An ordered supramolecular organic framework with uniform and tunable pore size and a preparation method thereof

Abstract

The application discloses an ordered supramolecular organic framework with uniform and adjustable pore size and a preparation method thereof, and the structural general formula of the supramolecular organic framework is shown in the formula, wherein the polymerization degree n is 5, 10, 20, 30 or 40. The method comprises the following steps: performing active polymerization on a phenyl isocyanide monomer by using a three-arm alkyne-Pd (II) catalyst to obtain a three-arm phenyl isocyanide polymer, performing a Pd (II)-mediated Sonogashira cross-coupling reaction on a functional urea pyrimidinone monomer of the alkyne to functionalize a terminal end of the three-arm phenyl isocyanide polymer after polymerization, then adding a reagent A to perform a reaction, and performing self-assembly driven by intermolecular hydrogen bonds of terminal Upy units to obtain the ordered supramolecular organic framework. The preparation method of the supramolecular organic framework is simple in operation and simple in synthesis, and has great potential application value in the fields of biomedicine, nanotechnology, intelligent materials, photoelectric materials and the like.

Description

Technical Field

[0001] This invention relates to the field of functional polymers and polymer reactions, specifically to an ordered supramolecular organic framework with uniform and adjustable pore size and its preparation method. Background Technology

[0002] Polyisocyanates (PI) were among the first chiral helical polymers discovered to possess a stable helical conformation. Their main carbon chains contain a π-conjugated C=N bond, causing the polymer backbone to twist and form a stable helical structure. PIs are stable, have simple polymerization methods, and maintain their helical structure well in both solution and solid states, showing broad application prospects in chiral adsorption, enantiomeric crystallization, asymmetric catalysis, and chiral resolution. Furthermore, the rigid structure of the PI backbone allows for the incorporation into supramolecular organic frameworks, resulting in an ordered supramolecular organic framework with uniform and tunable pore sizes. This endows supramolecular organic framework materials with novel properties and functions, leading to functional polymers with new structures and properties. These have significant research value and application prospects in chiral molecule recognition, asymmetric catalysis, enantiomeric separation, drug carriers, and liquid crystal displays.

[0003] Supramolecular organic frameworks (SOFs) are periodic, extended structures assembled from structural units via intermolecular hydrogen bonds, and are currently the most widely studied and systematically researched class of supramolecular frameworks. Compared to MOFs and COFs, supramolecular organic frameworks are simpler to prepare and have lower framework density. More importantly, these materials can be effectively recycled through simple dissolution and recrystallization. However, due to the weak supramolecular forces, the removal of guest molecules from the framework often leads to the collapse of the framework structure, thus limiting the development and application of SOF materials. In recent years, through rational design and development, SOF materials with good thermal stability have been successfully prepared, greatly promoting the application of these materials in many fields.

[0004] In existing technologies, to obtain crystalline porous materials with uniform pore size, large-sized nanomaterials are incorporated, which typically results in interpenetrating structures or fragile framework materials, thus producing amorphous materials with small pore sizes. Therefore, obtaining materials with uniform and tunable pore sizes has become one of the urgent problems to be solved. Summary of the Invention

[0005] The purpose of this invention is to provide an ordered supramolecular organic framework with uniform and adjustable pore size and its preparation method. The ordered supramolecular organic framework combines polyisocyanate with a supramolecular organic framework, is simple to operate and easy to synthesize, and has great potential value in the fields of fluorescent probes, biomedicine, nanotechnology, smart materials, and optoelectronic materials.

[0006] To achieve the above objectives, the present invention provides the following technical solution:

[0007] In one aspect of the invention, a three-armed phenylisocyanate polymer is provided. According to embodiments of the invention, the general chemical structural formula of the polymer is as follows:

[0008]

[0009] In the formula,

[0010] The degree of polymerization n = 5, 10, 20, 30 or 40.

[0011] In another aspect of the present invention, a method for preparing a three-armed phenylisocyanate polymer is provided. According to an embodiment of the present invention, the preparation method is as follows: a three-armed acetylene-Pd(II) catalyst is used to perform living polymerization of phenylisocyanate monomers to prepare the three-armed phenylisocyanate polymer.

[0012] In addition, the method for preparing a three-armed phenylisocyanate polymer according to the above embodiments of the present invention may also have the following additional technical features:

[0013] In some embodiments of the present invention, the living polymerization reaction is carried out under an anhydrous and oxygen-free nitrogen atmosphere, at a reaction temperature of 50–90°C, and for a reaction time of 6–24 h; solvent A is added during the living polymerization reaction, and solvent A is one or more of tetrahydrofuran, chloroform, and toluene.

[0014] The general structural formula of the three-armed alkyne-Pd(II) catalyst is:

[0015]

[0016] The molar ratio of the three-armed yne-Pd(II) catalyst to the phenylisocyanate monomer is 1:(5-40); when the amount of phenylisocyanate monomer added is 30-100 mg, the amount of solvent A added is 1-3 mL.

[0017] The synthetic route for the three-armed phenylisocyanate polymer is as follows:

[0018]

[0019] In another aspect of the present invention, a method for preparing a three-armed phenyl isonitrile polymer capped with an alkyne-functionalized ureidopyrimidinone monomer (Upy) is provided. According to an embodiment of the present invention, the method includes the following steps: terminal functionalization of the three-armed phenyl isonitrile polymer after polymerization is performed via a Pd(II)-mediated Sonogashira cross-coupling reaction of the alkyne-functionalized ureidopyrimidinone monomer (Upy), resulting in a star-shaped polymer with an alkyne-functionalized ureidopyrimidinone monomer (Upy) at each chain end, which is the three-armed phenyl isonitrile polymer capped with an alkyne-functionalized ureidopyrimidinone monomer (Upy).

[0020] Furthermore, the method for preparing a three-arm phenyl isonitrile polymer capped with an alkyne-functionalized ureidopyrimidinone monomer (Upy) according to the above embodiments of the present invention may also have the following additional technical features:

[0021] In some embodiments of the present invention, the Sonogashira cross-coupling reaction is carried out under anhydrous and oxygen-free nitrogen atmosphere, at a reaction temperature of 50–90°C, and for a reaction time of 6–24 h.

[0022] In the Sonogashira cross-coupling reaction, solvent A and solvent B are added, wherein the volume ratio of solvent A to solvent B is 1:1, and reagent B is one or both of triethylamine and diisopropylamine, and reagent A is one or more of tetrahydrofuran, chloroform, and toluene.

[0023] The molar ratio of the three-armed phenyl isonitrile polymer and the alkyne-functionalized ureidopyrimidinone monomer (Upy) is 1:5;

[0024] The general structural formula of the alkyne-functionalized ureidopyrimidinone monomer (Upy) is:

[0025] The synthetic route for the three-arm phenyl isonitrile polymer capped with alkyne-functionalized ureidopyrimidinone monomer (Upy) is as follows:

[0026]

[0027] The preparation method of alkyne-functionalized ureidopyrimidinone monomer (Upy) includes the following steps:

[0028] (1) In a round-bottom flask, 7-octynoic acid and diphenyl azidophosphate (DPPA) and solvent C were added to solvent B. The resulting mixture was vigorously stirred and heated at 50°C. After 2 hours, the reaction mixture was allowed to cool to room temperature, and TLC showed that the starting material was consumed. The crude product was concentrated and used directly in the next step, wherein solvent B was one or both of triethylamine and diisopropylamine, and solvent C was one or both of acetonitrile and dichloromethane.

[0029] (2) In a round-bottom flask, 2-amino-4-hydroxy-6-methylpyrimidine and DMAP were dissolved in pyridine. The resulting mixture was stirred at room temperature under dry nitrogen. After 30 minutes, the product from the previous step, dissolved in pyridine, was added, and the mixture was stirred overnight at room temperature. After concentration, it was purified by column chromatography to obtain the alkyne-functionalized ureidopyrimidinone monomer (Upy).

[0030] The synthetic route for this alkyne-functionalized ureidopyrimidinone monomer (Upy) is as follows:

[0031]

[0032] In another aspect of the present invention, the present invention provides a method for preparing a three-arm phenyl isonitrile polymer with alkyne-functionalized ureidopyrimidinone monomer (Upy) end-capped, which yields an alkyne-functionalized ureidopyrimidinone monomer (Upy) end-capped three-arm phenyl isonitrile polymer.

[0033] In addition, a three-arm phenyl isonitrile polymer capped with an alkyne-functionalized ureidopyrimidinone monomer (Upy) according to the above embodiments of the present invention may also have the following additional technical features:

[0034] In some embodiments of the present invention, the general chemical structural formula of the polymer is as follows:

[0035]

[0036] In the formula,

[0037]

[0038] Among them, the degree of polymerization n = 5, 10, 20, 30 or 40. The three-arm polyphenylisocyanate polymer with the above degree of polymerization can effectively control the pore size variation of the supramolecular organic framework.

[0039] In another aspect of the present invention, a method for preparing an ordered supramolecular organic framework with uniform and adjustable pore size is proposed. According to an embodiment of the present invention, the preparation method includes the following steps: adding a three-arm phenyl isonitrile polymer capped with the alkyne-functionalized ureidopyrimidinone monomer (Upy) to reagent A for reaction; and utilizing intermolecular hydrogen bonds driven by the terminal Upy units to drive self-assembly, thereby obtaining the ordered supramolecular organic framework. The reagent A is one or more of tetrahydrofuran, chloroform, and toluene.

[0040] Furthermore, the method for preparing an ordered supramolecular organic framework with uniform and adjustable pore size according to the above embodiments of the present invention may also have the following additional technical features:

[0041] In some embodiments of the present invention, the reaction is carried out in an anhydrous and oxygen-free nitrogen atmosphere at room temperature for 6 to 24 hours.

[0042] In another aspect, the present invention proposes an ordered supramolecular organic framework with uniform and tunable pore size. According to an embodiment of the present invention, the ordered supramolecular organic framework with uniform and tunable pore size is prepared by the method described above, and the structure of the ordered supramolecular organic framework is shown in the following general formula:

[0043]

[0044] In the formula,

[0045] R is

[0046] Among them, the degree of polymerization n = 5, 10, 20, 30 or 40. The three-arm polyphenylisocyanate polymer with the above degree of polymerization can effectively control the pore size variation of the supramolecular organic framework.

[0047] Compared with the prior art, the beneficial effects of the present invention are:

[0048] (1) This invention utilizes a three-armed ytylene-Pd(II) catalyst to perform living polymerization of phenyl isonitrile monomers, thereby preparing a series of monomers with predictable M... n and very low M w / M n The three-armed star-shaped polyphenylisocyanate is well-defined, and the entire preparation method is simple, with undemanding experimental conditions and easy reaction.

[0049] (2) The end-functionalized three-arm phenyl isonitrile polymer of the present invention is simple to synthesize and can be obtained quickly and easily.

[0050] (3) The phenyl isonitrile polymer in this invention has a wide range of raw material sources; there are many types of catalysts used to catalyze the reaction of phenyl isonitrile monomers.

[0051] (4) The present invention controls the pore size of the supramolecular organic framework according to the different degrees of polymerization, thereby obtaining an ordered supramolecular organic framework with uniform and adjustable pore size.

[0052] (5) The supramolecular organic framework in this invention combines isonitriles with supramolecular organic frameworks, which has great application value in the fields of fluorescent probes, biomedicine, nanotechnology, smart materials, and optoelectronic materials. Attached Figure Description

[0053] Figure 1This is the 1H NMR spectrum of phenyl isonitrile monomer 1 in Example 1 of the present invention;

[0054] Figure 2 This is the 1H NMR spectrum of the three-arm yne-Pd(II) catalyst in Example 2 of this invention;

[0055] Figure 3 This is the 1H NMR spectrum of the three-armed polyphenylisocyanate polymer P1 in Example 2 of the present invention;

[0056] Figure 4 This is the 1H NMR spectrum of the alkyne-functionalized ureidopyrimidinone monomer (Upy) in Example 3 of the present invention;

[0057] Figure 5 This is the 1H NMR spectrum of the three-arm polyphenylisocyanate polymer P2 after being capped with alkyne-functionalized ureidopyrimidinone monomer (Upy) in Example 3 of the present invention;

[0058] Figure 6 This is a gel permeation chromatogram of the three-arm polyphenylisocyanate polymer P2, which is end-capped with alkyne-functionalized ureidopyrimidinone monomer (Upy) in Example 3 of this invention. In the figure, poly-1 10 -Upy、poly-1 20 -Upy、poly-1 30 -Upy、poly-1 40 -Upy are three-arm polyphenylisocyanate polymers capped with alkyne-functionalized ureidopyrimidinone monomers (Upy) with degrees of polymerization of 10, 20, 30, and 40, respectively.

[0059] Figure 7 This is a dynamic light scattering analysis diagram of supramolecular organic frameworks (SOFs) with different degrees of polymerization in Embodiment 4 of this invention. In the diagram, SOFs... 10 SOF 20 SOF 30 SOF 40 These are assembled supramolecular organic frameworks (SOFs) with polymerization degrees of 10, 20, 30, and 40, respectively.

[0060] Figure 8 These are the 1H NMR spectra of the supramolecular organic framework (SOFs) before and after assembly in Embodiment 4 of this invention; Detailed Implementation

[0061] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0062] Example 1

[0063] The method for synthesizing phenyl isonitrile monomer 1 includes the following steps:

[0064] (1) Weigh N-benzyloxycarbonyl-2-methylalanine, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDCI), and DMAP sequentially, place them in a 250 mL two-necked flask, add dichloromethane to the flask, stir on a stirring table until the solids dissolve, then add n-decyl alcohol, and continue stirring at room temperature. Concentrate the filtrate under reduced pressure to obtain the crude product, separate the crude product by column chromatography, and collect product 3.

[0065] (2) Weigh product 3 and palladium on carbon separately and put them into a 250mL double-necked flask. Add tetrahydrofuran to the double-necked flask. First, replace the reaction system with N2 atmosphere, and then replace the reaction system with H2 atmosphere. Stir the reaction at room temperature under H2 atmosphere. After the reaction is completed, filter with diatomaceous earth to remove palladium on carbon. The filtrate is concentrated and product 4 does not need further purification and can be used directly for the next reaction.

[0066] (3) Weigh p-nitrobenzoic acid and EDCI sequentially into a 250mL two-necked flask, add dichloromethane, stir until the solid dissolves, and then add product 4. Concentrate the filtrate under reduced pressure to obtain the crude product, and then obtain product 5.

[0067] (4) Weigh product 5 and palladium on carbon into a 250 mL double-necked flask. After adding tetrahydrofuran to the double-necked flask, first replace the reaction system with N2 atmosphere, then replace the reaction system with H2 atmosphere. Stir the reaction at room temperature overnight under H2 atmosphere. After the reaction is complete, filter out the palladium on carbon using diatomaceous earth, collect the filtrate, and concentrate the filtrate. Compound 6 does not need further purification and can be used directly in the next step of the reaction.

[0068] (5) Weigh compound 6 into a 250 mL double-necked flask, replace the reaction system with a N2 atmosphere (using an oil pump), and dissolve compound 6 in ethyl acetate using a syringe under N2 atmosphere. Then place the reaction flask in an ice bath at 0°C. Prepare formic anhydride in advance: mix acetic anhydride and formic acid, and stir the mixture under N2 atmosphere for 3 hours. Slowly add the prepared formic anhydride dropwise to the reaction flask containing compound 6 using a syringe, monitoring the reaction progress using TLC. After the reaction is complete, concentrate the filtrate under reduced pressure to obtain the crude product, and then filter to obtain compound 7.

[0069] (6) Weigh compound 7 and place it in a 250 mL double-necked flask. Replace the reaction system with an N2 atmosphere. Under the N2 atmosphere, add dichloromethane to the reaction flask using a syringe. After compound 7 dissolves, add triethylamine under the N2 atmosphere using a syringe. Place the reaction flask in an ice bath at 0°C and stir. Weigh triphosgene (BTC), dissolve it in solvent C, and slowly add it dropwise to the above reaction flask under an N2 atmosphere. The reaction progress is monitored using TLC during the dropwise addition process. After the reaction is complete, concentrate the filtrate under reduced pressure to obtain the crude product. Separate the crude product by column chromatography to obtain phenylisocyanate monomer 1. The structural formula of phenylisocyanate monomer 1 is:

[0070]

[0071] The route for synthesizing product 1 in this embodiment is as follows:

[0072]

[0073] The phenyl isonitrile monomer 1 in this embodiment was analyzed by 1H NMR spectroscopy. The benzene ring signal in phenyl isonitrile monomer 1 could be observed, as shown in the 1H NMR spectrum. Figure 1 As shown.

[0074] Example 2

[0075] The method for synthesizing the three-armed phenylisocyanate polymer P1 includes the following steps:

[0076] A three-armed ytylene-Pd(II) catalyst and the phenyl isonitrile monomer 1 prepared in Example 1 were added to a polymerization flask. Under anhydrous and oxygen-free conditions, the mixture was evacuated and purged with nitrogen. Dry chloroform was added, and the reaction was refluxed at 55°C for 24 h. The reaction was terminated by adding methanol. The resulting product was washed with methanol and then vacuum dried until its mass remained constant to obtain a three-armed star-shaped phenyl isonitrile polymer P1. The general structural formula of the three-armed ytylene-Pd(II) catalyst is as follows:

[0077]

[0078] The general structural formula of the three-armed phenylisocyanate polymer P1 is:

[0079]

[0080] In the formula,

[0081] Where n = 5, 10, 20, 30 or 40.

[0082] The route for synthesizing the three-armed polyphenylisocyanate polymer P1 in this embodiment is as follows:

[0083]

[0084] The three-armed yne-Pd(II) catalyst and the three-armed polyphenylisocyanate polymer P1 in this embodiment were analyzed by 1H NMR spectroscopy. The triethyl signal in the three-armed yne-Pd(II) catalyst could be observed, as shown in the 1H NMR spectrum. Figure 2 As shown; the side benzene ring signal in the three-arm polyphenylisocyanate polymer P1 can be observed, as shown in the 1H NMR spectrum. Figure 3 As shown.

[0085] Example 3

[0086] The method for synthesizing the terminally functionalized three-arm phenylisocyanate polymer P2 includes the following steps:

[0087] (1) Preparation of alkyne-functionalized ureidopyrimidinone monomer (Upy)

[0088] In a round-bottom flask, 7-octylene acid, diphenyl azidophosphate (DPPA), and triethylamine were added to acetonitrile. The resulting mixture was heated with vigorous stirring at 50°C for 2 hours. The reaction mixture was then allowed to cool to room temperature, and TLC showed that the starting material had been consumed. The concentrate yielded a crude product, which was used directly in the next step.

[0089] In a round-bottom flask, 2-amino-4-hydroxy-6-methylpyrimidine and DMAP were dissolved in pyridine. The resulting mixture was stirred at room temperature under dry nitrogen. After 30 minutes, the product from the previous step, dissolved in pyridine, was added, and the mixture was stirred overnight at room temperature. After concentration, the mixture was purified by column chromatography to give the alkyne-functionalized ureidopyrimidinone monomer (Upy).

[0090] The synthetic route for this alkyne-functionalized ureidopyrimidinone monomer (Upy) is as follows:

[0091]

[0092] (2) The three-arm phenyl isonitrile polymer P1 prepared in Example 2, the alkyne-functionalized ureidopyrimidinone monomer (Upy), and cuprous iodide were added to a polymerization flask. Under anhydrous and oxygen-free conditions, the mixture was evacuated and purged with nitrogen. Dry tetrahydrofuran and triethylamine were added, and the mixture was refluxed at 55°C for 24 h. The reaction was terminated by adding methanol. The resulting product was washed with methanol and then dried under vacuum until its mass remained unchanged to obtain the terminally functionalized three-arm phenyl isonitrile polymer P2. The general structural formula of the alkyne-functionalized ureidopyrimidinone monomer (Upy) is:

[0093] The general structural formula of the terminally functionalized three-arm phenylisocyanate polymer P2 is:

[0094]

[0095] In the formula,

[0096]

[0097] Where n = 5, 10, 20, 30 or 40, the above-mentioned degree of polymerization of the three-arm polyphenylisocyanate polymer can effectively control the pore size variation of the supramolecular organic framework.

[0098] The synthetic route for the terminally functionalized three-arm phenylisocyanate polymer P2 is as follows:

[0099]

[0100] The alkyne-functionalized ureidopyrimidinone monomer (Upy) and the three-armed phenylisocyanate polymer P2 in this embodiment were analyzed by 1H NMR and gel permeation chromatography. Alkyne and amino signals in the alkyne-functionalized ureidopyrimidinone monomer (Upy) were observed, as shown in the 1H NMR spectrum. Figure 4 As shown; the side benzene ring signal in the three-arm phenyl isonitrile polymer P2 and the signal in the alkyne-functionalized ureidopyrimidinone monomer (Upy) can be observed, as shown in the 1H NMR spectrum. Figure 5 As shown in the figure; gel permeation chromatogram analysis of the three-arm phenylisocyanate polymer P2 shows that the elution time of the three-arm phenylisocyanate polymer P2 with different degrees of polymerization is significantly advanced, further confirming the successful synthesis of three-arm phenylisocyanate polymer P2 with different degrees of polymerization. The gel permeation chromatograms are shown in the figure. Figure 6 As shown.

[0101] Example 4

[0102] The preparation method of an ordered supramolecular organic framework with uniform and tunable pore size is as follows:

[0103] The terminally functionalized three-arm phenyl isonitrile polymer P2 prepared in Example 3 was added to a polymerization flask. Under anhydrous and oxygen-free conditions, the mixture was evacuated and purged with nitrogen. Dry chloroform was added, and the reaction was carried out at room temperature for 24 hours. Utilizing the intermolecular hydrogen bonds driven self-assembly of the terminal Upy units, a well-defined supramolecular organic framework with a predetermined and highly uniform pore size was achieved in chloroform. The general structural formula of the supramolecular organic framework (SOF) is as follows:

[0104]

[0105] In the formula,

[0106] R is

[0107] Among them, the degree of polymerization n = 5, 10, 20, 30 or 40. The three-arm polyphenylisocyanate polymer with the above degree of polymerization can effectively control the pore size variation of the supramolecular organic framework.

[0108] Dynamic light scattering analysis and pre- and post-polymerization 1H NMR spectra were performed on the supramolecular organic framework (SOFs) in this embodiment. The change in particle size of supramolecular organic framework SOFs with different degrees of polymerization further confirmed the influence of different degrees of polymerization on supramolecular organic framework SOFs. The dynamic light scattering spectra are shown below. Figure 7 As shown; analysis of the 1H NMR spectra of supramolecular organic framework (SOFs) before and after assembly reveals that amino signals can be observed in the SOFs before and after assembly. The 1H NMR spectra are shown below. Figure 8 As shown.

[0109] The above description is merely an example and illustration of the structure of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the structure of the present invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.

Claims

1. A method for preparing a three-arm phenyl isonitrile polymer capped with an alkyne-functionalized ureidopyrimidinone monomer, characterized in that: By using the Sonogashira cross-coupling reaction of Pd(II)-mediated alkyne-functionalized ureidopyrimidinone monomers, the end-functionalization of the three-arm phenylisocyanate polymer after polymerization was obtained, resulting in a star-shaped polymer with alkyne-functionalized ureidopyrimidinone monomers at each chain end, which is the three-arm phenylisocyanate polymer after end-capping with alkyne-functionalized ureidopyrimidinone monomers. The general chemical structural formula of the three-armed phenylisocyanate polymer is as follows: ， In the formula, , The degree of polymerization n = 5, 10, 20, 30 or 40.

2. The method for preparing a three-arm phenyl isonitrile polymer capped with an alkyne-functionalized ureidopyrimidinone monomer according to claim 1, characterized in that: The preparation method of the three-armed phenylisocyanate polymer is as follows: the phenylisocyanate monomer is prepared by living polymerization using a three-armed acetylene-Pd(II) catalyst.

3. The method for preparing a three-arm phenyl isonitrile polymer capped with an alkyne-functionalized ureidopyrimidinone monomer according to claim 2, characterized in that: The living polymerization reaction is carried out under anhydrous and oxygen-free nitrogen atmosphere, at a reaction temperature of 50–90°C, and for a reaction time of 6–24 h. Solvent A is added during the living polymerization reaction, and solvent A is one or more of tetrahydrofuran, chloroform, and toluene. The general structural formula of the three-armed alkyne-Pd(II) catalyst is: ； The molar ratio of the three-armed yne-Pd(II) catalyst to the phenylisocyanate monomer is 1:(5-40); When the amount of phenylisocyanate monomer added is 30-100 mg, the amount of solvent A added is 1-3 mL.

4. The method for preparing a three-arm phenyl isonitrile polymer capped with an alkyne-functionalized ureidopyrimidinone monomer according to claim 1, characterized in that: The Sonogashira cross-coupling reaction was carried out under anhydrous and oxygen-free nitrogen atmosphere at a temperature of 50–90°C for a time of 6–24 h. In the Sonogashira cross-coupling reaction, reagent A and reagent B are added, wherein the volume ratio of reagent A to reagent B is 1:1, and reagent B is one or both of triethylamine and diisopropylamine, and reagent A is one or more of tetrahydrofuran, chloroform, and toluene. The molar ratio of the three-armed phenylisocyanate polymer to the alkyne-functionalized ureidopyrimidinone monomer is 1:5; The general structural formula of the alkyne-functionalized ureidopyrimidinone monomer is: .

5. A method for preparing a three-arm phenyl isonitrile polymer with alkyne-functionalized ureidopyrimidinone monomer-terminated according to any one of claims 1-4.

6. The three-arm phenyl isonitrile polymer capped with an alkyne-functionalized ureidopyrimidinone monomer according to claim 5, characterized in that, The general chemical structural formula of the end-capped polymer is as follows: ， In the formula, ， ， The degree of polymerization n = 5, 10, 20, 30 or 40.

7. A method for preparing an ordered supramolecular organic framework with uniform and adjustable pore size, characterized in that: The three-arm phenyl isonitrile polymer capped with the alkyne-functionalized ureidopyrimidinone monomer (Upy) according to claim 5 is added to reagent C for reaction. Self-assembly driven by intermolecular hydrogen bonds of the terminal Upy unit is used to obtain the ordered supramolecular organic framework. The reagent C is one or more of tetrahydrofuran, chloroform, and toluene.

8. The method for preparing an ordered supramolecular organic framework with uniform and adjustable pore size according to claim 7, characterized in that: The reaction was carried out under anhydrous and oxygen-free nitrogen atmosphere at room temperature for 6–24 hours.

9. An ordered supramolecular organic framework with uniform and tunable pore size, characterized in that: The ordered supramolecular organic framework is prepared according to the preparation method of claim 7, and the structure of the ordered supramolecular organic framework is shown in the following general formula: ， In the formula, R is , , The degree of polymerization n = 5, 10, 20, 30 or 40.

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