A mechanoluminescent manganese-based halide and methods of making and using the same

Abstract

The application discloses a force-induced luminescent manganese-based halide and a preparation method and application thereof, relates to the field of luminescent materials, and has a chemical general formula of A-MnX4; wherein, the A group has a structural formula as shown in (I) or (II); X includes at least one of Cl and Br; and X and A are connected by a hydrogen bond. A chiral manganese-based metal halide is formed by combining a chiral organic cation and manganese halide through a hydrogen bond, so that the chirality of the organic cation is transmitted to the manganese halide, the manganese-based metal halide has chirality, and the manganese-based metal halide has the characteristics of force-induced luminescence (ML) and circularly polarized light (CPL), and can be applied to multiple confidential information encryption as an intelligent stimulus-response luminescent material.

Description

Technical Field

[0001] This invention relates to the field of luminescent materials, and particularly to a mechanoluminescent manganese-based halide, its preparation method, and its applications. Background Technology

[0002] Metal halides (HMHs) are a new class of optoelectronic materials with unique host-guest structures, showing great potential for applications in white light-emitting diodes, X-ray scintillators, and fluorescent sensors. However, the fact that the luminescence of metal halides is mainly caused by optical or electrical excitation limits their further application in diverse environments. Summary of the Invention

[0003] The main objective of this invention is to provide a mechanoluminescent manganese-based halide, its preparation method, and its application, aiming to provide a manganese-based halide with circularly polarized light emission characteristics that can be mechanoluminescent.

[0004] To achieve the above objectives, this invention proposes a mechanoluminescent manganese-based halide with the general chemical formula: A-MnX4;

[0005] Wherein: Group A has a structural formula as shown in (Ⅰ) or (Ⅱ):

[0006]

[0007] X includes at least one of Cl and Br;

[0008] X and A are connected by hydrogen bonds.

[0009] This invention also proposes a method for preparing mechanoluminescent manganese-based halides, comprising the following steps:

[0010] 2,4-bis(diphenylphosphine)pentane was mixed with manganese halide and reacted in acid to obtain a mixed solution;

[0011] The solvent is mixed with the mixture, the solvent is evaporated, and methemoluminescent manganese-based halides are crystallized out.

[0012] Optionally, the manganese halide includes at least one of MnBr4, MnBr3Cl, MnBr2Cl2, MnBrCl3, and MnCl4.

[0013] Optionally, the 2,4-bis(diphenylphosphine)pentane includes (2R,4R)-(+)-2,4-bis(diphenylphosphine)pentane (RR-BDPP) or (2S,4S)-(-)-2,4-bis(diphenylphosphine)pentane (SS-BDPP).

[0014] Optionally, the solvent includes at least one of methanol, ethanol, acetone and acetonitrile.

[0015] Optionally, the acid includes at least one of HBr and HCl.

[0016] Optionally, the step of mixing 2,4-bis(diphenylphosphine)pentane with manganese halide and reacting it in acid to obtain a mixed solution includes:

[0017] The reaction temperature is 70–150 °C; and / or,

[0018] The reaction time is 0.1 to 3 hours.

[0019] Optionally, in the process of mixing the solvent with the mixture, evaporating the solvent, and crystallizing out the metronic manganese-based halide:

[0020] The volatilization temperature is 35–80℃; and / or,

[0021] The cooling rate during crystallization is 0.05–20 °C / min.

[0022] This invention also proposes an anti-counterfeiting device, comprising an encryption material, wherein the encryption material comprises the aforementioned mechanoluminescent manganese-based halide, or a mechanoluminescent manganese-based halide prepared by the aforementioned method. The mechanoluminescent manganese-based halide has the general chemical formula: A-MnX 4， Wherein: Group A has a structural formula as shown in (Ⅰ) or (Ⅱ):

[0023]

[0024] X includes at least one of Cl and Br;

[0025] X and A are connected by hydrogen bonds.

[0026] This invention also proposes a pressure sensing device, comprising a pressure-sensing material, wherein the pressure-sensing material comprises the aforementioned mechanoluminescent manganese-based halide, or a mechanoluminescent manganese-based halide prepared by the aforementioned method. The mechanoluminescent manganese-based halide has the general chemical formula: A-MnX 4， Wherein: Group A has a structural formula as shown in (Ⅰ) or (Ⅱ):

[0027]

[0028] X includes at least one of Cl and Br;

[0029] X and A are connected by hydrogen bonds.

[0030] In the technical solution of this invention, a chiral manganese-based metal halide is formed by hydrogen bonding between a chiral organic cation and manganese halide in a large conjugated system. This transfers the chirality of the organic cation to the manganese halide, giving the manganese-based metal halide chirality and the characteristics of mechanoluminescence and circularly polarized light. It can be used as a smart stimulus-response luminescent material for encryption of multiple confidential information. Attached Figure Description

[0031] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the structures shown in these drawings without creative effort.

[0032] Figure 1 The XRD patterns of the mechanoluminescent manganese-based halides and corresponding standard powders of Examples 1 and 3 of this invention are shown.

[0033] Figure 2 The circular dichroism spectrum, photoluminescence spectrum, and circularly polarized light emission spectrum of the mechanoluminescent manganese-based halides in Examples 1 and 3 of the present invention are shown.

[0034] Figure 3 This is the mechanoluminescence spectrum of the mechanoluminescent manganese-based halide of Example 1 of the present invention under a force of 30 N;

[0035] Figure 4 The images show the mechanoluminescence spectra of the luminescent manganese-based halides of Example 1 of the present invention under different force values.

[0036] Figure 5 The images show the mechanoluminescence spectra of the luminescent manganese-based halides of Example 3 of the present invention under different force values.

[0037] Figure 6 The images show the polarization dependence ML intensity and CPML patterning effect of the mechanoluminescent manganese-based halides in Embodiments 1 and 3 of the present invention when the linear polarizer is rotated at different angles, as well as the decryption effect of the encrypted information.

[0038] Figure 7 The polarization-dependent ML spectra of the mechanoluminescent manganese-based halide of Embodiment 1 of the present invention when the linear polarizer is rotated at different angles under the action of a 30N force.

[0039] Figure 8 The polarization-dependent ML spectra of the mechanoluminescent manganese-based halide of Embodiment 3 of the present invention when the linear polarizer is rotated at different angles under the action of a 30N force.

[0040] Figure 9 The polarization-dependent ML spectra of mechanoluminescent manganese-based halides of Examples 1 and 3 when a 1:1 racemic mixture is subjected to a 30N force and the linear polarizer is rotated at different angles.

[0041] Figure 10 The polarization-dependent ML spectra of the manganese-based halide of Comparative Example 2 of the present invention when the linear polarizer is rotated at different angles under the action of a 30N force.

[0042] Figure 11 The polarization-dependent ML spectra of the manganese-based halide of Comparative Example 3 of the present invention when the linear polarizer is rotated at different angles under the action of a 30N force.

[0043] Figure 12 The ML spectrum of the mechanoluminescent manganese-based halide of Example 1 of the present invention after three cycles under a force of 30N;

[0044] Figure 13 These are schematic diagrams of the crystal structures of the mechanoluminescent manganese-based halides in Examples 1 and 3 of the present invention;

[0045] Figure 14 This is a schematic diagram of the crystal structure of the mechanoluminescent manganese-based halide in Embodiment 2 of the present invention;

[0046] Figure 15 This is a schematic diagram of the crystal structure of the mechanoluminescent manganese-based halide of Comparative Example 2 of the present invention.

[0047] The objectives, features, and advantages of this invention will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation

[0048] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Where the manufacturers of reagents or instruments are not specified, they are all conventional products that can be purchased commercially. Furthermore, the meaning of "and / or" throughout the text includes three parallel solutions; for example, "A and / or B" includes solution A, or solution B, or a solution where both A and B are satisfied simultaneously. In addition, the technical solutions of the various embodiments can be combined with each other, but this must be based on the ability of those skilled in the art to implement them. When the combination of technical solutions is contradictory or cannot be implemented, it should be considered that such a combination of technical solutions does not exist and is not within the scope of protection claimed by the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0049] In view of this, the present invention provides a mechanoluminescent manganese-based halide, which aims to provide a mechanoluminescent manganese-based halide with circularly polarized light emission characteristics.

[0050] In this invention, the general chemical formula of the mechanoluminescent manganese-based halide is: A-MnX4;

[0051] Wherein: Group A has a structural formula as shown in (Ⅰ) or (Ⅱ):

[0052]

[0053] X includes at least one of Cl and Br;

[0054] X and A are connected by hydrogen bonds.

[0055] In the technical solution of this invention, a chiral manganese-based metal halide is formed by hydrogen bonding between a chiral organic cation and manganese halide in a large conjugated system. This transfers the chirality of the organic cation to the manganese halide, giving the manganese-based metal halide chirality and thus the characteristics of mechanoluminescence (ML) and circularly polarized light (CPL). It can be used as a smart stimulus-response luminescent material for encryption of multiple confidential information.

[0056] The sensitivity of mechanoluminescence can be attributed to the abundant hydrogen bonding interactions between inorganic anions and chiral organic cations within the crystal structure, as well as the molecular rigidity resulting from their close packing. These factors make chiral manganese-based metal halides highly sensitive to mechanical stress stimuli.

[0057] It should be noted that X can only be selected from at least one of Cl and Br to achieve mechanoluminescence with circularly polarized light characteristics. When X is selected from I, it is impossible to obtain a manganese-based metal halide with mechanoluminescence and circularly polarized light characteristics. A must be a chiral bisphenylphosphine pentane, that is, A must be a phenylphosphine pentane with both left-handed and right-handed structures, so that the chirality of the A group can be transferred to the manganese halide through hydrogen bonding, achieving the emission of mechanoluminescent circularly polarized light. In particular, when X is entirely selected from Br, a chiral manganese-based metal halide with high mechanical stress sensitivity can be obtained, which can detect ML emission even under a force of 0.1 N, and the ML emission under force-stimulation exhibits circularly polarized light.

[0058] Through hydrogen bonding, the chirality of the A group can be transferred to manganese halide, achieving circularly polarized positive light emission from manganese halide.

[0059] The A group of chiral ligands possesses a large conjugated system, which not only facilitates the formation of abundant hydrogen bonds but also promotes chiral transfer and mechanoluminescence emission in chiral halides. Furthermore, the large molecular volume of the A group increases the distance between inorganic components, thereby enhancing the response sensitivity of the chiral halides. Therefore, constructing zero-dimensional chiral manganese halides using the A group of chiral ligands can achieve mechanoluminescence emission of chiral halides.

[0060] This invention also proposes a method for preparing mechanoluminescent manganese-based halides, comprising the following steps:

[0061] 2,4-bis(diphenylphosphine)pentane was mixed with manganese halide and reacted in acid to obtain a mixed solution;

[0062] The solvent is mixed with the mixture, the solvent is evaporated, and methemoluminescent manganese-based halides are crystallized out.

[0063] 2,4-bis(diphenylphosphine)pentane gains a hydrogen atom in the presence of acid, forming a positively charged cation, while the inorganic manganese halide cluster is negatively charged. The organic 2,4-bis(diphenylphosphine)pentane and the inorganic manganese halide cluster are linked by weak interactions such as ionic interactions and hydrogen bonds, forming a zero-dimensional organic-inorganic hybrid manganese halide. Among them, (2R,4R)-(+)-2,4-bis(diphenylphosphine)pentane or (2S,4S)-(-)-2,4-bis(diphenylphosphine)pentane has a large conjugated system, which is conducive to the formation of hydrogen bonds and the separation of the luminescent centers between the inorganic manganese halide clusters. Therefore, this zero-dimensional organic-inorganic hybrid manganese halide exhibits strong emission and highly sensitive mechanoluminescence. Simultaneously, (2R,4R)-(+)-2,4-bis(diphenylphosphine)pentane or (2S,4S)-(-)-2,4-bis(diphenylphosphine)pentane are chiral, and the luminescent centers of the induced inorganic manganese halide clusters, through hydrogen bonding interactions, are also chiral, thus forming circularly polarized light emission. Combined with the mechanoluminescence properties, this zero-dimensional organic-inorganic hybrid manganese halide exhibits unique mechano-induced circularly polarized light emission.

[0064] It should be noted that the molar ratio of 2,4-bis(diphenylphosphine)pentane to manganese halide can be (0.67–1):1. Within this mass ratio range, hydrogen bonding between 2,4-bis(diphenylphosphine)pentane and manganese halide can be achieved. Increasing the number of hydrogen bonds in the mechanoluminescent manganese-based halide improves the sensitivity of mechanoluminescence. The molar ratio of 2,4-bis(diphenylphosphine)pentane to manganese halide can be 0.67:1, 0.7:1, 0.75:1, 0.8:1, 0.85:1, 0.9:1, 0.95:1, or 1:1. To further improve the purity and yield of the mechanoluminescent manganese-based halide, the molar ratio of 2,4-bis(diphenylphosphine)pentane to manganese halide is preferably 1:1.

[0065] In any embodiment of the present invention, the manganese halide includes at least one of MnBr4, MnBr3Cl, MnBr2Cl2, MnBrCl3, and MnCl4. Using at least one of the above-mentioned manganese halides can improve the sensitivity and luminescence effect of mechanoluminescence of manganese-based halides.

[0066] In any embodiment of the present invention, the 2,4-bis(diphenylphosphine)pentane comprises (2R,4R)-(+)-2,4-bis(diphenylphosphine)pentane or (2S,4S)-(-)-2,4-bis(diphenylphosphine)pentane. (2R,4R)-(+)-2,4-bis(diphenylphosphine)pentane and (2S,4S)-(-)-2,4-bis(diphenylphosphine)pentane are a pair of 2,4-bis(diphenylphosphine)pentanes having a levorotatory structure and a dextrorotatory structure, which allows the mechanoluminescent manganese-based halides to exhibit circularly polarized light characteristics while simultaneously exhibiting mechanoluminescence, further improving the mechanoluminescence sensitivity of the mechanoluminescent manganese-based halides.

[0067] In any embodiment of the present invention, the solvent includes at least one selected from methanol, ethanol, acetone, and acetonitrile. Using at least one of the above solvents facilitates the dissolution of the mechanoluminescent manganese-based halide while simultaneously allowing for solvent evaporation, thus promoting the crystallization and precipitation of the mechanoluminescent manganese-based halide to obtain a crystal structure.

[0068] In any embodiment of the present invention, the acid includes at least one of HBr and HCl. Using at least one of the above-mentioned acidic substances can provide H atoms, making 2,4-bis(diphenylphosphine)pentane positively charged, thus facilitating hydrogen bonding between 2,4-bis(diphenylphosphine)pentane and manganese halide. This increases the number of hydrogen bonds in the mechanoluminescent manganese-based halide, thereby improving the sensitivity of the mechanoluminescence of the manganese-based halide. It should be noted that in the embodiments of the present invention, the main function of the acid is to provide H atoms; therefore, the present invention does not limit the concentration of the acid. In some embodiments, HCl can be 5% to 37% by mass, and HBr can be 5% to 68.85% by mass.

[0069] In any embodiment of the present invention, the step of mixing 2,4-bis(diphenylphosphine)pentane with manganese halide and reacting it in acid to obtain a mixed solution includes:

[0070] The reaction temperature is 70–150℃. Within this temperature range, increasing the reaction rate and reducing side reactions is beneficial for the dissolution of the highly mechanoluminescent manganese-based halides in the solvent. The reaction temperature can be 70℃, 80℃, 90℃, 100℃, 110℃, 120℃, 130℃, 140℃, or 150℃.

[0071] In any embodiment of the present invention, the reaction time is 0.1 to 3 hours. Within this reaction time, the yield of mechanoluminescent manganese-based halides can be increased. The reaction time can be 0.1 hours, 0.5 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours, or 3 hours.

[0072] In any embodiment of the present invention, the process of mixing the solvent with the mixture, evaporating the solvent, and crystallizing out the metronoluminescent manganese-based halide is as follows:

[0073] The evaporation temperature is 35–80℃. Within this temperature range, the solvent evaporation rate can be increased, thus improving the crystallization rate. The evaporation temperature can be 40℃, 45℃, 50℃, 55℃, or 60℃.

[0074] In any embodiment of the present invention, the cooling rate for crystallization is 0.05–20 °C / min. Within this cooling rate range, a suitable cooling rate can be selected according to the required crystal size. It should be noted that in this application, the size of the mechanoluminescent manganese-based halide crystals can be controlled by controlling the cooling rate of crystallization. The slower the cooling rate, the larger the mechanoluminescent manganese-based halide crystals; the faster the cooling rate, the smaller the mechanoluminescent manganese-based halide crystals. The cooling rate for crystallization can be 0.05 °C / min, 1 °C / min, 5 °C / min, 10 °C / min, 12 °C / min, 15 °C / min, or 20 °C / min.

[0075] This invention also proposes an anti-counterfeiting device, comprising an encryption material, wherein the encryption material comprises the aforementioned mechanoluminescent manganese-based halide, or a mechanoluminescent manganese-based halide prepared by the aforementioned method for preparing mechanoluminescent manganese-based halides. The anti-counterfeiting device incorporates all the technical solutions of the aforementioned mechanoluminescent manganese-based halide, and thus possesses all the beneficial effects of the aforementioned mechanoluminescent manganese-based halide; these will not be elaborated upon further here.

[0076] This invention also proposes a pressure sensing device, comprising a pressure-sensing material, wherein the pressure-sensing material comprises the aforementioned mechanoluminescent manganese-based halide, or a mechanoluminescent manganese-based halide prepared by the aforementioned method. The pressure sensing device incorporates all the technical solutions of the aforementioned mechanoluminescent manganese-based halide, and therefore possesses all the beneficial effects of the aforementioned mechanoluminescent manganese-based halide, which will not be elaborated upon here.

[0077] The technical solution of the present invention will be further described in detail below with reference to specific embodiments and accompanying drawings. It should be understood that the following embodiments are only used to explain the present invention and are not intended to limit the present invention.

[0078] Example 1

[0079] A mechanoluminescent manganese-based halide with the general chemical formula A-MnX4, where X is Br, and the structural formula of A is shown in formula (Ⅰ):

[0080]

[0081] Example 2

[0082] A mechanoluminescent manganese-based halide with the general chemical formula A-MnX4, wherein X is Cl, and the structural formula of A is shown in formula (Ⅰ):

[0083]

[0084] Example 3

[0085] A mechanoluminescent manganese-based halide with the general chemical formula A-MnX4, wherein X is Br, and the structural formula of A is shown in formula (II):

[0086]

[0087] Example 4

[0088] A mechanoluminescent manganese-based halide with the general chemical formula A-MnX4, wherein X4 is Cl2Br2, and the structural formula of A is shown in formula (Ⅰ):

[0089]

[0090] Example 5

[0091] A method for preparing a mechanoluminescent manganese-based halide, with the same chemical structure as in Example 1, includes the following steps:

[0092] 1 mol of (2R,4R)-(+)-2,4-bis(diphenylphosphine)pentane (RR-BDPP) and 1 mol of MnBr2 were placed in a 50 mL glass bottle, 15 mL of HBr (40% by mass) was added, the mixture was heated to 100 °C and stirred until a uniform suspension was formed. The reaction was allowed to proceed for 2 h. If the mixture stuck to the glass bottle wall or agglomerated, it could be dispersed by ultrasonic vibration to obtain a mixed solution.

[0093] Ethanol was mixed with the mixture, and the ethanol solution was slowly evaporated in a vacuum drying oven at 35°C to reduce solubility. The mixture was cooled at 0.05°C / min to crystallize and generate mechanoluminescent manganese-based halide crystals.

[0094] Example 6

[0095] A method for preparing a mechanoluminescent manganese-based halide, with the same chemical structure as in Example 2, includes the following steps:

[0096] 1 mol of (2R,4R)-(+)-2,4-bis(diphenylphosphine)pentane (RR-BDPP) and 1 mol of MnCl2 were placed in a 50 mL glass bottle, 15 mL of HCl (37% by mass) was added, the mixture was heated to 70 °C and stirred until a uniform suspension was formed. The reaction was allowed to proceed for 3 h. If the mixture stuck to the glass bottle wall or agglomerated, it could be dispersed by ultrasonic vibration to obtain a mixed solution.

[0097] Ethanol was mixed with the mixture, and the ethanol solution was slowly evaporated in a vacuum drying oven at 45°C to reduce solubility. The mixture was then cooled at 5°C / min to crystallize and generate mechanoluminescent manganese-based halide crystals.

[0098] Example 7

[0099] A method for preparing a mechanoluminescent manganese-based halide, with the same chemical structure as in Example 3, includes the following steps:

[0100] 1 mol of (2S,4S)-(-)-2,4-bis(diphenylphosphine)pentane (SS-BDPP) and 1 mol of MnBr2 were placed in a 50 mL glass bottle, 15 mL of HBr (40% by mass) was added, the mixture was heated to 150 °C and stirred until a uniform suspension was formed. The reaction was allowed to proceed for 0.1 h. If the mixture stuck to the glass bottle wall or agglomerated, it could be dispersed by ultrasonic vibration to obtain a mixed solution.

[0101] Mixing ethanol with the mixture and heating it at 60°C to evaporate the ethanol solution and reduce its solubility, followed by rapid cooling at 20°C / min for rapid crystallization, can generate manganese-based halide microcrystals with mechanoluminescence.

[0102] Example 8

[0103] A method for preparing a mechanoluminescent manganese-based halide, with the same chemical structure as in Example 4, includes the following steps:

[0104] 1 mol of (2R,4R)-(+)-2,4-bis(diphenylphosphine)pentane (RR-BDPP) was placed in a 50 mL glass bottle with 0.5 mol of MnBr2 and 0.5 mol of MnCl2. 15 mL of HBr (40% by mass) was added. The mixture was heated to 100 °C and stirred until a uniform suspension was formed. The reaction was allowed to proceed for 2 h. If the mixture stuck to the glass bottle wall or agglomerated, it could be dispersed by ultrasonic vibration to obtain a mixed solution.

[0105] Ethanol was mixed with the mixture, and the ethanol solution was heated at 80°C to evaporate and reduce the solubility. The solution was then cooled at 10°C / min to crystallize and generate mechanoluminescent manganese-based halide crystals.

[0106] Comparative Example 1

[0107] Comparative Example 1 is the same as Example 1 except that X is I.

[0108] Since Comparative Example 1 does not contain Cl or Br, it cannot form a mechanoluminescent manganese-based halide with circularly polarized light. The inability of I halides to form mechanoluminescent manganese-based halides with circularly polarized light is related to their luminescence efficiency; typically, zero-dimensional metallic manganese iodide halides do not emit light.

[0109] Comparative Example 2

[0110] Compared with Example 1, Comparative Example 2 has the following structure, except for the A group, which is shown in Formula (Ⅲ):

[0111]

[0112] Because Comparative Example 2 lacks 2,4-bis(diphenylphosphine)pentane, it is impossible to form a manganese-based halide crystal with circularly polarized light that exhibits mechanoluminescence. The generation of mechanoluminescence is related to the crystal structure, including the size and configuration of the organic cation, as well as the interaction between the organic cation and the inorganic metal cluster, and is also related to the luminescence efficiency of the metal halide. When A changes, the corresponding crystal structure and the luminescence efficiency of the formed metal halide both change; therefore, sufficient excitation energy cannot be generated under mechanical force, resulting in the failure of mechanoluminescence.

[0113] Comparative Example 3

[0114] Comparative Example 3 is a non-chiral doped inorganic crystal CaZnOS:Mn.

[0115] Performance testing

[0116] The mechanoluminescent manganese-based halide crystals and corresponding standard powders from Examples 1 and 3 were subjected to X-ray diffraction (XRD). The results are as follows: Figure 1 As shown, by Figure 1 It can be seen that the XRD patterns of the mechanoluminescent manganese halide crystals of Examples 1 and 3 are consistent with those of the corresponding standard powders, indicating that the phase purity of the mechanoluminescent manganese halide crystals prepared in Examples 1 and 3 is very high.

[0117] The mechanoluminescent manganese-based halide crystals of Examples 1 and 3 were subjected to circular dichroism (CD) spectroscopy analysis, such as... Figure 2 a and Figure 2 As shown in b, it is demonstrated that the chirality of the chiral ligand RR-BDPP in Example 1 and the chiral ligand SS-BDPP in Example 3 is transferred to the inorganic luminescent center manganese bromide through hydrogen bonding interactions.

[0118] The mechanoluminescent manganese-based halide crystals of Examples 1 and 3 were subjected to photoluminescence (PL) analysis, such as... Figure 2 As shown in Figure c, the PL emission peaks of Examples 1 and 3 are at 523 nm, with a full width at half maximum (FWHM) of 48 nm, which can be attributed to typical tetrahedral coordinated Mn(II) ions from... 4 T1 to 6 The electronic transition of A1 is shown in the figure as green fluorescence.

[0119] The mechanoluminescent manganese-based halide crystals of Examples 1 and 3 were analyzed by circularly polarized light luminescence (CPL), such as... Figure 2 As shown in d, under 363nm ultraviolet light excitation, the CPL signals of Examples 1 and 3 were observed to be mirror-symmetric, with a peak at 530nm.

[0120] The mechanoluminescent manganese-based halide crystal from Example 1 was subjected to mechanoluminescence (ML) testing under a force of 30 N, and the results were compared with photoluminescence (PL) spectra. Figure 3 As shown, the mechanoluminescence (ML) spectrum of Example 1 under 30N force is almost identical to the photoluminescence (PL) spectrum under 363nm ultraviolet light excitation, indicating that both ML and PL emissions are attributed to Mn(II) ions emanating from the Mn(II) ions. 4 T1 to 6 Electron transition of A1.

[0121] The luminescence of the mechanoluminescent manganese-based halide crystals from Examples 1 and 3 was detected under different force values, and the results are as follows: Figure 4 and Figure 5As shown, Examples 1 and 3 exhibited unusual sensitivity to mechanical stress. ML spectra under different stresses showed that the ML intensity of Example 1 increased with increasing mechanical stress, and ML emission could be detected even under a force of 0.1 N. This indicates that the mechanoluminescent manganese-based halides possess high luminescence sensitivity.

[0122] To verify the mechanoluminescence circularly polarized emission (CPML) of manganese-based halides in Examples 1 and 3, a quarter-wave plate (λ / 4 plate) and a linear polarizer were installed between the test sample and the spectrometer. Figure 6 a) The ML generated in Examples 1 and 3 is converted into linearly polarized light after passing through a λ / 4 plate. The intensity of the ML changes drastically as the linearly polarized plate rotates at different angles. For example... Figure 6 b and Figure 7-8 As shown, the ML intensity of Examples 1 and 3 exhibits a clear polarization dependence, showing distinct and opposite changes with different rotation angles between the λ / 4 plate and the linear polarizer. For example, the stronger ML intensity of Example 1 appears at 90° and 270°, while the stronger ML intensity of Example 3 appears at 0° and 180°. In contrast, under the same experimental conditions, the ML intensity of the 1:1 racemic mixture of Examples 1 and 3 did not show this change. Figure 6 b and Figure 9 Furthermore, the ML intensity of the non-chiral HMH material in Comparative Example 2 and the non-chiral doped inorganic crystal CaZnOS:Mn in Comparative Example 3 also does not exhibit this polarization dependence. Figure 10-11 Therefore, the force-induced circularly polarized light emission (CPML) performance of Examples 1 and 3 has been demonstrated.

[0123] The unique CPML properties of Examples 1 and 3 endow them with great potential as stimulus-response materials for advanced data encryption applications. Figure 6 As shown in Figure c, the sensitive mechanical stress-response luminescence and CPML properties of Examples 1 and 3 can be used to design data-double-encrypted materials. Depending on the chirality, the CPML of Examples 1 and 3 is decoded into binary data of "1" or "0" to store digitally processable information. Specifically, the output of Example 1 is defined as "1", while the output of Example 3 is defined as "0". The encrypted information based on Examples 1 and 3 is decrypted using binary ASCII (American Standard Code for Information Interchange). For example, the digital information "2023" encrypted by Examples 1 and 3 can be successfully decrypted using ASCII code. Figure 6 c).

[0124] Writing lightly on the interlayer film of R / S-1 microcrystals with a pen produces a noticeable green glow, which ensures the application of Examples 1 and 3 in advanced data encryption. For example... Figure 6 As shown in Figure d, the patterns of CPML in Examples 1 and 3 are displayed. Long-exposure photography can clearly record the handwritten information "2023" and "CPML" on the microcrystalline sandwich PET films of Examples 1 and 3. Therefore, combining the mechanoluminescence properties of Examples 1 and 3 and their sensitivity to mechanical force, as well as the irreversible destructive luminescence property caused by the fracture-mechanical luminescence mechanism, a safe and reliable data encoding and storage platform can be established. This allows Examples 1 and 3 to become intelligent stimulus-response materials for anti-counterfeiting and information encryption, especially for high-end goods with irreversible destructive advanced anti-counterfeiting and encryption, such as destructive anti-counterfeiting at the packaging of high-end wines, advanced information encryption and non-replicability of military or commercial secrets, or the transmission of information that is destructive after one use. The fracture-mechanical luminescence mechanism of Examples 1 and 3 leads to irreversible destructive luminescence properties such as... Figure 12 As shown, after the microcrystalline samples of Examples 1 and 3 were tested for ML spectra once under mechanical force, the ML emission intensity of the second and third tests was reduced by more than 90% compared with the first test, and the emission was almost undetectable. This is very beneficial for its irreversible and destructive advanced anti-counterfeiting and encryption applications.

[0125] The crystal structures of Examples 1 and 3 are as follows: Figure 13 As shown, Figure 13 (a) and (b) show the crystal structures of Examples 1 and 3, respectively, mainly consisting of the ligands of Examples 1 and 3, and the inorganic center [MnBr4]. 2- And a symmetrical crystal structure along the b-axis. Figure 13 (c) and 13(d) show the hydrogen bonding environments of Examples 1 and 3, respectively. Mn, C, N, P, H, and Br atoms are represented by purple, gray, blue, orange, white, and dark yellow, respectively. The MnBr4 unit is represented as a green polyhedron. For clarity, the covalent bonds between C, N, P, and H atoms are simplified to lines, and black lines represent mirror surfaces.

[0126] The crystal structure of Example 2 is as follows Figure 14 As shown, the crystal structure of Comparative Example 2 is as follows: Figure 15 As shown.

[0127] The above are merely preferred embodiments of the present invention and do not limit the patent scope of the present invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the patent protection scope of the present invention.

Claims

1. A mechanoluminescent manganese-based halide, characterized in that, The general chemical formula is: H₂A-MnX₄. Wherein: Group A has a structural formula as shown in (Ⅰ) or (Ⅱ): （Ⅰ） （Ⅱ） X is at least one of Cl and Br; X and A are connected by hydrogen bonds; The simplest molecular formula of the mechanoluminescent manganese-based halide is C0. 29 H 32 P2MnX4.

2. A method for preparing a mechanoluminescent manganese-based halide as described in claim 1, characterized in that, Includes the following steps: 2,4-bis(diphenylphosphine)pentane was mixed with manganese halide and reacted in acid to obtain a mixed solution; The solvent is mixed with the mixture, the solvent is evaporated, and methemoluminescent manganese-based halides are crystallized out. The 2,4-bis(diphenylphosphine)pentane is (2R,4R)-(+)-2,4-bis(diphenylphosphine)pentane or (2S,4S)-(-)-2,4-bis(diphenylphosphine)pentane; The acid is at least one of HBr and HCl; The manganese halide is at least one of MnBr2 and MnCl2.

3. The method for preparing mechanoluminescent manganese-based halides as described in claim 2, characterized in that, The solvent includes at least one of methanol, ethanol, acetone and acetonitrile.

4. The method for preparing mechanoluminescent manganese-based halides as described in claim 2, characterized in that, The step involves mixing 2,4-bis(diphenylphosphine)pentane with manganese halide and reacting the mixture in acid to obtain a final solution. The reaction temperature is 70~150℃; and / or, The reaction time is 0.1~3h.

5. The method for preparing mechanoluminescent manganese-based halides as described in claim 2, characterized in that, In the process of mixing the solvent with the mixture, evaporating the solvent, and crystallizing out the methemoluminescent manganese-based halide: The volatilization temperature is 35~80℃; and / or, The cooling rate for crystallization is 0.05~20℃ / min.

6. An anti-counterfeiting device, characterized in that, The invention includes encryption materials, which include mechanoluminescent manganese-based halides as described in claim 1, or mechanoluminescent manganese-based halides prepared by the method for preparing mechanoluminescent manganese-based halides as described in any one of claims 2 to 5.

7. A pressure sensing device, characterized in that, The material includes a pressure-sensitive material, which includes a mechanoluminescent manganese-based halide as described in claim 1, or a mechanoluminescent manganese-based halide prepared by the method described in any one of claims 2 to 5.

Images