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Journal of the American Chemical Society
mL) solution of Ce(NO3)3ꢁ6H2O (0.044 g, 0.10 mmol). The
Author Contributions
1
2
3
4
solution was sealed in a glass jar, heated at 110 °C for 24 h,
and then cooled to room temperature. Pale yellow needleꢀ
shaped crystals formed, which were filtered and washed briefꢀ
ly with the mother liquor. Yield: 22 mg (44%). Anal. Calcd for
Ce2C48H96O21N6: C, 41.97; H, 7.04; N, 6.12. Found: C, 42.10;
§ These authors contributed equally to this work.
Notes
The authors declare no competing financial interests.
5
H, 6.88; N, 6.07. FTꢀIR (Nujol mull):
C=O(nonꢀcoordinating DEF), 1680 (s);
DEF), 1650 (s);
OꢀC=O, 1570 (s) cmꢀ1.
ν
OH, 3444 (m, br);
C=O(coordinating
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ACKNOWLEDGMENT
ν
ν
This work was supported by the Basic Science Research Program
through the National Research Foundation of Korea (NRF) fundꢀ
ed by the Ministry of Education, Science and Technology (No.
2010ꢀ0009063), the Ministry of Knowledge Economy (MKE),
Korea Institute for Advancement of Technology (KIAT) through
the InterꢀER Cooperation Projects, and the Human Resources
Development of the Korea Institute of Energy Technology Evalꢀ
uation and Planning (KETEP) grant funded by the Korea governꢀ
ment Ministry of Knowledge Economy (No. 20114030200010).
ν
Preparation of npꢀCeO2. Solid CeꢀaphꢀMOF was ground into
a powder and then heated at 5 oC/min under a nitrogen flow of
60 mL/min. After reaching the target temperature of 500 °C,
the material was maintained at that temperature for 12 h and
then cooled to room temperature. The resultant black solid was
ground into a powder. The powder was heated 1 oC/min to 300
oC under an oxygen flow of 100 mL/min. After the material
was maintained at this temperature for 2 h and then cooled to
room temperature, pale yellow npꢀCeO2 was obtained.
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REFERENCES
(1) Davis, M. E. Nature 2002, 417, 813.
(2) Kresge, C. T.; Leonowicz, M. E.; Roth, W. J.; Vartuli, J. C.;
Beck, J. S. Nature 1992, 359, 710.
(3) Corma, A. Chem. Rev. 1997, 97, 2373.
(4) Wan, Y.; Zhao, D. Chem. Rev. 2008, 107, 2821.
(5) Schüth, F. Chem. Mater. 2001, 13, 3184.
(6) Ren, Y.; Ma, Z.; Bruce, P. G. Chem. Soc. Rev. 2012, 41, 4909.
(7) Lee, J.; Orilall, M. C.; Warren, S. C.; Kamperman, M.; DiSalvo,
F. J.; Wiesner, U. Nat. Mater. 2008, 7, 222.
(8) Yang, P.; Zhao, D.; Margolese, D. I.; Chmelka, B. F.; Stucky, G.
D. Nature 1998, 396, 152.
(9) Grosso, D.; Boissière, C.; Smarsly, B.; Brezesinski, T.; Pinna,
N.; Albouy, P. A.; Amenitsch, H.; Antonietti M.; Sanchez, C.
Nat. Mater. 2004, 3, 787.
(10) Yang, H.; Zhao, D. J. Mater. Chem. 2005, 15, 1217.
(11) Corma, A.; Atienzar, P.; Garcia, H.; ChaneꢀChing, J.ꢀY. Nat.
Mater. 2004, 3, 394.
(12) Buonsanti, R.; Pick, T. E.; Krins, N.; Richardson, T. J.; Helms ,
B. A.; Milliron, D. J. Nano Lett. 2012, 12, 3872.
(13) Kondo, J. N.; Domen, K. Chem. Mater. 2008, 20, 835.
(14) Yaghi, O. M.; O'Keeffe, M.; Ockwig, N. W.; Chae, H. K.; Edꢀ
daoudi, M.; Kim, J. Nature 2003, 423, 705.
(15) Tranchemontagne, D. J.; MendozaꢀCortes, J. L.; O’Keeffe, M.;
Yaghi, O. M. Chem. Soc. Rev. 2009, 38, 1257.
(16) Murray, L. J.; Dincă, M.; Long, J. R. Chem. Soc. Rev. 2009, 38,
1294.
(17) Makal, T. A.; Li, J.ꢀR.; Lu, W.; Zhou, H. ꢀC. Chem. Soc. Rev.
2012, 41, 7761.
(18) Corma, A.; Garcia, H.; Xamena, F. X. L. I. Chem. Rev. 2010,
110, 4606.
(19) Bureekaew, S.; Sato, H.; Matsuda, R.; Kubota, Y.; Hirose, R.;
Kim, J.; Kato, K.; Takata, M.; Kitagawa, S. Angew. Chem. Int.
Ed. 2010, 49, 7660.
(20) Pramanik, S.; Zheng, C.; Zhang, X.; Emge, T. J.; Li, J. J. Am.
Chem. Soc. 2011, 133, 4153.
Preparation of arꢀMgO. Mg3(bpdc)3(DMA)4 (MgꢀarꢀMOF)
o
o
was heated at 5 C/min to 600 C under a nitrogen flow of 60
mL/min. The material was maintained at this temperature for
12 h and then cooled to room temperature.
Gas Sorption Study. The nitrogen adsorptionꢀdesorption isoꢀ
therms were measured at 77 K on a BELsorpꢀMAX adsorption
analyzer. Prior to adsorption measurement the samples were
o
evacuated at 200 C under vacuum (p < 10ꢀ5 mbar) for 12 h.
The specific surface area was determined from the linear part
of the BET equation, and the total pore volume was calculated
from the amount adsorbed at a relative pressure of about 0.99.
The results were summarized in Table S5.
SingleꢀCrystal Xꢀray Crystallography. A singleꢀcrystal of 1
was mounted on the top of a capillary with Paratone oil. Difꢀ
fraction data were collected at 173 K using a Rigaku Rꢀaxis
Rapid II diffractometer (Mo Kα, λ = 0.71073 Å), which was
equipped with an Xꢀray diffraction camera system with an
imaging plate. Full sphere data were collected for all the crysꢀ
tals, and the raw data were processed and scaled using the
RapidAuto software suite.44 The crystal structures were solved
by direct methods45 and refined by fullꢀmatrix leastꢀsquares
refinement using the SHELXLꢀ97 computer program.44 The
positions of all nonꢀhydrogen atoms were refined with anisoꢀ
tropic displacement factors. The hydrogen atoms were posiꢀ
tioned geometrically using a riding model. For 1, the electron
density of the disordered guest molecules was flattened using
the ‘SQUEEZE’ option of the program PLATON.46 The crysꢀ
tallographic data and selected bond lengths and angles of 1 are
summarized in Tables S6 and S7.
(21) Rocca, J. D.; Liu, D.; Lin, W. Acc. Chem. Res. 2011, 44, 957.
(22) Yang, S. J.; Park, C. R. Adv. Mater. 2012, 24, 4010.
(23) Yang, S. J.; Kim T.; Im J. H.; Kim, Y. S.; Lee, K.; Jung, H.;
Park, C. R. Chem. Mater. 2012, 24, 464.
(24) Hu, J.; Wang, H.; Gao, Q.; Guo, H. Carbon, 2010, 48, 3599.
(25) Chaikittisilp, W.; Hu, M.; Wang, H.; Huang, H.ꢀS.; Fujita, T.;
Wu, K. C.ꢀW.; Chen, L. ꢀC. Yamauchi Y.; Ariga, K. Chem.
Commun. 2012, 48, 7259.
(26) Lim, S.; Suh, K.; Kim, Y.; Yoon, M.; Park, H.; Dybtsev, D. N.;
Kim, K. Chem. Commun. 2012, 48, 7447.
(27) Jiang, H.ꢀL.; Liu, B.; Lan, Y. ꢀQ.; Kuratani, K.; Akita, T.;
Shioyama, H.; Zong, F.; Xu, Q. J. Am. Chem. Soc. 2011, 133,
11854.
ASSOCIATED CONTENT
Supporting Information
Crystallographic data as a CIF file, Table S1ꢀ7, Figures S1−13,
and related references. This material is available free of charge via
AUTHOR INFORMATION
Corresponding Author
hoirimoon@unist.ac.kr; shjoo@unist.ac.kr
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