High and low temperature activated luminescent manganese(ii) complexes, methods of preparation and use thereof
By preparing manganese(II) complexes with alkoxy chains, the luminescence intensity control at high and low temperatures was achieved, solving the problem of luminescence regulation of phosphorescent manganese(II) complexes and promoting their application in security anti-counterfeiting and information security.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- THE HONG KONG POLYTECHNIC UNIV SHENZHEN RES INST
- Filing Date
- 2024-08-12
- Publication Date
- 2026-05-19
AI Technical Summary
In the existing technology, the luminescence regulation of phosphorescent manganese(II) complexes is difficult, and luminescence activation by both high and low temperature stimulation methods has not been achieved.
Luminescent manganese(II) complexes with alkoxy chains that can be activated at high and low temperatures were developed. DEtPO-MnX2 and DISPO-MnX2 compounds were prepared by stirring with manganese tetrahydrate in a specific solvent under an inert atmosphere, and their luminescence properties were controlled by temperature changes.
Significantly enhanced luminescence intensity of manganese(II) complexes at high and low temperatures was achieved, expanding their application in security and anti-counterfeiting and information security fields, especially enabling information decryption and reading through temperature control.
Smart Images
Figure CN119119124B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of organic optoelectronic functional materials technology, and in particular to luminescent manganese(II) complexes that can be activated at high and low temperatures, their preparation methods, and their applications. Background Technology
[0002] As a new class of luminescent materials, phosphorescent manganese(II) complexes possess advantages such as high photoluminescence quantum efficiency, low cost, low toxicity, and simple synthesis, and have been widely applied in fields such as organic light-emitting diodes, information security, X-ray imaging, and optoelectronic switches. It is well known that the luminescence of phosphorescent manganese(II) complexes is relatively stable and very difficult to control. Currently, a few ionic manganese(II) complexes quench their luminescence by adsorbing small guest molecules (including water, methanol, and ethylene glycol). To date, no simultaneous activation of manganese(II) complex luminescence through both high and low temperature stimulation has been reported. Summary of the Invention
[0003] In view of the shortcomings of the prior art, the purpose of this invention is to provide luminescent manganese(II) complexes that can be activated at high and low temperatures, their preparation methods and applications. The aim is to develop manganese(II) complexes with high and low temperature luminescence activation characteristics and to expand the application of manganese(II) complexes in the field of safety.
[0004] The technical solution of the present invention is as follows:
[0005] In a first aspect, the present invention provides a luminescent manganese(II) complex that can be activated at high and low temperatures, wherein the luminescent manganese(II) complex has one or more of the following structural formulas:
[0006]
[0007] Where X = Cl, Br, or I.
[0008] Optionally, the luminescent manganese(II) complex has one or two of the following structural formulas:
[0009]
[0010] A second aspect of the present invention provides a method for preparing the high- and low-temperature activatable luminescent manganese(II) complex, comprising the steps of:
[0011] Provide DEtPO, the structure of which is:
[0012] Under an inert atmosphere, the DEtPO and manganese halide tetrahydrate were mixed in a first solvent and stirred at 50-60°C for 6-10 hours to obtain DEtPO-MnX2.
[0013] Alternatively, a DISPO may be provided, the structure of which is as follows:
[0014] Under an inert atmosphere, DISPO and manganese halide tetrahydrate are mixed in a second solvent and stirred at 50-60°C for 6-10 hours to obtain DISPO-MnX2.
[0015] Optionally, the first solvent is at least one of methanol and ethanol;
[0016] The DEtPO and manganese halide tetrahydrate were mixed in a first solvent at a molar ratio of 1:1.
[0017] Optionally, the second solvent is at least one of methanol and ethanol;
[0018] The DISPO and manganese halide tetrahydrate are mixed in a second solvent at a molar ratio of 1:1.
[0019] A third aspect of the present invention provides the application of the high- and low-temperature activatable luminescent manganese(II) complex in security and anti-counterfeiting.
[0020] In a fourth aspect, the present invention provides an anti-counterfeiting label, wherein the anti-counterfeiting label is prepared on filter paper by comprising the high- and low-temperature luminescent manganese(II) complexes DEtPO-MnX2 and DMePO-MnX2 described in the present invention;
[0021] Alternatively, the anti-counterfeiting label is prepared on filter paper by comprising the luminescent manganese(II) complexes DISPO-MnX2 and DMePO-MnX2, which are capable of being activated at high and low temperatures as described in this invention;
[0022] When X in DMePO-MnX2 is Br, the structural formula of DMePO-MnX2 is:
[0023] A fifth aspect of the present invention provides the application of the high- and low-temperature activatable luminescent manganese(II) complex in information security.
[0024] Optionally, the information security includes the decryption and reading of information.
[0025] Beneficial Effects: This invention provides two neutral manganese(II) complex materials with luminescent activation properties. Compared with existing neutral manganese(II) complex materials, the manganese(II) complexes provided by this invention introduce multiple alkoxy chains into the molecules, which is beneficial for adsorbing water molecules from the air, thereby achieving dual-temperature control of the luminescent properties of the manganese(II) complex materials. This invention can significantly enhance the luminescence intensity of the two manganese(II) complex materials by lowering and raising the temperature. In addition, utilizing their high and low temperature luminescent activation properties, security anti-counterfeiting labels can be prepared, which greatly promotes the application of manganese(II) complex materials in the field of information security. Furthermore, highly secure binary code information has been developed using manganese(II) complex materials, and temperature is used to achieve information decryption and reading. Attached Figure Description
[0026] Figure 1 This is a schematic diagram of the crystal structure of DEtPO-MnBr2 in Example 1 of the present invention.
[0027] Figure 2 The image shows the change in the emission spectrum of DEtPO-MnBr2 with increasing temperature in Example 1 of this invention. The inset is a photograph of DEtPO-MnBr2 at room temperature and high temperature, and the direction of the black dashed arrow indicates the direction of temperature increase.
[0028] Figure 3 The image shows the change in the emission spectrum of DEtPO-MnBr2 as the temperature decreases in Example 1 of this invention. The inset is a photograph of DEtPO-MnBr2 at room temperature and low temperature, and the direction of the black dashed arrow indicates the direction of temperature decrease.
[0029] Figure 4 This is an image of the high-temperature anti-counterfeiting label in Embodiment 1 of the present invention.
[0030] Figure 5 This is a high-security binary code information diagram in Embodiment 1 of the present invention, where a is a schematic diagram of encryption diagrams prepared with different materials, b is a luminescence image under different temperatures and ultraviolet light irradiation, and c is a schematic diagram of information encryption and decryption based on the luminescence image. Detailed Implementation
[0031] This invention provides luminescent manganese(II) complexes that can be activated at high and low temperatures, their preparation methods, and their applications. To make the objectives, technical solutions, and effects of this invention clearer and more explicit, the invention is further described in detail below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
[0032] This invention provides luminescent manganese(II) complexes that can be activated at high and low temperatures, wherein the structural formula of the luminescent manganese(II) complexes is one or more of the following:
[0033]
[0034] Where X = Cl, Br, or I.
[0035] In embodiments of the present invention, two neutral manganese(II) complex materials with luminescent activation properties are provided. Compared with existing neutral manganese(II) complex materials, the manganese(II) complexes provided in the embodiments of the present invention introduce multiple alkoxy chains into the molecule. Water molecules can form hydrogen bonds with the oxygen atoms in the alkoxy chains, adsorbing water molecules from the air through hydrogen bonds. The non-radiative transitions of the intramolecular alkoxy chains and water molecules cause the manganese(II) complex to exhibit very weak luminescence under normal conditions. At low temperatures, the vibration of the molecular system is suppressed, resulting in a significant increase in the luminescence intensity of the manganese(II) complex. At high temperatures, water molecules are removed, and the luminescence of the manganese(II) complex is also enhanced, thereby achieving dual-temperature control of the luminescence characteristics of the manganese(II) complex material.
[0036] In embodiments of the present invention, the luminescence intensity of the two manganese(II) complex materials can be significantly enhanced by lowering and raising the temperature. Furthermore, their high and low temperature luminescence activation characteristics can be utilized to prepare secure anti-counterfeiting labels, which greatly advances the application of manganese(II) complex materials in the field of information security. In addition, highly secure binary code information has been developed using manganese(II) complex materials, and temperature is used to achieve information decryption and reading.
[0037] In one embodiment, the luminescent manganese(II) complex has one or two of the following structural formulas:
[0038]
[0039] Both compounds, DEtPO-MnBr2 and DISPO-MnBr2, exhibit temperature-controlled luminescence activation properties.
[0040] This invention provides a method for preparing the high- and low-temperature activatable luminescent manganese(II) complex, comprising the following steps:
[0041] Provide DEtPO, the structure of which is:
[0042] Under an inert atmosphere, DEtPO and manganese halide tetrahydrate are mixed in a first solvent and stirred at 50-60°C for 6-10 hours (e.g., 8 hours) to obtain DEtPO-MnX2.
[0043] In one embodiment, the first solvent is at least one of methanol and ethanol.
[0044] In one embodiment, the DEtPO and manganese halide tetrahydrate are mixed in a first solvent at a molar ratio of 1:1.
[0045] This invention provides a method for preparing the high- and low-temperature activatable luminescent manganese(II) complex, comprising the following steps:
[0046] Provide DISPO, the structural formula of which is
[0047] Under an inert atmosphere, DISPO and manganese halide tetrahydrate are mixed in a second solvent and stirred at 50-60°C for 6-10 hours (e.g., 8 hours) to obtain DISPO-MnX2.
[0048] In one embodiment, the second solvent is at least one of methanol and ethanol.
[0049] In one embodiment, the DISPO and manganese halide tetrahydrate are mixed in a second solvent at a molar ratio of 1:1.
[0050] This invention provides the application of the high- and low-temperature activatable luminescent manganese(II) complex in security and anti-counterfeiting.
[0051] This invention provides an anti-counterfeiting label, wherein the anti-counterfeiting label is prepared on filter paper by comprising the high- and low-temperature luminescent manganese(II) complexes DEtPO-MnX2 and DMePO-MnX2 described in this invention;
[0052] Alternatively, the anti-counterfeiting label is prepared on filter paper by comprising the luminescent manganese(II) complexes DISPO-MnX2 and DMePO-MnX2, which are capable of being activated at high and low temperatures as described in the embodiments of the present invention.
[0053] When X in DMePO-MnX2 is Br, the structural formula of DMePO-MnX2 is:
[0054] Given the temperature-controlled luminescence activation behavior of manganese(II) complexes, their potential applications in anti-counterfeiting have been further explored. For example, anti-counterfeiting labels were prepared on filter paper using reported DMePO-MnBr2 and temperature-activated DEtPO-MnBr2 crystal powders. Under ultraviolet light and at room temperature, the pattern only displays partial information, while the complete pattern can be read under ultraviolet light and high temperature.
[0055] This invention provides the application of the high- and low-temperature activatable luminescent manganese(II) complex in information security.
[0056] For example, high-security binary code information was developed using DEtPO, DMePO-MnBr2, and DEtPO-MnBr2, and temperature was used to decrypt and read the information.
[0057] The present invention will be further described below through specific embodiments.
[0058] Since DEtPO-MnBr2 and DISPO-MnBr2 have similar synthesis methods and photophysical properties, DEtPO-MnBr2 will be used as an example for detailed explanation below.
[0059] Example 1: Preparation, characterization, testing and application of compound DEtPO-MnBr2
[0060] 1. Preparation of compound DEtPO-MnBr2, the preparation method is as follows:
[0061]
[0062] First, under a nitrogen atmosphere, compound 1 was dissolved in 1.2 mL of triethyl phosphite, heated at 120 °C for 8 h, then evaporated under reduced pressure, and purified by column chromatography to obtain compound DEtPO.
[0063] 1 H NMR (DMSO-d6, 600MHz, δ): 8.03 (d, J = 11.4Hz, 2H), 7.48 (d, J = 11.4Hz, 2H), 7.37 (t, J=11.4Hz,2H),4.03-3.96(m,8H),3.61(d,J=31.8Hz,4H),1.13(t,J=10.2Hz,12H); 13 C NMR(DMSO-d6,100MHz,δ):153.89,153.80,128.78,128.73,123.69,123.67,123.14,123.11,119.71,119.68,116.46,116.37,61.63(d, 3 J 31P-13C =6.3Hz),26.69,25.32,16.12,16.14; 31 P NMR (DMSO-d6, 162MHz, δ): 25.36.
[0064] Then, under a nitrogen atmosphere, the compound DEtPO was dissolved in methanol, and manganese bromide tetrahydrate was added at a molar ratio of 1:1. The mixture was stirred at 50°C for 8 hours, and then evaporated under reduced pressure to obtain the complex DEtPO-MnBr2.
[0065] 2. Characterization and photophysical property testing of DEtPO-MnBr2
[0066] DEtPO-MnBr2 was dissolved in a mixed solvent of dichloromethane and ethyl acetate. Single crystals of DEtPO-MnBr2 were collected by slow evaporation, and their single crystal structures were obtained, such as... Figure 1 As shown.
[0067] The changes in the emission spectrum of DEtPO-MnBr2 powder with increasing temperature were tested. The inset shows photographs of DEtPO-MnBr2 at room temperature (300K) and high temperature (420K), as shown below. Figure 2 As shown. From Figure 2 It can be seen that the luminescence intensity of DEtPO-MnBr2 powder gradually increases with increasing temperature, indicating that it has the ability to activate the luminescence crystallization of manganese(II) complexes at high temperature.
[0068] The changes in the emission spectrum of DEtPO-MnBr2 powder with decreasing temperature were tested. The inset shows photographs of DEtPO-MnBr2 at room temperature (300K) and low temperature (200K), as shown below. Figure 3 As shown. From Figure 3 It can be seen that the luminescence intensity of DEtPO-MnBr2 powder gradually increases with decreasing temperature, indicating that it has the ability to activate the luminescence crystallization of manganese(II) complexes at low temperature.
[0069] 3. Applications in anti-counterfeiting and information security
[0070] Due to the unique temperature-controlled luminescence activation behavior of DEtPO-MnBr2, its potential application in anti-counterfeiting has been further explored. The specific operational steps are as follows: Anti-counterfeiting labels are prepared on filter paper using the previously reported DMePO-MnBr2 and temperature-activated DEtPO-MnBr2 crystal powder. Under ultraviolet light and at room temperature, the pattern only displays partial information, while under ultraviolet light and high temperature, the complete pattern can be read (see...). Figure 4 ).
[0071] Furthermore, highly secure binary code information was developed using DEtPO, DMePO-MnBr2, and DEtPO-MnBr2. Combined with... Figure 5 As shown in a, b, and c, points emitting green light are defined as outputting a code of "1", while others are outputting a code of "0". Under ultraviolet light and at room temperature, the binary code can be decoded as "@@@@@". However, when the temperature drops from 298K to 200K or rises to 400K, some points also emit a strong green light, causing the binary code to be decoded again as the actual information "POLYU". Therefore, these results indicate that DEtPO-MnBr2 and DISPO-MnBr2 have high development potential in anti-counterfeiting and information security applications.
[0072] In summary, the manganese(II) complex provided by this invention has high and low temperature luminescence activation characteristics; high temperature information display is achieved using DEtPO-MnBr2 and the previously reported DMePO-MnBr2; and highly secure binary code information is developed using DEtPO, DMePO-MnBr2 and DEtPO-MnBr2.
[0073] It should be understood that the application of the present invention is not limited to the examples above. Those skilled in the art can make improvements or modifications based on the above description, and all such improvements and modifications should fall within the protection scope of the appended claims.
Claims
1. A luminescent manganese(II) complex that can be activated at high and low temperatures, characterized in that, The luminescent manganese(II) complex has one or more of the following structural formulas: Where X = Cl, Br, or I.
2. The luminescent manganese(II) complex that can be activated at high and low temperatures according to claim 1, characterized in that, The luminescent manganese(II) complex has one or two of the following structural formulas: 。 3. A method for preparing the high- and low-temperature activatable luminescent manganese(II) complex according to claim 1, characterized in that, Including the following steps: Provide DEtPO, the structure of which is: ; Under an inert atmosphere, the DEtPO was mixed with manganese halide tetrahydrate in a first solvent at 50-60 °C. o Stirring at C for 6-10 h yields DEtPO-MnX2; Alternatively, a DISPO may be provided, the structure of which is as follows: ; Under an inert atmosphere, the DISPO was mixed with manganese halide tetrahydrate in a second solvent at 50-60 °C. o Stirring at C for 6-10 h yields DISPO-MnX2.
4. The method for preparing the high- and low-temperature activatable luminescent manganese(II) complex according to claim 3, characterized in that, The first solvent is at least one of methanol and ethanol; The DEtPO and manganese halide tetrahydrate were mixed in a first solvent at a molar ratio of 1:
1.
5. The method for preparing the high- and low-temperature activatable luminescent manganese(II) complex according to claim 3, characterized in that, The second solvent is at least one of methanol and ethanol; The DISPO and manganese halide tetrahydrate are mixed in a second solvent at a molar ratio of 1:
1.
6. The application of the high- and low-temperature luminescent manganese(II) complex as described in any one of claims 1-2 in security and anti-counterfeiting.
7. An anti-counterfeiting label, characterized in that, The anti-counterfeiting label is prepared on filter paper by comprising the high- and low-temperature luminescent manganese(II) complexes DEtPO-MnX2 and DMePO-MnX2 as described in claim 1; Alternatively, the anti-counterfeiting label is prepared on filter paper by comprising the luminescent manganese(II) complexes DISPO-MnX2 and DMePO-MnX2, which are capable of being activated at high and low temperatures as described in claim 1. When X in DMePO-MnX2 is Br, the structural formula of DMePO-MnX2 is: .
8. The application of the high- and low-temperature luminescent manganese(II) complex as described in any one of claims 1-2 in information security.
9. The application according to claim 8, characterized in that, Information security refers to the decryption and reading of information.