Communication
ChemComm
with non-metalated PCN-308 as a catalyst showed no activity in the
borylation reaction. The borylated products could also be obtained
9 Q.-H. Xia, H.-Q. Ge, C.-P. Ye, Z.-M. Liu and K.-X. Su, Chem. Rev.,
2
005, 105, 1603.
1
0 M. Rimoldi, A. Nakamura, N. A. Vermeulen, J. J. Henkelis, A. K.
Blackburn, J. T. Hupp, J. F. Stoddart and O. K. Farha, Chem. Sci.,
2016, 7, 4980.
from the homogeneous catalytic counterpart, [(CO Me) ]tpy-
2
3
Co(OAc) , under the same conditions. However, the yields were
2
1
1
1
1
1 L. Zhang, J. Chen, T. Fan, K. Shen, M. Jiang and Y. Li, Chem.
Commun., 2018, 54, 4188.
2 J. S. Qin, S. Yuan, C. Lollar, J. Pang, A. Alsalme and H. C. Zhou,
Chem. Commun., 2018, 54, 4231.
much lower, demonstrating the necessity of active site isolation in
the MOF struts (Table S5, ESI†). Co@PCN-308 can be easily
separated and recovered from the reaction system by filtration.
Its structural integrity was evaluated by the PXRD patterns, which
deviate slightly from that of the as-synthesized PCN-308 (Fig. S26,
3 X. Wang, W. Lu, Z.-Y. Gu, Z. Wei and H.-C. Zhou, Chem. Commun.,
2016, 52, 1926.
4 A. Togni and L. M. Venanzi, Angew. Chem., Int. Ed., 1994, 33, 497.
ESI†). The catalyst could also be reused for at least three cycles 15 Y. Zhang, X. Yang and H.-C. Zhou, Polyhedron, 2018, 154, 189.
6 K. Manna, T. Zhang, F. X. Greene and W. Lin, J. Am. Chem. Soc.,
015, 137, 2665.
1
without remarkable loss of catalytic activity (Fig. S27, ESI†).
2
In summary, a tritopic terpyridine-based linker (H TPY) was
3
17 T. Sawano, N. C. Thacker, Z. Lin, A. R. McIsaac and W. Lin, J. Am.
Chem. Soc., 2015, 137, 12241.
judiciously designed and utilized to construct a mesoporous
MOF, PCN-308, with predictable b-cristobalite topology. Due to
the direct one-pot synthesis, the terpyridine-based chelating
sites were evenly distributed on the scaffold, which could be
easily accessed by post-synthetic metalation of redox-active
metal ions under mild conditions. The scaffolded MOF materials,
Fe@PCN-308 and Co@PCN-308, contained high loadings of
catalytic centers and turned out to be efficient catalysts for
alkene expoxidation and arene borylation, respectively. This
work exemplified the introduction of terpyridine-based pincer
complexes into 3D mesoporous MOF structures, providing a
successful approach to utilize the MOF scaffold in the preparation
of pincer-type heterogeneous catalysts.
1
8 C. Zhu, Q. Xia, X. Chen, Y. Liu, X. Du and Y. Cui, ACS Catal., 2016,
, 7590.
6
19 Y. Wang, H. Cui, Z. W. Wei, H. P. Wang, L. Zhang and C. Y. Su,
Chem. Sci., 2017, 8, 775.
2
2
0 C. Wang, J. L. Wang and W. Lin, J. Am. Chem. Soc., 2012, 134, 19895.
1 S. A. Burgess, A. Kassie, S. A. Baranowski, K. J. Fritzsching,
K. Schmidt-Rohr, C. M. Brown and C. R. Wade, J. Am. Chem. Soc.,
2016, 138, 1780.
2
2
2
2
2
2
2 J. He, N. W. Waggoner, S. G. Dunning, A. Steiner, V. M. Lynch and
S. M. Humphrey, Angew. Chem., Int. Ed. Engl., 2016, 55, 12351.
3 A. M. Rasero-Almansa, A. Corma, M. Iglesias and F. S ´a nchez,
ChemCatChem, 2013, 5, 3092.
4 A. M. Rasero-Almansa, A. Corma, M. Iglesias and F. S ´a nchez,
ChemCatChem, 2014, 6, 1794.
5 P. Liu, C.-Y. Zhou, S. Xiang and C.-M. Che, Chem. Commun., 2010,
46, 2739.
6 N. G. L ´e onard, M. J. Bezdek and P. J. Chirik, Organometallics, 2016,
This work was supported by the Center for Gas Separations
Relevant to Clean Energy Technologies, an Energy Frontier
Research Center funded by the U.S. Department of Energy, Office
of Science, Office of Basic Energy Sciences (DE-SC0001015), U.S.
Department of Energy, Office of Fossil Energy, National Energy
36, 142.
7 A. Winter, G. R. Newkome and U. S. Schubert, ChemCatChem, 2011,
3, 1384.
2
2
8 E. Peris and R. H. Crabtree, Chem. Soc. Rev., 2018, 47, 1959.
9 M. Zheng, H. Tan, Z. Xie, L. Zhang, X. Jing and Z. Sun, ACS Appl.
Mater. Interfaces, 2013, 5, 1078.
Technology Laboratory (DE-FE0026472) and Robert A. Welch 30 J. Zhang, W. Yang, X.-Y. Wu, L. Zhang and C.-Z. Lu, Cryst. Growth
Des., 2015, 16, 475.
1 W. Wang, Z. Xiao, H. Lin, R. Wang, L. Zhang and D. Sun, RSC Adv.,
Foundation through a Welch Endowed Chair to H. J. Z. (A-0030).
The authors also acknowledge the financial support of NPRP award
NPRP9-377-1-080 from the Qatar National Research Fund.
3
2016, 6, 16575.
32 Y. L. Gai, F. L. Jiang, L. Chen, Y. Bu, M. Y. Wu, K. Zhou, J. Pan and
M. C. Hong, Dalton Trans., 2013, 42, 9954.
3
3
3 Z. Lin, N. C. Thacker, T. Sawano, T. Drake, P. Ji, G. Lan, L. Cao,
S. Liu, C. Wang and W. Lin, Chem. Sci., 2018, 9, 143.
4 L. Cao, Z. Lin, F. Peng, W. Wang, R. Huang, C. Wang, J. Yan, J. Liang,
Z. Zhang, T. Zhang, L. Long, J. Sun and W. Lin, Angew. Chem., Int.
Ed., 2016, 55, 4962.
Conflicts of interest
There are no conflicts to declare.
3
5 M. J. Cliffe, E. Castillo-Martinez, Y. Wu, J. Lee, A. C. Forse, F. C. N.
Firth, P. Z. Moghadam, D. Fairen-Jimenez, M. W. Gaultois, J. A. Hill,
O. V. Magdysyuk, B. Slater, A. L. Goodwin and C. P. Grey, J. Am.
Chem. Soc., 2017, 139, 5397.
Notes and references
1
2
H. C. Zhou, J. R. Long and O. M. Yaghi, Chem. Rev., 2012, 112, 673.
H. Furukawa, K. E. Cordova, M. O’Keeffe and O. M. Yaghi, Science, 36 M. Zhao, Q. Lu, Q. Ma and H. Zhang, Small Methods, 2017, 1, 1600030.
2
013, 341, 1230444.
37 W. Xu, K. B. Thapa, Q. Ju, Z. Fang and W. Huang, Coord. Chem. Rev.,
2018, 373, 199.
3
4
H. Wang, Q.-L. Zhu, R. Zou and Q. Xu, Chemistry, 2017, 2, 52.
P. Ramaswamy, N. E. Wong and G. K. Shimizu, Chem. Soc. Rev., 38 D. Feng, K. Wang, J. Su, T. F. Liu, J. Park, Z. Wei, M. Bosch, A. Yakovenko,
014, 43, 5913. X. Zou and H. C. Zhou, Angew. Chem., Int. Ed. Engl., 2015, 54, 149.
I. Nath, J. Chakraborty and F. Verpoort, Chem. Soc. Rev., 2016, 45, 4127. 39 H. Liu, C. Xu, D. Li and H.-L. Jiang, Angew. Chem., Int. Ed., 2018,
2
5
6
M. Rimoldi, A. J. Howarth, M. R. DeStefano, L. Lin, S. Goswami,
P. Li, J. T. Hupp and O. K. Farha, ACS Catal., 2016, 7, 997.
L. Zhu, X. Q. Liu, H. L. Jiang and L. B. Sun, Chem. Rev., 2017,
57, 5379.
40 I. Accelrys, Accelerys Materials Studio Release Notes, Accelrys Software
Inc., 2010.
41 J. V. Obligacion, S. P. Semproni and P. J. Chirik, J. Am. Chem. Soc.,
2014, 136, 4133.
7
8
1
17, 8129.
S. Yuan, L. Feng, K. Wang, J. Pang, M. Bosch, C. Lollar, Y. Sun,
J. Qin, X. Yang and P. Zhang, Adv. Mater., 2018, 1704303.
42 T. Zhang, K. Manna and W. Lin, J. Am. Chem. Soc., 2016, 138, 3241.
Chem. Commun.
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