Crystal compound, preparation method thereof and application of crystal compound in X-ray detection, imaging and anti-counterfeiting encryption

Abstract

The invention discloses a crystal compound, a preparation method thereof and application of the crystal compound in X-ray detection, imaging and anti-counterfeiting encryption, and belongs to the technical field of crystals. The molecular formula of the crystal compound is [Cu (totp) (CH3CN) 3] [Cu2I3 (totp) (PN)]. (CH3CN), wherein totp is tris (o-tolyl) phosphine; and PN is diphenyl-2-pyridine phosphine. The crystal compound disclosed by the invention is simple in preparation method, and has the characteristics of large mass attenuation coefficient of X-ray energy, high light yield and low detection limit when being used as a material of an X-ray detector. The compound also has the characteristic of structural transformation in solvents such as methanol, ethanol, acetone, dichloromethane, tetrahydrofuran and the like, and meanwhile, the conversion of luminescence color under the excitation of 365nm ultraviolet light and X rays is accompanied. The material can be applied to the aspects of scintillator materials, room-temperature X-ray radiation indirect detection materials, radiation detection dosimeters, X-ray scintillator medical imaging, anti-counterfeiting encryption and the like.

Description

Technical Field

[0001] This application relates to the application of a crystalline compound and its preparation method in X-ray detection, imaging, and anti-counterfeiting encryption, and belongs to the field of crystal technology. Background Technology

[0002] Scintillators, as key functional materials for converting high-energy rays (X-rays, gamma rays, etc.) into visible light, play an irreplaceable role in fields such as medical imaging, high-energy physics detection, security inspection, industrial non-destructive testing, and nuclear reaction monitoring. Traditional inorganic scintillators mostly possess high atomic numbers and densities, exhibiting strong X-ray absorption capabilities. Currently, bismuth germanate (Bi4Ge3O4) exhibits excellent performance. 12 Cesium iodide (CsI:Tl), thallium-doped cesium iodide (Cd2O2S, GOS), and gadolinium oxysulfide (Gd2O2S, GOS) have been widely used in commercial radiation detectors. However, their long reaction times and demanding processes result in high production costs, hindering their widespread use. Traditional organic scintillators (OCS) possess significant advantages such as strong processing performance, diverse structures, and large-area fabrication capabilities, making them highly promising for flexible X-ray detection. However, their insufficient X-ray absorption leads to low radiative efficiency, limiting the development of OCS materials. Therefore, developing novel scintillators that combine high luminous yield, high stability, low cost, and large-area fabrication capabilities has become an urgent industry need. Summary of the Invention

[0003] The purpose of this invention is to overcome the defects of the prior art and provide a crystalline compound that solves the problems of high cost and demanding production of traditional inorganic materials and low radiation luminescence efficiency of traditional organic materials due to insufficient X-ray absorption.

[0004] The method for preparing the crystalline compound of this invention is simple, and as a material for X-ray detectors, it features high light yield and low detection limit. This compound also exhibits structural transformation properties in solvents such as methanol, ethanol, acetone, dichloromethane, and tetrahydrofuran, accompanied by color changes in emission under 365nm ultraviolet light and X-ray excitation. It can be applied to scintillator materials, room-temperature X-ray radiation indirect detection materials, radiation dosimeters, X-ray scintillator medical imaging, anti-counterfeiting encryption, and other fields.

[0005] According to the first aspect of this application, a crystalline compound is provided.

[0006] A crystalline compound having the molecular formula [Cu(totp)(CH3CN)3][Cu2I3(totp)(PN)]·(CH3CN); Wherein, totp is tris(o-tolyl)phosphine; PN stands for diphenyl-2-pyridinium phosphine.

[0007] Wherein, totp is tris(o-tolyl)phosphine, with the following structural formula: .

[0008] PN is diphenyl-2-pyridinephosphine, with the following structural formula: .

[0009] Alternatively, the PN ligand can be replaced with a triphenylphosphine ligand; The triphenylphosphine ligands are selected from at least one of triphenylphosphine, tris(m-tolyl)phosphine, tris(p-tolyl)phosphine, tris(4-fluorophenyl)phosphine, tris(4-chlorophenyl)phosphine, tris(3-fluorophenyl)phosphine, and tris(3-chlorophenyl)phosphine.

[0010] Optionally, the structure of the crystalline compound is: consisting of a [Cu₂I₃(totp)(PN)] group. - An anionic unit, one [Cu(totp)(CH3CN)3] + It consists of a cation unit and a free CH3CN molecule.

[0011] Optionally, the crystalline compound belongs to the trigonal crystal system with space group . R-3c .

[0012] Optionally, the unit cell parameters of the crystalline compound are: a = 15.3083 Å, b = 15.3083 Å, c =102.4462 Å, α = 90°, β = 90°, γ = 120°, Z = 12, cell volume is 20064.3(6) Å 3 .

[0013] According to a second aspect of this application, a method for preparing a crystalline compound is provided.

[0014] The method for preparing the crystalline compound described above involves dissolving cuprous iodide in a solvent to obtain solution I; dissolving tris(o-tolyl)phosphine and PN ligand in a solvent to obtain solution II; mixing solution I and solution II, sealing the mixture, and allowing it to stand and evaporate until crystals precipitate; washing and drying the mixture to obtain the crystalline compound.

[0015] Optionally, the molar ratio of cuprous iodide, PN ligand, and tris(o-tolyl)phosphine is 1.5~3:1:0.5~1.

[0016] Specifically, the molar ratio of cuprous iodide, PN ligand, and tris(o-tolyl)phosphine is 3:1:2.

[0017] Optionally, the solvent is selected from acetonitrile.

[0018] Optionally, the total molar amount of reactants to the volume ratio of solvent is 1 mol: 15~60 mL.

[0019] In a preferred embodiment, the method for preparing the crystalline compound includes: dissolving cuprous iodide in acetonitrile, dissolving tris(o-tolyl)phosphine and the corresponding triphenylphosphine ligand in acetonitrile, mixing the two solutions in a reactor, sealing the mixture with plastic wrap at room temperature and allowing it to stand or slowly evaporate; after a period of time, white crystals precipitate. After filtration, washing, and drying, the crystalline compound is obtained.

[0020] According to a third aspect of this application, an application of a crystalline compound is provided.

[0021] The aforementioned crystalline compounds are used as scintillator materials and indirect X-ray radiation detection materials. Furthermore, the crystalline compounds are used as room-temperature X-ray radiation indirect detection materials.

[0022] The aforementioned crystalline compounds have applications in imaging and anti-counterfeiting encryption. Furthermore, they are used in radiation detection dosimeters and X-ray scintillator medical imaging.

[0023] Specific application methods include: obtaining powder from crystalline compounds through grinding, etc., and mixing the powder with organosilicon to obtain scintillation films for X-ray imaging.

[0024] The beneficial effects that this application can produce include: (1) The present invention adopts a low-cost solution synthesis method and utilizes the synergistic advantage of self-assembly between inorganic and organic building blocks to obtain a compound with a crystal structure, [Cu(totp)(CH3CN)3][Cu2I3(totp)(PN)]·(CH3CN), which solves the problems of complex synthesis process and high production cost of existing commercial X-ray detection crystalline scintillator materials.

[0025] (2) The [Cu(totp)(CH3CN)3][Cu2I3(totp)(PN)]·(CH3CN) crystal of the present invention exhibits a highly efficient photocurrent response under X-rays. Utilizing the synergistic effect of the self-assembly of inorganic and organic components into a supramolecular network, it exhibits a large mass attenuation coefficient for X-ray energy, high light yield, and low detection limit. Compared with traditional inorganic scintillator materials, the [Cu(totp)(CH3CN)3][Cu2I3(totp)(PN)]·(CH3CN) crystal of the present invention has lower cost and a simpler synthesis method, while also having a stronger X-ray blocking ability compared with traditional organic scintillators.

[0026] (3) In addition, this compound also exhibits the characteristic of undergoing structural transformation in solvents such as methanol, ethanol, acetone, dichloromethane, and tetrahydrofuran, accompanied by a change in emission color under 365nm ultraviolet light and X-ray excitation. Therefore, the [Cu(totp)(CH3CN)3][Cu2I3(totp)(PN)]·(CH3CN) crystal of the present invention can be applied to scintillator bulk materials, room temperature X-ray radiation indirect detection materials, radiation detection dosimeters, X-ray scintillator medical imaging, and anti-counterfeiting encryption. Attached Figure Description

[0027] Figure 1 This is a schematic diagram of the asymmetrical unit of [Cu(totp)(CH3CN)3][Cu2I3(totp)(PN)]·(CH3CN) in Example 1; Figure 2 This is a schematic diagram of the structure of [Cu(totp)(CH3CN)3][Cu2I3(totp)(PN)]·(CH3CN) in Example 1; Figure 3 The X-ray powder diffraction pattern of [Cu(totp)(CH3CN)3][Cu2I3(totp)(PN)]·(CH3CN) from Example 1 is shown below. Figure 4 The infrared absorption spectrum of [Cu(totp)(CH3CN)3][Cu2I3(totp)(PN)]·(CH3CN) from Example 1 is shown below. Figure 5 The UV-Vis absorption spectrum of [Cu(totp)(CH3CN)3][Cu2I3(totp)(PN)]·(CH3CN) from Example 1 is shown. Figure 6 The RL spectra of [Cu(totp)(CH3CN)3][Cu2I3(totp)(PN)]·(CH3CN) and BGO with the same cross-sectional area and thickness; Figure 7The dose-rate dependent RL intensity of [Cu(totp)(CH3CN)3][Cu2I3(totp)(PN)]·(CH3CN) and BGO in the range of 0.0281–4.34 μGry / s. Detailed Implementation

[0028] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0029] Unless otherwise specified, all raw materials used in the embodiments of this application were purchased through commercial channels.

[0030] Unless otherwise specified, all test methods are standard and all instrument settings are those recommended by the manufacturer.

[0031] The analysis method in the embodiments of this application is as follows: The instrument used to collect X-ray single-crystal diffraction structure data was: Rigaku FR-X Microfocus X.

[0032] The X-ray powder diffraction test was conducted using a Miniflex 600 instrument under ambient temperature and pressure conditions, with scanning parameters ranging from 5° to 65°.

[0033] The instrument used for infrared absorption spectroscopy testing was a VERTEX 70.

[0034] The instrument used for ultraviolet-visible absorption spectroscopy was a PerkinElmer Lambda 950.

[0035] The detector used for the RL spectroscopy test was the PMT detector of the Edinburgh FLS 920 fluorescence spectrometer.

[0036] Example 1 3 mmol of CuI was dissolved in 130 mL of acetonitrile, and 2 mmol of tris(o-tolyl)phosphine and 1 mmol of diphenyl-2-pyridinephosphine were dissolved in 130 mL of acetonitrile. The mixture was placed in a 300 mL container, sealed, and allowed to stand at room temperature for two weeks. The precipitated crystals were collected, washed three times with acetonitrile, filtered, and dried to obtain white flaky crystals.

[0037] After X-ray diffraction (as shown in the attached image) Figure 3 As shown), infrared absorption (as attached) Figure 4 (as shown) and ultraviolet-visible absorption (as attached) Figure 5Tests (as shown) confirmed that the obtained white, flaky crystals have the chemical formula [Cu(totp)(CH3CN)3][Cu2I3(totp)(PN)]·(CH3CN) (totp represents tris(o-tolyl)phosphine, and PN represents diphenyl-2-pyridinium phosphine), belonging to the trigonal crystal system with space group 1. R-3c The unit cell parameters are a = 15.3083 Å, b = 15.3083 Å, c = 102.4462 Å, α = 90°, β = 90°, γ = 120°, Z = 12, cell volume is 20064.3(6) Å 3 The asymmetric units of [Cu(totp)(CH3CN)3][Cu2I3(totp)(PN)]·(CH3CN) are shown in the appendix. Figure 1 The structural schematic diagram of [Cu(totp)(CH3CN)3][Cu2I3(totp)(PN)]·(CH3CN) is shown in the attached diagram. Figure 2 As shown, its structure consists of a [Cu₂I₃(totp)(PN)] layer. – An anionic unit, one [Cu(totp)CH3CN)3] + It consists of a cation unit and a free CH3CN molecule.

[0038] The white flaky crystals [Cu(totp)(CH3CN)3][Cu2I3(totp)(PN)]·(CH3CN) obtained in Example 1 were ground into powder. The powder was then mixed with silicone to obtain a scintillation film for X-ray imaging.

[0039] Light yield is the total number of visible (or near-visible) photons emitted by a scintillator after absorbing ionizing radiation (gamma rays, X-rays, or charged particles) of a unit energy (typically 1 MeV). A higher light yield indicates a higher luminous efficiency of the scintillator under X-ray excitation. The RL spectra of [Cu(totp)(CH3CN)3][Cu2I3(totp)(PN)]·(CH3CN) with the same cross-sectional area and thickness as BGO are attached. Figure 6 As shown, the light yield of [Cu(totp)(CH3CN)3][Cu2I3(totp)(PN)]·(CH3CN) is 14832 photons MeV. -1 The value is relatively large.

[0040] The detection limit reflects the sensitivity of a radiation detector to X-rays and defines the minimum dose rate required for actual X-ray detection or imaging. The X-ray detection sensitivity of [Cu(totp)(CH3CN)3][Cu2I3(totp)(PN)]·(CH3CN) is shown in the attached figure. Figure 7 As shown in the figure. The results show that the detection limit of [Cu(totp)(CH3CN)3][Cu2I3(totp)(PN)]·(CH3CN) is 22.49 nGy s. -1 The detection limit is low.

[0041] Therefore, the above tests show that the [Cu(totp)(CH3CN)3][Cu2I3(totp)(PN)]·(CH3CN) crystal compound of the present invention is suitable as a material for X-ray detectors, and has the characteristics of large mass attenuation coefficient for X-ray energy, high light yield and low detection limit.

[0042] Example 2 When 50 mg of the sample was immersed in 3 mL of methanol and the container was sealed, it was left at room temperature for 2 hours. The original white flaky crystals turned yellow. Under 365 nm ultraviolet light excitation, the original blue light was converted into yellow light.

[0043] Example 3 When 50 mg of the sample was immersed in 3 mL of ethanol, the container was sealed, and left at room temperature for 2 hours, the original white flaky crystals turned yellow. Under 365 nm ultraviolet light excitation, the original blue light was converted into yellow light.

[0044] Example 4 When 50 mg of sample was immersed in 3 mL of acetone, the container was sealed, and left at room temperature for 2 hours, the original white flaky crystals turned yellow. Under 365 nm ultraviolet light excitation, the original blue light was converted into yellow light.

[0045] Example 5 When 50 mg of sample was immersed in 3 mL of dichloromethane, the container was sealed, and left at room temperature for 2 hours, the original white flaky crystals turned yellow. Under 365 nm ultraviolet light excitation, the original blue light was converted into orange light.

[0046] Example 6 When 50 mg of sample was immersed in 3 mL of tetrahydrofuran, the container was sealed, and left at room temperature for 2 hours, the original white flaky crystals turned light green. Under 365 nm ultraviolet light excitation, the original blue light was converted into green light.

[0047] Therefore, the above examples demonstrate that the [Cu(totp)(CH3CN)3][Cu2I3(totp)(PN)]·(CH3CN) crystal compound of the present invention has the characteristic of undergoing structural transformation in solvent, and has the potential for anti-counterfeiting and encryption applications.

[0048] 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 crystalline compound, characterized in that, The molecular formula of the crystalline compound is [Cu(totp)(CH3CN)3][Cu2I3(totp)(PN)]·(CH3CN); Wherein, totp is tris(o-tolyl)phosphine; PN stands for diphenyl-2-pyridinium phosphine.

2. The crystalline compound according to claim 1, characterized in that, PN ligands can be replaced with triphenylphosphine ligands; The triphenylphosphine ligands are selected from at least one of triphenylphosphine, tris(m-tolyl)phosphine, tris(p-tolyl)phosphine, tris(4-fluorophenyl)phosphine, tris(4-chlorophenyl)phosphine, tris(3-fluorophenyl)phosphine, and tris(3-chlorophenyl)phosphine.

3. The crystalline compound according to claim 1, characterized in that, The structure of the crystalline compound is: consisting of a [Cu₂I₃(totp)(PN)] group. - An anionic unit, one [Cu(totp)CH3CN)3] + It consists of a cation unit and a free CH3CN molecule.

4. The crystalline compound according to claim 1, characterized in that, The crystalline compound belongs to the trigonal crystal system, with space group . R-3c ; Preferably, the cell parameters of the crystalline compound are as follows: a = 15.3083 Å, b = 15.3083 Å, c = 102.4462Å, α = 90°, β = 90°, γ = 120°, Z = 12, cell volume is 20064.3(6) Å 3 .

5. A method for preparing the crystalline compound according to any one of claims 1 to 4, characterized in that, Dissolve cuprous iodide in a solvent to obtain solution I; dissolve tris(o-tolyl)phosphine and PN ligand in a solvent to obtain solution II; mix solution I and solution II, seal and allow to stand to evaporate until crystals precipitate, wash and dry to obtain the crystalline compound.

6. The preparation method according to claim 5, characterized in that, The molar ratio of cuprous iodide, PN ligand, and tris(o-tolyl)phosphine is 1.5~3:1:0.5~1.

7. The preparation method according to claim 5, characterized in that, The solvent is selected from acetonitrile.

8. The preparation method according to claim 5, characterized in that, The total molar amount of reactants to the volume ratio of solvent is 1 mol: 15~60 mL.

9. The application of the crystalline compound according to any one of claims 1 to 5 as a scintillator material or an indirect X-ray radiation detection material.

10. The application of the crystal compound according to any one of claims 1 to 5 in the fields of imaging and anti-counterfeiting encryption.

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