A tetraphenylethylene embedded core crown ether bicyclic compound and its synthesis method

Abstract

The present invention discloses a tetraphenylethylene-embedded core-type crown ether bicyclic compound and a synthesis method thereof. The present invention reacts a di-p-toluenesulfonyl ester-modified glycol chain with 4,4-dihydroxybenzophenone to obtain diketone and monoketone derivatives, and then respectively undergoes intramolecular or intermolecular McMurray coupling reactions to obtain a series of crown ether bicyclic molecules with aggregation-induced emission properties. Furthermore, in the crown ether bicyclic molecule of a specific structure, the production of two specific isomers (symmetrical and asymmetric structures) can be regulated by changing the equivalent ratio of zinc powder and titanium tetrachloride in the McMurray reaction. The core-embedded tetraphenylethylene crown ether bicyclic molecule provided by the present invention has excellent fluorescence properties and high fluorescence quantum yield, and the synthesis method is efficient and simple.

Description

Technical Field

[0001] The present invention belongs to the field of luminescent materials, and specifically relates to a tetraphenylethylene (TPE) embedded core-type crown ether bicyclic compound and a synthesis method thereof, specifically a method for synthesizing a class of core-embedded tetraphenylethylene crown ether bicyclic macrocyclic compounds and isomers thereof. Background Art

[0002] Fluorescent macrocyclic molecules, as important components of macrocyclic chemical systems, play a vital role in bioimaging, sensors, anti-counterfeiting materials, and other fields due to their excellent luminescence properties. The aggregation-induced emission (AIE) effect can effectively address the fluorescence quenching problem of organic luminescent molecules in the aggregated state. Tetraphenylethylene (TPE), an AIE molecule with stable optical properties, simple structure, and easy modification, serves as one of the most ideal building blocks for the construction of fluorescent macrocyclic molecules.

[0003] Crown ethers, as first-generation macrocyclic molecules, have attracted widespread attention for their unique binding selectivity and tunable binding strength for various metal ions and organic salts. However, limitations such as their simple backbone structure and lack of luminescence have hindered their further development. If crown ethers can be effectively combined with TPE groups through orthogonal design strategies, and this can be used to prepare crown ether molecules with novel structures, rich photophysical properties, and fluorescent properties, it would further expand the structural diversity of crown ethers and their application in the field of functional materials.

[0004] Based on this, the present invention provides a series of TPE-embedded core-type crown ether bicyclic molecules. One type is a cis-crown ether bicyclic CEx (x = 1-10) with identical or different cavity sizes on both sides. Furthermore, in the semi-rigid structures CE5 and CE8, by varying the amounts of zinc powder and titanium tetrachloride in the McMurray coupling reaction, the production of two specific symmetric / asymmetric stable conformers (sym-CEx and asym-CEx, x = 5, 8) can be regulated. Only a single conformation is produced in the more rigid structure CE1 and the more flexible structure CE10. Also provided are methods for synthesizing cis-crown ether bicyclic CE6 and CE7 with different cavity sizes on both sides, as well as a method for synthesizing a gem-crown ether bicyclic g-CEy (y = 4) with the same cavity size on both sides. Summary of the Invention

[0005] The purpose of the present invention is to address the problems in the prior art and provide a tetraphenylethylene (TPE) embedded core-type crown ether bicyclic compound and a synthesis method thereof. The crown ether bicyclic molecule prepared by the present invention has typical AIE properties and a high fluorescence quantum yield. By changing the feed equivalent of zinc powder and titanium tetrachloride in the McMurray reaction, two conformational isomers can be selectively synthesized in a crown ether bicyclic compound of a specific structure. The present invention synthesizes a series of diketone or monoketone molecules of different structures as raw materials and uses intramolecular or intermolecular McMurray coupling reactions. The synthesis method is simple and efficient, and is of great significance for the preparation of macrocyclic molecules with excellent fluorescence properties. Compared with TPE-modified monocyclic molecules, the TPE embedded core in the bicyclic can greatly restrict the rotation of the TPE, resulting in a macrocyclic molecule with even better aggregation-induced emission properties.

[0006] The purpose of the present invention can be achieved by the following solutions:

[0007] The present invention provides a tetraphenylethylene (TPE) embedded core crown ether bicyclic compound, which is one of a cis crown ether bicyclic compound and a gem crown ether bicyclic compound;

[0008] The general formula of cis-crown ether bicyclic compounds is as follows:

[0009]

[0010] Wherein, a and b are integers from 0 to 3 respectively;

[0011] The general formula of geminal crown ether bicyclic compounds is as follows:

[0012]

[0013] Wherein, e and f are integers ranging from 0 to 2 respectively.

[0014] The smaller the ring size of the cis-crown ether bicyclic compound in the present invention (the number of O atoms is less than 4), the more distorted the torsion angle of the core TPE benzene ring in the product structure after the intramolecular McMurray coupling reaction is, and the target product cannot be obtained. The larger the ring size (the number of O atoms is greater than 7), the more flexible the structure of the product after the intramolecular McMurray coupling reaction is, and the reaction activity is reduced, so the target product cannot be obtained. The smaller the ring size of the gem-crown ether bicyclic compound (the number of O atoms is less than 5), the less likely it is to obtain a monoketone compound connected intramolecularly due to the angle of benzophenone. The larger the ring size (the number of O atoms is greater than 7), the lower the yield of the monoketone compound, and the more likely it is a diketone compound.

[0015] As one embodiment of the present invention, the cis-crown ether bicyclic compound includes a crown ether bicyclic compound A having the same cavity size on both sides, and a crown ether bicyclic compound B having different cavity sizes on both sides;

[0016] Crown ether bicyclic compound A: a=b, an integer from 0 to 3 (a=b=0-3);

[0017] Crown ether bicyclic compound B: a≠b, an integer of 0-3 (a≠b=0-3).

[0018] As one embodiment of the present invention, when a=b=1 or a=b=2, the cis-crown ether bicyclic compound includes two isomers (symmetrical structure and asymmetric structure): a cis-symmetrical crown ether bicyclic compound and a cis-asymmetric crown ether bicyclic compound.

[0019] Preferably, as shown in Table 1 below, the cis-crown ether bicyclic compounds include compounds CE1-10, wherein CE5 includes two isomers: sym-CE5 (symmetrical) and asym-CE5 (asymmetric); CE8 includes two isomers: sym-CE8 (symmetrical) and asym-CE8 (asymmetric).

[0020] Table 1

[0021]

[0022] Preferably, the crown ether bicyclic compound A is one of the following compounds: compound CE1, compound CE5, compound CE8, compound CE10;

[0023] The details are as follows:

[0024] When a=b=0, the crown ether bicyclic compound A is compound CE1, and its specific chemical formula and crystal structure are as follows:

[0025]

[0026] When a=b=1, the crown ether bicyclic compound A is compound CE5, including compound sym-CE5 (symmetrical) and compound asym-CE5 (asymmetric);

[0027] The specific chemical formula and crystal structure of compound sym-CE5 are as follows:

[0028]

[0029] The specific chemical formula and crystal structure of the compound asym-CE5 are as follows:

[0030]

[0031] When a=b=2, the crown ether bicyclic compound A is CE8, including the compound sym-CE8 (symmetrical) and the compound asym-CE8 (asymmetric);

[0032] The specific chemical formula and crystal structure of compound sym-CE8:

[0033]

[0034] The specific chemical formula and crystal structure of compound asym-CE8:

[0035]

[0036] When a=b=3, the crown ether bicyclic compound A is compound CE10, with the specific chemical formula and crystal structure:

[0037]

[0038] Preferably, the crown ether bicyclic compound B is one of the following compounds: compound CE6, compound CE7; specifically:

[0039] When a=2 and b=1, the crown ether bicyclic compound B is compound CE6, and its specific chemical formula and crystal structure are as follows:

[0040]

[0041] When a=3 and b=1, the crown ether bicyclic compound B is compound CE7, and its specific chemical formula and crystal structure are as follows:

[0042]

[0043] As one embodiment of the present invention, the geminal crown ether bicyclic compound includes a crown ether bicyclic compound C having the same cavity size on both sides and a crown ether bicyclic compound D having different cavity sizes on both sides;

[0044] Crown ether bicyclic compound C: e=f, an integer from 0 to 2 (e=f=0-2);

[0045] Crown ether bicyclic compound D: e≠f, which is an integer from 0 to 2 (e≠f=0-2).

[0046] Preferably, as shown in Table 2 below, the geminal crown ether bicyclic compound includes compound g-CE1-6;

[0047] Table 2

[0048]

[0049] Preferably, when e=f=1, the crown ether bicyclic compound C is compound g-CE4, and its specific chemical formula and crystal structure are as follows:

[0050]

[0051] Crown ether bicyclic compound A is a type of cis-crown ether bicyclic compound (including symmetrical and asymmetrical structures) with the same cavity size on both sides of the TPE embedded core.

[0052] Crown ether bicyclic compound B is a type of cis-crown ether bicyclic compound with different cavity sizes on both sides of the TPE embedded core.

[0053] Crown ether bicyclic compound C is a geminal crown ether bicyclic compound with the same cavity size on both sides of the TPE embedded core.

[0054] Crown ether bicyclic compound D is a geminal crown ether bicyclic compound with different cavity sizes on both sides of the TPE embedded core.

[0055] The present invention also provides a method for synthesizing a tetraphenylethylene (TPE) embedded core cis-crown ether bicyclic compound (Compound A, Compound B), comprising the following steps:

[0056] Under a protective atmosphere, the compound diketone, zinc powder and anhydrous tetrahydrofuran are weighed and stirred to dissolve, the obtained mixed solution is cooled to -20 to 0°C, titanium tetrachloride is added, and after the addition is complete, the reaction solution is heated to 60-80°C and refluxed for 12-18 hours. After the reaction is completed, a saturated sodium bicarbonate solution is added to quench the reaction, the reaction solution is filtered and the filtrate is washed with water, the organic phases are collected and combined and dried over anhydrous sodium sulfate, and the obtained crude product is purified by column chromatography to obtain the TPE embedded core cis-crown ether bicyclic compound.

[0057] As an embodiment of the present invention, the protective gas is nitrogen.

[0058] As one embodiment of the present invention, the structural formula of the compound diketone is as follows:

[0059]

[0060] Wherein, m and n are integers of 2-5 respectively.

[0061] In one embodiment of the present invention, the molar ratio of the diketone, zinc powder, and titanium tetrachloride is 1 mmol: 5-40 mmol: 2.5-20 mmol. The molar ratio of zinc powder to titanium tetrachloride is preferably 2:1.

[0062] As one embodiment of the present invention, when m=n=3 or m=n=4 in the structural formula of the compound diketone, different compound diketones are selected and the amount of the raw materials is changed to obtain crown ether bicyclic compounds with different structures;

[0063] The molar ratio of the compound diketone, zinc powder and titanium tetrachloride is 1:5-10:2.5-5, and the obtained crown ether bicyclic compound is a cis-asymmetric crown ether bicyclic compound (asym-CE5, asym-CE8);

[0064] When the molar ratio of zinc powder to the diketone compound is greater than 10:1 and the molar ratio of titanium tetrachloride to the diketone compound is greater than 5:1 (the molar ratio of the diketone compound, zinc powder, and titanium tetrachloride is 1:10 to 40:5 to 20, excluding 1:10:5), the resulting crown ether bicyclic compound is a mixture of cis-asymmetric crown ether bicyclic compounds (asym-CE5, asym-CE8) and cis-symmetric crown ether bicyclic compounds (sym-CE5, sym-CE8). Under these conditions, a mixture of cis-asymmetric and symmetric crown ether bicyclic compounds is obtained, and the ratio of the two decreases with increasing zinc powder equivalents.

[0065] In the structural formula of the compound diketone, except for the case where m=n=3 or m=n=4, the molar ratio of the compound diketone, zinc powder and titanium tetrachloride is 1:5-40:2.5-20, and the obtained crown ether bicyclic compound is a cis single conformation crown ether bicyclic compound.

[0066] As a preferred embodiment, the specific examples are as follows:

[0067] Table 3

[0068]

[0069] When m=1 and n=1-5, the glycol chain length is too short, which may cause the torsion angle of the core TPE benzene ring in the product structure after the intramolecular McMurray coupling reaction to be too distorted, and thus the target product cannot be obtained.

[0070] When m>5 and n>1, the glycol chain length is too long, which may cause the product structure after the intramolecular McMurray coupling reaction to be too flexible and the reaction activity to be reduced, so the target product cannot be obtained.

[0071] As one embodiment of the present invention, the usage ratio of zinc powder and anhydrous tetrahydrofuran is 5-40 mmol:5 mL.

[0072] As one embodiment of the present invention, the stirring time is 1-3 hours.

[0073] As one embodiment of the present invention, the usage ratio of saturated sodium bicarbonate solution and zinc powder is 20 mL: 5-40 mmol.

[0074] As one embodiment of the present invention, the number of water washings is preferably 3-5 times.

[0075] As one embodiment of the present invention, the eluent used for column chromatography purification is ethyl acetate and petroleum ether in a volume ratio of 1:2 to 1:1.

[0076] As one embodiment of the present invention, when m=n, the synthesis method of the compound diketone is as follows:

[0077] Under a protective atmosphere (nitrogen), 4,4-dihydroxybenzophenone, a glycol chain modified with di-p-toluenesulfonyl ester, anhydrous potassium carbonate, and anhydrous acetonitrile were mixed and stirred under heating reflux. After the reaction, the reaction solution was washed with deionized water and extracted with dichloromethane. The organic phase was dried and dried under reduced pressure. The crude product was separated and purified by column chromatography to obtain a white solid compound, diketone.

[0078] Preferably, the structural formula of the glycol chain modified by di-p-toluenesulfonyl ester is as follows:

[0079] h is an integer from 1 to 5.

[0080] Preferably, the usage ratio of 4,4-dihydroxybenzophenone, di-p-toluenesulfonyl ester-modified glycol chain, anhydrous potassium carbonate, and anhydrous acetonitrile is 1.0 mmol: 2.1-2.5 mmol: 20-40 mmol: 10-15 mL.

[0081] Preferably, the stirring reaction temperature is 90° C. and the time is 24 hours.

[0082] Preferably, the organic phase is dried over anhydrous sodium sulfate. The reaction solution is washed three times with deionized water and then extracted three times with dichloromethane.

[0083] Preferably, the separation and purification is performed by column chromatography, and the eluents used are ethyl acetate and petroleum ether in a volume ratio of 1:2 to 1:1.

[0084] As one embodiment of the present invention, when m≠n, the synthesis method of the compound diketone is as follows:

[0085] S1. Under a protective atmosphere (nitrogen), weigh anhydrous potassium carbonate and anhydrous DMF, stir and dissolve them, heat the reaction solution, condense and reflux, slowly add a DMF mixed solution of 4,4'-dihydroxybenzophenone and di-p-toluenesulfonyl ester-modified glycol chain 1, and after the addition is complete, continue to stir the reaction solution under reflux. After the reaction is completed, filter out anhydrous potassium carbonate, concentrate under reduced pressure to remove the solvent, wash the crude product with water, extract with ethyl acetate, combine the organic phases and dry them with anhydrous sodium sulfate; the crude product is separated and purified by silica gel column chromatography to obtain a white solid product;

[0086] S2. Under a protective atmosphere (nitrogen), anhydrous potassium carbonate, the white solid product obtained in step S1, potassium iodide and anhydrous acetonitrile were weighed and stirred to dissolve, the reaction solution was heated, condensed and refluxed, and an anhydrous acetonitrile solution of the glycol chain 2 modified with di-p-toluenesulfonyl ester was slowly added dropwise. After the addition was complete, the reaction solution was stirred under reflux for 24 hours. After the reaction was completed, the solution was cooled to room temperature, the anhydrous potassium carbonate was filtered off, and the solvent was removed by concentration under reduced pressure. The crude product was washed with water, extracted with ethyl acetate, and the organic phases were combined and dried over anhydrous sodium sulfate. The crude product was separated and purified by silica gel column chromatography to obtain a white powdery solid compound diketone.

[0087] Preferably, the di-p-toluenesulfonyl ester-modified glycol chain 1 and the di-p-toluenesulfonyl ester-modified glycol chain 2 are compounds with different h values ​​in the following formula:

[0088] h is an integer from 1 to 5.

[0089] Preferably, in step S1, the ratio of anhydrous potassium carbonate, anhydrous DMF, and DMF mixed solution is 6.0 mmol:150 mL:100 mL. In 100 mL of the DMF mixed solution, the content of 4,4'-dihydroxybenzophenone is 8.0 mmol, and the content of di-p-toluenesulfonyl ester-modified glycol chain 1 is 4.0 mmol.

[0090] Preferably, in step S1, the reaction solution is heated to 100° C. and refluxed for 30 minutes, and the reaction solution is stirred under reflux for 16-24 hours.

[0091] Preferably, in step S1, the solvents used for separation and purification by silica gel column chromatography are ethyl acetate and petroleum ether in a volume ratio of 2:1.

[0092] Preferably, in step S2, the ratio of anhydrous potassium carbonate, the white solid product obtained in step S1, potassium iodide, anhydrous acetonitrile, and anhydrous acetonitrile solution is 16.94 mmol:1.02 mmol:0.08 mmol:40 mL:200 mL. The content of di-p-toluenesulfonyl ester-modified glycol chain 2 in 200 mL of anhydrous acetonitrile solution is 0.85 mmol.

[0093] Preferably, in step S2, the reaction solution is heated to 90° C. and refluxed for 30 minutes, and the reaction solution is stirred under reflux for 16-24 hours.

[0094] Preferably, in step S2, the eluent used for separation and purification by silica gel column chromatography is ethyl acetate and petroleum ether in a volume ratio of 1:2.

[0095] The present invention also provides a method for synthesizing a TPE-embedded geminal crown ether bicyclic compound (Compound C, Compound D), comprising the following steps:

[0096] Under a protective atmosphere (nitrogen), zinc powder, compound monoketone, and anhydrous tetrahydrofuran were weighed and stirred to dissolve. The reaction solution was cooled to -20-0°C, titanium tetrachloride was added, and after the addition was completed, the reaction solution was heated to 60-80°C and refluxed with stirring for 12-18 hours. After the reaction was completed, a saturated sodium bicarbonate solution was added to quench the reaction. The reaction solution was filtered and the filtrate was washed with water. The organic phases were collected and combined and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography (ethyl acetate:petroleum ether) to obtain a TPE embedded core geminal crown ether bicyclic compound.

[0097] As one embodiment of the present invention, the structural formula of the compound monoketone is as follows:

[0098]

[0099] Wherein, w is an integer of 0-3. As one embodiment of the present invention, the usage ratio of zinc powder, compound monoketone, anhydrous tetrahydrofuran, and titanium tetrachloride is 7.2 mmol:0.72 mmol:6-9 mL:3.6 mmol.

[0100] As one embodiment of the present invention, the quenching reaction is achieved by adding a saturated NaHCO3 solution. The organic phase is dried over anhydrous sodium sulfate.

[0101] As one embodiment of the present invention, the eluent used for separation and purification by column chromatography includes petroleum ether and dichloromethane in a volume ratio of 1:1 to 1:4.

[0102] As one embodiment of the present invention, the synthesis method of the monoketone compound is as follows:

[0103] Under a protective atmosphere (nitrogen), 4,4-dihydroxybenzophenone, anhydrous potassium carbonate and anhydrous acetonitrile were weighed and stirred to dissolve, the reaction solution was heated to reflux, condensed, and anhydrous acetonitrile solution of a glycol chain modified with di-p-toluenesulfonate was slowly added dropwise. After the addition was completed, the reaction solution was continued to react under reflux; after the reaction was completed, the reaction solution was filtered, the filtrate was dried, the crude product was dissolved in dichloromethane, and then washed with water, the organic phases were collected and combined and dried over anhydrous sodium sulfate, the solution was dried, and the crude product was purified by column chromatography to obtain a white solid compound monoketone.

[0104] Preferably, the ratio of 4,4-dihydroxybenzophenone, anhydrous potassium carbonate, anhydrous acetonitrile, and anhydrous acetonitrile solution is 1.0 mmol: 20.0 mmol: 250 mL: 30 mL, wherein the content of di-p-toluenesulfonate-modified glycol chains in 30 mL of anhydrous acetonitrile solution is 1.0 mmol.

[0105] Preferably, the reaction solution is heated to 80-100° C., condensed and refluxed for 1-2 hours, and then refluxed for 16-24 hours.

[0106] Preferably, the eluent used for column chromatography purification is ethyl acetate and petroleum ether in a volume ratio of 1:2 to 1:1.

[0107] The present invention also provides an application of the tetraphenylethylene (TPE) embedded core-type crown ether bicyclic compound in metal ion recognition and detection, fluorescence sensing, and light-emitting devices.

[0108] Compared with the prior art, the present invention has the following beneficial effects:

[0109] (1) Four types of crown ether bicyclic molecules with tetraphenylethylene (TPE) embedded in the core are provided. The molecules have excellent aggregation-induced emission properties and high fluorescence quantum yield.

[0110] (2) The crown ether cavities on both sides give the bicyclic molecule the host-guest complexing ability unique to crown ethers. At the same time, the size of the crown ether cavity can be controlled, and it has the ability to recognize and bind different guest molecules or metal ions.

[0111] (3) The preparation route of bicyclic molecules is simple and efficient, and crown ether bicyclic compounds with various cavity sizes can be obtained, which has universal applicability. BRIEF DESCRIPTION OF THE DRAWINGS

[0112] Other features, objects and advantages of the present invention will become more apparent upon reading the detailed description of non-limiting embodiments with reference to the following drawings:

[0113] Figure 1 For compound diketone 0 1 H NMR spectrum (400 MHz, CDCl3, 298 K);

[0114] Figure 2 For compound diketone 0 13 C NMR spectrum (100 MHz, CDCl3, 298 K);

[0115] Figure 3 For compound diketone 1 1 H NMR spectrum (400 MHz, CDCl3, 298 K);

[0116] Figure 4 For compound diketone 1 13 C NMR spectrum (100 MHz, CDCl3, 298 K);

[0117] Figure 5 is the HR-ESI-MS spectrum of compound diketone 1;

[0118] Figure 6 For compound diketone 2 1 H NMR spectrum (400 MHz, CDCl3, 298 K);

[0119] Figure 7 For compound diketone 2 13 C NMR spectrum (100 MHz, CDCl3, 298 K);

[0120] Figure 8 is the HR-ESI-MS spectrum of compound diketone 2;

[0121] Figure 9 For compound diketone 3 1 H NMR spectrum (400 MHz, CDCl3, 298 K);

[0122] Figure 10 For compound diketone 3 13 C NMR spectrum (100 MHz, CDCl3, 298 K);

[0123] Figure 11 is the HR-ESI-MS spectrum of compound diketone 3;

[0124] Figure 12 For compound diketone 4 1 H NMR spectrum (400 MHz, CDCl3, 298 K);

[0125] Figure 13 For compound diketone 4 13 C NMR spectrum (100 MHz, CDCl3, 298 K);

[0126] Figure 14 is the HR-ESI-MS spectrum of compound diketone 4;

[0127] Figure 15 The synthetic route of compound CEx (x=6,11);

[0128] Figure 16 For compound asym-CE5 1 H NMR spectrum (400 MHz, CDCl3, 298 K);

[0129] Figure 17 For compound asym-CE5 13 C NMR spectrum (100 MHz, CDCl3, 298 K);

[0130] Figure 18 HR-ESI-MS spectrum of compound asym-CE5;

[0131] Figure 19 For compound sym-CE5 1 H NMR spectrum (400 MHz, CDCl3, 298 K);

[0132] Figure 20 For compound sym-CE5 13 C NMR spectrum (100 MHz, CDCl3, 298 K);

[0133] Figure 21 is the HR-ESI-MS spectrum of compound sym-CE5;

[0134] Figure 22 For compound asym-CE8 1 H NMR spectrum (400 MHz, CDCl3, 298 K);

[0135] Figure 23 For compound asym-CE8 13 C NMR spectrum (100 MHz, CDCl3, 298 K);

[0136] Figure 24 HR-ESI-MS spectrum of compound asym-CE8;

[0137] Figure 25 For compound sym-CE8 1 H NMR spectrum (400 MHz, CDCl3, 298 K);

[0138] Figure 26 For compound sym-CE8 13 C NMR spectrum (100 MHz, CDCl3, 298 K);

[0139] Figure 27 is the HR-ESI-MS spectrum of compound sym-CE8;

[0140] Figure 28 The synthetic route of compound CEx (x = 1, 10);

[0141] Figure 29 For compound CE1 1 H NMR spectrum (400 MHz, CDCl3, 298 K);

[0142] Figure 30 Compound CE1 13 C NMR spectrum (100 MHz, CDCl3, 298 K);

[0143] Figure 31 is the HR-ESI-MS spectrum of compound CE1;

[0144] Figure 32 Compound CE10 1 H NMR spectrum (400 MHz, CDCl3, 298 K);

[0145] Figure 33 Compound CE10 13 C NMR spectrum (100 MHz, CDCl3, 298 K);

[0146] Figure 34 is the HR-ESI-MS spectrum of compound CE10;

[0147] Figure 35 The synthetic route of compound CEx (x=6,7);

[0148] Figure 36 is the synthetic route of compound 1-1;

[0149] Figure 37 Compound 1-1 1 H NMR spectrum (400 MHz, CDCl3, 298 K);

[0150] Figure 38 Compound 1-1 1 H NMR spectrum (400 MHz, DMSO-d6, 298 K);

[0151] Figure 39 Compound 1-1 13 C NMR spectrum (100 MHz, CDCl3, 298 K);

[0152] Figure 40 The synthetic route of compound diketone 5 is shown below;

[0153] Figure 41 For compound diketone 5 1 H NMR spectrum (400 MHz, CDCl3, 298 K);

[0154] Figure 42 For compound diketone 5 13 C NMR spectrum (100 MHz, CDCl3, 298 K);

[0155] Figure 43 is the HR-ESI-MS spectrum of compound diketone 5;

[0156] Figure 44 The synthetic route of compound diketone 6 is shown below;

[0157] Figure 45 For compound diketone 6 1 H NMR spectrum (400 MHz, CDCl3, 298 K);

[0158] Figure 46 For compound diketone 6 13 C NMR spectrum (100 MHz, CDCl3, 298 K);

[0159] Figure 47 is the HR-ESI-MS spectrum of compound diketone 6;

[0160] Figure 48 is the synthetic route of compound CE6;

[0161] Figure 49 For compound CE6 1 H NMR spectrum (400 MHz, CDCl3, 298 K);

[0162] Figure 50 For compound CE6 13 C NMR spectrum (100 MHz, CDCl3, 298 K);

[0163] Figure 51 is the HR-ESI-MS spectrum of compound CE6;

[0164] Figure 52 is the synthetic route of compound CE7;

[0165] Figure 53 Compound CE7 1 H NMR spectrum (400 MHz, CDCl3, 298 K);

[0166] Figure 54 Compound CE7 13 C NMR spectrum (100 MHz, CDCl3, 298 K);

[0167] Figure 55 is the HR-ESI-MS spectrum of compound CE7;

[0168] Figure 56 The synthetic route of compound g-CEy (y=1-6);

[0169] Figure 57 The synthetic route of compound monoketone 1 is shown;

[0170] Figure 58 For compound monoketone 1 1 H NMR spectrum (400 MHz, CDCl3, 298 K);

[0171] Figure 59 For compound monoketone 1 13 C NMR spectrum (100 MHz, CDCl3, 298 K);

[0172] Figure 60 is the HR-ESI-MS spectrum of compound monoketone 1;

[0173] Figure 61 is the synthetic route of compound g-CE4;

[0174] Figure 62 For compound g-CE4 1 H NMR spectrum (400 MHz, CDCl3, 298 K);

[0175] Figure 63 For compound g-CE4 13 C NMR spectrum (100 MHz, CDCl3, 298 K);

[0176] Figure 64 is the HR-ESI-MS spectrum of compound g-CE4;

[0177] Figure 65 for 1 H NMR spectra (400 MHz, CDCl3, 298 K): corresponding CE5 products under different reaction conditions;

[0178] Figure 66 for 1 H NMR spectra (400 MHz, CDCl3, 298 K): corresponding CE8 products under different reaction conditions;

[0179] Figure 67 for 1 H NMR spectra (400 MHz, CDCl3, 298 K): corresponding CE1 products under different reaction conditions;

[0180] Figure 68 for 1 H NMR spectra (400 MHz, CDCl3, 298 K): corresponding CE10 products under different reaction conditions;

[0181] Figure 69 This is the absolute fluorescence quantum yield diagram of compound sym-CE5 solid powder:

[0182] Figure 70 The fluorescence emission intensity change spectrum of compound sym-CE5 in a chloroform / acetone mixed solution (acetone content ranging from 0% to 95%);

[0183] Figure 71 is the crystal structure data of compound CE1;

[0184] Figure 72 The crystal structure data of compound sym-CE5;

[0185] Figure 73 The crystal structure data of compound asym-CE5;

[0186] Figure 74 The crystal structure data of compound asym-CE8;

[0187] Figure 75 is the crystal structure data of compound CE10;

[0188] Figure 76 is the crystal structure data of compound CE6;

[0189] Figure 77 is the crystal structure data of compound CE7;

[0190] Figure 78 The crystal structure data of compound g-CE4. DETAILED DESCRIPTION

[0191] The present invention is described in detail below with reference to the accompanying drawings and specific embodiments. The following examples are implemented under the premise of the technical solution of the present invention, provide detailed implementation methods and specific operating procedures, and will help those skilled in the art to further understand the present invention. It should be pointed out that the scope of protection of the present invention is not limited to the following embodiments, and a number of adjustments and improvements made under the premise of the concept of the present invention all fall within the scope of protection of the present invention.

[0192] Example 1

[0193] The synthesis process of diketone molecules is as follows:

[0194]

[0195] Synthesis of the diketone compound: Under nitrogen protection, a solution of 4,4-dihydroxybenzophenone (1.0 mmol), a di-p-toluenesulfonyl ester-modified glycol chain (2.5 mmol), anhydrous potassium carbonate (20.0 mmol), and anhydrous acetonitrile (10 mL) was stirred and reacted. The reaction solution was heated to 90°C and refluxed for 24 hours. After the reaction, the reaction solution was washed three times with deionized water and extracted three times with dichloromethane. The combined organic phases were dried over anhydrous sodium sulfate and dried under reduced pressure. The crude product was purified by column chromatography (ethyl acetate:petroleum ether = 2:1, v / v) to obtain the diketone compound as a white solid.

[0196] The raw materials with different m values ​​and the corresponding obtained diketone compounds are shown in Table 4 below:

[0197] Table 4

[0198]

[0199]

[0200] The details are as follows:

[0201] Compound diketone 0 (m=1):

[0202] White solid compound diketone 0 (0.12 g, yield: 22%);

[0203] Compound diketone 0 1 H NMR spectrum (400 MHz, CDCl3, 298 K) Figure 1 As shown; Compound diketone 0 13 CNMR spectrum (100MHz, CDCl3, 298K) Figure 2 As shown;

[0204] 1 H NMR (400MHz, CDCl3, 298K) δ (ppm): 7.68 (d, J = 8.7Hz, 8H), 6.91 (d, J = 8.8Hz, 8H), 4.20-4.16 (m, 8H), 3.91-3.88 (m, 8H). 13 C NMR (100MHz, CDCl3, 298K) δ (ppm): 194.3, 162.1, 132.0, 130.8, 114.3, 68.0. HR-ESI-MS: m / z [M+Na] + calcd for[C 38 H 40 O 10 Na] + 679.2519, found 679.2520.

[0205] Compound diketone 1 (m=2):

[0206] White solid compound diketone 1 (0.11 g, yield: 32%).

[0207] Compound diketone 1 1 H NMR spectrum (400 MHz, CDCl3, 298 K) Figure 2 As shown; Compound diketone 1 13 CNMR spectrum (100MHz, CDCl3, 298K) Figure 3As shown; the HR-ESI-MS spectrum of compound diketone 1 is as shown Figure 5 As shown;

[0208] 1 H NMR (400MHz, CDCl3, 298K) δ (ppm): 7.68 (d, J = 8.7Hz, 8H), 6.90 (d, J = 8.8Hz, 8H), 4.17-4.11 (m, 8H), 3.91-3.86 (m, 8H), 3.75 (s, 8H). 13 C NMR (100MHz, CDCl3, 298K) δ (ppm): 194.3, 162.1, 132.1, 130.7, 114.1, 71.0, 69.6, 67.5. HR-ESI-MS: m / z [M+Na] + calcdfor[C 38 H 40 O 10 Na] + 679.2519, found 679.2520.

[0209] Compound diketone 2 (m=3):

[0210] White solid compound diketone 2 (0.16 g, yield: 43%).

[0211] Compound diketone 2 1 H NMR spectrum (400 MHz, CDCl3, 298 K) Figure 6 As shown; Compound diketone 2 13 CNMR spectrum (100MHz, CDCl3, 298K) Figure 7 As shown; the HR-ESI-MS spectrum of compound diketone 2 is as shown Figure 8 As shown;

[0212] 1 H NMR (400MHz, CDCl3, 298K), δ (ppm): 7.69 (d, J = 8.6Hz, 8H), 6.90 (d, J = 8.6Hz, 8H), 4.13 (s, 8H), 3.89 (s, 8H), 3.72 (d, J = 8.1Hz, 16H). 13 C NMR (100MHz, CDCl3, 298K) δ (ppm): 194.3, 162.1, 132.2, 130.8, 114.0, 70.92, 70.87, 69.6, 67.7. HR-ESI-MS: m / z [M+Na] + calcd for[C 42 H 48 O12 Na] + 767.3043, found 767.3035.

[0213] Compound diketone 3 (m=4):

[0214] White solid compound diketone 3 (0.16 g, yield: 38%).

[0215] Compound diketone 3 1 H NMR spectrum (400 MHz, CDCl3, 298 K) Figure 9 As shown; Compound diketone 3 13 CNMR spectrum (100MHz, CDCl3, 298K) Figure 10 As shown; the HR-ESI-MS spectrum of compound diketone 3 is as shown Figure 11 As shown;

[0216] 1 H NMR (400MHz, CDCl3, 298K) δ (ppm): 7.71 (d, J = 8.7Hz, 8H), 6.92 (d, J = 8.7Hz, 8H), 4.18-4.13 (m, 8H), 3.88-3.85 (m, 8H), 3.73-3.66 (m, 24H). 13 C NMR (100MHz, CDCl3, 298K) δ (ppm): 194.4, 162.1, 132.2, 130.8, 114.1, 71.0, 70.7, 69.6, 67.7. HR-ESI-MS: m / z [M+H] + calcd for[C 46 H 57 O 14 ] + 833.3748, found 833.3749.

[0217] Compound diketone 4 (m=5):

[0218] Compound diketone 4 1 H NMR spectrum (400 MHz, CDCl3, 298 K) Figure 12 As shown; Compound diketone 4 13 CNMR spectrum (100MHz, CDCl3, 298K) Figure 13 As shown; the HR-ESI-MS spectrum of compound diketone 4 is as shown Figure 14 As shown;

[0219] White solid compound diketone 4 (0.16 g, yield: 35%). 1H NMR (400MHz, CDCl3, 298K) δ (ppm): 7.72 (d, J = 8.7Hz, 8H), 6.93 (d, J = 8.7Hz, 8H), 4.19-4.13 (m, 8H), 3.88-3.83 (m, 8H), 3.72-3.63 (m, 32H). 13 C NMR (100MHz, CDCl3, 298K) δ (ppm): 194.4, 162.1, 132.2, 130.8, 114.1, 70.94, 70.71, 70.69, 70.64, 69.55, 67.7. HR-ESI-MS: m / z [M+Na] + calcd for[C 50 H 64 O 16 Na] + 943.4092, found 943.4101.

[0220] Example 2

[0221] This embodiment provides a method for synthesizing a cis-crown ether bicyclic compound (compound CEx (x=5,8)) with the same cavity size on both sides of a TPE embedded core. The isomer reaction scheme is shown below ( Figure 15 ):

[0222]

[0223] (1) Compound asym-CEx (x = 5, 8):

[0224] Under nitrogen, the compound diketone (1.0 mmol), zinc powder (10.0 mmol), and anhydrous tetrahydrofuran (5 mL) prepared in Example 1 were weighed and dissolved with stirring. The reaction solution was cooled to -10°C, and titanium tetrachloride (5.0 mmol) was slowly added dropwise. After the addition was complete, stirring was continued in an ice bath for 1 hour. The reaction solution was returned to room temperature and heated to 70°C. Stirring was continued under reflux for 12 hours. After the reaction was completed, saturated sodium bicarbonate solution (20 mL) was added to quench the reaction. The reaction solution was filtered and the filtrate was washed three times with water. The organic phases were collected and combined and dried over anhydrous sodium sulfate. The organic phases were evaporated to dryness under reduced pressure to obtain a solid that was separated and purified by column chromatography (ethyl acetate:petroleum ether = 1:2, v / v) to obtain asym-CEx (x = 5, 8) as a white solid.

[0225] Using compound diketone 2, asym-CE5 (42%) was obtained; using compound diketone 3, asym-CE8 (32%) was obtained.

[0226] The specific analysis of the obtained compound is as follows:

[0227] Compound asym-CE5 (m=3):

[0228] White solid compound asym-CE5 (0.30 g, yield: 42%);

[0229] Compound asym-CE5 1 H NMR spectrum (400 MHz, CDCl3, 298 K) Figure 16 As shown; Compound asym-CE5 13 C NMR spectrum (100 MHz, CDCl3, 298 K) Figure 17 As shown; the HR-ESI-MS spectrum of compound asym-CE5 is shown Figure 18 As shown;

[0230] 1 H NMR (400MHz, CDCl3, 298K) δ (ppm): 6.91 (d, J = 8.4Hz, 8H), 6.68 (d, J = 8.6Hz, 8H), 4.19-4.15 (m, 8H), 3.78-3.74 (m, 8H), 3.62 (s, 16H). 13 C NMR (100MHz, CDCl3, 298K) δ (ppm): 157.1, 136.8, 132.5, 114.5, 71.2, 70.7, 69.8, 68.0. HR-ESI-MS: m / z [M+H] + calcdfor[C 42 H 49 O 10 ] + 713.3326, found 713.3317.

[0231] Compound asym-CE8:

[0232] White solid compound asym-CE8 (0.26 g, yield: 32%);

[0233] Compound asym-CE8 1 H NMR spectrum (400 MHz, CDCl3, 298 K) Figure 22 As shown; Compound asym-CE8 13 C NMR spectrum (100 MHz, CDCl3, 298 K) Figure 23 As shown; the HR-ESI-MS spectrum of compound asym-CE8 is as shown Figure 24 As shown;

[0234] 1H NMR (400MHz, CDCl3, 298K) δ (ppm): 6.91 (d, J = 4.8Hz, 8H), 6.65 (d, J = 8.0Hz, 8H), 4.10 (s, 8H), 3.81-3.78 (m, 8H), 3.67 (d, J = 5.5Hz, 24H). 13 C NMR (100MHz, CDCl3, 298K) δ (ppm): 157.0, 139.1, 136.8, 132.5, 114.0, 71.1, 70.7, 70.5, 69.5, 67.7. HR-ESI-MS: m / z [M+H] + calcd for[C 46 H 57 O 12 ] + 801.3850, found 801.3845.

[0235] (2) Compound sym-CEx (x = 5, 8):

[0236] Under nitrogen protection, the compound diketone (1.0 mmol), zinc powder (40.0 mmol), and anhydrous tetrahydrofuran (5 mL) prepared in Example 1 were weighed and stirred to dissolve. The reaction solution was cooled to -10°C, and titanium tetrachloride (20.0 mmol) was slowly added dropwise. After the addition was complete, stirring was continued in an ice bath for 1 hour. The reaction solution was returned to room temperature and heated to 70°C, and stirring was continued under reflux for 12 hours. After the reaction was completed, saturated sodium bicarbonate solution (20 mL) was added to quench the reaction. The reaction solution was filtered and the filtrate was washed three times with water. The organic phases were collected and combined and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography with ethyl acetate and petroleum ether (1:2, v / v) as the eluent to obtain asym-CEx, a white solid compound. Then, sym-CEx (x = 5, 8) was further obtained under the same eluent conditions.

[0237] Using compound diketone 2, asym-CE5 (4%) and sym-CE5 (32%) were obtained; using compound diketone 3, asym-CE8 (5%) and sym-CE8 (21%) were obtained.

[0238] The specific analysis of the obtained compound is as follows:

[0239] Compound sym-CE5:

[0240] White solid compound sym-CE5 (0.23 g, yield: 32%);

[0241] Compound sym-CE5 1H NMR spectrum (400 MHz, CDCl3, 298 K) Figure 19 As shown; Compound sym-CE5 13 C NMR spectrum (100 MHz, CDCl3, 298 K) Figure 20 As shown; the HR-ESI-MS spectrum of compound sym-CE5 is shown Figure 21 As shown;

[0242] 1 H NMR (400MHz, CDCl3, 298K) δ (ppm): 6.88 (d, J = 8.8Hz, 8H), 6.82 (d, J = 8.8Hz, 8H), 4.25-4.20 (m, 8H), 3.79-3.76 (m, 8H), 3.64 (s, 16H). 13 C NMR (100MHz, CDCl3, 298K) δ (ppm): 157.3, 134.7, 131.1, 115.1, 71.2, 70.9, 70.3, 68.7. HR-ESI-MS: m / z [M+H] + calcdfor[C 42 H 49 O 10 ] + 713.3326, found 713.3363.

[0243] Compound sym-CE8:

[0244] White solid compound sym-CE8 (0.17 g, yield: 21%).

[0245] Compound sym-CE8 1 H NMR spectrum (400 MHz, CDCl3, 298 K) Figure 25 As shown; Compound sym-CE8 13 C NMR spectrum (100 MHz, CDCl3, 298 K) Figure 26 As shown; the HR-ESI-MS spectrum of compound sym-CE8 is as shown Figure 27 As shown;

[0246] 1 H NMR (400MHz, CDCl3, 298K) δ (ppm): 6.87 (d, J = 8.1Hz, 8H), 6.78 (d, J = 8.3Hz, 8H), 4.18 (s, 8H), 3.81 (s, 8H), 3..68 (d, J = 11.3Hz, 24H). 13C NMR (100MHz, CDCl3, 298K) δ (ppm): 157.2, 134.7, 131.1, 114.5, 71.1, 70.7, 70.6,, 69.8, 68.0. HR-ESI-MS: m / z [M+Na] + calcd for[C 46 H 56 O 12 Na] + 823.3669, found 823.3681.

[0247] Example 3

[0248] This embodiment provides a method for synthesizing a cis-crown ether bicyclic compound (CEx, x=1, 10) with the same cavity size on both sides of a TPE embedded core. The reaction scheme is as follows ( Figure 28 ):

[0249]

[0250] Compound CEx (x = 1, 10): Under nitrogen, dissolve the diketone compound (1.0 mmol), zinc powder (10.0 mmol), and anhydrous tetrahydrofuran (5 mL) in a stirred solution. The reaction mixture was cooled to -10°C and titanium tetrachloride (5.0 mmol) was slowly added dropwise. Stirring continued in an ice bath for 1 hour after the addition was complete. The reaction mixture was allowed to return to room temperature and then heated to 70°C, where it was stirred under reflux. After completion, saturated sodium bicarbonate solution (20 mL) was added to quench the reaction. The reaction mixture was filtered and the filtrate was washed three times with water. The organic phases were combined and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography (eluent: ethyl acetate:petroleum ether = 1:2, v / v) to obtain Compound CEx (x = 1, 10) as a white solid.

[0251] Using compound diketone 1, compound CE1 (33%) was obtained; using compound diketone 4, compound CE10 (29%) was obtained.

[0252] The specific analysis of the obtained compound is as follows:

[0253] Compound CE1:

[0254] White solid compound CE1 (0.21 g, yield: 33%).

[0255] Compound CE1 1 H NMR spectrum (400 MHz, CDCl3, 298 K) Figure 29 As shown; Compound CE1 13C NMR spectrum (100 MHz, CDCl3, 298 K) Figure 30 As shown; the HR-ESI-MS spectrum of compound CE1 is as shown Figure 31 As shown;

[0256] 1 H NMR (400MHz, CDCl3, 298K) δ (ppm): 6.90 (d, J = 3.5Hz, 8H), 6.71 (d, J = 8.2Hz, 8H), 4.25 (s, 8H), 3.73-3.70 (m, 8H), 3.55 (s, 8H). 13 C NMR (100MHz, CDCl3, 298K) δ (ppm): 157.2, 140.2, 136.5, 132.3, 115.2, 71.4, 70.8, 68.5. HR-ESI-MS: m / z [M+Na] + calcd for[C 38 H 40 O8Na] + 647.2621, found 647.2614.

[0257] Compound CE10:

[0258] Yellow solid compound CE10 (0.26 g, yield: 29%).

[0259] Compound CE10 1 H NMR spectrum (400 MHz, CDCl3, 298 K) Figure 32 As shown; Compound CE10 13 CNMR spectrum (100MHz, CDCl3, 298K) Figure 33 As shown; the HR-ESI-MS spectrum of compound CE10 is as shown Figure 34 As shown;

[0260] 1 H NMR (400MHz, CDCl3, 298K) δ (ppm): 6.90 (d, J = 8.6Hz, 8H), 6.65 (d, J = 8.7Hz, 8H), 4.10-4.04 (m, 8H), 3.83-3.79 (m, 8H), 3.67 (d, J = 11.1Hz, 32H). 13 C NMR (100MHz, CDCl3, 298K) δ (ppm): 156.0, 137.7, 135.8, 131.5, 112.7, 69.96, 69.82, 69.66, 69.62, 68.6, 66.3. HR-ESI-MS: m / z [M+Na] +calcd for[C 50 H 64 O 14 Na] + 911.4194, found 911.4189.

[0261] Example 4

[0262] This embodiment provides a method for synthesizing a cis-crown ether bicyclic compound (CEx, x=6, 7) with different cavities on both sides of a TPE embedded core. The synthetic route is shown below ( Figure 35 ):

[0263]

[0264] 1. The synthesis process of compound 1-1 is as follows ( Figure 36 ):

[0265]

[0266] Under nitrogen, anhydrous potassium carbonate (0.8 g, 6.0 mmol) and anhydrous DMF (150 mL) were stirred and dissolved. The reaction mixture was heated to 100°C and refluxed for 30 minutes. A mixture of 4,4'-dihydroxybenzophenone (1.72 g, 8.0 mmol) and tetraethylene glycol di-p-toluenesulfonate (2.0 g, 4.0 mmol) in DMF (100 mL) was slowly added dropwise. After the addition was complete, the reaction mixture was stirred under reflux. After the reaction was complete, the anhydrous potassium carbonate was filtered off, and the solvent was concentrated under reduced pressure. The crude product was washed three times with water, extracted with ethyl acetate, and the organic phases were combined and dried over anhydrous sodium sulfate. The crude product was purified by silica gel column chromatography (ethyl acetate:petroleum ether = 2:1, v / v) to obtain the white solid product 1-1 (0.75 g, yield: 32%).

[0267] Compound 1-1 1 H NMR spectrum (400 MHz, CDCl3, 298 K) Figure 37 As shown; Compound 1-1 1 H NMR spectrum (400 MHz, DMSO-d6, 298 K) Figure 38 As shown; Compound 1-1 13 C NMR spectrum (100 MHz, CDCl3, 298 K) Figure 39 As shown;

[0268] 1H NMR (400MHz, CDCl3, 298K) δ (ppm): 7.68 (dd, J=14.1, 8.5Hz, 8H), 6.88 (dd, J=1 0.7,8.8Hz,8H),4.17-4.10(m,4H),3.89-3.84(m,4H),3.73(d,J=5.5Hz,8H). 1 HNMR (400MHz, DMSO-d6, 298K) δ (ppm): 10.30 (s, 2H), 7.65 (d, J = 8.2Hz, 4H), 7.60 (d, J = 8.1Hz, 4H ),7.05(d,J=8.2Hz,4H),6.87(d,J=7.9Hz,4H),4.17(s,4H),3.77(s,4H),3.57(d,J=8.8Hz,8H). 13 C NMR (100MHz, CDCl3, 298K) δ (ppm): 194.88, 162.84, 161.95, 161.44, 132.54, 132.15, 130.94, 129.38, 115.26, 114.01, 70.79, 70.61, 69.53, 67.55.

[0269] 2. The synthesis process of compound diketone 5 is as follows ( Figure 40 ):

[0270]

[0271] Under nitrogen, anhydrous potassium carbonate (2.34 g, 16.94 mmol), compound 1-1 (0.57 g, 1.02 mmol), potassium iodide (0.16 g, 0.08 mmol), and anhydrous acetonitrile (40 mL) were stirred and dissolved. The reaction solution was heated to 90°C and refluxed for 30 minutes. A solution of tetraethylene glycol di-p-toluenesulfonate (0.50 g, 0.85 mmol) in anhydrous acetonitrile (200 mL) was slowly added dropwise. After the addition was complete, the reaction solution was stirred under reflux for 24 hours. After the reaction was completed, the reaction solution was cooled to room temperature. The anhydrous potassium carbonate was filtered off, and the solvent was removed by concentration under reduced pressure. The crude product was washed three times with water and extracted with ethyl acetate. The organic phases were combined and dried over anhydrous sodium sulfate. The crude product was purified by silica gel column chromatography (ethyl acetate:petroleum ether = 1:2, v / v) to obtain diketone 5 as a white powdery solid (0.36 g, yield: 44%).

[0272] Compound diketone 5 1 H NMR spectrum (400 MHz, CDCl3, 298 K) Figure 41 As shown; Compound diketone 5 13CNMR spectrum (100MHz, CDCl3, 298K) Figure 42 As shown; the HR-ESI-MS spectrum of compound diketone 5 is as shown Figure 43 As shown;

[0273] 1 H NMR (400MHz, CDCl3, 298K) δ (ppm): 7.70 (d, J = 8.0Hz, 8H), 6.92 (d, J = 8.3Hz, 8H ), 4.14 (d, J = 6.1Hz, 8H), 3.88 (d, J = 3.4Hz, 8H), 3.70 (dd, J = 10.4, 9.2Hz, 20H). 13 C NMR(100MHz,CDCl3,298K)δ(ppm):194.30,162.05,132.17,130.76,130.73,11 4.04,70.98,70.91,70.84,70.75,69.56,67.69,67.67.HR-ESI-MS:m / z[M+Na] + calcd.for[C 44 H 52 O 13 Na] + 811.3306, found 811.3303.

[0274] 3. The synthesis process of compound diketone 6 is as follows ( Figure 44 ):

[0275]

[0276] Under nitrogen, anhydrous potassium carbonate (1.95 g, 14.14 mmol), compound 1-1 (0.48 g, 0.85 mmol), potassium iodide (0.01 g, 0.07 mmol), and anhydrous acetonitrile (50 mL) were stirred and dissolved. The reaction solution was heated to 90°C and refluxed for 30 minutes. A solution of pentaethylene glycol bis(p-toluenesulfonate) (0.42 g, 0.70 mmol) in anhydrous acetonitrile (100 mL) was slowly added dropwise. After the addition was complete, the reaction solution was stirred under reflux for 24 hours. After the reaction was completed, the reaction solution was cooled to room temperature. The anhydrous potassium carbonate was filtered off, and the solvent was removed by concentration under reduced pressure. The crude product was washed three times with water, extracted with ethyl acetate, and the organic phases were combined and dried over anhydrous sodium sulfate. The crude product was purified by silica gel column chromatography (ethyl acetate:petroleum ether = 1:1, v / v) to obtain diketone 6 as a white powdery solid (0.32 g, yield: 63%).

[0277] Compound diketone 6 1H NMR spectrum (400 MHz, CDCl3, 298 K) Figure 45 As shown; Compound diketone 6 13 CNMR spectrum (100MHz, CDCl3, 298K) Figure 46 As shown; the HR-ESI-MS spectrum of compound diketone 6 is as shown Figure 47 As shown;

[0278] 1 H NMR (400MHz, CDCl3, 298K) δ (ppm): 7.70 (d, J = 8.7Hz, 8H), 6.91 (d, J = 8.6Hz, 8H), 4.19-4.09 (m, 8H), 3.90-3.83 (m, 8H), 3.73-3.59 (m, 24H). 13 C NMR (100MHz, CDCl3, 298K) δ (ppm): 194.30, 162.10, 132.16, 130.86, 130.80, 114.1 1,70.97,70.86,70.75,70.70,69.61,69.58,67.75,67.71.HR-ESI-MS:m / z[M+Na] + calcd.for[C 46 H 57 O 14 ] + 833.3748, found 833.3750.

[0279] 4. The synthesis process of compound CE6 is as follows ( Figure 48 ):

[0280]

[0281] Under nitrogen, zinc powder (0.08 g, 1.27 mmol), compound diketone 5 (0.10 g, 0.13 mmol), and anhydrous tetrahydrofuran (5 mL) were weighed and dissolved with stirring. The reaction solution was cooled to -20°C, and titanium tetrachloride (0.07 mL, 0.63 mmol) was slowly added. After the addition was complete, the reaction solution was heated to 80°C and refluxed for 12 hours. After the reaction was completed, saturated NaHCO3 solution (20 mL) was added to quench the reaction. The mixture was filtered and separated by extraction. The organic phases were combined and dried over anhydrous sodium sulfate. The solvent was then evaporated to dryness to obtain the crude product, which was separated and purified by column chromatography (petroleum ether:dichloromethane = 1:1, v / v) to obtain Compound CE6 as a white solid (0.02 g, yield: 19%).

[0282] Compound CE6 1H NMR spectrum (400 MHz, CDCl3, 298 K) Figure 49 As shown; Compound CE6 13 C NMR spectrum (100 MHz, CDCl3, 298 K) Figure 50 As shown; the HR-ESI-MS spectrum of compound CE6 is shown Figure 51 As shown;

[0283] 1 H NMR (400MHz, CDCl3, 298K) δ (ppm): 6.91 (t, J=8.9Hz, 8H), 6.66 (dd, J=8.5, 5.4Hz, 8H ),4.19-4.14(m,4H),4.13-4.08(m,4H),3.81-3.75(m,8H),3.65(t,J=11.3Hz,20H). 13 C NMR (100MHz, CDCl3, 298K) δ (ppm): 157.08, 157.01, 139.25, 137.00, 136.60, 132.47, 114.42, 114.04,71.21,71.12,70.69,70.66,70.50,69.70,69.52,67.97,67.71.HR-ESI-MS:m / z[M+H] + calcd.for[C 44 H 53 O 11 ] + 757.3588, found 757.3589.

[0284] 5. The synthesis process of compound CE7 is as follows ( Figure 52 ):

[0285]

[0286] Under nitrogen, zinc powder (0.3 g, 4.8 mmol), compound diketone 6 (0.10 g, 0.12 mmol), and anhydrous tetrahydrofuran (5 mL) were weighed and dissolved with stirring. The reaction solution was cooled to -20°C, and titanium tetrachloride (0.07 mL, 0.63 mmol) was slowly added. After the addition was complete, the reaction solution was heated to 80°C and refluxed for 12 hours. After the reaction was completed, saturated NaHCO3 solution (20 mL) was added to quench the reaction. The mixture was filtered and separated by extraction. The organic phases were combined and dried over anhydrous sodium sulfate. The solvent was then evaporated to dryness to obtain the crude product, which was separated and purified by column chromatography (petroleum ether:dichloromethane = 1:2, v / v) to obtain Compound CE7 as a white solid (0.06 g, yield: 19%).

[0287] Compound CE7 1 H NMR spectrum (400 MHz, CDCl3, 298 K) Figure 53 As shown; Figure 54 Compound CE7 13 CNMR spectrum (100MHz, CDCl3, 298K) Figure 54 As shown; Figure 55 The HR-ESI-MS spectrum of compound CE7 is shown in Figure 2. Figure 55 As shown;

[0288] 1 H NMR (400MHz, CDCl3, 298K) δ (ppm): 6.90 (br d, 8H), 6.66 (d, J = 5.1Hz, 8H), 4.11 (br d, 8H), 3.83-3.73 (m, 8H), 3.69-3.61 (m, 24H). 13 C NMR (100MHz, CDCl3, 298K) δ (ppm): 157.2, 139.1, 137.2, 136.4, 132.5, 115.6, 115.1, 114.1, 71.4, 70.5, 69.7, 68.0, 67.4. HR-ESI-MS: m / z [M+H] + calcd.for[C 46 H 56 O 12 Na] + 823.3669, found 823.3684.

[0289] Example 5

[0290] This embodiment provides a method for synthesizing a TPE-embedded geminal crown ether bicyclic compound (g-CEy, y=1-6). The synthetic route is shown below ( Figure 56 ):

[0291]

[0292] 1. The synthesis process of compound monoketone 1 is as follows ( Figure 57 ):

[0293]

[0294] Under nitrogen protection, 4,4-dihydroxybenzophenone (0.21 g, 1.0 mmol), anhydrous potassium carbonate (2.76 g, 20.0 mmol), and anhydrous acetonitrile (250 mL) were weighed and stirred to dissolve. The reaction solution was heated to 90°C and refluxed for 1 hour. A solution of tetraethylene glycol bis(p-toluenesulfonate) (0.26 g, 0.5 mmol) in anhydrous acetonitrile (30 mL) was slowly added dropwise. After the addition was complete, the reaction solution was refluxed for 24 hours. After the reaction was completed, the reaction solution was filtered, the filtrate was dried, and the crude product was dissolved in dichloromethane (50 mL) and washed with water (100 mL × 3). The organic phases were collected and combined and dried over anhydrous sodium sulfate. After the solution was dried, the crude product was purified by column chromatography (ethyl acetate: petroleum ether = 1:2, v / v) to obtain a white solid compound monoketone 1 (0.12 g, yield: 30%).

[0295] Compound monoketone 1 1 H NMR spectrum (400 MHz, CDCl3, 298 K) Figure 58 As shown; Compound monoketone 1 13 CNMR spectrum (100MHz, CDCl3, 298K) Figure 59 As shown; the HR-ESI-MS spectrum of compound monoketone 1 is as shown Figure 60 As shown;

[0296] 1 H NMR (400MHz, CDCl3, 298K) δ (ppm): 7.69 (d, J = 8.8Hz, 4H), 7.17 (d, J = 8.8Hz, 4H), 4 .43-4.37(m,4H),3.82-3.77(m,4H),3.64(s,,4H),3.57(dd,J=13.3,5.3Hz,8H). 13 CNMR(100MHz,CDCl3,298K)δ(ppm):195.26,162.65,131.77,131.11,115.60,71.52,70.90,70.88,70.34,68.35.HR-ESI-MS:m / z[M+H] + calcd.for[C 23 H 29 O7] + 417.1913,found417.1917.

[0297] 2. The synthesis process of compound g-CE4 is as follows ( Figure 61 ):

[0298]

[0299] Under nitrogen, zinc powder (0.48 g, 7.2 mmol), compound monoketone 1 (0.30 g, 0.72 mmol), and anhydrous tetrahydrofuran (9 mL) were weighed and dissolved with stirring. The reaction solution was cooled to -20°C, and titanium tetrachloride (0.39 mL, 3.6 mmol) was slowly added. After the addition was complete, the reaction solution was heated to 80°C and refluxed with stirring for 12 hours. After the reaction was completed, saturated NaHCO3 solution (20 mL) was added to quench the reaction. The mixture was filtered and separated by extraction. The organic phases were combined and dried over anhydrous sodium sulfate. The solvent was then evaporated to dryness to obtain the crude product, which was separated and purified by column chromatography (petroleum ether:dichloromethane = 1:2, v / v) to obtain compound g-CE4 as a white solid (0.09 g, yield: 30%).

[0300] Compound g-CE4 1 H NMR spectrum (400 MHz, CDCl3, 298 K) Figure 62 As shown; Compound g-CE4 13 CNMR spectrum (100MHz, CDCl3, 298K) Figure 63 As shown; the HR-ESI-MS spectrum of compound g-CE4 is as shown Figure 64 As shown;

[0301] 1 H NMR (400MHz, CDCl3, 298K) δ (ppm): 6.89 (d, J = 8.6 Hz, 8H), 6.76 (d, J = 8.6 Hz, 8H), 4.26 -4.22(m,8H),3.76-3.72(m,8H),3.59-3.56(m,8H),3.49-3.45(m,8H),3.38(s,8H). 13 C NMR (100MHz, CDCl3, 298K) δ (ppm): 157.07, 138.00, 137.26, 132.08, 115.01, 70.92, 70.62, 70.51, 70.45, 67.85. HR-ESI-MS: m / z [M+H] + calcd.for[C 46 H 57 O 12 ] + 801.3850, found801.3857.

[0302] Example 6

[0303] The synthesis method of compound CEx (x=5,8) in this example is basically the same as that in Example 2, and compounds with other proportions (compound diketone, zinc powder, titanium tetrachloride) are prepared, as shown in Table 5 below:

[0304] Table 5

[0305]

[0306] Under different reaction conditions, the corresponding CE5 products 1 H NMR spectrum (400 MHz, CDCl3, 298 K) Figure 65 As shown; under different reaction conditions, the corresponding CE8 products 1 H NMR spectrum (400 MHz, CDCl3, 298 K) Figure 66 shown.

[0307] It can be found that in the preparation method described in the present application, in the step, when the molar ratio of diketone 2 (diketone 3): zinc powder: titanium tetrachloride is 1:10:5, the nuclear magnetic resonance spectrum shows that the obtained product is asym-CE5 (asym-CE8).

[0308] In the preparation method described in this patent application, in the step, when the molar ratio of diketone 2 (diketone 3): zinc powder: titanium tetrachloride is 1:40:20, the nuclear magnetic resonance spectrum shows that the main product obtained is sym-CE5 (sym-CE8).

[0309] Example 6

[0310] The synthesis method of compound CEx (x=1, 10) in this example is basically the same as that in Example 3. Compounds with other proportions (compound diketone, zinc powder, titanium tetrachloride) were prepared, as shown in Table 6 below:

[0311] Table 6

[0312]

[0313] Under different reaction conditions, the corresponding CE1 products 1 H NMR spectrum (400 MHz, CDCl3, 298 K) Figure 67 As shown; under different reaction conditions, the corresponding CE10 products 1 H NMR spectrum (400 MHz, CDCl3, 298 K) Figure 61 shown.

[0314] It can be found that in the preparation method described in the present invention, in the steps, when the molar ratio of diketone 1 (diketone 4): zinc powder: titanium tetrachloride is 1:10:5 and 1:40:20, the nuclear magnetic resonance spectrum shows that the obtained products are all single conformation CE1 (CE10).

[0315] Application Examples

[0316] Fluorescence quantum yield test: The solid powder was directly tested using an Edinburgh FLS1000 steady-state transient fluorescence spectrometer with an excitation wavelength of 350 nm. Figure 69 Absolute fluorescence quantum yield of compound sym-CE5 solid powder:

[0317] The fluorescence quantum yield of sym-CE5 is 27.92%, indicating that compound sym-CE5 has excellent aggregation-induced emission properties and high fluorescence quantum yield.

[0318] Fluorescence emission spectrum test: using Edinburgh FLS1000 steady-state transient fluorescence spectrometer, the excitation wavelength was 350nm, and the compound sym-CE5 was dissolved in chloroform to a concentration of 1×10 -3 mol / L stock solution was further diluted to 2×10 -5 mol / L solution for testing.

[0319] Fluorescence emission intensity change spectrum of compound sym-CE5 in chloroform / acetone mixed solution (acetone content ranging from 0% to 95%):

[0320] like Figure 70 As shown in the figure, compound sym-CE5 has a certain degree of fluorescence emission in chloroform solution. With the increase of the content of poor solvent acetone, the fluorescence intensity of compound sym-CE5 gradually increases and reaches the maximum value when the acetone content is 90%, indicating that compound sym-CE5 has typical aggregation-induced emission properties.

[0321] XRD single crystal diffraction test: A Bruker D8 350 X-ray single crystal diffractometer was used to test the single crystal of the compound.

[0322] The crystal structure data of compound CE1 are as follows Figure 71 As shown;

[0323] The crystal structure data of compound sym-CE5 are as follows Figure 72 As shown;

[0324] The crystal structure data of compound asym-CE5 are as follows Figure 73 As shown;

[0325] The crystal structure data of compound asym-CE8 are as follows Figure 74 As shown;

[0326] The crystal structure data of compound CE10 are as follows Figure 75 As shown;

[0327] The crystal structure data of compound CE6 are as follows Figure 76 As shown;

[0328] The crystal structure data of compound CE7 are as follows Figure 77 As shown;

[0329] The crystal structure data of compound g-CE4 are as follows Figure 78 As shown;

[0330] The above describes the specific embodiments of the present invention. It should be understood that the present invention is not limited to the above specific embodiments, and those skilled in the art may make various variations or modifications within the scope of the claims, which do not affect the essence of the present invention.

Claims

1. A tetraphenylethylene embedded core crown ether bicyclic compound, characterized in that: It is one of the cis-crown ether bicyclic compounds and gem-crown ether bicyclic compounds; The general formula of cis-crown ether bicyclic compounds is as follows: ， Wherein, a and b are integers from 0 to 3 respectively; The general formula of geminal crown ether bicyclic compounds is as follows: ， Wherein, e and f are integers ranging from 0 to 2 respectively.

2. The tetraphenylethylene embedded core crown ether bicyclic compound according to claim 1, characterized in that When a=b=1 or a=b=2, the cis-crown ether bicyclic compound includes two isomers: cis-symmetrical crown ether bicyclic compound and cis-asymmetric crown ether bicyclic compound; When a=b=1, The specific chemical formula and crystal structure of the cis-symmetrical crown ether bicyclic compound are as follows: ， The specific chemical formula and crystal structure of the cis-asymmetric crown ether bicyclic compound are as follows: ； When a=b=2, The specific chemical formula and crystal structure of the cis-symmetrical crown ether bicyclic compound: ； The specific chemical formula and crystal structure of the cis-asymmetric crown ether bicyclic compound: 。 3. A method for synthesizing a tetraphenylethylene embedded core crown ether bicyclic compound as claimed in claim 1, characterized in that: The synthesis method of a cis-crown ether bicyclic compound comprises the following steps: Under a protective atmosphere, the compound diketone, zinc powder and anhydrous tetrahydrofuran are weighed and stirred to dissolve, the obtained mixed solution is cooled to -20~0°C, titanium tetrachloride is added, and after the addition is complete, the reaction solution is heated to 60-80°C and refluxed for 12-18 hours; after the reaction is completed, the reaction is quenched, the reaction solution is filtered and the filtrate is washed with water, the organic phases are collected and combined and dried, and the obtained crude product is purified by column chromatography to obtain the tetraphenylethylene embedded core cis-crown ether bicyclic compound; The structural formula of the compound diketone is as follows: ； Wherein, m and n are integers of 2-5 respectively.

4. The method for synthesizing a tetraphenylethylene embedded core crown ether bicyclic compound according to claim 3, wherein: When m=n, the synthesis method of the compound diketone is as follows: Under nitrogen protection, 4,4-dihydroxybenzophenone, di-p-toluenesulfonyl ester-modified glycol chain, anhydrous potassium carbonate, and anhydrous acetonitrile are mixed, and the reaction solution is continued to be stirred under heating reflux. After the reaction is completed, the reaction solution is washed with deionized water and then extracted with dichloromethane. The organic phase is dried and then dried under reduced pressure. The obtained crude product is separated and purified by column chromatography to obtain a white solid compound diketone; The structural formula of the glycol chain modified with di-p-toluenesulfonyl ester is as follows: ; h is an integer from 1 to 5; When m≠n, the synthesis method of the compound diketone is as follows: S1. Under a protective atmosphere, anhydrous potassium carbonate and anhydrous DMF were weighed and stirred to dissolve, the reaction solution was heated, condensed and refluxed, and a DMF mixed solution of 4,4'-dihydroxybenzophenone and di-p-toluenesulfonyl ester-modified glycol chain 1 was slowly added dropwise. After the addition was complete, the reaction solution was stirred under reflux for 24 hours; after the reaction was completed, the mixture was filtered and concentrated under reduced pressure, the crude product was washed with water, extracted with ethyl acetate, and the organic phases were combined and dried; the crude product was separated and purified by silica gel column chromatography to obtain a white solid product; S2. Under a protective atmosphere, anhydrous potassium carbonate, the white solid product obtained in step S1, potassium iodide, and anhydrous acetonitrile were weighed and dissolved with stirring, the reaction solution was heated, condensed and refluxed, and an anhydrous acetonitrile solution of the glycol chain 2 modified with di-p-toluenesulfonyl ester was slowly added dropwise. After the addition was complete, the reaction solution was stirred under reflux for 24 hours. After the reaction was completed, the solution was cooled to room temperature, filtered, and concentrated under reduced pressure. The crude product was washed with water, extracted with ethyl acetate, and the organic phases were combined and dried. The crude product was separated and purified by silica gel column chromatography to obtain a white powdery solid compound diketone. The glycol chain 1 modified with di-p-toluenesulfonyl ester and the glycol chain 2 modified with di-p-toluenesulfonyl ester are compounds with different h values ​​in the following formula: ; h is an integer from 1 to 5.

5. The method for synthesizing a tetraphenylethylene embedded core crown ether bicyclic compound according to claim 3, wherein: The molar ratio of the used compounds diketone, zinc powder and titanium tetrachloride is 1:5-40:2.5-20.

6. The method for synthesizing a tetraphenylethylene embedded core crown ether bicyclic compound according to claim 5, characterized in that: When m=n=3 or m=n=4 in the structural formula of the compound diketone, different compound diketones are selected and the amount of the raw materials is changed to obtain crown ether bicyclic compounds with different structures; The molar ratio of the compound diketone, zinc powder and titanium tetrachloride is 1:5-10:2.5-5, and the obtained crown ether bicyclic compound is a cis-asymmetric crown ether bicyclic compound; When the molar ratio of zinc powder to compound diketone is higher than 10:1 and the molar ratio of titanium tetrachloride to compound diketone is higher than 5:1, the obtained crown ether bicyclic compound is a mixture of a cis-asymmetric crown ether bicyclic compound and a cis-symmetric crown ether bicyclic compound; In the structural formula of the compound diketone, except for the case where m=n=3 or m=n=4, the molar ratio of the compound diketone, zinc powder, and titanium tetrachloride is 1:5~40:2.5~20, and the obtained crown ether bicyclic compound is a cis single conformation crown ether bicyclic compound.

7. A method for synthesizing a tetraphenylethylene embedded core crown ether bicyclic compound as claimed in claim 1, characterized in that: The synthesis method of the geminal crown ether bicyclic compound comprises the following steps: Under a protective atmosphere, zinc powder, a monoketone compound, and anhydrous tetrahydrofuran were weighed and stirred to dissolve. The reaction solution was cooled to -20-0°C, titanium tetrachloride was added, and after the addition was completed, the reaction solution was heated to 60-80°C and refluxed for 12-18 hours. After the reaction was completed, the reaction was quenched, the reaction solution was filtered, and the filtrate was washed with water. The organic phases were collected, combined, and dried, and the crude product was purified by column chromatography to obtain a tetraphenylethylene-embedded core gem-crown ether bicyclic compound. The structural formula of the compound monoketone is as follows: Wherein, w is an integer from 0 to 3.

8. The method for synthesizing a tetraphenylethylene embedded core crown ether bicyclic compound according to claim 7, characterized in that: The synthesis method of the compound monoketone is as follows: Under a protective atmosphere, 4,4-dihydroxybenzophenone, anhydrous potassium carbonate and anhydrous acetonitrile were weighed and stirred to dissolve, the reaction solution was heated to reflux, condensed, and anhydrous acetonitrile solution of a glycol chain modified with di-p-toluenesulfonate was slowly added dropwise. After the addition was completed, the reaction solution was continued to react under reflux; after the reaction was completed, the reaction solution was filtered, the filtrate was dried, the crude product was dissolved in dichloromethane, and then washed with water, the organic phases were collected and combined and dried over anhydrous sodium sulfate, the solution was dried, and the crude product was purified by column chromatography to obtain a white solid compound monoketone.

9. The method for synthesizing a tetraphenylethylene embedded core crown ether bicyclic compound according to claim 7, characterized in that: The dosage ratio of zinc powder, compound monoketone, anhydrous tetrahydrofuran, and titanium tetrachloride is 7.2 mmol: 0.72 mmol: 6~9 mL: 3.6 mmol.

10. Use of the tetraphenylethylene embedded core crown ether bicyclic compound as claimed in claim 1 in fluorescent sensing and light-emitting devices.

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