Bio-based doped material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence as well as preparation method and application of bio-based doped material

Abstract

The invention discloses a bio-based doped material with multiple stimulation responsiveness and ultra-long room temperature phosphorescence as well as a preparation method and application of the bio-based doped material. According to the invention, cyclodextrin is used as a doping host material, a boric acid-based compound is used as a guest material, the boric acid-based compound is doped in a binary system taking cyclodextrin as a host, intersection between systems is enhanced by using a synergistic effect of strong hydrogen bonds, C-O-B covalent cross-linking and host-guest encapsulation, and meanwhile, non-radiative transition is remarkably inhibited; therefore, the bio-based doped material with multiple stimulation responsiveness and ultra-long room-temperature phosphorescence is obtained.

Description

Technical Field

[0001] The present invention relates to the technical field of organic luminescent materials, and in particular to a bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence, and a preparation method and application thereof. Background Art

[0002] Pure organic ultra-long room temperature phosphorescent materials have shown great development potential in the field of advanced organic optoelectronic functional materials due to their unique optical properties and advantages. In order to overcome the defects of phosphorescent emission, it is an effective design strategy to use polymer doping or small molecule matrix doping to construct a rigid microenvironment and then suppress its non-radiative transition to achieve efficient and long-life organic room temperature phosphorescent emission. However, commonly used petroleum-based polymers usually have low biocompatibility and degradability, and their application scenarios are extremely limited. In addition, the application of stimulus-responsive organic room temperature phosphorescent materials that can respond effectively to external changes in a timely manner in the fields of information storage, anti-counterfeiting, biosensing, etc. is expanding year by year, but currently such materials are mostly seen in single simple stimulation modes and response output scenarios.

[0003] Therefore, it is necessary to develop a class of room temperature phosphorescent materials that can have multiple stimulus response properties while combining efficient ultra-long room temperature phosphorescence properties and sustainable recycling, thereby providing a new perspective for the construction of recyclable ultra-long room temperature phosphorescent materials and opening up new paths for broader application scenarios. Summary of the invention

[0004] In order to solve the above problems, the present application provides a bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence, and a preparation method and application thereof.

[0005] In a first aspect, an embodiment of the present application provides a bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence, comprising a host material and a guest material, wherein the host material is a cyclodextrin having 6-8 D-pyranose glucose units, and the guest material is a boric acid-based compound having a conjugated structure.

[0006] In some embodiments, the structural formula of the host material is at least one of formula (H1) to formula (H3),

[0007]

[0008] The structural formula of the guest material is at least one of formula (G1) to formula (G10),

[0009]

[0010] In some embodiments, the phosphorescence lifetime of the bio-based dopant material is ≥ 0.1 ms, and the absolute phosphorescence quantum yield of the bio-based dopant material is ≥ 0.1%.

[0011] In some embodiments, the bio-based doping material has light-activated stimulus responsiveness, and the light-activated stimulus responsiveness includes: under ultraviolet light irradiation at different times, the phosphorescence intensity of the bio-based doping material is different.

[0012] In some embodiments, the bio-based doping material has excitation wavelength stimulus responsiveness, and the excitation wavelength stimulus responsiveness includes: under the irradiation of excitation light of different wavelengths, the phosphorescence intensity of the bio-based doping material is different.

[0013] In some embodiments, the bio-based doping material has mechanical force stimulation responsiveness, and the mechanical force stimulation responsiveness includes: the phosphorescence intensity of the bio-based doping material is different under different grinding times.

[0014] In some embodiments, the bio-based doping material has temperature stimulus responsiveness, and the temperature stimulus responsiveness includes: at different temperatures, the phosphorescence intensity of the bio-based doping material is different, wherein the temperature range is -196°C-140°C.

[0015] In some embodiments, the bio-based doping material has humidity stimulus responsiveness, and the humidity stimulus responsiveness includes: the phosphorescence intensity of the bio-based doping material is different under different humidity, wherein the humidity range is 20%-80%.

[0016] In the second aspect, an embodiment of the present application provides a method for preparing a bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence, comprising the following steps: adding a host material and a guest material to water, ultrasonically dispersing them at 50-80°C, heating them in an oven at 60-100°C for 4-12 hours, and then drying them in an oven at 100-150°C to obtain the bio-based doping material, wherein the host material is a cyclodextrin having 6-8 D-pyranose units, and the guest material is a boric acid-based compound having a conjugated structure.

[0017] In a third aspect, the embodiments of the present application provide a bio-based doped material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence for use in optoelectronic devices, display materials, information storage materials, ultraviolet tracking materials or anti-counterfeiting materials.

[0018] The bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence provided in the embodiments of the present application has the following technical effects:

[0019] (1) The present invention uses cyclodextrin as a doping host material and a boric acid compound as a guest material to prepare a bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence. The raw materials used are all pure organic compounds, which have high biocompatibility and good sustainability. They are widely available and commercially available, and the preparation method is simple and efficient, and the price is low and economical.

[0020] (2) The bio-based doping material provided in the embodiments of the present application has multiple stimulus responsiveness, and the photophysical properties of the bio-based doping material are efficient and stable, and can be used in the air with the aid of light activation without the need for inert gas protection or an absolute vacuum environment;

[0021] (3) The bio-based doped material provided in the embodiments of the present application has a high absolute phosphorescence quantum yield and can respond to external light, excitation light wavelength, mechanical force, temperature and humidity. The bio-based doped material has an ultra-long luminescence lifetime and is suitable for optoelectronic devices, display materials, information storage or anti-counterfeiting materials and other fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative work.

[0023] Figure 1 Phosphorescence spectra of bio-based doping materials with multi-stimulus responsiveness and ultra-long room temperature phosphorescence provided in some embodiments of the present application;

[0024] Figure 2 Phosphorescence lifetime spectra of bio-based doping materials with multiple stimulus responsiveness and ultra-long room temperature phosphorescence provided in some embodiments of the present application;

[0025] Figure 3 Photos of the luminescence changes of the bio-based doping materials with multiple stimulus responsiveness and ultra-long room temperature phosphorescence before and after excitation with ultraviolet light of different wavelengths provided in some embodiments of the present application;

[0026] Figure 4 Phosphorescence spectra of bio-based doping materials with multiple stimulus responsiveness and ultra-long room temperature phosphorescence after irradiation with different excitation light wavelengths provided in some embodiments of the present application;

[0027] Figure 5 Phosphorescence spectra of bio-based doping materials with multiple stimulus responsiveness and ultra-long room temperature phosphorescence at different grinding times provided in some embodiments of the present application;

[0028] Figure 6Photoluminescence quantum yield diagram of bio-based doping materials with multiple stimulus responsiveness and ultra-long room temperature phosphorescence provided in some embodiments of the present application;

[0029] Figure 7 Phosphorescence spectra of bio-based doping materials with multiple stimulus responsiveness and ultra-long room temperature phosphorescence after irradiation with different excitation light wavelengths provided in some embodiments of the present application;

[0030] Figure 8 Phosphorescence spectra of bio-based doping materials with multi-stimulus responsiveness and ultra-long room temperature phosphorescence under ultraviolet light irradiation at different times provided in some embodiments of the present application;

[0031] Fig. 9 Phosphorescence spectra of bio-based doping materials with multi-stimulus responsiveness and ultra-long room temperature phosphorescence at different temperatures provided in some embodiments of the present application;

[0032] Fig.10 Phosphorescence spectra of bio-based doping materials with multi-stimulus responsiveness and ultra-long room temperature phosphorescence at different humidity levels provided in some embodiments of the present application;

[0033] Fig.11 Photos of the luminescence changes of the bio-based doping materials with multiple stimulus responsiveness and ultra-long room temperature phosphorescence before and after ultraviolet light excitation provided in some embodiments of the present application;

[0034] Fig.12 Schematic diagram of the application of bio-based doping materials with multiple stimulus responsiveness and ultra-long room temperature phosphorescence provided in some embodiments of the present application. DETAILED DESCRIPTION

[0035] In order to facilitate the understanding of this specification, the specification will be described more fully below with reference to the relevant drawings. The preferred embodiments of this specification are given in the drawings. However, this specification can be implemented in many different forms without departing from the core spirit of this specification and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of this specification more thorough and comprehensive.

[0036] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art to which this specification belongs. The terms used herein in this specification are only for the purpose of describing specific embodiments and are not intended to limit this specification. The term "and / or" used herein includes any and all combinations of one or more of the related listed items.

[0037] In the first aspect, the embodiments of the present application provide a bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence, including a host material and a guest material, the host material is a cyclodextrin having 6-8 D-pyranose units, and the guest material is a boric acid-based compound having a conjugated structure.

[0038] In the embodiments of the present application, cyclodextrin is used as the doping host material and a boric acid compound is used as the guest material. The boric acid compound is doped into a binary system with cyclodextrin as the host. The synergistic effects of strong hydrogen bonds, COB covalent crosslinking and host-guest encapsulation are utilized to enhance the cross-linking between systems, while significantly suppressing non-radiative transitions, thereby obtaining a bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence.

[0039] In some embodiments, the structural formula of the host material is at least one of Formula (H1)-Formula (H3),

[0040]

[0041] Among them, the inventors found through a large number of experiments that the main material using cyclodextrin with 8 D-pyranose units (i.e., cyclodextrin corresponding to H1) can be a bio-based doping material with better stimulus responsiveness and ultra-long room temperature phosphorescence properties.

[0042] The structural formula of the guest material is at least one of formula (G1) to formula (G10),

[0043]

[0044] In some embodiments, the phosphorescence lifetime of the bio-based dopant material is ≥ 0.1 ms, and the absolute phosphorescence quantum yield of the bio-based dopant material is ≥ 0.1%.

[0045] In some embodiments, the bio-based dopant material has light-activated stimulus responsiveness, and the light-activated stimulus responsiveness includes: under different durations of ultraviolet light irradiation, the phosphorescence intensity of the bio-based dopant material is different. In the embodiment of the present application, the luminescence performance of the bio-based dopant material can be regulated by changing the ultraviolet light irradiation method, wherein the duration of ultraviolet light irradiation can be between 0 and 6000 seconds.

[0046] In some embodiments, the bio-based doping material has excitation wavelength stimulus responsiveness, and the excitation wavelength stimulus responsiveness includes: under the irradiation of excitation light of different wavelengths, the phosphorescence intensity of the bio-based doping material is different. In the embodiment of the present application, the luminescence performance of the bio-based doping material can be regulated by changing the excitation light wavelength, wherein the excitation wavelength range can be between 200nm-450nm, for example, it can be 200nm, 250nm, 300nm, 350nm, 400nm, 450nm or any wavelength between any two of the above wavelengths.

[0047] In some embodiments, the bio-based doping material has mechanical force stimulation responsiveness, and the mechanical force stimulation responsiveness includes: the phosphorescence intensity of the bio-based doping material is different at different grinding times. In the embodiment of the present application, the luminescence performance of the bio-based doping material can be regulated by physical grinding, wherein the physical grinding time can be between 0 seconds and 20 minutes, for example, the grinding time can be 0 seconds, 10 seconds, 30 seconds, 60 seconds, 2 minutes, 5 minutes, 10 minutes, 15 minutes, 20 minutes or any grinding time between any two of the above time lengths.

[0048] In some embodiments, the bio-based doping material has temperature stimulus responsiveness, and the temperature stimulus responsiveness includes: at different temperatures, the phosphorescence intensity of the bio-based doping material is different, wherein the temperature range is -196°C-140°C. In the embodiment of the present application, the luminescence performance of the bio-based doping material can be regulated by changing the temperature. For example, the temperature can be -196°C, -190°C, -180°C, -170°C, -160°C, -150°C, -140°C, -130°C, -120°C, -100°C, -80°C, -60°C, -40°C, -20°C, 0°C, 20°C, 40°C, 60°C, 80°C, 100°C, 120°C, 140°C or any temperature between any two of the above temperature values.

[0049] In some embodiments, the bio-based doping material has humidity stimulus responsiveness, and the humidity stimulus responsiveness includes: the phosphorescence intensity of the bio-based doping material is different under different humidity, wherein the humidity range is 20%-80%. In the embodiment of the present application, the luminescence performance of the bio-based doping material can be regulated by changing the humidity. For example, the humidity can be 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80% or any humidity between any two of the above humidity values.

[0050] In the second aspect, an embodiment of the present application provides a method for preparing a bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence, comprising the following steps: adding a host material and a guest material to water, ultrasonically dispersing them at 50-80°C, heating them in an oven at 60-100°C for 4-12 hours, and then drying them in an oven at 100-150°C to obtain the bio-based doping material, wherein the host material is a cyclodextrin having 6-8 D-pyranose units, and the guest material is a boric acid-based compound having a conjugated structure.

[0051] For example, the host material and the guest material can be purified in advance, placed in a container, added with a solvent medium (ultrapure water), and evenly dispersed by ultrasound at 50-80°C, then heated in an oven at 60-100°C for 4-12 hours, and then dried in an oven at 100-150°C to obtain a bio-based doped material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence.

[0052] In a third aspect, the embodiments of the present application provide a bio-based doped material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence for use in optoelectronic devices, display materials, information storage materials, ultraviolet tracking materials or anti-counterfeiting materials.

[0053] The following are specific preparation examples involved in the above content of the present disclosure. It should be clear that the following examples are only for illustrating the above-disclosed bio-based doping materials with multiple stimulus responsiveness and ultra-long room temperature phosphorescence and their preparation methods and applications, and the specific implementation methods and parameters used therein are only one or several methods that conform to the many processes and methods described above. Those skilled in the art can use other parameters according to the content introduced in this specification to prepare bio-based doping materials with multiple stimulus responsiveness and ultra-long room temperature phosphorescence according to the above method without deviating from the core spirit disclosed in the application.

[0054] Example 1

[0055] The present embodiment provides a bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence, including a host material and a guest material, wherein the structural formula of the host material is shown in formula (H1), and the structural formula of the guest material is shown in formula (G1). For the sake of ease of description, the bio-based doping material provided in this embodiment is represented as G1-H1.

[0056]

[0057] The preparation method of the bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence provided in this embodiment includes the following steps: placing compound G1 (1.33 mg, 1 mol%) and H1 (1 g) in a 10 ml screw-cap bottle, adding 5 ml of ultrapure water and then ultrasonically dispersing them at 50°C for 30 minutes to make them uniformly dispersed, placing the dispersed mixture in an oven at 80°C for 6 hours, and then drying it at 120°C for 30 minutes. The obtained product appears as a white to light yellow powder after removing the light.

[0058] Figure 1 shows the phosphorescence spectrum of the bio-based doping material provided in Example 1, Figure 2 shows the phosphorescence lifetime spectrum of the bio-based doping material provided in Example 1, Figure 3 The photo shows the luminescence change of the bio-based doping material provided in Example 1 before and after ultraviolet light excitation of different wavelengths. The luminescence performance of the bio-based doping material with multi-stimulus responsiveness and ultra-long room temperature phosphorescence prepared in Example 1 was tested, and the test results showed that its phosphorescence emission peak was around 440nm, the phosphorescence lifetime was 0.31s, and the photoluminescence quantum yield was 6.1%.

[0059] Figure 4 The phosphorescence spectra of the bio-based doping material provided in Example 1 after irradiation with different excitation light wavelengths are shown. Figure 4 It can be seen that the bio-based doping material provided in Example 1 has excitation wavelength stimulus responsiveness, and after changing the excitation light wavelength, the phosphorescence emission wavelength of the bio-based doping material is different.

[0060] Figure 5 The phosphorescence spectra of the bio-based doping material provided in Example 1 at different grinding times are shown. Figure 5 It can be seen that the bio-based doping material provided in Example 1 is responsive to mechanical force stimulation, and the corresponding phosphorescence intensity varies when the physical grinding time of the bio-based doping material is changed.

[0061] Example 2

[0062] The present embodiment provides a bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence, including a host material and a guest material, wherein the structural formula of the host material is shown in formula (H1), and the structural formula of the guest material is shown in formula (G2). For the sake of ease of description, the bio-based doping material provided in this embodiment is represented as G2-H1.

[0063]

[0064]

[0065] The preparation method of the bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence provided in this embodiment includes the following steps: placing compound G2 (0.63 mg, 0.3 mol%) and H1 (1 g) in a 10 ml screw-cap bottle, adding 5 ml of ultrapure water and then ultrasonically dispersing them at 50° C. for 30 minutes, heating the dispersed mixture in an oven at 80° C. for 6 hours, and then drying at 120° C. for 30 minutes. The obtained product appears as a white to light yellow powder after removing the light.

[0066] The luminescent properties of the bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence prepared in Example 2 were tested. Figure 6 The photoluminescence quantum yield diagram of the bio-based doping material provided in Example 2 is shown. The test results show that its phosphorescence emission peak is around 470nm, the phosphorescence lifetime is 4.65s, the photoluminescence quantum yield is 8.4%, and the phosphorescence quantum yield after light activation is 38.6%.

[0067] Figure 7 The phosphorescence spectra of the bio-based doping material provided in Example 2 after irradiation with different excitation light wavelengths are shown. Figure 7 It can be seen that the bio-based doping material provided in Example 2 has excitation wavelength stimulus responsiveness. After changing the excitation light wavelength, the phosphorescence emission wavelength and intensity of the bio-based doping material are different.

[0068] Figure 8 The phosphorescence spectra of the bio-based doping material provided in Example 2 under ultraviolet light irradiation at different times are shown. Figure 8 It can be seen that the bio-based doping material provided in Example 2 has light-activated stimulus responsiveness, and the phosphorescence intensity of the bio-based doping material is different under ultraviolet light irradiation at different times.

[0069] Fig. 9 The phosphorescence spectra of the bio-based doping material provided in Example 2 at different temperatures are shown. Fig. 9 It can be seen that the bio-based doping material provided in Example 2 has temperature stimulus responsiveness, and the phosphorescence intensity of the bio-based doping material is different at different temperatures.

[0070] Fig.10 The phosphorescence spectra of the bio-based doping material provided in Example 2 at different humidity levels are shown. Fig.10 It can be seen that the bio-based doping material provided in Example 2 is responsive to humidity stimulation, and the phosphorescence intensity of the bio-based doping material is different under different environmental humidity conditions.

[0071] Example 3

[0072] The present embodiment provides a bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence, including a host material and a guest material, wherein the structural formula of the host material is shown in formula (H1), and the structural formula of the guest material is shown in formula (G3). For the sake of ease of description, the bio-based doping material provided in this embodiment is represented as G3-H1.

[0073]

[0074] The preparation method of the bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence provided in this embodiment includes the following steps: placing compound G3 (1.33 mg, 1 mol%) and H1 (1 g) in a 10 ml screw-cap bottle, adding 5 ml of ultrapure water and then ultrasonically dispersing them at 50°C for 30 minutes to make them uniformly dispersed, placing the dispersed mixture in an oven at 80°C for 6 hours, and then drying it at 120°C for 30 minutes. The obtained product appears as a white to light yellow powder after removing the light.

[0075] Figure 3 The photographs of the luminescence changes of the bio-based doping material provided in Example 3 before and after ultraviolet light excitation of different wavelengths are shown. The luminescence performance of the bio-based doping material with multi-stimulus responsiveness and ultra-long room temperature phosphorescence prepared in Example 3 was tested, and the test results showed that its phosphorescence emission peak was around 510nm, the phosphorescence lifetime was 0.22s, and the photoluminescence quantum yield was 4.7%.

[0076] Example 4

[0077] The present embodiment provides a bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence, including a host material and a guest material, wherein the structural formula of the host material is shown in formula (H1), and the structural formula of the guest material is shown in formula (G4). For the sake of ease of description, the bio-based doping material provided in this embodiment is represented as G4-H1.

[0078]

[0079] The preparation method of the bio-based doping material with multi-stimulus responsiveness and ultra-long room temperature phosphorescence provided in this embodiment includes the following steps: placing compound G4 (1.33 mg, 1 mol%) and H1 (1 g) in a 10 ml screw-cap bottle, adding 5 ml of ultrapure water and then ultrasonically dispersing them at 50°C for 30 minutes to make them uniformly dispersed, placing the dispersed mixture in an oven at 80°C for 6 hours, and then drying it at 120°C for 30 minutes. The obtained product appears as a white to light yellow powder after removing the light.

[0080] Figure 3The photographs of the luminescence changes of the bio-based doping material provided in Example 4 before and after ultraviolet light excitation of different wavelengths are shown. The luminescence performance of the bio-based doping material with multi-stimulus responsiveness and ultra-long room temperature phosphorescence prepared in Example 4 was tested, and the test results showed that its phosphorescence emission peak was around 535nm, the phosphorescence lifetime was 0.72s, and the photoluminescence quantum yield was 22.2%.

[0081] Example 5

[0082] The present embodiment provides a bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence, including a host material and a guest material, wherein the structural formula of the host material is shown in formula (H1), and the structural formula of the guest material is shown in formula (G5). For the sake of ease of description, the bio-based doping material provided in this embodiment is represented as G5-H1.

[0083]

[0084] The preparation method of the bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence provided in this embodiment includes the following steps: placing compound G5 (1.90 mg, 1 mol%) and H1 (1 g) in a 10 ml screw-cap bottle, adding 5 ml of ultrapure water and then ultrasonically dispersing them at 50° C. for 30 minutes, heating the dispersed mixture in an oven at 80° C. for 6 hours, and then drying at 120° C. for 30 minutes. The obtained product appears as a white to light yellow powder after removing the light.

[0085] Figure 3 The photo shows the luminescence change of the bio-based doping material provided in Example 5 before and after ultraviolet light excitation of different wavelengths. The luminescence performance of the bio-based doping material with multi-stimulus responsiveness and ultra-long room temperature phosphorescence prepared in Example 5 was tested, and the test results showed that its phosphorescence emission peak was around 605nm, the phosphorescence lifetime was 0.14s, and the phosphorescence quantum yield was 46.2%.

[0086] Example 6

[0087] The present embodiment provides a bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence, including a host material and a guest material, wherein the structural formula of the host material is shown in formula (H1), and the structural formula of the guest material is shown in formula (G6). For the sake of ease of description, the bio-based doping material provided in this embodiment is represented as G6-H1.

[0088]

[0089] The preparation method of the bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence provided in this embodiment includes the following steps: placing compound G6 (2.21 mg, 1 mol%) and H1 (1 g) in a 10 ml screw-cap bottle, adding 5 ml of ultrapure water and then ultrasonically dispersing them at 50°C for 30 minutes to make them uniformly dispersed, placing the dispersed mixture in an oven at 80°C for 6 hours, and then drying it at 120°C for 30 minutes. The obtained product appears as a white to light yellow powder after removing the light.

[0090] The luminescence performance of the bio-based doped material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence prepared in Example 6 was tested. The test results showed that its phosphorescence emission peak was around 455 nm and the phosphorescence lifetime was 1.17 s.

[0091] Example 7

[0092] The present embodiment provides a bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence, including a host material and a guest material, wherein the structural formula of the host material is shown in formula (H1), and the structural formula of the guest material is shown in formula (G7). For the sake of ease of description, the bio-based doping material provided in this embodiment is represented as G7-H1.

[0093]

[0094] The preparation method of the bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence provided in this embodiment includes the following steps: placing compound G7 (1.53 mg, 1 mol%) and H1 (1 g) in a 10 ml screw-cap bottle, adding 5 ml of ultrapure water and then ultrasonically dispersing them at 50°C for 30 minutes to make them uniformly dispersed, placing the dispersed mixture in an oven at 80°C for 6 hours, and then drying it at 120°C for 30 minutes. The obtained product appears as a white to light yellow powder after removing the light.

[0095] The luminescent properties of the bio-based doped material with multi-stimulus responsiveness and ultra-long room temperature phosphorescence prepared in Example 7 were tested. The test results showed that its phosphorescence emission peak was around 495 nm and the phosphorescence lifetime was 0.21 s.

[0096] Example 8

[0097] The present embodiment provides a bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence, including a host material and a guest material, wherein the structural formula of the host material is shown in formula (H1), and the structural formula of the guest material is shown in formula (G8). For the sake of ease of description, the bio-based doping material provided in this embodiment is represented as G8-H1.

[0098]

[0099] The preparation method of the bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence provided in this embodiment includes the following steps: placing compound G8 (1.54 mg, 1 mol%) and H1 (1 g) in a 10 ml screw-cap bottle, adding 5 ml of ultrapure water and then ultrasonically dispersing them at 50°C for 30 minutes to make them uniformly dispersed, placing the dispersed mixture in an oven at 80°C for 6 hours, and then drying it at 120°C for 30 minutes. The obtained product appears as a white to light yellow powder after removing the light.

[0100] The luminescence performance of the bio-based doped material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence prepared in Example 8 was tested. The test results showed that its phosphorescence emission peak was around 490nm and the phosphorescence lifetime was 0.32s.

[0101] Example 9

[0102] The present embodiment provides a bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence, including a host material and a guest material, wherein the structural formula of the host material is shown in formula (H1), and the structural formula of the guest material is shown in formula (G9). For the sake of ease of description, the bio-based doping material provided in this embodiment is represented as G9-H1.

[0103]

[0104] The preparation method of the bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence provided in this embodiment includes the following steps: placing compound G9 (1.90 mg, 1 mol%) and H1 (1 g) in a 10 ml screw-cap bottle, adding 5 ml of ultrapure water and then ultrasonically dispersing them at 50°C for 30 minutes to make them uniformly dispersed, placing the dispersed mixture in an oven at 80°C for 6 hours, and then drying it at 120°C for 30 minutes. The obtained product appears as a white to light yellow powder after removing the light.

[0105] The luminescent properties of the bio-based doped material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence prepared in Example 9 were tested. The test results showed that its phosphorescence emission peak was around 570 nm and the phosphorescence lifetime was 0.13 s.

[0106] Example 10

[0107] The present embodiment provides a bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence, including a host material and a guest material, wherein the structural formula of the host material is shown in formula (H1), and the structural formula of the guest material is shown in formula (G10). For the sake of ease of description, the bio-based doping material provided in this embodiment is represented as G10-H1.

[0108]

[0109] The preparation method of the bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence provided in this embodiment includes the following steps: placing compound G10 (1.72 mg, 1 mol%) and H1 (1 g) in a 10 ml screw-cap bottle, adding 5 ml of ultrapure water and then ultrasonically dispersing them at 50°C for 30 minutes to make them uniformly dispersed, placing the dispersed mixture in an oven at 80°C for 6 hours, and then drying it at 120°C for 30 minutes. The obtained product appears as a white to light yellow powder after removing the light.

[0110] The luminescent properties of the bio-based doped material with multi-stimulus responsiveness and ultra-long room temperature phosphorescence prepared in Example 10 were tested. The test results showed that its phosphorescence emission peak was around 520 nm and the phosphorescence lifetime was 0.90 s.

[0111] Embodiment 11

[0112] The present embodiment provides a bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence, including a host material and a guest material, wherein the structural formula of the host material is shown in formula (H2), and the structural formula of the guest material is shown in formula (G2). For the sake of ease of description, the bio-based doping material provided in this embodiment is represented as G2-H2.

[0113]

[0114] The preparation method of the bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence provided in this embodiment includes the following steps: placing compound G2 (0.72 mg, 0.3 mol%) and H2 (1 g) in a 10 ml screw-cap bottle, adding 5 ml of ultrapure water and then ultrasonically dispersing them at 50°C for 30 minutes to make them uniformly dispersed, placing the dispersed mixture in an oven at 80°C for 6 hours, and then drying it at 120°C for 30 minutes. The obtained product appears as a white to light yellow powder after removing the light.

[0115] Fig.11 A photograph showing the luminescence changes of the bio-based doping material provided in Example 11 before and after ultraviolet light excitation is shown.

[0116] The luminescence performance of the bio-based doped material with multi-stimulus responsiveness and ultra-long room temperature phosphorescence prepared in Example 11 was tested. The test results showed that its phosphorescence emission peak was around 470nm and the phosphorescence lifetime was 0.96s.

[0117] Example 12

[0118] The present embodiment provides a bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence, including a host material and a guest material, wherein the structural formula of the host material is shown in formula (H3), and the structural formula of the guest material is shown in formula (G2). For the sake of ease of description, the bio-based doping material provided in this embodiment is represented as G2-H3.

[0119]

[0120] The preparation method of the bio-based doping material with multi-stimulus responsiveness and ultra-long room temperature phosphorescence provided in this embodiment includes the following steps: placing compound G2 (0.83 mg, 0.3 mol%) and H3 (1 g) in a 10 ml screw-cap bottle, adding 5 ml of ultrapure water and then ultrasonically dispersing them at 50° C. for 30 minutes, heating the dispersed mixture in an oven at 80° C. for 6 hours, and then drying at 120° C. for 30 minutes. The obtained product appears as a white to light yellow powder after removing the light.

[0121] Fig.11 A photograph showing the luminescence changes of the bio-based doping material provided in Example 12 before and after ultraviolet light excitation is shown.

[0122] The luminescence performance of the bio-based doped material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence prepared in Example 12 was tested. The test results showed that its phosphorescence emission peak was around 470nm and the phosphorescence lifetime was 0.74s.

[0123] Application Examples

[0124] Different doping systems are loaded into a black container and then arranged into different combination queues. Fig.12 (a) shows the combined queues of different doping systems (G2-H1, G4-H1, G5-H1). Fig.12 As shown in (a), a color and time-dependent information storage device is developed by combining three-dimensional color coding and Morse coding. When the 310nm ultraviolet irradiation is turned off, different queues show different 3D color coding, which can be scanned to obtain information 1. Subsequently, due to the relatively short afterglow of G5-H1, after two seconds, only the Morse code queue composed of G2-H1 (blue) and G4-H1 (green) can be seen, giving information 2. Similarly, if other color codes are designed, different information and Morse codes will be obtained. The process only requires moving the position of the container and turning the 310nm ultraviolet light on and off, making the information storage device universal and reusable.

[0125] Fig.12 (b) shows a schematic diagram of preparing a redrawable afterglow pattern using water as ink. Fig.12As shown in (b), the letter patterns "F", "A" and "N" are written with water on G2-H1, G4-H1 and G5-H1. The quenched letters "F", "A" and "N" will contrast with the phosphorescence of the doping system. Then, these letters can be thermally erased, allowing the next drawing to begin.

[0126] Fig.12 (c) shows a schematic diagram of the scanning path recognition of ultraviolet rays. Fig.12 (c) shows the movement paths A and B of the 310 nm light source. After the UV source is moved, the points irradiated earlier show weaker afterglow, while the points irradiated later show stronger afterglow.

[0127] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0128] The above-described embodiments only express several embodiments of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for those of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. It should be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments on the basis of the technical solutions provided by the present invention are all within the protection scope of the claims attached to the present invention. Therefore, the protection scope of the patent of the present invention shall be based on the attached claims, and the description and drawings may be used to interpret the contents of the claims.

Claims

1. A bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence, characterized in that: The invention comprises a main material and a guest material, wherein the main material is cyclodextrin with 6 to 8 D-pyranose glucose units, and the guest material is a boric acid compound with a conjugated structure.

2. The bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence according to claim 1, characterized in that: The structural formula of the host material is at least one of formula (H1) to formula (H3), The structural formula of the guest material is at least one of formula (G1) to formula (G10), 3. The bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence according to claim 1, characterized in that: The phosphorescence lifetime of the bio-based doping material is ≥0.1 ms, and the absolute phosphorescence quantum yield of the bio-based doping material is ≥0.1%.

4. The bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence according to claim 1, characterized in that: The bio-based doping material has light-activated stimulus responsiveness, and the light-activated stimulus responsiveness includes: under ultraviolet light irradiation at different times, the phosphorescence intensity of the bio-based doping material is different.

5. The bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence according to claim 1, characterized in that: The bio-based doping material has excitation wavelength stimulus responsiveness, and the excitation wavelength stimulus responsiveness includes: under the irradiation of excitation light of different wavelengths, the phosphorescence intensity of the bio-based doping material is different.

6. The bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence according to claim 1, characterized in that: The bio-based doping material has mechanical force stimulation responsiveness, and the mechanical force stimulation responsiveness includes: the phosphorescence intensity of the bio-based doping material is different under different grinding times.

7. The bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence according to claim 1, characterized in that: The bio-based doping material has temperature stimulus responsiveness, and the temperature stimulus responsiveness includes: at different temperatures, the phosphorescence intensity of the bio-based doping material is different, wherein the temperature range is -196°C-140°C.

8. The bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence according to claim 1, characterized in that: The bio-based doping material has humidity stimulus responsiveness, and the humidity stimulus responsiveness includes: the phosphorescence intensity of the bio-based doping material is different under different humidity, wherein the humidity range is 20%-80%.

9. A method for preparing a bio-based doping material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence, characterized in that: The method comprises the following steps: adding a main material and a guest material into water, ultrasonically dispersing them at 50-80°C, heating them in an oven at 60-100°C for 4-12 hours, and then drying them in an oven at 100-150°C to obtain the bio-based doping material, wherein the main material is a cyclodextrin having 6-8 D-pyranose glucose units, and the guest material is a boric acid-based compound having a conjugated structure.

10. Use of the bio-based doped material with multiple stimulus responsiveness and ultra-long room temperature phosphorescence as described in any one of claims 1 to 9 in optoelectronic devices, display materials, information storage materials, ultraviolet tracking materials or anti-counterfeiting materials.

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