Because Cu(OAc)2ꢀH2O comprises of a basic anion, we have used
Cu(OAc)2ꢀH2O instead of solid 1 to conduct the catalytic
experiment. The product yield can reach to 42% after 3.5 h,
which indicates that Cu(OAc)2ꢀH2O prompted catalytic reaction is
faster than that of 1 (18% after 3.5 h). However, the Cu(OAc)2ꢀH2O
catalyzed product yield cannot be significantly improved when
the reaction time was prolonged, which is similar to the
literature reports.11,12 When Cu(NO3)ꢀ3H2O was used as a
catalyst, and H4pdtc and HL were used as additives, no
product was detected. These results indicate that the catalytic
centers might be partially ligated by the nitrate anions, or even
further blocked by the ligands, which cannot be easily accessed
by the substrates.
c = 21.500(2) A, a = 100.072(9)1, b = 93.060(7)1, g = 106.834(8)1,
V = 3142.5(5) A3, and Z = 2, T = 293 K, Rint = 0.0623, Dc = 1.092
g cmꢂ3, m = 1.612 mmꢂ1, F(000) = 1050, R1 = 0.1221, wR2 = 0.2661,
and S = 1.058.
z A typical procedure for the Henry reaction catalyzed by MOF 1: to
a solution of CH3NO2 (0.6 mL) and 4-nitrobenzaldehyde (8 mg,
0.05 mmol), catalyst 1 (10 mol%) was added. The mixture was heated
at 70 1C for 36 h, which was subsequently quenched by centrifugation
and filtration. The filtrate was evaporated under reduced pressure at
room temperature. The crude product was passed through a column of
silica gel using petroleum ether and ethyl acetate as eluent followed by
vacuum evaporation at room temperature. The identity of the product
was determined by 1H-NMR spectroscopy, while the yield was
obtained by HPLC analysis using an Ultimate XB-C18 column
(5 mm, 4.6 ꢁ 250 mm2).
1 (a) S. Kitagawa, R. Kitaura and S.-i. Noro, Angew. Chem., Int.
Ed., 2004, 43, 2334; (b) J. Long and O. M. Yaghi, Chem. Soc. Rev.,
2009, 38(5), 1213.
2 (a) O. Ohmori and M. Fujita, Chem. Commun., 2004, 1586;
(b) J.-P. Zhang and S. Kitagawa, J. Am. Chem. Soc., 2008, 130,
907; (c) P. A. Maggard, B. Yan and J. Luo, Angew. Chem., Int. Ed.,
2005, 44, 2553; (d) B. Chen, M. Eddaoudi, T. M. Reineke,
J. W. Kampf, M. O’keeffe and O. M. Yaghi, J. Am. Chem. Soc.,
2000, 122, 11559.
After a mixture of 1 and nitromethane was heated at 70 1C
for 36 h under stirring, elementary analysis showed that only
6 ꢁ 10ꢂ3 percent of the copper cations were released into the
solution. The filtrate was subsequently used to react with
4-nitrobenzaldehyde at 70 1C for another 36 h. HPLC analysis
suggests that the mixture is unreactive, which thus demon-
strated the heterogeneous catalytic behavior of 1 in nature.
Catalyst 1 can be simply recovered by filtration, which was
subsequently used in the successive runs without decreasing
the catalytic activity (Table 1, entry 9). A PXRD pattern for
the recovered material showed that the structural integrity of
the catalyst was maintained during the catalytic process.
In summary, we have employed two kinds of pyridine
carboxylate ligands to construct a novel 3D porous MOF 1
containing very large 1D opening channels. The coordination
sites of one kind of copper atom are accessible, and the water
ligands can be substituted by pyridine and EtOH molecules.
The immobilized catalytically active copper centers in the
channel walls of 1 can prompt the Henry reaction of benz-
aldehydes with nitroalkanes, which is superior to that of its
compositions as the homogeneous metal coordination sites are
easily ligated by the counter ions.
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D.-Y. Hong, J.-S. Chang, S. H. Jhung, Y.-K. Seo, J. Kim,
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Int. Ed., 2008, 47, 4144; (d) S. Horike, M. Dinca, K. Tamaki and
J. R. Long, J. Am. Chem. Soc., 2008, 130, 5854; (e) M. Banerjee,
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38, 1477; (b) L. J. Murray, M. Dinca and J. R. Long, Chem. Soc.
Rev., 2009, 38, 1294; (c) M. Dinca and J. R. Long, Angew. Chem.,
Int. Ed., 2008, 47, 6766; (d) S. Xiang, W. Zhou, Z. Zhang,
M. A. Green, Y. Lin and B. Chen, Angew. Chem., Int. Ed., 2010,
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E. B. Lobkovsky, Adv. Mater., 2007, 19, 1693; (b) K.-L. Wong,
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6312; (b) Z. Wang, K. K. Tanabe and S. M. Cohen, Inorg. Chem.,
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Y. Yoshida, S. Isoda and S. Kitagawa, Angew. Chem., Int. Ed.,
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This work was financially supported by the NSF of China
(Grant No. 21073158), Zhejiang Provincial Natural Science
Foundation of China (Grant No. Z4100038) and the
Fundamental Research Funds for the Central Universities
(Grant No. 2010QNA3013).
Notes and references
z Synthesis of [Cu3(pdtc)L2(H2O)3]ꢀ2DMFꢀ10H2O (1): after a solution
of Cu(NO3)ꢀ3H2O (3 mg, 0.012 mmol) and H4pdtc (3 mg, 0.012 mmol)
in H2O (2.4 mL) was stirred at room temperature for 10 h, 3.6 mL
solution of HL in DMF (5.0 mmol Lꢂ1) was added. The resulting
mixture was sealed in a capped vial at 90 1C, which formed green
crystals of 1 after one day (yield: 56%). Anal. Calcd for 1 (%): H, 4.84;
C, 40.65; N, 5.51. Found: H, 4.78; C, 40.67; N, 5.56. IR (KBr pellet)
cmꢂ1: 776(w), 817(w), 852(w), 1156(w), 1319(s), 1384(s), 1544(w),
1613(s). Synthesis of [Cu3(pdtc)L2(H2O)(EtOH)(Py)] (2): the freshly
prepared sample of 1 was washed by ethanol three times, which was
subsequently immersed in a mixed solvent of pyridine and ethanol
(VPyridine/VEtOH = 1/100) at room temperature for one week to yield
blue crystals of 2.
7 (a) A.-H. Yang, H. Zhang, P. Yin, H.-L. Gao, J.-Z. Cui and B. Ding,
Inorg. Chem. Commun., 2010, 13, 1304; (b) S.-T. Yan, L.-X. Shi,
F.-F. Sun and C.-D. Wu, CrystEngComm, 2010, 12, 3437.
8 A. L. Spek, PLATON,
a multipurpose crystallographic tool,
Utrecht University, Utrecht, The Netherlands, 2001.
9 (a) N. Ono, The Nitro Group in Organic Synthesis, Wiley-VCH,
New York, 2001; (b) B. M. Trost and V. S. C. Yeh, Angew. Chem.,
Int. Ed., 2002, 41, 861; (c) Y. Xiong, F. Wang, X. Huang, Y. Wen
and X. Feng, Chem.–Eur. J., 2007, 13, 829.
10 (a) K. R. Reddy, C. V. Rajasekhar and G. G. Krishna, Synth.
Commun., 2007, 37, 1971; (b) J. Tian, N. Yamagiwa, S. Matsunaga
and M. Shibasaki, Angew. Chem., Int. Ed., 2002, 41, 3636;
(c) S. Jammi and T. Punniyamurthy, Eur. J. Inorg. Chem., 2009,
2508; (d) T. Arai, M. Watanabe and A. Yanagisawa, Org. Lett.,
2007, 9, 3595.
y Crystal data for [Cu3(pdtc)L2(H2O)3]ꢀ2DMFꢀ10H2O (1): C43H61Cu3-
ꢀ
N5O27, Mr = 1270.59, triclinic, space group P1, a = 10.0358(6) A,
b = 15.9728(9) A, c = 21.559(1) A, a = 98.333(5)1, b = 93.782(5)1,
g = 107.759(5)1, V = 3234.1(3) A3, and Z = 2, T = 293 K, Rint = 0.0612,
Dc
=
1.305 gꢀcmꢂ3
,
m
=
1.817 mmꢂ1
R1 = 0.0573, wR2 = 0.1272, and S = 0.959. Crystal data for
,
F(000)
=
1314,
11 S. Jammi, M. A. Ali, S. Sakthivel, L. Rout and T. Punniyamurthy,
Chem.–Asian J., 2009, 4, 314.
[Cu3(pdtc)L2(H2O)(EtOH)(Py)] (2): C44H32Cu3N6O11, Mr = 1011.38,
ꢀ
triclinic, space group P1, a = 9.9506(7) A, b = 15.682(2) A,
12 Y. Xiong, F. Wang, X. Huang, Y. Wen and X. Feng, Chem.–Eur.
J., 2007, 13, 829.
c
2930 Chem. Commun., 2011, 47, 2928–2930
This journal is The Royal Society of Chemistry 2011