Aryl ketone derivatives containing tetraphenyl ethylene and carbazole units, methods of making and uses thereof
By preparing aryl ketone derivatives containing tetraphenylethylene and carbazole units, the problem of insufficient color and fluorescence intensity changes in traditional mechanochromic materials under external stimuli has been solved, achieving high-contrast fluorescence recording and inkless writing effects, and is recyclable.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- QINGHAI UNIVERSITY
- Filing Date
- 2023-12-22
- Publication Date
- 2026-05-19
AI Technical Summary
Traditional mechanochromic materials are difficult to achieve significant fluorescence color changes and fluorescence emission intensity changes under external stimuli, which cannot meet the requirements of high-contrast fluorescence recording.
This material was prepared by using an aryl ketone derivative containing tetraphenylethylene and carbazole units via a specific synthetic route. Under external force, the color was significantly altered and the fluorescence emission intensity was enhanced, making it suitable for use in inkless writing materials.
It achieves significant color change and increased fluorescence intensity under external force, making it suitable for high-contrast fluorescent recording and inkless writing. The material synthesis steps are simple and it can be recycled and reused.
Smart Images
Figure CN117700352B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of mechanochromic materials technology, and more specifically, to aryl ketone derivatives containing tetraphenylethylene and carbazole units, their preparation methods, and their applications. Background Technology
[0002] Because mechanochromatic materials are simple to obtain, easy to control, and environmentally friendly compared to other stimulus-induced color-changing materials, fluorescent molecular switches that respond to external stimuli, especially in the solid state, have received widespread attention in recent years. The emission color transition of these molecular switches can be triggered by various stimuli, such as force, ultraviolet / visible light, heat, acids / bases, and chemical vapors. However, for traditional mechanochromatic fluorescent materials, external stimuli generally only result in a noticeable change in fluorescence color. For high-contrast fluorescence recording, not only is a clear transition between two fluorescence colors before and after external stimuli required, but also a rapid change in fluorescence emission intensity, which is difficult to achieve with traditional mechanochromatic fluorescent materials.
[0003] In view of this, the present invention is proposed. Summary of the Invention
[0004] The purpose of this invention is to provide aryl ketone derivatives containing tetraphenylethylene and carbazole units, their preparation methods, and their applications. The aryl ketone derivatives containing tetraphenylethylene and carbazole units provided in this invention exhibit not only significant color changes upon application of force but also a substantial increase in fluorescence emission intensity, enabling high-contrast fluorescence recording and allowing for wide application in inkless writing.
[0005] This invention is implemented as follows:
[0006] In a first aspect, the present invention provides an aryl ketone derivative containing tetraphenylene and carbazole units, the structural formula of which is shown below:
[0007]
[0008] Secondly, the present invention provides a method for preparing the aryl ketone derivative containing tetraphenylethylene and carbazole units as described in the foregoing embodiments, comprising synthesis according to the following synthetic route:
[0009]
[0010] The target product is an aryl ketone derivative containing tetraphenylethylene and carbazole units.
[0011] In an optional embodiment, the step of forming compound 3 includes: mixing compound 1, compound 2, carbonate, ammonium substance and catalyst to carry out a reaction;
[0012] Preferably, the compound 1, the compound 2, the carbonate, the ammonium substance, and the solvent are mixed and then reacted with a Pd catalyst under an inert gas atmosphere.
[0013] In an optional embodiment, the molar ratio of compound 1 to compound 2 is 1:1.5-2.5; the molar ratio of compound 1 to the carbonate is 1:3-5; the molar ratio of compound 1 to the ammonium compound is 1:0.1-0.2; and the molar ratio of compound 1 to the catalyst is 1:0.005-0.01.
[0014] Preferably, the carbonate comprises sodium carbonate;
[0015] The ammonium compound includes tetrabutylammonium bisulfate; the catalyst includes Pd(PPh3)4;
[0016] Preferably, the reaction conditions include a temperature of 70-90°C and a time of 20-26 hours.
[0017] In an optional embodiment, the step of forming the target product includes: mixing compound 3, compound 4, carbonate, ammonium substance and catalyst to react;
[0018] Preferably, the reaction includes: mixing the compound 3, the compound 4, the carbonate, and the ammonium substance with a solvent, and then reacting them with a Pd catalyst under an inert gas atmosphere.
[0019] In an optional embodiment, the molar ratio of compound 3 to compound 4 is 1:1.1-1.5; the molar ratio of compound 3 to the carbonate is 1:3-4; the molar ratio of compound 3 to the ammonium compound is 1:0.1-0.15; and the molar ratio of compound 1 to the catalyst is 1:0.02-0.03.
[0020] Preferably, the carbonate comprises sodium carbonate;
[0021] The ammonium compound includes tetrabutylammonium bisulfate; the catalyst includes Pd(PPh3)4;
[0022] Preferably, the reaction conditions include a temperature of 70-90°C and a time of 20-26 hours.
[0023] Thirdly, the present invention provides the application of the aryl ketone derivative containing tetraphenylethylene and carbazole units described in the foregoing embodiments in the preparation of mechanochromic materials.
[0024] Fourthly, the present invention provides a mechanochromic material, the raw materials of which include the aryl ketone derivative containing tetraphenylethylene and carbazole units as described in the foregoing embodiments.
[0025] Fifthly, the present invention provides a method for recycling mechanochromic materials, comprising: adding the used mechanochromic material into an organic solvent for recrystallization.
[0026] In an optional embodiment, the organic solvent is a mixed solvent formed by mixing at least one of aliphatic hydrocarbon solvents (including but not limited to petroleum ether, n-hexane, n-heptane, etc.) and alcohol solvents with a haloalkane solvent.
[0027] Preferably, the volume ratio of at least one of the aliphatic hydrocarbon solvent and the alcohol solvent to the haloalkane solvent is 3-6:1;
[0028] Preferably, the volume ratio of the aliphatic hydrocarbon solvent to the haloalkane solvent is 3-6:1.
[0029] The present invention has the following beneficial effects: The aryl ketone derivative containing tetraphenylethylene and carbazole units provided in the embodiments of the present invention has a simple preparation route and high synthesis yield. Moreover, the derivative has obvious differences in color and fluorescence intensity before and after stress, which can be used for inkless writing and can also be used for writing on confidential and secure materials. Attached Figure Description
[0030] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.
[0031] Figure 1 The fluorescence spectra of the aryl ketone derivative containing tetraphenylene and carbazole units prepared in Example 1 of the present invention before and after stress.
[0032] Figure 2 The fluorescence images of the aryl ketone derivative containing tetraphenylene and carbazole units prepared in Example 1 of the present invention before and after stress.
[0033] Figure 3 The result diagram provided for detection example 3 of the present invention;
[0034] Figure 4 The fluorescence spectra of compound 5 before and after stress are provided as a comparative example of this invention.
[0035] Figure 5The fluorescence images of compound 5 before and after being subjected to force are provided as a comparative example of this invention. Detailed Implementation
[0036] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.
[0037] Currently, there are not many reported organic compounds that exhibit photoluminescence responses in the solid state. Among them, tetraphenylethylene derivatives are a class of molecules that have attracted widespread attention and have high utilization rates. Based on tetraphenylethylene, researchers have also designed many materials with photostimulation-responsive properties. For example, the compound TPE-MN is a "turn-on" type multistimulus-responsive material. Although this compound has tetraphenylethylene units with AIE activity, it forms a loose molecular stack under hydrogen bonding, resulting in almost no fluorescence emission in the crystalline state. Differential scanning calorimetry, powder diffraction XRD, and various photophysical analyses show that the loose crystalline stack provides sufficient space for molecular rotation and vibration, leading to solid-state fluorescence quenching. This loose crystalline stack will be disrupted by mechanical force or ultraviolet light irradiation, and the compound will produce a fluorescence peak with a maximum emission wavelength of 562 nm. However, current reports on such molecules are still very limited, and their quantity and optical properties are far from meeting the needs of the ever-growing field of materials science.
[0038] In a first aspect, the present invention provides an aryl ketone derivative containing tetraphenylene and carbazole units, the structural formula of which is shown below:
[0039]
[0040] Secondly, the present invention provides a method for preparing the aryl ketone derivative containing tetraphenylethylene and carbazole units as described in the foregoing embodiments, comprising synthesis according to the following synthetic route:
[0041]
[0042] The target product is an aryl ketone derivative containing tetraphenylethylene and carbazole units. Specifically, the reaction includes: mixing compound 1, compound 2, the carbonate, and the ammonium compound with a solvent (e.g., a mixture of toluene and water), and then reacting the mixture with a catalyst under an inert gas atmosphere (e.g., nitrogen). The catalyst can be a Pd catalyst, including but not limited to Pd(PPh3)4; the carbonate includes but is not limited to sodium carbonate; the ammonium compound includes but is not limited to tetrabutylammonium bisulfate; and the reaction conditions include a temperature of 70-90°C and a time of 20-26 hours.
[0043] The molar ratio of compound 1 to compound 2 is 1:1.5-2.5; the molar ratio of compound 1 to the carbonate is 1:3-5; the molar ratio of compound 1 to the ammonium substance is 1:0.1-0.2; and the molar ratio of compound 1 to the catalyst is 1:0.005-0.01.
[0044] Compound 3, compound 4, the carbonate, and the ammonium compound are mixed with a solvent (e.g., a mixture of toluene and water) and reacted with a catalyst under an inert gas atmosphere (e.g., nitrogen). The catalyst may be a Pd catalyst, including but not limited to Pd(PPh3)4; the carbonate includes but is not limited to sodium carbonate; the ammonium compound includes but is not limited to tetrabutylammonium bisulfate; the reaction conditions include a temperature of 70-90°C and a time of 20-26 hours.
[0045] The molar ratio of compound 3 to compound 4 is 1:1.1-1.5; the molar ratio of compound 3 to carbonate is 1:3-4; the molar ratio of compound 3 to ammonium is 1:0.1-0.15; and the molar ratio of compound 1 to catalyst is 1:0.02-0.03.
[0046] This aryl ketone derivative, containing tetraphenylethylene and carbazole units, exhibits a significant color change and a dramatic shift in fluorescence intensity upon stress. Therefore, it can be used as a mechanochromic material or an inkless writing material, suitable for writing on secure and confidential materials. Furthermore, the synthesis of this derivative is simple; tetraphenylethylene can be synthesized in just two steps, with high yields in each step.
[0047] Thirdly, the present invention provides the application of the aryl ketone derivative containing tetraphenylethylene and carbazole units described in the foregoing embodiments in the preparation of mechanochromic materials.
[0048] Fourthly, the present invention provides a mechanochromic material, the raw materials of which include the aryl ketone derivative containing tetraphenylethylene and carbazole units as described in the foregoing embodiments.
[0049] Fifthly, the present invention provides a method for recycling mechanochromic materials, comprising: adding the used mechanochromic material into an organic solvent for recrystallization.
[0050] The organic solvent is a mixed solvent formed by mixing at least one of aliphatic hydrocarbon solvents (including but not limited to petroleum ether, n-hexane, n-heptane, etc.) and alcohol solvents with a haloalkane solvent; for example, the volume ratio of at least one of the aliphatic hydrocarbon solvents and the alcohol solvents to the haloalkane solvent is 3-6:1; specifically, the volume ratio of the aliphatic hydrocarbon solvent to the haloalkane solvent is 3-6:1.
[0051] The features and performance of the present invention will be further described in detail below with reference to embodiments.
[0052] Example 1
[0053] This invention provides an aryl ketone derivative (hereinafter also referred to as TPE-BZ-C2) containing tetraphenylethylene and carbazole units, with the following structural formula:
[0054]
[0055] This embodiment also provides a method for preparing the above-mentioned aryl ketone derivatives containing tetraphenylethylene and carbazole units, which are synthesized according to the following synthetic route:
[0056]
[0057] The specific steps are as follows:
[0058] Synthesis of compound 3 ((4-bromophenyl)(4'-(1,2,2-tristyryl)-[1,1'-diphenyl]-4-yl)methyl ketone): Compound 1 (30.00 g, 65.44 mmol), compound 2 (45.00 g, 132.35 mmol), anhydrous Na2CO3 (24.60 g, 232.10 mmol), and tetrabutylammonium hydrogen sulfate (TBAHS, 3.70 g, 10.90 mmol) were placed in a 2000 mL three-necked flask, and 1200 mL of a toluene-water mixture (v / v = 3 / 2) was added. Under N2 protection, Pd(PPh3)4 (0.50 g, 0.43 mmol) was added, and the reaction was stirred at 80 °C for 24 h under N2 protection. After the reaction was completed, the system was cooled to room temperature, and the reaction solution was separated. The lower aqueous phase was extracted with DCM, and the organic phases were combined, dried over anhydrous Na2SO4, filtered, and the solvent was removed by rotary evaporation to obtain the crude product. The crude product was purified by silica gel column chromatography using petroleum ether / DCM (v / v = 1 / 2) as the eluent to obtain a white solid (28.60 g, 73%). 1HNMR (600MHz, CDCl3) δ7.85 (d, J = 8.4Hz, 2H), 7.72-7.66 (m, 6H), 7.43 (d, J = 8.4Hz, 2H), 7.16-7.06 (m, 17H); HRMS (Q Exactive Orbitrap MS, APCI) m / z: [M+H] + Calcd forC 37 H 26 NOS 532.1735; Found 532.1746.Anal.Calcd(%)for C 39 H 27 BrO: C 79.19, H 4.60; Found: C 79.38, H 4.72.
[0059] Synthesis of the target molecule TPE-BZ-C2 ((4-(9-ethyl-9H-carbazole-2-yl)phenyl)(4'-(1,2,2-tristyryl)-[1,1'-diphenyl]-4-yl)methyl ketone): Compound 3 (2.25 g, 3.80 mmol), compound 4 (1.50 g, 4.67 mmol), anhydrous Na2CO3 (1.50 g, 14.15 mmol), and tetrabutylammonium hydrogen sulfate (TBAHS, 0.18 g, 0.53 mmol) were placed in a 250 mL three-necked flask, and 70 mL of a toluene-water mixture (v / v = 3 / 2) was added. Under N2 protection, Pd(PPh3)4 (100 mg, 0.087 mmol) was added, and the reaction was stirred at 80 °C for 24 h under N2 protection. After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was separated. The lower aqueous phase was extracted with DCM, and the organic phases were combined, dried over anhydrous Na2SO4, and filtered. The solvent was removed by rotary evaporation to obtain the crude product. The crude product was purified by silica gel column chromatography using petroleum ether / DCM (v / v = 2 / 3) as the eluent to obtain a white solid (2.23 g, 83%). 1HNMR (600MHz, CDCl3) δ8.22(d,J=8.4Hz,1H),8.17(d,J=7.2Hz,1H),7.98(d,J=8.4Hz,2H),7.9 4(d,J=8.4Hz,2H),7.89(d,J=8.4Hz,2H),7.72(d,J=8.4Hz,2H),7.69(s,1H),7.57(d,J=8.4Hz, 1H),7.53(t,J=7.8Hz,J=7.2Hz,1H),7.47(t,J=8.4Hz,J=8.4Hz,3H),7.30(d,J=7.2Hz,1H),7. 18-7.10(m,15H),7.09-7.07(m,2H),4.50-4.47(m,2H),1.52(t,J=7.2Hz,J=7.2Hz,3H); HRMS(Q Exactive Orbitrap MS,APCI)m / z:[M+H] + Calcd for C 53 H 40 NO 706.3110;Found 706.3106.Anal.Calcd(%)forC 53 H 39 NO: C 90.18, H 5.57, N 1.98; Found: C 90.28, H 5.69, N 1.85.
[0060] Comparative Example
[0061] This comparative example provides a tetraphenylethylene derivative 5, the structural formula and synthetic route of which are as follows:
[0062]
[0063] Its synthesis is as follows:
[0064] Synthesis of compound 5 (bis(4'-(1,2,2-tristyryl)-[1,1'-diphenyl]-4-yl) methyl ketone): Compound 1 (60.00 g, 130.89 mmol), compound 2 (22.25 g, 65.44 mmol), anhydrous Na2CO3 (49.00 g, 462.32 mmol), and tetrabutylammonium hydrogen sulfate (TBAHS, 7.40 g, 21.80 mmol) were placed in a 2000 mL three-necked flask, and 1400 mL of a toluene-water mixture (v / v = 3 / 2) was added. Under N2 protection, Pd(PPh3)4 (1.00 g, 0.86 mmol) was added, and the reaction was stirred at 80 °C for 24 h under N2 protection. After the reaction was completed, the system was cooled to room temperature, and the reaction solution was separated. The lower aqueous phase was extracted with DCM, and the organic phases were combined, dried with anhydrous Na2SO4, filtered, and the solvent was removed by rotary evaporation to obtain the crude product. The crude product was purified by silica gel column chromatography using petroleum ether / DCM (v / v = 2 / 5) as the eluent to obtain a light yellow solid (46.90 g, 85%). 1 HNMR(600MHz, CDCl3)δ7.88(d,J=7.8Hz,4H),7.69(d,J=7.8Hz,4H),7.44(d,J=7.8Hz,4H),7.17-7.07(m,34H); Anal.Calcd(%)for C 65 H 46 O: C 92.60, H 5.50; Found: C 92.85, H 5.72.
[0065] Detection Example 1
[0066] The fluorescence spectra of the tetraphenylethylene derivatives provided in the above examples and comparative examples were detected, and their fluorescence images were obtained under a UV lamp (365 nm). The tetraphenylethylene derivatives were each ground in an agate mill under the same conditions for 5 minutes, and then the fluorescence spectra of the ground products were tested again, and their fluorescence images were obtained under a UV lamp (365 nm). The results are shown in [reference needed]. Figure 1-2 and Figure 4-5 .
[0067] according to Figure 1 and Figure 2It was found that the initial powder of the target molecule TPE-BZ-C2 emitted only extremely weak blue fluorescence at a wavelength of 451 nm, which was almost invisible to the naked eye, and its solid-state luminescence efficiency was only 0.22%. The ground powder exhibited bright yellow-green fluorescence, with a maximum emission wavelength at 490 nm, and a solid-state luminescence efficiency as high as 33.12%, which was 150.5 times that of the initial powder. The above test results show that TPE-BZ-C2 exhibits a more significant mechanoinduced fluorescence enhancement behavior, that is, TPE-BZ-C2 exhibits a high-contrast "turn-on" type MFC phenomenon.
[0068] according to Figure 4 and Figure 5 It can be seen that the initial crystalline powder of compound 5 in the comparative example exhibits a blue-green fluorescence color, with a maximum emission wavelength of 479 nm and a solid-state luminescence efficiency of 41.62%. After grinding the initial powder of compound 5 in the comparative example, its fluorescence color did not change and remained blue-green. The maximum emission peak underwent a slight red shift to 483 nm, and the solid-state luminescence efficiency also changed very little, remaining at 40.48%. Therefore, compound 5 in the comparative example does not possess mechanochromatic fluorescence properties.
[0069] In summary, even though they are all tetraphenylethylene derivatives, not all tetraphenylethylene derivatives can be used as mechanochromic materials. Some tetraphenylethylene derivatives do not change their fluorescent color and intensity even after being subjected to force, and therefore cannot be used as inkless writing materials.
[0070] Detection Example 2
[0071] Each of the above-mentioned ground aryl ketone derivatives containing tetraphenylethylene and carbazole units was placed in 10-100 ml of a mixed solvent (V). DCM V 石油醚 The mixture was recrystallized at 40°C in a ratio of 1:5, and then subjected to fluorescence detection.
[0072] It was found that the fluorescence intensity of the ground material returned to its original state after recrystallization, and the fluorescence intensity increased again after writing. This indicates that the aryl ketone derivative containing tetraphenylethylene and carbazole units provided in the embodiments of the present invention has recyclability and reusability.
[0073] Detection Example 3
[0074] The aryl ketone derivative containing tetraphenylethylene and carbazole units prepared in Example 1 was coated on filter paper. The three characters "New Era" were written with a metal spatula using normal writing pressure. Under a 365nm ultraviolet light, the bright yellow-green characters, distinct from the dark blue background, were visible (see [link to example]). Figure 3 This indicates that the aryl ketone derivatives containing tetraphenylethylene and carbazole units provided in the embodiments of the present invention are fluorescently sensitive to mechanical force.
[0075] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.
Claims
1. An aryl ketone derivative containing tetraphenylethylene and carbazole units, characterized in that, Its structural formula is shown below: 。 2. A method for preparing an aryl ketone derivative containing tetraphenylethylene and carbazole units as described in claim 1, characterized in that, This includes synthesis following the synthetic pathway: The target product is an aryl ketone derivative containing tetraphenylene and carbazole units; The steps for forming compound 3 are as follows: compound 1, compound 2, carbonate, ammonium compounds, and solvent are mixed and reacted with a Pd catalyst under an inert gas atmosphere. The steps to form the target product are as follows: after mixing the compound 3, compound 4, carbonate, ammonium substance and solvent, the mixture is reacted with the Pd catalyst under an inert gas atmosphere; The carbonate is sodium carbonate; the ammonium compound is tetrabutylammonium hydrogen sulfate.
3. The preparation method according to claim 2, characterized in that, The molar ratio of compound 1 to compound 2 is 1:1.5-2.5; the molar ratio of compound 1 to the carbonate is 1:3-5; the molar ratio of compound 1 to the ammonium substance is 1:0.1-0.2; and the molar ratio of compound 1 to the Pd catalyst is 1:0.005-0.
01.
4. The preparation method according to claim 2, characterized in that, The Pd catalyst is Pd(PPh3)4.
5. The preparation method according to claim 2, characterized in that, The reaction conditions include a temperature of 70-90℃ and a time of 20-26 hours.
6. The preparation method according to claim 2, characterized in that, The molar ratio of compound 3 to compound 4 is 1:1.1-1.5; the molar ratio of compound 3 to carbonate is 1:3-4; the molar ratio of compound 3 to ammonium is 1:0.1-0.15; and the molar ratio of compound 1 to catalyst is 1:0.02-0.
03.
7. The use of an aryl ketone derivative containing tetraphenylethylene and carbazole units as described in claim 1 in the preparation of mechanochromic materials.
8. A mechanochromic material, characterized in that, Its raw materials include the aryl ketone derivatives containing tetraphenylethylene and carbazole units as described in claim 1.
9. A method for recycling mechanochromic materials, characterized in that, include: The used mechanochromic material of claim 8 is added to an organic solvent for recrystallization.
10. The method for recycling mechanochromic materials according to claim 9, characterized in that, The organic solvent is a mixed solvent formed by mixing at least one of aliphatic hydrocarbon solvents and alcohol solvents with a haloalkane solvent.
11. The method for recycling mechanochromic materials according to claim 10, characterized in that, The volume ratio of at least one of the aliphatic hydrocarbon solvent and the alcohol solvent to the haloalkane solvent is 3-6:
1.
12. The method for recycling mechanochromic materials according to claim 11, characterized in that, The volume ratio of the aliphatic hydrocarbon solvent to the haloalkane solvent is 3-6:1.