Thiophene functionalized column [5] arene and preparation method and application thereof

Abstract

The invention discloses thiophene functionalized column [5] arene as well as a preparation method and application thereof, and belongs to the technical field of organic synthesis. On the basis of the characteristic that thiophene ring ligands are selectively complexed with cadmium ions, coordination functional groups at the upper edge and the lower edge of column [5] arene are fully utilized, and a click reaction between a column [5] arene precursor with azide groups and a thiophene derivative containing alkynyl is realized under the action of a copper catalyst, so that the thiophene functionalized column [5] arene is rapidly and efficiently obtained, and the yield of the thiophene functionalized column [5] arene is improved. The thiophene functionalized column [5] arene prepared by the invention is a simple, rapid and sensitive cadmium ion detection reagent, the concentration of cadmium ions can be quantitatively analyzed according to the ultraviolet absorption intensity change of the thiophene functionalized column [5] arene solution before and after the cadmium ions are added, and the thiophene functionalized column [5] arene has a wide application prospect in the fields of water sample environments and life systems.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic synthesis, and in particular relates to a thiophene functionalized column [5] aromatic hydrocarbon and a preparation method and application thereof. Background Art

[0002] Cadmium ions are easily absorbed and accumulated by living organisms, causing irreversible damage to the environment and organisms. Therefore, it is of great significance to detect the cadmium ion content in environmental systems and life systems. At present, the widely used methods for metal ion detection include atomic absorption spectroscopy, inductively coupled plasma mass spectrometry, and electrochemical analysis. However, these methods require expensive and complex instruments and skilled professionals in the process of detecting metal ions. The analysis process is cumbersome, the detection and analysis time is long, and the analysis cost is high. These are the shortcomings of the above analysis methods. The fluorescent probe detection method has the characteristics of high selectivity, high sensitivity, visual recognition, simple operation, and low intracellular toxicity, which makes it not only widely used in material detection, but also an important tool for sensor analysis in environmental science and life science. In recent years, many materials for identifying cadmium ions have been reported, but the synthesis steps of these materials are cumbersome, and the selectivity and sensitivity are low, resulting in reduced applicability of the identification materials. Based on this, the development of new identification materials for detecting cadmium ions has important research value for the fluorescent imaging diagnosis and analysis of cadmium ions in the environment or life system.

[0003] In the field of organic chemistry and materials science, macrocyclic compounds have been widely studied due to their unique molecular structure and properties. Among them, pillar[n]arene, as a type of cyclic macromolecule formed by benzene rings bridged by methylene, has become a research hotspot in the fields of supramolecular chemistry, host-guest recognition, controlled drug release, artificial transmembrane channels, catalysis and nanomaterials due to its high symmetry, rigidity and unique electron-rich cavity structure. Thiophene, as a sulfur-containing heterocyclic compound, has excellent electron transport properties and unique chemical properties and is widely used in organic electronic materials, drug molecules and functional polymer materials. However, the traditional preparation method of thiophene-functionalized pillar[5]arene often has the disadvantages of complicated steps, harsh reaction conditions and low yield, which is difficult to meet the needs of practical applications. Therefore, it is particularly important to develop an efficient, simple and high-yield preparation method of thiophene-functionalized pillar[5]arene. Summary of the invention

[0004] The technical problem to be solved by the present invention is to provide a thiophene functionalized column [5] aromatic hydrocarbon and its preparation method and application, so as to solve the technical problems that the synthesis steps of the existing thiophene functionalized column [5] aromatic hydrocarbon are complicated and the yield is not high enough.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is: to provide a thiophene functionalized pillar [5] aromatic hydrocarbon, the structural formula of which is:

[0006]

[0007] The present invention also discloses a method for preparing thiophene-functionalized pillar [5] aromatic hydrocarbons, comprising the following steps: using a para-substituted phenolic compound and a halogenated hydrocarbon as initial raw materials, using an iodine salt as a catalyst in an alkaline environment, and generating a pillar [5] aromatic hydrocarbon monomer through a double nucleophilic substitution reaction between the halogenated hydrocarbon and the para-substituted phenolic compound; subsequently, generating a pillar [5] aromatic hydrocarbon intermediate through Lewis acid catalysis, and then refluxing the pillar [5] aromatic hydrocarbon intermediate with an azide salt, and reacting the obtained product with an alkynyl thiophene compound and an azide group through a click reaction to generate a triazole bridge structure unit, thereby realizing the connection between thiophene and the pillar [5] aromatic hydrocarbon skeleton, and finally obtaining thiophene-functionalized pillar [5] aromatic hydrocarbons.

[0008] On the basis of the above technical solution, the present invention can also be improved as follows:

[0009] Further, the following steps are included:

[0010] S1. Dissolve a para-substituted phenol compound and a halogenated hydrocarbon in an organic solvent, then add an inorganic base and an iodized salt to the reaction system under a protective atmosphere, and react at 80-90° C. for 2-24 hours to obtain a column [5] aromatic hydrocarbon monomer; the molar ratio of the para-substituted phenol compound, the halogenated hydrocarbon, the inorganic base and the iodized salt is 0.5-1.5:3.5-4.5:1.5-3.5:0.04-0.06;

[0011] S2, dissolving the column [5] aromatic monomer and the raw material 1 in an organic solvent, then adding a Lewis acid catalyst and stirring the reaction for 1-3 hours, and finally adding an inorganic base to quench the reaction to obtain a column [5] aromatic intermediate; the raw material 1 is polyformaldehyde or triformaldehyde; the ratio of the column [5] aromatic monomer, the raw material 1, the Lewis acid catalyst and the inorganic base is 0.5-1.5 mol: 2.8-3.2 mol: 3.5-5.5 mol: 100-300 mL;

[0012] S3, dissolving the column [5] aromatic hydrocarbon intermediate and the azide salt in an organic solvent at a molar ratio of 0.5-1.5:12-17, and then reacting at 70-90° C. for 4-7 hours in a protective atmosphere to obtain the azidated column [5] aromatic hydrocarbon;

[0013] S4. Dissolve the azidated column [5] aromatic hydrocarbon, alkynyl thiophene compound, copper salt and sodium L-ascorbate in water at a molar ratio of 0.5-1.5:12-17:0.5-1.5:1.5-2.5, and then react in a protective atmosphere for 46-50 hours to obtain thiophene functionalized column [5] aromatic hydrocarbon.

[0014] Furthermore, the para-substituted phenol compound is hydroquinone, the halogenated hydrocarbon is 1,4-dibromobutane or 1,4-diiodobutane, the inorganic base is K2CO3, KOH, Na2CO3, NaHCO3 or NaOH, the iodine salt is KI or NaI, and the Lewis acid catalyst is boron trifluoride etherate or ferric chloride.

[0015] Furthermore, the azide salt is potassium azide or sodium azide, the alkynyl thiophene compound is 2-ethynyl thiophene, 2-ethynyl-3-methylthiophene, 3-ethynyl thiophene, 2-bromo-5-ethynyl thiophene, 2-ethyl-5-ethynyl thiophene, 5-ethynyl thiophene-2-carboxaldehyde, 2-ethynyl-5-methylthiophene or 5-ethynyl-2,3-dimethylthiophene, the alkynyl group serves as the reactive group of the click reaction and the coordination site of the thiophene metal ion, and the copper salt is copper sulfate.

[0016] Furthermore, the reaction temperature in S1 is 85°C and the reaction time is 13h; the reaction temperature in S3 is 80°C and the reaction time is 5h.

[0017] Furthermore, the heating rate during the reaction in S1 and S3 is 2-5°C / min.

[0018] Furthermore, the organic solvent is acetonitrile, dichloromethane or dimethylformamide (DMF).

[0019] Furthermore, the protective atmosphere gas is argon.

[0020] The invention also discloses the application of thiophene functionalized column [5] aromatic hydrocarbon in the preparation of cadmium pollution detection material.

[0021] The beneficial effects of the present invention are:

[0022] 1. Significantly improved efficiency: The present invention utilizes copper-catalyzed azide-alkyne click reaction (CuAAC) to achieve rapid introduction of thiophene groups onto column[5]arene. The process is simple, the reaction conditions are mild and the reaction rate is fast, which greatly shortens the synthesis cycle, improves production efficiency and reduces production costs.

[0023] 2. High product purity and stable yield: The present invention can stably obtain high-yield thiophene functionalized column [5] aromatics. At the same time, the post-treatment process using column chromatography can effectively remove impurities, improve the purity of the product, and ensure the quality and application effect of the product.

[0024] 3. Environmental protection and sustainability: The raw materials used in the present invention are all common organic chemicals, and the reaction conditions are mild, which reduces the generation of harmful by-products and reduces pollution to the environment.

[0025] 4. The thiophene functionalized column [5] aromatic hydrocarbon prepared by the present invention is a simple, rapid and sensitive cadmium ion detection reagent, which can quantitatively analyze the cadmium ion concentration by the change of the ultraviolet absorption intensity of the thiophene functionalized column [5] aromatic hydrocarbon solution before and after the addition of cadmium ions, and has broad application prospects in the fields of water sample environment and life system. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 Fourier transform infrared spectra of thiophene functionalized pillar[5]arene;

[0027] Figure 2 The UV-visible absorption spectrum of thiophene-functionalized pillar[5]arene;

[0028] Figure 3 This is the H NMR spectrum of thiophene functionalized column[5]arene;

[0029] Figure 4 UV-visible absorption spectra of thiophene-functionalized pillar[5]arene before and after recognition of cadmium ions. DETAILED DESCRIPTION

[0030] The specific embodiments of the present invention are described below to facilitate the understanding of the present invention by those skilled in the art. If the specific conditions are not specified in the examples, the methods are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturers are not specified in the reagents or instruments used, they are all conventional products that can be purchased commercially. However, it should be clear that the present invention is not limited to the scope of the specific embodiments. For those skilled in the art, as long as various changes are within the spirit and scope of the present invention defined and determined by the attached claims, these changes are obvious, and all inventions and creations using the concept of the present invention are protected.

[0031] Example 1

[0032] A method for preparing thiophene functionalized column [5] aromatic hydrocarbons comprises the following steps:

[0033] S1. Dissolve hydroquinone (15.00 g, 136.22 mmol) and 1,4-dibromobutane (65.91 mL, 544.90 mmol) in 300 mL of acetonitrile. After the solid is completely dissolved, introduce argon protection into the reaction system. Then, add anhydrous K2CO3 (41.42 g, 299.69 mmol) and KI (1.13 g, 6.81 mmol) under stirring, and then heat to 85°C and condense and reflux for 13 h. After the reaction is completed, wash the solid impurities with dichloromethane for many times, filter, and finally concentrate under reduced pressure at 25°C to remove acetonitrile and dichloromethane. Purify and separate by column chromatography (eluent is petroleum ether: dichloromethane = 2:1, V / V) to obtain a white powder, i.e., column [5] aromatic monomer.

[0034] S2, column [5] aromatic monomer (1.5 g, 3.95 mmol) and paraformaldehyde (0.355 g, 11.84 mmol) were dissolved in 300 mL of dichloromethane. After the solid was completely dissolved, boron trifluoride ether (C4H) was added to the reaction system. 10 BF3O (2.48mL, 19.73mmol) was stirred for reaction for 2h until the color of the reaction solution turned dark green. Finally, 200mL, 10wt% NaHCO3 was added to quench the reaction. At this time, the color of the reaction solution turned light yellow. The reaction solution was poured into a 1000mL pear-shaped separatory funnel, and the upper aqueous phase was discarded after standing for stratification. The lower organic phase was collected and concentrated under reduced pressure at 25°C. The mixture was separated and purified by column chromatography (eluent was petroleum ether: dichloromethane = 2:1, V / V) to obtain a white solid powder, i.e., decabromobutoxy-column[5]arene. The structural formula of decabromobutoxy-column[5]arene is:

[0035]

[0036] S3. Decabromobutoxy-column[5]arene (1.00 g, 502.33 μmol) was dissolved in 50 mL of DMF, followed by the addition of potassium azide (0.61 g, 7.53 mmol), argon was introduced into the reaction system, and the temperature was raised to 80° C. for 5 h. Finally, the light yellow reaction solution was poured into a beaker containing 400 mL of distilled water and stirred for 30 min. The solution was filtered and washed with distilled water (20 mL×3). The organic phase was dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation under reduced pressure at 25° C. to obtain a white solid, i.e., azidized-column[5]arene, with a yield of 87%.

[0037] S4, dissolve the azidation column [5] aromatic hydrocarbon (0.1 g, 62.04 μmol), 2-alkynylthiophene (0.1 g, 0.93 mmol), copper sulfate pentahydrate (15.49 mg, 62.04 μmol) and sodium L-ascorbate (24.58 mg, 124.08 μmol) in 1 mL of water, and then react for 48 h in an argon atmosphere; after the reaction is completed, pour the reaction solution into 100 mL of ice water, add 100 mL of dichloromethane and The organic phase was collected and washed three times with 100 mL of saturated sodium carbonate solution, and then washed three times with 100 mL of saturated saline, 0.1 M EDTA-2Na solution and deionized water, respectively. The organic phase was dried over anhydrous sodium sulfate and filtered to obtain a brown solution. After the solvent was removed by vacuum concentration, the solution was purified by column chromatography (DCM: MeOH = 30: 1, V / V) to obtain a light brown foamy solid, i.e., thiophene functionalized column [5] aromatic hydrocarbons, with a yield of 89%.

[0038] Figure 1This is the Fourier transform infrared spectrum of thiophene functionalized column [5] aromatic hydrocarbon. It can be seen from the figure that its characteristic infrared absorption peak is 700 cm -1 (CS),796cm -1 (CH),846cm -1 (CH),932cm -1 (CH),1045cm -1 (COC),1204cm -1 (COC),1290cm -1 (N=N),1401cm -1 (C=C),1465cm -1 (C=C),1499cm -1 (C=C),1590cm -1 (CN),1631cm -1 (N=N),1655cm -1 (C=C),2862cm -1 (-CH2-),2929cm -1 (-CH2-),3113cm -1 (CH), comprehensive analysis shows that the infrared spectrum is completely consistent with the theoretical structure of the synthetic product thiophene-functionalized pillar[5]arene, and it can be concluded that the target compound is a pillararene derivative.

[0039] Figure 2 This is the UV-visible absorption spectrum of thiophene functionalized pillar[5]arene. It can be seen from the figure that its characteristic absorption peak is in the range of 200-240nm, and it is concluded that the maximum absorption peak of the compound is 205nm. It is possible that the π-π transition of the thiophene ring leads to strong absorption at a lower wavelength. At the same time, there are interactions such as the conjugation effect and steric hindrance effect between the thiophene ring and pillar[5]arene.

[0040] Figure 3 Thiophene-functionalized column[5]arene 1 H NMR spectrum. From the figure, it can be seen that the characteristic proton shift of column [5] aromatics is: 1H NMR (400MHz, DMSO-d6) δ8.46 (s, 1H), 7.49 (dd, J = 5.1, 1.2 Hz, 1H), 7.38 (dd, J = 3.6, 1.2 Hz, 1H), 7.09 (dd, J = 5.1, 3.6 Hz, 1H), 6.66 (s, 1H), 4.40 (s, 2H), 3.86 (s, 1H), 3.57 (s, 2H), 2.01 (t, J = 7.3 Hz, 2H), 1.65 (s, 2H), wherein the peak shift of the bridging methylene proton signal is δ = 3.86 ppm, which indicates that the target compound is a columnar aromatic derivative. Taking the chemical shift of the ortho-proton of thiophene δ=8.46ppm as a benchmark, the integral ratio of its characteristic proton signal peak is 1:1:1:1:2:2:2:2:2:1:1. The experimental value is consistent with the ratio of the number of protons in the molecule, and it can be concluded that this molecule is the target molecule.

[0041] Example 2

[0042] A method for preparing thiophene functionalized column [5] aromatic hydrocarbons comprises the following steps:

[0043] S1. Dissolve hydroquinone (15.00 g, 136.22 mmol) and 1,4-diiodobutane (65.91 mL, 544.90 mmol) in 300 mL of acetonitrile. After the solid is completely dissolved, introduce argon protection into the reaction system. Then, add anhydrous Na2CO3 (41.42 g, 299.69 mmol) and NaI (1.13 g, 6.81 mmol) under stirring, and then heat to 80°C and reflux for 24 h. After the reaction, wash the solid impurities with dichloromethane for several times, filter, and finally concentrate under reduced pressure at 25°C to remove acetonitrile and dichloromethane. Purify and separate by column chromatography (eluent is petroleum ether: dichloromethane = 2:1, V / V) to obtain a white powder, i.e., column [5] aromatic monomer.

[0044] S2, column [5] aromatic monomer (1.5 g, 3.95 mmol) and paraformaldehyde (0.355 g, 11.84 mmol) were dissolved in 300 mL of dichloromethane. After the solid was completely dissolved, boron trifluoride ether (C4H) was added to the reaction system. 10 BF3O (2.48 mL, 19.73 mmol) was stirred for 3 h until the color of the reaction solution turned dark green, and finally 10 mL of NaHCO3 was added to quench the reaction, at which time the color of the reaction solution turned light yellow; the reaction solution was poured into a 1000 mL pear-shaped separatory funnel, and the upper aqueous phase was discarded after standing for stratification, and the lower organic phase was collected and concentrated under reduced pressure at 25°C, and separated and purified by column chromatography (eluent: petroleum ether: dichloromethane = 2:1, V / V) to obtain a white solid powder, i.e., column [5] aromatic intermediate;

[0045] S3, dissolving the column [5] aromatic hydrocarbon intermediate (1.00 g, 502.33 μmol) in 50 mL of DMF, then adding potassium azide (0.61 g, 7.53 mmol), introducing argon into the reaction system, and heating to 90° C. for 4 h, finally pouring the light yellow reaction solution into a beaker containing 400 mL of distilled water and stirring for 30 min, filtering, washing the filtrate with distilled water (20 mL×3), drying the organic phase with anhydrous sodium sulfate, and removing the solvent by vacuum rotary evaporation at 25° C. to obtain a white solid, i.e., azidized column [5] aromatic hydrocarbon;

[0046] S4, dissolve the azidation column [5] aromatic hydrocarbon (0.1 g, 62.04 μmol), 2-alkynylthiophene (0.1 g, 0.93 mmol), copper sulfate pentahydrate (15.49 mg, 62.04 μmol) and sodium L-ascorbate (24.58 mg, 124.08 μmol) in 1 mL of water, and then react in an argon atmosphere for 46-50 h; after the reaction is completed, pour the reaction solution into 100 mL of ice water and add 100 mL The product was extracted and separated with dichloromethane, and the organic phase was collected and washed three times with 100 mL of saturated sodium carbonate solution, and then washed three times with 100 mL of saturated brine, 0.1 M EDTA-2Na solution and deionized water respectively. The organic phase was dried over anhydrous sodium sulfate and filtered to obtain a brown solution. After the solvent was removed by vacuum concentration, the solution was purified by column chromatography (DCM: MeOH = 30:1, V / V) to obtain a light brown foamy solid, i.e., thiophene functionalized column [5] aromatic hydrocarbon.

[0047] Example 3

[0048] A method for preparing thiophene functionalized column [5] aromatic hydrocarbons comprises the following steps:

[0049] S1. Dissolve hydroquinone (15.00 g, 136.22 mmol) and 1,4-dibromobutane (65.91 mL, 544.90 mmol) in 200 mL of acetonitrile. After the solid is completely dissolved, introduce argon protection into the reaction system. Then, add anhydrous K2CO3 (41.42 g, 299.69 mmol) and KI (1.13 g, 6.81 mmol) under stirring, and then heat to 90°C and condense and reflux for 2 h. After the reaction is completed, wash the solid impurities with dichloromethane for many times, filter, and finally concentrate under reduced pressure at 25°C to remove acetonitrile and dichloromethane. Purify and separate by column chromatography (eluent is petroleum ether: dichloromethane = 2:1, V / V) to obtain a white powder, i.e., column [5] aromatic monomer.

[0050] S2. Dissolve column [5] aromatic monomer (1.5 g, 3.95 mmol) and trioxymethylene (0.355 g, 11.84 mmol) in 300 mL of dichloromethane. After the solid is completely dissolved, add ferric chloride (2.48 mL, 19.73 mmol) to the reaction system and stir to react for 1 hour until the color of the reaction solution changes to dark green. Finally, add 10 mL of NaHCO3 to quench the reaction. At this time, the color of the reaction solution changes to light yellow. Pour the reaction solution into a 1000 mL pear-shaped separatory funnel, let it stand for stratification, discard the upper aqueous phase, collect the lower organic phase, concentrate under reduced pressure at 25°C, and separate and purify by column chromatography (the eluent is petroleum ether: dichloromethane = 2:1, V / V) to obtain a white solid powder, i.e., decabromobutoxy column [5] aromatic.

[0051] S3. Decabromobutoxy-column[5]arene (1.00 g, 502.33 μmol) was dissolved in 50 mL of DMF, followed by the addition of potassium azide (0.61 g, 7.53 mmol), argon was introduced into the reaction system, and the temperature was raised to 70°C for 7 h. Finally, the light yellow reaction solution was poured into a beaker containing 400 mL of distilled water and stirred for 30 min. The solution was filtered and washed with distilled water (20 mL×3). The organic phase was dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation under reduced pressure at 25°C to obtain a white solid, i.e., azidized-column[5]arene.

[0052] S4, dissolve the azidation column [5] aromatic hydrocarbon (0.1 g, 62.04 μmol), 2-alkynylthiophene (0.1 g, 0.93 mmol), copper sulfate pentahydrate (15.49 mg, 62.04 μmol) and sodium L-ascorbate (24.58 mg, 124.08 μmol) in 1 mL of water, and then react in an argon atmosphere for 46-50 h; after the reaction is completed, pour the reaction solution into 100 mL of ice water and add 100 mL The product was extracted and separated with dichloromethane, and the organic phase was collected and washed three times with 100 mL of saturated sodium carbonate solution, and then washed three times with 100 mL of saturated brine, 0.1 M EDTA-2Na solution and deionized water respectively. The organic phase was dried over anhydrous sodium sulfate and filtered to obtain a brown solution. After the solvent was removed by vacuum concentration, the solution was purified by column chromatography (DCM: MeOH = 30:1, V / V) to obtain a light brown foamy solid, i.e., thiophene functionalized column [5] aromatic hydrocarbon.

[0053] Experimental example: Cadmium ion recognition ability

[0054] Taking the thiophene functionalized column [5] aromatic hydrocarbon prepared in Example 1 as an example, 100 mL of 5×10 -5M thiophene functionalized column [5] aromatic hydrocarbon-methanol solution and cadmium chloride-methanol solution were set aside, and then 1 mL of thiophene functionalized column [5] aromatic hydrocarbon-methanol solution and 1 mL of cadmium chloride-methanol solution were mixed evenly and fixed to 5 mL as the test solution, and 1 mL of thiophene functionalized column [5] aromatic hydrocarbon-methanol solution was diluted to 5 mL as the reference solution. The metal ion Cd was detected by UV spectroscopy. 2+ The recognition ability is measured by comparing the UV absorption curve of the solution to be tested with the UV absorption curve of the solution to be tested. If the wavelength of the maximum absorption peak in the UV absorption curve is shifted or the intensity is significantly changed, it indicates that complexation has occurred.

[0055] The results are as follows Figure 4 As shown, when 1:1 equivalent of Cd was added to the aromatic solution of thiophene functionalized column [5] 2+ After that, the ultraviolet absorption of the solution to be tested was significantly reduced, indicating that the thiophene functionalized column [5] aromatic hydrocarbon prepared by the present invention has a strong affinity for Cd 2+ It has remarkable UV recognition capability.

Claims

1. A thiophene functionalized pillar[5]arene, characterized in that: The structural formula of the thiophene functionalized column [5] aromatic hydrocarbon is:

2. The method for preparing thiophene functionalized column [5] aromatic hydrocarbons according to claim 1, characterized in that: The method comprises the following steps: using a para-substituted phenol compound and a halogenated hydrocarbon as initial raw materials, using an iodine salt as a catalyst in an alkaline environment, generating a column [5] aromatic hydrocarbon monomer through a dinucleophilic substitution reaction between the halogenated hydrocarbon and the para-substituted phenol compound; subsequently generating a column [5] aromatic hydrocarbon intermediate through Lewis acid catalysis, and then refluxing the column [5] aromatic hydrocarbon intermediate with an azide salt, and reacting the obtained product with an alkynyl thiophene compound and an azide group through a click reaction to generate a triazole bridging structural unit, thereby realizing the connection between thiophene and the column [5] aromatic hydrocarbon skeleton, and finally obtaining thiophene functionalized column [5] aromatic hydrocarbon.

3. The method for preparing thiophene functionalized column [5] aromatics according to claim 2, characterized in that: The following steps are involved: S1. Dissolve a para-substituted phenol compound and a halogenated hydrocarbon in an organic solvent, then add an inorganic base and an iodized salt to the reaction system under a protective atmosphere, and react at 80-90° C. for 2-24 hours to obtain a column [5] aromatic hydrocarbon monomer; the molar ratio of the para-substituted phenol compound, the halogenated hydrocarbon, the inorganic base and the iodized salt is 0.5-1.5:3.5-4.5:1.5-3.5:0.04-0.06; S2, dissolving the column [5] aromatic hydrocarbon monomer and raw material 1 in an organic solvent, then adding a Lewis acid catalyst and stirring the reaction for 1-3 hours, and finally adding an inorganic base to quench the reaction to obtain a column [5] aromatic hydrocarbon intermediate; the raw material 1 is polyformaldehyde or triformaldehyde; the ratio of the column [5] aromatic hydrocarbon monomer, raw material 1, Lewis acid catalyst and inorganic base is 0.5-1.5 mol: 2.8-3.2 mol: 3.5-5.5 mol: 100-300 mL; S3, dissolving the column [5] aromatic hydrocarbon intermediate and the azide salt in an organic solvent at a molar ratio of 0.5-1.5:12-17, and then reacting at 70-90° C. for 4-7 hours in a protective atmosphere to obtain the azidated column [5] aromatic hydrocarbon; S4. Dissolve the azidated column [5] aromatic hydrocarbon, alkynyl thiophene compound, copper salt and sodium L-ascorbate in water at a molar ratio of 0.5-1.5:12-17:0.5-1.5:1.5-2.5, and then react in a protective atmosphere for 46-50 hours to obtain thiophene functionalized column [5] aromatic hydrocarbon.

4. The method for preparing thiophene functionalized column [5] aromatic hydrocarbons according to claim 3, characterized in that: The para-substituted phenol compound is hydroquinone, the halogenated hydrocarbon is 1,4-dibromobutane or 1,4-diiodobutane, the inorganic base is K2CO3, KOH, Na2CO3, NaHCO3 or NaOH, the iodine salt is KI or NaI, and the Lewis acid catalyst is boron trifluoride etherate or ferric chloride.

5. The method for preparing thiophene functionalized column [5] aromatics according to claim 3, characterized in that: The azide salt is potassium azide or sodium azide, the alkynyl thiophene compound is 2-ethynyl thiophene, 2-ethynyl-3-methylthiophene, 3-ethynyl thiophene, 2-bromo-5-ethynyl thiophene, 2-ethyl-5-ethynyl thiophene, 5-ethynyl thiophene-2-carboxaldehyde, 2-ethynyl-5-methylthiophene or 5-ethynyl-2,3-dimethylthiophene, and the copper salt is copper sulfate.

6. The method for preparing thiophene functionalized column [5] aromatics according to claim 3, characterized in that: The reaction temperature in S1 is 85° C. and the reaction time is 13 h; the reaction temperature in S3 is 80° C. and the reaction time is 5 h.

7. The method for preparing thiophene functionalized column [5] aromatics according to claim 3, characterized in that: The heating rate during the reaction in S1 and S3 is 2-5°C / min.

8. The method for preparing thiophene functionalized column [5] aromatics according to claim 3, characterized in that: The organic solvent is acetonitrile, dichloromethane or dimethylformamide.

9. The method for preparing thiophene functionalized column [5] aromatics according to claim 3, characterized in that: The protective atmosphere is argon.

10. Use of the thiophene functionalized column [5] aromatic hydrocarbon according to claim 1 in the preparation of cadmium pollution detection materials.

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