Preparation and application of copper complexes based on 1,10-phenanthroline derivatives

Abstract

This invention relates to the preparation and application of copper complexes based on 1,10-phenanthroline derivatives. The copper complex uses 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene or bis(2-diphenylphosphinephenyl) ether as a diphosphine ligand, 2-(thiophene-2-yl)-1H-imidazolium[4,5-f][1,10]phenanthroline (a 1,10-phenanthroline derivative containing a thiophene group) as a diamine ligand, and tetrafluoroborate as a counterion. The copper complex of this invention exhibits aggregation-induced luminescence properties in solution, and this is further demonstrated by the interaction of the sulfur atom on the thiophene group with Hg... 2+ The interaction between them enables rapid and sensitive detection of Hg in solution systems. 2+ The detection.

Description

Technical Field

[0001] This invention relates to the field of stoichiometric reagents, specifically to the synthesis of tetracoordinated copper complexes of 1,10-phenanthroline derivatives containing thiophene groups and their use as phosphorescent probes in the detection of Hg. 2+ Applications in [the field]. Background Technology

[0002] Mercury is a silvery-white metal, Hg 2+ This is its common form of existence. Hg 2+ As a typical toxic heavy metal ion, Hg's toxicity manifests in its ease of binding to sulfhydryl, amino, carboxyl, and phosphate groups, affecting the activity of enzymes or functional groups associated with these groups, thereby hindering cellular biological activity and normal metabolism. 2+ Methylmercury can be converted into methylmercury by microorganisms in water. Methylmercury accumulates in organisms through the food chain and enters the human body. When methylmercury accumulates to a certain concentration in the human body, it can cause serious harm such as nausea, vomiting, abdominal pain, kidney damage, and damage to the central nervous system, and may even be life-threatening. Therefore, the concentration of Hg in environmental samples is crucial. 2+ Monitoring is of great importance.

[0003] Currently detecting Hg 2+ Methods include dithizone spectrophotometry, atomic fluorescence spectrometry, and cold atomic absorption spectrometry. These methods are widely used, but they all require complex instruments and cumbersome pretreatment procedures, making them unsuitable for rapid and on-site detection of Hg. 2+ Photochemical sensors based on fluorescent and phosphorescent materials possess advantages such as good selectivity, fast response speed, high sensitivity, and simple operation, and are widely used in the qualitative and quantitative detection of metal ions. Compared with fluorescent materials, phosphorescent sensing materials have advantages such as better thermal stability, optical stability, and higher quantum yield. They also possess a significant advantage of a larger Stokes shift, which is beneficial for distinguishing background fluorescence interference. Among phosphorescent sensing materials, iridium complexes have been extensively studied; however, iridium is expensive and has low reserves, hindering its large-scale commercial production. Furthermore, tetracoordinated copper complexes prepared with inexpensive copper as the core typically exhibit weak or no luminescence in solution due to the Jameer-Taylor effect in the excited state, significantly limiting their application in phosphorescent chemical sensing.

[0004] The literature Inorg. Chem., 2011, 50, 7412-7420 reports a sulfur-containing iridium complex that can react with Hg via sulfur atoms. 2+ The interaction between them enables the control of Hg 2+While the luminescence of this complex is detectable, its preparation cost is relatively high due to the use of the noble metal iridium as the luminescent center. The literature *Chinese J. Struct. Chem.* 2020, 39, 1314-1322 discloses three tetracoordinate copper complexes based on 1,10-phenanthroline derivatives and diphosphine ligands. These complexes exhibit strong luminescence in the solid state, but their luminescence in solution is very weak, limiting their application in solution. Summary of the Invention

[0005] The purpose of this invention is to address the limitations of current technologies by providing a copper complex based on a 1,10-phenanthroline derivative containing a thiophene group, its preparation method, and its applications. This copper complex uses 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene or bis(2-diphenylphosphinephenyl) ether as a diphosphine ligand, 2-(thiophene-2-yl)-1H-imidazolium[4,5-f][1,10]phenanthroline, a phenanthroline derivative containing a thiophene group, as a diamine ligand, and tetrafluoroborate as a counterion. The copper complex of this invention exhibits aggregation-induced emission properties in solution, and this emission occurs through the interaction of the sulfur atom on the thiophene group with Hg... 2+ The interaction between them enables rapid and sensitive detection of Hg in solution systems. 2+ The detection.

[0006] The technical solution of this invention is as follows:

[0007] A copper complex based on a thiophene-containing 1,10-phenanthroline derivative has the following structural formula:

[0008]

[0009] The method for preparing copper complexes based on thiophene-containing 1,10-phenanthroline derivatives includes the following steps:

[0010] Under nitrogen protection, tetraethyl cyano copper tetrafluoroborate and diphosphine ligand were placed in a reactor, dissolved in dichloromethane, and reacted at room temperature for 0.5–1 h. Then, an ethanol solution of 2-(thiophene-2-yl)-1H-imidazolium[4,5-f][1,10]phenanthroline was added, and the reaction was continued for 5–8 h to obtain the copper complex.

[0011] In the aforementioned step, the molar ratio of tetrafluoroborate tetraethyl copper cyanide and diphosphine ligand is 1:1.0 to 1.5.

[0012] The diphosphine ligand is 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene or bis(2-diphenylphosphine) ether;

[0013] In the aforementioned steps, the molar ratio of tetrafluoroborate tetraethyl copper cyanoate and 2-(thiophene-2-yl)-1H-imidazolium[4,5-f][1,10]phenanthroline is 1:1.0 to 1.5;

[0014] In the steps described above, 10-100 mL of dichloromethane is added for every millimole of tetrafluoroborate tetraethyl copper; 10-100 mL of ethanol is added for every millimole of 2-(thiophene-2-yl)-1H-imidazol[4,5-f][1,10]phenanthroline.

[0015] The aforementioned application of copper complexes based on thiophene-containing 1,10-phenanthroline derivatives is used to identify Hg in solution. 2+ .

[0016] Specifically, it includes one of the following three methods:

[0017] Method 1 includes the following steps:

[0018] A mixed test solution is prepared by adding the test aqueous solution to an acetonitrile solution containing 80%-90% water of the copper complex. Under 365nm ultraviolet light, when the copper complex changes from its original yellow color to colorless as observed with the naked eye, it indicates the presence of Hg in the test aqueous solution. 2+ .

[0019] In the mixed test solution, the concentration of the copper complex was 5.0 × 10⁻⁶. -6 mol / L~5.0×10 -2 mol / L, the mixed test solution contains Hg 2+ The concentration range for ions is 5.0 × 10⁻⁶. -7 mol / L~5.0mol / L;

[0020] The volume ratio of the acetonitrile solution of the copper complex to the aqueous solution of the test sample is 10–500:1;

[0021] When the copper complex changes from its original yellow color to colorless as observed by the naked eye, the preferred molar ratio is determined to be: copper complex: Hg 2+ Ions = 0.1 to 10:1;

[0022] Method 2 includes the following steps:

[0023] A mixed test solution was prepared by adding the test aqueous solution to an acetonitrile solution containing 80%-90% water of the copper complex. The emission intensity change at the maximum emission peak of the mixed solution was measured using a fluorescence spectrometer. When the emission intensity quenching exceeded 50%, it indicated that the test aqueous solution contained Hg. 2+ ;

[0024] In the mixed test solution, the concentration of the copper complex was 5.0 × 10⁻⁶. -6mol / L~5.0×10 -2 mol / L, the mixed test solution contains Hg 2+ The concentration range for ions is 5.0 × 10⁻⁶. -7 mol / L~5.0mol / L;

[0025] In the test procedure, the volume ratio of the acetonitrile solution of the copper complex to the aqueous solution to be tested is 10–500:1;

[0026] When the emission intensity quenching at the maximum emission peak exceeds 50%, the preferred molar ratio is: copper complex: Hg 2+ Ions = 0.1 to 10:1;

[0027] Alternatively, method three includes the following steps:

[0028] A mixed test solution was prepared by adding the test aqueous solution to an acetonitrile solution containing 80%-90% water of the copper complex. The absorption intensity of the mixed solution at 290 nm was measured using a UV-Vis spectrophotometer. When the decrease in absorbance exceeded 10%, it indicated the presence of Hg in the test aqueous solution. 2+ .

[0029] In the mixed test solution, the concentration of the copper complex was 5.0 × 10⁻⁶. -6 mol / L~5.0×10 -2 mol / L, the mixed test solution contains Hg 2+ The concentration range for ions is 5.0 × 10⁻⁶. -7 mol / L~5.0mol / L;

[0030] In the test procedure, the volume ratio of the acetonitrile solution of the copper complex to the aqueous solution to be tested is 10–500:1;

[0031] When the decrease in absorption intensity of the copper complex at 290 nm exceeds 10%, the preferred molar ratio is determined to be: copper complex: Hg. 2+ Ions = 0.1 to 10:1;

[0032] The aqueous solution to be tested contains Hg 2+ Ag + K + Pb 2+ Cu 2+ Ni 2+ Na + Cd 2+ Co 2+ Zn 2+ Mg 2+ One or more ions in it.

[0033] The essential features of this invention are:

[0034] In current technologies, four-coordinate copper complexes exhibit weak luminescence in solution systems due to the Jan-Taylor effect, making them unsuitable for ion detection. This invention presents an ionic copper complex with a 1,10-phenanthroline derivative as the diamine ligand, containing a thiophene unit. The luminescence is achieved through the lone pair electrons of the sulfur atom on this unit interacting with Hg. 2+ The network interaction between them enables the control of Hg 2+ Selective recognition of Hg. This type of copper complex exhibits aggregation-induced luminescence, overcoming the weak luminescence of tetracoordinate copper complexes in solution, thus enabling selective recognition of Hg in solution. 2+ Specificity testing.

[0035] The beneficial effects of this invention are as follows:

[0036] (1) The 1,10-phenanthroline derivative containing a thiophene group in this invention can form a stable complex with metallic copper. The synthesis steps are simple, the yield is high, and the preparation cost is low. The planar configuration of the 1,10-phenanthroline derivative ligands results in layer-by-layer stacking at high concentrations, causing the copper complex to exhibit strong aggregation-induced luminescence in a mixed solution of acetonitrile and water. This provides a basis for detecting Hg using changes in phosphorescence emission intensity of the copper complex in solution. 2+ Provided conditions. Through the sulfur atom on the thiophene unit in the complex and Hg 2+ The network effect enables Hg 2+ Selective identification with a detection limit as low as 5.0 × 10⁻⁶. -7 mol / L.

[0037] (2) The copper complex described in this invention can be used to detect Hg using phosphorescence emission spectroscopy and ultraviolet-visible absorption spectroscopy. 2+ Qualitative and quantitative detection. When Hg is added to a mixed solution of acetonitrile and water of the complex... 2+ At this time, the emission intensity at the maximum emission peak decreases by 50% to 98%. When Hg is added to a mixed solution of acetonitrile and water of the copper complex... 2+ At that time, the absorbance of the complex at 290 nm decreased by 10%–70%. These two copper complexes have an effect on Hg in aqueous solution. 2+ Their high sensitivity and selectivity demonstrate their application value in the fields of phosphorescence sensing and ultraviolet absorption sensing. Attached Figure Description

[0038] Figure 1 This is a graph showing the aggregation-induced emission test results of the complex Cu1 obtained in Example 4;

[0039] Figure 2 The complex Cu1 obtained in Example 5 is related to Hg. 2+ Changes in the phosphorescence spectrum in response;

[0040] Figure 3 The graph shows the selectivity test results of the complex Cu1 obtained in Example 6 to several common metal ions;

[0041] Figure 4 The complex Cu1 obtained in Example 7 is related to Hg. 2+ Competitive test results with common metal ions;

[0042] Figure 5 This is a graph showing the aggregation-induced emission test results of the complex Cu2 obtained in Example 8;

[0043] Figure 6 The complex Cu2 obtained in Example 9 is related to Hg. 2+ Changes in the phosphorescence spectrum in response;

[0044] Figure 7 The graph shows the selectivity test results of the complex Cu2 obtained in Example 10 to several common metal ions;

[0045] Figure 8 The complex Cu2-Hg obtained in Example 11 2+ Competitive test results with common metal ions;

[0046] Figure 9 The complex Cu1 obtained in Example 12 is related to Hg. 2+ The UV-Vis absorption spectrum of the response;

[0047] Figure 10 The complex Cu2-Hg obtained in Example 13 2+ The UV-Vis absorption spectrum of the response. Detailed Implementation

[0048] The present invention will be further described below through specific embodiments, but these are not intended to limit the invention.

[0049] The complexes of this invention can be synthesized via the following route:

[0050]

[0051] Example 1:

[0052] Preparation of ligand 2-(thien-2-yl)-1H-imidazol[4,5-f][1,10]phenanthroline: 1.0 mmol of 1,10-phenanthroline-5,6-dione, 20.0 mmol of ammonium acetate, and 1.2 mmol of 2-thienylcarbaldehyde were placed in a 100 mL three-necked round-bottom flask. 35 mL of glacial acetic acid was added under nitrogen protection, and the mixture was reacted at 120 °C in the dark for 3 h. After the reaction was completed, the pH of the reaction solution was adjusted to 7 with ammonia at 0 °C, and then filtered under reduced pressure. The solid product was collected and washed with ethanol to obtain ligand 2-(thien-2-yl)-1H-imidazol[4,5-f][1,10]phenanthroline.

[0053] Example 2:

[0054] Preparation of the ionic copper complex Cu1: 0.50 mmol of tetraethyl copper tetrafluoroborate and 0.50 mmol of 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene were dissolved in 10 mL of dichloromethane and reacted at room temperature for 30 min. Then, 10 mL of an ethanol solution containing 0.50 mmol of 2-(thiophene-2-yl)-1H-imidazolium[4,5-f][1,10]phenanthroline was added, and the reaction was continued for 5 hours. After the reaction was complete, the solvent was evaporated to obtain the crude product. Finally, the crude product was purified by column chromatography using dichloromethane and methanol (volume ratio = 30:1 to 10:1) as eluent to obtain the complex Cu1.

[0055] Complex Cu1 passed through 1 H NMR, 13 C10 NMR and mass spectrometry characterization confirmed the correct structure, and the data are as follows:

[0056] 1 H NMR (400MHz, DMSO-d6) δ9.01(d,J=8.2Hz,2H),8.47(d,J=4.6Hz,2H),7.97(d,J=3.6Hz,1H),7.87(d,J=7.8Hz,4H),7.82(d,J=4.9Hz,1 H),7.33(t,J=4.3Hz,1H),7.25(dt,J=15.0,7.6Hz,7H),7.09(t,J=7.6Hz,9H),6.90(q,J=6.1Hz,8H),6.57–6.51(m,2H),1.75(s,6H). 13C NMR(101MHz,DMSO-d6)δ154.87,154.80,154.74,145.80,140.43,138.02,134.97,134.30,132.94,132.86 ,132.78,131.91,131.74,131.53,131.17,130.45,129.22,128.36,125.76,125.02,124.53,36.35,28.54.

[0057] MS(ESI) m / z: Experimental value: m / z 943.1851 [M–BF4] + Theoretical value: m / z 943.1853.

[0058] Example 3:

[0059] Preparation of the copper complex Cu2: 0.50 mmol of tetraethyl copper tetrafluoroborate and 0.50 mmol of bis(2-diphenylphosphine) ether were dissolved in 10 mL of dichloromethane and reacted at room temperature for 30 min. Then, 10 mL of an ethanol solution containing 0.50 mmol of 2-(thiophene-2-yl)-1H-imidazolium[4,5-f][1,10]phenanthroline was added, and the reaction was continued for 5 hours. After the reaction was complete, the solvent was evaporated to obtain the crude product. Finally, the crude product was purified by column chromatography using dichloromethane and methanol (volume ratio = 30:1 to 10:1) as eluent to obtain the complex Cu2.

[0060] Complex Cu2 passed through 1 H NMR, 13 C10 NMR and mass spectrometry characterization confirmed the correct structure, and the data are as follows:

[0061] 1 H NMR (400MHz, DMSO-d6) δ9. 1 H NMR (400MHz, DMSO-d6) δ8.99(d,J=8.2Hz,2H),8.81(d,J=4.7Hz,2H),7.95(d,J=3.7Hz,1H),7.87(t,J=6.6Hz,2H),7.79(d,J=4.9Hz,1H),7 .45–7.40(m,2H),7.28(t,J=7.5Hz,5H),7.17(t,J=7.7Hz,10H),7.08(t,J=7.6Hz,2H),6.95(t,J=6.3Hz,8H),6.65(dt,J=7.7,4.1Hz,2H). 13C NMR (101MHz, CDCl3) δ158.43,148.55,146.99,141.11,134.39,133.07,132.99,132.91,132.12,132.01,130.94,130.7 7,130.59,130.17,129.00,128.80,128.75,128.70,128.52,128.19,125.19,124.69,124.25,124.11,123.97,120.45.

[0062] MS(ESI) m / z: Experimental value: m / z 903.1538 [M–BF4] + Theoretical value: m / z 903.1575.

[0063] Example 4:

[0064] Aggregation-induced emission properties of complex Cu1: Take 10 1cm quartz cuvettes and add 2.5×10⁻⁶ ppm of the complex to each cuvette according to the specified ratio. -4 An acetonitrile solution of complex Cu1, along with acetonitrile and deionized water, was prepared such that the water content of the acetonitrile solution of complex Cu1 was 0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, and 90%, respectively. The concentration of complex Cu1 in the aqueous acetonitrile solution was 2.5 × 10⁻⁶ mol / L. -5 The concentration was mol / L. After standing for a while, the emission spectrum of the mixed solution was tested. The test results are attached. Figure 1 As shown in the figure, the emission intensity of the complex Cu1 increases significantly with increasing water content, reaching a 200-fold increase when the water content reaches 90%. Under 365 nm ultraviolet light irradiation, the solution emits a bright yellow light. The experimental results indicate that the complex Cu1 exhibits significant aggregation-induced emission properties, which can be used for phosphorescent emission spectroscopy in the detection of Hg. 2+ Provide excellent conditions.

[0065] Example 5:

[0066] Complex Cu1 against Hg 2+ Phosphorescence spectrum test of the response: Take a quartz cuvette with a diameter of 1 cm, add 2 mL of 2.5 × 10⁻⁶ ppm solution. -5 An acetonitrile solution of complex Cu1 with a water content of 90% (mol / L) was prepared. Then, 5 μL, 10 μL, 15 μL, 20 μL, 25 μL, 30 μL, 35 μL, 40 μL, 45 μL, 50 μL, 55 μL, 60 μL, 65 μL, 70 μL, 75 μL, 80 μL, 85 μL, 90 μL, 95 μL, and 100 μL of 1×10⁻⁶ mol / L solution were gradually added to the above cuvettes. -3mol / L Hg 2+ The aqueous solution was mixed thoroughly and allowed to stand for a short time before the emission spectrum of the solution was measured. The test results are shown in the appendix. Figure 2 As can be seen from the graph, with Hg 2+ With the addition of [unspecified ingredient], the emission intensity at the maximum emission wavelength of 560 nm gradually decreases. In the complex Cu1 and Hg [unspecified ingredient]... 2+ Within a molar ratio of 0 to 1:1, the emission intensity decreases linearly. Under 365 nm ultraviolet light irradiation, the copper complex gradually changes from its original yellow color to colorless, as observed by the naked eye. When the complex Cu1 and Hg... 2+ When the molar ratio exceeds 1:1, the emission intensity of the copper complex does not change significantly. This demonstrates that the Cu1 complex can achieve emission of Hg... 2+ Quantitative detection.

[0067] Example 6:

[0068] Complex Cu1 against Hg 2+ Selectivity test of response: Take 11 1cm quartz cuvettes and add 2mL of 2.5×10⁻⁶ solution to each. -5 An acetonitrile solution of the complex Cu1 with a water content of 90% (mol / L) was prepared, and then 50 μL of 1×10 mol / L solution was added to each of the above cuvettes. -3 mol / L Hg 2+ Ag + K + Pb 2+ Cu 2+ Ni 2+ Na + Cd 2+ Co 2+ Zn 2+ Mg 2+ After mixing the aqueous solution and allowing it to stand for a short time, the emission spectra of the solutions were measured. The test results are shown in the appendix. Figure 3 From the graph, we can clearly observe that, except for Hg 2+ In addition, the addition of other ions such as Ag + K + Pb 2+ Cu 2+ Ni 2+ Na + Cd 2+ Co 2+ Zn 2+ Mg 2+ The addition of Hg had little effect on the emission intensity of the Cu1 complex at the maximum emission wavelength of 560 nm, and the emission color of the copper complex did not change significantly under 365 nm ultraviolet light irradiation. 2+Subsequently, the emission intensity of the complex Cu1 at 560 nm was quenched by 98%. Under 365 nm ultraviolet light irradiation, the copper complex was observed to change from its original yellow color to colorless, clearly distinguishable from the colors of solutions containing other metal ions. Experimental results indicate that the complex Cu1 can be used for Hg... 2+ Specificity identification.

[0069] Example 7:

[0070] Complex Cu1 against Hg 2+ Competitive test of response: Take 10 1cm quartz cuvettes and add 2mL of 2.5×10 -5 An acetonitrile solution of the complex Cu1 with a water content of 90% (mol / L) was prepared. Then, 50 μL of a 1×10⁻⁶ solution was added to each of the above cuvettes. -3 Ag mol / L + K + Pb 2+ Cu 2+ Ni 2+ Na + Cd 2+ Co 2+ Zn 2+ Mg 2+ An aqueous solution was added, and after standing for a short time, the emission spectra of each solution were measured. Then, 50 μL of 1×10⁻⁶ solution was added to these cuvettes. -3 mol / L Hg 2+ The emission spectra of each aqueous solution were tested again, and the results are attached. Figure 4 The dotted column represents the emission intensity of Cu1 acetonitrile solution at 560 nm; the oblique line column represents the emission intensity of Cu1 acetonitrile solution at 560 nm. + K + Pb 2+ Cu 2+ Ni 2+ Na + Cd 2+ Co 2+ Zn 2+ Mg 2+ The emission intensity at 560 nm; the horizontally filled column represents the addition of Hg to the above mixed solution. 2+ The emission intensity at 560 nm was then compared. It was found that adding Ag... + K + Pb 2+ Cu 2+ Ni 2+ Na + Cd 2+ Co 2+ Zn 2+ Mg2+ The effect on the emission peak intensity of the complex is minimal. Under 365nm ultraviolet light irradiation, the emission color and brightness are the same as those without Ag. + K + Pb 2+ Cu 2+ Ni 2+ Na + Cd 2+ Co 2+ Zn 2+ Mg 2+ The aqueous solutions showed almost no difference. However, with Hg... 2+ The addition of [a specific ingredient] resulted in a 98% quenching of the emission intensity at 560 nm. Under 365 nm ultraviolet light irradiation, the emission color of the copper complex changed from yellow to colorless, as observed by the naked eye. These results demonstrate that the complex Cu1 can still achieve [a specific effect] in the presence of other metal ions, thus inhibiting the emission of Hg [a specific substance]. 2+ Effective detection.

[0071] Example 8:

[0072] Aggregation-induced emission properties of the complex Cu2: Take 10 1 cm quartz cuvettes and add 2.5 × 10⁻⁶ ppm of Cu2+ to each cuvette according to the specified ratio. -4 An acetonitrile solution of complex Cu2, acetonitrile, and deionized water were used to prepare an acetonitrile solution of complex Cu2 with water contents of 0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, and 90%, respectively. The concentration of complex Cu2 in the aqueous acetonitrile solution was 2.5 × 10⁻⁶ mol / L. -5 The concentration was mol / L. After standing for a while, the emission spectrum of the mixed solution was tested. The test results are attached. Figure 5 As shown in the figure, the emission intensity of the Cu2 complex increases with increasing water content, reaching a 45-fold increase when the water content reaches 80%. Under 365 nm UV irradiation, the luminescence of the solution is significantly enhanced. Experimental results indicate that the Cu2 complex exhibits significant aggregation-induced emission properties, which can be used for phosphorescent emission spectroscopy in the detection of Hg. 2+ Provide excellent conditions.

[0073] Example 9:

[0074] Complex Cu2 with Hg 2+ Phosphorescence spectrum test of the response: Take a 1cm quartz cuvette and add 2mL of 2.5×10 -5An acetonitrile solution of the complex Cu2 (mol / L, water content 80%) was prepared. Then, 5 μL, 10 μL, 15 μL, 20 μL, 25 μL, 30 μL, 35 μL, 40 μL, 45 μL, 50 μL, 55 μL, 60 μL, 65 μL, 70 μL, 75 μL, 80 μL, 85 μL, 90 μL, 95 μL, and 100 μL of 1×10⁻⁶ mol / L Cu2+ solution were gradually added to the above cuvettes. -3 mol / L Hg 2+ The aqueous solution was allowed to stand for a short time before its emission spectrum was measured. The results are shown in the appendix. Figure 6 As can be seen from the figure, in the complex Cu2 and Hg 2+ The molar ratio is in the range of 0 to 1:1, with Hg 2+ With the addition of [unspecified ingredient], the emission intensity at the maximum emission wavelength of 550 nm gradually decreased. Under 365 nm ultraviolet light irradiation, the copper complex was observed to gradually change from its original yellow color to colorless. When the complex Cu2+ reacts with Hg... 2+ When the molar ratio exceeds 1:1, the emission intensity of the copper complex does not change significantly. This demonstrates that the Cu2 complex can achieve emission of Hg... 2+ Quantitative detection.

[0075] Example 10:

[0076] Complex Cu2 with Hg 2+ Selectivity test of response: Take 11 1cm quartz cuvettes and add 2mL of 2.5×10⁻⁶ solution to each. -5 An acetonitrile solution of the complex Cu2 with a water content of 80% (mol / L) was prepared, and then 50 μL of 1×10 mol / L solution was added to each of the above cuvettes. -3 mol / L Hg 2+ Ag + K + Pb 2+ Cu 2+ Ni 2+ Na + Cd 2+ Co 2+ Zn 2+ Mg 2+ The aqueous solution was allowed to stand for a short time, and the emission spectra of the solutions were measured. The test results are shown in the appendix. Figure 7 From the graph, we can clearly observe that, except for Hg 2+ In addition, the addition of other ions such as Ag + K + Pb 2+ Cu 2+ Ni 2+ Na + Cd 2+ Co 2+Zn 2+ Mg 2+ The addition of Hg had little effect on the emission intensity of the Cu2 complex at the maximum emission wavelength of 550 nm, and the luminescence color of the copper complex did not change significantly under 365 nm ultraviolet light irradiation. 2+ Subsequently, the emission intensity of the Cu2+ complex changed significantly, with a 98% quenching at 550 nm. Under 365 nm UV irradiation, the copper complex changed from its original yellow color to colorless, clearly distinguishable from solutions containing other metal ions. Experimental results indicate that the Cu2+ complex can be used for Hg... 2+ Specificity identification.

[0077] Example 11:

[0078] Complex Cu2 with Hg 2+ Competitive test of response: Take 10 1cm quartz cuvettes and add 2mL of 2.5×10 -5 An acetonitrile solution of the complex Cu2+ with a water content of 80% (mol / L) was prepared. Then, 50 μL of a 1×10⁻⁶ solution was added to each of the above cuvettes. -3 Ag mol / L + K + Pb 2+ Cu 2+ Ni 2+ Na + Cd 2+ Co 2+ Zn 2+ Mg 2+ An aqueous solution was added, and after standing for a short time, the emission spectra of each solution were measured. Then, 50 μL of 1×10⁻⁶ solution was added to these cuvettes. -3 mol / L Hg 2+ The emission spectra of each aqueous solution were tested again, and the results are attached. Figure 8 The dotted column represents the emission intensity of Cu2 acetonitrile solution at 550 nm; the oblique line column represents the emission intensity of Cu2 acetonitrile solution at 550 nm. + K + Pb 2+ Cu 2+ Ni 2+ Na + Cd 2+ Co 2+ Zn 2+ Mg 2+ The emission intensity at 550 nm; the horizontally filled column represents the addition of Hg to the above mixed solution. 2+ The emission intensity at 550 nm was then compared. It was found that adding Ag... + K+ Pb 2+ Cu 2+ Ni 2+ Na + Cd 2+ Co 2+ Zn 2+ Mg 2+ The effect on the emission peak intensity is minimal. Under 365nm ultraviolet light irradiation, the emission color and brightness are the same as without Ag. + K + Pb 2+ Cu 2+ Ni 2+ Na + Cd 2+ Co 2+ Zn 2+ Mg 2+ The aqueous solutions showed almost no difference. However, with Hg... 2+ The addition of [a specific ingredient] resulted in a 98% quenching of emission intensity at 550 nm, and under 365 nm UV irradiation, the copper complex changed from its original yellow color to colorless, as observed with the naked eye. These results demonstrate that the Cu2+ complex can still achieve [a specific effect] on Hg [a specific substance] in the presence of other metal ions. 2+ Effective detection.

[0079] Example 12:

[0080] Complex Cu1 against Hg 2+ Selectivity test of UV-Vis absorption spectroscopy response: Take 11 1cm quartz cuvettes and add 2mL of 2.5×10⁻⁶ solution to each. -5 An acetonitrile solution of the complex Cu1 with a water content of 90% (mol / L) was prepared, and then 50 μL of 1×10 mol / L solution was added to each of the above cuvettes. -3 mol / L Hg 2+ Ag + K + Pb 2+ Cu 2+ Ni 2+ Na + Cd 2+ Co 2+ Zn 2+ Mg 2+ The aqueous solution was allowed to stand for a short time, and then the ultraviolet-visible absorption spectra of the solution were measured. The test results are shown in the appendix. Figure 9 From the graph, it can be observed that, except for Hg 2+ In addition, the addition of other ions such as Ag + K + Pb 2+ Cu 2+ Ni2+ Na + Cd 2+ Co 2+ Zn 2+ Mg 2+ The addition of Hg has little effect on the UV-Vis absorption spectrum of the complex Cu1, with minimal changes in the intensity of each absorption peak. 2+ Subsequently, the absorption spectrum of the complex Cu1 changed significantly, with a 45% decrease in absorbance at 290 nm. Experimental results indicate that the complex Cu1 can achieve Hg control by altering the UV-Vis absorption spectrum. 2+ Specificity identification.

[0081] Example 13:

[0082] Complex Cu2 with Hg 2+ Selectivity test of UV-Vis absorption spectroscopy response: Take 11 1cm quartz cuvettes and add 2mL of 2.5×10⁻⁶ solution to each. -5 An acetonitrile solution of the complex Cu2 with a water content of 80% (mol / L) was prepared, and then 50 μL of 1×10 mol / L solution was added to each of the above cuvettes. -3 mol / L Hg 2+ Ag + K + Pb 2+ Cu 2+ Ni 2+ Na + Cd 2+ Co 2+ Zn 2+ Mg 2+ The aqueous solution was allowed to stand for a short time, and then the ultraviolet-visible absorption spectra of the solution were measured. The test results are shown in the appendix. Figure 10 From the graph, it can be observed that, except for Hg 2+ In addition, the addition of other ions such as Ag + K + Pb 2+ Cu 2+ Ni 2+ Na + Cd 2+ Co 2+ Zn 2+ Mg 2+ The addition of Hg has little effect on the UV-Vis absorption spectrum of the complex Cu2, with minimal changes in the intensity of each absorption peak. 2+ Subsequently, the absorption spectrum of the complex Cu2 changed significantly, with a 70% decrease in absorbance at 290 nm. Experimental results indicate that the complex Cu2 can achieve Hg control by altering the UV-Vis absorption spectrum. 2+ Specificity identification.

[0083] Matters not covered in this invention are common knowledge.

Claims

1. A copper complex based on a 1,10-phenanthroline derivative containing a thiophene group, characterized by the following structural formula: 。 2. The method for preparing copper complexes based on 1,10-phenanthroline derivatives containing thiophene groups as described in claim 1, characterized in that the method comprises the following steps: Under nitrogen protection, tetraethyl copper tetrafluoroborate and diphosphine ligand were placed in a reactor, dissolved in dichloromethane, and reacted at room temperature for 0.5 to 1 h. Then, an ethanol solution of 2-(thiophene-2-yl)-1H-imidazolium[4,5-f][1,10]phenanthroline was added, and the reaction was continued for 5 to 8 h to obtain the copper complex. in, The molar ratio of tetraethyl copper tetrafluoroborate to diphosphine ligand is 1:1.0~1.5; the molar ratio of tetraethyl copper tetrafluoroborate to 2-(thiophene-2-yl)-1H-imidazolium[4,5-f][1,10]phenanthroline is 1:1.0~1.

5. The diphosphine ligand is 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene or bis(2-diphenylphosphine) ether.

3. The method for preparing copper complexes based on 1,10-phenanthroline derivatives containing thiophene groups as described in claim 2, characterized in that 10-100 mL of dichloromethane is added per millimole of copper tetrafluoroborate. Add 10-100 mL of ethanol to each millimole of 2-(thiophene-2-yl)-1H-imidazol[4,5-f][1,10]phenanthroline.

4. The application of the copper complex based on a thiophene-containing 1,10-phenanthroline derivative as described in claim 1, characterized in that it is used to identify Hg in solution. 2+ The application in question is for the diagnosis or treatment of non-disease purposes.

5. The application of the copper complex based on a thiophene-containing 1,10-phenanthroline derivative as described in claim 4, characterized in that it comprises one of the following three methods: Method 1 includes the following steps: A mixed test solution is prepared by adding the test aqueous solution to an acetonitrile solution containing 80%-90% water of the copper complex. Under 365 nm ultraviolet light, when the copper complex changes from its original yellow color to colorless as observed with the naked eye, it indicates the presence of Hg in the test aqueous solution. 2+ ; In the mixed test solution, the concentration of the copper complex was 5.0 × 10⁻⁶. -6 mol / L ~ 5.0 × 10 -2 mol / L; Copper complex: Hg 2+ Ions = 0.1~10:1; Method 2 includes the following steps: A mixed test solution was prepared by adding the test aqueous solution to an acetonitrile solution containing 80%-90% water of the copper complex. The emission intensity change at the maximum emission peak of the mixed solution was measured using a fluorescence spectrometer. When the emission intensity quenching exceeded 50%, it indicated that the test aqueous solution contained Hg. 2+ ; In the mixed test solution, the concentration of the copper complex was 5.0 × 10⁻⁶. -6 mol / L ~ 5.0 × 10 -2 mol / L; Copper complex: Hg 2+ Ions = 0.1~10:1; Alternatively, method three includes the following steps: A mixed test solution was prepared by adding the test aqueous solution to an acetonitrile solution containing 80%-90% water of the copper complex. The absorption intensity of the mixed solution at 290 nm was measured using a UV-Vis spectrophotometer. When the decrease in absorbance exceeded 10%, it indicated the presence of Hg in the test aqueous solution. 2+ Copper complex: Hg 2+ Ions = 0.1~10:1; In the mixed test solution, the concentration of the copper complex was 5.0 × 10⁻⁶. -6 mol / L ~ 5.0 × 10 -2 mol / L.

6. The application of the copper complex based on a thiophene-containing 1,10-phenanthroline derivative as described in claim 5, characterized in that, in methods one, two, and three, the mixed test solution contains Hg. 2+ The concentration range for ions is 5.0 × 10⁻⁶. -7 mol / L~5.0mol / L.

7. The application of the copper complex based on the thiophene group-containing 1,10-phenanthroline derivative as described in claim 5, characterized in that in methods one, two and three, the volume ratio of the acetonitrile solution of the copper complex to the aqueous solution to be tested is 10~500:1.

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