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Article

Two Interpenetrated Zn(II) Coordination Polymers: Synthesis, Topological Structures, and Property

School of Chemistry and Chemical Engineering, Fuyang Normal University, Fuyang 236041, China
*
Author to whom correspondence should be addressed.
Crystals 2019, 9(11), 601; https://doi.org/10.3390/cryst9110601
Submission received: 1 November 2019 / Revised: 12 November 2019 / Accepted: 14 November 2019 / Published: 17 November 2019
(This article belongs to the Special Issue Crystal Structure and Thermal Studies of Coordination Compounds)

Abstract

:
Two interpenetrated coordination polymers (CPs) {[Zn1(L)(NO2pbda)]n[Zn2(L)(NO2pbda)]n} (1) and [Zn(L)(Brpbda)]n (2) were prepared by reactions of zinc sulfate heptahydrate with N-donor ligands of 1,4-di(1H-imidazol-4-yl)benzene (L) and auxiliary carboxylic acids of nitroterephthalic acid (H2NO2pbda) and 2,5-dibromoterephthalic acid (H2Brpbda), respectively. The structures of the CPs were characterized by Fourier-Transform Infrared (IR) spectroscopy, elemental analysis, and single-crystal X-ray diffraction. The coordination polymer 1 has two different (4, 4) sql 2D layer structures based on the [Zn(L)(NO2pbda)] moiety, which results in inclined interpenetration with a 2D + 2D → 3D architecture, while the CP 2 exhibits a 3-fold interpenetrating dmp network. The diffuse reflectance spectra are also investigated for the CPs 1 and 2.

1. Introduction

The design of metal–organic coordination polymers (CPs), as one of the most active research areas, has acquired great attention in recent years, due to their intriguing structures and significant applications [1,2,3,4,5,6,7]. Recently, luminescent coordination polymers have been widely employed to detect guest molecules with high sensitivity and selectivity. For example, two CPs, {[Cd2L2(H2O)4]·H2O}n and {[Zn2L2(H2O)4]·H2O}n (H2L = 5-(1H-1,2,4-triazol-1-yl)isophthalic acid), can serve as highly selective and sensitive fluorescent probes toward CrVI-anions (CrO42− and Cr2O72−) [8]. In crystal engineering, the most important factors in assembling desirable CPs are the rational choosing of the bridging ligand and metal centers; in addition, other reaction conditions, such as solvent, temperature, pH value, and the nature of anions, can affect the resulting framework [9,10,11,12,13]. It should be mentioned that the length, rigidity, functional groups, coordination modes, or substituents of organic ligands can decide the final frameworks of CPs [14,15]. Generally, two important kinds of ligands, including N-donor and O-donor organic compounds, are widely used to construct diverse CPs, due to their various coordination modes and modifiable backbones [16,17]. Noticeably, rigid rod-type ligands, including 4,4΄-bipyridine (bpy), terephthalic acid, or their analogues, often act as pillars in building a rich variety of new entangled CPs [18,19], while the flexible ligands have different shapes associated with the trans or gauche conformation, favoring the formation of interesting entanglements [20,21]. More recently, a new type of rigid N-donor ligand, including the 4-imidazolyl group, has been designed by our group, and employed to fabricate porous crystalline materials with good gas adsorption properties [22,23,24,25,26,27,28,29,30,31,32,33,34]. Moreover, a series of diverse CPs have been built through the mixed system of imidazole and polycarboxylates [25,26]. Taking into account their good compatibility for the N/O donor mixed system, we choose different carboxylic acids with distinct natures, together with the rigid rod-type 1,4-di(1H-imidazol-4-yl)benzene (L) ligand to build novel CPs as our continual work. In this contribution, we report two Zn(II) CPs of {[Zn1(L)(NO2pbda)]n[Zn2(L)(NO2pbda)]n} (1) and [Zn(L)(Brpbda)] (2) by reactions of zinc sulfate heptahydrate with mixed ligands of L and nitroterephthalic acid (H2NO2pbda), and 2,5-dibromoterephthalic acid (H2Brpbda), respectively.

2. Materials and Methods

2.1. Materials and Techniques

The L organic ligand was synthesized according to the literature [27]. The infrared spectrum was recorded on a Bruker Vector 22 FTIR spectrophotometer (Instrument Inc., Karlsruhe, Germany). Elemental analyses were performed on a PerkinElmer 2400 elemental analyzer (PerkinElmer, Waltham, MA, USA). The UV–vis spectra were recorded using a computer-controlled PE Lambda 900 UV–vis spectrometer (PerkinElmer, USA). Thermogravimetric analyses (TGA) were analyzed by a simultaneous SDT 2960 thermal analyzer (Thermal Analysis Instrument Inc., New Castle, DE, USA). 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.

2.2. Synthesis of {[Zn1(L)(NO2pbda)]n[Zn2(L)(NO2pbda)]n} (1)

Mixtures of ZnSO4·7H2O (28.7 mg, 0.1 mmol), L (21.2 mg, 0.1 mmol), H2NO2pbda (21.1 mg, 0.1 mmol), and H2O (10 mL) were adjusted to pH = 7 with an NaOH solution (0.2 mol L−1), and were placed in a 25 mL Teflon-lined container and heated to 160 °C for 72 h. Brown block crystals of 1 were collected, with a yield of 69%, at room temperature. Anal. calcd for C20H13N5O6Zn (%): C, 49.56; H, 2.70; N, 14.45. Found: C, 49.38; H, 2.56; N, 14.62. IR: 3447 (w), 3141 (w), 1628 (vs), 1528 (s), 1488 (m), 1377 (m), 1346 (vs), 1264 (w), 1179 (w), 1124 (w), 1073 (w), 948 (w), 837 (m), 816 (m), 785 (w), 651 (w), 612 (w), 521 (w), 489 (w), 421 (w).

2.3. Synthesis of [Zn2(L)(Brpbda)2]n (2)

The same synthetic method as above was used, except that H2NO2pbda was replaced by H2Brpbda (32.4 mg, 0.01 mmol). Brown block crystals of 2 were obtained (yield: 61%). Anal. calcd for C20H10Br2N4O4Zn (%): C, 40.34; H, 1.69; N, 9.41. Found: C, 40.19; H, 1.75; N, 9.29. IR: 3465 (m), 3386 (m), 3126 (m), 2856 (m), 1638 (s), 1581 (s), 1545 (s), 1489 (m), 1412 (s), 1359 (m), 1272 (w), 1182 (m), 1172 (m), 1145 (m), 1132 (s), 1081 (m), 968 (m), 838 (m), 818 (s), 798 (m), 679 (m), 648 (m), 628 (w), 530 (w), 459 (w).

2.4. Crystallographic Data Collection and Refinements

The data collection for CPs 12 was carried out on a Bruker Smart Apex CCD area-detector diffractometer. The diffraction data and structural analysis were integrated using the SAINT program and the SADABS program, and anisotropically, on F2 by the full-matrix least-squares technique, respectively [28,29,30]. The details of the crystal parameters are summarized in Table 1; selected bond lengths and angles are listed in Table S1. CCDC: 1959065, 1959064 for 1 and 2. The atoms of C, O, and Br for CP 2 are disordered and split into (C5, C5B), (C6A, C6B), (C7A, C7B), (C8A, C8B), (C9A, C9B), (C10A, C10B), (O1A, O1B), (O2A, O2B), and (Br1A, Br1B). 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: [email protected]).

3. Results

3.1. Structural Descriptions

3.1.1. Structure of {[Zn1(L)(NO2pbda)]n[Zn2(L)(NO2pbda)]n} (1)

Single-crystal structural analysis reveals that CP 1 crystallizes in a monoclinic form with space group P 1 (Table 1). The asymmetric unit has two sets of [Zn(L)(NO2pbda)] units, and each unit includes a distinct Zn(II) atom, one L ligand, and one NO2pbda2−. Both of the Zn(II) atoms possess a N2O2 donor set, forming 4-coordinated tetrahedral coordination geometry (Figure 1a). The Zn−O bond distances range from 1.939(3) to 2.015(3) Å and the Zn−N bond distances range from 1.980(4) to 2.000(4) Å; the coordination angles around Zn(II) range from 94.83(14)° to 128.61(17)° (Table S1). Noticeably, in each independent set of [Zn(L)(NO2pbda)]n, the NO2pbda2− ligands act as linear ligands to link two Zn(II) atoms by the opposite carboxylate groups in the µ1-η1:η0-monodentate mode, forming a one-dimensional (1D) chain [Zn(NO2pbda)]n. The linear L ligands connect 1D chains into two-dimensional (2D) [Zn(L)(NO2pbda)]n layers (Figure 1b), which can be considered as 44-sql topology, by taking Zn(II) atoms as 4-connecting nodes, and the L and NO2pbda2− ligands as 2-connectors. Thus, two L ligands together with two NO2pbda2− units, connect four Zn(II) atoms to afford a [Zn4(L)2(NO2pbda2−)2] square unit, where the lateral Zn···Zn distances are around 9.10 and 13.36 Å. The rhombus has large rectangular windows, which permit inclined interpenetration for these two distinct [Zn(L)(NO2pbda)] layers, with an angle of 66.24°, forming the 2D + 2D → 3D inclined polycatenation framework (Figure 1c,d) [31,32].

3.1.2. Structure of [Zn(L)(Brpbda)]n (2)

A different H2Brpbda acid with a Br atom substituent group replaced H2NO2pbda in the reaction of 1, and the new compound of 2, possessing 3-fold interpenetrating dmp topology was obtained. Complex 2 crystallizes in the orthorhombic P nna space group, quite different from the monoclinic space group, P 1, in 1. The asymmetric unit includes half of the [Zn(L)(Brpbda)] units, namely half of a distinct Zn(II) atom, a Brpbda2− anion, and an L unit, respectively. As shown in Figure 2a, the Zn1 atom is coordinated by two oxygen atoms (O1, O1A) from two different Brpbda2− anions, and two nitrogen atoms (N3, N3A) of two L ligands, forming distorted tetrahedral coordination geometry. In 2, each Brpbda2− anion links two adjacent Zn2+ ions by two carboxyl groups using the µ1-η1:η0-monodentate coordination mode, generating a 1D zigzag chain along the a axis (Figure 2b). Similarly, the linear L ligands act as 2-connectors to link Zn(II) atoms to form 1D zigzag chains. As a consequence, these 1D chains are interconnected to afford a 3D coordination framework (Figure 2c). Topologically, both the μ2-Brpbda2− anions and the L ligands are linear 2-connectors, while each Zn(II) atom is a 4-connector to connect the other four Zn(II) atoms by two Brpbda2− and two L ligands. Thus, the network of 2 is a 4-connected dmp net with a (65·8) topology [33,34]. Due to the great void of each single net, it permits the inclusion of another two independent equivalent networks, resulting in a 3-fold interpenetrating dmp net (Figure 2d).

3.2. Thermal Analyses and X-Ray Power Diffraction Analyses

The stability of CPs 1 and 2 was evaluated by thermogravimetric analysis (TGA); the analysis results are listed in Figure S1. The results of TGA for CPs 1 and 2 showed no weight losses for the crystalline materials until the frameworks collapses at about 195 and 245 ºC respectively, indicating that the frameworks of compounds 12 contain no guest molecules, which is consistent with their structures, as evidenced by the analysis of the crystal structures. The diffraction peaks of as-synthesized CPs 1 and 2 fit well with the simulated power X-ray diffraction (PXRD) patterns from single crystal results. The result confirms that the as-synthesized crystalline materials of 1 and 2 are phase purities, as shown in Figure S2.

3.3. IR and Diffuse Reflectance Spectra

IR spectra of CPs 1 and 2 were recorded between 4000 and 400 cm−1. The characteristic peak with vibrational bands, 1638–1528 cm−1, disappear around 1700 cm−1, which means the carboxylic groups are deprotonated. The infrared spectra of L indicate the prominent characteristic absorption bands at 1528–1489 and 1270–1124 cm−1, attributed to its aromatic rings [35].
The UV–vis absorption spectra of 1 and 2 in their solid states were recorded in Figure 3. The L ligand shows intense absorption peaks ranging from 250 to 300 nm, which belongs to π−π* transitions [36]. Obviously, the CPs 1 and 2 showed similar absorption bands in the UV region, which correspond to intraligand π → π* and n → π* transitions. Furthermore, the diffuse reflectance data obtained were transformed into a Kubelka–Munk function to get their band gaps (Eg), which can be employed to evaluate the semiconductivity of the CPs. The values of Eg are estimated as 3.52 and 2.59 eV for CPs 1 and 2 (Figure 4), which were determined by a direct band gap semiconductor: (Ahν)2 = B(hν − Eg). The values of Eg for CPs 1 and 2 are comparatively a little higher than the series of Ni(II) compounds [37], and the as-synthesized crystalline materials may be optical semiconductors [38].

4. Conclusions

Two interpenetrated Zn(II) CPs based on mixed N-donor and O-donor ligands of L and aromatic dicarboxylic acid were prepared with reactions of zinc sulfate heptahydrate by hydrothermal reaction. The natures of the different substituent groups of auxiliary dicarboxylic acid ligands make different structures for CPs 1 and 2. The compounds 1 and 2 are 2D + 2D → 3D-inclined polycatenation structures or 3-fold interpenetrating dmp networks, due to different substituent groups from nitroterephthalic acid and 2,5-dibromoterephthalic acid. The UV–vis absorption spectra of 1 and 2 were investigated. The results have further confirmed that the mixed system of N/O-donor ligands is a favorable strategy for building diverse coordination polymers.

Supplementary Materials

The following are available online at https://www.mdpi.com/2073-4352/9/11/601/s1. Figure S1 and S2 represent TGA and PXRD. Selected bond lengths and bond angles are listed in Table S1.

Author Contributions

Z.-W.H. and C.-J.L. did the experiments and analyzed the data. W.-D.L. and S.-S.H. made the measurements. S.-S.C. charged the project.

Funding

Thanks for the funding of the Cooperative Project of Fuyang Government (XDHX201707) and the youth talent program (gxbjZD19).

Conflicts of Interest

The authors declare no conflict of interest.

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Figure 1. (a) The coordination environment of the Zn(II) atoms in 1. Symmetry code: A x, 1+y, 1+z, B −1+x, y, z, C x, 1+y, z. (b) 2D polycatenation of 1. (c) The 3D framework built from 2D + 2D → 3D interpenetration. (d) Schematic representation of inclined interpenetration in 1.
Figure 1. (a) The coordination environment of the Zn(II) atoms in 1. Symmetry code: A x, 1+y, 1+z, B −1+x, y, z, C x, 1+y, z. (b) 2D polycatenation of 1. (c) The 3D framework built from 2D + 2D → 3D interpenetration. (d) Schematic representation of inclined interpenetration in 1.
Crystals 09 00601 g001
Figure 2. (a) The coordination environment of the Zn(II) atoms in 2. Symmetry code: A 2−x, 1−y, 1−z, B x, 0.5−y, 0.5−z, C 0.5−x, −y, z. (b) 1D chains of [Zn(II) (Brpbda2−)] and [Zn(II)(L)] in 2. (c) 3D framework of 2. (d) Schematic representation of the 3-fold interpenetrating dmp net with a (65·8) topology.
Figure 2. (a) The coordination environment of the Zn(II) atoms in 2. Symmetry code: A 2−x, 1−y, 1−z, B x, 0.5−y, 0.5−z, C 0.5−x, −y, z. (b) 1D chains of [Zn(II) (Brpbda2−)] and [Zn(II)(L)] in 2. (c) 3D framework of 2. (d) Schematic representation of the 3-fold interpenetrating dmp net with a (65·8) topology.
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Figure 3. The UV–vis spectra for the CPs 12.
Figure 3. The UV–vis spectra for the CPs 12.
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Figure 4. The Eg values for CPs 12 treated with the Kumble–Munk function.
Figure 4. The Eg values for CPs 12 treated with the Kumble–Munk function.
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Table 1. Crystallographic data and structure refinement details for coordination polymers (CPs) 1 and 2.
Table 1. Crystallographic data and structure refinement details for coordination polymers (CPs) 1 and 2.
12
Empirical formulaC20H13N5O6ZnC20H10Br2N4O4Zn
Formula weight484.72595.51
Temperature/K296(2)296(2)
Crystal systemTriclinicOrthorhombic
Space groupP 1P nna
a9.037(2)11.0101(10)
b9.141(2)14.6802(14)
c12.948(314.8721(13)
α107.832(3)90
β95.123(3)90
γ108.233(3)90
V3)946.6(4)2403.8(4)
Z, Dcalc/(Mg/m3)2, 1.7014, 1.646
F(000)4921160
θ range/°1.69–25.993.59–25.01
Reflections collected713126144
Independent reflections59422088
Goodness-of-fit on F20.9971.094
R1 [I > 2σ (I)] a0.03980.0989
wR2 [I > 2σ (I)] b0.08190.2401
aR1 = Σ||Fo| − |Fc||/Σ|Fo|. b wR2 = |Σw(|Fo|2 − |Fc|2)|/Σ|w(Fo)2|1/2, where w = 1/[σ2(Fo2) + (aP)2 + bP]. P = (Fo2 + 2Fc2)/3.

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MDPI and ACS Style

He, Z.-W.; Liu, C.-J.; Li, W.-D.; Han, S.-S.; Chen, S.-S. Two Interpenetrated Zn(II) Coordination Polymers: Synthesis, Topological Structures, and Property. Crystals 2019, 9, 601. https://doi.org/10.3390/cryst9110601

AMA Style

He Z-W, Liu C-J, Li W-D, Han S-S, Chen S-S. Two Interpenetrated Zn(II) Coordination Polymers: Synthesis, Topological Structures, and Property. Crystals. 2019; 9(11):601. https://doi.org/10.3390/cryst9110601

Chicago/Turabian Style

He, Zi-Wei, Chang-Jie Liu, Wei-Dong Li, Shuai-Shuai Han, and Shui-Sheng Chen. 2019. "Two Interpenetrated Zn(II) Coordination Polymers: Synthesis, Topological Structures, and Property" Crystals 9, no. 11: 601. https://doi.org/10.3390/cryst9110601

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