Crystal compound M4X4 (Py) 4 as well as preparation method and application thereof in X-ray detection, imaging and nonlinearity
By preparing the crystalline compound M4X4(Py)4, the problems of single function and complex synthesis of traditional materials have been solved, and efficient optical response and detection performance have been achieved, making it suitable for a variety of high-tech applications.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- FUJIAN INST OF RES ON THE STRUCTURE OF MATTER CHINESE ACAD OF SCI
- Filing Date
- 2025-11-28
- Publication Date
- 2026-04-10
AI Technical Summary
Existing scintillators and ultraviolet nonlinear crystal materials suffer from functional limitations. Traditional scintillators have weak nonlinear optical responses, and ultraviolet nonlinear crystals lack radiative emission capabilities. Furthermore, their synthesis processes are complex and costly, while emerging perovskite systems exhibit unstable structures and poor environmental durability.
A crystalline compound, M4X4(Py)4, was developed. Through a low-cost solution synthesis method, the synergistic advantages of self-assembly of inorganic and organic building blocks were utilized to prepare a multifunctional crystal with scintillation and nonlinear properties. Flexible thin film technology was employed to solve the problem of flexibility in traditional materials.
It achieves efficient light response and frequency doubling response, has high light yield and high X-ray detection sensitivity, and low detection limit. It is suitable for room temperature X-ray radiation detection and imaging, and can be applied to fields such as all-solid-state laser technology, optical computing, communication, information encryption, and biological imaging.
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Figure CN121825533A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to a kind of crystal compounds M4X4 (Py) 4 and its preparation method and application in X-ray detection, imaging, nonlinear, belong to crystal technical field. BACKGROUND
[0002] Scintillators are a class of functional materials that can convert high-energy ionizing radiation into ultraviolet or visible light, which is crucial in radiation detection, medical imaging, industrial non-destructive testing and high-energy physics. Ultraviolet nonlinear optical crystals promote the generation of short-wavelength lasers through second harmonic generation (SHG), which is an indispensable capability for advanced lithography, high-resolution imaging, and laser communication systems. Developing bifunctional materials with both scintillation and ultraviolet nonlinear properties not only aligns with the development trend of hetero-integration of optoelectronic devices, but also has the potential to make breakthroughs in the forefront fields of spatiotemporal coupling of deep ultraviolet coherent light sources, X-ray imaging, and multi-channel sensing integrated systems. However, existing material systems generally face the problem of functional singularity: traditional scintillators, such as Bi4Ge3O 12 (BGO) and CSI (Tl), have been extensively studied and commercialized with high luminous efficiency, but their nonlinear optical response is very weak. Ultraviolet nonlinear crystals (such as KBe2BO3F2 (KBBF), BaB2O4 (BBO), and KH2PO4 (KDP)) have high frequency multiplication effects, but lack radiation light-emitting capability. Emerging perovskite systems show promising dual functionality, but face inherent limitations, including structural instability due to ion migration tendency in low-dimensional halide frameworks, and compromised environmental durability due to low lattice formation energy.
[0003] Therefore, it is promising and urgently needed to develop new scintillating materials and nonlinear response bifunctional crystals with simple solution synthesis, excellent comprehensive scintillation performance, and high frequency response. SUMMARY
[0004] The present application aims to overcome the technical defects of existing single-function crystals, and provides a crystal compound, which solves the problems of traditional scintillators, such as complex synthesis, high production cost, difficulty in flexible imaging, weak nonlinear response or no response; and commercial ultraviolet nonlinear crystals, such as complex synthesis process, high production cost, lack of radiation light-emitting capability, etc.
[0005] According to the first aspect of the present application, a class of crystal compounds M4X4 (Py) 4 is provided. The crystal compound can be used as a multifunctional scintillation, nonlinear, and two-photon absorption crystal.
[0006] A class of crystal compounds M4X4 (Py) 4, wherein the organic ligand Py has the following general structure:
[0007] wherein R1, R2, R3 are independently selected from H, CH3, CH2CH3, NH3, F, Cl, Br or I; M is selected from Cu + , and X is selected from Cl, Br or I.
[0008] Optionally, the crystal compound M4X4(Py)4 has a structure in which [Cu4X4] clusters are connected to Py through Cu-N bonds, and these units are partitioned by Py into relatively independent parts, forming a zero-dimensional structure.
[0009] Optionally, the crystal compound M4X4(Py)4 belongs to the tetragonal system, and the space group is I -4.
[0010] Optionally, the crystal compound M4X4(Py)4 is Cu4I4(3Cl-py)4.
[0011] Optionally, the unit cell parameters of Cu4I4(3Cl-py)4 are: a = 14.0558 Å, b = 14.0558 Å, c = 8.0369 Å, α = 90°, β = 90°, gamma = 90°, Z = 8, and the unit cell volume is 1587.81(11 ) Å 3 .
[0012] According to a second aspect of the present application, a preparation method of a crystal compound M4X4(Py)4 is provided. The preparation method is simple, uses a low-cost solution synthesis process, and uses the synergistic advantages of self-assembly between inorganic units and organic units to solve the problem that a single inorganic component or a single organic component cannot achieve a function.
[0013] The preparation method of the crystal compound M4X4(Py)4 described above comprises: placing a mixed solution containing MX, an organic ligand Py, and a reaction medium in a container, reacting, filtering or volatilizing, washing, and drying to obtain the crystal compound M4X4(Py)4.
[0014] Optionally, the molar ratio of MX to the organic ligand Py is 0.8-3:1.
[0015] Optionally, the total number of moles of MX and the organic ligand Py and the volume of the reaction medium are in a ratio of 1 mmol: 10-50 mL.
[0016] Optionally, the MX is Cul, CuBr or CuCl.
[0017] Optionally, the reaction medium is selected from at least one of saturated aqueous potassium iodide, acetonitrile, acetone, dichloromethane, ethanol, methanol, N,N-dimethylformamide, N,N-dimethylacetamide.
[0018] Optionally, the reaction temperature is 10-30°C, and the reaction time is 1-30 minutes.
[0019] Optionally, the reaction temperature is room temperature.
[0020] Optionally, the reaction time is 10 minutes.
[0021] As a preferred embodiment, the preparation method comprises: placing the metal salt corresponding to M and the organic ligand corresponding to Py into a glass beaker, reacting at room temperature for 1-30 minutes, filtering (volatilizing), washing, and drying to obtain the crystal compound.
[0022] As a specific embodiment, the preparation method comprises: adding the metal salt corresponding to M, the 3Cl-Py corresponding to Py, and a reaction medium into a reactor, stirring at room temperature, reacting for 10 minutes, filtering, washing, and drying to obtain the crystal compound.
[0023] According to a third aspect of the present application, a flexible film is provided.
[0024] A flexible film, comprising microcrystals and organic polymers. The microcrystals are selected from the crystal compound M4X4(Py)4 described above.
[0025] Optionally, the organic polymers are selected from at least one of polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVDF), polysulfone, polydimethylsiloxane (PDMS), and resin.
[0026] According to a fourth aspect of the present application, a preparation method of a flexible film is provided. The flexible film is prepared by physically mixing microcrystal powder and organic polymers. The problem of difficulty in flexible of traditional inorganic materials is solved.
[0027] The preparation method of the flexible film described above comprises: mixing the microcrystal powder, the organic polymers, and an organic solvent, placing them on a substrate, and volatilizing to obtain the flexible film. or mixing MX, organic ligand Py, organic polymers, and an organic solvent, reacting, placing the mixture on a substrate, and volatilizing to obtain the flexible film.
[0028] Optionally, the organic solvent is selected from at least one of N,N-dimethylformamide, N,N-dimethylacetamide, acetone, acetonitrile, and dichloromethane.
[0029] According to the fifth aspect of this application, the application of a class of crystalline compounds M4X4(Py)4 is provided.
[0030] Applications of the aforementioned crystalline compound M4X4(Py)4 as a scintillation material, nonlinear material, two-photon material, or room-temperature X-ray radiation detection material The aforementioned crystalline compound M4X4(Py)4 has applications in radiation detection dosimeters, room temperature X-ray flexible imaging, all-solid-state laser technology, optical computing, optical switches, long-distance communication, information encryption and anti-counterfeiting, biological imaging, medical, lighting, ultraviolet devices, quantum technology, micro-nano manufacturing, biomedical or optoelectronic devices.
[0031] In this application, the room temperature is 25°C.
[0032] The beneficial effects that this application can produce include: (1) This invention employs a low-cost solution synthesis method, utilizing the synergistic advantage of self-assembly between inorganic and organic building blocks, to obtain the crystalline compound Cu4X4(Py)4, thus solving the problem of functional singularity commonly faced by existing material systems: traditional scintillators, such as Bi4Ge3O 12 (BGO) and CSI (Tl) have been studied in detail and commercialized with high luminous efficiency, but their nonlinear optical response is very weak. Ultraviolet nonlinear crystals, while possessing high-frequency multiplication effects, lack radiative luminescence capabilities. Furthermore, they suffer from complex fabrication processes and high production costs.
[0033] (2) The Cu4X4(Py)4 crystal of the present invention exhibits a highly efficient photoresponse under X-rays, a highly efficient frequency doubling response under lasers, and a two-photon phenomenon. Utilizing the synergistic effect of the self-assembly of inorganic and organic components, it exhibits a large light yield, high X-ray detection sensitivity, low detection limit, high X-ray imaging resolution, and high nonlinear frequency doubling response. Compared with the traditional scintillator material BGO, the Cu4X4(Py)4 crystal of the present invention has a larger light yield. Compared with the traditional nonlinear material KDP, the Cu4X4(Py)4 crystal of the present invention has a larger SHG. At the same time, it has a stronger X-ray blocking ability compared with organic scintillators. Therefore, the Cu4X4(Py)4 crystal of the present invention can be applied to room temperature X-ray radiation detection materials, radiation detection dosimeters, room temperature X-ray flexible imaging; all-solid-state laser technology, optical computing, optical switches, long-distance communication, information encryption and anti-counterfeiting, bioimaging, medical, lighting, ultraviolet devices, quantum technology, micro-nano manufacturing, biomedical and optoelectronic devices, etc. Attached Figure Description
[0034] Figure 1 Here are schematic diagrams of the structure of Cu4I4(3Cl-py)4 in Example 1: (a) is a schematic diagram of the structure of [Cu4I4] tetramer, and (b) is a schematic diagram of the structure of Cu4I4(3Cl-py)4. Figure 2 The X-ray powder diffraction pattern of Cu4I4(3Cl-py)4 in Example 1 is shown below. Figure 3 Thermogravimetric analysis (TGA) chromatogram of Cu4I4(3Cl-py)4 from Example 1; Figure 4 The attenuation efficiency of Cu4I4(3Cl-py)4 for X-ray energy in Example 1; Figure 5 The infrared absorption spectrum of Cu4I4(3Cl-py)4 in Example 1 is shown below. Figure 6 The excitation and emission fluorescence spectra of Cu4I4(3Cl-py)4 in Example 1 are shown. Figure 7 The quantum yield spectrum of Cu4I4(3Cl-py)4 in Example 1 is shown. Figure 8 The UV absorption spectrum of Cu4I4(3Cl-py)4 in Example 1 is shown below. Figure 9 The image shows the X-ray scintillation response spectrum of Cu4I4(3Cl-py)4 in Example 1. Figure 10 The scintillation yield spectrum of Cu4I4(3Cl-py)4 in Example 1 is shown. Figure 11 The X-ray irradiation stability spectrum of Cu4I4(3Cl-py)4 in Example 1 is shown. Figure 12 The X-ray detection limit of Cu4I4(3Cl-py)4 in Example 1; Figure 13 The nonlinear response of Cu4I4(3Cl-py)4 in Example 1 to a 1064 nm laser; Figure 14 The nonlinear response of different Cu4I4(3Cl-py)4 particles in Example 1 to a 1064 nm laser. Figure 15 The image shows the two-photon absorption spectrum of Cu4I4(3Cl-py)4 from Example 1.
[0035] Figure 16The image above shows the flexible Cu4I4(3Cl-py)4 thin film in Example 8. The image below shows the film under sunlight without the 365 nm UV lamp on, and the image below shows the light emission of the film when the 365 nm UV lamp is on. Figure 17 The imaging line pairs of the flexible Cu4I4(3Cl-py)4 thin film in Example 8; Figure 18 Example X-ray imaging spectrum of Cu4I4(3Cl-py)4 in Example 8 Figure 1 The top image corresponds to the image under sunlight when X-rays are off, and the bottom image corresponds to the image when X-rays are on. Figure 19 Example X-ray imaging spectrum of Cu4I4(3Cl-py)4 in Example 8 Figure 2 The top image corresponds to the image under sunlight when X-rays are off, and the bottom image corresponds to the image when X-rays are on. Detailed Implementation
[0036] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.
[0037] Unless otherwise specified, all raw materials used in the embodiments of this application were purchased through commercial channels.
[0038] Unless otherwise specified, all test methods are standard and all instrument settings are those recommended by the manufacturer.
[0039] The analysis method in the embodiments of this application is as follows: Single-crystal structure characterization: collected on a Rigaku FR-X type single-crystal diffractometer, Mo target, Ka Radiation source (λ = 0.7107 nm), test temperature 293 K.
[0040] Thermogravimetric analysis: performed using a METTLER TOLEDO TGA / DSC 1 thermogravimetric analyzer.
[0041] Photoluminescence spectroscopy, quantum yield, and decay lifetime: performed using an FLS1000 fluorescence spectrometer.
[0042] Scintillation performance (scintillation intensity, X-ray detection limit, and X-ray irradiation stability) was determined on an X-ray scintillation spectrometer.
[0043] XRD: Performed using a Rigaku Miniflex 600 X-ray diffractometer.
[0044] Example 1 CuI (0.1 mmol) and 3Cl-py (0.1 mmol) were placed in a 10 mL glass beaker in a 1:1 molar ratio. Then, 5 mL of dichloromethane solvent was added to the mixture and the container was placed to react. The reaction temperature was room temperature and the reaction time was 10 minutes. After the reaction was completed, the mixture was filtered, washed with dichloromethane, and dried to obtain light yellow transparent blocky crystals Cu4I4(3Cl-py)4.
[0045] Example 2 CuI (0.2 mmol) and 3Cl-py (0.1 mmol) were placed in a 10 mL glass beaker in a 2:1 molar ratio. Then, 5 mL of dichloromethane solvent was added to the mixture and the container was placed in the container for reaction. The reaction temperature was room temperature and the reaction time was 10 minutes. After the reaction was completed, the mixture was filtered, washed with dichloromethane, and dried to obtain light yellow transparent blocky crystals Cu4I4(3Cl-py)4.
[0046] Example 3 200 mg of polymethyl methacrylate (PMMA) was added to 1.5 mL of dichloromethane and stirred until completely dissolved. Then, 0.1 mmol of cuprous iodide and 0.1 mmol of 3-chloropyridine were added, and the mixture was placed in a glass vial and stirred with a magnetic stir bar. The reaction was carried out at room temperature until the solution became clear. The mixture was then poured onto a glass substrate, and after the solvent evaporated, a colorless and transparent film was formed.
[0047] Example 4 200 mg of polysulfone organic polymer was added to 1.5 mL of dichloromethane and stirred until completely dissolved. Then, 0.1 mmol of cuprous iodide and 0.1 mmol of 3-chloropyridine were added, and the mixture was placed in a glass vial and stirred with a magnetic stir bar. The reaction was carried out at room temperature until the solution became clear. The mixture was then poured onto a glass substrate, and after the solvent evaporated, a colorless and transparent film was formed.
[0048] Example 5 200 mg of polyvinylidene fluoride (PVDF) was added to 1.5 mL of dichloromethane and stirred until completely dissolved. Then, 0.1 mmol of cuprous iodide and 0.1 mmol of 3-chloropyridine were added, and the mixture was placed in a glass vial and stirred with a magnetic stir bar. The reaction was carried out at room temperature until the solution became clear. The mixture was then poured onto a glass substrate, and after the solvent evaporated, a colorless and transparent film was formed.
[0049] Example 6 300 mg of polysulfone organic polymer was added to 1.5 mL of DMA organic solvent and stirred until completely dissolved. Then, 800 mg of thoroughly ground Cu₄I₄(3Cl-py)₄ was added and stirred until homogeneous. The homogeneous mixture was poured onto a PET substrate and a flexible film was prepared by a blade coating method.
[0050] Example 7 300 mg of polymethyl methacrylate (PMMA) organic polymer was added to 1.5 mL of DMF organic solvent and stirred until completely dissolved. Then, 800 mg of thoroughly ground Cu₄I₄(3Cl-py)₄ was added and stirred until homogeneous. The homogeneous mixture was poured onto a PET substrate and a flexible film was prepared by a blade coating method.
[0051] Example 8 300 mg of polyvinylidene fluoride (PVDF) organic polymer was added to 1.5 mL of DMF organic solvent and stirred until completely dissolved. Then, 800 mg of thoroughly ground Cu₄I₄(3Cl-py)₄ was added and stirred until homogeneous. The homogeneous mixture was poured onto a PET substrate and a flexible film was prepared by a blade coating method.
[0052] Characterization test The Cu4I4(3Cl-py)4 of Example 1, after single-crystal structure characterization, belongs to the tetragonal crystal system with space group . I -4. The cell parameters are: a = 14.0558 Å, b = 14.0558 Å, c = 8.0369 Å, α = 90°, β = 90°, gamma = 90°, Z = 8, the unit cell volume is 1587.81(11) Å 3 . Figure 1 The diagram shows the structure of Cu4I4(3Cl-py)4 in Example 1. (a) is a schematic diagram of the structure of the [Cu4I4] tetramer, and (b) is a schematic diagram of the structure of Cu4I4(3Cl-py)4. The [Cu4I4] cluster is connected to 3-chloropyridine (3-Cl-py) via Cu-N bonds. Figure 1 a). Subsequently, these units were fragmented into relatively independent parts by 3-chloropyridine, forming a zero-dimensional structure ( Figure 1 b).
[0053] Figure 2The X-ray powder diffraction pattern of Cu4I4(3Cl-py)4 in Example 1 shows that the measured data agrees with the theoretical simulation data, proving that the prepared compound has high purity.
[0054] Figure 3 The thermogravimetric analysis (TGA) curve of Cu4I4(3Cl-py)4 in Example 1 shows that Cu4I4(3Cl-py)4 can exist stably at 105 degrees Celsius.
[0055] Figure 4 The attenuation efficiency of Cu4I4(3Cl-py)4 for X-ray energy in Example 1 shows that, using commercial BGO as a reference standard, Cu4I4(3Cl-py)4 has good attenuation efficiency for X-rays.
[0056] Figure 5 The infrared absorption spectrum of Cu4I4(3Cl-py)4 in Example 1 shows that CuI and 3Cl-py are coordinated, and Cu4I4(3Cl-py)4 was successfully prepared.
[0057] Figure 6 The excitation and emission fluorescence spectra of Cu4I4(3Cl-py)4 in Example 1 show that the optimal excitation and emission of Cu4I4(3Cl-py)4 are at 370 nm and 585 nm, respectively.
[0058] Figure 7 The quantum yield spectrum of Cu4I4(3Cl-py)4 in Example 1 shows that Cu4I4(3Cl-py)4 has an excellent quantum yield of up to 80.67%.
[0059] Figure 8 The image shows the UV absorption spectrum of Cu4I4(3Cl-py)4 from Example 1. It can be seen that Cu4I4(3Cl-py)4 has a large absorption in the range of 365-375 nm.
[0060] Figure 9 The image shows the X-ray scintillation response spectrum of Cu4I4(3Cl-py)4 in Example 1. It can be seen that Cu4I4(3Cl-py)4 exhibits an enhanced response to increasing X-ray dose rate.
[0061] Figure 10 The image shows the scintillation light yield spectrum of Cu4I4(3Cl-py)4 in Example 1. It can be seen that Cu4I4(3Cl-py)4 has a high light yield, which is superior to that of the commercial material BGO.
[0062] Figure 11The X-ray irradiation stability spectrum of Cu4I4(3Cl-py)4 in Example 1 shows that Cu4I4(3Cl-py)4 maintains good light output stability under continuous X-ray irradiation.
[0063] Figure 12 The X-ray detection limit of Cu4I4(3Cl-py)4 in Example 1 is shown to be 25.67 nGy s. -1 Low X-ray detection limit, lower than BGO's 62.43 nGy s -1 .
[0064] Figure 13 The nonlinear response of Cu4I4(3Cl-py)4 to a 1064 nm laser in Example 1 shows that Cu4I4(3Cl-py)4 has an excellent second-order nonlinear response, which is superior to that of the commercial material KDP.
[0065] Figure 14 The nonlinear response of different Cu4I4(3Cl-py)4 particles to a 1064 nm laser in Example 1 shows that Cu4I4(3Cl-py)4 exhibits phase matching at different grain sizes.
[0066] Figure 15 The two-photon absorption spectrum of Cu4I4(3Cl-py)4 in Example 1 shows that the slope is close to 2, indicating that Cu4I4(3Cl-py)4 has two-photon absorption capability.
[0067] Figure 16 The image above shows the flexible Cu4I4(3Cl-py)4 thin film in Example 8. The top image corresponds to the image under sunlight without the 365 nm UV lamp on, while the bottom image corresponds to the luminescence image of the thin film when the 365 nm UV lamp is on. It can be seen that Cu4I4(3Cl-py)4 has good flexibility.
[0068] Figure 17 The image shows the line pairs of the flexible Cu4I4(3Cl-py)4 thin film in Example 8. It can be seen that the flexible film can achieve a high resolution of 20.0 line pairs / mm.
[0069] Figure 18 Example X-ray imaging spectrum of Cu4I4(3Cl-py)4 in Example 8 Figure 1 The top image corresponds to the image under sunlight when X-rays are off, and the bottom image corresponds to the image when X-rays are on. It can be seen that the flexible film can clearly show the spring inside the capsule.
[0070] Figure 19Example X-ray imaging spectrum of Cu4I4(3Cl-py)4 in Example 8 Figure 2 The top image corresponds to the image under sunlight without X-rays, while the bottom image corresponds to the image with X-rays on. As can be seen, the internal structure of the earphone can be clearly observed through the flexible film.
[0071] 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 class of crystalline compounds, M4X4(Py)4, characterized in that, In the crystalline compound M4X4(Py)4, the organic ligand Py has the following general structural formula. Among them, R1, R2, and R3 are independently selected from H, CH3, CH2CH3, NH3, F, Cl, Br, or I; M is selected from Cu + X is selected from Cl, Br or I.
2. The crystalline compound M4X4(Py)4 according to claim 1, characterized in that, The structure of the crystal compound M4X4(Py)4 is as follows: [Cu4X4] clusters are connected to Py through Cu-N bonds, and these units are divided into relatively independent parts by Py to form a zero-dimensional structure.
3. The crystalline compound M4X4(Py)4 according to claim 1, characterized in that, The crystalline compound M4X4(Py)4 belongs to the tetragonal crystal system and has a space group of [missing information]. I -4; Preferably, the crystalline compound M4X4(Py)4 is Cu4I4(3Cl-py)4; Preferably, the cell parameters of Cu4I4(3Cl-py)4 are: a = 14.0558 Å, b = 14.0558 Å, c =8.0369 Å, α = 90°, β = 90°, γ = 90°, Z = 8, the unit cell volume is 1587.81(11) Å 3 .
4. The method for preparing the crystalline compound M4X4(Py)4 according to any one of claims 1 to 3, characterized in that, The preparation method includes: A mixed solution containing MX, organic ligand Py, and reaction medium is placed in a container, reacted, filtered or evaporated, washed, and dried to obtain the crystalline compound M4X4(Py)4.
5. The preparation method according to claim 4, characterized in that, The molar ratio of MX to the organic ligand Py is 0.8 to 3:1; Preferably, the total molar number of MX and the organic ligand Py and the volume ratio of the reaction medium are 1 mmol: 10~50 mL; Preferably, MX is CuI, CuBr, or CuCl; The reaction medium is selected from at least one of saturated potassium iodide aqueous solution, acetonitrile, acetone, dichloromethane, ethanol, methanol, N,N-dimethylformamide, and N,N-dimethylacetamide.
6. The preparation method according to claim 4, characterized in that, The reaction temperature is 10~30°C, and the reaction time is 1~30 minutes.
7. A flexible film, characterized in that, The flexible film comprises microcrystals and organic polymers; The microcrystals are selected from the crystalline compound M4X4(Py)4 as described in any one of claims 1 to 3.
8. The method for preparing the flexible thin film according to claim 7, characterized in that, Microcrystalline powder, organic polymer, and organic solvent are mixed, placed on a substrate, and volatilized to obtain the flexible film. Alternatively, MX, organic ligand Py, organic polymer, and organic solvent can be mixed, reacted, and then the mixture can be placed on a substrate and evaporated to obtain the flexible film.
9. The application of the crystalline compound M4X4(Py)4 according to any one of claims 1 to 3 as a scintillation material, nonlinear material, two-photon material or room-temperature X-ray radiation detection material.
10. The application of the crystal compound M4X4(Py)4 according to any one of claims 1 to 3 in the fields of radiation detection dosimeters, room temperature X-ray flexible imaging, all-solid-state laser technology, optical computing, optical switches, long-distance communication, information encryption and anti-counterfeiting, bioimaging, medical, lighting, ultraviolet devices, quantum technology, micro-nano manufacturing, biomedical or optoelectronic devices.