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The high uptake capacity of 10 for CO2 and H2 was studied
theoretically as well.
Table 2 Cycloaddition of various epoxides with CO2 through purging of
atmospheric air at 298 K
We gratefully acknowledge the financial support received
from the MNRE, New Delhi, India (to P. K. B and D. D.). P.K.B.
and P. K. C. thank DST for JCB Fellowships. V. S. thanks
University Grants Commission (UGC), New Delhi, India.
Entry
1
Epoxide
Product
Time (h)
24
Yields (%)
62
2
24
45
Conflicts of interest
There are no conflicts to declare.
3
4
24
8
57
30
Notes and references
1 (a) Q. Wang, J. Luo, Z. Zhong and A. Borgna, Energy Environ. Sci.,
2011, 4, 42–55; (b) H. Y. Cho, D.-A. Yanga, J. Kim, S. Y. Jeong and
¨
W.-S. Ahn, Catal. Today, 2012, 185, 35–40; (c) R. Dawson, E. Stockel,
J. R. Holst, D. J. Adams and A. I. Cooper, Energy Environ. Sci., 2011, 4,
4239–4245.
(Scheme S2, ESI†) for this CO2 fixation reaction was similar to
those reported by other groups using paddle-wheel Cu2(COO)4
SBUs and TBAB as co-catalysts.14 10 promoted the ring-opening
of the epoxide with the help of Bu4NBr to afford a Cu-bound
alkoxide in an SN2-type reaction. The subsequent addition of
CO2 to the ring-opened epoxide was preferred by the presence
of Bu4NBr, which stabilized the polarized intermediate resulting in
a metal carbonate capable of cyclization to form a cyclic carbonate
with the regeneration of the catalyst. In the absence of the
co-catalyst TBAB, the reaction catalysed by 10 yielded 19% after
8 h. Furthermore, in the absence of 10, the same reaction catalysed
by the co-catalyst TBAB alone gave only 10% yield. The combination
of 10 and TBAB afforded the optimal yields (Table 1, entry 1).
The excellent catalytic activity of 10 for the chemical fixation
of CO2 enthused us to further explore this reaction through
purging of atmospheric air. The results were quite interesting
(Table 2) and the product yield was 45% based on 2-(chloro-
methyl)oxirane as a substrate at room temperature for 15 h of
reaction. The yield could be increased up to 62% when the
reaction was continued for 24 h. The results with other epoxides
were also encouraging as collected in Table 2.
In summary, the new linker described herein formed a
thermally stable 3D framework with Cu(II) ions under solvo-
thermal conditions. Both the metal bound and lattice solvent
molecules could be removed upon heating to afford a highly
porous compound whose overall architecture was maintained.
The presence of free amino groups in the channels along with
uncoordinated metal centers led to very high H2 and CO2
adsorption by the MOF. Even CH4 adsorption was very high.
The adsorbed CO2 could easily be converted to cyclic carbo-
nates on reacting with epoxides at room temperature. Most
importantly, the MOF could convert CO2 from laboratory
air and make a cyclic carbonate in the presence of an epoxide.
2 (a) K. Biggadike, R. M. Angell, C. M. Burgess, R. M. Farrell, A. P.
Hancock, A. J. Harker, W. R. Irving, C. Loannou, P. A. Procopiou, R. E.
Shaw, Y. E. Solanke, O. M. P. Singh, M. A. Snowden, R. J. Stubbs,
S. Walton and H. E. Weston, J. Med. Chem., 2000, 43, 19–21;
(b) A. A. G. Shaikh and S. Sivaram, Chem. Rev., 1996, 96, 951–976.
3 J. Ma, N. Sun, X. Zhang, N. Zhao, F. Xiao, W. Wei and Y. Sun, Catal.
Today, 2009, 148, 221–231.
4 R. L. Paddock and S. B. T. Nguyen, J. Am. Chem. Soc., 2001, 123,
11498–11499.
5 D. J. Darensbourg and M. W. Holtcamp, Coord. Chem. Rev., 1996,
153, 155–174.
6 (a) C. D. N. Gomes, O. Jacquet, C. Villiers, P. Thuery, M. Ephritikhine
and T. A. Cantat, Angew. Chem., Int. Ed., 2012, 51, 187–190; (b) X.-B.
Lu and D. J. Darensbourg, Chem. Soc. Rev., 2012, 41, 1462–1484;
(c) K. Iizuka, T. Wato, Y. Miseki, K. Saito and A. Kudo, J. Am. Chem.
Soc., 2011, 133, 20863–20868; (d) S. Lin, C. S. Diercks, Y.-B. Zhang,
N. Kornienko, E. M. Nichols, Y. Zhao, A. R. Paris, D. Kim, P. Yang,
O. M. Yaghi and C. J. Chang, Science, 2015, 349, 1208–1213.
7 (a) S. Fukuoka, M. Kawamura, K. Komiya, M. Tojo, H. Hachiya,
K. Hasegawa, M. Aminaka, H. Okamoto, I. Fukawa and S. Konno,
Green Chem., 2003, 5, 497–507; (b) M. Yoshida and M. Ihara,
Chem. – Eur. J., 2004, 10, 2886–2893.
8 L. Schlapbach and A. Zu¨ttel, Nature, 2001, 414, 353–358.
9 G. S. Pawley, J. Appl. Crystallogr., 1981, 14, 357–361.
10 A. L. Spek, J. Appl. Crystallogr., 2003, 36, 7–13.
´
11 (a) G. Ferey, C. Mellot-Draznieks, C. Serre, F. Millange, J. Dutour,
S. Surble and I. Margiolaki, Science, 2005, 309, 2040–2042; (b) L.-G.
Qiu, T. Xu, Z.-Q. Li, W. Wang, Y. Wu, X. Jiang, X.-Y. Tian and
L.-D. Zhang, Angew. Chem., Int. Ed., 2008, 47, 9487–9491.
12 (a) S. Bourrelly, P. L. Llewellyn, C. Serre, F. Millange, T. Loiseau and
´
G. Ferey, J. Am. Chem. Soc., 2005, 127, 13519–13521; (b) I. Senkovska
and S. Kaskel, Microporous Mesoporous Mater., 2008, 112, 108–115;
(c) H. Wu, W. Zhou and T. Yildirim, J. Am. Chem. Soc., 2009, 131,
4995–5000; (d) P. D. C. Dietzel, V. Besikiotis and R. Blom, J. Mater.
Chem., 2009, 19, 7362–7370; (e) X.-S. Wang, S. Ma, K. Rauch, J. M.
´
Simmons, D. Yuan, X. Wang, T. Yildirim, W. C. Cole, J. J. Lopez,
A. D. Meijere and H.-C. Zhou, Chem. Mater., 2008, 20, 3145–3152.
13 (a) D. De, T. K. Pal, S. Neogi, S. Senthilkumar, D. Das, S. S. Gupta
and P. K. Bharadwaj, Chem. – Eur. J., 2016, 22, 3387–3396; (b) T. K.
Pal, D. De, S. Senthilkumar, S. Neogi and P. K. Bharadwaj, Inorg.
Chem., 2016, 55, 7835–7842.
14 P.-Z. Li, X.-J. Wang, J. Liu, J. S. Lim, R. Zou and Y. Zhao, J. Am. Chem.
Soc., 2016, 138, 2142–2145.
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