Co-crystal Materials Based on Tetraaryladamantane Crystallization Partners, Their Preparation Methods and Applications in Molecular Co-crystals and Structure Identification

Abstract

The present invention discloses a eutectic material based on a tetraaryl adamantane crystallization co - former, its preparation method, and its application in molecular eutectics and structure identification. The eutectic material of the present invention is a host - guest complex formed by a tetraaryl adamantane crystallization co - former and an oily guest molecule. The eutectic material is prepared by mixing the tetraaryl adamantane crystallization co - former, the oily guest molecule, and chlorobenzene, and heating the mixture on a heating plate to obtain a mixed solution; then placing the mixed solution in a constant - temperature water - bath device and controlling its temperature to decrease to room temperature along with the water - bath temperature, thereby obtaining the eutectic material based on the tetraaryl adamantane crystallization co - former. The eutectic material prepared by the present invention is a material with stable structure, and the preparation method is simple to operate and has good repeatability, providing a good basis for the application of this method in molecular eutectics and structure and absolute configuration identification.

Description

Technical Field

[0001] The present invention relates to the technical field of supramolecular eutectic materials, and particularly to a eutectic material based on a tetraaryladamantane crystallization partner, a preparation method thereof, and applications in molecular eutectics and structure identification. Background Art

[0002] Molecules with different absolute configurations behave differently in a chiral environment. In life, there are many such molecules, such as the active sites of enzymes or receptors. A large number of new molecules with unknown stereochemical configurations have been obtained through organic chemical synthesis or natural product methods. If there is no reliable method to determine the absolute configuration of the new molecules, the most undesirable situations will occur. For example, before the absolute configuration was determined by anomalous dispersion X-ray crystallography, we were unable to distinguish the D / L enantiomers of sugar molecules. Therefore, the identification of their absolute configuration is often the top priority in structure analysis. Single-crystal X-ray diffraction is an important means for identifying the structure of organic compounds. Different from verification methods such as nuclear magnetic resonance and mass spectrometry, single-crystal X-ray diffraction can directly observe the structure of molecules, and its results are more definite and more reliable. However, many small molecules or highly flexible molecules are not easy to crystallize, but produce oils, glasses, amorphous precipitates or disordered solids. For example, vaseline, or some compounds such as the flexible small molecule n-heptane, are difficult to obtain crystals. Then how to obtain the crystal structures of these small molecules?

[0003] To solve this problem, the Mokoto Fujita team proposed the method of "crystalline sponges". Organic guest small molecules enter and arrange in the appropriately sized pores of metal-organic frameworks (Nature 2013, 495, 461-466). It does not require any crystallization process for the target molecule. The sample is dissolved, dropped onto the crystalline sponge, the solvent evaporates, and the target molecule will automatically penetrate into the interior of the crystalline sponge and achieve long-range ordered arrangement in the pores. At the same time, it can be used for crystal structure analysis of nanogram-scale compounds. In theory, one (80×80×80μm 3) The crystal sponge can achieve the structural analysis of 26 ng of the target molecule. Further, it can be combined with high-performance liquid chromatography to achieve direct structural analysis of a small amount of mixed products, and finally the absolute configuration of the molecule can be determined. The team of Michael D. Ward used a hydrogen-bond framework composed of guanidinium cations and organic sulfonate anions to encapsulate a wide range of guest molecules into the crystal channels to identify the structure of the guest molecules (Science 1997, 276, 575-579). In addition, the Richert team proposed that tetraaryladamantanes (TAAs) are prone to co-crystallize with liquid small-molecule compounds that are difficult to crystallize in the form of inclusion complexes. They heated and dissolved the adamantane crystallization partner solid powder and the liquid oily small-molecule that is difficult to crystallize at a high temperature of 150 °C, and then cooled and precipitated to obtain a co-crystal, in order to quickly determine the absolute configuration of the small molecule (Angew. Chem. Int. Ed. 2020, 59, 15875-15879).

[0004] However, their work requires heating the solid powder of the TAAs host molecule and the guest molecule in the liquid state at a high temperature to dissolve them. The deficiencies of the above work are as follows: 1. TAAs are not suitable for the structural identification of organic molecules with poor thermal stability or those that decompose upon heating; 2. The channels formed by TAAs in the above work are relatively small and can only accommodate organic molecules with relatively small volumes, and larger molecules cannot enter the cavity; 3. In the above work, they did not use a solvent, resulting in many failed cases because the liquid guest molecules could not dissolve the solid powder of the TAAs host molecule well. Summary of the Invention

[0005] Aiming at the deficiencies of the prior art, the present invention provides a co-crystalline material based on a tetraaryladamantane crystallization partner, its preparation method and its application in molecular co-crystallization and structural identification. The 1,3,5,7-tetrakis(4-(10-methoxyanthracen-9-yl)phenyl)adamantane used in the present invention introduces anthracene rings and phenyl groups on the basis of adamantane, expanding the cavity of the host molecule and enabling it to accommodate larger-volume organic molecules. Moreover, by using a solvent to assist dissolution, the solid powder of the TMAPA host molecule can be well dissolved at a lower temperature, thus better realizing co-crystallization.

[0006] The technical solution of the present invention is as follows:

[0007] An object of the present invention is to provide a co-crystalline material based on a tetraaryladamantane crystallization partner, and the co-crystalline material is a host-guest complex formed by a tetraaryladamantane crystallization partner and an oily guest molecule.

[0008] Further, the tetraaryl adamantane crystallization co - former is 1,3,5,7 - tetrakis(4-(10 - methoxyanthracen - 9 - yl)phenyl)adamantane (abbreviated as TMAPA); the oily guest molecules include one or more of cis - jasmone, linalool, geranyl acetate, and S - 1 - phenylethylamine.

[0009] Further, the mass - to - volume ratio of the tetraaryl adamantane crystallization co - former to the oily guest molecules is 2 mg:50 - 100 μL.

[0010] Another object of the present invention is to protect a preparation method of the eutectic material based on the tetraaryl adamantane crystallization co - former, and the preparation method includes the following steps:

[0011] S1: Weigh the tetraaryl adamantane crystallization co - former and the oily guest molecules for standby;

[0012] S2: Mix the tetraaryl adamantane crystallization co - former, the oily guest molecules and chlorobenzene, and place them on a heating plate for heating to obtain a mixed solution;

[0013] S3: Heat the constant - temperature water - bath device to a set temperature;

[0014] S4: Place the mixed solution in step S2 into the constant - temperature water - bath device in step S3, and gradually lower the temperature of the water - bath device to room temperature. The temperature of the mixed solution drops to room temperature as the water - bath temperature decreases, and a eutectic material based on the tetraaryl adamantane crystallization co - former is obtained.

[0015] Further, in step S2, the mass - to - volume ratio of the tetraaryl adamantane crystallization co - former, the oily guest molecules and chlorobenzene is 2 mg:50 - 100 μL:10 - 100 μL; the temperature of the heating plate is 90 - 110 °C, and the heating time is 0.5 - 2 min.

[0016] Further, in step S3, the set temperature ≤ the temperature of the heating plate in S2.

[0017] Further, in step S4, gradually lowering the temperature of the water - bath device to room temperature means lowering the temperature to room temperature at a rate of 1 - 3 °C / h.

[0018] Another object of the present invention is to protect the tetraaryl adamantane crystallization co - former, specifically to protect 1,3,5,7 - tetrakis(4-(10 - methoxyanthracen - 9 - yl)phenyl)adamantane (abbreviated as TMAPA),

[0019] Another object of the present invention is to protect a method for synthesizing 1,3,5,7-tetrakis(4-(10-methoxyanthracen-9-yl)phenyl)adamantane, and the specific synthesis route is as follows:

[0020]

[0021] Among them, I is 1-bromoadamantane; II is tetraphenyladamantane; III is tetrabromotetraphenyladamantane; IV is tetrabromotetraphenyltetrakis(pinacolato)boronate adamantane; V is anthrone; VI is 9-methoxyanthracene; VII is 9-bromo-10-methoxyanthracene.

[0022] The specific synthesis steps are as follows:

[0023] 1. Synthesis of tetraphenyladamantane: Under an argon atmosphere, 1-bromoadamantane (5.00 g, 37.9 mmol) and anhydrous aluminum chloride (0.22 g, 2.20 mmol) were added to a flask (or other container), benzene (90 mL) and tert-butyl bromide (5.30 mL, 45.8 mmol) were added to the flask (or other container) with a syringe, and then it was refluxed overnight. The reaction mixture was cooled to room temperature, and the formed precipitate was filtered out. The product was dried under reduced pressure overnight to obtain the product tetraphenyladamantane (4.1 g, 88%).

[0024] 2. Synthesis of tetrabromotetraphenyladamantane: Tetraphenyladamantane (1.5 g, 2.57 mmol) and iron powder (0.02 g, 0.36 mmol) were weighed and added to a 100 mL Schlenk tube, suspended in 10 mL of chloroform, and a mixed solution of liquid bromine (0.32 mL, 7.08 mmol) and 10 mL of chloroform was slowly added dropwise under an ice bath, and the reaction was carried out at 80 °C for 24 h. After the reaction was completed, it was cooled to room temperature, filtered by suction, the filter cake was taken, washed several times with absolute ethanol, and dried to obtain the pure product tetrabromotetraphenyladamantane (1.1 g, 75%).

[0025] 3. Synthesis of tetrabromotetraphenyltetrakis(pinacolato)boronate adamantane: Potassium acetate (8.5 g, 37.9 mmol), tetrabromobenzeneadamantane (1.2 g, 2 mmol), and bis(pinacolato)diboron (3 g, 12 mmol) were added to a 250 mL three-necked flask, and a nitrogen balloon was added in the middle, and evacuated and filled with nitrogen three times. Anhydrous and oxygen-free DMSO was added to the three-necked flask with a syringe, and the reaction was carried out at 100 °C for 48 h. After the reaction was completed, it was cooled to room temperature, water was added to precipitate a solid, and the crude product was obtained by filtration, and purified by silica gel column chromatography to obtain tetrabromotetraphenyltetrakis(pinacolato)boronate adamantane (0.8 g, 55%).

[0026] 4. Synthesis of 9-methoxyanthracene: Under an argon atmosphere, a solution of anthrone (3.23 g, 17.7 mmol) and potassium carbonate (5.9 g, 46.1 mmol) in acetone (120 mL) was added to a 100 mL round-bottom flask. Dimethyl sulfate (10 mL, 62.2 mmol) was added to the solution, and the reaction mixture was refluxed for 12 hours. After cooling, water was added to the mixture, and the product was extracted with a mixture of cyclohexane and dichloromethane. The combined organic layers were washed with water and brine, dried over anhydrous Na2SO4, and filtered. The solvent was removed under vacuum, and recrystallization from a solution of cyclohexane and dichloromethane gave light yellow crystals of 9-methoxyanthracene (3.61 g, 73%).

[0027] 5. Synthesis of 9-bromo-10-methoxyanthracene: A solution of 9-methoxyanthracene (1.12 g, 7.30 mmol) in DMF (30 mL) was added to a 50 mL round-bottom flask under an argon atmosphere and cooled in an ice bath. NBS (1.88 g, 9.15 mmol) in DMF (20 mL) was added dropwise to the solution through an addition funnel over 50 minutes, and the mixture was stirred overnight. Then, the reaction mixture was washed with water and extracted with dichloromethane. After drying over anhydrous Na2SO4, the solvent was removed under vacuum, and silica gel column chromatography gave light yellow solid 9-bromo-10-methoxyanthracene (1.8 g, 77%)

[0028] 6. Synthesis of TMAPA: 9-bromo-10-methoxyanthracene (0.34 g, 1.4 mmol), sodium carbonate (1.6 g, 7 mmol), tetrabromotetraphenyltetrakis(pinacolato)adamantane (0.27 g, 0.2 mmol), and tetrakis(triphenylphosphine)palladium (0.07 g, 0.057 mmol) were added to a 250 mL three-necked flask under a nitrogen atmosphere, and 80 mL of a degassed mixture of DMSO and water was added to the three-necked flask under vacuum. After the reaction was completed and cooled to room temperature, water was added to the mixture. The combined organic layers were washed with water and brine, dried over anhydrous sodium sulfate, and filtered. The solvent was removed under vacuum, and the crude product was purified by silica gel column chromatography to give the product TMAPA (0.2 g, 68%).

[0029] Another object of the present invention is to protect the application of a eutectic material based on a tetraaryladamantane crystallization co-crystal, wherein the eutectic material based on a tetraaryladamantane crystallization co-crystal is used for the structural identification of oily guest molecules; the oily guest molecules include one or more of cis-jasmone, linalool, geranyl acetate, and S-1-phenylethylamine.

[0030] Further, the specific steps for the structural identification of the oily guest are as follows:

[0031] (1) Prepare the eutectic material according to the preparation method of the eutectic material based on a tetraaryladamantane crystallization co-crystal described above;

[0032] (2) Select single crystals from the eutectic material under a microscope, determine them using a single crystal X-ray diffractometer, and collect diffraction data;

[0033] (3) Refine the unit cell and restore the data for the obtained diffraction data, and finally perform single crystal analysis to obtain the precise structure and absolute configuration of the guest molecule.

[0034] Since the detection object of the single crystal diffraction instrument must be a single crystal. However, the guest molecules described in the present invention are all liquids and cannot form single crystals by themselves. After adding TMAPA in the present invention, based on the fact that TMAPA will form a co-crystal with the guest molecule, single crystal testing can thus be carried out. Further by analyzing the data, the structures of TMAPA and the guest molecule can be seen, and the two molecules exist simultaneously, thereby realizing the determination of the structure of the guest molecule that cannot be detected alone.

[0035] The beneficial technical effects of the present invention are as follows:

[0036] The co-crystalline material based on the tetraaryl adamantane crystallization partner described in the present invention is a material with a stable structure, and the preparation method is simple to operate and has good repeatability. After crystal structure analysis and refinement, the overall quality of the data is good and the R value is low. There are no disordered components in the guest molecule, and at the same time, only a few restrictive instructions need to be applied to the guest molecule to obtain reasonable structure information. It provides a good foundation for the future application of this method in the identification of molecular co-crystals, structures and absolute configurations.

[0037] The present invention is based on TMAPA having a structure similar to a regular tetrahedron: 1. (1) Using adamantane as the core, adamantane has a shape, symmetry and rigidity conducive to rapid crystallization, and adamantane has the ability to induce the formation of a diamond structure, thus being conducive to crystallization into a porous material. (2) Based on using adamantane as the core, benzene rings and anthracene rings are introduced. They have strong rigidity and are easy to crystallize. The arms are lengthened, which can greatly expand the cavity, making up for the deficiency in the work of Richert that co-crystals cannot be formed for molecules with larger molecular volumes. (3) The presence of alkoxy groups on the anthracene ring makes it present a shape closer to a sphere, making the adjacent molecules pack more densely. Moreover, the alkoxy groups can adopt different conformations similar to tweezers, which helps to accommodate different guest molecules. (4) The alkoxy groups in the crystallization partner can rotate, presenting a higher polar surface, thus serving as a hydrogen bond acceptor or surface interaction of a dipole in the guest molecule. (5) At a relatively low temperature (about 90 °C), the host molecule TMAPA, the guest molecule and the solvent are added. The addition of the solvent can well dissolve the solid powder of TMAPA, making up for the problem in the work of Richert that the solid host molecule cannot be dissolved. Description of the Drawings

[0038] Figure 1 The chemical structures of 1,3,5,7-tetrakis(4-(10-methoxyanthracen-9-yl)phenyl)adamantane and four oily guest molecules.

[0039] Figure 2 The cocrystal structure of TMAPA and cis-jasmone in Example 1 of the present invention.

[0040] Figure 3 The cocrystal structure of TMAPA and linalool in Example 2 of the present invention.

[0041] Figure 4 The cocrystal structure of TMAPA and geranyl acetate in Example 3 of the present invention.

[0042] Figure 5 The cocrystal structure of TMAPA and S-1-phenylethylamine in Example 4 of the present invention. Detailed implementation manners

[0043] The present invention will be specifically described below in conjunction with the accompanying drawings and examples.

[0044] TMAPA used in the present invention is an example of a tetraaryladamantane crystallization chaperone.

[0045] The present invention is committed to developing a preparation method of a cocrystal material based on a tetraaryladamantane crystallization chaperone; and taking this as an example, exploring and verifying the application prospect of this method in molecular cocrystals and the identification of structure and absolute configuration.

[0046] The specific formation mechanism of the present invention is as follows: When a liquid small molecule analyte that is difficult to crystallize tries to find a binding site, the crystallization sponge remains rigid, while the adamantane host undergoes nucleation and crystal growth solvated by the guest molecule. When it enters one of the accessible conformations and crystal systems, it will find a molecular arrangement suitable for the analyte and itself to obtain a single crystal, and the absolute configuration of the chiral compound can be directly determined.

[0047] Based on the above principle, the present invention uses the synthesized tetraaryladamantane crystallization chaperone to prepare a cocrystal material, and uses this cocrystal material to determine the structure of guest molecules that are difficult to crystallize alone.

[0048] The tetraaryladamantane crystallization chaperone used is 1,3,5,7-tetrakis(4-(10-methoxyanthracen-9-yl)phenyl)adamantane (abbreviated as TMAPA for 1,3,5,7-tetrakis(4-(10-methoxyanthracen-9-yl)phenyl)adamantane), and its synthesis route is as follows:

[0049]

[0050] Among them, I is 1-bromoadamantane; II is tetraphenyladamantane; III is tetrabromotetraphenyladamantane; IV is tetrabromotetraphenyltetrakis(pinacolato)borate adamantane; V is anthrone; VI is 9-methoxyanthracene; VII is 9-bromo-10-methoxyanthracene.

[0051] The specific synthesis steps are as follows:

[0052] 1. Synthesis of tetraphenyladamantane: Under an argon atmosphere, 1-bromoadamantane (5.00 g, 37.9 mmol) and anhydrous aluminum chloride (0.22 g, 2.20 mmol) were added to a flask (or other container), and benzene (90 mL) and tert-butyl bromide (5.30 mL, 45.8 mmol) were added to the flask (or other container) with a syringe. Then it was refluxed overnight. The reaction mixture was cooled to room temperature, and the formed precipitate was filtered out. The product was dried under reduced pressure overnight to obtain the product tetraphenyladamantane (4.1 g, 88%).

[0053] 2. Synthesis of tetrabromotetraphenyladamantane: Tetraphenyladamantane (1.5 g, 2.57 mmol) and iron powder (0.02 g, 0.36 mmol) were weighed and added to a 100 mL Schlenk tube, and suspended in 10 mL of chloroform. Under an ice bath, a mixed solution of bromine (0.32 mL, 7.08 mmol) and 10 mL of chloroform was slowly added dropwise, and the reaction was carried out at 80 °C for 24 h. After the reaction was completed, it was cooled to room temperature, filtered by suction, the filter cake was obtained, washed several times with absolute ethanol, and dried to obtain the pure product tetrabromotetraphenyladamantane (1.1 g, 75%).

[0054] 3. Synthesis of tetrabromotetraphenyltetrakis(pinacolato)borate adamantane: Potassium acetate (8.5 g, 37.9 mmol), tetrabromobenzyladamantane (1.2 g, 2 mmol), and bis(pinacolato)diboron (3 g, 12 mmol) were added to a 250 mL three-necked flask, and a nitrogen balloon was added in the middle, and evacuated and filled three times. Anhydrous and oxygen-free DMSO was added to the three-necked flask with a syringe, and the reaction was carried out at 100 °C for 48 h. After the reaction was completed, it was cooled to room temperature, water was added to precipitate a solid, and the crude product was obtained by filtration. The product was purified by silica gel column chromatography to obtain tetrabromotetraphenyltetrakis(pinacolato)borate adamantane (0.8 g, 55%).

[0055] 4. Synthesis of 9-methoxyanthracene: Under an argon atmosphere, a solution of anthrone (3.23 g, 17.7 mmol) and potassium carbonate (5.9 g, 46.1 mmol) in acetone (120 mL) was added to a 100 mL round-bottom flask. Dimethyl sulfate (10 mL, 62.2 mmol) was added to the solution, and the reaction mixture was refluxed for 12 hours. After cooling, water was added to the mixture, and the product was extracted with a mixture of cyclohexane and dichloromethane. The combined organic layers were washed with water and brine, dried over anhydrous Na2SO4, and filtered. The solvent was removed under vacuum, and recrystallization from a solution of cyclohexane and dichloromethane gave light yellow crystals of 9-methoxyanthracene (3.61 g, 73%).

[0056] 5. Synthesis of 9-bromo-10-methoxyanthracene: A solution of 9-methoxyanthracene (1.12 g, 7.30 mmol) in DMF (30 mL) was added to a 50 mL round-bottom flask under an argon atmosphere and cooled in an ice bath. NBS (1.88 g, 9.15 mmol) in DMF (20 mL) was added dropwise to the solution through an addition funnel over 50 minutes, and the mixture was stirred overnight. Then, the reaction mixture was washed with water and extracted with dichloromethane. After drying over anhydrous Na2SO4, the solvent was removed under vacuum, and silica gel column chromatography gave light yellow solid 9-bromo-10-methoxyanthracene (1.8 g, 77%).

[0057] 6. Synthesis of TMAPA: 9-bromo-10-methoxyanthracene (0.34 g, 1.4 mmol), sodium carbonate (1.6 g, 7 mmol), tetrabromotetraphenyltetrakis(pinacolato)adamantane (0.27 g, 0.2 mmol), and tetrakis(triphenylphosphine)palladium (0.07 g, 0.057 mmol) were added to a 250 mL three-necked flask under a nitrogen atmosphere, and 80 mL of a degassed mixture of DMSO and water was added to the three-necked flask under vacuum. After the reaction was completed and cooled to room temperature, water was added to the mixture. The combined organic layers were washed with water and brine, dried over anhydrous sodium sulfate, and filtered. The solvent was removed under vacuum, and the crude product was purified by silica gel column chromatography to give the product TMAPA (0.2 g, 68%).

[0058] The present invention uses 1,3,5,7-tetrakis(4-(10-methoxyanthracen-9-yl)phenyl)adamantane (abbreviated as TMAPA) synthesized by the above method as the main raw material, and uses pure oil-like guest molecules (including one of cis-jasmone, linalool, geranyl acetate, S-1-phenylethylamine) and chlorobenzene molecules as solvents. By using the method of cooling crystallization and adjusting conditions such as the initial heating temperature, cooling rate, and solvent ratio, a eutectic material based on tetraaryladamantane crystallization co-crystals is prepared. The detailed molecular structure is shown in Figure 1 .

[0059] The present invention will be further described below through examples and comparative examples.

[0060] Example 1

[0061] A eutectic material based on tetraaryladamantane crystallization co-crystals, and its preparation method includes the following steps:

[0062] Step 1: Weigh 2 mg of TMAPA synthesized by the above method and set it aside; Pipette 55 μL of cis-jasmone and set it aside; Pipette 50 μL of chlorobenzene solvent and set it aside;

[0063] Step 2: Mix the TMAPA, cis-jasmone, and chlorobenzene solvent weighed in Step 1 in a sample bottle, and place it on a heating plate. Set the heating temperature to 90 °C and heat for 1 min until a clear and transparent mixture is obtained;

[0064] Step 3: Turn on the constant temperature water bath and set the temperature to 90 °C. Wait until the water bath temperature reaches the set value and stabilizes;

[0065] Step 4: Quickly transfer the sample bottle containing the mixture prepared in Step 2 to the water bath in Step 3.

[0066] Step 5: Gradually lower the temperature of the water bath to room temperature at a cooling rate of 3 °C / hour, so that the temperature of the mixture in the sample bottle slowly decreases with the water bath temperature. After reaching room temperature, yellow block-shaped single crystals are obtained, which are the TMAPA eutectic material.

[0067] For the structural identification of the oil-like guest using the eutectic material based on tetraaryladamantane crystallization co-crystals, the specific method is as follows:

[0068] Under a microscope, select transparent crystals with appropriate size and regular shape from the eutectic obtained in Step 5. Collect diffraction data on a Bruker SCD D8 single crystal X-ray diffractometer using a copper target at 193 K.

[0069] The obtained diffraction data was subjected to unit cell refinement and data reduction on APEX software, and then single crystal analysis was performed on Olex2 software to obtain the precise structure of the guest molecule. It was found that the guest molecule was cis-jasmone (the cocrystal data of TMAPA and cis-jasmone is shown in Table 1, and the cocrystal structure is as Figure 2 shown).

[0070] Table 1: Cocrystal data of TMAPA and cis-jasmone

[0071]

[0072]

[0073] Example 1 was repeated 3 times, and the repetition rate of the obtained cocrystal material of TMAPA and cis-jasmone reached 100%.

[0074] Example 2

[0075] A cocrystal material based on a tetraaryladamantane crystallization coformer, and its preparation method includes the following steps:

[0076] Step 1: Weigh 2 mg of TMAPA synthesized by the above method and set aside; Pipette 55 μL of linalool and set aside; Pipette 50 μL of chlorobenzene solvent and set aside;

[0077] Step 2: Mix the TMAPA and linalool weighed in Step 1 in a sample bottle, and place it on a heating plate. Set the heating temperature to 90 °C and heat for 1 min until a clear and transparent mixture is obtained;

[0078] Step 3: Turn on a constant temperature water bath and set the temperature to 90 °C. Wait until the water bath temperature reaches the set value and stabilizes;

[0079] Step 4: Quickly transfer the sample bottle containing the mixture prepared in Step 2 to the water bath in Step 3.

[0080] Step 5: Gradually reduce the temperature of the water bath to room temperature at a rate of 3 °C per hour, so that the temperature of the mixture in the sample bottle slowly decreases with the water bath temperature. After reaching room temperature, yellow block-shaped single crystals are obtained, which are the cocrystal material of TMAPA.

[0081] The identification method for the structure of the oily guest using the cocrystal material based on the tetraaryladamantane crystallization coformer is as follows:

[0082] Under a microscope, select transparent crystals with appropriate size and regular shape from the cocrystal obtained in Step 5. Collect diffraction data on a Bruker SCD D8 single crystal X-ray diffractometer using a copper target at 193 K.

[0083] The obtained diffraction data was subjected to unit cell refinement and data reduction on the APEX software, and then single crystal analysis was carried out on the Olex2 software to obtain the precise structure of the guest molecule. It was found that the guest molecule was linalool. (The eutectic data of TMAPA and linalool are shown in Table 2, and the eutectic structure is as Figure 3 shown).

[0084] Table 2: Eutectic data of TMAPA and linalool.

[0085]

[0086]

[0087] Example 2 was repeated 3 times, and the repetition rate of the obtained eutectic material of TMAPA and linalool reached 100%.

[0088] Example 3

[0089] A eutectic material based on a tetraaryladamantane crystallization co - former, and its preparation method includes the following steps:

[0090] Step 1: Weigh 2 mg of TMAPA synthesized by the above method and set it aside; Pipette 55 μL of geranyl acetate and set it aside; Pipette 50 μL of chlorobenzene solvent and set it aside;

[0091] Step 2: Mix the TMAPA and geranyl acetate weighed in Step 1 in a sample bottle, and place it on a heating plate. Set the heating temperature to 90 °C and heat for 1 min until a clear and transparent mixture is obtained;

[0092] Step 3: Turn on a constant temperature water bath and set the temperature to 90 °C. Wait until the water bath temperature reaches the set value and stabilizes;

[0093] Step 4: Quickly transfer the sample bottle containing the mixture prepared in Step 2 to the water bath in Step 3.

[0094] Step 5: Gradually reduce the temperature of the water bath at a rate of 3 °C per hour to room temperature, so that the temperature of the mixture in the sample bottle slowly decreases with the water bath temperature. After reaching room temperature, yellow block - shaped single crystals are obtained, which are the TMAPA eutectic material.

[0095] The identification method for the structure of an oily guest using the eutectic material based on a tetraaryladamantane crystallization co - former is as follows:

[0096] Under a microscope, select transparent crystals with appropriate size and regular shape from the eutectic obtained in Step 5. Collect diffraction data on a Bruker SCD D8 single crystal X - ray diffractometer using a copper target at 193 K.

[0097] The obtained diffraction data was subjected to unit cell refinement and data reduction on the APEX software, and then single crystal analysis was performed on the Olex2 software to obtain the precise structure of the guest molecule. It was found that the guest molecule was geranyl acetate (The eutectic data of TMAPA and geranyl acetate are shown in Table 3, and the eutectic structure is as Figure 4 shown).

[0098] Table 3: Eutectic data of TMAPA and geranyl acetate

[0099]

[0100]

[0101] Example 3 was repeated 3 times, and the repetition rate of the obtained eutectic material of TMAPA and geranyl acetate reached 100%.

[0102] Example 4

[0103] A eutectic material based on a tetraaryl adamantane crystallization co - former, and its preparation method includes the following steps:

[0104] Step 1: Weigh 2 mg of TMAPA synthesized by the above method and set it aside; Pipette 55 μL of S - 1 - phenylethylamine and set it aside; Pipette 50 μL of chlorobenzene solvent and set it aside;

[0105] Step 2: Mix the TMAPA and S - 1 - phenylethylamine weighed in Step 1 in a sample bottle, and place it on a heating plate. Set the heating temperature to 90 °C and heat for 1 min until a clear and transparent mixture is obtained;

[0106] Step 3: Turn on the constant temperature water bath and set the temperature to 90 °C. Wait until the water bath temperature reaches the set value and stabilizes;

[0107] Step 4: Quickly transfer the sample bottle containing the mixture prepared in Step 2 to the water bath in Step 3.

[0108] Step 5: Gradually reduce the temperature of the water bath at a rate of 3 °C / hour to room temperature, so that the temperature of the mixture in the sample bottle slowly decreases with the water bath temperature. After reaching room temperature, yellow block - shaped single crystals are obtained, which are the TMAPA eutectic material.

[0109] The method for identifying the structure of an oily guest using the eutectic material based on a tetraaryl adamantane crystallization co - former is as follows:

[0110] Under a microscope, select transparent crystals with appropriate size and regular shape from the eutectic obtained in Step 5. Collect diffraction data on a Bruker SCD D8 single - crystal X - ray diffractometer using a copper target at 193 K.

[0111] The obtained diffraction data was subjected to unit cell refinement and data reduction on APEX software, and then single crystal analysis was carried out on Olex2 software to obtain the precise structure of the guest molecule. It was found that the guest molecule was S-1-phenylethylamine, and its Flack parameter was 0.04(1). Its absolute configuration was also determined (the co-crystal data of TMAPA and S-1-phenylethylamine is shown in Table 4, and the co-crystal structure is as Figure 5 shown).

[0112] Table 4: Co-crystal data of TMAPA and S-1-phenylethylamine

[0113]

[0114]

[0115] Example 4 was repeated 3 times, and the repetition rate of the obtained co-crystal material of TMAPA and S-1-phenylethylamine reached 100%.

[0116] Example 5

[0117] A co-crystal material based on a tetraaryl adamantane crystallization partner, and its preparation method includes the following steps:

[0118] Step 1: Weigh 2 mg of TMAPA synthesized by the above method and set it aside; Pipette 85 μL of cis-jasmone and set it aside; Pipette 80 μL of chlorobenzene solvent and set it aside;

[0119] Step 2: Mix the TMAPA, cis-jasmone and chlorobenzene solvent weighed in Step 1 in a sample bottle, and place it on a heating plate. Set the heating temperature to 90 °C and heat for 1.5 min until a clear and transparent mixture is obtained;

[0120] Step 3: Turn on a constant temperature water bath and set the temperature to 90 °C. Wait until the water bath temperature reaches the set value and stabilizes;

[0121] Step 4: Quickly transfer the sample bottle containing the mixture prepared in Step 2 to the water bath in Step 3.

[0122] Step 5: Gradually reduce the temperature of the water bath at a rate of 2 °C / hour to room temperature, so that the temperature of the mixture in the sample bottle slowly decreases with the water bath temperature. After reaching room temperature, yellow block-shaped single crystals are obtained, which are the TMAPA co-crystal material.

[0123] The oil-like guest structure was identified using the co-crystal material based on the tetraaryl adamantane crystallization partner. The specific method is as follows:

[0124] Under a microscope, transparent crystals with appropriate size and regular shape were selected from the co-crystals obtained in Step 5. Diffraction data was collected on a Bruker SCD D8 single crystal X-ray diffractometer using a copper target at 193 K.

[0125] The obtained diffraction data was subjected to unit cell refinement and data reduction on the APEX software, and then single crystal analysis was performed on the Olex2 software to obtain the precise structure of the guest molecule, and it was found that the guest molecule was cis-jasmone.

[0126] Example 6

[0127] A cocrystal material based on a tetraaryl adamantane crystallization partner, and its preparation method includes the following steps:

[0128] Step 1: Weigh 2 mg of TMAPA synthesized by the above method and set aside; Pipette 85 μL of linalool and set aside; Pipette 80 μL of chlorobenzene solvent and set aside;

[0129] Step 2: Mix the TMAPA and linalool weighed in Step 1 in a sample bottle, and place it on a heating plate. Set the heating temperature to 90 °C and heat for 1.5 min until a clear and transparent mixture is obtained;

[0130] Step 3: Turn on the constant temperature water bath and set the temperature to 90 °C. Wait until the water bath temperature reaches the set value and stabilizes;

[0131] Step 4: Quickly transfer the sample bottle containing the mixture prepared in Step 2 to the water bath in Step 3.

[0132] Step 5: Gradually reduce the temperature of the water bath at a rate of 2 °C per hour to room temperature, so that the temperature of the mixture in the sample bottle slowly decreases with the water bath temperature. After reaching room temperature, yellow block-shaped single crystals are obtained, which are the cocrystal materials of TMAPA.

[0133] The structure identification of the oily guest was carried out using the cocrystal material based on the tetraaryl adamantane crystallization partner. The specific method is as follows:

[0134] Under the microscope, select transparent crystals with appropriate size and regular shape from the cocrystals obtained in Step 5. Use a copper target on a Bruker SCD D8 single crystal X-ray diffractometer to collect diffraction data at 193 K.

[0135] The obtained diffraction data was subjected to unit cell refinement and data reduction on the APEX software, and then single crystal analysis was performed on the Olex2 software to obtain the precise structure of the guest molecule, and it was found that the guest molecule was linalool.

[0136] Example 7

[0137] A cocrystal material based on a tetraaryl adamantane crystallization partner, and its preparation method includes the following steps:

[0138] Step 1: Weigh 2 mg of TMAPA synthesized by the above method for standby; Pipette 85 μL of geranyl acetate for standby; Pipette 80 μL of chlorobenzene solvent for standby;

[0139] Step 2: Mix the TMAPA and geranyl acetate weighed in Step 1 in a sample bottle, and place it on a heating plate. Set the heating temperature to 90 °C and heat for 1.5 min until a clear and transparent mixture is obtained;

[0140] Step 3: Turn on the constant temperature water bath and set the temperature to 90 °C. Wait until the water bath temperature reaches the set value and stabilizes;

[0141] Step 4: Quickly transfer the sample bottle containing the mixture prepared in Step 2 to the water bath in Step 3.

[0142] Step 5: Gradually reduce the temperature of the water bath to room temperature at a rate of 2 °C per hour, so that the temperature of the mixture in the sample bottle slowly decreases with the water bath temperature. After reaching room temperature, yellow block-shaped single crystals are obtained, which are the TMAPA cocrystal material.

[0143] Use the cocrystal material based on tetraaryladamantane crystallization partner to identify the structure of the oily guest. The specific method is as follows:

[0144] Under a microscope, select transparent crystals with appropriate size and regular shape from the cocrystals obtained in Step 5. Use a copper target on a Bruker SCD D8 single crystal X-ray diffractometer to collect diffraction data at 193 K.

[0145] Perform unit cell refinement and data reduction on the obtained diffraction data using APEX software, and then perform single crystal analysis using Olex2 software to obtain the precise structure of the guest molecule. It is found that the guest molecule is geranyl acetate.

[0146] Example 8

[0147] A cocrystal material based on tetraaryladamantane crystallization partner, and its preparation method includes the following steps:

[0148] Step 1: Weigh 2 mg of TMAPA synthesized by the above method for standby; Pipette 85 μL of S-1-phenylethylamine for standby; Pipette 80 μL of chlorobenzene solvent for standby;

[0149] Step 2: Mix the TMAPA and S-1-phenylethylamine weighed in Step 1 in a sample bottle, and place it on a heating plate. Set the heating temperature to 90 °C and heat for 1.5 min until a clear and transparent mixture is obtained;

[0150] Step 3: Turn on the constant temperature water bath and set the temperature to 90 °C. Wait until the water bath temperature reaches the set value and stabilizes;

[0151] Step 4: Quickly transfer the sample bottle containing the mixed solution prepared in Step 2 to the water bath in Step 3.

[0152] Step 5: Gradually reduce the temperature of the water bath to room temperature at a rate of 2 °C per hour, so that the temperature of the mixed solution in the sample bottle slowly decreases with the water bath temperature. After reaching room temperature, yellow block-shaped single crystals are obtained, which are the TMAPA eutectic material.

[0153] For the structural identification of oily guest using the eutectic material based on tetraaryladamantane crystallization co - former, the specific method is as follows:

[0154] Under a microscope, select transparent crystals with appropriate size and regular shape from the eutectic obtained in Step 5. Use a copper target on a Bruker SCD D8 single - crystal X - ray diffractometer to collect diffraction data at 193K.

[0155] Refine the unit cell and reduce the data of the obtained diffraction data on the APEX software, and then perform single - crystal analysis on the Olex2 software to obtain the precise structure of the guest molecule. It is found that the guest molecule is S - 1 - phenylethylamine, its Flack parameter is 0.04(1), and its absolute configuration is also determined.

[0156] Example 9

[0157] A eutectic material based on tetraaryladamantane crystallization co - former, its preparation method includes the following steps:

[0158] Step 1: Weigh 2 mg of TMAPA synthesized by the above method and set it aside; Pipette 100 μL of S - 1 - phenylethylamine and set it aside; Pipette 10 μL of chlorobenzene solvent and set it aside;

[0159] Step 2: Mix the TMAPA and S - 1 - phenylethylamine weighed in Step 1 in a sample bottle, and place it on a heating plate. Set the heating temperature to 110 °C and heat for 2 min until a clear and transparent mixed solution is obtained;

[0160] Step 3: Turn on the constant - temperature water bath and set the temperature to 110 °C. Wait until the water bath temperature reaches the set value and stabilizes;

[0161] Step 4: Quickly transfer the sample bottle containing the mixed solution prepared in Step 2 to the water bath in Step 3.

[0162] Step 5: Gradually reduce the temperature of the water bath to room temperature at a rate of 1 °C per hour, so that the temperature of the mixed solution in the sample bottle slowly decreases with the water bath temperature. After reaching room temperature, yellow block - shaped single crystals are obtained, which are the TMAPA eutectic material.

[0163] For the structural identification of oily guest using the eutectic material based on tetraaryladamantane crystallization co - former, the specific method is as follows:

[0164] Under a microscope, select transparent crystals with appropriate size and regular shape from the eutectic obtained in Step 5. Use a copper target on a Bruker SCD D8 single crystal X-ray diffractometer to collect diffraction data at 193K.

[0165] Refine the unit cell and reduce the data of the obtained diffraction data on the APEX software, and then perform single crystal analysis on the Olex2 software to obtain the precise structure of the guest molecule. It is known that the guest molecule is S-1-phenethylamine, and its Flack parameter is 0.04(1), and its absolute configuration is also determined.

[0166] Example 10

[0167] A eutectic material based on a tetraaryl adamantane crystallization partner, and its preparation method includes the following steps:

[0168] Step 1: Weigh 2 mg of TMAPA synthesized by the above method for standby; pipette 80 μL of S-1-phenethylamine for standby; pipette 100 μL of chlorobenzene solvent for standby;

[0169] Step 2: Mix the TMAPA and S-1-phenethylamine weighed in Step 1 in a sample bottle, and place it on a heating plate. Set the heating temperature to 100 °C and heat for 0.5 min until a clear and transparent mixture is obtained;

[0170] Step 3: Turn on a constant temperature water bath and set the temperature to 100 °C. Wait until the water bath temperature reaches the set value and stabilizes;

[0171] Step 4: Quickly transfer the sample bottle containing the mixture prepared in Step 2 to the water bath in Step 3.

[0172] Step 5: Gradually reduce the temperature of the water bath at a rate of 2 °C / hour to room temperature, so that the temperature of the mixture in the sample bottle slowly decreases with the water bath temperature. After reaching room temperature, yellow block-shaped single crystals are obtained, which are the TMAPA eutectic material.

[0173] Use the eutectic material based on the tetraaryl adamantane crystallization partner to identify the structure of the oily guest. The specific method is as follows:

[0174] Under a microscope, select transparent crystals with appropriate size and regular shape from the eutectic obtained in Step 5. Use a copper target on a Bruker SCD D8 single crystal X-ray diffractometer to collect diffraction data at 193K.

[0175] The obtained diffraction data was subjected to unit cell refinement and data reduction on the APEX software, and then single crystal analysis was carried out on the Olex2 software to obtain the precise structure of the guest molecule. It was found that the guest molecule was S-1-phenylethylamine, with a Flack parameter of 0.04(1), and its absolute configuration was also determined.

[0176] Comparative Example 1

[0177] A eutectic material based on a tetraaryl adamantane crystallization co - former was prepared in the same manner as in Example 1, except that in Step 2, the heating time was 0.3 min. Finally, a yellow powder was obtained, but the TMAPA eutectic material was not obtained.

[0178] Comparative Example 2

[0179] A eutectic material based on a tetraaryl adamantane crystallization co - former was prepared in the same manner as in Example 2, except that in Step 2, the heating time was 0.3 min. Finally, a yellow powder was obtained, but the TMAPA eutectic material was not obtained.

[0180] Comparative Example 3

[0181] A eutectic material based on a tetraaryl adamantane crystallization co - former was prepared in the same manner as in Example 3, except that in Step 2, the heating time was 0.3 min. Finally, a yellow powder was obtained, but the TMAPA eutectic material was not obtained.

[0182] Comparative Example 4

[0183] A eutectic material based on a tetraaryl adamantane crystallization co - former was prepared in the same manner as in Example 4, except that in Step 2, the heating time was 0.3 min. Finally, a yellow powder was obtained, but the TMAPA eutectic material was not obtained.

[0184] Comparative Example 5

[0185] A eutectic material based on a tetraaryl adamantane crystallization co - former was prepared in the same manner as in Example 1, except that in Step 2, the heating time was 3 min. Finally, a yellow powder was obtained, but the TMAPA eutectic material was not obtained.

[0186] Comparative Example 6

[0187] A eutectic material based on a tetraaryl adamantane crystallization co - former was prepared in the same manner as in Example 2, except that in Step 2, the heating time was 3 min. Finally, a yellow powder was obtained, but the TMAPA eutectic material was not obtained.

[0188] Comparative Example 7

[0189] A eutectic material based on a tetraaryladamantane crystallization co - former, its preparation is the same as that of Example 3, except that in Step 2, the heating time is 3 min. Finally, a yellow powder is obtained, but the TMAPA eutectic material is not obtained.

[0190] Comparative Example 8

[0191] A eutectic material based on a tetraaryladamantane crystallization co - former, its preparation is the same as that of Example 4, except that in Step 2, the heating time is 3 min. Finally, a yellow powder is obtained, but the TMAPA eutectic material is not obtained.

[0192] Comparative Example 9

[0193] A eutectic material based on a tetraaryladamantane crystallization co - former, its preparation is the same as that of Example 1, except that in Step 1, the amount of the oily guest cis - jasmone is 15 μL. Finally, a yellow powder is obtained, but the TMAPA eutectic material is not obtained.

[0194] Comparative Example 10

[0195] A eutectic material based on a tetraaryladamantane crystallization co - former, its preparation is the same as that of Example 2, except that in Step 1, the amount of the oily guest linalool is 15 μL. Finally, a yellow powder is obtained, but the TMAPA eutectic material is not obtained.

[0196] Comparative Example 11

[0197] A eutectic material based on a tetraaryladamantane crystallization co - former, its preparation is the same as that of Example 3, except that in Step 1, the amount of the oily guest geranyl acetate is 15 μL. Finally, a yellow powder is obtained, but the TMAPA eutectic material is not obtained.

[0198] Comparative Example 12

[0199] A eutectic material based on a tetraaryladamantane crystallization co - former, its preparation is the same as that of Example 4, except that in Step 1, the amount of the oily guest S - 1 - phenylethylamine is 15 μL. Finally, a yellow powder is obtained, but the TMAPA eutectic material is not obtained.

[0200] Comparative Example 13

[0201] A eutectic material based on a tetraaryladamantane crystallization co - former, its preparation is the same as that of Example 1, except that in Step 1, the amount of the oily guest cis - jasmone is 15 μL. Finally, a yellow powder is obtained, but the TMAPA eutectic material is not obtained.

[0202] Comparative Example 14

[0203] A cocrystal material based on a tetraaryl adamantane crystallization partner, the preparation of which is the same as that of Example 2, except that in Step 1, the dosage of the oily guest linalool is 15 μL. Finally, a yellow powder was obtained, but the TMAPA cocrystal material was not obtained.

[0204] Comparative Example 15

[0205] A cocrystal material based on a tetraaryl adamantane crystallization partner, the preparation of which is the same as that of Example 3, except that in Step 1, the dosage of the oily guest geranyl acetate is 15 μL. Finally, a yellow powder was obtained, but the TMAPA cocrystal material was not obtained.

[0206] Comparative Example 16

[0207] A cocrystal material based on a tetraaryl adamantane crystallization partner, the preparation of which is the same as that of Example 4, except that in Step 1, the dosage of the oily guest S-1-phenylethylamine is 15 μL. Finally, a yellow powder was obtained, but the TMAPA cocrystal material was not obtained.

[0208] Comparative Example 17

[0209] A cocrystal material based on a tetraaryl adamantane crystallization partner, the preparation of which is the same as that of Example 1, except that in Step 1, the dosage of the chlorobenzene solvent is 8 μL. Finally, a yellow powder was obtained, but the TMAPA cocrystal material was not obtained.

[0210] Comparative Example 18

[0211] A cocrystal material based on a tetraaryl adamantane crystallization partner, the preparation of which is the same as that of Example 2, except that in Step 1, the dosage of the chlorobenzene solvent is 8 μL. Finally, a yellow powder was obtained, but the TMAPA cocrystal material was not obtained.

[0212] Comparative Example 19

[0213] A cocrystal material based on a tetraaryl adamantane crystallization partner, the preparation of which is the same as that of Example 3, except that in Step 1, the dosage of the chlorobenzene solvent is 8 μL. Finally, a yellow powder was obtained, but the TMAPA cocrystal material was not obtained.

[0214] Comparative Example 20

[0215] A cocrystal material based on a tetraaryl adamantane crystallization partner, the preparation of which is the same as that of Example 4, except that in Step 1, the dosage of the chlorobenzene solvent is 8 μL. Finally, a yellow powder was obtained, but the TMAPA cocrystal material was not obtained.

[0216] Comparative Example 21

[0217] A eutectic material based on a tetraaryl adamantane crystallization co - former, the preparation of which is the same as that of Example 1, except that in Step 1, the amount of chlorobenzene solvent used is 130 μL. Finally, a yellow powder is obtained, but the TMAPA eutectic material is not obtained.

[0218] Comparative Example 22

[0219] A eutectic material based on a tetraaryl adamantane crystallization co - former, the preparation of which is the same as that of Example 2, except that in Step 1, the amount of chlorobenzene solvent used is 130 μL. Finally, a yellow powder is obtained, but the TMAPA eutectic material is not obtained.

[0220] Comparative Example 23

[0221] A eutectic material based on a tetraaryl adamantane crystallization co - former, the preparation of which is the same as that of Example 3, except that in Step 1, the amount of chlorobenzene solvent used is 130 μL. Finally, a yellow powder is obtained, but the TMAPA eutectic material is not obtained.

[0222] Comparative Example 24

[0223] A eutectic material based on a tetraaryl adamantane crystallization co - former, the preparation of which is the same as that of Example 4, except that in Step 1, the amount of chlorobenzene solvent used is 130 μL. Finally, a yellow powder is obtained, but the TMAPA eutectic material is not obtained.

[0224] Comparative Example 25

[0225] A eutectic material based on a tetraaryl adamantane crystallization co - former, the preparation of which is the same as that of Example 1, except that in Step 5, the cooling rate is 10 °C / h. Finally, a yellow powder is obtained, but the TMAPA eutectic material is not obtained.

[0226] Comparative Example 26

[0227] A eutectic material based on a tetraaryl adamantane crystallization co - former, the preparation of which is the same as that of Example 2, except that in Step 5, the cooling rate is 10 °C / h. Finally, a yellow powder is obtained, but the TMAPA eutectic material is not obtained.

[0228] Comparative Example 27

[0229] A eutectic material based on a tetraaryl adamantane crystallization co - former, the preparation of which is the same as that of Example 3, except that in Step 5, the cooling rate is 10 °C / h. Finally, a yellow powder is obtained, but the TMAPA eutectic material is not obtained.

[0230] Comparative Example 28

[0231] A eutectic material based on a tetraaryl adamantane crystallization co - former, its preparation is the same as that of Example 4, except that in step five, the cooling rate is 10 °C / h. Finally, a yellow powder is obtained, but the TMAPA eutectic material is not obtained.

[0232] Comparative Example 29

[0233] A eutectic material based on a tetraaryl adamantane crystallization co - former, its preparation is the same as that of Example 1, except that in step five, the cooling rate is 0.1 °C / h. Finally, a yellow powder is obtained, but the TMAPA eutectic material is not obtained.

[0234] Comparative Example 30

[0235] A eutectic material based on a tetraaryl adamantane crystallization co - former, its preparation is the same as that of Example 2, except that in step five, the cooling rate is 0.1 °C / h. Finally, a yellow powder is obtained, but the TMAPA eutectic material is not obtained.

[0236] Comparative Example 31

[0237] A eutectic material based on a tetraaryl adamantane crystallization co - former, its preparation is the same as that of Example 3, except that in step five, the cooling rate is 0.1 °C / h. Finally, a yellow powder is obtained, but the TMAPA eutectic material is not obtained.

[0238] Comparative Example 32

[0239] A eutectic material based on a tetraaryl adamantane crystallization co - former, its preparation is the same as that of Example 4, except that in step five, the cooling rate is 0.1 °C / h. Finally, a yellow powder is obtained, but the TMAPA eutectic material is not obtained.

[0240] Figure 2-5 The eutectic structures of TMAPA and different guests in Examples 1 - 4 of the present invention are shown in Figure 2-5 It can be seen that when the ratio among TMAPA, guest molecules and the solvent is appropriate, the guest molecules exist around the host molecule TMAPA and are arranged orderly in the cavity of the host TMAPA. When the ratio of solvent molecules to guest molecules is too high or too low, no eutectic crystal can be obtained and the structure of the guest molecules cannot be obtained.

[0241] The above - mentioned are only the preferred embodiments of the present invention, and the present invention is not limited to the above examples. It can be understood that other improvements and changes directly derived or associated by those skilled in the art without departing from the spirit and concept of the present invention should be considered as included within the protection scope of the present invention.

Claims

1. A eutectic material based on a tetraaryl adamantane crystallization co - former, characterized in that, The eutectic material is a host-guest complex formed by a tetraaryladamantane crystallization partner and an oily guest molecule; The tetraaryladamantane crystallization partner is 1,3,5,7-tetra(4-(10-methoxyanthracen-9-yl)phenyl)adamantane.

2. The eutectic material according to claim 1, wherein The oily guest molecule includes one or more of cis-jasmone, linalool, geranyl acetate, and S-1-phenylethylamine.

3. The eutectic material according to claim 1, wherein The mass-volume ratio of the tetraaryladamantane crystallization partner to the oily guest molecule is 2 mg: 50 - 100 μL.

4. The eutectic material according to claim 3, characterized in that, The synthesis route of the tetraaryladamantane crystallization partner is as follows:

5. A method for preparing a eutectic material based on a tetraaryl adamantane crystallization co - former according to any one of claims 1 - 4, characterized in that, The preparation method includes the following steps: S1: Weigh the tetraaryladamantane crystallization partner and the oily guest molecule and set aside. S2: Mix the tetraaryladamantane crystallization partner, the oily guest molecule, and chlorobenzene, and heat them on a heating plate to obtain a mixed solution. S3: Heat the constant temperature water bath device to the set temperature. S4: Place the mixed solution from step S2 into the constant temperature water bath device in step S3, and gradually lower the temperature of the water bath device to room temperature. The temperature of the mixed solution drops to room temperature as the water bath temperature decreases, obtaining a eutectic material based on the tetraaryladamantane crystallization partner.

6. The preparation method according to claim 5, wherein, In step S2, the mass-volume ratio of the tetraaryladamantane crystallization partner, the oily guest molecule, and chlorobenzene is 2 mg: 50 - 100 μL: 10 - 100 μL; the temperature of the heating plate is 90 - 110 °C, and the heating time is 0.5 - 2 min.

7. The preparation method according to claim 5, characterized in that, In step S3, the set temperature ≤ the temperature of the heating plate in S2.

8. The preparation method according to claim 5, characterized in that, In step S4, gradually lowering the temperature of the water bath device to room temperature means lowering it to room temperature at a rate of 1 - 3 °C / h.

9. Use of the eutectic material based on a tetraaryl adamantane crystallization co - former according to any one of claims 1 - 4, characterized in that, The eutectic material based on the tetraaryladamantane crystallization partner is used for the structural identification of oily guest molecules; the oily guest molecule includes one or more of cis-jasmone, linalool, geranyl acetate, and S-1-phenylethylamine.

10. The application according to claim 9, characterized in that, The specific steps for the structural identification of the oily guest molecule are as follows: (1) Prepare the eutectic material according to the preparation method described in claim 5. (2) Under a microscope, select single crystals from the eutectic material and measure them with a single crystal X-ray diffractometer to collect diffraction data. (3) Refine the unit cell and reduce the data for the obtained diffraction data, and finally perform single crystal analysis to obtain the precise structure and absolute configuration of the guest molecule.

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