A fused heterocyclic polymer containing a biisoquinoline structure, its preparation method and application

Abstract

The application discloses a fused heterocyclic polymer containing a biisoquinoline structure and a preparation method and application thereof, and relates to the technical field of fused heterocyclic polymer preparation. The preparation method comprises the following steps: adding an internal alkyne monomer, a benzoin monomer, an ammonium salt, a rhodium catalyst, an acid and an oxidant into a solvent, and obtaining the fused heterocyclic polymer containing the biisoquinoline structure after reaction; the structural general formula of the internal alkyne monomer is as follows: the structural general formula of the benzoin monomer is as follows: the structural general formula of the fused heterocyclic polymer is as follows: R1 and R2 are independently aryl, aryl derivatives, unsubstituted alkyl or substituted alkyl; R3 and R4 are independently aryl, aryl derivatives, aliphatic groups, hydrogen atoms, halogen atoms, nitro groups, cyano groups or bioactive fragments; and x, y and z are independently integers between 1 and 200. The preparation method is simple and efficient, the target product can be obtained through only one step of reaction, the yield is high, and the raw materials used are cheap.

Description

Technical Field

[0001] This invention relates to the field of fused heterocyclic polymer preparation technology, and in particular to a fused heterocyclic polymer containing a biisoquinoline structure, its preparation method, and its application. Background Technology

[0002] Fused heterocyclic polymers containing quinoline or isoquinoline structures are an important class of functional polymers. Due to their excellent chemical stability, good mechanical properties, unique metal coordination and chelating abilities, and excellent photoelectric properties, they have attracted widespread attention in many fields, showing promising applications in stimulus-responsive polymers, high-temperature conductive polymers, electroluminescent or electrochromic devices, and bio / chemical fluorescence sensors. Among these, the preparation methods for polyquinoline materials have been relatively well-developed, and they can be obtained through oxidative polymerization or electro-oxidative polymerization of quinoline monomers. Substituent-containing polyquinolines are mostly prepared using phenylacetonitrile derivatives as raw materials via acid-catalyzed Friedlander synthesis. In recent years, two-component and multi-component cyclization polymerization based on amine monomers has also been applied to the preparation of substituted polyquinolines. In contrast, the development of methods for preparing polyisoquinoline materials remains extremely slow. Existing methods for preparing polyisoquinolines are difficult to produce functional polymers containing repeating units of biisoquinoline (a bicyclic structure formed by two isoquinoline units connected by a biphenyl bridge).

[0003] Furthermore, in current research, biisoquinoline structures mainly appear in small molecule form. These materials play a crucial role in various fields such as drug manufacturing, biomedicine, and optical applications due to their unique axial chirality and potential optical activity. Compared to small molecule materials, the physicochemical properties of polymers can be finely controlled by adjusting multiple parameters such as degree of polymerization, molecular weight distribution, topology, and morphology, while exhibiting superior mechanical strength, thermal stability, and processing performance. However, limited by existing synthetic methods for polyisoquinoline polymers, the preparation, properties, and applications of polymer materials containing biisoquinoline structures still require further exploration. Moreover, maintaining the monomer structure from racemization during synthesis to obtain chiral fused heterocyclic polymers with potential applications in chiral recognition and asymmetric catalysis remains a significant technical challenge.

[0004] Therefore, developing a simple and efficient method to prepare fused heterocyclic functional polymers containing biisoquinoline structures is of great value in both academic research and industrial applications. It will help promote the development of chiral fluorescent functional polymers with high chiral purity and superior fluorescence properties, and advance related technological fields. Summary of the Invention

[0005] In view of the shortcomings of the prior art, the purpose of this invention is to provide a fused heterocyclic polymer containing a biisoquinoline structure, its preparation method and application, and to provide a simple and efficient method to prepare fused heterocyclic functional polymers containing a biisoquinoline structure, so as to solve the problem that existing polyisoquinoline preparation methods are difficult to prepare functional polymer materials containing biisoquinoline repeating units.

[0006] The technical solution of the present invention is as follows:

[0007] A first aspect of the present invention provides a method for preparing a fused heterocyclic polymer containing a biisoquinoline structure, comprising the following steps:

[0008] An endyne monomer, a benzoyl monomer, an ammonium salt, a rhodium catalyst, an acid, and an oxidant are added to a solvent, and after reaction, the fused heterocyclic polymer containing the biisoquinoline structure is obtained.

[0009] The general structural formula of the internal alkyne monomer is shown in formula (I):

[0010]

[0011] The general structural formula of the benzoyl monomer is shown in formula (II):

[0012]

[0013] The general structural formula of the fused heterocyclic polymer containing the biisoquinoline structure is shown in formula (III):

[0014]

[0015] In formulas (I) and (III), R1 and R2 are each independently an aryl group (such as phenyl, substituted phenyl, naphthyl, substituted naphthyl, etc., but not limited to this), an aryl derivative (such as heteroaryl, specifically pyridine group, thiophene group, furan group, indole group, etc.), an unsubstituted alkyl group (such as methyl, ethyl, propyl, butyl, etc., but not limited to this), or a substituted alkyl group (e.g., alkoxy, etc., but not limited to this);

[0016] In formulas (II) and (III), R3 and R4 are located at any possible position on their respective benzene rings; R3 and R4 are each independently an aryl group, an aryl derivative, an aliphatic group (the aliphatic group can be an aliphatic group containing an ester group or an aliphatic group without an ester group; for example, the aliphatic group can be an unsubstituted alkyl group; it can also be a substituted alkyl group, such as an alkylamine group, an alkoxy group, an allyl group, an alkyl ester group, etc., but not limited thereto; the aliphatic group can also be a fatty alcohol group), a hydrogen atom, a halogen atom (such as F, Cl, Br or I, etc.), a nitro group, a cyano group, or a bioactive fragment, wherein the bioactive fragment includes one of terpenes, steroids, and vitamins;

[0017] In equation (III), x, y, and z are each an integer between 1 and 200 (specifically, they can be 1, 2, 5, 10, 15, 20, 50, 70, 80, 100, 120, 130, 150, 180, or 200, etc.).

[0018] The preparation method provided by this invention is simple and efficient, requiring only one step—a one-pot reaction of CH activation / cyclization catalyzed by rhodium—to obtain the target product. The polymerization yield is high, the raw materials are inexpensive and readily available, and the prepared fused heterocyclic polymer containing a biisoquinoline structure has a high molecular weight (weight-average molecular weight of 10,000-30,000, polymer dispersibility index of 1.2-1.8), excellent solution or aggregate fluorescence properties, and exhibits good circular dichroism signals through chiral induction. It has unique potential application value in the field of chiral fluorescent functional polymers. This invention effectively solves the problem that existing polyisoquinoline preparation methods are difficult to use to prepare functional polymers containing biisoquinoline repeating units.

[0019] In this invention, aryl and aryl derivative groups can provide a good conjugation effect, which can improve the stability of polymer molecules and regulate the luminescent properties of polymers. Aliphatic groups can adjust the solubility of polymer molecules, increase the rotational hindrance of polymer molecules, and at the same time change the polarity of molecules.

[0020] In this invention, the role of ammonium salt is to provide amino groups as a nitrogen source, the role of acid is to provide an acidic environment to promote the activation and cyclization of the reaction, and the role of oxidant is to promote catalytic cycling.

[0021] Optionally, the ammonium salt includes at least one of ammonium acetate, ammonium chloride, ammonium carbonate, and hydroxylamine hydrochloride, but is not limited thereto;

[0022] The rhodium catalyst comprises one of dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer, {(dichloro)(16bR)-1,2,3-trimethyl-2H-cyclopentyl[b]-[6,7]cyclooctane[2,1-a:3,4-a']binaphthylrhodium(III) dimer} and {(diiodo)(13bS)-7,13-dimethoxy-1,2,3,4,10,12-hexahydro-8H-cyclopentane[5,6]cyclononane[1,2,3-cd:1,9,8-c'd']spirocyclic rhodium(III) dimer}, or the rhodium catalyst comprises (13bR)H-cyclopentadien[6,7]cyclooctane[2,1-A:3,4-A']dinaphthalene, 4,7-dihydro-2,8-dimethoxy and RhCl3;

[0023] The acid includes, but is not limited to, glacial acetic acid, p-toluenesulfonic acid, benzoic acid, and tervastatin;

[0024] The oxidant includes at least one of copper acetate monohydrate, copper sulfate pentahydrate, and copper chloride, but is not limited thereto;

[0025] The solvent includes, but is not limited to, at least one of methanol, 2,2,2-trifluoroethanol, hexafluoroisopropanol, ethanol, and isopropanol.

[0026] Optionally, the reaction conditions are as follows:

[0027] Under an inert gas atmosphere or an air atmosphere, the reaction temperature is 80–120℃ (e.g., 80℃, 90℃, 100℃, 110℃ or 120℃, etc.), and the reaction time is 1–24h (e.g., 1h, 2h, 5h, 10h, 15h, 20h or 24h, etc.).

[0028] In this invention, the reaction can be carried out in an inert gas atmosphere or an air atmosphere.

[0029] Optionally, the molar ratio of the endoyne monomer, benzoyl monomer, ammonium salt, rhodium catalyst, acid, and oxidant is 1:(0.75-2):(7-14):(0.05-0.2):(6-10):(2-6); for example, the molar ratio of the endoyne monomer, benzoyl monomer, ammonium salt, rhodium catalyst, acid, and oxidant can be 1:0.75:7:0.05:6:2, 1:1:10:0.1:8:4, 1:2:14:0.2:10:6, 1:1:12:0.2:10:4, or 1:1.5:11:0.15:9:5, etc.

[0030] The reaction concentration of the endoyne monomer is 0.05–0.3 mol / L, for example, it can be 0.05 mol / L, 0.1 mol / L, 0.15 mol / L, 0.2 mol / L, 0.25 mol / L or 0.3 mol / L, etc.

[0031] Optionally, after the reaction and before obtaining the fused heterocyclic polymer containing the biisoquinoline structure, the following steps are further included:

[0032] The reaction solution obtained after the reaction was cooled to room temperature and filtered to obtain the filtrate.

[0033] The filtrate is added to a precipitant for precipitation, and then filtered and dried.

[0034] The polymer products obtained in this invention are easy to separate; a high-purity fused heterocyclic polymer containing a biisoquinoline structure can be obtained simply by precipitating it once in a precipitant.

[0035] In this invention, specifically, the reaction solution obtained after the reaction is cooled to room temperature, diluted with dichloromethane, and then simply filtered through neutral alumina to obtain a filtrate. The filtrate is then added to a precipitant for precipitation. After filtration, the precipitate is collected and dried to constant weight to obtain a fused heterocyclic polymer containing a biisoquinoline structure.

[0036] Optionally, the precipitant includes at least one of diethyl ether, acetone, and n-hexane, but is not limited thereto.

[0037] Optionally, R1 is selected from one of the following structural formulas 1 to 26, R2 is selected from one of the following structural formulas 27 to 41, and R3 and R4 are each independently selected from one of the following structural formulas 27 to 42:

[0038]

[0039]

[0040] Indicates the connection point; m, p, q, r, s, t, f are each an independent integer between 1 and 20 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20, etc.); u, v are each an independent integer between 0 and 20 (e.g., 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20, etc.);

[0041] X is an oxygen atom, a sulfur atom, or a selenium atom;

[0042] R, R', and R" are each independently a hydrogen atom, a halogen atom (such as F, Cl, Br, or I), an unsubstituted alkyl group, a substituted alkyl group (such as alkoxy, alkylamine, allyl, alkyl ester, etc., but not limited to these), a nitro group, a cyano group, an aryl group (such as phenyl, naphthyl, anthracene, etc.), an aryl derivative (such as heteroaryl, specifically pyridine, thiophene, furan, indole, etc.), or a bioactive fragment, wherein the bioactive fragment includes one of terpenes, steroids, fatty alcohols, and vitamins.

[0043] A second aspect of the present invention provides a fused heterocyclic polymer containing a biisoquinoline structure, wherein the general structural formula of the fused heterocyclic polymer containing the biisoquinoline structure is:

[0044]

[0045] R1 and R2 are each independently an aryl group, an aryl derivative, an unsubstituted alkyl group, or a substituted alkyl group (such as an alkoxy group, but not limited to this).

[0046] R3 and R4 are located at any possible position on their respective benzene rings; R3 and R4 are each independently an aryl group, an aryl derivative, an aliphatic group (the aliphatic group can be an aliphatic group containing an ester group or an aliphatic group without an ester group; for example, the aliphatic group can be an unsubstituted alkyl group; it can also be an unsubstituted alkyl group, such as an alkylamine group, an alkoxy group, an allyl group, an alkyl ester group, etc., but not limited thereto; the aliphatic group can also be a fatty alcohol group), a hydrogen atom, a halogen atom, a nitro group, a cyano group, or a bioactive fragment, wherein the bioactive fragment includes one of terpenes, steroids, and vitamins;

[0047] Each of the x, y, and z groups is an independent integer between 1 and 200 (specifically, it can be 1, 2, 5, 10, 15, 20, 50, 70, 80, 100, 120, 130, 150, 180, or 200, etc.).

[0048] Optionally, R1 is selected from one of the following structural formulas 1 to 26, R2 is selected from one of the following structural formulas 27 to 41, and R3 and R4 are each independently selected from one of the following structural formulas 27 to 42:

[0049]

[0050]

[0051] in, Indicates the connection point; m, p, q, r, s, t, f are each an independent integer between 1 and 20 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20, etc.); u, v are each an independent integer between 0 and 20 (e.g., 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20, etc.); X is an oxygen atom, a sulfur atom, or a selenium atom; R, R', and R" are each independently a hydrogen atom, a halogen atom (such as F, Cl, Br, or I), an unsubstituted alkyl group, a substituted alkyl group (e.g., alkoxy, alkylamine, allyl, alkyl ester, etc., but not limited to these), a nitro group, a cyano group, an aryl group, an aryl derivative (such as heteroaryl, specifically pyridine, thiophene, furan, indole, etc.), or a bioactive fragment, wherein the bioactive fragment includes one of terpenes, steroids, fatty alcohols, and vitamins.

[0052] A third aspect of the present invention provides the application of a fused heterocyclic polymer containing a biisoquinoline structure prepared by the preparation method described above, and / or a fused heterocyclic polymer containing a biisoquinoline structure described above, as an aggregation-induced emission material or a chiral fluorescent material.

[0053] Beneficial Effects: The preparation method provided by this invention is simple and efficient, requiring only one step—a one-pot reaction of CH activation / cyclization catalyzed by rhodium—to obtain the target product. The polymerization yield is high, the raw materials are inexpensive and readily available, and the prepared fused heterocyclic polymer containing the biisoquinoline structure has a high molecular weight (weight-average molecular weight of 10,000-30,000, polymer dispersity index of 1.2-1.8), excellent solution or aggregate fluorescence properties, and exhibits good circular dichroism signals through chiral induction. It has unique potential application value in the field of chiral fluorescent functional polymers. This invention effectively solves the problem that existing polyisoquinoline preparation methods are difficult to use to prepare functional polymers containing biisoquinoline repeating units. Attached Figure Description

[0054] Figure 1 The image shows the 1H NMR spectrum of the fused heterocyclic polymer P1 prepared in Example 1 in deuterated dichloromethane.

[0055] Figure 2 The image shows the 1H NMR spectrum of the fused heterocyclic polymer P2 prepared in Example 2 in deuterated dichloromethane.

[0056] Figure 3 The image shows the 1H NMR spectrum of the fused heterocyclic polymer P3 prepared in Example 3 in deuterated dichloromethane.

[0057] Figure 4The image shows the 1H NMR spectrum of the fused heterocyclic polymer P4 prepared in Example 4 in deuterated dichloromethane.

[0058] Figure 5 The image shows the 1H NMR spectrum of the fused heterocyclic polymer P5 prepared in Example 5 in deuterated dichloromethane.

[0059] Figure 6 The image shows the 1H NMR spectrum of the fused heterocyclic polymer P6 prepared in Example 6 in deuterated dichloromethane.

[0060] Figure 7 (A) is the photoluminescence curve of fused heterocyclic polymer P6 in Example 6 in N,N-dimethylformamide solutions with different water contents; (B) is the photoluminescence curve of fused heterocyclic polymer P5 in Example 5 in N,N-dimethylformamide solutions with different water contents; (C) is the photoluminescence curve of fused heterocyclic polymer P2 in Example 2 and fused heterocyclic polymer P4 in Example 4 in solution and aggregated states; (D) is the trend of fluorescence emission intensity change of fused heterocyclic polymer P5 in Example 5 and fused heterocyclic polymer P6 in Example 6 in N,N-dimethylformamide solutions with different water contents.

[0061] Figure 8 The absorption spectrum and circular dichroism chromatogram of the chiral fused heterocyclic polymer containing the biisoquinoline structure prepared in Example 7 in N,N-dimethylformamide solution are shown. Detailed Implementation

[0062] This invention provides a fused heterocyclic polymer containing a biisoquinoline structure, its preparation method, and its applications. To make the objectives, technical solutions, and effects of this invention clearer and more explicit, the invention is further described in detail below. It should be understood that the specific embodiments described herein are only for explaining the invention and are not intended to limit the invention.

[0063] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of this invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0064] The present invention will be further described below through specific embodiments.

[0065] Unless otherwise specified, all raw materials used in the following examples are commercially available products.

[0066] In the following examples, 4,4'-(1,4-hexendioxy)bis(diphenylacetylene) was prepared according to the method disclosed in the literature (Gao, M.; Lam, JWY; Liu, Y.; Li, J.; Tang, BZ Polymer Chemistry 2013, 4(9), 2841-2849.).

[0067] 1,1'-[1,2-bis[4-(2-phenylethynyl)phenyl]-1,2-vinyl]bisbenzene was prepared according to the method disclosed in the literature (Gao, M.; Lam, JWY; Liu, Y.; Li, J.; Tang, BZPolymer Chemistry 2013, 4(9), 2841-2849.).

[0068] Example 1

[0069] This embodiment provides a fused heterocyclic polymer containing a biisoquinoline structure (i.e., fused heterocyclic polymer P1), whose structural formula is:

[0070]

[0071] This embodiment also provides a method for preparing the above-mentioned fused heterocyclic polymer containing a biisoquinoline structure, wherein the synthetic route of the fused heterocyclic polymer containing a biisoquinoline structure is as follows:

[0072]

[0073] The preparation method of fused heterocyclic polymers containing a biisoquinoline structure includes the following steps:

[0074] Following the synthetic route described above, under air conditions, 94.1 mg of 4,4'-(1,4-hexendioxy)bis(diphenylacetylene), 42.1 mg of bibenzoyl, 185.0 mg of ammonium acetate (NH4OAc), 24.7 mg of dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer ([Cp*RhCl2]2), 160 mg of copper(II) acetate hydrate (Cu(OAc)2·H2O), and 0.114 mL of glacial acetic acid (AcOH) were dissolved in 2 mL of dry hexafluoroisopropanol (HFIP), and the reaction was stirred at 120 °C for 24 h. After the reaction was complete, the mother liquor was diluted with 2 mL of dichloromethane, filtered through a 2 cm high neutral alumina column, and then precipitated directly in 100 mL of diethyl ether solution. The precipitate was collected and dried under vacuum at 65 °C to constant weight to obtain a fused heterocyclic polymer containing a biisoquinoline structure (i.e., fused heterocyclic polymer P1), with a yield of 93.9%, an absolute weight-average molecular weight of 22800 g / mol, and a polymer dispersibility index (PDI) of 1.70.

[0075] The 1H NMR spectrum of the fused heterocyclic polymer P1 prepared in deuterated dichloromethane in Example 1 is shown below. Figure 1 As shown. From Figure 1 As can be seen, the solvent peak and water peak of deuterated dichloromethane are located at 5.32 ppm and 1.52 ppm, respectively. All other peaks are hydrogen atom signals from the fused heterocyclic polymer P1, and several characteristic hydrogen atom signals can be assigned accordingly. The peak at 4.0 ppm is a characteristic hydrogen atom peak on the methylene group attached to an oxygen atom on the alkyl chain.

[0076] Example 2

[0077] This embodiment provides a fused heterocyclic polymer containing a biisoquinoline structure (i.e., fused heterocyclic polymer P2), whose structural formula is:

[0078]

[0079] This embodiment also provides a method for preparing the above-mentioned fused heterocyclic polymer containing a biisoquinoline structure, wherein the synthetic route of the fused heterocyclic polymer containing a biisoquinoline structure is as follows:

[0080]

[0081] The preparation method of fused heterocyclic polymers containing a biisoquinoline structure includes the following steps:

[0082] Following the synthetic route described above, under air conditions, 94.1 mg of 4,4'-(1,4-hexendioxy)bis(diphenylacetylene), 65.4 mg of dimethyl 4,4'-oxaloyldibenzoate, 185.0 mg of ammonium acetate, 24.7 mg of dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer, 160 mg of copper(II) acetate hydrate, and 0.114 mL of glacial acetic acid were dissolved in 2 mL of dry hexafluoroisopropanol, and the mixture was stirred at 120 °C for 24 h. After the reaction was complete, the mother liquor was diluted with 2 mL of dichloromethane, filtered through a 2 cm high neutral alumina column, and then precipitated directly in 100 mL of diethyl ether solution. The precipitate was collected and dried under vacuum at 65 °C to constant weight to obtain a fused heterocyclic polymer containing a biisoquinoline structure (fused heterocyclic polymer P2) with a yield of 98.0%, an absolute weight-average molecular weight of 32700 g / mol, and a PDI of 1.52.

[0083] The 1H NMR spectrum of the fused heterocyclic polymer P2 prepared in deuterated dichloromethane in Example 2 is shown below. Figure 2 As shown. From Figure 2As can be seen, the solvent peak and water peak of deuterated dichloromethane are located at 5.32 ppm and 1.52 ppm, respectively. All other peaks are hydrogen atom signals from the fused heterocyclic polymer P2, and several characteristic hydrogen atom signals can be assigned accordingly. Specifically, the peak at 3.8 ppm is the characteristic peak of the methoxy group in the fused heterocyclic polymer P2, and the peak at 4.0 ppm is the characteristic peak of the hydrogen atom on the methylene group attached to the oxygen atom in the alkyl chain.

[0084] Example 3

[0085] This embodiment provides a fused heterocyclic polymer containing a biisoquinoline structure (i.e., fused heterocyclic polymer P3), whose structural formula is:

[0086]

[0087] This embodiment also provides a method for preparing the above-mentioned fused heterocyclic polymer containing a biisoquinoline structure, wherein the synthetic route of the fused heterocyclic polymer containing a biisoquinoline structure is as follows:

[0088]

[0089] The preparation method of fused heterocyclic polymers containing a biisoquinoline structure includes the following steps:

[0090] Following the synthetic route described above, under air conditions, 94.1 mg of 4,4'-(1,4-hexendioxy)bis(diphenylacetylene), 64.5 mg of 4,4-di-tert-butylbenzoyl, 185.0 mg of ammonium acetate, 24.7 mg of dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer, 160 mg of copper(II) acetate hydrate, and 0.114 mL of glacial acetic acid were dissolved in 2 mL of dry hexafluoroisopropanol, and the mixture was stirred at 120 °C for 24 h. After the reaction was complete, the mother liquor was diluted with 2 mL of dichloromethane, filtered through a 2 cm high neutral alumina column, and then directly precipitated in 100 mL of diethyl ether solution. The precipitate was collected and dried under vacuum at 65 °C to constant weight to obtain a fused heterocyclic polymer containing a biisoquinoline structure (i.e., fused heterocyclic polymer P3) with a yield of 48.8%, an absolute weight-average molecular weight of 41700 g / mol, and a PDI of 2.22.

[0091] The 1H NMR spectrum of the fused heterocyclic polymer P3 prepared in deuterated dichloromethane in Example 3 is shown below. Figure 3 As shown. From Figure 3As can be seen, the solvent peak and water peak of deuterated dichloromethane are located at 5.32 ppm and 1.52 ppm, respectively. All other peaks are hydrogen atom signals from the fused heterocyclic polymer P3, and several characteristic hydrogen atom signals can be assigned accordingly. Specifically, the peak at 1.2 ppm is the characteristic peak of the hydrogen atom of the methyl group in the fused heterocyclic polymer P3, and the peak at 4.0 ppm is the characteristic peak of the hydrogen atom of the methylene group attached to oxygen on the alkyl chain.

[0092] Example 4

[0093] This embodiment provides a fused heterocyclic polymer containing a biisoquinoline structure (i.e., fused heterocyclic polymer P4), whose structural formula is:

[0094]

[0095] This embodiment also provides a method for preparing the above-mentioned fused heterocyclic polymer containing a biisoquinoline structure, wherein the synthetic route of the fused heterocyclic polymer containing a biisoquinoline structure is as follows:

[0096]

[0097] The preparation method of fused heterocyclic polymers containing a biisoquinoline structure includes the following steps:

[0098] Following the synthetic route described above, under air conditions, 94.1 mg of 4,4'-(1,4-hexendioxy)bis(diphenylacetylene), 54.1 mg of 3,3'-dimethoxybenzoyl, 185.0 mg of ammonium acetate, 24.7 mg of dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer, 160 mg of copper(II) acetate hydrate, and 0.114 mL of glacial acetic acid were dissolved in 2 mL of dry hexafluoroisopropanol, and the mixture was stirred at 120 °C for 24 h. After the reaction was complete, the mother liquor was diluted with 2 mL of dichloromethane, filtered through a 2 cm high neutral alumina column, and then precipitated directly in 100 mL of diethyl ether solution. The precipitate was collected and dried under vacuum at 65 °C to constant weight to obtain a fused heterocyclic polymer containing a biisoquinoline structure (i.e., fused heterocyclic polymer P4) with a yield of 16.6%, an absolute weight-average molecular weight of 23100 g / mol, and a PDI of 1.48.

[0099] The 1H NMR spectrum of the fused heterocyclic polymer P4 prepared in deuterated dichloromethane in Example 4 is shown below. Figure 4 As shown. From Figure 4As can be seen, the solvent peak and water peak of deuterated dichloromethane are located at 5.32 ppm and 1.52 ppm, respectively. All other peaks are hydrogen atom signals from the fused heterocyclic polymer P4, and several characteristic hydrogen atom signals can be assigned accordingly. Specifically, the peaks at 3.3-4.2 ppm include the characteristic peaks of hydrogen atoms from the methoxy group in the fused heterocyclic polymer P4, as well as the characteristic peaks of hydrogen atoms from the methylene group attached to oxygen on the alkyl chain.

[0100] Example 5

[0101] This embodiment provides a fused heterocyclic polymer containing a biisoquinoline structure (i.e., fused heterocyclic polymer P5), whose structural formula is:

[0102]

[0103] This embodiment also provides a method for preparing the above-mentioned fused heterocyclic polymer containing a biisoquinoline structure, wherein the synthetic route of the fused heterocyclic polymer containing a biisoquinoline structure is as follows:

[0104]

[0105] The preparation method of fused heterocyclic polymers containing a biisoquinoline structure includes the following steps:

[0106] Following the synthetic route described above, under air conditions, 94.1 mg of 4,4'-(1,4-hexendioxy)bis(diphenylacetylene), 54.1 mg of 2,2-dimethoxybenzoyl, 185.0 mg of ammonium acetate, 24.7 mg of dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer, 160 mg of copper(II) acetate hydrate, and 0.114 mL of glacial acetic acid were dissolved in 2 mL of dry hexafluoroisopropanol, and the mixture was stirred at 120 °C for 24 h. After the reaction was complete, the mother liquor was diluted with 2 mL of dichloromethane, filtered through a 2 cm high neutral alumina column, and then precipitated directly in 100 mL of diethyl ether solution. The precipitate was collected and dried under vacuum at 65 °C to constant weight to obtain a fused heterocyclic polymer containing a biisoquinoline structure (i.e., fused heterocyclic polymer P5) with a yield of 89.5%, an absolute weight-average molecular weight of 21800 g / mol, and a PDI of 1.28.

[0107] The 1H NMR spectrum of the fused heterocyclic polymer P5 prepared in this embodiment in deuterated dichloromethane is shown below. Figure 5 As shown. From Figure 5As can be seen, the solvent peak and water peak of deuterated dichloromethane are located at 5.32 ppm and 1.52 ppm, respectively. All other peaks are hydrogen atom signals from the fused heterocyclic polymer P5, and several characteristic hydrogen atom signals can be assigned accordingly. The peaks at 3.3-4.1 ppm include characteristic peaks of hydrogen atoms from the methoxy group in fused heterocyclic polymer P5, as well as characteristic peaks of hydrogen atoms from the methylene group attached to oxygen on the alkyl chain. The peak at [position missing] is also a characteristic peak of hydrogen atoms from the methoxy group in fused heterocyclic polymer P5.

[0108] Example 6

[0109] This embodiment provides a fused heterocyclic polymer containing a biisoquinoline structure (i.e., fused heterocyclic polymer P6), whose structural formula is:

[0110]

[0111] This embodiment also provides a method for preparing the above-mentioned fused heterocyclic polymer containing a biisoquinoline structure, wherein the synthetic route of the fused heterocyclic polymer containing a biisoquinoline structure is as follows:

[0112]

[0113] The preparation method of fused heterocyclic polymers containing a biisoquinoline structure includes the following steps:

[0114] Under air conditions, 106.5 mg of 1,1'-[1,2-bis[4-(2-phenylethynyl)phenyl]-1,2-vinyl]bisbenzene, 42.1 mg of bibenzoyl, 185.0 mg of ammonium acetate, 24.7 mg of dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer, 160 mg of copper(II) acetate hydrate, and 0.114 mL of glacial acetic acid were added to 2 mL of dry hexafluoroisopropanol solution and dissolved. The mixture was stirred at 120 °C for 24 h. After the reaction was complete, the mother liquor was diluted with 2 mL of dichloromethane, filtered through a 2 cm high neutral alumina column, and then directly precipitated in 100 mL of diethyl ether solution. The precipitate was collected and dried under vacuum at 65 °C to constant weight to obtain a fused heterocyclic polymer containing a biisoquinoline structure (i.e., fused heterocyclic polymer P6) with a yield of 61.2%, an absolute weight-average molecular weight of 18900 g / mol, and a PDI of 1.19.

[0115] The 1H NMR spectrum of the fused heterocyclic polymer P6 prepared in this embodiment in deuterated dichloromethane is shown below. Figure 6 As shown. From Figure 6 As can be seen, the solvent peak and water peak of deuterated dichloromethane are located at 5.32 ppm and 1.52 ppm, respectively. All other peaks are P6 hydrogen atom signals.

[0116] Photoluminescence curves and fluorescence emission intensity trends of the fused heterocyclic polymers P2 (Example 2), P4 (Example 4), P5 (Example 5), and P6 (Example 6) in N,N-dimethylformamide solutions with different water contents (i.e., mixed solutions of N,N-dimethylformamide and water with different water contents, wherein the volume contents of water are 0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, and 90%, respectively). The results are as follows: Figure 7 As shown in the figure. The luminescence curves and fluorescence emission intensity trends of the fused heterocyclic polymer P6 prepared in Example 6 in N,N-dimethylformamide solutions with different water contents are shown in the figure. Figure 7 As shown in (A) and (D), where I represents the luminescence intensity in N,N-dimethylformamide solutions with different water contents and I0 represents the luminescence intensity in pure N,N-dimethylformamide solution, it can be seen that the fluorescence emission intensity of the fused heterocyclic polymer P6 gradually increases with increasing water content, and is still stronger at 90% water content than at 0% water content, proving that the fused heterocyclic polymer P6 exhibits aggregation-induced emission and has excellent aggregated state fluorescence performance. Specifically, this is due to the intramolecular motion-restricted (RIM) mechanism. In the tetraphenylethylene group, the benzene ring can rotate freely and consume energy through non-radiative pathways. However, when the tetraphenylethylene group aggregates in the polymer, these rotations return to restriction, thereby suppressing non-radiative relaxation channels and enhancing the radiative emission of the excited state.

[0117] As shown in (C) of 7, fused heterocyclic polymers P2 and P4 exhibit good fluorescence in N,N-dimethylformamide solution (solution state) with 0% water content. However, the fluorescence intensity of fused heterocyclic polymers P2 and P4 is weaker in N,N-dimethylformamide solution (aggregated state) with 90% water content than in N,N-dimethylformamide solution (solution state) with 0% water content. This indicates that fused heterocyclic polymers P2 and P4 exhibit aggregation-induced quenching effect.

[0118] As shown in (B) and (D) of 7, in N,N-dimethylformamide, the fluorescence emission intensity of fused heterocyclic polymer P5 gradually weakens with the increase of water content, exhibiting aggregation-induced quenching phenomenon. The above results indicate that fused heterocyclic polymers P2, P4, and P5 have aggregation-induced quenching properties.

[0119] Example 7

[0120] This embodiment provides a method for preparing a chiral fused heterocyclic polymer containing a biisoquinoline structure (chiral fused heterocyclic polymer P5, denoted as P5-chiral), comprising the following steps:

[0121] Under air conditions, 47.05 mg of 4,4'-(1,4-hexendioxy)bis(diphenylacetylene), 27.05 mg of 2,2-dimethoxybenzoyl, 92.5 mg of ammonium acetate, 24.76 mg of chiral catalyst {(dichloro)(16bR)-1,2,3-trimethyl-2H-cyclopentyl[b]-[6,7]cyclooctane[2,1-a:3,4-a']binaphthylrhodium(III) dimer}, 80 mg of copper(II) acetate hydrate, and 0.057 mL of glacial acetic acid were added. The acid was dissolved in 1 mL of dry hexafluoroisopropanol solution and stirred at 120 °C for 24 h. After the reaction was complete, the mother liquor was diluted with 2 mL of dichloromethane, filtered through a 2 cm high neutral alumina column, and then directly precipitated in 100 mL of diethyl ether solution. The precipitate was collected and dried under vacuum at 65 °C to constant weight to obtain a chiral fused heterocyclic polymer containing a biisoquinoline structure, namely P5-chiral, with a yield of 91.8%, an absolute weight-average molecular weight of 26500 g / mol, and a PDI of 1.38.

[0122] In this embodiment, the use of a chiral catalyst induces the formation of an optically active chiral fused heterocyclic polymer P5. Simultaneously, this embodiment also employs the same method to induce the formation of chiral fused heterocyclic polymers P3 (denoted as P3-chiral) and P4 (denoted as P4-chiral) using a chiral catalyst. The absorption spectra of P3-chiral, P4-chiral, and P5-chiral polymers in N,N-dimethylformamide solution are shown below. Figure 8 The image above) and the circular dichroism (CD) spectrum ( Figure 8 (See the image below) Figure 8 As shown. From Figure 8 The results show that the generated polymer has a positive CD signal in the 270-340 nm range, which corresponds to the absorption of the polymer, indicating that the above method has prepared a fused heterocyclic polymer with a specific axial chiral stereostructure.

[0123] In summary, this invention provides a fused heterocyclic polymer containing a biisoquinoline structure, its preparation method, and its applications. The preparation method provided by this invention is simple, requiring only one step—a one-pot reaction of CH activation / cyclization catalyzed by rhodium—to obtain the target product. The polymerization yield is good, and the raw materials used are inexpensive and readily available. The prepared fused heterocyclic polymer containing a biisoquinoline structure has a high molecular weight (weight-average molecular weight of 10,000-30,000, PDI of 12,000-18), excellent solution-state or aggregate-state fluorescence properties, and can exhibit good circular dichroism signals through chiral induction. It has unique potential application value in the field of chiral fluorescent functional polymers.

[0124] It should be understood that the application of the present invention is not limited to the examples above. Those skilled in the art can make improvements or modifications based on the above description, and all such improvements and modifications should fall within the protection scope of the appended claims.

Claims

1. A process for the preparation of a fused heterocyclic polymer containing a biisoquinoline structure, characterized by, The method comprises the following steps: adding an internal alkyne monomer, a benzil monomer, an ammonium salt, a rhodium catalyst, an acid and an oxidant into a solvent, and obtaining the fused heterocyclic polymer containing a biisoquinoline structure after reaction; The internal alkyne monomer has a structural general formula as shown in formula (I): The benzil monomer has a structural general formula as shown in formula (II): The fused heterocyclic polymer containing a biisoquinoline structure has a structural general formula as shown in formula (III): In formula (III), x, y and z are each independently an integer between 1 and 200. In formula (I) and formula (III), R1 is selected from an unsubstituted alkyl group, a substituted alkyl group or one of the following structural formula 1 to structural formula 26; R2 is selected from an unsubstituted alkyl group, a substituted alkyl group or one of the following structural formula 28 to structural formula 41. In formula (II) and formula (III), R3 and R4 are located at any possible position of the respective benzene ring; R3 and R4 are each independently an aliphatic group, a hydrogen atom, a halogen atom, a nitro group, a cyano group, a first bioactive fragment or one of the following structural formula 29 to structural formula 41, wherein the first bioactive fragment includes one of terpenes, steroids and vitamins. represents a connection; m, p, r, s, t, f are each independently an integer between 1 and 20; v is an integer between 0 and 20; X is an oxygen atom, a sulfur atom or a selenium atom; R, R' and R" are each independently a hydrogen atom, a halogen atom, an unsubstituted alkyl group, a substituted alkyl group, a nitro group, a cyano group, an aryl group or a second bioactive fragment, said second bioactive fragment comprising one of a terpenoid, a steroid, a fatty alcohol and a vitamin.

2. The production method according to claim 1, characterized by, The ammonium salt includes at least one of ammonium acetate, ammonium chloride, ammonium carbonate and hydroxylamine hydrochloride. The rhodium catalyst includes one of dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer, {(dichloro)(16bR)-1,2,3-trimethyl-2H-cyclopenta[b]-[6,7]cyclooctane[2,1-a:3,4-a']dinaphthalene rhodium(III) dimer} and {(diiodo)(13bS)-7,13-dimethoxy-1,2,3,4,10,12-hexahydro-8H-cyclopenta[5,6]cyclononane[1,2,3-cd:1,9,8-c'd']spiro rhodium(III) dimer}, or the rhodium catalyst includes (13bR)H-cyclopenta[6,7]cycloocta[2,1-A:3,4-A']dinaphthalene, 4,7-dihydro-2,8-dimethoxy and RhCl3. The acid includes at least one of glacial acetic acid, p-toluenesulfonic acid, benzoic acid and pivalic acid. The oxidant includes at least one of copper acetate monohydrate, copper sulfate pentahydrate and copper chloride. The solvent includes at least one of methanol, 2,2,2-trifluoroethanol, hexafluoroisopropanol, ethanol and isopropanol.

3. The preparation method according to claim 1, characterized in that, The reaction conditions are as follows: The reaction temperature is 80-120°C under an inert gas atmosphere or an air atmosphere, and the reaction time is 1-24h.

4. The production method according to claim 1, characterized by, The molar ratio of the internal alkyne monomer, the benzil monomer, the ammonium salt, the rhodium catalyst, the acid and the oxidant is 1:(0.75-2):(7-14):(0.05-0.2):(6-10):(2-6). The reaction concentration of the internal alkyne monomer is 0.05-0.3mol / L.

5. The preparation method according to claim 3, characterized in that, After the reaction, the method further comprises the following steps: The reaction solution obtained after the reaction is cooled to room temperature, and a filtrate is obtained after filtration. The filtrate is added into a precipitant for precipitation, and then filtration and drying are performed.

6. The production method according to claim 5, wherein The precipitant includes at least one of diethyl ether, acetone and n-hexane.

7. The method of any one of claims 1-6, wherein, R1is q is an integer between 1 and 20; or, R2 is or, R3, R4are each independently wherein u is an integer between 0 and 20.

8. A fused heterocyclic polymer containing a biisoquinoline structure, characterized by The structure general formula of the fused heterocyclic polymer containing a biisoquinoline structure is: wherein, x, y, z are each group of integers between 1 and 200; R1 is selected from unsubstituted alkyl, substituted alkyl or one of the following structural formula 1 to structural formula 26; R2 is selected from unsubstituted alkyl, substituted alkyl or one of the following structural formula 28 to structural formula 41; R3, R4 are located at any possible position on the respective benzene ring; R3, R4 are each independently an aliphatic group, a hydrogen atom, a halogen atom, a nitro group, a cyano group, a first bioactive fragment including one of terpenes, steroids and vitamins or one of the following structural formula 29 to structural formula 41; represents a connection; m, p, r, s, t, f are each independently an integer between 1 and 20; v is an integer between 0 and 20; X is an oxygen atom, a sulfur atom or a selenium atom; R, R' and R" are each independently a hydrogen atom, a halogen atom, an unsubstituted alkyl group, a substituted alkyl group, a nitro group, a cyano group, an aryl group or a second bioactive fragment, said second bioactive fragment comprising one of a terpenoid, a steroid, a fatty alcohol and a vitamin.

9. The fused heterocyclic polymer containing a biisoquinoline structure according to claim 8, wherein, R1is q is an integer between 1 and 20; or, R2 is or, R3, R4are each independently wherein u is an integer between 0 and 20.

10. Use of the fused heterocyclic polymer containing a biisoquinoline structure prepared by the preparation method of any one of claims 1-7 and / or the fused heterocyclic polymer containing a biisoquinoline structure of any one of claims 8-9 in preparation of an aggregation-induced emission material or a chiral fluorescent material.

Images