Kinetically Controlled Reticular Assembly of a Chemically Stable Mesoporous Ni(II)-Pyrazolate Metal-Organic Framework

Article abstract of DOI:10.1021/jacs.0c05074

The application scope of metal-organic frameworks (MOFs) is severely restricted by their weak chemical stability and limited pore size. A robust MOF with large mesopores is highly desired, yet poses a great synthetic challenge. Herein, two chemically stable Ni(II)-pyrazolate MOFs, BUT-32 and -33, were constructed from a conformation-matched elongated pyrazolate ligand through the isoreticular expansion. The two MOFs share the same sodalite-type net, but have different pore sizes due to the network interpenetration in BUT-32. Controlled syntheses of the two MOFs have been achieved through precisely tuning reaction conditions, where the microporous BUT-32 was demonstrated to be a thermodynamically stable product while the mesoporous BUT-33 is kinetically favored. To date, BUT-32 represents the first example of Ni4-pyrazolate MOF whose structure was unambiguously determined by single-crystal X-ray diffraction. Interestingly, the kinetic product BUT-33 integrates 2.6 nm large mesopores with accessible Ni(II) active sites and remarkable chemical stability even in 4 M NaOH aqueous solution and 1 M Grignard reagent. This MOF thus demonstrated an excellent catalytic performance in carbon-carbon coupling reactions, superior to other Ni(II)-MOFs including BUT-32. These findings highlight the importance of kinetic control in the reticular synthesis of mesoporous MOFs, as well as their superiority in heterogeneous catalysis.

Full text of DOI:10.1021/jacs.0c05074

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Article
Kinetically Controlled Reticular Assembly of a Chemically
Stable Mesoporous Ni(II)-Pyrazolate Metal-Organic Framework
Tao He, Zhehao Huang, Shuai Yuan, Xiu-Liang Lv, Xiang-
Jing Kong, Xiaodong Zou, Hong-Cai Zhou, and Jian-Rong Li
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.0c05074 • Publication Date (Web): 11 Jul 2020
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Kinetically Controlled Reticular Assembly of a Chemically Stable
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[a]
[b]
[c]
[a,c]
[a]
[b]
Tao He, Zhehao Huang, Shuai Yuan, Xiu-Liang Lv, Xiang-Jing Kong, Xiaodong Zou,
[c]
[a]
Hong-Cai Zhou, and Jian-Rong Li*
[a]
Beijing Key Laboratory for Green Catalysis and Separation, Department of Environmental Chemical Engineering,
Beijing University of Technology, Beijing, 100124, P. R. China
[
b]
Department of Materials and Environmental Chemistry, Stockholm University, Stockholm, 10691, Sweden
Department of Chemistry, Texas A&M University, College Station, Texas 77843-3255, United States
[c]
ABSTRACT: The application scope of metal-organic frameworks (MOFs) is severely restricted by their weak chemical
stability and limited pore size. A robust MOF with large mesopores is highly desired, yet poses a great synthetic challenge.
Herein, two chemically stable Ni(II)-pyrazolate MOFs, BUT-32 and -33 were constructed from a conformation-matched
elongated pyrazolate ligand through the isoreticular expansion. The two MOFs share the same sodalite-type net, but have
different pore sizes due to the network interpenetration in BUT-32. Controlled syntheses of the two MOFs have been
achieved through precisely tuning reaction conditions, where the microporous BUT-32 was demonstrated to be a
thermodynamically stable product while the mesoporous BUT-33 is kinetically favored. To date, BUT-32 represents the first
4
example of Ni -pyrazolate MOF whose structure was unambiguously determined by single-crystal X-ray diffraction.
Interestingly, the kinetic product BUT-33 integrates 2.6 nm large mesopores with accessible Ni(II) active sites and
remarkable chemical stability even in 4 M NaOH aqueous solution and 1 M Grignard reagent. This MOF thus demonstrated
an excellent catalytic performance in carbon-carbon coupling reactions, superior to other Ni(II)-MOFs including BUT-32.
These findings highlight the importance of kinetic control in the reticular synthesis of mesoporous MOFs, as well as their
superiority in heterogeneous catalysis.
carboxylate MOFs have ushered in a research boom since
INTRODUCTION
2
1
the discovery of UiO-66. Despite good stability beyond
most reported MOFs, Zr(IV)-MOFs are vulnerable to strong
Lewis bases (entities with high alkalinity or
nucleophilicity), while alkaline/nucleophilic conditions are
more pervasive in practical applications, such as in many
As a family of porous crystalline materials assembled by
organic and inorganic building units, metal−organic
frameworks (MOFs) have achieved tremendous advances
in chemistry and material science due to their structural
and functional diversity. Essentially, the modular nature
of MOFs endows them with tailorable composition,
adjustable architecture, and tunable property.
intrinsic merits enable MOFs to perform superiorly over
traditional porous materials in various applications, such
as gas storage and separation, chemical sensing,
heterogeneous catalysis.
1–3
2
2–24
catalytic coupling reactions.
Another family of stable
MOFs are those based on azolate ligands and low-valent
transition metal ions, which usually exhibit excellent
alkaline robustness compared to their carboxylate
4–6
These
1
1,22,24,25
counterparts.
As predicted by the pKa value for the
7
,8
9–11
and
deprotonation of N–H entities, ligands functionalized with
pyrazole (pKa = 19.8, the highest among azoles) are of
particular interest for the construction of alkali-resistant
1
2,13
Although plenty of MOFs have
been synthesized and utilized, the inherent framework
instability and small pore size have limited their further
engagement in many critical applications under harsh
1
7,25–27
frameworks.
However, stable MOFs always suffer
from difficult crystallization. Due to the trade-off effect
between crystallinity and stability of products, pyrazolate
(denoted as pz thereafter) MOFs poses a synthetic
challenge against the easy availability of Zr(IV)-MOF single
1
4–19
conditions.
To extend the application scope of MOFs beyond the
current state of art, the high chemical stability of MOFs is a
prerequisite. According to Pearson’s hard/soft acid/base
principle, chemically stable MOFs can be assembled by
either carboxylate ligands with high-valent transition
metal ions (Cr(III), Al(III), Zr(IV), Ti(IV), et al.) or azolate
ligands with low-valent transition metal ions (Ni(II), Zn(II),
27
crystals by a modulating method.
As demonstrated previously, pz based ligands are
capable of forming chemically stable MOFs with divalent
transition metal ions, such as Ni(II).
2
2,24,25,27–29
3
–
3 2
Representative examples are Ni (BTP) (BTP = 1,3,5-
20
Co(II), et al.). As a typical example of the former, Zr(IV)-
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2
5
tris(pyrazolate-4-yl)benzene),
Ni
8
(OH)
4 2
(H O)
2
(BDP)
6
reported again by Long and co-workers can be referred,
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(
BDP = 1,4-bis(4-pyrazolate)benzene), PCN-601, and
2–
30
22
with which a two-dimensional MOF was obtained. The
40
2
4
3–
PCN-602. Among them, the sodalite-type Ni
represents suitable candidate for heterogeneous
catalysis, due to its rich open Ni(II) sites and high chemical
stability. However, the relatively small pore aperture of
this MOF potentially limits the mass transfer during
3
(BTP)
2
BTPP shows a similar length and connectivity but
3
–
a
different conformation from the TPTA . The DFT
optimized molecular structures indicate a co-planar
2
5
3–
3–
conformation for both BTP and TPTA (Figure 1).
However, the steric interaction between hydrogen atoms
3
1–33
3–
catalysis.
from central and peripheral phenyl rings of BTPP forces
4
1
the pz moieties to rotate off the central plane. When the
Reticular chemistry is a well-developed guideline for the
judicious design and synthesis of MOFs with known
topology and varied pore apertures and functionalities,
which has contributed a lot in the expansion of MOF
To enlarge the pores of MOFs, isoreticular
expansion through reticular chemistry was rather
3
–
central benzene ring in BTPP was changed to a triazine
core without hydrogen atoms, the distortion of ligand
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TPTA would be diminished. Therefore, BTP and TPTA
3–
3
4–36
could form sodalite-type structures, whereas BTPP gave
rise to a different MOF with much lower porosity.
library.
40
3
4–39
applicable.
By adopting this methodology, the central
task to approach a mesoporous sodalite-type framework is
the rational linker elongation to amplify the voids and
meanwhile match conformation with the coordination
4 8 4
environment of Ni pz clusters (as Ni thereafter) formed
in Ni (BTP)
3
2
.
In this work, we constructed two chemically stable
Ni(II)-pz MOFs, BUT-32 and -33 (BUT = Beijing University
of Technology) as the extended versions of the sodalite-
type Ni
3 2
(BTP) , by using the judiciously designed planar
ligand, 2,4,6-tris(4-(pyrazolate-4-yl)phenyl)-1,3,5-triazine
3
–
(TPTA ). The two MOFs have the same composition of
Ni (TPTA) , but were obtained as different phases with
3
2
distinct pore sizes, under different reaction conditions. The
structure of BUT-32 was determined by single-crystal X-
ray diffraction (SXRD), being the first example of Ni -Pz
4
MOF whose structure was unambiguously determined by
SXRD to the best of our knowledge. A two-fold network
interpenetration occurs in BUT-32, which was
demonstrated as a thermodynamically stable product;
while the kinetically favored BUT-33 is non-
interpenetrated with mesopores. The synthesis of two
MOFs could be readily tuned by varying synthetic
conditions. Interestingly, BUT-33 represents
a rare
example of MOF catalysts that inherently integrates large
mesopores, excellent chemical stability, and rich active
Ni(II) sites. It shows high catalytic activity toward the
cross-coupling of aryl halides with aryl Grignard reagents
and the homo-coupling of aryl Grignard reagents under
ambient conditions. Thus, this MOF demonstrates the
superiority of kinetically controlled reticular synthesis of
mesoporous MOFs for catalyzing important organic
reactions. As a heterogeneous catalyst with non-noble
metal Ni(II), the application of BUT-33 would also help to
achieve the “green” production of fine chemicals.
3
–
Figure 1. Optimized molecular structures of (a) BTP , (b)
3
–
3–
BTPP , and (c) TPTA (optimized by Materials Studio
software).
Synthesis and structural determination. Typical
solvothermal reaction of H
3
TPTA with Ni(NO
3 2 2
) ·6H O in
O with trace acetic
acid as the modulator at 150 C for staying 72 h afforded
BUT-32 as yellow cubic crystals (Figure 2a and Table S1).
SXRD analysis shows that BUT-32 has a two-fold
interpenetrated framework structure (Crystal parameters
and structural refinement are provided in Table S2). To
N,N-dimethylformamide (DMF) and H
2
o
RESULTS AND DISCUSSION
4
date, to the best of our knowledge, this is the first Ni -pz
MOF whose structure was unambiguously identified by
Structural design. The sodalite-type Ni
initially reported by Long and co-workers. To access an
extended structure with the same topology and larger
3
(BTP)
2
was
2
5
SXRD.
pores, we elongated the original H
longer one, namely H TPTA under the guidance of reticular
chemistry. It should be noted that the planar conformation
3
BTP ligand acid to a
It should be pointed out that the synthesis of Ni -pz
MOFs is fairly tough, especially obtaining bigger single
crystals suitable for SXRD characterization. By varying a
series of factors (including the reaction temperature, metal
species, metal/ligand ratio, solvent, and modulator), the
synthetic conditions for BUT-32 crystals were well
4
3
3
–
of TPTA is critical for the successful formation of targeted
sodalite-type structure. For the comparison in constructing
3 3
the MOFs, another elongated ligand acid H BTPP (H BTPP
=
1,3,5-tris((1H-pyrazol-4-yl)phenylene)benzene)
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Figure 2. (a) Photograph showing the yellow cubic crystals of BUT-32. (b) Ni pz cluster (structurally simplified as green cuboid)
3−
and TPTA ligand (structurally simplified blue triangle). (c) Photograph showing the microcrystalline powder of BUT-33. (d)
Structure of BUT-32 with a two-fold framework interpenetration. (e) The the-a topological net of BUT-32 and -33. (f) Structure of
BUT-33 showing two kinds of pores.
Figure 3. 2D slice cuts from the reconstructed 3D reciprocal
lattice of BUT-33 showing the (a) hk0 and (b) hhl planes (inset
is the crystal from which the cRED data were collected), and
(c) Pawley fitting of BUT-33 against PXRD data (λ = 1.54178
Å).
Figure 4. The comparison of (a) PXRD patterns and (b) N
adsorption/desorption isotherms of BUT-32 and BUT-33.
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established (see Section 3 in the Supporting Information). cavity enclosing a sphere of diameter 27.8 Å, which show
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We found that several factors affected the reaction rate,
thereby the nucleation and growth of BUT-32 crystals,
among which the selection of metal salt plays a crucial role.
open 3D channels with aperture of 22.4 Å, running along
three crystallographic axial directions (Figure 2f). Two
such identical frameworks interpenetrate with each other
to form the final structure of BUT-32 (Figure 2d). Although
the network interpenetration in BUT-32 gives rise to
denser Ni(II) active sites, the second framework occupies
the mesopores in the single framework with only the
smaller octahedral cages accessible. Moreover, most of the
Ni-active sites are also blocked by the interpenetrated
framework.
The use of Ni(NO
3 2 2
) ·6H O could effectively slow the
reaction with H TPTA and avoid the immediate formation
3
of precipitate, offering opportunity for accessing good
BUT-32 crystals. Besides, the addition of appropriate
amount of acetic acid and water in DMF can also slow
down the reaction by inhibiting the deprotonation of
ligands, and result in final bigger single crystals in a
prolonged reaction time.
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To obtain the non-interpenetrated Ni (TPTA) (BUT-33)
with large mesopores and more accessible Ni(II) active
sites, multiple factors were varied in the typical
solvothermal synthesis (without stirring) including the
metal precursor, metal/ligand ratio, solvents, modulators,
reaction time, and temperature. Regrettably, all the trials
gave rise to BUT-32 or amorphous materials. We reason
3
–
that
the
interpenetrated
structure
might
be
thermodynamically more favorable than the non-
interpenetrated one. The quest for extended MOFs with
larger pores by linker elongation tends to weaken the
robustness of frameworks. In this case, framework
interpenetration, which usually leads to smaller cavity and
o
Figure 5. PXRD patterns for the reaction products of Ni(OAc)
(
2
·4H
2
O and H
3
TPTA (a) for different reaction time at 100 C and
o
b) with different adding amount of AcOH at 150 C. (c) Proposed reaction mechanism and (d) energy diagram for the
formation of BUT-32 and BUT-33 (k is the rate constant, K represents the equilibrium constant, E
ΔE shows the energy change).
a
is the activation energy, and
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denser framework packing through beneficial framework–
framework interactions, is able to enhance the
rotation electron diffraction (cRED) was firstly applied to
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determine the structure of BUT-33 (Figure 3a and 3b). The
unit cell parameters of this material were then refined
against its PXRD pattern by Pawley method (Figure 3c),
and the final structure was refined against the cRED data.
The crystallographic details are given in Table S4, and the
details of data collection and refinement are summarized
in Table S5 (also see the Section 6 in Supporting
Information). As shown in Figure 2f, BUT-33 has exactly
4
2–
thermodynamic stability and thus preferred in products.
4
7
In typical MOF synthesis, particularly stable MOFs,
competing reagent or acid is often involved to inhibit the
4
8
ligand substitution process during the MOF formation. As
a result of the slow nucleation rate, highly crystalline
product can be obtained. However, when multiple phases
coexist in the same system, such process always yields the
most thermodynamically stable product, which may not be
the desired structure. To achieve the targeting non-
interpenetrated structure, we further tuned the synthetic
conditions, specifically toward the kinetically controlled
process (Table S3, Figure S1 and S2, Section 5 in
Supporting Information for more details). Given that
3
–
the single the-a net connected by Ni
ligands. The powder X-ray diffraction (PXRD) pattern
(Figure 4a) and N adsorption isotherm (Figure 4b) of
4
clusters and TPTA
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BUT-33 differ greatly from those of BUT-32. Both the
diffraction peaks shifted to lower degrees and the step-
wise N
2
adsorption isotherm suggest the existence of
4
9,50
2 2 3
Ni(OAc) ·4H O could generate precipitate with H TPTA
larger pores in the non-interpenetrated net of BUT-33.
rapidly at room temperature, this reaction shows some
kinetic features, which was indeed not applicable for
growing single crystals of the interpenetrated BUT-32
under typical solvothermal conditions (see Section 3 in the
Supporting Information). It might be suitable for the fast
synthesis of the non-interpenetrated BUT-33. To make the
process more kinetically favored, we conducted the
By eliminating the framework interpenetration, the
enlarged pores in BUT-33 would facilitate the diffusion of
reactants and products throughout the porous framework
when used in catalysis.
For an in-depth understanding of product formation in
this “stirring” reaction, the synthetic conditions were
systematically explored (see section 5 in the supporting
information). It was found that BUT-33 formed rapidly (< 2
h) in the absence of acid modulator, and increasing
reaction of Ni(OAc)
stirring without adding any modulator, at a higher
nucleation rate (see section in the supporting
2 2 3
·4H O and H TPTA under vigorous
5
o
temperature from 100 to 150 C further accelerated its
information). Finally, a yellow microcrystalline powder of
formation (Figure 5a). However, prolonging the reaction
time led to gradual transformation from BUT-33 to BUT-
32, indicating BUT-32 a thermodynamically more stable
product. Moreover, adding more acetic acid as the
o
BUT-33 was obtained at 150 C for 2 h (Figure 2c).
As shown in Figure S3 and S4, BUT-33 formed as cubic
nanocrystals with the diameter of 150-300 nm. Continuous
2
Figure 6. N adsorption/desorption isotherms measured at 77 K for (a) BUT-32 and (b) BUT-33 samples after different
treatments (inset shows DFT pore size distribution in the corresponding MOF, which was evaluated by using the N
2
adsorption data). PXRD patterns of (c) BUT-32 and (d) BUT-33 for the simulated, as-synthesized, and treated samples.
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modulator could inhibit the formation of BUT-33 and
directly resulted in the interpenetrated BUT-32 (Figure
5b).
The thermogravimetric analysis indicates that BUT-32
and -33 can be thermally stable up to 398 and 380 C
(Figure S5), respectively. The chemical stability of them
was firstly tested by incubating as-synthesized samples in
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o
In virtue of the above experimental results and the MOF
formation equilibrium (Figure 5c), we rationalize that the
addition of acetic acid will increase the concentration of
proton, thereby inhibiting the ligand deprotonation
process. Consequently, the equilibrium will shift towards
free ligands and metals, preventing the formation of BUT-
HCl aqueous solution (pH = 3) and NaOH aqueous solution
o
(
4 M) at room temperature (RT, 25 C), as well as in boiling
water for 24 h, respectively. The PXRD patterns of treated
samples are well retained (Figure 6c and 6d),
demonstrating high acid/base resistance. Two MOFs were
also exposed to 1 M Grignard reagent phenylmagnesium
bromide at RT for 24 h. The maintained crystallinity of
their PXRD patterns implies structure integrity, showing
good chemical stability (Figure 6c and 6d). In addition, the
almost unaltered N sorption isotherms of BUT-32 and -33
2
samples after all treatments further confirm their chemical
stability (Figure 6a and 6b).
3
3. However, as BUT-32 is a thermodynamically favored
product, there is sufficient thermodynamic driving force to
promote the equilibrium towards its formation. This
further validates our hypothesis that BUT-32 is
thermodynamically more stable than BUT-33. Another
control experiment was then performed to explore the
transformation between the two MOFs in the presence of
acid modulator (Section 5 in the Supporting Information).
The results show that the pre-synthesized BUT-33 could
convert to BUT-32 within 2 h when adding acetic acid. The
more acid was added, the more BUT-32 was observed in
products, until a complete conversion to BUT-32 with 30
μL of acetic acid in a 4 mL DMF system (see PXRD patterns
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
Carbon−Carbon Coupling Catalysis. Given the
existence of rich active Ni(II) sites and good chemical
stability, BUT-32 and -33 were utilized as heterogeneous
catalysts for carbon-carbon (C−C) coupling reactions.
Preliminary experiments were carried out to examine the
catalytic activity of these two MOFs toward the Kumada-
Tamao-Corriu (KTC) cross-coupling. Bromobenzene (1a)
and 4-methoxyphenyl magnesium bromide (2a) were
2
in Figure S2a and N adsorption isotherms in Figure S2b).
The proposed reaction equilibrium can also explain the
observed conversion from BUT-33 to thermodynamically
stable BUT-32.
5
1
selected as substrates in the model reaction. The initial
catalytic test was carried out by mixing 1a (0.1 g), 2a (1.53
mL), and BUT-32 or -33 (10 mg) in 6 mL of THF at RT.
BUT-32 delivered the target cross-coupling product 4-
methoxy-1,1'-biphenyl (3a) in a 41% yield after 5 h, along
with a small amount of homo-coupled 4,4'-dimethoxy-1,1'-
biphenyl (4a) with a 9% yield as by-product (Table S7,
entry 1). By contrast, BUT-33 can deliver double higher
yields for 3a (81%) and 4a (15%) under the same
conditions (Table S7, entry 2). The enhanced catalytic
activity of the non-interpenetrated BUT-33 could be
attributed to the large mesopores and rich accessible Ni(II)
sites. However, the small micropores of BUT-32 indeed
hinder reactants from accessing the active Ni(II) sites and
limit the mass transfer, as indicated by the simulated
accessible pore surface (Figure S6).
To gain an insight into the thermodynamics on two
MOFs’ formation, DFT calculations were also briefly
conducted on the reaction (Section 7 in the Supporting
Information). The energy changes of producing BUT-33
and -32 are evaluated to be −526.5 and −584.9 kJ/mol per
Ni
3
(TPTA)
2
unit, respectively. As illustrated in Figure 5d,
1
is larger than that of ΔE ,
the absolute value of ΔE
2
implying that the interpenetrated BUT-32 is more
thermodynamically favored. Such a conclusion is in good
agreement with those derived from the experiments
above. All these results unambiguously justify that the
control over framework interpenetration for the
kinetic/thermodynamic products can be realized via finely
tuning the synthetic conditions, offering a general route to
regulate pore size and chemistry of MOFs.
We then optimized the reaction conditions with BUT-33
as the catalyst, and the related catalytic results are
summarized in Table S7. Control experiment was
conducted in the absence of nickel-based compounds, in
which no 3a formed and 4a was obtained in a low yield of
11% (Table S7, entry 3). Different temperatures and
solvents were then attempted (Table S7, entries 4–9).
Interestingly, with the temperature increasing, the yield of
the cross-coupling product 3a decreases while the homo-
coupling by-product 4a increases. However, the substrate
Porosity and stability. To assess the porosity and
2
stability of BUT-32 and -33, N sorption measurements
were performed at 77 K. The isotherms of BUT-32 show a
3
–1
2
N uptake of 595 cm g at 1 atm, and give an evaluated
2
–1
Brunauer-Emmett-Teller (BET) surface area of 1757 m g
Figure 6a), belonging to the Type-I adsorption isotherm.
By contrast, the sorption isotherms of BUT-33 show a N
(
2
3
–1
uptake of 1226 cm g at 1 atm, with an evaluated BET
2
–1
surface area of 3898 m
g
(Figure 6b). Stepwise N
2
o
reactivity greatly diminishes below 0 C. Clearly, the
adsorption/desorption isotherms are observed in BUT-33,
49,50
temperature can affect the reaction activity and selectivity
of coupling products. We thus take the RT as the reaction
temperature. The dosage of BUT-33 and reaction time
were also varied for better yields (Table S7, entry 10-13).
Considering together the conversion and selectivity, the
reaction of 1a and 2a in the presence of 15 mg of BUT-33 at
RT for 5 h, generating 3a with an 86% yield, provides the
best solution.
a
signature for mesoporous MOFs.
Pore size
adsorption
distributions were then calculated from the N
2
data using a DFT method. One type of pore (with the
diameter of about 18 Å) is confirmed in BUT-32 (Figure 6a
insert), and two types (with diameters of about 18 and 26
Å, respectively) in BUT-33 (Figure 6b insert), both being in
agreement with their crystal structures. The pore
parameters of BUT-33 are far more larger than those of
BUT-32 and similar Ni(II)-based MOFs reported in
literatures, as listed in Table S6.
We further exploited BUT-32 and -33 in the Grignard
reagent homo-coupling reaction using 2a as the substrate.
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Journal of the American Chemical Society
The reaction was initially performed under the same
conditions with those for above mentioned cross-coupling,
tends to decompose under basic conditions, whereas the
small pore sizes of Ni-BDP and Ni (BTP) limit the
diffusion of reagents. Indeed, BUT-33 also shows
comparable activity with homogeneous Ni(II) catalysts
1
2
3
4
5
6
7
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
3
2
but the yield of the homo-coupled product 4a was only
14% (Table S8, entry 1). It has been reported that oxidants
are required to convert Ni(0) intermediates back to their
(Table 1 Entry 7), highlighting the importance of highly
5
2
51–55
active Ni(II) state to fulfill the catalytic cycle. Several
oxidants and other reaction variables, including solvent,
temperature, and dosage were then examined (Table 1 and
S6). It was found that BUT-33 can promote the generation
of 4a in an 86% yield from 2a when employing 1,2-
accessible metal sites in the catalysis.
In addition, to
evaluate the regeneration ability of BUT-33 for these
coupling catalyses, it was isolated at the end of the reaction
and reused for the next run. The catalytic reactivity was
maintained for at least three cycles without significant
decrease in yield, demonstrating fine recyclability of this
MOF catalyst (Figure S7, Table 1, Entry 12 and 13).
o
dibromoethane as an oxidant at 25 C for 30 min.
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
Table 1. Homo-coupling reactions catalyzed by Ni(II)-
CONCLUSION
a
based catalysts.
In summary, two chemically stable Ni
and -33 were constructed as the extension of sodalite-type
Ni (BTP) by using a conformation-matched elongated
4
-pz MOFs, BUT-32
MgBr
BUT-33, BrCH2CH2Br
THF, RT, 0.5 h
R
3
2
R
3–
R
pyrazolate ligand TPTA , under the guidance of reticular
chemistry. Fine control over synthetic conditions can
reliably tune between the thermodynamic product
interpenetrated microporous BUT-32 and the kinetic
product non-interpenetrated mesoporous BUT-33. The
advantaged combination of excellent chemical stability,
large mesopores, and abundant accessible Ni(II) sites
makes the BUT-33 an outstanding catalytic platform for
various C−C coupling reactions. This work thus not only
2
4
Product
No.
4a
Yieldb
Entry
Catalyst
R
1
2
3
4
5
6
7
8
9
BUT-33
BUT-33
BUT-33
BUT-33
BUT-33
BUT-33
p-OCH3 (2a)
86
92
93
92
96
96
55
66
41
47
59
83
81
p-CH3 (2b)
m-OCH3 (2c)
m-CH3 (2d)
H (2e)
C(CH3)3 (2f)
OCH3 (2a)
OCH3 (2a)
OCH3 (2a)
OCH3 (2a)
OCH3 (2a)
OCH3 (2a)
OCH3 (2a)
4b
4c
4d
4e
4f
4a
4a
4a
4a
achieved
the
effective
control
of
framework
interpenetration in MOFs for constructing mesoporous
materials, but also expanded the application of stable
mesoporous MOFs in catalyzing important organic
transformations. Furthermore, the discovery of recyclable
MOF catalysts provides a promising way to push
heterogeneous organic catalysis toward the sustainable
process.
NiCl
2
BUT-32
MOF-74-Ni
Ni-BDP
1
1
1
1
0
1
2
3
3
Ni (BTP)
2
4a
4a
4a
BUT-33 cycle 2
BUT-33 cycle 3
EXPERIMENTAL SECTION
a
2 2
Dry THF (6 mL), BrCH CH Br (1.27 mmol), catalysts
Synthesis of BUT-32. H
Ni(NO ·6H O (0.024 mmol, 7 mg) were dissolved in DMF
1 mL) and deionized water (0.1 mL) under ultrasound. 15
3
TPTA (0.008 mmol, 4 mg) and
(
0
containing 0.01 mmol Ni) and 0.5 M of Grignard reagent (2a,
.64 mmol), 25 C; H NMR yield.
3
)
2
2
o
b 1
(
μL of acetic acid was added to the solution as the
With optimized conditions in hand, we further expanded
modulator. The vessel was placed into the autoclave and
the scope of KTC cross-coupling reaction catalyzed by
BUT-33. The reactions proceed well with different kinds of
aryl halides and aryl Grignard reagents (Table S9). Various
halides (1a−1c) with varied reactivity were checked with
Grignard reagent 2a under similar conditions, and the
corresponding biaryl product 3a was delivered in all cases,
giving moderate to good yields (59−96%). When using the
halide 1a, altering Grignard reagents to 2b−d also revealed
good reaction compatibility, and the products (3b−3d)
were obtained in high yields from 80 to 91%. The scope of
Grignard reagent homo-coupling catalyzed by BUT-33 was
next examined. As shown in Table 1 Entry 1-6, a wide
range of Grignard reagents with different substituents are
converted into corresponding products (4a−4f) with high
yields (86−96%). The catalytic performance of BUT-33 is
compared with other Ni(II)-MOFs and homogeneous Ni(II)
catalysts. It was found that the 4a yield of using BUT-33 is
much higher than those of using BUT-32, MOF-74-Ni, Ni-
o
tightly sealed, then heated in an oven of 150 C for 72 h.
After cooling down to RT, the yellow cubic crystals (3 mg
of activated sample, 63% yield based on the H TPTA) were
3
collected by filtration, washed with DMF (2 × 10 mL) and
acetone (3 × 10 mL), and dried under reduced pressure at
RT. Anal. Calc. (%) for Ni
21.27; found C, 60.64; H, 3.21; N, 21.03.
Synthesis of BUT-33. H TPTA (0.04 mmol, 20 mg) was
ultrasonically dissolved in 4 mL of DMF in a 15 mL high-
pressure vessel. To the solution Ni(OAc) ·4H O (0.06
3 60 36
C H N18 C, 60.81; H, 3.06; N,
3
2
2
mmol, 15 mg) was added. The vessel was then tightly
sealed and the mixture was stirred for 3 minutes at RT, to
give green precipitate. The resulting mixture was then
o
heated in an oil bath of 150 C for 2 h, and a transformation
from the green precipitate to a yellow solid was observed
in the first 30 minutes of the reaction. After cooling down
to RT, the yellow solid (16 mg of activated sample, 67%
yield based on the H TPTA) was collected by filtration, and
3
washed with DMF (2 × 10 mL), acetone (3 × 10 mL) and
dried under reduced pressure at RT. Anal. Calc. (%) for
3 2
BDP, and Ni (BTP) (Table 1 Entry 8-11) due to its
framework stability and highly accessible Ni(II) sites
within mesoporous channels. On the contrary, MOF-74-Ni
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Journal of the American Chemical Society
Page 8 of 11
Ni C H N18 C, 60.81; H, 3.06; N, 21.27; found C, 60.94; H, mixture was stirred at RT for 5 h. After the reaction
3 60 36
1
2
3
4
5
6
7
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
3.17; N, 21.13.
completed, the catalyst was removed by centrifugation,
and the supernatant was concentrated under vacuum. The
yield of the crude product was determined by H NMR,
with dimethyl sulfone as the internal standard. Finally, the
product 3a was isolated by column chromatography on
silica gel using n-hexane as the eluent.
Structural determination of BUT-32. The single-
crystal diffraction data for BUT-32 were collected with a
Rigaku MicroMax-007HF High-intensity Microfocus
Rotating Anode X-ray Generator equipped with a mirror-
monochromatic enhanced Cu-Kα radiation (λ = 1.54184 Å).
The datasets were corrected by empirical absorption
correction using spherical harmonics, implemented in the
SCALE3 ABSPACK scaling algorithm. The structure was
solved using the direct methods and refined by full-matrix
least-squares on F with anisotropic displacement using
the SHELXTL software package. Hydrogen atoms of
ligands were refined with isotropic displacement
parameters. For this MOF, the volume fraction of
disordered solvents in pores could not be modeled in
terms of atomic sites, but was treated by using the MASK
1
Homo-coupling
of
aryl
Grignard
reagents
(exemplified by 2a with BUT-33). To a Schlenk tube was
added 1,2-dibromoethane (0.24 mg, 1.27 mmol), BUT-33
(10 mg, 0.008 mmol) and dry THF (6 mL) at RT. 4-
Methoxyphenyl magnesium bromide (2a, 1.27 mL, 0.64
mmol, 0.5 M in THF) was then slowly added into the
resulting reaction mixture. The mixture was stirred at RT
for 30 minutes. After the reaction was completed, the
catalyst was removed by centrifugation, and the
supernatant was concentrated under vacuum. The yield of
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
2
5
7
58
1
routine in the Olex2 software package.
Crystal
the crude product was determined by H NMR with
parameters and structure refinement are summarized in
Table S3.
dimethyl sulfone as the internal standard. The product 4a
was finally isolated by column chromatography on silica
gel using n-hexane as the eluent.
Structural determination of BUT-33. Electron
crystallography was applied to determine the structure of
nanocrystal BUT-33. The unit cell and space group were
successfully determined from cRED data, and the structure
was solved directly by using Shelx. Pawley method was
applied to refine the unit cell parameters, and the final
structure was refined against ED data (Table S4 and S5).
The cRED data were collected using the software
ASSOCIATED CONTENT
Supporting Information. Materials and instruments,
synthesis of H
refinement, computational details, general characterizations
FT-IR, TGA), and additional tables and figures.
3
TPTA, details of MOFs synthesis, structure
(
Crystal data for BUT-32 (CIF)
Crystal data for BUT-33 (CIF)
5
9
Instamatic. A single-tilt tomography holder was used for
the data collection, which could tilt from –70° to +70° in
the transmission electron microscope (TEM). The aperture
used for cRED data collection was about 1.0 μm in
AUTHOR INFORMATION
Corresponding Author
–
1
diameter. The speed of goniometer tilt was 0.45° s , and
the exposure time was 0.5 s per frame. Data was collected
within 4 min to minimize the beam damage and to
maximize the data quality. The covered tilt angle is
103.63°.
*E-mail: jrli@bjut.edu.cn
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
We acknowledge financial support from the National Natural
Science Foundation of China (No. 51621003, 21771012).
Sample activation and gas adsorption.60 Before gas
adsorption measurements, samples of BUT-32 and -33
powder (about 80 mg for each) were soaked in 15 mL of
o
DMF for 24 h at 60 C. The samples collected by decanting
REFERENCES
were then soaked in 15 mL of acetone for another 48 h,
when fresh solvents were exchanged thrice every day.
After solvent exchange, the samples were loaded in a
sample tube and further activated under high vacuum at an
optimized temperature of 120 °C. Then, the N adsorption
2
tests were conducted at 77 K in a liquid nitrogen bath.
(1)
metal-organic frameworks. Chem. Rev. 2012, 112 (2), 673–674.
2) Furukawa, H.; Cordova, K. E.; O'Keeffe, M.; Yaghi, O. M.
Zhou, H.-C.; Long, J. R.; Yaghi, O. M. Introduction to
(
The chemistry and applications of metal-organic frameworks.
Science 2013, 341 (6149), 1230444.
(3)
Li, B.; Wen, H.-M.; Cui, Y.; Zhou, W.; Qian, G.; Chen, B.
Stability Test. The as-synthesized BUT-32 and -33
samples (60 mg for each) were soaked in pH = 3 HCl, 4 M
NaOH aqueous solutions, and 1 M phenylmagnesium
bromide (10 mL) at RT, as well as in boiling water for 24 h,
respectively. Then, the samples were collected by
filtration, washed with water, and soaked in acetone for
Emerging Multifunctional Metal-Organic Framework Materials.
Adv. Mater. 2016, 28 (40), 8819–8860.
(4)
Islamoglu, T.; Goswami, S.; Li, Z.; Howarth, A. J.; Farha, O.
K.; Hupp, J. T. Postsynthetic Tuning of Metal-Organic Frameworks
for Targeted Applications. Acc. Chem. Res. 2017, 50 (4), 805–813.
(5)
Cui, Y.; Li, B.; He, H.; Zhou, W.; Chen, B.; Qian, G. Metal-
Organic Frameworks as Platforms for Functional Materials. Acc.
Chem. Res. 2016, 49 (3), 483–493.
2
further PXRD and N adsorption investigations.
Cross-coupling of aryl halogens and aryl Grignard
reagents (exemplified by 1a and 2a with BUT-33). To a
Schlenk tube was added bromobenzene (1a, 0.1 g, 0.64
mmol), BUT-33 (10 mg, 0.008 mmol) and dry THF (6 mL)
under N atmosphere at RT. 4-Methoxyphenyl magnesium
2
bromide (2a, 1.53 mL, 0.76 mmol, 0.5 M in THF) was then
slowly added into the resulting mixture, and then the
(6)
metal-organic frameworks. Coord. Chem. Rev. 2019, 399, 213023.
7) Yu, J.; Xie, L.-H.; Li, J.-R.; Ma, Y.; Seminario, J. M.;
Balbuena, P. B. CO Capture and Separations Using MOFs:
Computational and Experimental Studies. Chem. Rev. 2017, 117
14), 9674–9754.
Ali Akbar Razavi, S.; Morsali, A. Linker functionalized
(
2
(
ACS Paragon Plus Environment

Page 9 of 11
Journal of the American Chemical Society
(
8)
Frameworks for Separation. Adv. Mater. 2018, 30 (37), 1705189.
9) Koo, W.-T.; Jang, J.-S.; Kim, I.-D. Metal-Organic
Frameworks for Chemiresistive Sensors. Chem 2019, 5 (8), 1938–
963.
10) Wang, H.; Lustig, W. P.; Li, J. Sensing and capture of toxic
Zhao, X.; Wang, Y.; Li, D.-S.; Bu, X.; Feng, P. Metal-Organic
(26) Bordwell, F. G. Equilibrium acidities in dimethyl
sulfoxide solution. Acc. Chem. Res. 1988, 21 (12), 456–463.
(27) Zhang, Y.-Z.; He, T.; Kong, X.-J.; Bian, Z.-X.; Wu, X.-Q.; Li,
J.-R. Single-Crystal Synthesis and Structures of Highly Stable Ni8-
Pyrazolate-Based Metal–Organic Frameworks. ACS Mater
Lett.2019, 1 (1), 20–24.
1
2
3
4
5
6
7
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
(
1
(
and hazardous gases and vapors by metal-organic frameworks.
Chem. Soc. Rev. 2018, 47 (13), 4729–4756.
(28) Zhang, J.-P.; Zhang, Y.-B.; Lin, J.-B.; Chen, X.-M. Metal
azolate frameworks: from crystal engineering to functional
materials. Chem. Rev. 2012, 112 (2), 1001–1033.
(29) Pettinari, C.; Tăbăcaru, A.; Galli, S. Coordination
polymers and metal–organic frameworks based on
poly(pyrazole)-containing ligands. Coord. Chem. Rev. 2016, 307,
1–31.
(30) Padial, N. M.; Procopio, E. Q.; Montoro, C.; Lopez, E.;
Oltra, J. E.; Colombo, V.; Maspero, A.; Masciocchi, N.; Galli, S.;
Senkovska, I.; Kaskel, S.; Barea, E.; Navarro, J. A. Highly
hydrophobic isoreticular porous metal-organic frameworks for
the capture of harmful volatile organic compounds. Angew. Chem.
Int. Ed. 2013, 52 (32), 8290–8294.
(31) Guan, H.-Y.; LeBlanc, R. J.; Xie, S.-Y.; Yue, Y. Recent
progress in the syntheses of mesoporous metal–organic
framework materials. Coord. Chem. Rev. 2018, 369, 76–90.
(32) Liu, D.; Zou, D.; Zhu, H.; Zhang, J. Mesoporous Metal-
Organic Frameworks: Synthetic Strategies and Emerging
Applications. Small 2018, 14 (37), 1801454.
(33) Peng, L.; Yang, S.; Jawahery, S.; Moosavi, S. M.; Huckaba,
A. J.; Asgari, M.; Oveisi, E.; Nazeeruddin, M. K.; Smit, B.; Queen, W.
L. Preserving Porosity of Mesoporous Metal-Organic Frameworks
through the Introduction of Polymer Guests. J. Am. Chem. Soc.
2019, 141 (31), 12397–12405.
(34) Yaghi, O. M.; Kalmutzki, M. J.; Diercks, C. S. Introduction
to Reticular Chemistry; Wiley, 2019.
(35) Deng, H.; Grunder, S.; Cordova, K. E.; Valente, C.;
Furukawa, H.; Hmadeh, M.; Gandara, F.; Whalley, A. C.; Liu, Z.;
Asahina, S.; Kazumori, H.; O'Keeffe, M.; Terasaki, O.; Stoddart, J. F.;
Yaghi, O. M. Large-pore apertures in a series of metal-organic
frameworks. Science 2012, 336 (6084), 1018–1023.
(36) Guillerm, V.; Grancha, T.; Imaz, I.; Juanhuix, J.; Maspoch,
D. Zigzag Ligands for Transversal Design in Reticular Chemistry:
Unveiling New Structural Opportunities for Metal-Organic
Frameworks. J. Am. Chem. Soc. 2018, 140 (32), 10153–10157.
(37) Towsif Abtab, S. M.; Alezi, D.; Bhatt, P. M.; Shkurenko, A.;
Belmabkhout, Y.; Aggarwal, H.; Weseliński, Ł. J.; Alsadun, N.;
Samin, U.; Hedhili, M. N.; Eddaoudi, M. Reticular Chemistry in
Action: A Hydrolytically Stable MOF Capturing Twice Its Weight in
Adsorbed Water. Chem 2018, 4 (1), 94–105.
(38) Diercks, C. S.; Liu, Y.; Cordova, K. E.; Yaghi, O. M. The role
of reticular chemistry in the design of CO2 reduction catalysts.
Nat. Mater. 2018, 17 (4), 301–307.
(39) Yaghi, O. M. Reticular Chemistry in All Dimensions. ACS
Cent. Sci. 2019, 5 (8), 1295–1300.
(40) Tăbăcaru, A.; Galli, S.; Pettinari, C.; Masciocchi, N.;
McDonald, T. M.; Long, J. R. Nickel(II) and copper(I,II)-based
metal-organic frameworks incorporating an extended tris-
pyrazolate linker. CrystEngComm 2015, 17 (27), 4992–5001.
(41) Dincă, M.; Dailly, A.; Tsay, C.; Long, J. R. Expanded
Sodalite-Type Metal-Organic Frameworks: Increased Stability and
H2 Adsorption through Ligand-Directed Catenation. Inorg. Chem.
2008, 47 (1), 11–13.
(42) Cheetham, A. K.; Kieslich, G.; Yeung, H.-H.
Thermodynamic and Kinetic Effects in the Crystallization of
Metal-Organic Frameworks. Acc. Chem. Res. 2018, 51 (3), 659–
667.
(
11) Wang, B.; Wang, P.; Xie, L.-H.; Lin, R.-B.; Lv, J.; Li, J.-R.;
Chen, B. A stable zirconium based metal-organic framework for
specific recognition of representative polychlorinated dibenzo-p-
dioxin molecules. Nat. Commun. 2019, 10 (1), 3861.
(12) Rogge, S. M. J.; Bavykina, A.; Hajek, J.; Garcia, H.; Olivos-
Suarez, A. I.; Sepúlveda-Escribano, A.; Vimont, A.; Clet, G.; Bazin,
P.; Kapteijn, F.; Daturi, M.; Ramos-Fernandez, E. V.; Llabrés i, I. X.
F. X.; Van Speybroeck, V.; Gascon, J. Metal-organic and covalent
organic frameworks as single-site catalysts. Chem. Soc. Rev. 2017,
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
4
6 (11), 3134–3184.
(13) Dhakshinamoorthy, A.; Li, Z.; Garcia, H. Catalysis and
photocatalysis by metal organic frameworks. Chem. Soc. Rev.
018, 47 (22), 8134–8172.
14) Howarth, A. J.; Liu, Y.; Li, P.; Li, Z.; Wang, T. C.; Hupp, J.
2
(
T.; Farha, O. K. Chemical, thermal and mechanical stabilities of
metal–organic frameworks. Nat. Rev. Mater. 2016, 1 (3), 15018.
(15) Wang, C.; Liu, X.; Demir, N. K.; Chen, J. P.; Li, K.
Applications of water stable metal-organic frameworks. Chem.
Soc. Rev. 2016, 45 (18), 5107–5134.
(
16) Emerson, A. J.; Hawes, C. S.; Marshall, M.; Knowles, G. P.;
Chaffee, A. L.; Batten, S. R.; Turner, D. R. High-Connectivity
Approach to a Hydrolytically Stable Metal–Organic Framework
for CO
618.
17) Rieth, A. J.; Wright, A. M.; Dincă, M. Kinetic stability of
2
Capture from Flue Gas. Chem. Mater. 2018, 30 (19), 6614–
6
(
metal-organic frameworks for corrosive and coordinating gas
capture. Nat. Rev. Mater. 2019, 4 (11), 708–725.
(
18) Ding, M.; Cai, X.; Jiang, H.-L. Improving MOF stability:
approaches and applications. Chem. Sci. 2019, 10 (44), 10209–
0230.
19) Leubner, S.; Zhao, H.; Van Velthoven, N.; Henrion, M.;
1
(
Reinsch, H.; De Vos, D. E.; Kolb, U.; Stock, N. Expanding the Variety
of Zirconium-based Inorganic Building Units for Metal-Organic
Frameworks. Angew. Chem. Int. Ed. 2019, 58 (32), 10995–11000.
(20) Yuan, S.; Feng, L.; Wang, K.; Pang, J.; Bosch, M.; Lollar, C.;
Sun, Y.; Qin, J.; Yang, X.; Zhang, P.; Wang, Q.; Zou, L.; Zhang, Y.;
Zhang, L.; Fang, Y.; Li, J.; Zhou, H.-C. Stable Metal-Organic
Frameworks: Design, Synthesis, and Applications. Adv. Mater.
2
018, 30 (37), 1704303.
(
21) Cavka, J. H.; Jakobsen, S.; Olsbye, U.; Guillou, N.;
Lamberti, C.; Bordiga, S.; Lillerud, K. P. A new zirconium inorganic
building brick forming metal organic frameworks with
exceptional stability. J. Am. Chem. Soc. 2008, 130 (42), 13850–
1
3851.
22) Wang, K.; Lv, X.-L.; Feng, D.; Li, J.; Chen, S.; Sun, J.; Song,
(
L.; Xie, Y.; Li, J.-R.; Zhou, H.-C. Pyrazolate-Based Porphyrinic Metal-
Organic Framework with Extraordinary Base-Resistance. J. Am.
Chem. Soc. 2016, 138 (3), 914–919.
(
23) Bai, Y.; Dou, Y.; Xie, L.-H.; Rutledge, W.; Li, J.-R.; Zhou, H.-
C. Zr-based metal-organic frameworks: design, synthesis,
structure, and applications. Chem. Soc. Rev. 2016, 45 (8), 2327–
2367.
(24) Lv, X.-L.; Wang, K.; Wang, B.; Su, J.; Zou, X.; Xie, Y.; Li, J.-
R.; Zhou, H.-C. A Base-Resistant Metalloporphyrin Metal-Organic
Framework for C-H Bond Halogenation. J. Am. Chem. Soc. 2017,
1
39 (1), 211–217.
(43) Marshall, R. J.; Lennon, C. T.; Tao, A.; Senn, H. M.; Wilson,
C.; Fairen-Jimenez, D.; Forgan, R. S. Controlling interpenetration
through linker conformation in the modulated synthesis of Sc
metal–organic frameworks. J. Mater. Chem. A 2018, 6 (3), 1181–
1187.
(
25) Colombo, V.; Galli, S.; Choi, H. J.; Han, G. D.; Maspero, A.;
Palmisano, G.; Masciocchi, N.; Long, J. R. High thermal and
chemical stability in pyrazolate-bridged metal–organic
frameworks with exposed metal sites. Chem. Sci. 2011, 2 (7),
1
311–1319.
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 10 of 11
(
44) Kollias, L.; Cantu, D. C.; Tubbs, M. A.; Rousseau, R.;
C-C bond formation reactions. Dalton Trans. 2016, 45 (17), 7312–
7319.
(52) Kiefer, G.; Jeanbourquin, L.; Severin, K. Oxidative
Coupling Reactions of Grignard Reagents with Nitrous Oxide.
Angew. Chem. Int. Ed. 2013, 52 (24), 6302–6305.
(53) Ackermann, L.; Born, R.; Spatz, J. H.; Meyer, D. Efficient
aryl-(hetero)aryl coupling by activation of C-Cl and C-F bonds
using nickel complexes of air-stable phosphine oxides. Angew.
Chem. Int. Ed. 2005, 44 (44), 7216–7219.
(54) Cahiez, G.; Moyeux, A.; Cossy, J. Grignard Reagents and
Non-Precious Metals: Cheap and Eco-Friendly Reagents for
Developing Industrial Cross-Couplings. A Personal Account. Adv.
Synth. Catal. 2015, 357 (9), 1983–1989.
1
2
3
4
5
6
7
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
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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
Glezakou, V. A.; Salvalaglio, M. Molecular Level Understanding of
the Free Energy Landscape in Early Stages of Metal-Organic
Framework Nucleation. J. Am. Chem. Soc. 2019, 141 (14), 6073–
6
081.
45) Bara, D.; Wilson, C.; Mörtel, M.; Khusniyarov, M. M.; Ling,
(
S.; Slater, B.; Sproules, S.; Forgan, R. S. Kinetic Control of
Interpenetration in Fe-Biphenyl-4,4′-dicarboxylate Metal-Organic
Frameworks by Coordination and Oxidation Modulation. J. Am.
Chem. Soc. 2019, 141, 8346–8357.
(
46) Ferguson, A.; Liu, L.; Tapperwijn, S. J.; Perl, D.; Coudert,
F.-X.; Van Cleuvenbergen, S.; Verbiest, T.; van der Veen, M. A.;
Telfer, S. G. Controlled partial interpenetration in metal-organic
frameworks. Nat. Chem. 2016, 8 (3), 250–257.
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
(55) Xue, F.; Zhao, J.; Hor, T. S.; Hayashi, T. Nickel-catalyzed
three-component domino reactions of aryl Grignard reagents,
alkynes, and aryl halides producing tetrasubstituted alkenes. J.
Am. Chem. Soc. 2015, 137 (9), 3189–3192.
(
47) Verma, G.; Butikofer, S.; Kumar, S.; Ma, S. Regulation of
the Degree of Interpenetration in Metal-Organic Frameworks.
Top. Curr. Chem. 2019, 378 (1), 4.
(
48) Schaate, A.; Roy, P.; Godt, A.; Lippke, J.; Waltz, F.;
(56) Oxford Diffraction CrysAlis Pro software. 2010, Ver.
1.171.34, Yarnton, Oxfordshire. Oxford Diffraction Ltd.
(57) Sheldrick, G. M. A short history of SHELX. Acta Cryst.
2007, 64 (1), 112–122.
(58) Rees, B.; Jenner, L.; Yusupov, M. Bulk-solvent correction
in large macromolecular structures. Acta Cryst. 2005, 61 (9),
1299-1301.
(59) Cichocka, M. O.; Ångström, J.; Wang, B.; Zou, X.; Smeets,
S. High-throughput continuous rotation electron diffraction data
acquisition via software automation. J. Appl. Crystallogr. 2018, 51,
1652–1661.
Wiebcke, M.; Behrens, P. Modulated synthesis of Zr-based metal-
organic frameworks: from nano to single crystals. Chem.-Eur. J.
011, 17 (24), 6643–6651.
(
Evaluation of the BET Theory for the Characterization of Meso
and Microporous MOFs. Small Methods 2018, 2 (11), 1800173.
(50) Ullah, S.; Bustam, M. A.; Assiri, M. A.; Al-Sehemi, A. G.;
Gonfa, G.; Mukhtar, A.; Abdul Kareem, F. A.; Ayoub, M.; Saqib, S.;
Mellon, N. B. Synthesis and characterization of mesoporous MOF
UMCM-1 for CO
modeling and thermodynamic study. Micropor. Mesopor. Mater.
2
49) Ambroz, F.; Macdonald, T. J.; Martis, V.; Parkin, I. P.
2 4
/CH adsorption; an experimental, isotherm
(60) He, T.; Zhang, Y.-Z.; Kong, X.-J.; Yu, J.; Lv, X.-L.; Wu, Y.;
Guo, Z.-J.; Li, J.-R. Zr(IV)-Based Metal-Organic Framework with T-
Shaped Ligand: Unique Structure, High Stability, Selective
2
020, 294, 109844.
(51) Teo, W. J.; Wang, Z.; Xue, F.; Andy Hor, T. S.; Zhao, J.
Cyclopentadienyl nickel(ii) N,C-chelating benzothiazolyl NHC
complexes: synthesis, characterization and application in catalytic
2
–
Detection, and Rapid Adsorption of Cr
O
2 7
in Water. ACS Appl.
Mater. Interfaces 2018, 10 (19), 16650–16659.
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