Synthesis, structures and luminescent properties of two coordination polymers based on 5-(4-carboxyphenyl)-2, 6-pyridinedicarboxylic acid

Article abstract of DOI:10.1002/zaac.201200394

Two coordination polymers, Zn₇O(cpda)₃(OH) ₃ (1) and [Tb(H₂cpda)(Hcpda)(H₂O)] ·(H₂O) (2) (H₃cpda = 5-(4-carboxyphenyl)-2, 6-pyridinedicarboxylic acid), were synthesized and chara

Full text of DOI:10.1002/zaac.201200394

ARTICLE
DOI: 10.1002/zaac.201200394
Synthesis, Structures and Luminescent Properties of Two Coordination
Polymers Based on 5-(4-Carboxyphenyl)-2,6-Pyridinedicarboxylic Acid
[a]
[a]
[a]
[a]
[a]
Wenqian Zhang, Jiancan Yu, Yuanjing Cui,* Xingtang Rao, Yu Yang, and
Guodong Qian*[
a]
Keywords: Coordination polymers; Heterocycle polycarboxylate ligands; Crystal structure; Luminescence
Abstract. Two coordination polymers, Zn
Tb(H cpda)(Hcpda)(H O)]·(H O) (2) (H cpda = 5-(4-carboxyphenyl)- minescent measurements indicate that complex 1 shows strong ligand-
,6-pyridinedicarboxylic acid), were synthesized and characterized by to-metal charge transfer (LMCT) luminescence, while complex 2 exhi-
7 3 3
O(cpda) (OH) (1) and high thermal stability and complex 2 exhibits 1D chain structure. Lu-
[
2
2
2
3
2
3
+
elemental analysis, FTIR spectroscopy, TGA, PXRD, and single-crys-
bits the characteristic emission of Tb ions.
tal X-ray diffraction. Complex 1 has a 3D framework structure with
ligands.[14,15] Among previous reports, organic aromatic poly-
carboxylate ligands are most extensively used because they can
adopt a variety of coordination modes and result in diverse
Introduction
Over the past decades, design and synthesis of metal-organic
frameworks (MOFs) or coordination polymers have attracted
[16–19]
multidimensional structures.
great interest not only because of their fascinating topological
Compared with organic aromatic polycarboxylate ligands,
N-heterocycle polycarboxylate ligands have another nitrogen
coordination site, so its coordination modes are more abundant.
Using this kind of ligands, such as pyridine-2,6-dicarboxylic
architectures,[
1–3]
but also their potential applications in a wide
variety of fields, such as gas storage, catalysts, magnetism,
light emitting device, and chemical sensing.[
with traditional inorganic or organic luminescent materials,
MOFs assemble by the inorganic and the organic moieties,
both of which can provide the platforms to generate lumines-
cence. Meanwhile metal-ligand charge transfer related lumi-
4–11]
Compared
acid, pyridine-2,4,6-tricarboxylic acid, pyridine-2,3,5,6-tetra-
[20–25]
carboxylates,
a variety of MOFs have been synthesized.
5
-(4-carboxyphenyl)-2,6-pyridinedicarboxylic acid (H cpda)
3
contains one nitrogen atom and three carboxyl groups, that
make it has potential diverse chelating and bridging modes, so
it is a good candidate ligand for constructing MOFs. But to
nescence within MOFs can add another dimensional lumines-
cent functionalities.[
2,32–35]
Furthermore, some guest molecules
within MOFs are also able to emit and/or induce lumines-
the best of our knowledge, only one MOF based on this ligand
cence.[
2,33]
Thus, MOFs can be used as excellent multifunc-
[26]
was reported so far.
Herein, using this ligand we synthe-
tional luminescent materials.
sized two novel coordination polymers, Zn O(cpda) (OH) (1)
7
3
3
However, it is still a challenge for chemists to construct
novel metal-organic frameworks that have expected applica-
tions and intriguing structures, due to the coordination arrange-
ment affected by many subtle factors, such as the structural
characteristic of organic ligands, temperature, molar ratio of
and [Tb(H cpda)(Hcpda)(H O)]·(H O) (2), by solvothermal re-
2
2
2
action. In this paper we describe the synthesis, structure, and
luminescence studies of the two novel coordination polymers.
[12,13]
the materials, counter anions, pH value, etc.
It has been
Results and Discussion
proven that the selection of appropriate ligands is an efcient
method for the construction of novel MOF materials, and great
efforts have been devoted to the design of suitable organic
Crystal Structures Description
Single-crystal X-ray structural analysis reveals that
*
*
Dr. Y. Cui
Zn O(cpda) (OH) (1) crystallizes in the rhombohedral space
7
3
3
E-Mail: cuiyj@zju.edu.cn
Prof. Dr. G. Qian
¯
group R3 and exhibits a 3D network. As shown in Figure 1a,
the H cpda ligand has only one coordination mode, in which
E-Mail: gdqian@zju.edu.cn
3
2
+
[
a] State Key Laboratory of Silicon Materials
Cyrus Tang Center for Sensor Materials and Applications
Department of Materials Science and Engineering
Zhejiang University
each H cpda ligand connects six Zn ions. Three kinds of
crystallographically independent Zn ions exist in the asym-
3
2+
metry unit: Zn1, Zn2, and Zn3, as shown in Figure 1b–c. Zn1
and Zn2 are five-coordinate and Zn3 is four-coordinate. Zn1
Hangzhou, 310027, China
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.201200394 or from the au-
thor.
is surrounded by one nitrogen atom of one H cpda ligand,
3
three oxygen atoms of two different H cpda ligands and one
3
4
30
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2013, 639, (2), 430–434

Coordination Polymers Based on 5-(4-Carboxyphenyl)-2,6-Pyridinedicarboxylic Acid
4
Figure 2. (a) 12-Membered ring and Zn O SBU; (b) the 2D layer structure simplified by SBU; (c) the 3D framework of 1 viewed along the
a axis.
oxygen atom of one coordinated hydroxyl group (Figure 1b). water molecule. The coordination arrangement of Tb3+ ion is
Zn2 is surrounded by three oxygen atoms of three different a distorted dicapped trigonal prismatic (Figure 3b). The neigh-
H cpda ligands, one oxygen atom of a hydroxyl group and one boring Tb3+ ions (distance between them 6.4296 Å) are con-
3
single oxygen atom (O8) (Figure 1c). Zn3 is surrounded by nected by monodentate carboxyl groups of the H cpda ligands,
3
three oxygen atoms of three different H cpda ligands and one and give rise to a zigzag 1D chain (Figure 3c). From Figure 4,
3
single oxygen atom (O8) (Figure 1d). Interestingly, three Zn2 we can see that the neighboring 1D chains are packed together
and one Zn3 together with one O8 form a special Zn O tetrahe- to form a 2D layer structure through the π–π interactions
4
dron, while six Zn1 atoms alternatingly connect with six O1 (3.542 Å) and hydrogen bonding interactions (2.477 Å). Fur-
atoms to form a Zn–O 12-membered ring (Figure 2a). Mean- ther, there are some H cpda ligands with uncoordinated car-
3
while, the Zn O secondary building unit and the 12-member boxyl groups acting as hydrogen bonding acceptor that extend
4
ring are connected by a bridge oxygen atom O7 and another the 2D layer into 3D framework. The π–π interactions and
oxygen atom O3 from another ligand. In this way, both the 12- hydrogen bonding interactions play an important role in con-
member ring and Zn O SBU yield a complete layer (Fig- structing and stabilizing of the crystal structure of 2.
4
ure 2b). Furthermore, the layers are connected by the H cpda
3
ligands between the layers like pillars to hold a robust 3D
framework structure (Figure 2c).
Figure 3. (a) Coordination environment of the Tb3+ atom; (b) the dis-
torted dicapped trignoal prismatic arrangement; (c) the zigzag 1D
chain.
Phase Purity and Thermal Stability
3
Figure 1. (a) Coordination mode of H cpda; (b–d) three kinds of crys-
tallographically independent Zn2+ ions with different coordination
modes.
To investigate the phase purity of the as-synthesized samples
of 1 and 2, powder X-ray diffractions and elemental analyses
Single-crystal X-ray structural analysis reveals that were carried out. Figure S1 (Supporting Information) shows
[
Tb(H cpda)(Hcpda)(H O)]·(H O) (2) crystallizes in the mo- that the powder X-ray diffraction patterns of as-synthesized
2
2
2
noclinic space group C2/c and shows a 1D structure. The samples are agreed well with the simulated ones from the sin-
asymmetric unit consists of one Tb3 ion, two H cpda ligands, gle crystal structure analyses. Coupled with the elemental
+
3
and one coordinated water molecule (Figure 3a). The H cpda analyses presented in the experimental, the phase purity of the
3
ligand shows two kinds of coordination modes: one act as as-synthesized samples is confirmed.
bridging ligand, the other act as terminal ligand. And Tb3+ ion
The thermal stability of both coordination polymers were
is eight-coordinate by two nitrogen atoms and six oxygen examined by thermogravimetric analysis (TGA) from room
atoms, in which six from two tridentate cheated ONO atoms temperature to 900 °C (Figure 5). The TGA curve of 1 indi-
of two H cpda ligands, one oxygen atom from neighboring cates that 1 can be stable up to 440 °C, and it quickly starts
3
H cpda ligand, and another one oxygen atom from coordinated losing weight and collapses above 440 °C. The high thermal
3
Z. Anorg. Allg. Chem. 2013, 430–434
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
431

W. Zhang, J. Yu, Y. Cui, X. Rao, Y. Yang, G. Qian
ARTICLE
Figure 4. (a) 3D structure of 2 viewed along the b axis; (b) the π–π interaction and hydrogen bond of the 2D layer structure; (c) hydrogen
bonding interactions in two adjacent layers.
stability of 1 is mainly attributed to the strong metal-carboxyl-
[31]
ate and nitrogen interactions.
The TGA curve of 2 shows
that 2 exhibits three weight loss steps. The first event take
place from 110 to 200 °C, that may be related to the release of
one coordinated water molecule (found 2.22%; calcd. 2.41%).
The other two steps from 215 to 380 °C and from 390 to
850 °C, respectively, which correspond to the removal and de-
composition of the H cpda ligand. The residue might be Tb O
3
4
7
(found 24.24%; calcd. 24.38%).
Figure 5. TGA curve for complex 1 and 2 under nitrogen.
Figure 6. Luminescence emission spectra of H
cited at 367 nm (a), and 2 excited at 335 nm (b).
3
cpda ligand and 1 ex-
Luminescent Properties
Taking into account of the excellent luminescent properties
1
0
3+
of MOFs with central d metal and Ln ions, the solid-state 367 nm excitation (Figure 6a), which may be attributed to the
luminescent spectra of compounds 1 and 2 and corresponding π–π* transition. Under the same excitation, complex 1 exhibits
ligand were studied at room temperature. The excitation spec- much enhanced blue emission and the maximum emission
tra of 1, 2, and H cpda ligand are shown in Figure S2 (Sup- shifts to 470 nm (Figure 6a). The enhancement and red-shift
3
porting Information). The free H cpda ligand exhibits a broad of the emission may be attributed to the coordination of the
3
2+
emission band with the maximum emission at 449 nm under H cpda ligand to Zn that increases the rigidity of the ligand
3
4
32
www.zaac.wiley-vch.de
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2013, 430–434

Coordination Polymers Based on 5-(4-Carboxyphenyl)-2,6-Pyridinedicarboxylic Acid
3
and thus reduces the loss of energy via radiationless decay of 5-(4-Carboxyphenyl)-2,6-Pyridinedicarboxylic Acid (H cpda): A
[
32]
mixture of dimethyl 4-chloropyridine-2,6-dicarboxylate (6.89 g,
30 mmol), 4-carbomethoxyphenylboronic acid pinacol ester(9.43 g,
6 mmol), KI (24.9 g, 150 mmol), K CO (12.4 g, 90 mmol), and CsF
13.67 g, 90 mmol) was dissolved in dried 1,4-dioxane (250 mL),
which was purged with argon and stirred for half an hour at room
temperature. Afterwards, Pd(PPh (0.4 g, 0.035 mmol) was added
the intraligand emission excited state.
The emission spectra
of 2 consist of four characteristic emission band of Tb3+ lo-
cated at about 489, 546, 582, and 622 nm under 335 nm exci-
tation, which are assigned to the transitions of the Tb from
D Ǟ F (J = 6, 5, 4, 3), respectively (Figure 6b), However,
the main intraligand band disappeares. These phenomena sug-
gest that the H cpda ligand absorbs and transfers energy ef-
3
(
2
3
3+
5
7
4
J
3 4
)
and the mixture was heated at 90 °C for 8 h. After cooling to room
temperature, the precipitate was filtered off, and the filtrate was re-
3
3
+
ficiently to the central metal ions of Tb , which is well moved under reduced pressure. The residue was purified by silca gel
knowed by ligand-to-metal charge transfer (LMCT).
[
33–35]
columnchromatography with dichloromethane/ethyl acetate (40:1) to
give dimethyl 5-(4-carboxyphenyl)pyridine-2,6-dicarboxylate as a
white solid. A suspension of diester in 1 m NaOH was stirred at 80 °C
for 2 h. The solution was cooled with ice and acidied with HCl to pH
Conclusions
2. The white precipitate was collected to give H
based on dimethyl 4-chloropyridine-2,6-dicarboxylate. H NMR
3
cpda in 65% yield
1
Two novel coordination polymers based on 5-(4-car- (DMSO): δ = 8.03 (d, 2 H), 8.08 (d, 2 H), 8.49 (s, 2 H) ppm.
boxyphenyl)-2,6-pyridinedicarboxylic acid were successfully
synthesized by solvothermal reaction. Complex 1 has a 3D
framework structure and exhibits high thermal stability up to
C
14
H
9
NO
6
: calcd. C 58.54; H 3.16; N 4.88%; found: C 58.03; H 3.10;
N 4.74%.
4
40 °C. 3D supramolecular structure of complex 2 is struc-
7 3 3 3 2 2
Zn O(cpda) (OH) (1): Zn(NO ) ·6H O (0.0223 g, 0.075 mmol),
–
1
tured by connecting 1D chain substructure through π–π inter- H cpda (0.0144g, 0.05 mmol), HCl (12 mol·L , 20uL), H O (6 mL),
3
2
actions and hydrogen bond interactions. Moreover, complexes and ethanol(2 mL) were added into a 25 mL Teon high temperature
and 2 exhibit strong LMCT luminescence and characteristic kettle and kept at 170 °C for 48 h. After the mixture had slowly cooled
1
3
+
to room temperature, colorless rhombus-like crystals were obtained in
emission of Tb ions, respectively, under UV light excitation,
which makes them excellent candidates in light-emitting de-
vices applications.
75% yield based on Zn(NO
3 2 2 21 3 7
) ·6H O. C42H N O22Zn : calcd. C
36.59; H 1.52; N 3.05%; found: C 36.90; H 1.63; N 3.11%. IR (KBr):
ν˜ = 3480 (s), 1687 (s), 1646 (m), 1604 (s), 1572 (m), 1463 (w), 1445
(
9
w), 1410 (m), 1385 (m), 1329 (m), 1261 (w), 1077 (w), 1011 (w),
05 (w), 862 (w), 778 (m), 748 (w), 699 (w), 530 (w) cm .
–
1
Experimental Section
[
6
(
Tb(H
2
cpda)(Hcpda)(H
2
O)]·(H
2
O) (2): A mixture of Tb(NO
cpda (0.0144 g, 0.05 mmol), HCl
O (8 mL) was added into a 25 mL Teon
3 3
) ·
Materials and Methods: All the chemicals were commercially avail-
H
2
O (0.012 g, 0.025 mmol), H
3
able and used without further purication. Dimethyl 4-chloropyridine-
–
1
12 mol·L , 20 μL), and H
2
2
1
,6-dicarboxylate was synthesized according to the literature.[27,28]
high temperature kettle and kept at 120 °C for 48 h. After the mixture
was slowly cooled to room temperature, colorless rod-like crystals
H NMR spectra were performed with a Bruker Avance DMX500
spectrometer using tetramethylsilane (TMS) as an internal standard.
Infrared spectra (IR) were recorded with a Thermo Fisher Nicolet iS10
spectrometer using KBr pellets. Elemental analyses for C, H, N were
performed with an EA1112 microelemental analyzer manufactured by
Thermo Electron Corporation. Powder X-ray diffraction (PXRD) pat-
terns were collected in the 2θ = 3–60° range with an X’Pert PRO
were obtained in 55% yield based on Tb(NO
14Tb: calcd. C 43.84; H 2.48; N 3.65%; found: C 43.65;
H 2.41; N 3.66%. IR (KBr): ν˜ = 3440 (s), 1681 (s), 1596 (s), 1450
m), 1420 (m), 1350 (m), 1315 (w), 1286 (m), 1185 (w), 1129 (w),
071 (w), 1014 (w), 918 (w), 859 (w), 809 (w), 773 (m), 764 (m), 728
3 3 2
) ·6H O.
28 19 2
C H N O
(
1
–
1
(
m), 532 (w) cm .
α
diffractometer with Cu-K (λ = 1.541 Å) radiation at room tempera-
ture. Thermogravimetric analyses (TGA) were carried out with a
Netzsch TG209F3 with a heating rate of 1 K·min–1 in a nitrogen atmo-
X-ray Data Collection and Structural Determination: Crystallo-
sphere. Luminescence spectra for the solid samples were recorded with graphic measurement for complex 1 and 2 was taken with a Oxford
a Hitachi F4500 fluorescence spectrometer. The photomultiplier tube
Xcalibur Gemini Ultra diffractometer with an Atlas detector using
voltage was 700 V and the scan speed was 240 nm per min, while the
graphitemonochromatic Mo-Kα radiation (λ = 0.71073 Å) at 293 K.
slit widths of excitation and emission spectra were 2.5 nm and 2.5 nm The determination of the unit cells and data collections for the crystals
for H
3
cpda and 1, 1.0 nm and 1.0 nm for 2, respectively.
of 1 and 2 were performed with CrysAlisPro. The data sets were cor-
rected by empirical absorption correction using spherical harmonics,
[
29]
4-Carbomethoxyphenylboronic Acid Pinacol Ester: Methyl 4-bro-
implemented in SCALE3 ABSPACK scaling algorithm.
The struc-
mobenzoate (10 g, 46.5 mmol), bis(pinacolato)diboron (15.35 g,
ture was solved by direct methods, and rened by a full-matrix least-
[
30]
60.3 mmol), KOAc (13.7 g, 139.5 mmol), and Pd(PPh
3
)
2
Cl
2
(0.5 g,
square method with the SHELX-97 program package.
All non-hy-
0
.7 mmol) were dissolved in 1,4-dioxane (250 mL), subsequently the
drogen atoms including solvent molecules were located successfully
from Fourier maps and were rened anisotropically. Hydrogen atoms
mixture was heated at 80 °C for 4 h. After cooling to room tempera-
ture, the precipitate was filtered off, and the filtrate was removed under on carbon atoms were generated geometrically. The hydrogen atoms
reduced pressure. The residue was purified by silca gel column-
of the water molecules were clearly visible in different maps and were
chromatography with petroleum ether/ethyl acetate (8:1) to give 4- handled in the subsequent renement with xed isotropic displacement
carbomethoxyphenylboronic acid pinacol ester in 60% yield based on
parameters. Crystallographic data for 1 and 2 are summarized in
Table 1, the selected bond lengths and angles are listed in Table S1
and S2 (Supporting Information), respectively.
1
methyl 4-bromobenzoate. H NMR (CDCl
s, 3 H), 7.88 (d, 2 H), 8.04 (d, 2 H).
3
): δ = 1.37 (s, 12 H), 3.93
(
Z. Anorg. Allg. Chem. 2013, 430–434
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
433

W. Zhang, J. Yu, Y. Cui, X. Rao, Y. Yang, G. Qian
ARTICLE
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Wavelength /Å
Crystal system
Space group
a /Å
b /Å
c /Å
α /°
C
42
H
21
N
3
O
22Zn
7
C
28 19 2
H N O14Tb
675.
1377.21
293(2)
0.71073 A
rhombohedral
R3
13.6884(10)
13.6884(10)
39.877(3)
90
766.37
293(2)
0.71073
monoclinic
C2/c
28.2602(11)
6.9089(3)
30.2153(10)
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90
120
6470.8(8)
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2.121
99.598
90
5816.9(4)
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γ /°
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4
F(000)
4080
3024
Crystal size /mm–3
0.35ϫ0.28ϫ0.22 0.32ϫ0.26ϫ0.22
2
Goodness of t on F
2
1.034
0.0243, 0.0566
0.0301, 0.0588
1.144
a)
R
1
, wR
, wR
2
[I Ͼ 2σ(I)
(all data)
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0.0945, 0.2260
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Acknowledgements
This work was supported by the National Natural Science Foundation
of China (Nos. 51010002, 51272229 and 51272231) and the Funda-
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