A novel polyoxometalate-encapsulating 3D polycatenated metal-organic framework

Article abstract of DOI:10.1016/j.jssc.2019.120905

A novel polyoxometalate-encapsulating polycatenated metal-organic framework, (bib)_0.5[Cu₂(bib)_3.5(GeW₁₂O₄₀)]·H₂O (1) (bib = 1,4-bis(1-imidazol-yl)-2,5-dimethyl benzene), has been synthesize

Full text of DOI:10.1016/j.jssc.2019.120905

Journal of Solid State Chemistry 278 (2019) 120905
Contents lists available at ScienceDirect
Journal of Solid State Chemistry
journal homepage: www.elsevier.com/locate/jssc
A novel polyoxometalate-encapsulating 3D polycatenated
metal-organic framework
Shaobin Li a , Borong Lu , Jianjiao Xin , Li Zhang
,
*
a
b
a
,
**
, Jing Pan , Yue Chen , Xiaoguo Tan
a
a
a
a
College of Materials Science and Engineering, Qiqihar University, Qiqihar, 161006, China
College of Chemistry and Chemical Engineering, Qiqihar University, Qiqihar, 161006, China
b
A R T I C L E I N F O
A B S T R A C T
A novel polyoxometalate-encapsulating polycatenated metal-organic framework, (bib)0.5[Cu (bib)3.5(GeW12O40)]⋅
Keywords:
Polyoxometalate
Polycatenated frameworks
Entanglement compound
Electrocatalytic property
2
H
2
O (1) (bib ¼ 1,4-bis(1-imidazol-yl)-2,5-dimethyl benzene), has been synthesized under hydrothermal conditions.
In compound 1, 1D molecular ladders and 2D square grid layers is further catenated to the two adjacent such motifs
in inclined fashion to give an 1Dþ2D→3D polycatenaned metal-organic framework with nanotube channels, in
which nanosized Keggin anions as guests are encapsulated for the first time. Compound 1 represents a first case of
Keggin-type polyoxometalate-encapsulating 1Dþ2D→3D polycatenated metal-organic framework. The electro-
chemical studies show that modified electrode of 1 exhibits highly efficient electrocatalytic activity toward
-
reduction of inorganic molecule bromate (BrO
3
). The electrocatalytic reaction mechanism of 1-GCE toward
reduction of BrO-
has been illuminated. The photoluminescence property of 1 was also investigated.
3
1. Introduction
electrochemistry and catalysis [10–18]. The construction of functional
POM-based metal-organic frameworks (MOFs) is usually achieved by
Entangled systems represent one fascinating subject in the coordi-
using a one-pot synthetic method in the presence of organic linkers or
ligand-supported metal moieties [19–22]. Although scores of POM-based
MOFs have been reported, the rational syntheses of POM-based MOFs
with special structural features, such as entangled POM-based MOFs,
remain as challenges [23,24]. Such materials can be able to combine the
flexible structure feature of entanglement with the unique physical and
chemical properties of POMs, and may find broader applications in the
materials science field [25].
nation polymer. Entanglement compounds such as interpenetrating,
polyrotaxane, polycatenane and polyknotting as well as self-threading,
have attracted considerable attention due to not only their abundant
architectures and topologies, but also potential applications [1–6]. As
important members in the realm of entangled networks, polycatenated
and polyrotaxane-like networks have special structural features. As
defined by Carlucci, Ciani, and Proserpio, polycatenation can be
described as a type of entanglement in which the component motifs have
lower dimensionality than that of the resulting architectures, and each
individual motif is catenated only with the surrounding ones not with all
the others [7,8]. Although the 2D→3D parallel or inclined catenation of
layers is not very unusual, the polycatenation of different motifs is
extremely rare in both inorganic and coordination polymer chemistry
Among rapidly increased POM-based MOFs, those that show poly-
catenaned structures have been seldom observed so far. Lu et al. made an
important breakthrough in 2010, in which Keggin-type polyoxoanions
played a template role to direct formation of the silver-triazole (1,2,4-
6þ
triazole) polycatenaned framework with adamantine-like [Ag24(trz)18
]
nanocages [26]. Recently, the progress of the POM-based entangled
structures was well-documented in organized by Su, Lan and their co-
[
9].
Polyoxometalates (POMs), as a class of nanosized transitionmetal
workers, which spans
a comprehensive range and classifies the
oxide clusters, are attracting more and more interest due to their virtually
unmatched range of properties. It is this unique range of properties that
qualifies POMs as desirable building blocks for the designed construction
of functional materials with applications in, for instance, magnetism,
POM-based polycatenaned structures into three categories: (i) 0D→3D,
(ii) 1D→3D and (iii) 2D→3D, according to the dimensions of their single
motifs in these compounds [25]. However, until now, we found that all of
the reported POM-based polycatenated MOFs were constructed from
1
*
Corresponding author.
*
* Corresponding author.
E-mail addresses: qqhrlsb1022@126.com (S. Li), zhangli10227@126.com (L. Zhang).
https://doi.org/10.1016/j.jssc.2019.120905
Received 21 June 2019; Received in revised form 8 August 2019; Accepted 8 August 2019
Available online 8 August 2019
0022-4596/© 2019 Elsevier Inc. All rights reserved.

S. Li et al.
Journal of Solid State Chemistry 278 (2019) 120905
identical motifs catenaned interact on each other [27]. The example of
POM-based polycatenated MOFs constructed by different motifs is not
observed so far. Consequently, the construction of new kinds of
POM-based polycatenated MOFs is still a difficult task in POM chemistry.
With this aim in mind, we chose a straight, rigid N-containing ligand
bib (1,4-bis(1-imidazol-yl)-2,5-dimethyl benzene) and Keggin-type pol-
3. Results and discussion
3.1. X-ray crystallography
Single crystal X-ray diffraction data collection of 1 was performed
using a Bruker Smart Apex CCD diffractometer with Mo-Ka radiation
(λ ¼ 0.71073 Å) at 293 K. Absorption corrections were applied by using
the multi-scan program SADABS [28]. The structures were solved by
direct methods, and non-hydrogen atoms were refined anisotropically by
least-squares on F2 using the SHELXTL program [29]. The hydrogen
atoms of organic ligands were generated geometrically for 1. During the
refinement, the command “ISOR” was used to restrain the non-H atoms
with ADP and NPD problems. A summary of the crystal data, data
collection, and refinement parameters for 1 are listed in Table 1. The
selected bond lengths and angles for 1 are listed in Table S1. Crystallo-
graphic data for the structures reported in this paper have been deposited
in the Cambridge Crystallographic Data Center with CCDC Number:
4ꢀ
yanion (GeW12O40 ) in our synthetic strategy, based on the following
considerations: (i) straight rigid, when coordinated with transition-metal
ions, have shown the ability to produce 1D ladders and 2D square grid
layers, which contribute to forming polycatenated networks. (ii) Keggin
POMs not only possess orbicular shapes, as templates directing to the
formation of porous polycatenated networks with adjustable sizes, but
also exhibit reversible uptake of 24-electrons, and the fast, reversible
multi-electron transfer demonstrated by POMs makes them well suited
for electrocatalysts. Fortunately, this effort has led to the isolation of the
first Keggin-type polyoxometalate-encapsulating 1Dþ2D→3D poly-
catenated metal-organic framework.
1935349.
2. Experimental section
3.2. Structure description of compound 1
2
.1. Materials and general methods
Green block crystals of compound 1 were obtained by heating a
All of chemicals were commercially purchased and used without
mixture of H
hydrothermal conditions. The formula of the product was determined to
be (bib)0.5[Cu (bib)3.5(GeW12 40)]⋅H O on the basis of the combined
4 2 2 4 3
GeW12O40, CuCl ⋅2H O, bib and NH VO in water under
purification. Elemental analyses (C, H and N) were performed on a Per-
kinElmer 2400 CHN Elemental Analyzer, and that of Cu and W were
carried out with a Leaman inductively coupled plasma (ICP) spectrom-
eter. The FT-IR spectrum was recorded from KBr pellets in the range
2
O
2
results of X-ray single-crystal structure analysis, elemental analysis and
X-ray photoemission spectrum (XPS). Single crystal X-ray diffraction
analysis reveals that 1 is a polyoxometalate-encapsulating 1Dþ2D→3D
polycatenated metal-organic framework. It crystallizes in the monoclinic
-
1
4
000–400 cm with a Nicolet AVATAR FT-IR360 spectrometer. The
powder X-ray diffraction (PXRD) data were collected on a Rigaku
RINT2000 diffractometer at room temperature. X-ray photoelectron
spectroscopy (XPS) was measured on a spectrometer (Escalabmkii, Model
space group P2
1
/n. The asymmetric unit of 1 includes one Keggin cluster
4-
[
GeW12O ] (abbreviated to GeW12), two Cu cations, four bib ligands
40
2
50) with an Al K (1486.8 eV) achromatic X-ray source. The nitrogen
and one free water molecular (Fig. S2). There are two crystallographi-
cally independent Cu ions with two kinds of coordination modes
Fig. S3). Cu1 is six-coordination in distorted octahedral geometry, and
achieved by two oxygen atom (O10, O20) from the GeW12 anion and four
nitrogen atoms (N9, N11, N12 and N14) from four bib ligands. Cu2 is
four-coordination in a “seesaw” geometry, and achieved by two oxygen
atoms (O6 and O22) from the GeW12 anions and two nitrogen atoms (N7
and N13) from two bib ligands (Fig. S3).
adsorption-desorption isotherms of the samples were conducted by using
a Micromeritics TriStar II 3020. All the electrochemical measurements
were carried out on Metrohm PGSTAT 128 N electrochemical worksta-
tion using modified GCE (d ¼ 3 mm) served as the working electrode in
electrochemical experiments, a platinum wire as the counter electrode,
and a Ag/AgCl electrode as the reference electrode, respectively.
(
2
.2. Synthesis of compound 1
One structural feature of 1 is the unusual 1Dþ2D→3D polycatenated
metal-organic frameworks constructed by the 1D molecular ladder and 2D
4
A mixture of H GeW12
2 2
O40 (0.32 g, 0.17 mmol), CuCl ⋅2H O (0.16 g,
0
.9 mmol), bib (0.06 g, 0.25 mmol), NH
4
VO (187 mg, 1.6 mmol), and
3
Table 1
water (10 mL) was stirred for 1 h. The resulting solution was transferred
to a Teflon lined autoclave and kept under autogenous pressure at 170 C
ꢁ
Crystal data and structure refinements for 1.
for 4 days with a pH ¼ 3.8 adjusted by 3 M HCl. After slow cooling to
room temperature, green block crystals of 1 were filtered, washed with
distilled water and dried at room temperature (Yield, 53%, based on W)
Compound
1
Formula
Formula weight
Crystal system
Space group
a/Å
C
56 2 41 12
H58Cu GeN16O W
4014.96
Monoclinic
P2(1)/n
15.140(5)
24.343(5)
24.332(5)
99.411(5)
8847(4)
4
3.014
293(2)
16.424
51313
(
Fig. S1). The reproducibility of 1 is good. The final pH value of the so-
lution after the reaction is approximate to 4.0. Anal. Calcd for
58Cu GeN16 12: C 16.74, H 1.45, N 5.58, Cu 3.16, W 54.92%;
Found: C 16.83, H 1.52, N 5.68, Cu 3.23, W 55.21%.
C
56
H
2
41
O W
b/Å
c/Å
ꢁ
β/
3
V/Å
2
.3. Preparation of working electrode
Z
D
calcd/g cm-3
A mixture of 2 mg of carbon black and the desired amount of samples
T/K
(
2 mg) was co-grounded for 45 min. Prior to be modified, the GCE was
μ
/mm-1
Refl. Measured
Refl. Unique
polished carefully with 0.05 m alumina powders and then cleaned with
μ
16019
0.0541
1.055
0.0417/0.1083
deionized water. Catalyst ink was prepared by mixing 4 mg of the pre-
pared catalyst powders into water (0.25 ml) and ethanol (0.75 ml) then
ultrasonically dispersed for 40 min. Then, an aqueous dispersion was
R
int
2
GoF on F
R1/wR2 [I ꢂ 2
σ
(I)]
transferred onto the washed GCE (5
perature before electrochemical experiments.
μ
L) and dried in air at room tem-
P
P
R
1
¼
kF
o
k–jF
c
2
k/ jF
o
j.
P
P
2
2
2)2]1/2.
wR
2
¼
[w(F
o
─F
c
) ]/ [w(F
o
2

S. Li et al.
Journal of Solid State Chemistry 278 (2019) 120905
44
-sql layer, which can be described as follows: (i) On the one hand, Cu1
the bib ligand and water molecule. The PXRD patterns for 1 are presented
in Fig. S9. The diffraction peaks of both simulated and experimental
patterns match well in key positions. The difference in reflection in-
tensities between the simulated and the experimental patterns may be
due to the different preferred orientation of the powder samples.
atoms alternately connect
2
μ -mode bib ligands leading to a (4, 4)-con-
nected 2D Cu1-bib layer with quadrangular windows (The dimension of
each window is ca. 13.254 ꢃ 13.342 Å, Fig. 1b). There exist the left- and
right-handed helical chains running along the [100] direction with an
identical screw-pitch of ca. 24.32 Å (Fig. 1a). On the other hand, Cu2
atoms connect one
forming a Cu (bib)
μ
2
-mode bib ligand and two
μ
1
-mode bib ligands
3.3.3. BET measurements
2
3
fragment. The adjacent Cu (bib)
2
3
fragment connect by
2
The BET measurement of 1 has been investigated. The N adsorption-
intermolecular hydrogen bondings (C13ꢀH13⋯N7 ¼ 2.458 Å), a 1D mo-
lecular ladder with the dimension of 13.542 ꢃ 15.117 Å was constructed
desorption isotherm of 1 shows a typical type IV isotherm with a hys-
teresis loop (Fig. S10). The BET surface area was estimated to be 84.4
2
-1
(
Fig. S4). Interestingly, 1D molecular ladders and 2D square grid layers is
m g . Meanwhile, the porosities of 1 are calculated by a PLATON pro-
grams [34]. Calculations using PLATON reveal that the effective free
further catenated to the two adjacent such motifs in inclined fashion via
one loop links to give an 1Dþ2D→3D polycatenaned metal-organic
framework with nanotube channels along a axis, the channels possess
approximate dimensions of 15.117 ꢃ 14.175 Å(Fig. 2a and Fig. S5). The
topology of 1Dþ2D→3D polycatenaned MOF has been presented in
Fig. 2b.
3
3
volume is 660.4 Å equal to 7.5% of the crystal volume 8847.0 Å for 1.
The structure of polycatenated metal-organic framework encapsulated by
GeW12 clusters in 1 with proper BET surface could enhance electro-
catalytic activity.
Interestingly, the GeW12 polyanions acting as four-connected tem-
plates are encapsulated into the square windows of nanotube channels
and connect the 1D þ 2D→3D polycatenated framework via sharing four
Cu ions (Fig. 3). In previously reported cases of polycatenations, even
more rare are the cases of polycatenation of motifs of different dimen-
sionality (1Dþ2D→3D). Compound 1 represents a first case of Keggin-
type polyoxometalate-encapsulating 1Dþ2D→3D polycatenated metal-
organic framework.
3
.4. Voltammetric behavior of 1-GCE
The POMs possess the ability of undergoing reversible multi-electron
redox processes, which makes them very attractive in chemically-
modified electrode and the electrocatalytic study [35]. The cyclic vol-
tammetric behavior for 1-GCE was studied in 1 M H
In the potential range of -0.65 to 0.40 V, there exist three redox peaks
2 4
SO solution (Fig. 4).
0
0
with half-wave potentials E1/2 at -0.12 V(II-II ), -0.38 V(III-III ) and
0.52 V (IV-IV’), which can be ascribed to redox processes of three
-
two-electron tungsten-centered [36,37]. In addition, there is one irre-
3
3
.3. Analyses of BVS, XPS, IR, PXRD and BET
versible anodic peak (I) at þ0.18 V, which is assigned to the oxidation of
II
I
one-electron copper-centered (Cu → Cu ) in 1 [38,39]. As shown in the
.3.1. BVS and XPS
In 1, all W atoms are in þVI oxidation state obtained by BVS calcu-
-1
insert of Fig. 4, when the scan rates are varied from 0.05 to 0.25 V s , the
peak potentials change gradually: the cathodic peak potentials shift to-
ward the negative direction and the corresponding anodic peak poten-
tials to the positive direction with increasing scan rates. The peak
currents are proportional to the scan rate, which indicate that the redox
processes are surface-controlled [40].
lation [30]. All Cu atoms are in the þII oxidation state, confirmed by their
octahedral coordination environments, green block crystal color and BVS
calculation. The XPS spectrum exhibits that 1 contains W, C, N, O and Cu
atoms (Fig. S6). As shown in Fig. S7, the XPS high-resolution Cu2p
(
934.2, 943.5, 954.2 and 963.6 eV) peaks and W4f (35.3 and 37.5 eV)
peaks further confirms the oxidation states of Cu(II) and W(VI) in 1 [31].
ꢀ
3.5. Electrocatalytic reduction of BrO
3
3
.3.2. IR spectrum and XRD measurements
The IR spectra of compound 1, H GeW12
ꢀ
4
O40 and bib ligand are shown
Bromate (BrO
3
), a disinfection by-product, is formed when ozone
in Fig. S8. From the results of IR spectra analysis, the characteristic peaks
(used to disinfect drinking-water) reacts with naturally occurring bro-
mide in drinking water [41]. BrO ions are suspected to act as carcino-
3
gens that may cause a range of cancers [42]. Solid state electrochemistry
at 967, 892, 807 and 751 cm- in 1 are attributed to
1
ν
as(W¼Ot),
ν
as(Ge–O),
ν
as(W–Ob) and
ν
as(W–Oc) from GeW12 clusters [32]. The
-1
characteristic peaks in the region of 1625–1068 cm could be ascribed to
was carried out by entrapping the compound in a GCE. The catalytic
ꢀ
the character peaks of bib ligand [33]. Furthermore, the character peaks
activity of 1-GCE towards BrO
3
reduction was examined, as shown in
ꢀ1
ꢀ
between 3081 and 3435 cm can be assigned to
υ(C-H) and
υ(O-H) of
Fig. 5. With the addition of BrO
3
, the cathodic peak IV substantially
4
Fig. 1. (a) The left-handed and right-handed helical chains. (b) A 2D 4 -sql layer connected by helical chains.
3

S. Li et al.
Journal of Solid State Chemistry 278 (2019) 120905
Fig. 2. (a) Details of the 1Dþ2D→3D polycatenated metal-organic framework. (b) The schematic view of polycatenated metal-organic framework in compound 1.
Fig. 3. (a) The GeW12 polyanions act as a 4-connected template in compound 1. (b) polyoxometalate-encapsulating 1Dþ2D→3D polycatenated metal-
organic frameworks.
GeWVI12
O
4ꢀ
-
GeWVI10WV
-
4ꢀ
(1)
(2)
(3)
2
2
O
40
GeWVI10WV
GeWVI
WV
4ꢀ
40
H
H
2
4
4
8
4
O
GeWVI
WV
40 þ 2Hþ þ 2e → H
-
GeWVI
WV
4ꢀ
40
8
6
6
6
O
Catalytic chemical steps:
GeWVI
WV
O
44 ꢀ0 þ BrO-
→ GeWVI12
O
4ꢀ
-
(4)
H
6
6
6
3
2
O
Additionally, the stability experiment for 1-GCE has been investi-
gated scanning for 100 cycles in 1 M H SO solution. As shown in
2
4
Fig. S11, it can be seen that the electrode exhibits almost no loss in the
current signal after 100 cycles.
3.6. Photoluminescent properties
The photoluminescence property of compound 1 was investigated in
the solid state at room temperature (Fig. 6). Further, in order to under-
stand the nature of the luminescence, the emission spectrum of bib ligand
was also investigated under identical experimental conditions. The bib
ligand displays photoluminescence with emission maxima ca. 421 nm
Fig. 4. Cyclic voltammograms for 1-GCE in 1 M H
rates (from inner to outer): 0.05, 0.10, 0.15, 0.20, 0.25 V s . The inset shows
plots of the anodic and the cathodic peak currents for II-II , III-III and IV-IV
againt scan rates.
2 4
SO solution at different scan
-
1
0
0
0
(λex ¼ 362 nm), and this emission band can be assigned to
π–π* transi-
tions of bib [46]. It is clear that there is one similar emission peaks at ca.
463 nm (λex ¼ 368 nm) for compound 1. Compared to the free bib ligand,
we can observe that the emission spectrum of compound 1 is red-shifted.
The emission peak intensity and red-shift of 1 compared to the bib ligand
can be attributable to ligand-to-metal charge transfer and/or the intra-
increased, while the corresponding anodic peak currents decreased. The
electrocatalytic efficiency of 1-GCE (based on calculation using CAT
ꢀ
formula) [43] toward the reduction of BrO
3
was ca. 96.7% containing
ꢀ
0
.8 mM BrO
3
. The electrocatalytic reaction mechanism of 1-GCE toward
can be described by the following equations (1)–(4) [44,45]:
-
BrO
3
ligand (π*-π) fluorescent emission [47–50].
Electrochemical reactions:
4

S. Li et al.
Journal of Solid State Chemistry 278 (2019) 120905
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://do
i.org/10.1016/j.jssc.2019.120905.
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