Crystal engineering of a microporous, catalytically active fcu topology MOF using a custom-designed metalloporphyrin linker

Article abstract of DOI:10.1002/anie.201205603

A 12-connected fcu metal-organic framework (MOF), MMPF-3, has been prepared using a Co^II metalloporphyrin. MMPF-3 is comprised of the same polyhedral supermolecular building blocks as the prototypal fcu-MOF, fcu-MOF-1, and its nanoscale cavities feature 18 catalytically active cobalt centers. The high density (ca. 5 cobalt sites/nm³) affords MMPF-3 superior performance in catalytic epoxidation of trans-stilbene compared to other MOFs. Copyright

Full text of DOI:10.1002/anie.201205603

Angewandte
Chemie
DOI: 10.1002/anie.201205603
Crystal Engineering
Crystal Engineering of a Microporous, Catalytically Active fcu
Topology MOF Using a Custom-Designed Metalloporphyrin Linker**
Le Meng, Qigan Cheng, Chungsik Kim, Wen-Yang Gao, Lukasz Wojtas, Yu-Sheng Chen,
Michael J. Zaworotko,* X. Peter Zhang,* and Shengqian Ma*
A major driving force behind the recent surge of interest in
metal–organic frameworks (MOFs)[1] lies with their amena-
bility to design using crystal engineering[2a–d] strategies. In
particular, MOFs with specific composition and topology can
be targeted by judicious selection of organic linkers and
metal-based molecular building blocks[2e–g] (MBBs) that serve
as nodes.[2] Furthermore, their modular nature means that
prototypal MOFs can serve as blueprints or platforms for
a plethora of derivatives with controlled pore size and surface
area, as exemplified by the practice of “reticular synthesis”.[3]
Such features make MOFs stand out over traditional porous
materials, and afford them with potential for use in gas
storage,[4] separation,[5] CO2 capture,[6] sensor,[7] catalysis,[8]
and other areas.[9]
High-symmetry MOFs based upon high-connectivity
polyhedral cage MBBs that are in effect supermolecular
building blocks (SBBs) can provide exquisite control over
structure because of their high connectivity and also afford
the features of confined nanospace[10] and extra-large surface
area.[11] Such MOFs have afforded superior performance in
the context of gas storage for hydrogen, methane, CO2, and
other gas molecules.[4,6,11,12] The nature of the nanospace in
SBB-based MOFs is such that they can encapsulate catalyti-
cally active species, for example, organometallics,[13] polyoxo-
metallates,[14] metalloporphyrins (porph@MOMs),[15] and
enzymes.[16] Along with encapsulation of catalysts, it is
possible to generate porphyrin-walled MOFs by custom-
designing metalloporphyrin moieties so that they can serve as
vertices and/or edges and/or faces. In principle, the metal
clusters residing on the vertices could also contribute as active
sites to achieve an even higher density of active sites than that
of porph@MOMs.[15] Polyhedral MOFs are therefore attrac-
tive targets as catalyst supports for heterogeneous catalysis.
However, although metallosalens and metalloporphyrins
have been utilized as linkers for catalytically active MOFs[17]
and polyhedral cage-containing metal–metalloporphyrin
frameworks exist,[18] MOFs sustained by catalytically active
metalloporphyrin linkers and catalytically active MBBs
remain unexplored.
Herein, we report such a MOF that based upon a pre-
viously reported fcu topology net built from 12-connected
cubohemioctahedral SBBs of formula [Co2(m2-H2O)(H2O)4]6-
(bdc)12 and benzoimidephenanthroline tetracarboxylate
(bipa-tc) linkers (Scheme 1a), fcu-MOF-1.[19] The new com-
[*] L. Meng, Q. Cheng, C. Kim, W.-Y. Gao, L. Wojtas,
Prof. M. J. Zaworotko, Prof. X. P. Zhang, Prof. S. Ma
Department of Chemistry, University of South Florida
4202 E. Fowler Avenue, Tampa, FL 33620 (USA)
E-mail: xtal@usf.edu
xpzhang@usf.edu
sqma@usf.edu
Homepage: http://sqma.myweb.usf.edu/
Scheme 1. The ligands that serve as linkers in fcu-MOF-1 and MMPF-
3: a) benzoimidephenanthrolinetetracarboxylic acid (H4bipa-tc) and
b) 5,15-bis(3,5-dicarboxyphenyl)-10,20-bis(2,6-dibromophenyl)porphyrin
(H4dcdbp).
Y.-S. Chen
ChemMatCARS, Center for Advanced Radiation Sources, the
University of Chicago
9700 S. Cass Avenue, Argonne, IL 60439 (USA)
pound, MMPF-3 (MMPF denotes metal–metalloporphyrin
framework), was prepared solvothermally from a novel
porphyrin ligand that is an analogue of bipa-tc, 5,15-bis(3,5-
dicarboxyphenyl)-10,20-bis(2,6-dibromophenyl)porphyrin
(dcdbp, Scheme 1b),[20] and Co(NO3)2. Cube-shaped, dark-
red crystals of MMPF-3, [Co2(m2-H2O)(H2O)4](Co-dcdbp)·-
(H2O)6·(C2H5OH)12·(DMF)12, (as determined by x-ray crys-
tallography, elemental analysis, and thermogravimetric anal-
ysis) were thereby harvested. Single-crystal X-ray diffraction
[**] The authors acknowledge the University of South Florida and the US
Department of Energy (DE-AR0000177) for financial for financial
support of this work. The authors thank Dr. Daqiang Yuan for help in
drawing structural pictures of MMPF-3. The crystal diffraction of
MMPF-3 was carried out at the Advanced Photon Source on
beamline 15ID-B of ChemMatCARS Sector 15 (NSF/CHE-0822838,
DE-AC02-06CH11357).
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/anie.201205603.
Angew. Chem. Int. Ed. 2012, 51, 1 – 5
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1
These are not the final page numbers!

.
Angewandte
Communications
studies were conducted at the Advanced Photon Source,
Argonne National Laboratory and revealed that MMPF-3
crystallizes in the same space group, Pa3, as fcu-MOF-1, with
a solvent-accessible volume of 60% as calculated from
PLATON.[20]
¯
That MMPF-3 exhibits permanent porosity was confirmed
by CO2 adsorption at 273 K, which revealed a surface area of
about 750 m2 gÀ1 using NLDFT analysis (Supporting Informa-
tion, Figure S5).[21] Given the high density of cobalt metal
centers in the truncated octahedral cages of MMPF-3, we
evaluated its catalytic performance in the context of epox-
idation of trans-stilbene, which has recently been studied in
cobalt-based MOFs.[22] We conducted assays for the epoxida-
tion of trans-stilbene using tert-butyl hydroperoxide (tbhp) as
oxidant in acetonitrile at 608C. Control experiments were
conducted for homogeneous cobalt(II)-metalated dcdbp (Co-
(dcdbp)), fcu-MOF-1, and a blank under the same conditions.
As revealed by Figure 2 and Table 1, MMPF-3 demonstrated
the most efficient catalytic activity for epoxidation of trans-
stilbene of the compounds studied in terms of both yield
(95.7% over 24 h) and selectivity (87.1% epoxide product).
This compares favorably to the corresponding values for
homogeneous Co(dcdbp) (60.4% yield, 67.0% epoxide), fcu-
MOF-1 (47.1% yield, 76.7% epoxide), and the blank (9.0%
a = 38.805(3) ꢀ, (39.288(2) ꢀ in fcu-MOF-1). As expected,
MMPF-3 is based upon Co2(m2-H2O)(H2O)4(COO)4 MBBs
(Supporting Information, Figure S2) that afford the cubohe-
mioctahedral SBBs that serve as 12-connected nodes (Fig-
ure 1a) in the resulting fcu topology network (Supporting
Information, Figure S3).
Figure 1. The three types of polyhedral cages present in MMPF-3:
a) cubohemioctahedron, b) truncated tetrahedron, and c) truncated
octahedron. d) 3D structure of MMPF-3 illustrating how its polyhedral
cages are connected. See also the Supporting Information, Figure S3,
which highlights how MMPF-3 is formed by linking the 12 vertices of
the cubohemioctahedral cage.
fcu-MOF-1 was targeted as a blueprint because it exhibits
three types of polyhedral cage: a cubohemioctahedron with
a window size of ca. 5.9 ꢀ and inner dimensions of about
7.3 ꢀ (atom-to-atom distance); a truncated tetrahedron in
which six linkers form the edges of the tetrahedron (2,6-
dibromophenyl moieties occupy the inner space of the cage,
Figure 1b); a truncated octahedron, with a window size of
about 9.2 ꢀ (atom to atom distance) and a cavity with an
internal volume of about 4000 ꢀ3 (Figure 1c). In the trun-
cated octahedral cage, twelve bipa-tc linkers form the main
edges of the octahedron. Furthermore, the SBBs occupy the
vertices in such a manner that one CoII cation of each Co2(m2-
H2O)(H2O)4(COO)4 MBB orients towards the center of the
cage. The equivalent nanoscopic polyhedron in MMPF-3
possesses twelve cobalt centers that orient towards the center
of the cage and therefore exhibits eighteen metal centers with
a density of about 5 Co/nm3. The three types of polyhedral
cage are interconnected (Figure 1d), and MMPF-3 possesses
Figure 2. Kinetic traces of trans-stilbene epoxidation catalyzed by
heterogeneous MMPF-3, homogenous Co(dcdbp), fcu-MOF-1, PPF-
1Co, and in the absence of catalyst (the molar ratio of trans-stilbene/
tbhp/catalyst was 1000:1500:1 for all of the catalytic assays).
Table 1: The epoxidation of trans-stilbene catalyzed by MMPF-3 and
related catalysts.[a]
Catalyst
Conversion [%][b]
Epoxide [%]
TOF[c] [hÀ1
]
MMPF-3
Co(dcdbp)
fcu-MOF-1
MMPF-2
PPF-1Co
blank
95.7
60.4
47.1
67.2
23.7
9.0
87.1
67.0
76.7
58.0
30.1
55.8
83.9
69
30
20
40
15
n.a.
64
MMPF-3[d]
94.4
[a] trans-Stilbene (1 mmol), tbhp (1.5 mmol), catalyst (0.001 mmol),
acetonitrile (5.0 mL) were stirred at 608C for 24 h. [b] After 24 h.
[c] Average over 12 h (n.a. =not applicable). [d] The eighth cycle.
2
www.angewandte.org
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2012, 51, 1 – 5
These are not the final page numbers!

Angewandte
Chemie
found: C 45.99, H 6.58, N, 7.85. The reaction was amplified to
hundreds of milligrams quantity using multiple tubes.
yield, 55.8% epoxide). The average turnover frequency
(TOF) in the first 12 hour was 69 hÀ1 for MMPF-3, almost
3.5 times faster than that of fcu-MOF-1. We attribute the
enhancement of catalytic performance in MMPF-3 versus fcu-
MOF-1 to the higher density of active cobalt centers in the
former and/or cooperative interactions between the active
centers.[17m] We also determined the catalytic activity for the
3D-channel cobalt-based porphyrin MOF MMPF-2, which
was recently reported by our group,[23] and the 2D-channel
MOF PPF-1Co that is based upon cobalt-metalated tetra-
Crystal Data for MMPF-3: C48H20Br4N4O14Co3, Mr = 1373.11,
3
¯
cubic, Pa3, a = 38.805(3), V= 58434(7) ꢀ , Z = 24, T= 100(2) K,
1calcd = 0.936 gcmÀ3, R1 (I > 2s(I)) = 0.1142, wR2 (all data) = 0.3275.
CCDC 891567 contains the supplementary crystallographic data for
this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
Full experimental details for ligand synthesis, structure drawings,
TGA plots, and gas sorption isotherms are presented in the
Supporting Information.
kis(4-carboxyphenyl)porphyrin
and
Co2(COO)4(H2O)2
MBBs.[24] Figure 2 reveals that MMPF-2 converts 67.2% of
substrate after 24 h (Table 1), whereas PPF-1Co converts only
23.7% (Table 1). We attribute the reduced catalytic activity in
these two porphyrin-based MOFs to misalignment (that is,
not oriented directly towards the channel center) or non-
alignment (oriented parallel to the channels) of the cobalt
centers, respectively. No detectable leaching of active site or
cobalt metal in the reaction solution was observed after
removal of MMPF-3 by filtration, and MMPF-3 can be reused
for eight cycles without significant drop in its catalytic activity
(Table 1). Our results therefore highlight how appropriately
designed polyhedral cages can serve as efficient nanoreactors.
However, it should be noted that several factors, for example,
amount of catalyst, oxidant, solvent, reaction temperature,
and time, can profoundly influence performance (for example
conversion, epoxide selectivity, TOF) in catalytic epoxidation
of trans-stilbene.[25] We are currently investigating these
factors in the context of MMPF-3 and are also studying
epoxidation of different olefin substrates with various molec-
ular sizes and shapes to assess whether or not size- and shape-
selectivity can be effected. These studies will be reported
separately in the near future.
Received: July 14, 2012
Revised: August 9, 2012
Published online: && &&, &&&&
Keywords: cobalt · crystal engineering ·
.
heterogeneous catalysis · metalloporphyrins · Metal–
organic frameworks
[1] a) S. Kitagawa, R. Kitaura, S. Noro, Angew. Chem. 2004, 116,
2388 – 2430; Angew. Chem. Int. Ed. 2004, 43, 2334 – 2375;
b) L. R. Macgillivray, Metal-Organic Frameworks: Design and
Application, Wiley, Hoboken, 2010; c) C. Janiak, J. Chem. Soc.
Dalton Trans. 2003, 2781 – 2804; d) H.-C. Zhou, J. R. Long, O. M.
Yaghi, Chem. Rev. 2012, 112, 673 – 674.
[2] a) G. R. Desiraju, Angew. Chem. 1995, 107, 2541 – 2558; Angew.
Chem. Int. Ed. Engl. 1995, 34, 2311 – 2327; b) G. R. Desiraju,
Angew. Chem. 2007, 119, 8492 – 8508; Angew. Chem. Int. Ed.
2007, 46, 8342 – 8356; c) B. Moulton, M. J. Zaworotko, Chem.
Rev. 2001, 101, 1629 – 1658; d) M. B. Andrews, C. L. Cahill,
Angew. Chem. 2012, 124, 6735 – 6738; Angew. Chem. Int. Ed.
2012, 51, 6631 – 6634; e) G. B. Gardner, D. Venkataraman, J. D.
Moore, S. Lee, Nature 1995, 374, 792 – 795; f) J. T. A. Jones, T.
Hasell, X. Wu, J. Bacsa, K. E. Jelfs, M. Schmidtmann, S. Y.
Chong, D. J. Adams, A. Trewin, F. Schiffmann, F. Cora, B. Slater,
A. Steiner, G. M. Day, A. I. Cooper, Nature 2011, 474, 367 – 371;
g) M. Eddaoudi, D. B. Moler, H. Li, B. Chen, T. M. Reineke, M.
OꢁKeeffe, O. M. Yaghi, Acc. Chem. Res. 2001, 34, 319 – 330.
[3] a) O. M. Yaghi, M. OꢁKeeffe, N. W. Ockwig, H. K. Chae, M.
Eddaoudi, J. Kim, Nature 2003, 423, 705 – 714; b) M. OꢁKeeffe,
Chem. Soc. Rev. 2009, 38, 1215 – 1217; c) D. J. Tranchemontagne,
J. L. Mendoza-Cortes, M. OꢁKeeffe, O. M. Yaghi, Chem. Soc.
Rev. 2009, 38, 1257 – 1283; d) M. OꢁKeeffe, O. M. Yaghi, Chem.
Rev. 2012, 112, 675 – 702.
[4] a) L. J. Murray, M. Dinca, J. R. Long, Chem. Soc. Rev. 2009, 38,
1294 – 1314; b) S. Ma, H.-C. Zhou, Chem. Commun. 2010, 46,
44 – 53; c) M. P. Suh, H. J. Park, T. K. Prasad, D.-W. Lim, Chem.
Rev. 2012, 112, 782 – 835.
[5] a) J.-R. Li, R. J. Kuppler, H.-C. Zhou, Chem. Soc. Rev. 2009, 38,
1477 – 1504; b) S. Ma, Pure Appl. Chem. 2009, 81, 2235 – 2251;
c) J.-R. Li, J. Sculley, H.-C. Zhou, Chem. Rev. 2012, 112, 869 –
932; d) H. Wu, Q. Gong, D. H. Olson, J. Li, Chem. Rev. 2012, 112,
836 – 868.
In summary, polyhedral cage-based nanoreactors that
exhibit a high density of about five catalytically active cobalt
centers per nm3 have been generated in MMPF-3 by
decoration of a previously known 12-connected MOF, fcu-
MOF-1, with
a
custom-designed CoII metalloporphyrin
ligand. MMPF-3 exhibits permanent microporosity and
demonstrates superior performance in the context of both
selectivity and overall conversion in catalytic epoxidation of
trans-stilbene when compared to the parent fcu-MOF-1 and
two other cobalt–porphyrin MOFs. The crystal engineering
approach for the generation of polyhedral cage-based nano-
reactors with a high density of catalytically active centers is
expected to be a broadly applicable approach for the
development of new classes of highly efficient heterogeneous
catalytic systems for epoxidation and related reactions.
Experimental Section
[6] a) J.-R. Li, Y. Ma, M. C. McCarthy, J. Sculley, J. Yu, H.-K. Jeong,
P. B. Balbuena, H.-C. Zhou, Coord. Chem. Rev. 2011, 255, 1791 –
1823; b) Y.-S. Bae, R. Q. Snurr, Angew. Chem. 2011, 123, 11790 –
11801; Angew. Chem. Int. Ed. 2011, 50, 11586 – 11596; c) K.
Sumida, D. L. Rogow, J. A. Mason, T. M. McDonald, E. D.
Bloch, Z. R. Herm, T.-H. Bae, J. R. Long, Chem. Rev. 2012, 112,
724 – 781; d) R. Vaidhyanathan, S. S. Iremonger, G. K. H. Shi-
mizu, P. G. Boyd, S. Alavi, T. K. Woo, Science 2010, 330, 650 –
653; e) W.-Y. Gao, W. Yan, R. Cai, K. Williams, A. Salas, L.
Wojtas, X. Shi, S. Ma, Chem. Commun. 2012, 48, 8898 – 8900.
Synthesis of MMPF-3: A mixture of 5,15-bis(3,5-dicarboxyphenyl)-
10,20-bis(2,6-dibromophenyl)porphyrin (dcdbp) (2.0 mg), Co-
(NO3)·6H2O (8.0 mg) and 1.2 mL mixed solvent (0.5 mL N,N’-
dimethylformamide (DMF), 0.5 mL ethanol, and 0.2 mL H2O) was
sealed in a Pyrex tube under vacuum and heated at 858C for 48 h. The
resulting dark red crystals were washed with DMF three times to give
MMPF-3 as pure crystals with formula of [Co2(m2-H2O)(H2O)4](Co-
dcdbp)·(H2O)6·(C2H5OH)12·(DMF)12 (yield: 70% based on dcdbp).
Elemental Analysis calcd(%) for MMPF-3: C 44.65, H 6.87, N 7.71;
Angew. Chem. Int. Ed. 2012, 51, 1 – 5
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
3
These are not the final page numbers!

.
Angewandte
Communications
[7] a) L. E. Kreno, K. Leong, O. K. Farha, M. Allendorf, R. P. V.
Duyne, J. T. Hupp, Chem. Rev. 2012, 112, 1105 – 1125; b) Y. Cui,
Y. Yue, G. Qian, B. Chen, Chem. Rev. 2012, 112, 1126 – 1162.
[8] a) M. Fujita, Y. J. Kwon, S. Washizu, K. Ogura, J. Am. Chem.
Soc. 1994, 116, 1151 – 1152; J. Y. Lee, O. K. Farha, J. Roberts,
K. A. Scheidt, S. T. Nguyen, J. T. Hupp, Chem. Soc. Rev. 2009, 38,
1450 – 1459; b) A. Corma, H. Garcıa, F. X. Llabrees i Xamena,
Chem. Rev. 2010, 110, 4606 – 4655; c) M. Yoon, R. Srirambalaji,
K. Kim, Chem. Rev. 2012, 112, 1196 – 1231.
[9] a) S. Ma, L. Meng, Pure Appl. Chem. 2011, 83, 167 – 188; b) C.
Wang, T. Zhang, W. Lin, Chem. Rev. 2012, 112, 1084 – 1104; c) W.
Zhang, R.-G. Xiong, Chem. Rev. 2012, 112, 1163 – 1195; d) S. M.
Cohen, Chem. Rev. 2012, 112, 970 – 1000; e) P. Horcajada, R.
Gref, T. Baati, P. K. Allan, G. Maurin, P. Couvreur, G. Ferey,
R. E. Morris, C. Serre, Chem. Rev. 2012, 112, 1232 – 1268; f) A.
Bꢂtard, R. A. Fischer, Chem. Rev. 2012, 112, 1055 – 1083.
[10] a) J. J. Perry IV, J. A. Perman, M. J. Zaworotko, Chem. Soc. Rev.
2009, 38, 1400 – 1417; b) Y. Inokuma, T. Arai, M. Fujita, Nat.
Chem. 2010, 2, 780 – 783; c) J. Zhang, J. T. Bu, S. Chen, T. Wu, S.
Zheng, Y. Chen, R. A. Nieto, P. Feng, X. Bu, Angew. Chem.
2010, 122, 9060 – 9063; Angew. Chem. Int. Ed. 2010, 49, 8876 –
8879; d) R. Chakrabarty, P. S. Mukherjee, P. J. Stang, Chem. Rev.
2011, 111, 6810 – 6918.
[11] a) O. K. Farha, O. Yazaydın, I. Eryazici, C. Malliakas, B. Hauser,
M. G. Kanatzidis, S. T. Nguyen, R. Q. Snurr, J. T. Hupp, Nat.
Chem. 2010, 2, 944 – 948; b) H. Furukawa, N. Ko, Y. B. Go, N.
Aratani, S. B. Choi, E. Choi, A. O. Yazaydin, R. Q. Snurr, M.
OꢁKeeffe, J. Kim, O. M. Yaghi, Science 2010, 329, 424 – 428.
[12] a) S. Ma, D. Sun, J. M. Simmons, C. D. Collier, D. Yuan, H.-C.
Zhou, J. Am. Chem. Soc. 2008, 130, 1012 – 1016; b) S. Xiang, W.
Zhou, Z. Zhang, M. A. Green, Y. Liu, B. Chen, Angew. Chem.
2010, 122, 4719 – 4722; Angew. Chem. Int. Ed. 2010, 49, 4615 –
4618.
[13] S. Hermes, M.-K. Schroter, R. Schmid, L. Khodeir, M. Muhler,
A. Tissler, R. W. Fischer, R. A. Fischer, Angew. Chem. 2005, 117,
6394 – 6397; Angew. Chem. Int. Ed. 2005, 44, 6237 – 6241.
[14] C. Y. Sun, S. X. Liu, D. D. Liang, K. Z. Shao, Y. H. Ren, Z. M.
Su, J. Am. Chem. Soc. 2009, 131, 1883 – 1888.
134, 13188 – 13191; c) Y. Chen, V. Lykourinou, T. Hoang, L.-J.
Ming, S. Ma, Inorg. Chem. 2012, DOI: 10.1021/ic301280n.
[17] a) M. C. Das, S. Xiang, Z. Zhang, B. Chen, Angew. Chem. 2011,
123, 10696 – 10707; Angew. Chem. Int. Ed. 2011, 50, 10510 –
10520; b) S. H. Cho, B. Q. Ma, S. T. Nguyen, J. T. Hupp, T. E.
Albrecht-Schmitt, Chem. Commun. 2006, 2563 – 2565; c) F.
Song, C. Wang, J. M. Falkowski, L. Ma, W. Lin, J. Am. Chem.
Soc. 2010, 132, 15390 – 15398; d) C. Zhu, G. Yuan, X. Chen, Z.
Yang, Y. Cui, J. Am. Chem. Soc. 2012, 134, 8058 – 8063; e) C. M.
Drain, A. Varotto, I. Radivojevic, Chem. Rev. 2009, 109, 1630 –
1658; f) K. S. Suslick, P. Bhyrappa, J.-H. Chou, M. E. Kosal, S.
Nakagaki, D. W. Smithenry, S. R. Wilson, Acc. Chem. Res. 2005,
38, 283 – 291; g) I. Goldberg, Chem. Commun. 2005, 1243 – 1254;
h) A. M. Shultz, O. K. Farha, J. T. Hupp, S. T. Nguyen, J. Am.
Chem. Soc. 2009, 131, 4204 – 4205; i) T. Lang, A. Guenet, E.
Graf, N. Kyritsakas, M. W. Hosseini, Chem. Commun. 2010, 46,
3508 – 3510; j) O. K. Farha, A. M. Shultz, A. A. Sarjeant, S. T.
Nguyen, J. T. Hupp, J. Am. Chem. Soc. 2011, 133, 5652 – 5655;
k) L. D. DeVries, P. M. Barron, E. P. Hurley, C. Hu, W. Choe, J.
Am. Chem. Soc. 2011, 133, 14848 – 14851; l) C. Zou, Z. Zhang, X.
Xu, Q. Gong, J. Li, C.-D. Wu, J. Am. Chem. Soc. 2011, 133, 87 –
90; m) X.-L. Yang, M.-H. Xie, C. Zou, Y. He, B. Chen, M.
OꢁKeeffe, C.-D. Wu, J. Am. Chem. Soc. 2012, 134, 10638 – 10645.
[18] a) X.-S. Wang, L. Meng, Q. Cheng, C. Kim, L. Wojtas, M.
Chrzanowski, Y.-S. Chen, X. P. Zhang, S. Ma, J. Am. Chem. Soc.
2011, 133, 16322 – 16325; b) X.-S. Wang, M. Chrzanowski, W.-Y.
Gao, L. Wojtas, Y.-S. Chen, M. J. Zaworotko, S. Ma, Chem. Sci.
2012, 3, 2823 – 2827.
[19] A. J. Cairns, J. A. Perman, L. Wojtas, V. C. Kravtsov, M. H.
Alkordi, M. Eddaoudi, M. J. Zaworotko, J. Am. Chem. Soc.
2008, 130, 1560 – 1561.
[20] Y. Chen, K. B. Fields, X. P. Zhang, J. Am. Chem. Soc. 2004, 126,
14718 – 14719.
[21] A. L. Spek, J. Appl. Crystallogr. 2003, 36, 7 – 13.
[22] J. Weber, J. Schmidt, A. Thomas, W. Bohlmann, Langmuir 2010,
26, 15650 – 15656.
[23] a) M. J. Beier, W. Kleist, M. T. Wharmby, R. Kissner, B.
Kimmerle, P. A. Wright, J.-D. Grunwaldt, A. Baiker, Chem.
Eur. J. 2012, 18, 887 – 898; b) J. Zhang, A. V. Biradar, S.
Pramanik, T. J. Emge, T. Asefa, J. Li, Chem. Commun. 2012,
48, 6541 – 6543.
[15] a) R. W. Larsen, L. Wojtas, J. Perman, R. L. Musselman, M. J.
Zaworotko, C. M. Vetromile, J. Am. Chem. Soc. 2011, 133,
10356 – 10359; b) Z. Zhang, L. Zhang, L. Wojtas, P. Nugent, M.
Eddaoudi, M. J. Zaworotko, J. Am. Chem. Soc. 2012, 134, 924 –
927; c) Z. Zhang, L. Zhang, L. Wojtas, M. Eddaoudi, M. J.
Zaworotko, J. Am. Chem. Soc. 2012, 134, 928 – 933.
[24] X.-S. Wang, M. Chrzanowski, C. Kim, W.-Y. Gao, L. Wojtas, Y.-S.
Chen, X. P. Zhang, S. Ma, Chem. Commun. 2012, 48, 7173 – 7175.
[25] E.-Y. Choi, C. A. Wray, C. Hu, W. Choe, CrystEngComm 2009,
11, 553 – 555.
[16] a) V. Lykourinou, Y. Chen, X.-S. Wang, L. Meng, T. Hoang, L.-J.
Ming, R. L. Musselman, S. Ma, J. Am. Chem. Soc. 2011, 133,
10382 – 10385; b) Y. Chen, V. Lykourinou, C. Vetromile, T.
Hoang, L.-J. Ming, R. Larsen, S. Ma, J. Am. Chem. Soc. 2012,
[26] a) C.-M. Che, J.-S. Huang, Chem. Commun. 2009, 3996 – 4015;
b) R. A. Sheldon, Metalloporphyrins in catalytic oxidations,
Marcel Dekker, New York, 1994; c) H.-J. Lu, X. P. Zhang,
Chem. Soc. Rev. 2011, 40, 1899 – 1909.
4
www.angewandte.org
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2012, 51, 1 – 5
These are not the final page numbers!

Angewandte
Chemie
Communications
Crystal Engineering
A 12-connected fcu metal–organic
framework (MOF), MMPF-3, has been
prepared using a CoII metalloporphyrin.
MMPF-3 is comprised of the same poly-
hedral supermolecular building blocks as
the prototypal fcu-MOF, fcu-MOF-1, and
its nanoscale cavities feature eighteen
catalytically active cobalt centers. The
high density (ca. 5 cobalt sites/nm3)
affords MMPF-3 superior performance in
catalytic epoxidation of trans-stilbene
compared to other MOFs.
L. Meng, Q. Cheng, C. Kim, W.-Y. Gao,
L. Wojtas, Y.-S. Chen, M. J. Zaworotko,*
X. P. Zhang,* S. Ma*
&&&& — &&&&
Crystal Engineering of a Microporous,
Catalytically Active fcu Topology MOF
Using a Custom-Designed
Metalloporphyrin Linker
Angew. Chem. Int. Ed. 2012, 51, 1 – 5
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
5
These are not the final page numbers!