Synthesis of Pyridinehydrazone-Conjugated Pillarene and Its Supramolecular Polymer Network and Its Application in Perchlorate Ion Separation

Abstract

The present invention discloses an A,A'-bipyridinehydrazone-functionalized conjugated pillar[5]arene macrocyclic molecule and a synthesis method thereof. The invention comprises reacting a bis(4-formylphenylboronic acid)-functionalized pillar[5]arene with 2-hydrazinepyridine through an imine condensation reaction to obtain an A,A'-bipyridinehydrazone-functionalized conjugated pillar[5]arene PYP5 having two rigid functional arms. The macrocyclic molecule PYP5 can self-assemble through multiple hydrogen bonds to form a supramolecular polymer network. Thanks to the "double-arm-macrocyclic synergistic effect" between the double arms of the pillar[5]arene and the ethoxy group, PYP5 can provide multiple "clustered hydrogen bonds" to tightly bind ClO4. − Therefore, the supramolecular polymer network can effectively treat ClO4 in water. − It can show good adsorption and separation performance and can effectively remove ClO4 in water − The removal rate can reach 99.24%. The A,A'-bispyridinehydrazone functionalized conjugated column[5] aromatic macrocyclic molecule provided by the present invention has good application prospects in the fields of supramolecular assembly, water pollutant removal, adsorption separation, etc.

Description

Technical Field

[0001] The present invention relates to a supramolecular polymer network based on A,A'-bipyridinehydrazone functionalized conjugated column[5] aromatic macrocyclic molecules and their assembly, and also relates to a supramolecular polymer network for efficiently removing ClO4 from water. − The application of the invention belongs to the fields of organic synthetic chemistry technology and adsorption separation technology. Background Art

[0002] Perchlorate (ClO4 − ) is a persistent and toxic inorganic pollutant. Unlike most other anions that can be precipitated from aqueous solutions by suitable precipitants, ClO4 − It is easily soluble in water, and no suitable precipitant can make ClO4 − It precipitates from water. Therefore, ClO4 is separated from water. − is a huge challenge. However, ClO4 − It is widely used as an oxidant or combustible source in rocket propellants, explosives, fireworks and airbag inflation systems. It has the characteristics of fast diffusion, high stability and difficulty in degradation. Once ClO4 − Entering the water system and food chain will seriously threaten human health and environmental safety. − It will inhibit the thyroid gland from absorbing iodide, thus interfering with the normal function of the human thyroid gland, affecting the development of embryos, pregnant women, lactating women and children, and seriously endangering human health. − Pollution control methods have become a research hotspot. − The main methods of pollution control include biotechnology, electrochemical reduction, chemical catalysis, ion exchange, activated carbon adsorption or other material adsorption. Although some progress has been made, how to quickly, efficiently, low-cost and non-secondary pollution treatment of ClO4 − Pollution remains a huge challenge. − Due to its non-volatility, high solubility and kinetic stability, conventional treatment technology is difficult to effectively remove ClO4 from water − However, the removal of pollutants from water by adsorption separation is still a simple, low-cost and easy-to-operate method. Therefore, the development of a method that can efficiently bind and separate ClO4 − There is a significant demand for materials.

[0003] With the rapid development of supramolecular chemistry, supramolecular polymer adsorption and separation materials based on macrocyclic assembly have attracted widespread attention due to their excellent host-guest complexing properties. Among the many macrocyclic hosts, pillar[n]arene, which was first reported by Ogoshi, has the advantages of being easy to synthesize and modify, having adjustable cavity size, being able to provide a variety of supramolecular interactions, and having strong complexing ability for guests. For example, fully ethyl pillar[5]arene can encapsulate straight-chain alkanes, and fully hydroxyl pillar[6]arene can well complex highly toxic paraquat. These examples are achieved by utilizing the electron-rich cavity of pillar[n]arene and CH···π interactions. It is worth mentioning that, taking pillar[5]arene as an example, there are ten alkoxy groups on both sides of its cavity, which can provide abundant CH···X (X=O, N, F, Cl, Br…) hydrogen bond donors, making it possible to effectively complex the target guest. However, reports on using multiple alkoxy groups on both sides of the pillar[5]arene cavity to bind the target guest by forming multiple hydrogen bonds are still very rare. Therefore, how to rationally and efficiently utilize these polyalkoxy groups to enhance the binding ability of pillar[5]arene to target objects is crucial for developing efficient macrocyclic supramolecular polymer materials for binding and separation of specific objects (such as ClO4 − ) provide important opportunities.

[0004] The present invention designs and synthesizes a novel macrocyclic molecule PYP5 based on A, A'-bipyridine hydrazone functionalized conjugated pillar[5]arene. First, in order to enhance the binding performance of pillar[5]arene, we use bipyridine hydrazone groups to rationally conjugate the A, A' positions of pillar[5]arene. Among them, the bipyridine hydrazone groups can serve as the two arms of the pillar[5]arene main body PYP5, acting as hydrogen bond donors and acceptors, and can synergistically interact with multiple ethoxy groups around the pillar[5]arene cavity to form ClO4 − Secondly, the conjugated functionalization model can enhance the rigidity of the two arms of PYP5 and facilitate the assembly of supramolecular polymer networks through multiple hydrogen bonds between the two arms of adjacent PYP5 molecules. The "clustered hydrogen bonds" based on the "double-arm-macrocycle synergy" will help realize the supramolecular polymer network to ClO4 in water. − and showed good adsorption separation effect. Summary of the Invention

[0005] The purpose of the present invention is to provide an A,A'-bipyridinehydrazone functionalized conjugated pillar[5]arene macrocyclic molecule and a supramolecular polymer network formed by its assembly;

[0006] Another object of the present invention is to provide the supramolecular polymer network as an adsorption material for efficiently removing ClO4 from water. − Application in.

[0007] 1. A, A'-Bispyridinehydrazone-functionalized conjugated column[5]arene macrocyclic molecules and their synthesis

[0008] The present invention comprises A, A'-bipyridine hydrazone functionalized conjugated column [5] aromatic macrocyclic molecule having the molecular formula: C 75 H 80 N6O8, marked as: PYP5, the structural formula is:

[0009] .

[0010] The present invention provides a method for synthesizing A, A'-bispyridylhydrazone functionalized conjugated pillar [5] aromatic hydrocarbon macrocyclic molecules: a bis-4-formylphenylboronic acid functionalized pillar [5] aromatic hydrocarbon p- Q is prepared by an imine condensation reaction with 2-hydrazinopyridine. The specific steps are as follows:

[0011] Functionalization of bis(4-formylphenylboronic acid) column[5]arene p- Q and 2-hydrazinepyridine were added to anhydrous ethanol, and then glacial acetic acid was added as a catalyst. Under nitrogen protection, the reaction was carried out at 80-85 ° C for 30-36 hours. After the reaction was completed, the product was filtered and washed to obtain the bipyridine hydrazone functionalized conjugated column [5] aromatic macrocyclic molecule PYP5.

[0012] Among them, bis(4-formylphenylboronic acid) functionalized pillar[5]arene p- The molar ratio of Q to 2-hydrazinopyridine is 1:2.1~1:3; double 4-formylphenylboronic acid functionalized column [5] aromatic hydrocarbon p- The molar ratio of Q to glacial acetic acid is 1:0.05~1:0.1.

[0013] p- The synthesis method of Q was referred to the literature H. Zhu, J. Liu, Y. Wu, L. Wang, H. Zhang, Q. Li,H. Wang, H. Xing, JL Sessler, F. Huang, J. Am. Chem. Soc. 2023, 145, 11130-11139.

[0014] The H NMR spectrum, C NMR spectrum and high resolution mass spectrum of the A, A'-bispyridylhydrazone functionalized conjugated column[5] aromatic macrocyclic molecule PYP5 are shown in Figure 1 、 Figure 2 、 Figure 3 .

[0015] The synthetic route of PYP5 is as follows:

[0016]

[0017] II. Crystal Growth and Crystal Structure of A, A'-Bispyridine Hydrazone-Functionalized Conjugated Pillar[5]Arene Macrocycle

[0018] At room temperature, the A, A'-bipyridinehydrazone functionalized conjugated column [5] aromatic macrocyclic molecule PYP5 was dissolved in a mixed solution of dichloromethane and acetone (dichloromethane and acetone volume ratio is 1:1), and slowly evaporated within 3 to 4 days to obtain high-quality colorless and transparent single crystals suitable for single crystal X-ray diffraction, and X-ray crystallographic analysis was performed. The crystal structure is shown in the figure below. Figure 4 Adjacent PYP5 molecules can assemble through multiple hydrogen bonds to form a supramolecular polymer network HBPC.

[0019] The supramolecular polymer network HBPC, which is formed by the assembly of A, A'-bipyridinehydrazone functionalized conjugated pillar[5] aromatic macrocyclic molecules, is first assembled through multiple NH···N hydrogen bonds between adjacent PYP5 molecules to form a one-dimensional chain supramolecular polymer ( Figure 5 ), and then the one-dimensional chain supramolecular polymers were assembled through CH···π interactions to form HBPC ( Figure 6 ).like Figure 7 As shown in Figure 2, the network exhibits a porous structure, and therefore, the N2 gas adsorption-desorption isotherm was measured at 77.3 K ( Figure 10 ), and the apparent surface area of ​​HBPC was obtained as 4.756 m using the Brunauer-Emmett-Teller (BET) model. 2 g -1 At the same time, the free volume (FV) calculated from the single crystal data is 1840.128 Å 3 , the free volume fraction (FVF) is as high as 46.09% ( Figure 11 ), for the adsorption of ClO4 − Provides a suitable pore structure.

[0020] 3. Supramolecular polymer networks as adsorption materials for the removal of ClO4 from water − Applications

[0021] A, A'-bipyridine hydrazone functionalized conjugated pillar[5]arene macrocyclic molecules are modified with rigid functional groups to expand the rigid conjugated structure of pillar[5]arene. At the same time, the rigid functional groups can serve as the "double arms" of the macrocyclic and form "clustered hydrogen bonds" with the pillar[5]arene ethoxy chains through the "double arms-macrocyclic synergy" strategy with the guest molecules, thereby achieving efficient complexation of the guest molecules. Based on this, in order to achieve ClO4 − To achieve efficient complexation and separation, we developed a supramolecular polymer network based on a novel “clustered hydrogen bonding enhanced host-guest binding” strategy.

[0022] 1. Adsorption performance of HBPC adsorption materials

[0023] In order to study the effect of HBPC on ClO4 − The removal performance of HBPC was determined by ion chromatography. − The adsorption rate can reach 99.24% ( Figure 12 ). Residual ClO4 − The concentration is lower than the World Health Organization drinking water quality standard, indicating that the HBPC material of the present invention can effectively remove ClO4 in aqueous solution. − Has good removal effect.

[0024] 2. Analysis of complexation mechanism

[0025] In order to study the supramolecular polymer network and ClO4 − We first performed HR-MS characterization to find out the complexation mechanism of monomer PYP5 and ClO4 − The complexation ratio is 1:2 ( Figure 13 ). We obtained loaded ClO4 − Host-guest single crystal, labeled as HBPC-ClO4 − In monomeric PYP5 ( Figure 4 , Figure 9 In the crystal structure of HBPC⊃ClO4, the bipyridine hydrazone faces the outside of the pillar[5]arene, and one of the pyridine N atoms is away from the pillar[5]arene cavity. − In the host-guest single crystal, when ClO4 is combined − When ClO4 − ( Figure 9 The pyridylhydrazone undergoes adaptive rotation due to the induction effect of the pyridylhydrazone, and the two pyridylhydrazone arms and the pillar[5]arene cavity synergistically bind ClO4 through multiple clustered hydrogen bonds. − The pyridine group on the bispyridinylhydrazone is protonated by obtaining a proton from the solvent and reacts with ClO4 − Form NH···O hydrogen bonds; at the same time, the methylene and methyl groups on the multiple ethoxy groups of columnar[5]arene react with ClO4 − Form multiple CH···O hydrogen bonds; in addition, the -NH groups on the hydrazone groups of adjacent monomer molecules also form multiple CH···O hydrogen bonds with ClO4 − ( Figure 8 ) form NH···O hydrogen bonds, all of which surround ClO4 − Clustered hydrogen bonds are formed around Figure 9 middle right), thus achieving the ClO4 −In addition, in order to conduct in-depth theoretical research and visualization of the “cluster hydrogen bond”, we used the IGMH method to calculate the hydrogen bond between monomer PYP5 and ClO4 based on crystal data. − The hydrogen bonds and weak interactions between them, where one molecule of PYP5 complexes two molecules of ClO4 − Marked as: PYP5⊃2ClO4 − .like Figure 15 As shown, ClO4 − It forms multiple NH···O and CH···O hydrogen bonds with the -NH on pyridine hydrazone, and the methyl and methylene groups on the ethoxy group. This further proves that monomer PYP5 can bind ClO4 through “clustered hydrogen bonds”. − Interestingly, HBPC complexes ClO4 − Then a single crystal to single crystal transition occurred ( Figure 8 At this time, HBPC is formed by π···π stacking, CH···π interaction and NH···O hydrogen bonding ( Figure 8 ) for assembly, and the network structure of HBPC is still maintained, which gives HBPC high efficiency in separating ClO4 − Excellent performance.

[0026] Subsequently, at room temperature, based on a constant concentration of PYP5 and different concentrations of ClO4 − carried out 1 H NMR titration experiments ( Figure 14 ). With ClO4 − With the increase of concentration, the protons on the conjugated bipyridine hydrazone arms H d 、 H f 、 H b and H a The signal peak of protons shifts to low field. H e The signal peak shifts to high field, indicating that the conjugated bipyridine hydrazone arm is bound to ClO4 − NH···O hydrogen bonds are formed between them. At the same time, the protons on the double arms of the pyridylhydrazone functionalization H c and H g The signal peak of the conjugated bipyridine hydrazone arm was shifted downfield, indicating that the conjugated bipyridine hydrazone arm was bound to ClO4. − A CH···O hydrogen bond is formed between them. The proton on the ethoxy group at the end of the column[5]arene cavity H j and H kThe signal peak of the column [5] aromatic hydrocarbon cavity also showed obvious chemical shift, which was attributed to the terminal ethoxy group of ClO4 − Multiple CH···O hydrogen bonds are formed between them. 1 H NMR titration experiments also support the relationship between PYP5 and ClO4 − The formation of "clustered hydrogen bonds" based on the "double-arm-macrocycle synergy" effect.

[0027] In order to gain a deeper understanding of the “clustered hydrogen bond” based on the “double-arm-macrocycle synergistic” effect, density functional theory (DFT) was used to further study the interaction between PYP5 and ClO4. − First, in order to clearly present the surface charge distribution before and after host-guest complexation ( Figure 16 ), the monomers PYP5 and ClO4 were calculated respectively. − and PYP5⊃2ClO4 − The electrostatic potential surface (ESP) of the column[5]arene is shown in Figure 1. The ESP indicates that the 8 ethoxy groups and the bipyridine hydrazone arms on the column[5]arene provide an electron-deficient environment, while ClO4 − It is electron-rich, which is beneficial for the monomer PYP5 to react with ClO4 − At the same time, in PYP5⊃2ClO4 − During the formation of the host-guest complex, electrons were redistributed. Subsequently, the complexation mechanism was also studied through the frontier molecular orbital data (highest occupied molecular orbital and lowest unoccupied molecular orbital, HOMO and LUMO) before and after host-guest complexation. Figure 17 As shown in Figure 2, the HOMO orbital of monomer PYP5 is mainly distributed in the pillar aromatic hydrocarbon cavity, while in the host-guest complex PYP5⊃2ClO4 − In the case of ClO4, the HOMO orbital is distributed in the guest − At the same time, the LUMO orbital is transferred from the double arm of the monomer PYP5 [5] aromatic functionalization to the single arm of the monomer PYP5. And the host-guest complex PYP5⊃2ClO4 is formed. − The energy gap difference after the reaction is 0.81 eV, which is smaller than that of monomer PYP5 (3.41 eV). These changes are caused by the charge transfer between molecules and the formation of multiple hydrogen bonds during the formation of the host-guest complex. In addition, the calculated energy gap between monomer PYP5 and ClO4 − The binding energy between PYP5 and ClO4 is -183.34 kcal / mol, indicating that − The above DFT calculation results show that PYP5 and ClO4 − The formation of "clustered hydrogen bonds" between the two provides a clear explanation and theoretical basis. Therefore, through crystal structure analysis, 1 H NMR titration experiments and DFT calculations fully demonstrate that PYP5 and ClO4− A "clustered hydrogen bond" based on the "double-arm-macrocycle synergistic" effect is formed between them, which significantly enhances the effect of PYP5 on ClO4 − adsorption separation ability.

[0028] In summary, the present invention provides a macrocyclic molecule based on A, A'-bipyridinehydrazone functionalized conjugated pillar[5]arene and a method for synthesizing the same. The macrocyclic molecule is prepared by reacting a bis(4-formylphenylboronic acid) functionalized pillar[5]arene with 2-hydrazinepyridine through an imine condensation reaction to obtain an A, A'-bipyridinehydrazone functionalized conjugated pillar[5]arene PYP5 having two rigid functional arms. Single crystal XRD analysis of PYP5 shows that the macrocyclic molecule PYP5 can self-assemble through multiple hydrogen bonds to form a supramolecular polymer network. Thanks to the "double-arm-macrocyclic synergistic effect" between the double arms of the pillar[5]arene and the ethoxy group, PYP5 can provide multiple "clustered hydrogen bonds" to tightly bind ClO4. − Therefore, the supramolecular polymer network can effectively treat ClO4 in water. − It can show good adsorption and separation performance and can effectively remove ClO4 in water − The removal rate can reach 99.24%. The A, A'-bipyridinehydrazone functionalized conjugated column[5] aromatic macrocyclic molecule provided by the present invention has good application prospects in the fields of supramolecular assembly, water pollutant removal, adsorption separation, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is the H NMR spectrum of the A, A'-bispyridinehydrazone functionalized conjugated column [5] aromatic macrocyclic molecule PYP5 of the present invention;

[0030] Figure 2 The carbon NMR spectrum of the A, A'-bispyridinehydrazone functionalized conjugated column [5] aromatic macrocyclic molecule PYP5 of the present invention;

[0031] Figure 3 This is the high-resolution mass spectrum of the A, A'-bispyridinehydrazone functionalized conjugated column [5] aromatic macrocyclic molecule PYP5 of the present invention;

[0032] Figure 4 The crystal structure diagram of the A, A'-bispyridinehydrazone functionalized conjugated pillar [5] aromatic macrocyclic molecule PYP5 of the present invention;

[0033] Figure 5 The single crystal structure of the present invention's A, A'-bipyridinehydrazone functionalized conjugated pillar[5]arene macrocyclic molecule PYP5 assembled into dimers and one-dimensional chain-like supramolecular polymers;

[0034] Figure 6The crystal structure of the supramolecular polymer network HBPC formed by the assembly of the A, A'-bipyridinehydrazone functionalized conjugated pillar[5]arene macrocyclic molecule PYP5 of the present invention;

[0035] Figure 7 The pore structure of the supramolecular polymer network HBPC formed by assembling the A, A'-bipyridinehydrazone functionalized conjugated pillar [5] aromatic macrocyclic molecule PYP5 of the present invention;

[0036] Figure 8 The supramolecular polymer network HBPC of the present invention A, A'-bispyridylhydrazone functionalized conjugated column [5] aromatic macrocyclic molecule PYP5 adsorbs ClO4 − The crystal structure after

[0037] Figure 9 The "double-arm-macrocycle synergistic" effect of the present invention "clustered hydrogen bond" combines ClO4 − Diagram of the action and mechanism of

[0038] Figure 10 The N2 adsorption-desorption isotherm of the supramolecular polymer network HBPC assembled by the A, A'-bipyridinehydrazone functionalized conjugated column [5] aromatic macrocyclic molecule PYP5 of the present invention;

[0039] Figure 11 FV and FVF of the A, A'-bipyridinehydrazone functionalized conjugated column [5] aromatic macrocyclic molecule PYP5 crystal of the present invention;

[0040] Figure 12 The HBPC adsorption material of the present invention is used to absorb ClO4 in water. − Removal effect diagram;

[0041] Figure 13 The present invention is A, A'-bispyridine hydrazone functionalized conjugated column [5] aromatic hydrocarbon macrocyclic monomer PYP5 complexed with two molecules of ClO4 − High-resolution mass spectrometry;

[0042] Figure 14 The present invention is A, A'-bispyridine hydrazone functionalized conjugated column [5] aromatic hydrocarbon macrocyclic molecule PYP5 in DMSO- d6 There are different molar equivalents of ClO4 − The part of time 1 H NMR titration hydrogen spectrum;

[0043] Figure 15 The present invention is A, A'-bispyridine hydrazone functionalized conjugated column [5] aromatic hydrocarbon macrocyclic molecule PYP5 complexed with ClO4 − Before and after IGMH diagram;

[0044] Figure 16The present invention is A, A'-bispyridine hydrazone functionalized conjugated column [5] aromatic hydrocarbon macrocyclic molecule PYP5 complexed with ClO4 − ESP diagram before and after;

[0045] Figure 17 The present invention is A, A'-bispyridine hydrazone functionalized conjugated column [5] aromatic hydrocarbon macrocyclic molecule PYP5 complexed with ClO4 − Frontier molecular orbital analysis diagram before and after. DETAILED DESCRIPTION

[0046] The following is a further description of the specific embodiments of the present invention with reference to the accompanying drawings and examples. The following examples are only used to illustrate the present invention and are not used to limit the scope of the present invention. The instruments and reagents used are all commercially available conventional products unless otherwise specified.

[0047] Example 1. Synthesis of Bispyridine Hydrazone Functionalized Conjugated Pillar[5] Arene Supramolecular Polymer Network

[0048] Functionalization of bis(4-formylphenylboronic acid) column[5]arene p- Q (200 mg, 0.1978 mmol) and 2-hydrazinepyridine (47.48 mg, 0.4351 mmol) were added to anhydrous ethanol (20 mL), and then a catalytic amount of glacial acetic acid was added dropwise. Under nitrogen protection, the reaction was carried out at 80-85 ° C for 30-36 h. After the reaction was completed, the product was filtered and washed several times to obtain A, A'-bipyridinehydrazone functionalized conjugated column [5] aromatic macrocyclic molecule (189 mg, 80%).

[0049] Crystal cultivation of A, A'-bipyridinehydrazone-functionalized conjugated pillar[5]arene macrocyclic molecules was performed, and single crystal XRD analysis of PYP5 showed that adjacent PYP5 molecules assembled through multiple hydrogen bonds to form a supramolecular polymer network HBPC.

[0050] Example 2: Supramolecular polymer network as adsorption material for removal of ClO4 from water − Applications

[0051] 5.0 mg of HBPC adsorbent material was added to 10 mL of sodium perchlorate aqueous solution (sodium perchlorate concentration was 5.0 mg / L), stirred at room temperature for 24 hours, separated by centrifuge, and the supernatant was filtered through a filter head. The HBPC crystal material was used to determine the ClO4 in aqueous solution using an ion chromatograph. − The adsorption rate (i.e. removal rate) can reach 99.24%, and the residual ClO4 − The concentration is lower than the World Health Organization's drinking water quality standard. The test results are as follows Figure 12 As shown, it is shown that the HBPC adsorption material of the present invention can absorb ClO4 in aqueous solution. −Has good removal effect.

[0052] Calculation method of adsorption (removal) rate:

[0053]

[0054] (Note: C R It is ClO4 − Residual concentration, C1 is ClO4 − The initial concentration, V R =V1).

Claims

1. An A, A'-bipyridinehydrazone functionalized conjugated pillar[5]arene macrocyclic molecule having the structural formula: 。 2. The method for synthesizing the A, A'-bispyridylhydrazone functionalized conjugated pillar[5]arene macrocyclic molecule as claimed in claim 1, wherein the bis-4-formylphenylboronic acid functionalized pillar[5]arene p- Q and 2-hydrazine pyridine are added to an organic solvent, followed by dropwise addition of glacial acetic acid as a catalyst. The reaction is carried out at 80-85°C for 30-36 hours under nitrogen protection. After the reaction is completed, the A, A'-bipyridine hydrazone functionalized conjugated column [5] aromatic macrocyclic molecule is obtained by filtration and washing. Bis(4-formylphenylboronic acid) functionalized column[5]arene p- The structural formula of Q is: 。 3. The method for synthesizing the A, A'-bipyridinehydrazone functionalized conjugated pillar[5]arene macrocyclic molecule according to claim 2, characterized in that: Bis(4-formylphenylboronic acid) functionalized column[5]arene p- The molar ratio of Q to 2-hydrazinopyridine is 1:2 to 1:

3.

4. The method for synthesizing the A, A'-bipyridinehydrazone functionalized conjugated pillar[5] aromatic macrocyclic molecule according to claim 2, characterized in that: The organic solvent is one of anhydrous methanol, anhydrous ethanol, THF and DMF.

5. The method for synthesizing the A, A'-bipyridinehydrazone functionalized conjugated pillar[5]arene macrocyclic molecule according to claim 2, characterized in that: Bis(4-formylphenylboronic acid) functionalized column[5]arene p- The molar ratio of Q to glacial acetic acid is 1:0.05~1:0.

1.

6. The novel macrocyclic molecule of A, A'-bipyridinehydrazone functionalized conjugated pillar[5]arene as claimed in claim 1 self-assembles into a supramolecular polymer network through multiple intermolecular hydrogen bonds.

7. The supramolecular polymer network formed by the assembly of the novel macrocyclic molecule of A, A'-bipyridinehydrazone functionalized conjugated column [5] aromatic hydrocarbon as claimed in claim 6 is used for the removal and separation of ClO4 for non-diagnostic and therapeutic purposes. − Application in.

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