A Flexible Metal-Organic Framework with 4-Connected Zr6 Nodes

Article abstract of DOI:10.1021/jacs.8b06789

Zr-based metal-organic frameworks (MOFs) have been known for their excellent stability; however, due to the high connectivity of the Zr₆ nodes, it is challenging to introduce flexibility into Zr-MOFs. Here we present a flexible Zr-MOF named NU-1400 comprising 4-connected Zr₆ nodes and tetratopic linkers. It exhibits guest-dependent structural flexibility with up to 48% contraction in the unit cell volume as evidenced by single-crystal X-ray diffraction studies. The expanded or contracted conformations of NU-1400 showed drastically different reactivity toward the hydrolysis of a nerve agent simulant owing to the size-selective effect toward the reactant.

Full text of DOI:10.1021/jacs.8b06789

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Communication
A Flexible Metal-Organic Framework with 4-Connected Zr6 Nodes
Yuanyuan Zhang, Xuan Zhang, Jiafei Lyu, Ken-ichi Otake, Xingjie Wang, Louis R. Redfern,
Christos D. Malliakas, Zhanyong Li, Timur Islamoglu, Bo Wang, and Omar K. Farha
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b06789 • Publication Date (Web): 16 Aug 2018
Downloaded from http://pubs.acs.org on August 16, 2018
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topology with diamond-shaped channels along the a axis (Figure 1).
The 4-connected Zr node resembles a distorted paddlewheel structure
where each pair of the carboxylate groups are on two of the adjacent
edges of the Zr octahedron (Scheme 1, center). The as-synthesized
NU-1400 from DEF (NU-1400-AS-DEF) also has four formate groups
volume shrinkage of 334 Å (Table S2). This is further confirmed in
variable temperature PXRD measurements, where a continuous expan-
sion along the c axis was observed as the temperature increases from
200 to 400 K (Figure S12).
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on each Zr
digested in a solution of NaOD/D
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node, as confirmed by the H NMR spectrum of NU-1400
O (Figure S2). The remaining co-
2
ordination sphere of each Zr ion is further fulfilled by hydroxy/water
−1
groups, as evidenced by the O-H stretching at 3650 cm in its diffuse
reflectance infrared Fourier transform spectrum (DRIFTS) (Figure
S3). Upon solvent exchange with acetone and subsequent thermal
activation (NU-1400-TA), the porosity of the material was evaluated by
argon sorption measurement at 87 K which showed type I adsorption
isotherm (Figure 2a). BET area and the total pore volume were calcu-
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lated to be 560 m /g and 0.23 cm /g respectively. Pore size distribution
based on DFT analysis indicates pore diameters of 5 Å and 8 Å (Figure
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b), in line with the pores along the b and c axis (Figure S4).
Thermogravimetric analysis and powder X-ray diffraction (PXRD)
indicated that NU-1400 did not decompose until 450 ºC under air
Figure S5–S7). The chemical stability of NU-1400-TA was tested by
(
soaking in hot water and solutions of pH = 1 and pH = 12 for 24 h,
where the crystallinity and porosity were maintained as evidenced by
PXRD (Figure 2c) and Ar sorption (Figure S8). These results demon-
strated that the thermal and chemical stability are not compromised by
Figure 2. Structural characterization and stability of NU-1400. a) Ar
sorption profile of NU-1400-TA. b) Pore size distribution of NU-1400-
TA based on Ar-87 K isotherm adsorption branch using DFT model. c)
PXRD patterns of NU-1400-TA after immersing in 0.1 M HCl solution,
the low connectivity of the Zr nodes in NU-1400.
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.01 M NaOH solution and 90 ºC water for 24 h. d) Experimental and
simulated PXRD patterns of NU-1400-AS-DEF, NU-1400-SA and NU-
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400-TA.
Given the differences between the PXRD pattern of NU-1400-AS-
DEF and the simulated one from the single crystal data (Figure 2d), we
suspect the degree of solvation and the guest solvent molecules must
also affect the flexibility of the MOF structure. To confirm our hypoth-
esis, single crystal X-ray diffraction data were collected after soaking the
single crystals of NU-1400-AS-DEF in water or ethanol (NU-1400-
water and NU-1400-EtOH) (Figure 3a; Table S1). X-ray quality crys-
tals of NU-1400-DMF were independently synthesized using DMF as
the solvent, where the resulting framework exhibits an isomorphous
structure (see SI). Structural analysis on these four samples indicates
that there is a monotonic increase in the length of the b axis and de-
crease in the c axis in the order of DMF, DEF, water and ethanol (Fig-
ure 3b,3c). Commensurate with these changes is the acute angle of the
diamond-shaped channels, decreasing from 71.8° in DMF to 47.1° in
Figure 1. Structure of NU-1400. a) The construction of NU-1400. b)
The framework topology of the lvt net (C, grey; O, red; Zr, green).
3
ethanol (Figure 3d). The unit cell volume changes from 12401 Å in
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DMF to 9379 Å in ethanol, corresponding to a ~32% decrease (Figure
One notable feature in the PXRD pattern of bulk NU-1400-AS-DEF
is the peak shift compared to the simulated pattern from single crystal
data (Figure 2d), indicative of guest-dependent structural changes. The
more distinct shifts in NU-1400-TA prompted us to obtain a crystal
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d).
structure of NU-1400 after supercritical CO
2
activation (NU-1400-SA,
a = 25.385(3) Å, b = 30.661(3) Å and c = 8.2771(9) Å at 200 K; Figure
3; Table S1), which matched well with the Le Bail fitting results of NU-
1400-TA (Figure S10). This entails a 51% decrease in the c axis and a
43% decrease in the unit cell volume as compared to NU-1400-AS-DEF,
suggesting much narrower channels in the activated samples (Figure
S11). This is not surprising given the computational prediction by Smit
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that lvt net is inclined to be flexible and the resemblance of the struc-
ture of NU-1400 to a foldable wine rack with diamond-shaped channels
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along the a axis.
The flexibility of NU-1400 was further probed by variable tempera-
ture (300, 250 and 200 K) single crystal X-ray diffraction studies using
the same NU-1400-AS-DEF crystal. A contraction in the c axis of ~ 0.51
Å is accompanied by an elongation in the b axis of ~ 0.15 Å as the tem-
perature decreases from 300 to 200 K, resulting in an overall unit cell
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Figure 3. Structural changes of NU-1400 in different solvents from
single crystal X-ray diffraction data. a) Structures of NU-1400-AS-DMF,
NU-1400-AS-DEF, NU-1400-water, NU-1400-EtOH and NU-1400-SA
viewed along a axis. b) Schematic representation of the changes of the
diamond-shape channel. c) and d) Unit cell parameters and volume
changes of NU-1400 in different solvents obtained from single-crystal
structure (200 K).
theless, the more energy demanding structural expansion process of
NU-1400-TA offers a stable “closed pore” form of NU-1400 under
ambient conditions in solutions.
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Owing to the Lewis acidity of Zr (IV), a number of Zr-MOFs have
been employed as catalysts in the hydrolysis of organophosphorus ester
bonds of nerve agents and simulants . We hypothesized that the varia-
ble pore sizes of different conformations of the flexible NU-1400 would
43
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make it promising for shape-selective catalysis. To test this hypothesis,
dimethyl 4-nitrophenyl phosphate (DMNP) was chosen as a substrate
because it has a size (7.4 Å × 5.0 Å of the smallest cross section) larger
than the window size of NU-1400-TA (Figure 5a,b). As a result,
DMNP will have limited access to the pores of NU-1400-TA while a
more expanded conformation can more readily accommodate it (Fig-
ure S16). The catalytic activity of NU-1400-TA was evaluated with 6
mol% of the MOF as a catalyst, and the DMNP conversion was moni-
tored by in situ P NMR measurements (Figure S17). The hydrolysis
conversion profile of NU-1400-TA is shown in Figure 5c, and the half-
life calculated based on the initial rate is about 80 min. In comparison, a
more expanded form of NU-1400 showed higher catalytic activity with
half-life of only 3 min, demonstrating that different configurations of
the framework influence the accessibility of DMNP to the Zr-node
active sites.
Theoretical predictions of the flexibility of MOFs are generally ob-
tained by assuming both the linker and the node to be rigid bodies;
therefore, flexible topologies must originate from the hinge-like motion
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of the joints between the two rigid components.
The reduction in
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the connectivity of the node and topicity of the linker allows for higher
degrees of freedom and thereby more flexibility in compatible topolo-
gies. Analysis of the structural details of NU-1400 in different forms
revealed that the deformation of the diamond-shaped channels is cor-
related to the bending of the carboxylate groups out of the plane of the
adjacent phenyl ring and the simultaneous twisting of the carboxylate
oxygen atoms around the phenyl-carboxy C-C bond (Figure 4a). This
torsional angle increases as the pore contracts, indicating additional
disruption of the conjugation between the carboxy group and the phe-
nyl ring (Figure 4b). The out-of-plane bending of the phenyl-carboxy
bond, however, first decreases as the pore contracted from NU-1400-
AS-DMF to NU-1400-water, but then increases as the pore further
contracts when soaked in ethanol (Figure 4b). A larger out-of-plane
phenyl-carboxy bending angle would endow extra strain and be less
energetically favorable owing to the rigidity of the TPDC linker. There-
fore, we postulated that the less bent carboxy group in NU-1400-water
indicates a stronger affinity of water to NU-1400, likely due to the
unique polarity and hydrogen-bonding ability of water compared to
3
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other solvents tested in this study. Different from the classic paddle-
wheel structure, where the O-O axis of adjacent carboxylate groups are
parallel to each other, there is a dihedral angle between the two adja-
cent carboxylate groups on the Zr node in NU-1400 (Scheme 1, cen-
6
ter). As a result, the carboxylate groups in NU-1400 have to both bend
and twist to accommodate the hinge-like motion.
Figure 5. Hydrolysis of DMNP. a) Hydrolysis reaction of DMNP. b)
Molecular size of DMNP. c) Hydrolysis profiles of DMNP with open-
pore form and narrow-pore form NU-1400.
In summary, a flexible Zr-MOF with 4 connected nodes has been
reported, and the guest- and temperature-dependent structural dynam-
ics have been studied by single-crystal X-ray diffraction. NU-1400 pos-
sesses one-dimensional diamond-shaped channels that exhibit variable
opening configurations in a single-crystal to single-crystal fashion.
Taking advantage of the structural flexibility, both contracted and ex-
panded forms of NU-1400 were tested as the catalysts for the hydroly-
sis of a nerve-agent simulant, DMNP, illustrating the potential applica-
tion as a Lewis acid catalyst with adjustable accessibility to the catalytic
sites. The intriguingly responsive properties of NU-1400 towards dif-
ferent solvents make it a promising candidate for selective adsorption
and separation of small molecules.
Figure 4. Origin of flexibility in NU-1400. a) Illustration of the main
contributions to the pore deformation. b) Details of phenyl-carboxy
bending angle and twisting angle changes in NU-1400.
ASSOCIATED CONTENT
Compared to the flexibility exhibited by NU-1400-AS-DEF in re-
sponse to guest molecules and temperatures, NU-1400-TA was found
to be more rigid. When immersed in different solvents at room temper-
ature, NU-1400-TA maintains its contracted conformation showing
little dependence on the solvent molecules (Figure S13). Variable
temperature PXRD patterns of NU-1400-TA collected from 200 to 400
K also show the structural rigidity under different temperatures (Figure
S14). However, the structure changes to an expanded conformation
when heated in a mixture of DMF and formic acid (Figure S15),
demonstrating that flexibility can be recovered in NU-1400-TA. Never-
Supporting Information
The Supporting Information is available free of charge on the ACS
Publications website.
Experimental details and characterization data (PDF)
Crystallographic data (CIF)
Corresponding Author
*
o-farha@northwestern.edu
Author Contributions
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Y.Z. and X.Z. contributed equally.
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Notes
The authors declare no competing financial interests.
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ACKNOWLEDGMENT
O.K.F. gratefully acknowledges support from the Defense Threat Re-
duction Agency (HDTRA1-18-1-0003). Y.Z. acknowledges support
from China Scholarship Council (CSC) during her visit to North-
western University. This work made use of the EPIC facility of North-
western University’s NUANCE Center, which has received support
from the Soft and Hybrid Nanotechnology Experimental (SHyNE)
Resource (NSF NNCI-1542205); the MRSEC program (NSF DMR-
2
017, 139, 356-362.
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(CHE-1048773 and DMR-0521267); Soft and Hybrid Nanotechnolo-
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of Illinois and International Institute for Nanotechnology (IIN).
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8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
5
ACS Paragon Plus Environment