Chiral pyrene derivative, process for its preparation and use thereof

Abstract

This invention belongs to the field of luminescent materials technology, specifically relating to a chiral pyrene derivative, its preparation method, and its applications. The preparation method of the pyrene derivative includes stepwise functionalization, obtaining the pyrene derivative through preliminary distillation, chromatography, and rotary evaporation. This invention, by introducing chiral groups into the structure of the pyrene derivative, enables effective control over the photophysical properties of the pyrene derivative, which is of great significance for the synthesis of pyrene-based luminescent materials with specific circularly polarized emission structures.

Description

Technical Field

[0001] This invention belongs to the field of luminescent materials technology, specifically relating to a chiral pyrene derivative, its preparation method, and its application. Background Technology

[0002] Chirality is a fundamental phenomenon prevalent in nature, defined as the spatial geometric characteristic that prevents an object from perfectly superimposing itself on its mirror image. In chemistry, chirality is primarily manifested at the molecular scale, with the most typical chiral molecules containing a chiral center. The most common chiral center is a saturated carbon atom bonded to four distinct atoms or groups. This unique property of chiral molecules makes them significant for research and application in multiple fields, including chemistry and biology. Extending the concept of chirality to the field of luminescent materials, we find that chiral circularly polarized luminescence (CPL) materials have attracted considerable attention due to their unique optical properties. These materials generate circularly polarized light during luminescence, an optical output characteristic that endows them with enormous application potential, suitable for core applications such as 3D display technology, optical data storage, and bioimaging. The luminescent properties of chiral CPL materials demonstrate broad development prospects in multiple high-tech fields such as optical information processing, sensor technology, and biomarking, further proving the importance and multifaceted nature of chirality in modern technology.

[0003] Pyrene is a polycyclic aromatic hydrocarbon with excellent luminescent properties. Pyrene-based derivatives are compounds formed by chemically modifying pyrene molecules, possessing unique optical and electronic properties and significant material application value, showing great potential in the field of luminescent materials. By introducing chiral structural units into the pyrene molecule, chiral pyrene-based derivatives can be prepared. These derivatives can generate strongly circularly polarized light in the excited state. Compared to traditional circularly polarized luminescent materials, these chiral pyrene-based derivatives exhibit higher luminescent efficiency and polarization degree, making them promising for broad applications in optical information processing and biomarking. Current research on the synthesis of chiral derivatives focuses on introducing chiral centers at specific positions in the pyrene molecule through specific synthetic pathways. Although existing methods have made some progress in constructing chiral pyrene-based derivatives, challenges remain in achieving a wider range of chiral center introductions. In particular, constructing chiral centers at different positions on the pyrene molecule is difficult due to the potential for similar chemical reactivity at these positions, making precise control and introduction of different chiral substituents during synthesis challenging.

[0004] Chinese patent CN120778703A discloses an organic chiral small molecule material and its preparation method. The organic chiral small molecule material is provided, and its structure is shown in formula (I).

[0005]

[0006] Although the solid form of the compound in this patent can be used to construct chiral structures, there is insufficient research on the performance optimization and systematic study of circularly polarized luminescence.

[0007] Chinese patent CN120623476A discloses a method for synthesizing chiral polyaniline nanomaterials and their application in the chiral crystallization of amino acids. The method involves ultrasonically dissolving monochiral tartaric acid, aniline monomer, and N-phenyl-p-phenylenediamine in water, then adding a certain volume of ammonium persulfate aqueous solution to initiate polymerization. After the reaction is complete, centrifugation yields polyaniline-tartaric acid (PANI-TA) chiral nanomaterials. However, this patented method is overly complex and requires stringent reaction conditions.

[0008] Chinese patent CN120571995A discloses a chiral noble metal nanocage synthesized using penicillamine-induced synthesis, its preparation method, and its application. The noble metals in the chiral noble metal nanocage are palladium, platinum, and gold, with a molar ratio of (16-18):(24-28):(56-59). The chiral noble metal nanocage has a three-dimensional chiral morphology induced by penicillamine chiral molecules, and its edge length is in the nanometer range. The cost of the noble metal nanocage prepared by this patent is relatively high. Summary of the Invention

[0009] In view of the shortcomings of the prior art, the technical problem to be solved by the present invention is to provide a pyrene derivative that, by combining a cyclohexanediamine chiral unit with a pyrene structure, can give it circularly polarized light emission characteristics; the present invention also provides its preparation method and application.

[0010] The technical solution adopted by this invention to solve its technical problem is: The pyrene derivative of this invention has the following structural formula:

[0011] in: The method for preparing the pyrene derivative includes the following steps: (1) Under a nitrogen atmosphere, 1,3-diformyl-7-tert-butylpyrene and glacial acetic acid were added to a dichloromethane solution containing (S,S)cyclohexanediamine and stirred to carry out a Schiff base reaction, yielding a pyrene derivative solution; wherein, 1,3-diformyl-7-tert-butylpyrene was added to the solution and stirred to obtain a pyrene derivative solution. S Py's organic solution is made from S The mixture of Py and dichloromethane solvent is used to obtain the product; (2) The pyrene derivative solution was diluted and washed, and the phases were separated to obtain an organic phase and an aqueous phase. The organic phase in the aqueous phase was extracted, and the organic phases were combined and dried to obtain an organic phase containing the pyrene derivative. (3) The organic phase containing pyrene derivatives was initially distilled, chromatographically analyzed and then rotary evaporated to obtain pyrene derivatives.

[0012] In step (1), the molar ratio of 1,3-dicarboxy-7-tert-butylpyrene, glacial acetic acid and cyclohexanediamine is 1:0.5:1.

[0013] In step (1), the organic solvent is dichloromethane, and the ratio of organic solvent, glacial acetic acid, cyclohexanediamine and 1,3-dicarboxy-7-tert-butylpyrene is 90-110:0.5:1:1; the organic solvent is in mL, the glacial acetic acid is in mL, the cyclohexanediamine is in g, and the 1,3-dicarboxy-7-tert-butylpyrene is in g.

[0014] In step (1), the stirring is thorough, the condensation reaction temperature is 25°C, and the condensation reaction time is 5-7 days.

[0015] In step (2), dilution is performed using deionized water, with a volume ratio of deionized water to the organic solvent in step (1) of 1:4.4-6.3. Washing is performed using a saturated sodium chloride solution, with a volume ratio of saturated sodium chloride solution to the organic solvent in step (1) of 1:4.4-6.3. Extraction is performed using an extractant, which is toluene or ethanol, and the extraction is performed 1-2 times. Drying is performed using anhydrous magnesium sulfate.

[0016] In step (3), the preliminary distillation is vacuum distillation with a pressure of 1-2 kPa and a distillation time of 10-20 min. The chromatography is performed using dichloromethane and petroleum ether as eluents with a volume ratio of 1:1-2. The rotary evaporation temperature is 40-50℃ and the rotary evaporation time is 10-20 min.

[0017] The reaction equation for preparing pyrene derivatives according to this invention is as follows:

[0018] This invention involves a stepwise functionalization of 1,3-diformyl-7-tert-butylpyrene, cyclohexanediamine, and glacial acetic acid through a mixed reaction under specific conditions. Cyclohexanediamine, as one of the reactants, undergoes a Schiff base reaction with 1,3-diformyl-7-tert-butylpyrene, inserting a chiral 1,2-cyclohexanediamine unit at the 1,3-aldehyde group to form a chiral pyrene derivative. This chiral structure gives the molecule a unique spatial configuration, acting as a "stereoscopic barrier" that effectively prevents tight π-π packing of molecules in the solid or aggregated state, resulting in a more uniform and stable pyrene derivative. The presence of the chiral center can influence the intensity of intramolecular charge transfer, thereby modulating the circularly polarized luminescence of the material and significantly improving the luminescence effect. During the reaction, glacial acetic acid provides an acidic environment to promote the reaction. The reaction is carried out under a nitrogen atmosphere to avoid side reactions such as oxidation. Finally, in the specific solvent dichloromethane, through a series of reaction steps, including dilution, washing, phase separation, extraction, drying, distillation, chromatography and rotary evaporation, the target product with chirality is obtained. This enables effective control of the photophysical properties of pyrene derivatives and is of great significance for the synthesis of pyrene-based luminescent materials with specific chiral structures.

[0019] The beneficial effects of this invention are: This invention introduces a chiral structure into a pyrene derivative, altering the electron cloud arrangement and spatial configuration of the molecule, thereby achieving a significant change in fluorescence properties. This chiral pyrene derivative has important potential applications in the field of optical materials.

[0020] This invention uses 1,3-diformyl-7-tert-butylpyrene and cyclohexanediamine as raw materials. The raw materials are inexpensive and readily available, the intermediates are simple to prepare and have stable properties, require no special storage conditions, and are low in cost. The prepared chiral pyrene derivatives have unique chiral characteristics, mild reaction conditions, simple operation, a concise overall synthetic route, high yield, low pollution, and no need for complex purification steps, making them easier to prepare and apply industrially. Attached Figure Description

[0021] Figure 1 This is the circularly polarized emission spectrum of the pyrene derivative prepared in Example 1 of this invention; Figure 2 It is a pyrene derivative prepared in Example 1 of this invention. S Py NMR hydrogen spectrum; Figure 3 It is a pyrene derivative prepared in Example 1 of this invention. R Py NMR hydrogen spectrum. Detailed Implementation

[0022] The present invention will be further described below with reference to embodiments: Example

[0023] The preparation method of pyrene derivatives includes the following steps: (1) Under a nitrogen atmosphere, 0.446 g of 1,3-dicarboxy-7-tert-butylpyrene, 0.114 g of cyclohexanediamine and 0.5 mL of glacial acetic acid solution were added to a dichloromethane solution and stirred at room temperature for 5 days to carry out a Schiff base reaction, yielding a pyrene derivative solution; (2) The pyrene derivative solution was diluted with 40 mL of deionized water and then washed with 40 mL of saturated sodium chloride solution to wash the impurities in the organic matter into the aqueous phase. The phases were separated to obtain an organic phase and an aqueous phase. The organic phase in the aqueous phase was then extracted with toluene twice. The organic phases were combined and dried with anhydrous magnesium sulfate to obtain an organic phase containing pyrene derivatives. (3) The organic phase containing the pyrene derivative was subjected to vacuum distillation at 1 kPa for 15 min, followed by gradient elution chromatography using dichloromethane and petroleum ether at a volume ratio of 1:1. The pyrene derivative was then obtained by rotary evaporation at 50 °C for 15 min. The pyrene derivative was a white solid with a yield of 67.7%. The circularly polarized emission spectrum of the pyrene derivative is shown in the figure below. Figure 1 As shown, the proton NMR spectrum is as follows: Figure 2 As shown, Example

[0024] The preparation method of pyrene derivatives includes the following steps: (1) Under a nitrogen atmosphere, 0.446 g of 1,3-dicarboxy-7-tert-butylpyrene and 0.114 g of cyclohexanediamine were added to a dichloromethane solution and stirred at room temperature for 5 days to carry out a Schiff base reaction, yielding a pyrene derivative solution; (2) The pyrene derivative solution was diluted with 40 mL of deionized water and then washed with 40 mL of saturated sodium chloride solution to wash the impurities in the organic matter into the aqueous phase. The phases were separated to obtain an organic phase and an aqueous phase. The organic phase in the aqueous phase was then extracted with toluene twice. The organic phases were combined and dried with anhydrous magnesium sulfate to obtain an organic phase containing pyrene derivatives. (3) The organic phase containing the pyrene derivative was subjected to vacuum distillation at 1 kPa for 15 min, followed by gradient elution chromatography using dichloromethane and petroleum ether in a volume ratio of 1:1. The pyrene derivative was then obtained by rotary evaporation at 50 °C for 15 min. The pyrene derivative was a yellowish-white solid with a yield of 21.5%. The circularly polarized emission spectrum of the pyrene derivative is shown in the figure below. Figure 1 As shown, the proton NMR spectrum is as follows: Figure 2 As shown, Example

[0025] The preparation method of pyrene derivatives includes the following steps: (1) Under a nitrogen atmosphere, 0.446 g of 1,3-dicarboxy-7-tert-butylpyrene, 0.114 g of cyclohexanediamine and 0.5 mL of glacial acetic acid were added to a dichloromethane solution and stirred at room temperature for 3 days to carry out a Schiff base reaction, yielding a pyrene derivative solution; (2) The pyrene derivative solution was diluted with 40 mL of deionized water and then washed with 40 mL of saturated sodium chloride solution to wash the impurities in the organic matter into the aqueous phase. The phases were separated to obtain an organic phase and an aqueous phase. The organic phase in the aqueous phase was then extracted with toluene twice. The organic phases were combined and dried with anhydrous magnesium sulfate to obtain an organic phase containing pyrene derivatives. (3) The organic phase containing the pyrene derivative was subjected to vacuum distillation at 2 kPa for 15 min, followed by gradient elution chromatography using dichloromethane and petroleum ether at a volume ratio of 1:2. The pyrene derivative was then obtained by rotary evaporation at 50 °C for 15 min. The pyrene derivative was a white solid with a yield of 41%. The circularly polarized emission spectrum of the pyrene derivative is shown in the figure below. Figure 1 As shown, the proton NMR spectrum is as follows: Figure 2 As shown, Comparative Example 1 The pyrene derivative was obtained using the preparation steps of Example 1 in Chinese Patent CN120778703A, with a yield of 67.7%.

[0026] Comparative Example 2 In step (1), potassium carbonate aqueous solution is not used; the remaining steps are as in Example 1. The resulting pyrene derivative is a yellowish-white solid with a yield of 21.5%. Comparative Example 3 Reducing the Schiff base reaction time yielded a pyrene derivative as a white solid with a yield of 41%.

[0027] Comparative Examples 1 and 2 show that glacial acetic acid, as a catalyst in the prior art, increases the yield of the Schiff base reaction; compared with Example 1, Comparative Example 3 shows that sufficient reaction time increases the yield of the Schiff base reaction.

Claims

1. A compound containing a pyrene derivative, characterized in that, The structure is as follows: 。 2. A method for preparing a pyrene derivative, characterized in that... Having chirality includes the following steps: (1) Under a nitrogen atmosphere, 1,3-diformyl-7-tert-butylpyrene and glacial acetic acid were added to a dichloromethane solution containing (S,S)cyclohexanediamine and stirred to carry out a Schiff base reaction, yielding a pyrene derivative solution; wherein, 1,3-diformyl-7-tert-butylpyrene was added to the solution and stirred to obtain a pyrene derivative solution. S Py's organic solution is made from S The mixture of Py and dichloromethane solvent is used to obtain the product; (2) The pyrene derivative solution was diluted and washed, and the phases were separated to obtain an organic phase and an aqueous phase. The organic phase in the aqueous phase was extracted, and the organic phases were combined and dried to obtain an organic phase containing the pyrene derivative. (3) The organic phase containing pyrene derivatives was initially distilled, chromatographically analyzed and then rotary evaporated to obtain pure chiral pyrene derivatives.

3. The method for preparing the pyrene derivative according to claim 2, characterized in that... It is chiral, and the molar ratio of 1,3-dicarboxy-7-tert-butylpyrene, glacial acetic acid and cyclohexanediamine in step (1) is 1:0.5:

1.

4. The application of the pyrene derivative according to claim 2, characterized in that, In step (1), the organic solvent is dichloromethane, and the ratio of organic solvent, glacial acetic acid, cyclohexanediamine and 1,3-dicarboxy-7-tert-butylpyrene is 90-110:0.5:1:1; the organic solvent is in mL, the glacial acetic acid is in mL, the cyclohexanediamine is in g, and the 1,3-dicarboxy-7-tert-butylpyrene is in g.

5. The method for preparing the pyrene derivative according to claim 2, characterized in that, In step (1), the stirring is thorough, the Schiff base reaction temperature is 25℃, and the reaction time is 5-7 days.

6. The method for preparing the pyrene derivative according to claim 2, characterized in that, In step (2), dilution is performed using deionized water, with a volume ratio of deionized water to the organic solvent in step (1) of 1:4.4-6.

3. Washing is performed using a saturated sodium chloride solution, with a volume ratio of saturated sodium chloride solution to the organic solvent in step (1) of 1:4.4-6.

3. Extraction is performed using an extractant, which is dichloromethane, and the extraction is performed 1-2 times. Drying is performed using anhydrous magnesium sulfate.

7. The method for preparing the pyrene derivative according to claim 2, characterized in that, In step (3), the initial distillation is vacuum distillation with a pressure of 1-2 kPa and a distillation time of 10-20 min. The chromatography is performed using dichloromethane and petroleum ether as eluents with a volume ratio of 1:1-2. The rotary evaporation temperature is 40-50 ℃ and the rotary evaporation time is 10-20 min.

8. An application of the pyrene derivative according to claim 1, characterized in that, Pyrene derivatives are chiral and exhibit circularly polarized luminescence properties.

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