Template-Directed Synthesis of Photocatalyst-Encapsulating Metal-Organic Frameworks with Boosted Photocatalytic Activity

Article abstract of DOI:10.1021/acscatal.9b01783

In the past decade, the use of visible light to promote organic transformations has gained intense attention. In this study, we developed a template-directed synthesis method to use homogeneous Ru and Ir photocatalysts as structure-directing templates and succeeded to prepare a series of photocatalyst-encapsulating metal-organic frameworks (photocatalyst@MOFs) with zeolite-like structures. The open channels and polyhedral cages of MOFs effectively dispersed the encapsulated photocatalysts and facilitated the transport of reactants and products, leading to boosted catalytic activity and good reusability toward important organic reactions such as aerobic oxidation reaction of benzyl halides and the cyclization of tertiary anilines and maleimides under visible light. Moreover, we also demonstrate the versatility and universality of our templating strategy. It not only can form MOFs which cannot be accessed by other synthesis methods, but also can encapsulate various commercially available homogeneous photocatalysts into MOFs. This work explores an avenue to prepare heterogeneous photocatalysts to catalyze value-added reactions.

Full text of DOI:10.1021/acscatal.9b01783

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Article
Template-Directed Synthesis of Photocatalyst-Encapsulating
Metal-Organic Frameworks with Boosted Photocatalytic Activity
Xiaojie Yang, Tao Liang, Jiaxing Sun, Michael J. Zaworotko, Yao Chen, Peng Cheng, and Zhenjie Zhang
ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.9b01783 • Publication Date (Web): 10 Jul 2019
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Template-Directed Synthesis of Photocatalyst-Encapsulating Metal-
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†
, §
‡
¶
⊥
¶
†, §,*
Xiaojie Yang, Tao Liang, Jiaxing Sun, Michael J. Zaworotko, Yao Chen, Peng Cheng,
Zhang
Zhenjie
†,¶,§,*
†
College of Chemistry, Nankai University, Tianjin 300071, China
‡
Merck Center for Catalysis at Princeton University, Princeton, NJ 08544, USA
¶
State Key Laboratory of Medicinal Chemical Biology, Nankai University, Tianjin 300071, China
§
Key Laboratory of Advanced Energy Materials Chemistry, Ministry of Education, Nankai University, Tianjin 300071,
China
⊥
Department of Chemical Sciences, Bernal Institute, University of Limerick, Limerick V94T9PX, Republic of Ireland
Supporting Information Placeholder
ABSTRACT: In the past decade, the use of visible light to promote organic transformations has gained intense attention.
In this study, we developed a template-directed synthesis method to use homogenous Ru and Ir photocatalysts as
structure-directing templates and succeeded to prepare a series of photocatalyst-encapsulating metal-organic frameworks
(photocatalyst@MOFs) with zeolite-like structures. The open channels and polyhedral cages of MOFs allowed
effectively disperse the encapsulated photocatalysts and facilitated the transport of reactants and products, leading to
boosted catalytic activity and good reusability toward important organic reactions such as aerobic oxidation reaction of
benzyl halides and the cyclization of tertiary anilines and maleimides under visible light. Moreover, we also demonstrate
the versatility and universality of our templating strategy. It not only can form MOFs which cannot be accessed by other
synthesis methods, but also can encapsulate various commercially available homogeneous photocatalysts into MOFs.
This work explores a avenue to prepare heterogeneous photocatalysts to catalyze value-added reactions.
KEYWORDS: visible light, template-directed Synthesis, photocatalyst, metal-organic framework, aerobic oxidation
Utilization of visible light to promote organic
transformations has drawn great attention among the past
decade. Photo-induced electron transfer (PET) reaction
make efficient heterogeneous photocatalysts to reduce the
high cost, energy consumption and environmental
pollution is a campaign of the field.
1
is one of the key reactions of chemical conversion of light
energy, as well as synthetic organic photochemistry.
Immobilization homogenous catalysts into porous
solid supports has been proved to be a feasible strategy to
prepare heterogeneous catalysts. In the past two decades,
metal-organic frameworks (MOFs) have emerged as a
new class of crystalline porous solids with superior
advantages that surpass traditional porous materials (e.g.
zeolites, activated carbons, mesoporous silica) such as
2-3
Transition metal complexes such as polypyridine
2+
ruthenium(II) complexes ([Ru(bpy) ] , bpy = 2,2'-
3
bipyridine) were extensively employed as photocatalysts
to initiate PET reactions since they possess absorption in
4
the visible region and long excited state lifetime. For
instance, [Ru(bpy) ]Cl was used by MacMillan et al. as
photocatalysts for the aldehyde substitution reaction in
highest porosity, great structure versatility, tunable pore
3
2
7-9
size, and readily tailored functionality.
These
5
2
[
008, and its application was later expanded to enone
advantages offer MOFs great potential for applications as
6a
10
11-12
13-16
2+2] cycloaddition, reductive dehalogenation of alkyl
diverse as gas separation, gas storage,
etc.
catalysis
6b
6c
17-20
halides, , and amine α-functionalization. However,
most of photocatalysts used in these studies are
homogeneous, which unavoidably face the drawback of
traditional homogenous catalysts such as short life time,
hard to recycle, environmentally unfriendly. Thus, how to
Although many MOF-based photocatalysts have
been reported, most of them were focused upon non-
visible-light catalysis and did not involve organic
21-23
catalysis.
There are only a few successful examples to
employ MOFs as photocatalysts to catalyze organic
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reactions, and most related studies have focused on
covalently grafting photocatalytic moieties such as
2
+
[Ru(bpy)3]
modification or diffusion method.
Cohen's group reported a MOF analogue of UiO-67
on the ligands via post-synthetic
2
4-30
For instance,
2
+
which covalently grafted [Ru(bpy)3]
moieties to
3
1
effectively catalyze the oxidation of aryl boric acid. Lin
2
+
and co-workers incorporated [Ru(bpy)3] species on a
zirconium MOF to catalyze visible-light-driven proton
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reduction
reaction.
Currently,
encapsulating
2+
[
Ru(bpy) ] cations into MOFs’ cavities to form catalytic
3
Ru(bpy) @MOFs (@
=
encapsulating) remains
3
33-34
underexplored.
Template-directed synthesis method
has been proved to be an efficient and powerful tool to
afford control over both the structure and functionality
(
e.g. catalytic activity, chirality or fluorescence) of
35-36
MOFs.
For example, if catalysts can serve as
templates and remain present after synthesis of the MOFs,
i.e. ‘‘catalyst@MOFs’’, the catalytic activity can be
transferred from the templates to the formed
catalyst@MOFs (Figure 1a ). The pores of MOFs would
allow effectively disperse the encapsulated catalysts and
facilitate the transport of reactants and products, which
could result in high catalytic activity. Moreover, MOFs
can provide confined space and protection to the
encapsulated catalysts. Our group have long focus on
explore the generality of template-directed synthesis
method to discover new functional MOFs. For example,
we have used catalytic metalloporphyrins as templates to
Figure 1. (a) Illumination of the template-directed synthesis
37
strategy to prepare photocatalyst encapsulating zeolite-like
MOFs. (b) The sodalite-like cage consisted of 8 hexagons
and 6 squares and open channels surrounded by four
sodalite-like cages. (c) The 2D layer structure of
create a series of novel porphyrin@MOFs. We found
that porphyrins can template the formation of new MOFs
structures which cannot be accessed by other synthesis
methods, and the formed porphyrin@MOFs can
efficiently catalyze epoxidation reactions of alkene.
Herein, we developed a new approach to prepare
heterogeneous photocatalyst@MOFs using homogenous
photocatalysts as structure-directing agents. Interestingly,
using Ru or Ir photoactive moieties as templates, we were
able to obtain a series of porous zeolite-like MOFs with
sodalite-type cages. Moreover, in some MOF example,
2
+
Ru(bpy)
3 3
@NKMOF-7 with ordered [Ru(bpy) ] located in
the honeycomb cavity, and the structure illumination of
3
-
NBA .
Zeolite-like MOFs have attracted great attention owing
to their confined spaces and polyhedral-cage-based
structures, which offer potential for application as diverse
as shape- or size-selective catalysts, ion exchangers,
3
8
adsorbents (gas separation/storage). Exploring new
zeolite-like MOFs for catalysis applications is a campaign
in the field. For the first time, we used Ru(bpy) Cl as
2
+
we can precisely determine the encapsulated [Ru(bpy)3]
moieties without any disorder, which greatly facilitate the
understanding the guest-host interaction and the
templating mechanism. These photocatalyst@MOFs
possess high robustness and porosity, and can efficiently
catalyze the reaction of aerobic oxidation of benzyl
halides under visible light. Compared with homogeneous
catalyst, these materials showed improved catalytic
activity and good reusability.
3
2
templates and rigid tricarboxylate as ligands to prepare a
2
+
series of Ru(bpy) @MOFs with [Ru(bpy) ] moieties
3
3
encapsulating in the sodalite-type cages (Figure 1b).
Taking H TATB (2,4,6-tri(4-carboxyphenyl)-1,3,5-
3
triazine) as a representative, the reaction of CuCl 2H O
2
2
with H TATB and Ru(bpy) Cl in mixed solvent of
3
3
2
DMF/ethanol/water at 105 °C for 2 days afforded red
cubic crystals (Figure S1) of Ru(bpy) @NKMOF-4. By
3
contrast, the same synthesis reaction without adding
[Ru(bpy) ]Cl afforded different product (Figure S2),
3
2
indicative of its template effect. To the best of our
knowledge, NKMOF-4 has not been reported yet. These
results indicated template-directing synthesis can
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Cu2+ salt with H NBA and Ru(bpy) Cl afforded red
3 3 2
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generate new MOF structures which cannot be accessed
by other methods. Single-crystal X-ray determination
(SCXRD) revealed that NKMOF-4 exhibited a two-fold
interpenetrating framework crystallized in the cubic
space group Im-3m. In this structure, Cu atoms are five-
coordinated in square-pyramidal coordination geometry
finished by four carboxylate oxygen atoms and a chlorine.
Four crystalographically equivalent Cu atoms formed a
molecular building block (MBB) of chloride-centered
sheet-like crystals (Figure S1) of Ru(bpy) @NKMOF-7
3
which crystallized in the trigonal space group of P312.
On the contrary, the same synthesis reaction without
adding [Ru(bpy) ]Cl afforded a clear solution (Figure
3
2
S7), indicative of the template effect of [Ru(bpy) ]Cl . In
3
2
Ru(bpy) @NKMOF-7,
there
is
only
one
3
crystalographically equivalent Cu atom, which is 6-
coordinated with six carboxylate oxygens. The 3-
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-
-
square-planar [Cu (COO) Cl] .
A
supramolecular
connected [Cu(COO) ] MBBs can link with the 3-
4
8
3
3-
building block (SBB) of sodalite (SOD) cage with an
inner sphere space of diameter ~20 Å was formed via
connected NBA ligands to produce a two-dimensional
(2D) honeycomb net with hcb topology. These 2D
honeycomb nets further packed into a 3D supramolecular
structure via an ABA packing mode (Figure S8). Notably,
-
linking six [Cu (COO) Cl] squares with eight planar
4
8
3-
TATB ligands. A cubic packing of these sodalite cages
via sharing the [Cu (COO) Cl] squares further extended
-
2+
[Ru(bpy)3] cations can be precisely determined in the
4
8
the structure into a three-dimensional (3D) anionic
framework with intersected channels (Figure 1b) with
diameter ~20 Å. Interestingly, the intersected channels
are large enough to accommodate another set of 3D
cavity of the honeycomb net to balance the charge from
anionic framework (Figure 1c). Notably we found no
,
structural
distortion
for
Ru(bpy)3
in
Ru(bpy) @NKMOF-7. The well-defined position and
3
2+
anionic framework, thereby forming
a
two-fold
full
occupancy
of
[Ru(bpy)3]
cations
in
interpenetrating structure (Figure S3). Disordered
Ru(bpy) @NKMOF-7 can help to predict the position of
3
2+
+
2+
[
Ru(bpy)3] and [(CH ] NH ] cations in the cavities
[Ru(bpy) ] cations in other Ru(bpy) @MOFs. Based on
3 2
2
3
3
serve as counterions to balance the anionic framework.
To explore the generality of this template-directed
synthesis approach, we further studied two short planer
these results, we concluded that the coplanarity and C3
symmetry of ligands play key roles to generate the
sodalite-like structures.
One attractive advantage of zeolite-like MOFs is their
high structural stability. Thermogravimetric analysis
(Figure S9-12) together with powder X-ray diffraction
tricarboxylate ligands (H BTTC = benzo-tris-thiophene
3
carboxylic acid; H BTC = trimesic acid) with the same
3
symmetry and molecular shape as H TATB. We
3
successfully obtained Ru(bpy) @NKMOF-5 and
(PXRD) revealed that Ru(bpy) @NKMOF-4, -5 and -6
3
3
Ru(bpy) @NKMOF-6 which possessed the isostructural
exhibited
excellent
thermal
stability.
3
network as NKMOF-4. Noteworthily, the same synthesis
Ru(bpy) @NKMOF-4, -5 and -6 can maintain their
3
reaction as Ru(bpy) @NKMOF-5 without adding
crystallinity up to 220 °C heating (Figure S13-S15). In
3
[
Ru(bpy) ]Cl afforded different product (Figure S4),
addition, we found Ru(bpy) @NKMOFs were stable in
3
2
3
indicative of the template effect of [Ru(bpy) ]Cl . By
various solvents, which are essential for catalysis
application (Figure S16-19). To evaluate the porosity of
Ru(bpy) @NKMOFs, N sorption isotherms were then
3
2
contrast, NKMOF-6 can be obtained without adding
39
[
Ru(bpy) ]Cl as template (Figure S5). In addition,
3 2
3
2
because the sizes of sodalite cage (16 Å for
collected at 77 K. Ru(bpy) @NKMOFs were pre-
3
Ru(bpy) @NKMOF-5, 12 Å for Ru(bpy) @NKMOF-
exchanged with methanol and then activated via a
supercritical CO drying method. N sorption revealed
3
3
4
) are larger than the channel sizes (15 Å and 10 Å for
2
2
Ru(bpy) @NKMOF-5 and -4, respectively), there is no
that Ru(bpy) @NKMOF-4, -5 and -6 possess BET and
3
3
2
2
structural interpenetration observed for NKMOF-5 and
NKMOF-4. Due to the lack of long-range orderness of
Langmuir surface areas of 805 m /g and 965 m /g, 1481
m /g and 1882 m /g, 480 m /g and 588 m /g, respectively
(Figure S20, Table S2). Due to the pore blockage of
2
2
2
2
2+
encapsulated [Ru(bpy)3] moieties, we cannot fully
2+
2+
determine the position of [Ru(bpy)3] in NKMOF-4, -5
[Ru(bpy) ] counterions, no N adsorption was observed
3
2
and -6. However, based on the electron density maps, we
for Ru(bpy) @NKMOF-7, indicative of its nonporous
3
2+
observed [Ru(bpy)3] cations trapped in the sodalite
nature. The pore size distribution calculated on N2
cages (Figure S6).
sorption isotherms revealed that Ru(bpy) @NKMOF-4,
3
In order to further understand the reason H TATB,
-5 and -6 possessed pore sizes centered around 9 Å, 12 Å
and 8 Å, respectively (Figure S20), which are large
enough to accommodate catalysis substrates (Table S3
and S4). ICP-OES (Inductively coupled plasma - optical
3
H BTTC and H BTC form the same structure with
3
3
sodalite cages, we chose a non-planar ligand (H NBA =
3
4
,4',4''-nitrilotribenzoic acid) as comparison. In H NBA,
3
both the phenyl rings and carboxylic groups are not on the
emission spectrometry) analysis showed 60%, 52%, 42%
o
2+
same plane and with a large distortion angle ~89 (Figure
and
100%
[Ru(bpy)3]
loading
for
1
c), while all atoms in H TATB, H BTTC and H BTC
Ru(bpy) @NKMOF-4, -5, -6, and -7, respectively
3
3
3
3
possess good coplanarity. Interestingly, the reaction of
(100% loading: the anionic framework is fully balanced
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+
+
by [Ru(bpy) ] cations without [(CH ] NH ] ). Scanning
Methoxypyridine (20 mol%) in the presence of catalyst (0.5
3
3 2
2
b
1
c
electron microscope (SEM) and energy dispersive
spectrometry (EDS) further proved the uniform
dispersion of Ru species (Figure S21-24) in all
Ru(bpy) @NKMOFs.
Ru(bpy) @NKMOFs also proved the existence of 2,2'-
mol%) for 36 h. Determined by H NMR spectroscopy.
d
3 2
NKMOF-6 and Ru(bpy) Cl were added together. Using 2
e
eq pyridine as base, in absence of cocatalyst. In the
f
1
presence of 10 mol% 4-Methoxypyridine. Without 4-
H
NMR data of digested
3
g
Methoxypyridine. 15 W blue LEDs as light source.
3
2
+
bipyridine moieties from [Ru(bpy) ] (Figure S25-28).
3
For the reaction of aerobic oxidation of benzyl halide,40
in our initial investigation, we selected ethyl 2-bromo-2-
phenylacetate as the model substrate to explore the
optimal reaction conditions (Table 1). The reaction was
The open channels or polyhedral cages of MOFs would
allow effectively disperse the photocatalyst and facilitate
the transport of reactants and products, which could bring
high activity in catalytic reactions. Hence, the catalytic
activity of Ru(bpy) @NKMOFs were examined by two
model reactions, aerobic oxidation of benzyl halides and
the cyclization of tertiary anilines and maleimides under
visible light irradiation. Both reactions are important
organic reactions which have not been studied in MOF
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performed in the presence of Ru(bpy) @NKMOF-4 (0.5
3
3
mol%) (mass of catalyst is calculated on the basis of the
molecular formula (Table S2) and Ru loading) in DCM
for 36 h. The desired oxidation product was obtained in
40
41
6
7% yield (Table 1, entry 1). We screened various
solvents for the catalytic system (Table 1, entries 2-5) and
found DMA gave the product in 96% yield (TON = 192,
TOF = 5.33/h). Subsequently, we studied the influence of
materials yet. Ru(bpy) @NKMOF-4 was selected to be
3
a representative to optimize these reaction conditions.
These two reactions can utilize oxygen in the air and
belong to typical resource-saving oxidation reactions.
base to the catalytic activity of Ru(bpy) @NKMOF-4.
3
We found Li CO afforded the highest yield (96%), while
2
3
The UV-Vis absorption of Ru(bpy) @NKMOF-4
3
other inorganic base (Na CO ) and organic base
2
3
showed a strong broad absorption peak in 400-600 nm,
thus we selected a compact fluorescent lamp (CFL) as
light source for these reactions.
Table 1. Optimization of reaction condition of aerobic
oxidation of benzyl halide.
(pyridine) gave diminished yields of 62% and 75%,
respectively (Table 1, entry 6-7). Moreover, we found the
yield was reduced to 50% when reducing the dosage of
cocatalyst (4-methoxypyridine) (Table 1, entry 8), and
only trace product was detected when without cocatalyst
a
0
.5mol% Catalyst
Br
O
(Table 1, entry 9). Also, the yield was dropped to 70%
Li CO , 4-Methoxypyridine
2
3
COOEt
COOEt
when 15 W blue LEDs was used as light source (Table 1,
DMA, White light, 36 h
entry 10). The heterogeneity of Ru(bpy) @NKMOF-4
3
1a
2a
was verified via a hot-filtration experiment. After
removal of the catalyst after reacting for 10 h (yield
∼50%) reaction, no more product was detected during the
next 6 h under light irradiation (Figure 2a). Subsequently,
Yieldb
(%)
Entry
Catalyst
Base
Solvent
DCM
1
2
3
4
5
6
7
8
9
Ru(bpy)
Ru(bpy)
Ru(bpy)
Ru(bpy)
Ru(bpy)
Ru(bpy)
Ru(bpy)
Ru(bpy)
Ru(bpy)
Ru(bpy)
Ru(bpy)
Ru(bpy)
Ru(bpy)
None
3
3
3
3
3
3
3
3
3
3
3
3
3
@NKMOF-4
@NKMOF-4
@NKMOF-4
@NKMOF-4
@NKMOF-4
@NKMOF-4
@NKMOF-4
@NKMOF-4
@NKMOF-4
@NKMOF-4
@NKMOF-7
@NKMOF-6
@NKMOF-5
Li
Li
Li
Li
Li
2
2
2
2
2
CO
CO
CO
CO
CO
3
3
3
3
3
67
Toluene trace
DMF
76
after adding Ru(bpy) @NKMOF-4 back to the reaction
3
MeCN
DMA
DMA
DMA
DMA
DMA
DMA
DMA
DMA
DMA
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
DMA
DMA
DMA
DMA
89
system, the reaction continued and the yield reached to
96
75d
9
6% when extending the irradiation time to another 20 h.
Pyridine
Na CO
ICP-OES result of filtrated solution after the catalytic
reaction proved no leaching of catalytic species from
2
3
62
50e
Tracef
70g
Li
2
Li
2
Li
2
Li
2
Li
2
Li
2
Li
2
Li
2
Li
2
Li
2
Li
2
Li
2
Li
2
Li
2
Li
2
Li
2
Li
2
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
CO
3
Ru(bpy) @NKMOF-4 into solution. Moreover, we
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
further
compared
the
PXRD
patterns
of
1
1
1
0
1
2
Ru(bpy) @NKMOF-4 before and after catalytic
35
3
reaction,
and
found
the
crystallinity
of
94
13
14
86
Ru(bpy)
3
@NKMOF-4 catalyst fully retained (Figure
Trace
Trace
Trace
Trace
Trace
Trace
Trace
S30). There results revealed the excellent stability of
1
1
1
1
1
2
2
2
2
2
5
6
7
8
9
0
1
2
3
4
H
H
H
3
3
3
BTTC
Ru(bpy) @NKMOF-4 catalyst. To further explore the
3
BTC
advantage of heterogeneous catalyst, we tested the
TATB
reusability of Ru(bpy) @NKMOF-4 which could be
3
CuCl
2
easily recovered by filtration and reused for at least 5
times without significant loss of catalytic activity (Figure
NKMOF-6
HKUST-1
2b). All these results suggest that Ru(bpy) @NKMOF-
3
Ru(bpy)
3
Cl
2
85
86c
4 is a true heterogeneous catalyst which exhibits high
robustness and good reusability.
3 2
NKMOF-6+Ru(bpy) Cl
UiO-67-Ru
67
77
3
Ru(bpy) @MCM-41
a
Reactions were performed with ethyl 2-bromo-2-
phenylacetate (0.2 mmol), base (0.2 mmol), 4-
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Ru(bpy) @NKMOFs. Moreover, we encapsulated
3
4
2
Ru(bpy) species into MCM-41 via a diffusion method .
3
Although the Ru(bpy) @MCM-41 gave a 77% yield
3
(entry 24, Table 1), its reusability was bad because
Ru(bpy) @MCM-41 almost released all Ru(bpy) in the
3
3
first catalytic reaction cycle due to weak interaction
between Ru(bpy)3 species and MCM-41. Overall,
Ru(bpy) @NKMOFs systems showed great advantage
3
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
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3
3
3
3
4
4
4
4
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4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
attributed to their facile preparation, superior catalytic
activity and good reusability.
Figure 2. (a) Hot filtration experiment of
Ru(bpy) @NKMOF-4 as catalyst. Catalyst was added in
the initial 0-10 h; the catalyst was removed in 10-16 h;
catalyst was added back after 16 h. (b) Catalytic cycling
3
Table 2. Substrate expansion for the reaction of aerobic
a
oxidation of benzyl halides.
0.5mol% Catalyst
X
O
experiment of Ru(bpy)
3
@NKMOF-4 as catalyst.
Li2CO3, 4-Methoxypyridine
DMA, White light, 36 h
R2
R2
R1
R1
Photocatalytic activity of other Ru(bpy) @NKMOFs
3
1
2
was also investigated. Firstly, we tested the solid UV-Vis
spectra and found a strong broad absorption of 400-600
Entry
Reactants (1)
Products (2)
Yield b (%)
2a/96
2b/98
2c/96
nm for Ru(bpy) @NKMOF-5, -6 and -7 (Figure S31-
3
Br
O
3
3). This allows us to utilize white light as light sources.
1
2
3
4
5
6
7
8
COOEt
COOEt
Ethyl 2-bromo-2-phenylacetate was selected as the model
Br
COOEt
Cl
O
COOEt
Cl
substrate. Firstly, the nonporous Ru(bpy) @NKMOF-7
3
was chose as a comparison, which gave rise to a very low
yield of 35% (entry 11, Table 1) ascribed to the surface
Br
COOEt
F
O
COOEt
F
catalysis. By contrast, Ru(bpy) @NKMOF-5 and
3
Br
O
Ru(bpy) @NKMOF-6 gave yields of 86% and 94%,
COOMe
COOMe
2d/68
2e/73
3
respectively (entries 12-13, Table 1). These results
indicate that the porosity is necessary for high catalytic
activity. In addition, we also studied the time-dependent
Br
O
COOMe
Cl
COOMe
Cl
Br
O
O
O
O
2f/83
catalytic activity for Ru(bpy) @NKMOF-4, -5 and -6
3
compared with the homogenous Ru(bpy) Cl (Figure
Cl
3
2
2f/85
S34). In the initial 15 h, homogeneous Ru(bpy) Cl
O
O
O
3
2
Cl
catalyst showed faster and higher catalytic activity than
2g/43
Ru(bpy) @NKMOFs, possibly due to the faster substrate
F
F
F
F
3
a
diffusion into the catalytic site of homogenous system.
However, after 15 h, the catalytic efficiency of
Reaction were performed with reactant (1) (0.2 mmol),
Li CO (0.2 mmol), 4-Methoxypyridine (20 mol%) in the
presence of Ru(bpy) @NKMOF-4 (0.5 mol%) in DMA
2
3
Ru(bpy) @NKMOFs exceeded the homogeneous
3
3
b
1
(
1.0 mL) for 36 h. Determined by H NMR.
With the optimal reaction conditions in hand, we then
explored the reaction scope using various benzyl halides
Table 2). α-bromoarylacetic acid esters bearing various
catalyst, indicative of the advantage to use porous MOFs
as hosts. Moreover, we further explored which parts of
Ru(bpy) @NKMOFs contributed to the high catalytic
3
activity. Thus, we chose no catalyst, ligands, CuCl2,
NKMOF-6, HKUST-1 (a widely studied copper-based
MOF) as controls, which all afforded trace yield (entries
14-20, Table 1). By contrast, Ru(bpy) Cl afforded 85%
(
halides at the aryl ring (entries 1-5) all gave the
corresponding products in good to excellent yields (68%-
3
2
9
8%). The expansion of α-aryl carbonyl compounds to 2-
halo-1,2-diphenylethanones provided good yields (83%,
5% for Table 2, entries 6, 7, respectively) as well.
yield (entry 21). Therefore, we can conclude that the
catalytic activity of Ru(bpy) @NKMOFs came from the
3
8
2
+
photoactive [Ru(bpy)3] species. In addition, when
Although the oxidation of benzhydryl halides was not
effective under the current conditions, chloride as a
leaving group was tolerated in this transformation and
generated the desired product in 43% yield (entries 8).
In order to further study the advantage of
directly mixing NKMOF-6 (0.5 mol%) with Ru(bpy) Cl
3
2
(0.5 mol%), the yield was only 86% (entry 22, Table 1)
equivalent to the homogeneous Ru(bpy) Cl , while
3
2
Ru(bpy) @NKMOF-6 gave a boosted yield of 94%.
3
These results further revealed the importance and
necessity to encapsulate photocatalysts in the pores of
Ru(bpy) @NKMOFs
catalysts,
we
used
3
Ru(bpy) @NKMOFs to catalyze the cyclization of
3
4
1
MOFs. In addition, UiO-67-Ru which covalently
43
tertiary anilines with maleimides. As shown in Table 3,
2
+
grafted [Ru(bpy)3]
comparison. The yield was 67% (entry 23, Table 1),
which was much lower than those of
moieties was selected as a
substrates 3a (0.50 mmol), 4a (0.25 mmol), 1 mol%
Ru(bpy) @NKMOF-4 and solvent (3.0 mL) were added
3
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6
into a schlenk tube. Subsequently, the reaction tube was
5
6
7
8
9
1
3 mol% Ru(bpy) @NKMOF-4
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
93
3
irradiated by two 23 W compact fluorescent lamps at
room temperature. We found the product 5a was
generated in 58% yield after 36 h (Table 3, entry 1) using
DMF as solvent, while DCM or MeCN did not form
products (entries 2-3). To further optimize the reaction
conditions, we increased the amount of catalyst. When
4 mol% Ru(bpy)
3 mol% Ru(bpy)
3 mol% Ru(bpy)
3 mol% Ru(bpy)
3 mol% Ru(bpy)
None
3
3
3
3
3
@NKMOF-4
@NKMOF-4
@NKMOF-5
@NKMOF-6
@NKMOF-7
93
18c
83
89
0
32
photocatalyst (Ru(bpy) @NKMOF-4) were increased to
3
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
11
trace
trace
trace
trace
trace
trace
trace
78
2
mol% and 3 mol%, the yields increased to 73% and 93%,
respectively (entries 4-5). Yield did not further improve
with more catalyst loading (4 mol%, entry 6). With the
optimal reaction conditions, we can obtain a good yield
of 93% (TON = 31, TOF = 0.86/h) (entry 5), in contrast
1
1
2
3
3 mol% H
3 mol% H
3 mol% H
3
3
3
TATB
BTTC
BTC
14
15
to the result when homogeneous Ru(bpy) Cl (3 mol%)
3
2
3 mol% CuCl2
was applied (76%, entry 19). These results further
indicated that the porosity of MOFs was necessary to the
high catalytic activity. When the reaction atmosphere was
changed from air to argon, the yield decreased to 18%,
indicating the necessity of oxygen to the reaction (entry
1
6
3 mol% NKMOF-6
3 mol% HKUST-1
17
18
NKMOF-6 + Ru(bpy) Cl
3
2
1
9
Ru(bpy)
3
Cl
2
76
7
). It was found that Ru(bpy) @NKMOF-5 and -6 as
3
20
UiO-67-Ru
64
catalysts gave yields of 83% and 89%, respectively
Table 3, entry 8-9). By contrast, the nonporous
Ru(bpy) @NKMOF-7 gave a very low yield of 32%
a
(
Reaction condition: 3a (0.50 mmol), 4a (0.25 mmol), in 3.0
mL solvent and irradiation of two 23 W compact fluorescent
lamps for 36 h at rt. Determined by H NMR. Reaction
was performed under an argon atmosphere.
3
b
1
c
(Table 3, entry 10), possibly attributed to the surface
catalysis. To investigate which component played a key
role in the catalytic process, we carried out some control
experiments. It was found that the reaction did not take
place without catalyst, or in the presence of the ligands or
metal salts of MOFs (Table 3, entry 11-15). We also
found that pure copper-based MOFs including NKMOF-
A hot-filtration experiment was conducted to prove if
Ru(bpy)
Ru(bpy)
@NKMOFs belong to heterogenous catalysts.
@NKMOF-4 with the best catalytic
3
3
performance was selected as a representative. After
removal of MOF catalyst after reaction for 10 h (yield
50%), there was no more product detected during the next
12 h irradiation (Figure S35a). Subsequently, after adding
6
and HKUST-1 cannot catalyze the reaction (entry 16-
1
7). Moreover, when directly using a mixture of
NKMOF-6 (3 mol%) and Ru(bpy) Cl (3 mol%), the
3
2
yield was only 78% (entry 18) equivalent to the
homogeneous Ru(bpy) Cl (76%, entry 19), while
Ru(bpy) @NKMOF-4 back to the reaction solution, the
3
reaction continued and the yield can reach to 92% after
further extending the irradiation time of 14 h. ICP-OES
result of filtrated solution after catalysis reaction showed
trace amount (<0.3%) of Ru species. These results
together with the catalytic recycling experiments revealed
the excellent reusability of Ru(bpy)
(Figure S35b). We further compared the PXRD patterns
of Ru(bpy) @NKMOF-4 before and after catalytic
reaction, and found its crystallinity fully retained (Figure
S36). There results revealed the excellent stability of Ru
catalytic species in Ru(bpy) @NKMOFs. A time-
dependent catalytic activity for Ru(bpy) @NKMOF-4
compared with the homogenous Ru(bpy) Cl (Figure S37)
3
2
Ru(bpy) @NKMOF-6 showed a boosted yield of 89%.
3
These results further demonstrated the advantage to
encapsulate photocatalysts into porous MOFs.
Additionally, we selected UiO-67-Ru as a comparison,
and the yield was 64% (entry 20, Table 3) which was
@NKMOF-4
3
much lower than those of Ru(bpy) @NKMOFs.
3
Table 3. Optimization of reaction condition of cyclization of
3
a
tertiary anilines and maleimides.
O
O
3
Me
Catalyst
N
H
Me
N
Me
N
Me
O
3
DMF, air
H
visible light, 36 h
3
2
O
N
3a
4a
Me
5aa
further proved the superiority of our heterogeneous
catalysts.
Entry
Catalyst
Solvent
DMF
Yield b (%)
58
Under the optimal reaction conditions, we tested the
generality of the substrates with various substituted
tertiary N,N-dimethylanilines (3) and maleimides (4). As
shown in Table 4, the heterogeneous catalyst showed
good compatibility to broad functional groups. N-
aliphatic (such as methyl, benzyl) maleimides could
1
2
3
4
1 mol% Ru(bpy)
1 mol% Ru(bpy)
1 mol% Ru(bpy)
2 mol% Ru(bpy)
3
3
3
3
@NKMOF-4
@NKMOF-4
@NKMOF-4
@NKMOF-4
DCM
MeCN
DMF
trace
trace
73
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5
5
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generate the products 5b and 5c in 91% and 85% yield,
Ru(II)* was generated under irradiation of visible light
from the Ru(II) encapsulated heterogeneous
respectively (entries 2-3, Table 3). In addition, we found
that the electronic property of substituent groups on the
aryl ring of electron-deficient olefins (4) can influence the
reactivity. N-aryl maleimide substituted with halogen
atoms afforded their corresponding tetrahydroquinolines
photocatalyst. Pyridinium salt I could be generated by
reaction of 4-methoxypyridine with 1a as the literature
reported. 2a is efficiently produced from III with the
formation of the superoxide radical anions via the alkoxyl
radical intermediates IV. In this reaction, since MOFs did
not participate in the catalytic process, we believe that the
mechanism is completely consistent to the literature
5
d-5f with high (83%−90%) yields (entries 4-6). N-aryl
maleimide substituted with electron-donating groups
such as methoxyl generated its corresponding
tetrahydroquinoline 5g in a slightly lower yield (68%,
entries 7). We then shifted our attention to the scope of
tertiary anilines. 4-halo (3i, 3j), as well as unsubstituted
tertiary N,N-dimethylanilines (3h) could react with 4a to
form the corresponding tetrahydroquinolines (5h-5j) with
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
40
41
reports . In addition, on the basis of relevant literatures ,
the mechanism for the synthesis of tetrahydroquinolines
from tertiary anilines and maleimides is proposed in
Scheme S2. Initially, the Ru(bpy) (II) in heterogeneous
3
photocatalyst was irradiated to the photo-excited
7
0%−92% yields (entries 8-10). While 3-methyl N,N-
Ru(bpy) (II)* under visible light. Simultaneously, the
3
dimethylanilines (3k) resulted in the formation of a
mixture of 5k-1 and 5k-2, with a ratio of 1.4:1 according
single electron transfer from tertiary aniline 3a to the
photo-excited Ru(bpy) (II)* results in the generation of
3
1
to H NMR analysis. Interestingly, when 3a (4.0 equiv)
Ru(bpy) (I) and radical cation A, which is deprotonated
3
and di-N-substituted maleimides (1.0 equiv) were
irradiated for 36 h under the optimized conditions,
bicyclized compound 5l were formed in 48% yield (entry
to generate -aminoalkyl radical B. Then B reacts with
4a to generate intermediate C, which undergoes
cyclization to form radical D. Subsequently, D is
1
2).
converted to tetrahydroquinoline 5a by rapid oxidation of
-
Table 4. Substrate expansion of the reaction of tertiary
O . The proton eliminated from A is captured by HOO to
2
a
anilines with maleimides.
achieve hydrogen transfer to obtain H O .
2
2
R2
N
Furthermore, to illustrate the generality of this
templating approach to convert homogeneous visible
light catalyst into heterogeneous photocatalyst, another
two commercially available homogenous photocatalysts,
Ir(ppy) (ppy = 2-phenylpyridine) and Ru(phen) Cl
O
H
O
Me
N
Me
3 mol% catalyst
O
R1
R2
R1
N
H
DMF, air
visible light, 36 h
N
O
Me
5
3
4
3
3
2
R1
R2
5/Yield b (%)
(phen = 4,7-diphenyl-1,10-phenanthroline) were also
used as templates (Figure S38). Two new MOF materials
Entry
1
2
3
4
5
6
7
8
9
10
4-Me
4-Me
4-Me
4-Me
4-Me
4-Me
4-Me
H
Ph
5a/93
5b/91
5c/85
5d/90
5e/83
5f/86
5g/68
5h/71
5i/92
5j/70
isomorphic with Ru(bpy) @NKMOF-4 were obtained,
3
Me
named
as
Ru(ph) @NKMOF-4
and
3
Ir(ppy) @NKMOF-4. Their structures were further
Bn
3
verified by SCXRD and PXRD studies data (Figure S39).
ICP-OES analysis showed 20% and 8% catalyst loading,
4-FPh
4-ClPh
4-BrPh
4-OMePh
Ph
respectively. N sorption data proved their permanent
2
2
2
porosity (633 m /g, 564 m /g for Ir(ppy) @NKMOF-4
3
and Ru(phen) @NKMOF-4, respectively) and pore size
3
distribution (~9 Å, ~7 Å for Ir(ppy) @NKMOF-4 and
3
Ru(phen) @NKMOF-4, respectively) (Figure S40-41).
3
4-F
Ph
Notably, we found Ir(ppy) @NKMOF-4 and
3
Ru(phen) @NKMOF-4 showed better catalytic activity
3
4-Br
3-Me
Ph
than Ru(bpy) @NKMOF-4, which is consistent with the
3
11
Ph
5k-1, 5k-2 (1.4:1)/90
5l/48
catalysis trend of corresponding homogeneous
photocatalysts. For example, for the reaction of aerobic
di-N-substituted
maleimides
12
4-Me
c
oxidation of benzyl halide, Ir(ppy) @NKMOF-4 and
3
a
Reaction condition: tertiary N,N-dimethylanilines 3 (0.50
mmol), maleimides 4 (0.25 mmol), Ru(bpy) @NKMOF-4
3 mol%) in 3.0 mL solvent. Determined by H NMR. The
Ru(phen) @NKMOF-4 afforded the highest yield of
3
3
1
99% after light irradiation for 25 h, better than the 85%
b
c
(
yield for Ru(bpy) @NKMOF-4 (Figure S42).
3
substrate used here is 1,1'-(methylenebis(4,1-
phenylene))bis(1H-pyrrole-2,5-dione).
In conclusion, we developed a versatile template-
directed synthesis approach to prepare new types of
photocatalyst-encapsulating metal-organic frameworks
Herein, we proposed a mechanism for the catalytic of
the aerobic oxidation (Scheme S1). The excited state
(photocatalyst@MOFs) with zeolite-like structures. Due
to the high robustness, permeant porosity and protection
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(8) Lee, C. Y.; Farha, O. K.; Hong, B. J.; Sarjeant, A. A.; Nguyen, S.
effect of MOF matrixes, photocatalyst@MOFs showed
fascinating heterogeneous catalytic activity for the
reaction of aerobic oxidation of benzyl halides and the
cyclization of tertiary anilines and maleimides under
visible light. Interestingly, photocatalyst@MOFs
exhibited boosted photocatalytic activity compared with
their homogenous photocatalyst counterparts. It could be
because that the pores of MOFs can effectively disperse
the photocatalyst and facilitate the transport of reactants
and products, which is necessary to the high catalytic
activity. Moreover, we found the template-directed
strategy to convert homogenous catalysts into
heterogeneous systems showed high generality and can
be extended to more MOF or photocatalyst systems. This
research points out a new avenue to prepare highly
efficient heterogeneous photocatalysts and broaden the
catalytic application of MOF materials.
T.; Hupp, J. T. Light-Harvesting Metal-Organic Frameworks (MOFs):
Efficient Strut-to-Strut Energy Transfer in Bodipy and Porphyrin-
Based MOFs. J. Am. Chem. Soc. 2011, 133, 15858-15861.
(9) Shen, J. Q.; Liao, P. Q.; Zhou, D. D.; He, C. T.; Wu, J. X.; Zhang,
W. X.; Zhang, J. P.; Chen, X. M. Modular and Stepwise Synthesis of a
Hybrid Metal-Organic Framework for Efficient Electrocatalytic
Oxygen Evolution. J. Am. Chem. Soc. 2017, 139, 1778-1781.
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ASSOCIATED CONTENT
(14) Chughtai, A. H.; Ahmad, N.; Younus, H. A.; Laypkovc, A.;
Supporting Information. Synthesis, supplementary structural
figures, and supplementary characterization data, crystal
data (CIF). Supporting information for this article is given
via a link at the end of the document.
Verpoort, F. Metal-Organic Frameworks: Versatile Heterogeneous
Catalysts for Efficient Catalytic Organic Transformations. Chem. Soc.
Rev. 2015, 44, 6804-6849.
(15) Yoon, M.; Srirambalaji, R.; Kim, K. Homochiral Metal-Organic
Frameworks for Asymmetric Heterogeneous Catalysis. Chem. Rev.
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012, 112, 1196-1231.
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AUTHOR INFORMATION
(
Homochiral Metal-Organic Frameworks. Chem. Soc. Rev. 2009, 38,
1248-1256.
Corresponding Author
(17) Lykourinou, V.; Chen, Y.; Wang, X. S.; Meng, L.; Hoang, T.;
pcheng@nankai.edu.cn; zhangzhenjie@nankai.edu.cn
Ming, L. J.; Musselman, R. L.; Ma, S. Q. Immobilization of MP-11 into
a Mesoporous Metal-Organic Framework, MP-11@mesoMOF: A New
Platform for Enzymatic Catalysis. J. Am. Chem. Soc. 2011, 133, 10382-
10385.
(18) An, J.; Geib, S. J.; Rosi, N. L. Cation-Triggered Drug Release
from a Porous Zinc-Adeninate Metal-Organic Framework. J. Am.
Chem. Soc. 2009, 131, 8376-8377.
ACKNOWLEDGMENT
The authors acknowledge the support of National Natural
Science Foundation of China (21601093) and Tianjin
Natural Science Foundation of China (18JCZDJC37300).
(19) Horcajada, P.; Serre, C.; Vallet-Regi, M.; Sebban, M.; Taulelle,
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