A method for preparing high-order cyclic catenane supramolecular compounds

Abstract

The present invention discloses a method for preparing a high-order cyclic catenane supramolecular compound, which relates to the technical field of catenane supramolecular compounds. * 2M2(DHNDI)](OTf)2(M=Ir / Rh) is used as a basic unit, and a high-order cyclic organometallic 4-catenane supramolecular compound is efficiently prepared in one step through a coordination-driven self-assembly synthesis strategy guided by non-covalent bond forces. Based on the preparation method of the present invention, similar high-order cyclic 4-catenane structures can also be obtained after regulating the structure of the organic linking ligand and the type of metal center of the half-sandwich building unit, indicating that the preparation method has good broad spectrum. In the current preparation of catenane compounds, the preparation method of the present invention for organometallic high-order catenane supramolecular compounds has the characteristics of simple operation, high yield, wide applicability, good repeatability, etc.

Description

Technical Field

[0001] The present invention relates to the technical field of catenane supramolecular compounds, and in particular to a method for preparing high-order cyclic catenane supramolecular compounds. Background Art

[0002] Mechanically interlocked molecules (MIMs) have sparked considerable curiosity due to their aesthetic appeal and potential applications in smart materials, catalysts, and molecular machines. Currently, various molecular interlock types, including Borromean rings, Solomon knots, Stars of David, and interlocking cages, have been synthesized using templated approaches (transition metal templates, active metal templates, π-donor or π-acceptor templates, free radical pair templates, etc.) or template-free methods (electrostatic interactions, π-π stacking interactions, hydrogen bonding, solvent diversion effects, etc.). The synthesis of catenane compounds remains a hot topic in this field, at the forefront of efforts to fabricate artificial molecular machines and explore the dynamics of interlocked structures in polymers, MOFs, and other materials. Each significant advance in their research has implications not only for supramolecular chemistry but also for a range of scientific disciplines, from biology to soft matter physics. Consequently, chemists are actively pursuing further advancements in catenane research.

[0003] However, to this day, the catenane molecules synthesized by chemists are mainly low-order [2] catenane structures, and the design and synthesis of high-order [n] catenane (n>3) molecules is still a very challenging topic. There are only a few examples of high-order cyclic catenanes (catenanes formed by 3 or more single rings interlaced with each other and connected end to end). At the current stage, there is a lack of effective synthesis methods for high-order catenanes, especially for high-order catenanes with complex structures. Many high-order catenanes rely on template-directed synthesis of tetracationic cycloalkane π acceptors and crown ether-based π donors. However, their inherent limitations, cumbersome synthesis steps and low yields have restricted the development of high-order catenanes. At the same time, the means to achieve efficient synthesis of cyclic catenanes are relatively simple, mainly based on metal template synthesis strategies. Therefore, it is of great research significance to develop a method for preparing high-order cyclic catenanes with high yield and simple synthesis steps.

[0004] Coordination bonds, with their robust strength, reversibility, and geometrically distinct properties, have become one of the most powerful tools in supramolecular chemistry for assembling structurally specific supramolecular compounds. Coordination-driven self-assembly has also emerged as a popular method for constructing well-defined, discrete supramolecular coordination compounds, ranging from two-dimensional (2-D) polygons to three-dimensional (3-D) cages, prisms, and polyhedra. Compared to classical covalent synthesis methods, metal-ligand coordination approaches offer considerable synthetic advantages, such as fewer steps and the rapid and easy preparation of defect-free final products.

[0005] In recent years, the use of half-sandwich structures has also been proven to be one of the effective means of constructing catenane compounds. Compared with other methods, half-sandwich structures have many advantages. We can easily obtain the raw materials required for the reaction, such as [(p-cymene)-RuCl2]2 or [Cp * MCl2]2(Cp * =η 5 -C5Me5, M=Ir or Rh), they have high yield and good stability; the three elements Ru(II), Ir(III) and Rh(III) have six coordination sites during the coordination process, and half of the coordination sites of the metal are shielded by π-ligands, which is conducive to directional bonding; in addition, due to the symmetry of the cyclopentadienyl ring, this type of compound is very easy to crystallize, and we can use XRD and other methods to analyze it at the molecular level; finally, compounds containing semi-sandwich structure organometallic Ru, Ir, and Rh have very high application prospects in organic synthesis and catalysis, as well as optical properties. Summary of the Invention

[0006] The present invention aims to provide a method for preparing supramolecular compounds of higher-order cyclic catenanes. This method utilizes a coordination-driven self-assembly strategy and the synergistic effects of non-covalent bonds such as π-π stacking, intermolecular forces, and intramolecular forces, using linker ligands and semi-sandwich organometallic building blocks. This method has high application and research value in the synthesis of complex topological catenane structures through coordination supramolecular chemistry.

[0007] The purpose of the present invention can be achieved through the following technical solutions:

[0008] A method for preparing a high-order cyclic catenane supramolecular compound comprises the following steps:

[0009] A. Using 3-vinylpyridine, 4,7-dibromo-2,1,3-benzothiadiazole, triethanolamine, and palladium acetate as raw materials, adding N,N-dimethylformamide as solvent, reacting at 110° C. under an inert gas atmosphere for 2 days; after the reaction is completed, wait for the mixture to cool to room temperature, add water, and stir for 20 minutes to precipitate the product from the solution, filter with suction, take the filter residue, and dissolve it in dichloromethane, add anhydrous sodium sulfate and dry it for 30 minutes, filter with suction, and rotary evaporate to obtain a crude product; purify the product by column chromatography separation method (dichloromethane / ethyl acetate), which is 4,7-bis[(E)-2-(pyridin-3-yl)vinyl]benzo[c][1,2,5]thiadiazole.

[0010] B. 4-iodine pyridine, trimethylsilyl acetylene, cuprous iodide, and tetrakis(triphenylphosphine)palladium were used as raw materials, tetrahydrofuran and triethylamine were added as solvents, and the mixture was reacted in the dark at 80° C. under an inert gas atmosphere for 1 day; after the reaction was completed, the mixture was cooled to room temperature, dichloromethane was added, and the mixture was stirred for 20 minutes. The mixture was filtered with suction, and the filtrate was extracted with dichloromethane and water three times. The organic phase was added with anhydrous sodium sulfate and dried for 30 minutes, then filtered with suction, and the filtrate was rotary evaporated to obtain the product 4-((trimethylsilyl)ethynyl)pyridine.

[0011] C. The product 4-((trimethylsilyl)ethynyl)pyridine prepared in step B and potassium carbonate were used as raw materials, methanol was added as solvent, and the mixture was reacted for 2 hours under light-shielding conditions. After the reaction, the mixture was filtered and rotary evaporated to obtain the product 4-ethynylpyridine.

[0012] D. The product prepared in step C, 4-ethynylpyridine, 4,7-dibromo-2,1,3-benzothiadiazole, cuprous iodide, and tetrakis(triphenylphosphine)palladium were used as raw materials, tetrahydrofuran and triethylamine were added as solvents, and the mixture was reacted in the dark at 80° C. under an inert gas atmosphere for 1 day; after the reaction was completed, it was cooled to room temperature, dichloromethane was added, stirred for 20 minutes, filtered, and the filtrate was extracted with dichloromethane and water three times, the organic phase was added with anhydrous sodium sulfate and dried for 30 minutes, then filtered, the filtrate was taken, and the crude product was obtained by rotary evaporation; the product was purified by column chromatography separation (dichloromethane / ethyl acetate / petroleum ether), which was 4,7-bis(pyridin-3-ylethynyl)benzo[c][1,2,5]thiadiazole.

[0013] E. At room temperature, [Cp * Silver trifluoromethanesulfonate was added to an anhydrous methanol solution of 2Ir2(DHNDI)]Cl2, and the mixture was stirred thoroughly in the dark. After 2 hours, the white precipitate of silver chloride was removed by centrifugation. The product prepared in step A was then added to the supernatant after centrifugation to react. The reaction was terminated after about 12 hours. The supernatant was centrifuged and transferred to a test tube. A small amount of buffer layer solution was slowly added, followed by a large amount of ether. The mixture was allowed to stand for 2 days to obtain crystals in the buffer layer.

[0014] F、[Cp * 2Ir2(DHNDI)]Cl2 is replaced by [Cp * 2Rh2(DHNDI)]Cl2, repeat the operation of step E to obtain crystals.

[0015] G. Replace the product obtained in step A with 4,7-bis(pyridin-3-ylethynyl)benzo[c][1,2,5]thiadiazole obtained in step D, and repeat the operation of step E to obtain crystals.

[0016] Preferably, in step A, the inert gas is argon.

[0017] Preferably, in step A, the molar ratio of 3-vinylpyridine, 4,7-dibromo-2,1,3-benzothiadiazole, triethanolamine and palladium acetate is 40:17:68:2.

[0018] Preferably, in step B, the inert gas is argon.

[0019] Preferably, in step B, the molar ratio of 4-iodopyridine, trimethylsilylacetylene, cuprous iodide and tetrakis(triphenylphosphine)palladium is 18:27:3:1.

[0020] Preferably, in step C, the molar ratio of 4-((trimethylsilyl)ethynyl)pyridine to potassium carbonate is 2:3.

[0021] Preferably, in step D, the molar ratio of 4-ethynylpyridine, 4,7-dibromo-2,1,3-benzothiadiazole, cuprous iodide and tetrakis(triphenylphosphine)palladium is 90:20:5:2.

[0022] Preferably, in step E, the building block [Cp * The molar ratio of 2Ir2(DHNDI)]Cl2 to silver trifluoromethanesulfonate is 1:2.

[0023] Preferably, in step E, the binuclear precursor [Cp * Cp in 2Ir2(DHNDI)]Cl2 * is pentamethylcyclopentadiene; DHNDI is N,N'-dihydroxynaphthalene diimide.

[0024] Preferably, in step E, the buffer layer solution is a mixed solution of methanol and diethyl ether, and the volume ratio of methanol to diethyl ether is 1:1.

[0025] The method of the present invention prepares a novel high-order organometallic catenane supramolecular compound, enabling the efficient preparation of cyclic 4-catenane structures. Furthermore, the method can effectively prepare the desired cyclic 4-catenane structures by selecting different half-sandwich metal elements or connecting ligands.

[0026] Beneficial effects of the present invention:

[0027] 1. The preparation method of the present invention utilizes a strategy of coordination-driven self-assembly and synergistic non-covalent bonding to construct higher-order catenanes. Through the combined action of coordination and non-covalent bonds, complex and stable topological structures can be formed. This preparation method is simple, widely applicable, has high yields, and good reproducibility. It provides an effective and feasible approach for obtaining currently difficult-to-obtain higher-order catenane compounds.

[0028] 2. The high-order cyclic organometallic 4-catenanes prepared in the present invention have novel structures and complex topological structures, and have potential application prospects in the field of coordination supramolecular chemistry. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] The present invention will be further described below with reference to the accompanying drawings.

[0030] Figure 1 Schematic diagram of the synthesis of the organometallic catenane supramolecular compound of the present invention;

[0031] Figure 2 This is a flow chart of obtaining the organometallic catenane supramolecular compound in Example 5;

[0032] Figure 3 (a) Crystal structure diagram of the organometallic catenane supramolecular compound in Example 5; (b) Crystal structure diagram of the organometallic catenane supramolecular compound in Example 5 distinguished by four colors (top view); (c) Ball-and-stick model of the organometallic catenane supramolecular compound in Example 5; (d) Space-filling model of the organometallic catenane supramolecular compound in Example 5;

[0033] Figure 4 is a repeating unit structure diagram of the organometallic catenane supramolecular compound in Example 5;

[0034] Figure 5 is the infrared spectrum of the organometallic catenane supramolecular compound in Example 5;

[0035] Figure 6 : is the crystal structure diagram of the organometallic catenane supramolecular compound in Example 6;

[0036] Figure 7 is the infrared spectrum of the organometallic catenane supramolecular compound in Example 6;

[0037] Figure 8 is a crystal structure diagram of the organometallic catenane supramolecular compound in Example 7;

[0038] Figure 9 is the infrared spectrum of the organometallic catenane supramolecular compound in Example 7; DETAILED DESCRIPTION

[0039] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0040] Example 1

[0041] The preparation method of 4,7-bis[(E)-2-(pyridin-3-yl)vinyl]benzo[c][1,2,5]thiadiazole comprises the following steps:

[0042] 3-Vinylpyridine (428.97 mg, 4.00 mmol), 4,7-dibromo-2,1,3-benzothiadiazole (499.74 mg, 1.70 mmol), triethanolamine (1014.97 mg, 6.8 mmol), and palladium acetate (44.90 mg, 0.20 mmol) were used as raw materials. 20 mL of N,N-dimethylformamide was added as solvent and the reaction was carried out at 110°C under an inert gas atmosphere for 2 days. After the reaction was completed, the mixture was cooled to room temperature, 400 mL of water was added, and the mixture was stirred for 20 minutes to precipitate the product from the solution. The residue was filtered and dissolved in dichloromethane. Anhydrous sodium sulfate was added and dried for 30 minutes. The crude product was obtained by filtration and rotary evaporation. The product was purified by column chromatography (dichloromethane / ethyl acetate), 4,7-bis[(E)-2-(pyridin-3-yl)vinyl]benzo[c][1,2,5]thiadiazole, with a yield of 72%.

[0043] Example 2

[0044] The preparation method of 4-((trimethylsilyl)ethynyl)pyridine comprises the following steps:

[0045] 4-iodopyridine (918.00 mg, 4.5 mmol), trimethylsilyl acetylene (662.99 mg, 6.75 mmol), cuprous iodide (142.84 mg, 0.75 mmol), and tetrakis(triphenylphosphine)palladium (288.90 mg, 0.25 mmol) were used as raw materials. 6 mL of tetrahydrofuran and 6 mL of triethylamine were added as solvents. The mixture was reacted at 80°C under an inert gas atmosphere in the dark for 1 day. After the reaction was completed, the mixture was cooled to room temperature, dichloromethane was added, and the mixture was stirred for 20 minutes. The mixture was filtered with suction, and the filtrate was extracted with dichloromethane and water three times. The organic phase was dried over anhydrous sodium sulfate for 30 minutes, then filtered with suction, and the filtrate was rotary evaporated to obtain the product.

[0046] Example 3

[0047] The preparation method of 4-ethynylpyridine comprises the following steps:

[0048] The product prepared in Example 2, 4-((trimethylsilyl)ethynyl)pyridine, and potassium carbonate (932.92 mg, 6.75 mmol) were used as raw materials, and 10 mL of methanol was added as solvent. The mixture was reacted in the dark for 2 hours. After the reaction, the mixture was filtered and rotary evaporated to obtain the product.

[0049] Example 4

[0050] The preparation method of 4,7-bis(pyridin-3-ylethynyl)benzo[c][1,2,5]thiadiazole comprises the following steps:

[0051] The product prepared in Example 3, 4-ethynylpyridine, 4,7-dibromo-2,1,3-benzothiadiazole (293.96 mg, 1 mmol), cuprous iodide (47.61 mg, 0.25 mmol), and tetrakis(triphenylphosphine)palladium (57.78 mg, 0.05 mmol) were used as raw materials. 6 mL of tetrahydrofuran and 6 mL of triethylamine were added as solvents. The mixture was reacted in the dark at 80° C. under an inert gas atmosphere for 1 day. After the reaction was completed, the mixture was cooled to room temperature, dichloromethane was added, stirred for 20 minutes, filtered, and the filtrate was extracted three times with dichloromethane and water. The organic phase was added with anhydrous sodium sulfate and dried for 30 minutes. Then, the mixture was filtered, and the filtrate was rotary evaporated to obtain a crude product. The product was purified by column chromatography (dichloromethane / ethyl acetate / petroleum ether), which was 4,7-bis(pyridin-3-ylethynyl)benzo[c][1,2,5]thiadiazole, with a yield of 65%.

[0052] Example 5

[0053] Preparation method of high-order cyclic organometallic-4-catenanes, the synthesis diagram is as follows Figure 1 As shown, the following steps are included:

[0054] At room temperature, [Cp * Silver trifluoromethanesulfonate (15.42 mg, 0.06 mmol) was added to an anhydrous methanol solution of 2Ir2(DHNDI)]Cl2, and the mixture was stirred thoroughly under light-shielding conditions. After 2 hours, the mixture was centrifuged to remove the white precipitate of silver chloride. The product prepared in step A was then added to the supernatant after centrifugation to react. After about 12 hours, the reaction was terminated, and the supernatant was transferred to a test tube. A small amount of buffer layer solution (methanol / ether) was slowly added, and then a large amount of ether was added. The mixture was allowed to stand for 2 days, and crystals ( Figure 2 ), yield: 96%. FT-IR (cm -1 )v=3450(s),1636(m),1380(m),1261(m),1172(w),1024(w),748(w),639(w).( Figure 5 )

[0055] The spectrum and crystal structure of the high-order cyclic organometallic-4-catenane single crystal prepared in Example 5 are as follows: Figure 3-Figure 5 As shown. By X-ray single crystal diffraction, IR and 1H NMR characterization shows that we have successfully prepared a high-order cyclic-4-catenane supramolecular compound. And single crystal X-ray diffraction analysis shows that it is a very rare topological structure, composed of four metal organic macrocycles that cross each other end to end to form a cyclic catenane with 8 intersection points ( Figure 3 a). Using different colors to distinguish each ring, it can be clearly seen that its four rings are cross-connected with each other ( Figure 3 b). Through the ball-and-stick model ( Figure 3 c) All Cp * Ir is represented by dots, and the bridging ligand N,N'-dihydroxynaphthalene diimide and the connecting ligand are represented by straight lines, which can more clearly show its structural characteristics. Under the space expansion model, it can also be observed that there is a cavity in the center ( Figure 3 d). We also marked the forces supporting the catenane structure, and only retained one repeating structural unit for ease of observation ( Figure 4 ). It is not difficult to see that π-π stacking plays an indispensable role in this structure, because the two benzene ring structures in DHNDI provide a large number of conjugated surfaces, and the distance between the parallel benzothiadiazole group and the DHNDI group is between 3.34 and They form a π-π stacking effect at the junction of each two rings, allowing the four large rings to maintain this topological structure. In addition, we can also see that many other types of forces play a role in this structure, such as the hydrogen bonds formed between CH···S and CH···O molecules, and the intramolecular forces formed by CH···N, which lead to the deformation of the olefin bond, which is also a necessary condition for the formation and stability of the cyclic-4-catenane structure.

[0056] Example 6

[0057] Experiments on changing metal elements in the method of the present invention from Example 5:

[0058] [Cp * 2Ir2(DHNDI)]Cl2 is replaced by [Cp * 2Rh2(DHNDI)]Cl2, without changing other conditions, repeat the operation of Example 5 to obtain a crystal. The crystal structure and infrared spectrum of the high-order cyclic organometallic-4-catenane single crystal prepared in Example 3 are shown in FIG. Figure 6-Figure 7 As shown. It can be seen that its structure is very similar to that in Example 5. This shows that the preparation method of the present invention is applicable to the semi-sandwich structure building unit of different metal elements. FT-IR (cm -1 )v=3444(s),2925(w),1630(m),1265(m),1175(w),1037(w),751(w),642(w).( Figure 7 )

[0059] Example 7

[0060] Experiments from Example 5 on changing the linking ligand of the method of the present invention:

[0061] The 4,7-bis[(E)-2-(pyridin-3-yl)vinyl]benzo[c][1,2,5]thiadiazole prepared in Example 1 was replaced with 4,7-bis(pyridin-3-ylethynyl)benzo[c][1,2,5]thiadiazole, and the operation of Example 5 was repeated without changing other conditions to obtain a crystal. The crystal structure and infrared spectrum of the high-order cyclic organometallic-4-catenane single crystal prepared in Example 4 are shown in FIG. Figure 8-Figure 9 As shown. It can be seen that its structure is very similar to that in Example 5. This shows that the preparation method of the present invention is applicable to different connecting ligands. FT-IR (cm -1 )v=3440(m),2923(w),1627(s),1385(m),1260(s),1154(s),1131(s),745(w),636(m),515(w).( Figure 9 )

[0062] In summary, the above-mentioned implementation case is based on the strategy of coordination-driven self-assembly and non-covalent bond synergy, and utilizes a semi-sandwich structure building unit and a connecting ligand to synthesize a high-order cyclic-4-catenane supramolecular compound in one step. It can be seen from the results that the method of the present invention can simply and efficiently prepare high-order cyclic-4-catenane supramolecular compounds with a yield of up to 94%, and through experiments of changing metal elements and changing connecting ligands, it can be concluded that it is applicable to other metal elements and different ligands, which shows that the applicability of the present invention is very strong and can be used under different conditions. The present invention provides a simple and feasible strategy for the preparation of high-order catenane.

[0063] The above detailed description of the analytical methods involved in the present invention provides a detailed introduction. It should be noted that the above description is intended solely to help those skilled in the art better understand the methods and concepts of the present invention, and is not intended to limit the relevant content. Without departing from the principles of the present invention, those skilled in the art may make appropriate adjustments or modifications to the present invention, and such adjustments and modifications shall also fall within the scope of protection of the present invention.

Claims

1. A method for preparing a high-order cyclic catenane supramolecular compound, characterized in that: The following steps are involved: A. Using 3-vinylpyridine, 4,7-dibromo-2,1,3-benzothiadiazole, triethanolamine, and palladium acetate as raw materials, adding N,N-dimethylformamide as solvent, reacting at 110 ° C under an inert gas atmosphere for 2 days, and purifying after the reaction to obtain the product 4,7-bis[( E )-2-(pyridin-3-yl)vinyl]benzo[ c ][1,2,5]thiadiazole; B. Using 4-iodopyridine, trimethylsilyl acetylene, cuprous iodide, and tetrakis(triphenylphosphine)palladium as raw materials, adding tetrahydrofuran and triethylamine as solvents, reacting in an inert gas atmosphere at 80°C in the dark for 1 day, and purifying after the reaction to obtain the product 4-((trimethylsilyl)ethynyl)pyridine; C. The product 4-((trimethylsilyl)ethynyl)pyridine prepared in step B and potassium carbonate were used as raw materials, methanol was added as a solvent, and the mixture was reacted for 2 hours under dark conditions. After the reaction, the mixture was filtered and rotary evaporated to obtain the product 4-ethynylpyridine; D. The product prepared in step C, 4-ethynylpyridine, 4,7-dibromo-2,1,3-benzothiadiazole, cuprous iodide, and tetrakis(triphenylphosphine)palladium were used as raw materials, tetrahydrofuran and triethylamine were added as solvents, and the mixture was reacted in an inert gas atmosphere at 80° C. in the dark for 1 day. After the reaction, the product was purified to obtain 4,7-bis(pyridin-3-ylethynyl)benzo[ c ][1,2,5]thiadiazole; E. At room temperature, [Cp * Silver trifluoromethanesulfonate was added to an anhydrous methanol solution of 2Ir2(DHNDI)]Cl2, and the mixture was stirred thoroughly in the dark. After 2 hours, the mixture was centrifuged to remove the white precipitate of silver chloride. The product prepared in step A was then added to the supernatant after centrifugation to carry out the reaction. The reaction was terminated after 12 hours, and the supernatant was transferred to a test tube by centrifugation. A small amount of buffer layer solution was slowly added, and then a large amount of ether was added. The mixture was allowed to stand for 2 days to obtain crystals in the buffer layer. The binuclear precursor [Cp * Cp in 2Ir2(DHNDI)]Cl2 * is pentamethylcyclopentadiene; DHNDI is N,N'-dihydroxynaphthalene diimide; F、[Cp * 2Ir2(DHNDI)]Cl2 is replaced by [Cp * 2Rh2(DHNDI)]Cl2, repeat the operation of step E to obtain crystals; G. Replace the product obtained in step A with 4,7-bis(pyridin-3-ylethynyl)benzo[ c ][1,2,5]thiadiazole, repeat the operation of step E to obtain crystals.

2. The method for preparing a high-order cyclic catenane supramolecular compound according to claim 1, wherein: Purification process in step A: After the reaction is completed, the mixture is cooled to room temperature, water is added, and the mixture is stirred for 20 minutes to precipitate the product from the solution. The residue is filtered, and the residue is taken and dissolved in dichloromethane. Anhydrous sodium sulfate is added and dried for 30 minutes. The crude product is filtered and rotary evaporated to obtain the crude product; the product is purified by column chromatography to obtain the product; Purification process in step B: After the reaction is completed, the mixture is cooled to room temperature, dichloromethane is added, stirred for 20 minutes, filtered, the filtrate is extracted three times with dichloromethane and water, the organic phase is added with anhydrous sodium sulfate and dried for 30 minutes, then filtered, the filtrate is taken, and the product 4-((trimethylsilyl)ethynyl)pyridine is obtained by rotary evaporation; Purification process in step D: After the reaction is completed, wait for it to cool to room temperature, add dichloromethane, stir for 20 minutes, filter, take the filtrate, extract with dichloromethane and water three times, add anhydrous sodium sulfate to the organic phase and dry for 30 minutes, then filter, take the filtrate, and rotary evaporate to obtain a crude product; and obtain the product by column chromatography separation.

3. The method for preparing a high-order cyclic catenane supramolecular compound according to claim 1, wherein: In step A and step B, the inert gas is argon.

4. The method for preparing a high-order cyclic catenane supramolecular compound according to claim 1, wherein: In step A, the molar ratio of 3-vinylpyridine, 4,7-dibromo-2,1,3-benzothiadiazole, triethanolamine, and palladium acetate is 40:17:68:

2.

5. The method for preparing a high-order cyclic catenane supramolecular compound according to claim 1, wherein: In step B, the molar ratio of 4-iodopyridine, trimethylsilyl acetylene, cuprous iodide, and tetrakis(triphenylphosphine)palladium is 18:27:3:

1.

6. The method for preparing a high-order cyclic catenane supramolecular compound according to claim 1, wherein: In step C, the molar ratio of 4-((trimethylsilyl)ethynyl)pyridine and potassium carbonate is 2:

3.

7. The method for preparing a high-order cyclic catenane supramolecular compound according to claim 1, wherein: In step D, the molar ratio of 4-ethynylpyridine, 4,7-dibromo-2,1,3-benzothiadiazole, cuprous iodide, and tetrakis(triphenylphosphine)palladium is 90:20:5:

2.

8. The method for preparing a high-order cyclic catenane supramolecular compound according to claim 1, wherein: In step E, the building block [Cp * The molar ratio of 2Ir2(DHNDI)]Cl2 to silver trifluoromethanesulfonate is 1:

2.

9. The method for preparing a high-order cyclic catenane supramolecular compound according to claim 1, wherein: In step E, the buffer layer solution is a mixed solution of methanol and diethyl ether, and the volume ratio of methanol to diethyl ether is 1:1.

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