A chiral biphenyl aromatic macrocyclic compound and its complex, preparation method and application

Abstract

The present invention provides a chiral biphenyl aromatic hydrocarbon macrocyclic compound and its complex, preparation method and application, belonging to the field of organic material technology. The present invention provides a specific structural formula of a chiral biphenyl aromatic hydrocarbon macrocyclic compound, wherein the 2,4-position pentaphenyl tricyclic perhydroxyl group is dissolved in an aprotic polar solvent, potassium iodide is added, and the reaction is carried out under the action of a base to obtain a reaction liquid, which is then separated by column chromatography to obtain a chiral biphenyl aromatic hydrocarbon macrocyclic compound. The present invention introduces a chiral side chain into the achiral pentaphenyl macrocycle by covalent modification, and further dopes it into a polymer to prepare a chiral polymer film exhibiting good circular dichroism absorption and fluorescence properties. The chiral biphenyl aromatic hydrocarbon macrocyclic compound and the complex provided by the present invention have a simple preparation method, convenient modification, and simple separation, so that the compound and the complex have broad application prospects in chiral display devices and encryption materials.

Description

Technical Field

[0001] The present invention relates to the technical field of organic materials, and in particular to a chiral biphenyl aromatic macrocyclic compound and a composite thereof, a preparation method and an application thereof. Background Art

[0002] Chiral molecules primarily include central chiral molecules, axial chiral molecules, planar chiral molecules, and helical chiral molecules. Due to their importance and role in disciplines and industries such as chemistry and chemical engineering, life sciences and medicine, and materials science, the catalytic asymmetric synthesis of these chiral molecules has long been a core and cutting-edge research area in synthetic chemistry. Chiral luminescent materials, due to their unique left-handed and right-handed structures, can emit not only conventional photoluminescence but also circularly polarized light (CPL). Devices capable of directly emitting circularly polarized electroluminescence (CPEL) using chiral luminescent materials as luminescent centers, known as CP-OLEDs, have great potential for application in 3D displays.

[0003] Circularly polarized luminescence (CPL) is the phenomenon in which a chiral luminophore emits left-handed and right-handed circularly polarized light under excitation with unpolarized light. In recent years, CPL materials have attracted interest due to their applications in chemical and biological sensing, chiral optical materials, asymmetric catalysis, optoelectronic devices, and other fields. However, traditional organic light-emitting materials exhibit problems such as decreased fluorescence and CPL performance and low asymmetry factors when aggregated, which limits the practical application of CPL materials. Chiral compounds with circularly polarized luminescence have shown good application prospects in liquid crystal displays, biosensors, information storage, and other fields. Therefore, the development of a chiral compound with high quantum yield and asymmetry factor is of great significance and is conducive to improving the practical application value of chiral light-emitting materials. Summary of the Invention

[0004] The purpose of the present invention is to provide a chiral biphenyl aromatic macrocyclic compound and its complex, preparation method and application. A chiral biphenyl aromatic macrocyclic compound is obtained by introducing a chiral side chain into an achiral pentadiphenyl macrocycle through covalent modification. The chiral biphenyl aromatic macrocyclic compound is further doped into a polymer to prepare a chiral polymer film, which exhibits good circular dichroism absorption and fluorescence properties, significantly expanding the application potential of the biphenyl aromatic macrocycle.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] In a first aspect, the present invention provides a chiral biphenyl aromatic macrocyclic compound having the following structure:

[0007]

[0008] In a second aspect, the present invention further provides a method for preparing the chiral biphenyl aromatic macrocyclic compound, comprising the following steps:

[0009] The 2,4-position pentadiphenyl tricyclic perhydroxyl group is dissolved in a non-protonic polar solvent, potassium iodide is added, and the mixture is reacted under the action of a base to obtain a reaction solution, and the reaction solution is separated by column chromatography to obtain a chiral biphenyl aromatic macrocyclic compound.

[0010] Furthermore, the aprotic polar solvent is N,N-dimethylformamide or acetone.

[0011] Furthermore, the base includes at least one of cesium carbonate, potassium carbonate, potassium hydroxide, and sodium hydroxide.

[0012] Furthermore, the preparation method specifically includes:

[0013] Dissolve the 2,4-pentaphenyl tricyclic perhydroxyl group and (S)-2-methylbutyl p-toluenesulfonate in N,N-dimethylformamide solution at an equivalent ratio of 1:24, then add 24.1 equivalents of potassium iodide and 36 equivalents of cesium carbonate, stir until completely dissolved, protect with nitrogen, continue stirring, and heat under reflux overnight to react;

[0014] The reaction process was monitored by thin-layer chromatography. After the reaction was completed, the reaction solution was cooled to room temperature and transferred to a separatory funnel. Water was added and shaken to precipitate a brown upper solid. The solid and solution in the separatory funnel were then filtered, the upper solid was collected and dried, and the sample was separated by column chromatography to obtain a chiral biphenyl aromatic macrocyclic compound.

[0015] In a third aspect, the present invention further provides a complex prepared by the chiral biphenyl aromatic macrocyclic compound and a polymer, wherein the complex is a chiral polymer film prepared by doping the chiral biphenyl aromatic macrocyclic compound into a polymer.

[0016] In a fourth aspect, the present invention further provides a method for preparing a complex of the chiral biphenyl aromatic macrocyclic compound and a polymer, comprising the following steps:

[0017] In a round-bottom flask, 1 g of polyvinyl alcohol (PVA) and 15 mL of water were added in sequence according to the set ratio, and a magnetic particle was added. After stirring and heating for a set time under certain temperature conditions, stirring and heating were stopped. After standing and ultrasonication, 1 mL of PVA solution was taken and 0.66 mg of chiral biphenyl aromatic macrocyclic compound was dissolved in 0.25 mL of tetrahydrofuran. The solution was mixed and shaken, ultrasonicated, dropped onto a glass plate, and dried to obtain a PVA film doped with a chiral macrocycle, i.e., a composite, and the mass ratio of PVA to chiral macrocycle was 100:1.

[0018] In a fifth aspect, the present invention further provides use of the complex described in the third aspect or the complex prepared by the preparation method described in the fourth aspect as a chiral luminescent material.

[0019] The beneficial effects of the present invention compared with the prior art are:

[0020] (1) In the present invention, a chiral biphenyl aromatic macrocyclic compound is obtained by covalently modifying an achiral pentphenyl macrocycle and introducing a chiral side chain. The chiral biphenyl aromatic macrocyclic compound is further doped into a polymer to prepare a chiral polymer film exhibiting good circular dichroism absorption and fluorescence properties.

[0021] (2) The present invention addresses the problems of cumbersome synthesis and low yield of chiral macrocycles and provides a simple and efficient method for synthesizing chiral biphenyl aromatic hydrocarbon macrocycles. The method uses 2,4-pentabiphenyl tricyclic perhydroxyl groups and (S)-2-methylbutyl p-toluenesulfonate and other reactants to synthesize supramolecular chiral macrocycles in one pot to obtain a chiral biphenyl aromatic hydrocarbon derivative, which significantly expands the application potential of biphenyl aromatic hydrocarbon macrocycles.

[0022] (3) The chiral biphenyl aromatic macrocyclic compound of the present invention is simple to synthesize, convenient to modify, and simple to separate, which makes it have broad application prospects in chiral display devices and encryption materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0024] Figure 1 is the nuclear magnetic spectrum of the chiral biphenyl aromatic macrocyclic compound of the present invention;

[0025] Figure 2 Schematic diagram of the doping of chiral biphenyl aromatic macrocyclic compounds and polymers under natural light and 365nm ultraviolet light;

[0026] Figure 3 is the UV-visible absorption spectrum of the PVA film and the composite of the present invention;

[0027] Figure 4 is the circular dichroism spectrum of the complex. DETAILED DESCRIPTION

[0028] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0029] It should be understood that the terms described herein are intended only to describe particular embodiments and are not intended to limit the present invention. In addition, for numerical ranges herein, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each smaller range between any intermediate value within a stated value or stated range and any other stated value or intermediate value within the stated range is also encompassed by the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded within the scope.

[0030] Unless otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of any conflict with any incorporated document, the contents of this specification shall prevail.

[0031] The raw materials used in the present invention are all commercially available except for the 2,4-pentaphenyl tricyclic perhydroxyl group, which is synthesized according to the literature (Aggregate.2024, e607).

[0032] The present invention provides a chiral biphenyl aromatic macrocyclic compound having the following structure:

[0033]

[0034] The NMR spectrum of the chiral biphenyl aromatic macrocyclic compound with the above structure is as follows: Figure 1 shown. Figure 1 This indicates that the chiral biphenyl aromatic macrocyclic compound prepared by the present invention has high purity; the highly symmetrical NMR peaks in the aromatic region indicate that the chiral biphenyl aromatic macrocyclic compound is symmetrical in solution, and the asymmetric NMR peaks in the aliphatic region confirm the introduction of chiral side chains.

[0035] The present invention also provides a method for preparing the chiral biphenyl aromatic macrocyclic compound, comprising the following steps:

[0036] The 2,4-position pentadiphenyl tricyclic perhydroxyl group is dissolved in a non-protonic polar solvent, potassium iodide is added, and the mixture is reacted under the action of a base to obtain a reaction solution, and the reaction solution is separated by column chromatography to obtain a chiral biphenyl aromatic macrocyclic compound.

[0037] For example, the aprotic polar solvent is N,N-dimethylformamide or acetone. The base includes at least one of cesium carbonate, potassium carbonate, potassium hydroxide, and sodium hydroxide.

[0038] Example 1

[0039] This embodiment specifically discloses the preparation method of the chiral biphenyl aromatic hydrocarbon macrocyclic compound, as follows:

[0040]

[0041] First, the raw materials were added in the prescribed equivalent ratio of 2,4-pentaphenyl tri-ring perhydroxyl group: (S)-2-methylbutyl p-toluenesulfonate: cesium carbonate: potassium iodide = 1:24:36:24.1. Specifically, 0.72g of 2,4-pentaphenyl tri-ring perhydroxyl group (synthesized according to Aggregate.2024, e607), 4.3g of cesium carbonate, 1.45g of potassium carbonate, and 1.92mL of (S)-2-methylbutyl p-toluenesulfonate were added sequentially to a 250mL two-necked round-bottom flask. 50mL of dry N,N-dimethylformamide was then added. After setting up the reaction, stirring was initiated, N2 was evacuated, N2 protection was established, and the reaction was heated under reflux overnight. The reaction was monitored by thin-layer chromatography (TLC). After the reaction is completed, the reaction solution is cooled to room temperature, transferred to a separatory funnel, added with a large amount of water, shaken, and a brown upper solid is precipitated. The mixed system in the separatory funnel is then transferred to a funnel in batches for filtration, the upper solid is collected, the sample is mixed and dried, and the product is separated by column chromatography (petroleum ether / dichloromethane, 3:1, v / v) to obtain the product.

[0042] Biphenylarene chiral macrocycle: 1 H NMR (400MHz, CDCl3) δ7.70(s,4H),7.62(d,J=8.1Hz,4H),7.57(d,J=8.1Hz,4H),7.04(s,2H),6.52(s,2H),3.98(s,2H),3.88-3.71(m ,8H),1.83(dp,J=13.2,6.5Hz,4H),1.38-1.18(m,8H),0.98(dd,J=10.3,6.8Hz,12H),0.90(dt,J=11.4,7.4Hz,12H).m / z=2215.3909.

[0043] The present invention also provides a complex prepared by the chiral biphenyl aromatic hydrocarbon macrocyclic compound and a polymer. The complex is a chiral polymer film prepared by doping the chiral biphenyl aromatic hydrocarbon macrocyclic compound into a polymer.

[0044] like Figure 2 As shown, under natural light, the polymer itself is colorless, and it is also colorless after being doped with the chiral biphenyl aromatic macrocycle; under 365nm ultraviolet light excitation, the polymer itself is colorless, and it shows bright blue after being doped with the chiral biphenyl aromatic macrocycle. Figure 2Description: The prepared complex exhibits blue fluorescence under 365nm ultraviolet light excitation and has good fluorescence properties; the luminescence properties of the complex are not related to the polymer, but come from the doping of the chiral biphenyl aromatic macrocycle.

[0045] The present invention also provides a method for preparing a complex prepared from the chiral biphenyl aromatic macrocyclic compound and a polymer, comprising the following steps:

[0046] In a round-bottom flask, polyvinyl alcohol (PVA) and water are added in sequence according to a set ratio, and a magnet is added. After stirring and heating for a set time under certain temperature conditions, stirring and heating are stopped. After standing and ultrasonication, a certain amount of PVA solution is taken and a solution obtained by dissolving a chiral biphenyl aromatic macrocyclic compound in tetrahydrofuran is added. The mixture is mixed and shaken, ultrasonicated, and dripped onto a glass plate. The mixture is dried to obtain a PVA film doped with a chiral macrocycle, i.e., a composite.

[0047] Example 2

[0048] This embodiment specifically discloses a method for preparing a complex prepared from the chiral biphenyl aromatic macrocyclic compound and a polymer, as follows:

[0049] Weigh 1 g of polyvinyl alcohol (PVA) and pour it into a 50 mL round-bottom flask, add 15 mL of water, add a magnet, stir and heat at 50-90 ° C (preferably 90 ° C) for 2-12 hours (preferably 3 hours), turn off the heating and stirring, let it stand for 10-30 minutes (preferably 20 minutes), ultrasonicate for 5-15 minutes (preferably 10 minutes), take out 1 mL of PVA solution with a rubber-tipped dropper, add a solution of 0.66 g of a chiral biphenyl aromatic macrocyclic compound dissolved in 0.5 mL of tetrahydrofuran, shake, ultrasonicate for 10 minutes, drop it onto a glass plate, place it in an oven, and dry it at 60 ° C to obtain a PVA film doped with a chiral macrocycle, wherein the mass ratio of PVA to the chiral macrocycle in this film is 100:1.

[0050] Example 3

[0051] The present invention also provides the use of the complex or the complex prepared by the preparation method described in Example 2 as a chiral luminescent material.

[0052] Test example

[0053] The preparation and comparative analysis of PVA film and chiral macrocyclic@PVA film are as follows:

[0054] Weigh 1g of polyvinyl alcohol (PVA) into a 50mL round-bottom flask, add 15mL of water, and a magnetic stirrer. Stir and heat at 90°C for 3 hours. Turn off the heat and stirring, let it stand for 20 minutes, sonicate for 10 minutes, and then drip 1mL onto a glass plate with a pipette. The flask is then placed in an oven at 60°C to obtain a PVA film. Remove 1mL and add a solution containing 0.66g of a chiral macrocycle dissolved in 0.5mL of tetrahydrofuran. Shake and sonicate for 10 minutes. The resulting solution is then dripped onto a glass plate and dried in an oven at 60°C to obtain a PVA film doped with the chiral macrocycle.

[0055] The obtained PVA film and the PVA film doped with chiral macrocycle were tested for UV-visible absorption spectrum and circular dichroism spectrum. Figure 3 and Figure 4 As shown, the UV-visible absorption spectrum shows that the complex (chiral macrocycle @PVA film) has a good UV absorption peak at 250-400 nm, and the circular dichroism spectrum shows that the signal of the complex (chiral macrocycle @PVA film) is obvious. Compared with the PVA film, the chiral polymer film prepared in the present invention exhibits good circular dichroism absorption properties and fluorescence properties.

[0056] Among them, when testing the CD of the composite, the PVA film was used as the background to obtain the CD spectrum of the composite. Figure 4 This is the CD image after deducting the PVA film.

[0057] The present invention discloses a synthesis method and application of a chiral biphenyl aromatic macrocyclic compound. An achiral pentaphenyl macrocycle is obtained by covalently modifying it and introducing a chiral side chain. The chiral side chain is then doped into a polymer to prepare a chiral polymer film exhibiting good circular dichroism absorption and fluorescence properties.

[0058] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited to the specific details in the above-mentioned embodiments. Those skilled in the art will appreciate that, without departing from the spirit and scope of the present invention, a variety of equivalent replacements, modifications or improvements may be made to the technical solutions of the present invention and their embodiments, and these all fall within the scope of the present invention. It should also be noted that, in the absence of contradiction, the various specific technical features described in the above-mentioned specific embodiments may be combined in any suitable manner to avoid unnecessary repetition. In addition, any combination may be performed between the various embodiments of the present invention, and as long as they do not violate the concept of the present invention, they shall also be regarded as the contents disclosed by the present invention.

Claims

1. A chiral biphenyl aromatic macrocyclic compound, characterized in that: Has the following structure:

2. A method for preparing a chiral biphenyl aromatic macrocyclic compound as claimed in claim 1, characterized in that: The following steps are involved: The 2,4-position pentadiphenyl tricyclic perhydroxyl group is dissolved in a non-protonic polar solvent, potassium iodide is added, and the mixture is reacted under the action of a base to obtain a reaction solution, and the reaction solution is separated by column chromatography to obtain a chiral biphenyl aromatic macrocyclic compound.

3. The method for preparing a chiral biphenyl aromatic macrocyclic compound according to claim 2, wherein: The aprotic polar solvent is N,N-dimethylformamide or acetone.

4. The method for preparing a chiral biphenyl aromatic macrocyclic compound according to claim 2, wherein: The base includes at least one of cesium carbonate, potassium carbonate, potassium hydroxide and sodium hydroxide.

5. The method for preparing a chiral biphenyl aromatic macrocyclic compound according to claim 2, wherein: The preparation method specifically comprises: Dissolve the 2,4-pentaphenyl tricyclic perhydroxyl group and (S)-2-methylbutyl p-toluenesulfonate in N,N-dimethylformamide solution according to a predetermined ratio, then add a predetermined amount of potassium iodide and sodium carbonate, stir until completely dissolved, protect with nitrogen, continue stirring, and heat under reflux overnight to carry out the reaction; The reaction process was monitored by thin-layer chromatography. After the reaction was completed, the reaction solution was cooled to room temperature and transferred to a separatory funnel. Water was added and shaken to precipitate a brown upper solid. The solid and solution in the separatory funnel were then filtered, the upper solid was collected and dried, and the sample was separated by column chromatography to obtain a chiral biphenyl aromatic macrocyclic compound.

6. The method for preparing a chiral biphenyl aromatic macrocyclic compound according to claim 5, wherein: The reaction requires the addition of raw materials according to a set equivalent ratio: 2,4-pentaphenyl tricyclic perhydroxyl group: (S)-2-methylbutyl p-toluenesulfonate: cesium carbonate: potassium iodide = 1:24:36:24.

1.

7. A complex prepared from the chiral biphenyl aromatic macrocyclic compound of claim 1 and a polymer, characterized in that: The composite is a chiral polymer film prepared by doping the chiral biphenyl aromatic macrocyclic compound into a polymer.

8. The method for preparing the composite according to claim 7, characterized in that: The following steps are involved: In a round-bottom flask, polyvinyl alcohol (PVA) and water are added in sequence according to a set ratio, and a magnet is added. After stirring and heating for a set time under certain temperature conditions, stirring and heating are stopped. After standing and ultrasonication, a certain amount of PVA solution is taken and a solution obtained by dissolving a chiral biphenyl aromatic macrocyclic compound in tetrahydrofuran is added. The mixture is mixed and shaken, ultrasonicated, and dripped onto a glass plate. The mixture is dried to obtain a PVA film doped with a chiral macrocycle, i.e., a composite.

9. Use of the complex according to claim 7 or the complex prepared by the preparation method according to claim 8 as a chiral luminescent material.

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