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Journal of the American Chemical Society
rative Access Team (MRCAT, Sectors 10 BM and 10ID) opera-
tions are supported by the Department of Energy and the MRCAT
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member institutions. J.T.M. and J.R.G. were supported by the U.S.
Department of Energy, Office of Basic Energy Sciences, Chemical
Sciences under Contract DE-AC-02-06CH11357. The authors
would like to thank both KACST and NU for their continued sup-
port of this research. M.H.B. thanks DFG for a Postdoctoral Re-
search Fellowship Award.
MOF, Metal-organic framework; CP-450, Cytochrome P-450;
DMF, N,N-dimethylformamide; DEF, N,N-diethylformamide;
TMS-N3, Azidotrimethylsilane; H4TBAPy, 1,3,6,8-tetrakis(p-ben-
zoic acid)pyrene; FeTCP-Cl, meso-tetra(4-carboxyphenyl)porphy-
rin-FeIII chloride; DRIFTS, Diffuse reflectance infrared Fourier
transform spectroscopy, PDF, Pair distribution function; XANES,
K-edge X-ray Absorption Near-Edge Structure; EXAFS, Extended
X-Ray Absorption Fine Structure.
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13. (a) Lee, J.; Farha, O. K.; Roberts, J.; Scheidt, K.; Nguyen, S.
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21. At this time, the specific location of the each additional benzoic
acid molecule in the as-synthesized Hf-1, Hf-NU-1000, NU-1000
or PCN-222/MOF-545 farmeworks should be similar to what we
published previously (Deria, P.; Mondloch, J. E.; Tylianakis, E.;
Ghosh, P.; Bury, W.; Snurr, R. Q.; Hupp, J. T.; Farha, O. K. J. Am.
Chem. Soc. 2013, 135, 16801−16804. Deria, P.; Bury, W.; Hupp,
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hands, each attempt at preparing the aforementioned structures re-
sults in the inclusion of exactly four benzoic acid molecules per
node, as determined by comparing the ratio of benzoic acid and the
tetra-acid linker using 1H-NMR spectroscopy, and leads us to con-
clude that the node is responsible for the accumulated benzoic ac-
ids. Looking at the crystal structure of NU-1000 we envision that
four benzoates could function as ligands to the four most exposed
metal atoms on the node, pointing the aromatic ring into the large
hexagonal pore of the framework.
22. After further investigation it was found that the low Fe:Hf ra-
tio was a consequence of a mathematical error and that the as-syn-
thesized material was in fact fully metalated.
23. To activate Hf-2 toward catalysis, FeCl3 was used to ensure
complete metalation of the porphyrin functionality. The in situ gen-
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Am. Chem. Soc. 2011, 133, 12940–12943.
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