Chiral cyclophane molecule BinapoBox4PF6 as well as preparation method and application thereof

Abstract

The invention discloses a chiral cyclophane molecule BinapoBox.4PF6 as well as a preparation method and application thereof, belongs to the field of macrocyclic molecule research, and particularly relates to a chiral cyclophane molecule as well as a preparation method and application thereof. The invention aims to solve the problems that the existing chiral aromatic dye is high in synthesis cost and the process of inducing an achiral compound to generate chirality is complicated. The structural general formula of the chiral cyclophane molecule BinapoBox. 4PF6 disclosed by the invention is C92H70F24N4O2P6, and the structural general formula is shown in the description. The chiral cyclophane molecule BinapoBox.4PF6 and the aromatic dye have excellent binding capacity and special fluorescent property, so that the chiral cyclophane molecule BinapoBox.4PF6 becomes a good chiral host material for preparing a chiral host-achiral object assembly (CPL) material. The complex synthesis modification is avoided, the expensive liquid crystal material is also avoided, and the cost can be greatly reduced by amplifying equivalent batch preparation. The chiral cyclophane molecule disclosed by the invention is a novel chiral cyclophane product which can be recycled and has universality.

Description

Technical Field

[0001] The present invention belongs to the field of macrocyclic molecule research, and specifically relates to a chiral cyclophane molecule, a preparation method and application thereof; Background Art

[0002] The use of macrocyclic synthetic receptors for molecular recognition is an important research area in supramolecular chemistry; pioneering examples on this topic date back to the 1980s; macrocyclic models are key to further understanding the remarkable properties exhibited by proteins: high binding affinity, superior binding selectivity and extreme catalytic properties;

[0003] In supramolecular chemistry, cyclophane is an artificial receptor, which is a cage-type macrocyclic compound formed by connecting two or more aromatic compounds with a short spacer (bridge). By changing or regulating the type of aromatic compound, the type and number of bridges, it is very convenient to give cyclophane physical and chemical properties such as hydrogen bonding, electrostatic interaction, hydrophobic interaction, π-π, ion-π interaction, etc., so that it has some characteristics of crown ether, cyclodextrin and multidentate ligand. With the development of cyclophane chemistry, more and more cyclophane compounds, especially chiral cyclophane compounds (belonging to CPL materials) have been synthesized. Because they have many properties such as molecular recognition and optical properties, they are used in host-guest chemistry, analytical chemistry, catalysts, artificial enzymes, drugs, etc. There are huge application potentials in the fields of chemistry and materials science; there are many types of cyclophanes, with different functions and strong applicability. The design and synthesis of cyclophanes with special functions will still be one of the hot spots of future research; in addition, cyclophanes have multiple active sites and their cavity sizes and have specific recognition properties for substrates, which provide a feasible basis for the development of dynamic chemistry, dynamic materials, smart materials, nanomaterials, chemistry and art, and supramolecular polymer chemistry; although many cyclophanes have been synthesized, due to the current synthetic methods, there are few reports of chiral cyclophanes; however, we believe that with the deepening of chiral cyclophane chemistry research, the problems in the development of chiral cyclophane chemistry will be solved, and chiral cyclophane chemistry will gradually become an important research. At present, the synthesis of chiral aromatic dyes still relies on liquid phase separation and asymmetric synthesis, which makes the price of chiral compounds very expensive. Therefore, the development of new chiral compounds that rely on non-covalent bonds to induce chirality is still one of the hot spots of chiral chemistry, especially for inducing chirality of non-chiral luminophores to prepare multicolor CPL, which has received widespread attention. There are currently three common schemes for inducing chirality in achiral aromatic dyes: modification of chiral organic dyes, supramolecular assemblies, and liquid crystal doping; for example, in order to obtain organic CPL (circularly polarized luminescence) active materials, combining the chiral part with the luminophore through a covalent bond is the most common approach. However, cumbersome synthesis processes are sometimes unavoidable. In addition, the CPL activity of the obtained CPL materials is unpredictable. Similarly, inorganic CPL active materials also require difficult inorganic synthesis by loading chiral sources on prefabricated nanomaterials. Therefore, it is very meaningful to develop a simple and universal method for manufacturing CPL active materials. Summary of the invention

[0004] In order to solve the problems of high synthesis cost of existing chiral aromatic dyes and complicated process of inducing chirality of achiral compounds, the present invention proposes a chiral cyclophane molecule BinapoBox·4PF6 and its preparation method and application

[0005] The structural formula of the chiral cyclophane molecule BinapoBox·4PF6 of the present invention is:

[0006]

[0007] The chiral cyclophane molecule BinapoBox·4PF6 has the general structural formula of C 92 H 70 F 24 N4O2P6.

[0008] The preparation method of the chiral cyclophane molecule BinapoBox·4PF6 is carried out according to the following steps:

[0009] Step 1, Synthesis of 1,4-bis(bromomethyl)benzene:

[0010] 7.1-7.2 g of N-bromosuccinimide and 160-170 mg of azobisisobutyronitrile are added to 60-70 mL of an acetonitrile solution of p-xylene; after stirring under reflux for 16-17 hours, the mixture is evaporated in vacuo and purified by chromatography to obtain 1,4-bis(bromomethyl)benzene;

[0011] The ratio of the mass of xylene to the volume of acetonitrile in the xylene-acetonitrile solution is 2-3 g: 60-90 mL;

[0012] Step 2: Synthesis of 4,4'-di(pyridin-4-yl)-1,1'-biphenyl:

[0013] 15-20 mL of dry N,N-dimethylformamide was degassed by bubbling N2 for 2 hours, followed by the addition of 468-500 mg of 4,4'-dibromo-1,1'-biphenyl, 80-90 mg of Pd(PPh3)4, 400-500 mg of 4-pyridineboric acid and 2.5-3.0gCs2CO3, heating the mixture to 110°C and maintaining for 24 hours to form a suspension, evaporating the solvent, extracting the remaining residue with chloroform, washing the extracted product with K2CO3 solution and saturated brine in turn, drying the product after washing with MgSO4, then removing the chloroform by evaporation and concentration, adding 5-10mL of dichloromethane to dissolve the solid product obtained by evaporation and concentration, adding 100-120mL of n-hexane to the obtained solution for precipitation, washing the obtained solid product with 10-20mL of n-hexane, and recrystallizing with 10-20mL of ethyl acetate after washing to obtain 4,4'-di(pyridin-4-yl)-1,1'-biphenyl;

[0014] Step 3: Synthesis of (R)-4,4-bis-4-pyridyl-1,1'-binaphthyl-2,2'-bisdiphenylphosphine:

[0015] 3.25-3.5 g (R)-4,4-dibromo-1,1'-binaphthyl-2,2'-bisdiphenylphosphine, 0.07-0.10 g Pd(PPh3)4, 1.08-1.20 g 4-pyridineboric acid and 2.21-2.50 g K2CO3 are placed in a mixture of 150-200 mL 1,4-dioxane and water, heated under reflux for 7 days in a nitrogen atmosphere, the obtained organic phase is washed with 275-300 mL H2O, the solvent is evaporated, and the remaining solid is recrystallized from propan-2-ol;

[0016] The volume ratio of 1,4-dioxane to water in the mixed solution of 1,4-dioxane and water is 2:1;

[0017] Step 4: Synthesis of bis(4-bromomethylbenzyl)(4,4′-(4,4′-biphenyl)bipyridinium-1-ium)bis(hexafluorophosphate):

[0018] ① In a round-bottom three-necked flask, add 5.14-5.2 g of 1,4-bis(bromomethyl)benzene prepared in step 1 to a mixture of 240 mL of CH2Cl2 and acetonitrile, heat and stir in an oil bath at 50°C until all the solid matter is dissolved; then increase the oil bath temperature to 90°C to obtain a reaction solution;

[0019] The volume ratio of CH2Cl2 to acetonitrile in the mixture of CH2Cl2 and acetonitrile is 1:1;

[0020] ②, add 0.6-0.7g of 4,4'-di(pyridin-4-yl)-1,1'-biphenyl prepared in step 2 to 120-150mL of acetonitrile, and then titrate it into the reaction solution obtained in step ① within 4 hours, reflux and heat for 24-30 hours, cool to room temperature, filter and collect the yellow precipitate, and wash with CH2Cl2 to obtain a yellow solid; dissolve the yellow solid in 1-1.5L methanol below room temperature, and then add 400-500mg NH4PF6 and 1L H2O below room temperature, and precipitate to obtain bis(4-bromomethylbenzyl)(4,4'-(4,4'-biphenyl)bipyridin-1-ium)bis(hexafluorophosphate);

[0021] Step 5: Synthesis of chiral cyclophane molecule BinapoBox·4PF6:

[0022] 0.11-0.12 g of (R)-4,4-bis-4-pyridyl-1,1'-binaphthyl-2,2'-bisdiphenylphosphine prepared in step 3, 0.35-0.40 g of bis(4-bromomethylbenzyl)(4,4'-(4,4'-biphenyl)bipyridinium-1-ium)bis(hexafluorophosphate) prepared in step 4 and 0.027-0.030 g of tetrabutylammonium iodide were added to 180-200 mL of dry acetonitrile and stirred at 80-90° C. for 72-80 min. 80h, then add 3mL of concentrated hydrochloric acid to stop the reaction, filter and collect the precipitate, then wash the precipitate with acetone and CH2Cl2 in turn to remove residual tetrabutylammonium iodide, dissolve the precipitate in 500-600mL of 60°C methanol, and then add an aqueous solution of NH4PF6 to obtain a solid product. After the reaction, collect the precipitate and filter it, dissolve the product in 10mL of acetonitrile to obtain a reaction solution, and place the reaction solution in an isopropyl ether vapor environment for 2-3 crystallizations to complete.

[0023] The chiral cyclophane molecule BinapoBox·4PF6 is used to prepare CPL active materials in combination with aromatic dyes. The preparation method is carried out according to the following steps:

[0024] 1. mixing a chiral cyclophane and a solvent to obtain a chiral cyclophane solution;

[0025] The solvent is acetonitrile or methanol;

[0026] The concentration of the chiral cyclophane solution is 1×10 -6 ~1×10 -2 mol / L;

[0027] 2. Dissolve the aromatic dye in the same solvent as in step 1, and then add it to the chiral cyclophane solution prepared in step 1 to complete the preparation of the CPL active material;

[0028] The concentration of the aromatic dye is 0.01-0.1 mol / L;

[0029] The molar ratio of the aromatic dye to the chiral cyclophane is (1-4):1.

[0030] The principles and beneficial effects of the present invention are:

[0031] 1. The principle of induction of the chiral cyclophane molecule BinapoBox·4PF6 of the present invention is that the unique box structure of the chiral cyclophane molecule can effectively bind to the aromatic molecule through the π-π interaction, and the axial chirality is transferred to the aromatic dye through the rotation of the chiral binaphthol unit of the cyclophane, thereby achieving chiral induction and preparing materials with chiral optical properties.

[0032] 2. The chiral cyclopan molecule BinapoBox·4PF6 of the present invention has excellent binding ability and special fluorescence properties with aromatic dyes, making the chiral cyclopan molecule BinapoBox·4PF6 a good chiral host material for preparing chiral host-achiral guest assembly CPL materials. The present invention avoids cumbersome synthetic modifications and also avoids expensive liquid crystal materials. It can be prepared in batches by enlarging equivalents, greatly reducing costs. In addition, because the chiral cyclopan molecule BinapoBox·4PF6 of the present invention uses non-covalent bonds to induce guest chirality, it is less difficult to replace the guest. It can be washed with organic solvents to replace different guest molecules for recycling, and is suitable for most aromatic small molecule dyes. It is a new chiral cyclopan product that can be recycled and has universality.

[0033] 3. The chiral cyclophane molecule BinapoBox·4PF6 of the present invention is an organic small molecule, the raw materials for preparation are easily obtained, and the preparation cost is low. Compared with inorganic nanomaterials, organic synthesis modification, liquid crystal doping, etc., the preparation cost of chiral optically active materials can be greatly reduced.

[0034] 4. The chiral cyclophane molecule BinapoBox·4PF6 of the present invention has a box-like structure, which enables it to spatially recognize aromatic hydrocarbons, that is, the chiral cyclophane molecule can be used to form cyclophane-aromatic hydrocarbons by combining with aromatic hydrocarbons. The CPL of cyclophane-aromatic hydrocarbons and the CPL of the chiral cyclophane molecule can be compared to achieve qualitative analysis of aromatic hydrocarbon compounds; when the chiral cyclophane molecule BinapoBox·4PF6 is combined with different aromatic hydrocarbons, the dihedral angle information of the cyclophane binaphthyl part will change, which will lead to changes in the CPL spectrum, causing g lum The chiral information of each aromatic hydrocarbon on binaphthyl changes differently, which makes the qualitative analysis of aromatic hydrocarbons more accurate. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 The CD absorption change diagram of cyclophane combined with different equivalents of 4-(perylene-3-yl)pyridine dye guest;

[0036] Figure 2 This is the fluorescence spectrum change diagram (PL spectrum) of cyclophane combined with different equivalents of 4-(perylene-3-yl)pyridine dye guests. DETAILED DESCRIPTION

[0037] The technical solution of the present invention is not limited to the specific implementation modes listed below, but also includes any reasonable combination of the specific implementation modes.

[0038] Specific implementation method 1: The structural formula of the chiral cyclophane molecule BinapoBox·4PF6 in this implementation method is:

[0039]

[0040] The chiral cyclophane molecule BinapoBox·4PF6 has the general structural formula of C 92 H 70 F 24 N4O2P6.

[0041] 1. The principle of induction of the chiral cyclophane molecule BinapoBox·4PF6 in this embodiment is that the unique box structure of the chiral cyclophane molecule can effectively bind to the aromatic molecule through the π-π interaction, and the axial chirality is transferred to the aromatic dye through the rotation of the chiral binaphthol unit of the cyclophane, thereby achieving chiral induction and preparing materials with chiral optical properties.

[0042] 2. The chiral cyclopan molecule BinapoBox·4PF6 of this embodiment has excellent binding ability and special fluorescent properties with aromatic dyes, making the chiral cyclopan molecule BinapoBox·4PF6 a good chiral host material for preparing chiral host-achiral guest assembly CPL materials. This embodiment avoids cumbersome synthetic modifications and also avoids expensive liquid crystal materials. It can be prepared in batches by enlarging equivalents, greatly reducing costs. In addition, because the chiral cyclopan molecule BinapoBox·4PF6 of this embodiment uses non-covalent bonds to induce guest chirality, guest replacement is less difficult, and organic solvents can be used to wash and replace different guest molecules for recycling. It is also suitable for most aromatic small molecule dyes and is a new chiral cyclopan product that can be recycled and has universality.

[0043] 3. The chiral cyclophane molecule BinapoBox·4PF6 in this embodiment is an organic small molecule, the raw materials for preparation are easily available, and the preparation cost is low. Compared with inorganic nanomaterials, organic synthesis modification, liquid crystal doping, etc., the preparation cost of chiral optically active materials can be greatly reduced.

[0044] 4. The chiral cyclopan molecule BinapoBox·4PF6 of this embodiment has a box-like structure, which enables it to spatially recognize aromatic hydrocarbons. That is, the chiral cyclopan molecules can be combined with aromatic hydrocarbons to form cyclopan-aromatic hydrocarbons. The CPL of cyclopan-aromatic hydrocarbons and the CPL of the chiral cyclopan molecules can be compared to achieve qualitative analysis of aromatic hydrocarbon compounds. When the chiral cyclopan molecule BinapoBox·4PF6 combines with different aromatic hydrocarbons, the dihedral angle information of the cyclopan-binaphthyl part will change, which will lead to changes in the CPL spectrum, causing g lum The chiral information of each aromatic hydrocarbon on binaphthyl changes differently, which makes the qualitative analysis of aromatic hydrocarbons more accurate.

[0045] Specific embodiment 2: The preparation method of the chiral cyclophane molecule BinapoBox·4PF6 in this embodiment is carried out according to the following steps:

[0046] Step 1, Synthesis of 1,4-bis(bromomethyl)benzene:

[0047] 7.1-7.2 g of N-bromosuccinimide and 160-170 mg of azobisisobutyronitrile are added to 60-70 mL of an acetonitrile solution of p-xylene; after stirring under reflux for 16-17 hours, the mixture is evaporated in vacuo and purified by chromatography to obtain 1,4-bis(bromomethyl)benzene;

[0048] The ratio of the mass of xylene to the volume of acetonitrile in the xylene-acetonitrile solution is 2-3 g: 60-90 mL;

[0049] Step 2: Synthesis of 4,4'-di(pyridin-4-yl)-1,1'-biphenyl:

[0050] 15-20 mL of dry N,N-dimethylformamide was degassed by bubbling N2 for 2 hours, followed by the addition of 468-500 mg of 4,4'-dibromo-1,1'-biphenyl, 80-90 mg of Pd(PPh3)4, 400-500 mg of 4-pyridineboric acid and 2.5-3.0gCs2CO3, heating the mixture to 110°C and maintaining for 24 hours to form a suspension, evaporating the solvent, extracting the remaining residue with chloroform, washing the extracted product with K2CO3 solution and saturated brine in turn, drying the product after washing with MgSO4, then removing the chloroform by evaporation and concentration, adding 5-10mL of dichloromethane to dissolve the solid product obtained by evaporation and concentration, adding 100-120mL of n-hexane to the obtained solution for precipitation, washing the obtained solid product with 10-20mL of n-hexane, and recrystallizing with 10-20mL of ethyl acetate after washing to obtain 4,4'-di(pyridin-4-yl)-1,1'-biphenyl;

[0051] Step 3: Synthesis of (R)-4,4-bis-4-pyridyl-1,1'-binaphthyl-2,2'-bisdiphenylphosphine:

[0052] 3.25-3.5 g (R)-4,4-dibromo-1,1'-binaphthyl-2,2'-bisdiphenylphosphine, 0.07-0.10 g Pd(PPh3)4, 1.08-1.20 g 4-pyridineboric acid and 2.21-2.50 g K2CO3 are placed in a mixture of 150-200 mL 1,4-dioxane and water, heated under reflux for 7 days in a nitrogen atmosphere, the obtained organic phase is washed with 275-300 mL H2O, the solvent is evaporated, and the remaining solid is recrystallized from propan-2-ol;

[0053] The volume ratio of 1,4-dioxane to water in the mixed solution of 1,4-dioxane and water is 2:1;

[0054] Step 4: Synthesis of bis(4-bromomethylbenzyl)(4,4′-(4,4′-biphenyl)bipyridinium-1-ium)bis(hexafluorophosphate):

[0055] ① In a round-bottom three-necked flask, add 5.14-5.2 g of 1,4-bis(bromomethyl)benzene prepared in step 1 to a mixture of 240 mL of CH2Cl2 and acetonitrile, heat and stir in an oil bath at 50°C until all the solid matter is dissolved; then increase the oil bath temperature to 90°C to obtain a reaction solution;

[0056] The volume ratio of CH2Cl2 to acetonitrile in the mixture of CH2Cl2 and acetonitrile is 1:1;

[0057] ②, add 0.6-0.7g of 4,4'-di(pyridin-4-yl)-1,1'-biphenyl prepared in step 2 to 120-150mL of acetonitrile, and then titrate it into the reaction solution obtained in step ① within 4 hours, reflux and heat for 24-30 hours, cool to room temperature, filter and collect the yellow precipitate, and wash with CH2Cl2 to obtain a yellow solid; dissolve the yellow solid in 1-1.5L methanol below room temperature, and then add 400-500mg NH4PF6 and 1L H2O below room temperature, and precipitate to obtain bis(4-bromomethylbenzyl)(4,4'-(4,4'-biphenyl)bipyridin-1-ium)bis(hexafluorophosphate);

[0058] Step 5: Synthesis of chiral cyclophane molecule BinapoBox·4PF6:

[0059] 0.11-0.12 g of (R)-4,4-bis-4-pyridyl-1,1'-binaphthyl-2,2'-bisdiphenylphosphine prepared in step 3, 0.35-0.40 g of bis(4-bromomethylbenzyl)(4,4'-(4,4'-biphenyl)bipyridinium-1-ium)bis(hexafluorophosphate) prepared in step 4 and 0.027-0.030 g of tetrabutylammonium iodide were added to 180-200 mL of dry acetonitrile and stirred at 80-90° C. for 72-80 min. 80h, then add 3mL of concentrated hydrochloric acid to stop the reaction, filter and collect the precipitate, then wash the precipitate with acetone and CH2Cl2 in turn to remove residual tetrabutylammonium iodide, dissolve the precipitate in 500-600mL of 60°C methanol, and then add an aqueous solution of NH4PF6 to obtain a solid product. After the reaction, collect the precipitate and filter it, dissolve the product in 10mL of acetonitrile to obtain a reaction solution, and place the reaction solution in an isopropyl ether vapor environment for 2-3 crystallizations to complete.

[0060] 1. The principle of induction of the chiral cyclophane molecule BinapoBox·4PF6 in this embodiment is that the unique box structure of the chiral cyclophane molecule can effectively bind to the aromatic molecule through the π-π interaction, and the axial chirality is transferred to the aromatic dye through the rotation of the chiral binaphthol unit of the cyclophane, thereby achieving chiral induction and preparing materials with chiral optical properties.

[0061] 2. The chiral cyclopan molecule BinapoBox·4PF6 of this embodiment has excellent binding ability and special fluorescent properties with aromatic dyes, making the chiral cyclopan molecule BinapoBox·4PF6 a good chiral host material for preparing chiral host-achiral guest assembly CPL materials. This embodiment avoids cumbersome synthetic modifications and also avoids expensive liquid crystal materials. It can be prepared in batches by enlarging equivalents, greatly reducing costs. In addition, because the chiral cyclopan molecule BinapoBox·4PF6 of this embodiment uses non-covalent bonds to induce guest chirality, guest replacement is less difficult, and organic solvents can be used to wash and replace different guest molecules for recycling. It is also suitable for most aromatic small molecule dyes and is a new chiral cyclopan product that can be recycled and has universality.

[0062] 3. The chiral cyclophane molecule BinapoBox·4PF6 in this embodiment is an organic small molecule, the raw materials for preparation are easily available, and the preparation cost is low. Compared with inorganic nanomaterials, organic synthesis modification, liquid crystal doping, etc., the preparation cost of chiral optically active materials can be greatly reduced.

[0063] 4. The chiral cyclopan molecule BinapoBox·4PF6 of this embodiment has a box-like structure, which enables it to spatially recognize aromatic hydrocarbons. That is, the chiral cyclopan molecules can be combined with aromatic hydrocarbons to form cyclopan-aromatic hydrocarbons. The CPL of cyclopan-aromatic hydrocarbons and the CPL of the chiral cyclopan molecules can be compared to achieve qualitative analysis of aromatic hydrocarbon compounds. When the chiral cyclopan molecule BinapoBox·4PF6 combines with different aromatic hydrocarbons, the dihedral angle information of the cyclopan-binaphthyl part will change, which will lead to changes in the CPL spectrum, causing g lum The chiral information of each aromatic hydrocarbon on binaphthyl changes differently, which makes the qualitative analysis of aromatic hydrocarbons more accurate.

[0064] Specific implementation method three: This implementation method is different from specific implementation method two in that: the developing solvents used in the chromatography purification in step 1 are petroleum ether and dichloromethane, and the volume ratio of petroleum ether to dichloromethane is 1:1.

[0065] Specific embodiment 4: This embodiment differs from specific embodiment 2 in that: the remaining residue in step 2 is extracted 3 times with chloroform, and the volume of chloroform used each time is 20-30 mL.

[0066] Specific implementation method five: This implementation method is different from specific implementation method two in that: when the K2CO3 solution is used to wash the extracted product in step 2, 30 to 40 mL of K2CO3 solution is used each time, and the product is washed three times in total; when saturated salt water is used to wash the extracted product, 30 to 40 mL of saturated salt water is used each time, and the product is washed twice in total.

[0067] Specific implementation method 6: This implementation method is different from the specific implementation method 2 in that the mass fraction of the K2CO3 solution in step 2 is 10%.

[0068] Specific implementation method seven: This implementation method is different from specific implementation method two in that: the concentration of the concentrated hydrochloric acid in step five is 12 mol / L.

[0069] Specific embodiment eight: This embodiment differs from specific embodiment two in that: in step five, the precipitate is washed three times with acetone and CH2Cl2 in sequence, each time using 3-5 mL acetone and 3-5 mL CH2Cl2, respectively.

[0070] Specific implementation method 9: The difference between this implementation method and specific implementation method 2 is that the mass fraction of NH4PF6 in the NH4PF6 aqueous solution in step 5 is 5%.

[0071] Specific embodiment 10: In this embodiment, the chiral cyclophane molecule BinapoBox·4PF6 is used to prepare CPL active materials in combination with aromatic dyes. The preparation method is carried out according to the following steps:

[0072] 1. mixing a chiral cyclophane and a solvent to obtain a chiral cyclophane solution;

[0073] The solvent is acetonitrile or methanol;

[0074] The concentration of the chiral cyclophane solution is 1×10 -6 ~1×10 -2 mol / L;

[0075] 2. Dissolve the aromatic dye in the same solvent as in step 1, and then add it to the chiral cyclophane solution prepared in step 1 to complete the preparation of the CPL active material;

[0076] The concentration of the aromatic dye is 0.01-0.1 mol / L;

[0077] The molar ratio of the aromatic dye to the chiral cyclophane is (1-4):1.

[0078] 1. The principle of induction of the chiral cyclophane molecule BinapoBox·4PF6 in this embodiment is that the unique box structure of the chiral cyclophane molecule can effectively bind to the aromatic molecule through the π-π interaction, and the axial chirality is transferred to the aromatic dye through the rotation of the chiral binaphthol unit of the cyclophane, thereby achieving chiral induction and preparing materials with chiral optical properties.

[0079] 2. The chiral cyclopan molecule BinapoBox·4PF6 of this embodiment has excellent binding ability and special fluorescent properties with aromatic dyes, making the chiral cyclopan molecule BinapoBox·4PF6 a good chiral host material for preparing chiral host-achiral guest assembly CPL materials. This embodiment avoids cumbersome synthetic modifications and also avoids expensive liquid crystal materials. It can be prepared in batches by enlarging equivalents, greatly reducing costs. In addition, because the chiral cyclopan molecule BinapoBox·4PF6 of this embodiment uses non-covalent bonds to induce guest chirality, guest replacement is less difficult, and organic solvents can be used to wash and replace different guest molecules for recycling. It is also suitable for most aromatic small molecule dyes and is a new chiral cyclopan product that can be recycled and has universality.

[0080] 3. The chiral cyclophane molecule BinapoBox·4PF6 in this embodiment is an organic small molecule, the raw materials for preparation are easily available, and the preparation cost is low. Compared with inorganic nanomaterials, organic synthesis modification, liquid crystal doping, etc., the preparation cost of chiral optically active materials can be greatly reduced.

[0081] 4. The chiral cyclopan molecule BinapoBox·4PF6 of this embodiment has a box-like structure, which enables it to spatially recognize aromatic hydrocarbons. That is, the chiral cyclopan molecules can be combined with aromatic hydrocarbons to form cyclopan-aromatic hydrocarbons. The CPL of cyclopan-aromatic hydrocarbons and the CPL of the chiral cyclopan molecules can be compared to achieve qualitative analysis of aromatic hydrocarbon compounds. When the chiral cyclopan molecule BinapoBox·4PF6 combines with different aromatic hydrocarbons, the dihedral angle information of the cyclopan-binaphthyl part will change, which will lead to changes in the CPL spectrum, causing g lum The chiral information of each aromatic hydrocarbon on binaphthyl changes differently, which makes the qualitative analysis of aromatic hydrocarbons more accurate.

[0082] Embodiment 1:

[0083] The structural formula of the chiral cyclophane molecule BinapoBox·4PF6 of the present invention is:

[0084]

[0085] The chiral cyclophane molecule BinapoBox·4PF6 has the general structural formula of C92 H 70 F 24 N4O2P6;

[0086] The preparation method of the chiral cyclophane molecule BinapoBox·4PF6 is carried out according to the following steps:

[0087] Step 1, Synthesis of 1,4-bis(bromomethyl)benzene:

[0088] 7.1 g of N-bromosuccinimide and 160 mg of azobisisobutyronitrile were added to 60 mL of p-xylene in acetonitrile; after stirring under reflux for 16 hours, the mixture was evaporated in vacuo and purified by chromatography to obtain 1,4-bis(bromomethyl)benzene as a white powder with a yield of 87%;

[0089] The ratio of the mass of xylene to the volume of acetonitrile in the xylene-acetonitrile solution is 2 g:60 mL;

[0090] The developing solvents used in the chromatography purification are petroleum ether and dichloromethane, and the volume ratio of petroleum ether to dichloromethane is 1:1;

[0091] Step 2: Synthesis of 4,4'-di(pyridin-4-yl)-1,1'-biphenyl:

[0092] 15 mL of dry N,N-dimethylformamide was degassed by bubbling N2 for 2 hours, followed by the addition of 468 mg of 4,4'-dibromo-1,1'-biphenyl, 80 mg of Pd(PPh3)4, 400 mg of 4-pyridineboric acid and 2.5 g of Cs2CO3, and the mixture was heated to 110°C and maintained for 24 hours to form a suspension, and the remaining residue after evaporation of the solvent was extracted with chloroform, and the extracted product was washed with K2CO3 solution and saturated brine in sequence, and the product obtained after washing was dried with MgSO4, and then the chloroform was removed by evaporation and concentration, and 5 mL of dichloromethane was added to dissolve the solid product obtained by evaporation and concentration, and 100 mL of n-hexane was added to the obtained solution for precipitation, and the obtained solid product was washed with 10 mL of n-hexane, and recrystallized with 10 mL of ethyl acetate after washing to obtain 4,4'-di(pyridin-4-yl)-1,1'-biphenyl;

[0093] The remaining residue was extracted with chloroform three times, each time using a volume of 20 mL of chloroform;

[0094] When the K2CO3 solution is used to wash the extracted product, 30 mL of K2CO3 solution is used each time, and the product is washed 3 times in total; when the saturated saline solution is used to wash the extracted product, 30 mL of saturated saline solution is used each time, and the product is washed 2 times in total;

[0095] The mass fraction of the K2CO3 solution is 10%;

[0096] Step 3: Synthesis of (R)-4,4-bis-4-pyridyl-1,1'-binaphthyl-2,2'-bisdiphenylphosphine:

[0097] 3.25 g (R)-4,4-dibromo-1,1'-binaphthyl-2,2'-bisdiphenylphosphine, 0.07 g Pd(PPh3)4, 1.08 g 4-pyridineboronic acid and 2.21 g K2CO3 were placed in a mixture of 150 mL 1,4-dioxane and water, heated under reflux for 7 days in a nitrogen atmosphere, and the obtained organic phase was washed with 275 mL H2O. After evaporating the solvent, the remaining solid was recrystallized from propan-2-ol; the yield was 84%;

[0098] The volume ratio of 1,4-dioxane to water in the mixed solution of 1,4-dioxane and water is 2:1;

[0099] Step 4: Synthesis of bis(4-bromomethylbenzyl)(4,4′-(4,4′-biphenyl)bipyridinium-1-ium)bis(hexafluorophosphate):

[0100] ① In a round-bottom three-necked flask, add 5.14 g of 1,4-bis(bromomethyl)benzene prepared in step 1 to a mixture of 240 mL of CH2Cl2 and acetonitrile, heat and stir in an oil bath at 50°C until all the solid matter is dissolved; then increase the oil bath temperature to 90°C to obtain a reaction solution;

[0101] The volume ratio of CH2Cl2 to acetonitrile in the mixture of CH2Cl2 and acetonitrile is 1:1;

[0102] ②, add 0.6g of 4,4'-di(pyridin-4-yl)-1,1'-biphenyl prepared in step 2 to 120mL of acetonitrile, and then titrate it into the reaction solution obtained in step ① within 4h, reflux and heat for 24h, cool to room temperature, filter and collect the yellow precipitate, wash with CH2Cl2 to obtain a yellow solid; dissolve the yellow solid in 1L of methanol below room temperature, and then add 400mgNH4PF6 and 1L of H2O below room temperature, and obtain bis(4-bromomethylbenzyl)(4,4'-(4,4'-biphenyl)bipyridin-1-ium)bis(hexafluorophosphate) after precipitation;

[0103] Step 5: Synthesis of chiral cyclophane molecule BinapoBox·4PF6:

[0104] 0.11 g of (R)-4,4-bis-4-pyridyl-1,1'-binaphthyl-2,2'-bisdiphenylphosphine prepared in step 3, 0.35 g of bis(4-bromomethylbenzyl)(4,4'-(4,4'-biphenyl)bipyridinium-1-ium)bis(hexafluorophosphate) prepared in step 4 and 0.027 g of tetrabutylammonium iodide were added to 180 mL of dry acetonitrile, stirred at 80° C. for 72 h, then 3 mL of concentrated hydrochloric acid was added to stop the reaction, and the precipitate was filtered and collected. Then, the precipitate was washed with acetone and CH2Cl2 in order to remove the residual tetrabutylammonium iodide, and the precipitate was dissolved in 500 mL of methanol at 60°C, and then an aqueous solution of NH4PF6 was added to obtain a solid product. After the reaction, the precipitate was collected and filtered, and the product was dissolved in 10 mL of acetonitrile to obtain a reaction solution, and the reaction solution was placed in an isopropyl ether vapor environment for three crystallizations to complete the process; the obtained chiral cyclopentane molecule BinapoBox·4PF6 was a yellow solid with a yield of 37%;

[0105] The concentration of the concentrated hydrochloric acid is 12 mol / L;

[0106] The precipitate was washed with acetone and CH2Cl2 three times in sequence, using 4 mL acetone and 4 mL CH2Cl2 acetone and CH2Cl2 respectively each time;

[0107] The mass fraction of NH4PF6 in the aqueous solution of NH4PF6 is 5%;

[0108] The method for preparing CPL active materials by combining the chiral cyclophane molecule BinapoBox·4PF6 with aromatic dyes is carried out according to the following steps:

[0109] 1. Mixing chiral cyclophane and acetonitrile to obtain a chiral cyclophane solution; measuring the CD (circular dichroism) absorption change diagram of the chiral cyclophane solution under 365nm light excitation; Figure 1 The CD absorption change diagram of cyclophane combined with different equivalents of 4-(perylene-3-yl)pyridine dye guest;

[0110] The concentration of the chiral cyclophane solution is 1×10 -6 mol / L;

[0111] 2. Dissolve the aromatic dye in acetonitrile and add it to the chiral cyclophane solution prepared in step 1 to complete the preparation of the CPL active material. Measure the fluorescence emission change of the mixed solution under 365nm light excitation; Figure 2 The fluorescence spectrum change diagram (PL spectrum) of cyclophane combined with different equivalents of 4-(perylene-3-yl)pyridine dye guest;

[0112] The concentration of the aromatic dye is 0.01 mol / L;

[0113] The molar ratio of the aromatic dye to the chiral cyclophane is 1:1;

[0114] Figure 1 The CD absorption change diagram of cyclophane combined with different equivalents of 4-(perylene-3-yl)pyridine dye guest; Figure 2 The fluorescence spectrum change diagram (PL spectrum) of cyclophane combined with different equivalents of 4-(perylene-3-yl)pyridine dye guest. The CD (circular dichroism) absorption change diagram ( Figure 1 ) and the fluorescence emission change diagram obtained in step 2 ( Figure 2 ) were compared and it was found that a new absorption signal appeared in the absorption band of the dye, indicating that the non-chiral dye showed a chiral optical signal; the PL spectrum of the dye could be observed through the change of fluorescence emission, and the solution of the dye had no PL spectrum at this excitation wavelength, indicating that the cyclopentane host and the dye guest formed a host-guest complex and there was an obvious energy transfer process.

Claims

1. A chiral cyclophane molecule BinapoBox·4PF6, characterized in that: The structural formula of the chiral cyclophane molecule BinapoBox·4PF6 is: The chiral cyclophane molecule BinapoBox·4PF6 has the general structural formula of C 92 H 70 F 24 N4O2P6.

2. The method for preparing the chiral cyclophane molecule BinapoBox·4PF6 according to claim 1, characterized in that: The preparation method of the chiral cyclophane molecule BinapoBox·4PF6 is carried out according to the following steps: Step 1, Synthesis of 1,4-bis(bromomethyl)benzene: 7.1-7.2 g of N-bromosuccinimide and 160-170 mg of azobisisobutyronitrile are added to 60-70 mL of an acetonitrile solution of p-xylene; after stirring under reflux for 16-17 hours, the mixture is evaporated in vacuo and purified by chromatography to obtain 1,4-bis(bromomethyl)benzene; The ratio of the mass of xylene to the volume of acetonitrile in the xylene-acetonitrile solution is 2-3 g: 60-90 mL; Step 2: Synthesis of 4,4'-di(pyridin-4-yl)-1,1'-biphenyl: 15-20 mL of dry N,N-dimethylformamide was degassed by bubbling N2 for 2 h, followed by the addition of 468-500 mg of 4,4'-dibromo-1,1'-biphenyl, 80-90 mg of Pd(PPh3)4, 400-500 mg of 4-pyridineboronic acid and 2.5-3.0 g of Cs2CO3, heating the mixture to 110°C and maintaining it for 24 hours to form a suspension, extracting the remaining residue after evaporating the solvent with chloroform, washing the extracted product with K2CO3 solution and saturated brine in turn, drying the product after washing with MgSO4, and then removing the chloroform by evaporation and concentration, adding 5-10 mL of dichloromethane to dissolve the solid product obtained by evaporation and concentration, adding 100-120 mL of n-hexane to the obtained solution for precipitation, washing the obtained solid product with 10-20 mL of n-hexane, and recrystallizing with 10-20 mL of ethyl acetate after washing to obtain 4,4'-di(pyridin-4-yl)-1,1'-biphenyl; Step 3: Synthesis of (R)-4,4-bis-4-pyridyl-1,1'-binaphthyl-2,2'-bisdiphenylphosphine: 3.25-3.5 g (R)-4,4-dibromo-1,1'-binaphthyl-2,2'-bisdiphenylphosphine, 0.07-0.10 g Pd(PPh3)4, 1.08-1.20 g 4-pyridineboric acid and 2.21-2.50 g K2CO3 are placed in a mixture of 150-200 mL 1,4-dioxane and water, heated under reflux for 7 days in a nitrogen atmosphere, the obtained organic phase is washed with 275-300 mL H2O, the solvent is evaporated, and the remaining solid is recrystallized from propan-2-ol; The volume ratio of 1,4-dioxane to water in the mixed solution of 1,4-dioxane and water is 2:1; Step 4: Synthesis of bis(4-bromomethylbenzyl)(4,4′-(4,4′-biphenyl)bipyridinium-1-ium)bis(hexafluorophosphate): ①. In a round-bottom three-necked flask, add 5.14-5.2 g of 1,4-bis(bromomethyl)benzene prepared in step 1 to a mixture of 240 mL of CH2Cl2 and acetonitrile, heat and stir in an oil bath at 50°C until all the solid matter is dissolved; then increase the oil bath temperature to 90°C to obtain a reaction solution; The volume ratio of CH2Cl2 to acetonitrile in the mixture of CH2Cl2 and acetonitrile is 1:1; ②, add 0.6-0.7g of 4,4'-di(pyridin-4-yl)-1,1'-biphenyl prepared in step 2 to 120-150mL of acetonitrile, and then titrate it into the reaction solution obtained in step ① within 4 hours, reflux and heat for 24-30 hours, cool to room temperature, filter and collect the yellow precipitate, and wash with CH2Cl2 to obtain a yellow solid; dissolve the yellow solid in 1-1.5L methanol below room temperature, and then add 400-500mg NH4PF6 and 1L H2O below room temperature, and precipitate to obtain bis(4-bromomethylbenzyl)(4,4'-(4,4'-biphenyl)bipyridin-1-ium)bis(hexafluorophosphate); Step 5: Synthesis of chiral cyclophane molecule BinapoBox·4PF6: 0.11-0.12 g of (R)-4,4-bis-4-pyridyl-1,1'-binaphthyl-2,2'-bisdiphenylphosphine prepared in step 3, 0.35-0.40 g of bis(4-bromomethylbenzyl)(4,4'-(4,4'-biphenyl)bipyridinium-1-ium)bis(hexafluorophosphate) prepared in step 4 and 0.027-0.030 g of tetrabutylammonium iodide were added to 180-200 mL of dry acetonitrile and stirred at 80-90° C. for 72-80 min. 80h, then add 3mL of concentrated hydrochloric acid to stop the reaction, filter and collect the precipitate, then wash the precipitate with acetone and CH2Cl2 in turn to remove residual tetrabutylammonium iodide, dissolve the precipitate in 500-600mL of 60°C methanol, and then add an aqueous solution of NH4PF6 to obtain a solid product. After the reaction, collect the precipitate and filter it, dissolve the product in 10mL of acetonitrile to obtain a reaction solution, and place the reaction solution in an isopropyl ether vapor environment for 2-3 crystallizations to complete.

3. The method for preparing the chiral cyclophane molecule BinapoBox·4PF6 according to claim 1, characterized in that: The developing solvents used in the chromatographic purification in step 1 are petroleum ether and dichloromethane, and the volume ratio of petroleum ether to dichloromethane is 1:

1.

4. The method for preparing the chiral cyclophane molecule BinapoBox·4PF6 according to claim 1, characterized in that: The remaining residue in step 2 was extracted with chloroform three times, with the volume of chloroform used each time being 20 to 30 mL.

5. The method for preparing the chiral cyclophane molecule BinapoBox·4PF6 according to claim 1, characterized in that: When the product obtained by extraction is washed with K2CO3 solution in step 2, 30-40 mL of K2CO3 solution is used each time, and the washing is performed 3 times in total; When the extracted product is washed with saturated saline, 30 to 40 mL of saturated saline is used each time, and the washing is performed twice in total.

6. The method for preparing the chiral cyclophane molecule BinapoBox·4PF6 according to claim 1, characterized in that: The mass fraction of the K2CO3 solution in step 2 is 10%.

7. The method for preparing the chiral cyclophane molecule BinapoBox·4PF6 according to claim 1, characterized in that: The concentration of the concentrated hydrochloric acid in step 5 is 12 mol / L.

8. The method for preparing the chiral cyclophane molecule BinapoBox·4PF6 according to claim 1, characterized in that: As described in step 5, the precipitate is washed three times with acetone and CH2Cl2, using 3-5 mL acetone and 3-5 mL CH2Cl2 respectively each time.

9. The method for preparing the chiral cyclophane molecule BinapoBox·4PF6 according to claim 1, characterized in that: The mass fraction of NH4PF6 in the aqueous solution of NH4PF6 in step 5 is 5%.

10. The use of the chiral cyclophane molecule BinapoBox·4PF6 as claimed in claim 1, characterized in that: The chiral cyclophane molecule BinapoBox·4PF6 is used to combine with aromatic dyes to prepare CPL active materials. The preparation method is carried out according to the following steps:

1. mixing a chiral cyclophane and a solvent to obtain a chiral cyclophane solution; The solvent is acetonitrile or methanol; The concentration of the chiral cyclophane solution is 1×10 -6 ~1×10 -2 mol / L; 2. Dissolve the aromatic dye in the same solvent as in step 1, and then add it to the chiral cyclophane solution prepared in step 1 to complete the preparation of the CPL active material; The concentration of the aromatic dye is 0.01-0.1 mol / L; The molar ratio of the aromatic dye to the chiral cyclophane is (1-4):1.

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