Cluster nuclearity control and modulated hydrothermal synthesis of functionalized Zr12 metal-organic frameworks

Article abstract of DOI:10.1039/c8dt05060k

The synthesis of chemically stable metal-organic frameworks (MOFs) in benign solvents is a key step towards their scalable production and commercialization. Extending the modulated hydrothermal (MHT) synthesis approach for zirconium (Zr) MOFs, we herein demonstrate cluster nuclearity control over the secondary building units (SBUs) to target Zr₆-based and Zr₁₂-based phases for the Zr terephthalate (Zr-BDC) system. Different functional groups (-NH₂, -NO₂, -Br, -F₄) can be incorporated into Zr₁₂-BDC, providing an avenue to further tune the chemical properties of these promising MOFs.

Full text of DOI:10.1039/c8dt05060k

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January 2016 Pages 1–398
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ISSN 1477-9226
PAPER
Joseph T. Hupp, Omar K. Farha et al.
Efficient extraction of sulfate from water using
framework
a Zr-metal–organic
rsc.li/dalton

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DOI: 10.1039/C8DT05060K
Journal Name
COMMUNICATION
Cluster nuclearity control and modulated hydrothermal synthesis
of functionalized Zr metal-organic frameworks
1
2
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
a
a
a
a
Shing Bo Peh, Youdong Cheng, Jian Zhang, Yuxiang Wang, Ger Hui Chan, Jian Wang, and Dan
,
a
Zhao*
DOI: 10.1039/x0xx00000x
www.rsc.org/
The synthesis of chemically stable metal-organic frameworks substoichiometric connectivity.14,
15
A
further source of
(
MOFs) in benign solvents is a key step towards their scalable structural diversity is through variations in cluster nuclearity.
production and commercialization. Extending the modulated While the hexanuclear SBU is found in majority of Zr structures,
hydrothermal (MHT) synthesis approach for zirconium (Zr) MOFs, other Group IV SBUs have been discovered, such as the chain-
we herein demonstrate cluster nuclearity control over the based SBU of the MIL-140 series, as well as dodecanuclear Zr12
1
6-20
6
secondary building units (SBUs) to target Zr -based and Zr12-based and Hf12 SBUs.
Significantly, several isoreticular analogues
phases for the Zr terephthalate (Zr-BDC) system. Different have been isolated for these building blocks, extending the
2
1-26
2
functional groups (-NH , -NO
2
, -Br, -F
4
) can be incorporated into scope of molecular design for Group IV MOFs.
We have
Zr12-BDC, providing an avenue to further tune the chemical previously reported the use of modulated hydrothermal (MHT)
property of these promising MOFs.
synthesis approach to obtain functionalized variants of UiO-66
1
2
with different terephthalate-based ligands. In the present
contribution, we show the capability of MHT approach to tune
the cluster nuclearity in the Zr-BDC MOF series by synthesizing
MOFs are a class of porous materials which have garnered
widespread research interests due to their tunable porosity,
composition and functionality.
predictable combination of structurally encoded building
blocks implies the engineering of novel MOFs to address global
1
,
2
The prospect of the
dodecanuclear analogues bearing –NO
functionalities. In particular, Zr12-BDC-NH
2
catalytic performance over its Zr counterpart (i.e. UiO-66-NH )
2 2 4
, –NH , –Br, or –F
2
shows improved
6
3
, 4
challenges in energy and environment. To further align this
goal of rational design with the demands of commercialization,
increasing attention has been diverted towards the
exploration of stable, high nuclearity building blocks as well as
the compatibility of MOF synthesis with cheaper and greener
solvents.5
in the tandem deacetylation-Knoevenagel condensation
cascade reaction.
Various topological outcomes exist for the self-assembly of
Zr carboxylate clusters with linear ditopic linkers – including
8, 27, 28
fcu, bcu, and reo structures.
The fcu net is predicted by
-7
the minimal transitivity principle upon combining
Among the high connectivity inorganic building blocks, the
9, 29
6 6
cubooctahedral Zr /Hf clusters with linear ditopic linkers.
hexanuclear SBU based on Group IV metals (herein M
Hf, or Ce) is highly significant in the rational design of water-
stable frameworks. Since the pioneering synthesis of the Zr
6
, M = Zr,
The reo topology is a derivative net arising from the systematic
absence of ligands at the corner positions of the cubic unit
30
6
cell. The existence of reo nanodomains in UiO-66(Hf) was
terephthalate MOF UiO-66 by a simple self-assembly of the
observed by Goodwin’s group under high monocarboxylate
8
constituent reactants, synthetic developments have revealed
28
concentrations. Such systematic absences have also been
highly reproducible SBU formation conditions through the
31
reported for sulfonate-decorated linkers.
dimerization of Zr /Hf clusters by bridging hydroxo ligands to
form a distinct SBU – (M12(μ -O) (μ -OH) (μ-OH) ) – opens
access to Zr/Hf MOFs exhibiting two additional topologies,
The in-situ
involvement of monocarboxylate additives (termed
6
6
modulators).9 Such robustness of the M
, 10
SBU has permitted
6
3
8
3
8
6
commercially relevant solvent substitutions, in particular by
water, and even solvent-free techniques for scale-up
25, 32
namely hcp and hxl.
The resultant materials differ from
production.1
1-13
Group IV MOFs incorporating linear ditopic
the fcu structure in their stacking pattern, and consequently
manifest distinct X-ray diffraction peaks for (002), (100), and
linkers have exhibited interesting behaviours such as
(
101) crystal planes in the low angle region. Based on the
simulated structure of Zr12-BDC (Fig. 1c), these occur at 5.0°,
.2° and 7.6° respectively, which may be used for positive
a. Department of Chemical and Biomolecular Engineering, National University of
Singapore, 4 Engineering Drive 4, 117585 Singapore
7
Electronic Supplementary Information (ESI) available: Experimental methods and phase identification.
detailed data. See DOI: 10.1039/x0xx00000x
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Considering the feasibility in synthesizing Zr12-BDC at reflux
View Article Online
DOI: 10.1039/C8DT05060K
temperature, a second round of optimization was performed
2
at 120 °C. At this temperature, Zr12-BDC-NH crystallized within
a narrow range of modulator concentration (60-90 eq. to
linker, Fig. S1 and S2a). Moreover, the phase transition relative
to the modulator concentration is inverted when compared to
the solvothermal preparation of UiO-67(Hf). Specifically, the
increase of modulator concentration above 120 eq. resulted in
preferential formation of Zr -BDC-NH over Zr12-BDC-NH . This
6 2 2
is presumably because the solubility effect of the liquid
modulator (acetic acid, AA) is opposite in the two situations.
4
’4-Biphenyldicarboxylic acid (BPDC, the linker for UiO-67 (Hf))
has a higher solubility in dimethylformamide (DMF) than in AA,
3
6
whereas BDC has a higher solubility in AA than in water. Thus,
the increase of AA concentration under MHT conditions will
elevate the linker concentration in the reaction mixture and
6 2
accelerate nucleation of Zr -BDC-NH . To investigate the
solubility hypothesis, we replaced varying portions of water by
methanol (MeOH) as a ‘good’ solvent and investigated the
phase behaviour under various modulator concentrations. At
1
6
Fig. 1. (a) Crystal structure representation of Zr -BDC. Left to right: View from [10 ]
direction, [001] direction, and polyhedral representation. (b) Crystal structure
representation of Zr12-BDC. Left to right: View along [100] direction, [001] direction and
9
0 eq. AA, replacement of half the solvent volume by MeOH
led to the formation of Zr -BDC-NH instead of Zr12-BDC-NH
Fig. S2b). In addition, we explored the use of dimethyl
6
2
2
(
6
polyhedral representation. (c) Simulated and experimental PXRD patterns of Zr - and
Zr12- BDC. Note: Zr12-BDC may exhibit 2D layered hxl or 3D hcp topology. The optimized aminoterephthalate as an alternative precursor. The in-situ
condition in this study yields hcp phase of Zr12-BDC. (d) Experimental PXRD patterns of
the synthesized Zr12-BDC analogues. Herein, the notation Zr12-BDC-X is used to
acknowledge the nuclearity difference without making assumptions on the structure,
due to the possible in-situ transformation between different phases.
hydrolysis of ester based precursors has been used previously
to improve the purity of specific kinetic MOF analogues, such
3
7
as MIL-100(Al). Under the employed conditions, the use of
ester precursor did not have a major effect on the phase
domains (Fig. S1).
4
Zr12-BDC-H and Hf12-BDC-F were reported by our group
previously.9, 17 These phases were attained by modified
protocols, and the X-ray diffraction patterns were assigned to
the hcp phase by Hartmann et al. and Grey et al.,
respectively.3
isolation of Hf12-BDC and Zr12-BDC-F
we have successfully incorporated –NO
functionalities into the Zr12-BDC framework using the MHT
3,
34
In addition, the latter work reported the
. Building on these results,
, –NH , –Br, and –F
4
4
2
2
3
4
method (Fig. 1d). Except Zr12-BDC-F
4
,
the remaining
analogues are yet to be reported by solution-based synthetic
processes. We note that an amino-functionalized UiO-66 thin
film prepared by gas-phase deposition was observed to exhibit
hexagonal morphology, but no bulk phase preparation was
reported.35 The self-assembly of Zr12-BDC-X involves two
independent processes, specifically (1) the cluster dimerization
Fig. 2. (a) Scheme of functionalized Zr12-BDC-X with indicative pore apertures
of Zr
6
to form Zr12 clusters, and (2) linker replacement of
2 2 4
(left to right: X = NO , NH , Br, F ). (b) FT-IR spectra of Zr12-BDC-X. (c) Nitrogen
2
5
capping monocarboxylates to form the extended framework.
sorption isotherms at 77 K for functionalized Zr12-BDC-X (adsorption, filled;
desorption, empty).
Considering the involvement of hydroxo ligands to bridge the
clusters, it is likely that the progress of the first step is
promoted under hydrolytic conditions. In this study, we thus
increased simultaneously the reaction temperature (favoring
hydrolysis) and modulator concentration (to reduce nucleation)
Fourier-transform infrared (FT-IR) spectra (Fig. 2b) and N
2
sorption isotherms at 77 K (Fig. 2c) were collected for the
functionalized Zr12-BDC-X MOF samples. The linker
to yield the desired hcp phase for four cases (X = H, NO
and F , see ESI for optimized reaction conditions). For Zr12
BDC-NH , although the product showed X-ray diffraction
2
, Br,
-
1
carboxylates generate two sharp peaks at around 1400 cm
4
-
and 1600 cm- in the FT-IR spectra, corresponding to the
1
2
symmetric and asymmetric C-O stretching vibrations
patterns consistent with the desired structure, the yield and
quality were negatively affected.
8, 38
respectively.
Given the increased nuclearity of the Zr12
cluster based
cluster, the samples are less porous than Zr
6
analogues, with measured Brunauer-Emmett-Teller (BET)
2
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surface areas ranging from 272 m g (Zr12-BDC-F
COMMUNICATION
2
-1
) to 622 m2 the likelihood of forming the hcp structure.45 Specifically, the
View Article Online
4
-1
DOI: 10.1039/C8DT05060K
and BDC-Br exhibit respectively bent
g
(Zr12-BDC). The isotherms exhibit microporous feature for carboxylates in BDC-F
4
4
6, 47
the most part, with some hystereses at high partial pressures, and non-coplanar conformations.
which can be attributed to interparticle voids from aggregated To further investigate the feasibility of exfoliating Zr12-BDC-
X, the -NH and -F functionalized analogues were subject to
sonication treatment in MeOH before morphological
characterization. The sonically-treated Zr12-BDC-NH contained
3
9
crystals and possible crystal defects.
2
4
2
numerous particles with terraced morphology, evidencing
their degradation under cavitation forces (Fig. 3d, left). High-
resolution TEM and selected area electron diffraction (SAED)
confirmed the retention of hexagonal order (Fig. 3e-f). Atomic
force microscopy (AFM) for sonication-treated Zr12-BDC-NH
2
revealed shape-similar particles of decreasing thicknesses (10
to 20 nm) and lateral size (Fig. S7a). Under the same treatment,
Zr12-BDC-F
Fig. S7b). Hence, the spontaneous 3D-to-2D transition may be
a prerequisite to derive high aspect ratio materials from the
4
separated into layers with thicknesses of 2-4 nm
(
Fig. 3. Morphological characterization of Zr12-BDC-NH
NH . (d, e) TEM images of Zr12-BDC-NH (sonicated fragment). (f) Selected area electron
diffraction (SAED) image of Zr12-BDC-NH (sonicated fragment).
2
: (a-c) SEM images of Zr12-BDC- Zr12 cluster-based MOFs.
2
2
The high aspect ratio morphologies, coupled with the small
size of the dispersed particles, may be advantageous for
2
4
2
catalysis. While access to the porous cages in the fcu
structure is restricted by small window apertures, the 1D
channels of the hcp structure (Fig. 2b) allow facile mass
transfer of reagents. Recently, Momeni and Cramer predicted
by simulation the superior hydrolytic activities of Zr12-cluster
based MOFs with coordinatively unsaturated metal sites,
which function as Lewis acids. We used the tandem
deacetalization-Knoevenagel condensation reaction to
investigate the possible differences in catalytic activity
Two-dimensional (2D) materials have been attracting wide
research interests for diverse applications including electronics,
4
0, 41
catalysis and membrane separations.
The short diffusive
lengths and readily accessible active sites, combined with the
facile installation of chemical functionalities, make 2D MOFs
4
2
ideal materials for catalytic applications. The spontaneous
48
transformation of Hf12-based hcp UiO-67(Hf) and hcp UiO-66-
4
F (Hf) led Grey et al. to propose hcp-hxl transformation as a
1
7, 34
potential route to other 2D MOF nanomaterials.
We
between Zr
6
-BDC-NH
2
and Zr12-BDC-NH
2
arising from the
sought to test this hypothesis by examining the delamination
characteristics of different functionalized Zr12-cluster based
MOFs. Fig. 3a shows the morphology of the Zr12-BDC-NH . The
2
49, 50
change in SBU nuclearity.
First, benzaldehyde dimethyl
acetal, a, is deprotected by Lewis acids into benzaldehyde, b,
which is subsequently condensed with malononitrile under
basic catalysis to form benzylidene malononitrile, c. Acetal
protection is commonly adopted to protect aldehyde carbonyls
from unwanted reactions, while products of the Knoevenagel
condensation serve as important intermediates for various
as-prepared samples appear as intergrown florets of
hexagonal nanoplates, which are clearly distinct from the
3
3, 43
6
typical octahedral morphology of Zr -BDC crystals.
However, the different functionalized samples exhibited
differing stabilities with regards to delamination. The as-
prepared Zr12-BDC-F exhibited high X-ray diffraction peak
4
intensity for the (100) reflection compared to the (101)
reflection, suggesting a lower degree of ordering for the latter
Fig. 1d). The (002) and (101) reflections disappeared after
51
pharmaceuticals. The multi-step reaction hence facilitates
the comparison of the node-specific Lewis acidity and the
linker-centred Lewis basic activity for the two materials. The
progress of the tandem reaction was monitored by H NMR in
deuterated chloroform. The overall conversion and yields for
each step were calculated by integrating characteristic peak
areas for a, b, and c (Table 1). The catalyst concentration was
1
(
storage of the sample in air for 4 weeks, yielding a
characteristic pattern for 2D materials (Fig. S6a). The -Br and -
NO
transformation according to their X-ray diffraction patterns
Fig. S3b). On the other hand, even after prolonged storage in
air, no discernable change in powder X-ray diffraction (PXRD)
patterns occurred in Zr12-BDC and Zr12-BDC-NH . Clearly, the
2
functionalized samples also underwent visible structural
optimized at 55 °C. At 100 mg loading, Zr12-BDC-H and Zr12
BDC-NH attained conversions of 94.5% and 99% after 24 h,
respectively, which are slightly higher than that of Zr -BDC-NH
92.7%). The catalyst-free control reflected a conversion of 6.5%
-
2
(
6
2
(
2
to b due to the absence of catalyst, whereas no c was detected.
With respect to a, the yield of final product c was only 31.6%
easiness of 3D-to-2D structural transformation in Zr12 cluster
based MOFs depends strongly on the chemical nature of the
bridging linkers. We postulate two possible contributions to
rationalize the observed stability trend. Firstly, the presence of
electron-withdrawing substituents stabilizes the conjugate
base of the carboxylate linkers, thus weakening the
coordination bond and favouring the exfoliation. Secondly,
deviations from linearity in the bridging linkers may diminish
under the catalysis of Zr
and 91.8%, respectively, when Zr12-BDC-H and Zr12-BDC-NH
was used. To study the contribution of Lewis acidic sites,
digestion experiments in basic D O were performed on the Zr12
MOFs to estimate the defects density. The modulator to linker
ratio (m ) was tabulated in Table S3. The density of Lewis
6 2
-BDC-NH , which increased to 64.5%
2
2
4
4
R
acidic sites did not appear to be increased in the Zr12
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Journal Name
framework (m
modulated Zr
R
= 0.05 for Zr12-BDC-H vs. < 0.2 for acetic acid- This work was supported by the Ministry ofViEewduArctiaclteioOnnline-
-BDC-H). The improved accessibility to active Singapore (MOE AcRF Tier 1 R-279-000D-O4I7: 210-1.110329,/CR8-2D7T095-006000K-
6
sites and higher reactivity of the Zr12 sites may have led to the 540-114), and the Agency for Science, Technology and
superior activity.48 Despite strong dependence of Knoevenagel Research (PSF 1521200078, IRG A1783c0015, and IAF-PP
condensation on the polarity of the reaction media, the A1789a0024).
2
efficiency of Zr12-BDC-NH for the same reaction remained
comparable to the previously reported MOF catalysts (Table
S4) even in deuterated chloroform (ε = 4.8) and nearly
stoichiometric quantities of the starting reagents. The stability
of the catalysts was ascertained by PXRD studies (Fig. S11).
Conflicts of interest
The authors declare no competing financial interests.
Zr12-BDC-NH
2
did not show signs of degradation during
recovery or immersion in aqueous solutions of varying pH Notes and references
values (1-10), indicating retention of the MOF structure.
1
2
3
H.-C. Zhou, J. R. Long and O. M. Yaghi, Chem. Rev., 2012, 112,
73-674.
Table 1. Conversions and yields of tandem deacetalization-Knoevenagel condensation
reactions catalyzed by Zr-MOFs.
6
H. Furukawa, K. E. Cordova, M. O’Keeffe and O. M. Yaghi,
Science, 2013, 341.
X. Zhao, Y. Wang, D.-S. Li, X. Bu and P. Feng, Adv. Mater.,
2
018, 30, 1705189.
4
5
S.-L. Li and Q. Xu, Energy Environ Sci, 2013, 6, 1656-1683.
S. Yuan, J.-S. Qin, C. T. Lollar and H.-C. Zhou, ACS Cent. Sci.,
2
018, 4, 440-450.
P. A. Julien, C. Mottillo and T. Friscic, Green Chem., 2017, 19,
729-2747.
6
7
2
Catalyst
Loading (mg)
Conv.
%)
6.5
Y
(%)
6.5
b
Y
c
(%)
-
S. Yuan, L. Feng, K. Wang, J. Pang, M. Bosch, C. Lollar, Y. Sun,
J. Qin, X. Yang, P. Zhang, Q. Wang, L. Zou, Y. Zhang, L. Zhang,
Y. Fang, J. Li and H.-C. Zhou, Adv. Mater., 2018, 30, 1704303.
J. H. Cavka, S. Jakobsen, U. Olsbye, N. Guillou, C. Lamberti, S.
Bordiga and K. P. Lillerud, J. Am. Chem. Soc., 2008, 130,
13850-13851.
(
N.A.
0
8
Zr12 BDC-NH
Zr12 BDC-NH
Zr12 BDC-NH
Zr12 BDC-H
2
2
2
25
31.0
49.5
99.0
94.3
92.7
98.4
95.3
95.1
9.0
0.5
22.0
49.0
91.8
64.5
31.6
91.8
94.8
94.7
50
9
1
1
V. Guillerm, S. Gross, C. Serre, T. Devic, M. Bauer and G.
Ferey, Chem. Commun., 2010, 46, 767-769.
100
100
100
100
100
100
7.2
29.8
61.1
6.6
0 S. Andreas, R. Pascal, G. Adelheid, L. Jann, W. Florian, W.
Michael and B. Peter, Chem. Eur. J., 2011, 17, 6643-6651.
1 F. Ragon, B. Campo, Q. Yang, C. Martineau, A. D. Wiersum, A.
Lago, V. Guillerm, C. Hemsley, J. F. Eubank, M.
Vishnuvarthan, F. Taulelle, P. Horcajada, A. Vimont, P. L.
Llewellyn, M. Daturi, S. Devautour-Vinot, G. Maurin, C. Serre,
T. Devic and G. Clet, J. Mater. Chem. A, 2015, 3, 3294-3309.
2 Z. Hu, Y. Peng, Z. Kang, Y. Qian and D. Zhao, Inorg. Chem.,
6 2
Zr BDC-NH
Recycle 1
Recycle 2
Recycle 3
0.4
0.4
1
1
Reaction conditions: benzaldehyde dimethyl acetal (1.0 mmol), malononitrile (1.1
2
015, 54, 4862-4868.
mmol), CDCl
3
(1.5 mL), and catalyst; reaction temperature 55 °C; reaction time 24
3 M. Rubio-Martinez, C. Avci-Camur, A. W. Thornton, I. Imaz,
1
h. The conversions and yields were determined by H NMR.
D. Maspoch and M. R. Hill, Chem. Soc. Rev., 2017, 46, 3453-
3
480.
In summary, we have prepared five functionalized Zr12
-
1
4 H. Wu, Y. S. Chua, V. Krungleviciute, M. Tyagi, P. Chen, T.
Yildirim and W. Zhou, J. Am. Chem. Soc., 2013, 135, 10525-
10532.
cluster based MOFs on the basis of functionalized
terephthalate linkers using a modulated hydrothermal (MHT)
synthesis approach, thus illustrating the feasibility of MHT in
tuning the nuclearity of MOF SBUs. Spontaneous 3D-to-2D
structure transformation was observed for certain variants.
1
1
5 G. C. Shearer, S. Chavan, S. Bordiga, S. Svelle, U. Olsbye and
K. P. Lillerud, Chem. Mater., 2016, 28, 3749-3761.
6 V. Guillerm, F. Ragon, M. Dan-Hardi, T. Devic, M.
Vishnuvarthan, B. Campo, A. Vimont, G. Clet, Q. Yang, G.
Maurin, G. Férey, A. Vittadini, S. Gross and C. Serre, Angew.
Chem. Int. Ed., 2012, 51, 9267-9271.
7 M. J. Cliffe, E. Castillo-Martínez, Y. Wu, J. Lee, A. C. Forse, F.
C. N. Firth, P. Z. Moghadam, D. Fairen-Jimenez, M. W.
Gaultois, J. A. Hill, O. V. Magdysyuk, B. Slater, A. L. Goodwin
and C. P. Grey, J. Am. Chem. Soc., 2017, 139, 5397-5404.
Zr12-BDC-NH
2
was shown to exhibit distinct catalytic behaviour
for the tandem deacetalization-Knoevenagel
from Zr -BDC-NH
6
2
1
condensation reaction, due to the improved access to amine
active sites in the MOF. The findings indicate that cluster
condensation may be employed as a general strategy to fine-
tune MOF properties without expending the linker degrees of 18 P. Ji, K. Manna, Z. Lin, X. Feng, A. Urban, Y. Song and W. Lin,
freedom, paving
a
route to desired morphologies and
J. Am. Chem. Soc., 2017, 139, 7004-7011.
1
2
2
9 S. Waitschat, H. Reinsch and N. Stock, Chem. Commun.,
porosities in Zr-MOFs.
2
016, 52, 12698-12701.
0 A. A. Bezrukov, K. W. Tornroos, E. Le Roux and P. D. C.
Dietzel, Chem. Commun., 2018, 54, 2735-2738.
Acknowledgements
1 C. He, K. Lu, D. Liu and W. Lin, J. Am. Chem. Soc., 2014, 136,
5
181-5184.
4
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Pleas De ad l to o nn oT tr aa nd sj au cs t ti omn as rgins
Journal Name
COMMUNICATION
2
2
2
2
2
2 C. He, K. Lu and W. Lin, J. Am. Chem. Soc., 2014, 136, 12253- 50 Y. Zhang, Y. Wang, L. Liu, N. Wei, M.-L. Gao, D. ZVhieawoAratinclde OZn.-liBne.
2256. Han, Inorg. Chem., 2018, 57, 2193-2198.
1
DOI: 10.1039/C8DT05060K
3 R. Xu, Y. Wang, X. Duan, K. Lu, D. Micheroni, A. Hu and W. 51 L. Zhu, X.-Q. Liu, H.-L. Jiang and L.-B. Sun, Chem. Rev., 2017,
Lin, J. Am. Chem. Soc., 2016, 138, 2158-2161.
117, 8129-8176.
4 K. Lu, C. He, N. Guo, C. Chan, K. Ni, R. R. Weichselbaum and
W. Lin, J. Am. Chem. Soc., 2016, 138, 12502-12510.
5 R. Dai, F. Peng, P. Ji, K. Lu, C. Wang, J. Sun and W. Lin, Inorg.
Chem., 2017, 56, 8128-8134.
6 K. Ni, G. Lan, C. Chan, B. Quigley, K. Lu, T. Aung, N. Guo, P. La
Riviere, R. R. Weichselbaum and W. Lin, Nat. Commun.,
2
018, 9, 2351.
2
2
7 S. Yuan, L. Zou, H. Li, Y.-P. Chen, J. Qin, Q. Zhang, W. Lu, M. B.
Hall and H.-C. Zhou, Angew. Chem. Int. Ed., 2016, 55, 10776-
1
0780.
8 M. J. Cliffe, W. Wan, X. Zou, P. A. Chater, A. K. Kleppe, M. G.
Tucker, H. Wilhelm, N. P. Funnell, F.-X. Coudert and A. L.
Goodwin, Nat. Commun., 2014, 5, 4176.
2
3
3
3
3
9 O. Delgado Friedrichs, M. O'Keeffe and O. M. Yaghi, Acta
Cryst. A, 2003, 59, 22-27.
0 V. Bon, V. Senkovskyy, I. Senkovska and S. Kaskel, Chem.
Commun., 2012, 48, 8407-8409.
1 J. M. Taylor, T. Komatsu, S. Dekura, K. Otsubo, M. Takata and
H. Kitagawa, J. Am. Chem. Soc., 2015, 137, 11498-11506.
2 S. Waitschat, H. Reinsch, M. Arpacioglu and N. Stock,
CrystEngComm, 2018, 20, 5108-5111.
3 M. Ermer, J. Mehler, M. Kriesten, Y. S. Avadhut, P. S. Schulz
and M. Hartmann, Dalton Trans., 2018, DOI:
1
0.1039/C8DT02999G.
3
4 F. C. N. Firth, M. Cliffe, D. Vulpe, M. Peyman, D. Fairen-
Jimenez, B. Slater and C. Grey, ChemRxiv Preprint, 2018, DOI:
1
0.26434/chemrxiv.7301951.v1.
3
3
3
5 K. B. Lausund, V. Petrovic and O. Nilsen, Dalton Trans., 2017,
6, 16983-16992.
6 Q.-b. Wang, H.-b. Xu and X. Li, Fluid Phase Equilib., 2005,
33, 81-85.
7 C. Volkringer, D. Popov, T. Loiseau, G. Férey, M.
Burghammer, C. Riekel, M. Haouas and F. Taulelle, Chem.
Mater., 2009, 21, 5695-5697.
4
2
3
8 M. Kandiah, M. H. Nilsen, S. Usseglio, S. Jakobsen, U. Olsbye,
M. Tilset, C. Larabi, E. A. Quadrelli, F. Bonino and K. P.
Lillerud, Chem. Mater., 2010, 22, 6632-6640.
3
4
9 J. Landers, G. Y. Gor and A. V. Neimark, Colloids Surf. A, 2013,
4
37, 3-32.
0 G. R. Bhimanapati, Z. Lin, V. Meunier, Y. Jung, J. Cha, S. Das,
D. Xiao, Y. Son, M. S. Strano, V. R. Cooper, L. Liang, S. G.
Louie, E. Ringe, W. Zhou, S. S. Kim, R. R. Naik, B. G. Sumpter,
H. Terrones, F. Xia, Y. Wang, J. Zhu, D. Akinwande, N. Alem, J.
A. Schuller, R. E. Schaak, M. Terrones and J. A. Robinson, ACS
Nano, 2015, 9, 11509-11539.
4
1 C. Tan, X. Cao, X.-J. Wu, Q. He, J. Yang, X. Zhang, J. Chen, W.
Zhao, S. Han, G.-H. Nam, M. Sindoro and H. Zhang, Chem.
Rev., 2017, 117, 6225-6331.
4
4
2 M. Zhao, Y. Huang, Y. Peng, Z. Huang, Q. Ma and H. Zhang,
Chem. Soc. Rev., 2018, 47, 6267-6295.
3 Y. Zhao, Q. Zhang, Y. Li, R. Zhang and G. Lu, ACS Appl. Mater.
Interfaces, 2017, 9, 15079-15085.
4
4
4 D. R. Eaton and K. L. Chua, Can. J. Chem., 1971, 49, 56-66.
5 V. Guillerm, T. Grancha, I. Imaz, J. Juanhuix and D. Maspoch,
J. Am. Chem. Soc., 2018, 140, 10153-10157.
4
4
4
4
6 C. Seidel, C. Lorbeer, J. Cybińska, A.-V. Mudring and U.
Ruschewitz, Inorg. Chem., 2012, 51, 4679-4688.
7 M. Eddaoudi, J. Kim, M. O'Keeffe and O. M. Yaghi, J. Am.
Chem. Soc., 2002, 124, 376-377.
8 M. R. Momeni and C. J. Cramer, Chem. Mater., 2018, 30,
4
432-4439.
9 H. Liu, F.-G. Xi, W. Sun, N.-N. Yang and E.-Q. Gao, Inorg.
Chem., 2016, 55, 5753-5755.
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