A silver-sulfur cluster with six cores, and a preparation method and application thereof
By synthesizing the hexanuclear silver-sulfur cluster Ag6(TS)6 through solution reaction at room temperature or low temperature, the problems of harsh synthesis conditions and limited light output of existing scintillation materials have been solved, enabling applications of efficient X-ray detection and imaging.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- FUJIAN INST OF RES ON THE STRUCTURE OF MATTER CHINESE ACAD OF SCI
- Filing Date
- 2023-05-31
- Publication Date
- 2026-04-17
AI Technical Summary
Existing scintillator materials have demanding synthesis conditions, long cycles, and limited light output, making it difficult to meet the requirements of economic efficiency, environmental protection, and high sensitivity.
The hexanuclear silver-sulfur cluster Ag6(TS)6 was synthesized by solution reaction at room temperature or low temperature. The silver source was stabilized by a complexing agent to form a trigonal crystal structure compound with efficient X-ray attenuation and thermally activated delayed fluorescence properties.
It achieves efficient X-ray light output, stable thermal decomposition temperature and radiation resistance, simplifies the preparation process, reduces costs, and is suitable for X-ray detection and imaging.
Smart Images
Figure CN116854640B_ABST
Abstract
Description
Technical Field
[0001] This application relates to a hexanuclear silver-sulfur cluster, its preparation method, and its application, belonging to the field of crystal technology. Background Technology
[0002] With the rapid development of science and technology, radiation detectors play a vital role in fields such as medical diagnosis and treatment, homeland security, astrophysics, and space exploration. Currently, the most widely used radiation detectors are scintillation detectors, in which scintillation materials are the core materials that determine the detector's performance. Scintillation materials are functional materials capable of absorbing the energy of high-energy rays or particles such as X-rays and gamma rays and converting it into low-energy ultraviolet to near-infrared light. Currently, commercially available typical scintillation materials mainly include NaI:Tl and Bi4Ge3O. 12 Materials such as BGO and LaBr3 are used, with NaI:Tl exhibiting high light yield but being prone to deliquescence, thus limiting its practical applications. The growth conditions for BGO and LaBr3 crystals are demanding, requiring reaction temperatures above 1000℃ and long reaction cycles. The development of an economically sound, environmentally friendly, and energy-saving society places higher demands on the design of scintillation materials. The goal is to create simple, easily synthesized, stable, and highly sensitive radiation-responsive materials. Hybrid crystalline scintillation materials have attracted widespread attention due to their advantages, including availability through simple solution reactions, rich and designable structures, and adjustable functions; however, their relatively limited light output restricts their development. Summary of the Invention
[0003] In view of the above, this application aims to solve at least one of the problems existing in the prior art, such as harsh reaction conditions, long synthesis cycle, and limited light output. This application provides a hexanuclear silver-sulfur cluster Ag6(TS)6 that can be easily synthesized through solution reaction at room temperature or under low-temperature solvothermal reaction conditions. This compound contains abundant heavy metal elements, enabling efficient X-ray attenuation; furthermore, this compound exhibits thermally activated delayed fluorescence properties, which are beneficial for triplet exciton emission under X-ray radiation, thereby achieving high X-ray light output.
[0004] According to one aspect of this application, a hexanuclear silver-sulfur cluster is provided, the chemical formula of which is Ag6(TS)6, wherein TS represents the structural formula shown in Formula I below:
[0005]
[0006] In Formula I, R1 and R2 are independently selected from methyl, ethyl, phenyl, halogen, and hydroxyl.
[0007] Optionally, the hexanuclear silver-sulfur cluster belongs to the trigonal crystal system; the space group is
[0008] Optionally, in the unit cell parameters of the hexanuclear silver-sulfur cluster,
[0009] Preferably,
[0010] More preferably,
[0011] Optionally, in the unit cell parameters of the hexanuclear silver-sulfur cluster, α = 90°, β = 90°, γ = 120°, Z = 36; the unit cell volume is:
[0012] Optionally, in Formula I, R1 and R2 are methyl groups. In this case, the chemical formula of the hexanuclear silver-sulfur cluster is Ag6(dmpymt)6, where dmpymt represents deprotonated 2-mercapto-4,6-dimethylpyrimidine.
[0013] Optionally, the photoluminescence quantum yield of the hexanuclear silver-sulfur cluster is ≥80%.
[0014] Preferably, the photoluminescence quantum yield of the hexanuclear silver-sulfur cluster is ≥85%.
[0015] More preferably, the photoluminescence quantum yield of the hexanuclear silver-sulfur cluster is ≥90%.
[0016] Optionally, the decay lifetime of the hexanuclear silver-sulfur cluster is ≥10 μs.
[0017] Optionally, the decay lifetime of the hexanuclear silver-sulfur cluster is 10-25 μs.
[0018] Preferably, the decay lifetime of the hexanuclear silver-sulfur cluster is 12-20 μs.
[0019] Optionally, the X-ray light output of the hexanuclear silver-sulfur cluster is ≥10,000 photons / MeV.
[0020] Preferably, the X-ray light output of the hexanuclear silver-sulfur cluster is ≥11,000 photons / MeV.
[0021] More preferably, the X-ray light output of the hexanuclear silver-sulfur cluster is ≥12,000 photons / MeV.
[0022] Optionally, the lower limit of X-ray detection for the hexanuclear silver-sulfur cluster is ≤300 nGy / s.
[0023] Preferably, the lower limit of X-ray detection for the hexanuclear silver-sulfur cluster is ≤250 nGy / s.
[0024] More preferably, the lower limit of X-ray detection for the hexanuclear silver-sulfur cluster is ≤220 nGy / s.
[0025] Optionally, the X-ray imaging resolution of the hexanuclear silver-sulfur cluster is ≥10 lp / mm.
[0026] Preferably, the X-ray imaging resolution of the hexanuclear silver-sulfur cluster is ≥15 lp / mm.
[0027] Optionally, the thermal decomposition temperature of the hexanuclear silver-sulfur cluster is ≥250℃.
[0028] Preferably, the thermal decomposition temperature of the hexanuclear silver-sulfur cluster is ≥280℃.
[0029] More preferably, the thermal decomposition temperature of the hexanuclear silver-sulfur cluster is ≥300℃.
[0030] According to this application, the hexanuclear silver-sulfur cluster Ag6(TS)6 belongs to the trigonal crystal system; space group is [missing information].
[0031] In the unit cell parameters, Preferably, More preferably, α = 90°, β = 90°, γ = 120°, Z = 36; cell volume is This compound is typically a pale yellow, transparent, blocky crystal with a zero-dimensional hexanuclear structure, and exhibits a dazzling green light when excited by light with wavelengths of 290-450 nm and X-rays.
[0032] According to another aspect of this application, a method for preparing the hexanuclear silver-sulfur clusters as described above is provided, comprising:
[0033] In the presence of a complexing agent, a raw material containing a thiol compound corresponding to Formula I and a silver source is reacted in a reaction medium, and the product is separated and washed to obtain the hexanuclear silver-sulfur cluster.
[0034] Optionally, the silver source is selected from at least one of AgNO3, AgCl, and AgBr.
[0035] Optionally, the thiol compound is 2-mercapto-4,6-dimethylpyrimidine.
[0036] Optionally, the molar ratio of the thiol compound to the silver source is 1:1-2.
[0037] Optionally, the molar ratio of the thiol compound to the silver source is independently selected from any value or a range between 1:1.0, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, and 1:2.0.
[0038] In one embodiment, the molar ratio of the thiol compound to the silver source is 1:1.0-1.2.
[0039] Optionally, the complexing agent is selected from at least one of ethylenediamine and triethylamine.
[0040] According to this application, by introducing a complexing agent into the reaction system, the silver source first forms a complex, which helps to maintain the stable existence of the silver source and makes it easier for it to participate in the reaction of the above-mentioned thiol compounds.
[0041] Optionally, the molar ratio of the thiol compound to the complexing agent is 1:0.05-0.2.
[0042] Optionally, the molar ratio of the thiol compound to the complexing agent is independently selected from any value or a range between 1:0.05, 1:0.06, 1:0.07, 1:0.08, 1:0.09, 1:0.10, 1:0.11, 1:0.12, 1:0.13, 1:0.14, 1:0.15, 1:0.16, 1:0.17, 1:0.18, 1:0.19, and 1:0.20.
[0043] In one embodiment, the molar volume ratio of the thiol compound to the complexing agent is 1 mol: 0.1-0.2 ml.
[0044] Optionally, the reaction medium comprises methanol and DMF, wherein the volume ratio of methanol to DMF is 3:1-2.
[0045] Optionally, in the reaction medium, the volume ratio of methanol to DMF is independently selected from any value or a range between any two of 3:1.0, 3:1.1, 3:1.2, 3:1.3, 3:1.4, 3:1.5, 3:1.6, 3:1.7, 3:1.8, 3:1.9, and 3:2.0.
[0046] In one embodiment, the volume ratio of methanol to DMF in the reaction medium is 3:1.0 to 3:1.2.
[0047] Optionally, the ratio of the molar number of the thiol compound to the total volume of methanol and DMF contained in the reaction medium is 0.02-0.12 mmol: 4-6 mL.
[0048] Optionally, in the above proportional relationship, the molar number of the thiol compound is independently selected from any value or a range between any two of 0.02 mmol, 0.03 mmol, 0.04 mmol, 0.05 mmol, 0.06 mmol, 0.07 mmol, 0.08 mmol, 0.09 mmol, 0.10 mmol, 0.11 mmol, and 0.12 mmol; and the total volume of methanol and DMF contained in the reaction medium is independently selected from any value or a range between any two of 4.0 mL, 4.1 mL, 4.2 mL, 4.3 mL, 4.4 mL, 4.5 mL, 4.6 mL, 4.7 mL, 4.8 mL, 4.9 mL, 5.0 mL, 5.1 mL, 5.2 mL, 5.3 mL, 5.4 mL, 5.5 mL, 5.6 mL, 5.7 mL, 5.8 mL, 5.9 mL, and 6.0 mL.
[0049] Preferably, the ratio of the molar number of the thiol compound to the total volume of methanol and DMF contained in the reaction medium is 0.03-0.10 mmol: 4-5 mL.
[0050] Optionally, the reaction medium may further comprise at least one selected from acetone and acetonitrile.
[0051] Optionally, the reaction medium comprises methanol, DMF and acetone, wherein the volume ratio of methanol, DMF and acetone is 3:1-2:1-2.
[0052] Optionally, the reaction medium comprises methanol, DMF, and acetonitrile, wherein the volume ratio of methanol, DMF, and acetonitrile is 3:1-2:1-2.
[0053] According to this application, the reaction can be carried out by a volatilization reaction at room temperature or by a solvothermal reaction.
[0054] Optionally, the reaction is a volatilization reaction at room temperature, and the volatilization time is 4-72 hours.
[0055] According to this application, the term "normal temperature" means, for example, 15°C, 16°C, 17°C, 18°C, 19°C, 20°C, 21°C, 22°C, 23°C, 24°C, 25°C, 26°C, or a range of any two of these temperatures.
[0056] Optionally, the volatilization time of the room temperature volatilization reaction is independently selected from any value or a range between 4h, 8h, 12h, 16h, 20h, 24h, 28h, 32h, 36h, 40h, 44h, 48h, 52h, 56h, 60h, 64h, 68h, and 72h.
[0057] Optionally, the reaction is a solvothermal reaction, with a temperature of 90-120℃ and a time of 12-72h.
[0058] Optionally, the temperature of the solvothermal reaction is independently selected from any value or a range between any two of 90°C, 93°C, 95°C, 98°C, 100°C, 102°C, 105°C, 107°C, 110°C, 113°C, 115°C, 118°C, and 120°C.
[0059] Optionally, the time of the solvothermal reaction is independently selected from any value or a range between 12h, 16h, 20h, 24h, 28h, 32h, 36h, 40h, 44h, 48h, 52h, 56h, 60h, 64h, 68h, and 72h.
[0060] In one specific implementation, the method includes the following steps:
[0061] A mercapto compound corresponding to Formula I and a silver source in a molar ratio of 1:1-2, along with methanol and DMF in a volume ratio of 3:1-2, are placed in a beaker or glass vial. Then, 0.1-0.2 mL of triethylamine or ethylenediamine is added to initiate the reaction. The reaction is carried out at room temperature for 4-72 h, or at 90-120 °C for 12-72 h. After the reaction is completed, the mixture is cooled to room temperature, the solid product is filtered, and washed with a mixed solvent of ethanol and DMF to obtain pale yellow, transparent, blocky hexanuclear silver-sulfur clusters.
[0062] In another specific implementation, the method includes the following steps:
[0063] 2-Mercapto-4,6-dimethylpyrimidine and a silver source in a molar ratio of 1:1-2, along with methanol, acetone / acetonitrile, and DMF in a volume ratio of 3:1-2:1-2, were placed in a beaker or glass vial. Then, 0.1-0.2 mL of triethylamine or ethylenediamine was added to initiate the reaction. The reaction temperature was room temperature or 90-120℃, and the reaction time was 4-72 h. After the reaction was completed, the mixture was cooled to room temperature, the solid product was filtered, and washed with a mixed solvent of ethanol and DMF to obtain pale yellow, transparent, blocky crystalline hexanuclear silver-sulfur clusters Ag6(dmpymt)6.
[0064] According to another aspect of this application, the hexanuclear silver-sulfur clusters described above, and the hexanuclear silver-sulfur clusters prepared by the method described above, are provided for use as thermally activated delayed fluorescence luminescent materials and X-ray scintillation detection materials.
[0065] Optionally, the hexanuclear silver-sulfur clusters are used in light-emitting diodes, radiation detection dosimeters, and X-ray scintillator medical imaging.
[0066] The beneficial effects that this application can produce include:
[0067] 1) The hexanuclear silver-sulfur clusters according to this application can achieve efficient X-ray attenuation, have high structural thermal stability and radiation resistance, and exhibit thermally activated delayed fluorescence characteristics and high quantum yield, thus achieving high X-ray light output.
[0068] 2) The preparation method of the hexanuclear silver-sulfur cluster according to this application can be achieved simply through solution reaction under relatively mild conditions, with low cost and strong industrial feasibility.
[0069] 3) The hexanuclear silver-sulfur clusters according to this application can be used as X-ray scintillation materials to achieve X-ray scintillation detection with high sensitivity, low detection limit, high imaging resolution and stable light response. Attached Figure Description
[0070] Figure 1 This is a schematic diagram of the three-dimensional structure of the hexanuclear silver-sulfur cluster according to this application.
[0071] Figure 2 This is the X-ray powder diffraction pattern of sample 1 in Example 1 of this application.
[0072] Figure 3 This is the thermogravimetric spectrum of sample 1 in Example 1 of this application.
[0073] Figure 4 This is the photoluminescence spectrum of sample 1 in Example 1 of this application.
[0074] Figure 5 This is the quantum yield spectrum of sample 1 in Example 1 of this application.
[0075] Figure 6 This is the fitted curve of the variable temperature lifetime-temperature of sample 1 in Example 1 of this application.
[0076] Figure 7 This is the scintillation emission curve of sample 1 in Example 1 of this application.
[0077] Figure 8 This is the X-ray response sensitivity curve of sample 1 in Example 1 of this application.
[0078] Figure 9 This is the X-ray detection limit curve of sample 1 in Example 1 of this application.
[0079] Figure 10 The following are the characterization results of the scintillation screen film prepared for sample 1 in Example 1 of this application, wherein (A) is an optical imaging photograph of the film; (B) is a scanning electron microscope photograph of the film; and (C) is an X-ray imaging resolution curve of the film. Detailed Implementation
[0080] As previously stated, this application relates to a hexanuclear silver-sulfur cluster, its preparation method, and its applications. The chemical formula of the hexanuclear silver-sulfur cluster is Ag6(TS)6, where TS represents the structural formula shown in Formula I below:
[0081]
[0082] In Formula I, R1 and R2 are independently selected from methyl, ethyl, phenyl, halogen, and hydroxyl.
[0083] According to this application, the hexanuclear silver-sulfur cluster belongs to the trigonal crystal system; space group is In the unit cell parameters, Preferred More α = 90°, β = 90°, γ = 120°, Z = 36; cell volume is
[0084] According to the schematic diagram of the three-dimensional structure of the hexanuclear silver-sulfur cluster in this application, as shown below... Figure 1 As shown.
[0085] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.
[0086] Experimental methods not specified in the following examples are generally performed under standard conditions or as recommended by the manufacturer.
[0087] Unless otherwise specified, the raw materials and reagents used in the embodiments of this application were all purchased commercially.
[0088] The analytical measuring instruments used in the embodiments of this application are as follows:
[0089] Single-crystal structure characterization: collected on a Rigaku FR-X type single-crystal diffractometer, Mo target, K α Radiation source (λ=0.7107nm), test temperature 273K.
[0090] Thermogravimetric analysis: performed using a METTLER TOLEDO thermogravimetric analyzer.
[0091] Photoluminescence spectroscopy, quantum yield, and decay lifetime: performed using an FLS1000 fluorescence spectrometer.
[0092] Scintillation performance (X-ray response sensitivity, X-ray detection limit, and X-ray imaging resolution) was measured on an X-ray scintillation spectrometer (self-built).
[0093] XRD: Performed using a Rigaku Miniflex 600 X-ray diffractometer.
[0094] Scanning electron microscopy: Performed using a JSM6700-F scanning electron microscope.
[0095] Example 1
[0096] AgNO3 (0.03 mmol) and 2-mercapto-4,6-dimethylpyrimidine (0.03 mmol) were placed in a 10 mL glass vial at a 1:1 molar ratio. Methanol (3 mL), acetone (2 mL), DMF (1 mL), and triethylamine (0.1 mL) were then added for a solvothermal reaction. The reaction was carried out at 90 °C for 72 h. After the reaction was complete, the mixture was cooled to room temperature, the solid product was filtered, and washed with a mixed solvent of ethanol and DMF (1:1, v / v) to obtain pale yellow, transparent, blocky crystals. The obtained crystals were designated as Sample 1.
[0097] X-ray powder diffraction was performed on sample 1 prepared in Example 1, and the results are as follows: Figure 2 As shown. By Figure 2 As can be seen, the position of the peak in the XRD spectrum of sample 1 is completely consistent with the simulation results, confirming that the sample is indeed a pure phase, namely the hexanuclear silver-sulfur cluster Ag6(dmpymt)6.
[0098] Thermogravimetric analysis was performed on sample 1, and the results are as follows: Figure 3 As shown. By Figure 3 As can be seen, Sample 1 remains stable below approximately 300°C, exhibiting excellent thermal stability. Furthermore, Sample 1 maintains its structural integrity even after immersion in water for 3 months or in solutions with pH = 4-9 for 2 days. Moreover, under at least 10 hours of continuous X-ray irradiation (irradiation conditions: X-ray tube voltage 50 kV, X-ray dose rate 12.4 mGy / s), the scintillation performance of Sample 1 did not show a significant decrease. These properties are uncommon in silver clusters protected by monolayer ligands.
[0099] The photoluminescence properties of sample 1 at room temperature were analyzed, and the results are as follows: Figure 4 and Figure 5 As shown, Sample 1, when excited at 300-450 nm (optimal excitation wavelength 365 nm), exhibits green light emission at 530 nm. Figure 5 As can be seen, the photoluminescence quantum yield (PLQY) of sample 1 is as high as 91.6%. Such a high quantum yield is also uncommon in silver clusters.
[0100] The temperature-dependent photoluminescence properties of sample 1 were analyzed, and the results are as follows: Figure 6 As shown, the lifetime of sample 1 gradually decreases with increasing temperature. The fitting results demonstrate that the energy level difference ΔE between the singlet state S1 and the triplet state T1... ST The voltage is 0.113 eV, which meets the conditions for the thermally activated delayed fluorescence property. (From...) Figure 6Furthermore, it can be seen that the fitting curve of Sample 1 is in the plateau region below 180K, proving that Sample 1 mainly emits phosphorescence within this temperature range; the fitting curve of Sample 1 at 298K shows a downward trend, proving that the luminescence of Sample 1 at 298K consists of thermally activated delayed fluorescence and phosphorescence. Therefore, temperature-dependent spectral testing proves that the high quantum yield of Sample 1 originates from the combined contribution of thermally activated delayed fluorescence and phosphorescence.
[0101] The scintillation luminescence properties of sample 1 were characterized, and the results are as follows: Figure 7-9 As shown. According to Figure 7 The scintillation emission spectra of sample 1 at different radiation dose rates were obtained. Figure 8 . Figure 8 This indicates that the scintillation intensity of Sample 1 exhibits a good linear relationship with the dose rate, and the slope of the data line is proportional to the sample's response sensitivity. Therefore, Sample 1 demonstrates better response sensitivity than commercially available BGO. Furthermore, Figure 9 The detection limit of sample 1 was 208.65 nGy / s, which is 26 times lower than the detection limit of commercial BGO (765.11 nGy / s).
[0102] Thin-film imaging was performed on sample 1. 200 mg of sample 1 was placed in 2 mL of ethanol and sonicated for 2 hours to obtain a microcrystalline suspension of sample 1. This microcrystalline suspension was then dropped onto a 3 × 3 cm... 2 On a quartz substrate, a low-speed spin coating at 300 rpm is then performed to obtain... Figure 10 The scintillation film shown is used in X-ray imaging experiments, achieving a spatial resolution of 16 lp / mm.
[0103] Example 2
[0104] AgCl (0.05 mmol) and 2-mercapto-4,6-dimethylpyrimidine (0.05 mmol) were placed in a 10 mL glass vial at a 1:1 molar ratio. Methanol (3 mL), acetone (1 mL), DMF (1 mL), and ethylenediamine (0.1 mL) were then added for a solvothermal reaction. The reaction was carried out at 90 °C for 72 h. After the reaction was complete, the mixture was cooled to room temperature, the solid product was filtered, and washed with a mixture of ethanol and DMF (1:1, v / v) to obtain pale yellow, transparent, blocky crystals. The obtained crystals were designated as Sample 2, and XRD characterization confirmed that this sample was a hexanuclear silver-sulfur cluster Ag6(dmpymt)6.
[0105] Example 3
[0106] AgNO3 (0.03 mmol) and 2-mercapto-4,6-dimethylpyrimidine (0.03 mmol) were placed in a 10 mL glass vial at a 1:1 molar ratio. Methanol (3 mL), acetonitrile (2 mL), DMF (1 mL), and triethylamine (0.1 mL) were then added for a solvothermal reaction. The reaction was carried out at 100 °C for 72 h. After the reaction was complete, the mixture was cooled to room temperature, the solid product was filtered, and washed with a mixture of ethanol and DMF (1:1, v / v) to obtain pale yellow, transparent, blocky crystals. The obtained crystals were designated as Sample 3, and XRD characterization confirmed that this sample was a hexanuclear silver-sulfur cluster Ag6(dmpymt)6.
[0107] Example 4
[0108] AgNO3 (0.1 mmol) and 2-mercapto-4,6-dimethylpyrimidine (0.1 mmol) were placed in a 10 mL glass vial at a 1:1 molar ratio. Methanol (3 mL), acetonitrile (1 mL), DMF (1 mL), and ethylenediamine (0.2 mL) were then added for a solvothermal reaction at 120 °C for 72 h. After the reaction, the mixture was cooled to room temperature, the solid product was filtered, and washed with a 1:1 mixture of ethanol and DMF (v / v) to obtain pale yellow, transparent, blocky crystals. The obtained crystals were designated as Sample 4, and XRD characterization confirmed that this sample was a hexanuclear silver-sulfur cluster Ag6(dmpymt)6.
[0109] Example 5
[0110] AgNO3 (0.1 mmol) and 2-mercapto-4,6-dimethylpyrimidine (0.1 mmol) were placed in a 10 mL glass vial at a 1:1 molar ratio. Methanol (3 mL), acetone (2 mL), DMF (1 mL), and ethylenediamine (0.2 mL) were then added for a solvothermal reaction at 100 °C for 48 h. After the reaction, the mixture was cooled to room temperature, the solid product was filtered, and washed with a mixture of ethanol and DMF (1:1, v / v) to obtain pale yellow, transparent, blocky crystals. The obtained crystals were designated as Sample 5, and XRD characterization confirmed that this sample was a hexanuclear silver-sulfur cluster Ag6(dmpymt)6.
[0111] Example 6
[0112] AgNO3 (0.08 mmol) and 2-mercapto-4,6-dimethylpyrimidine (0.08 mmol) were placed in a 25 mL beaker at a 1:1 molar ratio. Methanol (3 mL), acetone (2 mL), DMF (1 mL), and triethylamine (0.2 mL) were then added, and the mixture was allowed to evaporate at room temperature for 4 hours. A pale yellow, transparent, blocky crystalline product gradually formed at the bottom of the beaker. The solid product was filtered and washed with a mixture of ethanol and DMF (1:1, v / v) to obtain pale yellow, transparent, blocky crystals. This crystal was designated as sample 6, and XRD characterization confirmed that it was a hexanuclear silver-sulfur cluster Ag6(dmpymt)6.
[0113] Example 7
[0114] AgNO3 (0.08 mmol) and 2-mercapto-4,6-dimethylpyrimidine (0.08 mmol) were placed in a 25 mL beaker at a 1:1 molar ratio. Methanol (3 mL), acetonitrile (2 mL), DMF (1 mL), and triethylamine (0.2 mL) were then added, and the mixture was allowed to evaporate at room temperature for 12 h. A pale yellow, transparent, blocky crystalline product gradually formed at the bottom of the beaker. The solid product was filtered and washed with a mixture of ethanol and DMF (1:1, v / v) to obtain pale yellow, transparent, blocky crystals. This crystal was designated as sample 7, and XRD characterization confirmed that it was a hexanuclear silver-sulfur cluster Ag6(dmpymt)6.
[0115] Example 8
[0116] AgNO3 (0.1 mmol) and 2-mercapto-4,6-dimethylpyrimidine (0.1 mmol) were placed in a 25 mL beaker at a 1:1 molar ratio. Methanol (3 mL), acetonitrile (2 mL), DMF (1 mL), and ethylenediamine (0.1 mL) were then added, and the mixture was allowed to evaporate at room temperature for 24 h. A pale yellow, transparent, blocky crystalline product gradually formed at the bottom of the beaker. The solid product was filtered and washed with a mixture of ethanol and DMF (1:1, v / v) to obtain pale yellow, transparent, blocky crystals. This crystal was designated as sample 8, and XRD characterization confirmed it to be a hexanuclear silver-sulfur cluster Ag6(dmpymt)6.
[0117] Example 9
[0118] AgNO3 (0.1 mmol) and 2-mercapto-4,6-dimethylpyrimidine (0.1 mmol) were placed in a 25 mL beaker at a 1:1 molar ratio. Methanol (3 mL), acetone (2 mL), DMF (1 mL), and ethylenediamine (0.1 mL) were then added, and the mixture was allowed to evaporate at room temperature for 48 h. A pale yellow, transparent, blocky crystalline product gradually formed at the bottom of the beaker. The solid product was filtered and washed with a mixture of ethanol and DMF (1:1, v / v) to obtain pale yellow, transparent, blocky crystals. This crystal was designated as sample 9, and XRD characterization confirmed it to be a hexanuclear silver-sulfur cluster Ag6(dmpymt)6.
[0119] Example 10
[0120] AgNO3 (0.1 mmol) and 2-mercapto-4,6-diphenylpyrimidine (0.1 mmol) were placed in a 25 mL beaker at a 1:1 molar ratio. Methanol (3 mL), acetone (2 mL), DMF (1 mL), and ethylenediamine (0.1 mL) were then added, and the mixture was allowed to evaporate at room temperature for 48 h. A pale yellow, transparent, blocky crystalline product gradually formed at the bottom of the beaker. The solid product was filtered and washed with a mixture of ethanol and DMF (1:1, v / v) to obtain pale yellow, transparent, blocky crystals. This crystal was designated as sample 10.
[0121] Example 11
[0122] AgNO3 (0.08 mmol) and 2-mercapto-4,6-diphenylpyrimidine (0.08 mmol) were placed in a 25 mL beaker at a 1:1 molar ratio. Methanol (3 mL), acetonitrile (2 mL), DMF (1 mL), and ethylenediamine (0.1 mL) were then added for a solvothermal reaction. The reaction temperature was 100 °C, and the reaction time was 48 h. A pale yellow, transparent, blocky crystalline product gradually formed at the bottom of the beaker. The solid product was filtered and washed with a mixture of ethanol and DMF (1:1, v / v) to obtain pale yellow, transparent, blocky crystals. This crystal was designated as Sample 11.
[0123] Example 12
[0124] AgNO3 (0.08 mmol) and 2-mercapto-4,6-dibromopyrimidine (0.08 mmol) were placed in a 25 mL beaker at a 1:1 molar ratio. Methanol (3 mL), acetonitrile (2 mL), DMF (1 mL), and ethylenediamine (0.1 mL) were then added for a solvothermal reaction. The reaction temperature was 90 °C, and the reaction time was 48 h. A pale yellow, transparent, blocky crystalline product gradually formed at the bottom of the beaker. The solid product was filtered and washed with a mixture of ethanol and DMF (1:1, v / v) to obtain pale yellow, transparent, blocky crystals. This crystal was designated as Sample 12.
[0125] Example 13
[0126] AgNO3 (0.08 mmol) and 2-mercapto-4,6-dihydroxypyrimidine (0.08 mmol) were placed in a 25 mL beaker at a 1:1 molar ratio. Methanol (3 mL), acetonitrile (2 mL), DMF (1 mL), and ethylenediamine (0.1 mL) were then added for a solvothermal reaction. The reaction was carried out at 90 °C for 72 h. A pale yellow, transparent, blocky crystalline product gradually formed at the bottom of the beaker. The solid product was filtered and washed with a mixture of ethanol and DMF (1:1, v / v) to obtain pale yellow, transparent, blocky crystals. This crystal was designated as Sample 13.
[0127] The performance of samples 2-13 was tested using the same experimental procedure as that of sample 1. The results show that the detection performance of samples 2-13 is similar to that of sample 1, with slight differences in specific values.
[0128] The above descriptions are merely several embodiments of this application and are not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, these embodiments are not intended to limit this application. Any modifications or alterations made by those skilled in the art using the disclosed technical content without departing from the scope of the technical solution of this application are equivalent to equivalent implementations and fall within the scope of the technical solution of this application.
Claims
1. A hexanuclear silver-sulfur cluster, characterized in that, The chemical formula of the hexanuclear silver-sulfur cluster is Ag6(TS)6, where TS represents the structural formula shown in Formula I below: (I) In Formula I, R1 and R2 are independently selected from methyl groups; and the hexanuclear silver-sulfur cluster belongs to the trigonal crystal system with space group I. The unit cell parameters are a = 13.5907(3) Å, b = 13.5907(3) Å, c = 43.6638(10) Å. α =90°, β =90°, γ =120°, Z=36, cell volume is V=6984.5(3) ų; the photoluminescent quantum yield of the hexanuclear silver-sulfur cluster is ≥80%.
2. The hexanuclear silver-sulfur cluster according to claim 1, characterized in that... The photoluminescence quantum yield is ≥85%.
3. The hexanuclear silver-sulfur cluster according to claim 1, characterized in that, The photoluminescent quantum yield of the hexanuclear silver-sulfur cluster is ≥80%; The decay lifetime of the hexanuclear silver-sulfur cluster is ≥10 μs; The X-ray light output of the hexanuclear silver-sulfur cluster is ≥10,000 photons / MeV; The lower limit of X-ray detection for the hexanuclear silver-sulfur cluster is ≤300 nGy / s; The X-ray imaging resolution of the hexanuclear silver-sulfur cluster is ≥10 lp / mm; The thermal decomposition temperature of the hexanuclear silver-sulfur cluster is ≥250℃.
4. A method for preparing hexanuclear silver-sulfur clusters according to any one of claims 1-3, characterized in that, include: In the presence of a complexing agent, a raw material containing a thiol compound corresponding to Formula I and a silver source is reacted in a reaction medium, and the product is separated and washed to obtain the hexanuclear silver-sulfur cluster.
5. The method according to claim 4, characterized in that, The silver source is selected from at least one of AgNO3, AgCl, and AgBr; The thiol compound is 2-mercapto-4,6-dimethylpyrimidine; The molar ratio of the thiol compound to the silver source is 1:1-2; The complexing agent is selected from at least one of ethylenediamine and triethylamine; The molar ratio of the thiol compound to the complexing agent is 1:0.05-0.
2.
6. The method according to claim 4, characterized in that, The reaction medium contains methanol and DMF, wherein the volume ratio of methanol to DMF is 3:1-2; The ratio of the molar number of the thiol compound to the total volume of methanol and DMF contained in the reaction medium is 0.02-0.12 mmol: 4-6 mL.
7. The method according to claim 4, characterized in that, The reaction is a volatilization reaction at room temperature, with a volatilization time of 4-72 h; The reaction is a solvothermal reaction, with a temperature of 90-120℃ and a time of 12-72 h.
8. The application of hexanuclear silver-sulfur clusters according to any one of claims 1-3, and hexanuclear silver-sulfur clusters prepared by the method according to any one of claims 4-7, as thermally activated delayed fluorescence luminescent materials and X-ray scintillation detection materials.
9. The application according to claim 8, characterized in that, The hexanuclear silver-sulfur clusters are used in light-emitting diodes, radiation detection dosimeters, and X-ray scintillator medical imaging.