ELECTROCHEMICAL BIOSENSOR, OR SENSING MEMBRANE FOR ELECTROCHEMICAL BIOSENSOR CONTAINING TRANSITION METAL COMPLEX OR OXIDATION-REDUCTION POLYMER

Abstract

The present invention relates to: a transition metal complex having a bidentate ligand which includes pyrazole, triazole, tetrazole, oxadiazole, thiadiazole, or the like, wherein the transition metal complex can be used as an electron transfer mediator in a continuous blood glucose monitor and the like for measuring blood glucose concentration; and an oxidation-reduction polymer comprising same. The transition metal complex and the oxidation-reduction polymer can quickly and smoothly exchange electrons between an enzyme and an electrode, and thus can be effectively used in a continuous blood glucose biosensor.

Claims

1. A transition metal complex, which is a compound of the following Chemical formula 1, or a salt compound thereof:
[M(L).sub.a(X.sub.1).sub.b].sup.cd(X.sub.2)[Chemical formula 1] in the formula, M is one kind transition metal selected from the group consisting of Fe, Ru, and Os, and L is a bidentate ligand comprising pyridine; and one structure selected from the group consisting of pyrazole, triazole, tetrazole, oxadiazole and thiadiazole, and the pyridine is pyridine unsubstituted, or substituted with 1 to 4 selected from the group consisting of C.sub.1-4 alkyl group, C.sub.1-4 alkoxy group, (CH2)-OC.sub.1-4 alkyl group, (CH2CH2)-OC.sub.1-4 alkyl group, and C.sub.1-4 alkylamino group, and the one selected from the group consisting of pyrazole, triazole, tetrazole, and oxadiazole, is each independently unsubstituted, or substituted with 1 to 3 selected from the group consisting of C.sub.1-4 alkyl group, C.sub.1-4 alkoxy group, (CH2)-OC.sub.1-4 alkyl group, (CH2CH2)-OC.sub.1-4 alkyl group, ##STR00122## and C.sub.1-4 alkylamino group, and R.sub.4 is hydrogen or substituted or unsubstituted C.sub.1-4 alkyl, and n is an integer selected from 1 to 4, and a is 2 or 3, and in the substituted C.sub.1-4 alkyl group, C.sub.1-4 alkoxy group, (CH2)-OC.sub.1-4 alkyl group, (CH2CH2)-OC.sub.1-4 alkyl group or C.sub.1-4 alkylamino group, a hydrogen atom is substituted with a halogen atom of F, Cl, Br or I, cyano group, hydroxy group, thiol group, nitro group, amino group, imino group, azido group, amidino group, hydrazine group, hydrazono group, oxo group, carbonyl group, carbamyl group, ester group, ether group, carboxyl group or salt thereof, sulfonic acid group or salt thereof, or phosphoric acid or salt thereof, and X.sub.1 is one kind halogen atom selected from the group consisting of F, Cl, Br and I, and b is 0, 1, or 2, and c is an integer selected from 1 to 3, and X.sub.2 is one kind counter ion selected from the group consisting of F, Cl, Br, I and PF.sub.6, and d is 0, 1, 2, or 3.

2. The transition metal complex or salt compound thereof according to claim 1, wherein the transition metal complex is a compound of the following Chemical formula 2: ##STR00123## in the formula, R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are each independently hydrogen, C.sub.1-4 alkyl group, C.sub.1-4 alkoxy group, (CH2)-OC.sub.1-4 alkyl group, (CH2CH2)-OC.sub.1-4 alkyl group, or C.sub.1-4 alkylamino group, and n is 0, and at least one of W, Y, Z, and V is nitrogen (N), and W is nitrogen (N) or carbon (C), and Y, Z, and V are each independently nitrogen (N), sulfur (S), oxygen (O), or carbon (C), and R.sub.1, R.sub.2, and R.sub.3 are each independently hydrogen, C.sub.1-4 alkyl group, C.sub.1-4 alkoxy group, (CH2)-OC.sub.1-4 alkyl group, (CH2CH2)-OC.sub.1-4 alkyl group, ##STR00124## or C.sub.1-4 alkylamino group, and the C.sub.1-4 alkyl group, C.sub.1-4 alkoxy group, (CH2)-OC.sub.1-4 alkyl group, (CH2CH2)-OC.sub.1-4 alkyl group, R.sub.4, n, or C.sub.1-4 alkylamino group are the same as defined in claim 1, and M, a, X.sub.1, b, c, X.sub.2 and d are the same as defined in claim 1.

3. The transition metal complex or salt compound thereof according to claim 2, wherein the compound of Chemical formula 2 is a compound selected from the group consisting of compounds of the following Chemical formula 3 to Chemical formula 25: ##STR00125## ##STR00126## ##STR00127## ##STR00128## ##STR00129##

4. An oxidation-reduction polymer, represented by a compound of the following Chemical formula 26 or Chemical formula 27: ##STR00130## in the formula, m or o is each an integer selected from 10 to 600, and M, L, a, X.sub.1 and X.sub.2 are each the same as defined in claim 1.

5. The oxidation-reduction polymer according to claim 4, wherein the compound of Chemical formula 26 or Chemical formula 27 is a compound selected from the group consisting of compounds of the following Chemical formulas 28 to 45: ##STR00131## ##STR00132## ##STR00133## ##STR00134## ##STR00135## in the formula, m and o are each the same as defined in claim 5.

6. The oxidation-reduction polymer according to claim 4, which is represented by the following Chemical formula 46 or Chemical formula 47, wherein the oxidation-reduction polymer further comprises a crosslinkable functional group: ##STR00136## A.sub.D is one kind selected from the group consisting of primary and secondary amine groups, ammonium group, halogen group, epoxy group, azide group, acrylate group, alkenyl group, alkynyl group, thiol group, isocyanate, alcohol group, silane group, and ##STR00137## and the R.sub.5 is hydrogen or substituted or unsubstituted C.sub.1-4 alkyl, and the n is an integer selected from 1 to 4, and q is an integer selected from 1 to 10, and m, o, or p is each an integer selected from 10 to 600, and M, L, a, X.sub.1 and X.sub.2 are each the same defined in claim 1.

7. The oxidation-reduction polymer according to claim 6, wherein the compound of Chemical formula 46 or Chemical formula 47 is a compound selected from the group consisting of compounds of the following Chemical formula 48 to Chemical formula 60: ##STR00138## ##STR00139## ##STR00140## ##STR00141## in the formula, m, o and p are the same as defined in claim 7.

8. An electrochemical biosensor comprising the transition metal complex or salt compound thereof of any one of claims 1 to 3; or the oxidation-reduction polymer of any one of claims 4 to 7.

9. The electrochemical biosensor according to claim 8, wherein the electrochemical biosensor is insertable into the body.

10. A sensing membrane for an electrochemical biosensor comprising an enzyme capable of oxidizing-reducing a liquid biological sample; and the transition metal complex or salt compound thereof of any one of claims 1 to 3; or the oxidation-reduction polymer of any one of claims 4 to 7 as an electron transfer mediator.

11. The sensing membrane for an electrochemical biosensor according to claim 10, wherein the enzyme is at least one selected from the group consisting of dehydrogenase, oxidase and esterase.

12. The sensing membrane according to claim 11, wherein the enzyme is at least one selected from the group consisting of glucose dehydrogenase, glutamate dehydrogenase, glucose oxidase, cholesterol oxidase, cholesterol esterase, lactate oxidase, ascorbic acid oxidase, alcohol oxidase, alcohol dehydrogenase and bilirubin oxidase.

13. The sensing membrane according to claim 11, additionally comprising at least one cofactor selected from the group consisting of flavin adenine dinucleotide (FAD), nicotinamide adenine dinucleotide (NAD), and pyrroloquinoline quinone (PQQ).

14. The sensing membrane according to claim 10, further comprising a carbon nanotube.

15. The sensing membrane according to claim 10, wherein the liquid biological sample is at least one selected from the group consisting of a patient's tissue fluid, blood, cell, plasma, serum, urine, cyst fluid and saliva.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0131] FIG. 1a to FIG. 10 are cyclic voltammetry curves showing electrochemical characteristics of the transition metal complex having the bidentate ligand comprising pyrazole, triazole, tetrazole, oxadiazole, or thiadiazole according to the present invention.

[0132] {Chemical formula 3 (FIG. 1a), Chemical formula 4 (FIG. 1b), Chemical formula 9 (FIG. 1c), Chemical formula 11 (FIG. 1d), Chemical formula 14 (FIG. 1e), Chemical formula 15 (FIG. 1f), Chemical formula 16 (FIG. 1g), Chemical formula 17 (FIG. 1h), Chemical formula 18 (FIG. 1i), Chemical formula 20 (FIG. 1j), Chemical formula 22 (FIG. 1k), Chemical formula 23 (FIG. 1l), Chemical formula 24 (FIG. 1m), Chemical formula 25 (FIG. 1n), Chemical formula 3, 4, 11, 14, 15, 16 (FIG. 1o)}

[0133] FIG. 2 is a cyclic voltammetry curves showing electrochemical characteristics of the oxidation-reduction polymer comprising the transition metal complex according to the present invention.

[0134] FIG. 3 is a cyclic voltammetry curves showing electrochemical characteristics of the oxidation-reduction polymer comprising the transition metal complex according to the present invention and a crosslinkable functional group.

[0135] FIG. 4 shows a potential of an electrode to which the oxidation-reduction polymer according to the present invention is applied.

[0136] FIG. 5 and FIG. 6 are graphs which show that all the electrodes to which the oxidation-reduction polymer according to the present invention is applied showed the linearity for glucose at a concentration of 10 mM or less, and showed similar sensitivity, even though voltage lower than the comparative group electrode was applied.

[0137] FIG. 7 is a graph which shows that all the electrodes to which the oxidation-reduction polymer according to the present invention is applied showed sensitivity for glucose at voltage lower than the comparative group electrode.

MODE FOR INVENTION

[0138] Hereinafter, the present invention will be described in more detail by the following examples. However, the following examples illustrate the present invention only, but the contents of the present invention are not limited by the following examples.

Example 1: Preparation of Transition Metal Complex According to the Present Invention

Example 1.1. Synthesis of transition metal complex of Chemical formula 3

1) Synthesis of 2-(1H-pyrazol-1-yl)pyridine

[0139] ##STR00023##

[0140] A reflux condenser and a gas inlet were equipped to a 250 mL two-neck round bottom flask, and pyrazole 4.7 g (69 mmol) and potassium butoxide 9.3 g (83 mmol) were added, and dissolved in anhydrous dimethylsulfoxide 40 mL in an argon gas atmosphere. To this reaction mixture, 2-fluoropyrifine 8.0 g (83 mmol) was added and heated to 100 C. in an argon gas atmosphere and stirred for 4 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and extracted with water (100 mL) and ethylacetate (100 mL3). Organic layers were collected and dried with magnesium sulfate and concentrated under reduced pressure to obtain a transparent, colorless solid. (7.2 g, 72%)

2) Synthesis of Os(pzpy).SUB.2.Cl.SUB.2 .[Chemical formula 3]

[0141] ##STR00024##

[0142] Potassium hexachloroosmate(IV) 5.0 g (10 mmol) and 2-(1H-pyrazol-1-yl)pyridine 2.9 g (20 mmol) prepared in 1) above were added in a 500 mL shrink flask, and dissolved in 200 mL ethylene glycol in an argon gas atmosphere, and then argon degassing was performed for 15 minutes. This reaction mixture was heated to 180 C. and stirred for 1 hour. After completing the reaction, the reaction mixture was cooled to a room temperature and produced red precipitates were filtered under reduced pressure and removed. The filtrate was dropped in a sodium dithionite 1.0 M aqueous solution (250 mL), thereby obtaining precipitates of the reduced osmium complex. The produced solid was filtered under reduced pressure and washed with water several times, and then dried in a vacuum oven of 40 C. to obtain a green final compound osmium complex. (4.0 g, 75%) HRMS (.sup.192Os): m/z 552.0240([M.sup.+] required 552.0261)

[0143] The entire preparation method of the compound of Chemical formula 3 is as the following Reaction formula 1.

##STR00025##

Example 1.2. Synthesis of Transition Metal Complex of Chemical Formula 4

1) Synthesis of 2-methyl-6-(1H-pyrazol-1-yl)pyridine

[0144] ##STR00026##

[0145] A reflux condenser and a gas inlet were equipped to a 250 mL two-neck round bottom flask, and pyrazole 2.0 g (30 mmol) and potassium tertiary butoxide 4.0 g (36 mmol) were added and dissolved in an anhydrous dimethylsulfoxide 20 mL in an argon gas atmosphere. 2-fluoro-5-methyl pyridine 5.0 g (36 mmol) was added to this reaction mixture and heated to 100 C. in an argon gas atmosphere and stirred for 4 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and extracted with water (100 mL) and ethylacetate (100 mL3). Organic layers were collected and concentrated under reduced pressure and after removing the solvent, it was purified by column chromatography using ethylacetate and hexane as developing solvents. (hexane:ethylacetate=5:1) Finally, 2-methyl-6-(1H-pyrazol-1-yl)pyridine of a transparent solid was obtained. (1.4 g, 30%)

2) Synthesis of Os(pz-2-Me-py).SUB.2.Cl.SUB.2 .[Chemical formula 4]

[0146] ##STR00027##

[0147] Potassium hexachloroosmate(IV) 1.5 g (3.1 mmol) and 2-(1H-pyrazol-1-yl)pyridine 1.0 g (6.3 mmol) prepared in 1) above were added in a 250 mL shrink flask, and dissolved in 50 mL ethylene glycol in an argon gas atmosphere, and then argon degassing was performed for 15 minutes. This reaction mixture was heated to 180 C. and stirred for 1 hour. After completing the reaction, the reaction mixture was cooled to a room temperature and produced red precipitates were filtered under reduced pressure and removed. The filtrate was dropped in a sodium dithionite 1.0 M aqueous solution (250 mL), thereby obtaining precipitates of the reduced osmium complex. The produced solid was filtered under reduced pressure and washed with water and acetonitrile several times, and then dried in a vacuum oven to obtain a green final compound osmium complex. (0.27 g, 15%) HRMS (.sup.192Os): m/z 580.0569([M.sup.+] required 580.0574)

[0148] The entire preparation method of the compound of Chemical formula 4 is as the following Reaction formula 2.

##STR00028##

Example 1.3. Synthesis of Transition Metal Complex of Chemical Formula 5

1) Synthesis of 4-methoxy-2-(1H-pyrazol-1-yl)pyridine

[0149] ##STR00029##

[0150] A reflux condenser and a gas inlet were equipped to a 250 mL two-neck round bottom flask, and pyrazole 2.0 g (30 mmol) and potassium tertiary butoxide 4.0 g (36 mmol) were added and dissolved in an anhydrous dimethylsulfoxide 20 mL in an argon gas atmosphere. 2-bromo-4-methoxy pyridine 6.7 g (36 mmol) was added to this reaction mixture and heated to 100 C. in an argon gas atmosphere and stirred for 8 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and extracted with water (100 mL) and ethylacetate (100 mL3). Organic layers were collected and concentrated under reduced pressure and after removing the solvent, it was purified by column chromatography using ethylacetate and hexane as developing solvents. (hexane: ethylacetate=3:1) Finally, 4-methoxy-2-(1H-pyrazol-1-yl)pyridine of a transparent solid was obtained. (4.0 g, 63%)

2) Synthesis of Os(pz-4-Meo-py).SUB.2.Cl.SUB.2 .[Chemical formula 5]

[0151] ##STR00030##

[0152] Potassium hexachloroosmate(IV) 2.0 g (4.2 mmol) and 4-methoxy-2-(1H-pyrazol-1-yl)pyridine 1.5 g (8.3 mmol) prepared in 1) above were added in a 250 mL shrink flask, and dissolved in 50 mL ethylene glycol in an argon gas atmosphere, and then argon degassing was performed for 15 minutes. This reaction mixture was heated 10 to 180 C. and stirred for 1 hour. After completing the reaction, the reaction mixture was cooled to a room temperature and produced red precipitates were filtered under reduced pressure and removed. The filtrate was dropped in a sodium dithionite 1.0 M aqueous solution (250 mL), thereby obtaining precipitates of the reduced osmium complex. The produced solid was filtered under reduced pressure and washed with water and acetonitrile several times, and then dried in a vacuum oven to obtain a green final compound osmium complex. (2.0 g, 78%) HRMS (.sup.192Os): m/z 612.0460([M.sup.+] required 612.0472)

[0153] The entire preparation method of the compound of Chemical formula 5 is as the following Reaction formula 3.

##STR00031##

Example 1.4. Synthesis of Transition Metal Complex of Chemical Formula 6

1) Synthesis of 4-methyl-2-(1H-pyrazol-1-yl)pyridine

[0154] ##STR00032##

[0155] A reflux condenser and a gas inlet were equipped to a 250 mL two-neck round bottom flask, and pyrazole 2.0 g (30 mmol) and potassium tertiary butoxide 4.0 g (36 mmol) were added and dissolved in an anhydrous dimethylsulfoxide 20 mL in an argon gas atmosphere. 2-bromo-4-methyl pyridine 6.2 g (36 mmol) was added to this reaction mixture and heated to 100 C. in an argon gas atmosphere and stirred for 8 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and extracted with water (100 mL) and ethylacetate (100 mL3). Organic layers were collected and concentrated under reduced pressure and after removing the solvent, it was purified by column chromatography using ethylacetate and hexane as developing solvents. (hexane: ethylacetate=3:1) Finally, 4-methoxy-2-(1H-pyrazol-1-yl)pyridine of a transparent solid was obtained. (3.5 g, 61%)

2) Synthesis of Os(pz-4-Me-py).SUB.2.Cl.SUB.2 .[Chemical formula 6]

[0156] ##STR00033##

[0157] Potassium hexachloroosmate(IV) 2.0 g (4.2 mmol) and 4-methyl-2-(1H-pyrazol-1-yl)pyridine 1.3 g (8.3 mmol) prepared in 1) above were added in a 250 mL shrink flask, and dissolved in 50 mL ethylene glycol in an argon gas atmosphere, and then argon degassing was performed for 15 minutes. This reaction mixture was heated to 180 C. and stirred for 1 hour. After completing the reaction, the reaction mixture was cooled to a room temperature and produced red precipitates were filtered under reduced pressure and removed. The filtrate was dropped in a sodium dithionite 1.0 M aqueous solution (250 mL), thereby obtaining precipitates of the reduced osmium complex. The produced solid was filtered under reduced pressure and washed with water and acetonitrile several times, and then dried in a vacuum oven to obtain a green final compound osmium complex. (1.0 g, 42%) HRMS (.sup.192Os): m/z 580.0561([M.sup.+] required 580.0574)

[0158] The entire preparation method of the compound of Chemical formula 6 is as the following Reaction formula 4.

##STR00034##

Example 1.5. Synthesis of Transition Metal Complex of Chemical Formula 7

1) Synthesis of 4-methyl-2-(3-methyl-1H-pyrazol-1-yl)pyridine

[0159] ##STR00035##

[0160] A reflux condenser and a gas inlet were equipped to a 250 mL two-neck round bottom flask, and 3-methylpyrazole 2.5 g (30 mmol) and potassium tertiary butoxide 4.0 g (36 mmol) were added and dissolved in an anhydrous dimethylsulfoxide 20 mL in an argon gas atmosphere. 2-bromo-4-methyl pyridine 6.2 g (36 mmol) was added to this reaction mixture and heated to 100 C. in an argon gas atmosphere and stirred for 18 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and extracted with water (100 mL) and ethylacetate (100 mL3). Organic layers were collected and concentrated under reduced pressure and after removing the solvent, it was purified by column chromatography using ethylacetate and hexane as developing solvents. (hexane: ethylacetate=3:1) Finally, 4-methyl-2-(3-methyl-1H-pyrazol-1-yl)pyridine of a transparent solid was obtained. (4.2 g, 80%)

2) Synthesis of Os(3-Me-pz-4-Me-py).SUB.2.Cl.SUB.2 .[Chemical formula 7]

[0161] ##STR00036##

[0162] Potassium hexachloroosmate(IV) 2.0 g (4.2 mmol) and 4-methyl-2-(3-methyl-1H-pyrazol-1-yl)pyridine 1.4 g (8.3 mmol) prepared in 1) above were added in a 250 mL shrink flask, and dissolved in 50 mL ethylene glycol in an argon gas atmosphere, and then argon degassing was performed for 15 minutes. This reaction mixture was heated to 180 C. and stirred for 1 hour. After completing the reaction, the reaction mixture was cooled to a room temperature and produced red precipitates were filtered under reduced pressure and removed. The filtrate was dropped in a sodium dithionite 1.0 M aqueous solution (250 mL), thereby obtaining precipitates of the reduced osmium complex. The produced solid was filtered under reduced pressure and washed with water and acetonitrile several times, and then dried in a vacuum oven to obtain a green final compound osmium complex. (2.0 g, 78%) HRMS (.sup.192Os): m/z 608.0875([M.sup.+] required 608.0887)

[0163] The entire preparation method of the compound of Chemical formula 7 is as the following Reaction formula 5.

##STR00037##

Example 1.6. Synthesis of Transition Metal Complex of Chemical Formula 8

1) Synthesis of 4-methoxy-2-(3-methyl-1H-pyrazol-1-yl)pyridine

[0164] ##STR00038##

[0165] A reflux condenser and a gas inlet were equipped to a 250 mL two-neck round bottom flask, and 3-methylpyrazole 2.5 g (30 mmol) and potassium tertiary butoxide 4.0 g (36 mmol) were added and dissolved in an anhydrous dimethylsulfoxide 20 mL in an argon gas atmosphere. 2-bromo-4-methoxy pyridine 6.7 g (36 mmol) was added to this reaction mixture and heated to 100 C. in an argon gas atmosphere and stirred for 18 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and extracted with water (100 mL) and ethylacetate (100 mL3). Organic layers were collected and concentrated under reduced pressure and after removing the solvent, it was purified by column chromatography using ethylacetate and hexane as developing solvents. (hexane: ethylacetate=3:1) Finally, 4-methoxy-2-(3-methyl-1H-pyrazol-1-yl)pyridine of a transparent solid was obtained. (3.0 g, 53%)

2) Synthesis of Os(3-Me-p-4-MeO-py).SUB.2.Cl.SUB.2 .[Chemical formula 8]

[0166] ##STR00039##

[0167] Potassium hexachloroosmate(IV) 2.0 g (4.2 mmol) and 4-methoxy-2-(3-methyl-1H-pyrazol-1-yl)pyridine 1.5 g (8.3 mmol) prepared in 1) above were added in a 250 mL shrink flask, and dissolved in 50 mL ethylene glycol in an argon gas atmosphere, and then argon degassing was performed for 15 minutes. This reaction mixture was heated to 180 C. and stirred for 1 hour. After completing the reaction, the reaction mixture was cooled to a room temperature and produced red precipitates were filtered under reduced pressure and removed. The filtrate was dropped in a sodium dithionite 1.0 M aqueous solution (250 mL), thereby obtaining precipitates of the reduced osmium complex. The produced solid was filtered under reduced pressure and washed with water and acetonitrile several times, and then dried in a vacuum oven to obtain a green final compound osmium complex. (1.0 g, 37%) HRMS (.sup.1920s): m/z 640.0775([M.sup.+] required 640.0785)

[0168] The entire preparation method of the compound of Chemical formula 8 is as the following Reaction formula 6.

##STR00040##

Example 1.7. Synthesis of Transition Metal Complex of Chemical Formula 9

1) Synthesis of 4-methyl-2-(4-methyl-1H-pyrazol-1-yl)pyridine

[0169] ##STR00041##

[0170] A reflux condenser and a gas inlet were equipped to a 250 mL two-neck round bottom flask, and 4-methylpyrazole 2.5 g (30 mmol) and potassium tertiary butoxide 4.0 g (36 mmol) were added and dissolved in an anhydrous dimethylsulfoxide 20 mL in an argon gas atmosphere. 2-bromo-4-methyl pyridine 6.2 g (36 mmol) was added to this reaction mixture and heated to 100 C. in an argon gas atmosphere and stirred for 18 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and extracted with water (100 mL) and ethylacetate (100 mL3). Organic layers were collected and concentrated under reduced pressure and after removing the solvent, it was purified by column chromatography using ethylacetate and hexane as developing solvents. (hexane: ethylacetate=3:1) Finally, 4-methyl-2-(4-methyl-1H-pyrazol-1-yl)pyridine of a transparent solid was obtained. (4.5 g, 86%)

2) Synthesis of Os(4-Me-pz-4-Me-py).SUB.2.Cl.SUB.2 .[Chemical formula 9]

[0171] ##STR00042##

[0172] Potassium hexachloroosmate(IV) 5.0 g (10 mmol) and 4-methyl-2-(4-methyl-1H-pyrazol-1-yl)pyridine 4.1 g (21 mmol) prepared in 1) above were added in a 250 mL shrink flask, and dissolved in 100 mL ethylene glycol in an argon gas atmosphere, and then argon degassing was performed for 15 minutes. This reaction mixture was heated to 180 C. and stirred for 1 hour. After completing the reaction, the reaction mixture was cooled to a room temperature and produced red precipitates were filtered under reduced pressure and removed. The filtrate was dropped in a sodium dithionite 1.0 M aqueous solution (250 mL), thereby obtaining precipitates of the reduced osmium complex. The produced solid was filtered under reduced pressure and washed with water and acetonitrile several times, and then dried in a vacuum oven to obtain a green final compound osmium complex. (5.5 g, 91%) HRMS (.sup.192Os): m/z 608.0871([M.sup.+] required 608.0887)

[0173] The entire preparation method of the compound of Chemical formula 9 is as the following Reaction formula 7.

##STR00043##

Example 1.8. Synthesis of transition metal complex of Chemical formula 10

1) Synthesis of 4-methoxy-2-(4-methyl-1H-pyrazol-1-yl)pyridine

[0174] ##STR00044##

[0175] A reflux condenser and a gas inlet were equipped to a 250 mL two-neck round bottom flask, and 4-methylpyrazole 2.5 g (30 mmol) and potassium tertiary butoxide 4.0 g (36 mmol) were added and dissolved in an anhydrous dimethylsulfoxide 20 mL in an argon gas atmosphere. 2-bromo-4-methoxy pyridine 6.7 g (36 mmol) was added to this reaction mixture and heated to 100 C. in an argon gas atmosphere and stirred for 18 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and extracted with water (100 mL) and ethylacetate (100 mL3). Organic layers were collected and concentrated under reduced pressure and after removing the solvent, it was purified by column chromatography using ethylacetate and hexane as developing solvents. (hexane: ethylacetate=3:1) Finally, 4-methoxy-2-(4-methyl-1H-pyrazol-1-yl)pyridine of a transparent solid was obtained. (2.8 g, 50%)

2) Synthesis of Os(4-Me-pz4-MeO-py).SUB.2.Cl.SUB.2 .[Chemical formula 10]

[0176] ##STR00045##

[0177] Potassium hexachloroosmate(IV) 3.0 g (6.2 mmol) and 4-methoxy-2-(4-methyl-1H-pyrazol-1-yl)pyridine 2.4 g (12 mmol) prepared in 1) above were added in a 250 mL shrink flask, and dissolved in 60 mL ethylene glycol in an argon gas atmosphere, and then argon degassing was performed for 15 minutes. This reaction mixture was heated to 180 C. and stirred for 1 hour. After completing the reaction, the reaction mixture was cooled to a room temperature and produced red precipitates were filtered under reduced pressure and removed. The filtrate was dropped in a sodium dithionite 1.0 M aqueous solution (250 mL), thereby obtaining precipitates of the reduced osmium complex. The produced solid was filtered under reduced pressure and washed with water and acetonitrile several times, and then dried in a vacuum oven to obtain a green final compound osmium complex. (2.3 g, 58%) HRMS (.sup.192Os): m/z 640.0792([M.sup.+] required 640.0785)

[0178] The entire preparation method of the compound of Chemical formula 10 is as the following Reaction formula 8.

##STR00046##

Example 1.9. Synthesis of Transition Metal Complex of Chemical Formula 11

1) Synthesis of (pyridin-2-yl)amidrazone

[0179] ##STR00047##

[0180] 2-cyanopyridine 5.2 g (50 mmol) and hydrazine hydrates 2.7 g (55 mmol) were added in a 100 mL two-neck round bottom flask, and ethanol 4 mL was added and they were stirred at a room temperature for 24 hours. After completing the reaction, the reaction mixture was filtered under reduced pressure to remove remaining solvents, and washed with benzene. The filtered solid was recrystallized in toluene to obtain (pyridin-2-yl)amidrazone. (4.2 g, 61%)

2) Synthesis of 2-(1,3-dimethyl-1H-1,2,4-triazol-5-yl)pyridine

[0181] ##STR00048##

[0182] (Pyridin-2-yl)amidrazone prepared in 1) above 2.0 g (15 mmol) and sodium carbonate 1.6 g (15 mmol) were added in a 50 mL shrink flask, and dimethyl acetamide 15 mL and tetrahydrofuran 5 mL which were solvents were added and they were stirred at 0 C. Additionally, anhydrous dimethyl acetamide 5 mL and acetyl chloride 1.1 mL (15 mmol) were added to a 10 mL round bottom flask, and it was blocked with a rubber septa, and then it was dropped to the reaction mixture through a cannula under argon and it was stirred at a room temperature for 5 hours. After completing the reaction, the reaction mixture was filtered under reduced pressure to remove remaining solvents and it was washed with ethanol and distilled water to obtain a white solid. The white solid and ethylene glycol 20 mL were added in a 50 mL one-neck flask, and it was heated to 190 C. and stirred for 30 minutes. After completing the reaction, the reaction mixture was cooled to a room temperature and the ethylene glycol solvent was removed through distillation under reduced pressure to finally obtain 2-(5-R-2H-1,2,4-triazol-3-yl)pyridine of a yellow solid. (0.22 g, 9%)

[0183] 2-(3-methyl-1H-1,2,4-triazol-5-yl)pyridine 0.22 g (1.4 mmol) was added in a 50 mL one-neck flask, and it was dissolved in anhydrous dimethyl formamide 5 mL in an argon gas atmosphere, and then sodium hydride 83 mg (2.0 mmol) was added. This reaction mixture was stirred to a room temperature for 20 minutes and iodomethane 0.3 g (2.0 mmol) was added in an argon gas atmosphere, and then it was stirred at a room temperature for 24 hours again. After completing the reaction, the reaction mixture was extracted with water (100 mL) and ethylacetate (100 mL3). Organic layers were collected and concentrated under reduced pressure and purified by column chromatography using ethylacetate and hexane as developing solvents. (hexane: ethylacetate=7:3) Finally, 2-(1,3-dimethyl-1H-1,2,4-triazol-5-yl)pyridine was obtained. (83 mg, 34%)

3) Synthesis of Os(Dmtz-py).SUB.2.Cl.SUB.2 .[Chemical formula 11]

[0184] ##STR00049##

[0185] Potassium hexachloroosmate(IV) 14 mg (28.7 mmol) and 2-(1,3-dimethyl-1H-1,2,4-triazol-5-yl)pyridine 10 mg (57 umol) prepared in 2) above were added in a 5 mL Corn vial, and dissolved in 2 mL ethylene glycol in an argon gas atmosphere, and then argon degassing was performed for 15 minutes. This reaction mixture was heated to 180 C. and stirred for 1 hour. After completing the reaction, the reaction mixture was cooled to a room temperature and produced red precipitates were filtered under reduced pressure and removed. The filtrate was dropped in a sodium dithionite 1.0 M aqueous solution (10 mL), thereby obtaining precipitates of the reduced osmium complex. The produced solid was filtered under reduced pressure and washed with water several times, and then dried in a vacuum oven of 40 C. to obtain a brown final compound osmium complex. (15 mg, 86%) HRMS (.sup.192Os): m/z 610.0797([M.sup.+] required 610.0792)

[0186] The entire preparation method of the compound of Chemical formula 11 is as the following Reaction formula 9.

##STR00050##

Example 1.10. Synthesis of Transition Metal Complex of Chemical Formula 12

1) Synthesis of 5-methyl-3-(pyridin-2-yl)-1,2,4-oxadiazole

[0187] ##STR00051##

[0188] A reflux condenser and a gas inlet were equipped to a 250 mL two-neck round bottom flask, and ammonium hydroxyl chloride 7.0 g (0.1 mol) and potassium hydroxide 6.0 g (0.1 mol) were added in methanol 100 ml, and it was heated to 100 C. and stirred for 30 minutes. The produced potassium chloride was concentrated under reduced pressure and removed, and pyridine carbonitrile 7.0 g (60 mmol) was added to the filtered reaction solution and heated to 100 C., and stirred for 1 hour. After completing the reaction, the mixture was concentrated under reduced pressure and washed with distilled water to obtain hydroxy picolinimidamide of a transparent solid. (9.0 g, 65%)

[0189] A reflux condenser and a gas inlet were equipped to a 250 mL two-neck round bottom flask, and hydroxy picolinimidamide 1.0 g (7.3 mmol), pyridine 1.0 g (12.3 mmol), and acetyl chloride 0.7 g (8.8 mmol) were added to tetrahydrofuran 60 ml, and it was heated to 110 C. and stirred for 8 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and extracted with water (100 mL) and ethylacetate (100 mL3). Organic layers were concentrated under reduced pressure and after removing solvents, 5-methyl-3-(pyridin-2-yl)-1,2,4-oxadiazole of a transparent solid was obtained. (0.85 g, 72%)

2) Synthesis of Os(Me-oxz-py).SUB.2.Cl.SUB.2 .[Chemical formula 12]

[0190] ##STR00052##

[0191] Potassium hexachloroosmate(IV) 0.6 g (1.4 mmol) and 5-methyl-3-(pyridin-2-yl)-1,2,4-oxadiazole 0.5 g (2.9 mmol) prepared in 1) above were added in a 250 mL shrink flask, and dissolved in 50 mL ethylene glycol in an argon gas atmosphere, and then argon degassing was performed for 15 minutes. This reaction mixture was heated to 180 C. and stirred for 20 minutes. After completing the reaction, the reaction mixture was cooled to a room temperature and produced red precipitates were filtered under reduced pressure and removed. The filtrate was dropped in a sodium dithionite 1.0 M aqueous solution (30 mL), thereby obtaining precipitates of the reduced osmium complex. The produced solid was filtered under reduced pressure and washed with water and acetonitrile several times, and then dried in a vacuum oven to obtain a yellow-brown final compound osmium complex. (0.6 g, 70%)

[0192] The entire preparation method of the compound of Chemical formula 12 is as the following Reaction formula 10.

##STR00053##

Example 1.11. Synthesis of Transition Metal Complex of Chemical Formula 13

1) Synthesis of 2-(1-butyl-1H-1,2,3-triazol-4-yl)pyridine

[0193] ##STR00054##

[0194] 1-bromobutane 2.0 g (14 mmol) and sodium azide 0.9 g (14 mmol) were added in a 250 mL round bottom flask, and anhydrous dimethylformamide of 50 mL was added and it was stirred at a room temperature for 24 hours. After completing the reaction, this reaction mixture was extracted with water (100 mL) and diethylether (100 mL3). Organic layers were collected and dried with magnesium sulfate, and concentrated under reduced pressure, and after removing solvents, without additional purification, the next reaction was progressed. 1-azidobutane and 2-ethynylpyridine 1.5 g (14 mmol) were added in a 250 mL two-neck round bottom flask, and tetrahydrofuran/water (40 mL/40 mL) was added and stirred at a room temperature. Sodium ascorbate 0.3 g (1.4 mmol) and copper sulfate 23 mg (0.14 mmol) were added to this reaction mixture, and argon degassing was performed for 15 minutes, and then it was stirred at a room temperature for 2 hours. After completing the reaction, the reaction mixture was extracted with water (100 mL) and ethylacetate (100 mL3), and organic layers were collected and dried with magnesium sulfate. This solution was concentrated under reduced pressure and solvents were removed and it was purified by column chromatography using ethylacetate and hexane as developing solvents. (hexane: ethylacetate=1:4) Finally, 2-(1-(2-methoxyethynyl)-1H-1,2,3-triazol-4-yl)pyridine was obtained. (1.5 g, 52%)

2) Synthesis of Os(3-Bu-tz-py).SUB.2.Cl.SUB.2 .[Chemical formula 13]

[0195] ##STR00055##

[0196] Potassium hexachloroosmate(IV) 0.5 g (1.0 mmol) and 2-(1-butyl-1H-1,2,3-triazol-4-yl)pyridine 0.4 g (2.0 mmol) prepared in 1) above were added in a 100 mL shrink flask, and dissolved in 15 mL ethylene glycol in an argon gas atmosphere, and then argon degassing was performed for 15 minutes. This reaction mixture was heated to 180 C. and stirred for 1 hour. After completing the reaction, the reaction mixture was cooled to a room temperature and produced red precipitates were filtered under reduced pressure and removed. The filtrate was dropped in a sodium dithionite 1.0 M aqueous solution (200 mL), thereby obtaining precipitates of the reduced osmium complex. The produced solid was filtered under reduced pressure and washed with water several times, and then dried in a vacuum oven of 40 C. to obtain a final compound osmium complex. (0.4 g, 56%)

[0197] The entire preparation method of the compound of Chemical formula 13 is as the following Reaction formula 11.

##STR00056##

Example 1.12. Synthesis of Transition Metal Complex of Chemical Formula 14

1) Synthesis of 13-bromo-2,5,8,11-tetraoxatridecane

[0198] ##STR00057##

[0199] Tetraethylene glycol monomethyl ether 2.0 g (9.6 mmol) and tetrabromomethane 3.8 g (11.5 mmol) were added in a 250 mL round bottom flask, and dissolved in dichloromethane 50 mL, and then stirred at 0 C. using an ice tank. After that, during maintaining 0 C., triphenylphosphine 3.0 g (11.5 mmol) was subdivided for 15 minutes and slowly added and stirred at a room temperature for 2 hours. After completing the reaction, the reaction mixture was extracted with water (100 mL) and dichloromethane (100 mL3). Organic layers were collected and concentrated under reduced pressure and purified by column chromatography using ethylacetate and hexane as developing solvents. (hexane: ethylacetate=2:1 (methanol 8%)) Finally, 13-bromo-2,5,8,11-tetraoxatridecane of yellow oil was obtained. (1.4 g, 54%)

2) Synthesis of 2-(1-(2,5,8,11-tetraoxatridecan-13-yl)-1H-1,2,3,-triazol-4-yl)pyridine

[0200] ##STR00058##

[0201] 13-bromo-2,5,8,11-tetraoxatridecane 1.4 g (5.2 mmol) prepared in 1) above and sodium azide 0.34 g (5.2 mmol) were added in a 250 mL round bottom flask, and anhydrous dimethylformamide of 40 mL was added and stirred at a room temperature for 24 hours. After completing the reaction, this reaction mixture was extracted with water (100 mL) and diethylether (100 mL3). Organic layers were collected and dried with magnesium sulfate, and concentrated under reduced pressure, and after removing solvents, without additional purification, the next reaction was progressed. 13-azido-2,5,8,11-tetraoxatridecane and 2-ethynylpyridine 0.8 g (7.7 mmol) were added in a 250 mL two-neck round bottom flask, and tetrahydrofuran/water (40 mL/40 mL) was added and stirred at a room temperature. Sodium ascorbate 0.15 g (0.8 mmol), and cooper sulfate 12 mg (0.08 mmol) were added to this reaction mixture and argon degassing was performed for 15 minutes, and then it was stirred at a room temperature for 2 hours. After completing the reaction, the reaction mixture was extracted with water (100 mL) and ethylacetate (100 mL3), and organic layers were collected and layers were collected and dried with magnesium sulfate. This solution was concentrated under reduced pressure and solvents were removed, and it was purified by column chromatography using ethyl acetate and hexane as developing solvents. (hexane: ethylacetate=1:2 (methanol 5%)) Finally, 2-(1-(2,5,8,11-tetraoxatridecan-13-yl)-1H-1,2,3,-triazol-4-yl)pyridine was obtained. (0.86 g, 43%)

3) Synthesis of Os(3-tz-teg-py).SUB.2.Cl.SUB.2 .[Chemical formula 14]

[0202] ##STR00059##

[0203] Potassium hexachloroosmate(IV) 0.1 g (0.21 mmol) and 2-(1-(2,5,8,11-tetraoxatridecan-13-yl)-1H-1,2,3,-triazol-4-yl)pyridine 0.14 g (0.42 mmol) prepared in 2) above were added in a 50 mL shrink flask, and dissolved in 15 mL ethylene glycol in an argon gas atmosphere, and then argon degassing was performed for 15 minutes. This reaction mixture was heated to 180 C. and stirred for 1 hour. After completing the reaction, the reaction mixture was cooled to a room temperature and produced red precipitates were filtered under reduced pressure and removed. The filtrate was dropped in a sodium dithionite 1.0 M aqueous solution (10 mL), thereby obtaining precipitates of the reduced osmium complex. The produced solid was filtered under reduced pressure and washed with water several times, and then dried in a vacuum oven of 40 C. to obtain a black-purple final compound osmium complex. (0.1 g, 56%)

[0204] The entire preparation method of the compound of Chemical formula 14 is as the following Reaction formula 12.

##STR00060##

Example 1.13. Synthesis of Transition Metal Complex of Chemical Formula 15

1) Synthesis of 2-(1-(2-methoxyethynyl)-1H-1,2,3-triazol-4-yl)pyridine

[0205] ##STR00061##

[0206] 2-Bromoethyl methyl ether 2.0 g (14 mmol) and sodium azide 0.1 g (14 mmol) were added in a 250 mL round bottom flask, and anhydrous dimethylformamide of 50 mL was added and stirred at a room temperature for 24 hours. After completing the reaction, this reaction mixture was extracted with water (100 mL) and diethylether (100 mL3). Organic layers were collected and concentrated under reduced pressure and after removing the solvent, without addition purification, the next reaction was progressed. 2-azidoethyl methyl ether and 2-ethynyl pyridine 1.5 g (14 mmol) were added in a 250 mL two-neck round bottom flask, and tetrahydrofuran/water (40 mL/40 mL) was added, and stirred at a room temperature. Sodium ascorbate 0.28 g (1.4 mmol) and copper sulfate 0.02 g (0.14 mmol) were added to this reaction mixture, and argon degassing was performed for 15 minutes, and then it was stirred at a room temperature for 2 hours. After completing the reaction, the reaction mixture was extracted with water (100 mL) and ethylacetate (100 mL3). Organic layers were collected and dried with magnesium sulfate. This solution was concentrated under reduced pressured to remove solvents, and it was purified by column chromatography using ethylacetate and hexane as developing solvents. (hexane: ethylacetate=1:4) Finally, 2-(1-(2-methoxyethynyl)-1H-1,2,3-triazol-4-yl)pyridine was obtained. (1.5 g, 52%)

2) Synthesis of Os(3-mo-tz-py).SUB.2.Cl.SUB.2 .[Chemical formula 15]

[0207] ##STR00062##

[0208] Potassium hexachloroosmate(IV) 0.5 g (1.0 mmol) and 2-(1-(2-methoxyethynyl)-1H-1,2,3-triazol-4-yl)pyridine 0.4 g (2.1 mmol) prepared in 1) above were added in a 100 mL shrink flask, and dissolved in 15 mL ethylene glycol in an argon gas atmosphere, and then argon degassing was performed for 15 minutes. This reaction mixture was heated to 180 C. and stirred for 1 hour. After completing the reaction, the reaction mixture was cooled to a room temperature and produced red precipitates were filtered under reduced pressure and removed. The filtrate was dropped in a sodium dithionite 1.0 M aqueous solution (200 mL), thereby obtaining precipitates of the reduced osmium complex. The produced solid was filtered under reduced pressure and washed with water several times, and then dried in a vacuum oven of 40 C. to obtain a green final compound osmium complex. (0.4 g, 56%) HRMS (.sup.192OS): m/z 670.09967([M.sup.+] required 670.10)

[0209] The entire preparation method of the compound of Chemical formula 15 is as the following Reaction formula 13.

##STR00063##

Example 1.14. Synthesis of Transition Metal Complex of Chemical Formula 16

1) Synthesis of 2-(1H-tetrazole-5-yl)pyridine

[0210] ##STR00064##

[0211] A reflux condenser and a gas inlet were equipped to a 250 mL two-neck round bottom flask, and sodium azide 1.3 g (19.2 mmol), 2-ethynyl pyridine 2.0 g (19.2 mmol) and copper sulfate 96 mg (0.38 mmol) were added and dissolved in an anhydrous dimethylsulfoxide 40 mL in an argon gas atmosphere. For this reaction mixture, argon degassing was performed for 15 minutes, and then it was heated to 140 C. and stirred for 3 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and extracted with water (100 mL) and ethylacetate (100 mL3), and organic layers were collected and dried with magnesium sulfate. This solution was concentrated under reduced pressure to remove solvents, and finally, 2-(1H-tetrazole-5-yl)pyridine of a yellow solid was obtained. (1.1 g, 41%)

2) Synthesis of 2-(1-methyl-1H-tetrazole-5-yl)pyridine

[0212] ##STR00065##

[0213] A reflux condenser and a gas inlet were equipped to a 100 mL two-neck round bottom flask, and 2-(1H-tetrazole-5-yl)pyridine 1.0 g (6.8 mmol) prepared in 1) above was added and dissolved in an anhydrous tetrahydrofuran (30 mL) in an argon gas atmosphere, and then sodium hydride 0.4 g (10 mmol) was added. This reaction mixture was stirred at a room temperature for 30 minutes, and iodomethane 1.5 g (10 mmol) was added in an argon gas atmosphere, and then it was heated to 80 C. and stirred for 3 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and extracted with water (100 mL) and ethylacetate (100 mL3). Organic layers were concentrated under reduced pressure and after removing the solvent, it was purified by column chromatography using ethylacetate and hexane as developing solvents. (hexane: ethylacetate=1:3) Finally, 2-(1-methyl-1H-tetrazole-5-yl)pyridine was obtained. (0.4 g. 40%)

3) Synthesis of Os(tetraz-py).SUB.2.Cl.SUB.2 .[Chemical formula 16]

[0214] ##STR00066##

[0215] Potassium hexachloroosmate(IV) 0.10 g (0.21 mmol) and 2-(1-methyl-1H-tetrazole-5-yl)pyridine 0.7 g (0.42 mmol) prepared in 2) above were added in a 50 mL shrink flask, and dissolved in 5 mL ethylene glycol in an argon gas atmosphere, and then argon degassing was performed for 15 minutes. This reaction mixture was heated 15 to 180 C. and stirred for 1 hour. After completing the reaction, the reaction mixture was cooled to a room temperature and produced red precipitates were filtered under reduced pressure and removed. The filtrate was dropped in a sodium dithionite 1.0 M aqueous solution (200 mL), thereby obtaining precipitates of the reduced osmium complex. The produced solid was filtered under reduced pressure and washed with water several times, and then dried in a vacuum oven of 40 C. to obtain a green final compound osmium complex. (0.1 g, 84%) HRMS (.sup.192OS): m/z 584.0383([M.sup.+] required 584.04)

[0216] The entire preparation method of the compound of Chemical formula 16 is as the following Reaction formula 14.

##STR00067##

Example 1.15. Synthesis of Transition Metal Complex of Chemical Formula 17

1) Synthesis of 2-(1H-1,2,4-triazol-1-yl)pyridine

[0217] ##STR00068##

[0218] A reflux condenser and a gas inlet were equipped to a 250 mL two-neck round bottom flask, and 1H-1,2,4 triazole 3.0 g (43 mmol) and potassium tertiary butoxide 5.8 g (52 mmol) were added and dissolved in an anhydrous dimethylsulfoxide 40 mL in an argon gas atmosphere. 2-fluoropyridine 5.0 g (52 mmol) was added to this reaction mixture and heated to 100 C. in an argon gas atmosphere and stirred for 4 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and extracted with water (100 mL) and ethylacetate (100 mL3). Organic layers were collected and concentrated under reduced pressure and after removing the solvent, it was purified by column chromatography using ethylacetate and hexane as developing solvents. (hexane: ethylacetate=5:1) Finally, 2-(1H-1,2,4-triazol-1-yl)pyridine of a transparent solid was obtained. (4.3 g, 57%)

2) Synthesis of Os(1,2,4tz-py).SUB.2.Cl.SUB.2 .[Chemical formula 17]

[0219] ##STR00069##

[0220] Potassium hexachloroosmate(IV) 0.6 g (1.4 mmol) and 2-(1H-1,2,4-triazol-1-yl)pyridine 0.4 g (2.9 mmol) prepared in 1) above were added in a 250 mL shrink flask, and dissolved in 50 mL ethylene glycol in an argon gas atmosphere, and then argon degassing was performed for 15 minutes. This reaction mixture was heated to 180 C. and stirred for 30 minutes. After completing the reaction, the reaction mixture was cooled to a room temperature and produced red precipitates were filtered under reduced pressure and removed. The filtrate was dropped in a sodium dithionite 1.0 M aqueous solution (30 mL), thereby obtaining precipitates of the reduced osmium complex. The produced solid was filtered under reduced pressure and washed with water and acetonitrile several times, and then dried in a vacuum oven to obtain a crimson final compound osmium complex. (0.3 g, 62%)

[0221] The entire preparation method of the compound of Chemical formula 17 is as the following Reaction formula 15.

##STR00070##

Example 1.16. Synthesis of Transition Metal Complex of Chemical Formula 18

1) Synthesis of 2-(1H-1,2,3-triazol-1-yl)pyridine

[0222] ##STR00071##

[0223] A reflux condenser and a gas inlet were equipped to a 250 mL two-neck round bottom flask, and 1H-1,2,3 triazole 3.0 g (43 mmol) and potassium tertiary butoxide 5.8 g (52 mmol) were added and dissolved in an anhydrous dimethylsulfoxide 40 mL in an argon gas atmosphere. 2-fluoropyridine 5.0 g (52 mmol) was added to this reaction mixture and heated to 100 C. in an argon gas atmosphere and stirred for 4 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and extracted with water (100 mL) and ethylacetate (100 mL3). Organic layers were collected and concentrated under reduced pressure and after removing the solvent, it was purified by column chromatography using ethylacetate and hexane as developing solvents. (hexane: ethylacetate=5:1) Finally, 2-(1H-1,2,3-triazol-1-yl)pyridine of a transparent solid was obtained. (3.5 g, 56%)

2) Synthesis of Os(1,2,3tz-py).SUB.2.Cl.SUB.2 .[Chemical formula 18]

[0224] ##STR00072##

[0225] Potassium hexachloroosmate(IV) 0.6 g (1.4 mmol) and 2-(1H-1,2,3-triazol-1-yl)pyridine 0.4 g (2.9 mmol) prepared in 1) above were added in a 250 mL shrink flask, and dissolved in 50 mL ethylene glycol in an argon gas atmosphere, and then argon degassing was performed for 15 minutes. This reaction mixture was heated to 180 C. and stirred for 30 minutes. After completing the reaction, the reaction mixture was cooled to a room temperature and produced red precipitates were filtered under reduced pressure and removed. The filtrate was dropped in a sodium dithionite 1.0 M aqueous solution (30 mL), thereby obtaining precipitates of the reduced osmium complex. The produced solid was filtered under reduced pressure and washed with water and acetonitrile several times, and then dried in a vacuum oven to obtain a green final compound osmium complex. (0.4 g, 69%)

[0226] The entire preparation method of the compound of Chemical formula 18 is as the following Reaction formula 16.

##STR00073##

Example 1.17. Synthesis of Transition Metal Complex of Chemical Formula 19

1) Synthesis of 2-(1-methyl-1H-1,2,4-triazol-5-yl)pyridine

[0227] ##STR00074##

[0228] 2-(1H-1,2,4-triazol-5-yl)pyridine 1.0 g (6.8 mmol) and sodium hydride 0.4 g (0.01 mmol) were added in a 100 mL two-neck round bottom flask, and dissolved in anhydrous dimethylsulfoxide 50 mL. Methyl iodide 1.4 g (0.01 mmol) was dropped in this reaction mixture using a dropping funnel, and stirred at a room temperature for 24 hours. After completion, the reaction mixture was extracted with water (100 mL) and ethylacetate (100 mL3). Organic layers were collected and concentrated under reduced pressure, and after removing solvents, it was purified by column chromatography using ethylacetate and hexane as developing solvents. (hexane: ethylacetate=5:1) Finally, 2-(1-methyl-1H-1,2,4-triazol-5-yl)pyridine of a transparent solid was obtained. (0.9 g, 86%)

2) Synthesis of Os(4-Me-1,2,4tz-py).SUB.2.Cl.SUB.2 .[Chemical formula 19]

[0229] ##STR00075##

[0230] Potassium hexachloroosmate(IV) 0.6 g (1.4 mmol) and 2-(1-methyl-1H-1,2,4-triazol-5-yl)pyridine 0.5 g (2.9 mmol) prepared in 1) above were added in a 250 mL shrink flask, and dissolved in 50 mL ethylene glycol in an argon gas atmosphere, and then argon degassing was performed for 15 minutes. This reaction mixture was heated to 180 C. and stirred for 1 hour. After completing the reaction, the reaction mixture was cooled to a room temperature and produced red precipitates were filtered under reduced pressure and removed. The filtrate was dropped in a sodium dithionite 1.0 M aqueous solution (30 mL), thereby obtaining precipitates of the reduced osmium complex. The produced solid was filtered under reduced pressure and washed with water and acetonitrile several times, and then dried in a vacuum oven to obtain a green final compound osmium complex. (0.2 g, 25%).

[0231] The entire preparation method of the compound of Chemical formula 19 is as the following Reaction formula 17.

##STR00076##

Example 1.18. Synthesis of Transition Metal Complex of Chemical Formula 20

1) Synthesis of 2-(3,4-dimethyl-1H-pyrazol-1-yl)-4-methylpyridine

[0232] ##STR00077##

[0233] A reflux condenser and a gas inlet were equipped to a 250 mL two-neck round bottom flask, and 3,4-dimethylpyrazole 2.1 g (22 mmol) and potassium tertiary butoxide 2.5 g (22 mmol) were added and dissolved in an anhydrous dimethylsulfoxide 20 mL in an argon gas atmosphere. 2-bromo-4-methyl pyridine 3.5 g (20 mmol) was added to this reaction mixture and heated to 100 C. in an argon gas atmosphere and stirred for 18 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and extracted with water (100 mL) and ethylacetate (100 mL3). Organic layers were collected and concentrated under reduced pressure and after removing the solvent, it was purified by column chromatography using ethylacetate and hexane as developing solvents. (hexane: ethylacetate=3:1) Finally, 4-methyl-2-(3-methyl-1H-pyrazol-1-yl)pyridine of a transparent solid was obtained. (2.4 g, 63%)

2) Synthesis of Os(3,4-DiMe-pz-4-Me-py).SUB.2.Cl.SUB.2 .[Chemical formula 20]

[0234] ##STR00078##

[0235] Potassium hexachloroosmate(IV) 0.5 g (1.0 mmol) and 2-(3,4-dimethyl-1H-pyrazol-1-yl)-4-methylpyridine 0.4 g (2.0 mmol) prepared in 1) above were added in a 50 mL shrink flask, and dissolved in 15 mL ethylene glycol in an argon gas atmosphere, and then argon degassing was performed for 15 minutes. This reaction mixture was heated to 180 C. and stirred for 1 hour. After completing the reaction, the reaction mixture was cooled to a room temperature and produced red precipitates were filtered under reduced pressure and removed. The filtrate was dropped in a sodium dithionite 1.0 M aqueous solution (100 mL), thereby obtaining precipitates of the reduced osmium complex. The produced solid was filtered under reduced pressure and washed with water and acetonitrile several times, and then dried in a vacuum oven to obtain a green final compound osmium complex. (0.4 g, 62%) HRMS (.sup.192Os): m/z 636.1205([M.sup.+] required 636.1200)

[0236] The entire preparation method of the compound of Chemical formula 20 is as the following Reaction formula 18.

##STR00079##

Example 1.19. Synthesis of Transition Metal Complex of Chemical Formula 21

1) Synthesis of 2-(3,4-dimethyl-1H-pyrazol-1-yl)-4-methoxypyridine

[0237] ##STR00080##

[0238] A reflux condenser and a gas inlet were equipped to a 50 mL two-neck round bottom flask, and 3,4-dimethylpyrazole 0.6 g (6 mmol) and potassium tertiary butoxide 0.7 g (6 mmol) were added and dissolved in an anhydrous dimethylsulfoxide 8 mL in an argon gas atmosphere. 2-bromo-4-methoxy pyridine 1.0 g (5. mmol) was added to this reaction mixture and heated to 80 C. in an argon gas atmosphere and stirred for 6 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and extracted with water (50 mL) and ethylacetate (50 mL3). Organic layers were collected and concentrated under reduced pressure and after removing the solvent, it was purified by column chromatography using ethylacetate and hexane as developing solvents. (hexane: ethylacetate=3:1) Finally, 4-methyl-2-(3-methyl-1H-pyrazol-1-yl)pyridine of a transparent solid was obtained. (0.4 g, 37%)

2) Synthesis of Os(3,4-DiMe-pz-4-MeO-py).SUB.2.Cl.SUB.2 .[Chemical formula 21]

[0239] ##STR00081##

[0240] Potassium hexachloroosmate(IV) 0.5 g (1.0 mmol) and 2-(3,4-dimethyl-1H-pyrazol-1-yl)-4-methoxypyridine 0.4 g (2.0 mmol) prepared in 1) above were added in a 50 mL shrink flask, and dissolved in 15 mL ethylene glycol in an argon gas atmosphere, and then argon degassing was performed for 15 minutes. This reaction mixture was heated to 180 C. and stirred for 30 minutes. After completing the reaction, the reaction mixture was cooled to a room temperature and produced red precipitates were filtered under reduced pressure and removed. The filtrate was dropped in a sodium dithionite 1.0 M aqueous solution (100 mL), thereby obtaining precipitates of the reduced osmium complex. The produced solid was filtered under reduced pressure and washed with water and acetonitrile several times, and then dried in a vacuum oven to obtain a brown final compound osmium complex. (0.4 g, 64%) HRMS (.sup.192Os): m/z 668.1103([M.sup.+] required 668.1098)

[0241] The entire preparation method of the compound of Chemical formula 21 is as the following Reaction formula 19.

##STR00082##

Example 1.20. Synthesis of Transition Metal Complex of Chemical Formula 22

1) Synthesis of N,N-dimethyl-2-(4-methyl-1H-pyrazol-1-yl)pyridine-4-amine

[0242] ##STR00083##

[0243] A reflux condenser and a gas inlet were equipped to a 50 mL two-neck round bottom flask, and 4-dimethylamino-2-bromo pyridine 1.0 g (5.0 mmol), 4-methylpyrazole 1.2 g (15 mmol), cooper iodide 0.14 g (0.75 mmol), L-proline 0.17 g (1.5 mmol) and cesium carbonate 4.1 g (12.5 mmol) were added and dissolved in an anhydrous dimethylformamide 20 mL in an argon gas atmosphere. This reaction mixture was heated to 120 C. and stirred for 20 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and extracted with water (50 mL) and ethylacetate (50 mL3). Organic layers were collected and concentrated under reduced pressure and after removing the solvent, it was purified by column chromatography using ethylacetate and hexane as developing solvents. (hexane: ethylacetate=5:1) Finally, N,N-dimethyl-2-(4-methyl-1H-pyrazol-1-yl)pyridine-4-amine of a white solid was obtained. (0.5 g, 50%)

2) Synthesis of Os(4-Me-pz-4-DiAM-py).SUB.2.Cl.SUB.2 .[Chemical formula 22]

[0244] ##STR00084##

[0245] Potassium hexachloroosmate(IV) 0.6 g (1.2 mmol) and N,N-dimethyl-2-(4-methyl-1H-pyrazol-1-yl)pyridine-4-amine 0.5 g (2.4 mmol) prepared in 1) above were added in a 50 mL shrink flask, and dissolved in 15 mL ethylene glycol in an argon gas atmosphere, and then argon degassing was performed for 15 minutes. This reaction mixture was heated to 180 C. and stirred for 30 minutes. After completing the reaction, the reaction mixture was cooled to a room temperature and produced red precipitates were filtered under reduced pressure and removed. The filtrate was dropped in a sodium dithionite 1.0 M aqueous solution (100 mL), thereby obtaining precipitates of the reduced osmium complex. The produced solid was filtered under reduced pressure and washed with water and acetonitrile several times, and then dried in a vacuum oven to obtain a black-red final compound osmium complex. (0.5 g, 75%) HRMS (.sup.192Os): m/z 666.1421([M.sup.+] required 666.1418)

[0246] The entire preparation method of the compound of Chemical formula 22 is as the following Reaction formula 20.

##STR00085##

Example 1.21. Synthesis of transition metal complex of Chemical formula 23

1) Synthesis of Ru(DMSO).SUB.4.Cl.SUB.2

[0247] ##STR00086##

[0248] RuCl.sub.3*xH.sub.2O 0.9 g (4.3 mmol) and anhydrous dimethylsulfoxide (5 mL) were added in a 50 mL shrink flask and degassing was performed in an argon gas atmosphere for 10 minutes. This dark red suspension was heated to 170 C. and stirred for 30 minutes. After maintaining this temperature, until the color of this reaction solution was changed to dark yellow, the temperature was lowered to a room temperature to terminate the reaction. Acetone of 4 mL was added to this reaction solution and it was cooled to 0 C., and then left still for 45 hours. The produced solid was filtered under reduced pressure and washed with cool acetone. Finally, Ru(DMSO).sub.4Cl.sub.2 of a yellow solid was obtained. Without additional purification, it was used for the next reaction. (1.5 g, 75%)

2) Synthesis of Ru(pzpy).SUB.2.Cl.SUB.2 .[Chemical formula 23]

[0249] ##STR00087##

[0250] Ru(DMSO).sub.4Cl.sub.2 0.4 g (0.86 mmol), 2-(1H-pyrazol-1-yl)pyridine 0.25 g (1.7 mmol) prepared in the above experimental example, lithium chloride 1.8 g (43.0 mmol) and anhydrous dimethylformaide (15 mL) were added in a 50 mL shrink flask and degassing was performed for 10 minutes in an argon gas atmosphere. For light blocking, this reaction container was wrapped with aluminum foil and then it was stirred at 150 C. for 4 hours. After completing the reaction, acetone of 50 mL was added to the dark purple reaction solution and cooled at 0 C. for 24 hours. The black-purple solid was filtered under reduced pressure, and for removal of lithium chloride and by-products, it was washed with acetone until the color of the filtrate became transparent. The remaining dark purple solid was dried in a vacuum oven to obtain a final compound ruthenium complex. After that, it was left still for 45 hours. The produced solid was filtered under reduced pressure and washed with cold acetone. Finally, Ru(DMSO).sub.4Cl.sub.2 of a yellow solid was obtained. (0.25 g, 55%) HRMS: m/z 461.9710([M.sup.+] required 461.9690)

[0251] The entire preparation method of the compound of Chemical formula 23 is as the following Reaction formula 21.

##STR00088##

Example 1.22. Synthesis of Transition Metal Complex of Chemical Formula 24

1) Synthesis of Ru(4-Me-pz4-Me-py).SUB.2.Cl.SUB.2 .[Chemical formula 24]

[0252] ##STR00089##

[0253] Ru(DMSO).sub.4Cl.sub.2 0.4 g (0.86 mmol), 4-methyl-2-(4-methyl-1H-pyrazol-1-yl)pyridine 0.3 g (1.7 mmol) prepared in the above experimental example, lithium chloride 1.8 g (43.0 mmol) and anhydrous dimethylformaide (15 mL) were added in a 50 mL shrink flask and degassing was performed for 10 minutes in an argon gas atmosphere. For light blocking, this reaction container was wrapped with aluminum foil and then it was stirred at 150 C. for 4 hours. After completing the reaction, acetone of 50 mL was added to the dark purple reaction solution and cooled at 0 C. for 24 hours. The black-purple solid was filtered under reduced pressure, and for removal of lithium chloride and by-products, it was washed with acetone until the color of the filtrate became transparent. The remaining dark purple solid was dried in a vacuum oven to obtain a final compound ruthenium complex. (0.1 g, 23%) HRMS: m/z 518.0321([M.sup.+] required 518.0316)

[0254] The entire preparation method of the compound of Chemical formula 24 is as the following Reaction formula 22.

##STR00090##

Example 1.23. Synthesis of Transition Metal Complex of Chemical Formula 25

1) Synthesis of Fe(pzpy).SUB.2.Cl.SUB.2 .[Chemical formula 25]

[0255] ##STR00091##

[0256] FeCl.sub.3 1.6 g (10.0 mmol), 2-(1H-pyrazol-1-yl)pyridine 1.5 g (10.0 mmol) prepared in the experimental example, terephthalic acid 3.3 g (20.0 mmol), sodium hydroxide 0.8 g (20 mmol) and anhydrous ethanol (30 mL) were added in a 100 mL shrink flask, and degassing was performed in an argon gas atmosphere for 10 minutes. This reaction solution was stirred at 50 C. for 96 hours. After completing the reaction, the temperature was lowered to a room temperature, and the produced black-red solid was filtered under reduced pressure and washed with acetone. The black-red solid was dried in a vacuum oven to obtain a final compound iron complex. (1.0 g, 24%) HRMS: m/z 415.9971 ([M.sup.+] required 415.9995)

Example 2: Synthesis of Oxidation-Reduction Polymer Comprising the Transition Metal Complex According to the Present Invention

Example 2.1. Synthesis of Oxidation-Reduction Polymer of Chemical Formula 28

[0257] ##STR00092##

[0258] A reflux condenser, a gas inlet and a thermometer were equipped to a 100 mL three-neck round bottom flask, and Os(pzpy).sub.2Cl.sub.2 [Chemical formula 3] 0.12 g (0.22 mmol) prepared in Example 1.1. was added and completely dissolved in ethanol 10 mL in an argon gas atmosphere. Polyvinyl imidazole (Mn=10,000 g/mol) 0.1 g completely dissolved in ethanol 20 mL was added to this reaction mixture and heated to 100 C. and stirred for 2 days. After completing the reaction, the reaction mixture was cooled to a room temperature and dropped in diethyl ether to obtain polymer precipitates. The produced solids were filtered under reduced pressure and washed with diethyl ether several times, and then dried in a vacuum oven of 40 C. for 24 hours to finally obtain a dark green oxidation-reduction polymer (PVIOs(pzpy).sub.2Cl) of Chemical formula 25 of 0.2 g. (0.20 g, 91%)

Example 2.2. Synthesis of Oxidation-Reduction Polymer of Chemical Formula 29

[0259] ##STR00093##

[0260] A reflux condenser, a gas inlet and a thermometer were equipped to a 100 mL three-neck round bottom flask, and Os(pz-2-Me-py).sub.2Cl.sub.2 [Chemical formula 4] 0.13 g (0.22 mmol) prepared in Example 1.2. was added and completely dissolved in ethanol 10 mL in an argon gas atmosphere. Polyvinyl imidazole (Mn=10,000 g/mol) 0.1 g completely dissolved in ethanol 20 mL was added to this reaction mixture and heated to 100 C. and stirred for 2 days. After completing the reaction, the reaction mixture was cooled to a room temperature and dropped in diethyl ether to obtain polymer precipitates. The produced solids were filtered under reduced pressure and washed with diethyl ether several times, and then dried in a vacuum oven of 40 C. for 24 hours to finally obtain a dark green oxidation-reduction polymer (PVIOs(pz-2-Mepy).sub.2Cl) of Chemical formula 26 of 0.2 g. (0.20 g, 87%)

Example 2.3. Synthesis of Oxidation-Reduction Polymer of Chemical Formula 30

[0261] ##STR00094##

[0262] Os(pz-4-MeO-py).sub.2Cl.sub.2 [Chemical formula 5] 0.13 g (0.22 mmol) prepared in Example 1.3. was added in a 100 mL shrink flask and completely dissolved in ethanol 10 mL in an argon gas atmosphere. Polyvinyl imidazole (Mn=10,000 g/mol) 0.1 g completely dissolved in ethanol 20 mL was added to this reaction mixture and heated to 120 C. and stirred for 24 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and dropped in diethyl ether to obtain polymer precipitates. The produced solids were filtered under reduced pressure and washed with diethyl ether several times, and then dried in a vacuum oven of 40 C. for 24 hours to finally obtain a dark green oxidation-reduction polymer (PVIOs(pz-4-MeO-py).sub.2CI) of Chemical formula 27 of 0.2 g. (0.21 g, 89%)

Example 2.4. Synthesis of Oxidation-Reduction Polymer of Chemical Formula 31

[0263] ##STR00095##

[0264] Os(pz-4-Me-py).sub.2Cl.sub.2 [Chemical formula 6] 0.31 g (0.53 mmol) prepared in Example 1.4. was added in a 100 mL shrink flask and completely dissolved in ethanol 10 mL in an argon gas atmosphere. Polyvinyl imidazole (Mn=10,000 g/mol) 0.2 g completely dissolved in ethanol 30 mL was added to this reaction mixture and heated to 120 C. and stirred for 36 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and dropped in diethyl ether to obtain polymer precipitates. The produced solids were filtered under reduced pressure and washed with diethyl ether several times, and then dried in a vacuum oven of 40 C. for 24 hours to finally obtain a dark green oxidation-reduction polymer (PVIOs(pz-4-Me-py).sub.2CI) of Chemical formula 28 of 0.4 g. (0.4 g, 78%)

Example 2.5 Synthesis of Oxidation-Reduction Polymer of Chemical Formula 32

[0265] ##STR00096##

[0266] Os(3-Me-pz-4-Me-py).sub.2Cl.sub.2 [Chemical formula 7] 0.27 g (0.44 mmol) prepared in Example 1.5. was added in a 100 mL shrink flask and completely dissolved in ethanol 20 mL in an argon gas atmosphere. Polyvinyl imidazole (Mn=10,000 g/mol) 0.2 g completely dissolved in ethanol 30 mL was added to this reaction mixture and heated to 120 C. and stirred for 24 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and dropped in diethyl ether to obtain polymer precipitates. The produced solids were filtered under reduced pressure and washed with diethyl ether several times, and then dried in a vacuum oven of 40 C. for 24 hours to finally obtain a dark green oxidation-reduction polymer (PVIOs(3-Me-pz-4-Me-py).sub.2Cl) of Chemical formula 29 of 0.4 g. (0.41 g, 87%)

Example 2.6. Synthesis of Oxidation-Reduction Polymer of Chemical Formula 33

[0267] ##STR00097##

[0268] Os(3-Me-pz-4-MeO-py).sub.2Cl.sub.2 [Chemical formula 8] 0.14 g (0.22 mmol) prepared in Example 1.6. was added in a 100 mL shrink flask and completely dissolved in ethanol 10 mL in an argon gas atmosphere. Polyvinyl imidazole (Mn=10,000 g/mol) 0.1 g completely dissolved in ethanol 20 mL was added to this reaction mixture and heated to 120 C. and stirred for 24 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and dropped in diethyl ether to obtain polymer precipitates. The produced solids were filtered under reduced pressure and washed with diethyl ether several times, and then dried in a vacuum oven of 40 C. for 24 hours to finally obtain a dark green oxidation-reduction polymer (PVIOs(3-Me-pz-4-MeO-py).sub.2Cl) of Chemical formula 30 of 0.22 g. (0.22 g, 92%)

Example 2.7. Synthesis of Oxidation-Reduction Polymer of Chemical Formula 34

[0269] ##STR00098##

[0270] Os(4-Me-pz-4-Me-py).sub.2Cl.sub.2 [Chemical formula 9] 0.8 g (1.32 mmol) prepared in Example 1.7. was added in a 250 mL shrink flask and completely dissolved in ethanol 50 mL in an argon gas atmosphere. Polyvinyl imidazole (Mn=10,000 g/mol) 0.5 g completely dissolved in ethanol 50 mL was added to this reaction mixture and heated to 120 C. and stirred for 24 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and dropped in diethyl ether to obtain polymer precipitates. The produced solids were filtered under reduced pressure and washed with diethyl ether several times, and then dried in a vacuum oven of 40 C. for 24 hours to finally obtain a dark green oxidation-reduction polymer (PVIOs(4-Me-pz-4-Me-py).sub.2Cl) of Chemical formula 31 of 1.21 g. (1.21 g, 93%)

Example 2.8. Synthesis of Oxidation-Reduction Polymer of Chemical Formula 35

[0271] ##STR00099##

[0272] Os(4-Me-pz-4-MeO-py).sub.2Cl.sub.2 [Chemical formula 10] 0.14 g (0.22 mmol) prepared in Example 1.8. was added in a 100 mL shrink flask and completely dissolved in ethanol 10 mL in an argon gas atmosphere. Polyvinyl imidazole (Mn=10,000 g/mol) 0.1 g completely dissolved in ethanol 20 mL was added to this reaction mixture and heated to 120 C. and stirred for 24 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and dropped in diethyl ether to obtain polymer precipitates. The produced solids were filtered under reduced pressure and washed with diethyl ether several times, and then dried in a vacuum oven of 40 C. for 24 hours to finally obtain a dark green oxidation-reduction polymer (PVIOs(4-Me-pz-4-MeO-py).sub.2Cl) of Chemical formula 32 of 0.20 g. (0.20 g, 83%)

Example 2.9. Synthesis of Oxidation-Reduction Polymer of Chemical Formula 36

[0273] ##STR00100##

[0274] A reflux condenser, a gas inlet and a thermometer were equipped to a 100 mL three-neck round bottom flask, and Os(Dmtz-py).sub.2Cl.sub.2 [Chemical formula 11] 0.13 g (0.22 mmol) prepared in Example 1.9. was added and completely dissolved in ethanol 10 mL in an argon gas atmosphere. Polyvinyl imidazole (Mn=10,000 g/mol) 0.1 g completely dissolved in ethanol 20 mL was added to this reaction mixture and heated to 100 C. and stirred for 2 days. After completing the reaction, the reaction mixture was cooled to a room temperature and dropped in diethyl ether to obtain polymer precipitates. The produced solids were filtered under reduced pressure and washed with diethyl ether several times, and then dried in a vacuum oven of 40 C. for 24 hours to finally obtain a brown oxidation-reduction polymer (PVIOs(Dmtz-py).sub.2Cl) of Chemical formula 33 of 0.15 g. (0.15 g, 65%)

Example 2.10. Synthesis of Oxidation-Reduction Polymer of Chemical Formula

[0275] ##STR00101##

[0276] A reflux condenser, a gas inlet and a thermometer were equipped to a 100 mL three-neck round bottom flask, and Os(3-Bu-tz-py).sub.2Cl.sub.2 [Chemical formula 13] 0.12 g (0.18 mmol) prepared in Example 1.11. was added and completely dissolved in ethanol 10 mL in an argon gas atmosphere. Polyvinyl imidazole (Mn=10,000 g/mol) 85 mg completely dissolved in ethanol 20 mL was added to this reaction mixture and heated to 100 C. and stirred for 2 days. After completing the reaction, the reaction mixture was cooled to a room temperature and dropped in diethyl ether to obtain polymer precipitates. The produced solids were filtered under reduced pressure and washed with diethyl ether several times, and then dried in a vacuum oven of 40 C. for 24 hours to finally obtain a red PVIOs polymer (PVIOs(3-Bu-tz-py).sub.2Cl) of Chemical formula 34 of 0.2 g. (0.2 g. 95%)

Example 2.11. Synthesis of Oxidation-Reduction Polymer of Chemical Formula 38

[0277] ##STR00102##

[0278] A reflux condenser, a gas inlet and a thermometer were equipped to a 100 mL three-neck round bottom flask, and Os(3-motz-py).sub.2Cl.sub.2 [Chemical formula 15] 0.15 g (0.22 mmol) prepared in Example 1.13. was added and completely dissolved in ethanol 10 mL in an argon gas atmosphere. Polyvinyl imidazole (Mn=10,000 g/mol) 0.1 g completely dissolved in ethanol 20 mL was added to this reaction mixture and heated to 100 C. and stirred for 2 days. After completing the reaction, the reaction mixture was cooled to a room temperature and dropped in diethyl ether to obtain polymer precipitates. The produced solids were filtered under reduced pressure and washed with diethyl ether several times, and then dried in a vacuum oven of 40 C. for 24 hours to finally obtain a brown oxidation-reduction polymer (PVIOs(3-motz-py).sub.2Cl) of Chemical formula 35 of 0.12 g. (0.12 g, 48%)

Example 2.12. Synthesis of Oxidation-Reduction Polymer of Chemical Formula 39

[0279] ##STR00103##

[0280] A reflux condenser, a gas inlet and a thermometer were equipped to a 100 mL three-neck round bottom flask, and Os(1,2,3-tz-py).sub.2Cl.sub.2 [Chemical formula 18] 0.12 g (0.22 mmol) prepared in Example 1.16. was added and completely dissolved in ethanol 10 mL in an argon gas atmosphere. Polyvinyl imidazole (Mn=10,000 g/mol) 0.1 g completely dissolved in ethanol 20 mL was added to this reaction mixture and heated to 110 C. and stirred for 2 days. After completing the reaction, the reaction mixture was cooled to a room temperature and dropped in diethyl ether to obtain polymer precipitates. The produced solids were filtered under reduced pressure and washed with diethyl ether several times, and then dried in a vacuum oven of 40 C. for 24 hours to finally obtain a red oxidation-reduction polymer (PVIOs(1,2,3-tz-py).sub.2Cl) of Chemical formula 36 of 0.22 g. (0.21 g, 96%)

Example 2.13. Synthesis of Oxidation-Reduction Polymer of Chemical Formula 40

[0281] ##STR00104##

[0282] Os(3,4-DiMe-pz-4-Me-py).sub.2Cl.sub.2 [Chemical formula 20] 0.17 g (0.27 mmol) prepared in Example 1.18. was added in a 100 mL shrink flask and completely dissolved in ethanol 15 mL in an argon gas atmosphere. Polyvinyl imidazole (Mn=10,000 g/mol) 0.1 g completely dissolved in ethanol 20 mL was added to this reaction mixture and heated to 120 C. and stirred for 24 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and dropped in diethyl ether to obtain polymer precipitates. The produced solids were filtered under reduced pressure and washed with diethyl ether several times, and then dried in a vacuum oven of 40 C. for 24 hours to finally obtain a dark green oxidation-reduction polymer (PVIOs(3,4-DiMe-pz-4-Me-py).sub.2Cl) of Chemical formula 37 of 0.22 g. (0.22 g, 81%)

Example 2.14. Synthesis of Oxidation-Reduction Polymer of Chemical Formula 41

[0283] ##STR00105##

[0284] Os(3,4-Dime-pz-4-MeO-py).sub.2Cl.sub.2 [Chemical formula 21] 0.29 g (0.43 mmol) prepared in Example 1.19. was added in a 100 mL shrink flask and completely dissolved in ethanol 20 mL in an argon gas atmosphere. Polyvinyl imidazole (Mn=10,000 g/mol) 0.2 g completely dissolved in ethanol 30 mL was added to this reaction mixture and heated to 120 C. and stirred for 48 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and dropped in diethyl ether to obtain polymer precipitates. The produced solids were filtered under reduced pressure and washed with diethyl ether several times, and then dried in a vacuum oven of 40 C. for 24 hours to finally obtain a brown oxidation-reduction polymer (PVIOs(3,4-Dime-pz-4-MeO-py).sub.2CI) of Chemical formula 38 of 0.40 g. (0.40 g, 81%)

Example 2.15. Synthesis of Oxidation-Reduction Polymer of Chemical Formula 42

[0285] ##STR00106##

[0286] Os(4-Me-pz-4-DiAM-py).sub.2Cl.sub.2 [Chemical formula 22] 0.18 g (0.27 mmol) prepared in Example 1.20. was added in a 100 mL shrink flask and completely dissolved in ethanol 20 mL in an argon gas atmosphere. Polyvinyl imidazole (Mn=10,000 g/mol) 0.1 g completely dissolved in ethanol 20 mL was added to this reaction mixture and heated to 120 C. and stirred for 18 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and dropped in diethyl ether to obtain polymer precipitates. The produced solids were filtered under reduced pressure and washed with diethyl ether several times, and then dried in a vacuum oven of 40 C. for 24 hours to finally obtain a brown oxidation-reduction polymer (PVIOs(4-Me-pz-4-DiAM-py).sub.2CI) of Chemical formula 39 of 0.24 g. (0.24 g, 86%)

Example 2.16. Synthesis of Oxidation-Reduction Polymer of Chemical Formula

[0287] ##STR00107##

[0288] Os(4-Me-pz-4-DiAM-py).sub.2Cl.sub.2 [Chemical formula 22] 0.5 g (0.76 mmol) prepared in Example 1.20. was added in a 250 mL shrink flask and completely dissolved in ethanol 60 mL in an argon gas atmosphere. Polyvinyl pyridine (Mn=160,000 g/mol) 0.32 g completely dissolved in ethanol 30 mL was added to this reaction mixture and heated to 120 C. and stirred for 24 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and dropped in diethyl ether to obtain polymer precipitates. The produced solids were filtered under reduced pressure and washed with diethyl ether several times, and then dried in a vacuum oven of 40 C. for 24 hours to finally obtain a brown oxidation-reduction polymer (PVPOs(4-Me-pz-4-DiAM-py).sub.2Cl) of Chemical formula 40 of 0.70 g. (0.70 g, 85%)

Example 2.17. Synthesis of Oxidation-Reduction Polymer of Chemical Formula 44

[0289] ##STR00108##

[0290] Ru(4-Me-pz4-Me-py).sub.2Cl.sub.2 [Chemical formula 24] 0.14 g (0.27 mmol) prepared in Example 1.22. was added in a 100 mL shrink flask and completely dissolved in ethanol 30 mL in an argon gas atmosphere. Polyvinyl imidazole (Mn=10,000 g/mol) 0.1 g completely dissolved in ethanol 20 mL was added to this reaction mixture and heated to 100 C. and stirred for 12 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and dropped in diethyl ether to obtain polymer precipitates. The produced solids were filtered under reduced pressure and washed with diethyl ether several times, and then dried in a vacuum oven of 40 C. for 24 hours to finally obtain a dark green oxidation-reduction polymer (PVIRu(4-Me-pz4-Me-py).sub.2Cl) of Chemical formula 44 of 0.24 g. (0.2 g, 83%)

Example 2.18. Synthesis of Oxidation-Reduction Polymer of Chemical Formula 45

[0291] ##STR00109##

[0292] Fe(pzpy).sub.2Cl.sub.2 [Chemical formula 25] 0.11 g (0.27 mmol) prepared in Example 1.23. was added in a 100 mL shrink flask and completely dissolved in ethanol 25 mL in an argon gas atmosphere. Polyvinyl imidazole (Mn=10,000 g/mol) 0.1 g completely dissolved in ethanol 20 mL was added to this reaction mixture and heated to 80 C. and stirred for 24 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and dropped in diethyl ether to obtain polymer precipitates. The produced solids were filtered under reduced pressure and washed with diethyl ether several times, and then dried in a vacuum oven of 40 C. for 24 hours to finally obtain a red-brown oxidation-reduction polymer (PVIFe(pzpy).sub.2Cl) of Chemical formula 45 of 0.1 g. (0.1 g, 47%)

Example 3. Synthesis of Oxidation-Reduction Polymer Comprising the Transition Metal Complex According to the Present Invention and a Crosslinkable Functional Group

Example 3.1. Synthesis of Oxidation-Reduction Polymer of Chemical Formula 48

[0293] ##STR00110##

[0294] A reflux condenser, a gas inlet and a thermometer were equipped to a 100 mL three-neck round bottom flask, and the [Chemical formula 28] polymer prepared in Example 2.1. of 0.2 g was added and completely dissolved in methanol in an argon gas atmosphere. 2-bromoethylamine 20 mg (0.1 mmol) was added to this reaction mixture and heated to 80 C. and stirred for 24 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and dropped in diethyl ether to obtain polymer precipitates. The produced solids were filtered under reduced pressure and washed with diethyl ether several times. In order to exchange a Br ion comprised in the reactant to a Cl ion, the solids filtered in a 200 mL beaker and water 50 mL were added and dissolved all, and then an ion exchange resin (AG1x4) 20 mL was added and stirred for 24 hours. This reaction mixture was filtered under reduced pressure to remove the resin and the filtered aqueous solution was lyophilized to remove water, thereby finally obtaining a green [Chemical formula 48] polymer of 0.2 g. (0.2 g. 90%)

Example 3.2. Synthesis of Oxidation-Reduction Polymer of Chemical Formula 49

[0295] ##STR00111##

[0296] A reflux condenser, a gas inlet and a thermometer were equipped to a 100 mL three-neck round bottom flask, and the [Chemical formula 30] polymer prepared in Example 2.3. of 0.2 g was added and completely dissolved in methanol in an argon gas atmosphere. 2-bromoethylamine 20 mg (0.1 mmol) was added to this reaction mixture and heated to 80 C. and stirred for 24 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and dropped in diethyl ether to obtain polymer precipitates. The produced solids were filtered under reduced pressure and washed with diethyl ether several times. In order to exchange a Br ion comprised in the reactant to a Cl ion, the solids filtered in a 200 mL beaker and water 50 mL were added and dissolved all, and then an ion exchange resin (AG1x4) 20 mL was added and stirred for 24 hours. This reaction mixture was filtered under reduced pressure to remove the resin and the filtered aqueous solution was lyophilized to remove water, thereby finally obtaining a green [Chemical formula 49] polymer of 0.2 g. (0.2 g. 90%)

Example 3.3. Synthesis of Oxidation-Reduction Polymer of Chemical Formula 50

[0297] ##STR00112##

[0298] A reflux condenser, a gas inlet and a thermometer were equipped to a 100 mL three-neck round bottom flask, and the [Chemical formula 31] polymer prepared in Example 2.4. of 0.4 g was added and completely dissolved in methanol in an argon gas atmosphere. 2-bromoethylamine 50 mg (0.25 mmol) was added to this reaction mixture and heated to 80 C. and stirred for 24 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and dropped in diethyl ether to obtain polymer precipitates. The produced solids were filtered under reduced pressure and washed with diethyl ether several times. In order to exchange a Br ion comprised in the reactant to a Cl ion, the solids filtered in a 200 mL beaker and water 50 mL were added and dissolved all, and then an ion exchange resin (AG1x4) 20 mL was added and stirred for 24 hours. This reaction mixture was filtered under reduced pressure to remove the resin and the filtered aqueous solution was lyophilized to remove water, thereby finally obtaining a green [Chemical formula 50] polymer of 0.41 g. (0.41 g. 91%)

Example 3.4. Synthesis of Oxidation-Reduction Polymer of Chemical Formula 51

[0299] ##STR00113##

[0300] A reflux condenser, a gas inlet and a thermometer were equipped to a 100 mL three-neck round bottom flask, and the [Chemical formula 34] polymer prepared in Example 2.7. of 0.4 g was added and completely dissolved in methanol in an argon gas atmosphere. 2-bromoethylamine 50 mg (0.25 mmol) was added to this reaction mixture and heated to 80 C. and stirred for 24 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and dropped in diethyl ether to obtain polymer precipitates. The produced solids were filtered under reduced pressure and washed with diethyl ether several times. In order to exchange a Br ion comprised in the reactant to a Cl ion, the solids filtered in a 200 mL beaker and water 50 mL were added and dissolved all, and then an ion exchange resin (AG1x4) 20 mL was added and stirred for 24 hours. This reaction mixture was filtered under reduced pressure to remove the resin and the filtered aqueous solution was lyophilized to remove water, thereby finally obtaining a green [Chemical formula 51] polymer of 0.4 g. (0.4 g. 90%)

Example 3.5. Synthesis of Oxidation-Reduction Polymer of Chemical Formula 52

[0301] ##STR00114##

[0302] A reflux condenser, a gas inlet and a thermometer were equipped to a 100 mL three-neck round bottom flask, and the [Chemical formula 35] polymer prepared in Example 2.8. of 0.2 g was added and completely dissolved in methanol in an argon gas atmosphere. 2-bromoethylamine 20 mg (0.1 mmol) was added to this reaction mixture and heated to 80 C. and stirred for 24 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and dropped in diethyl ether to obtain polymer precipitates. The produced solids were filtered under reduced pressure and washed with diethyl ether several times. In order to exchange a Br ion comprised in the reactant to a Cl ion, the solids filtered in a 200 mL beaker and water 50 mL were added and dissolved all, and then an ion exchange resin (AG1x4) 20 mL was added and stirred for 24 hours. This reaction mixture was filtered under reduced pressure to remove the resin and the filtered aqueous solution was lyophilized to remove water, thereby finally obtaining a green [Chemical formula 52] polymer of 0.2 g. (0.2 g. 90%)

Example 3.6. Synthesis of Oxidation-Reduction Polymer of Chemical Formula 53

[0303] ##STR00115##

[0304] A reflux condenser, a gas inlet and a thermometer were equipped to a 100 mL three-neck round bottom flask, and the [Chemical formula 40] polymer prepared in Example 2.13. of 0.2 g was added and completely dissolved in methanol in an argon gas atmosphere. 2-bromoethylamine 20 mg (0.1 mmol) was added to this reaction mixture and heated to 80 C. and stirred for 24 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and dropped in diethyl ether to obtain polymer precipitates. The produced solids were filtered under reduced pressure and washed with diethyl ether several times. In order to exchange a Br ion comprised in the reactant to a Cl ion, the solids filtered in a 200 mL beaker and water 50 mL were added and dissolved all, and then an ion exchange resin (AG1x4) 20 mL was added and stirred for 24 hours. This reaction mixture was filtered under reduced pressure to remove the resin and the filtered aqueous solution was lyophilized to remove water, thereby finally obtaining a green [Chemical formula 53] polymer of 0.2 g. (0.2 g. 90%)

Example 3.7. Synthesis of Oxidation-Reduction Polymer of Chemical Formula 54

[0305] ##STR00116##

[0306] A reflux condenser, a gas inlet and a thermometer were equipped to a 100 mL three-neck round bottom flask, and the [Chemical formula 41] polymer prepared in Example 2.14. of 0.2 g was added and completely dissolved in methanol in an argon gas atmosphere. 2-bromoethylamine 20 mg (0.1 mmol) was added to this reaction mixture and heated to 80 C. and stirred for 24 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and dropped in diethyl ether to obtain polymer precipitates. The produced solids were filtered under reduced pressure and washed with diethyl ether several times. In order to exchange a Br ion comprised in the reactant to a Cl ion, the solids filtered in a 200 mL beaker and water 50 mL were added and dissolved all, and then an ion exchange resin (AG1x4) 20 mL was added and stirred for 24 hours. This reaction mixture was filtered under reduced pressure to remove the resin and the filtered aqueous solution was lyophilized to remove water, thereby finally obtaining a green [Chemical formula 54] polymer of 0.2 g. (0.2 g. 90%)

EXAMPLE 3.8. Synthesis of Oxidation-Reduction Polymer of Chemical Formula 57

[0307] ##STR00117##

[0308] A reflux condenser, a gas inlet and a thermometer were equipped to a 100 mL three-neck round bottom flask, and the [Chemical formula 42] polymer prepared in Example 2.15. of 0.2 g was added and completely dissolved in methanol in an argon gas atmosphere. 2-bromoethylamine 20 mg (0.1 mmol) was added to this reaction mixture and heated to 80 C. and stirred for 24 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and dropped in diethyl ether to obtain polymer precipitates. The produced solids were filtered under reduced pressure and washed with diethyl ether several times. In order to exchange a Br ion comprised in the reactant to a Cl ion, the solids filtered in a 200 mL beaker and water 50 mL were added and dissolved all, and then an ion exchange resin (AG1x4) 20 mL was added and stirred for 24 hours. This reaction mixture was filtered under reduced pressure to remove the resin and the filtered aqueous solution was lyophilized to remove water, thereby finally obtaining a red [Chemical formula 57] polymer of 0.2 g. (0.2 g. 90%)

Example 3.9. Synthesis of Oxidation-Reduction Polymer of Chemical Formula 58

[0309] ##STR00118##

[0310] A reflux condenser, a gas inlet and a thermometer were equipped to a 100 mL three-neck round bottom flask, and the [Chemical formula 43] polymer prepared in Example 2.16. of 0.4 g was added and completely dissolved in methanol in an argon gas atmosphere. 2-bromoethylamine 30 mg (0.15 mmol) was added to this reaction mixture and heated to 80 C. and stirred for 24 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and dropped in diethyl ether to obtain polymer precipitates. The produced solids were filtered under reduced pressure and washed with diethyl ether several times. In order to exchange a Br ion comprised in the reactant to a Cl ion, the solids filtered in a 200 mL beaker and water 50 mL were added and dissolved all, and then an ion exchange resin (AG1x4) 20 mL was added and stirred for 24 hours. This reaction mixture was filtered under reduced pressure to remove the resin and the filtered aqueous solution was lyophilized to remove water, thereby finally obtaining a red [Chemical formula 58] polymer of 0.41 g. (0.41 g. 95%)

Example 3.10. Synthesis of Oxidation-Reduction Polymer of Chemical Formula 59

[0311] ##STR00119##

[0312] A reflux condenser, a gas inlet and a thermometer were equipped to a 100 mL three-neck round bottom flask, and the [Chemical formula 34] polymer prepared in Example 2.7. of 0.4 g was added and completely dissolved in methanol in an argon gas atmosphere. Diethylene glycol-2-bromoethylmethylether 24 mg (0.1 mmol) was added to this reaction mixture and heated to 80 C. and stirred for 24 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and dropped in diethyl ether to obtain polymer precipitates. The produced solids were filtered under reduced pressure and washed with diethyl ether several times. In order to exchange a Br ion comprised in the reactant to a Cl ion, the solids filtered in a 200 mL beaker and water 50 mL were added and dissolved all, and then an ion exchange resin (AG1x4) 20 mL was added and stirred for 24 hours. This reaction mixture was filtered under reduced pressure to remove the resin and the filtered aqueous solution was lyophilized to remove water, thereby finally obtaining a green [Chemical formula 59] polymer of 0.4 g. (0.4 g. 94%)

Example 3.11. Synthesis of Oxidation-Reduction Polymer of Chemical Formula 60

[0313] ##STR00120##

[0314] A reflux condenser, a gas inlet and a thermometer were equipped to a 100 mL three-neck round bottom flask, and the [Chemical formula 44] polymer prepared in Example 2.17. of 0.4 g was added and completely dissolved in methanol in an argon gas atmosphere. 2-bromoethylamine 30 mg (0.15 mmol) was added to this reaction mixture and heated to 80 C. and stirred for 24 hours. After completing the reaction, the reaction mixture was cooled to a room temperature and dropped in diethyl ether to obtain polymer precipitates. The produced solids were filtered under reduced pressure and washed with diethyl ether several times. In order to exchange a Br ion comprised in the reactant to a Cl ion, the solids filtered in a 200 mL beaker and water 50 mL were added and dissolved all, and then an ion exchange resin (AG1x4) 20 mL was added and stirred for 24 hours. This reaction mixture was filtered under reduced pressure to remove the resin and the filtered aqueous solution was lyophilized to remove water, thereby finally obtaining a red [Chemical formula 60] polymer of 0.35 g. (0.35 g. 81%)

Experimental Example 1: Confirmation of Electrochemical Characteristics of the Transition Metal Complexes and Oxidation-Reduction Polymers According to the Present Invention Using Cyclic Voltammetry

[0315] In order to confirm the performance as an electron transfer mediator of the transition metal complex having a bidentate ligand comprising pyrazole, triazole, tetrazole, oxadiazole or thiadiazole or the like and oxidation-reduction polymer comprising the same according to the present invention, electrochemical characteristics was measured using cyclic voltammetry according to the following experimental method.

Experimental Method

[0316] 1. 20 mg of each compound (transition metal complex) of Chemical formulas 3, 4, 9, 11, 14, 15, 16, 17, 18, 20, 22, 23, 24, and 25 according to the present invention was dissolved in 0.1 M tetrabutylammonium perchlorate dimethyl sulfoxide solution of 2 mL.

[0317] 20 mg of each compound of Chemical formulas 28, 34, 40, and 42 (oxidation-reduction polymer) and compound of Chemical formulas 48, 51, 57, and 59 (oxidation-reduction polymer comprising a crosslinkable functional group) according to the present invention was dissolved in deionized water and 0.1 M sodium chloride solution of 5 mL. As a comparison group, 20 mg of the compound of the following Chemical formula 61 was dissolved in deionized water and 0.1 M sodium chloride solution of 5 mL.

##STR00121## [0318] 2. In order to remove oxygen in the solution, degassing was performed with argon for 510 minutes. [0319] 3. A working electrode, a reference electrode, and a counter electrode were connected to the solution in which oxygen was degassed, and a change in electrical signals according to a change in voltage was measured in an argon gas atmosphere. [0320] 4. This experimental result was shown in Table 1 to Table 3, and FIG. 1a to FIG. 10o, FIG. 2 and FIG. 3 below.

[0321] The experimental results of each compound was shown corresponding to the drawings below:

[0322] Chemical formula 3 (FIG. 1a), Chemical formula 4 (FIG. 1b), Chemical formula 9 (FIG. 1c), Chemical formula 11 (FIG. 1d), Chemical formula 14 (FIG. 1e), Chemical formula 15 (FIG. 1f), Chemical formula 16 (FIG. 1g), Chemical formula 17 (FIG. 1h), Chemical formula 18 (FIG. 1i), Chemical formula 20 (FIG. 1j), Chemical formula 22 (FIG. 1k), Chemical formula 23 (FIG. 1l), Chemical formula 24 (FIG. 1m), Chemical formula 25 (FIG. 1n), Chemical formula 3, 4, 11, 14, 15, 16 (FIG. 10o),

[0323] Chemical formula 3 (comparison group), 28, 34, 40, 42 (FIG. 2),

[0324] Chemical formula 28 (comparison group), 48, 51, 57, 59, 61 (comparison group) (FIG. 3).

Experimental Materials/Conditions

[0325] Working electrode: Free carbon electrode (dia: 3.0 mm) [0326] Reference electrode: Ag/AgCl electrode [0327] Counter electrode: Platinum rod [0328] Test parameters [0329] Equipment: EmStat(PalmSens Co.) [0330] Technique: cyclic voltammetry [0331] Potential range: 1.01.0V [0332] Scan rate: 10 mV/s

TABLE-US-00001 TABLE 1 Transition metal complex E.sub.pc (V) E.sub.pa (V) [Chemical formula3] 0.03 0.12 [Chemical formula4] 0.05 0.12 [Chemical formula 9] 0.08 0.18 [Chemical formula 11] 0.16 0.27 [Chemical formula 14] 0.18 0.26 [Chemical formula 15] 0.04 0.16 [Chemical formula 16] 0.26 0.10 [Chemical formula 17] 0.42 0.56 [Chemical formula 18] 0.40 0.49 [Chemical formula 20] 0.1 0.24 [Chemical formula 22] 0.32 0.47 [Chemical formula 23] 0.50 0.60 [Chemical formula 24] 0.49 0.36 [Chemical formula 25] 0.71 0.63

TABLE-US-00002 TABLE 2 Oxidation-reduction complex E.sub.pc (V) E.sub.pa (V) [Chemical formula3] 0.03 0.12 [Chemical formula 28] 0.33 0.17 [Chemical formula 34] 0.24 0.14 [Chemical formula 40] 0.26 0.12 [Chemical formula 42] 0.12 0.03

TABLE-US-00003 TABLE 3 Oxidation-reduction complex comprising a crosslinkable functional group E.sub.pc (V) E.sub.pa (V) [Chemical formula 48] 0.33 0.17 [Chemical formula 51] 0.26 0.14 [Chemical formula 57] 0.15 0.05 [Chemical formula 59] 0.26 0.13 [Chemical formula 61] 0.39 0.29

[0333] As shown in Table 1 and FIG. 1a to FIG. 1o above, it was confirmed that the transition metal complex according to the present invention had various potential values depending on the ligand type.

[0334] As shown in Table 2 and FIG. 2 above, it was confirmed that the intrinsic potential value of the complex was changed when the transition metal complex according to the present invention was synthesized to an oxidation-reduction polymer.

[0335] In addition, as shown in Table 3 and FIG. 3 above, it was confirmed that it did not affect the potential value of the oxidation-reduction polymer, when a crosslinkable functional group was introduced to the oxidation-reduction polymer according to the present invention. Furthermore, it was confirmed that the compounds of Chemical formulas 48, 51, 57, and 59 showed lower potential values compared to the compound of Chemical formula 61, which is a conventionally known control group, so they could act as an oxidation-reduction mediator with high efficiency.

Experimental Example 2: Preparation of Electrochemical Sensor for Continuous Blood Glucose Measurement Comprising the Oxidation-Reduction Polymer According to the Present Invention

[0336] In order to produce an electrochemical sensor (electrochemical biosensor) comprising an electron transfer mediator of the oxidation-reduction polymer according to the present invention, a sensor was produced by the following method.

Experimental Method

[0337] 1. The compounds of Chemical formulas 48, 51, 53, and 59 according to the present invention and the compound of Number 61 as a comparison group were dissolved in an aqueous solution with oxidoreductase (glucose dehydrogenase), a carbon nanotube (CNT), a non-ionic surfactant (Triton-X) and a crosslinking material (polyethylene glycol diglycidylether), respectively, and each solution was prepared using stirring and ultrasonic dispersion methods. [0338] 2. In order to manufacture a continuous blood glucose electrochemical sensor, each solution prepared was aliquoted on an electrode printed with carbon paste and coated, and then cured through a crosslinking reaction at a room temperature for 24 hours. After curing, the manufactured sensor was washed using distilled water. [0339] 3. As a method for comparing the electron transfer performance manufactured above with the electrode comprising Chemical formula 61, cyclic voltammetry was used. [0340] 4. This experimental result was shown in Table 4 and FIG. 4 below, respectively.

Experimental Materials/Conditions

[0341] Working electrode: Electrode manufactured above [0342] Reference electrode: Ag/AgCl electrode [0343] Counter electrode: Platinum wire [0344] Electrolyte: Physiological saline solution containing phosphate buffer (Phosphate buffer with NaCl solution) [0345] Test parameters [0346] Equipment: EmStat(PalmSens Co.) [0347] Technique: cyclic voltammetry [0348] Potential range: 0.30.4V [0349] Scan rate: 10 mV/s

TABLE-US-00004 TABLE 4 Electrochemical sensor for continuous blood glucose measurement comprising oxidation-reduction polymer E.sup.0 (mV) E.sub.c E.sub.a (mV) I.sub.pa (A) [Chemical formula 48] 133.3 110.7 40.1 [Chemical formula 51] 99.2 97.7 91.1 [Chemical formula 53] 100.7 83.3 71.0 [Chemical formula 59] 106.7 49 15.0 [Chemical formula 61] 216.2 147.6 129.6

[0350] As shown in Table 4 and FIG. 4 above, the potential (E) of the electrode to which the oxidation-reduction polymer according to the present invention was applied had a lower potential than the comparison group electrode. This is the result similar to Experimental example 1, and in addition, through this experiment, it was confirmed that the working voltage of the electrochemical sensor for continuous blood glucose measurement could be stably used even at a lower voltage than the comparison group.

Experimental Example 3: Comparison of Sensitivity to Change in Glucose Concentration of Electrochemical Sensor for Continuous Blood Glucose Measurement

[0351] 1. The electrodes manufactured in Experimental example 2 above using the compounds of Chemical formulas 51, 53 according to the present invention, and as a comparison group, No. 61 compound were compared by performing chronoamperometry in a 0100 mM glucose solution. [0352] 2. The voltage applied when chronoamperometry was performed was 0.15 V for the electrode using the compound of 51, 53, and 0.25 V for the electrode using the compound of the comparison group No. 61. [0353] 3. The glucose concentration was 0.01, 0.05, 0.1, 0.5, 1, 5, 10, 50, or 100 mM, and a high concentration glucose solution was injected into physiological saline solution containing phosphate buffer at intervals of 200 seconds to reach each concentration. Each experiment was performed for 50 minutes. [0354] 4. This experimental result was shown in FIG. 5 and FIG. 6 below, respectively.

Experimental Materials/Conditions

[0355] Working electrode: Electrode manufactured above [0356] Reference electrode: Ag/AgCl electrode [0357] Counter electrode: Platinum wire [0358] Electrolyte: Physiological saline solution containing phosphate buffer (Phosphate buffer with NaCl solution) [0359] Test parameters [0360] Equipment: EmStat(PalmSens Co.) [0361] Technique: chronoamperometry [0362] Potential range: 0.15 V, 0.25 V

[0363] As shown in FIGS. 5 and 6, all the electrodes in which the oxidation-reduction polymer according to the present invention showed the linearity to glucose at a concentration of 10 mM or less, and showed similar sensitivity even though a lower voltage than the comparison group electrode was applied. In particular, based on that in the electrodes to which the compounds 51, 53 were applied, current at a concentration of 100 mM was larger than the comparison group, the maximum enzyme activity (V.sub.max) seems to be about 1.22 times larger than the comparison group.

Experimental Example 4: Comparison of Glucose Sensitivity According to Voltage Increase of Electrochemical Sensor for Continuous Blood Glucose Measurement

[0364] 1. The electrodes manufactured in Experimental example 2 above using the compounds of Chemical formulas 51, 53 according to the present invention, and as a comparison group, No. 61 compound were compared by performing multistep voltammetry (multi-potential step) in a glucose solution of 400 mM. [0365] 2. During performing the multistep voltammetry, by maintaining the voltage at a voltage from 0.2 V to 0.35 V at intervals of 0.05 V between them for 300 seconds, the current was observed. [0366] 3. This experimental result was shown in FIG. 7 below, respectively.

Experimental Materials/Conditions

[0367] Working electrode: Electrode manufactured above [0368] Reference electrode: Ag/AgCl electrode [0369] Counter electrode: Platinum wire [0370] Electrolyte: Physiological saline solution containing phosphate buffer (Phosphate buffer with NaCl solution) [0371] Test parameters [0372] Equipment: EmStat(PalmSens Co.) [0373] Technique: multi-potential step [0374] Potential range: 0.20.35 V

[0375] As shown in FIG. 7, it can be confirmed that all the electrodes in which the oxidation-reduction polymer according to the present invention is applied show sensitivity to glucose at a lower voltage than the comparison group electrode.