A naphthobis-triazole derivative chromophore, light conversion material and preparation method thereof

Abstract

This invention provides a naphthobistriazole derivative chromophore, a light-converting material, and a method for preparing the same. The naphthobistriazole derivative chromophore is characterized by having the structural formula shown in Formula I: In Formula I, X is selected from -N(A0)-, and A0 is independently selected from any one of hydrogen, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, acyloxy, aryl, heteroaryl, and amino. This invention develops a naphthobistriazole light-converting agent material system. These compounds can be used as chromophores to provide the desired optical properties and good photostability. These chromophores can be used as light-converting agents in various luminescent material applications, including in light-converting films.

Description

Technical Field

[0001] This invention relates to the field of luminescent materials technology, and in particular to a naphthobistriazole derivative chromophore, a light conversion material, and a method for preparing the same. Background Technology

[0002] Light conversion films are widely used in agriculture and photovoltaics. The light conversion agent is the core material of the film, capable of absorbing and converting specific wavelengths of sunlight to improve light energy utilization. Its performance directly affects the performance and application effect of the light conversion film. Most existing organic light conversion agents still have many drawbacks, such as low color purity, poor stability, and low quantum efficiency.

[0003] To address the aforementioned problems, researchers have turned their attention to aromatic ring compounds with π-conjugated structures. Among these, nitrogen-containing heterocyclic materials are a class of luminescent materials with relatively excellent performance; however, most existing organic luminescent dyes typically exhibit poor photostability, such as imidazole derivatives, carbazole derivatives, oxadiazoles, and triazine derivatives. Therefore, there is an urgent need to develop a new luminescent dye system to solve the problem of poor optical stability in purely organic luminescent agents. Summary of the Invention

[0004] In view of the shortcomings of the prior art described above, the purpose of this invention is to provide a naphthobistriazole derivative chromophore, a light conversion material and a method for preparing the same, in order to solve the problem of poor optical stability of existing pure organic light conversion agents.

[0005] To achieve the above and other related objectives, the present invention provides a chromophore of a naphthobistriazole derivative, the structural formula of which is shown in Formula I:

[0006] ;

[0007] In Formula I, X is selected from -N(A0)-, and A0 is independently selected from hydrogen, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, acyloxy, aryl, heteroaryl and amino.

[0008] R1 and R2 are any one of alkoxy, aryloxy, acyloxy, alkyl, aryl, heteroaryl, and amino.

[0009] Preferably, R1 and R2 are phenyl groups.

[0010] Preferably, the substituent of the phenyl group is selected from any one of alkyl, alkoxy, aryl, heteroaryl, and amino groups.

[0011] The present invention also provides a chromophore of a naphthobistriazole derivative, the structural formula of which is shown in Formula II:

[0012] ;

[0013] In Formula II, each R is independently selected from any one of hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryloxy, acyloxy, aryl, heteroaryl, and amino.

[0014] The present invention also provides a chromophore of a naphthobistriazole derivative, the structural formula of which is shown in Formula III:

[0015] ;

[0016] In Formula III, R1, R2, R3, and R4 are each independently selected from any one of alkyl, cycloalkyl, alkenyl, alkynyl, aryloxy, acyloxy, aryl, heteroaryl, and amino groups.

[0017] Preferably, R1, R2, R3, and R4 are not all H, and each is independently selected from any one of the following groups:

[0018] (1) C1~C6 alkyl, cycloalkyl or alkoxy; (2) (3) .

[0019] The present invention also provides a chromophore of a naphthobistriazole derivative, the structural formula of which is shown in Formula IV:

[0020] ;

[0021] In Formula IV, D1 and D2 are each independently selected from any one of hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryloxy, acyloxy, aryl, heteroaryl and amino.

[0022] The present invention also provides a light conversion material comprising an optically transparent polymer matrix and a luminescent dye, wherein the luminescent dye comprises at least one of the above-mentioned naphthobistriazole derivative chromophores.

[0023] Preferably, the optically transparent polymer matrix is ​​selected from one or more of ethylene-vinyl acetate copolymer (EVA), polyethylene (PE), polyvinyl alcohol copolymer (POE), and polymethyl methacrylate (PMMA).

[0024] Preferably, the content of the luminescent dye is 0.2~0.5wt%, based on the mass of the optically transparent polymer matrix.

[0025] Preferably, the thickness of the light conversion material is 30~50μm.

[0026] Preferably, the spin coating speed is 500~700 r / min.

[0027] This invention also provides a method for preparing a light conversion material, comprising the following steps:

[0028] (1) Dissolve the polymer matrix in an organic solvent to obtain a polymer matrix solution;

[0029] (2) Mix the polymer matrix solution and the luminescent dye evenly to obtain a dye / polymer mixture;

[0030] (3) Spin-coating the dye / polymer mixture onto the substrate surface and drying it to obtain the light conversion material.

[0031] Preferably, the organic solvent is selected from one or more of tetrahydrofuran (THF), cyclopentanone, and dioxane.

[0032] As described above, the present invention has the following beneficial effects:

[0033] (1) The present invention develops a naphthobistriazole light conversion agent material system. These compounds can be used as chromophores that provide the required optical properties and good photostability. The above-mentioned chromophores can be used as light conversion agents in various light-emitting material application fields, including in light conversion films.

[0034] (2) The light conversion material of the present invention uses a luminescent dye containing the above-mentioned chromophore with good photostability, which can stably absorb and convert specific wavelengths in sunlight and improve the light energy utilization rate. Attached Figure Description

[0035] Figure 1 The fluorescence emission spectrum of the light conversion material prepared in the example is shown.

[0036] Figure 2 The image shows the ultraviolet absorption spectrum of the light conversion material prepared in the example.

[0037] Figure 3 The transmission spectrum of the light conversion material prepared in the example is shown. Detailed Implementation

[0038] The following specific examples illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and various details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention.

[0039] It should be noted that the process equipment or apparatus not specifically mentioned in the following embodiments are all conventional equipment or apparatus in the art.

[0040] Furthermore, it should be understood that the existence of other method steps before or after the combined steps, or the insertion of other method steps between these explicitly mentioned steps, does not preclude the existence of other method steps before or after the combined steps, or the insertion of other method steps between these explicitly mentioned steps, unless otherwise stated. It should also be understood that the combined connection relationship between one or more devices / apparatus mentioned in this invention does not preclude the existence of other devices / apparatus before or after the combined devices / apparatus, or the insertion of other devices / apparatus between these explicitly mentioned devices / apparatus, unless otherwise stated. Moreover, unless otherwise stated, the numbering of each method step is merely a convenient tool for identifying each method step, and not for limiting the order of the method steps or limiting the scope of the invention. Changes or adjustments to their relative relationships, without substantially altering the technical content, should also be considered within the scope of the invention.

[0041] The atom designations for the naphthobistriazole system provided in this application are as follows:

[0042]

[0043] The substituents are located at positions 3, 6, 7, and 8 of the naphthobistriazole system.

[0044] The term "alkyl" refers to a fully saturated acyclic aliphatic hydrocarbon group (i.e., composed of carbon and hydrogen, and without double or triple bonds) that is branched or straight-chain. Alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, and hexyl.

[0045] As used in this application, the term "cycloalkyl" refers to a saturated aliphatic ring system group having 3-20 carbon atoms, including but not limited to cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, etc.

[0046] As used in this application, the term "alkenyl" refers to a monovalent straight-chain or branched group containing 2 to 20 carbon atoms with a carbon double bond, including but not limited to propenyl, propenyl, 2-methylpropenyl, butenyl, butenyl, etc.

[0047] As used in this application, the term "alkynyl" refers to a monovalent straight-chain or branched group containing 2 to 20 carbon atoms with a carbon triple bond, including but not limited to prop-1-alkynyl, but-1-alkynyl, but-2-alkynyl, etc.

[0048] As used in this application, the term "alkoxy" refers to a straight-chain or branched alkyl group covalently bonded to a parent molecule via an -O- linker. Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, butoxy, n-butoxy, sec-butoxy, and tert-butoxy.

[0049] As used in this application, the term "aryloxy group" refers to an aryl group that is covalently bonded to the parent molecule via an -O- linker.

[0050] As used in this application, the term "acyloxy group" refers to a carbonyl group that is covalently bonded to the parent molecule via an -O- linker.

[0051] As used in this application, the term "aryl" refers to an allotropic aromatic group, whether it is a single ring or multiple fused rings. Examples of aryl groups include, but are not limited to, phenyl, naphthyl, phenanthryl, tetraphenyl, fluorenyl, pyrene, etc.

[0052] As used in this application, the term "heteroaryl" refers to an aromatic group containing one or more heteroatoms, whether in a single ring or multiple fused rings. When two or more heteroatoms are present, they may be the same or different. In a fused ring system, one or more heteroatoms may be present in only one ring. Examples of heteroaryl groups include, but are not limited to, benzothiazolyl, benzooxazinyl, quinazolinyl, quinolinyl, isoquinolinyl, quinoxalolinyl, pyridyl, pyrroleyl, oxazolyl, indoleyl, thiazolyl, etc.

[0053] As used in this application, the term "heteroatoms" refers to S (sulfur), N (nitrogen), and O (oxygen).

[0054] The term "amino" as used in this application refers to –NR'R''.

[0055] As used in this application, the term "cyclic amino" refers to a secondary or tertiary amine in the cyclic moiety. Examples of cyclic amino groups include, but are not limited to, acridine, piperidinyl, and N-methylpiperidinyl.

[0056] In some implementation schemes, the chromophore is as shown in Formula III.

[0057] ;

[0058] R1, R2, R3, and R4 are not all H, and are independently selected from any one of the following groups:

[0059] (1) C1~C6 alkyl, cycloalkyl or alkoxy; (2) (3) .

[0060] This invention provides a method for preparing chromophores from naphthobistriazole derivatives, which includes the following steps according to the synthetic route:

[0061]

[0062] (1) Synthesis of N,N'-(naphthalene-1,5-diyl)bis(4-methylbenzenesulfonamide) (intermediate 1):

[0063] Weigh 1.58 g (10 mmol) of naphthalene-1,4-diamine and 4-methylbenzenesulfonyl chloride (4.54 g, 23.8 mmol), and add 5 mL of pyridine to a 250 mL two-necked round-bottom flask. Under nitrogen protection, add 30 mL of toluene and heat under reflux for 2.5 h. Cool to room temperature, add 300 mL of petroleum ether to the reaction solution to obtain a large amount of precipitate. Filter, wash the filter cake with 1 M hydrochloric acid and water, recrystallize with acetonitrile, and filter again to obtain a gray crude product (3 g, 65%). The crude product can be used directly in the next step without further purification.

[0064] Synthesis of N,N'-(2,6-dinitronaphthalene-1,5-diyl)bis(4-methylbenzenesulfonamide) (intermediate 2):

[0065] Intermediate 1 (2.0 g, 4.3 mmol) and sodium nitrite (0.1 g, 1.45 mmol) were weighed and added to a 500 mL round-bottom flask. 20 mL of acetic acid solution was added, and the mixture was cooled to 0 °C. A mixed solution of 70% HNO3 (3 mL) and acetic acid (2 mL) was added dropwise to the reaction mixture. After stirring for 30 minutes, the mixture was removed from the low-temperature bath and slowly brought to room temperature with stirring for 2 hours. After the reaction was complete, the brown impurities were removed by filtration. The resulting filter cake was washed three times with cold acetic acid and ethanol, respectively, and dried to obtain a brown crude product. The crude product was placed in a 500 mL round-bottom flask, and the system was heated to 120 °C with stirring. Pyridine was slowly added until the solid powder was completely dissolved. Then, deionized water was slowly added until new solid precipitated. Finally, pyridine was slowly added again until the solid was completely dissolved again. The entire system was left at room temperature for 24 hours, and then filtered to obtain a yellow crystalline powder (1.48 g, yield 62%). Its 1H NMR characterization is as follows: 1 H NMR (600 MHz, DMSO-d6) δ10.92 (s, 2H), 7.90-7.83 (m, 4H), 7.37 (d, J = 6.5 Hz, 4H), 7.29 (d, J = 6.5Hz, 4H), 2.35 (s, 6H).

[0066] Synthesis of 2,6-dinitronaphthalene-1,5-diamine (intermediate 3):

[0067] Intermediate 2 (3.49 g, 6.23 mmol) was weighed and added to a 250 mL round-bottom flask, followed by 60 mL of concentrated H₂SO₄. The mixture was heated to approximately 45 °C and maintained at this temperature for 2 h. After the reaction was complete, the mixture was cooled to room temperature, and the dark, clear reaction solution was poured into a large amount of ice-water mixture, yielding a large precipitate. The precipitate was filtered, washed with water, and dried to give a deep purple product (1.2 g, 75%). Its 1H NMR characterization is as follows: 1 H NMR (600 MHz, DMSO-d6) δ 8.39 (d, J = 6.5 Hz, 2H), 8.01-7.99 (d, J = 6.5 Hz, 2H), 7.65-7.63 (s, 4H).

[0068] Synthesis of 1,2,5,6-naphthyltetramine tetrahydrochloride (intermediate 4):

[0069] Intermediate 3 (1.02 g, 4.11 mmol) and stannous chloride dihydrate (9.05 g, 40.1 mmol) were weighed into a 250 mL two-necked round-bottom flask. Under nitrogen protection, a mixture of 40 mL ethanol and 12 mL concentrated hydrochloric acid was added. The mixture was heated to 90 °C and maintained for 12 h. After the reaction was completed, it was cooled to room temperature. The mixture was then poured into 100 mL of cold concentrated hydrochloric acid. The precipitated solid was separated by suction filtration, washed with hydrochloric acid, and dried under vacuum to obtain a off-white 1,2,5,6-naphthyltetramine hydrochloride. Because it is easily oxidized and deteriorated in air, it needs to be stored under a nitrogen atmosphere; therefore, no further purification or structural characterization was performed.

[0070] Synthesis of 1,6-dihydro-naphtho[1,2-d:5,6-d′]bis[1,2,3]-triazole (intermediate 5):

[0071] Under nitrogen protection, intermediate 4 (2.27 g, 3.4 mmol) was dissolved in 10 mL of acetic acid, and the solution was stirred for 30 min. Sodium nitrite (1.74 g, 3.7 mmol) was then dissolved in 20 mL of water and mixed with the solution. The reaction mixture was allowed to react at room temperature for 3 h to form a dark brown precipitate (1.72 g, 79%). The reaction mixture was filtered, washed with methanol, and dried to give a dark brown solid. No further processing was required for the next step.

[0072] Synthesis of 2,7-diethyl-2,7-dihydronaphtho[1,2-d:5,6-d']bis([1,2,3]-triazole) (intermediate 6)

[0073] Intermediate 5 (1.70 g, 1 mmol) was weighed and added to a 100 mL round-bottom flask along with bromoethane (2.65 g, 3 mmol), potassium tert-butoxide (2.18 g, 2.4 mmol), and tetrabutylammonium bromide (0.52 g, 0.2 mmol). 20 mL of ethanol was added as a solvent, and the mixture was refluxed at 80 °C for 12 h under a nitrogen atmosphere. After the reaction was complete, heating was stopped, and the mixture was allowed to cool completely. The mixture was then extracted with water and dichloromethane, and the organic phase was collected. The solution was dehydrated, filtered, and rotary evaporated to obtain a solid sample. Purification by column chromatography yielded a white-gray solid (1.50 g, 69%). Its 1H NMR characterization is as follows: 1 H NMR (400 MHz, CDCl3)δ 8.42 (d, J = 9.1 Hz, 2H), 7.93 (d, J = 9.1 Hz, 2H), 4.86 -4.73 (m, 4H), 1.76-1.66 (m, 6H).

[0074] Synthesis of 5,10-dibromo-2,7-diethyl-2,7-dihydronaphtho[1,2-d:5,6-d']bis([1,2,3]-triazole) (intermediate 7)

[0075] Intermediate 6 (0.20 g, 3.2 mmol) was weighed into a 100 mL round-bottom flask, and 20 mL of HBr was added. The temperature was increased until the solid was completely dissolved. Liquid bromine (0.35 g, 9.6 mmol) was added dropwise to the mixture, and the mixture was refluxed overnight. After the reaction was complete, excess sodium bisulfite solution was added, and the crude product was poured into water. Extraction was performed with water and dichloromethane, and the organic phase was collected. Dehydration was performed, and the sample was filtered and rotary evaporated to obtain a solid sample. Purification was performed by column chromatography to obtain a white solid (0.10 g, 33%). Its 1H NMR characterization is as follows: 1 H NMR (400 MHz, CDCl3) δ 8.58 (s, 2H), 4.82 (q, J = 7.3 Hz, 4H), 1.72 (t, J = 7.3 Hz, 6H).

[0076] Synthesis of .5,10-bis(4-tert-butyl)phenyl-2,7-diethyl-2,7-dihydronaphtho[1,2-d:5,6-d']bis([1,2,3]-triazole) (product 8)

[0077] Intermediate 7 (0.10 g, 1 mmol), 4-tert-butylphenylboronic acid (0.11 g, 2.5 mmol), anhydrous potassium carbonate (0.20 g, 6 mmol), and tetrakis(triphenylphosphine)palladium (0.014 g, 0.05 mmol) were weighed and added to a 100 mL two-necked flask, and the mixture was purged under a nitrogen atmosphere. 10 mL of toluene solvent and 1 mL of deionized water were added, and the mixture was stirred and heated to 90 °C. The reaction was allowed to proceed for 12 h under condensation. After the reaction was complete, the heating was stopped, and the mixture was allowed to cool completely. The mixture was then extracted with water and dichloromethane, and the organic phase was collected. The solution was dehydrated, filtered, and rotary evaporated to obtain a solid sample. The solid was purified by column chromatography to obtain a white solid (0.2 g, 60%). Its 1H NMR characterization is as follows: 1 H NMR (400 MHz, CDCl3) δ 8.70 (s, 2H), 8.20 (d,J = 8.4 Hz, 4H), 7.60 (t, J = 12.8 Hz, 4H), 4.93 (q, J = 7.4 Hz, 4H), 1.83(t, J = 7.3 Hz, 6H), 1.44 (s, 18H).

[0078] This application provides a luminescent dye that uses the product 8 obtained above as a chromophore.

[0079] This application also provides a light conversion material, comprising an optically transparent polymer matrix and the aforementioned luminescent dye. Based on the mass of the optically transparent polymer matrix, the luminescent dye content is 0.3 wt%, and the thickness of the light conversion material is 40 μm. The polymer matrix is ​​EVA.

[0080] This application also provides a method for preparing a light conversion material, including the following steps:

[0081] (i) Dissolve the polymer matrix in tetrahydrofuran (THF) in the predetermined ratio described above to obtain a polymer matrix solution;

[0082] (ii) A polymer mixture containing a luminescent dye is prepared by mixing a polymer matrix solution with a luminescent dye at a predetermined weight ratio to obtain a dye / polymer mixture;

[0083] (iii) The dye / polymer mixture is directly cast onto a quartz substrate and then spin-coated using a spin coater to form a dye / polymer film, followed by drying of the polymer film;

[0084] (IV) The film thickness was controlled to be 40 μm by changing the dye / polymer solution concentration and spin coating speed, and the spin coating speed was 600 r / min.

[0085] The performance of the light conversion material prepared in this embodiment was tested, and the results are shown in Table 1:

[0086] Table 1. Performance test results of light conversion materials .

[0087] The fluorescence emission spectrum of the light conversion material (light conversion film) prepared in this embodiment is as follows: Figure 1 As shown, from Figure 1 It can be seen that the main peak of fluorescence emission of the light conversion material thin film prepared in the example is 435 nm, the fluorescence spectrum covers the blue light region of the visible light, and there is almost no emission in the ultraviolet region (<400 nm).

[0088] The ultraviolet absorption spectrum of the light conversion material (light conversion film) prepared in this embodiment is as follows: Figure 2 As shown, from Figure 2 It can be seen that the main absorption peak of the absorption spectrum is located at 360 nm, and the absorption spectrum covers the 300-400 nm ultraviolet light region.

[0089] The transmission spectrum of the light conversion material (light conversion film) prepared in this embodiment is as follows: Figure 3 As shown, from Figure 3 It can be seen that almost no ultraviolet light below 400 nm is transmitted, while the transmittance in the visible light region is almost 100%, indicating that the film of the embodiment can effectively absorb and block ultraviolet light and has a high visible light transmittance.

[0090] The above embodiments are for illustrating the implementation schemes disclosed in this invention and should not be construed as limiting the invention. Furthermore, various modifications listed herein, as well as variations in the methods and compositions of the invention, will be apparent to those skilled in the art without departing from the scope and spirit of the invention. Although the invention has been specifically described in conjunction with various specific preferred embodiments, it should be understood that the invention should not be limited to these specific embodiments. In fact, various modifications as described above that are obvious to those skilled in the art to obtain the invention should be included within the scope of this invention.

Claims

1. A chromophore of a naphthobistriazole derivative, characterized in that, The structural formula is shown in Formula I: ； In Formula I, X is selected from -N(A0)-, and A0 is independently selected from any one of hydrogen, alkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, acyloxy, aryl, heteroaryl and amino. R1 and R2 are independently selected from any one of alkoxy, aryloxy, acyloxy, alkyl, aryl, heteroaryl, and amino.

2. The chromophore of the naphthobistriazole derivative according to claim 1, characterized in that: R1 and R2 are phenyl groups.

3. The chromophore of the naphthobistriazole derivative according to claim 2, characterized in that: The substituents of the phenyl group are selected from any one of alkyl, alkoxy, aryl, heteroaryl, and amino groups.

4. A chromophore of a naphthobistriazole derivative, characterized in that, The structural formula is shown in Formula II: ； In Formula II, each R is independently selected from any one of hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryloxy, acyloxy, aryl, heteroaryl, and amino.

5. A chromophore of a naphthobistriazole derivative, characterized in that, The structural formula is shown in Formula III: ； In Formula III, R1, R2, R3, and R4 are any one of alkyl, cycloalkyl, alkenyl, alkynyl, aryloxy, acyloxy, aryl, heteroaryl, and amino.

6. The chromophore of the naphthobistriazole derivative according to claim 5, characterized in that: R1, R2, R3, and R4 are not all H, and are independently selected from any one of the following groups: (1) C1~C6 alkyl, cycloalkyl or alkoxy; (2) (3) .

7. A chromophore of a naphthobistriazole derivative, characterized in that, The structural formula is shown in Formula IV: ； In Formula IV, D1 and D2 are each independently selected from any one of hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryloxy, acyloxy, aryl, heteroaryl, and amino.

8. A light conversion material, characterized in that: It includes an optically transparent polymer matrix and a luminescent dye, wherein the luminescent dye includes at least one chromophore of a naphthobistriazole derivative as described in any one of claims 1 to 7; The optically transparent polymer matrix is ​​selected from one or more of ethylene-vinyl acetate copolymer, polyethylene, polyvinyl alcohol copolymer and polymethacrylate.

9. The light conversion material according to claim 8, characterized in that: Based on the mass of the optically transparent polymer matrix, the content of the luminescent dye is 0.2~0.5wt%; the thickness of the light conversion material is 30~50μm.

10. A method for preparing the light conversion material as described in claim 8 or 9, characterized in that: Includes the following steps: (1) Dissolve the polymer matrix in an organic solvent to obtain a polymer matrix solution; (2) Mix the polymer matrix solution and the luminescent dye evenly to obtain a dye / polymer mixture; (3) Spin-coating the dye / polymer mixture onto the substrate surface and drying it to obtain the light conversion material; the spin-coating speed is 500~700r / min.

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