Synthesis of a Water-Stable Zn(Ⅱ)-Based Metal-Organic Framework for Luminescence Detecting Fe3+ and 2, 6-Dichloro-4-nitroaniline

Xiao-Qing WANG Xue-Hui MA Dou-Dou FENG Jing TANG Dan WU

Citation:  Xiao-Qing WANG, Xue-Hui MA, Dou-Dou FENG, Jing TANG, Dan WU. Synthesis of a Water-Stable Zn(Ⅱ)-Based Metal-Organic Framework for Luminescence Detecting Fe3+ and 2, 6-Dichloro-4-nitroaniline[J]. Chinese Journal of Inorganic Chemistry, 2022, 38(1): 137-144. doi: 10.11862/CJIC.2022.015 shu

一种水稳性的Zn基金属-有机框架的合成及其对铁离子及2,6-二氯-4-硝基苯胺的荧光识别

    通讯作者: 王晓晴, xqwang@nuc.edu.cn
  • 基金项目:

    国家自然科学基金 21601163

    国家自然科学基金 22078309

    山西省高等学校科技创新项目 2019L0579

    中北大学青年学术带头人 QX201906

摘要: 以3,5-双(4-羧基苯氧基)吡啶(H2bcpp)和1,4-双(1-咪唑基)苯(1,4-bib)为配体,通过溶剂热法构筑了一个新型的热稳定性和水稳定性的Zn(Ⅱ)基金属-有机框架:[Zn2(bcpp)2(1,4-bib)2]·1.5H2O(1)。配合物1属于单斜晶系,I2/a空间群,具有一维管状结构。相邻的一维结构通过相互穿插形成一个三维超分子结构。此外,配合物1具有良好的荧光性,能够对水溶液中的铁离子及农药2,6-二氯-4-硝基苯胺实现高灵敏及高选择的荧光猝灭检测。

English

  • Currently, the large discharge of hazardous pollutants from agriculture, mines, and factories has brought serious damage to the ecological environment and physical health. For example, organochlorine pesticides have been widely applied to kill off insect pests and improve the yield of crops[1]. The 2, 6-dichloro-4-nitroaniline (DCN) is one of organochlorine pesticides, which is a broad- spectrum insect killer and can be used to prevent cotton rotten bells, wheat powdery mildew, and garden stuff rot[2]. Whereas the degradation of DCN needs a long time, and the ingestion of DCN residues on food can damage the immune system of humans and cause cancer or other illnesses. Moreover, Fe3+ ions exist in living systems that take part in some cellular processes, such as oxygen transport and hemoglobin formation[3]. However, the excess of Fe3+ ions can lead to some diseases of proteins and nucleic acids. Thus, exploring a rapid and effective detecting method to sense metal ions and organochlorine pesticides is significant.

    The fluorescence sensor exhibits rapid response, high sensitivity, selectivity, and simple operation for detecting pollutants. Recently, metal-organic frameworks (MOFs) as novel fluorescence sensors have been used to detect pollutants, including heavy metal cations (Fe3+, Hg2+, Cu2+), inorganic anions (F-, Cr2O42-, MnO42-), pesticides (organochlorine pesticides, organophosphorus pesticides), nitrobenzene, and so on[4-8], which can be attributed to their high surface areas, diverse chemical and physical properties, excellent fluorescence properties and abundant action sites. Among them, these MOFs based on d10 metal centers (Zn2+, Cd2+) and the conjugated ligands have been potentially used as photoluminescent probe materials to detect pollutants due to their excellent fluorescence properties. Nevertheless, the stability of MOFs is still a significant challenge for practical applications as fluorescence sensors in an aqueous solution.

    The hard-soft acid-base (HSAB) theory indicates that the Zn(Ⅱ) is a relatively soft-acid ion, which has stronger coordination bonding with the soft-base N-donor ligands[9]. But the strong coordination bonds could lead to poor crystallinity. Based on the guidelines, we chose mixed ligands (rigid N-donor ligand and flexible carboxylic ligand) to construct a 1D rhombic nanotube structure with high stability and crystallinity, [Zn2(bcpp)2(1, 4-bib)2]·1.5H2O (1) (H2bcpp=3, 5-bis(4-carboxylphenoxy)pyridine, 1, 4-bib=1, 4-bis(1-imidazoly)benzene). Based on the high water stability and excellent luminescent property, complex 1 was used as a multi-responsive sensor to detect metal ions and pesticides in aqueous solutions and real samples.

    All reagents and materials were commercially available and used directly without further purification. The ligands H2bcpp and 1, 4-bib were obtained from Jinan Henhua Sci. & Technol. Co., Ltd. Powder X-ray diffraction (PXRD) patterns were performed with a Rigaku Dmax 2500 diffractometer (XRD, Cu , λ = 0.154 nm, U =40 kV, I=25 mA, 2θ =5°-50°). Infrared spectra were obtained at FTIR-8400S spectrometer and thermogravimetric analysis (TGA) curves were carried out with a ZCT-A analyzer. UV-Vis absorption experiments were performed with a Shimadzu UV-2600 spectrophotometer. Photo-luminescence spectra were taken on a Hitachi F-4600 fluorescence spectrophotometer.

    A mixture of Zn(NO3)2·6H2O (0.016 mmol, 4.8 mg), H2bcpp (0.008 0 mmol, 2.8 mg), 1, 4-bib (0.016 mmol, 3.4 mg) in EtOH/H2O (4.0 mL, 1∶3, V/V) was sealed in a 25 mL reactor, heated to 120 ℃ for 55 h, and then cooled to room temperature. Colorless block crystals were obtained by washed with EtOH, filtration and dried in air. Anal. Calad. for C68H52N8O8Zn2(%): C, 65.81; H, 4.19; N, 9.03. Found(%): C, 65.77; H, 4.22; N, 9.06. IR(KBr, cm-1): 3 789(w), 3 122(w), 2 358(s), 1 674(m), 1 677(w), 1 569(m), 1 554(m), 1 539(m), 1 521(w), 1 488(m), 1 452(m), 1 429(m), 1 406(m), 1 379(m), 1 307(m), 1 294(m), 1 263(m), 1 026(m), 999 (m), 954(w), 838(m), 729(m), 653(m) (Fig.S1, Supporting information).

    The crystal data of 1 were collected on a Rigaku Oxford Diffraction XtaLAB Synergy-S diffractometer with Cu radiation (λ =0.154 184 nm) at 150 K. Its structure was solved by the superfilp method in Olex2 program. All non hydrogen atoms were refined on F2 with full-matrix least-squares procedures in SHELXL-2016. Some free disordered solvent molecules were removed with the PLATON/SQUEEZE routine. The SQUEEZE result reveals a residual electron density of 141 electrons/cell (Z=8) which corresponds to the residual electron density of 1.5 H2O molecules. The free 1.5 H2O molecules were also proved by the TGA and elemental analysis. The crystal data and refined parameters are presented in Table 1. Some selected bond distanced and angles are listed in Table S1.

    Table 1

    Table 1.  Crystal data and refined parameters of complex 1
    下载: 导出CSV
    Parameter 1
    Formula C68H52N8O8Zn2
    Formula weight 1 239.91
    Crystal system Monoclinic
    Space group I2/a
    a / nm 1.683 61(3)
    b / nm 2.566 63(4)
    c / nm 2.778 46(5)
    β/(°) 98.905(2)
    Z 8
    V / nm3 11.861 6(4)
    Dc / (g·cm-3) 1.389
    μ / mm-1 1.520
    F(000) 5 120.0
    Unique reflection 39 446
    Observed reflection [I > 2σ(I)] 11 716
    Parameter 1 162
    GOF 1.070
    Final R indices [I > 2σ(I)] R1=0.072 1, wR2=0.205 0
    R indices (all data) R1=0.085 2, wR2=0.215 9

    CCDC: 2095435.

    Single crystal X ray diffraction analysis presents that complex 1 crystallizes in the monoclinic with space group I2/a. Fig. 1a displays that the asymmetric unit contains two Zn(Ⅱ) ions, two bcpp2- ligands, two 1, 4-bib ligands, where the free disordered solvent molecules are omitted. The dihedral angles between two benzene rings in two different bcpp2- ligands are 40.941(331)° and 50.180(265)°, respectively (Fig. S2). Both Zn(Ⅱ) ion are four coordinated by two nitrogen atoms from different 1, 4-bib ligands and two oxygen atoms from two bcpp2- ligands with a distorted tetrahedral geometry. The average bond distances of Zn—N and Zn—O are in the ranges of 0.200 2 0.202 7 nm and 0.187 7-0.202 8 nm, respectively, which are in accordance with the reported values previously[10].

    Figure 1

    Figure 1.  Asymmetric unit of 1 with 50% thermal ellipsoid probability (a); 1D tubular structure of complex 1 along b axis (b) and along a axis (c) with 50% thermal ellipsoid probability

    All of the hydrogen atoms are omitted for clarity

    In complex 1, H2bcpp ligands are completely deprotonated. Each carboxylate group of bcpp2- bridges one Zn(Ⅱ) ion, which exhibits the coordination mode of η1. Two bcpp2- ligands bridge two Zn(Ⅱ) ion to form a ring. The adjacent rings are linked by two 1, 4-bib ligands, to form a 1D tubular structure with a rhombic channel (the diagonal length of 1.5 nm×1.9 nm, Fig. 1b and 1c). Because of the large rhombic windows in 1, the adjacent 1D tubular structures are interpenetrated with each other. Moreover, the imidazole rings of the adjacent 1, 4-bib ligands exist two ππ stacking interactions with face-to-face fashion, but two imidazole rings are not exactly parallel (Fig. 2a). One is the π stacking interaction between Cg1 plane and Cg3 plane (Cg1: N5-C75-N6-C77-C76, Cg3: N9-C87-N10-C89-C88, centroid…centroid 0.376 93 nm, dihedral angle 4.7°). The other is the π -stacking interaction between Cg2 plane and Cg4 plane (Cg2: N7-C85-C84-N8-C86, Cg4: N11-C96-C97-N12-C98, centroid…centroid 0.378 77 nm, dihedral angle 1.4°). The adjacent 1D tubular structures are interpenetrated and linked by weak π-stacking interactions to form a 3D supramolecular structure (Fig. 2b).

    Figure 2

    Figure 2.  (a) π-stacking interaction in complex 1; (b) 3D supramolecular structure of 1 viewed along b axis with 50% thermal ellipsoid probability

    The thermal stability of 1 was studied under an N2 atmosphere from 50 to 700 ℃ (Fig. S3). Complex 1 displayed a weight loss of 2.2% between 50 and 113 ℃ because of the loss of one and a half free H2O molecules (Calcd. 2.1%). There was a platform from 113 to 326 ℃. Subsequently, there was a rapid weight loss beyond 326 ℃ that indicates the decomposition of 1. Furthermore, the PXRD pattern of 1 can match the simulated one, indicating its phase purity. The PXRD pattern of 1 after being soaked in boiling water almost had no change compared with the simulated one, indicating its water stability (Fig. 3).

    Figure 3

    Figure 3.  PXRD patterns of complex 1, 1 after soaking in boiling water for 24 h, and 1 after detecting various analytes

    The solid state luminescence emission spectra of H2bcpp (λex=355 nm), 1, 4-bib (λex=353 nm), and 1 (λex= 355 nm) were investigated at room temperature (Fig. 4). H2bcpp and 1, 4-bib showed the main emission peaks at 463.8 and 475.2 nm, respectively. Their emission peaks may be ascribed to π* → π or π* → n[11-12] transitions. Complex 1 exhibited a single intense broad emission band at 461.4 nm, which was close to the emission peak of H2bcpp. Compared with the emission peaks of H2bcpp and 1, 4-bib, complex 1 presented a 2.4 nm blue shift and 13.8 nm blue shift in the luminescence emission spectrum, respectively. Considering that Zn2+ ions have a d10 configuration, the luminescence emission spectrum of 1 can be assigned to the metal to ligand charge transfer (MLCT) or ligand to metal charge transfer (LMCT) [13-18]. The slightly blue shifted emission bands can be attributed to the coordination effects. Based on the good luminescence property of complex 1, we further studied the luminescence sensing activity of complex 1.

    Figure 4

    Figure 4.  Solid-state luminescence emission spectra of H2bcpp, 1, 4-bib, and complex 1 at 298 K

    The detection ability of complex 1 for Fe3+ ions has been explored in an aqueous solution. The powder sample of 1 (2.0 mg) was evenly dispersed into 2.0 mL of 10 mmol·L-1 M(NO3)n aqueous solution (Mn+=Na+, Zn2+, Ni2+, Mg2+, Mn2+, Ca2+, Ba2+, Cu2+, Cd2+, Pb2+, Co2+, Cr3+, Fe2+, Al3+, Fe3+). The fluorescence emission spectra of the dispersed suspensions were measured at λex= 355 nm. As shown in Fig. 5a, the luminescence intensity of 1 has an almost completely quenching with the addition of Fe3+, indicating the excellent sensing ability for Fe3+. The titration experiment was further performed to explore the sensing ability for Fe3+ ions (Fig. 5b). With adding the Fe3+ solution, the fluorescence intensity of 1 dropped gradually with a high fluorescent quenching efficiency of 93.3% in the presence of 1.3 mmol·L-1 Fe3+ solution. Moreover, the low Fe3+ concentration and the fluorescence intensity exhibited a good linear relationship (Fig. 5c), which can be fitted to a line by Stern -Volmer relationship: I0/I=cFe3+Ksv+1, where I0 and I are the luminescence intensities of 1 without and with the addition of Fe3+, respectively; Ksv is the Stern-Volmer constant. The Ksv was calculated to be 4.90×103 L·mol-1. The limit of detection (LOD) was about 1.8 μmol·L-1 calculated by 3σ/Ksv[19]. Compared with some reported MOFs based fluorescence sensors, complex 1 exhibited a comparable or lower LOD for sensing Fe3+ in an aqueous solution (Table S2).

    Figure 5

    Figure 5.  (a) Fluorescence intensity of 1 in aqueous solutions containing various metal cations at 461.4 nm (λex=355 nm); (b) Titration experiment of 1 for detecting Fe3+; (c) Stern-Volmer plot of 1 for sensing Fe3+ in aqueous solution; (d) Repeatability experiment of 1 for detecting Fe3+

    Furthermore, selectivity and recyclability are also important for evaluating the detecting ability of 1. Thus, the anti-interference fluorescence detection experiments for Fe3+ ions were explored by adding Fe3+ ions into the suspension of complex 1 with various metal cations. It was found that the Fe3+ for the fluorescence intensity of complex 1 still had an outstanding quenching effect (Fig. S4). The result indicates that complex 1 exhibits good selectivity for Fe3+. In addition, the recyclability of 1 for the detection of Fe3+ was verified by the cyclic tests. After repeated for five cycles, the fluorescence sensitivity remained almost unchanged (Fig. 5d). The results suggest that complex 1 has high sensitivity, selectivity, and recyclability for sensing Fe3+. In addition, we conducted a timedependent experiment and found that the fluorescence intensity decreased rapidly in 30 s and remained unchanged in 360 s (Fig. S5a). Herein, the recognition mechanism of 1 for sensing Fe3+ has been investigated. The PXRD peaks of complex 1 before and after recognizing Fe3+ ions almost had no change, indicating the structure of complex 1 keeps perfectly (Fig. 3). Compared with the UV-Vis spectra of other metal ions, the UV-Vis absorption spectra of Fe3+ had the greatest extent overlaps with the excitation spectra of complex 1 (Fig. S6a), which suggests that there is an inner filter effect (IFE) between complex 1 and Fe3+. The excitation energy of complex 1 is absorbed by Fe3+, which leads to fluorescence quenching[20-21]. IR spectra, where 1@Fe3+ showed new peaks at 1 745 and 1 411 cm-1 compared with complex 1 (Fig.S1), further indicate that there is a weak interaction between complex 1 and Fe3+.

    Organochlorine pesticides as a class of widely-used pesticides have gained numerous attention from environmentalists because residual organochlorine pesticides are harmful to the environment and human health. Thus, we try to investigate the detection ability of 1 (λex =355 nm) for organochlorine pesticides in an aqueous solution. Herein, we selected eight pesticides to explore, including carbaryl, chlorobenzene (CB), atrazine, 2,4-dichlorobenzene (2,4-DCP), 1,2-dichlorobenzene (1,2-DiCB), 1,2,4-trichlorobenzene (1,2,4-TriCB), 1,2,4,5-tetrachlorobenzene (1,2,4,5-TetraCB), and DCN. As shown in Fig. 6a, DCN shows the highest quenching efficiency for the fluorescence intensity of 1 (81.8%). The titration experiments exhibited that the fluorescence intensity of 1 gradually reduced with adding DCN solution (Fig. 6b). In addition, the DCN concentration and the fluorescence intensity of complex 1 exhibited a good linear relationship (Fig. 6c). The Ksv for DCN was 2.06×104 L·mol-1, and the LOD was about 0.44 μmol·L-1, indicating the excellent sensitivity of 1 for DCN. Moreover, the selective and the anti interference ability were investigated, which are shown in Fig. 6d and Fig.S7. The time-dependence experiment of complex 1 for DCN further proves that complex 1 has high stability (Fig. S5b). The results displayed high selectivity and recyclability, indicating that complex 1 is a potential fluorescent sensor for detecting DCN. Furthermore, 1 has higher sensitivity and lower LOD compared with some reported MOF fluorescent probes for detecting DCN (Table S3).

    Figure 6

    Figure 6.  (a) Fluorescence intensity of 1 in various organochlorine pesticides at 461.4 nm (λex=355 nm); (b) Titration experiment of 1 for DCN; (c) Stern-Volmer plot of 1 for sensing DCN; (d) Repeatability experiment of 1 for DCN

    Additionally, the sensing ability of 1 for DCN in real samples, such as the concentrated juices of grapes, nectarines, and carrots, was also investigated (Fig. S8). Their Ksv and LOD values are listed in Table S4. Notably, the LOD values were all lower than the maximum DCN residue reported in China National Food Safety Standards[22]. The results indicate the excellent selectivity, sensitivity, and recyclability of 1 for detecting DCN in aqueous solution and real samples. At the same time, complex 1 had a high recovery rate in these real samples (Table 2). Furthermore, the sensing mechanism of 1 was investigated. As shown in Fig. S6b, the excitation spectrum of complex 1 has a major overlap with the UV spectrum, indicating that there is an IFE [25-26] between DCN and complex 1. DCN absorbs the excitation energy of complex 1, resulting in fluorescence quenching.

    Table 2

    Table 2.  Determination of DCN in real samples
    下载: 导出CSV
    Sample Added / (μmol·L-1) Recovery / % Average recovery / % RSD* / %
    Carrot 10 94.1 94.7 0.17
    20 95.1 0.48
    30 94.8 1.28
    Grape 10 103.0 99.7 0.85
    20 100.8 2.43
    30 95.2 1.46
    Nectarine 10 110.1 99.2 1.22
    20 92.9 1.35
    30 94.6 2.01
    * Relative standard deviation, n=3.

    In summary, a novel water-stable Zn(Ⅱ)-based MOF (1) was constructed with a flexible carboxylic ligand 3, 5-bis(4-carboxylphenoxy)pyridine and a rigid N-donor ligand 1, 4-bis(1-imidazoly)benzene. Complex 1 exhibits a 1D tubular structure, where the adjacent 1D tubular structures are interpenetrated with each other to obtain a 3D supramolecular structure. Furthermore, the photoluminescence property of 1 was investigated, which indicates that 1 can be used to detect Fe3+ ion and pesticide DCN in an aqueous solution. The LOD values for Fe3+ ion and DCN in aqueous solutions are 1.8 and 0.44 μmol·L-1, respectively. The results suggested that complex 1 can be used as a "turn-off" fluorescence probe to trace Fe3+ ion and pesticide DCN with high selectivity, sensitivity, and recyclability.


    Supporting information is available at http://www.wjhxxb.cn
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  • Figure 1  Asymmetric unit of 1 with 50% thermal ellipsoid probability (a); 1D tubular structure of complex 1 along b axis (b) and along a axis (c) with 50% thermal ellipsoid probability

    All of the hydrogen atoms are omitted for clarity

    Figure 2  (a) π-stacking interaction in complex 1; (b) 3D supramolecular structure of 1 viewed along b axis with 50% thermal ellipsoid probability

    Figure 3  PXRD patterns of complex 1, 1 after soaking in boiling water for 24 h, and 1 after detecting various analytes

    Figure 4  Solid-state luminescence emission spectra of H2bcpp, 1, 4-bib, and complex 1 at 298 K

    Figure 5  (a) Fluorescence intensity of 1 in aqueous solutions containing various metal cations at 461.4 nm (λex=355 nm); (b) Titration experiment of 1 for detecting Fe3+; (c) Stern-Volmer plot of 1 for sensing Fe3+ in aqueous solution; (d) Repeatability experiment of 1 for detecting Fe3+

    Figure 6  (a) Fluorescence intensity of 1 in various organochlorine pesticides at 461.4 nm (λex=355 nm); (b) Titration experiment of 1 for DCN; (c) Stern-Volmer plot of 1 for sensing DCN; (d) Repeatability experiment of 1 for DCN

    Table 1.  Crystal data and refined parameters of complex 1

    Parameter 1
    Formula C68H52N8O8Zn2
    Formula weight 1 239.91
    Crystal system Monoclinic
    Space group I2/a
    a / nm 1.683 61(3)
    b / nm 2.566 63(4)
    c / nm 2.778 46(5)
    β/(°) 98.905(2)
    Z 8
    V / nm3 11.861 6(4)
    Dc / (g·cm-3) 1.389
    μ / mm-1 1.520
    F(000) 5 120.0
    Unique reflection 39 446
    Observed reflection [I > 2σ(I)] 11 716
    Parameter 1 162
    GOF 1.070
    Final R indices [I > 2σ(I)] R1=0.072 1, wR2=0.205 0
    R indices (all data) R1=0.085 2, wR2=0.215 9
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    Table 2.  Determination of DCN in real samples

    Sample Added / (μmol·L-1) Recovery / % Average recovery / % RSD* / %
    Carrot 10 94.1 94.7 0.17
    20 95.1 0.48
    30 94.8 1.28
    Grape 10 103.0 99.7 0.85
    20 100.8 2.43
    30 95.2 1.46
    Nectarine 10 110.1 99.2 1.22
    20 92.9 1.35
    30 94.6 2.01
    * Relative standard deviation, n=3.
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文章相关
  • 发布日期:  2022-01-10
  • 收稿日期:  2021-05-24
  • 修回日期:  2021-10-21
通讯作者: 陈斌, bchen63@163.com
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