An oxadiazolone copper (I) organometallic complex, its preparation method, and its applications.

Abstract

This invention discloses an oxadiazolone-based copper(I) organometallic complex, named 5-(4-methoxyphenyl)-3-(8-quinolinyl)-1,3,4-oxadiazol-2-one cuprous chloride metal complex. The crystal of this oxadiazolone-based copper(I) organometallic complex belongs to the orthorhombic crystal system, with space group Pbca and unit cell parameters α = 90.00°, β = 90.00°, and γ = 90.00°. This oxadiazolone-based copper(I) organometallic complex of the present invention can emit fluorescence, allowing for the detection of low concentrations of carbon disulfide or ferric ions using fluorescence emission spectroscopy. Furthermore, the crystalline material of this complex exhibits high thermal stability.

Description

Technical Field

[0001] This invention relates to the field of fluorescence detection technology, specifically to an oxadiazolone copper(I) metal-organic complex, its preparation method, and its application. Background Technology

[0002] Metal ions are widely present in environmental ecosystems, and their detection has always been a focus of research. Among the many transition metal ions, Fe... 3+ Iron is an essential trace element for humans and other organisms, playing a vital role in cell metabolism and enzyme catalysis. However, when serum iron levels exceed the normal range, it can lead to an increased incidence of certain diseases, such as cancer, and diseases of organs like the liver, heart, and kidneys.

[0003] On the other hand, with the rapid development of industry and human social activities, a large amount of chemical pollutants such as volatile organic compounds (VOCs) are released into the environment. VOCs can lead to climate change and ozone layer depletion, and at certain concentrations, they can also trigger a series of human diseases. For example, carbon disulfide, as an important chemical product, is widely used in organic synthesis, dyes, synthetic resins, and automobiles. However, long-term exposure to low concentrations of this substance in living and production environments can cause severe harm to the human body, damaging the nervous system and blood vessels.

[0004] Currently detecting Fe 3+ There are many methods for detecting Fe2+, such as atomic absorption spectroscopy, inductively coupled plasma atomic emission spectroscopy, electrochemical methods, and chromatography. However, these methods are often limited by high equipment costs and complex sample preparation. Therefore, it is necessary to explore a rapid, simple, and real-time method for detecting Fe2+. 3+ The method of detecting carbon disulfide is a current research direction in the field of environmental protection testing. Among them, the molecular spectrometry method uses optical probes to detect Fe. 3+ Fe ions are a class of ions that have been studied in greater depth in recent years. For example, Chinese patent applications with publication numbers CN108949157A and CN107312022A both disclose a method for detecting Fe. 3+ Probes are available, but most of these probes only show one signal, namely ultraviolet absorption or fluorescence emission, which makes the detection of Fe... 3+ Its capabilities are limited by testing conditions and affected by environmental changes.

[0005] Metal-organic frameworks (MOFs) are a novel type of sensing material with functional structures, attracting increasing attention in fluorescence detection, particularly in the detection of metal ions and small organic molecules. Current research in this field mainly focuses on the detection of single-type substances, without addressing the simultaneous detection of different categories. Summary of the Invention

[0006] The technical problem to be solved by the present invention is how to provide a method that can simultaneously detect different types of oxadiazolone copper (I) metal organometallic complexes.

[0007] The present invention solves the above-mentioned technical problems through the following technical means:

[0008] An oxadiazolone copper(I) metal-organic complex, named 5-(4-methoxyphenyl)-3-(8-quinolinyl)-1,3,4-oxadiazol-2-one cuprous chloride metal complex, has the chemical formula Cu(MPQOO)(Cl), wherein MPQOO is 5-(4-methoxyphenyl)-3-(8-quinolinyl)-1,3,4-oxadiazol-2-one, and the structural formula of the complex is [not specified].

[0009]

[0010] The oxadiazolone copper(I) organometallic complexes have the following structural features:

[0011] The central Cu(I) ion is tetrahedrally coordinated, forming a tetrahedral geometry with two N atoms and two chloride ions from a single MPQOO ligand. MPQOO is a bidentate chelate ligand that forms a six-membered ring with the central Cu(I). Each chloride atom bridges two adjacent Cu(I) atoms, forming a one-dimensional chain. The bond length between Cu(I) and N is... The bond length of Cu(Ⅰ)-Cl is The bond angle of N-Cu(Ⅰ)-Cl is 97.93(17)°-123.10(12)°, and the bond angle of Cl-Cu(Ⅰ)-Cl is 114.85(12)°.

[0012] Beneficial effects: The oxadiazolone copper (I) metal-organic complex of the present invention can emit fluorescence, and low concentrations of carbon disulfide or ferric ions can be detected by fluorescence emission spectroscopy. At the same time, the complex has high thermal stability as a crystal material.

[0013] Preferably, the crystals of the oxadiazolone copper(I) organometallic complexes belong to the orthorhombic crystal system, with space group Pbca and cell parameters as follows: α=90.00°, β=90.00°, γ=90.00°.

[0014] The preparation method of the above-mentioned oxadiazolone copper(I) metal organometallic complex is as follows: cuprous chloride dihydrate and MPQOO are added to a mixed solvent formed by deionized water and organic matter, reacted at 60-100℃ for 3 days, cooled to room temperature, filtered and washed to obtain the oxadiazolone copper(I) metal organometallic complex.

[0015] Beneficial effects: This invention uses a solvothermal method to prepare oxadiazolone copper(I) organometallic complexes with high yield. Experiments show that crystals cannot form when the reaction temperature is below 60℃, and the product is easily carbonized when the reaction temperature is above 100℃.

[0016] Preferably, the MPQOO is prepared according to the method described in the literature (Xu Heng, Yang Ping, Gui Naicheng, et al. Journal of Luminescence, 2022, 43(10): 1636-1644.); the specific preparation method is as follows:

[0017] (1) Preparation of 4-methoxy-N'-(8-quinolinyl)benzoylhydrazine:

[0018] 4-Methoxybenzoyl chloride (1.70 g, 10 mmol) was diluted with 20 mL of dichloromethane (DCM). 1.59 g, 10 mmol of dried 8-hydrazinoquinoline was dissolved in 20 mL of DCM. Triethylamine (1.52 g, 15 mmol) was added. The mixture was cooled to 0-10 °C under nitrogen protection, and the DCM solution of 4-methoxybenzoyl chloride was slowly added dropwise at this temperature. After the addition was complete, the mixture was stirred for half an hour. After the reaction was complete, the reaction solution was washed with water and NaHCO3 aqueous solution, separated, and the aqueous phase was extracted with 50 mL of DCM. The organic layers were combined, and the organic phase was concentrated under vacuum. The concentrate was recrystallized from ethyl acetate / petroleum ether (EA / PE) at a volume ratio of 1:2 to obtain solid 4-methoxy-N'-(8-quinolinyl)benzoylhydrazine with a melting point of 160.3-161.2 °C, consistent with literature values.

[0019] (2) Preparation of 5-(4-methoxyphenyl)-3-(8-quinolinyl)-1,3,4-oxadiazol-2-one:

[0020] Triphosgene (5.994 g, 20 mmol) was dissolved in 10 mL of DCM. 1.465 g, 5 mmol of dried 4-methoxy-N'-(8-quinolinyl)benzoylhydrazine was dissolved in 20 mL of DCM. Triethylamine (2.02 g, 20 mmol) was added. The mixture was cooled to 0-10 °C under nitrogen protection, and the DCM solution of triphosgene was added dropwise at this temperature. After the addition was complete, the mixture was stirred for half an hour. After the reaction was complete, the mixture was filtered. The filtrate was concentrated to dryness under vacuum at 40 °C. EA was added to the solid, and the mixture was stirred and filtered again. The filtrate was further concentrated to dryness, and PE was added and stirred. The mixture was then filtered to obtain 5-(4-methoxyphenyl)-3-(8-quinolinyl)-1,3,4,-oxadiazol-2-one solid with a melting point of 174.6-175.9 °C, consistent with literature values.

[0021] Preferably, the mixed solvent is deionized water-acetone, and the molar ratio of deionized water to acetone is 1-3:4.

[0022] Beneficial effects: The mixed solvent of the present invention is deionized water-acetone. Other solvents are difficult to generate complex crystals, and different volume ratios of the mixed solvents will directly affect the yield of the target complex. When the molar ratio of deionized water to acetone is 2:3, the yield is the highest.

[0023] Application of the above-mentioned oxadiazolone copper(I) organometallic complexes in fluorescent probes.

[0024] Preferably, it is used to detect low concentrations of carbon disulfide or ferric ions.

[0025] Preferably, the specific operation involves adding the oxadiazolone copper(I) metal organometallic complex to acetonitrile solvent to prepare a suspension, injecting it into a cuvette, measuring its fluorescence emission spectrum, and then successively adding pure carbon disulfide to the cuvette, measuring the fluorescence emission spectrum of the suspension each time, establishing a linear equation between the concentration of the oxadiazolone copper(I) metal organometallic complex and the concentration of carbon disulfide, thereby detecting the concentration of carbon disulfide.

[0026] Preferably, the specific operation involves adding the oxadiazolone copper(I) metal-organic complex to a tetrahydrofuran solvent to prepare a suspension, injecting it into a cuvette, and measuring its fluorescence emission spectrum. Then, Fe(NO3)3 aqueous solution is added to the cuvette sequentially, and the fluorescence emission spectrum of the suspension is measured each time. This establishes the relationship between the oxadiazolone copper(I) metal-organic complex and Fe... 3+ A linear equation for concentration, thus enabling the detection of Fe. 3+ The concentration.

[0027] Preferably, the specific operation involves adding the oxadiazolone copper(I) metal organometallic complex to a tetrahydrofuran solvent to prepare a suspension, which is then injected into a cuvette, and Fe is removed from the suspension. 3+ Besides aqueous solutions containing other metal ions, the fluorescence emission spectra of solutions containing other ions were tested, and an equal amount of Fe was added. 3+ Aqueous solutions were analyzed to measure the fluorescence emission spectra of solutions containing mixed ions, and the oxadiazolone copper(I) organometallic complexes with Fe were determined. 3+ A linear equation for concentration, thus enabling the detection of Fe. 3+ The concentration.

[0028] Preferably, the concentration range for detecting carbon disulfide is 1.65 × 10⁻⁶. -3 -2.98×10 -2 mol / L, detection of Fe 3+ The concentration range is 1.00 × 10⁻⁶. -5 -1.5×10 -4 mol / L.

[0029] Beneficial effects: The oxadiazolone copper (I) metal-organic complex of the present invention can be used as a fluorescent probe to detect both low concentrations of carbon disulfide and low concentrations of ferric ions in the environment.

[0030] The preparation method of the oxadiazolone copper (I) organometallic complex of the present invention is simple, and the complex is effective in detecting Fe. 3+ It has a strong ability to resist interference from other ions.

[0031] The advantages of this invention are:

[0032] The oxadiazolone copper (I) organometallic complex of the present invention can emit fluorescence, and low concentrations of carbon disulfide or ferric ions can be detected by fluorescence emission spectroscopy. At the same time, the complex has high thermal stability as a crystal material.

[0033] This invention employs a solvothermal method to prepare oxadiazolone copper(I) organometallic complexes with high yields. Experiments show that crystals cannot form when the reaction temperature is below 60°C, and the product is prone to carbonization when the reaction temperature is above 100°C.

[0034] The preparation method of the oxadiazolone copper (I) organometallic complex of the present invention is simple, and the complex is effective in detecting Fe. 3+ It has a strong ability to resist interference from other ions. Attached Figure Description

[0035] Figure 1 This is a diagram of the asymmetric unit structure of the oxadiazolone copper (I) organometallic complex in Example 2;

[0036] Figure 2 This is a one-dimensional chain structure diagram of the oxadiazolone copper (I) organometallic complex in Example 2;

[0037] Figure 3 Thermogravimetric analysis diagram of the oxadiazolone copper (I) organometallic complex in Example 2;

[0038] Figure 4 The concentration in Example 6 was 1.20 × 10⁻⁶. -3 Fluorescence emission spectrum of a suspension of mol / L oxadiazolone copper(I) metal-organic complex / acetonitrile after the addition of CS2; the data indicated by the arrows in the figure are the concentrations of added carbon disulfide;

[0039] Figure 5 The concentration in Example 7 was 1.20 × 10⁻⁶. -3 Fluorescence emission spectrum of a suspension of 1 mol / L oxadiazolone copper (I) metal organometallic complex / tetrahydrofuran with added ferric ions; the data indicated by the arrows in the figure are the concentrations of added ferric ions;

[0040] Figure 6 The concentration in Example 8 was 1.20 × 10⁻⁶. -3 Fluorescence emission intensity bar chart of mol / L oxadiazolone copper (I) metal organometallic complex / tetrahydrofuran suspension, and other metal ions interfering with ferric ions. Detailed Implementation

[0041] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0042] Unless otherwise specified, all test materials and reagents used in the following examples are commercially available.

[0043] Unless otherwise specified in the embodiments, the techniques or conditions described in the literature in this field or in accordance with the product manual may be followed.

[0044] Example 1

[0045] 5-(4-methoxyphenyl)-3-(8-quinolinyl)-1,3,4-oxadiazol-2-one was synthesized according to the method in the literature (Xu Heng, Yang Ping, Gui Naicheng, et al. Journal of Luminescence, 2022, 43(10): 1636~1644.). The specific preparation method is as follows:

[0046] (1) Preparation of 4-methoxy-N'-(8-quinolinyl)benzoylhydrazine:

[0047] 4-Methoxybenzoyl chloride (1.70 g, 10 mmol) was diluted with 20 mL of dichloromethane (DCM). 1.59 g, 10 mmol of dried 8-hydrazinoquinoline was dissolved in 20 mL of DCM. Triethylamine (1.52 g, 15 mmol) was added. The mixture was cooled to 0-10 °C under nitrogen protection, and the DCM solution of 4-methoxybenzoyl chloride was slowly added dropwise at this temperature. After the addition was complete, the mixture was stirred for half an hour. After the reaction was complete, the reaction solution was washed with water and NaHCO3 aqueous solution, separated, and the aqueous phase was extracted with 50 mL of DCM. The organic layers were combined, and the organic phase was concentrated under vacuum. The concentrate was recrystallized from ethyl acetate / petroleum ether (EA / PE) at a volume ratio of 1:2 to obtain solid 4-methoxy-N'-(8-quinolinyl)benzoylhydrazine with a melting point of 160.3-161.2 °C, consistent with literature values.

[0048] (2) Preparation of 5-(4-methoxyphenyl)-3-(8-quinolinyl)-1,3,4-oxadiazol-2-one:

[0049] Triphosgene (5.994 g, 20 mmol) was dissolved in 10 mL of DCM. 1.465 g, 5 mmol of dried 4-methoxy-N'-(8-quinolinyl)benzoylhydrazine was dissolved in 20 mL of DCM. Triethylamine (2.02 g, 20 mmol) was added. The mixture was cooled to 0-10 °C under nitrogen protection, and the DCM solution of triphosgene was added dropwise at this temperature. After the addition was complete, the mixture was stirred for half an hour. After the reaction was complete, the mixture was filtered. The filtrate was concentrated to dryness under vacuum at 40 °C. EA was added to the solid, and the mixture was stirred and filtered again. The filtrate was further concentrated to dryness, and PE was added and stirred. The mixture was then filtered to obtain 5-(4-methoxyphenyl)-3-(8-quinolinyl)-1,3,4-oxadiazol-2-one solid with a melting point of 174.6–175.9 °C, consistent with literature values.

[0050] Example 2

[0051] The preparation method of the oxadiazolone copper(I) organometallic complex in this embodiment is as follows:

[0052] CuCl₂·2H₂O (34.1 mg, 0.2 mmol), the synthesized 5-(4-fluorophenyl)-3-(8-quinolinyl)-1,3,4,-oxadiazol-2-one (61.4 mg, 0.2 mmol), and 10 mL of a mixed solvent (deionized water and acetone in a volume ratio of 1:4) were added to a 25 mL high-pressure reactor. The reactor was heated to 60 °C and maintained at this temperature for 3 days. After the reactor cooled to room temperature, bright yellow needle-like crystals were obtained. The mixture was filtered, and the filter cake was washed with ethanol to obtain 33.05 mg of single crystals of the target complex. The yield was calculated to be 39.5% based on 5-(4-fluorophenyl)-3-(8-quinolinyl)-1,3,4,-oxadiazol-2-one.

[0053] Figure 1 and Figure 2 The diagrams shown are the asymmetric unit structure and the one-dimensional chain structure of the oxadiazolone copper (I) organometallic complex in Example 2, respectively, demonstrating that the prepared oxadiazolone copper (I) organometallic complex is a metal-organic framework complex. Figure 3 The thermogravimetric analysis (TGA) curve of the oxadiazolone-based copper (I) organometallic complex in Example 2 shows that the complex is stable with no mass loss between 25-283℃; thermal decomposition begins between 283-354℃, and the rapid weight loss corresponds to the collapse of the oxadiazolone and quinoline ring skeleton and the dissociation of coordinated Cl ions, indicating that the prepared oxadiazolone-based copper (I) organometallic complex is a material with good thermal stability.

[0054] Example 3

[0055] The preparation method of the oxadiazolone copper(I) organometallic complex in this embodiment is as follows:

[0056] CuCl·2H₂O (34.1 mg, 0.2 mmol), the synthesized 5-(4-fluorophenyl)-3-(8-quinolinyl)-1,3,4,-oxadiazol-2-one (61.4 mg, 0.2 mmol), and 10 mL of a mixed solvent (deionized water and acetone in a volume ratio of 2:3) were added to a 25 mL high-pressure reactor. The mixture was heated to 80 °C and maintained at this temperature for 3 days. After cooling to room temperature, bright yellow needle-like crystals were obtained. The mixture was filtered, and the filter cake was washed with ethanol to obtain 38.24 mg of single crystals of the target complex. The yield was calculated to be 45.7% based on 5-(4-fluorophenyl)-3-(8-quinolinyl)-1,3,4,-oxadiazol-2-one.

[0057] Example 4

[0058] The preparation method of the oxadiazolone copper(I) organometallic complex in this embodiment is as follows:

[0059] CuCl·2H₂O (34.1 mg, 0.2 mmol), the synthesized 5-(4-fluorophenyl)-3-(8-quinolinyl)-1,3,4,-oxadiazol-2-one (61.4 mg, 0.2 mmol), and 10 mL of a mixed solvent (deionized water and acetone in a 3:2 ratio) were added to a 25 mL high-pressure reactor. The reactor was heated to 100 °C and maintained at this temperature for 3 days. After the reactor cooled to room temperature, bright yellow needle-like crystals were obtained. The mixture was filtered, and the filter cake was washed with ethanol to obtain 27.36 mg of single crystals of the target complex. The yield was calculated to be 32.7% based on 5-(4-fluorophenyl)-3-(8-quinolinyl)-1,3,4,-oxadiazol-2-one.

[0060] Example 5

[0061] The structure of the oxadiazolone copper (I) organometallic complex prepared in Example 2 was determined.

[0062] A single crystal measuring 0.150 × 0.120 × 0.100 mm was selected and analyzed at 296 K using a Bruker Smart APEX IICCD single crystal diffractometer with graphite-monochromated Mo-kα rays. For incident radiation, X-ray single-crystal diffraction data were collected using scanning methods. The unit cell parameters were refined using the least squares method, and the crystal structure was resolved using the SHELXL-97 direct method. All non-hydrogen atoms underwent anisotropic refinement using the full-matrix least squares method, and the positions of H atoms were determined by theoretical model calculations. Some parameters from the crystal diffraction data collection and structure refinement are shown in Table 1. The crystal structure is as follows: Figure 1-2 As shown.

[0063] Table 1 shows the crystallographic data of oxadiazolone copper (I) organometallic complexes.

[0064]

[0065]

[0066] Table 1

[0067] Example 6

[0068] The oxadiazolone copper(I) organometallic complex prepared in Example 2 was used as a fluorescent probe to detect low concentrations of carbon disulfide. The specific operation is as follows:

[0069] 2.0 mg of an oxadiazolone copper (I) organometallic complex was added to 4 mL of acetonitrile solvent and dispersed ultrasonically to prepare a solution of 1.20 × 10⁻⁶. -3 A suspension of mol / L was prepared. The suspension was injected into a 2 mL cuvette, and the fluorescence emission spectrum was measured using a Hitachi F-4500 fluorescence spectrometer. Then, pure carbon disulfide was added to the suspension one at a time, and the fluorescence emission spectrum of the suspension was measured each time.

[0070] The relationship between the I0 / I value of the oxadiazolone copper (Ⅰ) metal organometallic complex / acetonitrile suspension and the concentration (C) of the analyte CS2 is shown in Table 2.

[0071] Table 2 shows the linear relationship (λ) between the I0 / I value of the complex / acetonitrile suspension and the concentration (C) of the analyte CS2. em =434nm(λ) ex =337nm))

[0072] <![CDATA[I0 / I=0.99318+11.2094×[CS2]]]> 0.9979 <![CDATA[1.65×10 -3 -2.98×10 -2 ]]>

[0073] The relative fluorescence intensity (I0 / I) measured above, where I0 and I are the fluorescence intensities of the suspension at CS2 concentrations of 0 and C, respectively, are shown in Table 2. According to Table 2, at 1.65 × 10⁻⁶... -3 -2.98×10 -2 The fluorescence intensity showed a good linear relationship with the concentration of CS2 in the mol / L range, thus enabling the detection of low concentrations of CS2.

[0074] As the concentration of carbon disulfide increases, the fluorescence intensity of the complex suspension decreases rapidly. When the amount of carbon disulfide added is 0.36 mol / L, such as Figure 4 As shown, the fluorescence intensity changes little, and the excitation wavelength in this embodiment is 337 nm.

[0075] Example 7

[0076] The oxadiazolone copper(I) organometallic complex prepared in Example 2 was used as a fluorescent probe to detect low concentrations of ferric ions. The specific operation is as follows:

[0077] 2.0 mg of an oxadiazolone copper (I) organometallic complex was added to 4 mL of tetrahydrofuran solvent and dispersed ultrasonically to prepare a solution of 1.20 × 10⁻⁶. -3 A 0.1 mol / L ferric nitrate aqueous solution was added to a 2 mL cuvette, and the fluorescence emission spectrum was measured using a Hitachi F-4500 fluorescence spectrometer. Then, 0.1 mol / L ferric nitrate aqueous solution was added to the cuvette one by one, and the fluorescence emission spectrum of the suspension was measured each time.

[0078] Determination of the I0 / I value of oxadiazolone copper (I) metal organometallic complex / tetrahydrofuran solution and the analyte Fe 3+ The relationship between concentration (C) and the measurement results are shown in Table 3.

[0079] Table 3 shows the I0 / I values ​​of the complex / tetrahydrofuran solution and the analyte Fe. 3+ Linear relationship of concentration (C) (λ) em =456nm(λ) ex =335nm))

[0080] <![CDATA[I0 / I=0.97102+4.026×10 3 [Fe 3+ ]]]> 0.9926 <![CDATA[1.00×10 -5 -1.5×10 -4 ]]>

[0081] The relative fluorescence intensity (I0 / I) measured above, where I0 and I are Fe, respectively. 3+ Table 3 shows the fluorescence intensity of the suspension at concentrations of 0 and C. At 1.00 × 10⁻⁶, the fluorescence intensity is highest at concentrations of 0 and C. -5 -1.5×10 -4 Fluorescence intensity and Fe in the range of mol / L 3+ The concentration showed a good linear relationship, thus enabling the detection of low concentrations of Fe. 3+ .

[0082] With Fe 3+ As the concentration increases, the fluorescence intensity of the complex suspension decreases rapidly, when Fe... 3+ The concentration reached an addition amount of 9.7 × 10⁻⁶. -4 At mol / L, such as Figure 5 As shown, the fluorescence intensity changes little, and the excitation wavelength in this embodiment is 335 nm.

[0083] Example 8

[0084] The oxadiazolone copper (I) organometallic complex prepared in Example 2 was used as a fluorescent probe to detect low concentrations of ferric ions (in the presence of other metal ions). The specific operation is as follows:

[0085] 2.0 mg of an oxadiazolone copper (I) organometallic complex was added to 4 mL of tetrahydrofuran solvent and dispersed ultrasonically to prepare a solution with a concentration of 1.2 × 10⁻⁶. -3 A solution of mol / L was prepared. The solution was injected into a 2 mL cuvette, and the excitation wavelength was 335 nm. The fluorescence intensity of the solution was measured using a Hitachi F-4500 fluorescence spectrometer. em =Fluorescence intensity at 456nm (emission wavelength), and then add 5μL (0.1mol / L) of Fe removal agent. 3+ For nitrate solutions containing other metals, the fluorescence intensity of the solution at the emission wavelength was measured, and the results are as follows: Figure 6 The complex plus other metal ions were used as shown. Then, 5 μL (0.1 mol / L) of ferric nitrate aqueous solution was added, and the fluorescence intensity of the mixed ionic solution at the emission wavelength was measured. The results are as follows: Figure 6 In the middle complex + other metal ions + Fe 3+ As shown, by Figure 6 It can be seen that other metal ions affect Fe 3+ Fluorescence detection is virtually unaffected, and the excitation wavelength in this embodiment is 335 nm.

[0086] The oxadiazolone copper (I) organometallic complex of the present invention can emit fluorescence, and low concentrations of carbon disulfide or ferric ions can be detected by fluorescence emission spectroscopy. At the same time, the complex has high thermal stability as a crystal material.

[0087] This invention employs a solvothermal method to prepare oxadiazolone copper(I) organometallic complexes with high yields. Experiments show that crystals cannot form when the reaction temperature is below 60°C, and the product is prone to carbonization when the reaction temperature is above 100°C.

[0088] The preparation method of the oxadiazolone copper (I) organometallic complex of the present invention is simple, and the complex is effective in detecting Fe. 3+ It has a strong ability to resist interference from other ions.

[0089] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. An oxadiazolone copper(I) organometallic complex, characterized in that, The complex is named 5-(4-methoxyphenyl)-3-(8-quinolinyl)-1,3,4-oxadiazol-2-one cuprous chloride metal complex, with the chemical formula Cu(MPQOO)(Cl), where MPQOO is 5-(4-methoxyphenyl)-3-(8-quinolinyl)-1,3,4-oxadiazol-2-one. The structural formula of the complex is [not specified]. 。 2. The oxadiazolone copper(I) organometallic complex according to claim 1, characterized in that, The complex is a crystal belonging to the orthorhombic crystal system with space group Pbca and cell parameters a = 6.9108(4) Å, b = 19.6152(12) Å, c = 24.2313(15) Å; α = 90.00°, β = 90.00°, γ = 90.00°.

3. The method for preparing oxadiazolone copper(I) organometallic complexes as described in claim 1 or 2, characterized in that, The preparation method involves adding cuprous chloride dihydrate and MPQOO to a mixed solvent formed by deionized water and acetone, reacting at 60-100℃ for 3 days, cooling to room temperature, filtering, and washing to obtain oxadiazolone copper(I) organometallic complexes.

4. The preparation method according to claim 3, characterized in that, The molar ratio of deionized water to acetone is 1-3:

4.

5. The application of the oxadiazolone copper (I) organometallic complex as described in claim 1 or 2 in the detection of carbon disulfide or ferric ions.

6. The application according to claim 5, characterized in that, The detection range for carbon disulfide concentration is 1.65 × 10⁻⁶. -3 -2.98×10 -2 mol / L, detection of Fe 3+ The concentration range is 1.00 × 10⁻⁶. -5 -1.5×10 -4 mol / L.

7. The application according to claim 6, characterized in that, The specific procedure involves adding the oxadiazolone copper(I) metal organometallic complex to acetonitrile solvent to prepare a suspension, which is then injected into a cuvette to measure its fluorescence emission spectrum. Pure carbon disulfide is then added to the cuvette sequentially, and the fluorescence emission spectrum of the suspension is measured each time. A linear equation is established between the concentration of the oxadiazolone copper(I) metal organometallic complex and the concentration of carbon disulfide, thereby detecting the concentration of carbon disulfide.

8. The application according to claim 6, characterized in that, The specific procedure involves adding the oxadiazolone copper(I) metal-organic complex to tetrahydrofuran solvent to prepare a suspension, which is then injected into a cuvette to measure its fluorescence emission spectrum. Subsequently, Fe(NO3)3 aqueous solution is added to the cuvette sequentially, and the fluorescence emission spectrum of the suspension is measured each time. This establishes the relationship between the oxadiazolone copper(I) metal-organic complex and Fe... 3+ A linear equation for concentration, thus enabling the detection of Fe. 3+ The concentration.

9. The application according to claim 8, characterized in that, The specific procedure involves adding the oxadiazolone copper (I) metal-organic complex to a tetrahydrofuran solvent to prepare a suspension, which is then poured into a cuvette. Fe is removed from the suspension and added separately. 3+ Besides aqueous solutions containing other metal ions, the fluorescence emission spectra of solutions containing other ions were tested, and an equal amount of Fe was added. 3+ Aqueous solutions were analyzed to measure the fluorescence emission spectra of solutions containing mixed ions, and the oxadiazolone copper(I) organometallic complexes with Fe were determined. 3+ A linear equation for concentration, thus enabling the detection of Fe. 3+ The concentration.

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