English

• 1. INTRODUCTION

  In recent years, metal-organic frameworks (MOFs) have been considered as one of the most important materials categories^{[1, 2]}. The combination of various metal clusters and ligands is arranged in a large number of geometric shapes, resulting in an ever-expanding MOF family^[3-6]. The structural diversity present in MOFs has significantly expanded the application of these new materials, benefiting from the tunable structure, controllable porosity and high crystal-linity^[7-9]. MOFs have shown great potential in various applications, such as gas storage and separation, drug release, biomedical delivery, chemical sensing, etc^[10-14]. Luminescent metal-organic frameworks have shown great potential in chemical sensors, biological probes in terms of the advantages of sensitivity, intelligence and simple operation of fluorescence detection^[15-17].

  A class of molecules with "aggregation-induced emission (AIE)" effect was first discovered and reported by Tang group^[18]. To date, tetraphenylethylene (TPE) has become one of the most popular AIE chromophores due to its simple molecular structure and excellent AIE properties, and has been widely used as an important component of many luminescent materials^{[19, 20]}. Significantly, it also supplies the great advantages to construct AIE-dominated MOFs. For instances, some TPE-based MOFs reported by Li group have been used to detect nitro-explosives^[21]. Ma and co-workers have demonstrated TPE-based MOFs could cat as the sensor of Cr₂O₇^2–[22]. This kind of luminescent MOFs is attracting increasingly attention in the field of sensing.

  Pesticides are widely used in agriculture, but their residues will cause serious damages to ecological security and harm to human health and quality of life through the food chain. Therefore, rapid and selective detection of pesticides has become one of the most urgent problems in human health and environmental protection. For example, 2, 6-dichloro-4-nitroaniline (DCN) is a widely used pesticide belonging to the toxic category IV. At the same time, degradation of DCN is slow. It can remain in environmental conditions for a long time. At present, the commonly used methods of DCN detection include ion migration spectroscopy, high performance liquid chromatography (HPLC) or other advanced instruments that require expensive and complex analysis. Here, we use a TPE-based ligand (TCPP) which exhibits significant AIE property as a pillar connector to prepare a new columnar layered luminescent MOF, the compound shows high-performance sensitivity to 2, 6-di-chloro-4-nitroaniline (DCN).

  2. EXPERIMENTAL

  2.1 Materials and methods

  All solvents and reagents were commercially available and used without further purification. Powder X-ray diffraction (PXRD) was measured on a D/Max-2500 diffractometer using CuKα (λ = 1.5418 Å) beam at room temperature. Thermogravimetric analyses (TGA) were conducted on a Netszch TGA 209 F3 thermogravimeter at a heating rate of 5 ℃·min^–1 in air atmosphere. Elemental analyses for C, H and N were performed on a PerkinElmer 240 microelemental analyzer. Room-temperature emission and excitation spectra for the samples were recorded by a Hitachi F7000 fluorescence spectrometer.

  2.2 Synthesis of 1

  [(CH₃)₂NH₂][In(TCPP)_4/3]_n·(DMF)(H₂O) 1 was synthesized as below: H₄TCPP (180 mg, 0.023 mmol) and In(NO)₃·4H₂O (15 mg, 0.05 mmol) were added in 6 mL DMF/dioxane/H₂O (v: v: v = 4:1:1) solution, then four drops of nitric acid (3 M) were added in the 20 mL vial, leading to yellow block crystals at 120 ℃ after 2 days, which were washed with DMF for three times (yield: 65.0%). Anal. Calcd. for C₅₉H₄₇InN₂O₉ (%): C, 66.85; H, 4.44; N, 2.64. Found (%): C, 67.09; H, 4.68; N, 2.71.

  Complex 1 crystallizes in cubic with space group P4/ncc, a = 10.2202(11), b = 10.2202(11), c = 43.217(5) Å, V = 4514.1(11) ų, Z = 4, D_c = 1.359 g/m³, F(000) = 1896 and μ = 0.579 mm^–1. A total of 2002 reflections were obtained and 1284 unique (R_int = 0.1423) were collected in the range of 3.39 < θ < 24.99° by an ω scan mode, of which 1952 with I > 2σ(I) were used in the succeeding refinement. The final R = 0.1287, wR = 0.3353 (w = 1/[σ²(F_o²) + (0.1187P)² + 84.5200P], where P = (F_o² + 2F_c²)/3), (Δρ)_max = 1.205, (Δρ)_min = –1.038 e/ų, (Δ/σ)_max = 0.0000 and S = 1.062.

  2.3 X-ray collection and structure determination

  Crystallographic data for compound 1 (0.12 mm × 0.12 mm × 0.15 mm) were collected on a Rigaku Supernova diffractometer with a CCD detector using graphite-monochromatic MoKα radiation (λ = 0.71073 Å) at 120 K. The structure was determined by direct methods and refined by full-matrix least-squares method with the OLEX2.0 program package^[23]. All non-hydrogen atoms were located successfully from Fourier maps and were refined anisotropically. The disordered guests DMF and H₂O molecules could not be located successfully from Fourier maps, and the highly disordered lattice guest molecules were removed using the SQUEEZE procedure by PLATON^[24].

  2.4 Fluorescence sensing methodology

  The luminescent properties of 1 were examined in the solid state, water and organic solvent at room temperature. Prior to measurement, compound 1 was washed by DMF and ethanol. Then the solid sample was ground into powder and used for sensing measurements. All titrations were carried out by gradually adding solutions of the analytes into the aqueous suspension of compound 1. The details are as follows: the standard suspensions were prepared by adding grinding sample (2 mg) into aqueous solution with a same volume (2 mL), then treated by ultrasonication for 0.5 h. The excitation wavelength was 370 nm while the slit width of both source and detector for the excitation and the emission were kept at 5 nm to maintain consistency, then the emission spectra were recorded. The quenching efficiency defined by (I₀ − I)/I₀ × 100 %, where I₀ and I are the luminescence intensities of sensor before and after the addition of analytes, respectively. The following nitro compounds were selected as analytes: 2, 4-dinitrotoluene (2, 4-DNT), bromobenzene(BrB), benzyl alcohol (BnOH), benzimidazole (Bim) and 2, 6-dichloro-4-nitroaniline (DCN).

  Table 1

  

  Table 1.  Selected Bond Distances (Å) and Bond Angles (^o) for Compound 1

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  Bond	Dist.		Bond	Dist.
  In(1)–O(11)	2.252(10)		In(1)–O(2)	2.29(2)
  In(1)–O(1)	2.252(10)		In(1)–O(21)	2.29(2)
  In(1)–O(12)	2.252(10)		In(1)–O(22)	2.29(2)
  In(1)–O(13)	2.252(10)		In(1)–O(23)	2.29(2)
  Angle	(º)		Angle	(º)
  O(1)–In(1)–O(11)	124.8(3)		O(21)–In(1)–O(13)	81.0(6)
  O(12)–In(1)–O(1)	81.9(5)		O(21)–In(1)–O(12)	154.2(6)
  O(12)–In(1)–O(11)	124.8(3)		O(21)–In(1)–O(1)	80.8(5)
  O(13)–In(1)–O(1)	124.8(3)		O(22)–In(1)–O(11)	80.8(5)
  O(13)–In(1)–O(11)	81.9(5)		O(23)–In(1)–O(11)	81.0(6)
  O(13)–In(1)–O(12)	124.8(3)		O(22)–In(1)–O(1)	81.0(6)
  O(22)–In(1)–O(13)	154.2(6)		O(21)–In(1)–O(11)	54.4(7)
  O(23)–In(1)–O(1)	154.2(6)		O(23)–In(1)–O(2)	103.9(4)
  O(2)–In(1)–O(13)	80.8(5)		O(21)–In(1)–O(2)	103.9(5)
  O(23)–In(1)–O(12)	80.8(5)		O(23)–In(1)–O(22)	103.9(5)
  O(23)–In(1)–O(13)	54.4(7)		O(22)–In(1)–O(2)	121.4(8)
  O(2)–In(1)–O(12)	81.0(6)		O(21)–In(1)–O(22)	103.9(4)
  O(2)–In(1)–O(11)	154.2(6)		O(21)–In(1)–O(23)	121.4(8)
  O(22)–In(1)–O(12)	54.4(7)		O(2)–In(1)–O(1)	54.4(7)
  Symmetry codes: 1: 1/2 + y, 1 – x, 1 – z; 2: 3/2 – x, 1/2 – y, z; 3: 1 – y, –1/2 + x, 1 – z; 4: 1/2 + y, – 1/2 + x, 3/2 – z

  3. RESULTS AND DISCUSSION

  3.1 Structure analysis

  Single-crystal X-ray diffraction analysis revealed that compound 1 crystallizes in space group P4/ncc. The asymmetric unit contains one independent In³⁺ ion and third-four TCPP ligand. Each In³⁺ ion is eight-coordinated by eight oxygen atoms of four carboxylate groups from four TCPP ligands to form the four-connected building unit [In(COO)₄]^– (Fig. 1a). The carboxylate groups adopt a chelating coordination model to connect In³⁺ ions to result in an anionic 3D framework [In(COO)₄]^– with a (4, 4)-connected network (Fig. 1b). Compound 1 contains one-dimensional (1D) channels along the c axis (Fig. 1d). Due to the large size of TCPP, a 4-fold interpenetrated net is formed (Fig. 1e). The anionic framework is balanced by [(CH₃)₂NH₂]⁺ counterions. The void space accounts for approximately 14.6 % of the whole crystal volume without the consideration of solvents as obtained by PLATON analysis.

  Figure 1

  

  Figure 1.  (a) Coordination environment of In³⁺ ion; (b) Coordination model of TCPP ligand; (c) Single framework along the a axis; (d) 3D single framework of compound 1 along the c axis; (e) 4-Fold interpenetrated structure of 1 along the c axis

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  3.2 Fluorescent properties

  The luminescent properties of compound 1 were studied. Compound 1 in solid state exhibits blue emission with the maximum value at 467 nm (λ_ex = 340 nm), which is mainly ascribed to the TCPP ligand (Fig. 2a). The quantum yield of compound 1 is up to 54.82%. The results indicate that compound 1 has the high-performance luminescent property.

  Figure 2

  

  Figure 2.  Solid-state emission spectra of 1, free TCPP at room temperature (Black line for compound and red line for TCPP)

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  3.3 PXRD properties and IR spectra

  In order to check the phase purity of compound 1, the powder X-ray diffraction (PXRD) pattern of 1 was checked at room temperature (Fig. 3a). The peak positions of simulated and experimental PXRD patterns are in agreement with each other, demonstrating the single phase purity of the products. IR spectra display characteristic absorption bands for water molecules, carboxylate, and the carbon-carbon double bonds. As shown in Fig. 3b, compound 1 shows the broad absorption band at 3409 cm^–1, indicating the presence of ν_O−H stretching frequencies of coordinated water molecules. And the strong band at 1635 cm^–1 is the characteristic stretching vibration of ν_C=H. The strong band at 1689 cm^–1 is the characteristic stretching vibration of COO^– of compound 1.

  Figure 3

  

  Figure 3.  PXRD patterns for complex 1: the as-synthesized patterns and the simulated based on X-ray single-crystal data (left); IR spectra of compound 1 (right)

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  3.4 Thermal property

  To investigate the thermal behavior of 1, thermogravimetric (TG) analysis study was carried out on preweighed samples under N₂ atmosphere at a heating rate of 5 ℃/min (Fig. 4). The TG plot of compound 1 indicated no obvious weight loss up to 400 ℃, confirming no guest molecule resides in the framework of 1. The framework decomposition started from 400 ℃.

  Figure 4

  

  Figure 4.  TGA plot of compound 1

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  3.5 Sensing of nitro-compounds

  Based on the good luminescent emission and electronicrich framework, the detection capacity of compound 1 against nitro-compounds was carried out. The detection of nitroaromatic compounds was performed in aqueous solution. As shown in Fig. 5, the emission intensity of compound 1 is greatly quenched with the addition of 2, 6-dichloro-4-nitroaniline (DCN). It is worth noting that the fluorescence intensity could be decreased as much as 80% by 6 μL (6.25 ppm) DCN and the fluorescence intensity of compound 1 was almost completely quenched when the concentration of DCN is only up to 20 μL (20.83 ppm), while the other four compounds 2, 4-DNT, Bim, BnOH and BrB have no obvious fluorescence quenching effect on compound 1. These results suggest that compound 1 shows remarkable sensitivity and selectivity to DCN.

  Figure 5

  

  Figure 5.  Emission spectra of compound 1 (50 μg/mL) upon the addition of DCN at concentrations from 0 to 20 μL (right). UV absorption spectra of various nitro-compounds (0.1 mM) (right)

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  Figure 6

  

  Figure 6.  Emission spectra of compound 1 (50 μg/mL) upon the addition of 2, 4-DNT (left) and Bim (right) in water at concentrations from 0 to 120 μL

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  Figure 7

  

  Figure 7.  Emission spectra of compound 1 (50 μg/mL) upon the addition of BnOH (left) and BrB (right) in water at concentrations from 0 to 120 μL

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  Besides, the sensing mechanism was investigated. Compound 1 could serve as an electron donor due to electron-rich TPE in the framework, whereas DCN is an electron-deficient compound. The electron transfer from compound 1 to DCN easily occurred, which caused the fluorescence quenching. Meanwhile, as shown in Fig. 5 (right), UV-vis absorption shows the emission spectrum (260~450 nm) of the donor (compound 1) and the absorption spectrum (300~450 nm) of the acceptor (DCN) has large overlap, indicating the existence of resonance energy transfer, while there is no overlap with the other four analytes. The facts reveal that the high sensitivity and selectivity of 1 toward DCN could be mainly attributed to the electron transfer and resonance energy transfer effect between the framework and the analytes.

  4. CONCLUSION

  In summary, a water-stable indium-organic framework based on TCPP has been synthesized. Compound 1 could act as a highly sensitive fluorescent probe towards a widely used pesticide DCN. The detection limit of compound 1 toward DCN is as low as 20.83 ppm. Importantly, the quenching performances could be confirmed by the electron transfer and resonance energy transfer effect between the framework and the analytes. This work provides an effective route to design and synthesize functional MOFs as fluorescent sensors for DCN.

  
  
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• 

  Figure 1  (a) Coordination environment of In³⁺ ion; (b) Coordination model of TCPP ligand; (c) Single framework along the a axis; (d) 3D single framework of compound 1 along the c axis; (e) 4-Fold interpenetrated structure of 1 along the c axis

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  Figure 2  Solid-state emission spectra of 1, free TCPP at room temperature (Black line for compound and red line for TCPP)

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  Figure 3  PXRD patterns for complex 1: the as-synthesized patterns and the simulated based on X-ray single-crystal data (left); IR spectra of compound 1 (right)

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  Figure 4  TGA plot of compound 1

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  Figure 5  Emission spectra of compound 1 (50 μg/mL) upon the addition of DCN at concentrations from 0 to 20 μL (right). UV absorption spectra of various nitro-compounds (0.1 mM) (right)

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  Figure 6  Emission spectra of compound 1 (50 μg/mL) upon the addition of 2, 4-DNT (left) and Bim (right) in water at concentrations from 0 to 120 μL

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  Figure 7  Emission spectra of compound 1 (50 μg/mL) upon the addition of BnOH (left) and BrB (right) in water at concentrations from 0 to 120 μL

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  Table 1.  Selected Bond Distances (Å) and Bond Angles (^o) for Compound 1

  Bond	Dist.		Bond	Dist.
  In(1)–O(11)	2.252(10)		In(1)–O(2)	2.29(2)
  In(1)–O(1)	2.252(10)		In(1)–O(21)	2.29(2)
  In(1)–O(12)	2.252(10)		In(1)–O(22)	2.29(2)
  In(1)–O(13)	2.252(10)		In(1)–O(23)	2.29(2)
  Angle	(º)		Angle	(º)
  O(1)–In(1)–O(11)	124.8(3)		O(21)–In(1)–O(13)	81.0(6)
  O(12)–In(1)–O(1)	81.9(5)		O(21)–In(1)–O(12)	154.2(6)
  O(12)–In(1)–O(11)	124.8(3)		O(21)–In(1)–O(1)	80.8(5)
  O(13)–In(1)–O(1)	124.8(3)		O(22)–In(1)–O(11)	80.8(5)
  O(13)–In(1)–O(11)	81.9(5)		O(23)–In(1)–O(11)	81.0(6)
  O(13)–In(1)–O(12)	124.8(3)		O(22)–In(1)–O(1)	81.0(6)
  O(22)–In(1)–O(13)	154.2(6)		O(21)–In(1)–O(11)	54.4(7)
  O(23)–In(1)–O(1)	154.2(6)		O(23)–In(1)–O(2)	103.9(4)
  O(2)–In(1)–O(13)	80.8(5)		O(21)–In(1)–O(2)	103.9(5)
  O(23)–In(1)–O(12)	80.8(5)		O(23)–In(1)–O(22)	103.9(5)
  O(23)–In(1)–O(13)	54.4(7)		O(22)–In(1)–O(2)	121.4(8)
  O(2)–In(1)–O(12)	81.0(6)		O(21)–In(1)–O(22)	103.9(4)
  O(2)–In(1)–O(11)	154.2(6)		O(21)–In(1)–O(23)	121.4(8)
  O(22)–In(1)–O(12)	54.4(7)		O(2)–In(1)–O(1)	54.4(7)
  Symmetry codes: 1: 1/2 + y, 1 – x, 1 – z; 2: 3/2 – x, 1/2 – y, z; 3: 1 – y, –1/2 + x, 1 – z; 4: 1/2 + y, – 1/2 + x, 3/2 – z

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•