An antiferromagnetic metalloring pyrazolate (Pz) framework with [Cu12(μ2-OH)12(Pz)12] nodes for separation of C2H2/CH4 mixture

Article abstract of DOI:10.1039/c8ta04498h

The search for functional metalloring organic frameworks (MROFs) has been of continuous interest in the fields of both molecular rings and metal-organic frameworks (MOFs) due to their importance in many multifunctional applications. Herein, a hierarchical pyrazolate framework MROF-12 with the topology of the Schl?fli symbol {4⁶⁰.6⁶} is reported, which is constructed by an elongated rigid ligand and attractive metalloring cluster nodes [Cu₁₂(μ₂-OH)₁₂(Pz)₁₂]. MROF-12 not only adopts the unique functionalities of the metalloring clusters but also inherits the porous properties of MOFs. The large [Cu₁₂(μ₂-OH)₁₂(Pz)₁₂] metalloring nodes with the diameter of 12.202 ? endow MROF-12 with excellent stability and antiferromagnetism, and they are bridged by linear pyrazolate ligands (H₂NDI) to form micro-mesoporous MROF with permanent porosity. The activated sample MROF-12a can exhibit a relatively high Brunauer-Emmett-Teller/Langmuir surface area (460.7/571.9 m² g^-1) as well as pore volume of 0.240 cm³ g^-1. Dynamic fixed bed breakthrough experiments indicate that the separation of C₂H₂/CH₄ or CO₂/CH₄ mixtures can be efficiently achieved through a column packed with MROF-12a solid.

Full text of DOI:10.1039/c8ta04498h

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ISSN 2050-7488
PAPER
Kun Chang, Zhaorong Chang et al.
Bubble-template-assisted synthesis of hollow fullerene-like
MoS nanocages as a lithium ion battery anode material
2
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ARTICLE
An Antiferromagnetic Metalloring Pyrazolate (Pz) Framework with
Cu (µ -OH) (Pz) ] Nodes for Separation of C H /CH Mixture
[
1
2
2
12
12
2
2
4
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
a
a
a
a
*ab
Ziyin Li, Yingxiang Ye, Zizhu Yao, Junzhi Guo, Quanjie Lin, Jindan Zhang, Zhangjing Zhang,
*a
*ab
Fangfang Wei and Shengchang Xiang
DOI: 10.1039/x0xx00000x
The search for functional metalloring organic frameworks (MROFs) has been of continuous interest in the fields of both
molecular rings and metal–organic frameworks (MOFs), given their importance in a plethora of multifunctional
www.rsc.org/
60
6
applications. Here, a hierarchically pyrazolate framework MROF-12 with the topology of the Schläfli symbol {4 .6 } is
reported which is building up by elongated rigid ligand and attractive metalloring cluster nodes [Cu12(µ -OH)12(Pz)12].
MROF-12 not only adopts the unique functionalities of the metalloring clusters but also inherits the porous properties of
MOFs. The large [Cu12(µ -OH)12(Pz)12] metalloring nodes with the diameter of 12.202 Å endow MROF-12 with excellent
stability and antiferromagnetism, which are bridged by linear pyrazolate ligands (H NDI) to form micro-mesoporous MROF
with permanent porosity. The activated sample MROF-12a was found to exhibit the relatively high Brunauer-Emmett-
2
2
2
2
-1
3
-1
Teller/Langmuir surface area (460.7/571.9 m g ) as well as the pore volume of 0.240 cm g . Dynamic fixed bed
breakthrough experiments indicate that the separation of C /CH or CO /CH mixtures can be efficiently achieved
through column packed with MROF-12a solid.
2
H
2
4
2
4
a
development of MROFs is still in its infancy, and focusing on the
4
,6
Introduction
linkage of metalloring clusters with carboxylate ligands (Table S1).
Meanwhile, the performance of these reported MROFs is relatively
single. The MROFs with multi-functions and bridged by pyrazolate
ligands has not been explored so far, although pyrazolate ligands
can endow the MROFs with excellent stability, novel structure, and
Molecular rings, ranging from simple benzene rings to sophisticated
metalloring structures, represent one of the essential structural
1
motifs in chemistry. High-nuclearity metalloring (cyclic- and wheel-
type) has blossomed into a promising topic of modern coordination
chemistry and attracted increasing attention due to their
interesting structural features and their potential applications as
1
2
fantastic properties.
In this work, we chose elongated rigid bi-pyrazolate ligand (2,7-
bis(3,5-dimethyl)dipyrazol-1,4,5,8-naphthalene-tetracarboxydiimide,
H NDI) as bridging linker and [Cu (µ -OH) (Pz) ] (Pz = 3,5-
2
3
multifunctional materials, including magnetism, electricity, ion
4
5
2
12
2
12
12
exchange, and luminescence . Using high-nuclearity metalloring
dimethyl-pyrazole) metalloring clusters as nodes to form
a
clusters as supermolecular building units (SBUs) and bridging by
6
hierarchically porous multifunctional MROF material {Cu (NDI) (µ -
1
2
6
2
organic ligands to form metalloring organic frameworks (MROFs) , a
7
,8
OH) ·6H O·15MeOH·6DMF} (MROF-12). The diameter for [Cu (µ -
12 2 12 2
new subgroup of metal–organic frameworks (MOFs) , not only
8
b,9,10
OH) (Pz) ] is of 12.202 Å, larger than most of the reported
1
2
12
,6
inherits the porous properties of MOFs
but also adopts the
4
MROFs, and metalloring endows it’s material with excellent
stability and antiferromagnetism. MROF-12 can not only remain
intact in acid-base solution range from pH 2 to 13, but also resist
unique functionalities of the metalloring clusters. Meanwhile, high-
nuclearity metalloring clusters can contribute to construct novel
topology with high-connected networks and prevent structural
o
9
d,11
against the temperature up to 400 C. The stability of MROF-12 is
interpenetration.
The ability to control the structures of MROFs
6
f
higher than that of our previous reported MROF-1 with same
is a key concern for exploitation of their properties. However, the
4
2 4 6 6 6 2
topology, and that of H Na [Cu12(OH) (pz) (BTC) ]·23H O reported
by Wang’s group with similar metalloring cluster. These can be
ascribed to the usage of pyrazolate ligands to construct metalloring
clusters with more resistance against heat. The dynamic fixed bed
breakthrough experiments further indicates that MROF-12a can
2 2 4 2 4
efficiently separate C H /CH or CO /CH mixtures. Especially
among the reported MROFs with similar structures, multifunctional
MROF-12 not only has the unique functionalities of the metalloring
clusters, but also inherits the porous properties of MOFs.
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edges (Fig. 1d). The connection of two types of polyhedral cages
extends to form a three-dimension framework, generating three
Results and Discussion
2
different channels with an approximate size of 4.60 × 9.61 Å and
diameters of 9.35 Å and 9.81 Å, respectively (Fig. 1e). For the sake
of clarity, if simplify [Cu12(µ
2
-OH)12(Pz)12] clusters as twelve
connected nodes, MROF-12 adopts the topology with the Schläfli
6
0
6
symbol of {4 .6 }, which is same as our compound MROF-1 with
6
+
[
In
6
(thb)
6
]
metalloring nodes (thb = 2,5-thiophenedicarboxylate)
6
f
linked by 4,4′-biphenyldicarboxylate (Figs. 1f, S3 and Table S5).
However, the pore size of these two MROFs are completely
different with the consideration of the torsional difference between
the 12-connected polyhedral prisms in the two cluster nodes (Fig
S3). [Cu (µ -OH) (Pz) ] cluster can be seen as hexagonal antiprism,
Figure 1. The structure of MROF-12. (a) The [Cu (µ -OH) (Pz) ]
1
2
2
12
12
1
2
2
12
6+
12
metalloring SBU. Two types of polyhedral cages observed in MROF-
2: one dodecahedral cage (Cage-I, orange) (b) and another
where [In
6
(thb)
6
]
can be seen as hexagonal prism, leading to
1
different stacking patterns in structures through the respective rigid
octahedral cage (Cage-II, bright green) (c). (d) Two types of
6
f
linkers (Figs. S3, S4 and Table S5). After elimination of guest
polyhedral cages interlock each other in MROF-12. (e) The
2
-
metalloring SBU is bridged by NDI ligands to generate a 3D solvent molecules, the total accessible volumes in MROF-12 is 43.9%
1
2
framework with three types of channels (channel-A, green; channel- by using the PLATON software.
B, pink; channel-C, lavender). (f) Simplifing [Cu12(µ -OH)12(Pz)12
clusters as 12-connected nodes or hexagonal antiprism to from a 3D
2 4 6 6 6 2
H Na [Cu12(OH) (pz) (BTC) ]·23H O reported by Wang et al. have
2
]
On the other hand, both our compound MROF-12 and
4
6
0
6
topological net {4 .6 }.
the similar dodeca-nuclear metalloring clusters, but there are two
distinct aspects between their structures. One is the different
MROF-12 was synthesized via solvothermal reaction of
2
+
coordination geometry for the Cu atoms, the planar coordination
mode in the [Cu12(µ -OH)12(Pz)12] clusters in the former which is
completed by two pyrazole groups and two μ
quadrangular pyramid geometry in the [Cu12(OH)
clusters in the latter which is completed by one pyrazole, two μ
3 2 2 2
Cu(NO ) ·3H O, H NDI and 1,2,4-triazole in DMF/methanol solution
o
2
at 80 C for one day. The single crystal X-ray diffraction reveals that
-
2
-OH anions, and the
MROF-12 crystallizes in trigonal space group P3. There are four
2
+
6
(pz)
6
(COO)18
]
-
equivalent and crystallographically independent Cu ions as
2
-
2
2
coordinating with two N atoms from two NDI ligands and two μ -
-
2
+
OH anions and two carboxylates (Fig. S5). An O atom from one of
OH groups (Fig. S1). Adjacent Cu ions are held by one bidentate
bridging Pz ligand and one μ -OH group. Twelve Cu ions combined
to form a puckered cyclic-type [Cu12(µ -OH)12(Pz)12] SBU with its
center at the Wyckoff position of 1a (Fig. 1a). In [Cu12(µ -OH)12(Pz)12
SBU, μ -OH group at the inner- and Pz at the outer surface,
accompanied with an external diameter of 18.395 Å and a central
2
+
the two carboxylates occupies the axial position of the Cu atom in
the latter MROF, which may lead to its less stability than MROF-12.
Another is the different ligands, the long and linear bi-pyrazolate
2
2
2
]
ligand H
micropore and mesopore, while the triangular carboxylate ligand
may endow H Na [Cu12(OH) (pz) (BTC) ]·23H O with larger porosity
than MROF-12. The significant difference in the structures for the
three similar MROFs (MROF-12, MROF-1 and
Na [Cu12(OH) (pz) (BTC) ]·23H O) encourages us to further
exploit their properties.
2
NDI may bring MROF-12 with the co-existence of
2
2
4
6
6
6
2
cavity of 12.202 Å in diameter (Figs. 1a and S1). Each [Cu12(µ
OH)12(Pz)12] node connects with neighboring [Cu12(µ -OH)12(Pz)12
2
-
]
2
2
-
nodes through NDI linkers to produce two types of polyhedral
H
2
4
6
6
6
2
cages, one dodecahedron (Cage-I) is centered at the Wyckoff
2
position of 1a with the dimension of 18.52 × 52.20 Å and another
octahedron (Cage II) centered at 3d with the dimension of 26.35 ×
2
4
5.12 Å (Figs. 1b and 1c). For cage I, it is constructed by eight
2
-
[
[
Cu12(µ
Cu12(µ
2
-OH)12(Pz)12] SBUs and twelve NDI ligands, in which eight
2
-
2
-OH)12(Pz)12] SBUs as vertices and twelve NDI ligands as
2
-
edges. As its equator has no NDI occupied, each triangle face of
2
-
the dodecahedron is composed of two NDI edges and three
Cu12(µ -OH)12(Pz)12] vertices. The most striking feature of the Cage
[
2
I in MROF-12 is the self-interlock of the neighboring Cage I along Figure 2. Powder X-ray diffraction patterns of MROF-12 under
the c axis, the center of which can sever as the vertice of the variable (a) temperature and (b) pH conditions.
neighboring one (Figs. 1e and S2). At the same time, the Cage I is
The purity of the as-synthesized MROF-12 was examined by
also linked by the adjacent Cage I through sharing one edge. The
2
-
similarities between simulated and experimental powder X-ray
diffraction (PXRD) patterns (Fig. S7). The PXRD pattern of the
MROF-12 is coincident with the simulated from the single crystal
data, indicating a good purity and homogeneity of the compound.
The stability is still a significant weakness for most of the porous
Cage II consists of eight [Cu12(µ
ligands, in which the quadrangle in equator is contained six
Cu (µ -OH) (Pz) ] SBUs. In general, Cage I is interlocked with six
2
-OH)12(Pz)12] SBUs and twelve NDI
[
1
2
2
12
12
Cage II by sharing the centre of the Cage I. Similarly, Cage II is linked
by six Cage I as sharing four triangle faces accompany with two
2
| J. Name., 2012, 00, 1-3
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MOFs, limiting the practical applications, which is likely to behavior because of the hierarchical size channel effect. The
disintegrate or shrink into nonporous frameworks upon thermal, Brunauer-Emmett-Teller (BET)/Langmuir surface area of MROF-12a
1
4
2
-1
vacuum treatment or exposure even to moist air.
The is 460.7/571.9 m g (Fig. 3a). The BET surface area is higher than
2
-1 6f
thermogravimetric analysis (TGA) measurements were performed the value of our previously reported MROF-1 (80.8 m g ), but
2
-
to study the thermal stability of the as-synthesized samples. TGA for lower than the one of H
2
Na
4 6 6 6 2
[Cu12(OH) (pz) (BTC) ]·23H O (813 m g
o
1 4
MROF-12 reveals two weight loss of 12.3% from 30 to 102 C and
) , which is in line with the structural analysis mentioned above
o
3
-1
9
.2% till to 264 C, which one is in agreement with the weight of (Table S1). The pore volume for MROF-12a is of 0.240 cm g ,
3
-1
2 3
two H O and five CH OH molecules (calcd. 12.5%) and the other is slightly smaller than the value (0.392 cm g ) obtained from the
two DMF molecules (calcd. 9.2%) (Fig. S8). Finally, MROF-12 shows crystal density and the total accessible volumes by Platon. The pore
o
a plateau up to 481 C following with sharp weight loss, indicating size distribution of MROF-12a was calculated by employing
1
7,18
the collapse of the frameworks. However, the variable-temperature NLDFT,
showing the coexistence of micro- and mesopores as the
PXRD indicates that MROF-12 could keep its structure intact up to major pores located at 0.60, 0.87, 1.08, and 1.20 nm. The
o
4
00 C which slightly lower than the result of TGA, owing to the lack experimental micropore-size distribution (< 10 Å) in MROF-12a is
of N atmosphere in the test process. MROF-12 shows better heat- found to be conform to its simulated pore-size distribution by
stability
Na [Cu12(OH)
metalloring clusters, as the pyrazolate ligands H
material with excellent stability and rigid metalloring cluster than
2
o
19
than
(pz)
MROF-1
]·23H O (250 C) with similar topology or above (Figs. 3b and S9). The permanent porosity and suitable pore
2 4
NDI can offer the sizes of MROF-12a promote us to examine its C s (C , C H ,
(160
C)
and Zeo++ software, which is also close to the structural analysis
o
H
2
4
6
6
(BTC)
6
2
2
2
0,21
2
H
2
2
C
2
H
6
)/C
1
adsorption and separation performance.
1
5
carboxylic ligands. To further demonstrate the chemical stability
of MROF-12, we have treated its samples under different conditions caused worldwide concerns. Natural gas (75–90% CH
Fig. 2b). The framework of MROF-12 still retain in aqueous most promising clean energy and important chemical raw material,
solutions with pH values in the range of 2−13 over 12 hours. and the purification of which has become the key to the
Currently, energy crisis has created some serious problems and
22
4
) as the
(
9
f,23,24
Although some reported MOFs present water tolerance or chemical improvement of energy efficiency.
2 2
Moreover, acetylene (C H )
stability in acidic or basic media, very few MOFs were found to be is important chemical feedstock in various chemical
1
2a,16
resistant to both strong acid and base.
transformations which mainly generated from the thermal cracking
2
5
of natural gas. Therefore, the separation of light hydrocarbon
mixtures can not only upgrade the quality of natural gas but also
provide an alternative chemical source of C H for further chemical
2
2
2
6
processing and conversion.
Traditionally, light hydrocarbon
separations are performed by cryogenic distillation, which is very
27
costly and energy consuming. Recently, an alternative and energy-
28
efficient strategy is using porous materials, such as zeolites,
29
30
31
porous carbons, porous polymer, and MOFs.
Among these porous materials, MOFs have demonstrated
significant promise for adsorption and separation because of their
3
2
structural visualization and chemical tailorability. In MROF-12a, it
only adsorbs limited amounts of CH at 296 K or 273 K with sharp
4
contrast to C
the C , C
2
s adsorption (Figs. 3c and S10). At 296 K and 1 atm,
2
H
2
2
H
4
, and C
2
3
H
6
−1
uptake capacities of MROF-12a are 63.25,
4
8.99, and 43.99 cm g , respectively, which are 4.45, 3.45, and
3
−1
Figure 3. (a) N
2
4
sorption isotherm of MROF-12a at 77 K. (b) The 3.09 times higher than CH (14.22 cm ·g ). Such a discrimination of
pore-size distribution of MROF-12a from CO adsorption at 273 K
2
adsorption capacities enables MROF-12a to be a very promising
(
red) and N
density functional theory, NLDFT). (c) C H , C H , C H , and CH
4
2
sorption at 77 K (dark) (calculated by the non-local
material for the selective separation of C s from CH . To confirm the
2
4
2
2
2
4
2
6
adsorption selectivities in MROF-12a, the widely used Henry’s law
sorption isotherms of MROF-12a at 296 K. (d) Column breakthrough
experiment for a C /CH /He = 5/5/90 gas mixture was carried out
on MROF-12a at 296 K and 1 bar.
33
34
selectivity and ideal adsorbed solution theory (IAST) calculation
are applied to estimate the C s/CH adsorption selectivities. The
Henry’s law selectivities for C H /CH , C H /CH , C H /CH are 36.2,
2
H
2
4
2
4
2
6
4
2
4
4
2
2
4
The fresh MROF-12 samples were guest-exchanged with acetone 19.6, 23.4 at 296 K and 47.2, 23.8, 30.7 at 273 K, respectively, which
and then activated under high vacuum at 333 K to generate the is figured up according to the equation S = K (i)/K (CH ) (Table S6).
ij
H
H
4
desolvated MROF-12a. The PXRD pattern of MROF-12a shows that The IAST calculation for C H /CH (50:50, v:v), C H /CH (50:50, v:v)
2
6
4
2
4
4
the peaks keep the positions, indicating the maintenance of the and C H /CH (50:50, v:v) at 296 and 273 K were expressed in Fig.
2
2
4
frameworks (Fig. S7). Its permanent porosity has also been S17. It is clear to read that the IAST adsorption selectivities for C H ,
2
6
established by N sorption at 77 K, displaying typical type-I sorption C H , and C H over CH are 19.0, 15.7, and 22.8, respectively, at
2
2
4
2
2
4
behavior and appearing to have pronounced hysteretic sorption 296 K under 100 kPa. It should be noted that the C s/CH4
2
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2 2 4
selectivities of MROF-12a, especially for C H /CH , under ambient
conditions were higher than many MOFs materials such as
3
5
36
37
38
Zn (BTA) (TDA) , ZJU-31a , UTSA-33a , and QMOF-1a . The
5
6
2
2 2 4
isosteric enthalpy (Qst) for MROF-12a towards C H and CH are
calculated on the basis of the virial method and the van’t Hoff
isochore by fitting the adsorption isotherms at 273K and 296 K (Figs.
2 2
S11-S15). The enthalpy at zero coverage Qst,n=0 for C H adsorption
on MROF-12a is 17.8 kJ/mol, which is lower than that of some
representative porous MOFs with relatively high C H /CH
4
2
2
separation selectivity, and obviously lower than the energy
Figure 4. (a) Magnetic exchange scheme and coupling constants
consumption (110.2 kJ/mol) on industrial cryogenic distillation used to fit the magnetic properties of the [Cu (µ -OH) (Pz) ]
1
2
2
12
12
9
d,9f,23b,39,40
which calculated by Aspen Plus (Fig. S20).
with relatively high C /CH selectivity and low Qst can be an
excellent candidate for the practical separation of C /CH
Dynamic breakthrough experiments were conducted to confirm
the selective adsorption of C s over CH in the practical adsorption
process. A representative C /CH /He (5/5/90) mixture was flowed
over a packed column of MROF-12a with a total flow of 6.5 mL
m m
MROF-12a cluster in MROF-12. (b) Plots of χ (black squares) and χ T (blue
circles) versus T for MROF-12. The solid red line represents the best
fit to the experimental data.
2
H
2
4
2
H
2
4
.
4
7
Hamiltonian :
2
4
ꢆꢆ
ꢆꢈ
2
H
2
4
ꢎꢎꢏ
Ĥ ꢀ ꢁꢂꢃ ŜꢄŜꢄꢅꢆ ꢇ ŜꢆŜꢆꢈꢉ ꢇ ꢊꢋ ꢌ ꢃ Ŝ
ꢌ
ꢄ
ꢄꢍꢆ
ꢄꢍꢆ
−1
min at 296 K. As shown in Fig. 3d, the separation of the C H /CH
4
Where J is the exchange coupling constant between the nearest
2
2
mixture can be efficiently achieved. It is noted that a roll-up neighbor Cu atoms, Ŝ is a spin operator of each Cu center whose
i
behavior was observed for methane due to a partial substitution of suffix is identical to that shown in Fig. 4a, μ is the Bohr magneton,
B
the adsorbed methane on the adsorption sites by C H with
ꢎꢎꢏ
g is the spectroscopic splitting factor, and ꢌ is the applied magnetic
2
2
4
1
4
stronger adsorptive action in the gas mixtures. CH was detected
field vector. As it can be seen, the molar χ increases with
decreasing temperature up to 2 K while χ T value decreases
m
downstream shortly after the gas mixture was introduced into the
column (90 s), while C H was not detected until a breakthrough
m
2
2
monotonically upon cooling and tends to vanish when the
temperature approaches zero, indicating the occurrence of an
time of 1530 s. Breakthrough time is linked with the dynamic
adsorption capacity. The dynamic C adsorption capacity was
2 2
H
2
antiferromagnetic (AF) interaction exchange between [Cu12(µ -
−1
3
−1
found to be 0.29 mmol g , based on which, the separation factor
m
OH)12(Pz)12] metalloring clusters. A molar χ T of 4.5 cm K mol is
was 6.82. The separation factor for MROF-12a is higher than the
expected for twelve magnetically isolated Cu(II) centers. In contrast,
25b
values of mesoporous-organosilicas (s-PMO-2, 5.2)
and MOFs
the smaller experimentally χ T value of MROF-12 at 300 K is about
m
42
3
−1
(
NKMOF-1-Ni, 6.6) but the C H enthalpy is obviously lower than
2
2
1.08 cm K mol , and further suggests that there is AF coupling
between the Cu(II) ions in the metalloring ensuring a diamagnetic S
these materials (Table S7). This result suggests that MROF-12a is
promising for selective separation of C /CH /He (5/5/90) mixture.
MROF-12 is the first metalloring organic framework that has been
used to separate C from C /CH mixtures (Table S1).
2
H
2
4
=
0 ground state. In order to give a quantitative explanation, these
magnetic data have been fitted to spin models that take into
account the structural features of these [Cu12(µ -OH)12(Pz)12
2
H
2
2
H
2
4
]
2
4
8
Additionally, there is significant differences in the adsorption
clusters using the package MAGPACK. The best fit for the
capacity of CO and CH in MROF-12a, the equimolar CO /CH gas
2
4
2
4
experimental data to our [Cu (µ -OH) (Pz) ] metalloring model
1
2
2
12
12
2
6b,43
−1
mixture was conducted (Figs. S11 and S19).
breakthrough curve, the CO /CH mixture is clearly separated by
MROF-12a. CO is detected after a certain time of 552 s and the
From the
was found for J= -1.96 cm and g=2.10. These results are in good
2
4
agreement with the ring compounds where the Cu(II) ions are
4
8,49
2
bridged by hydroxyl groups.
As indicated by the crystal structure
-1
amount of CO
on the CO adsorption capacity, the separation factor of CO
.50, comparable with UiO-66 (1.90) and slightly lower than
2
captured in the MROF-12a is 0.52 mmol g . Based
of MROF-12, the Cu(II) centers are extended by NDI ligands to
generate a 3D framework, and the Cu···Cu distance through the
ligand bridges are in the range of 3.163 to 3.169 Å. There are weak
2
2
/CH is
4
44
1
2
−
45
46
Co(bdp) (bdp = 1,4-benzenedipyrazolate) (5.70) , ZJNU-59 (4.2) ,
2
intramolecular interactions with the [Cu12(µ -OH)12(Pz)12] clusters in
2
6b
and ZJNU-54 (5.2) . The result indicates that MROF-12a is also
the structure, and the distance across the ligands is too great for
any real magnetic super-exchange. These characteristics indicate
that there are AF interactions between the adjacent Cu(II) ions
suitable for the separation of CO /CH mixture, and which provides
2
4
insights for the further study of MROFs for gas separations.
Magnetic susceptibility data were collected for MROF-12 based
on crystalline samples over the temperature range of 2–300 K
50
mediated through hydroxyl groups.
Experimental
Materials and Measurements: 1,4,5,8-Naphthalenetetra
m m m
under the field of 1 kOe. The plots of χ and χ T (χ = magnetic
susceptibility) versus T for MROF-12 are depicted in Fig. 4.
Considering the magnetic interaction originates from twelve
equivalent copper(II) ions (S = 1/2), strongly coupled in a
metalloring, can be represented by using the isotropic
Carboxylicdianhydride (NDA) and 1,2,4-Triazole were purchased
3 2 2
from J&K Chemical Co., Ltd.. Cu(NO ) ·3H O, acetylacetone, sodium
nitrite, and other reagents were purchased from Shanghai Chemical
This journal is © The Royal Society of Chemistry 20xx
4
| J. Name., 2012, 00, 1-3
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J oP ul er na as el o df oM na ot et rai ad lj su Cs th me ma ri sg ti rn ys A
View Article Online
DOI: 10.1039/C8TA04498H
Journal Name
ARTICLE
ꢛ
Reagent Co.. N,N-Dimethylformamide (DMF), methanol, and other
aqueous solutions were reagent grade and used without further
ꢑꢄꢒ
ꢗ
ꢐꢄ ꢀ
× ꢕ ꢖꢆ − ꢙ ꢚꢛ
ꢈꢈ. ꢓ × ꢔ
ꢗꢘ
ꢘ
−
1
purification. The ligand H
2
NDI was synthesized similar to published where q is the equilibrium adsorption capacity of gas i (mmol g ),
i
5
0
procedure.
Ci is the feed gas concentration, V is the volumetric feed flow rate
3
−1
The Powder X-ray diffraction (PXRD) for samples were tested by (cm min ), t is the adsorption time (min), F and F are the inlet and
0
3
PANalytical X’Pert powder diffractometer with equipped with a Cu- outlet gas molar flow rates, respectively, and m is the mass of the
sealed tube (λ = 1.541874 Å) (40 kV and 40 mA over the 2θ range of adsorbent (g).
o
5
-30 ) which further compared to the simulated pattern that
3 2 2
Synthesis of MROF-12. A mixture of Cu(NO ) ·3H O (0.0242 g, 0.1
produced by the Mercury V1.4 program and single-crystal mmol), H NDI (0.0227 g, 0.05 mmol), and 1,2,4-Triazole (0.0061 g,
2
diffraction data. The Elemental analyses (C, H and N) and Fourier 0.1 mmol) was dissolved in DMF/MeOH (6 mL/1 mL) in a screw-
transform infrared (KBr pellets) spectra were performed on a capped vial. After addition of 0.5 mL of HCl (1 M, aq), the vial was
o
Perkin-Elmer 240C analyzer and Thermo Nicolet 5700 FT-IR heated at 80 C for 1 day under autogenous pressure. Green
-
1
instruments with the range of 400~4000 cm , respectively. The prismatic crystals were obtained after filtration, washed with DMF,
o
data of Thermal analysis from 30 to 800 C were carried out on a and dried in air. Yield 46% (based on H NDI). Elemental analysis
2
METTLER TGA/ SDTA 851 thermal analyzer which heat at a rate of calcd
(%)
for
12 6 2 12 2
{Cu (NDI) (µ -OH) ·6H O·15MeOH·6DMF}
o
-1
1
0 C min under nitrogen atmosphere. The simulated surface area (Cu C177H222N O ): C, 45.15; N, 12.49; H, 4.71. Found: C, 44.08; N,
1
2
42 63
and pore-size distribution were calculated by using the open-source 12.75; H, 4.68.
1
9
software Zeo++ . The magnetic susceptibilities of the crystalline
MROF-12 were measured with a Quantum Design MPMS-XL SQUID
susceptometer under an applied magnetic field of 1 kOe in the 2–
Conclusions
3
00 K range. Diamagnetic corrections were made using Pascal's
5
1
constants.
In summary, we have demonstrated that a multifunctional and
hierarchically porous pyrazolate metalloring organic
Single crystal X-ray structure determination. Data collection and
structural analysis were collected at 100 K for MROF-12 by an framework (MROF-12) can be constructed from elongated
Agilent Technologies Super Nova Single Crystal Diffractometer rigid ligand and large metalloring cluster nodes [Cu12(µ
2
-
OH)12(Pz)12] (Pz = pyrazole). The attractive metalloring cluster
with the diameter of ca. 12.202 Å, endows MROF-12 with
antiferromagnetism and excellent stability. MROF-12 can not
only remain intact in the solution range from pH 2 to 13, but
also resist against the heat up to 400 C. Gas adsorptions imply
that the activated sample MROF-12a has the potential
which equipped with graphite monochromatic Cu Kα radiation (λ =
.54184 Å). The structure of MROF-12 was solved by the program
1
5
2
53
Olex2 and refined with the ShelXL . All nonhydrogen atoms in
structure were refined with anisotropic displacement parameters.
The hydrogen atoms on the ligands were placed in idealized
o
positions and refined using
a
riding model. We employed application in selective adsorption toward C2s/C1 mixtures
54
55
PLATON /SQUEEZE to calculate the diffraction contribution of the and dynamic column breakthrough experiment further
indicates that MROF-12a can effectively separate C
(
flow conditions. Our investigation provides insights for the
design and synthesis of high-nuclearity MROFs with a stable
and meso-/micro-porous framework for the separation of gas
mixtures.
2 2 4
H /CH /He
solvent molecules and thereby produce a set of solvent-free
diffraction intensities. The detailed crystallographic data and
structure refinement parameters for MROF-12 are summarized in
Supplementary Table S2 (CCDC-1835951). These data can be
obtained freely from the Cambridge Crystallographic Data Centre
via www.ccdc.cam.ac.uk/data_request/cif.
5/5/90 v/v/v) or CO /CH (50/50 v/v) mixtures under kinetic
2
4
Column Breakthrough Experiments. The mixed-gas breakthrough
separation experiment was conducted at 296 K using a labscale fix-
Conflicts of interest
bed reactor and monitored by a gas chromatograph (GC126) There are no conflicts to declare.
Scheme S1). In a typical experiment, ∼0.2 g of MROF-12 was
(
packed into a quartz glass column (the quartz glass column was 45
cm in length with a 5.5 mm inner (8 mm outer) diameter) with silica Acknowledgements
wool filling the void space. The sorbent was activated in situ in the
column with a vacuum pump at 333 K for 24 h. A helium flow (10
This work was financially supported by the National Natural
Science Foundation of China (21273033, 21673039 and
−1
mL min ) was used after the activation process to purge the
adsorbent. The flow of He was then turned off, while a gas mixture
2
1573042) and Fujian Science and Technology Department
(50:50, (2014J06003). S. X. gratefully acknowledges the support of the
v/v) at 4.1 mL min were allowed to flow into the column. The Recruitment Program of Global Young Experts.
complete breakthrough of C and other species was indicated by
−1
2 2 4 2 4
of C H /CH /He (5:5:90, v/v/v) at 6.5 mL min or CO /CH
−1
2 2
H
the downstream gas composition reaching that of the feed gas. On
the basis of the mass balance, the gas adsorption capacities can be
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This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
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