Development of metal-organic framework (MOF)-B12 system as new bio-inspired heterogeneous catalyst

Article abstract of DOI:10.1016/j.jorganchem.2014.11.015

Abstract A novel bimetal complex {Zn₄Ru₂(bpdc)₄·4C₂NH₈·9DMF}_n (1) (H₂bpdc = 4,4′-biphenyldicarboxylic acid) was synthesized by the solvothermal method. The results of the X-ray crystallographic analysis revealed that 1 crystallizes in the orthorhombic Pna2₁ space group, which has a 3D 2-fold interpenetrated hex framework, with open channel sizes along the [010] direction of ca. 1.4 nm × 1.4 nm. The photosensitizer [Ru(bpy)₃]²⁺ was adsorbed into the 1 to form Ru@MOF by cation exchanging. A cobalamin derivative (B₁₂), heptamethyl cobyrinate, was also effectively immobilized on Ru@MOF, and the resulting hybrid complex, B₁₂-Ru@MOF, exhibited a high reactivity for the dechlorination reaction of 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane (DDT) under an N₂ atmosphere by visible light irradiation in the solid state. The catalysis of B₁₂-Ru@MOF can still reach more than a ca. 80% conversion after third recyclings. Furthermore, the heterogeneous catalyst, B₁₂-Ru@MOF, was useful for the cobalamin-dependent reaction, such as the 1,2-migration of the acetyl group.

Full text of DOI:10.1016/j.jorganchem.2014.11.015

Journal of Organometallic Chemistry xxx (2014) 1e7
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Development of metal-organic framework (MOF)-B system as new
12
bio-inspired heterogeneous catalyst
Jing Xu b, Hisashi Shimakoshi a , Yoshio Hisaeda a
a
,
,
*
, *
a
Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University, Fukuoka 819-0395, Japan
Key Laboratory of Atmospheric Environment Monitoring and Pollution Control, School of Environment Science and Technology,
b
Nanjing University of Information Science and Technology, Nanjing 210044, China
a r t i c l e i n f o
a b s t r a c t
0
Article history:
Received 6 October 2014
Received in revised form
A novel bimetal complex {Zn Ru (bpdc) $4C NH $9DMF} (1) (H bpdc ¼ 4,4 -biphenyldicarboxylic acid)
4
2
4
2
8
n
2
was synthesized by the solvothermal method. The results of the X-ray crystallographic analysis revealed
that 1 crystallizes in the orthorhombic Pna2 space group, which has a 3D 2-fold interpenetrated hex
1
11 November 2014
framework, with open channel sizes along the [010] direction of ca. 1.4 nm ꢀ 1.4 nm. The photosensitizer
Accepted 12 November 2014
Available online xxx
2þ
[
Ru(bpy)
3
]
was adsorbed into the 1 to form Ru@MOF by cation exchanging. A cobalamin derivative
(
B
12), heptamethyl cobyrinate, was also effectively immobilized on Ru@MOF, and the resulting hybrid
complex, B12eRu@MOF, exhibited a high reactivity for the dechlorination reaction of 1,1-bis(4-
chlorophenyl)-2,2,2-trichloroethane (DDT) under an N atmosphere by visible light irradiation in the
solid state. The catalysis of B12eRu@MOF can still reach more than a ca. 80% conversion after third
recyclings. Furthermore, the heterogeneous catalyst, B12eRu@MOF, was useful for the cobalamin-
dependent reaction, such as the 1,2-migration of the acetyl group.
Keywords:
Metal-organic framework
Cation exchanging
2
B
12
Heterogeneous catalyst
Recycle use
© 2014 Elsevier B.V. All rights reserved.
Introduction
perchlorate (Scheme 1), are used as efficient catalysts for a number
of chemical transformations due to their rich redox and coordina-
The chemistry of metal-organic frameworks (MOFs) has rapidly
evolved in recent years. They are a class of crystalline materials,
which are constructed from well-defined molecular building blocks
and metal or metal-cluster connecting nodes. Most MOF research
has focused on the storage and separation of small gaseous mole-
cules by taking advantage of their high microporosities [1e3].
However, numerous recent reports have demonstrated that active
functional groups can be rationally designed and incorporated into
MOFs to create hybrid materials with potential applications,
including chemical sensing [4e7], catalysis [8e12], biomedical
imaging [13e15], and drug delivery [16e18].
tion chemistry [23,24] as well as a high nucleophilicity toward
various alkyl halides in its Co(I) state [25]. The radical reactions
have been widely used to synthesize complicated compounds
because of the high selectivity under relatively mild conditions
among the numerous synthetic methods. However, the alkyl radical
formed by visible light irradiation has too short a lifetime to
migrate, so it is difficult for the 1,2-migration reaction to occur
using the normal B12 catalytic systems [26e28].
To develop the advantage of MOFs and B12, we adopted the
absorption method that enables immobilization of the B12 de-
rivatives into the MOFs. It is expected that the pores of MOF can
capture the radical to prolong its lifetime, then selectively catalyze
the reaction. In this study, a porous MOF was synthesized by the
solvothermal method, which can adsorb the cobalamin derivative
(B12) and Ru(II) photosensitizer by cation exchange, and the
At the same time, bioorganometallic cobalamin (B12)-dependent
enzymes catalyzes various molecular transformations that are of
particular interest from the viewpoint of biological chemistry as
well as synthetic organic chemistry and catalytic chemistry
[19e22]. Cobalamin derivatives, such as heptamethyl cobyrinate
B12eRu@MOF hybrid was explored for the dechlorination reaction
and 1,2-migration reaction in the solid state. As B12eRu@MOF
works as a heterogeneous catalyst, we can separate the products
and catalyst after the reaction for reuse. This is the first example of
the B12 catalysis using the MOF system.
*
Corresponding authors. Tel./fax: þ81 92 802 2830.
E-mail addresses: shimakoshi@mail.cstm.kyushu-u.ac.jp (H. Shimakoshi),
yhisatcm@mail.cstm.kyushu-u.ac.jp (Y. Hisaeda).
http://dx.doi.org/10.1016/j.jorganchem.2014.11.015
0
022-328X/© 2014 Elsevier B.V. All rights reserved.
Please cite this article in press as: J. Xu, et al., Journal of Organometallic Chemistry (2014), http://dx.doi.org/10.1016/j.jorganchem.2014.11.015

2
J. Xu et al. / Journal of Organometallic Chemistry xxx (2014) 1e7
the single net (Fig. 1d). It is noteworthy that there is still free space
(
Fig. 1c) which was calculated by the PLATON [31] analysis of 49.3%
3
(3992.4 Å per unit) filled by DMF molecules and its decomposed
þ
product (C
2
NH
8
).
Stability and gas sorption property of complex 1
Stability information about the porous structure is required and
the results of the TGA analysis not only indicate the thermal sta-
bility of the MOF, but also turn out to be decisive data to ensure an
optimized temperature of activation to remove the guest mole-
cules. For complex 1, the TGA data revealed a steady weight loss
ꢂ
between about 50 and 250 C, which correspond to the loss of the
þ
solvent DMF molecules (calcd. 20.38%, found 20.45%) and C
2
NH
8
cations (calcd. 5.71%, found 5.85%). No weight loss then occurred
ꢂ
until approximately 330 C, when the entire structure starts to
decompose as shown in Fig. 3. According to the TGA results, the
ꢂ
framework 1 is stable even up to 330 C. Before the gas adsorption
tests, the activation for removing the guest molecules from the
pores by heating in a vacuum is a required pre-treatment and the
as-synthesized crystal samples were heated at the optimized
ꢂ
temperature of 100 C for 20 h. The adsorption isotherm for 1 is
shown in Fig. 3 inset, in which complex 1 shows a comparatively
3
ꢁ1
high adsorption amount of CO
at STP) corresponding to 1 CO
uptake is nearly 4 times higher than that of N
at STP). The Langmuir and BET surface areas estimated from the CO
2
at 195 K and 1 atm. (40.13 cm g
2
molecule per formula unit. The CO
2
3
ꢁ1
2
at 77 K (9.17 cm g
2
2
ꢁ1
adsorption isotherm are 119.73 and 85.64 m g , respectively. The
high affinity for CO of 1 may be due to the unsaturated metal sites
Scheme 1.
2
in 1 associated with the pore structure as revealed in other MOF
materials [32,33]. Thus, complex 1 may have a potential application
in the separation of CO /N mixtures and it is possible to adsorb
2 2
Results and discussion
other molecules in the cavity or on the surface of its framework.
Description of crystal structures
Complex {Zn
X-ray diffraction analysis revealed that 1 crystallizes in the ortho-
rhombic form with the space group of Pna2 and the asymmetric
unit has a Ru(II) atom, two Zn(II) atoms, four 4,4 -biphenyldi-
Ru
4 2
(bpdc)
4
$4C
2
NH
8
$9DMF}
n
(1). The results of the
Preparation and characterization of Ru@MOF and B12eRu@MOF
3 2
We used the MOF as a supporter to immobilize [Ru(II) (bpy) ]Cl
and B12 complexes (Scheme 1) by a cation exchange reaction. This
cation or anion exchange of MOFs is useful method for function-
1
0
2
ꢁ
þ
carboxylate ligands (bpdc ), four C
2
NH
8
(protonated dimethyl
amine) molecules decomposed by the DMF solvent and nine DMF
alizing MOFs [34e42]. First, we tried to absorb [Ru(II) (bpy)
form Ru@MOF. The color of the [Ru(II) (bpy) ]Cl ethanol solution
disappeared by stirring with MOF 1, and the UVevis spectra of the
3 2
]Cl to
molecules. The bpdc2 ligands have three coordination modes
Scheme 1). Every Ru(II) center with an octahedral coordination
geometry is six-coordinated by six oxygen atoms from six different
ꢁ
3
2
(
2
þ
solution proved the adsorption of [Ru(II) (bpy)
3
]
in the cavity of
2
ꢁ
bpdc ligands (four (b) and two (c) coordinated modes). Crystal
view of 1 is shown in Fig. 1. The schematic drawings of 1 based on
the crystal structure are also shown in Fig. 2. And as shown in
Fig. 1a, two Zn(II) atoms are five-coordinated with a distorted
trigonal bipyramid coordination geometry by five oxygen atoms
the MOF (Fig. 4). The IR spectra showed that the surface of the
Ru@MOFs is the same as MOF though the two samples have
different colors (Fig. S1). It was calculated from the ICP-MS data
that molar ratio of Ru/MOF is 3:1. The cation exchange efficiency of
þ
Ru photosensitizer considered as {[Ru(bpy)
as 75% in Ru@MOF.
3
]Cl} form is estimated
2
ꢁ
from four different bpdc ligands (one (a), two (b) and one (c)
coordinated modes). The RueO and ZneO bond lengths are in the
range of 2.049(1)e2.109(9) Å and 1.909(1)ꢁ1.970(1) Å, respectively
as listed in Table 2.
Next, it is very important to adsorb the B12 complex in order to
construct the B12eRu@MOF as a catalysis system. We used a hep-
tamethyl cobyrinate perchlorate for the B12 complex (Scheme 1).
The UVevis spectra illustrated that the heptamethyl cobyrinate was
adsorbed by Ru@MOF (Fig. 5). The evidence for the adsorption of
the B12 complex onto Ru@MOF was obtained by an ESR analysis,
and the well-defined Co(II) low spin signal typical for heptamethyl
cobyrinate was observed as shown in Fig. 6 [43]. The amount of B12
molecules was also calculated from the ICP-MS analysis of which
the molar ratio of B12/MOF is 1:15. Given the size of the B12 and the
cavity size of Ru@MOF, the number of adsorbed B12 molecules were
By carefully observing the structure, the connections of the
2
ꢁ
central ZneRueZn and linear linker of the bpdc ligand make the
complex have a 3D framework with large channels as illustrated in
Fig. 1b. Each ZneRueZn unit acts as an 8-connecting node, and the
topology can be described as hex net with the short Schl €a fli sym-
6
18
3
bols of (3 .4 .5 .6) [29,30]. There is a large void in the single net of
the complex as mentioned above, the open channel sizes along the
[
010] direction are ca.1.4 nm ꢀ 1.4 nm (Fig.1b), and according to the
2
þ
famous Aristotle's observation that “nature abhors a vacuum”,
interpenetration inevitably occurred. We found that there were
two individual 3D hex nets interpenetrating due to the large void in
smaller than that of [Ru(bpy)
3
]
. Actually, when we first adsorbed
B
12 complex in the MOF, the obtained B12-MOF did not adsorb
2þ
[Ru(bpy)
3
]
. Thus, it is likely that B12 complex is existed around
2
þ
the surface of MOF, whereas small [Ru(bpy)
3
]
is existed in cavity
Please cite this article in press as: J. Xu, et al., Journal of Organometallic Chemistry (2014), http://dx.doi.org/10.1016/j.jorganchem.2014.11.015

J. Xu et al. / Journal of Organometallic Chemistry xxx (2014) 1e7
3
Fig. 1. (a) Coordination environment of Zn1, Zn2 and Ru in 1 with the ellipsoids drawn at the 50% probability level, and hydrogen atoms were omitted for clarity. (b) A single 3D
framework from the c axis and polyhedron presentations of ZneRueZn metals. (c) The space filling mode of 2-fold interpenetrating structure. (d) Topological representation of the
2-fold interpenetrating hex network of 1.
of MOF in B12eRu@MOF. In this way, the order of adsorbed mo-
lecular is important for synthesis of B12eRu@MOF.
bis(4-chlorophenyl)-2,2-dichloroethane (DDD) as the major prod-
uct (Eq. (1)). The dechlorination reaction did not proceed in the
dark as shown by entry 2 in Table 3. In this system, excess of trie-
thanolamine was used as sacrificial reductant for photosensitizer
recovery during the catalytic reaction. Moreover, B12eRu@MOF can
be recovered by filtration and subsequently reused several times
and maintain its catalytic efficiency as shown by entries 3 and 4 in
Table 3.
Catalytic process of B12eRu@MOF system
The dechlorination of DDT was carried out as shown in Table 3.
As DDT was irradiated with visible light in the presence of
B
12eRu@MOF for 4 h, the DDT was almost decomposed to form 1,1-
Fig. 2. (a) ZneRueZn unit structure of 1. (b) Schematic drawing of 1 based on crystal structure.
Please cite this article in press as: J. Xu, et al., Journal of Organometallic Chemistry (2014), http://dx.doi.org/10.1016/j.jorganchem.2014.11.015

4
J. Xu et al. / Journal of Organometallic Chemistry xxx (2014) 1e7
Table 1
Crystallographic data for 1.
Chemical formula
147 159 13 2 4
C H N O41Ru Zn
M
3227.48
Orthorhombic
Pna2
24.572(6)
14.514(4)
22.314(5)
90
Crystal system
Space group
a, Å
b, Å
c, Å
1
ꢂ
b,
3
V, Å
Z
7958(3)
2
T, K
93
8.57
1.347
ꢁ
1
m
(MoK
a
), cm
ꢁ
3
Dcalcd, g cm
l
, Å
0.71073
0.0992
0.1213
0.3152
R
R
wR
int
a
1
[I > 2
s
(I)]
s
2
[I > 2
(I)]b
P
P
a
R
1
¼
jjF
o
j ꢁ jF
c
2
jj= jF
o
2
j.
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
P
Pꢀ
2
1=2
2
2
b
wR
2
¼ ꢀ wðjF
o
j
ꢁ jF
c
j Þꢀ= ꢀwðF
o
Þ ꢀ
,
where
w ¼ 1=½s ðF Þ
o
2
2
2
.
Fig. 3. TGA curves of complex 1, inset graph is gas adsorption isotherms (CO
of 1 (filled symbols: adsorption; open symbols: desorption).
2 2
and N )
þðaPÞ þ bPꢃ; P ¼ ðF þ 2F Þ=3
o
c
(1)
A reaction mechanism is proposed as follows: The Co(II) com-
plex is reduced to the Co(I) species by the photosensitizer in the
cavity of MOF by visible light irradiation, and the alkylated complex
may be formed by the reaction of the Co(I) with DDT. The CoeC
bond of the alkylated complex should be subsequently cleaved by
photolysis to form the substrate radical and Co(II) species. The
substrate radical will abstract H to form DDD [43].
Fig. 4. UVevis spectral change of [Ru(bpy)
MOF 1.
3 2
]Cl ethanol solution in the presence of
The catalytic reaction was also carried out using 2-acetyl-1-
bromo-2-ethoxycarbonylpropane as a substrate (Eq. (2)). After a
2
4-h reaction by visible light irradiation, conversion of the sub-
Table 2
strate reached 82% and the acetyl migrated product was formed as
the main product in 68% yield as shown by entry 1 in Table 4. When
EtOH was used as the reaction solvent, conversion of the substrate
ꢂ
Selected bond lengths [Å] and angles [ ] for 1.
1a
O(005)eRu(02)#1
O(008)eRu(02)#3
O(22)eZn(01)#4
O(24)eRu(02)
O(26)eZn(01)#5
O(00)#1eZn(03)
O(00)#4eRu(02)
O(24)eRu(02)eO(005)#6
O(005)#6eRu(02)eO(00)#4
2.064(9) O(006)eZn(03)#2
2.080(9) O(009)eZn(01)
1.920(7) O(23)eZn(03)
2.049(10) O(25)eRu(02)#5
1.947(10) O(27)eZn(03)
1.935(10) O(00)#3eZn(01)#1
2.077(9) Ru(02)eO(007)#2
177.7(4) O(24)eRu(02)eO(00)#4
92.9(4) O(24)eRu(02)eO(008)#2
1.909(10)
1.949(7)
1.954(7)
2.109(9)
1.970(11)
1.927(10)
2.094(9)
85.3(4)
91.7(4)
O(005)#6eRu(02)eO(008)#2 90.1(4) O(00)#4eRu(02)eO(008)#2 176.7(4)
O(24)eRu(02)eO(007)#2
O(00)#4eRu(02)eO(007)#2
O(24)eRu(02)eO(25)#7
O(00)#4eRu(02)eO(25)#7
O(22)#8eZn(01)eO(009)
94.6(4) O(005)#6eRu(02)eO(007)#2 86.8(4)
87.9(4) O(008)#2eRu(02)eO(007)#2 91.0(4)
85.9(4) O(005)#6eRu(02)eO(25)#7
92.8(4)
95.3(4) O(007)#2eRu(02)eO(25)#7 176.9(4)
104.6(4) O(22)#8eZn(01)eO(26)#7
107.6(5)
119.5(4)
95.6(4)
O(006)#3eZn(03)eO(00)#1 114.4(5) O(26)#7eZn(01)eO(009)
O(00)#1eZn(03)eO(23)
O(00)#1eZn(03)eO(27)
O(23)eZn(03)eO(27)
108.7(4) O(006)#3eZn(03)eO(23)
113.7(4) O(006)#3eZn(03)eO(27)
106.9(5)
115.5(5)
a
Symmetry transformations used to generate equivalent atoms:#1: x þ 1/
, ꢁy þ 2/5, z,#2: x ꢁ 1/2, ꢁy þ 3/2, z,#3: x þ 1/2, ꢁy þ 3/2, z,#4: x þ 1/2, ꢁy þ 3/2,
2
z þ 1,#5: x þ 1/2, ꢁy þ 1/2, z,#6: x ꢁ 1/2, ꢁy þ 5/2, z,#7: x ꢁ 1/2, ꢁy þ 1/2, z,#8:
Fig. 5. UVevis spectral change of heptametyl cobyrinate perchlorate ethanol solution
in the presence of Ru@MOF.
x ꢁ 1/2, ꢁy þ 3/2, z ꢁ 1.
Please cite this article in press as: J. Xu, et al., Journal of Organometallic Chemistry (2014), http://dx.doi.org/10.1016/j.jorganchem.2014.11.015

J. Xu et al. / Journal of Organometallic Chemistry xxx (2014) 1e7
5
Table 4
1
, 2-Migration reaction of acetyl group catalyzed by B12eRu@MOF systema.
Entry Catalyst
Solvent Conversionb Products yieldc
%)
(
Acetyl-migrated Reduced
product
product
1
2
3
4
5
B
12eRu@MOF Et
2
O
82
45
e
68
22
e
13
17
e
B12eRu@MOF EtOH
Ru@MOF
Et
12eRu@MOF Et
12, Ru
2
O
O
d
e
B
B
2
e
e
e
EtOH
54
7
35
a
2
1,2-Migration reactions were carried out in 5 mL of solvent under N atmo-
sphere with irradiation by a 200 W tungsten lamp (
l
ꢄ 420 nm) for 24 h. Initial
concentration: catalyst, 20 mg; substrate, 0.05 mmol; triethanolamine, 0.5 mmol.
b
Conversion was determined by the recovery of substrate.
Products were analyzed by GCeMS.
The reaction was carried out in the dark.
3 2
Heptamethyl cobyrinate perchlorate and [Ru(bpy) ]Cl were used.
c
d
e
2
Fig. 6. ESR spectra for B12eRu@MOF at 100 K under N .
Based on these results, we proposed the reaction mechanism
shown in Fig. 7. The Co(II) complex is reduced to Co(I) by electron
2
þ
transfer from the [Ru(bpy)
3
]
photosensitizer, and the super-
was only 45% and the yield of the acetyl migrated product
decreased to 22% with formation of a simply reduced product
nucleophilic Co(I) species reacts with the substrate to form an
alkylated cobalt complex. Visible light irradiation should induce a
cleavage of the carbonecobalt bond of the alkylated cobalt complex
to generate an alkyl radical intermediate A and Co(II) species
(
entry 2 in Table 4) since the charge neutral Co(I) state of B12 formed
in the catalytic cycle should be dissolved in ethanol and some
amount of B12 should be desorbed from the MOF during the stirring
process. Actually, the reaction did not proceed without B12 using
Ru@MOF as the catalyst (entry 3 in Table 4). Furthermore, the 1,2-
mirgration did not proceed in the dark in which the photosensi-
tizer can't work (entry 4 in Table 4). When we used B12 and Ru(b-
[28,44]. The hydrogen radical abstraction from the solvent may
produce the simple reduced product. While the channel of MOF can
prolong the lifetime of the radical intermediate A, it had enough
time convert to the acetyl migrated radical B. The radical B may
abstract a hydrogen radical to form the acetyl migrated product.
3 2
py) Cl in the absence of MOF, the conversion of the substrate is
lower and the main product is the simple reduced product as
shown by entry 5 in Table 4. Therefore, it is deduced that the
immobilization of both the B12 and Ru photosensitizer in the MOF
should facilitate photo-induced electron transfer from the Ru
photosensitizer to B12 and can enhance the 1,2-migration reaction.
Conclusion
A new bimetal MOF was synthesized by the solvothermal
method, which has a 3D 2-fold interpenetrated hex topology. The
(
2)
framework of complex 1 has a high stability and showed a gas
adsorption property. Furthermore, the cationic [Ru(bpy)
B12 are easy to immobilize into the MOF by cation exchange re-
Table 3
Dechlorination of DDT catalyzed by B12eRu@MOF systema.
2þ
3
] and
Conversionb (%)
Products yieldc
Entry
Recycle
actions. The B12eRu@MOF hybrid material worked as a heteroge-
neous catalyst for the dechlorination and 1,2-migration reactions in
the solid state and was recycled for the catalytic reaction. This is the
first example of B12 catalysis using the MOF system, and research is
now in progress on further applications of the MOF system
involving bioorganometallic B12 reactions.
DDD
1
2
3
4
1st
1st
2nd
3rd
100
e
99
d
e
e
89
76
77
63
e
a
Dechlorination were carried out in 5 mL of Et
2
O under N
2
atmosphere with
irradiation by a 200 W tungsten lamp (
catalyst, 20 mg; substrate, 0.05 mmol; triethanolamine, 2.5 mmol.
l
ꢄ 420 nm) for 4 h. Initial concentration:
Experimental section
b
Conversion was determined by the recovery of substrate.
Products were analyzed by H NMR.
The reaction was carried out in the dark.
Small amount of other dechlorinated products such as 1,1 -(2,2-
c
d
e
1
Reagents and apparatus
0
dichloroethenylidene) bis(4-chlorobenzene) (DDE) and 1,1-bis(4-chlorophenyl)-2-
chloroethane (DDMS) were formed.
All chemicals were obtained from commercial sources and were
of GR/AR grade. 2-Acetyl-1-bromo-2-ethoxycarbonylpropane was
Please cite this article in press as: J. Xu, et al., Journal of Organometallic Chemistry (2014), http://dx.doi.org/10.1016/j.jorganchem.2014.11.015

6
J. Xu et al. / Journal of Organometallic Chemistry xxx (2014) 1e7
Fig. 7. Proposed catalytic mechanism for B12eRu@MOF.
synthesized by a literature method [44]. The heptamethyl cobyri-
nate perchlorate was also synthesized by a literature method
rotating anode generator. The data frames were integrated using
SAINT (Version 6.45) [47] and merged to give a unique data set for
the structure determination. Empirical absorption corrections by
SADABS [48] were carried out. The structure was solved by a direct
method and refined by a full-matrix least-squares technique on all
F2 data using the SHELX suite of programs [49]. Non-hydrogen
atoms were refined with anisotropic displacement factors. The
details of the crystal parameters, data collection and refinements
for 1 are summarized in Table 1. Selected bond lengths and angles
for 1 are listed in Table 2.
[45,46]. The IR spectra (KBr pellets) were recorded by a JASCO FT/IR-
4
60 Plus KH spectrometer. Elemental analyses for C, H and N were
obtained from the Service Center of Elementary Analysis of Organic
Compounds at Kyushu University. The UVevis absorption spectra
1
were recorded by a Hitachi U-3310 spectrophotometer. The H NMR
spectra were recorded by a Bruker Avance 500 spectrometer. The
GCeMS were obtained using a Shimadzu GC-QP5050A equipped
with a J&W Scientific DB-1 column (length 30 m; ID 0.25 mm, film
0
.25
mm). The ESR spectra were obtained using a Bruker EMX-Plus
X-band spectrometer at 100 K under N
analyses (TGA) were performed using a TGA Hitachi TG/DTA 7300
2
. The thermogravimetric
Synthesis of Ru@MOF
ꢂ
instrument heating from room temperature to 750 C under N
2
at
Ru@MOF is prepared by mixing the complex 1 (MOF) (100 mg)
with the EtOH solution of [Ru(bpy) ]Cl (75 mg) and stirring for 5 h,
3 2
then washing several times with EtOH to give a apricot solid. The
ꢂ
the heating rate of 20 C/min. Gas sorption experiments were
carried out using a Belsorp-max volumetric gas sorption instru-
ment. Samples were outgassed under a high vacuum (less than
2þ
amount of [Ru(bpy)
3
]
in the MOF was determined by ICP-MS as
ꢁ
5
ꢂ
10
Torr) at 100 C for 20 h, and the sample was weighed before
ꢁ1
0.09 mmol/100 mg MOF. IR (KBr pellet, cm ): 3072 (ms), 1684 (s),
and after the degassing procedure to confirm the complete evac-
uation of the solvents. ICP-MS analyses were obtained using an
Agilent Technologies Agilent 7500C.
1
606 (s), 1541 (s), 1423 (ms), 1394 (s), 1179 (ms), 1005 (ms), 847 (s),
770 (s), 703 (ms), 679 (m) (Fig. S1).
Synthesis of B12eRu@MOF
12eRu@MOF was prepared by mixing the Ru@MOF (200 mg)
Synthesis of complex 1 (MOF)
B
The MOF {Zn
4
Ru
2
(bpdc)
4
$4C
2
NH
8
$9DMF}
n
was prepared by the
with the EtOH solution of B12 (heptamethyl cobyrinate perchlorate)
(10 mg) and stirring for 5 h, then washing several times with EtOH
addition of 2.0 mg (0.004 mmol) of Ru(bpy)
2
Cl
2
, 21.0 mg
0
2þ
(
0.09 mmol) of 4,4 -biphenyldicarboxylic acid (H
2
bpdc) and 11.8 mg
to give a brown solid. The amounts of B and [Ru(bpy)3] were
1
2
ꢁ
3
(
0.04 mmol) of Zn(NO
3
)
2
$6H
2
O in a solvent mixture of 0.45 mL DMF
determined by ICP-MS as 2.8 ꢀ 10 mmol and 0.126 mmol/200 mg
ꢁ
1
with 10
m
L AcOH under solvothermal conditions. Dark red crystals
MOF, respectively. IR (KBr pellet, cm ): 3415 (ms), 1606 (s), 1538
(s), 1393 (s), 1005 (ms), 855 (s), 771 (s), 681 (m) (Fig. S1).
ꢂ
were obtained at 100 C after 6 days with a yield of 36%. Anal. Calcd.
for C147
C, 54.24%; H, 4.78%; N, 5.82%. IR (KBr pellet, cm ): 3069 (ms), 1660
s), 1606 (s), 1541 (s), 1387 (s), 1177 (ms), 1005 (ms), 847 (s), 770 (s),
03 (ms), 681 (m) (Fig. S1).
159 13 2 4
H N O41Ru Zn (1): C, 54.82%; H, 4.85%; N, 5.66%. Found:
ꢁ1
General procedure of catalytic photoreaction
(
7
A
typical example of the photoreaction catalyzed by
12eRu@MOF is shown below. In the presence of a sacrificial re-
agent (triethanolamine), 20 mg of the catalyst and 0.05 mmol
substrate in 5 mL of diethyl ether were stirred in a N atmosphere
with irradiation by a 200 W tungsten lamp through a cut-off filter
ꢄ 420 nm). After the photoreaction, the product was extracted by
diethyl ether and hexane, then washed by water for several times.
B
Crystal structure determination
2
The crystallographic data of 1 were collected at 93 K by a Bruker
APEX II ULTRA CCD system equipped with graphite-
(l
monochromated MoK
a
radiation (
l
¼ 0.71073 Å) and a 2 kW
Please cite this article in press as: J. Xu, et al., Journal of Organometallic Chemistry (2014), http://dx.doi.org/10.1016/j.jorganchem.2014.11.015

J. Xu et al. / Journal of Organometallic Chemistry xxx (2014) 1e7
[12] J.L. Wang, C. Wang, W.B. Lin, ACS Catal. 2 (2012) 2630e2640.
7
The organic layer was analyzed by GCeMS using diphenyl as the
[13] K.E. deKrafft, Z. Xie, G. Cao, S. Tran, L. Ma, O.Z. Zhou, W. Lin, Angew. Chem. Int.
Ed. Engl. 48 (2009) 9901e9904.
internal standard. For the dechlorination of DDT, the product was
analyzed and quantified by a H NMR measurement using 1,4-
1
[14] R.J. Della, W. Lin, Eur. J. Inorg. Chem. 24 (2010) 3725e3734.
dioxane as the internal standard. The recovered catalyst was
washed with Et O, dried under vacuum, then reused again.
2
[15] D. Liu, R.C. Huxford, W. Lin, Angew. Chem. Int. Ed. Engl. 50 (2011) 3696e3700.
[
[
16] W.J. Rieter, K.M. Pott, K.M. Taylor, W. Lin, J. Am. Chem. Soc. 130 (2008)
1584e11585.
17] W. Lin, W.J. Rieter, K.M. Taylor, Angew. Chem. Int. Ed. Engl. 48 (2009)
650e658.
1
Acknowledgments
[18] C. Wang, D.M. Liu, W.B. Lin, J. Am. Chem. Soc. 135 (2013) 13222e13234.
[
19] K. oꢀ Proinsias, M. Giedyk, D. Gryko, Chem. Soc. Rev. 42 (2013) 6606e6619.
[
20] K. Gruber, B. Puffer, B. Kr €a utler, Chem. Soc. Rev. 40 (2011) 4346e4363.
This study was partially supported by the Global COE Program
“
Science for Future Molecular Systems” from the Ministry of Edu-
[21] W. Buckel, B.T. Golding, Annu. Rev. Microbiol. 60 (2006) 27e49.
[
[
[
22] K.L. Brown, Chem. Rev. 105 (2005) 2075e2149.
23] M.A. Jabbar, H. Shimakoshi, Y. Hisaeda, Chem. Commun. (2007) 1653e1655.
24] H. Shimakoshi, M. Tokunaga, Y. Hisaeda, Dalton Trans. (2004) 878e882.
cation, Culture, Sports, Science and Technology (MEXT) of Japan,
and a Grant-in-Aid for Challenging Exploratory Research (No.
2
2
4655134) and a Grant-in-Aid for Scientific Research (C) (No.
3550125) from the Japan Society for the Promotion of Science
[25] Y. Hisaeda, H. Shimakoshi, in: K.M. Kadish, K.M. Smith, R. Guilard (Eds.), In
Handbook of Porphyrin Science, vol. 10, World Scientific, 2010, pp. 313e370.
[
[
[
[
[
[
26] Y. Murakami, Y. Hisaeda, A. Ogawa, T. Ohno, J. Chem. Soc. Perkin Trans. 2
1995) 189e191.
27] Y. Murakami, Y. Hisaeda, X.M. Song, T. Ohno, J. Chem. Soc. Perkin Trans. 2
(1992) 1527e1528.
28] Y. Murakami, Y. Hisaeda, J. Kikuchi, T. Ohno, M. Suzuki, Y. Matsuda,
T. Matsuura, J. Chem. Soc. Perkin Trans. 2 (1988) 1237e1246.
29] The Reticular Chemistry Structure Resource at the website of O'Keeffe group
(http://rcsr.anu.edu.au/).
30] A.F. Well, Three-dimensional Nets and Polyhedra, Wiley-Inter-Science, New
York, 1977.
(
JSPS), and the 2014 Tokuyama Science Foundation.
(
Appendix A. Supplementary material
CCDC 1024277 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge from
The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.
uk/data_request/cif.
31] A.L. Spek, PLATON, a Multipurpose Crystallographic Tool, Utrecht University,
Utrecht, The Netherlands, 2003.
[
[
[
32] A.X. Zhu, J.B. Lin, J.P. Zhang, X.M. Chen, Inorg. Chem. 48 (2009) 3882e3889.
33] B. Mu, F. Li, K.S. Walton, Chem. Commun. (2009) 2493e2495.
34] O.M. Yaghi, H. Li, J. Am. Chem. Soc. 117 (1995) 10401e10402.
Appendix B. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.jorganchem.2014.11.015.
[35] S.R. Halper, L. Do, J.R. Stork, S.M. Cohen, J. Am. Chem. Soc. 128 (2006)
5255e15268.
36] F. Nouar, J. Eckert, J.F. Eubank, P. Forster, M. Eddaoudi, J. Am. Chem. Soc. 131
2009) 2864e2870.
[37] J. An, N.L. Rosi, J. Am. Chem. Soc. 132 (2010) 5578e5579.
1
[
(
References
[
38] E.Q. Procopio, F. Linares, C. Montoro, V. Colombo, A. Maspero, E. Barea,
[
1] H.X. Deng, S. Grunder, K.E. Cordova, C. Valente, H. Furukawa, M. Hmadeh,
J.A.R. Navarro, Angew. Chem. Int. Ed. 49 (2010) 7308e7311.
F. G aꢀ ndara, A.C. Whalley, Z. Liu, S. Asahina, H. Kazumori, M. O'Keeffe,
[39] S. Yang, G.S.B. Martin, J.J. Titman, A.J. Blake, D.R. Allan, N.R. Champness,
M. Schr
o€ der, Inorg. Chem. 50 (2011) 9374e9384.
O. Terasaki, J.F. Stoddart, O.M. Yaghi, Science 336 (2012) 1018e1023.
2] M.M. Deshmukh, M. Ohba, S. Kitagawa, S. Sakaki, J. Am. Chem. Soc. 135 (2013)
[
[
[
[40] M. Kim, J.F. Cahill, H.H. Fei, K.A. Prather, S.M. Cohen, J. Am. Chem. Soc. 134
(2012) 18082e18088.
[41] M. Sadakiyo, H. Kasai, K. Kato, M. Takata, M. Yamauchi, J. Am. Chem. Soc. 136
(2014) 1702e1705.
[42] T.K. Maji, R. Matsuda, S. Kitagawa, Nat. Mater. 6 (2014) 142e148.
[43] H. Shimakoshi, L. Li, M. Nishi, Y. Hisaeda, Chem. Commun. 47 (2011)
10921e10923.
[44] Y. Murakami, Y. Hisaeda, T. Ozaki, T. Tashiro, T. Ohno, Y. Tani, Y. Matsuda, Bull.
Chem. Soc. Jpn. 60 (1987) 311e324.
[45] L. Werthemann, ETH Zürich (No. 4097), Dissertation, Juris Druck and Verlag,
Zürich, 1968.
[46] Y. Murakami, Y. Hisaeda, A. Kajihara, Bull. Chem. Soc. Jpn. 56 (1982)
3642e3646.
[47] SAINT, Data Reduction Software, Version 6.45A, Bruker Advanced X-ray So-
lution, Inc., Madison,WI, 2001.
[48] G.M. Sheldrick, SADABS, University of Goettingen, Germany, 1996.
[49] G.M. Sheldrick, SHELXL97 and SHELXS97, University of Goettingen, Germany,
1997.
4840e4849.
3] N. Yanai, T. Uemura, M. Inoue, R. Matsuda, T. Fukushima, M. Tsujimoto,
S. Isoda, S. Kitagawa, J. Am. Chem. Soc. 134 (2012) 4501e4504.
4] M.D. Allendorf, R.J. Houk, L. Andruszkiewicz, A.A. Talin, J. Pikarsky,
A. Choudhury, K.A. Gall, P.J. Hesketh, J. Am. Chem. Soc. 130 (2008)
14404e14405.
[
[
5] A. Lan, K. Li, H. Wu, D.H. Olson, T.J. Emge, W. Ki, M. Hong, J.E. Li, Angew. Chem.
Int. Ed. Engl. 48 (2009) 2334e2338.
6] Z. Xie, L. Ma, K.E. deKrafft, A. Jin, W. Lin, J. Am. Chem. Soc. 131 (2009)
922e923.
[7] G. Lu, J.T. Hupp, J. Am. Chem. Soc. 132 (2010) 7832e7833.
[8] C. Wang, M. Zheng, W.B. Lin, J. Phys. Chem. Lett. 2 (2011) 1701e1709.
[9] J.M. Falkowski, T. Sawano, T. Zhang, G. Tsun, Y. Chen, J.V. Lockard, W.B. Lin,
J. Am. Chem. Soc. 136 (2014) 5213e5216.
[
[
10] L. Ma, J.M. Falkowski, C. Abney, W. Lin, Nat. Chem. 2 (2010) 838e846.
11] L.C. Li, R. Matsuda, I. Tanaka, H. Sato, P. Kanoo, H.J. Jeon, M.L. Foo,
A. Wakamiya, Y. Murata, S. Kitagawa, J. Am. Chem. Soc. 136 (2014)
7543e7546.
Please cite this article in press as: J. Xu, et al., Journal of Organometallic Chemistry (2014), http://dx.doi.org/10.1016/j.jorganchem.2014.11.015