Synthesis, Crystal Structures, and Properties of a New Supramolecular Polymer Based on Mixed Imidazole and Carboxylate Ligands
College of Chemistry & Chemical Engineering, Fuyang Normal University, Fuyang 236041, China
*
Author to whom correspondence should be addressed.
Crystals 2017, 7(7), 210; https://doi.org/10.3390/cryst7070210
Submission received: 5 June 2017
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Revised: 1 July 2017
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Accepted: 2 July 2017
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Published: 13 July 2017
Abstract
:One new coordination polymer, namely, [Cd3(H2L)3(Pza)2(H2O)2]n (1) was synthesized by the reaction of Cd(NO3)2·4H2O with 1,4-di(1H-imidazol-4-yl)benzene (H2L) and 3,5-pyrazoledicarboxylic acid (H3pza) and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis, and powder X-ray diffraction (PXRD). The H3pza ligand was completely deprotonated to pza3−, which bridged the Cd2+ to form one-dimensional (1D) chain. The adjacent 1D chains were further linked into the two-dimensional (2D) layer by the linear H2L ligands. The weak interaction, including hydrogen bonds and π−π stacking interactions, extends the 2D layers into three-dimensional (3D) supramolecular polymer. Complex 1 shows intense light blue emission in the solid state at room temperature.
1. Introduction
In the recent years, rational design and successful construction of metal-organic frameworks (MOFs) has become an expanding research topic in the fields of synthetic chemistry and materials science not only because of their intriguing variety of architectures and captivating topologies but also their potentially multi-field applications in numerous areas in fluorescence, gas adsorption/separation, magnetic properties, electrochemistry, catalysis, and so on [1,2,3,4,5,6,7,8]. The MOFs possessing versatile structures and desired properties are mainly dependent on the appropriate organic linkers [9,10], and the external synthesis conditions such as pH values, molar ratio of reactants, reaction temperatures, solvent system, and counter anions play important roles in deciding the resulting architectures [11,12,13]. Up to now, the N- or O-donor organic ligands have been employed extensively to construct functional coordination polymers [14,15,16]. Particularly, the N-donor compounds such as imidazole, pyrazole, triazole, and tetrazole can exhibit flexible coordination modes and afford more predictable coordination modes, as a result, these types of ligands have been extensively employed to construct diverse complexes.
In our previous studies, we have elaborately designed the series of 4-imidazole-containing imidazole ligands such as 1,4-di(1H-imidazol-4-yl)benzene and 1,3,5-tri(1H-imidazol-4-yl)benzene and successfully synthesized the porous MOFs based on the metal-imidazolate building units, showing favorable gas adsorption, especially selective adsorption property for CO2 molecules [17,18]. Considering that a mixed ligand assembly strategy incorporating imidazole-containing ligands and polycarboxylates can effectively construct diverse topological networks, we have employed the 4-imidazolyl-containing ligands to build some novel frameworks together with different carboxylate ligands [19,20].
As an extension of our previous work, we apply the 4-imidazoly-containing ligand of 1,4-di(1H-imidazol-4-yl)benzene to build new coordination polymer together with dicarboxylic acid of a 3,5-pyrazoledicarboxylic acid containing pyzole parent nucleus. Here, we report the synthesis and crystal structure of a new coordination polymer of [Cd3(H2L)3(Pza)2(H2O)2]n (1) obtained by the reaction of these mixed ligands with CdCl2·2.5H2O under hydrothermal condition.
2. Results and Discussion
2.1. Structural Description of [Cd3(H2L)3(Pza)2(H2O)2]n (1)
Single crystal X-ray diffraction analysis reveals that [Cd3(H2L)3(Pza)2(H2O)2]n crystallizes in triclinic P-1 space group. The asymmetric unit of 1 contains two crystallographically independent Cd(II) atoms, one and a half L ligands, one completely deprotonated pza3−, and one coordinated water molecule. It should be mentioned that both H2L and H3pza have active hydrogen atoms in the heterocyclic rings, and can deprotonate to be anion ligands, but the H2L keeps a neutral ligand and three active protons from the carboxyl groups and pyzole of H3Pza completely deprotonated to be pza3−, in this sense, the complex keep neutral. As shown in Figure 1, the Cd1 center is sitting on an inversion center and has octahedral coordination geometry with N4O2 binding set coordinated by two pairs of atoms (O(4), N(7) and O(4A), N(7A)) from two distinct pza3− ligands and another two nitrogen atoms (N5, N5A) from two other H2L ligands. The Cd–N distances are 2.299(2) and 2.3449(19) Å while the Cd–O distance is 2.3324(18) Å, and the coordination angles around Cd(1) are in the range of 73.27(6)°~180.0° (Table 1). In this complex, both of carboxyl group in µ1-η1:η0-monodentate coordination mode from pza3− ligand together with adjacent N atom chelate with one Cd(II) atom, in return, each pza3− ligand acts as a μ2-bridge to link two Cd(II) atoms. This connection makes a one-dimensional (1D) chain of [Cd3(Pza)2] (Figure 2). These adjacent 1D chains are connected by linear H2L ligand into two-dimensional (2D) layer structure (Figure 3). Particularly, the NH or N atom of imidazolyl groups and the carboxyl group, can act as hydrogen bonding donor or acceptor, thus easily benefiting the construction of supramolecular structures. Therefore, there exists rich hydrogen bonding interaction in this complex, and the N−H···O and C−H···O (N(2)···O(1) 2.738(3) Å, N(2)–H(2A)···O(1) 160°; N(4)···O(3) 2.744(3) Å, N(4)–H(4A)···O(3) 176°; N(6)···O(3) 2.745(3) Å, N(6)–H(6)···O(3) 161°; C(4)···O(1) 3.071(3) Å, C(4)–H(4)···O(1) 117°) hydrogen bond exist among the 2D layers highlighted in pink dotted lines (Table 2), moreover, the classic weak π−π stacking interactions also exist between the two neighboring 2D layers. The two imidazole rings of the H2L ligands between the adjacent 2D layers are parallel and are separated by a centroid−centroid distance of 3.86 Å, indicating the presence of π−π stacking interactions [21]. Generally, the weak interactions of hydrogen bonding and π−π stacking interactions further link the 2D layers into three-dimensional (3D) supramolecular polymer (Figure 4).
2.2. Thermal Analysis and Powder X-ray Diffraction Analysis
Complex 1 was examined by thermogravimetric analysis (TGA) to investigate the thermal stability of supramolecular architecture in the N2 atmosphere from 25–750 °C, and the result is shown in Figure 5. For 1, weight loss of 2.93 % was observed in the temperature range of 80–105 °C, which corresponds to the exclusion of coordinated water molecules (calcd 2.75 % for 1), and further weight loss was observed at about 320 °C, owing to the decomposition of the framework of 1. A powder XRD experiment was carried out to confirm the phase purity of bulk sample, and the experimental pattern of the as-synthesized sample can be considered comparable to the corresponding simulated one, indicating the phase purity of the sample (Figure 6).
2.3. Photoluminescent Property
Inorganic–organic hybrid complexes, especially comprising the d10 closed-shell metal center and aromatic-containing system, have been reported to have the ability to adjust the emission through incorporation of metal centers, which impetus us to investigate the fluorescence property [22,23,24]. In this paper, the solid-state photoluminescent property of complex 1 as well as the organic ligands has been investigated in the solid state at room temperature as depicted in Figure 7. The free H2L ligand shows intense emission band at 455 nm upon excitation at 342 nm, which may be attributed to π* → π transition of the intraligands because the aromatic nucleus of H2L ligand are coplane [25]. However, the H3pza nearly does not show fluorescence because the fluorescent emission of benzene-dicarboxylate ligands resulting from the π* → n transition is very weak compared with that of the π* → π transition of the H2L ligand, therefore, benzene-carboxylate ligands almost have no contribution to the fluorescent emission of as-synthesized coordination polymers [16,26]. It can be seen that complex 1 exhibits strong broad blue photoluminescence with emission maxima at 420 nm upon excitation at 338 nm. By contrast with the free ligand, the emission bands of complex 1 are 35 nm blue-shifted. Such board emission bands may be tentatively assigned to ligand-to-metal charge transfer (LMCT) [27,28]. In addition, the Figure 7 shows that the luminescence intensity of 1 has increased compared with the free ligand under the same conditions, which may mainly originate from the coordination interactions between the metal Cd(II) atom and the ligand, which enhanced its conformational rigidity and then decreased the nonradiative energy loss [29].
3. Experimental Section
3.1. Materials and Instrumentation
All the chemicals and solvents used in this experiment were of reagent grade without further purification. Elemental analyses were performed on a Perkin-Elmer 240C Elemental Analyzer (PerkinElmer, Waltham, USA). IR spectra were recorded on a Bruker Vector 22 FT-IR spectrophotometer (Instrument Inc., Karlsruhe, Germany) using KBr pellets. Thermogravimetric analyses (TGA) were performed on a simultaneous SDT 2960 thermal analyzer (Thermal Analysis Instrument Inc., New Castle, DE, USA) under nitrogen with a heating rate of 10 °C min−1. Power X-ray diffraction (PXRD) patterns were measured on a Shimadzu XRD-6000 X-ray diffractometer (Shimadzu Corporation, Kyoto, Japan) with CuKα (λ = 1.5418 Å) radiation at room temperature. The fluorescent spectra were measured using a Perkin Elmer LS-55B fluorescence spectrometer (PerkinElmer, Billerica, MA, USA).
3.2. Synthesis of [Cd3(H2L)3(Pza)2(H2O)2]n (1)
A mixture of H2L (0.021 g, 0.1 mmol), H3Pza (0.0308 g, 0.1 mmol), CdCl2·2.5H2O (0.0228 g, 0.1 mmol) and NaOH (0.004 g, 0.1 mmol) in 10 mL H2O was sealed in a 20 mL Teflon-lined stainless steel container and heated at 180 °C for 48 h. Coloress block crystals of 1 were collected with a yield of 52% by filtration and washed with water and ethanol for several times. Anal. Calcd. (%) for C46H36N16O10Cd3: C, 42.17; H, 2.77; N, 17.11. Found (%): C, 42.36; H, 2.92; N, 17.31. IR(KBr): 3371−2545(m), 1598(vs), 1551(vs), 1512(m), 1392(vs), 1298(m), 1190(m), 1171(m), 1129(s), 1059(w), 955(m), 859(s), 829(m), 788(s), 705(m), 650(m), 510(m) cm−1.
3.3. Crystal Structure Determination
The single crystal data of [Cd3(H2L)3(Pza)2(H2O)2]n (1) was collected on a Bruker Smart APEX CCD diffractometer with graphite-monochromated MoKα radiation (λ = 0.71073 Å) at 293(2) K. The structure was solved by direct method and refined by full-matrix least squares on F2 using the SHELX-97 program [30]. The hydrogen atoms were generated geometrically. The crystallographic data and structural refinement are listed in Table 3.
Crystallographic data for the structure reported in this paper has been deposited with the Cambridge Crystallographic Data Centre as supplementary publication Nos. CCDC 1554215 for 1. Copy of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (Fax: +44-1223-336-033; E-Mail: deposit@ccdc.cam.ac.uk).
4. Conclusions
In summary, we have successfully obtained a new coordination polymer [Cd3(H2L)3(Pza)2(H2O)2]n (1) by the reaction of Cd(II) salt with mixed imidazole and carboxylate ligands. The H3Pza was completely deprotonated to pza3− anions that connected Cd(II) into infinite 1D chain structure. The adjacent 1D chains were further linked to form a 2D network by rigid ditopic H2L ligands. Furthermore, the 3D coordination polymer was generated by the classic weak hydrogen bond and π−π stacking interactions. Moreover, the complex 1 exhibits blue photoluminescence emission at 420 nm upon excitation at 338 nm.
Acknowledgments
This project was supported by Natural Science Foundation of Fuyang (KJ2011B123).
Author Contributions
Zhu Mei-An and Shi Shan-Shan synthesize the organic compounds. Han Shuai-Shuai and Mei Jin synthesized the metal coordination polymers. Chen Shui-Sheng designed the method and guided the manuscript.
Conflicts of Interest
The authors declare no conflict of interest.
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Figure 1.
The coordination environment of Cd(II) ion in 1 with the ellipsoids drawn at the 30% probability level. The hydrogen atoms are omitted for clarity. Symmetry code: A 1 − x, −y, 3 − z, B −1 + x, y, 1 + z, C 1 − x, 1 − y, 2 − z, D 2 − x, −y, 2 − z.
Figure 1.
The coordination environment of Cd(II) ion in 1 with the ellipsoids drawn at the 30% probability level. The hydrogen atoms are omitted for clarity. Symmetry code: A 1 − x, −y, 3 − z, B −1 + x, y, 1 + z, C 1 − x, 1 − y, 2 − z, D 2 − x, −y, 2 − z.
Figure 2.
1D chain structure of 1.
Figure 3.
2D layer structure of 1.
Figure 4.
3D supramolecular network structure of 1 linked by hydrogen bonding (pink dotted line) and π···π stacking interactions by a centroid−centroid distance of 3.86 Å (blue dotted line).
Figure 4.
3D supramolecular network structure of 1 linked by hydrogen bonding (pink dotted line) and π···π stacking interactions by a centroid−centroid distance of 3.86 Å (blue dotted line).
Figure 5.
Thermal analysis curve of the complex 1.
Figure 6.
Simulated and experimental XRPD patterns of supramolecular polymer 1.
Figure 7.
Solid-state photoluminescent spectra of 1 and H2L ligand at room temperature.
Table 1.
Selected bond lengths (Å) and bond angles (°) for 1.
| Bond | d | Bond | d |
|---|---|---|---|
| Cd(1)–N(5) | 2.299(2) | Cd(1)–O(4) | 2.3324(18) |
| Cd(1)–N(7) | 2.3449(19) | Cd(2)–N(3) | 2.258(2) |
| Cd(2)–N(1) ii | 2.245(2) | Cd(2)–N(8) iii | 2.3473(19) |
| Cd(2)–O(2) | 2.4204(17) | Cd(2)–O(5) | 2.481(2) |
| Angle | ω | Angle | ω |
| N(5) i–Cd(1)–N(5) | 180.000(1) | N(5) i–Cd(1)–O(4) | 86.21(8) |
| N(5)–Cd(1)–O(4) | 93.79(8) | O(4)–Cd(1)–O(4) i | 180.0 |
| N(5) i–Cd(1)–N(7) | 93.10(7) | N(5)–Cd(1)–N(7) | 86.90(7) |
| O(4)–Cd(1)–N(7) | 73.27(6) | O(4) i–Cd(1)–N(7) | 106.73(6) |
| O(4)–Cd(1)–N(7) i | 106.73(6) | N(7)–Cd(1)–N(7) i | 180.00(6) |
| N(1) ii–Cd(2)–N(3) | 146.85(8) | N(1) ii–Cd(2)–N(8) iii | 116.08(8) |
| N(3)–Cd(2)–N(8) iii | 92.92(7) | N(1) ii–Cd(2)–O(2) iii | 86.93(7) |
| N(3)–Cd(2)–O(2) iii | 119.34(8) | N(8) iii–Cd(2)–O(2) iii | 70.78(6) |
| N(1) ii–Cd(2)–O(2) | 87.58(7) | N(3)–Cd(2)–O(2) | 86.32(7) |
| N(8) iii–Cd(2)–O(2) | 128.20(6) | O(2) iii–Cd(2)–O(2) | 65.03(7) |
| N(1) ii–Cd(2)–O(5) | 80.02(7) | N(3)–Cd(2)–O(5) | 81.14(8) |
| N(8) iii–Cd(2)–O(5) | 96.39(7) | O(2) iii–Cd(2)–O(5) | 155.45(8) |
| O(2)–Cd(2)–O(5) | 134.25(7) |
Symmetry codes: (i) –x + 1, −y, −z + 3 (ii) x − 1, y, z + 1; (iii) –x + 1, −y + 1, −z + 2.
Table 2.
Hydrogen Bond Lengths (Å) and Bond Angles (°) for 1.
| D–H···A | d(D–H) | d(H···A) | d(D···A) | ∠DHA |
|---|---|---|---|---|
| O(5)–H(5W1)···O(4) a | 0.83 | 1.90 | 2.722(3) | 173(3) |
| N(2)–H(2A)···O(1) b | 0.8600 | 1.9100 | 2.738(3) | 160.00 |
| N(4)–H(4A)···O(3) c | 0.8600 | 1.8900 | 2.744(3) | 176.00 |
| N(6)–H(6)···O(3) d | 0.8600 | 1.9200 | 2.745(3) | 161.00 |
| C(4)–H(4)···O(1) b | 0.9300 | 2.5300 | 3.071(3) | 117.00 |
| C(12)–H(12)···O(5) e | 0.9300 | 2.4900 | 3.033(3) | 117.00 |
Symmetry codes: (a) x, 1 + y, −1 + z; (b) 1 − x, 1 − y, 1 − z; (c) 1 − x, -y, 2 − z; (d) 1 + x, y, z; (e) 1 + x, y, −1 + z.
Table 3.
Crystallographic data and structure refinement for 1.
| Empirical Formula | C46H36N16O10Cd3 |
|---|---|
| Formula weight | 1310.14 |
| Temperature/K | 296(2) |
| Crystal system | Triclinic |
| Space group | P-1 |
| a/Å | 9.5416(10) |
| b/Å | 11.3868(12) |
| c/Å | 12.8411(14) |
| α/° | 65.8260(10) |
| β/° | 77.4100(10) |
| γ/° | 80.1150(10) |
| Volume/Å3 | 1236.9(2) |
| Z | 1 |
| ρcalcmg/mm3 | 1.759 |
| μ/mm−1 | 1.353 |
| S | 1.090 |
| F(000) | 648 |
| Index ranges | −11 ≤ h ≤ 11, −13 ≤ k ≤ 14, −16 ≤ l ≤ 15 |
| Reflections collected | 9658 |
| Independent reflections | 5038 |
| Data/restraints/parameters | 5038/2/348 |
| Goodness-of-fit on F2 | 1.090 |
| Final R indexes [I ≥ 2σ(I)] | R1 = 0.0225, wR2 = 0.0619 |
| Final R indexes [all data] | R1 = 0.0259, wR2 = 0.0639 |
| Largest diff. peak/hole / e Å−3 | 1.298/−0.327 |
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Zhu, M.-A.; Shi, S.-S.; Han, S.-S.; Mei, J.; Chen, S.-S. Synthesis, Crystal Structures, and Properties of a New Supramolecular Polymer Based on Mixed Imidazole and Carboxylate Ligands. Crystals 2017, 7, 210. https://doi.org/10.3390/cryst7070210
AMA Style
Zhu M-A, Shi S-S, Han S-S, Mei J, Chen S-S. Synthesis, Crystal Structures, and Properties of a New Supramolecular Polymer Based on Mixed Imidazole and Carboxylate Ligands. Crystals. 2017; 7(7):210. https://doi.org/10.3390/cryst7070210
Chicago/Turabian StyleZhu, Mei-An, Shan-Shan Shi, Shuai-Shuai Han, Jin Mei, and Shui-Sheng Chen. 2017. "Synthesis, Crystal Structures, and Properties of a New Supramolecular Polymer Based on Mixed Imidazole and Carboxylate Ligands" Crystals 7, no. 7: 210. https://doi.org/10.3390/cryst7070210
APA StyleZhu, M.-A., Shi, S.-S., Han, S.-S., Mei, J., & Chen, S.-S. (2017). Synthesis, Crystal Structures, and Properties of a New Supramolecular Polymer Based on Mixed Imidazole and Carboxylate Ligands. Crystals, 7(7), 210. https://doi.org/10.3390/cryst7070210
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