Unilateral functionalized column [5] arene, metal supramolecular polymer constructed by unilateral functionalized column [5] arene and application

Abstract

The invention provides unilateral functionalized column [5] arene, a metal supramolecular polymer constructed by coordination and orthogonal assembly of the unilateral functionalized column [5] arene and metal through host-guest interaction and application of the unilateral functionalized column [5] arene. The invention designs and synthesizes a unilateral functionalized column [5] arene DNBP5 with a novel structure. The molecule simultaneously contains a column [5] arene cavity capable of generating subject-object interaction with a guest molecule and a pyridine group capable of generating coordination interaction with metal ions. DNBP5 is used as a subject, disulfide bond connected bilateral secondary ammonium salt modified G-2SNHP is used as an object, silver ions are used as metal ions, and the metal supramolecular polymer is obtained through orthogonal assembly in a chloroform solution through subject-object interaction and metal coordination interaction. The polymer can form thermal response type gel when the concentration in chloroform is greater than or equal to 100 mM, the phase transition temperature is 45-50 DEG C, and the polymer has a reversible sol-gel conversion behavior, so that the polymer has a wide application prospect in the field of stimulation response intelligent materials.

Description

Technical Field

[0001] This invention belongs to the field of supramolecular chemistry technology, specifically relating to a single-sided functionalized columnar aromatic hydrocarbon (DNBP5) and its metal supramolecular polymer constructed by orthogonal assembly with metal coordination through host-guest interaction and application. Background Technology

[0002] Supramolecular chemistry is the science that studies non-covalent interactions between molecules (such as hydrogen bonds, van der Waals forces, hydrophobic interactions, host-guest interactions, and metal coordination) and the functions of their assemblies. Among these, orthogonal assembly strategies, which utilize two or more different types of non-covalent interactions to synergistically drive molecular assembly, provide a powerful tool for constructing complex and diverse supramolecular materials.

[0003] Columnar aromatics, as fifth-generation macrocyclic host molecules, have attracted widespread attention in supramolecular chemistry since their first reported synthesis in 2008 due to their unique rigid columnar structure, electron-rich cavities, and ease of functionalization. Compared to other macrocyclic hosts such as crown ethers, cyclodextrins, calixarnes, and cucurbiturates, columnar aromatics offer convenient conditions for constructing host-guest assemblies and diverse stimulus-responsive supramolecular polymer materials. In recent years, with the continuous development of organic synthesis methodologies and supramolecular chemistry, various functionalized columnar aromatics have been reported and further applied in multiple fields such as materials science, environmental science, sensing and detection, adsorption separation, cell imaging, and catalysis.

[0004] Metal coordination is a type of non-covalent interaction between ligands and metal ions, characterized by strong and controllable bonding ability and high directionality. Furthermore, due to the unique photophysical, redox, magnetic, and electrochromic properties of ligands and metal ions, utilizing metal-ligand bonds to drive the formation of discrete metal supramolecular structures has proven to be an efficient strategy for preparing metal supramolecular polymer materials with novel structures, controllable morphologies, well-defined configurations, and diverse functions.

[0005] However, there are relatively few studies on functionalized pillar [5] aromatics with multiple assembly sites (e.g., possessing both host-guest recognition sites and metal coordination sites) that have been reported so far, and on their orthogonal assembly through host-guest interactions and metal coordination interactions to construct metal supramolecular polymer materials. Therefore, the design and synthesis of functionalized pillar [5] aromatics with multiple assembly sites, and the exploration of their application in constructing metal supramolecular polymer materials and related smart gel materials under the synergistic assembly of multiple non-covalent bonds, have important theoretical significance and application value. Summary of the Invention

[0006] The primary objective of this invention is to provide a unilaterally functionalized columnar aromatic hydrocarbon [5] with specific recognition sites and metal coordination sites, and a method for its synthesis. Another objective of this invention is to provide a method for constructing metal supramolecular polymers based on the aforementioned unilaterally functionalized columnar aromatic hydrocarbon [5] DNBP5 through orthogonal assembly of host-guest interactions and metal coordination interactions, and its applications.

[0007] I. Single-sided energy-column[5] Aromatic DNBP5 and its synthesis method The molecular formula of the single-sided functionalized columnar aromatic hydrocarbon DNBP5 is C 67 H 71 N3O 12 The structural formula is: .

[0008] The method for synthesizing the aromatic DNBP5 by a single-sided energy column [5] includes the following steps: (1) The single-sided hexacarbon brominated [5] aromatic hydrocarbon DBCP5 and 6-hydroxy-2-naphthaldehyde were refluxed in acetonitrile solution at 85~90℃ for 40~50 hours under nitrogen atmosphere. After the reaction, the intermediate DCNP5 was obtained by column chromatography. The molar ratio of the single-sided hexacarbon brominated [5] aromatic hydrocarbon DBCP5 to 6-hydroxy-2-naphthaldehyde was 1:2~1:3.

[0009] (2) DCNP5 and isoniazid were refluxed in anhydrous ethanol solution at 75-78°C for 6-10 hours under acetic acid catalysis. After the reaction was completed, the single-sided functionalized columnar aromatic hydrocarbon DNBP5 was obtained by recrystallization. The molar ratio of isoniazid to DCNP5 was 1:1 to 1:2.

[0010] The synthesis of the single-sided hexa-carbon brominated columnar aromatic hydrocarbon DBCP5 is described in the literature: J.-D. Ding, J.-F. Chen, Q.Lin, H. Yao, Y.-M. Zhang, and T.-B. Wei*, Polym. Chem ., 2018, 9, 5370-5376. II. Metal supramolecular polymers and their preparation methods The metal supramolecular polymer of the present invention is based on a single-sided functionalized columnar aromatic hydrocarbon DNBP5 as the host, and a double-sided secondary ammonium salt modified G-2SNHP connected by disulfide bonds as the guest, with silver ions as the metal ions, and is orthogonally assembled in chloroform solution through host-guest interaction and metal coordination interaction; the molar ratio of the host DNBP5, silver ions and guest G-2SNHP is 2:1:2.

[0011] The molecular formula of the single-sided functionalized columnar aromatic hydrocarbon DNBP5 is C67 H 71 N3O 12 The structural formula is: ; The molecular formula of G-2SNHP modified with a disulfide bond-linked bilateral secondary ammonium salt is C. 46 H 72 N8O6S2 2+ The structural formula is: The structure of metal supramolecular polymers is as follows: Figure 17 .

[0012] Preparation method of metal supramolecular polymer materials: DNBP5, G-2SNHP and silver trifluoromethanesulfonate are dissolved in chloroform solution in a molar ratio of 2:1:2 and stirred at room temperature for 8-10 hours. Metal supramolecular polymers can be formed through synergistic orthogonal assembly of host-guest interactions and metal coordination interactions.

[0013] For the synthesis of G-2SNHP, please refer to the literature: Y.-F. Li, X. Wang, C.-Y. Wang, and Y.-W. Yang*, "Multi-stimuli-responsive supramolecular polymer via orthogonal pillararene-based host−guest and π−πinteractions" Tetrahedron , 2023, 149, 133718. III. Metal supramolecular polymer gel The metal supramolecular polymer gel (G-2SNHP⊂DNBP5@Ag-G) provided by this invention is formed from the above-mentioned metal supramolecular polymer material at a minimum concentration of 100 mM in chloroform solution. This metal supramolecular polymer gel exhibits good reversible sol-gel interconversion behavior under heating and cooling conditions, with a phase transition temperature of 45℃~50℃. The gel possesses elastic-dominant rheological properties, satisfying the following rheological properties: SLB value < 0.5, and elastic modulus G' > viscous modulus G'.

[0014] This invention also provides the application of the above-mentioned metal supramolecular polymers in the preparation of stimulus-responsive smart materials. The metal supramolecular polymers can form thermoresponsive gels, exhibiting sol-gel interconversion behavior at 45℃ to 50℃, and their gels possess good elasticity and a stable network structure.

[0015] IV. Study on the self-assembly performance of DNBP5 We investigated the form of the product molecule DNBP5 in deuterated chloroform using a two-dimensional ROESY experiment. Figure 7 As shown, due to the hydrogen proton H on the hollow benzene ring of DNBP5 k The hydrogen proton H on the methylene bridge n And the hydrogen proton H on the methoxy group o At high concentrations, the π−π and CH···π interactions clearly show the ROE correlation signal. However, no ROE correlation signal was found between the protons on the cavity phenyl group of columnar aromatic DNBP5 and the protons on its alkyl chain or other positions, which strongly suggests that there is no self-encapsulated structure in DNBP5.

[0016] V. Study on the photophysical properties of DNBP5 Furthermore, we investigated the fluorescence emission spectra of DNBP5 in DMSO solutions with different water contents. In pure DMSO (good solvent) solution, the fluorescence intensity of DNBP5 at 442 nm was relatively weak. However, when the water (poor solvent) content increased to 30%, the fluorescence emission gradually increased and was accompanied by a significant red shift. Further increasing the water content to 90% resulted in the strongest fluorescence intensity of DNBP5, and the emission peak position remained unchanged. Figure 8 This result indicates that the fluorescence emission of DNBP5 can be attributed to a well-developed supramolecular assembly-induced emission enhancement (SAIEE) mechanism.

[0017] VI. Based on DNBP5 and Ag + Construction and characterization of metal coordination assemblies Because the DNBP5 molecule is modified with a pyridinium group, the nitrogen atom on the pyridinium group can undergo metal coordination with silver ions. We characterized this metal coordination process using proton nuclear magnetic resonance spectroscopy. Figure 9 As shown, after adding 0.5 equivalents of silver ions to DNBP5, the proton signal H on the pyridinium group of DNBP5 was found to be present. b Compared to before, it shows a significant shift to higher fields, while the proton signal H g The magnetron sputtering then shifts to a lower field. Simultaneously, the NMR spectrum of the mixture exhibits significant broadening compared to the single DNBP5 1H NMR spectrum. These phenomena indicate that the pyridinyl group in DNBP5 undergoes metal coordination with the silver ion, forming a larger molecular weight dimer. Furthermore, we characterized the morphology of the coordinated dimer using SEM experiments, finding that the constructed metal-coordinated assemblies exhibit an irregular coral-like morphology. Figure 10 ).

[0018] VII. Characterization Study of Subject-Object Interactions between Subject DNBP5 and Object G-2SNHP Since DNBP5 itself does not have a self-encapsulating structure, we used a simulated host methoxy homogeneous aromatic hydrocarbon [5] (DMP5) to study the interaction between the host and guest. Figure 11 As shown, when different proportions of G-2SNHP were gradually added to a deuterated chloroform solution of DMP5, the hydrogen protons (H2) on the triazole group in G-2SNHP gradually shifted to the higher field, indicating a significant host-guest inclusion interaction. Simultaneously, in the high-resolution mass spectrum (… Figure 12 The peak at m / z = 1558.7545 can be attributed to the host-guest complex [2DNBP5@G-2SNHP], and no other related peaks with complexation ratios appear, indicating that the host DNBP5 and the guest G-2SNHP form a host-guest complex with a binding ratio of 2:1.

[0019] VIII. Preparation and Structural Characterization of Three-Component Metal Supramolecular Polymers DNBP5 and Ag were confirmed + After determining the binding ratio between DNBP5 and G-2SNHP, we used DNBP5:Ag + A series of metal supramolecular polymers at different concentrations (2, 5, 10, 20, 40, 60, and 80 mM) were prepared using a molar ratio of G-2SNHP = 2:1:2, and were subsequently characterized by 1H NMR spectroscopy. Figure 13 As shown, when the concentration gradually increases, the hydrogen protons H in DNBP5... a The gradual shift towards a lower field indicates the presence of intermolecular hydrogen bonding in adjacent linear supramolecular polymers. Simultaneously, the hydrogen protons H in the naphthyl group... e-j The gradual shift towards higher fields indicates the presence of π···π in the naphthalene ring portion. Stacking. Furthermore, the signal peaks broaden significantly at high concentrations, strongly suggesting the formation of high molecular weight metal supramolecular polymers.

[0020] In summary, DNBP5, Ag + Under the synergistic drive of metal coordination and host-guest inclusion interactions, DNBP5, G-2SNHP, and other molecules orthogonally assemble to form a linear supramolecular polymer. Simultaneously, due to the presence of acylhydrazone bonds in the DNBP5 molecule, which serve as excellent hydrogen bond donor / acceptor sites, intermolecular hydrogen bonds can form between adjacent linear supramolecular polymers. Therefore, at certain concentrations, the linear supramolecular polymers further form a cross-linked metal supramolecular polymer network through intermolecular hydrogen bonding and π···π stacking interactions. This property lays a solid foundation for the preparation of metal supramolecular polymer gels.

[0021] IX. Preparation, Characterization, and Optical Microrheological Properties Study of Metal Supramolecular Polymer Gels Since DNBP5, silver trifluoromethanesulfonate, and G-2SNHP all exhibit good solubility in chloroform solution, we used the inversion method to test the minimum gelling concentration in chloroform solution. Figure 14 As shown, we prepared a series of metal supramolecular polymers at different concentrations (20 mM, 50 mM, 75 mM, and 100 mM). After complete dissolution and overnight incubation at room temperature, we found that only at 100 mM could a stable metal supramolecular polymer gel (G-2SNHP⊂DNBP5@Ag-G) be formed. This metal supramolecular polymer gel exhibited good sol-gel interconversion behavior under heating and cooling conditions, with a phase transition temperature of 45℃~50℃. Furthermore, we characterized the microstructure of G-2SNHP⊂DNBP5@Ag-G using SEM, revealing a relatively regular blocky structure. Figure 15 ).

[0022] Next, we investigated the optical microrheological properties of the metal supramolecular polymer gel using an optical microrheometer. The solid-liquid equilibrium (SLB) value represents the ratio of liquid to solid behavior in the sample. An SLB value greater than 0.5 indicates that liquid behavior dominates in the sample, while an SLB value less than 0.5 indicates that solid behavior dominates. When 0 < SLB < 0.5, the gel is closer to elastic properties. Figure 16 As shown in figure a, the SLB value of the metal supramolecular polymer gel (G-2SNHP⊂DNBP5@Ag-G) falls between 0 and 0.5, indicating that its solid behavior is greater than its liquid behavior, and the gel is more elastic. Meanwhile, the root mean square displacement (MSD) is calculated using decorrelation curves to determine the root mean square displacement of scattering particles in the sample; its value is related to the viscoelasticity of the gel sample. Specifically, the lower the plateau of the MSD curve, the stronger the gel's elasticity. Figure 16 As shown in b, at room temperature, the MSD of G-2SNHP⊂DNBP5@Ag-G exhibits a low plateau, indicating that the metal supramolecular polymer gel possesses high crosslinking strength and a more stable network structure. Furthermore, the elastic modulus (G') represents the elastic energy temporarily stored in the soft matter to resist external forces. We tested the elastic modulus (G') and viscous modulus (G") of G-2SNHP⊂DNBP5@Ag-G. Figure 16 As shown in c, within the measured frequency range, the elastic modulus (G') of G-2SNHP⊂DNBP5@Ag-G is higher than its viscous modulus (G"), indicating that the metal supramolecular polymer gel exhibits the characteristics of an elastic material.

[0023] In summary, this invention designs and synthesizes a novel single-sided functionalized columnar [5]arene DNBP5. This molecule simultaneously contains a columnar [5]arene cavity that can interact with guest molecules as a host-guest interaction and a pyridine group that can coordinate with metal ions. Utilizing the host-guest interaction between the columnar [5]arene cavity of DNBP5 and the secondary ammonium salt group of G-2SNHP, as well as the interaction between the pyridine group of DNBP5 and Ag... + Through metal coordination interactions, orthogonal assembly driven by multiple non-covalent interactions was successfully achieved, constructing a metal supramolecular polymer material. This metal supramolecular polymer material can form a stable metal supramolecular polymer gel at a specific concentration. The prepared metal supramolecular polymer gel exhibits good thermal responsiveness and a reversible sol-gel phase transition behavior, which makes it promising for applications in the field of stimulus-responsive smart materials. Attached Figure Description

[0024] Figure 1 The hydrogen NMR spectrum of DCNP5; Figure 2 The image shows the carbon NMR spectrum of DCNP5. Figure 3 The matrix-assisted laser ablation time-of-flight mass spectrum of DCNP5; Figure 4 The hydrogen NMR spectrum of DNBP5; Figure 5 The carbon NMR spectrum of DNBP5; Figure 6 The matrix-assisted laser desorption / ionization time-of-flight mass spectrum of DNBP5; Figure 7 Two-dimensional ROESY spectrum of DNBP5 at 20 mM (600 MHz, CDCl3, 298 K); Figure 8 The fluorescence emission spectra of DNBP5 at different water contents are shown. Figure 9 The proton NMR spectrum of DNBP5 coordinated with silver ions; Figure 10 SEM image of DNBP5 after coordination with silver ions; Figure 11The NMR titration spectra (400 MHz, CDCl3, 298 K) between DMP5 and G-2SNHP are shown. (a) to (j) represent the molar ratios between the model host DMP5 and the guest G-2SNHP as follows: [DMP5] / [G-2SNHP] = 0:10, [DMP5] / [G-2SNHP] = 1:9, [DMP5] / [G-2SNHP] = 2:8, [DMP5] / [G-2SNHP] = 3:7, [DMP5] / [G-2SNHP] = 4:6, [DMP5] / [G-2SNHP] = 5:5, [DMP5] / [G-2SNHP] = 6:4, [DMP5] / [G-2SNHP] = 8:2, [DMP5] / [G-2SNHP] = 9:1 ...1, [DMP5] / [G-2SNHP] = 4:1, [DMP5] / [G-2SNHP] = 4:1, [DMP5] / [G-2SNHP] = 4:1, [DMP5] / [G-2SNHP] = 4:1, [DMP5] / [G-2SNHP] = 4:1, [DMP5] / [G-2SNHP] = 4:1, [DMP5] / [G-2SNHP] = 4:1, [DMP5] / [G-2SNHP] = 4:1, [DMP5] = 10:0; Figure 12 Mass spectra of host-guest complexes formed by DNBP5 and G-2SNHP; Figure 13 The concentration NMR spectra of the three-component metal supramolecular polymer (400 MHz, CDCl3, 298 K) are shown in (1) to (7), which represent the 1H NMR spectra of the three-component metal supramolecular polymer at concentrations of 2 mM, 5 mM, 10 mM, 20 mM, 40 mM, 60 mM and 80 mM, respectively. Figure 14 Preparation and thermal response diagram of a three-component metal supramolecular polymer gel; Figure 15 SEM image of the three-component metal supramolecular polymer gel; Figure 16 The optical microrheological properties characterization diagrams of the three-component metal supramolecular polymer gel are shown, where (a) is the solid-liquid equilibrium value of the metal supramolecular polymer gel, (b) is the root mean square displacement of the metal supramolecular polymer gel, and (c) is the curve of the elastic modulus (G') and viscous modulus (G'') of the metal supramolecular polymer gel as a function of frequency. Figure 17 This is a structural diagram of a metal supramolecular polymer. Detailed Implementation

[0025] The following description, in conjunction with the accompanying drawings and examples, further illustrates the specific embodiments of the present invention. These examples are for illustrative purposes only and are not intended to limit the scope of the invention.

[0026] The synthesis, characterization and assembly application of the single-sided functionalized column[5] aromatic hydrocarbon of the present invention will be further illustrated below through specific examples.

[0027] Example 1 Synthesis of DNBP5, an aromatic hydrocarbon, from a single-sided functionalized column [5]. (1) First, add 1.24 g, 1.38 mmol of single-sided hexacarbon brominated [5] aromatics DBCP5 and KI (0.23 g, 1.38 mmol, KI is used to activate bromine atoms) to 150 mL of acetonitrile solvent and stir at room temperature for 30 minutes; then add K2CO3 (1.55 g, 11.23 mmol) and 6-hydroxy-2-naphthaldehyde (0.58 g, 3.36 mmol) to the above mixed solution and reflux at 85 °C for 48 hours under nitrogen protection. After the reaction is complete, filter to remove inorganic salts, wash the filter cake with DCM, combine the collected filtrates, and distill them under reduced pressure to obtain crude product. Column chromatography separation yields yellow solid powder DCNP5 (0.65 g, 48%).

[0028] The 1H NMR spectrum of DCNP5 is as follows: Figure 1 As shown, 1 H NMR (400 MHz, CDCl3, 298 K) δ (ppm): 10.10 (s, 1H), 8.25 (d, J = 1.6 Hz, 1H), 7.96 –7.84 (m, 2H), 7.78 (d, J = 8.5 Hz, 1H), 7.22 (dd, J = 8.9, 2.2 Hz, 1H), 7.18 –7.13 (m, 1H), 6.79 (td, J = 4.8, 4.3, 2.8Hz, 10H), 4.06 (t, J = 6.3 Hz, 2H), 3.89 (t, J = 6.1 Hz, 2H), 3.76 (q, J = 2.8, 1.9Hz, 10H), 3.68–3.63 (m, 27H), 1.93–1.75 (m, 4H), 1.58 (dq, J = 20.2, 7.0 Hz, 4H). The carbon NMR spectrum of DCNP5 is as follows: Figure 2 As shown, 13 C NMR (101 MHz, CDCl3, 298 K) δ(ppm): 192.01,159.80, 150.88, 150.86, 150.81, 150.79, 150.76, 150.11, 138.34,134.28,132.28, 131.06,128.32, 128.31, 128.28, 128.23, 128.21, 128.19, 127.85,127.71, 123.58, 120.20, 115.05, 114.24, 114.18, 114.14, 114.06, 106.81,68.36,68.05, 55.86, 55.83, 55.78, 55.74, 29.76, 29.72, 29.67, 29.59, 29.00, 26.92, 26.10, 25.88. The mass spectra of DCNP5 are as follows: Figure 3 As shown, MS (MALDI-TOF): m / z calcd. for [M] + C 61 H 66 O 12 , 990.4554, found [M] + 990.1082. [M+Na] + C 61 H 66 O 12 Na, 1013.4446, found [M+Na] + 1013.1710.

[0029] (2) Naphthaldehyde-modified columnar aromatic hydrocarbon DCNP5 (1.29 g, 1.30 mmol) and isoniazid (0.15 g, 1.1 mmol) were refluxed in 25 mL of anhydrous ethanol solution at 78 °C for 8 hours under the catalysis of acetic acid (2 mL). After the reaction was completed, the mixture was cooled to room temperature, the solvent was removed by vacuum distillation, and the crude product was recrystallized to obtain the final product DNBP5 as a pale yellow solid powder in 81% yield.

[0030] The proton NMR spectrum is as follows Figure 4 As shown, 1 H NMR (400 MHz, CDCl3, 298 K) δ (ppm): 10.26 (d, J =50.3 Hz, 1H), 8.89 – 8.63 (m, 2H), 8.46 (s, 1H), 8.04 – 7.92 (m, 1H),7.85 (d, J= 6.1 Hz, 1H), 7.80 – 7.63 (m, 4H), 7.18 – 7.04 (m, 2H), 6.83 – 6.71 (m,10H), 4.07 – 3.96(m, 2H), 3.87 (t, J = 6.1 Hz, 2H), 3.77 (d, J = 10.2 Hz, 10H), 3.64 (s, 27H), 1.89 – 1.73 (m, 4H), 1.62 – 1.46 (m, 4H). The carbon NMR spectrum of DNBP5 is as follows: Figure 5 As shown, 13 C NMR (101 MHz, CDCl3, 298 K) δ (ppm): 158.49, 151.09, 150.89, 150.83,150.79, 150.77, 150.75, 150.73, 150.58, 150.08, 149.82, 129.97,129.61,129.41,128.66, 128.37, 128.28, 128.20, 127.53, 123.87, 123.75, 121.20,119.75, 115.02, 114.16, 114.09, 114.01, 106.80, 68.40, 67.95, 58.24, 55.85, 55.81, 55.77, 29.72, 29.70, 29.66, 29.62, 29.53, 29.10, 26.13, 25.95. The mass spectra of DNBP5 are as follows: Figure 6 As shown, MS (MALDI-TOF): m / z calcd. for [M+Na] + C 67 H 71 N3O 12 Na, 1132.4930;Found 1132.1291.

[0031] Example 2: Preparation and characterization of DNBP5-based self-assembly and its metal coordination assemblies Accurately weigh DNBP5 (0.0111 g, 20 mmol) solid powder and silver trifluoromethanesulfonate (0.0013 g, 10 mmol) into an NMR tube. Dissolve the DNBP5 and silver ions completely in 0.5 mL of deuterated chloroform, shake well, and let stand at room temperature for 0.5 hours to obtain the metal coordination assembly of DNBP5 and silver ions. Then, perform 1H NMR characterization at room temperature. Figure 9 .

[0032] A mixture of DNBP5 (0.0222 g, 40 mmol) and silver trifluoromethanesulfonate (0.0026 g, 20 mmol) was thoroughly dissolved in chloroform solution and then dropped onto a silicon wafer. After vacuum drying, the metal coordination assembly sample was obtained and subsequently characterized by scanning electron microscopy. Figure 10 .

[0033] Example 3: Fluorescence emission spectroscopy test of DNBP5 at different water contents Accurately weigh 0.0022 g (0.002 mol) of DNBP5 and dissolve it in 10 mL of DMSO solution to initially prepare a solution with a concentration of 2 × 10⁻⁶. -4 A stock solution of mol / L is prepared for later use.

[0034] Prepare 10 clean test tubes and number them sequentially. First, use a pipette to sequentially pipette the prepared DNBP5 DMSO solution (C = 2 × 10⁻⁶). -4 Prepare 0.5 mL of each of the following test tubes: 0.5 mL of distilled water (mol / L); then, sequentially pipette 0, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, and 4.5 mL of distilled water into the aforementioned test tubes; finally, dilute to 5 mL with pure DMSO solution, mix thoroughly, and let stand for 5 minutes to obtain a series of test solutions with water contents of 0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, and 90% (C = 2 × 10⁻⁶). -5 (mol / L). Fluorescence emission spectra were measured at an excitation wavelength of 350 nm, as follows: Figure 8 .

[0035] Example 4: Construction of a three-component metal supramolecular polymer Accurately weigh DNBP5 (0.2219 g, 40 mmol), silver trifluoromethanesulfonate (0.0257 g, 20 mmol), and G-2SNHP (0.2373 g, 40 mmol) and dissolve them in 5 mL of chloroform solution. Stir thoroughly at room temperature for 10 hours. The corresponding metal supramolecular polymer can be constructed under the synergistic drive of multiple non-covalent interactions.

[0036] Example 5: Preparation and application of metal supramolecular polymer gels Accurately weighed DNBP5 (0.0666 g, 200 mmol), silver trifluoromethanesulfonate (0.0077 g, 100 mmol), and G-2SNHP (0.0712 g, 200 mmol) were dissolved in a glass vial containing 0.3 mL of chloroform solution under heating conditions. After complete dissolution, the solution was allowed to stand overnight at room temperature, resulting in the formation of a homogeneous metal supramolecular polymer gel (G-2SNHP⊂DNBP5@Ag-G). This metal supramolecular gel exhibited good reversible gel / sol phase transition behavior under heating and cooling conditions, indicating that this supramolecular gel can serve as a good stimulus-responsive smart material.

Claims

1. A unilateral functionalized columnar aromatic hydrocarbon [5], characterized in that, The structural formula of the single-sided functionalized columnar aromatic DNBP5[5] is as follows: 。 2. The method for synthesizing unilateral functionalized column [5] aromatics according to claim 1, characterized in that, The method for synthesizing the unilateral functionalized column[5] aromatic DNBP5 includes the following steps: (1) The single-sided six-carbon chain brominated column[5] aromatic hydrocarbon DBCP5 was reacted with 6-hydroxy-2-naphthaldehyde, potassium carbonate and potassium iodide in acetonitrile solution and refluxed at 85~90℃ for 40~50 hours under nitrogen atmosphere. After the reaction, the intermediate DCNP5 was obtained by column chromatography. The structural formula of the single-sided six-carbon-chain brominated columnar aromatic hydrocarbon DBCP5[5] is as follows: ； The structural formula of DCNP5 is: (2) DCNP5 and isoniazid were refluxed in anhydrous ethanol solution at 75-78°C for 6-10 hours under acetic acid catalysis. After the reaction was completed, the single-sided functionalized columnar aromatic DNBP5 was obtained by recrystallization.[5] 3. The method for synthesizing unilateral functionalized column [5] aromatics according to claim 2, characterized in that, In step (1), the molar ratio of the single-sided six-carbon chain brominated columnar aromatic hydrocarbon DBCP5 to 6-hydroxy-2-naphthaldehyde is 1:2 to 1:3; in step (2), the molar ratio of the isoniazid to DCNP5 is 1:1 to 1:

2.

4. A metal supramolecular polymer based on unilaterally functionalized column[5]arene is formed by unilaterally functionalized column[5]arene DNBP5 as the host, G-2SNHP modified by disulfide-linked bilateral secondary ammonium salt as the guest, and silver ions as the metal ions, which are orthogonally assembled in chloroform solution through host-guest interaction and metal coordination. The structural formula of the single-sided functionalized columnar aromatic DNBP5[5] is as follows: ； The structural formula of G-2SNHP modified with a disulfide bond-linked bilateral secondary ammonium salt is: 。 5. The metal supramolecular polymer according to claim 4, characterized in that, The molar ratio of the host DNBP5, silver ions, and guest G-2SNHP is 2:1:

2.

6. A method for preparing a metal supramolecular polymer as described in claim 4 or 5, characterized in that, DNBP5, G-2SNHP and silver trifluoromethanesulfonate were dissolved in chloroform solution and stirred at room temperature for 8-10 hours. The metal supramolecular polymer was constructed through orthogonal assembly of host-guest interaction and metal coordination interaction.

7. A metal supramolecular polymer gel, characterized in that, It is formed from the metal supramolecular polymer of any one of claims 4-6 at a concentration ≥100 mM in chloroform solution.

8. The metal supramolecular polymer gel according to claim 7, characterized in that, The gel exhibits sol-gel interconversion behavior under heating and cooling conditions, with a phase transition temperature of 45℃~50℃.

9. The application of the metal supramolecular polymer of claim 4 in the preparation of stimulus-responsive smart gel materials, characterized in that, A reversible sol-gel conversion is achieved through temperature triggering.

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