Condensed ring phosphorescent compounds, methods of making and using the same
By designing and synthesizing nitrogen-containing fused ring compounds, the problems of short lifespan and easy bleaching of phosphorescent materials with heavy metal complexes have been solved, providing phosphorescent compounds with long afterglow in the range of several seconds, which are suitable for high-end printing, information storage, intelligent sensing and anti-counterfeiting labeling and other fields.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- GUANGZHOU LIJING OPTICAL TECHNOLOGY CO LTD
- Filing Date
- 2026-01-30
- Publication Date
- 2026-07-21
AI Technical Summary
Existing heavy metal complex phosphorescent materials have short triplet exciton lifetimes, are easily photobleached, and their phosphorescence performance deteriorates in complex application systems, making it difficult to meet the needs of dynamic display and long-term tracking. At the same time, they have high synthesis costs and pose a significant risk of environmental pollution.
By developing nitrogen-containing fused-ring compounds and using specific compound design and synthesis methods, phosphorescent compounds with long afterglow lifetimes of several seconds were prepared. These compounds exhibit excellent resistance to photobleaching and solvent elution, and can be applied in luminescent materials.
It achieves long afterglow emission characteristics on the order of several seconds, significantly extending the material's service life and improving its stability and performance in complex environments. It is suitable for high-end printing, information storage, intelligent sensing, and anti-counterfeiting labeling.
Smart Images
Figure CN122427136A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of luminescent materials technology. More specifically, it relates to a class of fused-ring phosphorescent compounds, their preparation methods, and applications. Background Technology
[0002] Phosphorescence refers to the emission of light emitted when a substance absorbs light energy, forms a triplet exciton through intersystem crossing, and then radiatively transitions back to its ground state. Because the radiative transition of the triplet exciton is a spin-forbidden process, traditional fluorescent materials can only emit light using singlet excitons, with a theoretical upper limit of only 25% for internal quantum efficiency. This bottleneck restricts the performance improvement of luminescent materials. The discovery of heavy metal complex phosphorescent materials has completely broken this limitation, among which Ir... 3+ Pt 2+ Transition metal complexes with phosphorescent elements as the core can efficiently promote intersystem crossings and achieve efficient phosphorescence emission by leveraging strong spin-orbit coupling, making them a research hotspot in the field of luminescent materials.
[0003] However, existing heavy metal complex phosphorescent materials have short triplet exciton lifetimes (typically less than 20 milliseconds), making it difficult to meet the continuous luminescence requirements of dynamic displays and long-term tracking applications. Furthermore, the synthesis of these materials is demanding and costly, and the use of heavy metals can easily cause environmental pollution. Against this backdrop, pure organic phosphorescent materials, due to their ease of preparation and environmental friendliness, have gradually become a new research direction in the field of phosphorescent materials. However, pure organic systems still face key challenges: first, the materials are prone to photobleaching under continuous illumination, leading to a sharp decline in phosphorescence lifetime and luminescence intensity; second, when added to complex application systems such as inks and coatings, interactions with solvent molecules can cause a significant decrease or even complete quenching of phosphorescence performance, severely restricting their practical applications.
[0004] Therefore, developing phosphorescent compounds that combine resistance to photobleaching and solvent elution has become a pressing challenge in this field. Summary of the Invention
[0005] This invention addresses the shortcomings of existing phosphorescent materials, such as poor resistance to photobleaching and solvent elution, and aims to provide a class of fused-ring phosphorescent compounds, their preparation methods, and applications.
[0006] The first object of the present invention is to provide a class of nitrogen-containing fused-ring compounds or pharmaceutically acceptable salts thereof.
[0007] A second object of the present invention is to provide a method for preparing the nitrogen-containing fused-ring compound or a pharmaceutically acceptable salt thereof.
[0008] A third objective of this invention is to provide the application of the nitrogen-containing fused-ring compound in the preparation of luminescent materials.
[0009] A fourth objective of this invention is to provide a luminescent material.
[0010] The fifth objective of this invention is to provide the application of the nitrogen-containing fused ring compound or the luminescent material in the preparation of smart display materials, information storage and encryption anti-counterfeiting materials, and optoelectronic and sensor devices.
[0011] The above-mentioned objective of this invention is achieved through the following technical solution:
[0012] This invention protects a class of nitrogen-containing fused-ring compounds or pharmaceutically acceptable salts thereof, having the structure of Formula I:
[0013] Ⅰ In Formula I, Ar-1 is selected from any one of phenyl, naphthyl, phenanthryl, and pyrene. The Ar-2 is selected from any one of phenyl, naphthyl, phenanthryl, and pyrene; The A is selected from The n represents the number of A on Ar-1, and n is any integer in the range of 1 to 5; The R is selected from , , , , , , , , , Any one of them; The R 1 Selected from C 1～6 Any one of the alkyl groups.
[0014] The nitrogen-containing fused-ring compound provided by this invention exhibits a longer afterglow lifetime of several seconds, compared to the millisecond-level luminescence duration of existing phosphorescent compounds. This meets the core requirement of continuous luminescence in scenarios such as dynamic displays and long-term tracking. In the photobleaching resistance test, the compound can basically maintain its initial luminescence intensity after continuous strong light irradiation. In the solvent elution resistance test, it shows that the compound's luminescence performance does not significantly decrease after immersion in organic solvents, effectively solving the problem of easy failure of existing materials in complex organic systems. Based on these advantages, this compound shows significant application value in fields such as high-end printing, high-density information storage, intelligent sensing, and anti-counterfeiting labels.
[0015] Preferably, the Ar-1 is selected from any one of phenyl, 1-naphthyl, and 2-naphthyl; The Ar-2 is selected from , , , , , , , , , , Any one of them; n is any integer in the range of 1 to 3; The R is selected from , , Any one of them; The R 1 Selected from C 1～3 Any one of the alkyl groups.
[0016] As a specific implementable method, the nitrogen-containing fused ring compound is any one of the following structural formulas I-1 to I-5: .
[0017] This invention also protects a method for preparing the nitrogen-containing fused-ring compound or a pharmaceutically acceptable salt thereof, the preparation of the nitrogen-containing fused-ring compound comprising the following steps: S1: In the presence of the first organic solvent and the first catalyst, compound 1 and compound 2 are reacted completely, and after post-treatment, compound 3, i.e., a carboxylic acid derivative, is obtained; S2: In the presence of a second organic solvent, a carboxylic acid activator, and a second catalyst, compounds 3 and 4 are reacted completely. After post-treatment, compound I, the target compound, is obtained. ; The Ar-1, Ar-2, A, n, R, R 1 The definition is the same as above.
[0018] Preferably, in step S1, the first organic solvent is selected from at least one of toluene, dimethylformamide, ethylene glycol dimethyl ether, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, and dimethyl sulfoxide.
[0019] Further, in step S1, the first organic solvent is toluene, dimethylformamide, or ethylene glycol dimethyl ether.
[0020] Preferably, in step S1, the first catalyst is selected from at least one of polyphosphoric acid and boric acid.
[0021] Furthermore, in step S1, the first catalyst is polyphosphoric acid or boric acid.
[0022] Preferably, in step S1, the reaction is carried out under the protection of a protective gas.
[0023] Furthermore, the protective gas is selected from any one of nitrogen, helium, and argon.
[0024] More preferably, the protective gas is nitrogen.
[0025] Preferably, in step S1, the post-processing includes cooling, precipitation, filtration, washing, and purification.
[0026] Furthermore, the precipitation is achieved by adding a poor solvent to the mixture after the reaction is completed, thereby promoting the precipitation of the precipitate.
[0027] More preferably, the volume ratio of the mixture to the undesirable solvent is 1:(0.8 to 1.2), and even more preferably 1:1.
[0028] More preferably, the undesirable solvent is selected from at least one of water, n-heptane, and petroleum ether.
[0029] More preferably, the undesirable solvent is selected from at least one of water and n-heptane.
[0030] Furthermore, the washing process involves washing with water and ethanol sequentially.
[0031] Further, the purification involves adding an organic solvent to the washed precipitate for recrystallization. The organic solvent is preferably an ethyl acetate-dichloromethane mixed solvent (the volume ratio of ethyl acetate to dichloromethane is 0.8-1.2:0.8-1.2, more preferably 1:1) or a petroleum ether-ethyl acetate mixed solvent (the volume ratio of petroleum ether to ethyl acetate is 0.8-1.2:0.8-1.2, more preferably 1:1).
[0032] As a specific optional implementation, in step S1, the post-treatment involves adding water or n-heptane, which is equal to the total volume of the mixture after the reaction, filtering to collect the precipitate, washing the precipitate with water and ethanol in sequence, and then recrystallizing with a mixed solvent of ethyl acetate and dichloromethane in a volume ratio of 1:1 to obtain a carboxylic acid derivative.
[0033] Preferably, in step S1, the reaction temperature is 80–150°C, more preferably 90–130°C.
[0034] Preferably, in step S1, the reaction time is 2 to 16 hours, more preferably 4 to 12 hours.
[0035] Preferably, in step S1, the molar ratio of compound 1 to compound 2 is 1:(1 to 1.5), more preferably 1:1.2.
[0036] Preferably, in step S1, the molar ratio of compound 1 to the first catalyst is 1:(0.1 to 0.3), more preferably 1:0.2.
[0037] Preferably, in step S2, the second organic solvent is selected from at least one of dichloromethane, chloroform, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, and dimethyl sulfoxide.
[0038] More preferably, in step S2, the second organic solvent is dichloromethane.
[0039] Preferably, in step S2, the second catalyst is selected from at least one of 4-dimethylaminopyridine and 4-pyrrolidinylpyridine.
[0040] Further, in step S2, the second catalyst is 4-dimethylaminopyridine.
[0041] Preferably, in step S2, the carboxylic acid activator is selected from at least one of N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride and N,N'-dicyclohexylcarbodiimide.
[0042] Further, in step S2, the carboxylic acid activator is N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride.
[0043] Preferably, in step S2, the post-processing includes filtration, washing, and purification.
[0044] Furthermore, the washing process involves sequentially washing with a sodium bicarbonate solution and a sodium chloride solution.
[0045] Further, the purification involves adding an organic solvent to the washed precipitate for recrystallization. The organic solvent is preferably a petroleum ether-dichloromethane mixed solvent (the volume ratio of petroleum ether to dichloromethane is 1.6-2.4:0.8-1.2, more preferably 2:1) or a petroleum ether-ethyl acetate mixed solvent (the volume ratio of petroleum ether to ethyl acetate is 1.6-2.4:0.8-1.2, more preferably 2:1).
[0046] As a specific optional implementation, in step S2, the post-treatment involves filtering the crude product after the reaction is completed, washing the crude product sequentially with saturated sodium bicarbonate solution and saturated sodium chloride solution, and then recrystallizing it with a petroleum ether-dichloromethane mixed solvent at a volume ratio of 2:1 to obtain the target compound.
[0047] Preferably, in step S2, the reaction time is 2 to 4 hours, more preferably 3 hours.
[0048] Preferably, in step S2, the molar ratio of compound 3 to compound 4 is 1:(1 to 1.5), more preferably 1:1.2.
[0049] Preferably, in step S2, the molar ratio of compound 3 to the second catalyst is 1:(0.1 to 0.3), more preferably 1:0.2.
[0050] Preferably, in step S2, the molar ratio of compound 3 to carboxylic acid activator is 1:(1 to 1.5), more preferably 1:1.2.
[0051] This invention also protects the use of the nitrogen-containing fused ring compound in the preparation of luminescent materials.
[0052] The present invention also protects a luminescent material comprising at least one of the nitrogen-containing fused ring compounds.
[0053] Preferably, the luminescent material further comprises a resin, more preferably a cured synthetic resin.
[0054] Optionally, the curable synthetic resin includes a photocurable synthetic resin or a thermocurable synthetic resin.
[0055] Specifically, the photocurable synthetic resin may include a UV-curable acrylic resin, and the thermocurable synthetic resin may include a thermocurable epoxy resin.
[0056] This invention also protects the application of the nitrogen-containing fused ring compound or the luminescent material in the preparation of smart display materials, information storage and encryption anti-counterfeiting materials, and optoelectronic and sensor devices.
[0057] The present invention has the following beneficial effects: 1. Compared to the millisecond-level luminescence duration of existing phosphorescent materials, the nitrogen-containing fused ring compound provided by this invention has a luminescence characteristic of several seconds, making it irreplaceable in core scenarios such as dynamic display and long-term tracking. 2. This compound also has excellent anti-photobleaching properties, which can significantly extend the effective service life of materials and significantly reduce product replacement costs caused by photoaging, making it especially suitable for application scenarios that require long-term exposure to strong light. 3. This compound also exhibits excellent solvent elution resistance. When the material comes into contact with organic solvents (such as printing inks and cleaning agents) or in a humid environment, it can effectively prevent dissolution, peeling or performance degradation, significantly improving the material's environmental adaptability and durability. Attached Figure Description
[0058] Figure 1 In Figure A, the fluorescence and phosphorescence spectra of the target compound obtained in Example 4 are compared. Figure 1 B in the figure is a comparison of the fluorescence spectrum and phosphorescence spectrum of the target compound obtained in Example 5.
[0059] Figure 2In the figure, A represents the phosphorescence spectrum of the target compound obtained in Example 1; Figure 2 B in the figure represents the phosphorescence spectrum of the target compound obtained in Example 2; Figure 2 C in the figure represents the phosphorescence spectrum of the target compound obtained in Example 3.
[0060] Figure 3 In the figure, A represents the phosphorescence attenuation curves of the target compounds obtained in Examples 1-3; Figure 3 B in the figure represents the phosphorescence decay curve of the target compound obtained in Examples 4-5.
[0061] Figure 4 The images show the phosphorescence spectrum changes of the carboxylic acid derivative and the target compound obtained in Example 4 after they were mixed and cured with UV-curable acrylic resin and then eluted with ethanol. In the images, "A" represents the carboxylic acid derivative in Example 4 and "B" represents the target compound obtained in Example 4.
[0062] Figure 5 The image shows the phosphorescence spectrum changes before and after 10x simulated sunlight irradiation following the curing of the target compound obtained in Example 4 with UV-curable acrylic resin. Detailed Implementation
[0063] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, but the embodiments do not limit the present invention in any way. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in this technical field.
[0064] Unless otherwise specified, all reagents and materials used in the following examples are commercially available.
[0065] The UV-curable acrylic resin used in this invention is from Changxing Chemical Industry Co., Ltd., model number 621A-80; the thermosetting epoxy resin used is from Baling Petrochemical Branch (Yueyang) of China Petrochemical Corporation Asset Management Co., Ltd., model number CYD-128 / E-51.
[0066] Example 1 Synthesis of 2-(acryloyloxy)ethyl-4-(pyrene[4,5-d]oxazol-10-yl)benzoate The reaction pathway of the target compound is shown below: .
[0067] The specific preparation includes the following steps: 5-Aminopyrene-4-phenol (1.0 equivalent), terephthalic acid (1.2 equivalent), and polyphosphoric acid (0.2 equivalent, Sinopharm, CAS: 8017-16-1) were dissolved in ethylene glycol dimethyl ether and reacted at 130°C for 6 h under nitrogen protection. After the reaction was complete, the mixture was cooled to room temperature, and water with an equal volume to the total volume of the mixture was added, resulting in the precipitation of a large amount of solid. The solid was collected by filtration and washed successively with cold water and ethanol to obtain a crude carboxylic acid derivative. Finally, the product was purified by recrystallization (using a 1:1 volume ratio of ethyl acetate to dichloromethane mixture as the solvent) to obtain the carboxylic acid derivative (orange-yellow solid). The carboxylic acid derivative (1.0 equivalent), hydroxyethyl acrylate (1.2 equivalent), and 4-dimethylaminopyridine (0.2 equivalent) were dissolved in dichloromethane, and N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (1.2 equivalent) was added. The mixture was stirred at room temperature for 3 h. After the reaction was completed, the crude product was obtained by filtration and washed successively with saturated sodium bicarbonate solution and saturated brine. Finally, it was purified by recrystallization (using a petroleum ether-dichloromethane mixed solvent with a volume ratio of 2:1) to obtain an orange-yellow solid, which is the target compound 2-(acryloyloxy)ethyl-4-(pyrene[4,5-d]oxazol-10-yl)benzoate.
[0068] Its structure was confirmed by ¹H NMR (DMSO-d6, 500MHz) δ: 9.01 (d, J =8.0Hz, 1H), 8.96 (d, J =8.0Hz, 1H), 8.80-8.74 (m, 2H), 8.25 (d, J =8.0Hz, 1H), 8.20 (d, J =8.0Hz, 1H), 8.05 (d, J =8.5Hz, 2H, Ar-H), 7.85 (d, J =8.5Hz, 2H, Ar-H), 6.40 (dd, J =17.3, 1.5Hz, 1H, CHH=CH-), 6.15 (dd, J =17.3, 10.4Hz, 1H, -CH=), 5.95 (dd, J =10.4, 1.5Hz, 1H, CHH=CH-), 4.55-4.50 (m, 4H, -OCH2CH2O-), 4.30 (t, J =5.0Hz, 2H, -OCH2-), 4.15 (t, J =5.0Hz, 2H, -OCH2-). MALDI-TOF (m / z): [M] + calcd.for C29 H 19 NO5, 461.13; found, 461.16.
[0069] Example 2 Synthesis of 2-methacryloyloxyethyl-4-(phenanthro[9,10-d]oxazol-2-yl)benzoate The reaction pathway of the target compound is shown below: .
[0070] 10-Aminophenanthrene-9-phenol (1.0 equivalent), terephthalic acid (1.2 equivalent), and polyphosphoric acid (0.2 equivalent) were dissolved in dimethylformamide and reacted under nitrogen protection at 120°C for 5 h with stirring. After the reaction was complete, the mixture was cooled to room temperature, and water with an equal volume to the total volume of the mixture was added, resulting in the precipitation of a large amount of solid. The solid was collected by filtration and washed successively with cold water and ethanol to obtain a crude carboxylic acid derivative. Finally, the product was purified by recrystallization (using a 1:1 volume ratio of ethyl acetate to dichloromethane mixture as the solvent) to obtain a carboxylic acid derivative (light yellow solid). The carboxylic acid derivative (1.0 equivalent), hydroxyethyl methacrylate (1.2 equivalent), and 4-dimethylaminopyridine (0.2 equivalent) were dissolved in dichloromethane, and N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (1.2 equivalent) was added. The mixture was stirred at room temperature for 3 h. After the reaction was complete, the crude product was obtained by filtration and washed successively with saturated sodium bicarbonate solution and saturated brine. Finally, the product was purified by recrystallization (using a petroleum ether-dichloromethane mixture with a volume ratio of 2:1) to obtain a light yellow solid, which is the target compound 2-methacryloyloxyethyl-4-(phenanthro[9,10-d]oxazol-2-yl)benzoate.
[0071] Its structure was confirmed by ¹H NMR (DMSO-d6, 500MHz) δ: 9.50 (d, J =8.5Hz, 1H, Phen-H), 9.15 (d, J =8.5Hz, 1H, Phen-H), 8.95 (d, J =8.0Hz, 1H, Phen-H), 8.65 (t, J =7.5Hz, 1H, Phen-H), 8.45 (t, J =7.5Hz, 1H, Phen-H), 8.30 (d, J =8.0Hz, 1H, Phen-H), 8.25 (d, J =8.5Hz, 2H, Ar-H), 8.05 (d, J=8.5Hz, 2H, Ar-H), 6.25 (s, 1H, =CH2), 5.85 (s, 1H, =CH2), 4.55 (t, J =4.5Hz, 2H, -OCH2-), 4.40 (t, J =4.5Hz, 2H, -OCH2-), 2.05 (s, 3H, -CH3). MALDI-TOF (m / z): [M] + calcd.for C 28 H 20 NO5, 450.1341; found, 450.14.
[0072] Example 3 Synthesis of 2-methacryloyloxyethyl-4-(naphtho[1,2-d]oxazol-2-yl)benzoate The reaction pathway of the target compound is shown below: .
[0073] 1-Aminonaphthyl-2-phenol (1.0 equivalent), terephthalic acid (1.2 equivalent), and polyphosphoric acid (0.2 equivalent) were dissolved in dimethylformamide and reacted under nitrogen protection at 120°C for 4 h with stirring. After the reaction was complete, the mixture was cooled to room temperature, and water with an equal volume to the total volume of the mixture was added, resulting in the precipitation of a large amount of solid. The solid was collected by filtration and washed successively with cold water and ethanol to obtain a crude carboxylic acid derivative. Finally, the product was purified by recrystallization (using a 1:1 volume ratio of ethyl acetate to dichloromethane mixture as the solvent) to obtain a carboxylic acid derivative (light yellow solid). The carboxylic acid derivative (1.0 equivalent), hydroxyethyl methacrylate (1.2 equivalent), and 4-dimethylaminopyridine (0.2 equivalent) were dissolved in dichloromethane, and N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (1.2 equivalent) was added. The mixture was stirred at room temperature for 3 h. After the reaction was complete, the crude product was obtained by filtration and washed successively with saturated sodium bicarbonate solution and saturated brine. Finally, the product was purified by recrystallization (using a petroleum ether-dichloromethane mixture with a volume ratio of 2:1) to obtain a light yellow solid, which is the target compound 2-methacryloyloxyethyl-4-(naphtho[1,2-d]oxazol-2-yl)benzoate.
[0074] Its structure was confirmed by ¹H NMR spectroscopy (DMSO-d6, 500 MHz) and the results were: δ: 8.90 (d, J =8.5Hz, 1H, Naph-H), 8.55 (d, J =8.0Hz, 1H, Naph-H), 8.20 (d, J =8.5Hz, 2H, Ar-H), 7.85 (d,J =8.5Hz, 2H, Ar-H), 7.75-7.55 (m, 3H, Naph-H), 6.20 (s, 1H, =CH2), 5.80 (s, 1H, =CH2), 4.50 (t, J =4.5Hz, 2H, -OCH2-), 4.35 (t, J =4.5Hz, 2H, -OCH2-), 2.05 (s, 3H, -CH3). MALDI-TOF (m / z): [M] + calcd.for C 24 H 19 NO5, 401.13; found, 401.16.
[0075] Example 4 Synthesis of 2-Acryloyloxyethyl 6-(phenanthro[9,10-d]oxazol-2-yl)naphthalene-2-carboxylate The reaction pathway of the target compound is shown below: .
[0076] 10-Aminophenanthrene-9-phenol (1.0 equivalent), 2,6-naphthalenedicarboxylic acid (1.2 equivalent), and boric acid (0.2 equivalent) were dissolved in toluene and reacted at 90°C for 12 h under nitrogen protection. After the reaction was complete, the mixture was cooled to room temperature, and a large amount of solid precipitated after adding an amount of n-heptane equal to the total volume of the mixture. The solid was collected by filtration and washed with ethanol to obtain a crude carboxylic acid derivative. Finally, the product was purified by recrystallization (using a 1:1 volume ratio of ethyl acetate to dichloromethane mixture as solvent) to obtain a carboxylic acid derivative (light yellow solid). The carboxylic acid derivative (1.0 equivalent), hydroxyethyl acrylate (1.2 equivalent), and 4-dimethylaminopyridine (0.2 equivalent) were dissolved in dichloromethane, and N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (1.2 equivalent) was added. The mixture was stirred at room temperature for 3 h. After the reaction was complete, the crude product was obtained by filtration and washed successively with saturated sodium bicarbonate solution and saturated brine. Finally, the product was purified by recrystallization (using a petroleum ether-dichloromethane mixture with a volume ratio of 2:1) to obtain a light yellow solid, which is the target compound 2-acryloyloxyethyl 6-(phenanthro[9,10-d]oxazol-2-yl)naphthalene-2-carboxylate.
[0077] Its structure was confirmed by ¹H NMR (DMSO-d6, 500MHz) δ: 9.50 (d, J =8.5Hz, 1H, Phen-H), 9.15 (d, J =8.5Hz, 1H, Phen-H), 9.00 (s, 1H, Naph-H), 8.95 (d,J =8.0Hz, 1H, Phen-H), 8.65 (t, J =7.5Hz, 1H, Phen-H), 8.45 (t, J =7.5Hz, 1H, Phen-H), 8.30 (d, J =8.0Hz, 1H, Phen-H), 8.25 (d, J =8.5Hz, 1H, Naph-H), 8.15 (d, J =8.5Hz, 1H, Naph-H), 7.90 (d, J =8.5Hz, 1H, Naph-H), 7.75 (d, J =8.5Hz, 1H, Naph-H), 7.65 (t, J =7.5Hz, 1H, Naph-H), 7.55 (t, J =7.5Hz, 1H, Naph-H), 6.40 (dd, J =17.3, 1.5Hz, 1H, CHH=CH-), 6.15 (dd, J =17.3, 10.4Hz, 1H, -CH=), 5.95 (dd, J =10.4, 1.5Hz, 1H, CHH=CH-), 4.60 (t, J =4.5Hz, 2H, -OCH2-), 4.45 (t, J =4.5Hz, 2H, -OCH2-). MALDI-TOF (m / z): [M] + calcd.for C 31 H 21 NO5, 487.1419; found, 487.15.
[0078] Example 5 Synthesis of glycidyl-2-methyl 6-(naphtho[2,1-d]oxazol-2-yl)naphthalene-2-carboxylate The reaction pathway of the target compound is shown below: .
[0079] 2-Aminonaphth-1-phenol (1.0 equivalent), 2,6-naphthalenedicarboxylic acid (1.2 equivalent), and boric acid (0.2 equivalent) were dissolved in ethylene glycol dimethyl ether and reacted at 120°C for 4 h under nitrogen protection. After the reaction was complete, the mixture was cooled to room temperature, and water with an equal volume to the total volume of the mixture was added, resulting in the precipitation of a large amount of solid. The solid was collected by filtration and washed successively with cold water and ethanol to obtain a crude carboxylic acid derivative. Finally, the product was purified by recrystallization (using a 1:1 volume ratio of ethyl acetate to dichloromethane mixture as the solvent) to obtain the carboxylic acid derivative (a light yellow solid). The carboxylic acid derivative (1.0 equivalent), glycidyl ether (1.2 equivalent), and 4-dimethylaminopyridine (0.2 equivalent) were dissolved in dichloromethane, and N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (1.2 equivalent) was added. The mixture was stirred at room temperature for 3 h. After the reaction was completed, the crude product was obtained by filtration and washed successively with saturated sodium bicarbonate solution and saturated brine. Finally, it was purified by recrystallization (using a petroleum ether-dichloromethane mixed solvent with a volume ratio of 2:1) to obtain a light yellow solid, which is the target compound glycidyl 2-methyl 6-(naphtho[2,1-d]oxazol-2-yl)naphthalene-2-carboxylate.
[0080] Its structure was confirmed by ¹H NMR (DMSO-d6, 500MHz) δ: 9.15 (d, J =8.5Hz, 1H, Naph-H), 8.90 (s, 1H, Naph-H), 8.55 (d, J =8.0Hz, 1H, Naph-H), 8.30-8.20 (m, 2H, Naph-H), 8.10 (d, J =8.5Hz, 1H, Naph-H), 7.95 (d, J =8.5Hz, 1H, Naph-H), 7.80-7.50 (m, 5H, Naph-H), 4.45 (dd, J =11.5, 3.0Hz, 1H, -OCH2-), 4.30 (dd, J =11.5, 6.0Hz, 1H, -OCH2-), 3.95-3.90 (m, 1H, -CH(O)CH2-), 3.25 (t, J =5.0Hz, 1H, -OCH2CH-), 2.80 (dd, J =5.0, 4.0Hz, 1H, -OCH2CH-). MALDI-TOF (m / z): [M+H] + calcd.for C 25 H 18 NO4, 396.1230; found, 396.12 ([M]+ calcd.for C 25 H 17 NO4, 395.1158).
[0081] Test Example 1: Phosphorescence Property Test The phosphorescence properties of the target compounds obtained in Examples 1-5 were tested. The target compounds obtained in Examples 1-4 were cured with UV-curable acrylic resin at 50 mW / cm² for 5 seconds (the mass ratio of the target compound to the UV-curable acrylic resin was 1:200). The target compound obtained in Example 5 was cured with thermosetting epoxy resin at 100°C for 15 minutes (the mass ratio of the target compound to the thermosetting epoxy resin was 1:200). Fluorescence spectroscopy was performed using an Edinburgh Instruments FLS1000 steady-state and transient fluorescence spectrometer. The spectra were adjusted to "Steady-State Fluorescence" for fluorescence spectroscopy, "Steady-State Phosphorescence" for phosphorescence spectroscopy, and "Time-Resolved Phosphorescence" for phosphorescence decay curve testing.
[0082] The fluorescence and phosphorescence spectra of the target compounds obtained in Examples 4 and 5 are compared as follows: Figure 1 As shown.
[0083] The phosphorescence spectra of the target compounds obtained in Examples 1-3 are as follows: Figure 2 As shown.
[0084] Figure 1 , Figure 2 The results show that the target compound molecules exhibit strong phosphorescence properties after curing in the resin.
[0085] The phosphorescence decay curve test results of the target compounds obtained in Examples 1-5 are as follows: Figure 3 As shown, the time-resolved phosphorescence intensity curves of the phosphorescence peaks after curing the target compounds obtained in Examples 1-3 with UV-curable acrylic resin show a phosphorescence duration of approximately 3 seconds and lifetimes of 323 ms, 305 ms, and 314 ms, respectively. The fluorescence and phosphorescence spectra of the target compound obtained in Example 4 after curing with UV-curable acrylic resin show a phosphorescence duration of approximately 5 seconds and a lifetime of 456 ms. The fluorescence and phosphorescence spectra of the target compound obtained in Example 5 after curing with thermosetting epoxy resin show a phosphorescence duration of approximately 1 second and a lifetime of 120 ms.
[0086] Test Example 2 Solvent Eluting Resistance Test The target compound obtained in Example 4 was used as a representative compound for solvent elution test. Specifically, the carboxylic acid derivative and the target compound obtained in Example 4 were mixed with UV-curable acrylic resin and cured (curing steps and conditions were the same as in Test Example 1). The mixture was then soaked in ethanol for 24 h and the phosphorescence spectra before and after soaking were recorded.
[0087] Experimental results are as follows Figure 4 As shown, although the carboxylic acid derivative exhibited a strong phosphorescence emission peak before immersion, the peak intensity almost decreased to 0 after immersion, indicating poor bonding stability with the resin matrix. In contrast, the final product of Example 4 maintained the same phosphorescence spectrum peak position before and after immersion, with a complete peak shape and only a slight decrease in intensity, demonstrating excellent solvent elution resistance. This result fully confirms that the target compound obtained in Example 4 forms a stable covalent cross-linked structure with the resin matrix, effectively solving the problem of traditional phosphorescent compounds being easily eluted by solvents.
[0088] The solvent elution resistance of the target compounds in other embodiments is similar and will not be described again here.
[0089] Test Example 3: Light Bleaching Resistance Test Using the target compound obtained in Example 4 as a representative compound, a photobleaching resistance test was conducted. The target compound obtained in Example 4 was cured in UV-curable acrylate (curing steps and conditions were the same as in Test Example 1), and then subjected to 10 times simulated sunlight (with standard solar irradiance (AM1.5G, 1000W / m²)). 2 (Using this as a reference, the simulated light irradiance is 10000 W / m².) 2 Irradiate for 72 hours and record the phosphorescence spectra before and after irradiation.
[0090] Experimental results are as follows Figure 5 As shown, the phosphorescence intensity of the target compound obtained in Example 4 did not decrease significantly before and after irradiation, and the peak shape and position remained stable, exhibiting excellent photobleaching resistance. This result demonstrates that the compound provided by the present invention has strong photobleaching resistance, solving the defect of traditional phosphorescent materials being prone to failure under outdoor or long-term light exposure conditions, and providing a guarantee for the long-term application of materials in high-end printing, information storage, intelligent sensing, and anti-counterfeiting labeling fields.
[0091] The photobleaching resistance of the target compounds in other embodiments is similar and will not be described again here.
[0092] In summary, the compounds provided by this invention not only possess a long afterglow lifetime on the order of several seconds, surpassing the short-lived luminescence characteristics of traditional phosphorescent materials, but also exhibit excellent photostability, superior resistance to photobleaching, and outstanding solvent elution resistance. These properties can significantly extend the material's lifespan under light exposure and improve its structural and performance reliability in complex systems such as organic solvents and humid environments. This enables the materials to meet the stringent requirements for long-term application in high-end printing, information storage, intelligent sensing, and anti-counterfeiting labeling fields.
[0093] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.
Claims
1. A class of nitrogen-containing fused-ring compounds or pharmaceutically acceptable salts thereof, characterized in that, It has the structure of Formula I: Ⅰ In Formula I, Ar-1 is selected from any one of phenyl, naphthyl, phenanthryl, and pyrene. The Ar-2 is selected from any one of phenyl, naphthyl, phenanthryl, and pyrene; The A is selected from The n represents the number of A on Ar-1, and n is any integer in the range of 1 to 5; The R is selected from , , , , , , , , , Any one of them; The R 1 Selected from C 1～6 Any one of the alkyl groups.
2. The nitrogen-containing fused-ring compound or a pharmaceutically acceptable salt thereof as described in claim 1, characterized in that, The Ar-1 is selected from any one of phenyl, 1-naphthyl, and 2-naphthyl; The Ar-2 is selected from , , , , , , , , , , Any one of them; n is any integer in the range of 1 to 3; The R is selected from , , Any one of them; The R 1 Selected from C 1～3 Any one of the alkyl groups.
3. The nitrogen-containing fused-ring compound or a pharmaceutically acceptable salt thereof as described in claim 1, characterized in that, The nitrogen-containing fused ring compound is any one of the following structural formulas I-1 to I-5: 。 4. A method for preparing the nitrogen-containing fused-ring compound or a pharmaceutically acceptable salt thereof according to any one of claims 1 to 3, characterized in that, The preparation of the nitrogen-containing fused ring compound includes the following steps: S1: In the presence of the first organic solvent and the first catalyst, compound 1 and compound 2 are reacted completely, and after post-treatment, compound 3, i.e., a carboxylic acid derivative, is obtained; S2: In the presence of a second organic solvent, a carboxylic acid activator, and a second catalyst, compounds 3 and 4 are reacted completely. After post-treatment, compound I, the target compound, is obtained. ； The Ar-1, Ar-2, A, n, R, R 1 The definition is consistent with that of any one of claims 1 to 3.
5. The method as described in claim 4, characterized in that, In step S1, the first catalyst is selected from at least one of polyphosphoric acid and boric acid.
6. The method as described in claim 4, characterized in that, In step S2, the second catalyst is selected from at least one of 4-dimethylaminopyridine and 4-pyrrolidinylpyridine.
7. The method as described in claim 4, characterized in that, In step S2, the carboxylic acid activator is selected from at least one of N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride and N,N'-dicyclohexylcarbodiimide.
8. The use of the nitrogen-containing fused ring compound according to any one of claims 1 to 3 in the preparation of luminescent materials.
9. A luminescent material, characterized in that, It includes at least one of the nitrogen-containing fused ring compounds according to any one of claims 1 to 3.
10. The application of the nitrogen-containing fused ring compound according to any one of claims 1 to 3 or the luminescent material according to claim 9 in the preparation of smart display materials, information storage and encryption anti-counterfeiting materials, optoelectronic and sensor devices.