Organic-inorganic hybrid compound as well as preparation method and application thereof

Abstract

The invention discloses an organic-inorganic hybrid compound as well as a preparation method and application thereof, and belongs to the field of optical functional materials. The chemical formula of the organic-inorganic hybrid compound is [Ga (C2H6OS) 6] (SbBr6), the organic-inorganic hybrid compound belongs to a trigonal system, the space group is the [Ga (C2H6OS) 6] (SbBr6) crystal provided by the invention, and the preparation method is simple. The organic-inorganic hybrid compound has yellow green photoluminescence and radiation luminescence properties, and the [Ga (C2H6OS) 6] (SbBr6) (at) PDMS fluorescent screen provided by the invention has high spatial resolution X-ray imaging performance. The compound has wide practical application value in the field of X-ray imaging.

Description

Technical Field

[0001] The present application relates to an organic-inorganic hybrid compound and a preparation method and application thereof, belonging to the field of optical functional materials. Background Art

[0002] Luminescent materials have broad application potential in fields such as light-emitting diodes and X-ray imaging. Organic-inorganic hybrid compounds, particularly organic-inorganic hybrid metal halides, offer a wide range of structural types and are easily prepared using low-cost solution or solvent methods. These compounds offer the advantages of simple preparation processes and low costs, making them a crucial research area for the development of high-performance, low-cost luminescent materials.

[0003] Although a large number of organic-inorganic hybrid metal halide luminescent materials have been reported, there are relatively few reports on hybrid bromides containing bimetallic elements. To date, there have been no reports on bimetallic hybrid bromides containing both gallium (Ga) and antimony (Sb). Summary of the Invention

[0004] According to a first aspect of the present application, an organic-inorganic hybrid compound is provided.

[0005] An organic-inorganic hybrid compound, wherein the chemical formula of the organic-inorganic hybrid compound is [Ga(C2H6OS)6](SbBr6).

[0006] Optionally, the crystal structure of the organic-inorganic hybrid compound is:

[0007] By isolated [Ga(C2H6OS)6] 3+ Cationic clusters and (SbBr6) 3- The anionic octahedron forms a zero-dimensional structure through electrostatic interaction.

[0008] Optionally, the asymmetric unit of the structure includes 1 Ga atom, 1 Sb atom, 1 Br atom, 1 S atom, 1 O atom, 2 C atoms and 6 H atoms; the S atom, 1 O atom and two methyl groups (C(1)H3 and C(2)H3) form a C2H6OS unit;

[0009] Ga is an octahedral coordination structure, bonding with the six O atoms in the C2H6OS unit to form [Ga(C2H6OS)6] 3+ Cationic clusters;

[0010] Sb is an octahedral coordination structure, bonding with six Br atoms to form (SbBr6) 3- anionic octahedron;

[0011] Isolated [Ga(C2H6OS)6] 3+Cationic clusters and (SbBr6) 3- Anionic octahedra are arranged alternately and separated from each other, and form a zero-dimensional overall structure through electrostatic interaction.

[0012] Optionally, the organic-inorganic hybrid compound belongs to the trigonal system, and the space group is The cell parameters are α = β = 90°, γ = 120°, Z = 3.

[0013] Specifically,

[0014] Optionally, the organic-inorganic hybrid compound has photoluminescence properties, and the excitation peak is located at a wavelength of 365 nm, and the emission peak is located at 540 nm.

[0015] Optionally, the organic-inorganic hybrid compound exhibits yellow-green fluorescence under 365 nm ultraviolet light irradiation.

[0016] Optionally, the organic-inorganic hybrid compound has radioluminescence properties, and the emission peak is located at 545 nm under X-ray excitation;

[0017] Optionally, the organic-inorganic hybrid compound exhibits yellow-green fluorescence under 50 kV X-ray excitation.

[0018] According to a second aspect of the present application, a preparation method of an organic-inorganic hybrid compound is provided. The preparation method is simple, and can obtain the organic-inorganic hybrid compound crystal with high purity and high crystallinity.

[0019] The preparation method of the organic-inorganic hybrid compound described above, the preparation method comprises:

[0020] The raw materials of SbBr3, Ga2O3, HBr and DMSO are mixed and placed in a sealed container, crystallized, and cooled to obtain the organic-inorganic hybrid compound.

[0021] Optionally, the amount ratio of SbBr3, Ga2O3, HBr and DMSO is 0.15 mmol: 0.3-0.5 mmol: 0.2-0.3 mL: 0.8-1.5 mL;

[0022] Among them, HBr is a 40wt% HBr solution.

[0023] Optionally, the crystallization temperature is 100-150°C, and the time is 18-36h.

[0024] Optionally, 0.15 mmol (34.2 mg) of SbBr3, 0.4 mmol (75.0 mg) of Ga2O3, 0.25 mL of 40 wt% HBr solution, and 1.0 mL of DMSO are loaded into a 25 mL Teflon-lined autoclave, sealed, and heated at 120°C for 24 hours for crystallization, and then cooled to room temperature at a rate of 5°C / hour. After the reaction is completed, the organic-inorganic hybrid compound crystals are obtained after washing, suction filtration, and drying.

[0025] Optionally, the preparation method comprises:

[0026] (a) 0.15 mmol (34.2 mg) of SbBr3, 0.4 mmol (75.0 mg) of Ga2O3, 0.25 mL of 40 wt% HBr solution, and 1.0 mL of DMSO are loaded into a 25 mL Teflon-lined autoclave, sealed, and heated at a crystallization temperature of 120°C for 24 hours for crystallization;

[0027] (b) After the crystallization is completed, the temperature is lowered to room temperature at a rate of 5°C / hour, and the organic-inorganic hybrid compound crystals are obtained after washing, suction filtration, and drying.

[0028] According to a third aspect of the present application, an application of an organic-inorganic hybrid compound is provided.

[0029] An application of the organic-inorganic hybrid compound described above in X-ray imaging.

[0030] Optionally, the organic-inorganic hybrid compound is prepared into a powder, uniformly dispersed in PDMS, and then prepared into a scintillation fluorescent screen for X-ray imaging by spin coating, heating and drying, and curing into a film.

[0031] In the present application, “room temperature” refers to 20±5°C.

[0032] In the present application, DMSO refers to dimethyl sulfoxide, which is a sulfur-containing organic compound with a molecular formula of C2H6OS.

[0033] In the present application, PDMS refers to polydimethylsiloxane, which is a high molecular polymer with a chemical formula of (C2H6OSi) n .

[0034] The beneficial effects that can be produced by the present application include:

[0035] (1) The present application provides a new organic-inorganic hybrid compound [Ga(C2H6OS)6](SbBr6) with excellent photoluminescence and radiation luminescence properties, which has potential application value as a luminescent material.

[0036] (2) The organic-inorganic hybrid compound [Ga(C2H6OS)6](SbBr6) crystals provided herein exhibit bright yellow-green broadband photoluminescence under 365nm ultraviolet excitation, with a central wavelength of 540nm, a full width at half maximum of 115nm, and a Stokes shift of 175nm. This fluorescence property, with its wide half-width and large Stokes shift, is advantageous for its application as a photoluminescent material.

[0037] (3) The organic-inorganic hybrid compound [Ga(C2H6OS)6](SbBr6) crystal provided in this application exhibits bright yellow-green broadband radiation luminescence under X-ray excitation, with a central wavelength of 545nm, a full width at half maximum of 115nm, and a light yield of 13500 photons MeV -1 [Ga(C2H6OS)6](SbBr6) crystals exhibit high light yield, which is beneficial for their application as scintillation luminescent materials.

[0038] (4) This application also provides a method for preparing the organic-inorganic hybrid compound [Ga(C2H6OS)6](SbBr6), which uses a solvent method to prepare a crystalline sample. The method is simple and can produce high-purity, high-crystallinity [Ga(C2H6OS)6](SbBr6) crystals.

[0039] (5) The [Ga(C2H6OS)6](SbBr6)@PDMS phosphor screen provided in this application exhibits clear X-ray imaging performance with a spatial resolution of 10 lp mm -1 , which has potential application value in X-ray imaging, safety inspection and industrial non-destructive testing. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 The following are photographs of the [Ga(C2H6OS)6](SbBr6) crystal provided in Example 1 of the present application, taken under natural light and 365nm ultraviolet light. (a) is a photograph taken under natural light; (b) is a photograph taken under 365nm ultraviolet light.

[0041] Figure 2 This is a schematic diagram of the [Ga(C2H6OS)6](SbBr6) crystal structure provided in Example 1 of the present application.

[0042] Where (a) is (SbBr6) 3- Schematic diagram of anion octahedron; (b) is [Ga(C2H6OS)6] 3+ Schematic diagram of the cation cluster; (c) is a schematic diagram of the unit cell structure.

[0043] Figure 3is the X-ray powder diffraction pattern of [Ga(C2H6OS)6](SbBr6) powder provided by Embodiment 1 of the present application. Wherein (a) is the pattern obtained by X-ray diffraction test after sample 1 is ground into powder, and (b) is the X-ray diffraction pattern fitted according to the crystal structure analyzed by single crystal X-ray diffraction.

[0044] Figure 4 is the morphology image of [Ga(C2H6OS)6](SbBr6) crystal provided by Embodiment 1 of the present application under scanning electron microscope.

[0045] Figure 5 is the energy dispersive X-ray spectrum (EDS) of [Ga(C2H6OS)6](SbBr6) crystal provided by Embodiment 1 of the present application.

[0046] Figure 6 is the fluorescence excitation and emission spectrum of [Ga(C2H6OS)6](SbBr6) provided by Embodiment 1 of the present application.

[0047] Figure 7 is the fluorescence decay curve of [Ga(C2H6OS)6](SbBr6) provided by Embodiment 1 of the present application.

[0048] Figure 8 is the photo of [Ga(C2H6OS)6](SbBr6) crystal under X-ray radiation provided by Embodiment 1 of the present application.

[0049] Figure 9 is the emission spectrum of [Ga(C2H6OS)6](SbBr6) crystal under X-ray radiation excitation provided by Embodiment 1 of the present application.

[0050] Figure 10 is the emission spectrum of [Ga(C2H6OS)6](SbBr6) and reference sample LuAG:Ce under the same X-ray excitation condition provided by Embodiment 1 of the present application.

[0051] Figure 11 is the photo of [Ga(C2H6OS)6](SbBr6)@PDMS fluorescent screen under natural light and 365nm ultraviolet light irradiation provided by Embodiment 4 of the present application. Wherein (a) is the photo under natural light irradiation; and (b) is the photo under 365nm ultraviolet light irradiation.

[0052] Figure 12 is the X-ray imaging photo of [Ga(C2H6OS)6](SbBr6)@PDMS fluorescent screen to remote controller provided by Embodiment 4 of the present application.

[0053] Figure 13This is an X-ray imaging photograph of the [Ga(C2H6OS)6](SbBr6)@PDMS fluorescent screen provided in Example 4 of the present application against the standard test pattern plate. DETAILED DESCRIPTION

[0054] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0055] Unless otherwise specified, the raw materials in the examples of this application were purchased through commercial channels.

[0056] Unless otherwise specified, conventional methods were used for testing, and instrument settings were those recommended by the manufacturer.

[0057] Example 1 Preparation of [Ga(C2H6OS)6](SbBr6) Crystals by Solvent Method

[0058] The raw materials, accurately weighed in the ratio of 0.15 mmol (34.2 mg) SbBr₃, 0.4 mmol (75.0 mg) Ga₂O₃, 0.25 mL 40 wt% HBr solution, and 1.0 mL DMSO, were added to a 25 mL polytetrafluoroethylene-lined hydrothermal synthesis reactor. After sealing, the reaction was placed in an electric forced-air drying oven and heated from 20°C to 120°C at a rate of 30°C / h, then maintained at 120°C for 24 hours, and finally slowly cooled to room temperature at a rate of 5°C / h. After the reaction was complete, the reaction was repeatedly rinsed with anhydrous ethanol and filtered, and then air-dried to obtain transparent rhombohedral [Ga(C₂H₂OS)₆](SbBr₆) crystals. Under ultraviolet light excitation, the crystals exhibited yellow-green fluorescence.

[0059] Figure 1 The following are photographs of sample 1# crystals; (a) is taken under natural light; (b) is taken under 365nm UV light, with a scale of approximately 0.5mm. As can be seen from the images, the resulting crystals are transparent, regular rhombohedral hexahedrons; under 365nm UV light, the crystals exhibit bright yellow-green fluorescence.

[0060] Crystal structure analysis of [Ga(C2H6OS)6](SbBr6)

[0061] The structure of the samples was elucidated using single crystal X-ray diffraction and powder X-ray diffraction methods.

[0062] The single crystal X-ray diffraction data were collected using a single crystal X-ray diffractometer (model: XtaLABSynergy R) from Rigaku Corporation of Japan, and the data were restored using the CrysAlis software that comes with the instrument. The X-ray light source used for single crystal diffraction was graphite monochromatized Mo-Kα rays with a wavelength of Data collection was completed at a low temperature of 100 K. Crystal structure analysis and refinement were completed using the SHELXL-2019 software package, and the crystal structure diagram was drawn using Diamond software.

[0063] Powder X-ray diffraction was performed using a Bruker powder X-ray diffractometer (model: D8-ADVANCE) at room temperature; the X-ray source was a Cu target (wavelength ), the scanning step size is 0.02.

[0064] Single crystal X-ray diffraction results show that the chemical formula of the sample is [Ga(C2H6OS)6](SbBr6), belonging to the trigonal system, and the space group is The unit cell parameters are α=β=90°,γ=120°,Z=3. Among them, the typical representative is, the unit cell parameters are α = β = 90°, γ = 120°, Z = 3. Table 1 shows the crystallographic data of the single crystal X-ray diffraction structure analysis results.

[0065] Table 1

[0066]

[0067]

[0068] The crystal structure diagram of the organic-inorganic hybrid compound [Ga(C2H6OS)6](SbBr6) is shown in FIG. Figure 2 As shown, where (a) is (SbBr6) 3- Schematic diagram of anion octahedron; (b) is [Ga(C2H6OS)6] 3+ Schematic diagram of the cation cluster; (c) is a schematic diagram of the unit cell structure.

[0069] The crystal structure of the organic-inorganic hybrid compound [Ga(C2H6OS)6](SbBr6) is composed of isolated [Ga(C2H6OS)6] 3+ Cationic clusters and (SbBr6) 3- The anion octahedron forms a zero-dimensional structure through electrostatic interaction. The asymmetric unit of this structure includes 1 Ga atom, 1 Sb atom, 1 Br atom, 1 S atom, 1 O atom, 2 C atoms and 6 H atoms. The S atom, 1 O atom and two methyl groups (C(1)H3 and C(2)H3) form a C2H6OS unit. Ga is in an octahedral coordination configuration and bonds with the O atoms in the six C2H6OS units to form [Ga(C2H6OS)6] 3+Cationic cluster; Sb is octahedral coordination configuration, bonding with six Br atoms to form (SbBr6) 3- Anionic octahedron; isolated [Ga(C2H6OS)6] 3+ Cationic cluster and (SbBr6) 3- Anionic octahedrons are alternately arranged and separated from each other, and form a zero-dimensional overall structure through electrostatic interaction.

[0070] Figure 3 The result is powder X-ray diffraction test. The powder X-ray diffraction pattern (a) obtained by X-ray diffraction test after sample 1# is ground into powder is compared with the powder X-ray diffraction pattern (b) obtained by fitting the crystal structure analyzed by single crystal X-ray diffraction. The diffraction peak position and peak intensity in the experimental pattern and the fitting pattern are consistent, which indicates that the obtained sample has very high purity. Moreover, the diffraction peaks in the experimental pattern are relatively sharp, which indicates that the obtained sample has high crystallinity.

[0071] SEM morphology observation and EDS element composition analysis of [Ga(C2H6OS)6](SbBr6) crystal

[0072] The morphology of the crystal sample was observed by scanning electron microscope (SEM) (Japan Electronics, FESEM, JSM6700F), and the micro-area element composition of the crystal sample was analyzed by energy dispersive X-ray spectrometer (EDS) (Oxford INCA) equipped with the SEM.

[0073] SEM morphology observation shows that [Ga(C2H6OS)6](SbBr6) crystal presents regular rhombohedron morphology Figure 4 EDS element analysis shows that the molar ratio of Ga / Sb / Br / S is 1.0:1.2:5.6:5.2, which is basically consistent with the element ratio in the molecular formula Figure 5

[0074] Example 2: Test of photoluminescence properties of [Ga(C2H6OS)6](SbBr6) crystal

[0075] The fluorescence excitation spectrum and emission spectrum of [Ga(C2H6OS)6](SbBr6) were tested at room temperature by using FLS950 fluorescence spectrometer of Edinburgh Company in the United Kingdom, and the time-resolved fluorescence decay data collected by using picosecond pulse semiconductor laser with wavelength of 375 nm as light source.

[0076] The strongest excitation peak of [Ga(C2H6OS)6](SbBr6) is located at 365 nm, and the strongest emission peak is located at 540 nm Figure 6 ​Under 365nm excitation, the emission spectrum exhibits a broadband Gaussian emission centered at 540nm; its full width at half maximum (FWHM) is measured to be 115nm, and its Stokes shift is as high as 175nm. A large Stokes shift effectively avoids self-absorption and facilitates efficient fluorescence emission.

[0077] The time-resolved decay data of the 540 nm emission were measured using a 375 nm picosecond pulse laser, and the fluorescence decay curve was fitted with a single exponential function, and the fluorescence lifetime was estimated to be 0.82 μs ( Figure 7 ).

[0078] Example 3: Test of the radioluminescence properties of [Ga(C2H6OS)6](SbBr6) crystals

[0079] Radioluminescence spectra were collected using a fluorescence spectrometer (Ocean Optics, QEPRO-N500-slitsize) equipped with an X-ray source (Ametek Mini-X X-ray tube, target: Mo, Pmax = 6 W, Vmax = 50 kV, Imax = 120 μA). X-ray dose was measured using a LANDAUER microSTAR-II dosimeter. Light yield was measured using a commercially available LuAG:Ce scintillator as a reference sample.

[0080] Under X-ray radiation, the bright green fluorescence of [Ga(C2H6OS)6](SbBr6) crystal can be directly observed by naked eyes ( Figure 8 ), indicating that [Ga(C2H6OS)6](SbBr6) has radioluminescence properties.

[0081] Corresponding to an X-ray dose rate of 50,000 μGyair s-1, the central peak of the radioluminescence spectrum is located at 545 nm, and the full width at half maximum (FWHM) is 115 nm, which is similar to the emission spectrum under ultraviolet light excitation ( Figure 9 ).

[0082] Commercially available LuAG:Ce scintillator (light output 25000 photons MeV -1 ) was used as a reference sample. By comparing the integrated intensity of the X-ray radiation emission spectrum measured under the same experimental conditions, the light yield of [Ga(C2H6OS)6](SbBr6) was calculated to be 13500 photons MeV -1 ( Figure 10 ).

[0083] Example 4 Preparation of [Ga(C2H6OS)6](SbBr6)@PDMS phosphor screen

[0084] The [Ga(C2H6OS)6](SbBr6) thin film phosphor screen was prepared by spin coating. [Ga(C2H6OS)6](SbBr6) crystals were ground into a uniform powder. 100 mg of [Ga(C2H6OS)6](SbBr6) powder was weighed and dispersed in 5 mL of PDMS. The mixture was then magnetically stirred and ultrasonicated to produce a colloidal mixture. After vacuum degassing, the colloidal mixture was spin-coated at 500 rpm and then annealed in an oven at 100°C to prepare the [Ga(C2H6OS)6](SbBr6)@PDMS thin film phosphor screen.

[0085] like Figure 11 As shown, the prepared [Ga(C2H6OS)6](SbBr6)@PDMS fluorescent screen exhibits bright yellow-green fluorescence under ultraviolet light (b).

[0086] Example 5 X-ray imaging experiment of [Ga(C2H6OS)6](SbBr6)@PDMS fluorescent screen.

[0087] An X-ray light source (Ametek Mini-X X-ray tube, target: Mo, Pmax = 6 W, Vmax = 50 kV, Imax = 120 μA) was used as the excitation light source. The X-ray source, imaging object, [Ga(C2H6OS)6](SbBr6)@PDMS fluorescent screen, and digital camera were placed in this order to conduct X-ray imaging experiments.

[0088] like Figure 12 As shown in the figure, with the remote control as the imaging object, the X-ray imaging image shows obvious brightness differences, clearly showing the internal details of the remote control. Figure 13 As shown in the image, based on the X-ray imaging of the standard test pattern plate, the X-ray imaging spatial resolution of the [Ga(C2H6OS)6](SbBr6)@PDMS phosphor screen is estimated to be about 10lp mm -1 .

[0089] The above descriptions are merely a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application discloses the preferred embodiments as above, they are not intended to limit the present application. Any technical personnel familiar with the present profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. An organic-inorganic hybrid compound, characterized in that The chemical formula of the organic-inorganic hybrid compound is [Ga(C2H6OS)6](SbBr6).

2. The organic-inorganic hybrid compound according to claim 1, characterized in that The crystal structure of the organic-inorganic hybrid compound is: By isolated [Ga(C2H6OS)6] 3+ Cationic clusters and (SbBr6) 3- The anionic octahedron forms a zero-dimensional structure through electrostatic interaction; Preferably, the asymmetric unit of the structure includes 1 Ga atom, 1 Sb atom, 1 Br atom, 1 S atom, 1 O atom, 2 C atoms and 6 H atoms; the S atom, 1 O atom and two methyl groups (C(1)H3 and C(2)H3) form a C2H6OS unit; Ga is an octahedral coordination structure, bonding with the six O atoms in the C2H6OS unit to form [Ga(C2H6OS)6] 3+ Cationic clusters; Sb is an octahedral coordination structure, bonding with six Br atoms to form (SbBr6) 3- anionic octahedron; Isolated [Ga(C2H6OS)6] 3+ Cationic clusters and (SbBr6) 3- The anionic octahedra are arranged alternately and separated from each other, forming a zero-dimensional overall structure through electrostatic interaction.

3. The organic-inorganic hybrid compound according to claim 1, characterized in that The organic-inorganic hybrid compound belongs to the trigonal system, and the space group is The unit cell parameters are α=β=90°, γ=120°, Z=3; Preferably, 4. The organic-inorganic hybrid compound according to claim 1, characterized in that The organic-inorganic hybrid compound has a photoluminescent property, with an excitation peak at a wavelength of 365 nm and an emission peak at 540 nm; Preferably, the organic-inorganic hybrid compound exhibits yellow-green fluorescence under 365nm ultraviolet light.

5. The organic-inorganic hybrid compound according to claim 1, characterized in that The organic-inorganic hybrid compound has a radiofluorescent property, and under X-ray excitation, the emission peak is located at 545nm; Preferably, the organic-inorganic hybrid compound exhibits yellow-green fluorescence under 50 kV X-ray excitation.

6. The method for preparing the organic-inorganic hybrid compound according to any one of claims 1 to 5, characterized in that: The preparation method comprises: The raw materials of SbBr3, Ga2O3, HBr and DMSO are mixed, placed in a sealed container, crystallized, and cooled to obtain the organic-inorganic hybrid compound.

7. The preparation method according to claim 6, characterized in that The usage ratio of SbBr3, Ga2O3, HBr, and DMSO is 0.15mmol: 0.3-0.5mmol: 0.2-0.3mL: 0.8-1.5mL; Wherein, HBr is a 40 wt% HBr solution.

8. The preparation method according to claim 6, characterized in that The crystallization temperature is 100-150° C., and the crystallization time is 18-36 hours.

9. Use of the organic-inorganic hybrid compound according to any one of claims 1 to 5 in X-ray imaging.

10. The use according to claim 9, characterized in that The organic-inorganic hybrid compound is prepared into powder, uniformly dispersed in PDMS, and then spin-coated, heated and dried, and solidified into a film to prepare a fluorescent screen used as a scintillating fluorescent screen for X-ray imaging.

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