A class of scintillator materials based on phosphonium ion derivatives, and preparation method and application thereof

Abstract

The application provides a kind of scintillator material based on phosphonium ion derivative and its preparation method and application. The material decouples high-energy ray absorption and luminescence function, uses bulky organic anion containing heavy atoms as high-energy ray absorption unit, and realizes efficient ray absorption by high atomic number. At the same time, the phosphonium cation with thermal activation delayed fluorescence (TADF) characteristics is used as the luminescence unit, and the single line and triplet excitons are captured by TADF mechanism to realize efficient radiation luminescence. The scintillator material is simple to synthesize, has high luminescence efficiency, good solubility, low glass transition temperature, and can be used to prepare large-area transparent scintillator film with high doping concentration by solution processing technology, or glass scintillator screen by melting method. The scintillator screen based on this kind of material can achieve high spatial resolution and radiation luminescence performance, and is suitable for radiation detection, medical imaging, safety inspection and other applications.

Description

Technical Field

[0001] This invention relates to the fields of organic scintillator materials and radiation detection, X-ray imaging, neutron imaging and gamma-ray imaging, specifically to a class of scintillator materials based on phosphonium ion derivatives, their preparation methods and applications. Background Technology

[0002] Scintillator materials, due to their ability to convert ionizing radiation such as high-energy X-rays, gamma rays, and neutron fluxes into visible light, have significant application value in fields such as radiation detection, medical imaging, security inspection, non-destructive testing, and space exploration. Currently, the mainstream scintillators used in commercial applications are mainly based on inorganic crystal materials and plastic scintillators, such as Bi4Ge3O4. 12 (BGO), CsI:Tl, and EJ-276D are examples of materials used in scintillator fabrication. However, both types of materials have their own inherent limitations. Inorganic crystals typically require high temperatures or harsh conditions for synthesis, resulting in high production costs and energy consumption. Furthermore, some systems involve heavy metals or toxic elements, posing environmental pollution risks. Their poor processing performance also hinders the fabrication of large-area, flexible scintillator films using simple processes, limiting their application in portable imaging devices and imaging scenarios with irregular structures. Traditional plastic scintillators, on the other hand, are mainly composed of light elements such as carbon, hydrogen, oxygen, and nitrogen, resulting in low atomic numbers and inherently weak absorption of high-energy rays such as X-rays and gamma rays, thus limiting their detection efficiency.

[0003] To address the aforementioned issues, organic light-emitting materials have attracted widespread attention in recent years due to their advantages such as good solution processability, mild synthesis conditions, low cost, and environmental friendliness, and are expected to replace traditional inorganic scintillators in the fabrication of large-area, flexible imaging films. However, existing organic scintillator materials still face two key bottlenecks in practical applications: firstly, the absorption efficiency of high-energy rays is proportional to the fourth power of the atomic number of the material (attenuation coefficient μ ∝ Z). 4 Organic compounds are mainly composed of light elements with low atomic numbers, which naturally result in a weaker absorption capacity for high-energy rays such as X-rays and gamma rays. Secondly, in organic light-emitting materials, a large number of excitons are generated when high-energy rays interact with organic molecules, of which about 75% are triplet excitons. However, traditional organic scintillator materials mainly rely on singlet excitons for light emission. Triplet excitons are difficult to utilize effectively due to spin confinement, resulting in low exciton utilization and poor radiative emission performance. Summary of the Invention

[0004] To address the technical problems of weak absorption and low exciton utilization in existing organic scintillators, this invention provides a class of organic scintillator materials based on phosphonium ion derivatives. These materials decouple X-ray absorption from luminescence. Specifically, the bulky organic anions containing heavy atoms serve as high-energy X-ray absorption units, achieving efficient X-ray absorption due to their high atomic numbers. Simultaneously, the phosphonium cations, possessing thermally activated delayed fluorescence (TADF) properties, serve as luminescence units, capturing both singlet and triplet excitons through the TADF mechanism, thus achieving efficient luminescence. By separating absorption and emission functions, the organic scintillator materials of this invention effectively avoid the fluorescence quenching problem caused by the direct introduction of heavy atoms in traditional organic scintillator materials. Energy can be directly transferred unidirectionally, thereby simultaneously achieving strong X-ray absorption and high luminescence efficiency. Furthermore, these materials exhibit good solution processability or melt processing characteristics, allowing for the fabrication of large-area transparent scintillator films or glassy scintillator screens with high doping concentrations through simple processes, making them suitable for applications such as high-resolution X-ray imaging and radiation detection.

[0005] This invention provides derivatives based on phosphonium ions, as shown in Formula I, or Formula II, or Formula III or IV:

[0006] Where R is the same or different, and is independently selected from hydrogen, C 1-30 Halogenated alkyl, halogen, cyano, C 1-30 Alkyl, -NHC 1-30 Alkyl, -N(C) 1-30 Alkyl)2, C 6-20 The aryl group, a 5-20 membered heteroaryl group, and one of the groups shown in Formula 1 to Formula 24, wherein at least one R group in Formula I to Formula IV is selected from one of the groups shown in Formula 1 to Formula 24; R1 may be the same or different, and are independently selected from hydrogen and C. 1-30 Halogenated alkyl, halogen, cyano, C 1-30 Alkyl, C 6-20 Aryl, -NHC 1-30 Alkyl, -N(C) 1-30 alkyl)2 and one of the groups shown in formulas 1 to 24;

[0007] In this context, the dashed line (--) indicates a connection point that connects to another unit; R6, R7, R8, R9, R 10 R 11 R 12 R 13 R 14 R 15 R 16R 17 R 18 R 19 R 20 R 21 R 22 R 23 R 24 R 25 R 26 R 27 and R 28 They may be the same or different, and are independently selected from hydrogen, deuterium, tritium, halogen, amino, hydroxyl, cyano, and C. 1-30 Alkyl, Halogenated C 1-30 Alkyl, C 1-30 Alkoxy, -NHC 1-30 Alkyl, -N(C) 1-30 Alkyl group 2, halogenated C 1-30 Alkoxy, C 6-20 Aryl, C 3-20 One of the following: cycloalkyl, 3-20 membered heterocyclic, 5-20 membered heteroaryl and groups shown in Formula 1 to Formula 24; D is an electron-donating group selected from one of Formula 1 to Formula 24, forming an electron-donating group with a dendritic structure; L is selected from ClO4 - BF4 - BBr4 - SeF6 2- SeF5 - SeBr5 - SeBr6 2- SbF6 - PtBr6 2- PtI6 2- NO3 - And one of the structures shown in equations Ia to IXa below:

[0008] R 30 Whether the two are the same or different, they are each independently selected from hydrogen and C. 1-30 Halogenated alkyl, halogen, cyano, C 1-30 Alkyl, -NHC 1-30 Alkyl, -N(C) 1-30 Alkyl)2, C 6-20 One of the aryl group and the 5-20 heteroaryl group.

[0009] According to embodiments of the present invention, R may be the same or different, and is independently selected from hydrogen and C. 1-12 Halogenated alkyl, halogen, cyano, C 1-12 Alkyl, -NHC 1-12 Alkyl, -N(C) 1-12 Alkyl)2, C6-14 The aryl group, a 5-14 heteroaryl group, and one of the groups shown in Formula 1 to Formula 24, wherein one of the R groups in Formula I to Formula IV is selected from one of the groups shown in Formula 1 to Formula 24.

[0010] According to some specific embodiments of the present invention, R may be the same or different, and is independently selected from hydrogen, C 1-6 Halogenated alkyl, halogen, cyano, C 1-6 Alkyl, -NHC 1-6 Alkyl, -N(C) 1-6 Alkyl)2, C 6-14 The aryl group, a 5-14 heteroaryl group, and one of the groups shown in Formula 1 to Formula 24, wherein one of the R groups in Formula I to Formula IV is selected from one of the groups shown in Formula 1 to Formula 24.

[0011] According to embodiments of the present invention, R1 may be the same or different, and is independently selected from hydrogen, C 1-12 Halogenated alkyl, halogen, cyano, C 1-12 Alkyl, C 6-20 Aryl, -NHC 1-12 Alkyl, -N(C) 1-12 Alkyl)2 and one of the groups shown in Formulas 1 to 24.

[0012] According to some specific embodiments of the present invention, R1 may be the same or different, and is independently selected from hydrogen, C 1-6 Halogenated alkyl, halogen, cyano, C 1-6 Alkyl, C 6-20 Aryl, -NHC 1-6 Alkyl, -N(C) 1-6 Alkyl)2 and one of the groups shown in Formulas 1 to 24.

[0013] According to some specific embodiments of the present invention, the phosphonium ion-based derivatives shown in Formula I or Formula II are selected from the following structures:

[0014] Wherein, R is selected from the following groups: R6, R7, R8, and R9 may be the same or different, and are independently selected from hydrogen, deuterium, or tritium. Ra, Rb, and Rc may be the same or different, and are independently selected from C. 1-12 Alkyl, Halogenated C 1-12 Alkyl, C 1-12 Alkoxy, -NHC 1-12 Alkyl, -N(C) 1-12 Alkyl group 2, halogenated C 1-12 Alkoxy, C 6-14 Aryl, C 3-14Cycloalkyl, 3-14 membered heterocyclic or 5-14 membered heteroaryl, such as C 1-6 Alkyl groups, such as methyl, ethyl, or propyl; R1 is selected from C 1-30 Alkyl, such as C 3-28 Alkyl groups, such as C 4-25 Alkyl groups, such as n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecanyl, n-eicosyl, n-monodecyl, n-dioctyl, n-tridecyl, n-tetradecyl, or n-pentadecanyl; L is selected from or , where R 30 Selected from halogens; for example, L is selected from... , where R 30 Selected from Cl, Br, or I.

[0015] According to the present invention, the phosphonium-based derivative is preferably one of the compounds shown in Formulas I-1 to II-5: .

[0016] The present invention also provides a method for preparing the phosphonium ion-based derivative as described above, comprising: reacting a halide salt of the cationic portion of the phosphonium ion-based derivative of Formula I with an alkali metal salt containing anionic portion to obtain the phosphonium ion-based derivative of Formula I. Alternatively, the halide of the cationic portion of the derivative of formula II based on phosphonium ions can be reacted with an alkali metal salt containing the anionic portion to obtain the derivative of formula II based on phosphonium ions. Alternatively, the halide of the cationic portion of the derivative of formula III based on phosphonium ions can be reacted with an alkali metal salt containing the anionic portion to obtain the derivative of formula III based on phosphonium ions. Alternatively, the halide of the cationic portion of the derivative of Formula IV based on phosphonium ions can be reacted with an alkali metal salt containing the anionic portion to obtain the derivative of Formula IV based on phosphonium ions.

[0017] The present invention also provides the use of phosphonium ion-based derivatives as described above, in the preparation of organic scintillators.

[0018] According to embodiments of the present invention, the applications of the organic scintillator include, but are not limited to, medical diagnostics, industrial non-destructive testing, radiation detection, and other fields, such as radiation detection, X-ray imaging, neutron imaging, and gamma-ray imaging.

[0019] According to an embodiment of the present invention, the derivative is used as a luminescent material in the preparation of an organic scintillator.

[0020] The present invention also provides a scintillator material comprising at least one of the phosphonium ion-based derivatives as described above, or Formula I, or Formula II, or Formula III or IV.

[0021] The present invention also provides the application of the scintillator material described above in radiation detection, X-ray imaging, neutron imaging and gamma-ray imaging.

[0022] The present invention also provides an X-ray imaging thin film comprising a polymer matrix and an organic scintillator doping material; the organic scintillator doping material comprising at least one of the phosphonium ion-based derivatives as shown in Formula I, or Formula II, or Formula III or IV as described above.

[0023] Compared with the prior art, the derivatives of the present invention have the following advantages: (1) The scintillator material based on phosphonium ion derivatives described in this invention has the advantages of high radiation intensity and strong X-ray absorption capacity, and is a class of efficient and stable organic scintillator materials.

[0024] (2) The scintillator material based on phosphonium ion derivatives described in this invention has the characteristics of good solubility in organic solvents and low glass transition temperature. It is very suitable for preparing transparent imaging films through solution processing technology, and is also suitable for preparing undoped glassy transparent scintillator screens through melting method, thereby greatly reducing the film preparation cost in industrial practice.

[0025] (3) The triazine derivative-based scintillator material described in this invention has low raw material cost, simple and efficient synthesis, and economic advantages in industrial application.

[0026] In summary, the organic scintillator material of this invention exhibits strong X-ray absorption capacity, high exciton utilization, and can achieve both high absorption and high luminescence efficiency. This type of material decouples X-ray absorption and luminescence functions, employing bulky organic anions containing heavy atoms as X-ray absorption units, utilizing their high atomic numbers to achieve efficient X-ray absorption; simultaneously, it employs phosphonium cations with TADF properties as luminescence units, capturing both singlet and triplet excitons through the TADF mechanism to achieve efficient luminescence.

[0027] The scintillator material provided by this invention not only possesses excellent luminous efficiency and radiation absorption capacity, but also exhibits good solubility and melt processability. It can be used to prepare large-area transparent scintillator films or glassy scintillator screens with high doping concentrations through simple processes such as solution evaporation and coating. This type of material also exhibits good radiation stability and humidity stability, making it suitable for practical application environments. These characteristics give the derivatives of this invention significant economic advantages in industrial practice, making them suitable for various application scenarios and demonstrating promising industrialization prospects.

[0028] Terminology Definitions and Explanations Unless otherwise defined, all technical terms herein have the same meaning as commonly understood by one of ordinary skill in the art to which the subject matter of the claims pertains.

[0029] The term "halogen" refers to fluorine, chlorine, bromine, and iodine.

[0030] "Halogenation" refers to the replacement of a substance by one or more halogens.

[0031] Term "C" 1-30 "alkyl" should be understood to refer to a straight-chain or branched saturated monovalent hydrocarbon group having 1 to 30 carbon atoms, preferably "C". 1-12 Alkyl or C 1-6 Alkyl group. For example, "C 1-6 "Alkyl" means a straight-chain or branched alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, or 1,2-dimethylbutyl, or their isomers.

[0032] Term "C" 6-20 "Aryl" should be understood to represent an aromatic monocyclic, bicyclic, or tricyclic hydrocarbon ring having 6 to 20 carbon atoms, preferably "C". 6-14 "Aromatic". The term "C" 6-14 "Aryl" should be understood to preferably represent a monovalent aromatic or partially aromatic monocyclic, bicyclic, or tricyclic hydrocarbon ring ("C") having 6, 7, 8, 9, 10, 11, 12, 13, or 14 carbon atoms. 6-14 Aryl), particularly a ring with 6 carbon atoms (“C6 aryl”), such as phenyl; or biphenyl, or a ring with 9 carbon atoms (“C9 aryl”), such as indenyl or indenyl, or a ring with 10 carbon atoms (“C9 aryl”). 10Aryl groups, such as tetrahydronaphthyl, dihydronaphthyl, or naphthyl, or rings with 13 carbon atoms (“C”). 13 Aryl groups, such as fluorene groups, or rings with 14 carbon atoms (“C”). 14 Aryl groups, such as anthracene groups, or rings with 16 carbon atoms (“C”). 16 Aryl), such as pyrene. When the C 6-22 When the base is substituted, it can be a single substitution or multiple substitutions. Furthermore, there are no restrictions on the substitution site; for example, it can be an ortho, para, or meta substitution.

[0033] The term "5-20-membered heteroaryl" should be understood to include monovalent monocyclic, bicyclic, or tricyclic aromatic ring systems having 5 to 20 ring atoms and containing 1 to 5 heteroatoms independently selected from N, O, and S, for example, "5-14-membered heteroaryl". The term "5-14-membered heteroaryl" should also be understood to include monovalent monocyclic, bicyclic, or tricyclic aromatic ring systems having 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14 ring atoms, particularly 5, 6, 9, or 10 carbon atoms, and containing 1 to 5, preferably 1 to 3, heteroatoms independently selected from N, O, and S, and, in each case, may be benzofused. Specifically, the heteroaryl group is selected from thienyl, furanyl, pyrroleyl, oxazolyl, thiazolyl, imidazoleyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl, and their benzo[derivatives], such as benzofuranyl, benzothienyl, benzooxazolyl, benzoisooxazolyl, benzoimidazolyl, benzotriazolyl, indazole, indolyl, isindolyl, etc.; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and their benzo[derivatives], such as quinolinyl, quinazolinyl, isoquinolinyl, etc.; or acrylinyl, inazinyl, purinyl, and their benzo[derivatives]; or terpenolyl, phthalazinyl, quinazolinyl, quinoxolinyl, naphridinyl, pteridinyl, carbazolyl, acridineyl, phenazinyl, phenothiazinyl, phenothiazinyl, etc. Attached Figure Description

[0034] Figure 1 These are schematic diagrams of the crystal structures of the compounds shown in formulas I-1, I-2, and I-3; Figure 2 The absorption spectra of the compounds shown in formulas I-1, I-2 and I-3 and their photoluminescence spectra at 300 K are shown. Figure 3 These are the photoluminescence spectra of the compounds shown in formulas II-1, II-2, II-3, II-4 and II-5 at 300 K; Figure 4 These are transient spectral lifetime diagrams of the compounds shown in formulas I-1, I-2 and I-3 at 300 K; Figure 5 The transient spectral lifetime diagrams of the compounds shown in formulas II-1, II-2, II-3, II-4 and II-5 at 300 K are shown. Figure 6 These are the radiative emission spectra of the compounds shown in formulas I-1, I-2 and I-3 at 300 K; Figure 7 These are the radiative emission spectra of the compounds shown in formulas II-1, II-2, II-3, II-4 and II-5 at 300 K; Figure 8 These are the radiation luminescence stability test results of the compounds shown in formulas I-1, I-2 and I-3 at 300 K; Figure 9 The graphs show the radiation luminescence stability of the compounds represented by formulas II-1, II-2, II-3, II-4 and II-5 at 300 K. Figure 10 The image shows the appearance of a 60wt% doped transparent thin film prepared using the compounds shown in Formulas I-2 and I-3. Figure 11 This is an image of a glassy molten transparent film prepared using the compound shown in Formula II-5; Figure 12 These are the thermogravimetric analysis (TGA) plots of the compounds shown in formulas I-1, I-2, and I-3; Figure 13 These are thermogravimetric (TGA) plots of the compounds shown in formulas II-1, II-2, II-3, II-4, and II-5; Figure 14 This is an X-ray imaging effect diagram of the transparent scintillating screen provided in Example 10.

[0035] Figure 15 This is an X-ray imaging effect diagram of the transparent scintillating screen provided in Example 11.

[0036] Figure 16 This is an X-ray imaging effect diagram of the transparent scintillating screen provided in Example 12. Detailed Implementation

[0037] The present invention is illustrated in detail through the following embodiments, but the invention is not limited thereto. Based on the description of the present invention, those skilled in the art can implement the present invention within the entire scope disclosed herein without requiring inventive effort, prepare the scintillator material described in the present invention, fabricate this material into a transparent scintillator screen, and directly apply the imaging thin film to applications such as radiation detection, X-ray imaging, gamma-ray imaging, and neutron imaging, or use the method of the present invention.

[0038] Example 1 9,9-Dimethyl-10-[4-(triphenyl-λ) 4 Synthetic method of [-phosphoalkyl)phenyl]-9,10-dihydroacrylidine bromide:

[0039] Under nitrogen protection, 9,9-dimethyl-9,10-dihydroacridine (30 mmol, 6.28 g), 1-bromo-4-iodobenzene (33 mmol, 9.33 g), cuprous iodide (6 mmol, 1.14 g), (1S,2S)-cyclohexane-1,2-diamine (3 mmol, 0.35 g), and sodium tert-butoxide (60 mmol, 5.77 g) were added to a three-necked flask, followed by 40 mL of dried 1,4-dioxane. The reaction mixture was stirred overnight at 110 °C. The 1,4-dioxane was removed by vacuum distillation, and the reaction mixture was extracted three times with dichloromethane and brine. After drying over anhydrous sodium sulfate, the crude product was purified by silica gel column chromatography to give a white solid, 10-(4-bromophenyl)-9,9-dimethyl-9,10-dihydroacridine, in 80% yield.

[0040] Under nitrogen protection, 10-(4-bromophenyl)-9,9-dimethyl-9,10-dihydroacridine (5 mmol, 1.82 g), triphenylphosphine (5.2 mmol, 1.36 g), nickel bromide (1 mmol, 0.22 g), and dry ethylene glycol (15 mL) were added to a double-necked flask. The reaction mixture was refluxed at 180 °C for 12 hours. After the reaction was complete, a large amount of saturated brine was added, the mixture was filtered, the filter cake was collected and washed with a large amount of water. The crude solid was washed three times successively with dichloromethane and saturated brine. The combined organic phases were dried over anhydrous sodium sulfate and concentrated. Column chromatography purification gave the target product 9,9-dimethyl-10-[4-(triphenyl-λ)] 4 [-phosphoalkyl)phenyl]-9,10-dihydroacridine bromide, a yellow-green solid, in 89% yield.

[0041] The relative molecular mass percentages of each element (C / H / N) obtained from elemental analysis are: C, 74.81; H, 5.26; N, 2.21; theoretical values ​​of elemental analysis are: C, 74.76; H, 5.31; N, 2.24.

[0042] Example 2 Synthetic method of the compound shown in Formula I-1:

[0043] The compound 9,9-dimethyl-10-[4-(triphenyl-λ) prepared in Example 1 was used. 4[-phosphonyl)phenyl]-9,10-dihydroacrylidine bromide (2 mmol) was dissolved in dichloromethane (30 mL), followed by the addition of sodium tetra(4-chlorophenyl)borate. The mixture was stirred at room temperature for 2 hours. After the reaction was complete, the mixture was filtered, and the filtrate was purified by column chromatography to give the green compound of formula I-1 in 99% yield.

[0044] The relative molecular mass percentages of each element (C / H / N) obtained from elemental analysis are: C, 75.62; H, 5.80; N, 1.32. The theoretical values ​​of elemental analysis are: C, 75.39; H, 4.92; N, 1.40.

[0045] Example 3 Synthetic method of the compound shown in Formula I-2:

[0046] By replacing sodium tetra(4-chlorophenyl)borate with sodium tetra(4-bromophenyl)borate, the compound shown in Formula I-2 was obtained by the same synthesis method as in Example 2, with an overall yield of 98%.

[0047] The relative molecular mass percentages of each element (C / H / N) obtained from elemental analysis are: C, 65.25; H, 4.87; N, 1.09. The theoretical values ​​of elemental analysis are: C, 64.05; H, 4.18; N, 1.19.

[0048] Example 4 Synthetic method of the compound shown in Formula I-3:

[0049] By replacing sodium tetra(4-chlorophenyl)borate with sodium tetra(4-iodophenyl)borate, the compounds shown in Formula I-3 were obtained by the same synthesis method as in Example 2, with an overall yield of 99%.

[0050] The relative molecular mass percentages of each element (C / H / N) obtained from elemental analysis are: C, 57.51; H, 4.19; N, 1.01. The theoretical values ​​of elemental analysis are: C, 55.25; H, 3.61; N, 1.02.

[0051] Example 5 Synthetic method of the compound shown in Formula II-1:

[0052] Where n is 7.

[0053] Under nitrogen protection, the reactant 10-(4-bromophenyl)-9,9-dimethyl-9,10-dihydroacridine (10 mmol, 3.64 g) was reacted with n-butyllithium (11 mmol, 2.5 M, 4.4 ml) in anhydrous diethyl ether at -78 °C for 1 hour. Then, diphenylphosphine chloride (10 mmol, 1.86 g) was added, followed by stirring and natural warming to room temperature. The reaction continued for 24 hours. After the reaction was complete, a small amount of water was added to quench the reaction, and the diethyl ether was removed by vacuum distillation. The intermediate 10-(4-(diphenylphosphino)phenyl)-9,9-dimethyl-9,10-dihydroacridine was obtained by column chromatography.

[0054] Under nitrogen protection, the reactant 10-(4-(diphenylphosphino)phenyl)-9,9-dimethyl-9,10-dihydroacridine (5 mmol, 2.35 g) and excess 1-bromononane were heated to reflux in ethylene glycol and stirred continuously for 12 hours. After the reaction was completed, a large amount of water was added to wash away the ethylene glycol. The crude product obtained was separated by column chromatography to obtain the intermediate 10-[4-(eicosanoyldiphenyl-λ] 4 [-phosphoalkyl)phenyl]-9,9-dimethyl-9,10-dihydroacrylidine bromide.

[0055] Under nitrogen protection, the reactant 10-[4-(eicosyldiphenyl-λ)] 4 [-phosphonyl)phenyl]-9,9-dimethyl-9,10-dihydroacrylidine bromide (3 mmol) was dissolved in dichloromethane (30 mL), followed by the addition of sodium tetra(4-bromophenyl)borate. The mixture was stirred at room temperature for 2 hours. After the reaction was complete, the mixture was filtered, and the filtrate was purified by column chromatography to give the compound shown in green formula II-1, with an overall yield of 57%.

[0056] The relative molecular mass percentages of each element (C / H / N) obtained from elemental analysis are: C, 64.47; H, 5.01; N, 1.05. The theoretical values ​​of elemental analysis are: C, 64.36; H, 5.16; N, 1.14.

[0057] Example 6 Synthesis method of the compound shown in Formula II-2: The synthesis method is the same as in Example 5, except that the reactant bromoalkane is replaced with 1-bromododecane. The compound shown in Formula II-2 is obtained by the same synthesis method as in Example 5, with an overall yield of 62%.

[0058] The relative molecular mass percentages of each element (C / H / N) obtained from elemental analysis are: C, 65.27; H, 5.61; N, 1.05. The theoretical values ​​of elemental analysis are: C, 65.07; H, 5.46; N, 1.10.

[0059] Example 7 Synthesis method of the compound shown in Formula II-3: The synthesis method is the same as in Example 5, except that the reactant bromoalkane is replaced with 1-bromopentadecane. The compound shown in Formula II-3 is obtained by the same synthesis method as in Example 5, with an overall yield of 55%.

[0060] The relative molecular mass percentages of each element (C / H / N) obtained from elemental analysis are: C, 65.82; H, 5.91; N, 1.07. The theoretical values ​​of elemental analysis are: C, 65.72; H, 5.75; N, 1.06.

[0061] Example 8 Synthesis method of the compound shown in Formula II-4: The synthesis method is the same as in Example 5, except that the reactant bromoalkane is replaced with 1-bromooctadecane. The compound shown in Formula II-4 is obtained by the same synthesis method as in Example 5, with an overall yield of 66%.

[0062] The relative molecular mass percentages of each element (C / H / N) obtained from elemental analysis are: C, 66.37; H, 5.11; N, 1.05. The theoretical values ​​of elemental analysis are: C, 66.34; H, 6.01; N, 1.03.

[0063] Example 9 Synthesis method of the compound shown in Formula II-5: The synthesis method is the same as in Example 5, except that the reactant bromoalkane is replaced with 1-bromotetracosane. The compound shown in Formula II-5 is obtained by the same synthesis method as in Example 5, with an overall yield of 58%.

[0064] The relative molecular mass percentages of each element (C / H / N) obtained from elemental analysis are: C, 67.33; H, 6.39; N, 1.02. The theoretical values ​​of elemental analysis are: C, 67.11; H, 6.34; N, 0.99.

[0065] Figure 1 These are schematic diagrams of the crystal structures of the compounds shown in formulas I-1, I-2, and I-3.

[0066] Figure 2 These are the absorption spectra of the compounds shown in formulas I-1, I-2, and I-3, and their photoluminescence spectra at 300 K; Figure 2 These compounds emit green light with a peak emission wavelength of 520 nm.

[0067] Figure 3 The figures show the photoluminescence spectra of compounds represented by formulas II-1, II-2, II-3, II-4, and II-5 at 300 K; as can be seen from the figures, these compounds emit green light with a peak emission value of 503 nm.

[0068] Figure 4The transient spectral lifetimes of the compounds shown in formulas I-1, I-2, and I-3 at 300 K are shown in the figure. As can be seen from the figure, these compounds have a relatively short luminescence lifetime of about 1.2 microseconds.

[0069] Figure 5 The transient spectral lifetimes of compounds represented by formulas II-1, II-2, II-3, II-4, and II-5 at 300 K are shown in the figure. As can be seen from the figure, these compounds have a relatively short luminescence lifetime of about 1.3 microseconds.

[0070] Figure 6 The figures show the radiative emission spectra of the compounds represented by formulas I-1, I-2, and I-3 at 300 K. As can be seen from the figures, the radiative emission spectra of these compounds are consistent with the photoluminescence spectra, indicating that their radiative emission still originates from cations with TADF properties.

[0071] Figure 7 The figures show the radiative emission spectra of compounds represented by formulas II-1, II-2, II-3, II-4, and II-5 at 300 K. As can be seen from the figures, the radiative emission spectra of these compounds are consistent with the photoluminescence spectra, indicating that their radiative emission still originates from cations with TADF properties.

[0072] Figure 8 The graphs show the radioluminescence stability of the compounds represented by formulas I-1, I-2, and I-3 at 300 K; as can be seen from the graphs, these compounds have good X-ray irradiation stability.

[0073] Figure 9 The graphs show the radioluminescence stability of compounds II-1, II-2, II-3, II-4 and II-5 at 300 K; the graphs show that these compounds have good X-ray irradiation stability.

[0074] Figure 10 The image shows the appearance of a 60wt% doped transparent thin film prepared using the compounds shown in Formulas I-2 and I-3. As can be seen from the image, these compounds can be used to prepare highly doped transparent scintillating screens via solution processing.

[0075] Figure 11 The image shows the appearance of a glassy molten transparent film prepared using the compound shown in Formula II-5; as can be seen from the image, this compound can be used to prepare a glassy transparent scintillating screen by melting.

[0076] Figure 12 These are thermogravimetric analysis (TGA) graphs of the compounds represented by formulas I-1, I-2, and I-3; the graphs show that these compounds have good thermal stability.

[0077] Figure 13These are thermogravimetric analysis (TGA) graphs of the compounds represented by formulas II-1, II-2, II-3, II-4, and II-5; the graphs show that these compounds have good thermal stability.

[0078] Figure 14 This is an X-ray imaging effect diagram of the transparent scintillating screen provided in Example 10.

[0079] Figure 15 This is an X-ray imaging effect diagram of the transparent scintillating screen provided in Example 11.

[0080] Figure 16 This is an X-ray imaging effect diagram of the transparent scintillating screen provided in Example 12.

[0081] Example 10 The compound of formula I-2 obtained in Example 3 was used as a dopant to prepare X-ray imaging thin films. Device fabrication steps: The compound shown in Formula I-2 and the polymer matrix polymethyl methacrylate (PMMA) were simultaneously dissolved in N,N-dimethylformamide (DMF) at a mass ratio of 6:4. The total concentration of compound I-2 and the polymer matrix was approximately 30 mg / mL. The solution was then poured into a flat-bottomed mold and heated until the solvent evaporated completely, yielding a transparent scintillator film. Figure 10 Imaging films prepared using I-2 as a dopant exhibit high spatial resolution, with line-pair card display resolution greater than 20 lp / mm. Figure 14 The maximum spatial resolution calculated using the hypotenuse method MTF is 97.8 lp / mm.

[0082] Based on this flickering screen, X-ray imaging was performed on a chip, dried fish, and a 400-mesh copper mesh. The resulting images are shown below. Figure 14 It can be seen that the scintillation screen prepared based on the compound shown in Formula I-2 has excellent X-ray imaging effect.

[0083] Example 11 The compounds of formula I-3 synthesized in Example 4 were used as dopant materials to prepare X-ray imaging thin films. Device fabrication steps: The compound shown in Formula I-3 and PMMA were simultaneously dissolved in DMF at a mass ratio of 6:4, with a total concentration of approximately 30 mg / mL. The solution was then poured into a flat-bottomed mold and heated until the solvent evaporated completely, yielding a transparent scintillator film. Figure 10 Imaging films prepared using I-3 as a dopant exhibit high spatial resolution, with line-pair card display resolution greater than 20 lp / mm. Figure 15 The maximum spatial resolution calculated using the hypotenuse method MTF is 82.6 lp / mm.

[0084] Based on this flickering screen, X-ray imaging was performed on a chip, dried fish, and a 400-mesh copper mesh. The resulting images are shown below. Figure 15 It can be seen that the scintillation screen prepared based on the compound shown in Formula I-3 has excellent X-ray imaging effect.

[0085] Example 12 The compound of formula II-5 obtained in Example 9 was prepared into an X-ray imaging thin film by a melt method. Device fabrication steps: Place the compound shown in Formula II-5 into a flat-bottomed mold, add more material until the compound melts, and spread it by scraping (a transparent glassy scintillator film can also be prepared by casting or self-leveling methods), and then cool to obtain a transparent glassy scintillator film. Figure 11 The glassy fused scintillation screen prepared with the compound shown in Formula II-5 has high spatial resolution, with a line-to-card display resolution greater than 20 lp / mm. Figure 16 Using the hypotenuse method, the maximum spatial resolution calculated by MTF is 86.6 lp / mm, which can realize dynamic X-ray imaging.

[0086] Based on the imaging effect of this vitreous scintillation screen on real objects, such as... Figure 16 It can be seen that the scintillation screen prepared based on the compound shown in Formula II-5 has excellent X-ray imaging effect. Dynamic X-ray imaging of iohexol solution shows that the scintillation screen can be used in the field of dynamic X-ray imaging (the imaging effects of other II series compounds II-1, II-2, II-3 and II-4 in this application are basically the same as those of the compound shown in Formula II-5).

[0087] The test results above demonstrate that the imaging film prepared using the derivative described in this invention as a scintillator material exhibits extremely high imaging resolution. Furthermore, its preparation process is simple, it demonstrates good irradiation stability, and it is inexpensive. These characteristics are all beneficial for its application in industrial practice.

[0088] The exemplary embodiments of the present invention have been described above. However, the scope of protection of the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made by those skilled in the art within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. Derivatives based on phosphonium ions as shown in Formula I, or Formula II, or Formula III or IV: in, R may be the same or different, and they are independently selected from hydrogen and C. 1-30 Halogenated alkyl, halogen, cyano, C 1-30 Alkyl, -NHC 1-30 Alkyl, -N(C) 1-30 Alkyl)2, C 6-20 The aryl group, a 5-20 membered heteroaryl group, and one of the groups shown in Formula 1 to Formula 24, wherein at least one R group in Formula I to Formula IV is selected from one of the groups shown in Formula 1 to Formula 24; R1 may be the same or different, and are independently selected from hydrogen and C. 1-30 Halogenated alkyl, halogen, cyano, C 1-30 Alkyl, C 6-20 Aryl, -NHC 1-30 Alkyl, -N(C) 1-30 alkyl)2 and one of the groups shown in formulas 1 to 24; In this context, the dashed line (--) indicates a connection point that connects to another unit; R6, R7, R8, R9, R 10 R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 R 21 R 22 R 23 R 24 R 25 R 26 R 27 and R 28 They may be the same or different, and are independently selected from hydrogen, deuterium, tritium, halogen, amino, hydroxyl, cyano, and C. 1-30 Alkyl, Halogenated C 1-30 Alkyl, C 1-30 Alkoxy, -NHC 1-30 Alkyl, -N(C) 1-30 Alkyl group 2, halogenated C 1-30 Alkoxy, C 6-20 Aryl, C 3-20 One of the following: cycloalkyl, 3-20 membered heterocyclic, 5-20 membered heteroaryl and groups shown in Formula 1 to Formula 24; D is an electron-donating group selected from one of Formula 1 to Formula 24, forming an electron-donating group with a dendritic structure; L is selected from ClO4 - BF4 - BBr4 - SeF6 2- SeF5 - SeBr5 - SeBr6 2- SbF6 - PtBr6 2- PtI6 2- NO3 - And one of the structures shown in equations Ia to IXa below: R 30 Whether the two are the same or different, they are each independently selected from hydrogen and C. 1-30 Halogenated alkyl, halogen, cyano, C 1-30 Alkyl, C 1-30 alkylamine group, C 6-20 One of the aryl group and the 5-20 heteroaryl group.

2. The derivative according to claim 1, wherein, R may be the same or different, and they are independently selected from hydrogen and C. 1-12 Halogenated alkyl, halogen, cyano, C 1-12 Alkyl, -NHC 1-12 Alkyl, -N(C) 1-12 Alkyl)2, C 6-14 The aryl group, a 5-14 heteroaryl group, and one of the groups shown in Formula 1 to Formula 24, wherein one of the R groups in Formula I to Formula IV is selected from one of the groups shown in Formula 1 to Formula 24.

3. The derivative according to claim 1, wherein, R1 may be the same or different, and are independently selected from hydrogen and C. 1-12 Halogenated alkyl, halogen, cyano, C 1-12 Alkyl, C 6-20 Aryl, -NHC 1-12 Alkyl, -N(C) 1-12 Alkyl)2 and one of the groups shown in Formulas 1 to 24.

4. The derivative according to claim 1, wherein, The derivative is selected from the following structures: Wherein, R is selected from the following groups: R6, R7, R8, and R9 may be the same or different, and are independently selected from hydrogen, deuterium, or tritium. Ra, Rb, and Rc may be the same or different, and are independently selected from C. 1-12 Alkyl, Halogenated C 1-12 Alkyl, C 1-12 Alkoxy, -NHC 1-12 Alkyl, -N(C) 1-12 Alkyl)2, Halogenated C 1-12 Alkoxy, C 6-14 Aryl, C 3-14 Cycloalkyl, 3-14 membered heterocyclic or 5-14 membered heteroaryl; R1 is selected from C 1-30 alkyl; L is selected from or , where R 30 Selected from halogens.

5. The derivative according to any one of claims 1-4, wherein, The derivative is one of the compounds shown in Formulas I-1 to II-5 below: 。 6. A method for preparing the derivative according to any one of claims 1-5, wherein, include: The halide of the cationic portion of the derivative based on phosphonium ions shown in Formula I is reacted with an alkali metal salt containing anionic portion to obtain the derivative based on phosphonium ions shown in Formula I. Alternatively, the halide of the cationic portion of the derivative of formula II based on phosphonium ions can be reacted with an alkali metal salt containing the anionic portion to obtain the derivative of formula II based on phosphonium ions. Alternatively, the halide of the cationic portion of the derivative of formula III based on phosphonium ions can be reacted with an alkali metal salt containing anionic portions to obtain the derivative of formula III based on phosphonium ions. Alternatively, the halide of the cationic portion of the derivative of Formula IV based on phosphonium ions can be reacted with an alkali metal salt containing the anionic portion to obtain the derivative of Formula IV based on phosphonium ions.

7. Use of the derivative according to any one of claims 1-5 in the preparation of organic scintillators.

8. The use according to claim 7, wherein, The applications of the organic scintillator include medical diagnostics, industrial non-destructive testing, and radiation detection.

9. A scintillator material comprising at least one of the derivatives according to any one of claims 1-5.

10. An X-ray imaging thin film comprising a polymer matrix and an organic scintillator doping material; said organic scintillator doping material comprising at least one of the derivatives of any one of claims 1-5.

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