A urea decorated (3,24)-connected rht-type metal-organic framework exhibiting high gas uptake capability and catalytic activity

Article abstract of DOI:10.1039/c5ce00625b

A (3,24)-connected rht-type metal organic framework (MOF Cu-UBTA) containing a urea group was readily prepared by the solvothermal reaction between a hexacarboxylate ligand and Cu(NO₃)₂. Gas sorption investigations demonstrated its h

Full text of DOI:10.1039/c5ce00625b

View Article Online
View Journal
CrystEngComm
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: X. Wang, J. Li, Q.
Li, P. Li, H. Lu, Q. Lao, R. Ni, Y. Shi and Y. Zhao, CrystEngComm, 2015, DOI: 10.1039/C5CE00625B.
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Accepted Manuscripts are published online shortly after
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the Ethical guidelines still
apply. In no event shall the Royal Society of Chemistry be held
responsible for any errors or omissions in this Accepted Manuscript
or any consequences arising from the use of any information it
contains.
www.rsc.org/crystengcomm

Page 1 of 5
CrystEngComm
View Article Online
DOI: 10.1039/C5CE00625B
Journal Name
RSCPublishing
COMMUNICATION
A urea decorated (3,24)-connected rht-type
metal-organic framework exhibiting high gas
uptake capability and catalytic activity†
Cite this: DOI: 10.1039/x0xx00000x
Xiao-Jun Wang,*a Jian Li,a Qiu-Yan Li,a Pei-Zhou Li,b Han Lu,a Qianying
Lao,a Rui Ni,a Yanhui Shi,a and Yanli Zhao*b
Received 00th January 2012,
Accepted 00th January 2012
DOI: 10.1039/x0xx00000x
www.rsc.org/
A (3,24)-connected rht-type metal organic framework (MOF most of research attention regarding rhtꢀMOFs has mainly been
Cu-UBTA) containing urea group was readily prepared by devoted into the gas storage and separation.27ꢀ45 However, only
the solvothermal reaction between a hexacarboxylate ligand a few rare examples exploited their potential applications in the
and Cu(NO3)2. Gas sorption investigations demonstrated its other areas except gas uptake has been reported so far.49,50 To
high porosity and high uptake capacities for CO2 and H2. our knowledge, Shi’s group reported the first example of
Moreover, the MOF can act as an efficiently heterogeneous luminescent rhtꢀMOF ZnꢀTDPAT (TDPAT = 2,4,6ꢀtris(3,5ꢀ
catalyst for Friedel-Craft alkylation of
indole with nitroalkenes.
N
-methyl pyrrole or dicarboxyl phenylamino)ꢀ1,3,5ꢀtriazine), which serve as a dual
functional sensor for quantitatively detecting the concentration
of nitrobenzene and temperature.50
Metalꢀorganic frameworks (MOFs) are wellꢀdefined porous and
crystalline solids consisting of metal ions or metalꢀcontaining
clusters connected to multidentate organic linkers via metal
coordination bonds.1ꢀ7 Due to their hybrid inorganicꢀorganic
compositions, the structures and properties of MOFs can be
easily tuned through judicious combination of metal centres and
organic linkers toward specific applications,1ꢀ7 such as gas
storage and separation,8ꢀ14 heterogeneous catalysis15ꢀ19 and
sensing.20ꢀ23
One of possible reasons for limiting the applications of rht
ꢀ
MOFs should be ascribed to the slow development of novel
ligands with functional groups. Recently, we reported a porous
rhtꢀMOF Cu-ABTA in which acylamide group was used to
replace one of triazole units in parent MOF NTU-105
,
suggesting that (3,24)ꢀconnected rhtꢀtopological MOFs could
be constructed from a suitable unsymmetrical hexacarboxylate
acid ligand.51 Along with this research line, herein, we designed
and synthesized another unsymmetrical hexacarboxylate ligand
H6-L having a urea group (Fig. 1), which can act as a
hydrogenꢀbondꢀdonating catalytic site52,53. Then, a copper(II)
rhtꢀtype MOF Cu-UBTA was successfully prepared with this
new ligand. As expected, MOF Cu-UBTA exhibited high
porosity with high uptake capacities for CO2 and H2. Moreover,
In comparison to the purely inorganic porous materials (for
example activated porous carbons), the inherent modular nature
of MOFs highly enables the rational design and preparation of
these materials with preꢀdetermined ordered structures and
topologies via reticular synthesis.24ꢀ26 Recently, it has been
evidenced that a (3,24)ꢀconnected rhtꢀtopology could serve as
an ideal blueprint for the development of MOFs,27 in which a
24ꢀconnected paddlewheelꢀbased supermolecular building
block (SBB) with rhombicuboctahedral geometry linked
it can efficiently catalyze FriedelꢀCraft alkylation of
pyrrole or indole with nitroalkenes.
Nꢀmethyl
The unsymmetrical hexacarboxylate linker 5,5'ꢀ(4,4'ꢀ(5ꢀ(3ꢀ
(3,5ꢀdicarboxyphenyl)ureido)ꢀ1,3ꢀphenylene)bis(1 ꢀ1,2,3ꢀ
H
through t
rigonal (3ꢀconnected) nodes.28ꢀ45 These isoreticular
triazoleꢀ4,1ꢀdiyl))diisophthalic acid (H6-L)was synthesized as
described in Scheme S1 (in ESI). Similar to the ligands
constructed in our group,6,7,39,43,51 herein, we still used the click
reaction and condensation reaction to design and synthesize the
target ligand H6-L. Specifically, 3,5ꢀdiiodophenyl isocyanate
was reacted with diꢀtertꢀbutyl 5ꢀaminoisophthalate to get the
ureaꢀfunctionalized precursor compound diꢀtertꢀbutyl 5ꢀ(3ꢀ(3,5ꢀ
MOFs are typically prepared by the solvothermal reaction
between copper(II) ions and an overꢀall C3ꢀsymmetrical
hexacarboxylate acid linker composed of three coplanar
isophthalates.46ꢀ48 Owing to the highly connected framework
presented in these rhtꢀMOFs, they possess several specific
advantages, such as the robust framework with high surface
area and high concentration of openꢀmetal sites. Therefore,
diiodophenyl)ureido)isophthalate (
1
), which was converted into
This journal is © The Royal Society of Chemistry 2012
J. Name., 2012, 00, 1-3 | 1

CrystEngComm
Page 2 of 5
View Article Online
COMMUNICATION
Journal Name
DOI: 10.1039/C5CE00625B
diꢀtertꢀbutyl 5ꢀ(3ꢀ(3,5ꢀdiethynylphenyl)ureido)isophthalate (
2
)
The desolvated samples were prepared by exchanging the
by Sonogashira reaction with (trimethylsilyl)acetylene and solvent in the fresh MOF Cu-UBTA with dichloromethane,
subsequent deprotection with tetraꢀnꢀbutylammonium fluoride. followed by evacuation under high vacuum at 60 and 120 °C,
Then, the click reaction of diethynyl
2 and diꢀtertꢀbutyl 5ꢀ respectively. PXRD patterns of the activated samples exhibited
azidoisophthalate gave the tertꢀbutyl ester tBu6-L, which was a good agreement with the simulated one from its crystal data
deprotected with trifluoroacetic acid to get the ligand H6-L in a (Fig. S3 in ESI), indicating the retention of the framework
high yield.
during the activation process. To confirm the permanent
porosity of MOF Cu-UBTA, nitrogen sorption at 77 K was
performed as shown in Fig. 2. It was found that the N2 sorption
isotherm exhibits a reversible pseudoꢀtype I with a small step
before the plateau appears, suggesting the presence of both
microꢀ and mesopores within the framework. The Brunauer–
Emmett–Teller (BET) surface area was calculated to be 3134
m2 gꢀ1, which is very close to our reported MOF NTU-105 and
comparable with some rhtꢀMOFs (Table S2 in ESI).
180
120
60
300
200
100
0
Fig. 1 Molecular structure of the ligand hexacarboxylate acid H6-L (left) and
single crystal structure of (3,24)-connected rht-topological framework in MOF
Cu-UBTA (right).
H2 @ 77 K
CO2 @ 273 K
A typical solvothermal reaction of H6-L with Cu(NO3)2 in
N,
Nꢀdimethylformamide (DMF) at 75 °C for 3 days afforded
MOF Cu-UBTA (Cu3( )(H2O)3·10DMF·9H2O) as block
L
greenꢀblue crystals. Powder Xꢀray diffraction (PXRD)
measurements confirmed the phase purity of its bulk sample.
Singleꢀcrystal Xꢀray diffraction studies revealed that MOF Cu-
UBTA was crystallized in the tetragonal space group I4/m with
N
2
@ 273 K
600
0
0
200
400
800
Pressure / mmHg
unitꢀcell dimensions
(Table S1 in ESI). In the crystal structure of MOF Cu-UBTA
as anticipated, each 3ꢀconnected organic linker connects with
a = b = 31.4206 Å and c = 44.8239 Å
,
Fig. 3 Gas sorption isotherms of MOF Cu-UBTA for CO2 and N2 measured at 273 K,
and H2 measured at 77 K.
L
three 24ꢀconnected rhombicuboctahedral SBBs, thus generating
a (3,24)ꢀconnected rhtꢀtopological framework (Fig. 1).
In order to evaluate the potential application of MOF Cu-
UBTA in gas storage and separation, we further investigated its
gas uptake capacities towards CO2 and H2. As shown in Fig. 3,
the CO2 sorption isotherm was measured at 273 K, revealing an
uptake of 165 cm3 gꢀ1 (32.4 wt%) at 1 bar. This value is still
among the high CO2 uptake ability reported for MOFs,55,56 and
even higher than some of its isoreticular rhtꢀMOFs, such as rhtꢀ
MOFꢀ945 (Table S2 in ESI). As for nitrogen, the N2 uptake of
MOF Cu-UBTA was only 2.6 cm3 gꢀ1 at 273 K and 1 bar,
suggesting its high selectivity towards CO2 over N2. Besides,
the H2 sorption isotherm of MOF Cu-UBTA demonstrates a H2
uptake capacity as high as 281 cm3 gꢀ1 (2.51wt%) at 77 K and 1
bar (Fig. 3), which is greater than MOFs PCNꢀ6X series under
the same conditions (Table S2 in ESI). Then, the isosteric heat
of adsorption (Qst) for H2 was calculated from the isotherms at
77 and 87 K by using the ClausiusꢀClapeyron equation,
providing that the Qst value for MOF Cu-UBTA decreased
from 6.23 to 5.13 kJ molꢀ1 in the uptake range of 6ꢀ164 cm3 gꢀ1.
Similarly, the high performance of MOF Cu-UBTA for CO2
and H2 sorption should also be attributed to the high density of
open copper sites and coordinationꢀfree nitrogenꢀrich triazole
moieties within the robust rhtꢀframework.27ꢀ45
800
0.08
600
0.06
400
0.04
0.02
200
0.02
0.04
0.06
Relative Pressure P/P
0
0
0.0
0.2
0.4
0.6
0.8
1.0
Relative Pressure P/P
0
Fig. 2 Nitrogen sorption isotherm for MOF Cu-UBTA at 77 K (STP = standard
temperature and pressure; filled symbols, absorption; open symbols, desorption.
Inset shows the BET specific surface area plot).
The total accessible volume of MOF Cu-UBTA after the
removal of the guest solvents and coordinated water molecules
was estimated to be 76% using the PLATON/VOID routine.54
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 2012

Page 3 of 5
Journal Name
CrystEngComm
View Article Online
DOI: 1C0.O10M39M/CU5CNEI0C0A62T5IOB N
Since a functional urea group was introduced into MOF Cu- coupled plasma (ICP) analysis to be 0.5% 1st run, 1.1% 2nd run,
UBTA via ligand preꢀdesign, in order to validate its catalytic and 1.8% 3rd run, respectively. These results confirmed the high
activity, we also employed a simple Friedel–Crafts alkylation stability of MOF Cu-UBTA in the catalytic reaction. Finally,
of
N
ꢀmethylpyrrole and transꢀβꢀnitrostyrene (2 :1 molar ratio) we preliminarily extended the scope of the substrate including
as a model reaction.53 As shown in Fig. 4, the reaction with 5%
Nꢀmethyl indole and other nitroalkenes, giving the desired
molar MOF Cu-UBTA as catalyst was performed in CH3CN at products with good to excellent yields (Table S3 in ESI).
1
60 °C and monitored by H NMR spectroscopy. The desired
product was obtained in 85% yield after 48 h. No significant
increase was observed with further extension of reaction time.
Whereas only a trace of product was found in the control
experiment without catalyst, this indicates that MOF Cu-UBTA
can effectively catalyze the Friedel–Crafts reaction.
Conclusions
In summary, we have successfully constructed a novel ureaꢀ
containing rhtꢀtype MOF Cu-UBTA via the rational ligand preꢀ
design. The rhtꢀMOF demonstrated a large porosity as well as
high CO2 and H2 uptake capacities. More importantly, the ureaꢀ
functionalized rhtꢀMOF Cu-UBTA can act as a highly efficient
heterogeneous catalyst for FriedelꢀCrafts reactions, due to the
synergistic effect of urea groups and open metal sites within the
robust framework. To the best of our knowledge, this is the first
example of rhtꢀtype MOFs based catalyst. Furthermore, it is
expected that more multiꢀfunctional rhtꢀMOFs with novel
properties will be constructed by the sophisticated ligand design
with functional groups. Such research efforts are currently
underway in our group.
N
NO2
catalyst (5% mol)
NO2
+
N
CH3CN, 60 o
C
(2.0 equiv)
100
75
50
25
0
MOF Cu-UBTA
MOF NTU-105
Control
Acknowledgements
The work was financially supported from National Natural
Science Foundation of China (21302072), Natural Science
Foundation of Jiangsu Province (BK20130226), Natural
Science Foundation of Jiangsu Higher Education Committee
(13KJB150014), Scientific Research Foundation for the
Returned Overseas Chinese Scholars, State Education Ministry
of China, and the Priority Academic Program Development of
Jiangsu Higher Education Institutions (PAPD). The work was
also supported by the National Research Foundation (NRF),
Prime Minister’s Office, Singapore under its NRF Fellowship
(NRF2009NRFꢀRF001ꢀ015) and Campus for Research
Excellence and Technological Enterprise (CREATE)
Programme–Singapore Peking University Research Centre for a
Sustainable LowꢀCarbon Future, as well as the NTUꢀA*Star
Centre of Excellence for Silicon Technologies (A*Star SERC
No.: 112 351 0003).
0
15
30
45
60
75
Time / h
Fig. 4 Catalytic activities of MOF Cu-UBTA, NTU-105 and a control.
Next, to understand the role of urea unit played in the
catalytic reaction, we utilized the similar MOF NTU-105
without urea to repeat this reaction under the same conditions.
It was found that MOF NTU-105 exhibited a lower catalytic
activity in relative to Cu-UBTA (Fig. 4). This confirms that the
urea group in rhtꢀMOF Cu-UBTA can also work as hydrogenꢀ
bondꢀdonating site to catalyze Friedel–Crafts reaction. On the
other hand, the yield of product catalyzed by MOF NTU-105 is
medium 48% after 48 h, which should be attributed the Lewis
acidic open copper sites in the framework. Thus, we believe
that the high catalytic activity of MOF Cu-UBTA should
originate from the synergistic effect of open metal site and urea
group within the framework.
Meanwhile, the recyclability of MOF Cu-UBTA
heterogeneous catalyst for the reaction was also investigated,
which can be easily isolated from the reaction system by a
simple centrifugation. It was reused for three times without
obvious loss of the catalytic activity (81% for 2nd run, 75% for
3rd run). PXRD patterns for recycled catalyst revealed that
MOF Cu-UBTA maintained its crystalline structure and
framework after catalysis (Fig. S3 in ESI). Besides, the low
concentration (by mass%) of Cu2+ in reaction solution after
catalysis and removal of MOF, was determined by inductively
Notes and references
aJiangsu Key Laboratory of Green Synthetic Chemistry for Functional
Materials, School of Chemistry and Chemical Engineering, Jiangsu
Normal University, Xuzhou 221116, P. R. China. Eꢀmail:
xjwang@jsnu.edu.cn
bDivision of Chemistry and Biological Chemistry, School of Physical and
Mathematical Sciences, Nanyang Technological University, 637371,
Singapore. Eꢀmail: zhaoyanli@ntu.edu.sg
†Electronic Supplementary Information (ESI) available: Detailed
experimental procedure, IR spectra, PXRD patterns, TGA, table of Xꢀray
data of CuꢀUBTA, gas adsorption data. CCDC 1056256. For ESI and
crystallographic data in CIF or other electronic format see
DOI: 10.1039/c000000x/
This journal is © The Royal Society of Chemistry 2012
J. Name., 2012, 00, 1-3 | 3

CrystEngComm
Page 4 of 5
VJieowuArrtnicalelONnlainme e
COMMUNICATION
DOI: 10.1039/C5CE00625B
1 H.ꢀC. Zhou and S. Kitagawa, Chem. Soc. Rev., 2014, 43, 5415.
2 H. Furukawa, K. E. Cordova, M. O’Keeffe and O. M. Yaghi, Science
2013, 341, 1230444.
32 Y. Yan, I. Telepeni, S. Yang, X. Lin, W. Kockelmann, A. Dailly, A. J.
Blake, W. Lewis, G. S. Walker, D. R. Allan, S. A. Barnett, N. R.
Champness and M. Schröder, J. Am. Chem. Soc., 2010, 132, 4092.
33 O. K. Farha, A. Özgür Yazaydın, I. Eryazici, C. D. Malliakas, B. G.
Hauser, M. G. Kanatzidis, S. T. Nguyen, R. Q. Snurr and J. T. Hupp,
,
3 H.ꢀC. Zhou, J. R. Long and O. M. Yaghi, Chem. Rev., 2012, 112, 673.
4 J. R. Long and O. M. Yaghi, Chem. Soc. Rev., 2009, 38, 1213.
5 J.ꢀC. Tan and B. Civalleri, CrystEngComm, 2015, 17, 197.
Nat Chem, 2010, 2, 944.
6 P.ꢀZ. Li, X.ꢀJ. Wang, K. Zhang, A. Nalaparaju, R. Zou, R. Zou, J. Jiang 34 B. Zheng, J. Bai, J. Duan, L. Wojtas and M. J. Zaworotko, J. Am.
and Y. Zhao, Chem. Commun., 2014, 50, 4683. Chem. Soc., 2011, 133, 748.
7 X.ꢀJ. Wang, P.ꢀZ. Li, L. Liu, Q. Zhang, P. Borah, J. D. Wong, X. X. 35 B. Li, Z. Zhang, Y. Li, K. Yao, Y. Zhu, Z. Deng, F. Yang, X. Zhou,
Chan, G. Rakesh, Y. Li and Y. Zhao, Chem. Commun., 2012, 48
,
G. Li, H. Wu, N. Nijem, Y. J. Chabal, Z. Lai, Y. Han, Z. Shi, S. Feng
10286.
and J. Li, Angew. Chem. Int. Ed., 2012, 51, 1412.
8 S. Yang, A. J. RamirezꢀCuesta, R. Newby, V. GarciaꢀSakai, P. Manuel, 36 O. K. Farha, C. E. Wilmer, I. Eryazici, B. G. Hauser, P. A. Parilla, K.
S. K. Callear, S. I. Campbell, C. C. Tang and M. Schröder, Nat
Chem, 2015, , 121.
O’Neill, A. A. Sarjeant, S. T. Nguyen, R. Q. Snurr and J. T. Hupp, J.
Am. Chem. Soc., 2012, 134, 9860.
7
9 J.ꢀR. Li, J. Sculley and H.ꢀC. Zhou, Chem. Rev., 2012, 112, 869.
10 B. Van de Voorde, B. Bueken, J. Denayer and D. De Vos, Chem. Soc.
Rev., 2014, 43, 5766.
37 X. Zhao, D. Sun, S. Yuan, S. Feng, R. Cao, D. Yuan, S. Wang, J. Dou
and D. Sun, Inorg. Chem., 2012, 51, 10350.
38 O. K. Farha, I. Eryazici, N. C. Jeong, B. G. Hauser, C. E. Wilmer, A.
A. Sarjeant, R. Q. Snurr, S. T. Nguyen, A. Ö. Yazaydın and J. T.
Hupp, J. Am. Chem. Soc., 2012, 134, 15016.
11 Y. He, W. Zhou, G. Qian and B. Chen, Chem. Soc. Rev., 2014, 43
,
5657.
12 E. Barea, C. Montoro and J. A. R. Navarro, Chem. Soc. Rev., 2014, 39 X.ꢀJ. Wang, P.ꢀZ. Li, Y. Chen, Q. Zhang, H. Zhang, X. X. Chan, R.
43, 5419.
Ganguly, Y. Li, J. Jiang and Y. Zhao, Sci. Rep., 2013,
40 Y. Yan, M. Suyetin, E. Bichoutskaia, A. J. Blake, D. R. Allan, S. A.
Barnett and M. Schroder, Chem. Sci., 2013, , 1731.
3, 1149.
13 J. B. DeCoste and G. W. Peterson, Chem. Rev., 2014, 114, 5695.
14 P.ꢀZ. Li and Y. Zhao, Chem. Asian J., 2013,
8
, 1680.
4
15 M. Yoon, R. Srirambalaji and K. Kim, Chem. Rev., 2012, 112, 1196.
16 J. Liu, L. Chen, H. Cui, J. Zhang, L. Zhang and C.ꢀY. Su, Chem. Soc.
Rev., 2014, 43, 6011.
41
C. E. Wilmer, O. K. Farha, T. Yildirim, I. Eryazici, V.
Krungleviciute, A. A. Sarjeant, R. Q. Snurr and J. T. Hupp, Energy
Environ. Sci., 2013,
6, 1158.
17 A. Dhakshinamoorthy and H. Garcia, Chem. Soc. Rev., 2014, 43
,
42 G. Barin, V. Krungleviciute, D. A. GomezꢀGualdron, A. A. Sarjeant,
5750.
R. Q. Snurr, J. T. Hupp, T. Yildirim and O. K. Farha, Chem. Mater.
,
18 M. Zhao, S. Ou and C.ꢀD. Wu, Acc. Chem. Res., 2014, 47, 1199.
19 H. Fei and S. M. Cohen, J. Am. Chem. Soc., 2015, 137, 2191.
2014, 26, 1912.
43 X.ꢀJ. Wang, J. Li, P.ꢀZ. Li, L.ꢀB. Xing, H. Lu, H. Wu, Y. Shi, R. Zou
and Y. Zhao, Inorg. Chem. Commun., 2014, 46, 13.
20 L. E. Kreno, K. Leong, O. K. Farha, M. Allendorf, R. P. Van Duyne
and J. T. Hupp, Chem. Rev., 2012, 112, 1105.
44 K. Liu, B. Li, Y. Li, X. Li, F. Yang, G. Zeng, Y. Peng, Z. Zhang, G.
Li, Z. Shi, S. Feng and D. Song, Chem. Commun., 2014, 50, 5031.
21 Z. Hu, B. J. Deibert and J. Li, Chem. Soc. Rev., 2014, 43, 5815.
22 A. Douvali, A. C. Tsipis, S. V. Eliseeva, S. Petoud, G. S. 45 R. Luebke, L. J. Weselinski, Y. Belmabkhout, Z. Chen, L. Wojtas and
Papaefstathiou, C. D. Malliakas, I. Papadas, G. S. Armatas, I. M. Eddaoudi, Cryst. Growth Des., 2014, 14, 414.
Margiolaki, M. G. Kanatzidis, T. Lazarides and M. J. Manos, Angew. 46 Y. He, B. Li, M. O'Keeffe and B. Chen, Chem. Soc. Rev., 2014, 43
Chem. Int. Ed., 2015, 54, 1651. 5618.
23 Y. Guo, X. Feng, T. Han, S. Wang, Z. Lin, Y. Dong and B. Wang, J. 47 V. Guillerm, D. Kim, J. F. Eubank, R. Luebke, X. Liu, K. Adil, M. S.
Am. Chem. Soc., 2014, 136, 15485. Lah and M. Eddaoudi, Chem. Soc. Rev., 2014, 43, 6141.
24 M. O’Keeffe, M. A. Peskov, S. J. Ramsden and O. M. Yaghi, Acc. 48 Y. Yan, S. Yang, A. J. Blake and M. Schröder, Acc. Chem. Res.
Chem. Res., 2008, 41, 1782. 2014, 47, 296.
25 O. M. Yaghi, M. O'Keeffe, N. W. Ockwig, H. K. Chae, M. Eddaoudi 49 D. Ma, B. Li, X. Zhou, Q. Zhou, K. Liu, G. Zeng, G. Li, Z. Shi and S.
and J. Kim, Nature, 2003, 423, 705. Feng, Chem. Commun., 2013, 49, 8964.
26 M. Eddaoudi, J. Kim, N. Rosi, D. Vodak, J. Wachter, M. O'Keeffe 50 Z. Zhu, Y.ꢀL. Bai, L. Zhang, D. Sun, J. Fang and S. Zhu, Chem.
and O. M. Yaghi, Science, 2002, 295, 469. Commun., 2014, 50, 14674.
27 J. F. Eubank, F. Nouar, R. Luebke, A. J. Cairns, L. Wojtas, M. 51 J. Li, P.ꢀZ. Li, Q.ꢀY. Li, Y. Cao, H. Lu, H. Wu, F. Li, Y. Shi, X.ꢀJ.
,
,
Alkordi, T. Bousquet, M. R. Hight, J. Eckert, J. P. Embs, P. A.
Georgiev and M. Eddaoudi, Angew. Chem. Int. Ed., 2012, 51, 10099.
28 F. Nouar, J. F. Eubank, T. Bousquet, L. Wojtas, M. J. Zaworotko and
M. Eddaoudi, J. Am. Chem. Soc., 2008, 130, 1833.
Wang and Y. Zhao, RSC Adv., 2014, 4, 53975.
52 J. M. Roberts, B. M. Fini, A. A. Sarjeant, O. K. Farha, J. T. Hupp and
K. A. Scheidt, J. Am. Chem. Soc., 2012, 134, 3334.
53 X.ꢀW. Dong, T. Liu, Y.ꢀZ. Hu, X.ꢀY. Liu and C.ꢀM. Che, Chem.
Commun., 2013, 49, 7681.
29 D. Zhao, D. Yuan, D. Sun and H.ꢀC. Zhou, J. Am. Chem. Soc., 2009,
131, 9186.
54 A. Spek, Acta Crystallogr., Sect. D, 2009, 65, 148.
30 Y. Yan, X. Lin, S. Yang, A. J. Blake, A. Dailly, N. R. Champness, P. 55 K. Sumida, D. L. Rogow, J. A. Mason, T. M. McDonald, E. D. Bloch,
Hubberstey and M. Schroder, Chem. Commun., 2009, 1025.
31 D. Yuan, D. Zhao, D. Sun and H.ꢀC. Zhou, Angew. Chem. Int. Ed.
2010, 49, 5357.
Z. R. Herm, T.ꢀH. Bae and J. R. Long, Chem. Rev., 2012, 112, 724.
,
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 2012

Page 5 of 5
CrystEngComm
View Article Online
DOI: 10.1039/C5CE00625B
TOC
A urea decorated (3,24)-connected rht-type metal-organic framework exhibiting high gas
uptake capability and catalytic activity
Xiao-Jun Wang, Jian Li, Qiu-Yan Li, Pei-Zhou Li, Han Lu, Qianying Lao, Rui Ni, Yanhui Shi, and Yanli Zhao
A urea decorated rht-MOF exhibited high gas uptake for CO2 and H2 as well as worked as a heterogeneous catalyst
for Friedel-Craft reactions.