An extremely sensitive detection of aqueous-phase hg 2+ Photochromic luminescent crystalline materials and methods for their preparation

Abstract

The application discloses a kind of extremely sensitive detection water-phase Hg 2+ Photochromic luminescent crystal material and preparation method thereof, first based on 9,10- Bis (di (pyrimidine-5-yl) methylene) -9,10-dihydroanthracene photochromic functional ligand Preparation of photochromic luminescent crystal material [Cd (L) (OBA)] n , method is simple, synthesis route is simple and easy to control, product yield can reach 38.4%, suitable for industrial production.The material can be used for detecting water-phase Hg 2+ , compared with prior art, the crystal material is used for detection, and it is simple and reliable, and the quenching constant of luminescence quenching for detecting water-phase Hg 2+ It is as high as 8.31 x 10 4 M ‑1 , detection limit is as low as 7.62 x 10 ‑7 M, it is currently extremely sensitive detection Hg 2+ Luminescent crystal material, has broad application prospect.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of photochromic luminescent detection functional materials, and particularly relates to a photochromic luminescent crystal material for extremely sensitive detection of Hg 2+ in an aqueous phase and a preparation method thereof. BACKGROUND

[0002] Mercury ion (Hg 2+ ) is one of the most important and most deadly heavy metal ions. Hg 2+ is widely used in industry. Due to industrial emissions and the like, Hg 2+ is easily accumulated in water, air and soil in the daily environment. Hg 2+ has terrible toxicity, and it poses a great threat to the environment and public health. Among them, mercury can damage the brain, heart, kidney and other organs. Even at low concentrations, the accumulation of mercury can cause serious damage to the human body.

[0003] Luminescent metal-organic framework detection materials have the advantages of convenient, rapid, sensitive and selective detection, and have been developed and applied in the field of luminescent detection. The organic ligand plays a decisive role in the luminescent detection performance of the metal-organic framework crystal material.

[0004] In recent years, organic photochromic molecules have been widely studied and applied in biological probes, cell imaging, anti-counterfeiting materials and the like. However, organic photochromic molecular materials often cannot meet the development of science and technology and the increasing material life needs of people. Therefore, it is of great significance to develop organic photochromic molecules as functional organic ligands to construct luminescent detection functional metal-organic framework crystal materials. SUMMARY

[0005] This part aims to summarize some aspects of the embodiments of the present application and briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this part and the abstract and title of the specification of the present application in order to avoid obscuring the purpose of this part, the abstract and the title of the specification. Such simplifications or omissions cannot be used to limit the scope of the present application.

[0006] In view of the above and / or problems existing in the prior art, the present application is proposed.

[0007] Therefore, the purpose of the present application is to overcome the deficiencies in the prior art, and to provide a photochromic luminescent crystal material, comprising,

[0008] The photochromic luminescent crystal material is a three-dimensional structure, and the cell parameters thereof are: α = 90°, β = 90°, γ = 90°, and the cell volume is Z = 8.

[0009] The chemical formula of the light-induced luminescent crystal material is [Cd(L)(OBA)] n , wherein L represents 9,10-bis(di(pyrimidin-5-yl)methylene)-9,10-dihydroanthracene, OBA represents 4,4-diphenyl ether dicarboxylic acid, and n is an arbitrary value.

[0010] Another object of the present application is to provide a preparation method of a light-induced luminescent crystal material.

[0011] To solve the above technical problems, the present application provides the following technical solutions: comprising,

[0012] The cadmium acetate dihydrate, 9,10-bis(di(pyrimidin-5-yl)methylene)-9,10-dihydroanthracene, and 4,4-diphenyl ether dicarboxylic acid are added to a mixed solvent of water and ethanol to prepare a mixed solution by stirring;

[0013] The mixed solution is placed in a sealed reaction kettle for heating reaction, and then slowly cooled to room temperature. The product is filtered, washed, and dried to obtain the light-induced luminescent crystal material [Cd(L)(OBA)] n .

[0014] As a preferred solution of the preparation method of the light-induced luminescent crystal material, the molar ratio of the cadmium acetate dihydrate, 9,10-bis(di(pyrimidin-5-yl)methylene)-9,10-dihydroanthracene, and 4,4-diphenyl ether dicarboxylic acid is 1:0.25-0.75:0.5-1.5.

[0015] As a preferred solution of the preparation method of the light-induced luminescent crystal material, the volume ratio of water and ethanol in the mixed solvent is 1:0.5-2.

[0016] As a preferred solution of the preparation method of the light-induced luminescent crystal material, the volume of the mixed solvent of water and ethanol required for 0.1 mmol of cadmium acetate dihydrate is 3-12 ml.

[0017] As a preferred solution of the preparation method of the light-induced luminescent crystal material, the heating reaction is carried out at a temperature of 100-180°C for 48-84 h.

[0018] As a preferred solution of the preparation method of the light-induced luminescent crystal material, the cooling to room temperature is carried out at a rate of 2-5°C / h.

[0019] Another object of the present application is to provide an application of the light-induced luminescent crystal material in detecting Hg 2+ in water.

[0020] As a preferred scheme of the application of the photochromic luminescent crystal material in detecting Hg 2+ in water phase, wherein: the luminescence quenching constant of the photochromic luminescent crystal material after photochromic luminescence quenching is 8.31*10 2+ M. 4 M. -1 .

[0021] As a preferred scheme of the application of the photochromic luminescent crystal material in detecting Hg 2+ in water phase, wherein: the detection limit of the photochromic luminescent crystal material after photochromic luminescence quenching in detecting Hg 2+ in water phase is 7.62*10 -7 M.

[0022] The present application has the following beneficial effects:

[0023] The present application first synthesizes a photochromic luminescent crystal material [Cd(L)(OBA)] based on 9,10-bis(di(pyrimidin-5-yl)methylene)-9,10-dihydroanthracene photochromic functional organic ligand n , and the synthesis method is extremely simple, the route is mild and easy to control, and the obtained material [Cd(L)(OBA)] n can be used for detecting Hg 2+ in water phase, compared with the prior art, the crystal material is simple and reliable in application, the luminescence quenching constant of the photochromic luminescent crystal material after photochromic luminescence quenching in detecting Hg 2+ in water phase is as high as 8.31*10 4 M -1 , and the detection limit is as low as 7.62*10 -7 M, which is a photochromic luminescent crystal material for extremely sensitive detection of Hg 2+ at present, and has wide application prospect. BRIEF DESCRIPTION OF DRAWINGS

[0024] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed in the embodiment description will be briefly introduced as follows. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor. Among them:

[0025] Figure 1 It is a three-dimensional crystal structure diagram of the crystal material [Cd(L)(OBA)] n prepared in example 1 of the present application.

[0026] Figure 2 It is a three-dimensional crystal structure diagram of the crystal material [Cd(L)(OBA)]n Powder X-ray diffraction pattern.

[0027] Figure 3 Crystalline material [Cd(L)(OBA)] prepared for Example 1 of the present invention n Excitation, emission spectra of the water suspension (0.1 mg / mL) before color change.

[0028] Figure 4 Crystalline material [Cd(L)(OBA)] prepared for Example 1 of the present invention n Excitation, emission spectra of the water suspension (0.1 mg / mL) after color change.

[0029] Figure 5 Luminescent crystalline material [Cd(L)(OBA)] prepared for Example 1 of the present invention n Luminescence intensity change curve of the water suspension of the luminescent crystalline material [Cd(L)(OBA)] prepared for Example 1 of the present invention

[0030] Figure 6 Crystalline material [Cd(L)(OBA)] prepared for Example 1 of the present invention n Quenching constant curve of divalent mercury ion detection.

[0031] Figure 7 Crystalline material [Cd(L)(OBA)] prepared for Example 1 of the present invention n Detection limit curve of divalent mercury ion detection.

[0032] Figure 8 Quenching efficiency graph of the water suspension of the luminescent crystalline material [Cd(L)(OBA)] prepared for Example 1 of the present invention n Quenching efficiency graph of the water suspension of the luminescent crystalline material [Cd(L)(OBA)] prepared for Example 1 of the present invention DETAILED DESCRIPTION

[0033] In order to make the above objectives, features and advantages of the present invention more apparent, specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

[0034] In the following description, a lot of specific details are set forth in order to facilitate a full and thorough understanding of the present invention, but the present invention can also be implemented in other ways different from those described herein, and those skilled in the art can make similar generalizations without departing from the scope of the present invention, so the present invention is not limited to the specific embodiments disclosed below.

[0035] Second, the "one embodiment" or "an embodiment" referred to herein means a specific feature, structure, or characteristic under discussion. Each of the various embodiments presented in this specification are not necessarily mutually exclusive, but can be selectively implemented in various embodiments of the application.

[0036] The chemical reagents used in the embodiments of the present application are all commercially available analytical pure unless otherwise specified.

[0037] The yield calculation method in the embodiments of the present application is based on L to calculate the yield, and the calculation steps are:

[0038] m (actual crystal) / m (L complete reaction)

[0039] Example 1

[0040] The embodiment provides a preparation method of a photochromic luminescent crystal material, specifically:

[0041] 1) 0.1 mmol of cadmium acetate dihydrate, 0.05 mmol of 9,10-bis(di(pyrimidin-5-yl) methylene)-9,10-dihydroanthracene, and 0.1 mmol of 4,4-diphenyl ether dicarboxylic acid are added to 6 mL of mixed solvent (V water:V ethanol = 1:1) and stirred to prepare a mixed solution;

[0042] 2) The prepared mixed solution is placed in a sealed reaction kettle and heated to 140 DEG C for 72 h, slowly cooled to room temperature at a rate of 5 DEG C / h, and then the product is filtered, washed with deionized water and ethanol, and vacuum dried at 80 DEG C for 30 min, to obtain a crystal material [Cd(L)(OBA)] n , and the yield is 38.4%.

[0043] The single crystal structure of the crystal material of the present application is determined by using a Bruker D8 VENTURE X-ray single crystal diffractometer, and the crystal structure determination data are shown in Table 1.

[0044] Table 1 Crystal structure determination data

[0045]

[0046]

[0047] Figure 1 The crystal three-dimensional structure diagram of the crystal material [Cd(L)(OBA)] n prepared in the embodiment.

[0048] Figure 2 The crystal material [Cd(L)(OBA)] n The powder X-ray diffraction spectrum, and from Table 1, the unit cell parameters are: a = 90°, b = 90°, g = 90°, and the unit cell volume is Z = 8.

[0049] Figure 3 , Figure 4 crystal material [Cd(L)(OBA)] prepared in the embodiment n Excitation and emission spectra of the water suspension (0.1 mg / mL) before and after discoloration; crystal material [Cd(L)(OBA)] n The excitation and emission spectra after photochromism have a significant red shift.

[0050] Application test

[0051] Figure 5 crystal material [Cd(L)(OBA)] prepared in the embodiment n 2+ The luminescence intensity change curve of the water suspension of the crystal material [Cd(L)(OBA)] prepared in the embodiment 2+ to which different volumes of Hg n aqueous solution with a concentration of 1 mmol / L were added can be seen that, as the amount of Hg 2+ increases gradually, the luminescence intensity of the suspension quenches gradually.

[0052] Figure 6 , Figure 7 The photochromic crystal material [Cd(L)(OBA)] prepared in the embodiment n 2+ The quenching constant curve and the detection limit curve of the water-phase Hg 4 detection show that the quenching constant of the luminescence of the material after photochromism for the water-phase metronidazole is as high as 8.31 x 10 -1 M -7 , and the detection limit is as low as 7.62 x 10 2+ M, indicating that the detection material provided in the embodiment can detect the water-phase Hg n very sensitively.

[0053] Comparative Example 1

[0054] The water suspension of the luminescent crystal material [Cd(L)(OBA)] prepared in Example 1 n + + 2+ 3+ + 2+ 2+ 3+ 2+ was added with different cations (Na + , K + , Mg 2+ , Al 3+ , Ag + , Cd 2+ , Zn 2+ , Cr 3+ , Hg 2+ ) with the same concentration and the same volume, and the quenching efficiency was detected to obtain a quenching efficiency comparison chart as shown in Figure 8 It can be seen that only Hg2+ The luminescent crystal material [Cd(L)(OBA)] prepared in the present application can cause n Significant emission quenching occurs, i.e., the [Cd(L)(OBA)] obtained in the present application n Hg 2+ has a specific detection effect.

[0055] Example 2

[0056] The difference between this example and Example 1 is that the molar mass of 4,4-diphenyl ether dicarboxylic acid is adjusted to 0.025 mmol, and the rest of the preparation process is the same as that of Example 1, and the photochromic luminescent crystal material [Cd(L)(OBA)] of this example is obtained. n The calculated yield is 26.9%.

[0057] Example 3

[0058] The difference between this example and Example 1 is that the molar mass of 9,10-bis(di(pyrimidin-5-yl)methylene)-9,10-dihydroanthracene is adjusted to 0.075 mmol, and the rest of the preparation process is the same as that of Example 1, and the photochromic luminescent crystal material [Cd(L)(OBA)] of this example is obtained. n The calculated yield is 35.3%.

[0059] Comparative Example 2

[0060] The difference between this example and Example 1 is that the molar ratio of cadmium acetate dihydrate, 9,10-bis(di(pyrimidin-5-yl)methylene)-9,10-dihydroanthracene, and 4,4-diphenyl ether dicarboxylic acid is adjusted to 1:1:1, and the rest of the preparation process is the same as that of Example 1. The solution is clear and no crystals are formed, and the preparation is unsuccessful.

[0061] Table 2 is the synthesis conditions of Examples 1-3 and Comparative Example 2 and the yield under the corresponding conditions.

[0062] Table 2

[0063]

[0064] As can be seen from Table 2, the yield of the synthesized product is related to the molar ratio of the organic complex and 4,4-diphenyl ether dicarboxylic acid, and the photochromic luminescent crystal material cannot be successfully synthesized when the molar ratio is 1:1.

[0065] Example 4

[0066] The difference between this example and Example 1 is that the cooling rate is adjusted to 2°C / h, and the rest of the preparation process is the same as that of Example 1, and the photochromic luminescent crystal material [Cd(L)(OBA)] of this example is obtained. nThe calculated yield is 36.2%.

[0067] Comparative Example 3

[0068] The difference between this comparative example and Example 1 is that the cooling rate is adjusted to 1°C / h, and the rest of the preparation process is the same as Example 1. There is no obvious improvement in yield, and the experimental process is slow, resulting in unnecessary waste of resources.

[0069] Comparative Example 4

[0070] The difference between this comparative example and Example 1 is that the cooling rate is adjusted to 6°C / h, and the rest of the preparation process is the same as Example 1. The crystal crystallization is affected, the quality is poor, and the subsequent test cannot be carried out.

[0071] Table 3 is the synthesis conditions of Example 1, Example 4, and Comparative Examples 3 and 4, and the yield under the corresponding conditions.

[0072] Table 3

[0073]

[0074] As can be seen from Table 3, the yield of the synthesized product is related to the cooling rate. When the cooling rate is 2-5°C / h, the photoluminescent crystal material can be successfully prepared, while too high or too low cooling rate cannot better synthesize the photoluminescent crystal material.

[0075] Example 5

[0076] The difference between this example and Example 1 is that the volume of the mixed solvent is adjusted to 9mL (Vwater:Vethanol=1:1), and the rest of the preparation process is the same as Example 1. The photoluminescent crystal material [Cd(L)(OBA)] of this example is obtained. n The calculated yield is 28.5%.

[0077] Comparative Example 5

[0078] The difference between this comparative example and Example 1 is that the volume of the mixed solvent is adjusted to 2mL (Vwater:Vethanol=1:1), and the rest of the preparation process is the same as Example 1. It cannot be successfully prepared.

[0079] Comparative Example 6

[0080] The difference between this comparative example and Example 1 is that the volume of the mixed solvent is adjusted to 13mL (Vwater:Vethanol=1:1), and the rest of the preparation process is the same as Example 1. It cannot be successfully prepared.

[0081] Table 4 is the synthesis conditions of Example 1, Example 5, and Comparative Examples 5 and 6, and the yield under the corresponding conditions.

[0082] Table 4

[0083]

[0084] As can be seen from Table 4, the yield of the synthetic product is related to the volume of the mixed solvent, and the photochromic luminescent crystal material cannot be successfully synthesized when the volume of the mixed solvent is too high or too low.

[0085] Example 6

[0086] The difference between this example and Example 1 is that the reaction temperature is adjusted to 100°C, and the rest of the preparation process is the same as that of Example 1, thereby obtaining the photochromic luminescent crystal material [Cd(L)(OBA)] of this example. n The calculated yield is 5.4%.

[0087] Example 7

[0088] The difference between this example and Example 1 is that the reaction temperature is adjusted to 180°C, and the rest of the preparation process is the same as that of Example 1, thereby obtaining the photochromic luminescent crystal material [Cd(L)(OBA)] of this example. n The calculated yield is 17.3%.

[0089] Comparative Example 7

[0090] The difference between this example and Example 1 is that the reaction temperature is adjusted to 190°C, and the rest of the preparation process is the same as that of Example 1. The photochromic luminescent crystal material cannot be successfully synthesized.

[0091] Table 5 is the synthesis conditions of Example 1, Example 6, Example 7 and Comparative Example 7 and the yield under the corresponding conditions.

[0092] Table 5

[0093]

[0094]

[0095] As can be seen from Table 5, the yield of the synthetic product is related to the heating temperature, and the photochromic luminescent crystal material cannot be successfully synthesized when the heating temperature is too high.

[0096] Example 8

[0097] The difference between this example and Example 1 is that the volume ratio of water and ethanol in the mixed solvent is adjusted to 1:0.5, and the rest of the preparation process is the same as that of Example 1, thereby obtaining the photochromic luminescent crystal material [Cd(L)(OBA)] of this example. n The calculated yield is 13.2%.

[0098] Example 9

[0099] The difference between the present example and Example 1 is that the volume ratio of water and ethanol in the mixed solvent is adjusted to 1:2, and the rest of the preparation process is the same as that of Example 1, so as to obtain the photochromic luminescent crystal material [Cd(L)(OBA)] of the present example. n The calculated yield is 15.6%.

[0100] Comparative Example 8

[0101] The difference between the present comparative example and Example 1 is that the volume ratio of water and ethanol in the mixed solvent is adjusted to 1:3, and the rest of the preparation process is the same as that of Example 1. The solution is clear, and no crystal is generated, so that the preparation is unsuccessful.

[0102] Comparative Example 9

[0103] The difference between the present comparative example and Example 1 is that no ethanol is added in the mixed solvent, and the rest of the preparation process is the same as that of Example 1. The solution is turbid, and a large amount of precipitate is generated, so that no crystal is generated, and the preparation is unsuccessful.

[0104] Table 6 is the synthesis conditions of Example 1, Example 8, Example 9, Comparative Example 8 and Comparative Example 9, and the yield under the corresponding conditions.

[0105] Table 6

[0106]

[0107]

[0108] As can be seen from Table 6, the yield of the synthesized product is related to the volume ratio of water and ethanol in the mixed solvent. When the volume ratio of water and ethanol in the mixed solvent is too large or too small, the photochromic luminescent crystal material cannot be successfully synthesized.

[0109] Comparative Example 10

[0110] The difference between the present comparative example and Example 1 is that the cadmium acetate dihydrate is replaced by cadmium nitrate tetrahydrate, and the rest of the preparation process is the same as that of Example 1. The solution is turbid, and a large amount of precipitate is generated, so that no crystal is generated, and the preparation is unsuccessful.

[0111] Comparative Example 11

[0112] The difference between the present comparative example and Example 1 is that the cadmium acetate dihydrate is replaced by cadmium chloride pentahydrate, and the rest of the preparation process is the same as that of Example 1. The solution is turbid, and a large amount of precipitate is generated, so that no crystal is generated, and the preparation is unsuccessful.

[0113] In summary, the present application provides a kind of Hg 2+The preparation method and product of the photochromic luminescent crystal material, the synthesis route is simple and easy to control, the product yield can reach 38.4%, and is suitable for industrial production and popularization. Compared with the prior art, the crystal material is simple and reliable in detection, the quenching constant of the luminescence quenching detection of water phase Hg 2+ is up to 8.31*10 4 M -1 , and the detection limit is as low as 7.62*10 -7 M, which is a luminescent crystal material for extremely sensitive detection of Hg 2+ , and has wide application prospect.

[0114] It should be noted that the above examples are only used to illustrate the technical solutions of the present application and are not limiting. Although the present application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solutions of the present application can be modified or replaced by equivalents without departing from the spirit and scope of the present application, and they should be included in the scope of the present application.

Claims

1. A photochromic luminescent crystalline material, characterized in that: Comprising, The photochromic luminescent crystalline material is a three-dimensional structure with the cell parameters: a = 29.1944(16) A, b = 9.8282(5) A, c = 26.5748(13) A, a = 90°, b = 90°, g = 90°, and the cell volume is 7625.1(7) A 3 , Z = 8. Chemical formula: [Cd(L)(OBA)] n wherein L represents 9,10-bis(di(pyrimidin-5-yl)methylene)-9,10-dihydroanthracene, OBA represents 4,4-diphenyl ether dicarboxylic acid, and n is an arbitrary value.

2. The method for preparing the photochromic luminescent crystal material as described in claim 1, characterized in that: Comprising, The cadmium acetate dihydrate, 9,10-bis(di(pyrimidin-5-yl)methylene)-9,10-dihydroanthracene, and 4,4-diphenyl ether dicarboxylic acid are added to a mixed solvent of water and ethanol to prepare a mixed solution by stirring; The mixed solution is placed in a closed reaction kettle for heating reaction, and then slowly reduced to room temperature. The product is filtered, washed and dried to obtain a photochromic luminescent crystal material [Cd(L)(OBA)] n ; The molar ratio of the cadmium acetate dihydrate, 9,10-bis(di(pyrimidin-5-yl)methylene)-9,10-dihydroanthracene, and 4,4-diphenyl ether dicarboxylic acid is 1:0.25-0.75:0.5-1.5; The cooling rate is 2-5℃ / h; The volume ratio of water to ethanol in the mixed solvent is 1:0.5-2; The volume of the mixed solvent of water and ethanol required for every 0.1 mmol of cadmium acetate dihydrate is 3-12 mL; The heating temperature is 100-180℃, and the heating reaction time is 48-84 h.

3. Use of the photochromic luminescent crystalline material prepared according to the process of claim 2 for detecting Hg in aqueous phases. 2+ ​ 4. Use of the photochromic luminescent crystalline material according to claim 3 for the detection of Hg in aqueous phases, characterized in that: 2+ The photochromic luminescent crystal material undergoes photochromic quenching, and its luminescence is detected in aqueous phase Hg. 2+ The quenching constant is 8.31 × 10⁻⁶. 4 M -1 . ​ 5. Use of the photochromic luminescent crystalline material according to claim 3 for the detection of Hg in aqueous phases, characterized in that: 2+ Detection of water phase Hg by photochromic luminescent crystal material after photochromic luminescence quenching 2+ The detection limit is 7.62 x 10 -7 M. ​

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