Crystal sponge based on column [5] arene metal organic framework and preparation and application thereof

Abstract

The invention discloses crystal sponge based on a column [5] arene metal organic framework, a preparation method of the crystal sponge and application of the crystal sponge in compound crystal structure determination. The crystal sponge has a three-dimensional frame structure formed by coordination of pyridine nitrogen atoms in EtP5BPPy molecules and carboxylic acid groups in H4L1 molecules with Zn < 2 + >; the molecular structure of EtP5BPPy is shown in the specification, and the molecular structure of # imgabs0 # H4L1 is shown in the specification. A preparation method of # imgabs1 # comprises the following steps: completely dissolving EtP5BPPy, H4L1 and soluble Zn < 2 + > salt in a solvent, and reacting at 80-100 DEG C to obtain the crystal sponge.

Description

Technical Field

[0001] The present invention relates to the field of crystalline framework materials based on macrocyclic aromatic hydrocarbons, and in particular to a crystalline sponge based on a pillar[5]arene metal organic framework, a preparation method thereof, and an application thereof in the crystal structure determination of compounds such as natural products and drugs containing alkyl chains. Background Art

[0002] Structural determination is undoubtedly the core content of chemical research. As we all know, the most intuitive and accurate structural determination analysis method is single crystal X-ray diffraction (SCXRD) analysis. The SCXRD method requires the substance to be in a crystalline state, which makes it very important to grow high-quality single crystals. However, many compounds containing alkyl chains tend to form oil phases or amorphous phases during the single crystal growth process, so their crystal structures cannot be obtained. Metal organic frameworks (MOFs) are crystalline frameworks with ordered periodic structures. In the past decade, methods for determining the structure of substances by complexing target molecules into MOFs have been developed. For example, the "Crystalline Sponge" method reported by Fujita's research group is a revolutionary technology that determines the structure of molecules by accommodating target molecules into the pores of MOFs (Nature [J], 2013, 495, 461-466). This strategy relying on weak interactions solves the problem of determining the crystal structure of amorphous compounds and realizes the structural analysis of many organic molecules. In addition, another reported method, the "Coordinative Alignment" strategy reported by the Yaghi research group, focuses on solving the problem of determining the crystal structure of molecules with coordination groups such as carboxylic acid compounds (Science [J], 2016, 353, 808-811). However, most of the current MOF-based structure determination strategies rely on non-specific interactions to complex the guest. For some specific compounds closely related to natural products and drugs, such as molecules containing long alkyl chains, it is currently impossible to systematically solve their structure determination problems. Even if these molecules are complexed into MOF pores, they are generally quite disordered in SCXRD analysis. Therefore, this problem still needs to be solved by a highly selective method.

[0003] The Chinese patent document with publication number CN116333328A discloses a novel method for preparing a copper-based pyridine fluorene crystal sponge and its application. The copper-based pyridine fluorene crystal sponge provided by the patented technology is stable in the air and has high stability in common solvents; the prepared crystal sponge does not need to be activated; the successfully prepared crystal sponge can be directly used for soaking and testing the structure of the guest molecule, eliminating the complicated activation process. The preparation method of the crystal sponge is simple, the raw materials are easily available, and it has good repeatability, high yield, and a wide range of applications.

[0004] The patent specification with publication number CN117384139A discloses a novel method for preparing carbazole crystal sponge and its application. The carbazole crystal sponge provided by the patent technology has high stability in a variety of common solvents; the prepared crystal sponge does not need to be activated; the successfully prepared crystal sponge can be directly used for soaking and testing the structure of the guest molecule, eliminating the complicated activation process and making the operation more convenient. The preparation method of the crystal sponge is simple, the raw materials are easily available, and the repeatability is good and the yield is high.

[0005] However, none of the above methods can order the target molecules containing flexible alkyl chains in the crystal sponge.

[0006] Using a specific host-guest recognition interaction and using a crystalline framework material containing a supramolecular macrocycle to order the target molecule is a very effective method for structure determination. Therefore, in summary, finding a new method that can both quickly complex the target molecule and order the target molecule has become the key to determining the crystal structure of natural products or drugs containing alkyl chains. Summary of the invention

[0007] In view of the above technical problems and the shortcomings in the art, the present invention provides a crystal sponge based on a pillar[5]arene metal organic framework. By introducing pillar[5]arene into MOFs, accessible recognition sites can be provided for guest molecules, and at the same time, the long-range order of target molecules containing long alkyl chains can be promoted within the framework, which will be able to solve the problem of structural determination of such molecules. The crystal sponge of the present invention can complex guests containing long alkyl chains based on the host-guest recognition of "pillar[5]arene / alkyl chain". The crystal sponge of the present invention can be applied to the determination of a variety of molecules containing alkyl chains and reveal all of their single crystal structures. This article also reveals for the first time the crystal structure of a new drug called triheptanoin (Dojolvi).

[0008] A crystalline sponge based on pillar[5]arene metal organic framework, characterized by the interaction of the pyridinic nitrogen atom of EtP5BPPy with the carboxylic acid group of H4L1 (tetrakis(4-carboxybiphenyl)ethylene, CAS No. 1610858-96-2) via Zn 2+ The three-dimensional framework structure formed by coordination;

[0009] The molecular structure of EtP5BPPy is shown below:

[0010]

[0011] The molecular structure of H4L1 is shown below (where H4 can represent the 4 H atoms in the molecular structure of H4L1):

[0012]

[0013] The three-dimensional framework structure formed is shown below (see also Figure 5 ):

[0014]

[0015] The present invention also provides a method for preparing the crystal sponge based on pillar [5] aromatic metal organic framework, comprising: 2+ The salt is completely dissolved in the solvent, and the reaction is performed at 80-100° C. to obtain the crystalline sponge based on the pillar [5] aromatic metal organic framework.

[0016] The preparation method of the crystal sponge based on pillar [5] aromatic metal organic framework, the soluble Zn 2+ The salt may be zinc nitrate hexahydrate or the like.

[0017] In the method for preparing the crystalline sponge based on column [5] aromatic metal organic framework, the solvent may include at least one of N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), and N,N-diethylformamide (DEF), preferably DMF.

[0018] In the method for preparing the crystal sponge based on pillar [5] aromatic metal organic framework, the solvent may also contain acetic acid.

[0019] In the method for preparing the crystal sponge based on pillar[5]arene metal organic framework, the reaction time of the reaction can be 24 to 72 hours.

[0020] In the method for preparing the crystal sponge based on pillar [5] aromatic metal organic framework, the heating rate of the reaction can be 1°C / min, the cooling rate after the reaction is completed can be 0.2°C / min, and the cooling end point can be room temperature.

[0021] The method for preparing the crystalline sponge based on pillar [5] aromatic metal organic framework can further include separating and washing the crude product after the reaction is completed to obtain the crystalline sponge based on pillar [5] aromatic metal organic framework. Furthermore, the washing can include washing the crude product with N,N-dimethylformamide.

[0022] The present invention also provides an application of the crystal sponge based on pillar [5] aromatic metal organic framework in the determination of the crystal structure of a compound, and the application may include: the crystal sponge based on pillar [5] aromatic metal organic framework adsorbs and complexes the compound and then performs crystal structure determination. The compound may be a natural product, a drug, etc.

[0023] In some embodiments, the compound may contain a chain alkyl structure.

[0024] In some embodiments, the compound may include at least one of dihydrojasmone, butyldecanoate, bisabolol, cis-11-hexadecanal, isooctyl palmitate, methyl palmitoleate, methyl erucate, triheptanoin, and the like.

[0025] The crystal sponge based on pillar[5]arene metal organic framework can effectively adsorb and complex target compound molecules and determine their crystal structures. The adsorption and complexation temperature can be room temperature, 20-35°C, etc., and the adsorption and complexation time can be 2-60 minutes, for example, ten minutes, etc. During the adsorption and complexation process, the crystal sponge of the present invention accommodates flexible target guest compound molecules. Since pillar[5]arene is embedded in the crystalline framework material, the originally flexible and disordered target molecules can become ordered in the framework system.

[0026] The present invention also provides a method for determining the crystal structure of a compound, comprising: immersing the crystal sponge based on the column [5] aromatic metal organic framework in a liquid sample of a compound to be tested for adsorption and complexation, and performing single crystal X-ray diffraction analysis after the adsorption and complexation is completed to determine the molecular crystal structure of the compound to be tested.

[0027] In the compound crystal structure determination method, the volume of the liquid sample of the compound to be tested can be 5 to 20 μL.

[0028] In the compound crystal structure determination method, the side length of the crystal sponge based on the pillar[5]arene metal organic framework can be 50 to 200 μm.

[0029] In the compound crystal structure determination method, the compound to be tested may be a natural product, a drug, etc.

[0030] In some embodiments, the test compound may contain a chain alkyl structure.

[0031] In some embodiments, the test compound may include at least one of dihydrojasmone, butyl decanolactone, bisabolol, cis-11-hexadecanal, isooctyl palmitate, methyl palmitoleate, methyl erucate, triheptanoin, and the like.

[0032] In the compound crystal structure determination method, the adsorption and complexation temperature can be room temperature, 20-35° C., etc., and the adsorption and complexation time can be 2-60 minutes, such as ten minutes.

[0033] The crystal sponge of the present invention can effectively adsorb target molecules from natural products and drugs containing alkyl chains, has low energy consumption, fast equilibrium time and simple operation, and overcomes the problems of the current crystal sponge system, such as long operation process, poor selectivity and highly disordered target molecules.

[0034] Due to the specific recognition of pillar [5] aromatics and molecules containing alkyl chains, the crystal sponge based on pillar [5] aromatics of the present invention can specifically complex and adsorb target molecules in the sample liquid. The crystal sponge based on pillar [5] aromatics is stable at room temperature and is suitable for various target molecules.

[0035] As a general inventive concept, the present invention also provides a columnar [5] aromatic hydrocarbon material having the structure shown below:

[0036]

[0037] Compared with the prior art, the present invention has the following beneficial effects: the target molecule adsorption and complexation process is fast and easy to operate, and can be carried out at room temperature without the need for complex equipment; the crystalline material used has a good recognition effect and the recognition process is very fast. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 Schematic diagram of the synthesis route of the pillar[5]arene-based ligand EtP5BPPy in Example 1;

[0039] Figure 2 is the H NMR of the pillar[5]arene-based ligand EtP5BPPy in Example 1 ( 1 H NMR) spectrum;

[0040] Figure 3 The carbon NMR ( 13 C NMR) spectrum;

[0041] Figure 4 is a high-resolution mass spectrometer of the column [5] aromatic-based ligand EtP5BPPy in Example 1;

[0042] Figure 5 Schematic diagram of the synthesis route of the crystalline sponge EtP5-MOF-2 based on the pillar [5]arene metal organic framework in Example 2;

[0043] Figure 6 Schematic diagram of the crystal structure of the pillar [5] aromatic metal organic framework-based crystal sponge EtP5-MOF-2 of Example 2;

[0044] Figure 7 The crystal sponge EtP5-MOF-2 based on column [5] aromatic metal organic framework of Example 2 after digestion 1 H NMR spectrum;

[0045] Figure 8 is a powder X-ray diffraction (PXRD) pattern of the crystalline sponge of Example 2;

[0046] Fig. 9 195K CO2 adsorption isotherm diagram of the crystalline sponge EtP5-MOF-2 of Example 2;

[0047] Fig.10 are the chemical structural formulas of target molecules 1 to 8 of Examples 3 to 10;

[0048] Fig.11 This is a schematic diagram of the crystal structure of the target molecule 1 of Example 3 being complexed in the crystal sponge EtP5-MOF-2;

[0049] Fig.12 This is a schematic diagram of the crystal structure of the target molecule 2 of Example 4 being complexed in the crystal sponge EtP5-MOF-2;

[0050] Fig.13 This is a schematic diagram of the crystal structure of the target molecule 3 of Example 5 being complexed in the crystal sponge EtP5-MOF-2;

[0051] Fig.14 This is a schematic diagram of the crystal structure of the target molecule 4 of Example 6 being complexed in the crystal sponge EtP5-MOF-2;

[0052] Fig.15 This is a schematic diagram of the crystal structure of the target molecule 5 of Example 7 being complexed in the crystal sponge EtP5-MOF-2;

[0053] Fig.16 This is a schematic diagram of the crystal structure of the target molecule 6 of Example 8 being complexed in the crystal sponge EtP5-MOF-2;

[0054] Fig.17 This is a schematic diagram of the crystal structure of the target molecule 7 of Example 9 being complexed in the crystal sponge EtP5-MOF-2;

[0055] Fig.18 This is a schematic diagram of the crystal structure of the target molecule 8 of Example 10 complexed in the crystal sponge EtP5-MOF-2. DETAILED DESCRIPTION

[0056] The present invention will be further described below in conjunction with the accompanying drawings and specific examples. It should be understood that these examples are only intended to illustrate the present invention and are not intended to limit the scope of the present invention. The operating methods in the following examples without specifying specific conditions are usually carried out under conventional conditions or under conditions recommended by the manufacturer.

[0057] H4L1 is commercially available, CAS No. 1610858-96-2.

[0058] EtP5(OTf)2 can be prepared according to existing technology, for example, refer to Chem.Eur.J.2018, 24, 4264-4267 or J.Am.Chem.Soc.2021, 143, 11976-11981, etc.

[0059] During SCXRD data collection, single crystal samples were stored at 193 K, 221 K, 238 K, and 300 K. Anisotropic refinement was performed on F2 using the intrinsic phase method and weighted full-matrix least squares with the SHELXT and SHELXL programs and the olex2 graphical interface. The residual electron density in the solvent accessible gaps due to disordered solvent molecules was treated with the PLATON SQUEEZE program 2.

[0060] Example 1

[0061] The preparation of the pillar[5]arene-based ligand EtP5BPPy was carried out by the following synthetic route: Figure 1 As shown, specifically:

[0062] EtP5(OTf)2 (1.10 g, 1.00 mmol), (4-(pyridin-4-yl)phenyl)boric acid (597 mg, 3.00 mmol), K2CO3 (414 mg, 3.00 mmol), Pd(dppf)Cl2 (146 mg, 200 μmol) and dicyclohexyl(2',6'-dimethoxy-2-biphenyl)phosphine (Sphos, 205 mg, 500 μmol) were added to 100 mL of a mixed solvent (dioxane / water, 4:1 v / v). The mixture was heated at reflux at 90 °C under an argon atmosphere for 48 hours. After cooling, the crude product was concentrated and recrystallized (acetone / methanol) to give pale yellow EtP5BPPy crystals (560 mg, 50%). 1 H NMR (500MHz, CDCl3, 298K) δ (ppm): 8.68–8.67 (d, J = 5Hz, 4H), 7.78–7.77 (d, J = 4Hz, 4H), 7.76–7.75 (d, J = 5Hz, 4H), 7.25–7.2 4(d,J=5Hz,4H),7.11(s,2H),6.75(s,2H),6.72(s,2H),6.56(s,2H),5.78(s,2H),3.87–3.39(m,26H),1.30–0.93(m,24H). 13C (500MHz, CDCl3, 298K) δ (ppm): 166.37, 145.60, 145.20, 144.97, 144.74, 143.2 9,138.56,135.06,131.95,131.33,127.34,125.46,124.69,124.49,124.25,122 .87,121.65,116.65,111.01,110.58,110.27,110.08,59.79,59.48,58.94,58.6 9,55.64,28.87,25.37,24.31,16.30,10.55,10.26,9.99,9.75,9.45; HRMS[M+H] + [C 73 H 76 N2O8+H] + Calculated value: 1109.5663; tested value: 1109.5677.

[0063] Figure 1-4 The synthetic route of the pillar[5]arene-based ligand EtP5BPPy prepared in this example is shown. 1 HNMR, 13 C NMR and high-resolution mass spectrometry.

[0064] Example 2

[0065] Preparation of pillar[5]arene metal organic framework-based crystalline sponge, the synthetic route is as follows Figure 5 As shown, specifically:

[0066] Column [5] aromatic hydrocarbon EtP5BPPy (11.1 mg, 10.0 μmol), tetrakis(4-carboxybiphenyl)ethylene H4L1 (8.10 mg, 10.0 μmol) and Zn(NO3)2·6H2O (5.95 mg, 20.0 μmol) were prepared into a suspension (4 mL) of DMF and placed in a 4 mL vial. Then, 160 μL of acetic acid was added and the mixture was sonicated for 2 minutes. The suspension was then aspirated by a syringe and filtered with an organic filter to obtain a transparent solution. The solution was sealed and heated at 1 °C min. -1 The mixture was heated to 90 °C at a constant heating rate of 0.2 °C min -1 The product was cooled to room temperature at a constant cooling rate of . A single crystal suitable for single crystal X-ray diffraction (SCXRD) measurement was obtained and washed six times with 12 mL of DMF, each time with an interval of about half a day. The product was a transparent light yellow crystal, recorded as EtP5-MOF-2. The characterization data of the product prepared in this example are as follows: EtP5-MOF-2, 1H NMR(500MHz, DMSO-d6:DCl=100:1,298K)δ9.06–9.05(d,J=5Hz,4H),8.53–8.51(d,J=10Hz,4H),8.08–7.06(d,J =10Hz,4H),7.98–7.96(d,J=10Hz,8H),7.78–7.76(d,J=10Hz,8H),7.63–7.61(d,J=10Hz,8H),7.42–7.40(d,J= 10Hz,4H),7.21–7.19(d,J=10Hz,10H),6.77(s,2H),6.72(s,2H),6.58(s,2H),5.82(s,2H),3.91–3.41(m,26H) ,1.29–1.27(t,J=10Hz,6H), 1.17–1.13(t,J=20Hz,6H), 1.04–1.01(t,J=15Hz,6H), 0.97–0.93(t,J=20Hz,6H).

[0067] Figure 5 , Figure 6 The structure of the crystalline sponge based on pillar[5]arene metal-organic framework prepared in this example is shown. Figure 7 , Figure 8 , Fig. 9 The prepared pillar[5]arene-based 1 H NMR spectrum, PXRD spectrum and CO2 adsorption results show that the obtained crystalline sponge based on pillar[5]arene has good crystallinity and porosity.

[0068] Example 3

[0069] The mother liquor of the EtP5-MOF-2 single crystal prepared in Example 2 was poured out. The obtained crystals were washed three times with DMF (10 mL) to remove unreacted substances. The obtained crystals (side length 50-200 μm) were then immersed in a solution containing the target molecule 1 (dihydrojasmone, structure see Fig.10 , 20 μL) in a 2 mL vial and allowed to stand at room temperature for 10 minutes, after which the single crystal was ready for SCXRD testing. The SCXRD data collected after the test were analyzed by single crystal analysis to obtain the single crystal structure of the target molecule 1 complexed in EtP5-MOF-2. Fig.11 The structure of the pillar[5]arene metal organic framework-based crystalline sponge complexed with the target molecule 1 prepared in this example is shown, proving that this method can be used for the structural determination of the target molecule.

[0070] Table 1 shows the crystal data of the crystal sponge@dihydrojasmone complex obtained after the crystal sponge was soaked in dihydrojasmone.

[0071] Table 1

[0072]

[0073] Example 4

[0074] The mother liquor of the EtP5-MOF-2 single crystal prepared in Example 2 was poured out. The obtained crystals were washed three times with DMF (10 mL) to remove unreacted substances. The obtained crystals (side length 50-200 μm) were then immersed in a solution containing the target molecule 2 (butyl-decanoic acid lactone, structure see Fig.10 , 20 μL) in a 2 mL vial and allowed to stand at room temperature for 10 minutes, after which the single crystal was ready for SCXRD testing. The SCXRD data collected after the test were analyzed by single crystal analysis to obtain the single crystal structure of the target molecule 2 complexed in EtP5-MOF-2. Fig.12 The structure of the pillar[5]arene metal organic framework-based crystal sponge complexed with the target molecule 2 prepared in this example is shown, proving that this method can be used for the structural determination of the target molecule.

[0075] Table 2 shows the crystal data of the crystal sponge@butyl-decanoic acid complex obtained after the crystal sponge was soaked in butyl-decanoic acid.

[0076] Table 2

[0077]

[0078] Example 5

[0079] The mother liquor of the EtP5-MOF-2 single crystal prepared in Example 2 was poured out. The obtained crystals were washed three times with DMF (10 mL) to remove unreacted substances. The obtained crystals (side length 50-200 μm) were then immersed in a solution containing the target molecule 3 (bisabolol, structure see Fig.10 , 20 μL) in a 2 mL vial and allowed to stand at room temperature for 10 minutes, after which the single crystal was used for SCXRD testing. The SCXRD data collected after the test were analyzed by single crystal analysis to obtain the single crystal structure of the target molecule 3 complexed in EtP5-MOF-2. Fig.13 The structure of the pillar[5]arene metal organic framework-based crystal sponge complexed with the target molecule 3 prepared in this example is shown, proving that this method can be used for the structural determination of the target molecule.

[0080] Table 3 shows the crystal data of the crystal sponge@bisabolol complex obtained after the crystal sponge was soaked in bisabolol.

[0081] Table 3

[0082]

[0083] Example 6

[0084] The mother liquor of the EtP5-MOF-2 single crystal prepared in Example 2 was poured out. The obtained crystals were washed three times with DMF (10 mL) to remove unreacted substances. The obtained crystals (side length 50-200 μm) were then immersed in a solution containing the target molecule 4 (cis-11-hexadecanal, structure see Fig.10 , 20 μL) in a 2 mL vial and allowed to stand at room temperature for 10 minutes, after which the single crystal was used for SCXRD testing. The SCXRD data collected after the test were analyzed by single crystal analysis to obtain the single crystal structure of the target molecule 4 complexed in EtP5-MOF-2. Fig.14 The structure of the pillar[5]arene metal organic framework-based crystal sponge complexed with the target molecule 4 prepared in this example is shown, proving that this method can be used for the structural determination of the target molecule.

[0085] Table 4 shows the crystal data of the crystal sponge@cis-11-hexadecanal complex obtained after the crystal sponge was soaked in cis-11-hexadecanal.

[0086] Table 4

[0087]

[0088] Example 7

[0089] The mother liquor of the EtP5-MOF-2 single crystal prepared in Example 2 was poured out. The obtained crystals were washed three times with DMF (10 mL) to remove unreacted substances. The obtained crystals (side length 50-200 μm) were then immersed in a solution containing the target molecule 5 (isooctyl palmitate, structure see Fig.10 , 20 μL) in a 2 mL vial and allowed to stand at room temperature for 10 minutes, after which the single crystal was used for SCXRD testing. The SCXRD data collected after the test were analyzed by single crystal analysis to obtain the single crystal structure of the target molecule 5 complexed in EtP5-MOF-2. Fig.15 The structure of the pillar[5]arene metal organic framework-based crystal sponge complexed with the target molecule 5 prepared in this example is shown, proving that this method can be used for the structural determination of the target molecule.

[0090] Table 5 shows the crystal data of the crystal sponge@isooctyl palmitate complex obtained after the crystal sponge was soaked in isooctyl palmitate.

[0091] Table 5

[0092]

[0093] Example 8

[0094] The mother liquor of the EtP5-MOF-2 single crystal prepared in Example 2 was poured out. The obtained crystals were washed three times with DMF (10 mL) to remove unreacted substances. The obtained crystals (side length 50-200 μm) were then immersed in a solution containing the target molecule 6 (methyl palmitoleate, structure see Fig.10 , 20 μL) in a 2 mL vial and allowed to stand at room temperature for 10 minutes, after which the single crystal was used for SCXRD testing. The SCXRD data collected after the test were analyzed by single crystal analysis to obtain the single crystal structure of the target molecule 6 complexed in EtP5-MOF-2. Fig.16 The structure of the pillar[5]arene metal organic framework-based crystal sponge complexed with the target molecule 6 prepared in this example is shown, proving that this method can be used for the structural determination of the target molecule.

[0095] Table 6 shows the crystal data of the crystal sponge@methyl palmitoleate complex obtained after the crystal sponge was soaked in methyl palmitoleate.

[0096] Table 6

[0097]

[0098] Example 9

[0099] The mother liquor of the EtP5-MOF-2 single crystal prepared in Example 2 was poured out. The obtained crystals were washed three times with DMF (10 mL) to remove unreacted substances. The obtained crystals (side length 50-200 μm) were then immersed in a solution containing the target molecule 7 (methyl erucate, structure see Fig.10 , 20 μL) in a 2 mL vial and allowed to stand at room temperature for 10 minutes, after which the single crystal was used for SCXRD testing. The SCXRD data collected after the test were analyzed by single crystal analysis to obtain the single crystal structure of the target molecule 7 complexed in EtP5-MOF-2. Fig.17 The structure of the pillar[5]arene metal organic framework-based crystal sponge complexed with the target molecule 7 prepared in this example is shown, proving that this method can be used for the structural determination of the target molecule.

[0100] Table 7 shows the crystal data of the crystal sponge@methyl erucate complex obtained after the crystal sponge was soaked in methyl erucate.

[0101] Table 7

[0102]

[0103] Example 10

[0104] The mother liquor of the EtP5-MOF-2 single crystal prepared in Example 2 was poured out. The obtained crystals were washed three times with DMF (10 mL) to remove unreacted substances. The obtained crystals (side length 50-200 μm) were then immersed in a solution containing the target molecule 8 (triheptanoin, structure see Fig.10 , 20 μL) in a 2 mL vial and allowed to stand at room temperature for 10 minutes, after which the single crystal was ready for SCXRD testing. The SCXRD data collected after the test were analyzed by single crystal analysis to obtain the single crystal structure of the target molecule 8 complexed in EtP5-MOF-2. Fig.18 The structure of the pillar[5]arene metal organic framework-based crystal sponge complexed with the target molecule 8 prepared in this example is shown, proving that this method can be used for the structural determination of the target molecule.

[0105] Table 8 shows the crystal data of the crystal sponge@triheptanoin complex obtained after the crystal sponge was soaked in triheptanoin.

[0106] Table 8

[0107]

[0108] In addition, it should be understood that after reading the above description of the present invention, those skilled in the art may make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the claims attached to this application.

Claims

1. A crystalline sponge based on pillar[5]arene metal organic framework, characterized in that: The pyridine nitrogen atom in the EtP5BPPy molecule and the carboxylic acid group in the H4L1 molecule interact with each other through the Zn 2+ The three-dimensional framework structure formed by coordination; The molecular structure of EtP5BPPy is shown below: The molecular structure of H4L1 is shown below:

2. The method for preparing a crystalline sponge based on pillar[5]arene metal organic framework according to claim 1, characterized in that: include: EtP5BPPy, H4L1 and soluble Zn 2+ The salt is completely dissolved in the solvent, and the reaction is performed at 80-100° C. to obtain the crystalline sponge based on the pillar [5] aromatic metal organic framework.

3. The method for preparing a crystalline sponge based on pillar[5]arene metal organic framework according to claim 2, characterized in that: The solvent includes at least one of N,N-dimethylformamide, N,N-dimethylacetamide, and N,N-diethylformamide; The solvent contains acetic acid.

4. The method for preparing a crystalline sponge based on pillar[5]arene metal organic framework according to claim 2, characterized in that: The reaction time of the reaction is 24 to 72 hours.

5. The method for preparing a crystalline sponge based on pillar[5]arene metal organic framework according to claim 2, characterized in that: After the reaction is completed, the crude product is separated and washed to obtain the crystalline sponge based on the column [5] aromatic metal organic framework; The washing comprises washing the crude product with N,N-dimethylformamide.

6. The use of the crystal sponge based on pillar[5]arene metal organic framework according to claim 1 in the determination of the crystal structure of a compound, characterized in that: The application includes: the crystal sponge based on the pillar [5] aromatic metal organic framework adsorbs and complexes the compound and then performs crystal structure determination.

7. The use according to claim 6, characterized in that: The compound contains a chain alkyl structure.

8. The use according to claim 6, characterized in that: The compound comprises at least one of dihydrojasmone, butyl decalactone, bisabolol, cis-11-hexadecanal, isooctyl palmitate, methyl palmitoleate, methyl erucate and triheptanoin.

9. A method for determining the crystal structure of a compound, characterized in that: include: The crystal sponge based on the column [5] aromatic metal organic framework described in claim 1 is immersed in a liquid sample of the compound to be tested for adsorption and complexation. After the adsorption and complexation are completed, a single crystal X-ray diffraction analysis is performed to determine the molecular crystal structure of the compound to be tested.

10. A columnar aromatic material having the structure shown below:

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