Chiral biphenyl aromatic hydrocarbon macrocyclic compound and compound, preparation method and application thereof

Abstract

The invention provides a chiral biphenyl aromatic hydrocarbon macrocyclic compound and a compound, a preparation method and application thereof, and belongs to the technical field of organic materials. The specific structural formula of the chiral biphenyl aromatic hydrocarbon macrocyclic compound is given, 2, 4-position pentaphenyl three-membered ring complete hydroxyl is dissolved in an aprotic polar solvent, potassium iodide is added, reaction is performed under the action of alkali to obtain reaction liquid, and the chiral biphenyl aromatic hydrocarbon macrocyclic compound is obtained through column chromatography separation. The chiral polymer film is obtained by introducing an achiral pentaphenyl macroring into a chiral side chain through covalent modification and further doping the achiral pentaphenyl macroring into a polymer, and the chiral polymer film can be prepared and shows good circular dichroism absorption property and fluorescent property. The preparation method of the chiral biphenyl aromatic hydrocarbon macrocyclic compound and the compound provided by the invention is simple and convenient, convenient to modify and simple to separate, so that the compound and the compound have wide application prospects in the aspects of chiral display devices, encryption materials and the like.

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 mainly include central chiral molecules, axial chiral molecules, planar chiral molecules and helical chiral molecules. Due to their status and role in disciplines and industries such as chemistry and chemical engineering, life and medicine, and materials, the catalytic asymmetric synthesis of these chiral molecules has always been the core and frontier research field of synthetic chemistry. Chiral luminescent materials have special left-handed and right-handed structures. In addition to emitting ordinary photoluminescence, they can also emit circularly polarized light (CPL). The chiral luminescent materials are used as the luminescent center to prepare devices that can directly emit circularly polarized electroluminescence (CPEL), namely CP-OLEDs, which have great application prospects in the field of 3D display.

[0003] Circularly polarized luminescence (CPL) is the phenomenon that a chiral luminophore emits left-handed and right-handed circularly polarized light under the excitation of unpolarized light. In recent years, CPL materials have attracted people's interest due to their applications in chemical and biological sensing, chiral optical materials, asymmetric catalysis, optoelectronic devices, etc. However, traditional organic light-emitting materials will show problems of decreased fluorescence and CPL performance and low asymmetry factor when aggregated, which limits the practical application of CPL materials. Chiral compounds with circularly polarized luminescence have shown good application prospects in liquid crystal display, biosensing, information storage, etc. Therefore, it is of great significance to develop a chiral compound with high quantum yield and asymmetry factor, which 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 pentaphenyl macrocycle through covalent modification, and then further doped into a polymer to prepare a chiral polymer film, which exhibits good circular dichroism absorption properties 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 also provides a method for preparing the chiral biphenyl aromatic macrocyclic compound, comprising the following steps:

[0009] The 2,4-position pentadiphenyl tricyclic perhydroxyl groups are dissolved in a non-protonic polar solvent, potassium iodide is added, and a reaction liquid is obtained under the action of a base. The reaction liquid 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 comprises:

[0013] Dissolve the 2,4-position 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 also provides a method for preparing a complex prepared from the chiral biphenyl aromatic macrocyclic compound and a polymer, comprising the following steps:

[0017] In a round-bottom flask, 1g polyvinyl alcohol PVA and 15mL water are added in sequence according to the set ratio, and a magnetic particle is added. After stirring and heating for a set time under certain temperature conditions, stirring and heating are stopped. After standing and ultrasonication, 1mL PVA solution is taken, and 0.25mL tetrahydrofuran is added to dissolve 0.66mg of chiral biphenyl aromatic macrocyclic compound to obtain a solution. The solution is 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 is 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 pentaphenyl macrocycle into a chiral side chain, and then further doped into a polymer to prepare a chiral polymer film, which exhibits good circular dichroism absorption and fluorescence properties.

[0021] (2) The present invention provides a simple and efficient method for synthesizing chiral biphenyl aromatic hydrocarbon macrocycles to address the problems of complicated synthesis and low yield of chiral macrocycles. The method uses 2,4-pentabiphenyl tricyclic perhydroxyl groups and (S)-2-methylbutyl p-toluenesulfonate and other reactants to synthesize a supramolecular chiral macrocycle in a one-pot manner 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, so that it has 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 drawings required for use in the embodiments will be briefly introduced below. 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 creative labor.

[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 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 should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

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

[0030] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation 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 a conflict with any incorporated document, the content of this specification shall prevail.

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

[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 groups are dissolved in a non-protonic polar solvent, potassium iodide is added, and a reaction liquid is obtained under the action of a base. The reaction liquid 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 a method for preparing the chiral biphenyl aromatic macrocyclic compound, as follows:

[0040]

[0041] First, the raw materials were added according to the set equivalent ratio, 2,4-pentaphenyl tricyclic perhydroxyl: (S)-2-methylbutyl p-toluenesulfonate: cesium carbonate: potassium iodide = 1:24:36:24.1. Specifically, 0.72g of 2,4-pentaphenyl tricyclic perhydroxyl (synthesized by reference 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 to a 250mL double-necked round-bottom flask in sequence, and then 50mL of dry N,N-dimethylformamide was added. After the reaction was set up, stirring was started and N 2 , do N 2 Protect, heat under reflux overnight to react. Monitor the reaction by thin layer chromatography (TLC). After the reaction is completed, wait for the reaction solution to cool to room temperature, transfer it to a separatory funnel, add a large amount of water, shake, precipitate a brown upper solid, then transfer the mixed system in the separatory funnel to the funnel for suction filtration in batches, collect the upper solid, mix the sample and spin dry, and separate by column chromatography (petroleum ether / dichloromethane, 3:1, v / v) to obtain the product.

[0042] Biphenyl aromatic chiral macrocycle: 1 H NMR (400 MHz, CDCl 3 )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),1.8 3(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 macrocyclic compound and a polymer. The complex is a chiral polymer film prepared by doping the chiral biphenyl aromatic 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 the excitation of 365nm ultraviolet light, the polymer itself is colorless, and it shows bright blue after being doped with the chiral biphenyl aromatic macrocycle. Figure 2Description: The prepared complex shows blue fluorescence under 365nm ultraviolet light excitation and has good fluorescence properties; the luminescent properties of the complex have nothing to do with 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 by 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 tetrahydrofuran is added to dissolve the chiral biphenyl aromatic macrocyclic compound to obtain a solution, mixed and shaken, ultrasonicated, dripped onto a glass plate, and 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 1g of polyvinyl alcohol (PVA) and pour it into a 50mL round-bottom flask, add 15mL 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 stand for 10-30 minutes (preferably 20 minutes), ultrasonicate for 5-15 minutes (preferably 10 minutes), take out 1mL of PVA solution with a rubber-tipped dropper, add a solution of 0.66g of chiral biphenyl aromatic macrocyclic compound dissolved in 0.5mL of tetrahydrofuran, oscillate, ultrasonicate for 10 minutes, drop onto a glass plate, place in an oven, and dry at 60°C to obtain a PVA film doped with a chiral macrocycle, in which the mass ratio of PVA to chiral macrocycle 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) and pour it into a 50mL round-bottom flask, add 15mL of water, add a magnet, stir and heat at 90℃ for 3 hours, turn off the heating and stirring, let it stand for 20 minutes, ultrasonicate for 10 minutes, drip 1mL onto a glass plate with a rubber dropper, place it in an oven, and dry it at 60℃ to obtain a PVA film. Take out 1mL and add a solution of 0.66g of chiral macrocycle dissolved in 0.5mL of tetrahydrofuran, shake, ultrasonicate for 10 minutes, drip it onto a glass plate, place it in an oven, and dry it at 60℃ to obtain a PVA film doped with 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 composite (chiral macrocycle @PVA film) has a good UV absorption peak at 250-400nm, and the circular dichroism spectrum shows that the signal of the composite (chiral macrocycle @PVA film) is obvious. Compared with the PVA film, the chiral polymer film prepared by 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 is used as the background to obtain the CD spectrum of the composite. Figure 4 This is the CD image after the PVA film has been deducted.

[0057] The invention discloses a synthesis method and application of a chiral biphenyl aromatic macrocyclic compound, wherein an achiral pentaphenyl macrocyclic compound is introduced into a chiral side chain through covalent modification, and then further doped into a polymer to prepare a chiral polymer film, which exhibits good circular dichroism absorption properties 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 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 solution of the present invention and its embodiments, which all fall within the scope of the present invention. It should also be noted that, in the absence of contradictions, the various specific technical features described in the above specific embodiments may be combined in any suitable manner to avoid unnecessary duplication. In addition, any combination of the various embodiments of the present invention may also be performed, 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: It 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 groups are dissolved in a non-protonic polar solvent, potassium iodide is added, and a reaction liquid is obtained under the action of a base. The reaction liquid 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, characterized in that: 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, characterized in that: The alkali 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, characterized in that: 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 set ratio, add a set amount of potassium iodide and sodium carbonate, stir until completely dissolved, protect with nitrogen, continue stirring, and heat under reflux overnight to react; 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, characterized in that: The reaction requires the input of raw materials according to a set equivalent ratio, 2,4-pentaphenyl tricyclic perhydroxy: (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 and a polymer according to claim 1, 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 tetrahydrofuran is added to dissolve the chiral biphenyl aromatic macrocyclic compound to obtain a solution, mixed and shaken, ultrasonicated, dripped onto a glass plate, and 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.

Images