Preparation method of palladium-based sulfur-containing organic macrocycle crystallization partner and application thereof in structural determination of flavonoid compounds

Abstract

The application belongs to the technical field of crystal synthesis and structure identification, and particularly relates to a preparation method of a palladium-based sulfur-containing organic macrocycle crystal chaperone and application thereof in structure determination of flavonoid compounds. The palladium-based sulfur-containing organic macrocycle crystal chaperone has elements of C, H, N, O, S and Pd, and a structure as shown in a formula, and can be directly used for structure determination of flavone aglycone, monoside, diside, triside and other flavonoid compounds. The palladium-based sulfur-containing organic macrocycle crystal chaperone has simple preparation process, high yield, and when used for host-guest crystal culture, does not need to be derivatized and modified, and is simple to operate. Meanwhile, the preparation raw material of the crystal chaperone is simple and easy to obtain, has good repeatability, high yield, wide application range, and indicates good application prospect.

Description

Technical Field

[0001] This invention belongs to the field of crystal synthesis and structure identification technology, specifically relating to a method for preparing a palladium-based sulfur-containing organic macrocyclic crystallization chaperone and its application in the determination of the structure of flavonoids. Background Technology

[0002] Due to the wide distribution, complex structure, and high variability of flavonoids (e.g., aglycones, glycosylated derivatives, methylated products, isoprene derivatives, oligomers, and polymers), their structural identification faces significant challenges. The presence of flavonoid aglycone isomers, the diversity of glycosylation modes, and the complex stereochemical relationships and variable glycosidic bond linkages between sugar units all significantly increase the difficulty of structural resolution. Furthermore, differences in the position of aglycone functional groups (e.g., hydroxyl and methoxy groups) or differences in glycosyl composition (e.g., deoxyglucose groups) can lead to multiple structural isomers of the same flavonoid compound, further increasing the complexity of their separation and identification. Therefore, the structural characterization of flavonoids typically requires the comprehensive use of multiple spectroscopic analysis techniques, including nuclear magnetic resonance spectroscopy (1D, 2D NMR), mass spectrometry (MS), ultraviolet-visible absorption spectroscopy (UV-Vis), infrared spectroscopy (IR), and circular dichroism spectroscopy (CD). However, even with this multi-method strategy, the structures of some complex flavonoids may still be misidentified, necessitating verification and correction through subsequent experiments.

[0003] Single-crystal X-ray diffraction (SCXRD) is one of the most reliable techniques for determining molecular structures, providing atomic-level structural precision and stereochemical conformations. However, a key prerequisite for SCXRD is obtaining high-quality crystals of suitable size. In recent years, novel assisted crystallization techniques have made significant progress in the field of compound structure identification: on the one hand, porous network framework systems with pre-formed pores, such as "crystal sponges," can selectively adsorb guest molecules of specific sizes into the pores and achieve structural resolution. However, the pore size and spatial configuration of such frameworks are relatively fixed, which significantly limits their substrate applicability; on the other hand, crystallization companion systems with guest-adaptive properties, such as Ag3Pz3 and FPOC, can achieve co-crystallization with complex guest molecules of different sizes through spatial structure adaptability and multiple non-covalent interactions. However, existing crystallization partners still have limitations in the structural identification of flavonoids. For example, co-crystallization of Ag3Pz3 with flavonoids requires acetylation modification, which can easily lead to complex product structures; co-crystallization of supramolecular systems such as cyclodextrins can only bind a few flavonoids; and co-crystallization of glycosyltransferases with flavonoids has low resolution and cannot meet the needs of atomic-level structural analysis.

[0004] Therefore, the preparation of a crystallization mate that enables high-resolution structural analysis of flavonoids is of significant scientific importance and has broad application prospects. Summary of the Invention

[0005] To address the problems existing in the prior art, this invention provides a method for preparing a palladium-based sulfur-containing organic macrocyclic crystallizer and its application in the structural determination of flavonoids. The preparation method of this crystallizer is simple, uses readily available raw materials, has good reproducibility, and high yield, making it suitable for the structural identification of complex flavonoids.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: The first aspect of this invention provides a palladium-based sulfur-containing organic macrocyclic crystallizer, wherein the elements of the palladium-based sulfur-containing organic macrocyclic crystallizer are C, H, N, O, S, and Pd, and the structural formula is: The palladium-based sulfur-containing organic ring crystal companion is triclinic, with space group P-1 and cell parameters: a=16.58, b=18.83, c=19.41 Å, α=63.62°, β=81.27°, γ=80.29°, and cell volume of 5332.7(3) Å. 3 .

[0007] A second aspect of this invention provides a method for preparing the above-mentioned palladium-based sulfur-containing organic macrocyclic crystallization chaperone, comprising the following steps: Step S1: Under an inert gas atmosphere, an organic solvent was added to a mixture of thiourea and 4-cyanopyridine, followed by the addition of a sodium hydride paraffin oil dispersion in batches. The reaction system was first stirred at room temperature, then heated to continue the reaction. After the reaction was completed, the solution was cooled to room temperature and quenched in ice water. The pH of the solution system was adjusted to neutral, then filtered and the filtrate was discarded. The obtained solid precipitate was collected and washed successively with deionized water and methanol to obtain intermediate 1, whose structural formula is: Step S2: The intermediate 1 obtained in step S1 and N,N-diisopropylethylamine were added to an organic solvent, followed by the addition of iodomethane solution; the reaction system was first stirred at room temperature, then heated to continue the reaction; after the reaction was completed, it was naturally cooled to room temperature; the precipitated solid was removed by filtration, the filtrate was collected and concentrated under reduced pressure; the residue obtained by concentration was redissolved in tetrahydrofuran solvent, and then deionized water was added to precipitate the solid. The obtained solid was washed with diethyl ether to obtain ligand 2, whose structural formula is: Step S3: The ligand 2 obtained in step S2 and the cis-terminated palladium (II) complex are dissolved in an organic solvent and heated to react. After the reaction is complete, the mixture is cooled to room temperature, and excess ethyl acetate solvent is added to the reaction solution until a precipitate is formed. The solid precipitate is collected by centrifugation and dried to obtain the palladium-based sulfur-containing organic macrocyclic crystallizer.

[0008] Further, in step S1, the equivalent ratio of thiourea to 4-cyanopyridine is 1:2~4; with thiourea as 1 equivalent, the equivalent of sodium hydride is 1.2~1.6.

[0009] Furthermore, the equivalent ratio of thiourea to 4-cyanopyridine is 1:2; with thiourea as 1 equivalent, the equivalent of sodium hydride is 1.2.

[0010] Furthermore, in step S1, the stirring time at room temperature is 2-4 hours; the temperature for continuing the reaction by heating is 80-100℃, and the time is 24-48 hours.

[0011] Furthermore, the stirring time at room temperature is 2 hours; the temperature for further reaction is raised to 80°C for 24 hours.

[0012] Further, in step S2, the equivalent ratio of intermediate 1 to iodomethane is 1:1 to 3.0; with intermediate 1 as 1 equivalent, the equivalent of N,N-diisopropylethylamine is 1.0 to 6.0.

[0013] Furthermore, the equivalent ratio of intermediate 1 to iodomethane is 1:1; with intermediate 1 as 1 equivalent, the equivalent of N,N-diisopropylethylamine is 2.0.

[0014] Furthermore, in step S2, the stirring time at room temperature is 2-4 hours; the temperature for continuing the reaction by heating is 70-90°C, and the time is 48-72 hours.

[0015] Furthermore, the stirring time at room temperature is 2 hours; the temperature for further reaction is 70°C, and the time is 48 hours.

[0016] A third aspect of this invention provides the application of the above-mentioned palladium-based sulfur-containing organic macrocyclic crystallizer in the determination of the structure of flavonoids, wherein the method of application is as follows: The palladium-based sulfur-containing organic macrocyclic crystallizer was dissolved in an organic solvent with a flavonoid compound. After evaporation, a cocrystal sample of the host-guest complex was obtained. The obtained cocrystal sample was collected and subjected to X-ray single-crystal diffraction analysis. The palladium-based sulfur-containing organic macrocyclic crystallizer of the present invention can be directly used for the crystal culture of flavonoid compounds. The culture process does not require high temperature, is simple to operate, and has good application prospects.

[0017] Furthermore, the evaporation time is 2-4 days.

[0018] Furthermore, the flavonoid compound is any one of apigenin, phlorizin, cosmosiderin, neohesperidin dihydrochalcone, rosin, and privetin.

[0019] Compared with the prior art, the beneficial effects of the present invention are: (1) The method for preparing palladium-based sulfur-containing organic macrocyclic crystallizers in this invention is simple to operate and has simple synthesis steps, without the need for cumbersome column chromatography purification methods; the prepared crystallizers have high purity and can be directly used for the structural determination of flavonoids.

[0020] (2) The raw materials for preparing palladium-based sulfur-containing organic macrocyclic crystallizers of the present invention are readily available, and the preparation method has good reproducibility and high yield.

[0021] (3) The palladium-based sulfur-containing organic macrocyclic crystallizer prepared by the present invention has good hydrophilicity and is suitable for the structural identification of amphiphilic flavonoids.

[0022] (4) In the process of culturing crystals, the present invention does not require complicated chemical structural modification of the compound, and the structure identification of flavonoids can be directly achieved by using palladium-based sulfur-containing organic macrocyclic crystallization companion.

[0023] In summary, this invention provides a new research approach for the determination of flavonoids, expands the application scope of crystallization partners, and has broad application prospects. Attached Figure Description

[0024] Figure 1 This is a synthetic route diagram for intermediate 1 and ligand 2.

[0025] Figure 2 The hydrogen spectrum of intermediate 1 is shown below.

[0026] Figure 3 This is the carbon spectrum of intermediate 1.

[0027] Figure 4 This is the hydrogen spectrum of ligand 2.

[0028] Figure 5 This is the carbon spectrum of ligand 2.

[0029] Figure 6 This is a synthetic route diagram for palladium-based sulfur-containing organic macrocycles (PdS-MOM).

[0030] Figure 7 This is the proton NMR spectrum of a palladium-based sulfur-containing organic macrocycle (PdS-MOM).

[0031] Figure 8The crystal diagram of palladium-based sulfur-containing organic macrocycle (PdS-MOM) includes: crystal structure diagram (a) and unit cell packing diagram (b).

[0032] Figure 9 The crystal diagram of PdS-MOM@Apigenin in Example 4 includes: chemical structure diagram of Apigenin (a), crystal structure diagram of Apigenin (b), crystal structure diagram of host and guest (c), and unit cell packing diagram (d).

[0033] Figure 10 The crystal diagram of PdS-MOM@Phlorizin in Example 5 includes: a chemical structure diagram of Phlorizin (a), a crystal structure diagram of Phlorizin (b), a crystal structure diagram of the host and guest (c), and a unit cell packing diagram (d).

[0034] Figure 11 The crystal diagram of PdS-MOM@Apigenin 7-glucoside in Example 6 includes: chemical structure diagram of Apogenin 7-glucoside (a), crystal structure diagram of Apogenin 7-glucoside (b), crystal structure diagram of host and guest (c), and unit cell packing diagram (d).

[0035] Figure 12 The crystal diagram of PdS-MOM@Neosperidin dihydrochalcone in Example 7 includes: chemical structure diagram of Neosperidin dihydrochalcone (a), crystal structure diagram of Neosperidin dihydrochalcone (b), crystal structure diagram of host and guest (c), and unit cell packing diagram (d).

[0036] Figure 13 The crystal diagram of PdS-MOM@Rhoifolin in Example 8 includes: chemical structure diagram of Rhoifolin (a), crystal structure diagram of Rhoifolin (b), crystal structure diagram of host and guest (c), and unit cell packing diagram (d).

[0037] Figure 14 The crystal diagram of PdS-MOM@Ligustroflavone in Example 9 includes: chemical structure diagram of Ligustroflavone (a), crystal structure diagram of Ligustroflavone (b), crystal structure diagram of host and guest (c), and unit cell packing diagram (d). Detailed Implementation

[0038] The specific embodiments of the present invention will be further described below. It should be noted that these descriptions are for the purpose of aiding understanding the present invention, but do not constitute a limitation thereof. Furthermore, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0039] Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods, and the experimental materials used in the following embodiments are all available through conventional commercial channels.

[0040] Example 1: Preparation of palladium-based sulfur-containing organic macrocyclic crystallization chaperone (1) Thiourea (0.05 mol, 1.0 eq) and 4-cyanopyridine (0.1 mol, 2.0 eq) were dissolved in dry dimethyl sulfoxide (180 mL). Sodium hydride (approximately 60% paraffin oil dispersion, approximately 0.06 mol, 1.2 eq) was slowly added in portions with stirring. After stirring at room temperature for 2 hours, the temperature was raised to 80 °C and reacted for 24 hours. After cooling to room temperature, the solution was poured into an ice-water system, and the pH of the reaction solution was adjusted to neutral with 2N H2SO4. The solid was collected by vacuum filtration, and the filter cake was washed successively with water and methanol. After vacuum drying, intermediate 1 was obtained as an orange solid (10.2 g, yield: 76.3%).

[0041] The synthetic route of intermediate 1 obtained in step (1) is shown below. Figure 1 The hydrogen spectrum is shown below. Figure 2 The proton spectrum data are as follows: 1 ¹H NMR (400 MHz, DMSO-d⁶, 298 K) δ 8.90–8.86 (m, 4H), 8.32 (d, J = 5.5 Hz, 4H); carbon spectrum shown in [reference needed]. Figure 3 The carbon spectrum data are as follows: 13 C NMR (151 MHz, DMSO-d6) δ 187.90, 164.42, 150.00, 141.20, 122.64. The structural formula of intermediate 1 is: (2) Intermediate 1 (3.74 mmol, 1.0 eq) was suspended in dry tetrahydrofuran (40.0 mL), and N,N-diisopropylethylamine (7.48 mmol, 2.0 eq) was slowly added to the reaction system. After stirring at room temperature for 2 hours, 5.0 mL of dry tetrahydrofuran solution of iodomethane (3.74 mmol, 1.0 eq) was slowly added dropwise. After the addition was complete, the temperature was raised to 70 °C and the reaction was carried out for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, the precipitated solid was removed by filtration, the filtrate was collected and concentrated under reduced pressure. The concentrated residue was redissolved in a small amount of tetrahydrofuran, and then deionized water was added to promote the precipitation of the precipitate. The obtained solid was washed with diethyl ether and dried under vacuum to obtain ligand 2, a white solid (646.5 mg, yield: 61%).

[0042] The synthetic route of ligand 2 obtained in step (2) is shown below. Figure 1 The hydrogen spectrum is shown below. Figure 4 The proton spectrum data are as follows: 1 ¹H NMR (400 MHz, Chloroform-d, 298 K): δ 8.89–8.84 (m, 4H), 8.43–8.40 (m, 4H), 2.75 (s, 3H); carbon spectrum shown in [reference needed]. Figure 5 The carbon spectrum data are as follows: 13 C NMR (100 MHz, Chloroform-d, 298 K): δ 184.89, 169.13, 150.81, 142.71, 122.45, 13.93. The structural formula of ligand 2 is: (3) A mixture of cis-[Pd(TMEDA)(NO3)2] (0.04 mmol, 1.0 eq) and ligand 2 (0.04 mmol, 1.0 eq) was dissolved in 0.8 mL DMSO and heated at 60 °C for 12 h to obtain a clear homogeneous solution. After the reaction solution was cooled to room temperature, excess ethyl acetate was added to the system to induce precipitation of the product. The solid-liquid mixture was centrifuged, the supernatant was discarded, and the solid precipitate was separated. The precipitate was dried under reduced pressure for 12 h to obtain a palladium-based sulfur-containing organic macrocycle (PdS-MOM) as a yellow solid (21.6 mg, yield: 86.0%).

[0043] The synthetic route of the palladium-based sulfur-containing organocyclic macrocycle (PdS-MOM) obtained in step (3) is shown below. Figure 6 The hydrogen spectrum is shown below. Figure 7 The proton spectrum data are as follows: 1¹H NMR (400 MHz, DMSO-d6, 298 K): δ 9.57 (s, 6H), 9.44 (s, 6H), 8.87 (s, 6H), 8.56 (s, 6H), 3.05 (s, 12H), 2.69 (s, 9H), 2.64 (s, 36H). The structural formula of the palladium-based sulfur-containing organomacrocycle (PdS-MOM) is as follows: (4) Dissolve 1 μmol of palladium-based sulfur-containing organic macrocyclic compound in 0.15 mL of a methanol-acetonitrile mixture and place it in a capped liquid chromatography vial. Insert a syringe needle into the cap of the vial to control the rate of solvent evaporation. Place the vial at 20°C for slow evaporation. After 2-3 days of solvent evaporation, colorless blocky crystals will precipitate at the bottom of the vial.

[0044] The crystal obtained in step (4) was subjected to single-crystal X-ray diffraction analysis using a D8 Venture (Bruker Diffraction) single-crystal X-ray diffractometer, and modeled and refined using OLEX2 software. The results showed that non-hydrogen atoms were anisotropically refined, and hydrogen atoms were fixed using a riding model. The elements were C, H, N, O, Pd, and S. The obtained crystallographic parameters are shown in Table 1, and the crystal structure diagram is shown in [Table 1]. Figure 8 .

[0045] Table 1. Crystal parameters of palladium-based sulfur-containing organomacrocyclic crystallizers molecular weight 2362.35 Temperature / K 150.00(2) Crystal system triclinic Space Group P-1 a / Å 16.5801(6) b / Å 18.8353(7) c / Å 19.4108(7) α / ° 63.6240(10) β / ° 81.266(2) γ / ° 80.2930(10) <![CDATA[Volume / Å 3 > 5332.7(3) Z 2 <![CDATA[ρ 计算 (g / cm 3 )]]> 1.471 <![CDATA[μ / mm -1 ]]> 5.383 F(000) 2448.0 <![CDATA[Crystal size / mm 3 > 0.182 × 0.163 × 0.101 radiation CuKα (λ = 1.54178) Data collection 2θ range / ° 5.272 to 144.776 Index range -20 ≤ h ≤20, 23 ≤ k ≤ 22, 23 ≤ l ≤23 Collected reflections 106856 Independent reflection <![CDATA[20896 [R int = 0.0420, R sigma = 0.0302]]]> Data / Constraints / Parameters 20896 / 1250 / 1183 <![CDATA[F 2 goodness of fit 1.035 The final R-index [I>=2σ(I)] <![CDATA[R1 = 0.0495, wR2 = 0.1451]]> Final R-index [All Data] <![CDATA[R1 = 0.0515, wR2 = 0.1468]]> <![CDATA[maximum difference; peak / valley / e Å -3 > 1.43 / -1.53 Example 2: Preparation of palladium-based sulfur-containing organic macrocyclic crystallization chaperone (1) Thiourea (0.05 mol, 1.0 eq) and 4-cyanopyridine (0.15 mol, 3.0 eq) were dissolved in dry dimethyl sulfoxide (180 mL). Sodium hydride (approximately 60% paraffin oil dispersion, approximately 0.07 mol, 1.4 eq) was slowly added in portions with stirring. After stirring at room temperature for 3 hours, the temperature was raised to 90 °C and reacted for 36 hours. After cooling to room temperature, the solution was poured into an ice-water system, and the pH of the reaction solution was adjusted to neutral with 2N H2SO4. The solid was collected by vacuum filtration, and the filter cake was washed successively with water and methanol. After vacuum drying, intermediate 1 was obtained as an orange solid (8.03 g, yield: 60.1%).

[0046] (2) Intermediate 1 (3.74 mmol, 1.0 eq) was suspended in dry tetrahydrofuran (40.0 mL), and N,N-diisopropylethylamine (14.96 mmol, 4.0 eq) was slowly added to the reaction system. After stirring at room temperature for 3 hours, 5.0 mL of dry tetrahydrofuran solution containing iodomethane (7.48 mmol, 2.0 eq) was slowly added dropwise. After the addition was complete, the temperature was raised to 80 °C and the reaction was carried out for 60 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, the precipitated solid was removed by filtration, the filtrate was collected and concentrated under reduced pressure. The concentrated residue was redissolved in a small amount of tetrahydrofuran, and then deionized water was added to promote the precipitation of the precipitate. The obtained solid was washed with diethyl ether and dried under vacuum to obtain ligand 2, which was a white solid (397.7 mg, yield: 37.8%).

[0047] (3) A mixture of cis-[Pd(TMEDA)(NO3)2] (1.6 mmol, 1.0 eq) and ligand 2 (1.6 mmol, 1.0 eq) was dissolved in 25 mL DMSO and heated at 60 °C for 12 h to obtain a clear homogeneous solution. After the reaction solution was cooled to room temperature, excess ethyl acetate was added to the system to induce precipitation of the product. The solid-liquid mixture was centrifuged, the supernatant was discarded, and the solid precipitate was separated. The precipitate was dried under reduced pressure for 12 h to obtain a palladium-based sulfur-containing organic macrocycle (PdS-MOM) as a yellow solid (838 mg, yield: 85.4%).

[0048] (4) Dissolve 1 μmol of palladium-based sulfur-containing organic macrocyclic compound in 0.15 mL of a methanol-acetonitrile mixture and place it in a capped liquid chromatography vial. Insert a syringe needle into the cap of the vial to control the rate of solvent evaporation. Place the vial at 20°C for slow evaporation. After 2-3 days of solvent evaporation, colorless blocky crystals will precipitate at the bottom of the vial.

[0049] Single-crystal diffraction experiments confirmed that the composition and structure of the palladium-based sulfur-containing organic macrocyclic (PdS-MOM) crystallization companion obtained in Example 1 were consistent.

[0050] Example 3: Preparation of palladium-based sulfur-containing organic macrocyclic crystallization chaperone (1) Thiourea (0.05 mol, 1.0 eq) and 4-cyanopyridine (0.2 mol, 4.0 eq) were dissolved in dry dimethyl sulfoxide (180 mL). Sodium hydride (approximately 60% paraffin oil dispersion, approximately 0.08 mol, 1.6 eq) was slowly added in portions with stirring. After stirring at room temperature for 4 hours, the mixture was heated to 100 °C and reacted for 48 hours. After cooling to room temperature, the solution was poured into an ice-water system, and the pH of the reaction solution was adjusted to neutral with 2N H2SO4. The solid was collected by vacuum filtration, and the filter cake was washed successively with water and methanol. After vacuum drying, intermediate 1 was obtained as an orange solid (7.48 g, yield: 56.0%).

[0051] (2) Intermediate 1 (3.74 mmol, 1.0 eq) was suspended in dry tetrahydrofuran (40.0 mL), and N,N-diisopropylethylamine (22.44 mmol, 6.0 eq) was slowly added to the reaction system. After stirring at room temperature for 4 hours, 5.0 mL of dry tetrahydrofuran solution containing iodomethane (11.22 mmol, 3.0 eq) was slowly added dropwise. After the addition was complete, the temperature was raised to 90 °C and the reaction was carried out for 72 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, the precipitated solid was removed by filtration, the filtrate was collected and concentrated under reduced pressure. The concentrated residue was redissolved in a small amount of tetrahydrofuran, and then deionized water was added to promote the precipitation of the precipitate. The obtained solid was washed with diethyl ether and dried under vacuum to obtain ligand 2, which was a white solid (276.8 mg, yield: 26.3%).

[0052] (3) A mixture of cis-[Pd(TMEDA)(NO3)2] (1.0 mmol, 1.0 eq) and ligand 2 (1.0 mmol, 1.0 eq) was dissolved in 15 mL DMSO and heated at 60 °C for 12 h to obtain a clear homogeneous solution. After the reaction solution was cooled to room temperature, excess ethyl acetate was added to the system to induce precipitation of the product. The solid-liquid mixture was centrifuged, the supernatant was discarded, and the solid precipitate was separated. The precipitate was dried under reduced pressure for 12 h to obtain a palladium-based sulfur-containing organic macrocycle (PdS-MOM) as a yellow solid (550 mg, yield: 87.5%).

[0053] (4) Dissolve 1 μmol of palladium-based sulfur-containing organic macrocyclic compound in 0.15 mL of a methanol-acetonitrile mixture and place it in a capped liquid chromatography vial. Insert a syringe needle into the cap of the vial to control the rate of solvent evaporation. Place the vial at 20°C for slow evaporation. After 2-3 days of solvent evaporation, colorless blocky crystals will precipitate at the bottom of the vial.

[0054] Single-crystal diffraction experiments confirmed that the composition and structure of the palladium-based sulfur-containing organic macrocyclic (PdS-MOM) crystallization companion obtained in Example 1 were consistent.

[0055] Example 4: Palladium-based sulfur-containing organic macrocyclic crystallizer used for structural identification of apigenin The palladium-based sulfur-containing organic macrocyclic crystallizer (PdS-MOM) prepared in Example 1 was dissolved in an acetonitrile-methanol mixed solvent (5:1, v / v) to prepare a 6.7 mM solution. 150 μL of this solution was taken, and 1.7 mg of apigenin was added. The resulting homogeneous yellow solution was transferred to a 2.0 mL capped liquid chromatography vial. A syringe needle was inserted into the cap of the vial to control the solvent evaporation rate. The vial was placed at 20°C for slow evaporation. After 1–3 days of solvent evaporation, yellow blocky crystals precipitated at the bottom of the vial.

[0056] Select crystals of suitable size, and then collect diffraction data using a single-crystal X-ray diffractometer, D8 Venture (Bruker Diffraction). Diffraction data were acquired at a low temperature of 150 K under Cu Kα (λ = 1.54184 Å) X-ray conditions, and then the diffraction data were reconstructed using the Apex 5 package. The reconstructed diffraction data were then used for structural analysis using the direct method in the SHEXLE package, and the structure was determined based on F... 2 The coordinates of each atom were refined using a full-matrix least-squares method. Anisotropy was applied to all non-hydrogen atoms except for solvent molecules. The refinement results are shown in Table 2, and the X-ray diffraction results of the single crystal are shown in [Table 2]. Figure 9 The figure includes the chemical structure diagram of Phloriziin (a), the crystal structure diagram of Phloriziin (b), the crystal structure diagram of the host and guest (c), and the unit cell packing diagram (d).

[0057] Table 2. Crystal data of PdS-MOM@Apigenin host-guest complexes molecular weight 4651.31 Temperature / K 150.00(10) Crystal system triclinic Space Group P-1 a / Å 16.7956(12) b / Å 21.0328(15) c / Å 31.883(2) α / ° 93.551(3) β / ° 99.004(3) γ / ° 105.742(3) <![CDATA[Volume / Å 3 > 10642.2(13) Z 2 <![CDATA[ρ 计算 (g / cm 3 )]]> 1.452 <![CDATA[μ / mm -1 ]]> 5.272 F(000) 4778.0 <![CDATA[Crystal size / mm 3 > 0.13 × 0.12 × 0.1 radiation CuKα (λ = 1.54184) Data collection 2θ range / ° 2.822 to 134.706 Index range -20 ≤ h ≤ 20, -25 ≤ k ≤ 25, -38 ≤ l ≤ 38 Collected reflections 230384 Independent reflection <![CDATA[37702 [R int = 0.0584, R sigma = 0.0376]]]> Data / Constraints / Parameters 37702 / 3487 / 2675 <![CDATA[F 2 goodness of fit 1.034 The final R-index [I>=2σ(I)] <![CDATA[R1 = 0.0941, wR2 = 0.2839]]> Final R-index [All Data] <![CDATA[R1 = 0.1005, wR2 = 0.2900]]> <![CDATA[Maximum difference value; peak / valley / e Å -3 > 2.50 / -1.44 Flack parameters <![CDATA[C 164 H 217.5 N 68.5 O 42 Pd6S6]]> The experimental results in Table 2 demonstrate that the crystallization companion (PdS-MOM) prepared in Example 1 can stably form a co-crystallization system with flavonoid aglycones, and obtain single crystal samples of the corresponding host-guest complex (PdS-MOM@Apigenin). This allows for the determination of the crystal structure of flavonoids, and is characterized by its simple operation and high accuracy.

[0058] Example 5: Palladium-based sulfur-containing organic macrocyclic crystallizer used for the structural identification of phlorizin The palladium-based sulfur-containing organic macrocyclic crystallizer (PdS-MOM) prepared in Example 1 was dissolved in an acetonitrile-methanol mixture (5:1, v / v) to prepare a 6.7 mM solution. 150 μL of this solution was taken, and 0.9 mg of phlorizin was added. The resulting homogeneous yellow solution was transferred to a 2.0 mL capped liquid chromatography vial. A syringe needle was inserted into the cap of the vial to control the solvent evaporation rate. The vial was placed at 20°C for slow evaporation. After 1–3 days of solvent evaporation, yellow blocky crystals precipitated at the bottom of the vial.

[0059] Select crystals of suitable size, and then collect diffraction data using a single-crystal X-ray diffractometer, D8 Venture (Bruker Diffraction). Diffraction data were acquired at a low temperature of 150 K under Cu Kα (λ = 1.54184 Å) X-ray conditions, and then the diffraction data were reconstructed using the Apex 5 package. The reconstructed diffraction data were then used for structural analysis using the direct method in the SHEXLE package, and the structure was determined based on F... 2 The atomic coordinates were refined using a full-matrix least-squares method. Anisotropy was applied to all non-hydrogen atoms, except for solvent molecules. The refinement results are shown in Table 3, and the X-ray diffraction results of the single crystal are shown in [Table 3]. Figure 10 The figure includes the chemical structure diagram of Phloriziin (a), the crystal structure diagram of Phloriziin (b), the crystal structure diagram of the host and guest (c), and the unit cell packing diagram (d).

[0060] Table 3. Crystal data of PdS-MOM@Phlorizin host-guest complexes molecular weight 4933.28 Temperature / K 150 Crystal system triclinic Space Group P1 a / Å 15.644(3) b / Å 19.675(3) c / Å 20.279(3) α / ° 61.249(6) β / ° 82.701(8) γ / ° 78.593(8) <![CDATA[Volume / Å 3 > 5360.2(15) Z 1 <![CDATA[ρ 计算 (g / cm 3 )]]> 1.528 <![CDATA[μ / mm -1 ]]> 5.345 F(000) 2542.0 <![CDATA[Crystal size / mm 3 > 0.152 × 0.089 × 0.072 radiation CuKα (λ = 1.54178) Data collection 2θ range / ° 4.974 to 138.08 Index range -18 ≤ h ≤ 18, -23 ≤ k ≤ 23, -24 ≤ l ≤ 24 Collected reflections 102635 Independent reflection <![CDATA[35811 [R int = 0.0605, R sigma = 0.0662]]]> Data / Constraints / Parameters 35811 / 1435 / 2795 <![CDATA[F 2 goodness of fit 1.064 The final R-index [I>=2σ(I)] <![CDATA[R1 = 0.0762, wR2 = 0.2049]]> Final R-index [All Data] <![CDATA[R1 = 0.0819, wR2 = 0.2102]]> <![CDATA[Maximum difference value; peak / valley / e Å -3 > 2.44 / -1.71 Flack parameters 0.285(12) The experimental results in Table 3 demonstrate that the crystallization companion (PdS-MOM) prepared in Example 1 can stably form a co-crystallization system with flavonoid monosaccharides, and obtain single crystal samples of the corresponding host-guest complex (PdS-MOM@Phlorizin). This allows for the determination of the crystal structure of flavonoids, and is characterized by its simple operation and high accuracy.

[0061] Example 6: Palladium-based sulfur-containing organic macrocyclic crystallization chaperone used for the structural identification of cosmososide The palladium-based sulfur-containing macrocyclic crystalline chalcogenide (PdS-MOM) prepared in Example 1 was dissolved in an acetonitrile-methanol mixture (5:1, v / v) to prepare a 6.7 mM solution. 150 μL of this solution was taken, and 0.7 mg of apigenin-7-glucoside was added. The resulting homogeneous yellow solution was transferred to a 2.0 mL capped liquid chromatography vial. A syringe needle was inserted into the cap of the vial to control the solvent evaporation rate. The vial was placed at 20°C for slow evaporation. After 1–3 days of solvent evaporation, yellow blocky crystals precipitated at the bottom of the vial.

[0062] Select crystals of suitable size, and then collect diffraction data using a single-crystal X-ray diffractometer, D8 Venture (Bruker Diffraction). Diffraction data were acquired at a low temperature of 150 K under Cu Kα (λ = 1.54184 Å) X-ray conditions, and then the diffraction data were reconstructed using the Apex 5 package. The reconstructed diffraction data were then used for structural analysis using the direct method in the SHEXLE package, and the structure was determined based on F... 2 The coordinates of each atom were refined using a full-matrix least-squares method. Anisotropy was applied to all non-hydrogen atoms, except for solvent molecules. The refinement results are shown in Table 4, and the X-ray diffraction results of the single crystal are shown in [Table 4]. Figure 11 The figure includes the chemical structure diagram of Apigenin-7-glucoside (a), the crystal structure diagram of Apigenin-7-glucoside (b), the crystal structure diagram of the host and guest (c), and the unit cell packing diagram (d).

[0063] Table 4. Crystal data of PdS-MOM@Apigenin-7-glucoside host-guest complexes molecular weight 4975.11 Temperature / K 150 Crystal system triclinic Space Group P-1 a / Å 18.9111(7) b / Å 21.6550(8) c / Å 28.8814(11) α / ° 94.445(2) β / ° 104.6240(10) γ / ° 95.3410(10) <![CDATA[Volume / Å 3 > 11331.8(7) Z 2 <![CDATA[ρ 计算 (g / cm 3 )]]> 1.458 <![CDATA[μ / mm -1 ]]> 5.099 F(000) 5146.0 <![CDATA[Crystal size / mm 3 > 0.13 × 0.12 × 0.1 radiation CuKα (λ = 1.54178) Data collection 2θ range / ° 3.178 to 144.776 Index range -22 ≤ h ≤ 23, -26 ≤ k ≤ 26, -35 ≤ l ≤ 35 Collected reflections 208697 Independent reflection <![CDATA[44644 [R int = 0.0468, R sigma = 0.0351]]]> Data / Constraints / Parameters 44644 / 2157 / 2778 <![CDATA[F 2 goodness of fit 1.075 The final R-index [I>=2σ(I)] <![CDATA[R1 = 0.0692, wR2 = 0.2010]]> Final R-index [All Data] <![CDATA[R1 = 0.0744, wR2 = 0.2055]]> <![CDATA[maximum difference value; peak / valley / e Å -3 > 1.26 / -1.19 The experimental results in Table 4 demonstrate that the crystallization companion (PdS-MOM) prepared in Example 1 can stably form a co-crystallization system with flavonoid monosaccharides, and obtain single crystal samples of the corresponding host-guest complex (PdS-MOM@Apigenin-7-glucoside). This allows for the determination of the crystal structure of flavonoids, and is characterized by its simple operation and high accuracy.

[0064] Example 7: Palladium-based sulfur-containing organic macrocyclic crystallization chalcogenide used for structural identification of neohesperidin dihydrochalcone The palladium-based sulfur-containing organic macrocyclic crystallizer (PdS-MOM) prepared in Example 1 was dissolved in an acetonitrile-methanol mixture (5:1, v / v) to prepare a 6.7 mM solution. 150 μL of this solution was taken, and 0.6 mg of neohesperidin dihydrochalcone was added. The resulting homogeneous yellow solution was transferred to a 2.0 mL capped liquid chromatography vial. A syringe needle was inserted into the cap of the vial to control the solvent evaporation rate. The vial was placed at 20°C for slow evaporation. After 1–3 days of solvent evaporation, yellow blocky crystals precipitated at the bottom of the vial.

[0065] Select crystals of suitable size, and then collect diffraction data using a single-crystal X-ray diffractometer, D8 Venture (Bruker Diffraction). Diffraction data were acquired at a low temperature of 150 K under Cu Kα (λ = 1.54184 Å) X-ray conditions, and then the diffraction data were reconstructed using the Apex 5 package. The reconstructed diffraction data were then used for structural analysis using the direct method in the SHEXLE package, and the structure was determined based on F... 2 The coordinates of each atom were refined using a full-matrix least-squares method. Anisotropy was applied to all non-hydrogen atoms, except for solvent molecules. The refinement results are shown in Table 5, and the X-ray diffraction results of the single crystal are shown in [Table 5]. Figure 12 The figure includes the chemical structure diagram of Neohesperidin dihydrochalcone (a), the crystal structure diagram of Neohesperidin dihydrochalcone (b), the crystal structure diagram of the host and guest (c), and the unit cell packing diagram (d).

[0066] Table 5. Crystal data of PdS-MOM@Neohesperidin dihydrochalcone host-guest complexes molecular weight 5864.53 Temperature / K 150.00(2) Crystal system triclinic Space Group P1 a / Å 16.6594(7) b / Å 20.0068(9) c / Å 21.4558(9) α / ° 96.294(2) β / ° 101.581(2) γ / ° 109.789(2) <![CDATA[Volume / Å 3 > 6468.4(5) Z 1 <![CDATA[ρ 计算 (g / cm 3 )]]> 1.506 <![CDATA[μ / mm -1 ]]> 4.640 F(000) 3049.0 <![CDATA[Crystal size / mm 3 > 0.198 × 0.123 × 0.099 radiation CuKα (λ = 1.54178) Data collection 2θ range / ° 4.784 to 133.18 Index range -19 ≤ h ≤ 19, -23 ≤ k ≤ 23, -25 ≤ l ≤ 25 Collected reflections 171291 Independent reflection <![CDATA[43644 [R int = 0.0466, R sigma = 0.0404]]]> Data / Constraints / Parameters 43644 / 2835 / 3033 <![CDATA[F 2 goodness of fit 0.991 The final R-index [I>=2σ(I)] <![CDATA[R1 = 0.0760, wR2 = 0.2489]]> Final R-index [All Data] <![CDATA[R1 = 0.0832, wR2 = 0.2681]]> <![CDATA[Maximum difference; peak / valley / e Å -3 > 3.14 / -1.08 Flack parameters 0.339(6) The experimental results in Table 5 demonstrate that the crystallization companion (PdS-MOM) prepared in Example 1 can stably form a co-crystallization system with flavonoid disaccharides, and obtain single crystal samples of the corresponding host-guest complex (PdS-MOM@Neohesperidin dihydrochalcone). This allows for the determination of the crystal structure of flavonoids, and is characterized by its simple operation and high accuracy.

[0067] Example 8: Palladium-based sulfur-containing organic macrocyclic crystallizer used for the structural identification of rhubarb glycoside The palladium-based sulfur-containing organic macrocyclic crystallizer (PdS-MOM) prepared in Example 1 was dissolved in an acetonitrile-methanol mixture (5:1, v / v) to prepare a 6.7 mM solution. 150 μL of this solution was taken, and 1.0 mg of rhoifolin was added. The resulting homogeneous yellow solution was transferred to a 2.0 mL capped liquid chromatography vial. A syringe needle was inserted into the cap of the vial to control the solvent evaporation rate. The vial was placed at 20°C for slow evaporation. After 1–3 days of solvent evaporation, yellow blocky crystals precipitated at the bottom of the vial.

[0068] Select crystals of suitable size, and then collect diffraction data using a single-crystal X-ray diffractometer, D8 Venture (Bruker Diffraction). Diffraction data were acquired at a low temperature of 150 K under Cu Kα (λ = 1.54184 Å) X-ray conditions, and then the diffraction data were reconstructed using the Apex 5 package. The reconstructed diffraction data were then used for structural analysis using the direct method in the SHEXLE package, and the structure was determined based on F... 2 The coordinates of each atom were refined using a full-matrix least-squares method. Anisotropy was applied to all non-hydrogen atoms, except for solvent molecules. The refinement results are shown in Table 6, and the X-ray diffraction results of the single crystal are shown in [Table 6]. Figure 13 The figure includes the chemical structure diagram of Rhoifolin (a), the crystal structure diagram of Rhoifolin (b), the crystal structure diagram of the host and guest (c), and the unit cell packing diagram (d).

[0069] Table 6. Crystal data of PdS-MOM@Rhoifolin host-guest complexes molecular weight 5329.20 Temperature / K 154.70(2) Crystal system triclinic Space Group P1 a / Å 16.2822(6) b / Å 18.7397(6) c / Å 21.1024(7) α / ° 83.7900(10) β / ° 70.5570(10) γ / ° 86.3700(10) <![CDATA[Volume / Å 3 > 6033.5(4) Z 1 <![CDATA[ρ 计算 (g / cm 3 )]]> 1.467 <![CDATA[μ / mm -1 ]]> 4.887 F(000) 2768.0 <![CDATA[Crystal size / mm 3 > 0.143 × 0.112 × 0.078 radiation CuKα (λ = 1.54178) Data collection 2θ range / ° 4.46 to 145.52 Index range -20 ≤ h ≤ 20, -23 ≤ k ≤ 23, -26 ≤ l ≤ 26 Collected reflections 163123 Independent reflection <![CDATA[44235 [R int = 0.0497, R sigma = 0.0465]]]> Data / Constraints / Parameters 44235 / 2189 / 2767 <![CDATA[F 2 goodness of fit 1.075 The final R-index [I>=2σ(I)] <![CDATA[R1 = 0.0532, wR2 = 0.1495]]> Final R-index [All Data] <![CDATA[R1 = 0.0562, wR2 = 0.1528]]> <![CDATA[Maximum difference value; peak / valley / e Å -3 > 1.09 / -0.78 Flack parameters 0.332(6) The experimental results in Table 6 demonstrate that the crystallization companion (PdS-MOM) prepared in Example 1 can stably form a co-crystallization system with flavonoid disaccharides, and obtain single crystal samples of the corresponding host-guest complex (PdS-MOM@Rhoifolin). This allows for the determination of the crystal structure of flavonoids, and is characterized by its simple operation and high accuracy.

[0070] Example 9: Palladium-based sulfur-containing organic macrocyclic crystallizer used for the structural identification of ligustrazine. The palladium-based sulfur-containing organic macrocyclic crystallizer (PdS-MOM) prepared in Example 1 was dissolved in an acetonitrile-methanol mixture (5:1, v / v) to prepare a 6.7 mM solution. 150 μL of this solution was taken, and 0.9 mg of ligustroflavone was added. The resulting homogeneous yellow solution was transferred to a 2.0 mL capped liquid chromatography vial. A syringe needle was inserted into the cap of the vial to control the solvent evaporation rate. The vial was placed at 20°C for slow evaporation. After 1–3 days of solvent evaporation, yellow blocky crystals precipitated at the bottom of the vial.

[0071] Select crystals of suitable size, and then collect diffraction data using a single-crystal X-ray diffractometer, D8 Venture (Bruker Diffraction). Diffraction data were acquired at a low temperature of 150 K under Cu Kα (λ = 1.54184 Å) X-ray conditions, and then the diffraction data were reconstructed using the Apex 5 package. The reconstructed diffraction data were then used for structural analysis using the direct method in the SHEXLE package, and the structure was determined based on F... 2 The coordinates of each atom were refined using a full-matrix least-squares method. Anisotropy was applied to all non-hydrogen atoms, except for solvent molecules. The refinement results are shown in Table 7, and the X-ray diffraction results of the single crystal are shown in [Table 7]. Figure 14 The figure includes the chemical structure diagram of Ligustroflavone (a), the crystal structure diagram of Ligustroflavone (b), the crystal structure diagram of the host and guest (c), and the unit cell packing diagram (d).

[0072] Table 7. Crystal data of PdS-MOM@Ligustroflavone host-guest complexes molecular weight 5544.89 Temperature / K 150.0 Crystal system triclinic Space Group P1 a / Å 16.4330(6) b / Å 18.7383(7) c / Å 21.2946(7) α / ° 84.605(2) β / ° 70.292(2) γ / ° 86.785(2) <![CDATA[Volume / Å 3 > 6143.7(4) Z 1 <![CDATA[ρ 计算 (g / cm 3 )]]> 1.499 <![CDATA[μ / mm -1 ]]> 4.850 F(000) 2885.0 <![CDATA[Crystal size / mm 3 > 0.165 × 0.145 × 0.134 radiation CuKα (λ = 1.54178) Data collection 2θ range / ° 4.422 to 144.704 Index range -20 ≤ h ≤ 20, -22 ≤ k ≤ 23, -26 ≤ l ≤ 26 Collected reflections 166086 Independent reflection <![CDATA[45582 [R int = 0.0525, R sigma = 0.0474]]]> Data / Constraints / Parameters 45582 / 1279 / 2380 <![CDATA[F 2 goodness of fit 1.080 The final R-index [I>=2σ(I)] <![CDATA[R1 = 0.0618, wR2 = 0.1748]]> Final R-index [All Data] <![CDATA[R1 = 0.0697, wR2 = 0.1962]]> <![CDATA[Maximum difference; peak / valley / e Å -3 > 1.66 / -1.32 Flack parameters 0.112(5) The experimental results in Table 7 demonstrate that the crystallization companion (PdS-MOM) prepared in Example 1 can stably form a co-crystallization system with flavonoid trisaccharides, and obtain single crystal samples of the corresponding host-guest complex (PdS-MOM@Ligustroflavone). This allows for the determination of the crystal structure of flavonoids, and is characterized by its simple operation and high accuracy.

[0073] The experimental results in Examples 4-9 demonstrate that the palladium-based sulfur-containing organic macrocyclic crystallization chaperone (PdS-MOM) prepared in this invention can be used to resolve the crystal structures of flavonoids that are difficult to identify using conventional methods. When using this crystallization chaperone, no chemical derivatization of the flavonoid compounds is required; the host-guest complex crystals can be obtained through co-crystallization, and the structures of flavonoid aglycones, monosaccharides, disaccharides, and trisaccharides can be directly resolved, making the overall operation simple. Furthermore, the preparation process of PdS-MOM is simple, the raw materials are readily available, and the synthesis process exhibits good reproducibility and high product yield. Considering these advantages, this crystallization chaperone has broad application prospects in the field of flavonoid structure identification.

[0074] The embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments. For those skilled in the art, various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention, and these variations still fall within the protection scope of the present invention.

Claims

1. A palladium-based sulfur-containing organic macrocyclic crystallizer, characterized in that, The palladium-based sulfur-containing organic macrocyclic crystallization chaperone has the elements C, H, N, O, S, and Pd, and its structural formula is: The palladium-based sulfur-containing organic ring crystal companion is triclinic, with space group P-1 and cell parameters: a=16.58, b=18.83, c=19.41 Å, α=63.62°, β=81.27°, γ=80.29°, and cell volume of 5332.7(3) Å. 3 .

2. A method for preparing a palladium-based sulfur-containing organic macrocyclic crystallization chaperone as described in claim 1, characterized in that, Includes the following steps: Step S1: Under an inert gas atmosphere, add an organic solvent to a mixture of thiourea and 4-cyanopyridine, followed by the addition of a sodium hydride paraffin oil dispersion in batches; stir the reaction system at room temperature first, then heat it to continue the reaction; after the reaction is complete, cool the solution to room temperature and quench it in ice water; adjust the pH of the solution system to neutral, filter it and discard the filtrate. The collected solid precipitate was washed successively with deionized water and methanol to obtain intermediate 1, whose structural formula is: Step S2: The intermediate 1 obtained in step S1 and N,N-diisopropylethylamine were added to an organic solvent, followed by the addition of iodomethane solution; the reaction system was first stirred at room temperature, then heated to continue the reaction; after the reaction was completed, it was naturally cooled to room temperature; the precipitated solid was removed by filtration, the filtrate was collected and concentrated under reduced pressure; the residue obtained by concentration was redissolved in tetrahydrofuran solvent, and then deionized water was added to precipitate the solid. The obtained solid was washed with diethyl ether to obtain ligand 2, whose structural formula is: Step S3: Dissolve the ligand 2 obtained in step S2 and the cis-terminated palladium (II) complex in an organic solvent and heat to react; after the reaction is completed, cool to room temperature and add excess ethyl acetate solvent to the reaction solution until a precipitate is precipitated; collect the solid precipitate by centrifugation and dry it to obtain the palladium-based sulfur-containing organic macrocyclic crystallizer.

3. The preparation method according to claim 2, characterized in that, In step S1, the equivalent ratio of thiourea to 4-cyanopyridine is 1:2~4; with thiourea as 1 equivalent, the equivalent of sodium hydride is 1.2~1.

6.

4. The preparation method according to claim 2, characterized in that, In step S1, the stirring time at room temperature is 2-4 hours; the temperature for continuing the reaction is 80-100℃, and the time is 24-48 hours.

5. The preparation method according to claim 2, characterized in that, In step S2, the equivalent ratio of intermediate 1 to iodomethane is 1:1 to 3.0; with intermediate 1 as 1 equivalent, the equivalent of N,N-diisopropylethylamine is 1.0 to 6.

0.

6. The preparation method according to claim 2, characterized in that, In step S2, the stirring time at room temperature is 2-4 hours; the temperature for continuing the reaction is 70-90℃, and the time is 48-72 hours.

7. The application of the palladium-based sulfur-containing organic macrocyclic crystallizer as described in claim 1 in the determination of the structure of flavonoids, characterized in that, The method of application is as follows: The palladium-based sulfur-containing organic macrocyclic crystallizer and flavonoids were dissolved in an organic solvent, and after volatilization, a cocrystal sample of the host-guest complex was obtained. The obtained cocrystal sample was collected and subjected to X-ray single-crystal diffraction analysis.

8. The application according to claim 7, characterized in that, The evaporation time is 2-4 days.

9. The application according to claim 7, characterized in that, The flavonoids are any one of apigenin, phloroglucinol, cosmosin, neohesperidin dihydrochalcone, rosin, and privetin.

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