Novel microporous metal-organic framework exhibiting high acetylene and methane storage capacities

Article abstract of DOI:10.1021/acs.inorgchem.5b00194

A new organic hexacarboxylic acid, 5,5′,5″-(9H-carbazole-3,6,9-triyl)triisophthalic acid (H₆CTIA), was developed to construct its first microporous metal-organic framework (MOF), Cu₆(CTIA)₂ (ZJU-70). With open metal sites and suitable pore sizes, this MOF exhibits high acetylene and methane storage capacities at room temperature.

Full text of DOI:10.1021/acs.inorgchem.5b00194

Article
pubs.acs.org/IC
Novel Microporous Metal−Organic Framework Exhibiting High
Acetylene and Methane Storage Capacities
Xing Duan,† Chuande Wu,‡ Shengchang Xiang,§ Wei Zhou,∥,⊥ Taner Yildirim,∥,# Yuanjing Cui,†
Yu Yang,† Banglin Chen,*,†,∇,△ and Guodong Qian*,†
†State Key Laboratory of Silicon Materials, Cyrus Tang Center for Sensor Materials and Applications, School of Materials Science &
‡
Engineering, and Department of Chemistry, Zhejiang University, Hangzhou 310027, China
§Fujian Provincial Key Laboratory of Polymer Materials, Fujian Normal University, 3 Shangsan Road, Cangshang Region, Fuzhou
350007, China
∥NIST Center for Neutron Research, Gaithersburg, Maryland 20899-6102, United States
⊥Department of Materials Science and Engineering, University of Maryland, College Park, Maryland 20742, United States
#Department of Materials Science and Engineering, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6272, United States
∇Department of Chemistry, University of Texas at San Antonio, One UTSA Circle, San Antonio, Texas 78249-0698, United States
△Department of Chemistry, Faculty of Science, King Abdulaziz University, Jeddah 22254, Saudi Arabia
S
* Supporting Information
ABSTRACT: A new organic hexacarboxylic acid, 5,5′,5″-(9H-
carbazole-3,6,9-triyl)triisophthalic acid (H6CTIA), was devel-
oped to construct its first microporous metal−organic
framework (MOF), Cu6(CTIA)2 (ZJU-70). With open metal
sites and suitable pore sizes, this MOF exhibits high acetylene
and methane storage capacities at room temperature.
apertures, exhibits a high volumetric working capacity of 183
cc(STP)/cc. During our extensive studies on diverse organic
ligands for their assembly of porous multifunctional MOFs, a
new hexacarboxylic acid, 5,5′,5″-(9H-carbazole-3,6,9-triyl)-
triisophthalic acid (H6CTIA), which can construct the MOF
material with a high density of open metal sites, was designed
and synthesized. This new organic linker can be considered as
an H6BHB analogue in which the central benzene ring in
H6BHB was replaced by the carbazole moiety in H6CTIA. The
H6CTIA linker, which is less symmetric, can result in
noninterpenetrated frameworks. At the same time, it offers an
approach to bring in a new connection manner of building
units, and the obtained MOFs can possess new topologies and
interesting properties. Herein we report the first example of
porous MOFs from this new hexacarboxylate linker,
Cu6(CTIA)2 (ZJU-70; ZJU = Zhejiang University). As
expected, the resulting MOF ZJU-70 does have open copper
metal sites and suitable pore sizes once it was suitably activated.
As a result, the activated ZJU-70a exhibits high acetylene (191
cm3 g−1 at 298 K and 1 bar) and methane (178 cm3 (STP)
cm−3 at 35 bar and 211 cm3 (STP) cm−3 at 65 bar) uptake at
room temperature.
INTRODUCTION
■
Methane and acetylene are promising fuel alternatives for future
vehicle and residential usage. Realization of suitable materials
for large amounts of methane and acetylene storage at room
temperature can significantly promote the eventual wide
applications of these two gas resources for our daily life.1,2
Microporous metal−organic frameworks (MOFs) are very
attractive for such an important application because of their
tunable pore spaces and immobilized functional sites for the
recognition of molecules.3−16
In the pursuit of MOFs for large amounts of gas storage,
deliberate synthesis and choice of organic linkers are very
important, which have been clearly demonstrated by a series of
MOFs containing meta-benzenedicarboxylate units.14−16 These
organic units not only enforce the generation of open metal
sites on the paddle-wheel Cu2(COO)4 copper sites, but also
systematically tune the pores to efficiently make use of the pore
spaces. Self-assembly of the organic linker H6BHB (H6BHB =
3,3′,3″,5,5′,5″-benzene-1,3,5-triylhexabenzoic acid) and the
paddle-wheel Cu2(COO)4 SBU generates UTSA-20, which
has a high density of open copper sites and high methane
storage capacities.15b Hupp’s group uses a series of hexacarbox-
ylic acid linkers to construct isoreticular MOFs NU-111,15c
NU-125,15d NU-138,15e NU-139,15e and NU-14015e with
varying pore sizes. Among them, NU-125, with suitable pore
Received: January 26, 2015
© XXXX American Chemical Society
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Scheme 1. Synthetic Route to the Organic Linker Used To Construct ZJU-70
chromatography (silica gel, ethyl acetate/petroleum ether, 1:8 v/v).
Yield: 66%. 1H NMR (500 MHz, CDCl3): δ = 1.37 (m, 12 H), 3.95 (s,
6 H), 8.64 (d, 2 H), 8.76 (s, 1 H) ppm.
EXPERIMENTAL SECTION
■
Materials, Measurements, and X-ray Collection and Struc-
1
ture Determination. H NMR spectra, elemental analyses, powder
5-Aminoisophthalic acid dimethyl ester (24g) was added into
hydrochloric acid (6 M, 270 mL) and cooled to 0 °C. Sodium nitrite
solution (1.7 M, 70 mL) was added gradually to produce a solution of
diazonium chloride. The resulting solution was introduced to a
solution containing 25.2 g of KI and 240 mL of H2O under stirring at a
temperature below 0 °C. After the addition was completed, 480 mL of
CCl2H2 was added, and the reaction mixture was kept stirring under
room temperature overnight. The organic layer was separated and
washed three times with water, dried with MgSO4, filtered, and
concentrated in a vacuum. The crude product was purified by column
chromatography (silica gel, ethyl acetate/petroleum ether, 1:15 v/v) to
X-ray diffraction (PXRD) studies, thermogravimetric analyses (TGA),
gas sorption isotherms, and single X-ray crystallographic measure-
ments were carried out through the commercially available instru-
ments. The details can be found in the Supporting Information. High-
pressure CH4 sorption isotherms were measured using a computer-
controlled Sieverts-type apparatus.17
Isosteric Heat of Adsorption. The binding energies of CH4 and
C2H2 in ZJU-70a are reflected in the isosteric heat of adsorption, Qst,
defined as
⎛
⎜
⎝
⎞
⎟
⎠
∂ ln p
∂T
1
Q st = RT2
obtain dimethyl 5-iodoisophthalate. Yield: 85%. H NMR (500 MHz,
CDCl3): δ = 3.95 (s, 6 H), 8.52 (d, 2 H), 8.61 (s, 1 H) ppm.
Dimethyl 5-(3,6-dibromo-9H-carbazol-9-yl)isophthalate was synthe-
sized by stirring a mixture of 3,6-dibromo-9H-carbazole (3 g),
dimethyl 5-iodoisophthalate (4.43 g), potassium carbonate (1.55 g),
and copper powder (7.38g) at 175 °C for 24 h and afterward extracted
with dichloromethane (100 mL). The organic layer was dried with
anhydrous MgSO4, and the solvent was removed in a vacuum. The
crude product was purified by column chromatography (silica gel,
dichloromethane/petroleum ether, 1:1 v/v). Yield: 60%. 1H NMR
(500 MHz, CDCl3): δ = 3.95 (s, 6 H), 7.22 (d, 2 H), 7.51 (d, 2 H),
8.20 (s, 2 H), 8.37 (s, 2 H), 8.79 (s, 1 H) ppm.
Dimethyl 5-(3,6-dibromo-9H-carbazol-9-yl)isophthalate (3 g),
dimethyl (5-pinacolboryl)isopthalate (5.57 g), and K2CO3 (8 g)
were added to 1,4-dioxane (100 mL), and the mixture was deaerated
under Ar for 15 min. Pd(PPh3)4 (0.47g) was added to the reaction
mixture with stirring, and the mixture heated to 80 °C for 3 days under
Ar. Afterward it was extracted with trichloromethane (150 mL). The
organic layer was separated and dried with anhydrous MgSO4, and the
solvent was removed in a vacuum. The crude product was purified by
column chromatography to obtain hexamethyl 5,5′,5″-(9H-carbazole-
3,6,9-triyl)triisophthalate. Yield: 56.2%. 1H NMR (500 MHz, CDCl3):
δ = 4.00 (s, 18 H), 7.28 (d, 1 H), 7.44 (d, 1 H), 7.54 (d, 1 H), 7.75 (d,
1 H), 8.35 (d, 2 H), 8.44 (s, 2 H), 8.51 (s, 2 H), 8,56 (s, 2 H), 8.66 (s,
1 H), 8.72 (s, 1 H), 8.81 (s, 1 H) ppm.
q
(1)
These values were determined using the pure component isotherm fits.
Synthesis of the Organic Linker H6CTIA. H6CTIA was
synthesized via Suzuki coupling followed by hydrolysis and acid-
ification as shown in Scheme 1.
5-Aminoisophthalic acid dimethyl ester (50g) was added into 15%
hydrobromic acid (900 mL) and cooled to 0 °C. Sodium nitrite
solution (2.5 M, 120 mL) was added gradually under fast stirring to
produce the solution of diazonium bromide. The resulting solution
was introduced to a solution containing CuBr (49 g) and 15%
hydrobromic acid (450 mL) at a temperature below 0 °C. After all the
reactants had been added, the resulting solution was left overnight with
stirring at room temperature. The solution was filtrated, and the filter
cake was dissolved in CCl2H2, dried with MgSO4, filtered, and
concentrated in a vacuum to get the crude product. It was purified by
column chromatography (silica gel, ethyl acetate/petroleum ether, 1:8
v/v) to obtain dimethyl 5-bromobenzene-1,3-dicarboxylate as a white
1
powder. Yield: 85%. H NMR (500 MHz, CDCl3): δ = 3.95 (s, 6 H),
8.35 (d, 2 H), 8.61 (s, 1 H) ppm.
Dimethyl (5-pinacolboryl)isopthalate was synthesized by stirring
the mixture of dimethyl 5-bromobenzene-1,3-dicarboxylate (5.4 g),
bis(pinacolato)diborane (6.0 g), potassium acetate (5.6 g), Pd-
(dppf)2Cl2 (0.2 g), and dried 1,4-dioxane (50 mL) at 70 °C for 24
h and afterward extracted with ethyl acetate (20 mL). The organic
layer was dried with anhydrous MgSO4, and the solvent was removed
in a vacuum to get the crude product. It was purified by column
Hexamethyl 5,5′,5″-(9H-carbazole-3,6,9-triyl)triisophthalate (5 g)
was then suspended in a mixture of 1,4-dioxane (40 mL), to which 150
mL of NaOH (15.5 g) aqueous solution was added. The mixture was
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stirred under reflux overnight. Dilute HCl was added to the remaining
aqueous solution until the solution was at pH = 2. The solid was
collected by filtration, washed with water, and dried to give 5,5′,5″-
(9H-carbazole-3,6,9-triyl)triisophthalic acid (H6CTIA) (96.7% yield).
1H NMR (500 MHz, DMSO): δ = 7.59 (d, 2 H), 7.91 (d, 2 H), 8.42
(s, 2 H), 8.49 (s, 2 H), 8.61 (s, 4 H), 8.64 (s, 1 H), 9.04 (s, 2 H), 13.47
(s, 6 H) ppm.
space accounts for approximately 62.5% of the whole crystal
volume (17 006 Å3 out of the 27 228 Å3 per unit cell volume)
by PLATON analysis.18
The activated ZJU-70a shows a type I sorption isotherm and
takes up a 461 cm3/g amount of N2 at 77 K and 1 bar (Figure
2). The Brunauer−Emmett−Teller (BET) and Langmuir
Synthesis of ZJU-70. A mixture of H6CTIA (2 mg, 0.003 mmol)
and Cu(NO3)2·2.5H2O (2.916 mg, 0.012 mmol) was dissolved in
DMF/EtCN/H2O (2.6 mL, 10:1:2, v/v) in a screw-capped vial. After
HNO3 (140 μL) (69%, aq) was added to the mixture, the vial was
capped and placed in an oven at 80 °C for 72 h. The resulting blue
ellipsoidal-shaped single crystals were washed with DMF several times
to give ZJU-70. Anal. Calcd for [Cu6(C72H30N2O24)(H2O)6]
(C3H7NO)12(H2O)9(C2H3N)5 (C118H159N19O51Cu6): C, 46.61; H,
5.28; N, 8.75. Found: C, 46.64; H, 5.26; N, 8.69.
RESULTS AND DISCUSSION
■
The organic ligand H6CTIA was readily synthesized via a Pd-
catalyzed Suzuki coupling reaction. The solvothermal reaction
of the linker H6CTIA with Cu(NO3)2 in DMF/EtCN/H2O in
the presence of a small amount of nitric acid at 80 °C for 72 h
yielded small ellipsoidal-shaped blue crystals of ZJU-70. The
structure was examined by single-crystal and powder X-ray
diffraction studies (Figure S1) and thermogravimetric analysis
(Figure S2).
Figure 2. N2 sorption isotherm of ZJU-70a at 77 K.
ZJU-70 adopts a three-dimensional (3D) framework that
crystallizes in the orthorhombic space group Cmc21. As
expected, the structure of ZJU-70 is constructed by three
isophthalate groups in H6CTIA linked through Cu2(COO)4
SBUs (Figure 1a) to form a 3D porous framework (Figure 1c
surface areas of ZJU-70a are 1791 and 1999 m2/g, respectively.
Its pore volume is 0.676 cm3/g. The calculated BET from its X-
ray single-crystal structure is 2509 m2/g, which is higher than
the experimentally measured one, indicating a certain degree of
framework deformation during the activation. The PXRD
pattern of activated sample after the gas sorption measurements
shows that the MOF still retains its crystallinity (Figure S1).
The pore size distribution basically corresponds to the pore
sizes from single-crystal X-ray diffraction (Figure S3). The
moderately high porosity and the high density of open copper
sites of ZJU-70a prompted us to check its possible application
for acetylene and methane storage.
The interesting structure characteristics of ZJU-70a and open
CuII sites of the MOF motivated us to carry out their gas
storage application. As show in Figure 3a, ZJU-70a exhibits
quite high acetylene uptakes. The C2H2 uptakes are 235 cm3
g−1 at 273 K and 1 bar and 191 cm3 g−1 at 298 and 1 bar. Its
gravimetric C2H2 uptake at room temperature and 1 bar is
among the very best MOFs for acetylene storage.4d,19 The
molecular dimensions20 and kinetic diameter21 of acetylene are
3.32 × 3.34 × 5.7 Å3 and 3.3 Å, which are in conformity with
the pore sizes of ZJU-70a. So we speculate that both the
suitable pore sizes/curvatures and high density of open copper
sites within ZJU-70a play important roles for the high storage
of acetylene. As shown in the Figure 3a inset, the corresponding
adsorption enthalpy for C2H2 is around 17.2 kJ/mol at zero
coverage, slighter lower than those reported.4d,22 When the
adsorption step occurs, the adsorption enthalpies of C2H2
increase to 22.4 kJ/mol, then decline.
Methane adsorption isotherms for ZJU-70a were carried out
using a high-pressure volumetric Sievert apparatus17 up to 65
bar. The excess methane isotherms for ZJU-70a are shown in
Figure.S4. Given the fact that the total volumetric methane
storage might be even more important than the total
gravimetric one in order to fully utilize the space, we estimated
the total volumetric methane storage capacities as well. Figure
3b shows the total volumetric methane uptake isotherms at 273
and 298 K. Under 65 bar, the total volumetric uptakes of ZJU-
Figure 1. X-ray single-crystal structure of ZJU-70 showing (a) each
hexacarboxylate ligand connects with six Cu2(COO)4 clusters; (b) the
channel along the a-axis and (4,6)-connected topology with a Schlafli
̈
symbol of (4264)3(466485)2; (c) the structure viewed along the a-axis
showing the irregular pore diameter in the range 4.4 to 9.6 Å; (d) the
structure viewed along the a-axis displaying an open Cu2+ site.
and d). The overall topology is a (4, 6)-connected binodal
(4264)3(466485)2 net if the organic ligand and the Cu2(COO)4
are taken as 6- and 4-connected nodes, respectively (Figure 1b).
ZJU-70 exhibits two different types of irregular pores along the
a-axes in the range 4.4 to 9.6 Å, taking into account the van der
Waals radii (Figure 1c). The pores are filled with terminal water
molecules and free solvent molecules. Once the terminal water
and free guest molecules were removed after thermal activation,
the open copper sites can be generated (Figure 1d). The void
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Figure 3. Gas sorption isotherms of ZJU-70a for (a) C2H2 at 273 and 298 K and (b) high-pressure CH4 at 273 and 298 K. Inset: Isosteric heats of
adsorption of C2H2 and CH4 calculated using the virial method. Solid symbols: adsorption, open symbols: desorption.
70a for methane can reach 238 and 211 cm3 (STP) cm−3 at 273
Notes
and 298 K, respectively, featuring ZJU-70a as one of the very
few MOF materials with high methane storage.1c Its methane
storage capacity of 178 cm3 (STP) cm−3 at 298 K and 35 bar is
also comparable to those found in the reported MOFs ZJU-
25,23 ZJU-35,24 NOTT-102,25 and IRMOF-6.26 We speculate
that both the suitable pore spaces and high density of open
copper sites within ZJU-70a make the contribution to the high
methane storage. Considering 5 and 65 bar as the specific lower
and upper pressure limit, respectively, the methane working
amount of ZJU-70a is 135 cm3 (STP) cm−3 (from 65 to 5 bar),
which is moderately high. The initial Qst of CH4 adsorption is
15.2 kJ mol−1, as shown in the inset of Figure 3b. The Qst of
CH4 adsorption does not change significantly with the CH4
loading.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported by the National Natural Science
Foundation of China (Grants 51272231 and 51229201),
Program for Innovative Research Team in University of
Ministry of Education of China (IRT13R54), Grant AX-1730
from the Welch Foundation (B.C.), and the Zhejiang Provincial
Natural Science Foundation of China (No. LZ15E020001).
REFERENCES
■
(1) (a) Liu, K.; Li, B.; Li, Y.; Li, X.; Yang, F.; Zeng, G.; Peng, Y.;
Zhang, Z.; Li, G.; Shi, Z.; Feng, S.; Song, D. Chem. Commun. 2014, 50,
5031−5033. (b) Asadi, T.; Ehsani, M. R.; Ribeiro, A. M.; Loureiro, J.
M.; Rodrigues, A. E. Chem. Eng. Technol. 2013, 36, 1231−1239.
(c) He, Y.; Zhou, W.; Qian, G.; Chen, B. Chem. Soc. Rev. 2014, 43,
5657−5678.
CONCLUSIONS
■
In conclusion, we have developed a novel aromatic
hexacarboxylic acid and constructed its first 3D microporous
metal−organic framework. ZJU-70a exhibits moderately high
storage capacities for both acetylene and methane. Given the
fact that this organic linker is unique, it will be more extensively
explored with other types of metal ions/clusters for the
construction of a variety of MOFs; thus a number of new MOF
materials will be emerging for their diverse usages.
(2) (a) Samsonenko, D. G.; Kim, H.; Sun, Y.; Kim, G. H.; Lee, H. S.;
Kim, K. Chem.Asian J. 2007, 2, 484−488. (b) Li, J. R.; Tao, Y.; Yu,
Q.; Bu, X. H.; Sakamoto, H.; Kitagawa, S. Chem.Eur. J. 2008, 14,
2771−2776. (c) Zhang, Z.; Xiang, S.; Chen, B. CrystEngComm 2011,
13, 5983−5992. (d) Hou, X.; He, P.; Li, H.; Wang, X. J. Phys. Chem. C
2013, 117, 2824−2834.
(3) (a) Suh, M. P.; Park, H. J.; Prasad, T. K.; Lim, D. Chem. Rev.
2012, 112, 782−835. (b) Sumida, K.; Rogow, D.; Mason, J.;
McDonald, T.; Bloch, E.; Herm, Z.; Bae, T.; Long, J. R. Chem. Rev.
2012, 112, 724−781. (c) He, Y.; Zhou, W.; Krishna, R.; Chen, B.
Chem. Commun. 2012, 48, 11813−11831. (d) Cai, J.; Rao, X.; He, Y.;
Yu, J.; Wu, C.; Zhou, W.; Yildirim, T.; Chen, B.; Qian, G. Chem.
Commun. 2014, 50, 1552−1554. (e) Liao, P.; Zhou, D.; Zhu, A.; Jiang,
L.; Lin, R.; Zhang, J.; Chen, X. J. Am. Chem. Soc. 2012, 134, 17380−
ASSOCIATED CONTENT
■
S
* Supporting Information
Synthesis of the organic linker H6CTIA, TGA and high-
pressure excess CH4 sorption isotherm, and single X-ray
crystallographic data (CCDC 1026814) given in CIF format.
This material is available free of charge via the Internet at
http://pubs.acs.org.
́
17383. (f) Gandara, F.; Furukawa, H.; Lee, S.; Yaghi, O. M. J. Am.
Chem. Soc. 2014, 136, 5271−5274. (g) Gedrich, K.; Senkovska, I.;
Klein, N.; Stoeck, U.; Henschel, A.; Lohe, M. R.; Baburin, I. A.;
Mueller, U.; Kaskel, S. Angew. Chem., Int. Ed. 2010, 49, 8489−8492.
(h) Ma, S. Q.; Zhou, H. C. Chem. Commun. 2010, 46, 44−53. (i) Gao,
W.; Wojtas, L.; Ma, S. Q. Chem. Commun. 2014, 50, 5316−5318.
(j) Liu, J.; Thallapally, P. K.; McGrail, B. P.; Brown, D. R.; Liu, J.
Chem. Soc. Rev. 2012, 41, 2308−2322. (k) Lu, W.; Wei, Z.; Gu, Z.; Liu,
T.; Park, J.; Park, J.; Tian, J.; Zhang, M.; Zhang, Q.; Gentle, T., III;
Bosch, M.; Zhou, H. Chem. Soc. Rev. 2014, 43, 5561−5593.
AUTHOR INFORMATION
■
Corresponding Authors
*E-mail: banglin.chen@utsa.edu. Fax: (+1) 210-458-7428.
*E-mail: gdqian@zju.edu.cn.
Author Contributions
(4) (a) Li, J.; Sculley, J.; Zhou, H. Chem. Rev. 2012, 112, 869−932.
(b) Lan, Y.; Jiang, H.; Li, S.; Xu, Q. Adv. Mater. 2011, 23, 5015−5020.
(c) He, Y.; Tan, Y.; Zhang, J. Chem. Commun. 2013, 49, 11323−
11325. (d) He, Y.; Krishna, R.; Chen, B. Energy Environ. Sci. 2012, 5,
The manuscript was written through contributions of all
authors. All authors have given approval to the final version of
the manuscript.
D
DOI: 10.1021/acs.inorgchem.5b00194
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
9107−9120. (e) Li, B.; Wen, H. M.; Zhou, W.; Chen, B. J. Phys. Chem.
Lett. 2014, 5, 3468−3479.
(22) Xu, H.; He, Y.; Zhang, Z.; Xiang, S.; Cai, J.; Cui, Y.; Yang, Y.;
Qian, G.; Chen, B. J. Mater. Chem. A 2013, 1, 77−81.
(23) Duan, X.; Yu, J.; Cai, J.; He, Y.; Wu, C.; Zhou, W.; Yildirim, T.;
Zhang, Z.; Xiang, S.; O’Keeffe, M.; Chen, B.; Qian, G. Chem. Commun.
2013, 49, 2043−2045.
(5) (a) Lee, J.; Farha, O. K.; Roberts, J.; Scheidt, K. A.; Nguyen, S. T.;
Hupp, J. T. Chem. Soc. Rev. 2009, 38, 1450−1459. (b) Liu, J.; Chen, L.;
Cui, H.; Zhang, J.; Zhang, L.; Su, C. Y. Chem. Soc. Rev. 2014, 43,
6011−6061. (c) Jiang, H. L.; Feng, D.; Liu, T. F.; Li, J. R.; Zhou, H. C.
J. Am. Chem. Soc. 2012, 134, 14690−14693. (d) Hu, Y.; Verdegaal, W.
M.; Yu, S. H.; Jiang, H. L. ChemSusChem 2014, 7, 734−737.
(6) (a) Cui, Y.; Yue, Y.; Qian, G.; Chen, B. Chem. Rev. 2012, 112,
1126−1162. (b) Chen, B.; Xiang, S.; Qian, G. Acc. Chem. Res. 2010,
43, 1115−1124. (c) Kang, Y.; Wang, F.; Zhang, J.; Bu, X. J. Am. Chem.
Soc. 2012, 134, 17881−17884.
(24) Kong, G. Q.; Han, Z. D.; He, Y.; Ou, S.; Zhou, W.; Yildirim, T.;
Krishna, R.; Zou, C.; Chen, B.; Wu, C. D. Chem.Eur. J. 2013, 19,
14886−14894.
(25) He, Y.; Zhou, W.; Yildirim, T.; Chen, B. Energy Environ. Sci.
2013, 6, 2735−2744.
(26) Eddaoudi, M.; Kim, J.; Rosi, N.; Vodak, D.; Wachter, J.;
O’Keeffe, M.; Yaghi, O. M. Science 2002, 295, 469−472.
(7) (a) Della Rocca, J.; Liu, D.; Lin, W. Acc. Chem. Res. 2011, 44,
957−968. (b) Horcajada, P.; Gref, R.; Baati, T.; Allan, P. K.; Maurin,
G.; Couvreur, P.; Fer
112, 1232−1268.
́
ey, G.; Morris, R. E.; Serre, C. Chem. Rev. 2012,
(8) (a) Li, L.; Tang, S.; Wang, C.; Lv, X.; Jiang, M.; Wu, H.; Zhao, X.
Chem. Commun. 2014, 50, 2304−2307. (b) Li, L.; Bell, J. G.; Tang, S.;
Lv, X.; Wang, C.; Xing, Y.; Zhao, X.; Thomas, K. M. Chem. Mater.
2014, 26, 4679−4695.
(9) (a) Pang, J.; Jiang, F.; Wu, M.; Yuan, D. Q.; Zhou, K.; Qian, J.;
Su, K.; Hong, M. Chem. Commun. 2014, 50, 2834−2836. (b) Wen, H.
M.; Li, B.; Yuan, D. Q.; Wang, H.; Yildirim, T.; Zhou, W.; Chen, B. J.
Mater. Chem. A 2014, 2, 11516−11522. (c) Qian, J.; Jiang, F.; Zhang,
L.; Su, K.; Pan, J.; Li, Q.; Yuan, D.; Hong, M. Chem. Commun. 2014,
50, 1678−1681.
́ ́
(10) (a) Gomez-Gualdron, D. A.; Gutov, O. V.; Krungleviciute, V.;
Borah, B.; Mondloch, J. E.; Hupp, J. T.; Yildirim, T.; Farha, O. K.;
Snurr, R. Q. Chem. Mater. 2014, 26, 5632−5639. (b) Barin, G.;
Krungleviciute, V.; Gutov, O.; Hupp, J. T.; Yildirim, T.; Farha, O. K.
Inorg. Chem. 2014, 53, 6914−6919.
(11) (a) Caskey, S. R.; Wong-Foy, A. G.; Matzger, A. J. J. Am. Chem.
Soc. 2008, 130, 10870−10871. (b) Liu, B.; Wong-Foy, A. G.; Matzger,
A. J. Chem. Commun. 2013, 49, 1419−1421.
(12) Mason, J. A.; Veenstrab, M.; Long, J. R. Chem. Sci. 2014, 5, 32−
51.
(13) (a) Wilmer, C. E.; Farha, O. K.; Yildirim, T.; Eryazici, I.;
Krungleviciute, V.; Sarjeant, A. A.; Snurr, R. Q.; Hupp, J. T. Energy
Environ. Sci. 2013, 6, 1158−1163. (b) Liu, D.; Wu, H.; Wang, S.; Xie,
Z.; Li, J.; Lin, W. Chem. Sci. 2012, 3, 3032−3037. (c) Kennedy, R. D.;
Krungleviciute, V.; Clingerman, D. J.; Mondloch, J. E.; Peng, Y.;
Wilmer, C. E.; Sarjeant, A. A.; Snurr, R. Q.; Hupp, J. T.; Yildirim, T.;
Farha, O. K.; Mirkin, C. A. Chem. Mater. 2013, 25, 3539−3543.
(14) Nouar, F.; Eubank, J. F.; Bousquet, T.; Wojtas, L.; Zaworotko,
M. J.; Eddaoudi, M. J. Am. Chem. Soc. 2008, 130, 1833−1835.
(15) (a) He, Y.; Li, B.; O’Keeffe, M.; Chen, B. Chem. Soc. Rev. 2014,
43, 5618−5656. (b) Guo, Z.; Wu, H.; Srinivas, G.; Zhou, Y.; Xiang, S.;
Chen, Z.; Yang, Y.; Zhou, W.; O’Keeffe, M.; Chen, B. Angew. Chem.,
Int. Ed. 2011, 50, 3178−3181. (c) Farha, O. K.; Wilmer, C. E.;
Eryazici, I.; Hauser, B. G.; Parilla, P. A.; O’ Neill, K.; Sarjeant, A. A.;
Nguyen, S. T.; Snurr, R. Q.; Hupp, J. T. J. Am. Chem. Soc. 2012, 134,
9860−9863. (d) Wilmer, C. E.; Farha, O. K.; Yildirim, T.; Eryazici, I.;
Krungleviciute, V.; Sarjeant, A. A.; Snurr, R. Q.; Hupp, J. T. Energy
Environ. Sci. 2013, 6, 1158−1163. (e) Barin, G.; Krungleviciute, V.;
Gomez-Gualdron, D. A.; Sarjeant, A. A.; Snurr, R. Q.; Hupp, J. T.;
Yildirim, T.; Farha, O. K. Chem. Mater. 2014, 26, 1912−1917.
(16) Yuan, D.; Zhao, D.; Sun, D.; Zhou, H. Angew. Chem., Int. Ed.
2010, 49, 5357−5361.
(17) Zhou, W.; Wu, H.; Hartman, M. R.; Yildirim, T. J. Phys. Chem. C
2007, 111, 16131−16137.
(18) Spek, L. PLATON; The University of Utrecht: Utrecht, The
Netherlands, 1999.
(19) Xiang, S.; Zhou, W.; Gallegos, J. M.; Liu, Y.; Chen, B. J. Am.
Chem. Soc. 2009, 131, 12415−12419.
(20) Reid, C. R.; Thomas, K. M. J. Phys. Chem. B 2001, 105, 10619−
10629.
(21) Uchida, S.; Kawahara, R.; Ogasawara, Y.; Mizuno, N. Dalton
Trans. 2013, 42, 16209−16215.
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DOI: 10.1021/acs.inorgchem.5b00194
Inorg. Chem. XXXX, XXX, XXX−XXX