An aggregation-induced emission macrocycle compound and a preparation method and application thereof

Abstract

This patent application discloses an aggregation-induced emission (AIE) macrocyclic compound, its preparation method, and its applications. This AIE macrocyclic compound uses aromatic amide trimers or dimers as building blocks, and is cyclized in one step via a Friedel-Crafts reaction. The synthetic route is simple and yields high amounts, providing a new approach for constructing a new class of rigid aromatic amide macrocycles. Experiments have shown that this type of macrocycle possesses electron-rich cavities, demonstrating application potential in the supramolecular field; this type of macrocycle also exhibits aggregation-induced emission (AIE) properties, making it applicable to the field of organic photoluminescent materials.

Description

Technical Field

[0001] This patent application relates to the field of organic light-emitting materials technology, and more specifically, to aggregation-induced emission macrocyclic compounds, their preparation methods, and applications. Background Technology

[0002] Organic light emitters have made significant progress in fields such as sensing, anti-counterfeiting, optical communication, bioimaging, and display lighting due to their excellent material properties. Conjugated organic light emitters based on fused aromatic rings can be easily excited due to the extended π-electron system allowed by their planar conformation, and can generate strong emission in dilute solutions through radiative relaxation.

[0003] However, due to the formation of excimers, these luminescent materials suffer severe emission quenching during self-aggregation, which greatly limits their practical applications. In stark contrast, some compounds based on structurally hindered π-coupling frameworks, despite exhibiting weak luminescence in dilute solutions, display strong emission in the aggregated state, a phenomenon known as AIE (Alignment-Induced Emission), thus showing broad application prospects. To date, AIE has received extensive research and attention, and has been used to guide the synthesis and application of highly efficient aggregated-state luminescent materials.

[0004] Macrocyclic molecules, as important components of supramolecular chemistry systems, play crucial roles in host-guest chemistry, self-assembly, molecular machines, and drug delivery. Aromatic amide macrocycles, as a class of rigid planar macrocyclic molecules with hydrogen-bonded skeletons and electrically rich cavities, show potential applications in host-guest recognition, liquid crystal materials, efficient rotaxane construction, and catalysis. However, existing aromatic amide macrocycles are often difficult to synthesize, have low yields, and have limited research on luminescence. Developing a simple and efficient one-step cyclization strategy is of great significance. Summary of the Invention

[0005] To overcome one of the problems existing in the prior art, the primary objective of this patent application is to provide an aggregation-induced emission macrocyclic compound that overcomes the shortcomings of traditional aromatic amide macrocyclic synthesis, such as long synthesis steps, low yield, and weak luminescence (quantum yield less than 1%).

[0006] Another objective of this patent application is to provide a method for preparing the above-mentioned aggregation-induced emission macrocyclic compound.

[0007] Another objective of this patent application is to provide applications of the aforementioned aggregation-induced emission macrocyclic compounds.

[0008] The above-mentioned objective of this patent application is achieved through the following technical solution:

[0009] An aggregation-induced emission macrocyclic compound having one of the following molecular structures:

[0010]

[0011] Equation (I); Equation (II);

[0012]

[0013] Formula (Ⅲ);

[0014] R1 to R6 are independently selected from hydrocarbon groups of C1 to C16.

[0015] Preferably, R1 to R6 are independently selected from one of the following structures:

[0016] , , , , , , , .

[0017] More preferably, R1 to R6 are independently selected from one of the following structures: , , , .

[0018] This patent application also provides a method for preparing the above-mentioned aggregation-induced emission macrocyclic compound, comprising the following steps:

[0019] S1. Synthesize aniline derivatives (4,6-dialkoxyaniline, 4,6-dialkoxym-phenylenediamine) and benzoic acid derivatives (4,6-dialkoxybenzoic acid, 4,6-dialkoxym-phenylenediamine).

[0020] S2. The benzoic acid derivative and acylation reagent obtained in step S1 are dissolved in an organic solvent, a catalyst is added and the reaction is completed, and then post-processed. The resulting product is added to an organic solvent containing the aniline derivative and the acid-binding agent, the reaction is completed and then post-processed to obtain an aromatic amide trimer (T1 or T2) or a dimer compound (D). The structural formulas of T1, T2 and D are shown below:

[0021]

[0022]

[0023] Wherein, R1 to R6 are independently selected from hydrocarbon groups of C1 to C16.

[0024] S3. Dissolve the aromatic amide trimer or dimer obtained in step S2 in an organic solvent, add paraformaldehyde and Lewis acid and react completely. After post-treatment, the aggregation-induced emission macrocyclic compound with the structure shown in formulas (I), (II), and (III) is obtained.

[0025] Preferably, the organic solvent is dichloromethane, the acylation reagent is oxaloyl chloride, the catalyst is N,N-dimethylformamide, and the acid-binding agent is triethylamine.

[0026] Preferably, in step S2, the molar ratio of the benzoic acid derivative, acylation reagent, acid-binding agent, and aniline derivative is (1~2):(2~4):(2~4):(1~2).

[0027] Preferably, in step S3, the organic solvent is DCM, the paraformaldehyde is trioxyformaldehyde, and the Lewis acid is a boron trifluoride ether complex.

[0028] Preferably, in step S3, the molar ratio of the aromatic amide trimer / dimer compound, paraformaldehyde, and Lewis acid is 1:(0.4~0.6):(3~4).

[0029] This patent application also provides the application of the above-mentioned aggregation-induced emission macrocyclic compounds in host-guest recognition and organic photoluminescent materials.

[0030] Preferably, the applications of the above-mentioned aggregation-induced emission macrocyclic compounds in host-guest recognition and organic photoluminescent materials include applications in adsorption separation, fluorescence sensing, and light-emitting devices.

[0031] Compared with the prior art, the beneficial effects of this patent application are:

[0032] The luminescent macrocyclic AIE compound provided in this patent application uses aromatic amide trimers or dimers as building blocks, and is cyclized in one step via Friedel-Crafts reaction. The synthetic route is simple and yields high amounts, offering a new approach for constructing novel aromatic amide macrocycles. Experiments demonstrate that stable intramolecular hydrogen bonds not only restrict intramolecular motion in the aggregated state, thus endowing the macrocycle with AIE properties, but also force the carbonyl group towards the macrocycle cavity, potentially enabling strong complexation of electroless guests. Therefore, it can be applied in the field of organic photoluminescent materials and shows potential for host-guest recognition. Attached Figure Description

[0033] Figure 1 The hydrogen nuclear magnetic resonance spectrum of compound M1b prepared in Example 7 of this patent application.

[0034] Figure 2 The superimposed proton NMR spectra of compound T1b prepared in Example 3 of this patent application and compound M1b prepared in Example 7 are shown.

[0035] Figure 3 The mass spectrum of compound M1b prepared in Example 7 of this patent application is shown.

[0036] Figure 4 This is a single crystal image of compound M1b prepared in Example 7 of this patent application.

[0037] Figure 5 The fluorescence quantum yield diagram of compound M1b prepared in Example 7 of this patent application in powder form.

[0038] Figure 6 The photoluminescence spectra of compound M1b prepared in Example 7 of this patent application in mixed solutions of tetrahydrofuran / water with different water contents. Detailed Implementation

[0039] The embodiments of this patent application will be described in detail below with reference to examples. However, those skilled in the art will understand that the following examples are for illustrative purposes only and should not be construed as limiting the scope of this patent application. Where specific conditions are not specified in the examples, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0040] It should be noted that:

[0041] Unless otherwise specified, all embodiments and preferred embodiments mentioned herein can be combined to form new technical solutions.

[0042] In this patent application, unless otherwise specified, percentage (%) or parts refer to weight percentage or parts relative to the composition.

[0043] Unless otherwise specified, the components or preferred components involved in this patent application may be combined with each other to form new technical solutions.

[0044] In this patent application, unless otherwise stated, the numerical range "a~b" represents an abbreviation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "1~5" means that all real numbers between "1~5" have been listed herein, and "1~5" is simply an abbreviation of these numerical combinations.

[0045] The “scope” disclosed in this patent application may be in the form of a lower limit and an upper limit, and may be one or more lower limits and one or more upper limits, respectively.

[0046] In this patent application, unless otherwise stated, the various reactions or operation steps may be performed sequentially or in a particular order. Preferably, the reaction methods described herein are performed sequentially.

[0047] Unless otherwise stated, the technical and scientific terms used herein have the same meanings as those familiar to a person skilled in the art. Furthermore, any methods or materials similar to or equivalent to those described herein may also be used in this patent application.

[0048] This patent application provides an aggregation-induced emission macrocyclic compound having one of the following molecular structures:

[0049]

[0050] Equation (I); Equation (II);

[0051]

[0052] Formula (Ⅲ);

[0053] R1 to R6 are independently selected from hydrocarbon groups of C1 to C16.

[0054] In some preferred embodiments, R1 to R6 are independently selected from one of the following structures:

[0055] , , , , , , , .

[0056] In some preferred embodiments, R1 to R6 are independently selected from one of the following structures:

[0057] , , , .

[0058] This patent application also provides a method for preparing the above-mentioned aggregation-induced emission macrocyclic compound, comprising the following steps:

[0059] S1. Synthesize aniline derivatives (4,6-dialkoxyaniline, 4,6-dialkoxym-phenylenediamine) and benzoic acid derivatives (4,6-dialkoxybenzoic acid, 4,6-dialkoxym-phenylenediamine).

[0060] S2. The benzoic acid derivative and acylation reagent obtained in step S1 are dissolved in an organic solvent, a catalyst is added and the reaction is completed, and then post-processed. The resulting product is added to an organic solvent containing the aniline derivative and the acid-binding agent, the reaction is completed and then post-processed to obtain an aromatic amide trimer (T1 or T2) or a dimer compound (D). The structural formulas of T1, T2 and D are shown below:

[0061]

[0062]

[0063] Wherein, R1 to R6 are independently selected from hydrocarbon groups of C1 to C16.

[0064] S3. Dissolve the aromatic amide trimer or dimer obtained in step S2 in an organic solvent, add paraformaldehyde and Lewis acid and react completely. After post-treatment, the aggregation-induced emission macrocyclic compound with the structure shown in formulas (I), (II), and (III) is obtained.

[0065] The aggregation-induced emission macrocyclic compounds in this patent application are synthesized in a one-step Friedel-Crafts reaction using aromatic amide trimers or dimers as building blocks, yielding a novel class of macrocyclic luminescent compounds in high yield. The robust intramolecular hydrogen bonds endow these aromatic amide macrocycles with electron-rich cavities and the AIE effect.

[0066] Based on a rational molecular design, in the luminescent macrocyclic AIE compound of this patent application, the amide proton can form a stable intramolecular hydrogen bond with the oxygen atom of the alkoxy group adjacent to the amide bond, thereby restricting intramolecular motion in the aggregated state, reducing nonradiative relaxation, and thus exhibiting the AIE effect. Furthermore, because the plane containing the amide bond is effectively fixed, the carbonyl group is forced towards the macrocyclic cavity, which is expected to specifically bind electron-deficient guests, thus showing potential applications in the supramolecular field.

[0067] In the preparation method described in this patent application, the organic solvent is dichloromethane, the acylation reagent is oxalyl chloride, the catalyst is N,N-dimethylformamide, and the acid-binding agent is triethylamine.

[0068] In the preparation method described in this patent application, in step S2, the molar ratio of the benzoic acid derivative, acylation reagent, acid-binding agent, and aniline derivative is (1~2):(2~4):(2~4):(1~2).

[0069] In the preparation method described in this patent application, in step S3, the organic solvent is DCM, the paraformaldehyde is trioxyformaldehyde, and the Lewis acid is boron trifluoride diethyl ether complex.

[0070] In the preparation method described in this patent application, in step S3, the molar ratio of the aromatic amide trimer / dimer compound, paraformaldehyde, and Lewis acid is 1:(0.4~0.6):(3~4).

[0071] This patent application also provides the application of the above-mentioned aggregation-induced emission macrocyclic compounds in host-guest recognition and organic photoluminescent materials.

[0072] In some preferred embodiments, the above-mentioned aggregation-induced emission macrocyclic compounds are used in host-guest recognition and organic photoluminescent materials, including applications in adsorption separation, fluorescence sensing, and light-emitting devices.

[0073] The preparation method of the aggregation-induced emission macrocyclic compound in this patent application will be described in detail below with specific embodiments.

[0074] Example 1

[0075] The synthesis of 4,6-dialkoxyaniline, 4,6-dialkoxym-phenylenediamine, 4,6-dialkoxybenzoic acid, and 4,6-dialkoxyimolecular-weight phthalic acid. This patent application provides the following methods for preparing 4,6-diisobutoxym-phenylenediamine and 2,4-dibutoxybenzoic acid:

[0076]

[0077] 1,5-Difluoro-2,4-dinitrobenzene (2.0 g, 10 mmol) and triethylamine (4.0 g, 20 mmol) were dissolved in 50 mL of isobutanol and reacted at 65 °C for 12 h. The solvent was removed by filtration under reduced pressure, and the precipitate was washed three times with petroleum ether to give compound 3 (2.4 g, 77%).

[0078] Compound 3 (1.5 g, 5 mmol) and wet palladium on carbon (150 mm g) were dispersed in a mixed solvent of dichloromethane and methanol (50 mL, CH2Cl2 / CH3OH, 1:1, v / v) and stirred at room temperature for 12 h. The palladium on carbon was removed by filtration under reduced pressure, and the solvent was removed by distillation under reduced pressure to give 4,6-diisobutoxym-phenylenediamine (1.25 g, 99%).

[0079] Methyl 4,6-dihydroxybenzoate (3.4 g, 20 mmol) and potassium carbonate (11 g, 80 mmol) were dispersed in 80 mL of dry N,N-dimethylformamide (DMF) and activated at 90 °C for 1 h. Then, bromobutane (6.3 g, 46 mmol) was added, and the mixture was stirred at 110 °C for 6 h. Potassium carbonate was removed by vacuum filtration, and the solvent was removed by vacuum distillation. The mixture was extracted three times with ethyl acetate and saturated brine. The solvent was removed by vacuum distillation, and the mixture was purified by column chromatography to give compound 7 (5.4 g, 97%).

[0080] Compound 7 (2.8 g, 10 mmol) was dissolved in a mixed solvent of tetrahydrofuran (THF) and methanol (50 mL, THF / CH3OH 1:1, v / v), and then an aqueous solution of sodium hydroxide (0.8 g, 20 mmol) was added. The reaction mixture was reacted at 70 °C for 2 h. After the reaction solution was cooled to room temperature, concentrated hydrochloric acid was added to adjust the pH to 1-2. The solvent was removed by vacuum distillation, and the mixture was extracted three times with ethyl acetate and saturated brine, followed by vacuum distillation to obtain 2,4-dibutoxybenzoic acid (2.6 g, 98%).

[0081] Example 2

[0082] The synthesis of aromatic amide trimer T1a, the structural formula of which and the synthetic route are shown below:

[0083]

[0084]

[0085] 2,4-Dibutoxybenzoic acid (2.7 g, 10 mmol) and oxalyl chloride (2.5 g, 20 mmol) were dissolved in dry dichloromethane (40 mL), and dry DMF (20 μL) was added. The mixture was stirred at room temperature for 2 h. The solvent and oxalyl chloride were then removed by vacuum distillation. A solution of 4,6-dimethoxym-phenylenediamine (841 mg, 5 mmol) and triethylamine (2.0 g, 20 mmol) in dry dichloromethane was added, and the mixture was stirred at room temperature for 1 h. The solution was concentrated by vacuum distillation, and methanol was added to reprecipitate the precipitate. The precipitate was then collected by vacuum filtration to give T1a (2.6 g, 78%).

[0086] Example 3

[0087] The synthesis of aromatic amide trimer T1b, the structural formula of which and the synthetic route are shown below:

[0088]

[0089]

[0090] 2,4-Dibutoxybenzoic acid (2.7 g, 10 mmol) and oxalyl chloride (2.5 g, 20 mmol) were dissolved in dry dichloromethane (40 mL), and dry DMF (20 μL) was added. The mixture was stirred at room temperature for 2 h. The solvent and oxalyl chloride were then removed by vacuum distillation. A solution of 4,6-diisobutoxym-phenylenediamine (1260 mg, 5 mmol) and triethylamine (2.0 g, 20 mmol) in dry dichloromethane was added, and the mixture was stirred at room temperature for 1 h. The solution was concentrated by vacuum distillation, and methanol was added to reprecipitate the precipitate. The precipitate was then collected by vacuum filtration to give T1b (3.0 g, 80%).

[0091] Example 4

[0092] The synthesis of aromatic amide trimer T2, the structural formula of T1b and the synthetic route are shown below:

[0093]

[0094]

[0095] 4,6-Di(2-ethylhexyloxy)isophthalic acid (980 g, 5 mmol) and oxalyl chloride (1.3 g, 10 mmol) were dissolved in dry dichloromethane (40 mL), and dry DMF (20 μL) was added. The mixture was stirred at room temperature for 2 h. The solvent and oxalyl chloride were then removed by vacuum distillation. A solution of 2,4-dimethoxyaniline (1530 mg, 10 mmol) and triethylamine (2.0 g, 20 mmol) in dry dichloromethane was added, and the mixture was stirred at room temperature for 1 h. The solution was concentrated by vacuum distillation, and methanol was added to reprecipitate the precipitate. The precipitate was then collected by vacuum filtration to give T2 (2.9 g, 84%).

[0096] Example 5

[0097] The synthesis of aromatic amide dimer compound D, the structural formula of which and the synthetic route are shown below:

[0098]

[0099]

[0100] 2,4-Dibutoxybenzoic acid (2.7 g, 10 mmol) and oxalyl chloride (2.5 g, 20 mmol) were dissolved in dry dichloromethane (40 mL), and dry DMF (20 μL) was added. The mixture was stirred at room temperature for 2 h. The solvent and oxalyl chloride were then removed by vacuum distillation. A solution of 2,4-dimethoxyaniline (1530 mg, 10 mmol) and triethylamine (2.0 g, 20 mmol) in dry dichloromethane was added, and the mixture was stirred at room temperature for 1 h. The solution was concentrated by vacuum distillation, and methanol was added to reprecipitate the precipitate. The precipitate was then collected by vacuum filtration to give the aromatic amide dimer compound D (3.5 g, 87%).

[0101] Example 6

[0102] The synthesis of the luminescent macroring M1a, the structural formula of which and the synthetic route are shown below:

[0103]

[0104]

[0105] The T1a (665 mg, 1 mmol) prepared in Example 2 and trioxymethylene (36 mg, 0.4 mmol) were dispersed in dry dichloromethane (150 mL), and a boron trifluoride diethyl ether complex (425 mg, BF3, 48 wt%, 3 mmol) was added. The reaction was carried out at room temperature for 72 h. Then, water was added to quench the reaction, and the mixture was extracted three times with dichloromethane / water. The solvent was then removed by vacuum distillation, and the mixture was purified by column chromatography to obtain compound M1a (3.0 g, 80%).

[0106] Example 7

[0107] The synthesis of the luminescent macroring M1b, the structural formula of which and the synthesis route are shown below:

[0108]

[0109]

[0110] The T1b (749 mg, 1 mmol) prepared in Example 3 and trioxymethylene (36 mg, 0.4 mmol) were dispersed in dry dichloromethane (150 mL), and a boron trifluoride diethyl ether complex (425 mg, BF3, 48 wt%, 3 mmol) was added. The reaction was carried out at room temperature for 72 h. Then, water was added to quench the reaction, and the mixture was extracted three times with dichloromethane / water. The solvent was then removed by vacuum distillation, and the mixture was purified by column chromatography to obtain compound M1b (580 mg, 76%).

[0111] Example 8

[0112] The synthesis of the luminescent macroring M2, the structural formula of which and the synthesis route are shown below:

[0113]

[0114]

[0115] T2 (581 mg, 1 mmol) prepared in Example 4 and paraformaldehyde (36 mg, 0.4 mmol) were dispersed in dry dichloromethane (150 mL), and boron trifluoride diethyl ether complex (425 mg, BF3, 48 wt%, 3 mmol) were added. The reaction was carried out at room temperature for 72 h. Then, water was added to quench the reaction, and the mixture was extracted three times with dichloromethane / water. The solvent was then removed by vacuum distillation, and the mixture was purified by column chromatography to obtain compound M2 (494 mg, 83%).

[0116] Example 9

[0117] The synthesis of the luminescent macroring M3, the structural formula of which and the synthesis route are shown below:

[0118]

[0119]

[0120] The compound D (402 mg, 1 mmol) prepared in Example 5 and trioxymethylene (36 mg, 0.4 mmol) were dispersed in dry dichloromethane (100 mL), and a boron trifluoride diethyl ether complex (425 mg, BF3, 48 wt%, 3 mmol) was added. The reaction was carried out at room temperature for 72 h. Then, water was added to quench the reaction, and the mixture was extracted three times with dichloromethane / water. The solvent was then removed by vacuum distillation, and the mixture was purified by column chromatography to obtain compound M3 (278 mg, 67%).

[0121] Performance testing

[0122] This application uses the compound prepared in Example 7 as an example for performance testing. In the macrocyclic compounds prepared in other examples, because the amide proton can form a stable intramolecular hydrogen bond with the oxygen atom of the alkoxy group adjacent to the amide bond, on the one hand, intramolecular motion in the aggregated state is effectively suppressed, thereby reducing nonradiative relaxation and exhibiting the AIE effect; on the other hand, the intramolecular hydrogen bonding simultaneously forces the carbonyl group toward the macrocyclic cavity, which is expected to achieve strong complexation of the electron-deficient guest. Therefore, the macrocyclic compounds prepared in other examples all have the same effects as the compound obtained in Example 7.

[0123] 1H NMR spectroscopy: A Bruker Avance III 400 MHz NMR spectrometer was used, with deuterated chloroform as the solvent. Figure 1 As shown, the peak energies of the molecular proton spectrum correspond one-to-one with the target compound, and the number is reasonable. For example... Figure 2 As shown, the differences between the fragments and the macrocycle in the superimposed proton spectra further confirm the formation of the macrocycle.

[0124] Mass spectrometry detection: The M1b obtained in Example 7 was dissolved in dichloromethane to prepare a solution with a concentration of 1 mg / mL. Mass spectrometry analysis was performed using a Thermo Fisher TSQ Endura ultra-high performance liquid chromatography-tandem triple quadrupole mass spectrometer. Figure 3 As shown in the figure, the m / z value of 1522.94348 (z=2) corresponds to the complexation of one H group by each of the two M1b molecules. + The results (m / z=1522.94316) are consistent. Combining the above results of 1H NMR and mass spectrometry, it can be seen that the compound obtained in Example 7 has the structure shown in M1b.

[0125] XRD Single Crystal Diffraction Analysis: The single crystal was analyzed using an Agilent Xcalibur EX-ray single crystal diffractometer, and its crystal structure is as follows. Figure 4 As shown in the figure. The results demonstrate that the obtained diffraction structure conforms to the target macrocyclic compound M1b, and the target macrocyclic compound exhibits an electron-rich cavity, indicating its potential for effective binding with electron-deficient guests.

[0126] Fluorescence quantum yield detection: Using an Edinburgh FLS980 excitation wavelength of 365 nm, the powder prepared in Example 7 was directly used for testing. Figure 5 As shown, compound M1b exhibits blue-white light in powder form and has a fluorescence quantum efficiency of 10.96%, which is much higher than that of traditional aromatic amide macrocycles that are almost non-emitting (whose quantum yield is less than 1%).

[0127] Fluorescence emission spectroscopy detection: A multifunctional spectrometer HPX-200C-HP-DUV was used with an excitation wavelength of 330 nm. The compound obtained in Example 7 was dissolved in THF to prepare a 1×10⁻⁶ solution. -3 The mother liquor, at a concentration of mol / L, was further diluted with THF and water in different volume ratios to obtain a concentration of 1×10⁻⁶. -5 A solution of mol / L was used for testing. Figure 6 As shown, compound M1b is almost non-emissive in THF, but when the water content exceeds 50%, the luminescence of the macrocyclic compound is effectively activated and further enhanced with increasing water content, reaching a maximum at 90% water content, proving that the macrocyclic compound has a typical AIE effect.

[0128] This patent application describes a novel class of macrocyclic luminescent compounds containing aromatic amide trimers or dimers, which are cyclized in a one-step Friedel-Crafts reaction using aromatic amide trimers or dimers as building blocks, achieving high yields. The robust intramolecular hydrogen bonds endow these aromatic amide macrocycles with electron-rich cavities and the AIE effect.

[0129] Based on a rational molecular design, in the luminescent macrocyclic AIE compound of this patent application, the amide proton can form a stable intramolecular hydrogen bond with the oxygen atom of the alkoxy group adjacent to the amide bond, thereby restricting intramolecular motion in the aggregated state, reducing nonradiative relaxation, and thus exhibiting the AIE effect. Furthermore, because the plane containing the amide bond is effectively fixed, the carbonyl group is forced towards the macrocyclic cavity, which is expected to specifically bind electron-deficient guests, thus showing potential applications in the supramolecular field.

[0130] The aggregation-induced emission macrocyclic compound of this patent application combines AIE with an aromatic amide macrocycle, which can not only effectively enhance the emission of the macrocycle itself, but also endow the macrocycle with richer functions because the charged cavity is expected to specifically complex deficient guests.

[0131] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "illustrative embodiment," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with an embodiment or example is included in at least one embodiment or example of this patent application. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0132] Although several embodiments of this patent application have been shown and described, those skilled in the art will understand that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of this patent application, the scope of which is defined by the claims and their equivalents.

Claims

1. An aggregation-induced emission macrocyclic compound, characterized in that, The aggregation-induced emission macrocyclic compound has one of the following molecular structures: Equation (I); Equation (II); Wherein, R1 to R4 are independently selected from one of the following structures: 、 、 、 、 、 、 、 。 2. The aggregation-induced emission macrocyclic compound according to claim 1, characterized in that, R1 to R4 are independently selected from one of the following structures: 、 、 、 。 3. The method for preparing the aggregation-induced emission macrocyclic compound according to any one of claims 1 to 2, characterized in that, Includes the following steps: S1. Synthesizing aniline derivatives and benzoic acid derivatives, wherein the aniline derivative is 4,6-dialkoxyaniline or 4,6-dialkoxym-phenylenediamine, and the benzoic acid derivative is 4,6-dialkoxybenzoic acid or 4,6-dialkoxym-phenylenediamine; S2. The benzoic acid derivative and acylation reagent obtained in step S1 are dissolved in an organic solvent, a catalyst is added and the reaction is completed, and then post-processed. The resulting product is added to an organic solvent containing the aniline derivative and the acid-binding agent, the reaction is completed and then post-processed to obtain an aromatic amide trimer T1 or T2. The structural formulas of T1 and T2 are shown below: ； Wherein, R1 to R4 are independently selected from one of the following structures: 、 、 、 、 、 、 、 ； S3. Dissolve the aromatic amide trimer compound obtained in step S2 in an organic solvent, add paraformaldehyde and Lewis acid and react completely. After post-treatment, the aggregation-induced emission macrocyclic compound with the structure shown in formula (I) and (II) is obtained.

4. The method for preparing the aggregation-induced emission macrocyclic compound according to claim 3, characterized in that, The organic solvent in steps S2 and S3 is dichloromethane, the acylation reagent is oxalyl chloride, the catalyst is N,N-dimethylformamide, and the acid-binding agent is triethylamine.

5. The method for preparing the aggregation-induced emission macrocyclic compound according to claim 3, characterized in that, In step S2, the molar ratio of the benzoic acid derivative, acylation reagent, acid-binding agent, and aniline derivative is (1~2):(2~4):(2~4):(1~2).

6. The method for preparing the aggregation-induced emission macrocyclic compound according to claim 3, characterized in that, In step S3, the paraformaldehyde is trioxymethylene, and the Lewis acid is a boron trifluoride ether complex.

7. The method for preparing the aggregation-induced emission macrocyclic compound according to claim 3, characterized in that, In step S3, the molar ratio of the aromatic amide trimer compound, paraformaldehyde, and Lewis acid is 1:(0.4~0.6):(3~4). 。 8. The use of the aggregation-induced emission macrocyclic compound according to any one of claims 1 to 2 as an AIE material.

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