Pore space partition by symmetry-matching regulated ligand insertion and dramatic tuning on carbon dioxide uptake

Article abstract of DOI:10.1021/ja512137t

Metal-organic frameworks (MOFs) with the highest CO₂ uptake capacity are usually those equipped with open metal sites. Here we seek alternative strategies and mechanisms for developing high-performance CO₂ adsorbents. We demonstrate that through a ligand insertion pore space partition strategy, we can create crystalline porous materials (CPMs) with superior CO₂ uptake capacity. Specifically, a new material, CPM-33b-Ni without any open metal sites, exhibits the CO₂ uptake capacity comparable to MOF-74 with the same metal (Ni) at 298 K and 1 bar.

Full text of DOI:10.1021/ja512137t

Communication
pubs.acs.org/JACS
Pore Space Partition by Symmetry-Matching Regulated Ligand
Insertion and Dramatic Tuning on Carbon Dioxide Uptake
Xiang Zhao,† Xianhui Bu,*,‡ Quan-Guo Zhai,† Huy Tran,‡ and Pingyun Feng*,†
†Department of Chemistry, University of California, 501 Big Springs Road, Riverside, California 92521, United States and
‡Department of Chemistry and Biochemistry, California State University, Long Beach, 1250 Bellflower Boulevard, Long Beach,
California 90840, United States
S
* Supporting Information
ABSTRACT: Metal−organic frameworks (MOFs) with
the highest CO2 uptake capacity are usually those
equipped with open metal sites. Here we seek alternative
strategies and mechanisms for developing high-perform-
ance CO2 adsorbents. We demonstrate that through a
ligand insertion pore space partition strategy, we can create
crystalline porous materials (CPMs) with superior CO2
uptake capacity. Specifically, a new material, CPM-33b-Ni
without any open metal sites, exhibits the CO2 uptake
capacity comparable to MOF-74 with the same metal (Ni)
at 298 K and 1 bar.
rystalline porous materials have attracted much attention
Cdue to their useful porosity and compositional and
architectural diversity.1,2 The relatively simple chemistry allows
one to achieve intricate design and precise control over
geometry and functionality.3 It has now become important to
realize the fine control over materials properties for specific
purposes.4 Creating CPMs with open metal sites (OMSs) is
among the most successful strategies to improve gas sorption
properties.5−7 On the other hand, OMSs could lead to
decreased framework rigidity and may also be subject to
competitive attacks by species other than desired adsorbates.8
Therefore, development of alternative strategies for creating
high-performance adsorbents is beneficial.9
During adsorption, MOFs with a large cavity are expected to
promote a greater portion of guest−guest interactions
Figure 1. Illustration of pore space partition through symmetry-
matching regulated ligand insertion. (a) Viewed along c axis and (b)
side view of the channels showing the cylindrical channel before and
after partition (green: Ni, red: O, blue: N, gray: C).
(especially with increasing pressure) among the total combined
host−guest and guest−guest interactions. For efficient capture
of small gas molecules at ambient conditions, maximizing host−
guest interactions by encaging gas molecules in snug pockets of
pore space can be a fruitful approach. To put this concept into
practice, we have proposed the pore space partition concept
and reported several strategies.10 The essence of these strategies
is to anchor a metal ion or cluster at the cage or channel centers
and run hooks (functional groups) from the framework to such
metal species, thereby partitioning the pore space into multiple
domains.
In this report, MIL-88 type structures were selected as the
prototype framework to demonstrate the above strategy. MIL-
88, [M3O(H2O)2X(L)3]·guest (M = Fe, Cr; X = F, Cl, acetate;
L = fdc, bdc, ndc, bpdc) represents an isoreticular series of
MOFs built from metal trimers and linear dicarboxylate
ligands.11−14 Their network topology was assigned as the 6-
connected acs net and features hexagonal-shaped channels
along the c-axis, together with trigonal bipyrimidal cages.
Here, we report a new pore space partition strategy:
symmetry-matching regulated ligand insertion (Figure 1a).
The strategy entails the insertion of a secondary ligand (Ls)
into a primary framework and utilizes the symmetry and size
matching between Ls and the geometrical pattern of framework
coordination sites and dimension of channels.
Received: November 27, 2014
© XXXX American Chemical Society
A
DOI: 10.1021/ja512137t
J. Am. Chem. Soc. XXXX, XXX, XXX−XXX

Journal of the American Chemical Society
Communication
Table 1. Crystal Data of CPM-33, 34, 35, and 37
a
b
code
formula
a,b (Å)
c (Å)
R (F)
CPM-33a
CPM-33b
CPM-33c
CPM-33d
CPM-34
CPM-35
CPM-37
Ni3OH(bdc)3tpt
16.7775(12)
16.7427(4)
16.7446(6)
16.7342(3)
16.6706(2)
16.6492(15)
20.6087(2)
15.184(3)
15.3279(8)
15.1964(9)
15.2330(5)
20.9026(4)
25.836(3)
0.029
0.052
0.055
0.059
0.036
0.036
0.1071
Ni3OH(dhbdc)3tpt
Ni3OH(NH2bdc)3tpt
Ni3OH(1,4-ndc)3tpt
Ni3OH(2,6-ndc)3tpt
Ni3OH(bpdc)3tpt
Ni3OH(bpdc)3tpbtc
22.7238(5)
a
b
The space group of CPM-33d and CPM-34 adopt P-31c, while all other compounds adopt P63/mmc. bdc = benzene-1,4-dicarboxylate, dhbdc =
2,5-dihydroxybenzene-1,4-dicarboxylate, NH2bdc = 2-aminobenzene-1,4-dicarboxylate, 1,4-ndc = naphthalene-1,4-dicarboxylate, 2,6-ndc =
naphthalene-2,6-dicarboxylate, bpdc = biphenyl-4,4′-dicarboxylate, tpt =2,4,6-tri(4-pyridinyl)-1,3,5-triazine, tpbtc = N,N′,N″-tri(4-pyridinyl)-1,3,5-
benzenetricarboxamide.
In MIL-88, the metals in the trimeric clusters are terminated
by pendant ligands (such as water, halide, or acetate) on three
axial positions. These pendant groups can be removed or
exchanged, leaving potential open metal sites.15 Furthermore,
on each layer along the ab plane, three such M−L bonds from
three different trimers adopt C3 symmetry and point to the
center of hexagonal channel. Such geometric features make it
possible to fit in planar tritopic ligands with C3 symmetry,
which can occupy all three OMSs simultaneously. In this work,
we examined our strategy with select C3 ligands including 2,4,6-
tri(4-pyridyl)-1,3,5-triazine (tpt) (Figure 1a).
and stabilize the snapshots of two different states during
“breathing”. CPM-35 and -37 illustrate this success (Figure 2a).
MIL-88 frameworks are flexible and well known for their
giant swelling effect due to the loss or gain of guest species.11
Such flexibility intrinsic in MIL-88 structural type relaxes the
size-matching requirement and makes it easier to select a C3
ligand to fit in the channel. Thus, MIL-88 provides an ideal
platform to test our pore space partition strategy.
The synthesis was performed using stoichiometric amount of
metal nitrates, dicarboxylic acids, and the neutral tritopic
ligands tpt or its extended derivative N,N′,N″-tri(4-pyridinyl)-
1,3,5-benzene-tricarboxamide (tpbtc) in DMF or DMA. Single
crystal X-ray crystallography data confirmed the success of this
partitioning strategy. By using different combinations of
dicarboxylic acid and tritopic ligands, single crystals of seven
isoreticular MOFs were obtained (Table 1). In contrast to the
original MIL-88 structures in which the trimers are 6-
connected, trimers in CPMs reported here are 9-connected
(Figure S3) with their three axial positions occupied by pyridyl
groups from tpt or tpbtc ligands.
The immediate result from the partition strategy is the loss of
OMSs, which are now occupied by tpt ligand. In addition, the
framework is rigidified and no longer breathable. The
rigidification leads to well-defined and potentially more stable
structures. Such partitioning does not affect the trigonal
bipyramidal cage (Figure S2), however, the original large
continuous hexagonal channel has now been partitioned by the
tpt ligand into infinite number of finite segments. For example,
MIL-88b has a continuous cylindrical channel of ∼10.4 Å in
diameter, but infinite in length. By partitioning with tpt ligand,
the channel in CPM-33a was fragmented into numerous small
segments of 4.5 Å in length (Figure 1b) with potential for
enhanced confinement effects. The tpt ligand is expected to
provide additional sites of adsorption for gas molecules and
allows the pore space to be utilized more efficiently for some
specific applications.
Figure 2. Two methods for the control of pore properties, leading to
an entire structural family. (a) By fixing Lp (the primary ligand which is
a dicarboxylate here) and tuning Ls, the unit cell on the ab plane can
be accurately defined. CPM-35 and -37 represent the stabilized
snapshots of two different states (a more open and a less open state)
during framework breathing of MIL-88d. (b) By fixing Ls and tuning
Lp, the height of cylindrical pores and the density of extra host surface
for host−guest interaction can be tuned.
Without the use of our pore partitioning strategy, MIL-88d can
expand and shrink with its a (or b) axis drifting within the range
between 10 Å (the collapsed form) and 20 Å (the open form).
In comparison, with the support from rigid ligand tpt and tpbtc,
CPM-35 and CPM-37 have the a (or b) axis of 16.6 and 20.6 Å,
respectively. These two captured states correspond to a less
open form and a more open form during the breathing process
of flexible MIL-88d. Clearly, it should be feasible to capture
other intermediate breathing states, given proper ligand choice.
The control of pore properties extends beyond the diameter
of the cylindrical pore. The height of each segment of
cylindrical pore can also be varied by adjusting the length of
In addition to the pore space partition, the fine control over
pore properties can be accomplished by choosing appropriate
ligand combinations. In particular, we were even able to capture
B
DOI: 10.1021/ja512137t
J. Am. Chem. Soc. XXXX, XXX, XXX−XXX

Journal of the American Chemical Society
Communication
the dicarboxylate ligand, as illustrated by CPM-35, -34, and -33
containing bpdc, ndc, and bdc, respectively (Figure 2b). These
ligands have quite different lengths, however, they can form the
same structure type with almost the same length on the a (or b)
axis (determined by the same tpt ligand) and yet the
dramatically different c axis (determined by the dicarboxylic
acid). Along with this variation in the length of the c axis is the
increased density of the effective host surface exposed to the
adsorbate. For example, CPM-35 provides the extra surface
from tpt every 10.0 Å. In contrast, CPM-33 provides the extra
surface from tpt every 4.5 Å, which is more than twice denser
than in CPM-35.
A series of isoreticular phases with exactly the same backbone
with CPM-33a, but with additional -OH, -NH2 groups and
extended aromatic ring attached to the bdc, have also been
made (Table 1). Of particular interest is CPM-33b made from
H2dhbdc. In the fully deprotonated −4 form, H2dhbdc (also
denoted as H2bdc-(OH)2) was used to build the well-known
MOF-74 family,16,17 which has shown superior gas sorption
properties for many gases. However, this ligand is not very
commonly seen in other MOF structure types, and its hydroxyl
group usually does not undergo deprotonation.18 In this work,
the joint use of Lp and Ls ligands suppressed the formation of
MOF-74-Ni and led to the creation of MIL-88-type topology
with elegantly partitioned pore space and gas uptake capacity
comparable to MOF-74-Ni.
value reported for MIL-88 or related structures (Table S1). It
should be noted that CPM-33a does not have any exposed
metal sites and the pore space partition likely plays a significant
role in its high CO2 uptake.
With two -OH sites on the benzene ring, CPM-33b showed
even greater CO2 uptake capacity. Under 1 bar, CPM-33b can
adsorb 173.9 cm3/g at 273 K and 126.4 cm3/g at 298 K. Such
uptake values at both temperatures are impressive, and the
uptake capacity under ambient condition is comparable to
MOF-74-Ni and MOF-74-Zn (Table S2).5a,6a To the best of
our knowledge, under ambient condition, the gravimetric value
of CPM-33b (Ni in this case) is only lower than MOF-74(Mg,
Co) (for volumetric uptake capacity, two other MOFs, UTSA-
16 and SIFSIX-2-Cu-i, are also higher).6a,9a,b This gravimetric
value represents the highest CO2 uptake capacity among MOFs
without open metal sites. When converting the sorption
amount to the numbers of CO2 molecules adsorbed in each
unit cell, it shows that ∼2 CO2 molecules are captured at 0.1
bar and ∼12 CO2 molecules are captured at 1 bar.
With CO2 sorption isotherms at two different temperatures,
the isosteric heat plot for CO2 sorption is obtained for both
compounds (Figure 3c). Without open metal sites, both
compounds show a moderate isosteric heat. At zero coverage,
the Qst for CPM-33a is estimated to be −22.5 kJ/mol. CPM-
33b shows a slightly higher Qst of −25.0 kJ/mol.
CPM-33a and -33b were selected for gas sorption studies.
From N2 gas sorption (Figure 3a), the surface areas were
The superior sorption performance of CPM-33b for CO2
prompted us to study the sorption of several fuel molecules
such as H2, C2H2, and CH4 (Figure 3d). Under 1 bar, it can
adsorb 220.8 cm3/g H2 at 77 K. Also its uptake capacity for
CH4 and C2H2 reaches 41.3 and 162.5 cm3/g, respectively at
273 K. Its corresponding value at 298 K is 26.5 and 150.7 cm3/
g for CH4 and C2H2, respectively (Figures S5 and S6).
In summary, we have introduced a novel symmetry-matching
regulated ligand insertion strategy to partition the pore space in
CPMs. Through this strategy, fine tailoring of the pore
properties can be achieved. By introducing the tripyridyl-type
ligand into the synthesis of MIL-88 type structure, a family of
Ni-trimer-based MOFs have been obtained. The gas sorption
study shows that the CPM-33 family exhibits superior CO2
uptake capacity. In particular, CPM-33b has the highest
gravimetric CO2 uptake value among MOFs without open
metal sites and is comparable to MOF-74-Ni. Importantly, we
believe this study reveals a promising family of materials for gas
sorption applications. Similar to the MOF-74 platform, which
can incorporate different divalent metal ions to allow dramatic
tuning of gas sorption properties, the metal trimer based
structure platform here bestows even more versatility, because
they can potentially incorporate more types of metal ions (even
with different charges, Mg, Zn, Co, Ni, Fe, Cr, Sc, V, In, or their
mixtures) into the structure. Furthermore, greater flexibility can
be achieved not only by tuning metal cations but also by
controlling both primary and secondary ligands. This opens up
numerous opportunities to tune the functionalities and
properties of the materials. As demonstrated here, a small
change on the ligand can dramatically improve the CO2 uptake
capacity of the material. Thus, it is expected a great potential
can be reached in this family of the materials in properties and
applications.
Figure 3. Gas sorption study on compounds CPM-33a and -33b. (a)
N2 sorption isotherm at 77 K. (b) CO2 sorption at 273 and 298 K,
respectively. (c) Isosteric heat plots with low CO2 loading. (d) H2,
C2H2, and CH4 sorption isotherms for CPM-33b.
estimated to be 966 and 808 m2/g obtained from BET method
and 1257 and 1119 m2/g from Langmuir method, respectively.
The surface area of CPM-33b is slightly lower than CPM-33a,
probably due to the reduced pore space caused by protruding
-OH groups on the dhbdc ligand.
For CO2 (Figure 3b), the uptake of CPM-33a under 1 bar
reaches 137.2 cm3/g at 273 K and 73.6 cm3/g at 298 K,
respectively. This value is exceptionally high compared to the
C
DOI: 10.1021/ja512137t
J. Am. Chem. Soc. XXXX, XXX, XXX−XXX

Journal of the American Chemical Society
Communication
(9) (a) Nugent, P.; Belmabkhout, Y.; Burd, S. D.; Cairns, A. J.;
Luebke, R.; Forrest, K.; Pham, T.; Ma, S.; Space, B.; Wojtas, L.;
Eddaoudi, M.; Zaworotko, M. J. Nature 2013, 495, 80. (b) Xiang, S.;
He, Y.; Zhang, Z.; Wu, H.; Zhou, W.; Krishna, R.; Chen, B. Nat.
Commun. 2012, 3, 954. (c) Li, J.-R.; Yu, J.; Lu, W.; Sculley, J.;
Balbuena, P. B.; Zhou, H.-C. Nat. Commun. 2013, 4, 1538.
(d) McDonald, T. M.; D’Alessandro, D. M.; Krishna, R.; Long, J. R.
Chem. Sci. 2011, 2, 2022. (e) An, J.; Geib, S. J.; Rosi, N. J. Am. Chem.
Soc. 2009, 132, 38. (f) Lin, Q.; Wu, T.; Zheng, S.-T.; Bu, X.; Feng, P. J.
Am. Chem. Soc. 2012, 134, 784. (g) Cui, P.; Ma, Y.-G.; Li, H.-H.; Zhao,
B.; Li, J.-R.; Cheng, P.; Balbuena, P. B.; Zhou, H. C. J. Am. Chem. Soc.
2012, 134, 18892. (h) Wang, F.; Fu, H. R.; Kang, Y.; Zhang, J. Chem.
Commun. 2014, 50, 12065.
(10) (a) Zheng, S.-T.; Bu, J. T.; Li, Y.; Wu, T.; Zuo, F.; Feng, P.; Bu,
X. J. Am. Chem. Soc. 2010, 132, 17062. (b) Bu, F.; Lin, Q.; Zhai, Q.;
Wang, L.; Wu, T.; Zheng, S.-T.; Bu, X.; Feng, P. Angew. Chem., Int. Ed.
2012, 51, 8538. (c) Zheng, S.-T.; Wu, T.; Irfanoglu, B.; Zuo, F.; Feng,
P.; Bu, X. Angew. Chem., Int. Ed. 2011, 50, 8034. (d) Zheng, S.-T.; Wu,
T.; Zuo, F.; Chou, C.-T.; Feng, P.; Bu, X. J. Am. Chem. Soc. 2012, 134,
1934. (e) Zheng, S.-T.; Mao, C.; Wu, T.; Lee, S.; Feng, P.; Bu, X. J.
Am. Chem. Soc. 2012, 134, 11936. (f) Zheng, S.-T.; Zhao, X.; Lau, S.;
Fuhr, A.; Feng, P.; Bu, X. J. Am. Chem. Soc. 2013, 135, 10270.
ASSOCIATED CONTENT
■
S
* Supporting Information
Experimental details, additional figures, and cif file. This
material is available free of charge via the Internet at http://
pubs.acs.org.
AUTHOR INFORMATION
■
Corresponding Authors
*xianhui.bu@csulb.edu
*pingyun.feng@ucr.edu
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
The research is supported by the U.S. Department of Energy,
Office of Basic Energy Sciences, Division of Materials Sciences
and Engineering under Award DE-FG02-13ER46972 (P.F.).
(11) (a) Serre, C.; Mellot-Draznieks, C.; Surble,
Filinchuk, Y.; Ferey, G. Science 2007, 315, 1828. (b) Serre, C.;
Millange, F.; Surble, S.; Ferey, G. Angew. Chem., Int. Ed. 2004, 43,
6286. (c) Mellot-Draznieks, C.; Serre, C.; Surble, S.; Audebrand, N.;
Ferey, G. J. Am. Chem. Soc. 2005, 127, 16273.
(12) (a) Sudik, A. C.; Cote, A. P.; Yaghi, O. M. Inorg. Chem. 2005,
́
S.; Audebrand, N.;
REFERENCES
■
́
(1) (a) Furukawa, H.; Cordova, K. E.; O’Keeffe, M.; Yaghi, O. M.
Science 2013, 341, 123044. (b) Horcajada, P.; Gref, R.; Baati, T.; Allan,
́
́
́
P. K.; Maurin, G.; Couvreur, P.; Ferey, G.; Morris, R. E.; Serre, C.
́
Chem. Rev. 2012, 112, 1232. (c) Schoedel, A.; Zaworotko, M. J. Chem.
Sci. 2014, 5, 1269. (d) Zhou, H.-C.; Long, J.; Yaghi, O. M. Chem. Rev.
2012, 112, 673.
̂
́
44, 2998. (b) Ma, S.; Simmons, J. M.; Yuan, D.; Li, J.-R.; Weng, W.;
Liu, D.-J.; Zhou, H.-C. Chem. Commun. 2009, 4049.
(2) (a) Parnham, E. R.; Morris, R. E. Acc. Chem. Res. 2007, 40, 1005.
(b) Wu, H. H.; Gong, Q. H.; Olson, D. H.; Li, J. Chem. Rev. 2012, 112,
836. (c) Mohideen, M. I. H.; Xiao, B.; Wheatley, P. S.; McKinlay, A.
C.; Li, Y.; Slawin, A. M. Z.; Aldous, D. W.; Cessford, N. F.; Duren, T.;
Zhao, X. B.; Gill, R.; Thomas, K. M.; Griffin, J. M.; Ashbrook, S. E.;
Morris, R. E. Nat. Chem. 2011, 3, 304. (d) Takaishi, S.; DeMarco, E. J.;
Pellin, M. J.; Farha, O. K.; Hupp, J. T. Chem. Sci. 2013, 4, 1509.
(3) (a) Perry, J. J.; Perman, J. A.; Zaworotko, M. J. Chem. Soc. Rev.
2009, 38, 1400. (b) Cohen, S. M. Chem. Rev. 2012, 112, 970.
(13) (a) Ibarra, I. A.; Lin, X.; Yang, S.; Blake, A. J.; Walker, G. S.;
Barnett, S. A.; Allan, D. R.; Champness, N. R.; Hubberstey, P.;
Schroder, M. Chem.Eur. J. 2010, 16, 13671. (b) Dietzel, P. D. C.;
̈
Blom, R.; Fjellvag, H. Dalton Trans. 2006, 2055.
̊
(14) (a) Horcajada, P.; Salles, F.; Wuttke, S.; Devic, T.; Heurtaux, D.;
Maurin, G.; Vimont, A.; Daturi, M.; David, O.; Magnier, E.; Stock, N.;
́
Filinchuk, Y.; Popov, D.; Riekel, C.; Ferey, G.; Serre, C. J. Am. Chem.
Soc. 2011, 133, 17839−17847. (b) McKinlay, A. C.; Eubank, J. F.;
Wuttke, S.; Xiao, B.; Wheadey, P. S.; Bazin, P.; Lavalley, J. C.; Daturi,
M.; Vimont, A.; De Weireld, G.; Horcajada, P.; Serre, C.; Morris, R. E.
Chem. Mater. 2013, 25, 1592.
̈
(c) Farha, O. K.; Yazaydın, A. O.; Eryazici, I.; Malliakas, C. D.; Hauser,
B. G.; Kanatzidis, M. G.; Nguyen, S. T.; Snurr, R. Q.; Hupp, J. T. Nat.
Chem. 2010, 2, 944.
(15) (a) Hwang, K. Y.; Hong, D.-Y.; Chang, J. S.; Jhung, S. H.; Seo1,
(4) (a) Fei, H.; Shin, J. W.; Meng, Y. S.; Adelhardt, M.; Sutter, J.;
Meyer, K.; Cohen, S. M. J. Am. Chem. Soc. 2014, 136, 4965. (b) Stavila,
V.; Talin, A. A.; Allendorf, M. D. Chem. Soc. Rev. 2014, 43, 5994.
(c) Stavila, V.; Bhakta, R. K.; Alam, T. M.; Majzoub, E. H.; Allendorf,
M. D. ACS Nano 2012, 6, 9807. (d) Sun, C.-Y.; Wang, X.-L.; Zhang,
X.; Qin, C.; Li, P.; Su, Z.-M.; Zhu, D.-X.; Shan, G. G.; Shao, K. Z.; Wu,
H.; Li, J. Nat. Commun. 2013, 4, 2717. (e) Zhao, X.; Bu, X.; Wu, T.;
Zheng, S.-T.; Wang, L.; Feng, P. Nat. Commun. 2013, 4, 2344.
(5) (a) Sumida, K.; Rogow, D. L.; Mason, J. A.; McDonald, T. M.;
Block, E. D.; Herm, Z. R.; Bae, T.-H.; Long, J. R. Chem. Rev. 2012,
́
Y. K.; Kim, J.; Vimont, A.; Daturi, M.; Serre, C.; Ferey, G. Angew.
Chem., Int. Ed. 2008, 47, 4144. (b) Mao, C.; Kudla, R. A.; Zuo, F.;
Zhao, X.; Mueller, L. J.; Bu, X.; Feng, P. J. Am. Chem. Soc. 2014, 136,
7579.
(16) (a) Dietzel, P. D. C.; Johnsen, R. E.; Blom, R.; Fjellvag, H.
Chem.Eur. J. 2008, 14, 2389. (b) Dietzel, P. D. C.; Morita, Y.; Blom,
R.; Fjellvag, H. Angew. Chem., Int. Ed. 2005, 44, 6354. (c) Dietzel, P. D.
C.; Panella, B.; Hirscher, M.; Blom, R.; Fjellvag, H. Chem. Commun.
2006, 959.
(17) Deng, H.; Grunder, S.; Cordova, K. E.; Valente, C.; Furukawa,
̆
112, 724. (b) Dinca, M.; Dailly, A.; Liu, Y.; Brown, C. M.; Neumann,
́
H.; Hmadeh, M.; Gandara, F.; Whalley, A. C.; Liu, Z.; Asahina, S.;
Kazumori, H.; O’Keeffe, M.; Terasaki, O.; Stoddart, J. F.; Yaghi, O. M.
Science 2012, 336, 1018.
(18) Furukawa, H.; Gandara, F.; Zhang, Y.-B.; Jiang, J.; Queen, W. L.;
́
Hudson, M. R.; Yaghi, O. M. J. Am. Chem. Soc. 2014, 136, 4369.
D. A.; Long, J. R. J. Am. Chem. Soc. 2006, 128, 16876. (c) Demessence,
A.; D’Alessandro, D. M.; Foo, M. L.; Long, J. R. J. Am. Chem. Soc.
2009, 131, 8784.
(6) (a) Caskey, S. R.; Wong-Foy, A. G.; Matzger, A. J. J. Am. Chem.
Soc. 2008, 130, 10870. (b) Britt, D.; Furukawa, H.; Wang, B.; Glover,
T. G.; Yaghi, O. M. Proc. Natl. Acad. Sci. U.S.A. 2009, 106, 20637.
̈
(c) Yazaydin, A. O.; Snurr, R. Q.; Park, T.-H.; Koh, K.; Liu, J.; LeVan,
M. D.; Benin, A. I.; Jakubczak, P.; Lanuza, M.; Galloway, D. B.; Low, J.
L.; Willis, R. R. J. Am. Chem. Soc. 2009, 131, 18198.
(7) (a) Li, B. Y.; Zhang, Z. J.; Li, Y.; Yao, K. X.; Zhu, Y. H.; Deng, Z.
Y.; Yang, F.; Zhou, X. J.; Li, G. H.; Wu, H. H.; Nijem, N.; Chabal, Y. J.;
Shi, Z.; Feng, S. H.; Li, J. Angew. Chem., Int. Ed. 2012, 51, 1412.
(b) Luo, J.; Wang, J.; Li, G.; Huo, Q.; Liu, Y. Chem. Commun. 2013,
49, 11433. (c) Xiang, S.; Zhou, W.; Gallegos, J. M.; Liu, Y.; Chen, B. J.
Am. Chem. Soc. 2009, 131, 12415.
(8) Kizzie, A. C.; Wong Foy, A. G.; Matzger, A. J. Langmuir 2011, 27,
6368.
D
DOI: 10.1021/ja512137t
J. Am. Chem. Soc. XXXX, XXX, XXX−XXX