Chiral compound, preparation method and application thereof
By linking fluorescent groups and alkyl chains to the cyclohexanediamine molecular backbone, chiral compounds with excellent chiral luminescence and gelation properties were prepared, solving the problem of low asymmetry factor in circularly polarized luminescence in existing technologies and realizing the efficient construction of circularly polarized luminescent materials.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- THE NAT CENT FOR NANOSCI & TECH NCNST OF CHINA
- Filing Date
- 2026-03-03
- Publication Date
- 2026-06-26
AI Technical Summary
Existing chiral luminescent organogel factors suffer from low circular polarization luminescence asymmetry factors, making it difficult to efficiently construct circular polarization luminescent materials.
Chiral compounds with excellent chiral luminescence and gelling properties were prepared by linking fluorescent groups and alkyl chains to the cyclohexanediamine molecular backbone. A gelling factor with circularly polarized luminescence was prepared by a simple synthetic process.
This study demonstrated that chiral compounds exhibit good gelation properties and a high circular polarization luminescence asymmetry factor in multiple solvents, enabling the efficient construction of circular polarization luminescent material systems.
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Figure CN122277445A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of organic light-emitting materials technology, and in particular to a chiral compound, its preparation method, and its application. Background Technology
[0002] In recent years, research on circularly polarized luminescent materials has been gaining momentum, primarily due to their broad application potential in cutting-edge fields such as optical displays, information storage, optoelectronic devices, and bioimaging. This has sparked deep interest and attention from the scientific community. Chiral organic fluorescent molecules are particularly noteworthy. Due to their unique circularly polarized luminescence properties and vast application prospects, they have firmly established themselves at the core of chiral luminescent materials research, becoming a focal point for scientists to pursue and explore in depth.
[0003] The fibrous network structures formed by the self-assembly of low molecular mass organogelators (LMOGs) from the molecular to the micrometer scale, and the physicochemical properties of the resulting thermoreversible gels, have attracted considerable interest. Below the gelation temperature, LMOGs aggregate into fibers, strands, and bands through hydrogen bonding, π-π stacking interactions, van der Waals forces, ion-ion interactions, and host-guest interactions, connecting at "nodes" to form a network that holds the liquid in place through surface tension and capillary forces. Currently, developing supramolecular gelling agents based on novel non-covalent interactions, expanding the application areas of supramolecular gels, and elucidating their gelation mechanisms remain key research challenges and cutting-edge topics in this field.
[0004] Currently, chiral luminescent organogel factors face significant challenges in circularly polarized luminescence. Specifically, these molecules generally exhibit low circularly polarized luminescence asymmetry factors (glum). Summary of the Invention
[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide a chiral compound with excellent chiral luminescence properties and gelation properties, as well as its preparation method and application.
[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: In a first aspect, the present invention provides a chiral compound having the structure shown in formula (I) or formula (II): ; Wherein, R1 is any one of alkyl groups having 6-18 carbon atoms.
[0007] The chiral compounds of this invention have fluorescent groups attached to the cyclohexanediamine molecular backbone. This allows for the utilization of the axial chiral structure of the cyclohexanediamine molecular backbone, exhibiting excellent chiral properties, and the attachment of fluorescent groups yields chiral fluorescent molecules capable of emitting light at specific wavelengths. Studies have shown that the (R,R) type chiral compound of formula (I) of this invention exhibits a strong absorption peak in the ultraviolet absorption spectrum near 335 nm, a maximum fluorescence peak at 424 nm, a circular dichroism signal near 424 nm, and a circularly polarized emission signal near 440 nm, with a circular polarization emission asymmetry factor of approximately 0.01. The circular dichroism and circular polarization emission spectra of the (S,S) type chiral compound of formula (II) are mirror images of those of the (R,R) type chiral compound of formula (I).
[0008] Furthermore, the chiral compounds of the present invention also have alkyl chains attached to the cyclohexanediamine molecular backbone, giving them good gelling properties. Thus, the chiral compounds of the present invention can simultaneously exhibit excellent chiral luminescence and gelling properties, expanding the range of fluorescent molecules selected for preparing circularly polarized luminescent materials, thereby enabling the efficient construction of circularly polarized luminescent material systems; and can also serve as gelling materials for constructing chiral luminescent supramolecular gels.
[0009] The chiral compound of this invention successfully connects a fluorescent group and an alkyl chain backbone to the cyclohexanediamine molecular backbone simultaneously, solving the problem in the prior art that cyclohexanediamine with two luminescent groups at two sites has poor gelation performance, while connecting two alkyl chain backbones has good gelation performance but no luminescence performance.
[0010] In a preferred embodiment of the chiral compound of the present invention, R1 is any one of alkyl groups having 8-18 carbon atoms. Experiments have shown that when R1 has 8-18 carbon atoms, the chiral compound of the present invention exhibits better gel-forming properties.
[0011] In a preferred embodiment of the chiral compound of the present invention, the number of carbon atoms in R1 is even; more preferably, the number of carbon atoms in R1 is 18.
[0012] Secondly, the present invention provides a method for preparing a chiral compound, comprising the following steps: The trans-N-Boc-1,2-diaminocyclohexane was subjected to an amidation reaction with (b) 1-pyrene carboxylic acid or 1-pyrene carboxylate to obtain trans-N-Boc-2-(pyrene-1-carbamoyl)-1-aminocyclohexane; Trans-N-Boc-2-(pyrene-1-formamido)-1-aminocyclohexane was subjected to a Boc deprotection reaction, followed by neutralization of the reaction system to obtain trans-1-(pyrene-1-formamido)-2-aminocyclohexane. trans-1-(pyrene-1-formamido)-2-aminocyclohexane with C 6-18 Alkyl isocyanates undergo addition reactions to yield trans-1-(pyrene-1-formamido)-2-(3-C) 6-18 Alkylurea)cyclohexane, which is the chiral compound.
[0013] In preparing chiral compounds, this invention uses trans-N-Boc-1,2-diaminocyclohexane as a raw material. This allows for the utilization of the axial chiral structure of cyclohexanediamine, resulting in compounds exhibiting excellent chiral properties. Furthermore, it fully utilizes the two linkage sites on the cyclohexanediamine molecular skeleton.
[0014] This invention employs a simple synthesis process to prepare a gel factor with circularly polarized luminescence.
[0015] In a preferred embodiment of the method for preparing the chiral compound of the present invention, (a) trans-N-Boc-1,2-diaminocyclohexane is (1R,2R)-trans-N-Boc-1,2-diaminocyclohexane, and the chiral compound is (1R,2R)-trans-1-(pyrene-1-formamido)-2-(3-C 6-18 Alkylurea) cyclohexane (its structure is shown in formula (I) above); Alternatively, (a) trans-N-Boc-1,2-diaminocyclohexane may be (1S,2S)-trans-N-Boc-1,2-diaminocyclohexane, and the chiral compound may be (1S,2S)-trans-1-(pyrene-1-formamido)-2-(3-C 6-18 Alkyl urea) Cyclohexane (its structure is shown in formula (II) above).
[0016] The structure of (1R,2R)-trans-N-Boc-1,2-diaminocyclohexane is shown in formula (1) below, and the structure of (1S,2S)-trans-N-Boc-1,2-diaminocyclohexane is shown in formula (2) below: .
[0017] As a preferred embodiment of the preparation method of the chiral compound of the present invention, the preparation method of trans-N-Boc-2-(pyrene-1-formamido)-1-aminocyclohexane is as follows: the preparation raw materials including (a) trans-N-Boc-1,2-diaminocyclohexane, (b) 1-pyrene carboxylic acid or 1-pyrene carboxylate, catalyst and organic solvent are subjected to an amidation reaction by heating under alkaline conditions and reflux. After the reaction is completed, the reaction system is neutralized with acid, and then impurities are removed and purified to obtain trans-N-Boc-2-(pyrene-1-formamido)-1-aminocyclohexane.
[0018] In a preferred embodiment of the preparation method of the chiral compound of the present invention, the raw material further includes triethylamine.
[0019] In a preferred embodiment of the method for preparing the chiral compound of the present invention, the catalyst comprises 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC·HCl) and 1-hydroxybenzotriazole (HOBt).
[0020] In a preferred embodiment of the method for preparing the chiral compound of the present invention, the organic solvent is dichloromethane.
[0021] As a preferred embodiment of the preparation method of the chiral compound of the present invention, the method of removing impurities and purifying is as follows: water is added to the reaction system after neutralization with acid, impurities are removed by extraction, and then the solvent in the target phase obtained by extraction is removed to obtain a crude product; the crude product is purified by silica column chromatography to obtain trans-N-Boc-2-(pyrene-1-formamido)-1-aminocyclohexane.
[0022] In a preferred embodiment of the method for preparing the chiral compound of the present invention, in the amidation reaction, the molar ratio of (a) trans-N-Boc-1,2-diaminocyclohexane to (b) 1-pyrenic acid or 1-pyrenic acid ester is 1:(0.7-1.3). And / or, the temperature of the amidation reaction is 60-70°C; And / or, the amidation reaction takes more than 72 hours.
[0023] In a preferred embodiment of the method for preparing the chiral compound of the present invention, in the addition reaction, trans-1-(pyrene-1-formamido)-2-aminocyclohexane reacts with C 6-18 The molar ratio of alkyl isocyanates is 1:(1.0-1.5).
[0024] In a preferred embodiment of the method for preparing the chiral compound of the present invention, the temperature of the addition reaction is 70-80°C.
[0025] In a preferred embodiment of the method for preparing the chiral compound of the present invention, the addition reaction takes 12 hours or more.
[0026] As a preferred embodiment of the method for preparing the chiral compound of the present invention, the C 6-18 Alkyl isocyanate is C 8-18 Alkyl isocyanate.
[0027] As a preferred embodiment of the method for preparing the chiral compound of the present invention, the C 6-18 In alkyl isocyanates, the number of carbon atoms in the alkyl group is even. More preferably, the C6-18 The alkyl isocyanate is octadecyl isocyanate.
[0028] Thirdly, the present invention provides the application of the above-mentioned chiral compound or the chiral compound prepared by the above-mentioned method as a gelling agent in the preparation of gels.
[0029] Fourthly, the present invention provides the application of the above-mentioned chiral compounds or chiral compounds prepared by the above-mentioned preparation methods in the preparation of circularly polarized light-emitting materials or in optical displays, information storage, optoelectronic devices or bioimaging.
[0030] Compared with the prior art, the beneficial effects of the present invention are as follows: The chiral compounds of the present invention exhibit good gelling properties in multiple solvents and have high g values, and can be used as chiral fluorescent gel materials.
[0031] The chiral compound of this invention has a circular polarization luminescence asymmetry factor of about 0.01, which improves its luminescence performance. It can be used to prepare circular polarization luminescent materials, thereby enabling the efficient construction of circular polarization luminescent material luminescence systems and forming strong colloids in multiple solvents.
[0032] This invention solves the problem that obtaining chiral pure organic fluorescent molecules usually requires costly chiral separation methods, making it difficult to efficiently construct circularly polarized luminescence systems. Attached Figure Description
[0033] To more clearly illustrate the technical solutions in this invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.
[0034] Figure 1 This is a synthetic route diagram of the chiral compound in Example 1 of the present invention.
[0035] Figure 2 These are the UV-Vis absorption spectra of the chiral compound at different concentrations in Example 1 of this invention.
[0036] Figure 3 This is a circular dichroism absorption spectrum of the chiral compound at different concentrations in Example 1 of the present invention.
[0037] Figure 4 These are fluorescence spectra of the chiral compound at different concentrations in Example 1 of this invention.
[0038] Figure 5 These are circularly polarized emission spectra of the chiral compound at different concentrations in Example 1 of this invention.
[0039] Figure 6 This is a spectrum showing the asymmetry factor of the circularly polarized luminescence of the chiral compound in Example 1 of the present invention as a function of wavelength.
[0040] Figure 7 This is a circular dichroism absorption spectrum of the chiral compound at different concentrations in Example 2 of the present invention.
[0041] Figure 8 This is a circularly polarized emission spectrum of the chiral compound at different concentrations in Example 2 of the present invention.
[0042] Figure 9 This is a graph showing the gelation results of the chiral compound in different solvents in Example 1 of the present invention. Detailed Implementation
[0043] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of this invention. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.
[0044] Example 1 An embodiment of the chiral compound and its preparation method of the present invention is provided. The chiral compound in this embodiment is (1R,2R)-trans-1-(pyrene-1-formamido)-2-(3-octadecylureo)cyclohexane, with the following structural formula: .
[0045] The preparation process of the chiral compound in this embodiment is as follows: Figure 1 As shown, the specific preparation method is as follows: a. 2.6 g (12.1 mmol) of (1R,2R)-trans-N-Boc-1,2-diaminocyclohexane and 2.5 g (10.2 mmol) of 1-pyrene carboxylic acid were reacted with 2.3 g (12.0 mmol) of EDC·HCl and 1.6 g (11.8 mmol) of HOBt in 250 mL of dichloromethane for 3 days as catalysts and 15 mL of triethylamine as a solvent. After cooling to room temperature, the mixture was neutralized with dilute hydrochloric acid, and impurities were extracted with pure water. The solvent was then removed, and the mixture was purified by silica column chromatography (eluent DCM: methanol = 4:1) to obtain (1R,2R)-trans-N-Boc-2-(pyrene-1-carboxamido)-1-aminocyclohexane. b. Dissolve 1.5 g (3.40 mmol) of (1R,2R)-trans-N-Boc-2-(pyrene-1-carbamoyl)-1-aminocyclohexane in 250 mL of dichloromethane, add 10 mL of trifluoroacetic acid, stir at room temperature for 2 days, remove the solvent, dissolve in 5 mL of THF, add to 250 mL of saturated NaHCO3 solution to precipitate, filter and wash with pure water to obtain (1R,2R)-trans-1-(pyrene-1-carbamoyl)-2-aminocyclohexane; c. Dissolve 0.50 g (1.46 mmol) of (1R,2R)-trans-1-(pyrene-1-carbamate)-2-aminocyclohexane in THF and react it with 0.48 g (1.61 mmol) of octadecyl isocyanate in an addition reaction at 80 °C for 12 hours to obtain (1R,2R)-trans-1-(pyrene-1-carbamate)-2-(3-octadecylureo)cyclohexane, which is the chiral compound.
[0046] The obtained chiral compound was characterized by nuclear magnetic resonance (NMR). The results are as follows: ¹H NMR (400 MHz, Chloroform-d) δ 8.40 (s, ¹H), 8.32 – 7.64 (m, 8H), 3.99 (d, J = 86.1 Hz, 2H), 2.76 (d, J = 67.9 Hz, 2H), 2.27 (d, J = 49.5 Hz, 2H), 1.96 – 1.75 (m, 2H), 1.33 – 0.31 (m, 39H). Calculated M = 637.9368, ESI [M+K] + 675.6750.
[0047] Example 2 One embodiment of the chiral compound and its preparation method of the present invention is (1S,2S)-trans-1-(pyrene-1-formamido)-2-(3-octadecylureo)cyclohexane, with the following structural formula: .
[0048] The preparation method of the chiral compound in this embodiment is as follows: a. 2.6 g (12.1 mmol) of (1S,2S)-trans-N-Boc-1,2-diaminocyclohexane and 2.97 g (12.1 mmol) of 1-pyrene carboxylic acid were reacted with 2.3 g (12.0 mmol) of EDC·HCl and 1.6 g (11.8 mmol) of HOBt in 250 mL of dichloromethane for 3 days as catalysts and 15 mL of triethylamine as a solvent. After cooling to room temperature, the mixture was neutralized with dilute hydrochloric acid, and impurities were extracted with pure water. The solvent was then removed, and the mixture was purified by silica column chromatography (eluent DCM: methanol = 4:1) to obtain (1S,2S)-trans-N-Boc-2-(pyrene-1-carboxamido)-1-aminocyclohexane. b. Dissolve 1.5 g (3.40 mmol) of (1S,2S)-trans-N-Boc-2-(pyrene-1-formamido)-1-aminocyclohexane in 250 mL of dichloromethane, add 10 mL of trifluoroacetic acid, stir at room temperature for 2 days, remove the solvent, dissolve in 5 mL of THF, add to 250 mL of saturated NaHCO3 solution to precipitate, filter and wash with pure water to obtain (1S,2S)-trans-1-(pyrene-1-formamido)-2-aminocyclohexane; c. Dissolve 0.50 g (1.46 mmol) of (1S,2S)-trans-1-(pyrene-1-carbamate)-2-aminocyclohexane in THF and react it with 0.52 g (1.75 mmol) of octadecyl isocyanate in an addition reaction at 80 °C for 12 hours to obtain (1S,2S)-trans-1-(pyrene-1-carbamate)-2-(3-octadecylureo)cyclohexane, which is the chiral compound.
[0049] Example 3 One embodiment of the chiral compound and its preparation method of the present invention, wherein the structural formula of the chiral compound in this embodiment is: .
[0050] The preparation process of the chiral compound in this embodiment is as follows: Figure 1 As shown, the specific preparation method is as follows: a. 2.6 g (12.1 mmol) of (1R,2R)-trans-N-Boc-1,2-diaminocyclohexane and 2.1 g (8.5 mmol) of 1-pyrene carboxylic acid were reacted under reflux in 250 mL of dichloromethane for 3 days with 2.3 g (12.0 mmol) of EDC·HCl and 1.6 g (11.8 mmol) of HOBt as catalysts and 15 mL of triethylamine as a solvent. After cooling to room temperature, the mixture was neutralized with dilute hydrochloric acid, and impurities were extracted with pure water. The solvent was then removed, and the mixture was purified by silica column chromatography (eluent DCM: methanol = 4:1) to obtain (1R,2R)-trans-N-Boc-2-(pyrene-1-carboxamido)-1-aminocyclohexane. b. Dissolve 1.5 g (3.40 mmol) of (1R,2R)-trans-N-Boc-2-(pyrene-1-carbamoyl)-1-aminocyclohexane in 250 mL of dichloromethane, add 10 mL of trifluoroacetic acid, stir at room temperature for 2 days, remove the solvent, dissolve in 5 mL of THF, add to 250 mL of saturated NaHCO3 solution to precipitate, filter and wash with pure water to obtain (1R,2R)-trans-1-(pyrene-1-carbamoyl)-2-aminocyclohexane; c. Dissolve 0.5 g (1.46 mmol) of (1R,2R)-trans-1-(pyrene-1-carbamate)-2-aminocyclohexane in THF and react it with 0.31 g (1.46 mmol) of dodecyl isocyanate in a reaction at 75 °C for 12 hours to obtain (1R,2R)-trans-1-(pyrene-1-carbamate)-2-(3-dodecylureo)cyclohexane, which is the chiral compound.
[0051] Example 4 One embodiment of the chiral compound and its preparation method of the present invention, wherein the structural formula of the chiral compound in this embodiment is: .
[0052] The preparation process of the chiral compound in this embodiment is as follows: Figure 1 As shown, the specific preparation method is as follows: a. 2.6 g (12.1 mmol) of (1R,2R)-trans-N-Boc-1,2-diaminocyclohexane and 3.9 g (15.7 mmol) of 1-pyrene carboxylic acid were reacted under reflux in 250 mL of dichloromethane for 3 days with 2.3 g (12.0 mmol) of EDC·HCl and 1.6 g (11.8 mmol) of HOBt as catalysts and 15 mL of triethylamine as a solvent. After cooling to room temperature, the mixture was neutralized with dilute hydrochloric acid, and impurities were extracted with pure water. The solvent was then removed, and the mixture was purified by silica column chromatography (eluent DCM: methanol = 4:1) to obtain (1R,2R)-trans-N-Boc-2-(pyrene-1-carboxamido)-1-aminocyclohexane. b. Dissolve 1.5 g (3.40 mmol) of (1R,2R)-trans-N-Boc-2-(pyrene-1-carbamoyl)-1-aminocyclohexane in 250 mL of dichloromethane, add 10 mL of trifluoroacetic acid, stir at room temperature for 2 days, remove the solvent, dissolve in 5 mL of THF, add to 250 mL of saturated NaHCO3 solution to precipitate, filter and wash with pure water to obtain (1R,2R)-trans-1-(pyrene-1-carbamoyl)-2-aminocyclohexane; c. Dissolve 0.5 g (1.46 mmol) of (1R,2R)-trans-1-(pyrene-1-carbamate)-2-aminocyclohexane in THF and react it with 0.29 g (2.19 mmol) of hexyl isocyanate in an addition reaction at 70 °C for 12 hours to obtain (1R,2R)-trans-1-(pyrene-1-carbamate)-2-(3-hexaalkylureo)cyclohexane, which is the chiral compound.
[0053] Example 1 Using toluene as a solvent, the (1R,2R)-trans-1-(pyrene-1-formamido)-2-(3-octadecylureo)cyclohexane from Example 1 was prepared to a concentration of 1×10⁻⁶. -4 mol / L, 5×10 -4 mol / L, 1×10 -3 mol / L and 5×10 -3 The UV-Vis absorption spectrum, circular dichroism absorption spectrum, fluorescence spectrum, and circularly polarized emission spectrum of the solution at different concentrations were tested, as well as the variation of its circularly polarized emission asymmetry factor (g-value) with wavelength.
[0054] Meanwhile, using toluene as a solvent, the (1S,2S)-trans-1-(pyrene-1-formamido)-2-(3-octadecylureo)cyclohexane from Example 2 was prepared to a concentration of 1×10⁻⁶. -4 mol / L, 5×10 -4 mol / L, 1×10 -3 mol / L and 5×10 - 3 The circular dichroism absorption spectrum and circular polarization emission spectrum of the solution at different concentrations were tested.
[0055] The testing instruments and conditions are as follows: Ultraviolet-Vis absorption spectroscopy (UV-Vis): UV-Vis spectra were measured using a Shimadzu UV-2600 spectrometer, with a test range of 200-600 nm and a fast scan rate. Experimental samples were measured in 2 mm quartz cuvettes.
[0056] Circular dichroism (CD) absorption spectroscopy: Circular dichroism absorption spectra were measured using a JASCO J-1500 spectrophotometer, with a measurement range of 200-600 nm and a scan rate of 200 nm / min. Experimental samples were measured in 2 mm quartz cuvettes.
[0057] Fluorescence spectroscopy (FL): Fluorescence spectra were measured using a Hitachi F-4500 fluorescence spectrometer. The measurement voltage was 400V, the slit width was 5nm, the excitation wavelength was 320nm, the test range was 360-600nm, and the scan rate was 500nm / min. The experimental samples were measured in a 2mm quartz cuvette.
[0058] Circularly polarized emission spectroscopy (CPL): Circularly polarized emission spectra were measured using a JASCO CPL-300 circularly polarized emission spectrometer. The measurement voltage was adjusted to a DC value of 0.5V, the slit width was 3000 μm, the excitation wavelength was 320 nm, the test range was 360-600 nm, and the scan rate was 200 nm / min. Experimental samples were measured in 2 mm quartz cuvettes. Data were analyzed using SpectraManager software to derive the fluorescence asymmetry factor of the samples from the circularly polarized emission spectra. g lum .
[0059] Example 1: UV-Vis absorption spectra of chiral compounds at different concentrations are as follows Figure 2 As shown, the circular dichroism absorption spectrum is as follows: Figure 3 As shown, the fluorescence spectrum is as follows Figure 4 As shown, the circularly polarized emission spectrum is as follows Figure 5 As shown, the spectrum of the asymmetry factor of circularly polarized luminescence as a function of wavelength is as follows: Figure 6 As shown. Example 2: Circular dichroism absorption spectra of the chiral compound at different concentrations are shown below. Figure 7 As shown, the circularly polarized emission spectrum is as follows Figure 8 As shown.
[0060] Depend on Figures 2-8As can be seen, the UV absorption spectrum of (1R,2R)-trans-1-(pyrene-1-formamido)-2-(3-octadecylureo)cyclohexane has a strong absorption peak near 335 nm; the circular dichroism spectra of (1R,2R)-trans-1-(pyrene-1-formamido)-2-(3-octadecylureo)cyclohexane and (1S,2S)-trans-1-(pyrene-1-formamido)-2-(3-octadecylureo)cyclohexane are mirror images of each other, with (1R,2R)-trans-1-(pyrene-1-formamido)-2-(3-octadecylureo)cyclohexane showing a positive circular dichroism signal near 367 nm; and (1R,2R)-trans-1-(pyrene-1-formamido)-2-(3-octadecylureo)cyclohexane... The maximum peak position of the fluorescence spectrum of cyclohexane is 424 nm; the circularly polarized emission spectra of (1R,2R)-trans-1-(pyrene-1-formamido)-2-(3-octadecylureo)cyclohexane and (1S,2S)-trans-1-(pyrene-1-formamido)-2-(3-octadecylureo)cyclohexane are mirror images of each other, and (1R,2R)-trans-1-(pyrene-1-formamido)-2-(3-octadecylureo)cyclohexane has a positively polarized emission signal near 424 nm.
[0061] The UV absorption and fluorescence spectra of (1S,2S)-trans-1-(pyrene-1-formamido)-2-(3-octadecylureo)cyclohexane are similar to those of (1R,2R)-trans-1-(pyrene-1-formamido)-2-(3-octadecylureo)cyclohexane.
[0062] like Figure 6 As shown, the circularly polarized emission asymmetry factor of axially chiral (1R,2R)-trans-1-(pyrene-1-formamido)-2-(3-octadecylureo)cyclohexane is approximately 0.01.
[0063] Example 2: Display of gelation state Weigh 5 mg of (1R,2R)-trans-1-(pyrene-1-formamido)-2-(3-C) into a 1 cm diameter, 5 mL sample vial. 18 Alkylurea) Cyclohexane (the chiral compound obtained in Example 1), 1 mL of solvent was added, and the mixture was heated in a heating mantle until the supramolecular molecules were completely dissolved. The hot solution was then slowly cooled to room temperature and allowed to stand for 3 hours. The following conditions were observed: 1) If the system did not flow when the sample vial was inverted, a stable gel had formed, denoted as "G"; 2) If only a partial gel formed, denoted as "PG"; 3) If a precipitate formed, denoted as "P"; 4) If the system remained a clear solution, denoted as "S". If the supramolecular molecules were insoluble in the solvent at the start of heating, denoted as "I". The minimum gel concentration is the minimum mass of supramolecular molecules required to form a stable gel at 25°C.
[0064] The gelation results of the chiral compounds of the present invention in different solvents are shown in Table 1 and Figure 9 below.
[0065] Table 1
[0066] As can be seen from Table 1 and Figure 9, the chiral compounds of the present invention can form strong colloids in a variety of solvents.
[0067] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims
1. A chiral compound, characterized in that, The chiral compound has the structure shown in formula (I) or formula (II): ； Wherein, R1 is any one of alkyl groups having 6-18 carbon atoms.
2. The chiral compound according to claim 1, characterized in that, R1 is any one of alkyl groups having 8-18 carbon atoms.
3. The chiral compound according to claim 1 or 2, characterized in that, The number of carbon atoms in R1 is even; preferably, the number of carbon atoms in R1 is 18.
4. A method for preparing a chiral compound, characterized in that, Includes the following steps: The trans-N-Boc-1,2-diaminocyclohexane was subjected to an amidation reaction with (b) 1-pyrene carboxylic acid or 1-pyrene carboxylate to obtain trans-N-Boc-2-(pyrene-1-carbamoyl)-1-aminocyclohexane; Trans-N-Boc-2-(pyrene-1-formamido)-1-aminocyclohexane was subjected to a Boc deprotection reaction, followed by neutralization of the reaction system to obtain trans-1-(pyrene-1-formamido)-2-aminocyclohexane. trans-1-(pyrene-1-formamido)-2-aminocyclohexane with C 6-18 Alkyl isocyanates undergo addition reactions to yield trans-1-(pyrene-1-formamido)-2-(3-C) 6-18 Alkylurea)cyclohexane, which is the chiral compound.
5. The method for preparing the chiral compound according to claim 4, characterized in that, The (a) trans-N-Boc-1,2-diaminocyclohexane is (1R,2R)-trans-N-Boc-1,2-diaminocyclohexane, and the chiral compound is (1R,2R)-trans-1-(pyrene-1-formamido)-2-(3-C 6-18 Alkylurea) Cyclohexane; Alternatively, (a) trans-N-Boc-1,2-diaminocyclohexane may be (1S,2S)-trans-N-Boc-1,2-diaminocyclohexane, and the chiral compound may be (1S,2S)-trans-1-(pyrene-1-formamido)-2-(3-C 6-18 Alkylurea) Cyclohexane.
6. The method for preparing the chiral compound according to claim 4 or 5, characterized in that, The preparation method of the trans-N-Boc-2-(pyrene-1-formamido)-1-aminocyclohexane is as follows: the raw materials including (a) trans-N-Boc-1,2-diaminocyclohexane, (b) 1-pyrene carboxylic acid or 1-pyrene carboxylate, catalyst and organic solvent are subjected to an amidation reaction under alkaline conditions by heating and reflux. After the reaction is completed, the reaction system is neutralized with acid, and then impurities are removed and purified to obtain trans-N-Boc-2-(pyrene-1-formamido)-1-aminocyclohexane. Preferably, the raw materials for preparation further include triethylamine; And / or, the catalyst comprises 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and 1-hydroxybenzotriazole; And / or, the organic solvent is dichloromethane.
7. The method for preparing the chiral compound according to any one of claims 4-6, characterized in that, In the amidation reaction, the molar ratio of (a) trans-N-Boc-1,2-diaminocyclohexane to (b) 1-pyrene carboxylic acid or 1-pyrene carboxylate is 1:(0.7-1.3). And / or, the temperature of the amidation reaction is 60-70°C; And / or, the amidation reaction takes more than 72 hours.
8. The method for preparing the chiral compound according to claim 4 or 5, characterized in that, In the addition reaction, trans-1-(pyrene-1-formamido)-2-aminocyclohexane reacts with C 6-18 The molar ratio of alkyl isocyanates is 1:(1.0-1.5). And / or, the temperature of the addition reaction is 70-80°C; And / or, the addition reaction takes more than 12 hours.
9. The use of the chiral compound according to any one of claims 1-3 or the chiral compound prepared by any one of claims 4-8 as a gelling agent in the preparation of gels.
10. The chiral compound according to any one of claims 1-3 or the chiral compound prepared by any one of claims 4-8, in the preparation of circularly polarized light-emitting materials or in optical displays, information storage, optoelectronic devices or bioimaging.