CN113088278B - Room-temperature phosphorescent material and preparation method thereof - Google Patents

Room-temperature phosphorescent material and preparation method thereof Download PDF

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CN113088278B
CN113088278B CN202110387050.XA CN202110387050A CN113088278B CN 113088278 B CN113088278 B CN 113088278B CN 202110387050 A CN202110387050 A CN 202110387050A CN 113088278 B CN113088278 B CN 113088278B
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organic
phosphorescent material
cyclodextrin
acid
supramolecular polymer
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CN113088278A (en
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马骧
孙思宇
田禾
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East China University of Science and Technology
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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    • 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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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom

Abstract

The application discloses a room temperature phosphorescent material and a preparation method thereof, the room temperature phosphorescent material with fluid property is formed by a method of blending a plurality of hydrogen bond multi-component systems and organic phosphors, the preparation method is simple and convenient, and the obtained room temperature phosphorescent material has high luminous efficiency and universal applicability.

Description

Room-temperature phosphorescent material and preparation method thereof
Technical Field
The application relates to the technical field of organic luminescent materials, in particular to a room-temperature phosphorescent material and a preparation method thereof.
Background
The organic room temperature phosphorescent material has wide application in the fields of chemical sensing, biological imaging and organic photoelectric materials, but all the organic room temperature phosphorescent materials are solid light-emitting materials or solution light-emitting materials at present. The organic room temperature phosphorescent material which can emit light in solid can emit light only in crystalline state, polymer doping or polymer copolymerization, the preparation condition is highly complex, and the applicability is narrow; however, the reports of the solution-state luminescent organic phosphorescent material are rare, the broad spectrum property is lacked, the luminous efficiency is extremely low, and the effective application cannot be developed. Therefore, it is necessary to develop an organic room temperature phosphorescent material having fluid properties with general applicability.
In order to overcome the conditions of complex preparation and poor applicability of the conventional organic phosphorescent material, a series of organic room temperature phosphorescent supramolecular polymers with fluid properties are prepared by a strategy of inducing solid melting point reduction through hydrogen bonds, the organic phosphor can emit light in a fluid matrix, and the preparation strategy is extremely simple and convenient and is suitable for large-scale industrial preparation. Meanwhile, the organic room temperature phosphorescent material prepared by the invention has high luminous efficiency and has great significance for the development and application of the organic room temperature phosphorescent material.
Disclosure of Invention
The invention provides a room temperature phosphorescent material and a preparation method thereof.
The application provides a preparation method of a room-temperature phosphorescent material, which comprises the following steps: step (1): heating organic acid and organic alcohol to react to form a supramolecular polymer, dropwise adding organic phosphor dispersion liquid into the supramolecular polymer, and continuously heating until the supramolecular polymer shows high viscosity and no steam is generated; step (2): and drying to obtain the room temperature phosphorescent material.
Optionally, in some embodiments herein, the supramolecular polymer is a multi-component supramolecular material that is constructed based on non-covalent interactions.
Optionally, in some embodiments of the present application, in step (1), the organic acid and the organic alcohol solution are heated to 120-180 ℃, and after the organic acid and the solvent in the organic alcohol solution are volatilized, the supramolecular polymer is formed; preferably, the organic acid and the organic alcohol solution are heated to 140-160 ℃; preferably, the organic acid and the organic alcohol solution are heated to 150 ℃.
Alternatively, in some embodiments herein, the melting point of the resulting supramolecular polymer is significantly lower than the organic acid and the organic alcohol because a large number of intermolecular hydrogen bonds may be formed upon reaction of the organic acid and the organic alcohol.
Alternatively, in some embodiments of the present application, the organic phosphor dispersion is an organic solvent having water solubility in which the organic phosphor is dispersed.
Optionally, in some embodiments of the present application, in the step (2), the product obtained in the step (1) is dried in a heating vacuum drying oven for 10 to 14 hours to obtain the pure organic room temperature phosphorescent material; preferably, the product obtained in the step (12) is placed in a heating vacuum drying oven to be dried for 11-13 hours, and the pure organic room temperature phosphorescent material is obtained; preferably, the product obtained in the step (1) is dried in a heating vacuum drying oven for 12 hours to obtain the pure organic room temperature phosphorescent material.
Correspondingly, the application also provides the room temperature phosphorescent material prepared by the preparation method, the room temperature phosphorescent material comprises a host material and a guest material, the host material is a supramolecular polymer, the guest material is an organic phosphor, and the supramolecular polymer is obtained by heating and reacting organic alcohol and organic acid.
Alternatively, in some embodiments of the present application, the purely organic room temperature phosphorescent material has fluid properties.
Optionally, in some embodiments of the present application, the kinds and doping ratio of the organic acid and the organic alcohol are not limited; preferably, the organic acid is a small molecular organic acid with a relative molecular mass of 50 to 500; preferably, the organic acid is any one or mixture of two of small molecular organic acids such as malic acid and citric acid; preferably, the organic alcohol is an organic alcohol containing two or more hydroxyl groups in the molecule; preferably, the organic alcohol is any one or a mixture of two of alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin and delta-cyclodextrin.
Optionally, in some embodiments of the present application, the kind and doping ratio of the organic phosphor are not limited, and preferably, the organic phosphor is any one or more of pure organic phosphors such as bromonaphthalene, N-substituted naphthalimide, benzil, and the like; wherein, the substituent in the N-substituted bromonaphthalimide is not limited.
The method for blending the supermolecule polymer with a large number of hydrogen bonds and the organic phosphor is adopted to form the pure organic room temperature phosphorescent material with the fluid property, the preparation method is simple and convenient, and the obtained pure organic room temperature phosphorescent material is high in luminous efficiency and has universal applicability.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a flow chart of a preparation method of a pure organic room temperature phosphorescent material;
FIG. 2 is a phosphorescence spectrum of the pure organic room temperature phosphorescent material provided in example 1;
FIG. 3 is a life curve of the pure organic room temperature phosphorescent material provided in example 1;
FIG. 4 is a graph of rheological data (scanning frequency on abscissa) of a pure organic room temperature phosphorescent material provided in example 1;
FIG. 5 is a phosphorescence spectrum of the pure organic room temperature phosphorescent material provided in example 2;
FIG. 6 is a life curve of the pure organic room temperature phosphorescent material provided in example 2;
FIG. 7 is a graph of rheological data (scanning frequency on abscissa) of a pure organic room temperature phosphorescent material provided in example 2;
FIG. 8 is a phosphorescence spectrum of the pure organic room temperature phosphorescent material provided in example 3;
FIG. 9 is a life curve of the pure organic room temperature phosphorescent material provided in example 3;
FIG. 10 is a graph of rheological data (scanning frequency on the abscissa) for a purely organic room temperature phosphorescent material provided in example 3.
Detailed Description
The technical solutions in the embodiments of the present application will be described clearly and completely with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only some embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The embodiment of the application provides a room-temperature phosphorescent material and a preparation method thereof. The following are detailed descriptions. It should be noted that the following description of the embodiments is not intended to limit the preferred order of the embodiments.
The pure organic material of the invention refers to a phosphorescent material of which both the host material and the guest material are organic compounds, compared with the traditional phosphorescent material based on inorganic or metal organic compounds.
The room temperature phosphorescent material is a phosphorescent material with efficient phosphorescent emission at room temperature, and the room temperature is 18-27 ℃.
FIG. 1 is a flow chart of a method for preparing a pure organic room temperature phosphorescent material.
1) Firstly, a watch glass is placed on a heating table, the aqueous solution of the organic acid and the organic alcohol is heated to 150 ℃, and because a large number of intermolecular hydrogen bonds can be formed between the organic acid and the organic alcohol, the supermolecular polymer with a melting point which is obviously lower than that of the organic acid and the organic alcohol can be formed after the water in the aqueous solution is volatilized.
2) In the process of forming the supramolecular polymer, the organic phosphor is dispersed in a corresponding organic solvent with water solubility, and is gradually dripped into a supramolecular system, and heating is continuously carried out until the supramolecular polymer shows high viscosity, so as to obtain high-viscosity fluid.
3) And (3) placing the high-viscosity fluid obtained in the step into a heating vacuum drying oven for drying for 12 hours, and finally obtaining the pure organic room-temperature phosphorescent material with the fluid property.
The first embodiment,
The embodiment provides a preparation method of a pure organic room temperature phosphorescent material, which specifically comprises the following steps:
1) Firstly, a watch glass is placed on a heating table, an aqueous solution of malic acid (organic acid) and cyclodextrin (organic alcohol) is heated to 150 ℃, and because a large amount of intermolecular hydrogen bonds can be formed between the organic acid and the organic alcohol, a supramolecular polymer with a melting point which is obviously lower than that of the organic acid and the organic alcohol can be formed after water in the aqueous solution is volatilized.
2) In the process of forming the supramolecular polymer, 1-bromonaphthalene (organic phosphor) is dispersed in a corresponding organic solvent with water solubility, and is gradually dripped into a supramolecular system, and heating is continued until the supramolecular polymer shows high viscosity.
3) And (3) placing the high-viscosity fluid obtained in the step into a heating vacuum drying oven for drying for 12 hours, and finally obtaining the pure organic room-temperature phosphorescent material with fluid property. The absolute phosphorescence quantum yield (integrating sphere method) is 30%, the emission peaks are about 500nm and 525nm (figure 2), the service life is 7.13ms (figure 3), the loss modulus is constantly larger than the storage modulus, and the prepared pure organic room temperature phosphorescence material has fluid properties (figure 4).
Example II,
The embodiment provides a preparation method of a pure organic room temperature phosphorescent material, which specifically comprises the following steps: 1) Firstly, a watch glass is placed on a heating table, an aqueous solution of citric acid (organic acid) and cyclodextrin (organic alcohol) is heated to 150 ℃, and because a large amount of intermolecular hydrogen bonds can be formed between the organic acid and the organic alcohol, a supramolecular polymer with a melting point which is obviously lower than that of the organic acid and the organic alcohol can be formed after water in the aqueous solution is volatilized.
2) In the process of forming the supramolecular polymer, N-propyl bromonaphthalimide (organic phosphor) is dispersed in a corresponding organic solvent with water solubility, and is gradually dripped into a supramolecular system, and heating is continued until the supramolecular polymer shows high viscosity.
3) And (3) placing the high-viscosity fluid obtained in the step into a heating vacuum drying oven for drying for 12 hours, and finally obtaining the pure organic room-temperature phosphorescent material with the fluid property. The absolute phosphorescence quantum yield (integrating sphere method) is 17%, the emission peaks are about 565nm and 500nm (figure 5), the service life is 4.95ms (figure 6), the loss modulus is constantly larger than the storage modulus, and the prepared pure organic room temperature phosphorescence material has fluid properties (figure 7).
Example III,
The embodiment provides a preparation method of a pure organic room temperature phosphorescent material, which specifically comprises the following steps:
1) Firstly, a watch glass is placed on a heating table, an aqueous solution of citric acid (organic acid) and cyclodextrin (organic alcohol) is heated to 150 ℃, and because a large amount of intermolecular hydrogen bonds can be formed between the organic acid and the organic alcohol, a supramolecular polymer with a melting point which is obviously lower than that of the organic acid and the organic alcohol can be formed after water in the aqueous solution is volatilized.
2) In the process of forming the supramolecular polymer, benzil (organic phosphor) is dispersed in a corresponding organic solvent with water solubility, and gradually dripped into a supramolecular system, and heating is continued until the supramolecular polymer shows high viscosity.
3) And (3) placing the high-viscosity fluid obtained in the step into a heating vacuum drying oven for drying for 12 hours, and finally obtaining the pure organic room-temperature phosphorescent material with the fluid property. The absolute phosphorescence quantum yield (integrating sphere method) is 10.2%, the emission peak is at 566nm (figure 8), the service life is 0.096ms (figure 9), the loss modulus is constantly larger than the storage modulus, and the prepared pure organic room temperature phosphorescence material has the fluid property (figure 10).
The above embodiments are only used to help understand the method and the core concept of the present application; meanwhile, for those skilled in the art, according to the idea of the present application, the specific implementation manner and the application scope may be changed, and in summary, the content of the present specification should not be construed as a limitation to the present application.

Claims (5)

1. A method of preparing a phosphorescent material, the method comprising the steps of:
step (1): heating organic acid and organic alcohol to react to form a supramolecular polymer, dropwise adding organic phosphor dispersion liquid into the supramolecular polymer, and continuously heating until no steam is generated;
step (2): drying to obtain the phosphorescent material;
wherein the organic acid is selected from at least one of malic acid or citric acid, and the organic alcohol is selected from at least one of alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin or delta-cyclodextrin;
the organic phosphor is selected from the group consisting of bromonaphthalene,N-at least one of a substituted bromonaphthalimide or benzil;
the melting point of the supramolecular polymer is lower than the organic acid and the organic alcohol;
the phosphorescent material has fluid properties.
2. The method according to claim 1, wherein in the step (1), the organic acid and the organic alcohol solution are heated to 120 to 180 ℃ and the supramolecular polymer is formed after the organic acid and the solvent in the organic alcohol solution are volatilized.
3. The method according to claim 1, wherein the organic phosphor dispersion is prepared by: the organic phosphor dispersion liquid is obtained by dispersing an organic phosphor in an organic solvent having water solubility.
4. The method according to claim 1, wherein in the step (2), the product obtained in the step (1) is dried in a heating vacuum drying oven for 10-14 hours to obtain the phosphorescent material.
5. The phosphorescent material prepared by the preparation method of any one of claims 1 to 4, wherein the phosphorescent material comprises a host material and a guest material, the host material is a supramolecular polymer, the guest material is an organic phosphor, and the supramolecular polymer is obtained by heating and reacting an organic alcohol and an organic acid;
wherein the organic acid is selected from at least one of malic acid or citric acid, and the organic alcohol is selected from at least one of alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin or delta-cyclodextrin;
the organic phosphor is selected from the group consisting of bromonaphthalene,N-at least one of a substituted bromonaphthalimide or benzil;
the supramolecular polymer has a melting point lower than the organic acid and the organic alcohol;
the phosphorescent material has fluid properties.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2789685B1 (en) * 1999-02-15 2001-05-04 Univ Lille Sciences Tech PROCESS FOR MANUFACTURING SOLUBLE AND INSOLUBLE POLYMERS BASED ON CYCLODEXTRIN (S) AND / OR DERIVATIVES OF CYCLODEXTRIN (S) AND SOLUBLE POLYMERS BASED ON CYCLODEXTRIN (S) AND / OR DERIVATIVES OF CYCLODEXTRIN (S)
CN106749773B (en) * 2017-01-06 2019-09-03 华东理工大学 The preparation method of pure organic cyclodextrin main body derivative with efficient room temperature phosphorescent emissions

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