Circularly polarized luminescent material with chiral optical waveguide performance and application thereof

Abstract

The invention discloses a circularly polarized luminescent material with chiral optical waveguide performance and application thereof. According to the invention, the chiral AIE micromolecules are utilized to form the chiral transistor through self-assembly, and the chiral transistor has relatively strong circular polarization performance; when the chiral transistor is used for an optical waveguide experiment, it is found that chiral light is transmitted along the transistor, and chiral optical signals output by the chiral light are consistent in the front-back direction. The organic supramolecular crystal material with circularly polarized luminescence and chiral optical waveguide performance provided by the invention has new discovery and combination in the field of chiral optics, has potential application value in optical devices and optical application directions, is simple in preparation method, provides a new way and thinking for researching novel chiral supramolecular functional materials, and has wide application prospects. And a novel effective functional material is provided for chiral optical information transmission.

Description

Technical Field

[0001] The present invention relates to a circularly polarized luminescent material with chiral optical waveguide properties and its applications, belonging to the field of circularly polarized luminescence. Background Art

[0002] Circularly polarized luminescence (CPL) materials have unique advantages such as high light energy utilization efficiency, low energy consumption, and high imaging contrast, showing great application prospects in scientific fields such as information encryption, light-emitting diodes, liquid crystal displays, anti-counterfeiting materials, nonlinear optics, biological probes, and three-dimensional displays. Supramolecular materials constructed by intermolecular or intramolecular non-covalent interactions (such as hydrogen bonds, van der Waals forces, electrostatic interactions, halogen bonds, π-π stacking, hydrophilic-hydrophobic interactions, etc.) have become an effective way to construct circularly polarized luminescence systems. From molecules to supramolecules, supramolecular materials in various macroscopic states such as helical fibers, nanoparticles, nanoribbons, and nanotubes can be constructed, bringing new opportunities to the field of circularly polarized luminescence. However, simultaneously obtaining a high quantum yield (φf) and a large absolute emission asymmetry factor (g lum ) for CPL supramolecular materials remains an urgent problem to be solved. Supramolecular crystals formed by non-covalent bonding provide new ideas for this problem due to their outstanding optical properties.

[0003] As a medium for transmitting light waves, optical waveguides play an important role in optical sensing and optical signal processing. Optical waveguides based on chiral media have good application prospects in related fields such as micro-nano optical devices, optical coupling, and optical signal communication due to their optical rotation properties and polarization manipulation capabilities. Chiral dielectric materials generally include crystals with chiral small molecules, materials with chiral structural monomers, and materials with chiral geometric arrangements. However, due to the irregularity of the materials and the fixed vibration plane of linearly polarized light that does not rotate, the transmission of linearly polarized light does not have directionality. Therefore, exploring new chiral supramolecular materials as polarizers to transmit chiral light has become a new research goal. Based on the above research problems, the present invention has obtained supramolecular chiral transistors with CPL characteristics through the self-assembly of simple chiral fluorescent molecules. As a medium for light wave transmission, chiral transistors output linearly polarized light in the form of circularly polarized light. When a beam of linearly polarized light irradiates the chiral transistor, its inherent CPL signal will be generated. When CPL light is transmitted through the chiral transistor and detected at each port of the transistor, the CPL signal will be detected. The transmission of circularly polarized light is achieved through enantiomeric chiral transistors, and it is believed that this property can be used as a new type of chiral fiber optic sensor. Moreover, both M-configured and P-configured chiral transistors have corresponding circularly polarized light, providing a feasible path for the encryption of fiber optic sensors. Summary of the Invention

[0004] The object of the present invention is to provide a circularly polarized luminescent material with chiral optical waveguide properties. The present invention uses chiral AIE organic small molecules R–TPE-CSC or S–TPE-CSC as assembly units, and under the conditions of a specific solvent, forms self-assembled bodies with a nanosphere structure through self-assembly; after a certain aging time, the self-assembled bodies with a nanosphere structure fuse to form fibrous organic transistors, and at the same time, it is found that such transistors have strong circularly polarized light properties. The present invention uses such transistors to conduct chiral optical waveguide experiments and finds that the transistors have good chiral light transmission functions and can be used as optical information transmission tools.

[0005] The chiral AIE organic small molecules R–TPE-CSC or S–TPE-CSC used in the present invention are tetraphenylethylene derivatives, and the structural formulas of the chiral AIE organic small molecules R–TPE-CSC or S–TPE-CSC are shown as follows:

[0006]

[0007] The synthesis method of R–TPE-CSC is: under the condition of the presence of triethylamine, TPE-4OH reacts with (1R)-(+)-10-camphorsulfonyl chloride through an acyl chloride reaction;

[0008] The acyl chloride reaction is carried out in dichloromethane;

[0009] Under ice bath conditions, the (1R)-(+)-10-camphorsulfonyl chloride solution is dropped into the TPE-4OH solution, and stirred at room temperature for 3 - 12 hours.

[0010] The synthesis method of S–TPE-CSC is: under the condition of the presence of triethylamine, TPE-4OH reacts with (1S)-(+)-10-camphorsulfonyl chloride through an acyl chloride reaction;

[0011] The acyl chloride reaction is carried out in dichloromethane;

[0012] Under ice bath conditions, the (1S)-(+)-10-camphorsulfonyl chloride solution is dropped into the TPE-4OH solution, and stirred at room temperature for 3 - 12 hours.

[0013] The application of the chiral AIE organic small molecules provided by the present invention in the preparation of circularly polarized luminescent materials with chiral optical waveguide properties also belongs to the protection scope of the present invention.

[0014] The circularly polarized luminescent material with chiral optical waveguide properties provided by the present invention is self-assembled from the chiral AIE organic small molecules as assembly units.

[0015] The circularly polarized luminescent material of the present invention has circularly polarized light properties and chiral light transmission functions;

[0016] The circularly polarized luminescent material of the present invention is a chiral supramolecular crystal material, and its morphology observed by SEM is a fibrous transistor.

[0017] The present invention also provides a preparation method of the circularly polarized luminescent material, comprising the following steps:

[0018] Using the chiral AIE organic small molecule as an assembly unit, in a specific solvent, a self-assembled body with a nanosphere structure is formed by self-assembly; after aging, the self-assembled body of the nanostructure fuses to form a fibrous organic transistor, which is the circularly polarized luminescent material.

[0019] Preferably, the specific solvent is a methanol-chloroform mixed system, and the volume ratio of the two is 7:3 - 9:1, preferably 7:3, 8:2 or any range value composed of the two;

[0020] Preferably, the assembly concentration of the chiral AIE organic small molecule is 1 - 3 mg / mL.

[0021] Preferably, the aging time is more than 48 hours.

[0022] The circularly polarized luminescent material with chiral optical waveguide properties provided by the present invention is a chiral supramolecular crystal material with circularly polarized light properties and chiral optical waveguide applications. It has the application prospect of chiral supramolecular crystal materials in the field of light-emitting devices, and also has the application prospect of chiral supramolecular crystal materials in the fields of optical information transmission and encryption storage, catalysis, and gas adsorption and separation. The application of chiral optical waveguides also provides effective application value for chiral optical information transmission.

[0023] The present invention has the following technical effects:

[0024] (1) The present invention prepares a fibrous organic supramolecular transistor material by self-assembly and aging means of organic AIE small molecules. This is a novel chiral supramolecular crystal material, and it is found by detection that the transistor has strong circularly polarized luminescent properties.

[0025] (2) Through the process of aging in time, the nanospherical self-assembled body fuses and grows into a transistor material, which is a novel chiral crystal material and has potential application value in the fields of catalysis, adsorption and separation, etc.

[0026] (3) The chiral supramolecular transistor prepared by the present invention can perform chiral optical information transmission, solves the problem of chiral optical information transmission, and can be used as a chiral optical fiber material for optical information storage and encryption.

[0027] The organic supramolecular crystal material with circularly polarized luminescence and chiral optical waveguide properties provided by the present invention has new discoveries and combinations in the field of chiral optics, has potential application value in the direction of optical devices and optical applications, and has a simple preparation method, providing a new way of thinking for the research of new chiral supramolecular functional materials, and also providing a new and effective functional material for chiral optical information transmission. Description of the Drawings

[0028] Figure 1 SEM image of the process of forming a supramolecular transistor by the aging of chiral AIE organic small molecule R–TPE-CSC supramolecular assembly.

[0029] Figure 2 Optical microscope image of the supramolecular transistor formed by the aging of chiral AIE organic small molecule R–TPE-CSC supramolecular assembly.

[0030] Figure 3 Macroscopic state diagram of the assembly finally formed by chiral AIE organic small molecule R–TPE-CSC in mixed solvents with different ratios.

[0031] Figure 4 CPL spectrum of the supramolecular transistor formed by chiral AIE organic small molecules R–TPE-CSC and S–TPE-CSC in the state of methanol:chloroform = 8:2.

[0032] Figure 5 Fluorescence microscope of the supramolecular transistor formed by chiral AIE organic small molecule R–TPE-CSC in the state of methanol:chloroform = 8:2.

[0033] Figure 6 Single crystal structure analysis of the supramolecular transistor formed by chiral AIE organic small molecule R–TPE-CSC in the state of methanol:chloroform = 8:2.

[0034] Figure 7 Optical chiral waveguide data of the supramolecular transistor formed by chiral AIE organic small molecules R–TPE-CSC and S–TPE-CSC in the state of methanol:chloroform = 8:2.

[0035] Figure 8 1H nuclear magnetic resonance spectrum of chiral AIE organic small molecule R–TPE-CSC.

[0036] Figure 9 1H nuclear magnetic resonance spectrum of chiral AIE organic small molecule S–TPE-CSC. Detailed Description of the Invention

[0037] The present invention will be further described in detail below in conjunction with specific embodiments. The provided embodiments are only for clarifying the present invention and not for limiting the scope of the present invention. The following provided embodiments can be used as a guide for those of ordinary skill in the art to make further improvements and do not constitute any limitation to the present invention in any way.

[0038] In the following experimental methods of the embodiments, unless otherwise specified, they are all conventional methods and are carried out according to the techniques or conditions described in the literature in this field or according to the product instructions. The materials, reagents, etc. used in the following embodiments, unless otherwise specified, can all be obtained from commercial channels.

[0039] Example 1. Synthesis of S–TPE-CSC

[0040] Dissolve TPE-4OH (tetrahydroxytetraphenylethylene) (198.22 mg, 0.5 mmol) (purchased from Jilin Yanshen Technology Co., Ltd.) in 100 mL of dichloromethane, and add triethylamine (252.98 mg, 2.5 mmol). Dissolve (1S)-(+)-10-camphorsulfonyl chloride (626.85 mg, 2.5 mmol) (purchased from InnoChem Co., Ltd.) in 10 ml of dichloromethane, and drop it into the TPE-4OH solution through a constant-pressure dropping funnel under an ice bath condition at 0 °C, and stir at room temperature for 4 hours. Then concentrate it to 20 ml by rotary evaporation, and then drop it into 500 ml of ethanol, and filter out a large amount of white precipitate formed by ultrasonic precipitation with a filtering device. 600 mg of white solid powder is obtained, and the yield is 95.8%. The structure characterization data is as Figure 9 shown.

[0041]

[0042] Example 2. Synthesis of R–TPE-CSC

[0043] Dissolve TPE-4OH (198.22 mg, 0.5 mmol) (purchased from Jilin Yanshen Technology Co., Ltd.) in 100 mL of dichloromethane, and add triethylamine (252.98 mg, 2.5 mmol). Dissolve (1R)-(+)-10-camphorsulfonyl chloride (626.85 mg, 2.5 mmol) (purchased from InnoChem Co., Ltd.) in 10 ml of dichloromethane, and drop it into the TPE-4OH solution through a constant-pressure dropping funnel under an ice bath condition at 0 °C, and stir at room temperature for 4 hours. Then concentrate it to 20 ml by rotary evaporation, and then drop it into 500 ml of ethanol, and filter out a large amount of white precipitate formed by ultrasonic precipitation with a filtering device. 606 mg of white solid powder is obtained, and the yield is 96.7%. The structure characterization data is as Figure 8 shown.

[0044]

[0045] Example 3

[0046] 1.5 mg of chiral AIE organic small molecule R–TPE-CSC or S–TPE-CSC was subjected to supramolecular self-assembly in 1 mL of a mixed solvent, and the mixed solvent was methanol: chloroform (CH 3 OH:CHCl 3 ), and the solvent (volume) ratio was 8:2. Through an aging time of 12 hours, it can be seen by SEM that the self-assembled morphology is spherical nanoparticles; after aging for 36 hours and 48 hours, it can be seen that the nanospheres fuse into long strips; finally, after the aging process of 72 hours, a fibrous transistor-like shape is formed, as shown in Figure 1 shown. The tubular characteristics can also be directly observed through an optical microscope, as shown in Figure 2 shown.

[0047] Through the self-assembly aging process, an organic supramolecular chiral crystal material was obtained, and the macroscopic states of different solvent ratios are shown in Figure 3 shown, a bright and shiny fibrous supramolecular crystal material. It can be seen that at different solvent ratios, only (CH 3 OH:CHCl 3 ), with a volume ratio of 9:1 - 7:3, can obtain a fibrous supramolecular crystal material. By circular polarization spectroscopy and detecting the above-mentioned chiral supramolecular transistor material, it was found that the supramolecular crystal material of the present invention has strong circularly polarized luminescence properties, as shown in Figure 4 shown. A blue light CPL signal was observed near the emission wavelength of 410 nm. At the same time, it was observed by fluorescence microscopy that the chiral supramolecular transistor has blue light emission, as shown in Figure 5 shown. Figure 6 Single crystal analysis of the transistor was shown, thereby verifying its crystal configuration.

[0048] The chiral supramolecular transistor of the present invention shows good chiral optical information and has potential application value in optical information encryption and 3D display. In addition, chiral optical waveguide experiments were carried out on the transistor of the present invention, and it was found that it has good chiral light transmission performance and can be used as a good chiral light transmission material, as shown in Figure 7 shown. It shows that chiral optical waveguide experiments were carried out on the chiral transistor constructed by R–TPE-CSC or S–TPE-CSC, and there is a slight loss of chiral light during the transmission process. M1 is the chiral crystal of the left-handed configuration corresponding to R–TPE-CSC, and P1 is the chiral crystal of the right-handed configuration corresponding to S–TPE-CSC, indicating that the chiral transistor of the present invention is not only an excellent circularly polarized luminescence material but also a new type of chiral optical waveguide material, and at the same time has good chiral optical activity and optical properties, providing a broad prospect for the further application of this material.

[0049] Example 4

[0050] 3 mg of chiral AIE organic small molecule R–TPE-CSC or S–TPE-CSC was subjected to supramolecular self-assembly in 1 mL of a mixed solvent, and the mixed solvent was methanol: chloroform (CH 3 OH:CHCl 3 ), and the solvent (volume) ratio was 8:2. After the aging process, a fibrous transistor-like shape was also formed, and at the same time, it also had chiral optical waveguide properties.

[0051] Comparative Example 1

[0052] 1.5 mg of chiral AIE organic small molecule R–TPE-CSC or S–TPE-CSC was subjected to supramolecular self-assembly in 1 mL of a mixed solvent, and the mixed solvent was methanol: chloroform (CH 3 OH:CHCl 3 ), and the solvent (volume) ratio was 6:4. This system was in a solution state, and after the aging process, it still remained in the solution state, and no assembly precipitated.

[0053] Comparative Example 2

[0054] 1.5 mg of chiral AIE organic small molecule R–TPE-CSC or S–TPE-CSC was subjected to supramolecular self-assembly in 1 mL of an organic solvent, and the organic solvent was chloroform (CHCl 3 ). This system was in a solution state, and after the aging process, it still remained in the solution state, and no assembly precipitated.

[0055] Comparative Example 3

[0056] 1.5 mg of chiral AIE organic small molecule R–TPE-CSC or S–TPE-CSC was subjected to supramolecular self-assembly in 1 mL of an organic solvent, and the organic solvent was methanol (CH 3 OH). The solvent could not completely dissolve the molecule, and the system was in a mixed state, and uniform supramolecular assembly could not be carried out.

[0057] Comparative Example 4

[0058] 1.5 mg of chiral AIE organic small molecule R–TPE-CSC or S–TPE-CSC was subjected to supramolecular self-assembly in 1 mL of a mixed solvent, and the mixed solvent was DMF: water, and the solvent (volume) ratio was 2:8. This system was always in an assembled state, without an aging process, and no fibrous transistor-like shape was formed.

[0059] The supramolecular assembly material constructed by the chiral AIE organic small molecule R–TPE-CSC or S–TPE-CSC provided by the present invention is a rare crystal material, which mainly depends on the regulation of specific solvent systems and appropriate assembly conditions such as assembly concentration. Moreover, the formed supramolecular crystal material has a fiber tubular structure and excellent circular polarization performance. By using this novel chiral transistor, chiral optical waveguide performance can be achieved, making it a transmission channel for chiral light, and it can be used as a chiral optical fiber for further applications. The novel supramolecular crystal material of the present invention is a rare crystal material with circularly polarized light performance, which can be further used for the application development of optical information encryption storage and optical devices, etc. The chiral optical waveguide performance also provides a new path and choice for the development and evolution of this chiral crystal material, solving the problem that it is difficult for chiral light to be effectively transmitted within the material.

[0060] The present invention has been described in detail above. For those skilled in the art, without departing from the purpose and scope of the present invention and without unnecessary experiments, the present invention can be implemented within a relatively wide range under equivalent parameters, concentrations and conditions. Although specific embodiments of the present invention are given, it should be understood that the present invention can be further improved. In short, according to the principle of the present invention, this application intends to cover any changes, uses or improvements to the present invention, including changes made with conventional techniques known in the art that depart from the scope disclosed in this application.

Claims

1. A chiral AIE organic small molecule R-TPE-CSC or S-TPE-CSC, the structural formula of which is as follows:

2. Use of the chiral AIE organic small molecule according to claim 1 in the preparation of circularly polarized luminescent materials with chiral optical waveguide properties.

3. A circularly polarized luminescent material with chiral light waveguide performance, which is self-assembled by using the chiral AIE organic small molecule as an assembly unit according to claim 1.

4. The circularly polarized luminescent material according to claim 3, characterized in that: The circularly polarized luminescent material has circularly polarized light performance and chiral light transmission function.

5. The method for preparing the circularly polarized luminescent material according to claim 3 or 4, comprising the following steps: The chiral AIE organic small molecule is used as an assembly unit to form a self-assembled body with a nanosphere structure in a specific solvent by self-assembly; after aging, the self-assembled body of the nanostructure fuses to form a fibrous organic transistor, which is the circularly polarized luminescent material.

6. The preparation method according to claim 5, characterized in that: The specific solvent is a methanol-chloroform mixed system, and the volume ratio of the two is 7:3-9:

1.

7. The preparation method according to claim 5 or 6, characterized in that: The assembly concentration of the chiral AIE organic small molecule is 1-3 mg / mL.

8. The preparation method according to any one of claims 5 to 7, characterized in that: The aging time is more than 48 hours.

9. Application of the circularly polarized luminescent material according to claim 3 or 4 in optical information transmission, optical data storage and encryption.

10. Use of the circularly polarized luminescent material according to claim 3 or 4 in the fields of catalysis and gas adsorption and separation.

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