A carbazole terpyridine ruthenium complex oxygen detection probe and its preparation method and application

Abstract

The present invention provides a carbazole terpyridine ruthenium complex or its salt, or its solvate. The present invention also provides a method for synthesizing the carbazole terpyridine ruthenium complex. The present invention further provides a probe. The present invention further provides the use of the above-mentioned carbazole terpyridine ruthenium complex or its salt, or its solvate, and / or the above-mentioned probe in detecting oxygen. The present invention provides a carbazole terpyridine ruthenium complex oxygen detection probe and its preparation method and application, which uses carbazole terpyridine as an optical signal reporting group to prepare a molecular fluorescent probe that can be used to detect oxygen, and generates singlet oxygen by reacting with oxygen under light conditions and continuing to react with singlet oxygen to obtain an oxidation product with significantly enhanced fluorescence, thereby achieving highly selective, in-situ, and real-time response to oxygen.

Description

Technical Field

[0001] The invention belongs to the technical field of optical sensing detection, and specifically relates to a carbazole terpyridine ruthenium complex oxygen detection probe and a preparation method and application thereof. Background Art

[0002] Oxygen is an important signal molecule in organisms. Hypoxia is associated with a variety of diseases. Long-term hypoxia can cause permanent damage or even endanger life. Therefore, the detection of oxygen is crucial for biomedicine and environmental monitoring. Optical oxygen detection sensors can quickly adapt to the surrounding environment and have the advantages of fast detection speed and easy portability. They can be used in extreme environments such as toxic and strong radiation environments, and are therefore widely used.

[0003] At present, the working principle of most optical oxygen probes is based on the fluorescence quenching principle of oxygen on luminescent probe molecules, which uses the ability of oxygen to dynamically quench the emitted light to reduce the fluorescence intensity and fluorescence lifetime of the emitted light. Ruthenium (II) polypyridine complexes have unique photophysical and photochemical properties, strong fluorescence lifetime and anti-photobleaching ability, and are an ideal fluorescent indicator, showing great application prospects in molecular sensing.

[0004] In order to obtain an oxygen detection reagent with excellent performance, it is crucial to develop a small molecule ruthenium (II) polypyridine complex with high sensitivity and rapid response. Currently, several ruthenium complexes have been used in the research of oxygen detection, but there are few probes that enhance the fluorescence intensity of emitted light. Summary of the invention

[0005] In view of the shortcomings of the prior art described above, the object of the present invention is to provide a carbazole terpyridine ruthenium complex oxygen detection probe and its preparation method and application, so as to solve the problem in the prior art of lack of detection probes that can achieve high selectivity, in situ and real-time response for oxygen detection.

[0006] To achieve the above-mentioned object and other related objects, the present invention provides a carbazole terpyridine ruthenium complex or its salt, or its solvate, in a first aspect, wherein the complex has a structural formula as shown in the following formula I:

[0007]

[0008] The second aspect of the present invention provides a method for synthesizing a carbazole terpyridine ruthenium complex, comprising the following steps:

[0009] 1) reacting N-ethylcarbazole-3-carboxaldehyde with 2-acetylpyridine to obtain a compound of formula II;

[0010]

[0011] 2) reacting the compound of formula II with ruthenium trichloride trihydrate and potassium borofluoride to obtain the desired compound of formula I;

[0012]

[0013] The third aspect of the present invention provides a probe, comprising the above-mentioned carbazole terpyridine ruthenium complex or its salt, or its solvate.

[0014] The fourth aspect of the present invention provides the use of the above-mentioned carbazole terpyridine ruthenium complex or its salt, or its solvate, and / or the above-mentioned probe in detecting oxygen.

[0015] As described above, the present invention provides a carbazole terpyridine ruthenium complex oxygen detection probe and its preparation method and application, which have the following beneficial effects:

[0016] (1) The present invention provides a carbazole terpyridine ruthenium complex oxygen detection probe and its preparation method and application. Through a simple, easy and low-cost preparation method, carbazole terpyridine is used as an optical signal reporter group to prepare a molecular fluorescent probe that can be used to detect oxygen.

[0017] (2) The present invention provides a carbazole terpyridine ruthenium complex oxygen detection probe and its preparation method and application. The ruthenium complex modified with carbazole terpyridine increases the fluorescence intensity of the emitted light, and can react with oxygen under light conditions to generate singlet oxygen and continue to react with singlet oxygen to obtain an oxidation product with significantly enhanced fluorescence, thereby achieving highly selective, in-situ, and real-time response to oxygen.

[0018] (3) The present invention provides a carbazole terpyridine ruthenium complex oxygen detection probe and its preparation method and application. Carbazole terpyridine can also be used as a platform to design probes that recognize various molecules or ions. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 Shown is the ultraviolet absorption spectrum of the compound of formula I obtained in Example 3 of the present invention.

[0020] Figure 2 Shown is the fluorescence emission spectrum of the compound of formula I obtained in Example 4 of the present invention.

[0021] Figure 3 It is shown as the compound of formula II obtained in Example 1 of the present invention 1 H NMR (400MHz) nuclear magnetic spectrum.

[0022] Figure 4 It is shown as the compound of formula II obtained in Example 1 of the present invention 13 C NMR (100MHz) nuclear magnetic spectrum.

[0023] Figure 5 It is shown as the compound of formula I obtained in Example 2 of the present invention 1 H NMR (400MHz) nuclear magnetic spectrum.

[0024] Figure 6 It is shown as the compound of formula I obtained in Example 2 of the present invention 13 C NMR (100MHz) nuclear magnetic spectrum.

[0025] Figure 7 Shown is the mass spectrum of the compound of formula I obtained in Example 2 of the present invention. DETAILED DESCRIPTION

[0026] After extensive research, the inventors of the present invention provide a carbazole terpyridine ruthenium complex or its salt, or its solvate as an oxygen detection probe. The inventors of the present invention have found that the probe increases the fluorescence intensity of the emitted light, can react with oxygen under light conditions to generate singlet oxygen, and continue to react with singlet oxygen to obtain an oxidation product with significantly enhanced fluorescence, so as to detect oxygen. On this basis, the present invention is completed.

[0027] Definition of terms

[0028] Unless otherwise specified, the following words, phrases and symbols used in this specification generally have the meanings described below.

[0029] In general, the nomenclature used in the present invention (e.g., IUPAC nomenclature) and the laboratory procedures described below (including for cell culture, organic chemistry, analytical chemistry, and pharmacology, etc.) are those well known and commonly used in the art. Unless otherwise defined, all scientific and technical terms used herein in conjunction with the present disclosure described herein have the same meanings as commonly understood by those skilled in the art. In addition, in the claims and / or the specification, when the term "one" or "an" is used in conjunction with the term "comprising" or a noun, its meaning may be "one", but it is also consistent with the meaning of "one or more", "at least one" and "one or more than one". Similarly, the term "another" or "other" can mean at least a second or more.

[0030] It should be understood that whenever various aspects are described herein with the terms "including" or "comprising," other similar aspects described by "consisting of" and / or "consisting essentially of" are also provided.

[0031] The salts or solvates of the complex of formula I disclosed in the present invention are also included in the scope of the present disclosure.

[0032] In the present invention, the term "salt" refers to non-toxic inorganic or organic acid and / or base addition salts. Examples include sulfates, hydrochlorides, citrates, maleates, sulfonates, citrates, lactates, tartrates, fumarates, phosphates, dihydrogenphosphates, pyrophosphates, metaphosphates, oxalates, malonates, benzoates, mandelates, succinates, glycolates or p-toluenesulfonates, etc.

[0033] In the present invention, the term "solvate" refers to a compound of the present disclosure or a salt thereof, which contains a stoichiometric or non-stoichiometric amount of a solvent bound by forces between non-covalent molecules. Preferred solvents are volatile and non-toxic and can be administered to humans in very small doses. Examples of solvents include, but are not limited to, water, isopropanol, ethanol, methanol, DMSO, ethyl acetate, acetic acid, and ethanolamine.

[0034] Complex

[0035] The first aspect of the present invention provides a carbazole terpyridine ruthenium complex or a salt thereof, or a solvate thereof, wherein the complex has a structural formula as shown in the following formula I:

[0036]

[0037] The above-mentioned carbazole terpyridine ruthenium complex is a ruthenium complex modified by carbazole terpyridine.

[0038] Synthesis method

[0039] The second aspect of the present invention provides a method for synthesizing a carbazole terpyridine ruthenium complex, comprising the following steps:

[0040] 1) reacting N-ethylcarbazole-3-carboxaldehyde with 2-acetylpyridine to obtain a compound of formula II;

[0041]

[0042] 2) reacting the compound of formula II with ruthenium trichloride trihydrate and potassium borofluoride to obtain the desired compound of formula I;

[0043]

[0044] In the above step 1), the first step reaction is to conduct a first mixing reaction of N-ethylcarbazole-3-carboxaldehyde with a first alkaline compound, 2-acetylpyridine and a first solvent, and then add a second alkaline compound for a second mixing reaction, and the obtained precipitate is the compound of formula II.

[0045] In a specific embodiment, the molar ratio of N-ethylcarbazole-3-carboxaldehyde, the first basic compound and 2-acetylpyridine is 0.8-1.2:2:1.8-2.2, specifically, the molar ratio is 0.8-1.0:2:1.8-2.0, 0.8-1.0:2:2.0-2.2, 1.0-1.2:2:1.8-2.0, 1.0-1.2:2:2.0-2.2, preferably 1:2:2.

[0046] In a specific embodiment, the ratio of the added molar number mmol of the N-ethylcarbazole-3-carboxaldehyde to the added volume mL of the first solvent is 8-12:40, specifically, the ratio between the two is 8-10:40, 10-12:40, preferably 10:40.

[0047] In one embodiment, the first mixing reaction is stirring and mixing, and the stirring time is 25-35 minutes, preferably 30 minutes. The first mixing reaction is to make the reactants mix evenly. The first mixing reaction can be heated to reflux.

[0048] In a specific embodiment, the first alkaline compound is a commonly used strong base, specifically including but not limited to sodium hydroxide, calcium hydroxide, potassium hydroxide, preferably potassium hydroxide.

[0049] In a specific embodiment, the first solvent is a commonly used alcohol, specifically including but not limited to methanol, ethanol, propanol, preferably ethanol.

[0050] In a specific embodiment, the ratio of the added molar number mmol of the N-ethylcarbazole-3-carboxaldehyde to the added volume mL of the second basic compound is 8-12:25, specifically, the ratio between the two is 8-10:25, 10-12:25, preferably 10:25.

[0051] In a specific embodiment, the second alkaline compound is a commonly used weak base, specifically including but not limited to ammonia water, iron hydroxide, aluminum hydroxide, preferably ammonia water.

[0052] In a preferred embodiment, when the second alkaline compound is aqueous ammonia, the concentration of ammonia in the aqueous ammonia is 24-26 wt %, preferably 25 wt %.

[0053] In a specific embodiment, the second mixing reaction is stirring mixing, and the stirring time is 46-50 hours, preferably 48 hours.

[0054] In one embodiment, the second mixing reaction is carried out at room temperature, which is 15-40°C.

[0055] In one embodiment, the precipitate is filtered, washed, and recrystallized.

[0056] In a preferred embodiment, the filtration is a conventional filtration method, such as membrane filtration.

[0057] In a preferred embodiment, the washing liquid used in the washing is alcohol.

[0058] In a further preferred embodiment, the alcohol specifically includes but is not limited to methanol, ethanol, propanol, preferably ethanol.

[0059] In a further preferred embodiment, the washing number is at least 1 time, preferably 2 times.

[0060] In a further preferred embodiment, the ratio of the molar number mmol of the N-ethylcarbazole-3-carboxaldehyde added to the volume mL of the washing liquid added per washing is 8-12:5, specifically, the ratio between the two is 8-10:5, 10-12:5, preferably 10:5.

[0061] In a preferred embodiment, the recrystallization is a conventional recrystallization method. Specifically, the recrystallization is to place the washed precipitate in a saturated acetonitrile solution, and after the acetonitrile evaporates, supersaturated precipitation is carried out to achieve recrystallization.

[0062] In the above step 2), the second step reaction is to carry out a third mixing reaction of the compound of formula II with ruthenium trichloride trihydrate, a second solvent and a catalyst under an inert gas atmosphere, and then add the obtained reaction solution to potassium borofluoride (KBF4) for a fourth mixing reaction, and the obtained precipitate is the compound of formula I. The compound of formula I can be represented as CaTpRuII.

[0063] In a specific embodiment, the molar ratio of the compound of formula II to ruthenium trichloride trihydrate is 1:0.5-0.7, specifically, the molar ratio is 1:0.5-0.6, 1:0.6-0.7, preferably 1:0.6.

[0064] In a specific embodiment, the ratio of the added molar number mmol of the compound of formula II to the added volume mL of the second solvent is 1:5-7. Specifically, the ratio between the two is 1:5-6, 1:6-7, and preferably 1:6.

[0065] In a specific embodiment, the ratio of the added molar number mmol of the compound of formula II to the added volume μL of the catalyst is 1:90-110. Specifically, the ratio between the two is 1:90-100, 1:100-110, and preferably 1:100.

[0066] In a specific embodiment, the second solvent is a commonly used alcohol, specifically including but not limited to methanol, ethanol, ethylene glycol, propanol, preferably ethylene glycol.

[0067] In a specific embodiment, the catalyst is N-ethylmorpholine (NMP).

[0068] In a specific embodiment, the inert gas is a conventionally used inert gas, specifically including but not limited to helium, neon, argon, krypton, nitrogen (N2), preferably nitrogen (N2).

[0069] In one embodiment, the reaction time of the third mixing reaction is 22-26 hours, preferably 24 hours. The third mixing reaction may be heated to reflux.

[0070] In one embodiment, the reaction solution obtained after the third mixing reaction is cooled to room temperature.

[0071] In one embodiment, the potassium fluoroborate (KBF4) is a saturated KBF4 aqueous solution. The reaction solution is added to the potassium fluoroborate slowly.

[0072] In a specific embodiment, the ratio of the added molar number mmol of the compound of formula II to the added volume mL of potassium borofluorate is 1:35-45. Specifically, the ratio between the two is 1:35-40, 1:40-45, and preferably 1:40.

[0073] In a specific embodiment, the reaction time of the fourth mixing reaction is 30-60 min.

[0074] In a specific embodiment, the precipitate is a brown-red precipitate.

[0075] In one embodiment, the precipitate is filtered, dried, washed and purified.

[0076] In a preferred embodiment, the filtration is a conventional filtration method, such as membrane filtration.

[0077] In a preferred embodiment, the drying is a conventional drying method, such as oven drying.

[0078] In a preferred embodiment, the washing solution used for the washing and purification is a mixture of acetonitrile and diethyl ether.

[0079] In a further preferred embodiment, in the washing liquid, the volume ratio of acetonitrile to diethyl ether is 1:1-3, preferably 1:2.

[0080] In a further preferred embodiment, the washing and purification is performed at least once, preferably three times.

[0081] In a further preferred embodiment, the ratio of the number of moles of the compound of formula II added in mmol to the volume of the washing liquid added in mL for each washing is 1:10-30. Specifically, the ratio between the two is 1:15-20, 1:15-25, and preferably 1:20.

[0082] application

[0083] The third aspect of the present invention provides a probe, comprising the above-mentioned carbazole terpyridine ruthenium complex or its salt, or its solvate.

[0084] The fourth aspect of the present invention provides the use of the above-mentioned carbazole terpyridine ruthenium complex or its salt, or its solvate, and / or the above-mentioned probe in detecting oxygen.

[0085] The present invention is further described below in conjunction with specific examples. It should be understood that these examples are only used to illustrate the present invention and are not used to limit the scope of protection of the present invention.

[0086] The following describes the embodiments of the present invention through specific examples, and those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and the details in this specification can also be modified or changed in various ways based on different viewpoints and applications without departing from the spirit of the present invention.

[0087] It should be noted that the process equipment or devices not specifically specified in the following embodiments are all conventional equipment or devices in the art; all pressure values ​​and ranges refer to relative pressures.

[0088] In addition, it should be understood that one or more method steps mentioned in the present invention do not exclude the existence of other method steps before or after the combination step or the insertion of other method steps between these explicitly mentioned steps, unless otherwise specified; it should also be understood that the combination connection relationship between one or more devices / apparatuses mentioned in the present invention does not exclude the existence of other devices / apparatuses before or after the combination device / apparatus or the insertion of other devices / apparatuses between these explicitly mentioned two devices / apparatuses, unless otherwise specified. Moreover, unless otherwise specified, the numbering of each method step is only a convenient tool for identifying each method step, and is not intended to limit the order of arrangement of each method step or the scope of the present invention. Changes or adjustments in their relative relationships should also be regarded as the scope of the present invention without substantially changing the technical content.

[0089] Example 1

[0090] Take 2.23g N-ethylcarbazole-3-carboxaldehyde (10mmol), 1.12g KOH (20mmol), and 2.4g 2-acetylpyridine (20mmol), add them into 40mL ethanol for the first mixing reaction, mix well, and stir for 30 minutes. The molar ratio of N-ethylcarbazole-3-carboxaldehyde, KOH, and 2-acetylpyridine is 1:2:2.

[0091] Then 25 mL of 25 wt% concentrated ammonia water was added to carry out a second mixing reaction at room temperature, and the mixture was stirred for 48 hours. A large amount of precipitate appeared. The precipitate was the compound of formula II. After filtering, it was washed twice with 5 mL of ethanol each time, and the compound of formula II was recrystallized in acetonitrile. 1.8 g of the compound of formula II was obtained. Since the theoretical yield was 10 mmol, the yield was 42.3%.

[0092] The NMR data of the compound of formula II are as follows: Figure 3 , 4 shown.

[0093] like Figure 3 As shown, 1 H NMR (400MHz, DMSO-d6) δ (ppm) 8.85 (s, 2H), 8.80 (s, 3H), 8.70 (, J = 8.0Hz, 2H), 8.41 (d, J = 7.8Hz, 1H), 8.07-8.42 (m, 3H), 7.80 ( d,J=8.4Hz,1H),7.67(d,J=8.2Hz,1H),7.56-7.50(m,3H),7.26(t,J=7.4Hz,1H),4.51(q,J=6.9Hz,2H),1.37(t,J=6.9Hz,3H).

[0094] like Figure 4 As shown, 13 C NMR(100MHz,DMSO-d6)δ(ppm)155.51,155.23,150.43,149.26,140.20,140.09,137.36,128.15,126.19, 124.66,124.36,123.02,122.31,121.00,120.92,119.17,119.01,117.88,109.85,109.32,37.12,13.69.

[0095] Example 2

[0096] Take 0.426g of the compound of formula II prepared in Example 1 (1mmol) and 156mg of ruthenium trichloride trihydrate (0.6mmol), add 6m ethylene glycol and 100μL N-ethylmorpholine, and carry out the third mixing reaction for 24 hours under N2 atmosphere to obtain a reaction solution. After the reaction solution is cooled, the reaction solution is slowly dripped into 40mL saturated KBF4 aqueous solution for the fourth mixing reaction, and a large amount of brown-red precipitate is precipitated, and the precipitate is the compound of formula I. After filtering and drying the precipitate, it is washed and purified 3 times with acetonitrile-ether with a volume ratio of 1:2 in an amount of 15mL each time to obtain a purified compound of formula I. 202mg of the compound of formula I is obtained, and since the theoretical yield is 0.5mmol, the yield obtained is 36.0%.

[0097] The NMR data of the compound of formula I obtained are as follows: Figure 5 , 6 As shown, the mass spectrum data of the compound of formula I obtained is as follows Figure 7 shown.

[0098] like Figure 5 As shown, 1 H NMR (400MHz, DMSO-d6) δ (ppm) 9.02 (s, 4H), 9.32 (s, 2H), 9.2 (d, J = 8.0Hz, 4H), 8.62 (d, J = 8.3Hz, 2H), 8.41 (d, J = 7.5Hz, 2H), 8.12 (t, J = 7.6Hz, 4H), 8.03 (d,J=8.6Hz,2H),7.78(d,J=8.2Hz,2H),7.63-7.59(m,6H),7.40(t,J=7.3H z,2H),7.33(t,J=6.3Hz,4H),4.64(q,J=6.8Hz,4H),1.47(t,J=6.8Hz,6H).

[0099] like Figure 6 As shown, 13 C NMR (100MHz, DMSO-d6) δ (ppm) 158.34, 155.02, 152.24, 148.12, 140.86, 140.39, 137.99, 127.75, 126. 70,126.62,125.57,124.80,123.15,122.53,120.68,120.14,119.64,110.06,109.90,37.39,13.96.

[0100] like Figure 7 As shown, ESI-HRMS: calcd.m / z 477.1366for[M] 2+, found m / z 477.1435for[M] 2+ .

[0101] Example 3

[0102] The compound of formula I prepared in Example 2 was used as a probe for ultraviolet absorption spectrum measurement. In the specific measurement, the main concentration was 10 μM and the test system was an aqueous solution. The ultraviolet absorption spectra were measured after nitrogen was bubbled in for 2 minutes, oxygen was bubbled in for 10 seconds, 40 seconds and 70 seconds, respectively. The measurement results are shown in Figure 1 . Figure 1 In the figure, the CaTpRuII N2 curve represents the ultraviolet absorption spectrum measured by the probe after nitrogen was bubbled for 2 minutes, CaTpRuIIO2 10s represents the ultraviolet absorption spectrum measured by the probe after oxygen was bubbled for 10 seconds, CaTpRuIIO2 40s represents the ultraviolet absorption spectrum measured by the probe after oxygen was bubbled for 40 seconds, and CaTpRuIIO2 70s represents the ultraviolet absorption spectrum measured by the probe after oxygen was bubbled for 70 seconds.

[0103] like Figure 1 As shown, at 499 nm, the ultraviolet absorption peaks of the four curves gradually increase with the increase of oxygen concentration, so oxygen detection can be achieved.

[0104] Example 4

[0105] The compound of formula I prepared in Example 2 was used as a probe for fluorescence emission spectrum measurement. In the specific measurement, the main concentration was 10 μM, the excitation wavelength was 280 nm, and the test system was an aqueous solution. The fluorescence emission spectra were measured after bubbling nitrogen for 2 minutes, bubbling oxygen for 40 seconds, 70 seconds, 110 seconds, 140 seconds, 180 seconds, 210 seconds, 250 seconds, 300 seconds, 350 seconds, 400 seconds, 450 seconds, and 600 seconds, respectively. The measurement results are shown in Figure 2 . Figure 2 In the figure, the CaTpRuII N2 curve represents the fluorescence emission spectrum of the probe measured after nitrogen was bubbled for 2 minutes, and CaTpRuIIO2 40s, 70s, 110s, 140s, 180s, 210s, 250s, 300s, 350s, 400s, 450s, and 600s represent the fluorescence emission spectra of the probe measured after oxygen was bubbled for 40 seconds, 70 seconds, 110 seconds, 140 seconds, 180 seconds, 210 seconds, 250 seconds, 300 seconds, 350 seconds, 400 seconds, 450 seconds, and 600 seconds, respectively.

[0106] like Figure 2 As shown, at 411 nm and 650 nm, the fluorescence emission peaks of the probe gradually increase with the increase of oxygen concentration, thus realizing the detection of oxygen.

[0107] In summary, the present invention provides a carbazole terpyridine ruthenium complex oxygen detection probe and its preparation method and application, using carbazole terpyridine as an optical signal reporter group to prepare a molecular fluorescent probe that can be used to detect oxygen, and reacts with oxygen under light conditions to generate singlet oxygen and continues to react with singlet oxygen to obtain an oxidation product with significantly enhanced fluorescence, thereby achieving high selectivity, in-situ, and real-time response to oxygen. Therefore, the present invention effectively overcomes various shortcomings in the prior art and has a high industrial utilization value.

[0108] The above embodiments are merely illustrative of the principles and effects of the present invention, and are not intended to limit the present invention. Anyone familiar with the art may modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by a person of ordinary skill in the art without departing from the spirit and technical concept disclosed by the present invention shall still be covered by the claims of the present invention.

Claims

1. A carbazole terpyridine ruthenium complex, wherein the complex has the structural formula shown in the following formula I:

2. A method for synthesizing a carbazole terpyridine ruthenium complex, comprising the following steps: 1) reacting N-ethylcarbazole-3-carboxaldehyde with 2-acetylpyridine to obtain a compound of formula II; 2) reacting the compound of formula II with ruthenium trichloride trihydrate and potassium borofluoride to obtain the desired compound of formula I; In step 1), the first step reaction is to conduct a first mixing reaction of N-ethylcarbazole-3-carboxaldehyde with a first alkaline compound, 2-acetylpyridine, and a first solvent, and then add a second alkaline compound to conduct a second mixing reaction, and the obtained precipitate is the compound of formula II; The first alkaline compound is a strong base; the first alkaline compound includes sodium hydroxide, calcium hydroxide, and potassium hydroxide; the second alkaline compound is a weak base; the second alkaline compound includes ammonia water, iron hydroxide, and aluminum hydroxide.

3. The method for synthesizing the carbazole terpyridine ruthenium complex according to claim 2, characterized in that: Includes any one or more of the following conditions: A1) the molar ratio of the N-ethylcarbazole-3-carboxaldehyde, the first basic compound and 2-acetylpyridine is 0.8-1.2:2:1.8-2.2; A2) the ratio of the number of moles of N-ethylcarbazole-3-carboxaldehyde added to the volume of the first solvent added is 8-12:40, mmol / mL; A3) the first mixing reaction is stirring and mixing, and the stirring time is 25-35min; A4) the first solvent is an alcohol; A5) the ratio of the molar number of the N-ethylcarbazole-3-carboxaldehyde added to the volume of the second basic compound added is 8-12:25, mmol / mL; A6) the second mixing reaction is stirring and mixing, and the stirring time is 46-50 hours; A7) The precipitate is filtered, washed and recrystallized.

4. The method for synthesizing the carbazole terpyridine ruthenium complex according to claim 3, characterized in that: A9) includes any one or more of the following conditions: A71) The filtration is membrane filtration; A72) the washing liquid used in the washing is alcohol; A73) the washing number is at least 1; A74) the ratio of the number of moles of N-ethylcarbazole-3-carboxaldehyde added to the volume of the washing solution added per washing is 8-12:5, mmol / mL; A75) The recrystallization is performed by placing the washed precipitate in a saturated acetonitrile solution, and after the acetonitrile evaporates, supersaturated precipitation is carried out to achieve recrystallization.

5. The method for synthesizing the carbazole terpyridine ruthenium complex according to claim 2, characterized in that: The second step reaction is to carry out a third mixing reaction of the compound of formula II with ruthenium trichloride trihydrate, a second solvent and a catalyst under an inert gas atmosphere, and then add potassium borofluorite to carry out a fourth mixing reaction of the obtained reaction solution, and the obtained precipitate is the compound of formula I.

6. The method for synthesizing the carbazole terpyridine ruthenium complex according to claim 5, characterized in that: Includes any one or more of the following conditions: B1) the molar ratio of the compound of formula II to ruthenium trichloride trihydrate is 1:0.5-0.7; B2) the ratio of the molar number of the compound of formula II added to the volume of the second solvent added is 1:5-7, mmol / mL; B3) the ratio of the molar number of the compound of formula II added to the volume of the catalyst added is 1:90-110, mmol / μL; B4) the second solvent is an alcohol; B5) the catalyst is N-ethylmorpholine; B6) the inert gas is selected from one of helium, neon, argon, krypton or nitrogen; B7) the reaction time of the third mixing reaction is 22-26 hours; B8) the reaction solution obtained after the third mixing reaction is cooled; B9) the potassium borofluoride is a saturated KBF4 aqueous solution; B10) the ratio of the molar number of the compound of formula II added to the volume of potassium fluoroborate added is 1:35-45, mmol / mL; B11) the reaction time of the fourth mixing reaction is 30-60min; B12) The precipitate is filtered, dried, washed and purified.

7. The method for synthesizing the carbazole terpyridine ruthenium complex according to claim 6, characterized in that: B12) includes any one or more of the following conditions: B121) The filtration is membrane filtration; B122) The drying is oven drying; B123) The washing solution used in the washing and purification is a mixture of acetonitrile and ether; B124) the washing and purification is performed at least once; B125) The ratio of the number of moles of the compound of formula II added to the volume of the washing liquid added per washing is 1:10-30, mmol / mL.

8. A probe comprising the carbazole terpyridine ruthenium complex according to claim 1.

9. Use of the carbazole terpyridine ruthenium complex according to claim 1 and / or the probe according to claim 8 in detecting oxygen.

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