Electrochemical biosensor containing a transition metal complex or redox polymer or sensing membrane for an electrochemical biosensor

Abstract

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

Description

TECHNICAL FIELD

[0001] The present application relates to a transition metal complex having a bidentate ligand including pyrazole, triazole, tetrazole, oxadiazole, or thiadiazole, etc., and an electrochemical biosensor using the same. BACKGROUND

[0002] In recent years, from the medical field to the environmental and food fields, there is increasing interest in developing biosensors for quantitative and qualitative analysis of target analytes. In particular, biosensors using enzymes are chemical sensors for selectively detecting and measuring chemical substances contained in a sample by using a functional substance of a living organism or a biological detection function in which a living organism such as a microorganism is sensitively reacted with a specific substance, and most of them have been developed for medical measurement use, and in addition, research is also actively conducted in the fields of application in food engineering and environmental measurement.

[0003] Periodic measurement of blood glucose is very important in diabetes management, and thus various blood glucose meters are being manufactured so that blood glucose can be easily measured using a portable measuring instrument. The operating principle of such a biosensor is based on an optical method or an electrochemical method, and unlike a biosensor by a conventional optical method, such an electrochemical biosensor is capable of reducing the influence of oxygen and has the advantage of being able to be used without separately reprocessing a sample even if the sample is turbid. Therefore, various electrochemical biosensors having accuracy and precision are widely used.

[0004] The electrochemical blood glucose sensor currently commercialized mainly uses an enzyme electrode, and more specifically, has a structure in which glucose oxidase is immobilized on an electrode that can convert an electrical signal by a chemical or physical method. Such an electrochemical blood glucose sensor is based on the principle of measuring the glucose concentration in an analyte by measuring the current generated by transferring electrons when glucose in the analyte such as blood is oxidized by an enzyme. In the case of a biosensor using an enzyme electrode, there is a problem that it is not easy to directly transfer electrons generated when a substrate is oxidized to an electrode due to too far distance from the active center of the enzyme. Therefore, in order to easily perform such an electron transfer reaction, it is necessary to require an oxidation-reduction mediator, i.e., an electron transfer mediator. Therefore, the type of enzyme to be used and the characteristics of the electron transfer mediator are most significantly determined the characteristics of the electrochemical biosensor for measuring blood glucose.

[0005] In the development trend of blood glucose sensors, in order to block the change in the measured value due to the difference in the oxygen partial pressure (pO2) depending on the blood (venous blood, capillary blood, etc.), it is converted to use GDH in which oxygen is excluded from the enzyme reaction, instead of GOX in which oxygen participates in the enzymatic reaction with glucose in blood, and in the case of an electron transfer medium, instead of ferricyanide having a humidity-dependent sensitive stability, it has been replaced by an organic compound such as a quinone derivative (phenanthrolinequinone, quinonediimine, etc.) or an organometallic compound such as an osmium complex having excellent stability depending on temperature and humidity.

[0006] The most commonly used electron transfer medium includes potassium ferricyanide [K3Fe(CN)6], and since it is inexpensive and has strong reactivity, it is suitable for all sensors using FAD-GOX, PQQ-GDH, or FAD-GOX. However, the sensor using such an electron transfer medium has a measurement error due to interfering substances such as uric acid or gentisic acid present in blood, and is easily deteriorated by temperature and humidity, and thus should be particularly careful in manufacturing and storage, and since the background current changes after long-term storage, it is difficult to accurately detect low concentrations of glucose.

[0007] Ruthenium hexammine chloride [Ru(NH3)6Cl3] has higher redox stability than ferricyanide, and thus, a biosensor using such an electron transfer medium has the advantages of being easy to manufacture and store, and having high stability since the background current changes little even during long-term storage, but since the reactivity does not match the use of FAD-GDH, there is a disadvantage that it is difficult to manufacture it as a commercially useful sensor.

[0008] In addition, in using such a biosensor, accurate and rapid measurement with a small amount of sample is a very important issue in maximizing user convenience.

[0009] Therefore, there is still a need to develop a new electron transfer medium that can overcome the disadvantages of conventional electron transfer media and shorten the measurement time.

[0010] On the other hand, a continuous glucose monitoring (CGM) system is used to manage a disease such as diabetes by continuously observing blood glucose, but in a conventional enzyme sensor, blood sampling from a fingertip causes significant pain due to a needle during the blood sampling process, so the measurement frequency is limited, and thus cannot be used for such a CGM. To solve these problems, a modified enzyme sensor that can be attached in the body and minimizes invasiveness has recently been developed. In the case of a blood glucose monitoring enzyme sensor, since a part of the sensor enters the human body, problems caused by the loss of an electron transfer mediator in the human body are prevented by fixation with a polymer such as polyvinylpyridine or polyvinylimidazole, so that an electron transfer mediator including a transition metal as described above is absorbed by the human body and causes toxicity and side effects.

[0011] Accordingly, in order to develop a new electron transfer mediator suitable for a CGMS sensor, conventionally, a redox polymer of an enzyme sensor is mainly prepared and used by fixing a transition metal electron transfer mediator including a bipyridine and a bismidazole ligand on a polymer backbone. In this context, the inventors of the present application have confirmed that when a transition metal complex having a bidentate ligand includes a heterocyclic compound including a pyrazole, a triazole, a tetrazole, an oxadiazole, or a thiadiazole, etc. in addition to a bipyridine and a bismidazole ligand, all of the above requirements can be satisfied, thereby completing the present application. SUMMARY

[0012] TECHNICAL PROBLEM

[0013] The present application provides a transition metal complex or a salt compound thereof having a bidentate ligand including a heterocyclic structure such as a pyrazole, a triazole, a tetrazole, an oxadiazole, or a thiadiazole, etc., in which the synthesis of various derivatives and the introduction of functional groups are easy.

[0014] In one embodiment, the transition metal complex can be a transition metal complex or a salt compound thereof having a bidentate ligand including a pyridine; and one structure selected from the group consisting of a pyrazole, a triazole, a tetrazole, an oxadiazole, and a thiadiazole.

[0015] Another object of the present application is to provide a redox polymer including the transition metal complex or the salt compound thereof.

[0016] Another object of the present application is to provide the transition metal complex or the salt compound thereof and / or the redox polymer including the same to a device.

[0017] In one embodiment, the device can be a device for an electron transfer mediator, especially an electrochemical biosensor. In one embodiment, the device can be inserted into the body. In one embodiment, the electrochemical biosensor can be a blood glucose sensor.

[0018] Another object of the present application is to provide a sensing membrane for an electrochemical biosensor, which includes an enzyme capable of oxidizing a liquid biological sample; and a transition metal complex or a salt compound thereof and / or a redox polymer including the transition metal complex or the salt compound thereof.

[0019] Technical Solution

[0020] In one aspect, the present application provides a transition metal complex or a salt compound thereof having a bidentate ligand (hereinafter also referred to as "bidentate ligand"), the bidentate ligand including: a pyridine; and one structure selected from the group consisting of a pyrazole, a triazole, a tetrazole, an oxadiazole, and a thiadiazole.

[0021] Specifically, the transition metal complex can be a compound of the following Chemical Formula 1.

[0022] [Chemical Formula 1]

[0023] [M(L) a (X1) b ] c d(X2)

[0024] In this formula,

[0025] M is one transition metal selected from the group consisting of Fe, Ru, and Os, and

[0026] L is a bidentate ligand including: a pyridine; and one structure selected from the group consisting of a pyrazole, a triazole, a tetrazole, an oxadiazole, and a thiadiazole, and

[0027] a is 2 or 3, and

[0028] X1 is one halogen atom selected from the group consisting of F, Cl, Br, and I, and

[0029] b is 0, 1, or 2, and

[0030] c is an integer selected from 1 to 3 (for example, 1, 2, or 3), and

[0031] X2 is one counter ion selected from the group consisting of F, Cl, Br, I, and PF6, and

[0032] d is 0, 1, or 2.

[0033] Hereinafter, the present application will be described in detail.

[0034] Unless otherwise defined, all technical terms used in this disclosure have the same meaning as commonly understood by one of ordinary skill in the art related to the present disclosure. Also, in the description of the present disclosure, preferred methods or samples are described, but methods or samples similar or equivalent to those described also are included in the scope of the present disclosure. Furthermore, numerical values described in the present disclosure are considered to include the meaning of "about" even if not specified. The contents of all publications described in the present disclosure are incorporated by reference in their entireties.

[0035] Definitions of the groups used in the present specification will be described in detail. Each group has the following definition and is used in the same meaning as commonly understood by a person skilled in the art unless otherwise specified.

[0036] In the present disclosure, "halo" or "halogen" means, for example, fluorine, chlorine, bromine, and iodine.

[0037] In the present disclosure, "alkyl" means an aliphatic hydrocarbon radical and includes all straight chain or branched chain hydrocarbon radicals. For example, aliphatic hydrocarbons having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, pentyl, isopentyl, neopentyl, 1-ethylpropyl, hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, and 2-ethylbutyl, but are not limited thereto. Unless otherwise specified, alkyl can mean alkyl having 1 to 6 carbon atoms, 1 to 5 carbon atoms, 1 to 4 carbon atoms, 1 to 3 carbon atoms, 1 to 2 carbon atoms, 2 to 6 carbon atoms, 2 to 5 carbon atoms, 2 to 4 carbon atoms, 2 to 3 carbon atoms, 3 to 6 carbon atoms, 3 to 5 carbon atoms, 3 to 4 carbon atoms, 1 carbon atom, 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbon atoms, or 6 carbon atoms.

[0038] In the present disclosure, "alkoxy" represents an -O-alkyl or alkyl-O- group, and herein, alkyl is the same as defined above. For example, groups such as methoxy, ethoxy, n-propoxy, n-butoxy, and t-butoxy are included, but are not limited thereto. Alkoxy can be substituted with at least one suitable group or unsubstituted.

[0039] In the present disclosure, the term "hydroxy" or "hydroxyl" alone or in combination with another term means -OH.

[0040] In the present disclosure, "amino" represents -NH2, and "nitro" represents -NO2.

[0041] In the present specification, "aryl group" means a monovalent aromatic ring having, for example, 6 to 20 carbon atoms, 6 to 12 carbon atoms, or 6 to 10 carbon atoms, which is generated by removing one hydrogen atom in one carbon atom in a parent aromatic ring system. The aryl group can include a bicyclic radical including an aromatic ring fused with a saturated or partially unsaturated ring. An exemplary aryl group can include a radical generated from benzene (phenyl), a substituted phenyl, a biphenyl, a naphthyl, a tetrahydronaphthyl, a fluorenyl, a toluyl, a naphthyl, an anthryl, an indenyl, an indanyl, and the like, but is not limited thereto. The aryl group can be substituted with at least one suitable group or unsubstituted.

[0042] In the present specification, unless specifically mentioned, "substitution" can be at least one hydrogen atom substituted with one to three selected from the group consisting of a halogen atom (for example, F, Cl, Br, or I), a cyano group, a hydroxyl group, a sulfanyl group, a nitro group, an amino group, an imino group, an azido group, a guanyl group, a hydrazine group, a hydrazone group, an oxo group, a carbonyl group, a carbamoyl group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid or a salt thereof, a phosphoric acid or a salt thereof, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a haloalkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a haloalkynyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a 5- to 12-membered heterocycloalkyl group, a 5- to 12-membered heteroaryl group, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, and an arylthio group having 6 to 10 carbon atoms.

[0043] The transition metal complex provided in the present specification can be a compound of the following Chemical Formula 1.

[0044] [Chemical Formula 1]

[0045] [M(L) a (X1) b ] c d(X2)

[0046] In the formula,

[0047] M is one transition metal selected from the group consisting of Fe, Ru, and Os, and

[0048] L is a bidentate ligand including pyridine; and one structure selected from the group consisting of pyrazole, triazole, tetrazole, oxadiazole, and thiadiazole, and

[0049] a is 2 or 3, and

[0050] X1 is one halogen atom selected from the group consisting of F, Cl, Br, and I, and

[0051] b is 0, 1, or 2, and

[0052] c is an integer selected from 1 to 3 (e.g., 1, 2, or 3), and

[0053] X2 is a counter ion selected from the group consisting of F, Cl, Br, I, and PF6, and

[0054] d can be 0, 1, or 2.

[0055] Pyridine can be unsubstituted or selected from C. 1-4 Alkyl, C 1-4 Alkyl group, -(CH2)-OC 1-4 Alkyl group, -(CH2CH2)-OC 1-4 -alkyl and C 1-4 At least one of the groups consisting of alkylamino groups (e.g., 1 to 4, 1, 2, 3 or 4) is substituted.

[0056] Pyrazole, triazole, tetraazole, oxadiazole, or thiadiazole may each be unsubstituted or selected from C. 1-4 Alkyl, C 1-4 Alkyl group, -(CH2)-OC 1-4 Alkyl group, -(CH2CH2)-OC 1-4 -alkyl, and C 1-4 At least one of the groups consisting of alkylamino groups (e.g., 1 to 3, 1, 2 or 3) is substituted.

[0057] R'4 can be hydrogen or a substituted or unsubstituted C. 1-4 Alkyl group, and n' can be an integer selected from 1 to 4, such as 1, 2, 3 or 4.

[0058] C 1-4 Alkyl, alkoxy, or alkylamino can mean having 1 to 4, 1 to 3, 1 to 2, 2 to 4, 2 to 3, 3 to 4, 1, 2, 3, or 4 carbon atoms.

[0059] C 1-4 Alkyl, C 1-4 Alkyl group, -(CH2)-OC 1-4 Alkyl group, -(CH2CH2)-OC 1-4 -alkyl or C 1-4 Alkylamino groups can be unsubstituted or substituted. In substituted C... 1-4 Alkyl, C 1-4 Alkyl group, -(CH2)-OC 1-4 Alkyl group, -(CH2CH2)-OC 1-4 -alkyl or C1-4 In the alkylamino group, the hydrogen atom can be substituted with a halogen atom of F, Cl, Br or I, a cyano group, a hydroxyl group, a sulfanyl group, a nitro group, an amino group, an imino group, an azido group, an amidino group, a hydrazino group, a hydrazone group, an oxyl group, a carbonyl group, a carbamoyl group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, or phosphoric acid or a salt thereof.

[0060] Specifically, the transition metal complex can be a compound of the following Chemical Formula 2.

[0061] [Chemical Formula 2]

[0062]

[0063] In this formula,

[0064] R1, R2, R3, and R4 are each independently hydrogen, C 1-4 alkyl, C 1-4 alkoxy, (CH2)-O-C 1-4 alkyl, (CH2CH2)O-C 1-4 alkyl, or C 1-4 alkylamino, and

[0065] n is 0, and

[0066] at least one of W', Y', Z', and V' is nitrogen (N), and

[0067] W' is nitrogen (N) or carbon (C), and

[0068] Y', Z', and V' are each independently nitrogen (N), sulfur (S), oxygen (O), or carbon (C), and

[0069] R'1, R'2, and R'3 are each independently hydrogen, C 1-4 alkyl, C 1-4 alkoxy, -(CH2)-O-C 1-4 alkyl, -(CH2CH2)-O-C 1-4 alkyl, or C 1-4 alkylamino, and

[0070] the dotted line means bonding or no bonding, and

[0071] R'4 can be hydrogen or a substituted or unsubstituted C 1-4 alkyl group, and

[0072] n' can be an integer selected from 1 to 4, for example, 1, 2, 3, or 4, and

[0073] M, a, X1, b, c, X2, and d are as defined in Chemical Formula 1 above.

[0074] C1-4 alkyl, C 1-4 alkoxy, -(CH2)-O-C 1-4 alkyl, -(CH2CH2)-O-C 1-4 -alkyl or C 1-4 The alkylamino groups can each be unsubstituted or substituted, and the substitution is as described above.

[0075] Specifically, the transition metal complex can be a compound selected from the group consisting of Chemical Formula 3 to Chemical Formula 25.

[0076] [Chemical Formula 3]

[0077]

[0078] [Chemical Formula 4]

[0079]

[0080] [Chemical Formula 5]

[0081]

[0082] [Chemical Formula 6]

[0083]

[0084] [Chemical Formula 7]

[0085]

[0086] [Chemical Formula 8]

[0087]

[0088] [Chemical Formula 9]

[0089]

[0090] [Chemical Formula 10]

[0091]

[0092] [Chemical Formula 11]

[0093]

[0094] [Chemical Formula 12]

[0095]

[0096] [Chemical Formula 13]

[0097]

[0098] [Formula 14]

[0099]

[0100] [Formula 15]

[0101]

[0102] [Formula 16]

[0103]

[0104] [Formula 17]

[0105]

[0106] [Formula 18]

[0107]

[0108] [Formula 19]

[0109]

[0110] [Formula 20]

[0111]

[0112] [Formula 21]

[0113]

[0114] [Formula 22]

[0115]

[0116] [Formula 23]

[0117]

[0118] [Formula 24]

[0119]

[0120] [Formula 25]

[0121]

[0122] In one embodiment, the transition metal complex according to the present application can include a transition metal complex in an oxidation state, especially a trivalent osmium complex or a divalent osmium complex. As an oxidizing agent for the oxidation treatment, a commonly used oxidizing agent can be used. Examples of the oxidizing agent can be at least one selected from the group consisting of NaOCl, H2O2, O2, O3, PbO2, MnO2, KMnO4, ClO2, F2, Cl2, H2CrO4, N2O, Ag2O, OsO4, H2S2O8, cerium ammonium nitrate (CAN), pyridinium chlorochromate, and 2,2'-dipyridyl disulfide. Further, when the transition metal complex includes a compound in an oxidation state and a reduction state, the transition metal complex in the oxidation state or a salt compound thereof can be provided by the oxidation treatment.

[0123] The transition metal complex according to the present application can be in the form of a salt compound with a suitable counter ion and / or having an ion, and the salt compound can have a high solubility in water, an aqueous solution, or an organic solvent. In the salt compound, when it is composed of a small counter anion such as F - , Cl - , and Br - , etc., it tends to have a high solubility in water or an aqueous solution, and when it is composed of a large counter anion such as hexafluorophosphate (PF6 - ) and tetrafluoroborate (BF4 - ), etc., it tends to have a high solubility in an organic solvent. Examples of the counter anion can be at least one selected from the group consisting of a halide selected from the group consisting of F, Cl, Br, and I, hexafluorophosphate, and tetrafluoroborate.

[0124] In another aspect, the present application provides a redox polymer including a transition metal complex or a salt compound thereof, and including a polymer backbone such as polyvinylimidazole (PVI) and polyvinylpyridine (PVP), etc.

[0125] Specifically, the redox polymer can be a compound of Chemical Formula 26 or Chemical Formula 27:

[0126] [Chemical Formula 26]

[0127]

[0128] [Chemical Formula 27]

[0129]

[0130] In this formula,

[0131] M is one transition metal selected from the group consisting of Fe, Ru, and Os, and

[0132] L is a bidentate ligand comprising a pyridine; and a structure selected from the group consisting of a pyrazole, a triazole, a tetrazole, an oxadiazole, and a thiadiazole, and

[0133] a is 2 or 3, and

[0134] X1is a halogen atom selected from the group consisting of F, Cl, Br, and I, and

[0135] X2is a counter ion selected from the group consisting of F, Cl, Br, I, and PF6, and

[0136] m or o is an integer selected from 10 to 600, respectively.

[0137] The pyridine can be unsubstituted, or substituted with at least one (e.g., 1, 2, 3, or 4) selected from the group consisting of C 1-4 alkyl, C 1-4 alkoxy, -(CH2)-O-C 1-4 alkyl, -(CH2CH2)-O-C 1-4 -alkyl, and C 1-4 alkylamino.

[0138] The pyrazole, the triazole, the tetrazole, the oxadiazole, or the thiadiazole can be unsubstituted, or substituted with at least one (e.g., 1, 2, or 3) selected from the group consisting of C 1-4 alkyl, C 1-4 alkoxy, -(CH2)-O-C 1-4 alkyl, -(CH2CH2)-O-C 1-4 -alkyl, and C 1-4 alkylamino.

[0139] Specifically, the redox polymer can be a compound selected from the following Chemical Formula 28 to Chemical Formula 45:

[0140] [Chemical Formula 28]

[0141]

[0142] [Chemical Formula 29]

[0143]

[0144] [Chemical Formula 30]

[0145]

[0146] [Chemical Formula 31]

[0147]

[0148] [Chemical Formula 32]

[0149]

[0150] [Chemical Formula 33]

[0151]

[0152] [Chemical Formula 34]

[0153]

[0154] [Chemical Formula 35]

[0155]

[0156] [Chemical Formula 36]

[0157]

[0158] [Chemical Formula 37]

[0159]

[0160] [Chemical Formula 38]

[0161]

[0162] [Chemical Formula 39]

[0163]

[0164] [Chemical Formula 40]

[0165]

[0166] [Chemical Formula 41]

[0167]

[0168] [Chemical Formula 42]

[0169]

[0170] [Chemical Formula 43]

[0171]

[0172] [Chemical Formula 44]

[0173]

[0174] [Chemical Formula 45]

[0175]

[0176] In the formula,

[0177] m or o is the same as defined in Chemical Formula 26 or Chemical Formula 27 above.

[0178] In another aspect, in the present application, the redox polymer further includes a cross-linkable functional group, and can be a compound of the following Chemical Formula 46 or Chemical Formula 47.

[0179] [Chemical Formula 46]

[0180]

[0181] [Chemical Formula 47]

[0182]

[0183] In the formula,

[0184] M is one transition metal selected from the group consisting of Fe, Ru, Os, Rh, and Ir,

[0185] L is a bidentate ligand including pyridine; and one structure selected from the group consisting of pyrazole, triazole, tetrazole, oxadiazole, and thiadiazole, and

[0186] a is 2 or 3, and

[0187] X1is one halogen atom selected from the group consisting of F, Cl, Br, and I, and

[0188] X2is one counter ion selected from the group consisting of F, Cl, Br, I, and PF6, and

[0189] A D is one selected from the group consisting of primary and secondary amine groups, ammonium groups, halogen groups, epoxy groups, azido groups, acrylate groups, alkenyl groups, alkynyl groups, thio groups, isocyanate groups, alcohol groups, silane groups, and

[0190] R5’is hydrogen or a substituted or unsubstituted C 1-4 alkyl group, and

[0191] N”is an integer selected from 1 to 4, and

[0192] q is an integer selected from 1 to 10, and

[0193] m, o, or p is an integer selected from 10 to 600, respectively.

[0194] The pyridine can be unsubstituted, or substituted with one selected from the group consisting of C 1-4 alkyl groups, C 1-4 alkoxy groups, -(CH2)-O-C 1-4 ​alkyl, -(CH2CH2)-O-C 1-4 -alkyl, and C 1-4 at least one (e.g., 1, 2, 3, or 4) of the group consisting of alkyl, C

[0195] pyrazole, triazole, tetrazole, oxadiazole, or thiadiazole can be unsubstituted, or substituted, respectively, by at least one selected from the group consisting of C 1-4 alkyl, C 1-4 alkoxy, -(CH2)-O-C 1-4 alkyl, -(CH2CH2)-O-C 1-4 -alkyl, and C 1-4 at least one (e.g., 1, 2, or 3) of the group consisting of alkyl, C

[0196] Specifically, the redox polymer can be a compound selected from the group consisting of Chemical Formula 48 to Chemical Formula 60.

[0197] [Chemical Formula 48]

[0198]

[0199] [Chemical Formula 49]

[0200]

[0201] [Chemical Formula 50]

[0202]

[0203] [Chemical Formula 51]

[0204]

[0205] [Chemical Formula 52]

[0206]

[0207] [Chemical Formula 53]

[0208]

[0209] [Chemical Formula 54]

[0210]

[0211] [Chemical Formula 55]

[0212]

[0213] [Chemical Formula 56]

[0214]

[0215] [Chemical Formula 57]

[0216]

[0217] [Chemical Formula 58]

[0218]

[0219] [Chemical Formula 59]

[0220]

[0221] [Chemical Formula 60]

[0222]

[0223] In another aspect, there is provided an apparatus comprising: a transition metal complex or a salt compound thereof; or a redox polymer.

[0224] In one embodiment, the apparatus can be an electrochemical biosensor.

[0225] In one embodiment, the apparatus can be inserted into the body, and in particular, can be an electrochemical biosensor insertable into the body.

[0226] In one embodiment, the electrochemical biosensor can be a blood glucose sensor, for example, an electrochemical glucose (blood sugar) sensor.

[0227] In one embodiment, the electrochemical biosensor can be a continuous blood glucose monitoring sensor.

[0228] As a composition of a continuous blood glucose monitoring sensor, the present application can include, for example, an electrode, an insulator, a substrate, a sensing layer including a redox polymer and a redox enzyme, a diffusion layer, and a protective layer, etc. In the case of an electrode, 2 electrodes such as a working electrode and a counter electrode can be included, and 3 electrodes such as a working electrode, a counter electrode, and a reference electrode can be included.

[0229] In one embodiment, the biosensor according to the present application can be an electrochemical biosensor manufactured by applying a reagent composition comprising: a transition metal complex or a salt compound thereof; or a redox polymer, and an enzyme capable of oxidizing and reducing a liquid biological sample after drying on a substrate having at least two, preferably two or three electrodes.

[0230] For example, a planar electrochemical biosensor is characterized in that a working electrode and a counter electrode are disposed on opposite sides of a substrate, and a sensing film of the present invention including a transition metal complex or a redox polymer is laminated on the working electrode, and in the electrochemical biosensor, an insulator, a diffusion layer, and a protective layer are sequentially laminated on both sides of the substrate in which the working electrode and the counter electrode are equipped.

[0231] As a specific aspect, the substrate can be made of at least one material selected from the group consisting of PET (polyethylene terephthalate), PC (polycarbonate), and PI (polyimide).

[0232] In addition, as the working electrode, carbon, gold, platinum, silver, or a silver / silver chloride electrode can be used.

[0233] Further, in the case of an electrochemical biosensor having two electrodes, the counter electrode functions as a reference electrode, and thus a gold, platinum, silver, or silver / silver chloride electrode can be used as the counter electrode, and in the case of an electrochemical biosensor having three electrodes including even a reference electrode, a gold, platinum, silver, or silver / silver chloride electrode can be used as the reference electrode, and a carbon electrode can be used as the counter electrode.

[0234] As the diffusion layer, Nafion, cellulose acetate, and silicone rubber can be used, and as the protective layer, silicone rubber, polyurethane, a polyurethane-based copolymer, or the like can be used, but is not limited thereto.

[0235] As non-limiting examples, in the case of two electrodes, silver chloride or silver can be used since the counter electrode also functions as a reference electrode, and in the case of three electrodes, silver chloride or silver can be used as the reference electrode, and a carbon electrode can be used as the counter electrode.

[0236] By changing the type of enzyme included in the reagent composition of the present invention, it can be applied to a biosensor for quantitative analysis of various substances such as cholesterol, lactate, creatinine, hydrogen peroxide, alcohol, amino acid, and glutamate.

[0237] On the other hand, there is provided a sensing film for an electrochemical biosensor, including an enzyme capable of oxidizing and reducing a liquid biological sample; and a transition metal complex or a salt compound thereof as an electron transfer medium; or a redox polymer.

[0238] The liquid biological sample can be one or more, two or more, three or more, four or more, or five or more selected from the group consisting of, for example, tissue fluid, blood, cells, plasma, serum, urine, cyst fluid, and saliva of a patient, but is not limited thereto.

[0239] In one embodiment, the enzyme can include at least one oxidoreductase selected from the group consisting of dehydrogenase, oxidase, and esterase; or

[0240] at least one oxidoreductase selected from the group consisting of dehydrogenase, oxidase, and esterase, and at least one co-factor selected from the group consisting of flavin adenine dinucleotide (FAD), nicotinamide adenine dinucleotide (NAD), and pyrroloquinoline quinone (PQQ).

[0241] Oxidoreductases are collectively enzymes that catalyze oxidation-reduction reactions of living organisms, and in the present invention, it means an enzyme that is reduced by reacting with a target substrate (e.g., a target substrate to be measured in the case of a biosensor). The thus-reduced enzyme reacts with an electron transfer medium, and then the target substrate is quantified by measuring a change in current generated at that time or the like. The oxidoreductase that can be used in the present invention can be at least one selected from the group consisting of various dehydrogenases, oxidases, esterases, and the like, and depending on the target substrate for oxidation-reduction or detection, among the enzymes belonging to the above-mentioned enzyme group, an enzyme that utilizes the target substrate as a substrate can be selected and used.

[0242] More specifically, the oxidoreductase can be at least one selected from the group consisting of glucose dehydrogenase, glutamate dehydrogenase, glucose oxidase, cholesterol oxidase, cholesterol esterase, lactic acid oxidase, ascorbic acid oxidase, alcohol oxidase, alcohol dehydrogenase, and bilirubin oxidase, and the like.

[0243] On the other hand, the oxidoreductase can include a co-factor that plays a role of storing hydrogen acquired by the oxidoreductase from the target substrate to be measured (e.g., a target substrate), and for example, it can be at least one selected from the group consisting of flavin adenine dinucleotide (FAD), nicotinamide adenine dinucleotide (NAD), and pyrroloquinoline quinone (PQQ), and the like.

[0244] For example, when blood glucose concentration is to be measured, glucose dehydrogenase (GDH) can be used as an oxidoreductase, and the glucose dehydrogenase can be flavin adenine dinucleotide-glucose dehydrogenase (FAD-GDH) including FAD as a co-factor and / or nicotinamide adenine dinucleotide-glucose dehydrogenase including FAD-GDH as a co-factor.

[0245] In one embodiment, the oxidoreductase enzyme that can be used can be at least one selected from the group consisting of FAD-GDH (e.g., EC 1.1.99.10, etc.), NAD-GDH (e.g., EC 1.1.1.47, etc.), PQQ-GDH (e.g., EC 1.1.5.2, etc.), glutamate dehydrogenase (e.g., 1.4.1.2, etc.), glucose oxidase (e.g., EC 1.1.3.4, etc.), cholesterol oxidase (e.g., EC 1.1.3.4, etc.), cholesterol esterase (e.g., EC 3.1.1.13, etc.), lactic acid oxidase (e.g., EC 1.1.3.2, etc.), ascorbic acid oxidase (e.g., EC 1.10.3.3, etc.), alcohol oxidase (e.g., EC 1.1.3.13, etc.), alcohol dehydrogenase (e.g., EC 1.1.1.1, etc.), and bilirubin oxidase (e.g., EC 1.3.3.5, etc.), etc.

[0246] Most preferably, the oxidoreductase enzyme is glucose dehydrogenase, which can maintain 70% or more of the activity in a buffer solution at 37°C for 1 week.

[0247] The sensing film according to the present application can contain 20 to 700 parts by weight, for example, 60 to 700 parts by weight, or 30 to 340 parts by weight of the oxidoreductase polymer, based on 100 parts by weight of the oxidoreductase enzyme. The content of the oxidoreductase polymer can be appropriately adjusted according to the activity of the oxidoreductase enzyme.

[0248] In addition, the sensing film according to the present application can further contain carbon nanotubes to improve the performance of the film. Specifically, when used together with a transition metal complex, especially osmium, the carbon nanotubes can further improve the performance of the sensing film as the speed of electron transfer increases.

[0249] In addition, the sensing film according to the present application can further include a crosslinking agent.

[0250] On the other hand, the sensing film according to the present application can additionally contain at least one additive selected from the group consisting of a surfactant, a water-soluble polymer, a quaternary ammonium salt, a fatty acid, and a thickening agent, etc., for the role of a dispersant during the dissolution of the reagent, the role of an adhesive during the preparation of the reagent, and the role of a stabilizer during long-term storage, etc.

[0251] The surfactant can function to uniformly spread the composition on the electrode in a uniform thickness and to aliquot when the composition is aliquoted. At least one selected from the group consisting of Triton X-100, sodium dodecyl sulfate, perfluoro octane sulfonate, sodium stearate, and the like can be used as the surfactant. The reagent composition according to the present application can contain the surfactant in an amount of 3 to 25 parts by weight, for example, 10 to 25 parts by weight, based on 100 parts by weight of the oxidoreductase, thereby enabling it to appropriately function to enable the reagent to be uniformly spread on the electrode and the reagent to be aliquoted in a uniform thickness when the reagent is aliquoted. For example, when the oxidoreductase having an activity of 700 U / mg is used, it can contain 10 to 25 parts by weight of the surfactant based on 100 parts by weight of the oxidoreductase, and when the activity of the oxidoreductase becomes higher than this value, the content of the surfactant can be adjusted to be lower than the above range.

[0252] The water-soluble polymer is a polymer carrier of the reagent composition, and can function to help the enzyme stabilization and dispersion. At least one selected from the group consisting of polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyperfluorosulfonate, hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), carboxymethyl cellulose (CMC), cellulose acetate, and polyamide, and the like can be used as the water-soluble polymer. The reagent composition according to the present application can contain 10 to 70 parts by weight, for example, 30 to 70 parts by weight of the water-soluble polymer based on 100 parts by weight of the oxidoreductase, thereby sufficiently and appropriately exhibiting the function to help the oxidoreductase stabilization and dispersion. For example, when the oxidoreductase having an activity of 700 U / mg is used, it can contain 30 to 70 parts by weight of the water-soluble polymer based on 100 parts by weight of the oxidoreductase, and when the activity of the oxidoreductase is higher than this value, the content of the water-soluble polymer can be adjusted to be lower than the above range.

[0253] The weight average molecular weight of the water-soluble polymer can be about 2,500 g / mol to 3,000,000 g / mol, for example, about 5,000 g / mol to 1,000,000 g / mol, thereby effectively functioning to help the carrier and the enzyme stabilization and dispersion.

[0254] The thickening agent functions to firmly attach the reagent to the electrode. At least one selected from the group consisting of cellulose hydroxyethyl ether (Natrosol) and diethylaminoethyl dextran hydrochloride (DEAE-Dextran hydrochloride), etc. can be used as the thickening agent. The electrochemical sensor according to the present application can contain 10 to 90 parts by weight, for example, 30 to 90 parts by weight of the thickening agent based on 100 parts by weight of the oxidoreductase. For example, when the oxidoreductase having an activity of 700 U / mg is used, it can contain 30 to 90 parts by weight of the thickening agent based on 100 parts by weight of the oxidoreductase, and when the activity of the oxidoreductase is higher than this value, the content of the thickening agent can be adjusted to be lower than the above range.

[0255] Advantageous Effects

[0256] The transition metal complex and the redox polymer according to the present application can easily adjust the potential value according to the type of the introduced ligand, and the size of the ligand is smaller than that of the conventional bipyridyl-based ligand, thus the electron transfer speed is increased, and thus the electrochemical biosensor applying the same has the advantage of rapid and economical detection. BRIEF DESCRIPTION OF DRAWINGS

[0257] Figures la to lo is a cyclic voltammogram showing the electrochemical characteristics of the transition metal complex having a bidentate ligand containing a pyrazole, a triazole, a tetrazole, an oxadiazole, or a thiadiazole according to the present application.

[0258] {Chemical Formula 3 Figure la ), Chemical Formula 4 Figure lb ), Chemical Formula 9 Figure lc ), Chemical Formula 11 Figure Id ), Chemical Formula 14 Figure le ), Chemical Formula 15 Figure If ), Chemical Formula 16 Figure lg ), Chemical Formula 17 Figure lh ), Chemical Formula 18 Figure li ), Chemical Formula 20 Figure lj ), Chemical Formula 22 Figure lk ), Chemical Formula 23 Figure ll ), Chemical Formula 24 Figure lm ), Chemical Formula 25 Figure ln ), Chemical Formula 3, Chemical Formula 4, Chemical Formula 11, Chemical Formula 14, Chemical Formula 15, Chemical Formula 16 Figure lo

[0259] Figure 2 is a cyclic voltammogram showing the electrochemical characteristics of the redox polymer containing the transition metal complex according to the present application.

[0260] Figure 3 ​is a cyclic voltammogram showing the electrochemical characteristics of a redox polymer containing a transition metal complex and a crosslinkable functional group according to the present application.

[0261] Figure 4 is a graph showing the potential of an electrode to which a redox polymer according to the present application is applied.

[0262] Figure 5 and Figure 6 is a graph showing that all electrodes to which a redox polymer according to the present application is applied show linear sensitivity to glucose at a concentration of 10 mM or less, and show similar sensitivity even if a voltage lower than that of a comparative group electrode is applied.

[0263] Figure 7 is a graph showing that all electrodes to which a redox polymer according to the present application is applied show sensitivity to glucose at a voltage lower than that of a comparative group electrode. DETAILED DESCRIPTION

[0264] Hereinafter, the present application will be described in more detail by the following examples. However, the following examples are merely illustrative of the present application, but the scope of the present application is not limited by the following examples.

[0265] Example 1: Preparation of a transition metal complex according to the present application

[0266] Example 1.1. Synthesis of a transition metal complex of Chemical Formula 3

[0267] 1) Synthesis of 2-(1H-pyrazol-1-yl)pyridine

[0268]

[0269] A reflux condenser and a gas inlet were fitted to a 250 mL two-necked round bottom flask, and pyrazole 4.7 g (69 mmol) and potassium butoxide 9.3 g (83 mmol) were added and dissolved in 40 mL of anhydrous dimethyl sulfoxide under an argon atmosphere. To this reaction mixture, 2-fluoropyridine 8.0 g (83 mmol) was added, and heated to 100°C under an argon atmosphere and stirred for 4 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature, and extracted with water (100 mL) and ethyl acetate (100 mL x 3). The organic layer was collected and dried with magnesium sulfate, and concentrated under reduced pressure to obtain a transparent colorless solid. (7.2 g, 72%)

[0270] 2) Synthesis of Os(pzpy)2Cl2 [Chemical Formula 3]

[0271]

[0272] Potassium osmate(VI) hexachloro 5.0 g (10 mmol) and 2-(1H-pyrazol-1-yl)pyridine prepared in 1) above 2.9 g (20 mmol) were added into a 500 mL shrink flask and dissolved in 200 mL of ethylene glycol under argon atmosphere, and then argon degassing was performed for 15 minutes. The reaction mixture was heated to 180°C and stirred for 1 hour. After the completion of the reaction, the reaction mixture was cooled to room temperature, and the resulting red precipitate was filtered and removed under reduced pressure. The filtrate was dropped into a 1.0 M aqueous solution of sodium dithionite (250 mL), thereby obtaining a precipitate of a reduced osmium complex. The resulting solid was filtered under reduced pressure and washed with water several times, and then dried in a vacuum oven at 40°C to obtain a green final compound, an osmium complex. (4.0 g, 75%) HRMS 192 Os): m / z 552.0240 ([M + ] requires 552.0261)

[0273] The complete preparation method of the compound of Chemical Formula 3 is shown in the following Reaction Formula 1.

[0274] [Reaction Formula 1]

[0275]

[0276] Example 1.2. Synthesis of a transition metal complex of Chemical Formula 4

[0277] 1) Synthesis of 2-methyl-6-(1H-pyrazol-1-yl)pyridine

[0278]

[0279] A reflux condenser and a gas inlet were attached to a 250 mL two-necked round bottom flask, and pyrazole 2.0 g (30 mmol) and potassium tert-butoxide 4.0 g (36 mmol) were added and dissolved in 20 mL of anhydrous dimethyl sulfoxide under an argon atmosphere. To the reaction mixture, 5.0 g (36 mmol) of 2-fluoro-5-methylpyridine was added, and heated to 100°C under an argon atmosphere and stirred for 4 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature, and extracted with water (100 mL) and ethyl acetate (100 mL x 3). The organic layer was collected and concentrated under reduced pressure, and after removing the solvent, purified by column chromatography using ethyl acetate and hexane as developing solvents. (Hexane: ethyl acetate = 5:1) 2-methyl-6-(1H-pyrazol-1-yl)pyridine was finally obtained as a transparent solid. (1.4 g, 30%)

[0280] 2) Synthesis of Os(pz-2-Me-py)2Cl2 [Chemical Formula 4]

[0281]

[0282] Potassium osmate(VI) hexachloride 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 to a 250 mL Schlenk flask and dissolved in 50 mL of ethylene glycol under an argon atmosphere, and then subjected to argon degassing for 15 minutes. The reaction mixture was heated to 180°C and stirred for 1 hour. After the completion of the reaction, the reaction mixture was cooled to room temperature, and the resulting red precipitate was filtered and removed under reduced pressure. The filtrate was dropped into a 1.0 M aqueous sodium dithionite solution (250 mL), thereby obtaining a precipitate of a reduced osmium complex. The resulting 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, an osmium complex.(0.27 g, 15%) HRMS 192 Os): m / z 580.0569 ([M + ] requires 580.0574)

[0283] The complete preparation method of the compound of Chemical Formula 4 is shown in the following Reaction Formula 2.

[0284] [Reaction Formula 2]

[0285]

[0286] Example 1.3. Synthesis of a transition metal complex of Chemical Formula 5

[0287] 1) Synthesis of 4-methoxy-2-(1H-pyrazol-1-yl)pyridine

[0288]

[0289] A reflux condenser and a gas inlet were attached to a 250 mL two-necked round bottom flask, and pyrazole 2.0 g (30 mmol) and potassium tert-butoxide 4.0 g (36 mmol) were added and dissolved in 20 mL of anhydrous dimethyl sulfoxide under an argon atmosphere. To this reaction mixture, 2-bromo-4-methoxypyridine 6.7 g (36 mmol) was added, heated to 100°C under an argon atmosphere, and stirred for 8 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature, and extracted with water (100 mL) and ethyl acetate (100 mL x 3). The organic layer was collected and concentrated under reduced pressure, and after removing the solvent, purified by column chromatography using ethyl acetate and hexane as developing solvents. (Hexane: ethyl acetate = 3:1) 4-methoxy-2-(1H-pyrazol-1-yl)pyridine was finally obtained as a transparent solid.(4.0 g, 63%)

[0290] 2) Synthesis of Os(pz-4-Meo-py)2Cl2 [Chemical Formula 5]

[0291]

[0292] Potassium osmate(VI) 2.0 g (4.2 mmol) and 4-methoxy-2-(1H-pyrazol-1-yl)pyridine prepared in 1) above 1.5 g (8.3 mmol) were added to a 250 mL Schlenk flask and dissolved in 50 mL of ethylene glycol under an argon atmosphere, and then argon degassing was performed for 15 minutes. The reaction mixture was heated to 180°C and stirred for 1 hour. After the completion of the reaction, the reaction mixture was cooled to room temperature, and the resulting red precipitate was filtered and removed under reduced pressure. The filtrate was dropped into a 1.0 M aqueous sodium dithionite solution (250 mL), thereby obtaining a precipitate of a reduced osmium complex. The resulting 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, an osmium complex. (2.0 g, 78%) HRMS (Os): m / z 612.0460 ([M 192 Os) : m / z 612.0460 ([M + ] requires 612.0472)

[0293] The complete preparation method of the compound of Chemical Formula 5 is shown in the following Reaction Formula 3.

[0294] [Reaction Formula 3]

[0295]

[0296] Example 1.4. Synthesis of a transition metal complex of Chemical Formula 6

[0297] 1) Synthesis of 4-methyl-2-(1H-pyrazol-1-yl)pyridine

[0298]

[0299] A reflux condenser and a gas inlet were attached to a 250 mL two-necked round bottom flask, and pyrazole 2.0 g (30 mmol) and potassium tert-butoxide 4.0 g (36 mmol) were added and dissolved in 20 mL of anhydrous dimethyl sulfoxide under an argon atmosphere. To this reaction mixture, 2-bromo-4-methylpyridine 6.2 g (36 mmol) was added, and heated to 100°C under an argon atmosphere and stirred for 8 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature, and extracted with water (100 mL) and ethyl acetate (100 mL x 3). The organic layer was collected and concentrated under reduced pressure, and after removing the solvent, purified by column chromatography using ethyl acetate and hexane as developing solvents (hexane: ethyl acetate = 3:1). 4-methoxy-2-(1H-pyrazol-1-yl)pyridine was finally obtained as a transparent solid. (3.5 g, 61%)

[0300] 2) Synthesis of Os(pz-4-Me-py)2Cl2 [Formula 6]

[0301]

[0302] Potassium osmate (IV) hexahydrate 2.0 g (4.2 mmol) and 4-methyl-2-(1 H-pyrazol-1 - yl)pyridine 1.3 g (8.3 mmol) prepared in 1 ) above were added to a 250 mL Schlenk flask and dissolved in 50 mL of ethylene glycol under argon atmosphere, followed by argon degassing for 15 minutes. The reaction mixture was heated to 180 °C and stirred for 1 hour. After completion of the reaction, the reaction mixture was cooled to room temperature and filtered under reduced pressure and the red precipitate produced was removed. The filtrate was dropped into a 1.0 M aqueous solution of sodium hydrosulfite (250 mL) to obtain a precipitate 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 the green final compound osmium complex. (1.0 g, 42%) HRMS (ESI+) m / z 580.0561 ([M - Cl]2+, 100%), 582.0583 ([M - Cl]2+, 50%), 584.0605 ([M - Cl]2+, 25%). 192 Os): m / z 580.0561 ([M - Cl]2+, 100%), 582.0583 ([M - Cl]2+, 50%), 584.0605 ([M - Cl]2+, 25%). + 580.0574) required

[0303] The complete preparation method of the compound of Formula 6 is shown in the following Reaction Scheme 4.

[0304] [Reaction Scheme 4]

[0305]

[0306] Example 1.5. Synthesis of transition metal complex of Formula 7

[0307] 1) Synthesis of 4-methyl-2-(3-methyl-1 H-pyrazol-1 -yl)pyridine

[0308]

[0309] A reflux condenser and a gas inlet were attached to a 250 mL two-necked round bottom flask, and 3-methylpyrazole 2.5 g (30 mmol) and potassium tert-butoxide 4.0 g (36 mmol) were added and dissolved in 20 mL of anhydrous dimethyl sulfoxide under an argon atmosphere. To this reaction mixture, 2-bromo-4-methylpyridine 6.2 g (36 mmol) was added, heated to 100°C under an argon atmosphere, and stirred for 18 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature, and extracted with water (100 mL) and ethyl acetate (100 mL x 3). The organic layer was collected and concentrated under reduced pressure, and after the removal of the solvent, purified by column chromatography using ethyl acetate and hexane as developing solvents (hexane: ethyl acetate = 3:1). Finally, 4-methyl-2-(3-methyl-1H-pyrazol-1-yl)pyridine was obtained as a transparent solid. (4.2 g, 80%)

[0310] 2) Synthesis of Os(3-Me-pz-4-Me-py)2Cl2 [Formula 7]

[0311]

[0312] Potassium hexachloroosmate (IV) 2.0 g (4.2 mmol) and 4-methyl-2-(3-methyl-1H-pyrazol-1-yl)pyridine prepared in 1) above 1.4 g (8.3 mmol) were added to a 250 mL Schlenk flask, and dissolved in 50 mL of ethylene glycol under an argon atmosphere, followed by argon degassing for 15 minutes. The reaction mixture was heated to 180°C and stirred for 1 hour. After the completion of the reaction, the reaction mixture was cooled to room temperature, filtered and the generated red precipitate was removed under reduced pressure. The filtrate was dropped into a 1.0 M aqueous solution of sodium hydrosulfite (250 mL), thereby obtaining a precipitate of a reduced osmium complex. The generated solid was filtered under reduced pressure and washed with water and acetonitrile several times, and then dried in a vacuum oven to obtain the final compound, a green osmium complex. (2.0 g, 78%) HRMS (ESI+) m / z 608.0875 ([M-OH]+, 100%), 630.0735 ([M-Cl]+, 50%). 192 Os): m / z 608.0875 ([M-OH]+, 100%), 630.0735 ([M-Cl]+, 50%). + 608.0887) required

[0313] The complete preparation method of the compound of Formula 7 is shown in the following Reaction Scheme 5.

[0314] [Reaction Scheme 5]

[0315]

[0316] Example 1.6. Synthesis of a transition metal complex of Formula 8

[0317] 1) Synthesis of 4-methoxy-2-(3-methyl-1H-pyrazol-1-yl)pyridine

[0318]

[0319] A reflux condenser and a gas inlet were attached to a 250 mL two-necked round bottom flask, and 3-methylpyrazole 2.5 g (30 mmol) and potassium tert-butoxide 4.0 g (36 mmol) were added and dissolved in 20 mL of anhydrous dimethyl sulfoxide under an argon atmosphere. To this reaction mixture, 2-bromo-4-methoxypyridine 6.7 g (36 mmol) was added, heated to 100°C under an argon atmosphere, and stirred for 18 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature, and extracted with water (100 mL) and ethyl acetate (100 mL x 3). The organic layer was collected and concentrated under reduced pressure, and after removing the solvent, purified by column chromatography using ethyl acetate and hexane as developing solvents (hexane: ethyl acetate = 3:1). Finally, 4-methoxy-2-(3-methyl-1H-pyrazol-1-yl)pyridine was obtained as a transparent solid. (3.0 g, 53%)

[0320] 2) Synthesis of Os(3-Me-p-4-MeO-py)2Cl2 [Formula 8]

[0321]

[0322] Potassium hexachloroosmate (IV) 2.0 g (4.2 mmol) and 4-methoxy-2-(3-methyl-1H-pyrazol-1-yl)pyridine prepared in 1) above 1.5 g (8.3 mmol) were added to a 250 mL Schlenk flask, and dissolved in 50 mL of ethylene glycol under an argon atmosphere, followed by argon degassing for 15 minutes. The reaction mixture was heated to 180°C and stirred for 1 hour. After the completion of the reaction, the reaction mixture was cooled to room temperature, filtered and the generated red precipitate was removed under reduced pressure. The filtrate was dropped into a 1.0 M aqueous solution of sodium hydrosulfite (250 mL), thereby obtaining a precipitate of a reduced osmium complex. The generated solid was filtered under reduced pressure and washed with water and acetonitrile several times, and then dried in a vacuum oven to obtain the final compound, a green osmium complex. (1.0 g, 37%) HRMS (ESI+) m / z 640.0775 ([M-OH]+, 100%), 662.0735 ([M-Cl]+, 50%). 192 Os): m / z 640.0775 ([M-OH]+, 100%), 662.0735 ([M-Cl]+, 50%). + 640.0785 is required)

[0323] The complete preparation method of the compound of Formula 8 is shown in the following Reaction Scheme 6.

[0324] [Reaction Scheme 6]

[0325]

[0326] Example 1.7. Synthesis of a transition metal complex of Formula 9

[0327] 1) Synthesis of 4-methyl-2-(4-methyl-lH-pyrazol-l-yl)pyridine

[0328]

[0329] A reflux condenser and a gas inlet were equipped to a 250 mL two-necked round bottom flask, and 4-methylpyrazole 2.5 g (30 mmol) and potassium tert-butoxide 4.0 g (36 mmol) were dissolved in 20 mL of anhydrous dimethyl sulfoxide under an argon atmosphere. To this reaction mixture, 2-bromo-4-methylpyridine 6.2 g (36 mmol) was added, heated to 100°C under an argon atmosphere, and stirred for 18 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature, and extracted with water (100 mL) and ethyl acetate (100 mL x 3). The organic layer was collected and concentrated under reduced pressure, and after removing the solvent, purified by column chromatography using ethyl acetate and hexane as developing solvents (hexane: ethyl acetate = 3: 1). Finally, 4-methyl-2-(4-methyl-lH-pyrazol-l-yl)pyridine was obtained as a transparent solid. (4.5 g, 86%)

[0330] 2) Synthesis of Os(4-Me-pz-4-Me-py)2Cl2 [Formula 9]

[0331]

[0332] Potassium hexachloroosmate (IV) 5.0 g (10 mmol) and 4-methyl-2-(4-methyl-lH-pyrazol-l-yl)pyridine prepared in 1) above 4.1 g (21 mmol) were added to a 250 mL Schlenk flask, and dissolved in 100 mL of ethylene glycol under an argon atmosphere, followed by argon degassing for 15 minutes. The reaction mixture was heated to 180°C and stirred for 1 hour. After the completion of the reaction, the reaction mixture was cooled to room temperature, filtered and the generated red precipitate was removed under reduced pressure. The filtrate was dropped into a 1.0 M aqueous solution of sodium hydrosulfite (250 mL), thereby obtaining a precipitate of a reduced osmium complex. The generated solid was filtered under reduced pressure and washed with water and acetonitrile several times, and then dried in a vacuum oven to obtain the final compound, the green osmium complex. (5.5 g, 91%) HRMS (ESI+) m / z 608.0871 ([M-Os] requires 608.0887) 192 Os): m / z 608.0871 ([M-Os] requires 608.0887) + ] requires 608.0887)

[0333] The complete preparation method of the compound of Formula 9 is shown in the following Reaction Scheme 7.

[0334] [Reaction Scheme 7]

[0335]

[0336] Example 1.8. Synthesis of transition metal complex of Chemical Formula 10

[0337] 1) Synthesis of 4-methoxy-2-(4-methyl-lH-pyrazol-l-yl)pyridine

[0338]

[0339] A reflux condenser and a gas inlet were attached to a 250 mL two-necked round bottom flask, and 4-methylpyrazole 2.5 g (30 mmol) and potassium tert-butoxide 4.0 g (36 mmol) were dissolved in 20 mL of anhydrous dimethyl sulfoxide under an argon atmosphere. To this reaction mixture, 2-bromo-4-methoxypyridine 6.7 g (36 mmol) was added, heated to 100°C under an argon atmosphere, and stirred for 18 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature, and extracted with water (100 mL) and ethyl acetate (100 mL x 3). The organic layer was collected and concentrated under reduced pressure, and after removing the solvent, purified by column chromatography using ethyl acetate and hexane as developing solvents (hexane: ethyl acetate = 3: 1). 4-methoxy-2-(4-methyl-lH-pyrazol-l-yl)pyridine was finally obtained as a transparent solid. (2.8 g, 50%)

[0340] 2) Synthesis of Os(4-Me-pz 4-MeO-py)2Cl2 [Chemical Formula 10]

[0341]

[0342] Potassium hexachloroosmate (IV) 3.0 g (6.2 mmol) and 4-methoxy-2-(4-methyl-lH-pyrazol-l-yl)pyridine prepared in 1) above 2.4 g (12 mmol) were added to a 250 mL Schlenk flask, and dissolved in 60 mL of ethylene glycol under an argon atmosphere, followed by argon degassing for 15 minutes. The reaction mixture was heated to 180°C and stirred for 1 hour. After the completion of the reaction, the reaction mixture was cooled to room temperature, filtered and the generated red precipitate was removed under reduced pressure. The filtrate was dropped into a 1.0 M aqueous solution of sodium hydrosulfite (250 mL), thereby obtaining a precipitate of a reduced osmium complex. The generated solid was filtered under reduced pressure and washed with water and acetonitrile several times, and then dried in a vacuum oven to obtain the final compound, an osmium complex, as a green color. (2.3 g, 58%) HRMS (ESI+) m / z 640.0792 ([M-Os]+, 100%), 642.0812 ([M-Os]+, 80%), 644.0832 ([M-Os]+, 60%), 646.0852 ([M-Os]+, 40%). 192 Os): m / z 640.0792 ([M-Os]+, 100%), 642.0812 ([M-Os]+, 80%), 644.0832 ([M-Os]+, 60%), 646.0852 ([M-Os]+, 40%). + 640.0785) required

[0343] The complete preparation method of the compound of Chemical Formula 10 is shown in the following Reaction Formula 8.

[0344] [Reaction Formula 8]

[0345]

[0346] Example 1.9. Synthesis of transition metal complex of Chemical Formula 11

[0347] 1) Synthesis of (pyridin-2-yl)amidrazones

[0348]

[0349] 2-cyanopyridine 5.2 g (50 mmol) and hydrazine hydrate 2.7 g (55 mmol) were added to a 100 mL two-necked round-bottom flask, and 4 mL of ethanol was added, and they were stirred at room temperature for 24 hours. After the reaction was completed, the reaction mixture was filtered under reduced pressure to remove the remaining solvent, and washed with benzene. The filtered solid was recrystallized in toluene to obtain (pyridin-2-yl)amidrazones. (4.2 g, 61%)

[0350] 2) Synthesis of 2-(1,3-dimethyl-1H-1,2,4-triazol-5-yl)pyridine

[0351]

[0352] (pyridin-2-yl)amidrazones 2.0 g (15 mmol) prepared in the above 1) and sodium carbonate 1.6 g (15 mmol) were added to a 50 mL Schlenk flask, and 15 mL of dimethylacetamide and 5 mL of tetrahydrofuran were added as solvents, and stirred at 0°C. In addition, 5 mL of anhydrous dimethylacetamide and 1.1 mL of acetyl chloride (15 mmol) were added to a 10 mL round-bottom flask, and closed with a rubber septum, and then dropped into the reaction mixture under argon through a cannula, and stirred at room temperature for 5 hours. After the reaction was completed, the reaction mixture was filtered under reduced pressure to remove the remaining solvent, and washed with ethanol and distilled water to obtain a white solid. The white solid and 20 mL of ethylene glycol were added to a 50 mL single-necked flask, and heated to 190°C and stirred for 30 minutes. After the reaction was completed, the reaction mixture was cooled to room temperature, and the ethylene glycol solvent was removed by distillation under reduced pressure to finally obtain 2-(5-R-2H-1,2,4-triazol-3-yl)pyridine as a yellow solid. (0.22 g, 9%)

[0353] To a 50 mL single neck flask, 2-(3-methyl-1H-1,2,4-triazol-5-yl)pyridine 0.22 g (1.4 mmol) was added and dissolved in 5 mL of anhydrous dimethylformamide under argon atmosphere, followed by the addition of sodium hydride 83 mg (2.0 mmol). The reaction mixture was stirred to room temperature for 20 minutes, and iodomethane 0.3 g (2.0 mmol) was added under argon atmosphere, followed by stirring again at room temperature for 24 hours. After the completion of the reaction, the reaction mixture was extracted with water (100 mL) and ethyl acetate (100 mL x 3). The organic layer was collected and concentrated under reduced pressure, and purified by column chromatography using ethyl acetate and hexane as developing solvents. (Hexane: ethyl acetate = 7:3) 2-(1,3-dimethyl-1H-1,2,4-triazol-5-yl)pyridine was finally obtained. (83 mg, 34%)

[0354] 3) Synthesis of Os(Dmtz-py)2Cl2 [Formula 11]

[0355]

[0356] 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 to a 5 mL Corn vial and dissolved in 2 mL of ethylene glycol under argon atmosphere, followed by argon degassing for 15 minutes. The reaction mixture was heated to 180°C and stirred for 1 hour. After the completion of the reaction, the reaction mixture was cooled to room temperature, and filtered and the generated red precipitate was removed under reduced pressure. The filtrate was dropped into a 1.0 M aqueous solution of sodium dithionite (10 mL), thereby obtaining a precipitate of a reduced osmium complex. The generated solid was filtered under reduced pressure and washed with water several times, and then dried in a vacuum oven at 40°C to obtain a brown final compound, an osmium complex. (15 mg, 86%) HRMS (ESI+) m / z 610.0797 ([M+H]+, 100%) 192 Os): m / z 610.0797 ([M + ] requires 610.0792)

[0357] The complete preparation method of the compound of Formula 11 is shown in the following Reaction Scheme 9.

[0358] [Reaction Scheme 9]

[0359]

[0360] Example 1.10. Synthesis of a transition metal complex of Formula 12

[0361] 1) Synthesis of 5-methyl-3-(pyridin-2-yl)-1,2,4-oxadiazole

[0362]

[0363] A reflux condenser and a gas inlet were fitted to a 250 mL two-necked round bottom flask, and hydroxylammonium chloride 7.0 g (0.1 mol) and potassium hydroxide 6.0 g (0.1 mol) were added to 100 mL of methanol and heated to 100°C and stirred for 30 minutes. The generated potassium chloride was concentrated and removed under reduced pressure, and to the filtered reaction solution, pyridine nitrile 7.0 g (60 mmol) was added and heated to 100°C and stirred for 1 hour. After the completion of the reaction, the mixture was concentrated under reduced pressure and washed with distilled water to obtain hydroxyl pyridine amide as a transparent solid. (9.0 g, 65%)

[0364] A reflux condenser and a gas inlet were fitted to a 250 mL two-necked round bottom flask, and hydroxyl pyridine amide 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 60 mL of tetrahydrofuran and heated to 110°C and stirred for 8 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature and extracted with water (100 mL) and ethyl acetate (100 mL x 3). The organic layer was concentrated under reduced pressure, and after the removal of the solvent, 5-methyl-3-(pyridin-2-yl)-1,2,4-oxadiazole was obtained as a transparent solid. (0.85 g, 72%)

[0365] 2) Synthesis of Os(Me-oxz-py)2Cl2 [Chemical Formula 12]

[0366]

[0367] Potassium hexachloroosmate (IV) 0.6 g (1.4 mmol) and 5-methyl-3-(pyridin-2-yl)-1,2,4-oxadiazole prepared in 1) above 0.5 g (2.9 mmol) were added to a 250 mL Schlenk flask and dissolved in 50 mL of ethylene glycol under an argon atmosphere, followed by argon degassing for 15 minutes. The reaction mixture was heated to 180°C and stirred for 20 minutes. After the completion of the reaction, the reaction mixture was cooled to room temperature and filtered and the generated red precipitate was removed under reduced pressure. The filtrate was dropped into a 1.0 M aqueous solution of sodium dithionite (30 mL), thereby obtaining a precipitate of a reduced osmium complex. The generated solid was filtered under reduced pressure and washed with water and acetonitrile several times, and then dried in a vacuum oven to obtain the final compound, an osmium complex, as a yellowish brown solid. (0.6 g, 70%)

[0368] The complete preparation method of the compound of Chemical Formula 12 is shown in the following Reaction Formula 10.

[0369]

[0370] Example 1.11. Synthesis of transition metal complex of Chemical Formula 13

[0371] 1) Synthesis of 2-(1-butyl-1H-1,2,3-triazol-4-yl)pyridine

[0372]

[0373] To a 250 mL round bottom flask was added 1-bromobutane 2.0 g (14 mmol) and sodium azide 0.9 g (14 mol) and added 50 mL of anhydrous dimethylformamide and stirred at room temperature for 24 hours. After completion of the reaction, the reaction mixture was extracted with water (100 mL) and diethyl ether (100 mL x 3). The organic layer was collected and dried over magnesium sulfate and concentrated under reduced pressure and after removal of the solvent, the next reaction was carried out without additional purification. To a 250 mL two necked round bottom flask was added 1-azidobutane and 2-ethynylpyridine 1.5 g (14 mmol) and added tetrahydrofuran / water (40 mL / 40 mL) and stirred at room temperature. To this reaction mixture was added sodium ascorbate 0.3 g (1.4 mmol) and copper sulfate 23 mg (0.14 mmol) and argon degassed for 15 minutes and then stirred at room temperature for 2 hours. After completion of the reaction, the reaction mixture was extracted with water (100 mL) and ethyl acetate (100 mL x 3) and the organic layer was collected and dried over magnesium sulfate. This solution was concentrated under reduced pressure and the solvent was removed and purified by column chromatography using ethyl acetate and hexane as developing solvents (hexane: ethyl acetate = 1:4). 2-(1-(2-methoxyethynyl)-1H-1,2,3-triazol-4-yl)pyridine was obtained finally. (1.5 g, 52%)

[0374] 2) Synthesis of Os(3-Bu-tz-py)2Cl2 [Chemical Formula 13]

[0375]

[0376] Potassium osmate(VI) 0.5 g (1.0 mmol) and 2-(1-butyl-1H-1,2,3-triazol-4-yl)pyridine prepared in 1) above 0.4 g (2.0 mmol) were added to a 100 mL Schlenk flask and dissolved in 15 mL of ethylene glycol under an argon atmosphere, and then argon degassing was performed for 15 minutes. The reaction mixture was heated to 180°C and stirred for 1 hour. After the completion of the reaction, the reaction mixture was cooled to room temperature, and the resulting red precipitate was filtered and removed under reduced pressure. The filtrate was dropped into a 1.0 M aqueous solution of sodium dithionite (200 mL), thereby obtaining a precipitate of a reduced osmium complex. The resulting solid was filtered under reduced pressure and washed with water several times, and then dried in a vacuum oven at 40°C to obtain the final compound, an osmium complex. (0.4 g, 56%)

[0377] The complete preparation method of the compound of Chemical Formula 13 is shown in the following Reaction Formula 11.

[0378] [Reaction Formula 11]

[0379]

[0380] Example 1.12. Synthesis of a transition metal complex of Chemical Formula 14

[0381] 1) Synthesis of 13-bromo-2,5,8,11-tetraoxatridecan

[0382]

[0383] Tetraethylene glycol monomethyl ether 2.0 g (9.6 mmol) and tetra- bromomethane 3.8 g (11.5 mmol) were added to a 250 mL round bottom flask and dissolved in 50 mL of dichloromethane, and then stirred at 0°C using a freezer. Thereafter, triphenylphosphine 3.0 g (11.5 mmol) was subdivided for 15 minutes while maintaining 0°C, and slowly added and stirred at room temperature for 2 hours. After the completion of the reaction, the reaction mixture was extracted with water (100 mL) and dichloromethane (100 mL x 3). The organic layer was collected and concentrated under reduced pressure, and purified by column chromatography using ethyl acetate and hexane as developing solvents (hexane: ethyl acetate = 2:1 (methanol 8%)). 13-bromo-2,5,8,11-tetraoxatridecan was finally obtained as a yellow oil. (1.4 g, 54%)

[0384] 2) Synthesis of 2-(1-(2,5,8,11-tetraoxatridecan-13-yl)-1H-1,2,3-triazol-4-yl)pyridine

[0385]

[0386] The 13-bromo-2,5,8,11-tetraoxatridecan-13-ol 1.4 g (5.2 mmol) prepared in the above 1) and sodium azide 0.34 g (5.2 mmol) were added to a 250 mL round bottom flask, and 40 mL of anhydrous dimethylformamide was added and stirred at room temperature for 24 hours. After the completion of the reaction, the reaction mixture was extracted with water (100 ml) and diethyl ether (100 mL x 3). The organic layer was collected and dried with magnesium sulfate, and concentrated under reduced pressure, and after removing the solvent, the next reaction was performed without additional purification. The 13-azido-2,5,8,11-tetraoxatridecan and 2-ethynylpyridine 0.8 g (7.7 mmol) were added to a 250 mL two-necked round bottom flask, and tetrahydrofuran / water (40 mL / 40 mL) was added and stirred at room temperature. To this reaction mixture, sodium ascorbate 0.15 g (0.8 mmol) and copper sulfate 12 mg (0.08 mmol) were added, and argon degassing was performed for 15 minutes, and then it was stirred at room temperature for 2 hours. After the completion of the reaction, the reaction mixture was extracted with water (100 mL) and ethyl acetate (100 mL x 3), and the organic layer was collected, and the layers were collected and dried with magnesium sulfate. The solution was concentrated under reduced pressure and the solvent was removed, and purified by column chromatography using ethyl acetate and hexane as developing solvents (hexane: ethyl acetate = 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%)

[0387] 3) Synthesis of Os(3-tz-teg-py)2Cl2 [Chemical Formula 14]

[0388]

[0389] 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 the above 2) were added to a 50 mL Schlenk flask, and dissolved in 15 mL of ethylene glycol under an argon atmosphere, and then argon degassing was performed for 15 minutes. The reaction mixture was heated to 180°C and stirred for 1 hour. After the completion of the reaction, the reaction mixture was cooled to room temperature, and filtered and the generated red precipitate was removed under reduced pressure. The filtrate was dropped into a 1.0 M aqueous solution of sodium dithionite (10 mL), thereby obtaining a precipitate of a reduced osmium complex. The generated solid was filtered under reduced pressure and washed with water several times, and then dried in a vacuum oven at 40°C to obtain the final compound, an osmium complex, as a black purple color. (0.1 g, 56%)

[0390] The complete preparation method of the compound of Chemical Formula 14 is shown in the following Reaction Formula 12.

[0391] [Reaction Formula 12]

[0392]

[0393] Example 1.13. Synthesis of transition metal complex of Chemical Formula 15

[0394] 1) Synthesis of 2-(1-(2-methoxyethynyl)-1H-1,2,3-triazol-4-yl)pyridine

[0395]

[0396] 2.0 g (14 mmol) of 2-bromoethyl methyl ether and 0.1 g (14 mol) of sodium azide were added to a 250 mL round-bottom flask, and 50 mL of anhydrous dimethylformamide was added and stirred at room temperature for 24 hours. After the reaction was completed, the reaction mixture was extracted with water (100 ml) and diethyl ether (100 ml x 3). The organic layer was collected and concentrated under reduced pressure, and after the solvent was removed, no additional purification was performed, and the next reaction was performed. 2-Azidoethyl methyl ether and 1.5 g (14 mmol) of 2-ethynylpyridine were added to a 250 mL two-necked round-bottom flask, and tetrahydrofuran / water (40 mL / 40 mL) was added and stirred at room temperature. To the reaction mixture, 0.28 g (1.4 mmol) of sodium ascorbate and 0.02 g (0.14 mmol) of copper sulfate were added, and argon degassing was performed for 15 minutes, and then it was stirred at room temperature for 2 hours. After the reaction was completed, the reaction mixture was extracted with water (100 ml) and ethyl acetate (100 mL x 3). The organic layer was collected and dried with magnesium sulfate. The solution was concentrated under reduced pressure to remove the solvent, and purified by column chromatography using ethyl acetate and hexane as developing solvents (hexane: ethyl acetate = 1:4). 2-(1-(2-methoxyethynyl)-1H-1,2,3-triazol-4-yl)pyridine was finally obtained. (1.5 g, 52%)

[0397] 2) Synthesis of Os(3-mo-tz-py)2Cl2 [Chemical Formula 15]

[0398]

[0399] Potassium osmate(VI) 0.5 g (1.0 mmol) and 2-(1-(2-methoxyethynyl)-1H-1,2,3- triazol-4-yl)pyridine prepared in 1) above 0.4 g (2.1 mmol) were added to a 100 mL Schlenk flask and dissolved in 15 mL of ethylene glycol under an argon atmosphere, and then argon degassing was performed for 15 minutes. The reaction mixture was heated to 180°C and stirred for 1 hour. After the reaction was completed, the reaction mixture was cooled to room temperature, and the resulting red precipitate was filtered and removed under reduced pressure. The filtrate was dropped into a 1.0 M aqueous solution of sodium dithionite (200 mL), thereby obtaining a precipitate of a reduced osmium complex. The resulting solid was filtered under reduced pressure and washed with water several times, and then dried in a vacuum oven at 40°C to obtain a green final compound, an osmium complex. (0.4 g, 56%) HRMS (ESI+) m / z 670.9967 ([M-H]-, C24H18N10O6S2 requires 670.10). 192 OS) : m / z 670.9967 ([M + ] requires 670.10)

[0400] The complete preparation method of the compound of Chemical Formula 15 is shown in the following Reaction Formula 13.

[0401] [Reaction Formula 13]

[0402]

[0403] Example 1.1. Synthesis of a transition metal complex of Chemical Formula 16

[0404] 1) Synthesis of 2-(1H-tetrazol-5-yl)pyridine

[0405]

[0406] A reflux condenser and a gas inlet were attached to a 250 mL two-necked round bottom flask, and sodium azide 1.3 g (19.2 mmol), 2-ethynylpyridine 2.0 g (19.2 mol), and copper sulfate 96 mg (0.38 mmol) were added and dissolved in 40 mL of anhydrous dimethyl sulfoxide under an argon atmosphere. For the reaction mixture, argon degassing was performed for 15 minutes, and then it was heated to 140°C and stirred for 3 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, extracted with water (100 mL) and ethyl acetate (100 mL x 3), and the organic layer was collected and dried with magnesium sulfate. The solution was concentrated under reduced pressure to remove the solvent, and finally 2-(1H-tetrazol-5-yl)pyridine was obtained as a yellow solid. (1.1 g, 41%)

[0407] 2) Synthesis of 2-(1-methyl-1H-tetrazol-5-yl)pyridine

[0408]

[0409] A reflux condenser and a gas inlet were attached to a 100 mL two-necked round bottom flask, and 2-(1H-tetrazol-5-yl)pyridine 1.0 g (6.8 mmol) prepared in 1) above was dissolved in anhydrous tetrahydrofuran (30 mL) under an argon atmosphere, and then sodium hydride 0.4 g (10 mmol) was added. The reaction mixture was stirred at room temperature for 30 minutes, iodomethane 1.5 g (10 mmol) was added under an argon atmosphere, and then it was heated to 80°C and stirred for 3 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature, and extracted with water (100 mL) and ethyl acetate (100 mL x 3). The organic layer was concentrated under reduced pressure, and after removing the solvent, purification was performed by column chromatography using ethyl acetate and hexane as developing solvents (hexane: ethyl acetate = 1:3). Finally, 2-(1-methyl-1H-tetrazol-5-yl)pyridine was obtained. (0.4 g, 40%)

[0410] 3) Synthesis of Os(tetraz-py)2Cl2 [Chemical Formula 16]

[0411]

[0412] Potassium hexachloroosmate (IV) 0.10 g (0.21 mmol) and 2-(1-methyl-1H-tetrazol-5-yl)pyridine 0.7 g (0.42 mmol) prepared in 2) above were added to a 50 mL Schlenk flask, and dissolved in 5 mL of ethylene glycol under an argon atmosphere, and then argon degassing was performed for 15 minutes. The reaction mixture was heated to 180°C and stirred for 1 hour. After the completion of the reaction, the reaction mixture was cooled to room temperature, and filtered and the generated red precipitate was removed under reduced pressure. The filtrate was dropped into a 1.0 M aqueous solution of sodium dithionite (200 mL), thereby obtaining a precipitate of a reduced osmium complex. The generated solid was filtered under reduced pressure and washed with water several times, and then dried in a vacuum oven at 40°C to obtain the final compound, a green osmium complex. (0.1 g, 84%) HRMS (ESI+) m / z 584.0383 ([M-OH]+, 100%), 584.04 (100%) (ESI-) 192 OS): m / z 584.0383 ([M + ] requires 584.04)

[0413] The complete preparation method of the compound of Chemical Formula 16 is shown in the following Reaction Scheme 14.

[0414] [Reaction Scheme 14]

[0415]

[0416] Example 1.15. Synthesis of a transition metal complex of Chemical Formula 17

[0417] 1) Synthesis of 2-(1H-1,2,4-triazol-1-yl)pyridine

[0418]

[0419] A reflux condenser and a gas inlet were equipped to a 250 mL two-necked round bottom flask, and 1H-1, 2, 4-triazole 3.0 g (43 mmol) and potassium tert-butoxide 5.8 g (52 mmol) were added and dissolved in 40 mL of anhydrous dimethyl sulfoxide under an argon atmosphere. To this reaction mixture, 5.0 g (52 mmol) of 2-fluoropyridine was added, and heated to 100°C under an argon atmosphere and stirred for 4 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature, and extracted with water (100 mL) and ethyl acetate (100 mL x 3). The organic layer was collected and concentrated under reduced pressure, and after removing the solvent, purified by column chromatography using ethyl acetate and hexane as developing solvents (hexane: ethyl acetate = 5:1). 2-(1H-1, 2, 4-triazol-1-yl)pyridine was finally obtained as a transparent solid. (4.3 g, 57%)

[0420] 2) Synthesis of Os(1,2,4tz-py)2Cl2 [Chemical Formula 17]

[0421]

[0422] 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 to a 250 mL Schlenk flask and dissolved in 50 mL of ethylene glycol under an argon atmosphere, followed by argon degassing for 15 minutes. The reaction mixture was heated to 180°C and stirred for 30 minutes. After the completion of the reaction, the reaction mixture was cooled to room temperature, filtered and the generated red precipitate was removed under reduced pressure. The filtrate was dropped into a 1.0 M aqueous solution of sodium hydrosulfite (30 mL), thereby obtaining a precipitate of a reduced osmium complex. The generated solid was filtered under reduced pressure and washed with water and acetonitrile several times, and then dried in a vacuum oven to obtain the final compound, an osmium complex, as a deep red color. (0.3 g, 62%)

[0423] The complete preparation method of the compound of Chemical Formula 17 is shown in the following Reaction Formula 15.

[0424] [Reaction Formula 15]

[0425]

[0426] Example 1.16. Synthesis of a transition metal complex of Chemical Formula 18

[0427] 1) Synthesis of 2-(1H-1, 2, 3-triazol-1-yl)pyridine

[0428]

[0429] A reflux condenser and a gas inlet were equipped to a 250 mL two-necked round bottom flask, and 1H-1,2,3-triazole 3.0 g (43 mmol) and potassium tert-butoxide 5.8 g (52 mmol) were added and dissolved in 40 mL of anhydrous dimethyl sulfoxide under an argon atmosphere. To this reaction mixture, 2-fluoropyridine 5.0 g (52 mmol) was added, and heated to 100°C under an argon atmosphere and stirred for 4 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature, and extracted with water (100 mL) and ethyl acetate (100 mL x 3). The organic layer was collected and concentrated under reduced pressure, and after removing the solvent, purified by column chromatography using ethyl acetate and hexane as developing solvents (hexane: ethyl acetate = 5:1). 2-(1H-1,2,3-triazol-1-yl)pyridine was finally obtained as a transparent solid. (3.5 g, 56%)

[0430] 2) Synthesis of Os(1,2,3tz-py)2Cl2 [Chemical Formula 18]

[0431]

[0432] Potassium hexachloroosmate (IV) 0.6 g (1.4 mmol) and 2-(1H-1,2,3-triazol-1-yl)pyridine prepared in 1) above 0.4 g (2.9 mmol) were added to a 250 mL Schlenk flask, and dissolved in 50 mL of ethylene glycol under an argon atmosphere, followed by argon degassing for 15 minutes. The reaction mixture was heated to 180°C and stirred for 30 minutes. After the completion of the reaction, the reaction mixture was cooled to room temperature, and filtered and the generated red precipitate was removed under reduced pressure. The filtrate was dropped into a 1.0 M aqueous solution of sodium hydrosulfite (30 mL), thereby obtaining a precipitate of a reduced osmium complex. The generated solid was filtered under reduced pressure and washed with water and acetonitrile several times, and then dried in a vacuum oven to obtain the final compound, an osmium complex, as green. (0.4 g, 69%)

[0433] The complete preparation method of the compound of Chemical Formula 18 is shown in the following Reaction Scheme 16.

[0434] [Reaction Scheme 16]

[0435]

[0436] Example 1.17. Synthesis of a transition metal complex of Chemical Formula 19

[0437] 1) Synthesis of 2-(1-methyl-1H-1,2,4-triazol-5-yl)pyridine

[0438]

[0439] Into a 100 mL two-necked round bottom flask, 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 and dissolved in 50 mL of anhydrous dimethyl sulfoxide. Methyl iodide 1.4 g (0.01 mol) was added dropwise to the reaction mixture using a dropping funnel and stirred at room temperature for 24 hours. After completion, the reaction mixture was extracted with water (100 mL) and ethyl acetate (100 mL x 3). The organic layer was collected and concentrated under reduced pressure, and after removing the solvent, purified by column chromatography using ethyl acetate and hexane as developing solvents (hexane: ethyl acetate = 5:1). Finally, 2-(1-methyl-1H-1,2,4-triazol-5-yl)pyridine was obtained as a transparent solid. (0.9 g, 86%)

[0440] 2) Synthesis of Os(4-Me-1,2,4tz-py)2Cl2 [Formula 19]

[0441]

[0442] Into a 250 mL Schlenk flask, potassium hexachloroosmate (IV) 0.6 g (1.4 mmol) and 2-(1-methyl-1H-1,2,4-triazol-5-yl)pyridine prepared in 1) above 0.5 g (2.9 mmol) were added and dissolved in 50 mL of ethylene glycol under an argon atmosphere, followed by argon degassing for 15 minutes. The reaction mixture was heated to 180°C and stirred for 1 hour. After completion of the reaction, the reaction mixture was cooled to room temperature, filtered and the generated red precipitate was removed under reduced pressure. The filtrate was dropped into a 1.0 M aqueous solution of sodium hydrosulfite (30 mL), thereby obtaining a precipitate of a reduced osmium complex. The generated solid was filtered under reduced pressure and washed with water and acetonitrile several times, and then dried in a vacuum oven to obtain the final compound, a green osmium complex. (0.2 g, 25%).

[0443] The complete preparation method of the compound of Formula 19 is shown in the following Reaction Formula 17.

[0444] [Reaction Formula 17]

[0445]

[0446] Example 1.18. Synthesis of a transition metal complex of Formula 20

[0447] 1) Synthesis of 2-(3,4-dimethyl-1H-pyrazol-1-yl)-4-methylpyridine

[0448]

[0449] A reflux condenser and a gas inlet were attached to a 250 mL two-necked round bottom flask, 3,4-dimethylpyrazole 2.1 g (22 mmol) and potassium tert-butoxide 2.5 g (22 mmol) were added and dissolved in 20 mL of anhydrous dimethyl sulfoxide under an argon atmosphere. To this reaction mixture, 2-bromo-4-methylpyridine 3.5 g (20 mmol) was added and heated to 100°C under an argon atmosphere and stirred for 18 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature and extracted with water (100 mL) and ethyl acetate (100 mL x 3). The organic layer was collected and concentrated under reduced pressure, and after removing the solvent, purified by column chromatography using ethyl acetate and hexane as developing solvents (hexane: ethyl acetate = 3:1). 4-methyl-2-(3-methyl-1H-pyrazol-1-yl)pyridine was obtained as a transparent solid. (2.4 g, 63%)

[0450] 2) Synthesis of Os(3,4-DiMe-pz-4-Me-py)2Cl2 [Formula 20]

[0451]

[0452] Potassium hexachloroosmate (IV) 0.5 g (1.0 mmol) and 2-(3,4-dimethyl-1H-pyrazol-1-yl)-4-methylpyridine prepared in 1) above 0.4 g (2.0 mmol) were added to a 50 mL Schlenk flask and dissolved in 15 mL of ethylene glycol under an argon atmosphere, followed by argon degassing for 15 minutes. The reaction mixture was heated to 180°C and stirred for 1 hour. After the completion of the reaction, the reaction mixture was cooled to room temperature and filtered and the generated red precipitate was removed under reduced pressure. The filtrate was dropped into a 1.0 M aqueous solution of sodium dithionite (100 mL), thereby obtaining a precipitate of a reduced osmium complex. The generated solid was filtered under reduced pressure and washed with water and acetonitrile several times, and then dried in a vacuum oven to obtain the final compound, a green osmium complex. (0.4 g, 62%) HRMS (ESI+) m / z 636.1205 ([M - Cl]2+, 100%), 636.1200 (ESI+) [M - Cl]2+, 100%) 192 Os): m / z 636.1205 ([M - Cl]2+, 100%), 636.1200 (ESI+) [M - Cl]2+, + 636.1200) required

[0453] The complete preparation method of the compound of Formula 20 is shown in the following Reaction Scheme 18.

[0454] [Reaction Scheme 18]

[0455]

[0456] Example 1.19. Synthesis of a transition metal complex of Formula 21

[0457] 1) Synthesis of 2-(3,4-dimethyl-1H-pyrazol-1-yl)-4-methoxypyridine

[0458]

[0459] A reflux condenser and a gas inlet were equipped to a 50 mL two-necked round bottom flask, 3,4-dimethylpyrazole 0.6 g (6 mmol) and potassium tert-butoxide 0.7 g (6 mmol) were added and dissolved in 8 mL of anhydrous dimethyl sulfoxide under an argon atmosphere. 2-bromo-4-methoxypyridine 1.0 g (5 mmol) was added and heated to 80°C under an argon atmosphere and stirred for 6 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature and extracted with water (50 mL) and ethyl acetate (50 mL x 3). The organic layer was collected and concentrated under reduced pressure, and after removing the solvent, purified by column chromatography using ethyl acetate and hexane as developing solvents (hexane: ethyl acetate = 3:1). 4-methyl-2-(3-methyl-1H-pyrazol-1-yl)pyridine was obtained as a transparent solid. (0.4 g, 37%)

[0460] 2) Synthesis of Os(3,4-DiMe-pz-4-MeO-py)2Cl2 [Formula 21]

[0461]

[0462] 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) were added to a 50 mL Schlenk flask and dissolved in 15 mL of ethylene glycol under an argon atmosphere, followed by argon degassing for 15 minutes. The reaction mixture was heated to 180°C and stirred for 30 minutes. After the completion of the reaction, the reaction mixture was cooled to room temperature and filtered under reduced pressure and the resulting red precipitate was removed. The filtrate was dropped into a 1.0 M aqueous solution of sodium hydrosulfite (100 mL), thereby obtaining a precipitate of a reduced osmium complex. The resulting solid was filtered under reduced pressure and washed with water and acetonitrile several times, and then dried in a vacuum oven to obtain the final compound, a brown osmium complex. (0.4 g, 64%) HRMS (Os): m / z 668.1103 ([M 192 Os): 668.1098) + 668.1098)

[0463] The complete preparation method of the compound of Formula 21 is shown in the following Reaction Scheme 19.

[0464] [Reaction Scheme 19]

[0465]

[0466] Example 1.20. Synthesis of a transition metal complex of Formula 22

[0467] 1) Synthesis of N,N-dimethyl-2-(4-methyl-1H-pyrazol-1-yl)pyridine-4-amine

[0468]

[0469] A reflux condenser and inlet were fitted into a 50 mL two-necked round-bottom flask, and 1.0 g (5.0 mmol) of 4-dimethylamino-2-bromopyridine, 1.2 g (15 mmol) of 4-methylpyrazole, 0.14 g (0.75 mmol) of copper iodide, 0.17 g (1.5 mmol) of L-proline, and 4.1 g (12.5 mmol) of cesium carbonate were added and dissolved in 20 mL of anhydrous dimethylformamide under an argon atmosphere. The reaction mixture was heated to 120 °C and stirred for 20 hours. After the reaction was complete, the reaction mixture was cooled to room temperature and extracted with water (50 mL) and ethyl acetate (50 mL × 3). The organic layer was collected and concentrated under reduced pressure, and after solvent removal, purified by column chromatography using ethyl acetate and hexane as developing solvents (hexane:ethyl acetate = 5:1). The final product was N,N-dimethyl-2-(4-methyl-1H-pyrazole-1-yl)pyridine-4-amine as a white solid. (0.5g, 50%)

[0470] 2) Synthesis of Os(4-Me-pz-4-DiAM-py)2Cl2 [Chemical Formula 22]

[0471]

[0472] 0.6 g (1.2 mmol) of potassium hexachloroosmium(IV) and 0.5 g (2.4 mmol) of N,N-dimethyl-2-(4-methyl-1H-pyrazol-1-yl)pyridine-4-amine prepared in step 1) above were added to a 50 mL Schlenk flask and dissolved in 15 mL of ethylene glycol under an argon atmosphere, followed by argon degassing for 15 min. The reaction mixture was heated to 180 °C and stirred for 30 min. After the reaction was complete, the reaction mixture was cooled to room temperature and filtered under reduced pressure to remove the resulting red precipitate. The filtrate was added dropwise to a 1.0 M aqueous solution of sodium dithionite (100 mL) to obtain a precipitate of the reduced osmium complex. The resulting solid was filtered under reduced pressure and washed several times with water and acetonitrile, then dried in a vacuum oven to obtain the final compound, a dark red osmium complex (0.5 g, 75%). HRMS ( 192 Os): m / z 666.1421([m + ]Requirement 666.1418)

[0473] The complete preparation method of the compound of chemical formula 22 is shown in the following reaction formula 20.

[0474] [Reaction Formula 20]

[0475]

[0476] Example 1.21. Synthesis of transition metal complex of Chemical Formula 23

[0477] 1) Synthesis of Ru(DMSO)4Cl2

[0478]

[0479] RuCl3*xH2O 0.9 g (4.3 mmol) and anhydrous dimethyl sulfoxide (5 mL) were added to a 50 mL Schlenk flask and degassed for 10 minutes under argon atmosphere. This dark red suspension was heated to 170 °C and stirred for 30 minutes. After maintaining the temperature, until the color of the reaction solution changed to dark yellow, the temperature was decreased to room temperature to terminate the reaction. To the reaction solution, 4 mL of acetone was added and it was cooled to 0 °C, then left to stand for 4-5 hours. The resulting solid was filtered under reduced pressure and washed with cold acetone. Ru(DMSO)4Cl2 was finally obtained as a yellow solid. It was used for the next reaction without additional purification. (1.5 g, 75%)

[0480] 2) Synthesis of Ru(pzpy)2Cl2 [Chemical Formula 23]

[0481]

[0482] Ru(DMSO)4Cl2 0.4 g (0.86 mmol), 2-(1H-pyrazol-1-yl)pyridine prepared in the above experimental example 0.25 g (1.7 mmol), lithium chloride 1.8 g (43.0 mmol) and anhydrous dimethylformamide (15 mL) were added to a 50 mL Schlenk flask and degassed for 10 minutes under argon atmosphere. To shield light, the reaction vessel was wrapped with aluminum foil, then stirred at 150 °C for 4 hours. After the completion of the reaction, 50 mL of acetone was added to the deep purple reaction solution and cooled at 0 °C for 24 hours. The black purple solid was filtered under reduced pressure, and to remove lithium chloride and by-products, it was washed with acetone until the color of the filtrate became transparent. The remaining deep purple solid was dried in a vacuum oven to obtain the final compound ruthenium complex. After that, it was left to stand for 4-5 hours. The resulting solid was filtered under reduced pressure and washed with cold acetone. Ru(DMSO)4Cl2 was finally obtained as a yellow solid. (0.25 g, 55%) HRMS: m / z 461.9710 ([M-H]-) required 461.9690 + ] requires 461.9690

[0483] The complete preparation method of the compound of Chemical Formula 23 is shown in the following Reaction Formula 21.

[0484]

[0485] Example 1.22. Synthesis of transition metal complex of formula 24

[0486] 1) Synthesis of Ru(4-Me-pz4-Me-py)2Cl2 [formula 24]

[0487]

[0488] Ru(DMSO)4Cl20.4 g (0.86 mmol), 4-methyl-2-(4-methyl-lH-pyrazol-l-yl)pyridine 0.3 g (1.7 mmol) prepared in the above experimental example, lithium chloride 1.8 g (43.0 mmol), and anhydrous dimethylformamide (15 mL) were added to a 50 mL Schlenk tube and degassed for 10 minutes under argon atmosphere. To shield light, the reaction vessel was wrapped with aluminum foil, and then stirred at 150 °C for 4 hours. After the reaction was completed, 50 mL of acetone was added to the deep purple reaction solution and cooled at 0 °C for 24 hours. The black purple solid was filtered under reduced pressure, and to remove lithium chloride and by-products, washed with acetone until the color of the filtrate became transparent. The remaining deep purple solid was dried in a vacuum oven to obtain the final compound ruthenium complex. (0.1 g, 23%) HRMS: m / z 518.0321 ([M + ] requires 518.0316)

[0489] The complete preparation method of the compound of formula 24 is shown in the following reaction formula 22.

[0490]

[0491] Example 1.23. Synthesis of transition metal complex of formula 25

[0492] 1) Synthesis of Fe(pzpy)2Cl2 [formula 25]

[0493]

[0494] FeCl3 1.6 g (10.0 mmol), 2-(1 H-pyrazol-1 -yl)pyridine 1.5 g (10.0 mol), terephthalic acid 3.3 g (20.0 mmol), sodium hydroxide 0.8 g (20 mmol) and anhydrous ethanol (30 mL) prepared in the experimental example were added to a 100 mL Schlenk bottle and degassed for 10 minutes under argon atmosphere. The reaction solution was stirred at 50°C for 96 hours. After completion of the reaction, the temperature was reduced to room temperature and the resulting black red solid was filtered under reduced pressure and washed with acetone. The black red solid was dried in a vacuum oven to obtain the final compound iron complex. (1.0 g, 24%) HRMS: m / z 415.9971 ([M + ] requires 415.9995)

[0495] Example 2: Synthesis of a redox polymer comprising a transition metal complex according to the application

[0496] Example 2.1. Synthesis of a redox polymer of formula 28

[0497]

[0498] A reflux condenser, gas inlet and thermometer were fitted to a 100 mL three-necked round bottom flask and Os(pzpy)2Cl2 [formula 3] 0.12 g (0.22 mmol) prepared in example 1.1 was added and completely dissolved in 10 mL ethanol under argon atmosphere. 0.1 g of polyvinylimidazole (Mn= 10,000 g / mol) completely dissolved in 20 mL ethanol was added to the reaction mixture and heated to 100°C and stirred for 2 days. After completion of the reaction, the reaction mixture was cooled to room temperature and dropped into diethyl ether to obtain polymer precipitate. The resulting solid was filtered under reduced pressure and washed several times with diethyl ether and then dried in a vacuum oven at 40°C for 24 hours to finally obtain 0.2 g of dark green redox polymer of formula 25 (PVI-Os(pzpy)2Cl). (0.20 g, 91 %)

[0499] Example 2.2. Synthesis of a redox polymer of formula 29

[0500]

[0501] A reflux condenser, gas inlet and thermometer were fitted to a 100 mL three-necked round bottom flask and Os(pz-2-Me-py)2Cl2 [Formula 4] 0.13 g (0.22 mmol) prepared in Example 1.2 was added and completely dissolved in 10 mL of ethanol under argon atmosphere. 0.1 g of polyvinylimidazole (Mn = 10,000 g / mol) completely dissolved in 20 mL of ethanol was added to the reaction mixture and heated to 100 °C and stirred for 2 days. After completion of the reaction, the reaction mixture was cooled to room temperature and dropped into ether to obtain polymer precipitate. The resulting solid was filtered under reduced pressure and washed with ether several times and then dried in a vacuum oven at 40 °C for 24 h to finally obtain 0.2 g of dark green redox polymer of Formula 26 (PVI-Os(pz-2-Mepy)2Cl). (0.20 g, 87%)

[0502] Example 2.3. Synthesis of redox polymer of Formula 30

[0503]

[0504] Example 1.3. Synthesis of redox polymer of Formula 27

[0505] Example 2.4. Synthesis of redox polymer of Formula 31

[0506]

[0507] Os(pz-4-Me-py)2Cl2[Formula 6] 0.31 g (0.53 mmol) prepared in Example 1.4 was added to a 100 mL Schlenk flask and completely dissolved in 10 mL of ethanol under argon atmosphere. 0.2 g of polyvinylimidazole (Mn= 10,000 g / mol) completely dissolved in 30 mL of ethanol was added to the reaction mixture and heated to 120 °C and stirred for 36 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and dropped into diethyl ether to obtain polymer precipitates. The resulting solid was filtered under reduced pressure and washed with diethyl ether several times, then dried in a vacuum oven at 40 °C for 24 hours to finally obtain 0.4 g of dark green redox polymer of Formula 28 (PVI-Os(pz-4-Me-py)2Cl). (0.4 g, 78%)

[0508] Example 2.5. Synthesis of redox polymer of Formula 32

[0509]

[0510] Os(3-Me-pz-4-Me-py)2Cl2[Formula 7] 0.27 g (0.44 mmol) prepared in Example 1.5 was added to a 100 mL Schlenk flask and completely dissolved in 20 mL of ethanol under argon atmosphere. 0.2 g of polyvinylimidazole (Mn= 10,000 g / mol) completely dissolved in 30 mL of ethanol was added to the reaction mixture and heated to 120 °C and stirred for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and dropped into diethyl ether to obtain polymer precipitates. The resulting solid was filtered under reduced pressure and washed with diethyl ether several times, then dried in a vacuum oven at 40 °C for 24 hours to finally obtain 0.4 g of dark green redox polymer of Formula 29 (PVI-Os(3-Me-pz-4-Me-py)2Cl). (0.41 g, 87%)

[0511] Example 2.6. Synthesis of redox polymer of Formula 33

[0512]

[0513] Os(3-Me-pz-4-MeO-py)2Cl2[Formula 8] 0.14 g (0.22 mmol) prepared in Example 1.6 was added to a 100 mL Schlenk flask and completely dissolved in 10 mL of ethanol under argon atmosphere. 0.1 g of polyvinylimidazole (Mn= 10,000 g / mol) completely dissolved in 20 mL of ethanol was added to the reaction mixture and heated to 120 °C and stirred for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and dropped into diethyl ether to obtain polymer precipitates. The resulting solid was filtered under reduced pressure and washed with diethyl ether several times, then dried in a vacuum oven at 40 °C for 24 hours to finally obtain 0.22 g of a dark green redox polymer of Formula 30 (PVI-Os(3-Me-pz-4-MeO-py)2Cl). (0.22 g, 92%)

[0514] Example 2.7. Synthesis of a redox polymer of Formula 34

[0515]

[0516] Os(4-Me-pz-4-Me-py)2Cl2[Formula 9] 0.8 g (1.32 mmol) prepared in Example 1.7 was added to a 250 mL Schlenk flask and completely dissolved in 50 mL of ethanol under argon atmosphere. 0.5 g of polyvinylimidazole (Mn= 10,000 g / mol) completely dissolved in 50 mL of ethanol was added to the reaction mixture and heated to 120 °C and stirred for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and dropped into diethyl ether to obtain polymer precipitates. The resulting solid was filtered under reduced pressure and washed with diethyl ether several times, then dried in a vacuum oven at 40 °C for 24 hours to finally obtain 1.21 g of a dark green redox polymer of Formula 31 (PVI-Os(4-Me-pz-4-Me-py)2Cl). (1.21 g, 93%)

[0517] Example 2.8. Synthesis of a redox polymer of Formula 35

[0518]

[0519] Os(4-Me-pz-4-MeO-py)2Cl2[Formula 10] 0.14 g (0.22 mmol) prepared in Example 1.8 was added to a 100 mL Schlenk flask and completely dissolved in 10 mL of ethanol under argon atmosphere. 0.1 g of polyvinylimidazole (Mn= 10,000 g / mol) completely dissolved in 20 mL of ethanol was added to the reaction mixture and heated to 120 °C and stirred for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and dropped into diethyl ether to obtain polymer precipitate. The resulting solid was filtered under reduced pressure and washed with diethyl ether several times, then dried in a vacuum oven at 40 °C for 24 hours to finally obtain 0.20 g of greenish red polyoxometalate (PVI-Os(4-Me-pz-4-MeO-py)2Cl) of Formula 32. (0.20 g, 83%)

[0520] Example 2.9. Synthesis of polyoxometalate of Formula 36

[0521]

[0522] A reflux condenser, gas inlet, and a thermometer were fitted to a 100 mL three-necked round bottom flask and Os(Dmtz-py)2Cl2[Formula 11] 0.13 g (0.22 mmol) prepared in Example 1.9 was added and completely dissolved in 10 mL of ethanol under argon atmosphere. 0.1 g of polyvinylimidazole (Mn= 10,000 g / mol) completely dissolved in 20 mL of ethanol was added to the reaction mixture and heated to 100 °C and stirred for 2 days. After the reaction was completed, the reaction mixture was cooled to room temperature and dropped into diethyl ether to obtain polymer precipitate. The resulting solid was filtered under reduced pressure and washed with diethyl ether several times, then dried in a vacuum oven at 40 °C for 24 hours to finally obtain 0.15 g of brown polyoxometalate (PVI-Os(Dmtz-py)2Cl) of Formula 33. (0.15 g, 65%)

[0523] Example 2.10. Synthesis of polyoxometalate of Formula 37

[0524]

[0525] A reflux condenser, gas inlet, and thermometer were fitted to a 100 mL three-necked round bottom flask and 0.12 g of Os(3-Bu-tz-py)2Cl2[Formula 13] prepared in Example 1.11 (0.18 mmol) was added and completely dissolved in 10 mL of ethanol under an argon atmosphere. 85 mg of polyvinylimidazole (Mn= 10,000 g / mol) completely dissolved in 20 mL of ethanol was added to the reaction mixture and heated to 100 °C and stirred for 2 days. After the reaction was completed, the reaction mixture was cooled to room temperature and dropped into diethyl ether to obtain a polymer precipitate. The resulting solid was filtered under reduced pressure and washed with diethyl ether several times, then dried in a vacuum oven at 40 °C for 24 hours to finally obtain 0.2 g of a red PVI-Os polymer of Formula 34 (PVI-Os(3-Bu-tz-py)2Cl).

[0526] (0.2 g, 95%)

[0527] Example 2.11. Synthesis of Redox Polymer of Formula 38

[0528]

[0529] A reflux condenser, gas inlet, and thermometer were fitted to a 100 mL three-necked round bottom flask and 0.12 g of Os(3-Bu-tz-py)2Cl2[Formula 13] prepared in Example 1.11 (0.18 mmol) was added and completely dissolved in 10 mL of ethanol under an argon atmosphere. 85 mg of polyvinylimidazole (Mn= 10,000 g / mol) completely dissolved in 20 mL of ethanol was added to the reaction mixture and heated to 100 °C and stirred for 2 days. After the reaction was completed, the reaction mixture was cooled to room temperature and dropped into diethyl ether to obtain a polymer precipitate. The resulting solid was filtered under reduced pressure and washed with diethyl ether several times, then dried in a vacuum oven at 40 °C for 24 hours to finally obtain 0.2 g of a red PVI-Os polymer of Formula 34 (PVI-Os(3-Bu-tz-py)2Cl).

[0530] Example 2.12. Synthesis of Redox Polymer of Formula 39

[0531]

[0532] A reflux condenser, gas inlet and thermometer were fitted to a 100 mL three-necked round bottom flask and Os(l,2,3-tz-py)2Cl2[Formula 18] 0.12 g (0.22 mmol) prepared in Example 1.16 was added and completely dissolved in 10 mL of ethanol under argon atmosphere. 0.1 g of polyvinylimidazole (Mn= 10,000 g / mol) completely dissolved in 20 mL of ethanol was added to the reaction mixture and heated to 110 °C and stirred for 2 days. After completion of the reaction, the reaction mixture was cooled to room temperature and dropped into diethyl ether to obtain polymer precipitate. The resulting solid was filtered under reduced pressure and washed with diethyl ether several times and then dried in a vacuum oven at 40 °C for 24 h to finally obtain 0.22 g of redox polymer of Formula 36 (PVIOs(l,2,3-tz-py)2Cl). (0.21 g, 96%)

[0533] Example 2.13. Synthesis of redox polymer of Formula 40

[0534]

[0535] Example 1.18. Synthesis of Os(3,4-DiMe-pz-4-Me-py)2Cl2[Formula 20] 0.17 g (0.27 mmol) prepared in Example 1.18 was added to a 100 mL Schlenk flask and completely dissolved in 15 mL of ethanol under argon atmosphere. 0.1 g of polyvinylimidazole (Mn= 10,000 g / mol) completely dissolved in 20 mL of ethanol was added to the reaction mixture and heated to 120 °C and stirred for 24 h. After completion of the reaction, the reaction mixture was cooled to room temperature and dropped into diethyl ether to obtain polymer precipitate. The resulting solid was filtered under reduced pressure and washed with diethyl ether several times and then dried in a vacuum oven at 40 °C for 24 h to finally obtain 0.22 g of dark green redox polymer of Formula 37 (PVI-Os(3,4-DiMe-pz-4-Me-py)2Cl). (0.22 g, 81%)

[0536] Example 2.14. Synthesis of redox polymer of Formula 41

[0537]

[0538] Os(3,4-Dime-pz-4-MeO-py)2Cl2[Formula 21] 0.29 g (0.43 mmol) prepared in Example 1.19 was taken in a 100 mL Schlenk tube and completely dissolved in 20 mL of ethanol under argon atmosphere. 0.2 g of polyvinylimidazole (Mn= 10,000 g / mol) completely dissolved in 30 mL of ethanol was added to the reaction mixture and heated to 120 °C and stirred for 48 h. After completion of the reaction, the reaction mixture was cooled to room temperature and dropped into diethyl ether to get the polymer precipitate. The resulting solid was filtered under reduced pressure and washed with diethyl ether for several times and then dried in a vacuum oven at 40 °C for 24 h to finally obtain 0.40 g of brownish red redox polymer of Formula 38 (PVI-Os(3,4-Dime-pz-4-MeO-py)2Cl). (0.40 g, 81 %)

[0539] Example 2.15. Synthesis of redox polymer of Formula 42

[0540]

[0541] Os(4-Me-pz-4-DiAM-py)2Cl2[Formula 22] 0.18 g (0.27 mmol) prepared in Example 1.20 was taken in a 100 mL Schlenk tube and completely dissolved in 20 mL of ethanol under argon atmosphere. 0.1 g of polyvinylimidazole (Mn= 10,000 g / mol) completely dissolved in 20 mL of ethanol was added to the reaction mixture and heated to 120 °C and stirred for 18 h. After completion of the reaction, the reaction mixture was cooled to room temperature and dropped into diethyl ether to get the polymer precipitate. The resulting solid was filtered under reduced pressure and washed with diethyl ether for several times and then dried in a vacuum oven at 40 °C for 24 h to finally obtain 0.24 g of brownish red redox polymer of Formula 39 (PVI-Os(4-Me-pz-4-DiAM-py)2Cl). (0.24 g, 86 %)

[0542] Example 2.16. Synthesis of redox polymer of Formula 43

[0543]

[0544] Os(4-Me-pz-4-DiAM-py)2Cl2[Formula 22] 0.5 g (0.76 mmol) prepared in Example 1.20 was taken in a 250 mL Schlenk flask and completely dissolved in 60 mL of ethanol under argon atmosphere. 0.32 g of polyvinylpyridine (Mn= 160,000 g / mol) completely dissolved in 30 mL of ethanol was added to the reaction mixture and heated to 120 °C and stirred for 24 h. After completion of the reaction, the reaction mixture was cooled to room temperature and dropped into diethyl ether to get the polymer precipitate. The resulting solid was filtered under reduced pressure and washed with diethyl ether for several times and then dried in a vacuum oven at 40 °C for 24 h to finally obtain 0.70 g of a brownish red redox polymer of Formula 40 (PVP-Os(4-Me-pz-4-DiAM-py)2Cl). (0.70 g, 85%)

[0545] Example 2.17. Synthesis of redox polymer of Formula 44

[0546]

[0547] Ru(4-Me-pz4-Me-py)2Cl2[Formula 24] 0.14 g (0.27 mmol) prepared in Example 1.22 was taken in a 100 mL Schlenk flask and completely dissolved in 30 mL of ethanol under argon atmosphere. 0.1 g of polyvinylimidazole (Mn= 10,000 g / mol) completely dissolved in 20 mL of ethanol was added to the reaction mixture and heated to 100 °C and stirred for 12 h. After completion of the reaction, the reaction mixture was cooled to room temperature and dropped into diethyl ether to get the polymer precipitate. The resulting solid was filtered under reduced pressure and washed with diethyl ether for several times and then dried in a vacuum oven at 40 °C for 24 h to finally obtain 0.24 g of a dark green redox polymer of Formula 44 (PVI-Ru(4-Me-pz4-Me-py)2Cl). (0.2 g, 83%)

[0548] Example 2.18. Synthesis of redox polymer of Formula 45

[0549]

[0550] Fe(pzpy)2Cl2[Chemical Formula 25] 0.11 g (0.27 mmol) prepared in Example 1.23 was added to a 100 mL Schlenk flask and completely dissolved in 25 mL of ethanol under an argon atmosphere. 0.1 g of polyvinylimidazole (Mn= 10,000 g / mol) completely dissolved in 20 mL of ethanol was added to the reaction mixture, and heated to 80°C and stirred for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and dropped into diethyl ether to obtain a polymer precipitate. The resulting solid was filtered under reduced pressure and washed with diethyl ether several times, and then dried in a vacuum oven at 40°C for 24 hours to finally obtain 0.1 g of a red-brown redox polymer of Chemical Formula 45 (PVI-Fe(pzpy)2Cl). (0.1 g, 47%)

[0551] Example 3. Synthesis of a redox polymer comprising a transition metal complex according to the present application and a crosslinkable functional group

[0552] Example 3.1. Synthesis of a redox polymer of Chemical Formula 48

[0553]

[0554] A reflux condenser, a gas inlet, and a thermometer were attached to a 100 mL three-necked round-bottom flask, and 0.2 g of the [Chemical Formula 28] polymer prepared in Example 2.1 was added and completely dissolved in methanol under an argon atmosphere. To this reaction mixture, 2-bromoethylamine 20 mg (0.1 mmol) was added, and heated to 80°C and stirred for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and dropped into diethyl ether to obtain a polymer precipitate. The resulting solid was filtered under reduced pressure and washed with diethyl ether several times. To exchange the Br ion contained in the reactant to a Cl ion, the filtered solid and 50 mL of water were added and completely dissolved in a 200 mL beaker, and then 20 mL of ion exchange resin (AG1 x 4) was added and stirred for 24 hours. The reaction mixture was filtered under reduced pressure to remove the resin, and the filtered aqueous solution was freeze-dried to remove water, thereby finally obtaining 0.2 g of a green [Chemical Formula 48] polymer. (0.2 g, 90%)

[0555] Example 3.2. Synthesis of a redox polymer of Chemical Formula 49

[0556]

[0557] A reflux condenser, a gas inlet, and a thermometer were attached to a 100 mL three-necked round-bottom flask, and 0.2 g of the [Chemical Formula 30] polymer prepared in Example 2.3 was added and completely dissolved in methanol in an argon atmosphere. To this reaction mixture, 2-bromoethylamine 20 mg (0.1 mmol) was added, and heated to 80°C and stirred for 24 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature and dropped into diethyl ether to obtain a polymer precipitate. The resulting solid was filtered under reduced pressure and washed with diethyl ether several times. To exchange the Br ion contained in the reaction product to Cl ion, the filtered solid and 50 mL of water were added in a 200 mL beaker and completely dissolved, and then 20 mL of ion exchange resin (AG1x4) was added and stirred for 24 hours. The reaction mixture was filtered under reduced pressure to remove the resin, and the filtered aqueous solution was freeze-dried to remove water, thereby finally obtaining 0.2 g of a green [Chemical Formula 49] polymer. (0.2 g, 90%)

[0558] Example 3.3. Synthesis of a redox polymer of Chemical Formula 50

[0559]

[0560] A reflux condenser, a gas inlet, and a thermometer were attached to a 100 mL three-necked round-bottom flask, and 0.2 g of the [Chemical Formula 30] polymer prepared in Example 2.3 was added and completely dissolved in methanol in an argon atmosphere. To this reaction mixture, 2-bromoethylamine 20 mg (0.1 mmol) was added, and heated to 80°C and stirred for 24 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature and dropped into diethyl ether to obtain a polymer precipitate. The resulting solid was filtered under reduced pressure and washed with diethyl ether several times. To exchange the Br ion contained in the reaction product to Cl ion, the filtered solid and 50 mL of water were added in a 200 mL beaker and completely dissolved, and then 20 mL of ion exchange resin (AG1x4) was added and stirred for 24 hours. The reaction mixture was filtered under reduced pressure to remove the resin, and the filtered aqueous solution was freeze-dried to remove water, thereby finally obtaining 0.2 g of a green [Chemical Formula 49] polymer. (0.2 g, 90%)

[0561] Example 3.4. Synthesis of a redox polymer of Chemical Formula 51

[0562]

[0563] A reflux condenser, a gas inlet, and a thermometer were attached to a 100 mL three-necked round-bottom flask, and 0.2 g of the [Chemical Formula 35] polymer prepared in Example 2.8 was added and completely dissolved in methanol under an argon atmosphere. To this reaction mixture, 2-bromoethylamine 20 mg (0.1 mmol) was added, and heated to 80°C and stirred for 24 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature and dropped into diethyl ether to obtain a polymer precipitate. The resulting solid was filtered under reduced pressure and washed with diethyl ether several times. To exchange the Br ion contained in the reaction product to a CI ion, the filtered solid and 50 mL of water were added in a 200 mL beaker and completely dissolved, and then 20 mL of ion exchange resin (AG1x4) was added and stirred for 24 hours. The reaction mixture was filtered under reduced pressure to remove the resin, and the filtered aqueous solution was freeze-dried to remove water, thereby finally obtaining 0.2 g of a green [Chemical Formula 52] polymer. (0.2 g, 90%)

[0564] Example 3.5. Synthesis of a redox polymer of Chemical Formula 52

[0565]

[0566] A reflux condenser, a gas inlet, and a thermometer were attached to a 100 mL three-necked round-bottom flask, and 0.2 g of the [Chemical Formula 35] polymer prepared in Example 2.8 was added and completely dissolved in methanol under an argon atmosphere. To this reaction mixture, 2-bromoethylamine 20 mg (0.1 mmol) was added, and heated to 80°C and stirred for 24 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature and dropped into diethyl ether to obtain a polymer precipitate. The resulting solid was filtered under reduced pressure and washed with diethyl ether several times. To exchange the Br ion contained in the reaction product to a CI ion, the filtered solid and 50 mL of water were added in a 200 mL beaker and completely dissolved, and then 20 mL of ion exchange resin (AG1x4) was added and stirred for 24 hours. The reaction mixture was filtered under reduced pressure to remove the resin, and the filtered aqueous solution was freeze-dried to remove water, thereby finally obtaining 0.2 g of a green [Chemical Formula 52] polymer. (0.2 g, 90%)

[0567] Example 3.6. Synthesis of a redox polymer of Chemical Formula 53

[0568]

[0569] A reflux condenser, a gas inlet, and a thermometer were attached to a 100 mL three-necked round-bottom flask, and 0.2 g of the [Chemical Formula 40] polymer prepared in Example 2.13 was added and completely dissolved in methanol in an argon atmosphere. To this reaction mixture, 2-bromoethylamine 20 mg (0.1 mmol) was added, and heated to 80°C and stirred for 24 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature and dropped into diethyl ether to obtain a polymer precipitate. The resulting solid was filtered under reduced pressure and washed with diethyl ether several times. To exchange the Br ion contained in the reaction product to Cl ion, the filtered solid and 50 mL of water were added and completely dissolved in a 200 mL beaker, and then 20 mL of ion exchange resin (AG1x4) was added and stirred for 24 hours. The reaction mixture was filtered under reduced pressure to remove the resin, and the filtered aqueous solution was freeze-dried to remove water, thereby finally obtaining 0.2 g of a green [Chemical Formula 53] polymer. (0.2 g, 90%)

[0570] Example 3.7. Synthesis of a redox polymer of Chemical Formula 54

[0571]

[0572] A reflux condenser, a gas inlet, and a thermometer were attached to a 100 mL three-necked round-bottom flask, and 0.2 g of the [Chemical Formula 40] polymer prepared in Example 2.13 was added and completely dissolved in methanol in an argon atmosphere. To this reaction mixture, 2-bromoethylamine 20 mg (0.1 mmol) was added, and heated to 80°C and stirred for 24 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature and dropped into diethyl ether to obtain a polymer precipitate. The resulting solid was filtered under reduced pressure and washed with diethyl ether several times. To exchange the Br ion contained in the reaction product to Cl ion, the filtered solid and 50 mL of water were added and completely dissolved in a 200 mL beaker, and then 20 mL of ion exchange resin (AG1x4) was added and stirred for 24 hours. The reaction mixture was filtered under reduced pressure to remove the resin, and the filtered aqueous solution was freeze-dried to remove water, thereby finally obtaining 0.2 g of a green [Chemical Formula 53] polymer. (0.2 g, 90%)

[0573] Example 3.8. Synthesis of a redox polymer of Chemical Formula 57

[0574]

[0575] A reflux condenser, a gas inlet, and a thermometer were attached to a 100 mL three-necked round-bottom flask, and 0.2 g of the [Chemical Formula 42] polymer prepared in Example 2.15 was added and completely dissolved in methanol in an argon atmosphere. To this reaction mixture, 2-bromoethylamine 20 mg (0.1 mmol) was added, and heated to 80°C and stirred for 24 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature and dropped into diethyl ether to obtain a polymer precipitate. The resulting solid was filtered under reduced pressure and washed with diethyl ether several times. To exchange the Br ion contained in the reaction product to Cl ion, the filtered solid and 50 mL of water were added in a 200 mL beaker and completely dissolved, and then 20 mL of ion exchange resin (AG1x4) was added and stirred for 24 hours. The reaction mixture was filtered under reduced pressure to remove the resin, and the filtered aqueous solution was freeze-dried to remove water, thereby finally obtaining 0.2 g of a red [Chemical Formula 57] polymer. (0.2 g, 90%)

[0576] Example 3.9. Synthesis of a redox polymer of Chemical Formula 58

[0577]

[0578] A reflux condenser, a gas inlet, and a thermometer were attached to a 100 mL three-necked round-bottom flask, and 0.2 g of the [Chemical Formula 42] polymer prepared in Example 2.15 was added and completely dissolved in methanol in an argon atmosphere. To this reaction mixture, 2-bromoethylamine 20 mg (0.1 mmol) was added, and heated to 80°C and stirred for 24 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature and dropped into diethyl ether to obtain a polymer precipitate. The resulting solid was filtered under reduced pressure and washed with diethyl ether several times. To exchange the Br ion contained in the reaction product to Cl ion, the filtered solid and 50 mL of water were added in a 200 mL beaker and completely dissolved, and then 20 mL of ion exchange resin (AG1x4) was added and stirred for 24 hours. The reaction mixture was filtered under reduced pressure to remove the resin, and the filtered aqueous solution was freeze-dried to remove water, thereby finally obtaining 0.2 g of a red [Chemical Formula 57] polymer. (0.2 g, 90%)

[0579] Example 3.10. Synthesis of a redox polymer of Chemical Formula 59

[0580]

[0581] A reflux condenser, a gas inlet, and a thermometer were attached to a 100 mL three-necked round bottom flask, and 0.4 g of the [Chemical Formula 34] polymer prepared in Example 2.7 was added and completely dissolved in methanol in an argon atmosphere. To this reaction mixture, diethylene glycol-2-bromoethyl methyl ether 24 mg (0.1 mmol) was added, and heated to 80°C and stirred for 24 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature and dropped into diethyl ether to obtain a polymer precipitate. The resulting solid was filtered under reduced pressure and washed with diethyl ether several times. To exchange the Br ion contained in the reaction product to Cl ion, the filtered solid and 50 mL of water were added in a 200 mL beaker and completely dissolved, and then 20 mL of ion exchange resin (AG1x4) was added and stirred for 24 hours. The reaction mixture was filtered under reduced pressure to remove the resin, and the filtered aqueous solution was freeze-dried to remove water, thereby finally obtaining 0.4 g of a green [Chemical Formula 59] polymer. (0.4 g, 94%)

[0582] Example 3.11. Synthesis of a redox polymer of Chemical Formula 60

[0583]

[0584] A reflux condenser, a gas inlet, and a thermometer were attached to a 100 mL three-necked round bottom flask, and 0.4 g of the [Chemical Formula 34] polymer prepared in Example 2.7 was added and completely dissolved in methanol in an argon atmosphere. To this reaction mixture, diethylene glycol-2-bromoethyl methyl ether 24 mg (0.1 mmol) was added, and heated to 80°C and stirred for 24 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature and dropped into diethyl ether to obtain a polymer precipitate. The resulting solid was filtered under reduced pressure and washed with diethyl ether several times. To exchange the Br ion contained in the reaction product to Cl ion, the filtered solid and 50 mL of water were added in a 200 mL beaker and completely dissolved, and then 20 mL of ion exchange resin (AG1x4) was added and stirred for 24 hours. The reaction mixture was filtered under reduced pressure to remove the resin, and the filtered aqueous solution was freeze-dried to remove water, thereby finally obtaining 0.4 g of a green [Chemical Formula 59] polymer. (0.4 g, 94%)

[0585] Experimental Example 1: Confirmation of electrochemical properties of transition metal complexes and redox polymers according to the present application using cyclic voltammetry

[0586] To confirm the performance of the transition metal complexes having a bidentate ligand including a pyrazole, a triazole, a tetrazole, an oxadiazole, or a thiadiazole, etc. and the redox polymers including the complexes according to the present application as an electron transfer medium, the electrochemical properties were measured using cyclic voltammetry according to the following experimental method.

[0587] Experimental methods

[0588] 1. 20 mg of each compound (transition metal complex) of Formula 3, Formula 4, Formula 9, Formula 11, Formula 14, Formula 15, Formula 16, Formula 17, Formula 18, Formula 20, Formula 22, Formula 23, Formula 24, and Formula 25 according to the present application was dissolved in 2 mL of 0.1 M tetrabutylammonium perchlorate dimethyl sulfoxide solution.

[0589] 20 mg of the compounds (redox polymers) of Formula 28, Formula 34, Formula 40, and Formula 42 according to the present application and the compounds (redox polymers including crosslinkable functional groups) of Formula 48, Formula 51, Formula 57, and Formula 59 were dissolved in 5 mL of deionized water and 0.1 M sodium chloride solution. As a comparative group, 20 mg of the compound of Formula 61 below was dissolved in 5 mL of deionized water and 0.1 M sodium chloride solution.

[0590] [Formula 61]

[0591]

[0592] 2. To remove oxygen in the solution, degassed with argon for 5 to 10 minutes.

[0593] 3. The working electrode, reference electrode, and counter electrode were connected to the solution in which oxygen was degassed, and the change in the electrical signal with the change in voltage was measured in an argon atmosphere.

[0594] 4. The results of this experiment are shown in Tables 1 to 3 below and Figures la to lo , Figure 2 and Figure 3 respectively.

[0595] The experimental results for each compound correspond to the following figures:

[0596] Formula 3 Figure la , Formula 4 Figure lb , Formula 9 Figure lc , Formula 11 Figure Id , Formula 14 Figure le , Formula 15 Figure If , Formula 16 Figure lg , Formula 17 Figure lh , Formula 18 Figure li , Formula 20 Figure lj , Formula 22 Figure lk , Formula 23 Figure ll , Formula 24 Figure lm , Formula 25 Figure ln), Chemical Formula 3, Chemical Formula 4, Chemical Formula 11, Chemical Formula 14, Chemical Formula 15, Chemical Formula 16 Figure lo ),

[0597] Chemical Formula 3 (comparative group), Chemical Formula 28, 34, 40, 42 Figure 2 ),

[0598] Chemical Formula 28 (comparative group), Chemical Formula 48, Chemical Formula 51, Chemical Formula 57, Chemical Formula 59, Chemical Formula 61 (comparative group) Figure 3 )..

[0599] Experimental materials / conditions

[0600] Working electrode: Free carbon electrode (diameter: 3.0 mm)

[0601] Reference electrode: Ag / AgCl electrode

[0602] Counter electrode: Platinum rod

[0603] Test parameters

[0604] - Equipment: EmStat (PalmSens Co.)

[0605] - Technique: Cyclic voltammetry

[0606] - Potential range: -1.0 ~ 1.0 V

[0607] - Scan rate: 10 mV / s

[0608] [Table 1]

[0609] Transition metal complexes E pc (V)]]> E pa (V) <!-- 56 -->]]> [Chem. 3] 0.03 -0.12 [Chem. 4] 0.05 -0.12 [Chem. 9] -0.08 -0.18 [Chem. 11] -0.16 -0.27 [Chem. 14] -0.18 -0.26 [Chem. 15] 0.04 -0.16 [Chem. 16] 0.26 0.10 [Chem. 17] -0.42 -0.56 [Chem. 18] -0.40 -0.49 [Chem. 20] -0.1 -0.24 [Chem. 22] -0.32 -0.47 [Chem. 23] 0.50 0.60 [Chem. 24] 0.49 0.36 [Chem. 25] 0.71 0.63

[0610] [Table 2]

[0611] Redox complexes E pc (V)]]> E pa (V)]]> [Chem. 3] 0.03 -0.12 [Chem. 28] 0.33 0.17 [Chem. 34] 0.24 0.14 [Chem. 40] 0.26 0.12 [Chem. 42] 0.12 -0.03

[0612] [Table 3]

[0613]

[0614]

[0615] As shown in Table 1 and Table 2 above, it was confirmed that the transition metal complex according to the present application has various potential values depending on the type of ligand. Figures la to lo As shown in Table 1 and Table 2 above, it was confirmed that the intrinsic potential value of the transition metal complex according to the present application changes when the complex is synthesized as a redox polymer.

[0616] Figure 2

[0617] ​​In addition, as shown in Table 3 and Figure 3 above, it was confirmed that when a cross-linkable functional group was introduced into the redox polymer according to the present application, it did not affect the potential value of the redox polymer. Further, it was confirmed that the compounds of Chemical Formula 48, Chemical Formula 51, Chemical Formula 57, and Chemical Formula 59 showed lower potential values compared to the compound of Chemical Formula 61, which is a conventionally known control group, and thus they can efficiently function as a redox mediator.

[0618] Experimental Example 2: Preparation of an electrochemical sensor for continuous blood glucose measurement including a redox polymer according to the present application

[0619] In order to prepare an electrochemical sensor (an electrochemical biosensor) including an electron transfer mediator of a redox polymer according to the present application, the sensor was prepared by the following method.

[0620] Experimental methods

[0621] 1. The compounds of Chemical Formula 48, Chemical Formula 51, Chemical Formula 53, and Chemical Formula 59 of the present application and the compound No. 61 as a comparison group were respectively dissolved in an aqueous solution having a redox enzyme (glucose dehydrogenase), carbon nanotubes (CNT), a non-ionic surfactant (Triton-X), and a cross-linking material (polyethylene glycol diglycidyl ether), and each solution was prepared using a stirring and ultrasonic dispersion method.

[0622] 2. In order to manufacture a continuous blood glucose electrochemical sensor, an aliquot of each of the prepared solutions was coated on an electrode on which carbon paste was printed, and then cured for 24 hours at room temperature through a cross-linking reaction. After curing, the manufactured sensor was washed using distilled water.

[0623] 3. As a method of comparing the electron transfer performance of the above manufactured electrode with an electrode including Chemical Formula 61, a cyclic voltammetry method was used.

[0624] 4. The results of this experiment are shown in Table 4 and Figure 4 below, respectively.

[0625] Experimental materials / conditions

[0626] Working electrode: The above manufactured electrode

[0627] Reference electrode: Ag / AgCl electrode

[0628] Counter electrode: Platinum wire

[0629] Electrolyte: A physiological saline solution containing a phosphate buffer (a phosphate buffer having a NaCl solution)

[0630] Test parameters

[0631] - Equipment: EmStat (PalmSens Co.)

[0632] - Technique: Cyclic voltammetry

[0633] - Potential range: -0.3 ~ 0.4 V

[0634] - Scan rate: 10 mV / s

[0635] [Table 4]

[0636]

[0637] As shown in Table 4 and Figure 4 above, the potential (E 0 ) of the electrode to which the redox polymer according to the present application was applied had a lower potential than that of the comparative group electrode. This is a similar result to Experimental Example 1, and in addition, through this experiment, it was confirmed that the operating voltage of the electrochemical sensor for continuous blood glucose measurement can be stably used even at a lower voltage than the comparative group.

[0638] Experimental Example 3: Comparison of sensitivity of electrochemical sensor for continuous blood glucose measurement to glucose concentration change

[0639] 1. The electrodes manufactured in Experimental Example 2 above using the compounds of Chemical Formula 51 and Chemical Formula 53 according to the present application and the No. 61 compound of the comparative group were compared by chronoamperometry in a 0 ~ 100 mM glucose solution.

[0640] 2. The voltage applied when chronoamperometry was performed was 0.15 V for the electrode using the compound 51 and the compound 53, and 0.25 V for the electrode using the No. 61 compound of the comparative group.

[0641] 3. The glucose concentration was 0.01 mM, 0.05 mM, 0.1 mM, 0.5 mM, 1 mM, 5 mM, 10 mM, 50 mM, or 100 mM, and a high-concentration glucose solution was injected into a physiological saline solution containing a phosphate buffer at an interval of 200 seconds to reach each concentration. Each experiment was performed for 50 minutes.

[0642] 4. The results of this experiment are shown in Table 5 and Figure 5 and Figure 6 below, respectively.

[0643] Experimental materials / conditions

[0644] Working electrode: The above manufactured electrode

[0645] Reference electrode: Ag / AgCl electrode

[0646] Counter electrode: Platinum wire

[0647] Electrolytes: Physiological saline solution containing phosphate buffer (phosphate buffer with NaCl solution)

[0648] Test parameters

[0649] - Equipment: EmStat (PalmSens Co.)

[0650] -Technology: Chronoamperometry

[0651] Potential range: 0.15V, 0.25V

[0652] like Figure 5 As shown in Figure 6, all electrodes using the redox polymer according to the invention exhibit linear sensitivity to glucose at concentrations of 10 mM or lower, and similar sensitivity is observed even when a lower voltage is applied than that of the comparison group electrodes. In particular, based on the fact that the current at 100 mM concentration is greater in the electrodes where compounds 51 and 53 are applied than in the comparison group, the maximum enzyme activity (Vc) is significantly higher. max It appears to be about 1.2 to 2 times that of the comparison group.

[0653] Experimental Example 4: Comparison of glucose sensitivity based on voltage increase of electrochemical sensors used for continuous blood glucose measurement

[0654] 1. The electrodes made using compounds of chemical formulas 51 and 53 according to the present invention and compound No. 61 as a comparative group were compared by performing multi-stage voltammetry (multi-potential step) in a 400 mM glucose solution.

[0655] 2. During the multi-stage voltammetry process, the voltage is maintained at intervals of 0.05V from -0.2V to 0.35V for 300 seconds, and the current is observed.

[0656] 3. Next Figure 7 The results of the experiment are shown in the figures.

[0657] Experimental materials / conditions

[0658] Working electrode: The electrode manufactured as described above

[0659] Reference electrode: Ag / AgCl electrode

[0660] Counter electrode: Platinum wire

[0661] Electrolytes: Physiological saline solution containing phosphate buffer (phosphate buffer with NaCl solution)

[0662] Test parameters

[0663] - Device: EmStat (PalmSens Co.)

[0664] -Technology: Multipotential Step

[0665] Potential range: -0.2~0.35V

[0666] like Figure 7 As shown, it can be confirmed that all electrodes to which the redox polymer according to the invention is applied exhibit sensitivity to glucose at a lower voltage than the control group electrodes.

Claims

1. A transition metal complex or a salt compound thereof, the transition metal complex being a compound selected from the group consisting of Chemical Formula 3 to Chemical Formula 22: [Chemical Formula 3] [Chemical Formula 4] [Chemical Formula 5] [Chemical Formula 6] [Chemical Formula 7] [Chemical Formula 8] [Chemical Formula 9] [Chemical Formula 10] [Chemical Formula 11] [Chemical Formula 12] [Chemical Formula 13] [Chemical Formula 14] [Chemical Formula 15] [Chemical Formula 16] [Chemical Formula 17] [Chemical Formula 18] [Chemical Formula 19] [Chemical Formula 20] [Chemical Formula 21] and [Chemical Formula 22] 2. A redox polymer represented by a compound selected from the group consisting of Chemical Formula 28 to Chemical Formula 43: [Chemical Formula 28] [Chemical Formula 29] [Chemical Formula 30] [Chemical Formula 31] [Chemical Formula 32] [Chemical Formula 33] [Chemical Formula 34] [Chemical Formula 35] [Chemical Formula 36] [Chemical Formula 37] [Chemical Formula 38] [Chemical Formula 39] [Chemical Formula 40] [Chemical Formula 41] [Chemical Formula 42] and [Chemical Formula 43] In the formulae, m and o are each an integer selected from 10 to 600.

3. A redox polymer represented by a compound selected from the group consisting of Chemical Formula 48 to Chemical Formula 59: [Chemical Formula 48] [Chemical Formula 49] [Chemical Formula 50] [Chemical Formula 51] [Chemical Formula 52] [Chemical Formula 53] [Chemical Formula 54] [Chemical Formula 55] [Chemical Formula 56] [Chemical Formula 57] [Chemical Formula 58] and [Formula 59] In the formulae, m, o, and p are each an integer selected from 10 to 600.

4. An electrochemical biosensor comprising the transition metal complex or the salt compound thereof according to claim 1; or the redox polymer according to claim 2 or 3.

5. The electrochemical biosensor of claim 4, wherein, The electrochemical biosensor can be inserted into a body.

6. A sensing membrane for an electrochemical biosensor, comprising: an enzyme capable of oxidizing and reducing a liquid biological sample; and the transition metal complex or the salt compound thereof according to claim 1; or the redox polymer according to claim 2 or 3, as an electron transfer mediator.

7. The sensing membrane for an electrochemical biosensor of claim 6, wherein, The enzyme is at least one selected from the group consisting of a dehydrogenase, an oxidase, and an esterase.

8. The sensing membrane of claim 7, wherein, The enzyme is at least one selected from the group consisting of a glucose dehydrogenase, a glutamate dehydrogenase, a glucose oxidase, a cholesterol oxidase, a cholesterol esterase, a lactic acid oxidase, an ascorbic acid oxidase, an alcohol oxidase, an alcohol dehydrogenase, and a bilirubin oxidase.

9. The sensing membrane according to claim 7, further comprising at least one co-factor selected from the group consisting of flavin adenine dinucleotide (FAD), nicotinamide adenine dinucleotide (NAD), and pyrroloquinoline quinone (PQQ).

10. The sensing membrane according to claim 6, further comprising a carbon nanotube.

11. The sensing membrane of claim 6, wherein, The liquid biological sample is at least one selected from the group consisting of a tissue fluid, blood, cells, plasma, serum, urine, cyst fluid, and saliva of a patient.

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