4
122 Crystal Growth & Design, Vol. 10, No. 9, 2010
Fernandez et al.
T. and J.L. acknowledge the U.S. Department of Energy,
Officeof BasicEnergySciences, DivisionofMaterialsSciences
and Engineering, under Award KC020105-FWP12152 for
developing and characterizing the materials. C.H.F.P.
acknowledges support from the DOE/Office of Science, Division
of Chemical Sciences Geosciences, and Biosciences, for analyzing
the catalytic reactions. PNNL is a multiprogram national labora-
tory operated for DOE by Battelle under Contract DE-AC05-
carboxylate with large pores. Chem. Commun. 2007, 27, 2820–2822.
(
c) Salles, F.; Jobic, H.; Ghoufi, A.; Llewellyn, P. L.; Serre, C.; Bourrelly,
S.; Ferey, G.; Maurin, G. Transport Diffusivity of CO in the Highly
2
Flexible Metal-Organic Framework MIL-53(Cr). Angew. Chem., Int.
Ed 2009, 48 (44), 8335–8339. (d) Zhou, W.; Wu, H.; Yildirim, T.
Enhanced H-2 Adsorption in Isostructural Metal-Organic Frameworks
with Open Metal Sites: Strong Dependence of the Binding Strength on
Metal Ions. J. Am. Chem. Soc. 2008, 130 (46), 15268. (e) Maji, T. K.;
Matsuda, R.; Kitagawa, S. A flexible interpenetrating coordination
framework with a bimodal porous functionality. Nat. Mater. 2007, 6
76RL01830.
(
2), 142–148. (f ) Duriska, M. B.; Neville, S. M.; Lu, J. Z.; Iremonger,
S. S.; Boas, J. F.; Kepert, C. J.; Batten, S. R. Systematic Metal Variation
and Solvent and Hydrogen-Gas Storage in Supramolecular Nanoballs.
Angew. Chem., Int. Ed. 2009, 48 (47), 8919–8922.
Supporting Information Available: Details of experimental results,
thermal analysis, and PXRD measurements. This material is avail-
able free of charge via the Internet at http://pubs.acs.org.
(
3) (a) Hoskins, B. F.; Robson, R. Design and Construction of a New
Class of Scaffolding-Like Materials Comprising Infinite Polymeric
Frameworks of 3-D-Linked Molecular Rods;A Reappraisal of the
References
(
1) (a) Eddaoudi, M.; Li, H. L.; Yaghi, O. M. Highly porous and stable
metal-organic frameworks: Structure design and sorption proper-
ties. J. Am. Chem. Soc. 2000, 122 (7), 1391–1397. (b) Yaghi, O. M.;
O'Keeffe, M.; Ockwig, N. W.; Chae, H. K.; Eddaoudi, M.; Kim, J.
Reticular synthesis and the design of new materials. Nature 2003, 423
Zn(Cn)
2
and Cd(Cn)
2
Structures and the Synthesis and Structure of
][Cu(I)Zn(II)(CN)
and Cu(I)[4,4 ,4 ,4 -Tetracyanotetraphenylmethane]BF xC NO
the Diamond-Related Frameworks [N(CH
3
)
4
4
]
2
.
0
00 000
4
3
6
H
5
J. Am. Chem. Soc. 1990, 112 (4), 1546–1554. (b) Alkordi, M. H.; Liu, Y. L.;
Larsen, R. W.; Eubank, J. F.; Eddaoudi, M. Zeolite-like metal-organic frame-
works as platforms for applications: On metalloporphyrin-based catalysts. J.
Am. Chem. Soc. 2008, 130 (38), 12639. (c) Kishan, M. R.; Srinivas, N.;
Raghavan, K. V.; Kulkarni, S. J.; Sarma, J. A. R. P.; Vairamani, M. A novel,
shape-selective, zeolite-catalyzed synthesis of calix(4)pyrroles. Chem. Com-
mun. 2001, No. 21, 2226–2227. (d) Cheetham, A. K.; Rao, C. N. R.; Feller,
R. K. Structural diversity and chemical trends in hybrid inorganic-organic
framework materials. Chem. Commun. 2006, No. 46, 4780–4795. (e) Fujita,
M.; Kwon, Y. J.; Washizu, S.; Ogura, K. Preparation, Clathration Ability, and
Catalysis of a 2-Dimensional Square Network Material Composed of
(
6941), 705–714. (c) Lee, J.; Farha, O. K.; Roberts, J.; Scheidt, K. A.;
Nguyen, S. T.; Hupp, J. T. Metal-organic framework materials as
catalysts. Chem. Soc. Rev. 2009, 38 (5), 1450–1459. (d) Thallapally,
P. K.; Tian, J.; Kishan, M. R.; Fernandez, C. A.; Dalgarno, S. J.; McGrail,
P. B.; Warren, J. E.; Atwood, J. L. Flexible (Breathing) Interpenetrated
2
Metal-Organic Frameworks for CO Separation Applications. J. Am.
Chem. Soc. 2008, 130 (50), 16842–16843. (e) Furukawa, S.; Hirai, K.;
Nakagawa, K.; Takashima, Y.; Matsuda, R.; Tsuruoka, T.; Kondo, M.;
Haruki, R.; Tanaka, D.; Sakamoto, H.; Shimomura, S.; Sakata, O.;
Kitagawa, S. Heterogeneously Hybridized Porous Coordination Polymer
Crystals: Fabrication of Heterometallic Core-Shell Single Crystals with
an In-Plane Rotational Epitaxial Relationship. Angew. Chem., Int. Ed.
0
Cadmium(II) and 4,4 -Bipyridine. J. Am. Chem. Soc. 1994, 116 (3),
1151–1152.
(4) (a) Chang, J. S.; Park, S. E.; Gao, Q. M.; Ferey, G.; Cheetham, A. K.
Catalytic conversion of butadiene to ethylbenzene over the nano-
porous nickel(II) phosphate, VSB-1. Chem. Commun. 2001, No. 9,
859–860. (b) Xamena, F. X. L. I.; Abad, A.; Corma, A.; Garcia, H. MOFs
as catalysts: Activity, reusability and shape-selectivity of a Pd-containing
MOF. J. Catal. 2007, 250 (2), 294–298. (c) Farrusseng, D.; Aguado, S.;
Pinel, C. Metal-Organic Frameworks: Opportunities for Catalysis. An-
gew. Chem., Int. Ed. 2009, 48 (41), 7502–7513.
(5) Thallapally, P. K.; Fernandez, C. A.; Motkuri, R. K.; Nune, S. K.;
Liu, J.; Peden, C. H. F. Micro and mesoporous metal-organic
frameworks for catalysis applications. Dalton Trans. 2010, 39,
1692–1694.
(6) Eddaoudi, M.; Kim, J.; Rosi, N.; Vodak, D.; Wachter, J.; O’Keeffe,
M.; Yaghi, O. M. Systematic design of pore size and functionality in
isoreticular MOFs and their application in methane storage. Science
2002, 295 (5554), 469–472.
(7) Ravon, U.; Domine, M. E.; Gaudillere, C.; Desmartin-Chomel, A.;
Farrusseng, D. MOFs as acid catalysts with shape selectivity proper-
ties. New J. Chem. 2008, 32 (6), 937–940.
2009, 48 (10), 1766–1770. (f) Lin, X.; Jia, J. H.; Zhao, X. B.; Thomas,
K. M.; Blake, A. J.; Walker, G. S.; Champness, N. R.; Hubberstey, P.;
Schroder, M. High H-2 adsorption by coordination-framework materials.
Angew. Chem., Int. Ed. 2006, 45 (44), 7358–7364. (g) Dybtsev, D. N.;
Chun, H.; Kim, K. Rigid and flexible: A highly porous metal-organic
framework with unusual guest-dependent dynamic behavior. Angew.
Chem., Int. Ed. 2004, 43 (38), 5033–5036. (h) Murray, L. J.; Dinca, M.;
Long, J. R. Hydrogen storage in metal-organic frameworks. Chem. Soc.
Rev. 2009, 38 (5), 1294–1314. (i) Zhao, X. B.; Xiao, B.; Fletcher, A. J.;
Thomas, K. M.; Bradshaw, D.; Rosseinsky, M. J. Hysteretic adsorption
and desorption of hydrogen by nanoporous metal-organic frameworks.
Science 2004, 306 (5698), 1012–1015.
(
2) (a) Kishan, M. R.; Tian, J.; Thallapally, P. K.; Fernandez, C. A.;
Dalgarno, S. J.; Warren, J. E.; McGrail, B. P.; Atwood, J. L. Flexible
metal-organic supramolecular isomers for gas separation. Chem.
Commun. 2010, 46 (4), 538–540. (b) Horcajada, P.; Surble, S.; Serre, C.;
Hong, D. Y.; Seo, Y. K.; Chang, J. S.; Greneche, J. M.; Margiolaki, I.;
Ferey, G. Synthesis and catalytic properties of MIL-100(Fe), an iron(III)