X-ray luminescent crystal material containing heavy atoms as well as preparation method and application of X-ray luminescent crystal material
By introducing heavy atoms through multi-level supramolecular self-assembly at room temperature and pressure, a highly efficient and stable X-ray luminescent crystal material was prepared, solving the problems of high cost and high safety risks in traditional methods. This method achieves high luminescence performance and stability, making it suitable for X-ray detection and imaging.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- FUJIAN NORMAL UNIV
- Filing Date
- 2026-01-20
- Publication Date
- 2026-04-28
AI Technical Summary
In existing technologies, metal halide scintillators have small X-ray absorption cross sections and poor detection sensitivity. Furthermore, traditional methods for introducing heavy atoms require extreme synthesis conditions such as high temperature and high pressure, resulting in high costs, complex procedures, and safety risks.
Heavy atoms were introduced at room temperature and pressure using a multi-level supramolecular self-assembly method, and then diffused through a mixed solution of dihalogen-substituted p-phenylenediamine hydrobromide and crown ether with manganese bromide to form an X-ray luminescent crystal material.
It improves the luminescence performance and stability of X-ray luminescent materials, achieving a luminescence quantum yield of over 60%, reducing production costs, and enhancing safety and environmental friendliness, making it suitable for X-ray detection and imaging technologies.
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Figure CN121930822A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of luminescent materials technology, and in particular to an X-ray luminescent crystal material containing heavy atoms, its preparation method, and its application. Background Technology
[0002] Scintillators convert high-energy X-rays into ultraviolet-visible-near-infrared photons and are widely used in radiation detection, high-energy physics, aerospace, clinical diagnostic imaging, and many other fields. In recent years, metal halide materials have attracted significant research interest as next-generation scintillator materials due to their high luminous efficiency and microsecond-level short decay times. However, hybrid scintillators suffer from small X-ray absorption cross-sections and poor detection sensitivity due to their limited effective atomic numbers and low exciton utilization efficiency of organic components, which severely hinders their development and potential commercial applications. Typically, X-ray photons interact with heavy atoms through electron-electron scattering and Auger processes, generating a large number of secondary electrons and exciting the inner-shell electrons of the atoms. Introducing heavy atoms (atomic numbers: Cl = 17, Br = 35, I = 53) into the scintillator can enhance X-ray absorption and improve scintillator output.
[0003] Currently, the introduction of heavy atoms into scintillators is mainly achieved through crystal growth processes, such as the Czochralski method, crucible descent method, and molten salt method (Flux Growth). Compounds containing the target heavy element (such as PbO, WO3, Bi2O3, NaI, etc.) are directly added to the growth raw materials, and then melted and crystallized at high temperatures to form a uniform crystal. These extreme synthesis conditions, such as high temperature and high pressure, result in high costs, complex synthesis steps, and safety and environmental risks. Summary of the Invention
[0004] To address the problems of low quantum yield, poor stability, and insufficient X-ray luminescence performance in organic-inorganic metal halide materials, as well as the need for extreme synthesis conditions such as high temperature and high pressure required by traditional heavy atom introduction methods, this invention aims to provide a convenient and efficient method for preparing X-ray luminescent crystal materials by introducing heavy atoms, and its application. This invention utilizes a multi-level supramolecular self-assembly method to achieve the introduction of heavy atoms under ambient temperature and pressure conditions, enabling efficient and convenient synthesis of X-ray luminescent materials. By leveraging supramolecular interactions, it eliminates the need for cumbersome organic synthesis modifications, high temperature and high pressure, or strong acidic environments.
[0005] To achieve the above objectives, the present invention provides the following technical solution: One of the technical solutions of this invention is an X-ray luminescent crystal material containing heavy atoms, with the chemical formula 2XL@AMnBr4, wherein 2XL represents dihalogen-substituted p-phenylenediamine hydrobromide, the halogen atom is one or two of Cl, Br and I, and A represents crown ether.
[0006] More preferably, the 2XL is 2,5-dibromo-p-phenylenediamine hydrobromide, the A is 18-crown-6, and the X-ray luminescent crystal material containing heavy atoms belongs to the triclinic crystal system with space group p-1 and its unit cell parameters are a = 9.7790(2) Å, b = 12.5038(3) Å, c = 21.0568(3) Å, α = 5.990(2), β = 92.800(2), γ = 108.225(2), Z = 2.
[0007] The second technical solution of the present invention is a method for preparing the above-mentioned X-ray luminescent crystal material containing heavy atoms, comprising the following steps: Dissolve dihalogen-substituted p-phenylenediamine hydrobromide and crown ether in an alcohol solution to obtain a 2XL@ABr2 solution; Manganese bromide was dissolved in acetonitrile and then added to the 2XL@ABr2 solution to obtain a mixed solution; The mixture solution was stirred and then diffused with an ether solvent to obtain the X-ray luminescent crystal material containing heavy atoms.
[0008] The present invention discloses the following technical effects: 1. This invention is the first to achieve the introduction of heavy atoms into the organic cation module of an organic-inorganic hybrid metal halide through multi-level supramolecular self-assembly, thereby improving the luminescence performance and stability of X-ray luminescent materials, with a luminescence quantum yield exceeding 60%. The X-ray luminescent material provided by this invention, as a scintillator in the core component, can efficiently convert X-rays into visible light signals, providing more accurate and rapid analysis and detection for multiple fields such as security inspection, scientific research, and medical diagnosis.
[0009] 2. This invention utilizes a multi-level supramolecular self-assembly strategy for preparation. Based on the abundant hydrogen bonding between supramolecular macrocycles and metal halide clusters, it can conveniently introduce organic ammonium salts modified with different heavy atoms without being affected by steric hindrance, thus facilitating the preparation of X-ray luminescent materials with excellent performance and good stability, fully demonstrating the advantages of supramolecular interaction.
[0010] 3. The synthesis process of the X-ray luminescent material provided by this invention does not require cumbersome organic synthesis steps, high temperature and high pressure conditions, or strong acid environment, which can greatly reduce production costs, improve production safety, and conform to the concept of environmental protection and sustainable development. It successfully introduces heavy metal atoms and creates a brand-new, low-cost, convenient and fast method for synthesizing X-ray luminescent materials. Attached Figure Description
[0011] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0012] Figure 1 This is a schematic diagram of the single crystal structure a (asymmetric unit) and b (crystal stacking structure) of the X-ray luminescent material 2BrL@AMnBr4 in this invention.
[0013] Figure 2 These are the excitation spectra and emission spectra of the 2BrL@AMnBr4 and L@AMnBr4 crystal materials in this invention at different excitation wavelengths, where a is 2BrL@AMnBr4 and b is L@AMnBr4.
[0014] Figure 3 The fluorescence decay curves of the 2BrL@AMnBr4 and L@AMnBr4 crystal materials in this invention are shown.
[0015] Figure 4 The emission spectra (a) of the 2BrL@AMnBr4 crystal material under different X-ray radiation doses in this invention and the linear relationship (b) between the emission spectrum intensity and radiation dose under different X-ray radiation doses are shown.
[0016] Figure 5 The emission spectra of the L@AMnBr4 crystal material under different X-ray radiation doses are shown in Figure a, and the linear relationship between the emission spectrum intensity and the radiation dose under different X-ray radiation doses is shown in Figure b. Detailed Implementation
[0017] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.
[0018] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any stated value or intermediate value within a stated range, as well as each smaller range between any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.
[0019] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.
[0020] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be obvious to those skilled in the art. This specification and embodiments are merely exemplary.
[0021] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.
[0022] In this invention, room temperature is defined as 25±5 °C.
[0023] The first aspect of the present invention provides an X-ray luminescent crystal material containing heavy atoms, with the chemical formula 2XL@AMnBr4, wherein 2XL represents dihalogen-substituted p-phenylenediamine hydrobromide, the halogen atom is one or two of Cl, Br and I, and A represents crown ether.
[0024] In a preferred embodiment of the present invention, 2XL is 2,5-dibromo-p-phenylenediamine hydrobromide, A is 18-crown-6, and the X-ray luminescent crystal material containing heavy atoms belongs to the triclinic crystal system with space group p-1 and its cell parameters are a=9.7790(2) Å, b= 12.5038(3) Å, c= 21.0568(3) Å, α= 5.990(2), β= 92.800(2), γ=108.225(2), Z=2.
[0025] A second aspect of the present invention provides a method for preparing the above-mentioned X-ray luminescent crystal material containing heavy atoms, comprising the following steps: Dissolve dihalogen-substituted p-phenylenediamine hydrobromide and crown ether in an alcohol solution to obtain a 2XL@ABr2 solution; Manganese bromide was dissolved in acetonitrile and then added to the 2XL@ABr2 solution to obtain a mixed solution; The mixture solution was stirred and then diffused with an ether solvent to obtain the X-ray luminescent crystal material containing heavy atoms.
[0026] In a preferred embodiment of the present invention, the alcohol solution is methanol, ethanol or isopropanol.
[0027] In a preferred embodiment of the present invention, the molar ratio of the dihalogen-substituted p-phenylenediamine hydrobromide, crown ether, and manganese bromide is 1:(0.5~2):(0.5~2).
[0028] More preferably, the molar ratio of the dihalogen-substituted p-phenylenediamine hydrobromide, crown ether, and manganese bromide is 1:(1~2):(0.5~1).
[0029] More preferably, the molar ratio of the dihalogen-substituted p-phenylenediamine hydrobromide, crown ether, and manganese bromide is 1:2:1.
[0030] In a preferred embodiment of the present invention, the stirring temperature is room temperature and the stirring time is 1-2 hours.
[0031] In a preferred embodiment of the present invention, the ether solvent is diethyl ether or petroleum ether.
[0032] In a preferred embodiment of the present invention, the diffusion temperature is 25~35 ℃ and the time is 12~14 h.
[0033] The third aspect of the present invention provides an application of the above-mentioned X-ray luminescent crystal material containing heavy atoms in X-ray detection and imaging technology.
[0034] Unless otherwise specified, the technical solutions described in this invention are all conventional solutions in the field, and the reagents or raw materials used are all purchased from commercial channels or are publicly available unless otherwise specified.
[0035] To better understand the present invention, the following embodiments further illustrate the content of the present invention, but the content of the present invention is not limited to the following embodiments.
[0036] Example 1 The preparation method of 2BrL@AMnBr4 single crystal includes the following steps: The ligands 2,5-dibromo-p-phenylenediamine hydrobromide (2BrL, 0.49 g, 1.14 mmol) and 18-crown-6 (A, 0.50 g, 2.27 mmol) were dissolved in 2 mL of methanol to obtain a 2BrL@ABr2 solution. Manganese bromide (0.24 g, 1.14 mmol) was dissolved in 2 mL of acetonitrile and then added dropwise to the 2BrL@ABr2 solution to obtain a mixed solution. The mixed solution was stirred at room temperature for 1 hour to obtain a clear solution. Diethyl ether was diffused into the prepared clear solution at 30 °C for 12 hours to obtain green bulk crystals, which are the 2-XL@AMnBr4 single-crystal luminescent material. The space group of the 2-XL@AMnBr4 single crystal is p-1, and its cell parameters are a = 9.7790(2) Å, b = 12.5038(3) Å, c = 21.0568(3) Å, α = 5.990(2), β = 92.800(2), γ = 108.225(2), Z = 2.
[0037] A schematic diagram of the 2-XL@AMnBr4 crystal structure is shown below. Figure 1 As shown, the 2,5-dibromophenylenediamine cation passes through -NH3 + Hydrogen bonding interactions between the group and the crown ether form dumbbell-shaped organic cations, with the organic cation group and MnBr4... 2- The clusters are stabilized through hydrogen bonding and electrostatic interactions. In the organic cationic module, the -CH2 group of the crown ether and MnBr4... 2- The halide ions in the cluster have hydrogen bond interactions, and it is because of these interactions that 2BrL@ABr2 can exist stably.
[0038] Comparative Example 1 Same as Example 1, except that the complex cation (2BrL@A) formed by 2,5-dibromophenylenediamine and 18-crown-6 is used. 2+ Replace 2,5-dibromophenylenediamine as the cation (2BrL) 2+ Due to the steric hindrance caused by bromine substituents, it is impossible to obtain Mn-based metal halides with good luminescence properties and stability.
[0039] Comparative Example 2 The ligands p-phenylenediamine hydrobromide (L, 0.31 g, 1.14 mmol) and 18-crown-6 (A, 0.50 g, 2.27 mmol) were dissolved in 2 mL of methanol to obtain the L@ABr2 solution. Manganese bromide (0.24 g, 1.14 mmol) was dissolved in 2 mL of acetonitrile solution and then added dropwise to the L@ABr2 solution to obtain a mixed solution. The mixed solution was stirred at room temperature for 1 hour to obtain a clear solution. Diethyl ether was diffused into the clear solution at 30 °C for 12 hours to obtain green bulk crystals, which are the L@AMnBr4 single-crystal luminescent material.
[0040] Test Example 1: Luminescent Properties of Crystalline Materials Figure 2 These are the excitation spectra and emission spectra of 2BrL@AMnBr4 and L@AMnBr4 crystalline materials at different excitation wavelengths. These materials exhibit a strong absorption band at approximately 310 nm, and two typical absorption bands at 360–380 nm and 430–480 nm, which are attributed to the organic component and Mn, respectively. 2+ From the ground state ( 6 S) to excited state ( 4 D, 4 The electronic transition of G). After excitation, 2BrL@AMnBr4 and L@AMnBr4 exhibit green emission with a peak at 510-513 nm, and the emission wavelengths produced under different excitation wavelengths are similar, which is due to [MnBr4]. 2‒ Mn 2+ of 4 T1(G)→ 6 The A1(S) transition, 2BrL@AMnBr4 (luminescence quantum yield 68%) exhibits higher luminescence intensity compared to L@AMnBr4 (luminescence quantum yield 36%).
[0041] Perform lifetime testing on the samples, such as Figure 3 The fluorescence lifetime spectra of the manganese-based metal halide samples are shown, with fluorescence lifetimes of 201 μs and 263 μs, respectively.
[0042] Figure 4 Linear curves of X-ray dose rate versus X-ray irradiation intensity for manganese-based metal halides 2BrL@AMnBr4 over a wide range are presented. The detection limits of these manganese-based metal halide scintillators can be obtained through calculation and analysis. The detection limit for manganese-based metal halides is 24.07 nGy. air s -1 .
[0043] like Figure 5As shown, the X-ray detection performance of the manganese-based metal halide prepared in Comparative Example 2 is significantly worse than that in Example 1, with a detection limit of 642.33 nGy. air s -1 This further illustrates the significant positive effect of the introduction of heavy atoms on X-ray detection performance.
[0044] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.
Claims
1. An X-ray luminescent crystal material containing heavy atoms, characterized in that, The chemical formula is 2XL@AMnBr4, where 2XL represents dihalogen-substituted p-phenylenediamine hydrobromide, the halogen atom is one or two of Cl, Br and I, and A represents crown ether.
2. The X-ray luminescent crystal material containing heavy atoms according to claim 1, characterized in that, The 2XL is 2,5-dibromo-p-phenylenediamine hydrobromide, the A is 18-crown-6, and the X-ray luminescent crystal material containing heavy atoms belongs to the triclinic crystal system with space group p-1. Its unit cell parameters are a = 9.7790(2) Å, b = 12.5038(3) Å, c = 21.0568(3) Å, α = 5.990(2), β = 92.800(2), γ = 108.225(2), Z = 2.
3. The method for preparing the X-ray luminescent crystal material containing heavy atoms as described in claim 1, characterized in that, Includes the following steps: Dissolve dihalogen-substituted p-phenylenediamine hydrobromide and crown ether in an alcohol solution to obtain a 2XL@ABr2 solution; Manganese bromide was dissolved in acetonitrile and then added to the 2XL@ABr2 solution to obtain a mixed solution; The mixture solution was stirred and then diffused with an ether solvent to obtain the X-ray luminescent crystal material containing heavy atoms.
4. The preparation method according to claim 3, characterized in that, The alcohol solution is methanol, ethanol, or isopropanol.
5. The preparation method according to claim 3, characterized in that, The molar ratio of the dihalogen-substituted p-phenylenediamine hydrobromide, crown ether, and manganese bromide is 1:(0.5~2):(0.5~2).
6. The preparation method according to claim 3, characterized in that, The stirring temperature is room temperature, and the stirring time is 1~2 hours.
7. The preparation method according to claim 3, characterized in that, The ether solvent is diethyl ether or petroleum ether.
8. The preparation method according to claim 3, characterized in that, The diffusion occurs at a temperature of 25-35 °C for 12-14 h.
9. The application of the X-ray luminescent crystal material containing heavy atoms as described in claim 1 in X-ray detection and imaging technology.