JP2020082002A - Multi-electron oxidation-reduction catalyst - Google Patents

Abstract

To provide a multi-electron oxidation-reduction catalyst that has a higher catalytic activity and is excellent in catalytic activity especially in the production of hydrogen, without using expensive metals.SOLUTION: Provided is a multi-electron oxidation-reduction catalyst composed of a cyclic compound having a 7 to 14-membered-ring cucurbit structure and a bulky compound included in the cyclic compound, and in which the bulky compound is two molecules of a metalloporphyrin compound represented by the following chemical formula (I) and a metal pearene or a metal salen. In the above formula, M1 represents a transition metal element or a base metal element.SELECTED DRAWING: None

Description

The present invention relates to a novel supramolecular multi-electron redox catalyst in which a metalloporphyrin complex and a metal pialene or a metal salen are included inside a cyclic compound such as cucurbit[10]uril.

Hydrogen is in the limelight as a next-generation high-efficiency power generation means because of its high energy density and the fact that it does not emit carbon dioxide when burned. On the other hand, hydrogen has serious problems such that it is difficult to transport over a long distance because it is a gas at room temperature and atmospheric pressure, it easily leaks from a storage container, and it explodes when mixed with air. Therefore, it can be said that establishment of a methodology for stable storage of hydrogen is essential for realizing a hydrogen society in which hydrogen is effectively used as an energy source.
Introduction of hydrogen atoms (hydrogen carrier) into the compound is effective for stable storage of hydrogen. For example, compounds produced by reduction of carbon dioxide (formic acid, formaldehyde, methanol, methane) and compounds produced by reduction of nitrogen (hydrazine, ammonia) are treated as hydrogen carriers.
A conventional approach to efficiently generate a hydrogen carrier is a metal binuclear complex catalyst. Efficient hydrogen carrier generation is possible by the joint catalytic reaction of two metals. However, the conventional approach requires complicated molecular design and catalytic synthesis according to the chemical structure of the hydrogen carrier. ..
Therefore, in order to realize a hydrogen society, it is necessary to establish a unified catalyst technology that can be applied to various compounds that are attracting attention as hydrogen carriers. Further, from the viewpoint of avoiding resource depletion, it is required to use metals that are abundant in nature.
Therefore, various proposals have been made, for example, Non-Patent Document 1 proposes a binuclear metal complex using ruthenium, which is a rare metal, as a catalyst for generating ammonia. Further, Non-Patent Document 2 proposes a metal binuclear complex using ruthenium as a catalyst for generating formic acid.
In addition, the inventors of the present invention have disclosed in Patent Document 1 that a multi-electron redox catalyst capable of easily forming various structures in an aqueous solvent and exhibiting high redox reactivity by using a metal species that is abundant in nature. , A multi-electron redox catalyst in which two molecules of a cyclic compound having a 7 to 14-membered cucurbit structure, a metalloporphyrin compound, and a compound selected from the group consisting of metalloporphyrin compounds and metal bipyridine compounds are included Is proposed.

Japanese Patent Application No. 2017-158456

Y. Arikawa et al., J. Am. Chem. Soc., 2018, 140, 842~847. T, Ono et al., ChemCatChem, 2013, 5, 3897~3903.

However, in the catalyst proposed in the above-mentioned non-patent document, it is necessary to use an expensive metal such as ruthenium, and sufficient catalytic activity has not yet been obtained. Further, in the proposals of the above-mentioned patent documents, although a high catalytic activity is obtained, it is not possible to satisfy the demand for a higher catalytic activity, particularly a catalytic activity in hydrogen production. Therefore, there is a demand for the development of a catalyst having a higher catalytic activity, particularly a catalytic activity in the production of hydrogen.
Therefore, an object of the present invention is to provide a multi-electron redox catalyst which has a higher catalytic activity, especially a catalytic activity in hydrogen production, without using an expensive metal.

As a result of intensive studies to solve the above problems, the present inventors have found that a metal complex including a specific metal porphyrin and a specific metal salen with a cucurbit compound exhibits a high catalytic effect. Further, a compound effective in combination with porphyrin was investigated, and the present invention was completed.
That is, the present invention provides each of the following inventions.
A cyclic compound having a cucurbit structure of 1.7 to 14-membered ring;
A catalyst consisting of a bulky compound included in the cyclic compound,
The bulky compound includes a metalloporphyrin compound represented by the following chemical formula (I), a metalloporphyrin compound represented by the following chemical formula (I), the metal pierlen represented by the following chemical formula (II) or the following chemical formula (III). A multi-electron redox catalyst characterized by being two molecules with a metal salen represented by:

In the above formulas, M1 and M2 are the same or different atoms and represent a transition metal element or a base metal element.
R5 to R8 are the same or different groups and represent a hydrogen atom, an alkyl group or an alkoxy group.

INDUSTRIAL APPLICABILITY The multi-electron redox catalyst of the present invention is excellent in higher catalytic activity, particularly in hydrogen production, without using an expensive metal.

FIGS. 1A and 1B are tracking charts of the complex formation behavior of the multi-electron redox catalyst obtained in Example 1. 2A and 2B are tracking charts of the complex formation behavior of the multi-electron redox catalyst obtained in Example 2. 3A and 3B are tracking charts of the complex formation behavior of the multi-electron redox catalyst obtained in Example 3. FIGS. 4A and 4B are charts showing the results of job's plot obtained in Example 3. 5A and 5B are tracking charts of the complex formation behavior of the multi-electron redox catalyst obtained in Example 4. FIGS. 6A and 6B are tracking charts of the complex formation behavior of the multi-electron redox catalyst obtained in Example 5. 7A and 7B are tracking charts of the complex formation behavior of the multi-electron redox catalyst obtained in Example 6. 8A and 8B are tracking charts of the complex formation behavior of the multi-electron redox catalyst obtained in Example 7. FIG. 9 is a chart of the ultraviolet-visible absorption spectrum of FeTM-4-PyP/Co-Salen/CB[10] obtained in Example 8. FIG. 10 is a chart of an ultraviolet-visible absorption spectrum of FeTM-4-PyP/Co-Salen(OMe)/CB[10] obtained in Example 9. FIG. 11 is a chart of an ultraviolet-visible absorption spectrum of FeTM-4-PyP/Fe-Salen(OMe)/CB[10] obtained in Example 10. FIG. 12 is a chart of an ultraviolet-visible absorption spectrum of FeTM-4-PyP/Fe-Salen/CB[10] obtained in Example 11. FIG. 13 is a chart of an ultraviolet-visible absorption spectrum of FeTM-4-PyP/Fe-Pyalen/CB[10] obtained in Example 12. FIG. 14 is a chart of an ultraviolet-visible absorption spectrum of FeTM-4-PyP/Co-Pyalen/CB[10] obtained in Example 13. FIG. 15 is a chart of an ultraviolet-visible absorption spectrum of (trans-CoM4Py ₂ P) ₂ /CB[10] obtained in Example 14. FIG. 16 is a chart of an ultraviolet-visible absorption spectrum of (trans-ZnM4Py ₂ P) ₂ /CB[10] obtained in Example 15. FIG. 17 is a chart of the ultraviolet-visible absorption spectrum of (trans-FeM4Py ₂ P) ₂ /CB[10] obtained in Example 16. FIG. 18 is a chart showing the results of cyclic voltammetry measurement performed in Example 17. 19(a) and 19(b) are charts showing the results of gas chromatograph measurement after the glucose reforming reaction performed in Example 18, respectively. 20(a) and 20(b) are charts showing the results of the nitrogen reduction reaction performed in Example 19, (a) showing a cyclic voltammogram in a helium atmosphere, and (b) showing a nitrogen atmosphere. 3 shows a cyclic voltammogram in FIG.

Hereinafter, the present invention will be described in more detail.
The multi-electron redox catalyst of the present invention comprises a cyclic compound and a bulky compound included in the cyclic compound.
<Cyclic compound>
The compound used as the cyclic compound in the present invention is a compound having a cucurbit structure having a 7 to 14 membered ring, preferably a 10 to 14 membered ring, and most preferably a 10 membered ring (hereinafter referred to as "cucurbit compound").
Examples of the cucurbit compound include cucurbit[10]uril (hereinafter referred to as “CB[10]”), cucurbit[8]uril (hereinafter referred to as “CB[8]”), cucurbit[7]uril (hereinafter referred to as “CB”). [7]”, cucurbit[14]uril (hereinafter referred to as “CB[14]”), and the like. The structural formula of CB[10] is shown below.
The cucurbit compound can be obtained by a known method, for example, the method described in Examples.

<Bulk compound>
The bulky compound used in the present invention includes a metalloporphyrin compound represented by the following chemical formula (I), a metalloporphyrin compound represented by the following chemical formula (I), and a metal pierne represented by the following chemical formula (II) or It is two molecules with a metal salen represented by the following chemical formula (III).

R5, R6, R7, and R8 are the same or different substituents, and each represents a hydrogen atom, an alkyl group, or an alkoxy group.
The alkyl group and alkoxy group preferably have 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. Specifically, the alkyl _{group, -CH 3, -CH 2 CH 3} , -CH 2 CH 2 CH 3, can be cited such as _{-CH 2 CH 2 CH 2 CH 3} , as the alkoxy group, - OCH _3, -OCH ₂ CH _3, may be mentioned -CH ₂ CH ₂ OCH ₃ and the like.
M1 and M2 are the same or different atoms and represent a transition element and a base metal element.
Examples of the transition element include Fe, Ni, Cu, Ru, Ir, Rh and Re, and examples of the base metal element include Zn, Mg, Mn, Co and Mo.
The above M1 and M2 are particularly preferably Mo, Fe or Co.
The bulky compound can be obtained by using the method described in each example.
Specific examples of the metal porphyrin compound include the following compounds.
Specific examples of the metal pialene and the metal salen include the following compounds.

<Specific example>
Preferred examples of the multi-electron redox catalyst of the present invention composed of the above cyclic compound and the above bulky compound include compounds represented by the following structural formulas.

<Manufacturing method>
The multi-electron redox catalyst of the present invention was obtained after adding a cyclic compound to an aqueous solution of one bulky compound and performing a reaction by sonicating at 0 to 100° C. for 1 to 60 minutes. It is possible to obtain the reaction by adding another aqueous solution of the bulky compound to the aqueous solution, adding the buffer solution, and stirring and mixing.

<How to use/effect>
Although the multi-electron redox catalyst of the present invention can be used as a catalyst in various redox reactions, it can be particularly preferably used in the reaction systems described below, as compared with the case where no catalyst is used in these reaction systems. It is also possible to improve the reaction efficiency several times.
(Reaction system)
Reaction system using oxygen as a raw material and ascorbic acid as a reducing agent (four-electron reduction reaction of oxygen)
Electrode catalyst for hydrogen fuel cell (four-electron reduction reaction of oxygen at cathode electrode)
By using the reaction system carbon dioxide that uses hydrogen ions as a substrate and electrochemically generating hydrogen gas and the epoxy compound as a raw material, and the reaction system carbon dioxide that electrochemically reduces the reaction system carbon dioxide whose target is cyclocarbonate Electrochemical reaction system that produces hydrogen and oxygen Photochemical reaction system that produces hydrogen and oxygen by the decomposition of water A reaction system that uses water and alcohol as raw materials and carbon dioxide and hydrogen

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto.
Note that UV/vis spectrum measurement, which is a highly versatile method, was used to confirm the synthesis of the multi-electron redox catalyst. (See, for example, S. Liu et al., Angew. Chem. Int. Ed., 2008, 47, 2657-2660 as a prior article on the UV/vis spectrum measurement).
Example 1
Synthesis of multi-electron redox catalyst "CoTM-4-PyP/Co-Salen/CB[10]" of the present invention comprising CoTM-4-PyP/Co-Salen/CB[10].
(1) CoTM-4-PyP synthesis, (2) CB[10] synthesis, (3) Salen synthesis, (4) Co introduction into Salen (5) CoTM-4-PyP/CB[ 10] and (6) Co TM-4-PyP/Co-Salen/CB[10].
(1) Synthesis of CoTM-4-PyP As a starting material, 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine (manufactured by Aldrich), methyl p-toluenesulfonate (Tokyo Kasei) Co., Ltd.) and cobalt chloride hexahydrate (II) (manufactured by Kanto Kagaku).
(a) Synthesis of 5,10,15,20-tetra(4-methylpyridinium)-21H,23H-porphine (H2TM-4-PyP)
50 mg of 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine (0.081 mmol) and 10 mL of methyl p-toluenesulfonate (66.3 mmol), 30 mL of N,N- under a nitrogen atmosphere. The mixture was heated under reflux in dimethylformamide (DMF) at 110°C for 24 hours.
After 24 hours, the progress of the reaction was confirmed by silica TLC (acetonitrile/water/KNO3aq)=(8/2/1). DMF was removed by evaporation, and unreacted methyl p-toluenesulfonate was removed by liquid separation (chloroform/water). After liquid separation, ammonium hexafluorophosphate (NH4PF6) was added to the aqueous layer to obtain a purple solid. The purple solid was dissolved in acetone, and the purple solid produced by adding tetrabutylammonium chloride was collected by filtration to obtain the target product H2TM-4-PyP. The yield was 45.2 mg, and the yield was 68.2%.
The synthesis was confirmed by 1H-NMR according to the previous report.

(b) Synthesis of CoTM-4-PyP
H2TM-4-PyP (50 mg, 0.061 mmol) and cobalt chloride hexahydrate (II) (300 mg, 0.366 mmol) were dissolved in 76.8 mL of water and synthesized to pH 4 using hydrochloric acid, and the pH was adjusted to 100 under a nitrogen atmosphere. Heated to reflux at °C. The progress of the reaction was confirmed by silica TLC (acetonitrile/water/KNO3aq)=(8/2/1).
After the reaction, the reddish brown precipitate that had precipitated was removed by filtration, and ammonium hexafluorophosphate (NH4PF6) was added to the filtrate to obtain a purple solid. The purple solid was dissolved in acetone, and the purple solid generated by addition of tetrabutylammonium chloride was collected by filtration to obtain the target product CoTM-4-PyP. The yield was 60 mg, and the yield was 32.1%.

(2) Synthesis of CB[10] As a starting material, glycoluril (manufactured by Aldrich), paraformaldehyde (manufactured by Aldrich), cyanuric chloride (manufactured by Tokyo Kasei), 4-[(N-Boc)aminomethyl] Aniline (manufactured by Aldrich) was used.
(a) Synthesis of CB[5]/CB[10]
Glycoluril (53g, 0.37mol) and paraformaldehyde (23.6g, 0.75mol) were mixed well in powder form. Add 75.3 mL of concentrated hydrochloric acid cooled to 4°C. Stir in an ice bath until the solution gels. Next, the mixture was heated under reflux in an oil bath at 110° C. for 17 hours.
After the reaction, the reaction solution was diluted 10 times with water, the precipitated white solid was collected by filtration, and dried in a vacuum oven at 50° C. overnight. The target solid, CB[5]/CB[10], was obtained by repeatedly recrystallizing the obtained solid in concentrated hydrochloric acid at 100°C. The yield was 0.8 g, and the yield was 2%. The synthesis was confirmed by 1H-NMR measurement according to the previous report.

(b) Synthesis of guest molecule (intermediate 2) that removes internal CB[5]
(i) Synthesis of intermediate 1
4-[(N-Boc)aminomethyl]aniline (1.0 g, 4.5 mmol) was dissolved in 3.3 mL of tetrahydrofuran (THF). Cyanuric acid chloride (0.40 g, 2.2 mmol) and 0.67 mL of N,N-diisopropylethylamine were added to the solution, and the mixture was stirred at 0° C. for 2 hours and further at room temperature for 24 hours. After the reaction, the reaction solution was filtered and the solvent was evaporated to obtain the intermediate 1, which was the desired product. The yield was 0.95 g, and the yield was 86.4%.

(ii) Synthesis of intermediate 2
Intermediate 1 (0.3 g, 0.54 mmol) was dissolved in a mixed solvent of 5 mL of water/3 mL of trifluoroacetic acid, and the mixture was heated under reflux at 85° C. for 10 hours. After the reaction, the reaction solution was allowed to cool to room temperature and left standing in a refrigerator (4°C) for 1 day. The precipitated crystals were collected by filtration to obtain the intermediate product 2 as a target. The yield was 280 mg, and the yield was 92%. The synthesis was confirmed by 1H NMR measurement.

(b) Synthesis of CB[10]
CB[5]/CB[10] (0.70 g, 0.26 mmol) and intermediate 2 (0.73 g, 1.30 mmol) were dissolved in 170 mL of water, and the mixture was heated under reflux at 90°C for 30 minutes. After the reaction, the solution was air-cooled and the filtrate was collected by filtration. The filtrate was concentrated to 40 mL, allowed to stand in a refrigerator (4° C.) for 2 hours and filtered to collect the filtrate. The filtrate was evaporated to dryness, and the obtained solid was repeatedly washed with 50 mL of methanol to obtain CB[10].intermediate 2 (0.39 g, 0.18 mmol).
CB[10]-Intermediate 2 (0.37 g, 0.50 mmol) was suspended in 10 mL of acetic anhydride and heated under reflux at 100°C for 16 hours. The precipitate was collected by centrifugation and washed with 20 mL methanol, 20 mL dimethylsulfoxide, and 20 mL water. The solid was dried in a vacuum oven to obtain the target product, CB[10] (200 mg, 0.12 mmol). The yield was 73%.

(3) As a starting material for the synthesis of Salen, ethylenediamine (manufactured by Tokyo Kasei), salicylaldehyde (manufactured by Tokyo Kasei), o-vanillin (manufactured by Tokyo Kasei), 1.3 diaminopropane (manufactured by Tokyo Kasei), pyridine-2 -Carboxaldehyde (manufactured by Tokyo Kasei) was used.
Ethylenediamine (1.0 g, 0.017 mol) and salicylaldehyde (4.06 g, 0.033 mol) were added to 332.7 ml of methanol, and the mixture was stirred at room temperature for 1 day. The resulting precipitate was collected by filtration and dried in a vacuum oven at 30°C overnight. The amount of the target product was 2.60 g, and the yield was 58.3%. The synthesis was confirmed by ¹ H-NMR measurement according to the previous report.
(4) Synthesis of Co-Salen The above (3) (0.32 g, 1.2 mmol) was added to 50 ml of methanol, and cobalt chloride hexahydrate (II) (manufactured by Kanto Kagaku) (0.238 g, 1 mmol) was dissolved therein, Synthesized to pH 4 using hydrochloric acid, and stirred for 1 hour at room temperature. The precipitate was collected by filtration, washed well with acetone, and dried in a vacuum oven at 40° C. overnight to obtain 42 mg of the target product and 26.1% in yield. Confirmation of synthesis was performed by FAB-MS measurement.

(5) Synthesis of CoTM-4-PyP/CB[10]

CoTM-4-PyP 1.0 mg was dissolved in 5 mL water. 2.6 mg of CB[10] was added to the solution and sonicated at room temperature for 10 minutes. Unreacted CB[10] was removed by filtration to obtain CoTM-4-PyP/CB[10] as an aqueous solution. CoTM-4-PyP/CB[10] formation proceeded quantitatively. Confirmation of the synthesis was performed by UV/vis spectrum.
(6) Synthesis of CoTM-4-PyP/Co-Salen/CB[10]
In the formula, M represents Co.
As is clear from the results shown in Fig. 1(a), Co-Salen with different concentrations was added to CoTM-4-PyP/CB[10] with a constant concentration. A large change was observed in the belt. Further, as shown in FIG. 1(b), the plot at 434 nm shows a 1:1 fitting curve. From these, it can be seen that CoTM-4-PyP and Co-Salen form a binuclear complex inside CB[10].

[Example 2]
Synthesis of the multi-electron redox catalyst "CoTM-4-PyP/Fe-Salen/CB[10]" of the present invention comprising CoTM-4-PyP/Fe-Salen/CB[10].
The synthesis is (1) CoTM-4-PyP synthesis, (2) CB[10] synthesis, (3) Salen synthesis, (4) Metal introduction into Salen (5) CoTM-4-PyP/CB[ 10] and (6) Co TM-4-PyP/Fe 2 -Salen/CB[10] were synthesized in 6 steps.
(1) CoTM-4-PyP was synthesized in the same manner as in Example 1 above to obtain the target product.
(2) The synthesis of CB[10] was performed in the same manner as in Example 1 above to obtain the desired product.
(3) Salen was synthesized in the same manner as in Example 1 above to obtain the desired product.
(4) Synthesis of Fe-Salen (Fe introduction into Salen)
The above (3) (0.32 g, 1.2 mmol) was added to 50 ml of methanol, iron (II) chloride (manufactured by Kanto Chemical Co., Ltd.) (0.200 g, 1 mmol) was dissolved therein, and it was synthesized to pH 4 with hydrochloric acid, Stir for 1 hour at room temperature. The precipitate was collected by filtration, washed well with acetone, and dried in a vacuum oven at 40° C. overnight to obtain 103 mg of the target product and 31.9% in yield. Confirmation of synthesis was performed by FAB-MS measurement.
(5) Synthesis of CoTM-4-PyP/CB[10] The target product was obtained in the same manner as in Example 1 above.
(6) Synthesis of CoTM-4-PyP/Fe-Salen/CB[10]
In the formula, M represents Co.
The synthesis of CoTM-4-PyP/Fe-Salen/CB[10] was performed by adding Fe-Salen powder to an aqueous solution of CoTM-4-PyP/CB[10] to obtain the desired product. In this example, the following aqueous solutions were synthesized in order to perform measurement using ultraviolet/visible absorption spectra as confirmation of synthesis.
1) Methanol aqueous solution (160 μM)
2) 160 μM aqueous solution of Fe-Salen.
3) 160 μM aqueous solution of CoTM-4-PyP/CB[10].
Then, 1) was added to (2000-X) μL, 2) to X μL, and 3) to 500 μL, and the total amount was kept constant at 2500 μL. By changing the value of X, the change in absorption spectrum when different concentrations of Fe-Salen were added was tracked. The value of X was changed from 0 to 2000. Therefore, the concentration of Fe-Salen added was 0 to 160 μM. The results are shown in Figure 2.
As is clear from the results shown in Fig. 2(a), the addition of Fe-Salen with different concentrations to CoTM-4-PyP/CB[10] with a constant concentration resulted in the maximum absorption of the Soret band and Q. A large change was observed in the belt. Also, as shown in Fig. 2(b), the plot at 441 nm shows a 1:1 fitting curve, indicating that CoTM-4-PyP and Fe-Salen form a binuclear complex inside CB[10]. Recognize.

[Example 3]
Synthesis of the multi-electron redox catalyst "CoTM-4-PyP/Mo-Salen/CB[10]" of the present invention comprising CoTM-4-PyP/Mo-Salen/CB[10].
(1) CoTM-4-PyP synthesis, (2) CB[10] synthesis, (3) Salen synthesis, (4) Mo introduction into Salen (5) CoTM-4-PyP/CB[ 10] and (6) Co TM-4-PyP/Mo-Salen/CB[10].
(1) CoTM-4-PyP was synthesized in the same manner as in Example 1 above to obtain the target product.
(2) Synthesis of CB[10] was performed in the same manner as in Example 1 above to obtain the target product.
(3) Salen was synthesized in the same manner as in Example 1 above to obtain the desired product.
(4) Introduction of Mo to Salen
Salen (131.2 mg, 0.0489 mmol) synthesized by the above method was added to 35 ml of THF, and hexacarbonyl molybdenum (manufactured by Kanto Kagaku) (125 mg, 0.473 mmol) was added thereto, and the mixture was refluxed for 22 hours. The precipitate was filtered, washed with chloroform, and dried in a vacuum oven at 40° C. overnight to obtain 150 mg of the desired product in a yield of 74.6%. The synthesis was confirmed by ¹ H-NMR measurement according to the previous report.
(5) Synthesis of CoTM-4-PyP/CB[10] The target product was obtained in the same manner as in Example 1 above.
(6) Synthesis of CoTM-4-PyP/Mo-Salen/CB[10]
In the formula, M represents Co.
Different concentrations of Mo-Salen (0 to 20 μM) were added to CoTM-4-PyP/CB[10] (10 μM), and the change in absorption spectrum at that time was measured using ultraviolet and visible absorption spectra. The results are shown in FIGS. 3(a) and 3(b).
The job's Plot method was used to obtain the complex formation ratio. The ratio of CoTM-4-PyP/CB[10] and Mo-Salen synthesized at 20 μM was changed from 1:0 to 0:1, and the change in the maximum absorption spectrum was traced. The results are shown in FIGS. 4(a) and 4(b).
As is clear from the results shown in Fig. 3(a), the addition of different concentrations of Mo-Salen to CoTM-4-PyP/CB[10] with a constant concentration resulted in the maximum absorption of the Soret band and Q. A large change was observed in the belt. Further, as shown in FIG. 3(b), the plot at 441 nm shows a 1:1 fitting curve, and as shown in FIGS. 4(a) and 4(b), Job's Plot also shows CoTM- inside the CB[10]. It can be seen that 4-PyP and Mo-Salen form a binuclear complex.

[Example 4]
Synthesis of the multi-electron redox catalyst "CoTM-4-PyP/Co-Salen(OMe)/CB[10]" of the present invention comprising CoTM-4-PyP/Co-Salen(OMe)/CB[10].
(1) CoTM-4-PyP synthesis, (2) CB[10] synthesis, (3) Salen(OMe) synthesis, (4) Co introduction into Salen(OMe) (5) CoTM- It was carried out in 6 steps of 4-PyP/CB[10] synthesis and (6)Co™-4-PyP/Co-Salen(OMe)/CB[10] synthesis.
(1) CoTM-4-PyP was synthesized in the same manner as in Example 1 above to obtain the target product.
(2) Synthesis of CB[10] was performed in the same manner as in Example 1 above to obtain the target product.
(3) Synthesis of Salen(OMe) Ethylenediamine (1.0 g, 0.017 mol) and o-vanillin (manufactured by Tokyo Kasei) (5.06 g, 0.033 mol) were added to 332.7 ml of methanol, and the mixture was stirred at room temperature for 1 day. The resulting precipitate was collected by filtration and dried in a vacuum oven at 30°C overnight. The amount of the target product was 5.46 g, and the yield was 80.8%. The synthesis was confirmed by ¹ H-NMR measurement according to the previous report.
(4) Introduction of Co to Salen(OMe) The above (3) (400 mg, 1.2 mmol) was added to 50 ml of methanol, and cobalt chloride hexahydrate (II) (0.238 g, 1 mmol) was dissolved therein, Synthesized to pH 4 using hydrochloric acid, and stirred for 1 hour at room temperature. The precipitate was collected by filtration, washed well with acetone, and dried in a vacuum oven at 40° C. overnight to obtain the target product in an amount of 253 mg and 65.6%. Confirmation of synthesis was performed by FAB-MS measurement.
(5) Synthesis of CoTM-4-PyP/CB[10] The target product was obtained in the same manner as in Example 1 above.
(6) Synthesis of CoTM-4-PyP/Co-Salen(OMe)/CB[10]
In the formula, M represents Co.
CoTM-4-PyP/Co-Salen(OMe)/CB[10] is synthesized by adding Co-Salen(OMe) powder to CoTM-4-PyP/CB[10] aqueous solution. I got a thing. In this example, the following aqueous solutions were synthesized in order to perform measurement using ultraviolet/visible absorption spectra as confirmation of synthesis.
1) Methanol aqueous solution (160 μM)
2) 160 μM Co- Salen(OMe) solution
3) 160 μM aqueous solution of CoTM-4-PyP/CB[10] Then, 1) (2000-X) μL, 2) X μL, and 3) 500 μL were added, and the total amount was kept constant at 2500 μL. By changing the value of X, the change in absorption spectrum when different concentrations of Co-Salen(OMe) were added was tracked. The value of X was changed from 0 to 2000. Therefore, the concentration of Co-Salen(OMe) added was 0 to 160 μM. Results are shown in FIG.
As is clear from the results as shown in Fig. 5(a), Co-Salen(OMe) with different concentrations was added to CoTM-4-PyP/CB[10] with a constant concentration. A large change was observed in a certain Soret zone and Q zone. As shown in Fig. 5(b), the plot at 441 nm shows a 1:1 fitting curve, and CoTM-4-PyP and Co-Salen(OMe) form a binuclear complex inside CB[10]. I understand that

[Example 5]
Synthesis of multi-electron redox catalyst "CoTM-4-PyP/Fe-Salen(OMe)/CB[10]" of the present invention comprising CoTM-4-PyP/Fe-Salen(OMe)/CB[10].
(1) CoTM-4-PyP synthesis, (2) CB[10] synthesis, (3) Salen(OMe) synthesis, (4) Fe introduction into Salen(OMe) (5) CoTM- It was carried out in 6 steps of 4-PyP/CB[10] synthesis and (6)Co™-4-PyP/Fe-Salen(OMe)/CB[10] synthesis.
(1) CoTM-4-PyP was synthesized in the same manner as in Example 1 above to obtain the target product.
(2) Synthesis of CB[10] was performed in the same manner as in Example 1 above to obtain the target product.
(3) Salen(OMe) was synthesized in the same manner as in Example 4 above to obtain the desired product.
(4) The above (3) (400 mg, 1.2 mmol) was added to 50 ml of methanol, and iron (II) chloride (Kanto Chemical Co., Inc.) (0.200 g, 1 mmol) was dissolved therein, and the pH was adjusted to 4 with hydrochloric acid. Synthesized and stirred for 1 hour at room temperature. The precipitate was collected by filtration, washed well with acetone, and dried in a vacuum oven at 40° C. overnight to obtain 258 mg of the desired product and 67.5% yield. Confirmation of synthesis was performed by FAB-MS measurement.
(5) Synthesis of CoTM-4-PyP/CB[10] The target product was obtained in the same manner as in Example 1 above.
(6) Synthesis of CoTM-4-PyP/Fe- Salen(OMe)/CB[10]
In the formula, M represents Co.
CoTM-4-PyP/Fe-Salen(OMe)/CB[10] is synthesized by adding Fe-Salen(OMe) powder to CoTM-4-PyP/CB[10] aqueous solution. I got a thing. In this example, the following aqueous solutions were synthesized in order to perform measurement using ultraviolet/visible absorption spectra as confirmation of synthesis.
1) Methanol aqueous solution (160 μM)
2) 160 μM aqueous solution of Fe-Salen(OMe)
3) 160 μM aqueous solution of CoTM-4-PyP/CB[10] Then, 1) (2000-X) μL, 2) X μL, and 3) 500 μL were added, and the total amount was kept constant at 2500 μL. By changing the value of X, the change in the absorption spectrum when different concentrations of Fe-Salen(OMe) were added was tracked. The value of X was changed from 0 to 2000. Therefore, the concentration of Fe-Salen(OMe) added was 0 to 160 μM. Results are shown in FIG.
As is clear from the results as shown in Fig. 6(a), as a result of adding Fe-Salen(OMe) with different concentrations to CoTM-4-PyP/CB[10] with a constant concentration, the maximum absorption was observed. A large change was observed in a certain Soret zone and Q zone. As shown in Fig. 6(b), the plot at 441 nm shows a 1:1 fitting curve, and CoTM-4-PyP and Fe-Salen(OMe) form a binuclear complex inside CB[10]. I understand that

[Example 6]
Synthesis of the multi-electron redox catalyst "CoTM-4-PyP/Co-Pyalen/CB[10]" of the present invention comprising CoTM-4-PyP/Co-Pyalen/CB[10].
(1) CoTM-4-PyP, (2) CB[10], (3) 1.3-[Bis(Pyridine-2-Imino)] Propane (hereinafter Pyalen), (4) Introduction of Co into Pyalen (5) Synthesis of CoTM-4-PyP/CB[10] and (6) Synthesis of CoTM-4-PyP/Co-Pyalen/CB[10] were performed in 6 steps.
(1) CoTM-4-PyP was synthesized in the same manner as in Example 1 above to obtain the target product.
(2) Synthesis of CB[10] was performed in the same manner as in Example 1 above to obtain the target product.
(3) Synthesis of Pyalen Assemble a Dean-Stark apparatus, dissolve 1.3 diaminopropane (manufactured by Tokyo Chemical Industry Co., Ltd.) (0.74 g, 0.01 mol) in 50 ml of toluene, and further pyridine-2-carboxaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.). (2.14 g, 0.02 mol) was added. It was made to react until water did not come out to the Dean Stark tube. The reaction solution was evaporated to remove the solvent to obtain the desired product. The yield was 1.8 g, and the yield was 71.4%. The synthesis was confirmed by ¹ H-NMR measurement according to the previous report.
(4) The above (3) (300 mg, 1.2 mmol) was added to 50 ml of methanol, cobalt chloride hexahydrate (II) (0.238 g, 1 mmol) was dissolved therein, and it was synthesized to pH 4 with hydrochloric acid. And stirred for 1 hour at room temperature. The precipitate was collected by filtration, washed well with acetone, and dried in a vacuum oven at 40° C. overnight to obtain 300 mg of the desired product and a yield of 95.0%. Confirmation of synthesis was performed by FAB-MS measurement.
(5) Synthesis of CoTM-4-PyP/CB[10] The target product was obtained in the same manner as in Example 1 above.
(6) Synthesis of CoTM-4-PyP/ Co-Pyalen/CB[10]
In the formula, M represents Co.
CoTM-4-PyP/Co-Pyalen/CB[10] was synthesized by adding Co-Pyalen powder to an aqueous solution of CoTM-4-PyP/CB[10] to obtain the desired product. In this example, the following aqueous solutions were synthesized in order to perform measurement using ultraviolet/visible absorption spectra as confirmation of synthesis.
1) water
2) 160 μM aqueous solution of Co-Pyalen
3) 160 μM aqueous solution of CoTM-4-PyP/CB[10] Then, 1) (2000-X) μL, 2) X μL, and 3) 500 μL were added, and the total amount was kept constant at 2500 μL. By changing the value of X, the change in absorption spectrum when different concentrations of Co-Pyalen were added was tracked. The value of X was changed from 0 to 2000. Therefore, the concentration of Co-Pyalen added was 0 to 160 μM. The results are shown in Fig. 7.
As shown in Fig. 7(a), as is clear from the results, CoTM-PyaP/CB[10] with a constant concentration was added with different concentrations of Co-Pyalen. And a big change was observed in the Q band. As shown in Fig. 7(b), the plot at 441 nm shows a 1:1 fitting curve, indicating that CoTM-4-PyP and Co-Pyalen form a binuclear complex inside CB[10]. Recognize.

Example 7
Synthesis of multi-electron redox catalyst "CoTM-4-PyP/Fe-Pyalen/CB[10]" of the present invention comprising CoTM-4-PyP/Fe-Pyalen/CB[10].
The synthesis is as follows: (1) CoTM-4-PyP synthesis, (2) CB[10] synthesis, (3) Pyalen synthesis, (4) Fe introduction into Pyalen (5) CoTM-4-PyP/CB[ [10] and (6)Co™-4-PyP/Fe-Pyalen/CB[10] were synthesized in 6 steps.
(1) CoTM-4-PyP was synthesized in the same manner as in Example 1 above to obtain the target product.
(2) Synthesis of CB[10] was performed in the same manner as in Example 1 above to obtain the target product.
(3) Synthesis of Pyalen The desired product was obtained in the same manner as in Example 6 above.
(4) Fe introduction to Pyalen
The above (3) (300 mg, 1.2 mmol) was added to 50 ml of methanol, and iron (II) chloride (manufactured by Kanto Chemical Co., Ltd.) (0.200 g, 1 mmol) was dissolved therein, and synthesized to pH 4 with hydrochloric acid, Stir for 1 hour at room temperature. The precipitate was collected by filtration, washed well with acetone, and dried in a vacuum oven at 40° C. overnight to obtain the target product in an amount of 307 mg and a yield of 99.0%. Confirmation of synthesis was performed by FAB-MS measurement.
(5) Synthesis of CoTM-4-PyP/CB[10] The target product was obtained in the same manner as in Example 1 above.
(6) Synthesis of CoTM-4-PyP/Fe-Pyalen/CB[10]
In the formula, M represents Co.
The synthesis of CoTM-4-PyP/Fe-Pyalen/CB[10] was carried out by adding Fe-Pyalee powder to the CoTM-4-PyP/CB[10] aqueous solution to obtain the desired product. In this example, the following aqueous solutions were synthesized in order to perform measurement using ultraviolet/visible absorption spectra as confirmation of synthesis.
1) Methanol aqueous solution (160 μM)
2) 160 μM aqueous solution of Fe-Pyalen
3) 160 μM aqueous solution of CoTM-4-PyP/CB[10] Then, 1) (2000-X) μL, 2) X μL, and 3) 500 μL were added, and the total amount was kept constant at 2500 μL. By changing the value of X, the change in the absorption spectrum when different concentrations of Fe-Pyalen were added was tracked. The value of X was changed from 0 to 2000. Therefore, the concentration of Fe-Pyalen added was 0 to 160 μM. The results are shown in Fig. 8.
As is clear from the results as shown in FIG. 8(a), as a result of adding different concentrations of Fe-Pyalen to CoTM-4-PyP/CB[10] with a constant concentration, the maximum absorption of the Soret band And a big change was observed in the Q band. As shown in Fig. 8(b), the plot at 435 nm shows a 1:1 fitting curve, and CoTM-4-PyP and Fe-Pyalen form a binuclear complex inside CB[10]. I understand.

[Example 8]
Synthesis of multi-electron redox catalyst "FeTM-4-PyP/Co-Salen/CB[10]" of the present invention comprising FeTM-4-PyP/Co-Salen/CB[10].
Synthesis of (1) FeTM-4-PyP, (2) CB[10], (3) Co-Salen, (4) FeTM-4-PyP/CB[10], 5) FeTM-4-PyP/Co-Salen/CB[10] was synthesized in 5 steps.
(1) FeTM-4-PyP synthesis starting material, 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine (manufactured by Aldrich), methyl p-toluenesulfonate (Tokyo Kasei) Manufactured by Kanto Chemical Co., Ltd.) was used.
(a) Synthesis of 5,10,15,20-tetra(4-methylpyridinium)-21H,23H-porphine (H2TM-4-PyP) In the same manner as in the synthesis method described in Example 1, the target compound H2TM-4- Got PyP. The yield was 45.2 mg, and the yield was 68.2%. The synthesis was confirmed by 1H-NMR according to the previous report.

(b) Synthesis of Fe(III)-5,10,15,20-tetra(4-methylpyridinium)-21H,23H-porphine (FeTM-4-PyP)
H2TM-4-PyP (50 mg, 0.061 mmol) and iron(II) chloride (77 mg, 0.61 mmol) were dissolved in 20 mL of water, pH was adjusted to 4 with hydrochloric acid, and the mixture was heated at 100°C under nitrogen atmosphere. Heated to reflux. The progress of the reaction was confirmed by silica TLC (acetonitrile/water/KNO3aq)=(8/2/1).
After the reaction, the reddish brown precipitate that had precipitated was removed by filtration, and ammonium hexafluorophosphate (NH4PF6) was added to the filtrate to obtain a purple solid. The purple solid was dissolved in acetone, and the purple solid generated by the addition of tetrabutylammonium chloride was collected by filtration to obtain the desired product FeTM-4-PyP. The yield was 44.3 mg, and the yield was 80%.
(2) The synthesis of CB[10] was performed in the same manner as in Example 1 above to obtain the desired product.
(3) Co-Salen was synthesized in the same manner as in Example 1 above to obtain the target product.
(4) Synthesis of FeTM-4-PyP/CB[10]
FeTM-4-PyP 1.0 mg was dissolved in 5 mL of water. 2.6 mg of CB[10] was added to the solution and sonicated at room temperature for 10 minutes. Unreacted CB[10] was removed by filter filtration to obtain FeTM-4-PyP/CB[10] as an aqueous solution. FeTM-4-PyP/CB[10] formation proceeded quantitatively. Confirmation of the synthesis was performed by UV/vis spectrum.
(6) Synthesis of FeTM-4-PyP/Co-Salen/CB[10]
The synthesis of FeTM-4-PyP/Co-Salen/CB[10] was performed by adding Co-Salen powder to the FeTM-4-PyP/CB[10] aqueous solution to obtain the desired product.
The compound obtained by the synthesis was confirmed by measuring the UV-visible absorption spectrum. The results are shown in Fig. 9.
As is clear from the results shown in FIG. 9, the absorption band (Q band) of FeTM-4-PyP/CB[10] near 600 nm was shifted by a short wavelength. In addition, the absorbance of the absorption band (Soret band) derived from FeTM-4-PyP/CB[10] at 424 nm decreased. Such an absorption spectrum change is observed due to the interaction between aromatic rings. Therefore, it can be seen that inclusion of Co-Salen inside FeTM-4-PyP/CB[10], that is, FeTM-4-PyP/Co-Salen/CB[10] is formed.

[Example 9]
Synthesis of multi-electron redox catalyst "FeTM-4-PyP/Co-Salen(OMe)/CB[10]" of the present invention comprising FeTM-4-PyP/Co-Salen(OMe)/CB[10].
Synthesis of (1) FeTM-4-PyP, (2) CB[10], (3) Co-Salen(OMe), (4) FeTM-4-PyP/CB[10] The synthesis was performed in 5 steps of (5) FeTM-4-PyP/Co-Salen(OMe)/CB[10].
(1) FeTM-4-PyP was synthesized in the same manner as in Example 8 above to obtain the target product.
(2) Synthesis of CB[10] was performed in the same manner as in Example 1 above to obtain the target product.
(3) Synthesis of Co-Salen(OMe) was carried out in the same manner as in Example 4 above to obtain the desired product.
(4) FeTM-4-PyP/CB[10] was synthesized in the same manner as in Example 8 above to obtain the target product.
(5) Synthesis of FeTM-4-PyP/Co-Salen(OMe)/CB[10]
FeTM-4-PyP/Co-Salen(OMe )/CB[10] was synthesized by adding Co-Salen(OMe) powder to FeTM-4-PyP/CB[10] aqueous solution. I got a thing.

The compound obtained by the synthesis was confirmed by measuring the UV-visible absorption spectrum. The results are shown in FIG.
In FIG. 10, the blue line shows the absorption spectrum of FeTM-4-PyP/CB[10], and the red line shows the absorption spectrum of FeTM-4-PyP/Co-Salen(OMe)/CB[10]. As a result of evaluation by the difference spectrum, a new absorption band was observed at 400 nm. It is considered that this is due to the π-π charge transfer interaction between FeTM-4-PyP and Co-Salen(OMe) inside CB[10]. Therefore, it can be seen that FeTM-4-PyP/Co-Salen(OMe)/CB[10] is formed.

[Example 10]
The synthetic synthesis of the multi-electron redox catalyst "FeTM-4-PyP/Fe-Salen(OMe)/CB[10] of the present invention consisting of FeTM-4-PyP/Fe-Salen(OMe)/CB[10] is (1) FeTM-4-PyP synthesis, (2) CB[10] synthesis, (3) Fe-Salen(OMe) synthesis, (4) FeTM-4-PyP/CB[10] synthesis, ( 5) FeTM-4-PyP/Fe-Salen(OMe)/CB[10] was synthesized in 5 steps.
(1) FeTM-4-PyP was synthesized in the same manner as in Example 8 above to obtain the target product.
(2) Synthesis of CB[10] was performed in the same manner as in Example 1 above to obtain the target product.
(3) The synthesis of Fe-Salen(OMe) was performed in the same manner as in Example 5 above to obtain the desired product.
(4) FeTM-4-PyP/CB[10] was synthesized in the same manner as in Example 8 above to obtain the target product.
(5) Synthesis of FeTM-4-PyP/Fe-Salen(OMe)/CB[10]
The synthesis of FeTM-4-PyP/Fe-Salen(OMe)/CB[10] is carried out by adding Fe-Salen(OMe) powder to FeTM-4-PyP/CB[10] aqueous solution. I got a thing.


The compound obtained by the synthesis was confirmed by measuring the UV-visible absorption spectrum. The results are shown in Fig. 11.
In FIG. 11, the blue line is the absorption spectrum of FeTM-4-PyP/CB[10], and the red line is the absorption spectrum of FeTM-4-PyP/Fe-Salen(OMe)/CB[10]. A decrease in the absorbance derived from the FeTM-4-PyP skeleton was observed by adding Fe-Salen(OMe) powder and sonicating. This is considered to be because the environment around FeTM-4-PyP became hydrophobic due to inclusion of Fe-Salen(OMe). In addition, the absorption derived from FeTM-4-PyP/CB[10] near 600 nm was shifted by a short wavelength. It is considered that this is due to the association between FeTM-4-PyP and Fe-Salen(OMe). Therefore, it can be seen that FeTM-4-PyP/Fe-Salen(OMe)/CB[10] is formed.

[Example 11]
The synthetic synthesis of the multi-electron redox catalyst "FeTM-4-PyP/Fe-Salen/CB[10]" of the present invention consisting of FeTM-4-PyP/Fe-Salen/CB[10] is (1) FeTM- 4-PyP synthesis, (2)CB[10] synthesis, (3)Fe-Salen(OMe) synthesis, (4)FeTM-4-PyP/CB[10] synthesis, (5)FeTM-4 It was performed in 5 steps of the synthesis of -PyP/Fe-Salen/CB[10].
(1) FeTM-4-PyP was synthesized in the same manner as in Example 8 above to obtain the target product.
(2) Synthesis of CB[10] was performed in the same manner as in Example 1 above to obtain the target product.
(3) Fe-Salen was synthesized in the same manner as in Example 2 described above to obtain the desired product.
(4) FeTM-4-PyP/CB[10] was synthesized in the same manner as in Example 8 above to obtain the target product.
(5) Synthesis of FeTM-4-PyP/Fe-Salen/CB[10]
The synthesis of FeTM-4-PyP/Fe-Salen/CB[10] was carried out by adding Fe-Salen powder to the FeTM-4-PyP/CB[10] aqueous solution to obtain the desired product.

The compound obtained by the synthesis was confirmed by measuring the UV-visible absorption spectrum. Results are shown in FIG.
In FIG. 12, the blue line is the absorption spectrum of FeTM-4-PyP/CB[10], and the red line is the absorption spectrum of FeTM-4-PyP/Fe-Salen]CB[10]. A decrease in the absorbance derived from the FeTM-4-PyP skeleton was observed by adding Fe-Salen powder and sonicating. This is probably because the environment around FeTM-4-PyP became hydrophobic due to inclusion of Fe-Salen. In addition, the absorption derived from FeTM-4-PyP/CB[10] near 600 nm was shifted by a short wavelength. It is considered that this is due to the association between FeTM-4-PyP and Fe-Salen. Therefore, it is understood that FeTM-4-PyP/Fe-Salen/CB[10] is formed.

[Example 12]
The multi-electron redox catalyst of the present invention consisting of FeTM-4-PyP/Fe-Pyalen/CB[10], "FeTM-4-PyP/Fe-Pyalen/CB[10], was synthesized by (1) FeTM-4 -Synthesis of PyP, (2)CB[10], (3)Fe-Pyalen, (4)FeTM-4-PyP/CB[10], (5)FeTM-4-PyP/Fe -Performed in 5 steps of Pyalen/CB[10] synthesis.
(1) FeTM-4-PyP was synthesized in the same manner as in Example 8 above to obtain the target product.
(2) Synthesis of CB[10] was performed in the same manner as in Example 1 above to obtain the target product.
(3) Fe-Pyalen was synthesized in the same manner as in Example 7 to obtain the target product.
(4) FeTM-4-PyP/CB[10] was synthesized in the same manner as in Example 8 above to obtain the target product.
(5) Synthesis of FeTM-4-PyP/Fe-Pyalen/CB[10]
The synthesis of FeTM-4-PyP/Fe-Pyalen/CB[10] was carried out by adding Fe-Pyalen powder to the FeTM-4-PyP/CB[10] aqueous solution to obtain the desired product.
The compound obtained by the synthesis was confirmed by measuring the UV-visible absorption spectrum. The results are shown in Fig. 13.
As shown in Fig. 13, as a result of sequentially adding different concentrations of Fe-Pyalen to FeTM-4-PyP/CB[10] with a constant concentration, significant absorption spectrum changes were observed while maintaining the absorption points such as FeTM. Was done. In addition, a decrease in absorbance in the Soret band and a short wavelength shift in the Q band derived from FeTM-4-PyP/CB[10] were observed. These result from the interaction between FeTM-4-PyP and Fe-Pyalen inside CB[10]. Therefore, it can be seen that FeTM-4-PyP/Fe-Pyalen/CB[10] is formed.

[Example 13]
Synthesis of the multi-electron redox catalyst of the present invention "FeTM-4-PyP/Co-Pyalen/CB[10] consisting of FeTM-4-PyP/Co-Pyalen/CB[10] The synthesis is (1) FeTM-4 -PyP synthesis, (2)CB[10] synthesis, (3)Co-Pyalen synthesis, (4)FeTM-4-PyP/CB[10] synthesis, (5)FeTM-4-PyP/Co -Performed in 5 steps of Pyalen/CB[10] synthesis.
(1) FeTM-4-PyP was synthesized in the same manner as in Example 8 above to obtain the target product.
(2) Synthesis of CB[10] was performed in the same manner as in Example 1 above to obtain the target product.
(3) Synthesis of Co-Pyalen was performed in the same manner as in Example 6 above to obtain the target product.
(4) FeTM-4-PyP/CB[10] was synthesized in the same manner as in Example 8 above to obtain the target product.
(5) Synthesis of FeTM-4-PyP/Co-Pyalen/CB[10]
The synthesis of FeTM-4-PyP/Co-Pyalen/CB[10] was carried out by adding Co-Pyalen powder to the FeTM-4-PyP/CB[10] aqueous solution to obtain the desired product.

The compound obtained by the synthesis was confirmed by measuring the UV-visible absorption spectrum. The results are shown in Fig. 14.
As shown in FIG. 14, as a result of successively adding different concentrations of Co-Pyalen to FeTM-4-PyP/CB[10] having a constant concentration, the increase in absorbance and the Q band of 450 nm to 500 nm were observed. A long wavelength shift was observed. This is due to the electronic interaction between FeTM-4-PyP and Co-Pyalen inside CB[10]. Therefore, it can be seen that FeTM-4-PyP/Co-Pyalen/CB[10] is formed.

[Example 14]
Synthesis of _{(trans-CoM4Py 2 P) 2} / CB consisting [10] multi-electron redox catalyst _{"(trans-CoM4Py 2 P) 2} / CB [10]" _{is, (1) trans-H 2} M4Py 2 P Was carried out in three steps: (2) trans-CoM4Py ₂ P, and (3) (trans-CoM4Py ₂ P) ₂ /CB[10].
(1) Synthesis of trans-H ₂ M4Py ₂ P Pyrrole (Tokyo Kasei), paraformaldehyde (Aldrich), 4-pyridinecarbaldehyde (Kanto Kagaku), and cobalt(III) acetylacetonate were used as starting materials.
(A) Synthesis of dipyrromethane
Pyrrole (200 mL, 2.88 mol) and paraformaldehyde (0.75 g, 25 mmol) were mixed and degassed with nitrogen. The mixture was heated and stirred at 60°C to dissolve paraformaldehyde. The mixture was allowed to cool to room temperature, several drops of trifluoroacetic acid (TFA) were added, and the mixture was stirred at room temperature for 1 hour. Then, 0.75 g (19 mmol) of sodium hydroxide was added, and the mixture was further stirred at room temperature for 40 minutes. After stirring, the reaction solution was evaporated and the resulting viscous liquid was separated by silica gel column chromatography using chloroform as a developing solvent. The yield was 1.8 g, and the yield was 49%. The synthesis was confirmed by ¹ H NMR according to the previous report.
(b) Synthesis of trans-H ₂ 4Py ₂ P
1.8 g (12 mmol) of dipyrromethane was dissolved in 24 mL of propionic acid. 1.2 mL (12 mmol) of 4-pyridinecarboxaldehyde was dissolved in 24 mL of propionic acid. The above two propionic acid solutions were gradually added to 30 mL of propionic acid heated to 70° C., and the resulting solution was stirred at 70° C. for 18 hours. After the reaction, propionic acid was evaporated, and the obtained black solid was separated with basic alumina (chloroform/methanol=20/1) to remove the oligomer. Then, it was separated by silica gel chromatography (chloroform/methanol=95/5), and the second extracted compound was recovered. The obtained compound was further separated by high performance liquid chromatography (HPLC) to obtain 51 mg of trans-H ₂ 4Py ₂ P. The yield was 1.8%. The synthesis was confirmed by 1H NMR measurement according to the previous report.
(B) Synthesis of trans-H ₂ M4Py ₂ P
51 mg (0.11 mmol) of trans-H ₂ 4Py ₂ P was dissolved in a mixed solvent of chloroform:N,N-dimethylformamide (DMF) (4:1, 64 mL: 16 mL). 3.3 mL (53 mmol) of iodomethane was added, and the mixture was stirred at room temperature for 17 hours. After the reaction, the solution was evaporated, the obtained solid was dissolved in 5 mL of DMF, and the solution was added dropwise to 80 mL of diethyl ether. The purple precipitate thus deposited was collected by filtration to obtain trans-H ₂ M4Py ₂ P. The yield was quantitative. The synthesis was confirmed by 1H NMR measurement according to the previous report.
(2) Synthesis of trans-CoM4Py ₂ P
14 mg (0.019 mmol) of trans-H ₂ M4Py ₂ P and 13,5 mg (0.038 mmol) of cobalt acetylacetonate (Co(acac) ₃ ) were heated under reflux with 10 mL of methanol. The reaction was continued until the fluorescence derived from trans-H ₂ M4Py ₂ P disappeared by silica gel TLC (CH ₃ CN/H ₂ O/KNO ₃ sat=8/2/1). After completion of the reaction, the solvent was evaporated, washed with chloroform, and filtered to remove unreacted Co(acac) ₃ . The solid obtained by filtration was dissolved in water and treated with a chelate resin (Diaion CR20) and an ion exchange resin (Amberlite IRA-400J Cl). Evaporation of water gave trans-CoM4Py ₂ P. The yield was quantitative. The synthesis was confirmed by elemental analysis. trans-CoM4Py ₂ P・CH ₃ Cl・3.7H ₂ O (C ₃₃ H ₃₃ Cl ₆ CoN ₆ O ₄ ), Anal: C: 46.67, H: 3.92, N: 9.90.Found: C: 46.96, H: 3.83 , N: 9.95.
(3) Synthesis of (trans-CoM4Py ₂ P) ₂ /CB[10]
1.0 mg (0.0015 mmol) of trans-CoM4Py ₂ P was dissolved in 1.0 mL of water. 3.0 mg (0.0018 mmol) of powder CB[10] was added, and sonication was performed for 10 minutes at room temperature. After 10 minutes, the solution was filtered to obtain (trans-CoM4Py ₂ P) ₂ /CB[10] as an aqueous solution. The reaction proceeded quantitatively. The spectral change observed by the formation of (trans-CoM4Py ₂ P) ₂ /CB[10] is shown in FIG.
The blue line in FIG. 15 shows the absorption spectrum of trans-CoM4Py ₂ P alone, and the red line shows the absorption spectrum of (trans-CoM4Py ₂ P) ₂ /CB[10]. By including trans-CoM4Py ₂ P in CB[10], decrease in absorbance and broadening were observed. This is a typical spectral change seen by association of porphyrin complexes. From this, it is found that a structure in which trans-CoM4Py ₂ P is associated, that is, (trans-CoM4Py ₂ P) ₂ /CB[10] is formed inside CB[10].

[Example 15]
Synthesis of _{(trans-ZnM4Py 2 P) 2} / CB consisting [10] multi-electron redox catalyst _{"(trans-ZnM4Py 2 P) 2} / CB [10]".
The synthesis was performed in 3 steps: (1) synthesis of trans-H ₂ M4Py ₂ P, (2) synthesis of trans-ZnM4Py ₂ P, and (3) synthesis of (trans-ZnM4Py ₂ P) ₂ /CB[10]. ..
(1) trans-H ₂ M4Py ₄ P was obtained in the same manner as in Example 14 described above to obtain the desired product.
(2) Synthesis of trans-ZnM4Py ₂ P
17 mg (0.023 mmol) of trans-H ₂ M4Py ₂ P and 25 mg (0.183 mmol) of zinc chloride (ZnCl 2) were dissolved in 10 mL of water and stirred at room temperature for 17 hours. The reaction progress was followed by measuring the UV-visible absorption spectrum. After the reaction, the reaction solution was treated with a chelate resin (Diaion CR20) and an ion exchange resin (Amberlite IRA-400J Cl) and evaporated to obtain the target product trans-ZnM4Py ₂ P. The reaction proceeded quantitatively. The synthesis was confirmed by measuring the UV-visible absorption spectrum.
(3) Synthesis of (trans-ZnM4Py ₂ P) ₂ /CB[10]
1.0 mg (0.0016 mmol) of trans-ZnM4Py ₂ P was dissolved in 1.0 mL of water. 4.5 mg (0.0027 mmol) of powder CB[10] was added, and sonication was performed for 10 minutes at room temperature. After 10 minutes, the solution was filtered to obtain (trans-ZnM4Py ₂ P) ₂ /CB[10] as an aqueous solution. The reaction proceeded quantitatively. FIG. 16 shows the spectral change observed by the formation of (trans-ZnM4Py ₂ P) ₂ /CB[10].
In FIG. 16, the blue line shows the absorption spectrum of trans-ZnM4Py ₂ P alone and the red line shows the absorption spectrum of (trans-ZnM4Py ₂ P) ₂ /CB[10]. By including trans-ZnM4Py ₂ P in CB[10], decrease in absorbance and broadening were observed. This is a typical spectral change seen by association of porphyrin complexes. From this, it was confirmed that the structure in which CB[10] was associated with trans-ZnM4Py ₂ P, that is, (trans-ZnM4Py ₂ P) ₂ /CB[10] was formed.

[Example 16]
Synthesis of _{(trans-FeM4Py 2 P) 2} / CB consisting [10] multi-electron redox catalyst _{"(trans-FeM4Py 2 P) 2} / CB [10]" _{is, (1) trans-H 2} M4Py 2 P Of (2), trans-FeM4Py ₂ P, and (3) (trans-FeM4Py ₂ P) ₂ /CB[10].
(1) trans-H ₂ M4Py ₂ P was synthesized in the same manner as in Example 14 described above to obtain the target product.
(2) Synthesis of trans-FeM4Py ₂ P
trans-H ₂ M4Py dissolved ₂ P 35.0 mg (0.047 mmol) and iron (II) chloride tetrahydrate _{(FeCl 2 · 4H 2 O)} 123.0 mg of (0.619 mmol) in 10 mL of water, pH using hydrochloric acid Synthesized to 2.0 and stirred at 60° C. for 22 hours. The reaction was continued until the fluorescence derived from trans-H ₂ M4Py ₂ P disappeared by silica gel TLC (CH ₃ CN/H ₂ O/KNO ₃ sat=8/2/1). After the reaction, the solvent was evaporated, the solid was dissolved in water, and treated with a chelate resin (Diaion CR20) and an ion exchange resin (Amberlite IRA-400J Cl). Evaporation of water gave trans-FeM4Py ₂ P. The reaction proceeded quantitatively. The synthesis was confirmed by measuring the UV-visible absorption spectrum.
(3) Synthesis of (trans-FeM4Py ₂ P) ₂ /CB[10]
1.0 mg (0.0015 mmol) of trans-FeM4Py ₂ P was dissolved in 1.0 mL of water. 4.5 mg (0.0027 mmol) of powder CB[10] was added, and sonication was performed for 10 minutes at room temperature. After 10 minutes, the solution was filtered to obtain (trans-FeM4Py ₂ P) ₂ /CB[10] as an aqueous solution. The reaction proceeded quantitatively. FIG. 17 shows the spectral change observed by the formation of (trans-FeM4Py ₂ P) ₂ /CB[10].
In FIG. 17, the blue line shows the absorption spectrum of trans-FeM4Py ₂ P alone and the red line shows the absorption spectrum of (trans-FeM4Py ₂ P) ₂ /CB[10]. By including trans-FeM4Py ₂ P in CB[10], decrease in absorbance and broadening were observed. This is a typical spectral change seen by association of porphyrin complexes. From this, it was confirmed that a structure in which trans-FeM4Py ₂ P was associated, that is, (trans-FeM4Py ₂ P) ₂ /CB[10] was formed inside CB[10].

[Example 17]
As an example of the catalytic reaction, the electrochemical hydrogen generation reaction of (trans-CoM4Py ₂ P) ₂ /CB[10] was examined. 0.3 mM (trans-CoM4Py ₂ P) ₂ /CB[10] (Co ion conversion) was dissolved in various buffer solutions containing 50 mM NaCl as a supporting electrolyte, and argon bubbling was performed for 30 minutes to remove dissolved oxygen. Cyclic voltammetry measurement was performed at -1.5 to 0 V (vs Ag/AgCl) using a glassy carbon electrode as a working electrode, a silver-silver chloride electrode as a reference electrode, and a platinum electrode as a counter electrode. The results are shown in Fig. 18.
As shown in FIG. 18, a reduction current was observed in the 50 mM acetate buffer (pH 4.6). On the other hand, no reduction current was observed under more basic conditions (pH 7.0 and pH 11.1). From this, it is understood that the reduction current is derived from proton reduction, that is, hydrogen generation. Therefore, it is understood that the (trans-CoM4Py ₂ P) ₂ /CB[10] of the present invention is a useful multi-electron redox catalyst that electrochemically produces hydrogen in water.

[Example 18]
As an example of the catalytic reaction, hydrogen production by glucose reforming of (trans-CoM4Py ₂ P) ₂ /CB[10] was examined. Glucose 270 mg (1.5 mmol) and (trans-CoM4Py ₂ P) ₂ /CB[10] 4.5 mg (0.0015 mmol) were dissolved in 2.0 mL of 50 mM acetate buffer (pH 4,6) and the solution was mixed at 98°C for 14 The mixture was heated under reflux for an hour. The gas generated after the reaction was collected by a gas buret system, and the generated gas was identified by gas chromatography. The results are shown in FIGS. 19(a) and 19(b).
As shown in FIGS. 19A and 19B, hydrogen and carbon dioxide were detected in the mixed gas after the glucose reforming reaction. As a result of quantifying the generated hydrogen and carbon dioxide using a calibration curve, it can be seen that 13 μmol of hydrogen and 19 μmol of carbon dioxide are generated. From the above, it is understood that the (trans-CoM4Py ₂ P) ₂ /CB[10] multi-electron redox catalyst of the present invention is a useful catalyst that produces hydrogen by a glucose reforming reaction.

[Example 19]
As an example of the catalytic reaction, the electrochemical nitrogen reduction reaction of "CoTM-4-PyP/Mo-Salen/CB[10]" was examined. CoTM-4-PyP/Mo-Salen/CB[10] was dissolved in 50 mM phosphate buffer (pH 7.4) containing 50 mM sodium chloride (NaCl) as a supporting electrolyte. The resulting solution was bubbled with helium or nitrogen for 30 minutes or longer. The nitrogen reduction reaction of CoTM-4-PyP/Mo-Salen/CB[10] was investigated by comparing the reduction currents in the presence of helium bubbling and in the presence of nitrogen. The results are shown in Fig. 20.
From the comparison between FIGS. 20(a) and 20(b), an increase in reduction current was observed in a nitrogen atmosphere at -1.5 to -1.0 V (vs Ag/AgCl). This indicates that the proton reduction (hydrogen generation) occurred in the presence of helium, but the reduction reaction of the proton and nitrogen occurred in the nitrogen atmosphere. That is, it is understood that the CoTM-4-PyP/Mo-Salen/CB[10] of the present invention is a useful catalyst for electrochemically reducing nitrogen.

Claims (1)

A cyclic compound having a 7 to 14-membered cucurbit structure,
A catalyst comprising a bulky compound included in the cyclic compound,
The bulky compound includes a metalloporphyrin compound represented by the following chemical formula (I), a metalloporphyrin compound represented by the following chemical formula (I), the metal pierlen represented by the following chemical formula (II) or the following chemical formula (III). A multi-electron redox catalyst characterized by being two molecules with a metal salen represented by:

In the above formulas, M1 and M2 are the same or different atoms and represent a transition metal element or a base metal element.
R5 to R8 are the same or different groups and represent a hydrogen atom, an alkyl group or an alkoxy group.