethanol, acetone, toluene, tetrahydrofuran, styrene, styrene
oxide, benzyl alcohol, benzaldehyde and cyclohexanone (Figure
S34). Apparently, the inside pore space of CZJ-18(Cu) is readily
accessible to small organic molecules transferred through the
open channels, which would facilitate highly efficient catalysis.
To evaluate the accessibility of the porphyrin metal sites in
CZJ-18(M), we examined the catalytic properties of CZJ-18(Mn)
for epoxidation of olefins at room temperature. When a mixture
of styrene substrate, iodosylbenzene (PhIO) oxidant and CZJ-
18(Mn) catalyst in CH3CN was stirred at room temperature for
19 h, GC-MS analysis showed that styrene was almost fully
oxidized with 99% selectivity for the epoxide product (Table S2).
CZJ-18(Mn) is much superior to the homogeneous molecular
counterpart MnIIICl-Me8OCPP in terms of substrate conversion
(40%) and epoxide product selectivity (74%). CZJ-18(Mn) also
epoxidized a series of olefins under the identical conditions.
Accompanying increase of the substrate size, the conversion
decreases gradually, because the bulky substrates have
difficulty to access the active sites inside the pores of CZJ-
18(Mn). CZJ-18(Mn) is very stable, which can be simply
recovered and reused for six cycles with almost retained high
catalytic efficiency. In contrast, the recovered molecular catalyst
MnCl-Me8OCPP did not active after the second cycle. These
results indicate that incorporation of molecular bioinspired
catalysts into the platform would significantly improve the
catalytic efficiency and stability.
We have demonstrated that suspending redox-active metal
ions in the anionic pores of MOFs would endow almost full
available of the coordination sites of redox-active metal centers,
which results in most dangling bonds and empty d atomic
orbitals to maximize the catalytic efficiency.24 It is interesting that
the electronic charge of CZJ-18(M) is systematically tunable with
differently charged moieties. When 4-sulfobenzoate was used
instead of acetic acid during synthesis of these porous materials,
the anionic moieties were successfully incorporated into the
frameworks to form anionic CZJ-18(M)-SB. Treatment of CZJ-
18(Cu)-SB with a DMF solution of copper(II) perchlorate resulted
in a suspended ion catalyst (SIC) CZJ-18(Cu)-Cu, in which the
extra-framework counter ions were almost fully exchanged by
CuII ions as confirmed by ICP-MS and EDX spectroscopy.
Figure 2. The yields of aldehydes catalyzed by CZJ-18(Cu)-Cu at 65 oC for 16
h (red columns) and CZJ-18(Zn)-Cu at room temperature for 10 h irradiated by
visible light (blue columns). The numbers on the top of the columns are the
yields of aldehydes. The third and fourth columns are the results catalyzed by
Cu-Me8OCPP/Cu(ClO4)2 and Zn-Me8OCPP/Cu(ClO4)2, respectively.
Compared with those of Cu(ClO4)2, the binding energies of
porphyrin CuII 2p3/2 and 2p1/2 in CZJ-18(Cu)-SB are significantly
negative-shifted, because the binding energies are highly
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10.1002/anie.201810294
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COMMUNICATION
CZJ-18(Cu)-Cu exhibited unique property for selective
accumulation of substrate and release of product molecules.
When the conversion of benzyl alcohol reached to 56%, about
0.37 wt% benzyl alcohol and 0.12 wt% benzaldehyde were
detected from the collected solid catalyst. Moreover, when an
activated sample of CZJ-18(Cu)-Cu was immersed in mixed
benzyl alcohol and benzaldehyde (1:1 molar ratio) acetonitrile
solution at room temperature, it took up benzyl alcohol (1.3 wt%)
over benzaldehyde (0.44 wt%). These solid experimental results
confirmed the preferred sorption capability of CZJ-18(Cu)-Cu for
reactant molecules, which would significantly improve the
catalytic efficiency and reaction rate. CZJ-18(Cu)-Cu can be
reused for six cycles with almost retained high catalytic
efficiency. ICP-MS analysis revealed that the suspended copper
species did not leach into the supernate, which demonstrated
that confining copper cations in the negative-charged pores by
strong electrostatic interaction would prevent the leaching of
copper ions. PXRD pattern of the recovered solid is almost
identical to that of the as-synthesized one, which proved the
structural integrity of CZJ-18(Cu)-Cu during catalysis. CZJ-
18(Cu)-Cu is also highly efficient for selective aerobic oxidation
of a range of alcohols to afford valuable aldehydes under the
identical conditions. The turnover number reached to 17560 with
an average turnover frequency of 251 h−1 (Figure S41).
Even though the metalloporphyrin moieties in CZJ-18(M)-
Cu are almost inactive in the aerobic oxidation, however, they
might act as effective photosensitizers to absorb visible light for
the activation of O2 oxidant, which would endow the aerobic
oxidation reaction occur at room temperature.28 It is interesting
that CZJ-18(Zn)-Cu, consisting of ZnII-porphyrins as
photosensitizers, efficiently prompted the aerobic oxidation
reaction with high yield and selectivity for benzaldehyde product
under visible light irradiation (Figure 2 and Table S4). Without
SIC copper site in the anionic pores, CZJ-18(Zn)-SB is almost
inactive in the aerobic oxidation reaction. These results
demonstrated that ZnII-porphyrin is the efficient photosensitizer,
SIC CuII is the excellent redox-active center, and the
photocatalysis is the synergistic work of different active centers.
The catalytic properties of CZJ-18(Zn)-Cu are significantly
superior to those of the homogeneous mixture of Zn-
Me8L/Cu(ClO4)2 under the identical conditions. The improved
photocatalytic oxidation efficiency of CZJ-18(Zn)-Cu should be
attributed to incorporation of different active species in the pore
space/matrix that endow them easily cooperative work.29 CZJ-
18(Zn)-Cu further demonstrated widespread substrate tolerance,
which can photocatalytically oxidize various alcohols to afford
corresponding aldehydes under the identical conditions.
photocatalytic properties of the catalyst platform by tuning the
electronic coordination environment of CuII ions. In contrast, the
photocurrent density of blank FTO electrode is ignorable. These
results clearly demonstrated the excellent photocatalytic
properties of CZJ-18(Zn)-Cu in aerobic oxidation.
Figure 3. Transient photocurrent responses of CZJ-18(Zn)-Cu in 0.1 M
Bu4NClO4 acetonitrile solution at a bias of 0 V (vs. SCE electrode) at room
temperature under a 300 W Xenon lamp irradiation with a 400 nm light cut-off
filter.
Table 1. Asymmetric aldol addition reaction catalyzed by CZJ-18(Cu)-Proa.
Entry
1
Substrates
Yield(%)b
95
Anti:sync
5:1
ee(%)d
88
O
O
CHO
+
O2
N
2
3
>99
91
3:2
2:1
93e
71
CHO
+
O2N
CHO
+
O
O
NO2
4
83
3:1
73
CHO
NO2
+
CHO
O
5
6
82
96
-
29
61
+
O2N
O
1:1
CHO
+
O2N
The interesting photocatalytic results prompted us to study
the photoelectrochemical properties of CZJ-18(Zn)-Cu (Figure 3).
The as-synthesized CZJ-18(Zn)-Cu was deposited on fluorine-
doped tin oxide (FTO) surface. The photocurrent profile of the
photoelectrode indicates that CZJ-18(Zn)-Cu is highly
photoactive, which presents evident photo-generated current
responses to changes in the light on/off states in the presence of
co-catalyst TEMPO. The maximum photo-generated current
response value of CZJ-18(Zn)-Cu/FTO electrode is about 23 μA
cm-2. The maximum photo-generated current response value is
increased to 37 μA cm-2 in the presence of 2,2'-bipyridine, which
suggests that 2,2'-bipyridine plays important roles to improve the
[a] Reaction conditions: aldehyde (0.01 mmol), ketone (75 μL), catalyst (1
μmol), HBF4 (2 μmol), H2O (25 μL) and DMF (0.2 mL) were stirred at room
temperature for 4 days. [b] Isolated yield. [c] Determined by 1H NMR. [d]
Determined by HPLC on a chiral AD-H or AS-H column, and the ee value is for
the major anti isomer. [e] Catalyzed by L-proline.
Chiral catalysts consisting of carboxylate groups can also be
easily incorporated in CZJ-18(M) for highly efficient asymmetric
catalysis. We selected L-proline as a representative of chiral
organic catalysts to synthesize chiral catalyst CZJ-18(Cu)-Pro.30-
36
CZJ-18(Cu)-Pro efficiently catalyzed the aldol addition
reaction between cyclohexanone and 4-nitrobenzaldehyde,
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10.1002/anie.201810294
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COMMUNICATION
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to syn diastereomeric ratio (dr) of 5:1 and 88% ee for the anti
isomer (Table 1). In contrast, molecular L-proline resulted in low
diastereomeric ratio (3:2) with 93% ee for the anti isomer under
the same conditions. The improved dr catalyzed by
heterogeneous CZJ-18(Cu)-Pro may originate from the
restricted movement of the catalytic sites in the nanopore space,
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molecules and the confined formation of the cyclic transition
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properties in the asymmetric aldol reaction. CZJ-18(Cu)-Pro is
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reaction between various aldehydes and ketones.
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catalysis, photocatalysis and asymmetric catalysis. The catalyst
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catalyst systems, because incorporation of different active
species in the pore space/matrices would endow them
effectively cooperative work. Since a substantial number of
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COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
The
functionalities
of
a
Wei-Long He, Min Zhao, and Chuan-De
Wu*
metalloporphyrinic framework platform
are systematically tunable for highly
Page No. – Page No.
efficient
photocatalysis
bioinspired
and
catalysis,
asymmetric
A Versatile Metalloporphyrinic
Framework Platform for Highly
Efficient Bioinspired, Photo and
Asymmetric Catalysis
catalysis. This work demonstrates that
incorporation of different active
species in the pore space/matrices of
the platform would endow them
effectively cooperative catalysis.
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