Dual-functionalized metal-organic frameworks constructed from hexatopic ligand for selective CO2 adsorption

Article abstract of DOI:10.1021/ic502921j

A ligand design approach, which requires rational design of ligand based on the knowledge of specific target, was applied for the synthesis of two interesting and robust MOFs 1 and 2 containing unusual several types of copper(II) secondary building units

Full text of DOI:10.1021/ic502921j

Article
pubs.acs.org/IC
Dual-Functionalized Metal−Organic Frameworks Constructed from
Hexatopic Ligand for Selective CO2 Adsorption
Shi-Yuan Zhang, Xiaoping Zhang, Huimin Li, Zheng Niu, Wei Shi,* and Peng Cheng
Department of Chemistry, Key Laboratory of Advanced Energy Material Chemistry (MOE) and Collaborative Innovation Center of
Chemical Science and Engineering (Tianjin),Nankai University, Tianjin 300071, P. R. China
S
* Supporting Information
ABSTRACT: A ligand design approach, which requires
rational design of ligand based on the knowledge of specific
target, was applied for the synthesis of two interesting and
robust MOFs 1 and 2 containing unusual several types of
copper(II) secondary building units (SBUs). Thanks to
unsaturated metal centers (UMCs) and azo group, micro-
porous material 1 exhibited not only high CO2 uptake but also
an impressive selective adsorption of CO2 over CH4 and N2.
Moreover, a high H2 uptake of 1 was also observed.
containing groups into MOFs. The N-containing groups
serve as Lewis base sites with localized dipoles and induce
the dispersion and electrostatic forces from the quadrupole
moment of CO2. The higher CO2 uptake capacities at low
pressure can be observed in amine modified MOFs compared
with those of the parent materials.12 Besides, other types of N-
containing groups, for example, azo, triazole, tetrazole,
acylamide, also offer an enhancement of CO2-MOFs
interactions, exhibiting high CO2 uptake, Qst and selectivity.13
With the aim to construct porous MOFs featuring
aforementioned properties and based on our previous
study,14 we designed a hexacarboxylate ligand 1,2,3-tricarbox-
yl-(1′,2′,3′-tricarboxylazophenyl)benzene (H6TTAB) process-
ing polar and nonpolar regions, special orientations, and strong
steric hindrance of carboxylate groups. High symmetrical
polycarboxylate ligands, basically containing 1,3-benzenedicar-
boxylate moieties, will lead to a single SBU in crystal
structure.11a In comparison, multiple types of SBUs can be
generated with potential open Cu2+ sites by applying
asymmetrical 1,2,3-tricarboxylate ligand.15 Herein, we report
the synthesis, crystal structures of two new MOFs
[Cu6(TTAB)2(μ2-OH2)(H2O)8]·(DMF)4(H2O)6 (1) and
H2[Cu6(TTAB)2(μ3-OH)(μ2-OH)(H2O)8]·(DMF)3.5(H2O)6
(2) that integrates unusual different types of SBUs. The gas
adsorption behavior of 1 has also been investigated.
1. INTRODUCTION
Metal−organic frameworks (MOFs), constructed from metal-
based nodes (metal ions or metal-oxo clusters) and linkers
(multitopic organic ligands), have attracted tremendous
interest.1 Their modular nature with high surface area have
made them a promising class of solid state porous materials for
potential application in gas storage2 and separation,3 optical
sensing4 and catalysis.5 More recently, great attention has been
paid to energy/environment-related effluent CO2 capture and
separation using MOFs materials.6 In addition to high
gravimetric uptake and suitable thermodynamics and kinetics,
the optimal MOFs for CO2 separation should have ideal
isosteric heat of adsorption (Qst) that permits reversible
physical adsorption−desorption process.3b,7 Although numer-
ous MOFs with diverse structural and topological types have
been reported, rational design and assembly of functional
crystalline solid represents a huge challenge to meet the specific
criteria.
It is evident that crystal engineering8 facilitates the
development of targeted functional MOFs for CO2 adsorp-
tion/separation. As exemplified by framework topology,
secondary building units (SBUs)9 and directional linkers
together play a major role in the final CO2 sorption behavior.
One approach to improve CO2 affinity and selectively of MOFs
is to create unsaturated metal centers (UMCs) of SBUs.10
Typically, UMCs are obtained by removing terminal ligands
(e.g., H2O, CH3OH) upon heating under vacuum. The specific
interaction exists between charge-dense binding sites of UMCs
and CO2, which attributes to the great quadrupole moment and
polarizability of CO2. The exploitation of [Cu2(CO2)4]
paddlewheel SBU with axial open Cu2+ sites has achieved
fruitful results since the earliest studies of HKUST-1, which has
a relatively high Qst of 29.2 kJ mol−1.11 Another strategy used to
enhance CO2 adsorption is the decoration of nitrogen-
2. EXPERIMENTAL SECTION
2.1. Materials. The commercially available reagents were used
without further purification.
2.1.1. Synthesis of H6TTAB. The ligand H6TTAB was synthesized
according to the reported method.16 Synthetic details are described as
Received: December 9, 2014
© XXXX American Chemical Society
A
DOI: 10.1021/ic502921j
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
follow: A mixture of 5-nitrobenzene-1,2,3-tricarboxylic acid (2.55 g, 10
mmol), Zn (1.3 g, 20 mmol), and NaOH (1.2 g, 30 mmol) in a
mixture of ethanol (50 mL) and water (20 mL) was heated under
reflux. After 24 h, a yellow solid was obtained and collected by
filtration. The resultant solid was dissolved in 50 mL of NaOH (aq, 1
M) and filtered to remove any insoluble solids. The filtrate was
acidified to pH = 3 with HCl (aq, 3 M) to afford an orange precipitate.
The yellow solid 1,2,3-tricarboxyl-(1′,2′,3′-tricarboxylazophenyl)-
benzene (H6TTAB) was obtained by filtration and dried in air
Table 1. Crystal Data and Structure Refinement Details of 1
and 2
1
2
formula
fw
C48H66N8Cu6O43
1824.34
150(2)
orthorhombic
Pnma
C46.5H66.5N7.5Cu6O44.5
1823.83
150(2)
temp (K)
cryst system
space group
a (Å)
monoclinic
C2/c
1
(yield = 75%). H NMR (400 MHz, CDCl3): δ 8.39.
19.348(2)
21.110(2)
19.822(2)
90.00
29.303(3)
16.853(1)
26.713(2)
105.027(8)
12740.8(17)
8
2.1.2. Synthesis of 1. A mixture of CuCl2·2H2O (85 mg, 0.5 mmol),
H6TTAB (45 mg, 0.1 mmol), DMF (7.5 mL), and H2O (7.5 mL) was
sealed in a 23 mL Teflon-lined stainless steel vessel and heated at 90
°C for 3 days, and then cooled to room temperature. Dark green
polyhedral crystals were obtained as a pure phase, washed by DMF,
and dried at room temperature. Yield: 82%. IR (KBr, cm−1): 3400s,
2930w, 2361m, 1643vs, 1423vs, 1367vs, 1257w, 1097m, 819m, 729m,
660m, 486m. Elemental analysis calcd (%) for 1: C 31.60, H 3.65, N
6.14; found: C 31.54, H 3.76, N 6.48.
b (Å)
c (Å)
β (deg)
V (Å3)
Z
Dc (g·cm−3
8096.2(14)
4
)
1.497
1.901
μ (mm−1
F (000)
Rint
)
1.642
2.083
2824
5744
2.1.3. Synthesis of 2. A mixture of Cu(NO3)2·6H2O (122 mg, 0.5
mmol), H6TTAB (45 mg, 0.1 mmol), DMF (5 mL), and H2O (10
mL) was sealed in a 23 mL Teflon-lined stainless steel vessel and
heated at 100 °C for 3 days, and then cooled to room temperature.
Yellow green rod-like crystals were obtained as a pure phase, washed
by DMF, and dried at room temperature. Yield: 76%. IR (KBr, cm−1):
3424vs, 2964vs, 2916m, 2853w, 2361m, 1618s, 1578s, 1456s, 1419s,
1383vs, 1045m, 800w, 723m, 662w. Elemental analysis calcd (%) for
2: C 30.62, H 3.68, N 5.76; found: C 30.39, H 3.31, N 6.06.
2.2. Physical Measurements. Elemental analysis was performed
0.0455
0.0381
GOF
1.039
0.917
R1 (I > 2σ(I))
R2 (all data)
0.0528
0.0681
0.1231
0.1780
Δρmax (e Å−3
)
1.48
1.97
Δρmin (eÅ−3
)
−0.66
−1.76
water at 90 °C for 3 days. Single-crystal X-ray diffraction
analysis reveals that it crystallizes in orthorhombic space group
Pnma. The framework is built from two types of dimer SBUs
joined by 6-connected TTAB linker (Figure 1). One type of
dimer is paddlewheel SBU composed from two Cu2+ and four
carboxylate groups; the other one contains two square
pyramids Cu2+ that share one central μ2-oxo anion. Both
1
on a Perkin−Elmer 240 CHN elemental analyzer. H NMR spectrum
was recorded with a Bruker AV 400 spectrometer at 400 MHz.
Chemical shifts (δ values) were reported in ppm from internal Me4Si.
IR spectra were recorded in the range 400−4000 cm−1 on a Bruker
TENOR 27 spectrophotometer by using KBr pellets. Powder X-ray
diffraction measurements were recorded on a Rigaku D/Max-2500 X-
ray diffractometer using Cu Kα radiation. Thermal analyses (N2
atmosphere, heating rate of 1.5 °C/min) were carried out in a Labsys
NETZSCH TG 209 Setaram apparatus.
2.2.1. X-ray Structure Determination. The crystallographic data
were collected by an Oxford Supernova Single Crystal Diffractometer
equipped with graphite monochromatic Mo Kα radiation (λ = 0.71073
Å). Structures were solved by direct methods with SHELXS program
and refined by full-matrix least-squares techniques against F2 with the
SHELXL program package.17 All non-hydrogen atoms were refined
anisotropically except O14 in 1, and hydrogen atoms were located and
refined isotropically. The contribution of disordered solvent molecules
was treated as a diffuse using the Squeeze procedure in PLATON.18
The resulting new HKL4 files were used to further refine the
structures. Crystallographic data are shown in Table 1. CCDC-
1029791 and -1029792 (1 and 2) contain the supplementary
crystallographic data for this paper. These data can be obtained free
of charge via www.ccdc.cam.ac.uk.
2.2.2. Low-Pressure Sorption Experiments. All gas-adsorption
experiments were performed on a Quantachrome IQ2 automatic
volumetric instrument. All gases used were of 99.999% purity. The
methanol solvent-exchanged sample was degassed at 100 °C for 12h to
remove the guest molecules. The temperature for N2, H2, and Ar
sorption experiments was controlled by a refrigerated bath of liquid
nitrogen (77 K) or liquid argon (87 K). The N2 and Ar sorption
isotherms were recorded over the pressure range 10−7−1 bar at 77 and
87 K, respectively. The H2 sorption isotherms (77 and 87 K) were
carried out over the pressure range 10−3−1 bar. The CO2, CH4, and
N2 sorption isotherms (273 and 298 K) were measured in a
temperature-controlled water bath over the pressure range 10−3−1 bar.
3. RESULTS AND DISCUSSION
Figure 1. (a) Schematic representation of copper SBUs and
hexacarboxylate TTAB6− ligand. (b) Linkage of 4-connected copper
SBUs and 6-connected TTAB6−. (c) Schematic view of 3D framework
of 1. (d) 1D channels within 3D framework of 1.
3.1. Synthesis and Structures of 1 and 2. Dark green
crystals of 1 are obtained under solvothermal reaction of CuCl2·
2H2O with H6TTAB in N,N-dimethylformamide (DMF) and
B
DOI: 10.1021/ic502921j
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
dimer units are linked by four separate hexatopic organic linkers
to build up the 3D structure. The removal of terminal
coordinated water molecules of both dimers can generate
UMCs with open Cu2+ sites. Topology analysis reveals that 1
adopts a 4,4,4,6-c 4-nodal network with Schlafli symbol of
{42.62.82}{44.62}2{45.68.82}2 (Supporting Information Figure
S1). Careful examination of 1 shows that it has 1D solvent
accessible channel along [100] direction with an effective
diameter estimated to be 10.3 Å (considering van der Waals
radii). It is noteworthy that the dumbbell-shaped channels and
zigzag channels are also found along [010] and [001] directions
(Supporting Information Figure S2). The total free volume of 1
with removal of guest molecules is 53.4% (4320.0 Å3 of the unit
cell volume of 8096.2 Å3) by PLATON.18
Solvothermal reaction of Cu(NO3)2·6H2O with H6TTAB in
DMF and water at 100 °C for 3 days yields yellow green rod-
like crystals of 2. The crystallographic analysis reveals that 2
crystallizes in monoclinic space group C/2c and adopts an
unprecedented 3,4,5,6,8-connected network topology. As
shown in Figure 2, the structure of 2 contains two
(Supporting Information Figure S3). The topological point
symbol of 2 is {4·5·6}2{42·52·6·7}{44·54·62}2{44·54·64·72·8}2{46·
514·76·82}.
The control over structural features of 1 and 2 attributes to
the flexibility of TTAB6− ligand, temperature and DMF/H2O
ratio. In 1, two phenyl groups of TTAB6− are nearly
perpendicular to each other with an angle of 80.54°; while
the angles in 2 are reduced to 56.45° and 10.49°. Increased
temperature can provide higher energy thus facilitates the
rotation between two phenyl groups. In fact, the orientation of
TTAB6− ligand is responsible for the alignment of SBUs,
resulting in the structural variation of 1 and 2. In the other
aspect, the increased water amount during synthesis facilitates
the formation of different types of SBUs with terminal water
molecules, as evidenced by the DMF/H2O ratio in the
formulas. Indeed, more types of SBUs require certain
arrangement of TTAB6− ligands by rotation, which in turn
lower the symmetry of the lattice.
The phase purity of the bulk crystalline materials of 1 and 2
was confirmed by similarities between the calculated and as-
synthesized powder X-ray diffraction (PXRD) patterns,
respectively (Supporting Information Figure S4). The
thermogravimetric curve of 1 indicates an initial weight loss
of 31.0% from 25 to 110 °C, corresponding to the loss of
coordinated water molecules and guest molecules (calcd
31.5%). While 2 exhibits a gradual weight loss of 5.5% from
25 to 200 °C (Supporting Information Figure S5), correspond-
ing to the loss of guest water molecules (calcd 5.9%). At 237.5
°C, a weight loss of 29.1% is observed, indicating the loss of
DMF and coordinated water molecules (calcd 28.1%).
3.2. Gas Absorption Properties of 1. The interesting
structural and functional features of 1, that is, the narrow
channels with UMCs and localized dipoles of azo groups,
prompted us to evaluate the gas sorption behavior. Powder
XRD of MeOH-exchanged sample and activated sample
indicate the stability of the framework (Supporting Information
Figure S6). The permanent porosity has been confirmed by
individual N2 and Ar adsorption isotherm at 77 and 87 K
(Supporting Information Figure S7). 1 exhibits a type I
isotherm characteristic of microporous materials and reveals an
overall uptake of 347 (N2) and 388 (Ar) cm3 g−1 at 1 bar. The
apparent surface corresponds to a Brunauer−Emmet−Teller
(BET) surface area of 1224 (N2) and 1382 (Ar) cm3 g−1 and a
Langmuir surface area of 1393 (N2) and 1573 (Ar) cm3 g−1,
respectively. The volumetric H2 uptakes in 1 were collected at
77 and 87 K (Supporting Information Figure S8). All H2
isotherms exhibit rapid kinetics and good reversibility with H2
uptake capacity of 186.1 cm3 g−1 (1.66 wt %) at 77 K and 1.0
bar, and 131.5 cm3 g−1 (1.17 wt %) at 87 K and 1.0 bar.
Moreover, Qst for H2 was determined by Clausius−Clapeyron
equation and estimated to be 8.34 kJ mol−1 at zero coverage
(Supporting Information Figure S9). These values in H2
capacity and Qst are comparably higher than those of previously
reported porous MOFs.2b
Figure 2. (a) Schematic representation of four types of copper SBUs
and hexacarboxylate TTAB6− ligand. (b) Linkage of copper SBUs and
TTAB6−. (c) Schematic view of 3D framework of 2.
crystallographically independent TTAB6− ligands and four
types of Cu2+ SBUs. Four monodentated carboxylate groups
from four different TTAB6− ligands coordinate to Cu2+ center
that forms 4-connected (4-c) SBU. The 2-c SBU is based on a
five coordinated Cu2+ ion. The 3-c dimer SBU contains an
octahedral and a square pyramid sharing two μ2-oxo anions.
The 8-c penta-copper SBU can be regarded as the junction of
two Cu3O clusters. Specifically, the center Cu2+ adopts
octahedral coordination geometry, while the other two are
five coordinated. The μ3-O lies in the C3 axis of three Cu2+
atoms. It should be noted that water molecules in 2-c, 3-c and
8-c SBUs would generate potential UMCs through desolvation.
The TTAB6− ligands serve as 6-c nodes that further link these
Cu2+ SBUs. As a consequence, the assembly of these different
types of nodes results in a rare 3,4,5,6,8-c 5-nodal network
The special dual-functionalities in 1 prompt us to further
explore the potential applications toward CO2 capture and
separation. We have measured low pressure CO2, CH4 and N2
sorption data at 273 and 298 K, as shown in Figure 3. The CO2
uptake capacity of 1 reaches 140.0 cm3 g−1 at 273 K and 81.2
cm3 g−1 at 298 K, respectively, which is relatively high
compared to other classes of porous materials.3 Without the
large surface area and free volume, we attribute the high CO2
uptake to UMCs and azo groups, which serve as potential
C
DOI: 10.1021/ic502921j
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
4. CONCLUSIONS
In conclusion, a hexacarboxylate ligand containing azo group
has been successfully used for the construction of MOFs, 1 and
2, showing dual-functionalities and novel topologies. Micro-
porous MOF 1 exhibits a hydrogen uptake capacity of 1.66 wt
% at 77 K and 1 bar and a high CO2 uptake of 140.0 cm3 g−1 at
273 K. The utilization of UMCs and N-containing moieties
affords enhanced Qst and uptakes because of their special
interactions with gas molecules. The high CO2 affinity over
CH4 and N2, particularly at low pressure certainly renders 1 a
prospective material for low CO2 concentration purification.
These highly desirable features in the context of the
multicomponent gas adsorption will be needed to develop
MOFs for industrial applications.
ASSOCIATED CONTENT
■
S
* Supporting Information
Figure 3. Sorption isotherms for CO2, CH4, and N2 at 273 and 298 K.
(Adsorption and desorption branches are shown with closed and open
symbols, respectively.)
Additional single crystal X-ray analysis figures, powder X-ray
diffraction data, thermogravimetic measurements, gas sorption
data, and analyzing details. This material is available free of
charge via the Internet at http://pubs.acs.org.
binding sites for CO2 that facilitate the dipole−quadrupole
interactions. The Qst for CO2 was calculated to be 27.4 kJ mol−1
by fitting the 273 and 298 K isotherms to the virial equation,
indicating high affinity toward CO2 at low loading (Supporting
Information Figure S10 and Table S1). For comparison, the
CH4 and N2 uptakes for 1 at 1 atm were found to be 19.3 and
11.6 cm3 g−1 at 273 K, 10.4 and 4.8 cm3 g−1 at 298 K,
respectively. To predict the CO2 separation performance of 1 at
298 K, ideal adsorbed solution theory (IAST)19 calculations
were used for binary gas adsorption selectivity under practically
relevant conditions (Figure 4). In particular, 1 shows a high
AUTHOR INFORMATION
■
Corresponding Author
*E-mail: shiwei@nankai.edu.cn.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We thank the “973 program” (2012CB821702), the MOE
(NCET-13-0305, IRT-13R30 and IRT13022), and 111 Project
(B12015) for financial support.
REFERENCES
■
(1) (a) Moulton, B.; Zaworotko, M. J. Chem. Rev. 2001, 101, 1629−
1658. (b) Kitagawa, S.; Kitaura, R.; Noro, S.-i. Angew. Chem., Int. Ed.
2004, 43, 2334−2375. (c) Batten, S. R.; Neville, S. M.; Turner, D. R.
Coordination Polymers: Design, Analysis and Application; Royal Society
of Chemistry: Cambridge, U.K., 2009. (d) Metal−Organic Frameworks:
Design and Application; MacGillivray, L. R., Ed.; Wiley & Sons, Inc.:
Hoboken, NJ, 2010.
(2) (a) Li, J.-R.; Ma, Y.; McCarthy, M. C.; Sculley, J.; Yu, J.; Jeong,
H.-K.; Balbuena, P. B.; Zhou, H.-C. Coord. Chem. Rev. 2011, 255,
1791−1823. (b) Suh, M. P.; Park, H. J.; Prasad, T. K.; Lim, D. W.
Chem. Rev. 2012, 112, 782−835. (c) He, Y.; Zhou, W.; Qian, G.; Chen,
B. Chem. Soc. Rev. 2014, 43, 5657−5678.
(3) (a) Li, J.-R.; Sculley, J.; Zhou, H.-C. Chem. Rev. 2012, 112, 869−
932. (b) Sumida, K.; Rogow, D. L.; Mason, J. A.; McDonald, T. M.;
Bloch, E. D.; Herm, Z. R.; Bae, T.-H.; Long, J. R. Chem. Rev. 2012,
112, 724−781.
(4) (a) Kreno, L. E.; Leong, K.; Farha, O. K.; Allendorf, M.; Van
Duyne, R. P.; Hupp, J. T. Chem. Rev. 2012, 112, 1105−1125. (b) Cui,
Y.; Chen, B.; Qian, G. Coord. Chem. Rev. 2014, 273, 76−86.
(5) Lee, J.; Farha, O. K.; Roberts, J.; Scheidt, K. A.; Nguyen, S. T.;
Hupp, J. T. Chem. Soc. Rev. 2009, 38, 1450−1459.
(6) (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, 80−84. (b) Zhang,
Z.; Zhao, Y.; Gong, Q.; Li, Z.; Li, J. Chem. Commun. 2013, 49, 653−
661.
Figure 4. Calculated selectivity of CO2/CH4 (50:50) and CO2/N2
(10:90) at 298 K, respectively.
CO2/N2 selectivity of 29.1 in a 10:90 molar ratio of CO2 and
N2 mixture at 1 bar. The calculated CO2/CH4 selectivity is 10.5
at 1 bar from equimolar CO2 and CH4 mixture. The selectivity
of 1 for CO2 over CH4 and N2 under these conditions is
comparable to the majority of MOFs reported to date.3a,6b
Indeed, many MOFs with high selectivity have lower CO2
uptake than 1.3 Therefore, this material would be a promising
candidate for natural gas purification and postcombustion CO2
capture applications.
(7) Sayari, A.; Belmabkhout, Y.; Serna-Guerrero, R. Chem. Eng. J.
2011, 171, 760−774.
(8) Desiraju, G. R. Angew. Chem., Int. Ed. 2007, 46, 8342−8356.
D
DOI: 10.1021/ic502921j
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
(9) (a) Rosi, N. L.; Kim, J.; Eddaoudi, M.; Chen, B.; O’Keeffe, M.;
Yaghi, O. M. J. Am. Chem. Soc. 2005, 127, 1504−1518. (b) Perry, J. J.;
Perman, J. A.; Zaworotko, M. J. Chem. Soc. Rev. 2009, 38, 1400−1417.
(10) (a) Chen, B.; Xiang, S.; Qian, G. Acc. Chem. Res. 2010, 43,
1115−1124. (b) Caskey, S. R.; Wong-Foy, A. G.; Matzger, A. J. J. Am.
Chem. Soc. 2008, 130, 10870−10871.
(11) (a) Chui, S. S.-Y.; Lo, S. M.-F.; Charmant, J. P. H.; Orpen, A. G.;
Williams, I. D. Science 1999, 283, 1148−1150. (b) Montoro, C.;
Garcia, E.; Calero, S.; Perez-Fernandez, M. A.; Lopez, A. L.; Barea, E.;
Navarro, J. A. R. J. Mater. Chem. 2012, 22, 10155−10158. (c) Bordiga,
S.; Regli, L.; Bonino, F.; Groppo, E.; Lamberti, C.; Xiao, B.; Wheatley,
P. S.; Morris, R. E.; Zecchina, A. Phys. Chem. Chem. Phys. 2007, 9,
2676−2685.
(12) (a) Millward, A. R.; Yaghi, O. M. J. Am. Chem. Soc. 2005, 127,
17998−17999. (b) Couck, S.; Denayer, J. F. M.; Baron, G. V.; Remy,
T.; Gascon, J.; Kapteijn, F. J. Am. Chem. Soc. 2009, 131, 6326−6327.
(c) Vaidhyanathan, R.; Iremonger, S. S.; Shimizu, G. K. H.; Boyd, P.
G.; Alavi, S.; Woo, T. K. Science 2010, 330, 650−653. (d) Li, B.;
Zhang, Z.; Li, Y.; Yao, K.; Zhu, Y.; Deng, Z.; Yang, F.; Zhou, X.; Li, G.;
Wu, H.; Nijem, N.; Chabal, Y. J.; Lai, Z.; Han, Y.; Shi, Z.; Feng, S.; Li,
J. Angew. Chem., Int. Ed. 2012, 51, 1412−1415.
(13) (a) Zelen
̌ ́ ́ ́ ̌ ̌ ́ ́
ak, V.; Vargova, Z.; Almasi, M.; Zelenakova, A.;
Kuchar, J. Microporous Mesoporous Mater. 2010, 129, 354−359.
́
(b) Lin, J.-B.; Xue, W.; Zhang, J.-P.; Chen, X.-M. Chem. Commun.
2011, 47, 926−928. (c) Li, J.-R.; Tao, Y.; Yu, Q.; Bu, X.-H.; Sakamoto,
H.; Kitagawa, S. Chem.−Eur. J. 2008, 14, 2771−2776. (d) Zheng, B.;
Bai, J.; Duan, J.; Wojtas, L.; Zaworotko, M. J. J. Am. Chem. Soc. 2010,
133, 748−751.
(14) (a) Li, H.; Shi, W.; Zhao, K.; Niu, Z.; Li, H.; Cheng, P. Chem.−
Eur. J. 2013, 19, 3358−3365. (b) Li, H.; Shi, W.; Zhao, K.; Niu, Z.;
Chen, X.; Cheng, P. Chem.−Eur. J. 2012, 18, 5715−5723.
(15) Gutschke, S. O. H.; Price, D. J.; Powell, A. K.; Wood, P. T.
Angew. Chem., Int. Ed. 2001, 40, 1920−1923.
(16) Wang, S.; Wang, X.; Li, L.; Advincula, R. C. J. Org. Chem. 2004,
69, 9073−9084.
(17) Sheldrick, G. Acta Crystallogr. 2008, A64, 112−122.
(18) Spek, A. L. J. Appl. Crystallogr. 2003, 36, 7−13.
(19) Myers, A. L.; Prausnitz, J. M. AIChE J. 1965, 11, 121−127.
E
DOI: 10.1021/ic502921j
Inorg. Chem. XXXX, XXX, XXX−XXX