Post-synthetic transformation of a Zn(II) polyhedral coordination network into a new supramolecular isomer of HKUST-1

Article abstract of DOI:10.1039/c7cc04958g

A Zn-based porphyrin containing metal-organic material (porphMOM-1) was transformed into a novel Cu-based porphyrin-encapsulating metal-organic material (porph@HKUST-1-β) via a one-pot post-synthetic modification (PSM) process involving both metal ion exchange and linker installation of trimesic acid. HKUST-1-β is the first example of yao topology and is to our knowledge the first supramolecular isomer of the archetypal coordination network HKUST-1.

Full text of DOI:10.1039/c7cc04958g

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Post-Synthetic Transformation of a Zn(II) Polyhedral Coordination
Network into a New Supramolecular Isomer of HKUST-1
Received 00th January 20xx,
Accepted 00th January 20xx
Yao Chen,b,c Lukasz Wojtas,d Shengqian Ma,d Michael J. Zaworotko,e,* Zhenjie Zhang,a,b,
*
DOI: 10.1039/x0xx00000x
www.rsc.org/
A
Zn-based porphyrin containing metal-organic material PSM. For example, Zn(II) can coordinate to three carboxylate
(porphMOM-1) was transformed into a novel Cu-based porphyrin- ligands to form cationic triangular paddlewheel MBBs, [Zn2(COO)3]+,
encapsulating metal-organic material (porph@HKUST-1-β) via a or with four carboxylate ligands to form neutral square
one-pot post-synthetic modification (PSM) process involving both paddlewheel MBBs, [Zn2(COO)4] (Scheme 1, left).24-27 This in turn
metal ion exchange and linker installation of trimesic acid. HKUST- creates diversity in terms of possible MOM structures and
1-β is the first example of yao topology and is to our knowledge topologies as exemplified by the 1,3,5-benzentricarboxylate (btc)
the first supramolecular isomer of the archetypal coordination based MOMs formed by Zn(II) and Cu(II). Whereas Cu(II) and btc
network HKUST-1.
readily form the archetypal tbo topology coordination network
HKUST-1,28 which is based upon regular small rhombihexahedron
polyhedral cages sustained by 12 square paddlewheel moieties
(Scheme 1, right top). Zn(II) forms two nets based upon regular
polyhedral.29 USF-2, is isostructural with HKUST-1; USF-1, is based
upon regular small cubicuboctahedron polyhedral cages formed by
6 square paddlewheel moieties and 8 triangular paddlewheel
moieties (Scheme 1, right below). A CSD (Cambridge Structural
Database)30 survey revealed no entries for [Cu2(COO)3]+, which
suggests that the Cu analog of USF-1 is unlikely to be readily
accessible. In this contribution, we report that a new PSM process
involving both PSE and PSA in a one-pot reaction can exploit the
lability and structural diversity of a Zn(II) based MOM to generate a
novel Cu(II) network that is the first structural isomer of HKUST-1.
Post-synthetic modification (PSM) of metal-organic materials
(MOMs), also referred to as metal-organic frameworks, MOFs, or
porous coordination polymers, PCPs, is of topical interest because it
can afford new materials which might otherwise be difficult or
impossible to prepare directly.1-8 For example, postsynthetic metal
ion9-14 and ligand exchange (PSE)15-18 generates novel MOMs that
are otherwise inaccessible while incorporating functionality such as
catalytic sites and/or chirality. Postsynthetic ligand addition (PSA)
remains relatively underexplored vs. metal/ligand exchange.19-23
Examples of PSA include the following: insertion of a bidentate
spacer ligand (4,4′-diazabicyclo[2.2.2]octane) into a 2-D layered
MOM to generate a pillared 3-dimensional pcu MOM;19 insertion of
a bridging ligand (3,6-di(4-pyridyl)-1,2,4,5-tetrazine) into a 3D
MOM, thereby altering gas sorption properties;20 sequential linker
installation into multivariate Zr-MOMs with functional groups that
are precisely located;21 reversible linking of polyhedral cages into
3D nets.22
Zn(II) MOMs are well-suited for metal ion exchange given the
relative lability of d10 complexes.9-14 They also offer diverse
coordination geometries that afford multiple starting points for
Scheme 1. Left: Triangle paddlewheel (red) and square paddlewheels (green);
Right: small rhombihexahedron (up) and small cubicuboctahedron (down).
Reaction of H3btc, Zn(NO3)2 and 5,10,15,20-Tetrakis(4-
sulfonatophenyl)porphyrinato Iron (III) chloride (FeTPPS) in
DMA/H2O afforded red-violet prismatic crystals of porphMOM-1,
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[Zn24(btc)14(C44H24N4Fe(III))2(S)]n (S = DMA or H2O). porphMOM-1 unsurprising that no N2 uptake was observed for activated
crystallizes in the orthorhombic space group Pnma with a = porphMOM-1. Crystals of porphMOM-1 were subjected to metal
34.304(2) Å, b = 29.205(1) Å, c = 18.774(1) Å and V = 18809(2) Å3. ion exchange with Cu2+ cations in order to determine if this would
UV-Vis spectroscopy confirms the presence of FeTPPS in enhance structural and hydrolytic stability.31 porphMOM-1 crystals
porphMOM-1 (Scheme S1 and Fig. S1) and full loading of FeTPPS were immersed into 0.04 M Cu(NO3)2 methanol solution for 10 days
was confirmed via ICP-MS. A single crystal X-ray diffraction (SCXRD) with refreshment of the solution each day. ICP-MS analysis revealed
study revealed that porphMOM-1 is constructed from three kinds that only 17% of Zn atoms had been exchanged by Cu. This might be
of molecular building blocks (Fig. S2): [Zn2(COO)4] square a consequence of the Zn2(COO)3]+ moieties being unsuitable for
paddlewheels; pseudo [Zn2(COO)4] square paddlewheels (Zn is 4- exchange with Cu. We considered that structural and charge
coordinated to three carboxylate moieties and one sulfonate group; balance considerations might enable the [Zn2(COO)3]+ MBBs to
[Zn2(COO)3]+ triangular paddlewheels. The average Zn-O bond transform into [M2(COO)4] MBBs by installation of an additional
distance in these building blocks is ~1.97 Å, which is consistent with carboxylate moiety (Scheme 2). Moreover, the internal space of the
the expected values.31 porphMOM-1 is comprised of three polyhedral cages in porphMOM-1 are large enough to
polyhedral cages, the largest of which is an irregular polyhedron accommodate guest molecules such as btc (dimensions: ~7 Å × 8 Å).
that is based upon 6 [Zn2(COO)4] square paddlewheels and 6 We therefore attempted
a new PSM approach based upon
[Zn2(COO)3]+ triangular paddlewheels (Fig. 1a, 1b). The large cage combining PSE and PSA in one pot. Thus, porphMOM-1 crystals
(Fig. S3 and yellow sphere in Fig. 1a) possesses an inner diameter of were immersed in a MeOH solution of 0.04 M Cu(NO3)2 and 0.0005
~12 Å (after subtracting van der Waals radii) and cage windows of ~ M 1,3,5-H3btc for 10 days with refreshment of the solution every
8 Å × 9 Å. The middle-sized octahemioctahedral cage is formed day. ICP-MS analysis of the bulk sample determined that 75% of the
through linking 8 btc anions by 6 square paddlewheels and 6 Zn cations had been replaced by Cu. SCXRD subsequently revealed
triangular paddlewheel MBBs (Fig. 1c, violet cage in Fig. 1a). FeTPPS that porphMOM-1 had transformed to a new crystalline phase
anions lie in this octahemioctahedral cage and coordinate to the (porph@HKUST-1-β), [Cu12(1,3,5-btc)8·(C44H24N4Fe(III))(S)]n, with
axial sites of 2 square paddlewheels and 2 triangular paddlewheel unit cell parameters (a = 18.510(5) Å, b = 18.510(5) Å and c =
moieties through their sulfonato moieties. This cage possesses a 30.287(8) Å, V = 8987(4) Å3) in the hexagonal space group
spherical cavity of a diameter ~11 Å and square windows of ~8 Å × 8 P63/mmc. Notably, porph@HKUST-1-β could not be directly
Å, which is large enough for small substrates and gas molecules to synthesized (1,3,5-H3btc, Cu(NO3)2, FeTPPS, MeOH, room
access the Fe3+ centers. In addition, 6 square paddlewheels and 3 temperature). We observed that porph@HKUST-1-β retains the
triangular paddlewheels are linked by 3 btc anions to generate a prismatic morphology of its parent, porphMOM-1, indicative of a
small prismatic cage with a triangular window of ~5 Å × 5 Å and a single-crystal-to-single-crystal transformation (Fig. S4).14 SCXRD
rhombic window of ~6 Å × 9 Å (brown cage in Fig. 1a). By treating revealed that the three Zn MBBs in porphMOM-1 had each
btc ligands and triangle paddlewheels as 3-connected nodes, and transformed to [Cu2(COO)4] paddlewheel MBBs. Cu-O(carboxylate)
square paddlewheels as 4-connected nodes, the framework of bonds in porph@HKUST-1-β exhibit average lengths of ~1.945 Å,
porphMOM-1 (trapped porphyrins were omitted) can be described which is consistent with the values seen in other copper
as a 3,3,3,4-connected tse net.32,33
paddlewheel MOMs such as HKUST-1.28 Along the same lines, Cu-Cu
distances (2.753 and 2.785 Å) are much shorter than the Zn-Zn
distances (3.235, 3.445, 3.806 and 2.988 Å) in porphMOM-1. UV-Vis
spectroscopy confirmed that FeTPPS retained its Fe(III) centers (Fig.
S1). As revealed by Scheme 2, metal exchange in porphMOM-1 was
accompanied by insertion of carboxylate moieties from btc anions
to afford [Cu2(COO)4] MBBs (inserted btc ligands are highlighted in
space-filling mode in Fig. S3). PSM thereby afforded a polyhedral-
based framework with unprecedented topology. The additional btc
anions in effect convert the triangular paddlewheels in the largest
cage of porphMOM-1 (Fig. 1b and S3) into square paddlewheels,
thereby generating an irregular polyhedral cage with the same
connectivity as nanoball-2, first reported by us in 2001 (green cage
in Fig. 2a).34 The additional btc anions mean that the prismatic cages
(Fig. S3) are joined to two adjacent tetrahedral cages. The
framework of porph@HKUST-1-β can be regarded as a new
supramolecular isomer of HKUST-1 (3,4-connected tbo net) with
3,3,3,4,4 connectivity (point symbol: {62.82.102}3{62.83.10}3{63}7{83})
(Fig. S5). This new net has been entered into the RCSR database as
‘yao’. To clarify the difference between HKUST-1 and
porph@HKUST-1-β, the two frameworks are compared side by side
in Fig. S6. The tbo topology network of HKUST-1 is comprised of
three distinct polyhedral cages with stoichiometry 1:1:2: nanoball-1
Fig. 1. (a) Three types of polyhedral cages in porphMOM-1 (large cage filled in
yellow, middle cage filled in violet and prism cage filled in brown); (b) large cage
comprised of 6 triangular paddlewheel and 6 square paddlewheel moieties; (c)
middle cage which contains coordinated FeTPPS moieties (space-filling mode, Zn
green, S yellow, N blue, Fe purple).
porphMOM-1 was soaked in MeOH for 10 days and then
activated under vacuum. MOMs that are sustained by [Zn2(COO)3]+
MBBs are generally unstable after removal of solvent,24-26 so it is
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(also referred to as a small rhombihexahedron or MOP-1),35 an
As anticipated, permanent porosity is exhibited by
octahemioctahedral cage and a tetrahedral cage. porph@HKUST-1- porph@HKUST-1-β (Fig. 3). N2 sorption revealed that
β can also be disassembled into three distinct polyhedral cages: porph@HKUST-1-β adsorbs 241 cm3/g of N2 at 77 K and 1 bar,
nanoball-2, an octahemioctahedral cage and a tetrahedral cage, corresponding to a Langmuir surface area of 731 m2/g (BET surface
with stoichiometry of 1:1:2. nanoball-1 and nanoball-2, the large area: 705 m2/g). In contrast, porphMOM-1 is non-porous after
cavities, and their manner in which they are packed are what activation (Fig. 3), possibly due to the instability of triangular Zn
distinguish these two Cu-btc polymorphs. Specifically, in tbo the MBBs.24-26 Thermogravimetric analysis (TGA) revealed that
large cavities exhibit cubic close packing, whereas in yao they methanol-exchanged porphMOM-1 and porph@HKUST-1-β
exhibit hexagonal close packing. Fig. S7 compares nanoball-1 and undergo weight losses of ~10% and 12%, respectively, below 100˚C,
nanoball-2 and shows that they result from different connectivity of but that they are thermally stable to ~260˚C and 340˚C, respectively
12 copper square paddlewheels and 24 1,3-bdc (benzene-1,3- (Fig. S9). The enhanced thermal stability and permanent porosity of
dicarboxylate) moieties. In 2001, we reported the existence of porph@HKUST-1-β is presumably due to the transformation of the
nanoball-1 and nanball-2 as discrete cages and suggested that triangular Zn MBBs into [Cu2(COO)4] MBBs40 and the additional
nanoball-2 would have the potential to serve as a supramolecular connectivity of the network.
building blocks (SBB) to build 3D MOMs.34 porph@HKUST-1-β is to
our knowledge the first example of such a network. The existence
of both nanoball-1 and nanoball-2 can be ascribed to the “partial
flexibility” of 1,3-bdc moieties which can sustain twist angles of 0-
90o or bend angles of up to 29.7o (Fig. S8).36 In addition, as revealed
by SCXRD, FeTPPS anions are no longer coordinated and revert to
being encapsulated in the octahemioctahedral cages (Fig. 2b) of
porph@HKUST-1-β. This type of porphyrin encapsulation was seen
in FeTPPS@HKUST-1 and has been observed in other
porph@MOMs.37-39 It should be noted that FeTPPS can only be
encapsulated in the octahemioctahedral cages because the size and
symmetry of porphyrins perfectly fit the octahemioctahedral cages
but not the large nanoball-2 cage and small tetrahedral cage.37
Fig. 3. N2 sorption isotherms of porphMOM-1 and porph@HKUST-1-β at 77K.
Encapsulated Fe-porphyrin centers have the potential to enable
heterogeneous catalysis by serving as catalytically active sites that
mimic enzymatic heme centers (e.g. peroxidative oxygen
transfer).41 Polyphenols are routinely used for the evaluation of the
peroxidase activity of heme-based enzymes. Therefore, 1,2,3-
trihydroxybenzene (THB) (dimensions: ~5.7 Å × 5.8 Å) was selected
Scheme 2. A Zn based triangle paddlewheel MBB can transform into a Cu based
square paddlewheel MBB via a one-pot PSM process involving PSE of metal ion to evaluate the catalytic performance of porphMOM-1 and
exchange and PSA of ligand addition.
porph@HKUST-1-β by monitoring the oxidation of THB to the
purpurogallin dimer product at 420 nm in acetonitrile (ε = 4.32
mM−1 cm−1) at room temperature.42
Table 1. Catalytic oxidation of THB in the presence of 30 mM H2O2 in acetonitrile.
Initial rate
(mM/s)
Conversion (%)
Catalysts
(72h)
30.4
14.4
11.5
4.5
3.1
8.9
<1
FeTPPS
porph@HKUST-1-β
porphMOM-1
FeTPPS@HKUST-115b
HKUST-1
6.42 × 10-4
2.77 × 10-4
1.90 × 10-4
7.81 × 10-5
5.37 × 10-5
2.74 × 10-5
5.81 × 10-7
Hemin
Blank
The results of the catalytic studies are presented in Table 1 and
Fig. S10. They reveal that both porph@HKUST-1-β and porphMOM-
1 exhibit fast initial rates of 2.77×10-4 mM s-1 and 1.90×10-4 mM s-1
respectively, which are comparable to the homogeneous FeTPPS
system (6.42×10-4 mM s-1). In contrast, the initial rate exhibited by
Fig. 2. (a) Three types of polyhedral cages exist in porph@HKUST-1-β (nanoball-2,
green, octahemioctahedral cage, orange and tetrahedral cage, blue); (b)
octahemioctahedral cage with encapsulated FeTPPS moieties. FeTPPS moieties
are highlighted in space-filling mode (Cu cyan, S yellow, N blue, Fe purple).
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6
A. Shultz, A. Sarjeant, O. Farha, J. Hupp, S. Nguyen, J. Am. Chem. Soc. 2011,
133, 13252.
homogeneous Hemin is more than 10 times slower than
porph@HKUST-1-β whereas HKUST-1 reacts ~5 times slower with a
rate of 5.37×10-5 mM s-1. This suggests that catalytic activity can be
attributed to the FeTPPS in the framework rather than the Cu
paddlewheels given that THB is small enough to diffuse into the
porphyrin-containing cages. In addition, both porph@HKUST-1-β
and porphMOM-1 exhibit higher conversion than reported for
7
8
S. Yuan, Y.-K. Deng, D. Sun, Chem. Eur. J. 2014, 20, 10093.
S. Yuan, Y.-K. Deng, W.-M. Xuan, X.-P. Wang, S.-N. Wang, J.-M. Dou, D. Sun,
CrystEngComm 2014, 16, 3829.
9
M. Dincă, J. R. Long, J. Am. Chem. Soc. 2007, 129, 11172.
T. K. Prasad, D. H. Hong, M. P. Suh, Chem. Eur. J. 2010, 16, 14043.
J. Zhao, L. Mi, J. Hu, H. Hou, Y. Fan, J. Am. Chem. Soc. 2008, 130, 15222.
M. Lalonde, W. Bury, O. Karagiaridi, Z. Brown, J. T. Hupp, O. K. Farha, J.
Mater. Chem. A. 2013, 1, 5453.
10
11
12
FeTPPS@HKUST-1. porph@HKUST-1-β was chosen as
a
representative heterogeneous catalyst. The filtrate of
porph@HKUST-1-β after catalysis did not exhibit the characteristic
UV-Vis peak of FeTPPS (Fig. S1), indicating that no leaching of
FeTPPS had occurred during catalysis. Moreover, recyclability data
revealed that porph@HKUST-1-β can be reused for at least four
cycles without significant decrease of catalysis activity and loss of its
crystallinity (Fig. S11 and S12).
13
14
C. K. Brozek, M. Dincâ, Chem. Sci. 2012, 3, 2110
M. Kim, J. F. Cahill, H. Fei, K, A. Prather, S. M. Cohen, J. Am. Chem. Soc.
2012, 134, 18082.
15
16
17
18
19
M. Kondo, S. Furukawa, K. Hirai, S. Kitagawa, Angew. Chem. Int. Ed. 2010,
49, 5327.
B. J. Burnett, P. M. Barron, C. Hu, W. Choe, J. Am. Chem. Soc. 2011, 133,
9984.
O. Karagiaridi, M. B. Lalonde, W. Bury, A. A. Sarjeant, O. K. Farha, J. T. Hupp,
J. Am. Chem. Soc. 2012, 134, 18790.
In summary, we report herein a new PSM strategy that involves
postsynthetic metal ion exchange and ligand addition in a one-pot
T. Li, M. T. Kozlowski, E. A. Doud, M. N. Blakely, N. L. Rosi, J. Am. Chem. Soc.
2013, 135, 11688.
process.
A porphyrin linked MOM (porphMOM-1) thereby
R. Kitaura, F. Iwahori, R. Matsuda, S. Kitagawa, Y. Kubota, M. Takata, T. C.
Kobayashi, Inorg. Chem. 2004, 43, 6522
transforms into a porphyrin-encapsulating MOM (porph@HKUST-1-
β) in single-crystal to single-crystal fashion. Notably, HKUST-1-β is
the first example of a supramolecular isomer of the archetypal
coordination network HKUST-1 and results from its 12 square
paddlewheels forming an irregular polyhedral cage that is distinct
from the regular polyhedral cage observed in HKUST-1.
porph@HKUST-1-β was found to exhibit enhanced stability,
permanent porosity and biomimetic catalytic activity towards
oxidation of a polyphenol than porphMOM-1. This new PSE/PSA
strategy enriches the toolbox of PSM strategies and enables the
synthesis of a functional porous material that would otherwise be
difficult or impossible to achieve. Further, the concerted metal
exchange/ligand installation process is unlikely to be limited to the
specific case in question. Indeed, it should be general for MOFs that
are sustained by labile transition metals such as Zn(II) and Cd(II).
The data for porphMOM-1 was collected at the Advanced Photon
Source on beamline 15ID-C of ChemMatCARS Sector 15, which is
20
21
H. J. Park. Y. E. Cheon, M. P. Suh, Chem. Eur. J. 2010, 16, 11662.
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.
22
23
24
J.-R. Li, D. J. Timmons, H.-C. Zhou, J. Am. Chem. Soc. 2009, 131, 6368.
Z. Chen. S. Xiang, D. Zhao, B. Chen, Cryst. Growth Des. 2009, 9, 5293.
Z.-J. Zhang, W. Shi, Z. Niu, H.-H. Li, B. Zhao, P. Cheng, D.-Z. Liao, S.-P. Yan,
Chem. Commun. 2011, 47, 6425.
25
26
27
28
29
X.-R. Hao, X.-L. Wang, K.-Z. Shao, G.-S. Yang, Z.-M. Su, G. Yuan,
CrystEngComm. 2012, 14, 5596
H. Ma, S. Wang, H. Liu, F. Meng, W. Zheng, W. Gao, CrystEngComm. 2015,
17, 1001
D. Kim, X. Liu, M. Oh, X. Song, Y. Zou, D. Singh, K. S. Kim, M. S. Lah,
CrystEngComm. 2014, 16, 6391.
S. S. Chui, S. M. Lo, J. P. Charmant, A. G. Orpen, I. D. Williams, Science 1999,
283, 1148.
J. Lu, A. Mondal, B. Moulton, M. J. Zaworotko, Angew. Chem. Int. Ed. 2001,
113, 2171.
30
31
F. Allen, Acta Crystallogr. 2002, B58, 380.
M. K. Bhunia, J. T. Hughes, J. C. Fettinger, A. Navrotsky, Langmuir 2013, 29,
8140.
principally
supported
by
the
National
Science
32
33
M. Okeeffe, O. M. Yaghi, Chem. Rev. 2012, 112, 2.
M. Okeeffe, M. A. Peskov, S. Ramsden, O. M. Yaghi, Acc. Chem. Res. 2008,
41, 12.
Foundation/Department of Energy under grant number NSF/CHE-
0822838. The Advanced Photon Source is supported by the U. S.
Department of Energy, Office of Science, Office of Basic Energy
Sciences, under Contract No. DE-AC02-06CH11357. ZZ
acknowledges the China Young 1000 Talents program and NSFC NO.
21601093. MZ acknowledges the generous financial support of the
Science Foundation Ireland (Grant 13/RP/B2549). We thank Prof.
Peng Cheng and Prof. Wei Shi from Nankai University for their
assistance in measurement of ICP-MS.
34
35
B. Moulton, J. J. Lu, A. Mondal, M. J. Zaworotko, Chem. Commun. 2001, 863.
M. Eddaoudi, J. Kim, J. B. Wachter, H. K. Chae, M. O'Keeffe, O. M. Yaghi, J.
Am. Chem. Soc. 2001, 123, 4368.
36
37
Z. Zhang, L. Wojtas, M. J. Zaworotko, Cryst. Growth Des. 2011, 11, 1441.
Z. Zhang, L. Zhang, L. Wojtas, M. Eddaoudi, M. J. Zaworotko, J. Am. Chem.
Soc. 2012, 134, 928.
38
39
R. W. Larsen, L. Wojtas, J. Perman, R. L. Musselman, M. J. Zaworotko, C. M.
Vetromile, J. Am. Chem. Soc. 2011, 133, 10356.
R. W. Larsen, J. Miksovska, R. L. Musselman, L. Wojtas, J. Phys. Chem. A
2011, 115, 11519.
40
41
42
Z. Wei, W. Lu, H.-L. Jiang, H.-C. Zhou, Inorg. Chem. 2013, 52, 1164.
Y. Chen, T. Hoang, S. Ma, Inorg. Chem. 2012, 51, 12600.
Q. Wang, Z. Yang, L. Wang, M. Ma, B. Xu, Chem. Commun. 2007, 10, 1032.
Notes and References
1
S. Cohen, Chem. Rev. 2012, 112, 970.
2
S. R. Batten, S. M. Neville, D. R. Turner, Coordination Polymers: Design,
Analysis and Application; Royal Society of Chemistry, Cambridge, UK, 2009.
L. R. MacGillivray, Metal-Organic Frameworks: Design and Application, John
Wiley & Sons, Hoboken, New Jersey, 2010.
3
4
5
Z. Zhang, W.-Y. Gao, L. Wojtas, S. Ma, M. Eddaoudi, M. J. Zaworotko, Angew.
Chem. Int. Ed. 2012, 51, 9330.
K. L. Mulfort, O. K. Farha, C. L. Stern, A. A. Sarjeant, J. T. Hupp, J. Am. Chem.
Soc. 2009, 131, 3866.
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Communication
ChemComm
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DOI: 10.1039/C7CC04958G
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