Journal of the American Chemical Society
Page 8 of 10
Laboratory (DEꢀFE0026472) and Qatar National Research Fund
(NPRP9ꢀ377ꢀ1ꢀ080).
Figure 4. (a) Yields and (b) TON values of BrꢀPCNꢀ224(Fe)
in the oxidation reaction of 3ꢀmethyl pentane over the five
cycles.
1
2
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In summary, four isoreticular analogues of the PCNꢀ224(Fe)
have been successfully developed. By insertion of ethyl, broꢀ
mo, chloro, and fluoro units into the βꢀposition of TCPP ligand,
the four MOFs allow for a systematic single substitution study.
Incorporation of simple substitution groups remarkably inꢀ
creases both the activity and selectivity of MOFꢀembedded
iron sites for 3ꢀmethyl pentane oxidation catalysis without
directly changing the topological structure, crystallinity, and
porosity of the frameworks. Periphery modification of catalytꢀ
ic sites and single substitution engineering may prove to be
highly effective on the control over catalytic performance in
the context of many other MOFs. This study therefore introꢀ
duces a new strategy for tuning the catalytic properties of
MOFs and screening highꢀperformance catalysts through
modular chemistry.
ASSOCIATED CONTENT
Supporting Information. Full details for ligand synthesis and
sample characterization results are available free of charge via the
AUTHOR INFORMATION
Corresponding Author
*zhou@mail.chem.tamu.edu
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
The gas adsorption–desorption studies of this research was supꢀ
ported by the Center for Gas Separations Relevant to Clean Enerꢀ
gy Technologies, an Energy Frontier Research Center funded by
the US Department of Energy, Office of Science, Office of Basic
Energy Sciences under Award Number DEꢀSC0001015. Structurꢀ
al analyses were supported as part of the Hydrogen and Fuel Cell
Program under Award Number DEꢀEEꢀ0007049. We also
acknowledge the financial supports from U.S. Department of
Energy Office of Fossil Energy, National Energy Technology
(15) (a) Cui, Y.; Yue, Y.; Qian, G.; Chen, B. Chem. Rev. 2012, 112,
1126–1162. (b) Shustova, N. B.; Ong, T.ꢀC.; Cozzolino, A. F.; Michꢀ
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