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Keywords:

  • 3,5-Bis(imidazole-1-yl)pyridine;
  • Dicarboxylate ligands;
  • Coordination polymers;
  • X-ray diffraction;
  • Luminescence

Abstract

  1. Top of page
  2. Abstract
  3. Introduction
  4. Results and Discussion
  5. Conclusions
  6. Experimental Section
  7. Acknowledgements
  8. Supporting Information

Three metal coordination polymers [Zn(bdc)(L)(H2O)]n (1), [Co(pta)(L)(H2O)2]n (2), and [Cd(tda)(L)(H2O)]n (3) [H2bdc = 1,2-benzene dicarboxylate acid, H2pta = terephthalic acid, H2tda = 2,5-thiophenedicarboxylic acid, L = 3,5-bis(imidazole-1-yl)pyridine] were synthesized and structurally characterized by IR spectroscopy, elemental analysis, X-ray powder diffraction, and X-ray single crystal diffraction. Complex 1 shows a three-dimensional (3D) structure with cco topology with the symbol 65·8, whereas complex 2 features a 3D structure with cds topology with the symbol 65·8. Complex 3 has a 2D network constructed by the cadmium atoms bridged through the ligands tda and L. Their X-ray powder diffraction patterns were compared with the simulated ones. Moreover, their luminescent properties were investigated in the solid state at room temperature, and the thermogravimetric analyses were carried out to study the thermal stability of the 3D networks.


Introduction

  1. Top of page
  2. Abstract
  3. Introduction
  4. Results and Discussion
  5. Conclusions
  6. Experimental Section
  7. Acknowledgements
  8. Supporting Information

Over the past few years, metal-organic frameworks (MOFs) have attracted much attention not only due to their intriguing architectures and framework topologies but also their potential applications in the fields including, but not limited to, storage,1 gas separation,2 catalysis,3 magnetism,4 sensor5 and luminescence properties.6 Diverse architectures and functions of MOFs could be realized by the appropriate design and fine tuning of the bridging ligands and central metal atoms.7 Rigid ligands, such as benzenedicarboxylate ligands, were extensively utilized to construct a variety of MOFs due to their diverse coordination modes (monodetate, chelating, and bis-monodentate).8 Moreover, flexible ligands, such as 1,4-bis(imidazole-1-yl)-butane, were also employed for the construction of coordination networks with various structures and special functions,9 which enabled clarifying the detailed self-assembly process. Only recently, semirigid ligands have received remarkable attention. Compared to the above two kinds of ligands, semirigid ligands show only slight conformational changes during the assembly process,10 which enabled controlling the construction of architectures.

In this context, the semirigid organic linker 3,5-bis(imidazole-1-yl)pyridine was employed to provide cooperative coordination together with the rigid dicarboxylate groups (1,2-benzenedicarboxylate, terephthalate, and 2,5-thiophenedicarboxylate) to meet the requirement of coordination geometries of metal ions in the assembly process. The imidazole rings can only spin on the C–N single bonds to limit the flexibility of the linker, which would make the linkers point to some specific directions rather than in the disordered state. We herein report on three new coordination polymers obtained from the combination of L and the rigid dicarboxylate groups.

Results and Discussion

  1. Top of page
  2. Abstract
  3. Introduction
  4. Results and Discussion
  5. Conclusions
  6. Experimental Section
  7. Acknowledgements
  8. Supporting Information

Description of the Crystal Structures

[Zn(bdc)(L)(H2O)]n (1)

The structure of complex 1 is a 3D structure with cco topology. The asymmetric unit contains four crystallographically distinct ZnII ions, as depicted in Figure 1a. The coordination environment of the Zn1 atom has a tetrahedral arrangement with two carboxylate oxygen atoms and two nitrogen atoms. The coordination sphere of Zn2 and Zn3 are both defined by four oxygen atoms from two chelating bidentate carboxylate groups of one bdc anion, one carboxylate oxygen atom belonging to a monodentate carboxylate group of the other bdc anions, and two nitrogen atoms of L ligands. The equatorial plane of Zn2 is constituted by O12, N11, and O10 with N16 and O9 as axial ligand, and the Addison tau factor for Zn2 is 0.575, while the Addison tau factor for Zn3 is 0.812 with N5 and O1 as axial ligand. The structure of two zinc atoms is close to trigonal bipyramidal. The Zn4 ion is ligated by three oxygen atoms of bdc and two nitrogen atoms of L. As shown in Figure 1b, the L ligands connect ZnII ions to form a 1D zigzag chain. The 1D chains are further connected by bdc ligands to construct a 3D framework. If the ZnII ions and organic ligands can be viewed as nodes and linkers, respectively, the 3D structure can be simplified as cco topology with the point symbol 65·8 and long Vertex symbol [6.6.6.6.6(2).10(10)] (Figure 1c).11

[Co(pta)(L)(H2O)2]n (2)

The coordination environment of the central CoII atom in 2 is illustrated in Figure 2a. The CoII ion is situated in the center of the complex with two oxygen atoms belonging to two molecules of pta and two nitrogen atoms from L occupying each vertex of the equatorial sites, while two oxygen atoms deriving from two molecules of water are located in the apical positions along the axis to form a slightly distorted octahedral arrangement. All the carboxylate groups adopt a monodentate coordinating mode. In the framework, the cobalt atoms are serving as 4-connected nodes with a square planar arrangement of linkers. Moreover, two types of 1D wavy chains are observed, namely, chain 1 [Co–pta–Co]n and chain 2 [Co–L–Co–L–Co]n, which are crosslinked into a cavity-containing [Co6(pta)2(L)4] 2D sheet by two types of linkers [(L–Co–L) and (–pta–)] (see Figure 2b). Furthermore, the parallel pyridine and benzene rings of both ligands between adjacent 2D sheets are partly overlapping (zipper-like) with distances of 3.798 Å (centroid-to-centroid distances between the adjacent pyridine and benzene rings), suggesting that π–π interactions between the adjacent 2D sheets occur. Consequently, a highly ordered 3D network assembles, which is not interpenetrated (Figure 2c). As shown in Figure 2d, complex 2 shows a three-dimensional (3D) structure with cds topology 65·8 and long Vertex symbol [6.6.6.6.6(2)·8(2)].12

[Cd(tda)(L)(H2O)]n (3)

The structure of complex 3 is determined by X-ray single-crystal diffraction. As shown in Figure 3a, the cadmium(II) atom is surrounded by three carboxylate oxygen atoms and an aqua ligand at the basal positions, and two nitrogen atoms at the apical positions, showing a distorted octahedron arrangement. As shown in Figure 3b, two carboxylate groups adopt bis-monodentate coordination modes, and a carboxylate group adopts monodentate coordinating mode. The two carboxylate groups bridge between two cadmium atoms, forming an eight-membered ring (–Cd–O–C–O–Cd–O–C–O). The Cd–Cd separation in the ring is 4.599 Å. Meanwhile, the eight-membered ring is surrounded by four 18-membered rings consisting of two cadmium atoms bridged by a pta ligand and an L ligand. A two-dimensional layer structure is constructed in this way, as shown in Figure 3c.

XRPD Analyses and Luminescent Properties

The simulated and experimental X-ray powder diffraction patterns of 1, 2, and 3 are shown in Figure S1 (Supporting Information). All the peaks presented in the measured curves approximately match the simulated curves generated from single-crystal diffraction data, which clearly confirms the phase purity of the as-synthesized products.

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Figure 1. (a) Coordination environments of the zinc atoms in 1 (all hydrogen atoms are omitted for clarity). (b) The 1D chain constructed by ZnII ions and L ligands. (c) The 3D topological net for complex 1.

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thumbnail image

Figure 2. (a) Coordination environment of the CoII atom in 2 (all hydrogen atoms are omitted for clarity). (b) Two types of 1D wavy chains in complex 2. (c) π–π interactions between the adjacent 2D sheets in complex 2. (d) 3D topological net for complex 2.

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thumbnail image

Figure 3. (a) Coordination environment of the CdII atom in 3 (all hydrogen atoms are omitted for clarity). (b) The eight-membered ring and the 18-membered rings formed by the cadmium atoms bridged through the tda and the L ligands. (c) The 3D topological net for complex 3.

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The fluorescence emission spectra of 1, 2, and 3 and the ligands were measured in the solid state at room temperature. Intense luminescence emission bands are observed at 411 nm (λex = 292 nm) for all of the three complexes (Figure 4). In contrast, the L ligand has an emission band at 411 nm upon excitation at 322 nm. Intense fluorescence emission bands of H2bdc, H2pta, and H2tda are observed at 341 nm (λex = 284 nm), 380 nm (λex = 282 nm) and 417 nm (λex = 298 nm), respectively (Figure S2, Supporting Information). Compared with the fluorescence data of these three dicarboxylates, the fluorescence of complexes 1, 2, and 3 is unlikely arising from the auxiliary aromatic dicarboxylate ligands. The luminous mechanism for them might be intraligand fluorescent emission (π–π*).13 The different emission positions and intensities of the complexes compared with the L ligand might be attributed to the significant difference in their structures. The ligand coordination to the central metal atom might contribute to the enhancement of luminescence, which effectively increases the asymmetry and rigidity of the ligands, and thereby reduces the non-radiative decay of the intraligand excited state.14

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Figure 4. Comparison of the fluorescent emission spectra for complexes 13 with the L ligand in the solid state at room temperature.

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Thermogravimetric Analyses

To investigate the thermal stability of the three compounds, TG analyses were carried out with a Netzsch STA409PC instrument at a heating rate of 10 K·min–1 from 20 °C to 800 °C under nitrogen (flow rate = 60 mL·min–1).

As shown in Figure 5, complex 1 displays three weight loss stages. The weight loss of 2.52 % (calcd. 3.93 %) of the first step (20 °C–320 °C) corresponds to the release of the coordinated water molecule. The weight loss of 48.14 % (calcd. 46.04 %) in the second step, occurrs between 320 °C and 425 °C, corresponding to the complete decomposition of the L ligand, while the third step occurrs between 425 °C and 800 °C and results from the partial decomposition of the bdc ligand.

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Figure 5. TG curves of complexes 13.

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The TG curve of complex 2 indicates that this compound also shows three weight loss stages. The weight loss of 7.75 % (calcd. 7.66 %) in the temperature range of 150 °C–205 °C could be assigned to the release of the two coordinated water molecules. The weight loss of 45.36 % (calcd. 44.91 %) in the range of 205–455 °C indicates the decomposition of the L ligand, while the weight loss 31.91 % (calcd. 31.49 %) between 455 °C and 720 °C results from full decomposition of the pta ligand.

The weight loss of 3.42 % (calcd. 3.52 %) in the TG curve of complex 3 in the temperature range of 20–200 °C could be attributed to the release of one coordinated water molecule. The weight loss of 42.90 % (calcd. 41.27 %) in the temperature range of 200–420 °C indicates the complete decomposition of the ligand L, while the weight loss 30.12 % (calcd. 28.17 %) in the temperature range of 420–780 °C could be assigned to the decomposition of the tda ligand.

Conclusions

  1. Top of page
  2. Abstract
  3. Introduction
  4. Results and Discussion
  5. Conclusions
  6. Experimental Section
  7. Acknowledgements
  8. Supporting Information

Through self-assemblies of rigid carboxylates H2bdc with ZnII, H2pta with CoII, and H2tda with CdII in the presence of the unsymmetrical ligand L, we were able to construct three new coordination polymers [Zn(bdc)(L)(H2O)]n (1), [Co(pta)(L)(H2O)2]n (2), and [Cd(tda)(L)(H2O)]n (3). Similar to those reported in the corresponding references,15 the carboxylate groups in the three complexes coordinate to metal ions by chelating, monodentate, or bis-monodentate modes. Complex 1 shows a three-dimensional (3D) structure with cco topology with the symbol 65·8, whereas complex 2 features a 3D structure with cds topology with the symbol 65·8. For complex 3, a 2D network is constructed by cadmium atoms bridged through the tda and the L ligands. Luo et al. have reported the crystal structures of series of coordination polymers derived from just L ligand and metal ions without the participation of carboxylates,15 in which the anions of the metal salts were involved in the construction of coordination framework in either inner sphere or the outer sphere, because the L ligand itself does not have negative charges. Complexes 1 and 2 are similar to the previously reported structure [Zn(pta)(L)(H2O)2]n, in which the metal ions are coordinated with both L ligands and the auxiliary carboxylates.15 Due to the usage of different secondary ligands, the structure of complex 1 has changed dramatically, and the carboxylate groups in complex 1 adopt both chelating and monodentate coordination modes, while the carboxylate groups in complex [Zn(pta)(L)(H2O)2]n adopt monodentate coordination modes. In complex 2, the substitution of ZnII with CoII has little impact on the structure and both adopt the monodentate coordination modes and their coordination environments are similar. This indicates that the change of the bridging ligands can influence the coordination environment of the central metal atoms, which can further influence the detailed architecture of the coordination polymers. The correctness of their crystal structures were confirmed by comparing their simulated X-ray powder diffraction patterns with the experimental ones. In addition, the complexes 1, 2, and 3 also exhibit emission in the solid state at room temperature. Compared with the L ligand, both of their excitation and emission peaks have changed. Finally, the thermogravimetric analyses were carried out to study the thermal stability of the 3D networks.

Experimental Section

  1. Top of page
  2. Abstract
  3. Introduction
  4. Results and Discussion
  5. Conclusions
  6. Experimental Section
  7. Acknowledgements
  8. Supporting Information

Materials and Analyses: All reagents and solvents employed were commercially available and used as received without further purification. Elemental analysis was carried out with a Carlo Erba 1106 full-automatic trace organic elemental analyzer. Fourier-transform infrared spectra (FT-IR) were recorded with a Bruker Tensor-27 FT-IR spectrometer with dry KBr pellets in the 400–4000 cm–1 range. X-ray powder diffraction (XRPD) measurements were performed with a Bruker D8 diffractometer operating at 40 kV and 40 mA using Cu-Kα radiation (λ = 0.15418 nm). Solid-state fluorescence spectra were recorded with a Hitachi F-4600 equipped with a xenon lamp and a quartz carrier at room temperature. Thermogravimetric measurements were made in air with a Netzsch STA409PC instrument at a heating rate of 10 K·min–1 from 20 °C to 800 °C under nitrogen (flow rate = 60 mL·min–1).

Synthesis of [Zn(bdc)(L)(H2O)]n (1): A mixture of Zn(NO3)2·6H2O (0.297 g, 1 mmol), H2bdc (0.242 g, 1 mmol), L (0.211 g, 1 mmol), NaOH (0.08 g, 2 mmol), and deionized water (18 mL) was sealed in a 25 mL Teflon-lined stainless steel vessel and heated at 160 °C for 96 h. After cooling to room temperature, the colorless block crystals were obtained and washed with alcohol several times (Yield: 41 % based on Zn). C19H15ZnN5O5: calcd. C 49.75, H 3.30, N 15.27 %; found. C 49.50, H 3.27, N 15.35 %. IR (KBr): equation image = 3106 br, 1609 s, 1443 m, 1374 m, 1313 m, 1248 m, 1120 m, 1068 m, 1010 m, 945 m, 840 m, 753 m, 699 m, 652 m, 475 m cm–1.

Synthesis of [Co(pta)(L)(H2O)2]n (2): A mixture of Co(NO3)2·6H2O (0.291 g, 1 mmol), terephthalic acid (0.166 g, 1 mmol), L (0.211 g, 1 mmol), NaOH (0.04 g, 1 mmol), and deionized water (18 mL) was sealed in a 25 mL Teflon-lined stainless steel vessel and heated at 160 °C for 96 h. After cooling to room temperature, the colorless block crystals were obtained and washed with ethanol several times. C19H17CoN5O6: calcd. C 48.52, H 3.64, N 14.89 %; found. C 48.56, H 3.67, N 14.86 %. IR (KBr): equation image = 3394 br, 3116 s, 1564 s, 1504 m, 1438 w, 1374 s, 1238 w, 1118 m, 1072 m, 931 m, 829 m, 752 m, 653 m cm–1.

Synthesis of [Cd(tda)(L)(H2O)]n (3): A mixture of Cd(NO)2·4H2O (0.308 g, 1 mmol), H2tda (0.172 g, 1 mmol), L (0.211 g, 1 mmol), NaOH (0.08 g, 2 mmol), and deionized water (18 mL) was sealed in a 25 mL Teflon-lined stainless steel vessel and heated at 160 °C for 96 h. After cooling to room temperature, the colorless block crystals were collected by filtration and washed by ethanol several times. C17H13CdN5O5S: calcd. C 48.52, H 2.56, N 13.68 %; found. C 48.56, H 2.57, N 13.69 %. IR (KBr): equation image = 3416 br, 3120 w, 1602 m, 1559 m, 1504 m, 1362 s, 1118 m, 774 m, 463 m cm–1.

Crystal Structure Determination: Diffraction intensity data of the single crystals of complexes 1, 2, and 3 were collected with a Bruker SMART APEXII CCD diffractometer equipped with a graphite monochromated Mo-Kα radiation (λ = 0.71073 Å) by using a φ and ω scan mode at 298(2) K. The programs used for data collection and cell refinement is the SMART and SAINT programs.16 Empirical absorption correction was applied using the SADABS programs.17 All structure solutions were performed with direct methods using SHELXS-97,18 and the structure refinement was done against F2 using SHELXL-97.19 All non-hydrogen atoms were found in the final difference Fourier map. Hydrogen atoms were fixed geometrically at calculated distances and allowed to ride on the parent non-hydrogen atoms. Positional and thermal parameters were refined by full-matrix least-squares method to convergence. The crystallographic data of complexes 1, 2, and 3 are summarized in Table 1. Selected bond lengths and angles for complexes 1, 2, and 3 are listed in Table 2.2

Table 1. Crystallographic data and structure refinement summary for complexes 1, 2, and 3.
 123
Empirical formulaC19H15ZnN5O5C19N5O6CoH17C17H13CdN5O5S
  1. a

    a) R = Σ(||Fo|–|Fc||)/Σ|Fo|. b) wR = [Σw(|Fo|2–|Fc|2)2w(Fo2)]1/2.

Formula weight1826.94470.31511.78
Crystal systemorthorhombicmonoclinicmonoclinic
Space groupP212121C2/cP21/c
a10.624(1)22.094(2)7.995(1)
b16.430(1)6.386(1)20.074(1)
c43.069(3).14.293(2)11.334(1)
β90106.994.5
Volume /Å37517.7(10)1929.4(4)1813.2(2)
Z444
Calculated density /mg·m–31.6211.6191.875
μ1.3420.9401.362
Independent reflections [I > 2σ(I)]10769472111167
F(000)37449641016
θ range for data collection1.33–23.241.93–25.052.03–27.51
Limiting indices–11 ≤ h ≤ 10–26 ≤ h ≤ 26–10 ≤ h ≤ 10
 –18 ≤ k ≤ 18–7 ≤ k ≤ 7–25 ≤ k ≤ 24
 –39 ≤ l ≤ 47–11 ≤ l ≤ 17–14 ≤ l ≤ 13
Goodness-of-fit on F21.0081.0321.012
R1a), wR2b) [I > 2σ(I)]R1 = 0.0532, wR2 = 0.1044R1 = 0.0252, wR2 = 0.0689R1 = 0.0297, wR2 = 0.0592
R1a), wR2b) (all data)R1 = 0.0938, wR2 = 0.1220R1 = 0.0266, wR2 = 0.0704R1 = 0.0442, wR2 = 0.0644
Largest diff. peak and hole /e·Å30.79 and –0.440.23 and –0.270.42 and –0.38
Table 2. Selected bond lengths /Å and angles /° for complexes 1, 2 and 3.
Zn(1)–O(6)[a]1.953(5)Zn(3)–O(1)[c]2.399(7)
Zn(1)–O(14)1.996(5)Zn(3)–O(2)[c]2.065(6)
Zn(1)–N(10)2.029(7)Zn(3)–O(3)1.959(6)
Zn(1)–N(15)2.000(6)Zn(3)–N(5)2.058(7)
Zn(2)–O(9)[b]2.371(8)Zn(3)–N(20)2.020(7)
Zn(2)–O(10)[b]2.188(8)Zn(4)–O(7)2.026(6)
Zn(2)–O(12)1.981(5)Zn(4)–O(16)1.957(5)
Zn(2)–N(11)2.026(6)Zn(4)–N(1)[d]2.038(7)
Zn(2)–N(16)2.041(6)Zn(4)–N(6)[e]2.003(6)
O(6)[a]–Zn(1)–O(14)111.2(3)O(2)[c]–Zn(3)–O(1)[c]57.4(2)
O(6)[a]–Zn(1)–N(10)99.9(3)O(3)–Zn(3)–O(1)[c]98.3(2)
O(6)[a]–Zn(1)–N(15)123.1(2)O(3)–Zn(3)–O(2)[c]145.3(3)
O(14)–Zn(1)–N(10)95.9(2)O(3)–Zn(3)–N(5)101.4(3)
O(14)–Zn(1)–N(15)111.6(2)O(3)–Zn(3)–N(20)105.4(3)
N(15)–Zn(1)–N(10)110.9(3)N(5)–Zn(3)–O(1)[c]150.6(3)
O(10)[b]–Zn(2)–O(9)[b]55.8(3)N(5)–Zn(3)–O(2)[c]94.9(3)
O(12)–Zn(2)–O(9)[b]95.9(3)N(20)–Zn(3)–O(1)[c]96.4(3)
O(12)–Zn(2)–O(10)[b]118.4(3)N(20)–Zn(3)–O(2)[c]101.9(3)
O(12)–Zn(2)–N(11)125.2(3)N(20)–Zn(3)–N(5)99.2(3)
O(12)–Zn(2)–N(16)102.3(3)O(7)–Zn(4)–N(1)[d]100.6(3)
N(11)–Zn(2)–O(9)[b]91.7(3)O(16)–Zn(4)–O(7)106.0(2)
N(11)–Zn(2)–O(10)[b]110.5(3)O(16)–Zn(4)–N(1)[d]95.5(3)
N(11)–Zn(2)–N(16)101.5(3)O(16)–Zn(4)–N(6)[e]106.7(3)
N(16)–Zn(2)–O(9)[b]145.0(3)N(6)[e]–Zn(4)–O(7)139.6(3)
N(16)–Zn(2)–O(10)[b]89.2(3)N(6)[e]–Zn(4)–N(1)[d]99.3(3)
Co(1)–N(1)2.125(1)Co(1)–O(1)[a]2.138(1)
Co(1)–N(1)[a]2.125(1)Co(1)–O(1w)2.122(1)
Co(1)–O(1)2.138(1)Co(1)–N(1w)[a]2.122(1)
N(1)–Co(1)–N(1)[a]180.0O(1w)–Co(1)–N(1)90.77(6)
N(1)–Co(1)–O(1)[a]93.07(5)O(1w)[a] –Co(1)–N(1)[a]90.77(6)
N(1)[a]–Co(1)–O(1)[a]86.93(5)O(1w)–Co(1)–O(1)88.46(5)
N(1)[a]–Co(1)–O(1)93.07(5)O(1w)[a] –Co(1)–O(1)[a]88.46(5)
N(1)–Co(1)–O(1)86.93(5)O(1w)–Co(1)–O(1)[a]91.54(5)
O(1)–Co(1)–O(1)[a]180.0O(1w)[a] –Co(1)–O(1)91.54(5)
O(1w)[a]–Co(1)–N(1)89.23(6)O(1w)[a] –Co(1)–O(1w)180.0
O(1w)–Co(1)–N(1)[a]89.23(6)  
Cd(1)–O(1w)2.428(2)Cd(1)–O(4)2.290(2)
Cd(1)–O(2)[a]2.374(2)Cd(1)–N(1)[a]2.270(2)
Cd(1)–O(3)[b]2.346(2)Cd(1)–N(5)2.279(2)
O(2)[a]–Cd(1)–O(1w)80.07(8)N(1)[a]–Cd(1)–O(3)[b]86.73(8)
O(3)[b]–Cd(1)–O(1w)168.70(7)N(1)[a]–Cd(1)–O(4)102.27(8)
O(3)[b]–Cd(1)–O(2)[a]93.33(7)N(1)[a]–Cd(1)–N(5)169.20(9)
O(4)–Cd(1)–O(1w)80.67(8)N(5)–Cd(1)–O(1w)88.17(8)
O(4)–Cd(1)–O(2)[a]160.70(7)N(5)–Cd(1)–O(2)[a]94.13(8)
O(4)–Cd(1)–O(3)[b]105.48(7)N(5)–Cd(1)–O(3)[b]83.13(8)
N(1)[a]–Cd(1)–O(1q)101.39(8)N(5)–Cd(1)–O(4)84.10(8)
N(1)[a]–Cd(1)–O(2)[a]82.71(7)  

Crystallographic data (excluding structure factors) for the structures in this paper have been deposited with the Cambridge Crystallographic Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK. Copies of the data can be obtained free of charge on quoting the depository numbers CCDC-919392 http://www.ccdc.cam.ac.uk/data_request/cif , CCDC-918010 http://www.ccdc.cam.ac.uk/data_request/cif , and CCDC-919393 http://www.ccdc.cam.ac.uk/data_request/cif (Fax: +44-1223-336-033; E-Mail: deposit@ccdc.cam.ac.uk, http://www.ccdc.cam.ac.uk).

Supporting Information (see footnote on the first page of this article): The non-hydrogen fractional atomic coordination and equivalent isotropic displacement parameters for complexes 1, 2, and 3. The simulated and experimental X-ray powder diffraction patterns of 1, 2, and 3. The fluorescent emission spectra for bdc, pta and tda ligands.

Acknowledgements

  1. Top of page
  2. Abstract
  3. Introduction
  4. Results and Discussion
  5. Conclusions
  6. Experimental Section
  7. Acknowledgements
  8. Supporting Information

We thank the support of this work by National Natural Science Foundation of China (No. 31200642), Special Funds for the Basic R&D Program in the Central Non-profit Research Institutes (No. 20603022012018), Special Scientific Research Funds for Central Non-profit Institutes, Chinese Academy of Fishery Sciences (No. 2013A1002), and Qingdao Municipal Science and Technology Plan Project (No. 12–1-4–12-(2)-jch).

Supporting Information

  1. Top of page
  2. Abstract
  3. Introduction
  4. Results and Discussion
  5. Conclusions
  6. Experimental Section
  7. Acknowledgements
  8. Supporting Information

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