Zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide as well as preparation method and application thereof

Abstract

The invention provides a zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide as well as a preparation method and application thereof, and belongs to the technical field of material science and photoelectricity. The preparation method comprises the following steps: grinding and uniformly mixing quaternary phosphonium ionic liquid, hydrated halogenated manganese salt and oxalic acid dihydrate to obtain a mixed material; and transferring the mixed material into a high-temperature reaction kettle, carrying out high-temperature reaction, cooling to room temperature, adding ethanol into the high-temperature reaction kettle, heating, recrystallizing, and cooling to obtain the zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide. According to the method, the defect that a traditional solvent volatilization method, a solvothermal method, a solvent diffusion method and the like highly depend on strong haloid acid and an organic solvent is overcome, and the technical problem of green controllable synthesis of the 0D Mn-OIMHs crystal is solved by adopting a green and environment-friendly ionothermal synthesis method.

Description

Technical Field

[0001] This invention belongs to the fields of materials science and optoelectronic technology, and particularly relates to a zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide, its preparation method and application. Background Technology

[0002] Zero-dimensional (0D) organic-inorganic hybrid metal halides (OIMHs) are promising optoelectronic materials derived from perovskites. Their advantages lie not only in reducing the toxicity of lead-based perovskites but also in the synergistic combination of organic cations and inorganic metal halide polyhedra. This hybrid structure allows for extensive tunability in composition, structure, dimensionality, band gap, and ultimately, luminescent properties. To improve the toxicity of lead-based perovskites, researchers have successfully replaced the toxic Pb at the b-site with various metal ions. 2+ including Cd 2+ Zn 2+ In 3+ Cu + Sb 3+ Mn 2+ Re 3+ (e.g. Eu) 3+ 、Tb 3+ Ho 3+ ), Zr 4+ Meanwhile, the organic cation library has been greatly expanded, no longer limited to the initial quaternary ammonium, but also including quaternary phosphonium, imidazole ionic liquids, piperazine ionic liquids, etc. These developments demonstrate the significant progress made in lead-free OIMH luminescent materials. Despite these achievements, major obstacles remain. Many low-dimensional (zero-dimensional, one-dimensional, two-dimensional) OIMHs exhibit self-trapped exciton (STE) photoluminescence characterized by a large Stokes shift, but this characteristic often hinders efficient blue light excitation, which is a fundamental requirement for high luminous efficiency in white light emitting diodes (WLEDs). Therefore, the development of bright and stable lead-free OIMHs remains of great significance.

[0003] In this context, 0D Mn-OIMHs exhibit significant advantages, including near-uniform PLQY (photoluminescence quantum yield), narrow emission linewidth (FWHM), and good stability, making them particularly attractive for WLED applications. Indeed, small FWHM and long-term stability are key benchmarks for high-performance phosphors. However, their synthesis currently relies primarily on methods using strong halogen acids (such as HCl, HBr, HI) and organic solvents, with varying and strictly controlled amounts of acid in each formulation. This dependence arises because strong halogen acids play three key roles: (1) increasing the solubility of reactants and stabilizing precursor solutions; (2) providing halide ions for coordination, providing protons to regulate pH, and promoting the stability of organic cations; and (3) maintaining the stability and purity of perovskites in acidic media. However, these methods are environmentally hazardous and lack versatility. Therefore, green and universally applicable synthesis strategies are crucial for the practical application of these materials. Summary of the Invention

[0004] To address the problems of traditional synthesis methods for OD Mn-OIMHs, such as solvent evaporation, solvent diffusion, and solvothermal methods, which are highly dependent on strong acids (e.g., HCl, HBr, HI) and organic solvents, easily causing environmental pollution and lacking universality, failing to fundamentally achieve green and controllable synthesis, this invention proposes a zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide, its preparation method, and its application.

[0005] To achieve the above objectives, the present invention provides the following technical solution:

[0006] This invention proposes a method for preparing zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halides (OD Mn-OIMHs), comprising the following steps:

[0007] Quaternary phosphorus ionic liquid, hydrated manganese halide salt and oxalic acid dihydrate are ground and mixed evenly to obtain a mixture.

[0008] The mixture was transferred to a high-temperature reactor for high-temperature reaction. After cooling to room temperature, ethanol was added to the high-temperature reactor, and the mixture was heated for recrystallization. After cooling, the zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide (OD Mn-OIMHs) was obtained.

[0009] The ratio of ethanol to quaternary phosphorus ionic liquid is 3 mL: 1 mol.

[0010] Furthermore, the molar ratio of the quaternary phosphonium-based ionic liquid, the hydrated manganese halide salt, and the oxalate dihydrate (ox) is 1:1:1.

[0011] Furthermore, the quaternary phosphonium-based ionic liquid is selected from methyltriphenylphosphonium bromide (CH3-Ph3P). + Br - ), Ethyltriphenylphosphonium bromide (C2H5-Ph3P) + Br - ), propyltriphenylphosphonium bromide (p-C3H7-Ph3P) + Br - ), isopropyltriphenylphosphonium bromide (i-C3H7-Ph3P) + Br - ), Cyclopropyltriphenylphosphonium bromide (C3H5-Ph3P) + Br - ), benzyltriphenylphosphonium bromide (PhCH2-Ph3P) + Br - ), tetraphenylphosphonium bromide (Ph4P) + Br - ), 2,4-dichloro-benzyltriphenylphosphonium bromide (2,4-DCl-PhCH2-Ph3P) + Cl - At least one of the following.

[0012] Furthermore, the hydrated manganese halide salt is manganese chloride tetrahydrate (MnCl2·4H2O) or manganese bromide tetrahydrate (MnBr2·4H2O).

[0013] Furthermore, the ratio of ethanol to quaternary phosphonium-based ionic liquid is 3 mL: 1 mol.

[0014] Furthermore, the high-temperature reaction is carried out at a temperature of 180°C for 3 days.

[0015] Furthermore, the temperature for the heating recrystallization is 120°C, and the time is 3 days.

[0016] This invention also proposes a zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide, which is prepared according to the above preparation method.

[0017] Furthermore, the chemical formula of the zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide is [R-Ph3P]2MnX4, where R is methyl, ethyl, propyl, isopropyl, cyclopropyl, benzyl or 2,4-dichlorobenzyl, and X is Cl, Br or a combination of Cl and Br.

[0018] This invention also proposes an application of the above-mentioned zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide in light-emitting devices.

[0019] Furthermore, the light-emitting device is a white light-emitting diode, and the zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide serves as a fluorescent material in the white light-emitting diode.

[0020] Compared with the prior art, the present invention has the following advantages and technical effects:

[0021] This invention relates to 0D Mn-OIMHs crystals, obtained by grinding and uniformly mixing quaternary phosphonium-based ionic liquid, hydrated manganese halide salt, and oxalic acid dihydrate in a molar ratio of 1:1:1, transferring the mixture to a high-temperature reactor, heating at 180°C for three days, and then adding a small amount of ethanol for recrystallization, resulting in a series of advanced optoelectronic materials with high luminescence performance. This invention avoids the drawbacks of traditional solvent evaporation, solvothermal, and solvent diffusion methods, which are highly dependent on strong halogen acids and organic solvents. It employs a green and environmentally friendly ionothermal synthesis method, achieving a green and controllable synthesis technology for 0D Mn-OIMHs crystals. The amount of ethanol used is a key factor in the formation of 0D Mn-OIMHs crystals (too much ethanol results in no crystals, while too little results in poor crystal morphology), affecting both the yield and morphology of the crystals. Attached Figure Description

[0022] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention. In the drawings:

[0023] Figure 1 The structural diagram of [2,4-DCl-PhCH2-Ph3P]2MnBr4 in Example 4 is shown.

[0024] Figure 2 The structural diagram of [2,4-DCl-PhCH2-Ph3P]2MnCl4 in Example 5 is shown.

[0025] Figure 3 The structural diagram of [p-C3H7-Ph3P]2MnBr4 in Example 9;

[0026] Figure 4 The structural diagram of [C3H5-Ph3P]2MnBr2Cl2 in Example 2;

[0027] Figure 5 The structural diagram of [C3H5-Ph3P]2MnBr4 in Example 1 is shown.

[0028] Figure 6 The structural diagram of [i-C3H7-Ph3P]2MnBr4 in Example 10;

[0029] Figure 7The structural diagram of [PhCH2-Ph3P]2MnBr2Cl2 in Example 3;

[0030] Figure 8 The structural diagram of [C2H5-Ph3P]2MnBr4 in Example 7 is shown.

[0031] Figure 9 The structural diagram of [CH3-Ph3P]2MnBr4 in Example 6 is shown.

[0032] Figure 10 The structural diagram of [Ph4P]2MnBr4 in Example 8;

[0033] Figure 11 The XRD pattern of [2,4-DCl-PhCH2-Ph3P]2MnBr4 in Example 4;

[0034] Figure 12 The XRD pattern of [2,4-DCl-PhCH2-Ph3P]2MnCl4 in Example 5;

[0035] Figure 13 The XRD pattern of [p-C3H7-Ph3P]2MnCl2Br2 in Example 9;

[0036] Figure 14 The XRD pattern of [C3H5-Ph3P]2MnBr2Cl2 in Example 2;

[0037] Figure 15 The XRD pattern of [C3H5-Ph3P]2MnBr4 in Example 1;

[0038] Figure 16 The XRD pattern of [i-C3H7-Ph3P]2MnBr4 in Example 10;

[0039] Figure 17 The XRD pattern of [PhCH2-Ph3P]2MnBr2Cl2 in Example 3;

[0040] Figure 18 The XRD pattern of [C2H5-Ph3P]2MnBr4 in Example 7;

[0041] Figure 19 The XRD pattern of [CH3-Ph3P]2MnBr4 in Example 6;

[0042] Figure 20 The XRD pattern of [Ph4P]2MnBr4 in Example 8;

[0043] Figure 21The photoluminescence spectra of the compounds prepared in Examples 1-10 are shown below.

[0044] Figure 22 The photoluminescence excitation spectra of the compounds prepared in Examples 1-10 are shown below.

[0045] Figure 23 Fluorescence quantum yield plots for the compounds prepared in Examples 1, 6, 7 and 9;

[0046] Figure 24 Fluorescence quantum yield diagrams of the compounds prepared in Examples 2-5, 8, and 10;

[0047] Figure 25 The fluorescence lifetime results are for the compounds in Examples 1, 6-10;

[0048] Figure 26 The fluorescence lifetime results are for the compounds in Examples 2-5. Detailed Implementation

[0049] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0050] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0051] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0052] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0053] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0054] This invention provides a method for preparing zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halides (0DMn-OIMHs), comprising the following steps:

[0055] Quaternary phosphorus ionic liquid, hydrated manganese halide salt and oxalic acid dihydrate are ground and mixed evenly to obtain a mixture.

[0056] The mixture was transferred to a high-temperature reactor for high-temperature reaction. After cooling to room temperature, ethanol was added to the high-temperature reactor, and the mixture was heated to recrystallize. After cooling, zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halides (0DMn-OIMHs) were obtained.

[0057] The ratio of ethanol to quaternary phosphorus ionic liquid is 3 mL: 1 mol.

[0058] In a preferred embodiment of the present invention, the molar ratio of quaternary phosphonium ionic liquid, hydrated manganese halide salt and oxalate dihydrate (ox) is 1:1:1.

[0059] In a preferred embodiment of the present invention, the quaternary phosphonium-based ionic liquid is selected from methyltriphenylphosphonium bromide (CH3-Ph3P). + Br - ), Ethyltriphenylphosphonium bromide (C2H5-Ph3P) + Br - ), propyltriphenylphosphonium bromide (p-C3H7-Ph3P) + Br - ), isopropyltriphenylphosphonium bromide (i-C3H7-Ph3P) + Br - ), Cyclopropyltriphenylphosphonium bromide (C3H5-Ph3P) + Br - ), benzyltriphenylphosphonium bromide (PhCH2-Ph3P) + Br - ), tetraphenylphosphonium bromide (Ph4P) + Br - ), 2,4-dichloro-benzyltriphenylphosphonium bromide (2,4-DCl-PhCH2-Ph3P) + Cl - At least one of the following.

[0060] In a preferred embodiment of the present invention, the hydrated manganese halide salt is manganese chloride tetrahydrate (MnCl2·4H2O) or manganese bromide tetrahydrate (MnBr2·4H2O).

[0061] In a preferred embodiment of the present invention, the ratio of ethanol to quaternary phosphonium ionic liquid is 3 mL: 1 mol.

[0062] In a preferred embodiment of the present invention, the high-temperature reaction is carried out at a temperature of 180°C for 3 days.

[0063] In a preferred embodiment of the present invention, the temperature for recrystallization is 120°C and the time is 3 days.

[0064] This invention also proposes a zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide, which is prepared according to the above preparation method.

[0065] In a preferred embodiment of the present invention, the general chemical formula of the zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide is [R-Ph3P]2MnX4, where R is methyl, ethyl, propyl, isopropyl, cyclopropyl, benzyl, or 2,4-dichlorobenzyl, and X is Cl, Br, or a combination of Cl and Br. For example, when cyclopropyltriphenylphosphonium bromide (C3H5-Ph3P) is used... + Br - When prepared from manganese bromide tetrahydrate (MnBr2·4H2O) and oxalic acid dihydrate (ox), the chemical formula of the resulting zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide is [C3H5-Ph3P]2MnBr4.

[0066] When methyltriphenylphosphonium bromide (CH3-Ph3P) + Br - When prepared from manganese chloride tetrahydrate (MnCl2·4H2O) and oxalic acid dihydrate (ox), the chemical formula of the resulting zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide is [C3H5-Ph3P]2MnBr2Cl2.

[0067] When benzyltriphenylphosphonium bromide (PhCH2-Ph3P) + Br - When prepared from manganese chloride tetrahydrate (MnCl2·4H2O) and oxalic acid dihydrate (ox), the chemical formula of the resulting zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide is [PhCH2-Ph3P]2MnBr2Cl2.

[0068] When 2,4-dichloro-benzyltriphenylphosphonium bromide (2,4-DCl-PhCH2-Ph3P) is used... + Cl -When prepared from manganese bromide tetrahydrate (MnBr2·4H2O) and oxalic acid dihydrate (ox), the chemical formula of the resulting zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide is [2,4-DCl-PhCH2-Ph3P]2MnBr4.

[0069] When 2,4-dichloro-benzyltriphenylphosphonium bromide (2,4-DCl-PhCH2-Ph3P) is used... + Cl - When prepared from manganese chloride tetrahydrate (MnCl2·4H2O) and oxalic acid dihydrate (ox), the chemical formula of the resulting zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide is [2,4-DCl-PhCH2-Ph3P]2MnCl4.

[0070] When methyltriphenylphosphonium bromide (CH3-Ph3P) + Br - When prepared from manganese bromide tetrahydrate (MnBr2·4H2O) and oxalic acid dihydrate (ox), the chemical formula of the resulting zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide is [CH3-Ph3P]2MnBr4.

[0071] When ethyltriphenylphosphonium bromide (C2H5-Ph3P) is used + Br - When prepared from manganese bromide tetrahydrate (MnBr2·4H2O) and oxalic acid dihydrate (ox), the chemical formula of the resulting zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide is [C2H5-Ph3P]2MnBr4.

[0072] When tetraphenylphosphonium bromide (Ph4P) is used + Br - When prepared from manganese bromide tetrahydrate (MnBr2·4H2O) and oxalic acid dihydrate (ox), the chemical formula of the resulting zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide is [Ph4P]2MnBr4.

[0073] When propyltriphenylphosphonium bromide (p-C3H7-Ph3P) is used + Br - When prepared from manganese bromide tetrahydrate (MnBr2·4H2O) and oxalic acid dihydrate (ox), the chemical formula of the resulting zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide is [p-C3H7-Ph3P]2MnCl2Br2.

[0074] When isopropyltriphenylphosphonium bromide (i-C3H7-Ph3P) is used +When prepared from raw materials, manganese bromide tetrahydrate (MnBr2·4H2O) and oxalic acid dihydrate (ox), the chemical formula of the resulting zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide is [i-C3H7-Ph3P]2MnBr4.

[0075] This invention also proposes an application of the above-mentioned zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide in light-emitting devices.

[0076] All raw materials used in the embodiments of this invention were purchased commercially.

[0077] The technical solution of the present invention will be further illustrated by the following embodiments.

[0078] Example 1

[0079] A method for preparing a zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide ([C3H5-Ph3P]2MnBr4) includes the following steps:

[0080] C3H5-Ph3P + Br - (404 mg, 1 mmol), MnBr2·4H2O (292 mg, 1 mmol) and ox (127 mg, 1 mmol) were ground in an agate mortar for 10 minutes to ensure that the reactants were mixed evenly and to obtain a mixture.

[0081] The mixture was transferred to a high-temperature reactor lined with tetrafluoroethylene, sealed with a stainless steel sleeve, and reacted at 180°C for 3 days. After cooling to room temperature, a brownish-yellow solid was obtained. Then, 3 mL of ethanol was added to the lining of the high-temperature reactor, sealed, and recrystallized at 120°C for 3 days. After natural cooling, light green blocky crystals were obtained, which were zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halides ([C3H5-Ph3P]2MnBr4), with a yield of 80%.

[0082] Example 2

[0083] A method for preparing a zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide ([C3H5-Ph3P]2MnBr2Cl2) is the same as in Example 1, except that MnBr2·4H2O (292 mg, 1 mmol) is replaced with an equimolar amount of MnCl2·4H2O (198 mg, 1 mmol), with a yield of 85%.

[0084] [C3H5-Ph3P]2MnBr4 (unit cell parameters: a=14.76, b=16.17, c=16.899, α=90, β=90, γ=90, V=4033.12) and [C3H5-Ph3P]2MnBr2Cl2 (unit cell parameters: a=14.66, b=15.96, c=16.82, α=90, β=90, γ=90, V=3934.97) are isomorphic and crystallize in orthorhombic space group P212121. The asymmetric units of both compounds include a tetrahedral [MnX4]. 2- And two organic cations. For [C3H5-Ph3P]2MnBr4, the Mn-Br bond length varies in the range of [C3H5-Ph3P]2MnBr4. arrive The Br-Mn-Br angle is between 105.78(2)° and 112.97(2)°. In the mixed halide compound [C3H5-Ph3P]2MnBr2Cl2, the Mn-Br bond length ranges from […]. The Mn-Cl bond length range is: The key angles (Br-Mn-Br, Cl-Mn-Br, Cl-Mn-Cl) range from 106.63(7)° to 113.19(8)°.

[0085] Example 3

[0086] A method for preparing a zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide ([PhCH2-Ph3P]2MnBr2Cl2) is the same as in Example 2, except that C3H5-Ph3P is used instead of the quaternary phosphonium cation. + Br - (404 mg, 1 mmol) was replaced with an equimolar amount of PhCH2-Ph3PBr (456 mg, 1 mmol), with a yield of 93%.

[0087] [PhCH2-Ph3P]2MnBr2Cl2 (unit cell parameters: a=10.32, b=12.28, c=18.21, α=105.90, β=92.36, γ=93.16, V=2213.99) crystallizes in the triclinic system, space group P-1. The asymmetric unit of [PhCH2-Ph3P]2MnCl2Br2 includes a tetrahedral [MnX4]. 2- And two organic cations. In [PhCH2-Ph3P]2MnCl2Br2, the Mn-Br / Cl bond length ranges from [PhCH2-Ph3P]2MnCl2Br2. The bond angle ranges from 106.877(15)° to 112.167(14)°.

[0088] Example 4

[0089] A method for preparing a zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide ([2,4-DCl-PhCH2-Ph3P]2MnBr4) is the same as in Example 1, except that C3H5-Ph3P is used instead of the quaternary phosphonium cation. + Br - (404 mg, 1 mmol) was replaced with an equimolar amount of 2,4-DCl-PhCH2-Ph3P Cl (458 mg, 1 mmol), with a yield of 82%.

[0090] [2,4-DCl-PhCH2-Ph3P]2MnBr4 (unit cell parameters: a=13.81, b=18.61, c=19.16, α=90, β=95.237, γ=90, V=4905.65) crystallizes in the monoclinic system, space group P21 / n. The asymmetric unit of [2,4-DCl-PhCH2-Ph3P]2MnBr4 includes a tetrahedral [MnBr4]. 2- Two organic cations and one water molecule. In [2,4-DCl-PhCH2-Ph3P]2MnBr4, the Mn-Br bond length ranges from […]. The Br-Mn-Br bond angle ranges from 108.34(3)° to 110.34(3)°.

[0091] Example 5

[0092] A method for preparing a zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide ([2,4-DCl-PhCH2-Ph3P]2MnCl4) is the same as in Example 4, except that MnBr2·4H2O is replaced with an equimolar amount of MnCl2·4H2O (198 mg, 1 mmol), and the yield is 84%.

[0093] [2,4-DCl-PhCH2-Ph3P]2MnCl4 (unit cell parameters: a=17.05, b=22.41, c=27.42, α=90, β=101.08, γ=90, V=10285.5) crystallizes in the monoclinic system, space group P21 / c. The asymmetric unit of [2,4-DCl-PhCH2-Ph3P]2MnCl4 includes a tetrahedral [MnCl4] unit cell. 2- Two organic cations, one water molecule, and one ethanol molecule. In [2,4-DCl-PhCH2-Ph3P]2MnCl4, the Mn-Cl bond length ranges from […]. The Cl-Mn-Cl bond angle ranges from 107.25(2)° to 111.53(2)°.

[0094] Example 6

[0095] A method for preparing a zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide ([CH3-Ph3P]2MnBr4) is the same as in Example 1, except that C3H5-Ph3P is used instead of the quaternary phosphonium cation. + Br - (404 mg, 1 mmol) was replaced with an equimolar amount of CH3-Ph3PBr (364 mg, 1 mmol), with a yield of 85%.

[0096] [CH3-Ph3P]2MnBr4 (unit cell parameters a=9.763, b=12.420, c=16.535, α=90, β=105.527, γ=90, V=1936.47) crystallizes in the monoclinic system, space group P21. The asymmetric unit of [CH3-Ph3P]2MnBr4 includes a tetrahedral [MnBr4]. 2- And two organic cations. In [CH3-Ph3P]2MnBr4, the Mn-Br bond length ranges from [CH3-Ph3P]2MnBr4 to [CH3-Ph3P]2MnBr4. The bond angle ranges from 107.166(3)° to 112.370(2)°.

[0097] Example 7

[0098] A method for preparing a zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide ([C2H5-Ph3P]2MnBr4) is the same as in Example 1, except that C3H5-Ph3P is used instead of the quaternary phosphonium cation. + Br - (404 mg, 1 mmol) was replaced with an equimolar amount of C2H5-Ph3PBr (379 mg, 1 mmol), with a yield of 82%.

[0099] [C2H5-Ph3P]2MnBr4 (unit cell parameters a = 12.27, b = 21.282, c = 16.385, α = 90, β = 110.717, γ = 90, V = 4001.9) crystallizes in the monoclinic system, space group Cc. The asymmetric unit of [C2H5-Ph3P]2MnBr4 includes a tetrahedral [MnBr4]. 2- And two organic cations. In [C2H5-Ph3P]2MnBr4, the Mn-Br bond length ranges from [C2H5-Ph3P]2MnBr4. The bond angle ranges from 106.242(94)° to 114.853(94)°.

[0100] Example 8

[0101] A method for preparing a zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide ([Ph4P]2MnBr4) is the same as in Example 1, except that C3H5-Ph3P is used instead of the quaternary phosphonium cation. + Br - (404 mg, 1 mmol) was replaced with an equimolar amount of Ph4P Br (428 mg, 1 mmol), with a yield of 90%.

[0102] [Ph4P]2MnBr4 (unit cell parameters a = 11.30, b = 19.82, c = 20.64, α = 90, β = 92.34, γ = 90, V = 4617.7) crystallizes in the monoclinic system, space group C2 / c. The asymmetric unit of [Ph4P]2MnBr4 includes a tetrahedral [MnBr4]. 2- And two organic cations. In [Ph4P]2MnBr4, the Mn-Br bond length ranges from [Ph4P]2MnBr4 to [Ph4P]2MnBr4. The bond angle ranges from 106.873(2)° to 111.912(2)°.

[0103] Example 9

[0104] A method for preparing a zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide ([p-C3H7-Ph3P]2MnCl2Br2) is the same as in Example 1, except that C3H5-Ph3P is used instead of the quaternary phosphonium cation. + Br - (404 mg, 1 mmol) was replaced with an equimolar amount of p-C3H7-Ph3P Cl (385 mg, 1 mmol), with a yield of 91%.

[0105] [p-C3H7-Ph3P]2MnCl2Br2 (unit cell parameters: a=18.14, b=13.10, c=17.07, α=90, β=98.63, γ=90, V=4010.85) crystallizes in the monoclinic system, space group P21 / c. The asymmetric unit of [p-C3H7-Ph3P]2MnCl2Br2 includes a tetrahedral [MnX4]. 2- And two organic cations. In [p-C3H7-Ph3P]2MnCl2Br2, the Mn-Br / Mn-Cl bond length ranges from [p-C3H7-Ph3P]2MnCl2Br2. The bond angle ranges from 107.25(2)° to 111.53(2)°.

[0106] Example 10

[0107] A method for preparing a zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide ([i-C3H7-Ph3P]2MnBr4) is the same as in Example 1, except that C3H5-Ph3P is used instead of the quaternary phosphonium cation.+ Br - (404 mg, 1 mmol) was replaced with an equimolar amount of i-C3H7-Ph3PBr (385 mg, 1 mmol), with a yield of 91%.

[0108] [i-C3H7-Ph3P]2MnBr4 (unit cell parameters: a=17.06, b=14.86, c=18.11, α=90, β=116.60, γ=90, V=4105.61) crystallizes in the monoclinic system, space group P21 / n. The asymmetric unit of [i-C3H7-Ph3P]2MnBr4 includes a tetrahedral [MnBr4]. 2- And two organic cations. In [i-C3H7-Ph3P]2MnBr4, the Mn-Br bond length ranges from [i-C3H7-Ph3P]2MnBr4. The bond angle ranges from 106.141(18)° to 113.106(19)°.

[0109] The structural diagram of [2,4-DCl-PhCH2-Ph3P]2MnBr4 in Example 4 is shown below. Figure 1 XRD pattern (see) Figure 11 ;

[0110] The structural diagram of [2,4-DCl-PhCH2-Ph3P]2MnCl4 in Example 5 is shown below. Figure 2 XRD pattern (see) Figure 12 ;

[0111] The structural diagram of [p-C3H7-Ph3P]2MnCl2Br2 in Example 9 is shown below. Figure 3 XRD pattern (see) Figure 13 ;

[0112] The structural diagram of [C3H5-Ph3P]2MnBr2Cl2 in Example 2 is shown below. Figure 4 XRD pattern (see) Figure 14 ;

[0113] The structural diagram of [C3H5-Ph3P]2MnBr4 in Example 1 is shown below. Figure 5 XRD pattern (see) Figure 15 ;

[0114] The structural diagram of [i-C3H7-Ph3P]2MnBr4 in Example 10 is shown below. Figure 6 XRD pattern (see) Figure 16 ;

[0115] The structural diagram of [PhCH2-Ph3P]2MnBr2Cl2 in Example 3 is shown below. Figure 7 XRD pattern (see) Figure 17 ;

[0116] The structural diagram of [C2H5-Ph3P]2MnBr4 in Example 7 is shown below. Figure 8 XRD pattern (see) Figure 18 ;

[0117] The structural diagram of [CH3-Ph3P]2MnBr4 in Example 6 is shown below. Figure 9 XRD pattern (see) Figure 19 ;

[0118] The structural diagram of [Ph4P]2MnBr4 in Example 8 is shown below. Figure 10 XRD pattern (see) Figure 20 .

[0119] Depend on Figures 1-10 It can be seen that all ten compounds consist of large cations surrounding a tetrahedron [MnX4]. 2- The surrounding area, and due to the different organic cations, has different crystal space groups.

[0120] Depend on Figures 11-20 It can be seen that the experimental XRD patterns of the ten compounds prepared in Examples 1-10 are in excellent agreement with the patterns simulated by single crystal data, confirming their high phase purity.

[0121] The photoluminescence (PL) spectra of the compounds prepared in Examples 1-10 are shown below. Figure 21 Photoluminescence excitation (PLE) spectrum is shown in Figure 22 It can be seen that the PLE spectrum exhibits peaks at 280-313 nm, 359-365 nm, 376 nm, 435 nm, 451 nm, and 469 nm, which are related to Mn. 2+ The five spectral bands corresponding to the electronic transitions are consistent. The PLE peak in the 280-313 nm range originates from Mn. 2+ From the ground state 6 A1 to excited state 4 A2, 4 T1 and 4 T2( 4 The electronic transition process at the F-level (dd transition). The peak near 359-365 nm is attributed to... 6 A1 to 4 The electronic transition process of E ( 4 D). The peak near 376nm belongs to 6 A1 to 4 The electronic transition process of T2 ( 4 D). The peaks near 435nm, 451nm, and 469nm belong to... 6 A1 to 4 A1( 4 G) 4T2( 4 G) and 4 T1( 4 The electronic transition process of G). The PL spectra of these Mn-based OIMHs show that the emission peaks of [C3H5-Ph3P]2MnBr4 and [C3H5-Ph3P]2MnBr2Cl2 are 516 nm, [PhCH2-Ph3P]2MnBr2Cl2 has a peak of 511 nm, [CH3-Ph3P]2MnBr4 has a peak of 507 nm, [C2H5-Ph3P]2MnBr4 has a peak of 520 nm, and [Ph4P]2MnBr4 has a peak of 515 nm. The emission peak values ​​of [2,4-DCl-PhCH2-Ph3P]2MnCl4 and [2,4-DCl-PhCH2-Ph3P]2MnBr4 are both 523 nm, while the emission peak values ​​of [i-C3H7-Ph3P]2MnBr4 and [p-C3H7-Ph3P]2MnBr4 are 508 nm and 523 nm, respectively. Furthermore, the emission spectra of these Mn-based OIMHs show that their full width at half maximum (FWHM) is very narrow: 48 nm for [C3H5-Ph3P]2MnBr4, 46 nm for [C3H5-Ph3P]2MnBr2Cl2, 43 nm for [PhCH2-Ph3P]2MnBr2Cl2, 48 nm for [C2H5-Ph3P]2MnBr4, and 47 nm for [Ph4P]2MnBr4. The CIE chromaticity coordinates of [C3H5-Ph3P]2MnBr4 are (0.1525, 0.6817), and the color purity of [C3H5-Ph3P]2MnBr4 is calculated to be 90% using the reference method. For [C3H5-Ph3P]2MnBr2Cl2, the CIE chromaticity coordinates are (0.1417, 0.6978), and the color purity is 94%. The CIE chromaticity coordinates of [PhCH2-Ph3P]2MnBr2Cl2 are (0.1053, 0.6399), and the color purity is 87%. For comparison, we also calculated the CIE chromaticity coordinates and color purity of the other three zero-dimensional mn-based OIMHs. The CIE chromaticity coordinates of [CH3-Ph3P]2MnBr4 are (0.09, 0.6614), [C2H5-Ph3P]2MnBr4 are (0.1905, 0.6993), and [Ph4P]2MnBr4 are (0.1332, 0.6867). The color purity of [CH3-Ph3P]2MnBr4 is 93%, [C2H5-Ph3P]2MnBr4 is 89%, and [Ph4P]2MnBr4 is 92%. These exceptional color purities (87-94%) highlight the strong potential of these materials in high-quality white LED (WLED) applications.

[0122] Fluorescence quantum yield plots of the compounds prepared in Examples 1, 6, 7, and 9 are shown in the figure. Figure 23 The fluorescence quantum yield plots of the compounds prepared in Examples 2-5, 8, and 10 are shown in the figure. Figure 24 It can be seen that, under 450 nm excitation, the fluorescence quantum yield (PLQY) of these Mn-based OIMHs is 67.14% for [C3H5-Ph3P]2MnBr4, 45.56% for [C3H5-Ph3P]2MnBr2Cl2, 92.76% for [PhCH2-Ph3P]2MnBr2Cl2, 72.63% for [CH3-Ph3P]2MnBr4, and [2,4-DCl-PhCH2-Ph3P]2MnBr4. The fluorescence lifetimes of [p-C3H7-Ph3P]2MnBr4 and [2,4-DCl-PhCH2-Ph3P]2MnBr4 were 65.98% and 66.27%, respectively; the fluorescence lifetimes (PLQY) of [i-C3H7-Ph3P]2MnBr4 and [p-C3H7-Ph3P]2MnBr4 were 76.65% and 75.79%, respectively; those of [C2H5-Ph3P]2MnBr4 were 80.69%; and those of [Ph4P]2MnBr4 were 47.72%. These six zero-dimensional Mn... 2+ The significant differences in PLQY among the OIMHs may stem from variations in the Mn-Mn distance and their different crystal structures.

[0123] The fluorescence lifetime results of compounds in Examples 1 and 6-10 are shown in [the table below]. Figure 25 The fluorescence lifetime results of the compounds in Examples 2-5 are shown in [the table below]. Figure 26 It can be seen that under 450 nm excitation, the lifetime of [C3H5-Ph3P]2MnBr4 at 516 nm is 297.82 μs. At the same excitation wavelength, the lifetimes of [C3H5-Ph3P]2MnBr2Cl2 at 516 nm are 632.89 μs, [PhCH2-Ph3P]2MnBr2Cl2 at 511 nm are 401.84 μs, [CH3-Ph3P]2MnBr4 at 512 nm are 308.99 μs, [C2H5-Ph3P]2MnBr4 at 512 nm are 311.77 μs, and [Ph4P]2MnBr4 at 515 nm are 334.70 μs. The fluorescence lifetimes of [2,4-DCl-PhCH2-Ph3P]2MnCl4 and [2,4-DCl-PhCH2-Ph3P]2MnBr4 were 2000.74 and 389.04 μs, respectively, while the fluorescence lifetimes of [i-C3H7-Ph3P]2MnBr4 and [p-C3H7-Ph3P]2MnBr4 were 320.73 and 774.18 μs, respectively. These are comparable to previously reported manganese-based hybrid metal halide luminescent materials.

[0124] In summary, manganese-based OIMHs have broad application prospects in the field of white light-emitting diodes (WLEDs) due to their high photoluminescence quantum yield. However, traditional synthesis routes usually require strong acids (HBr, HCl, HI) and large amounts of organic solvents. These methods cause environmental problems and often lack versatility. This invention solves these limitations by employing an ionothermal method. To further demonstrate the universality of this synthesis method, this invention successfully synthesized large single crystals of [C2H5-Ph3P]2MnBr4, [Ph4P]2MnBr4, and [CH3-Ph3P]2MnBr4 listed in Examples 1-10 by simply changing the quaternary phosphonium cation. This is sufficient to prove that the acid-free, minimal solvent method adopted in this invention has good versatility and practicality in the synthesis of crystals of this series of compounds.

[0125] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A method for preparing zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide, characterized in that, Includes the following steps: Quaternary phosphorus ionic liquid, hydrated manganese halide salt and oxalic acid dihydrate are ground and mixed evenly to obtain a mixture. The mixture was transferred to a high-temperature reactor for high-temperature reaction. After cooling to room temperature, ethanol was added to the high-temperature reactor, and the mixture was heated to recrystallize. After cooling, the zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide was obtained. The ratio of ethanol to quaternary phosphorus ionic liquid is 3 mL: 1 mol.

2. The method for preparing zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide according to claim 1, characterized in that, The molar ratio of the quaternary phosphonium-based ionic liquid, the hydrated manganese halide salt, and the oxalate dihydrate is 1:1:

1.

3. The method for preparing zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide according to claim 1, characterized in that, The quaternary phosphonium-based ionic liquid is selected from at least one of methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, isopropyltriphenylphosphonium bromide, cyclopropyltriphenylphosphonium bromide, benzyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, and 2,4-dichloro-benzyltriphenylphosphonium chloride.

4. The method for preparing zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide according to claim 1, characterized in that, The hydrated manganese halide salt is manganese chloride tetrahydrate or manganese bromide tetrahydrate.

5. The method for preparing zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide according to claim 1, characterized in that, The ratio of ethanol to quaternary phosphonium-based ionic liquid is 3 mL: 1 mol.

6. The method for preparing zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide according to claim 1, characterized in that, The high-temperature reaction was carried out at 180°C for 3 days.

7. The method for preparing zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide according to claim 1, characterized in that, The temperature for the heat recrystallization was 120°C, and the time was 3 days.

8. A zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide, characterized in that, It is prepared according to any one of claims 1-7.

9. The application of the zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide as described in claim 8 in a light-emitting device.

10. The application of the zero-dimensional manganese-based quaternary phosphonium cation organic-inorganic hybrid metal halide according to claim 9 in light-emitting devices, characterized in that, The light-emitting device is a white light-emitting diode.

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