CN-121991100-A - Asymmetric chiral luminescent material based on benzodiazole and preparation method and application thereof

Abstract

The invention discloses an asymmetric chiral luminescent material based on benzodiazole, a preparation method and application thereof, belonging to the technical field of organic photoelectric semiconductors, the luminescent material is of an asymmetric structure, has better chiral absorption and emission characteristics, and electron coupling between excited states is inhibited by symmetry break between chromophores in a spiral pi system. The chiral luminescent material has the advantages of simple synthetic route, controllable energy level, excellent luminescent behavior, low cost and good Circular Polarized Luminescence (CPL) signal characteristic, and can be widely applied to the fields of chiral filters, polarizers, sensor switches, organic photoelectric devices and the like.

Inventors

• FU NINA
• Jia Langlang
• ZHAO BAOMIN
• MU HUI

Assignees

• 南京邮电大学

Dates

Publication Date

20260508

Application Date

20260310

Claims (9)

1. 1. The asymmetric chiral luminescent material based on the benzodiazole is characterized by having the following structural general formula: ; Wherein, the R 1 is taken from unsubstituted C1-C24 straight chain alkyl, unsubstituted C1-C24 branched chain alkyl, unsubstituted phenyl or phenyl containing straight or branched chain alkyl; r 2 is selected from unsubstituted C1-C24 linear alkyl, unsubstituted C1-C24 branched alkyl, unsubstituted phenyl or phenyl containing linear or branched alkyl, m is an integer ranging from 0 to 3; X is O, S, se, N-R 3 , or ; R 3 is a substituted or unsubstituted C1-C24 straight-chain alkyl group, a substituted or unsubstituted C1-C24 branched-chain alkyl group, an unsubstituted C3-C24-containing alkoxy chain, an aryl group with 1-2C 1-C24 straight-chain alkyl groups or C1-C24 branched-chain alkyl groups; Y is selected from unsubstituted C1-C24 straight-chain alkyl, unsubstituted C1-C24 branched-chain alkyl, unsubstituted phenyl or CN; Ar is selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C4-C30 heteroaryl; by substituted is meant that at least one hydrogen of the substituent or compound is replaced with deuterium, halogen, cyano.
2. 2. The luminescent material according to claim 1, wherein the luminescent material has a general structural formula of one of the following structures: ; ; Wherein Ar and R 2 are one of the following structures: 。
3. 3. the luminescent material according to claim 1, wherein the luminescent material is one of the following structures: ; ; ; ; ; ; ; ; ; ; ; ; 。
4. 4. The luminescent material as claimed in claim 1, wherein, R 1 is taken from unsubstituted C1 to C24 linear alkyl; ar is selected from unsubstituted C6-C30 aryl or unsubstituted C4-C30 heteroaryl; R 2 is taken from unsubstituted C1-C24 linear alkyl and unsubstituted phenyl; x is O, S, se or N-R 3 ,R 3 is taken from unsubstituted C1-C24 straight chain alkyl.
5. 5. The luminescent material according to claim 1, wherein Ar and R 2 are one of the following structures: ; Wherein R 2 is unsubstituted phenyl or unsubstituted C1-C24 linear alkyl.
6. 6. The luminescent material according to claim 1, wherein the luminescent material is one of the following structures: ; ; ; ; 。
7. 7. the method for preparing a luminescent material as claimed in claim 1, comprising the steps of: (1) When X is O, S, se or N-R 3 , the preparation method comprises the following steps: step 1, synthesizing a compound II, wherein the reaction formula is as follows: ; step 1, under the protection of nitrogen or argon, using N, N-dimethylformamide as an organic solvent, wherein the reaction temperature is normal temperature, and the reaction time is 8-12 hours; Step 2, synthesizing a compound III, wherein the reaction formula is as follows: ; Step 2, reacting under the protection of nitrogen or argon and under the conditions of a catalyst, potassium carbonate, TBAB and a solvent, wherein the solvent is a mixture of toluene and water, the reaction temperature is 100-110 ℃, and the reaction time is 4-8 hours; (2) When X is The preparation method comprises the following steps: step I, synthesizing a compound IV, wherein the reaction formula is as follows: ; The method comprises the following steps of step I, carrying out under the protection of nitrogen or argon, wherein an organic solvent is N, N-dimethylformamide, the reaction temperature is normal temperature, and the reaction time is 8-12 hours; step II, synthesizing a compound V, wherein the reaction formula is as follows: ; Step II, under the protection of nitrogen or argon, under the conditions of a catalyst, potassium carbonate, TBAB and anhydrous toluene serving as an organic solvent, wherein the reaction temperature is 100-110 ℃ and the reaction time is 4-8 hours; the catalyst in step 2 and step II was Pd132, pd (dppf) Cl 2 DCM.
8. 8. A process for producing a luminescent material as claimed in claim 7, characterized in that, In step 1, compound I is reacted with The molar ratio of (2) is 1 (0.9-2.5); in step 2, compound II is reacted with The molar ratio of (1.5-2.5); step I, compounds IV and The molar ratio of (1.5-2.5); step II, compounds V and The molar ratio of (2) is 1 (1.5-2.5).
9. 9. Use of a luminescent material according to claim 1, for optoelectronic device or drug design and targeted therapy.

Description

Asymmetric chiral luminescent material based on benzodiazole and preparation method and application thereof Technical Field The invention belongs to the technical field of organic photoelectric semiconductors, and particularly relates to an asymmetric chiral luminescent material based on benzodiazole, and a preparation method and application thereof. Background The organic photoelectric semiconductor molecular material is a material system based on organic semiconductor molecules with designable structure and photoelectric property, and is the front direction of material science research. In recent years, with the continuous development of material systems, the organic circuit constructed by the method has great application potential in the fields of flexible display, bionic electronic skin, bionic visual system, bionic nervous system and the like, but has become one of important functional systems for constructing flexible electronic devices, and brings brand new opportunities for development of electronics. Chiral organic semiconductors have attracted extensive research interest in the organic photovoltaic field due to their novel properties. The chiral introduction into the organic semiconductor material can regulate and control the aggregation state structure, influence the carrier transportation and the performance of the photoelectric device, and promote the generation and development of circularly polarized light direct emitting and detecting materials and devices. The chiral organic semiconductor has wide application prospect in the fields of 3D display, quantum communication, information storage, processing and the like. Compared with the traditional organic photoelectric semiconductor, the chiral photoelectric semiconductor can enable electrons to move in a spiral mode, greatly improves the performance of the organic light emitting diode, and brings better display screens for televisions, smart phones and the like. In addition, the development of next-generation computing technologies such as spintronics and quantum computing is expected to be promoted. Disclosure of Invention In order to solve the defects of the prior art, the invention provides an asymmetric chiral luminescent material based on benzodiazole, a preparation method and application thereof, the preparation method of the invention can obtain chiral organic semiconductors which have more beneficial performance, richer structure and easier functionalization and large-scale production. In a first aspect, the invention provides an asymmetric chiral luminescent material based on benzodiazole, wherein the luminescent material has the following structural general formula: Wherein, the R 1 is taken from unsubstituted C1-C24 straight chain alkyl, unsubstituted C1-C24 branched chain alkyl, unsubstituted phenyl or phenyl containing straight or branched chain alkyl; r 2 is selected from unsubstituted C1-C24 linear alkyl, unsubstituted C1-C24 branched alkyl, unsubstituted phenyl or phenyl containing linear or branched alkyl, m is an integer ranging from 0 to 3; X is O, S, se, N-R 3, or ; R 3 is a substituted or unsubstituted C1-C24 straight-chain alkyl group, a substituted or unsubstituted C1-C24 branched-chain alkyl group, an unsubstituted C3-C24-containing alkoxy chain, an aryl group with 1-2C 1-C24 straight-chain alkyl groups or C1-C24 branched-chain alkyl groups; Y is selected from unsubstituted C1-C24 straight-chain alkyl, unsubstituted C1-C24 branched-chain alkyl, unsubstituted phenyl or CN; Ar is selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C4-C30 heteroaryl; by substituted is meant that at least one hydrogen of the substituent or compound is replaced with deuterium, halogen, cyano. Further, the structural general formula of the luminescent material is one of the following structures: ; Wherein Ar and R 2 are one of the following structures: 。 further, the luminescent material is one of the following structures: 。 Further, R 1 is taken from unsubstituted C1-C24 linear alkyl, ar is taken from unsubstituted C6-C30 aryl or unsubstituted C4-C30 heteroaryl, R 2 is taken from unsubstituted C1-C24 linear alkyl, unsubstituted phenyl, X is O, S, se or N-R 3,R3 is taken from unsubstituted C1-C24 linear alkyl. Further, ar and R 2 are one of the following structures: Wherein R 2 is unsubstituted phenyl or unsubstituted C1-C24 linear alkyl. Further, the luminescent material is one of the following structures: 。 in a second aspect, the present invention provides a method for preparing an asymmetric chiral luminescent material based on benzodiazole, comprising the steps of: (1) When X is O, S, se or N-R 3, the preparation method comprises the following steps: step 1, synthesizing a compound II, wherein the reaction formula is as follows: Step 1 is performed under the protection of nitrogen or argon, and in step 1, the compound I and the compound I are mixed The molar ratio of (1) is (0.9-2.5), the organic solvent