A compound having an aggregation-induced emission property and a preparation method thereof

Abstract

The application discloses a compound with an aggregation-induced emission property and a preparation method thereof, and has a general structure shown in the following formula (1): wherein R1 is O or NH, R2 is a single bond, a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group; R3 is H, a substituted or unsubstituted phenyl group, R4 and R5 are independently selected from H, a substituted or unsubstituted C 1～8 aliphatic hydrocarbon group, a C 1～4 alkoxy group, a diaryl amino group, a carbazolyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, and the aliphatic hydrocarbon group comprises at least one of an alkyl group, an alkenyl group or an alkynyl group. The structural compound of the application scheme has a weak light emission intensity in a solution and emits strong fluorescence in an aggregated state, and is an excellent aggregation-induced emission material and has a good application prospect.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of light-emitting materials, in particular to a compound with an aggregation-induced emission property and a preparation method thereof. BACKGROUND

[0002] In recent years, the research on organic light-emitting materials has made remarkable progress, and important applications have been achieved in the fields of display technology, lighting, sensors and biomedicine. However, the traditional organic light-emitting materials have the problem of aggregation-induced quenching (ACQ), that is, they emit strong fluorescence in a solution state, but the fluorescence is weakened or even quenched in a solid state, which limits their practical application in a thin film or other solid state.

[0003] In 2001, the research group of Academician Tang Benzhong discovered a series of 1-methyl-1,2,3,4,5-pentaphenyl-silole (MPPS) compounds, which are characterized in that the more the molecules are aggregated, the stronger the fluorescence is emitted (J.D. Luo, Z.L. Xie, J.W.Y. Lam, L. Cheng, H.Y. Chen, C.F. Qiu, H.S. Kwok, X.W. Zhan, Y.Q. Liu, D.B. Zhu, B.Z. Tang, Chem. Commun. 2001, 1740). The series of compounds can hardly emit fluorescence in a solution, but can emit strong fluorescence in a solid state. Therefore, the concept of "aggregation-induced emission" (AIE) is proposed, and the material is called an aggregation-induced emission material. The concept of aggregation-induced emission provides a new idea for solving the ACQ of light-emitting materials. In the past decade, due to the fact that the light-emitting efficiency of the material in a solid or aggregated state is much higher than that in a solution state, this has an important role in overcoming the aging problem of light-emitting materials and light-emitting devices and improving the light-emitting efficiency. Moreover, the material has a significant response to a chemical environment and can be applied to chemical / biological sensors as a stimulus-responsive material, so the research on the material has become a new topic and has made great progress. Therefore, developing new AIE materials has become a research hotspot at present. By regulating the molecular aggregation state and intermolecular interaction, the aggregation-induced emission effect can be realized, so as to improve the light-emitting efficiency and stability. In addition, the AIE material can also be functionally optimized through structural design and synthesis strategy to meet the needs of different application fields. Therefore, synthesizing new AIE materials and exploring practical applications in the fields of electronics, biological imaging and sensors will promote the technological progress and innovation in related fields.

[0004] Therefore, it is of great significance to develop a material with an aggregation-induced emission property. SUMMARY

[0005] The present application aims to at least solve one of the technical problems existing in the prior art. To this end, the present application proposes a compound having an aggregation-induced emission property.

[0006] The present application also proposes a preparation method of the compound.

[0007] The present application also proposes an application of the compound.

[0008] According to an aspect of the present application, a compound is proposed, having a general structure shown in the following formula (1):

[0009]

[0010] In the formula, R1 is O or NH, R2 is a single bond, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group; R3 is H, a substituted or unsubstituted phenyl group, R4 and R5 are independently selected from H, a substituted or unsubstituted C 1～8 aliphatic alkyl group, a C 1～4 alkoxy group, a diarylamine group, a carbazolyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, the aliphatic alkyl group including at least one of an alkyl group, an alkenyl group, or an alkynyl group.

[0011] According to a preferred embodiment of the present application, the compound has at least the following effect: the compound has a weak light emission intensity in a solution and emits strong fluorescence in an aggregated state, and is an excellent aggregation-induced emission material.

[0012] In some preferred embodiments of the present application, R2 is selected from one of the following structural formulas:

[0013]

[0014] In some preferred embodiments of the present application, R4 and R5 are independently selected from:

[0015]

[0016] wherein R6 and R7 are C 1～12 aliphatic alkyl groups.

[0017] In some preferred embodiments of the present application, the substitution is a substitution by a phenyl group, a halogen, an alkyl group, a halogenated alkyl group, or a cyano group.

[0018] In some preferred embodiments of the present application, the compound is selected from one of the following structural formulas:

[0019]

[0020] The application also provides a preparation method of the compound, comprising the following steps:

[0021] If R1 in the compound shown in formula (1) is O, then the compound shown in formula (2) is subjected to Knoevenagel condensation reaction with 1,3-cyclohexanedione, and the compound shown in formula (1) is obtained.

[0022] If R1 in the compound shown in formula (1) is NH, then the compound shown in formula (2) is subjected to Knoevenagel condensation reaction with 1,3-cyclohexanedione and ammonium acetate, and the compound shown in formula (1) is obtained.

[0023] The compound shown in formula (2) has the following general structure:

[0024]

[0025] According to a preferred embodiment of the application, at least the following effects are achieved: the application scheme synthesizes a novel AIE luminescent material oxatexane diketone derivative or acridinedione derivative by one-pot Knoevenagel condensation reaction of 1,3-cyclohexanedione and triphenylethylene or tetraphenylethylene groups. In the field of organic synthetic chemistry, Knoevenagel condensation reaction is an important reaction, which can be used for building carbon-carbon double bond and introducing functional groups. Triphenylethylene and tetraphenylethylene structures not only have obvious aggregation-induced emission performance, but also have high thermal stability and luminescent intensity, and are used for preparing organic electroluminescent devices and other luminescent materials, and have rich chemical structures and potential application value. 1,3-cyclohexanedione is an important organic compound, which is widely used in the fields of synthetic raw materials and pharmaceutical chemistry.

[0026] The application scheme synthesizes a compound with AIE performance by simple one-pot Knoevenagel condensation reaction of triphenylethylene or tetraphenylethylene derivative, 1,3-cyclohexanedione and ammonium acetate. Through the method, high yield, high selectivity, low cost and simple operation can be achieved. The application provides a reliable synthesis method, which can be applied to synthesis of various triphenylethylene or tetraphenylethylene derivatives and 1,3-cyclohexanedione derivatives, has wide applicability, and has good potential economic benefits and scalability.

[0027] In some preferred embodiments of the application, the compound shown in formula (2) can be used as raw material, and the aromatic aldehyde containing triphenylethylene or tetraphenylethylene is synthesized by means of Fu-Ke alkylation, amine alkylation, halogenation, Suzuki reaction, Heck reaction, Wittig reaction and the like. The synthesis can be carried out by using conventional organic synthesis method.

[0028] In some preferred embodiments of the present application, the compound of formula (2) is selected from at least one of the following structures:

[0029]

[0030] In some preferred embodiments of the present application, the Knoevenagel condensation reaction is catalyzed by a catalytic system, which comprises MgCl2 and acetic acid, and if R1 is O, the catalytic system further comprises urea. The compound of formula (1) includes xanthone derivatives and acridinedione derivatives. For xanthone derivatives, the preparation process comprises the following steps: synthesis of aromatic aldehyde group containing triphenyl ethylene or tetraphenyl ethylene; Knoevenagel condensation reaction of 1,3-cyclohexanedione and aromatic aldehyde group. For acridinedione derivatives, the main steps of synthesis are: synthesis of aromatic aldehyde group containing triphenyl ethylene or tetraphenyl ethylene; Knoevenagel condensation reaction of 1,3-cyclohexanedione, aromatic aldehyde group and ammonium acetate.

[0031] In some preferred embodiments of the present application, the Knoevenagel condensation reaction is carried out in a solvent system, which is selected from at least one of anhydrous ethanol or anhydrous methanol.

[0032] In summary, the present application provides an efficient synthesis method, which utilizes Knoevenagel condensation reaction of derivatives of triphenyl ethylene or tetraphenyl ethylene and 1,3-cyclohexanedione to realize the synthesis of target products. This method has the advantages of high yield, high selectivity and simplicity, and can provide important application value for the fields of organic synthesis chemistry and pharmaceutical chemistry.

[0033] The present application also provides the use of the above-mentioned compound in aggregation-induced emission.

[0034] In some embodiments of the present application, the aggregation-induced emission occurs in a poor solution; the poor solution is water.

[0035] The present application also provides the use of the above-mentioned compound in preparing a fluorescent sensor.

[0036] The present application also provides the use of the above-mentioned compound in preparing an organic light-emitting material.

[0037] The present application also provides the use of the above-mentioned compound in preparing a light-emitting device, a fluorescent probe, a fluorescent switch or a biological imaging agent.

[0038] The xanthene derivatives and acridine derivatives provided by the present application have the properties of piezochromism and recoverability in powder state, and have obvious aggregation-induced emission characteristics in poor solutions. The synthesis method is simple, the raw material cost is low, and the large-scale commercial production is easy. The powder of the series of products synthesized by the present application has good piezochromic performance, and has good potential application prospects in the fields of woven fabric crack detection, anti-counterfeiting technology, electroluminescent devices, fluorescent probes, fluorescent switches and biological imaging, thereby expanding the application field of AIE.

[0039] In the description of the present application, the term "aliphatic hydrocarbon group" refers to alkyl, alkenyl and alkynyl.

[0040] In the description of the present application, the term "alkyl" refers to a saturated linear or branched aliphatic hydrocarbon group.C 1～8 Examples of alkyl include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl.

[0041] In the description of the present application, the term "alkoxy" refers to a group of formula "-O-alkyl",C 1～4 Alkoxy includes methoxy, ethoxy, propoxy and butoxy.

[0042] In the description of the present application, the term "aryl" represents an aromatic hydrocarbon group comprising one or more phenyl groups, preferably an aromatic hydrocarbon group of 6 to 10 carbon atoms, preferably phenyl.

[0043] In the description of the present application, the term "substituted" means that the group can or can not be further substituted by one or more groups selected from alkyl, alkenyl, alkynyl, aryl, halo, haloalkyl, haloalkenyl, haloalkynyl, haloaryl, hydroxy, alkoxy, alkenoxy, aryloxy, benzyloxy, haloalkoxy, haloalkenoxy, haloaryloxy, heteroaryl, nitro, nitroalkyl, nitroalkenyl, nitroalkynyl, nitroaryl, nitroheterocyclyl, amino, alkylamino, dialkylamino, alkenylamino, alkynylamino, arylamino, diarylamino, phenylamino, diphenylamino, benzylamino, dibenzylamino, hydrazino, acyl, acylamino, diacylamino, acyloxy, heterocyclyl, heterocyclyloxy, heterocyclylamino, haloheterocyclyl, carboxyl ester, carboxyl, carboxylamide, mercapto, alkylthio, benzylthio, acylthio and phosphorus-containing groups.

[0044] In the description of the present application, the term "halogen" refers to fluorine, chlorine, bromine or iodine.

[0045] In the description of the application, the term "compound" refers to all stereoisomers, geometric isomers, tautomers, and isotopes of the described structure. Unless otherwise specified, a compound identified herein by name or structure as a particular tautomer is intended to include other tautomeric forms. It is understood that certain compounds provided herein can contain one or more asymmetric centers and thus can exist in enantiomeric or racemic mixtures, as mixtures of diastereomers, or as individual enantiomers and as mixtures of diastereomers.

[0046] In the description of the application, the term "tautomer" refers to a compound whose structure differs significantly in the arrangement of atoms but which exists in simple and rapid equilibrium, and it is understood that the compounds provided herein can be depicted as different tautomers, and when a compound has tautomeric forms, all tautomeric forms are within the scope of the application, and the naming of a compound does not exclude any tautomer.

[0047] Other features and advantages of the present application will be set forth in the description that follows, and in part will be apparent from the description, or can be learned by practice of the application. BRIEF DESCRIPTION OF DRAWINGS

[0048] The above and / or additional aspects and advantages of the present application will become apparent and be readily understood from the following description, taken in conjunction with the accompanying drawings, in which:

[0049] Figure 1 Figure 1 is a plot of the change in fluorescence intensity of a solution of the compound (9-(4-(1,2,2-triphenylvinyl)phenyl)-3,4,5,6,7,9-hexahydro-1H-xanthene-1,8(2H)-dione) prepared in Example 1 of the present application in tetrahydrofuran with different volume fractions of water added to the solution. DETAILED DESCRIPTION

[0050] The concept and technical effects of the present application will be described clearly and completely in conjunction with the examples below, so as to fully understand the purpose, features and effects of the present application. Obviously, the described examples are only a part of the examples of the present application, but not all examples, and other examples obtained by those skilled in the art based on the examples of the present application without creative labor are within the scope of protection of the present application. Unless otherwise specified, the experimental methods used in the examples are conventional methods; unless otherwise specified, the materials, reagents, etc. used are commercially available reagents and materials. Unless otherwise specified, the same parameters are used in each example. The examples described below are exemplary and are used to explain the present application, and cannot be understood as limiting the present application.

[0051] In the description of the application, the description of the terms "one embodiment", "some embodiments", "illustrative embodiment", "example", "specific example", or "some examples" means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the application. In the description, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0052] In the description of the application, room temperature refers to 25±5℃, and in the examples, it is specifically 25℃.

[0053] The application provides a class of xanthone derivatives or acridinedione derivatives containing triphenylethylene or tetraphenylethylene structures, the structure of which is shown in general formula (1):

[0054]

[0055] Among them, R1 is O, NH; R2 is a single bond, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl; R3 is H, substituted or unsubstituted phenyl, R4, R5 are independently selected from H, C 1～8 alkyl, C 1～4 alkoxy, diarylamine, carbazolyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and the aliphatic group includes at least one of alkyl, alkenyl or alkynyl.

[0056] The preparation process is as follows:

[0057] First step: synthesis of aromatic aldehyde containing triphenylethylene or tetraphenylethylene

[0058] Using diphenone derivative or triphenylethylene bromide as raw material, the aromatic aldehyde containing triphenylethylene or tetraphenylethylene is synthesized by conventional organic synthesis method, including Friedel-Crafts alkylation, amine alkylation, halogenation, Suzuki reaction, Heck reaction, Wittig reaction, etc. The structure is shown in general formula (2):

[0059]

[0060] The preferred structure of the aromatic aldehyde is as follows:

[0061]

[0062] Second step:

[0063] The intermediate synthesized is closed with 1,3-cyclohexanedione in anhydrous ethanol as solvent, under the catalysis of anhydrous MgCl2, acetic acid and urea to generate xanthone derivative, and the reaction formula is as follows:

[0064]

[0065] The intermediate, 1,3-cyclohexanedione and ammonium acetate are closed into acridinedione derivatives under the catalysis of anhydrous MgCl2 and acetic acid with ethanol as a solvent, and the reaction formula is as follows:

[0066]

[0067] The application designs a kind of xanthene dione derivatives and acridinedione derivatives and preparation method thereof, the synthesis of xanthene dione derivatives: aromatic aldehyde group compound containing triphenyl ethylene or tetraphenyl ethylene structure, 1,3-cyclohexanedione, urea, anhydrous MgCl2, acetic acid are synthesized by one-pot method;The synthesis of acridinedione derivatives: aromatic aldehyde group compound containing triphenyl ethylene or tetraphenyl ethylene structure, 1,3-cyclohexanedione, ammonium acetate, anhydrous MgCl2, acetic acid are synthesized by one-pot method.The xanthene dione derivatives and acridinedione derivatives containing triphenyl ethylene or tetraphenyl ethylene structure provided by the application have obvious aggregation-induced emission characteristics in poor solution, the synthesis method is simple, and raw material cost is low, easy to large-scale commercial production.The powder of the series of products synthesized by the scheme of the application has good pressure-induced color change performance, and is expected to have good potential application prospect in the fields of woven fabric crack detection, anti-counterfeiting technology, electroluminescent device, fluorescent probe, fluorescent switch and biological imaging, and expands the application field of AIE.

[0068] Example 1

[0069] A compound with aggregation-induced emission property is prepared in the embodiment, and the specific preparation process is as follows:

[0070] (1) Synthesis of intermediate tetraphenyl ethylene aldehyde:

[0071] Under N2 atmosphere, triphenyl bromo ethylene (3.35g, 10mmol) and 4-formyl phenyl boronic acid (1.5g, 10mmol) are added into a three-necked flask, then 50mL of tetrahydrofuran (THF), 18mL of 2mol / L potassium carbonate aqueous solution and 0.32g of tetrabutylammonium bromide (TBAB) (1.0mmol) are added, stirring at room temperature for half an hour and then adding Pd (PPh3)4 (0.010g, 8.7×10 - 3 mmol) and heating to 90℃ for 24h. Then the reaction solution is poured into water, extracted with ethyl acetate for three times, the organic layer is dried with anhydrous sodium sulfate, the solvent is removed by rotary evaporation under reduced pressure, and the product is purified by silica gel column chromatography, with a volume ratio of 1:2 of dichloromethane and n-hexane mixed solvent as eluent. 3.25g of product is obtained, with a yield of 97%.

[0072]

[0073] (2) Synthesis of target product

[0074] Example 1 1 : Synthesis of 9-(4-(1,2,2-triphenylvinyl)phenyl)-3,4,5,6,7,9- hexahydro-1 H-xanthene-1,8(2H)-dione:

[0075] TPEA (0.361 g, 1 mmol) and 30 mL of absolute ethanol were added into a three-neck flask and heated at 75 °C with vigorous stirring. After TPEA was completely dissolved, anhydrous magnesium chloride (0.019 g, 0.2 mmol) and catalyst acetic acid (9 mL, 30% of ethanol) were added and the stirring was continued for 10 min at 90 °C. Ammonium acetate (0.078 g, 1 mmol) and 1,3-cyclohexanedione (0.196 g, 2 mmol) were added into the flask and the reaction was continued for 24 h. The reaction mixture was filtered and the residue was washed with ethanol for 3 times to give a white powder (0.43 g, 79%).

[0076]

[0077] Example 2: Synthesis of 9-(4-(1,2,2-triphenylvinyl)phenyl)-3,4,6,7,9,10- hexahydroacridine-1,8(2H,5H)-dione:

[0078] TPEA (0.361 g, 1 mmol) and 30 mL of absolute ethanol were added into a three-neck flask and heated at 75 °C with vigorous stirring. After TPEA was completely dissolved, anhydrous magnesium chloride (0.019 g, 0.2 mmol) and catalyst acetic acid (9 mL, 30% of ethanol) were added and the stirring was continued for 10 min at 90 °C. Ammonium acetate (0.078 g, 1 mmol) and 1,3-cyclohexanedione (0.196 g, 2 mmol) were added into the flask and the reaction was continued for 24 h. The reaction mixture was filtered and the residue was washed with ethanol for 3 times to give a white powder (0.43 g, 79%).

[0079]

[0080] Example 2

[0081] A compound with aggregation-induced emission property was prepared in this example, and the specific preparation process is as follows:

[0082] (1) Synthesis of intermediate 4'-(1,2,2-triphenylvinyl) biphenyl-4-carbaldehyde:

[0083] Tetraphenyl ethylene bromide (4.11 g, 10.0 mmol) and 4-formylphenylboronic acid (1.49 g, 10.0 mmol) were added to a three-necked flask, 60 mL of tetrahydrofuran, 15 mL of 2M aqueous K2CO3, tetrabutylammonium bromide (TBAB) (0.64 g, 2.0 mmol) were added, and the mixture was stirred under argon for 40 min. A catalytic amount of Pd(PPh3)4was added, and the mixture was heated to 85°C in an oil bath for 24 h. The reaction was quenched with water, and the organic phase was dried over anhydrous sodium sulfate. The crude product was obtained by rotary evaporation under reduced pressure. The product was purified by column chromatography on silica gel using a mixture of n-hexane and dichloromethane (10:1 and 1:1 by volume) as the eluent. The pure product was obtained as a beige solid (3.3 g, 76% yield).

[0084]

[0085] (2) Synthesis of the target product

[0086] ① Synthesis of 9-(4',2',2'-triphenylvinyl)-[1,1'-biphenyl]-4-yl)-3,4,5,6,7,9-hexahydro-1H-xanthene-1,8(2H)-dione:

[0087] The target product 9-(4',2',2'-triphenylvinyl)-[1,1'-biphenyl]-4-yl)-3,4,5,6,7,9-hexahydro-1H-xanthene-1,8(2H)-dione was synthesized according to the procedure described in Example 1(2) under the heading of item ① by reacting 4'-(1,2,2-triphenyl ethylene) biphenyl-4-carboxaldehyde and 1,3-cyclohexanedione. The product was obtained as a gray powder (0.45 g, 73% yield).

[0088]

[0089] ② Synthesis of 9-(4'-(1,2,2-triphenylvinyl)-[1,1'-biphenyl]-4-yl)-3,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-dione:

[0090] The target product 9-(4'-(1,2,2-triphenylvinyl)-[1,1'-biphenyl]-4-yl)-3,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-dione was synthesized according to the procedure described in Example 1(2) under the heading of item ② by reacting 4'-(1,2,2-triphenyl ethylene) biphenyl-4-carboxaldehyde, 1,3-cyclohexanedione, and ammonium acetate. The product was obtained as a gray powder (0.44 g, 71% yield).

[0091]

[0092] Example 3

[0093] A compound having an aggregation-induced emission property was prepared according to the following procedure:

[0094] (1) Synthesis of intermediate 4-(2,2-diphenylvinyl)benzaldehyde:

[0095] Triphenyl ethylene bromide (3.35 g, 10.0 mmol) was dissolved in 20 mL of tetrahydrofuran and cooled to -78 °C. A 2.5 M n-butyllithium solution (4.0 mL, 10.0 mmol) was added dropwise. After 2 h of dropwise addition, N,N-dimethylformamide (1.46 g, 20.0 mL) was added and the temperature was allowed to rise to room temperature. The reaction was allowed to proceed for another 24 h. The reaction was quenched with water and the organic phase was dried over anhydrous sodium sulfate. The solvent was removed by rotary evaporation under reduced pressure to obtain a crude product. The product was purified by column chromatography using a mixture of n-hexane and dichloromethane (3:1, by volume) as the eluent. The pure product was obtained as a white solid (3.3 g, 81% yield).

[0096]

[0097] (2) Synthesis of target product

[0098] ① Synthesis of 9-(4-(2,2-diphenylvinyl)phenyl)-3,4,5,6,7,9-hexahydro-1H-xanthene-1,8(2H)-dione:

[0099] The target product 9-(4-(2,2-diphenylvinyl)phenyl)-3,4,5,6,7,9-hexahydro-1H-xanthene-1,8(2H)-dione was synthesized according to the procedure described in Example 1(2) by reacting 4-(2,2-diphenylvinyl)benzaldehyde with 1,3-cyclohexanedione. The pure product was obtained as a white powder (0.38 g, 80% yield).

[0100]

[0101] ② Synthesis of 9-(4-(2,2-diphenylvinyl)phenyl)-3,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-dione:

[0102] The target product 9-(4-(2,2-diphenylvinyl)phenyl)-3,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-dione was synthesized according to the procedure described in Example 1(2) by reacting 4-(2,2-diphenylvinyl)benzaldehyde, 1,3-cyclohexanedione, and ammonium acetate. The pure product was obtained as a white powder (0.36 g, 78% yield).

[0103]

[0104] Example 4

[0105] A compound having an aggregation-induced emission property was prepared according to the following procedure.

[0106] (1) Synthesis of intermediate 4'-(2,2-diphenylvinyl)-[1,1'-biphenyl]-4-carbaldehyde

[0107]

[0108] (2) Synthesis of target product

[0109] (1) Synthesis of intermediate 4'-(2,2-diphenylvinyl)-[1,1'-biphenyl]-4-carbaldehyde

[0110] The target product 9-(4'-(2,2-diphenylvinyl)-[1,1'-biphenyl]-4-yl)-3,4,6,7,9,10- hexahydroacridine-1,8(2H,5H)-dione was synthesized according to the procedure of Example 1 (2) SEQ. No. II, from 4'-(2,2-diphenylvinyl)-[1,1'-biphenyl]-4-carbaldehyde, 1,3- cyclohexanedione and ammonium acetate. The pure product was a white powder 0.4 g with a yield of 73%.

[0111]

[0112] (1) Synthesis of intermediate 4'-(2,2-diphenylvinyl)-[1,1'-biphenyl]-4-carbaldehyde

[0113] The target product 9-(4'-(2,2-diphenylvinyl)-[1,1'-biphenyl]-4-yl)-3,4,6,7,9,10- hexahydroacridine-1,8(2H,5H)-dione was synthesized according to the procedure of Example 1 (2) SEQ. No. II, from 4'-(2,2-diphenylvinyl)-[1,1'-biphenyl]-4-carbaldehyde, 1,3- cyclohexanedione and ammonium acetate. The pure product was a white powder 0.4 g with a yield of 73%.

[0114]

[0115] Example 5

[0116] A compound having an aggregation-induced emission property was prepared according to the following procedure.

[0117] (1) Synthesis of intermediate 5-(4-(1,2,2-triphenylvinyl)phenyl)thiophene-2- carboxaldehyde was performed according to the procedure described in Example 2(1) using 5-formyl-2-thiopheneboronic acid instead of 4-formylbenzeneboronic acid and bromotetraphenyl ethylene to give the target product as a light yellow powder 3.75 g in 85% yield.

[0118]

[0119] (2) Synthesis of the target product:

[0120] (1) Synthesis of 9-(5-(4-(1,2,2-triphenylvinyl)phenyl)thiophen-2-yl)-3,4,5,6,7,9- hexahydro-lH-xanthene-l,8(2H)-dione:

[0121] The target product 9-(5-(4-(1,2,2-triphenylvinyl)phenyl)thiophen-2-yl)-3,4,5,6,7,9- hexahydro-lH-xanthene-l,8(2H)-dione was synthesized according to the procedure described in Example 1(2)① using 5-(4-(1,2,2-triphenylvinyl)phenyl)thiophene-2-carboxaldehyde and 1,3- cyclohexanedione to give off-white powder 0.47 g in 75% yield.

[0122]

[0123] (2) Synthesis of the target product:

[0124] The target product 9-(5-(4-(1,2,2-triphenylvinyl)phenyl)thiophen-2-yl)-3,4,5,6,7,9- hexahydro-lH-xanthene-l,8(2H)-dione was synthesized according to the procedure described in Example 1(2)① using 5-(4-(1,2,2-triphenylvinyl)phenyl)thiophene-2-carboxaldehyde and 1,3- cyclohexanedione to give off-white powder 0.47 g in 75% yield.

[0125] yield 71%.

[0126]

[0127] Example 6

[0128] In this example, a compound having an aggregation-induced emission property was prepared, and the structure thereof is as follows:

[0129]

[0130] The specific preparation process is as follows:

[0131] (1) Synthesis of intermediate (E)-4'-(2-([1,1'-biphenyl]-4-yl)-1,2-diphenylvinyl)-[1,1'-biphenyl]-4- carbaldehyde:

[0132] (E)-4-(2-(4-bromophenyl)-1,2-diphenylvinyl)-1,1'-biphenyl reacted with 4-formylphenylboronic acid to obtain product (E)-4'-(2-([1,1'-biphenyl]-4-yl)-1,2-diphenylvinyl)-[1,1'-biphenyl]-4- carbaldehyde.

[0133]

[0134] (2) Synthesis of target product (E)-9-(4'-(2-([1,1'-biphenyl]-4-yl)-1,2-diphenylvinyl)-[1,1'-biphenyl]-4-yl)- 3,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-dione:

[0135] (E)-4'-(2-([1,1'-biphenyl]-4-yl)-1,2-diphenylvinyl)-[1,1'-biphenyl]-4-carbaldehyde reacted with 1,3- cyclohexanedione, ammonium acetate to obtain product (E)-9-(4'-(2-([1,1'-biphenyl]-4-yl)-1,2- diphenylvinyl)-[1,1'-biphenyl]-4-yl)-3,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-dione.

[0136]

[0137] The target compound was prepared and characterized by nuclear magnetic resonance.

[0138] Example 7

[0139] This example prepared a compound with aggregation-induced emission properties, and the structure is:

[0140]

[0141] The specific preparation process is as follows:

[0142] (1) Synthesis of intermediate (E)-9-(4-(2-(4-bromophenyl)-1,2-diphenylvinyl)phenyl)-9H-carbazole:

[0143] (E)-1,2-bis(4-bromophenyl)-1,2-diphenylvinyl reacted with 9H-carbazole under the catalysis of palladium diacetate and tri-tert-butyl phosphine to generate (E)-9-(4-(2-(4-bromophenyl)-1,2- diphenylvinyl)phenyl)-9H-carbazole.

[0144]

[0145] (2) Synthesis of intermediate (E)-4'-(2-(4-(9H-carbazol-9-yl)phenyl)-1,2-diphenylvinyl)-[1,1'-biphenyl]-4-carboxaldehyde:

[0146] (E)-9-(4-(2-(4-bromophenyl)-1,2-diphenylvinyl)phenyl)-9H-carbazole reacts with 4-formylphenylboronic acid to generate (E)-4'-(2-(4-(9H-carbazole-9-yl)phenyl)-1,2-diphenylvinyl)-[1,1'-biphenyl]-4-carbaldehyde.

[0147]

[0148] (3) Synthesis of the target product (E)-9-(4'-(2-(4-(9H-carbazol-9-yl)phenyl)-1,2-diphenylvinyl)-[1,1'-biphenyl]-4-yl)-3,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-dione:

[0149] (E)-4'-(2-(4-(9H-carbazole-9-yl)phenyl)-1,2-diphenylvinyl)-[1,1'-biphenyl]-4-carboxaldehyde reacts with 1,3-cyclohexanedione in the presence of acetic acid and MgCl2 catalyst to produce (E)-9-(4'-(2-(4-(9H-carbazole-9-yl)phenyl)-1,2-diphenylvinyl)-[1,1'-biphenyl]-4-yl)-3,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-dione.

[0150]

[0151] The target compound was prepared by nuclear magnetic resonance characterization.

[0152] Example 8

[0153] This embodiment prepared a compound with aggregation-induced emission properties, the structure of which is as follows:

[0154]

[0155] The specific preparation process is as follows:

[0156] (1) Synthesis of intermediate 4'-(1,2,2-triphenylvinyl)-[1,1'-biphenyl]-4-carboxaldehyde:

[0157] (2-(4-bromophenyl)ethylene-1,1,2-triyl)triphenyl reacts with 4-formylphenylboronic acid to give the product 4'-(1,2,2-triphenylvinyl)-[1,1'-biphenyl]-4-carboxaldehyde.

[0158]

[0159] (2) Synthesis of intermediate (E)-4-(2-(4'-(1,2,2-triphenylvinyl)-[1,1'-biphenyl]-4-yl)vinyl)benzaldehyde:

[0160] 4'-(1,2,2-triphenylvinyl)-[1,1'-biphenyl]-4-carboxaldehyde reacts with 4-aminobenzaldehyde to give the product (E)-4-(2-(4'-(1,2,2-triphenylvinyl)-[1,1'-biphenyl]-4-yl)vinyl)benzaldehyde.

[0161]

[0162] (3) Synthesis of the target product (E)-9-(4-(2-(4'-(1,2,2-triphenylvinyl)-[1,1'-biphenyl]-4-yl)vinyl)phenyl)-3,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-dione:

[0163] (E)-4-(2-(4'-(1,2,2-triphenylvinyl)-[1,1'-biphenyl]-4-yl)vinyl)benzaldehyde, reacted with 1,3-cyclohexanedione and ammonium acetate, yields (E)-9-(4-(2-(4'-(1,2,2-triphenylvinyl)-[1,1'-biphenyl]-4-yl)vinyl)phenyl)-3,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-dione.

[0164]

[0165] The target compound was prepared by nuclear magnetic resonance characterization.

[0166] Test case

[0167] This experimental example tested the structure of the compounds prepared in the examples and the maximum fluorescence emission wavelength, fluorescence quantum efficiency, and aggregation-induced emission effect of the solid powders. Among them:

[0168] Nuclear magnetic resonance (NMR) and mass spectrometry (MS) analyses confirmed that the products with the target structure were obtained in each embodiment of the present invention.

[0169] The maximum fluorescence emission wavelength of the solid powder was determined by using RF-5301pc fluorescence spectrophotometer of Shimadzu Corporation of Japan; the fluorescence quantum efficiency of the solid powder was determined by using the test system for the fluorescence quantum efficiency of the solid powder which was composed of Maya 2000Pro fiber spectrometer of Ocean Optics, C-701 integrating sphere of Blue-Scientific Corporation of USA and LLS-LED light source of Ocean Optics, and the method in the literature Adv. Mater. 1997, 9, 230-232 was referred to.

[0170] The determination results are shown in Table 1 below.

[0171] Table 1 Maximum fluorescence emission wavelength and fluorescence quantum efficiency of the solid powder of the compound in Examples 1-5

[0172]

[0173] Note: represents the maximum fluorescence emission wavelength of the solid powder of the sample, and Φ F represents the fluorescence quantum efficiency of the solid powder.

[0174] Only part of the detection results of the compounds are shown in the table, and the results of the compounds prepared in other examples are equivalent, and are not shown one by one to avoid redundancy.

[0175] In order to explore the AIE performance of the compound of the scheme, water, a poor solvent, was added to the tetrahydrofuran solution of the compound, and the fluorescence intensity of the solution was observed with the change of the water content. It can be seen from Figure 1 that when the water content is less than 90%, the fluorescence intensity and change of the solution are weak, but when the water content reaches 90%, the fluorescence intensity of the solution suddenly increases, which is 20 times that of the pure tetrahydrofuran solution. That is, the data show that the compound of the scheme has good AIE performance.

[0176] From the above results, it can be seen that the compounds of the scheme all have good aggregation-induced emission effect, and therefore have good application prospects in the fields of preparing organic light-emitting materials, fluorescence sensors, light-emitting devices, fluorescence probes, fluorescence switches or biological imaging agents, etc.

[0177] The above has made a detailed description of the embodiments of the present application, but the present application is not limited to the above embodiments, and various changes can be made within the knowledge range possessed by those skilled in the art without departing from the purpose of the present application.

Claims

1. A compound, characterized in that: A compound having a general structure as shown in formula (1): wherein R1 is O or NH, and R2 is a single bond or selected from one of the following structures: ； R3is H, substituted or unsubstituted phenyl, R4is H, R5is selected from H, substituted or unsubstituted C 1～8 fatty alkyl, C 1～4 alkoxy: The substitution is substituted by phenyl, halogen, alkyl, halogenated alkyl or cyano.

2. The compound of claim 1, wherein: The compound is selected from one of the following structures: 。 3. Process for the preparation of a compound according to any one of claims 1 to 2, characterized in that: The method comprises the following steps: If R1 in the compound shown in formula (1) is O, then the compound shown in formula (2) is subjected to Knoevenagel condensation reaction with 1,3-cyclohexanedione, and the compound shown in formula (1) is obtained; If R1 in the compound shown in formula (1) is NH, then the compound shown in formula (2) is subjected to Knoevenagel condensation reaction with 1,3-cyclohexanedione and ammonium acetate, and the compound shown in formula (1) is obtained; The general structure of the compound shown in formula (2) is as follows: 。 4. The method of claim 3, wherein: The compound shown in formula (2) is selected from at least one of the following structures: 。 5. The method of claim 3, wherein: The Knoevenagel condensation reaction occurs under catalysis of a catalytic system, the catalytic system comprises MgCl2 and acetic acid, and if R1 is O, the catalytic system further comprises urea; the Knoevenagel condensation reaction is performed in a solvent system, and the solvent system is selected from at least one of anhydrous ethanol or anhydrous methanol.

6. Use of the compound according to any one of claims 1 to 2 in aggregation-induced emission.

7. Use of the compound according to any one of claims 1 to 2 in preparation of a fluorescent sensor.

8. Use of the compound according to any one of claims 1 to 2 in preparation of an organic light-emitting material.

9. Use of the compound according to any one of claims 1 to 2 in preparation of a light-emitting device, a fluorescent probe, a fluorescent switch or a biological imaging agent.

Images