Preparation method and application of long-life organic room-temperature phosphorescent material based on filter paper substrate
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2022-10-13
- Publication Date
- 2026-08-11
AI Technical Summary
然而，目前有机发光材料领域已有的方法大部分都需要精巧的分子设计和复杂的合成手段
[0021]本发明的优点是：该制备方法合成步骤简单、收率高、成本低，适于规模化生产，可以应用于制备防伪标志。
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Abstract
Description
Technical Field
[0001] This invention relates to the field of luminescent materials technology, specifically to a method for preparing and applying a long-life organic room-temperature phosphorescent material based on a filter paper matrix. Background Technology
[0002] Organic room-temperature phosphorescent materials, due to their large Stokes shift, long decay lifetime, and long afterglow, have significant application value in fields such as anti-counterfeiting materials, molecular switches, and bioimaging. Compared with traditional inorganic or organometallic phosphorescent systems, pure organic room-temperature phosphorescent materials have advantages such as safety, non-toxicity, low cost, and good processability, showing broad application prospects. However, pure organic room-temperature phosphorescent materials are very scarce, and existing preparation processes are cumbersome and complex, with harsh synthesis conditions, severely limiting the large-scale application of phosphorescent materials. Therefore, it is essential to develop efficient, long-lifetime phosphorescent materials and explore their application value in cutting-edge scientific and technological fields.
[0003] Achieving high-efficiency pure organic phosphorescence emission at room temperature primarily hinges on effectively modulating intramolecular / intermolecular spin-orbit coupling to promote the intersystem crossing of singlet excitons into triplet excitons, thereby realizing high-efficiency phosphorescent pure organic RTP materials. However, most existing methods in the field of organic light-emitting materials require sophisticated molecular design and complex synthetic techniques. Filter paper offers advantages such as simple analytical methods, wide applicability, and ease of cutting; therefore, we developed a simple synthetic strategy for constructing pure organic room-temperature phosphorescent materials on filter paper substrates.
[0004] The heavy atoms in the compound can promote intersystem crossing (ISC) of the excited dye through external heavy atom effects, thereby inducing the generation of its excited triplet state. Simultaneously, phosphorescent molecules infiltrate into the filter paper fibers and become embedded, thus achieving rigidity and suppressing the nonradiative transition processes of the phosphor. In other words, the generation and stabilization of the dye's excited triplet state are both achieved through the same polymer matrix, thereby inducing room-temperature phosphorescence.
[0005] Based on the above analysis, this invention designs and synthesizes a long-life organic room-temperature phosphorescent material based on filter paper matrix, which can be applied in the fields of printing and anti-counterfeiting. This phosphorescent material features a simple preparation route, low cost, long luminescence lifetime, and low production cost, pointing to a direction for further research on organic room-temperature phosphorescent materials. Summary of the Invention
[0006] The purpose of this invention is to address the aforementioned problems by providing a simple preparation route for a filter paper matrix organic room temperature phosphorescent material, which also exhibits a long luminescence lifetime, and its application.
[0007] The technical solution of this invention:
[0008] This invention designs and synthesizes a low-cost, long-lifetime organic room-temperature phosphorescent material. The chemical formula of the phosphorescent molecule prepared in this invention is C0. 42 H 26 Br2N2O4S2, with a molecular weight of 846.6080, has the following molecular structure:
[0009]
[0010] The preparation steps are as follows:
[0011] 1) 1-Bromo-2-((4-fluorophenyl)sulfonyl)benzene: 2-Bromo-benzenesulfonyl chloride (2.0 g, 7.83 mmol) and fluorobenzene (2.2 mL, 23.49 mmol) were placed in a three-necked flask. Anhydrous ferric chloride (2.54 g, 15.66 mmol) was added under an argon atmosphere. The reaction was carried out at room temperature for 2 h, followed by quenching with 10 mL of 1M HCl. The mixture was extracted three times with dichloromethane, washed with water, and dried over anhydrous magnesium sulfate. After filtration under reduced pressure, the filtrate was purified by column chromatography (dichloromethane / petroleum ether, 1 / 2, v / v) to give a white solid (1.79 g, 72.5% yield).
[0012] The reaction formula is:
[0013]
[0014] 2) 5,11-Bis(4-(2-bromophenyl)sulfonyl)phenyl)-5,11-dihydroindolo[3,2-b]carbazole: Under a nitrogen atmosphere, 5,11-dihydroindolo[3,2-b]carbazole (271.7 mg, 1.06 mmol) was added to a three-necked flask, and 10 mL of DMF was added and stirred until dissolved. Potassium tert-butoxide (237.9 mg, 2.12 mmol) was added and stirred for 10 min, followed by the addition of 1-bromo-2-((4-fluorophenyl)sulfonyl)benzene (1 g, 3.17 mmol). The mixture was heated to 100 °C and stirred for 5 h. After the reaction was complete, the mixture was cooled to room temperature, and the reaction solution was poured into 20 mL of water for precipitation. The precipitate was filtered, washed with water, and a pale yellow solid (440.5 mg, yield 49.1%) was obtained. 1H NMR (400MHz, DMSO-d6) δ (ppm): 8.46 (d, J = 1.8Hz, 1H), 8.44 (d, J = 1.7Hz, 1H), 8.42 (d, J = 4.4Hz, 2H), 8.39 (s, 1H), 8.26 (d, J = 8.7Hz, 4H), 8.07 (d, J = 8. 6Hz, 4H), 7.94 (d, J=7.9Hz, 2H), 7.81 (t, J=7.6Hz, 3H), 7.74-7.69 (m, 2H), 7.54 (d, J=8.2Hz, 2H), 7.46 (t, J=7.7Hz, 2H), 7.30 (t, J=7.4Hz, 2H).MS (ESI + (m / z): [M+H]+calcd.for C 42 H 27 Br2N2O4S2 + :847.6155, found, 847.6140.
[0015] Reaction formula:
[0016]
[0017] The mass ratio of 2-bromo-benzenesulfonyl chloride, fluorobenzene, and anhydrous ferric chloride is 1:1.13:1.27.
[0018] The mass ratio of 1-bromo-2-((4-fluorophenyl)sulfonyl)benzene, 5,11-dihydroindolo[3,2-b]carbazole, and t-BuOK is 1:0.27:0.24.
[0019] The effects of long-life organic room-temperature phosphorescent materials based on filter paper matrix are as follows:
[0020] After drying the filter paper containing the compound molecules, a long afterglow phenomenon can be observed under ultraviolet light excitation (e.g., 365nm ultraviolet light excitation), with the phosphorescence lifetime reaching up to 760ms at room temperature.
[0021] The advantages of this invention are: the preparation method has simple synthesis steps, high yield, low cost, is suitable for large-scale production, and can be applied to the preparation of anti-counterfeiting marks. Attached Figure Description
[0022] Figure 1 The image shows the ultraviolet absorption spectrum of an organic room-temperature phosphorescent material based on filter paper.
[0023] Figure 2 Phosphorescence spectra of organic room-temperature phosphorescent materials on filter paper matrix before and after alkali addition.
[0024] Figure 3 Phosphorescence lifetime diagram of organic room temperature phosphorescent material based on filter paper. Detailed Implementation Plan
[0025] The present invention will be specifically described below through embodiments, but the present invention is not limited to the following embodiments.
[0026] Example:
[0027] This invention designs and synthesizes a low-cost, long-lifetime organic room-temperature phosphorescent material and its application. The chemical formula of the phosphorescent molecule prepared in this invention is C0. 42 H 26 Br2N2O4S2, with a molecular weight of 846.6080, has the following molecular structure:
[0028]
[0029] The preparation steps are as follows:
[0030] 1) 1-Bromo-2-((4-fluorophenyl)sulfonyl)benzene: 2-Bromo-benzenesulfonyl chloride (2.0 g, 7.83 mmol) and fluorobenzene (2.2 mL, 23.49 mmol) were placed in a three-necked flask. Anhydrous ferric chloride (2.54 g, 15.66 mmol) was added under an argon atmosphere. The reaction was carried out at room temperature for 2 h, followed by quenching with 10 mL of 1M HCl. The mixture was extracted three times with dichloromethane, washed with water, and dried over anhydrous magnesium sulfate. After filtration under reduced pressure, the filtrate was purified by column chromatography (dichloromethane / petroleum ether, 1 / 2, v / v) to give a white solid (1.79 g, 72.5% yield).
[0031] The reaction formula is:
[0032]
[0033] 2) 5,11-Bis(4-(2-bromophenyl)sulfonyl)phenyl)-5,11-dihydroindolo[3,2-b]carbazole: Under a nitrogen atmosphere, 5,11-dihydroindolo[3,2-b]carbazole (271.7 mg, 1.06 mmol) was added to a three-necked flask, and 10 mL of DMF was added and stirred until dissolved. Potassium tert-butoxide (237.9 mg, 2.12 mmol) was added and stirred for 10 min, followed by the addition of 1-bromo-2-((4-fluorophenyl)sulfonyl)benzene (1 g, 3.17 mmol). The mixture was heated to 100 °C and stirred for 5 h. After the reaction was complete, the mixture was cooled to room temperature, and the reaction solution was poured into 20 mL of water to precipitate. The precipitate was filtered, washed with water, and a pale yellow solid (440.5 mg, yield 49.1%) was obtained. 1H NMR (400MHz, DMSO-d6) δ (ppm): 8.46 (d, J = 1.8Hz, 1H), 8.44 (d, J = 1.7Hz, 1H), 8.42 (d, J = 4.4Hz, 2H), 8.39 (s, 1H), 8.26 (d, J = 8.7Hz, 4H), 8.07 (d, J = 8. 6Hz, 4H), 7.94 (d, J=7.9Hz, 2H), 7.81 (t, J=7.6Hz, 3H), 7.74-7.69 (m, 2H), 7.54 (d, J=8.2Hz, 2H), 7.46 (t, J=7.7Hz, 2H), 7.30 (t, J=7.4Hz, 2H).MS (ESI + (m / z): [M+H]+calcd.for C 42 H 27 Br2N2O4S2 + :847.6155, found, 847.6140.
[0034] Reaction formula:
[0035]
[0036] 3) Preparation of long-life organic room-temperature phosphorescent material based on filter paper: 20 mg of 5,11-bis(4-(2-bromophenyl)sulfonyl)phenyl)-5,11-dihydroindole[3,2-b]carbazole was added to 8 ml of DMF solution to obtain a saturated solution of the compound. The solution was heated at 120 °C for 10 min to dissolve it completely. The solution was then dropped onto filter paper moistened with potassium tert-butoxide. After the filter paper was dried, the long-life organic room-temperature phosphorescent material based on filter paper was obtained.
[0037] Figure 1 This is the ultraviolet absorption spectrum of the filter paper matrix organic room temperature phosphorescent material. As can be seen from the figure, the material has strong ultraviolet absorption at 340 nm.
[0038] Figure 2 This is the phosphorescence spectrum of the organic room-temperature phosphorescent material in the filter paper matrix. The vertical axis represents phosphorescence intensity (au), and the horizontal axis represents wavelength (nm). It can be seen that the filter paper undergoes a strong change after the addition of alkali. Under photoluminescence spectroscopy testing, it can emit both fluorescence with a wavelength of 423nm and phosphorescence with a wavelength of 500nm.
[0039] Figure 3 This is a phosphorescence lifetime diagram of an organic room-temperature phosphorescent material based on filter paper. The diagram shows that the material can be observed to have a long afterglow phenomenon under ultraviolet light excitation, and the phosphorescence lifetime can reach up to 760ms at room temperature.
Claims
1. An organic room-temperature phosphorescent material based on filter paper matrix, characterized in that... The molecular structure of the compound is as follows: 。