Organic-inorganic hybrid copper-based halide crystalline materials, methods of making and use

Abstract

The application belongs to the technical field of multifunctional photoelectric materials, and particularly relates to an organic-inorganic hybrid copper-based halide crystal material, a preparation method and application. R -2MePICu2X4, S -2MePICu2X4, R -2MePI)4Cu4X 12 or S -2MePI)4Cu4X 12 ; 2MePI is a 2-methylpiperazine cation, and X is a halogen. The application forms a coordination bond between monovalent metal Cu and a halogen, forms different inorganic cluster structures CuX, forms [Cu2X6] 4‑ or [Cu2X4] 2‑ units, and the 2-methylpiperazine cation is positively charged after protonation, and the formed CuX can achieve charge balance, so that the organic-inorganic hybrid copper-based halide crystal material is obtained through ionic bond interaction.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of multifunctional photoelectric materials, and particularly relates to an organic-inorganic hybrid copper-based halide crystal material and a preparation method and application thereof. BACKGROUND

[0002] Constructing advanced materials with integrated multiple properties in single crystal materials has attracted great research interest. In recent years, organic-inorganic hybrid metal halides have been considered as promising functional materials due to their structural diversity and excellent photophysical properties. Due to the high tunability of the structure of organic-inorganic hybrid metal halides, chiral groups can be reasonably introduced into the system as ligands or template cations to realize the construction of multifunctional materials. Chiral transmission from organic modules to inorganic components can be effectively realized not only through chemical bonds but also through weak interactions. The introduction of intrinsic chirality usually breaks the symmetry of the structure, thereby generating new photoelectric properties related to chirality, such as circular dichroism, circularly polarized luminescence, second harmonic generation, pyroelectricity, piezoelectricity, ferroelectricity, etc.

[0003] Among them, the introduction of chiral cations can further expand its development in the field of chiral photoelectricity, such as nonlinear optics, circularly polarized luminescence, ferroelectricity, thereby realizing the construction of multifunctional materials. However, it is difficult to obtain high-quality crystal samples after introducing chiral cations for constructing multifunctional metal halide systems, thereby it is difficult to establish a clear structure-effect relationship, which hinders the development of chiral multifunctional metal halide systems. SUMMARY

[0004] In order to solve the above problems, the application provides an organic-inorganic hybrid copper-based halide crystal material and a preparation method and application thereof.

[0005] The application solves the above technical problems through the following technical solutions.

[0006] The first object of the application is to provide an organic-inorganic hybrid copper-based halide crystal material, the chemical formula of the organic-inorganic hybrid copper-based halide crystal material is R -2MePICu2X4、 S -2MePICu2X4、 R -2MePI)4Cu4X 12 or S -2MePI)4Cu4X 12 , 2MePI is a 2-methylpiperazine cation, and X is a halogen.

[0007] The application constructs an organic-inorganic hybrid copper-based halide crystal material with 2-methylpiperazine cation, metal Cu and halogen. The monovalent metal Cu forms a coordination bond with halogen to form different inorganic cluster structures CuX, and form [Cu2X6] 4- or [Cu2X4] 2- units. The 2-methylpiperazine cation has two units of positive charge after being protonated, which can achieve charge balance with the formed CuX. Through ionic interaction, the organic-inorganic hybrid copper-based halide crystal material is obtained. In addition, since the 2-methylpiperazine cation and CuX can form hydrogen bond interaction, it is conducive to stabilizing the structure. Since the organic cation and the inorganic anion cluster are connected by non-covalent bonds such as ionic bonds, and the large lattice constant of the hybrid system, the hybrid metal halide system has a soft lattice characteristic. When the crystal material is excited by light, local distortion of the lattice is easily generated, and the exciton is trapped in the lattice by the generated lattice distortion, forming a self-trapped exciton. When the exciton relaxes back to the ground state, energy is released in the form of light, resulting in luminescence. The organic-inorganic hybrid copper-based halide has the advantages of adjustable emission peak position, high photoluminescence quantum yield, and large Stokes shift.

[0008] In some embodiments, X is Br or I. When X is Br, the organic-inorganic hybrid copper-based halide crystal material is R -2MePICu2Br4 or S -2MePICu2Br4. When X is I, the organic-inorganic hybrid copper-based halide crystal material is R -2MePI)4Cu4I 12 or S -2MePI)4Cu4I 12 . It should be noted that since Br - has a smaller radius of about 1.96 Å and a higher electronegativity of 2.96, it tends to form a stronger coordination bond. I - has a larger radius of about 2.20 Å and a lower electronegativity of 2.66, the coordination bond is weaker and the coordination mode is more flexible, and it is easy to form a high-dimensional structure. Therefore, when X is Br, a one-dimensional structure is formed by electrostatic interaction. When X is I, a two-dimensional structure is formed by electrostatic interaction. The one-dimensional structure or the two-dimensional structure is also related to the polarization ability of the halogen atom. The high polarizability of I - may promote the formation of more complex charge distribution and high dimensionality; while the rigidity of Br - tends to form a simple one-dimensional chain.

[0009] In some embodiments, the organic-inorganic hybrid copper-based halide crystal material belongs to the P 212121 space group of the orthorhombic system or P2221 space group; when the chemical formula of the organic-inorganic hybrid copper-based halide crystal material is R -2MePICu2Br4, the cell parameters are: a=6.1758(6) Å, b=13.7117(13) Å, c=15.3992(15) Å, α=β=γ=90°; when the chemical formula of the organic-inorganic hybrid copper-based halide crystal material is S -2MePICu2Br4, the cell parameters are: a=6.1758(6) Å, b=13.7117(13) Å, c=15.3992(15) Å, α=β=γ=90°; when the chemical formula of the organic-inorganic hybrid copper-based halide crystal material is R -2MePI)4Cu4I 12 , the cell parameters are: a=17.4929(15) Å, b=18.0250(14) Å, c=16.2543(13) Å, α=β=γ=90°; when the chemical formula of the organic-inorganic hybrid copper-based halide crystal material is S -2MePI)4Cu4I 12 , the cell parameters are: a=17.4929(15) Å, b=18.0250(14) Å, c=16.2543(13) Å, α=β=γ=90°; when the chemical formula of the organic-inorganic hybrid copper-based halide crystal material is

[0010] It should be noted that when X is Br, the organic-inorganic hybrid copper-based halide crystal material belongs to the P 212121 space group, when X is I, the organic-inorganic hybrid copper-based halide crystal material belongs to the P 2221 space group.

[0011] A second object of the present application is to provide a preparation method of the above-mentioned organic-inorganic hybrid copper-based halide crystal material, comprising the following steps:

[0012] After adding an acid reagent into cuprous halide and mixing uniformly, adding R- 2-methylpiperazine cation or S -2-methylpiperazine cation, through electrostatic interaction by solution method reaction, and obtaining the organic-inorganic hybrid copper-based halide crystal material after standing treatment.

[0013] It should be noted that the solution method is simpler for synthesis in the present application, and the one-dimensional or two-dimensional structure of the organic-inorganic hybrid copper-based halide crystal material formed by electrostatic interaction obtains a multifunctional copper-based material with fluorescence, second harmonic, and semiconductor properties, wherein the standing treatment time is 3d-5d.

[0014] In some embodiments, R -2-methylpiperazine cation or SThe molar ratio of 2-methylpiperazine cation to cuprous halide is 1:1 to 2.

[0015] In some embodiments, the molar volume ratio of cuprous halide to acid reagent is 1 mmol: 4 mL to 5 mL.

[0016] In some embodiments, the cuprous halide is cuprous bromide or cuprous iodide.

[0017] In some embodiments, the acid reagent is a mixture of hydrohalic acid and hypophosphorous acid in a volume ratio of 4 to 6:1, wherein the hydrohalic acid is hydrobromic acid. It should be noted that the purpose of using hydrobromic acid in this invention is to protonate the cations and provide a solvent environment, while the purpose of using hypophosphorous acid is to prevent the oxidation of cuprous ions.

[0018] In some embodiments, the reaction temperature is 110°C to 130°C and the reaction time is 3 min to 10 min.

[0019] A third objective of this invention is to provide the application of the above-mentioned organic-inorganic hybrid copper-based halide crystal materials in chiral multifunctional optoelectronic materials.

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

[0021] This invention provides an organic-inorganic hybrid copper-based halide crystal material. An organic-inorganic hybrid copper-based halide crystal material is constructed using 2-methylpiperazine cations, metallic Cu, and halogens. Different inorganic cluster structures, CuX, are formed by coordination bonds between the monovalent metal Cu and the halogens, resulting in [Cu2X6]. 4- Or [Cu2X4] 2- The 2-methylpiperazine cation, after protonation, carries two units of positive charge, which can achieve charge balance with the formed CuX. Through ionic bonding, an organic-inorganic hybrid copper-based halide crystal material is obtained. In addition, the hydrogen bonding between the 2-methylpiperazine cation and CuX is beneficial to the stability of the structure. Due to the non-covalent bonds such as ionic bonds between the organic cation and inorganic anion clusters and the large lattice constant of the hybrid system, the hybrid metal halide system has soft lattice characteristics. When the crystal material is photoexcited, local deformation of the lattice is easily generated. Excitons are trapped in the lattice by the generated lattice distortion, forming self-trapped excitons. When the excitons relax back to the ground state, they release energy in the form of light, producing luminescence. Organic-inorganic hybrid copper-based halides have advantages such as tunable emission peak position, high photoluminescence quantum yield, and large Stokes shift. Attached Figure Description

[0022] Figure 1 This is a structural diagram of the organic-inorganic hybrid copper-based halide crystal material prepared in Example 1 of the present invention.

[0023] Figure 2 Structure diagram of the organic-inorganic hybrid copper-based halide crystal material prepared in Example 2 of the present application.

[0024] Figure 3 Structure diagram of the organic-inorganic hybrid copper-based halide crystal material prepared in Example 3 and Example 4 of the present application.

[0025] Figure 4 PXRD test diagram of the organic-inorganic hybrid copper-based halide crystal material prepared in Example 1 and Example 2 of the present application, Figure 4 a is Example 1 and b is Example 2.

[0026] Figure 5 PXRD test diagram of the organic-inorganic hybrid copper-based halide crystal material prepared in Example 3 and Example 4 of the present application, Figure 5 a is Example 3 and b is Example 4.

[0027] Figure 6 UV-visible diffuse reflectance test diagram of the organic-inorganic hybrid copper-based halide crystal material prepared in Example 2 and Example 4 of the present application.

[0028] Figure 7 Fluorescence spectrum diagram of the organic-inorganic hybrid copper-based halide crystal material prepared in Example 1 to Example 4 of the present application.

[0029] Figure 8 Second harmonic generation test diagram of the organic-inorganic hybrid copper-based halide crystal material prepared in Example 2 and Example 4 of the present application. DETAILED DESCRIPTION

[0030] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative labor fall within the protection scope of the present application.

[0031] It should be noted that the professional terms used in the present application are only for the purpose of describing the specific embodiments, and are not intended to limit the protection scope of the present application. Unless otherwise specified, the various raw materials, reagents, instruments and equipment used in the following embodiments of the present application can be purchased from the market or prepared by the existing method.

[0032] The following will be further described through specific embodiments.

[0033] Example 1

[0034] The embodiment provides an organic-inorganic hybrid copper-based halide crystal material, a structural diagram of the organic-inorganic hybrid copper-based halide crystal material is as shown in Figure 1 The chemical formula of the organic-inorganic hybrid copper-based halide crystal material is R -2MePICu2Br4, 2MePI is a 2-methylpiperazine cation.

[0035] The preparation method of the organic-inorganic hybrid copper-based halide crystal material comprises the following steps:

[0036] 1 mmol, 0.143 g of cuprous bromide is weighed into a 25 mL beaker, 4 mL of hydrobromic acid and 0.8 mL of hypophosphorous acid are added, and stirring is performed on a magnetic stirrer at 120 DEG C for 20 min to obtain a colorless clear solution; 1 mmol, 0.100 g of R -2-methylpiperazine cation is added to the colorless clear solution, heating is continued for 3 min, and the solution is cooled at room temperature; colorless needle-shaped crystals are obtained after three days, which are the organic-inorganic hybrid copper-based halide crystal material.

[0037] Embodiment 2

[0038] The embodiment provides an organic-inorganic hybrid copper-based halide crystal material, a structural diagram of the organic-inorganic hybrid copper-based halide crystal material is as shown in Figure 2 The chemical formula of the organic-inorganic hybrid copper-based halide crystal material is S -2MePICu2Br4, 2MePI is a 2-methylpiperazine cation.

[0039] The preparation method of the organic-inorganic hybrid copper-based halide crystal material comprises the following steps:

[0040] 1 mmol, 0.143 g of cuprous bromide is weighed into a 25 mL beaker, 4 mL of hydrobromic acid and 0.8 mL of hypophosphorous acid are added, and stirring is performed on a magnetic stirrer at 120 DEG C for 20 min to obtain a colorless clear solution; 1 mmol, 0.100 g of S -2-methylpiperazine cation is added to the colorless clear solution, heating is continued for 3 min, and the solution is cooled at room temperature; colorless needle-shaped crystals are obtained after three days, which are the organic-inorganic hybrid copper-based halide crystal material.

[0041] Embodiment 3

[0042] The embodiment provides an organic-inorganic hybrid copper-based halide crystal material, a structural diagram of the organic-inorganic hybrid copper-based halide crystal material is as shown in Figure 3 The chemical formula of the organic-inorganic hybrid copper-based halide crystal material is R -2MePI)4Cu4I 12, 2MePI is 2-methylpiperazine cation.

[0043] The preparation method of the above-mentioned organic-inorganic hybrid copper-based halide crystal material comprises the following steps:

[0044] Take 1 mmol, 0.190 g of cuprous iodide and place it in a 25 mL beaker, add 4 mL of hydroiodic acid and 0.8 mL of hypophosphorous acid, stir on a magnetic stirrer at 120°C for 20 min to obtain a colorless clear solution; add 1 mmol, 0.100 g of R -2-methylpiperazine cation to the colorless clear solution, continue to heat for 3 min, stand and cool at room temperature, and obtain colorless needle-shaped crystals after three days, which are the organic-inorganic hybrid copper-based halide crystal material.

[0045] Example 4

[0046] The present example provides an organic-inorganic hybrid copper-based halide crystal material, and a structural diagram of the organic-inorganic hybrid copper-based halide crystal material is as shown in Figure 4 The chemical formula of the organic-inorganic hybrid copper-based halide crystal material is S -2MePI)4Cu4I 12 , 2MePI is 2-methylpiperazine cation.

[0047] The preparation method of the above-mentioned organic-inorganic hybrid copper-based halide crystal material comprises the following steps:

[0048] Take 1 mmol, 0.190 g of cuprous iodide and place it in a 25 mL beaker, add 4 mL of hydroiodic acid and 0.8 mL of hypophosphorous acid, stir on a magnetic stirrer at 120°C for 20 min to obtain a colorless clear solution; add 1 mmol, 0.100 g of S -2-methylpiperazine cation to the colorless clear solution, continue to heat for 3 min, stand and cool at room temperature, and obtain colorless needle-shaped crystals after three days, which are the organic-inorganic hybrid copper-based halide crystal material.

[0049] The organic-inorganic hybrid copper-based halide crystal materials prepared in Examples 1-4 are subjected to structure and performance testing, and the results are as follows:

[0050] SCXRD test: Single crystal diffraction data were collected at 298 K temperature using a Bruker D8 Venture single crystal diffractometer with Mo Ka radiation, and the data were reduced by the Bruker APEX3 program. The initial structure was solved by the direct method of the Olex2 software, which is an integrated SHELXTL package. The coordinates of all non-hydrogen atoms were determined by the difference Fourier method, and then anisotropic least-squares refinement based on F2was performed. The positions of hydrogen atoms were determined by theoretical hydrogenation.

[0051] RXRD test: Powder diffraction data were collected at 298 K using a SmartLab X-ray powder diffractometer, and the PXRD pattern was simulated by the Mercury software based on the obtained crystal data.

[0052] UV-Vis diffuse reflectance test: A UV-3600i Plus UV-Vis near-infrared spectrophotometer was used to collect UV-Vis diffuse reflectance spectral data. The reflectance spectrum was converted into an absorption spectrum according to the Kubelka-Munk function: a / S = F(R) = (1−R) 2 / (2R), where S is the scattering coefficient, a is the absorption coefficient, and R is the reflectivity.

[0053] Steady-state photoluminescence spectrum test: A LabRAM HR Evolution laser confocal micro-Raman spectrometer was used to collect steady-state fluorescence spectra at room temperature with a 325 nm laser as the light source.

[0054] Powder frequency doubling test: The powder frequency doubling test was performed on a modified Kurtz-NLO system, using a Nd:YAG laser with an output pulse energy of 350 mV as the excitation light source, and the wavelength was 1064 nm.

[0055] Figure 1 Structure diagram of the organic-inorganic hybrid copper-based halide crystal material prepared for Example 1 of the present application. As shown in Figure 1 , the organic-inorganic hybrid copper-based halide crystal material belongs to the orthorhombic P 212121space group; the chemical formula of the organic-inorganic hybrid copper-based halide crystal material is R -2MePICu2Br4, the unit cell parameters are: a = 6.1758(6) Å, b = 13.7117(13) Å, c = 15.3992(15) Å, α = β = γ = 90°; a one-dimensional chain structure is formed by [CuBr3] corner sharing, and the protonated R -2-methylpiperazine is orderly arranged between the inorganic chains.

[0056] Figure 2Structure of the organic-inorganic hybrid copper halide crystalline material prepared for Example 2 of the present invention. As shown in Figure 2 Figure 1, the organic-inorganic hybrid copper halide crystalline material crystallizes in the orthorhombic space group P 2121; the chemical formula of the organic-inorganic hybrid copper halide crystalline material is S -2MePICu2Br4, with unit cell parameters of a = 6.168(2) Å, b = 13.698(5) Å, c = 15.386(6) Å, a = b = g = 90°; a one-dimensional chain structure is formed through [CuBr3] corner sharing, with protonated S -2-methylpiperazine ordered arranged between the inorganic chains.

[0057] Figure 3 Structure of the organic-inorganic hybrid copper halide crystalline material prepared for Example 3 and Example 4 of the present invention. As shown in Figure 3 Figure 2, when the halogen is changed from Br to I, a two-dimensional layered iodide is constructed, the organic-inorganic hybrid copper halide crystalline material crystallizes in the orthorhombic space group P 2221, and the chemical formula of the organic-inorganic hybrid copper halide crystalline material is R -2MePI)4Cu4I 12 , with unit cell parameters of a = 17.4929(15) Å, b = 18.0250(14) Å, c = 16.2543(13) Å, a = b = g = 90°; a two-dimensional layer of anions [Cu4I 12 ] 8- is formed, and the layer is balanced by [R-2-H2MePI] 2+ cations. The monovalent copper ion forms a four-coordinated mode with four iodine ions, and the [CuI4] tetrahedron is connected through common corners to form a two-dimensional layered structure. When the chemical formula of the organic-inorganic hybrid copper halide crystalline material is S -2MePI)4Cu4I 12 , with unit cell parameters of a = 17.481(2) Å, b = 18.021(2) Å, c = 16.259(2) Å, a = b = g = 90°, the two-dimensional layer of anions [Cu4I 2+ ] is balanced by [S-2-H2MePI] 12 cations, and the monovalent copper ion forms a four-coordinated mode with four iodine ions, and the [CuI4] tetrahedron is connected through common corners to form a two-dimensional layered structure.

[0058] Figure 4 PXRD test pattern of the organic-inorganic hybrid copper halide crystalline material prepared for Example 1 and Example 2 of the present invention, wherein the a pattern is Example 1, and the b pattern is Example 2. As shown in Figure 4As shown, the measured PXRD pattern is consistent with the simulated SCXRD pattern, confirming that both crystalline materials are pure phases.

[0059] Figure 5 The images show the PXRD patterns of the organic-inorganic hybrid copper-based halide crystal materials prepared in Examples 3 and 4 of this invention. Figure 5 Figure a in the diagram represents Example 3, and Figure b represents Example 4. Figure 5 As shown, the measured PXRD pattern is consistent with the simulated SCXRD pattern, confirming that both crystalline materials are pure phases.

[0060] Figure 6 The images show the UV-Vis diffuse reflectance test results of the organic-inorganic hybrid copper-based halide crystal materials prepared in Examples 2 and 4 of this invention. Figure 6 As shown, the organic-inorganic hybrid copper-based halide crystal material prepared in Example 2 S The band gap of -2MePICu2Br4 is 3.8 eV. The organic-inorganic hybrid copper-based halide crystal material prepared in Example 4 ( S -2MePI)4Cu4I 12 The band gap is 3.7 eV.

[0061] Figure 7 The images show the fluorescence spectra of the organic-inorganic hybrid copper-based halide crystal materials prepared in Examples 1 to 4 of this invention. Figure 7 As shown, the organic-inorganic hybrid copper-based halide crystal materials prepared in Examples 1 and 2 exhibit weak photoluminescence properties under 325 nm ultraviolet light excitation.

[0062] Figure 8 The above are frequency doubling test patterns of the organic-inorganic hybrid copper-based halide crystal materials prepared in Examples 2 and 4 of this invention. Figure 8 As shown, the inorganic-inorganic hybrid copper-based halide crystal material prepared in Example 2 S The frequency doubling performance of the -2MePICu2Br4 powder sample was 0.071×KH2PO4. Example 4 prepared an inorganic-inorganic hybrid copper-based halide crystal material (…). S -2MePI)4Cu4I 12 The frequency doubling performance of the powder sample is 0.069 × KH2PO4.

[0063] It is to be understood that every range of values disclosed herein is to be understood to encompass any and every sub-range of values within the range. Although the preferred embodiments of the invention have been described above, it will be appreciated that those skilled in the art, on consideration of this disclosure, will be able to devise additional embodiments that, although not explicitly described or shown herein, nonetheless fall within the scope of the present invention. Accordingly, the appended claims are intended to include within their scope all such alternatives, modifications and variations as fall within the scope of the present invention. Various features and aspects of the present invention will become apparent from the following examples, which are intended only to exemplify the invention. It should be understood, of course, that in the various examples of the present invention, the specific phrasing of the claims will depend on the exact nature of the claims sought.

[0064] Obviously, numerous modifications and variations of the present application are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims and their equivalents, the present application can be practiced otherwise than as specifically described herein.

Claims

1. An organic-inorganic hybrid copper-based halide crystalline material, characterized in that, The chemical formula of the organic-inorganic hybrid copper-based halide crystalline material is R - 2MePICu2Br4, S - 2MePICu2Br4, R - 2MePI)4Cu4I 12 or S - 2MePI)4Cu4I 12 ; 2MePI is a 2-methylpiperazine cation; R - 2MePICu2Br4and S - 2MePICu2Br4belongs to the orthorhombic system P 212121 space group; R -2MePI)4Cu4I 12 and S -2MePI)4Cu4I 12 belonging to the orthorhombic system P 2221 space group;​ When the chemical formula of the organic-inorganic hybrid copper-based halide crystalline material is R -2MePICu2Br4, with the unit cell parameters: a = 6.1758(6) Å, b = 13.7117(13) Å, c = 15.3992(15) Å, α = β = γ = 90°; When the chemical formula of the organic-inorganic hybrid copper-based halide crystalline material is S -2MePICu2Br4, with the unit cell parameters: a = 6.168(2) Å, b = 13.698(5) Å, c = 15.386(6) Å, α = β = γ = 90°; When the chemical formula of the organic-inorganic hybrid copper-based halide crystalline material is R -2MePI)4Cu4I 12 with the unit cell parameters a = 17.4929(15) Å, b = 18.0250(14) Å, c = 16.2543(13) Å, α = β = γ = 90°; When the chemical formula of the organic-inorganic hybrid copper-based halide crystalline material is S -2MePI)4Cu4I 12 with the unit cell parameters a = 17.481(2) Å, b = 18.021(2) Å, c = 16.259(2) Å, α = β = γ = 90°.

2. A method of producing the organic-inorganic hybrid copper-based halide crystal material according to claim 1, characterized by, The method comprises the following steps: After adding acid reagent into cuprous halide, mix well, then add R- 2-methylpiperazine cation or S 2-methylpiperazine cation, electrostatic interaction is carried out by solution method reaction, and organic-inorganic hybrid copper-based halide crystal material is obtained after standing treatment.

3. The method of producing an organic-inorganic hybrid copper-based halide crystal material according to claim 2, characterized by, R - a 2-methylpiperazine cation or S - the molar ratio between the 2-methylpiperazine cation and the cuprous halide is 1 : 1 to 2.

4. The method of producing an organic-inorganic hybrid copper-based halide crystal material according to claim 2, characterized by, The cuprous halide is cuprous bromide or cuprous iodide.

5. The method of producing an organic-inorganic hybrid copper-based halide crystal material according to claim 2, wherein The molar volume ratio of the cuprous bromide and the acid reagent is 1 mmol:4 mL-5 mL.

6. The method of producing an organic-inorganic hybrid copper-based halide crystal material according to claim 2, wherein The acid reagent is a mixture of a hydrogen halide acid and hypophosphorous acid with a volume ratio of 4-6:1, and the hydrogen halide acid is hydrobromic acid.

7. The method of producing an organic-inorganic hybrid copper-based halide crystal material according to claim 2, wherein The reaction temperature is 110-130 DEG C, and the reaction time is 3-10 min.

8. The use of the organic-inorganic hybrid copper-based halide crystal material in claim 1 in a chiral multifunctional optoelectronic material.

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