An unprecedented "strongly" self-catenated MOF containing inclined catenated honeycomb-like units

Article abstract of DOI:10.1039/c5dt04679c

A 3D 4-coordinated self-catenated metal-organic framework {[Co(bibp)(1,4-chdc)]·2H₂O}_n (1) (bibp = 4,4′-bis(1-imidazolyl)biphenyl, 1,4-H₂chdc = 1,4-cyclohexanedicarboxylic acid) has been synthesized by hydrothermal reaction and its structure has been determined. This framework buries an unprecedented 4-coordinated self-catenated net that can be represented as an array of honeycomb-like units catenated in an inclined mode, with the highest topological density among the 4-coordinated nets that occur in crystal structures. Additionally, the thermogravimetric, photo-catalytic and electrochemical behaviors have been investigated.

Full text of DOI:10.1039/c5dt04679c

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An Unprecedented Densely SelfꢀCatenated Metal−Organic Framework
Containing Inclined Catenated Honeycombꢀlike Units with the Highest
Topological Density among 4ꢀCoordinated Nets
a
b
c
c
a,
JuꢀMeng Hu , Vladislav A. Blatov , Baoyi Yu , Kristof Van Hecke , GuangꢀHua Cui *
5
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5
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DOI: 10.1039/b000000x [DO NOT ALTER/DELETE THIS TEXT]
A 3D 4ꢀcoordinated selfꢀcatenated metal–organic framework
view，the topological nets built from 4ꢀcoordinated (4ꢀc) nets
1
1
2
{[Co(bibp)(1,4ꢀchdc)]·2H O}
(1)
(bibp
1,4ꢀH chdc
=
=
40 draw much attention both thanks to their practical significance
(all zeolites are 4ꢀc nets) and from a theoretical point of view:
many 4ꢀc nets have been deduced and summarized, firstly by
2
n
4
1
,4´ꢀbis(1ꢀimidazolyl)biphenyl,
,4ꢀcyclohexanedicarboxylic acid) has been synthesized under
2
4
5
hydrothermal reaction and its structure has been determined.
This framework buries an unprecedented 4ꢀcoordinated
selfꢀcatenated net that can be represented as an array 45 natural structures of ice IV and coesite, and the latter has been
Wells, followed by several comprehensive discussions. Two
known examples of 4ꢀcoordinated selfꢀpenetrating nets are the
6
honeycombꢀlike units catenated in an inclined mode, with the
highest topological density among the 4ꢀcoordinated nets that
occurred in crystal structures. Additionally, the
thermogravimetric, photoꢀcatalytic and electrochemical
behaviors have been investigated.
mimicked in [Ag(2ꢀethpyz) ][SbF ] (2ꢀethpyz=2ꢀethylpyrazine).
2 6
Recently, Gong et al. reported two metal–organic frameworks
built by an amide derivative and organodicarboxyl coꢀligands,
5
exhibiting 3ꢀfold interpenetration of 6 .8ꢀmok nets, which are
7
50 4ꢀcoordinated selfꢀcatenated. As has been proved, by using the
coꢀligands of an exoꢀbidentate Nꢀheterocycle and dicarboxylate
ligands, together with the suited transition metal ions, it is
possible to synthesize the selfꢀcatenated MOFs. As our
The rational design and syntheses of metal–organic
frameworks (MOFs) have attracted particular interest due to their
fascinating structural complexity and potential application in
8
continuing efforts, we herein report a new 3D 4ꢀcoordinated
1
electrochemistry, catalysis, gas sorption and magnetism. In the
5
6
6
5
0
5
selfꢀcatenated
MOF
{[Co(bibp)(1,4ꢀchdc)]·2H O}
(1)
2
n
2
3
3
5
0
5
realm of MOFs, topology control is fundamental for determining
(
1,4ꢀH chdc
=
1,4ꢀcyclohexanedicarboxylic acid; bibp
=
2
2
the properties and applications of the crystalline materials.
4
,4´ꢀbis(1ꢀimidazolyl)biphenyl), which is an unprecedented
Therefore, the structural investigation of intricate entangled
structures for coordination frameworks, such as the most familiar
interpenetrating nets, selfꢀpenetrating nets, polyrotaxane
structures etc. has attracted great attention. Selfꢀcatenated
framework structures are a subclass of entanglements with
“strongly” selfꢀcatenated MOF and provides the highest
topological density for the 4ꢀcoordinated nets that occurred in
9
crystal structures up to now. The bibp ligand was prepared
1
0
according to the previously reported synthetic procedure.
Compound was prepared by hydrothermal reaction,
performed in a 25 mL Teflonꢀlined stainless steel vessel at
40 °C for 72 h.‡ Singleꢀcrystal Xꢀray diffraction analysis
1
3
fascinating topological properties. These species are single nets,
but have the peculiarity that the smallest topological rings are
catenated by the other smallest rings belonging to the same
network. However, the study of selfꢀcatenated networks, being
considered as extended periodic equivalents of molecular knots,
1
reveals that compound 1§ is a 3D coordination polymer, which
crystallized in the monoclinic space group C2/c. The asymmetric
unit consists of one Co(II) ion, two distinct half molecules of the
3
a
2
ꢀ
remains largely unexplored.
bibp ligand, two different half ligands of the 1,4ꢀchdc anion,
with e,eꢀtransꢀconformation and e,eꢀcisꢀconformation,
From both zeolite chemistry and crystal engineering points of
a
70 respectively, as well as two lattice water molecules. As depicted
in Figure 1a, the Co(II) center is tetraꢀcoordinated and shows a
distorted [CoN O ] tetrahedral geometry, ligated by two
College of Chemical Engineering, North China University of Science
and Technology, 46 West Xinhua Road, Tangshan, 063009, Hebei, PR
China Fax: +86ꢀ0315ꢀ2592170; Eꢀmail: tscghua@126.com
b
2
2
Samara Center for Theoretical Materials Science (SCTMS), Samara
carboxylato oxygen atoms (O2, O3) from two different
State Aerospace University named after academician S.P. Korolyev
(
2–
National Research University), Moskovskoye Shosse 34, Samara 443086,
1,4ꢀchdc ligands and two nitrogen atoms (N1, N3) from two
Russia. Eꢀmail: blatov@samsu.ru
7
5
distinct transꢀcoordinated bibp ligands with Co–N distances of
c
Department of Inorganic and Physical Chemistry, Ghent University,
2
.018(4) Å and 2.050(4) Å. The Co1–O bond lengths are 1.990(4)
Krijgslaan 281 S3, Bꢀ9000 Ghent, Belgium
†
Electronic Supplementary Information (ESI) available: Electrochemical
Å and 2.016(4) Å, respectively, and the coordination angles
around Co1 hold within the range of 90.89(16)–122.41(18)°,
which is in accord with previously reported values for Co(II)
experiment, Catalysis Experiments, the topology of 1, selected bonds and
angles, FTIR, TGA, XRPD, UV/Vis absorption spectrum of 1, and the
absorption
spectra
of
the
MO
solution.
See
11
http://dx.doi.org/10.1039/b000000x/
80 complexes.
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In 1, the bibp ligands adopt a bisꢀmonodendate bridging mode,
linking the adjacent Co atoms together, and further assemble into
an infinite 1D [Co(bibp)] zigzag chain with Co···Co distances of
n
1
7.691 Å and 18.035 Å, respectively, and a Co···Co···Co angle
5
of the infinite 1D chain of 79.637° (Figure 1b). The 1D
2–
[
Co(bibp)]n chains are further linked through e,eꢀtransꢀchdc
1
1
ligands, acting in a ꢁ ꢀη :η coordination mode to result in the
2
3
formation of a 2D 6 ꢀhcb network (Figure 1c). There are
7
8ꢀmembered macrocycles in the 2D sheet, formed by four bibp
2
ꢀ
10
and two e,eꢀtransꢀchdc ligands together with six Co(II) atoms.
Furthermore, such 2D layers are extended by e,eꢀcisꢀchdc
ligands with a Co···Co distance of 10.8196(11) Å to complete the
2–
1
2
Fig. 2 A fragment of the underlying net cgh5. The fragments formed by
ꢀ and 10ꢀmembered rings are highlighted by different colors.
complicated 3D framework structure (Figure 1d).
6
The selfꢀcatenation can be conceived with the procedure of the
network decomposition, which we have already used for other
14
selfꢀcatenated structures.
The procedure consists in
a
4
4
5
0
5
0
subsequent breaking of independent edges (links) of the network,
until it is split into motifs that are not selfꢀcatenated. In case of
cgh5, this procedure gives the only way of such kind of splitting:
breaking bonds with one of the dicarboxylate ligands leads to two
_
sets of honeycombꢀlike layers (311) and (311) that cross each
other in an inclined fashion and form a polycatenated 3D array
(Figure 3). Recently, we have already obtained a 4ꢀcoordinated
selfꢀcatenated net that also contains catenated honeycomb layers,
14a
but in a parallel mode. Probably, the inclined catenation of the
layers, which favors their close arrangement, is the reason of the
high topological density of the net.
Fig. 1 (a) Coordination environment around the Co(II) centers in the
complex 1. Hydrogen atoms are omitted for clarity. Symmetry codes: A:
ꢀx+1/2, ꢀyꢀ1/2, ꢀz; B: ꢀx, ꢀy, ꢀz+1; C: ꢀx, ꢀy+1, ꢀz; D: ꢀx+1, y, ꢀz+1/2; (b) A
view of the 1D zigzag chain by bibp ligands and Co(II) centers; (c) The
3
2
1
D 6 ꢀhcb layer network of 1. (d) 3D packing of 1 constructed from bibp,
2ꢀ
,4ꢀchdc ligands and Co(II) ions.
The coordination network was simplified and analyzed with
1
3
1
2
2
3
3
5
0
5
0
5
the ToposPro program package. We have used the standard
simplification mode, with the Co(II) atoms and organic ligands
were treated as the nodes of the underlying net. Since all the
ligands are bridging they were transformed to edges of the
simplified net, which became uninodal, i.e. only the metal centers
remained as nodes. Each metal center is connected to four ligands,
i.e. the resulting underlying topology is 4ꢀcoordinated. It has the
Fig. 3 Representation of the cgh5 underlying net as an inclined
_
polycatenation of two sets of honeycombꢀlike layers (311) and (311). The
links between the layers are shown as dashed lines.
3
3
point symbol {6 .10 } and vertex symbol (6.10 .6.10 .6.10 )
and has never occurred before in any crystal structure according
to the TOPOS TTD Collection. Furthermore, there are no other
4ꢀcoordinated nets that are even locally similar to this net by the
method of mutual connection of the rings. We have deposited this
1
2
12
12
ꢀ
1
The IR spectrum between 400 and 4000 cm (Figure S1†)
1
3
ꢀ1
exhibits two characteristic bands at 1592 and 1381 cm attributed
to the vCOO asymmetric and symmetric stretching vibration. The
OꢀH stretching broad band of the crystalline water is observed at
ꢀ
1
topology under the name cgh5. A close inspection of the network 55 3416 cm . The characteristic bands for the bibp ligand are at
ꢀ
1
showed that it is strongly catenated; all 6ꢀ and 10ꢀmembered
rings of the nodes are crossed by other rings (Figure 2). Moreover,
the strong selfꢀcatenation provides an extremely high topological
density: TD10 = 5035, which is the number of nodes within the
first 10 coordination spheres of a given node. Up to now this is 60 has lost all lattice water molecules (6.40 % obsd; 6.52 % calcd).
the highest value for the 4ꢀcoordinated nets that occur in crystal
structures; according to the RCSR database the leaders are the
elv net (TD10 = 21922) and the ten net (TD10 = 6747), but both of
them were discovered in modeled structures.
1513, 1305 and 1066 cm , which can be assigned to the νC=C
C=N stretching vibration.
The thermal gravimetric curve of complex 1 exhibits two steps
of weight loss (Figure S2†). In the first region of 72−116 °C, it
,
ν
From 118 to 355 °C, the TGA curve of complex 1 passes through
a plateau region, after which the material undergoes a rapid
decomposition. The second step with a mass loss of 80.19 %
occurs in the temperature region of 355−592 °C, corresponding
1
0
3
c
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to the burning of the organic ligands (79.89 % calcd). The
remaining weight corresponds to the formation of CoO (13.41 %
obsd; 13.59 % calcd). Therefore, this material displays rather 40 oxidizing sulfate radicals (SO ·) and further increase the
changed obviously, from red to light pink or even colorless. The
complex can catalyze persulfate to produce more strongly
ꢀ
4
high thermal stability after removal of the water solvates and that
might be attributed to the high selfꢀcatenation.
The electrochemical behavior of the 1ꢀmodified carbon paste
efficiency of the pollutant degradation significantly in the
photoꢀFentonꢀlike process. For the sake of comparison, the total
catalytic degradation efficiency of the control experiment without
catalyst and equimolar amount of CoCl ·6H O as catalyst only
5
0
5
0
5
electrode (1ꢀCPE) in 1.0 M H SO4 aqueous solution under
2
2
2
different scan rates was investigated. Before the experiments, the 45 reached 14.21% and 21.40%, respectively, which indicated that
phase purity of the sample was confirmed by a comparison of
experimental and simulated powder Xꢀray diffraction. The
diffraction peaks of the experimental and simulated patterns are
well matched in key positions, indicating phase purity of the bulk
there is almost no reaction going on between the persulfate and
methyl orange. Additionally, after successive cycles for
degradation experiments under the same conditions, the
photoꢀcatalytic activity of residual amount of catalyst (1) was
1
1
2
2
samples (Figure S3†). It can be seen from Figure 4 that in the 50 slightly decreasing due to leaching of metal ion, however it still
potential range from 600 to ꢀ400 mV, there is no redox peak at
the bare CPE. Nevertheless, a redox couple was observed at the
modified 1ꢀCPE, which should be attributed to the redox of
can be well considered that the residual catalyst of 1 and the
crystals used for powder Xꢀray diffraction are homogeneous
(Figure S3†). Therefore, the complex exhibits higher stability and
reproducibility for the degradation of methyl orange in the
III
II 15
Co /Co . The mean peak potential E1/2 = (E +E )/2 is 31mV
(
pa
pc
ꢀ
1
100 mVs ). It is wellꢀknown that the scan rate has a remarkable 55 photoꢀFentonꢀlike process.
influence on the electrochemical property. With the scan rates
ꢀ
1
increasing in the range from 20 to 250 mVs , the reduction peak
potentials shifted to the negative direction and the relevant
oxidation peak potentials shifted to the positive direction. The
redox peak currents are proportional to the scan rates, which
demonstrate that the redox of 1ꢀCPE is a surfaceꢀconfined
16
process.
Fig. 5 Experimental results of the catalytic degradation of methyl orange.
In summary, a 3D 4ꢀconnected coordination network with
3
3
unusual {6 .10 } cgh5 topology has been synthesized and
topologically analyzed. This coordination framework shows a
strongly selfꢀcatenated structure, containing inclined catenated
honeycombꢀlike units with the highest topological density for
6
6
7
0
5
0
4
ꢀcoordinated nets that occur in crystal structures. Additionally,
Fig. 4 Cyclic voltammograms of the 1ꢀCPE in 1.0 M H
2 4
SO aqueous
this coordination polymer displays higher thermal stability and
favorable photoꢀcatalytic capacities, as well as the
electrochemical activity.
solution at different scan rates (from inner to outer: the bare CPE, 20, 40,
ꢀ1
6
0, 80, 100, 120, 140, 160, 180, 200, 250 mV s ). The inset shows the
plots of the anodic and cathodic peak currents against scan rates.
We thank the financial support by the National Natural Science
The UVꢀassisted photocatalytic experiments for degrading
methyl orange (MO) were carried out and the detailed
photoꢀFentonꢀlike process is given in the supporting
Foundation
FoundationꢀSteel and Iron Foundation of Hebei Province
(B2015209299), the Hercules Foundation (project
of
China
(51474086),
Natural
Science
17
information. The diffuseꢀreflectance UVꢀvis spectrum of 1
reveals the absorption features in the UV region (Figure S4†). As
shown in Figure S5†, the absorption peak of MO decreased
obviously with increasing reaction time for 1 under UV
irradiation. It can be clearly seen that the rapid degradation
ensues and degradation efficiency can reach 76.1% for 1 within
30 min; after which methyl orange oxidation proceeds at a
reduced rate, reaching up to 92.8% for 1 in 120 min in the
photoꢀFentonꢀlike process (Figure 5). The color of the solution
AUGE/11/029‘‘3DꢀSPACE: 3D Structural Platform Aiming for
Chemical Excellence’’) and the Research Fund–Flanders (FWO).
3
0
Notes and references
‡Synthesis of 1: The mixture of CoCl
,4ꢀH chdc (0.20 mmol, 33.6 mg), bibp (0.10 mmol, 28.6 mg), NaOH
0.40 mmol, 16.0 mg) and distilled water (10mL) was stirred under
2 2
·6H O (0.2 mmol, 47.6 mg),
1
2
35
(
7
5
ambient conditions until it was homogeneous, and was then sealed in a 25
mL Teflonꢀlined stainless steel vessel and heated at 140 °C for 72 h. After
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slowly cooling to room temperature, purple block crystals of 1 were
collected in 16% yield (based on bibp). Anal. Calcd. for C26H28CoN O : C,
4 6
35 5. (a) M. O’keeffe, N. Brese, Acta Crystallogr., Sect. A: Found.
Crystallogr., 1992, A48, 663. (b) M. O’keeffe, Acta Crystallogr.,
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Crystallogr., Sect. A: Found. Crystallogr., 1995, A51, 916.
5
6.63; H, 5.12; N, 10.16. Found: C, 56.45; H, 5.06; N, 10.01.
Crystal data for 1: C26 , M = 551.45, Monoclinic C2/c, a =
= 90°,
= 90°, V = 5170.9(3) Å , ρ = 1.417 g cm . Final R = 0.0632,
= 0.1565 (for I > 2σ), GOF = 1.086, and Z = 8. CCDC 1420840. For
crystallographic data in CIF or other electronic format see DOI:
0.1039/********.
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Graphical Abstract
An Unprecedented Densely SelfꢀCatenated Metal−Organic Framework
Containing Inclined Catenated Honeycombꢀlike Units with the Highest
Topological Density among 4ꢀCoordinated Nets
a
b
c
c
a,
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JuꢀMeng Hu , Vladislav A. Blatov , Baoyi Yu , Kristof Van Hecke , GuangꢀHua Cui *
A 3D 4ꢀcoordinated selfꢀcatenated metal–organic framework {[Co(bibp)(1,4ꢀchdc)]·2H O} (1) (bibp =
2
n
4
,4´ꢀbis(1ꢀimidazolyl)biphenyl, 1,4ꢀH chdc = 1,4ꢀcyclohexanedicarboxylic acid) has been synthesized under
2
hydrothermal reaction. This framework buries an unprecedented 4ꢀcoordinated selfꢀcatenated net that can be
represented as an array honeycombꢀlike units catenated in an inclined mode, with the highest topological density
among the 4ꢀcoordinated nets that occurred in crystal structures. Additionally, the thermogravimetric, photoꢀcatalytic
and electrochemical behaviors have been investigated.
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This journal is © The Royal Society of Chemistry [year]
Dalton Transactions, [year], [vol], 00–00
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