Three new polycatenation networks based on 4,4′-oxybis(benzoate) and Bis(imidazole) Ligands: Synthesis, structure and photoluminescence

Article abstract of DOI:10.1002/ejic.201000832

In this paper we report three new metal-organic frameworks (MOFs), [Zn(oba)(L1)_0.5(H₂O)]_n (1), [Zn ₂(oba)₂(L2)₂](H₂O)₃ (2) and [Co(oba)(L1)]_n (3) [oba = 4,4

Full text of DOI:10.1002/ejic.201000832

FULL PAPER
DOI: 10.1002/ejic.201000832
Three New Polycatenation Networks Based on 4,4Ј-Oxybis(benzoate) and
Bis(imidazole) Ligands: Synthesis, Structure and Photoluminescence
Yun Xu,[a] Pang-Kuan Chen,[a] Yun-Xia Che,[a] and Ji-Min Zheng*[a]
Keywords: Metal-organic frameworks / Structure elucidation / Luminescence / Polycatenation
In this paper we report three new metal–organic frameworks
(MOFs), [Zn(oba)(L1)0.5(H2O)]n (1), [Zn2(oba)2(L2)2](H2O)3 (2)
and [Co(oba)(L1)]n (3) [oba = 4,4Ј-oxybis(benzoate), L1 = 1,4-
bis(imidazol-1-ylmethyl)benzene, L2 = 1,4-bis(imidazol-1-
yl)benzene] that have been obtained under hydrothermal
conditions and characterized by single-crystal X-ray diffrac-
tion, powder X-ray diffraction (PXRD), infrared spectroscopy
(IR), thermogravimetric analysis (TGA) and elemental analy-
sis (EA). A structural investigation revealed that all three co-
ordination compounds present polycatenation features. Inter-
estingly, 1 shows a rare 1DǞ2D structure formed by the cat-
enation of 1D ladders. Both 2 and 3, however, are unusual
cases that have 3D frameworks constructed from 2D 44-sql
layers by parallel polycatenation. The photoluminescence
properties of 1 and 2 have also been investigated.
preparation of desired compounds. Typically, the poly-
catenation system is generated from the presence of a large
free space within the single net.[13,14a,14b] It is recognized
that the formation of a polycatenation system is favourable
when a flexible long ligand is applied.[16] Taking into ac-
count these considerations, we employed 4,4Ј-oxybis(benzo-
ate), which has proven to be an ideal ligand for forming
interpenetrating networks due to the flexible nature of the
–O– spacer between the two phenyl groups and its variabil-
ity in coordination modes.[17,18] To pursue the possibility of
increasing the dimensionality, two neutral N-donor ligands
(L1 and L2) were chosen for our synthetic strategy because
they have different chain lengths and potential bendability
in terms of their molecular structures (Scheme 1). As a con-
tinuation of our work on entangled networks,[16d,19] we
herein report three new polycatenation networks, [Zn-
(oba)(L1)0.5(H2O)]n (1), [Zn2(oba)2(L2)2](H2O)3 (2) and
[Co(oba)(L1)]n (3). Compound 1 exhibits 1DǞ2D poly-
catenation and is quite distinct from 2 and 3, which are two
rare examples of parallel polycatenation (2DǞ3D).
Introduction
Metal–organic frameworks have attracted much atten-
tion largely due to their possible applications in catalysis,
sorption, magnetism and non-linear optics.[1–5] Their intri-
guing structures and topological studies are still of great
interest.[6] What is particularly important, in addition to the
associated preparative strategy, is to be able to correlate
functionalities with molecular structures. By doing so, re-
searchers will be able to access the optimized synthetic
strategy for the desired compound.[7] Currently, an interest-
ing area of research is the construction of entangled net-
works as a new class of potential materials,[8–12] for exam-
ple, penetration, (poly)catenation and (poly)knotting net-
works. Of these entanglements, the phenomenon of inter-
penetration, which happens when two or more identical in-
dependent networks pass through each other so that they
cannot be untangled without breaking some covalent
bonds, has been extensively investigated.[13] Most of these
networks are confined to those with the same dimensional-
ity as their constituent motifs.[14] In comparison with the
widely studied interpenetrating networks, polycatenation
networks, which lead to an increase in dimensionality
(1D+1DǞ2D, 2D+2DǞ3D, 1D+2DǞ3D, 1D+1DǞ3D),
have been less explored.[14c,15]
In recognition of the close relationship between the
chemical topology of the target supramolecular compound
and the structural particularity of the organic ligand, we
can selectively design ligands with special features for the
[a] Department of Chemistry, Nankai University,
Tianjin 300071, P. R. China
Fax: +86-22-23508056
E-mail: jmzheng@nankai.edu.cn
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201000832.
Scheme 1. Molecular structures of the ligands used in this study.
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Oxybis(benzoate) and Bis(imidazole) Polycatenation Networks
ladders is 76.840°. Until now, to the best of our knowledge,
there is only one example of 1DǞ2D polycatenation based
on this type of ladder.[20]
Results and Discussion
Crystal Structure of 1: Single-crystal X-ray diffraction
analysis revealed that compound 1 crystallizes in the mono-
clinic space group C2/c. The asymmetry unit of 1 consists
of one ZnII ion, one oba2– anion, half of a L1 ligand and
one coordinated water molecule. As shown in Figure 1, the
Zn1 atom is pentacoordinated by three carboxylic oxygen
atoms from two different oba2– anions [Zn1–O 1.990(2)–
2.461(2) Å], one Owater atom [Zn1–O6 1.997(2) Å] and one
NL1 atom [Zn1–N1 1.993(3) Å] to give a distorted square
pyramidal geometry. Each Zn atom is connected to three
others through one L1 and two oba2– ligands, thus leading
to the generation of a single flat ladder with the Zn···Zn
separation in the range of 13.679–14.391 Å (Figure 2). As
depicted in Figure 3, two flat ladders run in parallel direc-
tions and are laterally catenated by two other parallel lad-
ders on each side to form 2D entangled layers. A better
insight into the nature of this intricate framework can be
achieved by the application of a topological approach. As
shown in Figure 3 (b), the angle between two catenation
Crystal Structure of 2: When the L2 ligand was used in-
stead of the L1 ligand in 1, an unusual 2DǞ3D parallel
polycatenation framework, 2, was obtained. The structure
of 2 is composed of one Zn atom, one oba2– anion, one L2
ligand and one and a half molecules of water. As illustrated
in Figure 4, the tetracoordinated Zn atom in the tetrahedral
coordination environment is ligated to two L2 [Zn–N
2.005(3)–2.035(3) Å] and two bi-monodendate oba2– li-
gands [Zn–O 1.950(3)–1.973(3) Å]. Four Zn atoms are
interlinked through oba2– and L2 to form a 4-connected
2D corrugated layered structure with a 44-sql topology.[21]
Within each layer, two square windows with dimensions of
14.359ϫ13.514 and 14.359ϫ13.464 Å based on the metal–
metal distance are observed. Further inspection indicates
that the oba2– ligands adopt a V-shaped conformation due
to the rotation of the two phenyl groups around the –O–
spacer in between. More importantly, the V-shaped bridges
protrude away from the 44-sql sheet on both sides and thus
they can readily catenate with two others (one above and
one below). As a result, an infinite 3D framework is
achieved by polycatenation of the 44-sql sheet (Figure 5).
As shown in Figure 6, each 44-sql sheet is penetrated in par-
allel by two others (“above” and “below”) leading to a
2DǞ3D polycatenation network. The total volume for po-
tential solvent intercalation was evaluated to be 111.5 Å3,
equal to 8.9% of the volume of the unit cell (1250.5 Å3).[22]
Figure 1. View of the local coordination environment of the Zn
atom in 1. Hydrogen atoms have been omitted for clarity.
Figure 4. The local coordination environment of the Zn atom in 2.
Hydrogen atoms and lattice water have been omitted for clarity.
Figure 2. A single flat ladder of 1.
Figure 3. (a) View of the 1DǞ2D polycatenation of compound 1.
(b) Schematic representation of the 1DǞ2D catenation of 1.
Figure 5. View of the catenation of three adjacent layers for com-
pound 2.
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Y. Xu, P.-K. Chen, Y.-X. Che, J.-M. Zheng
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1.985(3)–2.264(3) Å] and two nitrogen atoms from two L1
ligands with a Co–N distance ranging from 2.044(3) to
2.045(3) Å to give a considerably distorted square pyrami-
dal geometry. Four Co atoms are interlinked through oba2–
and L1 to form a 4-connected 2D corrugated layered struc-
ture with 44-sql topology. In this case, the oba2– anions
adopt the μ1:η1,η0 and μ1:η1,η1 coordination modes. Fur-
ther studies suggested that the overall structure of 3 is very
similar to 2, that is, compound 3 also forms a 2DǞ3D
polycatenation net constructed from a 44-sql undulating
sheet with a “thickness” of 14.483 Å (Figure 8, Figure S1
in the Supporting Information).
Figure 6. View of the undulating 44-sql sheet of 2 and, following
catenation, schematic representation of the 3D parallel polycaten-
ation of sql observed for 2 with a degree of catenation, doc = 2.
We were aware that a small number of polycatenation
structures have previously been reported. For example, Ci-
ani and coworkers studied the 2DǞ3D [Ag(sebn)2]X (X =
SbF6, CF3SO3) network that is simultaneously catenated by
two others due to the thickness of the 2D diamond-66
sheets.[23] Another interesting example of a 2DǞ3D net-
work is the copper compound [Cu4(p-BDC)3(bipy)2] of Wil-
liams and coworkers.[24] The component motif of this
framework exhibits a thick double-layered 2D structure
with 5-connected 4862 topology and two others are cate-
nated with the top and bottom layers of the same species.
Very recently, Ma and coworkers described a Cd-containing
polymer showing 2DǞ3D parallel polycatenation architec-
ture based on oba2– and L1 ligands.[18b] And here, com-
pound 2 demonstrates that the use of ligand L2 is also ad-
visable to generate 2DǞ3D parallel polycatenation net-
works.
Figure 8. View of the catenation of three adjacent layers for com-
pound 3.
Comparison of the Structures 1–3: The three coordination
compounds 1–3 were successfully synthesized by using V-
shaped H2oba ligand and long-chain bis(imidazole)-based
ligands and structurally characterized. The pure phases of
compounds 1–3 were confirmed by powder X-ray diffrac-
tion measurements (Figure S2). All the structures present
polycatenation networks: 1 displays a rare 1DǞ2D poly-
catenation, whereas 2 and 3 are examples of 2DǞ3D par-
allel polycatenation networks. What are the differences be-
tween these structures that are of significance? Compounds
1 (L1) and 2 (L2) differ in their organic ligands and 1 (Zn)
and 3 (Co) differ in their metal atoms. Therefore, the V-
shaped oba2– anion and the neutral bis(imidazole) ligands
have an effect on the desired structures as well as the metal
sources used.
Crystal Structure of 3: When a CoII ion was used instead
of the ZnII ion in 1, 2DǞ3D parallel polycatenation frame-
work 3 was obtained. The structure of 3 contains one Co
atom, one oba2– anion and one L1 ligand. As illustrated in
Figure 7, the Co atom is coordinated by three carboxylic
oxygen atoms from two different oba2– anions [Co–O
Photoluminescence of 1 and 2: Photoluminescence experi-
ments on the Zn-containing compounds 1 and 2, with typi-
cal d10 transition-metal configurations, were performed at
room temperature in the solid state.[25] As shown in Fig-
ure 9, an intense luminescence peak at around 388 nm was
detected in the emission spectrum of 1 when it was excited
at 332 nm. However, the luminescence peak of compound
2 is clearly blue-shifted to 316 nm (λex = 298 nm) relative
to that of compound 1. The emission bands for free L1 and
L2 occur at 451 (λex = 379 nm) and 335 nm (λex = 299 nm),
respectively. In addition, the free H2oba ligand shows an
emission peak at about 318 nm (λex = 303 nm). Accord-
ingly, each of the two emission bands in 1 and 2 can be
attributed to ligand-to-metal charge-transfer (LMCT) tran-
sitions (Figure 9).
Figure 7. The local coordination environment for the Co atom in
3. Hydrogen atoms have been omitted for clarity.
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Oxybis(benzoate) and Bis(imidazole) Polycatenation Networks
Experimental Section
Materials and General Procedures: Solvents and starting materials
were purchased commercially and used as received without further
purification. Ligand L2 was synthesized as reported previously.[26]
The IR spectra were recorded as KBr pellets with a Nicolet Magna-
FT-IR 560 spectrometer in the range 4000–400 cm–1. Elemental
analysis was performed with a Perkin–Elmer 240 analyser. The
photoluminescence measurements were carried out on crystalline
samples at room temperature and the spectra were collected with a
Hitachi F-2500FL spectrophotometer. Thermogravimetric analyses
(TGA) were performed with a standard TG-DTA analyser under a
flow of nitrogen at a heating rate of 5 °C/min for all measurements.
Powder diffraction data were collected with a Rigaku D/max-RC
diffractometer using a Cu target (λ = 1.54060 Å) operated at 50 kV
and 180 mA.
Synthesis of [Zn(oba)(L1)0.5(H2O)]n (1): A mixture of Zn(NO3)2·
6H2O (0.15 g, 0.5 mmol), H2oba (0.13 g, 0.5 mmol) and L1 (0.12 g,
0.5 mmol) was dissolved in distilled water (8 mL). The pH value
was then adjusted to 5.5 with a 1 m NaOH solution and the re-
sulting mixture was transferred and sealed in a 25 mL Teflon®-
lined stainless-steel vessel. This was then heated at 160 °C for 3 d.
Afterwards the reactor was slowly cooled to room temperature and
white rod-shaped crystals were filtered off and dried in air; yield
Figure 9. Excitation and emission spectra of 1, 2 and the three li-
gands [symbols: the down triangle depict the excitation and emis-
sion spectra of 1; the stars depict the excitation and emission spec-
tra of 2; the circles depict the excitation and emission spectra of
the H2oba ligand; the diamonds depict the excitation and emission
spectra of the L1 ligand; the left triangles depict the excitation and
emission spectra of L2, solid symbol (EM) and point symbol (EX)].
96.3 mg, 42% (based on Zn). IR (KBr): ν = 3393 (m), 3127 (m),
˜
1626 (s), 1592 (m), 1343 (s), 1236 (s), 1095 (m), 884 (m), 777
(m) cm–1. C21H17N2O6 Zn (458.76): calcd. C 54.98, H 3.74, N 6.11;
found C 54.95, H 3.70, N 6.13.
TG Analysis of 1–3: Thermogravimetric analyses were
performed on to assess the thermal stability of 3D com-
pounds 1–3. Their TG curves are presented in Figure S3.
At about 138 °C, compound 1 shows a weight loss corre-
sponding to coordinated water (calcd. 3.92%; found
3.98%). Rapid weight loss was detected from 281 to 620 °C,
which has been attributed to the decomposition of the L1
and oba2– ligands. The remaining residue was presumed to
be ZnO (calcd. 17.66%; found 17.61%). At about 43 °C,
compound 2 showed a weight loss corresponding to lattice
water (calcd. 4.83%; found 4.87%). The host framework
was stable up to 370 °C at which temperature it starts to
Synthesis of [Zn2(oba)2(L2)2](H2O)3 (2): A mixture of Zn(NO3)2·
6H2O (0.15 g, 0.5 mmol), H2oba (0.13 g, 0.5 mmol) and L2 (0.11 g,
0.5 mmol) was dissolved in distilled water (8 mL). The pH value
was then adjusted to 6.5 with a 1 m NaOH solution and the re-
sulting mixture was transferred and sealed in a 25 mL Teflon®-
lined stainless-steel vessel. This was then heated at 160 °C for 3 d.
Afterwards the reactor was slowly cooled to room temperature and
light-yellow block-shaped crystals were filtered off and dried in air;
yield 142.5 mg, 51% (based on Zn). IR (KBr): ν = 3437 (s), 3136
˜
(m), 1609 (s), 1532 (m), 1389 (s), 1217 (m), 1164 (m), 1134 (m),
decompose until above 670 °C. In contrast, the decomposi- 1067 (m), 961 (m), 839 (m), 773 (m), 645 (m) cm–1.
C52H42N8O13Zn2 (1117.68): calcd. C 55.88, H 3.79, N 10.03; found
C 55.83, H 3.75, N 9.98.
tion of compound 3 occurs in a lower temperature range
(342–646 °C). The remaining residue was presumed to be a
1:1 CoO/CoCO3 mixture (calcd. 17.54%; found 17.62%).
Synthesis of [Co(oba)(L1)]n (3): A mixture of CoCl2·6H2O (0.12 g,
0.5 mmol), H2oba (0.13 g, 0.5 mmol) and L1 (0.12 g, 0.5 mmol)
was dissolved in distilled water (8 mL). The pH value was then
adjusted to 6.5 with a 1 m NaOH solution and the resulting mixture
was transferred and sealed in a 25 mL Teflon®-lined stainless-steel
vessel. This was then heated at 160 °C for 3 d. Afterwards the reac-
tor was slowly cooled to room temperature and purple block-
shaped crystals were filtered off and dried in air; yield 149.4 mg,
Conclusions
Three new polycatenation compounds based on the
oba2– and bis(imidazole) ligands have been synthesized un-
der hydrothermal conditions and structurally characterized.
Compound 1 is a rare 1DǞ2D parallel polycatenation
based on a flat ladder whereas 2 and 3 are novel 2DǞ3D
parallel polycatenation networks based on the undulating
44-sql sheet. This investigation has demonstrated an effec-
tive synthetic strategy for the synthesis of polycatenation
systems by controlling the rigidity of the N-donor ligands
incorporated with flexible V-shaped exo-bidentate mole-
cules, which play a crucial role in the formation of 2D (4,4)
layers with arc-shaped bridges. Both the organic ligands
and metal atoms are crucial for the construction of the de-
sired frameworks. The application of this methodology to
other functional materials is ongoing.
54% (based on Co). IR (KBr): ν = 3424 (m), 3111 (m), 1599 (s),
˜
1565 (m), 1384 (m), 1231 (m), 1162 (m), 1110 (m), 879 (m), 832 (m),
715 (m), 659 (m) cm–1. C28H22CoO5N4 (553.43): calcd. C 60.77, H
4.00, N 10.12; found C 60.72, H 4.03, N 10.11.
X-ray Crystallographic Determinations: Single-crystal analyses were
performed with the RAXIS-RAPID AUTO CCD diffractometer
systems (Mo-Kα radiation, λ = 0.71073 Å) for 1, 2 and 3. All data
were corrected for absorption effects by semiempirical methods
using the SADABS program.[27] The program SAINT was applied
to the integration of the diffraction profiles.[27] Data analyses were
carried out with the program XPREP.[28] Structures were solved by
direct methods using SHELXS-97 following structure refinement
on F2 with the program SHELXL-97.[28] All non-hydrogen atoms
Eur. J. Inorg. Chem. 2010, 5478–5483
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Crystal data and experimental details are summarized in Table 1.
Selected bonds and angles are listed in Table S1.
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Empirical formula
Mr
Temperature [K]
Crystal system
Space group
a [Å]
b [Å]
c [Å]
α [°]
β [°]
C21H17N2O6Zn C52H42N8O13Zn2 C28H22CoN4O5
458.76
293(2)
1117.68
298(2)
553.43
298(2)
monoclinic
C2/c
triclinic
P1
monoclinic
P21/c
¯
22.880(5)
12.496(3)
22.617(8)
8.8207(18)
11.273(2)
14.120(3)
112.20(3)
98.62(3)
98.91(3)
1250.5(4)
1
9.2422(18)
14.546(3)
18.867(4)
143.126(12)
102.24(3)
γ [°]
[12]
V [Å3]
3880.2(19)
8
2478.8(9)
4
Z
dcalcd. [gcm–3]
μ [mm–1]
θ range [°]
Completeness [%]
1.571
1.484
1.483
[13]
[14]
1.308
1.033
0.740
1.88–27.86
99.2
3.00–29.80
99.8
3.01–27.48
99.9
Goodness-of-fit on F2 1.100
1.048
0.943
Final R indices
R1 = 0.0574, R1 = 0.0517,
wR2 = 0.1280 wR2 = 0.1248
R1 = 0.0694,
wR2 = 0.1140
[IϾ2σ(I)][a]
[a] R1 = ∑(||Fo – Fc||)/∑|Fo|; wR2 = [∑w(Fo – Fc ) /∑w(Fo2)2]½.
2
2 2
[15]
CCDC-784326 (for 1), -722327 (for 2) and -722328 (for 3) contain
the supplementary crystallographic data for this paper. These data
can be obtained free of charge from The Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
Supporting Information (see also the footnote on the first page of
this article): Additional plots of the structures, tables of bond
lengths and angles for all the compounds and the experimental
PXRD of the three complexes.
[16]
[17]
Acknowledgments
The authors thank the National Natural Science Foundation of
China (50872057) for the financial support of this work.
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Received: August 2, 2010
Published Online: October 25, 2010
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© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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