Pyridine hydrazone conjugated pillar arene, synthesis of supramolecular polymer network of pyridine hydrazone conjugated pillar arene and application of pyridine hydrazone conjugated pillar arene in perchlorate ion separation

Abstract

The invention discloses an A, A '-bipyridine hydrazone functionalized conjugated column [5] arene macrocyclic molecule and a synthesis method thereof, and the A, A'-bipyridine hydrazone functionalized conjugated column [5] arene PYP5 with two rigid functional arms is obtained through an imine condensation reaction of bi-4-formylphenylboronic acid functionalized column [5] arene and 2-hydrazinopyridine. The macrocyclic molecule PYP5 can be self-assembled through multiple hydrogen bonds to form a supramolecular polymer network. Benefited from a double-arm-macrocyclic synergistic effect between double arms of column [5] arene and ethyoxyl, PYP5 can provide a plurality of cluster hydrogen bonds to be tightly combined with ClO4. Therefore, the supramolecular polymer network can show good adsorption and separation performance on ClO4 in water, ClO4 in water can be effectively removed, and the removal rate can reach 99.24%. The A, A '-bispyridine hydrazone functionalized conjugated column [5] arene macrocyclic molecule provided by the invention has a good application prospect in the fields of supramolecular assembly, removal of pollutants in water, adsorption separation and the like.

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 method for efficiently removing ClO4 from water using the supramolecular polymer network. − The application of the invention belongs to the technical field of organic synthetic chemistry and the technical field of adsorption separation. 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 − Soluble in water, 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, it is necessary to develop 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 extensive attention due to their excellent host-guest complexing properties. Among the numerous macrocyclic hosts, pillar[n]arene, 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, all-ethyl pillar[5]arene can encapsulate straight-chain alkanes, and all-hydroxy 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 provides a new opportunity for the development of 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 reasonably 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 cooperate with multiple ethoxy groups around the pillar[5]arene cavity through synergistic action with 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 "two-arm-macrocycle synergy" will help realize the supramolecular polymer network for ClO4 in water. − and showed good adsorption and 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; Another object of the present invention is to provide the supramolecular polymer network as an adsorbent material for efficiently removing ClO4 from water − Application in.

[0006] 1. A, A'-Bispyridinehydrazone-functionalized conjugated column[5]aromatic macrocyclic molecule and its synthesis The present invention comprises A, A'-bipyridinehydrazone functionalized conjugated column [5] aromatic macrocyclic molecule having the molecular formula: C 75 H 80 N6O8, marked as: PYP5, structural formula: .

[0007] The present invention provides a method for synthesizing an A, A'-bipyridinehydrazone functionalized conjugated column [5] aromatic macrocyclic molecule: a bis-4-formylphenylboronic acid functionalized column [5] aromatic p- Q is prepared by an imine condensation reaction with 2-hydrazinopyridine. The specific steps are as follows: Functionalization of bis(4-formylphenylboronic acid) column[5]arene p- Q and 2-hydrazinopyridine are added to anhydrous ethanol, followed by dropwise addition of glacial acetic acid as a catalyst. The mixture is reacted at 80-85°C for 30-36 hours under nitrogen protection. After the reaction is completed, the mixture is filtered and washed to obtain the bipyridinehydrazone functionalized conjugated column [5] aromatic macrocyclic molecule PYP5.

[0008] Among them, the bis(4-formylphenylboronic acid) functionalized column[5]arene p- The molar ratio of Q to 2-hydrazinopyridine is 1:2.1~1:3; Bis(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.

[0009] p- The synthesis method of Q is based on 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. The H NMR, C NMR and HRMS spectra of the A, A'-bipyridinehydrazone functionalized conjugated column [5] aromatic macrocyclic molecule PYP5 are shown in Figures 2 and 3, respectively. Figure 1 , Figure 2 , Figure 3 .

[0010] The synthetic route of PYP5 is as follows: II. Crystal Growth and Crystal Structure of A, A'-Bispyridine Hydrazone-Functionalized Conjugated Column [5] Aromatic Macrocyclic Molecules 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 (the volume ratio of dichloromethane to acetone was 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. The crystal structure is shown in the figure Figure 4 Adjacent PYP5 molecules can assemble through multiple hydrogen bonds to form a supramolecular polymer network HBPC.

[0011] The supramolecular polymer network HBPC, which is formed by the assembly of A, A'-bipyridinehydrazone-functionalized conjugated pillars[5]arene macrocyclic molecules, is first assembled through multiple NH···N hydrogen bonds between adjacent PYP5 molecules to form a one-dimensional chain-like 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, the network exhibits a porous structure, and therefore, the N2 gas adsorption-desorption isotherms were measured at 77.3 K ( Fig.10 ), and the apparent surface area of ​​HBPC was obtained using the Brunauer-Emmett-Teller (BET) model to be 4.756 m 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% ( Fig.11 ), for the adsorption of ClO4 − A suitable pore structure is provided.

[0012] 3. Supramolecular polymer networks as adsorbents for removal of ClO4 from water − Applications 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 of ions, we developed a supramolecular polymer network based on a novel “clustered hydrogen bonding enhanced host-guest binding” strategy.

[0013] 1. Adsorption performance of HBPC adsorption materials In order to study the effect of HBPC on ClO4 −The removal performance of HBPC-based materials was determined by ion chromatography to determine the removal performance of ClO4 in aqueous solution. − The adsorption rate can reach 99.24% ( Fig.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.

[0014] 2. Analysis of complexation mechanism In order to study the supramolecular polymer network and ClO4 − We first performed HR-MS characterization and found that the monomer PYP5 and ClO4 − The complexation ratio is 1:2 ( Fig.13 ). We obtained the loaded ClO4 − Host-guest single crystals, labeled as HBPC-ClO4 − In monomeric PYP5 ( Figure 4 , Fig. 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 − ( Fig. 9 The pyridylhydrazone undergoes adaptive rotation due to the induction of the pyridylhydrazone. The two pyridylhydrazone arms and the column[5]arene cavity synergistically bind ClO4 through multiple clustered hydrogen bonds. − The pyridine group on the bipyridine hydrazone 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 bond with ClO4 − ( Figure 8 ) form NH···O hydrogen bonds, all of which surround ClO4 − The surrounding "clustered hydrogen bonds" ( Fig. 9 Right), thus achieving the ClO4 − In addition, in order to conduct in-depth theoretical research and visualization of "cluster hydrogen bonds", we used the IGMH method to calculate the hydrogen bonds 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 −Labeled as: PYP5⊃2ClO4 − .like Fig.15 As shown, ClO4 − Multiple NH···O and CH···O hydrogen bonds are formed with the -NH on pyridine hydrazone, and the methyl and methylene groups on the ethoxyl 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 bonded 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.

[0015] Subsequently, at room temperature, based on a constant concentration of PYP5 and different concentrations of ClO4 − Conducted 1 H NMR titration experiments ( Fig.14 ). With the 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 of the signal shifts to the 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. H j and H k The signal peak of also showed obvious chemical shift, which was attributed to the terminal ethoxy group of the aromatic hydrocarbon cavity of column [5] and 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.

[0016] In order to gain a deeper understanding of the “clustered hydrogen bond” based on the “double-arm-macrocycle synergy” 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 ( Fig.16 ), the monomers PYP5 and ClO4 were calculated respectively. − and PYP5⊃2ClO4 − The electrostatic potential surface (ESP) of the column[5]arene was shown in Figure 1. The ESP showed that the eight ethoxy groups and the bipyridine hydrazone arm on the column[5]arene provided an electron-deficient environment, while ClO4 − 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 the host-guest complexation. Fig.17 As shown in Figure 2, the HOMO orbital of monomer PYP5 is mainly distributed in the pillar aromatic cavity, while in the host-guest complex PYP5⊃2ClO4 − In the case of ClO4, the HOMO orbital is distributed in − At the same time, the LUMO orbital is transferred from the double arm of the monomer PYP5 pillar [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 them provides a clear explanation and theoretical basis. 1 H NMR titration experiments and DFT calculations fully demonstrate that PYP5 and ClO4 − A "clustered hydrogen bond" based on the "double-arm-macrocycle synergy" effect was formed between them, which significantly enhanced the effect of PYP5 on ClO4 − adsorption separation ability.

[0017] In summary, the present invention provides a macrocyclic molecule based on A, A'-bipyridinehydrazone functionalized conjugated pillar[5]arene and a synthesis method thereof, wherein the A, A'-bipyridinehydrazone functionalized conjugated pillar[5]arene PYP5 having two rigid functional arms is obtained by reacting the bi-4-formylphenylboronic acid functionalized pillar[5]arene with 2-hydrazinepyridine through an imine condensation reaction. 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. Benefiting from 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 is effective for the ClO4 − It can show good adsorption and separation performance and can effectively remove ClO4 from 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

[0018] Figure 1 The nuclear magnetic resonance hydrogen spectrum of the A, A'-bipyridinehydrazone functionalized conjugated column [5] aromatic macrocyclic molecule PYP5 of the present invention; Figure 2 The carbon NMR spectrum of the A, A'-bipyridinehydrazone functionalized conjugated column [5] aromatic macrocyclic molecule PYP5 of the present invention; Figure 3 This is the high-resolution mass spectrum of the A, A'-bipyridinehydrazone functionalized conjugated column [5] aromatic macrocyclic molecule PYP5 of the present invention; Figure 4 The crystal structure diagram of the A, A'-bipyridinehydrazone functionalized conjugated column [5] aromatic macrocyclic molecule PYP5 of the present invention; Figure 5 The single crystal structure of the A, A'-bipyridinehydrazone functionalized conjugated pillar [5] aromatic macrocyclic molecule PYP5 assembled into dimers and one-dimensional chain-like supramolecular polymers of the present invention; Figure 6 The crystal structure of the supramolecular polymer network HBPC formed by assembling the A, A'-bipyridinehydrazone functionalized conjugated column [5] aromatic macrocyclic molecule PYP5 of the present invention; Figure 7 The pore structure of the supramolecular polymer network HBPC formed by assembling the A, A'-bipyridinehydrazone functionalized conjugated column [5] aromatic macrocyclic molecule PYP5 of the present invention; Figure 8The supramolecular polymer network HBPC of the A, A'-bipyridinehydrazone functionalized conjugated column [5] aromatic macrocyclic molecule PYP5 of the present invention adsorbs ClO4 − The crystal structure after Fig. 9 The "double-arm-macrocycle synergy" effect of the present invention "clustered hydrogen bond" combines ClO4 − The action and mechanism diagram; Fig.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; Fig.11 FV and FVF of the A, A'-bipyridinehydrazone functionalized conjugated column [5] aromatic macrocyclic molecule PYP5 crystal of the present invention; Fig.12 The HBPC adsorption material of the present invention is used for ClO4 in water − Removal effect diagram; Fig.13 The present invention is A, A'-bipyridine hydrazone functionalized conjugated column [5] aromatic hydrocarbon macrocyclic monomer PYP5 complexed with two molecules of ClO4 − High-resolution mass spectrometry; Fig.14 The present invention is A, A'-bipyridine hydrazone functionalized conjugated column [5] aromatic macrocyclic molecule PYP5 in DMSO- d6 There are different molar equivalents of ClO4 − The part of time 1 H NMR titration hydrogen spectrum; Fig.15 The present invention is A, A'-bipyridine hydrazone functionalized conjugated column [5] aromatic macrocyclic molecule PYP5 complexed with ClO4 − IGMH images before and after; Fig.16 The present invention is A, A'-bipyridine hydrazone functionalized conjugated column [5] aromatic macrocyclic molecule PYP5 complexed with ClO4 − ESP diagram before and after; Fig.17 The present invention is A, A'-bipyridine hydrazone functionalized conjugated column [5] aromatic macrocyclic molecule PYP5 complexed with ClO4 − Frontier molecular orbital analysis diagram before and after. DETAILED DESCRIPTION

[0019] The specific implementation modes of the present invention are further described below in conjunction with 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.

[0020] Example 1. Synthesis of Bispyridine Hydrazone Functionalized Conjugated Column [5] Arene Supramolecular Polymer Network 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 mixture was reacted at 80-85 °C for 30-36 h. After the reaction, the mixture was filtered and washed several times to obtain A, A'-bipyridinehydrazone functionalized conjugated column [5] aromatic macrocyclic molecule (189 mg, 80%).

[0021] 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.

[0022] Example 2: Supramolecular polymer network as adsorbent for removal of ClO4 from water − Applications 5.0 mg of HBPC adsorption 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 the precipitate in a 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 Fig.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.

[0023] Calculation method of adsorption (removal) rate: (Description: C R It is ClO4 − Residual concentration, C1 is ClO4 − The initial concentration, V R =V1).

Claims

1. An A, A'-bipyridinehydrazone functionalized conjugated column [5] aromatic macrocyclic molecule having the structural formula: 。 2. The method for synthesizing the A, A'-bipyridinehydrazone 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 column [5] aromatic 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 column [5] aromatic macrocyclic molecule according to claim 2, characterized in that: The organic solvent is one of anhydrous methanol, anhydrous ethanol, THF, DMF and the like.

5. The method for synthesizing the A, A'-bipyridinehydrazone functionalized conjugated column [5] aromatic macrocyclic molecule as claimed in 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 A, A'-bipyridinehydrazone functionalized conjugated column [5] aromatic novel macrocyclic molecule as claimed in claim 1 forms a supramolecular polymer network through multiple intermolecular hydrogen bonds self-assembled.

7. The A, A'-bipyridinehydrazone functionalized conjugated column [5] as claimed in claim 6 is a novel macrocyclic molecule of aromatic hydrocarbons, which is assembled to form a supramolecular polymer network for efficient removal and separation of ClO4 − Application in.

Images