Flexible Zirconium MOFs as Bromine-Nanocontainers for Bromination Reactions under Ambient Conditions

Article abstract of DOI:10.1002/anie.201709186

A series of flexible MOFs (PCN-605, PCN-606, and PCN-700) are synthesized and applied to reversible bromine encapsulation and release. The chemical stability of these Zr-MOFs ensures the framework's integrity during the bromine adsorption, while the framework's flexibility allows for structural adaptation upon bromine uptake to afford stronger host–guest interactions and therefore higher bromine adsorption capacities. The flexible MOFs act as bromine-nanocontainers which elongate the storage time of volatile halides under ambient conditions. Furthermore, the bromine pre-adsorbed flexible MOFs can be used as generic bromine sources for bromination reactions giving improved yields and selectivities under ambient conditions when compared with liquid bromine.

Full text of DOI:10.1002/anie.201709186

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Accepted Article
Title: Flexible Zr-MOFs as Bromine-Nanocontainers for Bromination
Reactions under Ambient Conditions
Authors: Jiandong Pang, Shuai Yuan, Dongying Du, Christina Lollar,
Liangliang Zhang, Mingyan Wu, Daqiang Yuan, Hongcai
Zhou, and Maochun Hong
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201709186
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10.1002/anie.201709186
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COMMUNICATION
Flexible Zr-MOFs as Bromine-Nanocontainers for Bromination
Reactions under Ambient Conditions
Jiandong Pang[a,b,c]⁺, Shuai Yuan[b]⁺, Dongying Du[d], Christina Lollar[b], Liangliang Zhang[b], Mingyan
Wu[a]*, Daqiang Yuan[a], Hong-Cai Zhou[b]* and Maochun Hong[a]
Dedicated to the 80th birthday for Prof. Academician Xin-Tao Wu
Abstract: A series of flexible MOFs (PCN-605, -606 and -700) are
synthesized and applied to reversible bromine encapsulation and
release. The chemical stability of these Zr-MOFs ensures the
framework’s integrity during the bromine adsorption, while the
framework’s flexibility allows for structural adaptation upon bromine
uptake to afford stronger host-guest interactions and therefore higher
bromine adsorption capacities. The flexible MOFs act as bromine-
nanocontainers which elongate the storage time of volatile halides
under ambient conditions. Furthermore, the bromine pre-adsorbed
flexible MOFs can be used as generic bromine sources for
bromination reactions with improved yields and selectivities under
ambient conditions as compared with liquid bromine.
fascinating examples includes the breathing phenomenon in
response to guest adsorption as well as huge thermal expansions
under thermal treatment.[5] Intrinsic structural flexibility could lead
to intriguing properties in gas storage, separation, and catalysis.[6]
Additionally, the pore environment of FMOFs can be changed by
the breathing behavior which in turn modulates the catalytic
activity.[7] Therefore, tremendous efforts are made to construct
FMOFs and understand their structure-property relationships.
Brominations are an important class of organic transformation
essential for both laboratory research and modern industry. Liquid
bromine is the most commonly-used bromination reagent with a
high reactivity in bromination reactions. However, the safe
storage and utilization of liquid bromine still remain challenging
because of its highly volatile. Recently, a large number of rigid
porous materials including MOFs were explored as iodine
absorbents with relatively high adsorption capacities.[8]
Commendably, a redox-active MOF, Co2Cl2BTDD, was employed
for the reversible capture and release of gaseous Cl2 and Br2.[9]
FMOFs that undergo structure evolution upon guest uptake are
particularly promising for adsorption and storage applications
because this can lead to increased adsorption enthalpy,
enhanced selectivity and high usable storage capacities. For
example, the Long group developed a series of FMOFs for
methane storage with intrinsic thermal management.[10] The
unique adsorption behavior of FMOFs motivates us to study their
performance for liquid bromine adsorption and release. As we all
know, most FMOFs are constructed through labile coordination
bonds between low-valence metals and organic ligands, which
are often sensitive to air moisture, aqueous solutions, acid, or
base. However, halogens undergo partial hydrolysis to generate
acidic species, which can induce framework decomposition.
Therefore, we aim to develop chemically stable and inert MOFs
with structural flexibility for specific halogen adsorption. It has
been shown that porous MOFs based on Zr6 clusters are stable
towards acidic conditions due to the high-valent zirconium ions.
Bearing this in mind, we focus on the design and synthesis of the
Zr-based MOFs with structural flexibility.
Metal-organic frameworks (MOFs), also referred to as porous
coordination networks (PCNs), have been extensively
investigated as a class of functional solid-state porous materials
in the past two decades. Their structural and functional tunability
has led to fascinating developments with respect to applications
in gas storage and separation, chemical sensing, heterogeneous
catalysis and so on.[1] According to the literature, most reported
MOFs with permanent porosities can be attributed to the second-
generation of organic-inorganic hybrid porous materials.[2] On
account of their rigidity, this kind of MOF can maintain its original
porosity even after the removal of guest molecules.[3] However,
flexible porous materials which can respond to various external
stimuli via structural transitions while maintaining crystallinity are
urgently desired for intelligent technology development.
Fortunately, the emergence of flexible MOFs (FMOFs) shines
a ray of light on research for smart materials.[4] FMOFs possess
properties that are quite unique from rigid MOFs. Some
[a]
[b]
Dr. J. Pang, Dr. M. Wu, Dr. D. Yuan, Prof. Dr. M. Hong
State Key Lab of Structure Chemistry, Fujian Institute of Research
on the Structure of Mater, Chinese Academy of Sciences
Fuzhou, 350002, Fujian (China)
E-mail: wumy@fjirsm.ac.cn
Dr. J. Pang, S. Yuan, C. Lollar, Dr. L. Zhang, Prof. Dr. H.-C. Zhou
Department of Chemistry
To obtain flexible Zr-MOFs, a topology guided design was
adopted. The Hupp group has computationally predicted a series
of Zr-MOFs with different linkers and classified them by
topology.[11] Meanwhile, Smit et al also studied the predicted
flexibility of MOFs based on its crystal topology.[12] Accordingly, a
high degree of flexibility is expected if Zr-MOFs adopt bcu, flu, or
scu topologies. With this in mind, PCN-605, -606, and -700
systems were designed from the topological viewpoint and their
flexibilities were evaluated. For comparison, the bromine
adsorption performance of a rigid MOF (UiO-67) with similar
porosity was also investigated.
Texas A&M University
College Station, TX 77843 (USA)
E-mail: zhou@chem.tamu.edu
[c]
[d]
Dr. J. Pang
University of Chinese Academy of Sciences
Beijing, 100049 (China)
Dr. D. Du
Department of Chemistry
Northeast Normal University
Changchun, 130024 (China)
[⁺]
These authors contributed equally to this work.
Supporting information for this article is given via a link at the end of
the document.
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10.1002/anie.201709186
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COMMUNICATION
Figure 1. Structural comparison of UiO-67, PCN-700, PCN-605 and PCN-606. (a) UiO-67 with fcu topology is composed of 12-connected Zr6 clusters and linear
ligands while PCN-700 with bcu topology is composed of 8-connected Zr6 clusters and dimethylated linear ligands. (b) The tetratopic ligand with various substituents
adopt a Td or D2h symmetry, respectively, and further bridges the 8-connected Zr6 clusters to form PCN-605 and -606 series with flu or scu topologies.
The bcu structure consisting of 8-connected Zr6 clusters and
linear linkers was reported by our group as PCN-700.[7a] It can be
regarded as a structural derivative of UiO-67 by partial elimination
of linkers. UiO-67 with fcu topology possesses a rigid framework,
which is constructed by 12-connected Zr6 clusters and linear
BPDC ligands. However, the introduction of the dimethylated
linear carboxylate ligands (Me2-BPDC) gives rise to the deduction
form of the fcu topology by exclusion of four linkers in the
equatorial plane of the octahedral cluster (Figure 1a). The
symmetry of the crystal is reduced from cubic to tetragonal with
the topology of the framework changing from fcu to bcu and thus
the framework flexibility emerges.
Zr-MOFs with flu topology were also documented, however,
the flexibility is rarely studied. For example, UMCM-312, reported
by Matzger and coworkers, was composed of 8-connected Zr6
clusters and tetratopic linkers with a tetrahedral geometry.[13] The
rotations and deformations of the tetratopic ligands resulting from
biphenyl groups can bring about flexibility in the framework.
Introducing bulky substitutes on the 2,2’-positions of biphenyl
moieties could potentially restrict the rotations and deformations
of linkers and thereby tune the flexibility of the frameworks. In light
of this, two tetratopic ligands with different substitutes, 2,2’-H-
H4TPCB, and 2,2’-OH-H4TPCB were selected, giving rise to the
PCN-605 series (which was also termed UMCM-312 when 2,2’-
H-H4TPCB was used). In PCN-605, the tetratopic ligand adopts a
Td symmetry due to the free rotation of the C-C bond between the
two phenyl rings which is similar to the role of H4MTBC in PCN-
521.[14] Thus, if we simplify the ligands as 4-connected nodes and
the Zr6 clusters as 8-connected nodes, PCN-605 adopts the {4,8}-
c
flu network with the topological point symbol of
{412.612.84}{46}2.[15]
In order to obtain FMOFs with scu topology, a planar ligand
should be utilized as the linker. On the basis of our previous work,
a series of 4,4’-substituted ligands of H4TPCB, 4,4’-OMe-H4TPCB,
4,4’-OH-H4TPCB, and 4,4’-NH2-H4TPCB were selected to
maintain the coplanar nature of inner biphenyl fragments.
Theoretically, a redox balance exists for the hydroxyl or amino
group functionalized biphenyl moieties, which will lead to the
coplanar configuration of the biphenyl (Figure S1). Solvothermal
reactions of the planar tetratopic ligands and ZrCl4 give another
type of three-dimensional framework termed the PCN-606 series.
Single-crystal X-ray diffraction experiments at 100 K revealed that
PCN-606 crystallized in the orthorhombic space group Cmmm. As
expected, the inner biphenyl ring of the ligand is inclined to be
coplanar because of the presence of the two substituents on the
tetracarboxylate ligands. These series of tetratopic ligands adopt
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10.1002/anie.201709186
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COMMUNICATION
D2h symmetry rather than Td symmetry, which has been observed
in previous research.[16] However, the outer benzoate group is far
from coplanar to the biphenyl core with a dihedral angle of 54.28o.
show higher bromine uptake capacities than that of the rigid MOF,
because the FMOFs may adopt larger pore configurations when
immersed into the bromine solution. Luckily, single crystal data of
the four MOFs were also measured after bromine adsorption,
which were named PCN-605-H-Br, PCN-606-OMe-Br, PCN-700-
Br, and UiO-67-Br. It should be noted that free Br atoms can be
located in the pores of the FMOFs but cannot be located in UiO-
67 because of the high symmetry. This single crystal data
revealed that bromine molecules were encapsulated into the
pores of the MOFs. Interestingly, the crystallographic a axis of the
three FMOFs (c axis for PCN-700-Br) expand with coefficients of
4.5%, 3.6%, and 1.2% respectively after bromine adsorption
compared with the as-synthesized ones, indicating the expansion
of the pores in the FMOFs. However, the unit cell parameters of
the rigid framework UiO-67 remained almost unchanged (Figure
2).
Bromination reactions should typically be performed under low
temperatures in order to improve the reaction selectivity and
efficiency when using liquid bromine. The slow release of bromine
from the MOFs’ pores into the reaction system may also decrease
the bromination rate, which is similar to dropwise addition of
bromine under low temperature. In order to verify the above idea,
the four bromine pre-absorbed MOFs materials were tested as
halogenation agents for binaphthol under ambient condition. The
reaction systems were vibrated on a vortexer overnight and the
Finally,
a
large rhombic one-dimensional channel of
approximately 15 × 30 Å was observed along the crystallographic
c axis. From the topological point of view, if the ligands were
regarded as 4-connected nodes and the Zr6 clusters as 8-
connected nodes, PCN-606 adopts the {4,8}-c scu network with
the topological point symbol of {416.612}{44.62}2 (Figure 1b).
Because of the flexibility of the frameworks, activation of the
FMOFs using conventional methods (solvent exchange followed
by degas under high temperatures) failed. Thus, super-critical
CO2 was used to active the samples in order to confirm the
permanent porosity of these flexible MOFs. As shown in Figure
S4, PCN-606-OH shows the highest N2 adsorption amount of 630
cm3 g-1, while PCN-606-OMe exhibits the lowest N2 uptake of 280
cm3 g-1 at 77 K (1 atm).
bromination reaction results are listed in Table 1.
Table 1. Bromination of binaphthol utilizing the bromine pre-absorbed
MOFs.a
MOFs
Yield
35 %
86 %
74 %
18 %
46 %
PCN-605-H-Br
PCN-606-OMe-Br
PCN-700-Br
UiO-67-Br
Liquid bromine
Figure 2. Structure of (a) PCN-605-H, (b) PCN-606-OMe, (c) PCN-700, and (d)
UiO-67 before (left) and after (right) bromine adsorption. The one-dimensional
channels of the flexible MOFs expand after bromine adsorption while the
channels in rigid MOFs remain unchanged. Color codes: gray C, red O, blue Zr,
green Br.
a
The MOF-loaded bromine was added in 20% excess. The reaction mixture
were vibrated overnight at room temperature before worked up.
Surprisingly, the efficiency of binaphthol bromination using
bromine pre-absorbed FMOFs are much higher than the rigid
MOF and even higher than directly using liquid bromine under
ambient conditions. Furthermore, PCN-606-OMe-Br and PCN-
700-Br show excellent repeatability in bromine capture and
release capacities with bromination yields of 75% and 62% after
three cycles of adsorption-bromination tests, respectively. This
indicates that these two FMOFs show promise in practical
applications. It should be noted that the volatilization of the
bromine in FMOFs is much slower than that in the liquid state at
room temperature. Almost all of liquid bromine was gasified within
one hour while more than 80 percent of bromine remained in
FMOFs after 24 hours, when the same amount of bromine in liquid
state and pre-absorbed MOFs were placed under ambient
conditions.
Considering that the hydroxyl and amino groups may be
sensitive to bromine, two analogues without these functional
groups, PCN-605-H and PCN-606-OMe, were used to capture
bromine. A fresh, crystalline sample of PCN-605-H, PCN-606-
OMe, PCN-700, and UiO-67 were immersed into a 1 mol•L-1
cyclohexane solution of liquid bromine formed after solvent
exchange with acetone and then cyclohexane for three times
respectively. The sample color gradually changed from colorless
to yellow and then dark red as bromine diffused into the pores of
the MOF. UV-Vis analysis also indicated that the concentration of
bromine in cyclohexane decreased with time (Figure S2).
According to the UV-Vis results, the total bromine uptake of PCN-
605-H, PCN-606-OMe, PCN-700, and UiO-67 are 4.2, 3.7, 2.6,
and 1.9 g•g-1, respectively. As expected, these three FMOFs
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[4]
[5]
a) A. Schneemann, V. Bon, I. Schwedler, I. Senkovska, S. Kaskel, R. A.
Fischer, Chem. Soc. Rev. 2014, 43, 6062-6096; b) Z. Chang, D. H. Yang,
J. Xu, T. L. Hu, X. H. Bu, Adv. Mater. 2015, 27, 5432-5441.
In addition, PCN-606-OMe-Br and PCN-700-Br were also used
for bromination of biphenols and anilines under ambient
conditions. As shown in Table S2, the bromination yields of 4,4’-
biphenol and p-anisidine are much higher than would be obtained
using liquid bromine, indicating that these bromine pre-absorbed
FMOFs can be used as generic bromine sources for bromination
reactions.[17]
a) I. Grobler, V. J. Smith, P. M. Bhatt, S. A. Herbert, L. J. Barbour, J. Am.
Chem. Soc. 2013, 135, 6411-6414; b) S. Yang, L. Liu, J. Sun, K. M.
Thomas, A. J. Davies, M. W. George, A. J. Blake, A. H. Hill, A. N. Fitch,
C. C. Tang, M. Schroder, J. Am. Chem. Soc. 2013, 135, 4954-4957; c)
H. L. Zhou, Y. B. Zhang, J. P. Zhang, X. M. Chen, Nat. Commun. 2015,
6, 6917; d) S. Krause, V. Bon, I. Senkovska, U. Stoeck, D. Wallacher, D.
M. Tobbens, S. Zander, R. S. Pillai, G. Maurin, F. X. Coudert, S. Kaskel,
Nature 2016, 532, 348-352; e) J. Pang, C. Liu, Y. Huang, M. Wu, F. Jiang,
D. Yuan, F. Hu, K. Su, G. Liu, M. Hong, Angew. Chem. Int. Ed.2016, 55,
7478-7482.
In conclusion, a series of FMOFs have been synthesized on the
basis of linear or tetratopic organic ligands and 8-connected Zr6
clusters. Taking advantage of the flexible frameworks, these
materials show higher bromine adsorption capacities than the
rigid MOF. Additionally, the bromine pre-adsorbed FMOFs can be
utilized as bromine sources under ambient conditions, and the
efficiency of the bromination reaction for organic starting
molecules can be significantly improved.
The flexible and chemically stable Zr-MOFs developed in this
work shall provide versatile platforms for the study of fundamental
science and applications in gas storage, separation, drug delivery
and catalysis.
[6]
[7]
M. K. Taylor, T. Runcevski, J. Oktawiec, M. I. Gonzalez, R. L. Siegelman,
J. A. Mason, J. Ye, C. M. Brown, J. R. Long, J. Am. Chem. Soc. 2016,
138, 15019-15026.
a) S. Yuan, W. Lu, Y. P. Chen, Q. Zhang, T. F. Liu, D. Feng, X. Wang, J.
Qin, H. C. Zhou, J. Am. Chem. Soc. 2015, 137, 3177-3180; b) S. Yuan,
Y. P. Chen, J. Qin, W. Lu, X. Wang, Q. Zhang, M. Bosch, T. F. Liu, X.
Lian, H. C. Zhou, Angew. Chem. Int. Ed. 2015, 54, 14696-14700; c) C.
X. Chen, Z. Wei, J. J. Jiang, Y. Z. Fan, S. P. Zheng, C. C. Cao, Y. H. Li,
D. Fenske, C. Y. Su, Angew. Chem. Int. Ed. 2016, 55, 9932-9936; d) S.
Yuan, Y. P. Chen, J. S. Qin, W. Lu, L. Zou, Q. Zhang, X. Wang, X. Sun,
H. C. Zhou, J. Am. Chem. Soc. 2016, 138, 8912-8919; e) S. Yuan, L.
Zou, H. Li, Y. P. Chen, J. Qin, Q. Zhang, W. Lu, M. B. Hall, H. C. Zhou,
Angew. Chem. Int. Ed. 2016, 55, 10776-10780.
Acknowledgements
[8]
[9]
a) J. T. Hughes, D. F. Sava, T. M. Nenoff, A. Navrotsky, J. Am. Chem.
Soc. 2013, 135, 16256-16259; b) H. Kitagawa, H. Ohtsu, M. Kawano,
Angew. Chem. Int. Ed. 2013, 52, 12395-12399; c) K. S. Subrahmanyam,
C. D. Malliakas, D. Sarma, G. S. Armatas, J. Wu, M. G. Kanatzidis, J.
Am. Chem. Soc. 2015, 137, 13943-13948; d) Z. Yan, Y. Yuan, Y. Tian,
D. Zhang, G. Zhu, Angew. Chem. Int. Ed. 2015, 54, 12733-12737.
Y. Tulchinsky, C. H. Hendon, K. A. Lomachenko, E. Borfecchia, B. C.
Melot, M. R. Hudson, J. D. Tarver, M. D. Korzynski, A. W. Stubbs, J. J.
Kagan, C. Lamberti, C. M. Brown, M. Dinca, J. Am. Chem. Soc. 2017,
139, 5992-5997.
This work was financially supported by the Strategic Priority
Research Program of the Chinese Academy of Sciences
(XDB20000000). The gas sorption studies were supported by the
Center for Gas Separations Relevant to Clean Energy
Technologies, an Energy Frontier Research Center funded by the
U.S. Department of Energy, Office of Science, Office of Basic
Energy Sciences (DE-SC0001015). Structural analyses were
supported by the Robert A. Welch Foundation through a Welch
Endowed Chair to HJZ (A-0030). The National Science
Foundation Graduate Research Fellowship (DGE: 1252521) are
gratefully acknowledged. The authors also acknowledge the
financial supports of U.S. Department of Energy Office of Fossil
Energy, National Energy Technology Laboratory (DE-
FE0026472) and National Science Foundation Small Bussiness
Innovation Research (NSF-SBIR) under Grant No. (1632486).
The authors also acknowledge the financial supports of 973
Program (2014CB932101 and 2013CB933200), National Nature
Science Foundation of China (21390392 and 21731006), CAS
[10] J. A. Mason, J. Oktawiec, M. K. Taylor, M. R. Hudson, J. Rodriguez, J.
E. Bachman, M. I. Gonzalez, A. Cervellino, A. Guagliardi, C. M. Brown,
P. L. Llewellyn, N. Masciocchi, J. R. Long, Nature 2015, 527, 357-361.
[11] P. Deria, D. A. Gomez-Gualdron, I. Hod, R. Q. Snurr, J. T. Hupp, O. K.
Farha, J. Am. Chem. Soc. 2016, 138, 14449-14457.
[12] M. Witman, S. Ling, S. Jawahery, P. G. Boyd, M. Haranczyk, B. Slater,
B. Smit, J. Am. Chem. Soc. 2017, 139, 5547-5557.
[13] J. L. Ma, L. D. Tran, A. J. Matzger, Cryst. Growth Des. 2016, 16, 4148-
4153.
[14] M. Zhang, Y. P. Chen, M. Bosch, T. Gentle, 3rd, K. Wang, D. Feng, Z. U.
Wang, H. C. Zhou, Angew. Chem. Int. Ed. 2014, 53, 815-818.
[15] V. A. Blatov, A. P. Shevchenko, D. M. Proserpio, Cryst. Growth Des.
2014, 14, 3576-3586.
(QYZDY-SSW-SLH025),
Youth
Innovation
Promotion
Association CAS, and Chun Miao Project of Haixi Institutes
(CMZX-2016-001). S. Yuan also acknowledges the Dow
Chemical Graduate Fellowship.
[16] J. Pang, F. Jiang, M. Wu, C. Liu, K. Su, W. Lu, D. Yuan, M. Hong, Nat.
Commun. 2015, 6, 7575.
[17] T. Osako, Y. Uozumi, Org. Lett. 2014, 16, 5866-5869.
Keywords: metal-organic frameworks • flexible • structural
transformation • bromine-nanocontainers • bromination reactions
[1]
a) B. Li, H.-M. Wen, W. Zhou, Jeff Q. Xu, B. Chen, Chem 2016, 1, 557-
580; b) K. Sumida, D. L. Rogow, J. A. Mason, T. M. McDonald, E. D.
Bloch, Z. R. Herm, T. H. Bae, J. R. Long, Chem. Rev. 2012, 112, 724-
781; c) N. S. Bobbitt, M. L. Mendonca, A. J. Howarth, T. Islamoglu, J. T.
Hupp, O. K. Farha, R. Q. Snurr, Chem. Soc. Rev. 2017; d) X. Lian, Y.
Fang, E. Joseph, Q. Wang, J. Li, S. Banerjee, C. Lollar, X. Wang, H. C.
Zhou, Chem. Soc. Rev. 2017; e) L. B. Sun, X. Q. Liu, H. C. Zhou, Chem.
Soc. Rev. 2015, 44, 5092-5147; f) J. Jiang, Y. Zhao, O. M. Yaghi, J. Am.
Chem. Soc. 2016, 138, 3255-3265.
[2]
[3]
E. J. Carrington, C. A. McAnally, A. J. Fletcher, S. P. Thompson, M.
Warren, L. Brammer, Nat. Chem. 2017, 9, 882-889.
S. Horike, S. Shimomura, S. Kitagawa, Nat. Chem. 2009, 1, 695-704.
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Entry for the Table of Contents
COMMUNICATION
A series of flexible Zr-based metal-
organic frameworks (MOFs) are
designed and synthesized under a
topology guided strategy. These
MOFs show significant structural
transformation during desolvation and
bromine adsorption. In addition, the
bromine pre-adsorbed flexible MOFs
can be used as generic bromine
sources for bromination reactions with
improved yields and selectivities
under ambient conditions as
J. Pang, S. Yuan, D. Du, C. Lollar, L.
Zhang, M. Wu*, D. Yuan, H.-C. Zhou*,
M. Hong
Page No. – Page No.
Flexible Zr-MOFs as Bromine-
Nanocontainers for Bromination
Reactions under Ambient Conditions
compared with liquid bromine.
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