CN112321531A - Organic room temperature phosphorescent material and preparation method and application thereof - Google Patents
Organic room temperature phosphorescent material and preparation method and application thereof Download PDFInfo
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- 229950000688 phenothiazine Drugs 0.000 claims description 26
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 238000001514 detection method Methods 0.000 claims description 4
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- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 6
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Images
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
- C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
- C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
- C07D279/18—[b, e]-condensed with two six-membered rings
- C07D279/22—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
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Abstract
The invention discloses an organic room temperature phosphorescent material and a preparation method and application thereof. The structure of the phosphorescent material is shown as formula (I), (II) or (III). These molecules each contain one or more phenothiazine units, and when dispersed and immobilized in the rigid matrix PMMA, the material doped with these molecules can be induced to produce room temperature phosphorescence under excitation by UV light. Phenothiazine-derivative molecules promote the conversion of oxygen molecules in the matrix material to singlet oxygen during light induction, and when the oxygen molecules are greatly consumed, these phenothiazine-derivative molecules emit phosphorescence because the rigid environment provided by the matrix inhibits non-radiative energy dissipation. Heating or standing the activated material for a long time can re-inactivate the material, and the process can be repeated. The molecule can realize the light-induced information writing and erasing in the transparent polymer matrix material, provides material support for the organic light information storage and reading and writing, and has strong practicability.
Description
Technical Field
The invention relates to the field of room temperature phosphorescent materials, in particular to an organic room temperature phosphorescent material and a preparation method and application thereof.
Background
Phosphorescent materials are very widely used in life, and because phosphorescence generation depends on small probability transition of triplet excitons in quantum mechanics, such materials often exhibit a very long emission lifetime compared to fluorescence. Such as emergency lights and a range of night-light products, take advantage of the long-life characteristics of phosphorescence. The method also has high application value in the aspects of biological imaging, anti-counterfeiting encryption and optical storage. However, these applications are currently based on inorganic phosphorescent materials, and are particularly represented by rare earth activated aluminate phosphorescent materials. However, the material has the defects of high energy consumption, complex process, poor flexibility, high biological toxicity and the like in the preparation process.
In contrast, organic room temperature phosphorescent materials have significant advantages in applications where the organic materials can be simply spin-coated, drop-cast or evaporated onto various substrates. Organic Light Emitting Diodes (OLEDs), which are currently commercially available, are good examples, and can display information content by fluorescence and/or phosphorescence. However, due to the weak spin-orbit coupling of organic molecules, the non-radiative rate constant is large, and triplet excitons are readily quenched by oxygen, leading to the extreme challenge of achieving visible organophosphorous at ambient conditions (nat. Commun.2019,10,2111; J.am. chem. Soc.2018,140, 10734-10739).
Some studies have attempted to solve the difficulties of organic materials in phosphorescent emission at room temperature, such as achieving phosphorescent emission by tight crystal packing or by reducing oxygen permeability by special host molecules and thus suppressing non-radiative decay. In order to meet the flexible processing requirements, phosphor and phosphor doping are commonly used in printed materials. These doped materials are briefly activated under Ultraviolet (UV) or thermally induced conditions to effect writing and/or erasing of information. However, powder samples, including quantum dot materials, are highly susceptible to the generation of opaque particles in the matrix, which can affect material performance. The organic material can realize the molecular-level dispersion in the matrix, has good oxygen isolation and rigid environment, and retains the phosphorescence characteristics, thereby obtaining the pure and transparent phosphorescence material. Some studies achieve phosphorescence emission in materials by inducing cross-linked polymerization of organic molecules, but this approach can only be written once and does not achieve reversible phosphorescence emission (nat. commun.2019,10,2111; science. advances.2018,4, eaas 9732; adv. funct. mater.2019,29,1807599).
In the aspects of information encryption, anti-counterfeiting and display, materials are often required to be capable of being written and erased with information for multiple times. An efficient way to achieve this is to synthesize suitable molecules that can remove molecular oxygen by uv excitation in the host material, avoiding quenching of phosphorescence by oxygen. This process is now common in liquid environments, exciting singlet oxygen to interact with surrounding solvent molecules and disappear in the local environment of the emitter, causing phosphorescent emission. In such systems, phosphorescence generation is dependent on the choice of solvent molecules and cannot be applied to solid or gel materials. The directly synthesized polymer phosphorescent material is difficult to erase information, and is generally realized by re-dissolution, which obviously cannot meet the requirements of wider application.
In view of the above, it is necessary to provide a technical solution to the above problems.
Disclosure of Invention
One of the objects of the present invention is: the phosphorescent material can be used for repeatedly writing and erasing information, has special light-induced room-temperature phosphorescent property, can be flexibly processed, and greatly expands the practical value of the phosphorescent material.
In order to achieve the purpose, the invention adopts the following technical scheme:
an organic room temperature phosphorescent material comprises any one of phosphorescent materials shown in a formula (I), a formula (II) and a formula (III);
the invention discloses an organic room temperature phosphorescent material, wherein each molecule contains one or more phenothiazine units, and when the molecules are dispersed and fixed in a rigid matrix PMMA, the material doped with the molecules can be induced to generate room temperature phosphorescence under the excitation of an ultraviolet lamp. Phenothiazine-derivative molecules promote the conversion of oxygen molecules in the matrix material to singlet oxygen during light induction, and when the oxygen molecules are greatly consumed, these phenothiazine-derivative molecules emit phosphorescence because the rigid environment provided by the matrix inhibits non-radiative energy dissipation. Heating or standing the activated material for a long time can re-inactivate the material, and the process can be repeated. The molecule can realize the light-induced information writing and erasing in the transparent polymer matrix material, provides material support for the organic light information storage and reading and writing, and has strong practicability.
Preferably, the formula (I) is obtained by coupling reaction of phenothiazine and monohalogenated benzene; the formula (II) is obtained by coupling reaction of phenothiazine and para-substituted halogenated benzene; the formula (III) is obtained by coupling reaction of phenothiazine and 1,3, 5-substituted halogenated benzene.
Wherein:
structural formula of phenothiazine is
(a)；
The structural formula of the monohalogenated benzene is
(b)；
The structural formula of the para-substituted halogenated benzene is
(c)；
The structural formula of the 1,3, 5-substituted halogenated benzene is shown in the specification
(d)；
Wherein R ═ Br, I; r1＝Br,I；R2＝Br,I；R3＝Br,I。
Preferably, in the formula (I), the ratio of the amounts of the substances of the phenothiazine and the monohalogenated benzene is (1-2): 1; in the formula (II), the amount ratio of the phenothiazine to the substance of the para-substituted halogenated benzene is (2-3) to 1; in the formula (III), the amount ratio of the phenothiazine to the 1,3, 5-substituted halogenated benzene is (3-5): 1.
another object of the present invention is to provide a method for preparing the organic room temperature phosphorescent material, which comprises the following steps:
mixing any one of phosphorescent materials in a formula (I), a formula (II) and a formula (III) with polymethyl methacrylate according to a mass ratio of (0.01-10): 100, mixing to form a membrane, volatilizing and drying to obtain a membrane material;
and (2) activating the membrane material by adopting ultraviolet light with the wavelength of 254-395 nm for irradiation at the temperature of 20-25 ℃, wherein the membrane material of the part irradiated by the ultraviolet light has the effect of room temperature phosphorescence, so that the organic room temperature phosphorescence material is obtained.
Preferably, the wavelength of the ultraviolet light is 365-375 nm. More preferably, the wavelength of the ultraviolet light is 365nm or 375 nm.
Preferably, the organic room temperature phosphorescent material loses room temperature phosphorescent characteristics when heated at a temperature of 60-120 ℃. The heating time can be specifically selected according to the thickness of the organic room temperature phosphorescent material, and can be specifically 0.1-600 s.
After the phosphorescent material of any one of the formula (I), the formula (II) and the formula (III) is doped into a polymethyl methacrylate (PMMA) matrix, the mixed material can realize room temperature phosphorescent emission after being irradiated under an ultraviolet lamp for a certain time, namely, the material has the room temperature phosphorescent characteristic of light activation, the activation is local, only the irradiated part shows the room temperature phosphorescent characteristic, and the non-activated part does not have the room temperature phosphorescent characteristic (RTP). In addition, the activated part can be inactivated again after heating, and can be activated by light again after inactivation, so that the cycle of light activation-heat inactivation-light activation is realized.
Preferably, the preparation method of any one of the formula (I), the formula (II) and the formula (III): under inert atmosphere, phenothiazine, halogenated benzene, alkali, palladium catalyst and tert-butylphosphine are dissolved in organic solvent, and heating reflux is carried out to obtain any one of formula (I), formula (II) and formula (III); wherein the heating reflux temperature is 90-120 ℃, and the time is 12-48 h.
Preferably, the heating reflux temperature is 100-110 ℃, and the time is 18-32 h.
Preferably, the mass ratio of the phenothiazine, the halogenated benzene, the alkali, the palladium catalyst and the tert-butyl phosphine is 1: (1-3): (0.01-0.5): (0.005-0.05).
Preferably, the halogenated benzene is any one of monohalogenated benzene, para-substituted halogenated benzene and 1,3, 5-substituted halogenated benzene; the alkali is any one of potassium tert-butoxide, sodium tert-butoxide, potassium carbonate, sodium carbonate and cesium carbonate; the palladium catalyst is any one of palladium acetate, diphenylphosphinoferrocene palladium dichloride, tetratriphenylphosphine palladium, dichlorotriphenylphosphine palladium and palladium-carbon.
Preferably, the organic solvent is toluene or xylene; the inert atmosphere is nitrogen.
The invention also aims to provide application of the organic room temperature phosphorescent material, which can be used for information storage, anti-counterfeiting and encryption, and crack detection of the polymethyl methacrylate material.
Compared with the prior art, the invention has the beneficial effects that:
1) the room-temperature phosphorescent material provided by the invention is a pure organic compound, has a light-induced activation characteristic after being doped with PMMA, and is high in response speed, high in luminous intensity and high in phosphorescence quantum yield.
2) The pure organic room temperature phosphorescent material with light induction activity provided by the invention is easy to disperse in a transparent matrix material such as PMMA, can ensure high brightness and high-efficiency luminescence under the state of extremely low doping concentration, has low influence on the light transmission of the material, and is beneficial to application in transparent display.
3) Compared with the traditional inorganic phosphorescent material, the pure organic room-temperature phosphorescent material with the photoinduction activity provided by the invention has the advantages of simple and easily obtained preparation method, low cost and stronger processability.
4) The pure organic room temperature phosphorescent material with photoinduction activity provided by the invention can be subjected to patterning processing through screen printing, and greatly meets the requirements of various anti-counterfeiting and display scenes.
Drawings
FIG. 1 is a hydrogen nuclear magnetic diagram of the preparation of formula (I) in example 2 of the present invention.
FIG. 2 is a high-resolution mass spectrum of formula (I) obtained in example 2 of the present invention.
FIG. 3 is an in situ spectrum of a photoinduced room temperature phosphorescent material prepared in example 2 of the invention 5 seconds before photoactivation.
FIG. 4 is an in-situ spectrum of a photoinduced room temperature phosphorescent material prepared in example 2 of the invention during 50 seconds of photoactivation and with the excitation source turned off.
Fig. 5 is a graph showing the photoluminescence quantum yield of the photo-induced room temperature phosphorescent material prepared in example 2 of the present invention after photo-activation.
FIG. 6 is a graph showing the decay curve of phosphorescence at room temperature after light activation of the light-induced room temperature phosphorescent material prepared in example 2 of the present invention.
Fig. 7 is a photograph of luminescence after selective activation of the light-induced room temperature phosphorescent material prepared in example 2 of the present invention.
FIG. 8 is a hydrogen nuclear magnetic diagram of the preparation of formula (II) in example 3 of the present invention.
FIG. 9 is a high-resolution mass spectrum of formula (II) obtained in example 3 of the present invention.
FIG. 10 is an in-situ spectrum of the organic room temperature phosphorescent material prepared in example 3 of the present invention for 3 seconds before photo-activation.
FIG. 11 is an in-situ spectrum of an organic room temperature phosphorescent material prepared in example 3 of the present invention during 50 seconds of photoactivation and with the excitation source turned off.
Fig. 12 is a photoluminescence quantum yield of the organic room temperature phosphorescent material prepared in example 3 of the present invention after photoactivation.
Fig. 13 is a graph showing the decay curve of phosphorescence at room temperature after being activated by light for the organic phosphorescent material at room temperature prepared in example 3 of the present invention.
FIG. 14 shows the light-induced information writing and thermal erasing cycles of the organic room temperature phosphorescent material prepared in example 3 of the present invention.
FIG. 15 is a hydrogen nuclear magnetic diagram of the formula (III) prepared in example 4 of the present invention.
FIG. 16 is a high-resolution mass spectrum of formula (III) obtained in example 4 of the present invention.
FIG. 17 is an in-situ spectrum of the organic room temperature phosphorescent material prepared in example 4 of the present invention 3.5 seconds before photo-activation.
FIG. 18 is an in-situ spectrum of an organic room temperature phosphorescent material prepared in example 4 of the present invention during 50 seconds of photoactivation and with the excitation source turned off.
Fig. 19 is a photoluminescence quantum yield of the organic room temperature phosphorescent material prepared in example 4 of the present invention after photoactivation.
Fig. 20 is a graph showing the decay curve of phosphorescence at room temperature after being activated by light for the organic room temperature phosphorescent material prepared in example 4 of the present invention.
Fig. 21 shows a process of photo-induced RTP activation of the organic phosphorescent material at room temperature prepared in example 4 of the present invention.
Fig. 22 is a photo-induced phosphorescent ambient light patterning of an organic phosphorescent ambient light material prepared in example 4 of the present invention on a transparent substrate.
Fig. 23 shows that the organic room temperature phosphorescent molecules prepared in embodiment 4 of the present invention are doped into the PMMA material and are completely activated, and the latent cracks and the fracture cracks in the material are distinguished by the gray value of the light-emitting region, so as to implement crack detection.
Fig. 24 shows that the organic room temperature phosphorescent molecules prepared in example 4 of the present invention are doped into the PMMA material, and pattern printing is implemented by screen printing using the doped material as "ink" to obtain a screen printed pattern with light-induced room temperature phosphorescent characteristics.
Fig. 25 shows that the organic room temperature phosphorescent molecules prepared in embodiment 4 of the present invention are doped into a PMMA material and made into a thin film to implement the writing of flexible material graphics and text.
Detailed Description
In order to make the technical solutions and advantages of the present invention clearer, the present invention and its advantages will be described in further detail below with reference to the following detailed description and the accompanying drawings, but the embodiments of the present invention are not limited thereto.
Example 1
An organic room temperature phosphorescent material comprises any one of phosphorescent materials shown in a formula (I), a formula (II) and a formula (III);
further, the formula (I) is obtained by coupling reaction of phenothiazine and monohalogenated benzene; the formula (II) is obtained by coupling reaction of phenothiazine and para-substituted halogenated benzene; the formula (III) is obtained by coupling reaction of phenothiazine and 1,3, 5-substituted halogenated benzene.
Wherein:
structural formula of phenothiazine is
(a)；
The structural formula of the monohalogenated benzene is
(b)；
The structural formula of the para-substituted halogenated benzene is
(c)；
The structural formula of the 1,3, 5-substituted halogenated benzene is shown in the specification
(d)；
Wherein R ═ Br, I; r1＝Br,I；R2＝Br,I；R3＝Br,I。
Furthermore, in the formula (I), the ratio of the amounts of the substances of phenothiazine and monohalogenated benzene is (1-2) to 1; in the formula (II), the amount ratio of phenothiazine to para-substituted halogenated benzene is (2-3) to 1; in the formula (III), the amount ratio of the phenothiazine to the 1,3, 5-substituted halogenated benzene is (3-5): 1.
example 2
A method for preparing the organic room temperature phosphorescent material of embodiment 1, comprising the following steps:
s1, under the protection of nitrogen, taking 1.99g (10mmol) of phenothiazine2.04g (10mmol) of iodobenzene, 1.68g (15mmol) of potassium tert-butoxide (t-BuOK), 0.11g (0.5mmol) of palladium acetate (Pd (OAc))2) And 0.25mL (0.25mmol) of tri-tert-butylphosphine (P (t-Bu)3) Dissolved in 90mL of toluene solution and heated under reflux for 24 hours. Cooled to room temperature, the solvent was evaporated under heating, extracted with dichloromethane three times, and the organic phase was dried over anhydrous magnesium sulfate. Filtering to obtain crude product, and purifying by column chromatography to obtain product of formula (I), wherein the obtained product has mass of 2.6g and yield of 94.5%. The specific preparation reaction formula is as follows:
s2, dissolving 1.0mg of the product of the formula (I) obtained in S1 and 100mg of polymethyl methacrylate (PMMA) in 1.5mL of tetrahydrofuran solution, spin-coating to form a film at the rotating speed of 120r/min, and volatilizing and drying to obtain a film material; the resulting film material was then used for photophysical property testing.
And S3, irradiating by ultraviolet light with the wavelength of 375nm at the temperature of 20-25 ℃, activating the film material obtained in the S2, wherein the film material irradiated by the ultraviolet light has the effect of room temperature phosphorescence, and thus obtaining the organic room temperature phosphorescence material.
And (3) performing nuclear magnetic resonance spectrum and high-resolution mass spectrum characterization on the product obtained in the S1. The nuclear magnetic resonance spectrum is shown in figure 1:1H NMR(400MHz,CDCl3) δ 7.64(t, J ═ 7.6Hz,2H), 7.57-7.47 (m,1H),7.43(d, J ═ 7.9Hz,2H), 7.17-6.99 (m,2H),6.87(d, J ═ 7.3Hz,4H),6.24(d, J ═ 7.7Hz, 2H). The high resolution mass spectrum is shown in fig. 2: HRMS (ESI, acetonitrile/chloroform 1:1, pos. mode) m/z calculated for C18H13NS:275.0763[M+H]+,found:275.0752。
The organic room temperature phosphorescent material obtained in S3 was subjected to a test:
light activated process test: the spectral change was tested in situ under excitation of a 375nm UV lamp, as shown in FIG. 3. The phosphorescence peaks at 512nm and 545nm increase gradually from none to some extent as the UV excitation proceeds. The material rapidly increases in room temperature phosphorescence intensity during the first 5 seconds of uv excitation onset, after which continued excitation intensity increases more slowly and eventually maintains maximum intensity. As shown in fig. 4, the intensity remained substantially constant for 50 seconds of activation. The excitation light source is turned off and the phosphorescence gradually decays.
And (3) quantum yield test: as shown in fig. 5, the quantum yield before uv activation was only 1.82%, and when photo-activated, the material quantum yield reached 11.41%.
Phosphorescent lifetime test: as shown in fig. 6, the room temperature phosphorescent lifetime of the material after activation is 32 ms.
Fig. 7 shows a luminescent picture after selective activation of an organic room temperature phosphorescent material, in which a middle white region is a luminescent region after ultraviolet activation, a black portion outside a strip region inside a circular ring is an opaque medium blocking region, and a small circle in the center of the circular ring is also an opaque medium blocking region. The absence of RTP in the occluded areas and the presence of RTP in the active areas only is shown in fig. 7, which indicates that the material has excellent photo-induced RTP performance and that teletext writing can be achieved by selectively activating specific areas.
Example 3
A method for preparing the organic room temperature phosphorescent material of embodiment 1, comprising the following steps:
s1, under nitrogen protection, 3.98g (20mmol) of phenothiazine, 2.81g (10mmol) of p-bromoiodobenzene, 2.88g (30mmol) of sodium tert-butoxide (t-Buona), 0.11g (0.5mmol) of palladium acetate (Pd (OAc)2) And 0.25mL (0.25mmol) of tri-tert-butylphosphine (P (t-Bu)3) Dissolved in 120mL of a toluene solution and heated under reflux for 24 hours. Cooled to room temperature, the solvent was evaporated under heating, extracted with dichloromethane three times, and the organic phase was dried over anhydrous magnesium sulfate. Filtering to obtain crude product, and purifying by column chromatography to obtain product of formula (II) with mass of 3.8g and yield of 80.9%. The specific preparation reaction formula is as follows:
s2, dissolving 0.5mg and 100mg of polymethyl methacrylate (PMMA) of the product of the formula (I) obtained in the step S1 in 1.5mL of tetrahydrofuran solution, spin-coating to form a film at the rotating speed of 120r/min, and volatilizing and drying to obtain a film material; the resulting film material was then used for photophysical property testing.
And S3, irradiating by ultraviolet light with the wavelength of 375nm at the temperature of 20-25 ℃, activating the film material obtained in the S2, wherein the film material irradiated by the ultraviolet light has the effect of room temperature phosphorescence, and thus obtaining the organic room temperature phosphorescence material.
And (3) performing nuclear magnetic resonance spectrum and high-resolution mass spectrum characterization on the product obtained in the S1. The nuclear magnetic resonance spectrum is shown in FIG. 8:1H NMR(400MHz,CDCl3) δ 7.49(s,4H),7.12(d, J ═ 7.6Hz,4H),7.00(t, J ═ 7.7Hz,4H),6.91(t, J ═ 7.2Hz,4H),6.52(d, J ═ 8.1Hz, 4H). The high resolution mass spectrum is shown in fig. 9: HRMS (ESI, acetonitrile/chloroform 1:1, pos. mode) m/z calculated for C30H20N2S2:495.0960[M+H]+,found:495.0939。
The organic room temperature phosphorescent material obtained in S3 was subjected to a test:
light activated process test: as shown in fig. 10, the spectral change was tested in situ under excitation of a 375nm uv lamp. The phosphorescence peaks at 510nm and 540nm increase gradually from none to some extent as the uv excitation proceeds. The material rapidly increases in room temperature phosphorescence intensity during the first 3 seconds of uv excitation initiation, after which continued excitation intensity increases more slowly and eventually maintains to maximum intensity. As shown in fig. 11, the intensity remained substantially constant for 50 seconds of activation. The excitation light source is turned off and the phosphorescence gradually decays.
And (3) quantum yield test: as shown in fig. 12, the quantum yield before uv activation was only 2.48%, and after photo-activation, the material quantum yield reached 20.60%.
Phosphorescent lifetime test: as shown in fig. 13, the room temperature phosphorescent lifetime of the material after activation is 25 ms.
Fig. 14 shows a luminescent picture of the organic room temperature phosphorescent material after selective activation, in which 375nm ultraviolet light is transmitted through a hollow-out panda pattern tool and then radiated on the surface of the material, the material is selectively activated, and the activated area is the panda pattern on the hollow-out tool. When the material was irradiated with the transmitted UV light for 2 seconds, the partially activated pattern was visible by turning off the UV lamp (FIG. 14, panel B); when the activation time was increased to 10 seconds, the pattern became clearer (fig. 14, C). After the activated material is heated at 80 ℃ for 3 seconds, the pattern is excited by ultraviolet again, the pattern can be seen to disappear partially (figure D in figure 14), after the material is heated for 8 seconds, the pattern disappears completely, and the pattern information of the activated area is erased. When the other pattern is replaced again for activation, the pattern having the RTP characteristic is recovered (fig. 14, F). The process can be repeated to realize the cycle of light activation, heat inactivation and light activation, and the characteristic meets the application of the room temperature phosphorescent material in the fields of erasable information storage, anti-counterfeiting and encryption.
Example 4
A method for preparing the organic room temperature phosphorescent material of embodiment 1, comprising the following steps:
s1, under nitrogen protection, 5.97g (30mmol) of phenothiazine, 3.15g (10mmol) of 1,3,5 tribromobenzene, 2.88g (30mmol) of sodium tert-butoxide (t-BuONa), 0.22g (1.0mmol) of palladium acetate (Pd (OAc)2) And 0.25mL (0.5mmol) of tri-tert-butylphosphine (P (t-Bu)3) Dissolved in 200mL of a toluene solution and heated under reflux for 48 hours. Cooled to room temperature, the solvent was evaporated under heating, extracted with dichloromethane three times, and the organic phase was dried over anhydrous magnesium sulfate. Filtering to obtain crude product, and purifying by column chromatography to obtain product of formula (III) with mass of 4.2g and yield of 62.8%. The specific preparation reaction formula is as follows:
s2, dissolving 2.5mg of the product of the formula (I) obtained in S1 and 100mg of polymethyl methacrylate (PMMA) in 1.5mL of tetrahydrofuran solution, spin-coating to form a film at the rotating speed of 120r/min, and volatilizing and drying to obtain a film material; the resulting film material was then used for photophysical property testing.
And S3, irradiating by ultraviolet light with the wavelength of 375nm at the temperature of 20-25 ℃, activating the film material obtained in the S2, wherein the film material irradiated by the ultraviolet light has the effect of room temperature phosphorescence, and thus obtaining the organic room temperature phosphorescence material.
And (3) performing nuclear magnetic resonance spectrum and high-resolution mass spectrum characterization on the product obtained in the S1. The nuclear magnetic resonance spectrum is shown in FIG. 15:1H NMR(400MHz,CDCl3) δ 7.15(dd, J ═ 7.6,1.5Hz,6H), 7.10-6.99 (m,9H),6.94(t, J ═ 7.1Hz,6H),6.72(dd, J ═ 8.1,0.9Hz, 6H). The high resolution mass spectrum is shown in fig. 16: HRMS (ESI, acetonitrile/chloroform 1:1, pos. mode) m/z calculated for C42H27N3S3:670.1440[M+H]+,found:670.1414。
The organic room temperature phosphorescent material obtained in S3 was subjected to a test:
light activated process test: the spectral change was tested in situ under excitation of a 375nm UV lamp, as shown in FIG. 17. As the UV excitation proceeds, the phosphorescence peaks at 512nm and 542nm increase gradually from none to some extent. The material rapidly increases in room temperature phosphorescence intensity during the first 3.5 seconds of uv excitation initiation, after which continued excitation intensity increases slowly and eventually maintains maximum intensity. As shown in fig. 18, the intensity remained substantially constant for 50 seconds of activation. The excitation light source is turned off and the phosphorescence gradually decays.
And (3) quantum yield test: as shown in fig. 19, the quantum yield before uv activation was only 5.87%, and after photo-activation, the material quantum yield reached 22.97%.
Phosphorescent lifetime test: as shown in fig. 20, the room temperature phosphorescent lifetime of the material after activation was 30 ms.
As shown in fig. 21, the material is uv activated without zone selectivity, and as the activation proceeds, the zone of the material having RTP characteristics increases until the entire material is activated.
As shown in fig. 22, by spin-coating PMMA doped with formula (III) onto a transparent matrix material and activating by selective region, a pattern having phosphorescent emission ability can be obtained with a doping concentration of III: PMMA 1:400 (mass ratio).
As shown in fig. 23, when the PMMA material doped with formula (III) is fully activated, the crack detection can be realized by distinguishing the latent crack and the fracture crack in the material through the gray scale value of the light-emitting region, and the doping concentration is III: PMMA 1:1000 (mass ratio).
As shown in fig. 24, complicated graph content is screen-printed by using PMMA material doped with formula (III) as "ink", and graph with light-induced room temperature phosphorescence characteristic is obtained, wherein the doping concentration is III: PMMA 1:400 (mass ratio).
As shown in fig. 25, the photo-induced room temperature phosphorescent formula (III) is doped into the PMMA material, and the PMMA material is made into a thin film, so that the writing of the flexible material can be realized, wherein the doping concentration is III: PMMA (mass ratio) 1: 400.
The above-described embodiments are merely intended to facilitate an understanding of the method of the present invention and its core concepts. For those skilled in the art, after reading the present specification, modifications without inventive contribution can be made to the present embodiments as needed, and similar effects can be easily achieved without departing from the principles of the present invention. For example, a room temperature phosphorescent material having photoinduced properties can be obtained by simply increasing or decreasing the number of phenothiazine units, replacing substitution sites, introducing non-luminescent center modifications such as alkyl chains, replacing rigid media without using PMMA, changing linking units between phenothiazine units, or the like, or by chemically bonding phenothiazine units to natural or synthetic molecules, and such molecules that can obtain photoinduced room temperature phosphorescent materials from phenothiazine units are within the scope of the present invention.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (10)
1. An organic room temperature phosphorescent material is characterized in that the phosphorescent material comprises any one of phosphorescent materials shown in a formula (I), a formula (II) and a formula (III);
2. the organic room temperature phosphorescent material as claimed in claim 1, wherein the formula (I) is obtained by coupling reaction of phenothiazine and monohalogenated benzene; the formula (II) is obtained by coupling reaction of phenothiazine and para-substituted halogenated benzene; the formula (III) is obtained by coupling reaction of phenothiazine and 1,3, 5-substituted halogenated benzene.
3. The organic room temperature phosphorescent material as claimed in claim 2, wherein in the formula (I), the ratio of the amounts of the substances of the phenothiazine and the monohalobenzene is (1-2): 1; in the formula (II), the amount ratio of the phenothiazine to the substance of the para-substituted halogenated benzene is (2-3) to 1; in the formula (III), the amount ratio of the phenothiazine to the 1,3, 5-substituted halogenated benzene is (3-5): 1.
4. a method for preparing an organic room temperature phosphorescent material as described in any one of claims 1 to 3, which comprises the following steps:
mixing any one of phosphorescent materials in a formula (I), a formula (II) and a formula (III) with polymethyl methacrylate according to a mass ratio of (0.01-10): 100, mixing to form a membrane, volatilizing and drying to obtain a membrane material;
and (2) activating the membrane material by adopting ultraviolet light with the wavelength of 254-395 nm for irradiation at the temperature of 20-25 ℃, wherein the membrane material of the part irradiated by the ultraviolet light has the effect of room temperature phosphorescence, so that the organic room temperature phosphorescence material is obtained.
5. The method according to claim 4, wherein the wavelength of the ultraviolet light is 365-375 nm.
6. The preparation method according to claim 4, wherein the organic room temperature phosphorescent material loses room temperature phosphorescence characteristics when heated at a temperature of 60-120 ℃.
7. The method according to claim 4, wherein the method comprises any one of the following steps: under inert atmosphere, phenothiazine, halogenated benzene, alkali, palladium catalyst and tert-butylphosphine are dissolved in organic solvent, and heating reflux is carried out to obtain any one of formula (I), formula (II) and formula (III); wherein the heating reflux temperature is 90-120 ℃, and the time is 12-48 h.
8. The production method according to claim 7, wherein the substance of phenothiazine, halogenobenzene, base, palladium catalyst, and tert-butylphosphine is present in an amount ratio of 1: (1-3): (0.01-0.5): (0.005-0.05).
9. The production method according to claim 8, wherein the halogenated benzene is any one of monohalogenated benzene, para-substituted halogenated benzene, and 1,3, 5-substituted halogenated benzene; the alkali is any one of potassium tert-butoxide, sodium tert-butoxide, potassium carbonate, sodium carbonate and cesium carbonate; the palladium catalyst is any one of palladium acetate, diphenylphosphinoferrocene palladium dichloride, tetratriphenylphosphine palladium, dichlorotriphenylphosphine palladium and palladium-carbon.
10. Use of the organic room temperature phosphorescent material as claimed in any one of claims 1 to 3, for information storage, anti-counterfeiting and encryption, and crack detection of polymethyl methacrylate materials.
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