KR100994314B1 - Method for synthesizing metal-macrocyclic compound complex - Google Patents

Abstract

Metal-macrocyclic compound composites having improved stability and methods for preparing the same are disclosed. The method for preparing a metal-macrocyclic compound complex includes mixing a metal salt, a macrocyclic compound, and a base solution to form a mixed solution, and reacting the metal salt, macrocyclic compound, and the base solution in the mixed solution. do.

Metal salts, macrocyclic compounds, cucurbituril, catalysts, metal nanoparticles

Description

Method for synthesizing metal-macrocyclic compound complex

The present invention relates to metal nanoparticles, and more particularly to a metal- macrocyclic compound complex and a method for synthesizing thereof.

Since metal nanoparticles can be applied to various fields such as catalysts, optical devices, nanotechnology, biotechnology, etc., much research is being conducted. Such metal nanoparticles can be chemically reduced, thermally decomposed, microwave-irradiated, sonochemical or photo-ly-tical, electrons. It may be prepared using chemical reduction, seeding growth approaches, or the like. However, such a method is very complicated and requires external energy. Nevertheless, agglomeration may occur between adjacent metal nanoparticles, which may result in a problem that the stability of the nanoparticles is deteriorated.

An object of the present invention for solving the above problems is to provide a metal-macrocyclic compound complex and a method for synthesizing the improved stability.

The present invention for achieving the above object comprises the steps of forming a mixed solution by mixing a metal salt, a macrocyclic compound and a base solution and reacting the metal salt, macrocyclic compound and the base solution in the mixed solution It provides a method for synthesizing a metal-macrocyclic compound complex.

The metal salt is KAuCl ₄ , _{NaAuCl 4 · 2H 2 O, HAuCl} 4 · 3H 2 O, NaAuBr 4 · xH 2 O (x = 1 ~ 5), AuCl 3, AuBr 3, AuCl, AgNO 3, AgCl, AgBr, AgI, CH 3 COOAg or AgBF Can be _four . The macrocyclic compound may be cucurbituril. The cucurbituril may be a cucurbit [5] uril, a cucurbit [6] uril, a cucurbit [7] uril, a cucurbit [8] uril or a cucurbit [10] uril. The base solution may be a NaOH solution.

The mixed solution may be formed by mixing the metal salt, the macrocyclic compound and the base solution in the same step, and the mixed solution may be formed by mixing the metal salt and the macrocyclic compound and then adding a base solution. have. The reaction may be carried out at a temperature of room temperature to 65 ℃.

The present invention for achieving the above-described other object provides a metal-macrocyclic compound composite comprising a metal particle and a macrocyclic compound containing the metal particles in the cavity.

The metal particles may have an oxidation number of zero. The metal particles may be Au, Ag, Pt, Pd, Ru, Rh, Fe, Co, Ni, Cu, Zn or Ti.

According to the present invention, since the macrocyclic compound can protect the metal particles, it is possible to prevent the phenomenon of condensation generated when only the metal particles are provided, and the dispersion stability can be improved.

In addition, the metal-macrocyclic compound complex can be prepared at room temperature without supply of external energy, and the metal-macrocyclic compound complex can be prepared easily and simply by changing the reaction conditions without complicated equipment. In addition, no reducing agent such as alcohol is used, which is harmless to the human body and suitable for biological use.

As the invention allows for various changes and numerous embodiments, particular embodiments will be illustrated in the drawings and described in detail in the written description.

However, this is not intended to limit the present invention to specific embodiments, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

Hereinafter, with reference to the accompanying drawings, it will be described in detail a preferred embodiment of the present invention. Hereinafter, the same reference numerals are used for the same components in the drawings, and redundant description of the same components is omitted.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

Example 1 Preparation of Metal-Macrocyclic Compound Composites

Metal salts, macrocyclic compounds and base solutions may be mixed in a container to form a mixed solution. The metal salt and cucurbituril may be added by dissolving in an aqueous solvent. The aqueous solvent may be water or water containing an organic medium.

The metal salt is KAuCl ₄ , _{NaAuCl 4 · 2H 2 O, HAuCl} 4 · 3H 2 O, NaAuBr 4 · xH 2 O (x = 1 ~ 5), AuCl 3, AuBr 3, AuCl, AgNO 3, AgCl, AgBr, AgI, CH 3 COOAg or AgBF Can be _four . The macrocyclic compound may be a cucurbituril, and specifically, the cucurbituril may be a cucurbit [5] uril, a cucurbit [6] uril, a cucurbit [7] uril, a cucurbit [8] uril or a cucurbit [10] urilyl Can be. The appearance of the cucurbituril may have a amber shape, and may have a cavity having a diameter of about 0.73 nm therein. In addition, each of the top and bottom of the amber shape may be provided with inlets of 0.54nm, carbonyl groups (C = O) may be surrounded around the respective inlet circumference.

In the prior art, alcohol was used as the reducing agent. However, such reducing agents not only adversely affect the environment, but also have disadvantages that are unsuitable for use in biomedical medicine due to their toxicity to alcohol. However, in the present invention, using a NaOH solution as the base solution can prevent problems due to the toxicity of the solution.

The mixed solution may be formed by mixing the metal salt, the macrocyclic compound and the base solution in the same step, or by mixing the metal salt and the macrocyclic compound, and then adding the base solution.

The metal salt, macrocyclic compound and base solution in the mixed solution can be reacted. As a result, the metal particles reduced from the metal salt can form a metal-macrocyclic compound complex contained in the cavity of the macrocyclic compound. The metal particles may be Pt, Pd, Ru, Rh, Fe, Co, Ni, Cu, Zn or Ti, and the metal particles may have zero oxidation number.

Since the metal-macrocyclic compound composite formed as described above may protect the metal particles, the macrocyclic compound may prevent condensation occurring when the macrocyclic compound is provided only with metal particles, and the dispersion stability may be improved.

Since the metal salt, the macrocyclic compound and the base solution can promote the reaction only by shaking, the stirring treatment using a separate stirrer may not be performed. The reaction may be performed at a temperature range of room temperature to 65 ° C., and may be performed for 1 minute to 48 hours. In this case, when the reaction time is increased, the reaction may be further accelerated, and thus the reaction time may be reduced. The metal nanoparticles may have a size range of 1 nm to 1 μm, and may have a spherical shape. When the metal nanoparticles are provided in a spherical shape, the surface tension may be lowered and the adsorption force may be increased.

Preparation Example 1: Preparation of gold-macrocyclic compound composite (1)

Aqueous KAuCl ₄ solution (5 mM; 2 mL, Aldrich) and an aqueous Cucurbit [7] uril solution (5 mM; 2 mL, Unisearch) were mixed at room temperature. At this time, a yellow precipitate was formed in the vessel. An aqueous NaOH solution (40 mM; 4 mL, DC Chemical Co.) was added to the mixed aqueous solution of the aqueous KAuCl ₄ solution and the aqueous cucurbit [7] uril solution. At this time, the mixed aqueous solution in the vessel disappeared to a yellow precipitate became a transparent color.

The aqueous solution was reacted at room temperature (25 ° C.) to prepare a gold-macrocyclic compound complex in which Au ⁰ reduced from KAuCl ₄ was contained in the cavity of the cucurbit [7] uril. The gold-macrocyclic compound complex was formed after about 48 hours, and the aqueous solution in the vessel became red as the gold-macrocyclic compound complex was formed.

Preparation Example 2 Preparation of Gold- Macrocyclic Compound Composite (2)

In the same manner as in Preparation Example 1, in order to analyze the change in the shape and size of the gold-macrocyclic compound complex according to the temperature change, the aqueous solution was reacted at a temperature of 45 ℃. As such, when a temperature of 45 ° C. was added, the gold-macrocyclic compound complex was formed after 1 hour.

Preparation Example 3: Preparation of gold-macrocyclic compound composite (3)

In the same manner as in Preparation Example 1, in order to analyze the change in the shape and size of the gold-macrocyclic compound complex according to the temperature change, the aqueous solution was reacted at a temperature of 65 ℃. As such, when a temperature of 65 ° C. was added, a gold-macrocyclic compound complex was formed after 30 minutes.

Preparation Example 4 Preparation of Gold- Macrocyclic Compound Composite (4)

To perform the same as in Preparation Example 1, to analyze the change in the shape and size of the gold-macrocyclic compound complex according to the change in the concentration of NaOH aqueous solution, the concentration of NaOH 10mM; 4 mL, and the aqueous solution was reacted at room temperature to prepare a gold-macrocyclic compound complex.

Preparation Example 5 Preparation of Gold-Great Ring Compound Composite (5)

To perform the same as in Preparation Example 1, to analyze the change in the shape and size of the gold-macrocyclic compound complex according to the change in the concentration of NaOH aqueous solution, the concentration of the NaOH 60mM; 4 mL, and the aqueous solution was reacted at room temperature to prepare a gold-macrocyclic compound complex.

Preparation Example 6 Preparation of Silver-macrocyclic Compound Composite (1)

An aqueous AgNO ₃ solution (5 mM; 2 mL) and an aqueous Cucurbit [7] uril solution (5 mM; 2 mL) were mixed in a single vessel at room temperature. At this time, a yellow precipitate formed in the single vessel. An aqueous NaOH solution (40 mM; 4 mL) was added to the mixed aqueous solution of the AgNO ₃ aqueous solution and the Cucurbit [7] uril aqueous solution. At this time, the mixed aqueous solution in the single vessel disappeared to a yellow precipitate became a transparent color.

The aqueous solution was reacted at room temperature to prepare a silver-macrocyclic compound complex. The silver-macrocyclic compound complex was formed after about 15 minutes, and the silver-macrocyclic compound complex was formed, and the aqueous solution in the single vessel became a bronze color.

Preparation Example 7 Preparation of Silver- Macrocyclic Compound Composite Nanoparticles (2)

Performed in the same manner as in Preparation Example 6, in order to analyze the change in the shape and size of the silver-macrocyclic compound complex according to the change in the concentration of NaOH aqueous solution, the concentration of NaOH 10mM; The silver-macrocyclic compound complex was prepared at 4 mL.

Table 1 below shows the average size and shape of each of Preparation Examples 1 to 5 with different reaction conditions. Specifically, the reaction conditions vary the concentration and reaction temperature of the NaOH aqueous solution.

Kinds Gold salt and cucurbit [7] usil content (mM) NaOH aqueous solution concentration (mM) Reaction temperature
(℃) Average size (nm) shape Preparation Example 1 5/5 40 25 10.01 ± 1.61 rectangle Production Example 2 5/5 40 45 14.44 ± 3.79 rectangle Production Example 3 5/5 40 65 15.65 ± 4.55 rectangle Preparation Example 4 5/5 10 25 13.63 ± 2.39 rectangle Preparation Example 5 5/5 60 25 12.79 ± 2.89 rectangle

As can be seen from the results of Table 1, the gold-macrocyclic compound complexes synthesized in Preparation Examples 1 to 3 increased in size, but the gold-macrocyclic compound complexes did not show a significant difference. There was no change in the shape of the particles.

In addition, the gold-macrocyclic compound complexes synthesized in Preparation Examples 4, 2, and 5 were 10, 40, and 60 mM in NaOH aqueous solution, respectively, and the average size of the gold-macrocyclic compound complexes was 13.63 ± 2.39 nm, respectively. At 10.01 ± 1.61 nm and 12.79 ± 2.89 nm, the size of the gold-macrocyclic complexes did not depend on the concentration of aqueous NaOH solution.

Therefore, it can be seen that the size and shape of the gold-macrocyclic compound complexes according to the present invention do not depend on the reaction temperature and the concentration of NaOH aqueous solution.

Gold-macrocyclic compound complexes can be identified by color and UV-vis spectra of the mixture. 1A and 1B are graphs showing the optical properties of the materials used in Preparation Example 1, respectively.

Referring to FIG. 1A, the surface plasma resonance band of gold particles generally exhibits an absorption peak at 530 nm. As a result of measuring the surface plasma resonance of the aqueous solution of KAuCl ₄ , no peak appeared in the 530 nm wavelength region (a of FIG. 1A). In addition, in the aqueous solution of NaOH mixed with an aqueous solution of KAuCl ₄ , the absorption peak of gold did not appear (b of FIG. 1A). However, when Cucurbit [7] uril was added to the aqueous solution of KAuCl ₄ and NaOH, 48 hours later, the absorption peak of gold was observed in the 530 nm region. This may indicate that the cucurbit [7] uril acted as a reducing agent to reduce the gold salt to Au (Au ⁰ ).

Referring to FIG. 1B, the color of the mixed solution obtained by reacting the KAuCl ₄ aqueous solution, the cooker beet [7] uril, and the NaOH aqueous solution for 48 hours was observed, and the color of the mixed solution was red. This may indicate that gold (Au ⁰ ) was synthesized from the mixed solution.

2A and 2B are graphs showing optical property changes with reaction time in Preparation Example 7. FIG.

Referring to FIG. 2A, the NaOH aqueous solution containing the AgNO ₃ aqueous solution and the aqueous solution of Cucurbit [7] uril were mixed, and the surface plasmon resonance band was checked over time. As the reaction time increased, the absorbance increased. , The absorbance of each of these was noticeable in the region of about 439 nm.

Referring to FIG. 2B, as a result of confirming the absorbance with time in the 439 nm region, the reaction of the silver-macrocyclic compound complex proceeded most actively until 20 minutes after the reaction started, and the reaction was terminated at 48 minutes.

2A and 2B, the absorption intensity of the silver-macrocyclic compound complex depends on the reaction time at a wavelength of about 439 nm, and the synthesis time of the silver-macrocyclic compound complex is 1 minute to about 50 minutes. have.

3A to 3D show TEM images of a gold-macrocyclic compound composite according to Preparation Example 1.

3A to 3D, the gold-macrocyclic compound composite prepared in Preparation Example 1 has a uniform distribution and size as a whole in an aqueous solution, and it can be seen that it is spherical (FIGS. 3A to 3C). As a result of analyzing the diffraction pattern image inserted in FIG. 3B, it can be seen that the gold-macrocyclic compound complex has crystallinity and has a face-centered cubic lattice structure (FCC). 174 gold nanoparticles in a single container prepared in Preparation Example 1 was synthesized, it can be seen that the average nanoparticle size is 10.01 ± 1.60nm (Fig. 3d).

Figure 4a is a TEM image showing the gold-macrocyclic compound complex prepared in Preparation Example 3.

Referring to FIG. 4A, the gold-macrocyclic compound complex prepared by reacting at a temperature of 45 ° C. shows a spherical shape as a whole, and it can be seen that each particle is well dispersed without being aggregated.

Figure 4b is a graph showing the size of the gold-macrocyclic compound composite prepared in Preparation Example 3.

Referring to Figure 4b, it can be seen that the average size of the gold-macrocyclic compound complex prepared by reacting at a temperature of 45 ℃ is 14.44 ± 3.79nm.

Figure 5a is a TEM image showing the gold-macrocyclic compound complex prepared in Preparation Example 4.

Referring to FIG. 5A, the gold-macrocyclic compound complex prepared by reacting at a temperature of 65 ° C. shows a spherical shape as a whole, and it can be seen that each particle is well dispersed rather than aggregated.

Figure 5b is a graph showing the size of the gold-macrocyclic compound composite prepared in Preparation Example 4.

Referring to Figure 5b, it can be seen that the average size of the gold-macrocyclic compound complex prepared by reacting at a temperature of 65 ℃ is 15.65 ± 4.55nm.

6A to 6E are TEM images of the silver-macrocyclic compound composites prepared in Preparation Examples 7 and 8.

6A to 6D, the silver-macrocyclic compound complex (Preparation Example 7) prepared by adding 10 mM NaOH shows a spherical shape, and it can be seen that a large amount of silver-macrocyclic compound complexes are evenly dispersed. (FIGS. 6A and 6C). On the contrary, the silver-macrocyclic compound composite prepared by adding 40 mM NaOH (Preparation Example 8) is less silver-macro-compound than the silver-macrocyclic compound composite prepared by adding 10 mM NaOH (Preparation Example 7). Cyclic complexes were synthesized (FIG. 6B).

In addition, about 864 silver-macrocyclic compound composites (Preparation Example 7) prepared by adding 10 mM NaOH were synthesized, and the average size was about 5.53 ± 0.95 nm (FIG. 6C). Silver-macrocyclic compound complex (Preparation Example 8) prepared by adding 40 mM NaOH had an average particle size of 2.83 ± 0.85 nm (FIG. 6D). In addition, as a result of analyzing the diffraction pattern image of the silver-macrocyclic compound complex, it can be seen that the silver-macrocyclic compound complex has crystallinity and is a face-centered cubic lattice structure (FCC) (inset of FIG. 6D).

As described above, the present invention does not depend on the reaction temperature and the concentration of NaOH. This is related to the structure of us cucurbit [7]. That is, cucurbit [7] uril has a single macrocyclic molecule and has a unique structural arrangement. The amber molecule of the cucurbit [uril] has a carbonyl group around the upper and lower inlets, and a large cavity is provided at the center having a larger diameter than the inlet. In addition, the outer surface of the cooker bit [7] us is hard and the inside is empty, so that it is easy to accommodate the particles in the interior cavity. Accordingly, the cucurbit [7] uril may prevent the growth of metal particles and prevent a reaction from occurring on the surface of the metal particles.

7 is a graph showing the results of X-ray diffraction analysis of pure gold and silver particles.

Referring to FIG. 7, the gold and silver particles showed inherent peaks at each location. The gold and silver particles exhibited crystallinity at positions (111), (200), (220) and (311), which can prove that the gold and silver particles are the cubic structure of the FCC.

8 is a graph showing Fourier transform infrared spectroscopy (FT-IR) spectra of Cucurbit [7] uril, Preparation Example 1, and Preparation Example 7. FIG.

Referring to FIG. 8, the cucurbit [7] uril showed a sharp peak at 1728 cm ⁻¹ , indicating a general carbonyl group band (FIG. 8 a). The gold-macrocyclic compound complex appeared similar to the vibration tendency of cucurbit [7] uril except for the intensity of the peak and the position of the carbonyl group band when compared to the cucurbit [7] uril according to FIG. That is, the gold-macrocyclic compound complex was shifted from 1728 cm ^-1 to 1743 cm ^-1 in position when compared to the cucurbit [7] uril (b in FIG. 8). The silver-macrocyclic compound composite exhibited a vibrational tendency similar to that of cucurbit [7] uril in a of FIG. 8, and shifted the position of the carbonyl group to 1735 cm ⁻¹ (FIG. 8 c).

9 is a graph showing the absorbency (a) of 4-nitrophenol and the absorbency (b) of the mixed solution in which NaBH ₄ aqueous solution is mixed with the 4-nitrophenol.

Referring to FIG. 9, the absorption band of 4-nitrophenol showed a peak at about 316 nm (FIG. 9A). As the NaBH ₄ aqueous solution was added thereto, the band position of 4-nitrophenol was shifted from the peak of the absorption band from 316 nm to 400 nm (b in FIG. 9). This is considered to be because 4-nitrophenol was converted into 4-nitrophenolate by addition of aqueous NaBH ₄ solution.

10A and 10B are graphs showing the absorbance of a solution in which a gold-macrocyclic compound complex according to Preparation Example 1, 4-nitrophenol, and NaBH ₄ are mixed. Specifically, the absorbance when the mixed solution is reacted for 5 minutes (b), 10 minutes (c), 15 minutes (d) and 20 minutes (e) is shown. 10A and 10B show the absorbance of the solution in which 4-nitrophenol and NaBH ₄ are mixed.

Referring to FIG. 10A, in the 400 nm region corresponding to 4-nitrophenolate, the mixed solution of the gold-macrocyclic compound complex, 4-nitrophenol and NaBH ₄ was decreased as the reaction time was increased. Within minutes, the peak of 4-nitrophenolate almost disappeared. On the other hand, the absorption peak was generated in the region of 231nm and 298nm due to the 4-aminophenol produced by the reduction of 4-nitrophenolate, and the absorption rate of 4-aminolphenol also increased as the reaction time increased.

Therefore, when a gold-macrocyclic compound complex is added and mixed to a solution of 4-nitrophenol and NaBH ₄ , a reduction reaction may proceed. As the reaction time increases, 4-nitrophenolate is 4-aminophenol. It can be seen that the reaction is reduced to more active. In addition, it can be seen that the gold-macrocyclic compound complex serves as a catalyst for promoting the reduction reaction.

Referring to FIG. 10B, the peak in the 530 nm region represents a plasmon band of gold (Au ⁰ ) in the gold-macrocyclic compound complex. This may indicate that the reduction reaction is promoted by providing gold (Au ⁰ ) in the gold-macrocyclic compound complex.

Such a reduction reaction can also be confirmed through the color of the solution when mixing. Specifically, 4-nitrophenol exhibits a bright yellow color. However, when NaBH ₄ aqueous solution was added thereto, the color of the aqueous solution changed to light green. This is because 4-nitrophenol was converted into 4-nitrophenolate by the addition of the NaBH ₄ aqueous solution. Then, in the case of mixing the gold-macrocyclic compound complex according to an embodiment of the present invention to the mixed solution, after about 20 minutes the mixed solution disappeared and showed a transparent color. This indicates that 4-nitrophenol was reduced to 4-aminophenol. Such a result is that the metal-macrocyclic compound complex according to an embodiment of the present invention is more improved than the conventional catalyst when considering that the reaction time is 27 minutes when using the citrate used as a catalyst. It can be seen that the catalytic reaction.

Additionally, in order to determine the stability of the metal-macrocyclic compound conjugate according to an embodiment of the present invention, a gold-macrocyclic compound complex formed by reacting a mixed solution containing a gold salt, a base solution and a macrocyclic compound is about 15 After storage for days, the dispersion and surface plasmon resonance bands were checked.

As a result, the mixed solution maintained the red color when the gold-macrocyclic compound complex was produced, and the dispersion degree and the surface plasmon resonance band remained unchanged. Therefore, the stability of the metal nanoparticles according to the embodiment of the present invention was confirmed through such a result.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention as defined by the following claims It can be understood that

1A and 1B are graphs showing the optical properties of the materials used in Preparation Example 1, respectively.

2A and 2B are graphs showing optical property changes with reaction time in Preparation Example 7. FIG.

3A to 3D show TEM images of a gold-macrocyclic compound composite according to Preparation Example 1.

Figure 4a is a TEM image showing the gold-macrocyclic compound complex prepared in Preparation Example 3.

Figure 4b is a graph showing the size of the gold-macrocyclic compound composite prepared in Preparation Example 3.

Figure 5a is a TEM image showing the gold-macrocyclic compound complex prepared in Preparation Example 4.

Figure 5b is a graph showing the size of the gold-macrocyclic compound composite prepared in Preparation Example 4.

6A to 6E are TEM images of the silver-macrocyclic compound composites prepared in Preparation Examples 7 and 8.

7 is a graph showing the results of X-ray diffraction analysis of pure gold and silver particles.

8 is a graph showing Fourier transform infrared spectroscopy (FT-IR) spectra of Cucurbit [7] uril, Preparation Example 1, and Preparation Example 7. FIG.

9 is a graph showing the absorbency (a) of 4-nitrophenol and the absorbency (b) of the mixed solution in which NaBH ₄ aqueous solution is mixed with the 4-nitrophenol.

10A and 10B are graphs showing the absorbance of a solution in which a gold-macrocyclic compound complex according to Preparation Example 1, 4-nitrophenol, and NaBH ₄ are mixed.

Claims (13)

Mixing a metal salt, cooker bituril, and a base solution to form a mixed solution; And A method for synthesizing a metal-macrocyclic compound complex comprising reacting a metal salt, a cucurbituril, and a base solution in the mixed solution. The method of claim 1, The metal salt is KAuCl ₄ , _{NaAuCl 4 · 2H 2 O, HAuCl} 4 · 3H 2 O, NaAuBr 4 · xH 2 O (x = 1 ~ 5), AuCl 3, AuBr 3, AuCl, AgNO 3, AgCl, AgBr, AgI, CH 3 COOAg or AgBF ₄ guests Method for synthesizing metal-macrocyclic compound complex. delete The method of claim 1, The cucurbituril is a method for synthesizing a metal-macrocyclic compound complex which is cucurbit [5] uril, cucurbit [6] uril, cucurbit [7] uril, cucurbit [8] uril or cucurbit [10] uril. The method of claim 1, The base solution is a method of synthesizing a metal-macrocyclic compound complex is a NaOH solution. The method of claim 1, The mixed solution is a method for synthesizing the metal-macrocyclic compound complex, characterized in that the metal salt, the cooker bituril and the base solution is formed by mixing in the same step. The method of claim 1, The mixed solution is a method of synthesizing a metal-macrocyclic compound complex, characterized in that the metal salt and the cooker bituril after mixing, by adding a base solution. The method of claim 1, The reaction is a method of synthesizing a metal- macrocyclic compound complex carried out at a temperature of room temperature to 65 ℃. delete delete delete delete delete

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