Organic narrow-band afterglow material based on halo-benzene derivative and preparation and application methods thereof

Abstract

The invention discloses an organic narrow-band afterglow material based on a halo-benzene derivative and a preparation method and an application method of the organic narrow-band afterglow material. The organic narrow-band afterglow material comprises a subject component and an object component serving as a light-emitting dopant, wherein the object component is a halo-benzene derivative with a specific structure. The preparation method comprises the following steps: synthesizing the object component through Friedel-Crafts acylation reaction or Suzuki reaction, and combining the object component with the subject component through grinding crystallization or extrusion processing or pouring to obtain the organic narrow-band afterglow material. The obtained organic narrow-band afterglow material is narrow in emission half-peak width, long in luminescence service life, high in photoluminescence quantum yield and convenient to prepare.

Description

Technical Field

[0001] The present invention relates to the technical field of luminescent materials, in particular to an organic narrow-band luminescent material based on coronene derivatives. Background Art

[0002] Narrow-band afterglow materials have a small half-width and high color purity, and have obvious advantages in advanced display technology, optical sensing and detection, biomedical imaging and other fields.

[0003] However, the emission bands of most existing organic room temperature long afterglow materials are relatively wide. Studies have found that the main reasons for their large half-peak widths include: (1) structural vibration relaxation of the excited state; (2) oscillator coupling between the excited state and the ground state. In response to the above two factors, some recent studies in the field of organic light-emitting diodes have shown that the multi-resonance effect can make the highest occupied molecular orbital and the lowest unoccupied molecular orbital be located on different atoms, suppressing the oscillator coupling between the excited state and the ground state, and realizing the narrow-band emission of the luminescent material. A variety of preparation strategies for narrow-band luminescent materials for organic light-emitting diodes based on this effect have been proposed. For example, Hatakeyama et al. designed a series of organic narrow-band emitters based on the DABNA skeleton using the multiple resonance effects of boron and nitrogen atoms (Adv. Mater. 2016, 28, 2777–2781, etc.); You Jinsong, Bin Zhengyang et al. developed three organic narrow-band emitters, BF-PZ, MeBF-PZ and MeBF-MePZ, based on the BODIPY skeleton (Angew. Chem. Int. Ed. 2023, 62, e202306471).

[0004] However, the above research mainly focuses on electroluminescent narrow-band materials for organic light-emitting diodes and cannot be directly used to obtain narrow-band afterglow materials of photoluminescence.

[0005] On the other hand, the existing preparation strategies of organic narrow-band afterglow materials mainly focus on the narrow-band emission phenomenon caused by the multiple resonance effect. The half-width of the obtained organic narrow-band afterglow materials is usually 30-35nm, and the luminescence lifetime is 3-500ms. There are problems of too wide half-width and short luminescence lifetime. Summary of the invention

[0006] In view of the defects of the prior art, the purpose of the present invention is to provide a new organic narrow-band afterglow material based on coronene derivatives and a preparation and application method thereof, so as to solve the problems of the existing organic afterglow materials such as wide emission half-width, short luminescence lifetime and low photoluminescence quantum yield.

[0007] The technical solution of the present invention is as follows:

[0008] An organic narrow-band afterglow material based on a coronene derivative comprises a host component and a guest component as a luminescent dopant, wherein the guest component comprises a coronene derivative having the following structural formula:

[0009]

[0010] Among them, R1-R 11 Selected from -H or -D; R 12 Selected from -C or -S; R 13 Any one selected from -H, -D, -Br; R 14 Selected from -H, -D, Any one of R 15 Selected from -H, -Br,

[0011] Any one of R 16 Selected from -H or -D; R 17 Selected from any one of -H, -D, and -Br.

[0012] According to some preferred embodiments of the present invention, the structural formula of the coronene derivative is one or more of Formula (I) to Formula (XVIII):

[0013]

[0014]

[0015] According to some preferred embodiments of the present invention, the main component is selected from one or more of phenyl benzoate, polymethyl methacrylate, and dimethyl isophthalate.

[0016] According to some preferred embodiments of the present invention, the mass of the guest component is 0.001 to 0.1% of the mass of the host component.

[0017] The present invention further provides a method for preparing the above-mentioned organic narrow-band afterglow material, which comprises:

[0018] The guest component was synthesized by Friedel-Crafts acylation or Suzuki reaction;

[0019] The guest component and the host component are combined by grinding and crystallization or extrusion processing or casting to obtain the organic narrow-band afterglow material; wherein the grinding and crystallization is for non-polymer host components, and the extrusion processing or casting method is for polymer host components;

[0020] Wherein, the Friedel-Crafts acylation reaction comprises:

[0021] A first Friedel-Crafts acylation reaction, namely: mixing coronene, aluminum chloride and dichloromethane at a constant temperature of 0° C. to obtain a first mixed solution;

[0022] dissolving an acyl chloride compound in dichloromethane, and then adding the acyl chloride compound into the first mixed solution, reacting at room temperature to obtain the guest component;

[0023] or,

[0024] A second Friedel-Crafts acylation reaction, namely: mixing a phenyl acid or a phenyl acid derivative with ultra-dry dichloromethane, then slowly adding trifluoroacetic anhydride, then adding coronene, and then slowly adding trifluoromethanesulfonic acid, reacting at room temperature to obtain the guest component; wherein the phenyl acid derivative includes phenyl acid ester and / or phenyl acid salt;

[0025] The Suzuki reaction includes:

[0026] Mixing a bromine-substituted coronene derivative, a phenylboronic acid compound, palladium acetate, potassium carbonate and N,N'-dimethylformamide to obtain a second mixed solution, heating the second mixed solution at 75-85° C. for 5-7 hours to react, then cooling to room temperature, adding excess water, filtering and washing the generated precipitate to obtain the guest component;

[0027] The grinding crystallization comprises:

[0028] Dissolving the guest component in dichloromethane, and grinding and mixing with the host component to obtain a grinding mixture;

[0029] The ground mixture is melted until the dichloromethane is completely volatilized, then rapidly cooled and crystallized, then allowed to stand and returned to room temperature to obtain an organic narrow-band afterglow material;

[0030] The extrusion process comprises:

[0031] The powder of the guest component and the powder of the host component are uniformly mixed and dried, and then extruded to obtain an organic narrow-band afterglow material;

[0032] The pouring method comprises:

[0033] The guest component, azobisisobutyronitrile and the main component are added into a mold, prepolymerized after being fully mixed, then low-temperature polymerized and heated for shaping, and after being cooled to room temperature, demolded to obtain the organic narrow-band afterglow material.

[0034] The above preparation method of the present invention uses Friedel-Crafts acylation reaction or Suzuki reaction to modify the coronene molecule to obtain the main component. The synthesis steps only require 1-2 steps, and the highest yield can reach 77%. In particular, the Suzuki reaction has a wide range of substrate applicability and a mature raw material acquisition method, and the process is simple, the raw materials are easily available, and the cost is low.

[0035] It is worth noting that although the above preparation method of the present invention adopts known chemical reactions such as Friedel-Crafts acylation reaction and Suzuki reaction, the obtained coronene derivative with narrow-band afterglow performance at room temperature is a new structure not proposed in the prior art.

[0036] Compared with coronene, the coronene derivatives obtained in the present invention have significantly improved oscillator strength, enhanced absorption efficiency of the excitation light source, and improved photoluminescence quantum yield.

[0037] The organic narrow-band afterglow material of the present invention is based on the existing two-component doping strategy, and provides a rigid microenvironment through a specific main component (with no obvious absorption at a selected excitation wavelength), thereby effectively protecting the excited state of the coronene derivative.

[0038] Among the preferred main components in the organic narrow-band afterglow material of the present invention, the organic small molecule main component has a relatively low melting point and good processing performance, and the high molecule, ie, polymer-type main component has a mature processing technology, which is convenient for practical application.

[0039] The preparation method of the present invention increases the complexity of the chemical structure of the coronene derivative, strengthens the vibration mode in the radiation transition process, and concentrates these vibration modes near the main peak, effectively reducing the half-peak width of the emission spectrum and achieving narrow-band afterglow emission. This preparation strategy is different from the preparation strategy of the existing multiple resonance thermally activated delayed fluorescence (MR-TADF) system, which focuses on enhancing the rigid structure of the luminescent molecule, thereby suppressing the vibration coupling of the molecule to achieve narrow-band emission.

[0040] In the coronene derivatives obtained by the present invention, the properties of the lowest triplet excited state (T1 state) largely retain the characteristics of coronene, retain a smaller phosphorescence emission rate (kp), and endow the material with a longer luminescence lifetime, with the phosphorescence lifetime reaching the second level, which is not available in conventional MR-TADF materials (with a lifetime of microseconds to milliseconds).

[0041] According to some preferred embodiments of the present invention, the preparation method further comprises: purifying the prepared guest component and then combining it with the host component.

[0042] According to some preferred embodiments of the present invention, the acyl chloride compound is selected from p-bromobenzoyl chloride.

[0043] According to some preferred embodiments of the present invention, the phenyl acid or phenyl acid derivative is selected from one or more of 3-phenoxybenzoic acid, 4-carboxybenzoic acid ethyl ester, 2,4,6-tribromobenzoic acid, 4-methylthiobenzoic acid, 6-methoxy-2-naphthoic acid, piperic acid, sodium benzenesulfite, 3-phenoxybenzoic acid, 4-carboxybenzoic acid ethyl ester, and 4-methylthiobenzoic acid.

[0044] According to some preferred embodiments of the present invention, the bromine-substituted coronene derivative is selected from the compounds shown in Formula I:

[0045]

[0046] According to some preferred embodiments of the present invention, the phenylboronic acid compound is selected from one or more of phenylboronic acid, p-methoxyphenylboronic acid, 4-dimethylaminophenylboronic acid, 4-ethylphenylboronic acid, 3-methoxyphenylboronic acid, 4-ethoxyphenylboronic acid, 4-fluorophenylboronic acid, and 4-acetylphenylboronic acid.

[0047] According to some preferred embodiments of the present invention, in the first Friedel-Crafts acylation reaction, the molar ratio of the coronene to the acyl chloride compound is 1:1.1.

[0048] According to some preferred embodiments of the present invention, in the second Friedel-Crafts acylation reaction, the molar ratio of the coronene to the phenyl acid or phenyl acid derivative is 1:1.1.

[0049] According to some preferred embodiments of the present invention, in the Suzuki reaction, the molar ratio of the bromine-substituted coronene derivative to the phenylboronic acid compound is 1:1.2.

[0050] According to some preferred embodiments of the present invention, in the grinding crystallization, the melting temperature is 95-105°C, and the cooling adopts liquid nitrogen; in the extrusion processing, the extrusion molding temperature is 100-250°C; in the casting method, the pre-polymerization temperature is 80-90°C, the time is 10-20min, the low-temperature polymerization temperature is 55-65°C, the time is 3.5-4.5h, and the heating and shaping temperature is 115-125°C, and the time is 1.5-2.5h.

[0051] The present invention further provides some application methods of the above-mentioned organic narrow-band afterglow material, such as applying it to any of the following: display equipment, especially advanced display equipment, such as used to make low-power backlight panels, high-resolution displays, OLED or Micro-LED displays, etc.; medical imaging or medical sensing equipment, such as used as luminescent markers in organisms for localization and in vivo imaging of cells and proteins, and used as targeted optical sensors for detection of specific biomarkers; lighting or lighting decoration devices, such as used to make low-energy, long-luminous night lighting equipment or decorative lamps; environmental monitoring equipment, such as used as gas sensors or detectors for detecting water quality of specific pollutants; information encryption or information anti-counterfeiting devices, such as using the optical characteristics of materials to make encrypted and / or difficult-to-copy anti-counterfeiting marks.

[0052] The present invention has the following beneficial effects:

[0053] The organic narrow-band afterglow material of the present invention is a two-component host-guest system based on coronene derivative-type luminescent molecules and phenyl benzoate, polymethyl methacrylate, dimethyl isophthalate, etc., with simple ingredients and convenient preparation.

[0054] The organic narrow-band afterglow material of the present invention is a room temperature afterglow material, which has a very narrow half-peak width, a long luminescence life and a high photoluminescence quantum yield at room temperature, which can reach 11.2nm, 1.77s and 51.3% respectively;

[0055] The organic narrow-band afterglow material of the present invention provides a brand-new solution for the fields of advanced display technology, optical sensing and detection, biomedical imaging, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0056] Figure 1 These are the luminescence images of the 1-PhB-0.1% material of Example 1 under (A) 365nm ultraviolet light irradiation and after turning off the light; (B) room temperature steady-state luminescence spectrum under 383nm excitation wavelength, (C) room temperature delayed luminescence spectrum (1ms delay), and (D) luminescence decay curve at room temperature.

[0057] Figure 2 These are the luminescence images of the 2-PhB-0.1% material of Example 2 under (A) 365nm ultraviolet light irradiation and after turning off the light; (B) room temperature steady-state luminescence spectrum at 350nm excitation wavelength, (C) room temperature delayed luminescence spectrum (1ms delay), and (D) luminescence decay curve at room temperature.

[0058] Figure 3These are the luminescence images of the 3-PhB-0.1% material of Example 3 under (A) 365nm ultraviolet light irradiation and after turning off the light; (B) room temperature steady-state luminescence spectrum under 350nm excitation wavelength, (C) room temperature delayed luminescence spectrum (1ms delay), and (D) luminescence decay curve at room temperature.

[0059] Figure 4 These are the luminescence images of the 4-PhB-0.1% material of Example 4 under (A) 365nm ultraviolet light irradiation and after turning off the light; (B) room temperature steady-state luminescence spectrum under 350nm excitation wavelength, (C) room temperature delayed luminescence spectrum (1ms delay), and (D) luminescence decay curve at room temperature.

[0060] Figure 5 These are the luminescence images of the 5-PhB-0.1% material of Example 5 under (A) 365nm ultraviolet light irradiation and after turning off the light; (B) room temperature steady-state luminescence spectrum under 350nm excitation wavelength, (C) room temperature delayed luminescence spectrum (1ms delay), and (D) luminescence decay curve at room temperature.

[0061] Figure 6 These are the luminescence images of the 6-PhB-0.1% material of Example 6 under (A) 365nm ultraviolet light irradiation and after turning off the light; (B) room temperature steady-state luminescence spectrum under 350nm excitation wavelength, (C) room temperature delayed luminescence spectrum (1ms delay), and (D) luminescence decay curve at room temperature.

[0062] Figure 7 These are the luminescence images of the 7-PhB-0.1% material of Example 7 under (A) 365nm ultraviolet light irradiation and after turning off the light; (B) room temperature steady-state luminescence spectrum under 350nm excitation wavelength, (C) room temperature delayed luminescence spectrum (1ms delay), and (D) luminescence decay curve at room temperature.

[0063] Figure 8 These are the luminescence images of the 8-PhB-0.1% material of Example 8 under (A) 365nm ultraviolet light irradiation and after turning off the light; (B) room temperature steady-state luminescence spectrum under 350nm excitation wavelength, (C) room temperature delayed luminescence spectrum (1ms delay), and (D) luminescence decay curve at room temperature.

[0064] Fig. 9 These are the luminescence images of the 9-PhB-0.1% material of Example 9 under (A) 365nm ultraviolet light irradiation and after turning off the light; (B) room temperature steady-state luminescence spectrum under 350nm excitation wavelength, (C) room temperature delayed luminescence spectrum (1ms delay), and (D) luminescence decay curve at room temperature.

[0065] Fig.10These are the luminescence images of the 10-PhB-0.1% material of Example 10 under (A) 365nm ultraviolet light irradiation and after turning off the light; (B) room temperature steady-state luminescence spectrum under 350nm excitation wavelength, (C) room temperature delayed luminescence spectrum (1ms delay), and (D) luminescence decay curve at room temperature.

[0066] Fig.11 These are the luminescent images of the 11-DMI-0.02% material of Example 11 under (A) 365nm ultraviolet light irradiation and after turning off the light; (B) room temperature steady-state luminescence spectrum under 351nm excitation wavelength, (C) room temperature delayed luminescence spectrum (1ms delay), and (D) luminescence decay curve at room temperature.

[0067] Fig.12 These are the luminescent images of the 12-DMI-0.1% material of Example 12 under (A) 365nm ultraviolet light irradiation and after turning off the light; (B) room temperature steady-state luminescence spectrum under 366nm excitation wavelength, (C) room temperature delayed luminescence spectrum (1ms delay), and (D) luminescence decay curve at room temperature.

[0068] Fig.13 These are the luminescence images of the 13-DMI-0.1% material of Example 13 under (A) 365nm ultraviolet light irradiation and after turning off the light; (B) room temperature steady-state luminescence spectrum under 352nm excitation wavelength, (C) room temperature delayed luminescence spectrum (1ms delay), and (D) luminescence decay curve at room temperature.

[0069] Fig.14 These are the luminescence images of the 14-PhB-0.1% material of Example 14 under (A) 365nm ultraviolet light irradiation and after turning off the light; (B) room temperature steady-state luminescence spectrum under 365nm excitation wavelength, (C) room temperature delayed luminescence spectrum (1ms delay), and (D) luminescence decay curve at room temperature.

[0070] Fig.15 These are the luminescence images of the 15-PhB-0.1% material of Example 15 under (A) 365nm ultraviolet light irradiation and after turning off the lights; (B) room temperature steady-state luminescence spectrum under 365nm excitation wavelength, (C) room temperature delayed luminescence spectrum (1ms delay), and (D) luminescence decay curve at room temperature.

[0071] Fig.16 These are the luminescence images of the 16-PhB-0.1% material of Example 16 under (A) 365nm ultraviolet light irradiation and after turning off the light; (B) room temperature steady-state luminescence spectrum under 365nm excitation wavelength, (C) room temperature delayed luminescence spectrum (1ms delay), and (D) luminescence decay curve at room temperature.

[0072] Fig.17These are the luminescence images of the 17-PhB-0.1% material of Example 17 under (A) 365nm ultraviolet light irradiation and after turning off the light; (B) room temperature steady-state luminescence spectrum under 365nm excitation wavelength, (C) room temperature delayed luminescence spectrum (1ms delay), and (D) luminescence decay curve at room temperature.

[0073] Fig.18 These are the luminescence images of the 18-PhB-0.1% material of Example 18 under (A) 365nm ultraviolet light irradiation and after turning off the light; (B) room temperature steady-state luminescence spectrum under 365nm excitation wavelength, (C) room temperature delayed luminescence spectrum (1ms delay), and (D) luminescence decay curve at room temperature.

[0074] Fig.19 These are the luminescent images of the 3-PMMA-0.01%-E material of Example 19 under (A) sunlight, 365nm ultraviolet light and after turning off the lights; (B) room temperature steady-state luminescence spectrum under 350nm excitation wavelength, (C) room temperature delayed luminescence spectrum (1ms delay), and (D) luminescence decay curve at room temperature.

[0075] Fig. 20 These are the luminescence images of the 3-PMMA-0.01%-C material of Example 20 under (A) 365nm ultraviolet light irradiation and after turning off the light; (B) room temperature steady-state luminescence spectrum at 350nm excitation wavelength, (C) room temperature delayed luminescence spectrum (1ms delay), and (D) luminescence decay curve at room temperature. DETAILED DESCRIPTION

[0076] The present invention is described in detail below in conjunction with the embodiments and drawings, but it should be understood that the embodiments and drawings are only used to exemplify the present invention and do not constitute any limitation on the protection scope of the present invention. All reasonable changes and combinations within the scope of the inventive concept of the present invention fall within the protection scope of the present invention.

[0077] The test methods in the following examples are conventional methods unless otherwise specified, and the materials used in the examples are commercially available products unless otherwise specified.

[0078] Example 1

[0079] Organic narrow-band afterglow materials are prepared by the following process:

[0080]

[0081] 60 mg of coronene, 267 mg of aluminum chloride, and 2 mL of dichloromethane were mixed in a round-bottom flask and stirred in an ice bath for 10 min;

[0082] Dissolve 44 mg of p-bromobenzoyl chloride in 1 mL of dichloromethane, and slowly drip the p-bromobenzoyl chloride-dichloromethane solution into the round-bottom flask at a rate of 1 mL / 30 min;

[0083] After all the p-bromobenzoyl chloride-dichloromethane solution was dropped, the reaction was stirred at room temperature for 3 h. The crude product was subjected to rotary evaporation to remove the solvent and purified by silica gel column chromatography using petroleum ether / dichloromethane (3:1, v / v) as the eluent to obtain yellow solid compound 1.

[0084] A 0.25 mg / mL dichloromethane solution of compound 1 was prepared and mixed with phenyl benzoate (PhB) by grinding, wherein the mass ratio of compound 1 to phenyl benzoate was 1:1000;

[0085] The mixture was placed in an oven at 100°C to completely melt and evaporate the dichloromethane. Subsequently, the mixture was quickly cooled and crystallized in liquid nitrogen. After standing for several minutes and returning to room temperature, an organic narrow-band afterglow material 1-PhB-0.1% material was obtained.

[0086] The 1-PhB-0.1% material emits yellow-green light under 365nm ultraviolet light at room temperature. After the ultraviolet light is turned off, the yellow-green light continues for 10 seconds. Figure 1 (A) As shown. At a monitoring wavelength of 540nm and an excitation wavelength of 383nm, its room temperature steady-state luminescence spectrum is shown in the attached Figure 1 (B) shows the luminescence spectrum of room temperature with a delay of 1 ms. Figure 1 (C) shows the luminescence decay curve at room temperature. Figure 1 (D) as shown.

[0087] The luminescence peak of the 1-PhB-0.1% material is located at 540 nm, the half-peak width is 22.4 nm, and the photoluminescence quantum yield is 16.3%.

[0088] The hydrogen spectrum of compound 1 is as follows:

[0089] 1H NMR (500MHz, CDCl3, 298K) δ9.18–8.92 (m, 11H), 7.99 (d, J = 8.5Hz, 2H), 7.72 (d, J = 8.4Hz, 2H). FT-IR (KBr, cm-1): 3242.3,3 056.0,2956.1,2923.1,2852.0,1901.5,1727.9,1650.5,1601.2,1580.6,1564.8,1498.9,1480.8,1453.9,1396.8,1362.4 ,1346.1,1324.1,1305.7,1267.4,1215.0,1176.9,1168.3,1140.1,1073.4,1029.8,1014.2,972.3,924.4,902.4,847.9, 837.2,812.5,792.9,785.3,773.9,763.0,729.2,656.1,645.0,600.8,547.5,519.9,501.8,462.8,414.4.HRMS(positive ESI)m / z found(calcd forC 31 H 15 +H + ):483.0379(483.0385).

[0090] Example 2

[0091] Organic narrow-band afterglow materials are prepared by the following process:

[0092]

[0093] 48 mg of compound 1, 15 mg of phenylboronic acid, 2 mg of palladium acetate, 28 mg of potassium carbonate and 2 mL of N,N'-dimethylformamide (DMF) were mixed in a round-bottom flask, and the reaction mixture was heated at 80°C for 6 h. After cooling to room temperature, excess water was added to the reaction system, and the generated precipitate was filtered and washed with water to remove DMF;

[0094] The crude product was dissolved in dichloromethane, dried over anhydrous sodium sulfate, filtered and concentrated by rotary evaporation. Purification by silica gel column chromatography using petroleum ether / dichloromethane (1:1, v / v) as eluent gave yellow solid compound 2;

[0095] A 0.25 mg / mL dichloromethane solution of compound 2 was prepared and mixed with phenyl benzoate (PhB) by grinding, and the mass ratio of compound 2 to phenyl benzoate was 1:1000;

[0096] The mixture was then placed in an oven at 100°C to completely melt and evaporate the dichloromethane, and then quickly cooled and crystallized in liquid nitrogen. After standing for several minutes and returning to room temperature, 2-PhB-0.1% material was obtained.

[0097] The 2-PhB-0.1% material emits yellow-green light under 365nm ultraviolet light at room temperature. After the ultraviolet light is turned off, the yellow-green light continues for more than 10 seconds. Figure 2 (A) As shown. At a monitoring wavelength of 532nm and an excitation wavelength of 350nm, its room temperature steady-state luminescence spectrum is shown in the attached Figure 2 (B) shows the luminescence spectrum of room temperature with a delay of 1 ms. Figure 2 (C) shows the luminescence decay curve at room temperature. Figure 2 (D) as shown.

[0098] The luminescence peak of the 2-PhB-0.1% material is located at 532 nm, the half-peak width is 20.2 nm, and the photoluminescence quantum yield is 43.7%.

[0099] The hydrogen spectrum of compound 2 is as follows:

[0100] 1 H NMR (500MHz, CDCl3, 298K) δ9.18(d,J=8.8Hz,1H),9.07(s,1H),9.03–8.91(m,9H),8.18(d,J=8.2Hz,2H),7.77(d,J=8.3Hz,2H),7.70(d,J =7.7Hz,2H),7.50(t,J=7.5Hz,2H),7.44(d,J=7.4Hz,1H).FT-IR(KBr,cm-1):3051.6,3027.0,1897.3,1663.4,1597.8,1556.6,1502.6,1 484.6,1448.4,1404.0,1346.0,1325.2,1305.9,1292.6,1268.0,1220.3,1177.3,1169.0,1140.4,1074.5,1029.8,1006.8,995.4,973.9 ,925.6,888.6,851.8,838.3,797.0,769.3,747.4,694.6,660.1,645.3,630.0,607.1,568.8,549.7,511.1,468.1,413.8.HRMS(positive ESI)m / z found(calcd for C 37 H 20 O+H +):481.1570(481.1592).

[0101] Example 3

[0102] Organic narrow-band afterglow materials are prepared by the following process:

[0103]

[0104] 48 mg of compound 1, 18 mg of p-methoxyphenylboronic acid, 2 mg of palladium acetate, 28 mg of potassium carbonate and 2 mL of DMF were mixed in a round-bottom flask. The reaction mixture was heated at 80 °C for 6 h. After cooling to room temperature, excess water was added to the reaction system, and the resulting precipitate was filtered and washed with water to remove DMF;

[0105] The crude product was dissolved in dichloromethane, dried over anhydrous sodium sulfate, filtered and concentrated by rotary evaporation. Purification by silica gel column chromatography using petroleum ether / dichloromethane (1:1, v / v) as eluent gave yellow solid compound 3;

[0106] A 0.25 mg / mL dichloromethane solution of compound 3 was prepared and mixed with phenyl benzoate (PhB) by grinding, and the mass ratio of compound 3 to phenyl benzoate was 1:1000;

[0107] The mixture was placed in an oven at 100°C to completely melt and evaporate the dichloromethane, and then quickly cooled and crystallized in liquid nitrogen. After standing for several minutes and returning to room temperature, 3-PhB-0.1% material was obtained.

[0108] The 3-PhB-0.1% material emits yellow-green light under 365nm ultraviolet light at room temperature. After the ultraviolet light is turned off, the yellow-green light continues for more than 20 seconds. Figure 3 (A) As shown. At a monitoring wavelength of 531nm and an excitation wavelength of 350nm, its room temperature steady-state luminescence spectrum is shown in the attached Figure 3 (B) shows the luminescence spectrum of room temperature with a delay of 1 ms. Figure 3 (C) shows the luminescence decay curve at room temperature. Figure 3 (D) as shown.

[0109] The luminescence peak of the 3-PhB-0.1% material is located at 531 nm, the half-peak width is 13.6 nm, and the photoluminescence quantum yield is 51.3%.

[0110] The hydrogen spectrum of compound 3 is as follows:

[0111] 1H NMR (400MHz, CDCl3, 298K) δ9.15 (d, J=8.7Hz, 1H), 9.05 (s, 1H), 8.99–8.89 (m,9H),8.14(d,J=8.2Hz,2H),7.72(d,J=8.2Hz,2H),7.66–7.59(m,2H),7. 02(d,J=8.7Hz,2H),3.87(s,3H).FT-IR(KBr,cm-1):3017.8,2923.5,2833. 9,1898.5,1650.4,1598.2,1578.8,1556.4,1522.5,1494.9,1453.3,1438. 4,1400.1,1347.8,1325.6,1305.9,1295.8,1271.1,1249.3,1221.1,1180 .3,1140.4,1075.1,1039.9,1030.8,1012.2,999.5,974.0,925.6,895.7,8 48.5,827.2,812.3,794.9,777.7,767.0,718.7,682.0,659.6,644.5,632. 1,601.9,568.0,547.7,508.4,492.8,418.6,413.8,402.0.HRMS(positive ESI) m / z found (calcd for C 38 H 22 O2+H + ):511.1655 (511.1698).

[0113] Example 4

[0114] Organic narrow-band afterglow materials are prepared by the following process:

[0115]

[0116] 48 mg of compound 1, 20 mg of 4-dimethylaminophenylboronic acid, 2 mg of palladium acetate, 28 mg of potassium carbonate and 2 mL of DMF were mixed in a round-bottom flask. The reaction mixture was heated at 80 °C for 6 h. After cooling to room temperature, excess water was added to the reaction system, and the resulting precipitate was filtered and washed with water to remove DMF;

[0117] The crude product was dissolved in dichloromethane, dried over anhydrous sodium sulfate, filtered and concentrated by rotary evaporation. Purification by silica gel column chromatography using petroleum ether / dichloromethane (1:1, v / v) as eluent gave yellow solid compound 4;

[0118] A 0.25 mg / mL dichloromethane solution of compound 4 was prepared and mixed with phenyl benzoate (PhB) by grinding, and the mass ratio of compound 4 to phenyl benzoate was 1:1000;

[0119] The mixture was placed in an oven at 100°C to completely melt and evaporate the dichloromethane, and then quickly cooled and crystallized in liquid nitrogen. After standing for several minutes and returning to room temperature, 4-PhB-0.1% material was obtained.

[0120] The 4-PhB-0.1% material emits yellow-green light under 365nm ultraviolet light at room temperature. After the ultraviolet light is turned off, the yellow-green light continues for more than 15 seconds. Figure 4 (A) As shown. At a monitoring wavelength of 531nm and an excitation wavelength of 350nm, its room temperature steady-state luminescence spectrum is shown in the attached Figure 4 (B) shows the luminescence spectrum of room temperature with a delay of 1 ms. Figure 4 (C) shows the luminescence decay curve at room temperature. Figure 4 (D) as shown.

[0121] The luminescence peak of the 4-PhB-0.1% material is located at 531 nm, the half-peak width is 11.2 nm, and the photoluminescence quantum yield is 51.1%.

[0122] The hydrogen spectrum of compound 4 is as follows:

[0123] 1 H NMR (500MHz, CDCl3, 298K) δ9.18(d,J=8.8Hz,1H),9.08(s,1H),9.02–8.94(m,9H),8.14(d,J=8.3Hz,2H),7.75(d,J=8.3Hz,2 H),7.65(d,J=8.8Hz,2H),6.84(d,J=8.8Hz,2H),3.06(s,6H).FT-IR(KBr,cm-1):3051.5,2892.8,1891.3,1648.0,1594.7,15 32.4,1497.3,1443.8,1363.6,1325.3,1304.8,1269.3,1207.1,1178.8,1167.7,1139.3,1062.2,974.5,948.6,925.7,892. 0,848.1,818.9,809.2,791.1,781.8,769.9,718.2,679.9,660.5,613.7,567.1,546.4,508.8,436.7,418.3.HRMS(positive ESI)m / z found(calcd for C 39 H25 NO+H + ):524.2000(524.2014).

[0124] Example 5

[0125] Organic narrow-band afterglow materials are prepared by the following process:

[0126]

[0127] 48 mg of compound 1, 18 mg of 4-ethylphenylboronic acid, 2 mg of palladium acetate, 28 mg of potassium carbonate and 2 mL of DMF were mixed in a round-bottom flask. The reaction mixture was heated at 80 °C for 6 h. After cooling to room temperature, excess water was added to the reaction system, and the resulting precipitate was filtered and washed with water to remove DMF;

[0128] The crude product was dissolved in dichloromethane, dried over anhydrous sodium sulfate, filtered and concentrated by rotary evaporation. Purification by silica gel column chromatography using petroleum ether / dichloromethane (1:1, v / v) as eluent gave yellow solid compound 5;

[0129] A 0.25 mg / mL dichloromethane solution of compound 5 was prepared and mixed with phenyl benzoate (PhB) by grinding, and the mass ratio of compound 5 to phenyl benzoate was 1:1000;

[0130] The mixture was placed in an oven at 100°C to completely melt and evaporate the dichloromethane, and then quickly cooled and crystallized in liquid nitrogen. After standing for several minutes and returning to room temperature, 5-PhB-0.1% material was obtained.

[0131] The 5-PhB-0.1% material emits yellow-green light under 365nm ultraviolet light at room temperature. After turning off the ultraviolet light, the yellow-green light continues for more than 15 seconds. Figure 5 (A) As shown. At a monitoring wavelength of 531nm and an excitation wavelength of 350nm, its room temperature steady-state luminescence spectrum is shown in the attached Figure 5 (B) shows the luminescence spectrum of room temperature with a delay of 1 ms. Figure 5 (C) shows the luminescence decay curve at room temperature. Figure 5 (D) as shown.

[0132] The luminescence peak of the 5-PhB-0.1% material is located at 531 nm, the half-peak width is 11.6 nm, and the photoluminescence quantum yield is 40.9%.

[0133] The hydrogen spectrum of compound 5 is as follows:

[0134] 1H NMR (500MHz, CDCl3, 298K) δ9.19 (d, J=8.8Hz, 1H), 9.08 (s, 1H), 9.03–8.88 (m ,9H),8.18(d,J=8.2Hz,2H),7.78(d,J=8.1Hz,2H),7.65(d,J=8.0Hz,2H),7. 36(d,J=7.9Hz,2H),2.75(q,J=7.5Hz,2H),1.32(t,J=7.5Hz,3H).FT-IR(KBr ,cm-1):3021.0,2959.8,2924.4,2868.7,1900.7,1788.0,1657.4,1599.7,15 74.2,1553.2,1520.8,1501.6,1454.1,1420.6,1399.1,1347.9,1324.8,1306.0,1270.0,1222.0,1176.1,1168.5,1139.9,1073.9,1029.9,1005.7,973.9 ,926.1,894.7,844.9,813.2,789.9,767.1,775.6,733.1,711.6,680.3,663 .8,632.4,604.1,568.5,543.6,515.1,415.5,404.9.HRMS(positiveESI)m / z found(calcd for C 39 H 24 O+H + ):509.1879(509.1905).

[0135] Example 6

[0136] Organic narrow-band afterglow materials are prepared by the following process:

[0137]

[0138] 48 mg of compound 1, 18 mg of 3-methoxyphenylboronic acid, 2 mg of palladium acetate, 28 mg of potassium carbonate and 2 mL of DMF were mixed in a round-bottom flask. The reaction mixture was heated at 80 °C for 6 h. After cooling to room temperature, excess water was added to the reaction system, and the resulting precipitate was filtered and washed with water to remove DMF;

[0139] The crude product was dissolved in dichloromethane, dried over anhydrous sodium sulfate, filtered and concentrated by rotary evaporation. Purification by silica gel column chromatography using petroleum ether / dichloromethane (1:1, v / v) as eluent gave yellow solid compound 6;

[0140] A 0.25 mg / mL dichloromethane solution of compound 6 was prepared and mixed with phenyl benzoate (PhB) by grinding, and the mass ratio of compound 6 to phenyl benzoate was 1:1000;

[0141] The mixture was placed in an oven at 100°C to completely melt and evaporate the dichloromethane, and then quickly cooled and crystallized in liquid nitrogen. After standing for several minutes and returning to room temperature, 6-PhB-0.1% material was obtained.

[0142] The 6-PhB-0.1% material emits yellow-green light under 365nm ultraviolet light at room temperature. After the ultraviolet light is turned off, the yellow-green light continues for more than 15 seconds. Figure 6 (A) As shown. At a monitoring wavelength of 532nm and an excitation wavelength of 350nm, its room temperature steady-state luminescence spectrum is shown in the attached Figure 6 (B) shows the luminescence spectrum of room temperature with a delay of 1 ms. Figure 6 (C) shows the luminescence decay curve at room temperature. Figure 6 (D) as shown.

[0143] The 6-PhB-0.1% material has a luminescence peak at 532 nm, a half-peak width of 19.8 nm, and a photoluminescence quantum yield of 39.3%.

[0144] The hydrogen spectrum of compound 6 is as follows:

[0145] 1H NMR (500MHz, CDCl3, 298K) δ9.21–8.86 (m, 11H), 8.17 (d, J = 8.1Hz, 2H), 7.76 (d ,J=7.8Hz,2H),7.41(t,J=7.6Hz,1H),7.21(s,2H),6.97(d,J=7.8Hz,1H),3.8 9(s,3H).FT-IR(KBr,cm-1):3050.0,3021.4,2996.6,2956.5,2935.5,2832.4 ,1904.0,1660.4,1600.4,1582.3,1558.6,1533.5,1500.6,1479.9,1453.3,1 433.6,1400.6,1348.4,1326.4,1305.4,1290.1,1267.1,1221.9,1173.9,1140.1,1075.7,1053.7,1025.5,1012.7,973.6,960.5,825.8,888.2,873.6,852 .7,833.2,812.5,763.6,731.8,688.4,665.6,651.2,644.8,629.2,611.9,60 1.8,565.0,546.3,518.4,453.6,438.6,417.4,408.8,402.3.HRMS(positive ESI)m / z found(calcd for C 38 H 22 O2+H + ):511.1647(511.1698).

[0146] Example 7

[0147] Organic narrow-band afterglow materials are prepared by the following process:

[0148]

[0149] 48 mg of compound 1, 20 mg of 4-ethoxyphenylboronic acid, 2 mg of palladium acetate, 28 mg of potassium carbonate and 2 mL of DMF were mixed in a round-bottom flask. The reaction mixture was heated at 80 °C for 6 h. After cooling to room temperature, excess water was added to the reaction system, and the resulting precipitate was filtered and washed with water to remove DMF;

[0150] The crude product was dissolved in dichloromethane, dried over anhydrous sodium sulfate, filtered and concentrated by rotary evaporation. Purification by silica gel column chromatography using petroleum ether / dichloromethane (1:1, v / v) as eluent gave yellow solid compound 7;

[0151] A 0.25 mg / mL dichloromethane solution of compound 7 was prepared and mixed with phenyl benzoate (PhB) by grinding, and the mass ratio of compound 7 to phenyl benzoate was 1:1000;

[0152] The mixture was placed in an oven at 100°C to completely melt and evaporate the dichloromethane, and then quickly cooled and crystallized in liquid nitrogen. After standing for several minutes and returning to room temperature, 7-PhB-0.1% material was obtained.

[0153] The 7-PhB-0.1% material emits yellow-green light under 365nm ultraviolet light at room temperature. After turning off the ultraviolet light, the yellow-green light continues for 15 seconds. Figure 7 (A) As shown. At a monitoring wavelength of 531nm and an excitation wavelength of 350nm, its room temperature steady-state luminescence spectrum is shown in the attached Figure 7 (B) shows the luminescence spectrum of room temperature with a delay of 1 ms. Figure 7 (C) shows the luminescence decay curve at room temperature. Figure 7 (D) as shown.

[0154] The luminescence peak of the 7-PhB-0.1% material is located at 531 nm, the half-peak width is 15.0 nm, and the photoluminescence quantum yield is 47.0%.

[0155] The hydrogen spectrum of compound 7 is as follows:

[0156] 1H NMR (500MHz, CDCl3, 298K) δ9.09(d,J=8.8Hz,1H),8.99(s,1H),8.96–8.84(m,9H),8.07(d,J=8.2Hz,2H),7.66(d,J=8.2Hz,2H),7.56(d, J=8.6Hz,2H),6.94(d,J=8.6Hz,2H),4.05–4.01(m,2H),1.39(t,J=7.0Hz,3H).FT-IR(KBr,cm-1):3045.5,2974.2,2923.0,2870.5,1646 .5,1597.4,1555.7,1521.2,1494.3,1472.8,1453.3,1392.1,1348.7,1324.8,1305.4,1297.6,1271.7,1248.3,1222.6,1179.2,1140.5 ,1116.6,1074.3,1046.5,1001.9,973.7,925.6,897.2,843.4,792.6,777.8,767.7,735.6,725.1,683.9,545.0,514.5.HRMS(positive ESI)m / z found(calcd for C 39 H 24 O2+H + ):525.1822(525.1855).

[0157] Example 8

[0158] Organic narrow-band afterglow materials are prepared by the following process:

[0159]

[0160] 48 mg of compound 1, 17 mg of 4-fluorophenylboronic acid, 2 mg of palladium acetate, 28 mg of potassium carbonate and 2 mL of DMF were mixed in a round-bottom flask. The reaction mixture was heated at 80 °C for 6 h. After cooling to room temperature, excess water was added to the reaction system, and the resulting precipitate was filtered and washed with water to remove DMF;

[0161] The crude product was dissolved in dichloromethane, dried over anhydrous sodium sulfate, filtered and concentrated by rotary evaporation. It was purified by silica gel column chromatography using petroleum ether / dichloromethane (1:1, v / v) as eluent to obtain yellow solid compound 8;

[0162] A 0.25 mg / mL dichloromethane solution of compound 8 was prepared and mixed with phenyl benzoate (PhB) by grinding, and the mass ratio of compound 8 to phenyl benzoate was 1:1000;

[0163] The mixture was placed in an oven at 100°C to completely melt and evaporate the dichloromethane, and then quickly cooled and crystallized in liquid nitrogen. After standing for several minutes and returning to room temperature, 8-PhB-0.1% material was obtained.

[0164] The 8-PhB-0.1% material emits yellow-green light under 365nm ultraviolet light at room temperature. After turning off the ultraviolet light, the yellow-green light continues for 15 seconds. Figure 8 (A) As shown. At a monitoring wavelength of 532nm and an excitation wavelength of 350nm, its room temperature steady-state luminescence spectrum is shown in the attached Figure 8 (B) shows the luminescence spectrum of room temperature with a delay of 1 ms. Figure 8 (C) shows the luminescence decay curve at room temperature. Figure 8 (D) as shown.

[0165] The luminescence peak of the 8-PhB-0.1% material is located at 532 nm, the half-peak width is 19.8 nm, and the photoluminescence quantum yield is 31.8%.

[0166] The hydrogen spectrum of compound 8 is as follows:

[0167] 1 H NMR (500MHz, CDCl3, 298K) δ9.17(d,J=8.7Hz,1H),9.07(s,1H),9.04–8.90(m,9H),8.17(d,J=8.2Hz,2H),7.72(d,J=8.4Hz, 2H),7.65(d,J=6.2Hz,2H),7.19(t,J=8.6Hz,2H).FT-IR(KBr,cm-1):3050.5,2921.8,1887.4,1651.3,1601.1,1557.1,1518 .6,1493.2,1345.6,1326.0,1306.1,1271.8,1234.6,1178.9,1168.6,1157.2,1141.3,1095.3,1006.1,974.5,925.3,901.9 ,862.6,847.3,827.5,813.0,793.1,775.5,766.4,735.1,716.4,596.9,568.9,550.3,519.5,502.9,437.1.HRMS(positive ESI)m / z found(calcdfor C37H19FO+H+):499.1474(499.1498).

[0168] Example 9

[0169] Organic narrow-band afterglow materials are prepared by the following process:

[0170]

[0171] 48 mg of compound 1, 20 mg of 4-acetylphenylboronic acid, 2 mg of palladium acetate, 28 mg of potassium carbonate and 2 mL of DMF were mixed in a round-bottom flask. The reaction mixture was heated at 80 °C for 6 h. After cooling to room temperature, excess water was added to the reaction system, and the resulting precipitate was filtered and washed with water to remove DMF;

[0172] The crude product was dissolved in dichloromethane, dried over anhydrous sodium sulfate, filtered and concentrated by rotary evaporation. Purification by silica gel column chromatography using petroleum ether / dichloromethane (1:1, v / v) as eluent gave yellow solid compound 9;

[0173] A 0.25 mg / mL dichloromethane solution of compound 9 was prepared and mixed with phenyl benzoate (PhB) by grinding, and the mass ratio of compound 9 to phenyl benzoate was 1:1000;

[0174] The mixture was placed in an oven at 100°C to completely melt and evaporate the dichloromethane, and then quickly cooled and crystallized in liquid nitrogen. After standing for several minutes and returning to room temperature, 9-PhB-0.1% material was obtained.

[0175] The 9-PhB-0.1% material emits yellow-green light under 365nm ultraviolet light at room temperature. After turning off the ultraviolet light, the yellow-green light continues for 15 seconds. Fig. 9 (A) As shown. At a monitoring wavelength of 532nm and an excitation wavelength of 350nm, its room temperature steady-state luminescence spectrum is shown in the attached Fig. 9 (B) shows the luminescence spectrum of room temperature with a delay of 1 ms. Fig. 9 (C) shows the luminescence decay curve at room temperature. Fig. 9 (D) as shown.

[0176] The luminescence peak of the 9-PhB-0.1% material is located at 532 nm, the half-peak width is 11.8 nm, and the photoluminescence quantum yield is 41.3%.

[0177] The hydrogen spectrum of compound 9 is as follows:

[0178] 1H NMR (500MHz, CDCl3, 298K) δ9.21(d,J=8.6Hz,1H),9.09(s,1H),9.06–8.92(m,9H),8.23(d,J=8.2Hz,2H),8.11(d,J=8.2Hz,2H),7.8 2(t,J=7.8Hz,4H),2.69(s,3H).FT-IR(KBr,cm-1):3047.3,3016.4,1907.7,1679.5,1643.9,1621.1,1602.2,1551.9,1533.5,1498 .9,1452.9,1415.5,1395.4,1360.5,1325.0,1305.1,1266.2,1220.0,1179.3,1139.8,1076.3,1003.2,973.2,958.4,920.7,844.1 ,812.4,795.0,766.8,125.7,702.3,678.5,657.7,643.5,608.5,595.4,568.3,550.6,541.1,508.5,446.3.HRMS(positiveESI)m / z found(calcd for C 39 H 22 O2+H + ):523.1652(523.1698).

[0179] Example 10

[0180] Organic narrow-band afterglow materials are prepared by the following process:

[0181]

[0182] 200 mg of undeuterated compound 3 was treated with 300 mg of 10% palladium / activated carbon and 30 mL of heavy water in a 130 mL polytetrafluoroethylene-lined autoclave at 250°C for 24 h, with the internal pressure maintained at 4-5 MPa. The heating was turned off, and after the autoclave was slowly cooled to room temperature, the resulting reaction solution was extracted and separated with dichloromethane and saturated brine, and the organic phase was retained;

[0183] The organic layer was dried by adding anhydrous sodium sulfate, filtered, concentrated by rotary evaporation, and purified by silica gel column chromatography using petroleum ether / dichloromethane (1:1, v / v) as eluent to obtain yellow solid compound 10; 1 The deuterated yield was calculated by H NMR to be 50.6% (1,4-dioxane was used as an internal standard);

[0184] A 0.25 mg / mL dichloromethane solution of compound 10 was prepared and mixed with phenyl benzoate (PhB) by grinding, and the mass ratio of compound 10 to phenyl benzoate was 1:1000;

[0185] The mixture was placed in an oven at 100°C to completely melt and evaporate the dichloromethane, and then quickly cooled and crystallized in liquid nitrogen. After standing for several minutes and returning to room temperature, 10-PhB-0.1% material was obtained.

[0186] The 10-PhB-0.1% material emits yellow-green light under 365nm ultraviolet light at room temperature. After the ultraviolet light is turned off, the yellow-green light continues for more than 20 seconds. Fig.10 (A) As shown. At a monitoring wavelength of 531nm and an excitation wavelength of 350nm, its room temperature steady-state luminescence spectrum is shown in the attached Fig.10 (B) shows the luminescence spectrum of room temperature with a delay of 1 ms. Fig.10 (C) shows the luminescence decay curve at room temperature. Fig.10 (D) as shown.

[0187] The luminescence peak of the 10-PhB-0.1% material is located at 531 nm, and the half-peak width is 11.6 nm.

[0188] Embodiment 11

[0189] Organic narrow-band afterglow materials are prepared by the following process:

[0190]

[0191] 96 mg of compound 1, 50 mg of 3,5-dicarboxyphenylboronic acid, 55 mg of potassium carbonate, 4 mg of palladium acetate and 5 mL of DMF were mixed in a Shrek tube, a magnetic bar was added, and freeze-thaw cycles were repeated 3 times. After returning to room temperature, the reaction mixture was heated at 100°C for 10 h. After cooling to room temperature, excess water was added to the reaction system, and the generated precipitate was filtered and washed with water to remove DMF;

[0192] The crude product was dissolved in dichloromethane, dried over anhydrous sodium sulfate, filtered and concentrated by rotary evaporation. It was purified by silica gel column chromatography using petroleum ether / dichloromethane (3:1, v / v) as eluent to obtain brown-yellow solid compound 11;

[0193] A 1 mg / mL dichloromethane solution of compound 11 was prepared and mixed with dimethyl isophthalate (DMI) by grinding, and the mass ratio of compound 11 to dimethyl isophthalate was 1:5000;

[0194] The mixture was placed in an oven at 85°C until it was completely melted and the dichloromethane was completely volatilized, and then quickly cooled and crystallized in liquid nitrogen. After standing for several minutes and returning to room temperature, 11-DMI-0.02% material was obtained.

[0195] The 11-DMI-0.02% material emits yellow light under 365nm ultraviolet light at room temperature. After turning off the ultraviolet light, the yellow light continues for 19 seconds. Fig.11 (A) As shown. At a monitoring wavelength of 550nm and an excitation wavelength of 351nm, its room temperature steady-state luminescence spectrum is shown in the attached Fig.11 (B) shows the luminescence spectrum of room temperature with a delay of 1 ms. Fig.11 (C) shows the luminescence decay curve at room temperature. Fig.11 (D) as shown.

[0196] The luminescence peak of the 11-DMI-0.02% material is located at 550nm, and the half-peak width is 31.4nm.

[0197] Example 12

[0198] Organic narrow-band afterglow materials are prepared by the following process:

[0199]

[0200] Mix 86 mg of 3-phenoxybenzoic acid and 2 mL of ultra-dry dichloromethane in a round-bottom flask, slowly drip 84 μL of trifluoroacetic anhydride, stir for 5 min, add 90 mg of coronene, and slowly drip 28 μL of trifluoromethanesulfonic acid. Stir the reaction at room temperature for 3 h;

[0201] The crude product was evaporated to remove the solvent and purified by silica gel column chromatography using petroleum ether / dichloromethane (3:1, v / v) as eluent to obtain yellow solid compound 12;

[0202] A 1 mg / mL dichloromethane solution of compound 12 was prepared and mixed with dimethyl isophthalate (DMI) by grinding, the mass ratio of compound 12 to dimethyl isophthalate being 1:1000, and then the mixture was placed in an oven at 85°C until it was completely melted and the dichloromethane was completely volatilized, and then rapidly cooled and crystallized in liquid nitrogen. After standing for a few minutes and returning to room temperature, the 12-DMI-0.1% material was obtained.

[0203] The 12-DMI-0.1% material emits yellow-green light under 365nm ultraviolet light at room temperature. After the ultraviolet light is turned off, the yellow-green light continues for 18 seconds. Fig.12 (A) As shown. At a monitoring wavelength of 535nm and an excitation wavelength of 366nm, its room temperature steady-state luminescence spectrum is shown in the attached Fig.11(B) shows the luminescence spectrum of room temperature with a delay of 1 ms. Fig.11 (C) shows the luminescence decay curve at room temperature. Fig.11 (D) as shown.

[0204] The luminescence peak of the 12-DMI-0.1% material is located at 535nm, and the half-peak width is 23.2nm.

[0205] The hydrogen spectrum of compound 12 is as follows:

[0206] 1 H NMR (400MHz, CDCl3, 298K) δ9.11(d,J=8.8Hz,1H),8.94(s,1H),8.84–8.73(m,9H),7.80(dd,J=2.5,1 .6Hz,1H),7.73(dt,J=7.7,1.3Hz,1H),7.47(t,J=7.9Hz,1H),7.38–7.28(m,3H),7.11–7.03(m,3H).

[0207] Example 13

[0208] Organic narrow-band afterglow materials are prepared by the following process:

[0209]

[0210] Mix 64 mg of ethyl 4-carboxybenzoate and 2 mL of ultra-dry dichloromethane in a round-bottom flask, slowly drip 84 μL of trifluoroacetic anhydride, stir for 5 min, add 90 mg of coronene, and slowly drip 28 μL of trifluoromethanesulfonic acid, and stir the reaction at room temperature for 3 h;

[0211] The crude product was evaporated to remove the solvent and purified by silica gel column chromatography using petroleum ether / dichloromethane (1:1, v / v) as eluent to obtain yellow solid compound 13;

[0212] A 1 mg / mL dichloromethane solution of compound 13 was prepared and mixed with dimethyl isophthalate (DMI) by grinding, and the mass ratio of compound 13 to dimethyl isophthalate was 1:1000;

[0213] The mixture was placed in an oven at 85°C until it was completely melted and the dichloromethane was completely evaporated, and then quickly cooled and crystallized in liquid nitrogen. After standing for several minutes and returning to room temperature, 13-DMI-0.1% material was obtained.

[0214] The 13-DMI-0.1% material emits yellow-green light under 365nm ultraviolet light at room temperature. After the ultraviolet light is turned off, the yellow-green light continues for 22 seconds. Fig.13(A) As shown. At a monitoring wavelength of 538nm and an excitation wavelength of 352nm, its room temperature steady-state luminescence spectrum is shown in the attached Fig.13 (B) shows the luminescence spectrum of room temperature with a delay of 1 ms. Fig.13 (C) shows the luminescence decay curve at room temperature. Fig.13 (D) as shown.

[0215] The luminescence peak of the 13-DMI-0.1% material is located at 538 nm, and the half-peak width is 30.6 nm.

[0216] The hydrogen spectrum of compound 13 is as follows:

[0217] 1 H NMR (400MHz, Chloroform-d) δ9.14(d,J=8.8Hz,1H),8.94(s,1H),8.91–8.70(m,9H),8.30–8.02(m,4H),4.45(q,J=7.1Hz,2H),1.43(t,J=7.1Hz,3H).

[0218] Embodiment 14

[0219] Organic narrow-band afterglow materials are prepared by the following process:

[0220]

[0221] Mix 118 mg of 2,4,6-tribromobenzoic acid and 2 mL of ultra-dry dichloromethane in a round-bottom flask, slowly drip 84 μL of trifluoroacetic anhydride, stir for 5 min, add 90 mg of coronene, and slowly drip 28 μL of trifluoromethanesulfonic acid. Stir the reaction at room temperature for 3 h;

[0222] The crude product was evaporated to remove the solvent and purified by silica gel column chromatography using petroleum ether / dichloromethane (3:1, v / v) as eluent to obtain a light yellow solid compound 14;

[0223] A 1 mg / mL dichloromethane solution of compound 14 was prepared and mixed with phenyl benzoate (PhB) by grinding, and the mass ratio of compound 14 to phenyl benzoate was 1:1000;

[0224] The mixture was placed in an oven at 100°C to completely melt and evaporate the dichloromethane, and then quickly cooled and crystallized in liquid nitrogen. After standing for several minutes and returning to room temperature, 14-PhB-0.1% material was obtained.

[0225] The 14-PhB-0.1% material emits yellow-green light under 365nm ultraviolet light at room temperature. After turning off the ultraviolet light, the yellow-green light continues for 5 seconds. Fig.14(A) As shown. At a monitoring wavelength of 557nm and an excitation wavelength of 365nm, its room temperature steady-state luminescence spectrum is shown in the attached Fig.14 (B) shows the luminescence spectrum of room temperature with a delay of 1 ms. Fig.14 (C) shows the luminescence decay curve at room temperature. Fig.14 (D) as shown.

[0226] The luminescence peak of the 14-PhB-0.1% material is located at 557 nm, and the half-peak width is 33.8 nm.

[0227] The hydrogen spectrum of compound 14 is as follows:

[0228] 1 H NMR (400MHz, CDCl3, 298K) δ10.31(d,J=8.9Hz,1H),9.09(d,J=8.9Hz,1H),9.02(s,1H),8.95–8.76(m,8H),7.96(s,2H).

[0229] Embodiment 15

[0230] Organic narrow-band afterglow materials are prepared by the following process:

[0231]

[0232] 55 mg of 4-methylthiobenzoic acid and 2 mL of ultra-dry dichloromethane were mixed in a round-bottom flask, and 84 μL of trifluoroacetic anhydride was slowly added. After stirring for 5 min, 90 mg of coronene was added, and 28 μL of trifluoromethanesulfonic acid was slowly added. The reaction was stirred at room temperature for 3 h.

[0233] The crude product was evaporated to remove the solvent and purified by silica gel column chromatography using petroleum ether / dichloromethane (1:1, v / v) as eluent to obtain yellow solid compound 15;

[0234] A 1 mg / mL dichloromethane solution of compound 15 was prepared and mixed with phenyl benzoate (PhB) by grinding, and the mass ratio of compound 1 to phenyl benzoate was 1:1000;

[0235] The mixture was placed in an oven at 100°C to completely melt and evaporate the dichloromethane, and then rapidly cooled and crystallized in liquid nitrogen. After standing for several minutes to return to room temperature, 15-PhB-0.1% material was obtained.

[0236] The 15-PhB-0.1% material emits yellow-green light under 365nm ultraviolet light at room temperature. After turning off the ultraviolet light, the yellow-green light continues for 15 seconds. Fig.15(A) As shown. At a monitoring wavelength of 538nm and an excitation wavelength of 365nm, its room temperature steady-state luminescence spectrum is shown in the attached Fig.15 (B) shows the luminescence spectrum of room temperature with a delay of 1 ms. Fig.15 (C) shows the luminescence decay curve at room temperature. Fig.15 (D) as shown.

[0237] The luminescence peak of the 15-PhB-0.1% material is located at 537 nm, and the half-peak width is 24.4 nm.

[0238] The hydrogen spectrum of compound 15 is as follows:

[0239] 1 H NMR (500MHz, CDCl3, 298K) δ9.11 (s, 1H), 9.05–8.87 (m, 10H), 8.03 (s, 2H), 7.36 (s, 2H), 2.58 (d, J = 5.0Hz, 3H).

[0240] Example 16

[0241] Organic narrow-band afterglow materials are prepared by the following process:

[0242]

[0243] Mix 69 mg of 6-methoxy-2-naphthoic acid and 2 mL of ultra-dry dichloromethane in a round-bottom flask, slowly drop 84 μL of trifluoroacetic anhydride, stir for 5 min, add 90 mg of coronene, and slowly drop 28 μL of trifluoromethanesulfonic acid, and stir the reaction at room temperature for 2 h;

[0244] The crude product was evaporated to remove the solvent and purified by silica gel column chromatography using petroleum ether / dichloromethane (3:1, v / v) as eluent to obtain a light yellow solid compound 16;

[0245] A 1 mg / mL dichloromethane solution of compound 16 was prepared and mixed with phenyl benzoate (PhB) by grinding, and the mass ratio of compound 16 to phenyl benzoate was 1:1000;

[0246] The mixture was placed in an oven at 100°C to completely melt and evaporate the dichloromethane, and then rapidly cooled and crystallized in liquid nitrogen. After standing for several minutes to return to room temperature, 16-PhB-0.1% material was obtained.

[0247] The 16-PhB-0.1% material emits yellow-green light under 365nm ultraviolet light at room temperature. After the ultraviolet light is turned off, the yellow-green light continues for 13 seconds. Fig.16(A) As shown. At a monitoring wavelength of 533nm and an excitation wavelength of 365nm, its room temperature steady-state luminescence spectrum is shown in the attached Fig.16 (B) shows the luminescence spectrum of room temperature with a delay of 1 ms. Fig.16 (C) shows the luminescence decay curve at room temperature. Fig.16 (D) as shown.

[0248] The luminescence peak of the 16-PhB-0.1% material is located at 533 nm, and the half-peak width is 29.0 nm.

[0249] The hydrogen spectrum of compound 16 is as follows:

[0250] 1 H NMR (400MHz, CDCl3, 298K) δ9.11(d,J=8.8Hz,1H),9.05(s,1H),8.97–8.83(m,9H),8.36(d,J=1.6Hz,1H),8.28(dd,J=8.6, 1.8Hz,1H),7.91(d,J=8.7Hz,1H),7.65(d,J=9.0Hz,1H),7.23(d,J=2.5Hz,1H),7.13(dd,J=9.0,2.5Hz,1H),3.97(s,3H).

[0251] Embodiment 17

[0252] Organic narrow-band afterglow materials are prepared by the following process:

[0253]

[0254] Mix 69 mg of piperic acid and 2 mL of ultra-dry dichloromethane in a round-bottom flask, slowly drip 84 μL of trifluoroacetic anhydride, stir for 5 min, add 90 mg of coronene, and slowly drip 28 μL of trifluoromethanesulfonic acid. Stir the reaction at room temperature for 2 h;

[0255] The solvent of the obtained crude product was removed by rotary evaporation and purified by silica gel column chromatography using petroleum ether / dichloromethane (3:1, v / v) as eluent to obtain light yellow solid compound 17.

[0256] A 1 mg / mL dichloromethane solution of compound 17 was prepared and mixed with phenyl benzoate (PhB) by grinding, and the mass ratio of compound 17 to phenyl benzoate was 1:1000;

[0257] The mixture was placed in an oven at 100°C to completely melt and evaporate the dichloromethane, and then rapidly cooled and crystallized in liquid nitrogen. After standing for several minutes to return to room temperature, 17-PhB-0.1% material was obtained.

[0258] The 17-PhB-0.1% material emits yellow-green light under 365nm ultraviolet light at room temperature. After the ultraviolet light is turned off, the yellow-green light continues for 16 seconds. Fig.17 (A) As shown. At a monitoring wavelength of 536nm and an excitation wavelength of 365nm, its room temperature steady-state luminescence spectrum is shown in the attached Fig.17 (B) shows the luminescence spectrum of room temperature with a delay of 1 ms. Fig.17 (C) shows the luminescence decay curve at room temperature. Fig.17 (D) as shown.

[0259] The luminescence peak of the 17-PhB-0.1% material is located at 536 nm, and the half-peak width is 25.6 nm.

[0260] The hydrogen spectrum of compound 17 is as follows:

[0261] 1 H NMR (500MHz, CDCl3, 298K) δ9.04 (d, J=8.7Hz, 1H), 8.98–8.89 (m 10H),7.69(d,J=1.6Hz,1H),7.55(d,J=8.5Hz,1H),6.85(d,J=8.2Hz,1H),6.12(s,2H).

[0262] Embodiment 18

[0263] Organic narrow-band afterglow materials are prepared by the following process:

[0264]

[0265] Mix 54 mg of sodium benzene sulfite and 2 mL of ultra-dry dichloromethane in a round-bottom flask, slowly drip 84 μL of trifluoroacetic anhydride, stir for 5 min, add 90 mg of coronene, and slowly drip 28 μL of trifluoromethanesulfonic acid. Stir the reaction at room temperature for 2 h;

[0266] The crude product was evaporated to remove the solvent and purified by silica gel column chromatography using petroleum ether / dichloromethane (5:1, v / v) as eluent to obtain a light yellow solid compound 18;

[0267] A 1 mg / mL dichloromethane solution of compound 18 was prepared and mixed with phenyl benzoate (PhB) by grinding, and the mass ratio of compound 18 to phenyl benzoate was 1:1000;

[0268] The mixture was placed in an oven at 100°C to completely melt and evaporate the dichloromethane, and then rapidly cooled and crystallized in liquid nitrogen. After standing for several minutes to return to room temperature, 18-PhB-0.1% material was obtained.

[0269] The 18-PhB-0.1% material emits yellow-green light under 365nm ultraviolet light at room temperature. After the ultraviolet light is turned off, the yellow-green light continues for 11 seconds. Fig.18 (A) As shown. At a monitoring wavelength of 541nm and an excitation wavelength of 365nm, its room temperature steady-state luminescence spectrum is shown in the attached Fig.18 (B) shows the luminescence spectrum of room temperature with a delay of 1 ms. Fig.18 (C) shows the luminescence decay curve at room temperature. Fig.18 (D) as shown.

[0270] The luminescence peak of the 18-PhB-0.1% material is located at 541 nm, and the half-peak width is 40.2 nm.

[0271] The hydrogen spectrum of compound 18 is as follows:

[0272] 1 H NMR (400MHz, CDCl3, 298K) δ9.39(d,J=8.3Hz,1H),9.09(s,1H),8.95–8.82(m,8H),8.78(d,J=8.3Hz,1H),7.32(d,J=7.9Hz,2H),7.25–7.11(m,3H).

[0273] Embodiment 19

[0274] Organic narrow-band afterglow materials are prepared by the following process:

[0275] 500 g of granular polymethyl methacrylate (PMMA) and 50 mg of compound 3 solid powder were mixed evenly. The mixed pellets were dried and processed using an extruder. During the extrusion process, the feed port temperature was set to 100°C, and the temperatures of the screw and the extrusion outlet were maintained at 240°C to obtain solid cylindrical long strips of 3-PMMA-0.01%-E material, which was further granulated by a granulator to obtain afterglow pellets 3-PMMA-0.01%-E.

[0276] The 3-PMMA-0.01%-E material emits yellow-green light under 365nm ultraviolet light at room temperature. After the ultraviolet light is turned off, the yellow-green light continues for more than 20 seconds. Fig.19 (A) As shown. At a monitoring wavelength of 529nm and an excitation wavelength of 350nm, its room temperature steady-state luminescence spectrum is shown in the attached Fig.19 (B) shows the luminescence spectrum of room temperature with a delay of 1 ms. Fig.19 (C) shows the luminescence decay curve at room temperature. Fig.19 (D) as shown.

[0277] The luminescence peak of the 3-PMMA-0.01%-E material is located at 529 nm, and the half-peak width is 23.6 nm.

[0278] Embodiment 20

[0279] Organic narrow-band afterglow materials are prepared by the following process:

[0280] 1.0 mg of compound 3, 10.0 mg of azobisisobutyronitrile and 1.0 g of polymethyl methacrylate (PMMA) were added to the mold and thoroughly mixed by ultrasound to obtain a yellow solution. The solution was prepolymerized at 85°C for 15 minutes, and the mold was transferred to a low-temperature polymerization at 60°C for 4 hours. The solution was then transferred to an oven at 120°C and heated for 2 hours. After naturally cooling to room temperature, the solution was demolded to obtain 3-PMMA-0.01%-C material.

[0281] The 3-PMMA-0.01%-C material emits yellow-green light under 365nm ultraviolet light at room temperature. After the ultraviolet light is turned off, the yellow-green light continues for more than 20 seconds. Fig. 20 (A) As shown. At a monitoring wavelength of 529nm and an excitation wavelength of 350nm, its room temperature steady-state luminescence spectrum is shown in the attached Fig. 20 (B) shows the luminescence spectrum of room temperature with a delay of 1 ms. Fig. 20 (C) shows the luminescence decay curve at room temperature. Fig. 20 (D) as shown.

[0282] The luminescence peak of the 3-PMMA-0.01%-C material is located at 529 nm, and the half-peak width is 23.6 nm.

[0283] The above embodiments are only preferred implementations of the present invention, and the protection scope of the present invention is not limited to the above embodiments. All technical solutions under the concept of the present invention belong to the protection scope of the present invention. It should be pointed out that for ordinary technicians in this technical field, improvements and modifications without departing from the principle of the present invention should also be regarded as the protection scope of the present invention.

Claims

1. An organic narrow-band afterglow material based on a coronene derivative, comprising a host component and a guest component as a luminescent dopant, characterized in that: The guest component includes a coronene derivative having the following structural formula: Among them, R1-R 11 Selected from -H or -D; R 12 Selected from -C or -S; R 13 Any one selected from -H, -D, -Br; R 14 Selected from -H, -D, Any of; R 15 Selected from -H, -Br, Any of; R 16 Selected from -H or -D; R 17 Selected from any one of -H, -D, and -Br.

2. The organic narrow-band afterglow material according to claim 1, characterized in that: The structural formula of the coronene derivative is one or more of formula (I) to formula (XVIII):

3. The organic narrow-band afterglow material according to claim 1, characterized in that: The main component is selected from one or more of phenyl benzoate, polymethyl methacrylate, and dimethyl isophthalate.

4. The organic narrow-band afterglow material according to claim 1, characterized in that: The mass of the guest component is 0.001 to 0.1% of the mass of the host component.

5. The method for preparing the organic narrow-band afterglow material according to any one of claims 1 to 4, characterized in that: It includes: The guest component was synthesized by Friedel-Crafts acylation or Suzuki reaction; The guest component and the host component are combined by grinding and crystallization or extrusion processing or casting to obtain the organic narrow-band afterglow material; wherein the grinding and crystallization is for non-polymer host components, and the extrusion processing or casting method is for polymer host components; Wherein, the Friedel-Crafts acylation reaction comprises: A first Friedel-Crafts acylation reaction, namely: mixing coronene, aluminum chloride and dichloromethane at a constant temperature of 0° C. to obtain a first mixed solution; dissolving an acyl chloride compound in dichloromethane, and then adding the acyl chloride compound into the first mixed solution, reacting at room temperature to obtain the guest component; or, A second Friedel-Crafts acylation reaction, namely: mixing a phenyl acid or a phenyl acid derivative with ultra-dry dichloromethane, then slowly adding trifluoroacetic anhydride, then adding coronene, and then slowly adding trifluoromethanesulfonic acid, reacting at room temperature to obtain the guest component; wherein the phenyl acid derivative includes phenyl acid ester and / or phenyl acid salt; The Suzuki reaction includes: Mixing a bromine-substituted coronene derivative, a phenylboronic acid compound, palladium acetate, potassium carbonate and N,N'-dimethylformamide to obtain a second mixed solution, heating the second mixed solution at 75-85° C. for 5-7 hours to react, then cooling to room temperature, adding excess water, filtering and washing the generated precipitate to obtain the guest component; The grinding crystallization comprises: Dissolving the guest component in dichloromethane, and grinding and mixing with the host component to obtain a grinding mixture; The ground mixture is melted until the dichloromethane is completely volatilized, then rapidly cooled and crystallized, then allowed to stand and returned to room temperature to obtain an organic narrow-band afterglow material; The extrusion process comprises: The powder of the guest component and the powder of the host component are uniformly mixed and dried, and then extruded to obtain an organic narrow-band afterglow material; The pouring method comprises: The guest component, azobisisobutyronitrile and the main component are added into a mold, prepolymerized after being fully mixed, then low-temperature polymerized and heated for shaping, and after being cooled to room temperature, demolded to obtain the organic narrow-band afterglow material.

6. The preparation method according to claim 5, characterized in that: The method further comprises: purifying the prepared guest component and then combining it with the main component.

7. The preparation method according to claim 5, characterized in that: in, The acyl chloride compound is selected from p-bromobenzoyl chloride; the phenyl acid or phenyl acid derivative is selected from one or more of 3-phenoxybenzoic acid, ethyl 4-carboxybenzoate, 2,4,6-tribromobenzoic acid, 4-methylthiobenzoic acid, 6-methoxy-2-naphthoic acid, piperic acid, sodium benzenesulfite, 3-phenoxybenzoic acid, ethyl 4-carboxybenzoate, and 4-methylthiobenzoic acid; the bromine-substituted coronene derivative is selected from the compound shown in formula I; the phenylboronic acid compound is selected from one or more of phenylboronic acid, p-methoxyphenylboronic acid, 4-dimethylaminophenylboronic acid, 4-ethylphenylboronic acid, 3-methoxyphenylboronic acid, 4-ethoxyphenylboronic acid, 4-fluorophenylboronic acid, and 4-acetylphenylboronic acid.

8. The preparation method according to claim 5, characterized in that: In the first Friedel-Crafts acylation reaction, the molar ratio of the coronene to the acyl chloride compound is 1:1.1; in the second Friedel-Crafts acylation reaction, the molar ratio of the coronene to the phenyl acid or phenyl acid derivative is 1:1.1; in the Suzuki reaction, the molar ratio of the bromine-substituted coronene derivative to the phenylboronic acid compound is 1:1.

2.

9. The preparation method according to claim 5, characterized in that: In the grinding crystallization, the melting temperature is 95-105°C, and liquid nitrogen is used for cooling; in the extrusion processing, the extrusion molding temperature is 100-250°C; in the casting method, the pre-polymerization temperature is 80-90°C, the time is 10-20min, the low-temperature polymerization temperature is 55-65°C, the time is 3.5-4.5h, and the heating setting temperature is 115-125°C, and the time is 1.5-2.5h.

10. Application of the organic narrow-band afterglow material according to any one of claims 1 to 4 or the organic narrow-band afterglow material prepared by the preparation method according to any one of claims 5 to 9 in any of the following: display equipment, medical imaging or medical sensing equipment, lighting or lighting decoration equipment, environmental monitoring equipment, information encryption or information anti-counterfeiting equipment.

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