Organic luminescent material with mechanochromism and aggregation-induced emission properties and preparation method thereof
By synthesizing organic light-emitting materials with mechanochromic and aggregation-induced emission properties, the problems of insignificant fluorescence changes under external stimuli and luminescence quenching in the aggregated state of existing materials have been solved, thus realizing the application requirements of high-sensitivity sensors and information storage.
Patent Information
- Application Number
- CN202510988135.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-17
- Publication Date
- 2025-11-07
AI Technical Summary
Existing organic light-emitting materials do not show significant changes in fluorescence performance under external stimuli, and their light emission is quenched in the aggregated state, making it difficult to meet the needs of high-sensitivity sensors and information storage.
Design an organic light-emitting material with mechanochromic and aggregation-induced emission properties. Synthesize specific molecular structures through Suzuki-Miyaura coupling reaction, Knoevenagel reaction and Buchwald-Hartwig coupling reaction, and introduce tetraphenylethylene groups and aryl or heteroaryl groups to form a material with mechanochromic effect.
It achieves significant color or luminescence changes in materials under external force, enhances luminescence performance in the aggregated state, and is suitable for high-sensitivity optical sensors and writable/erasable information storage devices, showing promising application prospects.
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Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of organic synthesis and luminescent materials, and particularly relates to an organic luminescent material with mechanofluorochromism and aggregation-induced emission performance and a preparation method thereof. BACKGROUND
[0002] Mechanofluorochromism (MFC) refers to a substance that changes in fluorescence emission wavelength, intensity or lifetime under external force stimulation. The change is generally caused by the transformation of intermolecular interaction, molecular packing mode or molecular conformation. As an important part of stimulus-responsive materials, MFC materials are concerned due to their dynamic and reversible fluorescence emission adjustment, and have wide application potential.
[0003] Aggregation-Induced Emission (AIE) is a photophysical phenomenon discovered and defined by Professor Tang Benzhong's team in 2001. That is, a luminescent material does not emit light or emits weak light when it is dissolved in a good solvent in a molecular form, but the luminescent performance is significantly enhanced when it is aggregated in a poor solvent or in a solid form. Compared with the phenomenon of luminescence quenching of traditional fluorescent materials in a solid state or an aggregated state, AIE technology can overcome the shortcomings of traditional materials by designing and synthesizing specific molecular structures. Aggregation-induced emission has wide applications in sensing, biological imaging and diagnosis and treatment, optoelectronic devices and intelligent stimulus-responsive materials. Therefore, the development of new AIE materials has attracted high attention of researchers.
[0004] Therefore, it is of great significance to design and develop an organic luminescent material with mechanofluorochromism and aggregation-induced emission performance. SUMMARY
[0005] The application aims to solve the above-mentioned problems, and provides an organic luminescent material with mechanofluorochromism and aggregation-induced emission performance and a preparation method thereof.
[0006] To solve the above technical problems, the technical scheme provided by the application is as follows: an organic luminescent material with mechanofluorochromism and aggregation-induced emission performance, the structure general formula of the luminescent material is as follows:
[0007]
[0008] Preferably, Ar1 and Ar2 are aryl or heteroaryl.
[0009] Preferably, Ar1 is phenyl, biphenyl, naphthyl, anthracene, thienyl, furanyl, and Ar2 is phenothiazine, phenoxazine, naphthyl, anthracene.
[0010] Preferably, the structure general formula of Ar1 is as follows:
[0011]
[0012] Preferably, the Ar1 structural formula is as follows:
[0013]
[0014] A preparation method of an organic luminescent material with mechanochromic and aggregation-induced emission properties, the preparation steps are as follows:
[0015] S1, coupling bromotetraphenylethylene with aldehyde-based aromatic boronic acid or aldehyde-based aromatic boronic acid ester by Suzuki-Miyaura reaction;
[0016] S2, then coupling the coupling product with p-bromophenylacetonitrile to obtain a condensation product by Knoevenagel reaction;
[0017] S3, and then obtaining the corresponding target end product by Suzuki-Miyaura coupling reaction or Buchwald-Hartwig coupling reaction.
[0018] The application of an organic luminescent material with mechanochromic and aggregation-induced emission properties, the luminescent material is applied to sensors, data storage and anti-counterfeiting materials.
[0019] Compared with the prior art, the present application has the following advantages:
[0020] The present application provides an organic luminescent material with mechanochromic and aggregation-induced emission (AIE) properties and its preparation method and application. Through reasonable molecular structure design, the tetraphenylethylene group is taken as the core skeleton, and different aryl or heteroaryl groups (such as phenyl, biphenyl, naphthyl, anthracene, thiophene, furan, phenothiazine, phenoxazine, etc.) are introduced, which not only endows the material with excellent fluorescence performance, but also makes it have the ability to respond to external mechanical stimulation (i.e. mechanochromic effect). Through multi-step synthesis strategies such as Suzuki-Miyaura coupling reaction and Knoevenagel condensation, the target molecular structure can be efficiently constructed. The material of this kind shows obvious color or luminescence change under external force, and is suitable for constructing high-sensitivity optical sensors, writable / erasable information storage devices and high-safety anti-counterfeiting materials, and has good application prospect and practical value. BRIEF DESCRIPTION OF DRAWINGS
[0021] Figure 1 is the fluorescence spectrum of the compound TPE-Ph-CN-PTZ prepared in Example 1 of the present application before and after stress.
[0022] Figure 2is the compound TPE-Ph-CN-PTZ prepared by embodiment 1 of the present application, and the aggregation-induced emission property is measured.
[0023] Figure 3 is the fluorescence spectrum of the compound TPE-Ph-CN-EN before and after stress prepared by embodiment 2 of the present application.
[0024] Figure 4 is the aggregation-induced emission property of the compound TPE-Ph-CN-EN prepared by embodiment 2 of the present application.
[0025] Figure 5 is the fluorescence spectrum of the compound TPE-Th-CN-PTZ before and after stress prepared by embodiment 3 of the present application.
[0026] Figure 6 is the aggregation-induced emission property of the compound TPE-Th-CN-PTZ prepared by embodiment 3 of the present application. DETAILED DESCRIPTION
[0027] In the description of the present application, it should be understood that the terms "upper", "lower", "front", "back", "left", "right", "inner", "outer", "center" and the like indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, and are merely for the convenience of describing the present application and simplifying the description, and do not indicate or imply that the device or element referred to must have a particular orientation or configuration and operation, and therefore cannot be understood as a limitation on the present application.
[0028] In the description of the present application, it should be understood that unless otherwise explicitly specified and limited, the terms "provided with", "mounted", "connected", "linked" and the like should be understood broadly, for example, it can be fixedly connected, or it can be detachably connected, or it can be integrally connected, it can be mechanically connected, or it can be electrically connected, it can be directly connected, or it can be indirectly connected through an intermediate medium, it can be the communication between the two elements inside. For those skilled in the art, the specific meaning of the above terms in the present application can be understood according to the specific circumstances.
[0029] The present application will be further described in detail below with reference to the accompanying drawings.
[0030] The present application is an organic luminescent material with force-induced color change and aggregation-induced emission performance, the structure general formula is as follows:
[0031]
[0032] Among them: Ar1 and Ar2 are aryl or heteroaryl.
[0033] Preferably, Ar1 is phenyl, biphenyl, naphthyl, anthracenyl, thienyl, furanyl, and Ar2 is phenothiazine, phenoxazine, naphthyl, anthracenyl.
[0034] More preferably, Ar1 is selected from the following structures:
[0035]
[0036] More preferably, Ar2 is selected from the following structures:
[0037]
[0038] The synthesis method of the organic light-emitting material having the mechanochromic and aggregation-induced emission properties is a three-step reaction of Suzuki-Miyaura coupling reaction, Knoevenagel reaction, Buchwald-Hartwig coupling reaction, etc. to obtain the target end product.
[0039] The present application is further described below through specific examples, but the present application is not limited to this specific example.
[0040] Example 1
[0041] A compound (labeled as TPE-Ph-CN-PTZ) having the mechanochromic and aggregation-induced emission properties, the preparation method thereof comprises the following steps:
[0042] (1) Under nitrogen protection, 1-(4-bromophenyl)-1,2,2-triphenylstyrene (4.11 g, 10.0 mmol) and 4-formylphenylboronic acid (1.80 g, 12.0 mmol), potassium carbonate (3.46 g, 25.0 mmol), 1,1'-bis(diphenylphosphino)ferrocene palladium dichloride (366 mg, 0.5 mmol) are added to a Schlenk flask, 50 mL of a mixed solution of methanol and toluene (volume ratio 1:4) subjected to oxygen removal operation are added, and the reaction is stirred and refluxed for 16 h. The reaction is cooled to room temperature, TLC spotting is performed, after the reaction is completed, the cold reaction solution is poured into 100 mL of water, extraction is performed with dichloromethane. The organic phase is dried with anhydrous sodium sulfate, the solvent is removed, and separation and purification are performed with a silica gel column, using a mixed solvent of petroleum ether and ethyl acetate (volume ratio 15:1) as an eluent, to obtain 3.58 g of a light green solid compound A, with a yield of 82%.
[0043] The reaction formula of this step is as follows:
[0044]
[0045] (2) The compound A (2.18 g, 5.0 mmol) and p-bromophenylacetonitrile (980 mg, 5.0 mmol) were added to a round-bottom flask, dissolved in 20 mL of anhydrous ethanol, followed by the addition of potassium tert-butoxide (672 mg, 6.0 mmol), and the reaction was stirred and refluxed for 6 h. The reaction was monitored by thin layer chromatography (TLC) spotting, and after the reaction was completed, the system was cooled to room temperature, and suction filtration was performed to obtain 2.73 g of a yellow-green solid compound B, with a yield of 89%.
[0046] The reaction formula of this step is as follows:
[0047]
[0048] (3) Under nitrogen protection, compound B (1.23 g, 2.0 mmol) and phenothiazine (399 mg, 2.0 mmol), potassium tert-butoxide (336 mg, 3.0 mmol), bis(dibenzylideneacetone)palladium (113 mg, 0.2 mmol), and tri-tert-butylphosphonium tetrafluoroborate (116 mg, 0.4 mmol) were added to a Schlenk flask, 20 mL of dried toluene was added, and the reaction was stirred and refluxed for 24 h. After the reaction was cooled to room temperature, it was monitored by thin layer chromatography (TLC) spotting, and after the reaction was completed, the cold reaction liquid was poured into 20 mL of water, and extraction was performed using dichloromethane. The organic phase was dried with anhydrous sodium sulfate, the solvent was removed, and separation and purification were performed using a silica gel column, with a mixed solvent of petroleum ether and dichloromethane (volume ratio of 3:1) as the eluent, to obtain 1.07 g of an orange-yellow solid compound TPE-Ph-CN-PTZ, with a yield of 73%.
[0049] The reaction formula of this step is as follows:
[0050]
[0051] Example 2
[0052] A compound (labeled as TPE-Ph-CN-EN) having a mechanochromic and aggregation-induced emission property, which is different from the reference example 1 in that phenothiazine in the (3) step is replaced by 9-anthraceneboronic acid, has a preparation method comprising the following steps:
[0053] Compound B (1.23 g, 2.0 mmol) and 9-anthraceneboronic acid (533 mg, 2.4 mmol), potassium carbonate (692 mg, 5.0 mmol), 1,1'-bis(diphenylphosphino) ferrocene palladium dichloride (73.2 mg, 0.1 mmol) were added into a Schlenk flask under nitrogen protection, and a mixture of methanol and toluene (20 mL, volume ratio 1:4) which had been subjected to deoxygenation was added, and the reaction was stirred and refluxed for 16 h. The reaction was cooled to room temperature, and thin layer chromatography (TLC) was performed. After the reaction was completed, the cold reaction solution was poured into 50 mL of water, and dichloromethane was used for extraction. The organic phase was dried with anhydrous sodium sulfate, the solvent was removed, and the product was separated and purified by silica gel column chromatography using a mixture of petroleum ether and dichloromethane (volume ratio 3:1) as the eluent to obtain 968 mg of light green solid compound TPE-Ph-CN-EN with a yield of 68%.
[0054] The reaction formula of this step is as follows:
[0055]
[0056] Example 3
[0057] A compound (labeled as TPE-Th-CN-PTZ) having a mechanochromic and aggregation-induced emission property, which is different from the reference example 1 in that 4-formylphenylboronic acid in step (1) is replaced by 5-aldehyde-2-thiopheneboronic acid, and the preparation method thereof comprises the following steps:
[0058] (1) 1-(4-bromophenyl)-1,2,2-triphenylstyrene (4.11 g, 10.0 mmol) and 5-aldehyde-2-thiopheneboronic acid (1.87 g, 12.0 mmol), potassium carbonate (3.46 g, 25.0 mmol), 1,1'-bis(diphenylphosphino) ferrocene palladium dichloride (366 mg, 0.5 mmol) were added into a Schlenk flask under nitrogen protection, and a mixture of methanol and toluene (50 mL, volume ratio 1:4) which had been subjected to deoxygenation was added, and the reaction was stirred and refluxed for 16 h. The reaction was cooled to room temperature, and thin layer chromatography (TLC) was performed. After the reaction was completed, the cold reaction solution was poured into 100 mL of water, and dichloromethane was used for extraction. The organic phase was dried with anhydrous sodium sulfate, the solvent was removed, and the product was separated and purified by silica gel column chromatography using a mixture of petroleum ether and ethyl acetate (volume ratio 15:1) as the eluent to obtain 3.36 g of orange yellow solid compound C with a yield of 76%.
[0059] The reaction formula of this step is as follows:
[0060]
[0061] (2) The compound C (2.21 g, 5.0 mmol) and p-bromophenylacetonitrile (980 mg, 5.0 mmol) were added to a round-bottom flask, dissolved in 20 mL of anhydrous ethanol, followed by the addition of potassium tert-butoxide (672 mg, 6.0 mmol), and the reaction was stirred and refluxed for 6 h. The reaction was monitored by thin layer chromatography (TLC) spotting, and after the reaction was completed, the system was cooled to room temperature, and suction filtration was performed to obtain 2.58 g of a yellow-green solid compound B, with a yield of 83%.
[0062] The reaction formula of this step is as follows:
[0063]
[0064] (3) Under nitrogen protection, compound D (1.24 g, 2.0 mmol) and phenothiazine (399 mg, 2.0 mmol), potassium tert-butoxide (336 mg, 3.0 mmol), bis(dibenzylideneacetone)palladium (113 mg, 0.2 mmol), and tri-tert-butylphosphonium tetrafluoroborate (116 mg, 0.4 mmol) were added to a Schlenk flask, 20 mL of dried toluene was added, and the reaction was stirred and refluxed for 24 h. The reaction was cooled to room temperature, and thin layer chromatography (TLC) spotting was performed for monitoring, and after the reaction was completed, the cold reaction liquid was poured into 20 mL of water, and extraction was performed with dichloromethane. The organic phase was dried with anhydrous sodium sulfate, the solvent was removed, and silica gel column separation and purification were performed with a mixed solvent of petroleum ether and dichloromethane (3:1 by volume) as the eluent to obtain 1.03 g of an orange-red solid compound TPE-Th-CN-PTZ, with a yield of 70%.
[0065] The reaction formula of this step is as follows:
[0066]
[0067] Test Example
[0068] This test example tests the structure of the compound prepared in the examples, the change in the fluorescence emission wavelength of the solid powder mechano-chromic fluorescence, and the aggregation-induced emission effect.
[0069] In order to explore the mechano-chromic performance of the compounds in Examples 1-3 in the scheme of the application, the test results are shown in Table 1. The original fluorescence emission wavelength of the compound in Example 1 was 547 nm, and the fluorescence emission wavelength of the sample after rolling was 584 nm, with a 37 nm obvious red shift; the original fluorescence emission wavelength of the compound in Example 2 was 487 nm, and the fluorescence emission wavelength of the sample after rolling was 512 nm, with a 25 nm obvious red shift; the original fluorescence emission wavelength of the compound in Example 3 was 600 nm, and the fluorescence emission wavelength of the sample after rolling was 607 nm, with a 7 nm red shift but the change was not obvious.
[0070] Table 1 wavelength change of fluorescence emission of the solid powder of the compound in examples 1-3
[0071]
[0072] Note: Δλ = λground- λpristine
[0073] Only part of the test 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.
[0074] In order to explore the aggregation-induced emission performance of the compound in the scheme of the application, water, a poor solvent, is added to the tetrahydrofuran solution of the compound in examples 1-3, and the change of the fluorescence intensity of the solution is observed with different water content. From the above results, it can be seen that the AIE performance of the compound in example 1 is weak when the water content is less than 60%, but when the water content reaches 99%, the fluorescence intensity of the solution increases suddenly, which is 7.5 times that of the pure tetrahydrofuran solution, and the fluorescence emission wavelength has a relatively obvious red shift. Figure 2 From the above results, it can be seen that the AIE performance of the compound in example 2 is the weakest when the water content is 70%, and the fluorescence intensity gradually increases with the increase of the water content, and when the water content reaches 99%, the fluorescence intensity of the solution increases suddenly, which is 2 times that of the pure tetrahydrofuran solution. Figure 4 From the above results, it can be seen that the AIE performance of the compound in example 3 is the weakest when the water content is 80%, but when the water content reaches 99%, the fluorescence intensity of the solution increases suddenly, which is 6 times that of the pure tetrahydrofuran solution. The experimental data show that the compound in the scheme of the application has good AIE performance. Figure 6 From the above results, it can be seen that the AIE performance of the compound in example 3 is the weakest when the water content is 80%, but when the water content reaches 99%, the fluorescence intensity of the solution increases suddenly, which is 6 times that of the pure tetrahydrofuran solution. The experimental data show that the compound in the scheme of the application has good AIE performance.
[0075] From the above results, it can be seen that the compound in the scheme of the application has good mechanochromic and aggregation-induced emission performance, and therefore has good application prospect in the fields of sensor preparation, data storage and anti-counterfeiting materials.
[0076] The above describes the application and its embodiments, which are not restrictive, and the embodiment shown in the drawings is only one of the embodiments of the application, and the actual structure is not limited thereto. In general, if a person skilled in the art is inspired thereby, without departing from the purpose of the application, without creative design, similar structure modes and examples of the technical scheme should belong to the protection scope of the application.
Claims
1. An organic light-emitting material having a mechanochromic and an aggregation-induced emission property, characterized by The structural general formula of the light-emitting material is as follows:
2. The organic light-emitting material with mechanochromic and aggregation-induced emission properties according to claim 1, characterized in that, The Ar1 and Ar2 are aryl or heteroaryl. 3.The organic luminescent material with mechanochromic and aggregation-induced emission performance according to claim 2, characterized in that, The Ar1 is phenyl, biphenyl, naphthyl, anthracene, thienyl, furanyl, and the Ar2 is phenothiazine, phenoxazine, naphthyl, anthracene.
4. The organic luminescent material with mechanochromic and aggregation-induced emission properties according to claim 3, characterized in that, The structural general formula of the Ar1 is as follows: 5.The organic luminescent material with mechanochromic and aggregation-induced emission performance according to claim 3, wherein, The structural general formula of the Ar1 is as follows:
6. The method for preparing an organic light-emitting material with mechanochromic and aggregation-induced emission properties according to claim 1, characterized in that, The preparation steps are as follows: S1, coupling bromotetraphenyl ethylene with aldehyde aromatic boronic acid or aldehyde aromatic boronic acid ester by Suzuki-Miyaura reaction; S2, then coupling the product with p-bromophenylacetonitrile to obtain condensation product by Knoevenagel reaction; S3, then obtaining the corresponding target final product by Suzuki-Miyaura coupling reaction or Buchwald-Hartwig coupling reaction. 7.The application of the organic luminescent material with force-induced color change and aggregation-induced emission performance according to claim 1, wherein, The light-emitting material is applied to sensors, data storage and anti-counterfeiting materials.