Crystal, preparation method thereof and application of crystal as blue fluorescence scintillation material

Abstract

The invention discloses a crystal, a preparation method thereof and application of the crystal as a blue fluorescent scintillation material, and belongs to the field of luminescent crystals. The chemical formula of the crystal is as follows: [Pb (ADBA) (DMF)] n, wherein ADBA is a ligand formed by completely removing proton hydrogen from 9, 10-di (4-carboxyl phenyl) anthracene; the DMF is N, N-dimethyl formamide; n is infinity and represents continuous repetition and infinite extension. As a blue fluorescent scintillation material, the crystal shows macroscopic blue fluorescence under ultraviolet light and X-ray irradiation, and has potential application value in blue fluorescent materials, X-ray radiation detection materials and radiation detection dosimeters.

Description

Technical Field

[0001] This application relates to a crystal, its preparation method, and its application as a blue fluorescent scintillating material, belonging to the field of luminescent crystals. Background Technology

[0002] Scintillation materials are a class of functional materials capable of absorbing X-rays, gamma rays, or other high-energy particles and converting them into ultraviolet or visible light. They are widely used in radiation monitoring, security inspection, industrial flaw detection, and medical imaging. Traditional scintillation materials are mainly divided into inorganic and organic scintillation materials. Inorganic scintillation materials include PbWO4, NaI:Tl, and Bi4Ge3O. 12 (BGO), etc., possess excellent scintillation properties and high stability, but NaI:Tl is hygroscopic, limiting its application range. PbWO4, Bi4Ge3O 12 Bulk crystals such as (BGO) are difficult to prepare, have high production costs, and poor mechanical strength. Organic scintillators such as naphthalene, anthracene, bitetraphenyl, 1,3,5-triphenylbenzene, and their derivatives, while exhibiting fast decay times and luminescence intensities, have low light yields, poor radiation stability, and are highly susceptible to oxidation during use. Metal-organic frameworks (MOFs) are porous coordination polymers with a periodic network structure composed of metal nodes and organic ligands. They offer advantages such as structural designability, tunable performance, and low-cost solution processing. MOFs can leverage the synergistic effect of self-assembly between inorganic and organic building blocks, showing great potential in radiation detection and medical imaging. Summary of the Invention

[0003] The purpose of this invention is to provide a crystal, its preparation method, and its application as a blue fluorescent scintillation material. The crystal has good radiation stability and exhibits visible blue fluorescence under both ultraviolet light and X-ray irradiation.

[0004] According to the first aspect of this application, a crystal is provided.

[0005] A crystal, the chemical formula of which is shown below: [Pb(ADBA)(DMF)] n ADBA is a ligand formed after complete deprotonation of 9,10-bis(4-carboxyphenyl)anthracene; DMF is N,N -Dimethylformamide; n The value ∞ represents continuous repetition and infinite extension.

[0006] Optionally, the crystal has a one-dimensional structure; the smallest asymmetric structural unit of the one-dimensional structure is shown below; Pb 0.5 (ADBA) 0.5 (DMF) 0.5 The crystal is composed of an infinite number of Pb atoms. 0.5 (ADBA) 0.5 (DMF) 0.5 A one-dimensional chain composed of structural units.

[0007] Optionally, the Pb in the crystal is a five-coordinate Pb. 2+ Metal ions; The Pb 2+ Metal ions react with those from two ADBAs respectively 2– The four O atoms on the carboxylate group of the ligand and one O atom on the DMF are coordinated.

[0008] Optionally, the crystal belongs to the orthorhombic crystal system and has P NMA space group structure.

[0009] Optionally, the unit cell parameters of the crystal are: a = 8.70~8.71 Å, b = 31.70~31.71 Å, c = 9.38~9.39 Å, α = 90°, β = 90°, γ = 90°, Z = 4, V = 2588.50~2600 Å 3 .

[0010] Preferably, a = 8.703~8.704 Å, b = 31.704~31.705 Å, c = 9.380~9.382 Å, V =2588.50~2595.50 Å 3 .

[0011] Specifically, a = 8.7031(3) Å, b = 31.7048(8) Å, c = 9.3810(3) Å, V = 2588.50(14)Å 3 .

[0012] According to a second aspect of this application, a method for preparing a crystal is provided.

[0013] The method for preparing the crystal described above includes: placing a mixed solution containing 9,10-bis(4-carboxyphenyl)anthracene, a lead source, an organic acid, and a solvent in a sealed container and reacting to obtain the crystal.

[0014] Optionally, the lead source is selected from at least one of Pb(NO3)2, PbCl2, PbBr2 and PbI2.

[0015] Optionally, the organic acid is o-fluorobenzoic acid.

[0016] Optionally, the solvent is N , N -Dimethylformamide.

[0017] Optionally, the molar ratio of the lead source to 9,10-bis(4-carboxyphenyl)anthracene is 1.8:1 to 2:1; The molar amount of the lead source is expressed as the molar amount of Pb element in the lead source.

[0018] Specifically, the molar ratio of the lead source to 9,10-bis(4-carboxyphenyl)anthracene is 2:1.

[0019] Optionally, the ratio of lead source to solvent is 0.1 mmol : 2~5 mL.

[0020] Specifically, the ratio of lead source to solvent is 0.1 mmol : 3 mL.

[0021] Optionally, the amount of organic acid added is adjusted to adjust the pH of the mixed solution to 5-7.

[0022] Optionally, the reaction temperature is 80~120℃. o C, reaction time 24~72 h.

[0023] Preferably, the reaction temperature is 90~100℃. o C, the reaction time is 36~72 h.

[0024] Optionally, the temperature of the reaction is independently selected from 80°C. o C, 85 o C, 90 o C, 95 o C, 100 o C, 105 o C, 110 o C, 115 o C, 120 oAny value in C or a range of values ​​between any two.

[0025] Optionally, the reaction time is independently selected from any value of 24 h, 30 h, 36 h, 42 h, 48 h, 54 h, 60 h, 66 h, 72 h, or a range between any two.

[0026] In one preferred embodiment, the method for preparing the crystal includes: PbCl2 and 9,10-bis(4-carboxyphenyl)anthracene, in a molar ratio of 2:1, were placed in a 10 mL glass vial. DMF solvent was then added, followed by the addition of o-fluorobenzoic acid to adjust the pH to 5-7. A solvothermal reaction was then carried out, with a PbCl2 to DMF volume ratio of 0.1 mmol:3 mL. The reaction temperature was 90 °C. o At C, the reaction time was 72 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and washed with DMF to obtain yellow blocky crystals, which are the one-dimensional [Pb(ADBA)(DMF)] structures. n Its smallest asymmetric structural unit is Pb 0.5 (ADBA) 0.5 (DMF) 0.5 .

[0027] According to a third aspect of this application, a scintillation material is provided. This crystal, as a blue fluorescent scintillation material, exhibits visible blue fluorescence under both ultraviolet and X-ray irradiation, and has potential applications in blue fluorescent materials, X-ray radiation detection materials, and radiation dosimeters.

[0028] A scintillation material, wherein the scintillation material is selected from the crystals described above, or crystals prepared by the preparation method described above. The crystals synthesized by the above method exhibit good radiation stability when used as scintillation materials.

[0029] Optionally, the scintillating material emits blue fluorescence under ultraviolet light or X-ray irradiation.

[0030] Optionally, the wavelength of the ultraviolet light is 320~400 nm.

[0031] Optionally, the RGB color coordinates of the blue fluorescence are (0.16~0.20, 0.26~0.37).

[0032] Preferably, the color coordinates of the RGB color system are (0.180~0.189, 0.274~0.354).

[0033] Specifically, the color coordinates of the RGB color system are (0.184, 0.279).

[0034] Optionally, the luminescence lifetime of the scintillating material is 4.5~6.0 ns.

[0035] Preferably, the luminescence lifetime of the scintillating material is 5.20~5.70 ns.

[0036] Specifically, the luminescence lifetime of the scintillating material is 5.53 ns.

[0037] According to the fourth aspect of this application, an application is provided.

[0038] Applications of the crystals described above, the crystals prepared by the methods described above, or the scintillation materials described above in blue fluorescent materials, X-ray radiation detection materials, radiation dosimeters, and radiation imaging devices.

[0039] The beneficial effects that this application can produce include: (1) The crystal provided by the present invention is a blue fluorescent scintillation material. It exhibits visible blue fluorescence under ultraviolet light and X-ray irradiation at a wavelength of 365 nm. It can be used to make blue fluorescent materials, high-energy radiation detection materials and devices, etc.

[0040] (2) The crystal preparation method provided by the present invention is simple and suitable for large-scale industrial production. The prepared crystal has high purity and good crystallinity as a blue fluorescent scintillation material, and has good X-ray response sensitivity and irradiation stability. Attached Figure Description

[0041] Figure 1 This is a schematic diagram of the coordination environment of sample 1#.

[0042] Figure 2 It is sample #1, crystal material [Pb(ADBA)(DMF)] n X-ray powder diffraction pattern.

[0043] Figure 3 It is sample #1, crystal material [Pb(ADBA)(DMF)] n Photoluminescence spectrum.

[0044] Figure 4 It is sample #1, crystal material [Pb(ADBA)(DMF)] n The luminous color coordinate diagram.

[0045] Figure 5 It is sample #1, crystal material [Pb(ADBA)(DMF)] n The fluorescence lifetime spectrum.

[0046] Figure 6 It is sample #1, crystal material [Pb(ADBA)(DMF)]n The scintillation emission spectrum.

[0047] Figure 7 It is sample #1, crystal material [Pb(ADBA)(DMF)] n Linear graph of scintillation fluorescence intensity as a function of X-ray dose.

[0048] Figure 8 It is sample #1, crystal material [Pb(ADBA)(DMF)] n Irradiation stability diagram. Detailed Implementation

[0049] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0050] Unless otherwise specified, all raw materials used in the embodiments of this application were purchased through commercial channels.

[0051] Unless otherwise specified, all test methods are standard and all instrument settings are those recommended by the manufacturer.

[0052] Example 1 PbCl2 (0.1 mmol), 9,10-bis(4-carboxyphenyl)anthracene (0.05 mmol), and o-fluorobenzoic acid (0.3 mmol) were placed in a 10 mL glass vial in a molar ratio of 2:1:6. Then, DMF (3 mL) was added as solvent to obtain a mixed solution with pH = 6. This mixed solution was then reacted in a sealed container at a reaction temperature of 90°C. o At C, the reaction time was 48 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and washed with DMF to obtain yellow blocky crystals [Pb(ADBA)(DMF)]. n This is designated as sample 1#.

[0053] Example 2 Pb(NO3)2 (0.1 mmol), 9,10-bis(4-carboxyphenyl)anthracene (0.05 mmol), and o-fluorobenzoic acid (0.3 mmol) were placed in a 10 mL glass vial in a molar ratio of 2:1:6. Then, 3 mL of DMF solvent was added to obtain a mixed solution with pH = 6. This mixed solution was then reacted in a sealed container at a reaction temperature of 90°C. o At C, the reaction time was 72 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and washed with DMF to obtain yellow blocky crystals [Pb(ADBA)(DMF)]. n This is designated as sample 2#.

[0054] Example 3 PbCl2 (0.1 mmol), 9,10-bis(4-carboxyphenyl)anthracene (0.05 mmol), and o-fluorobenzoic acid (0.3 mmol) were placed in a 10 mL glass vial in a molar ratio of 2:1:6. Then, DMF (3 mL) was added as solvent to obtain a mixed solution with pH = 6. This mixed solution was then reacted in a sealed container at a reaction temperature of 100°C. o At C, the reaction time was 48 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and washed with DMF to obtain yellow blocky crystals [Pb(ADBA)(DMF)]. n This is designated as sample 3#.

[0055] Example 4 PbBr2 (0.1 mmol), 9,10-bis(4-carboxyphenyl)anthracene (0.05 mmol), and o-fluorobenzoic acid (0.3 mmol) were placed in a 10 mL glass vial in a molar ratio of 2:1:6. Then, 3 mL of DMF solvent was added to obtain a mixed solution with pH = 6. This mixed solution was then placed in a sealed container for reaction at 100°C. o At C, the reaction time was 72 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and washed with DMF to obtain yellow blocky crystals [Pb(ADBA)(DMF)]. n This is designated as sample 4#.

[0056] Test Example 1 [Pb(ADBA)(DMF)] n Structural characterization of crystalline materials The structure of sample 1# prepared in Example 1 was characterized.

[0057] Sample 1#[Pb(ADBA)(DMF)] n X-ray single-crystal diffraction tests were performed on a Rigaku FR-X single-crystal diffractometer (test conditions: Mo target, K α Radiation source ( λ = 0.07107 nm), after testing at 293 K, via Olex 2 1.2 Analyze the structure.

[0058] X-ray single-crystal diffraction analysis results show that the crystalline material structure of sample 1# is [Pb(ADBA)(DMF)]. n It belongs to the orthorhombic crystal system. P NMA space group. Cell parameters are... a = 8.7031(3) Å, b = 31.7048(8) Å, c = 9.3810(3)Å,α = 90°, β = 90°, γ = 90°, Z = 4, V = 2588.50(14) Å 3 .

[0059] The crystal material of sample 1# is [Pb(ADBA)(DMF)]. n A schematic diagram of the coordination environment is attached. Figure 1 As shown, the smallest asymmetric structural unit contains half of Pb. 2+ Metal ions, half of ADBA 2– The ligand and a half-coordinated DMF molecule. Pb 2+ The metal ion is coordinated with five oxygen atoms, four of which are derived from two ADBA atoms. 2– The carboxylate group of the ligand has an O atom derived from the coordinated DMF molecule. Its Pb–O bond length ranges from 2.386(4) to 2.614(5) Å, thus forming along… b A one-dimensional chain of axes.

[0060] The X-ray powder diffraction pattern of sample 1# is attached. Figure 2 As shown, the experimental results (1 represents sample 1#) are consistent with the simulation results (simulation line), indicating that the material is a pure phase.

[0061] Samples 2#, 3#, and 4# were tested using the same method as described above. The X-ray single-crystal diffraction analysis results of samples 2#, 3#, and 4# were consistent with those of sample 1#; the XRD test results of samples 2#, 3#, and 4# were consistent with those of sample 1#.

[0062] Test Example 2 [Pb(ADBA)(DMF)] n Photoluminescence performance testing of crystalline materials The photoluminescence properties of sample 1# prepared in Example 1 were tested.

[0063] Sample 1# [Pb(ADBA)(DMF)] n The photoluminescence properties of the crystalline materials were tested on an Edinburgh FL920.

[0064] Excitation and emission spectra are attached. Figure 3 As shown, under the optimal wavelength of 410 nm, the compound exhibits blue light emission at 470 nm.

[0065] The RGB color coordinates of this blue-emitting crystal material, calculated from the fluorescence color coordinates, are (0.184, 0.279), indicating blue light emission (e.g., ...). Figure 4 (As shown).

[0066] The luminescence lifetime was tested using an Edinburgh FL920 ns flash lamp and a PMT detector. The luminescence lifetime and fitted curves are attached. Figure 5 As shown, the luminescence lifetime test indicates that sample 1# [Pb(ADBA)(DMF)] n The lifetime of the crystal material is 5.53 ns, which is on the order of ns, indicating that the blue crystal emits fluorescence.

[0067] Samples 2#, 3#, and 4# were tested using the same method as described above. The photoluminescence performance test results of samples 2#, 3#, and 4# were consistent with those of sample 1#.

[0068] Test Example 3 [Pb(ADBA)(DMF)] n Scintillation performance test of crystalline materials The scintillation performance of sample 1# prepared in Example 1 was tested.

[0069] Sample 1# [Pb(ADBA)(DMF)] n The scintillation emission tests of the crystalline materials were performed on a self-built X-ray scintillation spectrometer. The main component of the instrument was an Edinburgh FLS 920 fluorescence spectrometer, with a high-purity tungsten target (Moxtek® MAGPRO X-ray sources) as the excitation source. The scintillation emission spectra are attached. Figure 6 Under X-ray irradiation with constant tube voltage and different tube currents, the compound consistently exhibited a scintillation signal at 464 nm, indicating that the compound possesses a highly efficient X-ray response. The linear spectrum of scintillation intensity as a function of X-ray dose is attached. Figure 7 As the X-ray dose increases, the intensity of the scintillation signal increases linearly, indicating a high response sensitivity to X-rays.

[0070] Samples 2#, 3#, and 4# were tested using the same method as described above. The results of the flickering performance tests for samples 2#, 3#, and 4# were consistent with those for sample 1#.

[0071] Test Example 4 [Pb(ADBA)(DMF)] n Irradiation stability testing of crystalline materials The irradiation stability of sample 1# prepared in Example 1 was tested.

[0072] Sample 1# [Pb(ADBA)(DMF)] n The irradiation stability of the crystalline materials was tested using a self-built X-ray scintillation spectrometer. The samples were irradiated with continuous high-dose-rate X-rays, and their luminescence intensity was recorded. Figure 8As shown, no obvious photoquenching was found at a cumulative irradiation dose of 456 Gy, indicating that it has good irradiation stability.

[0073] Samples 2#, 3#, and 4# were tested using the same method as described above. The irradiation stability test results for samples 2#, 3#, and 4# were consistent with those for sample 1#.

[0074] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A crystal, characterized in that, The chemical formula of the crystal is shown below: [Pb(ADBA)(DMF)] n ADBA is a ligand formed after complete deprotonation of 9,10-bis(4-carboxyphenyl)anthracene; DMF is N,N -Dimethylformamide; n The value ∞ represents continuous repetition and infinite extension.

2. The crystal according to claim 1, characterized in that, The crystal has a one-dimensional structure; the smallest asymmetric structural unit of the one-dimensional structure is shown below; Pb 0.5 (ADBA) 0.5 (DMF) 0.5 The crystal is composed of an infinite number of Pb atoms. 0.5 (ADBA) 0.5 (DMF) 0.5 A one-dimensional chain composed of structural units.

3. The crystal according to claim 1, characterized in that, The Pb in the crystal is a five-coordinate Pb. 2+ Metal ions; The Pb 2+ Metal ions react with those from two ADBAs respectively 2– The four O atoms on the carboxylate group of the ligand and one O atom on the DMF are coordinated.

4. The crystal according to claim 1, characterized in that, The crystal belongs to the orthorhombic crystal system and has P NMA space group structure; Preferably, the unit cell parameters of the crystal are: a = 8.70~8.71 Å, b = 31.70~31.71 Å, c = 9.38~9.39 Å, α = 90°, β = 90°, γ = 90°, Z = 4, V = 2588.50~2600 Å 3 ; Preferably, a = 8.703~8.704 Å, b = 31.704~31.705 Å, c = 9.380~9.382 Å, V =2588.50~2595.50 Å 3 ; Preferably, a = 8.7031(3) Å, b = 31.7048(8) Å, c = 9.3810(3) Å, V = 2588.50(14)Å 3 .

5. The method for preparing the crystal according to any one of claims 1 to 4, characterized in that, The preparation method includes: placing a mixed solution containing 9,10-bis(4-carboxyphenyl)anthracene, a lead source, an organic acid, and a solvent in a sealed container, reacting the solution to obtain the crystals.

6. The preparation method according to claim 5, characterized in that, The lead source is selected from at least one of Pb(NO3)2, PbCl2, PbBr2 and PbI2; Preferably, the organic acid is o-fluorobenzoic acid; Preferably, the solvent is N , N -Dimethylformamide; Preferably, the molar ratio of the lead source to 9,10-bis(4-carboxyphenyl)anthracene is 1.8:1 to 2:1; Wherein, the molar amount of the lead source is expressed as the molar amount of Pb element in the lead source; Preferably, the ratio of lead source to solvent is 0.1 mmol: 2 ~ 5 mL; Preferably, the amount of organic acid added is sufficient to adjust the pH of the mixed solution to 5-7.

7. The preparation method according to claim 5, characterized in that, The reaction temperature is 80~120 ℃, and the reaction time is 24~72 h; Preferably, the reaction temperature is 90~100℃. o C, the reaction time is 36~72 h.

8. A scintillating material, characterized in that, The scintillation material is selected from the crystals described in any one of claims 1 to 4, or the crystals prepared by the preparation method described in any one of claims 5 to 7.

9. The scintillation material according to claim 8, characterized in that, The scintillating material emits blue fluorescence under ultraviolet light or X-ray irradiation; Preferably, the wavelength of the ultraviolet light is 320~400 nm; Preferably, the RGB color coordinates of the blue fluorescence are (0.16~0.20, 0.26~0.37); Preferably, the color coordinates of the RGB color system are (0.180~0.189, 0.274~0.354); More preferably, the RGB color coordinates are (0.184, 0.279); Preferably, the luminescence lifetime of the scintillating material is 4.5~6.0 ns; Preferably, the luminescence lifetime of the scintillating material is 5.20~5.70 ns; More preferably, the luminescence lifetime of the scintillating material is 5.53 ns.

10. The application of the crystal according to any one of claims 1 to 4, the crystal prepared by the preparation method according to any one of claims 5 to 7, or the scintillation material according to claim 8 or 9 in blue fluorescent materials, X-ray radiation detection materials, radiation detection dosimeters, and radiation imaging devices.

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