An organic room-temperature phosphorescent material with controllable afterglow performance, its preparation method and application

Abstract

The present invention relates to the technical field of luminescent materials, and discloses an organic room-temperature phosphorescent material with controllable afterglow performance, a preparation method thereof, and an application thereof. The method includes the following steps: Step 1, dissolving a terpyridine derivative and a polymer in water to obtain a precursor solution; removing water by volatilization to obtain an organic room-temperature phosphorescent material; Step 2, soaking the organic room-temperature phosphorescent material in an aqueous solution containing lanthanide ions, and removing water by volatilization to obtain the organic room-temperature phosphorescent material with controllable afterglow performance; by regulating the concentration of lanthanide ions in the aqueous solution containing lanthanide ions, the afterglow performance of the organic room-temperature phosphorescent material is regulated, and the prepared material still has the advantage of transparency. On the other hand, the organic room-temperature phosphorescent material with controllable afterglow performance exhibits long-wavelength fluorescence emission and short-wavelength afterglow emission, greatly expanding the scope of practical applications.

Description

Technical Field

[0001] The present invention relates to the technical field of luminescent materials, and particularly relates to an organic room temperature phosphorescent material with controllable afterglow performance, a preparation method thereof, and an application thereof. Background Art

[0002] Organic room temperature phosphorescent materials are materials that can still continuously emit light at room temperature after removing the excitation light source. Due to their advantages such as long luminescence lifetime and large Stokes shift, they have broad application prospects in the fields of information encryption, information storage, biological imaging, etc. Currently, organic room temperature phosphorescent materials mostly focus on organic small molecule crystal room temperature phosphorescent materials. Usually, the method of crystal engineering is used to create a rigid environment inside to reduce the quenching of triplet excitons, thereby achieving long afterglow luminescence. However, most of the organic room temperature phosphorescent materials prepared by this method are in a crystal state, with disadvantages such as low transparency and poor processing performance, which greatly limit their development in practical applications.

[0003] In order to overcome the basic disadvantages of organic room temperature phosphorescent materials in the crystal state, polymer-based organic room temperature phosphorescent materials have gradually emerged. Due to their characteristics such as large relative molecular mass and long molecular chain length, polymers are expected to form a rigid environment inside through the entanglement of molecular chains and intramolecular interactions, inhibit the non-radiative transition of triplet excitons, and achieve long afterglow luminescence. Therefore, they also have characteristics such as flexibility, transparency, and easy modification, and have received extensive attention in the past few years. However, how to precisely optimize the performance of polymer-based organic room temperature phosphorescent materials, match specific application scenarios, and ensure their reliability and efficiency is still a formidable challenge.

[0004] To achieve this goal, researchers have made great efforts in developing viable strategies for regulating organic room-temperature phosphorescent materials. For example, the patent with publication number CN113582945A discloses a strategy for regulating phosphorescence lifetime and phosphorescence color by controlling the substituents of the phosphorescent group. For instance, Professor Tang Benzhong introduced different doping amounts of fluorescent dyes into the initial phosphorescent system through the method of energy resonance transfer, achieving not only color regulation but also phosphorescence lifetime regulation (Achieving Color-Tunable and Time-Dependent Organic Long Persistent Luminescence via Phosphorescence Energy Transfer for Advanced Anti-Counterfeiting, Adv. Funct. Mater. 2022, 2208895). However, the above-mentioned regulation strategies require a complex design process of phosphorescent groups or inevitably reduce the transmittance of organic room-temperature phosphorescent materials, making it difficult to meet further practical applications. Therefore, exploring a polymer-based organic room-temperature phosphorescent material that can simply and efficiently regulate afterglow performance and has the advantage of transparency has become an urgent problem to be solved. Summary of the Invention

[0005] The present invention provides a method for preparing an organic room-temperature phosphorescent material with controllable afterglow performance. Compared with the traditionally prepared organic room-temperature phosphorescent materials, by controlling the amount of lanthanide metal ions introduced, the regulation of the afterglow performance of the organic room-temperature phosphorescent material can be achieved, and the prepared material still has the advantage of transparency. On the other hand, the organic room-temperature phosphorescent material with controllable afterglow performance exhibits long-wavelength fluorescence emission and short-wavelength afterglow emission, greatly expanding the scope of practical applications.

[0006] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0007] A method for preparing an organic room-temperature phosphorescent material with controllable afterglow performance, comprising the steps of:

[0008] Step 1, dissolving a terpyridine derivative and a polymer in water to obtain a precursor solution; removing water by volatilization to obtain an organic room-temperature phosphorescent material;

[0009] Step 2, immersing the organic room-temperature phosphorescent material in an aqueous solution containing lanthanide ions, and removing water by volatilization to obtain the organic room-temperature phosphorescent material with controllable afterglow performance;

[0010] By regulating the concentration of lanthanide ions in the aqueous solution containing lanthanide ions, the regulation of the afterglow performance of the organic room-temperature phosphorescent material is achieved.

[0011] The terpyridine derivatives include one or more of terpyridine, terpyridine phenylboronic acid, 4,4',4”-trimethyl-terpyridine, 2,3,5,6-tetrapyridyl-pyrazine, and 4-terpyridine-4’-aniline.

[0012] The bipyridine phenylboronic acid includes 4'-(4-boronophenyl)-2,2':6',2”-terpyridine (4-TPYB(OH)2) and 4'-(3-boronyl)-2,2':6',2”-terpyridine; (3-([[2,2':6',2”-bipyridin]-4'-yl)phenyl)boronic acid (3-TPYB(OH)2), and their structures are as follows:

[0013]

[0014] The polymer includes one or more of polyvinyl alcohol, polyethylene glycol, and poly-N-hydroxyethyl acrylamide.

[0015] In some embodiments, when the terpyridine derivative is terpyridine phenylboronic acid, in step 1, the terpyridine derivative, the polymer, and ammonia water are dissolved in water to obtain a precursor solution. The molar ratio of ammonia water to terpyridine phenylboronic acid is 0.5-10:1.

[0016] In some embodiments, the lanthanide ions include one or more of europium ions, terbium ions, and lanthanum ions.

[0017] The aqueous solution containing lanthanide ions is an aqueous solution of lanthanide nitrate or chloride. Such as one or more of europium nitrate, terbium nitrate, europium chloride, and terbium chloride.

[0018] In some embodiments, the lanthanide ions are europium ions or terbium ions;

[0019] In some embodiments, in step 1, the mass of the terpyridine derivative is 0.1-1.8 wt% of the mass of the polymer. When the content of the terpyridine derivative is too high, the polymer matrix cannot effectively fix the phosphors, resulting in a decrease in intensity and lifetime, and a reduction in transparency.

[0020] In some embodiments, in step 2, the mass concentration of lanthanide ions in the aqueous solution containing lanthanide ions is 1-20 mg / mL. The inventors found that as the concentration of lanthanide ions increases, the afterglow duration of the organic room temperature phosphorescent material shortens. Therefore, by controlling the amount of europium and terbium ions introduced, precise regulation of the afterglow intensity and afterglow time can be achieved.

[0021] In some embodiments, the dissolution temperature in step 1 is 95-110 °C; it is appropriate to dissolve the terpyridine derivative to obtain a transparent and homogeneous precursor solution;

[0022] In some embodiments, the soaking time in step 2 is 30 s - 5 min; in some embodiments, the soaking time in step 2 is 60 s, 80 s, 100 s, 120 s, 150 s, 180 s, 200 s, 240 s, 270 s, or any value therebetween;

[0023] In some embodiments, the temperature for volatilizing and removing moisture is 50 - 80 °C, and the volatilization is for more than 0.5 h. Such as volatilizing for 0.5 - 3 h;

[0024] In some embodiments, the terpyridine derivative is terpyridine phenylboronic acid. The organic room temperature phosphorescent material prepared in step 1 emits blue fluorescence under ultraviolet light irradiation and emits blue afterglow after the ultraviolet light is turned off;

[0025] In some embodiments, when the lanthanide ion in step 2 is europium ion, the organic room temperature phosphorescent material with controllable afterglow performance prepared in step 2 emits red fluorescence under ultraviolet light irradiation and emits blue afterglow after the ultraviolet light is turned off;

[0026] In some embodiments, when the lanthanide ion in step 2 is terbium ion, the obtained organic room temperature phosphorescent material with controllable afterglow performance prepared in step 2 emits green fluorescence under ultraviolet light irradiation and emits blue afterglow after the ultraviolet light is turned off.

[0027] The present invention also provides an organic room temperature phosphorescent material with controllable afterglow performance prepared according to the described preparation method. As the mass concentration of the lanthanide ion in the aqueous solution containing the lanthanide ion increases, the phosphorescence lifetime and the afterglow duration of the organic room temperature phosphorescent material with controllable afterglow performance decrease.

[0028] The fluorescence spectrum of the organic room temperature phosphorescent material with controllable afterglow performance is redshifted compared to the organic room temperature phosphorescent material in step 1.

[0029] The transmittance of the organic room temperature phosphorescent material with controllable afterglow performance is not less than 90%.

[0030] The present invention provides the application of the described organic room temperature phosphorescent material with controllable afterglow performance in the fields of biological imaging, information encryption or anti-counterfeiting. The organic room temperature phosphorescent material prepared by the present invention has the effects of high transparency, and the afterglow intensity and afterglow time can be accurately regulated, and has good application prospects in the fields of biological imaging, information encryption or anti-counterfeiting, etc.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] (1) By controlling the amount of lanthanide ions introduced, the present invention realizes precise regulation of the afterglow intensity and afterglow time of the organic room temperature phosphorescent material. Compared with the traditional organic room temperature phosphorescent material, the organic room temperature phosphorescent material prepared by the present invention has the characteristics of long-wavelength fluorescence emission and short-wavelength afterglow emission.

[0033] (2) The organic room temperature phosphorescent materials prepared by the present invention all have the advantage of transparency. The preparation method and the solvent are both aqueous solutions, meeting the requirements of green chemistry.

[0034] (3) The organic room temperature phosphorescent materials with controllable afterglow performance prepared by the present invention have good application prospects in the fields of biological imaging, information encryption, anti-counterfeiting, etc. Description of the Drawings

[0035] Figure 1 Steady-state fluorescence and phosphorescence spectra of the organic room temperature phosphorescent material B prepared in Example 1.

[0036] Figure 2 Time-resolved emission decay of the organic room temperature phosphorescent material B prepared in Example 1.

[0037] Figure 3 Steady-state fluorescence and afterglow emission spectra of the organic room temperature phosphorescent material C prepared in Example 3.

[0038] Figure 4 Time-resolved emission decay of the organic room temperature phosphorescent material C prepared in Example 3.

[0039] Figure 5 Steady-state fluorescence and afterglow emission spectra of the organic room temperature phosphorescent material D prepared in Example 3.

[0040] Figure 6 Time-resolved emission decay of the organic room temperature phosphorescent material D prepared in Example 3.

[0041] Figure 7 Phosphorescence spectra and time-resolved emission decay of the organic room temperature phosphorescent material C prepared in Examples 1 - 7.

[0042] Figure 8 Phosphorescence spectra and time-resolved emission decay of the organic room temperature phosphorescent material D prepared in Examples 1 - 7.

[0043] Figure 9 UV transmittance spectra of the organic room temperature phosphorescent materials C and D prepared in Examples 1, 3, and 6.

[0044] Figure 10 Encoding and encryption application display in the field of information encryption prepared in Application Example 1. Detailed Description of the Invention

[0045] In order to make the objectives, technical solutions and advantages of the present invention more clear and understandable, the present invention will be further described in detail below in conjunction with embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention. Those skilled in the art who make modifications or equivalent replacements based on the understanding of the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention shall be covered by the protection scope of the present invention.

[0046] The raw materials used in the following specific embodiments are all purchased from the market, and the ammonia water is industrial ammonia water with a concentration of 25-28wt%.

[0047] Example 1

[0048] Step 1: Add 3 mg of terpyridine phenylboronic acid, 500 mg of polyvinyl alcohol (1799), and 1 ml of ammonia water to 7 ml of deionized water, and heat and stir at 96 °C for 45 minutes until completely dissolved to present a transparent and homogeneous state, obtaining precursor solution A; Take 2 ml of precursor solution A and drop it onto a 25 mm × 75 mm glass slide, and spread it evenly. Heat it at 65 °C for 90 minutes to volatilize and form a film, obtaining organic room temperature phosphorescent material B;

[0049] The organic room temperature phosphorescent material B prepared in this example was tested, and this organic room temperature phosphorescent material has obvious phosphorescent emission characteristics. As Figure 1 shown, the main peak of fluorescence emission of organic room temperature phosphorescent material B is located at 360 nm, and the main peak of phosphorescent emission is located at 450 nm. As Figure 2 shown, the calculated lifetime of organic room temperature phosphorescent material B after fitting is 629 ms, belonging to an ultra-long afterglow material.

[0050] Step 2: Immerse the prepared organic room temperature phosphorescent material B in an aqueous solution of europium ions with a concentration of 0.1 mg / mL for 150 seconds, then take it out and heat and volatilize at 65 °C for 1 hour to obtain organic room temperature phosphorescent material C with controllable afterglow performance.

[0051] Step 3: Immerse the prepared organic room temperature phosphorescent material B in an aqueous solution of terbium ions with a concentration of 0.1 mg / mL for 150 seconds, then take it out and heat and volatilize at 65 °C for 1 hour to obtain organic room temperature phosphorescent material D with controllable afterglow performance.

[0052] The calculated lifetime of organic room temperature phosphorescent material C after fitting is 537 ms, and the calculated lifetime of organic room temperature phosphorescent material D after fitting is 509 ms.

[0053] Example 2

[0054] Step 1: Add 3 mg of terpyridylphenylboronic acid, 500 mg of polyvinyl alcohol (1799), and 1 ml of ammonia water to 7 ml of deionized water. Heat and stir at 96 °C for 45 minutes until completely dissolved to form a transparent and homogeneous state, obtaining precursor solution A. Take 2 ml of precursor solution A and drop it onto a 25 mm × 75 mm glass slide, then spread it evenly. Heat at 65 °C for 90 minutes to volatilize and form a film, obtaining organic room-temperature phosphorescent material B.

[0055] Step 2: Immerse the obtained organic room-temperature phosphorescent material B in an aqueous solution of europium ions with a concentration of 0.5 mg / mL for 150 seconds, then take it out and heat and volatilize at 65 °C for 1 hour to obtain organic room-temperature phosphorescent material C with controllable afterglow performance.

[0056] Step 3: Immerse the obtained organic room-temperature phosphorescent material B in an aqueous solution of terbium ions with a concentration of 0.5 mg / mL for 150 seconds, then take it out and heat and volatilize at 65 °C for 1 hour to obtain organic room-temperature phosphorescent material D with controllable afterglow performance.

[0057] The calculated lifetime of the organic room-temperature phosphorescent material C after fitting is 521 ms, and the calculated lifetime of the organic room-temperature phosphorescent material D after fitting is 521 ms.

[0058] Example 3

[0059] Step 1: Add 3 mg of terpyridylphenylboronic acid, 500 mg of polyvinyl alcohol (1799), and 1 ml of ammonia water to 7 ml of deionized water. Heat and stir at 96 °C for 45 minutes until completely dissolved to form a transparent and homogeneous state, obtaining precursor solution A. Take 2 ml of precursor solution A and drop it onto a 25 mm × 75 mm glass slide, then spread it evenly. Heat at 65 °C for 90 minutes to volatilize and form a film, obtaining organic room-temperature phosphorescent material B.

[0060] Step 2: Immerse the obtained organic room-temperature phosphorescent material B in an aqueous solution of europium ions with a concentration of 1 mg / mL for 150 seconds, then take it out and heat and volatilize at 65 °C for 1 hour to obtain organic room-temperature phosphorescent material C with controllable afterglow performance.

[0061] Step 3: Immerse the obtained organic room-temperature phosphorescent material B in an aqueous solution of terbium ions with a concentration of 1 mg / mL for 150 seconds, then take it out and heat and volatilize at 65 °C for 1 hour to obtain organic room-temperature phosphorescent material D with controllable afterglow performance.

[0062] Test the obtained organic room-temperature phosphorescent material in this example. As Figure 3 shown, the main fluorescence emission peak of the organic room-temperature phosphorescent material C is located at 620 nm, and the main phosphorescence emission peak is located at 450 nm. As Figure 4 shown, the calculated lifetime of the organic room-temperature phosphorescent material C after fitting is 495 ms, belonging to an ultra-long afterglow material.

[0063] As Figure 5As shown, the main fluorescence emission peak of the organic room-temperature phosphorescent material D is located at 540 nm, and the main phosphorescence emission peak is located at 450 nm. As Figure 6 shown, the calculated lifetime of the organic room-temperature phosphorescent material D after fitting is 489 ms, belonging to the ultra-long afterglow material.

[0064] Example 4

[0065] Step 1: Add 3 mg of terpyridylphenylboronic acid, 500 mg of polyvinyl alcohol (1799), and 1 ml of ammonia water to 7 ml of deionized water, heat and stir at 96 °C for 45 minutes until completely dissolved to present a transparent and homogeneous state, obtaining the precursor solution A; take 2 ml of the precursor solution A and drop it onto a 25 mm × 75 mm glass slide, and spread it evenly, then heat and volatilize to form a film at 65 °C for 90 minutes to prepare the organic room-temperature phosphorescent material B;

[0066] Step 2: Immerse the prepared organic room-temperature phosphorescent material B in an aqueous solution of europium ions at 3 mg / mL for 150 seconds, then take it out and heat and volatilize at 65 °C for 1 hour to obtain the organic room-temperature phosphorescent material C with controllable afterglow performance.

[0067] Step 3: Immerse the prepared organic room-temperature phosphorescent material B in an aqueous solution of terbium ions at 3 mg / mL for 150 seconds, then take it out and heat and volatilize at 65 °C for 1 hour to obtain the organic room-temperature phosphorescent material D with controllable afterglow performance.

[0068] The calculated lifetime of the organic room-temperature phosphorescent material C after fitting is 490 ms, and the calculated lifetime of the organic room-temperature phosphorescent material D after fitting is 448 ms.

[0069] Example 5

[0070] Step 1: Add 3 mg of terpyridylphenylboronic acid, 500 mg of polyvinyl alcohol (1799), and 1 ml of ammonia water to 7 ml of deionized water, heat and stir at 96 °C for 45 minutes until completely dissolved to present a transparent and homogeneous state, obtaining the precursor solution A; take 2 ml of the precursor solution A and drop it onto a 25 mm × 75 mm glass slide, and spread it evenly, then heat and volatilize to form a film at 65 °C for 90 minutes to prepare the organic room-temperature phosphorescent material B;

[0071] Step 2: Immerse the prepared organic room-temperature phosphorescent material B in an aqueous solution of europium ions at 5 mg / mL for 150 seconds, then take it out and heat and volatilize at 65 °C for 1 hour to obtain the organic room-temperature phosphorescent material C with controllable afterglow performance.

[0072] Step 3: Immerse the prepared organic room-temperature phosphorescent material B in an aqueous solution of terbium ions at 5 mg / mL for 150 seconds, then take it out and heat and volatilize at 65 °C for 1 hour to obtain the organic room-temperature phosphorescent material D with controllable afterglow performance.

[0073] The calculated lifetime of the organic room-temperature phosphorescent material C is 492 ms, and the calculated lifetime of the organic room-temperature phosphorescent material D is 437 ms.

[0074] Example 6

[0075] Step 1: Add 3 mg of terpyridylphenylboronic acid, 500 mg of polyvinyl alcohol (1799), and 1 ml of ammonia water to 7 ml of deionized water. Heat and stir at 96 °C for 45 minutes until completely dissolved to form a transparent and homogeneous state, obtaining the precursor solution A. Take 2 ml of the precursor solution A and drop it onto a 25 mm × 75 mm glass slide, then spread it evenly. Heat and volatilize to form a film at 65 °C for 90 minutes to obtain the organic room-temperature phosphorescent material B.

[0076] Step 2: Immerse the prepared organic room-temperature phosphorescent material B in an aqueous solution of europium ions with a concentration of 10 mg / mL for 150 seconds, then take it out and heat and volatilize at 65 °C for 1 hour to obtain the organic room-temperature phosphorescent material C with controllable afterglow performance.

[0077] Step 3: Immerse the prepared organic room-temperature phosphorescent material B in an aqueous solution of terbium ions with a concentration of 10 mg / mL for 150 seconds, then take it out and heat and volatilize at 65 °C for 1 hour to obtain the organic room-temperature phosphorescent material D with controllable afterglow performance.

[0078] The calculated lifetime of the organic room-temperature phosphorescent material C is 450 ms, and the calculated lifetime of the organic room-temperature phosphorescent material D is 404 ms.

[0079] Example 7

[0080] Step 1: Add 3 mg of terpyridylphenylboronic acid, 500 mg of polyvinyl alcohol (1799), and 1 ml of ammonia water to 7 ml of deionized water. Heat and stir at 96 °C for 45 minutes until completely dissolved to form a transparent and homogeneous state, obtaining the precursor solution A. Take 2 ml of the precursor solution A and drop it onto a 25 mm × 75 mm glass slide, then spread it evenly. Heat and volatilize to form a film at 65 °C for 90 minutes to obtain the organic room-temperature phosphorescent material B.

[0081] Step 2: Immerse the prepared organic room-temperature phosphorescent material B in an aqueous solution of europium ions with a concentration of 20 mg / mL for 150 seconds, then take it out and heat and volatilize at 65 °C for 1 hour to obtain the organic room-temperature phosphorescent material C with controllable afterglow performance.

[0082] Step 3: Immerse the prepared organic room-temperature phosphorescent material B in an aqueous solution of terbium ions with a concentration of 20 mg / mL for 150 seconds, then take it out and heat and volatilize at 65 °C for 1 hour to obtain the organic room-temperature phosphorescent material D with controllable afterglow performance.

[0083] The calculated lifetime of the organic room-temperature phosphorescent material C is 307 ms, and the calculated lifetime of the organic room-temperature phosphorescent material D is 185 ms. The phosphorescence intensities of the organic room-temperature phosphorescent materials C and D tend to 0, and the visible phosphorescence effect disappears.

[0084] The phosphorescence spectra and time-resolved emission decays of the organic room-temperature phosphorescent materials C prepared in Examples 1-7 are summarized in Figure 7 It can be seen that as the concentration of europium ions in the immersion solution increases, the phosphorescence intensity of the material gradually decreases, and the phosphorescence lifetime of the material gradually decreases.

[0085] The phosphorescence spectra and time-resolved emission decays of the organic room-temperature phosphorescent materials D prepared in Examples 1-7 are summarized in Figure 8 It can be seen that as the concentration of terbium ions in the immersion solution increases, the phosphorescence intensity of the material gradually decreases, and the phosphorescence lifetime of the material gradually decreases.

[0086] The UV transmittance spectra of C and D of the organic room-temperature phosphorescent materials prepared in Examples 1, 3, and 6 are summarized in Figure 9 It can be seen that the material has good transparency, and the overall transmittance is above 90%.

[0087] Comparative Example 1

[0088] 3 mg of terpyridylphenylboronic acid and 500 mg of polyvinyl alcohol (1799) were added to 8 ml of deionized water, and the mixture was heated and stirred at 96 °C for 45 minutes until completely dissolved to present a transparent and homogeneous state, obtaining a precursor solution E;

[0089] 2 ml of the precursor solution E was taken and dropped onto a 25 mm × 75 mm glass slide and spread evenly, and then heated at 65 °C for 90 minutes to evaporate and form a film, obtaining an organic room-temperature phosphorescent material F;

[0090] The prepared organic room-temperature phosphorescent material F without adding ammonia water emits only about 2 s of dark blue afterglow after the UV lamp is turned off.

[0091] Comparative Example 2

[0092] 0.2 mg of terpyridylphenylboronic acid, 500 mg of polyvinyl alcohol (1799), and 1 ml of ammonia water were added to 7 ml of deionized water, and the mixture was heated and stirred at 96 °C for 45 minutes until completely dissolved to present a transparent and homogeneous state, obtaining a precursor solution A; 2 ml of the precursor solution A was taken and dropped onto a 25 mm × 75 mm glass slide and spread evenly, and then heated at 65 °C for 90 minutes to evaporate and form a film, obtaining an organic room-temperature phosphorescent material B;

[0093] It was observed that the visible phosphorescence effect of the organic room-temperature phosphorescent material B with too low doping amount of terpyridine derivative tended to disappear after the UV lamp was turned off.

[0094] Comparative Example 3

[0095] 11 mg of terpyridine phenylboronic acid, 500 mg of polyvinyl alcohol (1799), and 1 ml of ammonia water were added to 7 ml of deionized water, and the mixture was heated and stirred at 96 °C for 45 minutes until completely dissolved to present a transparent and homogeneous state, obtaining precursor solution A; 2 ml of precursor solution A was dropped onto a 25 mm × 75 mm glass slide and spread evenly, and then heated at 65 °C for 90 minutes to evaporate and form a film, obtaining organic room temperature phosphorescent material B;

[0096] It was observed that in this comparative example, for the organic room temperature phosphorescent material B with too high doping amount of terpyridine derivative, the visible transparency decreased under daylight lamp.

[0097] Comparative Example 4

[0098] Step 1, 3 mg of terpyridine phenylboronic acid, 500 mg of polyvinyl alcohol (1799), and 1 ml of ammonia water were added to 7 ml of deionized water, and the mixture was heated and stirred at 96 °C for 45 minutes until completely dissolved to present a transparent and homogeneous state, obtaining precursor solution A; 2 ml of precursor solution A was dropped onto a 25 mm × 75 mm glass slide and spread evenly, and then heated at 65 °C for 90 minutes to evaporate and form a film, obtaining organic room temperature phosphorescent material B;

[0099] Step 2, the obtained organic room temperature phosphorescent material B was immersed in an aqueous solution of europium ions with a concentration of 0.05 mg / mL for 150 seconds and then taken out, and heated and evaporated at 65 °C for 1 hour to obtain organic room temperature phosphorescent material C with controllable afterglow performance.

[0100] Step 3, the obtained organic room temperature phosphorescent material B was immersed in an aqueous solution of terbium ions with a concentration of 0.05 mg / mL for 150 seconds and then taken out, and heated and evaporated at 65 °C for 1 hour to obtain organic room temperature phosphorescent material D with controllable afterglow performance.

[0101] Under ultraviolet lamp irradiation, for the organic room temperature phosphorescent material C immersed in the aqueous solution of europium ions with too low concentration, a small amount of red clusters appeared on the basis of blue fluorescence, indicating uneven distribution of europium ions. Under ultraviolet lamp irradiation, for the organic room temperature phosphorescent material D immersed in the aqueous solution of terbium ions with too low concentration, a small amount of green clusters appeared on the basis of blue fluorescence, indicating uneven distribution of terbium ions.

[0102] Demonstration in the field of information encryption in Application Example 1

[0103] Such as Figure 10, The materials prepared in Example 3, Example 5, and Example 7 were combined together for a feasibility test of applications in the field of information encryption. The materials prepared in different examples were placed at different positions, and codes were defined by ourselves. It can be seen that when the ultraviolet lamp was turned off for 0.1 s, the signal emitted was "FOX", and when the ultraviolet lamp was turned off for 1.5 s, the signal emitted was "BEE". It can be seen that the organic room-temperature phosphorescent materials with controllable afterglow performance in the present invention can be used in the fields of biotechnology, information encryption, etc. The afterglow intensity and duration can be regulated by regulating the concentration of the lanthanide ion solution.

[0104] The above-described embodiments further illustrate the technical solutions of the present invention. It should be understood that these embodiments are only used to illustrate the present invention and are not used to limit the scope of the present invention. Any modifications, supplements, or substitutions in a similar manner within the principle scope of the present invention should be included within the protection scope of the present invention.

Claims

1. A preparation method of an organic room-temperature phosphorescent material with controllable afterglow performance, characterized in that, Including the steps: Step 1: Dissolve the terpyridine derivative and the polymer in water to obtain a precursor solution; remove the water by volatilization to obtain the organic room temperature phosphorescent material; Step 2: Immerse the organic room temperature phosphorescent material in an aqueous solution containing lanthanide ions, and remove the water by volatilization to obtain the organic room temperature phosphorescent material with controllable afterglow performance; the mass concentration of lanthanide ions in the aqueous solution containing lanthanide ions is 1-20 mg / mL; By regulating the concentration of lanthanide ions in the aqueous solution containing lanthanide ions, the afterglow performance of the organic room temperature phosphorescent material is regulated; The terpyridine derivative is one or more of terpyridine, terpyridine phenylboronic acid, 4,4',4”-trimethyl-terpyridine, 2,3,5,6-tetrapyridyl-pyrazine; When the terpyridine derivative is terpyridine phenylboronic acid, in Step 1, dissolve the terpyridine derivative, the polymer and ammonia water in water to obtain a precursor solution; The polymer includes one or more of polyvinyl alcohol, polyethylene glycol, poly-N-hydroxyethyl acrylamide; 2. The preparation method of the organic room temperature phosphorescent material with controllable afterglow performance according to claim 1, characterized in that, The lanthanide ions include one or more of europium ions, terbium ions, lanthanum ions; The aqueous solution containing lanthanide ions is an aqueous solution of lanthanide nitrate or chloride; 3. The preparation method of the organic room temperature phosphorescent material with controllable afterglow performance according to claim 1, characterized in that, In Step 1, the mass of the terpyridine derivative is 0.1-1.8 wt% of the mass of the polymer; 4. The preparation method of the organic room temperature phosphorescent material with controllable afterglow performance according to claim 1, characterized in that, The dissolution temperature in Step 1 is 95-110 °C; The immersion time in Step 2 is 30 s-5 min; The temperature for removing the water by volatilization is 50-80 °C, and the volatilization time is more than 0.5 h; 5. The organic room-temperature phosphorescent material with controllable afterglow performance prepared by the preparation method according to claims 1-4, characterized in that, As the mass concentration of lanthanide ions in the aqueous solution containing lanthanide ions increases, the phosphorescence lifetime of the organic room temperature phosphorescent material with controllable afterglow performance decreases, and the afterglow duration decreases; And / or, the fluorescence spectrum of the organic room temperature phosphorescent material with controllable afterglow performance is red-shifted compared with that of the organic room temperature phosphorescent material in Step 1; 6. The organic room temperature phosphorescent material with controllable afterglow performance according to claim 5, characterized in that, The transmittance of the organic room temperature phosphorescent material with controllable afterglow performance is not less than 90%; 7. Application of the organic room temperature phosphorescent material with controllable afterglow performance according to claim 5 in the fields of biological imaging, information encryption or anti-counterfeiting.

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