High-entropy charge transfer luminescent material as well as preparation method and application thereof

Abstract

The invention discloses a high-entropy charge transfer luminescent material and a preparation method and application thereof.The high-entropy charge transfer luminescent material comprises a diphenyl sulfone acceptor group and a 9, 9-dimethyl acridine donor group, the diphenyl sulfone acceptor group and the 9, 9-dimethyl acridine donor group serve as a charge transfer skeleton, and the diphenyl sulfone acceptor group and the 9, 9-dimethyl acridine donor group serve as the charge transfer skeleton. The disorder degree property of charge transfer is regulated and controlled by modification of an alkyl chain and a derivative group of the alkyl chain; the high-entropy charge transfer luminescent material can increase the disorder degree of charge transfer, has amide and derivative structure passivation groups thereof, and is beneficial to promoting a luminescent channel and morphology regulation and control; the high-entropy charge transfer luminescent material has important application value in the fields of organic light emitting diodes and perovskite light emitting diodes.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic semiconductor materials, and in particular relates to a high entropy charge transfer luminescent material and a preparation method and application thereof. Background Art

[0002] Charge transfer organic semiconductors, especially luminescent materials, can generally effectively regulate triplet exciton behavior. They are generally composed of electron donors and electron acceptors. Different donor-acceptor structures give them different triplet exciton behaviors. Due to its own advantages such as easy structural modification and wide sources, it can be applied to organic electroluminescent devices, quantum dot electroluminescent devices, perovskite light-emitting devices, etc. However, organic semiconductor materials with multiple functions such as high triplet energy levels, high exciton utilization, and weak coordination properties are still relatively scarce. In response to the above problems, a charge transfer skeleton was prepared, and alkyl chains and amide groups were introduced to achieve charge transfer disorder and structural passivation. Summary of the invention

[0003] To solve the above problems, the present invention proposes a high entropy charge transfer luminescent material and a preparation method and application thereof. The high entropy charge transfer luminescent material can increase the charge transfer disorder degree and has a passivation group of an amide and its derivative structure, which is beneficial to promote the regulation of luminescence channels and morphology. The high entropy charge transfer luminescent material has important application value in the field of organic light emitting diodes and perovskite light emitting diodes.

[0004] To achieve the above object, the present invention adopts the following technical solutions:

[0005] A high entropy charge transfer luminescent material, comprising a diphenyl sulfone acceptor group and a 9,9-dimethylacridine donor group, wherein the diphenyl sulfone acceptor group and the 9,9-dimethylacridine donor group are used as charge transfer skeletons and are modified by alkyl chains and derivative groups thereof; the structural formula of the high entropy charge transfer luminescent material is as follows:

[0006]

[0007] Wherein, R is a long alkyl chain embedded amide and its derivatives, and the length of the alkyl chain is carbon number ≥ 6.

[0008] Preferably, the long chain of R contains one or more of halogen, amide, and ether bond.

[0009] A method for preparing a high entropy charge transfer luminescent material comprises the following steps:

[0010] S1, bisphenol S and p-toluenesulfonyl chloride are mixed in a molar ratio of (1-2):1, and then dichloromethane is used as a solvent, 4-lutidine is used as a catalyst, triethylamine is added, and the reaction is performed to obtain an intermediate A;

[0011] The preparation route is as follows:

[0012]

[0013] S2. Using Williamson reaction, the intermediate A and the alkyl chain and its derivatives are mixed in a molar ratio of 1:(1-2), and then acetone is used as a solvent, and potassium carbonate is added in an amount of 1-2 times the equivalent of the alkyl chain and its derivatives, and intermediate B is obtained after substitution reaction;

[0014] The preparation route is as follows:

[0015]

[0016] S3, mixing the intermediate B and 9,9-dimethylacridine in a molar ratio of 1:(1-2), using acetonitrile as a solvent and tetrabutylammonium bromide as a phase transfer catalyst, adding sodium hydroxide, and obtaining a high entropy charge transfer luminescent material after the reaction;

[0017] The preparation route is as follows:

[0018]

[0019] Preferably, the general structural formula of the alkyl chain and its derivatives is as follows:

[0020]

[0021] Wherein, X is any one of F, Cl, Br or I; n≥6; R1 is one or more of halogen, amide, and ether bond.

[0022] Preferably, in step S1, the molar ratio of bisphenol S to p-toluenesulfonyl chloride is (1-1.2):1.

[0023] Preferably, in step S2, the molar ratio of the intermediate A to the alkyl chain and its derivatives is 1:(1-1.2).

[0024] Preferably, in step S3, the molar ratio of intermediate B to 9,9-dimethylacridine is 1:(1-1.2).

[0025] An application of a high entropy charge transfer luminescent material. The high entropy charge transfer luminescent material is used as a luminescent material in the field of organic light emitting diodes and perovskite light emitting diodes.

[0026] After adopting the above technical scheme, the present invention has the following beneficial effects: the high entropy charge transfer luminescent material of the present invention can increase the disorder of charge transfer, and at the same time has a passivation group of the structure of amide and its derivatives, which is beneficial to promote the regulation of light-emitting channels and morphology; the high entropy charge transfer luminescent material has important application value in the field of organic light-emitting diodes and perovskite light-emitting diodes. In addition, in step S1 of the present invention, p-toluenesulfonyl chloride is used to provide a pseudo-halogen group, and the reaction activity of the pseudo-halogen group is greater than that of the halogen, which is beneficial to the subsequent reaction; in step S1, bisphenol S is slightly excessive relative to p-toluenesulfonyl chloride, and the excess of bisphenol S can promote the unilateral substitution of the pseudo-halogen, which is beneficial to inhibit the occurrence of side reactions. In step S2, Williamson reaction is used for substitution, and the reaction conditions of the reaction are mild, and the reaction is rapid, with few by-products. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 is the hydrogen nuclear magnetic resonance spectrum of the target product prepared in Example 1 of the present invention;

[0028] Figure 2 is the carbon nuclear magnetic resonance spectrum of the target product prepared in Example 1 of the present invention;

[0029] Figure 3 is the hydrogen nuclear magnetic resonance spectrum of the target product prepared in Example 2 of the present invention;

[0030] Figure 4 is the carbon nuclear magnetic resonance spectrum of the target product prepared in Example 2 of the present invention;

[0031] Figure 5 is the hydrogen nuclear magnetic resonance spectrum of the target product prepared in Example 3 of the present invention;

[0032] Figure 6 This is the carbon NMR spectrum of the target product prepared in Example 3 of the present invention. DETAILED DESCRIPTION

[0033] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0034] like Figures 1 to 6 shown.

[0035] Example 1

[0036] S1. Weigh 2.5g (10mmol) of bisphenol S in a 50ml three-necked flask, add 10ml of triethylamine (Et3N) to dissolve, weigh 0.1g of 4-dimethylpyridine (DMAP) and add it to the three-necked flask, and place it on a stirring table with magnetic stirring at 35°C. Subsequently, take 1.9g (10mmol) of p-toluenesulfonyl chloride in a 50ml beaker, add 10ml of dichloromethane (DCM) to fully dissolve it, and use a syringe to slowly drip the dichloromethane (DCM) solution into the three-necked flask, and react at 35°C for 48h. After the reaction is completed, use a saturated sodium carbonate solution for separation, and then use a chromatography column for purification, and the developing solvent is a mixed solution of ethyl acetate and petroleum ether (petroleum ether: ethyl acetate = 5:1). Obtain intermediate A.

[0037] S2. Prepare intermediate B in one pot by Williamson reaction. Take 3.8g (10mmol) of intermediate A, 2.88g (12mmol) of alkyl chain and its derivative RX, 3.31g (24mmol) of K2CO3, add 50ml of acetone to dissolve, place the reaction on a magnetic stirrer, and react at room temperature for 12h. After the reaction is completed, purify using a chromatography column, and the developing solvent is a mixed solution of dichloromethane and petroleum ether (petroleum ether: dichloromethane = 4:1). Obtain intermediate B.

[0038] The structural formula of the alkyl chain and its derivative RX is shown below:

[0039]

[0040] S3, weigh 5.5g (10mmol) of intermediate B, add 50ml acetonitrile and stir to dissolve, add 1.5g NaOH, 0.5g tetrabutylammonium bromide (TBAB), stir at room temperature for 10min, then add 2.09g (10mmol) of 9,9-dimethylacridine, heat to 75°C, and react for 24h. After the reaction is completed, purify using a chromatography column, and the developing solvent is a mixed solution of dichloromethane and petroleum ether (petroleum ether: dichloromethane = 4:1). Obtain the target product, the structural formula is as follows:

[0041]

[0042] Example 2

[0043] S1. Weigh 3.0g bisphenol S (12mmol) in a 50ml three-necked flask, add 10ml triethylamine (Et3N) to dissolve, weigh 0.1g 4-dimethylpyridine (DMAP) and add it to the three-necked flask, and place it on a stirring table with magnetic stirring at 45°C. Subsequently, take 1.9g p-toluenesulfonyl chloride (10mmol) in a 50ml beaker, add 10ml dichloromethane (DCM) to fully dissolve it, and use a syringe to slowly drip the dichloromethane (DCM) solution into the three-necked flask, and react at 45°C for 24h. After the reaction is completed, use a saturated sodium carbonate solution for separation, and then use a chromatography column for purification, and the developing solvent is a mixed solution of ethyl acetate and petroleum ether (petroleum ether: ethyl acetate = 5:1). Obtain intermediate A.

[0044] S2. Prepare intermediate B in one pot by Williamson reaction. Take 3.8g (10mmol) of intermediate A, 3.1g (10mmol) of alkyl chain and its derivative RX, 1.38g (10mmol) of K2CO3, add 50ml of acetone to dissolve, place the reaction on a magnetic stirrer, and react at room temperature for 24h. After the reaction is completed, purify using a chromatography column, and the developing solvent is a mixed solution of ethyl acetate and petroleum ether (petroleum ether: ethyl acetate = 8:1). Obtain intermediate B.

[0045] The structural formula of the alkyl chain and its derivative RX is shown below:

[0046]

[0047] S3, weigh 6.18g (10mmol) of intermediate B, add 50ml acetonitrile and stir to dissolve, add 1.5g NaOH, 0.5g tetrabutylammonium bromide (TBAB), stir at room temperature for 10min, then add 2.51g (12mmol) of 9,9-dimethylacridine, heat to 85°C, and react for 12h. After the reaction is completed, purify using a chromatography column, and the developing solvent is a mixed solution of ethyl acetate and petroleum ether (petroleum ether: ethyl acetate = 6:1). Obtain the target product, the structural formula is as follows:

[0048]

[0049] Example 3

[0050] S1. Weigh 2.75g of bisphenol S (11mmol) in a 50ml three-necked flask, add 10ml of triethylamine (Et3N) to dissolve, weigh 0.1g of 4-dimethylpyridine (DMAP) and add it to the three-necked flask, and place it on a stirring table with magnetic stirring at 40°C. Subsequently, take 1.9g of p-toluenesulfonyl chloride (10mmol) in a 50ml beaker, add 10ml of dichloromethane (DCM) to fully dissolve it, and use a syringe to slowly drip the dichloromethane (DCM) solution into the three-necked flask, and react at 40°C for 36h. After the reaction is completed, use a saturated sodium carbonate solution for separation, and then use a chromatography column for purification, and the developing solvent is a mixed solution of ethyl acetate and petroleum ether (petroleum ether: ethyl acetate = 5:1). Obtain intermediate A.

[0051] S2. Prepare intermediate B in one pot by Williamson reaction. Take 3.8g (10mmol) of intermediate A, 3.07g (11mmol) of alkyl chain and its derivative RX, 2.28g (16.5mmol) of K2CO3, add 50ml of acetone to dissolve, place the reaction on a magnetic stirrer, and react at room temperature for 18h. After the reaction is completed, purify using a chromatography column, and the developing solvent is a mixed solution of ethyl acetate and petroleum ether (petroleum ether: ethyl acetate = 8:1). Obtain intermediate B.

[0052] The structural formula of the alkyl chain and its derivative RX is shown below:

[0053]

[0054] S3, weigh 5.86g (10mmol) of intermediate B, add 50ml acetonitrile and stir to dissolve, add 1.5g NaOH, 0.5g tetrabutylammonium bromide (TBAB), stir at room temperature for 10min, then add 2.30g (11mmol) of 9,9-dimethylacridine, heat to 80°C, and react for 18h. After the reaction is completed, purify using a chromatography column, and the developing solvent is a mixed solution of ethyl acetate and petroleum ether (petroleum ether: ethyl acetate = 6:1). Obtain the target product, the structural formula is as follows:

[0055]

[0056] The above is only a preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed by the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. A high entropy charge transfer luminescent material, characterized in that: The high entropy charge transfer luminescent material comprises a diphenyl sulfone acceptor group and a 9,9-dimethyl acridine donor group. The diphenyl sulfone acceptor group and the 9,9-dimethyl acridine donor group are used as charge transfer skeletons and are modified by alkyl chains and derivative groups thereof. The structural formula of the high entropy charge transfer luminescent material is shown below: Wherein, R is a long alkyl chain embedded amide and its derivatives, and the length of the alkyl chain is carbon number ≥ 6.

2. A high entropy charge transfer luminescent material according to claim 1, characterized in that: The long chain of R contains one or more of halogen, amide, and ether bond.

3. A method for preparing a high entropy charge transfer luminescent material as claimed in any one of claims 1 to 2, characterized in that: The following steps are involved: S1, bisphenol S and p-toluenesulfonyl chloride are mixed in a molar ratio of (1-2):1, and then dichloromethane is used as a solvent, 4-lutidine is used as a catalyst, triethylamine is added, and the reaction is performed to obtain an intermediate A; S2. Using Williamson reaction, the intermediate A and the alkyl chain and its derivatives are mixed in a molar ratio of 1:(1-2), and then acetone is used as a solvent, and potassium carbonate is added in an amount of 1-2 times the equivalent of the alkyl chain and its derivatives, and intermediate B is obtained after substitution reaction; S3. The intermediate B and 9,9-dimethylacridine are mixed in a molar ratio of 1:(1-2), and then acetonitrile is used as a solvent, tetrabutylammonium bromide is used as a phase transfer catalyst, and sodium hydroxide is added to obtain a high entropy charge transfer luminescent material after the reaction.

4. The method for preparing a high entropy charge transfer luminescent material according to claim 3, characterized in that: The general structural formula of the alkyl chain and its derivatives is shown below: Wherein, X is any one of F, Cl, Br or I; n≥6; R1 is one or more of halogen, amide, and ether bond.

5. The method for preparing a high entropy charge transfer luminescent material according to claim 3, characterized in that: In step S1, the molar ratio of bisphenol S to p-toluenesulfonyl chloride is (1-1.2):

1.

6. The method for preparing a high entropy charge transfer luminescent material according to claim 3, characterized in that: In step S2, the molar ratio of intermediate A to alkyl chain and its derivative is 1:(1-1.2).

7. The method for preparing a high entropy charge transfer luminescent material according to claim 3, characterized in that: In step S3, the molar ratio of intermediate B to 9,9-dimethylacridine is 1:(1-1.2).

8. An application of the high entropy charge transfer luminescent material according to any one of claims 1 to 2, characterized in that: The high entropy charge transfer luminescent material is used as a luminescent material in the fields of organic light emitting diodes and perovskite light emitting diodes.

Images