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    • 专利摘要:
    The present invention provides a phenothiazine-based nano-metal organic-framework material, which takes a compound of formula (I) as an organic ligand, and the structure of the formula (I) 5 is as follows: COOH N % > : N O N s COOH © Formula (I). A lHVIOFs sensor with high reactivity detects HClO with high selectivity, ensuring the accuracy of detection. The sensor has the advantages of being visible to the naked eyes as compared with common HClO sensors of the type of organic polymers.
    公开号:NL2024897A
    申请号:NL2024897
    申请日:2020-02-13
    公开日:2020-08-27
    发明作者:Li Yanan；Li Qianying；Guan Qun；Zhang Mingyue；Dong Yubin
    申请人:Univ Shandong；
    IPC主号:
    专利说明:

    PHENOTHIAZINE-BASED METAL-ORGANIC FRAMEWORK MATERIAL, AND
    PREPARATION METHOD AND USE THEREOF Field of the Invention The present invention relates to the technical field of sensors, and in particular to a phenothiazine-based metal-organic framework material, and a preparation method and use thereof. Background of the Invention The information disclosed in this section is only for the purpose of increasing understanding of the general background of the present invention, and is not necessarily regarded as an acknowledgement or any form of suggestion that this information constitutes the prior art already known to those of ordinary skills in the art. A metal-organic framework (MOF) is a hot research topic in recent years. Because of the porous structure characteristic and large specific surface area of the MOF, it has become the main theme of research in aspects of adsorption and separation. Subsequently, the researches of the catalytic and sensing properties of the MOF have become increasingly active, and many important advances have been made. In contrast, the preparation of a nano-scale porous MOF (NMOF) and the study of its physical and chemical properties have just started. NMOFs containing specific organic and inorganic functional groups can be designed and synthesized by a post-modification method or an in-situ assembly method, and these functionalized NMOFs have wide application prospects in sensing and biological imaging. In nature, HOC! is a weak acid (pKa = 7.63), which has high reactivity and transient activity in a physiological environment. However, maintaining a reasonable HOCI concentration in the physiological environment is essential for many cell functions. In general, the residual chlorine content in tap water is below 1 mg per liter, which is far below the WHO standard of 5 mg per liter. Chlorine has a pungent smell. Most people can smell the pungent smell when the chlorine content in water exceeds 2 mg per liter. As for chlorine of other forms existed in water, the "taste threshold" of most people is also lower than 5 mg per liter, and sensitive people can even taste the pungent smell when the content of chlorine is 0.3 mg per liter. The national standard stipulates that the residual chlorine content in the finished water > 0.3 mg/L, and the water supply company generally controls it between 0.3-0.5 mg/L, so as long as it does not exceed
    0.5 mg/L, there is no harm to human body. If it is greater than 0.8 mg/L, it indicates that the tap water should not be directly used for drinking. Therefore, it is very necessary to detect hypochlorous acid in tap water. Summary of the Invention An objective of the present invention is to provide a phenothiazine-based metal-organic framework material, and a preparation method and use thereof. The material has high selectivity for hypochlorous acid, can be used in detection of hypochlorous acid in tap water, and ensures the accuracy of the detection. Furthermore, the material can reactwith hypochlorous acid after contact to generate a product containing a sulfoxide structure, accompanied with obvious color changes, and can be used as a sensor visible to the naked eyes to quickly and conveniently detect hypochlorous acid in water. Furthermore, the reaction between the material and hypochlorous acid is reversible, such that the material can be recovered and recycled. In order to achieve the aforementioned objective, the present invention adopts the following technical solution. In a first aspect of the present invention, the present invention provides a compound of formula (I):
    COOH ® CyN
    SHE coon » Formula (1). In a second aspect of the present invention, the present invention provides a method for preparing a compound of formula (I), which includes performing the following reactions.
    on S$ — (Ay ~ vo COOCH, COOH DO Dd © > LEY oh oC Br NH Br | N LJ Oonk) Oonk) Dug HCOOH—= Cry Cy ) ys ] [ys Br Br H COOCH:; COOH B c D 1 Preferably, the method includes the following steps: (1) under the protection of nitrogen, reacting phenothiazine with 1,3-dibromopropane in a first solvent in the presence of a first base to obtain an intermediate A; (2) reacting 3,6-dibromo-1,2-phenylenediamine with formic acid in a second solvent under heating and refluxing to obtain an intermediate B; (3) reacting the intermediate A with the intermediate B in a third solvent in the presence of a second base under heating and refluxing to obtain an intermediate C; (4) under the protection of nitrogen, reacting the intermediate C and 4-methoxycarbonyl phenylboronic acid in a fourth solvent under the catalysis of cesium fluoride and triphenylphosphine palladium under heating and refluxing to obtain an intermediate D; and (5) hydrolyzing the intermediate D in a fifth solvent in the presence of a third base under heating and stirring to obtain a compound of formula (I). Preferably, in step (1), the first solvent is selected from one or more of dichloromethane, ethylene glycol, methanol, ethanol, toluene, tetrahydrofuran, N,N-dimethylformamide and dimethyl sulfoxide, and is preferably N,N-dimethylformamide.
    In the present invention, the reaction of step (1) is difficult to occur, and the selection of the first solvent will affect the synthesis of the intermediate A.
    In the aforementioned first solvent, the reaction of step (1) can be carried out, but the yield of the reaction is different, wherein when any one of N,N-dimethylformamide, methanol, toluene and dimethylsulfoxide is used as the first solvent, it is easier to carry out the reaction with higher yield, and the especially preferred solvent is N,N-dimethylformamide.
    Preferably, in step (1), the first base is selected from one or more of sodium hydroxide, potassium hydroxide, potassium carbonate and sodium carbonate, and is preferably potassium hydroxide.
    Preferably, in step (1), the reaction is carried out under stirring at room temperature, preferablyat 25°C.
    Preferably, in step (1), the molar ratio of phenothiazine, the first base, and 1,3-dibromopropane is 1:(1-2):(3-5), preferably 1:1-2:3, and more preferably 1:1:3. In the reaction of step (1), the molar ratio of phenothiazine, the first base and 1,3-dibromopropane is also an important factor affecting the reaction.
    Under an arbitrary molar ratio, the reaction of step (1) can be carried out, but the difference in yield is large.
    When the molar ratio of phenothiazine, the first base and 1,3-dibromopropane is 1:(1-2):(3-5), the reaction of step (1) is easier to carry out, and especially when the molar ratio is 1:1-2:3, more preferably 1:1:3, it is easier for the reaction of step (1) to obtain a higher yield.
    Preferably, in step (2), the second solvent is selected from one or more of methanol, ethanol and toluene, and is preferably methanol.
    Preferably, in step (2), the reaction temperature is not lower than 25°C, and preferably not higher than 100°C, and is preferably 62-70°C.
    The reaction temperature will affect the reaction of step (2). In the experiment, the applicant finds that at a lower reaction temperature such as 25°C or lower, the yield of the reaction is almost zero, and the reaction temperature being too high will also affect the process of the reaction.
    For example, when the temperature is higher than 100°C, the reaction is difficult to carry out, when the temperature is not lower than 85°C, the yield of the reaction will decrease, while when the temperature 1s 62-70°C, it is easier to obtain a higher yield.
    Preferably, in step (2), the molar ratio of 3,6-dibromo-1,2-phenylenediamine to formic acid is 1:(1-2), preferably 1:1.5-2, and more preferably 1:1.5 or 1:2. In the reaction of step (2), the molar ratio of 3,6-dibromo-1,2-phenylenediamine to formic acid is also an important factor affecting the reaction.
    Under an arbitrary molar ratio, the reaction of step (2) can be carried out, but the difference in the yield is large.
    When the molar ratio of 3,6-dibromo-1,2-phenylenediamine to formic acid is 1:1.5-2, the reaction of step (1) is easier to carry out, and especially when the molar ratio is 1:1.5 or 1:2, it is easier forthe reaction of step (2) to obtain a higher yield which can reach 100%. Preferably, in step (3), the third solvent is selected from one or more of methanol, ethanol and toluene, and is preferably ethanol or methanol.
    Preferably, in step (3), the second base is selected from one or more of sodium hydroxide, potassium hydroxide, potassium carbonate and sodium carbonate, and is preferably potassium carbonate.
    Preferably, in step (3), the reaction temperature is not lower than 25°C, and preferably not higher than 100°C, and is preferably 75-80°C; the reaction temperature will affect the reaction of step (3). In the experiment, the applicant finds that at a lower reaction temperature such as 25°C or lower, the yield of the reaction is 5 almost zero, and the reaction temperature being too high will also affect the process of the reaction.
    For example, when the temperature is higher than 100°C, the reaction is difficult to carry out, when the temperature reaches 85°C or higher, the yield of the reaction will begin to decrease, while when the temperature is 75-80°C, the reaction state is better.
    Preferably, in step (3), the molar ratio of the intermediate A, the intermediate B and the second baseis 1:(1-2):(1-3), preferably 1:1-2:3, and more preferably 1:1:3 or 1:2:3. In the reaction of step (3), the molar ratio of the intermediate A, the intermediate B, and the second base is also an important factor affecting the reaction.
    Under an arbitrary molar ratio, the reaction of step (3) can be carried out, but the degree of difficulty of the reaction is different, and the difference in the yield is also large.
    When the molar ratio of the intermediate A, the intermediate B, and the second base is 1:(1-2):(1-3), the reaction of the step (1) is easier to carry out, and especially when the molar ratio is 1:1-2:3, it is easier forthe reaction of the step (2) to obtain a higher yield.
    Especially when the molar ratio is 1:1:3 or 1:2:3, the reaction state is better.
    Preferably, in step (4), the fourth solvent is selected from one or more of dichloromethane, ethylene glycol, methanol, ethanol, toluene, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide and 1,4-dioxane, and is preferably tetrahydrofuran or 1,4-dioxane.
    Preferably, in step (4), the reaction temperature is not lower than 25°C, and preferably not higher than 150°C, and is preferably 90-100°C.
    The reaction temperature will affect the reaction of step (4). In the experiment, the applicant finds that at a lower reaction temperature such as 25°C or lower, the yield of the reaction is almost zero, and the reaction temperature being too high will also affect the process of the reaction.
    For example, when the temperature is higher than 150°C, the reaction is difficult to carry out, when the temperature reaches 85°C or lower but higher than 25°C, the yield of the reaction will begin to decrease, while when the temperature is 90-100°C, the reaction state is better.
    Preferably, in step (4), the molar ratio of the intermediate C, 4-methoxycarbonyl phenylboronic acid, cesium fluoride and triphenylphosphine palladium is 1:(1-3):(4-5):(0.3-0.5), and ispreferably 1:3:4.7:0.33.
    In the reaction of step (4), the molar ratio of the intermediate C, 4-methoxycarbonylphenylboronic acid, cesium fluoride and triphenylphosphine palladium is also an important factor affecting the reaction. Under an arbitrary molar ratio, the reaction of step (4) can be carried out, but the difficulty degree of the reaction is different, and the difference in yield is also large. When the molar ratio of the intermediate C, 4-methoxycarbonylphenylboronic acid, cesium fluoride and triphenylphosphine palladium is 1:(1-3):(4-5):(0.3-0.5), the reaction of step (4) is easier to carry out, and especially when the molar ratio is 1:3:4.7:0.33, the reaction state of step (4) is better.
    Preferably, in step (5), the fifth solvent is selected from one or more of water, dichloromethane, methanol, ethanol, toluene, tetrahydrofuran, N,N-dimethylformamide and 1,4-dioxane, and is preferably a water-methanol-tetrahydrofuran ternary mixed solvent system; and preferably, the volume ratio of water, methanol and tetrahydrofuran in the water-methanol-tetrahydrofuran ternary mixed solvent system is 1:1-2:1, and preferably 1:1:1.
    The selection of the fifth solvent will affect the progress of the reaction of step (5). When the fifth solvent is selected from one or more of water, dichloromethane, methanol, ethanol, toluene, tetrahydrofuran, N,N-dimethylformamide, and 1,4-dioxane, or a solvent similar to these solvents is selected, the reaction in step (5) can be carried out, but the difficulty of the reaction is different, and the yield is different. When the aforementioned solvents participate in the reaction in the form of a solvent combination or system, for example when the fifth solvent is selected from at least two of water, dichloromethane, methanol, ethanol, toluene, tetrahydrofuran, N,N-dimethylformamide, and 1,4-dioxane, the reaction is easier to carry out. Such a solvent combination or solvent system, such as a water-methanol-tetrahydrofuran system, a water-methanol system, a methanol-tetrahydrofuran system, a water-tetrahydrofuran system, etc, has a better reaction state, but when the solvent combination or solvent system contains tetrahydrofuran, the reaction is easier to carry out and the yield is correspondingly higher. In particular, when these solvent systems or solvent combinations are mixed in a specific volume ratio, it is more favorable to the reaction, such as water-methanol-tetrahydrofuran (1:2:1), water-methanol (1:1), methanol-tetrahydrofuran (1:1), water-tetrahydrofuran (1:1); more preferably, when the solvent system includes water, methanol, and tetrahydrofuran, the reaction state is better; and when the volume ratio is water-methanol-tetrahydrofuran (1:1-2:1), and preferably 1:1:1, it is easier to obtain a betteryield. Preferably, in step (5), the third base is selected from one or more of sodium hydroxide, potassium hydroxide, potassium carbonate and sodium carbonate, and is preferably sodium hydroxide. 5 Preferably, in step (5), the reaction temperature is 25-100°C, and preferably 40-60°C; The reaction temperature will affect the reaction of step (5). In the experiment, the applicant finds that when the lower reaction temperature is lower than 25°C, the reaction is difficult to carry out; when the reaction temperature is higher, such as close to 100°C, the yield of the reaction starts to decrease; while when the temperature is 40-60°C, the reaction state is better. Preferably, in step (5), the molar ratio of the intermediate D to the third base is 1:(20-25), and preferably 1:25. In a more specific embodiment, the method for preparing the compound of formula (I) of the present invention includes the following steps: (a) under the protection of nitrogen, putting phenothiazine, potassium hydroxide and anhydrous N,N-dimethylformamide into a two-necked round bottom flask, stirring for 30 min, then adding 1,3-dibromopropane and stirring at room temperature for 48 h, tracking the reaction result by TLC, pouring the mixture into water after ending of the reaction, and extracting with ethyl acetate for three times, merging the organic phases and drying, removing the solvent under reduced pressure, and then purifying through column chromatography separation to obtain the intermediate A; (b) putting 3,6-dibromo-1,2-phenylenediamine, formic acid and methanol into a one-neck round bottom flask, heating the mixture and refluxing for 24 h, and tracking the reaction result by TLC, removing the solvent under reduced pressure, and then purifying through column chromatography separation to obtain the intermediate B; BrN (TS
    H Br
    B (c) putting the intermediates obtained in steps (a) and (b), potassium carbonate and ethanol into a one-neck round bottom flask, heating the mixture and refluxing for 24 h, and tracking the reaction result by TLC, removing the solvent under reduced pressure after ending of thereaction, and then purifying through column chromatography separation to obtain the intermediate C, Br
    N >
    N Br 1
    N »! |
    C (d) under the protection of nitrogen, putting the intermediate C obtained in the step (c), 4-methoxycarbonyl phenylboronic acid, cesium fluoride and triphenylphosphine palladium into a three-necked round bottom flask, adding 1,4-dioxane, heating the mixture and refluxing for 24 h, and tracking the reaction result by TLC, removing the solvent is removed under reduced pressure after ending of the reaction, and then purifying through column chromatography separation to obtain the intermediate D; and COOCH,NCQ
    N LL >JD COOCH,
    D (e) putting the intermediate D obtained in step (d), sodium hydroxide, tetrahydrofuran, methanol and water into a one-neck round bottom flask, then respectively adding with, and hydrolyzing by heating under stirring at 40°C;after obtaining a clear clarified reaction solution, pouring the reaction solution into water to adjust the pH to be acidic to generate a white precipitate, carrying out suction filtering, washing with diethyl ether for three times, and air-drying to obtain the compound of formula (I).
    COOH ® (U)
    N 55 coo OS Formula (I) In a third aspect of the present invention, the present invention provides a metal-organic framework (NMOF) material which takes a compound of formula (I) as an organic ligand. The compound of formula (I) can be represented as H;L when used as an organic ligand. During preparation of the metal-organic framework material, after H>L is coordinated with the metal, the two hydrogens in H;L (i.e, the Hs in the two carboxyl groups) will be lost, and H,L. will exist in the form of L. Preferably, the metal-organic framework material is a nano metal-organic framework material, and its chemical formula is ZrsO4(OH)s(Cs6H25N304S)s, or it can also be written as ZrsOs(OH Le. In a fourth aspect of the present invention, the present invention provides a method for preparing the aforementioned nano-metal-organic framework material, which includes reacting H,L. with zirconium tetrachloride in a solvent to obtain the nano-metal-organic framework material. In the aforementioned preparation process, Hol. will lose two hydrogens after being coordinated with Zr. Preferably, the method for preparing the nano-metal-organic framework material includes the following steps: reacting H;L with zirconium tetrachloride react in a sixth solvent in an oven, cooling to room temperature, centrifuging, soaking in N,N-dimethylformamide, activating with ethanol, washing with diethyl ether, and air-drying to obtain the nano-metal-organic framework material as white powder. Preferably, the sixth solvent is N,N-dimethylformamide and acetic acid; preferably, the molar ratio of the organic ligand HL to zirconium tetrachloride is 4-5:7-8 (i.e., 1:1.4-2), preferably 1:1.4-1.6, and more preferably 5:8 (i.e, 1:1.6). The molar ratio of the organic ligand H:L to zirconium tetrachloride will affect the preparation of the material. When the molar ratio is lower than 1:1.4 (Le. 5.7) or higher than 1:2, thereaction becomes more difficult to carry out, and when the molar ratio is 1:1.4-2, especially 1:1.4-1.6, the reaction proceeds smoothly.
    Preferably, the reaction temperature is 100°C, and the reaction time is 24 h.
    In a fifth aspect of the present invention, the present invention provides the use of a compound of formula (I) as a ligand in the preparation of a metal-organic framework material.
    In a sixth aspect of the present invention, the present invention provides a sensor or detector including a metal-organic framework material which takes a compound of formula (I) as a ligand, or a metal-organic framework material as described above (ZrsO4(OH)4L). In a seventh aspect of the present invention, the present invention provides use of a metal-organic framework material which takes a compound of formula (I) as a ligand or a nano-metal-organic framework material as described above (Zr;O4(OH)4Ls) as a sensor or detector in tap water detection or HCIO detection.
    Alternatively, it provides the use of the sensor or detector provided in the sixth aspect of the present invention in tap water detection or HCIO detection.
    Preferably, in the aforementioned use, the tap water detection refers to detecting HCIO in tap water.
    Preferably, in the aforementioned use, the HCIO detection refers to detecting HCIO in tap water.
    In an eighth aspect of the present invention, the present invention provides a method for rapidly detecting HClO, which includes placing a metal-organic framework material which takes a compound of formula (I) as a ligand, a nano-metal-organic framework material as described above or the sensor or detector described in the sixth aspect of the present invention in an HCIO-containing environment; reacting the nano-metal-organic framework material with HCIO to generate a metal-organic framework material containing sulfoxide accompanied with a color change, such that HCIO is indicated by the color change.
    The gradation of the color varies according to the concentration of HCIO.
    Taking the nano-metal-organic framework material Zr;O:(OH)4Lg as an example, when HCIO is present, the color of the organic framework material will change from white color to different degrees of red (because hypochlorous acid will react with the material to generate a sulfoxide structure, i.e., generating a metal-organic framework material containing sulfoxide), such that the presence of HCIO can be detected or judged according to the color change that is visible to the naked eyes.
    Preferably, the HCIO-containing environment is preferably a water environment.
    The principle of detecting hypochlorous acid by the nano-metal-organic framework (NMOF) material or the sensor or detector of the present invention is that: the NMOF material or the sensor or detector can react with HCIO (mg) in tap water to generate a metal organic framework (NMOF) containing sulfoxide, accompanied with an obvious color change (the NMOF gradually changes from the originally white to red, and finally to purple red). Moreover, the NMOF has no such phenomenon with Ca ” Nat, K', Mg” and the like ions in water, and will not be interfered by Zn**, Cu *, Fe’, Fe ’, H,0,, SO,4%, NO, NO", Ba”, CI" and the like ions (with high selectivity for ClO’). Therefore, the NMOFs can be used as a sensor or detector that is visible to the naked eyes, to quickly and conveniently detect HCIO in tap water.
    The present invention has the following beneficial effects: (1) The NMOF with high reaction activity as provided by the present invention has the advantage of being visible to the naked eyes compared with HCIO sensors of the type of organic polymers. (2) Detecting HCIO by adopting the NMOF sensor with high reactivity of the present invention has high selectivity, can eliminate interference of other ions in water.
    Specifically, in the present invention, Zn’*, Ca", CIO’, Cu ’ Fe’’, Fe’, H,0,, SO”, K*, Mg", Na’, NOX, NO", Ba *, CT are respectively detected for fluorescence response intensities by using the NMOF sensor under the same conditions in an experiment, and the results are as shown in FIG. 16. Therefore, the NMOF of the present invention shows high selectivity to CIO” and ensures detection accuracy.
    Moreover, the NMOF of the present invention has very high concentration sensitivity to hypochlorous acid, and the fluorescence response of the NMOF is continuously enhanced with the increase of the concentration of hypochlorous acid, so that hypochlorous acid in tap water can be well detected. (3) The detection on HCIO by the NMOF of the present invention is reversible.
    The material that has been used for HCIO detection can be reduced for recycling, and the reduction process is still accompanied with a color change that is visible to the naked eyes.
    That is, the color will change from red to white again.
    This feature is conducive to the recovery and recycling of the material.
    Brief Description of the Drawings The accompanying drawings of the specification which form a part of the present invention are used for providing further understanding of the present invention.
    The illustrative embodimentsof the present invention and the description thereof are used for explaining the present invention, and do not constitute improper limit to the present invention.
    Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings, in which: FIG. 1 is a "H NMR spectrogram of an intermediate A prepared in Example 1; FIG. 2 is a '"H NMR spectrogram of an intermediate B prepared in Example 1; FIG. 3 is a '"H NMR spectrogram of an intermediate C prepared in Example 1; FIG. 4 is a '"H NMR spectrogram of an intermediate D prepared in Example 1; FIG. 5 is a 'H NMR spectrogram of the compound of formula (I) (i.e, the ligand H,L) prepared in Example 1; FIG. 6 is a powder x-ray diffraction pattern of the NMOF prepared in Example 2, where the left panel is a powder x-ray diffraction pattern of an untreated NMOF; and in the right panel, by taking the horizontal axis of coordinates as the bottom, three powder X-ray diffraction peak diagrams from bottom to top respectively correspond to the NMOF without any treatment (marked as controls, the peak diagram is the same as the left panel), the NMOFs oxidized by hypochlorous acid as added (marked as oxidation), the NMOF reduced by Vc as added (marked as reduction); from the comparison between the left and right panels, it can be seen that the structure of the NMOF is basically unchanged after oxidation and re-reduction; FIG. 7 is a solid ultraviolet spectrum of the NMOF prepared in Example 2; where 1 refers to the NMOF, I' refers to the NMOF oxidized by hypochlorous acid as added, and 1" refers to the NMOF reduced by Vc as added; FIG. 8 is an infrared spectrum of the NMOF prepared in Example 2, where after comparison of the three spectra, it can be seen that when hypochlorous acid is added, the NMOF will have a characteristic absorption peak (1046 cm!) of sulfoxide after being oxidized, and this peak disappears after the NMOF is reduced by Vc as added.
    FIG. 9 is a stereoscan photograph of NMOFs prepared in Example 2; FIG. 10 is a stereoscan photograph of the NMOFs prepared in Example 2 and after oxidation and reduction, where the stereoscan photograph of the control group shows that the material is a sheet-like NMOF, and the material is basically unchanged and is still the sheet-like NMOF after being oxidized (oxidized by hypochlorous acid as added) and reduced (reduced by Vc as added); FIG. 11 is a TGA spectrum of the NMOF prepared in Example 2, and it can be seen from thisfigure that, the NMOF has serious weight loss after subjected to 300°C and has good thermal stability.
    FIG. 12 is a BET series spectrum of the NMOF prepared in Example 2. FIG. 13 is a schematic color diagram of NMOFs prepared in Example 2 and after being oxidized by hypochlorous acid and being reduced by Vc; where the control group is original white NMOF powder (marked as control); after reacted with hypochlorous acid, the NMOF becomes red NMOF powder (marked as oxidation), after being reduced by Vc, the NMOF is turned back to white powder (marked as reduction). FIG. 14 is a fluorescence spectrum of NMOFs prepared in Example 2 (marked as control) and after being oxidized by hypochlorous acid (marked as oxidation) and being reduced by Vc (marked as reduction); from the control to the oxidation and to the reduction, the color will change from white to red and then to white; where the excitation wavelength is 323 nm, and the emission wavelength is 394-400 nm.
    FIG. 15 is a fluorescence spectrum of the NMOF prepared in Example 2 under different concentrations of hypochlorous acid; in this figure, the concentrations of hypochlorous acid corresponding to respective lines from bottom to top in the vertical direction at 400 nm are 0 mg/L, 0.3 mg/L, 0.5 mg/L, 0.8 mg/L, 2.0 mg/L and 5.0 mg/L respectively; and the excitation wavelength is 323 nm, and the emission wavelength is 394-400 nm; and FIG. 16 is a graph showing the experimental results of the specific fluorescence response of the NMOF prepared in Example 2 to CIO’, where the excitation wavelength is 323 nm and the emission wavelength is 394-400 nm.
    Detailed Description of Embodiments The present invention will be described in detail below in connection with specific examples.
    It should be understood that, the following examples are only intended to illustrate the present invention, rather than limiting the scope of the present invention.
    The experimental methods in the following embodiments which are not specified with specific conditions are generally carried out according to conventional conditions or according to the conditions recommended by the manufacturer.
    Unless otherwise defined, all professional and scientific terms used herein have the same meaning as those familiar to those skilled in the art.
    Furthermore, any method and material similar or equivalent to those recited can be applied to the method of the present invention.
    Thepreferred implementation methods and materials described herein are for the purpose of demonstration only. Example 1 Synthesis of Intermediate A Preparation example 1: under the protection of nitrogen, phenothiazine (25 mmol, 5 g), potassium hydroxide (25 mmol, 1.4 g) and anhydrous N,N-dimethylformamide (50 ml) were put into a 100 mL two-necked round bottom flask, and stirred for 30 min, and thenl,3-dibromopropane (75 mmol, 15.1 g) was added. The mixture was stirred at room temperature for 48 h, and the reaction result was tracked by TLC. The mixture was poured into 250 ml of water after ending of the reaction, and extracted with ethyl acetate for three times. The organic phases were merged and dried. The solvent was removed under reduced pressure, and then purification was carried out through column chromatography (petroleum ether) separation. 1.6 g of the intermediate A (with a yield of 20%) was obtained. The hydrogen spectrum of it was as shown in FIG. 1.
    IR (KBr pellet cm™): 3064 (m), 2960 (m), 2871 (m), 1485 (w), 1456 (s), 1331 (s), 1249 (s), 1038 (w), 757 (s), 728 (w).
    IH-NMR (400 MHz, DMSO-d6, 25°C, TMS, ppm): 7.21 (t, 1H, -C6H4-), 7.21 (t, 1H, -C6H4-), 7.20 (d, IH, -C6H4-), 7.20 (d, 1H, -C6H4-), 7.17 (d, IH, -C6H4-), 7.17 (d, 1H, -C6H4-), 6.97 (t, 1H, -C6H4-), 6.97 (t, IH, -C6H4-), 4.05 (t, 2H, -CH2-), 3.61 (t, 2H, -CH2-),
    2.19 (m, 2H, -CH2-). Elemental analysis (%) calcd: C 56.26, H 4.41, N 4.37; Found: C 56.22, H 4.49, N 4.44. In the synthesis of the intermediate A, the reaction solvent and the reactant dosage relation were studied as follows: 1) selection of the reaction solvent, as shown in Table 1: according to the above preparation process, N,N-dimethylformamide was replaced with the solvent shown in Table 1 to prepare the intermediate A. Table 1 Preparation
    Co owe [0 se 5 2) selection of the reactant dosage relation was as shown in Table 2: according to the above preparation process, reactants were added in the molar ratio shown in Table 2 to prepare the intermediate A. Table 2 The molar ratio of Preparation phenothiazine, the base and Yield (%) Example
    EE Synthesis of Intermediate B Preparation Example 1: 3,6-dibromo-1,2-phenylenediamine (10 mmol, 2.66 g), formic acid (15 mmol, 0.69 g), 50 mL of methanol were put into a 100 mL single-necked round bottom flask, the mixture was heated and refluxed at 65°C for 24 h, and the reaction result was tracked by TLC. The solvent was removed under reduced pressure, and then purification was carried out through column chromatography (dichloromethane) separation. The intermediate B (with a yield of 100%) was prepared. The hydrogen spectrum of it was as shown in FIG. 2. IR (KBr pellet cm™): 3326 (m), 2536 (m), 1489 (s), 1184 (m), 951 (w), 870 (w), 803 (s), 616 (w). 1H-NMR(400 MHz, DMSO-d6, 25°C, TMS, ppm): 8.85 (s, 1H, -CH-), 7.50 (s, 1H, -C6H2-),
    7.50 (s, IH, -C6H2-), 5.50 (s, IH, -NH-). Elemental analysis(%) calcd: C 30.47, H 1.46, N
    10.15; Found: C 30.52, H 1.49, N 10.34. In the synthesis of the intermediate B, the reaction solvent, the reactant dosage relation, and the reaction temperature were studied as follows: 1) selection of the reaction solvent, as shown in Table 3: according to the above preparation process, methanol was replaced with the solvent shown in Table 3 to prepare the intermediate B. Table 3 Preparation ewe
    2) selection of the reactant dosage relation was as shown in Table 4: according to the above preparation process, reactants were added in the molar ratio shown in Table 4 to prepare the intermediate B. Table 4 The molar ratio of Preparation 3,6-dibromo-1,2-phenylene Yield (%) Example TT | ee swe ww 3) selection of the reaction temperature, as shown in Table 5: according to the above preparation process, the temperature shown in Table 5 was used as the reaction temperature to prepare the intermediate B. Table 5 Preparation se A wm Synthesis of Intermediate C Preparation Example 1: the intermediate A (1 mmol, 0.276 g), the intermediate B (1 mmol,
    0.32 g), potassium carbonate (3 mmol, 0.414 g) and 50 mL of ethanol were put into a single-necked round bottom flask, the mixture was heated and refluxed at 75°C for 24 h, and the reaction result was tracked by TLC. The solvent was removed under reduced pressure after ending of the reaction, and then purification was carried out through column chromatography (dichloromethane) separation to obtain the intermediate C (with the yield of 55.5%). The hydrogen spectrum of it was as shown in FIG. 3. IR (KBr pellet cm™): 3064 (m), 2970 (m), 2871 (m), 1491 (s), 1456 (s), 1320 (w), 1155 (s), 918 (w), 751 (8), 730 (w), 630 (w). 1H-NMR (400 MHz, DMSO-d6, 25°C, TMS, ppm): 8.27 (s, IH, -CH-), 7.34 (s, 1H, -C6H2-),
    7.32 (s, IH, -C6H2-), 7.21 (t, 1H, -C6H4-), 7.21 (t, 1H, -C6H4-), 7.20 (d, 1H, -C6H4-), 7.20 (d, IH, -C6H4-), 7.04 (d, 1H, -C6H4-), 7.02 (d, 1H, -C6H4-), 6.98 (t, IH, -C6H4-), 6.96 (t, IH, -C6H4-), 4.59 (t, 2H, -CH2-), 3.99 (t, 2H, -CH2-), 2.27 (m, 2H, -CH2-). Elemental analysis(%) caled: C 51.28, H 4.44, N 8.16; Found: C 51.32, H 4.49, N 8.24.
    1) selection of the reaction solvent, as shown in Table 6: according to the above preparation process, ethanol was replaced with the solvent shown in Table 6 to prepare the intermediate C. Table 6 Third Solvent Yield (%) Example we 2) selection of the reactant dosage relation was as shown in Table 7: according to the above preparation process, reactants were added in the molar ratio shown in Table 7 to prepare the intermediate C. Table 7 The molar ratio of the Preparation intermediate A, the Yield (%) Example Te | 99 3) selection of the reaction temperature, as shown in Table 8: according to the above preparation process, the temperature shown in Table 8 was used as the reaction temperature to prepare the intermediate C. Table 8 Reaction temperature (°C) Yield (%) Example swe
    EE Synthesis of Intermediate D Preparation Example 1: under the protection of nitrogen, the intermediate C (1 mmol,
    0.515 g), 4-methoxycarbonylphenylboronic acid (3 mmol, 0.54 g), cesium fluoride (4.7 mmol,
    0.714 g) and triphenylphosphine palladium (0.33 mmol, 0.383 g)were put into a three-necked round-bottom flask, 1,4-dioxane (50 ml)was added, and the mixture was heated and refluxed at 90°C for 24 h, and the reaction result was tracked by TLC. The solvent was removed under reduced pressure after ending of the reaction, and then purification was carried out throughcolumn chromatography (dichloromethane:ethyl acetate = 10:1) separation to obtain the intermediate D (with the yield of 58%). The hydrogen spectrum of it was as shown in FIG. 4. IR (KBr pellet cm’): 3343 (m), 3051 (m), 2944 (m), 1715 (s), 1456 (m), 1375 (s), 1280 (s), 1188 (s), 1118 (s), 863 (s), 775 (s), 632 (w).
    1H-NMR (400 MHz, DMSO-d6, 25°C, TMS, ppm): 8.26 (s, IH, -CH-), 8.23 (s, 2H, -C6H2-), 8.09-8.06 (d, 2H, -C6H4-), 8.03-8.01 (d, 2H, -C6H4-), 7.63-7.61 (d, 2H, -C6H4-),
    7.63-7.60 (d, 2H, -C6H4-), 7.24-7.22 (t,2H, -C6H4-), 7.14-7.11 (d, 2H, -C6H4-), 7.09-7.06 (d, 2H, -C6H4-), 6.95-6.93 (t,2H, -C6H4-), 4.07 (t, 2H, -CH2), 3.90 (s, 3H, -CH3), 3.90(s, 3H, -CH3), 3.41 (t, 2H, -CH2), 1.57 (m, 2H, -CH2). Elemental analysis(®%) calcd: C 72.94, H 4.99, N 6.72; Found: C 72.81, H5.07, N 6.64. 1) selection of the reaction solvent, as shown in Table 9: according to the above preparation process, 1,4-dioxane was replaced with the solvent shown in Table 9 to prepare the intermediate D. Table 9 Preparation / Ce ewes | [meow | Ce ewe ewe Ewe Cee | amen | 2) selection of the reactant dosage relation was as shown in Table 10: according to the above preparation process, reactants were added in the molar ratio shown in Table 10 to prepare the intermediate D. Table 10 The molar ratio of the intermediate C, Preparation 4-methoxycarbonyl Example phenylboronic acid, cesium a fluoride and triphenylphosphineeww 3) selection of the reaction temperature, as shown in Table 11: according to the above preparation process, the temperature shown in Table 11 was used as the reaction temperature to prepare the intermediate D. Table 11 Preparation
    EE Synthesis of the compound of formula (I) Preparation Example 1: the intermediate D (1 mmol, 0.625 g), sodium hydroxide (25 mmol, 1.0 g), tetrahydrofuran (20 ml), methanol (20 ml), and water (20 ml)were put into a single-necked round bottom flask, then were respectively added, and the mixture was hydrolyzed by heating under stirring at 40°C. After a clearreaction solution was obtained, the reaction solution was poured into water to adjust the pH to be acidic to generate a white precipitate. The white precipitate was subjected to suction filtering, washed with diethyl ether for three times, and air-dried to obtain the compound of formula (T) (with the yield of 98%). The hydrogen spectrum of it was as shown in FIG. 5. IR (KBr pellet cmt): 2963 (m), 1688 (vs), 1607 (s), 1458 (s), 1424 (m), 1323 (s), 1294 (s), 1184 (s), 1016 (s), 769 (s), 743 (5), 547 (w). 1H-NMR(400 MHz, DMSO-d6, 25°C, TMS, ppm): 8.19 (s, IH, -CH-), 8.17 (s, 2H, -C6H2-), 8.05-8.04 (d, 2H, -C6H4-), 8.03-7.60 (d, 2H, -C6H4-), 7.57-7.55 (d, 2H, -C6H4-),
    7.23-7.22 (t, 2H, -C6H4-), 7.13-7.12 (d, 2H, -C6H4-), 7.08-6.94 (d, 2H, -C6H4-), 6.92-6.91 (t,2H, -C6H4-), 6.63-6.61 (t,2H, -C6H4-). Elemental analysis(%) calcd: € 72.34, H 4.55, N
    7.03; Found: C 72.66, H4.67, N 6.96. 1) selection of the reaction solvent, as shown in Table 12: according to the above preparation process, the water-methanol-tetrahydrofuran solvent system was replaced with the solvent shown in Table 12 to prepare the ligand H,L. Table 12
    CE | 2 Water-methanol-tetrahydrof en 4 Methanol-tetrahydrofuran Ee ee 2) selection of the reactant dosage relation was as shown in Table 13: according to the above preparation process, reactants were added in the molar ratio shown in Table 10 to prepare the ligand H:L.
    Table 13 Preparation The molar ratio of the Yield (%) ine mamatt OE 3) selection of the reaction temperature, as shown in Table 14: according to the above preparation process, the temperature shown in Table 14 was used as the reaction temperature to prepare the ligand H,L.
    Table 14 Reaction temperature (°C) Yield (%%) Example [ww Example 2 Synthesis of phenothiazine-based nano-MOF (or NMOF)
    Preparation Example 1: ZrCl, (9.60 mg, 0.040 mmol) and HL (0.025 mmol, 15 mg) were dissolved in N,N-dimethylformamide (3.2 mL), acetic acid (120 pL) was added, andthe mixture was placed in an oven at 100°C to react for 24 h, cooled to room temperature, centrifuged, soaked in N,N-dimethylformamide, activated with ethanol, washed with diethylether, and air-dried to obtain the compound 1 as white powder (with the yield of 80%). The stereoscan photograph of it was as shown in FIG. 9. The X-ray powder diffraction pattern of it was as shown in FIG. 6 (left panel). The ultraviolet spectrum of it was as shown in FIG. 7 (in FIG. 7, 1 referred to the prepared NMOF, I' referred to the NMOF oxidized by hypochlorous acid as added, and 1' referred to the NMOF reduced by Vc as added). The infrared spectrum ofit was as shown in FIG. 8. The TGA spectrum of it was as shown in FIG. 11; and the BET spectrum of it was as shown in FIG. 12. IR (KBr pellet cm™): 3338 (m), 2971 (m), 1592 (m), 1417 (s), 1250 (s), 1104 (w), 778 (s), 659 (s). In this example, the dosage of the reactants was selected, as shown in Table 15: according to the method of preparation example 1 described above, reactants were added in the molar ratio relationship shown in Table 15 to synthesize the nano-metal-organic framework material.
    Table 15 H,L and zirconium Preparation Molar Ratio Example 3 1) Color change of the powder when the NMOF reacts with HCIO 30 mg of the NMOF prepared in Example 2 was taken and put into a prepared circular groove.
    The powder that did not contact hypochlorous acid was white (as shown in the left panel 1 of FIG. 13). Then 286 uL of a sodium hypochlorite solution was taken and diluted in 1 mL of water to obtain a 0.1 mol/L sodium hypochlorite solution.
    Then 10 uL of the sodium hypochlorite solution was taken and added into the NMOF which was ultrasonically dispersed in water in advance, such that the NMOF immediately turned red.
    The mixture was centrifuged, washed with water, ethanol and diethyl ether, dried, and filled into the circular groove.
    That is, after hypochlorous acid was added, the color of the powder turned red (as shown in the left panel 2 of FIG. 13). The red powder was taken and ultrasonically dispersed in water, added with excess amount of a formulated 0.lmol/L Vc solution, such that the red powder immediately turned white.
    The mixture was centrifuged, washed with water, ethanol and diethyl ether, dried, and filled into the circular groove.
    That is, after reduction, the powder turned white (as shown in the right panel 1 of FIG. 13). In view of the above, the detection on hypochlorous acid by the NMOF was accompanied with a color change that is visible to the naked eyes.
    2) Reversibility of the fluorescence response of the NMOF to HCIO 1 mg of the dried NMOF (prepared in Example 2) was taken, ultrasonically dispersed in 1 mL of water, and measured for its fluorescence (the curve closest to the horizontal axis in FIG. 14), then 10 pL of the sodium hypochlorite solution freshly prepared in the above 1) was added, such that the solution immediately turned red, and then its fluorescence was measured (the uppermost curve in FIG. 14); then an excess amount of the Vc solution described in 1) was added, such that the solution immediately turned white, and then its fluorescence was measured (the curve closest to the horizontal axis in FIG. 14), where the excitation wavelength was 323 nm and the emission wavelength was 94-400 nm.
    As could be seen from FIG. 14, the detection on HCIO by the NMOF was reversible and had a color change that was visible to the naked eyes. 3) The fluorescence response of the NMOF to hypochlorous acid in tap water After consulting, according to the available chlorine content in tap water as stipulated by the state, sodium hypochlorite solutions of 0.3 mg/L, 0.5 mg/L, 0.8 mg/L, 2.0 mg/L. and 5.0 mg/L were prepared respectively.
    Then, 1 mg of the dried NMOF (prepared in Example 2) was taken, ultrasonically dispersed in 1 mL of water, added with the prepared sodium hypochlorite solution sequentially, and measured for its fluorescence (with the excitation wavelength of 323 nm, and the emission wavelength of 394-400 nm). The concentrations of hypochlorous acid corresponding to respective lines of the curve from bottom to top in the vertical direction at 400 nm in FIG. 15 were 0 mg/L, 0.3 mg/L, 0.5 mg/L, 0.8 mg/L, 2.0 mg/L, 5.0 mg/L respectively.
    As could be seen from FIG. 15, the NMOF had high sensitivity for detecting hypochlorous acid in tap water, and the fluorescence response of the NMOF increased with the increase of the hypochlorous acid concentration.
    Therefore, the NMOF of the present invention had high concentration sensitivity for hypochlorous acid, and could well detect hypochlorous acid in tap water. 4) Specific response of the NMOF to CIO’ 1 mg of the dried NMOF (prepared in Example 2) was taken, ultrasonically dispersed in ImL of water, diluted by 10 times, and then sequentially prepared into multiple NMOF solutions with a concentration of 0.1 mg/ml.
    The multiple NMOF solutions were respectively added with Zn", Ca”, CIO’, Cu”, Fe)", Fe ’, H,0,, SO”, K*, Mg ’ Na“, NO*, NO*, Ba ” Cl each at a concentration of 0.1 mol/L to measure fluorescence intensities (with an excitation wavelength of 323 nm, and an emission wavelength of 394-400 nm) respectively.
    The resultswere shown in FIG. 16. The results showed that under the same concentration condition, the NMOFs of the present invention showed extremely high fluorescence intensity for ClO” compared with other detection ions, indicating specificity and high selectivity for the C10". The above embodiments are preferred embodiments of the present invention.
    However, the implementation manners of the present invention are not limited by the above embodiments.
    Any other change, modification, substitution, combination, and simplification made without departing from the spiritual essence and principle of the present invention should be an equivalent replacement manner, and all are included in a claimed scope of the present invention.
    权利要求:
    Claims (46)
    [1]
    1. A composition of formula (I):
    COOH
    N CT) Eee
    J
    S COOH »Formula (I).
    [2]
    A method for preparing a composition of formula (I), comprising performing the following reactions: a, Oe
    S N COOCH COOH Br Br * HN gq Br 3 N (2®
    N.
    A N N 50 Or CN Br Br NN NN NH; N N N N + HCOOH - »> Ss () Ss] S NH, N Br Br H COOCH, COOH B Cc D I
    [3]
    Process according to claim 2, comprising the following steps: a) under the protection of nitrogen, reacting phenothiazine with 1,3-dibromopropane in a first solvent in the presence of a first base to obtain an intermediate A; b) reacting 3,6-dibromo-1,2-phenylenediamine with formic acid in a second solvent under heating and reflux to obtain an intermediate B; c) reacting the intermediate A with the intermediate B in a third solvent in the presence of a second base which is heated and refluxed to obtain an intermediate C: d) under the protection of nitrogen, whereby the intermediate C and 4- methoxycarbonylphenylboronic acid in a fourth solvent under the catalysis of cesium fluoride and triphenylphosphine palladium with heating and refluxing reacts to obtain an intermediate D; and e) hydrolyzing the intermediate D in a fifth solvent in the presence of a third base with heating and stirring to obtain a composition of formula (I).
    [4]
    The method of claim 3 wherein in step (a) the first solvent is selected from one or more of dichloromethane, ethylene glycol, methanol, ethanol, toluene, tetrahydrofuran, N, N-dimethylformamide and dimethyl sulfoxide.
    [5]
    The method of claim 4 wherein the first solvent is N-N-dimethylformamide.
    [6]
    A method according to any one of claims 3 to 5, wherein in step (a) the first base is selected from one or more of sodium hydroxide, potassium hydroxide, potassium carbonate and sodium carbonate.
    [7]
    The method of claim 6 wherein the first base is potassium hydroxide.
    [8]
    Process according to any one of claims 3 to 7, wherein in step (a) the reaction is carried out under stirring at room temperature, preferably at 25 ° C.
    [9]
    A method according to any one of claims 3 to 8, wherein in step (a) the molar ratio of phenothiazine, the first base, and 1,3-dibromopropane is 1: (1-2) :( 3-5).
    [10]
    The method of claim 10, wherein the molar ratio of phenothiazine, the first base, and 1,3-dibromopropane is 1: 1-2: 3, and more preferably 1: 1: 3.
    [11]
    A method according to any one of claims 3 to 10, wherein in step (b) the second solvent is selected from one or more of methanols, ethanol and toluene.
    [12]
    The method of claim 11, wherein the second solvent is and methanol.
    [13]
    Process according to any one of claims 3 to 12, wherein in step (b) the reaction temperature is not less than 25 ° C, and preferably not more than 100 ° C, and more preferably 62-70 ° C.
    [14]
    A method according to any one of claims 3 to 13, wherein in step (b) the molar ratio of 3,6-dibromo-1,2-phenylenediamine to formic acid is 1: (1-2).
    [15]
    A method according to claim 14, wherein the molar ratio of 3,6-dibromo-1,2-phenylenediamine to formic acid is preferably 1: 1.5-2, and preferably 1: 1.5 or 1: 2.
    [16]
    A method according to any one of claims 3 to 15, wherein in step (c) the third solvent is selected from one or more of methanol, ethanol and toluene.
    [17]
    The method of claim 16, wherein the third solvent is ethanol.
    [18]
    18. A method according to any one of claims 3 to 17, wherein in step (c) the second base is selected from one or more of sodium hydroxide, potassium hydroxide, potassium carbonate and sodium carbonate.
    [19]
    The method of claim 18, wherein the second base is potassium carbonate.
    [20]
    A method according to any one of claims 3 to 19, wherein in step (c) the reaction temperature is not less than 25 ° C, preferably 25-100 ° C, and more preferably 75-80 ° C.
    [21]
    A method according to any one of claims 3 to 20 wherein in step (c) the molar ratio of the intermediate A, the intermediate B and the second base is 1: (1-2) :( 1-3).
    [22]
    A method according to claim 21, wherein the molar ratio of the intermediate A, the intermediate B and the second base is 1: 1-2: 3, and preferably 1: 1: 3.
    [23]
    A method according to any one of claims 3 to 22, wherein in step (d) the fourth solvent is selected from one or more of dichloromethane, ethylene glycol, methanol, ethanol, toluene, tetrahydrofuran, N, N-dimethylformamide, dimethyl sulfoxide and 1 , 4-dioxane.
    [24]
    The method of claim 23, wherein the fourth solvent is tetrahydrofuran or 1,4-dioxane.
    [25]
    A method according to any one of claims 3 to 24, wherein in step (d), the reaction temperature is not less than 25 ° C, preferably 25-100 ° C, and more preferably 90- 100 ° C.
    [26]
    A method according to any one of claims 3 to 25, wherein in step (d) the molar ratio of intermediate C, 4-methoxycarbonylphenylboronic acid, cesium fluoride and triphenylphosphine palladium 1: (1-3) :( 4-5) :( 0.3 -0.5) 1s.
    [27]
    The method of claim 26, wherein the molar ratio of the intermediate C, 4-methoxycarbonylphenylboronic acid, cesium fluoride and triphenylphosphine palladium is 1: 3: 4.7: 0.33.
    [28]
    A method according to any of claims 3 to 27 wherein in step (e) the fifth solvent is selected from one or more water types, dichloromethane, methanol, ethanol, toluene, tetrahydrofuran, N, N-dimethylformamide and 1,4-dioxane .
    [29]
    The method of claim 28 wherein the fifth solvent is a water-methanol-tetrahydrofuran ternary mixed solvent system.
    [30]
    The method of claim 29 wherein the volume ratio of water, methanol, and tetrahydrofuran in the water-methanol-tetrahydrofuran ternary mixed solvent system is 1: 1-2: 1, and preferably 1: 1: 1.
    [31]
    A method according to any one of claims 3 to 30, wherein in step (e) the third base is selected from one or more of sodium hydroxide, potassium hydroxide, potassium carbonate and sodium carbonate.
    [32]
    The method of claim 31, wherein the third base is sodium hydroxide.
    [33]
    A method according to any one of claims 3 to 32, wherein in step (e) the reaction temperature is 25-100 ° C, and preferably 40-60 ° C.
    [34]
    A method according to any one of claims 3 to 33, wherein in step (e) the molar ratio of the intermediate D and the third base is 1: (20-25), and preferably 1:25.
    [35]
    35. A metal-organic framework material that takes a compound of formula (I) as an organic ligand, wherein the compound of formula (I) can be represented as HL when used as an organic ligand.
    [36]
    The metal-organic framing material of claim 35, wherein the metal-organic framing material is a nano-metal-organic framing material, and its chemical formula is Zr604 (OH) 4 (C16H23sN; 048) s.
    [37]
    A method for preparing the nano-metal-organic framework material according to claim 35 or 36, comprising reacting HL and zirconium tetrachloride in a solvent to obtain the nano-metal-organic framework material.
    [38]
    The method of claim 37 comprising the steps of: reacting H: L and zirconium tetrachloride in a sixth solvent in an oven, cooled to room temperature, centrifuged, soaked in N, N-dimethylformamide, activated with ethanol, washed with diethyl ether, and air dried to remove the nano-
    metal-organic frame material as a white powder.
    [39]
    The method of claim 38 wherein the sixth solvent is N, N-dimethylformamide and acetic acid.
    [40]
    A method according to any one of claims 37 to 39 wherein the molar ratio of the organic ligand H: L to zirconium tetrachloride is 4-5: 7-8, and preferably 5: 81s.
    [41]
    A method according to any one of claims 37 to 40, wherein the reaction temperature is 100 ° C and the reaction time is 24 hours.
    [42]
    42. Use of a composition of formula (I) as a ligand in the preparation of a metal-organic framework material.
    [43]
    A sensor or detector containing a metal-organic framework material that takes a compound of formula (I) as a ligand, or the metal-organic framework material according to claim 35 or 36.
    [44]
    44. Use of a metal-organic framework material taking a composition of formula (I) as a ligand or the nano-metal-organic framework material according to claim 35 or 36 as a sensor or detector in tap water detection or HCIO detection or using the sensor or the detector according to claim 43 in tap water detection or HC10 detection.
    [45]
    The use according to claim 44, wherein the tap water detection is to detect HCIO in tap water, preferably to detect HCIO in tap water.
    [46]
    A method for rapid detection of HCIO, comprising placing a metal-organic framework material that takes a compound of formula (I) as a ligand, or the nanometallic-organic framework material according to claim 35 or 36, or the sensor or detector according to claim 43 in an HCIO-containing environment; reacting the nanometallic organic frame material with HCIO to generate a metal organic frame material containing sulfoxide so that the color gradually changes from white to red to indicate HCIO by the color change.
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    CN201910116841.1A|CN109928966B|2019-02-15|2019-02-15|Metal organic framework material based on phenothiazine and preparation method and application thereof|
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