A new anionic metal-organic framework based on tetranuclear zinc clusters: Selective absorption of CO2 and luminescent response to lanthanide (III) ions

Article abstract of DOI:10.1016/j.ica.2018.05.039

A new anionic metal-organic framework, {[H₃O]₂[Zn₄(μ₄-O)(NSBPDC)₄]·16(H₂O)]}_n (1), was synthesized under solvothermal conditions using a predesigned multifunctional dicarboxylic

Full text of DOI:10.1016/j.ica.2018.05.039

Accepted Manuscript
Research paper
A new anionic metal-organic framework based on tetranuclear zinc clusters:
selective absorption of CO and luminescent response to lanthanide (III) ions
2
Ai-Ling Cheng, Juan Zhang, Ling-Ling Ren, En-Qing Gao
PII:
S0020-1693(18)30027-6
https://doi.org/10.1016/j.ica.2018.05.039
ICA 18290
DOI:
Reference:
To appear in:
Inorganica Chimica Acta
Received Date:
Revised Date:
Accepted Date:
5 January 2018
1 May 2018
28 May 2018
Please cite this article as: A-L. Cheng, J. Zhang, L-L. Ren, E-Q. Gao, A new anionic metal-organic framework based
on tetranuclear zinc clusters: selective absorption of CO and luminescent response to lanthanide (III) ions,
2
Inorganica Chimica Acta (2018), doi: https://doi.org/10.1016/j.ica.2018.05.039
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A new anionic metal-organic framework based on tetranuclear zinc clusters: selective
2
absorption of CO and luminescent response to lanthanide (III) ions
a,*
a
a
b
Ai-Ling Cheng , Juan Zhang , Ling-Ling Ren , En-Qing Gao
a
College of Chemistry and Molecular Engineering, East China Normal University, Shanghai
200240, PR China.
b
Shanghai Key Laboratory of Green Chemistry and Chemical Processes, College of Chemistry
and Molecular Engineering, East China Normal University, Shanghai 200062, PR China.
*
Corresponding authors.
Email address: alcheng@chem.ecnu.edu.cn (A.-L. Cheng)
Keywords: anionic; metal-organic framework; ultra-microporous; gas adsorption; luminescent
Abstract: A new anionic metal-organic framework, {[H
3
O]
2
[Zn
4 4
( -O)(NSBPDC)
4
]16(H
2 n
O)]}
(
1), was synthesized under solvothermal conditions using a predesigned multifunctional
dicarboxylic acid (H
2
NSBPDC = 6-nitro-2,2'-sulfone-4,4'-dicarboxylic acid). Complex 1 contains
( -O)(CO ] clusters, which are further linked by the bridging
ligands, generating a three-fold interpenetrated diamond-like network with ultra-microporous
channels. Gas adsorption studies reveal that 1 has good adsorption selectivity for CO over CH
and N . In addition, 1 can serve as a host to incorporate lanthanide cations via a targeted
ion-exchanged process. Notably, the structure of 1 can be dehydrated and rehydrated reversibly.
4
-connected tetrahedral [Zn
4
4
2 8
)
2
4
2
1. Introduction
Metal−organic frameworks (MOFs), as a new class of hybrid organic-inorganic materials, has
attracted considerable attention owing to their structural diversity and promising applications in
adsorption and separation, ion-exchange, catalysis, sensing and so on [1-8]. Therefore, a plethora
of MOFs with intriguing structures have been constructed by rational selection of metal ions (or
metal clusters) and organic ligands [9-11]. Significantly, polynuclear metal clusters (di-, tri-,
tetranuclear and even higher-nuclear clusters) usually possess high rigidity and well-established
geometries, which can be viewed as secondary building units (SBUs) to construct robust
high-connected MOFs with predictable topologies [12-14]. Among the various kinds of SBUs,
dinuclear copper and tetranuclear zinc clusters have been widely studied for the generation of
4 6
desirable MOFs. In particular, with the 6-connected octahedral [Zn O(COO) ] as SBUs, a series of
pcu type MOFs (IRMOFs) have been successfully synthesized by using different linear
decarboxylases as the ligands [13]. Additionally, by replacing the linear dicarboxylates with
slightly bent ligands [fluorene-2,7-dicarboxylate and N,Nʹ-bis(4-carboxyphenyl)urea], a rare 3D
kag type framework (2) and an unconventional flexible pcu type framework (3) based on
[
Zn
4 6 2
O(COO) (sol) ] (sol = DMSO/DMF) clusters have been obtained, respectively [15, 16]. The
above results indicate that the slight bending of the dicarboxylate ligands would affect the

4
connection mode of the Zn O cluster and then lead to different topologies. However, MOFs
constructed from polynuclear clusters as nodes and slightly bent dicarboxylates as linkers are still
limited.
On the other hand, technologies for CO
researches and industrial applications [17, 18]. In general, adsorption capacity and selectivity are
two main aspects to evaluate an adsorbent material for CO capture. Compared with traditional
porous adsorbent materials, MOFs have shown prominent advantages for potential applications in
CO capture, owing to their extra-high porosity and tunable pore environments [19-22]. In recent
decades, great efforts have been made to improve the adsorption properties of MOFs for CO , and
2
capture become increasingly significant in both academic
2
2
2
several efficient strategies have been developed [23-26]. For one thing, regulation of pore size
distribution. Recent studies suggested that MOFs featuring ultra-micropores ( 7 Å) are applicable
for separating gases with similar diameters during which the separation process is mainly based on
molecular sieving effect [26]. For another, on account of the intrinsic quadruple moment and weak
acidity of CO
methods: functionalization of the pore walls with basic or polar functional groups, such as –NH
NO , –CN, and so on; introduction of unsaturated coordinated metal centers (UMCs);
2 2
molecules, the affinity of adsorbents toward CO can be enhanced by the following
2
,
–
2
incorporation of electrostatic fields by design of charged skeletons. Though some progress has
been achieved in this domain, the relevant research is still far from enough. The enhanced
host–guest interactions and molecular sieve effect may enhance the adsorption performance
cooperatively, which can be realized by construction of MOFs featuring ultra-microporosity,
functional group decoration and charged skeleton.
In addition, MOFs decorated with functional groups can be applied not only to selective CO
2
separation, but also to some special areas including molecular recognition and catalysis [27].
Recently, we and others have reported series of sulfone-functionalized MOFs assembled from
metal motifs and a slightly bent functional dicarboxylate ligand, 2,2'-sulfone-4,4'-dicarboxylic
acid (H
2
SBPDC), some of which showed guest-responsive photoluminescence and gas adsorption
properties [28-33]. Along the line, 6-nitro-2,2'-sulfone-4,4'-dicarboxylic acid (H
2
NSBPDC) was
synthesized and first utilized to react with the zinc ion based on the following reasons: I. the nitro
group can increase the polarity of the ligand, which might lead to a stronger affinity of the final
2
framework to CO ; II. The active amino group may be introduced by the follow-on reduction of
the nitro group via the chemical modifications; III. Due to the facile tendency of zinc ions to
assemble clusters, it is possible to construct novel frameworks based on zinc clusters. In this
contribution, we report a new 3D porous framework, {(H
3
O)
2
][Zn
4
O(NSBPDC)
4
]16(H
2 n
O)} (1),
which is a three-fold interpenetrated diamond-like anionic network based on 4-connected
[
Zn
4
O(COO)
8
] clusters. As we expected, complex 1 not only shows good adsorption selectivity for
3+
CO
2
over CH and N , but also can serve as a host to incorporate Ln ions by cation-exchange.
4 2
Additionally, the structure of 1 exhibits a reversible dehydration and rehydration process.
2. Experimental

2.1 Materials and methods
All reagents were purchased commercially and used without further purification.
-nitro-2,2'-sulfone-4,4'-dicarboxylic acid (H NSBPDC) was prepared according to the literature
6
2
procedure [34], and the synthetic route is depicted in Scheme S1. The detailed description of the
general methods and X-ray Crystallography can be seen in the supporting information. The crystal
1
data of 1: Tetragonal, I4 /a, T = 296(2) K, a = b = 30.2890(14) Å, c = 8.1594(8) Å, α = β = γ =
3
9
0°, V = 7485.6(9) Å , Z = 16, no. of reflns measured = 47276, no. of independent reflns = 4671,
2
R
o
int = 0.0473, GOF = 1.051, R ((I) > 2σ(I)) = 0.0417, wR (F ) = 0.1225.
2.2 Synthesis of {(H
3
O)
2
[Zn
4
O(NSBPDC)
4 2 n
]16(H O)} (1)
A mixture of H
2
NSBPDC (20 mg, 0.057 mmol) and Zn(NO
3
)
2
6H
2 2
O (40 mg, 0.13 mmol) in H O
(
8 mL) and CH OH (3 mL) was stirred for 30 min in air at room temperature. The mixture was
3
then transferred and sealed in a 23 mL Teflon-lined autoclave, and heated at 172 °C for 5 days.
After cooling to ambient temperature slowly, pale brown needle crystals were isolated (55% yield
based on H
2
NSBPDC). Anal. Calcd. (%) for C56
H
58
N
4
O
51
S
4
Zn
: Zn 13.2%, found: Zn 13.1%. IR data
KBr, cm ): 1602s, 1538m, 1441w, 1388vs, 1178w, 1317，1193，1143.
4
: C 33.7, H 2.94, N 2.81. Found: C
32.9, H 2.90, N 2.62%. ICP analysis for C56H N O S Zn
58 4 51 4 4
-
1
(
3+
2
.3 Encapsulation of Ln in 1
The as-synthesized 1 (40 mg) was soaked in H
2
O-methanol (2 mL/1 mL) solutions of Ln(NO
3 3
)
-
1
3+
3+
3+
(
0.3 molL , Ln = Eu , Tb ) at 50℃ for 3 days. The exchanged samples were filtrated and
3+
thoroughly washed with water, and then dried in air to give Ln @1.
3. Results and Discussion
3.1 Description of the crystal structure
Fig. 1 Views showing the tetranuclear [Zn
4 8
O(COO) ] SBU (a) and the pseudo-tetrahedral connectivity of four SBUs
in 1 (b) . Hydrogen atoms have been omitted for clarity.

Fig. 2 Views showing the evolution of the pcu net (d), the kag net (e) and the diamond net (f) constructed by the
Zn O SBU (ac) in IRMOFs, 2 and 1, respectively.
4
Single-crystal X-ray diffraction analysis indicated that compound 1 crystallizes in the tetragonal
space group I4
1
/a and features a 3-fold interpenetrated 3D anionic diamond network base on
II
4
tetranuclear [Zn O(COO)
8
] clusters. In the cluster, each Zn ion (Zn1) resides at a crystallographic
2
-
ꢀ
site, and is surrounded by three carboxylate oxygen atoms from different NSBPDC ligands
and a central  -O atom, generating a distorted tetrahedral geometry (Fig. 1a). The ZnO bond
4
lengths are in the range of 1.946–2.009 Å, and the O-Zn-O angles range from 97.14 to 127.40°. In
addition, there is one carboxylate oxygen atom (O5) which is coordinated weakly to Zn1 with the
ZnO distance of 2.616 Å. Take into account the weak interaction, the coordination geometry
around Zn1 may be considered as a highly distorted square pyramidal geometry. Furthermore, four
Zn atoms are connected by one 
distances are in the range of 2.919–3.321 Å, and the Zn-O-Zn angles range from 96.6° to 116.3.
It is noteworthy that the clusters in 1 are different from the well-known [Zn O(COO) ] clusters in
IRMOFs [13] and [Zn O(COO) (DMSO) ] clusters in MOF (2) [15]. In each cluster of the
IRMOF-n series (Fig. 2a), four Zn atoms form an ideal tetrahedron around  -O. There is one
-carboxylate bridge on each edge of the Zn O tetrahedron, generating a 6-connected regular
octahedral SBU with the O symmetry. Then, the clusters are interlinked by the linear linkers to
give a 3D framework with pcu topology (Fig. 2d). As for 2, the Zn O cluster is also furnished by
six  -carboxylate bridges at the six edges, but the coordination of the additional DMSO
molecules to two Zn ions leads to a distorted Zn O tetrahedron (Fig. 2b) and a distorted octahedral
-connected SBU with the pseudo-D2h symmetry. The equatorial inter-link angles of the SBU
deviate significantly from 90° to 60° and 120°, which leads to the formation of a framework with
the kag topology (Fig. 2e). Differently, in each Zn O cluster of 1 (Fig. 1b, 2c), two nonadjacent
edges (Zn1AZn1B and Zn1CZn1D) of the tetrahedron is each bridged by two  -carboxylate
groups (ZnZn 2.919 Å, Zn-O-Zn 96.6), but no carboxylate bridge is involved in the remaining
4 4
-O to afford a distorted [Zn O] tetrahedron. The ZnZn
4
6
4
6
2
4

2
4
h
4
2
4
6
4
2

four edges (ZnZn 3.321 Å, Zn-O-Zn 116.3). Besides, each vertex of the tetrahedron is chelated
by one carboxylate group. As a result, each Zn O cluster is furnished by eight carboxylate groups
four bridging and four chelating). Instead of serving as 8-connected node, the [Zn O(COO)
SBU is 4-connected, with a pair of the dicarboxylate ligands as double linkers between
neighboring SBU (Fig. 1b). Each ligand binds one Zn O cluster in a bidentate chelating fashion
4
(
4
8
]
4
and another cluster in a bidentate bridging mode. The overall network of 1 shows the well-known
diamond (dia) topology (Fig. 2f, 3a). Owing to the large void generated in a single net, three
identical nets mutually interpenetrate in a normal way to generate a 3-fold interpenetrating
architecture (Fig. 3b) [35]. Notably, despite the interpenetration, the framework still exist 1D
channels along the c-axis with dimensions of 5.6 Å × 5.6 Å (measured between opposite oxygen
atoms of nitro groups with consideration of van der Waals radii) (Fig. 4a). Based on the PLATON
[
36] calculations, the void value of the channels comprises 23.3% of the crystal volume (1745.5
3
3
+
Å out of 7485.6 Å unit cell volume), in which the disordered H
molecules are filled. Combined with the charge balance considerations, TG and elemental
analyses, the chemical formula of 1 is determined as {(H O) [Zn O(NSBPDC) ]16(H O)}
3 2
O counterions and H O
3
2
4
4
2
n
.
Fig. 3 Views showing the diamond network (a) and 3-fold interpenetration of the network (b) in 1.
Hydrogen atoms and nitro groups in figure 3a are emitted for clarity.
Additionally, the diamond coordination framework and the 3-fold interpenetration is sustained by
extended interplanar – interactions (Fig. 4b). In particular, the two ligands that constitute the
double linkers between two SBUs are parallel with interplanar and centroid–centroid distances of
3.8 Å and 4.0 Å. Additionally, each ligand from one net stack in parallel to a neighboring ligand
from another net, with interplanar and centroid–centroid distances of 3.5 Å and 3.7 Å. Thus it can
be seen that the ligands form infinite – stacking arrays along the c direction. The structure
around a channel can be regarded as three double-stranded helical chains extending around the 4
1
screw axes in an ABCABC fashion along the c direction (A, B, C represent the double-stranded
helical chains from the three interpenetrated networks). Remarkably, all of the nitro and
sulfo-functional groups of the ligands are dangled on the inner walls of these channels, which
might provide uniform sites for host-guest interactions.

Fig. 4 Views showing the 1d channels along the c axis (a) and the parallel spiral packing of the double
linkers around a channel (b) in 1.
2 2
Inspections into the framework of 1 suggest that the functional groups (-SO , -NO ) might have
critical impacts on the packing mode of the structure. The electron drawing effect of the functional
groups might enhance the - stacking interactions between the benzene rings of the bridging
ligands, and the pairwise - stacking tends to arrange the linkers in parallel, leading to such a
diamond-like three-fold interpenetrated network based on 4-connected tetrahedral
[
Zn
4 4 2 8
( -O)(CO ) ] clusters.
3.2 Rehydration studies
Fig. 5 PXRD patterns for complex 1.
As shown in Fig. 5, the PXRD patterns of as-synthesized samples of 1 match well with the
simulated one, indicating the good phase purity of compound 1. Thermo gravimetric analysis
(
TGA) of 1 shows a weight loss of 15.4% (calc. 16.2%) from 50°C to 200 °C, corresponding to
the loss of eighteen H O molecules, and the framework begins to decompose above 350 °C (Fig.
2

S6). In addition, PXRD experiments under different temperatures were also performed to
investigate the thermal behavior of 1 upon removal of guest molecules. The studies show that the
framework begins to collapse upon heating at 150 °C (Fig. 5), which means that 1 loses its
2
crystallinity along with the loss of guest molecules. Presumably, along with the release of the H O
+
molecules, protons liberated from H
3
O
will combine with carboxylate groups, and the
2
+
coordination interactions between carboxylates and Zn ions will be weakened. This might be one
of the reasons for the collapse of the framework. However, the crystallinity of 1 can be regained
by exposing the amorphous material to water vapor for several hours at room temperature. The
above results indicate that the framework of 1 can be dehydrated and rehydrated reversibly.
3.3 Gas adsorption properties
Fig. 6 Gas adsorption isotherms of CO
2
and CH for 1 at 273K and 298K.
4
The presence of the charged skeleton and the polar group decorated pores encourage us to explore
the selective adsorption properties of 1 for CO . To prove our hypothesis, the sorption behavior of
CO and CH were investigated at 273 K (Fig. 6). Prior to gas sorption experiments, compound 1
was activated at 100 °C under vacuum for 6h. The largest uptake values for CO and CH are 44.5
is 10.9 times higher than that
adsorption experiment shows that 1 does not adsorb N molecules (Fig S7).
The results suggest that 1 may be suitable for the separation of CO over CH and N
To further estimate the affinity of the framework toward CO , the isosteric enthalpies of CO
adsorption (Qst) were calculated by the Clausisus–Clapeyron equation. At zero coverage, the Qst
2
2
4
2
4
3
-1
3
-1
cm g and 4.1 cm g at 1 atm, and the uptake capacity of 1 for CO
for CH . Moreover, N
2
4
2
2
2
4
2
.
2
2
-
1
value for CO
framework of 1 and CO
that of many reported MOFs featuring UMCs or charged skeletons, such as HKUST-1 (29.2
2
was 39.1 kJmol (Fig. S8), which indicates that the interactions between the
2
molecules are relatively strong. Noticeably, the Qst value of 1 exceeds
-
1
-1
kJmol ) [37], CPF-13 (28.2 kJmol ) [38] and [(CH
3
)
2
NH
2
]
3 4
[(Cu Cl)
3
(BTC)
8
]9DMA (25.38
-1
kJmol ) [39]. The high Qst value and good adsorption selectivity of CO
2
/CH
4
of 1 could be
attributed to the following two aspects: Firstly, the narrow pore size distribution of 1 (5.6 Å)
suggests that molecular sieve effect might play a key role for the high adsorption affinity.

2
Secondly, the interactions between the framework and adsorbed CO molecules (quadrupole
-39
2
moment -1.4×10 Cm ) can be further enhanced through charge-induced forces owing to the
presence of the decorated polar groups and charged skeleton. Moreover, there might be a
synergistic effect between the above two factors. Additionally, the low adsorption affinity of 1
toward CH
4
(perhaps caused by the low polarity of CH
[24].
.4 Encapsulation of Ln ions
4
) can be confirmed by the near-linear
adsorption isotherm of CH
4
3+
3
+
3
As described above, the anionic framework of 1 contains 1D channels dispersed with H O
cations, which makes it suitable for fabrication of Ln-doped luminescent materials via
3+
encapsulation of lanthanide cations. To load the Ln cations into the pores of 1, the solid sample
-
1
of 1 was immersed in methanol/H
2 3 3
O (1/2 v/v) solution containing Ln(NO ) (0.3 molL ,50℃)
3+
for ion exchange. As confirmed by ICP date, the doped amount of Ln ions is about 8.07% for
3
+
3+
2+
Tb and 5.72% for Eu (mol% compared with Zn ions), indicating that only a few parts of
+
3+
3+
3
H O cations have been exchanged by Ln ions. The PXRD patterns of the Ln @1 samples are
almost identical with that of the as-synthesized 1 (Fig. S9), which confirmed that the crystalline
integrity of the structure was maintained upon the lanthanide adsorption. Besides, the PXRD
3
+
patterns for Ln @1 shows two additional sets of peaks at slightly different values, suggesting that
3
+
a subtle structural change happens along with the encapsulation of Ln . However, the framework
of 1 will collapse irreversibly when continue to raise the ion-exchange temperature (Fig. S10).
Fig. 7 (a) Solid-state emission spectra of H
2
NSBPDC and 1 (ex = 290 nm); (b) Emission spectra of Eu@1 (ex
327 nm).
=
2
In addition, the solid emission properties of H NSBPDC, 1 and Ln@1 were investigated at room
temperature (Fig 7). As shown in Fig. 7a, compound 1 exhibits strong blue emission with a
maximum at 450 nm upon excitation at 290 nm, which is in accordance with that of the free
H NSBPDC ligand (em = 452nm, ex = 290nm). Thus, the luminescence of 1 can be attributed to
2
3
+
the intra-ligand ( *) charge transitions. In the case of Eu @1, the emission bands at 578 nm,
3
+
5
91 nm, 614 nm, 649 nm and 694 nm are consistent with the typical Eu ion emissions (ex = 327
5
7
nm), which are ascribed to D
0
 F
J
(J = 04) transitions. The strongest emission peak at 614 nm

5
7
can be assigned to the D
0
 F
2
transition. Simultaneously, the characteristic emission of 1 at
3+
4
50nm still retained, indicating that only part of the energy is transferred from 1 to the Eu
3
+
3+
centers. As for Tb @1, the characteristic emissions of Tb were not observed probably due to the
3+
mismatch of the energy levels of 1 and Tb .
4. Conclusions
In conclusion, an new anionic MOF (1) was constructed from 4-connected tetrahedral
Zn O(COO) ] clusters and a predesigned functional ligand (H NSBPDC). Complex 1 is a 3-fold
interpenetrated diamond-like network featuring 1D ultra-microporous channels. Gas adsorption
measurements showed that the adsorption heat for CO is relatively very high, and 1 could be
suitable for selective separation of CO over CH and N . The results reveal that the molecular
sieve effect and enhanced host–guest interactions can cooperatively improve the CO capture
[
4
8
2
2
2
4
2
2
3
+
performance. In addition, 1 can adsorb La ions via a targeted ion-exchanged process to form red
luminescent materials. These results will facilitate the exploration of novel multi-functional
2
materials for selective CO adsorption and light emission.
Notes
The authors declare no competing financial interest.
Acknowledgements
This work is financially supported by the National Natural Science Foundation of China (Grant no.
21201064).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the online version,
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Graphical Abstracts
A new anionic metal-organic framework based on the [Zn
4
4 2 8
( -O)(CO ) ] clusters: selective
2
absorption of CO and luminescent response to lanthanide (III) ions
a,*
a
a
b
Ai-Ling Cheng , Juan Zhang , Ling-Ling Ren , En-Qing Gao
An anionic MOF containing ultra-microporous channels decorated with polar groups is
synthesized and its selective adsorption properties are explored.

Research Highlights



A new anionic MOF (1) based on [Zn
The structure of 1 can be dehydrated and rehydrated reversibly.
1 has good adsorption selectivity for CO over CH and N
4
(
4 2 8
-O)(CO ) ] clusters was synthesized.
2
4
2
.