A type of Cl / Br halogen-doped ionic antimony complex and its preparation method and application

Abstract

The present invention belongs to the field of preparation and application of metal materials and relates to a class of Cl / Br halogen-doped ionic antimony complexes and their preparation methods and applications. The general structural formula of the complex is shown below: #imgabs0#, wherein R is methyl, ethyl, n-propyl or n-butyl; and x=0, 1, 2, 3, 4 or 5. The preparation method comprises the following steps: adding a benzylamine salt and antimony trichloride or antimony tribromide to a solvent in a molar ratio, reacting the mixture, and using ether as a reverse solvent to obtain a single crystal of the target product; or adding a benzylamine salt and antimony trichloride or antimony tribromide to a solvent in a molar ratio, and heating the mixture to obtain a single crystal of the target product. The luminescence properties of the material can be controlled by varying the halogen type or organic cation in the complex. Due to the advantages of the antimony complex, such as high stability, simple preparation, and high-efficiency, short-life luminescence, the ionic antimony complex has a wide range of uses and can be applied to fields such as X-ray imaging and lighting displays.

Description

Technical Field

[0001] The present invention belongs to the field of preparation and application of metal materials, and in particular relates to a Cl / Br halogen-doped ion-type antimony complex and a preparation method and application thereof. Background Art

[0002] In recent years, X-ray detection and imaging have attracted widespread attention and research due to their widespread applications in medical diagnosis, environmental monitoring, industrial flaw detection, safety inspection, and astronomical observation. Scintillators are crucial for indirect X-ray detector imaging. Scintillators achieve detection and imaging by converting X-rays into light. Due to their low cost, high efficiency, and excellent stability, indirect X-ray detection is widely used in conventional flat-panel X-ray detectors. Non-lead-based metal complexes such as Sn(II), Cu(I), and Mn(II) are considered promising X-ray scintillator materials due to their excellent luminescence properties. However, Sn(II) is easily oxidized to Sn(IV), resulting in poor stability. Manganese complexes typically luminesce from their inherent spin-orbit-forbidden dd transitions, resulting in lifetimes of hundreds of microseconds or even milliseconds, which cannot meet the requirements for fast X-ray scintillation response. Although these non-lead-based metal halide scintillators have experienced rapid development and achieved some breakthroughs in recent years, X-ray detectors that combine high stability with fast decay have yet to be realized. In addition, the central atomic numbers of these materials are relatively small, and their absorption capacity for X-rays is limited. Therefore, there is an urgent need to develop new scintillator materials with strong X-ray absorption, short luminescence lifetime and high stability to achieve high-performance X-ray detection.

[0003] In recent years, Sb has been widely studied in the field of optoelectronic devices such as light-emitting displays. 3+ Stereochemically active ns 2 Antimony complexes typically exhibit high-efficiency, short-lived luminescence due to their outer electron structure. Furthermore, the relatively high atomic number of Sb facilitates efficient X-ray absorption. Furthermore, antimony complexes offer advantages such as simple preparation and high stability. Therefore, antimony complexes are promising new scintillator materials for high-performance X-ray detectors. Summary of the Invention

[0004] The purpose of the present invention is to address the deficiencies in the prior art and propose a class of Cl / Br halogen-doped ionic antimony complexes, their preparation methods, and applications. Different photoconversions are achieved by regulating the halogen type and organic cations. The main research focuses on the responsiveness of this class of materials to X-rays, with applications in the fields of X-ray detection and imaging.

[0005] In order to achieve the above object, the present invention is achieved through the following technical solutions:

[0006] In a first aspect, the present invention provides a class of Cl / Br halogen-doped ionic antimony complexes, the general structural formula of which is as follows:

[0007]

[0008] Wherein, R is methyl, ethyl, n-propyl or n-butyl; x=0, 1, 2, 3, 4 or 5.

[0009] The complex is specifically one of the following structures:

[0010]

[0011] Wherein R is ethyl and x=4, its structural formula is as follows:

[0012]

[0013] Wherein R is ethyl and x=1, its structural formula is as follows:

[0014]

[0015] In a second aspect, the present invention provides a method for preparing a Cl / Br halogen-doped ionic antimony complex. The method comprises: adding a benzylamine salt and antimony trichloride or antimony tribromide in a molar ratio to a solvent for reaction, and using ether as a counter solvent to obtain a single crystal of the target product; or, adding a benzylamine salt and antimony trichloride or antimony tribromide in a molar ratio to a solvent, and heating the reaction to obtain a single crystal of the target product. The synthesis route is as follows:

[0016]

[0017] Where m=0, 1, 2, n=0, 1, 2.

[0018] Preferably, the heating temperature is 60-80°C.

[0019] When R is ethyl and x=4, the raw materials are added to a reaction flask in a molar ratio of benzyltriethylammonium bromide:benzyltriethylammonium chloride:antimony trichloride=1:1:1, and 5-10 ml of DMF solvent is added. The mixture is stirred for 6 hours. After sufficient dissolution, the reaction flask is placed in a beaker containing 20 ml of diethyl ether. The beaker is then sealed, and the diethyl ether evaporates into the reaction flask as a reverse solvent. The complex has good solubility in solvents such as DMF, but poor solubility in diethyl ether. When the diethyl ether evaporates into the DMF solution containing the complex, the complex precipitates in the form of microcrystals and slowly grows into single crystals. Finally, single crystals of the target product are obtained, which are washed with anhydrous diethyl ether and dried. The synthetic route is as follows:

[0020]

[0021] When R is ethyl and x=1, the raw materials are added to a reaction flask in a molar ratio of benzyltriethylammonium bromide:benzyltriethylammonium chloride:antimony tribromide=1:1:1, and 5-10 ml of acetonitrile are added and heated to obtain a clear solution at a temperature of 60-80°C for 1 hour. After cooling to room temperature, the solution is allowed to stand for a period of time to obtain a single crystal of the target product, which is then washed with anhydrous ether and dried. The synthetic route is as follows:

[0022]

[0023] In a third aspect, the present invention provides a class of Cl / Br halogen-doped ionic antimony complexes for use in the fields of optoelectronic display, bio-imaging and sensing, information recording, and printing.

[0024] Specifically, the antimony complex solution can be used as ink in the printing and printing fields;

[0025] The antimony complex can be made into a fluorescent powder to produce LED light bulbs of different colors;

[0026] The antimony complex can be used as a luminescent material that is responsive to X-rays and can be made into a flexible thin film scintillator screen for use in X-ray detection and imaging.

[0027] The antimony complex can be made into a flexible film, miniaturized, and applied in the optoelectronic field.

[0028] The present invention has the following beneficial effects: (1) The experimental synthesis in the preparation method of the antimony complex of the present invention is simple, and the ladder complex is synthesized using a "one-pot method", can be produced and applied on a large scale, and has low cost and low toxicity.

[0029] (2) The antimony complex prepared by the present invention has excellent photophysical properties, emits orange-yellow light in the solid state, and has a high quantum yield.

[0030] (3) The halogen-doped ionic ladder complex designed by the present invention can achieve light-controllable phenomena by changing the halogen type or organic cation.

[0031] (4) The ladder complex prepared by the present invention is responsive to X-rays and can be prepared into a flexible scintillator film for application in the field of X-ray detection and imaging. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 : Single crystal structures of antimony complex structures (a)-(f) of the present invention;

[0033] Figure 2 : Normalized emission spectra of the antimony complex structures (a)-(f) of the present invention;

[0034] Figure 3 : Solid-state photoluminescence decay curves of the antimony complex structures (a)-(c) of the present invention;

[0035] Figure 4 : CIE 1931 chromaticity diagram of the antimony complex structures (a)-(f) of the present invention;

[0036] Figure 5 : Thermogravimetric analysis curves of the antimony complex structures (a)-(c) of the present invention;

[0037] Figure 6 : X-ray response spectra of the antimony complex structures (a)-(c) of the present invention;

[0038] Figure 7 : X-ray linear response spectra of the antimony complex structures (a)-(c) of the present invention;

[0039] Figure 8 : Flexible thin film scintillator and imaging diagram prepared by the antimony complex structure (c) of the present invention. DETAILED DESCRIPTION

[0040] The present invention will be further described below with reference to the examples, but they are not intended to limit the present invention.

[0041] A type of Cl / Br halogen-doped ionic antimony complex, the general structural formula of the complex is as follows:

[0042]

[0043] Wherein, R is methyl, ethyl, n-propyl or n-butyl; x=0, 1, 2, 3, 4 or 5.

[0044] Specifically, the complex is one of the following structural formulas:

[0045]

[0046] A method for preparing a Cl / Br halogen-doped ionic antimony complex comprises: adding a benzylamine salt and antimony trichloride or antimony tribromide in a molar ratio to a solvent for reaction, and using ether as a counter solvent to obtain a single crystal of the target product; or adding a benzylamine salt and antimony trichloride or antimony tribromide in a molar ratio to a solvent for heating to react, to obtain a single crystal of the target product. The synthesis route is as follows:

[0047] Where m=0, 1, 2, n=0, 1, 2.

[0048] Furthermore, the heating temperature is 60-80°C.

[0049] The present invention selects ligands in which R is ethyl for research. Furthermore, by regulating the ratio of different halogen ions, different antimony complexes can be prepared. The structures of the six antimony complexes studied in the present invention are shown in the figure below:

[0050]

[0051] The specific synthesis method is as follows:

[0052]

[0053] Example 1: Preparation of antimony complex structure (a) single crystal

[0054] According to the molar ratio of benzyltriethylammonium chloride: antimony trichloride = 1:1, the raw materials were added to a reaction flask, and 5 mL of DMF solvent was added. After stirring for 6 hours, after sufficient dissolution, the reaction flask was placed in a beaker containing 20 mL of ether. The beaker was then sealed, and the ether was evaporated into the reaction flask as a reverse solvent. Finally, a single crystal of the target product was obtained, which was washed with anhydrous ether and dried to obtain a single crystal of structure (a).

[0055] Example 2: Preparation of antimony complex structure (b) single crystal

[0056] According to the molar ratio of benzyltriethylammonium bromide: benzyltriethylammonium chloride: antimony trichloride = 1:1:1, the raw materials were added to a reaction flask, and 5 mL of DMF solvent was added. After stirring for 6 hours, after sufficient dissolution, the reaction flask was placed in a beaker containing 20 mL of ether. The beaker was then sealed, and the ether was evaporated into the reaction flask as a reverse solvent. Finally, a single crystal of the target product was obtained, which was washed with anhydrous ether and dried to obtain a single crystal of structure (b).

[0057] Example 3: Preparation of antimony complex structure (c) single crystal

[0058] According to the molar ratio of benzyltriethylammonium bromide: antimony trichloride = 1:1, the raw materials were added to a reaction flask, and 5 mL of DMF solvent was added. After stirring for 6 hours, after sufficient dissolution, the reaction flask was placed in a beaker containing 20 mL of ether. The beaker was then sealed, and the ether was evaporated into the reaction flask as a reverse solvent to finally obtain a single crystal of the target product. It was washed with anhydrous ether and dried to obtain a single crystal of structure (c).

[0059] Example 4: Preparation of antimony complex structure (d) single crystal

[0060] According to the molar ratio of benzyltriethylammonium chloride: antimony tribromide = 1:1, the raw materials were added to a reaction flask, and 5 mL of DMF solvent was added. After stirring for 6 hours, after sufficient dissolution, the reaction flask was placed in a beaker containing 20 mL of ether. The beaker was then sealed, and the ether was evaporated into the reaction flask as a reverse solvent. Finally, a single crystal of the target product was obtained, which was washed with anhydrous ether and dried to obtain a single crystal of structure (d).

[0061] Example 5: Preparation of antimony complex structure (e) single crystal

[0062] The raw materials were added to a reaction flask in a molar ratio of benzyltriethylammonium bromide: benzyltriethylammonium chloride: antimony tribromide = 1:1:1, and 5 mL of acetonitrile was added and heated to obtain a clear solution. The heating temperature was 70°C and the heating time was 1 hour. After cooling to room temperature, the solution was allowed to stand for a period of time to obtain a single crystal of the target product, which was then washed with anhydrous ether and dried to obtain a single crystal of structure (e).

[0063] Example 6: Preparation of antimony complex structure (f) single crystal

[0064] The raw materials were added to a reaction flask in a molar ratio of benzyltriethylammonium bromide:antimony tribromide = 1:1, and 5 mL of acetonitrile was added and heated to obtain a clear solution. The heating temperature was 70°C and the heating time was 1 hour. After cooling to room temperature, the solution was allowed to stand for a period of time to obtain a single crystal of the target product, which was then washed with anhydrous ether and dried to obtain a single crystal of structure (f).

[0065] Example 7: Acquisition of SC-XRD data

[0066] SC-XRD data were obtained on a Bruker Smart Apex CCD diffractometer at room temperature using the ω-2θ scanning technique with graphite monochromator Mo-Kα The single crystal structures of structures (a)-(f) were solved and refined using Olex2 and SHELXS (full matrix least squares on F2). Figure 1 The crystals of structures (a)-(f) are orthorhombic, and the space group is the non-centrosymmetric space group P212121.

[0067] Example 8: Measurement of emission spectrum and luminescence lifetime decay curve

[0068] The emission spectra and luminescence lifetime decay curves were measured on an Edinburgh FLS-980 spectrophotometer. The emission spectra were obtained using a 450W xenon lamp in the range of 400nm-800nm. The normalized emission spectra of the antimony complexes of structures (a)-(f) are shown in Figure 2. Figure 2As shown, the emission characteristic peaks are in the range of 587nm-632nm. The corresponding CIE1931 chromaticity diagram is calculated and kneaded, which is consistent with the orange-yellow light emission; the luminescence lifetime decay curve test uses a 375nm laser. The solid-state photoluminescence decay curves of the antimony complexes of structures (a)-(c) are shown in Figure 3 As shown in Figure 3, it was found that with the incorporation of Br atoms, the solid-state luminescence lifetime decay curve of the antimony complex gradually decreased.

[0069] Example 9: TGA measurement

[0070] TGA measurements were performed using a NETZSCH STA-2500 Regulus thermal analyzer. The temperature was increased at a rate of 10 K / min over a range of 25–600 °C under a 30 mL / min nitrogen atmosphere. The thermogravimetric analysis curves of the antimony complexes of structures (a)–(c) are shown in Figure 1. Figure 5 As shown, the decomposition temperatures (Td) of the antimony complexes of structures (a)-(c) are all higher than 200°C.

[0071] Example 10: Measurement of irradiation emission spectrum and detection limit

[0072] The irradiation emission spectrum and detection limit were measured on an Edinburgh FLS-980 spectrophotometer. The irradiation intensity during measurement was 90.66nGy / s-920.10nGy / s. Figure 6 、 Figure 7 As shown, under X-ray irradiation, the irradiation intensity of this type of antimony complex has a certain linear relationship with the X-ray dose rate and a good detection limit.

[0073] Example 11: Preparation of flexible scintillator film

[0074] Based on the unique orange-yellow emission and high luminescence quantum efficiency of this type of organic-inorganic hybrid antimony complex, it is applied to the field of X-ray imaging.

[0075] Preparation of flexible scintillator film: Taking antimony complex structure C as an example, 0.1g of structure C scintillator and 0.5g of thermoplastic polyurethane elastomer (TPU) were added to a reaction bottle and dissolved with DMF at 60°C with stirring. After 30 minutes, a clear and transparent solution was obtained. The solution was then poured into a mold and placed in a vacuum drying oven at 40°C. After 24 hours, a flexible scintillator film was obtained. This scintillator film does not emit light under sunlight, only showing the translucent white color of the TPU film. However, it emits the color of the complex under ultraviolet and X-ray irradiation; Figure 8 As shown, the left picture shows a scintillator made of structure c antimony complex doped with TPU, which emits orange-yellow light under ultraviolet light. Due to the different absorption of X-rays by different metals, different spatial saturations are formed on the scintillator, and then optical imaging is performed to clearly observe the internal structure of the chip, such as Figure 8As shown in the figure on the right, this type of antimony complex has the advantages of simple synthesis, low cost, low toxicity, large-scale production, and excellent photophysical properties, making it a promising candidate for the next generation of emerging materials for X-ray detection and imaging.

[0076] The above shows and describes the basic principles, main features, and advantages of the present invention. However, the above is only a specific embodiment of the present invention, and the technical features of the present invention are not limited thereto. Any other implementation methods derived by any person skilled in the art without departing from the technical solution of the present invention should be included in the patent scope of the present invention.

Claims

1. Application of a class of Cl / Br halogen-doped ionic antimony complexes in the field of X-ray imaging, characterized in that: The general structural formula of the complex is as follows: Wherein, R is methyl, ethyl, n-propyl or n-butyl; x=0, 1, 2, 3, 4 or 5.

2. The use according to claim 1, characterized in that The preparation method of a type of Cl / Br halogen-doped ionic antimony complex is as follows: According to the molar ratio, benzylamino salt and antimony trichloride or antimony tribromide are added to a solvent and heated to react to obtain a single crystal of the target product. The synthetic route is as follows: wherein m=0, 1, 2, n=0, 1, 2, R is methyl, ethyl, n-propyl or n-butyl; and x=0, 1, 2, 3, 4 or 5.

3. The use according to claim 2, characterized in that The heating temperature is 60-80°C.

4. The use according to claim 2, characterized in that When R is ethyl and X=1, the preparation method of the Cl / Br halogen-doped ionic antimony complex is as follows: in a molar ratio of benzyltriethylammonium bromide:benzyltriethylammonium chloride:antimony tribromide=1:1:1, the raw materials are added to a reaction flask, and 5-10 ml of acetonitrile is added and heated to obtain a clear solution at a temperature of 60-80° C. for 1 hour. After cooling to room temperature, the solution is allowed to stand for a period of time to obtain a single crystal of the target product, which is then washed with anhydrous ether and dried. The synthetic route is as follows:

Images